1234	----	None 
12787	----	[Transcriber's notes: In the chemical equations, superscripts are indicated with a ^ and subscripts are indicated with a _. The affected item is enclosed in curly brackets {}. Examples are H^{+} for hydrogen ion and H_{2}O for water. Since the underscore is already being used in this project, italics are designated by an exclamation point before and after the italicized word or phrase.] AN INTRODUCTORY COURSE OF QUANTITATIVE CHEMICAL ANALYSIS WITH EXPLANATORY NOTES BY HENRY P. TALBOT PROFESSOR OF INORGANIC CHEMISTRY AT THE MASSACHUSETTS INSTITUTE OF TECHNOLOGY SIXTH EDITION, COMPLETELY REWRITTEN PREFACE This Introductory Course of Quantitative Analysis has been prepared to meet the needs of students who are just entering upon the subject, after a course of qualitative analysis. It is primarily intended to enable the student to work successfully and intelligently without the necessity for a larger measure of personal assistance and supervision than can reasonably be given to each member of a large class. To this end the directions are given in such detail that there is very little opportunity for the student to go astray; but the manual is not, the author believes, on this account less adapted for use with small classes, where the instructor, by greater personal influence, can stimulate independent thought on the part of the pupil. The method of presentation of the subject is that suggested by Professor A.A. Noyes' excellent manual of Qualitative Analysis. For each analysis the procedure is given in considerable detail, and this is accompanied by explanatory notes, which are believed to be sufficiently expanded to enable the student to understand fully the underlying reason for each step prescribed. The use of the book should, nevertheless, be supplemented by classroom instruction, mainly of the character of recitations, and the student should be taught to consult larger works. The general directions are intended to emphasize those matters upon which the beginner in quantitative analysis must bestow special care, and to offer helpful suggestions. The student can hardly be expected to appreciate the force of all the statements contained in these directions, or, indeed, to retain them all in the memory after a single reading; but the instructor, by frequent reference to special paragraphs, as suitable occasion presents itself, can soon render them familiar to the student. The analyses selected for practice are those comprised in the first course of quantitative analysis at the Massachusetts Institute of Technology, and have been chosen, after an experience of years, as affording the best preparation for more advanced work, and as satisfactory types of gravimetric and volumetric methods. From the latter point of view, they also seem to furnish the best insight into quantitative analysis for those students who can devote but a limited time to the subject, and who may never extend their study beyond the field covered by this manual. The author has had opportunity to test the efficiency of the course for use with such students, and has found the results satisfactory. In place of the usual custom of selecting simple salts as material for preliminary practice, it has been found advantageous to substitute, in most instances, approximately pure samples of appropriate minerals or industrial products. The difficulties are not greatly enhanced, while the student gains in practical experience. The analytical procedures described in the following pages have been selected chiefly with reference to their usefulness in teaching the subject, and with the purpose of affording as wide a variety of processes as is practicable within an introductory course of this character. The scope of the manual precludes any extended attempt to indicate alternative procedures, except through general references to larger works on analytical chemistry. The author is indebted to the standard works for many suggestions for which it is impracticable to make specific acknowledgment; no considerable credit is claimed by him for originality of procedure. For many years, as a matter of convenience, the classes for which this text was originally prepared were divided, one part beginning with gravimetric processes and the other with volumetric analyses. After a careful review of the experience thus gained the conclusion has been reached that volumetric analysis offers the better approach to the subject. Accordingly the arrangement of the present (the sixth) edition of this manual has been changed to introduce volumetric procedures first. Teachers who are familiar with earlier editions will, however, find that the order of presentation of the material under the various divisions is nearly the same as that previously followed, and those who may still prefer to begin the course of instruction with gravimetric processes will, it is believed, be able to follow that order without difficulty. Procedures for the determination of sulphur in insoluble sulphates, for the determination of copper in copper ores by iodometric methods, for the determination of iron by permanganate in hydrochloric acid solutions, and for the standardization of potassium permanganate solutions using sodium oxalate as a standard, and of thiosulphate solutions using copper as a standard, have been added. The determination of silica in silicates decomposable by acids, as a separate procedure, has been omitted. The explanatory notes have been rearranged to bring them into closer association with the procedures to which they relate. The number of problems has been considerably increased. The author wishes to renew his expressions of appreciation of the kindly reception accorded the earlier editions of this manual. He has received helpful suggestions from so many of his colleagues within the Institute, and friends elsewhere, that his sense of obligation must be expressed to them collectively. He is under special obligations to Professor L.F. Hamilton for assistance in the preparation of the present edition. HENRY P. TALBOT !Massachusetts Institute of Technology, September, 1921!. CONTENTS PART I. INTRODUCTION SUBDIVISIONS OF ANALYTICAL CHEMISTRY GENERAL DIRECTIONS Accuracy and Economy of Time; Notebooks; Reagents; Wash-bottles; Transfer of Liquids PART II. VOLUMETRIC ANALYSIS GENERAL DISCUSSION Subdivisions; The Analytical Balance; Weights; Burettes; Calibration of Measuring Devices GENERAL DIRECTIONS Standard and Normal Solutions !I. Neutralization Methods! ALKALIMETRY AND ACIDIMETRY Preparation and Standardization of Solutions; Indicators STANDARDIZATION OF HYDROCHLORIC ACID DETERMINATION OF TOTAL ALKALINE STRENGTH OF SODA ASH DETERMINATION OF ACID STRENGTH OF OXALIC ACID !II. Oxidation Processes! GENERAL DISCUSSION BICHROMATE PROCESS FOR THE DETERMINATION OF IRON DETERMINATION OF IRON IN LIMONITE BY THE BICHROMATE PROCESS DETERMINATION OF CHROMIUM IN CHROME IRON ORE PERMANGANATE PROCESS FOR THE DETERMINATION OF IRON DETERMINATION OF IRON IN LIMONITE BY THE PERMANGANATE PROCESS DETERMINATION OF IRON IN LIMONITE BY THE ZIMMERMANN-REINHARDT PROCESS DETERMINATION OF THE OXIDIZING POWER OF PYROLUSITE IODIMETRY DETERMINATION OF COPPER IN ORES DETERMINATION OF ANTIMONY IN STIBNITE CHLORIMETRY DETERMINATION OF AVAILABLE CHLORINE IN BLEACHING POWDER !III. Precipitation Methods! DETERMINATION OF SILVER BY THE THIOCYANATE PROCESS PART III. GRAVIMETRIC ANALYSIS GENERAL DIRECTIONS Precipitation; Funnels and Filters; Filtration and Washing of Precipitates; Desiccators; Crucibles and their Preparation for Use; Ignition of Precipitates DETERMINATION OF CHLORINE IN SODIUM CHLORIDE DETERMINATION OF IRON AND OF SULPHUR IN FERROUS AMMONIUM SULPHATE DETERMINATION OF SULPHUR IN BARIUM SULPHATE DETERMINATION OF PHOSPHORIC ANHYDRIDE IN APATITE ANALYSIS OF LIMESTONE Determination of Moisture; Insoluble Matter and Silica; Ferric Oxide and Alumina; Calcium; Magnesium; Carbon Dioxide ANALYSIS OF BRASS Electrolytic Separations; Determination of Lead, Copper, Iron and Zinc. DETERMINATION OF SILICA IN SILICATES PART IV. STOICHIOMETRY SOLUTIONS OF TYPICAL PROBLEMS PROBLEMS APPENDIX ELECTROLYTIC DISSOCIATION THEORY FOLDING OF A FILTER PAPER SAMPLE NOTEBOOK PAGES STRENGTH OF REAGENTS DENSITIES AND VOLUMES OF WATER CORRECTIONS FOR CHANGE OF TEMPERATURE OF STANDARD SOLUTIONS ATOMIC WEIGHTS LOGARITHM TABLES QUANTITATIVE CHEMICAL ANALYSIS PART I INTRODUCTION SUBDIVISIONS OF ANALYTICAL CHEMISTRY A complete chemical analysis of a body of unknown composition involves the recognition of its component parts by the methods of !qualitative analysis!, and the determination of the proportions in which these components are present by the processes of !quantitative analysis!. A preliminary qualitative examination is generally indispensable, if intelligent and proper provisions are to be made for the separation of the various constituents under such conditions as will insure accurate quantitative estimations. It is assumed that the operations of qualitative analysis are familiar to the student, who will find that the reactions made use of in quantitative processes are frequently the same as those employed in qualitative analyses with respect to both precipitation and systematic separation from interfering substances; but it should be noted that the conditions must now be regulated with greater care, and in such a manner as to insure the most complete separation possible. For example, in the qualitative detection of sulphates by precipitation as barium sulphate from acid solution it is not necessary, in most instances, to take into account the solubility of the sulphate in hydrochloric acid, while in the quantitative determination of sulphates by this reaction this solubility becomes an important consideration. The operations of qualitative analysis are, therefore, the more accurate the nearer they are made to conform to quantitative conditions. The methods of quantitative analysis are subdivided, according to their nature, into those of !gravimetric analysis, volumetric analysis!, and !colorimetric analysis!. In !gravimetric! processes the constituent to be determined is sometimes isolated in elementary form, but more commonly in the form of some compound possessing a well-established and definite composition, which can be readily and completely separated, and weighed either directly or after ignition. From the weight of this substance and its known composition, the amount of the constituent in question is determined. In !volumetric! analysis, instead of the final weighing of a definite body, a well-defined reaction is caused to take place, wherein the reagent is added from an apparatus so designed that the volume of the solution employed to complete the reaction can be accurately measured. The strength of this solution (and hence its value for the reaction in question) is accurately known, and the volume employed serves, therefore, as a measure of the substance acted upon. An example will make clear the distinction between these two types of analysis. The percentage of chlorine in a sample of sodium chloride may be determined by dissolving a weighed amount of the chloride in water and precipitating the chloride ions as silver chloride, which is then separated by filtration, ignited, and weighed (a !gravimetric! process); or the sodium chloride may be dissolved in water, and a solution of silver nitrate containing an accurately known amount of the silver salt in each cubic centimeter may be cautiously added from a measuring device called a burette until precipitation is complete, when the amount of chlorine may be calculated from the number of cubic centimeters of the silver nitrate solution involved in the reaction. This is a !volumetric! process, and is equivalent to weighing without the use of a balance. Volumetric methods are generally more rapid, require less apparatus, and are frequently capable of greater accuracy than gravimetric methods. They are particularly useful when many determinations of the same sort are required. In !colorimetric! analyses the substance to be determined is converted into some compound which imparts to its solutions a distinct color, the intensity of which must vary in direct proportion to the amount of the compound in the solution. Such solutions are compared with respect to depth of color with standard solutions containing known amounts of the colored compound, or of other similar color-producing substance which has been found acceptable as a color standard. Colorimetric methods are, in general, restricted to the determinations of very small quantities, since only in dilute solutions are accurate comparisons of color possible. GENERAL DIRECTIONS The following paragraphs should be read carefully and thoughtfully. A prime essential for success as an analyst is attention to details and the avoidance of all conditions which could destroy, or even lessen, confidence in the analyses when completed. The suggestions here given are the outcome of much experience, and their adoption will tend to insure permanently work of a high grade, while neglect of them will often lead to disappointment and loss of time. ACCURACY AND ECONOMY OF TIME The fundamental conception of quantitative analysis implies a necessity for all possible care in guarding against loss of material or the introduction of foreign matter. The laboratory desk, and all apparatus, should be scrupulously neat and clean at all times. A sponge should always be ready at hand, and desk and filter-stands should be kept dry and in good order. Funnels should never be allowed to drip upon the base of the stand. Glassware should always be wiped with a clean, lintless towel just before use. All filters and solutions should be covered to protect them from dust, just as far as is practicable, and every drop of solution or particle of precipitate must be regarded as invaluable for the success of the analysis. An economical use of laboratory hours is best secured by acquiring a thorough knowledge of the character of the work to be done before undertaking it, and then by so arranging the work that no time shall be wasted during the evaporation of liquids and like time-consuming operations. To this end the student should read thoughtfully not only the !entire! procedure, but the explanatory notes as well, before any step is taken in the analysis. The explanatory notes furnish, in general, the reasons for particular steps or precautions, but they also occasionally contain details of manipulation not incorporated, for various reasons, in the procedure. These notes follow the procedures at frequent intervals, and the exact points to which they apply are indicated by references. The student should realize that a !failure to study the notes will inevitably lead to mistakes, loss of time, and an inadequate understanding of the subject!. All analyses should be made in duplicate, and in general a close agreement of results should be expected. It should, however, be remembered that a close concordance of results in "check analyses" is not conclusive evidence of the accuracy of those results, although the probability of their accuracy is, of course, considerably enhanced. The satisfaction in obtaining "check results" in such analyses must never be allowed to interfere with the critical examination of the procedure employed, nor must they ever be regarded as in any measure a substitute for absolute truth and accuracy. In this connection it must also be emphasized that only the operator himself can know the whole history of an analysis, and only he can know whether his work is worthy of full confidence. No work should be continued for a moment after such confidence is lost, but should be resolutely discarded as soon as a cause for distrust is fully established. The student should, however, determine to put forth his best efforts in each analysis; it is well not to be too ready to condone failures and to "begin again," as much time is lost in these fruitless attempts. Nothing less than !absolute integrity! is or can be demanded of a quantitative analyst, and any disregard of this principle, however slight, is as fatal to success as lack of chemical knowledge or inaptitude in manipulation can possibly be. NOTEBOOKS Notebooks should contain, beside the record of observations, descriptive notes. All records of weights should be placed upon the right-hand page, while that on the left is reserved for the notes, calculations of factors, or the amount of reagents required. The neat and systematic arrangement of the records of analyses is of the first importance, and is an evidence of careful work and an excellent credential. Of two notebooks in which the results may be, in fact, of equal value as legal evidence, that one which is neatly arranged will carry with it greater weight. All records should be dated, and all observations should be recorded at once in the notebook. The making of records upon loose paper is a practice to be deprecated, as is also that of copying original entries into a second notebook. The student should accustom himself to orderly entries at the time of observation. Several sample pages of systematic records are to be found in the Appendix. These are based upon experience; but other arrangements, if clear and orderly, may prove equally serviceable. The student is advised to follow the sample pages until he is in a position to plan out a system of his own. REAGENTS The habit of carefully testing reagents, including distilled water, cannot be too early acquired or too constantly practiced; for, in spite of all reasonable precautionary measures, inferior chemicals will occasionally find their way into the stock room, or errors will be made in filling reagent bottles. The student should remember that while there may be others who share the responsibility for the purity of materials in the laboratory of an institution, the responsibility will later be one which he must individually assume. The stoppers of reagent bottles should never be laid upon the desk, unless upon a clean watch-glass or paper. The neck and mouth of all such bottles should be kept scrupulously clean, and care taken that no confusion of stoppers occurs. WASH-BOTTLES Wash-bottles for distilled water should be made from flasks of about 750 cc. capacity and be provided with gracefully bent tubes, which should not be too long. The jet should be connected with the tube entering the wash-bottle by a short piece of rubber tubing in such a way as to be flexible, and should deliver a stream about one millimeter in diameter. The neck of the flask may be wound with cord, or covered with wash-leather, for greater comfort when hot water is used. It is well to provide several small wash-bottles for liquids other than distilled water, which should invariably be clearly labeled. TRANSFER OF LIQUIDS Liquids should never be transferred from one vessel to another, nor to a filter, without the aid of a stirring rod held firmly against the side or lip of the vessel. When the vessel is provided with a lip it is not usually necessary to use other means to prevent the loss of liquid by running down the side; whenever loss seems imminent a !very thin! layer of vaseline, applied with the finger to the edge of the vessel, will prevent it. The stirring rod down which the liquid runs should never be drawn upward in such a way as to allow the solution to collect on the under side of the rim or lip of a vessel. The number of transfers of liquids from one vessel to another during an analysis should be as small as possible to avoid the risk of slight losses. Each vessel must, of course, be completely washed to insure the transfer of all material; but it should be remembered that this can be accomplished better by the use of successive small portions of wash-water (perhaps 5-10 cc.), if each wash-water is allowed to drain away for a few seconds, than by the addition of large amounts which unnecessarily increase the volume of the solutions, causing loss of time in subsequent filtrations or evaporations. All stirring rods employed in quantitative analyses should be rounded at the ends by holding them in the flame of a burner until they begin to soften. If this is not done, the rods will scratch the inner surface of beakers, causing them to crack on subsequent heating. EVAPORATION OF LIQUIDS The greatest care must be taken to prevent loss of solutions during processes of evaporation, either from too violent ebullition, from evaporation to dryness and spattering, or from the evolution of gas during the heating. In general, evaporation upon the steam bath is to be preferred to other methods on account of the impossibility of loss by spattering. If the steam baths are well protected from dust, solutions should be left without covers during evaporation; but solutions which are boiled upon the hot plate, or from which gases are escaping, should invariably be covered. In any case a watch-glass may be supported above the vessel by means of a glass triangle, or other similar device, and the danger of loss of material or contamination by dust thus be avoided. It is obvious that evaporation is promoted by the use of vessels which admit of the exposure of a broad surface to the air. Liquids which contain suspended matter (precipitates) should always be cautiously heated, since the presence of the solid matter is frequently the occasion of violent "bumping," with consequent risk to apparatus and analysis. PART II VOLUMETRIC ANALYSIS The processes of volumetric analysis are, in general, simpler than those of gravimetric analysis and accordingly serve best as an introduction to the practice of quantitative analysis. For their execution there are required, first, an accurate balance with which to weigh the material for analysis; second, graduated instruments in which to measure the volume of the solutions employed; third, standard solutions, that is, solutions the value of which is accurately known; and fourth, indicators, which will furnish accurate evidence of the point at which the desired reaction is completed. The nature of the indicators employed will be explained in connection with the different analyses. The process whereby a !standard solution! is brought into reaction is called !titration!, and the point at which the reaction is exactly completed is called the !end-point!. The !indicator! should show the !end-point! of the !titration!. The volume of the standard solution used then furnishes the measure of the substance to be determined as truly as if that substance had been separated and weighed. The processes of volumetric analysis are easily classified, according to their character, into: I. NEUTRALIZATION METHODS; such, for example, as those of acidimetry and alkalimetry. II. OXIDATION PROCESSES; as exemplified in the determination of ferrous iron by its oxidation with potassium bichromate. III. PRECIPITATION METHODS; of which the titration for silver with potassium thiocyanate solution is an illustration. From a somewhat different standpoint the methods in each case may be subdivided into (a) DIRECT METHODS, in which the substance to be measured is directly determined by titration to an end-point with a standard solution; and (b) INDIRECT METHODS, in which the substance itself is not measured, but a quantity of reagent is added which is known to be an excess with respect to a specific reaction, and the unused excess determined by titration. Examples of the latter class will be pointed out as they occur in the procedures. MEASURING INSTRUMENTS THE ANALYTICAL BALANCE For a complete discussion of the physical principles underlying the construction and use of balances, and the various methods of weighing, the student is referred to larger manuals of Quantitative Analysis, such as those of Fresenius, or Treadwell-Hall, and particularly to the admirable discussion of this topic in Morse's !Exercises in Quantitative Chemistry!. The statements and rules of procedure which follow are sufficient for the intelligent use of an analytical balance in connection with processes prescribed in this introductory manual. It is, however, imperative that the student should make himself familiar with these essential features of the balance, and its use. He should fully realize that the analytical balance is a delicate instrument which will render excellent service under careful treatment, but such treatment is an essential condition if its accuracy is to be depended upon. He should also understand that no set of rules, however complete, can do away with the necessity for a sense of personal responsibility, since by carelessness he can render inaccurate not only his own analyses, but those of all other students using the same balance. Before making any weighings the student should seat himself before a balance and observe the following details of construction: 1. The balance case is mounted on three brass legs, which should preferably rest in glass cups, backed with rubber to prevent slipping. The front legs are adjustable as to height and are used to level the balance case; the rear leg is of permanent length. 2. The front of the case may be raised to give access to the balance. In some makes doors are provided also at the ends of the balance case. 3. The balance beam is mounted upon an upright in the center of the case on the top of which is an inlaid agate plate. To the center of the beam there is attached a steel or agate knife-edge on which the beam oscillates when it rests on the agate plate. 4. The balance beam, extending to the right and left, is graduated along its upper edge, usually on both sides, and has at its extremities two agate or steel knife-edges from which are suspended stirrups. Each of these stirrups has an agate plate which, when the balance is in action, rests upon the corresponding knife-edge of the beam. The balance pans are suspended from the stirrups. 5. A pointer is attached to the center of the beam, and as the beam oscillates this pointer moves in front of a scale near the base of the post. 6. At the base of the post, usually in the rear, is a spirit-level. 7. Within the upright is a mechanism, controlled by a knob at the front of the balance case, which is so arranged as to raise the entire beam slightly above the level at which the knife-edges are in contact with the agate plates. When the balance is not in use the beam must be supported by this device since, otherwise, the constant jarring to which a balance is inevitably subjected, will soon dull the knife-edges, and lessen the sensitiveness of the balance. 8. A small weight, or bob, is attached to the pointer (or sometimes to the beam) by which the center of gravity of the beam and its attachments may be regulated. The center of gravity must lie very slightly below the level of the agate plates to secure the desired sensitiveness of the balance. This is provided for when the balance is set up and very rarely requires alteration. The student should never attempt to change this adjustment. 9. Below the balance pans are two pan-arrests operated by a button from the front of the case. These arrests exert a very slight upward pressure upon the pans and minimize the displacement of the beam when objects or weights are being placed upon the pans. 10. A movable rod, operated from one end of the balance case, extends over the balance beam and carries a small wire weight, called a rider. By means of this rod the rider can be placed upon any desired division of the scale on the balance beam. Each numbered division on the beam corresponds to one milligram, and the use of the rider obviates the placing of very small fractional weights on the balance pan. If a new rider is purchased, or an old one replaced, care must be taken that its weight corresponds to the graduations on the beam of the balance on which it is to be used. The weight of the rider in milligrams must be equal to the number of large divisions (5, 6, 10, or 12) between the central knife-edge and the knife-edge at the end of the beam. It should be noted that on some balances the last division bears no number. Each new rider should be tested against a 5 or 10-milligram weight. In some of the most recent forms of the balance a chain device replaces the smaller weights and the use of the rider as just described. Before using a balance, it is always best to test its adjustment. This is absolutely necessary if the balance is used by several workers; it is always a wise precaution under any conditions. For this purpose, brush off the balance pans with a soft camel's hair brush. Then note (1) whether the balance is level; (2) that the mechanism for raising and lowering the beams works smoothly; (3) that the pan-arrests touch the pans when the beam is lowered; and (4) that the needle swings equal distances on either side of the zero-point when set in motion without any load on the pans. If the latter condition is not fulfilled, the balance should be adjusted by means of the adjusting screw at the end of the beam unless the variation is not more than one division on the scale; it is often better to make a proper allowance for this small zero error than to disturb the balance by an attempt at correction. Unless a student thoroughly understands the construction of a balance he should never attempt to make adjustments, but should apply to the instructor in charge. The object to be weighed should be placed on the left-hand balance pan and the weights upon the right-hand pan. Every substance which could attack the metal of the balance pan should be weighed upon a watch-glass, and all objects must be dry and cold. A warm body gives rise to air currents which vitiate the accuracy of the weighing. The weights should be applied in the order in which they occur in the weight-box (not at haphazard), beginning with the largest weight which is apparently required. After a weight has been placed upon the pan the beam should be lowered upon its knife-edges, and, if necessary, the pan-arrests depressed. The movement of the pointer will then indicate whether the weight applied is too great or too small. When the weight has been ascertained, by the successive addition of small weights, to the nearest 5 or 10 milligrams, the weighing is completed by the use of the rider. The correct weight is that which causes the pointer to swing an equal number of divisions to the right and left of the zero-point, when the pointer traverses not less than five divisions on either side. The balance case should always be closed during the final weighing, while the rider is being used, to protect the pans from the effect of air currents. Before the final determination of an exact weight the beam should always be lifted from the knife-edges and again lowered into place, as it frequently happens that the scale pans are, in spite of the pan-arrests, slightly twisted by the impact of the weights, the beam being thereby virtually lengthened or shortened. Lifting the beam restores the proper alignment. The beam should never be set in motion by lowering it forcibly upon the knife-edges, nor by touching the pans, but rather by lifting the rider (unless the balance be provided with some of the newer devices for the purpose), and the swing should be arrested only when the needle approaches zero on the scale, otherwise the knife-edges become dull. For the same reason the beam should never be left upon its knife-edges, nor should weights be removed from or placed on the pans without supporting the beam, except in the case of the small fractional weights. When the process of weighing has been completed, the weight should be recorded in the notebook by first noting the vacant spaces in the weight-box, and then checking the weight by again noting the weights as they are removed from the pan. This practice will often detect and avoid errors. It is obvious that the weights should always be returned to their proper places in the box, and be handled only with pincers. It should be borne in mind that if the mechanism of a balance is deranged or if any substance is spilled upon the pans or in the balance case, the damage should be reported at once. In many instances serious harm can be averted by prompt action when delay might ruin the balance. Samples for analysis are commonly weighed in small tubes with cork stoppers. Since the stoppers are likely to change in weight from the varying amounts of moisture absorbed from the atmosphere, it is necessary to confirm the recorded weight of a tube which has been unused for some time before weighing out a new portion of substance from it. WEIGHTS The sets of weights commonly used in analytical chemistry range from 20 grams to 5 milligrams. The weights from 20 grams to 1 gram are usually of brass, lacquered or gold plated. The fractional weights are of German silver, gold, platinum or aluminium. The rider is of platinum or aluminium wire. The sets of weights purchased from reputable dealers are usually sufficiently accurate for analytical work. It is not necessary that such a set should be strictly exact in comparison with the absolute standard of weight, provided they are relatively correct among themselves, and provided the same set of weights is used in all weighings made during a given analysis. The analyst should assure himself that the weights in a set previously unfamiliar to him are relatively correct by a few simple tests. For example, he should make sure that in his set two weights of the same denomination (i.e., two 10-gram weights, or the two 100-milligram weights) are actually equal and interchangeable, or that the 500-milligram weight is equal to the sum of the 200, 100, 100, 50, 20, 20 and 10-milligram weights combined, and so on. If discrepancies of more than a few tenths of a milligram (depending upon the total weight involved) are found, the weights should be returned for correction. The rider should also be compared with a 5 or 10-milligram weight. In an instructional laboratory appreciable errors should be reported to the instructor in charge for his consideration. When the highest accuracy is desired, the weights may be calibrated and corrections applied. A calibration procedure is described in a paper by T.W. Richards, !J. Am. Chem. Soc.!, 22, 144, and in many large text-books. Weights are inevitably subject to corrosion if not properly protected at all times, and are liable to damage unless handled with great care. It is obvious that anything which alters the weight of a single piece in an analytical set will introduce an error in every weighing made in which that piece is used. This source of error is often extremely obscure and difficult to detect. The only safeguard against such errors is to be found in scrupulous care in handling and protection on the part of the analyst, and an equal insistence that if several analysts use the same set of weights, each shall realize his responsibility for the work of others as well as his own. BURETTES A burette is made from a glass tube which is as uniformly cylindrical as possible, and of such a bore that the divisions which are etched upon its surface shall correspond closely to actual contents. The tube is contracted at one extremity, and terminates in either a glass stopcock and delivery-tube, or in such a manner that a piece of rubber tubing may be firmly attached, connecting a delivery-tube of glass. The rubber tubing is closed by means of a glass bead. Burettes of the latter type will be referred to as "plain burettes." The graduations are usually numbered in cubic centimeters, and the latter are subdivided into tenths. One burette of each type is desirable for the analytical procedures which follow. PREPARATION OF A BURETTE FOR USE The inner surface of a burette must be thoroughly cleaned in order that the liquid as drawn out may drain away completely, without leaving drops upon the sides. This is best accomplished by treating the inside of the burette with a warm solution of chromic acid in concentrated sulphuric acid, applied as follows: If the burette is of the "plain" type, first remove the rubber tip and force the lower end of the burette into a medium-sized cork stopper. Nearly fill the burette with the chromic acid solution, close the upper end with a cork stopper and tip the burette backward and forward in such a way as to bring the solution into contact with the entire inner surface. Remove the stopper and pour the solution into a stock bottle to be kept for further use, and rinse out the burette with water several times. Unless the water then runs freely from the burette without leaving drops adhering to the sides, the process must be repeated (Note 1). If the burette has a glass stopcock, this should be removed after the cleaning and wiped, and also the inside of the ground joint. The surface of the stopcock should then be smeared with a thin coating of vaseline and replaced. It should be attached to the burette by means of a wire, or elastic band, to lessen the danger of breakage. Fill the burettes with distilled water, and allow the water to run out through the stopcock or rubber tip until convinced that no air bubbles are inclosed (Note 2). Fill the burette to a point above the zero-point and draw off the water until the meniscus is just below that mark. It is then ready for calibration. [Note 1: The inner surface of the burette must be absolutely clean if the liquid is to run off freely. Chromic acid in sulphuric acid is usually found to be the best cleansing agent, but the mixture must be warm and concentrated. The solution can be prepared by pouring over a few crystals of potassium bichromate a little water and then adding concentrated sulphuric acid.] [Note 2: It is always necessary to insure the absence of air bubbles in the tips or stopcocks. The treatment described above will usually accomplish this, but, in the case of plain burettes it is sometimes better to allow a little of the liquid to flow out of the tip while it is bent upwards. Any air which may be entrapped then rises with the liquid and escapes. If air bubbles escape during subsequent calibration or titration, an error is introduced which vitiates the results.] READING OF A BURETTE All liquids when placed in a burette form what is called a meniscus at their upper surfaces. In the case of liquids such as water or aqueous solutions this meniscus is concave, and when the liquids are transparent accurate readings are best obtained by observing the position on the graduated scales of the lowest point of the meniscus. This can best be done as follows: Wrap around the burette a piece of colored paper, the straight, smooth edges of which are held evenly together with the colored side next to the burette (Note 1). Hold the paper about two small divisions below the meniscus and raise or lower the level of the eyes until the edge of the paper at the back of the burette is just hidden from the eye by that in front (Note 2). Note the position of the lowest point of the curve of the meniscus, estimating the tenths of the small divisions, thus reading its position to hundredths of a cubic centimeter. [Note 1: The ends of the colored paper used as an aid to accurate readings may be fastened together by means of a gummed label. The paper may then remain on the burette and be ready for immediate use by sliding it up or down, as required.] [Note 2: To obtain an accurate reading the eye must be very nearly on a level with the meniscus. This is secured by the use of the paper as described. The student should observe by trial how a reading is affected when the meniscus is viewed from above or below. The eye soon becomes accustomed to estimating the tenths of the divisions. If the paper is held as directed, two divisions below the meniscus, one whole division is visible to correct the judgment. It is not well to attempt to bring the meniscus exactly to a division mark on the burette. Such readings are usually less accurate than those in which the tenths of a division are estimated.] CALIBRATION OF GLASS MEASURING DEVICES If accuracy of results is to be attained, the correctness of all measuring instruments must be tested. None of the apparatus offered for sale can be implicitly relied upon except those more expensive instruments which are accompanied by a certificate from the !National Bureau of Standards! at Washington, or other equally authentic source. The bore of burettes is subject to accidental variations, and since the graduations are applied by machine without regard to such variations of bore, local errors result. The process of testing these instruments is called !calibration!. It is usually accomplished by comparing the actual weight of water contained in the instrument with its apparent volume. There is, unfortunately, no uniform standard of volume which has been adopted for general use in all laboratories. It has been variously proposed to consider the volume of 1000 grams of water at 4°, 15.5°, 16°, 17.5°, and even 20°C., as a liter for practical purposes, and to consider the cubic centimeter to be one one-thousandth of that volume. The true liter is the volume of 1000 grams of water at 4°C.; but this is obviously a lower temperature than that commonly found in laboratories, and involves the constant use of corrections if taken as a laboratory standard. Many laboratories use 15.5°C. (60° F.) as the working standard. It is plain that any temperature which is deemed most convenient might be chosen for a particular laboratory, but it cannot be too strongly emphasized that all measuring instruments, including burettes, pipettes, and flasks, should be calibrated at that temperature in order that the contents of each burette, pipette, etc., shall be comparable with that of every other instrument, thus permitting general interchange and substitution. For example, it is obvious that if it is desired to remove exactly 50 cc. from a solution which has been diluted to 500 cc. in a graduated flask, the 50 cc. flask or pipette used to remove the fractional portion must give a correct reading at the same temperature as the 500 cc. flask. Similarly, a burette used for the titration of the 50 cc. of solution removed should be calibrated under the same conditions as the measuring flasks or pipettes employed with it. The student should also keep constantly in mind the fact that all volumetric operations, to be exact, should be carried out as nearly at a constant temperature as is practicable. The spot selected for such work should therefore be subject to a minimum of temperature variations, and should have as nearly the average temperature of the laboratory as is possible. In all work, whether of calibration, standardization, or analysis, the temperature of the liquids employed must be taken into account, and if the temperature of these liquids varies more than 3° or 4° from the standard temperature chosen for the laboratory, corrections must be applied for errors due to expansion or contraction, since volumes of a liquid measured at different times are comparable only under like conditions as to temperature. Data to be used for this purpose are given in the Appendix. Neglect of this correction is frequently an avoidable source of error and annoyance in otherwise excellent work. The temperature of all solutions at the time of standardization should be recorded to facilitate the application of temperature corrections, if such are necessary at any later time. CALIBRATION OF THE BURETTES Two burettes, one at least of which should have a glass stopper, are required throughout the volumetric work. Both burettes should be calibrated by the student to whom they are assigned. PROCEDURE.--Weigh a 50 cc., flat-bottomed flask (preferably a light-weight flask), which must be dry on the outside, to the nearest centigram. Record the weight in the notebook. (See Appendix for suggestions as to records.) Place the flask under the burette and draw out into it about 10 cc. of water, removing any drop on the tip by touching it against the inside of the neck of the flask. Do not attempt to stop exactly at the 10 cc. mark, but do not vary more than 0.1 cc. from it. Note the time, and at the expiration of three minutes (or longer) read the burette accurately, and record the reading in the notebook (Note 1). Meanwhile weigh the flask and water to centigrams and record its weight (Note 2). Draw off the liquid from 10 cc. to about 20 cc. into the same flask without emptying it; weigh, and at the expiration of three minutes take the reading, and so on throughout the length of the burette. When it is completed, refill the burette and check the first calibration. The differences in readings represent the apparent volumes, the differences in weights the true volumes. For example, if an apparent volume of 10.05 cc. is found to weigh 10.03 grams, it may be assumed with sufficient accuracy that the error in that 10 cc. amounts to -0.02 cc., or -0.002 for each cubic centimeter (Note 3). In the calculation of corrections the temperature of the water must be taken into account, if this varies more than 4°C. from the laboratory standard temperature, consulting the table of densities of water in the Appendix. From the final data, plot the corrections to be applied so that they may be easily read for each cubic centimeter throughout the burette. The total correction at each 10 cc. may also be written on the burette with a diamond, or etching ink, for permanence of record. [Note 1: A small quantity of liquid at first adheres to the side of even a clean burette. This slowly unites with the main body of liquid, but requires an appreciable time. Three minutes is a sufficient interval, but not too long, and should be adopted in every instance throughout the whole volumetric practice before final readings are recorded.] [Note 2: A comparatively rough balance, capable of weighing to centigrams, is sufficiently accurate for use in calibrations, for a moment's reflection will show that it would be useless to weigh the water with an accuracy greater than that of the readings taken on the burette. The latter cannot exceed 0.01 cc. in accuracy, which corresponds to 0.01 gram. The student should clearly understand that !all other weighings!, except those for calibration, should be made accurately to 0.0001 gram, unless special directions are given to the contrary. Corrections for temperature variations of less than 4°C. are negligible, as they amount to less than 0.01 gram for each 10 grams of water withdrawn.] [Note 3: Should the error discovered in any interval of 10 cc. on the burette exceed 0.10 cc., it is advisable to weigh small portions (even 1 cc.) to locate the position of the variation of bore in the tube rather than to distribute the correction uniformly over the corresponding 10 cc. The latter is the usual course for small corrections, and it is convenient to calculate the correction corresponding to each cubic centimeter and to record it in the form of a table or calibration card, or to plot a curve representing the values. Burettes may also be calibrated by drawing off the liquid in successive portions through a 5 cc. pipette which has been accurately calibrated, as a substitute for weighing. If many burettes are to be tested, this is a more rapid method.] PIPETTES A !pipette! may consist of a narrow tube, in the middle of which is blown a bulb of a capacity a little less than that which it is desired to measure by the pipette; or it may be a miniature burette, without the stopcock or rubber tip at the lower extremity. In either case, the flow of liquid is regulated by the pressure of the finger on the top, which governs the admission of the air. Pipettes are usually already graduated when purchased, but they require calibration for accurate work. CALIBRATION OF PIPETTES PROCEDURE.--Clean the pipette. Draw distilled water into it by sucking at the upper end until the water is well above the graduation mark. Quickly place the forefinger over the top of the tube, thus preventing the entrance of air and holding the water in the pipette. Cautiously admit a little air by releasing the pressure of the finger, and allow the level of the water to fall until the lowest point of the meniscus is level with the graduation. Hold the water at that point by pressure of the finger and then allow the water to run out from the pipette into a small tared, or weighed, beaker or flask. After a definite time interval, usually two to three minutes, touch the end of the pipette against the side of the beaker or flask to remove any liquid adhering to it (Note 1). The increase in weight of the flask in grams represents the volume of the water in cubic centimeters delivered by the pipette. Calculate the necessary correction. [Note 1: A definite interval must be allowed for draining, and a definite practice adopted with respect to the removal of the liquid which collects at the end of the tube, if the pipette is designed to deliver a specific volume when emptied. This liquid may be removed at the end of a definite interval either by touching the side of the vessel or by gently blowing out the last drops. Either practice, when adopted, must be uniformly adhered to.] FLASKS !Graduated or measuring flasks! are similar to the ordinary flat-bottomed flasks, but are provided with long, narrow necks in order that slight variations in the position of the meniscus with respect to the graduation shall represent a minimum volume of liquid. The flasks must be of such a capacity that, when filled with the specified volume, the liquid rises well into the neck. GRADUATION OF FLASKS It is a general custom to purchase the flasks ungraduated and to graduate them for use under standard conditions selected for the laboratory in question. They may be graduated for "contents" or "delivery." When graduated for "contents" they contain a specified volume when filled to the graduation at a specified temperature, and require to be washed out in order to remove all of the solution from the flask. Flasks graduated for "delivery" will deliver the specified volume of a liquid without rinsing. A flask may, of course, be graduated for both contents and delivery by placing two graduation marks upon it. PROCEDURE.--To calibrate a flask for !contents!, proceed as follows: Clean the flask, using a chromic acid solution, and dry it carefully outside and inside. Tare it accurately; pour water into the flask until the weight of the latter counterbalances weights on the opposite pan which equal in grams the number of cubic centimeters of water which the flask is to contain. Remove any excess of water with the aid of filter paper (Note 1). Take the flask from the balance, stopper it, place it in a bath at the desired temperature, usually 15.5° or 17.5°C., and after an hour mark on the neck with a diamond the location of the lowest point of the meniscus (Note 2). The mark may be etched upon the flask by hydrofluoric acid, or by the use of an etching ink now commonly sold on the market. To graduate a flask which is designed to !deliver! a specified volume, proceed as follows: Clean the flask as usual and wipe all moisture from the outside. Fill it with distilled water. Pour out the water and allow the water to drain from the flask for three minutes. Counterbalance the flask with weights to the nearest centigram. Add weights corresponding in grams to the volume desired, and add distilled water to counterbalance these weights. An excess of water, or water adhering to the neck of the flask, may be removed by means of a strip of clean filter paper. Stopper the flask, place it in a bath at 15.5°C. or 17.5°C. and, after an hour, mark the location of the lowest point of the meniscus, as described above. [Note 1: The allowable error in counterbalancing the water and weights varies with the volume of the flask. It should not exceed one ten-thousandth of the weight of water.] [Note 2: Other methods are employed which involve the use of calibrated apparatus from which the desired volume of water may be run into the dry flask and the position of the meniscus marked directly upon it. For a description of a procedure which is most convenient when many flasks are to be calibrated, the student is referred to the !Am. Chem J.!, 16, 479.] GENERAL DIRECTIONS FOR VOLUMETRIC ANALYSES It cannot be too strongly emphasized that for the success of analyses uniformity of practice must prevail throughout all volumetric work with respect to those factors which can influence the accuracy of the measurement of liquids. For example, whatever conditions are imposed during the calibration of a burette, pipette, or flask (notably the time allowed for draining), must also prevail whenever the flask or burette is used. The student should also be constantly watchful to insure parallel conditions during both standardization and analyst with respect to the final volume of liquid in which a titration takes place. The value of a standard solution is only accurate under the conditions which prevailed when it was standardized. It is plain that the standard solutions must be scrupulously protected from concentration or dilution, after their value has been established. Accordingly, great care must be taken to thoroughly rinse out all burettes, flasks, etc., with the solutions which they are to contain, in order to remove all traces of water or other liquid which could act as a diluent. It is best to wash out a burette at least three times with small portions of a solution, allowing each to run out through the tip before assuming that the burette is in a condition to be filled and used. It is, of course, possible to dry measuring instruments in a hot closet, but this is tedious and unnecessary. To the same end, all solutions should be kept stoppered and away from direct sunlight or heat. The bottles should be shaken before use to collect any liquid which may have distilled from the solution and condensed on the sides. The student is again reminded that variations in temperature of volumetric solutions must be carefully noted, and care should always be taken that no source of heat is sufficiently near the solutions to raise the temperature during use. Much time may be saved by estimating the approximate volume of a standard solution which will be required for a titration (if the data are obtainable) before beginning the operation. It is then possible to run in rapidly approximately the required amount, after which it is only necessary to determine the end-point slowly and with accuracy. In such cases, however, the knowledge of the approximate amount to be required should never be allowed to influence the judgment regarding the actual end-point. STANDARD SOLUTIONS The strength or value of a solution for a specific reaction is determined by a procedure called !Standardization!, in which the solution is brought into reaction with a definite weight of a substance of known purity. For example, a definite weight of pure sodium carbonate may be dissolved in water, and the volume of a solution of hydrochloric acid necessary to exactly neutralize the carbonate accurately determined. From these data the strength or value of the acid is known. It is then a !standard solution!. NORMAL SOLUTIONS Standard solutions may be made of a purely empirical strength dictated solely by convenience of manipulation, or the concentration may be chosen with reference to a system which is applicable to all solutions, and based upon chemical equivalents. Such solutions are called !Normal Solutions! and contain such an amount of the reacting substance per liter as is equivalent in its chemical action to one gram of hydrogen, or eight grams of oxygen. Solutions containing one half, one tenth, or one one-hundredth of this quantity per liter are called, respectively, half-normal, tenth-normal, or hundredth-normal solutions. Since normal solutions of various reagents are all referred to a common standard, they have an advantage not possessed by empirical solutions, namely, that they are exactly equivalent to each other. Thus, a liter of a normal solution of an acid will exactly neutralize a liter of a normal alkali solution, and a liter of a normal oxidizing solution will exactly react with a liter of a normal reducing solution, and so on. Beside the advantage of uniformity, the use of normal solutions simplifies the calculations of the results of analyses. This is particularly true if, in connection with the normal solution, the weight of substance for analysis is chosen with reference to the atomic or molecular weight of the constituent to be determined. (See problem 26.) The preparation of an !exactly! normal, half-normal, or tenth-normal solution requires considerable time and care. It is usually carried out only when a large number of analyses are to be made, or when the analyst has some other specific purpose in view. It is, however, a comparatively easy matter to prepare standard solutions which differ but slightly from the normal or half-normal solution, and these have the advantage of practical equality; that is, two approximately half-normal solutions are more convenient to work with than two which are widely different in strength. It is, however, true that some of the advantage which pertains to the use of normal solutions as regards simplicity of calculations is lost when using these approximate solutions. The application of these general statements will be made clear in connection with the use of normal solutions in the various types of volumetric processes which follow. I. NEUTRALIZATION METHODS ALKALIMETRY AND ACIDIMETRY GENERAL DISCUSSION !Standard Acid Solutions! may be prepared from either hydrochloric, sulphuric, or oxalic acid. Hydrochloric acid has the advantage of forming soluble compounds with the alkaline earths, but its solutions cannot be boiled without danger of loss of strength; sulphuric acid solutions may be boiled without loss, but the acid forms insoluble sulphates with three of the alkaline earths; oxalic acid can be accurately weighed for the preparation of solutions, and its solutions may be boiled without loss, but it forms insoluble oxalates with three of the alkaline earths and cannot be used with certain of the indicators. !Standard Alkali Solutions! may be prepared from sodium or potassium hydroxide, sodium carbonate, barium hydroxide, or ammonia. Of sodium and potassium hydroxide, it may be said that they can be used with all indicators, and their solutions may be boiled, but they absorb carbon dioxide readily and attack the glass of bottles, thereby losing strength; sodium carbonate may be weighed directly if its purity is assured, but the presence of carbonic acid from the carbonate is a disadvantage with many indicators; barium hydroxide solutions may be prepared which are entirely free from carbon dioxide, and such solutions immediately show by precipitation any contamination from absorption, but the hydroxide is not freely soluble in water; ammonia does not absorb carbon dioxide as readily as the caustic alkalies, but its solutions cannot be boiled nor can they be used with all indicators. The choice of a solution must depend upon the nature of the work in hand. A !normal acid solution! should contain in one liter that quantity of the reagent which represents 1 gram of hydrogen replaceable by a base. For example, the normal solution of hydrochloric acid (HCl) should contain 36.46 grams of gaseous hydrogen chloride, since that amount furnishes the requisite 1 gram of replaceable hydrogen. On the other hand, the normal solution of sulphuric acid (H_{2}SO_{4}) should contain only 49.03 grams, i.e., one half of its molecular weight in grams. A !normal alkali solution! should contain sufficient alkali in a liter to replace 1 gram of hydrogen in an acid. This quantity is represented by the molecular weight in grams (40.01) of sodium hydroxide (NaOH), while a sodium carbonate solution (Na_{2}CO_{3}) should contain but one half the molecular weight in grams (i.e., 53.0 grams) in a liter of normal solution. Half-normal or tenth-normal solutions are employed in most analyses (except in the case of the less soluble barium hydroxide). Solutions of the latter strength yield more accurate results when small percentages of acid or alkali are to be determined. INDICATORS It has already been pointed out that the purpose of an indicator is to mark (usually by a change of color) the point at which just enough of the titrating solution has been added to complete the chemical change which it is intended to bring about. In the neutralization processes which are employed in the measurement of alkalies (!alkalimetry!) or acids (!acidimetry!) the end-point of the reaction should, in principle, be that of complete neutrality. Expressed in terms of ionic reactions, it should be the point at which the H^{+} ions from an acid[Note 1] unite with a corresponding number of OH^{-} ions from a base to form water molecules, as in the equation H^{+}, Cl^{-} + Na^{+}, OH^{-} --> Na^{+}, Cl^{-} + (H_{2}O). It is not usually possible to realize this condition of exact neutrality, but it is possible to approach it with sufficient exactness for analytical purposes, since substances are known which, in solution, undergo a sharp change of color as soon as even a minute excess of H^{+} or OH^{-} ions are present. Some, as will be seen, react sharply in the presence of H^{+} ions, and others with OH^{-} ions. These substances employed as indicators are usually organic compounds of complex structure and are closely allied to the dyestuffs in character. [Note 1: A knowledge on the part of the student of the ionic theory as applied to aqueous solutions of electrolytes is assumed. A brief outline of the more important applications of the theory is given in the Appendix.] BEHAVIOR OF ORGANIC INDICATORS The indicators in most common use for acid and alkali titrations are methyl orange, litmus, and phenolphthalein. In the following discussion of the principles underlying the behavior of the indicators as a class, methyl orange and phenolphthalein will be taken as types. It has just been pointed out that indicators are bodies of complicated structure. In the case of the two indicators named, the changes which they undergo have been carefully studied by Stieglitz (!J. Am. Chem. Soc.!, 25, 1112) and others, and it appears that the changes involved are of two sorts: First, a rearrangement of the atoms within the molecule, such as often occurs in organic compounds; and, second, ionic changes. The intermolecular changes cannot appropriately be discussed here, as they involve a somewhat detailed knowledge of the classification and general behavior of organic compounds; they will, therefore, be merely alluded to, and only the ionic changes followed. Methyl orange is a representative of the group of indicators which, in aqueous solutions, behave as weak bases. The yellow color which it imparts to solutions is ascribed to the presence of the undissociated base. If an acid, such as HCl, is added to such a solution, the acid reacts with the indicator (neutralizes it) and a salt is formed, as indicated by the equation: (M.o.)^{+}, OH^{-} + H^{+}, Cl^{-} --> (M.o.)^{+} Cl^{-} + (H_{2}O). This salt ionizes into (M.o.)^{+} (using this abbreviation for the positive complex) and Cl^{-}; but simultaneously with this ionization there appears to be an internal rearrangement of the atoms which results in the production of a cation which may be designated as (M'.o'.)^{+}, and it is this which imparts a characteristic red color to the solution. As these changes occur in the presence of even a very small excess of acid (that is, of H^{+} ions), it serves as the desired index of their presence in the solution. If, now, an alkali, such as NaOH, is added to this reddened solution, the reverse series of changes takes place. As soon as the free acid present is neutralized, the slightest excess of sodium hydroxide, acting as a strong base, sets free the weak, little-dissociated base of the indicator, and at the moment of its formation it reverts, because of the rearrangement of the atoms, to the yellow form: OH^{-} + (M'.o'.)^{+} --> [M'.o'.OH] --> [M.o.OH]. Phenolphthalein, on the other hand, is a very weak, little-dissociated acid, which is colorless in neutral aqueous solution or in the presence of free H^{+} ions. When an alkali is added to such a solution, even in slight excess, the anion of the salt which has formed from the acid of the indicator undergoes a rearrangement of the atoms, and a new ion, (Ph')^{+}, is formed, which imparts a pink color to the solution: H^{+}, (Ph)^{-} + Na^{+}, OH^{-} --> (H_{2}O) + Na^{+}, (Ph)^{-} --> Na^{+}, (Ph')^{-} The addition of the slightest excess of an acid to this solution, on the other hand, occasions first the reversion to the colorless ion and then the setting free of the undissociated acid of the indicator: H^{+}, (Ph')^{-} --> H^{+}, (Ph)^{-} --> (HPh). Of the common indicators methyl orange is the most sensitive toward alkalies and phenolphthalein toward acids; the others occupy intermediate positions. That methyl orange should be most sensitive toward alkalies is evident from the following considerations: Methyl orange is a weak base and, therefore, but little dissociated. It should, then, be formed in the undissociated condition as soon as even a slight excess of OH^{-} ions is present in the solution, and there should be a prompt change from red to yellow as outlined above. On the other hand, it should be an unsatisfactory indicator for use with weak acids (acetic acid, for example) because the salts which it forms with such acids are, like all salts of that type, hydrolyzed to a considerable extent. This hydrolytic change is illustrated by the equation: (M.o.)^{+} C_{2}H_{3}O_{2}^{-} + H^{+}, OH^{-} --> [M.o.OH] + H^{+}, C_{2}H_{3}O_{2}^{-}. Comparison of this equation with that on page 30 will make it plain that hydrolysis is just the reverse of neutralization and must, accordingly, interfere with it. Salts of methyl orange with weak acids are so far hydrolyzed that the end-point is uncertain, and methyl orange cannot be used in the titration of such acids, while with the very weak acids, such as carbonic acid or hydrogen sulphide (hydrosulphuric acid), the salts formed with methyl orange are, in effect, completely hydrolyzed (i.e., no neutralization occurs), and methyl orange is accordingly scarcely affected by these acids. This explains its usefulness, as referred to later, for the titration of strong acids, such as hydrochloric acid, even in the presence of carbonates or sulphides in solution. Phenolphthalein, on the other hand, should be, as it is, the best of the common indicators for use with weak acids. For, since it is itself a weak acid, it is very little dissociated, and its nearly undissociated, colorless molecules are promptly formed as soon as there is any free acid (that is, free H^{+} ions) in the solution. This indicator cannot, however, be successfully used with weak bases, even ammonium hydroxide; for, since it is weak acid, the salts which it forms with weak alkalies are easily hydrolyzed, and as a consequence of this hydrolysis the change of color is not sharp. This indicator can, however, be successfully used with strong bases, because the salts which it forms with such bases are much less hydrolyzed and because the excess of OH^{-} ions from these bases also diminishes the hydrolytic action of water. This indicator is affected by even so weak an acid as carbonic acid, which must be removed by boiling the solution before titration. It is the indicator most generally employed for the titration of organic acids. In general, it may be stated that when a strong acid, such as hydrochloric, sulphuric or nitric acid, is titrated against a strong base, such as sodium hydroxide, potassium hydroxide, or barium hydroxide, any of these indicators may be used, since very little hydrolysis ensues. It has been noted above that the color change does not occur exactly at theoretical neutrality, from which it follows that no two indicators will show exactly the same end-point when acids and alkalis are brought together. It is plain, therefore, that the same indicator must be employed for both standardization and analysis, and that, if this is done, accurate results are obtainable. The following table (Note 1) illustrates the variations in the volume of an alkali solution (tenth-normal sodium hydroxide) required to produce an alkaline end-point when run into 10 cc. of tenth-normal sulphuric acid, diluted with 50 cc. of water, using five drops of each of the different indicator solutions. ==================================================================== | | | | INDICATOR | N/10 | N/10 |COLOR IN ACID|COLOR IN ALKA- | H_{2}SO_{4}| NaOH |SOLUTION |LINE SOLUTION _______________|____________|__________|_____________|______________ | cc. | cc. | cc. | Methyl orange | 10 | 9.90 | Red | Yellow Lacmoid | 10 | 10.00 | Red | Blue Litmus | 10 | 10.00 | Red | Blue Rosalic acid | 10 | 10.07 | Yellow | Pink Phenolphthalein| 10 | 10.10 | Colorless | Pink ==================================================================== It should also be stated that there are occasionally secondary changes, other than those outlined above, which depend upon the temperature and concentration of the solutions in which the indicators are used. These changes may influence the sensitiveness of an indicator. It is important, therefore, to take pains to use approximately the same volume of solution when standardizing that is likely to be employed in analysis; and when it is necessary, as is often the case, to titrate the solution at boiling temperature, the standardization should take place under the same conditions. It is also obvious that since some acid or alkali is required to react with the indicator itself, the amount of indicator used should be uniform and not excessive. Usually a few drops of solution will suffice. The foregoing statements with respect to the behavior of indicators present the subject in its simplest terms. Many substances other than those named may be employed, and they have been carefully studied to determine the exact concentration of H^{+} ions at which the color change of each occurs. It is thus possible to select an indicator for a particular purpose with considerable accuracy. As data of this nature do not belong in an introductory manual, reference is made to the following papers or books in which a more extended treatment of the subject may be found: Washburn, E.W., Principles of Physical Chemistry (McGraw-Hill Book Co.), (Second Edition, 1921), pp. 380-387. Prideaux, E.B.R., The Theory and Use of Indicators (Constable & Co., Ltd.), (1917). Salm, E., A Study of Indicators, !Z. physik. Chem.!, 57 (1906), 471-501. Stieglitz, J., Theories of Indicators, !J. Am. Chem. Soc.!, 25 (1903), 1112-1127. Noyes, A.A., Quantitative Applications of the Theory of Indicators to Volumetric Analysis, !J. Am. Chem. Soc.!, 32 (1911), 815-861. Bjerrum, N., General Discussion, !Z. Anal. Chem.!, 66 (1917), 13-28 and 81-95. Ostwald, W., Colloid Chemistry of Indicators, !Z. Chem. Ind. Kolloide!, 10 (1912), 132-146. [Note 1: Glaser, !Indikatoren der Acidimetrie und Alkalimetrie!. Wiesbaden, 1901.] PREPARATION OF INDICATOR SOLUTIONS A !methyl orange solution! for use as an indicator is commonly made by dissolving 0.05-0.1 gram of the compound (also known as Orange III) in a few cubic centimeters of alcohol and diluting with water to 100 cc. A good grade of material should be secured. It can be successfully used for the titration of hydrochloric, nitric, sulphuric, phosphoric, and sulphurous acids, and is particularly useful in the determination of bases, such as sodium, potassium, barium, calcium, and ammonium hydroxides, and even many of the weak organic bases. It can also be used for the determination, by titration with a standard solution of a strong acid, of the salts of very weak acids, such as carbonates, sulphides, arsenites, borates, and silicates, because the weak acids which are liberated do not affect the indicator, and the reddening of the solution does not take place until an excess of the strong acid is added. It should be used in cold, not too dilute, solutions. Its sensitiveness is lessened in the presence of considerable quantities of the salts of the alkalies. A !phenolphthalein solution! is prepared by dissolving 1 gram of the pure compound in 100 cc. of 95 per cent alcohol. This indicator is particularly valuable in the determination of weak acids, especially organic acids. It cannot be used with weak bases, even ammonia. It is affected by carbonic acid, which must, therefore, be removed by boiling when other acids are to be measured. It can be used in hot solutions. Some care is necessary to keep the volume of the solutions to be titrated approximately uniform in standardization and in analysis, and this volume should not in general exceed 125-150 cc. for the best results, since the compounds formed by the indicator undergo changes in very dilute solution which lessen its sensitiveness. The preparation of a !solution of litmus! which is suitable for use as an indicator involves the separation from the commercial litmus of azolithmine, the true coloring principle. Soluble litmus tablets are often obtainable, but the litmus as commonly supplied to the market is mixed with calcium carbonate or sulphate and compressed into lumps. To prepare a solution, these are powdered and treated two or three times with alcohol, which dissolves out certain constituents which cause a troublesome intermediate color if not removed. The alcohol is decanted and drained off, after which the litmus is extracted with hot water until exhausted. The solution is allowed to settle for some time, the clear liquid siphoned off, concentrated to one-third its volume and acetic acid added in slight excess. It is then concentrated to a sirup, and a large excess of 95 per cent. alcohol added to it. This precipitates the blue coloring matter, which is filtered off, washed with alcohol, and finally dissolved in a small volume of water and diluted until about three drops of the solution added to 50 cc. of water just produce a distinct color. This solution must be kept in an unstoppered bottle. It should be protected from dust by a loose plug of absorbent cotton. If kept in a closed bottle it soon undergoes a reduction and loses its color, which, however, is often restored by exposure to the air. Litmus can be employed successfully with the strong acids and bases, and also with ammonium hydroxide, although the salts of the latter influence the indicator unfavorably if present in considerable concentration. It may be employed with some of the stronger organic acids, but the use of phenolphthalein is to be preferred. PREPARATION OF STANDARD SOLUTIONS !Hydrochloric Acid and Sodium Hydroxide. Approximate Strength!, 0.5 N PROCEDURE.--Measure out 40 cc. of concentrated, pure hydrochloric acid into a clean liter bottle, and dilute with distilled water to an approximate volume of 1000 cc. Shake the solution vigorously for a full minute to insure uniformity. Be sure that the bottle is not too full to permit of a thorough mixing, since lack of care at this point will be the cause of much wasted time (Note 1). Weigh out, upon a rough balance, 23 grams of sodium hydroxide (Note 2). Dissolve the hydroxide in water in a beaker. Pour the solution into a liter bottle and dilute, as above, to approximately 1000 cc. This bottle should preferably have a rubber stopper, as the hydroxide solution attacks the glass of the ground joint of a glass stopper, and may cement the stopper to the bottle. Shake the solution as described above. [Note 1: The original solutions are prepared of a strength greater than 0.5 N, as they are more readily diluted than strengthened if later adjustment is desired. Too much care cannot be taken to insure perfect uniformity of solutions before standardization, and thoroughness in this respect will, as stated, often avoid much waste of time. A solution once thoroughly mixed remains uniform.] [Note 2: Commercial sodium hydroxide is usually impure and always contains more or less carbonate; an allowance is therefore made for this impurity by placing the weight taken at 23 grams per liter. If the hydroxide is known to be pure, a lesser amount (say 21 grams) will suffice.] COMPARISON OF ACID AND ALKALI SOLUTIONS PROCEDURE.--Rinse a previously calibrated burette three times with the hydrochloric acid solution, using 10 cc. each time, and allowing the liquid to run out through the tip to displace all water and air from that part of the burette. Then fill the burette with the acid solution. Carry out the same procedure with a second burette, using the sodium hydroxide solution. The acid solution may be placed in a plain or in a glass-stoppered burette as may be more convenient, but the alkaline solution should never be allowed to remain long in a glass-stoppered burette, as it tends to cement the stopper to the burette, rendering it useless. It is preferable to use a plain burette for this solution. When the burettes are ready for use and all air bubbles displaced from the tip (see Note 2, page 17) note the exact position of the liquid in each, and record the readings in the notebook. (Consult page 188.) Run out from the burette into a beaker about 40 cc. of the acid and add two drops of a solution of methyl orange; dilute the acid to about 80 cc. and run out alkali solution from the other burette, stirring constantly, until the pink has given place to a yellow. Wash down the sides of the beaker with a little distilled water if the solution has spattered upon them, return the beaker to the acid burette, and add acid to restore the pink; continue these alternations until the point is accurately fixed at which a single drop of either solutions served to produce a distinct change of color. Select as the final end-point the appearance of the faintest pink tinge which can be recognized, or the disappearance of this tinge, leaving a pure yellow; but always titrate to the same point (Note 1). If the titration has occupied more than the three minutes required for draining the sides of the burette, the final reading may be taken immediately and recorded in the notebook. Refill the burettes and repeat the titration. From the records of calibration already obtained, correct the burette readings and make corrections for temperature, if necessary. Obtain the ratio of the sodium hydroxide solution to that of hydrochloric acid by dividing the number of cubic centimeters of acid used by the number of cubic centimeters of alkali required for neutralization. The check results of the two titrations should not vary by more than two parts in one thousand (Note 2). If the variation in results is greater than this, refill the burettes and repeat the titration until satisfactory values are obtained. Use a new page in the notebook for each titration. Inaccurate values should not be erased or discarded. They should be retained and marked "correct" or "incorrect," as indicated by the final outcome of the titrations. This custom should be rigidly followed in all analytical work. [Note 1: The end-point should be chosen exactly at the point of change; any darker tint is unsatisfactory, since it is impossible to carry shades of color in the memory and to duplicate them from day to day.] [Note 2: While variation of two parts in one thousand in the values obtained by an inexperienced analyst is not excessive, the idea must be carefully avoided that this is a standard for accurate work to be !generally applied!. In many cases, after experience is gained, the allowable error is less than this proportion. In a few cases a larger variation is permissible, but these are rare and can only be recognized by an experienced analyst. It is essential that the beginner should acquire at least the degree of accuracy indicated if he is to become a successful analyst.] STANDARDIZATION OF HYDROCHLORIC ACID SELECTION AND PREPARATION OF STANDARD The selection of the best substance to be used as a standard for acid solutions has been the subject of much controversy. The work of Lunge (!Ztschr. angew. Chem.! (1904), 8, 231), Ferguson (!J. Soc. Chem. Ind.! (1905), 24, 784), and others, seems to indicate that the best standard is sodium carbonate prepared from sodium bicarbonate by heating the latter at temperature between 270° and 300°C. The bicarbonate is easily prepared in a pure state, and at the temperatures named the decomposition takes place according to the equation 2HNaCO_{3} --> Na_{2}CO_{3} + H_{2}O + CO_{2} and without loss of any carbon dioxide from the sodium carbonate, such as may occur at higher temperatures. The process is carried out as described below. PROCEDURE.--Place in a porcelain crucible about 6 grams (roughly weighed) of the purest sodium bicarbonate obtainable. Rest the crucible upon a triangle of iron or copper wire so placed within a large crucible that there is an open air space of about three eighths of an inch between them. The larger crucible may be of iron, nickel or porcelain, as may be most convenient. Insert the bulb of a thermometer reading to 350°C. in the bicarbonate, supporting it with a clamp so that the bulb does not rest on the bottom of the crucible. Heat the outside crucible, using a rather small flame, and raise the temperature of the bicarbonate fairly rapidly to 270°C. Then regulate the heat in such a way that the temperature rises !slowly! to 300°C. in the course of a half-hour. The bicarbonate should be frequently stirred with a clean, dry, glass rod, and after stirring, should be heaped up around the bulb of the thermometer in such a way as to cover it. This will require attention during most of the heating, as the temperature should not be permitted to rise above 310°C. for any length of time. At the end of the half-hour remove the thermometer and transfer the porcelain crucible, which now contains sodium carbonate, to a desiccator. When it is cold, transfer the carbonate to a stoppered weighing tube or weighing-bottle. STANDARDIZATION PROCEDURE.--Clean carefully the outside of a weighing-tube, or weighing-bottle, containing the pure sodium carbonate, taking care to handle it as little as possible after wiping. Weigh the tube accurately to 0.0001 gram, and record the weight in the notebook. Hold the tube over the top of a beaker (200-300 cc.) and cautiously remove the stopper, making sure that no particles fall from it or from the tube elsewhere than in the beaker. Pour out from the tube a portion of the carbonate, replace the stopper and determine approximately how much has been removed. Continue this procedure until 1.00 to 1.10 grams has been taken from the tube. Then weigh the tube accurately and record the weight under the first weight in the notebook. The difference in the two weights is the weight of the carbonate transferred to the beaker. Proceed in the same way to transfer a second portion of the carbonate from the tube to another beaker of about the same size as the first. The beakers should be labeled and plainly marked to correspond with the entries in the notebook. Pour over the carbonate in each beaker about 80 cc. of water, stir until solution is complete, and add two drops of methyl orange solution. Fill the burettes with the standard acid and alkali solutions, noting the initial readings of the burettes and temperature of the solutions. Run in acid from the burette, stirring and avoiding loss by effervescence, until the solution has become pink. Wash down the sides of the beaker with a !little! water from a wash-bottle, and then run in alkali from the other burette until the pink is replaced by yellow; then finish the titration as described on page 37. Note the readings of the burettes after the proper interval, and record them in the notebook. Repeat the procedure, using the second portion of sodium carbonate. Apply the necessary calibration corrections to the volumes of the solutions used, and correct for temperature if necessary. From the data obtained, calculate the volume of the hydrochloric acid solution which is equivalent to the volume of sodium hydroxide solution used in this titration. Subtract this volume from the volume of hydrochloric acid. The difference represents the volume of acid used to react with the sodium carbonate. Divide the weight of sodium carbonate by this volume in cubic centimeters, thus obtaining the weight of sodium carbonate equivalent to each cubic centimeter of the acid. From this weight it is possible to calculate the corresponding weight of HCl in each cubic centimeter of the acid, and in turn the relation of the acid to the normal. If, however, it is recalled that normal solutions are equivalent to each other, it will be seen that the same result may be more readily reached by dividing the weight in grams of sodium carbonate per cubic centimeter just found by titration by the weight which would be contained in the same volume of a normal solution of sodium carbonate. A normal solution of sodium carbonate contains 53.0 grams per liter, or 0.0530 gram per cc. (see page 29). The relation of the acid solution to the normal is, therefore, calculated by dividing the weight of the carbonate to which each cubic centimeter of the acid is equivalent by 0.0530. The standardization must be repeated until the values obtained agree within, at most, two parts in one thousand. When the standard of the acid solution has been determined, calculate, from the known ratio of the two solutions, the relation of the sodium hydroxide solution to a normal solution (Notes 1 and 2). [Note 1: In the foregoing procedure the acid solution is standardized and the alkali solution referred to this standard by calculation. It is equally possible, if preferred, to standardize the alkali solution. The standards in a common use for this purpose are purified oxalic acid (H_{2}C_{2}O_{4}.2H_{2}O), potassium acid oxalate (KHC_{2}O_{4}.H_{2}O or KHC_{2}O_{4}), potassium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O), or potassium acid tartrate (KHC_{4}O_{6}), with the use of a suitable indicator. The oxalic acid and the oxalates should be specially prepared to insure purity, the main difficulty lying in the preservation of the water of crystallization. It should be noted that the acid oxalate and the acid tartrate each contain one hydrogen atom replaceable by a base, while the tetroxalate contains three such atoms and the oxalic acid two. Each of the two salts first named behave, therefore, as monobasic acids, and the tetroxalate as a tribasic acid.] [Note 2: It is also possible to standardize a hydrochloric acid solution by precipitating the chloride ions as silver chloride and weighing the precipitate, as prescribed under the analysis of sodium chloride to be described later. Sulphuric acid solutions may be standardized by precipitation of the sulphate ions as barium sulphate and weighing the ignited precipitate, but the results are not above criticism on account of the difficulty in obtaining large precipitates of barium sulphate which are uncontaminated by inclosures or are not reduced on ignition.] DETERMINATION OF THE TOTAL ALKALINE STRENGTH OF SODA ASH Soda ash is crude sodium carbonate. If made by the ammonia process it may contain also sodium chloride, sulphate, and hydroxide; when made by the Le Blanc process it may contain sodium sulphide, silicate, and aluminate, and other impurities. Some of these, notably the hydroxide, combine with acids and contribute to the total alkaline strength, but it is customary to calculate this strength in terms of sodium carbonate; i.e., as though no other alkali were present. PROCEDURE.--In order to secure a sample which shall represent the average value of the ash, it is well to take at least 5 grams. As this is too large a quantity for convenient titration, an aliquot portion of the solution is measured off, representing one fifth of the entire quantity. This is accomplished as follows: Weigh out on an analytical balance two samples of soda ash of about 5 grams each into beakers of about 500 cc. capacity. (The weighings need be made to centigrams only.) Dissolve the ash in 75 cc. of water, warming gently, and filter off the insoluble residue; wash the filter by filling it at least three times with distilled water, and allowing it to drain, adding the washings to the main filtrate. Cool the filtrate to approximately the standard temperature of the laboratory, and transfer it to a 250 cc. measuring flask, washing out the beaker thoroughly. Add distilled water of laboratory temperature until the lowest point of the meniscus is level with the graduation on the neck of the flask and remove any drops of water that may be on the neck above the graduation by means of a strip of filter paper; make the solution thoroughly uniform by pouring it out into a dry beaker and back into the flask several times. Measure off 50 cc. of the solution in a measuring flask, or pipette, either of which before use should, unless they are dry on the inside, be rinsed out with at least two small portions of the soda ash solution to displace any water. If a flask is used, fill it to the graduation with the soda ash solution and remove any liquid from the neck above the graduation with filter paper. Empty it into a beaker, and wash out the small flask, unless it is graduated for !delivery!, using small quantities of water, which are added to the liquid in the beaker. A second 50 cc. portion from the main solution should be measured off into a second beaker. Dilute the solutions in each beaker to 100 cc., add two drops of a solution of methyl orange (Note 1) and titrate for the alkali with the standard hydrochloric acid solution, using the alkali solution to complete the titration as already prescribed. From the volumes of acid and alkali employed, corrected for burette errors and temperature changes, and the data derived from the standardization, calculate the percentage of alkali present, assuming it all to be present as sodium carbonate (Note 2). [Note 1: The hydrochloric acid sets free carbonic acid which is unstable and breaks down into water and carbon dioxide, most of which escapes from the solution. Carbonic acid is a weak acid and, as such, does not yield a sufficient concentration of H^{+} ions to cause the indicator to change to a pink (see page 32). The chemical changes involved may be summarized as follows: 2H^{+}, 2Cl^{-} + 2Na^{+}, CO_{3}^{--} --> 2Na^{+}, 2Cl^{-} + [H_{2}CO_{3}] --> H_{2}O + CO_{2}] [Note 2: A determination of the alkali present as hydroxide in soda ash may be determined by precipitating the carbonate by the addition of barium chloride, removing the barium carbonate by filtration, and titrating the alkali in the filtrate. The caustic alkali may also be determined by first using phenolphthalein as an indicator, which will show by its change from pink to colorless the point at which the caustic alkali has been neutralized and the carbonate has been converted to bicarbonate, and then adding methyl orange and completing the titration. The amount of acid necessary to change the methyl orange to pink is a measure of one half of the carbonate present. The results of the double titration furnish the data necessary for the determination of the caustic alkali and of the carbonate in the sample.] DETERMINATION OF THE ACID STRENGTH OF OXALIC ACID PROCEDURE.--Weigh out two portions of the acid of about 1 gram each. Dissolve these in 50 cc. of warm water. Add two drops of phenolphthalein solution, and run in alkali from the burette until the solution is pink; add acid from the other burette until the pink is just destroyed, and then add 0.3 cc. (not more) in excess. Heat the solution to boiling for three minutes. If the pink returns during the boiling, discharge it with acid and again add 0.3 cc. in excess and repeat the boiling (Note 1). If the color does not then reappear, add alkali until it does, and a !drop or two! of acid in excess and boil again for one minute (Note 2). If no color reappears during this time, complete the titration in the hot solution. The end-point should be the faintest visible shade of color (or its disappearance), as the same difficulty would exist here as with methyl orange if an attempt were made to match shades of pink. From the corrected volume of alkali required to react with the oxalic acid, calculate the percentage of the crystallized acid (H_{2}C_{2}O_{4}.2H_{2}O) in the sample (Note 3). [Note 1: All commercial caustic soda such as that from which the standard solution was made contains some sodium carbonate. This reacts with the oxalic acid, setting free carbonic acid, which, in turn, forms sodium bicarbonate with the remaining carbonate: H_{2}CO_{3} + Na_{2}CO_{3} --> 2HNaCO_{3}. This compound does not hydrolyze sufficiently to furnish enough OH^{-} ions to cause phenolphthalein to remain pink; hence, the color of the indicator is discharged in cold solutions at the point at which bicarbonate is formed. If, however, the solution is heated to boiling, the bicarbonate loses carbon dioxide and water, and reverts to sodium carbonate, which causes the indicator to become again pink: 2HNaCO_{3} --> H_{2}O + CO_{2} + Na_{2}CO_{3}. By adding successive portions of hydrochloric acid and boiling, the carbonate is ultimately all brought into reaction. The student should make sure that the difference in behavior of the two indicators, methyl orange and phenolphthalein, is understood.] [Note 2: Hydrochloric acid is volatilized from aqueous solutions, except such as are very dilute. If the directions in the procedure are strictly followed, no loss of acid need be feared, but the amount added in excess should not be greater than 0.3-0.4 cc.] [Note 3: Attention has already been called to the fact that the color changes in the different indicators occur at varying concentrations of H^{+} or OH^{-} ions. They do not indicate exact theoretical neutrality, but a particular indicator always shows its color change at a particular concentration of H^{+} or OH^{-} ions. The results of titration with a given indicator are, therefore, comparable. As a matter of fact, a small error is involved in the procedure as outlined above. The comparison of the acid and alkali solutions was made, using methyl orange as an indicator, while the titration of the oxalic acid is made with the use of phenolphthalein. For our present purposes the small error may be neglected but, if time permits, the student is recommended to standardize the alkali solution against one of the substances named in Note 1, page 41, and also to ascertain the comparative value of the acid and alkali solutions, using phenolphthalein as indicator throughout, and conducting the titrations as described above. This will insure complete accuracy.] II. OXIDATION PROCESSES GENERAL DISCUSSION In the oxidation processes of volumetric analysis standard solutions of oxidizing agents and of reducing agents take the place of the acid and alkali solutions of the neutralization processes already studied. Just as an acid solution was the principal reagent in alkalimetry, and the alkali solution used only to make certain of the end-point, the solution of the oxidizing agent is the principal reagent for the titration of substances exerting a reducing action. It is, in general, true that oxidizable substances are determined by !direct! titration, while oxidizing substances are determined by !indirect! titration. The important oxidizing agents employed in volumetric solutions are potassium bichromate, potassium permangenate, potassium ferricyanide, iodine, ferric chloride, and sodium hypochlorite. The important reducing agents which are used in the form of standard solutions are ferrous sulphate (or ferrous ammonium sulphate), oxalic acid, sodium thiosulphate, stannous chloride, arsenious acid, and potassium cyanide. Other reducing agents, as sulphurous acid, sulphureted hydrogen, and zinc (nascent hydrogen), may take part in the processes, but not as standard solutions. The most important combinations among the foregoing are: Potassium bichromate and ferrous salts; potassium permanganate and ferrous salts; potassium permanganate and oxalic acid, or its derivatives; iodine and sodium thiosulphate; hypochlorites and arsenious acid. BICHROMATE PROCESS FOR THE DETERMINATION OF IRON Ferrous salts may be promptly and completely oxidized to ferric salts, even in cold solution, by the addition of potassium bichromate, provided sufficient acid is present to hold in solution the ferric and chromic compounds which are formed. The acid may be either hydrochloric or sulphuric, but the former is usually preferred, since it is by far the best solvent for iron and its compounds. The reaction in the presence of hydrochloric acid is as follows: 6FeCl_{2} + K_{2}Cr_{2}O_{7} + 14HCl --> 6FeCl_{3} + 2CrCl_{3} + 2KCl + 7H_{2}O. NORMAL SOLUTIONS OF OXIDIZING OR REDUCING AGENTS It will be recalled that the system of normal solutions is based upon the equivalence of the reagents which they contain to 8 grams of oxygen or 1 gram of hydrogen. A normal solution of an oxidizing agent should, therefore, contain that amount per liter which is equivalent in oxidizing power to 8 grams of oxygen; a normal reducing solution must be equivalent in reducing power to 1 gram of hydrogen. In order to determine what the amount per liter will be it is necessary to know how the reagents enter into reaction. The two solutions to be employed in the process under consideration are those of potassium bichromate and ferrous sulphate. The reaction between them, in the presence of an excess of sulphuric acid, may be expressed as follows: 6FeSO_{4} + K_{2}Cr_{2}O_{7} + 7H_{2}SO_{4} --> 3Fe_{2}(SO_{4})_{3} + K_{2}SO_{4} + Cr_{2}(SO_{4})_{3} + 7H_{2}O. If the compounds of iron and chromium, with which alone we are now concerned, be written in such a way as to show the oxides of these elements in each, they would appear as follows: On the left-hand side of the equation 6(FeO.SO_{3}) and K_{2}O.2CrO_{3}; on the right-hand side, 3(Fe_{2}O_{3}.3SO_{3}) and Cr_{2}O_{3}.3SO_{3}. A careful inspection shows that there are three less oxygen atoms associated with chromium atoms on the right-hand side of the equation than on the left-hand, but there are three more oxygen atoms associated with iron atoms on the right than on the left. In other words, a molecule of potassium bichromate has given up three atoms of oxygen for oxidation purposes; i.e., a molecular weight in grams of the bichromate (294.2) will furnish 3 X 16 or 48 grams of oxygen for oxidation purposes. As this 48 grams is six times 8 grams, the basis of the system, the normal solution of potassium bichromate should contain per liter one sixth of 294.2 grams or 49.03 grams. A further inspection of the dissected compounds above shows that six molecules of FeO.SO_{3} were required to react with the three atoms of oxygen from the bichromate. From the two equations 3H_{2} + 3O --> 3H_{2}O 6(FeO.SO_{3}) + 3O --> 3(Fe_{2}O_{3}.3SO_{3}) it is plain that one molecule of ferrous sulphate is equivalent to one atom of hydrogen in reducing power; therefore one molecular weight in grams of ferrous sulphate (151.9) is equivalent to 1 gram of hydrogen. Since the ferrous sulphate crystalline form has the formula FeSO_{4}.7H_{2}O, a normal reducing solution of this crystalline salt should contain 277.9 grams per liter. PREPARATION OF SOLUTIONS !Approximate Strength 0.1 N! It is possible to purify commercial potassium bichromate by recrystallization from hot water. It must then be dried and cautiously heated to fusion to expel the last traces of moisture, but not sufficiently high to expel any oxygen. The pure salt thus prepared, may be weighed out directly, dissolved, and the solution diluted in a graduated flask to a definite volume. In this case no standardization is made, as the normal value can be calculated directly. It is, however, more generally customary to standardize a solution of the commercial salt by comparison with some substance of definite composition, as described below. PROCEDURE.--Pulverize about 5 grams of potassium bichromate of good quality. Dissolve the bichromate in distilled water, transfer the solution to a liter bottle, and dilute to approximately 1000 cc. Shake thoroughly until the solution is uniform. To prepare the solution of the reducing agent, pulverize about 28 grams of ferrous sulphate (FeSO_{4}.7H_{2}O) or about 40 grams of ferrous ammonium sulphate (FeSO_{4}.(NH_{4})_{2}SO_{4}.6H_{2}O) and dissolve in distilled water containing 5 cc. of concentrated sulphuric acid. Transfer the solution to a liter bottle, add 5 cc. concentrated sulphuric acid, make up to about 1000 cc. and shake vigorously to insure uniformity. INDICATOR SOLUTION No indicator is known which, like methyl orange, can be used within the solution, to show when the oxidation process is complete. Instead, an outside indicator solution is employed to which drops of the titrated solution are transferred for testing. The reagent used is potassium ferricyanide, which produces a blue precipitate (or color) with ferrous compounds as long as there are unoxidized ferrous ions in the titrated solution. Drops of the indicator solution are placed upon a glazed porcelain tile, or upon white cardboard which has been coated with paraffin to render it waterproof, and drops of the titrated solution are transferred to the indicator on the end of a stirring rod. When the oxidation is nearly completed only very small amounts of the ferrous compounds remain unoxidized and the reaction with the indicator is no longer instantaneous. It is necessary to allow a brief time to elapse before determining that no blue color is formed. Thirty seconds is a sufficient interval, and should be adopted throughout the analytical procedure. If left too long, the combined effect of light and dust from the air will cause a reduction of the ferric compounds already formed and a resultant blue will appear which misleads the observer with respect to the true end-point. The indicator solution must be highly diluted, otherwise its own color interferes with accurate observation. Prepare a fresh solution, as needed each day, by dissolving a crystal of potassium ferricyanide about the size of a pin's head in 25 cc. of distilled water. The salt should be carefully tested with ferric chloride for the presence of ferrocyanides, which give a blue color with ferric salts. In case of need, the ferricyanide can be purified by adding to its solution a little bromine water and recrystallizing the compound. COMPARISON OF OXIDIZING AND REDUCING SOLUTIONS PROCEDURE.--Fill one burette with each of the solutions, observing the general procedure with respect to cleaning and rinsing already prescribed. The bichromate solution is preferably to be placed in a glass-stoppered burette. Run out from a burette into a beaker of about 300 cc. capacity nearly 40 cc. of the ferrous solution, add 15 cc. of dilute hydrochloric acid (sp. gr. 1.12) and 150 cc. of water and run in the bichromate solution from another burette. Since both solutions are approximately tenth-normal, 35 cc. of the bichromate solution may be added without testing. Test at that point by removing a very small drop of the iron solution on the end of a stirring rod, mixing it with a drop of indicator on the tile (Note 1). If a blue precipitate appears at once, 0.5 cc. of the bichromate solution may be added before testing again. The stirring rod which has touched the indicator should be dipped in distilled water before returning it to the iron solution. As soon as the blue appears to be less intense, add the bichromate solution in small portions, finally a single drop at a time, until the point is reached at which no blue color appears after the lapse of thirty seconds from the time of mixing solution and indicator. At the close of the titration a large drop of the iron solution should be taken for the test. To determine the end-point beyond any question, as soon as the thirty seconds have elapsed remove another drop of the solution of the same size as that last taken and mix it with the indicator, placing it beside the last previous test. If this last previous test shows a blue tint in comparison with the fresh mixture, the end-point has not been reached; if no difference can be noted the reaction is complete. Should the end-point be overstepped, a little more of the ferrous solution may be added and the end-point definitely fixed. From the volumes of the solutions used, after applying corrections for burette readings, and, if need be, for the temperature of solutions, calculate the value of the ferrous solution in terms of the oxidizing solution. [Note 1: The accuracy of the work may be much impaired by the removal of unnecessarily large quantities of solution for the tests. At the beginning of the titration, while much ferrous iron is still present, the end of the stirring rod need only be moist with the solution; but at the close of the titration drops of considerable size may properly be taken for the final tests. The stirring rod should be washed to prevent transfer of indicator to the main solution. This cautious removal of solution does not seriously affect the accuracy of the determination, as it will be noted that the volume of the titrated solution is about 200 cc. and the portions removed are very small. Moreover, if the procedure is followed as prescribed, the concentration of unoxidized iron decreases very rapidly as the titration is carried out so that when the final tests are made, though large drops may be taken, the amount of ferrous iron is not sufficient to produce any appreciable error in results. If the end-point is determined as prescribed, it can be as accurately fixed as that of other methods; and if a ferrous solution is at hand, the titration need consume hardly more time than that of the permanganate process to be described later on.] STANDARDIZATION OF POTASSIUM BICHROMATE SOLUTIONS !Selection of a Standard! A substance which will serve satisfactorily as a standard for oxidizing solutions must possess certain specific properties: It must be of accurately known composition and definite in its behavior as a reducing agent, and it must be permanent against oxidation in the air, at least for considerable periods. Such standards may take the form of pure crystalline salts, such as ferrous ammonium sulphate, or may be in the form of iron wire or an iron ore of known iron content. It is not necessary that the standard should be of 100 per cent purity, provided the content of the active reducing agent is known and no interfering substances are present. The two substances most commonly used as standards for a bichromate solution are ferrous ammonium sulphate and iron wire. A standard wire is to be purchased in the market which answers the purpose well, and its iron content may be determined for each lot purchased by a number of gravimetric determinations. It may best be preserved in jars containing calcium chloride, but this must not be allowed to come into contact with the wire. It should, however, even then be examined carefully for rust before use. If pure ferrous ammonium sulphate is used as the standard, clear crystals only should be selected. It is perhaps even better to determine by gravimetric methods once for all the iron content of a large commercial sample which has been ground and well mixed. This salt is permanent over long periods if kept in stoppered containers. STANDARDIZATION PROCEDURE.--Weigh out two portions of iron wire of about 0.24-0.26 gram each, examining the wire carefully for rust. It should be handled and wiped with filter paper (not touched by the fingers), should be weighed on a watch-glass, and be bent in such a way as not to interfere with the movement of the balance. Place 30 cc. of hydrochloric acid (sp. gr. 1.12) in each of two 300 cc. Erlenmeyer flasks, cover them with watch-glasses, and bring the acid just to boiling. Remove them from the flame and drop in the portions of wire, taking great care to avoid loss of liquid during solution. Boil for two or three minutes, keeping the flasks covered (Note 1), then wash the sides of the flasks and the watch-glass with a little water and add stannous chloride solution to the hot liquid !from a dropper! until the solution is colorless, but avoid more than a drop or two in excess (Note 2). Dilute with 150 cc. of water and cool !completely!. When cold, add rapidly about 30 cc. of mercuric chloride solution. Allow the solutions to stand about three minutes and then titrate without further delay (Note 3), add about 35 cc. of the standard solution at once and finish the titration as prescribed above, making use of the ferrous solution if the end-point should be passed. From the corrected volumes of the bichromate solution required to oxidize the iron actually know to be present in the wire, calculate the relation of the standard solution to the normal. Repeat the standardization until the results are concordant within at least two parts in one thousand. [Note 1: The hydrochloric acid is added to the ferrous solution to insure the presence of at least sufficient free acid for the titration, as required by the equation on page 48. The solution of the wire in hot acid and the short boiling insure the removal of compounds of hydrogen and carbon which are formed from the small amount of carbon in the iron. These might be acted upon by the bichromate if not expelled.] [Note 2: It is plain that all the iron must be reduced to the ferrous condition before the titration begins, as some oxidation may have occurred from the oxygen of the air during solution. It is also evident that any excess of the agent used to reduce the iron must be removed; otherwise it will react with the bichromate added later. The reagents available for the reduction of iron are stannous chloride, sulphurous acid, sulphureted hydrogen, and zinc; of these stannous chloride acts most readily, the completion of the reaction is most easily noted, and the excess of the reagent is most readily removed. The latter object is accomplished by oxidation to stannic chloride by means of mercuric chloride added in excess, as the mercuric salts have no effect upon ferrous iron or the bichromate. The reactions involved are: 2FeCl_{3} + SnCl_{2} --> 2FeCl_{2} + SnCl_{4} SnCl_{2} + 2HgCl_{2} --> SnCl_{4} + 2HgCl The mercurous chloride is precipitated. It is essential that the solution should be cold and that the stannous chloride should not be present in great excess, otherwise a secondary reaction takes place, resulting in the reduction of the mercurous chloride to metallic mercury: SnCl_{2} + 2HgCl --> SnCl_{4} + 2Hg. The occurrence of this secondary reaction is indicated by the darkening of the precipitate; and, since potassium bichromate oxidizes this mercury slowly, solutions in which it has been precipitated are worthless as iron determinations.] [Note 3: The solution should be allowed to stand about three minutes after the addition of mercuric chloride to permit the complete deposition of mercurous chloride. It should then be titrated without delay to avoid possible reoxidation of the iron by the oxygen of the air.] DETERMINATION OF IRON IN LIMONITE PROCEDURE.--Grind the mineral (Note 1) to a fine powder. Weigh out accurately two portions of about 0.5 gram (Note 2) into porcelain crucibles; heat these crucibles to dull redness for ten minutes, allow them to cool, and place them, with their contents, in beakers containing 30 cc. of dilute hydrochloric acid (sp. gr. 1.12). Heat at a temperature just below boiling until the undissolved residue is white or until solvent action has ceased. If the residue is white, or known to be free from iron, it may be neglected and need not be removed by filtration. If a dark residue remains, collect it on a filter, wash free from hydrochloric acid, and ignite the filter in a platinum crucible (Note 3). Mix the ash with five times its weight of sodium carbonate and heat to fusion; cool, and disintegrate the fused mass with boiling water in the crucible. Unite this solution and precipitate (if any) with the acid solution, taking care to avoid loss by effervescence. Wash out the crucible, heat the acid solution to boiling, add stannous chloride solution until it is colorless, avoiding a large excess (Note 4); cool, and when !cold!, add 40 cc. of mercuric chloride solution, dilute to 200 cc., and proceed with the titration as already described. From the standardization data already obtained, and the known weight of the sample, calculate the percentage of iron (Fe) in the limonite. [Note 1: Limonite is selected as a representative of iron ores in general. It is a native, hydrated oxide of iron. It frequently occurs in or near peat beds and contains more or less organic matter which, if brought into solution, would be acted upon by the potassium bichromate. This organic matter is destroyed by roasting. Since a high temperature tends to lessen the solubility of ferric oxide, the heat should not be raised above low redness.] [Note 2: It is sometimes advantageous to dissolve a large portion--say 5 grams--and to take one tenth of it for titration. The sample will then represent more closely the average value of the ore.] [Note 3: A platinum crucible may be used for the roasting of the limonite and must be used for the fusion of the residue. When used, it must not be allowed to remain in the acid solution of ferric chloride for any length of time, since the platinum is attacked and dissolved, and the platinic chloride is later reduced by the stannous chloride, and in the reduced condition reacts with the bichromate, thus introducing an error. It should also be noted that copper and antimony interfere with the determination of iron by the bichromate process.] [Note 4: The quantity of stannous chloride required for the reduction of the iron in the limonite will be much larger than that added to the solution of iron wire, in which the iron was mainly already in the ferrous condition. It should, however, be added from a dropper to avoid an unnecessary excess.] DETERMINATION OF CHROMIUM IN CHROME IRON ORE PROCEDURE.--Grind the chrome iron ore (Note 1) in an agate mortar until no grit is perceptible under the pestle. Weigh out two portions of 0.5 gram each into iron crucibles which have been scoured inside until bright (Note 2). Weigh out on a watch-glass (Note 3), using the rough balances, 5 grams of dry sodium peroxide for each portion, and pour about three quarters of the peroxide upon the ore. Mix ore and flux by thorough stirring with a dry glass rod. Then cover the mixture with the remainder of the peroxide. Place the crucible on a triangle and raise the temperature !slowly! to the melting point of the flux, using a low flame, and holding the lamp in the hand (Note 4). Maintain the fusion for five minutes, and stir constantly with a stout iron wire, but do not raise the temperature above moderate redness (Notes 5 and 6). Allow the crucible to cool until it can be comfortably handled (Note 7) and then place it in a 300 cc. beaker, and cover it with distilled water (Note 8). The beaker must be carefully covered to avoid loss during the disintegration of the fused mass. When the evolution of gas ceases, rinse off and remove the crucible; then heat the solution !while still alkaline! to boiling for fifteen minutes. Allow the liquid to cool for a few minutes; then acidify with dilute sulphuric acid (1:5), adding 10 cc. in excess of the amount necessary to dissolve the ferric hydroxide (Note 9). Dilute to 200 cc., cool, add from a burette an excess of a standard ferrous solution, and titrate for the excess with a standard solution of potassium bichromate, using the outside indicator (Note 10). From the corrected volumes of the two standard solutions, and their relations to normal solutions, calculate the percentage of chromium in the ore. [Note 1: Chrome iron ore is essentially a ferrous chromite, or combination of FeO and Cr_{2}O_{3}. It must be reduced to a state of fine subdivision to ensure a prompt reaction with the flux.] [Note 2: The scouring of the iron crucible is rendered much easier if it is first heated to bright redness and plunged into cold water. In this process oily matter is burned off and adhering scale is caused to chip off when the hot crucible contracts rapidly in the cold water.] [Note 3: Sodium peroxide must be kept off of balance pans and should not be weighed out on paper, as is the usual practice in the rough weighing of chemicals. If paper to which the peroxide is adhering is exposed to moist air it is likely to take fire as a result of the absorption of moisture, and consequent evolution of heat and liberation of oxygen.] [Note 4: The lamp should never be allowed to remain under the crucible, as this will raise the temperature to a point at which the crucible itself is rapidly attacked by the flux and burned through.] [Note 5: The sodium peroxide acts as both a flux and an oxidizing agent. The chromic oxide is dissolved by the flux and oxidized to chromic anhydride (CrO_{3}) which combines with the alkali to form sodium chromate. The iron is oxidized to ferric oxide.] [Note 6: The sodium peroxide cannot be used in porcelain, platinum, or silver crucibles. It attacks iron and nickel as well; but crucibles made from these metals may be used if care is exercised to keep the temperature as low as possible. Preference is here given to iron crucibles, because the resulting ferric hydroxide is more readily brought into solution than the nickelic oxide from a nickel crucible. The peroxide must be dry, and must be protected from any admixture of dust, paper, or of organic matter of any kind, otherwise explosions may ensue.] [Note 7: When an iron crucible is employed it is desirable to allow the fusion to become nearly cold before it is placed in water, otherwise scales of magnetic iron oxide may separate from the crucible, which by slowly dissolving in acid form ferrous sulphate, which reduces the chromate.] [Note 8: Upon treatment with water the chromate passes into solution, the ferric hydroxide remains undissolved, and the excess of peroxide is decomposed with the evolution of oxygen. The subsequent boiling insures the complete decomposition of the peroxide. Unless this is complete, hydrogen peroxide is formed when the solution is acidified, and this reacts with the bichromate, reducing it and introducing a serious error.] [Note 9: The addition of the sulphuric acid converts the sodium chromate to bichromate, which behaves exactly like potassium bichromate in acid solution.] [Note 10: If a standard solution of a ferrous salt is not at hand, a weight of iron wire somewhat in excess of the amount which would be required if the chromite were pure FeO.Cr_{2}O_{3} may be weighed out and dissolved in sulphuric acid; after reduction of all the iron by stannous chloride and the addition of mercuric chloride, this solution may be poured into the chromate solution and the excess of iron determined by titration with standard bichromate solution.] PERMANGANATE PROCESS FOR THE DETERMINATION OF IRON Potassium permanganate oxidizes ferrous salts in cold, acid solution promptly and completely to the ferric condition, while in hot acid solution it also enters into a definite reaction with oxalic acid, by which the latter is oxidized to carbon dioxide and water. The reactions involved are these: 10FeSO_{4} + 2KMnO_{4} + 8H_{2}S_{4} --> 5Fe_{2}(SO_{4})_{3} + K_{2}SO_{4} + 2MnSO_{4} + 8H_{2}O 5C_{2}H_{2}O_{4}(2H_{2}O) + 2KMnO_{4} +3H_{2}SO_{4} --> K_{2}SO_{4} + 2MnSO_{4} + 10CO_{2} + 1 H_{2}O. These are the fundamental reactions upon which the extensive use of potassium permanganate depends; but besides iron and oxalic acid the permanganate enters into reaction with antimony, tin, copper, mercury, and manganese (the latter only in neutral solution), by which these metals are changed from a lower to a higher state of oxidation; and it also reacts with sulphurous acid, sulphureted hydrogen, nitrous acid, ferrocyanides, and most soluble organic bodies. It should be noted, however, that very few of these organic compounds react quantitatively with the permanganate, as is the case with oxalic acid and the oxalates. Potassium permanganate is acted upon by hydrochloric acid; the action is rapid in hot or concentrated solution (particularly in the presence of iron salts, which appear to act as catalyzers, increasing the velocity of the reaction), but slow in cold, dilute solutions. However, the greater solubility of iron compounds in hydrochloric acid makes it desirable to use this acid as a solvent, and experiments made with this end in view have shown that in cold, dilute hydrochloric acid solution, to which considerable quantities of manganous sulphate and an excess of phosphoric acid have been added, it is possible to obtain satisfactory results. It is also possible to replace the hydrochloric acid by evaporating the solutions with an excess of sulphuric acid until the latter fumes. This procedure is somewhat more time-consuming, but the end-point of the permanganate titration is more permanent. Both procedures are described below. Potassium permanganate has an intense coloring power, and since the solution resulting from the oxidation of the iron and the reduction of the permanganate is colorless, the latter becomes its own indicator. The slightest excess is indicated with great accuracy by the pink color of the solution. PREPARATION OF A STANDARD SOLUTION !Approximate Strength 0.1 N! A study of the reactions given above which represent the oxidation of ferrous compounds by potassium permanganate, shows that there are 2 molecules of KMnO_{4} and 10 molecules of FeSO_{4} on the left-hand side, and 2 molecules of MnSO_{4} and 5 molecules of Fe_{2}(SO_{4})_{5} on the right-hand side. Considering only these compounds, and writing the formulas in such a way as to show the oxides of the elements in each, the equation becomes: K_{2}O.Mn_{2}O_{7} + 10(FeO.SO_{3}) --> K_{2}O.SO_{3} + 2(MnO.SO_{3}) + 5(Fe_{2}O_{3}.3SO_{3}). From this it appears that two molecules of KMnO_{4} (or 316.0 grams) have given up five atoms (or 80 grams) of oxygen to oxidize the ferrous compound. Since 8 grams of oxygen is the basis of normal oxidizing solutions and 80 grams of oxygen are supplied by 316.0 grams of KMnO_{4}, the normal solution of the permanganate should contain, per liter, 316.0/10 grams, or 31.60 grams (Note 1). The preparation of an approximately tenth-normal solution of the reagent may be carried out as follows: PROCEDURE.--Dissolve about 3.25 grams of potassium permanganate crystals in approximately 1000 cc. of distilled water in a large beaker, or casserole. Heat slowly and when the crystals have dissolved, boil the solution for 10-15 minutes. Cover the solution with a watch-glass; allow it to stand until cool, or preferably over night. Filter the solution through a layer of asbestos. Transfer the filtrate to a liter bottle and mix thoroughly (Note 2). [Note 1: The reactions given on page 61 are those which take place in the presence of an excess of acid. In neutral solutions the reduction of the permanganate is less complete, and, under these conditions, two gram-molecular weights of KMnO_{4} will furnish only 48 grams of oxygen. A normal solution for use under these conditions should, therefore, contain 316.0/6 grams, or 52.66 grams.] [Note 2: Potassium permanganate solutions are not usually stable for long periods, and change more rapidly when first prepared than after standing some days. This change is probably caused by interaction with the organic matter contained in all distilled water, except that redistilled from an alkaline permanganate solution. The solutions should be protected from light and heat as far as possible, since both induce decomposition with a deposition of manganese dioxide, and it has been shown that decomposition proceeds with considerable rapidity, with the evolution of oxygen, after the dioxide has begun to form. As commercial samples of the permanganate are likely to be contaminated by the dioxide, it is advisable to boil and filter solutions through asbestos before standardization, as prescribed above. Such solutions are relatively stable.] COMPARISON OF PERMANGANATE AND FERROUS SOLUTIONS PROCEDURE.--Fill a glass-stoppered burette with the permanganate solution, observing the usual precautions, and fill a second burette with the ferrous sulphate solution prepared for use with the potassium bichromate. The permanganate solution cannot be used in burettes with rubber tips, as a reduction takes place upon contact with the rubber. The solution has so deep a color that the lower line of the meniscus cannot be detected; readings must therefore be made from the upper edge. Run out into a beaker about 40 cc. of the ferrous solution, dilute to about 100 cc., add 10 cc. of dilute sulphuric acid, and run in the permanganate solution to a slight permanent pink. Repeat, until the ratio of the two solutions is satisfactorily established. STANDARDIZATION OF A POTASSIUM PERMANGANATE SOLUTION !Selection of a Standard! Commercial potassium permanganate is rarely sufficiently pure to admit of its direct weighing as a standard. On this account, and because of the uncertainties as to the permanence of its solutions, it is advisable to standardize them against substances of known value. Those in most common use are iron wire, ferrous ammonium sulphate, sodium oxalate, oxalic acid, and some other derivatives of oxalic acid. With the exception of sodium oxalate, these all contain water of crystallization which may be lost on standing. They should, therefore, be freshly prepared, and with great care. At present, sodium oxalate is considered to be one of the most satisfactory standards. !Method A! !Iron Standards! The standardization processes employed when iron or its compounds are selected as standards differ from those applicable in connection with oxalate standards. The procedure which immediately follows is that in use with iron standards. As in the case of the bichromate process, it is necessary to reduce the iron completely to the ferrous condition before titration. The reducing agents available are zinc, sulphurous acid, or sulphureted hydrogen. Stannous chloride may also be used when the titration is made in the presence of hydrochloric acid. Since the excess of both the gaseous reducing agents can only be expelled by boiling, with consequent uncertainty regarding both the removal of the excess and the reoxidation of the iron, zinc or stannous chlorides are the most satisfactory agents. For prompt and complete reduction it is essential that the iron solution should be brought into ultimate contact with the zinc. This is brought about by the use of a modified Jones reductor, as shown in Figure 1. This reductor is a standard apparatus and is used in other quantitative processes. [Illustration: Fig. 1] The tube A has an inside diameter of 18 mm. and is 300 mm. long; the small tube has an inside diameter of 6 mm. and extends 100 mm. below the stopcock. At the base of the tube A are placed some pieces of broken glass or porcelain, covered by a plug of glass wool about 8 mm. thick, and upon this is placed a thin layer of asbestos, such as is used for Gooch filters, 1 mm. thick. The tube is then filled with the amalgamated zinc (Note 1) to within 50 mm. of the top, and on the zinc is placed a plug of glass wool. If the top of the tube is not already shaped like the mouth of a thistle-tube (B), a 60 mm. funnel is fitted into the tube with a rubber stopper and the reductor is connected with a suction bottle, F. The bottle D is a safety bottle to prevent contamination of the solution by water from the pump. After preparation for use, or when left standing, the tube A should be filled with water, to prevent clogging of the zinc. [Note 1: The use of fine zinc in the reductor is not necessary and tends to clog the tube. Particles which will pass a 10-mesh sieve, but are retained by one of 20 meshes to the inch, are most satisfactory. The zinc can be amalgamated by stirring or shaking it in a mixture of 25 cc. of normal mercuric chloride solution, 25 cc. of hydrochloric acid (sp. gr. 1.12) and 250 cc. of water for two minutes. The solution should then be poured off and the zinc thoroughly washed. It is then ready for bottling and preservation under water. A small quantity of glass wool is placed in the neck of the funnel to hold back foreign material when the reductor is in use.] STANDARDIZATION PROCEDURE.--Weigh out into Erlenmeyer flasks two portions of iron wire of about 0.25 gram each. Dissolve these in hot dilute sulphuric acid (5 cc. of concentrated acid and 100 cc. of water), using a covered flask to avoid loss by spattering. Boil the solution for two or three minutes after the iron has dissolved to remove any volatile hydrocarbons. Meanwhile prepare the reductor for use as follows: Connect the vacuum bottle with the suction pump and pour into the funnel at the top warm, dilute sulphuric acid, prepared by adding 5 cc. of concentrated sulphuric acid to 100 cc. of distilled water. See that the stopcock (C) is open far enough to allow the acid to run through slowly. Continue to pour in acid until 200 cc. have passed through, then close the stopcock !while a small quantity of liquid is still left in the funnel!. Discard the filtrate, and again pass through 100 cc. of the warm, dilute acid. Test this with the permanganate solution. A single drop should color it permanently; if it does not, repeat the washing, until assured that the zinc is not contaminated with appreciable quantities of reducing substances. Be sure that no air enters the reductor (Note 1). Pour the iron solution while hot (but not boiling) through the reductor at a rate not exceeding 50 cc. per minute (Notes 2 and 3). Wash out the beaker with dilute sulphuric acid, and follow the iron solution without interruption with 175 cc. of the warm acid and finally with 75 cc. of distilled water, leaving the funnel partially filled. Remove the filter bottle and cool the solution quickly under the water tap (Note 4), avoiding unnecessary exposure to the oxygen of the air. Add 10 cc. of dilute sulphuric acid and titrate to a faint pink with the permanganate solution, adding it directly to the contents of the vacuum flask. Should the end-point be overstepped, the ferrous sulphate solution may be added. From the volume of the solution required to oxidize the iron in the wire, calculate the relation to the normal of the permanganate solution. The duplicate results should be concordant within two parts in one thousand. [Note 1: The funnel of the reductor must never be allowed to empty. If it is left partially filled with water the reductor is ready for subsequent use after a very little washing; but a preliminary test is always necessary to safeguard against error. If more than a small drop of permanganate solution is required to color 100 cc. of the dilute acid after the reductor is well washed, an allowance must be made for the iron in the zinc. !Great care! must be used to prevent the access of air to the reductor after it has been washed out ready for use. If air enters, hydrogen peroxide forms, which reacts with the permanganate, and the results are worthless.] [Note 2: The iron is reduced to the ferrous condition by contact with the zinc. The active agent may be considered to be !nascent! hydrogen, and it must be borne in mind that the visible bubbles are produced by molecular hydrogen, which is without appreciable effect upon ferric iron. The rate at which the iron solution passes through the zinc should not exceed that prescribed, but the rate may be increased somewhat when the wash-water is added. It is well to allow the iron solution to run nearly, but not entirely, out of the funnel before the wash-water is added. If it is necessary to interrupt the process, the complete emptying of the funnel can always be avoided by closing the stopcock. It is also possible to reduce the iron by treatment with zinc in a flask from which air is excluded. The zinc must be present in excess of the quantity necessary to reduce the iron and is finally completely dissolved. This method is, however, less convenient and more tedious than the use of the reductor.] [Note 3: The dilute sulphuric acid for washing must be warmed ready for use before the reduction of the iron begins, and it is of the first importance that the volume of acid and of wash-water should be measured, and the volume used should always be the same in the standardizations and all subsequent analyses.] [Note 4: The end-point is more permanent in cold than hot solutions, possibly because of a slight action of the permanganate upon the manganous sulphate formed during titration. If the solution turns brown, it is an evidence of insufficient acid, and more should be immediately added. The results are likely to be less accurate in this case, however, as a consequence of secondary reactions between the ferrous iron and the manganese dioxide thrown down. It is wiser to discard such results and repeat the process.] [Note 5: The potassium permanganate may, of course, be diluted and brought to an exactly 0.1 N solution from the data here obtained. The percentage of iron in the iron wire must be taken into account in all calculations.] !Method B! !Oxalate Standards! PROCEDURE.--Weigh out two portions of pure sodium oxalate of 0.25-0.3 gram each into beakers of about 600 cc. capacity. Add about 400 cc. of boiling water and 20 cc. of manganous sulphate solution (Note 1). When the solution of the oxalate is complete, heat the liquid, if necessary, until near its boiling point (70-90°C.) and run in the standard permanganate solution drop by drop from a burette, stirring constantly until an end-point is reached (Note 2). Make a blank test with 20 cc. of manganous sulphate solution and a volume of distilled water equal to that of the titrated solution to determine the volume of the permanganate solution required to produce a very slight pink. Deduct this volume from the amount of permanganate solution used in the titration. From the data obtained, calculate the relation of the permanganate solution to the normal. The reaction involved is: 5Na_{2}C_{2}O_{4} + 2KMnO_{4} + 8H_{2}SO_{4} --> 5Na_{2}SO_{4} + K_{2}SO_{4} + 2MnSO_{4} + 10CO_{2} + 8H_{2}O [Note 1: The manganous sulphate titrating solution is made by dissolving 20 grams of MnSO_{4} in 200 cubic centimeters of water and adding 40 cc. of concentrated sulphuric acid (sp. gr. 1.84) and 40 cc. or phosphoric acid (85%).] [Note 2: The reaction between oxalates and permanganates takes place quantitatively only in hot acid solutions. The temperatures must not fall below 70°C.] DETERMINATION OF IRON IN LIMONITE !Method A! The procedures, as here prescribed, are applicable to iron ores in general, provided these ores contain no constituents which are reduced by zinc or stannous chloride and reoxidized by permanganates. Many iron ores contain titanium, and this element among others does interfere with the determination of iron by the process described. If, however, the solutions of such ores are treated with sulphureted hydrogen or sulphurous acid, instead of zinc or stannous chloride to reduce the iron, and the excess reducing agent removed by boiling, an accurate determination of the iron can be made. PROCEDURE.--Grind the mineral to a fine powder. Weigh out two portions of about 0.5 gram each into small porcelain crucibles. Roast the ore at dull redness for ten minutes (Note 1), allow the crucibles to cool, and place them and their contents in casseroles containing 30 cc. of dilute hydrochloric acid (sp. gr. 1.12). Proceed with the solution of the ore, and the treatment of the residue, if necessary, exactly as described for the bichromate process on page 56. When solution is complete, add 6 cc. of concentrated sulphuric acid to each casserole, and evaporate on the steam bath until the solution is nearly colorless (Note 2). Cover the casseroles and heat over the flame of the burner, holding the casserole in the hand and rotating it slowly to hasten evaporation and prevent spattering, until the heavy white fumes of sulphuric anhydride are freely evolved (Note 3). Cool the casseroles, add 100 cc. of water (measured), and boil gently until the ferric sulphate is dissolved; pour the warm solution through the reductor which has been previously washed; proceed as described under standardization, taking pains to use the same volume and strength of acid and the same volume of wash-water as there prescribed, and titrate with the permanganate solution in the reductor flask, using the ferrous sulphate solution if the end-point should be overstepped. From the corrected volume of permanganate solution used, calculate the percentage of iron (Fe) in the limonite. [Note 1: The preliminary roasting is usually necessary because, even though the sulphuric acid would subsequently char the carbonaceous matter, certain nitrogenous bodies are not thereby rendered insoluble in the acid, and would be oxidized by the permanganate.] [Note 2: The temperature of the steam bath is not sufficient to volatilize sulphuric acid. Solutions may, therefore, be left to evaporate overnight without danger of evaporation to dryness.] [Note 3: The hydrochloric acid, both free and combined, is displaced by the less volatile sulphuric acid at its boiling point. Ferric sulphate separates at this point, since there is no water to hold it in solution and care is required to prevent bumping. The ferric sulphate usually has a silky appearance and is easily distinguished from the flocculent silica which often remains undissolved.] !Zimmermann-Reinhardt Procedure! !Method (B)! PROCEDURE.--Grind the mineral to a fine powder. Weigh out two portions of about 0.5 gram each into small porcelain crucibles. Proceed with the solution of the ore, treat the residue, if necessary, and reduce the iron by the addition of stannous chloride, followed by mercuric chloride, as described for the bichromate process on page 56. Dilute the solution to about 400 cc. with cold water, add 10 cc. of the manganous sulphate titrating solution (Note 1, page 68) and titrate with the standard potassium permanganate solution to a faint pink (Note 1). From the standardization data already obtained calculate the percentage of iron (Fe) in the limonite. [Note 1: It has already been noted that hydrochloric acid reacts slowly in cold solutions with potassium permanganate. It is, however, possible to obtain a satisfactory, although somewhat fugitive end-point in the presence of manganous sulphate and phosphoric acid. The explanation of the part played by these reagents is somewhat obscure as yet. It is possible that an intermediate manganic compound is formed which reacts rapidly with the ferrous compounds--thus in effect catalyzing the oxidizing process. While an excess of hydrochloric acid is necessary for the successful reduction of the iron by stannous chloride, too large an amount should be avoided in order to lessen the chance of reduction of the permanganate by the acid during titration.] DETERMINATION OF THE OXIDIZING POWER OF PYROLUSITE INDIRECT OXIDATION Pyrolusite, when pure, consists of manganese dioxide. Its value as an oxidizing agent, and for the production of chlorine, depends upon the percentage of MnO_{2} in the sample. This percentage is determined by an indirect method, in which the manganese dioxide is reduced and dissolved by an excess of ferrous sulphate or oxalic acid in the presence of sulphuric acid, and the unused excess determined by titration with standard permanganate solution. PROCEDURE.--Grind the mineral in an agate mortar until no grit whatever can be detected under the pestle (Note 1). Transfer it to a stoppered weighing-tube, and weigh out two portions of about 0.5 gram into beakers (400-500 cc.) Read Note 2, and then calculate in each case the weight of oxalic acid (H_{2}C_{2}O_{4}.2H_{2}O) required to react with the weights of pyrolusite taken. The reaction involved is MnO_{2} + H_{2}C_{2}O_{4}(2H_{2}O) + H_{2}SO_{4} --> MnSO_{4} + 2CO_{2} + 4H_{2}O. Weigh out about 0.2 gram in excess of this quantity of !pure! oxalic acid into the corresponding beakers, weighing the acid accurately and recording the weight in the notebook. Pour into each beaker 25 cc. of water and 50 cc. of dilute sulphuric acid (1:5), cover and warm the beaker and its contents gently until the evolution of carbon dioxide ceases (Note 3). If a residue remains which is sufficiently colored to obscure the end-reaction of the permanganate, it must be removed by filtration. Finally, dilute the solution to 200-300 cc., heat the solution to a temperature just below boiling, add 15 cc. of a manganese sulphate solution and while hot, titrate for the excess of the oxalic acid with standard permanganate solution (Notes 4 and 5). From the corrected volume of the solution required, calculate the amount of oxalic acid undecomposed by the pyrolusite; subtract this from the total quantity of acid used, and calculate the weight of manganese dioxide which would react with the balance of the acid, and from this the percentage in the sample. [Note 1: The success of the analysis is largely dependent upon the fineness of the powdered mineral. If properly ground, solution should be complete in fifteen minutes or less.] [Note 2: A moderate excess of oxalic acid above that required to react with the pyrolusite is necessary to promote solution; otherwise the residual quantity of oxalic acid would be so small that the last particles of the mineral would scarcely dissolve. It is also desirable that a sufficient excess of the acid should be present to react with a considerable volume of the permanganate solution during the titration, thus increasing the accuracy of the process. On the other hand, the excess of oxalic acid should not be so large as to react with more of the permanganate solution than is contained in a 50 cc. burette. If the pyrolusite under examination is known to be of high grade, say 80 per cent pure, or above the calculation of the oxalic acid needed may be based upon an assumption that the mineral is all MnO_{2}. If the quality of the mineral is unknown, it is better to weigh out three portions instead of two and to add to one of these the amount of oxalic prescribed, assuming complete purity of the mineral. Then run in the permanganate solution from a pipette or burette to determine roughly the amount required. If the volume exceeds the contents of a burette, the amount of oxalic acid added to the other two portions is reduced accordingly.] [Note 3: Care should be taken that the sides of the beaker are not overheated, as oxalic acid would be decomposed by heat alone if crystallization should occur on the sides of the vessel. Strong sulphuric acid also decomposes the oxalic acid. The dilute acid should, therefore, be prepared before it is poured into the beaker.] [Note 4: Ferrous ammonium sulphate, ferrous sulphate, or iron wire may be substituted for the oxalic acid. The reaction is then the following: 2 FeSO_{4} + MnO_{2} + 2H_{2}SO_{4} --> Fe_{2}(SO_{4})_{3} + 2H_{2}O The excess of ferrous iron may also be determined by titration with potassium bichromate, if desired. Care is required to prevent the oxidation of the iron by the air, if ferrous salts are employed.] [Note 5: The oxidizing power of pyrolusite may be determined by other volumetric processes, one of which is outlined in the following reactions: MnO_{2} + 4HCl --> MnCl_{2} + Cl_{2} + 2H_{2}O Cl_{2} + 2KI --> I_{2} + 2KCl I_{2} + 2Na_{2}S_{2}O_{3} --> Na_{2}S_{4}O_{6} + 2NaI. The chlorine generated by the pyrolusite is passed into a solution of potassium iodide. The liberated iodine is then determined by titration with sodium thiosulphate, as described on page 78. This is a direct process, although it involves three steps.] IODIMETRY The titration of iodine against sodium thiosulphate, with starch as an indicator, may perhaps be regarded as the most accurate of volumetric processes. The thiosulphate solution may be used in both acid and neutral solutions to measure free iodine and the latter may, in turn, serve as a measure of any substance capable of liberating iodine from potassium iodide under suitable conditions for titration, as, for example, in the process outlined in Note 5 on page 74. The fundamental reaction upon which iodometric processes are based is the following: I_{2} + 2 Na_{2}S_{2}O_{3} --> 2 NaI + Na_{2}S_{4}O_{6}. This reaction between iodine and sodium thiosulphate, resulting in the formation of the compound Na_{2}S_{4}O_{6}, called sodium tetrathionate, is quantitatively exact, and differs in that respect from the action of chlorine or bromine, which oxidize the thiosulphate, but not quantitatively. NORMAL SOLUTIONS OF IODINE AND SODIUM THIOSULPHATE If the formulas of sodium thiosulphate and sodium tetrathionate are written in a manner to show the atoms of oxygen associated with sulphur atoms in each, thus, 2(Na_{2}).S_{2}O_{2} and Na_{2}O.S_{4}O_{5}, it is plain that in the tetrathionate there are five atoms of oxygen associated with sulphur, instead of the four in the two molecules of the thiosulphate taken together. Although, therefore, the iodine contains no oxygen, the two atoms of iodine have, in effect, brought about the addition of one oxygen atoms to the sulphur atoms. That is the same thing as saying that 253.84 grams of iodine (I_{2}) are equivalent to 16 grams of oxygen; hence, since 8 grams of oxygen is the basis of normal solutions, 253.84/2 or 126.97 grams of iodine should be contained in one liter of normal iodine solution. By a similar course of reasoning the conclusion is reached that the normal solution of sodium thiosulphate should contain, per liter, its molecular weight in grams. As the thiosulphate in crystalline form has the formula Na_{2}S_{2}O_{3}.5H_{2}O, this weight is 248.12 grams. Tenth-normal or hundredth-normal solutions are generally used. PREPARATION OF STANDARD SOLUTIONS !Approximate Strength, 0.1 N! PROCEDURE.--Weigh out on the rough balances 13 grams of commercial iodine. Place it in a mortar with 18 grams of potassium iodide and triturate with small portions of water until all is dissolved. Dilute the solution to 1000 cc. and transfer to a liter bottle and mix thoroughly (Note 1).[1] [Footnote 1: It will be found more economical to have a considerable quantity of the solution prepared by a laboratory attendant, and to have all unused solutions returned to the common stock.] Weigh out 25 grams of sodium thiosulphate, dissolve it in water which has been previously boiled and cooled, and dilute to 1000 cc., also with boiled water. Transfer the solution to a liter bottle and mix thoroughly (Note 2). [Note 1: Iodine solutions react with water to form hydriodic acid under the influence of the sunlight, and even at low room temperatures the iodine tends to volatilize from solution. They should, therefore, be protected from light and heat. Iodine solutions are not stable for long periods under the best of conditions. They cannot be used in burettes with rubber tips, since they attack the rubber.] [Note 2: Sodium thiosulphate (Na_{2}S_{2}O_{3}.5H_{2}O) is rarely wholly pure as sold commercially, but may be purified by recrystallization. The carbon dioxide absorbed from the air by distilled water decomposes the salt, with the separation of sulphur. Boiled water which has been cooled out of contact with the air should be used in preparing solutions.] INDICATOR SOLUTION The starch solution for use as an indicator must be freshly prepared. A soluble starch is obtainable which serves well, and a solution of 0.5 gram of this starch in 25 cc. of boiling water is sufficient. The solution should be filtered while hot and is ready for use when cold. If soluble starch is not at hand, potato starch may be used. Mix about 1 gram with 5 cc. of cold water to a smooth paste, pour 150 cc. of !boiling! water over it, warm for a moment on the hot plate, and put it aside to settle. Decant the supernatant liquid through a filter and use the clear filtrate; 5 cc. of this solution are needed for a titration. The solution of potato starch is less stable than the soluble starch. The solid particles of the starch, if not removed by filtration, become so colored by the iodine that they are not readily decolorized by the thiosulphate (Note 1). [Note 1: The blue color which results when free iodine and starch are brought together is probably not due to the formation of a true chemical compound. It is regarded as a "solid solution" of iodine in starch. Although it is unstable, and easily destroyed by heat, it serves as an indicator for the presence of free iodine of remarkable sensitiveness, and makes the iodometric processes the most satisfactory of any in the field of volumetric analysis.] COMPARISON OF IODINE AND THIOSULPHATE SOLUTIONS PROCEDURE.--Place the solutions in burettes (the iodine in a glass-stoppered burette), observing the usual precautions. Run out 40 cc. of the thiosulphate solution into a beaker, dilute with 150 cc. of water, add 1 cc. to 2 cc. of the soluble starch solution, and titrate with the iodine to the appearance of the blue of the iodo-starch. Repeat until the ratio of the two solutions is established, remembering all necessary corrections for burettes and for temperature changes. STANDARDIZATION OF SOLUTIONS Commercial iodine is usually not sufficiently pure to permit of its use as a standard for thiosulphate solutions or the direct preparation of a standard solution of iodine. It is likely to contain, beside moisture, some iodine chloride, if chlorine was used to liberate the iodine when it was prepared. It may be purified by sublimation after mixing it with a little potassium iodide, which reacts with the iodine chloride, forming potassium chloride and setting free the iodine. The sublimed iodine is then dried by placing it in a closed container over concentrated sulphuric acid. It may then be weighed in a stoppered weighing-tube and dissolved in a solution of potassium iodide in a stoppered flask to prevent loss of iodine by volatilization. About 18 grams of the iodide and twelve grams of iodine per liter are required for an approximately tenth-normal solution. An iodine solution made from commercial iodine may also be standardized against arsenious oxide (As_{4}O_{6}). This substance also usually requires purification by sublimation before use. The substances usually employed for the standardization of a thiosulphate solution are potassium bromate and metallic copper. The former is obtainable in pure condition or may be easily purified by re-crystallization. Copper wire of high grade is sufficiently pure to serve as a standard. Both potassium bromate and cupric salts in solution will liberate iodine from an iodide, which is then titrated with the thiosulphate solution. The reactions involved are the following: (a) KBrO_{3} + 6KI + 3H_{2}SO_{4} --> KBr + 3I_{2} + 3K_{2}SO_{4} + 3H_{2}O, (b) 3Cu + 8HNO_{3} --> 3Cu(NO_{3})_{2} + 2NO + 4H_{2}O, 2Cu(NO_{3})_{2} + 4KI --> 2CuI + 4KNO_{3} + I_{2}. Two methods for the direct standardization of the sodium thiosulphate solution are here described, and one for the direct standardization of the iodine solution. !Method A! PROCEDURE.--Weigh out into 500 cc. beakers two portions of about 0.150-0.175 gram of potassium bromate. Dissolve each of these in 50 cc. of water, and add 10 cc. of a potassium iodide solution containing 3 grams of the salt in that volume (Note 1). Add to the mixture 10 cc. of dilute sulphuric acid (1 volume of sulphuric acid with 5 volumes of water), allow the solution to stand for three minutes, and dilute to 150 cc. (Note 2). Run in thiosulphate solution from a burette until the color of the liberated iodine is nearly destroyed, and then add 1 cc. or 2 cc. of starch solution, titrate to the disappearance of the iodo-starch blue, and finally add iodine solution until the color is just restored. Make a blank test for the amount of thiosulphate solution required to react with the iodine liberated by the iodate which is generally present in the potassium iodide solution, and deduct this from the total volume used in the titration. From the data obtained, calculate the relation of the thiosulphate solution to a normal solution, and subsequently calculate the similar value for the iodine solution. [Note 1:--Potassium iodide usually contains small amounts of potassium iodate as impurity which, when the iodide is brought into an acid solution, liberates iodine, just as does the potassium bromate used as a standard. It is necessary to determine the amount of thiosulphate which reacts with the iodine thus liberated by making a "blank test" with the iodide and acid alone. As the iodate is not always uniformly distributed throughout the iodide, it is better to make up a sufficient volume of a solution of the iodide for the purposes of the work in hand, and to make the blank test by using the same volume of the iodide solution as is added in the standardizing process. The iodide solution should contain about 3 grams of the salt in 10 cc.] [Note 2: The color of the iodo-starch is somewhat less satisfactory in concentrated solutions of the alkali salts, notably the iodides. The dilution prescribed obviates this difficulty.] !Method B! PROCEDURE.--Weigh out two portions of 0.25-0.27 gram of clean copper wire into 250 cc. Erlenmeyer flasks (Note 1). Add to each 5 cc. of concentrated nitric acid (sp. gr. 1.42) and 25 cc. of water, cover, and warm until solution is complete. Add 5 cc. of bromine water and boil until the excess of bromine is expelled. Cool, and add strong ammonia (sp. gr. 0.90) drop by drop until a deep blue color indicates the presence of an excess. Boil the solution until the deep blue is replaced by a light bluish green, or a brown stain appears on the sides of the flask (Note 2). Add 10 cc. of strong acetic acid (sp. gr. 1.04), cool under the water tap, and add a solution of potassium iodide (Note 3) containing about 3 grams of the salt, and titrate with thiosulphate solution until the color of the liberated iodine is nearly destroyed. Then add 1-2 cc. of freshly prepared starch solution, and add thiosulphate solution, drop by drop, until the blue color is discharged. From the data obtained, including the "blank test" of the iodide, calculate the relation of the thiosulphate solution to the normal. [Note 1: While copper wire of commerce is not absolutely pure, the requirements for its use as a conductor of electricity are such that the impurities constitute only a few hundredths of one per cent and are negligible for analytical purposes.] [Note 2: Ammonia neutralizes the free nitric acid. It should be added in slight excess only, since the excess must be removed by boiling, which is tedious. If too much ammonia is present when acetic acid is added, the resulting ammonium acetate is hydrolyzed, and the ammonium hydroxide reacts with the iodine set free.] [Note 3: A considerable excess of potassium iodide is necessary for the prompt liberation of iodine. While a large excess will do no harm, the cost of this reagent is so great that waste should be avoided.] !Method C! PROCEDURE.--Weigh out into 500 cc. beakers two portions of 0.175-0.200 gram each of pure arsenious oxide. Dissolve each of these in 10 cc. of sodium hydroxide solution, with stirring. Dilute the solutions to 150 cc. and add dilute hydrochloric acid until the solutions contain a few drops in excess, and finally add to each a concentrated solution of 5 grams of pure sodium bicarbonate (NaHCO_{3}) in water. Cover the beakers before adding the bicarbonate, to avoid loss. Add the starch solution and titrate with the iodine to the appearance of the blue of the iodo-starch, taking care not to pass the end-point by more than a few drops (Note 1). From the corrected volume of the iodine solution used to oxidize the arsenious oxide, calculate its relation to the normal. From the ratio between the solutions, calculate the similar value for the thiosulphate solution. [Note 1: Arsenious oxide dissolves more readily in caustic alkali than in a bicarbonate solution, but the presence of caustic alkali during the titration is not admissible. It is therefore destroyed by the addition of acid, and the solution is then made neutral with the solution of bicarbonate, part of which reacts with the acid, the excess remaining in solution. The reaction during titration is the following: Na_{3}AsO_{3} + I_{2} + 2NaHCO_{3} --> Na_{3}AsO_{4} + 2NaI + 2CO_{2} + H_{2}O As the reaction between sodium thiosulphate and iodine is not always free from secondary reactions in the presence of even the weakly alkaline bicarbonate, it is best to avoid the addition of any considerable excess of iodine. Should the end-point be passed by a few drops, the thiosulphate may be used to correct it.] DETERMINATION OF COPPER IN ORES Copper ores vary widely in composition from the nearly pure copper minerals, such as malachite and copper sulphide, to very low grade materials which contain such impurities as silica, lead, iron, silver, sulphur, arsenic, and antimony. In nearly all varieties there will be found a siliceous residue insoluble in acids. The method here given, which is a modification of that described by A.H. Low (!J. Am. Chem. Soc.! (1902), 24, 1082), provides for the extraction of the copper from commonly occurring ores, and for the presence of their common impurities. For practice analyses it is advisable to select an ore of a fair degree of purity. PROCEDURE.-- Weigh out two portions of about 0.5 gram each of the ore (which should be ground until no grit is detected) into 250 cc. Erlenmeyer flasks or small beakers. Add 10 cc. of concentrated nitric acid (sp. gr. 1.42) and heat very gently until the ore is decomposed and the acid evaporated nearly to dryness (Note 1). Add 5 cc. of concentrated hydrochloric acid (sp. gr. 1.2) and warm gently. Then add about 7 cc. of concentrated sulphuric acid (sp. gr. 1.84) and evaporate over a free flame until the sulphuric acid fumes freely (Note 2). It has then displaced nitric and hydrochloric acid from their compounds. Cool the flask or beaker, add 25 cc. of water, heat the solution to boiling, and boil for two minutes. Filter to remove insoluble sulphates, silica and any silver that may have been precipitated as silver chloride, and receive the filtrate in a small beaker, washing the precipitate and filter paper with warm water until the filtrate and washings amount to 75 cc. Bend a strip of aluminium foil (5 cm. x 12 cm.) into triangular form and place it on edge in the beaker. Cover the beaker and boil the solution (being careful to avoid loss of liquid by spattering) for ten minutes, but do not evaporate to small volume. Wash the cover glass and sides of the beaker. The copper should now be in the form of a precipitate at the bottom of the beaker or adhering loosely to the aluminium sheet. Remove the sheet, wash it carefully with hydrogen sulphide water and place it in a small beaker. Decant the solution through a filter, wash the precipitated copper twice by decantation with hydrogen sulphide water, and finally transfer the copper to the filter paper, where it is again washed thoroughly, being careful at all times to keep the precipitated copper covered with the wash water. Remove and discard the filtrate and place an Erlenmeyer flask under the funnel. Pour 15 cc. of dilute nitric acid (sp. gr. 1.20) over the aluminium foil in the beaker, thus dissolving any adhering copper. Wash the foil with hot water and remove it. Warm this nitric acid solution and pour it slowly through the filter paper, thereby dissolving the copper on the paper, receiving the acid solution in the Erlenmeyer flask. Before washing the paper, pour 5 cc. of saturated bromine water (Note 3) through it and finally wash the paper carefully with hot water and transfer any particles of copper which may be left on it to the Erlenmeyer flask. Boil to expel the bromine. Add concentrated ammonia drop by drop until the appearance of a deep blue coloration indicates an excess. Boil until the deep blue is displaced by a light bluish green coloration, or until brown stains form on the sides of the flask. Add 10 cc. of strong acetic acid (Note 4) and cool under the water tap. Add a solution containing about 3 grams of potassium iodide, as in the standardization, and titrate with thiosulphate solution until the yellow of the liberated iodine is nearly discharged. Add 1-2 cc. of freshly prepared starch solution and titrate to the disappearance of the blue color. From the data obtained, calculate the percentage of copper (Cu) in the ore. [Note 1: Nitric acid, because of its oxidizing power, is used as a solvent for the sulphide ores. As a strong acid it will also dissolve the copper from carbonate ores. The hydrochloric acid is added to dissolve oxides of iron and to precipitate silver and lead. The sulphuric acid displaces the other acids, leaving a solution containing sulphates only. It also, by its dehydrating action, renders silica from silicates insoluble.] [Note 2: Unless proper precautions are taken to insure the correct concentrations of acid the copper will not precipitate quantitatively on the aluminium foil; hence care must be taken to follow directions carefully at this point. Lead and silver have been almost completely removed as sulphate and chloride respectively, or they too would be precipitated on the aluminium. Bismuth, though precipitated on aluminium, has no effect on the analysis. Arsenic and antimony precipitate on aluminium and would interfere with the titration if allowed to remain in the lower state of oxidation.] [Note 3: Bromine is added to oxidize arsenious and antimonious compounds from the original sample, and to oxidize nitrous acid formed by the action of nitric acid on copper and copper sulphide.] [Note 4: This reaction can be carried out in the presence of sulphuric and hydrochloric acids as well as acetic acid, but in the presence of these strong acids arsenic and antimonic acids may react with the hydriodic acid produced with the liberation of free iodine, thereby reversing the process and introducing an error.] DETERMINATION OF ANTIMONY IN STIBNITE Stibnite is native antimony sulphide. Nearly pure samples of this mineral are easily obtainable and should be used for practice, since many impurities, notably iron, seriously interfere with the accurate determination of the antimony by iodometric methods. It is, moreover, essential that the directions with respect to amounts of reagents employed and concentration of solutions should be followed closely. PROCEDURE.--Grind the mineral with great care, and weigh out two portions of 0.35-0.40 gram into small, dry beakers (100 cc.). Cover the beakers and pour over the stibnite 5 cc. of concentrated hydrochloric acid (sp. gr. 1.20) and warm gently on the water bath (Note 1). When the residue is white, add to each beaker 2 grams of powdered tartaric acid (Note 2). Warm the solution on the water bath for ten minutes longer, dilute the solution very cautiously by adding water in portions of 5 cc., stopping if the solution turns red. It is possible that no coloration will appear, in which case cautiously continue the dilution to 125 cc. If a red precipitate or coloration does appear, warm the solution until it is colorless, and again dilute cautiously to a total volume of 125 cc. and boil for a minute (Note 3). If a white precipitate of the oxychloride separates during dilution (which should not occur if the directions are followed), it is best to discard the determination and to start anew. Carefully neutralize most of the acid with ammonium hydroxide solution (sp. gr. 0.96), but leave it distinctly acid (Note 4). Dissolve 3 grams of sodium bicarbonate in 200 cc. of water in a 500 cc. beaker, and pour the cold solution of the antimony chloride into this, avoiding loss by effervescence. Make sure that the solution contains an excess of the bicarbonate, and then add 1 cc. or 2 cc. of starch solution and titrate with iodine solution to the appearance of the blue, avoiding excess (Notes 5 and 6). From the corrected volume of the iodine solution required to oxidize the antimony, calculate the percentage of antimony (Sb) in the stibnite. [Note 1: Antimony chloride is volatile with steam from its concentrated solutions; hence these solutions must not be boiled until they have been diluted.] [Note 2: Antimony salts, such as the chloride, are readily hydrolyzed, and compounds such as SbOCl are formed which are often relatively insoluble; but in the presence of tartaric acid compounds with complex ions are formed, and these are soluble. An excess of hydrochloric acid also prevents precipitation of the oxychloride because the H^{+} ions from the acid lessen the dissociation of the water and thus prevent any considerable hydrolysis.] [Note 3: The action of hydrochloric acid upon the sulphide sets free sulphureted hydrogen, a part of which is held in solution by the acid. This is usually expelled by the heating upon the water bath; but if it is not wholly driven out, a point is reached during dilution at which the antimony sulphide, being no longer held in solution by the acid, separates. If the dilution is immediately stopped and the solution warmed, this sulphide is again brought into solution and at the same time more of the sulphureted hydrogen is expelled. This procedure must be continued until the sulphureted hydrogen is all removed, since it reacts with iodine. If no precipitation of the sulphide occurs, it is an indication that the sulphureted hydrogen was all expelled on solution of the stibnite.] [Note 4: Ammonium hydroxide is added to neutralize most of the acid, thus lessening the amount of sodium bicarbonate to be added. The ammonia should not neutralize all of the acid.] [Note 5: The reaction which takes place during titration may be expressed thus: Na_{3}SbO_{3} + 2NaHCO_{3} + I_{2} --> Na_{3}SbO_{4} + 2NaI + H_{2}O + 2CO_{2}.] [Note 6: If the end-point is not permanent, that is, if the blue of the iodo-starch is discharged after standing a few moments, the cause may be an insufficient quantity of sodium bicarbonate, leaving the solution slightly acid, or a very slight precipitation of an antimony compound which is slowly acted upon by the iodine when the latter is momentarily present in excess. In either case it is better to discard the analysis and to repeat the process, using greater care in the amounts of reagents employed.] CHLORIMETRY The processes included under the term !chlorimetry! comprise those employed to determine chlorine, hypochlorites, bromine, and hypobromites. The reagent employed is sodium arsenite in the presence of sodium bicarbonate. The reaction in the case of the hypochlorites is NaClO + Na_{3}AsO_{3} --> Na_{3}AsO_{4} + NaCl. The sodium arsenite may be prepared from pure arsenious oxide, as described below, and is stable for considerable periods; but commercial oxide requires resublimation to remove arsenic sulphide, which may be present in small quantity. To prepare the solution, dissolve about 5 grams of the powdered oxide, accurately weighed, in 10 cc. of a concentrated sodium hydroxide solution, dilute the solution to 300 cc., and make it faintly acid with dilute hydrochloric acid. Add 30 grams of sodium bicarbonate dissolved in a little water, and dilute the solution to exactly 1000 cc. in a measuring flask. Transfer the solution to a dry liter bottle and mix thoroughly. It is possible to dissolve the arsenious oxide directly in a solution of sodium bicarbonate, with gentle warming, but solution in sodium hydroxide takes place much more rapidly, and the excess of the hydroxide is readily neutralized by hydrochloric acid, with subsequent addition of the bicarbonate to maintain neutrality during the titration. The indicator required for this process is made by dipping strips of filter paper in a starch solution prepared as described on page 76, to which 1 gram of potassium iodide has been added. These strips are allowed to drain and spread upon a watch-glass until dry. When touched by a drop of the solution the paper turns blue until the hypochlorite has all been reduced and an excess of the arsenite has been added. DETERMINATION OF THE AVAILABLE CHLORINE IN BLEACHING POWDER Bleaching powder consists mainly of a calcium compound which is a derivative of both hydrochloric and hypochlorous acids. Its formula is CaClOCl. Its use as a bleaching or disinfecting agent, or as a source of chlorine, depends upon the amount of hypochlorous acid which it yields when treated with a stronger acid. It is customary to express the value of bleaching powder in terms of "available chlorine," by which is meant the chlorine present as hypochlorite, but not the chlorine present as chloride. PROCEDURE.--Weigh out from a stoppered test tube into a porcelain mortar about 3.5 grams of bleaching powder (Note 1). Triturate the powder in the mortar with successive portions of water until it is well ground and wash the contents into a 500 cc. measuring flask (Note 2). Fill the flask to the mark with water and shake thoroughly. Measure off 25 cc. of this semi-solution in a measuring flask, or pipette, observing the precaution that the liquid removed shall contain approximately its proportion of suspended matter. Empty the flask or pipette into a beaker and wash it out. Run in the arsenite solution from a burette until no further reaction takes place on the starch-iodide paper when touched by a drop of the solution of bleaching powder. Repeat the titration, using a second 25 cc. portion. From the volume of solution required to react with the bleaching powder, calculate the percentage of available chlorine in the latter, assuming the titration reaction to be that between chlorine and arsenious oxide: As_{4}O_{6} + 4Cl_{2} + 4H_{2}O --> 2As_{2}O_{5} + 8HCl Note that only one twentieth of the original weight of bleaching powder enters into the reaction. [Note 1: The powder must be triturated until it is fine, otherwise the lumps will inclose calcium hypochlorite, which will fail to react with the arsenious acid. The clear supernatant liquid gives percentages which are below, and the sediment percentages which are above, the average. The liquid measured off should, therefore, carry with it its proper proportion of the sediment, so far as that can be brought about by shaking the solution just before removal of the aliquot part for titration.] [Note 2: Bleaching powder is easily acted upon by the carbonic acid in the air, which liberates the weak hypochlorous acid. This, of course, results in a loss of available chlorine. The original material for analysis should be kept in a closed container and protected form the air as far as possible. It is difficult to obtain analytical samples which are accurately representative of a large quantity of the bleaching powder. The procedure, as outlined, will yield results which are sufficiently exact for technical purposes.] III. PRECIPITATION METHODS DETERMINATION OF SILVER BY THE THIOCYANATE PROCESS The addition of a solution of potassium or ammonium thiocyanate to one of silver in nitric acid causes a deposition of silver thiocyanate as a white, curdy precipitate. If ferric nitrate is also present, the slightest excess of the thiocyanate over that required to combine with the silver is indicated by the deep red which is characteristic of the thiocyanate test for iron. The reactions involved are: AgNO_{3} + KSCN --> AgSCN + KNO_{3}, 3KSCN + Fe(NO_{3})_{3} --> Fe(SCN)_{3} + 3KNO_{3}. The ferric thiocyanate differs from the great majority of salts in that it is but very little dissociated in aqueous solutions, and the characteristic color appears to be occasioned by the formation of the un-ionized ferric salt. The normal solution of potassium thiocyanate should contain an amount of the salt per liter of solution which would yield sufficient (CNS)^{-} to combine with one gram of hydrogen to form HCNS, i.e., a gram-molecular weight of the salt or 97.17 grams. If the ammonium thiocyanate is used, the amount is 76.08 grams. To prepare the solution for this determination, which should be approximately 0.05 N, dissolve about 5 grams of potassium thiocyanate, or 4 grams of ammonium thiocyanate, in a small amount of water; dilute this solution to 1000 cc. in a liter bottle and mix as usual. Prepare 20 cc. of a saturated solution of ferric alum and add 5 cc. of dilute nitric acid (sp. gr. 1.20). About 5 cc. of this solution should be used as an indicator. STANDARDIZATION PROCEDURE.--Crush a small quantity of silver nitrate crystals in a mortar (Note 1). Transfer them to a watch-glass and dry them for an hour at 110°C., protecting them from dust or other organic matter (Note 2). Weigh out two portions of about 0.5 gram each and dissolve them in 50 cc. of water. Add 10 cc. of dilute nitric acid which has been recently boiled to expel the lower oxides of nitrogen, if any, and then add 5 cc. of the indicator solution. Run in the thiocyanate solution from a burette, with constant stirring, allowing the precipitate to settle occasionally to obtain an exact recognition of the end-point, until a faint red tinge can be detected in the solution. From the data obtained, calculate the relation of the thiocyanate solution to the normal. [Note 1: The thiocyanate cannot be accurately weighed; its solutions must, therefore, be standardized against silver nitrate (or pure silver), either in the form of a standard solution or in small, weighed portions.] [Note 2: The crystals of silver nitrate sometimes inclose water which is expelled on drying. If the nitrate has come into contact with organic bodies it suffers a reduction and blackens during the heating. It is plain that a standard solution of silver nitrate (made by weighing out the crystals) is convenient or necessary if many titrations of this nature are to be made. In the absence of such a solution the liability of passing the end-point is lessened by setting aside a small fraction of the silver solution, to be added near the close of the titration.] DETERMINATION OF SILVER IN COIN PROCEDURE.-- Weigh out two portions of the coin of about 0.5 gram each. Dissolve them in 15 cc. of dilute nitric acid (sp. gr. 1.2) and boil until all the nitrous compounds are expelled (Note 1). Cool the solution, dilute to 50 cc., and add 5 cc. of the indicator solution, and titrate with the thiocyanate to the appearance of the faint red coloration (Note 2). From the corrected volume of the thiocyanate solution required, calculate the percentage of silver in the coin. [Note 1: The reaction with silver may be carried out in nitric acid solutions and in the presence of copper, if the latter does not exceed 70 per cent. Above that percentage it is necessary to add silver in known quantity to the solution. The liquid must be cold at the time of titration and entirely free from nitrous compounds, as these sometimes cause a reddening of the indicator solution. All utensils, distilled water, the nitric acid and the beakers must be free from chlorides, as the presence of these will cause precipitation of silver chloride, thereby introducing an error.] [Note 2: The solution containing the silver precipitate, as well as those from the standardization, should be placed in the receptacle for "silver residues" as a matter of economy.] PART III GRAVIMETRIC ANALYSIS GENERAL DIRECTIONS Gravimetric analyses involve the following principal steps: first, the weighing of the sample; second, the solution of the sample; third, the separation of some substance from solution containing, or bearing a definite relation to, the constituent to be measured, under conditions which render this separation as complete as possible; and finally, the segregation of that substance, commonly by filtration, and the determination of its weight, or that of some stable product formed from it on ignition. For example, the gravimetric determination of aluminium is accomplished by solution of the sample, by precipitation in the form of hydroxide, collection of the hydroxide upon a filter, complete removal by washing of all foreign soluble matter, and the burning of the filter and ignition of the precipitate to aluminium oxide, in which condition it is weighed. Among the operations which are common to nearly all gravimetric analyses are precipitation, washing of precipitates, ignition of precipitates, and the use of desiccators. In order to avoid burdensome repetitions in the descriptions of the various gravimetric procedures which follow, certain general instructions are introduced at this point. These instructions must, therefore, be considered to be as much a part of all subsequent procedures as the description of apparatus, reagents, or manipulations. The analytical balance, the fundamentally important instrument in gravimetric analysis, has already been described on pages 11 to 15. PRECIPITATION For successful quantitative precipitations those substances are selected which are least soluble under conditions which can be easily established, and which separate from solution in such a state that they can be filtered readily and washed free from admixed material. In general, the substances selected are the same as those already familiar to the student of Qualitative Analysis. When possible, substances are selected which separate in crystalline form, since such substances are less likely to clog the pores of filter paper and can be most quickly washed. In order to increase the size of the crystals, which further promotes filtration and washing, it is often desirable to allow a precipitate to remain for some time in contact with the solution from which it has separated. The solution is often kept warm during this period of "digestion." The small crystals gradually disappear and the larger crystals increase in size, probably as the result of the force known as surface tension, which tends to reduce the surface of a given mass of material to a minimum, combined with a very slightly greater solubility of small crystals as compared with the larger ones. Amorphous substances, such as ferric hydroxide, aluminium hydroxide, or silicic acid, separate in a gelatinous form and are relatively difficult to filter and wash. Substances of this class also exhibit a tendency to form, with pure water, what are known as colloidal solutions. To prevent this as far as possible, they are washed with solutions of volatile salts, as will be described in some of the following procedures. In all precipitations the reagent should be added slowly, with constant stirring, and should be hot when circumstances permit. The slow addition is less likely to occasion contamination of the precipitate by the inclosure of other substances which may be in the solution, or of the reagent itself. FUNNELS AND FILTERS Filtration in analytical processes is most commonly effected through paper filters. In special cases these may be advantageously replaced by an asbestos filter in a perforated porcelain or platinum crucible, commonly known, from its originator, as a "Gooch filter." The operation and use of a filter of this type is described on page 103. Porous crucibles of a material known as alundum may also be employed to advantage in special cases. The glass funnels selected for use with paper filters should have an angle as near 60° as possible, and a narrow stem about six inches in length. The filters employed should be washed filters, i.e., those which have been treated with hydrochloric and hydrofluoric acids, and which on incineration leave a very small and definitely known weight of ash, generally about .00003 gram. Such filters are readily obtainable on the market. The filter should be carefully folded to fit the funnel according to either of the two well-established methods described in the Appendix. It should always be placed so that the upper edge of the paper is about one fourth inch below the top of the funnel. Under no circumstances should the filter extend above the edge of the funnel, as it is then utterly impossible to effect complete washing. To test the efficiency of the filter, fill it with distilled water. This water should soon fill the stem completely, forming a continuous column of liquid which, by its hydrostatic pressure, produces a gentle suction, thus materially promoting the rapidity of filtration. Unless the filter allows free passage of water under these conditions, it is likely to give much trouble when a precipitate is placed upon it. The use of a suction pump to promote filtration is rarely altogether advantageous in quantitative analysis, if paper filters are employed. The tendency of the filter to break, unless the point of the filter paper is supported by a perforated porcelain cone or a small "hardened filter" of parchment, and the tendency of the precipitates to pass through the pores of the filter, more than compensate for the possible gain in time. On the other hand, filtration by suction may be useful in the case of precipitates which do not require ignition before weighing, or in the case of precipitates which are to be discarded without weighing. This is best accomplished with the aid of the special apparatus called a Gooch filter referred to above. FILTRATION AND WASHING OF PRECIPITATES Solutions should be filtered while hot, as far as possible, since the passage of a liquid through the pores of a filter is retarded by friction, and this, for water at 100°C., is less than one sixth of the resistance at 0°C. When the filtrate is received in a beaker, the stem of the funnel should touch the side of the receiving vessel to avoid loss by spattering. Neglect of this precaution is a frequent source of error. The vessels which contain the initial filtrate should !always! be replaced by clean ones, properly labeled, before the washing of a precipitate begins. In many instances a finely divided precipitate which shows no tendency to pass through the filter at first, while the solution is relatively dense, appears at once in the washings. Under such conditions the advantages accruing from the removal of the first filtrate are obvious, both as regards the diminished volume requiring refiltration, and also the smaller number of washings subsequently required. Much time may often be saved by washing precipitates by decantation, i.e., by pouring over them, while still in the original vessel, considerable volumes of wash-water and allowing them to settle. The supernatant, clear wash-water is then decanted through the filter, so far as practicable without disturbing the precipitate, and a new portion of wash-water is added. This procedure can be employed to special advantage with gelatinous precipitates, which fill up the pores of the filter paper. As the medium from which the precipitate is to settle becomes less dense it subsides less readily, and it ultimately becomes necessary to transfer it to the filter and complete the washing there. A precipitate should never completely fill a filter. The wash-water should be applied at the top of the filter, above the precipitate. It may be shown mathematically that the washing is most !rapidly! accomplished by filling the filter well to the top with wash-water each time, and allowing it to drain completely after each addition; but that when a precipitate is to be washed with the !least possible volume! of liquid the latter should be applied in repeated !small! quantities. Gelatinous precipitates should not be allowed to dry before complete removal of foreign matter is effected. They are likely to shrink and crack, and subsequent additions of wash-water pass through these channels only. All filtrates and wash-waters without exception must be properly tested. !This lies at the foundation of accurate work!, and the student should clearly understand that it is only by the invariable application of this rule that assurance of ultimate reliability can be secured. Every original filtrate must be tested to prove complete precipitation of the compound to be separated, and the wash-waters must also be tested to assure complete removal of foreign material. In testing the latter, the amount first taken should be but a few drops if the filtrate contains material which is to be subsequently determined. When, however, the washing of the filter and precipitate is nearly completed the amount should be increased, and for the final test not less than 3 cc. should be used. It is impossible to trust to one's judgment with regard to the washing of precipitates; the washings from !each precipitate! of a series simultaneously treated must be tested, since the rate of washing will often differ materially under apparently similar conditions, !No exception can ever be made to this rule!. The habit of placing a clean common filter paper under the receiving beaker during filtration is one to be commended. On this paper a record of the number of washings can very well be made as the portions of wash-water are added. It is an excellent practice, when possible, to retain filtrates and precipitates until the completion of an analysis, in order that, in case of question, they may be examined to discover sources of error. For the complete removal of precipitates from containing vessels, it is often necessary to rub the sides of these vessels to loosen the adhering particles. This can best be done by slipping over the end of a stirring rod a soft rubber device sometimes called a "policeman." DESICCATORS Desiccators should be filled with fused, anhydrous calcium chloride, over which is placed a clay triangle, or an iron triangle covered with silica tubes, to support the crucible or other utensils. The cover of the desiccator should be made air-tight by the use of a thin coating of vaseline. Pumice moistened with concentrated sulphuric acid may be used in place of the calcium chloride, and is essential in special cases; but for most purposes the calcium chloride, if renewed occasionally and not allowed to cake together, is practically efficient and does not slop about when the desiccator is moved. Desiccators should never remain uncovered for any length of time. The dehydrating agents rapidly lose their efficiency on exposure to the air. CRUCIBLES It is often necessary in quantitative analysis to employ fluxes to bring into solution substances which are not dissolved by acids. The fluxes in most common use are sodium carbonate and sodium or potassium acid sulphate. In gravimetric analysis it is usually necessary to ignite the separated substance after filtration and washing, in order to remove moisture, or to convert it through physical or chemical changes into some definite and stable form for weighing. Crucibles to be used in fusion processes must be made of materials which will withstand the action of the fluxes employed, and crucibles to be used for ignitions must be made of material which will not undergo any permanent change during the ignition, since the initial weight of the crucible must be deducted from the final weight of the crucible and product to obtain the weight of the ignited substance. The three materials which satisfy these conditions, in general, are platinum, porcelain, and silica. Platinum crucibles have the advantage that they can be employed at high temperatures, but, on the other hand, these crucibles can never be used when there is a possibility of the reduction to the metallic state of metals like lead, copper, silver, or gold, which would alloy with and ruin the crucible. When platinum crucibles are used with compounds of arsenic or phosphorus, special precautions are necessary to prevent damage. This statement applies to both fusions and ignitions. Fusions with sodium carbonate can be made only in platinum, since porcelain or silica crucibles are attacked by this reagent. Acid sulphate fusions, which require comparatively low temperatures, can sometimes be made in platinum, although platinum is slightly attacked by the flux. Porcelain or silica crucibles may be used with acid fluxes. Silica crucibles are less likely to crack on heating than porcelain crucibles on account of their smaller coefficient of expansion. Ignition of substances not requiring too high a temperature may be made in porcelain or silica crucibles. Iron, nickel or silver crucibles are used in special cases. In general, platinum crucibles should be used whenever such use is practicable, and this is the custom in private, research or commercial laboratories. Platinum has, however, become so valuable that it is liable to theft unless constantly under the protection of the user. As constant protection is often difficult in instructional laboratories, it is advisable, in order to avoid serious monetary losses, to use porcelain or silica crucibles whenever these will give satisfactory service. When platinum utensils are used the danger of theft should always be kept in mind. PREPARATION OF CRUCIBLES FOR USE All crucibles, of whatever material, must always be cleaned, ignited and allowed to cool in a desiccator before weighing, since all bodies exposed to the air condense on their surfaces a layer of moisture which increases their weight. The amount and weight of this moisture varies with the humidity of the atmosphere, and the latter may change from hour to hour. The air in the desiccator (see above) is kept at a constant and low humidity by the drying agent which it contains. Bodies which remain in a desiccator for a sufficient time (usually 20-30 minutes) retain, therefore, on their surfaces a constant weight of moisture which is the same day after day, thus insuring constant conditions. Hot objects, such as ignited crucibles, should be allowed to cool in the air until, when held near the skin, but little heat is noticeable. If this precaution is not taken, the air within the desiccator is strongly heated and expands before the desiccator is covered. As the temperature falls, the air contracts, causing a reduction of air pressure within the covered vessel. When the cover is removed (which is often rendered difficult) the inrush of air from the outside may sweep light particles out of a crucible, thus ruining an entire analysis. Constant heating of platinum causes a slight crystallization of the surface which, if not removed, penetrates into the crucible. Gentle polishing of the surface destroys the crystalline structure and prevents further damage. If sea sand is used for this purpose, great care is necessary to keep it from the desk, since beakers are easily scratched by it, and subsequently crack on heating. Platinum crucibles stained in use may often be cleaned by the fusion in them of potassium or sodium acid sulphate, or by heating with ammonium chloride. If the former is used, care should be taken not to heat so strongly as to expel all of the sulphuric acid, since the normal sulphates sometimes expand so rapidly on cooling as to split the crucible. The fused material should be poured out, while hot, on to a !dry! tile or iron surface. IGNITION OF PRECIPITATES Most precipitates may, if proper precautions are taken, be ignited without previous drying. If, however, such precipitates can be dried without loss of time to the analyst (as, for example, over night), it is well to submit them to this process. It should, nevertheless, be remembered that a partially dried precipitate often requires more care during ignition than a thoroughly moist one. The details of the ignition of precipitates vary so much with the character of the precipitate, its moisture content, and temperature to which it is to be heated, that these details will be given under the various procedures which follow. DETERMINATION OF CHLORINE IN SODIUM CHLORIDE !Method A. With the Use of a Gooch Filter! PROCEDURE.--Carefully clean a weighing-tube containing the sodium chloride, handling it as little as possible with the moist fingers, and weigh it accurately to 0.0001 gram, recording the weight at once in the notebook (see Appendix). Hold the tube over the top of a beaker (200-300 cc.), and cautiously remove the stopper, noting carefully that no particles fall from it, or from the tube, elsewhere than into the beaker. Pour out a small portion of the chloride, replace the stopper, and determine by approximate weighing how much has been removed. Continue this procedure until 0.25-0.30 gram has been taken from the tube, then weigh accurately and record the weight beneath the first in the notebook. The difference of the two weights represents the weight of the chloride taken for analysis. Again weigh a second portion of 0.25-0.30 gram into a second beaker of the same size as the first. The beakers should be plainly marked to correspond with the entries in the notebook. Dissolve each portion of the chloride in 150 cc. of distilled water and add about ten drops of dilute nitric acid (sp. gr. 1.20) (Note 2). Calculate the volume of silver nitrate solution required to effect complete precipitation in each case, and add slowly about 5 cc. in excess of that amount, with constant stirring. Heat the solutions cautiously to boiling, stirring occasionally, and continue the heating and stirring until the precipitates settle promptly, leaving a nearly clear supernatant liquid (Note 3). This heating should not take place in direct sunlight (Note 4). The beaker should be covered with a watch-glass, and both boiling and stirring so regulated as to preclude any possibility of loss of material. Add to the clear liquid one or two drops of silver nitrate solution, to make sure that an excess of the reagent is present. If a precipitate, or cloudiness, appears as the drops fall into the solution, heat again, and stir until the whole precipitate has coagulated. The solution is then ready for filtration. Prepare a Gooch filter as follows: Fold over the top of a Gooch funnel (Fig. 2) a piece of rubber-band tubing, such as is known as "bill-tie" tubing, and fit into the mouth of the funnel a perforated porcelain crucible (Gooch crucible), making sure that when the crucible is gently forced into the mouth of the funnel an airtight joint results. (A small 1 or 1-1/4-inch glass funnel may be used, in which case the rubber tubing is stretched over the top of the funnel and then drawn up over the side of the crucible until an air-tight joint is secured.) [ILLUSTRATION: FIG. 2] Fit the funnel into the stopper of a filter bottle, and connect the filter bottle with the suction pump. Suspend some finely divided asbestos, which has been washed with acid, in 20 to 30 cc. of water (Note 1); allow this to settle, pour off the very fine particles, and then pour some of the mixture cautiously into the crucible until an even felt of asbestos, not over 1/32 inch in thickness, is formed. A gentle suction must be applied while preparing this felt. Wash the felt thoroughly by passing through it distilled water until all fine or loose particles are removed, increasing the suction at the last until no more water can be drawn out of it; place on top of the felt the small, perforated porcelain disc and hold it in place by pouring a very thin layer of asbestos over it, washing the whole carefully; then place the crucible in a small beaker, and place both in a drying closet at 100-110°C. for thirty to forty minutes. Cool the crucible in a desiccator, and weigh. Heat again for twenty to thirty minutes, cool, and again weigh, repeating this until the weight is constant within 0.0003 gram. The filter is then ready for use. Place the crucible in the funnel, and apply a gentle suction, !after which! the solution to be filtered may be poured in without disturbing the asbestos felt. When pouring liquid onto a Gooch filter hold the stirring-rod at first well down in the crucible, so that the liquid does not fall with any force upon the asbestos, and afterward keep the crucible will filled with the solution. Pour the liquid above the silver chloride slowly onto the filter, leaving the precipitate in the beaker as far as possible. Wash the precipitate twice by decantation with warm water; then transfer it to the filter with the aid of a stirring-rod with a rubber tip and a stream from the wash-bottle. Examine the first portions of the filtrate which pass through the filter with great care for asbestos fibers, which are most likely to be lost at this point. Refilter the liquid if any fibers are visible. Finally, wash the precipitate thoroughly with warm water until free from soluble silver salts. To test the washings, disconnect the suction at the flask and remove the funnel or filter tube from the suction flask. Hold the end of the tube over the mouth of a small test tube and add from a wash-bottle 2-3 cc. of water. Allow the water to drip through into the test tube and add a drop of dilute hydrochloric acid. No precipitate or cloud should form in the wash-water (Note 16). Dry the filter and contents at 100-110°C. until the weight is constant within 0.0003 gram, as described for the preparation of the filter. Deduct the weight of the dry crucible from the final weight, and from the weight of silver chloride thus obtained calculate the percentage of chlorine in the sample of sodium chloride. [Note 1: The washed asbestos for this type of filter is prepared by digesting in concentrated hydrochloric acid, long-fibered asbestos which has been cut in pieces of about 0.5 cm. in length. After digestion, the asbestos is filtered off on a filter plate and washed with hot, distilled water until free from chlorides. A small portion of the asbestos is shaken with water, forming a thin suspension, which is bottled and kept for use.] [Note 2: The nitric acid is added before precipitation to lessen the tendency of the silver chloride to carry down with it other substances which might be precipitated from a neutral solution. A large excess of the acid would exert a slight solvent action upon the chloride.] [Note 3: The solution should not be boiled after the addition of the nitric acid before the presence of an excess of silver nitrate is assured, since a slight interaction between the nitric acid and the sodium chloride is possible, by which a loss of chlorine, either as such or as hydrochloric acid, might ensue. The presence of an excess of the precipitant can usually be recognized at the time of its addition, by the increased readiness with which the precipitate coagulates and settles.] [Note 4: The precipitate should not be exposed to strong sunlight, since under those conditions a reduction of the silver chloride ensues which is accompanied by a loss of chlorine. The superficial alteration which the chloride undergoes in diffused daylight is not sufficient to materially affect the accuracy of the determination. It should be noted, however, that a slight error does result from the effect of light upon the silver chloride precipitate and in cases in which the greatest obtainable accuracy is required, the procedure described under "Method B" should be followed, in which this slight reduction of the silver chloride is corrected by subsequent treatment with nitric and hydrochloric acids.] [Note 5: The asbestos used in the Gooch filter should be of the finest quality and capable of division into minute fibrous particles. A coarse felt is not satisfactory.] [Note 6: The precipitate must be washed with warm water until it is absolutely free from silver and sodium nitrates. It may be assumed that the sodium salt is completely removed when the wash-water shows no evidence of silver. It must be borne in mind that silver chloride is somewhat soluble in hydrochloric acid, and only a single drop should be added. The washing should be continued until no cloudiness whatever can be detected in 3 cc. of the washings. Silver chloride is but slightly soluble in water. The solubility varies with its physical condition within small limits, and is about 0.0018 gram per liter at 18°C. for the curdy variety usually precipitated. The chloride is also somewhat soluble in solutions of many chlorides, in solutions of silver nitrate, and in concentrated nitric acid. As a matter of economy, the filtrate, which contains whatever silver nitrate was added in excess, may be set aside. The silver can be precipitated as chloride and later converted into silver nitrate.] [Note 7: The use of the Gooch filter commends itself strongly when a considerable number of halogen determinations are to be made, since successive portions of the silver halides may be filtered on the same filter, without the removal of the preceding portions, until the crucible is about two thirds filled. If the felt is properly prepared, filtration and washing are rapidly accomplished on this filter, and this, combined with the possibility of collecting several precipitates on the same filter, is a strong argument in favor of its use with any but gelatinous precipitates.] !Method B. With the Use of a Paper Filter! PROCEDURE.--Weigh out two portions of sodium chloride of about 0.25-0.3 gram each and proceed with the precipitation of the silver chloride as described under Method A above. When the chloride is ready for filtration prepare two 9 cm. washed paper filters (see Appendix). Pour the liquid above the precipitates through the filters, wash twice by decantation and transfer the precipitates to the filters, finally washing them until free from silver solution as described. The funnel should then be covered with a moistened filter paper by stretching it over the top and edges, to which it will adhere on drying. It should be properly labeled with the student's name and desk number, and then placed in a drying closet, at a temperature of about 100-110°C., until completely dry. The perfectly dry filter is then opened over a circular piece of clean, smooth, glazed paper about six inches in diameter, placed upon a larger piece about twelve inches in diameter. The precipitate is removed from the filter as completely as possible by rubbing the sides gently together, or by scraping them cautiously with a feather which has been cut close to the quill and is slightly stiff (Note 1). In either case, care must be taken not to rub off any considerable quantity of the paper, nor to lose silver chloride in the form of dust. Cover the precipitate on the glazed paper with a watch-glass to prevent loss of fine particles and to protect it from dust from the air. Fold the filter paper carefully, roll it into a small cone, and wind loosely around !the top! a piece of small platinum wire (Note 2). Hold the filter by the wire over a small porcelain crucible (which has been cleaned, ignited, cooled in a desiccator, and weighed), ignite it, and allow the ash to fall into the crucible. Place the crucible upon a clean clay triangle, on its side, and ignite, with a low flame well at its base, until all the carbon of the filter has been consumed. Allow the crucible to cool, add two drops of concentrated nitric acid and one drop of concentrated hydrochloric acid, and heat !very cautiously!, to avoid spattering, until the acids have been expelled; then transfer the main portion of the precipitate from the glazed paper to the cooled crucible, placing the latter on the larger piece of glazed paper and brushing the precipitate from the smaller piece into it, sweeping off all particles belonging to the determination. Moisten the precipitate with two drops of concentrated nitric acid and one drop of concentrated hydrochloric acid, and again heat with great caution until the acids are expelled and the precipitate is white, when the temperature is slowly raised until the silver chloride just begins to fuse at the edges (Note 3). The crucible is then cooled in a desiccator and weighed, after which the heating (without the addition of acids) is repeated, and it is again weighed. This must be continued until the weight is constant within 0.0003 gram in two consecutive weighings. Deduct the weight of the crucible, and calculate the percentage of chlorine in the sample of sodium chloride taken for analysis. [Note 1: The separation of the silver chloride from the filter is essential, since the burning carbon of the paper would reduce a considerable quantity of the precipitate to metallic silver, and its complete reconversion to the chloride within the crucible, by means of acids, would be accompanied by some difficulty. The small amount of silver reduced from the chloride adhering to the filter paper after separating the bulk of the precipitate, and igniting the paper as prescribed, can be dissolved in nitric acid, and completely reconverted to chloride by hydrochloric acid. The subsequent addition of the two acids to the main portion of the precipitate restores the chlorine to any chloride which may have been partially reduced by the sunlight. The excess of the acids is volatilized by heating.] [Note 2: The platinum wire is wrapped around the top of the filter during its incineration to avoid contact with any reduced silver from the reduction of the precipitate. If the wire were placed nearer the apex, such contact could hardly be avoided.] [Note 3: Silver chloride should not be heated to complete fusion, since a slight loss by volatilization is possible at high temperatures. The temperature of fusion is not always sufficient to destroy filter shreds; hence these should not be allowed to contaminate the precipitate.] DETERMINATION OF IRON AND OF SULPHUR IN FERROUS AMMONIUM SULPHATE, FESO_{4}.(NH_{4})_{2}SO_{4}.6H_{2}O DETERMINATION OF IRON PROCEDURE.--Weigh out into beakers (200-250 cc.) two portions of the sample (Note 1) of about 1 gram each and dissolve these in 50 cc. of water, to which 1 cc. of dilute hydrochloric acid (sp. gr. 1.12) has been added (Note 2). Heat the solution to boiling, and while at the boiling point add concentrated nitric acid (sp. gr. 1.42), !drop by drop! (noting the volume used), until the brown coloration, which appears after the addition of a part of the nitric acid, gives place to a yellow or red (Note 3). Avoid a large excess of nitric acid, but be sure that the action is complete. Pour this solution cautiously into about 200 cc. of water, containing a slight excess of ammonia. Calculate for this purpose the amount of aqueous ammonia required to neutralize the hydrochloric and nitric acids added (see Appendix for data), and also to precipitate the iron as ferric hydroxide from the weight of the ferrous ammonium sulphate taken for analysis, assuming it to be pure (Note 4). The volume thus calculated will be in excess of that actually required for precipitation, since the acids are in part consumed in the oxidation process, or are volatilized. Heat the solution to boiling, and allow the precipitated ferric hydroxide to settle. Decant the clear liquid through a washed filter (9 cm.), keeping as much of the precipitate in the beaker as possible. Wash twice by decantation with 100 cc. of hot water. Reserve the filtrate. Dissolve the iron from the filter with hot, dilute hydrochloric acid (sp. gr. 1.12), adding it in small portions, using as little as possible and noting the volume used. Collect the solution in the beaker in which precipitation took place. Add 1 cc. of nitric acid (sp. gr. 1.42), boil for a few moments, and again pour into a calculated excess of ammonia. Wash the precipitate twice by decantation, and finally transfer it to the original filter. Wash continuously with hot water until finally 3 cc. of the washings, acidified with nitric acid (Note 5), show no evidences of the presence of chlorides when tested with silver nitrate. The filtrate and washings are combined with those from the first precipitation and treated for the determination of sulphur, as prescribed on page 112. [Note 1: If a selection of pure material for analysis is to be made, crystals which are cloudy are to be avoided on account of loss of water of crystallization; and also those which are red, indicating the presence of ferric iron. If, on the other hand, the value of an average sample of material is desired, it is preferable to grind the whole together, mix thoroughly, and take a sample from the mixture for analysis.] [Note 2: When aqueous solutions of ferrous compounds are heated in the air, oxidation of the Fe^{++} ions to Fe^{+++} ions readily occurs in the absence of free acid. The H^{+} and OH^{-} ions from water are involved in the oxidation process and the result is, in effect, the formation of some ferric hydroxide which tends to separate. Moreover, at the boiling temperature, the ferric sulphate produced by the oxidation hydrolyzes in part with the formation of a basic ferric sulphate, which also tends to separate from solution. The addition of the hydrochloric acid prevents the formation of ferric hydroxide, and so far reduces the ionization of the water that the hydrolysis of the ferric sulphate is also prevented, and no precipitation occurs on heating.] [Note 3: The nitric acid, after attaining a moderate strength, oxidizes the Fe^{++} ions to Fe^{+++} ions with the formation of an intermediate nitroso-compound similar in character to that formed in the "ring-test" for nitrates. The nitric oxide is driven out by heat, and the solution then shows by its color the presence of ferric compounds. A drop of the oxidized solution should be tested on a watch-glass with potassium ferricyanide, to insure a complete oxidation. This oxidation of the iron is necessary, since Fe^{++} ions are not completely precipitated by ammonia. The ionic changes which are involved in this oxidation are perhaps most simply expressed by the equation 3Fe^{++} + NO_{3}^{-}+ 4H^{+} --> 3Fe^{+++} + 2H_{2}O + NO, the H^{+} ions coming from the acid in the solution, in this case either the nitric or the hydrochloric acid. The full equation on which this is based may be written thus: 6FeSO_{4} + 2HNO_{3} + 6HCl --> 2Fe_{2}(SO_{4})_{3} + 2FeCl_{3} + 2NO + 4H_{2}O, assuming that only enough nitric acid is added to complete the oxidation.] [Note 4: The ferric hydroxide precipitate tends to carry down some sulphuric acid in the form of basic ferric sulphate. This tendency is lessened if the solution of the iron is added to an excess of OH^{-} ions from the ammonium hydroxide, since under these conditions immediate and complete precipitation of the ferric hydroxide ensues. A gradual neutralization with ammonia would result in the local formation of a neutral solution within the liquid, and subsequent deposition of a basic sulphate as a consequence of a local deficiency of OH^{-} ions from the NH_{4}OH and a partial hydrolysis of the ferric salt. Even with this precaution the entire absence of sulphates from the first iron precipitate is not assured. It is, therefore, redissolved and again thrown down by ammonia. The organic matter of the filter paper may occasion a partial reduction of the iron during solution, with consequent possibility of incomplete subsequent precipitation with ammonia. The nitric acid is added to reoxidize this iron. To avoid errors arising from the solvent action of ammoniacal liquids upon glass, the iron precipitate should be filtered without unnecessary delay.] [Note 5: The washings from the ferric hydroxide are acidified with nitric acid, before testing with silver nitrate, to destroy the ammonia which is a solvent of silver chloride. The use of suction to promote filtration and washing is permissible, though not prescribed. The precipitate should not be allowed to dry during the washing.] !Ignition of the Iron Precipitate! Heat a platinum or porcelain crucible, cool it in a desiccator and weigh, repeating until a constant weight is obtained. Fold the top of the filter paper over the moist precipitate of ferric hydroxide and transfer it cautiously to the crucible. Wipe the inside of the funnel with a small fragment of washed filter paper, if necessary, and place the paper in the crucible. Incline the crucible on its side, on a triangle supported on a ring-stand, and stand the cover on edge at the mouth of the crucible. Place a burner below the front edge of the crucible, using a low flame and protecting it from drafts of air by means of a chimney. The heat from the burner is thus reflected into the crucible and dries the precipitate without danger of loss as the result of a sudden generation of steam within the mass of ferric hydroxide. As the drying progresses the burner may be gradually moved toward the base of the crucible and the flame increased until the paper of the filter begins to char and finally to smoke, as the volatile matter is expelled. This is known as "smoking off" a filter, and the temperature should not be raised sufficiently high during this process to cause the paper to ignite, as the air currents produced by the flame of the blazing paper may carry away particles of the precipitate. When the paper is fully charred, move the burner to the base of the crucible and raise the temperature to the full heat of the burner for fifteen minutes, with the crucible still inclined on its side, but without the cover (Note 1). Finally set the crucible upright in the triangle, cover it, and heat at the full temperature of a blast lamp or other high temperature burner. Cool and weigh in the usual manner (Note 2). Repeat the strong heating until the weight is constant within 0.0003 gram. From the weight of ferric oxide (Fe_{2}O_{3}) calculate the percentage of iron (Fe) in the sample (Note 3). [Note 1: These directions for the ignition of the precipitate must be closely followed. A ready access of atmospheric oxygen is of special importance to insure the reoxidation to ferric oxide of any iron which may be reduced to magnetic oxide (Fe_{3}O_{4}) during the combustion of the filter. The final heating over the blast lamp is essential for the complete expulsion of the last traces of water from the hydroxide.] [Note 2: Ignited ferric oxide is somewhat hygroscopic. On this account the weighings must be promptly completed after removal from the desiccator. In all weighings after the first it is well to place the weights upon the balance-pan before removing the crucible from the desiccator. It is then only necessary to move the rider to obtain the weight.] [Note 3: The gravimetric determination of aluminium or chromium is comparable with that of iron just described, with the additional precaution that the solution must be boiled until it contains but a very slight excess of ammonia, since the hydroxides of aluminium and chromium are more soluble than ferric hydroxide. The most important properties of these hydroxides, from a quantitative standpoint, other than those mentioned, are the following: All are precipitable by the hydroxides of sodium and potassium, but always inclose some of the precipitant, and should be reprecipitated with ammonium hydroxide before ignition to oxides. Chromium and aluminium hydroxides dissolve in an excess of the caustic alkalies and form anions, probably of the formula AlO_2^{-} and CrO_{2}^{-}. Chromium hydroxide is reprecipitated from this solution on boiling. When first precipitated the hydroxides are all readily soluble in acids, but aluminium hydroxide dissolves with considerable difficulty after standing or boiling for some time. The precipitation of the hydroxides is promoted by the presence of ammonium chloride, but is partially or entirely prevented by the presence of tartaric or citric acids, glycerine, sugars, and some other forms of soluble organic matter. The hydroxides yield on ignition an oxide suitable for weighing (Al_{2}O_{3}, Cr_{2}O_{3}, Fe_{2}O_{3}).] DETERMINATION OF SULPHUR PROCEDURE.--Add to the combined filtrates from the ferric hydroxide about 0.6 gram of anhydrous sodium carbonate; cover the beaker, and then add dilute hydrochloric acid (sp. gr. 1.12) in moderate excess and evaporate to dryness on the water bath. Add 10 cc. of concentrated hydrochloric acid (sp. gr. 1.20) to the residue, and again evaporate to dryness on the bath. Dissolve the residue in water, filter if not clear, transfer to a 700 cc. beaker, dilute to about 400 cc., and cautiously add hydrochloric acid until the solution shows a distinctly acid reaction (Note 1). Heat the solution to boiling, and add !very slowly! and with constant stirring, 20 cc. in excess of the calculated amount of a hot barium chloride solution, containing about 20 grams BaCl_{2}.2H_{2}O per liter (Notes 2 and 3). Continue the boiling for about two minutes, allow the precipitate to settle, and decant the liquid at the end of half an hour (Note 4). Replace the beaker containing the original filtrate by a clean beaker, wash the precipitated sulphate by decantation with hot water, and subsequently upon the filter until it is freed from chlorides, testing the washings as described in the determination of iron. The filter is then transferred to a platinum or porcelain crucible and ignited, as described above, until the weight is constant (Note 5). From the weight of barium sulphate (BaSO_{4}) obtained, calculate the percentage of sulphur (S) in the sample. [Note 1: Barium sulphate is slightly soluble in hydrochloric acid, even dilute, probably as a result of the reduction in the degree of dissociation of sulphuric acid in the presence of the H^{+} ions of the hydrochloric acid, and possibly because of the formation of a complex anion made up of barium and chlorine; hence only the smallest excess should be added over the amount required to acidify the solution.] [Note 2: The ionic changes involved in the precipitation of barium sulphate are very simple: Ba^{++} + SO_{4}^{--} --> [BaSO_{4}] This case affords one of the best illustrations of the effect of an excess of a precipitant in decreasing the solubility of a precipitate. If the conditions are considered which exist at the moment when just enough of the Ba^{++} ions have been added to correspond to the SO_{4}^{--} ions in the solution, it will be seen that nearly all of the barium sulphate has been precipitated, and that the small amount which then remains in the solution which is in contact with the precipitate must represent a saturated solution for the existing temperature, and that this solution is comparable with a solution of sugar to which more sugar has been added than will dissolve. It should be borne in mind that the quantity of barium sulphate in this !saturated solution is a constant quantity! for the existing conditions. The dissolved barium sulphate, like any electrolyte, is dissociated, and the equilibrium conditions may be expressed thus: (!Conc'n Ba^{++} x Conc'n SO_{4}^{--})/(Conc'n BaSO_{4}) = Const.!, and since !Conc'n BaSO_{4}! for the saturated solution has a constant value (which is very small), it may be eliminated, when the expression becomes !Conc'n Ba^{++} x Conc'n SO_{4}^{--} = Const.!, which is the "solubility product" of BaSO_{4}. If, now, an excess of the precipitant, a soluble barium salt, is added in the form of a relatively concentrated solution (the slight change of volume of a few cubic centimeters may be disregarded for the present discussion) the concentration of the Ba^{++} ions is much increased, and as a consequence the !Conc'n SO_{4}! must decrease in proportion if the value of the expression is to remain constant, which is a requisite condition if the law of mass action upon which our argument depends holds true. In other words, SO_{4}^{--} ions must combine with some of the added Ba^{++} ions to form [BaSO_{4}]; but it will be recalled that the solution is already saturated with BaSO_{4}, and this freshly formed quantity must, therefore, separate and add itself to the precipitate. This is exactly what is desired in order to insure more complete precipitation and greater accuracy, and leads to the conclusion that the larger the excess of the precipitant added the more successful the analysis; but a practical limit is placed upon the quantity of the precipitant which may be properly added by other conditions, as stated in the following note.] [Note 3: Barium sulphate, in a larger measure than most compounds, tends to carry down other substances which are present in the solution from which it separates, even when these other substances are relatively soluble, and including the barium chloride used as the precipitant. This is also notably true in the case of nitrates and chlorates of the alkalies, and of ferric compounds; and, since in this analysis ammonium nitrate has resulted from the neutralization of the excess of the nitric acid added to oxidize the iron, it is essential that this should be destroyed by repeated evaporation with a relatively large quantity of hydrochloric acid. During evaporation a mutual decomposition of the two acids takes place, and the nitric acid is finally decomposed and expelled by the excess of hydrochloric acid. Iron is usually found in the precipitate of barium sulphate when thrown down from hot solutions in the presence of ferric salts. This, according to Kuster and Thiel (!Zeit. anorg. Chem.!, 22, 424), is due to the formation of a complex ion (Fe(SO_{4})_{2}) which precipitates with the Ba^{++} ion, while Richards (!Zeit. anorg. Chem.!, 23, 383) ascribes it to hydrolytic action, which causes the formation of a basic ferric complex which is occluded in the barium precipitate. Whatever the character of the compound may be, it has been shown that it loses sulphuric anhydride upon ignition, causing low results, even though the precipitate contains iron. The contamination of the barium sulphate by iron is much less in the presence of ferrous than ferric salts. If, therefore, the sulphur alone were to be determined in the ferrous ammonium sulphate, the precipitation by barium might be made directly from an aqueous solution of the salt, which had been made slightly acid with hydrochloric acid.] [Note 4: The precipitation of the barium sulphate is probably complete at the end of a half-hour, and the solution may safely be filtered at the expiration of that time if it is desired to hasten the analysis. As already noted, many precipitates of the general character of this sulphate tend to grow more coarsely granular if digested for some time with the liquid from which they have separated. It is therefore well to allow the precipitate to stand in a warm place for several hours, if practicable, to promote ease of filtration. The filtrate and washings should always be carefully examined for minute quantities of the sulphate which may pass through the pores of the filter. This is best accomplished by imparting to the filtrate a gentle rotary motion, when the sulphate, if present, will collect at the center of the bottom of the beaker.] [Note 5: A reduction of barium sulphate to the sulphide may very readily be caused by the reducing action of the burning carbon of the filter, and much care should be taken to prevent any considerable reduction from this cause. Subsequent ignition, with ready access of air, reconverts the sulphide to sulphate unless a considerable reduction has occurred. In the latter case it is expedient to add one or two drops of sulphuric acid and to heat cautiously until the excess of acid is expelled.] [Note 6: Barium sulphate requires about 400,000 parts of water for its solution. It is not decomposed at a red heat but suffers loss, probably of sulphur trioxide, at a temperature above 900°C.] DETERMINATION OF SULPHUR IN BARIUM SULPHATE PROCEDURE.--Weigh out, into platinum crucibles, two portions of about 0.5 gram of the sulphate. Mix each in the crucible with five to six times its weight of anhydrous sodium carbonate. This can best be done by placing the crucible on a piece of glazed paper and stirring the mixture with a clean, dry stirring-rod, which may finally be wiped off with a small fragment of filter paper, the latter being placed in the crucible. Cover the crucible and heat until a quiet, liquid fusion ensues. Remove the burner, and tip the crucible until the fused mass flows nearly to its mouth. Hold it in that position until the mass has solidified. When cold, the material may usually be detached in a lump by tapping the crucible or gently pressing it near its upper edge. If it still adheres, a cubic centimeter or so of water may be placed in the cold crucible and cautiously brought to boiling, when the cake will become loosened and may be removed and placed in about 250 cc. of hot, distilled water to dissolve. Clean the crucible completely, rubbing the sides with a rubber-covered stirring-rod, if need be. When the fused mass has completely disintegrated and nothing further will dissolve, decant the solution from the residue of barium carbonate (Note 1). Pour over the residue 20 cc. of a solution of sodium carbonate and 10 cc. of water and heat to gentle boiling for about three minutes (Note 2). Filter off the carbonate and wash it with hot water, testing the slightly acidified washings for sulphate and preserving any precipitates which appear in these tests. Acidify the filtrate with hydrochloric acid until just acid, bring to boiling, and slowly add hot barium chloride solution, as in the preceding determination. Add also any tests from the washings in which precipitates have appeared. Filter, wash, ignite, and weigh. From the weight of barium sulphate, calculate the percentage of sulphur (S) in the sample. [Note 1: This alkaline fusion is much employed to disintegrate substances ordinarily insoluble in acids into two components, one of which is water soluble and the other acid soluble. The reaction involved is: BaSO_{4} + Na_{2}CO_{3}, --> BaCO_{3}, + Na_{2}SO_{4}. As the sodium sulphate is soluble in water, and the barium carbonate insoluble, a separation between them is possible and the sulphur can be determined in the water-soluble portion. It should be noted that this method can be applied to the purification of a precipitate of barium sulphate if contaminated by most of the substances mentioned in Note 3 on page 114. The impurities pass into the water solution together with the sodium sulphate, but, being present in such minute amounts, do not again precipitate with the barium sulphate.] [Note 2: The barium carbonate is boiled with sodium carbonate solution before filtration because the reaction above is reversible; and it is only by keeping the sodium carbonate present in excess until nearly all of the sodium sulphate solution has been removed by filtration that the reversion of some of the barium carbonate to barium sulphate is prevented. This is an application of the principle of mass action, in which the concentration of the reagent (the carbonate ion) is kept as high as practicable and that of the sulphate ion as low as possible, in order to force the reaction in the desired direction (see Appendix).] DETERMINATION OF PHOSPHORIC ANHYDRIDE IN APATITE The mineral apatite is composed of calcium phosphate, associated with calcium chloride, or fluoride. Specimens are easily obtainable which are nearly pure and leave on treatment with acid only a slight siliceous residue. For the purpose of gravimetric determination, phosphoric acid is usually precipitated from ammoniacal solutions in the form of magnesium ammonium phosphate which, on ignition, is converted into magnesium pyrophosphate. Since the calcium phosphate of the apatite is also insoluble in ammoniacal solutions, this procedure cannot be applied directly. The separation of the phosphoric acid from the calcium must first be accomplished by precipitation in the form of ammonium phosphomolybdate in nitric acid solution, using ammonium molybdate as the precipitant. The "yellow precipitate," as it is often called, is not always of a definite composition, and therefore not suitable for direct weighing, but may be dissolved in ammonia, and the phosphoric acid thrown out as magnesium ammonium phosphate from the solution. Of the substances likely to occur in apatite, silicic acid alone interferes with the precipitation of the phosphoric acid in nitric acid solution. PRECIPITATION OF AMMONIUM PHOSPHOMOLYBDATE PROCEDURE.--Grind the mineral in an agate mortar until no grit is perceptible. Transfer the substance to a weighing-tube, and weigh out two portions, not exceeding 0.20 gram each (Note 1) into two beakers of about 200 cc. capacity. Pour over them 20 cc. of dilute nitric acid (sp. gr. 1.2) and warm gently until solvent action has apparently ceased. Evaporate the solution cautiously to dryness, heat the residue for about an hour at 100-110°C., and treat it again with nitric acid as described above; separate the residue of silica by filtration on a small filter (7 cm.) and wash with warm water, using as little as possible (Note 2). Receive the filtrate in a beaker (200-500 cc.). Test the washings with ammonia for calcium phosphate, but add all such tests in which a precipitate appears to the original nitrate (Note 3). The filtrate and washings must be kept as small as possible and should not exceed 100 cc. in volume. Add aqueous ammonia (sp. gr. 0.96) until the precipitate of calcium phosphate first produced just fails to redissolve, and then add a few drops of nitric acid until this is again brought into solution (Note 4). Warm the solution until it cannot be comfortably held in the hand (about 60°C.) and, after removal of the burner, add 75 cc. of ammonium molybdate solution which has been !gently! warmed, but which must be perfectly clear. Allow the mixture to stand at a temperature of about 50 or 60°C. for twelve hours (Notes 5 and 6). Filter off the yellow precipitate on a 9 cm. filter, and wash by decantation with a solution of ammonium nitrate made acid with nitric acid.[1] Allow the precipitate to remain in the beaker as far as possible. Test the washings for calcium with ammonia and ammonium oxalate (Note 3). [Footnote 1: This solution is prepared as follows: Mix 100 cc. of ammonia solution (sp. gr. 0.96) with 325 cc. of nitric acid (sp. gr. 1.2) and dilute with 100 cc. of water.] Add 10 cc. of molybdate solution to the nitrate, and leave it for a few hours. It should then be carefully examined for a !yellow! precipitate; a white precipitate may be neglected. [Note 1: Magnesium ammonium phosphate, as noted below, is slightly soluble under the conditions of operation. Consequently the unavoidable errors of analysis are greater in this determination than in those which have preceded it, and some divergence may be expected in duplicate analyses. It is obvious that the larger the amount of substance taken for analysis the less will be the relative loss or gain due to unavoidable experimental errors; but, in this instance, a check is placed upon the amount of material which may be taken both by the bulk of the resulting precipitate of ammonium phosphomolybdate and by the excessive amount of ammonium molybdate required to effect complete separation of the phosphoric acid, since a liberal excess above the theoretical quantity is demanded. Molybdic acid is one of the more expensive reagents.] [Note 2: Soluble silicic acid would, if present, partially separate with the phosphomolybdate, although not in combination with molybdenum. Its previous removal by dehydration is therefore necessary.] [Note 3: When washing the siliceous residue the filtrate may be tested for calcium by adding ammonia, since that reagent neutralizes the acid which holds the calcium phosphate in solution and causes precipitation; but after the removal of the phosphoric acid in combination with the molybdenum, the addition of an oxalate is required to show the presence of calcium.] [Note 4: An excess of nitric acid exerts a slight solvent action, while ammonium nitrate lessens the solubility; hence the neutralization of the former by ammonia.] [Note 5: The precipitation of the phosphomolybdate takes place more promptly in warm than in cold solutions, but the temperature should not exceed 60°C. during precipitation; a higher temperature tends to separate molybdic acid from the solution. This acid is nearly white, and its deposition in the filtrate on long standing should not be mistaken for a second precipitation of the yellow precipitate. The addition of 75 cc. of ammonium molybdate solution insures the presence of a liberal excess of the reagent, but the filtrate should be tested as in all quantitative procedures. The precipitation is probably complete in many cases in less than twelve hours; but it is better, when practicable, to allow the solution to stand for this length of time. Vigorous shaking or stirring promotes the separation of the precipitate.] [Note 6: The composition of the "yellow precipitate" undoubtedly varies slightly with varying conditions at the time of its formation. Its composition may probably fairly be represented by the formula, (NH_{4})_{3}PO_{4}.12MoO_{3}.H_{2}O, when precipitated under the conditions prescribed in the procedure. Whatever other variations may occur in its composition, the ratio of 12 MoO_{3}:1 P seems to hold, and this fact is utilized in volumetric processes for the determination of phosphorus, in which the molybdenum is reduced to a lower oxide and reoxidized by a standard solution of potassium permanganate. In principle, the procedure is comparable with that described for the determination of iron by permanganate.] PRECIPITATION OF MAGNESIUM AMMONIUM PHOSPHATE PROCEDURE.--Dissolve the precipitate of phosphomolybdate upon the filter by pouring through it dilute aqueous ammonia (one volume of dilute ammonia (sp. gr. 0.96) and three volumes of water, which should be carefully measured), and receive the solution in the beaker containing the bulk of the precipitate. The total volume of nitrate and washings should not much exceed 100 cc. Acidify the solution with dilute hydrochloric acid, and heat it nearly to boiling. Calculate the volume of magnesium ammonium chloride solution ("magnesia mixture") required to precipitate the phosphoric acid, assuming 40 per cent P_{2}O_{5} in the apatite. Measure out about 5 cc. in excess of this amount, and pour it into the acid solution. Then add slowly dilute ammonium hydroxide (1 volume of strong ammonia (sp. gr. 0.90) and 9 volumes of water), stirring constantly until a precipitate forms. Then add a volume of filtered, concentrated ammonia (sp. gr. 0.90) equal to one third of the volume of liquid in the beaker (Note 1). Allow the whole to cool. The precipitated magnesium ammonium phosphate should then be definitely crystalline in appearance (Note 2). (If it is desired to hasten the precipitation, the solution may be cooled, first in cold and then in ice-water, and stirred !constantly! for half an hour, when precipitation will usually be complete.) Decant the clear liquid through a filter, and transfer the precipitate to the filter, using as wash-water a mixture of one volume of concentrated ammonia and three volumes of water. It is not necessary to clean the beaker completely or to wash the precipitate thoroughly at this point, as it is necessary to purify it by reprecipitation. [Note 1: Magnesium ammonium phosphate is not a wholly insoluble substance, even under the most favorable analytical conditions. It is least soluble in a liquid containing one fourth of its volume of concentrated aqueous ammonia (sp. gr. 0.90) and this proportion should be carefully maintained as prescribed in the procedure. On account of this slight solubility the volume of solutions should be kept as small as possible and the amount of wash-water limited to that absolutely required. A large excess of the magnesium solution tends both to throw out magnesium hydroxide (shown by a persistently flocculent precipitate) and to cause the phosphate to carry down molybdic acid. The tendency of the magnesium precipitate to carry down molybdic acid is also increased if the solution is too concentrated. The volume should not be less than 90 cc., nor more than 125 cc., at the time of the first precipitation with the magnesia mixture.] [Note 2: The magnesium ammonium phosphate should be perfectly crystalline, and will be so if the directions are followed. The slow addition of the reagent is essential, and the stirring not less so. Stirring promotes the separation of the precipitate and the formation of larger crystals, and may therefore be substituted for digestion in the cold. The stirring-rod must not be allowed to scratch the glass, as the crystals adhere to such scratches and are removed with difficulty.] REPRECIPITATION AND IGNITION OF MAGNESIUM AMMONIUM PHOSPHATE A single precipitation of the magnesium compound in the presence of molybdenum compounds rarely yields a pure product. The molybdenum can be removed by solution of the precipitate in acid and precipitation of the molybdenum by sulphureted hydrogen, after which the magnesium precipitate may be again thrown down. It is usually more satisfactory to dissolve the magnesium precipitate and reprecipitate the phosphate as magnesium ammonium phosphate as described below. PROCEDURE.--Dissolve the precipitate from the filter in a little dilute hydrochloric acid (sp. gr. 1.12), allowing the acid solution to run into the beaker in which the original precipitation was made (Note 1). Wash the filter with water until the wash-water shows no test for chlorides, but avoid an unnecessary amount of wash-water. Add to the solution 2 cc. (not more) of magnesia mixture, and then dilute ammonium hydroxide solution (sp. gr. 0.96), drop by drop, with constant stirring, until the liquid smells distinctly of ammonia. Stir for a few moments and then add a volume of strong ammonia (sp. gr. 0.90), equal to one third of the volume of the solution. Allow the solution to stand for some hours, and then filter off the magnesium ammonium phosphate, which should be distinctly crystalline in character. Wash the precipitate with dilute ammonia water, as prescribed above, until, finally, 3 cc. of the washings, after acidifying with nitric acid, show no evidence of chlorides. Test both filtrates for complete precipitation by adding a few cubic centimeters of magnesia mixture and allowing them to stand for some time. Transfer the moist precipitate to a weighed porcelain or platinum crucible and ignite, using great care to raise the temperature slowly while drying the filter in the crucible, and to insure the ready access of oxygen during the combustion of the filter paper, thus guarding against a possible reduction of the phosphate, which would result in disastrous consequences both to the crucible, if of platinum, and the analysis. Do not raise the temperature above moderate redness until the precipitate is white. (Keep this precaution well in mind.) Ignite finally at the highest temperature of the Tirrill burner, and repeat the heating until the weight is constant. If the ignited precipitate is persistently discolored by particles of unburned carbon, moisten the mass with a drop or two of concentrated nitric acid and heat cautiously, finally igniting strongly. The acid will dissolve magnesium pyrophosphate from the surface of the particles of carbon, which will then burn away. Nitric acid also aids as an oxidizing agent in supplying oxygen for the combustion of the carbon. From the weight of magnesium pyrophosphate (Mg_{2}P_{2}O_{7}) obtained, calculate the phosphoric anhydride (P_{2}O_{5}) in the sample of apatite. [Note 1: The ionic change involved in the precipitation of the magnesium compound is PO_{4}^{---} + NH_{4}^{+} + Mg^{++} --> [MgNH_{4}PO_{4}]. The magnesium ammonium phosphate is readily dissolved by acids, even those which are no stronger than acetic acid. This is accounted for by the fact that two of the ions into which phosphoric acid may dissociate, the HPO_{4}^{--} or H_{2}PO_{4}^{-} ions, exhibit the characteristics of very weak acids, in that they show almost no tendency to dissociate further into H^{+} and PO_{4}^{--} ions. Consequently the ionic changes which occur when the magnesium ammonium phosphate is brought into contact with an acid may be typified by the reaction: H^{+} + Mg^{++} + NH_{4}^{+} + PO_{4}^{---} --> Mg^{++} + NH_{4}^{+} + HPO_{4}^{--}; that is, the PO_{4}^{--} ions and the H^{+} ions lose their identity in the formation of the new ion, HPO_{4}^{--}, and this continues until the magnesium ammonium phosphate is entirely dissolved.] [Note 2: During ignition the magnesium ammonium phosphate loses ammonia and water and is converted into magnesium pyrophosphate: 2MgNH_{4}PO_{4} --> Mg_{2}P_{2}O_{7} + 2NH_{3} + H_{2}O. The precautions mentioned on pages 111 and 123 must be observed with great care during the ignition of this precipitate. The danger here lies in a possible reduction of the phosphate by the carbon of the filter paper, or by the ammonia evolved, which may act as a reducing agent. The phosphorus then attacks and injures a platinum crucible, and the determination is valueless.] ANALYSIS OF LIMESTONE Limestones vary widely in composition from a nearly pure marble through the dolomitic limestones, containing varying amounts of magnesium, to the impure varieties, which contain also ferrous and manganous carbonates and siliceous compounds in variable proportions. Many other minerals may be inclosed in limestones in small quantities, and an exact qualitative analysis will often show the presence of sulphides or sulphates, phosphates, and titanates, and the alkali or even the heavy metals. No attempt is made in the following procedures to provide a complete quantitative scheme which would take into account all of these constituents. Such a scheme for a complete analysis of a limestone may be found in Bulletin No. 700 of the United States Geological Survey. It is assumed that, for these practice determinations, a limestone is selected which contains only the more common constituents first enumerated above. DETERMINATION OF MOISTURE The determination of the amount of moisture in minerals or ores is often of great importance. Ores which have been exposed to the weather during shipment may have absorbed enough moisture to appreciably affect the results of analysis. Since it is essential that the seller and buyer should make their analyses upon comparable material, it is customary for each analyst to determine the moisture in the sample examined, and then to calculate the percentages of the various constituents with reference to a sample dried in the air, or at a temperature a little above 100°C., which, unless the ore has undergone chemical change because of the wetting, should be the same before and after shipment. PROCEDURE.--Spread 25 grams of the powdered sample on a weighed watch-glass; weigh to the nearest 10 milligrams only and heat at 105°C.; weigh at intervals of an hour, after cooling in a desiccator, until the loss of weight after an hour's heating does not exceed 10 milligrams. It should be noted that a variation in weight of 10 milligrams in a total weight of 25 grams is no greater relatively than a variation of 0.1 milligram when the sample taken weighs 0.25 gram DETERMINATION OF THE INSOLUBLE MATTER AND SILICA PROCEDURE.--Weigh out two portions of the original powdered sample (not the dried sample), of about 5 grams each, into 250 cc. casseroles, and cover each with a watch-glass (Note 1). Pour over the powder 25 cc. of water, and then add 50 cc. of dilute hydrochloric acid (sp. gr. 1.12) in small portions, warming gently, until nothing further appears to dissolve (Note 2). Evaporate to dryness on the water bath. Pour over the residue a mixture of 5 cc. of water and 5 cc. of concentrated hydrochloric acid (sp. gr. 1.2) and again evaporate to dryness, and finally heat for at least an hour at a temperature of 110°C. Pour over this residue 50 cc. of dilute hydrochloric acid (one volume acid (sp. gr. 1.12) to five volumes water), and boil for about five minutes; then filter and wash twice with the dilute hydrochloric acid, and then with hot water until free from chlorides. Transfer the filter and contents to a porcelain crucible, dry carefully over a low flame, and ignite to constant weight. The residue represents the insoluble matter and the silica from any soluble silicates (Note 3). Calculate the combined percentage of these in the limestone. [Note 1: The relatively large weight (5 grams) taken for analysis insures greater accuracy in the determination of the ingredients which are present in small proportions, and is also more likely to be a representative sample of the material analyzed.] [Note 2: It is plain that the amount of the insoluble residue and also its character will often depend upon the strength of acid used for solution of the limestone. It cannot, therefore, be regarded as representing any well-defined constituent, and its determination is essentially empirical.] [Note 3: It is probable that some of the silicates present are wholly or partly decomposed by the acid, and the soluble silicic acid must be converted by evaporation to dryness, and heating, into white, insoluble silica. This change is not complete after one evaporation. The heating at a temperature somewhat higher than that of the water bath for a short time tends to leave the silica in the form of a powder, which promotes subsequent filtration. The siliceous residue is washed first with dilute acid to prevent hydrolytic changes, which would result in the formation of appreciable quantities of insoluble basic iron or aluminium salts on the filter when washing with hot water. If it is desired to determine the percentage of silica separately, the ignited residue should be mixed in a platinum crucible with about six times its weight of anhydrous sodium carbonate, and the procedure given on page 151 should be followed. The filtrate from the silica is then added to the main filtrate from the insoluble residue.] DETERMINATION OF FERRIC OXIDE AND ALUMINIUM OXIDE (WITH MANGANESE) PROCEDURE.--To the filtrate from the insoluble residue add ammonium hydroxide until the solution just smells distinctly of ammonia, but do not add an excess. Then add 5 cc. of saturated bromine water (Note 1), and boil for five minutes. If the smell of ammonia has disappeared, again add ammonium hydroxide in slight excess, and 3 cc. of bromine water, and heat again for a few minutes. Finally add 10 cc. of ammonium chloride solution and keep the solution warm until it barely smells of ammonia; then filter promptly (Note 2). Wash the filter twice with hot water, then (after replacing the receiving beaker) pour through it 25 cc. of hot, dilute hydrochloric acid (one volume dilute HCl [sp. gr. 1.12] to five volumes water). A brown residue insoluble in the acid may be allowed to remain on the filter. Wash the filter five times with hot water, add to the filtrate ammonium hydroxide and bromine water as described above, and repeat the precipitation. Collect the precipitate on the filter already used, wash it free from chlorides with hot water, and ignite and weigh as described for ferric hydroxide on page 110. The residue after ignition consists of ferric oxide, alumina, and mangano-manganic oxide (Mn_{3}O_{4}), if manganese is present. These are commonly determined together (Note 3). Calculate the percentage of the combined oxides in the limestone. [Note 1: The addition of bromine water to the ammoniacal solutions serves to oxidize any ferrous hydroxide to ferric hydroxide and to precipitate manganese as MnO(OH)_{2}. The solution must contain not more than a bare excess of hydroxyl ions (ammonium hydroxide) when it is filtered, on account of the tendency of the aluminium hydroxide to redissolve. The solution should not be strongly ammoniacal when the bromine is added, as strong ammonia reacts with the bromine, with the evolution of nitrogen.] [Note 2: The precipitate produced by ammonium hydroxide and bromine should be filtered off promptly, since the alkaline solution absorbs carbon dioxide from the air, with consequent partial precipitation of the calcium as carbonate. This is possible even under the most favorable conditions, and for this reason the iron precipitate is redissolved and again precipitated to free it from calcium. When the precipitate is small, this reprecipitation may be omitted.] [Note 3: In the absence of significant amounts of manganese the iron and aluminium may be separately determined by fusion of the mixed ignited precipitate, after weighing, with about ten times its weight of acid potassium sulphate, solution of the cold fused mass in water, and volumetric determination of the iron, as described on page 66. The aluminium is then determined by difference, after subtracting the weight of ferric oxide corresponding to the amount of iron found. If a separate determination of the iron, aluminium, and manganese is desired, the mixed precipitate may be dissolved in acid before ignition, and the separation effected by special methods (see, for example, Fay, !Quantitative Analyses!, First Edition, pp. 15-19 and 23-27).] DETERMINATION OF CALCIUM PROCEDURE.--To the combined filtrates from the double precipitation of the hydroxides just described, add 5 cc. of dilute ammonium hydroxide (sp. gr. 0.96), and transfer the liquid to a 500 cc. graduated flask, washing out the beaker carefully. Cool to laboratory temperature, and fill the flask with distilled water until the lowest point of the meniscus is exactly level with the mark on the neck of the flask. Carefully remove any drops of water which are on the inside of the neck of the flask above the graduation by means of a strip of filter paper, make the solution uniform by pouring it out into a dry beaker and back into the flask several times. Measure off one fifth of this solution as follows (Note 1): Pour into a 100 cc. graduated flask about 10 cc. of the solution, shake the liquid thoroughly over the inner surface of the small flask, and pour it out. Repeat the same operation. Fill the 100 cc. flask until the lowest point of the meniscus is exactly level with the mark on its neck, remove any drops of solution from the upper part of the neck with filter paper, and pour the solution into a beaker (400-500 cc.). Wash out the flask with small quantities of water until it is clean, adding these to the 100 cc. of solution. When the duplicate portion of 100 cc. is measured out from the solution, remember that the flask must be rinsed out twice with that solution, as prescribed above, before the measurement is made. (A 100 cc. pipette may be used to measure out the aliquot portions, if preferred.) Dilute each of the measured portions to 250 cc. with distilled water, heat the whole to boiling, and add ammonium oxalate solution slowly in moderate excess, stirring well. Boil for two minutes; allow the precipitated calcium oxalate to settle for a half-hour, and decant through a filter. Test the filtrate for complete precipitation by adding a few cubic centimeters of the precipitant, allowing it to stand for fifteen minutes. If no precipitate forms, make the solution slightly acid with hydrochloric acid (Note 2); see that it is properly labeled and reserve it to be combined with the filtrate from the second calcium oxalate precipitation (Notes 3 and 4). Redissolve the calcium oxalate in the beaker with warm hydrochloric acid, pouring the acid through the filter. Wash the filter five times with water, and finally pour through it aqueous ammonia. Dilute the solution to 250 cc., bring to boiling, and add 1 cc. ammonium oxalate solution (Note 5) and ammonia in slight excess; boil for two minutes, and set aside for a half-hour. Filter off the calcium oxalate upon the filter first used, and wash free from chlorides. The filtrate should be made barely acid with hydrochloric acid and combined with the filtrate from the first precipitation. Begin at once the evaporation of the solutions for the determination of magnesium as described below. The precipitate of calcium oxalate may be converted into calcium oxide by ignition without previous drying. After burning the filter, it may be ignited for three quarters of an hour in a platinum crucible at the highest heat of the Bunsen or Tirrill burner, and finally for ten minutes at the blast lamp (Note 6). Repeat the heating over the blast lamp until the weight is constant. As the calcium oxide absorbs moisture from the air, it must (after cooling) be weighed as rapidly as possible. The precipitate may, if preferred, be placed in a weighted porcelain crucible. After burning off the filter and heating for ten minutes the calcium precipitate may be converted into calcium sulphate by placing 2 cc. of dilute sulphuric acid in the crucible (cold), heating the covered crucible very cautiously over a low flame to drive off the excess of acid, and finally at redness to constant weight (Note 7). From the weight of the oxide or sulphate, calculate the percentage of the calcium (Ca) in the limestone, remembering that only one fifth of the total solution is used for this determination. [Note 1: If the calcium were precipitated from the entire solution, the quantity of the precipitate would be greater than could be properly treated. The solution is, therefore, diluted to a definite volume (500 cc.), and exactly one fifth (100 cc.) is measured off in a graduated flask or by means of a pipette.] [Note 2: The filtrate from the calcium oxalate should be made slightly acid immediately after filtration, in order to avoid the solvent action of the alkaline liquid upon the glass.] [Note 3: The accurate quantitative separation of calcium and magnesium as oxalates requires considerable care. The calcium precipitate usually carries down with it some magnesium, and this can best be removed by redissolving the precipitate after filtration, and reprecipitation in the presence of only the small amount of magnesium which was included in the first precipitate. When, however, the proportion of magnesium is not very large, the second precipitation of the calcium can usually be avoided by precipitating it from a rather dilute solution (800 cc. or so) and in the presence of a considerable excess of the precipitant, that is, rather more than enough to convert both the magnesium and calcium into oxalates.] [Note 4: The ionic changes involved in the precipitation of calcium as oxalate are exceedingly simple, and the principles discussed in connection with the barium sulphate precipitation on page 113 also apply here. The reaction is C_{2}O_{4}^{--} + Ca^{++} --> [CaC_{2}O_{4}]. Calcium oxalate is nearly insoluble in water, and only very slightly soluble in acetic acid, but is readily dissolved by the strong mineral acids. This behavior with acids is explained by the fact that oxalic acid is a stronger acid than acetic acid; when, therefore, the oxalate is brought into contact with the latter there is almost no tendency to diminish the concentration of C_{2}O_{4}^{--} ions by the formation of an acid less dissociated than the acetic acid itself, and practically no solvent action ensues. When a strong mineral acid is present, however, the ionization of the oxalic acid is much reduced by the high concentration of the H^{+} ions from the strong acid, the formation of the undissociated acid lessens the concentration of the C_{2}O_{4}^{--} ions in solution, more of the oxalate passes into solution to re-establish equilibrium, and this process repeats itself until all is dissolved. The oxalate is immediately reprecipitated from such a solution on the addition of OH^{-} ions, which, by uniting with the H^{+} ions of the acids (both the mineral acid and the oxalic acid) to form water, leave the Ca^{++} and C_{2}O_{4}^{--} ions in the solution to recombine to form [CaC_{2}O_{4}], which is precipitated in the absence of the H^{+} ions. It is well at this point to add a small excess of C_{2}O_{4}^{--} ions in the form of ammonium oxalate to decrease the solubility of the precipitate. The oxalate precipitate consists mainly of CaC_{2}O_{4}.H_{2}O when thrown down.] [Note 5: The small quantity of ammonium oxalate solution is added before the second precipitation of the calcium oxalate to insure the presence of a slight excess of the reagent, which promotes the separation of the calcium compound.] [Note 6: On ignition the calcium oxalate loses carbon dioxide and carbon monoxide, leaving calcium oxide: CaC_{2}O_{4}.H_{2}O --> CaO + CO_{2} + CO + H_{2}O. For small weights of the oxalate (0.6 gram or less) this reaction may be brought about in a platinum crucible at the highest temperature of a Tirrill burner, but it is well to ignite larger quantities than this over the blast lamp until the weight is constant.] [Note 7: The heat required to burn the filter, and that subsequently applied as described, will convert most of the calcium oxalate to calcium carbonate, which is changed to sulphate by the sulphuric acid. The reactions involved are CaC_{2}O_{4} --> CaCO_{3} + CO, CaCO_{3} + H_{2}SO_{4} --> CaSO_{4} + H_{2}O + CO_{2}. If a porcelain crucible is employed for ignition, this conversion to sulphate is to be preferred, as a complete conversion to oxide is difficult to accomplish.] [Note 8: The determination of the calcium may be completed volumetrically by washing the calcium oxalate precipitate from the filter into dilute sulphuric acid, warming, and titrating the liberated oxalic acid with a standard solution of potassium permanganate as described on page 72. When a considerable number of analyses are to be made, this procedure will save much of the time otherwise required for ignition and weighing.] DETERMINATION OF MAGNESIUM PROCEDURE.--Evaporate the acidified filtrates from the calcium precipitates until the salts begin to crystallize, but do !not! evaporate to dryness (Note 1). Dilute the solution cautiously until the salts are brought into solution, adding a little acid if the solution has evaporated to very small volume. The solution should be carefully examined at this point and must be filtered if a precipitate has appeared. Heat the clear solution to boiling; remove the burner and add 25 cc. of a solution of disodium phosphate. Then add slowly dilute ammonia (1 volume strong ammonia (sp. gr. 0.90) and 9 volumes water) as long as a precipitate continues to form. Finally, add a volume of concentrated ammonia (sp. gr. 0.90) equal to one third of the volume of the solution, and allow the whole to stand for about twelve hours. Decant the solution through a filter, wash it with dilute ammonia water, proceeding as prescribed for the determination of phosphoric anhydride on page 122, including; the reprecipitation (Note 2), except that 3 cc. of disodium phosphate solution are added before the reprecipitation of the magnesium ammonium phosphate instead of the magnesia mixture there prescribed. From the weight of the pyrophosphate, calculate the percentage of magnesium oxide (MgO) in the sample of limestone. Remember that the pyrophosphate finally obtained is from one fifth of the original sample. [Note 1: The precipitation of the magnesium should be made in as small volume as possible, and the ratio of ammonia to the total volume of solution should be carefully provided for, on account of the relative solubility of the magnesium ammonium phosphate. This matter has been fully discussed in connection with the phosphoric anhydride determination.] [Note 2: The first magnesium ammonium phosphate precipitate is rarely wholly crystalline, as it should be, and is not always of the proper composition when precipitated in the presence of such large amounts of ammonium salts. The difficulty can best be remedied by filtering the precipitate and (without washing it) redissolving in a small quantity of hydrochloric acid, from which it may be again thrown down by ammonia after adding a little disodium phosphate solution. If the flocculent character was occasioned by the presence of magnesium hydroxide, the second precipitation, in a smaller volume containing fewer salts, will often result more favorably. The removal of iron or alumina from a contaminated precipitate is a matter involving a long procedure, and a redetermination of the magnesium from a new sample, with additional precautions, is usually to be preferred.] DETERMINATION OF CARBON DIOXIDE !Absorption Apparatus! [Illustration: Fig. 3] The apparatus required for the determination of the carbon dioxide should be arranged as shown in the cut (Fig. 3). The flask (A) is an ordinary wash bottle, which should be nearly filled with dilute hydrochloric acid (100 cc. acid (sp. gr. 1.12) and 200 cc. of water). The flask is connected by rubber tubing (a) with the glass tube (b) leading nearly to the bottom of the evolution flask (B) and having its lower end bent upward and drawn out to small bore, so that the carbon dioxide evolved from the limestone cannot bubble back into (b). The evolution flask should preferably be a wide-mouthed Soxhlet extraction flask of about 150 cc. capacity because of the ease with which tubes and stoppers may be fitted into the neck of a flask of this type. The flask should be fitted with a two-hole rubber stopper. The condenser (C) may consist of a tube with two or three large bulbs blown in it, for use as an air-cooled condenser, or it may be a small water-jacketed condenser. The latter is to be preferred if a number of determinations are to be made in succession. A glass delivery tube (c) leads from the condenser to the small U-tube (D) containing some glass beads or small pieces of glass rod and 3 cc. of a saturated solution of silver sulphate, with 3 cc. of concentrated sulphuric acid (sp. gr. 1.84). The short rubber tubing (d) connects the first U-tube to a second U-tube (E) which is filled with small dust-free lumps of dry calcium chloride, with a small, loose plug of cotton at the top of each arm. Both tubes should be closed by cork stoppers, the tops of which are cut off level with, or preferably forced a little below, the top of the U-tube, and then neatly sealed with sealing wax. The carbon dioxide may be absorbed in a tube containing soda lime (F) or in a Geissler bulb (F') containing a concentrated solution of potassium hydroxide (Note 2). The tube (F) is a glass-stoppered side-arm U-tube in which the side toward the evolution flask and one half of the other side are filled with small, dust-free lumps of soda lime of good quality (Note 3). Since soda lime contains considerable moisture, the other half of the right side of the tube is filled with small lumps of dry, dust-free calcium chloride to retain the moisture from the soda lime. Loose plugs of cotton are placed at the top of each arm and between the soda lime and the calcium chloride. The Geissler bulb (F'), if used, should be filled with potassium hydroxide solution (1 part of solid potassium hydroxide dissolved in two parts of water) until each small bulb is about two thirds full (Note 4). A small tube containing calcium chloride is connected with the Geissler bulb proper by a ground joint and should be wired to the bulb for safety. This is designed to retain any moisture from the hydroxide solution. A piece of clean, fine copper wire is so attached to the bulb that it can be hung from the hook above a balance pan, or other support. The small bottle (G) with concentrated sulphuric acid (sp. gr. 1.84) is so arranged that the tube (f) barely dips below the surface. This will prevent the absorption of water vapor by (F) or (F') and serves as an aid in regulating the flow of air through the apparatus. (H) is an aspirator bottle of about four liters capacity, filled with water; (k) is a safety tube and a means of refilling (H); (h) is a screw clamp, and (K) a U-tube filled with soda lime. [Note 1: The air current, which is subsequently drawn through the apparatus, to sweep all of the carbon dioxide into the absorption apparatus, is likely to carry with it some hydrochloric acid from the evolution flask. This acid is retained by the silver sulphate solution. The addition of concentrated sulphuric acid to this solution reduces its vapor pressure so far that very little water is carried on by the air current, and this slight amount is absorbed by the calcium chloride in (E). As the calcium chloride frequently contains a small amount of a basic material which would absorb carbon dioxide, it is necessary to pass carbon dioxide through (E) for a short time and then drive all the gas out with a dry air current for thirty minutes before use.] [Note 2: Soda-lime absorption tubes are to be preferred if a satisfactory quality of soda lime is available and the number of determinations to be made successively is small. The potash bulbs will usually permit of a larger number of successive determinations without refilling, but they require greater care in handling and in the analytical procedure.] [Note 3: Soda lime is a mixture of sodium and calcium hydroxides. Both combine with carbon dioxide to form carbonates, with the evolution of water. Considerable heat is generated by the reaction, and the temperature of the tube during absorption serves as a rough index of the progress of the reaction through the mass of soda lime. It is essential that soda lime of good quality for analytical purposes should be used. The tube should not contain dust, as this is likely to be swept away.] [Note 4: The solution of the hydroxide for use in the Geissler bulb must be highly concentrated to insure complete absorption of the carbon dioxide and also to reduce the vapor pressure of the solution, thus lessening the danger of loss of water with the air which passes through the bulbs. The small quantity of moisture which is then carried out of the bulbs is held by the calcium chloride in the prolong tube. The best form of absorption bulb is that to which the prolong tube is attached by a ground glass joint. After the potassium hydroxide is approximately half consumed in the first bulb of the absorption apparatus, potassium bicarbonate is formed, and as it is much less soluble than the carbonate, it often precipitates. Its formation is a warning that the absorbing power of the hydroxide is much diminished.] !The Analysis! PROCEDURE.-- Weigh out into the flask (B) about 1 gram of limestone. Cover it with 15 cc. of water. Weigh the absorption apparatus (F) or (F') accurately after allowing it to stand for 30 minutes in the balance case, and wiping it carefully with a lintless cloth, taking care to handle it as little as possible after wiping (Note 1). Connect the absorption apparatus with (e) and (f). If a soda-lime tube is used, be sure that the arm containing the soda lime is next the tube (E) and that the glass stopcocks are open. To be sure that the whole apparatus is airtight, disconnect the rubber tube from the flask (A), making sure that the tubes (a) and (b) do not contain any hydrochloric acid, close the pinchcocks (a) and (k) and open (h). No bubbles should pass through (D) or (G) after a few seconds. When assured that the fittings are tight, close (h) and open (a) cautiously to admit air to restore atmospheric pressure. This precaution is essential, as a sudden inrush of air will project liquid from (D) or (F'). Reconnect the rubber tube with the flask (A). Open the pinchcocks (a) and (k) and blow over about 10 cc. of the hydrochloric acid from (A) into (B). When the action of the acid slackens, blow over (slowly) another 10 cc. The rate of gas evolution should not exceed for more than a few seconds that at which about two bubbles per second pass through (G) (Note 2). Repeat the addition of acid in small portions until the action upon the limestone seems to be at an end, taking care to close (a) after each addition of acid (Note 3). Disconnect (A) and connect the rubber tubing with the soda-lime tube (K) and open (a). Then close (k) and open (h), regulating the flow of water from (H) in such a way that about two bubbles per second pass through (G). Place a small flame under (B) and !slowly! raise the contents to boiling and boil for three minutes. Then remove the burner from under (B) and continue to draw air through the apparatus for 20-30 minutes, or until (H) is emptied (Note 4). Remove the absorption apparatus, closing the stopcocks on (F) or stoppering the open ends of (F'), leave the apparatus in the balance case for at least thirty minutes, wipe it carefully and weigh, after opening the stopcocks (or removing plugs). The increase in weight is due to absorption of CO_{2}, from which its percentage in the sample may be calculated. After cleaning (B) and refilling (H), the apparatus is ready for the duplicate analysis. [Note 1: The absorption tubes or bulbs have large surfaces on which moisture may collect. By allowing them to remain in the balance case for some time before weighing, the amount of moisture absorbed on the surface is as nearly constant as practicable during two weighings, and a uniform temperature is also assured. The stopcocks of the U-tube should be opened, or the plugs used to close the openings of the Geissler bulb should be removed before weighing in order that the air contents shall always be at atmospheric pressure.] [Note 2: If the gas passes too rapidly into the absorption apparatus, some carbon dioxide may be carried through, not being completely retained by the absorbents.] [Note 3: The essential ionic changes involved in this procedure are the following: It is assumed that the limestone, which is typified by calcium carbonate, is very slightly soluble in water, and the ions resulting are Ca^{++} and CO_{3}^{--}. In the presence of H^{+} ions of the mineral acid, the CO_{3}^{--} ions form [H_{2}CO_{3}]. This is not only a weak acid which, by its formation, diminishes the concentration of the CO_{3}^{--} ions, thus causing more of the carbonate to dissolve to re-establish equilibrium, but it is also an unstable compound and breaks down into carbon dioxide and water.] [Note 4: Carbon dioxide is dissolved by cold water, but the gas is expelled by boiling, and, together with that which is distributed through the apparatus, is swept out into the absorption bulb by the current of air. This air is purified by drawing it through the tube (K) containing soda lime, which removes any carbon dioxide which may be in it.] DETERMINATION OF LEAD, COPPER, IRON, AND ZINC IN BRASS ELECTROLYTIC SEPARATIONS !General Discussion! When a direct current of electricity passes from one electrode to another through solutions of electrolytes, the individual ions present in these solutions tend to move toward the electrode of opposite electrical charge to that which each ion bears, and to be discharged by that electrode. Whether or not such discharge actually occurs in the case of any particular ion depends upon the potential (voltage) of the current which is passing through the solution, since for each ion there is, under definite conditions, a minimum potential below which the discharge of the ion cannot be effected. By taking advantage of differences in discharge-potentials, it is possible to effect separations of a number of the metallic ions by electrolysis, and at the same time to deposit the metals in forms which admit of direct weighing. In this way the slower procedures of precipitation and filtration may frequently be avoided. The following paragraphs present a brief statement of the fundamental principles and conditions underlying electro-analysis. The total energy of an electric current as it passes through a solution is distributed among three factors, first, its potential, which is measured in volts, and corresponds to what is called "head" in a stream of water; second, current strength, which is measured in amperes, and corresponds to the volume of water passing a cross-section of a stream in a given time interval; and third, the resistance of the conducting medium, which is measured in ohms. The relation between these three factors is expressed by Ohm's law, namely, that !I = E/R!, when I is current strength, E potential, and R resistance. It is plain that, for a constant resistance, the strength of the current and its potential are mutually and directly interdependent. As already stated, the applied electrical potential determines whether or not deposition of a metal upon an electrode actually occurs. The current strength determines the rate of deposition and the physical characteristics of the deposit. The resistance of the solution is generally so small as to fall out of practical consideration. Approximate deposition-potentials have been determined for a number of the metallic elements, and also for hydrogen and some of the acid-forming radicals. The values given below are those required for deposition from normal solutions at ordinary temperatures with reference to a hydrogen electrode. They must be regarded as approximate, since several disturbing factors and some secondary reactions render difficult their exact application under the conditions of analysis. They are: Zn Cd Fe Ni Pb H Cu Sb Hg Ag SO_{4} +0.77 +0.42 +0.34 +0.33 +0.13 0 -0.34 -0.67 -0.76 -0.79 +1.90 From these data it is evident that in order to deposit copper from a normal solution of copper sulphate a minimum potential equal to the algebraic sum of the deposition-potentials of copper ions and sulphate ions must be applied, that is, +1.56 volts. The deposition of zinc from a solution of zinc sulphate would require +2.67 volts, but, since the deposition of hydrogen from sulphuric acid solution requires only +1.90 volts, the quantitative deposition of zinc by electrolysis from a sulphuric acid solution of a zinc salt is not practicable. On the other hand, silver, if present in a solution of copper sulphate, would deposit with the copper. The foregoing examples suffice to illustrate the application of the principle of deposition potentials, but it must further be noted that the values stated apply to normal solutions of the compounds in question, that is, to solutions of considerable concentrations. As the concentration of the ions diminishes, and hence fewer ions approach the electrodes, somewhat higher voltages are required to attract and discharge them. From this it follows that the concentrations should be kept as high as possible to effect complete deposition in the least practicable time, or else the potentials applied must be progressively increased as deposition proceeds. In practice, the desired result is obtained by starting with small volumes of solution, using as large an electrode surface as possible, and by stirring the solution to bring the ions in contact with the electrodes. This is, in general, a more convenient procedure than that of increasing the potential of the current during electrolysis, although that method is also used. As already stated, those ions in a solution of electrolytes will first be discharged which have the lowest deposition potentials, and so long as these ions are present around the electrode in considerable concentration they, almost alone, are discharged, but, as their concentration diminishes, other ions whose deposition potentials are higher but still within that of the current applied, will also begin to separate. For example, from a nitric acid solution of copper nitrate, the copper ions will first be discharged at the cathode, but as they diminish in concentration hydrogen ions from the acid (or water) will be also discharged. Since the hydrogen thus liberated is a reducing agent, the nitric acid in the solution is slowly reduced to ammonia, and it may happen that if the current is passed through for a long time, such a solution will become alkaline. Oxygen is liberated at the anode, but, since there is no oxidizable substance present around that electrode, it escapes as oxygen gas. It should be noted that, in general, the changes occurring at the cathode are reductions, while those at the anode are oxidations. For analytical purposes, solutions of nitrates or sulphates of the metals are preferable to those of the chlorides, since liberated chlorine attacks the electrodes. In some cases, as for example, that of silver, solution of salts forming complex ions, like that of the double cyanide of silver and potassium, yield better metallic deposits. Most metals are deposited as such upon the cathode; a few, notably lead and manganese, separate in the form of dioxides upon the anode. It is evidently important that the deposited material should be so firmly adherent that it can be washed, dried, and weighed without loss in handling. To secure these conditions it is essential that the current density (that is, the amount of current per unit of area of the electrodes) shall not be too high. In prescribing analytical conditions it is customary to state the current strength in "normal densities" expressed in amperes per 100 sq. cm. of electrode surface, as, for example, "N.D_{100} = 2 amps." If deposition occurs too rapidly, the deposit is likely to be spongy or loosely adherent and falls off on subsequent treatment. This places a practical limit to the current density to be employed, for a given electrode surface. The cause of the unsatisfactory character of the deposit is apparently sometimes to be found in the coincident liberation of considerable hydrogen and sometimes in the failure of the rapidly deposited material to form a continuous adherent surface. The effect of rotating electrodes upon the character of the deposit is referred to below. The negative ions of an electrolyte are attracted to the anode and are discharged on contact with it. Anions such as the chloride ion yield chlorine atoms, from which gaseous chlorine molecules are formed and escape. The radicals which compose such ions as NO_{3}^{-} or SO_{4}^{--} are not capable of independent existence after discharge, and break down into oxygen and N_{2}O_{5} and SO_{3} respectively. The oxygen escapes and the anhydrides, reacting with water, re-form nitric and sulphuric acids. The law of Faraday expresses the relation between current strength and the quantities of the decomposition products which, under constant conditions, appear at the electrodes, namely, that a given quantity of electricity, acting for a given time, causes the separation of chemically equivalent quantities of the various elements or radicals. For example, since 107.94 grams of silver is equivalent to 1.008 grams of hydrogen, and that in turn to 8 grams of oxygen, or 31.78 grams of copper, the quantity of electricity which will cause the deposit of 107.94 grams of silver in a given time will also separate the weights just indicated of the other substances. Experiments show that a current of one ampere passing for one second, i.e., a coulomb of electricity, causes the deposition of 0.001118 gram of silver from a normal solution of a silver salt. The number of coulombs required to deposit 107.94 grams is 107.94/0.001118 or 96,550 and the same number of coulombs will also cause the separation of 1.008 grams of hydrogen, 8 grams of oxygen or 31.78 grams of copper. While it might at first appear that Faraday's law could thus be used as a basis for the calculation of the time required for the deposition of a given quantity of an electrolyte from solution, it must be remembered that the law expresses what occurs when the concentration of the ions in the solution is kept constant, as, for example, when the anode in a silver salt solution is a plate of metallic silver. Under the conditions of electro-analysis the concentration of the ions is constantly diminishing as deposition proceeds and the time actually required for complete deposition of a given weight of material by a current of constant strength is, therefore, greater than that calculated on the basis of the law as stated above. The electrodes employed in electro-analysis are almost exclusively of platinum, since that metal alone satisfactorily resists chemical action of the electrolytes, and can be dried and weighed without change in composition. The platinum electrodes may be used in the form of dishes, foil or gauze. The last, on account of the ease of circulation of the electrolyte, its relatively large surface in proportion to its weight and the readiness with which it can be washed and dried, is generally preferred. Many devices have been described by the use of which the electrode upon which deposition occurs can be mechanically rotated. This has an effect parallel to that of greatly increasing the electrode surface and also provides a most efficient means of stirring the solution. With such an apparatus the amperage may be increased to 5 or even 10 amperes and depositions completed with great rapidity and accuracy. It is desirable, whenever practicable, to provide a rotating or stirring device, since, for example, the time consumed in the deposition of the amount of copper usually found in analysis may be reduced from the 20 to 24 hours required with stationary electrodes, and unstirred solutions, to about one half hour. DETERMINATION OF COPPER AND LEAD PROCEDURE.--Weigh out two portions of about 0.5 gram each (Note 1) into tall, slender lipless beakers of about 100 cc. capacity. Dissolve the metal in a solution of 5 cc. of dilute nitric acid (sp. gr. 1.20) and 5 cc. of water, heating gently, and keeping the beaker covered. When the sample has all dissolved (Note 2), wash down the sides of the beaker and the bottom of the watch-glass with water and dilute the solution to about 50 cc. Carefully heat to boiling and boil for a minute or two to expel nitrous fumes. Meanwhile, four platinum electrodes, two anodes and two cathodes, should be cleaned by dipping in dilute nitric acid, washing with water and finally with 95 per cent alcohol (Note 3). The alcohol may be ignited and burned off. The electrodes are then cooled in a desiccator and weighed. Connect the electrodes with the binding posts (or other device for connection with the electric circuit) in such a way that the copper will be deposited upon the electrode with the larger surface, which is made the cathode. The beaker containing the solution should then be raised into place from below the electrodes until the latter reach nearly to the bottom of the beaker. The support for the beaker must be so arranged that it can be easily raised or lowered. If the electrolytic apparatus is provided with a mechanism for the rotation of the electrode or stirring of the electrolyte, proceed as follows: Arrange the resistance in the circuit to provide a direct current of about one ampere. Pass this current through the solution to be electrolyzed, and start the rotating mechanism. Keep the beaker covered as completely as possible, using a split watch-glass (or other device) to avoid loss by spattering. When the solution is colorless, which is usually the case after about 35 minutes, rinse off the cover glass, wash down the sides of the beaker, add about 0.30 gram of urea and continue the electrolysis for another five minutes (Notes 4 and 5). If stationary electrodes are employed, the current strength should be about 0.1 ampere, which may, after 12 to 15 hours, be increased to 0.2 ampere. The time required for complete deposition is usually from 20 to 24 hours. It is advisable to add 5 cc. of nitric acid (sp. gr. 1.2) if the electrolysis extends over this length of time. No urea is added in this case. When the deposition of the copper appears to be complete, stop the rotating mechanism and slowly lower the beaker with the left hand, directing at the same time a stream of water from a wash bottle on both electrodes. Remove the beaker, shut off the current, and, if necessary, complete the washing of the electrodes (Note 6). Rinse the electrodes cautiously with alcohol and heat them in a hot closet until the alcohol has just evaporated, but no longer, since the copper is likely to oxidize at the higher temperature. (The alcohol may be removed by ignition if care is taken to keep the electrodes in motion in the air so that the copper deposit is not too strongly heated at any one point.) Test the solution in the beaker for copper as follows, remembering that it is to be used for subsequent determinations of iron and zinc: Remove about 5 cc. and add a slight excess of ammonia. Compare the mixture with some distilled water, holding both above a white surface. The solution should not show any tinge of blue. If the presence of copper is indicated, add the test portion to the main solution, evaporate the whole to a volume of about 100 cc., and again electrolyze with clean electrodes (Note 7). After cooling the electrodes in a desiccator, weigh them and from the weight of copper on the cathode and of lead dioxide (PbO_{2}) on the anode, calculate the percentage of copper (Cu) and of lead (Pb) in the brass. [Note 1: It is obvious that the brass taken for analysis should be untarnished, which can be easily assured, when wire is used, by scouring with emery. If chips or borings are used, they should be well mixed, and the sample for analysis taken from different parts of the mixture.] [Note 2: If a white residue remains upon treatment of the alloy with nitric acid, it indicates the presence of tin. The material is not, therefore, a true brass. This may be treated as follows: Evaporate the solution to dryness, moisten the residue with 5 cc. of dilute nitric acid (sp. gr. 1.2) and add 50 cc. of hot water. Filter off the meta-stannic acid, wash, ignite in porcelain and weigh as SnO_{2}. This oxide is never wholly free from copper and must be purified for an exact determination. If it does not exceed 2 per cent of the alloy, the quantity of copper which it contains may usually be neglected.] [Note 3: The electrodes should be freed from all greasy matter before using, and those portions upon which the metal will deposit should not be touched with the fingers after cleaning.] [Note 4: Of the ions in solution, the H^{+}, Cu^{++}, Zn^{++}, and Fe^{+++} ions tend to move toward the cathode. The NO_{3}^{-} ions and the lead, probably in the form of PbO_{2}^{--} ions, move toward the anode. At the cathode the Cu^{++} ions are discharged and plate out as metallic copper. This alone occurs while the solution is relatively concentrated. Later on, H^{+} ions are also discharged. In the presence of considerable quantities of H^{+} ions, as in this acid solution, no Zn^{++} or Fe^{+++} ions are discharged because of their greater deposition potentials. At the anode the lead is deposited as PbO_{2} and oxygen is evolved. For the reasons stated on page 141 care must be taken that the solution does not become alkaline if the electrolysis is long continued.] [Note 5: Urea reacts with nitrous acid, which may be formed in the solution as a result of the reducing action of the liberated hydrogen. Its removal promotes the complete precipitation of the copper. The reaction is CO(NH_{2})_{2} + 2HNO_{2} --> CO_{2} + 2N_{2} + 3H_{2}O.] [Note 6: The electrodes must be washed nearly or quite free from the nitric acid solution before the circuit is broken to prevent re-solution of the copper. If several solutions are connected in the same circuit it is obvious that some device must be used to close the circuit as soon as the beaker is removed.] [Note 7: The electrodes upon which the copper has been deposited may be cleaned by immersion in warm nitric acid. To remove the lead dioxide, add a few crystals of oxalic acid to the nitric acid.] DETERMINATION OF IRON Most brasses contain small percentages of iron (usually not over 0.1 per cent) which, unless removed, is precipitated as phosphate and weighed with the zinc. PROCEDURE.--To the solution from the precipitation of copper and lead by electrolysis, add dilute ammonia (sp. gr. 0.96) until the precipitate of zinc hydroxide which first forms re-dissolves, leaving only a slight red precipitate of ferric hydroxide. Filter off the iron precipitate, using a washed filter, and wash five times with hot water. Test a portion of the last washing with a dilute solution of ammonium sulphide to assure complete removal of the zinc. The precipitate may then be ignited and weighed as ferric oxide, as described on page 110. Calculate the percentage of iron (Fe) in the brass. DETERMINATION OF ZINC PROCEDURE.--Acidify the filtrate from the iron determination with dilute nitric acid. Concentrate it to 150 cc. Add to the cold solution dilute ammonia (sp. gr. 0.96) cautiously until it barely smells of ammonia; then add !one drop! of a dilute solution of litmus (Note 1), and drop in, with the aid of a dropper, dilute nitric acid until the blue of the litmus just changes to red. It is important that this point should not be overstepped. Heat the solution nearly to boiling and pour into it slowly a filtered solution of di-ammonium hydrogen phosphate[1] containing a weight of the phosphate about equal to twelve times that of the zinc to be precipitated. (For this calculation the approximate percentage of zinc is that found by subtracting the sum of the percentages of the copper, lead and iron from 100 per cent.) Keep the solution just below boiling for fifteen minutes, stirring frequently (Note 2). If at the end of this time the amorphous precipitate has become crystalline, allow the solution to cool for about four hours, although a longer time does no harm (Note 3), and filter upon an asbestos filter in a porcelain Gooch crucible. The filter is prepared as described on page 103, and should be dried to constant weight at 105°C. [Footnote 1: The ammonium phosphate which is commonly obtainable contains some mono-ammonium salt, and this is not satisfactory as a precipitant. It is advisable, therefore, to weigh out the amount of the salt required, dissolve it in a small volume of water, add a drop of phenolphthalein solution, and finally add dilute ammonium hydroxide solution cautiously until the solution just becomes pink, but do not add an excess.] Wash the precipitate until free from sulphates with a warm 1 per cent solution of the di-ammonium phosphate, and then five times with 50 per cent alcohol (Note 4). Dry the crucible and precipitate for an hour at 105°C., and finally to constant weight (Note 5). The filtrate should be made alkaline with ammonia and tested for zinc with a few drops of ammonium sulphide, allowing it to stand (Notes 6, 7 and 8). From the weight of the zinc ammonium phosphate (ZnNH_{4}PO_{4}) calculate the percentage of the zinc (Zn) in the brass. [Note 1: The zinc ammonium phosphate is soluble both in acids and in ammonia. It is, therefore, necessary to precipitate the zinc in a nearly neutral solution, which is more accurately obtained by adding a drop of a litmus solution to the liquid than by the use of litmus paper.] [Note 2: The precipitate which first forms is amorphous, and may have a variable composition. On standing it becomes crystalline and then has the composition ZnNH_{4}PO_{4}. The precipitate then settles rapidly and is apt to occasion "bumping" if the solution is heated to boiling. Stirring promotes the crystallization.] [Note 3: In a carefully neutralized solution containing a considerable excess of the precipitant, and also ammonium salts, the separation of the zinc is complete after standing four hours. The ionic changes connected with the precipitation of the zinc as zinc ammonium phosphate are similar to those described for magnesium ammonium phosphate, except that the zinc precipitate is soluble in an excess of ammonium hydroxide, probably as a result of the formation of complex ions of the general character Zn(NH_{3})_{4}^{++}.] [Note 4: The precipitate is washed first with a dilute solution of the phosphate to prevent a slight decomposition of the precipitate (as a result of hydrolysis) if hot water alone is used. The alcohol is added to the final wash-water to promote the subsequent drying.] [Note 5: The precipitate may be ignited and weighed as Zn_{2}P_{2}O_{7}, by cautiously heating the porcelain Gooch crucible within a nickel or iron crucible, used as a radiator. The heating must be very slow at first, as the escaping ammonia may reduce the precipitate if it is heated too quickly.] [Note 6: If the ammonium sulphide produced a distinct precipitate, this should be collected on a small filter, dissolved in a few cubic centimeters of dilute nitric acid, and the zinc reprecipitated as phosphate, filtered off, dried, and weighed, and the weight added to that of the main precipitate.] [Note 7: It has been found that some samples of asbestos are acted upon by the phosphate solution and lose weight. An error from this source may be avoided by determining the weight of the crucible and filter after weighing the precipitate. For this purpose the precipitate may be dissolved in dilute nitric acid, the asbestos washed thoroughly, and the crucible reweighed.] [Note 8. The details of this method of precipitation of zinc are fully discussed in an article by Dakin, !Ztschr. Anal. Chem.!, 39 (1900), 273.] DETERMINATION OF SILICA IN SILICATES Of the natural silicates, or artificial silicates such as slags and some of the cements, a comparatively few can be completely decomposed by treatment with acids, but by far the larger number require fusion with an alkaline flux to effect decomposition and solution for analysis. The procedure given below applies to silicates undecomposable by acids, of which the mineral feldspar is taken as a typical example. Modifications of the procedure, which are applicable to silicates which are completely or partially decomposable by acids, are given in the Notes on page 155. PREPARATION OF THE SAMPLE Grind about 3 grams of the mineral in an agate mortar (Note 1) until no grittiness is to be detected, or, better, until it will entirely pass through a sieve made of fine silk bolting cloth. The sieve may be made by placing a piece of the bolting cloth over the top of a small beaker in which the ground mineral is placed, holding the cloth in place by means of a rubber band below the lip of the beaker. By inverting the beaker over clean paper and gently tapping it, the fine particles pass through the sieve, leaving the coarser particles within the beaker. These must be returned to the mortar and ground, and the process of sifting and grinding repeated until the entire sample passes through the sieve. [Note 1: If the sample of feldspar for analysis is in the massive or crystalline form, it should be crushed in an iron mortar until the pieces are about half the size of a pea, and then transferred to a steel mortar, in which they are reduced to a coarse powder. A wooden mallet should always be used to strike the pestle of the steel mortar, and the blows should not be sharp. It is plain that final grinding in an agate mortar must be continued until the whole of the portion of the mineral originally taken has been ground so that it will pass the bolting cloth, otherwise the sifted portion does not represent an average sample, the softer ingredients, if foreign matter is present, being first reduced to powder. For this reason it is best to start with not more than the quantity of the feldspar needed for analysis. The mineral must be thoroughly mixed after the grinding.] FUSION AND SOLUTION PROCEDURE.--Weigh into platinum crucibles two portions of the ground feldspar of about 0.8 gram each. Weigh on rough balances two portions of anhydrous sodium carbonate, each amounting to about six times the weight of the feldspar taken for analysis (Note 1). Pour about three fourths of the sodium carbonate into the crucible, place the latter on a piece of clean, glazed paper, and thoroughly mix the substance and the flux by carefully stirring for several minutes with a dry glass rod, the end of which has been recently heated and rounded in a flame and slowly cooled. The rod may be wiped off with a small fragment of filter paper, which may be placed in the crucible. Place the remaining fourth of the carbonate on the top of the mixture. Cover the crucible, heat it to dull redness for five minutes, and then gradually increase the heat to the full capacity of a Bunsen or Tirrill burner for twenty minutes, or until a quiet, liquid fusion is obtained (Note 2). Finally, heat the sides and cover strongly until any material which may have collected upon them is also brought to fusion. Allow the crucible to cool, and remove the fused mass as directed on page 116. Disintegrate the mass by placing it in a previously prepared mixture of 100 cc. of water and 50 cc. of dilute hydrochloric acid (sp. gr. 1.12) in a covered casserole (Note 3). Clean the crucible and lid by means of a little hydrochloric acid, adding this acid to the main solution (Notes 4 and 5). [Note 1: Quartz, and minerals containing very high percentages of silica, may require eight or ten parts by weight of the flux to insure a satisfactory decomposition.] [Note 2: During the fusion the feldspar, which, when pure, is a silicate of aluminium and either sodium or potassium, but usually contains some iron, calcium, and magnesium, is decomposed by the alkaline flux. The sodium of the latter combines with the silicic acid of the silicate, with the evolution of carbon dioxide, while about two thirds of the aluminium forms sodium aluminate and the remainder is converted into basic carbonate, or the oxide. The calcium and magnesium, if present, are changed to carbonates or oxides. The heat is applied gently to prevent a too violent reaction when fusion first takes place.] [Note 3: The solution of a silicate by a strong acid is the result of the combination of the H^{+} ions of the acid and the silicate ions of the silicate to form a slightly ionized silicic acid. As a consequence, the concentration of the silicate ions in the solution is reduced nearly to zero, and more silicate dissolves to re-establish the disturbed equilibrium. This process repeats itself until all of the silicate is brought into solution. Whether the resulting solution of the silicate contains ortho-silicic acid (H_{4}SiO_{4}) or whether it is a colloidal solution of some other less hydrated acid, such as meta-silicic acid (H_{2}SiO_{3}), is a matter that is still debatable. It is certain, however, that the gelatinous material which readily separates from such solutions is of the nature of a hydrogel, that is, a colloid which is insoluble in water. This substance when heated to 100°C., or higher, is completely dehydrated, leaving only the anhydride, SiO_{2}. The changes may be represented by the equation: SiO_{3}^{--} + 2H^{+} --> [H_{2}SiO_{3}] --> H_{2}O + SiO_{2}.] [Note 4: A portion of the fused mass is usually projected upward by the escaping carbon dioxide during the fusion. The crucible must therefore be kept covered as much as possible and the lid carefully cleaned.] [Note 5: A gritty residue remaining after the disintegration of the fused mass by acid indicates that the substance has been but imperfectly decomposed. Such a residue should be filtered, washed, dried, ignited, and again fused with the alkaline flux; or, if the quantity of material at hand will permit, it is better to reject the analysis, and to use increased care in grinding the mineral and in mixing it with the flux.] DEHYDRATION AND FILTRATION PROCEDURE.--Evaporate the solution of the fusion to dryness, stirring frequently until the residue is a dry powder. Moisten the residue with 5 cc. of strong hydrochloric acid (sp. gr. 1.20) and evaporate again to dryness. Heat the residue for at least one hour at a temperature of 110°C. (Note 1). Again moisten the residue with concentrated hydrochloric acid, warm gently, making sure that the acid comes into contact with the whole of the residue, dilute to about 200 cc. and bring to boiling. Filter off the silica without much delay (Note 2), and wash five times with warm dilute hydrochloric acid (one part dilute acid (1.12 sp. gr.) to three parts of water). Allow the filter to drain for a few moments, then place a clean beaker below the funnel and wash with water until free from chlorides, discarding these washings. Evaporate the original filtrate to dryness, dehydrate at 110°C. for one hour (Note 3), and proceed as before, using a second filter to collect the silica after the second dehydration. Wash this filter with warm, dilute hydrochloric acid (Note 4), and finally with hot water until free from chlorides. [Note 1: The silicic acid must be freed from its combination with a base (sodium, in this instance) before it can be dehydrated. The excess of hydrochloric acid accomplishes this liberation. By disintegrating the fused mass with a considerable volume of dilute acid the silicic acid is at first held in solution to a large extent. Immediate treatment of the fused mass with strong acid is likely to cause a semi-gelatinous silicic acid to separate at once and to inclose alkali salts or alumina. A flocculent residue will often remain after the decomposition of the fused mass is effected. This is usually partially dehydrated silicic acid and does not require further treatment at this point. The progress of the dehydration is indicated by the behavior of the solution, which as evaporation proceeds usually gelatinizes. On this account it is necessary to allow the solution to evaporate on a steam bath, or to stir it vigorously, to avoid loss by spattering.] [Note 2: To obtain an approximately pure silica, the residue after evaporation must be thoroughly extracted by warming with hydrochloric acid, and the solution freely diluted to prevent, as far as possible, the inclosure of the residual salts in the particles of silica. The filtration should take place without delay, as the dehydrated silica slowly dissolves in hydrochloric acid on standing.] [Note 3: It has been shown by Hillebrand that silicic acid cannot be completely dehydrated by a single evaporation and heating, nor by several such treatments, unless an intermediate filtration of the silica occurs. If, however, the silica is removed and the filtrates are again evaporated and the residue heated, the amount of silica remaining in solution is usually negligible, although several evaporations and filtrations are required with some silicates to insure absolute accuracy. It is probable that temperatures above 100°C. are not absolutely necessary to dehydrate the silica; but it is recommended, as tending to leave the silica in a better condition for filtration than when the lower temperature of the water bath is used. This, and many other points in the analysis of silicates, are fully discussed by Dr. Hillebrand in the admirable monograph on "The Analysis of Silicate and Carbonate Rocks," Bulletin No. 700 of the United States Geological Survey. The double evaporation and filtration spoken of above are essential because of the relatively large amount of alkali salts (sodium chloride) present after evaporation. For the highest accuracy in the determination of silica, or of iron and alumina, it is also necessary to examine for silica the precipitate produced in the filtrate by ammonium hydroxide by fusing it with acid potassium sulphate and solution of the fused mass in water. The insoluble silica is filtered, washed, and weighed, and the weight added to the weight of silica previously obtained.] [Note 4: Aluminium and iron are likely to be thrown down as basic salts from hot, very dilute solutions of their chlorides, as a result of hydrolysis. If the silica were washed only with hot water, the solution of these chlorides remaining in the filter after the passage of the original filtrate would gradually become so dilute as to throw down basic salts within the pores of the filter, which would remain with the silica. To avoid this, an acid wash-water is used until the aluminium and iron are practically removed. The acid is then removed by water.] IGNITION AND TESTING OF SILICA PROCEDURE.--Transfer the two washed filters belonging to each determination to a platinum crucible, which need not be previously weighed, and burn off the filter (Note 1). Ignite for thirty minutes over the blast lamp with the cover on the crucible, and then for periods of ten minutes, until the weight is constant. When a constant weight has been obtained, pour into the crucible about 3 cc. of water, and then 3 cc. of hydrofluoric acid. !This must be done in a hood with a good draft and great care must be taken not to come into contact with the acid or to inhale its fumes (Note 2!). If the precipitate has dissolved in this quantity of acid, add two drops of concentrated sulphuric acid, and heat very slowly (always under the hood) until all the liquid has evaporated, finally igniting to redness. Cool in a desiccator, and weigh the crucible and residue. Deduct this weight from the previous weight of crucible and impure silica, and from the difference calculate the percentage of silica in the sample (Note 3). [Note 1: The silica undergoes no change during the ignition beyond the removal of all traces of water; but Hillebrand (!loc. cit.!) has shown that the silica holds moisture so tenaciously that prolonged ignition over the blast lamp is necessary to remove it entirely. This finely divided, ignited silica tends to absorb moisture, and should be weighed quickly.] [Note 2: Notwithstanding all precautions, the ignited precipitate of silica is rarely wholly pure. It is tested by volatilisation of the silica as silicon fluoride after solution in hydrofluoric acid, and, if the analysis has been properly conducted, the residue, after treatment with the acids and ignition, should not exceed 1 mg. The acid produces ulceration if brought into contact with the skin, and its fumes are excessively harmful if inhaled.] [Note 3: The impurities are probably weighed with the original precipitate in the form of oxides. The addition of the sulphuric acid displaces the hydrofluoric acid, and it may be assumed that the resulting sulphates (usually of iron or aluminium) are converted to oxides by the final ignition. It is obvious that unless the sulphuric and hydrofluoric acids used are known to leave no residue on evaporation, a quantity equal to that employed in the analysis must be evaporated and a correction applied for any residue found.] [Note 4: If the silicate to be analyzed is shown by a previous qualitative examination to be completely decomposable, it may be directly treated with hydrochloric acid, the solution evaporated to dryness, and the silica dehydrated and further treated as described in the case of the feldspar after fusion. A silicate which gelatinizes on treatment with acids should be mixed first with a little water, and the strong acid added in small portions with stirring, otherwise the gelatinous silicic acid incloses particles of the original silicate and prevents decomposition. The water, by separating the particles and slightly lessening the rapidity of action, prevents this difficulty. This procedure is one which applies in general to the solution of fine mineral powders in acids. If a small residue remains undecomposed by the treatment of the silicate with acid, this may be filtered, washed, ignited and fused with sodium carbonate and a solution of the fused mass added to the original acid solution. This double procedure has an advantage, in that it avoids adding so large a quantity of sodium salts as is required for disintegration of the whole of the silicate by the fusion method.] PART IV STOICHIOMETRY The problems with which the analytical chemist has to deal are not, as a matter of actual fact, difficult either to solve or to understand. That they appear difficult to many students is due to the fact that, instead of understanding the principles which underlie each of the small number of types into which these problems may be grouped, each problem is approached as an individual puzzle, unrelated to others already solved or explained. This attitude of mind should be carefully avoided. It is obvious that ability to make the calculations necessary for the interpretation of analytical data is no less important than the manipulative skill required to obtain them, and that a moderate time spent in the careful study of the solutions of the typical problems which follow may save much later embarrassment. 1. It is often necessary to calculate what is known as a "chemical factor," or its equivalent logarithmic value called a "log factor," for the conversion of the weight of a given chemical substance into an equivalent weight of another substance. This is, in reality, a very simple problem in proportion, making use of the atomic or molecular weights of the substances in question which are chemically equivalent to each other. One of the simplest cases of this sort is the following: What is the factor for the conversion of a given weight of barium sulphate (BaSO_{4}) into an equivalent weight of sulphur (S)? The molecular weight of BaSO_{4} is 233.5. There is one atom of S in the molecule and the atomic weight of S is 32.1. The chemical factor is, therefore, 32.1/233.5, or 0.1375 and the weight of S corresponding to a given weight of BaSO_{4} is found by multiplying the weight of BaSO_{4} by this factor. If the problem takes the form, "What is the factor for the conversion of a given weight of ferric oxide (Fe_{2}O_{3}) into ferrous oxide (FeO), or of a given weight of mangano-manganic oxide (Mn_{3}O_{4}) into manganese (Mn)?" the principle involved is the same, but it must then be noted that, in the first instance, each molecule of Fe_{2}O_{3} will be equivalent to two molecules of FeO, and in the second instance that each molecule of Mn_{3}O_{4} is equivalent to three atoms of Mn. The respective factors then become (2FeO/Fe_{2}O_{3}) or (143.6/159.6) and (3Mn/Mn_{3}O_{4}) or (164.7/228.7). It is obvious that the arithmetical processes involved in this type of problem are extremely simple. It is only necessary to observe carefully the chemical equivalents. It is plainly incorrect to express the ratio of ferrous to ferric oxide as (FeO/Fe_{2}O_{3}), since each molecule of the ferric oxide will yield two molecules of the ferrous oxide. Mistakes of this sort are easily made and constitute one of the most frequent sources of error. 2. A type of problem which is slightly more complicated in appearance, but exactly comparable in principle, is the following: "What is the factor for the conversion of a given weight of ferrous sulphate (FeSO_{4}), used as a reducing agent against potassium permanganate, into the equivalent weight of sodium oxalate (Na_{2}C_{2}O_{4})?" To determine the chemical equivalents in such an instance it is necessary to inspect the chemical reactions involved. These are: 10FeSO_{4} + 2KMnO_{4} + 8H_{2}SO_{4} --> 5Fe_{2}(SO_{4})_{3} + K_{2}SO_{4} + 2MnSO_{4} + 8H_{2}O, 5Na_{2}C_{2}O_{4} + 2KMnO_{4} + 8H_{2}SO_{4} --> 5Na_{2}SO_{4} + 10CO_{2} + K_{2}SO_{4} + 2MnSO_{4} + 8H_{2}O. It is evident that 10FeSO_{4} in the one case, and 5Na_{2}C_{2}O_{4} in the other, each react with 2KMnO_{4}. These molecular quantities are therefore equivalent, and the factor becomes (10FeSO_{4}/5Na_{2}C_{2}O_{4}) or (2FeSO_{4}/Na_{2}C_{2}O_{4}) or (303.8/134). Again, let it be assumed that it is desired to determine the factor required for the conversion of a given weight of potassium permanganate (KMnO_{4}) into an equivalent weight of potassium bichromate (K_{2}Cr_{2}O_{7}), each acting as an oxidizing agent against ferrous sulphate. The reactions involved are: 10FeSO_{4} + 2KMnO_{4} + 8H_{2}SO_{4} --> 5Fe_{2}(SO_{4})_{3} + K_{2}SO_{4} + 2MnSO_{4} + 8H_{2}O, 6FeSO_{4} + K_{2}Cr_{2}O_{7} + 7H_{2}SO_{4} --> 3Fe_{2}(SO_{3})_{3} + K_{2}SO_{4} + Cr_{2}(SO_{4})_{3} + 7H_{2}O. An inspection of these equations shows that 2KMO_{4} react with 10FeSO_{4}, while K_{2}Cr_{2}O_{7} reacts with 6FeSO_{4}. These are not equivalent, but if the first equation is multiplied by 3 and the second by 5 the number of molecules of FeSO_{4} is then the same in both, and the number of molecules of KMnO_{4} and K_{2}Cr_{2}O_{7} reacting with these 30 molecules become 6 and 5 respectively. These are obviously chemically equivalent and the desired factor is expressed by the fraction (6KMnO_{4}/5K_{2}Cr_{2}O_{7}) or (948.0/1471.0). 3. It is sometimes necessary to calculate the value of solutions according to the principles just explained, when several successive reactions are involved. Such problems may be solved by a series of proportions, but it is usually possible to eliminate the common factors and solve but a single one. For example, the amount of MnO_{2} in a sample of the mineral pyrolusite may be determined by dissolving the mineral in hydrochloric acid, absorbing the evolved chlorine in a solution of potassium iodide, and measuring the liberated iodine by titration with a standard solution of sodium thiosulphate. The reactions involved are: MnO_{2} + 4HCl --> MnCl_{2} + 2H_{2}O + Cl_{2} Cl_{2} + 2KI --> I_{2} + 2KCl I_{2} + 2Na_{2}S_{2}O_{3} --> 2NaI + Na_{2}S_{4}O_{6} Assuming that the weight of thiosulphate corresponding to the volume of sodium thiosulphate solution used is known, what is the corresponding weight of manganese dioxide? From the reactions given above, the following proportions may be stated: 2Na_{2}S_{2}O_{3}:I_{2} = 316.4:253.9, I_{2}:Cl_{2} = 253.9:71, Cl_{2}:MnO_{2} = 71:86.9. After canceling the common factors, there remains 2Na_{2}S_{2}O_{3}:MnO_{2} = 316.4:86.9, and the factor for the conversion of thiosulphate into an equivalent of manganese dioxide is 86.9/316.4. 4. To calculate the volume of a reagent required for a specific operation, it is necessary to know the exact reaction which is to be brought about, and, as with the calculation of factors, to keep in mind the molecular relations between the reagent and the substance reacted upon. For example, to estimate the weight of barium chloride necessary to precipitate the sulphur from 0.1 gram of pure pyrite (FeS_{2}), the proportion should read 488. 120.0 2(BaCl_{2}.2H_{2}O):FeS_{2} = x:0.1, where !x! represents the weight of the chloride required. Each of the two atoms of sulphur will form upon oxidation a molecule of sulphuric acid or a sulphate, which, in turn, will require a molecule of the barium chloride for precipitation. To determine the quantity of the barium chloride required, it is necessary to include in its molecular weight the water of crystallization, since this is inseparable from the chloride when it is weighed. This applies equally to other similar instances. If the strength of an acid is expressed in percentage by weight, due regard must be paid to its specific gravity. For example, hydrochloric acid (sp. gr. 1.12) contains 23.8 per cent HCl !by weight!; that is, 0.2666 gram HCl in each cubic centimeter. 5. It is sometimes desirable to avoid the manipulation required for the separation of the constituents of a mixture of substances by making what is called an "indirect analysis." For example, in the analysis of silicate rocks, the sodium and potassium present may be obtained in the form of their chlorides and weighed together. If the weight of such a mixture is known, and also the percentage of chlorine present, it is possible to calculate the amount of each chloride in the mixture. Let it be assumed that the weight of the mixed chlorides is 0.15 gram, and that it contains 53 per cent of chlorine. The simplest solution of such a problem is reached through algebraic methods. The weight of chlorine is evidently 0.15 x 0.53, or 0.0795 gram. Let x represent the weight of sodium chloride present and y that of potassium chloride. The molecular weight of NaCl is 58.5 and that of KCl is 74.6. The atomic weight of chlorine is 35.5. Then x + y = 0.15 (35.5/58.5)x + (35.5/74.6)y = 0.00795 Solving these equations for x shows the weight of NaCl to be 0.0625 gram. The weight of KCl is found by subtracting this from 0.15. The above is one of the most common types of indirect analyses. Others are more complex but they can be reduced to algebraic expressions and solved by their aid. It should, however, be noted that the results obtained by these indirect methods cannot be depended upon for high accuracy, since slight errors in the determination of the common constituent, as chlorine in the above mixture, will cause considerable variations in the values found for the components. They should not be employed when direct methods are applicable, if accuracy is essential. PROBLEMS (The reactions necessary for the solution of these problems are either stated with the problem or may be found in the earlier text. In the calculations from which the answers are derived, the atomic weights given on page 195 have been employed, using, however, only the first decimal but increasing this by 1 when the second decimal is 5 or above. Thus, 39.1 has been taken as the atomic weight of potassium, 32.1 for sulphur, etc. This has been done merely to secure uniformity of treatment, and the student should remember that it is always well to take into account the degree of accuracy desired in a particular instance in determining the number of decimal places to retain. Four-place logarithms were employed in the calculations. Where four figures are given in the answer, the last figure may vary by one or (rarely) by two units, according to the method by which the problem is solved.) VOLUMETRIC ANALYSIS 1. How many grams of pure potassium hydroxide are required for exactly 1 liter of normal alkali solution? !Answer!: 56.1 grams. 2. Calculate the equivalent in grams (a) of sulphuric acid as an acid; (b) of hydrochloric acid as an acid; (c) of oxalic acid as an acid; (d) of nitric acid as an acid. !Answers!: (a) 49.05; (b) 36.5; (c) 63; (d) 63. 3. Calculate the equivalent in grams of (a) potassium hydroxide; (b) of sodium carbonate; (c) of barium hydroxide; (d) of sodium bicarbonate when titrated with an acid. !Answers!: (a) 56.1; (b) 53.8; (c) 85.7; (d) 84. 4. What is the equivalent in grams of Na_{2}HPO_{4} (a) as a phosphate; (b) as a sodium salt? !Answers!: (a) 47.33; (b) 71.0. 5. A sample of aqueous hydrochloric acid has a specific gravity of 1.12 and contains 23.81 per cent hydrochloric acid by weight. Calculate the grams and the milliequivalents of hydrochloric acid (HCl) in each cubic centimeter of the aqueous acid. !Answers!: 0.2667 gram; 7.307 milliequivalents. 6. How many cubic centimeters of hydrochloric acid (sp. gr. 1.20 containing 39.80 per cent HCl by weight) are required to furnish 36.45 grams of the gaseous compound? !Answer!: 76.33 cc. 7. A given solution contains 0.1063 equivalents of hydrochloric acid in 976 cc. What is its normal value? !Answer!: 0.1089 N. 8. In standardizing a hydrochloric acid solution it is found that 47.26 cc. of hydrochloric acid are exactly equivalent to 1.216 grams of pure sodium carbonate, using methyl orange as an indicator. What is the normal value of the hydrochloric acid? !Answer!: 0.4855 N. 9. Convert 42.75 cc. of 0.5162 normal hydrochloric acid to the equivalent volume of normal hydrochloric acid. !Answer!: 22.07 cc. 10. A solution containing 25.27 cc. of 0.1065 normal hydrochloric acid is added to one containing 92.21 cc. of 0.5431 normal sulphuric acid and 50 cc. of exactly normal potassium hydroxide added from a pipette. Is the solution acid or alkaline? How many cubic centimeters of 0.1 normal acid or alkali must be added to exactly neutralize the solution? !Answer!: 27.6 cc. alkali (solution is acid). 11. By experiment the normal value of a sulphuric acid solution is found to be 0.5172. Of this acid 39.65 cc. are exactly equivalent to 21.74 cc. of a standard alkali solution. What is the normal value of the alkali? !Answer!: 0.9432 N. 12. A solution of sulphuric acid is standardized against a sample of calcium carbonate which has been previously accurately analyzed and found to contain 92.44% CaCO_{3} and no other basic material. The sample weighing 0.7423 gram was titrated by adding an excess of acid (42.42 cc.) and titrating the excess with sodium hydroxide solution (11.22 cc.). 1 cc. of acid is equivalent to 0.9976 cc. of sodium hydroxide. Calculate the normal value of each. !Answers!: Acid 0.4398 N; alkali 0.4409 N. 13. Given five 10 cc. portions of 0.1 normal hydrochloric acid, (a) how many grams of silver chloride will be precipitated by a portion when an excess of silver nitrate is added? (b) how many grams of pure anhydrous sodium carbonate (Na_{2}CO_{3}) will be neutralized by a portion of it? (c) how many grams of silver will there be in the silver chloride formed when an excess of silver nitrate is added to a portion? (d) how many grams of iron will be dissolved to FeCl_{2} by a portion of it? (e) how many grams of magnesium chloride will be formed and how many grams of carbon dioxide liberated when an excess of magnesium carbonate is treated with a portion of the acid? !Answers!: (a) 0.1434; (b) 0.053; (c) 0.1079; (d) 0.0279; (e) 0.04765, and 0.022. 14. If 30.00 grams of potassium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O) are dissolved and the solution diluted to exactly 1 liter, and 40 cc. are neutralized with 20 cc. of a potassium carbonate solution, what is the normal value of the carbonate solution? !Answer!: 0.7084 N. 15. How many cubic centimeters of 0.3 normal sulphuric acid will be required to neutralize (a) 30 cc. of 0.5 normal potassium hydroxide; (b) to neutralize 30 cc. of 0.5 normal barium hydroxide; (c) to neutralize 20 cc. of a solution containing 10.02 grams of potassium bicarbonate per 100 cc.; (d) to give a precipitate of barium sulphate weighing 0.4320 gram? !Answers!: (a) 50 cc.; (b) 50 cc.; (c) 66.73 cc.; (d) 12.33 cc. 16. It is desired to dilute a solution of sulphuric acid of which 1 cc. is equivalent to 0.1027 gram of pure sodium carbonate to make it exactly 1.250 normal. 700 cc. of the solution are available. To what volume must it be diluted? !Answer!: 1084 cc. 17. Given the following data: 1 cc. of NaOH = 1.117 cc. HCl. The HCl is 0.4876 N. How much water must be added to 100 cc. of the alkali to make it exactly 0.5 N.? !Answer!: 9.0 cc. 18. What is the normal value of a sulphuric acid solution which has a specific gravity of 1.839 and contains 95% H_{2}SO_{4} by weight? !Answer!: 35.61 N. 19. A sample of Rochelle Salt (KNaC_{4}H_{4}O_{6}.4H_{2}O), after ignition in platinum to convert it to the double carbonate, is titrated with sulphuric acid, using methyl orange as an indicator. From the following data calculate the percentage purity of the sample: Wt. sample = 0.9500 gram H_{2}SO_{4} used = 43.65 cc. NaOH used = 1.72 cc. 1 cc. H_{2}SO_{4} = 1.064 cc. NaOH Normal value NaOH = 0.1321 N. !Answer!: 87.72 cc. 20. One gram of a mixture of 50% sodium carbonate and 50% potassium carbonate is dissolved in water, and 17.36 cc. of 1.075 N acid is added. Is the resulting solution acid or alkaline? How many cubic centimeters of 1.075 N acid or alkali will have to be added to make the solution exactly neutral? !Answers!: Acid; 1.86 cc. alkali. 21. In preparing an alkaline solution for use in volumetric work, an analyst, because of shortage of chemicals, mixed exactly 46.32 grams of pure KOH and 27.64 grams of pure NaOH, and after dissolving in water, diluted the solution to exactly one liter. How many cubic centimeters of 1.022 N hydrochloric acid are necessary to neutralize 50 cc. of the basic solution? !Answer!: 74.18 cc. 22. One gram of crude ammonium salt is treated with strong potassium hydroxide solution. The ammonia liberated is distilled and collected in 50 cc. of 0.5 N acid and the excess titrated with 1.55 cc. of 0.5 N sodium hydroxide. Calculate the percentage of NH_{3} in the sample. !Answer!: 41.17%. 23. In titrating solutions of alkali carbonates in the presence of phenolphthalein, the color change takes place when the carbonate has been converted to bicarbonate. In the presence of methyl orange, the color change takes place only when the carbonate has been completely neutralized. From the following data, calculate the percentages of Na_{2}CO_{3} and NaOH in an impure mixture. Weight of sample, 1.500 grams; HCl (0.5 N) required for phenolphthalein end-point, 28.85 cc.; HCl (0.5 N) required to complete the titration after adding methyl orange, 23.85 cc. !Answers!: 6.67% NaOH; 84.28% Na_{2}CO_{3}. 24. A sample of sodium carbonate containing sodium hydroxide weighs 1.179 grams. It is titrated with 0.30 N hydrochloric acid, using phenolphthalein in cold solution as an indicator and becomes colorless after the addition of 48.16 cc. Methyl orange is added and 24.08 cc. are needed for complete neutralization. What is the percentage of NaOH and Na_{2}CO_{3}? !Answers!: 24.50% NaOH; 64.92% Na_{2}CO_{3}. 25. From the following data, calculate the percentages of Na_{2}CO_{3} and NaHCO_{3} in an impure mixture. Weight of sample 1.000 gram; volume of 0.25 N hydrochloric acid required for phenolphthalein end-point, 26.40 cc.; after adding an excess of acid and boiling out the carbon dioxide, the total volume of 0.25 N hydrochloric acid required for phenolphthalein end-point, 67.10 cc. !Answer!: 69.95% Na_{2}CO_{3}; 30.02% NaHCO_{3}. 26. In the analysis of a one-gram sample of soda ash, what must be the normality of the acid in order that the number of cubic centimeters of acid used shall represent the percentage of carbon dioxide present? !Answer!: 0.4544 gram. 27. What weight of pearl ash must be taken for analysis in order that the number of cubic centimeters of 0.5 N acid used may be equal to one third the percentage of K_{2}CO_{3}? !Answer!: 1.152 grams. 28. What weight of cream of tartar must have been taken for analysis in order to have obtained 97.60% KHC_{4}H_{4}O_{6} in an analysis involving the following data: NaOH used = 30.06 cc.; H_{2}SO_{4} solution used = 0.50 cc.; 1 cc. H_{2}SO_{4} sol. = 0.0255 gram CaCO_{3}; 1 cc. H_{2}SO_{4} sol. = 1.02 cc. NaOH sol.? !Answer!: 2.846 grams. 29. Calculate the percentage of potassium oxide in an impure sample of potassium carbonate from the following data: Weight of sample = 1.00 gram; HCl sol. used = 55.90 cc.; NaOH sol. used = 0.42 cc.; 1 cc. NaOH sol. = 0.008473 gram of KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O; 2 cc. HCl sol. = 5 cc. NaOH sol. !Answer!: 65.68%. 30. Calculate the percentage purity of a sample of calcite (CaCO_{3}) from the following data: (Standardization); Weight of H_{2}C_{2}O_{4}.2H_{2}O = 0.2460 gram; NaOH solution used = 41.03 cc.; HCl solution used = 0.63; 1 cc. NaOH solution = 1.190 cc. HCl solution. (Analysis); Weight of sample 0.1200 gram; HCl used = 36.38 cc.; NaOH used = 6.20 cc. !Answer!: 97.97%. 31. It is desired to dilute a solution of hydrochloric acid to exactly 0.05 N. The following data are given: 44.97 cc. of the hydrochloric acid are equivalent to 43.76 cc. of the NaOH solution. The NaOH is standardized against a pure potassium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O) weighing 0.2162 gram and requires 49.14 cc. How many cc. of water must be added to 1000 cc. of the aqueous hydrochloric acid? !Answer!: 11 cc. 32. How many cubic centimeters of 3 N phosphoric acid must be added to 300 cc. of 0.4 N phosphoric acid in order that the resulting solution may be 0.6 N? !Answer!: 25 cc. 33. To oxidize the iron in 1 gram of FeSO_{4}(NH_{4})_{2}SO_{4}.6H_{2}O (mol. wgt. 392) requires 3 cc. of a given solution of HNO_{3}. What is the normality of the nitric acid when used as an acid? 6FeSO_{4} + 2HNO_{3} + 2H_{2}SO_{4} = 3Fe_{2}(SO_{4})_{3} + 2NO + 4H_{2}O. !Answer!: 0.2835 N. 34. The same volume of carbon dioxide at the same temperature and the same pressure is liberated from a 1 gram sample of dolomite, by adding an excess of hydrochloric acid, as can be liberated by the addition of 35 cc. of 0.5 N hydrochloric acid to an excess of any pure or impure carbonate. Calculate the percentage of CO_{2} in the dolomite. !Answer!: 38.5%. 35. How many cubic centimeters of sulphuric acid (sp. gr. 1.84, containing 96% H_{2}SO_{4} by weight) will be required to displace the chloride in the calcium chloride formed by the action of 100 cc. of 0.1072 N hydrochloric acid on an excess of calcium carbonate, and how many grams of CaSO_{4} will be formed? !Answers!: 0.298 cc.; 0.7300 gram. 36. Potassium hydroxide which has been exposed to the air is found on analysis to contain 7.62% water, 2.38% K_{2}CO_{3}. and 90% KOH. What weight of residue will be obtained if one gram of this sample is added to 46 cc. of normal hydrochloric acid and the resulting solution, after exact neutralization with 1.070 N potassium hydroxide solution, is evaporated to dryness? !Answer!: 3.47 grams. 37. A chemist received four different solutions, with the statement that they contained either pure NaOH; pure Na_{2}CO_{3}; pure NaHCO_{3}, or mixtures of these substances. From the following data identify them: Sample I. On adding phenolphthalein to a solution of the substance, it gave no color to the solution. Sample II. On titrating with standard acid, it required 15.26 cc. for a change in color, using phenolphthalein, and 17.90 cc. additional, using methyl orange as an indicator. Sample III. The sample was titrated with hydrochloric acid until the pink of phenolphthalein disappeared, and on the addition of methyl orange the solution was colored pink. Sample IV. On titrating with hydrochloric acid, using phenolphthalein, 15.00 cc. were required. A new sample of the same weight required exactly 30 cc. of the same acid for neutralization, using methyl orange. !Answers!: (a) NaHCO_{3}; (b) NaHCO_{3}+Na_{2}CO_{3}; (c)NaOH; (d) Na_{2}CO_{3}. 38. In the analysis of a sample of KHC_{4}H_{4}O_{6} the following data are obtained: Weight sample = 0.4732 gram. NaOH solution used = 24.97 cc. 3.00 cc. NaOH = 1 cc. of H_{3}PO_{4} solution of which 1 cc. will precipitate 0.01227 gram of magnesium as MgNH_{4}PO_{4}. Calculate the percentage of KHC_{4}H_{4}O_{6}. !Answer!: 88.67%. 39. A one-gram sample of sodium hydroxide which has been exposed to the air for some time, is dissolved in water and diluted to exactly 500 cc. One hundred cubic centimeters of the solution, when titrated with 0.1062 N hydrochloric acid, using methyl orange as an indicator, requires 38.60 cc. for complete neutralization. Barium chloride in excess is added to a second portion of 100 cc. of the solution, which is diluted to exactly 250 cc., allowed to stand and filtered. Two hundred cubic centimeters of this filtrate require 29.62 cc. of 0.1062 N hydrochloric acid for neutralization, using phenolphthalein as an indicator. Calculate percentage of NaOH, Na_{2}CO_{3}, and H_{2}O. !Answers!: 78.63% NaOH; 4.45% Na_{2}CO_{3}; 16.92% H_{2}O. 40. A sodium hydroxide solution (made from solid NaOH which has been exposed to the air) was titrated against a standard acid using methyl orange as an indicator, and was found to be exactly 0.1 N. This solution was used in the analysis of a material sold at 2 cents per pound per cent of an acid constituent A, and always mixed so that it was supposed to contain 15% of A, on the basis of the analyst's report. Owing to the carelessness of the analyst's assistant, the sodium hydroxide solution was used with phenolphthalein as an indicator in cold solution in making the analyses. The concern manufacturing this material sells 600 tons per year, and when the mistake was discovered it was estimated that at the end of a year the error in the use of indicators would either cost them or their customers $6000. Who would lose and why? Assuming the impure NaOH used originally in making the titrating solution consisted of NaOH and Na_{2}CO_{3} only, what per cent of each was present? !Answers!: Customer lost; 3.94% Na_{2}CO_{3}; 96.06% NaOH. 41. In the standardization of a K_{2}Cr_{2}O_{7} solution against iron wire, 99.85% pure, 42.42 cc. of the solution were added. The weight of the wire used was 0.22 gram. 3.27 cc. of a ferrous sulphate solution having a normal value as a reducing agent of 0.1011 were added to complete the titration. Calculate the normal value of the K_{2}Cr_{2}O_{7}. !Answer!: 0.1006 N. 42. What weight of iron ore containing 56.2% Fe should be taken to standardize an approximately 0.1 N oxidizing solution, if not more than 47 cc. are to be used? !Answer!: 0.4667 gram. 43. One tenth gram of iron wire, 99.78% pure, is dissolved in hydrochloric acid and the iron oxidized completely with bromine water. How many grams of stannous chloride are there in a liter of solution if it requires 9.47 cc. to just reduce the iron in the above? What is the normal value of the stannous chloride solution as a reducing agent? !Answer!: 17.92 grams; 0.1888 N. 44. One gram of an oxide of iron is fused with potassium acid sulphate and the fusion dissolved in acid. The iron is reduced with stannous chloride, mercuric chloride is added, and the iron titrated with a normal K_{2}Cr_{2}O_{7} solution. 12.94 cc. were used. What is the formula of the oxide, FeO, Fe_{2}O_{3}, or Fe_{3}O_{4}? !Answer!: Fe_{3}O_{4}. 45. If an element has 98 for its atomic weight, and after reduction with stannous chloride could be oxidized by bichromate to a state corresponding to an XO_{4}^{-} anion, compute the oxide, or valence, corresponding to the reduced state from the following data: 0.3266 gram of the pure element, after being dissolved, was reduced with stannous chloride and oxidized by 40 cc. of K_{2}Cr_{2}O_{7}, of which one cc. = 0.1960 gram of FeSO_{4}(NH_{4})_{2}SO_{4}.6H_{2}O. !Answer!: Monovalent. 46. Determine the percentage of iron in a sample of limonite from the following data: Sample = 0.5000 gram. KMnO_{4} used = 50 cc. 1 cc. KMnO_{4} = 0.005317 gram Fe. FeSO_{4} used = 6 cc. 1 cc. FeSO_{4} = 0.009200 gram FeO. !Answer!: 44.60%. 47. If 1 gram of a silicate yields 0.5000 gram of Fe_{2}O_{3} and Al_{2}O_{3} and the iron present requires 25 cc. of 0.2 N KMnO_{4}, calculate the percentage of FeO and Al_{2}O_{3} in the sample. !Answer!: 35.89% FeO; 10.03% Al_{2}O_{3}. 48. A sample of magnesia limestone has the following composition: Silica, 3.00%; ferric oxide and alumina, 0.20%; calcium oxide, 33.10%; magnesium oxide, 20.70%; carbon dioxide, 43.00%. In manufacturing lime from the above the carbon dioxide is reduced to 3.00%. How many cubic centimeters of normal KMnO_{4} will be required to determine the calcium oxide volumetrically in a 1 gram sample of the lime? !Answer!: 20.08 cc. 49. If 100 cc. of potassium bichromate solution (10 gram K_{2}Cr_{2}O_{7} per liter), 5 cc. of 6 N sulphuric acid, and 75 cc. of ferrous sulphate solution (80 grams FeSO_{4}.7H_{2}O per liter) are mixed, and the resulting solution titrated with 0.2121 N KMnO_{4}, how many cubic centimeters of the KMnO_{4} solution will be required to oxidize the iron? !Answer!: 5.70 cc. 50. If a 0.5000 gram sample of limonite containing 59.50 per cent Fe_{2}O_{3} requires 40 cc. of KMnO_{4} to oxidize the iron, what is the value of 1 cc. of the permanganate in terms of (a) Fe, (b) H_{2}C_{2}O_{4}.2H_{2}O? !Answers!: (a) 0.005189 gram; (b) 0.005859 gram. 51. A sample of pyrolusite weighing 0.6000 gram is treated with 0.9000 gram of oxalic acid. The excess oxalic acid requires 23.95 cc. of permanganate (1 cc. = 0.03038 gram FeSO_{4}.7H_{2}O). What is the percentage of MnO_{2}, in the sample? !Answer!: 84.47%. 52. A solution contains 50 grams of KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O per liter. What is the normal value of the solution (a) as an acid, and (b) as a reducing agent? !Answers!: (a) 0.5903 N; (b) 0.7872 N. 53. In the analysis of an iron ore containing 60% Fe_{2}O_{3}, a sample weighing 0.5000 gram is taken and the iron is reduced with sulphurous acid. On account of failure to boil out all the excess SO_{2}, 38.60 cubic centimeters of 0.1 N KMnO_{4} were required to titrate the solution. What was the error, percentage error, and what weight of sulphur dioxide was in the solution? !Answers!: (a) 1.60%; (b) 2.67%; (c) 0.00322 gram. 54. From the following data, calculate the ratio of the nitric acid as an oxidizing agent to the tetroxalate solution as a reducing agent: 1 cc. HNO_{3} = 1.246 cc. NaOH solution; 1 cc. NaOH = 1.743 cc. KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O solution; Normal value NaOH = 0.12. !Answer!: 4.885. 55. Given the following data: 25 cc. of a hydrochloric acid, when standardized gravimetrically as silver chloride, yields a precipitate weighing 0.5465 gram. 24.35 cc. of the hydrochloric acid are exactly equivalent to 30.17 cc. of KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O solution. How much water must be added to a liter of the oxalate solution to make it exactly 0.025 N as a reducing agent? !Answer!: 5564 cc. 56. Ten grams of a mixture of pure potassium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O) and pure oxalic acid (H_{2}C_{2}O_{4}.2H_{2}O) are dissolved in water and diluted to exactly 1000 cc. The normal value of the oxalate solution when used as an acid is 0.1315. Calculate the ratio of tetroxalate to oxalate used in making up the solution and the normal value of the solution as a reducing agent. !Answers!: 2:1; 0.1577 N. 57. A student standardized a solution of NaOH and one of KMnO_{4} against pure KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O and found the former to be 0.07500 N as an alkali and the latter exactly 0.1 N as an oxidizing agent. By coincidence, exactly 47.26 cc. were used in each standardization. Find the ratio of the oxalate used in the NaOH standardization to the oxalate used in the permanganate standardization. !Answer!: 1:1. 58. A sample of apatite weighing 0.60 gram is analyzed for its phosphoric anhydride content. If the phosphate is precipitated as (NH_{4})_{3}PO_{4}.12MoO_{3}, and the precipitate (after solution and reduction of the MoO_{3} to Mo_{24}O_{37}), requires 100 cc. of normal KMnO_{4} to oxidize it back to MoO_{3}, what is the percentage of P_{2}O_{5}? !Answer!: 33.81%. 59. In the analysis of a sample of steel weighing 1.881 grams the phosphorus was precipitated with ammonium molybdate and the yellow precipitate was dissolved, reduced and titrated with KMnO_{4}. If the sample contained 0.025 per cent P and 6.01 cc. of KMnO_{4} were used, to what oxide was the molybdenum reduced? 1 cc. KMnO_{4} = 0.007188 gram Na_{2}C_{2}O_{4}. !Answer!: Mo_{4}O_{5}. 60. What is the value of 1 cc. of an iodine solution (1 cc. equivalent to 0.0300 gram Na_{2}S_{2}O_{3}) in terms of As_{2}O_{3}? !Answer!: 0.009385 gram. 61. 48 cc. of a solution of sodium thiosulphate are required to titrate the iodine liberated from an excess of potassium iodide solution by 0.3000 gram of pure KIO_{3}. (KIO_{3} + 5KI + 3H_{2}SO_{4} = 3K_{2}SO_{4} + 3I_{2} + 3H_{2}O.) What is the normal strength of the sodium thiosulphate and the value of 1 cc. of it in terms of iodine? !Answers!: 0.1753 N; 0.02224 gram. 62. One thousand cubic centimeters of 0.1079 N sodium thiosulphate solution is allowed to stand. One per cent by weight of the thiosulphate is decomposed by the carbonic acid present in the solution. To what volume must the solution be diluted to make it exactly 0.1 N as a reducing agent? (Na_{2}S_{2}O_{3} + 2H_{2}CO_{3} = H_{2}SO_{3} + 2NaHCO_{3} + S.) !Answer!: 1090 cc. 63. An analyzed sample of stibnite containing 70.05% Sb is given for analysis. A student titrates it with a solution of iodine of which 1 cc. is equivalent to 0.004950 gram of As_{2}O_{3}. Due to an error on his part in standardization, the student's analysis shows the sample to contain 70.32% Sb. Calculate the true normal value of the iodine solution, and the percentage error in the analysis. !Answers!: 0.1000 N; 0.39%. 64. A sample of pyrolusite weighing 0.5000 gram is treated with an excess of hydrochloric acid, the liberated chlorine is passed into potassium iodide and the liberated iodine is titrated with sodium thiosulphate solution (49.66 grams of pure Na_{2}S_{2}O_{3}.5H_{2}O per liter). If 38.72 cc. are required, what volume of 0.25 normal permanganate solution will be required in an indirect determination in which a similar sample is reduced with 0.9012 gram H_{2}C_{2}O_{4}.2H_{2}O and the excess oxalic acid titrated? !Answer!: 26.22 cc. 65. In the determination of sulphur in steel by evolving the sulphur as hydrogen sulphide, precipitating cadmium sulphide by passing the liberated hydrogen sulphide through ammoniacal cadmium chloride solution, and decomposing the CdS with acid in the presence of a measured amount of standard iodine, the following data are obtained: Sample, 5.027 grams; cc. Na_{2}S_{2}O_{3} sol. = 12.68; cc. Iodine sol. = 15.59; 1 cc. Iodine sol. = 1.086 cc. Na_{2}S_{2}O_{3} sol.; 1 cc. Na_{2}S_{2}O_{3}= 0.005044 gram Cu. Calculate the percentage of sulphur. (H_{2}S + I_{2} = 2HI + S.) !Answer!: 0.107%. 66. Given the following data, calculate the percentage of iron in a sample of crude ferric chloride weighing 1.000 gram. The iodine liberated by the reaction 2FeCl_{3}+ 2HI = 2HCl + 2FeCl_{2} + I_{2} is reduced by the addition of 50 cc. of sodium thiosulphate solution and the excess thiosulphate is titrated with standard iodine and requires 7.85 cc. 45 cc. I_{2} solution = 45.95 cc. Na_{2}S_{2}O_{3} solution; 45 cc. As_{2}O_{3} solution = 45.27 cc. I_{2} solution. 1 cc. arsenite solution = 0.005160 gram As_{2}O_{3}. !Answer!: 23.77%. 67. Sulphide sulphur was determined in a sample of reduced barium sulphate by the evolution method, in which the sulphur was evolved as hydrogen sulphide and was passed into CdCl_{2} solution, the acidified precipitate being titrated with iodine and thiosulphate. Sample, 5.076 grams; cc. I_{2} = 20.83; cc. Na_{2}S_{2}O_{3} = 12.37; 43.45 cc. Na_{2}S_{2}O_{3} = 43.42 cc. I_{2}; 8.06 cc. KMnO_{4} = 44.66 cc. Na_{2}S_{2}O_{3}; 28.87 cc. KMnO_{4} = 0.2004 gram Na_{2}C_{2}O_{4}. Calculate the percentage of sulphide sulphur in the sample. !Answer!: 0.050%. 68. What weight of pyrolusite containing 89.21% MnO_{2} will oxidize the same amount of oxalic acid as 37.12 cc. of a permanganate solution, of which 1 cc. will liberate 0.0175 gram of I_{2} from KI? !Answer!: 0.2493 gram. 69. A sample of pyrolusite weighs 0.2400 gram and is 92.50% pure MnO_{2}. The iodine liberated from KI by the manganese dioxide is sufficient to react with 46.24 cc. of Na_{2}S_{2}O_{3} sol. What is the normal value of the thiosulphate? !Answer!:: 0.1105 N. 70. In the volumetric analysis of silver coin (90% Ag), using a 0.5000 gram sample, what is the least normal value that a potassium thiocyanate solution may have and not require more than 50 cc. of solution in the analysis? !Answer!: 0.08339 N. 71. A mixture of pure lithium chloride and barium bromide weighing 0.6 gram is treated with 45.15 cubic centimeters of 0.2017 N silver nitrate, and the excess titrated with 25 cc. of 0.1 N KSCN solution, using ferric alum as an indicator. Calculate the percentage of bromine in the sample. !Answer!: 40.11%. 72. A mixture of the chlorides of sodium and potassium from 0.5000 gram of a feldspar weighs 0.1500 gram, and after solution in water requires 22.71 cc. of 0.1012 N silver nitrate for the precipitation of the chloride ions. What are the percentages of Na_{2}O and K_{2}O in the feldspar? !Answer!: 8.24% Na_{2}O; 9.14% K_{2}O. GRAVIMETRIC ANALYSIS 73. Calculate (a) the grams of silver in one gram of silver chloride; (b) the grams of carbon dioxide liberated by the addition of an excess of acid to one gram of calcium carbonate; (c) the grams of MgCl_{2} necessary to precipitate 1 gram of MgNH_{4}PO_{4}. !Answers!: (a) 0.7526; (b) 0.4397; (c) 0.6940. 74. Calculate the chemical factor for (a) Sn in SnO_{2}; (b) MgO in Mg_{2}P_{2}O_{7}; (c) P_{2}O_{5} in Mg_{2}P_{2}O_{7}; (d) Fe in Fe_{2}O_{3}; (e) SO_{4} in BaSO_{4}. !Answers!: (a) 0.7879; (b) 0.3620; (c) 0.6378; (d) 0.6990; (e) 0.4115. 75. Calculate the log factor for (a) Pb in PbCrO_{4}; (b) Cr_{2}O_{3} in PbCrO_{4}; (c) Pb in PbO_{2} and (d) CaO in CaC_{2}O_{4}. !Answers!: (a) 9.8069-10, (b) 9.3713-10; (c) 9.9376-10; (d) 9.6415-10. 76. How many grams of Mn_{3}O_{4} can be obtained from 1 gram of MnO_{2}? !Answer!: 0.8774 gram. 77. If a sample of silver coin weighing 0.2500 gram gives a precipitate of AgCl weighing 0.2991 gram, what weight of AgI could have been obtained from the same weight of sample, and what is the percentage of silver in the coin? !Answers!: 0.4898 gr.; 90.05%. 78. How many cubic centimeters of hydrochloric acid (sp. gr. 1.13 containing 25.75% HCl by weight) are required to exactly neutralize 25 cc. of ammonium hydroxide (sp. gr. .90 containing 28.33% NH_{3} by weight)? !Answer!: 47.03 cc. 79. How many cubic centimeters of ammonium hydroxide solution (sp. gr. 0.96 containing 9.91% NH_{3} by weight) are required to precipitate the aluminium as aluminium hydroxide from a two-gram sample of alum (KAl(SO_{4})_{2}.12H_{2}O)? What will be the weight of the ignited precipitate? !Answers!: 2.26 cc.; 0.2154 gram. 80. What volume of nitric acid (sp. gr. 1.05 containing 9.0% HNO_{3} by weight) is required to oxidize the iron in one gram of FeSO_{4}.7H_{2}O in the presence of sulphuric acid? 6FeSO_{4} + 2HNO_{3} + 3H_{2}SO_{4} = 3Fe_{2}(SO_{4})_{3} + 2NO + 4H_{2}O. !Answer!: 0.80 cc. 81. If 0.7530 gram of ferric nitrate (Fe(NO_{3})_{3}.9H_{2}O) is dissolved in water and 1.37 cc. of HCl (sp. gr. 1.11 containing 21.92% HCl by weight) is added, how many cubic centimeters of ammonia (sp. gr. 0.96 containing 9.91% NH_{3} by weight) are required to neutralize the acid and precipitate the iron as ferric hydroxide? !Answer!: 2.63 cc. 82. To a suspension of 0.3100 gram of Al(OH)_{3} in water are added 13.00 cc. of aqueous ammonia (sp. gr. 0.90 containing 28.4% NH_{3} by weight). How many cubic centimeters of sulphuric acid (sp. gr. 1.18 containing 24.7% H_{2}SO_{4} by weight) must be added to the mixture in order to bring the aluminium into solution? !Answer!: 34.8 cc. 83. How many cubic centimeters of sulphurous acid (sp. gr. 1.04 containing 75 grams SO_{2} per liter) are required to reduce the iron in 1 gram of ferric alum (KFe(SO_{4})_{2}.12H_{2}O)? Fe_{2}(SO_{4})_{3} + SO_{2} + 2H_{2}O = 2FeSO_{4} + 2H_{2}SO_{4}. !Answer!: 0.85 cc. 84. How many cubic centimeters of a solution of potassium bichromate containing 26.30 grams of K_{2}Cr_{2}O_{7} per liter must be taken in order to yield 0.6033 gram of Cr_{2}O_{3} after reduction and precipitation of the chromium? K_{2}Cr_{2}O_{7} + 3SO_{2} + H_{2}SO_{4} = K_{2}SO_{4} + Cr_{2}(SO_{4})_{3} + H_{2}O. !Answer!: 44.39 cc. 85. How many cubic centimeters of ammonium hydroxide (sp. gr. 0.946 containing 13.88% NH_{3} by weight) are required to precipitate the iron as Fe(OH)_{3} from a sample of pure FeSO_{4}.(NH_{4})_{2}SO_{4}.6H_{2}O, which requires 0.34 cc. of nitric acid (sp. gr. 1.350 containing 55.79% HNO_{3} by weight) for oxidation of the iron? (See problem No. 80 for reaction.) !Answer!: 4.74 cc. 86. In the analysis of an iron ore by solution, oxidation and precipitation of the iron as Fe(OH)_{3}, what weight of sample must be taken for analysis so that each one hundredth of a gram of the ignited precipitate of Fe_{2}O_{3} shall represent one tenth of one per cent of iron? !Answer!: 6.99 grams. 87. What weight in grams of impure ferrous ammonium sulphate should be taken for analysis so that the number of centigrams of BaSO_{4} obtained will represent five times the percentage of sulphur in the sample? !Answer!: 0.6870 gram. 88. What weight of magnetite must be taken for analysis in order that, after precipitating and igniting all the iron to Fe_{2}O_{3}, the percentage of Fe_{2}O_{4} in the sample may be found by multiplying the weight in grams of the ignited precipitate by 100? !Answer!: 0.9665 gram. 89. After oxidizing the arsenic in 0.5000 gram of pure As_{2}S_{3} to arsenic acid, it is precipitated with "magnesia mixture" (MgCl_{2} + 2NH_{4}Cl). If exactly 12.6 cc. of the mixture are required, how many grams of MgCl_{2} per liter does the solution contain? H_{3}AsO_{4} + MgCl_{2} + 3NH_{4}OH = MgNH_{4}AsO_{4} + 2NH_{4}Cl + 3H_{2}O. !Answer!: 30.71 grams. 90. A sample is prepared for student analysis by mixing pure apatite (Ca_{3}(PO_{4})_{2}.CaCl_{2}) with an inert material. If 1 gram of the sample gives 0.4013 gram of Mg_{2}P_{2}O_{7}, how many cubic centimeters of ammonium oxalate solution (containing 40 grams of (NH_{4})_{2}C_{2}O_{4}.H_{2}O per liter) would be required to precipitate the calcium from the same weight of sample? !Answer!: 25.60 cc. 91. If 0.6742 gram of a mixture of pure magnesium carbonate and pure calcium carbonate, when treated with an excess of hydrochloric acid, yields 0.3117 gram of carbon dioxide, calculate the percentage of magnesium oxide and of calcium oxide in the sample. !Answers!: 13.22% MgO; 40.54% CaO. 92. The calcium in a sample of dolomite weighing 0.9380 gram is precipitated as calcium oxalate and ignited to calcium oxide. What volume of gas, measured over water at 20°C. and 765 mm. pressure, is given off during ignition, if the resulting oxide weighs 0.2606 gram? (G.M.V. = 22.4 liters; V.P. water at 20°C. = 17.4 mm.) !Answer!: 227 cc. 93. A limestone is found to contain 93.05% CaCO_{3}, and 5.16 % MgCO_{3}. Calculate the weight of CaO obtainable from 3 tons of the limestone, assuming complete conversion to oxide. What weight of Mg_{2}P_{2}O_{7} could be obtained from a 3-gram sample of the limestone? !Answers!: 1.565 tons; 0.2044 gram. 94. A sample of dolomite is analyzed for calcium by precipitating as the oxalate and igniting the precipitate. The ignited product is assumed to be CaO and the analyst reports 29.50% Ca in the sample. Owing to insufficient ignition, the product actually contained 8% of its weight of CaCO_{3}. What is the correct percentage of calcium in the sample, and what is the percentage error? !Answers!: 28.46%; 3.65% error. 95. What weight of impure calcite (CaCO_{3}) should be taken for analysis so that the volume in cubic centimeters of CO_{2} obtained by treating with acid, measured dry at 18°C. and 763 mm., shall equal the percentage of CaO in the sample? !Answer!: 0.2359 gram. 96. How many cubic centimeters of HNO_{3} (sp. gr. 1.13 containing 21.0% HNO_{3} by weight) are required to dissolve 5 grams of brass, containing 0.61% Pb, 24.39% Zn, and 75% Cu, assuming reduction of the nitric acid to NO by each constituent? What fraction of this volume of acid is used for oxidation? !Answers!: 55.06 cc.; 25%. 97. What weight of metallic copper will be deposited from a cupric salt solution by a current of 1.5 amperes during a period of 45 minutes, assuming 100% current efficiency? (1 Faraday = 96,500 coulombs.) !Answer!: 1.335 grams. 98. In the electrolysis of a 0.8000 gram sample of brass, there is obtained 0.0030 gram of PbO_{2}, and a deposit of metallic copper exactly equal in weight to the ignited precipitate of Zn_{2}P_{2}O_{7} subsequently obtained from the solution. What is the percentage composition of the brass? !Answers!: 69.75% Cu; 29.92% Zn; 0.33% Pb. 99. A sample of brass (68.90% Cu; 1.10% Pb and 30.00% Zn) weighing 0.9400 gram is dissolved in nitric acid. The lead is determined by weighing as PbSO_{4}, the copper by electrolysis and the zinc by precipitation with (NH_{4})_{2}HPO_{4} in a neutral solution. (a) Calculate the cubic centimeters of nitric acid (sp. gr. 1.42 containing 69.90% HNO_{3} by weight) required to just dissolve the brass, assuming reduction to NO. !Answer!: 2.48 cc. (b) Calculate the cubic centimeters of sulphuric acid (sp. gr. 1.84 containing 94% H_{2}SO_{4} by weight) to displace the nitric acid. !Answer!: 0.83 cc. (c) Calculate the weight of PbSO_{4}. !Answer!: 0.0152 gram. (d) The clean electrode weighs 10.9640 grams. Calculate the weight after the copper has been deposited. !Answer!: 11.6116 grams. (e) Calculate the grams of (NH_{4})_{2}HPO_{4} required to precipitate the zinc as ZnNH_{4}PO_{4}. !Answer!: 0.5705 gram. (f) Calculate the weight of ignited Zn_{2}P_{2}O_{7}. !Answer!: 0.6573 gram. 100. If in the analysis of a brass containing 28.00% zinc an error is made in weighing a 2.5 gram portion by which 0.001 gram too much is weighed out, what percentage error in the zinc determination would result? What volume of a solution of sodium hydrogen phosphate, containing 90 grams of Na_{2}HPO_{4}.12H_{2}O per liter, would be required to precipitate the zinc as ZnNH_{4}PO_{4} and what weight of precipitate would be obtained? !Answers!: (a) 0.04% error; (b) 39.97 cc.; (c) 1.909 grams. 101. A sample of magnesium carbonate, contaminated with SiO_{2} as its only impurity, weighs 0.5000 gram and loses 0.1000 gram on ignition. What volume of disodium phosphate solution (containing 90 grams Na_{2}HPO_{4}.12H_{2}O per liter) will be required to precipitate the magnesium as magnesium ammonium phosphate? !Answer!: 9.07 cc. 102. 2.62 cubic centimeters of nitric acid (sp. gr. 1.42 containing 69.80% HNO_{2} by weight) are required to just dissolve a sample of brass containing 69.27% Cu; 0.05% Pb; 0.07% Fe; and 30.61% Zn. Assuming the acid used as oxidizing agent was reduced to NO in every case, calculate the weight of the brass and the cubic centimeters of acid used as acid. !Answer!: 0.992 gram; 1.97 cc. 103. One gram of a mixture of silver chloride and silver bromide is found to contain 0.6635 gram of silver. What is the percentage of bromine? !Answer!: 21.30%. 104. A precipitate of silver chloride and silver bromide weighs 0.8132 gram. On heating in a current of chlorine, the silver bromide is converted to silver chloride, and the mixture loses 0.1450 gram in weight. Calculate the percentage of chlorine in the original precipitate. !Answer!: 6.13%. 105. A sample of feldspar weighing 1.000 gram is fused and the silica determined. The weight of silica is 0.6460 gram. This is fused with 4 grams of sodium carbonate. How many grams of the carbonate actually combined with the silica in fusion, and what was the loss in weight due to carbon dioxide during the fusion? !Answers!: 1.135 grams; 0.4715 gram. 106. A mixture of barium oxide and calcium oxide weighing 2.2120 grams is transformed into mixed sulphates, weighing 5.023 grams. Calculate the grams of calcium oxide and barium oxide in the mixture. !Answers!: 1.824 grams CaO; 0.3877 gram BaO. APPENDIX ELECTROLYTIC DISSOCIATION THEORY The following brief statements concerning the ionic theory and a few of its applications are intended for reference in connection with the explanations which are given in the Notes accompanying the various procedures. The reader who desires a more extended discussion of the fundamental theory and its uses is referred to such books as Talbot and Blanchard's !Electrolytic Dissociation Theory! (Macmillan Company), or Alexander Smith's !Introduction to General Inorganic Chemistry! (Century Company). The !electrolytic dissociation theory!, as propounded by Arrhenius in 1887, assumes that acids, bases, and salts (that is, electrolytes) in aqueous solution are dissociated to a greater or less extent into !ions!. These ions are assumed to be electrically charged atoms or groups of atoms, as, for example, H^{+} and Br^{-} from hydrobromic acid, Na^{+} and OH^{-} from sodium hydroxide, 2NH_{4}^{+} and SO_{4}^{--} from ammonium sulphate. The unit charge is that which is dissociated with a hydrogen ion. Those upon other ions vary in sign and number according to the chemical character and valence of the atoms or radicals of which the ions are composed. In any solution the aggregate of the positive charges upon the positive ions (!cations!) must always balance the aggregate negative charges upon the negative ions (!anions!). It is assumed that the Na^{+} ion, for example, differs from the sodium atom in behavior because of the very considerable electrical charge which it carries and which, as just stated, must, in an electrically neutral solution, be balanced by a corresponding negative charge on some other ion. When an electric current is passed through a solution of an electrolyte the ions move with and convey the current, and when the cations come into contact with the negatively charged cathode they lose their charges, and the resulting electrically neutral atoms (or radicals) are liberated as such, or else enter at once into chemical reaction with the components of the solution. Two ions of identically the same composition but with different electrical charges may exhibit widely different properties. For example, the ion MnO_{4}^{-} from permanganates yields a purple-red solution and differs in its chemical behavior from the ion MnO_{4}^{--} from manganates, the solutions of which are green. The chemical changes upon which the procedures of analytical chemistry depend are almost exclusively those in which the reacting substances are electrolytes, and analytical chemistry is, therefore, essentially the chemistry of the ions. The percentage dissociation of the same electrolyte tends to increase with increasing dilution of its solution, although not in direct proportion. The percentage dissociation of different electrolytes in solutions of equivalent concentrations (such, for example, as normal solutions) varies widely, as is indicated in the following tables, in which approximate figures are given for tenth-normal solutions at a temperature of about 18°C. ACIDS ========================================================================= | SUBSTANCE | PERCENTAGE DISSOCIATION IN | 0.1 EQUIVALENT SOLUTION _____________________________________________|___________________________ | HCl, HBr, HI, HNO_{3} | 90 | HClO_{3}, HClO_{4}, HMnO_{4} | 90 | H_{2}SO_{4} <--> H^{+} + HSO_{4}^{-} | 90 | H_{2}C_{2}O_{4} <--> H^{+} + HC_{2}O_{4}^{-} | 50 | H_{2}SO_{3} <--> H^{+} + HSO{_}3^{-} | 20 | H_{3}PO_{4} <--> H^{+} + H_{2}PO_{4}^{-} | 27 | H_{2}PO_{4}^{-} <--> H^{+} + HPO_{4}^{--} | 0.2 | H_{3}AsO_{4} <--> H^{+} + H_{2}AsO_{4}^{-} | 20 | HF | 9 | HC_{2}H_{3}O_{2} | 1.4 | H_{2}CO_{3} <--> H^{+} + HCO_{3}^{-} | 0.12 | H_{2}S <--> H^{+} + HS^{-} | 0.05 | HCN | 0.01 | ========================================================================= BASES ========================================================================= | SUBSTANCE | PERCENTAGE DISSOCIATION IN | 0.1 EQUIVALENT SOLUTION _____________________________________________|___________________________ | KOH, NaOH | 86 | Ba(OH)_{2} | 75 | NH_{4}OH | 1.4 | ========================================================================= SALTS ========================================================================= | TYPE OF SALT | PERCENTAGE DISSOCIATION IN | 0.1 EQUIVALENT SOLUTION _____________________________________________|___________________________ | R^{+}R^{-} | 86 | R^{++}(R^{-})_{2} | 72 | (R^{+})_{2}R^{--} | 72 | R^{++}R^{--} | 45 | ========================================================================= The percentage dissociation is determined by studying the electrical conductivity of the solutions and by other physico-chemical methods, and the following general statements summarize the results: !Salts!, as a class, are largely dissociated in aqueous solution. !Acids! yield H^{+} ions in water solution, and the comparative !strength!, that is, the activity, of acids is proportional to the concentration of the H^{+} ions and is measured by the percentage dissociation in solutions of equivalent concentration. The common mineral acids are largely dissociated and therefore give a relatively high concentration of H^{+} ions, and are commonly known as "strong acids." The organic acids, on the other hand, belong generally to the group of "weak acids." !Bases! yield OH^{-} ions in water solution, and the comparative strength of the bases is measured by their relative dissociation in solutions of equivalent concentration. Ammonium hydroxide is a weak base, as shown in the table above, while the hydroxides of sodium and potassium exhibit strongly basic properties. Ionic reactions are all, to a greater or less degree, !reversible reactions!. A typical example of an easily reversible reaction is that representing the changes in ionization which an electrolyte such as acetic acid undergoes on dilution or concentration of its solutions, !i.e.!, HC_{2}H_{3}O_{2} <--> H^{+} + C_{2}H_{3}O_{2}^{-}. As was stated above, the ionization increases with dilution, the reaction then proceeding from left to right, while concentration of the solution occasions a partial reassociation of the ions, and the reaction proceeds from right to left. To understand the principle underlying these changes it is necessary to consider first the conditions which prevail when a solution of acetic acid, which has been stirred until it is of uniform concentration throughout, has come to a constant temperature. A careful study of such solutions has shown that there is a definite state of equilibrium between the constituents of the solution; that is, there is a definite relation between the undissociated acetic acid and its ions, which is characteristic for the prevailing conditions. It is not, however, assumed that this is a condition of static equilibrium, but rather that there is continual dissociation and association, as represented by the opposing reactions, the apparent condition of rest resulting from the fact that the amount of change in one direction during a given time is exactly equal to that in the opposite direction. A quantitative study of the amount of undissociated acid, and of H^{+} ions and C_{2}H_{3}O_{2}^{-} ions actually to be found in a large number of solutions of acetic acid of varying dilution (assuming them to be in a condition of equilibrium at a common temperature), has shown that there is always a definite relation between these three quantities which may be expressed thus: (!Conc'n H^{+} x Conc'n C_{2}H_{3}O_{2}^{-})/Conc'n HC_{2}H_{3}O_{2} = Constant!. In other words, there is always a definite and constant ratio between the product of the concentrations of the ions and the concentration of the undissociated acid when conditions of equilibrium prevail. It has been found, further, that a similar statement may be made regarding all reversible reactions, which may be expressed in general terms thus: The rate of chemical change is proportional to the product of the concentrations of the substances taking part in the reaction; or, if conditions of equilibrium are considered in which, as stated, the rate of change in opposite directions is assumed to be equal, then the product of the concentrations of the substances entering into the reaction stands in a constant ratio to the product of the concentrations of the resulting substances, as given in the expression above for the solutions of acetic acid. This principle is called the !Law of Mass Action!. It should be borne in mind that the expression above for acetic acid applies to a wide range of dilutions, provided the temperature remains constant. If the temperature changes the value of the constant changes somewhat, but is again uniform for different dilutions at that temperature. The following data are given for temperatures of about 18°C.[1] ========================================================================== | | | | MOLAL | FRACTION | MOLAL CONCENTRA- | MOLAL CONCENTRA- | VALUE OF CONCENTRATION | IONIZED | TION OF H^{+} AND| TION OF UNDIS- | CONSTANT CONSTANT | | ACETATE^{-} IONS | SOCIATED ACID | ______________|__________|__________________|__________________|__________ | | | | 1.0 | .004 | .004 | .996 | .0000161 | | | | 0.1 | .013 | .0013 | .0987 | .0000171 | | | | 0.01 | .0407 | .000407 | .009593 | .0000172 | | | | =========================================================================== [Footnote 1: Alexander Smith, !General Inorganic Chemistry!, p. 579.] The molal concentrations given in the table refer to fractions of a gram-molecule per liter of the undissociated acid, and to fractions of the corresponding quantities of H^{+} and C_{2}H_{3}O_{2}^{-} ions per liter which would result from the complete dissociation of a gram-molecule of acetic acid. The values calculated for the constant are subject to some variation on account of experimental errors in determining the percentage ionized in each case, but the approximate agreement between the values found for molal and centimolal (one hundredfold dilution) is significant. The figures given also illustrate the general principle, that the !relative! ionization of an electrolyte increases with the dilution of its solution. If we consider what happens during the (usually) brief period of dilution of the solution from molal to 0.1 molal, for example, it will be seen that on the addition of water the conditions of concentration which led to equality in the rate of change, and hence to equilibrium in the molal solution, cease to exist; and since the dissociating tendency increases with dilution, as just stated, it is true at the first instant after the addition of water that the concentration of the undissociated acid is too great to be permanent under the new conditions of dilution, and the reaction, HC_{2}H_{3}O_{2} <--> H^{+} + C_{2}H_{3}O_{2}^{-}, will proceed from left to right with great rapidity until the respective concentrations adjust themselves to the new conditions. That which is true of this reaction is also true of all reversible reactions, namely, that any change of conditions which occasions an increase or a decrease in concentration of one or more of the components causes the reaction to proceed in one direction or the other until a new state of equilibrium is established. This principle is constantly applied throughout the discussion of the applications of the ionic theory in analytical chemistry, and it should be clearly understood that whenever an existing state of equilibrium is disturbed as a result of changes of dilution or temperature, or as a consequence of chemical changes which bring into action any of the constituents of the solution, thus altering their concentrations, there is always a tendency to re-establish this equilibrium in accordance with the law. Thus, if a base is added to the solution of acetic acid the H^{+} ions then unite with the OH^{-} ions from the base to form undissociated water. The concentration of the H^{+} ions is thus diminished, and more of the acid dissociates in an attempt to restore equilbrium, until finally practically all the acid is dissociated and neutralized. Similar conditions prevail when, for example, silver ions react with chloride ions, or barium ions react with sulphate ions. In the former case the dissociation reaction of the silver nitrate is AgNO_{3} <--> Ag^{+} + NO_{3}^{-}, and as soon as the Ag^{+} ions unite with the Cl^{-} ions the concentration of the former is diminished, more of the AgNO_{3} dissociates, and this process goes on until the Ag^{+} ions are practically all removed from the solution, if the Cl^{-} ions are present in sufficient quantity. For the sake of accuracy it should be stated that the mass law cannot be rigidly applied to solutions of those electrolytes which are largely dissociated. While the explanation of the deviation from quantitative exactness in these cases is not known, the law is still of marked service in developing analytical methods along more logical lines than was formerly practicable. It has not seemed wise to qualify each statement made in the Notes to indicate this lack of quantitative exactness. The student should recognize its existence, however, and will realize its significance better as his knowledge of physical chemistry increases. If we apply the mass law to the case of a substance of small solubility, such as the compounds usually precipitated in quantitative analysis, we derive what is known as the !solubility product!, as follows: Taking silver chloride as an example, and remembering that it is not absolutely insoluble in water, the equilibrium expression for its solution is: (!Conc'n Ag^{+} x Conc'n Cl^{-})/Conc'n AgCl = Constant!. But such a solution of silver chloride which is in contact with the solid precipitate must be saturated for the existing temperature, and the quantity of undissociated AgCl in the solution is definite and constant for that temperature. Since it is a constant, it may be eliminated, and the expression becomes !Conc'n Ag^{+} x Conc'n Cl^{-} = Constant!, and this is known as the solubility product. No precipitation of a specific substance will occur until the product of the concentrations of its ions in a solution exceeds the solubility product for that substance; whenever that product is exceeded precipitation must follow. It will readily be seen that if a substance which yields an ion in common with the precipitated compound is added to such a solution as has just been described, the concentration of that ion is increased, and as a result the concentration of the other ion must proportionately decrease, which can only occur through the formation of some of the undissociated compound which must separate from the already saturated solution. This explains why the addition of an excess of the precipitant is often advantageous in quantitative procedures. Such a case is discussed at length in Note 2 on page 113. Similarly, the ionization of a specific substance in solution tends to diminish on the addition of another substance with a common ion, as, for instance, the addition of hydrochloric acid to a solution of hydrogen sulphide. Hydrogen sulphide is a weak acid, and the concentration of the hydrogen ions in its aqueous solutions is very small. The equilibrium in such a solution may be represented as: (!(Conc'n H^{+})^{2} x Conc'n S^{--})/Conc'n H_{2}S = Constant!, and a marked increase in the concentration of the H^{+} ions, such as would result from the addition of even a small amount of the highly ionized hydrochloric acid, displaces the point of equilibrium and some of the S^{--} ions unite with H^{+} ions to form undissociated H_{2}S. This is of much importance in studying the reactions in which hydrogen sulphide is employed, as in qualitative analysis. By a parallel course of reasoning it will be seen that the addition of a salt of a weak acid or base to solutions of that acid or base make it, in effect, still weaker because they decrease its percentage ionization. To understand the changes which occur when solids are dissolved where chemical action is involved, it should be remembered that no substance is completely insoluble in water, and that those products of a chemical change which are least dissociated will first form. Consider, for example, the action of hydrochloric acid upon magnesium hydroxide. The minute quantity of dissolved hydroxide dissociates thus: Mg(OH)_{2} <--> Mg^{++} + 2OH^{-}. When the acid is introduced, the H^{+} ions of the acid unite with the OH^{-} ions to form undissociated water. The concentration of the OH^{-} ions is thus diminished, more Mg(OH)_{2} dissociates, the solution is no longer saturated with the undissociated compound, and more of the solid dissolves. This process repeats itself with great rapidity until, if sufficient acid is present, the solid passes completely into solution. Exactly the same sort of process takes place if calcium oxalate, for example, is dissolved in hydrochloric acid. The C_{2}O_{4}^{--} ions unite with the H^{+} ions to form undissociated oxalic acid, the acid being less dissociated than normally in the presence of the H^{+} ions from the hydrochloric acid (see statements regarding hydrogen sulphide above). As the undissociated oxalic acid forms, the concentration of the C_{2}O_{4}^{--} ions lessens and more CaC_{2}O_{4} dissolves, as described for the Mg(OH)_{2} above. Numerous instances of the applications of these principles are given in the Notes. Water itself is slightly dissociated, and although the resulting H^{+} and OH^{-} ions are present only in minute concentrations (1 mol. of dissociated water in 10^{7} liters), yet under some conditions they may give rise to important consequences. The term !hydrolysis! is applied to the changes which result from the reaction of these ions. Any salt which is derived from a weak base or a weak acid (or both) is subject to hydrolytic action. Potassium cyanide, for example, when dissolved in water gives an alkaline solution because some of the H^{+} ions from the water unite with CN^{-} ions to form (HCN), which is a very weak acid, and is but very slightly dissociated. Potassium hydroxide, which might form from the OH^{-} ions, is so largely dissociated that the OH^{-} ions remain as such in the solution. The union of the H^{+} ions with the CN^{-} ions to form the undissociated HCN diminishes the concentration of the H^{+} ions, and more water dissociates (H_{2}O <--> H^{+} + OH^{-}) to restore the equilibrium. It is clear, however, that there must be a gradual accumulation of OH^{-} ions in the solution as a result of these changes, causing the solution to exhibit an alkaline reaction, and also that ultimately the further dissociation of the water will be checked by the presence of these ions, just as the dissociation of the H_{2}S was lessened by the addition of HCl. An exactly opposite result follows the solution of such a salt as Al_{2}(SO_{4})_{3} in water. In this case the acid is strong and the base weak, and the OH^{-} ions form the little dissociated Al(OH)_{3}, while the H^{+} ions remain as such in the solution, sulphuric acid being extensively dissociated. The solution exhibits an acid reaction. Such hydrolytic processes as the above are of great importance in analytical chemistry, especially in the understanding of the action of indicators in volumetric analysis. (See page 32.) The impelling force which causes an element to pass from the atomic to the ionic condition is termed !electrolytic solution pressure!, or ionization tension. This force may be measured in terms of electrical potential, and the table below shows the relative values for a number of elements. In general, an element with a greater solution pressure tends to cause the deposition of an element of less solution pressure when placed in a solution of its salt, as, for instance, when a strip of zinc or iron is placed in a solution of a copper salt, with the resulting precipitation of metallic copper. Hydrogen is included in the table, and its position should be noted with reference to the other common elements. For a more extended discussion of this topic the student should refer to other treatises. POTENTIAL SERIES OF THE METALS __________________________________________________________________ | | | | POTENTIAL | | POTENTIAL | IN VOLTS | | IN VOLTS _____________________|___________|____________________|___________ | | | Sodium Na^{+} | +2.44 | Lead Pb^{++} | -0.13 Calcium Ca^{++} | | Hydrogen H^{+} | -0.28 Magnesium Mg^{++} | | Bismuth Bi^{+++}| Aluminum A1^{+++} | +1.00 | Antimony | -0.75 Manganese Mn^{++} | | Arsenic | Zinc Zn^{++} | +0.49 | Copper Cu^{++} | -0.61 Cadmium Cd^{++} | +0.14 | Mercury Hg^{+} | -1.03 Iron Fe^{++} | +0.063 | Silver Ag^{+} | -1.05 Cobalt Co^{++} | -0.045 | Platinum | Nickel Ni^{++} | -0.049 | Gold | Tin Sn^{++} | -0.085(?) | | _____________________|___________|____________________|__________ THE FOLDING OF A FILTER PAPER If a filter paper is folded along its diameter, and again folded along the radius at right angles to the original fold, a cone is formed on opening, the angle of which is 60°. Funnels for analytical use are supposed to have the same angle, but are rarely accurate. It is possible, however, with care, to fit a filter thus folded into a funnel in such a way as to prevent air from passing down between the paper and the funnel to break the column of liquid in the stem, which aids greatly, by its gentle suction, in promoting the rate of filtration. Such a filter has, however, the disadvantage that there are three thicknesses of paper back of half of its filtering surface, as a consequence of which one half of a precipitate washes or drains more slowly. Much time may be saved in the aggregate by learning to fold a filter in such a way as to improve its effective filtering surface. The directions which follow, though apparently complicated on first reading, are easily applied and easily remembered. Use a 6-inch filter for practice. Place four dots on the filter, two each on diameters which are at right angles to each other. Then proceed as follows: (1) Fold the filter evenly across one of the diameters, creasing it carefully; (2) open the paper, turn it over, rotate it 90° to the right, bring the edges together and crease along the other diameter; (3) open, and rotate 45° to the right, bring edges together, and crease evenly; (4) open, and rotate 90° to the right, and crease evenly; (5) open, turn the filter over, rotate 22-(1/2)° to the right, and crease evenly; (6) open, rotate 45° to the right and crease evenly; (7) open, rotate 45° to the right and crease evenly; (8) open, rotate 45° to the right and crease evenly; (9) open the filter, and, starting with one of the dots between thumb and forefinger of the right hand, fold the second crease to the left over on it, and do the same with each of the other dots. Place it, thus folded, in the funnel, moisten it, and fit to the side of the funnel. The filter will then have four short segments where there are three thicknesses and four where there is one thickness, but the latter are evenly distributed around its circumference, thus greatly aiding the passage of liquids through the paper and hastening both filtration and washing of the whole contents of the filter. !SAMPLE PAGES FOR LABORATORY RECORDS! !Page A! Date CALIBRATION OF BURETTE No. ___________________________________________________________________________ | | | | BURETTE | DIFFERENCE | OBSERVED | DIFFERENCE | CALCULATED READINGS | | WEIGHTS | | CORRECTION _______________|______________|______________|______________|______________ 0.02 | | 16.27 | | 10.12 | 10.10 | 26.35 | 10.08 | -.02 20.09 | 9.97 | 36.26 | 9.91 | -.06 30.16 | 10.07 | 46.34 | 10.08 | +.01 40.19 | 10.03 | 56.31 | 9.97 | -.06 50.00 | 9.81 | 66.17 | 9.86 | +.05 _______________|______________|______________|______________|______________ These data to be obtained in duplicate for each burette. !Page B! Date DETERMINATION OF COMPARATIVE STRENGTH HCl vs. NaOH ___________________________________________________________________________ | | DETERMINATION | I | II _________________________|________________________|________________________ | | | Corrected | Corrected Final Reading HCl | 48.17 48.08 | 43.20 43.14 Initial Reading HCl | 0.12 .12 | .17 .17 | ----- ----- | ----- ----- | 47.96 | 42.97 | | | Corrected | Corrected Final Reading HCl | 46.36 46.29 | 40.51 40.37 Initial Reading HCl | 1.75 1.75 | .50 .50 | ----- ----- | ----- ----- | 44.54 | 39.87 | | log cc. NaOH | 1.6468 | 1.6008 colog cc. HCl | 8.3192 | 8.3668 | ------ | ------ | 9.9680 - 10 | 9.9676 - 10 1 cc. HCl | .9290 cc. NaOH | .9282 cc. NaOH Mean | .9286 | _________________________|________________________|________________________ Signed !Page C! Date STANDARDIZATION OF HYDROCHLORIC ACID ===================================================================== | | Weight sample and tube| 9.1793 | 8.1731 | 8.1731 | 6.9187 | ------ | ------ Weight sample | 1.0062 | 1.2544 | | Final Reading HCl | 39.97 39.83 | 49.90 49.77 Initial Reading HCl | .00 .00 | .04 .04 | ----- ----- | ----- ----- | 39.83 | 49.73 | | Final Reading NaOH | .26 .26 | .67 .67 Initial Reading NaOH | .12 .12 | .36 .36 | --- --- | --- --- | .14 | .31 | | | .14 | .31 Corrected cc. HCl | 39.83 - ----- = 39.68 | 49.73 - ----- = 49.40 | .9286 | .9286 | | log sample | 0.0025 | 0.0983 colog cc | 8.4014 - 10 | 8.3063 - 10 colog milli equivalent| 1.2757 | 1.2757 | ------ | ------ | 9.6796 - 10 | 9.6803 - 10 | | Normal value HCl | .4782 | .4789 Mean | .4786 | | | ===================================================================== Signed !Page D! Date DETERMINATION OF CHLORINE IN CHLORIDE, SAMPLE No. ===================================================================== | | Weight sample and tube| 16.1721 | 15.9976 | 15.9976 | 15.7117 | ------- | ------- Weight sample | .1745 | .2859 | | Weight crucible | | + precipitate | 14.4496 | 15.6915 Constant weights | 14.4487 | 15.6915 | 14.4485 | | | Weight crucible | 14.2216 | 15.3196 Constant weight | 14.2216 | 15.3194 | | Weight AgCl | .2269 | .3721 | | log Cl | 1.5496 | 1.5496 log weight AgCl | 9.3558 - 10 | 9.5706 - 10 log 100 | 2.0000 | 2.0000 colog AgCl | 7.8438 - 10 | 7.7438 - 10 colog sample | 0.7583 | 0.5438 | ------- | ------- | 1.5075 | 1.5078 | | Cl in sample No. | 32.18% | 32.20% | | ===================================================================== Signed STRENGTH OF REAGENTS The concentrations given in this table are those suggested for use in the procedures described in the foregoing pages. It is obvious, however, that an exact adherence to these quantities is not essential. Approx. Approx. Grams relation relation per to normal to molal liter. solution solution Ammonium oxalate, (NH_{4})_{2}C_{2}O_{4}.H_{2}O 40 0.5N 0.25 Barium chloride, BaCl_{2}.2H_{2}O 25 0.2N 0.1 Magnesium ammonium chloride (of MgCl_{2}) 71 1.5N 0.75 Mercuric chloride, HgCl_{2} 45 0.33N 0.66 Potassium hydroxide, KOH (sp. gr. 1.27) 480 Potassium thiocyanate, KSCN 5 0.05N 0.55 Silver nitrate, AgNO_{3} 21 0.125N 0.125 Sodium hydroxide, NaOH 100 2.5N 2.5 Sodium carbonate. Na_{2}CO_{3} 159 3N 1.5 Sodium phosphate, Na_{2}HPO_{4}.12H_{2}O 90 0.5N or 0.75N 0.25 Stannous chloride, SnCl_{2}, made by saturating hydrochloric acid (sp. gr. 1.2) with tin, diluting with an equal volume of water, and adding a slight excess of acid from time to time. A strip of metallic tin is kept in the bottle. A solution of ammonium molybdate is best prepared as follows: Stir 100 grams of molybdic acid (MoO_{3}) into 400 cc. of cold, distilled water. Add 80 cc. of concentrated ammonium hydroxide (sp. gr. 0.90). Filter, and pour the filtrate slowly, with constant stirring, into a mixture of 400 cc. concentrated nitric acid (sp. gr. 1.42) and 600 cc. of water. Add to the mixture about 0.05 gram of microcosmic salt. Filter, after allowing the whole to stand for 24 hours. The following data regarding the common acids and aqueous ammonia are based upon percentages given in the Standard Tables of the Manufacturing Chemists' Association of the United States [!J.S.C.I.!, 24 (1905), 787-790]. All gravities are taken at 15.5°C. and compared with water at the same temperature. Aqueous ammonia (sp. gr. 0.96) contains 9.91 per cent NH_{3} by weight, and corresponds to a 5.6 N and 5.6 molal solution. Aqueous ammonia (sp. gr. 0.90) contains 28.52 per cent NH_{3} by weight, and corresponds to a 5.6 N and 5.6 molal solution. Hydrochloric acid (sp. gr. 1.12) contains 23.81 per cent HCl by weight, and corresponds to a 7.3 N and 7.3 molal solution. Hydrochloric acid (sp. gr. 1.20) contains 39.80 per cent HCl by weight, and corresponds to a 13.1 N and 13.1 molal solution. Nitric acid (sp. gr. 1.20) contains 32.25 per cent HNO_{3} by weight, and corresponds to a 6.1 N and 6.1 molal solution: Nitric acid (sp. gr. 1.42) contains 69.96 per cent HNO_{3} by weight, and corresponds to a 15.8 N and 15.8 molal solution. Sulphuric acid (sp. gr. 1.8354) contains 93.19 per cent H_{2}SO_{4} by weight, and corresponds to a 34.8 N or 17.4 molal solution. Sulphuric acid (sp. gr. 1.18) contains 24.74 per cent H_{2}SO_{4} by weight, and corresponds to a 5.9 N or 2.95 molal solution. The term !normal! (N), as used above, has the same significance as in volumetric analyses. The molal solution is assumed to contain one molecular weight in grams in a liter of solution. DENSITIES AND VOLUMES OF WATER AT TEMPERATURES FROM 15-30°C. Temperature Density. Volume. Centigrade. 4° 1.000000 1.000000 15° 0.999126 1.000874 16° 0.998970 1.001031 17° 0.998801 1.001200 18° 0.998622 1.001380 19° 0.998432 1.001571 20° 0.998230 1.001773 21° 0.998019 1.001985 22° 0.997797 1.002208 23° 0.997565 1.002441 24° 0.997323 1.002685 25° 0.997071 1.002938 26° 0.996810 1.003201 27° 0.996539 1.003473 28° 0.996259 1.003755 29° 0.995971 1.004046 30° 0.995673 1.004346 Authority: Landolt, Börnstein, and Meyerhoffer's !Tabellen!, third edition. CORRECTIONS FOR CHANGE OF TEMPERATURE OF STANDARD SOLUTIONS The values below are average values computed from data relating to a considerable number of solutions. They are sufficiently accurate for use in chemical analyses, except in the comparatively few cases where the highest attainable accuracy is demanded in chemical investigations. The expansion coefficients should then be carefully determined for the solutions employed. For a compilation of the existing data, consult Landolt, Börnstein, and Meyerhoffer's !Tabellen!, third edition. Corrections for 1 cc. Concentration. of solution between 15° and 35°C. Normal .00029 0.5 Normal .00025 0.1 Normal or more dilute solutions .00020 The volume of solution used should be multiplied by the values given, and that product multiplied by the number of degrees which the temperature of the solution varies from the standard temperature selected for the laboratory. The total correction thus found is subtracted from the observed burette reading if the temperature is higher than the standard, or added, if it is lower. Corrections are not usually necessary for variations of temperature of 2°C. or less. INTERNATIONAL ATOMIC WEIGHTS ========================================================== | | | | 1920 | | 1920 _________________|_________|___________________|__________ | | | Aluminium Al | 27.1 | Molybdenum Mo | 96.0 Antimony Sb | 120.2 | Neodymium Nd | 144.3 Argon A | 39.9 | Neon Ne | 20.2 Arsenic As | 74.96 | Nickel Ni | 58.68 Barium Ba | 137.37 | Nitrogen N | 14.008 Bismuth Bi | 208.0 | Osmium Os | 190.9 Boron B | 11.0 | Oxygen O | 16.00 Bromine Br | 79.92 | Palladium Pd | 106.7 Cadmium Cd | 112.40 | Phosphorus P | 31.04 Caesium Cs | 132.81 | Platinum Pt | 195.2 Calcium Ca | 40.07 | Potassium K | 39.10 Carbon C | 12.005 | Praseodymium Pr | 140.9 Cerium Ce | 140.25 | Radium Ra | 226.0 Chlorine Cl | 35.46 | Rhodium Rh | 102.9 Chromium Cr | 52.0 | Rubidium Rb | 85.45 Cobalt Co | 58.97 | Ruthenium Ru | 101.7 Columbium Cb | 93.1 | Samarium Sm | 150.4 Copper Cu | 63.57 | Scandium Sc | 44.1 Dysprosium Dy | 162.5 | Selenium Se | 79.2 Erbium Er | 167.7 | Silicon Si | 28.3 Europium Eu | 152.0 | Silver Ag | 107.88 Fluorine Fl | 19.0 | Sodium Na | 23.00 Gadolinium Gd | 157.3 | Strontium Sr | 87.63 Gallium Ga | 69.9 | Sulphur S | 32.06 Germanium Ge | 72.5 | Tantalum Ta | 181.5 Glucinum Gl | 9.1 | Tellurium Te | 127.5 Gold Au | 197.2 | Terbium Tb | 159.2 Helium He | 4.00 | Thallium Tl | 204.0 Hydrogen H | 1.008 | Thorium Th | 232.4 Indium In | 114.8 | Thulium Tm | 168.5 Iodine I | 126.92 | Tin Sn | 118.7 Iridium Ir | 193.1 | Titanium Ti | 48.1 Iron Fe | 55.84 | Tungsten W | 184.0 Krypton Kr | 82.92 | Uranium U | 238.2 Lanthanum La | 139.0 | Vanadium V | 51.0 Lead Pb | 207.2 | Xenon Xe | 130.2 Lithium Li | 6.94 | Ytterbium Yb | 173.5 Lutecium Lu | 175.0 | Yttrium Y | 88.7 Magnesium Mg | 24.32 | Zinc Zn | 65.37 Manganese Mn | 54.93 | Zirconium Zr | 90.6 Mercury Hg | 200.6 | | ========================================================== INDEX Acidimetry Acid solutions, normal standard Acids, definition of Acids, weak, action of other acids on action of salts on Accuracy demanded Alkalimetry Alkali solutions, normal standard Alumina, determination of in stibnite Ammonium nitrate, acid Analytical chemistry, subdivisions of Antimony, determination of, in stibnite Apatite, analysis of Asbestos filters Atomic weights, table of Balances, essential features of use and care of Barium sulphate, determination of sulphur in Bases, definition of Bichromate process for iron Bleaching powder, analysis of Brass, analysis of Burette, description of calibration of cleaning of reading of Calcium, determination of, in limestone Calibration, definition of of burettes of flasks Carbon dioxide, determination of, in limestone Chlorimetry Chlorine, gravimetric determination of Chrome iron ore, analysis of Coin, determination of silver in Colloidal solution of precipitates Colorimetric analyses, definition of Copper, determination of, in brass determination of in copper ores Crucibles, use of Crystalline precipitates Densities of water Deposition potentials Desiccators Direct methods Dissociation, degree of Economy of time Electrolytic dissociation, theory of Electrolytic separations, principles of End-point, definition of Equilibrium, chemical Evaporation of liquids Faraday's law Feldspar, analysis of Ferrous ammonium sulphate, analysis of Filters, folding of how fitted Filtrates, testing of Filtration Flasks, graduation of Funnels Fusions, removal of from crucibles General directions for gravimetric analysis volumetric analysis Gooch filter Gravimetric analysis, definition of Hydrochloric acid, standardization of Hydrolysis Ignition of precipitates Indicators, definition of for acidimetry preparation of Indirect methods Insoluble matter, determination of in limestone Integrity Iodimetry Ions, definition of Iron, gravimetric determination of volumetric determination of Jones reductor Lead, determination of in brass Limestone, analysis of Limonite, determination of iron in Liquids, evaporation of transfer of Litmus Logarithms Magnesium, determination of Mass action, law of Measuring instruments Methyl orange Moisture, determination of in limestone Neutralization methods Normal solutions, acid and alkali oxidizing agents reducing agents Notebooks, sample pages of Oxalic acid, determination of strength of Oxidation processes Oxidizing power of pyrolusite Permanganate process for iron Phenolphthalein Phosphoric anhydride, determination of Pipette, calibration of description of Platinum crucibles, care of Precipitates, colloidal crystalline ignition of separation from filter washing of Precipitation Precipitation methods (volumetric) Problems Pyrolusite, oxidizing power of Quantitative Analyses, subdivisions of Reagents, strength of Reducing solution, normal Reductor, Jones Reversible reactions Silica, determination of, in limestone determination of, in silicates purification of Silicic acid, dehydration of Silver, determination of in coin Soda ash, alkaline strength of Sodium chloride, determination of chlorine in Solubility product Solution pressure Solutions, normal standard Standardization, definition of Standard solutions, acidimetry and alkalimetry chlorimetry iodimetry oxidizing and reducing agents thiocyanate Starch solutions Stibnite, determination of antimony in Stirring rods Stoichiometry Strength of reagents Suction, use of Sulphur, determination of in ferrous ammonium sulphate in barium sulphate Temperature, corrections for Testing of washings Theory of electrolytic dissociation Thiocyanate process for silver Titration, definition of Transfer of liquids Volumetric analysis, definition of general directions Wash-bottles Washed filters Washing of precipitates Washings, testing of Water, ionization of densities of Weights, care of Zimmermann-Reinhardt method for iron Zinc, determination of, in brass 
1923	----	None 
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14218	----	Note: Project Gutenberg also has an HTML version of this file which includes the original illustrations. See 14218-h.htm or 14218-h.zip: (http://www.gutenberg.net/dirs/1/4/2/1/14218/14218-h/14218-h.htm) or (http://www.gutenberg.net/dirs/1/4/2/1/14218/14218-h.zip) THE STORY OF ALCHEMY AND THE BEGINNINGS OF CHEMISTRY by M. M. PATTISON MUIR, M.A. Fellow and Formerly Prælector in Chemistry of Gonville and Caius College, Cambridge With Eighteen Illustrations New and Enlarged Edition Hodder and Stoughton London, New York, Toronto [Illustration: AN ALCHEMICAL LABORATORY] "It is neither religious nor wise to judge that of which you know nothing." _A Brief Guide to the Celestial Ruby_, by PHILALETHES (17th century) * * * * * THE USEFUL KNOWLEDGE SERIES Cloth, One Shilling net each List of the first thirty-four volumes issued in the new style with Pictorial Wrappers:-- WIRELESS TELEGRAPHY. By ALFRED T. STORY. A PIECE OF COAL. By K.A. MARTIN, F.G.S. ARCHITECTURE. By P.L. WATERHOUSE. THE COTTON PLANT. By F. WILKINSON, F.G.S. PLANT LIFE. By GRANT ALLEN. WILD FLOWERS. By REV. PROF. G. HENSLOW, F.L.S., F.G.S. THE SOLAR SYSTEM. By G.F. CHAMBERS, F.R.A.S. ECLIPSES. By G.F. CHAMBERS, F.R.A.S. THE STARS. By G.F.CHAMBERS, F.R.A.S. THE WEATHER. By G.F. CHAMBERS, F.R.A.S. ANIMAL LIFE. By B. LINDSAY. GEOGRAPHICAL DISCOVERY. By JOSEPH JACOBS. THE ATMOSPHERE. By DOUGLAS ARCHIBALD, M.A. ALPINE CLIMBING. By FRANCIS GRIBBLE FOREST AND STREAM. By JAMES RODWAY, F.L.S. FISH LIFE. By W.P. PYCRAFT, F.Z.S. BIRD LIFE. By W.P. PYCRAFT, F.Z.S. PRIMITIVE MAN. By EDWARD CLODD. ANCIENT EGYPT. By ROBINSON SOUTTAR, M.A., D.C.L. STORY OF LOCOMOTION. By BECKLES WILLSON. THE EARTH IN PAST AGES. By H.G. SEELEY, F.R.S. THE EMPIRE. By E. SALMON. KING ALFRED. By SIR WALTER BESANT. LOST ENGLAND. By BECKLES WILLSON. ALCHEMY, OR THE BEGINNINGS OF CHEMISTRY. By M.M. PATTISON MUIR, M.A. THE CHEMICAL ELEMENTS. By M.M. PATTISON MUIR, M.A. THE WANDERINGS OF ATOMS. By M.M. PATTISON MUIR, M.A. GERM LIFE: BACTERIA. By H.W. CONN. LIFE IN THE SEAS. By SIDNEY J. HICKSON F.R.S. LIFE'S MECHANISM. By H.W. CONN. REPTILE LIFE. By W.P. PYCRAFT, F.Z.S. THE GRAIN OF WHEAT. By WILLIAM C. EDGAR. THE POTTER. By C.F. BINNS. * * * * * PREFACE. The Story of Alchemy and the Beginnings of Chemistry is very interesting in itself. It is also a pregnant example of the contrast between the scientific and the emotional methods of regarding nature; and it admirably illustrates the differences between well-grounded, suggestive, hypotheses, and baseless speculations. I have tried to tell the story so that it may be intelligible to the ordinary reader. M.M. PATTISON MUIR. CAMBRIDGE, November 1902. * * * * * NOTE TO NEW EDITION. A few small changes have been made. The last chapter has been re-written and considerably enlarged. M.M.P.M. FARNHAM, September 1913. * * * * * CONTENTS. CHAPTER I. THE EXPLANATION OF MATERIAL CHANGES GIVEN BY GREEK THINKERS II. A SKETCH OF ALCHEMICAL THEORY III. THE ALCHEMICAL NOTION OF THE UNITY AND SIMPLICITY OF NATURE IV. THE ALCHEMICAL ELEMENTS AND PRINCIPLES V. THE ALCHEMICAL ESSENCE VI. ALCHEMY AS AN EXPERIMENTAL ART VII. THE LANGUAGE OF ALCHEMY VIII. THE DEGENERACY OF ALCHEMY IX. PARACELSUS, AND SOME OTHER ALCHEMISTS X. SUMMARY OF THE ALCHEMICAL DOCTRINE--THE REPLACEMENT OF THE THREE PRINCIPLES OF THE ALCHEMISTS BY THE SINGLE PRINCIPLE OF PHLOGISTON XI. THE EXAMINATION OF THE PHENOMENA OF COMBUSTION XII. THE RECOGNITION OF CHEMICAL CHANGES AS THE INTERACTIONS OF DEFINITE SUBSTANCES XIII. THE CHEMICAL ELEMENTS CONTRASTED WITH THE ALCHEMICAL PRINCIPLES XIV. THE MODERN FORM OF THE ALCHEMICAL QUEST OF THE ONE THING INDEX LIST OF ILLUSTRATIONS FIG. AN ALCHEMICAL LABORATORY (Frontispiece) 1. THE MORTIFICATION OF METALS PRESENTED BY THE IMAGE OF A KING DEVOURING HIS SON 2 and 3. THE MORTIFICATION OF METALS PRESENTED BY IMAGES OF DEATH AND BURIAL 4 and 5. TWO MUST BE CONJOINED TO PRODUCE ONE 6. HERMETICALLY SEALING THE NECK OF A GLASS VESSEL 7. SEALING BY MEANS OF A MERCURY TRAP 8. AN ALCHEMICAL COMMON COLD STILL 9. A _BALNEUM MARIÆ_ 10. ALCHEMICAL DISTILLING APPARATUS 11. A PELICAN 12. AN ALCHEMIST WITH A RETORT 13. AN ALCHEMIST PREPARING OIL OF VITRIOL 14. ALCHEMICAL APPARATUS FOR RECTIFYING SPIRITS 15. PURIFYING GOLD PRESENTED BY THE IMAGE OF A SALAMANDER IN THE FIRE 16. PRIESTLEY'S APPARATUS FOR WORKING WITH GASES 17. APPARATUS USED BY LAVOISIER IN HIS EXPERIMENTS ON BURNING MERCURY IN AIR CHAPTER I THE EXPLANATION OF MATERIAL CHANGES GIVEN BY THE GREEK THINKERS. For thousands of years before men had any accurate and exact knowledge of the changes of material things, they had thought about these changes, regarded them as revelations of spiritual truths, built on them theories of things in heaven and earth (and a good many things in neither), and used them in manufactures, arts, and handicrafts, especially in one very curious manufacture wherein not the thousandth fragment of a grain of the finished article was ever produced. The accurate and systematic study of the changes which material things undergo is called chemistry; we may, perhaps, describe alchemy as the superficial, and what may be called subjective, examination of these changes, and the speculative systems, and imaginary arts and manufactures, founded on that examination. We are assured by many old writers that Adam was the first alchemist, and we are told by one of the initiated that Adam was created on the sixth day, being the 15th of March, of the first year of the world; certainly alchemy had a long life, for chemistry did not begin until about the middle of the 18th century. No branch of science has had so long a period of incubation as chemistry. There must be some extraordinary difficulty in the way of disentangling the steps of those changes wherein substances of one kind are produced from substances totally unlike them. To inquire how those of acute intellects and much learning regarded such occurrences in the times when man's outlook on the world was very different from what it is now, ought to be interesting, and the results of that inquiry must surely be instructive. If the reader turns to a modern book on chemistry (for instance, _The Story of the Chemical Elements_, in this series), he will find, at first, superficial descriptions of special instances of those occurrences which are the subject of the chemist's study; he will learn that only certain parts of such events are dealt with in chemistry; more accurate descriptions will then be given of changes which occur in nature, or can be produced by altering the ordinary conditions, and the reader will be taught to see certain points of likeness between these changes; he will be shown how to disentangle chemical occurrences, to find their similarities and differences; and, gradually, he will feel his way to general statements, which are more or less rigorous and accurate expressions of what holds good in a large number of chemical processes; finally, he will discover that some generalisations have been made which are exact and completely accurate descriptions applicable to every case of chemical change. But if we turn to the writings of the alchemists, we are in a different world. There is nothing even remotely resembling what one finds in a modern book on chemistry. Here are a few quotations from alchemical writings [1]: [1] Most of the quotations from alchemical writings, in this book, are taken from a series of translations, published in 1893-94, under the supervision of Mr A.E. Waite. "It is necessary to deprive matter of its qualities in order to draw out its soul.... Copper is like a man; it has a soul and a body ... the soul is the most subtile part ... that is to say, the tinctorial spirit. The body is the ponderable, material, terrestrial thing, endowed with a shadow.... After a series of suitable treatments copper becomes without shadow and better than gold.... The elements grow and are transmuted, because it is their qualities, not their substances which are contrary." (Stephanus of Alexandria, about 620 A.D.) "If we would elicit our Medecine from the precious metals, we must destroy the particular metalic form, without impairing its specific properties. The specific properties of the metal have their abode in its spiritual part, which resides in homogeneous water. Thus we must destroy the particular form of gold, and change it into its generic homogeneous water, in which the spirit of gold is preserved; this spirit afterwards restores the consistency of its water, and brings forth a new form (after the necessary putrefaction) a thousand times more perfect than the form of gold which it lost by being reincrudated." (Philalethes, 17th century.) "The bodily nature of things is a concealing outward vesture." (Michael Sendivogius, 17th century.) "Nothing of true value is located in the body of a substance, but in the virtue ... the less there is of body, the more in proportion is the virtue." (Paracelsus, 16th century.) "There are four elements, and each has at its centre another element which makes it what it is. These are the four pillars of the world.... It is their contrary action which keeps up the harmony and equilibrium of the mundane machinery." (Michael Sendivogius.) "Nature cannot work till it has been supplied with a material: the first matter is furnished by God, the second matter by the sage." (Michael Sendivogius.) "When corruptible elements are united in a certain substance, their strife must sooner or later bring about its decomposition, which is, of course, followed by putrefaction; in putrefaction, the impure is separated from the pure; and if the pure elements are then once more joined together by the action of natural heat, a much nobler and higher form of life is produced.... If the hidden central fire, which during life was in a state of passivity, obtain the mastery, it attracts to itself all the pure elements, which are thus separated from the impure, and form the nucleus of a far purer form of life." (Michael Sendivogius.) "Cause that which is above to be below; that which is visible to be invisible; that which is palpable to become impalpable. Again let that which is below become that which is above; let the invisible become visible, and the impalpable become palpable. Here you see the perfection of our Art, without any defect or diminution." (Basil Valentine, 15th century.) "Think most diligently about this; often bear in mind, observe and comprehend, that all minerals and metals together, in the same time, and after the same fashion, and of one and the same principal matter, are produced and generated. That matter is no other than a mere vapour, which is extracted from the elementary earth by the superior stars, or by a sidereal distillation of the macrocosm; which sidereal hot infusion, with an airy sulphurous property, descending upon inferiors, so acts and operates as that there is implanted, spiritually and invisibly, a certain power and virtue in those metals and minerals; which fume, moreover, resolves in the earth into a certain water, wherefrom all metals are thenceforth generated and ripened to their perfection, and thence proceeds this or that metal or mineral, according as one of the three principles acquires dominion, and they have much or little of sulphur and salt, or an unequal mixture of these; whence some metals are fixed--that is, constant or stable; and some are volatile and easily changeable, as is seen in gold, silver, copper, iron, tin, and lead." (Basil Valentine.) "To grasp the invisible elements, to attract them by their material correspondences, to control, purify, and transform them by the living power of the Spirit--this is true Alchemy." (Paracelsus.) "Destruction perfects that which is good; for the good cannot appear on account of that which conceals it.... Each one of the visible metals is a concealment of the other six metals." (Paracelsus.) These sayings read like sentences in a forgotten tongue. Humboldt tells of a parrot which had lived with a tribe of American Indians, and learnt scraps of their language; the tribe totally disappeared; the parrot alone remained, and babbled words in the language which no living human being could understand. Are the words I have quoted unintelligible, like the parrot's prating? Perhaps the language may be reconstructed; perhaps it may be found to embody something worth a hearing. Success is most likely to come by considering the growth of alchemy; by trying to find the ideas which were expressed in the strange tongue; by endeavouring to look at our surroundings as the alchemists looked at theirs. Do what we will, we always, more or less, construct our own universe. The history of science may be described as the history of the attempts, and the failures, of men "to see things as they are." "Nothing is harder," said the Latin poet Lucretius, "than to separate manifest facts from doubtful, what straightway the mind adds on of itself." Observations of the changes which are constantly happening in the sky, and on the earth, must have prompted men long ago to ask whether there are any limits to the changes of things around them. And this question must have become more urgent as working in metals, making colours and dyes, preparing new kinds of food and drink, producing substances with smells and tastes unlike those of familiar objects, and other pursuits like these, made men acquainted with transformations which seemed to penetrate to the very foundations of things. Can one thing be changed into any other thing; or, are there classes of things within each of which change is possible, while the passage from one class to another is not possible? Are all the varied substances seen, tasted, handled, smelt, composed of a limited number of essentially different things; or, is each fundamentally different from every other substance? Such questions as these must have pressed for answers long ago. Some of the Greek philosophers who lived four or five hundred years before Christ formed a theory of the transformations of matter, which is essentially the theory held by naturalists to-day. These philosophers taught that to understand nature we must get beneath the superficial qualities of things. "According to convention," said Democritus (born 460 B.C.), "there are a sweet and a bitter, a hot and a cold, and according to convention there is colour. In truth there are atoms and a void." Those investigators attempted to connect all the differences which are observed between the qualities of things with differences of size, shape, position, and movement of atoms. They said that all things are formed by the coalescence of certain unchangeable, indestructible, and impenetrable particles which they named atoms; the total number of atoms is constant; not one of them can be destroyed, nor can one be created; when a substance ceases to exist and another is formed, the process is not a destruction of matter, it is a re-arrangement of atoms. Only fragments of the writings of the founders of the atomic theory have come to us. The views of these philosophers are preserved, and doubtless amplified and modified, in a Latin poem, _Concerning the Nature of Things_, written by Lucretius, who was born a century before the beginning of our era. Let us consider the picture given in that poem of the material universe, and the method whereby the picture was produced.[2] [2] The quotations from Lucretius are taken from Munro's translation (4th Edition, 1886). All knowledge, said Lucretius, is based on "the aspect and the law of nature." True knowledge can be obtained only by the use of the senses; there is no other method. "From the senses first has proceeded the knowledge of the true, and the senses cannot be refuted. Shall reason, founded on false sense, be able to contradict [the senses], wholly founded as it is on the senses? And if they are not true, then all reason as well is rendered false." The first principle in nature is asserted by Lucretius to be that "Nothing is ever gotten out of nothing." "A thing never returns to nothing, but all things after disruption go back to the first bodies of matter." If there were not imperishable seeds of things, atoms, "first-beginnings of solid singleness," then, Lucretius urges, "infinite time gone by and lapse of days must have eaten up all things that are of mortal body." The first-beginnings, or atoms, of things were thought of by Lucretius as always moving; "there is no lowest point in the sum of the universe" where they can rest; they meet, clash, rebound, or sometimes join together into groups of atoms which move about as wholes. Change, growth, decay, formation, disruption--these are the marks of all things. "The war of first-beginnings waged from eternity is carried on with dubious issue: now here, now there, the life-bringing elements of things get the mastery, and are o'ermastered in turn; with the funeral wail blends the cry which babies raise when they enter the borders of light; and no night ever followed day, nor morning night, that heard not, mingling with the sickly infant's cries, the attendants' wailings on death and black funeral." Lucretius pictured the atoms of things as like the things perceived by the senses; he said that atoms of different kinds have different shapes, but the number of shapes is finite, because there is a limit to the number of different things we see, smell, taste, and handle; he implies, although I do not think he definitely asserts, that all atoms of one kind are identical in every respect. We now know that many compounds exist which are formed by the union of the same quantities by weight of the same elements, and, nevertheless, differ in properties; modern chemistry explains this fact by saying that the properties of a substance depend, not only on the kind of atoms which compose the minute particles of a compound, and the number of atoms of each kind, but also on the mode of arrangement of the atoms.[3] The same doctrine was taught by Lucretius, two thousand years ago. "It often makes a great difference," he said, "with what things, and in what positions the same first-beginnings are held in union, and what motions they mutually impart and receive." For instance, certain atoms may be so arranged at one time as to produce fire, and, at another time, the arrangement of the same atoms may be such that the result is a fir-tree. The differences between the colours of things are said by Lucretius to be due to differences in the arrangements and motions of atoms. As the colour of the sea when wind lashes it into foam is different from the colour when the waters are at rest, so do the colours of things change when the atoms whereof the things are composed change from one arrangement to another, or from sluggish movements to rapid and tumultuous motions. [3] See the chapter _Molecular Architecture_ in the _Story of the Chemical Elements_. Lucretius pictured a solid substance as a vast number of atoms squeezed closely together, a liquid as composed of not so many atoms less tightly packed, and a gas as a comparatively small number of atoms with considerable freedom of motion. Essentially the same picture is presented by the molecular theory of to-day. To meet the objection that atoms are invisible, and therefore cannot exist, Lucretius enumerates many things we cannot see although we know they exist. No one doubts the existence of winds, heat, cold and smells; yet no one has seen the wind, or heat, or cold, or a smell. Clothes become moist when hung near the sea, and dry when spread in the sunshine; but no one has seen the moisture entering or leaving the clothes. A pavement trodden by many feet is worn away; but the minute particles are removed without our eyes being able to see them. Another objector urges--"You say the atoms are always moving, yet the things we look at, which you assert to be vast numbers of moving atoms, are often motionless." Him Lucretius answers by an analogy. "And herein you need not wonder at this, that though the first-beginnings of things are all in motion, yet the sum is seen to rest in supreme repose, unless when a thing exhibits motions with its individual body. For all the nature of first things lies far away from our senses, beneath their ken; and, therefore, since they are themselves beyond what you can see, they must withdraw from sight their motion as well; and the more so, that the things which we can see do yet often conceal their motions when a great distance off. Thus, often, the woolly flocks as they crop the glad pastures on a hill, creep on whither the grass, jewelled with fresh dew, summons or invites each, and the lambs, fed to the full, gambol and playfully butt; all which objects appear to us from a distance to be blended together, and to rest like a white spot on a green hill. Again, when mighty legions fill with their movements all parts of the plains, waging the mimicry of war, the glitter lifts itself up to the sky, and the whole earth round gleams with brass, and beneath a noise is raised by the mighty tramplings of men, and the mountains, stricken by the shouting, echo the voices to the stars of heaven, and horsemen fly about, and suddenly wheeling, scour across the middle of the plains, shaking them with the vehemence of their charge. And yet there is some spot on the high hills, seen from which they appear to stand still and to rest on the plains as a bright spot." The atomic theory of the Greek thinkers was constructed by reasoning on natural phenomena. Lucretius constantly appeals to observed facts for confirmation of his theoretical teachings, or refutation of opinions he thought erroneous. Besides giving a general mental presentation of the material universe, the theory was applied to many specific transmutations; but minute descriptions of what are now called chemical changes could not be given in terms of the theory, because no searching examination of so much as one such change had been made, nor, I think, one may say, could be made under the conditions of Greek life. More than two thousand years passed before investigators began to make accurate measurements of the quantities of the substances which take part in those changes wherein certain things seem to be destroyed and other totally different things to be produced; until accurate knowledge had been obtained of the quantities of the definite substances which interact in the transformations of matter, the atomic theory could not do more than draw the outlines of a picture of material changes. A scientific theory has been described as "the likening of our imaginings to what we actually observe." So long as we observe only in the rough, only in a broad and general way, our imaginings must also be rough, broad, and general. It was the great glory of the Greek thinkers about natural events that their observations were accurate, on the whole, and as far as they went, and the theory they formed was based on no trivial or accidental features of the facts, but on what has proved to be the very essence of the phenomena they sought to bring into one point of view; for all the advances made in our own times in clear knowledge of the transformations of matter have been made by using, as a guide to experimental inquiries, the conception that the differences between the qualities of substances are connected with differences in the weights and movements of minute particles; and this was the central idea of the atomic theory of the Greek philosophers. The atomic theory was used by the great physicists of the later Renaissance, by Galileo, Gassendi, Newton and others. Our own countryman, John Dalton, while trying (in the early years of the 19th century) to form a mental presentation of the atmosphere in terms of the theory of atoms, rediscovered the possibility of differences between the sizes of atoms, applied this idea to the facts concerning the quantitative compositions of compounds which had been established by others, developed a method for determining the relative weights of atoms of different kinds, and started chemistry on the course which it has followed so successfully. Instead of blaming the Greek philosophers for lack of quantitatively accurate experimental inquiry, we should rather be full of admiring wonder at the extraordinary acuteness of their mental vision, and the soundness of their scientific spirit. The ancient atomists distinguished the essential properties of things from their accidental features. The former cannot be removed, Lucretius said, without "utter destruction accompanying the severance"; the latter may be altered "while the nature of the thing remains unharmed." As examples of essential properties, Lucretius mentions "the weight of a stone, the heat of fire, the fluidity of water." Such things as liberty, war, slavery, riches, poverty, and the like, were accounted accidents. Time also was said to be an accident: it "exists not by itself; but simply from the things which happen, the sense apprehends what has been done in time past, as well as what is present, and what is to follow after." As our story proceeds, we shall see that the chemists of the middle ages, the alchemists, founded their theory of material changes on the difference between a supposed essential substratum of things, and their qualities which could be taken off, they said, and put on, as clothes are removed and replaced. How different from the clear, harmonious, orderly, Greek scheme, is any picture we can form, from such quotations as I have given from their writings, of the alchemists' conception of the world. The Greeks likened their imaginings of nature to the natural facts they observed; the alchemists created an imaginary world after their own likeness. While Christianity was superseding the old religions, and the theological system of the Christian Church was replacing the cosmogonies of the heathen, the contrast between the power of evil and the power of good was more fully realised than in the days of the Greeks; a sharper division was drawn between this world and another world, and that other world was divided into two irreconcilable and absolutely opposite parts. Man came to be regarded as the centre of a tremendous and never-ceasing battle, urged between the powers of good and the powers of evil. The sights and sounds of nature were regarded as the vestments, or the voices, of the unseen combatants. Life was at once very real and the mere shadow of a dream. The conditions were favourable to the growth of magic; for man was regarded as the measure of the universe, the central figure in an awful tragedy. Magic is an attempt, by thinking and speculating about what we consider must be the order of nature, to discover some means of penetrating into the secret life of natural things, of realising the hidden powers and virtues of things, grasping the concealed thread of unity which is supposed to run through all phenomena however seemingly diverse, entering into sympathy with the supposed inner oneness of life, death, the present, past, and future. Magic grows, and gathers strength, when men are sure their theory of the universe must be the one true theory, and they see only through the glasses which their theory supplies. "He who knows himself thoroughly knows God and all the mysteries of His nature," says a modern writer on magic. That saying expresses the fundamental hypothesis, and the method, of all systems of magic and mysticism. Of such systems, alchemy was one. CHAPTER II. A SKETCH OF ALCHEMICAL THEORY. The system which began to be called _alchemy_ in the 6th and 7th centuries of our era had no special name before that time, but was known as _the sacred art, the divine science, the occult science, the art of Hermes_. A commentator on Aristotle, writing in the 4th century A.D., calls certain instruments used for fusion and calcination "_chuika organa_," that is, instruments for melting and pouring. Hence, probably, came the adjective _chyic_ or _chymic_, and, at a somewhat later time, the word _chemia_ as the name of that art which deals with calcinations, fusions, meltings, and the like. The writer of a treatise on astrology, in the 5th century, speaking of the influences of the stars on the dispositions of man, says: "If a man is born under Mercury he will give himself to astronomy; if Mars, he will follow the profession of arms; if Saturn, he will devote himself to the science of alchemy (_Scientia alchemiae_)." The word _alchemia_ which appears in this treatise, was formed by prefixing the Arabic _al_ (meaning _the_) to _chemia_, a word, as we have seen, of Greek origin. It is the growth, development, and transformation into chemistry, of this _alchemia_ which we have to consider. Alchemy, that is, _the_ art of melting, pouring, and transforming, must necessarily pay much attention to working with crucibles, furnaces, alembics, and other vessels wherein things are fused, distilled, calcined, and dissolved. The old drawings of alchemical operations show us men busy calcining, cohobating, distilling, dissolving, digesting, and performing other processes of like character to these. The alchemists could not be accused of laziness or aversion to work in their laboratories. Paracelsus (16th century) says of them: "They are not given to idleness, nor go in a proud habit, or plush and velvet garments, often showing their rings on their fingers, or wearing swords with silver hilts by their sides, or fine and gay gloves on their hands; but diligently follow their labours, sweating whole days and nights by their furnaces. They do not spend their time abroad for recreation, but take delight in their laboratories. They put their fingers among coals, into clay and filth, not into gold rings. They are sooty and black, like smiths and miners, and do not pride themselves upon clean and beautiful faces." In these respects the chemist of to-day faithfully follows the practice of the alchemists who were his predecessors. You can nose a chemist in a crowd by the smell of the laboratory which hangs about him; you can pick him out by the stains on his hands and clothes. He also "takes delight in his laboratory"; he does not always "pride himself on a clean and beautiful face"; he "sweats whole days and nights by his furnace." Why does the chemist toil so eagerly? Why did the alchemists so untiringly pursue their quest? I think it is not unfair to say: the chemist experiments in order that he "may liken his imaginings to the facts which he observes"; the alchemist toiled that he might liken the facts which he observed to his imaginings. The difference may be put in another way by saying: the chemist's object is to discover "how changes happen in combinations of the unchanging"; the alchemist's endeavour was to prove the truth of his fundamental assertion, "that every substance contains undeveloped resources and potentialities, and can be brought outward and forward into perfection." Looking around him, and observing the changes of things, the alchemist was deeply impressed by the growth and modification of plants and animals; he argued that minerals and metals also grow, change, develop. He said in effect: "Nature is one, there must be unity in all the diversity I see. When a grain of corn falls into the earth it dies, but this dying is the first step towards a new life; the dead seed is changed into the living plant. So it must be with all other things in nature: the mineral, or the metal, seems dead when it is buried in the earth, but, in reality, it is growing, changing, and becoming more perfect." The perfection of the seed is the plant. What is the perfection of the common metals? "Evidently," the alchemist replied, "the perfect metal is gold; the common metals are trying to become gold." "Gold is the intention of Nature in regard to all metals," said an alchemical writer. Plants are preserved by the preservation of their seed. "In like manner," the alchemist's argument proceeded, "there must be a seed in metals which is their essence; if I can separate the seed and bring it under the proper conditions, I can cause it to grow into the perfect metal." "Animal life, and human life also," we may suppose the alchemist saying, "are continued by the same method as that whereby the life of plants is continued; all life springs from seed; the seed is fructified by the union of the male and the female; in metals also there must be the two characters; the union of these is needed for the production of new metals; the conjoining of metals must go before the birth of the perfect metal." "Now," we may suppose the argument to proceed, "now, the passage from the imperfect to the more perfect is not easy. It is harder to practise virtue than to acquiesce in vice; virtue comes not naturally to man; that he may gain the higher life, he must be helped by grace. Therefore, the task of exalting the purer metals into the perfect gold, of developing the lower order into the higher, is not easy. If Nature does this, she does it slowly and painfully; if the exaltation of the common metals to a higher plane is to be effected rapidly, it can be done only by the help of man." So far as I can judge from their writings, the argument of the alchemists may be rendered by some such form as the foregoing. A careful examination of the alchemical argument shows that it rests on a (supposed) intimate knowledge of nature's plan of working, and the certainty that simplicity is the essential mark of that plan. That the alchemists were satisfied of the great simplicity of nature, and their own knowledge of the ways of nature's work, is apparent from their writings. The author of _The New Chemical Light_ (17th century) says: "Simplicity is the seal of truth.... Nature is wonderfully simple, and the characteristic mark of a childlike simplicity is stamped upon all that is true and noble in Nature." In another place the same author says: "Nature is one, true, simple, self-contained, created of God, and informed with a certain universal spirit." The same author, Michael Sendivogius, remarks: "It may be asked how I come to have this knowledge about heavenly things which are far removed beyond human ken. My answer is that the sages have been taught by God that this natural world is only an image and material copy of a heavenly and spiritual pattern; that the very existence of this world is based upon the reality of its heavenly archetype.... Thus the sage sees heaven reflected in Nature as in a mirror, and he pursues this Art, not for the sake of gold or silver, but for the love of the knowledge which it reveals." The _Only True Way_ advises all who wish to become true alchemists to leave the circuitous paths of pretended philosophers, and to follow nature, which is simple; the complicated processes described in books are said to be the traps laid by the "cunning sophists" to catch the unwary. In _A Catechism of Alchemy_, Paracelsus asks: "What road should the philosopher follow?" He answers, "That exactly which was followed by the Great Architect of the Universe in the creation of the world." One might suppose it would be easier, and perhaps more profitable, to examine, observe, and experiment, than to turn one's eyes inwards with the hope of discovering exactly "the road followed by the Great Architect of the Universe in the creation of the world." But the alchemical method found it easier to begin by introspection. The alchemist spun his universe from his own ideas of order, symmetry, and simplicity, as the spider spins her web from her own substance. A favourite saying of the alchemists was, "What is above is as what is below." In one of its aspects this saying meant, "processes happen within the earth like those which occur on the earth; minerals and metals live, as animals and plants live; all pass through corruption towards perfection." In another aspect the saying meant "the human being is the world in miniature; as is the microcosm, so is the macrocosm; to know oneself is to know all the world." Every man knows he ought to try to rise to better things, and many men endeavour to do what they know they ought to do; therefore, he who feels sure that all nature is fashioned after the image of man, projects his own ideas of progress, development, virtue, matter and spirit, on to nature outside himself; and, as a matter of course, this kind of naturalist uses the same language when he is speaking of the changes of material things as he employs to express the changes of his mental states, his hopes, fears, aspirations, and struggles. The language of the alchemists was, therefore, rich in such expressions as these; "the elements are to be so conjoined that the nobler and fuller life may be produced"; "our arcanum is gold exalted to the highest degree of perfection to which the combined action of nature and art can develop it." Such commingling of ethical and physical ideas, such application of moral conceptions to material phenomena, was characteristic of the alchemical method of regarding nature. The necessary results were; great confusion of thought, much mystification of ideas, and a superabundance of _views_ about natural events. When the author of _The Metamorphosis of Metals_ was seeking for an argument in favour of his view, that water is the source and primal element of all things, he found what he sought in the Biblical text: "In the beginning the spirit of God moved upon the face of the waters." Similarly, the author of _The Sodic Hydrolith_ clenches his argument in favour of the existence of the Philosopher's Stone, by the quotation: "Therefore, thus saith the Lord; behold I lay in Zion for a foundation a Stone, a tried Stone, a precious corner Stone, a sure foundation. He that has it shall not be confounded." This author works out in detail an analogy between the functions and virtues of the _Stone_, and the story of man's fall and redemption, as set forth in the Old and New Testaments. The same author speaks of "Satan, that grim pseudo-alchemist." That the attribution, by the alchemists, of moral virtues and vices to natural things was in keeping with some deep-seated tendency of human nature, is shown by the persistence of some of their methods of stating the properties of substances: we still speak of "perfect and imperfect gases," "noble and base metals," "good and bad conductors of electricity," and "laws governing natural phenomena." Convinced of the simplicity of nature, certain that all natural events follow one course, sure that this course was known to them and was represented by the growth of plants and animals, the alchemists set themselves the task, firstly, of proving by observations and experiments that their view of natural occurrences was correct; and, secondly, of discovering and gaining possession of the instrument whereby nature effects her transmutations and perfects her operations. The mastery of this instrument would give them power to change any metal into gold, the cure of all diseases, and the happiness which must come from the practical knowledge of the supreme secret of nature. The central quest of alchemy was the quest of an undefined and undefinable something wherein was supposed to be contained all the powers and potencies of life, and whatever makes life worth living. The names given to this mystical something were as many as the properties which were assigned to it. It was called _the one thing, the essence, the philosopher's stone, the stone of wisdom, the heavenly balm, the divine water, the virgin water, the carbuncle of the sun, the old dragon, the lion, the basilisk, the phoenix_; and many other names were given to it. We may come near to expressing the alchemist's view of the essential character of the object of their search by naming it _the soul of all things_. "Alchemy," a modern writer says, "is the science of the soul of all things." The essence was supposed to have a material form, an ethereal or middle nature, and an immaterial or spiritual life. No one might hope to make this essence from any one substance, because, as one of the alchemists says, "It is the attribute of God alone to make one out of one; you must produce one thing out of two by natural generation." The alchemists did not pretend to create gold, but only to produce it from other things. The author of _A Brief Guide to the Celestial Ruby_ says: "We do not, as is sometimes said, profess to create gold and silver, but only to find an agent which ... is capable of entering into an intimate and maturing union with the Mercury of the base metals." And again: "Our Art ... only arrogates to itself the power of developing, through the removal of all defects and superfluities, the golden nature which the baser metals possess." Bonus, in his tract on _The New Pearl of Great Price_ (16th century), says: "The Art of Alchemy ... does not create metals, or even develop them out of the metallic first-substance; it only takes up the unfinished handicraft of Nature and completes it.... Nature has only left a comparatively small thing for the artist to do--the completion of that which she has already begun." If the essence were ever attained, it would be by following the course which nature follows in producing the perfect plant from the imperfect seed, by discovering and separating the seed of metals, and bringing that seed under the conditions which alone are suitable for its growth. Metals must have seed, the alchemists said, for it would be absurd to suppose they have none. "What prerogative have vegetables above metals," exclaims one of them, "that God should give seed to the one and withhold it from the other? Are not metals as much in His sight as trees?" As metals, then, possess seed, it is evident how this seed is to be made active; the seed of a plant is quickened by descending into the earth, therefore the seed of metals must be destroyed before it becomes life-producing. "The processes of our art must begin with dissolution of gold; they must terminate in a restoration of the essential quality of gold." "Gold does not easily give up its nature, and will fight for its life; but our agent is strong enough to overcome and kill it, and then it also has power to restore it to life, and to change the lifeless remains into a new and pure body." The application of the doctrine of the existence of seed in metals led to the performance of many experiments, and, hence, to the accumulation of a considerable body of facts established by experimental inquiries. The belief of the alchemists that all natural events are connected by a hidden thread, that everything has an influence on other things, that "what is above is as what is below," constrained them to place stress on the supposed connexion between the planets and the metals, and to further their metallic transformations by performing them at times when certain planets were in conjunction. The seven principal planets and the seven principal metals were called by the same names: _Sol_ (gold), _Luna_ (silver), _Saturn_ (lead), _Jupiter_ (tin), _Mars_ (iron), _Venus_ (copper), and _Mercury_ (mercury). The author of _The New Chemical Light_ taught that one metal could be propagated from another only in the order of superiority of the planets. He placed the seven planets in the following descending order: Saturn, Jupiter, Mars, Sol, Venus, Mercury, Luna. "The virtues of the planets descend," he said, "but do not ascend"; it is easy to change Mars (iron) into Venus (copper), for instance, but Venus cannot be transformed into Mars. Although the alchemists regarded everything as influencing, and influenced by, other things, they were persuaded that the greatest effects are produced on a substance by substances of like nature with itself. Hence, most of them taught that the seed of metals will be obtained by operations with metals, not by the action on metals of things of animal or vegetable origin. Each class of substances, they said, has a life, or spirit (an essential character, we might say) of its own. "The life of sulphur," Paracelsus said, "is a combustible, ill-smelling, fatness.... The life of gems and corals is mere colour.... The life of water is its flowing.... The life of fire is air." Grant an attraction of like to like, and the reason becomes apparent for such directions as these: "Nothing heterogeneous must be introduced into our magistery"; "Everything should be made to act on that which is like it, and then Nature will perform her duty." Although each class of substances was said by the alchemists to have its own particular character, or life, nevertheless they taught that there is a deep-seated likeness between all things, inasmuch as the power of _the essence_, or _the one thing_, is so great that under its influence different things are produced from the same origin, and different things are caused to pass into and become the same thing. In _The New Chemical Light_ it is said: "While the seed of all things is one, it is made to generate a great variety of things." It is not easy now--it could not have been easy at any time--to give clear and exact meanings to the doctrines of the alchemists, or the directions they gave for performing the operations necessary for the production of the object of their search. And the difficulty is much increased when we are told that "The Sage jealously conceals [his knowledge] from the sinner and the scornful, lest the mysteries of heaven should be laid bare to the vulgar gaze." We almost despair when an alchemical writer assures us that the Sages "Set pen to paper for the express purpose of concealing their meaning. The sense of a whole passage is often hopelessly obscured by the addition or omission of one little word, for instance the addition of the word _not_ in the wrong place." Another writer says: "The Sages are in the habit of using words which may convey either a true or a false impression; the former to their own disciples and children, the latter to the ignorant, the foolish, and the unworthy." Sometimes, after descriptions of processes couched in strange and mystical language, the writer will add, "If you cannot perceive what you ought to understand herein, you should not devote yourself to the study of philosophy." Philalethes, in his _Brief Guide to the Celestial Ruby_, seems to feel some pity for his readers; after describing what he calls "the generic homogeneous water of gold," he says: "If you wish for a more particular description of our water, I am impelled by motives of charity to tell you that it is living, flexible, clear, nitid, white as snow, hot, humid, airy, vaporous, and digestive." Alchemy began by asserting that nature must be simple; it assumed that a knowledge of the plan and method of natural occurrences is to be obtained by thinking; and it used analogy as the guide in applying this knowledge of nature's design to particular events, especially the analogy, assumed by alchemy to exist, between material phenomena and human emotions. CHAPTER III. THE ALCHEMICAL CONCEPTION OF THE UNITY AND SIMPLICITY OF NATURE. In the preceding chapter I have referred to the frequent use made by the alchemists of their supposition that nature follows the same plan, or at any rate a very similar plan, in all her processes. If this supposition is accepted, the primary business of an investigator of nature is to trace likenesses and analogies between what seem on the surface to be dissimilar and unconnected events. As this idea, and this practice, were the foundations whereon the superstructure of alchemy was raised, I think it is important to amplify them more fully than I have done already. Mention is made in many alchemical writings of a mythical personage named _Hermes Trismegistus_, who is said to have lived a little later than the time of Moses. Representations of Hermes Trismegistus are found on ancient Egyptian monuments. We are told that Alexander the Great found his tomb near Hebron; and that the tomb contained a slab of emerald whereon thirteen sentences were written. The eighth sentence is rendered in many alchemical books as follows: "Ascend with the greatest sagacity from the earth to heaven, and then again descend to the earth, and unite together the powers of things superior and things inferior. Thus you will obtain the glory of the whole world, and obscurity will fly away from you." This sentence evidently teaches the unity of things in heaven and things on earth, and asserts the possibility of gaining, not merely a theoretical, but also a practical, knowledge of the essential characters of all things. Moreover, the sentence implies that this fruitful knowledge is to be obtained by examining nature, using as guide the fundamental similarity supposed to exist between things above and things beneath. The alchemical writers constantly harp on this theme: follow nature; provided you never lose the clue, which is simplicity and similarity. The author of _The Only Way_ (1677) beseeches his readers "to enlist under the standard of that method which proceeds in strict obedience to the teaching of nature ... in short, the method which nature herself pursues in the bowels of the earth." The alchemists tell us not to expect much help from books and written directions. When one of them has said all he can say, he adds--"The question is whether even this book will convey any information to one before whom the writings of the Sages and the open book of Nature are exhibited in vain." Another tells his readers the only thing for them is "to beseech God to give you the real philosophical temper, and to open your eyes to the facts of nature; thus alone will you reach the coveted goal." "Follow nature" is sound advice. But, nature was to be followed with eyes closed save to one vision, and the vision was to be seen before the following began. The alchemists' general conception of nature led them to assign to every substance a condition or state natural to it, and wherein alone it could be said to be as it was designed to be. Each substance, they taught, could be caused to leave its natural state only by violent, or non-natural, means, and any substance which had been driven from its natural condition by violence was ready, and even eager, to return to the condition consonant with its nature. Thus Norton, in his _Ordinal of Alchemy_, says: "Metals are generated in the earth, for above ground they are subject to rust; hence above ground is the place of corruption of metals, and of their gradual destruction. The cause which we assign to this fact is that above ground they are not in their proper element, and an unnatural position is destructive to natural objects, as we see, for instance, that fishes die when they are taken out of the water; and as it is natural for men, beasts, and birds to live in the air, so stones and metals are naturally generated under the earth." In his _New Pearl of Great Price_ (16th century), Bonus says:--"The object of Nature in all things is to introduce into each substance the form which properly belongs to it; and this is also the design of our Art." This view assumed the knowledge of the natural conditions of the substances wherewith experiments were performed. It supposed that man could act as a guide, to bring back to its natural condition a substance which had been removed from that condition, either by violent processes of nature, or by man's device. The alchemist regarded himself as an arbiter in questions concerning the natural condition of each substance he dealt with. He thought he could say, "this substance ought to be thus, or thus," "that substance is constrained, thwarted, hindered from becoming what nature meant it to be." In Ben Jonson's play called _The Alchemist_, Subtle (who is the alchemist of the play) says, " ... metals would be gold if they had time." The alchemist not only attributed ethical qualities to material things, he also became the guardian and guide of the moral practices of these things. He thought himself able to recall the erring metal to the path of metalline virtue, to lead the extravagant mineral back to the moral home-life from which it had been seduced, to show the doubting and vacillating salt what it was ignorantly seeking, and to help it to find the unrealised object of its search. The alchemist acted as a sort of conscience to the metals, minerals, salts, and other substances he submitted to the processes of his laboratory. He treated them as a wise physician might treat an ignorant and somewhat refractory patient. "I know what you want better than you do," he seems often to be saying to the metals he is calcining, separating, joining and subliming. But the ignorant alchemist was not always thanked for his treatment. Sometimes the patient rebelled. For instance, Michael Sendivogius, in his tract, _The New Chemical Light drawn from the Fountain of Nature and of Manual Experience_ (17th century), recounts _a dialogue between Mercury, the Alchemist, and Nature_. "On a certain bright morning a number of Alchemists met together in a meadow, and consulted as to the best way of preparing the Philosopher's Stone.... Most of them agreed that Mercury was the first substance. Others said, no, it was sulphur, or something else.... Just as the dispute began to run high, there arose a violent wind, which dispersed the Alchemists into all the different countries of the world; and as they had arrived at no conclusion, each one went on seeking the Philosopher's Stone in his own old way, this one expecting to find it in one substance, and that in another, so that the search has continued without intermission even unto this day. One of them, however, had at least got the idea into his head that Mercury was the substance of the Stone, and determined to concentrate all his efforts on the chemical preparation of Mercury.... He took common Mercury and began to work with it. He placed it in a glass vessel over the fire, when it, of course, evaporated. So in his ignorance he struck his wife, and said: 'No one but you has entered my laboratory; you must have taken my Mercury out of the vessel.' The woman, with tears, protested her innocence. The Alchemist put some more Mercury into the vessel.... The Mercury rose to the top of the vessel in vaporous steam. Then the Alchemist was full of joy, because he remembered that the first substance of the Stone is described by the Sages as volatile; and he thought that now at last he _must_ be on the right track. He now began to subject the Mercury to all sorts of chemical processes, to sublime it, and to calcine it with all manner of things, with salts, sulphur, metals, minerals, blood, hair, aqua fortis, herbs, urine, and vinegar.... Everything he could think of was tried; but without producing the desired effect." The Alchemist then despaired; after a dream, wherein an old man came and talked with him about the "Mercury of the Sages," the Alchemist thought he would charm the Mercury, and so he used a form of incantation. The Mercury suddenly began to speak, and asked the Alchemist why he had troubled him so much, and so on. The Alchemist replied, and questioned the Mercury. The Mercury makes fun of the philosopher. Then the Alchemist again torments the Mercury by heating him with all manner of horrible things. At last Mercury calls in the aid of Nature, who soundly rates the philosopher, tells him he is grossly ignorant, and ends by saying: "The best thing you can do is to give yourself up to the king's officers, who will quickly put an end to you and your philosophy." As long as men were fully persuaded that they knew the plan whereon the world was framed, that it was possible for them to follow exactly "the road which was followed by the Great Architect of the Universe in the creation of the world," a real knowledge of natural events was impossible; for every attempt to penetrate nature's secrets presupposed a knowledge of the essential characteristics of that which was to be investigated. But genuine knowledge begins when the investigator admits that he must learn of nature, not nature of him. It might be truly said of one who held the alchemical conception of nature that "his foible was omniscience"; and omniscience negatives the attainment of knowledge. The alchemical notion of a natural state as proper to each substance was vigorously combated by the Honourable Robert Boyle (born 1626, died 1691), a man of singularly clear and penetrative intellect. In _A Paradox of the Natural and Supernatural States of Bodies, Especially of the Air_, Boyle says:--"I know that not only in living, but even in inanimate, bodies, of which alone I here discourse, men have universally admitted the famous distinction between the natural and preternatural, or violent state of bodies, and do daily, without the least scruple, found upon it hypotheses and ratiocinations, as if it were most certain that what they call nature had purposely formed bodies in such a determinate state, and were always watchful that they should not by any external violence be put out of it. But notwithstanding so general a consent of men in this point, I confess, I cannot yet be satisfied about it in the sense wherein it is wont to be taken. It is not, that I believe, that there is no sense in which, or in the account upon which, a body may he said to be in its natural state; but that I think the common distinction of a natural and violent state of bodies has not been clearly explained and considerately settled, and both is not well grounded, and is oftentimes ill applied. For when I consider that whatever state a body be put into, or kept in, it obtains or retains that state, assenting to the catholic laws of nature, I cannot think it fit to deny that in this sense the body proposed is in a natural state; but then, upon the same ground, it will he hard to deny but that those bodies which are said to be in a violent state may also be in a natural one, since the violence they are presumed to suffer from outward agents is likewise exercised no otherwise than according to the established laws of universal nature." There must be something very fascinating and comforting in the alchemical view of nature, as a harmony constructed on one simple plan, which can be grasped as a whole, and also in its details, by the introspective processes of the human intellect; for that conception prevails to-day among those who have not investigated natural occurrences for themselves. The alchemical view of nature still forms the foundation of systems of ethics, of philosophy, of art. It appeals to the innate desire of man to make himself the measure of all things. It is so easy, so authoritative, apparently so satisfactory. No amount of thinking and reasoning will ever demonstrate its falsity. It can be conquered only by a patient, unbiassed, searching examination of some limited portion of natural events. CHAPTER IV. THE ALCHEMICAL ELEMENTS AND PRINCIPLES. The alchemists were sure that the intention of nature regarding metals was that they should become gold, for gold was considered to be the most perfect metal, and nature, they said, evidently strains after perfection. The alchemist found that metals were worn away, eaten through, broken, and finally caused to disappear, by many acid and acrid liquids which he prepared from mineral substances. But gold resisted the attacks of these liquids; it was not changed by heat, nor was it affected by sulphur, a substance which changed limpid, running mercury into an inert, black solid. Hence, gold was more perfect in the alchemical scale than any other metal. Since gold was considered to be the most perfect metal, it was self-evident to the alchemical mind that nature must form gold slowly in the earth, must transmute gradually the inferior metals into gold. "The only thing that distinguishes one metal from another," writes an alchemist who went under the name of Philalethes, "is its degree of maturity, which is, of course, greatest in the most precious metals; the difference between gold and lead is not one of substance, but of digestion; in the baser metal the coction has not been such as to purge out its metallic impurities. If by any means this superfluous impure matter could be organically removed from the baser metals, they would become gold and silver. So miners tell us that lead has in many cases developed into silver in the bowels of the earth, and we contend that the same effect is produced in a much shorter time by means of our Art." Stories were told about the finding of gold in deserted mines which had been worked out long before; these stories were supposed to prove that gold was bred in the earth. The facts that pieces of silver were found in tin and lead mines, and gold was found in silver mines, were adduced as proofs that, as the author of _The New Pearl of Great Price_ says, "Nature is continually at work changing other metals into gold, because, though in a certain sense they are complete in themselves, they have not yet reached the highest perfection of which they are capable, and to which nature has destined them." What nature did in the earth man could accomplish in the workshop. For is not man the crown of the world, the masterpiece of nature, the flower of the universe; was he not given dominion over all things when the world was created? In asserting that the baser metals could be transmuted into gold, and in attempting to effect this transmutation, the alchemist was not acting on a vague; haphazard surmise; he was pursuing a policy dictated by his conception of the order of nature; he was following the method which he conceived to be that used by nature herself. The transmutation of metals was part and parcel of a system of natural philosophy. If this transmutation were impossible, the alchemical scheme of things would be destroyed, the believer in the transmutation would be left without a sense of order in the material universe. And, moreover, the alchemist's conception of an orderly material universe was so intimately connected with his ideas of morality and religion, that to disprove the possibility of the great transmutation would be to remove not only the basis of his system of material things, but the foundations of his system of ethics also. To take away his belief in the possibility of changing other metals into gold would be to convert the alchemist into an atheist. How, then, was the transmutation to be accomplished? Evidently by the method whereby nature brings to perfection other living things; for the alchemist's belief in the simplicity and unity of nature compelled him to regard metals as living things. Plants are improved by appropriate culture, by digging and enriching the soil, by judicious selection of seed; animals are improved by careful breeding. By similar processes metals will be encouraged and helped towards perfection. The perfect state of gold will not be reached at a bound; it will be gained gradually. Many partial purifications will be needed. As _Subtle_ says in _The Alchemist_-- 'twere absurd To think that nature in the earth bred gold Perfect in the instant; something went before, There must be remote matter.... Nature doth first beget the imperfect, then Proceeds she to the perfect. At this stage the alchemical argument becomes very ultra-physical. It may, perhaps, be rendered somewhat as follows:-- Man is the most perfect of animals; in man there is a union of three parts, these are body, soul, and spirit. Metals also may be said to have a body, a soul, and a spirit; there is a specific bodily, or material, form belonging to each metal; there is a metalline soul characteristic of this or that class of metals; there is a spirit, or inner immaterial potency, which is the very essence of all metals. The soul and spirit of man are clogged by his body. If the spiritual nature is to become the dominating partner, the body must be mortified: the alchemists, of course, used this kind of imagery, and it was very real to them. In like manner the spirit of metals will be laid bare and enabled to exercise its transforming influences, only when the material form of the individual metal has been destroyed. The first thing to do, then, is to strip off and cast aside those properties of metals which appeal to the senses. "It is necessary to deprive matter of its qualities in order to draw out its soul," said Stephanus of Alexandria in the 7th century; and in the 17th century Paracelsus said, "Nothing of true value is located in the body of a substance, but in the virtue ... the less there is of body the more in proportion is the virtue." But the possession of the soul of metals is not the final stage: mastery of the soul may mean the power of transmuting a metal into another like itself; it will not suffice for the great transmutation, for in that process a metal becomes gold, the one and only perfect metal. Hence the soul also must be removed, in order that the spirit, the essence, the kernel, may be obtained. And as it is with metals, so, the alchemists argued, it is with all things. There are a few _Principles_ which may be thought of as conditioning the specific bodily and material forms of things; beneath these, there are certain _Elements_ which are common to many things whose principles are not the same; and, hidden by the wrappings of elements and principles, there is the one _Essence_, the spirit, the mystic uniting bond, the final goal of the philosopher. I propose in this chapter to try to analyse the alchemical conceptions of Elements and Principles, and in the next chapter to attempt some kind of description of the Essence. In his _Tract Concerning the Great Stone of the Ancient Sages_, Basil Valentine speaks of the "three Principles," salt, sulphur, and mercury, the source of which is the Elements. "There are four Elements, and each has at its centre another element which makes it what it is. These are the four pillars of the earth." Of the element _Earth_, he says:--"In this element the other three, especially fire, are latent.... It is gross and porous, specifically heavy, but naturally light.... It receives all that the other three project into it, conscientiously conceals what it should hide, and brings to light that which it should manifest.... Outwardly it is visible and fixed, inwardly it is invisible and volatile." Of the element _Water_, Basil Valentine says:--"Outwardly it is volatile, inwardly it is fixed, cold, and humid.... It is the solvent of the world, and exists in three degrees of excellence: the pure, the purer, and the purest. Of its purest substance the heavens were created; of that which is less pure the atmospheric air was formed; that which is simply pure remains in its proper sphere where ... it is guardian of all subtle substances here below." Concerning the element _Air_, he writes:--"The most noble Element of Air ... is volatile, but may be fixed, and when fixed renders all bodies penetrable.... It is nobler than Earth or Water.... It nourishes, impregnates, conserves the other elements." Finally, of the element _Fire_:--"Fire is the purest and noblest of all Elements, full of adhesive unctuous corrosiveness, penetrant, digestive, inwardly fixed, hot and dry, outwardly visible, and tempered by the earth.... This Element is the most passive of all, and resembles a chariot; when it is drawn, it moves; when it is not drawn, it stands still." Basil Valentine then tells his readers that Adam was compounded of the four pure Elements, but after his expulsion from Paradise he became subject to the various impurities of the animal creation. "The pure Elements of his creation were gradually mingled and infected with the corruptible elements of the outer world, and thus his body became more and more gross, and liable, through its grossness, to natural decay and death." The process of degeneration was slow at first, but "as time went on, the seed out of which men were generated became more and more infected with perishable elements. The continued use of corruptible food rendered their bodies more and more gross; and human life was soon reduced to a very brief span." Basil Valentine then deals with the formation of the three _Principles_ of things, by the mutual action of the four Elements. Fire acting on Air produced _Sulphur_; Air acting on Water produced _Mercury_; Water acting on Earth produced _Salt_. Earth having nothing to act on produced nothing, but became the nurse of the three Principles. "The three Principles," he says, "are necessary because they are the immediate substance of metals. The remoter substance of metals is the four elements, but no one can produce anything out of them but God; and even God makes nothing of them but these three Principles." To endeavour to obtain the four pure Elements is a hopeless task. But the Sage has the three Principles at hand. "The artist should determine which of the three Principles he is seeking, and should assist it so that it may overcome its contrary." "The art consists in an even mingling of the virtues of the Elements; in the natural equilibrium of the hot, the dry, the cold, and the moist." The account of the Elements given by Philalethes differs from that of Basil Valentine. Philalethes enumerates three Elements only: Air, Water, and Earth. Things are not formed by the mixture of these Elements, for "dissimilar things can never really unite." By analysing the properties of the three Elements, Philalethes reduced them finally to one, namely, Water. "Water," he says, "is the first principle of all things." "Earth is the fundamental Element in which all bodies grow and are preserved. Air is the medium into which they grow, and by means of which the celestial virtues are communicated to them." According to Philalethes, _Mercury_ is the most important of the three Principles. Although gold is formed by the aid of Mercury, it is only when Mercury has been matured, developed, and perfected, that it is able to transmute inferior metals into gold. The essential thing to do is, therefore, to find an agent which will bring about the maturing and perfecting of Mercury. This agent, Philalethes calls "Our divine Arcanum." Although it appears to me impossible to translate the sayings of the alchemists concerning Elements and Principles into expressions which shall have definite and exact meanings for us to-day, still we may, perhaps, get an inkling of the meaning of such sentences as those I have quoted from Basil Valentine and Philalethes. Take the terms _Fire_ and _Water_. In former times all liquid substances were supposed to be liquid because they possessed something in common; this hypothetical something was called the _Element, Water_. Similarly, the view prevailed until comparatively recent times, that burning substances burn because of the presence in them of a hypothetical imponderable fluid, called "_Caloric_"; the alchemists preferred to call this indefinable something an Element, and to name it _Fire_. We are accustomed to-day to use the words _fire_ and _water_ with different meanings, according to the ideas we wish to express. When we say "do not touch the fire," or "put your hand into the water," we are regarding fire and water as material things; when we say "the house is on fire," or speak of "a diamond of the first water," we are thinking of the condition or state of a burning body, or of a substance as transparent as water. When we say "put out the fire," or "his heart became as water," we are referring to the act of burning, or are using an image which likens the thing spoken of to a substance in the act of liquefying. As we do to-day, so the alchemists did before us; they used the words _fire_ and _water_ to express different ideas. Such terms as hardness, softness, coldness, toughness, and the like, are employed for the purpose of bringing together into one point of view different things which are alike in, at least, one respect. Hard things may differ in size, weight, shape, colour, texture, &c. A soft thing may weigh the same as a hard thing; both may have the same colour or the same size, or be at the same temperature, and so on. By classing together various things as hard or soft, or smooth or rough, we eliminate (for the time) all the properties wherein the things differ, and regard them only as having one property in common. The words hardness, softness, &c., are useful class-marks. Similarly the alchemical Elements and Principles were useful class-marks. We must not suppose that when the alchemists spoke of certain things as formed from, or by the union of, the same Elements or the same Principles, they meant that these things contained a common substance. Their Elements and Principles were not thought of as substances, at least not in the modern meaning of the expression, _a substance_; they were qualities only. If we think of the alchemical elements earth, air, fire, and water, as general expressions of what seemed to the alchemists the most important properties of all substances, we may be able to attach some kind of meaning to the sayings of Basil Valentine, which I have quoted. For instance, when that alchemist tells us, "Fire is the most passive of all elements, and resembles a chariot; when it is drawn, it moves; when it is not drawn, it stands still"--we may suppose he meant to express the fact that a vast number of substances can be burnt, and that combustion does not begin of itself, but requires an external agency to start it. Unfortunately, most of the terms which the alchemists used to designate their Elements and Principles are terms which are now employed to designate specific substances. The word _fire_ is still employed rather as a quality of many things under special conditions, than as a specific substance; but _earth_, _water_, _air_, _salt_, _sulphur_, and _mercury_, are to-day the names applied to certain groups of properties, each of which is different from all other groups of properties, and is, therefore, called, in ordinary speech, a definite kind of matter. As knowledge became more accurate and more concentrated, the words _sulphur_, _salt_, _mercury_, &c., began to be applied to distinct substances, and as these terms were still employed in their alchemical sense as compendious expressions for certain qualities common to great classes of substances, much confusion arose. Kunckel, the discoverer of phosphorus, who lived between 1630 and 1702, complained of the alchemists' habit of giving different names to the same substance, and the same name to different substances. "The sulphur of one," he says, "is not the sulphur of another, to the great injury of science. To that one replies that everyone is perfectly free to baptise his infant as he pleases. Granted. You may if you like call an ass an ox, but you will never make anyone believe that your ox is an ass." Boyle is very severe on the vague and loose use of words practised by so many writers of his time. In _The Sceptical Chymist_ (published 1678-9) he says: "If judicious men, skilled in chymical affairs, shall once agree to write clearly and plainly of them, and thereby keep men from being stunned, as it were, or imposed upon by dark and empty words; it is to be hoped that these [other] men finding, that they can no longer write impertinently and absurdly, without being laughed at for doing so, will be reduced either to write nothing, or books that may teach us something, and not rob men, as formerly, of invaluable time; and so ceasing to trouble the world with riddles or impertinences, we shall either by their books receive an advantage, or by their silence escape an inconvenience." Most of the alchemists taught that the elements produced what they called _seed_, by their mutual reactions, and the principles matured this seed and brought it to perfection. They supposed that each class, or kind, of things had its own seed, and that to obtain the seed was to have the power of producing the things which sprung from that seed. Some of them, however, asserted that all things come from a common seed, and that the nature of the products of this seed is conditioned by the circumstances under which it is caused to develop. Thus Michael Sendivogius writes as follows in _The New Chemical Light, drawn from the fountain of Nature and of Manual Experience_ (17th century):-- "Wherever there is seed, Nature will work through it, whether it be good or bad." "The four Elements, by their continued action, project a constant supply of seed to the centre of the earth, where it is digested, and whence it proceeds again in generative motions. Now the centre of the earth is a certain void place where nothing is at rest, and upon the margin or circumference of this centre the four Elements project their qualities.... The magnetic force of our earth-centre attracts to itself as much as is needed of the cognate seminal substance, while that which cannot be used for vital generation is thrust forth in the shape of stones and other rubbish. This is the fountain-head of all things terrestrial. Let us illustrate the matter by supposing a glass of water to be set in the middle of a table, round the margin of which are placed little heaps of salt, and of powders of different colours. If the water be poured out, it will run all over the table in divergent rivulets, and will become salt where it touches the salt, red where it touches the red powder, and so on. The water does not change the '_places_,' but the several '_places_' differentiate the water.[4] In the same way, the seed which is the product of the four Elements is projected in all directions from the earth-centre, and produces different things, according to the quality of the different places. Thus, while the seed of all things is one, it is made to generate a great variety of things.... So long as Nature's seed remains in the centre it can indifferently produce a tree or a metal, a herb or a stone, and in like manner, according to the purity of the place, it will produce what is less or more pure." [4] The author I am quoting had said--"Nature is divided into four '_places_' in which she brings forth all things that appear and that are in the shade; and according to the good or bad quality of the '_place_,' she brings forth good or bad things.... It is most important for us to know her '_places_' ... in order that we may join things together according to Nature." CHAPTER V. THE ALCHEMICAL ESSENCE. In the last chapter I tried to describe the alchemical view of the interdependence of different substances. Taking for granted the tripartite nature of man, the co-existence in him of body, soul, and spirit (no one of which was defined), the alchemists concluded that all things are formed as man is formed; that in everything there is a specific bodily form, some portion of soul, and a dash of spirit. I considered the term _soul_ to be the alchemical name for the properties common to a class of substances, and the term _spirit_ to mean the property which was thought by the alchemists to be common to all things. The alchemists considered it possible to arrange all substances in four general classes, the marks whereof were expressed by the terms hot, cold, moist, and dry; they thought of these properties as typified by what they called the four Elements--fire, air, water, and earth. Everything, they taught, was produced from the four Elements, not immediately, but through the mediation of the three Principles--mercury, sulphur, and salt. These Principles were regarded as the tools put into the hands of him who desired to effect the transmutation of one substance into another. The Principles were not thought of as definite substances, nor as properties of this or that specified substance; they were considered to be the characteristic properties of large classes of substances. The chemist of to-day places many compounds in the same class because all are acids, because all react similarly under similar conditions. It used to be said that every acid possesses more or less of _the principle of acidity_. Lavoisier changed the language whereby certain facts concerning acids were expressed. He thought that experiments proved all acids to be compounds of the element oxygen; and for many years after Lavoisier, the alchemical expression _the principle of acidity_ was superseded by the word _oxygen_. Although Lavoisier recognised that not every compound of oxygen is an acid, he taught that every acid is a compound of oxygen. We know now that many acids are not compounds of oxygen, but we have not yet sufficient knowledge to frame a complete definition of the term _acid_. Nevertheless it is convenient, indeed it is necessary, to place together many compounds which react similarly under certain defined conditions, and to give a common name to them all. The alchemists also classified substances, but their classification was necessarily more vague than ours; and they necessarily expressed their reasons for putting different substances in the same class in a language which arose out of the general conceptions of natural phenomena which prevailed in their time. The primary classification of substances made by the alchemists was expressed by saying; these substances are rich in the principle _sulphur_, those contain much of the principle _mercury_, and this class is marked by the preponderance of the principle _salt_. The secondary classification of the alchemists was expressed by saying; this class is characterised by dryness, that by moisture, another by coldness, and a fourth by hotness; the dry substances contain much of the element _Earth_, the moist substances are rich in the element _Water_, in the cold substances the element _Air_ preponderates, and the hot substances contain more of the element _Fire_ than of the other elements. The alchemists went a step further in their classification of things. They asserted that there is One Thing present in all things; that everything is a vehicle for the more or less perfect exhibition of the properties of the One Thing; that there is a Primal Element common to all substances. The final aim of alchemy was to obtain the One Thing, the Primal Element, the Soul of all Things, so purified, not only from all specific substances, but also from all admixture of the four Elements and the three Principles, as to make possible the accomplishment of any transmutation by the use of it. If a person ignorant of its powers were to obtain the Essence, he might work vast havoc and cause enormous confusion; it was necessary, therefore, to know the conditions under which the potencies of the Essence became active. Hence there was need of prolonged study of the mutual actions of the most seemingly diverse substances, and of minute and patient examination of the conditions under which nature performs her marvellous transmutations. The quest of the One Thing was fraught with peril, and was to be attempted only by those who had served a long and laborious apprenticeship. In _The Chemical Treatise of Thomas Norton, the Englishman, called Believe-me, or the Ordinal of Alchemy_ (15th century), the adept is warned not to disclose his secrets to ordinary people. "You should carefully test and examine the life, character, and mental aptitudes of any person who would be initiated in this Art, and then you should bind him, by a sacred oath, not to let our Magistery be commonly or vulgarly known. Only when he begins to grow old and feeble, he may reveal it to one person, but not to more, and that one man must be virtuous.... If any wicked man should learn to practise the Art, the event would be fraught with great danger to Christendom. For such a man would overstep all bounds of moderation, and would remove from their hereditary thrones those legitimate princes who rule over the peoples of Christendom." The results of the experimental examination of the compositions and properties of substances, made since the time of the alchemists, have led to the modern conception of the chemical element, and the isolation of about seventy or eighty different elements. No substance now called an element has been produced in the laboratory by uniting two, or more, distinct substances, nor has any been separated into two, or more, unlike portions. The only decided change which a chemical element has been caused to undergo is the combination of it with some other element or elements, or with a compound or compounds. But it is possible that all the chemical elements may be combinations of different quantities of one primal element. Certain facts make this supposition tenable; and some chemists expect that the supposition will be proved to be correct. If the hypothetical primal element should be isolated, we should have fulfilled the aim of alchemy, and gained the One Thing; but the fulfilment would not be that whereof the alchemists dreamed. Inasmuch as the alchemical Essence was thought of as the Universal Spirit to whose presence is due whatever degree of perfection any specific substance exhibits, it followed that the more perfect a substance the greater is the quantity of the Essence in it. But even in the most perfect substance found in nature--which substance, the alchemists said, is gold--the Essence is hidden by wrappings of specific properties which prevent the ordinary man from recognising it. Remove these wrappings from some special substance, and you have the perfect form of that thing; you have some portion of the Universal Spirit joined to the one general property of the class of things whereof the particular substance is a member. Then remove the class-property, often spoken of by the alchemists as _the life_, of the substance, and you have the Essence itself. The alchemists thought that to every thing, or at any rate to every class of things, there corresponds a more perfect form than that which we see and handle; they spoke of gold, and the _gold of the Sages_; mercury, and the _mercury of the Philosophers_; sulphur, and the _heavenly sulphur of him whose eyes are opened_. To remove the outer wrappings of ordinary properties which present themselves to the untrained senses, was regarded by the alchemists to be a difficult task; to tear away the soul (the class-property) of a substance, and yet retain the Essence which made that substance its dwelling place, was possible only after vast labour, and by the use of the proper agent working under the proper conditions. An exceedingly powerful, delicate, and refined agent was needed; and the mastery of the agent was to be acquired by bitter experience, and, probably, after many disappointments. "Gold," an alchemist tells us, "does not easily give up its nature, and will fight for its life; but our agent is strong enough to overcome and kill it, and then it also has the power to restore it to life, and to change the lifeless remains into a new and pure body." Thomas Norton, the author of _The Ordinal of Alchemy_, writing in the 15th century, says the worker in transmutations is often tempted to be in a hurry, or to despair, and he is often deceived. His servants will be either stupid and faithful, or quick-witted and false. He may be robbed of everything when his work is almost finished. The only remedies are infinite patience, a sense of virtue, and sound reason. "In the pursuit of our Art," he says, "you should take care, from time to time, to unbend your mind from its sterner employments with some convenient recreation." The choice of workmen to aid in the mechanical parts of the quest was a great trouble to the alchemists. On this subject Norton says--"If you would be free from all fear over the gross work, follow my counsel, and never engage married men; for they soon give in and pretend they are tired out.... Hire your workmen for certain stipulated wages, and not for longer periods than twenty-four hours at a time. Give them higher wages than they would receive elsewhere, and be prompt and ready in your payments." Many accounts are given by alchemical writers of the agent, and many names are bestowed on it. The author of _A Brief Guide to the Celestial Ruby_ speaks thus of the agent--"It is our doorkeeper, our balm, our honey, oil, urine, maydew, mother, egg, secret furnace, oven, true fire, venomous dragon, Theriac, ardent wine, Green Lion, Bird of Hermes, Goose of Hermogenes, two-edged sword in the hand of the Cherub that guards the Tree of Life.... It is our true secret vessel, and the Garden of the Sages in which our sun rises and sets. It is our Royal Mineral, our triumphant vegetable Saturnia, and the magic rod of Hermes, by means of which he assumes any shape he likes." Sometimes we are told that the agent is mercury, sometimes that it is gold, but not common mercury or common gold. "Supplement your common mercury with the inward fire which it needs, and you will soon get rid of all superfluous dross." "The agent is gold, as highly matured as natural and artificial digestion can make it, and a thousand times more perfect than the common metal of that name. Gold, thus exalted, radically penetrates, tinges, and fixes metals." The alchemists generally likened the work to be performed by their agent to the killing of a living thing. They constantly use the allegory of death, followed by resurrection, in describing the steps whereby the Essence was to be obtained, and the processes whereby the baser metals were to be partially purified. They speak of the mortification of metals, the dissolution and putrefaction of substances, as preliminaries to the appearance of the true life of the things whose outward properties have been destroyed. For instance, Paracelsus says: "Destruction perfects that which is good; for the good cannot appear on account of that which conceals it." The same alchemist speaks of rusting as the mortification of metals; he says: "The mortification of metals is the removal of their bodily structure.... The mortification of woods is their being turned into charcoal or ashes." Paracelsus distinguishes natural from artificial mortification, "Whatever nature consumes," he says, "man cannot restore. But whatever man destroys man can restore, and break again when restored." Things which had been mortified by man's device were considered by Paracelsus not to be really dead. He gives this extraordinary illustration of his meaning: "You see this is the case with lions, which are all born dead, and are first vitalised by the horrible noise of their parents, just as a sleeping person is awakened by a shout." The mortification of metals is represented in alchemical books by various images and allegories. Fig. I. is reduced from a cut in a 16th century work, _The Book of Lambspring, a noble ancient Philosopher, concerning the Philosophical Stone_. [Illustration: Here the father devours the son; The soul and spirit flow forth from the body. FIG. I.] The image used to set forth the mortification of metals is a king swallowing his son. Figs. II. and III. are reduced from Basil Valentine's _Twelve Keys_. Both of these figures represent the process of mortification by images connected with death and burial. [Illustration: FIG. II.] In his explanation (?) of these figures, Basil Valentine says:-- "Neither human nor animal bodies can be multiplied or propagated without decomposition; the grain and all vegetable seed, when cast into the ground, must decay before it can spring up again; moreover, putrefaction imparts life to many worms and other animalculæ.... If bread is placed in honey, and suffered to decay, ants are generated ... maggots are also developed by the decay of nuts, apples, and pears. The same thing may be observed in regard to vegetable life. Nettles and other weeds spring up where no such seed has ever been sown. This occurs only by putrefaction. The reason is that the soil in such places is so disposed, and, as it were, impregnated, that it produces these fruits; which is a result of the properties of sidereal influences; consequently the seed is spiritually produced in the earth, and putrefies in the earth, and by the operation of the elements generates corporeal matter according to the species of nature. Thus the stars and the elements may generate new spiritual, and ultimately, new vegetable seed, by means of putrefaction.... Know that, in like manner, no metallic seed can develop, or multiply, unless the said seed, by itself alone, and without the introduction of any foreign substance, be reduced to a perfect putrefaction." [Illustration: FIG. III.] The action of the mineral agent in perfecting substances is often likened by the alchemists to the conjoining of the male and the female, followed by the production of offspring. They insist on the need of a union of two things, in order to produce something more perfect than either. The agent, they say, must work upon something; alone it is nothing. The methods whereby the agent is itself perfected, and the processes wherein the agent effects the perfecting of the less perfect things, were divided into stages by the alchemists. They generally spoke of these stages as _Gates_, and enumerated ten or sometimes twelve of them. As examples of the alchemical description of these gates, I give some extracts from _A Brief Guide to the Celestial Ruby_. The first gate is _Calcination_, which is "the drying up of the humours"; by this process the substance "is concocted into a black powder which is yet unctuous, and retains its radical humour." When gold passes through this gate, "We observe in it two natures, the fixed and the volatile, which we liken to two serpents." The fixed nature is likened to a serpent without wings; the volatile, to a serpent with wings: calcination unites these two into one. The second gate, _Dissolution_, is likened to death and burial; but the true Essence will appear glorious and beautiful when this gate is passed. The worker is told not to be discouraged by this apparent death. _The mercury of the sages_ is spoken of by this author as the queen, and gold as the king. The king dies for love of the queen, but he is revived by his spouse, who is made fruitful by him and brings forth "a most royal son." Figs. IV. and V. are reduced from _The Book of Lambspring_; they express the need of the conjunction of two to produce one. [Illustration: Here you behold a great marvel-- Two Lions are joined into one. The spirit and soul must be united in their body. FIG. IV.] After dissolution came _Conjunction_, wherein the separated elements were combined. Then followed _Putrefaction_, necessary for the germination of the seed which had been produced by calcination, dissolution, and conjunction. Putrefaction was followed by _Congelation_ and _Citation_. The passage through the next gate, called _Sublimation_, caused the body to become spiritual, and the spiritual to be made corporal. _Fermentation_ followed, whereby the substance became soft and flowed like wax. Finally, by _Exaltation_, the Stone was perfected. [Illustration: Here are two birds, great and strong--the body and spirit; one devours the other. Let the body be placed in horse-dung, or a warm bath, the spirit having been extracted from it. The body has become white by the process, the spirit red by our art. All that exists tends towards perfection, and thus is the Philosopher's Stone prepared. FIG. V.] The author of _The Open Entrance_ speaks of the various stages in the perfecting of the agent as _regimens_. The beginning of the heating of gold with mercury is likened to the king stripping off his golden garments and descending into the fountain; this is the _regimen of Mercury_. As the heating is continued, all becomes black; this is the _regimen of Saturn_. Then is noticed a play of many colours; this is the _regimen of Jupiter_: if the heat is not regulated properly, "the young ones of the crow will go back to the nest." About the end of the fourth month you will see "the sign of the waxing moon," and all becomes white; this is the _regimen of the Moon_. The white colour gives place to purple and green; you are now in the _regimen of Venus_. After that, appear all the colours of the rainbow, or of a peacock's tail; this is the _regimen of Mars_. Finally the colour becomes orange and golden; this is the _regimen of the Sun_. The reader may wish to have some description of the Essence. The alchemists could describe it only in contraries. It had a bodily form, but its method of working was spiritual. In _The Sodic Hydrolith, or Water Stone of the Wise_ we are told:-- "The stone is conceived below the earth, born in the earth, quickened in heaven, dies in time, and obtains eternal glory.... It is bluish-grey and green.... It flows like water, yet it makes no wet; it is of great weight, and is small." Philalethes says, in _A Brief Guide to the Celestial Ruby_: "The Philosopher's Stone is a certain heavenly, spiritual, penetrative, and fixed substance, which brings all metals to the perfection of gold or silver (according to the quality of the Medicine), and that by natural methods, which yet in their effects transcend Nature.... Know then that it is called a stone, not because it is like a stone, but only because, by virtue of its fixed nature, it resists the action of fire as successfully as any stone. In species it is gold, more pure than the purest; it is fixed and incombustible like a stone, but its appearance is that of very fine powder, impalpable to the touch, sweet to the taste, fragrant to the smell, in potency a most penetrative spirit, apparently dry and yet unctuous, and easily capable of tinging a plate of metal.... If we say that its nature is spiritual, it would be no more than the truth; if we described it as corporeal, the expression would be equally correct." The same author says: "There is a substance of a metalline species which looks so cloudy that the universe will have nothing to do with it. Its visible form is vile; it defiles metalline bodies, and no one can readily imagine that the pearly drink of bright Phoebus should spring from thence. Its components are a most pure and tender mercury, a dry incarcerate sulphur, which binds it and restrains fluxation.... Know this subject, it is the sure basis of all our secrets.... To deal plainly, it is the child of Saturn, of mean price and great venom.... It is not malleable, though metalline. Its colour is sable, with intermixed argent which mark the sable fields with veins of glittering argent." In trying to attach definite meanings to the alchemical accounts of Principles, Elements, and the One Thing, and the directions which the alchemists give for changing one substance into others, we are very apt to be misled by the use of such an expression as _the transmutation of the elements_. To a chemist that phrase means the change of an element into another element, an element being a definite substance, which no one has been able to produce by the combination of two or more substances unlike itself, or to separate into two or more substances unlike itself. But whatever may have been the alchemical meaning of the word _element_, it was certainly not that given to the same word to-day. Nor did the word _transmutation_ mean to the alchemist what it means to the chemist. The facts which are known at present concerning the elements make unthinkable such a change as that of lead into silver; but new facts _may_ be discovered which will make possible the separation of lead into things unlike itself, and the production of silver by the combination of some of these constituents of lead. The alchemist supposed he knew such facts as enabled him not only to form a mental picture of the change of lead into silver, or tin into gold, but also to assert that such changes must necessarily happen, and to accomplish them. Although we are quite sure that the alchemist's facts were only imaginings, we ought not to blame him for his reasoning on what he took to be facts. Every metal is now said to be an element, in the modern meaning of that word: the alchemist regarded the metals as composite substances; but he also thought of them as more simple than many other things. Hence, if he was able to transmute one metal into another, he would have strong evidence in support of his general conception of the unity of all things. And, as transmutation meant, to the alchemist, the bringing of a substance to the condition of greatest perfection possible for that substance, his view of the unity of nature might be said to be proved if he succeeded in changing one of the metals, one of these comparatively simple substances, into the most perfect of all metals, that is, into gold. The transmutation of the baser metals into gold thus came to be the practical test of the justness of the alchemical scheme of things. Some alchemists assert they had themselves performed the great transmutation; others tell of people who had accomplished the work. The following story is an example of the accounts given of the making of gold. It is taken from _John Frederick Helvetius' Golden Calf, which the world worships and adores_ (17th century):-- "On the 27th December 1666, in the forenoon, there came to my house a certain man, who was a complete stranger to me, but of an honest grave countenance, and an authoritative mien, clothed in a simple garb.... He was of middle height, his face was long and slightly pock-marked, his hair was black and straight, his chin close-shaven, his age about forty-three or forty-four, and his native province, as far as I could make out, North Holland. After we had exchanged salutations, he asked me whether he might have some conversation with me. He wished to say something to me about the Pyrotechnic Art, as he had read one of my tracts (directed against the Sympathetic Powder of Dr Digby), in which I hinted a suspicion whether the Grand Arcanum of the Sages was not after all a gigantic hoax. He, therefore, took that opportunity of asking me whether I could not believe that such a grand mystery might exist in the nature of things, by means of which a physician could restore any patient whose vitals were not irreparably destroyed. I answered, 'Such a medicine would be a most desirable acquisition for any physician; nor can any man tell how many secrets there may be hidden in Nature; yet, though I have read much about the truth of this art, it has never been my good fortune to meet with a real master of the alchemical science.' ... After some further conversation, the Artist Elias (for it was he) thus addressed me: 'Since you have read so much in the works of the alchemists about this stone, its substance, its colour and its wonderful effects, may I be allowed the question, whether you have not prepared it yourself?' On my answering his question in the negative, he took out of his bag a cunningly-worked ivory box, in which were three large pieces of substance resembling glass, or pale sulphur, and informed me that here was enough of the tincture for the production of twenty tons of gold. When I had held the precious treasure in my hand for a quarter of an hour (during which time I listened to a recital of its wonderful curative properties), I was compelled to restore it to its owner, which I could not help doing with a certain degree of reluctance.... My request that he would give me a piece of his stone (though it were no larger than a coriander seed), he somewhat brusquely refused, adding, in a milder tone, that he could not give it me for all the wealth I possessed, and that not on account of its great preciousness, but for some other reason which it was not lawful for him to divulge.... Then he inquired whether I could not show him into a room at the back of the house, where we should be less liable to the observation of passers-by. On my conducting him into the state parlour (which he entered without wiping his dirty boots), he demanded of me a gold coin, and while I was looking for it, he produced from his breast pocket a green silk handkerchief, in which were folded up five medals, the gold of which was infinitely superior to that of my gold piece." Here follows the inscriptions on the medals. "I was filled with admiration, and asked my visitor whence he had obtained that wonderful knowledge of the whole world. He replied that it was a gift freely bestowed on him by a friend who had stayed a few days at his house." Here follows the stranger's account of this friend's experiments. "When my strange visitor had concluded his narrative, I besought him to give me a proof of his assertion, by performing the transmutatory operation on some metals in my presence. He answered evasively, that he could not do so then, but that he would return in three weeks, and that, if he was then at liberty to do so, he would show me something that would make me open my eyes. He appeared punctually to the promised day, and invited me to take a walk with him, in the course of which we discoursed profoundly on the secrets of Nature in fire, though I noticed that my companion was very chary in imparting information about the Grand Arcanum.... At last I asked him point blank to show me the transmutation of metals. I besought him to come and dine with me, and to spend the night at my house; I entreated; I expostulated; but in vain. He remained firm. I reminded him of his promise. He retorted that his promise had been conditional upon his being permitted to reveal the secret to me. At last, however, I prevailed upon him to give me a piece of his precious stone--a piece no larger than a grain of rape seed.... He bid me take half an ounce of lead ... and melt it in the crucible; for the Medicine would certainly not tinge more of the base metal than it was sufficient for.... He promised to return at nine o'clock the next morning.... But at the stated hour on the following day he did not make his appearance; in his stead, however, there came, a few hours later, a stranger, who told me that his friend the artist was unavoidably detained, but that he would call at three o'clock in the afternoon. The afternoon came; I waited for him till half-past seven o'clock. He did not appear. Thereupon my wife came and tempted me to try the transmutation myself. I determined however to wait till the morrow. On the morrow ... I asked my wife to put the tincture in wax, and I myself ... prepared six drachms of lead; I then cast the tincture, enveloped as it was in wax, on the lead; as soon as it was melted, there was a hissing sound and a slight effervescence, and after a quarter of an hour I found that the whole mass of lead had been turned into the finest gold.... We immediately took it to the goldsmith, who at once declared it the finest gold he had ever seen, and offered to pay fifty florins an ounce for it." He then describes various tests which were made to prove the purity of the gold. "Thus I have unfolded to you the whole story from beginning to end. The gold I still retain in my possession, but I cannot tell you what has become of the Artist Elias." CHAPTER VI. ALCHEMY AS AN EXPERIMENTAL ART. A modern writer, Mr A.E. Waite, in his _Lives of the Alchemystical Philosophers_, says: "The physical theory of transmutation is based on the composite character of the metals, on their generation in the bowels of the earth, and on the existence in nature of a pure and penetrating matter which applied to any substance exalts and perfects it after its own kind." It must he admitted that the alchemists could cite many instances of transmutations which seemed to lead to the conclusion, that there is no difference of kind between the metals and other substances such as water, acids, oils, resins, and wood. We are able to-day to effect a vast number of transformations wherein one substance is exchanged for another, or made to take the place of another. We can give fairly satisfactory descriptions of these changes; and, by comparing them one with another, we are able to express their essential features in general terms which can be applied to each particular instance. The alchemists had no searching knowledge of what may be called the mechanism of such changes; they gave an explanation of them which we must call incorrect, in the present state of our knowledge. But, as Hoefer says in his _Histoire de la Chimie_, "to jeer at [the alchemical] theory is to commit at once an anachronism and an injustice.... Unless the world should finish to-morrow, no one can have the pretension to suppose that our contemporaries have said the last word of science, and nothing will remain for our descendants to discover, no errors for them to correct, no theories for them to set straight." [Illustration: FIG. VI. _See p. 90._] [Illustration: FIG. VII. _See p. 90._] [Illustration: FIG. VIII. _See p. 91._] What kind of experimental evidence could an alchemist furnish in support of his theory of transmutation? In answering this question, I cannot do better than give a condensed rendering of certain pages in Hoefer's _Histoire de la Chimie_. The reader is supposed to be present at experiments conducted in the laboratory of a Grand Master of the Sacred Art in the 5th or 6th century. _Experiment_.--Ordinary water is boiled in an open vessel; the water is changed to a vapour which disappears, and a white powdery earth remains in the vessel. _Conclusion_.--Water is changed into air and earth. Did we not know that ordinary water holds certain substances in solution, and that boiling water acts on the vessel wherein it is boiled, we should have no objection to urge against this conclusion. It only remained to transmute fire that the transmutation of the four elements might be completed. _Experiment._--A piece of red-hot iron is placed in a bell-jar, filled with water, held over a basin containing water; the volume of the water decreases, and the air in the bell-jar takes fire when a lighted taper is brought into it. _Conclusion._--Water is changed into fire. That interpretation was perfectly reasonable at a time when the fact was unknown that water is composed of two gaseous substances; that one of these (oxygen) is absorbed by the iron, and the other (hydrogen) collects in the bell-jar, and ignites when brought into contact with a flame. _Experiment_.--Lead, or any other metal except gold or silver, is calcined in the air; the metal loses its characteristic properties, and is changed into a powdery substance, a kind of cinder or calx. When this cinder, which was said to be the result of the _death of the metal_, is heated in a crucible with some grains of wheat, one sees the metal revive, and resume its original form and properties. _Conclusion._--The metal which had been destroyed is revivified by the grains of wheat and the action of fire. Is this not to perform the miracle of the resurrection? No objection can he raised to this interpretation, as long as we are ignorant of the phenomena of oxidation, and the reduction of oxides by means of carbon, or organic substances rich in carbon, such as sugar, flour, seeds, etc. Grains of wheat were the symbol of life, and, by extension, of the resurrection and eternal life. [Illustration: FIG. IX. _See p. 91._] _Experiment_.--Ordinary lead is calcined in a cupel made of cinders or powdered bones; the lead is changed to a cinder which disappears into the cupel, and a button of silver remains. _Conclusion_.--The lead has vanished; what more natural than the conclusion that it has been transformed into silver? It was not known then that all specimens of lead contain more or less silver. [Illustration: FIG. X. _See p. 92._] _Experiment._-The vapour of arsenic bleaches copper. This fact gave rise to many allegories and enigmas concerning the means of transforming copper into silver. Sulphur, which acts on metals and changes many of them into black substances, was looked on as a very mysterious thing. It was with sulphur that the coagulation (solidification) of mercury was effected. _Experiment_.--Mercury is allowed to fall, in a fine rain, on to melted sulphur; a black substance is produced; this black substance is heated in a closed vessel, it is volatilised and transformed into a beautiful red solid. One could scarcely suppose that the black and the red substances are identical, if one did not know that they are composed of the same quantities of the same elements, sulphur and mercury. How greatly must this phenomenon have affected the imagination of the chemists of ancient times, always so ready to be affected by everything that seemed supernatural! Black and red were the symbols of darkness and light, of the evil and the good principle; and the union of these two principles represented the moral order. At a later time the idea helped to establish the alchemical doctrine that sulphur and mercury are the Principles of all things. _Experiment._--Various organic substances are analysed by heating in a distillation-apparatus; the products are, in each case, a solid residue, liquids which distil off, and certain spirits which are disengaged. The results supported the ancient theory which asserted that _earth_, _water_, _air_, and _fire_ are the four Elements of the world. The solid residue represented _earth_; the liquid products of the distillation, _water_; and the spirituous substances, _air_. _Fire_ was regarded sometimes as the means of purification, sometimes as the soul, or invisible part, of all substances. _Experiment_.-A strong acid is poured on to copper. The metal is attacked, and at last disappears, giving place to a green liquid, as transparent as water. A thin sheet of iron is plunged into the liquid; the copper re-appears, and the iron vanishes. What more simple than to conclude that the iron has been transformed into copper? Had lead, silver, or gold been used in place of copper, one would have said that the iron was transformed into lead, silver, or gold. In their search for "the pure and penetrating matter which applied to any substance exalts and perfects it after its own kind," the alchemists necessarily made many inventions, laid the foundation of many arts and manufactures, and discovered many facts of importance in the science of chemistry. The practitioners of the _Sacred Art_ of Egypt must have been acquainted with many operations which we now class as belonging to applied chemistry; witness, their jewellery, pottery, dyes and pigments, bleaching, glass-making, working in metals and alloys, and their use of spices, essential oils, and soda in embalming, and for other purposes. During the centuries when alchemy flourished, gunpowder was invented, the art of printing was established, the compass was brought into use, the art of painting and staining glass was begun and carried to perfection, paper was made from rags, practical metallurgy advanced by leaps and bounds, many new alloys of metals came into use, glass mirrors were manufactured, and considerable advances were made in practical medicine and sanitation. [Illustration: FIG. XI. _See p. 92._] Basil Valentine, who was one of the greatest alchemists of the 16th century, discovered many of the properties of the metal antimony, and prepared and examined many compounds of that metal; he made green vitriol from pyrites, brandy from fermented grape-juice, fulminating gold, sulphide of potash, and spirits of salt; he made and used baths of artificial mineral waters, and he prepared various metals by what are now called _wet methods_, for instance, copper, by immersing plates of iron in solutions of bluestone. He examined the air of mines, and suggested practical methods for determining whether the air in a mine was respirable. Hoefer draws attention to a remarkable observation recorded by this alchemist. Speaking of the "spirit of mercury," Basil Valentine says it is "the origin of all the metals; that spirit is nothing else than an air flying here and there without wings; it is a moving wind, which, after it has been chased from its home of Vulcan (that is, fire), returns to the chaos; then it expands and passes into the region of the air from whence it had come." As Hoefer remarks, this is perhaps one of the earliest accounts of the gas discovered by Priestley and studied by Lavoisier, the gas we now call oxygen, and recognise as of paramount importance in chemical reactions. [Illustration: FIG. XII. _See p. 92._] Besides discovering and recording many facts which have become part and parcel of the science of chemistry, the alchemists invented and used various pieces of apparatus, and conducted many operations, which are still employed in chemical laboratories. I shall reproduce illustrations of some of these processes and pieces of apparatus, and quote a few of the directions, given in a book, published in 1664, called _The Art of Distillation_, by John French, Dr. in Physick. The method recommended by French for hermetically sealing the neck of a glass vessel is shown in Fig. VI. p. 80. The neck of the vessel is surrounded by a tray containing burning coals; when the glass melts it is cut off by shears, and then closed by tongs, which are made hot before use. Fig. VII. p. 81, represents a method for covering an open vessel, air-tight, with a receptacle into which a substance may be sublimed from the lower vessel. The lettering explains the method of using the apparatus. French gives very practical directions and much sound advice for conducting distillations of various kinds. The following are specimens of his directions and advice:-- "When you put water into a seething Balneum wherein there are glasses let it be hot, or else thou wilt endanger the breaking of the glasses. "When thou takest any earthen, or glass vessel from the fire, expose it not to the cold aire too suddenly for fear it should break. "In all your operations diligently observe the processes which you read, and vary not a little from them, for sometimes a small mistake or neglect spoils the whole operation, and frustrates your expectations. "Try not at first experiments of great cost, or great difficulty; for it will be a great discouragement to thee, and thou wilt be very apt to mistake. "If any one would enter upon the practices of Chymistry, let him apply himself to some expert artist for to be instructed in the manual operation of things; for by this means he will learn more in two months, than he can by his practice and study in seven years, as also avoid much pains and cost, and redeem much time which else of necessity he will lose." Fig. VIII. p. 82, represents a common cold still, and Fig. IX. p. 84, is a sketch of an apparatus for distilling by the aid of boiling water. The bath wherein the vessels are placed in Fig. IX. was called by the alchemists _balneum Mariae_, from Mary the Jewess, who is mentioned in the older alchemical writings, and is supposed to have invented an apparatus of this character. Nothing definite is known of Mary the Jewess. A writer of the 7th century says she was initiated in the sacred art in the temple of Memphis; a legend prevailed among some of the alchemists that she was the sister of Moses. Fig. X. p. 85, represents methods of distilling with an apparatus for cooling the volatile products; the lower vessel is an _alembic_, with a long neck, the upper part of which passes through a vessel containing cold water. [Illustration: Fig XIII. _See p. 94._] Fig. XI. p. 88, shows a _pelican_, that is a vessel wherein a liquid might be heated for a long time, and the volatile products be constantly returned to the original vessel. Fig. XII. p. 89, represents a retort with a receiver. Some of the pieces of apparatus for distilling, which are described by French, are shown in the following figures. Besides describing apparatus for distilling, subliming, and other processes in the laboratory, French gives directions for making tinctures, essences, essential oils, spirits of salt, and pure saltpetre, oil of vitriol, butter of antimony, calces (or as we now say, oxides) of metals, and many other substances. He describes processes for making fresh water from salt, artificial mineral water, medicated hot baths for invalids (one of the figures represents an apparatus very like those advertised to-day as "Turkish baths at home"), and artificial precious stones; he tells how to test minerals, and make alloys, and describes the preparation of many substances made from gold and silver. He also gives many curious receipts; for instance, "To make Firre-trees appear in Turpentine," "To make a Plant grow in two or three hours," "To make the representation of the whole world in a Glass," "To extract a white Milkie substance from the raies of the Moon." [Illustration: FIG. XIV. _See p. 94._] The process of making oil of vitriol, by burning sulphur under a hood fitted with a side tube for the outflow of the oil of vitriol, is represented in Fig. XIII. p. 92. Fig. XIV. p. 93, is interesting; it is an apparatus for rectifying spirits, by distilling, and liquefying only the most volatile portions of the distillate. The spirituous liquor was heated, and the vapours caused to traverse a long zigzag tube, wherein the less volatile portions condensed to liquid, which flowed back into the vessel; the vapour then passed into another vessel, and then through a second zigzag tube, and was finally cooled by water, and the condensed liquid collected. This apparatus was the forerunner of that used to-day, for effecting the separation of liquids which boil at different temperatures, by the process called _fractional distillation_. We should never forget that the alchemists were patient and laborious workers, their theories were vitally connected with their practice, and there was a constant action and reaction between their general scheme of things and many branches of what we now call chemical manufactures. We may laugh at many of their theories, and regret that much useless material was accumulated by them; we may agree with Boyle (end of 17th century) when he likens the "hermetick philosophers," in their search for truth, to "the navigators of Solomon's Tarshish fleet, who brought home from their long and tedious voyages, not only gold, and silver, and ivory, but apes and peacocks too; for so the writings of several of your hermetick philosophers present us, together with divers substantial and noble experiments, theories, which either like peacocks' feathers make a great show but are neither solid nor useful; or else like apes, if they have some appearance of being rational, are blemished with some absurdity or other, that, when they are attentively considered make them appear ridiculous." But however we may condemn their method, because it rested on their own conception of what the order of nature must be, we cannot but praise their assiduity in conducting experiments and gathering facts. As Bacon says, in _De Augmentis Scientiarum_: "Alchemy may be compared to the man who told his sons that he had left them gold buried somewhere in his vineyard; where they by digging found no gold, but by turning up the mould about the roots of the vines, procured a plentiful vintage. So the search and endeavours to make gold have brought many useful inventions and instructive experiments to light." CHAPTER VII. THE LANGUAGE OF ALCHEMY The vagueness of the general conceptions of alchemy, and the attribution of ethical qualities to material things by the alchemists, necessarily led to the employment of a language which is inexact, undescriptive, and unsuggestive to modern ears. The same name was given to different things, and the same thing went under many names. In Chapter IV. I endeavoured to analyse two terms which were constantly used by the alchemists to convey ideas of great importance, the terms _Element_ and _Principle_. That attempt sufficed, at any rate, to show the vagueness of the ideas which these terms were intended to express, and to make evident the inconsistencies between the meanings given to the words by different alchemical writers. The story quoted in Chapter III., from Michael Sendivogius, illustrates the difficulty which the alchemists themselves had in understanding what they meant by the term _Mercury_; yet there is perhaps no word more often used by them than that. Some of them evidently took it to mean the substance then, and now, called mercury; the results of this literal interpretation were disastrous; others thought of mercury as a substance which could be obtained, or, at any rate, might be obtained, by repeatedly distilling ordinary mercury, both alone and when mixed with other substances; others used the word to mean a hypothetical something which was liquid but did not wet things, limpid yet capable of becoming solid, volatile yet able to prevent the volatilisation of other things, and white, yet ready to cause other white things to change their colour; they thought of this something, this soul of mercury, as having properties without itself being tangible, as at once a substance and not a substance, at once a bodily spirit and a spiritual body. It was impossible to express the alchemical ideas in any language save that of far-fetched allegory. The alchemical writings abound in such allegories. Here are two of them. The first allegory is taken from _The Twelve Keys_, of Basilius Valentinus, the Benedictine:-- "The eleventh key to the knowledge of the augmentation of our Stone I will put before you in the form of a parable. "There lived in the East a gilded knight, named Orpheus, who was possessed of immense wealth, and had everything that heart can wish. He had taken to wife his own sister, Euridice, who did not, however, bear him any children. This he regarded as the punishment of his sin in having wedded his own sister, and was instant in prayer to God both by day and by night, that the curse might be taken from him. One night when he was buried in a deep sleep, there came to him a certain winged messenger, named Phoebus, who touched his feet, which were very hot, and said: 'Thou noble knight, since thou hast wandered through many cities and kingdoms and suffered many things at sea, in battle, and in the lists, the heavenly Father has bidden me make known to thee the following means of obtaining thy prayer: Take blood from thy right side, and from the left side of thy spouse. For this blood is the heart's blood of your parents, and though it may seem to be of two kinds, yet, in reality, it is only one. Mix the two kinds of blood, and keep the mixture tightly enclosed in the globe of the seven wise Masters. Then that which is generated will be nourished with its own flesh and blood, and will complete its course of development when the Moon has changed for the eighth time. If thou repeat this process again and again, thou shalt see children's children, and the offspring of thy body shall fill the world.' When Phoebus had thus spoken, he winged his flight heavenward. In the morning the knight arose and did the bidding of the celestial messenger, and God gave to him and to his wife many children, who inherited their father's glory, wealth, and knightly honours from generation to generation." In the "Dedicatory Epistle" to his _Triumphal Chariot of Antimony_, Basil Valentine addresses his brother alchemists as follows:-- "Mercury appeared to me in a dream, and brought me back from my devious courses to the one way. 'Behold me clad not in the garb of the vulgar, but in the philosopher's mantle.' So he said, and straightway began to leap along the road in headlong bounds. Then, when he was tired, he sat down, and, turning to me, who had followed him in the spirit, bade me mark that he no longer possessed that youthful vigour with which he would at the first have overcome every obstacle, if he had not been allowed a free course. Encouraged by his friendly salutation, I addressed him in the following terms: 'Mercury, eloquent scion of Atlas, and father of all Alchemists, since thou hast guided me hitherto, shew me, I pray thee, the way to those Blessed Isles, which thou hast promised to reveal to all thine elect children. 'Dost thou remember,' he replied, that when I quitted thy laboratory, I left behind me a garment so thoroughly saturated with my own blood, that neither the wind could efface it, nor all-devouring time destroy its indelible essence? Fetch it hither to me, that I may not catch a chill from the state of perspiration in which I now am; but let me clothe myself warmly in it, and be closely incited thereto, so that I may safely reach my bride, who is sick with love. She has meekly borne many wrongs, being driven through water and fire, and compelled to ascend and descend times without number--yet has she been carried through it all by the hope of entering with me the bridal chamber, wherein we expect to beget a son adorned from his birth with the royal crown which he may not share with others. Yet may he bring his friends to the palace, where sits enthroned the King of Kings, who communicates his dignity readily and liberally to all that approach him.' "I brought him the garment, and it fitted him so closely, that it looked like an iron skin securing him against all the assaults of Vulcan. 'Let us proceed,' he then said, and straightway sped across the open field, while I boldly strove to keep up with my guide. "Thus we reached his bride, whose virtue and constancy were equal to his own. There I beheld their marvellous conjugal union and nuptial consummation, whence was born the son crowned with the royal diadem. When I was about to salute him as King of Kings and Lord of Lords, my Genius stood by me and warned me not to be deceived, since this was only the King's forerunner, but not the King himself whom I sought. "When I heard the admonition, I did not know whether to be sad or joyful. 'Depart,' then said Mercury, 'with this bridal gift, and when you come to those disciples who have seen the Lord himself, show them this sign.' And therewith he gave me a gold ring from his son's finger. 'They know the golden branch which must be consecrated to Proserpina before you can enter the palace of Pluto. When he sees this ring, perhaps one will open to you with a word the door of that chamber, where sits enthroned in his magnificence the Desire of all Nations, who is known only to the Sages.' "When he had thus spoken, the vision vanished, but the bridal gift which I still held in my hand shewed me that it had not been a mere dream. It was of gold, but to me more precious than the most prized of all metals. Unto you I will shew it when I am permitted to see your faces, and to converse with you freely. Till that earnestly wished-for time, I bid you farewell." One result of the alchemical modes of expression was, that he who tried to follow the directions given in alchemical books got into dire confusion. He did not know what substances to use in his operations; for when he was told to employ "the homogeneous water of gold," for example, the expression might mean anything, and in despair he distilled, and calcined, and cohobated, and tried to decompose everything he could lay hands on. Those who pretended to know abused and vilified those who differed from them. In _A Demonstration of Nature_, by John A. Mehung (17th century), Nature addresses the alchemical worker in the following words:-- "You break vials, and consume coals, only to soften your brains still more with the vapours. You also digest alum, salt, orpiment, and altrament; you melt metals, build small and large furnaces, and use many vessels; nevertheless I am sick of your folly, and you suffocate me with your sulphurous smoke.... You would do better to mind your own business, than to dissolve and distil so many absurd substances, and then to pass them through alembics, cucurbits, stills, and pelicans." Henry Madathanas, writing in 1622, says:-- "Then I understood that their purgations, sublimations, cementations, distillations, rectifications, circulations, putrefactions, conjunctions, calcinations, incinerations, mortifications, revivifications, as also their tripods, athanors, reverberatory alembics, excrements of horses, ashes, sand, stills, pelican-viols, retorts, fixations, etc., are mere plausible impostures and frauds." The author of _The Only Way_ (1677) says: "Surely every true Artist must look on this elaborate tissue of baseless operations as the merest folly, and can only wonder that the eyes of those silly dupes are not at last opened, that they may see something besides such absurd sophisms, and read something besides those stupid and deceitful books.... I can speak from bitter experience, for I, too, toiled for many years ... and endeavoured to reach the coveted goal by sublimation, distillation, calcination, circulation, and so forth, and to fashion the Stone out of substances such as urine, salt, atrament, alum, etc. I have tried hard to evolve it out of hairs, wine, eggs, bones, and all manner of herbs; out of arsenic, mercury, and sulphur, and all the minerals and metals.... I have spent nights and days in dissolving, coagulating, amalgamating, and precipitating. Yet from all these things I derived neither profit nor joy." Another writer speaks of many would-be alchemists as "floundering about in a sea of specious book-learning." If alchemists could speak of their own processes and materials as those authors spoke whom I have quoted, we must expect that the alchemical language would appear mere jargon to the uninitiated. In Ben Jonson's play _The Alchemist_, _Surley_, who is the sceptic of the piece, says to Subtle, who is the alchemist-- ... Alchemy is a pretty kind of game, Somewhat like tricks o' the cards, to cheat a man With charming ... What else are all your terms, Whereon no one of your writers 'grees with other? Of your elixir, your _lac virginis_, Your stone, your med'cine, and your chrysosperme, Your sal, your sulphur, and your mercury, Your oil of height, your tree of life, your blood, Your marchesite, your tutie, your magnesia, Your toad, your crow, your dragon, and your panther; Your sun, your moon, your firmament, your adrop, Your lato, azoch, zernich, chibrit, heutarit, And then your red man, and your white woman, With all your broths, your menstrues, and materials, Of lye and egg-shells, women's terms, man's blood, Hair o' the head, burnt clout, chalk, merds, and clay, Powder of bones, scalings of iron, glass, And moulds of other strange ingredients, Would burst a man to name? To which _Subtle_ answers, And all these named Intending but one thing; which art our writers Used to obscure their art. Was not all the knowledge Of the Egyptians writ in mystic symbols? Speak not the Scriptures oft in parables? Are not the choicest fables of the poets, That were the fountains and first springs of wisdom, Wrapp'd in perplexed allegories? The alchemists were very fond of using the names of animals as symbols of certain mineral substances, and of representing operations in the laboratory by what may be called animal allegories. The _yellow lion_ was the alchemical symbol of yellow sulphides, the _red lion_ was synonymous with cinnabar, and the _green lion_ meant salts of iron and of copper. Black sulphides were called _eagles_, and sometimes _crows_. When black sulphide of mercury is strongly heated, a red sublimate is obtained, which has the same composition as the black compound; if the temperature is not kept very high, but little of the red sulphide is produced; the alchemists directed to urge the fire, "else the black crows will go back to the nest." [Illustration: A salamander lives in the fire, which imparts to it a most glorious hue. This is the reiteration, gradation, and amelioration of the Tincture, or Philosopher's Stone; and the whole is called its Augmentation. FIG. XV.] The salamander was called the king of animals, because it was supposed that he lived and delighted in fire; keeping a strong fire alight under a salamander was sometimes compared to the purification of gold by heating it. Fig. XV., reduced from _The Book of Lambspring_ represents this process. The alchemists employed many signs, or shorthand expressions, in place of writing the names of substances. The following are a few of the signs which were used frequently. [Symbol: Saturn] Saturn, also lead; [Symbol: Jupiter] Jupiter, also tin; [Symbol: Mars-1] and [Symbol: Mars-2] Mars, also iron; [Symbol: Sun] Sol, also gold; [Symbol: Venus] Venus, also copper; [Symbol: Mercury-1], [Symbol: Mercury-2] and [Symbol: Mercury-3] Mercury; [Symbol: Moon] Luna, also silver; [Symbol: Sulphur] Sulphur; [Symbol: Vitriol] Vitriol; [Symbol: Fire] fire; [Symbol: Air] air; [Symbol: Water] and [Symbol: Aquarius] water; [Symbol: Earth] earth; [Symbol: Aqua Fortis] aqua fortis; [Symbol: Aqua Regis] aqua regis; [Symbol: Aqua Vitæ] aqua vitæ; [Symbol: Day] day; [Symbol: Night] night; [Symbol: Amalgam] Amalgam; [Symbol: Alembic] Alembic. CHAPTER VIII. THE DEGENERACY OF ALCHEMY. I have tried to show that alchemy aimed at giving experimental proof of a certain theory of the whole system of nature, including humanity. The practical culmination of the alchemical quest presented a threefold aspect; the alchemists sought the stone of wisdom, for by gaining that they gained the control of wealth; they sought the universal panacea, for that would give them the power of enjoying wealth and life; they sought the soul of the world, for thereby they could hold communion with spiritual existences, and enjoy the fruition of spiritual life. The object of their search was to satisfy their material needs, their intellectual capacities, and their spiritual yearnings. The alchemists of the nobler sort always made the first of these objects subsidiary to the other two; they gave as their reason for desiring to make gold, the hope that gold might become so common that it would cease to be sought after by mankind. The author of _An Open Substance_ says: "Would to God ... all men might become adepts in our art, for then gold, the common idol of mankind, would lose its value, and we should prize it only for its scientific teaching." But the desire to make gold must always have been a very powerful incentive in determining men to attempt the laborious discipline of alchemy; and with them, as with all men, the love of money was the root of much evil. When a man became a student of alchemy merely for the purpose of making gold, and failed to make it--as he always did--it was very easy for him to pretend he had succeeded in order that he might really make gold by cheating other people. Such a man rapidly degenerated into a charlatan; he used the language of alchemy to cover his frauds, and with the hope of deluding his dupes by high-sounding phrases. And, it must be admitted, alchemy lent itself admirably to imposture. It promised unlimited wealth; it encouraged the wildest dreams of the seeker after pleasure; and over these dreams it cast the glamour of great ideas, the idea of the unity of nature, and the idea of communion with other spheres of life, of calling in the help of 'inheritors of unfulfilled renown,' and so it seemed to touch to fine issues the sordidness of unblushing avarice. Moreover, the working with strange ingredients and odd-fashioned instruments, and the employment of mouth-filling phrases, and scraps of occult learning which seemed to imply unutterable things, gave just that pleasing dash of would-be wickedness to the process of consulting the alchemist which acts as a fascination to many people. The earnest person felt that by using the skill and knowledge of the alchemists, for what he deemed a good purpose, he was compelling the powers of evil to work for him and his objects. It was impossible that such a system as alchemy should appear to the plain man of the middle ages, when the whole scheme of life and the universe rested on a magical basis, to be more than a kind of magic which hovered between the black magic of the Sorcerer and the white magic of the Church. Nor is it to be wondered at that a system which lends itself to imposture so easily as alchemy did, should be thought of by the plain man of modern times as having been nothing but a machinery of fraud. It is evident from the _Canon's Yeoman's Tale_ in Chaucer, that many of those who professed to turn the base metals into gold were held in bad repute as early as the 14th century. The "false chanoun" persuaded the priest, who was his dupe, to send his servant for quicksilver, which he promised to make into "as good silver and as fyn, As ther is any in youre purse or myn"; he then gave the priest a "crosselet," and bid him put it on the fire, and blow the coals. While the priest was busy with the fire, This false chanoun--the foulè feend hym fecche!-- Out of his bosom took a bechen cole, In which ful subtilly was maad an hole, And therinne put was of silver lemaille An ounce, and stoppéd was withouten faille The hole with wex, to kepe the lemaille in. The "false chanoun" pretended to be sorry for the priest, who was so busily blowing the fire:-- Ye been right hoot, I se wel how ye swete; Have heer a clooth, and wipe awey the we't. And whylès that the preest wipèd his face, This chanoun took his cole with hardè grace, And leyde it above, upon the middèward Of the crosselet, and blew wel afterward. Til that the colès gonnè fastè brenne. As the coal burned the silver fell into the "crosselet." Then the canon said they would both go together and fetch chalk, and a pail of water, for he would pour out the silver he had made in the form of an ingot. They locked the door, and took the key with them. On returning, the canon formed the chalk into a mould, and poured the contents of the crucible into it. Then he bade the priest, Look what ther is, put in thin hand and grope, Thow fyndè shalt ther silver, as I hope. What, devel of hellè! Sholde it ellis be? Shavyng of silver silver is, _parde!_ He putte his hand in, and took up a teyne Of silver fyn, and glad in every veyne Was this preest, when he saugh that it was so. The conclusion of the _Canon's Yeoman's Tale_ shows that, in the 14th century, there was a general belief in the possibility of finding the philosopher's stone, and effecting the transmutation, although the common practitioners of the art were regarded as deceivers. A disciple of Plato is supposed to ask his master to tell him the "namè of the privee stoon." Plato gives him certain directions, and tells him he must use _magnasia_; the disciple asks-- 'What is Magnasia, good sire, I yow preye?' 'It is a water that is maad, I seye, Of elementés fourè,' quod Plato. 'Telle me the rootè, good sire,' quod he tho, Of that water, if it be yourè wille.' 'Nay, nay,' quod Plato, 'certein that I nylle; The philosophres sworn were everychoon That they sholden discovers it unto noon, Ne in no book it write in no manere, For unto Crist it is so lief and deere, That he wol nat that it discovered bee, But where it liketh to his deitee Man for tenspire, and eek for to deffende Whom that hym liketh; lo, this is the ende.' The belief in the possibility of alchemy seems to have been general sometime before Chaucer wrote; but that belief was accompanied by the conviction that alchemy was an impious pursuit, because the transmutation of baser metals into gold was regarded as trenching on the prerogative of the Creator, to whom alone this power rightfully belonged. In his _Inferno_ (which was probably written about the year 1300), Dante places the alchemists in the eighth circle of hell, not apparently because they were fraudulent impostors, but because, as one of them says, "I aped creative nature by my subtle art." In later times, some of those who pretended to have the secret and to perform great wonders by the use of it, became rich and celebrated, and were much sought after. The most distinguished of these pseudo-alchemists was he who passed under the name of Cagliostro. His life bears witness to the eagerness of human beings to be deceived. Joseph Balsamo was born in 1743 at Palermo, where his parents were tradespeople in a good way of business.[5] In the memoir of himself, which he wrote in prison, Balsamo seeks to surround his birth and parentage with mystery; he says, "I am ignorant, not only of my birthplace, but even of the parents who bore me.... My earliest infancy was passed in the town of Medina, in Arabia, where I was brought up under the name of Acharat." [5] The account of the life of Cagliostro is much condensed from Mr A.E. Waite's _Lives of the Alchemystical Philosophers_. When he was thirteen years of age, Balsamo's parents determined he should be trained for the priesthood, but he ran away from his school. He was then confined in a Benedictine monastery. He showed a remarkable taste for natural history, and acquired considerable knowledge of the use of drugs; but he soon tired of the discipline and escaped. For some years he wandered about in different parts of Italy, living by his wits and by cheating. A goldsmith consulted him about a hidden treasure; he pretended to invoke the aid of spirits, frightened the goldsmith, got sixty ounces of gold from him to carry on his incantations, left him in the lurch, and fled to Messina. In that town he discovered an aged aunt who was sick; the aunt died, and left her money to the Church. Balsamo assumed her family name, added a title of nobility, and was known henceforward as the Count Alessandro Cagliostro. In Messina he met a mysterious person whom he calls Altotas, and from whom, he says in his Memoir, he learnt much. The following account of the meeting of Balsamo and the stranger is taken from Waite's book: "As he was promenading one day near the jetty at the extremity of the port he encountered an individual singularly habited and possessed of a most remarkable countenance. This person, aged apparently about fifty years, seemed to be an Armenian, though, according to other accounts, he was a Spaniard or Greek. He wore a species of caftan, a silk bonnet, and the extremities of his breeches were concealed in a pair of wide boots. In his left hand he held a parasol, and in his right the end of a cord, to which was attached a graceful Albanian greyhound.... Cagliostro saluted this grotesque being, who bowed slightly, but with satisfied dignity. 'You do not reside in Messina, signor?' he said in Sicilian, but with a marked foreign accent. Cagliostro replied that he was tarrying for a few days, and they began to converse on the beauty of the town and on its advantageous situation, a kind of Oriental imagery individualising the eloquence of the stranger, whose remarks were, moreover, adroitly adorned with a few appropriate compliments." Although the stranger said he received no one at his house he allowed Cagliostro to visit him. After various mysterious doings the two went off to Egypt, and afterwards to Malta, where they performed many wonderful deeds before the Grand Master, who was much impressed. At Malta Altotas died, or, at anyrate, vanished. Cagliostro then travelled for some time, and was well received by noblemen, ambassadors, and others in high position. At Rome he fell in love with a young and beautiful lady, Lorenza Feliciani, and married her. Cagliostro used his young wife as a decoy to attract rich and foolish men. He and his wife thrived for a time, and accumulated money and jewels; but a confederate betrayed them, and they fled to Venice, and then wandered for several years in Italy, France, and England. They seem to have made a living by the sale of lotions for the skin, and by practising skilful deceptions. About the year 1770 Cagliostro began to pose as an alchemist. After another period of wandering he paid a second visit to London and founded a secret society, based on (supposed) Egyptian rites, mingled with those of freemasonry. The suggestion of this society is said to have come from a curious book he picked up on a second-hand stall in London. The society attracted people by the strangeness of its initiatory rites, and the promises of happiness and wellbeing made by its founder to those who joined it. Lodges were established in many countries, many disciples were obtained, great riches were amassed, and Cagliostro flourished exceedingly. In his _Histoire du Merveilleux dans les Temps modernes_, Figuier, speaking of Cagliostro about this period of his career, says: "He proclaimed himself the bearer of the mysteries of Isis and Anubis from the far East.... He obtained numerous and distinguished followers, who on one occasion assembled in great force to hear Joseph Balsamo expound to them the doctrines of Egyptian freemasonry. At this solemn convention he is said to have spoken with overpowering eloquence;... his audience departed in amazement and completely converted to the regenerated and purified masonry. None doubted that he was an initiate of the arcana of nature, as preserved in the temple of Apis at the era when Cambyses belaboured that capricious divinity. From this moment the initiations into the new masonry were numerous, albeit they were limited to the aristocracy of society. There are reasons to believe that the grandees who were deemed worthy of admission paid exceedingly extravagantly for the honour." Cagliostro posed as a physician, and claimed the power of curing diseases simply by the laying on of hands. He went so far as to assert he had restored to life the dead child of a nobleman in Paris; the discovery that the miracle was effected by substituting a living child for the dead one caused him to flee, laden with spoil, to Warsaw, and then to Strassburg. Cagliostro entered Strassburg in state, amid an admiring crowd, who regarded him as more than human. Rumour said he had amassed vast riches by the transmutation of base metals into gold. Some people in the crowd said he was the wandering Jew, others that he had been present at the marriage feast of Cana, some asserted he was born before the deluge, and one supposed he might be the devil. The goldsmith whom he had cheated of sixty ounces of gold many years before was in the crowd, and, recognising him, tried to stop the carriage, shouting: "Joseph Balsamo! It is Joseph! Rogue, where are my sixty ounces of gold?" "Cagliostro scarcely deigned to glance at the furious goldsmith; but in the middle of the profound silence which the incident occasioned among the crowd, a voice, apparently in the clouds, uttered with great distinctness the following words: 'Remove this lunatic, who is possessed by infernal spirits.' Some of the spectators fell on their knees, others seized the unfortunate goldsmith, and the brilliant cortege passed on" (Waite). From Strassburg Cagliostro* went to Paris, where he lived in great splendour, curing diseases, making gold and diamonds, mystifying and duping people of all ranks by the splendid ritual and gorgeous feasting of his secret society, and amassing riches. He got entangled in the affair of the Diamond Necklace, and left Paris. Trying to advance his society in Italy he was arrested by the agents of the Inquisition, and imprisoned, then tried, and condemned to death. The sentence was commuted to perpetual imprisonment. After two years in the prison of San Angelo he died at the age of fifty. *Transcriber's Note: Original "Cagliosto". CHAPTER IX. PARACELSUS AND SOME OTHER ALCHEMISTS. The accounts which have come to us of the men who followed the pursuit of the _One Thing_ are vague, scrappy, and confusing. Alchemical books abound in quotations from the writings of _Geber_. Five hundred treatises were attributed to this man during the middle ages, yet we have no certain knowledge of his name, or of the time or place of his birth. Hoefer says he probably lived in the middle of the 8th century, was a native of Mesopotamia, and was named _Djabar Al-Konfi_. Waite calls him _Abou Moussah Djafar al-Sofi_. Some of the mediæval adepts spoke of him as the King of India, others called him a Prince of Persia. Most of the Arabian writers on alchemy and medicine, after the 9th century, refer to Geber as their master. All the MSS. of writings attributed to Geber which have been examined are in Latin, but the library of Leyden is said to possess some works by him written in Arabic. These MSS. contain directions for preparing many metals, salts, acids, oils, etc., and for performing such operations as distillation, cupellation, dissolution, calcination, and the like. Of the other Arabian alchemists, the most celebrated in the middle ages were _Rhasis_, _Alfarabi_, and _Avicenna_, who are supposed to have lived in the 9th and 10th centuries. The following story of Alfarabi's powers is taken from Waite's _Lives of the Alchemystical Philosophers_:-- "Alfarabi was returning from a pilgrimage to Mecca, when, passing through Syria, he stopped at the Court of the Sultan, and entered his presence, while he was surrounded by numerous sage persons, who were discoursing with the monarch on the sciences. Alfarabi ... presented himself in his travelling attire, and when the Sultan desired he should be seated, with astonishing philosophical freedom he planted himself at the end of the royal sofa. The Prince, aghast at his boldness, called one of his officers, and in a tongue generally unknown commanded him to eject the intruder. The philosopher, however, promptly made answer in the same tongue: 'Oh, Lord, he who acts hastily is liable to hasty repentance.' The Prince was equally astounded to find himself understood by the stranger as by the manner in which the reply was given. Anxious to know more of his guest he began to question him, and soon discovered that he was acquainted with seventy languages. Problems for discussion were then propounded to the philosophers, who had witnessed the discourteous intrusion with considerable indignation and disgust, but Alfarabi disputed with so much eloquence and vivacity that he reduced all the doctors to silence, and they began writing down his discourse. The Sultan then ordered his musicians to perform for the diversion of the company. When they struck up, the philosopher accompanied them on a lute with such infinite grace and tenderness that he elicited the unmeasured admiration of the whole distinguished assembly. At the request of the Sultan he produced a piece of his own composing, sang it, and accompanied it with great force and spirit to the delight of all his hearers. The air was so sprightly that even the gravest philosopher could not resist dancing, but by another tune he as easily melted them to tears, and then by a soft unobtrusive melody he lulled the whole company to sleep." The most remarkable of the alchemists was he who is generally known as _Paracelsus_. He was born about 1493, and died about 1540. It is probable that the place of his birth was Einsiedeln, near Zurich. He claimed relationship with the noble family of Bombast von Hohenheim; but some of his biographers doubt whether he really was connected with that family. His name, or at any rate the name by which he was known, was Aureolus Philippus Theophrastus Bombast von Hohenheim. His father in alchemy, Trimethius, Abbot of Spannheim and then of Wurzburg, who was a theologian, a poet, an astronomer, and a necromancer, named him _Paracelsus_; this name is taken by some to be a kind of Græco-Latin paraphrase of von Hohenheim (of high lineage), and to mean "belonging to a lofty place"; others say it signifies "greater than Celsus," who was a celebrated Latin writer on medicine of the 1st century. Paracelsus studied at the University of Basle; but, getting into trouble with the authorities, he left the university, and for some years wandered over Europe, supporting himself, according to one account, by "psalm-singing, astrological productions, chiromantic soothsaying, and, it has been said, by necromantic practices." He may have got as far as Constantinople; as a rumour floated about that he received the Stone of Wisdom from an adept in that city. He returned to Basle, and in 1527 delivered lectures with the sanction of the Rector of the university. He made enemies of the physicians by abusing their custom of seeking knowledge only from ancient writers and not from nature; he annoyed the apothecaries by calling their tinctures, decoctions, and extracts, mere _soup-messes_; and he roused the ire of all learned people by delivering his lectures in German. He was attacked publicly and also anonymously. Of the pamphlets published against him he said, "These vile ribaldries would raise the ire of a turtle-dove." And Paracelsus was no turtle-dove. The following extract from (a translation of) the preface to _The Book concerning the Tinctures of the Philosophers written against those Sophists born since the Deluge_, shews that his style of writing was abusive, and his opinion of himself, to say the least, not very humble:-- "From the middle of this age the Monarchy of all the Arts has been at length derived and conferred on me, Theophrastus Paracelsus, Prince of Philosophy and Medicine. For this purpose I have been chosen by God to extinguish and blot out all the phantasies of elaborate and false works, of delusive and presumptuous words, be they the words of Aristotle, Galen, Avicenna, Mesva, or the dogmas of any among their followers. My theory, proceeding as it does from the light of Nature, can never, through its consistency, pass away or be changed; but in the fifty-eighth year after its millennium and a half it will then begin to flourish. The practice at the same time following upon the theory will be proved by wonderful and incredible signs, so as to be open to mechanics and common people, and they will thoroughly understand how firm and immovable is that Paracelsic Art against the triflings of the Sophists; though meanwhile that sophistical science has to have its ineptitude propped up and fortified by papal and imperial privileges.... So then, you wormy and lousy Sophist, since you deem the monarch of Arcana a mere ignorant, fatuous, and prodigal quack, now, in this mid age, I determine in my present treatise to disclose the honourable course of procedure in these matters, the virtues and preparation of the celebrated Tincture of the Philosophers for the use and honour of all who love the truth, and in order that all who despise the true arts may be reduced to poverty." The turbulent and restless spirit of Paracelsus brought him into open conflict with the authorities of Basle. He fled from that town in 1528, and after many wanderings, he found rest at Salzburg, under the protection of the archbishop. He died at Salzburg in 1541, in his forty-eighth year. The character and abilities of Paracelsus have been vastly praised by some, and inordinately abused by others. One author says of him: "He lived like a pig, looked like a drover, found his greatest enjoyment in the company of the most dissolute and lowest rabble, and throughout his glorious life he was generally drunk." Another author says: "Probably no physician has grasped his life's task with a purer enthusiasm, or devoted himself more faithfully to it, or more fully maintained the moral worthiness of his calling than did the reformer of Einsiedeln." He certainly seems to have been loved and respected by his pupils and followers, for he is referred to by them as "the noble and beloved monarch," "the German Hemes," and "our dear Preceptor and King of Arts." There seems no doubt that Paracelsus discovered many facts which became of great importance in chemistry: he prepared the inflammable gas we now call hydrogen, by the reaction between iron filings and oil of vitriol; he distinguished metals from substances which had been classed with metals but lacked the essential metalline character of ductility; he made medicinal preparations of mercury, lead and iron, and introduced many new and powerful drugs, notably laudanum. Paracelsus insisted that medicine is a branch of chemistry, and that the restoration of the body of a patient to a condition of chemical equilibrium is the restoration to health. Paracelsus trusted in his method; he was endeavouring to substitute direct appeal to nature for appeal to the authority of writers about nature. "After me," he cries, "you Avicenna, Galen, Rhasis, Montagnana and the others. You after me, not I after you. You of Paris, you of Montpellier, you of Swabia, of Meissen and Vienna; you who come from the countries along the Danube and the Rhine; and you, too, from the Islands of the Ocean. Follow me. It is not for me to follow you, for mine is the monarchy." But the work was too arduous, the struggle too unequal. "With few appliances, with no accurate knowledge, with no help from the work of others, without polished and sharpened weapons, and without the skill that comes from long handling of instruments of precision, what could Paracelsus effect in his struggle to wrest her secrets from nature? Of necessity, he grew weary of the task, and tried to construct a universe which should be simpler than that most complex order which refused to yield to his analysis." And so he came back to the universe which man constructs for himself, and exclaimed-- "Each man has ... all the wisdom and power of the world in himself; he possesses one kind of knowledge as much as another, and he who does not find that which is in him cannot truly say that he does not possess it, but only that he was not capable of successfully seeking for it." We leave a great genius, with his own words in our ears: "Have no care of my misery, reader; let me bear my burden myself. I have two failings: my poverty and my piety. My poverty was thrown in my face by a Burgomaster who had perhaps only seen doctors attired in silken robes, never basking in tattered rags in the sunshine. So it was decreed I was not a doctor. For my piety I am arraigned by the parsons, for ... I do not at all love those who teach what they do not themselves practise." CHAPTER X. SUMMARY OF THE ALCHEMICAL DOCTRINE.--THE REPLACEMENT OF THE THREE PRINCIPLES OF THE ALCHEMISTS BY THE SINGLE PRINCIPLE OF PHLOGISTON. The _Sacred Art_, which had its origin and home in Egypt, was very definitely associated with the religious rites, and the theological teaching, recognised by the state. The Egyptian priests were initiated into the mysteries of the divine art: and as the initiated claimed to imitate the work of the deity, the priest was regarded by the ordinary people as something more than a representative, as a mirror, of the divinity. The sacred art of Egypt was transmuted into alchemy by contact with European thought and handicrafts, and the tenets and mysticism of the Catholic Church; and the conception of nature, which was the result of this blending, prevailed from about the 9th until towards the end of the 18th century. Like its predecessor, alchemy postulated an orderly universe; but alchemy was richer in fantastic details, more picturesquely embroidered, more prodigal of strange fancies, than the sacred art of Egypt. The alchemist constructed his ordered scheme of nature on the basis of the supposed universality of life. For him, everything lived, and the life of things was threefold. The alchemist thought he recognised the manifestation of life in the form, or body, of a thing, in its soul, and in its spirit. Things might differ much in appearance, in size, taste, smell, and other outward properties, and yet be intimately related, because, according to the alchemist, they were produced from the same principles, they were animated by the same soul. Things might resemble one another closely in their outward properties and yet differ widely in essential features, because, according to the alchemist, they were formed from different elements, in their spiritual properties they were unlike. The alchemists taught that the true transformation, in alchemical language the transmutation, of one thing into another could be effected only by spiritual means acting on the spirit of the thing, because the transmutation consisted essentially in raising the substance to the highest perfection whereof it was capable; the result of this spiritual action might become apparent in the material form of the substance. In attempting to apply such vague conceptions as these, alchemy was obliged to use the language which had been developed for the expression of human emotions and desires, not only for the explanation of the facts it observed, but also for the bare recital of these facts. The outlook of alchemy on the world outside human beings was essentially anthropomorphic. In the image of man, the alchemist created his universe. In the times when alchemy was dominant, the divine scheme of creation, and the place given to man in that scheme, were supposed to be thoroughly understood. Everything had its place, designed for it from the beginning, and in that place it remained unless it were forced from it by violent means. A great part of the business of experimental alchemy was to discover the natural position, or condition, of each substance; and the discovery was to be made by interpreting the facts brought to light by observation and experiment by the aid of hypotheses deduced from the general scheme of things which had been formed independently of observation or experiment. Alchemy was a part of magic; for magic interprets and corrects the knowledge gained by the senses by the touchstone of generalisations which have been supplied, partly by the emotions, and partly by extra-human authority, and accepted as necessarily true. The conception of natural order which regulates the life of the savage is closely related to that which guided the alchemists. The essential features of both are the notion that everything is alive, and the persuasion that things can be radically acted on only by using life as a factor. There is also an intimate connexion between alchemy and witchcraft. Witches were people who were supposed to make an unlawful use of the powers of life; alchemists were often thought to pass beyond what is permitted to the creature, and to encroach on the prerogative of the Creator. The long duration of alchemy shows that it appealed to some deep-seated want of human beings. Was not that want the necessity for the realisation of order in the universe? Men were unwilling to wait until patient examination of the facts of their own nature, and the facts of nature outside themselves, might lead them to the realisation of the interdependence of all things. They found it easier to evolve a scheme of things from a superficial glance at themselves and their surroundings; naturally they adopted the easier plan. Alchemy was a part of the plan of nature produced by this method. The extraordinary dominancy of such a scheme is testified to by the continued belief in alchemy, although the one experiment, which seems to us to be the crucial experiment of the system, was never accomplished. But it is also to be remembered that the alchemists were acquainted with, and practised, many processes which we should now describe as operations of manufacturing and technical chemistry; and the practical usefulness of these processes bore testimony, of the kind which convinces the plain man, to the justness of their theories. I have always regarded two facts as most interesting and instructive: that the doctrine of the essential unity of all things, and the simplicity of natural order, was accepted for centuries by many, I think one may say, by most men, as undoubtedly a true presentation of the divine scheme of things; and, secondly, that in more recent times people were quite as certain of the necessary truth of the doctrine, the exact opposite of the alchemical, that the Creator had divided his creation into portions each of which was independent of all the others. Both of these schemes were formed by the same method, by introspection preceding observation; both were overthrown by the same method, by observation and experiment proceeding hand in hand with reasoning. In each case, the humility of science vanquished the conceit of ignorance. The change from alchemy to chemistry is an admirable example of the change from a theory formed by looking inwards, and then projected on to external facts, to a theory formed by studying facts, and then thinking about them. This change proceeded slowly; it is not possible to name a time when it may be said, here alchemy finishes and chemistry begins. To adapt a saying of one of the alchemists, quoted in a former chapter; alchemy would not easily give up its nature, and fought for its life; but an agent was found strong enough to overcome and kill it, and then that agent also had the power to change the lifeless remains into a new and pure body. The agent was the accurate and imaginative investigation of facts. The first great step taken in the path which led from alchemy to chemistry was the substitution of one Principle, the Principle of Phlogiston, for the three Principles of salt, sulphur, and mercury. This step was taken by concentrating attention and investigation, by replacing the superficial examination of many diverse phenomena by the more searching study of one class of occurrences. That the field of study should be widened, it was necessary that it should first be narrowed. Lead, tin, iron, or copper is calcined. The prominent and striking feature of these events is the disappearance of the metal, and the formation of something very unlike it. But the original metal is restored by a second process, which is like the first because it also is a calcination, but seems to differ from the first operation in that the burnt metal is calcined with another substance, with grains of wheat or powdered charcoal. Led thereto by their theory that destruction must precede re-vivification, death must come before resurrection, the alchemists confined their attention to one feature common to all calcinations of metals, and gave a superficial description of these occurrences by classing them together as processes of mortification. Sulphur, wood, wax, oil, and many other things are easily burned: the alchemists said, these things also undergo mortification, they too are killed; but, as "man can restore that which man has destroyed," it must be possible to restore to life the thing which has been mortified. The burnt sulphur, wood, wax, or oil, is not really dead, the alchemists argued; to use the allegory of Paracelsus, they are like young lions which are born dead, and are brought to life by the roaring of their parents: if we make a sufficiently loud noise, if we use the proper means, we shall bring life into what seems to be dead material. As it is the roaring of the parents of the young lions which alone can cause the still-born cubs to live, so it is only by the spiritual agency of life, proceeded the alchemical argument, that life can be brought into the mortified sulphur, wood, wax, and oil. The alchemical explanation was superficial, theoretical, in the wrong meaning of that word, and unworkable. It was superficial because it overlooked the fact that the primary calcination, the mortification, of the metals, and the other substances, was effected in the air, that is to say, in contact with something different from the thing which was calcined; the explanation was of the kind which people call theoretical, when they wish to condemn an explanation and put it out of court, because it was merely a re-statement of the facts in the language of a theory which had not been deduced from the facts themselves, or from facts like those to be explained, but from what were supposed to be facts without proper investigation, and, if facts, were of a totally different kind from those to which the explanation applied; and lastly, the explanation was unworkable, because it suggested no method whereby its accuracy could be tested, no definite line of investigation which might be pursued. That great naturalist, the Honourable Robert Boyle (born in 1626, died in 1691), very perseveringly besought those who examined processes of calcination to pay heed to the action of everything which might take part in the processes. He was especially desirous they should consider what part the air might play in calcinations; he spoke of the air as a "menstruum or additament," and said that, in such operations as calcination, "We may well take the freedom to examine ... whether there intervene not a coalition of the parts of the body wrought upon with those of the menstruum, whereby the produced concrete may be judged to result from the union of both." It was by examining the part played by the air in processes of calcination and burning that men at last became able to give approximately complete descriptions of these processes. Boyle recognised that the air is not a simple or elementary substance; he spoke of it as "a confused aggregate of effluviums from such differing bodies, that, though they all agree in constituting by their minuteness and various motions one great mass of fluid matter, yet perhaps there is scarce a more heterogeneous body in the world." Clement of Alexandria who lived in the end of the 2nd, and the early part of the 3rd, century A.D., seems to have regarded the air as playing a very important part in combustions; he said--"Airs are divided into two categories; an air for the divine flame, which is the soul; and a material air which is the nourisher of sensible fire, and the basis of combustible matter." Sentences like that I have just quoted are found here and there in the writings of the earlier and later alchemists; now and again we also find statements which may be interpreted, in the light of the fuller knowledge we now have, as indicating at least suspicions that the atmosphere is a mixture of different kinds of air, and that only some of these take part in calcining and burning operations. Those suspicions were confirmed by experiments on the calcination of metals and other substances, conducted in the 17th century by Jean Rey a French physician, and by John Mayow of Oxford. But these observations and the conclusions founded on them, did not bear much fruit until the time of Lavoisier, that is, towards the close of the 18th century. They were overshadowed and put aside by the work of Stahl (1660-1724). Some of the alchemists of the 14th, 15th and 16th centuries taught that combustion and calcination are processes wherein _the igneous principle_ is destroyed, using the word "destroyed" in its alchemical meaning. This description of processes of burning was much more in keeping with the ideas of the time than that given by Boyle, Rey and Mayow. It was adopted by Stahl, and made the basis of a general theory of those changes wherein one substance disappears and another, or others, very unlike it, are produced. That he might bring into one point of view, and compare the various changes effected by the agency of fire, Stahl invented a new Principle, which he named _Phlogiston_, and constructed an hypothesis which is generally known as the phlogistic theory. He explained, and applied, this hypothesis in various books, especially in one published at Halle in 1717. Stahl observed that many substances which differed much from one another in various respects were alike in one respect; they were all combustible. All the combustible substances, he argued, must contain a common principle; he named this supposed principle, _phlogiston_ (from the Greek word _phlogistos_ = burnt, or set on fire). Stahl said that the phlogiston of a combustible thing escapes as the substance burns, and, becoming apparent to the senses, is named fire or flame. The phlogiston in a combustible substance was supposed to be so intimately associated with something else that our senses cannot perceive it; nevertheless, the theory said, it is there; we can see only the escaping phlogiston, we can perceive only the phlogiston which is set free from its combination with other things. The theory thought of phlogiston as imprisoned in the thing which can be burnt, and as itself forming part of the prison; that the prisoner should be set free, the walls of the prison had to be removed; the freeing of the prisoner destroyed the prison. As escaping, or free, phlogiston was called fire, or flame, so the phlogiston in a combustible substance was sometimes called combined fire, or flame in the state of combination. A peculiarity of the strange thing called phlogiston was that it preferred to be concealed in something, hidden, imprisoned, combined; free phlogiston* was supposed to be always ready to become combined phlogiston. *Transcriber's Note: Original "phlogstion". The phlogistic theory said that what remains when a substance has been burnt is the original substance deprived of phlogiston; and, therefore, to restore the phlogiston to the product of burning is to re-form the combustible substance. But how is such a restoration of phlogiston to be accomplished? Evidently by heating the burnt thing with something which is very ready to burn. Because, according to the theory, everything which can be burnt contains phlogiston, the more ready a substance is to burn the richer it is in phlogiston; burning is the outrush of phlogiston, phlogiston prefers to be combined with something; therefore, if you mix what remains after burning, with something which is very combustible, and heat the mixture, you are bringing the burnt matter under conditions which are very favourable for the reception of phlogiston by it, for you are bringing it into intimate contact with something from which freedom-hating phlogiston is being forced to escape. Charcoal, sulphur, phosphorus, oils and fats are easily burnt; these substances were, therefore, chosen for the purpose of changing things which had been burnt into things which could again be burnt; these, and a few other substances like these, were classed together, and called _phlogisticating agents_. Very many of the substances which were dealt with by the experimenters of the last quarter of the 17th, and the first half of the 18th, century, were either substances which could be burned, or those which had been produced by burning; hence the phlogistic theory brought into one point of view, compared, and emphasised the similarities between, a great many things which had not been thought of as connected before that theory was promulgated. Moreover, the theory asserted that all combustible, or incinerable, things are composed of phlogiston, and another principle, or, as was often said, another element, which is different in different kinds of combustible substances. The metals, for instance, were said to be composed of phlogiston and an earthy principle or element, which was somewhat different in different metals. The phlogisteans taught that the earthy principle of a metal remains in the form of ash, cinders, or calx, when the metal is calcined, or, as they expressed it, when the metal is deprived of its phlogiston. The phlogistic theory savoured of alchemy; it postulated an undefined, undefinable, intangible Principle; it said that all combustible substances are formed by the union of this Principle with another, which is sometimes of an earthy character, sometimes of a fatty nature, sometimes highly volatile in habit. Nevertheless, the theory of Stahl was a step away from purely alchemical conceptions towards the accurate description of a very important class of changes. The principle of phlogiston could be recognised by the senses as it was in the act of escaping from a substance; and the other principle of combustible things was scarcely a Principle in the alchemical sense, for, in the case of metals at any rate, it remained when the things which had contained it were burnt, and could be seen, handled, and weighed. To say that metals are composed of phlogiston and an earthy substance, was to express facts in such a language that the expression might be made the basis of experimental inquiry; it was very different from the assertion that metals are produced by the spiritual actions of the three Principles, salt, mercury and sulphur, the first of which is not salt, the second is not mercury, and the third is not sulphur. The followers of Stahl often spoke of metals as composed of phlogiston and an _element_ of an earthy character; this expression also was an advance, from the hazy notion of _Element_ in purely alchemical writings, towards accuracy and fulness of description. An element was now something which could he seen and experimented with; it was no longer a semi-spiritual existence which could not be grasped by the senses. The phlogistic theory regarded the calcination of a metal as the separation of it into two things, unlike the metal, and unlike each other; one of these things was phlogiston, the other was an earth-like residue. The theory thought of the re-formation of a metal from its calx, that is, the earthy substance which remains after combustion, as the combination of two things to produce one, apparently homogeneous, substance. Metals appeared to the phlogisteans, as they appeared to the alchemists, to be composite substances. Processes of burning were regarded by alchemists and phlogisteans alike, as processes of simplification. The fact had been noticed and recorded, during the middle ages, that the earth-like matter which remains when a metal is calcined is heavier than the metal itself. From this fact, modern investigators of natural phenomena would draw the conclusion, that calcination of a metal is an addition of something to the metal, not a separation of the metal into different things. It seems impossible to us that a substance should be separated into portions, and one of these parts should weigh as much as, or more than, the whole. The exact investigation of material changes called chemistry rests on the statement that _mass_, and mass is practically measured by _weight_, is the one property of what we call matter, the determination whereof enables us to decide whether a change is a combination, or coalescence, of different things, or a separation of one thing into parts. That any part of a material system can be removed without the weight of the portion which remains being less than the original weight of the whole system, is unthinkable, in the present state of our knowledge of material changes. But in the 17th century, and throughout most of the 18th, only a few of those who examined changes in the properties of substances paid heed to changes of weight; they had not realised the importance of the property of mass, as measured by weight. The convinced upholder of the phlogistic theory had two answers to the argument, that, because the earth-like product of the calcination of a metal weighs more than the metal itself, therefore the metal cannot have lost something in the process; for, if one portion of what is taken away weighs more than the metal from which it has been separated, it is evident that the weight of the two portions into which the metal is said to have been divided must be considerably greater than the weight of the undivided metal. The upholders of the theory sometimes met the argument by saying, "Of course the calx weighs more than the metal, because phlogiston tends to lighten a body which contains it; and therefore the body weighs more after it has lost phlogiston than it did when the phlogiston formed part of it;" sometimes, and more often, their answer was--"loss or gain of weight is an accident, the essential thing is change of qualities." If the argument against the separation of a metal into two constituents, by calcination, were answered to-day as it was answered by the upholders of the phlogistic theory, in the middle of the 18th century, the answers would justly be considered inconsequent and ridiculous. But it does not follow that the statements were either far-fetched or absurd at the time they were made. They were expressed in the phraseology of the time; a phraseology, it is true, sadly lacking in consistency, clearness, and appropriateness, but the only language then available for the description of such changes as those which happen when metals are calcined. One might suppose that it must always have sounded ridiculous to say that the weight of a thing can be decreased by adding something to it, that part of a thing weighs more than the whole of it. But the absurdity disappears if it can be admitted that mass, which is measured by weight, may be a property like colour, or taste, or smell; for the colour, taste, or smell of a thing may certainly be made less by adding something else, and the colour, taste, or smell of a thing may also be increased by adding something else. If we did not know that what we call _quantity of substance_ is measured by the property named _mass_, we might very well accept the proposition that the entrance of phlogiston into a substance decreases the quantity, hence the mass, and, therefore, the weight, of the substance. Although Stahl and his followers were emerging from the trammels of alchemy, they were still bound by many of the conceptions of that scheme of nature. We have learned, in previous chapters, that the central idea of alchemy was expressed in the saying: "Matter must be deprived of its properties in order to draw out its soul." The properties of substances are everything to the modern chemist--indeed, such words as iron, copper, water, and gold are to him merely convenient expressions for certain definable groups of properties--but the phlogisteans regarded the properties of things, including mass, as of secondary importance; they were still trying to get beneath the properties of a thing, to its hypothetical essence, or substance. Looking back, we cannot think of phlogiston as a substance, or as a thing, in the modern meanings of these terms as they are used in natural science. Nowadays we think, we are obliged to think, of the sum of the quantities of all the things in the universe as unchanging, and unchangeable by any agency whereof we have definite knowledge. The meaning we give to the word _thing_ rests upon the acceptance of this hypothesis. But the terms _substance_, _thing_, _properties_ were used very vaguely a couple of centuries ago; and it would be truly absurd to carry back to that time the meanings which we give to these terms to-day, and then to brand as ridiculous the attempts of the men who studied, then, the same problems which we study now, to express the results of their study in generalisations which employed the terms in question, in what seems to us a loose, vague, and inexact manner. By asserting, and to some extent experimentally proving, the existence of one principle in many apparently very different substances (or, as would be said to-day, one property common to many substances), the phlogistic theory acted as a very useful means for collecting, and placing in a favourable position for closer inspection, many substances which would probably have remained scattered and detached from one another had this theory not been constructed. A single assumption was made, that all combustible substances are alike in one respect, namely, in containing combined fire, or phlogiston; by the help of this assumption, the theory of phlogiston emphasised the fundamental similarity between all processes of combustion. The theory of phlogiston was extraordinarily simple, compared with the alchemical vagaries which preceded it. Hoefer says, in his _Histoire de la Chimie_, "If it is true that simplicity is the distinctive character of verity, never was a theory so true as that of Stahl." The phlogistic theory did more than serve as a means for bringing together many apparently disconnected facts. By concentrating the attention of the students of material changes on one class of events, and giving descriptions of these events without using either of the four alchemical Elements, or the three Principles, Stahl, and those who followed him, did an immense service to the advancement of clear thinking about natural occurrences. The principle of phlogiston was more tangible, and more readily used, than the Salt, Sulphur, and Mercury of the alchemists; and to accustom people to speak of the material substance which remained when a metal, or other combustible substance, was calcined or burnt, as one of the _elements_ of the thing which had been changed, prepared the way for the chemical conception of an element as a definite substance with certain definite properties. In addition to these advantages, the phlogistic theory was based on experiments, and led to experiments, the results of which proved that the capacity to undergo combustion might be conveyed to an incombustible substance, by causing it to react with some other substance, itself combustible, under definite conditions. The theory thus prepared the way for the representation of a chemical change as an interaction between definite kinds of substances, marked by precise alterations both of properties and composition. The great fault of the theory of phlogiston, considered as a general conception which brings many facts into one point of view, and leads the way to new and exact knowledge, was its looseness, its flexibility. It was very easy to make use of the theory in a broad and general way; by stretching it here, and modifying it there, it seemed to cover all the facts concerning combustion and calcination which were discovered during two generations after the publication of Stahl's books. But many of the subsidiary hypotheses which were required to make the theory cover the new facts were contradictory, or at any rate seemed to be contradictory, of the primary assumptions of the theory. The addition of this ancillary machinery burdened the mechanism of the theory, threw it out of order, and finally made it unworkable. The phlogistic theory was destroyed by its own cumbersomeness. A scientific theory never lasts long if its fundamental assumptions are stated so loosely that they may be easily modified, expanded, contracted, and adjusted to meet the requirements of newly discovered facts. It is true that the theories which have been of the greatest service in science, as summaries of the relations between established facts, and suggestions of lines of investigation, have been stated in terms whose full meaning has gradually unfolded itself. But the foundations of these theories have been at once so rigidly defined and clearly stated as to be incapable of essential modification, and so full of meaning and widely applicable as to cover large classes of facts which were unknown when the theories were constructed. Of the founders of the lasting and expansible theories of natural science, it may be said, that "thoughts beyond their thoughts to those high bards were given." CHAPTER XI. THE EXAMINATION OF THE PHENOMENA OF COMBUSTION. The alchemists thought that the most effectual method of separating a complex substance into more simple substances was to subject it to the action of heat. They were constantly distilling, incinerating, subliming, heating, in order that the spirit, or inner kernel of things, might be obtained. They took for granted that the action of fire was to simplify, and that simplification proceeded whatever might be the nature of the substance which was subjected to this action. Boyle insisted that the effect of heating one substance may be, and often is, essentially different from the effect of heating another substance; and that the behaviour of the same substance when heated, sometimes varies when the conditions are changed. He takes the example of heating sulphur or brimstone: "Exposed to a moderate fire in subliming pots, it rises all into dry, and almost tasteless, flowers; whereas being exposed to a naked fire, it affords store of a saline and fretting liquor." Boyle thought that the action of fire was not necessarily to separate a thing into its principles or elements, but, in most cases, was either to rearrange the parts of the thing, so that new, and it might be, more complex things, were produced, or to form less simple things by the union of the substance with what he called, "the matter of fire." When the product of heating a substance, for example, tin or lead, weighed more than the substance itself, Boyle supposed that the gain in weight was often caused by the "matter of fire" adding itself to the substance which was heated. He commended to the investigation of philosophers this "subtil fluid," which is "able to pierce into the compact and solid bodies of metals, and add something to them that has no despicable weight upon the balance, and is able for a considerable time to continue fixed in the fire." Boyle also drew attention to the possibility of action taking place between a substance which is heated and some other substance, wherewith the original thing may have been mixed. In a word, Boyle showed that the alchemical assumption--fire simplifies--was too simple; and he taught, by precept and example, that the only way of discovering what the action of fire is, on this substance or on that, is to make accurate experiments. "I consider," he says, "that, generally speaking, to render a reason of an effect or phenomenon, is to deduce it from something else in nature more known than itself; and that consequently there may be divers kinds of degrees of explication of the same thing." Boyle published his experiments and opinions concerning the action of fire on different substances in the seventies of the 17th century; Stahl's books, which laid the foundation of the phlogistic theory, and confirmed the alchemical opinion that the action of fire is essentially a simplifying action, were published about forty years later. But fifty years before Boyle, a French physician, named Jean Rey, had noticed that the calcination of a metal is the production of a more complex, from a less complex substance; and had assigned the increase in weight which accompanies that operation to the attachment of particles of the air to the metal. A few years before the publication of Boyle's work, from which I have quoted, John Mayow, student of Oxford, recounted experiments which led to the conclusion that the air contains two substances, one of which supports combustion and the breathing of animals, while the other extinguishes fire. Mayow called the active component of the atmosphere _fiery air_; but he was unable to say definitely what becomes of this fiery air when a substance is burnt, although he thought that, in some cases, it probably attaches itself to the burning substances, by which, therefore, it may be said to be fixed. Mayow proved that the air wherein a substance is burnt, or an animal breathes, diminishes in volume during the burning, or the breathing. He tried, without much success, to restore to air that part of it which disappears when combustion, or respiration, proceeds in it. What happens when a substance is burnt in the air? The alchemists answered this question by asserting that the substance is separated or analysed into things simpler than itself. Boyle said: the process is not necessarily a simplification; it may be, and certainly sometimes is, the formation of something more complicated than the original substance, and when this happens, the process often consists in the fixation of "the matter of fire" by the burning substance. Rey said: calcination, of a metal at anyrate, probably consists in the fixation of particles of air by the substance which is calcined. Mayow answered the question by asserting, on the ground of the results of his experiments, that the substance which is being calcined lays hold of a particular constituent of the air, not the air as a whole. Now, it is evident that if Mayow's answer was a true description of the process of calcination, or combustion, it should be possible to separate the calcined substance into two different things, one of which would be the thing which was calcined, and the other would be that constituent of the air which had united with the burning, or calcining, substance. It seems clear to us that the one method of proving the accuracy of Mayow's supposition must be, to weigh a definite, combustible, substance--say, a metal; to calcine this in a measured quantity of air; to weigh the product, and to measure the quantity of air which remains; to separate the product of calcination into the original metal, and a kind of air or gas; to prove that the metal thus obtained is the same, and has the same weight, as the metal which was calcined; and to prove that the air or gas obtained from the calcined metal is the same, both in quality and quantity, as the air which disappeared in the process of calcination. This proof was not forthcoming until about a century after the publication of Mayow's work. The experiments which furnished the proof were rendered possible by a notable discovery made on the 1st of August 1774, by the celebrated Joseph Priestley. Priestley prepared many "airs" of different kinds: by the actions of acids on metals, by allowing vegetables to decay, by heating beef, mutton, and other animal substances, and by other methods. He says: "Having procured a lens of twelve inches diameter and twenty inches focal distance, I proceeded with great alacrity to examine, by the help of it, what kind of air a great variety of substances, natural and factitious, would yield.... With this apparatus, after a variety of other experiments.... on the 1st of August, 1774, I endeavoured to extract air from _mercurius calcinatus per se_; and I presently found that, by means of this lens, air was expelled from it very readily. Having got about three or four times as much as the bulk of my materials, I admitted water to it, and found that it was not imbibed by it. But what surprised me more than I can well express was, that a candle burned in this air with a remarkably vigorous flame.... I was utterly at a loss how to account for it." [Illustration: FIG. XVI.] The apparatus used by Priestley, in his experiments on different kinds of air, is represented in Fig. XVI., which is reduced from an illustration in Priestley's book on _Airs_. Priestley had made a discovery which was destined to change Alchemy into Chemistry. But he did not know what his discovery meant. It was reserved for the greatest of all chemists, Antoine Lavoisier, to use the fact stumbled on by Priestley. After some months Priestley began to think it possible that the new "air" he had obtained from calcined mercury might be fit for respiration. To his surprise he found that a mouse lived in this air much longer than in common air; the new air was evidently better, or purer, than ordinary air. Priestley measured what he called the "goodness" of the new air, by a process of his own devising, and concluded that it was "between four and five times as good as common air." Priestley was a thorough-going phlogistean. He seems to have been able to describe the results of his experiments only in the language of the phlogistic theory; just as the results of most of the experiments made to-day on the changes of compounds of the element carbon cannot be described by chemists except by making use of the conceptions and the language of the atomic and molecular theory.[6] [6] I have given numerous illustrations of the truth of this statement in the book, in this series, entitled _The Story of the Wanderings of Atoms_. The upholder of the phlogistic theory could not think of burning as possible unless there was a suitable receptacle for the phlogiston of the burning substance: when burning occurred in the air, the part played by the air, according to the phlogistic chemist, was to receive the expelled phlogiston; in this sense the air acted as the _pabulum_, or nourishment, of the burning substance. Inasmuch as substances burned more vigorously and brilliantly in the new air than in common air, Priestley argued that the new air was more ready, more eager, than ordinary air, to receive phlogiston; and, therefore, that the new air contained less phlogiston than ordinary air, or, perhaps, no phlogiston. Arguing thus, Priestley, of course, named the new aeriform substance _dephlogisticated air_, and thought of it as ordinary air deprived of some, or it might be all, of its phlogiston. The breathing of animals and the burning of substances were supposed to load the atmosphere with phlogiston. Priestley spoke of the atmosphere as being constantly "vitiated," "rendered noxious," "depraved," or "corrupted" by processes of respiration and combustion; he called those processes whereby the atmosphere is restored to its original condition (or "depurated," as he said), "dephlogisticating processes." As he had obtained his _dephlogisticated air_ by heating the calx of mercury, that is the powder produced by calcining mercury in the air, Priestley was forced to suppose that the calcination of mercury in the air must be a more complex occurrence than merely the expulsion of phlogiston from the mercury: for, if the process consisted only in the expulsion of phlogiston, how could heating what remained produce exceedingly pure ordinary air? It seemed necessary to suppose that not only was phlogiston expelled from mercury during calcination, but that the mercury also imbibed some portion, and that the purest portion, of the surrounding air. Priestley did not, however, go so far as this; he was content to suppose that in some way, which he did not explain, the process of calcination resulted in the loss of phlogiston by the mercury, and the gain, by the dephlogisticated mercury, of the property of yielding exceedingly pure or dephlogisticated air when it was heated very strongly. Priestley thought of properties in much the same way as the alchemists thought of them, as wrappings, or coverings of an essential something, from which they can be removed and around which they can again be placed. The protean principle of phlogiston was always at hand, and, by skilful management, was ready to adapt itself to any facts. Before the phenomena of combustion could be described accurately, it was necessary to do two things; to ignore the theory of phlogiston, and to weigh and measure all the substances which take part in some selected processes of burning. Looking back at the attempts made in the past to describe natural events, we are often inclined to exclaim, "Why did investigators bind themselves with the cords of absurd theories; why did they always wear blinkers; why did they look at nature through the distorting mists rising from their own imaginations?" We are too ready to forget the tremendous difficulties which beset the path of him who is seeking accurate knowledge. "To climb steep hills requires slow pace at first." Forgetting that the statements wherein the men of science of our own time describe the relations between natural events are, and must be, expressed in terms of some general conception, some theory, of these relations; forgetting that the simplest natural occurrence is so complicated that our powers of description are incapable of expressing it completely and accurately; forgetting the uselessness of disconnected facts; we are inclined to overestimate the importance of our own views of nature's ways, and to underestimate the usefulness of the views of our predecessors. Moreover, as naturalists have not been obliged, in recent times, to make a complete renunciation of any comprehensive theory wherein they had lived and moved for many years, we forget the difficulties of breaking loose from a way of looking at natural events which has become almost as real as the events themselves, of abandoning a language which has expressed the most vividly realised conceptions of generations of investigators, of forming a completely new mental picture of natural occurrences, and developing a completely new language for the expression of those conceptions and these occurrences. The younger students of natural science of to-day are beginning to forget what their fathers told them of the fierce battle which had to be fought, before the upholders of the Darwinian theory of the origin of species were able to convince those for whom the older view, that species are, and always have been, absolutely distinct, had become a matter of supreme scientific, and even ethical, importance. A theory which has prevailed for generations in natural science, and has been accepted and used by everyone, can be replaced by a more accurate description of the relations between natural facts, only by the determination, labour, and genius of a man of supreme power. Such a service to science, and humanity, was rendered by Darwin; a like service was done, more than three-quarters of a century before Darwin, by Lavoisier. Antoine Laurent Lavoisier was born in Paris in 1743. His father, who was a merchant in a good position, gave his son the best education which was then possible, in physical, astronomical, botanical, and chemical science. At the age of twenty-one, Lavoisier gained the prize offered by the Government for devising an effective and economical method of lighting the public streets. From that time until, on the 8th of May 1794, the Government of the Revolution declared, "The Republic has no need of men of science," and the guillotine ended his life, Lavoisier continued his researches in chemistry, geology, physics, and other branches of natural science, and his investigations into the most suitable methods of using the knowledge gained by naturalists for advancing the welfare of the community. In Chapter VI., I said that when an alchemist boiled water in an open vessel, and obtained a white earthy solid, in place of the water which disappeared, he was producing some sort of experimental proof of the justness of his assertion that water can be changed into earth. Lavoisier began his work on the transformations of matter by demonstrating that this alleged transmutation does not happen; and he did this by weighing the water, the vessel, and the earthy solid. Lavoisier had constructed for him a pelican of white glass (see Fig. XI., p. 88), with a stopper of glass. He cleaned, dried, and weighed this vessel; then he put into it rain-water which he had distilled eight times; he heated the vessel, removing the stopper from time to time to allow the expanding air to escape, then put in the stopper, allowed the vessel to cool, and weighed very carefully. The difference between the second and the first weighing was the weight of water in the vessel. He then fastened the stopper securely with cement, and kept the apparatus at a temperature about 30° or 40° below that of boiling water, for a hundred and one days. At the end of that time a fine white solid had collected on the bottom of the vessel. Lavoisier removed the cement from the stopper, and weighed the apparatus; the weight was the same as it had been before the heating began. He removed the stopper; air rushed in, with a hissing noise. Lavoisier concluded that air had not penetrated through the apparatus during the process of heating. He then poured out the water, and the solid which had formed in the vessel, set them aside, dried, and weighed the pelican; it had lost 17-4/10 grains. Lavoisier concluded that the solid which had formed in the water was produced by the solvent action of the water on the glass vessel. He argued that if this conclusion was correct, the weight of the solid must be equal to the loss of weight suffered by the vessel; he therefore separated the solid from the water in which it was suspended, dried, and weighed it. The solid weighed 4-9/10 grains. Lavoisier's conclusion seemed to be incorrect; the weight of the solid, which was supposed to be produced by the action of the water on the vessel, was 12-1/2 grains less than the weight of the material removed from the vessel. But some of the material which was removed from the vessel might have remained dissolved in the water: Lavoisier distilled the water, which he had separated from the solid, in a glass vessel, until only a very little remained in the distilling apparatus; he poured this small quantity into a glass basin, and boiled until the whole of the water had disappeared as steam. There remained a white, earthy solid, the weight of which was 15-1/2 grains. Lavoisier had obtained 4-9/10 + 15-1/2 = 20-2/5 grains of solid; the pelican had lost 17-2/5 grains. The difference between these weights, namely, 3 grains, was accounted for by Lavoisier as due to the solvent action of the water on the glass apparatus wherein it had been distilled, and on the glass basin wherein it had been evaporated to dryness. Lavoisier's experiments proved that when distilled water is heated in a glass vessel, it dissolves some of the material of the vessel, and the white, earthy solid which is obtained by boiling down the water is merely the material which has been removed from the glass vessel. His experiments also proved that the water does not undergo any change during the process; that at the end of the operation it is what it was at the beginning--water, and nothing but water. By this investigation Lavoisier destroyed part of the experimental basis of alchemy, and established the one and only method by which chemical changes can be investigated; the method wherein constant use is made of the balance. Lavoisier now turned his attention to the calcination of metals, and particularly the calcination of tin. Boyle supposed that the increase in weight which accompanies the calcination of a metal is due to the fixation of "matter of fire" by the calcining metal; Rey regarded the increase in weight as the result of the combination of the air with the metal; Mayow thought that the atmosphere contains two different kinds of "airs," and one of these unites with the heated metal. Lavoisier proposed to test these suppositions by calcining a weighed quantity of tin in a closed glass vessel, which had been weighed before, and should be weighed after, the calcination. If Boyle's view was correct, the weight of the vessel and the tin would be greater at the end than it was at the beginning of the operation; for "matter of fire" would pass through the vessel and unite with the metal. If there was no change in the total weight of the apparatus and its contents, and if air rushed in when the vessel was opened after the calcination, and the total weight was then greater than at the beginning of the process, it would be necessary to adopt either the supposition of Rey or that of Mayow. Lavoisier made a series of experiments. The results were these: there was no change in the total weight of the apparatus and its contents; when the vessel was opened after the calcination was finished, air rushed in, and the whole apparatus now weighed more than it did before the vessel was opened; the weight of the air which rushed in was exactly equal to the increase in the weight of the tin produced by the calcination, in other words, the weight of the inrushing air was exactly equal to the difference between the weights of the tin and the calx formed by calcining the tin. Lavoisier concluded that to calcine tin is to cause it to combine with a portion of the air wherein it is calcined. The weighings he made showed that about one-fifth of the whole weight of air in the closed flask wherein he calcined tin had disappeared during the operation. Other experiments led Lavoisier to suspect that the portion of the air which had united with the tin was different from the portion which had not combined with that metal. He, therefore, set himself to discover whether there are different kinds of "airs" in the atmosphere, and, if there is more than one kind of "air," what is the nature of that "air" which combines with a metal in the process of calcination. He proposed to cause a metallic calx (that is, the substance formed by calcining a metal in the air) to give up the "air" which had been absorbed in its formation, and to compare this "air" with atmospheric air. About this time Priestley visited Paris, saw Lavoisier, and told him of the new "air" he had obtained by heating calcined mercury. Lavoisier saw the great importance of Priestley's discovery; he repeated Priestley's experiment, and concluded that the air, or gas, which he refers to in his Laboratory Journal as "l'air dephlogistique de M. Priestley" was nothing else than the purest portion of the air we breathe. He prepared this "air" and burned various substances in it. Finding that very many of the products of these combustions had the properties of acids, he gave to the new "air" the name _oxygen_, which means _the acid-producer_. At a later time, Lavoisier devised and conducted an experiment which laid bare the change of composition that happens when mercury is calcined in the air. He calcined a weighed quantity of mercury for many days in a measured volume of air, in an apparatus arranged so that he was able to determine how much of the air disappeared during the process; he collected and weighed the red solid which formed on the surface of the heated mercury; finally he heated this red solid to a high temperature, collected and measured the gas which was given off, and weighed the mercury which was produced. The sum of the weights of the mercury and the gas which were produced by heating the calcined mercury was equal to the weight of the calcined mercury; and the weight of the gas produced by heating the calcined mercury was equal to the weight of the portion of the air which had disappeared during the formation of the calcined mercury. This experiment proved that the calcination of mercury in the air consists in the combination of a constituent of the air with the mercury. Fig. XVII. (reduced from an illustration in Lavoisier's Memoir) represents the apparatus used by Lavoisier. Mayow's supposition was confirmed. [Illustration: FIG. XVII.] Lavoisier made many more experiments on combustion, and proved that in every case the component of the atmosphere which he had named oxygen combined with the substance, or with some part of the substance, which was burned. By these experiments the theory of Phlogiston was destroyed; and with its destruction, the whole alchemical apparatus of Principles and Elements, Essences and Qualities, Souls and Spirits, disappeared. CHAPTER XII. THE RECOGNITION OF CHEMICAL CHANGES AS THE INTERACTIONS OF DEFINITE SUBSTANCES. The experimental study of combustion made by Lavoisier proved the correctness of that part of Stahl's phlogistic theory which asserted that all processes of combustion are very similar, but also proved that this likeness consists in the combination of a distinct gaseous substance with the material undergoing combustion, and not in the escape therefrom of the _Principle of fire_, as asserted by the theory of Stahl. After about the year 1790, it was necessary to think of combustions in the air as combinations of a particular gas, or _air_, with the burning substances, or some portions of them. This description of processes of burning necessarily led to a comparison of the gaseous constituent of the atmosphere which played so important a part in these processes, with the substances which were burned; it led to the examination of the compositions of many substances, and made it necessary to devise a language whereby these compositions could be stated clearly and consistently. We have seen, in former chapters, the extreme haziness of the alchemical views of composition, and the connexions between composition and properties. Although Boyle[7] had stated very lucidly what he meant by the composition of a definite substance, about a century before Lavoisier's work on combustion, nevertheless the views of chemists concerning composition remained very vague and incapable of definite expression, until the experimental investigations of Lavoisier enabled him to form a clear mental picture of chemical changes as interactions between definite quantities of distinct substances. [7] Boyle said, in 1689, "I mean by elements ... certain primitive and simple, or perfectly unmixed bodies; which not being made of any other bodies, or of one another, are the ingredients of which all those called perfectly mixt bodies are immediately compounded, and into which they are ultimately resolved." Let us consider some of the work of Lavoisier in this direction. I select his experimental examination of the interactions of metals and acids. Many experimenters had noticed that gases (or airs, as they were called up till near the end of the 18th century) are generally produced when metals are dissolving in acids. Most of those who noticed this said that the gases came from the dissolving metals; Lavoisier said they were produced by the decomposition of the acids. In order to study the interaction of nitric acid and mercury, Lavoisier caused a weighed quantity of the metal to react with a weighed quantity of the acid, and collected the gas which was produced; when all the metal had dissolved, he evaporated the liquid until a white solid was obtained; he heated this solid until it was changed to the red substance called, at that time, _red precipitate_, and collected the gas produced. Finally, Lavoisier strongly heated the red precipitate; it changed to a gas, which he collected, and mercury, which he weighed. The weight of the mercury obtained by Lavoisier at the end of this series of changes was the same, less a few grains, as the weight of the mercury which he had caused to react with the nitric acid. The gas obtained during the solution of the metal in the acid, and during the decomposition of the white solid by heat, was the same as a gas which had been prepared by Priestley and called by him _nitrous air_; and the gas obtained by heating the red precipitate was found to be oxygen. Lavoisier then mixed measured volumes of oxygen and "nitrous air," standing over water; a red gas was formed, and dissolved in the water, and Lavoisier proved that the water now contained nitric acid. The conclusions regarding the composition of nitric acid drawn by Lavoisier from these experiments was, that "nitric acid is nothing else than _nitrous air_, combined with almost its own volume of the purest part of atmospheric air, and a considerable quantity of water." Lavoisier supposed that the stages in the complete reaction between mercury and nitric acid were these: the withdrawal of oxygen from the acid by the mercury, and the union of the compound of mercury and oxygen thus formed with the constituents of the acid which remained when part of its oxygen was taken away. The removal of oxygen from nitric acid by the mercury produced _nitrous air_; when the product of the union of the oxide of mercury and the nitric acid deprived of part of its oxygen was heated, more nitrous air was given off, and oxide of mercury remained, and was decomposed, at a higher temperature, into mercury and oxygen. Lavoisier thought of these reactions as the tearing asunder, by mercury, of nitric acid into definite quantities of its three components, themselves distinct substances, nitrous air, water, and oxygen; and the combination of the mercury with a certain measurable quantity of one of these components, namely, oxygen, followed by the union of this compound of mercury and oxygen with what remained of the components of nitric acid. Lavoisier had formed a clear, consistent, and suggestive mental picture of chemical changes. He thought of a chemical reaction as always the same under the same conditions, as an action between a fixed and measurable quantity of one substance, having definite and definable properties, with fixed and measurable quantities of other substances, the properties of each of which were definite and definable. Lavoisier also recognised that certain definite substances could be divided into things simpler than themselves, but that other substances refused to undergo simplification by division into two or more unlike portions. He spoke of the object of chemistry as follows:--[8] "In submitting to experiments the different substances found in nature, chemistry seeks to decompose these substances, and to get them into such conditions that their various components may be examined separately. Chemistry advances to its end by dividing, sub-dividing, and again sub-dividing, and we do not know what will be the limits of such operations. We cannot be certain that what we regard as simple to-day is indeed simple; all we can say is, that such a substance is the actual term whereat chemical analysis has arrived, and that with our present knowledge we cannot sub-divide it." [8] I have given a free rendering of Lavoisier's words. In these words Lavoisier defines the chemical conception of _elements_; since his time an element is "the actual term whereat chemical analysis has arrived," it is that which "with our present knowledge we cannot sub-divide"; and, as a working hypothesis, the notion of _element_ has no wider meaning than this. I have already quoted Boyle's statement that by _elements_ he meant "certain primitive and simple bodies ... not made of any other bodies, or of one another." Boyle was still slightly restrained by the alchemical atmosphere around him; he was still inclined to say, "this _must_ be the way nature works, she _must_ begin with certain substances which are absolutely simple." Lavoisier had thrown off all the trammels which hindered the alchemists from making rigorous experimental investigations. If one may judge from his writings, he had not struggled to free himself from these trammels, he had not slowly emerged from the quagmires of alchemy, and painfully gained firmer ground; the extraordinary clearness and directness of his mental vision had led him straight to the very heart of the problems of chemistry, and enabled him not only calmly to ignore all the machinery of Elements, Principles, Essences, and the like, which the alchemists had constructed so laboriously, but also to construct, in place of that mechanism which hindered inquiry, genuine scientific hypotheses which directed inquiry, and were themselves altered by the results of the experiments they had suggested. Lavoisier made these great advances by applying himself to the minute and exhaustive examination of a few cases of chemical change, and endeavouring to account for everything which took part in the processes he studied, by weighing or measuring each distinct substance which was present when the change began, and each which was present when the change was finished. He did not make haphazard experiments; he had a method, a system; he used hypotheses, and he used them rightly. "Systems in physics," Lavoisier writes, "are but the proper instruments for helping the feebleness of our senses. Properly speaking, they are methods of approximation which put us on the track of solving problems; they are the hypotheses which, successively modified, corrected, and changed, by experience, ought to conduct us, some day, by the method of exclusions and eliminations, to the knowledge of the true laws of nature." In a memoir wherein he is considering the production of carbonic acid and alcohol by the fermentation of fruit-juice, Lavoisier says, "It is evident that we must know the nature and composition of the substances which can be fermented and the products of fermentation; for nothing is created, either in the operations of art or in those of nature; and it may be laid down that the quantity of material present at the beginning of every operation is the same as the quantity present at the end, that the quality and quantity of the principles[9] are the same, and that nothing happens save certain changes, certain modifications. On this principle is based the whole art of experimenting in chemistry; in all chemical experiments we must suppose that there is a true equality between the principles[10] of the substances which are examined and those which are obtained from them by analysis." [9, 10] Lavoisier uses the word _principle_, here and elsewhere, to mean a definite homogeneous substance; he uses it as synonymous with the more modern terms element and compound. If Lavoisier's memoirs are examined closely, it is seen that at the very beginning of his chemical inquiries he assumed the accuracy, and the universal application, of the generalisation "nothing is created, either in the operations of art or in those of nature." Naturalists had been feeling their way for centuries towards such a generalisation as this; it had been in the air for many generations; sometimes it was almost realised by this or that investigator, then it escaped for long periods. Lavoisier seems to have realised, by what we call intuition, that however great and astonishing may be the changes in the properties of the substances which mutually react, there is no change in the total quantity of material. Not only did Lavoisier realise and act on this principle, he also measured quantities of substances by the one practical method, namely, by weighing; and by doing this he showed chemists the only road along which they could advance towards a genuine knowledge of material changes. The generalisation expressed by Lavoisier in the words I have quoted is now known as the _law of the conservation of mass_; it is generally stated in some such form as this:--the sum of the masses of all the homogeneous substances which take part in a chemical (or physical) change does not itself change. The science of chemistry rests on this law; every quantitative analysis assumes the accuracy, and is a proof of the validity, of it.[11] [11] I have considered the law of the conservation of mass in some detail in Chapter IV. of _The Story of the Chemical Elements_. By accepting the accuracy of this generalisation, and using it in every experiment, Lavoisier was able to form a clear mental picture of a chemical change as the separation and combination of homogeneous substances; for, by using the balance, he was able to follow each substance through the maze of changes, to determine when it united with other substances, and when it separated into substances simpler than itself. CHAPTER XIII. THE CHEMICAL ELEMENTS CONTRASTED WITH THE ALCHEMICAL PRINCIPLES. It was known to many observers in the later years of the 17th century that the product of the calcination of a metal weighs more than the metal; but it was still possible, at that time, to assert that this fact is of no importance to one who is seeking to give an accurate description of the process of calcination. Weight, which measures mass or quantity of substance, was thought of, in these days, as a property like colour, taste, or smell, a property which was sometimes decreased, and sometimes increased, by adding one substance to another. Students of natural occurrences were, however, feeling their way towards the recognition of some property of substances which did not change in the haphazard way wherein most properties seemed to alter. Lavoisier reached this property at one bound. By his experimental investigations, he taught that, however greatly the properties of one substance may be masked, or altered, by adding another substance to it, yet the property we call mass, and measure by weight, is not affected by these changes; for Lavoisier showed, that the mass of the product of the union of two substances is always exactly the sum of the masses of these two substances, and the sum of the masses of the substances whereinto one substance is divided is always exactly equal to that mass of the substance which is divided. For the undefined, ever-changing, protean essence, or soul, of a thing which the alchemists thought of as hidden by wrappings of properties, the exact investigations of Lavoisier, and those of others who worked on the same lines as he, substituted this definite, fixed, unmodifiable property of mass. Lavoisier, and those who followed in his footsteps, also did away with the alchemical notion of the existence of an essential substratum, independent of changes in those properties of a substance which can be observed by the senses. For the experimental researches of these men obliged naturalists to recognise, that a change in the properties of a definite, homogeneous substance, such as pure water, pure chalk, or pure sulphur, is accompanied (or, as we generally say, is caused) by the formation of a new substance or substances; and this formation, this apparent creation, of new material, is effected, either by the addition of something to the original substance, or by the separation of it into portions which are unlike it, and unlike one another. If the change is a combination, or coalescence, of two things into one, then the mass, and hence the weight, of the product is equal to the sum of those masses, and hence those weights, of the things which have united to form it; if the change is a separation of one distinct substance into several substances, then the sum of the masses, and hence the weights, of the products is equal to that mass, and hence that weight, of the substance which has been separated. Consider the word _water_, and the substance represented by this word. In Chapter IV., I gave illustrations of the different meanings which have been given to this word; it is sometimes used to represent a material substance, sometimes a quality more or less characteristic of that substance, and sometimes a process to which that substance, and many others like it, may be subjected. But when the word _water_ is used with a definite and exact meaning, it is a succinct expression for a certain group, or collocation, of measurable properties which are always found together, and is, therefore, thought of as a distinct substance. This substance can be separated into two other substances very unlike it, and can be formed by causing these to unite. One hundred parts, by weight, of pure water are always formed by the union of 11.11 parts of hydrogen, and 88.89 parts of oxygen, and can be separated into these quantities of those substances. When water is formed by the union of hydrogen and oxygen, in the ratio of 11.11 parts by weight of the former to 88.89 of the latter, the properties of the two substances which coalesce to form it disappear, except their masses. It is customary to say that water _contains_ hydrogen and oxygen; but this expression is scarcely an accurate description of the facts. What we call _substances_ are known to us only by their properties, that is, the ways wherein they act on our senses. Hydrogen has certain definite properties, oxygen has other definite properties, and the properties of water are perfectly distinct from those of either of the substances which it is said to contain. It is, therefore, somewhat misleading to say that water _contains_ substances the properties whereof, except their masses, disappeared at the moment when they united and water was produced. Nevertheless we are forced to think of water as, in a sense, containing hydrogen and oxygen. For, one of the properties of hydrogen is its power to coalesce, or combine, with oxygen to form water, and one of the properties of oxygen is its ability to unite with hydrogen to form water; and these properties of those substances cannot be recognised, or even suspected, unless certain definite quantities of the two substances are brought together under certain definite conditions. The properties which characterise hydrogen, and those which characterise oxygen, when these things are separated from all other substances, can be determined and measured in terms of the similar properties of some other substance taken as a standard. These two distinct substances disappear when they are brought into contact, under the proper conditions, and something (water) is obtained whose properties are very unlike those of hydrogen or oxygen; this new thing can be caused to disappear, and hydrogen and oxygen are again produced. This cycle of changes can be repeated as often as we please; the quantities of hydrogen and oxygen which are obtained when we choose to stop the process are exactly the same as the quantities of those substances which disappeared in the first operation whereby water was produced. Hence, water is an intimate union of hydrogen and oxygen; and, in this sense, water may be said to contain hydrogen and oxygen. The alchemist would have said, the properties of hydrogen and oxygen are destroyed when these things unite to form water, but the essence, or substratum, of each remains. The chemist says, you cannot discover all the properties of hydrogen and oxygen by examining these substances apart from one another, for one of the most important properties of either is manifested only when the two mutually react: the formation of water is not the destruction of the properties of hydrogen and oxygen and the revelation of their essential substrata, it is rather the manifestation of a property of each which cannot be discovered except by causing the union of both. There was, then, a certain degree of accuracy in the alchemical description of the processes we now call chemical changes, as being the removal of the outer properties of the things which react, and the manifestation of their essential substance. But there is a vast difference between this description and the chemical presentment of these processes as reactions between definite and measurable quantities of elements, or compounds, or both, resulting in the re-distribution, of the elements, or the separation of the compounds into their elements, and the formation of new compounds by the re-combination of these elements. Let us contrast the two descriptions somewhat more fully. The alchemist wished to effect the transmutation of one substance into another; he despaired of the possibility of separating the Elements whereof the substance might be formed, but he thought he could manipulate what he called the _virtues_ of the Elements by a judicious use of some or all of the three Principles, which he named Sulphur, Salt, and Mercury. He could not state in definite language what he meant by these Principles; they were states, conditions, or qualities, of classes of substances, which could not be defined. The directions the alchemist was able to give to those who sought to effect the change of one thing into another were these. Firstly, to remove those properties which characterised the thing to be changed, and leave only the properties which it shared with other things like it; secondly, to destroy the properties which the thing to be changed possessed in common with certain other things; thirdly, to commingle the Essence of the thing with the Essence of something else, in due proportion and under proper conditions; and, finally, to hope for the best, keep a clear head, and maintain a sense of virtue. If he who was about to attempt the transmutation inquired how he was to destroy the specific properties, and the class properties, of the thing he proposed to change, and by what methods he was to obtain its Essence, and cause that Essence to produce the new thing, he would be told to travel along "the road which was followed by the Great Architect of the Universe in the creation of the world." And if he demanded more detailed directions, he would be informed that the substance wherewith his experiments began must first be mortified, then dissolved, then conjoined, then putrefied, then congealed, then cibated, then sublimed, and fermented, and, finally, exalted. He would, moreover, be warned that in all these operations he must use, not things which he could touch, handle, and weigh, but the _virtues_, the _lives_, the _souls_, of such things. When the student of chemistry desires to effect the transformation of one definite substance into another, he is told to determine, by quantitative experiments, what are the elements, and what the quantities of these elements, which compose the compound which he proposes to change, and the compound into which he proposes to change it; and he is given working definitions of the words _element_ and _compound_. If the compound he desires to produce is found to be composed of elements different from those which form the compound wherewith his operations begin, he is directed to bring about a reaction, or a series of reactions, between the compound which is to be changed, and some other collocation of elements the composition of which is known to be such that it can supply the new elements which are needed for the production of the new compound. Since Lavoisier realised, for himself, and those who were to come after him, the meaning of the terms _element_ and _compound_, we may say that chemists have been able to form a mental picture of the change from one definite substance to another, which is clear, suggestive, and consistent, because it is an approximately accurate description of the facts discovered by careful and penetrative investigations. This presentment of the change has been substituted for the alchemical conception, which was an attempt to express what introspection and reasoning on the results of superficial investigations, guided by specious analogies, suggested ought to be the facts. Lavoisier was the man who made possible the more accurate, and more far-reaching, description of the changes which result in the production of substances very unlike those which are changed; and he did this by experimentally analysing the conceptions of the element and the compound, giving definite and workable meanings to these conceptions, and establishing, on an experimental foundation, the generalisation that the sum of the quantities of the substances which take part in any change is itself unchanged. A chemical element was thought of by Lavoisier as "the actual term whereat analysis has arrived," a definite substance "which we cannot subdivide with our present knowledge," but not necessarily a substance which will never be divided. A compound was thought of by him as a definite substance which is always produced by the union of the same quantities of the same elements, and can be separated into the same quantities of the same elements. These conceptions were amplified and made more full of meaning by the work of many who came after Lavoisier, notably by John Dalton, who was born in 1766 and died in 1844. In Chapter I., I gave a sketch of the atomic theory of the Greek thinkers. The founder of that theory, who flourished about 500 B.C., said that every substance is a collocation of a vast number of minute particles, which are unchangeable, indestructible, and impenetrable, and are therefore properly called _atoms_; that the differences which are observed between the qualities of things are due to differences in the numbers, sizes, shapes, positions, and movements of atoms, and that the process which occurs when one substance is apparently destroyed and another is produced in its place, is nothing more than a rearrangement of atoms. The supposition that changes in the properties of substances are connected with changes in the numbers, movements, and arrangements of different kinds of minute particles, was used in a general way by many naturalists of the 17th and 18th centuries; but Dalton was the first to show that the data obtained by the analyses of compounds make it possible to determine the relative weights of the atoms of the elements. Dalton used the word _atom_ to denote the smallest particle of an element, or a compound, which exhibits the properties characteristic of that element or compound. He supposed that the atoms of an element are never divided in any of the reactions of that element, but the atoms of a compound are often separated into the atoms of the elements whereof the compound is composed. Apparently without knowing that the supposition had been made more than two thousand years before his time, Dalton was led by his study of the composition and properties of the atmosphere to assume that the atoms of different substances, whether elements or compounds, are of different sizes and have different weights. He assumed that when two elements unite to form only one compound, the atom of that compound has the simplest possible composition, is formed by the union of a single atom of each element. Dalton knew only one compound of hydrogen and nitrogen, namely, ammonia. Analyses of this compound show that it is composed of one part by weight of hydrogen and 4.66 parts by weight of nitrogen. Dalton said one atom of hydrogen combines with one atom of nitrogen to form an atom of ammonia; hence an atom of nitrogen is 4.66 times heavier than an atom of hydrogen; in other words, if the _atomic weight_ of hydrogen is taken as unity, the _atomic weight_ of nitrogen is expressed by the number 4.66. Dalton referred the atomic weights of the elements to the atomic weight of hydrogen as unity, because hydrogen is lighter than any other substance; hence the numbers which tell how much heavier the atoms of the elements are than an atom of hydrogen are always greater than one, are always positive numbers. When two elements unite in different proportions, by weight, to form more than one compound, Dalton supposed that (in most cases at any rate) one of the compounds is formed by the union of a single atom of each element; the next compound is formed by the union of one atom of the element which is present in smaller quantity with two, three, or more, atoms of the other element, and the next compound is formed by the union of one atom of the first element with a larger number (always, necessarily, a whole number) of atoms of the other element than is contained in the second compound; and so on. From this assumption, and the Daltonian conception of the atom, it follows that the quantities by weight of one element which are found to unite with one and the same weight of another element must always be expressible as whole multiples of one number. For if two elements, A and B, form a compound, that compound is formed, by supposition, of one atom of A and one atom of B; if more of B is added, at least one atom of B must be added; however much of B is added the quantity must be a whole number of atoms; and as every atom of B is the same in all respects as every other atom of B, the weights of B added to a constant weight of A must be whole multiples of the atomic weight of B. The facts which were available in Dalton's time confirmed this deduction from the atomic theory within the limits of experimental errors; and the facts which have been established since Dalton's time are completely in keeping with the deduction. Take, for instance, three compounds of the elements nitrogen and oxygen. That one of the three which contains least oxygen is composed of 63.64 _per cent._ of nitrogen, and 36.36 _per cent._ of oxygen; if the atomic weight of nitrogen is taken to be 4.66, which is the weight of nitrogen that combines with one part by weight of hydrogen, then the weight of oxygen combined with 4.66 of nitrogen is 2.66 (63.64:36.36 = 4.66:2.66). The weights of oxygen which combine with 4.66 parts by weight of nitrogen to form the second and third compounds, respectively, must be whole multiples of 2.66; these weights are 5.32 and 10.64. Now 5.32 = 2.66 x 2, and 10.64 = 2.66 x 4. Hence, the quantities by weight of oxygen which combine with one and the same weight of nitrogen are such that two of these quantities are whole multiples of the third quantity. Dalton's application of the Greek atomic theory to the facts established by the analyses of compounds enabled him to attach to each element a number which he called the atomic weight of the element, and to summarise all the facts concerning the compositions of compounds in the statement, that the elements combine in the ratios of their atomic weights, or in the ratios of whole multiples of their atomic weights. All the investigations which have been made into the compositions of compounds, since Dalton's time, have confirmed the generalisation which followed from Dalton's application of the atomic theory. Even if the theory of atoms were abandoned, the generalisation would remain, as an accurate and exact statement of facts which hold good in every chemical change, that a number can be attached to each element, and the weights of the elements which combine are in the ratios of these numbers, or whole multiples of these numbers. Since chemists realised the meaning of Dalton's book, published in 1808, and entitled, _A New System of Chemical Philosophy_, elements have been regarded as distinct and definite substances, which have not been divided into parts different from themselves, and unite with each other in definite quantities by weight which can be accurately expressed as whole multiples of certain fixed quantities; and compounds have been regarded as distinct and definite substances which are formed by the union of, and can be separated into, quantities of various elements which are expressible by certain fixed numbers or whole multiples thereof. These descriptions of elements and compounds are expressions of actual facts. They enable chemists to state the compositions of all the compounds which are, or can be, formed by the union of any elements. For example, let A, B, C, and D represent four elements, and also certain definite weights of these elements, then the compositions of all the compounds which can be formed by the union of these elements are expressed by the scheme A_{_n_} B_{_m_} C_{_p_} D_{_q_}, where _m_ _n_ _p_ and _q_ are whole numbers. These descriptions of elements and compounds also enable chemists to form a clear picture to themselves of any chemical change. They think of a chemical change as being; (1) a union of those weights of two, or more, elements which are expressed by the numbers attached to these elements, or by whole multiples of these numbers; or (2) a union of such weights of two, or more, compounds as can be expressed by certain numbers or by whole multiples of these numbers; or (3) a reaction between elements and compounds, or between compounds and compounds, resulting in the redistribution of the elements concerned, in such a way that the complete change of composition can be expressed by using the numbers, or whole multiples of the numbers, attached to the elements. How different is this conception of a change wherein substances are formed, entirely unlike those things which react to form them, from the alchemical presentment of such a process! The alchemist spoke of stripping off the outer properties of the thing to be changed, and, by operating spiritually on the soul which was thus laid bare, inducing the essential virtue of the substance to exhibit its powers of transmutation. But he was unable to give definite meanings to the expressions which he used, he was unable to think clearly about the transformations which he tried to accomplish. The chemist discards the machinery of virtues, souls, and powers. It is true that he substitutes a machinery of minute particles; but this machinery is merely a means of thinking clearly and consistently about the changes which he studies. The alchemist thought, vaguely, of substance as something underlying, and independent of, properties; the chemist uses the expression, this or that substance, as a convenient way of presenting and reasoning about certain groups of properties. It seems to me that if we think of _matter_ as something more than properties recognised by the senses, we are going back on the road which leads to the confusion of the alchemical times. The alchemists expressed their conceptions in what seems to us a crude, inconsistent, and very undescriptive language. Chemists use a language which is certainly symbolical, but also intelligible, and on the whole fairly descriptive of the facts. A name is given to each elementary substance, that is, each substance which has not been decomposed; the name generally expresses some characteristic property of the substance, or tells something about its origin or the place of its discovery. The names of compounds are formed by putting together the names of the elements which combine to produce them; and the relative quantities of these elements are indicated either by the use of Latin or Greek prefixes, or by variations in the terminal syllables of the names of the elements. CHAPTER XIV. THE MODERN FORM OF THE ALCHEMICAL QUEST OF THE ONE THING. The study of the properties of the elements shows that these substances fall into groups, the members of each of which are like one another, and form compounds which are similar. The examination of the properties and compositions of compounds has shown that similarity of properties is always accompanied by similarity of composition. Hence, the fact that certain elements are very closely allied in their properties suggests that these elements may also be allied in their composition. Now, to speak of the composition of an element is to think of the element as formed by the union of at least two different substances; it implies the supposition that some elements at any rate are really compounds. The fact that there is a very definite connexion between the values of the atomic weights, and the properties, of the elements, lends some support to the hypothesis that the substances we call, and are obliged at present to call, elements, may have been formed from one, or a few, distinct substances, by some process of progressive change. If the elements are considered in the order of increasing atomic weights, from hydrogen, whose atomic weight is taken as unity because it is the lightest substance known, to uranium, an atom of which is 240 times heavier than an atom of hydrogen, it is found that the elements fall into periods, and the properties of those in one period vary from element to element, in a way which is, broadly and on the whole, like the variation of the properties of those in other periods. This fact suggests the supposition--it might be more accurate to say the speculation--that the elements mark the stable points in a process of change, which has not proceeded continuously from a very simple substance to a very complex one, but has repeated itself, with certain variations, again and again. If such a process has occurred, we might reasonably expect to find substances exhibiting only minute differences in their properties, differences so slight as to make it impossible to assign the substances, definitely and certainly, either to the class of elements or to that of compounds. We find exactly such substances among what are called the _rare earths_. There are earth-like substances which exhibit no differences of chemical properties, and yet show minute differences in the characters of the light which they emit when they are raised to a very high temperature. The results of analysis by the spectroscope of the light emitted by certain elements at different temperatures may be reasonably interpreted by supposing that these elements are separated into simpler substances by the action on them of very large quantities of thermal energy. The spectrum of the light emitted by glowing iron heated by a Bunsen flame (say, at 1200° C. = about 2200° F.) shows a few lines and flutings; when iron is heated in an electric arc (say, to 3500° C. = about 6300° F.) the spectrum shows some two thousand lines; at the higher temperature produced by the electric spark-discharge, the spectrum shows only a few lines. As a guide to further investigation, we may provisionally infer from these facts that iron is changed at very high temperatures into substances simpler than itself. Sir Norman Lockyer's study of the spectra of the light from stars has shown that the light from those stars which are presumably the hottest, judging by the general character of their spectra, reveals the presence of a very small number of chemical elements; and that the number of spectral lines, and, therefore, the number of elements, increases as we pass from the hottest to cooler stars. At each stage of the change from the hottest to cooler stars certain substances disappear and certain other substances take their places. It may be supposed, as a suggestive hypothesis, that the lowering of stellar temperature is accompanied by the formation, from simpler forms of matter, of such elements as iron, calcium, manganese, and other metals. In the year 1896, the French chemist Becquerel discovered the fact that salts of the metal uranium, the atomic weight of which is 240, and is greater than that of any other element, emit rays which cause electrified bodies to lose their electric charges, and act on photographic plates that are wrapped in sheets of black paper, or in thin sheets of other substances which stop rays of light. The _radio-activity_ of salts of uranium was proved not to be increased or diminished when these salts had been shielded for five years from the action of light by keeping them in leaden boxes. Shortly after Becquerel's discovery, experiments proved that salts of the rare metal thorium are radio-active. This discovery was followed by Madame Curie's demonstration of the fact that certain specimens of _pitchblende_, a mineral which contains compounds of uranium and of many other metals, are extremely radio-active, and by the separation from pitchblende, by Monsieur and Madame Curie, of new substances much more radio-active than compounds of uranium or of thorium. The new substances were proved to be compounds chemically very similar to salts of barium. Their compositions were determined on the supposition that they were salts of an unknown metal closely allied to barium. Because of the great radio-activity of the compounds, the hypothetical metal of them was named _Radium_. At a later time, radium was isolated by Madame Curie. It is described by her as a white, hard, metal-like solid, which reacts with water at the ordinary temperature, as barium does. Since the discovery of radium compounds, many radio-active substances have been isolated. Only exceedingly minute quantities of any of them have been obtained. The quantities of substances used in experiments on radio-activity are so small that they escape the ordinary methods of measurement, and are scarcely amenable to the ordinary processes of the chemical laboratory. Fortunately, radio-activity can be detected and measured by electrical methods of extraordinary fineness, methods the delicacy of which very much more exceeds that of spectroscopic methods than the sensitiveness of these surpasses that of ordinary chemical analysis. At the time of the discovery of radio-activity, about seventy-five substances were called elements; in other words, about seventy-five different substances were known to chemists, none of which had been separated into unlike parts, none of which had been made by the coalescence of unlike substances. Compounds of only two of these substances, uranium and thorium, are radio-active. Radio-activity is a very remarkable phenomenon. So far as we know at present, radio-activity is not a property of the substances which form almost the whole of the rocks, the waters, and the atmosphere of the earth; it is not a property of the materials which constitute living organisms. It is a property of some thirty substances--of course, the number may be increased--a few of which are found widely distributed in rocks and waters, but none of which is found anywhere except in extraordinarily minute quantity. Radium is the most abundant of these substances; but only a very few grains of radium chloride can be obtained from a couple of tons of pitchblende. In Chapter X. of _The Story of the Chemical Elements_ I have given a short account of the outstanding phenomena of radio-activity; for the present purpose it will suffice to state a few facts of fundamental importance. Radio-active substances are stores of energy, some of which is constantly escaping from them; they are constantly changing without external compulsion, and are constantly radiating energy: all explosives are storehouses of energy which, or part of which, can be obtained from them; but the liberation of their energy must be started by some kind of external shock. When an explosive substance has exploded, its existence as an explosive is finished; the products of the explosion are substances from which energy cannot be obtained: when a radio-active substance has exploded, it explodes again, and again, and again; a time comes, sooner or later, when it has changed into substances that are useless as sources of energy. The disintegration of an explosive, started by an external force, is generally completed in a fraction of a second; change of condition changes the rate of explosion: the "half-life period" of each radio-active substance is a constant characteristic of it; if a gram of radium were kept for about 1800 years, half of it would have changed into radio-inactive substances. Conditions may be arranged so that an explosive remains unchanged--wet gun-cotton is not exploded by a shock which would start the explosion of dry gun-cotton--in other words, the explosion of an explosive can be regulated: the explosive changes of a radio-active substance, which are accompanied by the radiation of energy, cannot be regulated; they proceed spontaneously in a regular and definable manner which is not influenced by any external conditions--such as great change of temperature, presence or absence of other substances--so far as these conditions have been made the subject of experiment: the amount of activity of a radio-active substance has not been increased or diminished by any process to which the substance has been subjected. Explosives are manufactured articles; explosiveness is a property of certain arrangements of certain quantities of certain elements: so far as experiments have gone, it has not been found possible to add the property of radio-activity to an inactive substance, or to remove the property of radio-activity from an active substance; the cessation of the radio-activity of an active substance is accompanied by the disappearance of the substance, and the production of inactive bodies altogether unlike the original active body. Radio-active substances are constantly giving off energy in the form of heat, sending forth _rays_ which have definite and remarkable properties, and producing gaseous _emanations_ which are very unstable, and change, some very rapidly, some less rapidly, into other substances, and emit _rays_ which are generally the same as the rays emitted by the parent substance. In briefly considering these three phenomena, I shall choose radium compounds as representative of the class of radio-active substances. Radium compounds spontaneously give off energy in the form of heat. A quantity of radium chloride which contains 1 gram of radium continuously gives out, per hour, a quantity of heat sufficient to raise the temperature of 1 gram of water through 100° C., or 100 grams of water through 1° C. The heat given out by 1 gram of radium during twenty-four hours would raise the temperature of 2400 grams of water through 1° C.; in one year the temperature of 876,000 grams of water would be raised through 1° C.; and in 1800 years, which is approximately the half-life period of radium, the temperature of 1,576,800 _kilograms_ of water would be raised through 1° C. These results may be expressed by saying that if 1 gram (about 15 grains) of radium were kept until half of it had changed into inactive substances, and if the heat spontaneously produced during the changes which occurred were caused to act on water, that quantity of heat would raise the temperature of about 15½ tons of water from its freezing- to its boiling-point. Radium compounds send forth three kinds of rays, distinguished as _alpha_, _beta_, and _gamma_ rays. Experiments have made it extremely probable that the [alpha]-rays are streams of very minute particles, somewhat heavier than atoms of hydrogen, moving at the rate of about 18,000 miles per second; and that the [beta]-rays are streams of much more minute particles, the mass of each of which is about one one-thousandth of the mass of an atom of hydrogen, moving about ten times more rapidly than the [alpha]-particles, that is, moving at the rate of about 180,000 miles per second. The [gamma]-rays are probably pulsations of the ether, the medium supposed to fill space. The emission of [alpha]-rays by radium is accompanied by the production of the inert elementary gas, helium; therefore, the [alpha]-rays are, or quickly change into, rapidly moving particles of helium. The particles which constitute the [beta]-rays carry electric charges; these electrified particles, each approximately a thousand times lighter than an atom of hydrogen, moving nearly as rapidly as the pulsations of the ether which we call light, are named _electrons_. The rays from radium compounds discharge electrified bodies, ionise gases, that is, cause them to conduct electricity, act on photographic plates, and produce profound changes in living organisms. The radium emanation is a gas about 111 times heavier than hydrogen; to this gas Sir William Ramsay has given the name _niton_. The gas has been condensed to a colourless liquid, and frozen to an opaque solid which glows like a minute arc-light. Radium emanation gives off [alpha]-particles, that is, very rapidly moving atoms of helium, and deposits exceedingly minute quantities of a solid, radio-active substance known as radium A. The change of the emanation into helium and radium A proceeds fairly rapidly: the half-life period of the emanation is a little less than four days. This change is attended by the liberation of much energy. The only satisfactory mental picture which the facts allow us to form, at present, of the emission of [beta]-rays from radium compounds is that which represents these rays as streams of electrons, that is, particles, each about a thousand times lighter than an atom of hydrogen, each carrying an electric charge, and moving at the rate of about 180,000 miles per second, that is, nearly as rapidly as light. When an electric discharge is passed from a plate of metal, arranged as the kathode, to a metallic wire arranged as the anode, both sealed through the walls of a glass tube or bulb from which almost the whole of the air has been extracted, rays proceed from the kathode, in a direction at right angles thereto, and, striking the glass in the neighbourhood of the anode, produce a green phosphorescence. Facts have been gradually accumulated which force us to think of these _kathode rays_ as streams of very rapidly moving electrons, that is, as streams of extraordinarily minute electrically charged particles identical with the particles which form the [beta]-rays emitted by compounds of radium. The phenomena of radio-activity, and also the phenomena of the kathode rays, have obliged us to refine our machinery of minute particles by including therein particles at least a thousand times lighter than atoms of hydrogen. The term _electron_ was suggested, a good many years ago, by Dr Johnstone Stoney, for the unit charge of electricity which is carried by an atom of hydrogen when hydrogen atoms move in a liquid or gas under the directing influence of the electric current. Some chemists speak of the electrons, which are the [beta]-rays from radium, and the kathode rays produced in almost vacuous tubes, as non-material particles of electricity. Non-material means devoid of mass. The method by which approximate determinations have been made of the charges on electrons consists in measuring the ratio between the charges and the masses of these particles. If the results of the determinations are accepted, electrons are not devoid of mass. Electrons must be thought of as material particles differing from other minute material particles in the extraordinary smallness of their masses, in the identity of their properties, including their mass, in their always carrying electric charges, and in the vast velocity of their motion. We must think of an electron either as a unit charge of electricity one property of which is its minute mass, or as a material particle having an extremely small mass and carrying a unit charge of electricity: the two mental pictures are almost, if not quite, identical. Electrons are produced by sending an electric discharge through a glass bulb containing a minute quantity of air or other gas, using metallic plates or wires as kathode and anode. Experiments have shown that the electrons are identical in all their properties, whatever metal is used to form the kathode and anode, and of whatever gas there is a minute quantity in the bulb. The conclusion must be drawn that identical electrons are constituents of, or are produced from, very different kinds of chemical elements. As the facts about kathode rays, and the facts of radio-activity are (at present) inexplicable except on the supposition that these phenomena are exhibited by particles of extraordinary minuteness, and as the smallest particles with which chemists are concerned in their everyday work are the atoms of the elements, we seem obliged to think of many kinds of atoms as structures, not as homogeneous bodies. We seem obliged to think of atoms as very minute material particles, which either normally are, or under definite conditions may be, associated with electrically charged particles very much lighter than themselves, all of which are identical, whatever be the atoms with which they are associated or from which they are produced. In their study of different kinds of matter, chemists have found it very helpful to place in one class those substances which they have not been able to separate into unlike parts. They have distinguished this class of substances from other substances, and have named them _elements_. The expression _chemical elements_ is merely a summary of certain observed facts. For many centuries chemists have worked with a conceptual machinery based on the notion that matter has a grained structure. For more than a hundred years they have been accustomed to think of atoms as the ultimate particles with which they have had to deal. Working with this order-producing instrument, they have regarded the properties of elements as properties of the atoms, or of groups of a few of the atoms, of these substances. That they might think clearly and suggestively about the properties of elements, and connect these with other chemical facts, they have translated the language of sense-perceptions into the language of thought, and, for _properties of those substances which have not been decomposed_, have used the more fertile expression _atomic properties_. When a chemist thinks of an atom, he thinks of the minutest particle of one of the substances which have the class-mark _have-not-been-decomposed_, and the class-name _element_. The chemist does not call these substances elements because he has been forced to regard the minute particles of them as undivided, much less because he thinks of these particles as indivisible; his mental picture of their structure as an atomic structure formed itself from the fact that they had not been decomposed. The formation of the class _element_ followed necessarily from observed facts, and has been justified by the usefulness of it as an instrument for forwarding accurate knowledge. The conception of the elementary atom as a particle which had not been decomposed followed from many observed facts besides those concerning elements, and has been justified by the usefulness of it as an instrument for forwarding accurate knowledge. Investigations proved radio-activity to be a property of the very minute particles of certain substances, and each radio-active substance to have characteristic properties, among which were certain of those that belong to elements, and to some extent are characteristic of elements. Evidently, the simplest way for a chemist to think about radio-activity was to think of it as an atomic property; hence, as atomic properties had always been regarded, in the last analysis, as properties of elements, it was natural to place the radio-active substances in the class _elements_, provided that one forgot for the time that these substances have not the class-mark _have-not-been-decomposed_. As the facts of radio-activity led to the conclusion that some of the minute particles of radio-active substances are constantly disintegrating, and as these substances had been labelled _elements_, it seemed probable, or at least possible, that the other bodies which chemists have long called elements are not true elements, but are merely more stable collocations of particles than the substances which are classed as compounds. As compounds can be changed into certain other compounds, although not into any other compounds, a way seemed to be opening which might lead to the transformation of some elements into some other elements. The probability that one element might be changed into another was increased by the demonstration of the connexions between uranium and radium. The metal uranium has been classed with the elements since it was isolated in 1840. In 1896, Becquerel found that compounds of uranium, and also the metal itself, are radio-active. In the light of what is now known about radio-activity, it is necessary to suppose that some of the minute particles of uranium emit particles lighter than themselves, and change into some substance, or substances, different from uranium; in other words, it is necessary to suppose that some particles of uranium are spontaneously disintegrating. This supposition is confirmed by the fact, experimentally proved, that uranium emits [alpha]-rays, that is, atoms of helium, and produces a substance known as uranium X. Uranium X is itself radio-active; it emits [beta]-rays, that is, it gives off electrons. Inasmuch as all minerals which contain compounds of uranium contain compounds of radium also, it is probable that radium is one of the disintegration-products of uranium. The rate of decay of radium may be roughly expressed by saying that, if a quantity of radium were kept for ten thousand years, only about one per cent. of the original quantity would then remain unchanged. Even if it were assumed that at a remote time the earth's crust contained considerable quantities of radium compounds, it is certain that they would have completely disappeared long ago, had not compounds of radium been reproduced from other materials. Again, the most likely hypothesis is that compounds of radium are being produced from compounds of uranium. Uranium is a substance which, after being rightly classed with the elements for more than half a century, because it had not been separated into unlike parts, must now be classed with the radium-like substances which disintegrate spontaneously, although it differs from other radio-active substances in that its rate of change is almost infinitively slower than that of any of them, except thorium.[12] Thorium, a very rare metal, is the second of the seventy-five or eighty elements known when radio-activity was discovered, which has been found to undergo spontaneous disintegration with the emission of rays. The rate of change of thorium is considerably slower than that of uranium.[13] None of the other substances placed in the class of elements is radio-active. [12] The life-period of uranium is probably about eight thousand million years. [13] The life-period of thorium is possibly about forty thousand million years. On p. 192 I said, that when the radio-active substances had been labelled _elements_, the facts of radio-activity led some chemists to the conclusion that the other bodies which had for long been called by this class-name, or at any rate some of these bodies, are perhaps not true elements, but are merely more stable collocations of particles than the substances called compounds. It seems to me that this reasoning rests on an unscientific use of the term _element_; it rests on giving to that class-name the meaning, _substances asserted to be undecomposable_. A line of demarcation is drawn between _elements_, meaning thereby forms of matter said to be undecomposable but probably capable of separation into unlike parts, and _true elements_, meaning thereby groups of identical undecomposable particles. If one names the radio-active substances _elements_, one is placing in this class substances which are specially characterised by a property the direct opposite of that the possession of which by other substances was the reason for the formation of the class. To do this may be ingenious; it is certainly not scientific. Since the time of Lavoisier, since the last decade of the eighteenth century, careful chemists have meant by an element a substance which has not been separated into unlike parts, and they have not meant more than that. The term _element_ has been used by accurate thinkers as a useful class-mark which connotes a property--the property of not having been decomposed--common to all substances placed in the class, and differentiating them from all other substances. Whenever chemists have thought of elements as the ultimate kinds of matter with which the physical world is constructed--and they have occasionally so thought and written--they have fallen into quagmires of confusion. Of course, the elements may, some day, be separated into unlike parts. The facts of radio-activity certainly suggest some kind of inorganic evolution. Whether the elements are decomposed is to be determined by experimental inquiry, remembering always that no number of failures to simplify them will justify the assertion that they cannot be simplified. Chemistry neither asserts or denies the decomposability of the elements. At present, we have to recognise the existence of extremely small quantities, widely distributed in rocks and waters, of some thirty substances, the minute particles of which are constantly emitting streams of more minute, identical particles that carry with them very large quantities of energy, all of which thirty substances are characterised, and are differentiated from all other classes of substances wherewith chemistry is concerned, by their spontaneous mutability, and each is characterised by its special rate of change and by the nature of the products of its mutations. We have now to think of the minute particles of two of the seventy-five or eighty substances which until the other day had not been decomposed, and were therefore justly called elements, as very slowly emitting streams of minuter particles and producing characteristic products of their disintegration. And we have to think of some eighty substances as particular kinds of matter, at present properly called elements, because they are characterised, and differentiated from all other substances, by the fact that none of them has been separated into unlike parts. The study of radio-activity has introduced into chemistry and physics a new order of minute particles. Dalton made the atom a beacon-light which revealed to chemists paths that led them to wider and more accurate knowledge. Avogadro illuminated chemical, and also physical, ways by his conception of the molecule as a stable, although separable, group of atoms with particular properties different from those of the atoms which constituted it. The work of many investigators has made the old paths clearer, and has shown to chemists and physicists ways they had not seen before, by forcing them to think of, and to make use of, a third kind of material particles that are endowed with the extraordinary property of radio-activity. Dalton often said: "Thou knowest thou canst not cut an atom"; but the fact that he applied the term _atom_ to the small particles of compounds proves that he had escaped the danger of logically defining the atom, the danger of thinking of it as a particle which never can be cut. The molecule of Avogadro has always been a decomposable particle. The peculiarity of the new kind of particles, the particles of radio-active bodies, is, not that they can be separated into unlike parts by the action of external forces, but that they are constantly separating of their own accord into unlike parts, and that their spontaneous disintegration is accompanied by the production of energy, the quantity of which is enormous in comparison with the minuteness of the material specks which are the carriers of it. The continued study of the properties of the minute particles of radio-active substances--a new name is needed for those most mutable of material grains--must lead to discoveries of great moment for chemistry and physics. That study has already thrown much light on the phenomena of electric conductivity; it has given us the electron, a particle at least a thousand times lighter than an atom of hydrogen; it has shown us that identical electrons are given off by, or are separated from, different kinds of elementary atoms, under definable conditions; it has revealed unlooked-for sources of energy; it has opened, and begun the elucidation of, a new department of physical science; it has suggested a new way of attacking the old problem of the alchemists, the problem of the transmutation of the elements. The minute particles of two of the substances for many years classed as elements give off electrons; uranium and thorium are radio-active. Electrons are produced by sending an electric discharge through very small traces of different gases, using electrodes of different metals. Electrons are also produced by exposing various metals to the action of ultra-violet light, and by raising the temperature of various metals to incandescence. Electrons are always identical, whatever be their source. Three questions suggest themselves. Can the atoms of all the elements be caused to give off electrons? Are electrons normal constituents of all elementary atoms? Are elementary atoms collocations of electrons? These questions are included in the demand--Is it possible "to imagine a model which has in it the potentiality of explaining" radio-activity and other allied phenomena, as well as all other chemical and physical properties of elements and compounds? These questions are answerable by experimental investigation, and only by experimental investigation. If experimental inquiry leads to affirmative answers to the questions, we shall have to think of atoms as structures of particles much lighter than themselves; we shall have to think of the atoms of all kinds of substances, however much the substances differ chemically and physically, as collocations of identical particles; we shall have to think of the properties of atoms as conditioned, in our final analysis, by the number and the arrangement of their constitutive electrons. Now, if a large probability were established in favour of the view that different atoms are collocations of different numbers of identical particles, or of equal numbers of differently arranged identical particles, we should have a guide which might lead to methods whereby one collocation of particles could be formed from another collocation of the same particles, a guide which might lead to methods whereby one element could be transformed into another element. To attempt "to imagine a model which has in it the potentiality of explaining" radio-activity, the production of kathode rays, and the other chemical and physical properties of elements and compounds, might indeed seem to be a hopeless undertaking. A beginning has been made in the mental construction of such a model by Professor Sir J.J. Thomson. To attempt a description of his reasoning and his results is beyond the scope of this book.[14] [14] The subject is discussed in Sir J.J. Thomson's _Electricity and Matter_. The facts that the emanation from radium compounds spontaneously gives off very large quantities of energy, and that the emanation can easily be brought into contact with substances on which it is desired to do work, suggested to Sir William Ramsay that the transformation of compounds of one element into compounds of another element might possibly be effected by enclosing a solution of a compound along with radium emanation in a sealed tube, and leaving the arrangement to itself. Under these conditions, the molecules of the compound would be constantly bombarded by a vast number of electrons shot forth at enormous velocities from the emanation. The notion was that the molecules of the compound would break down under the bombardment, and that the atoms so produced might be knocked into simpler groups of particles--in other words, changed into other atoms--by the terrific, silent shocks of the electrons fired at them incessantly by the disintegrating emanation. Sir William Ramsay regards his experimental results as establishing a large probability in favour of the assertion that compounds of copper were transformed into compounds of lithium and sodium, and compounds of thorium, of cerium, and of certain other rare metals, into compounds of carbon. The experimental evidence in favour of this statement has not been accepted by chemists as conclusive. A way has, however, been opened which may lead to discoveries of great moment. Let us suppose that the transformation of one element into another element or into other elements has been accomplished. Let us suppose that the conception of elementary atoms as very stable arrangements of many identical particles, from about a thousand to about a quarter of a million times lighter than the atoms, has been justified by crucial experiments. Let us suppose that the conception of the minute grains of radio-active substances as particular but constantly changing arrangements of the same identical particles, stable groups of which are the atoms of the elements, has been firmly established. One result of the establishment of the electronic conception of atomic structure would be an increase of our wonder at the complexity of nature's ways, and an increase of our wonder that it should be possible to substitute a simple, almost rigid, mechanical machinery for the ever-changing flow of experience, and, by the use of that mental mechanism, not only to explain very many phenomena of vast complexity, but also to predict occurrences of similar entanglement and to verify these predictions. The results which have been obtained in the examination of radio-activity, of kathode rays, of spectra at different temperatures, and of phenomena allied to these, bring again into prominence the ancient problem of the structure of what we call matter. Is matter fundamentally homogeneous or heterogeneous? Chemistry studies the relations between the changes of composition and the changes of properties which happen simultaneously in material systems. The burning fire of wood, coal, or gas; the preparation of food to excite and to satisfy the appetite; the change of minerals into the iron, steel, copper, brass, lead, tin, lighting burning and lubricating oils, dye-stuffs and drugs of commerce; the change of the skins, wool, and hair of animals, and of the seeds and fibres of plants, into clothing for human beings; the manufacture from rags, grass, or wood of a material fitted to receive and to preserve the symbols of human hopes, fears, aspirations, love and hate, pity and aversion; the strange and most delicate processes which, happening without cessation, in plants and animals and men, maintain that balanced equilibrium which we call life; and, when the silver cord is being loosed and the bowl broken at the cistern, the awful changes which herald the approach of death; not only the growing grass in midsummer meadows, not only the coming of autumn "in dyed garments, travelling in the glory of his apparel," but also the opening buds, the pleasant scents, the tender colours which stir our hearts in "the spring time, the only pretty ring time, when birds do sing, ding-a--dong-ding": these, and a thousand other changes have all their aspects which it is the business of the chemist to investigate. Confronted with so vast a multitude of never-ceasing changes, and bidden to find order there, if he can--bidden, rather compelled by that imperious command which forces the human mind to seek unity in variety, and, if need be, to create a cosmos from a chaos; no wonder that the early chemists jumped at the notion that there must be, that there is, some _One Thing_, some _Universal Essence_, which binds into an orderly whole the perplexing phenomena of nature, some _Water of Paradise_ which is for the healing of all disorder, some "Well at the World's End," a draught whereof shall bring peace and calm security. The alchemists set forth on the quest. Their quest was barren. They made the great mistake of fashioning _The One Thing, The Essence, The Water of Paradise_, from their own imaginings of what nature ought to be. In their own likeness they created their goal, and the road to it. If we are to understand nature, they cried, her ways must be simple; therefore, her ways are simple. Chemists are people of a humbler heart. Their reward has been greater than the alchemists dreamed. By selecting a few instances of material changes, and studying these with painful care, they have gradually elaborated a general conception of all those transformations wherein substances are produced unlike those by the interaction of which they are formed. That general conception is now both widening and becoming more definite. To-day, chemists see a way opening before them which they reasonably hope will lead them to a finer, a more far-reaching, a more suggestive, at once a more complex and a simpler conception of material changes than any of those which have guided them in the past. INDEX Air, ancient views regarding, 129. ---- views of Mayow and Rey regarding, 129. Alchemical account of changes contrasted with chemical account, 169. ---- agent, the, 64. ---- allegories, examples of, 41, 97. ---- classification, 59. ---- doctrine of body, soul, and spirit of things, 48. ---- doctrine of transmutation, 47, 74, 123, 170. ---- language, 36, 96, 101, 102. ---- quest of the One Thing, modern form of, 179. ---- signs, 105. ---- theory, general sketch of, 26. Alchemists, character of, according to Paracelsus, 25. ---- made many discoveries, 87. ---- sketches of lives of some, 115. ---- their use of fanciful analogies, 31. Alchemy, beginnings of, 23. ---- change of, to chemistry, 126. ---- contrasted with chemistry, 202. ---- general remarks on, 123. ---- lent itself to imposture, 106. ---- object of, 9, 26, 32, 105. ---- probable origin of word, 25. ---- quotations to illustrate aims and methods of, 11-14. Alembic, 92. Apparatus and operations of alchemists, 90. Art, the sacred, 122. Atom, meaning given to word by Dalton, 173. Atomic theory of Greeks, 16. ---- additions made to, by Dalton, 21. ---- as described by Lucretius, 19. Atomic weight, 174. Atoms and electrons, 190, 198. Bacon's remarks on alchemy, 95. Balsamo, Joseph, 110. Basil Valentine, his description of the three principles, 51. ---- his description of the four elements, 49. ---- some of his discoveries, 88. Becquerel, his discovery of radiation of uranium, 181. Body, soul, and spirit of things, alchemical doctrine of, 48. Boyle, on calcination, 128. ---- on combustion, 141. ---- on elements, 161. ---- on the "hermetick philosophers," 95. ---- on the language of the alchemists, 55. ---- on the natural state of bodies, 43. Cagliostro, 110. Calcination, 129, 132, 135, 140, 142, 151, 155. Chaucer's _Canon's Yeoman's Tale_, 107. Chemical conception of material changes, 177. Chemistry, aim of, 9, 26, 160. ---- change from alchemy to, 126. ---- methods of, 10. ---- probable origin of word, 24. Classification, alchemical methods of, 59. Colours, Lucretius' explanation of differences between, 18. Combustion, 141. Compounds, chemical conception of, 171. Conservation of mass, 164. Curie, her discovery of radium, 182. Dalton's additions to the Greek atomic theory, 21, 172. Democritus, his saying about atoms, 15. Dephlogisticated air, 147. Destruction, thought by alchemists to precede restoration, 65, 127. Electrons, 187-189, 197, 198. Elements, alchemical, contrasted with chemical, 165; radio-active substances contrasted with, 190-192. ---- the alchemical, 49, 54, 60. ---- the chemical, 61, 62, 161. ---- use of word, by phlogisteans, 133. Essence, the alchemical, 32, 35, 49, 58, 72. Fire, different meanings of the word, 53. Gates, the alchemical, 69. Gold, considered by alchemists to be the most perfect metal, 40, 45. Greek thinkers, their atomic theory, 15. Hermes Trismegistus, 37. Kathode rays, 188. Language of alchemy, 96. ---- purposely made misleading, 36. Lavoisier on calcination, 153, 155. ---- his use of word _element_, 194. ---- his use of word _principle_, 163, _note_. ---- on object of chemistry, 160. ---- on oxygen, 155. ---- on systems in science, 163. ---- on the principle of acidity, 59, 155. ---- on the reactions of metals with acids, 158. ---- on the transmutation of water to earth, 152. Lockyer, on spectra of elements, 181. Lucretius, his theory of nature, 16. Magic, characteristics of, 23, 24. Material changes, Greek theory of, 15. Metals, alchemical connexion between, and plants, 34. ---- compared by alchemists with vegetables, 33. ---- mortification of, 65. ---- seed of, 34. ---- their desire to become gold, 40. ---- transmutation of, 33, 39, 46. Natural state of bodies, 39, 43. Oxygen, 144, 145. Paracelsus, his description of alchemists, 25. ---- his distinction between natural and artificial mortification, 65. ---- sketch of life of, 117. Pelican, 92. Perfection, alchemical teaching regarding, 27, 40. Phlogistic theory, 133, 139. Phlogiston, 126, 130, 137. Priestley, his discovery of oxygen, 144. Principles, the alchemical, 49, 51, 54, 60, 133. ---- Lavoisier's use of the word, 163, _note_. Radio-active substances, are they elements? 191, 194, 195; properties of, 185-187. Radio-activity, characteristics of, 183, 184; of radium, 186; of thorium, 193; of uranium, 193. Radium, emanation of, 187; heat from, 186; rays from, 186. Ramsay, on transmutation of elements, 199. Regimens, the alchemical, 72. Sacred art, the, 122. Scientific theories, general characters of, 21, 150. Seed, alchemical doctrine of, 56. Seeds of metals, 34. Simplicity, asserted by alchemists to be the mark of nature, 28, 38. ---- is not necessarily the mark of verity, 138. Solids, liquids, and gases, atomic explanation of, 19. Stahl, his phlogistic theory, 130. Stone, the philosopher's, 32, 35, 49, 58, 72. Thorium, radio-activity of, 183, 193. Transmutation, alchemical doctrine of, 47, 74, 123. ---- character of him who would attempt, 63. ---- of metals, 33, 39, 46, 74. ---- of metals into gold, alchemical account of, 75. ---- of water to earth, 151. Transmutations, apparent examples of, 82. Uranium, radio-activity of, 183, 192; relation of, to radium, 192, 193. Vegetables compared with metals by alchemists, 33. Water contains hydrogen and oxygen, examination of this phrase, 167. Water, different meanings of the word, 53, 167. 
14474	----	THE CHEMICAL HISTORY OF A CANDLE A COURSE OF LECTURES DELIVERED BEFORE A JUVENILE AUDIENCE AT THE ROYAL INSTITUTION BY MICHAEL FARADAY, D.C.L., F.R.S. EDITED BY WILLIAM CROOKES, F.C.S. A NEW IMPRESSION, WITH ILLUSTRATIONS LONDON CHATTO & WINDUS 1908 PREFACE From the primitive pine-torch to the paraffin candle, how wide an interval! between them how vast a contrast! The means adopted by man to illuminate his home at night, stamp at once his position in the scale of civilisation. The fluid bitumen of the far East, blazing in rude vessels of baked earth; the Etruscan lamp, exquisite in form, yet ill adapted to its office; the whale, seal, or bear fat, filling the hut of the Esquimaux or Lap with odour rather than light; the huge wax candle on the glittering altar, the range of gas lamps in our streets,--all have their stories to tell. All, if they could speak (and, after their own manner, they can), might warm our hearts in telling, how they have ministered to man's comfort, love of home, toil, and devotion. Surely, among the millions of fire-worshippers and fire-users who have passed away in earlier ages, _some_ have pondered over the mystery of fire; perhaps some clear minds have guessed shrewdly near the truth. Think of the time man has lived in hopeless ignorance: think that only during a period which might be spanned by the life of one man, has the truth been known. Atom by atom, link by link, has the reasoning chain been forged. Some links, too quickly and too slightly made, have given way, and been replaced by better work; but now the great phenomena are known--the outline is correctly and firmly drawn--cunning artists are filling in the rest, and the child who masters these Lectures knows more of fire than Aristotle did. The candle itself is now made to light up the dark places of nature; the blowpipe and the prism are adding to our knowledge of the earth's crust; but the torch must come first. Among the readers of this book some few may devote themselves to increasing the stores of knowledge: the Lamp of Science _must_ burn. "_Alere flammam._" W. CROOKES. CONTENTS. LECTURE I. A CANDLE: THE FLAME--ITS SOURCES--STRUCTURE--MOBILITY--BRIGHTNESS LECTURE II. BRIGHTNESS OF THE FLAME--AIR NECESSARY FOR COMBUSTION--PRODUCTION OF WATER LECTURE III. PRODUCTS: WATER FROM THE COMBUSTION--NATURE OF WATER--A COMPOUND--HYDROGEN LECTURE IV. HYDROGEN IN THE CANDLE--BURNS INTO WATER--THE OTHER PART OF WATER--OXYGEN LECTURE V. OXYGEN PRESENT IN THE AIR--NATURE OF THE ATMOSPHERE--ITS PROPERTIES--OTHER PRODUCTS FROM THE CANDLE--CARBONIC ACID--ITS PROPERTIES LECTURE VI. CARBON OR CHARCOAL--COAL GAS--RESPIRATION AND ITS ANALOGY TO THE BURNING OP A CANDLE--CONCLUSION LECTURE ON PLATINUM. NOTES. THE CHEMICAL HISTORY OF A CANDLE LECTURE I. A CANDLE: THE FLAME--ITS SOURCES--STRUCTURE--MOBILITY--BRIGHTNESS. I purpose, in return for the honour you do us by coming to see what are our proceedings here, to bring before you, in the course of these lectures, the Chemical History of a Candle. I have taken this subject on a former occasion; and were it left to my own will, I should prefer to repeat it almost every year--so abundant is the interest that attaches itself to the subject, so wonderful are the varieties of outlet which it offers into the various departments of philosophy. There is not a law under which any part of this universe is governed which does not come into play, and is touched upon in these phenomena. There is no better, there is no more open door by which you can enter into the study of natural philosophy, than by considering the physical phenomena of a candle. I trust, therefore, I shall not disappoint you in choosing this for my subject rather than any newer topic, which could not be better, were it even so good. And before proceeding, let me say this also--that though our subject be so great, and our intention that of treating it honestly, seriously, and philosophically, yet I mean to pass away from all those who are seniors amongst us. I claim the privilege of speaking to juveniles as a juvenile myself. I have done so on former occasions--and, if you please, I shall do so again. And though I stand here with the knowledge of having the words I utter given to the world, yet that shall not deter me from speaking in the same familiar way to those whom I esteem nearest to me on this occasion. And now, my boys and girls, I must first tell you of what candles are made. Some are great curiosities. I have here some bits of timber, branches of trees particularly famous for their burning. And here you see a piece of that very curious substance taken out of some of the bogs in Ireland, called _candle-wood_,--a hard, strong, excellent wood, evidently fitted for good work as a resister of force, and yet withal burning so well that where it is found they make splinters of it, and torches, since it burns like a candle, and gives a very good light indeed. And in this wood we have one of the most beautiful illustrations of the general nature of a candle that I can possibly give. The fuel provided, the means of bringing that fuel to the place of chemical action, the regular and gradual supply of air to that place of action--heat and light--all produced by a little piece of wood of this kind, forming, in fact, a natural candle. But we must speak of candles as they are in commerce. Here are a couple of candles commonly called dips. They are made of lengths of cotton cut off, hung up by a loop, dipped into melted tallow, taken out again and cooled, then re-dipped until there is an accumulation of tallow round the cotton. In order that you may have an idea of the various characters of these candles, you see these which I hold in my hand--they are very small, and very curious. They are, or were, the candles used by the miners in coal mines. In olden times the miner had to find his own candles; and it was supposed that a small candle would not so soon set fire to the fire-damp in the coal mines as a large one; and for that reason, as well as for economy's sake, he had candles made of this sort--20, 30, 40, or 60 to the pound. They have been replaced since then by the steel-mill, and then by the Davy-lamp, and other safety-lamps of various kinds. I have here a candle that was taken out of the _Royal George_[1], it is said, by Colonel Pasley. It has been sunk in the sea for many years, subject to the action of salt water. It shews you how well candles may be preserved; for though it is cracked about and broken a good deal, yet, when lighted, it goes on burning regularly, and the tallow resumes its natural condition as soon as it is fused. Mr. Field, of Lambeth, has supplied me abundantly with beautiful illustrations of the candle and its materials. I shall therefore now refer to them. And, first, there is the suet--the fat of the ox--Russian tallow, I believe, employed in the manufacture of these dips, which Gay Lussac, or some one who entrusted him with his knowledge, converted into that beautiful substance, stearin, which you see lying beside it. A candle, you know, is not now a greasy thing like an ordinary tallow candle, but a clean thing, and you may almost scrape off and pulverise the drops which fall from it without soiling anything. This is the process he adopted[2]:--The fat or tallow is first boiled with quick-lime, and made into a soap, and then the soap is decomposed by sulphuric acid, which takes away the lime, and leaves the fat re-arranged as stearic acid, whilst a quantity of glycerin is produced at the same time. Glycerin--absolutely a sugar, or a substance similar to sugar--comes out of the tallow in this chemical change. The oil is then pressed out of it; and you see here this series of pressed cakes, shewing how beautifully the impurities are carried out by the oily part as the pressure goes on increasing, and at last you have left that substance which is melted, and cast into candles as here represented. The candle I have in my hand is a stearin candle, made of stearin from tallow in the way I have told you. Then here is a sperm candle, which comes from the purified oil of the spermaceti whale. Here also are yellow bees-wax and refined bees-wax, from which candles are made. Here, too, is that curious substance called paraffin, and some paraffin candles made of paraffin obtained from the bogs of Ireland. I have here also a substance brought from Japan, since we have forced an entrance into that out-of-the-way place--a sort of wax which a kind friend has sent me, and which forms a new material for the manufacture of candles. And how are these candles made? I have told you about dips, and I will shew you how moulds are made. Let us imagine any of these candles to be made of materials which can be cast. "Cast!" you say. "Why, a candle is a thing that melts; and surely if you can melt it, you can cast it." Not so. It is wonderful, in the progress of manufacture, and in the consideration of the means best fitted to produce the required result, how things turn up which one would not expect beforehand. Candles cannot always be cast. A wax candle can never be cast. It is made by a particular process, which I can illustrate in a minute or two: but I must not spend much time on it. Wax is a thing which, burning so well, and melting so easily in a candle, cannot be cast. However, let us take a material that can be cast. Here is a frame, with a number of moulds fastened in it. The first thing to be done is to put a wick through them. Here is one--a plaited wick, which does not require snuffing[3]--supported by a little wire. It goes to the bottom, where it is pegged in--the little peg holding the cotton tight, and stopping the aperture, so that nothing fluid shall run out. At the upper part there is a little bar placed across, which stretches the cotton and holds it in the mould. The tallow is then melted, and the moulds are filled. After a certain time, when the moulds are cool, the excess of tallow is poured off at one corner, and then cleaned off altogether, and the ends of the wick cut away. The candles alone then remain in the mould, and you have only to upset them, as I am doing, when out they tumble, for the candles are made in the form of cones, being narrower at the top than at the bottom; so that what with their form and their own shrinking, they only need a little shaking, and out they fall. In the same way are made these candles of stearin and of paraffin. It is a curious thing to see how wax candles are made. A lot of cottons are hung upon frames, as you see here, and covered with metal tags at the ends to keep the wax from covering the cotton in those places. These are carried to a heater, where the wax is melted. As you see, the frames can turn round; and as they turn, a man takes a vessel of wax and pours it first down one, and then the next and the next, and so on. When he has gone once round, if it is sufficiently cool, he gives the first a second coat, and so on until they are all of the required thickness. When they have been thus clothed, or fed, or made up to that thickness, they are taken off, and placed elsewhere. I have here, by the kindness of Mr. Field, several specimens of these candles. Here is one only half-finished. They are then taken down, and well rolled upon a fine stone slab, and the conical top is moulded by properly shaped tubes, and the bottoms cut off and trimmed. This is done so beautifully that they can make candles in this way weighing exactly four, or six, to the pound, or any number they please. We must not, however, take up more time about the mere manufacture, but go a little further into the matter. I have not yet referred you to luxuries in candles (for there is such a thing as luxury in candles). See how beautifully these are coloured: you see here mauve, magenta, and all the chemical colours recently introduced, applied to candles. You observe, also, different forms employed. Here is a fluted pillar most beautifully shaped; and I have also here some candles sent me by Mr. Pearsall, which are ornamented with designs upon them, so that as they burn you have as it were a glowing sun above, and a bouquet of flowers beneath. All, however, that is fine and beautiful is not useful. These fluted candles, pretty as they are, are bad candles; they are bad because of their external shape. Nevertheless, I shew you these specimens sent to me from kind friends on all sides, that you may see what is done, and what may be done in this or that direction; although, as I have said, when we come to these refinements, we are obliged to sacrifice a little in utility. Now, as to the light of the candle. We will light one or two, and set them at work in the performance of their proper functions. You observe a candle is a very different thing from a lamp. With a lamp you take a little oil, fill your vessel, put in a little moss or some cotton prepared by artificial means, and then light the top of the wick. When the flame runs down the cotton to the oil, it gets extinguished, but it goes on burning in the part above. Now, I have no doubt you will ask, how is it that the oil, which will not burn of itself, gets up to the top of the cotton, where it will burn? We shall presently examine that; but there is a much more wonderful thing about the burning of a candle than this. You have here a solid substance with no vessel to contain it; and how is it that this solid substance can get up to the place where the flame is? How is it that this solid gets there, it not being a fluid? or, when it is made a fluid, then how is it that it keeps together? This is a wonderful thing about a candle. We have here a good deal of wind, which will help us in some of our illustrations, but tease us in others; for the sake, therefore, of a little regularity, and to simplify the matter, I shall make a quiet flame--for who can study a subject when there are difficulties in the way not belonging to it? Here is a clever invention of some costermonger or street stander in the market-place for the shading of their candles on Saturday nights, when they are selling their greens, or potatoes, or fish. I have very often admired it. They put a lamp-glass round the candle, supported on a kind of gallery, which clasps it, and it can be slipped up and down as required. By the use of this lamp-glass, employed in the same way, you have a steady flame, which you can look at, and carefully examine, as I hope you will do, at home. You see, then, in the first instance, that a beautiful cup is formed. As the air comes to the candle it moves upwards by the force of the current which the heat of the candle produces, and it so cools all the sides of the wax, tallow, or fuel, as to keep the edge much cooler than the part within; the part within melts by the flame that runs down the wick as far as it can go before it is extinguished, but the part on the outside does not melt. If I made a current in one direction, my cup would be lop-sided, and the fluid would consequently run over,--for the same force of gravity which holds worlds together holds this fluid in a horizontal position, and if the cup be not horizontal, of course the fluid will run away in guttering. You see, therefore, that the cup is formed by this beautifully regular ascending current of air playing upon all sides, which keeps the exterior of the candle cool. No fuel would serve for a candle which has not the property of giving this cup, except such fuel as the Irish bogwood, where the material itself is like a sponge, and holds its own fuel. You see now why you would have had such a bad result if you were to burn these beautiful candles that I have shewn you, which are irregular, intermittent in their shape, and cannot therefore have that nicely-formed edge to the cup which is the great beauty in a candle. I hope you will now see that the perfection of a process--that is, its utility--is the better point of beauty about it. It is not the best looking thing, but the best acting thing, which is the most advantageous to us. This good-looking candle is a bad burning one. There will be a guttering round about it because of the irregularity of the stream of air and the badness of the cup which is formed thereby. You may see some pretty examples (and I trust you will notice these instances) of the action of the ascending current when you have A little gutter run down the side of a candle, making it thicker there than it is elsewhere. As the candle goes on burning, that keeps its place and forms a little pillar sticking up by the side, because, as it rises higher above the rest of the wax or fuel, the air gets better round it, and it is more cooled and better able to resist the action of the heat at a little distance. Now, the greatest mistakes and faults with regard to candles, as in many other things, often bring with them instruction which we should not receive if they had not occurred. We come here to be philosophers; and I hope you will always remember that whenever a result happens, especially if it be new, you should say, "What is the cause? Why does it occur?" and you will in the course of time find out the reason. Then, there is another point about these candles which will answer a question,--that is, as to the way in which this fluid gets out of the cup, up the wick, and into the place of combustion. You know that the flames on these burning wicks in candles made of beeswax, stearin, or spermaceti, do not run down to the wax or other matter, and melt it all away, but keep to their own right place. They are fenced off from the fluid below, and do not encroach on the cup at the sides. I cannot imagine a more beautiful example than the condition of adjustment under which a candle makes one part subserve to the other to the very end of its action. A combustible thing like that, burning away gradually, never being intruded upon by the flame, is a very beautiful sight; especially when you come to learn what a vigorous thing flame is--what power it has of destroying the wax itself when it gets hold of it, and of disturbing its proper form if it come only too near. But how does the flame get hold of the fuel? There is a beautiful point about that--_capillary attraction_[4]. "Capillary attraction!" you say,--"the attraction of hairs." Well, never mind the name: it was given in old times, before we had a good understanding of what the real power was. It is by what is called capillary attraction that the fuel is conveyed to the part where combustion goes on, and is deposited there, not in a careless way, but very beautifully in the very midst of the centre of action which takes place around it. Now, I am going to give you one or two instances of capillary attraction. It is that kind of action or attraction which makes two things that do not dissolve in each other still hold together. When you wash your hands, you wet them thoroughly; you take a little soap to make the adhesion better, and you find your hand remains wet. This is by that kind of attraction of which I am about to speak. And, what is more, if your hands are not soiled (as they almost always are by the usages of life), if you put your finger into a little warm water, the water will creep a little way up the finger, though you may not stop to examine it. I have here a substance which is rather porous--a column of salt--and I will pour into the plate at the bottom, not water, as it appears, but a saturated solution of salt which cannot absorb more; so that the action which you see will not be due to its dissolving anything. We may consider the plate to be the candle, and the salt the wick, and this solution the melted tallow. (I have coloured the fluid, that you may see the action better.) You observe that, now I pour in the fluid, it rises and gradually creeps up the salt higher and higher; and provided the column does not tumble over, it will go to the top. [Illustration: Fig. 1.] If this blue solution were combustible, and we were to place a wick at the top of the salt, it would burn as it entered into the wick. It is a most curious thing to see this kind of action taking place, and to observe how singular some of the circumstances are about it. When you wash your hands, you take a towel to wipe off the water; and it is by that kind of wetting, or that kind of attraction which makes the towel become wet with water, that the wick is made wet with the tallow. I have known some careless boys and girls (indeed, I have known it happen to careful people as well) who, having washed their hands and wiped them with a towel, have thrown the towel over the side of the basin, and before long it has drawn all the water out of the basin and conveyed it to the floor, because it happened to be thrown over the side in such a way as to serve the purpose of a syphon.[5] That you may the better see the way in which the substances act one upon another, I have here a vessel made of wire gauze filled with water, and you may compare it in its action to the cotton in one respect, or to a piece of calico in the other. In fact, wicks are sometimes made of a kind of wire gauze. You will observe that this vessel is a porous thing; for if I pour a little water on to the top, it will run out at the bottom. You would be puzzled for a good while if I asked you what the state of this vessel is, what is inside it, and why it is there? The vessel is full of water, and yet you see the water goes in and runs out as if it were empty. In order to prove this to you, I have only to empty it. The reason is this,--the wire, being once wetted, remains wet; the meshes are so small that the fluid is attracted so strongly from the one side to the other, as to remain in the vessel although it is porous. In like manner the particles of melted tallow ascend the cotton and get to the top; other particles then follow by their mutual attraction for each other, and as they reach the flame they are gradually burned. Here is another application of the same principle. You see this bit of cane. I have seen boys about the streets, who are very anxious to appear like men, take a piece of cane, and light it and smoke it, as an imitation of a cigar. They are enabled to do so by the permeability of the cane in one direction, and by its capillarity. If I place this piece of cane on a plate containing some camphin (which is very much like paraffin in its general character), exactly in the same manner as the blue fluid rose through the salt will this fluid rise through the piece of cane. There being no pores at the side, the fluid cannot go in that direction, but must pass through its length. Already the fluid is at the top of the cane: now I can light it and make it serve as a candle. The fluid has risen by the capillary attraction of the piece of cane, just as it does through the cotton in the candle. Now, the only reason why the candle does not burn all down the side of the wick is, that the melted tallow extinguishes the flame. You know that a candle, if turned upside down, so as to allow the fuel to run upon the wick, will be put out. The reason is, that the flame has not had time to make the fuel hot enough to burn, as it does above, where it is carried in small quantities into the wick, and has all the effect of the heat exercised upon it. There is another condition which you must learn as regards the candle, without which you would not be able fully to understand the philosophy of it, and that is the vaporous condition of the fuel. In order that you may understand that, let me shew you a very pretty, but very common-place experiment. If you blow a candle out cleverly, you will see the vapour rise from it. You have, I know, often smelt the vapour of a blown-out candle--and a very bad smell it is; but if you blow it out cleverly, you will be able to see pretty well the vapour into which this solid matter is transformed. I will blow out one of these candles in such a way as not to disturb the air around it, by the continuing action of my breath; and now, if I hold a lighted taper two or three inches from the wick, you will observe a train of fire going through the air till it reaches the candle. I am obliged to be quick and ready, because, if I allow the vapour time to cool, it becomes condensed into a liquid or solid, or the stream of combustible matter gets disturbed. Now, as to the shape or form of the flame. It concerns us much to know about the condition which the matter of the candle finally assumes at the top of the wick--where you have such beauty and brightness as nothing but combustion or flame can produce. [Illustration: Fig. 2.] You have the glittering beauty of gold and silver, and the still higher lustre of jewels, like the ruby and diamond; but none of these rival the brilliancy and beauty of flame. What diamond can shine like flame? It owes its lustre at night-time to the very flame shining upon it. The flame shines in darkness, but the light which the diamond has is as nothing until the flame shine upon it, when it is brilliant again. The candle alone shines by itself, and for itself, or for those who have arranged the materials. Now, let us look a little at the form of the flame as you see it under the glass shade. It is steady and equal; and its general form is that which is represented in the diagram, varying with atmospheric disturbances, and also varying according to the size of the candle. It is a bright oblong--brighter at the top than towards the bottom--with the wick in the middle, and besides the wick in the middle, certain darker parts towards the bottom, where the ignition is not so perfect as in the part above. [Illustration: Fig. 3.] I have a drawing here, sketched many years ago by Hooke, when he made his investigations. It is the drawing of the flame of a lamp, but it will apply to the flame of a candle. The cup of the candle is the vessel or lamp, the melted spermaceti is the oil, and the wick is common to both. Upon that he sets this little flame, and then he represents what is true--a certain quantity of matter rising about it which you do not see, and which, if you have not been here before, or are not familiar with the subject, you will not know of. He has here represented the parts of the surrounding atmosphere that are very essential to the flame, and that are always present with it. There is a current formed, which draws the flame out--for the flame which you see is really drawn out by the current, and drawn upward to a great height--just as Hooke has here shewn you by that prolongation of the current in the diagram. You may see this by taking a lighted candle, and putting it in the sun so as to get its shadow thrown on a piece of paper. How remarkable it is that that thing which is light enough to produce shadows of other objects, can be made to throw its own shadow on a piece of white paper or card, so that you can actually see streaming round the flame something which is not part of the flame, but is ascending and drawing the flame upwards. Now, I am going to imitate the sunlight, by applying the voltaic battery to the electric lamp. You now see our sun, and its great luminosity; and by placing a candle between it and the screen, we get the shadow of the flame. [Illustration: Fig. 4.] You observe the shadow of the candle and of the wick; then there is a darkish part, as represented in the diagram, and then a part which is more distinct. Curiously enough, however, what we see in the shadow as the darkest part of the flame is, in reality, the brightest part; and here you see streaming upwards the ascending current of hot air, as shewn by Hooke, which draws out the flame, supplies it with air, and cools the sides of the cup of melted fuel. I can give you here a little further illustration, for the purpose of shewing you how flame goes up or down; according to the current. I have here a flame--it is not a candle flame--but you can, no doubt, by this time, generalise enough to be able to compare one thing with another. What I am about to do is to change the ascending current that takes the flame upwards into a descending current. This I can easily do by the little apparatus you see before me. The flame, as I have said, is not a candle flame, but it is produced by alcohol, so that it shall not smoke too much. I will also colour the flame with another substance[6], so that you may trace its course; for with the spirit alone you could hardly see well enough to have the opportunity of tracing its direction. By lighting this spirit-of-wine, we have then a flame produced; and you observe that when held in the air, it naturally goes upwards. [Illustration: Fig. 5] You understand now easily enough why flames go up under ordinary circumstances--it is because of the draught of air by which the combustion is formed. But now, by blowing the flame down, you see I am enabled to make it go downwards into this little chimney--the direction of the current being changed. Before we have concluded this course of lectures, we shall shew you a lamp in which the flame goes up and the smoke goes down, or the flame goes down and the smoke goes up. You see, then, that we have the power in this way of varying the flame in different directions. There are now some other points that I must bring before you. Many of the flames you see here vary very much in their shape by the currents of air blowing around them in different directions; but we can, if we like, make flames so that they will look like fixtures, and we can photograph them--indeed, we have to photograph them--so that they become fixed to us, if we wish to find out everything concerning them. That, however, is not the only thing I wish to mention. If I take a flame sufficiently large, it does not keep that homogeneous, that uniform condition of shape, but it breaks out with a power of life which is quite wonderful. I am about to use another kind of fuel, but one which is truly and fairly a representative of the wax or tallow of a candle. I have here a large ball of cotton, which will serve as a wick. And, now that I have immersed it in spirit and applied a light to it, in what way does it differ from an ordinary candle? Why, it differs very much in one respect, that we have a vivacity and power about it, a beauty and a life entirely different from the light presented by a candle. You see those fine tongues of flame rising up. You have the same general disposition of the mass of the flame from below upwards; but, in addition to that, you have this remarkable breaking out into tongues which you do not perceive in the case of a candle. Now, why is this? I must explain it to you, because when you understand that perfectly, you will be able to follow me better in what I have to say hereafter. I suppose some here will have made for themselves the experiment I am going to shew you. Am I right in supposing that anybody here has played at snapdragon? I do not know a more beautiful illustration of the philosophy of flame, as to a certain part of its history, than the game of snapdragon. First, here is the dish; and let me say, that when you play snapdragon properly, you ought to have the dish well-warmed; you ought also to have warm plums and warm brandy, which, however, I have not got. When you have put the spirit into the dish, you have the cup and the fuel; and are not the raisins acting like the wicks? I now throw the plums into the dish, and light the spirit, and you see those beautiful tongues of flame that I refer to. You have the air creeping in over the edge of the dish forming these tongues. Why? Because, through the force of the current and the irregularity of the action of the flame, it cannot flow in one uniform stream. The air flows in so irregularly that you have what would otherwise be a single image, broken up into a variety of forms, and each of these little tongues has an independent existence of its own. Indeed, I might say, you have here a multitude of independent candles. You must not imagine, because you see these tongues all at once, that the flame is of this particular shape. A flame of that shape is never so at any one time. Never is a body of flame, like that which you just saw rising from the ball, of the shape it appears to you. It consists of a multitude of different shapes, succeeding each other so fast that the eye is only able to take cognisance of them all at once. In former times, I purposely analysed a flame of that general character, and the diagram shews you the different parts of which it is composed. They do not occur all at once: it is only because we see these shapes in such rapid succession, that they seem to us to exist all at one time. [Illustration: Fig. 6.] It is too bad that we have not got further than my game of snapdragon; but we must not, under any circumstances, keep you beyond your time. It will be a lesson to me in future to hold you more strictly to the philosophy of the thing, than to take up your time so much with these illustrations. LECTURE II. A CANDLE: BRIGHTNESS OF THE FLAME--AIR NECESSARY FOR COMBUSTION--PRODUCTION OF WATER. We were occupied the last time we met in considering the general character and arrangement as regards the fluid portion of a candle, and the way in which that fluid got into the place of combustion. You see, when we have a candle burning fairly in a regular, steady atmosphere, it will have a shape something like the one shewn in the diagram, and will look pretty uniform, although very curious in its character. And now, I have to ask your attention to the means by which we are enabled to ascertain what happens in any particular part of the flame--why it happens, what it does in happening, and where, after all, the whole candle goes to: because, as you know very well, a candle being brought before us and burned, disappears, if burned properly, without the least trace of dirt in the candlestick--and this is a very curious circumstance. In order, then, to examine this candle carefully, I have arranged certain apparatus, the use of which you will see as I go on. Here is a candle: I am about to put the end of this glass tube into the middle of the flame--into that part which old Hooke has represented in the diagram as being rather dark, and which you can see at any time, if you will look at a candle carefully, without blowing it about. We will examine this dark part first. [Illustration: Fig. 7.] Now, I take this bent glass tube, and introduce one end into that part of the flame, and you see at once that something is coming from the flame, out at the other end of the tube; and if I put a flask there, and leave it for a little while, you will see that something from the middle part of the flame is gradually drawn out, and goes through the tube and into that flask, and there behaves very differently from what it does in the open air. It not only escapes from the end of the tube, but falls down to the bottom of the flask like a heavy substance, as indeed it is. We find that this is the wax of the candle made into a vaporous fluid--not a gas. (You must learn the difference between a gas and a vapour: a gas remains permanent, a vapour is something that will condense.) If you blow out a candle, you perceive a very nasty smell, resulting from the condensation of this vapour. That is very different from what you have outside the flame; and, in order to make that more clear to you, I am about to produce and set fire to a larger portion of this vapour--for what we have in the small way in a candle, to understand thoroughly, we must, as philosophers, produce in a larger way, if needful, that we may examine the different parts. And now Mr. Anderson will give me a source of heat, and I am about to shew you what that vapour is. Here is some wax in a glass flask, and I am going to make it hot, as the inside of that candle-flame is hot, and the matter about the wick is hot. [The Lecturer placed some wax in a glass flask, and heated it over a lamp.] Now, I dare say that is hot enough for me. You see that the wax I put in it has become fluid, and there is a little smoke coming from it. We shall very soon have the vapour rising up. I will make it still hotter, and now we get more of it, so that I can actually pour the vapour out of the flask into that basin, and set it on fire there. This, then, is exactly the same kind of vapour as we have in the middle of the candle; and that you may be sure this is the case, let us try whether we have not got here, in this flask, a real combustible vapour out of the middle of the candle. [Taking the flask into which the tube from the candle proceeded, and introducing a lighted taper.] See how it burns. Now, this is the vapour from the middle of the candle, produced by its own heat; and that is one of the first things you have to consider with respect to the progress of the wax in the course of its combustion, and as regards the changes it undergoes. I will arrange another tube carefully in the flame, and I should not wonder if we were able, by a little care, to get that vapour to pass through the tube to the other extremity, where we will light it, and obtain absolutely the flame of the candle at a place distant from it. Now, look at that. Is not that a very pretty experiment? Talk about laying on gas--why, we can actually lay on a candle! And you see from this that there are clearly two different kinds of action--one the _production_ of the vapour, and the other the _combustion_ of it--both of which take place in particular parts of the candle. [Illustration: Fig. 8] I shall get no vapour from that part which is already burnt. If I raise the tube (fig. 7) to the upper part of the flame, so soon as the vapour has been swept out, what comes away will be no longer combustible: It is already burned. How burned? Why, burned thus:--In the middle of the flame, where the wick is, there is this combustible vapour; on the outside of the flame is the air which we shall find necessary for the burning of the candle; between the two, intense chemical action takes place, whereby the air and the fuel act upon each other, and at the very same time that we obtain light the vapour inside is destroyed. If you examine where the heat of a candle is, you will find it very curiously arranged. Suppose I take this candle, and hold a piece of paper close upon the flame, where is the heat of that flame? Do you not see that it is _not_ in the inside? It is in a ring, exactly in the place where I told you the chemical action was; and even in my irregular mode of making the experiment, if there is not too much disturbance, there will always be a ring. This is a good experiment for you to make at home. Take a strip of paper, have the air in the room quiet, and put the piece of paper right across the middle of the flame (I must not talk while I make the experiment), and you will find that it is burnt in two places, and that it is not burnt, or very little so, in the middle; and when you have tried the experiment once or twice, so as to make it nicely, you will be very interested to see where the heat is, and to find that it is where the air and the fuel come together. This is most important for us as we proceed with our subject. Air is absolutely necessary for combustion; and, what is more, I must have you understand that _fresh_ air is necessary, or else we should be imperfect in our reasoning and our experiments. Here is a jar of air. I place it over a candle, and it burns very nicely in it at first, shewing that what I have said about it is true; but there will soon be a change. See how the flame is drawing upwards, presently fading, and at last going out. And going out, why? Not because it wants air merely, for the jar is as full now as it was before; but it wants pure, fresh air. The jar is full of air, partly changed, partly not changed; but it does not contain sufficient of the fresh air which is necessary for the combustion of a candle. These are all points which we, as young chemists, have to gather up; and if we look a little more closely into this kind of action, we shall find certain steps of reasoning extremely interesting. For instance, here is the oil-lamp I shewed you--an excellent lamp for our experiments--the old Argand lamp. I now make it like a candle [obstructing the passage of air into the centre of the flame]; there is the cotton; there is the oil rising up it; and there is the conical flame. It burns poorly, because there is a partial restraint of air. I have allowed no air to get to it, save round the outside of the flame, and it does not burn well. I cannot admit more air from the outside, because the wick is large; but if, as Argand did so cleverly, I open a passage to the middle of the flame, and so let air come in there, you will see how much more beautifully it burns. If I shut the air off, look how it smokes; and why? We have now some very interesting points to study. We have the case of the combustion of a candle; we have the case of a candle being put out by the want of air; and we have now the case of imperfect combustion; and this is to us so interesting, that I want you to understand it as thoroughly as you do the case of a candle burning in its best possible manner. I will now make a great flame, because we need the largest possible illustrations. Here is a larger wick [burning turpentine on a ball of cotton]. All these things are the same as candles, after all. If we have larger wicks, we must have a larger supply of air, or we shall have less perfect combustion. Look now at this black substance going up into the atmosphere; there is a regular stream of it. I have provided means to carry off the imperfectly burned part, lest it should annoy you. Look at the soots that fly off from the flame: see what an imperfect combustion it is, because it cannot get enough air. What, then, is happening? Why, certain things which are necessary to the combustion of a candle are absent, and very bad results are accordingly produced; but we see what happens to a candle when it is burnt in a pure and proper state of air. At the time when I shewed you this charring by the ring of flame on the one side of the paper, I might have also shewn you, by turning to the other side, that the burning of a candle produces the same kind of soot--charcoal or carbon. But, before I shew that, let me explain to you--as it is quite necessary for our purpose--that, though I take a candle and give you, as the general result, its combustion in the form of a flame, we must see whether combustion is always in this condition, or whether there are other conditions of flame; and we shall soon discover that there are, and that they are most important to us. I think, perhaps, the best illustration of such a point to us, as juveniles, is to shew the result of strong contrast. Here is a little gunpowder. You know that gunpowder burns with flame--we may fairly call it flame. It contains carbon and other materials, which altogether cause it to burn with a flame. And here is some pulverised iron, or iron filings. Now, I purpose burning these two things together. I have a little mortar in which I will mix them. (Before I go into these experiments, let me hope that none of you, by trying to repeat them, for fun's sake, will do any harm. These things may all be very properly used if you take care; but without that, much mischief will be done.) Well, then, here is a little gunpowder, which I put at the bottom of that little wooden vessel, and mix the iron filings up with it, my object being to make the gunpowder set fire to the filings and burn them in the air, and thereby shew the difference between substances burning with flame and not with flame. Here is the mixture; and when I set fire to it, you must watch the combustion, and you will see that it is of two kinds. You will see the gunpowder burning with a flame, and the filings thrown up. You will see them burning too, but without the production of flame. They will each burn separately. [The Lecturer then ignited the mixture.] There is the gunpowder, which burns with a flame; and there are the filings--they burn with a different kind of combustion. You see, then, these two great distinctions; and upon these differences depend all the utility and all the beauty of flame which we use for the purpose of giving out light. When we use oil, or gas, or candle, for the purpose of illumination, their fitness all depends upon these different kinds of combustion. There are such curious conditions of flame, that it requires some cleverness and nicety of discrimination to distinguish the kinds of combustion one from another. For instance, here is a powder which is very combustible, consisting, as you see, of separate little particles. It is called _lycopodium_[7], and each of these particles can produce a vapour, and produce its own flame; but, to see them burning, you would imagine it was all one flame. I will now set fire to a quantity, and you will see the effect. We saw a cloud of flame, apparently in one body; but that rushing noise [referring to the sound produced by the burning] was a proof that the combustion was not a continuous or regular one. This is the lightning of the pantomimes, and a very good imitation. [The experiment was twice repeated by blowing lycopodium from a glass tube through a spirit-flame.] This is not an example of combustion like that of the filings I have been speaking of, to which we must now return. Suppose I take a candle, and examine that part of it which appears brightest to our eyes. Why, there I get these black particles, which already you have seen many times evolved from the flame, and which I am now about to evolve in a different way. I will take this candle and clear away the gutterage, which occurs by reason of the currents of air; and if I now arrange a glass tube so as just to dip into this luminous part, as in our first experiment, only higher, you see the result. In place of having the same white vapour that you had before, you will now have a black vapour. There it goes, as black as ink. It is certainly very different from the white vapour; and when we put a light to it, we shall find that it does not burn, but that it puts the light out. Well, these particles, as I said before, are just the smoke of the candle; and this brings to mind that old employment which Dean Swift recommended to servants for their amusement, namely, writing on the ceiling of a room with a candle. But what is that black substance? Why, it is the same carbon which exists in the candle. How comes it out of the candle? It evidently existed in the candle, or else we should not have had it here. And now I want you to follow me in this explanation. You would hardly think that all those substances which fly about London, in the form of soots and blacks, are the very beauty and life of the flame, and which are burned in it as those iron filings were burned here. Here is a piece of wire gauze, which will not let the flame go through it; and I think you will see, almost immediately, that when I bring it low enough to touch that part of the flame which is otherwise so bright, that it quells and quenches it at once, and allows a volume of smoke to rise up. I want you now to follow me in this point,--that whenever a substance burns, as the iron filings burnt in the flame of gunpowder, without assuming the vaporous state (whether it becomes liquid or remains solid), it becomes exceedingly luminous. I have here taken three or four examples apart from the candle, on purpose to illustrate this point to you; because what I have to say is applicable to all substances, whether they burn or whether they do not burn,--that they are exceedingly bright if they retain their solid state, and that it is to this presence of solid particles in the candle-flame that it owes its brilliancy. Here is a platinum-wire, a body which does not change by heat. If I heat it in this flame, see how exceedingly luminous it becomes. I will make the flame dim, for the purpose of giving a little light only, and yet you will see that the heat which it can give to that platinum-wire, though far less than the heat it has itself, is able to raise the platinum-wire to a far higher state of effulgence. This flame has carbon in it; but I will take one that has no carbon in it. There is a material, a kind of fuel--a vapour, or gas, whichever you like to call it--in that vessel, and it has no solid particles in it; so I take that because it is an example of flame itself burning without any solid matter whatever; and if I now put this solid substance in it, you see what an intense heat it has, and how brightly it causes the solid body to glow. This is the pipe through which we convey this particular gas, which we call hydrogen, and which you shall know all about next time we meet. And here is a substance called oxygen, by means of which this hydrogen can burn; and although we produce, by their mixture, far greater heat[8] than you can obtain from the candle, yet there is very little light. If, however, I take a solid substance, and put that into it, we produce an intense light If I take a piece of lime, a substance which will not burn, and which will not vaporise by the heat (and because it does not vaporise, remains solid, and remains heated), you will soon observe what happens as to its glowing. I have here a most intense heat, produced by the burning of hydrogen in contact with the oxygen; but there is as yet very little light--not for want of heat, but for want of particles which can retain their solid state; but when I hold this piece of lime in the flame of the hydrogen as it burns in the oxygen, see how it glows! This is the glorious lime-light, which rivals the voltaic-light, and which is almost equal to sunlight. I have here a piece of carbon or charcoal, which will burn and give us light exactly in the same manner as if it were burnt as part of a candle. The heat that is in the flame of a candle decomposes the vapour of the wax, and sets free the carbon particles--they rise up heated and glowing as this now glows, and then enter into the air. But the particles when burnt never pass off from a candle in the form of carbon. They go off into the air as a perfectly invisible substance, about which we shall know hereafter. Is it not beautiful to think that such a process is going on, and that such a dirty thing as charcoal can become so incandescent? You see it comes to this--that all bright flames contain these solid particles; all things that burn and produce solid particles, either during the time they are burning, as in the candle, or immediately after being burnt, as in the case of the gunpowder and iron-filings,--all these things give us this glorious and beautiful light. I will give you a few illustrations. Here is a piece of phosphorus, which burns with a bright flame. Very well; we may now conclude that phosphorus will produce, either at the moment that it is burning or afterwards, these solid particles. Here is the phosphorus lighted, and I cover it over with this glass for the purpose of keeping in what is produced. What is all that smoke? That smoke consists of those very particles which are produced by the combustion of the phosphorus. Here, again, are two substances. This is chlorate of potassa, and this other sulphuret of antimony. I shall mix these together a little, and then they may be burnt in many ways. I shall touch them with a drop of sulphuric acid, for the purpose of giving you an illustration of chemical action, and they will instantly burn[9]. [The Lecturer then ignited the mixture by means of sulphuric acid.] Now, from the appearance of things, you can judge for yourselves whether they produce solid matter in burning. I have given you the train of reasoning which will enable you to say whether they do or do not; for what is this bright flame but the solid particles passing off? [Illustration: Fig. 9.] Mr. Anderson has in the furnace a very hot crucible,--I am about to throw into it some zinc filings, and they will burn with a flame like gunpowder. I make this experiment because you can make it well at home. Now, I want you to see what will be the result of the combustion of this zinc. Here it is burning--burning beautifully like a candle, I may say. But what is all that smoke, and what are those little clouds of wool which will come to you if you cannot come to them, and make themselves sensible to you in the form of the old philosophic wool, as it was called? We shall have left in that crucible, also, a quantity of this woolly matter. But I will take a piece of this same zinc and make an experiment a little more closely at home, as it were. You will have here the same thing happening. Here is the piece of zinc, there [pointing to a jet of hydrogen] is the furnace, and we will set to work and try and burn the metal. It glows, you see: there is the combustion, and there is the white substance into which it burns. And so, if I take that flame of hydrogen as the representative of a candle, and shew you a substance like zinc burning in the flame, you will see that it was merely during the action of combustion that this substance glowed--while it was kept hot; and if I take a flame of hydrogen, and put this white substance from the zinc into it, look how beautifully it glows, and just because it is a solid substance. I will now take such a flame as I had a moment since, and set free from it the particles of carbon. Here is some camphine, which will burn with a smoke; but if I send these particles of smoke through this pipe into the hydrogen flame, you will see they will burn and become luminous, because we heat them a second time. There they are. Those are the particles of carbon re-ignited a second time. They are those particles which you can easily see by holding a piece of paper behind them, and which, whilst they are in the flame, are ignited by the heat produced, and, when so ignited, produce this brightness. When the particles are not separated, you get no brightness. The flame of coal-gas owes its brightness to the separation, during combustion, of these particles of carbon, which are equally in that as in a candle. I can very quickly alter that arrangement. Here, for instance, is a bright flame of gas. Supposing I add so much air to the flame as to cause it all to burn before those particles are set free, I shall not have this brightness; and I can do that in this way:--If I place over the jet this wire-gauze cap, as you see, and then light the gas over it, it burns with a non-luminous flame, owing to its having plenty of air mixed with it before it burns; and if I raise the gauze, you see it does not burn below[10]. There is plenty of carbon in the gas; but, because the atmosphere can get to it, and mix with it before it burns, you see how pale and blue the flame is. And if I blow upon a bright gas-flame, so as to consume all this carbon before it gets heated to the glowing point, it will also burn blue: [The Lecturer illustrated his remarks by blowing on the gas-light.] The only reason why I have not the same bright light when I thus blow upon the flame is, that the carbon meets with sufficient air to burn it before it gets separated in the flame in a free state. The difference is solely due to the solid particles not being separated before the gas is burnt. You observe that there are certain products as the result of the combustion of a candle, and that of these products one portion may be considered as charcoal, or soot; that charcoal, when afterwards burnt, produces some other product; and it concerns us very much now to ascertain what that other product is. We shewed that something was going away; and I want you now to understand how much is going up into the air; and for that purpose we will have combustion on a little larger scale. From that candle ascends heated air, and two or three experiments will shew you the ascending current; but, in order to give you a notion of the quantity of matter which ascends in this way, I will make an experiment by which I shall try to imprison some of the products of this combustion. For this purpose I have here what boys call a fire-balloon. I use this fire-balloon merely as a sort of measure of the result of the combustion we are considering; and I am about to make a flame in such an easy and simple manner as shall best serve my present purpose. This plate shall be the "cup," we will so say, of the candle; this spirit shall be our fuel; and I am about to place this chimney over it, because it is better for me to do so than to let things proceed at random. [Illustration: Fig. 10.] Mr. Anderson will now light the fuel, and here at the top we shall get the results of the combustion. What we get at the top of that tube is exactly the same, generally speaking, as you get from the combustion of a candle; but we do not get a luminous flame here, because we use a substance which is feeble in carbon. I am about to put this balloon--not into action, because that is not my object--but to shew you the effect which results from the action of those products which arise from the candle, as they arise here from the furnace. [The balloon was held over the chimney, when it immediately commenced to fill.] You see how it is disposed to ascend; but we must not let it up, because it might come in contact with those upper gas-lights, and that would be very inconvenient. [The upper gas-lights were turned out, at the request of the Lecturer, and the balloon was allowed to ascend.] Does not that shew you what a large bulk of matter is being evolved? Now, there is going through this tube [placing a large glass tube over a candle] all the products of that candle, and you will presently see that the tube will become quite opaque. Suppose I take another candle, and place it under a jar, and then put a light on the other side, just to shew you what is going on. You see that the sides of the jar become cloudy, and the light begins to burn feebly. It is the products, you see, which make the light so dim, and this is the same thing which makes the sides of the jar so opaque. If you go home and take a spoon that has been in the cold air, and hold it over a candle--not so as to soot it--you will find that it becomes dim, just as that jar is dim. If you can get a silver dish, or something of that kind, you will make the experiment still better. And now, just to carry your thoughts forward to the time we shall next meet, let me tell you that it is _water_ which causes the dimness; and when we next meet. I will shew you that we can make it, without difficulty, assume the form of a liquid. LECTURE III. PRODUCTS: WATER FROM THE COMBUSTION--NATURE OF WATER--A COMPOUND--HYDROGEN. I dare say you will remember that when we parted we had just mentioned the word "products" from the candle. For when a candle burns we found we were able, by nice adjustment, to get various products from it. There was one substance which was not obtained when the candle was burning properly, which was charcoal or smoke; and there was some other substance that went upwards from the flame which did not appear as smoke, but took some other form, and made part of that general current which, ascending from the candle upwards, becomes invisible, and escapes. There were also other products to mention. You remember that in that rising current having its origin at the candle, we found that one part was condensable against a cold spoon, or against a clean plate, or any other cold thing, and another part was incondensable. We will first take the condensable part, and examine it; and, strange to say, we find that that part of the product is just water--nothing but water. On the last occasion I spoke of it incidentally, merely saying that water was produced among the condensable products of the candle; but to-day I wish to draw your attention to water, that we may examine it carefully, especially in relation to this subject, and also with respect to its general existence on the surface of the globe. Now, having previously arranged an experiment for the purpose of condensing water from the products of the candle, my next point will be to shew you this water; and perhaps one of the best means that I can adopt for shewing its presence to so many at once, is to exhibit a very visible action of water, and then to apply that test to what is collected as a drop at the bottom of that vessel. I have here a chemical substance, discovered by Sir Humphrey Davy, which has a very energetic action upon water, which I shall use as a test of the presence of water. If I take a little piece of it--it is called potassium, as coming from potash,--if I take a little piece of it, and throw it into that basin, you see how it shews the presence of water by lighting up and floating about, burning with a violent flame. I am now going to take away the candle which has been burning beneath the vessel containing ice and salt, and you see a drop of water--a condensed product of the candle--hanging from under the surface of the dish. [Illustration: Fig. 11.] I will shew you that potassium has the same action upon it as upon the water in that basin in the experiment we have just tried. See, it takes fire, and burns in just the same manner. I will take another drop upon this glass slab, and when I put the potassium on to it, you see at once, from its taking fire, that there is water present. Now, that water was produced by the candle. In the same manner, if I put this spirit-lamp under that jar, you will soon see the latter become damp, from the dew which is deposited upon it--that dew being the result of combustion; and I have no doubt you will shortly see by the drops of water which fall upon the paper below, that there is a good deal of water produced from the combustion of the lamp. I will let it remain, and you can afterwards see how much water has been collected. So, if I take a gas-lamp, and put any cooling arrangement over it, I shall get water--water being likewise produced from the combustion of gas. Here, in this bottle, is a quantity of water--perfectly pure, distilled water, produced from the combustion of a gas-lamp--in no point different from the water that you distil from the river, or ocean, or spring, but exactly the same thing. Water is one individual thing--it never changes. We can add to it by careful adjustment, for a little while, or we can take it apart, and get other things from it; but water, as water, remains always the same, either in a solid, liquid, or fluid state. Here, again [holding another bottle], is some water produced by the combustion of an oil-lamp. A pint of oil, when burnt fairly and properly, produces rather more than a pint of water. Here, again, is some water, produced by a rather long experiment from a wax candle. And so we can go on with almost all combustible substances, and find that if they burn with a flame, as a candle, they produce water. You may make these experiments yourselves. The head of a poker is a very good thing to try with, and if it remains cold long enough over the candle, you may get water condensed in drops on it; or a spoon or ladle, or anything else may be used, provided it be clean, and can carry off the heat, and so condense the water. And now--to go into the history of this wonderful production of water from combustibles, and by combustion--I must first of all tell you that this water may exist in different conditions; and although you may now be acquainted with all its forms, they still require us to give a little attention to them for the present, so that we may perceive how the water, whilst it goes through its Protean changes, is entirely and absolutely the same thing, whether it is produced from a candle, by combustion, or from the rivers or ocean. First of all, water, when at the coldest, is ice. Now, we philosophers---I hope that I may class you and myself together in this case--speak of water as water, whether it be in its solid, or liquid, or gaseous state,--we speak of it chemically as water. Water is a thing compounded of two substances, one of which we have derived from the candle, and the other we shall find elsewhere. Water may occur as ice; and you have had most excellent opportunities lately of seeing this. Ice changes back into water--for we had on our last Sabbath a strong instance of this change, by the sad catastrophe which occurred in our own house, as well as in the houses of many of our friends,--ice changes back into water when the temperature is raised: water also changes into steam when it is warmed enough. The water which we have here before us is in its densest state[11], and although it changes in weight, in condition, in form, and in many other qualities, it still is water; and whether we alter it into ice by cooling, or whether we change it into steam by heat, it increases in volume,--in the one case very strangely and powerfully, and in the other case very largely and wonderfully. For instance, I will now take this tin cylinder, and pour a little water into it; and seeing how much water I pour in, you may easily estimate for yourselves how high it will rise in the vessel: it will cover the bottom about two inches. I am now about to convert the water into steam, for the purpose of shewing to you the different volumes which water occupies in its different states of water and steam. Let us now take the case of water changing into ice: we can effect that by cooling it in a mixture of salt and pounded ice[12]; and I shall do so to shew you the expansion of water into a thing of larger bulk when it is so changed. These bottles [holding one] are made of strong cast iron, very strong and very thick--I suppose they are the third of an inch in thickness; they are very carefully filled with water, so as to exclude all air, and then they are screwed down tight. We shall see that when we freeze the water in these iron vessels, they will not be able to hold the ice, and the expansion within them will break them in pieces as these [pointing to some fragments] are broken, which have been bottles of exactly the same kind. I am about to put these two bottles into that mixture of ice and salt, for the purpose of shewing that when water becomes ice, it changes in volume in this extraordinary way. In the mean time look at the change which has taken place in the water to which we have applied heat--it is losing its fluid state. You may tell this by two or three circumstances. I have covered the mouth of this glass flask, in which water is boiling, with a watch-glass. Do you see what happens? It rattles away like a valve chattering, because the steam rising from the boiling water sends the valve up and down, and forces itself out, and so makes it clatter. You can very easily perceive that the flask is quite full of steam, or else it would not force its way out. You see, also, that the flask contains a substance very much larger than the water, for it fills the whole of the flask over and over again, and there it is blowing away into the air; and yet you cannot observe any great diminution in the bulk of the water, which shews you that its change of bulk is very great when it becomes steam. I have put our iron bottles containing water into this freezing mixture, that you may see what happens. No communication will take place, you observe, between the water in the bottles and the ice in the outer vessel. But there will be a conveyance of heat from the one to the other; and if we are successful--we are making our experiment in very great haste--I expect you will by-and-by, so soon as the cold has taken possession of the bottles and their contents, hear a pop on the occasion of the bursting of the one bottle or the other; and, when we come to examine the bottles, we shall find their contents masses of ice, partly enclosed by the covering of iron which is too small for them, because the ice is larger in bulk than the water. You know very well that ice floats upon water: if a boy falls through a hole into the water, he tries to get on the ice again to float him up. Why does the ice float?--think of that, and philosophise. Because the ice is larger than the quantity of water which can produce it; and therefore the ice weighs the lighter, and the water is the heavier. To return now to the action of heat on water. See what a stream of vapour is issuing from this tin vessel! You observe, we must have made it quite full of steam to have it sent out in that great quantity. And now, as we can convert the water into steam by heat, we convert it back into liquid water by the application of cold. And if we take a glass, or any other cold thing, and hold it over this steam, see how soon it gets damp with water; it will condense it until the glass is warm--it condenses the water which is now running down the sides of it. I have here another experiment to shew the condensation of water from a vaporous state back into a liquid state, in the same way as the vapour, one of the products of the candle, was condensed against the bottom of the dish, and obtained in the form of water; and to shew you how truly and thoroughly these changes take place, I will take this tin flask, which is now full of steam, and close the top. We shall see what takes place when we cause this water or steam to return back to the fluid state by pouring some cold water on the outside. [The Lecturer poured the cold water over the vessel, when it immediately collapsed.] You see what has happened. If I had closed the stopper, and still kept the heat applied to it, it would have burst the vessel; yet, when the steam returns to the state of water, the vessel collapses, there being a vacuum produced inside by the condensation of the steam. I shew you these experiments for the purpose of pointing out that in all these occurrences there is nothing that changes the water into any other thing--it still remains water; and so the vessel is obliged to give way, and is crushed inwards, as in the other case, by the further application of heat, it would have been blown outwards. [Illustration: Fig. 12.] And what do you think the bulk of that water is when it assumes the vaporous condition? You see that cube [pointing to a cubic foot]. There, by its side, is a cubic inch, exactly the same shape as the cubic foot, and that bulk of water [the cubic inch] is sufficient to expand into that bulk [the cubic foot] of steam; and, on the contrary, the application of cold will contract that large quantity of steam into this small quantity of water. [Illustration: Fig. 13.] [One of the iron bottles burst at that moment.] Ah! There is one of our bottles burst, and here you see is a crack down one side an eighth of an inch in width. [The other now exploded, sending the freezing mixture in all directions.] This other bottle is also broken; although the iron was nearly half-an-inch thick, the ice has burst it asunder. These changes always take place in water: they do not require to be always produced by artificial means,--we only use them here because we want to produce a small winter round that little bottle, instead of a long and severe one. But if you go to Canada, or to the North, you will find the temperature there out of doors will do the same thing as has been done here by the freezing mixture. To return to our quiet philosophy. We shall not in future be deceived, therefore, by any changes that are produced in water. Water is the same everywhere, whether produced from the ocean or from the flame of the candle. Where, then, is this water which we get from a candle? I must anticipate a little, and tell you. It evidently comes, as to part of it, from the candle; but is it within the candle beforehand? No. It is not in the candle; and it is not in the air round about the candle which is necessary for its combustion. It is neither in one nor the other, but it comes from their conjoint action, a part from the candle, a part from the air; and this we have now to trace, so that we may understand thoroughly what is the chemical history of a candle when we have it burning on our table. How shall we get at this? I myself know plenty of ways, but I want _you_ to get at it from the association in your own minds of what I have already told you. I think you can see a little in this way. We had just now the case of a substance which acted upon the water in the way that Sir Humphrey Davy shewed us[13], and which I am now going to recall to your minds by making again an experiment upon that dish. It is a thing which we have to handle very carefully, for you see, if I allow a little splash of water to come upon this mass, it sets fire to part of it; and if there were free access of air, it would quickly set fire to the whole. Now, this is a metal--a beautiful and bright metal--which rapidly changes in the air, and, as you know, rapidly changes in water. I will put a piece on the water, and you see it burns beautifully, making a floating lamp, using the water in the place of air. Again, if we take a few iron filings or turnings, and put them in water, we find that they likewise undergo an alteration. They do not change so much as this potassium does, but they change somewhat in the same way; they become rusty, and shew an action upon the water, though in a different degree of intensity to what this beautiful metal does: but they act upon the water in the same manner generally as this potassium. I want you to put these different facts together in your minds. I have another metal here [zinc], and when we examined it with regard to the solid substance produced by its combustion, we had an opportunity of seeing that it burned; and I suppose, if I take a little strip of this zinc and put it over the candle, you will see something half-way, as it were, between the combustion of potassium on the water and the action of iron,--you see there is a sort of combustion. It has burned, leaving a white ash or residuum, and here also we find that the metal has a certain amount of action upon water. By degrees we have learned how to modify the action of these different substances, and to make them tell us what we want to know. And now, first of all, I take iron. It is a common thing in all chemical reactions, where we get any result of this kind, to find that it is increased by the action of heat; and if we want to examine minutely and carefully the action of bodies one upon another, we often have to refer to the action of heat. You are aware, I believe, that iron-filings burn beautifully in the air; but I am about to shew you an experiment of this kind, because it will impress upon you what I am going to say about iron in its action on water. If I take a flame and make it hollow;--you know why, because I want to get air to it and into it, and therefore I make it hollow--and then take a few iron-filings and drop them into the flame, you see how well they burn. That combustion results from the chemical action which is going on when we ignite those particles. And so we proceed to consider these different effects, and ascertain what iron will do when it meets with water. It will tell us the story so beautifully, so gradually and regularly, that I think it will please you very much. I have here a furnace with a pipe going through it like an iron gun-barrel, and I have stuffed that barrel full of bright iron-turnings, and placed it across the fire, to be made red-hot. We can either send air through the barrel to come in contact with the iron, or we can send steam from this little boiler at the end of the barrel. Here is a stop-cock which shuts off the steam from the barrel until we wish to admit it. There is some water in these glass jars, which I have coloured blue, so that you may see what happens. Now, you know very well that any steam I might send through that barrel, if it went through into the water, would be condensed; for you have seen that steam cannot retain its gaseous form if it be cooled down. [Illustration: Fig. 14.] You saw it here [pointing to the tin flask] crushing itself into a small bulk, and causing the flask holding it to collapse; so that if I were to send steam through that barrel, it would be condensed--supposing the barrel were cold: it is, therefore, heated to perform the experiment I am now about to shew you. I am going to send the steam through the barrel in small quantities; and you shall judge for yourselves, when you see it issue from the other end, whether it still remains steam. Steam is condensible into water, and when you lower the temperature of steam, you convert it back into fluid water; but I have lowered the temperature of the gas which I have collected in this jar, by passing it through water after it has traversed the iron barrel, and still it does not change back into water. I will take another test and apply to this gas. (I hold the jar in an inverted position, or my substance would escape.) If I now apply a light to the mouth of the jar, it ignites with a slight noise. That tells you that it is not steam. Steam puts out a fire--it does not burn; but you saw that what I had in that jar burnt. We may obtain this substance equally from water produced from the candle-flame as from any other source. When it is obtained by the action of the iron upon the aqueous vapour, it leaves the iron in a state very similar to that in which these filings were after they were burnt. It makes the iron heavier than it was before. So long as the iron remains in the tube and is heated, and is cooled again without the access of air or water, it does not change in its weight; but after having had this current of steam passed over it, it then comes out heavier that it was before, having taken something out of the steam, and having allowed something else to pass forth, which we see here. And now, as we have another jar full, I will shew you something most interesting. It is a combustible gas; and I might at once take this jar and set fire to the contents, and shew you that it is combustible; but I intend to shew you more if I can. It is also a very light substance. Steam will condense: this body will rise in the air, and not condense. [Illustration: Fig. 15] Suppose I take another glass jar, empty of all but air: if I examine it with a taper, I shall find that it contains nothing but air. I will now take this jar full of the gas that I am speaking of, and deal with it as though it were a light body. I will hold both upside-down, and turn the one up under the other; and that which did contain the gas procured from the steam, what does it contain now? You will find it now only contains air. But look! Here is the combustible substance [taking the other jar] which I have poured out of the one jar into the other. It still preserves its quality, and condition, and independence, and therefore is the more worthy of our consideration, as belonging to the products of a candle. Now, this substance which we have just prepared by the action of iron on the steam or water, we can also get by means of those other things which you have already seen act so well upon the water. If I take a piece of potassium, and make the necessary arrangements, it will produce this gas; and if, instead, a piece of zinc, I find, when I come to examine it very carefully, that the main reason why this zinc cannot act upon the water continuously as the other metal does, is because the result of the action of the water envelopes the zinc in a kind of protecting coat. We have learned in consequence, that if we put into our vessel only the zinc and water, they by themselves do not give rise to much action, and we get no result. But suppose I proceed to dissolve off this varnish--this encumbering substance--which I can do by a little acid; the moment I do this, I find the zinc acting upon the water exactly as the iron did, but at the common temperature. The acid in no way is altered, except in its combination with the oxide of zinc, which is produced. I have now poured the acid into the glass, and the effect is as though I were applying heat to cause this boiling up. There is something coming off from the zinc very abundantly, which is not steam. There is a jar full of it; and you will find that I have exactly the same combustible substance remaining in the vessel, when I hold it upside-down, that I produced during the experiment with the iron barrel. This is what we get from water--the same substance which is contained in the candle. [Illustration: Fig. 16.] Let us now trace distinctly the connection between these two points. This is hydrogen--a body classed among those things which in Chemistry we call elements, because we can get nothing else out of them. A candle is not an elementary body, because we can get carbon out of it; we can get this hydrogen out of it, or at least out of the water which it supplies. And this gas has been so named hydrogen, because it is that element which, in association with another, generates water. [Footnote: [greek: hudos], "water," and [greek: gennao], "I generate."] Mr. Anderson having now been able to get two or three jars of gas, we shall have a few experiments to make, and I want to shew you the best way of making these experiments. I am not afraid to shew you, for I wish you to make experiments, if you will only make them with care and attention, and the assent of those around you. As we advance in Chemistry, we are obliged to deal with substances which are rather injurious, if in their wrong places--the acids, and heat, and combustible things we use, might do harm if carelessly employed. If you want to make hydrogen, you can make it easily from bits of zinc, and sulphuric or muriatic acid. Here is what in former times was called the "philosopher's candle." It is a little phial with a cork, and a tube or pipe passing through it. [Illustration: Fig. 17.] And I am now putting a few little pieces of zinc into it. This little instrument I am going to apply to a useful purpose in our demonstrations--for I want to shew you that you can prepare hydrogen, and make some experiments with it as you please at your own homes. Let me here tell you why I am so careful to fill this phial nearly, and yet not quite full. I do it because the evolved gas, which, as you have seen, is very combustible, is explosive to a considerable extent when mixed with air, and might lead to harm, if you were to apply a light to the end of that pipe before all the air had been swept out of the space above the water. I am now about to pour in the sulphuric acid. I have used very little zinc, and more sulphuric acid and water, because I want to keep it at work for some time. I therefore take care in this way to modify the proportions of the ingredients, so that I may have a regular supply--not too quick, and not too slow. Supposing I now take a glass and put it upside-down over the end of the tube, because the hydrogen is light I expect that it will remain in that vessel a little while. We will now test the contents of our glass to see if there be hydrogen in it. I think I am safe in saying we have caught some [applying a light]. There it is, you see. I will now apply a light to the top of the tube. There is the hydrogen burning. There is our philosophical candle. It is a foolish feeble sort of a flame, you may say; but it is so hot that scarcely any common flame gives out so much heat. It goes on burning regularly, and I am now about to put that flame to burn under a certain arrangement, in order that we may examine its results and make use of the information which we may thereby acquire. Inasmuch as the candle produces water, and this gas comes out of the water, let us see what this gives us by the same process of combustion that the candle went through when it burnt in the atmosphere; and for that purpose I am going to put the lamp under this apparatus, in order to condense whatever may arise from the combustion within it In the course of a short time you will see moisture appearing in the cylinder, and you will get the water running down the side; and the water from this hydrogen flame will have absolutely the same effect upon all our tests, being obtained by the same general process as in the former case. This hydrogen is a very beautiful substance. It is so light that it carries things up: it is far lighter than the atmosphere; and I dare say I can shew you this by an experiment which, if you are very clever, some of you may even have skill enough to repeat. Here is our generator of hydrogen, and here are some soap-suds. I have an india-rubber tube connected with the hydrogen generator, and at the end of the tube is a tobacco-pipe. [Illustration: Fig. 18.] I can thus put the pipe into the suds, and blow bubbles by means of the hydrogen. You observe how the bubbles fall downwards when I blow them with my warm breath; but notice the difference when I blow them with hydrogen. [The Lecturer here blew bubbles with hydrogen, which rose to the roof of the theatre.] It shews you how light this gas must be in order to carry with it not merely the ordinary soap-bubble, but the larger portion of a drop hanging to the bottom of it. I can shew its lightness in a better way than this; larger bubbles than these may be so lifted up; indeed, in former times balloons used to be filled with this gas. Mr. Anderson will fasten this tube on to our generator, and we shall have a stream of hydrogen here with which we can charge this balloon made of collodion. I need not even be very careful to get all the air out, for I know the power of this gas to carry it up. [Two collodion balloons were inflated, and sent up, one being held by a string.] Here is another larger one made of thin membrane, which we will fill and allow to ascend. You will see they will all remain floating about until the gas escapes. What, then, are the comparative weights of these substances? I have a table here which will shew you the proportion which their weights bear to each other. I have taken a pint and a cubic foot as the measures, and have placed opposite to them the respective figures. A pint measure of this hydrogen weighs three-quarters of our smallest weight (a grain), and a cubic foot weighs one-twelfth of an ounce; whereas a pint of water weighs 8,750 grains, and a cubic foot of water weighs almost 1,000 ounces. You see, therefore, what a vast difference there is between the weight of a cubic foot of water and a cubic foot of hydrogen. Hydrogen gives rise to no substance that can become solid, either during combustion or afterwards as a product of its combustion. But when it burns, it produces water only; and if we take a cold glass and put it over the flame, it becomes damp, and you have water, produced immediately in appreciable quantity; and nothing is produced by its combustion but the same water which you have seen the flame of the candle produce. It is important to remember that this hydrogen is the only thing in nature which furnishes water as the sole product of combustion. And now we must endeavour to find some additional proof of the general character and composition of water; and for this purpose I will keep you a little longer, so that at our next meeting we may be better prepared for the subject. We have the power of arranging the zinc which you have seen acting upon the water by the assistance of an acid, in such a manner as to cause all the power to be evolved in the place where we require it I have behind me a voltaic pile, and I am just about to shew you, at the end of this lecture, its character and power, that you may see what we shall have to deal with when next we meet. I hold here the extremities of the wires which transport the power from behind me, and which I shall cause to act on the water. We have previously seen what a power of combustion is possessed by the potassium, or the zinc, or the iron-filings; but none of them shew such energy as this. [The Lecturer here made contact between the two terminal wires of the battery, when a brilliant flash of light was produced.] This light is, in fact, produced by a forty-zinc power of burning: it is a power that I can carry about in my hands, through these wires, at pleasure--although, if I applied it wrongly to myself, it would destroy me in an instant, for it is a most intense thing, and the power you see here put forth while you count five [bringing the poles in contact, and exhibiting the electric light] is equivalent to the power of several thunder-storms, so great is its force[14]. And that you may see what intense energy it has, I will take the ends of the wires which convey the power from the battery, and with it I dare say I can burn this iron file. Now, this is a chemical power, and one which, when we next meet, I shall apply to water, and shew you what results we are able to produce. LECTURE IV. HYDROGEN IN THE CANDLE--BURNS INTO WATER--THE OTHER PART OF WATER--OXYGEN. I see you are not tired of the candle yet, or I am sure you would not be interested in the subject in the way you are. When our candle was burning, we found it produced water exactly like the water we have around us; and by further examination of this water we found in it that curious body, hydrogen--that light substance of which there is some in this jar. We afterwards saw the burning powers of that hydrogen, and that it produced water. And I think I introduced to your notice an apparatus which I very briefly said was an arrangement of chemical force, or power, or energy, so adjusted as to convey its power to us in these wires; and I said I should use that force to pull the water to pieces, to see what else there was in the water besides hydrogen; because, you remember, when we passed the water through the iron tube, we by no means got the weight of water back which we put in, in the form of steam, though we had a very large quantity of gas evolved. We have now to see what is the other substance present. That you may understand the character and use of this instrument, let us make an experiment or two. Let us put together, first of all, some substances, knowing what they are, and then see what that instrument does to them. There is some copper (observe the various changes which it can undergo), and here is some nitric acid, and you will find that this, being a strong chemical agent, will act very powerfully when I add it to the copper. It is now sending forth a beautiful red vapour; but as we do not want that vapour, Mr. Anderson will hold it near the chimney for a short time, that we may have the use and beauty of the experiment without the annoyance. The copper which I have put into the flask will dissolve: it will change the acid and the water into a blue fluid, containing copper and other things; and I propose then shewing you how this voltaic battery deals with it; and in the mean-time we will arrange another kind of experiment for you to see what power it has. This is a substance which is to us like water--that is to say, it contains bodies which we do not know of as yet, as water contains a body which we do not know as yet. Now, this solution of a salt[15] I will put upon paper, and spread about, and apply the power of the battery to it, and observe what will happen. Three or four important things will happen which we shall take advantage of. I place this wetted paper upon a sheet of tinfoil, which is convenient for keeping all clean, and also for the advantageous application of the power; and this solution, you see, is not at all affected by being put upon the paper or tinfoil, nor by anything else I have brought in contact with it yet, and which, therefore, is free to us to use as regards that instrument. But first let us see that our instrument is in order. Here are our wires. Let us see whether it is in the state in which it was last time. We can soon tell. As yet, when I bring them together, we have no power, because the conveyers--what we call the electrodes--the passages or ways for the electricity--are stopped; but now Mr. Anderson by that [referring to a sudden flash at the ends of the wires] has given me a telegram to say that it is ready. Before I begin our experiment I will get Mr. Anderson to break contact again at the battery behind me, and we will put a platinum-wire across to connect the poles, and then if I find I can ignite a pretty good length of this wire, we shall be safe in our experiment. Now you will see the power. [The connection was established, and the intermediate wire became red-hot.] There is the power running beautifully through the wire, which I have made thin on purpose to shew you that we have those powerful forces; and now, having that power, we will proceed with it to the examination of water. I have here two pieces of platinum, and if I lay them down upon this piece of paper [the moistened paper on the tinfoil], you will see no action; and if I take them up, there is no change that you can see, but the arrangement remains just as it was before. But, now, see what happens: if I take these two poles and put either one or the other of them down separately on the platinum-plates, they do nothing for me, both are perfectly without action; but if I let them both be in contact at the same moment, see what happens [a brown spot appeared under each pole of the battery]. Look here at the effect that takes place, and see how I have pulled something apart from the white--something brown; and I have no doubt, if I were to arrange it thus, and were to put one of the poles to the tinfoil on the other side of the paper--why, I get such a beautiful action upon the paper, that I am going to see whether I cannot write with it--a telegram, if you please. [The Lecturer here traced the word "juvenile" on the paper with one of the terminal wires.] See there how beautifully we can get our results! You see we have here drawn something, which we have not known about before, out of this solution. Let us now take that flask from Mr. Andersen's hands, and see what we can draw out of that. This, you know, is a liquid which we have just made up from copper and nitric acid, whilst our other experiments were in hand; and though I am making this experiment very hastily, and may bungle a little, yet I prefer to let you see what I do rather than prepare it beforehand. Now, see what happens. These two platinum-plates are the two ends (or I will make them so immediately) of this apparatus; and I am about to put them in contact with that solution just as we did a moment ago on the paper. It does not matter to us whether the solution be on the paper or whether it be in the jar, so long as we bring the ends of the apparatus to it. If I put the two platinums in by themselves, they come out as clean and as white as they go in [inserting them into the fluid without connecting them with the battery]; but when we take the power and lay that on [the platinums were connected with the battery and again dipped into the solution], this, you see [exhibiting one of the platinums], is at once turned into copper, as it were: it has become like a plate of copper; and that [exhibiting the other piece of platinum] has come out quite clean. If I take this coppered piece and change sides, the copper will leave the right-hand side and come over to the left side; what was before the coppered plate comes out clean, and the plate which was clean comes out coated with copper; and thus you see that the same copper we put into this solution we can also take out of it by means of this instrument. Putting that solution aside, let us now see what effect this instrument will have upon water. Here are two little platinum-plates which I intend to make the ends of the battery, and this (C) is a little vessel so shaped as to enable me to take it to pieces, and shew you its construction. In these two cups (A and B) I pour mercury, which touches the ends of the wires connected with the platinum-plates. In the vessel (C) I pour some water containing a little acid (but which is put only for the purpose of facilitating the action; it undergoes no change in the process), and connected with the top of the vessel is a bent glass tube (D), which may remind you of the pipe which was connected with the gun barrel in our furnace experiment, and which now passes under the jar (F). I have now adjusted this apparatus, and we will proceed to affect the water in some way or other. In the other case, I sent the water through a tube which was made red-hot; I am now going to pass the electricity through the contents of this vessel. Perhaps I may boil the water; if I do boil the water, I shall get steam; and you know that steam condenses when it gets cold, and you will therefore see by that whether I do boil the water or not. Perhaps, however, I shall not boil the water, but produce some other effect. You shall have the experiment and see. There is one wire which I will put to this side (A), and here is the other wire which I will put to the other side (B), and you will soon see whether any disturbance takes place. Here it is seeming to boil up famously; but does it boil? Let us see whether that which goes out is steam or not. I think you will soon see the jar (F) will be filled with vapour, if that which rises from the water is steam. But can it be steam? Why, certainly not; because there it remains, you see, unchanged. There it is standing over the water, and it cannot therefore be steam, but must be a permanent gas of some sort What is it? Is it hydrogen? Is it anything else? Well, we will examine it. If it is hydrogen, it will burn. [The Lecturer then ignited a portion of the gas collected, which burnt with an explosion.] [Illustration: Fig. 19] It is certainly something combustible, but not combustible in the way that hydrogen is. Hydrogen would not have given you that noise; but the colour of that light, when the thing did burn, was like that of hydrogen: it will, however, burn without contact with the air. That is why I have chosen this other form of apparatus, for the purpose of pointing out to you what are the particular circumstances of this experiment. In place of an open vessel I have taken one that is closed (our battery is so beautifully active that we are even boiling the mercury, and getting all things right--not wrong, but vigorously right); and I am going to shew you that that gas, whatever it may be, can burn without air, and in that respect differs from a candle, which cannot burn without the air. And our manner of doing this is as follows:--I have here a glass vessel (G) which is fitted with two platinum-wires (IK), through which I can apply electricity; and we can put the vessel on the air-pump and exhaust the air, and when we have taken the air out we can bring it here and fasten it on to this jar (F), and let into the vessel that gas which was formed by the action of the voltaic battery upon the water, and which we have produced by changing the water into it,--for I may go as far as this, and say we have really, by that experiment, changed the water into that gas. We have not only altered its condition, but we have changed it really and truly into that gaseous substance, and all the water is there which was decomposed by the experiment. As I screw this vessel (GH) on here (H), and make the tubes well connected, and when I open the stop-cocks (HHH), if you watch the level of the water (in F), you will see that the gas will rise. I will now close the stop-cocks, as I have drawn up as much as the vessel can hold, and being safely conveyed into that chamber, I will pass into it an electric spark from this Leyden jar (L), when the vessel, which is now quite clear and bright, will become dim. There will be no sound, for the vessel is strong enough to confine the explosion. [A spark was then passed through the jar, when the explosive mixture was ignited.] Did you see that brilliant light? If I again screw the vessel on to the jar, and open these stop-cocks, you will see that the gas will rise a second time. [The stop-cocks were then opened.] Those gases [referring to the gases first collected in the jar, and which had just been ignited by the electric spark] have disappeared, as you see: their place is vacant, and fresh gas has gone in. Water has been formed from them; and if we repeat our operation [repeating the last experiment], I shall have another vacancy, as you will see by the water rising. I always have an empty vessel after the explosion, because the vapour or gas into which that water has been resolved by the battery explodes under the influence of the spark, and changes into water; and by-and-by you will see in this upper vessel some drops of water trickling down the sides and collecting at the bottom. We are here dealing with water entirely, without reference to the atmosphere. The water of the candle had the atmosphere helping to produce it; but in this way it can be produced independently of the air. Water, therefore, ought to contain that other substance which the candle takes from the air, and which, combining with the hydrogen, produces water. Just now you saw that one end of this battery took hold of the copper, extracting it from the vessel which contained the blue solution. It was effected by this wire; and surely we may say, if the battery has such power with a metallic solution which we made and unmade, may we not find that it is possible to split asunder the component parts of the water, and put them into this place and that place? Suppose I take the poles--the metallic ends of this battery--and see what will happen with the water in this apparatus (fig. 20), where we have separated the two ends far apart. [Illustration: Fig. 20.] I place one here (at A), and the other there (at B), and I have little shelves with holes which I can put upon each pole, and so arrange them that whatever escapes from the two ends of the battery will appear as separate gases; for you saw that the water did not become vaporous, but gaseous. The wires are now in perfect and proper connection with the vessel containing the water; and you see the bubbles rising: let us collect these bubbles and see what they are. Here is a glass cylinder (O); I fill it with water and put it over one end (A) of the pile; and I will take another (H) and put it over the other end (B) of the pile. And so now we have a double apparatus, with both places delivering gas. Both these jars will fill with gas. There they go, that to the right (H) filling very rapidly; the one to the left (O) filling not so rapidly; and though I have allowed some bubbles to escape, yet still the action is going on pretty regularly; and were it not that one is rather smaller than the other, you would see that I should have twice as much in this (H) as I have in that (O). Both these gases are colourless; they stand over the water without condensing; they are alike in all things--I mean in all _apparent_ things; and we have here an opportunity of examining these bodies and ascertaining what they are. Their bulk is large, and we can easily apply experiments to them. I will take this jar (H) first, and will ask you to be prepared to recognise hydrogen. Think of all its qualities--the light gas which stood well in inverted vessels, burning with a pale flame at the mouth of the jar--and see whether this gas does not satisfy all these conditions. If it be hydrogen, it will remain here while I hold this jar inverted. [A light was then applied, when the hydrogen burnt] What is there now in the other jar? You know that the two together made an explosive mixture. But what can this be which we find as the other constituent in water, and which must therefore be that substance which made the hydrogen burn? We know that the water we put into the vessel consisted of the two things together. We find one of these is hydrogen: what must that other be which was in the water before the experiment, and which we now have by itself? I am about to put this lighted splinter of wood into the gas. The gas itself will not burn, but it will make the splinter of wood burn. [The Lecturer ignited the end of the wood, and introduced it into the jar of gas.] See how it invigorates the combustion of the wood, and how it makes it burn far better than the air would make it burn; and now you see by itself that every other substance which is contained in the water, and which, when the water was formed by the burning of the candle, must have been taken from the atmosphere. What shall we call it, A, B, or C? Let us call it O--call it "Oxygen:" it is a very good distinct-sounding name. This, then, is the oxygen which was present in the water, forming so large a part of it. We shall now begin to understand more clearly our experiments and researches; because, when we have examined these things once or twice, we shall soon see why a candle burns in the air. When we have in this way analysed the water--that is to say, separated, or electrolysed its parts out of it--we get two volumes of hydrogen, and one of the body that burns it. And these two are represented to us on the following diagram, with their weights also stated; and we shall find that the oxygen is a very heavy body by comparison with the hydrogen. It is the other element in water. I had better, perhaps, tell you now how we get this oxygen abundantly, having shewn you how we can separate it from the water. Oxygen, as you will immediately imagine, exists in the atmosphere; for how should the candle burn to produce water without it? _____________________ | | | | 1 | 8 | | | | | | Oxygen. | Oxygen, . . . . 88.9 | | | | |_________| Hydrogen, . . . 11.1 | Hydrogen. | ----- | | 9 Water,. . . . . 100.0 | | | | | | |___________| Such a thing would be absolutely impossible, and chemically impossible, without oxygen. [Illustration: Fig. 21.] Can we get it from the air? Well, there are some very complicated and difficult processes by which we can get it from the air; but we have better processes. There is a substance called the black oxide of manganese: it is a very black-looking mineral, but very useful, and when made red-hot it gives out oxygen. Here is an iron bottle which has had some of this substance put into it, and there is a tube fixed to it, and a fire ready made, and Mr. Anderson will put that retort into the fire, for it is made of iron, and can stand the heat. Here is a salt called chlorate of potassa, which is now made in large quantities for bleaching, and chemical and medical uses, and for pyrotechnic and other purposes. I will take some and mix it with some of the oxide of manganese (oxide of copper, or oxide of iron would do as well); and if I put these together in a retort, far less than a red heat is sufficient to evolve this oxygen from the mixture. I am not preparing to make much, because we only want sufficient for our experiments; only, as you will see immediately, if I use too small a charge, the first portion of the gas will be mixed with the air already in the retort, and I should be obliged to sacrifice the first portion of the gas, because it would be so much diluted with air; the first portion must therefore be thrown away. You will find in this case, that a common spirit-lamp is quite sufficient for me to get the oxygen, and so we shall have two processes going on for its preparation. See how freely the gas is coming over from that small portion of the mixture. We will examine it, and see what are its properties. Now, in this way we are producing, as you will observe, a gas just like the one we had in the experiment with the battery, transparent, undissolved by water, and presenting the ordinary visible properties of the atmosphere. (As this first jar contains the air, together with the first portions of the oxygen set free during the preparation, we will carry it out of the way, and be prepared to make our experiments in a regular, dignified manner.) And, inasmuch as that power of making wood, wax, or other things burn, was so marked in the oxygen we obtained by means of the voltaic battery from water, we may expect to find the same property here. We will try it You see there is the combustion of a lighted taper in air, and here is its combustion in this gas [lowering the taper into the jar]. See how brightly and how beautifully it burns! You can also see more than this,--you will perceive it is a heavy gas, whilst the hydrogen would go up like a balloon, or even faster than a balloon, when not encumbered with the weight of the envelope. [Illustration: Fig. 22.] You may easily see that although we obtained from water twice as much in volume of the hydrogen as of oxygen, it does not follow that we have twice as much in weight--because one is heavy, and the other a very light gas. We have means of weighing gases or air; but without stopping to explain, that, let me just tell you what their respective weights are. The weight of a pint of hydrogen is three-quarters of a grain; the weight of the same quantity of oxygen is nearly twelve grains. This is a very great difference. The weight of a cubit foot of hydrogen is one-twelfth of an ounce; and the weight of a cubit foot of oxygen is one ounce and a third. And so on we might come to masses of matter which may be weighed in the balance, and which we can take account of as to hundredweights and as to tons, as you will see almost immediately. Now, as regards this very property of oxygen supporting combustion, which we may compare to air, I will take a piece of candle to shew it you in a rough way, and the result will be rough. There is our candle burning in the air: how will it burn in oxygen? I have here a jar of this gas, and I am about to put it over the candle for you to compare the action of this gas with that of the air. Why, look at it: it looks something like the light you saw at the poles of the voltaic battery. Think how vigorous that action must be! And yet, during all that action, nothing more is produced than what is produced by the burning of the candle in air. We have the same production of water, and the same phenomena exactly, when we use this gas instead of air, as we have when the candle is burnt in air. But now we have got a knowledge of this new substance, we can look at it a little more distinctly, in order to satisfy ourselves that we have got a good general understanding of this part of the product of a candle. It is wonderful how great the supporting powers of this substance are as regards combustion. For instance, here is a lamp which, simple though it be, is the original, I may say, of a great variety of lamps which are constructed for divers purposes--for light-houses, microscopic illuminations, and other uses; and if it were proposed to make it burn very brightly, you would say, "If a candle burnt better in oxygen, will not a lamp do the same?" Why, it will do so. Mr. Anderson will give me a tube coming from our oxygen reservoir, and I am about to apply it to this flame, which I will previously make burn badly on purpose. There comes the oxygen: what a combustion that makes! But if I shut it off, what becomes of the lamp? [The flow of oxygen was stopped, and the lamp relapsed to its former dimness.] It is wonderful how, by means of oxygen, we get combustion accelerated. But it does not affect merely the combustion of hydrogen, or carbon, or the candle; but it exalts all combustions of the common kind. We will take one which relates to iron, for instance, as you have already seen iron burn a little in the atmosphere. Here is a jar of oxygen, and this is a piece of iron wire; but if it were a bar as thick as my wrist, it would burn the same. [Illustration: Fig. 23.] I first attach a little piece of wood to the iron, I then set the wood on fire and let them both down together into the jar. The wood is now alight, and there it burns as wood should burn in oxygen; but it will soon communicate its combustion to the iron. The iron is now burning brilliantly, and will continue so for a long time. As long as we supply oxygen, so long can we carry on the combustion of the iron, until the latter is consumed. We will now put that on one side, and take some other substance; but we must limit our experiments, for we have not time to spare for all the illustrations you would have a right to if we had more time. We will take a piece of sulphur--you know how sulphur burns in the air--well, we put it into the oxygen, and you will see that whatever can burn in air, can burn with a far greater intensity in oxygen, leading you to think that perhaps the atmosphere itself owes all its power of combustion to this gas. The sulphur is now burning very quietly in the oxygen; but you cannot for a moment mistake the very high and increased action which takes place when it is so burnt, instead of being burnt merely in common air. [Illustration: Fig. 24.] I am now about to shew you the combustion of another substance--phosphorus. I can do it better for you here than you can do it at home. This is a very combustible substance; and if it be so combustible in air, what might you expect it would be in oxygen? I am about to shew it to you not in its fullest intensity, for if I did so we should almost blow the apparatus up--I may even now crack the jar, though I do not want to break things carelessly. You see how it burns in the air. But what a glorious light it gives out when I introduce it into oxygen! [Introducing the lighted phosphorus into the jar of oxygen.] There you see the solid particles going off which cause that combustion to be so brilliantly luminous. Thus far we have tested this power of oxygen, and the high combustion it produces by means of other substances. We must now, for a little while longer, look at it as respects the hydrogen. You know, when we allowed the oxygen and the hydrogen derived from the water to mix and burn together, we had a little explosion. You remember, also, that when I burnt the oxygen and the hydrogen in a jet together, we got very little light, but great heat. I am now about to set fire to oxygen and hydrogen, mixed in the proportion in which they occur in water. Here is a vessel containing one volume of oxygen and two volumes of hydrogen. This mixture is exactly of the same nature as the gas we just now obtained from the voltaic battery: it would be far too much to burn at once; I have therefore arranged to blow soap-bubbles with it, and burn those bubbles, that we may see by a general experiment or two how this oxygen supports the combustion of the hydrogen. First of all, we will see whether we can blow a bubble. Well, there goes the gas [causing it to issue through a tobacco-pipe into some soap-suds]. Here I have a bubble. I am receiving them on my hand: and you will perhaps think I am acting oddly in this experiment; but it is to shew you that we must not always trust to noise and sounds, but rather to real facts. [Exploding a bubble on the palm of his hand.] I am afraid to fire a bubble from the end of the pipe, because the explosion would pass up into the jar and blow it to pieces. This oxygen then will unite with the hydrogen, as you see by the phenomena, and hear by the sound, with the utmost readiness of action, and all its powers are then taken up in its neutralisation of the qualities of the hydrogen. So now I think you will perceive the whole history of water with reference to oxygen and the air, from what we have before said. Why does a piece of potassium decompose water? Because it finds oxygen in the water. What is set free when I put it in the water, as I am about to do again? It sets free hydrogen, and the hydrogen burns; but the potassium itself combines with oxygen; and this piece of potassium, in taking the water apart--the water, you may say, derived from the combustion of the candle--takes away the oxygen which the candle took from the air, and so sets the hydrogen free; and even if I take a piece of ice, and put a piece of potassium upon it, the beautiful affinities by which the oxygen and the hydrogen are related are such, that the ice will absolutely set fire to the potassium. I shew this to you to-day, in order to enlarge your ideas of these things, and that you may see how greatly results are modified by circumstances. There is the potassium on the ice, producing a sort of volcanic action. It will be my place, when next we meet, having pointed out these anomalous actions, to shew you that none of these extra and strange effects are met with by us--that none of these strange and injurious actions take place when we are burning, not merely a candle, but gas in our streets, or fuel in our fireplaces, so long as we confine ourselves within the laws that Nature has made for our guidance. LECTURE V. OXYGEN PRESENT IN THE AIR--NATURE OF THE ATMOSPHERE--ITS PROPERTIES--OTHER PRODUCTS FROM THE CANDLE--CARBONIC ACID--ITS PROPERTIES. We have now seen that we can produce hydrogen and oxygen from the water that we obtained from the candle. Hydrogen, you know, comes from the candle, and oxygen, you believe, comes from the air. But then you have a right to ask me, "How is it that the air and the oxygen do not equally well burn the candle?" If you remember what happened when I put a jar of oxygen over a piece of candle, you recollect there was a very different kind of combustion to that which took place in the air. Now, why is this? It is a very important question, and one I shall endeavour to make you understand: it relates most intimately to the nature of the atmosphere, and is most important to us. We have several tests for oxygen besides the mere burning of bodies. You have seen a candle burnt in oxygen, or in the air; you have seen phosphorus burnt in the air, or in oxygen; and you have seen iron-filings burnt in oxygen. But we have other tests besides these, and I am about to refer to one or two of them for the purpose of carrying your conviction and your experience further. Here we have a vessel of oxygen. I will shew its presence to you: if I take a little spark and put it into that oxygen, you know, by the experience you gained the last time we met, what will happen; if I put that spark into the jar, it will tell you whether we have oxygen here or not. Yes! We have proved it by combustion; and now here is another test for oxygen, which is a very curious and useful one. I have here two jars full of gas, with a plate between them to prevent their mixing; I take the plate away, and the gases are creeping one into the other. "What happens?" say you: "they together produce no such combustion as was seen in the case of the candle." But see how the presence of oxygen is told by its association with this other substance[14]. What a beautifully coloured gas I have obtained in this way, shewing me the presence of the oxygen! In the same way we can try this experiment by mixing common air with this test-gas. Here is a jar containing air--such air as the candle would burn in--and here is a jar or bottle containing the test-gas. I let them come together over water, and you see the result: the contents of the test-bottle are flowing into the jar of air, and you see I obtain exactly the same kind of action as before, and that shews me that there is oxygen in the air--the very same substance that has been already obtained by us from the water produced by the candle. But then, beyond that, how is it that the candle does not burn in air as well as in oxygen? We will come to that point at once. I have here two jars; they are filled to the same height with gas, and the appearance to the eye is alike in both, and I really do not know at present which of these jars contains oxygen and which contains air, although I know they have previously been filled with these gases. But here is our test-gas, and I am going to work with the two jars, in order to examine whether there is any difference between them in the quality of reddening this gas. I am now going to turn this test-gas into one of the jars, and observe what happens. There is reddening, you see; there is then oxygen present. We will now test the other jar; but you see this is not so distinctly red as the first: and, further, this curious thing happens,--if I take these two gases and shake them well together with water, we shall absorb the red gas; and then, if I put in more of this test-gas and shake again, we shall absorb more; and I can go on as long as there be any oxygen present to produce that effect. If I let in air, it will not matter; but the moment I introduce water, the red gas disappears; and I may go on in this way, putting in more and more of the test-gas, until I come to something left behind which will not redden any longer by the use of that particular body that rendered the air and the oxygen red. Why is that? You see in a moment it is because there is, besides oxygen, something else present which is left behind. I will let a little more air into the jar, and if it turns red you will know that some of that reddening gas is still present, and that consequently it was not for the want of this producing body that that air was left behind. Now, you will begin to understand what I am about to say. You saw that when I burnt phosphorus in a jar, as the smoke produced by the phosphorus and the oxygen of the air condensed, it left a good deal of gas unburnt, just as this red gas left something untouched,--there was, in fact, this gas left behind, which the phosphorus cannot touch, which the reddening gas cannot touch, and this something is not oxygen, and yet is part of the atmosphere. So that is one way of opening out air into the two things of which it is composed--oxygen, which burns our candles, our phosphorus, or anything else; and this other substance--nitrogen--which will not burn them. This other part of the air is by far the larger proportion, and it is a very curious body, when we come to examine it; it is remarkably curious, and yet you say, perhaps, that it is very uninteresting. It is uninteresting in some respects because of this--that it shews no brilliant effects of combustion. If I test it with a taper as I do oxygen and hydrogen, it does not burn like hydrogen, nor does it make the taper burn like oxygen. Try it in any way I will, it does neither the one thing nor the other: it will not take fire; it will not let the taper burn; it puts out the combustion of everything. There is nothing that will burn in it in common circumstances. It has no smell; it is not sour; it does not dissolve in water; it is neither an acid nor an alkali; it is as indifferent to all our organs as it is possible for a thing to be. And you might say, "It is nothing; it is not worth chemical attention; what does it do in the air?" Ah! then come our beautiful and fine results shewn us by an observant philosophy. Suppose, in place of having nitrogen, or nitrogen and oxygen, we had pure oxygen as our atmosphere; what would become of us? You know very well that a piece of iron lit in a jar of oxygen goes on burning to the end. When you see a fire in an iron grate, imagine where the grate would go to if the whole of the atmosphere were oxygen. The grate would burn up more powerfully than the coals--for the iron of the grate itself is even more combustible than the coals which we burn in it. A fire put into the middle of a locomotive would be a fire in a magazine of fuel, if the atmosphere were oxygen. The nitrogen lowers it down and makes it moderate and useful for us, and then, with all that, it takes away with it the fumes that you have seen produced from the candle, disperses them throughout the whole of the atmosphere, and carries them away to places where they are wanted to perform a great and glorious purpose of good to man, for the sustenance of vegetation; and thus does a most wonderful work, although you say, on examining it, "Why, it is a perfectly indifferent thing." This nitrogen in its ordinary state is an inactive element; no action short of the most intense electric force, and then in the most infinitely small degree, can cause the nitrogen to combine directly with the other element of the atmosphere, or with other things round about it; it is a perfectly indifferent, and therefore to say, a safe substance. But before I take you to that result, I must tell you about the atmosphere itself. I have written on this diagram the composition of one hundred parts of atmospheric air:-- Bulk. Weight. Oxygen, . . . . . 20 22.3 Nitrogen, . . . . 80 77.7 ---- ----- l00 100.0 It is a true analysis of the atmosphere, so far as regards the quantity of oxygen and the quantity of nitrogen present. By our analysis, we find that 5 pints of the atmosphere contain only 1 pint of oxygen, and 4 pints, or 4 parts, of nitrogen by bulk. That is our analysis of the atmosphere. It requires all that quantity of nitrogen to reduce the oxygen down, so as to be able to supply the candle properly with fuel, so as to supply us with an atmosphere which our lungs can healthily and safely breathe; for it is just as important to make the oxygen right for us to breathe, as it is to make the atmosphere right for the burning of the fire and the candle. But now for this atmosphere. First of all, let me tell you the weight of these gases. A pint of nitrogen weighs 10-4/10 grains, or a cubic foot weighs 1-1/6 ounce. That is the weight of the nitrogen. The oxygen is heavier: a pint of it weighs 11-9/10 grains, and a cubic foot weighs 1-3/4 ounce. A pint of air weighs about 10-7/10 grains, and a cubic foot 1-1/5 ounce. [Illustration: Fig. 25.] You have asked me several times, and I am very glad you have, "How do you weigh gases?" I will shew you; it is very simple, and easily done. Here is a balance, and here a copper bottle, made as light as we can consistent with due strength, turned very nicely in the lathe, and made perfectly air-tight, with a stop-cock, which we can open and shut, which at present is open, and therefore allows the bottle to be full of air. I have here a nicely-adjusted balance, in which I think the bottle, in its present condition, will be balanced by the weight on the other side. And here is a pump by which we can force the air into this bottle, and with it we will force in a certain number of volumes of air, as measured by the pump. [Twenty measures were pumped in.] We will shut that in and put it in the balance. See how it sinks: it is much heavier than it was. By what? By the air that we have forced into it by the pump. There is not a greater _bulk_ of air, but there is the same bulk of _heavier_ air, because we have forced in air upon it. And that you may have a fair notion in your mind as to how much this air measures, here is a jar full of water. We will open that copper vessel into this jar, and let the air return to its former state. All I have to do now is to screw them tightly together, and to turn the taps, when there, you see, is the bulk of the twenty pumps of air which I forced into the bottle; and to make sure that we have been quite correct in what we have been doing, we will take the bottle again to the balance, and, if it is now counterpoised by the original weight, we shall be quite sure we have made our experiment correctly. [Illustration: Fig. 26.] It is balanced; so, you see, we can find out the weight of the extra volumes of air forced in, in that way, and by that means we are able to ascertain that a cubic foot of air weighs 1-1/5 ounce. But that small experiment will by no means convey to your mind the whole literal truth of this matter. It is wonderful how it accumulates when you come to larger volumes. This bulk of air [a cubic foot] weighs 1-1/5 ounce. What do you think of the contents of that box above there, which I have had made for the purpose? The air which is within that box weighs one pound--a full pound; and I have calculated the weight of the air in this room,--you would hardly imagine it, but it is above a ton. So rapidly do the weights rise up, and so important is the presence of the atmosphere, and of the oxygen and the nitrogen in it, and the use it performs in conveying things to and fro from place to place, and carrying bad vapours to places where they will do good instead of harm. Having given you that little illustration with respect to the weight of the air, let me shew you certain consequences of it. You have a right to them, because you would not understand so much without it. Do you remember this kind of experiment? Have you ever seen it? Suppose I take a pump somewhat similar to the one I had a little while ago to force air into the bottle, and suppose I place it in such a manner that by certain arrangements I can apply my hand to it: my hand moves about in the air so easily that it seems to feel nothing, and I can hardly get velocity enough by any motion of my own in the atmosphere to make sure that there is much resistance to it. [Illustration: Fig. 27.] But, when I put my hand here [on the air-pump receiver, which was afterwards exhausted], you see what happens. Why is my hand fastened to this place, and why am I able to pull this pump about? And see! how is it that I can hardly get my hand away? Why is this? It is the weight of the air--the weight of the air that is above. I have another experiment here, which I think will explain to you more about it. When the air is pumped from underneath the bladder which is stretched over this glass, you will see the effect in another shape: the top is quite flat at present, but I will make a very little motion with the pump, and now look at it--see how it has gone down, see how it is bent in. You will see the bladder go in more and more, until at last I expect it will be driven in and broken by the force of the atmosphere pressing upon it. [Illustration: Fig. 28.] [The bladder at last broke with a loud report.] Now, that was done entirely by the weight of the air pressing on it, and you can easily understand how that is. The particles that are piled up in the atmosphere stand upon each other, as these five cubes do. You can easily conceive that four of these five cubes are resting upon the bottom one, and if I take that away, the others will all sink down. So it is with the atmosphere: the air that is above is sustained by the air that is beneath; and when the air is pumped away from beneath them, the change occurs which you saw when I placed my hand on the air-pump, and which you saw in the case of the bladder, and which you shall see better here. I have tied over this jar a piece of sheet india-rubber, and I am now about to take away the air from the inside of the jar; and if you will watch the india-rubber--which acts as a partition between the air below and the air above--you will see, when I pump, how the pressure shews itself. See where it is going to--I can actually put my hand into the jar; and yet this result is only caused by the great and powerful action of the air above. How beautifully it shews this curious circumstance! Here is something that you can have a pull at, when I have finished to-day. It is a little apparatus of two hollow brass hemispheres, closely fitted together, and having connected with it a pipe and a cock, through which we can exhaust the air from the inside; and although the two halves are so easily taken apart, while the air is left within, yet you will see, when we exhaust it by-and-by, no power of any two of you will be able to pull them apart. Every square inch of surface that is contained in the area of that vessel sustains fifteen pounds by weight, or nearly so, when the air is taken out; and you may try your strength presently in seeing whether you can overcome that pressure of the atmosphere. Here is another very pretty thing--the boys' sucker, only refined by the philosopher. We young ones have a perfect right to take toys, and make them into philosophy, inasmuch as now-a-days we are turning philosophy into toys. Here is a sucker, only it is made of india-rubber: if I clap it upon the table, you see at once it holds. Why does it hold? I can slip it about, and yet if I try to pull it up, it seems as if it would pull the table with it I can easily make it slip about from place to place; but only when I bring it to the edge of the table can I get it off. It is only kept down by the pressure of the atmosphere above. We have a couple of them; and if you take these two and press them together, you will see how firmly they stick. And, indeed, we may use them as they are proposed to be used, to stick against windows, or against walls, where they will adhere for an evening, and serve to hang anything on that you want. I think, however, that you boys ought to be shewn experiments that you can make at home; and so here is a very pretty experiment in illustration of the pressure of the atmosphere. Here is a tumbler of water. Suppose I were to ask you to turn that tumbler upside-down, so that the water should not fall out, and yet not be kept in by your hand, but merely by using the pressure of the atmosphere. Could you do that? Take a wine-glass, either quite full or half-full of water, and put a flat card on the top, turn it upside-down, and then see what becomes of the card and of the water. The air cannot get in because the water by its capillary attraction round the edge keeps it out. I think this will give you a correct notion of what you may call the materiality of the air; and when I tell you that the box holds a pound of it, and this room more than a ton, you will begin to think that air is something very serious. I will make another experiment, to convince you of this positive resistance. There is that beautiful experiment of the popgun, made so well and so easily, you know, out of a quill, or a tube, or anything of that kind,--where we take a slice of potato, for instance, or an apple, and take the tube and cut out a pellet, as I have now done, and push it to one end. I have made that end tight; and now I take another piece and put it in: it will confine the air that is within the tube perfectly and completely for our purpose; and I shall now find it absolutely impossible by any force of mine to drive that little pellet close up to the other. It cannot be done. I may press the air to a certain extent, but if I go on pressing, long before it comes to the second, the confined air will drive the front one out with a force something like that of gunpowder; for gunpowder is in part dependent upon the same action that you see here exemplified. I saw the other day an experiment which pleased me much, as I thought it would serve our purpose here. (I ought to have held my tongue for four or five minutes before beginning this experiment, because it depends upon my lungs for success.) By the proper application of air I expect to be able to drive this egg out of one cup into the other by the force of my breath; but if I fail, it is in a good cause; and I do not promise success, because I have been talking more than I ought to do to make the experiment succeed. [The Lecturer here tried the experiment, and succeeded in blowing the egg from one egg-cup to the other.] You see that the air which I blow goes downwards between the egg and the cup, and makes a blast under the egg, and is thus able to lift a heavy thing--for a full egg is a very heavy thing for air to lift. If you want to make the experiment, you had better boil the egg quite hard first, and then you may very safely try to blow it from one cup to the other, with a little care. I have now kept you long enough upon this property of the weight of the air, but there is another thing I should like to mention. You saw the way in which, in this popgun, I was able to drive the second piece of potato half or two-thirds of an inch before the first piece started, by virtue of the elasticity of the air--just as I pressed into the copper bottle the particles of air by means of the pump. Now, this depends upon a wonderful property in the air, namely, its elasticity; and I should like to give you a good illustration of this. If I take anything that confines the air properly, as this membrane, which also is able to contract and expand so as to give us a measure of the elasticity of the air, and confine in this bladder a certain portion of air; and then, if we take the atmosphere off from the outside of it, just as in these cases we put the pressure on--if we take the pressure off, you will see how it will then go on expanding and expanding, larger and larger, until it will fill the whole of this bell-jar, shewing you that wonderful property of the air, its elasticity, its compressibility, and expansibility, to an exceedingly large extent, and which is very essential for the purposes and services it performs in the economy of creation. We will now turn to another very important part of our subject, remembering that we have examined the candle in its burning, and have found that it gives rise to various products. We have the products, you know, of soot, of water, and of something else which you have not yet examined. We have collected the water, but have allowed the other things to go into the air. Let us now examine some of these other products. Here is an experiment which I think will help you in part in this way. We will put our candle there, and place over it a chimney, thus. I think my candle will go on burning, because the air-passage is open at the bottom and the top. In the first place, you see the moisture appearing--that you know about. It is water produced from the candle by the action of the air upon its hydrogen. But, besides that, something is going out at the top: it is not moisture--it is not water--it is not condensible; and yet, after all, it has very singular properties. You will find that the air coming out of the top of our chimney is nearly sufficient to blow the light out I am holding to it; and if I put the light fairly opposed to the current, it will blow it quite out. You will say that is as it should be; and I am supposing that you think it ought to do so, because the nitrogen does not support combustion, and ought to put the candle out, since the candle will not burn in nitrogen. [Illustration: Fig. 29.] But is there nothing else there than nitrogen? I must now anticipate--that is to say, I must use my own knowledge to supply you with the means that we adopt for the purpose of ascertaining these things, and examining such gases as these. I will take an empty bottle--here is one--and if I hold it over this chimney, I shall get the combustion of the candle below sending its results into the bottle above; and we shall soon find that this bottle contains, not merely an air that is bad as regards the combustion of a taper put into it, but having other properties. Let me take a little quick-lime and pour some common water on to it--the commonest water will do. I will stir it a moment, then pour it upon a piece of filtering paper in a funnel, and we shall very quickly have a clear water proceeding to the bottle below, as I have here. I have plenty of this water in another bottle; but, nevertheless, I should like to use the lime-water that was prepared before you, so that you may see what its uses are. If I take some of this beautiful clear lime-water, and pour it into this jar, which has collected the air from the candle, you will see a change coming about. Do you see that the water has become quite milky? Observe, that will not happen with air merely. Here is a bottle filled with air; and if I put a little lime-water into it, neither the oxygen nor the nitrogen, nor anything else that is in that quantity of air, will make any change in the lime-water. It remains perfectly clear, and no shaking of that quantity of lime-water with that quantity of air in its common state will cause any change; but if I take this bottle with the lime-water, and hold it so as to get the general products of the candle in contact with it, in a very short time we shall have it milky. There is the chalk, consisting of the lime which we used in making the lime-water, combined with something that came from the candle--that other product which we are in search of, and which I want to tell you about to-day. This is a substance made visible to us by its action, which is not the action of the lime-water either upon the oxygen or upon the nitrogen, nor upon the water itself, but it is something new to us from the candle. And then we find this white powder, produced by the lime-water and the vapour from the candle, appears to us very much like whitening or chalk, and, when examined, it does prove to be exactly the same substance as whitening or chalk. So we are led, or have been led, to observe upon the various circumstances of this experiment, and to trace this production of chalk to its various causes, to give us the true knowledge of the nature of this combustion of the candle--to find that this substance, issuing from the candle, is exactly the same as that substance which would issue from a retort, if I were to put some chalk into it with a little moisture, and make it red-hot: you would then find that exactly the same substance would issue from it as from the candle. But we have a better means of getting this substance, and in greater quantity, so as to ascertain what its general characters are. We find this substance in very great abundance in a multitude of cases where you would least expect it. All limestones contain a great deal of this gas which issues from the candle, and which we call _carbonic acid_. All chalks, all shells, all corals contain a great quantity of this curious air. We find it fixed in these stones; for which reason Dr. Black called it "fixed air"--finding it in these fixed things like marble and chalk. He called it fixed air, because it lost its quality of air, and assumed the condition of a solid body. We can easily get this air from marble. Here is a jar containing a little muriatic acid, and here is a taper which, if I put it into that jar, will shew only the presence of common air. There is, you see, pure air down to the bottom; the jar is full of it Here is a substance--marble[17], a very beautiful and superior marble--and if I put these pieces of marble into the jar, a great boiling apparently goes on. That, however, is not steam--it is a gas that is rising up; and if I now search the jar by a candle, I shall have exactly the same effect produced upon the taper as I had from the air which issued from the end of the chimney over the burning candle. It is exactly the same action, and caused by the very same substance that issued from the candle; and in this way we can get carbonic acid in great abundance--we have already nearly filled the jar. We also find that this gas is not merely contained in marble. Here is a vessel in which I have put some common whitening--chalk, which has been washed in water and deprived of its coarser particles, and so supplied to the plasterer as whitening. Here is a large jar containing this whitening and water, and I have here some strong sulphuric acid, which is the acid you might have to use if you were to make these experiments (only, in using this acid with limestone, the body that is produced is an insoluble substance, whereas the muriatic acid produces a soluble substance that does not so much thicken the water). And you will seek out a reason why I take this kind of apparatus for the purpose of shewing this experiment. I do it because you may repeat in a small way what I am about to do in a large one. You will have here just the same kind of action; and I am evolving in this large jar carbonic acid, exactly the same in its nature and properties as the gas which we obtained from the combustion of the candle in the atmosphere. And no matter how different the two methods by which we prepare this carbonic acid, you will see, when we get to the end of our subject, that it is all exactly the same, whether prepared in the one way or in the other. We will now proceed to the next experiment with regard to this gas. What is its nature? Here is one of the vessels full, and we will try it, as we have done so many other gases, by combustion. You see it is not combustible, nor does it support combustion. Neither, as we know, does it dissolve much in water, because we collect it over water very easily. Then, you know that it has an effect, and becomes white in contact with lime-water; and when it does become white in that way, it becomes one of the constituents to make carbonate of lime or limestone. The next thing I must shew you is, that it really does dissolve a little in water, and therefore that it is unlike oxygen and hydrogen in that respect I have here an apparatus by which we can produce this solution. In the lower part of this apparatus is marble and acid, and in the upper part cold water. The valves are so arranged that the gas can get from one to the other. I will set it in action now, and you can see the gas bubbling up through the water, as it has been doing all night long, and by this time we shall find that we have this substance dissolved in the water. If I take a glass and draw off some of the water, I find that it tastes a little acid to the mouth: it is impregnated with carbonic acid; and if I now apply a little lime-water to it, that will give us a test of its presence. This water will make the lime-water turbid and white, which is proof of the presence of carbonic acid. Then it is a very weighty gas--it is heavier than the atmosphere. I have put their respective weights at the lower part of this table, along with, for comparison, the weights of the other gases we have been examining:-- Pint. Cubic Foot. Hydrogen, . . . . 3/4 grains. 1/12 ounce. Oxygen, . . . . 11-9/10 " 1-1/2 " Nitrogen, . . . . 10-1/10 " 1-1/4 " Air,. . . . . . 10-7/16 " 1-3/8 " Carbonic acid, . . 16-1/3 " 1-9/10 " A pint of it weighs 16-1/3 grains, and a cubic foot weighs 1-9/10 ounce, almost two ounces. You can see by many experiments that this is a heavy gas. Suppose I take a glass containing nothing else but air, and from this vessel containing the carbonic acid I attempt to pour a little of this gas into that glass; I wonder whether any has gone in or not. I cannot tell by the appearance, but I can in this way [introducing the taper]. Yes, there it is, you see; and if I were to examine it by lime-water, I should find it by that test also. I will take this little bucket, and put it down into the well of carbonic acid--indeed, we too often have real wells of carbonic acid--and now, if there is any carbonic acid, I must have got to it by this time, and it will be in this bucket, which we will examine with a taper. There it is, you see; it is full of carbonic acid. [Illustration: Fig. 30.] There is another experiment by which I will shew you its weight. I have here a jar suspended at one end of a balance--it is now equipoised; but when I pour this carbonic acid into the jar on the one side which now contains air, you will see it sink down at once, because of the carbonic acid that I pour into it. And now, if I examine this jar with the lighted taper, I shall find that the carbonic acid has fallen into it, and it no longer has any power of supporting the combustion. If I blow a soap-bubble, which of course will be filled with air, and let it fall into this jar of carbonic acid, it will float. [Illustration: Fig. 31.] But I shall first of all take one of these little balloons filled with air. I am not quite sure where the carbonic acid is; we will just try the depth, and see whereabouts is its level. There, you see, we have this bladder floating on the carbonic acid; and if I evolve some more of the carbonic acid, the bladder will be lifted up higher. There it goes--the jar is nearly full; and now I will see whether I can blow a soap-bubble on that, and float it in the same way. [The Lecturer here blew a soap-bubble, and allowed it to fall into the jar of carbonic acid, when it floated in it midway.] It is floating, as the balloon floated, by virtue of the greater weight of the carbonic acid than of the air. And now, having so far given you the history of the carbonic acid--as to its sources in the candle, as to its physical properties and weight--when we next meet I shall shew you of what it is composed, and where it gets its elements from. LECTURE VI. CARBON OR CHARCOAL--COAL GAS--RESPIRATION AND ITS ANALOGY TO THE BURNING OF A CANDLE--CONCLUSION. A lady, who honours me by her presence at these Lectures, has conferred a still further obligation by sending me these two candles, which are from Japan, and, I presume, are made of that substance to which I referred in a former lecture. You see that they are even far more highly ornamented than the French candles; and, I suppose, are candles of luxury, judging from their appearance. They have a remarkable peculiarity about them--namely, a hollow wick,--that beautiful peculiarity which Argand introduced into the lamp, and made so valuable. To those who receive such presents from the East, I may just say that this and such like materials gradually undergo a change which gives them on the surface a dull and dead appearance; but they may easily be restored to their original beauty, if the surface be rubbed with a clean cloth or silk handkerchief, so as to polish the little rugosity or roughness: this will restore the beauty of the colours. I have so rubbed one of these candles, and you see the difference between it and the other which has not been polished, but which may be restored by the same process. Observe, also, that these moulded candles from Japan are made more conical than the moulded candles in this part of the world. I told you, when we last met, a good deal about carbonic acid. We found, by the lime-water test, that when the vapour from the top of the candle or lamp was received into bottles, and tested by this solution of lime-water (the composition of which I explained to you, and which you can make for yourselves), we had that white opacity which was in fact calcareous matter, like shells and corals, and many of the rocks and minerals in the earth. But I have not yet told you fully and clearly the chemical history of this substance--carbonic acid--as we have it from the candle, and I must now resume that subject. We have seen the products, and the nature of them, as they issue from the candle. We have traced the water to its elements, and now we have to see where are the elements of the carbonic acid supplied by the candle. A few experiments will shew this. You remember that when a candle burns badly, it produces smoke; but if it is burning well, there is no smoke. And you know that the brightness of the candle is due to this smoke, which becomes ignited. Here is an experiment to prove this: so long as the smoke remains in the flame of the candle and becomes ignited, it gives a beautiful light, and never appears to us in the form of black particles. I will light some fuel, which is extravagant in its burning. This will serve our purpose--a little turpentine on a sponge. You see the smoke rising from it, and floating into the air in large quantities; and, remember now, the carbonic acid that we have from the candle is from such smoke as that. To make that evident to you, I will introduce this turpentine burning on the sponge into a flask where I have plenty of oxygen, the rich part of the atmosphere, and you now see that the smoke is all consumed. This is the first part of our experiment; and now, what follows? The carbon which you saw flying off from the turpentine flame in the air is now entirely burned in this oxygen, and we shall find that it will, by this rough and temporary experiment, give us exactly the same conclusion and result as we had from the combustion of the candle. The reason why I make the experiment in this manner is solely that I may cause the steps of our demonstration to be so simple that you can never for a moment lose the train of reasoning, if you only pay attention. All the carbon which is burned in oxygen, or air, comes out as carbonic acid, whilst those particles which are not so burned shew you the second substance in the carbonic acid--namely, the carbon--that body which made the flame so bright whilst there was plenty of air, but which was thrown off in excess when there was not oxygen enough to burn it. I have also to shew you a little more distinctly the history of carbon and oxygen, in their union to make carbonic acid. You are now better able to understand this than before, and I have prepared three or four experiments by way of illustration. This jar is filled with oxygen, and here is some carbon which has been placed in a crucible, for the purpose of being made red-hot. I keep my jar dry, and venture to give you a result imperfect in some degree, in order that I may make the experiment brighter. I am about to put the oxygen and the carbon together. That this is carbon (common charcoal pulverised), you will see by the way in which it burns in the air [letting some of the red-hot charcoal fall out of the crucible]. I am now about to burn it in oxygen gas, and look at the difference. It may appear to you at a distance as if it were burning with a flame; but it is not so. Every little piece of charcoal is burning as a spark, and whilst it so burns it is producing carbonic acid. I specially want these two or three experiments to point out what I shall dwell upon more distinctly by-and-by--that carbon burns in this way, and not as a flame. Instead of taking many particles of carbon to burn, I will take a rather large piece, which will enable you to see the form and size; and to trace the effects very decidedly. Here is the jar of oxygen, and here is the piece of charcoal, to which I have fastened a little piece of wood, which I can set fire to, and so commence the combustion, which I could not conveniently do without. You now see the charcoal burning, but not as a flame (or if there be a flame, it is the smallest possible one, which I know the cause of--namely, the formation of a little carbonic oxide close upon the surface of the carbon). It goes on burning, you see, slowly producing carbonic acid by the union of this carbon or charcoal (they are equivalent terms) with the oxygen. I have here another piece of charcoal, a piece of bark, which has the quality of being blown to pieces--exploding as it burns. By the effect of the heat, we shall reduce the lump of carbon into particles that will fly off; still every particle, equally with the whole mass, burns in this peculiar way: it burns as a coal, and not like a flame. You observe a multitude of little combustions going on, but no flame. I do not know a finer experiment than this, to shew that carbon burns with a spark. Here, then, is carbonic acid formed from its elements. It is produced at once; and if we examined it by lime-water, you will see that we have the same substance which I have previously described to you. By putting together 6 parts of carbon by weight (whether it comes from the flame of a candle or from powdered charcoal) and 16 parts of oxygen by weight, we have 22 parts of carbonic acid; and, as we saw last time, the 22 parts of carbonic acid, combined with 28 parts of lime, produced common carbonate of lime. If you were to examine an oyster-shell, and weigh the component parts, you would find that every 50 parts would give 6 of carbon and 16 of oxygen, combined with 28 of lime. However, I do not want to trouble you with these minuti¾--it is only the general philosophy of the matter that we can now go into. See how finely the carbon is dissolving away [pointing to the lump of charcoal burning quietly in the jar of oxygen]. You may say that the charcoal is actually dissolving in the air round about; and if that were perfectly pure charcoal, which we can easily prepare, there would be no residue whatever. When we have a perfectly cleansed and purified piece of carbon, there is no ash left. The carbon burns as a solid dense body, that heat alone cannot change as to its solidity, and yet it passes away into vapour that never condenses into solid or liquid under ordinary circumstances; and what is more curious still, is the fact that the oxygen does not change in its bulk by the solution of the carbon in it. Just as the bulk is at first, so it is at last, only it has become carbonic acid. There is another experiment which I must give you before you are fully acquainted with the general nature of carbonic acid. Being a compound body, consisting of carbon and oxygen, carbonic acid is a body that we ought to be able to take asunder. And so we can. As we did with water, so we can with carbonic acid--take the two parts asunder. The simplest and quickest way is to act upon the carbonic acid by a substance that can attract the oxygen from it, and leave the carbon behind. You recollect that I took potassium and put it upon water or ice, and you saw that it could take the oxygen from the hydrogen. Now, suppose we do something of the same kind here with this carbonic acid. You know carbonic acid to be a heavy gas. I will not test it with lime-water, as that will interfere with our subsequent experiments; but I think the heaviness of the gas and the power of extinguishing flame will be sufficient for our purpose. I introduce a flame into the gas, and you will see whether it will be put out. You see the light is extinguished. Indeed, the gas may, perhaps, put out phosphorus, which, you know, has a pretty strong combustion. Here is a piece of phosphorus heated to a high degree. I introduce it into gas, and you observe the light is put out; but it will take fire again in the air, because there it re-enters into combustion. Now, let me take a piece of potassium, a substance which, even at common temperatures, can act upon carbonic acid, though not sufficiently for our present purpose, because it soon gets covered with a protecting coat; but if we warm it up to the burning point in air, as we have a fair right to do, and as we have done with phosphorus, you will see that it can burn in carbonic acid; and if it burns, it will burn by taking oxygen, so that you will see what is left behind. I am going, then, to burn this potassium in the carbonic acid, as a proof of the existence of oxygen in the carbonic acid. [In the preliminary process of heating, the potassium exploded.] Sometimes we get an awkward piece of potassium that explodes, or something like it, when it burns. I will take another piece; and now that it is heated, I introduce it into the jar, and you perceive that it burns in the carbonic acid--not so well as in the air, because the carbonic acid contains the oxygen combined; but it does burn, and takes away the oxygen. If I now put this potassium into water, I find that, besides the potash formed (which you need not trouble about), there is a quantity of carbon produced. I have here made the experiment in a very rough way; but I assure you that if I were to make it carefully, devoting a day to it, instead of five minutes, we should get all the proper amount of charcoal left in the spoon, or in the place where the potassium was burned, so that there could be no doubt as to the result. Here, then, is the carbon obtained from the carbonic acid, as a common black substance; so that you have the entire proof of the nature of carbonic acid as consisting of carbon and oxygen. And now, I may tell you, that _whenever_ carbon burns under common circumstances, it produces carbonic acid. Suppose I take this piece of wood, and put it into a bottle with lime-water. I might shake that lime-water up with wood and the atmosphere as long as I pleased, it would still remain clear as you see it; but suppose I burn the piece of wood in the air of that bottle. You, of course, know I get water. Do I get carbonic acid? [The experiment was performed.] There it is, you see--that is to say, the carbonate lime, which results from carbonic acid, and that carbonic acid must be formed from the carbon which comes from the wood, from the candle, or any other thing. Indeed, you have yourselves frequently tried a very pretty experiment, by which you may see the carbon in wood. If you take a piece of wood, and partly burn it, and then blow it out, you have carbon left. There are things that do not shew carbon in this way. A candle does not shew it, but it contains carbon. Here also is a jar of coal-gas, which produces carbonic acid abundantly. You do not see the carbon, but we can soon shew it to you. I will light it, and as long as there is any gas in this cylinder it will go on burning. You see no carbon, but you see a flame; and because that is bright, it will lead you to guess that there is carbon in the flame. But I will shew it to you by another process. I have some of the same gas in another vessel, mixed with a body that will burn the hydrogen of the gas, but will not burn the carbon. I will light them with a burning taper, and you perceive the hydrogen is consumed, but not the carbon, which is left behind as a dense black smoke. I hope that by these three or four experiments you will learn to see when carbon is present, and understand what are the products of combustion, when gas or other bodies are thoroughly burned in the air. Before we leave the subject of carbon, let us make a few experiments and remarks upon its wonderful condition as respects ordinary combustion. I have shewn you that the carbon in burning burns only as a solid body, and yet you perceive that, after it is burned, it ceases to be a solid. There are very few fuels that act like this. It is, in fact, only that great source of fuel, the carbonaceous series, the coals, charcoals, and woods, that can do it. I do not know that there is any other elementary substance besides carbon that burns with these conditions; and if it had not been so, what would happen to us? Suppose all fuel had been like iron, which, when it burns, burns into a solid substance. We could not then have such a combustion as you have in this fire-place. Here also is another kind of fuel which burns very well--as well as, if not better, than carbon--so well, indeed, as to take fire of itself when it is in the air, as you see [breaking a tube full of lead pyrophorus]. This substance is lead, and you see how wonderfully combustible it is. It is very much divided, and is like a heap of coals in the fireplace; the air can get to its surface and inside, and so it burns. But why does it not burn in that way now, when it is lying in a mass? [emptying the contents of the tube in a heap on to a plate of iron]. Simply because the air cannot get to it. Though it can produce a great heat, the great heat which we want in our furnaces and under our boilers, still that which is produced cannot get away from the portion which remains unburned underneath, and that portion, therefore, is prevented from coming in contact with the atmosphere, and cannot be consumed. How different is that from carbon. Carbon burns just in the same way as this lead does, and so gives an intense fire in the furnace, or wherever you choose to burn it; but then the body produced by its combustion passes away, and the remaining carbon is left clear. I shewed you how carbon went on dissolving in the oxygen, leaving no ash; whereas here [pointing to the heap of pyrophorus] we have actually more ash than fuel, for it is heavier by the amount of the oxygen which has united with it. Thus you see the difference between carbon and lead or iron: if we choose iron, which gives so wonderful a result in our application of this fuel, either as light or heat. If, when the carbon burnt, the product went off as a solid body, you would have had the room filled with an opaque substance, as in the case of the phosphorus; but when carbon burns, everything passes up into the atmosphere. It is in a fixed, almost unchangeable condition before the combustion; but afterwards it is in the form of gas, which it is very difficult (though we have succeeded) to produce in a solid or a liquid state. Now, I must take you to a very interesting part of our subject--to the relation between the combustion of a candle and that living kind of combustion which goes on within us. In every one of us there is a living process of combustion going on very similar to that of a candle; and I must try to make that plain to you. For it is not merely true in a poetical sense--the relation of the life of man to a taper; and if you will follow, I think I can make this clear. In order to make the relation very plain, I have devised a little apparatus which we can soon build up before you. Here is a board and a groove cut in it, and I can close the groove at the top part by a little cover. I can then continue the groove as a channel by a glass tube at each end, there being a free passage through the whole. Suppose I take a taper or candle (we can now be liberal in our use of the word "candle," since we understand what it means), and place it in one of the tubes; it will go on, you see, burning very well. You observe that the air which feeds the flame passes down the tube at one end, then goes along the horizontal tube, and ascends the tube at the other end in which the taper is placed. [Illustration: Fig. 32] If I stop the aperture through which the air enters, I stop combustion, as you perceive. I stop the supply of air, and consequently the candle goes out. But, now, what will you think of this fact? In a former experiment I shewed you the air going from one burning candle to a second candle. If I took the air proceeding from another candle, and sent it down by a complicated arrangement into this tube, I should put this burning candle out. But what will you say when I tell you that my breath will put out that candle? I do not mean by blowing at all, but simply that the nature of my breath is such that a candle cannot burn in it. I will now hold my mouth over the aperture, and without blowing the flame in any way, let no air enter the tube but what comes from my mouth. You see the result. I did not blow the candle out. I merely let the air which I expired pass into the aperture, and the result was that the light went out for want of oxygen, and for no other reason. Something or other--namely, my lungs--had taken away the oxygen from the air, and there was no more to supply the combustion of the candle. It is, I think, very pretty to see the time it takes before the bad air which I throw into this part of the apparatus has reached the candle. The candle at first goes on burning, but so soon as the air has had time to reach it, it goes out. And, now, I will shew you another experiment, because this is an important part of our philosophy. Here is a jar which contains fresh air, as you can see by the circumstance of a candle or gas-light burning it. I make it close for a little time, and by means of a pipe I get my mouth over it so that I can inhale the air. By putting it over water, in the way that you see, I am able to draw up this air (supposing the cork to be quite tight), take it into my lungs, and throw it back into the jar. [Illustration: Fig. 33.] We can then examine it, and see the result. You observe, I first take up the air, and then throw it back, as is evident from the ascent and descent of the water; and now, by putting a taper into the air, you will see the state in which it is, by the light being extinguished. Even one inspiration, you see, has completely spoiled this air, so that it is no use my trying to breathe it a second time. Now, you understand the ground of the impropriety of many of the arrangements among the houses of the poorer classes, by which the air is breathed over and over again, for the want of a supply, by means of proper ventilation, sufficient to produce a good result. You see how bad the air becomes by a single breathing; so that you can easily understand how essential fresh air is to us. To pursue this a little further, let us see what will happen with lime-water. Here is a globe which contains a little lime-water, and it is so arranged as regards the pipes, as to give access to the air within, so that we can ascertain the effect of respired or unrespired air upon it. Of course, I can either draw in air (through A), and so make the air that feeds my lungs go through the lime-water, or I can force the air out of my lungs through the tube (B), which goes to the bottom, and so shew its effect upon the lime-water. [Illustration: Fig. 34.] You will observe that, however long I draw the external air into the lime-water, and then through it to my lungs, I shall produce no effect upon the water--it will not make the lime-water turbid; but if I throw the air _from_ my lungs through the lime-water, several times in succession, you see how white and milky the water is getting, shewing the effect which expired air has had upon it; and now you begin to know that the atmosphere which we have spoiled by respiration is spoiled by carbonic acid, for you see it here in contact with the lime-water. I have here two bottles, one containing lime-water and the other common water, and tubes which pass into the bottles and connect them. The apparatus is very rough, but it is useful notwithstanding. [Illustration: Fig. 35.] If I take these two bottles, inhaling here and exhaling there, the arrangement of the tubes will prevent the air going backwards. The air coming in will go to my mouth and lungs, and in going out, will pass through the lime-water, so that I can go on breathing and making an experiment, very refined in its nature, and very good in its results. You will observe that the good air has done nothing to the lime-water; in the other case nothing has come to the lime-water but my respiration, and you see the difference in the two cases. Let us now go a little further. What is all this process going on within us which we cannot do without, either day or night, which is so provided for by the Author of all things that He has arranged that it shall be independent of all will? If we restrain our respiration, as we can to a certain extent, we should destroy ourselves. When we are asleep, the organs of respiration, and the parts that are associated with them, still go on with their action--so necessary is this process of respiration to us, this contact of the air with the lungs. I must tell you, in the briefest possible manner, what this process is. We consume food: the food goes through that strange set of vessels and organs within us, and is brought into various parts of the system, into the digestive parts especially; and alternately the portion which is so changed is carried through our lungs by one set of vessels, while the air that we inhale and exhale is drawn into and thrown out of the lungs by another set of vessels, so that the air and the food come close together, separated only by an exceedingly thin surface: the air can thus act upon the blood by this process, producing precisely the same results in kind as we have seen in the case of the candle. The candle combines with parts of the air, forming carbonic acid, and evolves heat; so in the lungs there is this curious, wonderful change taking place. The air entering, combines with the carbon (not carbon in a free state, but, as in this case, placed ready for action at the moment), and makes carbonic acid, and is so thrown out into the atmosphere, and thus this singular result takes place: we may thus look upon the food as fuel. Let me take that piece of sugar, which will serve my purpose. It is a compound of carbon, hydrogen, and oxygen, similar to a candle, as containing the same elements, though not in the same proportion--the proportions being as shewn in this table:-- SUGAR. Carbon, . . . . 72 _ Hydrogen, . . . 11 | | 99 Oxygen, . . . . 88_| This is, indeed, a very curious thing, which you can well remember, for the oxygen and hydrogen are in exactly the proportions which form water, so that sugar may be said to be compounded of 72 parts of carbon and 99 parts of water; and it is the carbon in the sugar that combines with the oxygen carried in by the air in the process of respiration--so making us like candles--producing these actions, warmth, and far more wonderful results besides, for the sustenance of the system, by a most beautiful and simple process. To make this still more striking, I will take a little sugar; or, to hasten the experiment, I will use some syrup, which contains about three-fourths of sugar and a little water. If I put a little oil of vitriol on it, it takes away the water, and leaves the carbon in a black mass. [The Lecturer mixed the two together.] You see how the carbon is coming out, and before long we shall have a solid mass of charcoal, all of which has come out of sugar. Sugar, as you know, is food, and here we have absolutely a solid lump of carbon where you would not have expected it. And if I make arrangements so as to oxidize the carbon of sugar, we shall have a much more striking result Here is sugar, and I have here an oxidizer--a quicker one than the atmosphere; and so we shall oxidize this fuel by a process different from respiration in its form, though not different in its kind. It is the combustion of the carbon by the contact of oxygen which the body has supplied to it. If I set this into action at once, you will see combustion produced. Just what occurs in my lungs--taking in oxygen from another source, namely, the atmosphere--takes place here by a more rapid process. You will be astonished when I tell you what this curious play of carbon amounts to. A candle will burn some four, five, six, or seven hours. What, then, must be the daily amount of carbon going up into the air in the way of carbonic acid! What a quantity of carbon must go from each of us in respiration! What a wonderful change of carbon must take place under these circumstances of combustion or respiration! A man in twenty-four hours converts as much as seven ounces of carbon into carbonic acid; a milch cow will convert seventy ounces, and a horse seventy-nine ounces, solely by the act of respiration. That is, the horse in twenty-four hours burns seventy-nine ounces of charcoal, or carbon, in his organs of respiration, to supply his natural warmth in that time. All the warm-blooded animals get their warmth in this way, by the conversion of carbon, not in a free state, but in a state of combination. And what an extraordinary notion this gives us of the alterations going on in our atmosphere. As much as 5,000,000 pounds, or 548 tons, of carbonic acid is formed by respiration in London alone in twenty-four hours. And where does all this go? Up into the air. If the carbon had been like the lead which I shewed you, or the iron which, in burning, produces a solid substance, what would happen? Combustion could not go on. As charcoal burns, it becomes a vapour and passes off into the atmosphere, which is the great vehicle, the great carrier for conveying it away to other places. Then, what becomes of it? Wonderful is it to find that the change produced by respiration, which seems so injurious to us (for we cannot breathe air twice over), is the very life and support of plants and vegetables that grow upon the surface of the earth. It is the same also under the surface, in the great bodies of water; for fishes and other animals respire upon the same principle, though not exactly by contact with the open air. Such fish as I have here [pointing to a globe of gold-fish] respire by the oxygen which is dissolved from the air by the water, and form carbonic acid; and they all move about to produce the one great work of making the animal and vegetable kingdoms subservient to each other. And all the plants growing upon the surface of the earth, like that which I have brought here to serve as an illustration, absorb carbon. These leaves are taking up their carbon from the atmosphere, to which we have given it in the form of carbonic acid, and they are growing and prospering. Give them a pure air like ours, and they could not live in it; give them carbon with other matters, and they live and rejoice. This piece of wood gets all its carbon, as the trees and plants get theirs, from the atmosphere, which, as we have seen, carries away what is bad for us and at the same time good for them,--what is disease to the one being health to the other. So are we made dependent, not merely upon our fellow-creatures, but upon our fellow-existers, all Nature being tied together by the laws that make one part conduce to the good of another. There is another little point which I must mention before we draw to a close--a point which concerns the whole of these operations, and most curious and beautiful it is to see it clustering upon and associated with the bodies that concern us--oxygen, hydrogen, and carbon, in different states of their existence. I shewed you just now some powdered lead, which I set burning[18]; and you saw that the moment the fuel was brought to the air, it acted, even before it got out of the bottle--the moment the air crept in, it acted. Now, there is a case of chemical affinity by which all our operations proceed. When we breathe, the same operation is going on within us. When we burn a candle, the attraction of the different parts one to the other is going on. Here it is going on in this case of the lead; and it is a beautiful instance of chemical affinity. If the products of combustion rose off from the surface, the lead would take fire, and go on burning to the end; but you remember that we have this difference between charcoal and lead--that, while the lead can start into action at once, if there be access of air to it, the carbon will remain days, weeks, months, or years. The manuscripts of Herculaneum were written with carbonaceous ink, and there they have been for 1,800 years or more, not having been at all changed by the atmosphere, though coming in contact with it under various circumstances. Now, what is the circumstance which makes the lead and carbon differ in this respect? It is a striking thing to see that the matter which is appointed to serve the purpose of fuel _waits_ in its action: it does not start off burning, like the lead and many other things that I could shew you; but which I have not encumbered the table with; but it waits for action. This waiting is a curious and wonderful thing. Candles--those Japanese candles, for instance--do not start into action at once, like the lead or iron (for iron finely divided does the same thing as lead), but there they wait for years, perhaps for ages, without undergoing any alteration. I have here a supply of coal-gas. The jet is giving forth the gas, but you see it does not take fire--it comes out into the air, but it waits till it is hot enough before it burns. If I make it hot enough, it takes fire. If I blow it out, the gas that is issuing forth waits till the light is applied to it again. It is curious to see how different substances wait--how some will wait till the temperature is raised a little, and others till it is raised a good deal. I have here a little gunpowder and some gun-cotton; even these things differ in the conditions under which they will burn. The gunpowder is composed of carbon and other substances, making it highly combustible; and the gun-cotton is another combustible preparation. They are both waiting, but they will start into activity at different degrees of heat, or under different conditions. By applying a heated wire to them, we shall see which will start first [touching the gun-cotton with the hot iron]. You see the gun-cotton has gone off, but not even the hottest part of the wire is now hot enough to fire the gunpowder. How beautifully that shews you the difference in the degree in which bodies act in this way! In the one case the substance will wait any time until the associated bodies are made active by heat; but in the other, as in the process of respiration, it waits no time. In the lungs, as soon as the air enters, it unites with the carbon; even in the lowest temperature which the body can bear short of being frozen, the action begins at once, producing the carbonic acid of respiration: and so all things go on fitly and properly. Thus you see the analogy between respiration and combustion is rendered still more beautiful and striking. Indeed, all I can say to you at the end of these lectures (for we must come to an end at one time or other) is to express a wish that you may, in your generation, be fit to compare to a candle; that you may, like it, shine as lights to those about you; that, in all your actions, you may justify the beauty of the taper by making your deeds honourable and effectual in the discharge of your duty to your fellow-men. LECTURE ON PLATINUM. [_Delivered before the_ ROYAL INSTITUTION, _on Friday, February 22, 1861._] Whether I was to have the honour of appearing before you this evening or not, seemed to be doubtful upon one or two points. One of these I will mention immediately; the other may or may not appear during the course of the hour that follows. The first point is this. When I was tempted to promise this subject for your attention this evening, it was founded upon a promise, and a full intent of performing that promise, on the part of my friend Deville, of Paris, to come here to shew before you a phenomenon in metallurgic chemistry not common. In that I have been disappointed. His intention was to have fused here some thirty or forty pounds of platinum, and so to have made manifest, through my mouth and my statement, the principles of a new process in metallurgy, in relation to this beautiful, magnificent, and valuable metal; but circumstances over which neither he nor I, nor others concerned, have sufficient control, have prevented the fulfilment of that intention; and the period at which I learned the fact was so recent, that I could hardly leave my place here to be filled by another, or permit you, who in your kindness have come to hear what might be said, to remain unreceived in the best manner possible to me under the circumstances. I therefore propose to state, as well as I can, what the principles are on which M. Deville proceeds, by means of drawings, and some subordinate or inferior experiments. The metal platinum, of which you see some very fine specimens on the table, has been known to us about a hundred years. It has been wrought in a beautiful way in this country, in France, and elsewhere, and supplied to the consumer in ingots of this kind, or in plates, such as we have here, or in masses, that by their very fall upon the table indicate the great weight of the substance, which is, indeed, nearly at the head of all substances in that respect. This substance has been given to us hitherto mainly through the philosophy of Dr. Wollaston, whom many of us know, and it is obtained in great purity and beauty. It is a very remarkable metal in many points, besides its known special uses. It usually comes to us in grains. Here is a very fine specimen of native platinum in grains. Here is also a nugget or ingot, and here are some small pieces gathered out of certain alluvial soils in Brazil, Mexico, California, and the Uralian districts of Russia. It is strange that this metal is almost always found associated with some four or five other metals, most curious in their qualities and characteristics. They are called platiniferous metals; and they have not only the relation of being always found associated in this manner, but they have other relations of a curious nature, which I shall point out to you by a reference to one of the tables behind me. This substance is always native--it is always in the metallic state; and the metals with which it is found connected, and which are rarely found elsewhere, are palladium, rhodium, iridium, osmium, and ruthenium. We have the names in one of the tables arranged in two columns, representing, as you see, two groups--platinum, iridium, and osmium constituting one group; and ruthenium, rhodium, and palladium the other. Three of these have the chemical equivalent of 98-1/2, and the others a chemical equivalent of about half that number. Then the metals of one group have an extreme specific gravity--platinum being, in fact, the lightest of the three, or as light as the lightest. Osmium has a specific gravity of 21.4, and is the heaviest body in nature; platinum is 21.15, and iridium the same; the specific gravity of the other three being only about half that, namely, 11.3, 12.1, and 11.8. Then there is this curious relation, that palladium and iridium are very much alike, so that you would scarcely know one from the other, though one has only half the weight of the other, and only half the equivalent power. So with iridium and rhodium, and osmium and ruthenium, which are so closely allied that they make pairs, being separated each from its own group. Then these metals are the most infusible that we possess. Osmium is the most difficult to fuse: indeed, I believe it never has been fused, while every other metal has. Ruthenium comes next, iridium next, rhodium next, platinum next (so that it ranks here as a pretty fusible metal, and yet we have been long accustomed to speak of the infusibility of platinum), and next comes palladium, which is the most fusible metal of the whole. It is a curious thing to see this fine association of physical properties coming out in metals which are grouped together somehow or other in nature, but, no doubt, by causes which are related to analogous properties in their situation on the surface of the earth, for it is in alluvial soils that these things are found. Now, with regard to this substance, let me tell you briefly how we get it. The process used to be this. The ore which I shewed you just now was taken, and digested in nitro-muriatic acid of a certain strength, and partly converted into a solution, with the leaving behind of certain bodies that I have upon the table. The platinum being dissolved with care in acids, to the solution the muriate of ammonia was added, as I am about to add it here. A yellow precipitate was then thrown down, as you perceive is the case now; and this, carefully washed and cleansed, gave us that body [pointing to a specimen of the chloride of platinum and ammonium], the other elements, or nearly all, being ejected. This substance being heated, gave us what we call platinum sponge, or platinum in the metallic state, so finely divided as to form a kind of heavy mass or sponge, which, at the time that Dr. Wollaston first sent it forth, was not fusible for the market or in the manufacturers' workshops, inasmuch as the temperature required was so high, and there were no furnaces that could bring the mass into a globule, and cause the parts to adhere together. Most of our metals that we obtain from nature, and work in our shops, are brought at last into a mass by fusion. I am not aware that there is in the arts or sciences any other than iron which is not so. Soft iron we do not bring together by fusion, but by a process which is analogous to the one that was followed in the case of platinum, namely, welding; for these divided grains of spongy platinum having been well washed and sunk in water for the purpose of excluding air, and pressed together, and heated, and hammered, and pressed again, until they come into a pretty close, dense, compact mass, did so cohere, that when the mass was put into the furnace of charcoal, and raised to a high temperature, the particles, at first infinitely divided--for they were chemically divided--adhered the one to the other, each to all the rest, until they made that kind of substance which you see here, which will bear rolling and expansion of every kind. No other process than that has hitherto been adopted for the purpose of obtaining this substance from the particles by solution, precipitation, ignition, and welding. It certainly is a very fine thing to see that we may so fully depend upon the properties of the various substances we have to deal with; that we can, by carrying out our processes, obtain a material like this, allowing of division and extension under a rolling mill--a material of the finest possible kind, the parts being held together, not with interstices, not with porosity, but so continuous that no fluids can pass between them; and, as Dr. Wollaston beautifully shewed, a globule of platinum fused by the voltaic battery and the oxy-hydrogen blowpipe, when drawn into a wire, was not sounder or stronger than this wire made by the curious coalescence of the particles by the sticking power that they had at high temperatures. This is the process adopted by Messrs. Johnson and Matthey, to whose great kindness I am indebted for these ingots and for the valuable assistance I have received in the illustrations. The treatment, however, that I have to bring before you is of another kind; and it is in the hope that we shall be able before long to have such a thing as the manufacture of platinum of this kind, that I am encouraged to come before you, and tell you how far Deville has gone in the matter, and to give you illustrations of the principles on which he proceeds. I think it is but fair that you should see an experiment shewing you the way in which we get the adhesion of platinum. Probably you all know of the welding of iron: you go into the smith's shop, and you see him put the handle of a poker on to the stem, and by a little management and the application of heat he makes them one. You have no doubt seen him put the iron into the fire and sprinkle a little sand upon it. He does not know the philosophy he calls into play when he sprinkles a little sand over the oxide of iron, but he has a fine philosophy there, or practises it, when he gets his welding. I can shew you here this beautiful circumstance of the sticking together of the particles up to the fullest possible intensity of their combination. If you were to go into the workshops of Mr. Matthey, and see them hammering and welding away, you would see the value of the experiment I am about to shew you. I have here some platinum-wire. This is a metal which resists the action of acids, resists oxidation by heat, and change of any sort; and which, therefore, I may heat in the atmosphere without any flux. I bend the wire so as to make the ends cross: these I make hot by means of the blowpipe, and then, by giving them a tap with a hammer, I shall make them into one piece. Now that the pieces are united, I shall have great difficulty in pulling them apart, though they are joined only at the point where the two cylindrical surfaces came together. And now I have succeeded in pulling the wire apart, the division is not at the point of welding, but where the force of the pincers has cut it, so that the junction we have effected is a complete one. This, then, is the principle of the manufacture and production of platinum in the old way. The treatment which Deville proposes to carry out, and which he has carried out to a rather large extent in reference to the Russian supply of platinum, is one altogether by heat, having little or no reference to the use of acids. That you may know what the problem is, look at this table, which gives you the composition of such a piece of platinum ore as I shewed you just now. Wherever it comes from, the composition is as complicated, though the proportions vary:-- Platinum, . . . . . 76.4 Iridium,. . . . . . 4.3 Rhodium,. . . . . . 0.3 Palladium,. . . . . 1.4 Gold, . . . . . . . 0.4 Copper, . . . . . . 4.1 Iron, . . . . . . . 11.7 Osmide of Iridium,. 0.5 Sand, . . . . . . . 1.4 ----- 100.5 This refers to the Uralian ore. In that state of combination, as shewn in the table, the iridium and osmium are found combined in crystals, sometimes to the amount of 0.5 per cent., and sometimes 3 or 4 per cent. Now, this Deville proposes to deal with in the dry way, in the place of dealing with it by any acid. I have here another kind of platinum; and I shew it to you for this reason. The Russian Government, having large stores of platinum in their dominions, have obtained it in a metallic state, and worked it into coin. The coin I have in my hand is a twelve silver rouble piece. The rouble is worth three shillings, and this coin is, therefore, of the value of thirty-six shillings. The smaller coin is worth half that sum; and the other, half of that. The metal, however, is unfit for coinage. When you have the two metals, gold and silver, used for coinage, you have a little confusion in the value of the two in the market; but when you have three precious metals (for you may call platinum a precious metal) worked into coin, they will be sure to run counter to one another. Indeed, the case did happen, that the price of platinum coin fixed by the Government was such, that it was worth while to purchase platinum in other countries, and make coin of it, and then take it into that country and circulate it. The result was, that the Russian Government stopped the issue. The composition of this coin is--platinum, 97.0; iridium, 1.2; rhodium, 0.5; palladium, 0.25; a little copper, and a little iron. It is, in fact, bad platinum: it scales, and it has an unfitness for commercial use and in the laboratory, which the other well-purified platinum has not. It wants working over again. Now, Deville's process depends upon three points,--upon intense heat, blowpipe action, and the volatility of certain metals. We know that there are plenty of metals that are volatile; but this, I think, is the first time that it has been proposed to use the volatility of certain metals--such as gold and palladium--for the purpose of driving them off and leaving something else behind. He counts largely upon the volatility of metals which we have not been in the habit of considering volatile, but which we have rather looked upon as fixed; and I must endeavour to illustrate these three points by a few experiments. Perhaps I can best show you what is required in the process of heating platinum by using that source of heat which we have here, and which seems to be almost illimitable--namely, the voltaic battery; for it is only in consequence of the heat that the voltaic battery affects the platinum. By applying the two extremities of the battery to this piece of platinum-wire, you will see what result we shall obtain. You perceive that we can take about this heating agent wherever we like, and deal with it as we please, limiting it in any way. I am obliged to deal carefully with it; but even that circumstance will have an interest for you in watching the experiment. Contact is now made. The electric current, when compressed into thin conducting-wires offering resistance, evolves heat to a large extent; and this is the power by which we work. You see the intense glow immediately imparted to the wire; and if I applied the heat continuously, the effect of the current would be to melt the wire. As soon as the contact is broken, the wire resumes its former appearance; and now that we make contact again, you perceive the glow as before. [The experiment was repeated several times in rapid succession.] You can see a line of light, though you can scarcely perceive the wire; and now that it has melted with the great heat, if you examine it, you will perceive that it is indeed a set of irregularities from end to end--a set of little spheres, which are strung upon an axis of platinum running through it. It is that wire which Mr. Grove described as being produced at the moment when fusion of the whole mass is commencing. In the same manner, if I take a tolerably thick piece of platinum, and subject it to the heat that can be produced by this battery, you will see the brilliancy of the effect produced. I shall put on a pair of spectacles for the experiment, as there is an injurious effect of the voltaic spark upon the eyes, if the action is continued; and it is neither policy nor bravery to subject any organ to unnecessary danger; and I want, at all events, to keep the full use of my eyes to the end of the lecture. You now see the action of the heat upon the piece of platinum--heat so great as to break in pieces the plate on which the drops of metal fall. You perceive, then, that we have sufficiently powerful sources of heat in nature to deal with platinum. I have here an apparatus by which the same thing can be shewn. Here is a piece of platinum, which is put into a crucible of carbon made at the end of one pole of the battery, and you will see the brilliant light that will be produced. There is our furnace, and the platinum is rapidly getting heated; and now you perceive that it is melted, and throwing off little particles. What a magnificent philosophical instrument this is. When you look at the result, which is lying upon the charcoal, you will see a beautifully fused piece of platinum. It is now a fiery globule, with a surface so bright, and smooth, and reflecting, that I cannot tell whether it is transparent, or opaque, or what. This, then, will give you an idea of what has to be done by any process that pretends to deal with thirty, or forty, or fifty pounds of platinum at once. Let me now tell you briefly what Deville proposes to do. First of all, he takes this ore, with its impurities, and mixes it (as he finds it essential and best) with its own weight of sulphuret of lead--lead combined with sulphur. Both the lead and the sulphur are wanted; for the iron that is there present, as you see by the table, is one of the most annoying substances in the treatment that you can imagine, because it is not volatile; and while the iron remains adhering to the platinum, the platinum will not flow readily. It cannot be sent away by a high temperature--sent into the atmosphere so as to leave the platinum behind. Well, then, a hundred parts of ore and a hundred parts of sulphuret of lead, with about fifty parts of metallic lead, being all mingled together in a crucible, the sulphur of the sulphuret takes the iron, the copper, and some of the other metals and impurities, and combines with them to form a slag; and as it goes on boiling and oxidising, it carries off the iron, and so a great cleansing takes place. Now, you ought to know that these metals, such as platinum, iridium, and palladium, have a strong affinity for such metals as lead and tin, and upon this a great deal depends. Very much depends upon the platinum throwing out its impurities of iron and so forth, by being taken up with the lead present in it. That you may have a notion of the great power that platinum has of combining with other metals, I will refer you to a little of the chemist's experience--his bad experience. He knows very well that if he takes a piece of platinum-foil, and heats a piece of lead upon it, or if he takes a piece of platinum-foil, such as we have here, and heats things upon it that have lead in them, his platinum is destroyed. I have here a piece of platinum, and if I apply the heat of the spirit-lamp to it, in consequence of the presence of this little piece of lead which I will place on it, I shall make a hole in the metal. The heat of the lamp itself would do no harm to the platinum, nor would other chemical means; but because there is a little lead present, and there is an affinity between the two substances, the bodies fuse together at once. You see the hole I have made. It is large enough to put your finger in, though the platinum itself was, as you saw, almost infusible, except by the voltaic battery. For the purpose of shewing this fact in a more striking manner, I have taken pieces of platinum-foil, tin-foil, and lead-foil, and rolled them together; and if I apply the blowpipe to them, you will have, in fact, a repetition on a larger scale of the experiment you saw just now when the lead and platinum came together, and one spoiled the other. When the metals are laid one upon the other, and folded together and heat applied, you will not only see that the platinum runs to waste, but that at the time when the platinum and lead are combined there is ignition produced--there is a power of sustaining combustion. I have taken a large piece, that you may see the phenomenon on a large scale. You saw the ignition and the explosion which followed, of which we have here the results--the consequence of the chemical affinity between the platinum and the metals combined with it, which is the thing upon which Deville founds his first result. When he has melted these substances and stirred them well up, and so obtained a complete mixture, he throws in air upon the surface to burn off all the sulphur from the remaining sulphuret of lead; and at last he gets an ingot of lead with platinum--much lead, comparatively, and little platinum. He gets that in the crucible with a lot of scoriæ and other things, which he treats afterwards. It is that platiniferous lead which we have to deal with in our future process. Now, let me tell you what he does with it. His first object is to get rid of the lead. He has thrown out all the iron, and a number of other things, and he has got this kind of compound indicated in the table. He may get it as high as 78 per cent. of platinum, and 22 of lead; or 5, or 10, or 15 of platinum, and 95, or 90, or 85 of lead (which he calls weak platinum), and he then places it in the kind of vessel that you see before you. Suppose we had the mixture here; we should have to make it hot, and then throw in air upon the surface. The combustible metal--that is, the lead--and the part that will oxidise, are thoroughly oxidised; the litharge would flow out in a fused state into a vessel placed to receive it, and the platinum remains behind. [Illustration: Fig. 36.] Here is the process which Deville adopts for the purpose of casting off the lead, after he has got out the platinum from the ore. (Having made use of your friend, you get rid of him as quickly as you can.) He gets his heat by applying the combination of oxygen and hydrogen, or of carburetted fuel, for the purpose of producing a fire. I have here a source of coal-gas; there I have a source of hydrogen; and here I have a source of oxygen. I have here also one of the blowpipes used by Deville in his process for working platinum in the way I have spoken of. There are two pipes, and one of them goes to the source of coal-gas, and the other to the supply of oxygen. [Illustration: Fig. 37.] By uniting these we obtain a flame of such a heat as to melt platinum. You will, perhaps, hardly imagine what the heat is, unless you have some proof of it; but you will soon see that I have actually the power of melting platinum. Here is a piece of platinum-foil running like wax under the flame which I am bringing to bear against it. The question, however, is whether we shall get heat enough to melt, not this small quantity, but large masses--many pounds of the metal. Having obtained heat like this, the next consideration is what vessel is he to employ which could retain the platinum when so heated, or bear the effects of the flame? Such vessels are happily well supplied at Paris, and are formed of a substance which surrounds Paris; it is a kind of chalk (called, I believe, by geologists, _calcaire grossière_), and it has the property of enduring an extreme degree of heat. I am now going to get the highest heat that we can obtain. First, I shew you the combustion of hydrogen by itself. I have not a large supply, because the coal-gas is sufficient for most of our purposes. If I put a piece of lime obtained from this chalk into the gas, you see we get a pretty hot flame, which would burn one's fingers a good deal But now let me subject a piece of it to the joint action of oxygen and hydrogen. I do this for the purpose of shewing you the value of lime as a material for the furnaces and chambers that are to contain the substances to be operated on, and that are consequently to sustain the action of this extreme heat. Here we have the hydrogen and the oxygen, which will give the most intense heat that can be obtained by chemical action; and if I put a piece of lime into the flame, we get what is called the lime-light. Now, with all the beauty and intensity of action which you perceive, there is no sensible deterioration of the lime except by the mechanical force of the current of gases rushing from the jet against the lime, sweeping away such particles as are not strongly aggregated. "Vapour of lime" some call it; and it may be so, but there is no other change of the lime than that under the action of heat of this highly-exalted chemical condition, though almost any other substance would melt at once. Then, as to the way in which the heat is applied to the substance. It is all very well for me to take a piece of antimony, and fuse it in the flame of a blowpipe. But if I tried this piece in the ordinary lamp flame, I should do nothing; if I tried a smaller piece, I should do little or nothing; and if I tried a still smaller piece, I should do little or nothing; yet I have a condition which will represent what Deville carries to the highest possible extent, and which we all carry to the highest extent, in the use of the blowpipe. Suppose I take this piece of antimony: I shall not be able to melt it in that flame of the candle by merely holding it there; yet, by taking pains, we can even melt a piece of platinum there. This is a preparation which I made for the purpose of proving the fusibility of platinum in a common candle. There is a piece of wire, drawn by that ingenious process of Dr. Wollaston's, not more than the three-thousandth part of an inch in diameter. He put the wire into the middle of a cylinder of silver, and drew both together until the whole compound was exceedingly thin; and then he dissolved away the silver by nitric acid. There was left in the centre a substance which I can scarcely see with an eye-glass, but which I know is there, and which I can make visible, as you see, by putting it into the candle, where the heat makes it glow like a spark. I have again and again tried this experiment up-stairs in my own room, and have easily fused this platinum-wire by a common candle. You see we have, therefore, heat enough in the candle, as in the voltaic battery, or in the highly-exalted combustion of the blowpipe, but we do not supply a continuous source of heat. In the very act of this becoming ignited, the heat radiates so fast that you cannot accumulate enough to cause the fusion of the wire, except under the most careful arrangement. Thus I cannot melt that piece of antimony by simply putting it into the candle; but if I put it upon charcoal, and drive the fiery current against it, there will be heat enough to melt it. The beauty of the blowpipe is, that it sends hot air (making hot air by the combustion of the flame) against the thing to be heated. I have only to hold the antimony in the course of that current, and particle by particle of the current impinges upon the antimony, and so we get it melted. You now see it red-hot, and I have no doubt it will continue to burn if I withdraw it from the flame and continue to force the air on it. Now, you see it burning without any heat but that of its own combustion, which I am keeping up by sending the air against it. It would go out in a moment if I took away the current of air from it; but there it is burning, and the more air I give it, by this or any other action, the better it is. So, then, we have here not merely a mighty source of heat, but a means of driving the heat forcibly against substances. Let me shew you another experiment with a piece of iron. It will serve two purposes--shewing you what the blowpipe does as a source of heat, and what it does by sending that heat where it is wanted. I have taken iron in contrast with silver or other metals, that you may see the difference of action, and so be more interested in the experiment. Here is our fuel, the coal-gas; and here our oxygen. Having thus my power of heat, I apply it to the iron, which, as you see, soon gets red-hot. It is now flowing about like a globule of melted mercury. But observe, I cannot raise any vapour: it is now covered with a coat of melted oxide, and unless I have a great power in my blowpipe, it is hardly possible to break through it. Now, then, you see these beautiful sparks: you have not only a beautiful kind of combustion, but you see the iron is being driven off, not producing smoke, but burning in a fixed condition. How different this is from the action of some other metals--that piece of antimony, for instance, which we saw just now throwing off abundance of fumes. We can, of course, burn away this iron by giving plenty of air to it; but with the bodies which Deville wants to expose to this intense heat he has not that means: the gas itself must have power enough to drive off the slag which forms on the surface of the metal, and power to impinge upon the platinum so as to get the full contact that he wants for the fusion to take place. We see here, then, the means to which he resorts--oxygen, and either coal-gas or water-gas[19], or pure hydrogen, for producing heat, and the blowpipe for the purpose of impelling the heated current upon the metals. I have two or three rough drawings here, representing the kind of furnaces which he employs. They are larger, however, than the actual furnaces he uses. Even the furnace in which he carries on that most serious operation of fusing fifty pounds of platinum at once is not much more than half the size of the drawing. It is made of a piece of lime below and a piece of lime above. You see how beautifully lime sustains heat without altering in shape; and you may have thought how beautifully it prevents the dissipation of the heat by its very bad conducting powers. [Illustration: Fig. 38] While the front part of the lime which you saw here was so highly ignited, I could at any moment touch the back of it without feeling any annoyance from the heat So, by having a chamber of lime of this sort, he is able to get a vessel to contain these metals with scarcely any loss of heat. He puts the blowpipes through these apertures, and sends down these gases upon the metals, which are gradually melted. He then puts in more metal through a hole at the top. The results of the combustion issue out of the aperture which you see represented. If there be strips of platinum, he pushes them through the mouth out of which the heated current is coming, and there they get red-hot and white-hot before they get into the bath of platinum. So he is able to fuse a large body of platinum in this manner. When the platinum is melted, he takes off the top and pours out from the bottom piece, like a crucible, and makes his cast. This is the furnace by which he fuses his forty pounds or fifty pounds of platinum at once. The metal is raised to a heat that no eye can bear. There is no light and shadow, no chiaro-oscuro there; all is the same intensity of glow. You look in, and you cannot see where the metal or the lime is; it is all as one. We have, therefore, a platform with a handle, which turns upon an axis, that coincides with the gutter that is formed for the pouring of the metal; and when all is known to be ready, by means of dark glasses, the workmen take off the top piece and lift up the handle, and the mould being then placed in a proper position, he knows that the issue of the metal will be exactly in the line of the axis. No injury has ever happened from the use of this plan. You know with what care it is necessary to carry such a vessel of mercury as we have here, for fear of turning it over on one side or the other; but if it be a vessel of melted platinum, the very greatest care must be used, because the substance is twice as heavy: yet no injury has been done to any of the workmen in this operation. I have said that Deville depends upon intense heat for carrying off vapour; and this brings me to the point of shewing how vapours are carried off. Here is a basin of mercury, which boils easily, as you know, and gives us the opportunity of observing the facts and principles which are to guide us. I have here two poles of the battery, and if I bring them into contact with the mercury, see what a development of vapour we have. The mercury is flying off rapidly; and I might, if I pleased, put all the company around me in a bath of mercury vapour. And so, if we take this piece of lead and treat it in the same way, it will also give off vapour. Observe the fumes that rise from it; and even if it was so far enclosed from the air that you could not form any litharge, you would still have those abundant fumes flying off. I may also take a piece of gold, and shew you the same thing. I have here a piece of gold which I put upon a clean surface of Paris limestone. Applying the heat of the blowpipe to it, you see how the heat drives off the vapour; and if you notice at the end of the Lecture, you will observe on the stone a purple patch of condensed gold. Thus you see a proof of the volatilisation of gold. It is the same with silver. You will not be startled if I sometimes use one agent and sometimes another to illustrate a particular point. The volatility of gold and silver is the same thing, whether it be effected by the voltaic battery or by the blowpipe. [A lump of silver was placed in a charcoal crucible between the poles of a voltaic battery.] Now, look at the fumes of silver, and observe the peculiar and beautiful green colour which they produce. We shall now shew you this same process of boiling the silver, cast on a screen from the electric lamp which you have before you; and while Dr. Tyndall is kindly getting the lamp ready for this purpose, let me tell you that Deville proposes to throw out in this way all these extraneous things that I have spoken of, except two--namely, iridium and rhodium. It so happens, as he says, that iridium and rhodium do make the metal more capable of resisting the attacks of acids than platinum itself. Alloys are compounded up to 25 per cent. of rhodium and iridium, by which the chemical inaction of the platinum is increased, and also its malleability and other physical properties. [The image of the voltaic discharge through vapour of silver was now thrown upon the screen.] What you have now on the screen is an inverted image of what you saw when we heated the silver before. The fine stream that you see around the silver is the discharge of the electric force that takes place, giving you that glorious green light which you see in the ray; and if Dr. Tyndall will open the top of the lamp, you will see the quantity of fumes that will come out of the aperture, shewing you at once the volatility of silver. I have now finished this imperfect account. It is but an apology for not having brought the process itself before you. I have done the best I could under the circumstances; and I know your kindness well, for if I were not aware that I might trust to it, I would not appear here so often as I have done. The gradual loss of memory and of my other faculties is making itself painfully evident to me, and requires, every time I appear before you, the continued remembrance of your kindness to enable me to get through my task. If I should happen to go on too long, or should fail in doing what you might desire, remember it is yourselves who are chargeable, by wishing me to remain. I have desired to retire, as I think every man ought to do before his faculties become impaired; but I must confess that the affection I have for this place, and for those who frequent this place, is such, that I hardly know when the proper time has arrived. NOTES. [Footnote 1: Page 16. The Royal George sunk at Spithead on The 29th of August, 1782. Colonel Pasley commenced operations for the removal of the wreck by the explosion of gunpowder, in August, 1839. The candle which Professor Faraday exhibited must therefore have been exposed to the action of salt water for upwards of fifty-seven years.] [Footnote 2: Page 17. The fat or tallow consists of a chemical combination of fatty acids with glycerine. The lime unites with the palmitic, oleic, and stearic acids, and separates the glycerine. After washing, the insoluble lime soap is decomposed with hot dilute sulphuric acid. The melted fatty acids thus rise as an oil to the surface, when they are decanted. They are again washed and cast into thin plates, which, when cold, are placed between layers of cocoa-nut matting, and submitted to intense hydraulic pressure. In this way the soft oleic acid is squeezed out, whilst the hard palmitic and stearic acids remain. These are further purified by pressure at a higher temperature, and washing in warm dilute sulphuric acid, when they are ready to be made into candles. These acids are harder and whiter than the fats from which they were obtained, whilst at the same time they are cleaner and more combustible.] [Footnote 3: Page 19. A little borax or phosphorus salt is sometimes added, in order to make the ash fusible.] [Footnote 4: Page 27. Capillary attraction or repulsion is the cause which determines the ascent or descent of a fluid in a capillary tube. If a piece of thermometer tubing, open at each end, be plunged into water, the latter will instantly rise in the tube considerably above its external level. If, on the other hand, the tube be plunged into mercury, a repulsion instead of attraction will be exhibited, and the level of the mercury will be lower in the tube than it is outside.] [Footnote 5: Page 29. The late Duke of Sussex was, we believe, the first to shew that a prawn might be washed upon this principle. If the tail, after pulling off the fan part, be placed in a tumbler of water, and the head be allowed to hang over the outside, the water will be sucked up the tail by capillary attraction, and will continue to run out through the head until the water in the glass has sunk so low that the tail ceases to dip into it.] [Footnote 6: Page 37. The alcohol had chloride of copper dissolved in it: this produces a beautiful green flame.] [Footnote 7: Page 54. Lycopodium is a yellowish powder found in the fruit of the club moss (_Lycopodium clavatum_). It is used in fireworks.] [Footnote 8: Page 58. Bunsen has calculated that the temperature of the oxyhydrogen blowpipe is 8061° Centigrade. Hydrogen burning in air has a temperature of 3259° C., and coal-gas in air, 2350° C.] [Footnote 9: Page 60. The following is the action of the sulphuric acid in inflaming the mixture of sulphuret of antimony and chlorate of potassa. A portion of the latter is decomposed by the sulphuric acid into oxide of chlorine, bisulphate of potassa, and perchlorate of potassa. The oxide of chlorine inflames the sulphuret of antimony, which is a combustible body, and the whole mass instantly bursts into flame.] [Footnote 10: Page 63. The "air-burner," which is of such value in the laboratory, owes its advantage to this principle. It consists of a cylindrical metal chimney, covered at the top with a piece of rather coarse iron-wire gauze. This is supported over an argand burner, in such a manner that the gas may mix in the chimney with an amount of air sufficient to burn the carbon and hydrogen simultaneously, so that there may be no separation of carbon in the flame with consequent deposition of soot. The flame, being unable to pass through the wire gauze, burns in a steady, nearly invisible manner above.] [Footnote 11: Page 74. Water is in its densest state at a temperature of 39.1° Fahrenheit] [Footnote 12: Page 74. A mixture of salt and pounded ice reduces the temperature from 32° F. to zero--the ice at the same time becoming fluid.] [Footnote 13: Page 82. Potassium, the metallic basis of potash, was discovered by Sir Humphrey Davy in 1807, who succeeded in separating it from potash by means of a powerful voltaic battery. Its great affinity for oxygen causes it to decompose water with evolution of hydrogen, which takes fire with the heat produced.] [Footnote 14: Page 98. Professor Faraday has calculated that there is as much electricity required to decompose one grain of water as there is in a very powerful flash of lightning.] [Footnote 15: Page 101. A solution of acetate of lead submitted to the action of the voltaic current, yields lead at the negative pole, and brown peroxide of lead at the positive pole. A solution of nitrate of silver, under the same circumstances, yields silver at the negative pole, and peroxide of silver at the positive pole.] [Footnote 16: Page 129. The gas which is thus employed as a test for the presence of oxygen, is the binoxide of nitrogen, or nitrous oxide. It is a colourless gas, which, when brought in contact with oxygen, unites with it, forming hyponitric acid, the red gas referred to.] [Footnote 17: Page 152. _Marble_ is a compound of carbonic acid and lime. The muriatic acid being the stronger of the two, takes the place of the carbonic acid, which escapes as a gas, the residue forming muriate of lime or chloride of calcium.] [Footnote 18: Page 186. _Lead pyrophorus_ is made by heating dry tartrate of lead in a glass tube (closed at one end, and drawn out to a fine point at the other) until no more vapours are evolved. The open end of the tube is then to be sealed before the blowpipe. When the tube is broken and the contents shaken out into the air, they burn with a red flash.] [Footnote 19: Page 216. _Water-gas_ is formed by passing vapour of water over red-hot charcoal or coke. It is a mixture of hydrogen and carbonic oxide; each of which is an inflammable gas.] Poster's note: "combustion that makes!" was corrected from a misprint "combusion that makes!" in the original. 
24591	----	None 
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31624	----	[Transcriber's Notes: The following errors are noted, but have not been corrected: Page 17, footnote: "plutomium" should be "plutonium" Page 8: "knowns" should be "knows" In element names, {} represents subscripted numbers and <> represents superscripted numbers. Readers may also refer to the HTML version of the text, in which super and subscripted numbers are represented visually. Italic emphasis is indicated by surrounding the word with _underscores_. Greek letters in the original text are marked in brackets, e. g. [alpha] or [gamma]. Table I (THE TRANSURANIUM ELEMENTS) has been moved from pages 12-13, in the middle of the book, to the end of the text.] A Brief History of ELEMENT DISCOVERY, SYNTHESIS, and ANALYSIS Glen W. Watson September 1963 [Illustration] LAWRENCE RADIATION LABORATORY University of California Berkeley and Livermore Operating under contract with the United States Atomic Energy Commission [Illustration: Radioactive elements: alpha particles from a speck of radium leave tracks on a photographic emulsion. (Occhialini and Powell, 1947)] A BRIEF HISTORY OF ELEMENT DISCOVERY, SYNTHESIS, AND ANALYSIS It is well known that the number of elements has grown from four in the days of the Greeks to 103 at present, but the change in methods needed for their discovery is not so well known. Up until 1939, only 88 naturally occurring elements had been discovered. It took a dramatic modern technique (based on Ernest O. Lawrence's Nobel-prize-winning atom smasher, the cyclotron) to synthesize the most recently discovered elements. Most of these recent discoveries are directly attributed to scientists working under the Atomic Energy Commission at the University of California's Radiation Laboratory at Berkeley. But it is apparent that our present knowledge of the elements stretches back into history: back to England's Ernest Rutherford, who in 1919 proved that, occasionally, when an alpha particle from radium strikes a nitrogen atom, either a proton or a hydrogen nucleus is ejected; to the Dane Niels Bohr and his 1913 idea of electron orbits; to a once unknown Swiss patent clerk, Albert Einstein, and his now famous theories; to Poland's Marie Curie who, in 1898, with her French husband Pierre laboriously isolated polonium and radium; back to the French scientist H. A. Becquerel, who first discovered something he called a "spontaneous emission of penetrating rays from certain salts of uranium"; to the German physicist W. K. Roentgen and his discovery of x rays in 1895; and back still further. During this passage of scientific history, the very idea of "element" has undergone several great changes. The early Greeks suggested earth, air, fire, and water as being the essential material from which all others were made. Aristotle considered these as being combinations of four properties: hot, cold, dry, and moist (see Fig. 1). [Illustration: Fig. 1. The elements as proposed by the early Greeks.] Later, a fifth "essence," ether, the building material of the heavenly bodies was added. Paracelsus (1493-1541) introduced the three alchemical symbols salt, sulfur, and mercury. Sulfur was the principle of combustability, salt the fixed part left after burning (calcination), and mercury the essential part of all metals. For example, gold and silver were supposedly different combinations of sulfur and mercury. Robert Boyle in his "Sceptical Chymist" (1661) first defined the word element in the sense which it retained until the discovery of radioactivity (1896), namely, a form of matter that could not be split into simpler forms. The first discovery of a true element in historical time was that of phosphorus by Dr. Brand of Hamburg, in 1669. Brand kept his process secret, but, as in modern times, knowledge of the element's existence was sufficient to let others, like Kunkel and Boyle in England, succeed independently in isolating it shortly afterward. As in our atomic age, a delicate balance was made between the "light-giving" (desirable) and "heat-giving" (feared) powers of a discovery. An early experimenter was at first "delighted with the white, waxy substance that glowed so charmingly in the dark of his laboratory," but later wrote, "I am not making it any more for much harm may come of it." Robert Boyle wrote in 1680 of phosphorus, "It shone so briskly and lookt so oddly that the sight was extreamly pleasing, having in it a mixture of strangeness, beauty and frightfulness." These words describe almost exactly the impressions of eye witnesses of the first atom bomb test at Alamagordo, New Mexico, July 16, 1945. For the next two and three-quarters centuries the chemists had much fun and some fame discovering new elements. Frequently there was a long interval between discovery and recognition. Thus Scheele made chlorine in 1774 by the action of "black manganese" (manganese dioxide) on concentrated muriatic acid (hydrochloric acid), but it was not recognized as an element till the work of Davy in 1810. Occasionally the development of a new technique would lead to the "easy" discovery of a whole group of new elements. Thus Davy, starting in 1807, applied the method of electrolysis, using a development of Volta's pile as a source of current; in a short time he discovered aluminum, barium, boron, calcium, magnesium, potassium, sodium, and strontium. The invention of the spectroscope by Bunsen and Kirchhoff in 1859 provided a new tool which could establish the purity of substances already known and lead to the discovery of others. Thus, helium was discovered in the sun's spectrum by Jansen and isolated from uranite by Ramsay in 1895. The discovery of radioactivity by Becquerel in 1896 (touched off by Roentgen's discovery of x rays the year before) gave an even more sensitive method of detecting the presence or absence of certain kinds of matter. It is well known that Pierre and Marie Curie used this new-found radioactivity to identify the new elements polonium and radium. Compounds of these new elements were obtained by patient fractional recrystallization of their salts. The "explanation" of radioactivity led to the discovery of isotopes by Rutherford and Soddy in 1914, and with this discovery a revision of our idea of elements became necessary. Since Boyle, it had been assumed that all atoms of the individual elements were identical and unlike any others, and could not be changed into anything simpler. Now it became evident that the atoms of radioactive elements were constantly changing into other elements, thereby releasing very large amounts of energy, and that many different forms of the same element (lead was the first studied) were possible. We now think of an element as a form of matter in which all atoms have the same nuclear charge. The human mind has always sought order and simplification of the external world; in chemistry the fruitful classifications were Dobereiner's Triads (1829), Newland's law of octaves (1865), and Mendeleev's periodic law (1869). The chart expressing this periodic law seemed to indicate the maximum extent of the elements and gave good hints "where to look for" and "the probable properties of" the remaining ones (see Fig. 2). By 1925, all but four of the slots in the 92-place file had been filled. The vacancies were at 43, 61, 85, and 87. [Illustration: Fig. 2. Periodic chart of the elements (1963)] Workers using traditional analytical techniques continued to search for these elements, but their efforts were foredoomed to failure. None of the nuclei of the isotopes of elements 43, 61, 85, and 87 are stable; hence weighable quantities of them do not exist in nature, and new techniques had to be developed before we could really say we had "discovered" them. In 1919, Rutherford accomplished scientifically what medieval alchemists had failed to do with "magic" experiments and other less sophisticated techniques. It wasn't gold (the goal of the alchemists) he found but something more valuable with even greater potential for good and evil: a method of transmuting one element into another. By bombarding nitrogen nuclei with alpha particles from radium, he found that nitrogen was changed into oxygen. The process for radioactive transmutation is somewhat like a common chemical reaction. An alpha particle, which has the same charge (+2) and atomic mass (4) as a helium nucleus, penetrates the repulsive forces of the nitrogen nucleus and deposits one proton and one neutron; this changes the nitrogen atom into an oxygen atom. The reaction is written {7}N<14> + {2}He<4> --> {1}H<1> + {8}O<17>. The number at the lower left of each element symbol in the above reaction is the proton number. This number determines the basic chemical identity of an atom, and it is this number scientists must change before one element can be transformed into another. The common way to accomplish this artificially is by bombarding nuclei with nuclear projectiles. Rutherford used naturally occurring alpha particles from radium as his projectiles because they were the most effective he could then find. But these natural alpha particles have several drawbacks: they are positively charged, like the nucleus itself, and are therefore more or less repulsed depending on the proton number of the element being bombarded; they do not move fast enough to penetrate the nuclei of heavier elements (those with many protons); and, for various other reasons (some of them unexplained), are inefficient in breaking up the nucleus. It is estimated that only 1 out of 300,000 of these alpha particles will react with nitrogen. Physicists immediately began the search for artificial means to accelerate a wider variety of nuclear particles to high energies. Protons, because they have a +1 charge rather than the +2 charge of the alpha particles, are repulsed less strongly by the positive charge on the nucleus, and are therefore more useful as bombarding projectiles. In 1929, E. T. S. Walton and J. D. Cockcroft passed an electric discharge through hydrogen gas, thereby removing electrons from the hydrogen atom; this left a beam of protons (i. e., hydrogen ions), which was then accelerated by high voltages. This Cockcroft-Walton voltage multiplier accelerated the protons to fairly high energies (about 800,000 electron volts), but the protons still had a plus charge and their energies were still not high enough to overcome the repulsive forces (Coulombic repulsion) of the heavier nuclei. A later development, the Van de Graaff electrostatic generator, produced a beam of hydrogen ions and other positively charged ions, and electrons at even higher energies. An early model of the linear accelerator also gave a beam of heavy positive ions at high energies. These were the next two instruments devised in the search for efficient bombarding projectiles. However, the impasse continued: neither instrument allowed scientists to crack the nuclei of the heavier elements. Ernest O. Lawrence's cyclotron, built in 1931, was the first device capable of accelerating positive ions to the very high energies needed. Its basic principle of operation is not difficult to understand. A charged particle accelerated in a cyclotron is analogous to a ball being whirled on a string fastened to the top of a pole. A negative electric field attracts the positively charged particle (ball) towards it and then switches off until the particle swings halfway around; the field then becomes negative in front of the particle again, and again attracts it. As the particle moves faster and faster it spirals outward in an ever increasing circle, something like a tether ball unwinding from a pole. The energies achieved would have seemed fantastic to earlier scientists. The Bevatron, a modern offspring of the first cyclotron, accelerates protons to 99.13% the speed of light, thereby giving them 6.2 billion electron volts (BeV). Another instrument, the heavy-ion linear accelerator (Hilac), accelerates ions as heavy as neon to about 15% the speed of light. It is called a linear accelerator because it accelerates particles in a straight line. Stanford University is currently (1963) in the process of building a linear accelerator approximately two miles long which will accelerate charged particles to 99.9% the speed of light. But highly accelerated charged particles did not solve all of science's questions about the inner workings of the nucleus. In 1932, during the early search for more efficient ways to bombard nuclei, James Chadwick discovered the neutron. This particle, which is neutral in charge and is approximately the same mass as a proton, has the remarkable quality of efficiently producing nuclear reactions even at very low energies. No one exactly knowns why. At low energies, protons, alpha particles, or other charged particles do not interact with nuclei because they cannot penetrate the electrostatic energy barriers. For example, slow positive particles pick up electrons, become neutral, and lose their ability to cause nuclear transformations. Slow neutrons, on the other hand, can enter nearly all atomic nuclei and induce fission of certain of the heavier ones. It is, in fact, these properties of the neutron which have made possible the utilization of atomic energy. With these tools, researchers were not long in accurately identifying the missing elements 43, 61, 85, and 87 and more--indeed, the list of new elements, isotopes, and particles now seems endless. Element 43 was "made" for the first time as a result of bombarding molybdenum with deuterons in the Berkeley cyclotron. The chemical work of identifying the element was done by Emilio Segrè and others then working at Palermo, Sicily, and they chose to call it technetium, because it was the element first made by artificial technical methods. Element 61 was made for the first time from the fission disintegration products of uranium in the Clinton (Oak Ridge) reactor. Marinsky and Glendenin, who did the chemical work of identification, chose to call it promethium because they wished to point out that just as Prometheus stole fire (a great force for good or evil) from the hidden storehouse of the gods and presented it to man, so their newly assembled reactor delivered to mankind an even greater force, nuclear energy. Element 85 is called astatine, from the Greek astatos, meaning "unstable," because astatine _is_ unstable (of course all other elements having a nuclear charge number greater than 84 are unstable, too). Astatine was first made at Berkeley by bombarding bismuth with alpha particles, which produced astatine and released two neutrons. The element has since been found in nature as a small constituent of the natural decay of actinium. The last of the original 92 elements to be discovered was element 87, francium. It was identified in 1939 by French scientist Marguerite Perey. Children have a game in which they pile blocks up to see how high they can go before they topple over. In medieval times, petty rulers in their Italian states vied with one another to see who could build the tallest tower. Some beautiful results of this game still remain in Florence, Siena, and other Italian hill cities. Currently, Americans vie in a similar way with the wheelbase and overall length of their cars. After 1934, the game among scientists took the form of seeing who could extend the length of the periodic system of the elements; as with medieval towers, it was Italy that again began with the most enthusiasm and activity under the leadership of Enrico Fermi. Merely adding neutrons would not be enough; that would make only a heavier isotope of the already known heaviest elements, uranium. However, if the incoming neutron caused some rearrangement within the nucleus and if it were accompanied by expulsion of electrons, that _would_ make a new element. Trials by Fermi and his co-workers with various elements led to unmistakeable evidence of the expulsion of electrons (beta activity) with at least four different rates of decay (half-lives). Claims were advanced for the creation of elements 93 and 94 and possibly further (the transuranium elements, Table I). Much difficulty was experienced, however, in proving that the activity really was due to the formation of elements 93 and 94. As more people became interested and extended the scope of the experiments, the picture became more confused rather than clarified. Careful studies soon showed that the activities did _not_ decay logarithmically--which means that they were caused by mixtures, not individual pure substances--and the original four activities reported by Fermi grew to at least nine. As a matter of fact, the way out of the difficulty had been indicated soon after Fermi's original announcement. Dr. Ida Noddack pointed out that no one had searched among the products of Fermi's experiment for elements _lighter_ than lead, but no one paid any attention to her suggestion at the time. The matter was finally cleared up by Dr. Otto Hahn and F. Strassmann. They were able to show that instead of uranium having small pieces like helium nuclei, fast electrons, and super-hard x-rays, knocked off as expected, the atom had split into two roughly equal pieces, together with some excess neutrons. This process is called nuclear fission. The two large pieces were unstable and decayed further with the loss of electrons, hence the [beta] activity. This process is so complicated that there are not, as originally reported, only four half-lives, but at least 200 different varieties of at least 35 different elements. The discovery of fission attended by the release of enormous amounts of energy led to feverish activity on the part of physicists and chemists everywhere in the world. In June 1940, McMillan and Abelson presented definite proof that element 93 had been found in uranium penetrated by neutrons during deuteron bombardment in the cyclotron at the University of California Radiation Laboratory. The California scientists called the newly discovered element neptunium, because it lies beyond the element uranium just as the planet Neptune lies beyond Uranus. The particular isotope formed in those first experiments was {93}Np<239>; this is read neptunium having a nuclear charge of 93 and an atomic mass number of 239. It has a half-life of 2.3 days, during which it gives up another electron ([beta] particle) and becomes element 94, or plutonium (so called after Pluto, the next planet beyond Neptune). This particular form of plutonium ({94}Pu<239>) has such a long half-life (24,000 years) that it could not be detected. The first isotope of element 94 to be discovered was Pu<238>, made by direct deuteron bombardment in the Berkeley 60-inch cyclotron by Radiation Laboratory scientists Seaborg, McMillan, Kennedy, and Wahl; it had an [alpha]-decay half-life of 86.4 years, which gave it sufficient radioactivity so that its chemistry could be studied. Having found these chemical properties in Pu<238>, experimenters knew {94}Pu<239> would behave similarly. It was soon shown that the nucleus of {94}Pu<239> would undergo fission in the same way as {92}U<235> when bombarded with slow neutrons and that it could be produced in the newly assembled atomic pile. Researchers wished to learn as much as possible about its chemistry; therefore, during the summer of 1942 two large cyclotrons at St. Louis and Berkeley bombarded hundreds of pounds of uranium almost continuously. This resulted in the formation of 200 micrograms of plutonium. From this small amount, enough of the chemical properties of the element were learned to permit correct design of the huge plutonium-recovery plant at Hanford, Washington. In the course of these investigations, balances that would weigh up to 10.5 mg with a sensitivity of 0.02 microgram were developed. The "test tubes" and "beakers" used had internal diameters of 0.1 to 1 mm and could measure volumes of 1/10 to 1/10,000 ml with an accuracy of 1%. The fact that there was no intermediate stage of experimentation, but a direct scale-up at Hanford of ten billion times, required truly heroic skill and courage. By 1944 sufficient plutonium was available from uranium piles (reactors) so that it was available as target material for cyclotrons. At Berkeley it was bombarded with 32-MeV doubly charged helium ions, and the following reactions took place: {94}Pu<239> ([alpha], n) {96}Cm<242> [alpha] / 150 days --> {94}Pu<238>. This is to be read: plutonium having an atomic number of 94 (94 positively charged protons in the nucleus) and a mass number of 239 (the whole atom weighs approximately 239 times as much as a proton), when bombarded with alpha particles (positively charged helium nuclei) reacts to give off a neutron and a new element, curium, that has atomic number 96 and mass number 242. This gives off alpha particles at such a rate that half of it has decomposed in 150 days, leaving plutonium with atomic number 94 and mass number 238. The radiochemical work leading to the isolation and identification of the atoms of element 96 was done at the metallurgical laboratory of the University of Chicago. The intense neutron flux available in modern reactors led to a new element, americium (Am), as follows: {94}Pu<239> (n, [gamma]) {94}Pu<240> (n, [gamma]) {94}Pu<241> [beta] --> {95}Am<241>. The notation (n, [gamma]) means that the plutonium absorbs a neutron and gives off some energy in the form of gamma rays (very hard x rays); it first forms {94}Pu<240> and then {94}Pu<241>, which is unstable and gives off fast electrons ([beta]), leaving {95}Am<241>. Berkelium and californium, elements 97 and 98, were produced at the University of California by methods analogous to that used for curium, as shown in the following equations: {95}Am<240> + [alpha] --> {97}Bk<243> + {0}n<1>, and {96}Cm<241> + [alpha] --> {98}Cf<244> + {0}n<1>. The next two elements, einsteinium ({99}Es) and fermium ({100}Fm), were originally found in the debris from the thermonuclear device "Mike," which was detonated on Eniwetok atoll November 1952. (This method of creating new substances is somewhat more extravagant than the mythical Chinese method of burning down a building to get a roast pig.) These elements have since been made in nuclear reactors and by bombardment. This time the "bullet" was N<14> stripped of electrons till it had a charge of +6, and the target was plutonium. Researchers at the University of California used new techniques in forming and identifying element 101, mendelevium. A very thin layer of {99}Es<253> was electroplated onto a thin gold foil and was then bombarded, from behind the layer, with 41-MeV [alpha] particles. Unchanged {99}Es<253> stayed on the gold, but those atoms hit by [alpha] particles were knocked off and deposited on a "catcher" gold foil, which was then dissolved and analyzed (Fig. 3). This freed the new element from most of the very reactive parent substances, so that analysis was easier. Even so, the radioactivity was so weak that the new element was identified "one atom at a time"; this is possible because its daughter element, fermium, spontaneously fissions and releases energy in greater bursts than any possible contaminant. [Illustration: Fig. 3. The production of mendelevium.] In 1957, in Stockholm, element 102 was reported found by an international team of scientists (who called it nobelium), but diligent and extensive research failed to duplicate the Stockholm findings. However, a still newer technique developed at Berkeley showed the footprints--if not the living presence--of 102 (see Fig. 4). The rare isotope curium-246 is coated on a small piece of nickel foil, enclosed in a helium-filled container, and placed in the heavy-ion linear accelerator (Hilac) beam. Positively charged atoms of element 102 are knocked off the foil by the beam, which is of carbon-12 or carbon-13 nuclei, and are deposited on a negatively charged conveyor apron. But element 102 doesn't live long enough to be actually measured. As it decays, its daughter product, {100}Fm<250>, is attracted onto a charged aluminum foil where it can be analyzed. The researchers have decided that the hen really did come first: they have the egg; therefore the hen must have existed. By measuring the time distance between target and daughter product, they figure that the hen-mother (element 102) must have a half-life of three seconds. [Illustration: Fig. 4. The experimental arrangement used in the discovery of element 102.] In an experiment completed in 1961, researchers at the University of California at Berkeley unearthed similar "footprints" belonging to element 103 (named lawrencium in honor of Nobel prizewinner Ernest O. Lawrence). They found that the bombardment of californium with boron ions released [alpha] particles which had an energy of 8.6 MeV and decayed with a half-life of 8 ± 2 seconds. These particles can only be produced by element 103, which, according to one scientific theory, is a type of "dinosaur" of matter that died out a few weeks after creation of the universe. The half-life of lawrencium (Lw) is about 8 seconds, and its mass number is thought to be 257, although further research is required to establish this conclusively. Research on lawrencium is complicated. Its total [alpha] activity amounts to barely a few counts per hour. And, since scientists had the [alpha]-particle "footprints" only and not the beast itself, the complications increased. Therefore no direct chemical techniques could be used, and element 103 was the first to be discovered solely by nuclear methods.[A] For many years the periodic system was considered closed at 92. It has now been extended by at least eleven places (Table I), and one of the extensions (plutonium) has been made in truckload lots. Its production and use affect the life of everyone in the United States and most of the world. Surely the end is again in sight, at least for ordinary matter, although persistent scientists may shift their search to the other-world "anti" particles. These, too, will call for very special techniques for detection of their fleeting presence. Early enthusiastic researchers complained that a man's life was not long enough to let him do all the work he would like on an element. The situation has now reached a state of equilibrium; neither man nor element lives long enough to permit all the desired work. [A] In August 1964 Russian scientists claimed that they created element 104 with a half-life of about 0.3 seconds by bombarding plutomium with accelerated neon-22 ions. Table I. THE TRANSURANIUM ELEMENTS ======================================================================== Element Name (Symbol) Mass Year Discovered; by whom; Number where; how ------------------------------------------------------------------------ 93 Neptunium (Np) 238 1940; E. M. McMillan, P. H. Abelson; University of California at Berkeley; slow-neutron bombardment of U<238> in the 60-inch cyclotron. ------------------------------------------------------------------------ 94 Plutonium (Pu) 238 1941; J. W. Kennedy, E. M. McMillan, G. T. Seaborg, and A. C. Wahl; University of California at Berkeley; 16-MeV deuteron bombardment of U<238> in the 60-inch cyclotron. (Pu) 239 Pu<239>; the fissionable isotope of plutonium, was also discovered in 1941 by J. W. Kennedy, G. T. Seaborg, E. Segrè and A. C. Wahl; University of California at Berkeley; slow-neutron bombardment of U<238> in the 60-inch cyclotron. ------------------------------------------------------------------------ 95 Americium (Am) 241 1944-45; Berkeley scientists A. Ghiorso, R. A. James, L. O. Morgan, and G. T. Seaborg at the University of Chicago; intense neutron bombardment of plutonium in nuclear reactors. ------------------------------------------------------------------------ 96 Curium (Cm) 242 1945; Berkeley scientists A. Ghiorso, R. A. James, and G. T. Seaborg at the University of Chicago; bombardment of Pu<239> by 32-MeV helium ions from the 60-inch cyclotron. ------------------------------------------------------------------------ 97 Berkelium (Bk) 243 1949; S. G. Thompson, A. Ghiorso, and G. T. Seaborg; University of California at Berkeley; 35-MeV helium-ion bombardment of Am<241>. ------------------------------------------------------------------------ 98 Californium (Cf) 245 1950; S. G. Thompson, K. Street, A. Ghiorso, G. T. Seaborg; University of California at Berkeley; 35-MeV helium-ion bombardment of Cm<242>. ------------------------------------------------------------------------ 99 Einsteinium (Es) 253 1952-53; A. Ghiorso, S. G. 100 Fermium (Fm) 255 Thompson, G. H. Higgins, G. T. Seaborg, M. H. Studier, P. R. Fields, S. M. Fried, H. Diamond, J. F. Mech, G. L. Pyle, J. R. Huizenga, A. Hirsch, W. M. Manning, C. I. Browne, H. L. Smith, R. W. Spence; "Mike" explosion in South Pacific; work done at University of California at Berkeley, Los Alamos Scientific Laboratory, and Argonne National Laboratory; both elements created by multiple capture of neutrons in uranium of first detonation of a thermonuclear device. The elements were chemically isolated from the debris of the explosion. ------------------------------------------------------------------------ 101 Mendelevium (Md) 256 1955; A. Ghiorso, B. G. Harvey, G. R. Choppin, S. G. Thompson, G. T. Seaborg; University of California at Berkeley; 41-MeV helium-ion bombardment of Es<253> in 60-inch cyclotron. ------------------------------------------------------------------------ 102 Unnamed[B] 254 1958; A. Ghiorso, T. Sikkeland, A. E. Larsh, R. M. Latimer; University of California, Lawrence Radiation Laboratory, Berkeley; 68-MeV carbon-ion bombardment of Cm<246> in heavy-ion linear accelerator (Hilac). ------------------------------------------------------------------------ 103 Lawrencium 257 1961; A. Ghiorso, T. Sikkeland, A. E. Larsh, R. M. Latimer; University of California, Lawrence Radiation Laboratory, Berkeley; 70-MeV boron-ion bombardment of Cf<250>, Cf<251>, and Cf<252> in Hilac. ======================================================================== [B] A 1957 claim for the synthesis and identification of element 102 was accepted at that time by the International Union of Pure and Applied Chemistry, and the name nobelium (symbol No) was adopted. The University of California scientists, A. Ghiorso et al., cited here believe they have disproved the earlier claim and have the right to suggest a different name for the element. 
3708	----	None 
37283	----	The Complete Art OF MAKING THE Chemical Fulminating Objects, _&c. &c. &c._ _Entered at Stationers' Hall._ _The whole Secret laid Open_, OR THE COMPLETE ART OF MAKING _THE CHEMICAL_ FULMINATING OBJECTS, _SUCH AS THE_ Lace, or Girt of Security, _Fulminating Letters_, _Balls_, _Bombs_, GARTERS, CARDS, SPIDERS, SEGARS, Chairs, Drawers, Boots, Shoes, &c. &c. FOURTH EDITION. LONDON: Published by J. JOHNSTON, 98, CHEAPSIDE, for the Author, 12, King-Street, Portman-Square, and sold by all Booksellers. ADDRESS TO THE READER. That Chemistry is one of the most sublime sciences is generally acknowledged; to it may be ascribed the brilliant discoveries lately made in the arts and sciences, and without whose aid the wonderful phenomena, which are the subject of the following pages, could never have been discovered. The Author has for some time observed the wonder occasioned by the introduction of the chemical _Fulminating Objects_ to the Public: they are indeed objects of wonder, and when it is considered how trifling a portion of matter it requires to produce effects so surprising, we cannot but hail that science as truly grand, which can create such rare productions, from what we daily handle, with such safety and unconcern, and without which we should be at a loss to carry on our intercourse in trade; I mean Silver, which is the basis of all the objects presented to view. I have long seen with astonishment the manufacture of these objects, and the knowledge of that manufacture confined to very few persons, and I considered that it could not but be very much wished by all who had witnessed these astonishing productions, to acquire a true knowledge of how, and by what means, they were produced; I therefore examined them minutely, and having discovered their composition, I have given them to the Public in an entire and perfect form, accompanied with patterns of the most difficult, and have enlarged them by several objects of my own invention. That they will be found an innocent amusement, as well as a safeguard, need not be doubted, and also tend to exemplify the astonishing powers of Chemistry, the study of which I would earnestly recommend to all who have not studied that science, and to those who have, to continue it with a steady perseverance. It is a study in itself truly sublime, it is highly conducive to morality, and tends most materially to convince every wavering or doubting mind, that the world we inhabit, and all its necessaries, its conveniences, its luxuries, and its blessings, are the work of that Divine Author "Who sees, with equal eye, as God of all, A hero perish, or a sparrow fall." _Pope._ Having said thus much, I can only assure my reader, that by adhering to the rules I have laid down in the following pages, they may enjoy a rational and innocent employment of time, and be able to inform learned enquirers the nature and properties of the objects of their leisure hours' amusement, and that it may inspire them with a thirst for nearer acquaintance with chemical truths, is the sincere wish of THE AUTHOR. _March 1, 1818._ _GENERAL_ OBSERVATIONS. In pointing out the method of forming the Fulminating objects I have endeavoured to be as explicit as possible; and I feel a confidence that every necessary information is here contained. The reason why I sometimes mention Fulminating Silver, and at others preface it by Brugnatelli's, is, that there are two kinds: one sold under the name of Fulminating Silver, the other called Brugnatelli's Fulminating Silver. The quantities here directed for each object must be strictly adhered to, as it is of too dangerous a nature to be increased in quantity, without the risk of accident. I must also beg great care will be observed in handling it, both before and after the objects are manufactured: with a trifling degree of caution, no accident can possibly occur; all that is required is to avoid heat and friction, as either in excess produces instant detonation. It is also necessary to guard against exploding the objects near the eyes; these precautions observed, no danger need be apprehended. The best place to purchase the principal materials are the undermentioned places: for the Fulminating Silver, and Brugnatelli's Ditto, is Messrs. Accum and Garden, Old Compton-Street, London, and every other Manufacturing Chemist; the glass globes, of all sizes, are to be had of F. Pastorelli, Barometer and Thermometer Manufacturer, No. 4, Cross-Street, Hatton-Garden, London. The spiders are to be had of most glass blowers--for the cards, &c. every one is aware where to apply. The glass composition is made as follows: take one ounce of gum arabic, and dissolve it in a quarter of a pint of water, boil it till tolerably thick, and then add as much coarse powdered glass as will form a very thick composition. N.B. When the glass composition cannot be conveniently obtained, glass paper may be used, pasted in the same way as directed for the composition. COMPLETE ART, &c. THE LACE, _Or Girt of Security_. The Lace or Girt is made of strong brace-web, after the manner and size of the paper pattern enclosed; the parts marked with ink are to be covered with the glass composition, to be laid on tolerably thick--say the thickness of a three shilling piece, and about an eighth of an inch broad in each place; let it remain until quite dry, and then sew it in like manner as the pattern, and from one to one grain and a half of Fulminating Silver to be enclosed in the part marked S; a piece of paper or silk well pasted on one side is then to be wrapped twice round in the same manner as the paper in the pattern is pinned; a strong lace-hole is then to be worked at each end--the manner of applying it is to hang it on two hooks, one on the door post, and the other on the door, taking care to place the part in such a position as to come in contact with the edge of the door, on its being opened, which will cause an immediate explosion louder than a musket. Hooks may also be placed on windows or shutters, and the Lace being hung on them will produce the same effect: a greater safeguard against midnight intruders has never been discovered. FULMINATING LETTERS. The letter inclosed is a pattern of the manner in which they are put together, an examination of which will give the true idea to every attentive observer: a sheet of paper should be used doubled, and cut according to pattern; two slips of parchment must be used instead of those of paper, as enclosed in the pattern letter. The ends marked with Ink must be slightly covered with glass composition, and about an eighth of an inch wide, they must then be laid separately to dry, and when quite dry they must be sewn at one edge as shewn in the pattern, you must then put one third of a grain of Brugnatelli's Fulminating Silver in between the parts marked S, a piece of coloured paper or ribbon is then to be pasted well on one side, and wound twice round in the same way as the paper is now pinned round. The parchment slips thus prepared, must be pasted at each end for about an inch, and so fastened to the letter marked with a cross; the letter is then to be folded, and no further sealing is required. It must here be observed, that although the pattern is in miniature, the directions here given are intended for a common size letter; all that is required to make it so, being to use longer strips of parchment, taking care that the parchment is always as long as the letter is wide. This letter may be sent to any part of the world, and on its being opened will cause a report nearly as loud as a pistol: it is consequently well adapted to prove a never-failing source of amusement. _FULMINATING_ BALLS & BOMBS. The ball comprises a glass globe rather larger than a pea, having a small aperture, into which should be put from one third to half a grain of Brugnatelli's Fulminating Silver: a piece of paper is then to be pasted carefully all over the ball, in order to cover the glass and prevent the escape of the Silver.--The method of using the balls is to throw them down smartly, or to place one under the ball of the heel and tread hard upon it, which causes an explosion equal to a pistol and free from danger; the latter method of using them is generally preferred, and is assuredly the most certain. * * * * * A Bomb consists of the same materials as a ball, only on a larger scale: the globe for a bomb is the size of a common nut, and the quantity of Brugnatelli's Fulminating Silver is from one grain to one grain and a half, according to the report wished to be produced. The way of applying bombs is by throwing them down with violence, and it should here be remembered that this is the less exceptionable method of using them: they should on no occasion be used, without apprising the bye-standers, nor must they ever be pressed on by the foot; as the shock produced by the detonation would be rather too violent. FULMINATING SPIDERS. The Spider is formed after the manner of the common spider, it has a glass body, into which is put one third of a grain of fulminating silver. The manner of using: being formed in every respect so as to resemble the spider, they may be left on the ground, in closets, or on any article of wearing apparel, from whence they will consequently soon be dislodged, and from the natural antipathy towards this disagreeable insect, there can be no doubt of its being soon trod upon, when, to the no small surprise of the treader, a report equal to that of a pistol will be produced.--Many persons apply them to Ladies' Dresses, but from the well-known delicacy of female nerves, it were better perhaps to abstain from this experiment. Observe, the spiders cannot be exploded but by pressure, which is best done by the foot. FULMINATING CARDS & SEGARS. The Card is of the pattern herein enclosed; it must be opened at one end with a pen-knife, as here shewn, into which opening put one-fourth, or one-third of a grain at most, of Fulminating Silver; the edges are then to be pasted slightly, and closed together; a notch should also be cut at the other end, as in the pattern. When dry it will be complete for use. The manner of using, is to take it by the notched end, and light the square end at the candle, when a sharp detonation ensues.--The Card should be three quarters of an inch wide, and from four to five inches in length. Cards thus prepared, have long sold in Paris under the denomination of "Detonating Cards." * * * * * The SEGAR is made by just opening the end of a common Segar, (which may be had at all Tobacconists) and gently placing within it one-fourth of a grain of Fulminating Silver between the leaves, the end is then to be closed again, and care taken to close it, so as to prevent the Powder falling out. This, on being set fire to, causes a loud explosion, and not a little disconcerts the nerves of the smoker; nor does it fail to move the risible features of the lookers-on. * * * * * The Segar, when exploded, may be smoked with perfect safety. _Fulminating Pins._ Take one third of a grain of Brugnatelli's Fulminating Silver, and enclose in a very small fold of paper; this enclose in a second paper, which has been previously pasted, and then let it be wrapped 2 or 3 times round a common pin, observing to leave the point clear.--Pins, thus prepared, may be stuck in the wick of the candle, in the candle itself, or thrown into the fire, and immediately on their taking fire a loud explosion will follow. Observe, not to place them too near any person's eyes, least, on an explosion, the pins should be thrown out, which might prove unpleasant. _FULMINATING_ WAX TAPERS. These Tapers are prepared by taking off a small part of the wax, near the tip of the wick, and putting one-third of a grain of Fulminating Silver in the wick, then replace the wax, and on its taking fire, a loud Detonation will be produced. FULMINATING GARTERS. The garter is formed of common tape, or of the common worsted binding, which should not exceed the length and breadth of the enclosed pattern; the parts marked with ink are to be covered with the glass composition in the same manner as directed for the Lace of Security; suffer it to remain till quite dry, and then sew it together as in the pattern; half a grain of the Fulminating Silver is then to be placed between the parts marked S, and a piece of paper or ribbon, well pasted on one side, is to be wrapped twice round in the same way as directed for the lace. The manner of applying it is, to take one end in each hand, and by suddenly pulling it, a loud report will be given, equal to a large pistol.--This experiment may also be performed by offering one end to another person, and requesting them to pull against you, or by giving them the garter, and desiring them to use it as first directed. Keep the garter below the eyes. _Fulminating Chairs_ Are thus prepared: Enclose half a grain of Brugnatelli's Fulminating Silver in a piece of glass paper, and that should be again enclosed in a square piece of tinfoil; this doubled in a very small compass may be placed immediately under the foot of a chair, and the chair placed very lightly upon it, or pasting it would be much better; be careful to stand the chair down very gently: on any one's setting down on a chair so prepared, a loud Detonation will follow.--This experiment is particularly innocent, and may be productive of much mirth. FULMINATING _DRAWERS_. The preparation for the drawers is the same as used for the chairs: it should be pasted directly under the drawer, or on the side; if the drawer be left partly open, the effect will more certainly be produced: on the drawer being opened or shut, a loud explosion will be caused. This experiment is also perfectly harmless, and as there could be no suspicion of the trick, it cannot fail to prove the source of much amusement, to create great surprise, and to cause many whimsical conjectures as to the origin of the wonderful phenomenon. _FULMINATING_ SNUFFERS. One fourth of a grain of Fulminating Silver is to be inclosed in a small piece of paper, and put inside the snuffers; on the snuffers being applied to the candle, a smart report will follow. Be careful to notice, that the snuffers are quite cold when the paper is introduced, as the heat would cause it to explode sooner than might be thought agreeable. FULMINATING BOOTS & SHOES. These are prepared by enclosing half a grain of Brugnatelli's Fulminating Silver in a fold of glass paper, and pasting it in the middle of a piece of court plaster; if the edges of the court plaster are then slightly wet, it will adhere, and must be placed in the middle of the heel of a boot or shoe, and by being pressed upon will detonate loudly. Observe, it must be fastened on the outside of the heel. This experiment may be easily accomplished, while you are left alone, in any apartment where boots or shoes are kept, and would cause a tolerable degree of astonishment to the wearer, on his placing his foot to the ground. FULMINATING _PIPE LIGHTS_. These lights are made by inserting one-third of a grain of Fulminating Silver, in one end of a piece of hemp-stalk, in the same way as directed for the Segars. A piece of stout deal shaving might be used, prepared in the same manner as directed for the Fulminating Cards. Be careful to notice, that, whatever is used, has some particular mark attached to it, so as to point out which end is to be lighted. _FULMINATING_ WALKING STICKS. These may be made by inclosing half a grain of Brugnatelli's Fulminating Silver in a small fold of glass paper, and putting it into a ferule, which ferule may be placed gently on the stick; and on its being applied to the ground, a loud explosion will take place. * * * * * A vast number of other Fulminating objects might be prepared by the same means as here used, as it must have been observed, the Silver detonates either by friction or heat. But great attention must be paid to the quantity of Fulminating Silver used, as very unpleasant consequences might arise from the use of too large a quantity; and on the other hand, no effect produced by too small a quantity; but from one fourth to half a grain will most commonly be found quite sufficient for those purposes that require handling; and here again let me impress it on the mind, how necessary it is to pay attention to the quantities I have here specified for each object: and let me request that it may in no one instance be exceeded. FINIS. _Printed by T. Hamblin, Garlick Hill, Thames Street._ 
17149	----	Note: Project Gutenberg also has an HTML version of this file which includes the original illustrations. See 17149-h.htm or 17149-h.zip: (http://www.gutenberg.net/dirs/1/7/1/4/17149/17149-h/17149-h.htm) or (http://www.gutenberg.net/dirs/1/7/1/4/17149/17149-h.zip) Transcriber's notes: Underscores before and after words denote italics. Underscore and {} denote subscripts. Footnotes moved to end of book. The book starts using the word "CHAPTER" only after its chapter number XI. I have left it the same in this text. The Century Books of Useful Science CREATIVE CHEMISTRY Descriptive of Recent Achievements in the Chemical Industries by EDWIN E. SLOSSON, M.S., PH.D. Literary Editor of _The Independent_, Associate in Columbia School of Journalism Author of "Great American Universities," "Major Prophets of Today," "Six Major Prophets," "On Acylhalogenamine Derivatives and the Beckmann Rearrangement," "Composition of Wyoming Petroleum," etc. With Many Illustrations [Illustration (Decorative)] New York The Century Co. Copyright, 1919, by The Century Co. Copyright, 1917, 1918, 1919, by The Independent Corporation Published, October, 1919 [Illustration: From "America's Munitions" THE PRODUCTION OF NEW AND STRONGER FORMS OF STEEL IS ONE OF THE GREATEST TRIUMPHS OF MODERN CHEMISTRY The photograph shows the manufacture of a 12-inch gun at the plant of the Midvale Steel Company during the late war. The gun tube, 41 feet long, has just been drawn from the furnace where it was tempered at white heat and is now ready for quenching.] TO MY FIRST TEACHER PROFESSOR E.H.S. BAILEY OF THE UNIVERSITY OF KANSAS AND MY LAST TEACHER PROFESSOR JULIUS STIEGLITZ OF THE UNIVERSITY OF CHICAGO THIS VOLUME IS GRATEFULLY DEDICATED CONTENTS I THREE PERIODS OF PROGRESS 3 II NITROGEN 14 III FEEDING THE SOIL 37 IV COAL-TAR COLORS 60 V SYNTHETIC PERFUMES AND FLAVORS 93 VI CELLULOSE 110 VII SYNTHETIC PLASTICS 128 VIII THE RACE FOR RUBBER 145 IX THE RIVAL SUGARS 164 X WHAT COMES FROM CORN 181 XI SOLIDIFIED SUNSHINE 196 XII FIGHTING WITH FUMES 218 XIII PRODUCTS OF THE ELECTRIC FURNACE 236 XIV METALS, OLD AND NEW 263 READING REFERENCES 297 INDEX 309 A CARD OF THANKS This book originated in a series of articles prepared for _The Independent_ in 1917-18 for the purpose of interesting the general reader in the recent achievements of industrial chemistry and providing supplementary reading for students of chemistry in colleges and high schools. I am indebted to Hamilton Holt, editor of _The Independent_, and to Karl V.S. Howland, its publisher, for stimulus and opportunity to undertake the writing of these pages and for the privilege of reprinting them in this form. In gathering the material for this volume I have received the kindly aid of so many companies and individuals that it is impossible to thank them all but I must at least mention as those to whom I am especially grateful for information, advice and criticism: Thomas H. Norton of the Department of Commerce; Dr. Bernhard C. Hesse; H.S. Bailey of the Department of Agriculture; Professor Julius Stieglitz of the University of Chicago; L.E. Edgar of the Du Pont de Nemours Company; Milton Whitney of the U.S. Bureau of Soils; Dr. H.N. McCoy; K.F. Kellerman of the Bureau of Plant Industry. E.E.S. LIST OF ILLUSTRATIONS The production of new and stronger forms of steel is one of the greatest triumphs of modern chemistry _Frontispiece_ FACING PAGE The hand grenades contain potential chemical energy capable of causing a vast amount of destruction when released 16 Women in a munition plant engaged in the manufacture of tri-nitro-toluol 17 A chemical reaction on a large scale 32 Burning air in a Birkeland-Eyde furnace at the DuPont plant 33 A battery of Birkeland-Eyde furnaces for the fixation of nitrogen at the DuPont plant 33 Fixing nitrogen by calcium carbide 40 A barrow full of potash salts extracted from six tons of green kelp by the government chemists 41 Nature's silent method of nitrogen fixation 41 In order to secure a new supply of potash salts the United States Government set up an experimental plant at Sutherland, California, for utilization of kelp 52 Overhead suction at the San Diego wharf pumping kelp from the barge to the digestion tanks 53 The kelp harvester gathering the seaweed from the Pacific Ocean 53 A battery of Koppers by-product coke-ovens at the plant of the Bethlehem Steel Company, Sparrows Point, Maryland 60 In these mixing vats at the Buffalo Works, aniline dyes are prepared 61 A paper mill in action 120 Cellulose from wood pulp is now made into a large variety of useful articles of which a few examples are here pictured 121 Plantation rubber 160 Forest rubber 160 In making garden hose the rubber is formed into a tube by the machine on the right and coiled on the table to the left 161 The rival sugars 176 Interior of a sugar mill showing the machinery for crushing cane to extract the juice 177 Vacuum pans of the American Sugar Refinery Company 177 Cotton seed oil as it is squeezed from the seed by the presses 200 Cotton seed oil as it comes from the compressors flowing out of the faucets 201 Splitting coconuts on the island of Tahiti 216 The electric current passing through salt water in these cells decomposes the salt into caustic soda and chlorine gas 217 Germans starting a gas attack on the Russian lines 224 Filling the cannisters of gas masks with charcoal made from fruit pits--Long Island City 225 The chlorpicrin plant at the Bdgewood Arsenal 234 Repairing the broken stern post of the _U.S.S. Northern Pacific_, the biggest marine weld in the world 235 Making aloxite in the electric furnaces by fusing coke and bauxite 240 A block of carborundum crystals 241 Making carborundum in the electric furnace 241 Types of gas mask used by America, the Allies and Germany during the war 256 Pumping melted white phosphorus into hand grenades filled with water--Edgewood Arsenal 257 Filling shell with "mustard gas" 257 Photomicrographs showing the structure of steel made by Professor E.G. Mahin of Purdue University 272 The microscopic structure of metals 273 INTRODUCTION BY JULIUS STIEGLITZ Formerly President of the American Chemical Society, Professor of Chemistry in The University of Chicago The recent war as never before in the history of the world brought to the nations of the earth a realization of the vital place which the science of chemistry holds in the development of the resources of a nation. Some of the most picturesque features of this awakening reached the great public through the press. Thus, the adventurous trips of the _Deutschland_ with its cargoes of concentrated aniline dyes, valued at millions of dollars, emphasized as no other incident our former dependence upon Germany for these products of her chemical industries. The public read, too, that her chemists saved Germany from an early disastrous defeat, both in the field of military operations and in the matter of economic supplies: unquestionably, without the tremendous expansion of her plants for the production of nitrates and ammonia from the air by the processes of Haber, Ostwald and others of her great chemists, the war would have ended in 1915, or early in 1916, from exhaustion of Germany's supplies of nitrate explosives, if not indeed from exhaustion of her food supplies as a consequence of the lack of nitrate and ammonia fertilizer for her fields. Inventions of substitutes for cotton, copper, rubber, wool and many other basic needs have been reported. These feats of chemistry, performed under the stress of dire necessity, have, no doubt, excited the wonder and interest of our public. It is far more important at this time, however, when both for war and for peace needs, the resources of our country are strained to the utmost, that the public should awaken to a clear realization of what this science of chemistry really means for mankind, to the realization that its wizardry permeates the whole life of the nation as a vitalizing, protective and constructive agent very much in the same way as our blood, coursing through our veins and arteries, carries the constructive, defensive and life-bringing materials to every organ in the body. If the layman will but understand that chemistry is the fundamental _science of the transformation of matter_, he will readily accept the validity of this sweeping assertion: he will realize, for instance, why exactly the same fundamental laws of the science apply to, and make possible scientific control of, such widely divergent national industries as agriculture and steel manufacturing. It governs the transformation of the salts, minerals and humus of our fields and the components of the air into corn, wheat, cotton and the innumerable other products of the soil; it governs no less the transformation of crude ores into steel and alloys, which, with the cunning born of chemical knowledge, may be given practically any conceivable quality of hardness, elasticity, toughness or strength. And exactly the same thing may be said of the hundreds of national activities that lie between the two extremes of agriculture and steel manufacture! Moreover, the domain of the science of the transformation of matter includes even life itself as its loftiest phase: from our birth to our return to dust the laws of chemistry are the controlling laws of life, health, disease and death, and the ever clearer recognition of this relation is the strongest force that is raising medicine from the uncertain realm of an art to the safer sphere of an exact science. To many scientific minds it has even become evident that those most wonderful facts of life, heredity and character, must find their final explanation in the chemical composition of the components of life producing, germinal protoplasm: mere form and shape are no longer supreme but are relegated to their proper place as the housing only of the living matter which functions chemically. It must be quite obvious now why thoughtful men are insisting that the public should be awakened to a broad realization of the significance of the science of chemistry for its national life. It is a difficult science in its details, because it has found that it can best interpret the visible phenomena of the material world on the basis of the conception of invisible minute material atoms and molecules, each a world in itself, whose properties may be nevertheless accurately deduced by a rigorous logic controlling the highest type of scientific imagination. But a layman is interested in the wonders of great bridges and of monumental buildings without feeling the need of inquiring into the painfully minute and extended calculations of the engineer and architect of the strains and stresses to which every pin and every bar of the great bridge and every bit of stone, every foot of arch in a monumental edifice, will be exposed. So the public may understand and appreciate with the keenest interest the results of chemical effort without the need of instruction in the intricacies of our logic, of our dealings with our minute, invisible particles. The whole nation's welfare demands, indeed, that our public be enlightened in the matter of the relation of chemistry to our national life. Thus, if our commerce and our industries are to survive the terrific competition that must follow the reëstablishment of peace, our public must insist that its representatives in Congress preserve that independence in chemical manufacturing which the war has forced upon us in the matter of dyes, of numberless invaluable remedies to cure and relieve suffering; in the matter, too, of hundreds of chemicals, which our industries need for their successful existence. Unless we are independent in these fields, how easily might an unscrupulous competing nation do us untold harm by the mere device, for instance, of delaying supplies, or by sending inferior materials to this country or by underselling our chemical manufacturers and, after the destruction of our chemical independence, handicapping our industries as they were in the first year or two of the great war! This is not a mere possibility created by the imagination, for our economic history contains instance after instance of the purposeful undermining and destruction of our industries in finer chemicals, dyes and drugs by foreign interests bent on preserving their monopoly. If one recalls that through control, for instance, of dyes by a competing nation, control is in fact also established over products, valued in the hundreds of millions of dollars, in which dyes enter as an essential factor, one may realize indeed the tremendous industrial and commercial power which is controlled by the single lever--chemical dyes. Of even more vital moment is chemistry in the domain of health: the pitiful calls of our hospitals for local anesthetics to alleviate suffering on the operating table, the frantic appeals for the hypnotic that soothes the epileptic and staves off his seizure, the almost furious demands for remedy after remedy, that came in the early years of the war, are still ringing in the hearts of many of us. No wonder that our small army of chemists is grimly determined not to give up the independence in chemistry which war has achieved for us! Only a widely enlightened public, however, can insure the permanence of what farseeing men have started to accomplish in developing the power of chemistry through research in every domain which chemistry touches. The general public should realize that in the support of great chemical research laboratories of universities and technical schools it will be sustaining important centers from which the science which improves products, abolishes waste, establishes new industries and preserves life, may reach out helpfully into all the activities of our great nation, that are dependent on the transformation of matter. The public is to be congratulated upon the fact that the writer of the present volume is better qualified than any other man in the country to bring home to his readers some of the great results of modern chemical activity as well as some of the big problems which must continue to engage the attention of our chemists. Dr. Slosson has indeed the unique quality of combining an exact and intimate knowledge of chemistry with the exquisite clarity and pointedness of expression of a born writer. We have here an exposition by a master mind, an exposition shorn of the terrifying and obscuring technicalities of the lecture room, that will be as absorbing reading as any thrilling romance. For the story of scientific achievement is the greatest epic the world has ever known, and like the great national epics of bygone ages, should quicken the life of the nation by a realization of its powers and a picture of its possibilities. CREATIVE CHEMISTRY La Chimie posséde cette faculté créatrice à un degré plus éminent que les autres sciences, parce qu'elle pénètre plus profondément et atteint jusqu'aux éléments naturels des êtres. --_Berthelot_. I THREE PERIODS OF PROGRESS The story of Robinson Crusoe is an allegory of human history. Man is a castaway upon a desert planet, isolated from other inhabited worlds--if there be any such--by millions of miles of untraversable space. He is absolutely dependent upon his own exertions, for this world of his, as Wells says, has no imports except meteorites and no exports of any kind. Man has no wrecked ship from a former civilization to draw upon for tools and weapons, but must utilize as best he may such raw materials as he can find. In this conquest of nature by man there are three stages distinguishable: 1. The Appropriative Period 2. The Adaptive Period 3. The Creative Period These eras overlap, and the human race, or rather its vanguard, civilized man, may be passing into the third stage in one field of human endeavor while still lingering in the second or first in some other respect. But in any particular line this sequence is followed. The primitive man picks up whatever he can find available for his use. His successor in the next stage of culture shapes and develops this crude instrument until it becomes more suitable for his purpose. But in the course of time man often finds that he can make something new which is better than anything in nature or naturally produced. The savage discovers. The barbarian improves. The civilized man invents. The first finds. The second fashions. The third fabricates. The primitive man was a troglodyte. He sought shelter in any cave or crevice that he could find. Later he dug it out to make it more roomy and piled up stones at the entrance to keep out the wild beasts. This artificial barricade, this false façade, was gradually extended and solidified until finally man could build a cave for himself anywhere in the open field from stones he quarried out of the hill. But man was not content with such materials and now puts up a building which may be composed of steel, brick, terra cotta, glass, concrete and plaster, none of which materials are to be found in nature. The untutored savage might cross a stream astride a floating tree trunk. By and by it occurred to him to sit inside the log instead of on it, so he hollowed it out with fire or flint. Later, much later, he constructed an ocean liner. Cain, or whoever it was first slew his brother man, made use of a stone or stick. Afterward it was found a better weapon could be made by tying the stone to the end of the stick, and as murder developed into a fine art the stick was converted into the bow and this into the catapult and finally into the cannon, while the stone was developed into the high explosive projectile. The first music to soothe the savage breast was the soughing of the wind through the trees. Then strings were stretched across a crevice for the wind to play upon and there was the Æolian harp. The second stage was entered when Hermes strung the tortoise shell and plucked it with his fingers and when Athena, raising the wind from her own lungs, forced it through a hollow reed. From these beginnings we have the organ and the orchestra, producing such sounds as nothing in nature can equal. The first idol was doubtless a meteorite fallen from heaven or a fulgurite or concretion picked up from the sand, bearing some slight resemblance to a human being. Later man made gods in his own image, and so sculpture and painting grew until now the creations of futuristic art could be worshiped--if one wanted to--without violation of the second commandment, for they are not the likeness of anything that is in heaven above or that is in the earth beneath or that is in the water under the earth. In the textile industry the same development is observable. The primitive man used the skins of animals he had slain to protect his own skin. In the course of time he--or more probably his wife, for it is to the women rather than to the men that we owe the early steps in the arts and sciences--fastened leaves together or pounded out bark to make garments. Later fibers were plucked from the sheepskin, the cocoon and the cotton-ball, twisted together and woven into cloth. Nowadays it is possible to make a complete suit of clothes, from hat to shoes, of any desirable texture, form and color, and not include any substance to be found in nature. The first metals available were those found free in nature such as gold and copper. In a later age it was found possible to extract iron from its ores and today we have artificial alloys made of multifarious combinations of rare metals. The medicine man dosed his patients with decoctions of such roots and herbs as had a bad taste or queer look. The pharmacist discovered how to extract from these their medicinal principle such as morphine, quinine and cocaine, and the creative chemist has discovered how to make innumerable drugs adapted to specific diseases and individual idiosyncrasies. In the later or creative stages we enter the domain of chemistry, for it is the chemist alone who possesses the power of reducing a substance to its constituent atoms and from them producing substances entirely new. But the chemist has been slow to realize his unique power and the world has been still slower to utilize his invaluable services. Until recently indeed the leaders of chemical science expressly disclaimed what should have been their proudest boast. The French chemist Lavoisier in 1793 defined chemistry as "the science of analysis." The German chemist Gerhardt in 1844 said: "I have demonstrated that the chemist works in opposition to living nature, that he burns, destroys, analyzes, that the vital force alone operates by synthesis, that it reconstructs the edifice torn down by the chemical forces." It is quite true that chemists up to the middle of the last century were so absorbed in the destructive side of their science that they were blind to the constructive side of it. In this respect they were less prescient than their contemned predecessors, the alchemists, who, foolish and pretentious as they were, aspired at least to the formation of something new. It was, I think, the French chemist Berthelot who first clearly perceived the double aspect of chemistry, for he defined it as "the science of analysis _and synthesis_," of taking apart and of putting together. The motto of chemistry, as of all the empirical sciences, is _savoir c'est pouvoir_, to know in order to do. This is the pragmatic test of all useful knowledge. Berthelot goes on to say: Chemistry creates its object. This creative faculty, comparable to that of art itself, distinguishes it essentially from the natural and historical sciences.... These sciences do not control their object. Thus they are too often condemned to an eternal impotence in the search for truth of which they must content themselves with possessing some few and often uncertain fragments. On the contrary, the experimental sciences have the power to realize their conjectures.... What they dream of that they can manifest in actuality.... Chemistry possesses this creative faculty to a more eminent degree than the other sciences because it penetrates more profoundly and attains even to the natural elements of existences. Since Berthelot's time, that is, within the last fifty years, chemistry has won its chief triumphs in the field of synthesis. Organic chemistry, that is, the chemistry of the carbon compounds, so called because it was formerly assumed, as Gerhardt says, that they could only be formed by "vital force" of organized plants and animals, has taken a development far overshadowing inorganic chemistry, or the chemistry of mineral substances. Chemists have prepared or know how to prepare hundreds of thousands of such "organic compounds," few of which occur in the natural world. But this conception of chemistry is yet far from having been accepted by the world at large. This was brought forcibly to my attention during the publication of these chapters in "The Independent" by various letters, raising such objections as the following: When you say in your article on "What Comes from Coal Tar" that "Art can go ahead of nature in the dyestuff business" you have doubtless for the moment allowed your enthusiasm to sweep you away from the moorings of reason. Shakespeare, anticipating you and your "Creative Chemistry," has shown the utter untenableness of your position: Nature is made better by no mean, But nature makes that mean: so o'er that art, Which, you say, adds to nature, is an art That nature makes. How can you say that art surpasses nature when you know very well that nothing man is able to make can in any way equal the perfection of all nature's products? It is blasphemous of you to claim that man can improve the works of God as they appear in nature. Only the Creator can create. Man only imitates, destroys or defiles God's handiwork. No, it was not in momentary absence of mind that I claimed that man could improve upon nature in the making of dyes. I not only said it, but I proved it. I not only proved it, but I can back it up. I will give a million dollars to anybody finding in nature dyestuffs as numerous, varied, brilliant, pure and cheap as those that are manufactured in the laboratory. I haven't that amount of money with me at the moment, but the dyers would be glad to put it up for the discovery of a satisfactory natural source for their tinctorial materials. This is not an opinion of mine but a matter of fact, not to be decided by Shakespeare, who was not acquainted with the aniline products. Shakespeare in the passage quoted is indulging in his favorite amusement of a play upon words. There is a possible and a proper sense of the word "nature" that makes it include everything except the supernatural. Therefore man and all his works belong to the realm of nature. A tenement house in this sense is as "natural" as a bird's nest, a peapod or a crystal. But such a wide extension of the term destroys its distinctive value. It is more convenient and quite as correct to use "nature" as I have used it, in contradistinction to "art," meaning by the former the products of the mineral, vegetable and animal kingdoms, excluding the designs, inventions and constructions of man which we call "art." We cannot, in a general and abstract fashion, say which is superior, art or nature, because it all depends on the point of view. The worm loves a rotten log into which he can bore. Man prefers a steel cabinet into which the worm cannot bore. If man cannot improve Upon nature he has no motive for making anything. Artificial products are therefore superior to natural products as measured by man's convenience, otherwise they would have no reason for existence. Science and Christianity are at one in abhorring the natural man and calling upon the civilized man to fight and subdue him. The conquest of nature, not the imitation of nature, is the whole duty of man. Metchnikoff and St. Paul unite in criticizing the body we were born with. St. Augustine and Huxley are in agreement as to the eternal conflict between man and nature. In his Romanes lecture on "Evolution and Ethics" Huxley said: "The ethical progress of society depends, not on imitating the cosmic process, still less on running away from it, but on combating it," and again: "The history of civilization details the steps by which man has succeeded in building up an artificial world within the cosmos." There speaks the true evolutionist, whose one desire is to get away from nature as fast and far as possible. Imitate Nature? Yes, when we cannot improve upon her. Admire Nature? Possibly, but be not blinded to her defects. Learn from Nature? We should sit humbly at her feet until we can stand erect and go our own way. Love Nature? Never! She is our treacherous and unsleeping foe, ever to be feared and watched and circumvented, for at any moment and in spite of all our vigilance she may wipe out the human race by famine, pestilence or earthquake and within a few centuries obliterate every trace of its achievement. The wild beasts that man has kept at bay for a few centuries will in the end invade his palaces: the moss will envelop his walls and the lichen disrupt them. The clam may survive man by as many millennia as it preceded him. In the ultimate devolution of the world animal life will disappear before vegetable, the higher plants will be killed off before the lower, and finally the three kingdoms of nature will be reduced to one, the mineral. Civilized man, enthroned in his citadel and defended by all the forces of nature that he has brought under his control, is after all in the same situation as a savage, shivering in the darkness beside his fire, listening to the pad of predatory feet, the rustle of serpents and the cry of birds of prey, knowing that only the fire keeps his enemies off, but knowing too that every stick he lays on the fire lessens his fuel supply and hastens the inevitable time when the beasts of the jungle will make their fatal rush. Chaos is the "natural" state of the universe. Cosmos is the rare and temporary exception. Of all the million spheres this is apparently the only one habitable and of this only a small part--the reader may draw the boundaries to suit himself--can be called civilized. Anarchy is the natural state of the human race. It prevailed exclusively all over the world up to some five thousand years ago, since which a few peoples have for a time succeeded in establishing a certain degree of peace and order. This, however, can be maintained only by strenuous and persistent efforts, for society tends naturally to sink into the chaos out of which it has arisen. It is only by overcoming nature that man can rise. The sole salvation for the human race lies in the removal of the primal curse, the sentence of hard labor for life that was imposed on man as he left Paradise. Some folks are trying to elevate the laboring classes; some are trying to keep them down. The scientist has a more radical remedy; he wants to annihilate the laboring classes by abolishing labor. There is no longer any need for human labor in the sense of personal toil, for the physical energy necessary to accomplish all kinds of work may be obtained from external sources and it can be directed and controlled without extreme exertion. Man's first effort in this direction was to throw part of his burden upon the horse and ox or upon other men. But within the last century it has been discovered that neither human nor animal servitude is necessary to give man leisure for the higher life, for by means of the machine he can do the work of giants without exhaustion. But the introduction of machines, like every other step of human progress, met with the most violent opposition from those it was to benefit. "Smash 'em!" cried the workingman. "Smash 'em!" cried the poet. "Smash 'em!" cried the artist. "Smash 'em!" cried the theologian. "Smash 'em!" cried the magistrate. This opposition yet lingers and every new invention, especially in chemistry, is greeted with general distrust and often with legislative prohibition. Man is the tool-using animal, and the machine, that is, the power-driven tool, is his peculiar achievement. It is purely a creation of the human mind. The wheel, its essential feature, does not exist in nature. The lever, with its to-and-fro motion, we find in the limbs of all animals, but the continuous and revolving lever, the wheel, cannot be formed of bone and flesh. Man as a motive power is a poor thing. He can only convert three or four thousand calories of energy a day and he does that very inefficiently. But he can make an engine that will handle a hundred thousand times that, twice as efficiently and three times as long. In this way only can he get rid of pain and toil and gain the wealth he wants. Gradually then he will substitute for the natural world an artificial world, molded nearer to his heart's desire. Man the Artifex will ultimately master Nature and reign supreme over his own creation until chaos shall come again. In the ancient drama it was _deus ex machina_ that came in at the end to solve the problems of the play. It is to the same supernatural agency, the divinity in machinery, that we must look for the salvation of society. It is by means of applied science that the earth can be made habitable and a decent human life made possible. Creative evolution is at last becoming conscious. II NITROGEN PRESERVER AND DESTROYER OF LIFE In the eyes of the chemist the Great War was essentially a series of explosive reactions resulting in the liberation of nitrogen. Nothing like it has been seen in any previous wars. The first battles were fought with cellulose, mostly in the form of clubs. The next were fought with silica, mostly in the form of flint arrowheads and spear-points. Then came the metals, bronze to begin with and later iron. The nitrogenous era in warfare began when Friar Roger Bacon or Friar Schwartz--whichever it was--ground together in his mortar saltpeter, charcoal and sulfur. The Chinese, to be sure, had invented gunpowder long before, but they--poor innocents--did not know of anything worse to do with it than to make it into fire-crackers. With the introduction of "villainous saltpeter" war ceased to be the vocation of the nobleman and since the nobleman had no other vocation he began to become extinct. A bullet fired from a mile away is no respecter of persons. It is just as likely to kill a knight as a peasant, and a brave man as a coward. You cannot fence with a cannon ball nor overawe it with a plumed hat. The only thing you can do is to hide and shoot back. Now you cannot hide if you send up a column of smoke by day and a pillar of fire by night--the most conspicuous of signals--every time you shoot. So the next step was the invention of a smokeless powder. In this the oxygen necessary for the combustion is already in such close combination with its fuel, the carbon and hydrogen, that no black particles of carbon can get away unburnt. In the old-fashioned gunpowder the oxygen necessary for the combustion of the carbon and sulfur was in a separate package, in the molecule of potassium nitrate, and however finely the mixture was ground, some of the atoms, in the excitement of the explosion, failed to find their proper partners at the moment of dispersal. The new gunpowder besides being smokeless is ashless. There is no black sticky mass of potassium salts left to foul the gun barrel. The gunpowder period of warfare was actively initiated at the battle of Cressy, in which, as a contemporary historian says, "The English guns made noise like thunder and caused much loss in men and horses." Smokeless powder as invented by Paul Vieille was adopted by the French Government in 1887. This, then, might be called the beginning of the guncotton or nitrocellulose period--or, perhaps in deference to the caveman's club, the second cellulose period of human warfare. Better, doubtless, to call it the "high explosive period," for various other nitro-compounds besides guncotton are being used. The important thing to note is that all the explosives from gunpowder down contain nitrogen as the essential element. It is customary to call nitrogen "an inert element" because it was hard to get it into combination with other elements. It might, on the other hand, be looked upon as an active element because it acts so energetically in getting out of its compounds. We can dodge the question by saying that nitrogen is a most unreliable and unsociable element. Like Kipling's cat it walks by its wild lone. It is not so bad as Argon the Lazy and the other celibate gases of that family, where each individual atom goes off by itself and absolutely refuses to unite even temporarily with any other atom. The nitrogen atoms will pair off with each other and stick together, but they are reluctant to associate with other elements and when they do the combination is likely to break up any moment. You all know people like that, good enough when by themselves but sure to break up any club, church or society they get into. Now, the value of nitrogen in warfare is due to the fact that all the atoms desert in a body on the field of battle. Millions of them may be lying packed in a gun cartridge, as quiet as you please, but let a little disturbance start in the neighborhood--say a grain of mercury fulminate flares up--and all the nitrogen atoms get to trembling so violently that they cannot be restrained. The shock spreads rapidly through the whole mass. The hydrogen and carbon atoms catch up the oxygen and in an instant they are off on a stampede, crowding in every direction to find an exit, and getting more heated up all the time. The only movable side is the cannon ball in front, so they all pound against that and give it such a shove that it goes ten miles before it stops. The external bombardment by the cannon ball is, therefore, preceded by an internal bombardment on the cannon ball by the molecules of the hot gases, whose speed is about as great as the speed of the projectile that they propel. [Illustration: © Underwood & Underwood THE HAND GRENADES WHICH THESE WOMEN ARE BORING will contain potential chemical energy capable of causing a vast amount of destruction when released. During the war the American Government placed orders for 68,000,000 such grenades as are here shown.] [Illustration: © International Film Service, Inc. WOMEN IN A MUNITION PLANT ENGAGED IN THE MANUFACTURE OF TRI-NITRO-TOLUOL, THE MOST IMPORTANT OF MODERN HIGH EXPLOSIVES] The active agent in all these explosives is the nitrogen atom in combination with two oxygen atoms, which the chemist calls the "nitro group" and which he represents by NO_{2}. This group was, as I have said, originally used in the form of saltpeter or potassium nitrate, but since the chemist did not want the potassium part of it--for it fouled his guns--he took the nitro group out of the nitrate by means of sulfuric acid and by the same means hooked it on to some compound of carbon and hydrogen that would burn without leaving any residue, and give nothing but gases. One of the simplest of these hydrocarbon derivatives is glycerin, the same as you use for sunburn. This mixed with nitric and sulfuric acids gives nitroglycerin, an easy thing to make, though I should not advise anybody to try making it unless he has his life insured. But nitroglycerin is uncertain stuff to keep and being a liquid is awkward to handle. So it was mixed with sawdust or porous earth or something else that would soak it up. This molded into sticks is our ordinary dynamite. If instead of glycerin we take cellulose in the form of wood pulp or cotton and treat this with nitric acid in the presence of sulfuric we get nitrocellulose or guncotton, which is the chief ingredient of smokeless powder. Now guncotton looks like common cotton. It is too light and loose to pack well into a gun. So it is dissolved with ether and alcohol or acetone to make a plastic mass that can be molded into rods and cut into grains of suitable shape and size to burn at the proper speed. Here, then, we have a liquid explosive, nitroglycerin, that has to be soaked up in some porous solid, and a porous solid, guncotton, that has to soak up some liquid. Why not solve both difficulties together by dissolving the guncotton in the nitroglycerin and so get a double explosive? This is a simple idea. Any of us can see the sense of it--once it is suggested to us. But Alfred Nobel, the Swedish chemist, who thought it out first in 1878, made millions out of it. Then, apparently alarmed at the possible consequences of his invention, he bequeathed the fortune he had made by it to found international prizes for medical, chemical and physical discoveries, idealistic literature and the promotion of peace. But his posthumous efforts for the advancement of civilization and the abolition of war did not amount to much and his high explosives were later employed to blow into pieces the doctors, chemists, authors and pacifists he wished to reward. Nobel's invention, "cordite," is composed of nitroglycerin and nitrocellulose with a little mineral jelly or vaseline. Besides cordite and similar mixtures of nitroglycerin and nitrocellulose there are two other classes of high explosives in common use. One is made from carbolic acid, which is familiar to us all by its use as a disinfectant. If this is treated with nitric and sulfuric acids we get from it picric acid, a yellow crystalline solid. Every government has its own secret formula for this type of explosive. The British call theirs "lyddite," the French "melinite" and the Japanese "shimose." The third kind of high explosives uses as its base toluol. This is not so familiar to us as glycerin, cotton or carbolic acid. It is one of the coal tar products, an inflammable liquid, resembling benzene. When treated with nitric acid in the usual way it takes up like the others three nitro groups and so becomes tri-nitro-toluol. Realizing that people could not be expected to use such a mouthful of a word, the chemists have suggested various pretty nicknames, trotyl, tritol, trinol, tolite and trilit, but the public, with the wilfulness it always shows in the matter of names, persists in calling it TNT, as though it were an author like G.B.S., or G.K.C, or F.P.A. TNT is the latest of these high explosives and in some ways the best of them. Picric acid has the bad habit of attacking the metals with which it rests in contact forming sensitive picrates that are easily set off, but TNT is inert toward metals and keeps well. TNT melts far below the boiling point of water so can be readily liquefied and poured into shells. It is insensitive to ordinary shocks. A rifle bullet can be fired through a case of it without setting it off, and if lighted with a match it burns quietly. The amazing thing about these modern explosives, the organic nitrates, is the way they will stand banging about and burning, yet the terrific violence with which they blow up when shaken by an explosive wave of a particular velocity like that of a fulminating cap. Like picric acid, TNT stains the skin yellow and causes soreness and sometimes serious cases of poisoning among the employees, mostly girls, in the munition factories. On the other hand, the girls working with cordite get to using it as chewing gum; a harmful habit, not because of any danger of being blown up by it, but because nitroglycerin is a heart stimulant and they do not need that. [Illustration: The Genealogical Tree of Nitric Acid From W.Q. Whitman's "The Story of Nitrates in the War," _General Science Quarterly_] TNT is by no means smokeless. The German shells that exploded with a cloud of black smoke and which British soldiers called "Black Marias," "coal-boxes" or "Jack Johnsons" were loaded with it. But it is an advantage to have a shell show where it strikes, although a disadvantage to have it show where it starts. It is these high explosives that have revolutionized warfare. As soon as the first German shell packed with these new nitrates burst inside the Gruson cupola at Liège and tore out its steel and concrete by the roots the world knew that the day of the fixed fortress was gone. The armies deserted their expensively prepared fortifications and took to the trenches. The British troops in France found their weapons futile and sent across the Channel the cry of "Send us high explosives or we perish!" The home Government was slow to heed the appeal, but no progress was made against the Germans until the Allies had the means to blast them out of their entrenchments by shells loaded with five hundred pounds of TNT. All these explosives are made from nitric acid and this used to be made from nitrates such as potassium nitrate or saltpeter. But nitrates are rarely found in large quantities. Napoleon and Lee had a hard time to scrape up enough saltpeter from the compost heaps, cellars and caves for their gunpowder, and they did not use as much nitrogen in a whole campaign as was freed in a few days' cannonading on the Somme. Now there is one place in the world--and so far as we know one only--where nitrates are to be found abundantly. This is in a desert on the western slope of the Andes where ancient guano deposits have decomposed and there was not enough rain to wash away their salts. Here is a bed two miles wide, two hundred miles long and five feet deep yielding some twenty to fifty per cent. of sodium nitrate. The deposit originally belonged to Peru, but Chile fought her for it and got it in 1881. Here all countries came to get their nitrates for agriculture and powder making. Germany was the largest customer and imported 750,000 tons of Chilean nitrate in 1913, besides using 100,000 tons of other nitrogen salts. By this means her old, wornout fields were made to yield greater harvests than our fresh land. Germany and England were like two duelists buying powder at the same shop. The Chilean Government, pocketing an export duty that aggregated half a billion dollars, permitted the saltpeter to be shoveled impartially into British and German ships, and so two nitrogen atoms, torn from their Pacific home and parted, like Evangeline and Gabriel, by transportation oversea, may have found themselves flung into each other's arms from the mouths of opposing howitzers in the air of Flanders. Goethe could write a romance on such a theme. Now the moment war broke out this source of supply was shut off to both parties, for they blockaded each other. The British fleet closed up the German ports while the German cruisers in the Pacific took up a position off the coast of Chile in order to intercept the ships carrying nitrates to England and France. The Panama Canal, designed to afford relief in such an emergency, caved in most inopportunely. The British sent a fleet to the Pacific to clear the nitrate route, but it was outranged and defeated on November 1, 1914. Then a stronger British fleet was sent out and smashed the Germans off the Falkland Islands on December 8. But for seven weeks the nitrate route had been closed while the chemical reactions on the Marne and Yser were decomposing nitrogen-compounds at an unheard of rate. England was now free to get nitrates for her munition factories, but Germany was still bottled up. She had stored up Chilean nitrates in anticipation of the war and as soon as it was seen to be coming she bought all she could get in Europe. But this supply was altogether inadequate and the war would have come to an end in the first winter if German chemists had not provided for such a contingency in advance by working out methods of getting nitrogen from the air. Long ago it was said that the British ruled the sea and the French the land so that left nothing to the German but the air. The Germans seem to have taken this jibe seriously and to have set themselves to make the most of the aerial realm in order to challenge the British and French in the fields they had appropriated. They had succeeded so far that the Kaiser when he declared war might well have considered himself the Prince of the Power of the Air. He had a fleet of Zeppelins and he had means for the fixation of nitrogen such as no other nation possessed. The Zeppelins burst like wind bags, but the nitrogen plants worked and made Germany independent of Chile not only during the war, but in the time of peace. Germany during the war used 200,000 tons of nitric acid a year in explosives, yet her supply of nitrogen is exhaustless. [Illustration: World production and consumption of fixed inorganic nitrogen expressed in tons nitrogen From _The Journal of Industrial and Engineering Chemistry_, March, 1919.] Nitrogen is free as air. That is the trouble; it is too free. It is fixed nitrogen that we want and that we are willing to pay for; nitrogen in combination with some other elements in the form of food or fertilizer so we can make use of it as we set it free. Fixed nitrogen in its cheapest form, Chile saltpeter, rose to $250 during the war. Free nitrogen costs nothing and is good for nothing. If a land-owner has a right to an expanding pyramid of air above him to the limits of the atmosphere--as, I believe, the courts have decided in the eaves-dropping cases--then for every square foot of his ground he owns as much nitrogen as he could buy for $2500. The air is four-fifths free nitrogen and if we could absorb it in our lungs as we do the oxygen of the other fifth a few minutes breathing would give us a full meal. But we let this free nitrogen all out again through our noses and then go and pay 35 cents a pound for steak or 60 cents a dozen for eggs in order to get enough combined nitrogen to live on. Though man is immersed in an ocean of nitrogen, yet he cannot make use of it. He is like Coleridge's "Ancient Mariner" with "water, water, everywhere, nor any drop to drink." Nitrogen is, as Hood said not so truly about gold, "hard to get and hard to hold." The bacteria that form the nodules on the roots of peas and beans have the power that man has not of utilizing free nitrogen. Instead of this quiet inconspicuous process man has to call upon the lightning when he wants to fix nitrogen. The air contains the oxygen and nitrogen which it is desired to combine to form nitrates but the atoms are paired, like to like. Passing an electric spark through the air breaks up some of these pairs and in the confusion of the shock the lonely atoms seize on their nearest neighbor and so may get partners of the other sort. I have seen this same thing happen in a square dance where somebody made a blunder. It is easy to understand the reaction if we represent the atoms of oxygen and nitrogen by the initials of their names in this fashion: NN + OO --> NO + NO nitrogen oxygen nitric oxide The --> represents Jove's thunderbolt, a stroke of artificial lightning. We see on the left the molecules of oxygen and nitrogen, before taking the electric treatment, as separate elemental pairs, and then to the right of the arrow we find them as compound molecules of nitric oxide. This takes up another atom of oxygen from the air and becomes NOO, or using a subscript figure to indicate the number of atoms and so avoid repeating the letter, NO_{2} which is the familiar nitro group of nitric acid (HO--NO_{2}) and of its salts, the nitrates, and of its organic compounds, the high explosives. The NO_{2} is a brown and evil-smelling gas which when dissolved in water (HOH) and further oxidized is completely converted into nitric acid. The apparatus which effects this transformation is essentially a gigantic arc light in a chimney through which a current of hot air is blown. The more thoroughly the air comes under the action of the electric arc the more molecules of nitrogen and oxygen will be broken up and rearranged, but on the other hand if the mixture of gases remains in the path of the discharge the NO molecules are also broken up and go back into their original form of NN and OO. So the object is to spread out the electric arc as widely as possible and then run the air through it rapidly. In the Schönherr process the electric arc is a spiral flame twenty-three feet long through which the air streams with a vortex motion. In the Birkeland-Eyde furnace there is a series of semi-circular arcs spread out by the repellent force of a powerful electric magnet in a flaming disc seven feet in diameter with a temperature of 6300° F. In the Pauling furnace the electrodes between which the current strikes are two cast iron tubes curving upward and outward like the horns of a Texas steer and cooled by a stream of water passing through them. These electric furnaces produce two or three ounces of nitric acid for each kilowatt-hour of current consumed. Whether they can compete with the natural nitrates and the products of other processes depends upon how cheaply they can get their electricity. Before the war there were several large installations in Norway and elsewhere where abundant water power was available and now the Norwegians are using half a million horse power continuously in the fixation of nitrogen and the rest of the world as much again. The Germans had invested largely in these foreign oxidation plants, but shortly before the war they had sold out and turned their attention to other processes not requiring so much electrical energy, for their country is poorly provided with water power. The Haber process, that they made most of, is based upon as simple a reaction as that we have been considering, for it consists in uniting two elemental gases to make a compound, but the elements in this case are not nitrogen and oxygen, but nitrogen and hydrogen. This gives ammonia instead of nitric acid, but ammonia is useful for its own purposes and it can be converted into nitric acid if this is desired. The reaction is: NN + HH + HH + HH --> NHHH + NHHH Nitrogen hydrogen ammonia The animals go in two by two, but they come out four by four. Four molecules of the mixed elements are turned into two molecules and so the gas shrinks to half its volume. At the same time it acquires an odor--familiar to us when we are curing a cold--that neither of the original gases had. The agent that effects the transformation in this case is not the electric spark--for this would tend to work the reaction backwards--but uranium, a rare metal, which has the peculiar property of helping along a reaction while seeming to take no part in it. Such a substance is called a catalyst. The action of a catalyst is rather mysterious and whenever we have a mystery we need an analogy. We may, then, compare the catalyst to what is known as "a good mixer" in society. You know the sort of man I mean. He may not be brilliant or especially talkative, but somehow there is always "something doing" at a picnic or house-party when he is along. The tactful hostess, the salon leader, is a social catalyst. The trouble with catalysts, either human or metallic, is that they are rare and that sometimes they get sulky and won't work if the ingredients they are supposed to mix are unsuitable. But the uranium, osmium, platinum or whatever metal is used as a catalyzing agent is expensive and although it is not used up it is easily "poisoned," as the chemists say, by impurities in the gases. The nitrogen and the hydrogen for the Haber process must then be prepared and purified before trying to combine them into ammonia. The nitrogen is obtained by liquefying air by cold and pressure and then boiling off the nitrogen at 194° C. The oxygen left is useful for other purposes. The hydrogen needed is extracted by a similar process of fractional distillation from "water-gas," the blue-flame burning gas used for heating. Then the nitrogen and hydrogen, mixed in the proportion of one to three, as shown in the reaction given above, are compressed to two hundred atmospheres, heated to 1300° F. and passed over the finely divided uranium. The stream of gas that comes out contains about four per cent. of ammonia, which is condensed to a liquid by cooling and the uncombined hydrogen and nitrogen passed again through the apparatus. The ammonia can be employed in refrigeration and other ways but if it is desired to get the nitrogen into the form of nitric acid it has to be oxidized by the so-called Ostwald process. This is the reaction: NH_{3} + 4O --> HNO_{3} + H_{2}O ammonia oxygen nitric acid water The catalyst used to effect this combination is the metal platinum in the form of fine wire gauze, since the action takes place only on the surface. The ammonia gas is mixed with air which supplies the oxygen and the heated mixture run through the platinum gauze at the rate of several yards a second. Although the gases come in contact with the platinum only a five-hundredth part of a second yet eighty-five per cent. is converted into nitric acid. The Haber process for the making of ammonia by direct synthesis from its constituent elements and the supplemental Ostwald process for the conversion of the ammonia into nitric acid were the salvation of Germany. As soon as the Germans saw that their dash toward Paris had been stopped at the Marne they knew that they were in for a long war and at once made plans for a supply of fixed nitrogen. The chief German dye factories, the Badische Anilin and Soda-Fabrik, promptly put $100,000,000 into enlarging its plant and raised its production of ammonium sulfate from 30,000 to 300,000 tons. One German electrical firm with aid from the city of Berlin contracted to provide 66,000,000 pounds of fixed nitrogen a year at a cost of three cents a pound for the next twenty-five years. The 750,000 tons of Chilean nitrate imported annually by Germany contained about 116,000 tons of the essential element nitrogen. The fourteen large plants erected during the war can fix in the form of nitrates 500,000 tons of nitrogen a year, which is more than twice the amount needed for internal consumption. So Germany is now not only independent of the outside world but will have a surplus of nitrogen products which could be sold even in America at about half what the farmer has been paying for South American saltpeter. Besides the Haber or direct process there are other methods of making ammonia which are, at least outside of Germany, of more importance. Most prominent of these is the cyanamid process. This requires electrical power since it starts with a product of the electrical furnace, calcium carbide, familiar to us all as a source of acetylene gas. If a stream of nitrogen is passed over hot calcium carbide it is taken up by the carbide according to the following equation: CaC_{2} + N_{2} --> CaCN_{2} + C calcium carbide nitrogen calcium cyanamid carbon Calcium cyanamid was discovered in 1895 by Caro and Franke when they were trying to work out a new process for making cyanide to use in extracting gold. It looks like stone and, under the name of lime-nitrogen, or Kalkstickstoff, or nitrolim, is sold as a fertilizer. If it is desired to get ammonia, it is treated with superheated steam. The reaction produces heat and pressure, so it is necessary to carry it on in stout autoclaves or enclosed kettles. The cyanamid is completely and quickly converted into pure ammonia and calcium carbonate, which is the same as the limestone from which carbide was made. The reaction is: CaCN_{2} + 3H_{2}O --> CaCO_{3} + 2NH_{3} calcium cyanamid water calcium carbonate ammonia Another electrical furnace method, the Serpek process, uses aluminum instead of calcium for the fixation of nitrogen. Bauxite, or impure aluminum oxide, the ordinary mineral used in the manufacture of metallic aluminum, is mixed with coal and heated in a revolving electrical furnace through which nitrogen is passing. The equation is: Al_{2}O_{3} + 3C + N_{2} --> 2AlN + 3CO aluminum carbon nitrogen aluminum carbon oxide nitride monoxide Then the aluminum nitride is treated with steam under pressure, which produces ammonia and gives back the original aluminum oxide, but in a purer form than the mineral from which was made 2AlN + 3H_{2}O --> 2NH_{3} + Al_{2}O_{3} Aluminum water ammonia aluminum oxide nitride The Serpek process is employed to some extent in France in connection with the aluminum industry. These are the principal processes for the fixation of nitrogen now in use, but they by no means exhaust the possibilities. For instance, Professor John C. Bucher, of Brown University, created a sensation in 1917 by announcing a new process which he had worked out with admirable completeness and which has some very attractive features. It needs no electric power or high pressure retorts or liquid air apparatus. He simply fills a twenty-foot tube with briquets made out of soda ash, iron and coke and passes producer gas through the heated tube. Producer gas contains nitrogen since it is made by passing air over hot coal. The reaction is: 2Na_{2}CO_{3} + 4C + N_{2} = 2NaCN + 3CO sodium carbon nitrogen sodium carbon carbonate cyanide monoxide The iron here acts as the catalyst and converts two harmless substances, sodium carbonate, which is common washing soda, and carbon, into two of the most deadly compounds known to man, cyanide and carbon monoxide, which is what kills you when you blow out the gas. Sodium cyanide is a salt of hydrocyanic acid, which for, some curious reason is called "Prussic acid." It is so violent a poison that, as the freshman said in a chemistry recitation, "a single drop of it placed on the tongue of a dog will kill a man." But sodium cyanide is not only useful in itself, for the extraction of gold and cleaning of silver, but can be converted into ammonia, and a variety of other compounds such as urea and oxamid, which are good fertilizers; sodium ferrocyanide, that makes Prussian blue; and oxalic acid used in dyeing. Professor Bucher claimed that his furnace could be set up in a day at a cost of less than $100 and could turn out 150 pounds of sodium cyanide in twenty-four hours. This process was placed freely at the disposal of the United States Government for the war and a 10-ton plant was built at Saltville, Va., by the Ordnance Department. But the armistice put a stop to its operations and left the future of the process undetermined. [Illustration: A CHEMICAL REACTION ON A LARGE SCALE From the chemist's standpoint modern warfare consists in the rapid liberation of nitrogen from its compounds] [Illustration: Courtesy of E.I. du Pont de Nemours Co. BURNING AIR IN A BIRKELAND-EYDE FURNACE AT THE DU PONT PLANT An electric arc consuming about 4000 horse-power of energy is passing between the U-shaped electrodes which are made of copper tube cooled by an internal current of water. On the sides of the chamber are seen the openings through which the air passes impinging directly on both sides of the surface of the disk of flame. This flame is approximately seven feet in diameter and appears to be continuous although an alternating current of fifty cycles a second is used. The electric arc is spread into this disk flame by the repellent power of an electro-magnet the pointed pole of which is seen at bottom of the picture. Under this intense heat a part of the nitrogen and oxygen of the air combine to form oxides of nitrogen which when dissolved in water form the nitric acid used in explosives.] [Illustration: Courtesy of E.I. du Pont de Nemours Co. A BATTERY OF BIRKELAND-EYDE FURNACES FOR THE FIXATION OF NITROGEN AT THE DU PONT PLANT] We might have expected that the fixation of nitrogen by passing an electrical spark through hot air would have been an American invention, since it was Franklin who snatched the lightning from the heavens as well as the scepter from the tyrant and since our output of hot air is unequaled by any other nation. But little attention was paid to the nitrogen problem until 1916 when it became evident that we should soon be drawn into a war "with a first class power." On June 3, 1916, Congress placed $20,000,000 at the disposal of the president for investigation of "the best, cheapest and most available means for the production of nitrate and other products for munitions of war and useful in the manufacture of fertilizers and other useful products by water power or any other power." But by the time war was declared on April 6, 1917, no definite program had been approved and by the time the armistice was signed on November 11, 1918, no plants were in active operation. But five plants had been started and two of them were nearly ready to begin work when they were closed by the ending of the war. United States Nitrate Plant No. 1 was located at Sheffield, Alabama, and was designed for the production of ammonia by "direct action" from nitrogen and hydrogen according to the plans of the American Chemical Company. Its capacity was calculated at 60,000 pounds of anhydrous ammonia a day, half of which was to be oxidized to nitric acid. Plant No. 2 was erected at Muscle Shoals, Alabama, to use the process of the American Cyanamid Company. This was contracted to produce 110,000 tons of ammonium nitrate a year and later two other cyanamid plants of half that capacity were started at Toledo and Ancor, Ohio. At Muscle Shoals a mushroom city of 20,000 sprang up on an Alabama cotton field in six months. The raw material, air, was as abundant there as anywhere and the power, water, could be obtained from the Government hydro-electric plant on the Tennessee River, but this was not available during the war, so steam was employed instead. The heat of the coal was used to cool the air down to the liquefying point. The principle of this process is simple. Everybody knows that heat expands and cold contracts, but not everybody has realized the converse of this rule, that expansion cools and compression heats. If air is forced into smaller space, as in a tire pump, it heats up and if allowed to expand to ordinary pressure it cools off again. But if the air while compressed is cooled and then allowed to expand it must get still colder and the process can go on till it becomes cold enough to congeal. That is, by expanding a great deal of air, a little of it can be reduced to the liquefying point. At Muscle Shoals the plant for liquefying air, in order to get the nitrogen out of it, consisted of two dozen towers each capable of producing 1765 cubic feet of pure nitrogen per hour. The air was drawn in through two pipes, a yard across, and passed through scrubbing towers to remove impurities. The air was then compressed to 600 pounds per square inch. Nine tenths of the air was permitted to expand to 50 pounds and this expansion cooled down the other tenth, still under high pressure, to the liquefying point. Rectifying towers 24 feet high were stacked with trays of liquid air from which the nitrogen was continually bubbling off since its boiling point is twelve degrees centigrade lower than that of oxygen. Pure nitrogen gas collected at the top of the tower and the residual liquid air, now about half oxygen, was allowed to escape at the bottom. The nitrogen was then run through pipes into the lime-nitrogen ovens. There were 1536 of these about four feet square and each holding 1600 pounds of pulverized calcium carbide. This is at first heated by an electrical current to start the reaction which afterwards produces enough heat to keep it going. As the stream of nitrogen gas passes over the finely divided carbide it is absorbed to form calcium cyanamid as described on a previous page. This product is cooled, powdered and wet to destroy any quicklime or carbide left unchanged. Then it is charged into autoclaves and steam at high temperature and pressure is admitted. The steam acting on the cyanamid sets free ammonia gas which is carried to towers down which cold water is sprayed, giving the ammonia water, familiar to the kitchen and the bathroom. But since nitric acid rather than ammonia was needed for munitions, the oxygen of the air had to be called into play. This process, as already explained, is carried on by aid of a catalyzer, in this case platinum wire. At Muscle Shoals there were 696 of these catalyzer boxes. The ammonia gas, mixed with air to provide the necessary oxygen, was admitted at the top and passed down through a sheet of platinum gauze of 80 mesh to the inch, heated to incandescence by electricity. In contact with this the ammonia is converted into gaseous oxides of nitrogen (the familiar red fumes of the laboratory) which, carried off in pipes, cooled and dissolved in water, form nitric acid. But since none of the national plants could be got into action during the war, the United States was compelled to draw upon South America for its supply. The imports of Chilean saltpeter rose from half a million tons in 1914 to a million and a half in 1917. After peace was made the Department of War turned over to the Department of Agriculture its surplus of saltpeter, 150,000 tons, and it was sold to American farmers at cost, $81 a ton. For nitrogen plays a double rôle in human economy. It appears like Brahma in two aspects, Vishnu the Preserver and Siva the Destroyer. Here I have been considering nitrogen in its maleficent aspect, its use in war. We now turn to its beneficent aspect, its use in peace. III FEEDING THE SOIL The Great War not only starved people: it starved the land. Enough nitrogen was thrown away in some indecisive battle on the Aisne to save India from a famine. The population of Europe as a whole has not been lessened by the war, but the soil has been robbed of its power to support the population. A plant requires certain chemical elements for its growth and all of these must be within reach of its rootlets, for it will accept no substitutes. A wheat stalk in France before the war had placed at its feet nitrates from Chile, phosphates from Florida and potash from Germany. All these were shut off by the firing line and the shortage of shipping. Out of the eighty elements only thirteen are necessary for crops. Four of these are gases: hydrogen, oxygen, nitrogen and chlorine. Five are metals: potassium, magnesium, calcium, iron and sodium. Four are non-metallic solids: carbon, sulfur, phosphorus and silicon. Three of these, hydrogen, oxygen and carbon, making up the bulk of the plant, are obtainable _ad libitum_ from the air and water. The other ten in the form of salts are dissolved in the water that is sucked up from the soil. The quantity needed by the plant is so small and the quantity contained in the soil is so great that ordinarily we need not bother about the supply except in case of three of them. They are nitrogen, potassium and phosphorus. These would be useless or fatal to plant life in the elemental form, but fixed in neutral salt they are essential plant foods. A ton of wheat takes away from the soil about 47 pounds of nitrogen, 18 pounds of phosphoric acid and 12 pounds of potash. If then the farmer does not restore this much to his field every year he is drawing upon his capital and this must lead to bankruptcy in the long run. So much is easy to see, but actually the question is extremely complicated. When the German chemist, Justus von Liebig, pointed out in 1840 the possibility of maintaining soil fertility by the application of chemicals it seemed at first as though the question were practically solved. Chemists assumed that all they had to do was to analyze the soil and analyze the crop and from this figure out, as easily as balancing a bank book, just how much of each ingredient would have to be restored to the soil every year. But somehow it did not work out that way and the practical agriculturist, finding that the formulas did not fit his farm, sneered at the professors and whenever they cited Liebig to him he irreverently transposed the syllables of the name. The chemist when he went deeper into the subject saw that he had to deal with the colloids, damp, unpleasant, gummy bodies that he had hitherto fought shy of because they would not crystallize or filter. So the chemist called to his aid the physicist on the one hand and the biologist on the other and then they both had their hands full. The physicist found that he had to deal with a polyvariant system of solids, liquids and gases mutually miscible in phases too numerous to be handled by Gibbs's Rule. The biologist found that he had to deal with the invisible flora and fauna of a new world. Plants obey the injunction of Tennyson and rise on the stepping stones of their dead selves to higher things. Each successive generation lives on what is left of the last in the soil plus what it adds from the air and sunshine. As soon as a leaf or tree trunk falls to the ground it is taken in charge by a wrecking crew composed of a myriad of microscopic organisms who proceed to break it up into its component parts so these can be used for building a new edifice. The process is called "rotting" and the product, the black, gummy stuff of a fertile soil, is called "humus." The plants, that is, the higher plants, are not able to live on their own proteids as the animals are. But there are lower plants, certain kinds of bacteria, that can break up the big complicated proteid molecules into their component parts and reduce the nitrogen in them to ammonia or ammonia-like compounds. Having done this they stop and turn over the job to another set of bacteria to be carried through the next step. For you must know that soil society is as complex and specialized as that above ground and the tiniest bacterium would die rather than violate the union rules. The second set of bacteria change the ammonia over to nitrites and then a third set, the Amalgamated Union of Nitrate Workers, steps in and completes the process of oxidation with an efficiency that Ostwald might envy, for ninety-six per cent. of the ammonia of the soil is converted into nitrates. But if the conditions are not just right, if the food is insufficient or unwholesome or if the air that circulates through the soil is contaminated with poison gases, the bacteria go on a strike. The farmer, not seeing the thing from the standpoint of the bacteria, says the soil is "sick" and he proceeds to doctor it according to his own notion of what ails it. First perhaps he tries running in strike breakers. He goes to one of the firms that makes a business of supplying nitrogen-fixing bacteria from the scabs or nodules of the clover roots and scatters these colonies over the field. But if the living conditions remain bad the newcomers will soon quit work too and the farmer loses his money. If he is wise, then, he will remedy the conditions, putting a better ventilation system in his soil perhaps or neutralizing the sourness by means of lime or killing off the ameboid banditti that prey upon the peaceful bacteria engaged in the nitrogen industry. It is not an easy job that the farmer has in keeping billions of billions of subterranean servants contented and working together, but if he does not succeed at this he wastes his seed and labor. The layman regards the soil as a platform or anchoring place on which to set plants. He measures its value by its superficial area without considering its contents, which is as absurd as to estimate a man's wealth by the size of his safe. The difference in point of view is well illustrated by the old story of the city chap who was showing his farmer uncle the sights of New York. When he took him to Central Park he tried to astonish him by saying "This land is worth $500,000 an acre." The old farmer dug his toe into the ground, kicked out a clod, broke it open, looked at it, spit on it and squeezed it in his hand and then said, "Don't you believe it; 'tain't worth ten dollars an acre. Mighty poor soil I call it." Both were right. [Illustration: Courtesy of American Cyanamid Co. FIXING NITROGEN BY CALCIUM CARBIDE A view of the oven room in the plant of the American Cyanamid Company. The steel cylinders standing in the background are packed with the carbide and then put into the ovens sunk in the floor. When these are heated internally by electricity to 2000 degrees Fahrenheit pure nitrogen is let in and absorbed by the carbide, making cyanamid, which may be used as a fertilizer or for ammonia.] [Illustration: Photo by International Film Service A BARROW FULL OF POTASH SALTS EXTRACTED FROM SIX TONS OF GREEN KELP BY THE GOVERNMENT CHEMISTS] [Illustration: NATURE'S SILENT METHOD OF NITROGEN FIXATION The nodules on the vetch roots contain colonies of bacteria which have the power of taking the free nitrogen out of the air and putting it in compounds suitable for plant food.] The modern agriculturist realizes that the soil is a laboratory for the production of plant food and he ordinarily takes more pains to provide a balanced ration for it than he does for his family. Of course the necessity of feeding the soil has been known ever since man began to settle down and the ancient methods of maintaining its fertility, though discovered accidentally and followed blindly, were sound and efficacious. Virgil, who like Liberty Hyde Bailey was fond of publishing agricultural bulletins in poetry, wrote two thousand years ago: But sweet vicissitudes of rest and toil Make easy labor and renew the soil Yet sprinkle sordid ashes all around And load with fatt'ning dung thy fallow soil. The ashes supplied the potash and the dung the nitrate and phosphate. Long before the discovery of the nitrogen-fixing bacteria, the custom prevailed of sowing pea-like plants every third year and then plowing them under to enrich the soil. But such local supplies were always inadequate and as soon as deposits of fertilizers were discovered anywhere in the world they were drawn upon. The richest of these was the Chincha Islands off the coast of Peru, where millions of penguins and pelicans had lived in a most untidy manner for untold centuries. The guano composed of the excrement of the birds mixed with the remains of dead birds and the fishes they fed upon was piled up to a depth of 120 feet. From this Isle of Penguins--which is not that described by Anatole France--a billion dollars' worth of guano was taken and the deposit was soon exhausted. Then the attention of the world was directed to the mainland of Peru and Chile, where similar guano deposits had been accumulated and, not being washed away on account of the lack of rain, had been deposited as sodium nitrate, or "saltpeter." These beds were discovered by a German, Taddeo Haenke, in 1809, but it was not until the last quarter of the century that the nitrates came into common use as a fertilizer. Since then more than 53,000,000 tons have been taken out of these beds and the exportation has risen to a rate of 2,500,000 to 3,000,000 tons a year. How much longer they will last is a matter of opinion and opinion is largely influenced by whether you have your money invested in Chilean nitrate stock or in one of the new synthetic processes for making nitrates. The United States Department of Agriculture says the nitrate beds will be exhausted in a few years. On the other hand the Chilean Inspector General of Nitrate Deposits in his latest official report says that they will last for two hundred years at the present rate and that then there are incalculable areas of low grade deposits, containing less than eleven per cent., to be drawn upon. Anyhow, the South American beds cannot long supply the world's need of nitrates and we shall some time be starving unless creative chemistry comes to the rescue. In 1898 Sir William Crookes--the discoverer of the "Crookes tubes," the radiometer and radiant matter--startled the British Association for the Advancement of Science by declaring that the world was nearing the limit of wheat production and that by 1931 the bread-eaters, the Caucasians, would have to turn to other grains or restrict their population while the rice and millet eaters of Asia would continue to increase. Sir William was laughed at then as a sensationalist. He was, but his sensations were apt to prove true and it is already evident that he was too near right for comfort. Before we were half way to the date he set we had two wheatless days a week, though that was because we persisted in shooting nitrates into the air. The area producing wheat was by decades:[1] THE WHEAT FIELDS OF THE WORLD Acres 1881-90 192,000,000 1890-1900 211,000,000 1900-10 242,000,000 Probable limit 300,000,000 If 300,000,000 acres can be brought under cultivation for wheat and the average yield raised to twenty bushels to the acre, that will give enough to feed a billion people if they eat six bushels a year as do the English. Whether this maximum is correct or not there is evidently some limit to the area which has suitable soil and climate for growing wheat, so we are ultimately thrown back upon Crookes's solution of the problem; that is, we must increase the yield per acre and this can only be done by the use of fertilizers and especially by the fixation of atmospheric nitrogen. Crookes estimated the average yield of wheat at 12.7 bushels to the acre, which is more than it is in the new lands of the United States, Australia and Russia, but less than in Europe, where the soil is well fed. What can be done to increase the yield may be seen from these figures: GAIN IN THE YIELD OF WHEAT IN BUSHELS PER ACRE 1889-90 1913 Germany 19 35 Belgium 30 35 France 17 20 United Kingdom 28 32 United States 12 15 The greatest gain was made in Germany and we see a reason for it in the fact that the German importation of Chilean saltpeter was 55,000 tons in 1880 and 747,000 tons in 1913. In potatoes, too, Germany gets twice as big a crop from the same ground as we do, 223 bushels per acre instead of our 113 bushels. But the United States uses on the average only 28 pounds of fertilizer per acre, while Europe uses 200. It is clear that we cannot rely upon Chile, but make nitrates for ourselves as Germany had to in war time. In the first chapter we considered the new methods of fixing the free nitrogen from the air. But the fixation of nitrogen is a new business in this country and our chief reliance so far has been the coke ovens. When coal is heated in retorts or ovens for making coke or gas a lot of ammonia comes off with the other products of decomposition and is caught in the sulfuric acid used to wash the gas as ammonium sulfate. Our American coke-makers have been in the habit of letting this escape into the air and consequently we have been losing some 700,000 tons of ammonium salts every year, enough to keep our land rich and give us all the explosives we should need. But now they are reforming and putting in ovens that save the by-products such as ammonia and coal tar, so in 1916 we got from this source 325,000 tons a year. [Illustration: Courtesy of _Scientific American_. Consumption of potash for agricultural purposes in different countries] Germany had a natural monopoly of potash as Chile had a natural monopoly of nitrates. The agriculture of Europe and America has been virtually dependent upon these two sources of plant foods. Now when the world was cleft in twain by the shock of August, 1914, the Allied Powers had the nitrates and the Central Powers had the potash. If Germany had not had up her sleeve a new process for making nitrates she could not long have carried on a war and doubtless would not have ventured upon it. But the outside world had no such substitute for the German potash salts and has not yet discovered one. Consequently the price of potash in the United States jumped from $40 to $400 and the cost of food went up with it. Even under the stimulus of prices ten times the normal and with chemists searching furnace crannies and bad lands the United States was able to scrape up less than 10,000 tons of potash in 1916, and this was barely enough to satisfy our needs for two weeks! [Illustration: What happened to potash when the war broke out. This diagram from the _Journal of Industrial and Engineering Chemistry_ of July, 1917, shows how the supply of potassium muriate from Germany was shut off in 1914 and how its price rose.] Yet potash compounds are as cheap as dirt. Pick up a handful of gravel and you will be able to find much of it feldspar or other mineral containing some ten per cent. of potash. Unfortunately it is in combination with silica, which is harder to break up than a trust. But "constant washing wears away stones" and the potash that the metallurgist finds too hard to extract in his hottest furnace is washed out in the course of time through the dropping of the gentle rain from heaven. "All rivers run to the sea" and so the sea gets salt, all sorts of salts, principally sodium chloride (our table salt) and next magnesium, calcium and potassium chlorides or sulfates in this order of abundance. But if we evaporate sea-water down to dryness all these are left in a mix together and it is hard to sort them out. Only patient Nature has time for it and she only did on a large scale in one place, that is at Stassfurt, Germany. It seems that in the days when northwestern Prussia was undetermined whether it should be sea or land it was flooded annually by sea-water. As this slowly evaporated the dissolved salts crystallized out at the critical points, leaving beds of various combinations. Each year there would be deposited three to five inches of salts with a thin layer of calcium sulfate or gypsum on top. Counting these annual layers, like the rings on a stump, we find that the Stassfurt beds were ten thousand years in the making. They were first worked for their salt, common salt, alone, but in 1837 the Prussian Government began prospecting for new and deeper deposits and found, not the clean rock salt that they wanted, but bittern, largely magnesium sulfate or Epsom salt, which is not at all nice for table use. This stuff was first thrown away until it was realized that it was much more valuable for the potash it contains than was the rock salt they were after. Then the Germans began to purify the Stassfurt salts and market them throughout the world. They contain from fifteen to twenty-five per cent. of magnesium chloride mixed with magnesium chloride in "carnallite," with magnesium sulfate in "kainite" and sodium chloride in "sylvinite." More than thirty thousand miners and workmen are employed in the Stassfurt works. There are some seventy distinct establishments engaged in the business, but they are in combination. In fact they are compelled to be, for the German Government is as anxious to promote trusts as the American Government is to prevent them. Once the Stassfurt firms had a falling out and began a cutthroat competition. But the German Government objects to its people cutting each other's throats. American dealers were getting unheard of bargains when the German Government stepped in and compelled the competing corporations to recombine under threat of putting on an export duty that would eat up their profits. The advantages of such business coöperation are specially shown in opening up a new market for an unknown product as in the case of the introduction of the Stassfurt salts into American agriculture. The farmer in any country is apt to be set in his ways and when it comes to inducing him to spend his hard-earned money for chemicals that he never heard of and could not pronounce he--quite rightly--has to be shown. Well, he was shown. It was, if I remember right, early in the nineties that the German Kali Syndikat began operations in America and the United States Government became its chief advertising agent. In every state there was an agricultural experiment station and these were provided liberally with illustrated literature on Stassfurt salts with colored wall charts and sets of samples and free sacks of salts for field experiments. The station men, finding that they could rely upon the scientific accuracy of the information supplied by Kali and that the experiments worked out well, became enthusiastic advocates of potash fertilizers. The station bulletins--which Uncle Sam was kind enough to carry free to all the farmers of the state--sometimes were worded so like the Kali Company advertising that the company might have raised a complaint of plagiarizing, but they never did. The Chilean nitrates, which are under British control, were later introduced by similar methods through the agency of the state agricultural experiment stations. As a result of all this missionary work, which cost the Kali Company $50,000 a year, the attention of a large proportion of American farmers was turned toward intensive farming and they began to realize the necessity of feeding the soil that was feeding them. They grew dependent upon these two foreign and widely separated sources of supply. In the year before the war the United States imported a million tons of Stassfurt salts, for which the farmers paid more than $20,000,000. Then a declaration of American independence--the German embargo of 1915--cut us off from Stassfurt and for five years we had to rely upon our own resources. We have seen how Germany--shut off from Chile--solved the nitrogen problem for her fields and munition plants. It was not so easy for us--shut off from Germany--to solve the potash problem. There is no more lack of potash in the rocks than there is of nitrogen in the air, but the nitrogen is free and has only to be caught and combined, while the potash is shut up in a granite prison from which it is hard to get it free. It is not the percentage in the soil but the percentage in the soil water that counts. A farmer with his potash locked up in silicates is like the merchant who has left the key of his safe at home in his other trousers. He may be solvent, but he cannot meet a sight draft. It is only solvent potash that passes current. In the days of our grandfathers we had not only national independence but household independence. Every homestead had its own potash plant and soap factory. The frugal housewife dumped the maple wood ashes of the fireplace into a hollow log set up on end in the backyard. Water poured over the ashes leached out the lye, which drained into a bucket beneath. This gave her a solution of pearl ash or potassium carbonate whose concentration she tested with an egg as a hydrometer. In the meantime she had been saving up all the waste grease from the frying pan and pork rinds from the plate and by trying out these she got her soap fat. Then on a day set apart for this disagreeable process in chemical technology she boiled the fat and the lye together and got "soft soap," or as the chemist would call it, potassium stearate. If she wanted hard soap she "salted it out" with brine. The sodium stearate being less soluble was precipitated to the top and cooled into a solid cake that could be cut into bars by pack thread. But the frugal housewife threw away in the waste water what we now consider the most valuable ingredients, the potash and the glycerin. But the old lye-leach is only to be found in ruins on an abandoned farm and we no longer burn wood at the rate of a log a night. In 1916 even under the stimulus of tenfold prices the amount of potash produced as pearl ash was only 412 tons--and we need 300,000 tons in some form. It would, of course, be very desirable as a conservation measure if all the sawdust and waste wood were utilized by charring it in retorts. The gas makes a handy fuel. The tar washed from the gas contains a lot of valuable products. And potash can be leached out of the charcoal or from its ashes whenever it is burned. But this at best would not go far toward solving the problem of our national supply. There are other potash-bearing wastes that might be utilized. The cement mills which use feldspar in combination with limestone give off a potash dust, very much to the annoyance of their neighbors. This can be collected by running the furnace clouds into large settling chambers or long flues, where the dust may be caught in bags, or washed out by water sprays or thrown down by electricity. The blast furnaces for iron also throw off potash-bearing fumes. Our six-million-ton crop of sugar beets contains some 12,000 tons of nitrogen, 4000 tons of phosphoric acid and 18,000 tons of potash, all of which is lost except where the waste liquors from the sugar factory are used in irrigating the beet land. The beet molasses, after extracting all the sugar possible by means of lime, leaves a waste liquor from which the potash can be recovered by evaporation and charring and leaching the residue. The Germans get 5000 tons of potassium cyanide and as much ammonium sulfate annually from the waste liquor of their beet sugar factories and if it pays them to save this it ought to pay us where potash is dearer. Various other industries can put in a bit when Uncle Sam passes around the contribution basket marked "Potash for the Poor." Wool wastes and fish refuse make valuable fertilizers, although they will not go far toward solving the problem. If we saved all our potash by-products they would not supply more than fifteen per cent. of our needs. Though no potash beds comparable to those of Stassfurt have yet been discovered in the United States, yet in Nebraska, Utah, California and other western states there are a number of alkali lakes, wet or dry, containing a considerable amount of potash mixed with soda salts. Of these deposits the largest is Searles Lake, California. Here there are some twelve square miles of salt crust some seventy feet deep and the brine as pumped out contains about four per cent. of potassium chloride. The quantity is sufficient to supply the country for over twenty years, but it is not an easy or cheap job to separate the potassium from the sodium salts which are five times more abundant. These being less soluble than the potassium salts crystallize out first when the brine is evaporated. The final crystallization is done in vacuum pans as in getting sugar from the cane juice. In this way the American Trona Corporation is producing some 4500 tons of potash salts a month besides a thousand tons of borax. The borax which is contained in the brine to the extent of 1-1/2 per cent. is removed from the fertilizer for a double reason. It is salable by itself and it is detrimental to plant life. Another mineral source of potash is alunite, which is a sort of natural alum, or double sulfate of potassium and aluminum, with about ten per cent. of potash. It contains a lot of extra alumina, but after roasting in a kiln the potassium sulfate can be leached out. The alunite beds near Marysville, Utah, were worked for all they were worth during the war, but the process does not give potash cheap enough for our needs in ordinary times. [Illustration: Photo by International Film Service IN ORDER TO SECURE A NEW SUPPLY OF POTASH SALTS The United States Government set up an experimental plant at Sutherland, California, for the utilization of kelp. The harvester cuts 40 tons of kelp at a load] [Illustration: THE KELP HARVESTER GATHERING THE SEAWEED FROM THE PACIFIC OCEAN] [Illustration: Courtesy of Hercules Powder Co. OVERHEAD SUCTION AT THE SAN DIEGO WHARF PUMPING KELP FROM THE BARGE TO THE DIGESTION TANKS] The tourist going through Wyoming on the Union Pacific will have to the north of him what is marked on the map as the "Leucite Hills." If he looks up the word in the Unabridged that he carries in his satchel he will find that leucite is a kind of lava and that it contains potash. But he will also observe that the potash is combined with alumina and silica, which are hard to get out and useless when you get them out. One of the lavas of the Leucite Hills, that named from its native state "Wyomingite," gives fifty-seven per cent. of its potash in a soluble form on roasting with alunite--but this costs too much. The same may be said of all the potash feldspars and mica. They are abundant enough, but until we find a way of utilizing the by-products, say the silica in cement and the aluminum as a metal, they cannot solve our problem. Since it is so hard to get potash from the land it has been suggested that we harvest the sea. The experts of the United States Department of Agriculture have placed high hopes in the kelp or giant seaweed which floats in great masses in the Pacific Ocean not far off from the California coast. This is harvested with ocean reapers run by gasoline engines and brought in barges to the shore, where it may be dried and used locally as a fertilizer or burned and the potassium chloride leached out of the charcoal ashes. But it is hard to handle the bulky, slimy seaweed cheaply enough to get out of it the small amount of potash it contains. So efforts are now being made to get more out of the kelp than the potash. Instead of burning the seaweed it is fermented in vats producing acetic acid (vinegar). From the resulting liquid can be obtained lime acetate, potassium chloride, potassium iodide, acetone, ethyl acetate (used as a solvent for guncotton) and algin, a gelatin-like gum. PRODUCTION OF POTASH IN THE UNITED STATES __________________________________________________________________________ | | | 1916 | 1917 Source | Tons K_{2}O | Per cent. | Tons K_{2}O | Per cent. | | of total | | of total | | production | | production ____________________|_____________|____________|_____________|____________ | | | | Mineral sources: | | | | Natural brines | 3,994 | 41.1 | 20,652 | 63.4 Altmite | 1,850 | 19.0 | 2,402 | 7.3 Dust from cement | | | | mills | | | 1,621 | 5.0 Dust from blast | | | | furnaces | | | 185 | 0.6 Organic Sources: | | | | Kelp | 1,556 | 16.0 | 3,752 | 10.9 Molasses residue | | | | from distillers | 1,845 | 19.0 | 2,846 | 8.8 Wood ashes | 412 | 4.2 | 621 | 1.9 Waste liquors | | | | from beet-sugar | | | | refineries | | | 369 | 1.1 Miscellaneous | | | | industrial | | | | wastes | 63 | .7 | 305 | 1.0 | ___________ | __________ | ___________ | __________ | | | | Total | 9,720 | 100.0 | 32,573 | 100.0 --From U S. Bureau of Mines Report, 1918. This table shows how inadequate was the reaction of the United States to the war demand for potassium salts. The minimum yearly requirements of the United States are estimated to be 250,000 tons of potash. This completes our survey of the visible sources of potash in America. In 1917 under the pressure of the embargo and unprecedented prices the output of potash (K_{2}O) in various forms was raised to 32,573 tons, but this is only about a tenth as much as we needed. In 1918 potash production was further raised to 52,135 tons, chiefly through the increase of the output from natural brines to 39,255 tons, nearly twice what it was the year before. The rust in cotton and the resulting decrease in yield during the war are laid to lack of potash. Truck crops grown in soils deficient in potash do not stand transportation well. The Bureau of Animal Industry has shown in experiments in Aroostook County, Maine, that the addition of moderate amounts of potash doubled the yield of potatoes. Professor Ostwald, the great Leipzig chemist, boasted in the war: America went into the war like a man with a rope round his neck which is in his enemy's hands and is pretty tightly drawn. With its tremendous deposits Germany has a world monopoly in potash, a point of immense value which cannot be reckoned too highly when once this war is going to be settled. It is in Germany's power to dictate which of the nations shall have plenty of food and which shall starve. If, indeed, some mineralogist or metallurgist will cut that rope by showing us a supply of cheap potash we will erect him a monument as big as Washington's. But Ostwald is wrong in supposing that America is as dependent as Germany upon potash. The bulk of our food crops are at present raised without the use of any fertilizers whatever. As the cession of Lorraine in 1871 gave Germany the phosphates she needed for fertilizers so the retrocession of Alsace in 1919 gives France the potash she needed for fertilizers. Ten years before the war a bed of potash was discovered in the Forest of Monnebruck, near Hartmannsweilerkopf, the peak for which French and Germans contested so fiercely and so long. The layer of potassium salts is 16-1/2 feet thick and the total deposit is estimated to be 275,000,000 tons of potash. At any rate it is a formidable rival of Stassfurt and its acquisition by France breaks the German monopoly. When we turn to the consideration of the third plant food we feel better. While the United States has no such monopoly of phosphates as Germany had of potash and Chile had of nitrates we have an abundance and to spare. Whereas we formerly _imported_ about $17,000,000 worth of potash from Germany and $20,000,000 worth of nitrates from Chile a year we _exported_ $7,000,000 worth of phosphates. Whoever it was who first noticed that the grass grew thicker around a buried bone he lived so long ago that we cannot do honor to his powers of observation, but ever since then--whenever it was--old bones have been used as a fertilizer. But we long ago used up all the buffalo bones we could find on the prairies and our packing houses could not give us enough bone-meal to go around, so we have had to draw upon the old bone-yards of prehistoric animals. Deposits of lime phosphate of such origin were found in South Carolina in 1870 and in Florida in 1888. Since then the industry has developed with amazing rapidity until in 1913 the United States produced over three million tons of phosphates, nearly half of which was sent abroad. The chief source at present is the Florida pebbles, which are dredged up from the bottoms of lakes and rivers or washed out from the banks of streams by a hydraulic jet. The gravel is washed free from the sand and clay, screened and dried, and then is ready for shipment. The rock deposits of Florida and South Carolina are more limited than the pebble beds and may be exhausted in twenty-five or thirty years, but Tennessee and Kentucky have a lot in reserve and behind them are Idaho, Wyoming and other western states with millions of acres of phosphate land, so in this respect we are independent. But even here the war hit us hard. For the calcium phosphate as it comes from the ground is not altogether available because it is not very soluble and the plants can only use what they can get in the water that they suck up from the soil. But if the phosphate is treated with sulfuric acid it becomes more soluble and this product is sold as "superphosphate." The sulfuric acid is made mostly from iron pyrite and this we have been content to import, over 800,000 tons of it a year, largely from Spain, although we have an abundance at home. Since the shortage of shipping shut off the foreign supply we are using more of our own pyrite and also our deposits of native sulfur along the Gulf coast. But as a consequence of this sulfuric acid during the war went up from $5 to $25 a ton and acidulated phosphates rose correspondingly. Germany is short on natural phosphates as she is long on natural potash. But she has made up for it by utilizing a by-product of her steelworks. When phosphorus occurs in iron ore, even in minute amounts, it makes the steel brittle. Much of the iron ores of Alsace-Lorraine were formerly considered unworkable because of this impurity, but shortly after Germany took these provinces from France in 1871 a method was discovered by two British metallurgists, Thomas and Gilchrist, by which the phosphorus is removed from the iron in the process of converting it into steel. This consists in lining the crucible or converter with lime and magnesia, which takes up the phosphorus from the melted iron. This slag lining, now rich in phosphates, can be taken out and ground up for fertilizer. So the phosphorus which used to be a detriment is now an additional source of profit and this British invention has enabled Germany to make use of the territory she stole from France to outstrip England in the steel business. In 1910 Germany produced 2,000,000 tons of Thomas slag while only 160,000 tons were produced in the United Kingdom. The open hearth process now chiefly used in the United States gives an acid instead of a basic phosphate slag, not suitable as a fertilizer. The iron ore of America, with the exception of some of the southern ores, carries so small a percentage of phosphorus as to make a basic process inadvisable. Recently the Germans have been experimenting with a combined fertilizer, Schröder's potassium phosphate, which is said to be as good as Thomas slag for phosphates and as good as Stassfurt salts for potash. The American Cyanamid Company is just putting out a similar product, "Ammo-Phos," in which the ammonia can be varied from thirteen to twenty per cent. and the phosphoric acid from twenty to forty-seven per cent. so as to give the proportions desired for any crop. We have then the possibility of getting the three essential plant foods altogether in one compound with the elimination of most of the extraneous elements such as lime and magnesia, chlorids and sulfates. For the last three hundred years the American people have been living on the unearned increment of the unoccupied land. But now that all our land has been staked out in homesteads and we cannot turn to new soil when we have used up the old, we must learn, as the older races have learned, how to keep up the supply of plant food. Only in this way can our population increase and prosper. As we have seen, the phosphate question need not bother us and we can see our way clear toward solving the nitrate question. We gave the Government $20,000,000 to experiment on the production of nitrates from the air and the results will serve for fields as well as firearms. But the question of an independent supply of cheap potash is still unsolved. IV COAL-TAR COLORS If you put a bit of soft coal into a test tube (or, if you haven't a test tube, into a clay tobacco pipe and lute it over with clay) and heat it you will find a gas coming out of the end of the tube that will burn with a yellow smoky flame. After all the gas comes off you will find in the bottom of the test tube a chunk of dry, porous coke. These, then, are the two main products of the destructive distillation of coal. But if you are an unusually observant person, that is, if you are a born chemist with an eye to by-products, you will notice along in the middle of the tube where it is neither too hot nor too cold some dirty drops of water and some black sticky stuff. If you are just an ordinary person, you won't pay any attention to this because there is only a little of it and because what you are after is the coke and gas. You regard the nasty, smelly mess that comes in between as merely a nuisance because it clogs up and spoils your nice, clean tube. Now that is the way the gas-makers and coke-makers--being for the most part ordinary persons and not born chemists--used to regard the water and tar that got into their pipes. They washed it out so as to have the gas clean and then ran it into the creek. But the neighbors--especially those who fished in the stream below the gas-works--made a fuss about spoiling the water, so the gas-men gave away the tar to the boys for use in celebrating the Fourth of July and election night or sold it for roofing. [Illustration: THE PRODUCTION OF COAL TAR A battery of Koppers by-product coke-ovens at the plant of the Bethlehem Steel Company, Sparrows Point, Maryland. The coke is being pushed out of one of the ovens into the waiting car. The vapors given off from the coal contain ammonia and the benzene compound used to make dyes and explosives] [Illustration: IN THESE MIXING VATS AT THE BUFFALO WORKS, ANILINE DYES ARE PREPARED] But this same tar, which for a hundred years was thrown away and nearly half of which is thrown away yet in the United States, turns out to be one of the most useful things in the world. It is one of the strategic points in war and commerce. It wounds and heals. It supplies munitions and medicines. It is like the magic purse of Fortunatus from which anything wished for could be drawn. The chemist puts his hand into the black mass and draws out all the colors of the rainbow. This evil-smelling substance beats the rose in the production of perfume and surpasses the honey-comb in sweetness. Bishop Berkeley, after having proved that all matter was in your mind, wrote a book to prove that wood tar would cure all diseases. Nobody reads it now. The name is enough to frighten them off: "Siris: A Chain of Philosophical Reflections and Inquiries Concerning the Virtues of Tar Water." He had a sort of mystical idea that tar contained the quintessence of the forest, the purified spirit of the trees, which could somehow revive the spirit of man. People said he was crazy on the subject, and doubtless he was, but the interesting thing about it is that not even his active and ingenious imagination could begin to suggest all of the strange things that can be got out of tar, whether wood or coal. The reason why tar supplies all sorts of useful material is because it is indeed the quintessence of the forest, of the forests of untold millenniums if it is coal tar. If you are acquainted with a village tinker, one of those all-round mechanics who still survive in this age of specialization and can mend anything from a baby-carriage to an automobile, you will know that he has on the floor of his back shop a heap of broken machinery from which he can get almost anything he wants, a copper wire, a zinc plate, a brass screw or a steel rod. Now coal tar is the scrap-heap of the vegetable kingdom. It contains a little of almost everything that makes up trees. But you must not imagine that all that comes out of coal tar is contained in it. There are only about a dozen primary products extracted from coal tar, but from these the chemist is able to build up hundreds of thousands of new substances. This is true creative chemistry, for most of these compounds are not to be found in plants and never existed before they were made in the laboratory. It used to be thought that organic compounds, the products of vegetable and animal life, could only be produced by organized beings, that they were created out of inorganic matter by the magic touch of some "vital principle." But since the chemist has learned how, he finds it easier to make organic than inorganic substances and he is confident that he can reproduce any compound that he can analyze. He cannot only imitate the manufacturing processes of the plants and animals, but he can often beat them at their own game. When coal is heated in the open air it is burned up and nothing but the ashes is left. But heat the coal in an enclosed vessel, say a big fireclay retort, and it cannot burn up because the oxygen of the air cannot get to it. So it breaks up. All parts of it that can be volatized at a high heat pass off through the outlet pipe and nothing is left in the retort but coke, that is carbon with the ash it contains. When the escaping vapors reach a cool part of the outlet pipe the oily and tarry matter condenses out. Then the gas is passed up through a tower down which water spray is falling and thus is washed free from ammonia and everything else that is soluble in water. This process is called "destructive distillation." What products come off depends not only upon the composition of the particular variety of coal used, but upon the heat, pressure and rapidity of distillation. The way you run it depends upon what you are most anxious to have. If you want illuminating gas you will leave in it the benzene. If you are after the greatest yield of tar products, you impoverish the gas by taking out the benzene and get a blue instead of a bright yellow flame. If all you are after is cheap coke, you do not bother about the by-products, but let them escape and burn as they please. The tourist passing across the coal region at night could see through his car window the flames of hundreds of old-fashioned bee-hive coke-ovens and if he were of economical mind he might reflect that this display of fireworks was costing the country $75,000,000 a year besides consuming the irreplaceable fuel supply of the future. But since the gas was not needed outside of the cities and since the coal tar, if it could be sold at all, brought only a cent or two a gallon, how could the coke-makers be expected to throw out their old bee-hive ovens and put in the expensive retorts and towers necessary to the recovery of the by-products? But within the last ten years the by-product ovens have come into use and now nearly half our coke is made in them. Although the products of destructive distillation vary within wide limits, yet the following table may serve to give an approximate idea of what may be got from a ton of soft coal: 1 ton of coal may give Gas, 12,000 cubic feet Liquor (Washings) ammonium sulfate (7-25 pounds) Tar (120 pounds) benzene (10-20 pounds) toluene (3 pounds) xylene (1-1/2 pounds) phenol (1/2 pound) naphthalene (3/8 pound) anthracene (1/4 pound) pitch (80 pounds) Coke (1200-1500 pounds) When the tar is redistilled we get, among other things, the ten "crudes" which are fundamental material for making dyes. Their names are: benzene, toluene, xylene, phenol, cresol, naphthalene, anthracene, methyl anthracene, phenanthrene and carbazol. There! I had to introduce you to the whole receiving line, but now that that ceremony is over we are at liberty to do as we do at a reception, meet our old friends, get acquainted with one or two more and turn our backs on the rest. Two of them, I am sure, you've met before, phenol, which is common carbolic acid, and naphthalene, which we use for mothballs. But notice one thing in passing, that not one of them is a dye. They are all colorless liquids or white solids. Also they all have an indescribable odor--all odors that you don't know are indescribable--which gives them and their progeny, even when odorless, the name of "aromatic compounds." [Illustration: Fig. 8. Diagram of the products obtained from coal and some of their uses.] The most important of the ten because he is the father of the family is benzene, otherwise called benzol, but must not be confused with "benzine" spelled with an _i_ which we used to burn and clean our clothes with. "Benzine" is a kind of gasoline, but benzene _alias_ benzol has quite another constitution, although it looks and burns the same. Now the search for the constitution of benzene is one of the most exciting chapters in chemistry; also one of the most intricate chapters, but, in spite of that, I believe I can make the main point of it clear even to those who have never studied chemistry--provided they retain their childish liking for puzzles. It is really much like putting together the old six-block Chinese puzzle. The chemist can work better if he has a picture of what he is working with. Now his unit is the molecule, which is too small even to analyze with the microscope, no matter how high powered. So he makes up a sort of diagram of the molecule, and since he knows the number of atoms and that they are somehow attached to one another, he represents each atom by the first letter of its name and the points of attachment or bonds by straight lines connecting the atoms of the different elements. Now it is one of the rules of the game that all the bonds must be connected or hooked up with atoms at both ends, that there shall be no free hands reaching out into empty space. Carbon, for instance, has four bonds and hydrogen only one. They unite, therefore, in the proportion of one atom of carbon to four of hydrogen, or CH_{4}, which is methane or marsh gas and obviously the simplest of the hydrocarbons. But we have more complex hydrocarbons such as C_{6}H_{14}, known as hexane. Now if you try to draw the diagrams or structural formulas of these two compounds you will easily get H H H H H H H | | | | | | | H-C-H H-C-C-C-C-C-C-H | | | | | | | H H H H H H H methane hexane Each carbon atom, you see, has its four hands outstretched and duly grasped by one-handed hydrogen atoms or by neighboring carbon atoms in the chain. We can have such chains as long as you please, thirty or more in a chain; they are all contained in kerosene and paraffin. So far the chemist found it east to construct diagrams that would satisfy his sense of the fitness of things, but when he found that benzene had the compostion C_{6}H_{6} he was puzzled. If you try to draw the picture of C_{6}H_{6} you will get something like this: | | | | | | -C-C-C-C-C-C- | | | | | | H H H H H H which is an absurdity because more than half of the carbon hands are waving wildly around asking to be held by something. Benzene, C_{6}H_{6}, evidently is like hexane, C_{6}H_{14}, in having a chain of six carbon atoms, but it has dropped its H's like an Englishman. Eight of the H's are missing. Now one of the men who was worried over this benzene puzzle was the German chemist, Kekulé. One evening after working over the problem all day he was sitting by the fire trying to rest, but he could not throw it off his mind. The carbon and the hydrogen atoms danced like imps on the carpet and as he watched them through his half-closed eyes he suddenly saw that the chain of six carbon atoms had joined at the ends and formed a ring while the six hydrogen atoms were holding on to the outside hands, in this fashion: H | C / \\ H-C C-H || | H-C C-H \ // C | H Professor Kekulé saw at once that the demons of his subconscious self had furnished him with a clue to the labyrinth, and so it proved. We need not suppose that the benzene molecule if we could see it would look anything like this diagram of it, but the theory works and that is all the scientist asks of any theory. By its use thousands of new compounds have been constructed which have proved of inestimable value to man. The modern chemist is not a discoverer, he is an inventor. He sits down at his desk and draws a "Kekulé ring" or rather hexagon. Then he rubs out an H and hooks a nitro group (NO_{2}) on to the carbon in place of it; next he rubs out the O_{2} of the nitro group and puts in H_{2}; then he hitches on such other elements, or carbon chains and rings as he likes. He works like an architect designing a house and when he gets a picture of the proposed compounds to suit him he goes into the laboratory to make it. First he takes down the bottle of benzene and boils up some of this with nitric acid and sulfuric acid. This he puts in the nitro group and makes nitro-benzene, C_{6}H_{5}NO_{2}. He treats this with hydrogen, which displaces the oxygen and gives C_{6}H_{5}NH_{2} or aniline, which is the basis of so many of these compounds that they are all commonly called "the aniline dyes." But aniline itself is not a dye. It is a colorless or brownish oil. It is not necessary to follow our chemist any farther now that we have seen how he works, but before we pass on we will just look at one of his products, not one of the most complicated but still complicated enough. [Illustration: A molecule of a coal-tar dye] The name of this is sodium ditolyl-disazo-beta-naphthylamine- 6-sulfonic-beta-naphthylamine-3.6-disulfonate. These chemical names of organic compounds are discouraging to the beginner and amusing to the layman, but that is because neither of them realizes that they are not really words but formulas. They are hyphenated because they come from Germany. The name given above is no more of a mouthful than "a-square-plus-two-a-b-plus-b-square" or "Third Assistant Secretary of War to the President of the United States of America." The trade name of this dye is Brilliant Congo, but while that is handier to say it does not mean anything. Nobody but an expert in dyes would know what it was, while from the formula name any chemist familiar with such compounds could draw its picture, tell how it would behave and what it was made from, or even make it. The old alchemist was a secretive and pretentious person and used to invent queer names for the purpose of mystifying and awing the ignorant. But the chemist in dropping the al- has dropped the idea of secrecy and his names, though equally appalling to the layman, are designed to reveal and not to conceal. From this brief explanation the reader who has not studied chemistry will, I think, be able to get some idea of how these very intricate compounds are built up step by step. A completed house is hard to understand, but when we see the mason laying one brick on top of another it does not seem so difficult, although if we tried to do it we should not find it so easy as we think. Anyhow, let me give you a hint. If you want to make a good impression on a chemist don't tell him that he seems to you a sort of magician, master of a black art, and all that nonsense. The chemist has been trying for three hundred years to live down the reputation of being inspired of the devil and it makes him mad to have his past thrown up at him in this fashion. If his tactless admirers would stop saying "it is all a mystery and a miracle to me, and I cannot understand it" and pay attention to what he is telling them they would understand it and would find that it is no more of a mystery or a miracle than anything else. You can make an electrician mad in the same way by interrupting his explanation of a dynamo by asking: "But you cannot tell me what electricity really is." The electrician does not care a rap what electricity "really is"--if there really is any meaning to that phrase. All he wants to know is what he can do with it. [Illustration: COMPARISON OF COAL AND ITS DISTILLATION PRODUCTS From Hesse's "The Industry of the Coal Tar Dyes," _Journal of Industrial and Engineering Chemistry_, December, 1914] The tar obtained from the gas plant or the coke plant has now to be redistilled, giving off the ten "crudes" already mentioned and leaving in the still sixty-five per cent. of pitch, which may be used for roofing, paving and the like. The ten primary products or crudes are then converted into secondary products or "intermediates" by processes like that for the conversion of benzene into aniline. There are some three hundred of these intermediates in use and from them are built up more than three times as many dyes. The year before the war the American custom house listed 5674 distinct brands of synthetic dyes imported, chiefly from Germany, but some of these were trade names for the same product made by different firms or represented by different degrees of purity or form of preparation. Although the number of possible products is unlimited and over five thousand dyes are known, yet only about nine hundred are in use. We can summarize the situation so: Coal-tar --> 10 crudes --> 300 intermediates --> 900 dyes --> 5000 brands. Or, to borrow the neat simile used by Dr. Bernhard C. Hesse, it is like cloth-making where "ten fibers make 300 yarns which are woven into 900 patterns." The advantage of the artificial dyestuffs over those found in nature lies in their variety and adaptability. Practically any desired tint or shade can be made for any particular fabric. If my lady wants a new kind of green for her stockings or her hair she can have it. Candies and jellies and drinks can be made more attractive and therefore more appetizing by varied colors. Easter eggs and Easter bonnets take on new and brighter hues. More and more the chemist is becoming the architect of his own fortunes. He does not make discoveries by picking up a beaker and pouring into it a little from each bottle on the shelf to see what happens. He generally knows what he is after, and he generally gets it, although he is still often baffled and occasionally happens on something quite unexpected and perhaps more valuable than what he was looking for. Columbus was looking for India when he ran into an obstacle that proved to be America. William Henry Perkin was looking for quinine when he blundered into that rich and undiscovered country, the aniline dyes. William Henry was a queer boy. He had rather listen to a chemistry lecture than eat. When he was attending the City of London School at the age of thirteen there was an extra course of lectures on chemistry given at the noon recess, so he skipped his lunch to take them in. Hearing that a German chemist named Hofmann had opened a laboratory in the Royal College of London he headed for that. Hofmann obviously had no fear of forcing the young intellect prematurely. He perhaps had never heard that "the tender petals of the adolescent mind must be allowed to open slowly." He admitted young Perkin at the age of fifteen and started him on research at the end of his second year. An American student nowadays thinks he is lucky if he gets started on his research five years older than Perkin. Now if Hofmann had studied pedagogical psychology he would have been informed that nothing chills the ardor of the adolescent mind like being set at tasks too great for its powers. If he had heard this and believed it, he would not have allowed Perkin to spend two years in fruitless endeavors to isolate phenanthrene from coal tar and to prepare artificial quinine--and in that case Perkin would never have discovered the aniline dyes. But Perkin, so far from being discouraged, set up a private laboratory so he could work over-time. While working here during the Easter vacation of 1856--the date is as well worth remembering as 1066--he was oxidizing some aniline oil when he got what chemists most detest, a black, tarry mass instead of nice, clean crystals. When he went to wash this out with alcohol he was surprised to find that it gave a beautiful purple solution. This was "mauve," the first of the aniline dyes. The funny thing about it was that when Perkin tried to repeat the experiment with purer aniline he could not get his color. It was because he was working with impure chemicals, with aniline containing a little toluidine, that he discovered mauve. It was, as I said, a lucky accident. But it was not accidental that the accident happened to the young fellow who spent his noonings and vacations at the study of chemistry. A man may not find what he is looking for, but he never finds anything unless he is looking for something. Mauve was a product of creative chemistry, for it was a substance that had never existed before. Perkin's next great triumph, ten years later, was in rivaling Nature in the manufacture of one of her own choice products. This is alizarin, the coloring matter contained in the madder root. It was an ancient and oriental dyestuff, known as "Turkey red" or by its Arabic name of "alizari." When madder was introduced into France it became a profitable crop and at one time half a million tons a year were raised. A couple of French chemists, Robiquet and Colin, extracted from madder its active principle, alizarin, in 1828, but it was not until forty years later that it was discovered that alizarin had for its base one of the coal-tar products, anthracene. Then came a neck-and-neck race between Perkin and his German rivals to see which could discover a cheap process for making alizarin from anthracene. The German chemists beat him to the patent office by one day! Graebe and Liebermann filed their application for a patent on the sulfuric acid process as No. 1936 on June 25, 1869. Perkin filed his for the same process as No. 1948 on June 26. It had required twenty years to determine the constitution of alizarin, but within six months from its first synthesis the commercial process was developed and within a few years the sale of artificial alizarin reached $8,000,000 annually. The madder fields of France were put to other uses and even the French soldiers became dependent on made-in-Germany dyes for their red trousers. The British soldiers were placed in a similar situation as regards their red coats when after 1878 the azo scarlets put the cochineal bug out of business. The modern chemist has robbed royalty of its most distinctive insignia, Tyrian purple. In ancient times to be "porphyrogene," that is "born to the purple," was like admission to the Almanach de Gotha at the present time, for only princes or their wealthy rivals could afford to pay $600 a pound for crimsoned linen. The precious dye is secreted by a snail-like shellfish of the eastern coast of the Mediterranean. From a tiny sac behind the head a drop of thick whitish liquid, smelling like garlic, can be extracted. If this is spread upon cloth of any kind and exposed to air and sunlight it turns first green, next blue and then purple. If the cloth is washed with soap--that is, set by alkali--it becomes a fast crimson, such as Catholic cardinals still wear as princes of the church. The Phoenician merchants made fortunes out of their monopoly, but after the fall of Tyre it became one of "the lost arts"--and accordingly considered by those whose faces are set toward the past as much more wonderful than any of the new arts. But in 1909 Friedlander put an end to the superstition by analyzing Tyrian purple and finding that it was already known. It was the same as a dye that had been prepared five years before by Sachs but had not come into commercial use because of its inferiority to others in the market. It required 12,000 of the mollusks to supply the little material needed for analysis, but once the chemist had identified it he did not need to bother the Murex further, for he could make it by the ton if he had wanted to. The coloring principle turned out to be a di-brom indigo, that is the same as the substance extracted from the Indian plant, but with the addition of two atoms of bromine. Why a particular kind of a shellfish should have got the habit of extracting this rare element from sea water and stowing it away in this peculiar form is "one of those things no fellow can find out." But according to the chemist the Murex mollusk made a mistake in hitching the bromine to the wrong carbon atoms. He finds as he would word it that the 6:6' di-brom indigo secreted by the shellfish is not so good as the 5:5' di-brom indigo now manufactured at a cheap rate and in unlimited quantity. But we must not expect too much of a mollusk's mind. In their cheapness lies the offense of the aniline dyes in the minds of some people. Our modern aristocrats would delight to be entitled "porphyrogeniti" and to wear exclusive gowns of "purple and scarlet from the isles of Elishah" as was done in Ezekiel's time, but when any shopgirl or sailor can wear the royal color it spoils its beauty in their eyes. Applied science accomplishes a real democracy such as legislation has ever failed to establish. Any kind of dye found in nature can be made in the laboratory whenever its composition is understood and usually it can be made cheaper and purer than it can be extracted from the plant. But to work out a profitable process for making it synthetically is sometimes a task requiring high skill, persistent labor and heavy expenditure. One of the latest and most striking of these achievements of synthetic chemistry is the manufacture of indigo. Indigo is one of the oldest and fastest of the dyestuffs. To see that it is both ancient and lasting look at the unfaded blue cloths that enwrap an Egyptian mummy. When Caesar conquered our British ancestors he found them tattooed with woad, the native indigo. But the chief source of indigo was, as its name implies, India. In 1897 nearly a million acres in India were growing the indigo plant and the annual value of the crop was $20,000,000. Then the fall began and by 1914 India was producing only $300,000 worth! What had happened to destroy this profitable industry? Some blight or insect? No, it was simply that the Badische Anilin-und-Soda Fabrik had worked out a practical process for making artificial indigo. That indigo on breaking up gave off aniline was discovered as early as 1840. In fact that was how aniline got its name, for when Fritzsche distilled indigo with caustic soda he called the colorless distillate "aniline," from the Arabic name for indigo, "anil" or "al-nil," that is, "the blue-stuff." But how to reverse the process and get indigo from aniline puzzled chemists for more than forty years until finally it was solved by Adolf von Baeyer of Munich, who died in 1917 at the age of eighty-four. He worked on the problem of the constitution of indigo for fifteen years and discovered several ways of making it. It is possible to start from benzene, toluene or naphthalene. The first process was the easiest, but if you will refer to the products of the distillation of tar you will find that the amount of toluene produced is less than the naphthalene, which is hard to dispose of. That is, if a dye factory had worked out a process for making indigo from toluene it would not be practicable because there was not enough toluene produced to supply the demand for indigo. So the more complicated napthalene process was chosen in preference to the others in order to utilize this by-product. The Badische Anilin-und-Soda Fabrik spent $5,000,000 and seventeen years in chemical research before they could make indigo, but they gained a monopoly (or, to be exact, ninety-six per cent.) of the world's production. A hundred years ago indigo cost as much as $4 a pound. In 1914 we were paying fifteen cents a pound for it. Even the pauper labor of India could not compete with the German chemists at that price. At the beginning of the present century Germany was paying more than $3,000,000 a year for indigo. Fourteen years later Germany was _selling_ indigo to the amount of $12,600,000. Besides its cheapness, artificial indigo is preferable because it is of uniform quality and greater purity. Vegetable indigo contains from forty to eighty per cent. of impurities, among them various other tinctorial substances. Artificial indigo is made pure and of any desired strength, so the dyers can depend on it. The value of the aniline colors lies in their infinite variety. Some are fast, some will fade, some will stand wear and weather as long as the fabric, some will wash out on the spot. Dyes can be made that will attach themselves to wool, to silk or to cotton, and give it any shade of any color. The period of discovery by accident has long gone by. The chemist nowadays decides first just what kind of a dye he wants, and then goes to work systematically to make it. He begins by drawing a diagram of the molecule, double-linking nitrogen or carbon and oxygen atoms to give the required intensity, putting in acid or basic radicals to fasten it to the fiber, shifting the color back and forth along the spectrum at will by introducing methyl groups, until he gets it just to his liking. Art can go ahead of nature in the dyestuff business. Before man found that he could make all the dyes he wanted from the tar he had been burning up at home he searched the wide world over to find colors by which he could make himself--or his wife--garments as beautiful as those that arrayed the flower, the bird and the butterfly. He sent divers down into the Mediterranean to rob the murex of his purple. He sent ships to the new world to get Brazil wood and to the oldest world for indigo. He robbed the lady cochineal of her scarlet coat. Why these peculiar substances were formed only by these particular plants, mussels and insects it is hard to understand. I don't know that Mrs. Cacti Coccus derived any benefit from her scarlet uniform when khaki would be safer, and I can't imagine that to a shellfish it was of advantage to turn red as it rots or to an indigo plant that its leaves in decomposing should turn blue. But anyhow, it was man that took advantage of them until he learned how to make his own dyestuffs. Our independent ancestors got along so far as possible with what grew in the neighborhood. Sweetapple bark gave a fine saffron yellow. Ribbons were given the hue of the rose by poke berry juice. The Confederates in their butternut-colored uniform were almost as invisible as if in khaki or _feldgrau_. Madder was cultivated in the kitchen garden. Only logwood from Jamaica and indigo from India had to be imported. That we are not so independent today is our own fault, for we waste enough coal tar to supply ourselves and other countries with all the new dyes needed. It is essentially a question of economy and organization. We have forgotten how to economize, but we have learned how to organize. The British Government gave the discoverer of mauve a title, but it did not give him any support in his endeavors to develop the industry, although England led the world in textiles and needed more dyes than any other country. So in 1874 Sir William Perkin relinquished the attempt to manufacture the dyes he had discovered because, as he said, Oxford and Cambridge refused to educate chemists or to carry on research. Their students, trained in the classics for the profession of being a gentleman, showed a decided repugnance to the laboratory on account of its bad smells. So when Hofmann went home he virtually took the infant industry along with him to Germany, where Ph.D.'s were cheap and plentiful and not afraid of bad smells. There the business throve amazingly, and by 1914 the Germans were manufacturing more than three-fourths of all the coal-tar products of the world and supplying material for most of the rest. The British cursed the universities for thus imperiling the nation through their narrowness and neglect; but this accusation, though natural, was not altogether fair, for at least half the blame should go to the British dyer, who did not care where his colors came from, so long as they were cheap. When finally the universities did turn over a new leaf and began to educate chemists, the manufacturers would not employ them. Before the war six English factories producing dyestuffs employed only 35 chemists altogether, while one German color works, the Höchster Farbwerke, employed 307 expert chemists and 74 technologists. This firm united with the six other leading dye companies of Germany on January 1, 1916, to form a trust to last for fifty years. During this time they will maintain uniform prices and uniform wage scales and hours of labor, and exchange patents and secrets. They will divide the foreign business _pro rata_ and share the profits. The German chemical works made big profits during the war, mostly from munitions and medicines, and will be, through this new combination, in a stronger position than ever to push the export trade. As a consequence of letting the dye business get away from her, England found herself in a fix when war broke out. She did not have dyes for her uniforms and flags, and she did not have drugs for her wounded. She could not take advantage of the blockade to capture the German trade in Asia and South America, because she could not color her textiles. A blue cotton dyestuff that sold before the war at sixty cents a pound, brought $34 a pound. A bright pink rhodamine formerly quoted at a dollar a pound jumped to $48. When one keg of dye ordinarily worth $15 was put up at forced auction sale in 1915 it was knocked down at $1500. The Highlanders could not get the colors for their kilts until some German dyes were smuggled into England. The textile industries of Great Britain, that brought in a billion dollars a year and employed one and a half million workers, were crippled for lack of dyes. The demand for high explosives from the front could not be met because these also are largely coal-tar products. Picric acid is both a dye and an explosive. It is made from carbolic acid and the famous trinitrotoluene is made from toluene, both of which you will find in the list of the ten fundamental "crudes." Both Great Britain and the United States realized the danger of allowing Germany to recover her former monopoly, and both have shown a readiness to cast overboard their traditional policies to meet this emergency. The British Government has discovered that a country without a tariff is a land without walls. The American Government has discovered that an industry is not benefited by being cut up into small pieces. Both governments are now doing all they can to build up big concerns and to provide them with protection. The British Government assisted in the formation of a national company for the manufacture of synthetic dyes by taking one-sixth of the stock and providing $500,000 for a research laboratory. But this effort is now reported to be "a great failure" because the Government put it in charge of the politicians instead of the chemists. The United States, like England, had become dependent upon Germany for its dyestuffs. We imported nine-tenths of what we used and most of those that were produced here were made from imported intermediates. When the war broke out there were only seven firms and 528 persons employed in the manufacture of dyes in the United States. One of these, the Schoelkopf Aniline and Chemical Works, of Buffalo, deserves mention, for it had stuck it out ever since 1879, and in 1914 was making 106 dyes. In June, 1917, this firm, with the encouragement of the Government Bureau of Foreign and Domestic Commerce, joined with some of the other American producers to form a trade combination, the National Aniline and Chemical Company. The Du Pont Company also entered the field on an extensive scale and soon there were 118 concerns engaged in it with great profit. During the war $200,000,000 was invested in the domestic dyestuff industry. To protect this industry Congress put on a specific duty of five cents a pound and an ad valorem duty of 30 per cent. on imported dyestuffs; but if, after five years, American manufacturers are not producing 60 per cent. in value of the domestic consumption, the protection is to be removed. For some reason, not clearly understood and therefore hotly discussed, Congress at the last moment struck off the specific duty from two of the most important of the dyestuffs, indigo and alizarin, as well as from all medicinals and flavors. The manufacture of dyes is not a big business, but it is a strategic business. Heligoland is not a big island, but England would have been glad to buy it back during the war at a high price per square yard. American industries employing over two million men and women and producing over three billion dollars' worth of products a year are dependent upon dyes. Chief of these is of course textiles, using more than half the dyes; next come leather, paper, paint and ink. We have been importing more than $12,000,000 worth of coal-tar products a year, but the cottonseed oil we exported in 1912 would alone suffice to pay that bill twice over. But although the manufacture of dyes cannot be called a big business, in comparison with some others, it is a paying business when well managed. The German concerns paid on an average 22 per cent. dividends on their capital and sometimes as high as 50 per cent. Most of the standard dyes have been so long in use that the patents are off and the processes are well enough known. We have the coal tar and we have the chemists, so there seems no good reason why we should not make our own dyes, at least enough of them so we will not be caught napping as we were in 1914. It was decidedly humiliating for our Government to have to beg Germany to sell us enough colors to print our stamps and greenbacks and then have to beg Great Britain for permission to bring them over by Dutch ships. The raw material for the production of coal-tar products we have in abundance if we will only take the trouble to save it. In 1914 the crude light oil collected from the coke-ovens would have produced only about 4,500,000 gallons of benzol and 1,500,000 gallons of toluol, but in 1917 this output was raised to 40,200,000 gallons of benzol and 10,200,000 of toluol. The toluol was used mostly in the manufacture of trinitrotoluol for use in Europe. When the war broke out in 1914 it shut off our supply of phenol (carbolic acid) for which we were dependent upon foreign sources. This threatened not only to afflict us with headaches by depriving us of aspirin but also to removed the consolation of music, for phenol is used in making phonographic records. Mr. Edison with his accustomed energy put up a factory within a few weeks for the manufacture of synthetic phenol. When we entered the war the need for phenol became yet more imperative, for it was needed to make picric acid for filling bombs. This demand was met, and in 1917 there were fifteen new plants turning out 64,146,499 pounds of phenol valued at $23,719,805. Some of the coal-tar products, as we see, serve many purposes. For instance, picric acid appears in three places in this book. It is a high explosive. It is a powerful and permanent yellow dye as any one who has touched it knows. Thirdly it is used as an antiseptic to cover burned skin. Other coal-tar dyes are used for the same purpose, "malachite green," "brilliant green," "crystal violet," "ethyl violet" and "Victoria blue," so a patient in a military hospital is decorated like an Easter egg. During the last five years surgeons have unfortunately had unprecedented opportunities for the study of wounds and fortunately they have been unprecedentedly successful in finding improved methods of treating them. In former wars a serious wound meant usually death or amputation. Now nearly ninety per cent. of the wounded are able to continue in the service. The reason for this improvement is that medicines are now being made to order instead of being gathered "from China to Peru." The old herb doctor picked up any strange plant that he could find and tried it on any sick man that would let him. This empirical method, though hard on the patients, resulted in the course of five thousand years in the discovery of a number of useful remedies. But the modern medicine man when he knows the cause of the disease is usually able to devise ways of counteracting it directly. For instance, he knows, thanks to Pasteur and Metchnikoff, that the cause of wound infection is the bacterial enemies of man which swarm by the million into any breach in his protective armor, the skin. Now when a breach is made in a line of intrenchments the defenders rush troops to the threatened spot for two purposes, constructive and destructive, engineers and warriors, the former to build up the rampart with sandbags, the latter to kill the enemy. So when the human body is invaded the blood brings to the breach two kinds of defenders. One is the serum which neutralizes the bacterial poison and by coagulating forms a new skin or scab over the exposed flesh. The other is the phagocytes or white corpuscles, the free lances of our corporeal militia, which attack and kill the invading bacteria. The aim of the physician then is to aid these defenders as much as possible without interfering with them. Therefore the antiseptic he is seeking is one that will assist the serum in protecting and repairing the broken tissues and will kill the hostile bacteria without killing the friendly phagocytes. Carbolic acid, the most familiar of the coal-tar antiseptics, will destroy the bacteria when it is diluted with 250 parts of water, but unfortunately it puts a stop to the fighting activities of the phagocytes when it is only half that strength, or one to 500, so it cannot destroy the infection without hindering the healing. In this search for substances that would attack a specific disease germ one of the leading investigators was Prof. Paul Ehrlich, a German physician of the Hebrew race. He found that the aniline dyes were useful for staining slides under the microscope, for they would pick out particular cells and leave others uncolored and from this starting point he worked out organic and metallic compounds which would destroy the bacteria and parasites that cause some of the most dreadful of diseases. A year after the war broke out Professor Ehrlich died while working in his laboratory on how to heal with coal-tar compounds the wounds inflicted by explosives from the same source. One of the most valuable of the aniline antiseptics employed by Ehrlich is flavine or, if the reader prefers to call it by its full name, diaminomethylacridinium chloride. Flavine, as its name implies, is a yellow dye and will kill the germs causing ordinary abscesses when in solution as dilute as one part of the dye to 200,000 parts of water, but it does not interfere with the bactericidal action of the white blood corpuscles unless the solution is 400 times as strong as this, that is one part in 500. Unlike carbolic acid and other antiseptics it is said to stimulate the serum instead of impairing its activity. Another antiseptic of the coal-tar family which has recently been brought into use by Dr. Dakin of the Rockefeller Institute is that called by European physicians chloramine-T and by American physicians chlorazene and by chemists para-toluene-sodium-sulfo-chloramide. This may serve to illustrate how a chemist is able to make such remedies as the doctor needs, instead of depending upon the accidental by-products of plants. On an earlier page I explained how by starting with the simplest of ring-compounds, the benzene of coal tar, we could get aniline. Suppose we go a step further and boil the aniline oil with acetic acid, which is the acid of vinegar minus its water. This easy process gives us acetanilid, which when introduced into the market some years ago under the name of "antifebrin" made a fortune for its makers. The making of medicines from coal tar began in 1874 when Kolbe made salicylic acid from carbolic acid. Salicylic acid is a rheumatism remedy and had previously been extracted from willow bark. If now we treat salicylic acid with concentrated acetic acid we get "aspirin." From aniline again are made "phenacetin," "antipyrin" and a lot of other drugs that have become altogether too popular as headache remedies--say rather "headache relievers." Another class of synthetics equally useful and likewise abused, are the soporifics, such as "sulphonal," "veronal" and "medinal." When it is not desired to put the patient to sleep but merely to render insensible a particular place, as when a tooth is to be pulled, cocain may be used. This, like alcohol and morphine, has proved a curse as well as a blessing and its sale has had to be restricted because of the many victims to the habit of using this drug. Cocain is obtained from the leaves of the South American coca tree, but can be made artificially from coal-tar products. The laboratory is superior to the forest because other forms of local anesthetics, such as eucain and novocain, can be made that are better than the natural alkaloid because more effective and less poisonous. I must not forget to mention another lot of coal-tar derivatives in which some of my readers will take a personal interest. That is the photographic developers. I am old enough to remember when we used to develop our plates in ferrous sulfate solution and you never saw nicer negatives than we got with it. But when pyrogallic acid came in we switched over to that even though it did stain our fingers and sometimes our plates. Later came a swarm of new organic reducing agents under various fancy names, such as metol, hydro (short for hydro-quinone) and eikongen ("the image-maker"). Every fellow fixed up his own formula and called his fellow-members of the camera club fools for not adopting it though he secretly hoped they would not. Under the double stimulus of patriotism and high prices the American drug and dyestuff industry developed rapidly. In 1917 about as many pounds of dyes were manufactured in America as were imported in 1913 and our _exports_ of American-made dyes exceeded in value our _imports_ before the war. In 1914 the output of American dyes was valued at $2,500,000. In 1917 it amounted to over $57,000,000. This does not mean that the problem was solved, for the home products were not equal in variety and sometimes not in quality to those made in Germany. Many valuable dyes were lacking and the cost was of course much higher. Whether the American industry can compete with the foreign in an open market and on equal terms is impossible to say because such conditions did not prevail before the war and they are not going to prevail in the future. Formerly the large German cartels through their agents and branches in this country kept the business in their own hands and now the American manufacturers are determined to maintain the independence they have acquired. They will not depend hereafter upon the tariff to cut off competition but have adopted more effective measures. The 4500 German chemical patents that had been seized by the Alien Property Custodian were sold by him for $250,000 to the Chemical Foundation, an association of American manufacturers organized "for the Americanization of such institutions as may be affected thereby, for the exclusion or elimination of alien interests hostile or detrimental to said industries and for the advancement of chemical and allied science and industry in the United States." The Foundation has a large fighting fund so that it "may be able to commence immediately and prosecute with the utmost vigor infringement proceedings whenever the first German attempt shall hereafter be made to import into this country." So much mystery has been made of the achievements of German chemists--as though the Teutonic brain had a special lobe for that faculty, lacking in other craniums--that I want to quote what Dr. Hesse says about his first impressions of a German laboratory of industrial research: Directly after graduating from the University of Chicago in 1896, I entered the employ of the largest coal-tar dye works in the world at its plant in Germany and indeed in one of its research laboratories. This was my first trip outside the United States and it was, of course, an event of the first magnitude for me to be in Europe, and, as a chemist, to be in Germany, in a German coal-tar dye plant, and to cap it all in its research laboratory--a real _sanctum sanctorum_ for chemists. In a short time the daily routine wore the novelty off my experience and I then settled down to calm analysis and dispassionate appraisal of my surroundings and to compare what was actually before and around me with my expectations. I found that the general laboratory equipment was no better than what I had been accustomed to; that my colleagues had no better fundamental training than I had enjoyed nor any better fact--or manipulative--equipment than I; that those in charge of the work had no better general intellectual equipment nor any more native ability than had my instructors; in short, there was nothing new about it all, nothing that we did not have back home, nothing--except the specific problems that were engaging their attention, and the special opportunities of attacking them. Those problems were of no higher order of complexity than those I had been accustomed to for years, in fact, most of them were not very complex from a purely intellectual viewpoint. There was nothing inherently uncanny, magical or wizardly about their occupation whatever. It was nothing but plain hard work and keeping everlastingly at it. Now, what was the actual thing behind that chemical laboratory that we did not have at home? It was money, willing to back such activity, convinced that in the final outcome, a profit would be made; money, willing to take university graduates expecting from them no special knowledge other than a good and thorough grounding in scientific research and provide them with opportunity to become specialists suited to the factory's needs. It is evidently not impossible to make the United States self-sufficient in the matter of coal-tar products. We've got the tar; we've got the men; we've got the money, too. Whether such a policy would pay us in the long run or whether it is necessary as a measure of military or commercial self-defense is another question that cannot here be decided. But whatever share we may have in it the coal-tar industry has increased the economy of civilization and added to the wealth of the world by showing how a waste by-product could be utilized for making new dyes and valuable medicines, a better use for tar than as fuel for political bonfires and as clothing for the nakedness of social outcasts. V SYNTHETIC PERFUMES AND FLAVORS The primitive man got his living out of such wild plants and animals as he could find. Next he, or more likely his wife, began to cultivate the plants and tame the animals so as to insure a constant supply. This was the first step toward civilization, for when men had to settle down in a community (_civitas_) they had to ameliorate their manners and make laws protecting land and property. In this settled and orderly life the plants and animals improved as well as man and returned a hundredfold for the pains that their master had taken in their training. But still man was dependent upon the chance bounties of nature. He could select, but he could not invent. He could cultivate, but he could not create. If he wanted sugar he had to send to the West Indies. If he wanted spices he had to send to the East Indies. If he wanted indigo he had to send to India. If he wanted a febrifuge he had to send to Peru. If he wanted a fertilizer he had to send to Chile. If he wanted rubber he had to send to the Congo. If he wanted rubies he had to send to Mandalay. If he wanted otto of roses he had to send to Turkey. Man was not yet master of his environment. This period of cultivation, the second stage of civilization, began before the dawn of history and lasted until recent times. We might almost say up to the twentieth century, for it was not until the fundamental laws of heredity were discovered that man could originate new species of plants and animals according to a predetermined plan by combining such characteristics as he desired to perpetuate. And it was not until the fundamental laws of chemistry were discovered that man could originate new compounds more suitable to his purpose than any to be found in nature. Since the progress of mankind is continuous it is impossible to draw a date line, unless a very jagged one, along the frontier of human culture, but it is evident that we are just entering upon the third era of evolution in which man will make what he needs instead of trying to find it somewhere. The new epoch has hardly dawned, yet already a man may stay at home in New York or London and make his own rubber and rubies, his own indigo and otto of roses. More than this, he can make gems and colors and perfumes that never existed since time began. The man of science has signed a declaration of independence of the lower world and we are now in the midst of the revolution. Our eyes are dazzled by the dawn of the new era. We know what the hunter and the horticulturist have already done for man, but we cannot imagine what the chemist can do. If we look ahead through the eyes of one of the greatest of French chemists, Berthelot, this is what we shall see: The problem of food is a chemical problem. Whenever energy can be obtained economically we can begin to make all kinds of aliment, with carbon borrowed from carbonic acid, hydrogen taken from the water and oxygen and nitrogen drawn from the air.... The day will come when each person will carry for his nourishment his little nitrogenous tablet, his pat of fatty matter, his package of starch or sugar, his vial of aromatic spices suited to his personal taste; all manufactured economically and in unlimited quantities; all independent of irregular seasons, drought and rain, of the heat that withers the plant and of the frost that blights the fruit; all free from pathogenic microbes, the origin of epidemics and the enemies of human life. On that day chemistry will have accomplished a world-wide revolution that cannot be estimated. There will no longer be hills covered with vineyards and fields filled with cattle. Man will gain in gentleness and morality because he will cease to live by the carnage and destruction of living creatures.... The earth will be covered with grass, flowers and woods and in it the human race will dwell in the abundance and joy of the legendary age of gold--provided that a spiritual chemistry has been discovered that changes the nature of man as profoundly as our chemistry transforms material nature. But this is looking so far into the future that we can trust no man's eyesight, not even Berthelot's. There is apparently no impossibility about the manufacture of synthetic food, but at present there is no apparent probability of it. There is no likelihood that the laboratory will ever rival the wheat field. The cornstalk will always be able to work cheaper than the chemist in the manufacture of starch. But in rarer and choicer products of nature the chemist has proved his ability to compete and even to excel. What have been from the dawn of history to the rise of synthetic chemistry the most costly products of nature? What could tempt a merchant to brave the perils of a caravan journey over the deserts of Asia beset with Arab robbers? What induced the Portuguese and Spanish mariners to risk their frail barks on perilous waters of the Cape of Good Hope or the Horn? The chief prizes were perfumes, spices, drugs and gems. And why these rather than what now constitutes the bulk of oversea and overland commerce? Because they were precious, portable and imperishable. If the merchant got back safe after a year or two with a little flask of otto of roses, a package of camphor and a few pearls concealed in his garments his fortune was made. If a single ship of the argosy sent out from Lisbon came back with a load of sandalwood, indigo or nutmeg it was regarded as a successful venture. You know from reading the Bible, or if not that, from your reading of Arabian Nights, that a few grains of frankincense or a few drops of perfumed oil were regarded as gifts worthy the acceptance of a king or a god. These products of the Orient were equally in demand by the toilet and the temple. The unctorium was an adjunct of the Roman bathroom. Kings had to be greased and fumigated before they were thought fit to sit upon a throne. There was a theory, not yet altogether extinct, that medicines brought from a distance were most efficacious, especially if, besides being expensive, they tasted bad like myrrh or smelled bad like asafetida. And if these failed to save the princely patient he was embalmed in aromatics or, as we now call them, antiseptics of the benzene series. Today, as always, men are willing to pay high for the titillation of the senses of smell and taste. The African savage will trade off an ivory tusk for a piece of soap reeking with synthetic musk. The clubman will pay $10 for a bottle of wine which consists mostly of water with about ten per cent. of alcohol, worth a cent or two, but contains an unweighable amount of the "bouquet" that can only be produced on the sunny slopes of Champagne or in the valley of the Rhine. But very likely the reader is quite as extravagant, for when one buys the natural violet perfumery he is paying at the rate of more than $10,000 a pound for the odoriferous oil it contains; the rest is mere water and alcohol. But you would not want the pure undiluted oil if you could get it, for it is unendurable. A single whiff of it paralyzes your sense of smell for a time just as a loud noise deafens you. Of the five senses, three are physical and two chemical. By touch we discern pressures and surface textures. By hearing we receive impressions of certain air waves and by sight of certain ether waves. But smell and taste lead us to the heart of the molecule and enable us to tell how the atoms are put together. These twin senses stand like sentries at the portals of the body, where they closely scrutinize everything that enters. Sounds and sights may be disagreeable, but they are never fatal. A man can live in a boiler factory or in a cubist art gallery, but he cannot live in a room containing hydrogen sulfide. Since it is more important to be warned of danger than guided to delights our senses are made more sensitive to pain than pleasure. We can detect by the smell one two-millionth of a milligram of oil of roses or musk, but we can detect one two-billionth of a milligram of mercaptan, which is the vilest smelling compound that man has so far invented. If you do not know how much a milligram is consider a drop picked up by the point of a needle and imagine that divided into two billion parts. Also try to estimate the weight of the odorous particles that guide a dog to the fox or warn a deer of the presence of man. The unaided nostril can rival the spectroscope in the detection and analysis of unweighable amounts of matter. What we call flavor or savor is a joint effect of taste and odor in which the latter predominates. There are only four tastes of importance, acid, alkaline, bitter and sweet. The acid, or sour taste, is the perception of hydrogen atoms charged with positive electricity. The alkaline, or soapy taste, is the perception of hydroxyl radicles charged with negative electricity. The bitter and sweet tastes and all the odors depend upon the chemical constitution of the compound, but the laws of the relation have not yet been worked out. Since these sense organs, the taste and smell buds, are sunk in the moist mucous membrane they can only be touched by substances soluble in water, and to reach the sense of smell they must also be volatile so as to be diffused in the air inhaled by the nose. The "taste" of food is mostly due to the volatile odors of it that creep up the back-stairs into the olfactory chamber. A chemist given an unknown substance would have to make an elementary analysis and some tedious tests to determine whether it contained methyl or ethyl groups, whether it was an aldehyde or an ester, whether the carbon atoms were singly or doubly linked and whether it was an open chain or closed. But let him get a whiff of it and he can give instantly a pretty shrewd guess as to these points. His nose knows. Although the chemist does not yet know enough to tell for certain from looking at the structural formula what sort of odor the compound would have or whether it would have any, yet we can divide odoriferous substances into classes according to their constitution. What are commonly known as "fruity" odors belong mostly to what the chemist calls the fatty or aliphatic series. For instance, we may have in a ripe fruit an alcohol (say ethyl or common alcohol) and an acid (say acetic or vinegar) and a combination of these, the ester or organic salt (in this case ethyl acetate), which is more odorous than either of its components. These esters of the fatty acids give the characteristic savor to many of our favorite fruits, candies and beverages. The pear flavor, amyl acetate, is made from acetic acid and amyl alcohol--though amyl alcohol (fusel oil) has a detestable smell. Pineapple is ethyl butyrate--but the acid part of it (butyric acid) is what gives Limburger cheese its aroma. These essential oils are easily made in the laboratory, but cannot be extracted from the fruit for separate use. If the carbon chain contains one or more double linkages we get the "flowery" perfumes. For instance, here is the symbol of geraniol, the chief ingredient of otto of roses: (CH_{3})_{2}C = CHCH_{2}CH_{2}C(CH_{3})_{2} = CHCH_{2}OH The rose would smell as sweet under another name, but it may be questioned whether it would stand being called by the name of dimethyl-2-6-octadiene-2-6-ol-8. Geraniol by oxidation goes into the aldehyde, citral, which occurs in lemons, oranges and verbena flowers. Another compound of this group, linalool, is found in lavender, bergamot and many flowers. Geraniol, as you would see if you drew up its structural formula in the way I described in the last chapter, contains a chain of six carbon atoms, that is, the same number as make a benzene ring. Now if we shake up geraniol and other compounds of this group (the diolefines) with diluted sulfuric acid the carbon chain hooks up to form a benzene ring, but with the other carbon atoms stretched across it; rather too complicated to depict here. These "bridged rings" of the formula C_{5}H_{8}, or some multiple of that, constitute the important group of the terpenes which occur in turpentine and such wild and woodsy things as sage, lavender, caraway, pine needles and eucalyptus. Going further in this direction we are led into the realm of the heavy oriental odors, patchouli, sandalwood, cedar, cubebs, ginger and camphor. Camphor can now be made directly from turpentine so we may be independent of Formosa and Borneo. When we have a six carbon ring without double linkings (cyclo-aliphatic) or with one or two such, we get soft and delicate perfumes like the violet (ionone and irone). But when these pass into the benzene ring with its three double linkages the odor becomes more powerful and so characteristic that the name "aromatic compound" has been extended to the entire class of benzene derivatives, although many of them are odorless. The essential oils of jasmine, orange blossoms, musk, heliotrope, tuberose, ylang ylang, etc., consist mostly of this class and can be made from the common source of aromatic compounds, coal tar. The synthetic flavors and perfumes are made in the same way as the dyes by starting with some coal-tar product or other crude material and building up the molecule to the desired complexity. For instance, let us start with phenol, the ill-smelling and poisonous carbolic acid of disagreeable associations and evil fame. Treat this to soda-water and it is transformed into salicylic acid, a white odorless powder, used as a preservative and as a rheumatism remedy. Add to this methyl alcohol which is obtained by the destructive distillation of wood and is much more poisonous than ordinary ethyl alcohol. The alcohol and the acid heated together will unite with the aid of a little sulfuric acid and we get what the chemist calls methyl salicylate and other people call oil of wintergreen, the same as is found in wintergreen berries and birch bark. We have inherited a taste for this from our pioneer ancestors and we use it extensively to flavor our soft drinks, gum, tooth paste and candy, but the Europeans have not yet found out how nice it is. But, starting with phenol again, let us heat it with caustic alkali and chloroform. This gives us two new compounds of the same composition, but differing a little in the order of the atoms. If you refer back to the diagram of the benzene ring which I gave in the last chapter, you will see that there are six hydrogen atoms attached to it. Now any or all these hydrogen atoms may be replaced by other elements or groups and what the product is depends not only on what the new elements are, but where they are put. It is like spelling words. The three letters _t_, _r_ and _a_ mean very different things according to whether they are put together as _art_, _tar_ or _rat_. Or, to take a more apposite illustration, every hostess knows that the success of her dinner depends upon how she seats her guests around the table. So in the case of aromatic compounds, a little difference in the seating arrangement around the benzene ring changes the character. The two derivatives of phenol, which we are now considering, have two substituting groups. One is--O-H (called the hydroxyl group). The other is--CHO (called the aldehyde group). If these are opposite (called the para position) we have an odorless white solid. If they are side by side (called the ortho position) we have an oil with the odor of meadowsweet. Treating the odorless solid with methyl alcohol we get audepine (or anisic aldehyde) which is the perfume of hawthorn blossoms. But treating the other of the twin products, the fragrant oil, with dry acetic acid ("Perkin's reaction") we get cumarin, which is the perfume part of the tonka or tonquin beans that our forefathers used to carry in their snuff boxes. One ounce of cumarin is equal to four pounds of tonka beans. It smells sufficiently like vanilla to be used as a substitute for it in cheap extracts. In perfumery it is known as "new mown hay." You may remember what I said on a former page about the career of William Henry Perkin, the boy who loved chemistry better than eating, and how he discovered the coal-tar dyes. Well, it is also to his ingenious mind that we owe the starting of the coal-tar perfume business which has had almost as important a development. Perkin made cumarin in 1868, but this, like the dye industry, escaped from English hands and flew over the North Sea. Before the war Germany was exporting $1,500,000 worth of synthetic perfumes a year. Part of these went to France, where they were mixed and put up in fancy bottles with French names and sold to Americans at fancy prices. The real vanilla flavor, vanillin, was made by Tiemann in 1874. At first it sold for nearly $800 a pound, but now it may be had for $10. How extensively it is now used in chocolate, ice cream, soda water, cakes and the like we all know. It should be noted that cumarin and vanillin, however they may be made, are not imitations, but identical with the chief constituent of the tonka and vanilla beans and, of course, are equally wholesome or harmless. But the nice palate can distinguish a richer flavor in the natural extracts, for they contain small quantities of other savory ingredients. A true perfume consists of a large number of odoriferous chemical compounds mixed in such proportions as to produce a single harmonious effect upon the sense of smell in a fine brand of perfume may be compounded a dozen or twenty different ingredients and these, if they are natural essences, are complex mixtures of a dozen or so distinct substances. Perfumery is one of the fine arts. The perfumer, like the orchestra leader, must know how to combine and coördinate his instruments to produce a desired sensation. A Wagnerian opera requires 103 musicians. A Strauss opera requires 112. Now if the concert manager wants to economize he will insist upon cutting down on the most expensive musicians and dropping out some of the others, say, the supernumerary violinists and the man who blows a single blast or tinkles a triangle once in the course of the evening. Only the trained ear will detect the difference and the manager can make more money. Suppose our mercenary impresario were unable to get into the concert hall of his famous rival. He would then listen outside the window and analyze the sound in this fashion: "Fifty per cent. of the sound is made by the tuba, 20 per cent. by the bass drum, 15 per cent. by the 'cello and 10 per cent. by the clarinet. There are some other instruments, but they are not loud and I guess if we can leave them out nobody will know the difference." So he makes up his orchestra out of these four alone and many people do not know the difference. The cheap perfumer goes about it in the same way. He analyzes, for instance, the otto or oil of roses which cost during the war $400 a pound--if you could get it at any price--and he finds that the chief ingredient is geraniol, costing only $5, and next is citronelol, costing $20; then comes nerol and others. So he makes up a cheap brand of perfumery out of three or four such compounds. But the genuine oil of roses, like other natural essences, contains a dozen or more constituents and to leave many of them out is like reducing an orchestra to a few loud-sounding instruments or a painting to a three-color print. A few years ago an attempt was made to make music electrically by producing separately each kind of sound vibration contained in the instruments imitated. Theoretically that seems easy, but practically the tone was not satisfactory because the tones and overtones of a full orchestra or even of a single violin are too numerous and complex to be reproduced individually. So the synthetic perfumes have not driven out the natural perfumes, but, on the contrary, have aided and stimulated the growth of flowers for essences. The otto or attar of roses, favorite of the Persian monarchs and romances, has in recent years come chiefly from Bulgaria. But wars are not made with rosewater and the Bulgars for the last five years have been engaged in other business than cultivating their own gardens. The alembic or still was invented by the Arabian alchemists for the purpose of obtaining the essential oil or attar of roses. But distillation, even with the aid of steam, is not altogether satisfactory. For instance, the distilled rose oil contains anywhere from 10 to 74 per cent. of a paraffin wax (stearopten) that is odorless and, on the other hand, phenyl-ethyl alcohol, which is an important constituent of the scent of roses, is broken up in the process of distillation. So the perfumer can improve on the natural or rather the distilled oil by leaving out part of the paraffin and adding the missing alcohol. Even the imported article taken direct from the still is not always genuine, for the wily Bulgar sometimes "increases the yield" by sprinkling his roses in the vat with synthetic geraniol just as the wily Italian pours a barrel of American cottonseed oil over his olives in the press. Another method of extracting the scent of flowers is by _enfleurage_, which takes advantage of the tendency of fats to absorb odors. You know how butter set beside fish in the ice box will get a fishy flavor. In _enfleurage_ moist air is carried up a tower passing alternately over trays of fresh flowers, say violets, and over glass plates covered with a thin layer of lard. The perfumed lard may then be used as a pomade or the perfume may be extracted by alcohol. But many sweet flowers do not readily yield an essential oil, so in such oases we have to rely altogether upon more or less successful substitutes. For instance, the perfumes sold under the names of "heliotrope," "lily of the valley," "lilac," "cyclamen," "honeysuckle," "sweet pea," "arbutus," "mayflower" and "magnolia" are not produced from these flowers but are simply imitations made from other essences, synthetic or natural. Among the "thousand flowers" that contribute to the "Eau de Mille Fleurs" are the civet cat, the musk deer and the sperm whale. Some of the published formulas for "Jockey Club" call for civet or ambergris and those of "Lavender Water" for musk and civet. The less said about the origin of these three animal perfumes the better. Fortunately they are becoming too expensive to use and are being displaced by synthetic products more agreeable to a refined imagination. The musk deer may now be saved from extinction since we can make tri-nitro-butyl-xylene from coal tar. This synthetic musk passes muster to human nostrils, but a cat will turn up her nose at it. The synthetic musk is not only much cheaper than the natural, but a dozen times as strong, or let us say, goes a dozen times as far, for nobody wants it any stronger. Such powerful scents as these are only pleasant when highly diluted, yet they are, as we have seen, essential ingredients of the finest perfumes. For instance, the natural oil of jasmine and other flowers contain traces of indols and skatols which have most disgusting odors. Though our olfactory organs cannot detect their presence yet we perceive their absence so they have to be put into the artificial perfume. Just so a brief but violent discord in a piece of music or a glaring color contrast in a painting may be necessary to the harmony of the whole. It is absurd to object to "artificial" perfumes, for practically all perfumes now sold are artificial in the sense of being compounded by the art of the perfumer and whether the materials he uses are derived from the flowers of yesteryear or of Carboniferous Era is nobody's business but his. And he does not tell. The materials can be purchased in the open market. Various recipes can be found in the books. But every famous perfumer guards well the secret of his formulas and hands it as a legacy to his posterity. The ancient Roman family of Frangipani has been made immortal by one such hereditary recipe. The Farina family still claims to have the exclusive knowledge of how to make Eau de Cologne. This famous perfume was first compounded by an Italian, Giovanni Maria Farina, who came to Cologne in 1709. It soon became fashionable and was for a time the only scent allowed at some of the German courts. The various published recipes contain from six to a dozen ingredients, chiefly the oils of neroli, rosemary, bergamot, lemon and lavender dissolved in very pure alcohol and allowed to age like wine. The invention, in 1895, of artificial neroli (orange flowers) has improved the product. French perfumery, like the German, had its origin in Italy, when Catherine de' Medici came to Paris as the bride of Henri II. She brought with her, among other artists, her perfumer, Sieur Toubarelli, who established himself in the flowery land of Grasse. Here for four hundred years the industry has remained rooted and the family formulas have been handed down from generation to generation. In the city of Grasse there were at the outbreak of the war fifty establishments making perfumes. The French perfumer does not confine himself to a single sense. He appeals as well to sight and sound and association. He adds to the attractiveness of his creation by a quaintly shaped bottle, an artistic box and an enticing name such as "Dans les Nues," "Le Coeur de Jeannette," "Nuit de Chine," "Un Air Embaumé," "Le Vertige," "Bon Vieux Temps," "L'Heure Bleue," "Nuit d'Amour," "Quelques Fleurs," "Djer-Kiss." The requirements of a successful scent are very strict. A perfume must be lasting, but not strong. All its ingredients must continue to evaporate in the same proportion, otherwise it will change odor and deteriorate. Scents kill one another as colors do. The minutest trace of some impurity or foreign odor may spoil the whole effect. To mix the ingredients in a vessel of any metal but aluminum or even to filter through a tin funnel is likely to impair the perfume. The odoriferous compounds are very sensitive and unstable bodies, otherwise they would have no effect upon the olfactory organ. The combination that would be suitable for a toilet water would not be good for a talcum powder and might spoil in a soap. Perfumery is used even in the "scentless" powders and soaps. In fact it is now used more extensively, if less intensively, than ever before in the history of the world. During the Unwashed Ages, commonly called the Dark Ages, between the destruction of the Roman baths and the construction of the modern bathroom, the art of the perfumer, like all the fine arts, suffered an eclipse. "The odor of sanctity" was in highest esteem and what that odor was may be imagined from reading the lives of the saints. But in the course of centuries the refinements of life began to seep back into Europe from the East by means of the Arabs and Crusaders, and chemistry, then chiefly the art of cosmetics, began to revive. When science, the greatest democratizing agent on earth, got into action it elevated the poor to the ranks of kings and priests in the delights of the palate and the nose. We should not despise these delights, for the pleasure they confer is greater, in amount at least, than that of the so-called higher senses. We eat three times a day; some of us drink oftener; few of us visit the concert hall or the art gallery as often as we do the dining room. Then, too, these primitive senses have a stronger influence upon our emotional nature than those acquired later in the course of evolution. As Kipling puts it: Smells are surer than sounds or sights To make your heart-strings crack. VI CELLULOSE Organic compounds, on which our life and living depend, consist chiefly of four elements: carbon, hydrogen, oxygen and nitrogen. These compounds are sometimes hard to analyze, but when once the chemist has ascertained their constitution he can usually make them out of their elements--if he wants to. He will not want to do it as a business unless it pays and it will not pay unless the manufacturing process is cheaper than the natural process. This depends primarily upon the cost of the crude materials. What, then, is the market price of these four elements? Oxygen and nitrogen are free as air, and as we have seen in the second chapter, their direct combination by the electric spark is possible. Hydrogen is free in the form of water but expensive to extricate by means of the electric current. But we need more carbon than anything else and where shall we get that? Bits of crystallized carbon can be picked up in South Africa and elsewhere, but those who can afford to buy them prefer to wear them rather than use them in making synthetic food. Graphite is rare and hard to melt. We must then have recourse to the compounds of carbon. The simplest of these, carbon dioxide, exists in the air but only four parts in ten thousand by volume. To extract the carbon and get it into combination with the other elements would be a difficult and expensive process. Here, then, we must call in cheap labor, the cheapest of all laborers, the plants. Pine trees on the highlands and cotton plants on the lowlands keep their green traps set all the day long and with the captured carbon dioxide build up cellulose. If, then, man wants free carbon he can best get it by charring wood in a kiln or digging up that which has been charred in nature's kiln during the Carboniferous Era. But there is no reason why he should want to go back to elemental carbon when he can have it already combined with hydrogen in the remains of modern or fossil vegetation. The synthetic products on which modern chemistry prides itself, such as vanillin, camphor and rubber, are not built up out of their elements, C, H and O, although they might be as a laboratory stunt. Instead of that the raw material of the organic chemist is chiefly cellulose, or the products of its recent or remote destructive distillation, tar and oil. It is unnecessary to tell the reader what cellulose is since he now holds a specimen of it in his hand, pretty pure cellulose except for the sizing and the specks of carbon that mar the whiteness of its surface. This utilization of cellulose is the chief cause of the difference between the modern world and the ancient, for what is called the invention of printing is essentially the inventing of paper. The Romans made type to stamp their coins and lead pipes with and if they had had paper to print upon the world might have escaped the Dark Ages. But the clay tablets of the Babylonians were cumbersome; the wax tablets of the Greeks were perishable; the papyrus of the Egyptians was fragile; parchment was expensive and penning was slow, so it was not until literature was put on a paper basis that democratic education became possible. At the present time sheepskin is only used for diplomas, treaties and other antiquated documents. And even if your diploma is written in Latin it is likely to be made of sulfated cellulose. The textile industry has followed the same law of development that I have indicated in the other industries. Here again we find the three stages of progress, (1) utilization of natural products, (2) cultivation of natural products, (3) manufacture of artificial products. The ancients were dependent upon plants, animals and insects for their fibers. China used silk, Greece and Rome used wool, Egypt used flax and India used cotton. In the course of cultivation for three thousand years the animal and vegetable fibers were lengthened and strengthened and cheapened. But at last man has risen to the level of the worm and can spin threads to suit himself. He can now rival the wasp in the making of paper. He is no longer dependent upon the flax and the cotton plant, but grinds up trees to get his cellulose. A New York newspaper uses up nearly 2000 acres of forest a year. The United States grinds up about five million cords of wood a year in the manufacture of pulp for paper and other purposes. In making "mechanical pulp" the blocks of wood, mostly spruce and hemlock, are simply pressed sidewise of the grain against wet grindstones. But in wood fiber the cellulose is in part combined with lignin, which is worse than useless. To break up the ligno-cellulose combine chemicals are used. The logs for this are not ground fine, but cut up by disk chippers. The chips are digested for several hours under heat and pressure with acid or alkali. There are three processes in vogue. In the most common process the reagent is calcium sulfite, made by passing sulfur fumes (SO_{2}) into lime water. In another process a solution of caustic of soda is used to disintegrate the wood. The third, known as the "sulfate" process, should rather be called the sulfide process since the active agent is an alkaline solution of sodium sulfide made by roasting sodium sulfate with the carbonaceous matter extracted from the wood. This sulfate process, though the most recent of the three, is being increasingly employed in this country, for by means of it the resinous pine wood of the South can be worked up and the final product, known as kraft paper because it is strong, is used for wrapping. But whatever the process we get nearly pure cellulose which, as you can see by examining this page under a microscope, consists of a tangled web of thin white fibers, the remains of the original cell walls. Owing to the severe treatment it has undergone wood pulp paper does not last so long as the linen rag paper used by our ancestors. The pages of the newspapers, magazines and books printed nowadays are likely to become brown and brittle in a few years, no great loss for the most part since they have served their purpose, though it is a pity that a few copies of the worst of them could not be printed on permanent paper for preservation in libraries so that future generations could congratulate themselves on their progress in civilization. But in our absorption in the printed page we must not forget the other uses of paper. The paper clothing, so often prophesied, has not yet arrived. Even paper collars have gone out of fashion--if they ever were in. In Germany during the war paper was used for socks, shirts and shoes as well as handkerchiefs and napkins but it could not stand wear and washing. Our sanitary engineers have set us to drinking out of sharp-edged paper cups and we blot our faces instead of wiping them. Twine is spun of paper and furniture made of the twine, a rival of rattan. Cloth and matting woven of paper yarn are being used for burlap and grass in the making of bags and suitcases. Here, however, we are not so much interested in manufactures of cellulose itself, that is, wood, paper and cotton, as we are in its chemical derivatives. Cellulose, as we can see from the symbol, C_{6}H_{10}O_{5}, is composed of the three elements of carbon, hydrogen and oxygen. These are present in the same proportion as in starch (C_{6}H_{10}O_{5}), while glucose or grape sugar (C_{6}H_{12}O_{6}) has one molecule of water more. But glucose is soluble in cold water and starch is soluble in hot, while cellulose is soluble in neither. Consequently cellulose cannot serve us for food, although some of the vegetarian animals, notably the goat, have a digestive apparatus that can handle it. In Finland and Germany birch wood pulp and straw were used not only as an ingredient of cattle food but also put into war bread. It is not likely, however, that the human stomach even under the pressure of famine is able to get much nutriment out of sawdust. But by digesting with dilute acid sawdust can be transformed into sugars and these by fermentation into alcohol, so it would be possible for a man after he has read his morning paper to get drunk on it. If the cellulose, instead of being digested a long time in dilute acid, is dipped into a solution of sulfuric acid (50 to 80 per cent.) and then washed and dried it acquires a hard, tough and translucent coating that makes it water-proof and grease-proof. This is the "parchment paper" that has largely replaced sheepskin. Strong alkali has a similar effect to strong acid. In 1844 John Mercer, a Lancashire calico printer, discovered that by passing cotton cloth or yarn through a cold 30 per cent. solution of caustic soda the fiber is shortened and strengthened. For over forty years little attention was paid to this discovery, but when it was found that if the material was stretched so that it could not shrink on drying the twisted ribbons of the cotton fiber were changed into smooth-walled cylinders like silk, the process came into general use and nowadays much that passes for silk is "mercerized" cotton. Another step was taken when Cross of London discovered that when the mercerized cotton was treated with carbon disulfide it was dissolved to a yellow liquid. This liquid contains the cellulose in solution as a cellulose xanthate and on acidifying or heating the cellulose is recovered in a hydrated form. If this yellow solution of cellulose is squirted out of tubes through extremely minute holes into acidulated water, each tiny stream becomes instantly solidified into a silky thread which may be spun and woven like that ejected from the spinneret of the silkworm. The origin of natural silk, if we think about it, rather detracts from the pleasure of wearing it, and if "he who needlessly sets foot upon a worm" is to be avoided as a friend we must hope that the advance of the artificial silk industry will be rapid enough to relieve us of the necessity of boiling thousands of baby worms in their cradles whenever we want silk stockings. On a plain rush hurdle a silkworm lay When a proud young princess came that way. The haughty daughter of a lordly king Threw a sidelong glance at the humble thing, Little thinking she walked in pride In the winding sheet where the silkworm died. But so far we have not reached a stage where we can altogether dispense with the services of the silkworm. The viscose threads made by the process look as well as silk, but they are not so strong, especially when wet. Besides the viscose method there are several other methods of getting cellulose into solution so that artificial fibers may be made from it. A strong solution of zinc chloride will serve and this process used to be employed for making the threads to be charred into carbon filaments for incandescent bulbs. Cellulose is also soluble in an ammoniacal solution of copper hydroxide. The liquid thus formed is squirted through a fine nozzle into a precipitating solution of caustic soda and glucose, which brings back the cellulose to its original form. In the chapter on explosives I explained how cellulose treated with nitric acid in the presence of sulfuric acid was nitrated. The cellulose molecule having three hydroxyl (--OH) groups, can take up one, two or three nitrate groups (--ONO_{2}). The higher nitrates are known as guncotton and form the basis of modern dynamite and smokeless powder. The lower nitrates, known as pyroxylin, are less explosive, although still very inflammable. All these nitrates are, like the original cellulose, insoluble in water, but unlike the original cellulose, soluble in a mixture of ether and alcohol. The solution is called collodion and is now in common use to spread a new skin over a wound. The great war might be traced back to Nobel's cut finger. Alfred Nobel was a Swedish chemist--and a pacifist. One day while working in the laboratory he cut his finger, as chemists are apt to do, and, again as chemists are apt to do, he dissolved some guncotton in ether-alcohol and swabbed it on the wound. At this point, however, his conduct diverges from the ordinary, for instead of standing idle, impatiently waving his hand in the air to dry the film as most people, including chemists, are apt to do, he put his mind on it and it occurred to him that this sticky stuff, slowly hardening to an elastic mass, might be just the thing he was hunting as an absorbent and solidifier of nitroglycerin. So instead of throwing away the extra collodion that he had made he mixed it with nitroglycerin and found that it set to a jelly. The "blasting gelatin" thus discovered proved to be so insensitive to shock that it could be safely transported or fired from a cannon. This was the first of the high explosives that have been the chief factor in modern warfare. But on the whole, collodion has healed more wounds than it has caused besides being of infinite service to mankind otherwise. It has made modern photography possible, for the film we use in the camera and moving picture projector consists of a gelatin coating on a pyroxylin backing. If collodion is forced through fine glass tubes instead of through a slit, it comes out a thread instead of a film. If the collodion jet is run into a vat of cold water the ether and alcohol dissolve; if it is run into a chamber of warm air they evaporate. The thread of nitrated cellulose may be rendered less inflammable by taking out the nitrate groups by treatment with ammonium or calcium sulfide. This restores the original cellulose, but now it is an endless thread of any desired thickness, whereas the native fiber was in size and length adapted to the needs of the cottonseed instead of the needs of man. The old motto, "If you want a thing done the way you want it you must do it yourself," explains why the chemist has been called in to supplement the work of nature in catering to human wants. Instead of nitric acid we may use strong acetic acid to dissolve the cotton. The resulting cellulose acetates are less inflammable than the nitrates, but they are more brittle and more expensive. Motion picture films made from them can be used in any hall without the necessity of imprisoning the operator in a fire-proof box where if anything happens he can burn up all by himself without disturbing the audience. The cellulose acetates are being used for auto goggles and gas masks as well as for windows in leather curtains and transparent coverings for index cards. A new use that has lately become important is the varnishing of aeroplane wings, as it does not readily absorb water or catch fire and makes the cloth taut and air-tight. Aeroplane wings can be made of cellulose acetate sheets as transparent as those of a dragon-fly and not easy to see against the sky. The nitrates, sulfates and acetates are the salts or esters of the respective acids, but recently true ethers or oxides of cellulose have been prepared that may prove still better since they contain no acid radicle and are neutral and stable. These are in brief the chief processes for making what is commonly but quite improperly called "artificial silk." They are not the same substance as silkworm silk and ought not to be--though they sometimes are--sold as such. They are none of them as strong as the silk fiber when wet, although if I should venture to say which of the various makes weakens the most on wetting I should get myself into trouble. I will only say that if you have a grudge against some fisherman give him a fly line of artificial silk, 'most any kind. The nitrate process was discovered by Count Hilaire de Chardonnet while he was at the Polytechnic School of Paris, and he devoted his life and his fortune trying to perfect it. Samples of the artificial silk were exhibited at the Paris Exposition in 1889 and two years later he started a factory at Basançon. In 1892, Cross and Bevan, English chemists, discovered the viscose or xanthate process, and later the acetate process. But although all four of these processes were invented in France and England, Germany reaped most benefit from the new industry, which was bringing into that country $6,000,000 a year before the war. The largest producer in the world was the Vereinigte Glanzstoff-Fabriken of Elberfeld, which was paying annual dividends of 34 per cent. in 1914. The raw materials, as may be seen, are cheap and abundant, merely cellulose, salt, sulfur, carbon, air and water. Any kind of cellulose can be used, cotton waste, rags, paper, or even wood pulp. The processes are various, the names of the products are numerous and the uses are innumerable. Even the most inattentive must have noticed the widespread employment of these new forms of cellulose. We can buy from a street barrow for fifteen cents near-silk neckties that look as well as those sold for seventy-five. As for wear--well, they all of them wear till after we get tired of wearing them. Paper "vulcanized" by being run through a 30 per cent. solution of zinc chloride and subjected to hydraulic pressure comes out hard and horny and may be used for trunks and suit cases. Viscose tubes for sausage containers are more sanitary and appetizing than the customary casings. Viscose replaces ramie or cotton in the Welsbach gas mantles. Viscose film, transparent and a thousandth of an inch thick (cellophane), serves for candy wrappers. Cellulose acetate cylinders spun out of larger orifices than silk are trying--not very successfully as yet--to compete with hog's bristles and horsehair. Stir powdered metals into the cellulose solution and you have the Bayko yarn. Bayko (from the manufacturers, Farbenfabriken vorm. Friedr. Bayer and Company) is one of those telescoped names like Socony, Nylic, Fominco, Alco, Ropeco, Ripans, Penn-Yan, Anzac, Dagor, Dora and Cadets, which will be the despair of future philologers. [Illustration: A PAPER MILL IN ACTION This photograph was taken in the barking room of the big pulp mill of the Great Northern Paper Company at Millinocket, Maine] [Illustration: CELLULOSE FROM WOOD PULP This is now made into a large variety of useful articles of which a few examples are here pictured] Soluble cellulose may enable us in time to dispense with the weaver as well as the silkworm. It may by one operation give us fabrics instead of threads. A machine has been invented for manufacturing net and lace, the liquid material being poured on one side of a roller and the fabric being reeled off on the other side. The process seems capable of indefinite extension and application to various sorts of woven, knit and reticulated goods. The raw material is cotton waste and the finished fabric is a good substitute for silk. As in the process of making artificial silk the cellulose is dissolved in a cupro-ammoniacal solution, but instead of being forced out through minute openings to form threads, as in that process, the paste is allowed to flow upon a revolving cylinder which is engraved with the pattern of the desired textile. A scraper removes the excess and the turning of the cylinder brings the paste in the engraved lines down into a bath which solidifies it. Tulle or net is now what is chiefly being turned out, but the engraved design may be as elaborate and artistic as desired, and various materials can be used. Since the threads wherever they cross are united, the fabric is naturally stronger than the ordinary. It is all of a piece and not composed of parts. In short, we seem to be on the eve of a revolution in textiles that is the same as that taking place in building materials. Our concrete structures, however great, are all one stone. They are not built up out of blocks, but cast as a whole. Lace has always been the aristocrat among textiles. It has maintained its exclusiveness hitherto by being based upon hand labor. In no other way could one get so much painful, patient toil put into such a light and portable form. A filmy thing twined about a neck or dropping from a wrist represented years of work by poor peasant girls or pallid, unpaid nuns. A visit to a lace factory, even to the public rooms where the wornout women were not to be seen, is enough to make one resolve never to purchase any such thing made by hand again. But our good resolutions do not last long and in time we forget the strained eyes and bowed backs, or, what is worse, value our bit of lace all the more because it means that some poor woman has put her life and health into it, netting and weaving, purling and knotting, twining and twisting, throwing and drawing, thread by thread, day after day, until her eyes can no longer see and her fingers have become stiffened. But man is not naturally cruel. He does not really enjoy being a slave driver, either of human or animal slaves, although he can be hardened to it with shocking ease if there seems no other way of getting what he wants. So he usually welcomes that Great Liberator, the Machine. He prefers to drive the tireless engine than to whip the straining horses. He had rather see the farmer riding at ease in a mowing machine than bending his back over a scythe. The Machine is not only the Great Liberator, it is the Great Leveler also. It is the most powerful of the forces for democracy. An aristocracy can hardly be maintained except by distinction in dress, and distinction in dress can only be maintained by sumptuary laws or costliness. Sumptuary laws are unconstitutional in this country, hence the stress laid upon costliness. But machinery tends to bring styles and fabrics within the reach of all. The shopgirl is almost as well dressed on the street as her rich customer. The man who buys ready-made clothing is only a few weeks behind the vanguard of the fashion. There is often no difference perceptible to the ordinary eye between cheap and high-priced clothing once the price tag is off. Jewels as a portable form of concentrated costliness have been in favor from the earliest ages, but now they are losing their factitious value through the advance of invention. Rubies of unprecedented size, not imitation, but genuine rubies, can now be manufactured at reasonable rates. And now we may hope that lace may soon be within the reach of all, not merely lace of the established forms, but new and more varied and intricate and beautiful designs, such as the imagination has been able to conceive, but the hand cannot execute. Dissolving nitrocellulose in ether and alcohol we get the collodion varnish that we are all familiar with since we have used it on our cut fingers. Spread it on cloth instead of your skin and it makes a very good leather substitute. As we all know to our cost the number of animals to be skinned has not increased so rapidly in recent years as the number of feet to be shod. After having gone barefoot for a million years or so the majority of mankind have decided to wear shoes and this change in fashion comes at a time, roughly speaking, when pasture land is getting scarce. Also there are books to be bound and other new things to be done for which leather is needed. The war has intensified the stringency; so has feminine fashion. The conventions require that the shoe-tops extend nearly to skirt-bottom and this means that an inch or so must be added to the shoe-top every year. Consequent to this rise in leather we have to pay as much for one shoe as we used to pay for a pair. Here, then, is a chance for Necessity to exercise her maternal function. And she has responded nobly. A progeny of new substances have been brought forth and, what is most encouraging to see, they are no longer trying to worm their way into favor as surreptitious surrogates under the names of "leatheret," "leatherine," "leatheroid" and "leather-this-or-that" but come out boldly under names of their own coinage and declare themselves not an imitation, not even a substitute, but "better than leather." This policy has had the curious result of compelling the cowhide men to take full pages in the magazines to call attention to the forgotten virtues of good old-fashioned sole-leather! There are now upon the market synthetic shoes that a vegetarian could wear with a clear conscience. The soles are made of some rubber composition; the uppers of cellulose fabric (canvas) coated with a cellulose solution such as I have described. Each firm keeps its own process for such substance a dead secret, but without prying into these we can learn enough to satisfy our legitimate curiosity. The first of the artificial fabrics was the old-fashioned and still indispensable oil-cloth, that is canvas painted or printed with linseed oil carrying the desired pigments. Linseed oil belongs to the class of compounds that the chemist calls "unsaturated" and the psychologist would call "unsatisfied." They take up oxygen from the air and become solid, hence are called the "drying oils," although this does not mean that they lose water, for they have not any to lose. Later, ground cork was mixed with the linseed oil and then it went by its Latin name, "linoleum." The next step was to cut loose altogether from the natural oils and use for the varnish a solution of some of the cellulose esters, usually the nitrate (pyroxylin or guncotton), more rarely the acetate. As a solvent the ether-alcohol mixture forming collodion was, as we have seen, the first to be employed, but now various other solvents are in use, among them castor oil, methyl alcohol, acetone, and the acetates of amyl or ethyl. Some of these will be recognized as belonging to the fruit essences that we considered in Chapter V, and doubtless most of us have perceived an odor as of over-ripe pears, bananas or apples mysteriously emanating from a newly lacquered radiator. With powdered bronze, imitation gold, aluminum or something of the kind a metallic finish can be put on any surface. Canvas coated or impregnated with such soluble cellulose gives us new flexible and durable fabrics that have other advantages over leather besides being cheaper and more abundant. Without such material for curtains and cushions the automobile business would have been sorely hampered. It promises to provide us with a book binding that will not crumble to powder in the course of twenty years. Linen collars may be water-proofed and possibly Dame Fashion--being a fickle lady--may some day relent and let us wear such sanitary and economical neckwear. For shoes, purses, belts and the like the cellulose varnish or veneer is usually colored and stamped to resemble the grain of any kind of leather desired, even snake or alligator. If instead of dissolving the cellulose nitrate and spreading it on fabric we combine it with camphor we get celluloid, a plastic solid capable of innumerable applications. But that is another story and must be reserved for the next chapter. But before leaving the subject of cellulose proper I must refer back again to its chief source, wood. We inherited from the Indians a well-wooded continent. But the pioneer carried an ax on his shoulder and began using it immediately. For three hundred years the trees have been cut down faster than they could grow, first to clear the land, next for fuel, then for lumber and lastly for paper. Consequently we are within sight of a shortage of wood as we are of coal and oil. But the coal and oil are irrecoverable while the wood may be regrown, though it would require another three hundred years and more to grow some of the trees we have cut down. For fuel a pound of coal is about equal to two pounds of wood, and a pound of gasoline to three pounds of wood in heating value, so there would be a great loss in efficiency and economy if the world had to go back to a wood basis. But when that time shall come, as, of course, it must come some time, the wood will doubtless not be burned in its natural state but will be converted into hydrogen and carbon monoxide in a gas producer or will be distilled in closed ovens giving charcoal and gas and saving the by-products, the tar and acid liquors. As it is now the lumberman wastes two-thirds of every tree he cuts down. The rest is left in the forest as stump and tops or thrown out at the mill as sawdust and slabs. The slabs and other scraps may be used as fuel or worked up into small wood articles like laths and clothes-pins. The sawdust is burned or left to rot. But it is possible, although it may not be profitable, to save all this waste. In a former chapter I showed the advantages of the introduction of by-product coke-ovens. The same principle applies to wood as to coal. If a cord of wood (128 cubic feet) is subjected to a process of destructive distillation it yields about 50 bushels of charcoal, 11,500 cubic feet of gas, 25 gallons of tar, 10 gallons of crude wood alcohol and 200 pounds of crude acetate of lime. Resinous woods such as pine and fir distilled with steam give turpentine and rosin. The acetate of lime gives acetic acid and acetone. The wood (methyl) alcohol is almost as useful as grain (ethyl) alcohol in arts and industry and has the advantage of killing off those who drink it promptly instead of slowly. The chemist is an economical soul. He is never content until he has converted every kind of waste product into some kind of profitable by-product. He now has his glittering eye fixed upon the mountains of sawdust that pile up about the lumber mills. He also has a notion that he can beat lumber for some purposes. VII SYNTHETIC PLASTICS In the last chapter I told how Alfred Nobel cut his finger and, daubing it over with collodion, was led to the discovery of high explosive, dynamite. I remarked that the first part of this process--the hurting and the healing of the finger--might happen to anybody but not everybody would be led to discovery thereby. That is true enough, but we must not think that the Swedish chemist was the only observant man in the world. About this same time a young man in Albany, named John Wesley Hyatt, got a sore finger and resorted to the same remedy and was led to as great a discovery. His father was a blacksmith and his education was confined to what he could get at the seminary of Eddytown, New York, before he was sixteen. At that age he set out for the West to make his fortune. He made it, but after a long, hard struggle. His trade of typesetter gave him a living in Illinois, New York or wherever he wanted to go, but he was not content with his wages or his hours. However, he did not strike to reduce his hours or increase his wages. On the contrary, he increased his working time and used it to increase his income. He spent his nights and Sundays in making billiard balls, not at all the sort of thing you would expect of a young man of his Christian name. But working with billiard balls is more profitable than playing with them--though that is not the sort of thing you would expect a man of my surname to say. Hyatt had seen in the papers an offer of a prize of $10,000 for the discovery of a satisfactory substitute for ivory in the making of billiard balls and he set out to get that prize. I don't know whether he ever got it or not, but I have in my hand a newly published circular announcing that Mr. Hyatt has now perfected a process for making billiard balls "better than ivory." Meantime he has turned out several hundred other inventions, many of them much more useful and profitable, but I imagine that he takes less satisfaction in any of them than he does in having solved the problem that he undertook fifty years ago. The reason for the prize was that the game on the billiard table was getting more popular and the game in the African jungle was getting scarcer, especially elephants having tusks more than 2-7/16 inches in diameter. The raising of elephants is not an industry that promises as quick returns as raising chickens or Belgian hares. To make a ball having exactly the weight, color and resiliency to which billiard players have become accustomed seemed an impossibility. Hyatt tried compressed wood, but while he did not succeed in making billiard balls he did build up a profitable business in stamped checkers and dominoes. Setting type in the way they did it in the sixties was hard on the hands. And if the skin got worn thin or broken the dirty lead type were liable to infect the fingers. One day in 1863 Hyatt, finding his fingers were getting raw, went to the cupboard where was kept the "liquid cuticle" used by the printers. But when he got there he found it was bare, for the vial had tipped over--you know how easily they tip over--and the collodion had run out and solidified on the shelf. Possibly Hyatt was annoyed, but if so he did not waste time raging around the office to find out who tipped over that bottle. Instead he pulled off from the wood a bit of the dried film as big as his thumb nail and examined it with that "'satiable curtiosity," as Kipling calls it, which is characteristic of the born inventor. He found it tough and elastic and it occurred to him that it might be worth $10,000. It turned out to be worth many times that. Collodion, as I have explained in previous chapters, is a solution in ether and alcohol of guncotton (otherwise known as pyroxylin or nitrocellulose), which is made by the action of nitric acid on cotton. Hyatt tried mixing the collodion with ivory powder, also using it to cover balls of the necessary weight and solidity, but they did not work very well and besides were explosive. A Colorado saloon keeper wrote in to complain that one of the billiard players had touched a ball with a lighted cigar, which set it off and every man in the room had drawn his gun. The trouble with the dissolved guncotton was that it could not be molded. It did not swell up and set; it merely dried up and shrunk. When the solvent evaporated it left a wrinkled, shriveled, horny film, satisfactory to the surgeon but not to the man who wanted to make balls and hairpins and knife handles out of it. In England Alexander Parkes began working on the problem in 1855 and stuck to it for ten years before he, or rather his backers, gave up. He tried mixing in various things to stiffen up the pyroxylin. Of these, camphor, which he tried in 1865, worked the best, but since he used castor oil to soften the mass articles made of "parkesine" did not hold up in all weathers. Another Englishman, Daniel Spill, an associate of Parkes, took up the problem where he had dropped it and turned out a better product, "xylonite," though still sticking to the idea that castor oil was necessary to get the two solids, the guncotton and the camphor, together. But Hyatt, hearing that camphor could be used and not knowing enough about what others had done to follow their false trails, simply mixed his camphor and guncotton together without any solvent and put the mixture in a hot press. The two solids dissolved one another and when the press was opened there was a clear, solid, homogeneous block of--what he named--"celluloid." The problem was solved and in the simplest imaginable way. Tissue paper, that is, cellulose, is treated with nitric acid in the presence of sulfuric acid. The nitration is not carried so far as to produce the guncotton used in explosives but only far enough to make a soluble nitrocellulose or pyroxylin. This is pulped and mixed with half the quantity of camphor, pressed into cakes and dried. If this mixture is put into steam-heated molds and subjected to hydraulic pressure it takes any desired form. The process remains essentially the same as was worked out by the Hyatt brothers in the factory they set up in Newark in 1872 and some of their original machines are still in use. But this protean plastic takes innumerable forms and almost as many names. Each factory has its own secrets and lays claim to peculiar merits. The fundamental product itself is not patented, so trade names are copyrighted to protect the product. I have already mentioned three, "parkesine," "xylonite" and "celluloid," and I may add, without exhausting the list of species belonging to this genus, "viscoloid," "lithoxyl," "fiberloid," "coraline," "eburite," "pulveroid," "ivorine," "pergamoid," "duroid," "ivortus," "crystalloid," "transparene," "litnoid," "petroid," "pasbosene," "cellonite" and "pyralin." Celluloid can be given any color or colors by mixing in aniline dyes or metallic pigments. The color may be confined to the surface or to the interior or pervade the whole. If the nitrated tissue paper is bleached the celluloid is transparent or colorless. In that case it is necessary to add an antacid such as urea to prevent its getting yellow or opaque. To make it opaque and less inflammable oxides or chlorides of zinc, aluminum, magnesium, etc., are mixed in. Without going into the question of their variations and relative merits we may consider the advantages of the pyroxylin plastics in general. Here we have a new substance, the product of the creative genius of man, and therefore adaptable to his needs. It is hard but light, tough but elastic, easily made and tolerably cheap. Heated to the boiling point of water it becomes soft and flexible. It can be turned, carved, ground, polished, bent, pressed, stamped, molded or blown. To make a block of any desired size simply pile up the sheets and put them in a hot press. To get sheets of any desired thickness, simply shave them off the block. To make a tube of any desired size, shape or thickness squirt out the mixture through a ring-shaped hole or roll the sheets around a hot bar. Cut the tube into sections and you have rings to be shaped and stamped into box bodies or napkin rings. Print words or pictures on a celluloid sheet, put a thin transparent sheet over it and weld them together, then you have something like the horn book of our ancestors, but better. Nowadays such things as celluloid and pyralin can be sold under their own name, but in the early days the artificial plastics, like every new thing, had to resort to _camouflage_, a very humiliating expedient since in some cases they were better than the material they were forced to imitate. Tortoise shell, for instance, cracks, splits and twists, but a "tortoise shell" comb of celluloid looks as well and lasts better. Horn articles are limited to size of the ceratinous appendages that can be borne on the animal's head, but an imitation of horn can be made of any thickness by wrapping celluloid sheets about a cone. Ivory, which also has a laminated structure, may be imitated by rolling together alternate white opaque and colorless translucent sheets. Some of the sheets are wrinkled in order to produce the knots and irregularities of the grain of natural ivory. Man's chief difficulty in all such work is to imitate the imperfections of nature. His whites are too white, his surfaces are too smooth, his shapes are too regular, his products are too pure. The precious red coral of the Mediterranean can be perfectly imitated by taking a cast of a coral branch and filling in the mold with celluloid of the same color and hardness. The clear luster of amber, the dead black of ebony, the cloudiness of onyx, the opalescence of alabaster, the glow of carnelian--once confined to the selfish enjoyment of the rich--are now within the reach of every one, thanks to this chameleon material. Mosaics may be multiplied indefinitely by laying together sheets and sticks of celluloid, suitably cut and colored to make up the picture, fusing the mass, and then shaving off thin layers from the end. That _chef d'oeuvre_ of the Venetian glass makers, the Battle of Isus, from the House of the Faun in Pompeii, can be reproduced as fast as the machine can shave them off the block. And the tesserae do not fall out like those you bought on the Rialto. The process thus does for mosaics, ivory and coral what printing does for pictures. It is a mechanical multiplier and only by such means can we ever attain to a state of democratic luxury. The product, in cases where the imitation is accurate, is equally valuable except to those who delight in thinking that coral insects, Italian craftsmen and elephants have been laboring for years to put a trinket into their hands. The Lord may be trusted to deal with such selfish souls according to their deserts. But it is very low praise for a synthetic product that it can pass itself off, more or less acceptably, as a natural product. If that is all we could do without it. It must be an improvement in some respects on anything to be found in nature or it does not represent a real advance. So celluloid and its congeners are not confined to the shapes of shell and coral and crystal, or to the grain of ivory and wood and horn, the colors of amber and amethyst and lapis lazuli, but can be given forms and textures and tints that were never known before 1869. Let me see now, have I mentioned all the uses of celluloid? Oh, no, there are handles for canes, umbrellas, mirrors and brushes, knives, whistles, toys, blown animals, card cases, chains, charms, brooches, badges, bracelets, rings, book bindings, hairpins, campaign buttons, cuff and collar buttons, cuffs, collars and dickies, tags, cups, knobs, paper cutters, picture frames, chessmen, pool balls, ping pong balls, piano keys, dental plates, masks for disfigured faces, penholders, eyeglass frames, goggles, playing cards--and you can carry on the list as far as you like. Celluloid has its disadvantages. You may mold, you may color the stuff as you will, the scent of the camphor will cling around it still. This is not usually objectionable except where the celluloid is trying to pass itself off for something else, in which case it deserves no sympathy. It is attacked and dissolved by hot acids and alkalies. It softens up when heated, which is handy in shaping it though not so desirable afterward. But the worst of its failings is its combustibility. It is not explosive, but it takes fire from a flame and burns furiously with clouds of black smoke. But celluloid is only one of many plastic substances that have been introduced to the present generation. A new and important group of them is now being opened up, the so-called "condensation products." If you will take down any old volume of chemical research you will find occasionally words to this effect: "The reaction resulted in nothing but an insoluble resin which was not further investigated." Such a passage would be marked with a tear if chemists were given to crying over their failures. For it is the epitaph of a buried hope. It likely meant the loss of months of labor. The reason the chemist did not do anything further with the gummy stuff that stuck up his test tube was because he did not know what to do with it. It could not be dissolved, it could not be crystallized, it could not be distilled, therefore it could not be purified, analyzed and identified. What had happened was in most cases this. The molecule of the compound that the chemist was trying to make had combined with others of its kind to form a molecule too big to be managed by such means. Financiers call the process a "merger." Chemists call it "polymerization." The resin was a molecular trust, indissoluble, uncontrollable and contaminating everything it touched. But chemists--like governments--have learned wisdom in recent years. They have not yet discovered in all cases how to undo the process of polymerization, or, if you prefer the financial phrase, how to unscramble the eggs. But they have found that these molecular mergers are very useful things in their way. For instance there is a liquid known as isoprene (C_{5}H_{8}). This on heating or standing turns into a gum, that is nothing less than rubber, which is some multiple of C_{5}H_{8}. For another instance there is formaldehyde, an acrid smelling gas, used as a disinfectant. This has the simplest possible formula for a carbohydrate, CH_{2}O. But in the leaf of a plant this molecule multiplies itself by six and turns into a sweet solid glucose (C_{6}H_{12}O_{6}), or with the loss of water into starch (C_{6}H_{10}O_{5}) or cellulose (C_{6}H_{10}O_{5}). But formaldehyde is so insatiate that it not only combines with itself but seizes upon other substances, particularly those having an acquisitive nature like its own. Such a substance is carbolic acid (phenol) which, as we all know, is used as a disinfectant like formaldehyde because it, too, has the power of attacking decomposable organic matter. Now Prof. Adolf von Baeyer discovered in 1872 that when phenol and formaldehyde were brought into contact they seized upon one another and formed a combine of unusual tenacity, that is, a resin. But as I have said, chemists in those days were shy of resins. Kleeberg in 1891 tried to make something out of it and W.H. Story in 1895 went so far as to name the product "resinite," but nothing came of it until 1909 when L.H. Baekeland undertook a serious and systematic study of this reaction in New York. Baekeland was a Belgian chemist, born at Ghent in 1863 and professor at Bruges. While a student at Ghent he took up photography as a hobby and began to work on the problem of doing away with the dark-room by producing a printing paper that could be developed under ordinary light. When he came over to America in 1889 he brought his idea with him and four years later turned out "Velox," with which doubtless the reader is familiar. Velox was never patented because, as Dr. Baekeland explained in his speech of acceptance of the Perkin medal from the chemists of America, lawsuits are too expensive. Manufacturers seem to be coming generally to the opinion that a synthetic name copyrighted as a trademark affords better protection than a patent. Later Dr. Baekeland turned his attention to the phenol condensation products, working gradually up from test tubes to ton vats according to his motto: "Make your mistakes on a small scale and your profits on a large scale." He found that when equal weights of phenol and formaldehyde were mixed and warmed in the presence of an alkaline catalytic agent the solution separated into two layers, the upper aqueous and the lower a resinous precipitate. This resin was soft, viscous and soluble in alcohol or acetone. But if it was heated under pressure it changed into another and a new kind of resin that was hard, inelastic, unplastic, infusible and insoluble. The chemical name of this product is "polymerized oxybenzyl methylene glycol anhydride," but nobody calls it that, not even chemists. It is called "Bakelite" after its inventor. The two stages in its preparation are convenient in many ways. For instance, porous wood may be soaked in the soft resin and then by heat and pressure it is changed to the bakelite form and the wood comes out with a hard finish that may be given the brilliant polish of Japanese lacquer. Paper, cardboard, cloth, wood pulp, sawdust, asbestos and the like may be impregnated with the resin, producing tough and hard material suitable for various purposes. Brass work painted with it and then baked at 300° F. acquires a lacquered surface that is unaffected by soap. Forced in powder or sheet form into molds under a pressure of 1200 to 2000 pounds to the square inch it takes the most delicate impressions. Billiard balls of bakelite are claimed to be better than ivory because, having no grain, they do not swell unequally with heat and humidity and so lose their sphericity. Pipestems and beads of bakelite have the clear brilliancy of amber and greater strength. Fountain pens made of it are transparent so you can see how much ink you have left. A new and enlarging field for bakelite and allied products is the making of noiseless gears for automobiles and other machinery, also of air-plane propellers. Celluloid is more plastic and elastic than bakelite. It is therefore more easily worked in sheets and small objects. Celluloid can be made perfectly transparent and colorless while bakelite is confined to the range between a clear amber and an opaque brown or black. On the other hand bakelite has the advantage in being tasteless, odorless, inert, insoluble and non-inflammable. This last quality and its high electrical resistance give bakelite its chief field of usefulness. Electricity was discovered by the Greeks, who found that amber (_electron_) when rubbed would pick up straws. This means simply that amber, like all such resinous substances, natural or artificial, is a non-conductor or di-electric and does not carry off and scatter the electricity collected on the surface by the friction. Bakelite is used in its liquid form for impregnating coils to keep the wires from shortcircuiting and in its solid form for commutators, magnetos, switch blocks, distributors, and all sorts of electrical apparatus for automobiles, telephones, wireless telegraphy, electric lighting, etc. Bakelite, however, is only one of an indefinite number of such condensation products. As Baeyer said long ago: "It seems that all the aldehydes will, under suitable circumstances, unite with the aromatic hydrocarbons to form resins." So instead of phenol, other coal tar products such as cresol, naphthol or benzene itself may be used. The carbon links (-CH_{2}-, methylene) necessary to hook these carbon rings together may be obtained from other substances than the aldehydes, for instance from the amines, or ammonia derivatives. Three chemists, L.V. Kedman, A.J. Weith and F.P. Broek, working in 1910 on the Industrial Fellowships of the late Robert Kennedy Duncan at the University of Kansas, developed a process using formin instead of formaldehyde. Formin--or, if you insist upon its full name, hexa-methylene-tetramine--is a sugar-like substance with a fish-like smell. This mixed with crystallized carbolic acid and slightly warmed melts to a golden liquid that sets on pouring into molds. It is still plastic and can be bent into any desired shape, but on further heating it becomes hard without the need of pressure. Ammonia is given off in this process instead of water which is the by-product in the case of formaldehyde. The product is similar to bakelite, exactly how similar is a question that the courts will have to decide. The inventors threatened to call it Phenyl-endeka-saligeno-saligenin, but, rightly fearing that this would interfere with its salability, they have named it "redmanol." A phenolic condensation product closely related to bakelite and redmanol is condensite, the invention of Jonas Walter Aylesworth. Aylesworth was trained in what he referred to as "the greatest university of the world, the Edison laboratory." He entered this university at the age of nineteen at a salary of $3 a week, but Edison soon found that he had in his new boy an assistant who could stand being shut up in the laboratory working day and night as long as he could. After nine years of close association with Edison he set up a little laboratory in his own back yard to work out new plastics. He found that by acting on naphthalene--the moth-ball stuff--with chlorine he got a series of useful products called "halowaxes." The lower chlorinated products are oils, which may be used for impregnating paper or soft wood, making it non-inflammable and impregnable to water. If four atoms of chlorine enter the naphthalene molecule the product is a hard wax that rings like a metal. Condensite is anhydrous and infusible, and like its rivals finds its chief employment in the insulation parts of electrical apparatus. The records of the Edison phonograph are made of it. So are the buttons of our blue-jackets. The Government at the outbreak of the war ordered 40,000 goggles in condensite frames to protect the eyes of our gunners from the glare and acid fumes. The various synthetics played an important part in the war. According to an ancient military pun the endurance of soldiers depends upon the strength of their soles. The new compound rubber soles were found useful in our army and the Germans attribute their success in making a little leather go a long way during the late war to the use of a new synthetic tanning material known as "neradol." There are various forms of this. Some are phenolic condensation products of formaldehyde like those we have been considering, but some use coal-tar compounds having no phenol groups, such as naphthalene sulfonic acid. These are now being made in England under such names as "paradol," "cresyntan" and "syntan." They have the advantage of the natural tannins such as bark in that they are of known strength and can be varied to suit. This very grasping compound, formaldehyde, will attack almost anything, even molecules many times its size. Gelatinous and albuminous substances of all sorts are solidified by it. Glue, skimmed milk, blood, eggs, yeast, brewer's slops, may by this magic agent be rescued from waste and reappear in our buttons, hairpins, roofing, phonographs, shoes or shoe-polish. The French have made great use of casein hardened by formaldehyde into what is known as "galalith" (i.e., milkstone). This is harder than celluloid and non-inflammable, but has the disadvantages of being more brittle and of absorbing moisture. A mixture of casein and celluloid has something of the merits of both. The Japanese, as we should expect, are using the juice of the soy bean, familiar as a condiment to all who patronize chop-sueys or use Worcestershire sauce. The soy glucine coagulated by formalin gives a plastic said to be better and cheaper than celluloid. Its inventor, S. Sato, of Sendai University, has named it, according to American precedent, "Satolite," and has organized a million-dollar Satolite Company at Mukojima. The algin extracted from the Pacific kelp can be used as a rubber surrogate for water-proofing cloth. When combined with heavier alkaline bases it forms a tough and elastic substance that can be rolled into transparent sheets like celluloid or turned into buttons and knife handles. In Australia when the war shut off the supply of tin the Government commission appointed to devise means of preserving fruits recommended the use of cardboard containers varnished with "magramite." This is a name the Australians coined for synthetic resin made from phenol and formaldehyde like bakelite. Magramite dissolved in alcohol is painted on the cardboard cans and when these are stoved the coating becomes insoluble. Tarasoff has made a series of condensation products from phenol and formaldehyde with the addition of sulfonated oils. These are formed by the action of sulfuric acid on coconut, castor, cottonseed or mineral oils. The products of this combination are white plastics, opaque, insoluble and infusible. Since I am here chiefly concerned with "Creative Chemistry," that is, with the art of making substances not found in nature, I have not spoken of shellac, asphaltum, rosin, ozocerite and the innumerable gums, resins and waxes, animal, mineral and vegetable, that are used either by themselves or in combination with the synthetics. What particular "dope" or "mud" is used to coat a canvas or form a telephone receiver is often hard to find out. The manufacturer finds secrecy safer than the patent office and the chemist of a rival establishment is apt to be baffled in his attempt to analyze and imitate. But we of the outside world are not concerned with this, though we are interested in the manifold applications of these new materials. There seems to be no limit to these compounds and every week the journals report new processes and patents. But we must not allow the new ones to crowd out the remembrance of the oldest and most famous of the synthetic plasters, hard rubber, to which a separate chapter must be devoted. VIII THE RACE FOR RUBBER There is one law that regulates all animate and inanimate things. It is formulated in various ways, for instance: Running down a hill is easy. In Latin it reads, _facilis descensus Averni._ Herbert Spencer calls it the dissolution of definite coherent heterogeneity into indefinite incoherent homogeneity. Mother Goose expresses it in the fable of Humpty Dumpty, and the business man extracts the moral as, "You can't unscramble an egg." The theologian calls it the dogma of natural depravity. The physicist calls it the second law of thermodynamics. Clausius formulates it as "The entropy of the world tends toward a maximum." It is easier to smash up than to build up. Children find that this is true of their toys; the Bolsheviki have found that it is true of a civilization. So, too, the chemist knows analysis is easier than synthesis and that creative chemistry is the highest branch of his art. This explains why chemists discovered how to take rubber apart over sixty years before they could find out how to put it together. The first is easy. Just put some raw rubber into a retort and heat it. If you can stand the odor you will observe the caoutchouc decomposing and a benzine-like liquid distilling over. This is called "isoprene." Any Freshman chemist could write the reaction for this operation. It is simply C_{10}H_{16} --> 2C_{5}H_{8} caoutchouc isoprene That is, one molecule of the gum splits up into two molecules of the liquid. It is just as easy to write the reaction in the reverse directions, as 2 isoprene--> 1 caoutchouc, but nobody could make it go in that direction. Yet it could be done. It had been done. But the man who did it did not know how he did it and could not do it again. Professor Tilden in May, 1892, read a paper before the Birmingham Philosophical Society in which he said: I was surprised a few weeks ago at finding the contents of the bottles containing isoprene from turpentine entirely changed in appearance. In place of a limpid, colorless liquid the bottles contained a dense syrup in which were floating several large masses of a yellowish color. Upon examination this turned out to be India rubber. But neither Professor Tilden nor any one else could repeat this accidental metamorphosis. It was tantalizing, for the world was willing to pay $2,000,000,000 a year for rubber and the forests of the Amazon and Congo were failing to meet the demand. A large share of these millions would have gone to any chemist who could find out how to make synthetic rubber and make it cheaply enough. With such a reward of fame and fortune the competition among chemists was intense. It took the form of an international contest in which England and Germany were neck and neck. [Illustration: Courtesy of the "India Rubber World." What goes into rubber and what is made out of it] The English, who had been beaten by the Germans in the dye business where they had the start, were determined not to lose in this. Prof. W.H. Perkin, of Manchester University, was one of the most eager, for he was inspired by a personal grudge against the Germans as well as by patriotism and scientific zeal. It was his father who had, fifty years before, discovered mauve, the first of the anilin dyes, but England could not hold the business and its rich rewards went over to Germany. So in 1909 a corps of chemists set to work under Professor Perkin in the Manchester laboratories to solve the problem of synthetic rubber. What reagent could be found that would reverse the reaction and convert the liquid isoprene into the solid rubber? It was discovered, by accident, we may say, but it should be understood that such advantageous accidents happen only to those who are working for them and know how to utilize them. In July, 1910, Dr. Matthews, who had charge of the research, set some isoprene to drying over metallic sodium, a common laboratory method of freeing a liquid from the last traces of water. In September he found that the flask was filled with a solid mass of real rubber instead of the volatile colorless liquid he had put into it. Twenty years before the discovery would have been useless, for sodium was then a rare and costly metal, a little of it in a sealed glass tube being passed around the chemistry class once a year as a curiosity, or a tiny bit cut off and dropped in water to see what a fuss it made. But nowadays metallic sodium is cheaply produced by the aid of electricity. The difficulty lay rather in the cost of the raw material, isoprene. In industrial chemistry it is not sufficient that a thing can be made; it must be made to pay. Isoprene could be obtained from turpentine, but this was too expensive and limited in supply. It would merely mean the destruction of pine forests instead of rubber forests. Starch was finally decided upon as the best material, since this can be obtained for about a cent a pound from potatoes, corn and many other sources. Here, however, the chemist came to the end of his rope and had to call the bacteriologist to his aid. The splitting of the starch molecule is too big a job for man; only the lower organisms, the yeast plant, for example, know enough to do that. Owing perhaps to the _entente cordiale_ a French biologist was called into the combination, Professor Fernbach, of the Pasteur Institute, and after eighteen months' hard work he discovered a process of fermentation by which a large amount of fusel oil can be obtained from any starchy stuff. Hitherto the aim in fermentation and distillation had been to obtain as small a proportion of fusel as possible, for fusel oil is a mixture of the heavier alcohols, all of them more poisonous and malodorous than common alcohol. But here, as has often happened in the history of industrial chemistry, the by-product turned out to be more valuable than the product. From fusel oil by the use of chlorine isoprene can be prepared, so the chain was complete. But meanwhile the Germans had been making equal progress. In 1905 Prof. Karl Harries, of Berlin, found out the name of the caoutchouc molecule. This discovery was to the chemists what the architect's plan of a house is to the builder. They knew then what they were trying to construct and could go about their task intelligently. Mark Twain said that he could understand something about how astronomers could measure the distance of the planets, calculate their weights and so forth, but he never could see how they could find out their names even with the largest telescopes. This is a joke in astronomy but it is not in chemistry. For when the chemist finds out the structure of a compound he gives it a name which means that. The stuff came to be called "caoutchouc," because that was the way the Spaniards of Columbus's time caught the Indian word "cahuchu." When Dr. Priestley called it "India rubber" he told merely where it came from and what it was good for. But when Harries named it "1-5-dimethyl-cyclo-octadien-1-5" any chemist could draw a picture of it and give a guess as to how it could be made. Even a person without any knowledge of chemistry can get the main point of it by merely looking at this diagram: C C C---C || || || | C--C C C--C C | | --> | | C C--C C C--C || || | || C C C---C [Illustration: isoprene _turns into_ caoutchouc] I have dropped the 16 H's or hydrogen atoms of the formula for simplicity's sake. They simply hook on wherever they can. You will see that the isoprene consists of a chain of four carbon atoms (represented by the C's) with an extra carbon on the side. In the transformation of this colorless liquid into soft rubber two of the double linkages break and so permit the two chains of 4 C's to unite to form one ring of eight. If you have ever played ring-around-a-rosy you will get the idea. In Chapter IV I explained that the anilin dyes are built up upon the benzene ring of six carbon atoms. The rubber ring consists of eight at least and probably more. Any substance containing that peculiar carbon chain with two double links C=C-C=C can double up--polymerize, the chemist calls it--into a rubber-like substance. So we may have many kinds of rubber, some of which may prove to be more useful than that which happens to be found in nature. With the structural formula of Harries as a clue chemists all over the world plunged into the problem with renewed hope. The famous Bayer dye works at Elberfeld took it up and there in August, 1909, Dr. Fritz Hofmann worked out a process for the converting of pure isoprene into rubber by heat. Then in 1910 Harries happened upon the same sodium reaction as Matthews, but when he came to get it patented he found that the Englishman had beaten him to the patent office by a few weeks. This Anglo-German rivalry came to a dramatic climax in 1912 at the great hall of the College of the City of New York when Dr. Carl Duisberg, of the Elberfeld factory, delivered an address on the latest achievements of the chemical industry before the Eighth--and the last for a long time--International Congress of Applied Chemistry. Duisberg insisted upon talking in German, although more of his auditors would have understood him in English. He laid full emphasis upon German achievements and cast doubt upon the claim of "the Englishman Tilden" to have prepared artificial rubber in the eighties. Perkin, of Manchester, confronted him with his new process for making rubber from potatoes, but Duisberg countered by proudly displaying two automobile tires made of synthetic rubber with which he had made a thousand-mile run. The intense antagonism between the British and German chemists at this congress was felt by all present, but we did not foresee that in two years from that date they would be engaged in manufacturing poison gas to fire at one another. It was, however, realized that more was at stake than personal reputation and national prestige. Under pressure of the new demand for automobiles the price of rubber jumped from $1.25 to $3 a pound in 1910, and millions had been invested in plantations. If Professor Perkin was right when he told the congress that by his process rubber could be made for less than 25 cents a pound it meant that these plantations would go the way of the indigo plantations when the Germans succeeded in making artificial indigo. If Dr. Duisberg was right when he told the congress that synthetic rubber would "certainly appear on the market in a very short time," it meant that Germany in war or peace would become independent of Brazil in the matter of rubber as she had become independent of Chile in the matter of nitrates. As it turned out both scientists were too sanguine. Synthetic rubber has not proved capable of displacing natural rubber by underbidding it nor even of replacing natural rubber when this is shut out. When Germany was blockaded and the success of her armies depended on rubber, price was no object. Three Danish sailors who were caught by United States officials trying to smuggle dental rubber into Germany confessed that they had been selling it there for gas masks at $73 a pound. The German gas masks in the latter part of the war were made without rubber and were frail and leaky. They could not have withstood the new gases which American chemists were preparing on an unprecedented scale. Every scrap of old rubber in Germany was saved and worked over and over and diluted with fillers and surrogates to the limit of elasticity. Spring tires were substituted for pneumatics. So it is evident that the supply of synthetic rubber could not have been adequate or satisfactory. Neither, on the other hand, have the British made a success of the Perkin process, although they spent $200,000 on it in the first two years. But, of course, there was not the same necessity for it as in the case of Germany, for England had practically a monopoly of the world's supply of natural rubber either through owning plantations or controlling shipping. If rubber could not be manufactured profitably in Germany when the demand was imperative and price no consideration it can hardly be expected to compete with the natural under peace conditions. The problem of synthetic rubber has then been solved scientifically but not industrially. It can be made but cannot be made to pay. The difficulty is to find a cheap enough material to start with. We can make rubber out of potatoes--but potatoes have other uses. It would require more land and more valuable land to raise the potatoes than to raise the rubber. We can get isoprene by the distillation of turpentine--but why not bleed a rubber tree as well as a pine tree? Turpentine is neither cheap nor abundant enough. Any kind of wood, sawdust for instance, can be utilized by converting the cellulose over into sugar and fermenting this to alcohol, but the process is not likely to prove profitable. Petroleum when cracked up to make gasoline gives isoprene or other double-bond compounds that go over into some form of rubber. But the most interesting and most promising of all is the complete inorganic synthesis that dispenses with the aid of vegetation and starts with coal and lime. These heated together in the electric furnace form calcium carbide and this, as every automobilist knows, gives acetylene by contact with water. From this gas isoprene can be made and the isoprene converted into rubber by sodium, or acid or alkali or simple heating. Acetone, which is also made from acetylene, can be converted directly into rubber by fuming sulfuric acid. This seems to have been the process chiefly used by the Germans during the war. Several carbide factories were devoted to it. But the intermediate and by-products of the process, such as alcohol, acetic acid and acetone, were in as much demand for war purposes as rubber. The Germans made some rubber from pitch imported from Sweden. They also found a useful substitute in aluminum naphthenate made from Baku petroleum, for it is elastic and plastic and can be vulcanized. So although rubber can be made in many different ways it is not profitable to make it in any of them. We have to rely still upon the natural product, but we can greatly improve upon the way nature produces it. When the call came for more rubber for the electrical and automobile industries the first attempt to increase the supply was to put pressure upon the natives to bring in more of the latex. As a consequence the trees were bled to death and sometimes also the natives. The Belgian atrocities in the Congo shocked the civilized world and at Putumayo on the upper Amazon the same cause produced the same horrible effects. But no matter what cruelty was practiced the tropical forests could not be made to yield a sufficient increase, so the cultivation of the rubber was begun by far-sighted men in Dutch Java, Sumatra and Borneo and in British Malaya and Ceylon. Brazil, feeling secure in the possession of a natural monopoly, made no effort to compete with these parvenus. It cost about as much to gather rubber from the Amazon forests as it did to raise it on a Malay plantation, that is, 25 cents a pound. The Brazilian Government clapped on another 25 cents export duty and spent the money lavishly. In 1911 the treasury of Para took in $2,000,000 from the rubber tax and a good share of the money was spent on a magnificent new theater at Manaos--not on setting out rubber trees. The result of this rivalry between the collector and the cultivator is shown by the fact that in the decade 1907-1917 the world's output of plantation rubber increased from 1000 to 204,000 tons, while the output of wild rubber decreased from 68,000 to 53,000. Besides this the plantation rubber is a cleaner and more even product, carefully coagulated by acetic acid instead of being smoked over a forest fire. It comes in pale yellow sheets instead of big black balls loaded with the dirt or sticks and stones that the honest Indian sometimes adds to make a bigger lump. What's better, the man who milks the rubber trees on a plantation may live at home where he can be decently looked after. The agriculturist and the chemist may do what the philanthropist and statesman could not accomplish: put an end to the cruelties involved in the international struggle for "black gold." The United States uses three-fourths of the world's rubber output and grows none of it. What is the use of tropical possessions if we do not make use of them? The Philippines could grow all our rubber and keep a $300,000,000 business under our flag. Santo Domingo, where rubber was first discovered, is now under our supervision and could be enriched by the industry. The Guianas, where the rubber tree was first studied, might be purchased. It is chiefly for lack of a definite colonial policy that our rubber industry, by far the largest in the world, has to be dependent upon foreign sources for all its raw materials. Because the Philippines are likely to be cast off at any moment, American manufacturers are placing their plantations in the Dutch or British possessions. The Goodyear Company has secured a concession of 20,000 acres near Medan in Dutch Sumatra. While the United States is planning to relinquish its Pacific possessions the British have more than doubled their holdings in New Guinea by the acquisition of Kaiser Wilhelm's Land, good rubber country. The British Malay States in 1917 exported over $118,000,000 worth of plantation-grown rubber and could have sold more if shipping had not been short and production restricted. Fully 90 per cent. of the cultivated rubber is now grown in British colonies or on British plantations in the Dutch East Indies. To protect this monopoly an act has been passed preventing foreigners from buying more land in the Malay Peninsula. The Japanese have acquired there 50,000 acres, on which they are growing more than a million dollars' worth of rubber a year. The British _Tropical Life_ says of the American invasion: "As America is so extremely wealthy Uncle Sam can well afford to continue to buy our rubber as he has been doing instead of coming in to produce rubber to reduce his competition as a buyer in the world's market." The Malaya estates calculate to pay a dividend of 20 per cent. on the investment with rubber selling at 30 cents a pound and every two cents additional on the price brings a further 3-1/2 per cent. dividend. The output is restricted by the Rubber Growers' Association so as to keep the price up to 50-70 cents. When the plantations first came into bearing in 1910 rubber was bringing nearly $3 a pound, and since it can be produced at less than 30 cents a pound we can imagine the profits of the early birds. The fact that the world's rubber trade was in the control of Great Britain caused America great anxiety and financial loss in the early part of the war when the British Government, suspecting--not without reason--that some American rubber goods were getting into Germany through neutral nations, suddenly shut off our supply. This threatened to kill the fourth largest of our industries and it was only by the submission of American rubber dealers to the closest supervision and restriction by the British authorities that they were allowed to continue their business. Sir Francis Hopwood, in laying down these regulations, gave emphatic warning "that in case any manufacturer, importer or dealer came under suspicion his permits should be immediately revoked. Reinstatement will be slow and difficult. The British Government will cancel first and investigate afterward." Of course the British had a right to say under what conditions they should sell their rubber and we cannot blame them for taking such precautions to prevent its getting to their enemies, but it placed the United States in a humiliating position and if we had not been in sympathy with their side it would have aroused more resentment than it did. But it made evident the desirability of having at least part of our supply under our own control and, if possible, within our own country. Rubber is not rare in nature, for it is contained in almost every milky juice. Every country boy knows that he can get a self-feeding mucilage brush by cutting off a milkweed stalk. The only native source so far utilized is the guayule, which grows wild on the deserts of the Mexican and the American border. The plant was discovered in 1852 by Dr. J.M. Bigelow near Escondido Creek, Texas. Professor Asa Gray described it and named it Parthenium argentatum, or the silver Pallas. When chopped up and macerated guayule gives a satisfactory quality of caoutchouc in profitable amounts. In 1911 seven thousand tons of guayule were imported from Mexico; in 1917 only seventeen hundred tons. Why this falling off? Because the eager exploiters had killed the goose that laid the golden egg, or in plain language, pulled up the plant by the roots. Now guayule is being cultivated and is reaped instead of being uprooted. Experiments at the Tucson laboratory have recently removed the difficulty of getting the seed to germinate under cultivation. This seems the most promising of the home-grown plants and, until artificial rubber can be made profitable, gives us the only chance of being in part independent of oversea supply. There are various other gums found in nature that can for some purposes be substituted for caoutchouc. Gutta percha, for instance, is pliable and tough though not very elastic. It becomes plastic by heat so it can be molded, but unlike rubber it cannot be hardened by heating with sulfur. A lump of gutta percha was brought from Java in 1766 and placed in a British museum, where it lay for nearly a hundred years before it occurred to anybody to do anything with it except to look at it. But a German electrician, Siemens, discovered in 1847 that gutta percha was valuable for insulating telegraph lines and it found extensive employment in submarine cables as well as for golf balls, and the like. Balata, which is found in the forests of the Guianas, is between gutta percha and rubber, not so good for insulation but useful for shoe soles and machine belts. The bark of the tree is so thick that the latex does not run off like caoutchouc when the bark is cut. So the bark has to be cut off and squeezed in hand presses. Formerly this meant cutting down the tree, but now alternate strips of the bark are cut off and squeezed so the tree continues to live. When Columbus discovered Santo Domingo he found the natives playing with balls made from the gum of the caoutchouc tree. The soldiers of Pizarro, when they conquered Inca-Land, adopted the Peruvian custom of smearing caoutchouc over their coats to keep out the rain. A French scientist, M. de la Condamine, who went to South America to measure the earth, came back in 1745 with some specimens of caoutchouc from Para as well as quinine from Peru. The vessel on which he returned, the brig _Minerva_, had a narrow escape from capture by an English cruiser, for Great Britain was jealous of any trespassing on her American sphere of influence. The Old World need not have waited for the discovery of the New, for the rubber tree grows wild in Annam as well as Brazil, but none of the Asiatics seems to have discovered any of the many uses of the juice that exudes from breaks in the bark. The first practical use that was made of it gave it the name that has stuck to it in English ever since. Magellan announced in 1772 that it was good to remove pencil marks. A lump of it was sent over from France to Priestley, the clergyman chemist who discovered oxygen and was mobbed out of Manchester for being a republican and took refuge in Pennsylvania. He cut the lump into little cubes and gave them to his friends to eradicate their mistakes in writing or figuring. Then they asked him what the queer things were and he said that they were "India rubbers." [Illustration: FOREST RUBBER Compare this tropical tangle and gnarled trunk with the straight tree and cleared ground of the plantation. At the foot of the trunk are cups collecting rubber juice.] [Illustration: PLANTATION RUBBER This spiral cut draws off the milk as completely and quickly as possible without harming the tree. The man is pulling off a strip of coagulated rubber that clogs it.] [Illustration: IN MAKING GARDEN HOSE THE RUBBER IS FORMED INTO A TUBE BY THE MACHINE ON THE RIGHT AND COILED ON THE TABLE TO THE LEFT] The Peruvian natives had used caoutchouc for water-proof clothing, shoes, bottles and syringes, but Europe was slow to take it up, for the stuff was too sticky and smelled too bad in hot weather to become fashionable in fastidious circles. In 1825 Mackintosh made his name immortal by putting a layer of rubber between two cloths. A German chemist, Ludersdorf, discovered in 1832 that the gum could be hardened by treating it with sulfur dissolved in turpentine. But it was left to a Yankee inventor, Charles Goodyear, of Connecticut, to work out a practical solution of the problem. A friend of his, Hayward, told him that it had been revealed to him in a dream that sulfur would harden rubber, but unfortunately the angel or defunct chemist who inspired the vision failed to reveal the details of the process. So Hayward sold out his dream to Goodyear, who spent all his own money and all he could borrow from his friends trying to convert it into a reality. He worked for ten years on the problem before the "lucky accident" came to him. One day in 1839 he happened to drop on the hot stove of the kitchen that he used as a laboratory a mixture of caoutchouc and sulfur. To his surprise he saw the two substances fuse together into something new. Instead of the soft, tacky gum and the yellow, brittle brimstone he had the tough, stable, elastic solid that has done so much since to make our footing and wheeling safe, swift and noiseless. The gumshoes or galoshes that he was then enabled to make still go by the name of "rubbers" in this country, although we do not use them for pencil erasers. Goodyear found that he could vary this "vulcanized rubber" at will. By adding a little more sulfur he got a hard substance which, however, could be softened by heat so as to be molded into any form wanted. Out of this "hard rubber" "vulcanite" or "ebonite" were made combs, hairpins, penholders and the like, and it has not yet been superseded for some purposes by any of its recent rivals, the synthetic resins. The new form of rubber made by the Germans, methyl rubber, is said to be a superior substitute for the hard variety but not satisfactory for the soft. The electrical resistance of the synthetic product is 20 per cent, higher than the natural, so it is excellent for insulation, but it is inferior in elasticity. In the latter part of the war the methyl rubber was manufactured at the rate of 165 tons a month. The first pneumatic tires, known then as "patent aerial wheels," were invented by Robert William Thomson of London in 1846. On the following year a carriage equipped with them was seen in the streets of New York City. But the pneumatic tire did not come into use until after 1888, when an Irish horse-doctor, John Boyd Dunlop, of Belfast, tied a rubber tube around the wheels of his little son's velocipede. Within seven years after that a $25,000,000 corporation was manufacturing Dunlop tires. Later America took the lead in this business. In 1913 the United States exported $3,000,000 worth of tires and tubes. In 1917 the American exports rose to $13,000,000, not counting what went to the Allies. The number of pneumatic tires sold in 1917 is estimated at 18,000,000, which at an average cost of $25 would amount to $450,000,000. No matter how much synthetic rubber may be manufactured or how many rubber trees are set out there is no danger of glutting the market, for as the price falls the uses of rubber become more numerous. One can think of a thousand ways in which rubber could be used if it were only cheap enough. In the form of pads and springs and tires it would do much to render traffic noiseless. Even the elevated railroad and the subway might be opened to conversation, and the city made habitable for mild voiced and gentle folk. It would make one's step sure, noiseless and springy, whether it was used individualistically as rubber heels or collectivistically as carpeting and paving. In roofing and siding and paint it would make our buildings warmer and more durable. It would reduce the cost and permit the extension of electrical appliances of almost all kinds. In short, there is hardly any other material whose abundance would contribute more to our comfort and convenience. Noise is an automatic alarm indicating lost motion and wasted energy. Silence is economy and resiliency is superior to resistance. A gumshoe outlasts a hobnailed sole and a rubber tube full of air is better than a steel tire. IX THE RIVAL SUGARS The ancient Greeks, being an inquisitive and acquisitive people, were fond of collecting tales of strange lands. They did not care much whether the stories were true or not so long as they were interesting. Among the marvels that the Greeks heard from the Far East two of the strangest were that in India there were plants that bore wool without sheep and reeds that bore honey without bees. These incredible tales turned out to be true and in the course of time Europe began to get a little calico from Calicut and a kind of edible gravel that the Arabs who brought it called "sukkar." But of course only kings and queens could afford to dress in calico and have sugar prescribed for them when they were sick. Fortunately, however, in the course of time the Arabs invaded Spain and forced upon the unwilling inhabitants of Europe such instrumentalities of higher civilization as arithmetic and algebra, soap and sugar. Later the Spaniards by an act of equally unwarranted and beneficent aggression carried the sugar cane to the Caribbean, where it thrived amazingly. The West Indies then became a rival of the East Indies as a treasure-house of tropical wealth and for several centuries the Spanish, Portuguese, Dutch, English, Danes and French fought like wildcats to gain possession of this little nest of islands and the routes leading thereunto. The English finally overcame all these enemies, whether they fought her singly or combined. Great Britain became mistress of the seas and took such Caribbean lands as she wanted. But in the end her continental foes came out ahead, for they rendered her victory valueless. They were defeated in geography but they won in chemistry. Canning boasted that "the New World had been called into existence to redress the balance of the Old." Napoleon might have boasted that he had called in the sugar beet to balance the sugar cane. France was then, as Germany was a century later, threatening to dominate the world. England, then as in the Great War, shut off from the seas the shipping of the aggressive power. France then, like Germany later, felt most keenly the lack of tropical products, chief among which, then but not in the recent crisis, was sugar. The cause of this vital change is that in 1747 Marggraf, a Berlin chemist, discovered that it was possible to extract sugar from beets. There was only a little sugar in the beet root then, some six per cent., and what he got out was dirty and bitter. One of his pupils in 1801 set up a beet sugar factory near Breslau under the patronage of the King of Prussia, but the industry was not a success until Napoleon took it up and in 1810 offered a prize of a million francs for a practical process. How the French did make fun of him for this crazy notion! In a comic paper of that day you will find a cartoon of Napoleon in the nursery beside the cradle of his son and heir, the King of Rome--known to the readers of Rostand as l'Aiglon. The Emperor is squeezing the juice of a beet into his coffee and the nurse has put a beet into the mouth of the infant King, saying: "Suck, dear, suck. Your father says it's sugar." In like manner did the wits ridicule Franklin for fooling with electricity, Rumford for trying to improve chimneys, Parmentier for thinking potatoes were fit to eat, and Jefferson for believing that something might be made of the country west of the Mississippi. In all ages ridicule has been the chief weapon of conservatism. If you want to know what line human progress will take in the future read the funny papers of today and see what they are fighting. The satire of every century from Aristophanes to the latest vaudeville has been directed against those who are trying to make the world wiser or better, against the teacher and the preacher, the scientist and the reformer. In spite of the ridicule showered upon it the despised beet year by year gained in sweetness of heart. The percentage of sugar rose from six to eighteen and by improved methods of extraction became finally as pure and palatable as the sugar of the cane. An acre of German beets produces more sugar than an acre of Louisiana cane. Continental Europe waxed wealthy while the British West Indies sank into decay. As the beets of Europe became sweeter the population of the islands became blacker. Before the war England was paying out $125,000,000 for sugar, and more than two-thirds of this money was going to Germany and Austria-Hungary. Fostered by scientific study, protected by tariff duties, and stimulated by export bounties, the beet sugar industry became one of the financial forces of the world. The English at home, especially the marmalade-makers, at first rejoiced at the idea of getting sugar for less than cost at the expense of her continental rivals. But the suffering colonies took another view of the situation. In 1888 a conference of the powers called at London agreed to stop competing by the pernicious practice of export bounties, but France and the United States refused to enter, so the agreement fell through. Another conference ten years later likewise failed, but when the parvenu beet sugar ventured to invade the historic home of the cane the limit of toleration had been reached. The Council of India put on countervailing duties to protect their homegrown cane from the bounty-fed beet. This forced the calling of a convention at Brussels in 1903 "to equalize the conditions of competition between beet sugar and cane sugar of the various countries," at which the powers agreed to a mutual suppression of bounties. Beet sugar then divided the world's market equally with cane sugar and the two rivals stayed substantially neck and neck until the Great War came. This shut out from England the product of Germany, Austria-Hungary, Belgium, northern France and Russia and took the farmers from their fields. The battle lines of the Central Powers enclosed the land which used to grow a third of the world's supply of sugar. In 1913 the beet and the cane each supplied about nine million tons of sugar. In 1917 the output of cane sugar was 11,200,000 and of beet sugar 5,300,000 tons. Consequently the Old World had to draw upon the New. Cuba, on which the United States used to depend for half its sugar supply, sent over 700,000 tons of raw sugar to England in 1916. The United States sent as much more refined sugar. The lack of shipping interfered with our getting sugar from our tropical dependencies, Hawaii, Porto Rico and the Philippines. The homegrown beets give us only a fifth and the cane of Louisiana and Texas only a fifteenth of the sugar we need. As a result we were obliged to file a claim in advance to get a pound of sugar from the corner grocery and then we were apt to be put off with rock candy, muscovado or honey. Lemon drops proved useful for Russian tea and the "long sweetening" of our forefathers came again into vogue in the form of various syrups. The United States was accustomed to consume almost a fifth of all the sugar produced in the world--and then we could not get it. [Illustration: MAP SHOWING LOCATION OF EUROPEAN BEET SUGAR FACTORIES--ALSO BATTLE LINES AT CLOSE OF 1918 ESTIMATED THAT ONE-THIRD OF WORLDS PRODUCTION BEFORE THE WAR WAS PRODUCED WITHIN BATTLE LINES Courtesy American Sugar Refining Co.] The shortage made us realize how dependent we have become upon sugar. Yet it was, as we have seen, practically unknown to the ancients and only within the present generation has it become an essential factor in our diet. As soon as the chemist made it possible to produce sugar at a reasonable price all nations began to buy it in proportion to their means. Americans, as the wealthiest people in the world, ate the most, ninety pounds a year on the average for every man, woman and child. In other words we ate our weight of sugar every year. The English consumed nearly as much as the Americans; the French and Germans about half as much; the Balkan peoples less than ten pounds per annum; and the African savages none. [Illustration: How the sugar beet has gained enormously in sugar content under chemical control] Pure white sugar is the first and greatest contribution of chemistry to the world's dietary. It is unique in being a single definite chemical compound, sucrose, C_{12}H_{22}O_{11}. All natural nutriments are more or less complex mixtures. Many of them, like wheat or milk or fruit, contain in various proportions all of the three factors of foods, the fats, the proteids and the carbohydrates, as well as water and the minerals and other ingredients necessary to life. But sugar is a simple substance, like water or salt, and like them is incapable of sustaining life alone, although unlike them it is nutritious. In fact, except the fats there is no more nutritious food than sugar, pound for pound, for it contains no water and no waste. It is therefore the quickest and usually the cheapest means of supplying bodily energy. But as may be seen from its formula as given above it contains only three elements, carbon, hydrogen and oxygen, and omits nitrogen and other elements necessary to the body. An engine requires not only coal but also lubricating oil, water and bits of steel and brass to keep it in repair. But as a source of the energy needed in our strenuous life sugar has no equal and only one rival, alcohol. Alcohol is the offspring of sugar, a degenerate descendant that retains but few of the good qualities of its sire and has acquired some evil traits of its own. Alcohol, like sugar, may serve to furnish the energy of a steam engine or a human body. Used as a fuel alcohol has certain advantages, but used as a food it has the disqualification of deranging the bodily mechanism. Even a little alcohol will impair the accuracy and speed of thought and action, while a large quantity, as we all know from observation if not experience, will produce temporary incapacitation. When man feeds on sugar he splits it up by the aid of air into water and carbon dioxide in this fashion: C_{12}H_{22}O_{11} + 12O_{2} --> 11H_{2}O + 12CO_{2} cane sugar oxygen water carbon dioxide When sugar is burned the reaction is just the same. But when the yeast plant feeds on sugar it carries the process only part way and instead of water the product is alcohol, a very different thing, so they say who have tried both as beverages. The yeast or fermentation reaction is this: C_{12}H_{22}O_{11} + H_{2}O --> 4C_{2}H_{6}O + 4CO_{2} cane sugar water alcohol carbon dioxide Alcohol then is the first product of the decomposition of sugar, a dangerous half-way house. The twin product, carbon dioxide or carbonic acid, is a gas of slightly sour taste which gives an attractive tang and effervescence to the beer, wine, cider or champagne. That is to say, one of these twins is a pestilential fellow and the other is decidedly agreeable. Yet for several thousand years mankind took to the first and let the second for the most part escape into the air. But when the chemist appeared on the scene he discovered a way of separating the two and bottling the harmless one for those who prefer it. An increasing number of people were found to prefer it, so the American soda-water fountain is gradually driving Demon Rum out of the civilized world. The brewer nowadays caters to two classes of customers. He bottles up the beer with the alcohol and a little carbonic acid in it for the saloon and he catches the rest of the carbonic acid that he used to waste and sells it to the drug stores for soda-water or uses it to charge some non-alcoholic beer of his own. This catering to rival trades is not an uncommon thing with the chemist. As we have seen, the synthetic perfumes are used to improve the natural perfumes. Cottonseed is separated into oil and meal; the oil going to make margarin and the meal going to feed the cows that produce butter. Some people have been drinking coffee, although they do not like the taste of it, because they want the stimulating effect of its alkaloid, caffein. Other people liked the warmth and flavor of coffee but find that caffein does not agree with them. Formerly one had to take the coffee whole or let it alone. Now one can have his choice, for the caffein is extracted for use in certain popular cold drinks and the rest of the bean sold as caffein-free coffee. Most of the "soft drinks" that are now gradually displacing the hard ones consist of sugar, water and carbonic acid, with various flavors, chiefly the esters of the fatty and aromatic acids, such as I described in a previous chapter. These are still usually made from fruits and spices and in some cases the law or public opinion requires this, but eventually, I presume, the synthetic flavors will displace the natural and then we shall get rid of such extraneous and indigestible matter as seeds, skins and bark. Suppose the world had always been used to synthetic and hence seedless figs, strawberries and blackberries. Suppose then some manufacturer of fig paste or strawberry jam should put in ten per cent. of little round hard wooden nodules, just the sort to get stuck between the teeth or caught in the vermiform appendix. How long would it be before he was sent to jail for adulterating food? But neither jail nor boycott has any reformatory effect on Nature. Nature is quite human in that respect. But you can reform Nature as you can human beings by looking out for heredity and culture. In this way Mother Nature has been quite cured of her bad habit of putting seeds in bananas and oranges. Figs she still persists in adulterating with particles of cellulose as nutritious as sawdust. But we can circumvent the old lady at this. I got on Christmas a package of figs from California without a seed in them. Somebody had taken out all the seeds--it must have been a big job--and then put the figs together again as natural looking as life and very much better tasting. Sugar and alcohol are both found in Nature; sugar in the ripe fruit, alcohol when it begins to decay. But it was the chemist who discovered how to extract them. He first worked with alcohol and unfortunately succeeded. Previous to the invention of the still by the Arabian chemists man could not get drunk as quickly as he wanted to because his liquors were limited to what the yeast plant could stand without intoxication. When the alcoholic content of wine or beer rose to seventeen per cent. at the most the process of fermentation stopped because the yeast plants got drunk and quit "working." That meant that a man confined to ordinary wine or beer had to drink ten or twenty quarts of water to get one quart of the stuff he was after, and he had no liking for water. So the chemist helped him out of this difficulty and got him into worse trouble by distilling the wine. The more volatile part that came over first contained the flavor and most of the alcohol. In this way he could get liquors like brandy and whisky, rum and gin, containing from thirty to eighty per cent. of alcohol. This was the origin of the modern liquor problem. The wine of the ancients was strong enough to knock out Noah and put the companions of Socrates under the table, but it was not until distilled liquors came in that alcoholism became chronic, epidemic and ruinous to whole populations. But the chemist later tried to undo the ruin he had quite inadvertently wrought by introducing alcohol into the world. One of his most successful measures was the production of cheap and pure sugar which, as we have seen, has become a large factor in the dietary of civilized countries. As a country sobers up it takes to sugar as a "self-starter" to provide the energy needed for the strenuous life. A five o'clock candy is a better restorative than a five o'clock highball or even a five o'clock tea, for it is a true nutrient instead of a mere stimulant. It is a matter of common observation that those who like sweets usually do not like alcohol. Women, for instance, are apt to eat candy but do not commonly take to alcoholic beverages. Look around you at a banquet table and you will generally find that those who turn down their wine glasses generally take two lumps in their demi-tasses. We often hear it said that whenever a candy store opens up a saloon in the same block closes up. Our grandmothers used to warn their daughters: "Don't marry a man who does not want sugar in his tea. He is likely to take to drink." So, young man, when next you give a box of candy to your best girl and she offers you some, don't decline it. Eat it and pretend to like it, at least, for it is quite possible that she looked into a physiology and is trying you out. You never can tell what girls are up to. In the army and navy ration the same change has taken place as in the popular dietary. The ration of rum has been mostly replaced by an equivalent amount of candy or marmalade. Instead of the tippling trooper of former days we have "the chocolate soldier." No previous war in history has been fought so largely on sugar and so little on alcohol as the last one. When the war reduced the supply and increased the demand we all felt the sugar famine and it became a mark of patriotism to refuse candy and to drink coffee unsweetened. This, however, is not, as some think, the mere curtailment of a superfluous or harmful luxury, the sacrifice of a pleasant sensation. It is a real deprivation and a serious loss to national nutrition. For there is no reason to think the constantly rising curve of sugar consumption has yet reached its maximum or optimum. Individuals overeat, but not the population as a whole. According to experiments of the Department of Agriculture men doing heavy labor may add three-quarters of a pound of sugar to their daily diet without any deleterious effects. This is at the rate of 275 pounds a year, which is three times the average consumption of England and America. But the Department does not state how much a girl doing nothing ought to eat between meals. Of the 2500 to 3500 calories of energy required to keep a man going for a day the best source of supply is the carbohydrates, that is, the sugars and starches. The fats are more concentrated but are more expensive and less easily assimilable. The proteins are also more expensive and their decomposition products are more apt to clog up the system. Common sugar is almost an ideal food. Cheap, clean, white, portable, imperishable, unadulterated, pleasant-tasting, germ-free, highly nutritious, completely soluble, altogether digestible, easily assimilable, requires no cooking and leaves no residue. Its only fault is its perfection. It is so pure that a man cannot live on it. Four square lumps give one hundred calories of energy. But twenty-five or thirty-five times that amount would not constitute a day's ration, in fact one would ultimately starve on such fare. It would be like supplying an army with an abundance of powder but neglecting to provide any bullets, clothing or food. To make sugar the sole food is impossible. To make it the main food is unwise. It is quite proper for man to separate out the distinct ingredients of natural products--to extract the butter from the milk, the casein from the cheese, the sugar from the cane--but he must not forget to combine them again at each meal with the other essential foodstuffs in their proper proportion. [Illustration: THE RIVAL SUGARS The sugar beet of the north has become a close rival of the sugar cane of the south] [Illustration: INTERIOR OF A SUGAR MILL SHOWING THE MACHINERY FOR CRUSHING CANE TO EXTRACT THE JUICE] [Illustration: Courtesy of American Sugar Refinery Co. VACUUM PANS OF THE AMERICAN SUGAR REFINERY COMPANY In these air-tight vats the water is boiled off from the cane juice under diminished atmospheric pressure until the sugar crystallizes out] Sugar is not a synthetic product and the business of the chemist has been merely to extract and purify it. But this is not so simple as it seems and every sugar factory has had to have its chemist. He has analyzed every mother beet for a hundred years. He has watched every step of the process from the cane to the crystal lest the sucrose should invert to the less sweet and non-crystallizable glucose. He has tested with polarized light every shipment of sugar that has passed through the custom house, much to the mystification of congressmen who have often wondered at the money and argumentation expended in a tariff discussion over the question of the precise angle of rotation of the plane of vibration of infinitesimal waves in a hypothetical ether. The reason for this painstaking is that there are dozens of different sugars, so much alike that they are difficult to separate. They are all composed of the same three elements, C, H and O, and often in the same proportion. Sometimes two sugars differ only in that one has a right-handed and the other a left-handed twist to its molecule. They bear the same resemblance to one another as the two gloves of a pair. Cane sugar and beet sugar are when completely purified the same substance, that is, sucrose, C_{12}H_{22}O_{11}. The brown and straw-colored sugars, which our forefathers used and which we took to using during the war, are essentially the same but have not been so completely freed from moisture and the coloring and flavoring matter of the cane juice. Maple sugar is mostly sucrose. So partly is honey. Candies are made chiefly of sucrose with the addition of glucose, gums or starch, to give them the necessary consistency and of such colors and flavors, natural or synthetic, as may be desired. Practically all candy, even the cheapest, is nowadays free from deleterious ingredients in the manufacture, though it is liable to become contaminated in the handling. In fact sugar is about the only food that is never adulterated. It would be hard to find anything cheaper to add to it that would not be easily detected. "Sanding the sugar," the crime of which grocers are generally accused, is the one they are least likely to be guilty of. Besides the big family of sugars which are all more or less sweet, similar in structure and about equally nutritious, there are, very curiously, other chemical compounds of altogether different composition which taste like sugar but are not nutritious at all. One of these is a coal-tar derivative, discovered accidentally by an American student of chemistry, Ira Remsen, afterward president of Johns Hopkins University, and named by him "saccharin." This has the composition C_{6}H_{4}COSO_{2}NH, and as you may observe from the symbol it contains sulfur (S) and nitrogen (N) and the benzene ring (C_{6}H_{4}) that are not found in any of the sugars. It is several hundred times sweeter than sugar, though it has also a slightly bitter aftertaste. A minute quantity of it can therefore take the place of a large amount of sugar in syrups, candies and preserves, so because it lends itself readily to deception its use in food has been prohibited in the United States and other countries. But during the war, on account of the shortage of sugar, it came again into use. The European governments encouraged what they formerly tried to prevent, and it became customary in Germany or Italy to carry about a package of saccharin tablets in the pocket and drop one or two into the tea or coffee. Such reversals of administrative attitude are not uncommon. When the use of hops in beer was new it was prohibited by British law. But hops became customary nevertheless and now the law requires hops to be used in beer. When workingmen first wanted to form unions, laws were passed to prevent them. But now, in Australia for instance, the laws require workingmen to form unions. Governments naturally tend to a conservative reaction against anything new. It is amusing to turn back to the pure food agitation of ten years ago and read the sensational articles in the newspapers about the poisonous nature of this dangerous drug, saccharin, in view of the fact that it is being used by millions of people in Europe in amounts greater than once seemed to upset the tender stomachs of the Washington "poison squads." But saccharin does not appear to be responsible for any fatalities yet, though people are said to be heartily sick of it. And well they may be, for it is not a substitute for sugar except to the sense of taste. Glucose may correctly be called a substitute for sucrose as margarin for butter, since they not only taste much the same but have about the same food value. But to serve saccharin in the place of sugar is like giving a rubber bone to a dog. It is reported from Europe that the constant use of saccharin gives one eventually a distaste for all sweets. This is quite likely, although it means the reversal within a few years of prehistoric food habits. Mankind has always associated sweetness with food value, for there are few sweet things found in nature except the sugars. We think we eat sugar because it is sweet. But we do not. We eat it because it is good for us. The reason it tastes sweet to us is because it is good for us. So man makes a virtue out of necessity, a pleasure out of duty, which is the essence of ethics. In the ancient days of Ind the great Raja Trishanku possessed an earthly paradise that had been constructed for his delectation by a magician. Therein grew all manner of beautiful flowers, savory herbs and delicious fruits such as had never been known before outside heaven. Of them all the Raja and his harems liked none better than the reed from which they could suck honey. But Indra, being a jealous god, was wroth when he looked down and beheld mere mortals enjoying such delights. So he willed the destruction of the enchanted garden. With drought and tempest it was devastated, with fire and hail, until not a leaf was left of its luxuriant vegetation and the ground was bare as a threshing floor. But the roots of the sugar cane are not destroyed though the stalk be cut down; so when men ventured to enter the desert where once had been this garden of Eden, they found the cane had grown up again and they carried away cuttings of it and cultivated it in their gardens. Thus it happened that the nectar of the gods descended first to monarchs and their favorites, then was spread among the people and carried abroad to other lands until now any child with a penny in his hand may buy of the best of it. So it has been with many things. So may it be with all things. X WHAT COMES FROM CORN The discovery of America dowered mankind with a world of new flora. The early explorers in their haste to gather up gold paid little attention to the more valuable products of field and forest, but in the course of centuries their usefulness has become universally recognized. The potato and tomato, which Europe at first considered as unfit for food or even as poisonous, have now become indispensable among all classes. New World drugs like quinine and cocaine have been adopted into every pharmacopeia. Cocoa is proving a rival of tea and coffee, and even the banana has made its appearance in European markets. Tobacco and chicle occupy the nostrils and jaws of a large part of the human race. Maize and rubber are become the common property of mankind, but still may be called American. The United States alone raises four-fifths of the corn and uses three-fourths of the caoutchouc of the world. All flesh is grass. This may be taken in a dietary as well as a metaphorical sense. The graminaceae provide the greater part of the sustenance of man and beast; hay and cereals, wheat, oats, rye, barley, rice, sugar cane, sorghum and corn. From an American viewpoint the greatest of these, physically and financially, is corn. The corn crop of the United States for 1917, amounting to 3,159,000,000 bushels, brought in more money than the wheat, cotton, potato and rye crops all together. When Columbus reached the West Indies he found the savages playing with rubber balls, smoking incense sticks of tobacco and eating cakes made of a new grain that they called _mahiz_. When Pizarro invaded Peru he found this same cereal used by the natives not only for food but also for making alcoholic liquor, in spite of the efforts of the Incas to enforce prohibition. When the Pilgrim Fathers penetrated into the woods back of Plymouth Harbor they discovered a cache of Indian corn. So throughout the three Americas, from Canada to Peru, corn was king and it has proved worthy to rank with the rival cereals of other continents, the wheat of Europe and the rice of Asia. But food habits are hard to change and for the most part the people of the Old World are still ignorant of the delights of hasty pudding and Indian pudding, of hoe-cake and hominy, of sweet corn and popcorn. I remember thirty years ago seeing on a London stand a heap of dejected popcorn balls labeled "Novel American Confection. Please Try One." But nobody complied with this pitiful appeal but me and I was sorry that I did. Americans used to respond with a shipload of corn whenever an appeal came from famine sufferers in Armenia, Russia, Ireland, India or Austria, but their generosity was chilled when they found that their gift was resented as an insult or as an attempt to poison the impoverished population, who declared that they would rather die than eat it--and some of them did. Our Department of Agriculture sent maize missionaries to Europe with farmers and millers as educators and expert cooks to serve free flapjacks and pones, but the propaganda made little impression and today Americans are urged to eat more of their own corn because the famished families of the war-stricken region will not touch it. Just so the beggars of Munich revolted at potato soup when the pioneer of American food chemists, Bumford, attempted to introduce this transatlantic dish. But here we are not so much concerned with corn foods as we are with its manufactured products. If you split a kernel in two you will find that it consists of three parts: a hard and horny hull on the outside, a small oily and nitrogenous germ at the point, and a white body consisting mostly of starch. Each of these is worked up into various products, as may be seen from the accompanying table. The hull forms bran and may be mixed with the gluten as a cattle food. The corn steeped for several days with sulfurous acid is disintegrated and on being ground the germs are floated off, the gluten or nitrogenous portion washed out, the starch grains settled down and the residue pressed together as oil cake fodder. The refined oil from the germ is marketed as a table or cooking oil under the name of "Mazola" and comes into competition with olive, peanut and cottonseed oil in the making of vegetable substitutes for lard and butter. Inferior grades may be used for soaps or for glycerin and perhaps nitroglycerin. A bushel of corn yields a pound or more of oil. From the corn germ also is extracted a gum called "paragol" that forms an acceptable substitute for rubber in certain uses. The "red rubber" sponges and the eraser tips to pencils may be made of it and it can contribute some twenty per cent. to the synthetic soles of shoes. [Illustration: CORN PRODUCTS] Starch, which constitutes fifty-five per cent. of the corn kernel, can be converted into a variety of products for dietary and industrial uses. As found in corn, potatoes or any other vegetables starch consists of small, round, white, hard grains, tasteless, and insoluble in cold water. But hot water converts it into a soluble, sticky form which may serve for starching clothes or making cornstarch pudding. Carrying the process further with the aid of a little acid or other catalyst it takes up water and goes over into a sugar, dextrose, commonly called "glucose." Expressed in chemical shorthand this reaction is C_{6}H_{10}O_{5} + H_{2}O --> C_{6}H_{12}O_{6} starch water dextrose This reaction is carried out on forty million bushels of corn a year in the United States. The "starch milk," that is, the starch grains washed out from the disintegrated corn kernel by water, is digested in large pressure tanks under fifty pounds of steam with a few tenths of one per cent. of hydrochloric acid until the required degree of conversion is reached. Then the remaining acid is neutralized by caustic soda, and thereby converted into common salt, which in this small amount does not interfere but rather enhances the taste. The product is the commercial glucose or corn syrup, which may if desired be evaporated to a white powder. It is a mixture of three derivatives of starch in about this proportion: Maltose 45 per cent. Dextrose 20 per cent. Dextrin 35 per cent. There are also present three- or four-tenths of one per cent. salt and as much of the corn protein and a variable amount of water. It will be noticed that the glucose (dextrose), which gives name to the whole, is the least of the three ingredients. Maltose, or malt sugar, has the same composition as cane sugar (C_{12}H_{22}O_{11}), but is not nearly so sweet. Dextrin, or starch paste, is not sweet at all. Dextrose or glucose is otherwise known; as grape sugar, for it is commonly found in grapes and other ripe fruits. It forms half of honey and it is one of the two products into which cane sugar splits up when we take it into the mouth. It is not so sweet as cane sugar and cannot be so readily crystallized, which, however, is not altogether a disadvantage. The process of changing starch into dextrose that takes place in the great steam kettles of the glucose factory is essentially the same as that which takes place in the ripening of fruit and in the digestion of starch. A large part of our nutriment, therefore, consists of glucose either eaten as such in ripe fruits or produced in the mouth or stomach by the decomposition of the starch of unripe fruit, vegetables and cereals. Glucose may be regarded as a predigested food. In spite of this well-known fact we still sometimes read "poor food" articles in which glucose is denounced as a dangerous adulterant and even classed as a poison. The other ingredients of commercial glucose, the maltose and dextrin, have of course the same food value as the dextrose, since they are made over into dextrose in the process of digestion. Whether the glucose syrup is fit to eat depends, like anything else, on how it is made. If, as was formerly sometimes the case, sulfuric acid was used to effect the conversion of the starch or sulfurous acid to bleach the glucose and these acids were not altogether eliminated, the product might be unwholesome or worse. Some years ago in England there was a mysterious epidemic of arsenical poisoning among beer drinkers. On tracing it back it was found that the beer had been made from glucose which had been made from sulfuric acid which had been made from sulfur which had been made from a batch of iron pyrites which contained a little arsenic. The replacement of sulfuric acid by hydrochloric has done away with that danger and the glucose now produced is pure. The old recipe for home-made candy called for the addition of a little vinegar to the sugar syrup to prevent "graining." The purpose of the acid was of course to invert part of the cane sugar to glucose so as to keep it from crystallizing out again. The professional candy-maker now uses the corn glucose for that purpose, so if we accuse him of "adulteration" on that ground we must levy the same accusation against our grandmothers. The introduction of glucose into candy manufacture has not injured but greatly increased the sale of sugar for the same purpose. This is not an uncommon effect of scientific progress, for as we have observed, the introduction of synthetic perfumes has stimulated the production of odoriferous flowers and the price of butter has gone up with the introduction of margarin. So, too, there are more weavers employed and they get higher wages than in the days when they smashed up the first weaving machines, and the same is true of printers and typesetting machines. The popular animosity displayed toward any new achievement of applied science is never justified, for it benefits not only the world as a whole but usually even those interests with which it seems at first to conflict. The chemist is an economizer. It is his special business to hunt up waste products and make them useful. He was, for instance, worried over the waste of the cores and skins and scraps that were being thrown away when apples were put up. Apple pulp contains pectin, which is what makes jelly jell, and berries and fruits that are short of it will refuse to "jell." But using these for their flavor he adds apple pulp for pectin and glucose for smoothness and sugar for sweetness and, if necessary, synthetic dyes for color, he is able to put on the market a variety of jellies, jams and marmalades at very low price. The same principle applies here as in the case of all compounded food products. If they are made in cleanly fashion, contain no harmful ingredients and are truthfully labeled there is no reason for objecting to them. But if the manufacturer goes so far as to put strawberry seeds--or hayseed--into his artificial "strawberry jam" I think that might properly be called adulteration, for it is imitating the imperfections of nature, and man ought to be too proud to do that. The old-fashioned open kettle molasses consisted mostly of glucose and other invert sugars together with such cane sugar as could not be crystallized out. But when the vacuum pan was introduced the molasses was impoverished of its sweetness and beet sugar does not yield any molasses. So we now have in its place the corn syrups consisting of about 85 per cent. of glucose and 15 per cent. of sugar flavored with maple or vanillin or whatever we like. It is encouraging to see the bill boards proclaiming the virtues of "Karo" syrup and "Mazola" oil when only a few years ago the products of our national cereal were without honor in their own country. Many other products besides foods are made from corn starch. Dextrin serves in place of the old "gum arabic" for the mucilage of our envelopes and stamps. Another form of dextrin sold as "Kordex" is used to hold together the sand of the cores of castings. After the casting has been made the scorched core can be shaken out. Glucose is used in place of sugar as a filler for cheap soaps and for leather. Altogether more than a hundred different commercial products are now made from corn, not counting cob pipes. Every year the factories of the United States work up over 50,000,000 bushels of corn into 800,000,000 pounds of corn syrup, 600,000,000 pounds of starch, 230,000,000 pounds of corn sugar, 625,000,000 pounds of gluten feed, 90,000,000 pounds of oil and 90,000,000 pounds of oil cake. Two million bushels of cobs are wasted every year in the United States. Can't something be made out of them? This is the question that is agitating the chemists of the Carbohydrate Laboratory of the Department of Agriculture at Washington. They have found it possible to work up the corn cobs into glucose and xylose by heating with acid. But glucose can be more cheaply obtained from other starchy or woody materials and they cannot find a market for the xylose. This is a sort of a sugar but only about half as sweet as that from cane. Who can invent a use for it! More promising is the discovery by this laboratory that by digesting the cobs with hot water there can be extracted about 30 per cent. of a gum suitable for bill posting and labeling. Since the starches and sugars belong to the same class of compounds as the celluloses they also can be acted upon by nitric acid with the production of explosives like guncotton. Nitro-sugar has not come into common use, but nitro-starch is found to be one of safest of the high explosives. On account of the danger of decomposition and spontaneous explosion from the presence of foreign substances the materials in explosives must be of the purest possible. It was formerly thought that tapioca must be imported from Java for making nitro-starch. But during the war when shipping was short, the War Department found that it could be made better and cheaper from our home-grown corn starch. When the war closed the United States was making 1,720,000 pounds of nitro-starch a month for loading hand grenades. So, too, the Post Office Department discovered that it could use mucilage made of corn dextrin as well as that which used to be made from tapioca. This is progress in the right direction. It would be well to divert some of the energetic efforts now devoted to the increase of commerce to the discovery of ways of reducing the need for commerce by the development of home products. There is no merit in simply hauling things around the world. In the last chapter we saw how dextrose or glucose could be converted by fermentation into alcohol. Since corn starch, as we have seen, can be converted into dextrose, it can serve as a source of alcohol. This was, in fact, one of the earliest misuses to which corn was put, and before the war put a stop to it 34,000,000 bushels went into the making of whiskey in the United States every year, not counting the moonshiners' output. But even though we left off drinking whiskey the distillers could still thrive. Mars is more thirsty than Bacchus. The output of whiskey, denatured for industrial purposes, is more than three times what is was before the war, and the price has risen from 30 cents a gallon to 67 cents. This may make it profitable to utilize sugars, starches and cellulose that formerly were out of the question. According to the calculations of the Forest Products Laboratory of Madison it costs from 37 to 44 cents a gallon to make alcohol from corn, but it may be made from sawdust at a cost of from 14 to 20 cents. This is not "wood alcohol" (that is, methyl alcohol, CH_{4}O) such as is made by the destructive distillation of wood, but genuine "grain alcohol" (ethyl alcohol, C_{2}H_{6}O), such as is made by the fermentation of glucose or other sugar. The first step in the process is to digest the sawdust or chips with dilute sulfuric acid under heat and pressure. This converts the cellulose (wood fiber) in large part into glucose ("corn sugar") which may be extracted by hot water in a diffusion battery as in extracting the sugar from beet chips. This glucose solution may then be fermented by yeast and the resulting alcohol distilled off. The process is perfectly practicable but has yet to be proved profitable. But the sulfite liquors of the paper mills are being worked up successfully into industrial alcohol. The rapidly approaching exhaustion of our oil fields which the war has accelerated leads us to look around to see what we can get to take the place of gasoline. One of the most promising of the suggested substitutes is alcohol. The United States is exceptionally rich in mineral oil, but some countries, for instance England, Germany, France and Australia, have little or none. The Australian Advisory Council of Science, called to consider the problem, recommends alcohol for stationary engines and motor cars. Alcohol has the disadvantage of being less volatile than gasoline so it is hard to start up the engine from the cold. But the lower volatility and ignition point of alcohol are an advantage in that it can be put under a pressure of 150 pounds to the square inch. A pound of gasoline contains fifty per cent. more potential energy than a pound of alcohol, but since the alcohol vapor can be put under twice the compression of the gasoline and requires only one-third the amount of air, the thermal efficiency of an alcohol engine may be fifty per cent. higher than that of a gasoline engine. Alcohol also has several other conveniences that can count in its favor. In the case of incomplete combustion the cylinders are less likely to be clogged with carbon and the escaping gases do not have the offensive odor of the gasoline smoke. Alcohol does not ignite so easily as gasoline and the fire is more readily put out, for water thrown upon blazing alcohol dilutes it and puts out the flame while gasoline floats on water and the fire is spread by it. It is possible to increase the inflammability of alcohol by mixing with it some hydrocarbon such as gasoline, benzene or acetylene. In the Taylor-White process the vapor from low-grade alcohol containing 17 per cent. water is passed over calcium carbide. This takes out the water and adds acetylene gas, making a suitable mixture for an internal combustion engine. Alcohol can be made from anything of a starchy, sugary or woody nature, that is, from the main substance of all vegetation. If we start with wood (cellulose) we convert it first into sugar (glucose) and, of course, we could stop here and use it for food instead of carrying it on into alcohol. This provides one factor of our food, the carbohydrate, but by growing the yeast plants on glucose and feeding them with nitrates made from the air we can get the protein and fat. So it is quite possible to live on sawdust, although it would be too expensive a diet for anybody but a millionaire, and he would not enjoy it. Glucose has been made from formaldehyde and this in turn made from carbon, hydrogen and oxygen, so the synthetic production of food from the elements is not such an absurdity as it was thought when Berthelot suggested it half a century ago. The first step in the making of alcohol is to change the starch over into sugar. This transformation is effected in the natural course of sprouting by which the insoluble starch stored up in the seed is converted into the soluble glucose for the sap of the growing plant. This malting process is that mainly made use of in the production of alcohol from grain. But there are other ways of effecting the change. It may be done by heating with acid as we have seen, or according to a method now being developed the final conversion may be accomplished by mold instead of malt. In applying this method, known as the amylo process, to corn, the meal is mixed with twice its weight of water, acidified with hydrochloric acid and steamed. The mash is then cooled down somewhat, diluted with sterilized water and innoculated with the mucor filaments. As the mash molds the starch is gradually changed over to glucose and if this is the product desired the process may be stopped at this point. But if alcohol is wanted yeast is added to ferment the sugar. By keeping it alkaline and treating with the proper bacteria a high yield of glycerin can be obtained. In the fermentation process for making alcoholic liquors a little glycerin is produced as a by-product. Glycerin, otherwise called glycerol, is intermediate between sugar and alcohol. Its molecule contains three carbon atoms, while glucose has six and alcohol two. It is possible to increase the yield of glycerin if desired by varying the form of fermentation. This was desired most earnestly in Germany during the war, for the British blockade shut off the importation of the fats and oils from which the Germans extracted the glycerin for their nitroglycerin. Under pressure of this necessity they worked out a process of getting glycerin in quantity from sugar and, news of this being brought to this country by Dr. Alonzo Taylor, the United States Treasury Department set up a special laboratory to work out this problem. John R. Eoff and other chemists working in this laboratory succeeded in getting a yield of twenty per cent. of glycerin by fermenting black strap molasses or other syrup with California wine yeast. During the fermentation it is necessary to neutralize the acetic acid formed with sodium or calcium carbonate. It was estimated that glycerin could be made from waste sugars at about a quarter of its war-time cost, but it is doubtful whether the process would be profitable at normal prices. We can, if we like, dispense with either yeast or bacteria in the production of glycerin. Glucose syrup suspended in oil under steam pressure with finely divided nickel as a catalyst and treated with nascent hydrogen will take up the hydrogen and be converted into glycerin. But the yield is poor and the process expensive. Food serves substantially the same purpose in the body as fuel in the engine. It provides the energy for work. The carbohydrates, that is the sugars, starches and celluloses, can all be used as fuels and can all--even, as we have seen, the cellulose--be used as foods. The final products, water and carbon dioxide, are in both cases the same and necessarily therefore the amount of energy produced is the same in the body as in the engine. Corn is a good example of the equivalence of the two sources of energy. There are few better foods and no better fuels. I can remember the good old days in Kansas when we had corn to burn. It was both an economy and a luxury, for--at ten cents a bushel--it was cheaper than coal or wood and preferable to either at any price. The long yellow ears, each wrapped in its own kindling, could be handled without crocking the fingers. Each kernel as it crackled sent out a blazing jet of oil and the cobs left a fine bed of coals for the corn popper to be shaken over. Driftwood and the pyrotechnic fuel they make now by soaking sticks in strontium and copper salts cannot compare with the old-fashioned corn-fed fire in beauty and the power of evoking visions. Doubtless such luxury would be condemned as wicked nowadays, but those who have known the calorific value of corn would find it hard to abandon it altogether, and I fancy that the Western farmer's wife, when she has an extra batch of baking to do, will still steal a few ears from the crib. XI SOLIDIFIED SUNSHINE All life and all that life accomplishes depend upon the supply of solar energy stored in the form of food. The chief sources of this vital energy are the fats and the sugars. The former contain two and a quarter times the potential energy of the latter. Both, when completely purified, consist of nothing but carbon, hydrogen and oxygen; elements that are to be found freely everywhere in air and water. So when the sunny southland exports fats and oils, starches and sugar, it is then sending away nothing material but what comes back to it in the next wind. What it is sending to the regions of more slanting sunshine is merely some of the surplus of the radiant energy it has received so abundantly, compacted for convenience into a portable and edible form. In previous chapters I have dealt with some of the uses of cotton, its employment for cloth, for paper, for artificial fibers, for explosives, and for plastics. But I have ignored the thing that cotton is attached to and for which, in the economy of nature, the fibers are formed; that is, the seed. It is as though I had described the aeroplane and ignored the aviator whom it was designed to carry. But in this neglect I am but following the example of the human race, which for three thousand years used the fiber but made no use of the seed except to plant the next crop. Just as mankind is now divided into the two great classes, the wheat-eaters and the rice-eaters, so the ancient world was divided into the wool-wearers and the cotton-wearers. The people of India wore cotton; the Europeans wore wool. When the Greeks under Alexander fought their way to the Far East they were surprised to find wool growing on trees. Later travelers returning from Cathay told of the same marvel and travelers who stayed at home and wrote about what they had not seen, like Sir John Maundeville, misunderstood these reports and elaborated a legend of a tree that bore live lambs as fruit. Here, for instance, is how a French poetical botanist, Delacroix, described it in 1791, as translated from his Latin verse: Upon a stalk is fixed a living brute, A rooted plant bears quadruped for fruit; It has a fleece, nor does it want for eyes, And from its brows two wooly horns arise. The rude and simple country people say It is an animal that sleeps by day And wakes at night, though rooted to the ground, To feed on grass within its reach around. But modern commerce broke down the barrier between East and West. A new cotton country, the best in the world, was discovered in America. Cotton invaded England and after a hard fight, with fists as well as finance, wool was beaten in its chief stronghold. Cotton became King and the wool-sack in the House of Lords lost its symbolic significance. Still two-thirds of the cotton crop, the seed, was wasted and it is only within the last fifty years that methods of using it have been developed to any extent. The cotton crop of the United States for 1917 amounted to about 11,000,000 bales of 500 pounds each. When the Great War broke out and no cotton could be exported to Germany and little to England the South was in despair, for cotton went down to five or six cents a pound. The national Government, regardless of states' rights, was called upon for aid and everybody was besought to "buy a bale." Those who responded to this patriotic appeal were well rewarded, for cotton rose as the war went on and sold at twenty-nine cents a pound. [ILLUSTRATION: PRODUCTS AND USES OF COTTONSEED] But the chemist has added some $150,000,000 a year to the value of the crop by discovering ways of utilizing the cottonseed that used to be thrown away or burned as fuel. The genealogical table of the progeny of the cottonseed herewith printed will give some idea of their variety. If you will examine a cottonseed you will see first that there is a fine fuzz of cotton fiber sticking to it. These linters can be removed by machinery and used for any purpose where length of fiber is not essential. For instance, they may be nitrated as described in previous articles and used for making smokeless powder or celluloid. On cutting open the seed you will observe that it consists of an oily, mealy kernel encased in a thin brown hull. The hulls, amounting to 700 or 900 pounds in a ton of seed, were formerly burned. Now, however, they bring from $4 to $10 a ton because they can be ground up into cattle-feed or paper stock or used as fertilizer. The kernel of the cottonseed on being pressed yields a yellow oil and leaves a mealy cake. This last, mixed with the hulls, makes a good fodder for fattening cattle. Also, adding twenty-five per cent. of the refined cottonseed meal to our war bread made it more nutritious and no less palatable. Cottonseed meal contains about forty per cent. of protein and is therefore a highly concentrated and very valuable feeding stuff. Before the war we were exporting nearly half a million tons of cottonseed meal to Europe, chiefly to Germany and Denmark, where it is used for dairy cows. The British yeoman, his country's pride, has not yet been won over to the use of any such newfangled fodder and consequently the British manufacturer could not compete with his continental rivals in the seed-crushing business, for he could not dispose of his meal-cake by-product as did they. [Illustration: Photo by Press Illustrating Service Cottonseed Oil As It Is Squeezed From The Seed By The Presses] [Illustration: Photo by Press Illustrating Service Cottonseed Oil As It Comes From The Compressors Flowing Out Of The Faucets When cold it is firm and white like lard] Let us now turn to the most valuable of the cottonseed products, the oil. The seed contains about twenty per cent. of oil, most of which can be squeezed out of the hot seeds by hydraulic pressure. It comes out as a red liquid of a disagreeable odor. This is decolorized, deodorized and otherwise purified in various ways: by treatment with alkalies or acids, by blowing air and steam through it, by shaking up with fuller's earth, by settling and filtering. The refined product is a yellow oil, suitable for table use. Formerly, on account of the popular prejudice against any novel food products, it used to masquerade as olive oil. Now, however, it boldly competes with its ancient rival in the lands of the olive tree and America ships some 700,000 barrels of cottonseed oil a year to the Mediterranean. The Turkish Government tried to check the spread of cottonseed oil by calling it an adulterant and prohibiting its mixture with olive oil. The result was that the sale of Turkish olive oil fell off because people found its flavor too strong when undiluted. Italy imports cottonseed oil and exports her olive oil. Denmark imports cottonseed meal and margarine and exports her butter. Northern nations are accustomed to hard fats and do not take to oils for cooking or table use as do the southerners. Butter and lard are preferred to olive oil and ghee. But this does not rule out cottonseed. It can be combined with the hard fats of animal or vegetable origin in margarine or it may itself be hardened by hydrogen. To understand this interesting reaction which is profoundly affecting international relations it will be necessary to dip into the chemistry of the subject. Here are the symbols of the chief ingredients of the fats and oils. Please look at them. Linoleic acid C_{18}H_{32}O_{2} Oleic acid C_{18}H_{34}O_{2} Stearic acid C_{18}H_{36}O_{2} Don't skip these because you have not studied chemistry. That's why I am giving them to you. If you had studied chemistry you would know them without my telling. Just examine them and you will discover the secret. You will see that all three are composed of the same elements, carbon, hydrogen, and oxygen. Notice next the number of atoms in each element as indicated by the little low figures on the right of each letter. You observe that all three contain the same number of atoms of carbon and oxygen but differ in the amount of hydrogen. This trifling difference in composition makes a great difference in behavior. The less the hydrogen the lower the melting point. Or to say the same thing in other words, fatty substances low in hydrogen are apt to be liquids and those with a full complement of hydrogen atoms are apt to be solids at the ordinary temperature of the air. It is common to call the former "oils" and the latter "fats," but that implies too great a dissimilarity, for the distinction depends on whether we are living in the tropics or the arctic. It is better, therefore, to lump them all together and call them "soft fats" and "hard fats," respectively. Fats of the third order, the stearic group, are called "saturated" because they have taken up all the hydrogen they can hold. Fats of the other two groups are called "unsaturated." The first, which have the least hydrogen, are the most eager for more. If hydrogen is not handy they will take up other things, for instance oxygen. Linseed oil, which consists largely, as the name implies, of linoleic acid, will absorb oxygen on exposure to the air and become hard. That is why it is used in painting. Such oils are called "drying" oils, although the hardening process is not really drying, since they contain no water, but is oxidation. The "semi-drying oils," those that will harden somewhat on exposure to the air, include the oils of cottonseed, corn, sesame, soy bean and castor bean. Olive oil and peanut oil are "non-drying" and contain oleic compounds (olein). The hard fats, such as stearin, palmitin and margarin, are mostly of animal origin, tallow and lard, though coconut and palm oil contain a large proportion of such saturated compounds. Though the chemist talks of the fatty "acids," nobody else would call them so because they are not sour. But they do behave like the acids in forming salts with bases. The alkali salts of the fatty acids are known to us as soaps. In the natural fats they exist not as free acids but as salts of an organic base, glycerin, as I explained in a previous chapter. The natural fats and oils consist of complex mixtures of the glycerin compounds of these acids (known as olein, stearin, etc.), as well as various others of a similar sort. If you will set a bottle of salad oil in the ice-box you will see it separate into two parts. The white, crystalline solid that separates out is largely stearin. The part that remains liquid is largely olein. You might separate them by filtering it cold and if then you tried to sell the two products you would find that the hard fat would bring a higher price than the oil, either for food or soap. If you tried to keep them you would find that the hard fat kept neutral and "sweet" longer than the other. You may remember that the perfumes (as well as their odorous opposites) were mostly unsaturated compounds. So we find that it is the free and unsaturated fatty acids that cause butter and oil to become rank and rancid. Obviously, then, we could make money if we could turn soft, unsaturated fats like olein into hard, saturated fats like stearin. Referring to the symbols we see that all that is needed to effect the change is to get the former to unite with hydrogen. This requires a little coaxing. The coaxer is called a catalyst. A catalyst, as I have previously explained, is a substance that by its mere presence causes the union of two other substances that might otherwise remain separate. For that reason the catalyst is referred to as "a chemical parson." Finely divided metals have a strong catalytic action. Platinum sponge is excellent but too expensive. So in this case nickel is used. A nickel salt mixed with charcoal or pumice is reduced to the metallic state by heating in a current of hydrogen. Then it is dropped into the tank of oil and hydrogen gas is blown through. The hydrogen may be obtained by splitting water into its two components, hydrogen and oxygen, by means of the electrical current, or by passing steam over spongy iron which takes out the oxygen. The stream of hydrogen blown through the hot oil converts the linoleic acid to oleic and then the oleic into stearic. If you figured up the weights from the symbols given above you would find that it takes about one pound of hydrogen to convert a hundred pounds of olein to stearin and the cost is only about one cent a pound. The nickel is unchanged and is easily separated. A trace of nickel may remain in the product, but as it is very much less than the amount dissolved when food is cooked in nickel-plated vessels it cannot be regarded as harmful. Even more unsaturated fats may be hydrogenated. Fish oil has hitherto been almost unusable because of its powerful and persistent odor. This is chiefly due to a fatty acid which properly bears the uneuphonious name of clupanodonic acid and has the composition of C_{18}H_{28}O_{2}. By comparing this with the symbol of the odorless stearic acid, C_{18}H_{36}O_{2}, you will see that all the rank fish oil lacks to make it respectable is eight hydrogen atoms. A Japanese chemist, Tsujimoto, has discovered how to add them and now the reformed fish oil under the names of "talgol" and "candelite" serves for lubricant and even enters higher circles as a soap or food. This process of hardening fats by hydrogenation resulted from the experiments of a French chemist, Professor Sabatier of Toulouse, in the last years of the last century, but, as in many other cases, the Germans were the first to take it up and profit by it. Before the war the copra or coconut oil from the British Asiatic colonies of India, Ceylon and Malaya went to Germany at the rate of $15,000,000 a year. The palm kernels grown in British West Africa were shipped, not to Liverpool, but to Hamburg, $19,000,000 worth annually. Here the oil was pressed out and used for margarin and the residual cake used for feeding cows produced butter or for feeding hogs produced lard. Half of the copra raised in the British possessions was sent to Germany and half of the oil from it was resold to the British margarin candle and soap makers at a handsome profit. The British chemists were not blind to this, but they could do nothing, first because the English politician was wedded to free trade, second, because the English farmer would not use oil cake for his stock. France was in a similar situation. Marseilles produced 15,500,000 gallons of oil from peanuts grown largely in the French African colonies--but shipped the oil-cake on to Hamburg. Meanwhile the Germans, in pursuit of their policy of attaining economic independence, were striving to develop their own tropical territory. The subjects of King George who because they had the misfortune to live in India were excluded from the British South African dominions or mistreated when they did come, were invited to come to German East Africa and set to raising peanuts in rivalry to French Senegal and British Coromandel. Before the war Germany got half of the Egyptian cottonseed and half of the Philippine copra. That is one of the reasons why German warships tried to check Dewey at Manila in 1898 and German troops tried to conquer Egypt in 1915. But the tide of war set the other way and the German plantations of palmnuts and peanuts in Africa have come into British possession and now the British Government is starting an educational campaign to teach their farmers to feed oil cake like the Germans and their people to eat peanuts like the Americans. The Germans shut off from the tropical fats supply were hard up for food and for soap, for lubricants and for munitions. Every person was given a fat card that reduced his weekly allowance to the minimum. Millers were required to remove the germs from their cereals and deliver them to the war department. Children were set to gathering horse-chestnuts, elderberries, linden-balls, grape seeds, cherry stones and sunflower heads, for these contain from six to twenty per cent. of oil. Even the blue-bottle fly--hitherto an idle creature for whom Beelzebub found mischief--was conscripted into the national service and set to laying eggs by the billion on fish refuse. Within a few days there is a crop of larvae which, to quote the "Chemische Zentralblatt," yields forty-five grams per kilogram of a yellow oil. This product, we should hope, is used for axle-grease and nitroglycerin, although properly purified it would be as nutritious as any other--to one who has no imagination. Driven to such straits Germany would have given a good deal for one of those tropical islands that we are so careless about. It might have been supposed that since the United States possessed the best land in the world for the production of cottonseed, coconuts, peanuts, and corn that it would have led all other countries in the utilization of vegetable oils for food. That this country has not so used its advantage is due to the fact that the new products have not merely had to overcome popular conservatism, ignorance and prejudice--hard things to fight in any case--but have been deliberately checked and hampered by the state and national governments in defense of vested interests. The farmer vote is a power that no politician likes to defy and the dairy business in every state was thoroughly organized. In New York the oleomargarin industry that in 1879 was turning out products valued at more than $5,000,000 a year was completely crushed out by state legislation.[2] The output of the United States, which in 1902 had risen to 126,000,000 pounds, was cut down to 43,000,000 pounds in 1909 by federal legislation. According to the disingenuous custom of American lawmakers the Act of 1902 was passed through Congress as a "revenue measure," although it meant a loss to the Government of more than three million dollars a year over what might be produced by a straight two cents a pound tax. A wholesale dealer in oleomargarin was made to pay a higher license than a wholesale liquor dealer. The federal law put a tax of ten cents a pound on yellow oleomargarin and a quarter of a cent a pound on the uncolored. But people--doubtless from pure prejudice--prefer a yellow spread for their bread, so the economical housewife has to work over her oleomargarin with the annatto which is given to her when she buys a package or, if the law prohibits this, which she is permitted to steal from an open box on the grocer's counter. A plausible pretext for such legislation is afforded by the fact that the butter substitutes are so much like butter that they cannot be easily distinguished from it unless the use of annatto is permitted to butter and prohibited to its competitors. Fradulent sales of substitutes of any kind ought to be prevented, but the recent pure food legislation in America has shown that it is possible to secure truthful labeling without resorting to such drastic measures. In Europe the laws against substitution were very strict, but not devised to restrict the industry. Consequently the margarin output of Germany doubled in the five years preceding the war and the output of England tripled. In Denmark the consumption of margarin rose from 8.8 pounds per capita in 1890 to 32.6 pounds in 1912. Yet the butter business, Denmark's pride, was not injured, and Germany and England imported more butter than ever before. Now that the price of butter in America has gone over the seventy-five cent mark Congress may conclude that it no longer needs to be protected against competition. The "compound lards" or "lard compounds," consisting usually of cottonseed oil and oleo-stearin, although the latter may now be replaced by hardened oil, met with the same popular prejudice and attempted legislative interference, but succeeded more easily in coming into common use under such names as "Cottosuet," "Kream Krisp," "Kuxit," "Korno," "Cottolene" and "Crisco." Oleomargarin, now generally abbreviated to margarin, originated, like many other inventions, in military necessity. The French Government in 1869 offered a prize for a butter substitute for the army that should be cheaper and better than butter in that it did not spoil so easily. The prize was won by a French chemist, Mége-Mouries, who found that by chilling beef fat the solid stearin could be separated from an oil (oleo) which was the substantially same as that in milk and hence in butter. Neutral lard acts the same. This discovery of how to separate the hard and soft fats was followed by improved methods for purifying them and later by the process for converting the soft into the hard fats by hydrogenation. The net result was to put into the hands of the chemist the ability to draw his materials at will from any land and from the vegetable and animal kingdoms and to combine them as he will to make new fat foods for every use; hard for summer, soft for winter; solid for the northerners and liquid for the southerners; white, yellow or any other color, and flavored to suit the taste. The Hindu can eat no fat from the sacred cow; the Mohammedan and the Jew can eat no fat from the abhorred pig; the vegetarian will touch neither; other people will take both. No matter, all can be accommodated. All the fats and oils, though they consist of scores of different compounds, have practically the same food value when freed from the extraneous matter that gives them their characteristic flavors. They are all practically tasteless and colorless. The various vegetable and animal oils and fats have about the same digestibility, 98 per cent.,[3] and are all ordinarily completely utilized in the body, supplying it with two and a quarter times as much energy as any other food. It does not follow, however, that there is no difference in the products. The margarin men accuse butter of harboring tuberculosis germs from which their product, because it has been heated or is made from vegetable fats, is free. The butter men retort that margarin is lacking in vitamines, those mysterious substances which in minute amounts are necessary for life and especially for growth. Both the claim and the objection lose a large part of their force where the margarin, as is customarily the case, is mixed with butter or churned up with milk to give it the familiar flavor. But the difficulty can be easily overcome. The milk used for either butter or margarin should be free or freed from disease germs. If margarin is altogether substituted for butter, the necessary vitamines may be sufficiently provided by milk, eggs and greens. Owing to these new processes all the fatty substances of all lands have been brought into competition with each other. In such a contest the vegetable is likely to beat the animal and the southern to win over the northern zones. In Europe before the war the proportion of the various ingredients used to make butter substitutes was as follows: AVERAGE COMPOSITION OF EUROPEAN MARGARIN Per Cent. Animal hard fats 25 Vegetable hard fats 35 Copra 29 Palm-kernel 6 Vegetable soft fats 26 Cottonseed 13 Peanut 6 Sesame 6 Soya-bean 1 Water, milk, salt 14 ___ 100 This is not the composition of any particular brand but the average of them all. The use of a certain amount of the oil of the sesame seed is required by the laws of Germany and Denmark because it can be easily detected by a chemical color test and so serves to prevent the margarin containing it from being sold as butter. "Open sesame!" is the password to these markets. Remembering that margarin originally was made up entirely of animal fats, soft and hard, we can see from the above figures how rapidly they are being displaced by the vegetable fats. The cottonseed and peanut oils have replaced the original oleo oil and the tropical oils from the coconut (copra) and African palm are crowding out the animal hard fats. Since now we can harden at will any of the vegetable oils it is possible to get along altogether without animal fats. Such vegetable margarins were originally prepared for sale in India, but proved unexpectedly popular in Europe, and are now being introduced into America. They are sold under various trade names suggesting their origin, such as "palmira," "palmona," "milkonut," "cocose," "coconut oleomargarin" and "nucoa nut margarin." The last named is stated to be made of coconut oil (for the hard fat) and peanut oil (for the soft fat), churned up with a culture of pasteurized milk (to impart the butter flavor). The law requires such a product to be branded "oleomargarine" although it is not. Such cases of compulsory mislabeling are not rare. You remember the "Pigs is Pigs" story. Peanut butter has won its way into the American menu without any camouflage whatever, and as a salad oil it is almost equally frank about its lowly origin. This nut, which grows on a vine instead of a tree, and is dug from the ground like potatoes instead of being picked with a pole, goes by various names according to locality, peanuts, ground-nuts, monkey-nuts, arachides and goobers. As it takes the place of cotton oil in some of its products so it takes its place in the fields and oilmills of Texas left vacant by the bollweevil. The once despised peanut added some $56,000,000 to the wealth of the South in 1916. The peanut is rich in the richest of foods, some 50 per cent. of oil and 30 per cent. of protein. The latter can be worked up into meat substitutes that will make the vegetarian cease to envy his omnivorous neighbor. Thanks largely to the chemist who has opened these new fields of usefulness, the peanut-raiser got $1.25 a bushel in 1917 instead of the 30 cents that he got four years before. It would be impossible to enumerate all the available sources of vegetable oils, for all seeds and nuts contain more or less fatty matter and as we become more economical we shall utilize of what we now throw away. The germ of the corn kernel, once discarded in the manufacture of starch, now yields a popular table oil. From tomato seeds, one of the waste products of the canning factory, can be extracted 22 per cent. of an edible oil. Oats contain 7 per cent. of oil. From rape seed the Japanese get 20,000 tons of oil a year. To the sources previously mentioned may be added pumpkin seeds, poppy seeds, raspberry seeds, tobacco seeds, cockleburs, hazelnuts, walnuts, beechnuts and acorns. The oil-bearing seeds of the tropics are innumerable and will become increasingly essential to the inhabitants of northern lands. It was the realization of this that brought on the struggle of the great powers for the possession of tropical territory which, for years before, they did not think worth while raising a flag over. No country in the future can consider itself safe unless it has secure access to such sources. We had a sharp lesson in this during the war. Palm oil, it seems, is necessary for the manufacture of tinplate, an industry that was built up in the United States by the McKinley tariff. The British possessions in West Africa were the chief source of palm oil and the Germans had the handling of it. During the war the British Government assumed control of the palm oil products of the British and German colonies and prohibited their export to other countries than England. Americans protested and beseeched, but in vain. The British held, quite correctly, that they needed all the oil they could get for food and lubrication and nitroglycerin. But the British also needed canned meat from America for their soldiers and when it was at length brought to their attention that the packers could not ship meat unless they had cans and that cans could not be made without tin and that tin could not be made without palm oil the British Government consented to let us buy a little of their palm oil. The lesson is that of Voltaire's story, "Candide," "Let us cultivate our own garden"--and plant a few palm trees in it--also rubber trees, but that is another story. The international struggle for oil led to the partition of the Pacific as the struggle for rubber led to the partition of Africa. Theodor Weber, as Stevenson says, "harried the Samoans" to get copra much as King Leopold of Belgium harried the Congoese to get caoutchouc. It was Weber who first fully realized that the South Sea islands, formerly given over to cannibals, pirates and missionaries, might be made immensely valuable through the cultivation of the coconut palms. When the ripe coconut is split open and exposed to the sun the meat dries up and shrivels and in this form, called "copra," it can be cut out and shipped to the factory where the oil is extracted and refined. Weber while German Consul in Samoa was also manager of what was locally known as "the long-handled concern" (_Deutsche Handels und Plantagen Gesellschaft der Südsee Inseln zu Hamburg_), a pioneer commercial and semi-official corporation that played a part in the Pacific somewhat like the British Hudson Bay Company in Canada or East India Company in Hindustan. Through the agency of this corporation on the start Germany acquired a virtual monopoly of the transportation and refining of coconut oil and would have become the dominant power in the Pacific if she had not been checked by force of arms. In Apia Bay in 1889 and again in Manila Bay in 1898 an American fleet faced a German fleet ready for action while a British warship lay between. So we rescued the Philippines and Samoa from German rule and in 1914 German power was eliminated from the Pacific. During the ten years before the war, the production of copra in the German islands more than doubled and this was only the beginning of the business. Now these islands have been divided up among Australia, New Zealand and Japan, and these countries are planning to take care of the copra. But although we get no extension of territory from the war we still have the Philippines and some of the Samoan Islands, and these are capable of great development. From her share of the Samoan Islands Germany got a million dollars' worth of copra and we might get more from ours. The Philippines now lead the world in the production of copra, but Java is a close second and Ceylon not far behind. If we do not look out we will be beaten both by the Dutch and the British, for they are undertaking the cultivation of the coconut on a larger scale and in a more systematic way. According to an official bulletin of the Philippine Government a coconut plantation should bring in "dividends ranging from 10 to 75 per cent. from the tenth to the hundredth year." And this being printed in 1913 figured the price of copra at 3-1/2 cents, whereas it brought 4-1/2 cents in 1918, so the prospect is still more encouraging. The copra is half fat and can be cheaply shipped to America, where it can be crushed in the southern oilmills when they are not busy on cottonseed or peanuts. But even this cost of transportation can be reduced by extracting the oil in the islands and shipping it in bulk like petroleum in tank steamers. In the year ending June, 1918, the United States imported from the Philippines 155,000,000 pounds of coconut oil worth $18,000,000 and 220,000,000 pounds of copra worth $10,000,000. But this was about half our total importations; the rest of it we had to get from foreign countries. Panama palms may give us a little relief from this dependence on foreign sources. In 1917 we imported 19,000,000 whole coconuts from Panama valued at $700,000. [Illustration: SPLITTING COCONUTS ON THE ISLAND OF TAHITI After drying in the sun the meat is picked and the oil extracted for making coconut butter] [Illustration: From "America's Munitions" THE ELECTRIC CURRENT PASSING THROUGH SALT WATER IN THESE CELLS DECOMPOSES THE SALT INTO CAUSTIC SODA AND CHLORINE GAS There were eight rooms like this in the Edgewood plant, capable of producing 200,000 pounds of chlorine a day] A new form of fat that has rapidly come into our market is the oil of the soya or soy bean. In 1918 we imported over 300,000,000 pounds of soy-bean oil, mostly from Manchuria. The oil is used in manufacture of substitutes for butter, lard, cheese, milk and cream, as well as for soap and paint. The soy-bean can be raised in the United States wherever corn can be grown and provides provender for man and beast. The soy meal left after the extraction of the oil makes a good cattle food and the fermented juice affords the shoya sauce made familiar to us through the popularity of the chop-suey restaurants. As meat and dairy products become scarcer and dearer we shall become increasingly dependent upon the vegetable fats. We should therefore devise means of saving what we now throw away, raise as much as we can under our own flag, keep open avenues for our foreign supply and encourage our cooks to make use of the new products invented by our chemists. CHAPTER XII FIGHTING WITH FUMES The Germans opened the war using projectiles seventeen inches in diameter. They closed it using projectiles one one-hundred millionth of an inch in diameter. And the latter were more effective than the former. As the dimensions were reduced from molar to molecular the battle became more intense. For when the Big Bertha had shot its bolt, that was the end of it. Whomever it hit was hurt, but after that the steel fragments of the shell lay on the ground harmless and inert. The men in the dugouts could hear the shells whistle overhead without alarm. But the poison gas could penetrate where the rifle ball could not. The malignant molecules seemed to search out their victims. They crept through the crevices of the subterranean shelters. They hunted for the pinholes in the face masks. They lay in wait for days in the trenches for the soldiers' return as a cat watches at the hole of a mouse. The cannon ball could be seen and heard. The poison gas was invisible and inaudible, and sometimes even the chemical sense which nature has given man for his protection, the sense of smell, failed to give warning of the approach of the foe. The smaller the matter that man can deal with the more he can get out of it. So long as man was dependent for power upon wind and water his working capacity was very limited. But as soon as he passed over the border line from physics into chemistry and learned how to use the molecule, his efficiency in work and warfare was multiplied manifold. The molecular bombardment of the piston by steam or the gases of combustion runs his engines and propels his cars. The first man who wanted to kill another from a safe distance threw the stone by his arm's strength. David added to his arm the centrifugal force of a sling when he slew Goliath. The Romans improved on this by concentrating in a catapult the strength of a score of slaves and casting stone cannon balls to the top of the city wall. But finally man got closer to nature's secret and discovered that by loosing a swarm of gaseous molecules he could throw his projectile seventy-five miles and then by the same force burst it into flying fragments. There is no smaller projectile than the atom unless our belligerent chemists can find a way of using the electron stream of the cathode ray. But this so far has figured only in the pages of our scientific romancers and has not yet appeared on the battlefield. If, however, man could tap the reservoir of sub-atomic energy he need do no more work and would make no more war, for unlimited powers of construction and destruction would be at his command. The forces of the infinitesimal are infinite. The reason why a gas is so active is because it is so egoistic. Psychologically interpreted, a gas consists of particles having the utmost aversion to one another. Each tries to get as far away from every other as it can. There is no cohesive force; no attractive impulse; nothing to draw them together except the all too feeble power of gravitation. The hotter they get the more they try to disperse and so the gas expands. The gas represents the extreme of individualism as steel represents the extreme of collectivism. The combination of the two works wonders. A hot gas in a steel cylinder is the most powerful agency known to man, and by means of it he accomplishes his greatest achievements in peace or war time. The projectile is thrown from the gun by the expansive force of the gases released from the powder and when it reaches its destination it is blown to pieces by the same force. This is the end of it if it is a shell of the old-fashioned sort, for the gases of combustion mingle harmlessly with the air of which they are normal constituents. But if it is a poison gas shell each molecule as it is released goes off straight into the air with a speed twice that of the cannon ball and carries death with it. A man may be hit by a heavy piece of lead or iron and still survive, but an unweighable amount of lethal gas may be fatal to him. Most of the novelties of the war were merely extensions of what was already known. To increase the caliber of a cannon from 38 to 42 centimeters or its range from 30 to 75 miles does indeed make necessary a decided change in tactics, but it is not comparable to the revolution effected by the introduction of new weapons of unprecedented power such as airplanes, submarines, tanks, high explosives or poison gas. If any army had been as well equipped with these in the beginning as all armies were at the end it might easily have won the war. That is to say, if the general staff of any of the powers had had the foresight and confidence to develop and practise these modes of warfare on a large scale in advance it would have been irresistible against an enemy unprepared to meet them. But no military genius appeared on either side with sufficient courage and imagination to work out such schemes in secret before trying them out on a small scale in the open. Consequently the enemy had fair warning and ample time to learn how to meet them and methods of defense developed concurrently with methods of attack. For instance, consider the motor fortresses to which Ludendorff ascribes his defeat. The British first sent out a few clumsy tanks against the German lines. Then they set about making a lot of stronger and livelier ones, but by the time these were ready the Germans had field guns to smash them and chain fences with concrete posts to stop them. On the other hand, if the Germans had followed up their advantage when they first set the cloud of chlorine floating over the battlefield of Ypres they might have won the war in the spring of 1915 instead of losing it in the fall of 1918. For the British were unprepared and unprotected against the silent death that swept down upon them on the 22nd of April, 1915. What happened then is best told by Sir Arthur Conan Doyle in his "History of the Great War." From the base of the German trenches over a considerable length there appeared jets of whitish vapor, which gathered and swirled until they settled into a definite low cloud-bank, greenish-brown below and yellow above, where it reflected the rays of the sinking sun. This ominous bank of vapor, impelled by a northern breeze, drifted swiftly across the space which separated the two lines. The French troops, staring over the top of their parapet at this curious screen which ensured them a temporary relief from fire, were observed suddenly to throw up their hands, to clutch at their throats, and to fall to the ground in the agonies of asphyxiation. Many lay where they had fallen, while their comrades, absolutely helpless against this diabolical agency, rushed madly out of the mephitic mist and made for the rear, over-running the lines of trenches behind them. Many of them never halted until they had reached Ypres, while others rushed westwards and put the canal between themselves and the enemy. The Germans, meanwhile, advanced, and took possession of the successive lines of trenches, tenanted only by the dead garrisons, whose blackened faces, contorted figures, and lips fringed with the blood and foam from their bursting lungs, showed the agonies in which they had died. Some thousands of stupefied prisoners, eight batteries of French field-guns, and four British 4.7's, which had been placed in a wood behind the French position, were the trophies won by this disgraceful victory. Under the shattering blow which they had received, a blow particularly demoralizing to African troops, with their fears of magic and the unknown, it was impossible to rally them effectually until the next day. It is to be remembered in explanation of this disorganization that it was the first experience of these poison tactics, and that the troops engaged received the gas in a very much more severe form than our own men on the right of Langemarck. For a time there was a gap five miles broad in the front of the position of the Allies, and there were many hours during which there was no substantial force between the Germans and Ypres. They wasted their time, however, in consolidating their ground, and the chance of a great coup passed forever. They had sold their souls as soldiers, but the Devil's price was a poor one. Had they had a corps of cavalry ready, and pushed them through the gap, it would have been the most dangerous moment of the war. A deserter had come over from the German side a week before and told them that cylinders of poison gas had been laid in the front trenches, but no one believed him or paid any attention to his tale. War was then, in the Englishman's opinion, a gentleman's game, the royal sport, and poison was prohibited by the Hague rules. But the Germans were not playing the game according to the rules, so the British soldiers were strangled in their own trenches and fell easy victims to the advancing foe. Within half an hour after the gas was turned on 80 per cent. of the opposing troops were knocked out. The Canadians, with wet handkerchiefs over their faces, closed in to stop the gap, but if the Germans had been prepared for such success they could have cleared the way to the coast. But after such trials the Germans stopped the use of free chlorine and began the preparation of more poisonous gases. In some way that may not be revealed till the secret history of the war is published, the British Intelligence Department obtained a copy of the lecture notes of the instructions to the German staff giving details of the new system of gas warfare to be started in December. Among the compounds named was phosgene, a gas so lethal that one part in ten thousand of air may be fatal. The antidote for it is hexamethylene tetramine. This is not something the soldier--or anybody else--is accustomed to carry around with him, but the British having had a chance to cram up in advance on the stolen lecture notes were ready with gas helmets soaked in the reagent with the long name. The Germans rejoiced when gas bombs took the place of bayonets because this was a field in which intelligence counted for more than brute force and in which therefore they expected to be supreme. As usual they were right in their major premise but wrong in their conclusion, owing to the egoism of their implicit minor premise. It does indeed give the advantage to skill and science, but the Germans were beaten at their own game, for by the end of the war the United States was able to turn out toxic gases at a rate of 200 tons a day, while the output of Germany or England was only about 30 tons. A gas plant was started at Edgewood, Maryland, in November, 1917. By March it was filling shell and before the war put a stop to its activities in the fall it was producing 1,300,000 pounds of chlorine, 1,000,000 pounds of chlorpicrin, 1,300,000 pounds of phosgene and 700,000 pounds of mustard gas a month. Chlorine, the first gas used, is unpleasantly familiar to every one who has entered a chemical laboratory or who has smelled the breath of bleaching powder. It is a greenish-yellow gas made from common salt. The Germans employed it at Ypres by laying cylinders of the liquefied gas in the trenches, about a yard apart, and running a lead discharge pipe over the parapet. When the stop cocks are turned the gas streams out and since it is two and a half times as heavy as air it rolls over the ground like a noisome mist. It works best when the ground slopes gently down toward the enemy and when the wind blows in that direction at a rate between four and twelve miles an hour. But the wind, being strictly neutral, may change its direction without warning and then the gases turn back in their flight and attack their own side, something that rifle bullets have never been known to do. [Illustration: © International Film Service GERMANS STARTING A GAS ATTACK ON THE RUSSIAN LINES Behind the cylinders from which the gas streams are seen three lines of German troops waiting to attack. The photograph was taken from above by a Russian airman] [Illustration: © Press Illustrating Service FILLING THE CANNISTERS OF GAS MASKS WITH CHARCOAL MADE FROM FRUIT PITS IN LONG ISLAND CITY] Because free chlorine would not stay put and was dependent on the favor of the wind for its effect, it was later employed, not as an elemental gas, but in some volatile liquid that could be fired in a shell and so released at any particular point far back of the front trenches. The most commonly used of these compounds was phosgene, which, as the reader can see by inspection of its formula, COCl_{2}, consists of chlorine (Cl) combined with carbon monoxide (CO), the cause of deaths from illuminating gas. These two poisonous gases, chlorine and carbon monoxide, when mixed together, will not readily unite, but if a ray of sunlight falls upon the mixture they combine at once. For this reason John Davy, who discovered the compound over a hundred years ago, named it phosgene, that is, "produced by light." The same roots recur in hydrogen, so named because it is "produced from water," and phosphorus, because it is a "light-bearer." In its modern manufacture the catalyzer or instigator of the combination is not sunlight but porous carbon. This is packed in iron boxes eight feet long, through which the mixture of the two gases was forced. Carbon monoxide may be made by burning coke with a supply of air insufficient for complete combustion, but in order to get the pure gas necessary for the phosgene common air was not used, but instead pure oxygen extracted from it by a liquid air plant. Phosgene is a gas that may be condensed easily to a liquid by cooling it down to 46 degrees Fahrenheit. A mixture of three-quarters chlorine with one-quarter phosgene has been found most effective. By itself phosgene has an inoffensive odor somewhat like green corn and so may fail to arouse apprehension until a toxic concentration is reached. But even small doses have such an effect upon the heart action for days afterward that a slight exertion may prove fatal. The compound manufactured in largest amount in America was chlorpicrin. This, like the others, is not so unfamiliar as it seems. As may be seen from its formula, CCl_{3}NO_{2}, it is formed by joining the nitric acid radical (NO_{2}), found in all explosives, with the main part of chloroform (HCCl_{3}). This is not quite so poisonous as phosgene, but it has the advantage that it causes nausea and vomiting. The soldier so affected is forced to take off his gas mask and then may fall victim to more toxic gases sent over simultaneously. Chlorpicrin is a liquid and is commonly loaded in a shell or bomb with 20 per cent. of tin chloride, which produces dense white fumes that go through gas masks. It is made from picric acid (trinitrophenol), one of the best known of the high explosives, by treatment with chlorine. The chlorine is obtained, as it is in the household, from common bleaching powder, or "chloride of lime." This is mixed with water to form a cream in a steel still 18 feet high and 8 feet in diameter. A solution of calcium picrate, that is, the lime salt of picric acid, is pumped in and as the reaction begins the mixture heats up and the chlorpicrin distils over with the steam. When the distillate is condensed the chlorpicrin, being the heavier liquid, settles out under the layer of water and may be drawn off to fill the shell. Much of what a student learns in the chemical laboratory he is apt to forget in later life if he does not follow it up. But there are two gases that he always remembers, chlorine and hydrogen sulfide. He is lucky if he has escaped being choked by the former or sickened by the latter. He can imagine what the effect would be if two offensive fumes could be combined without losing their offensive features. Now a combination something like this is the so-called mustard gas, which is not a gas and is not made from mustard. But it is easily gasified, and oil of mustard is about as near as Nature dare come to making such sinful stuff. It was first made by Guthrie, an Englishman, in 1860, and rediscovered by a German chemist, Victor Meyer, in 1886, but he found it so dangerous to work with that he abandoned the investigation. Nobody else cared to take it up, for nobody could see any use for it. So it remained in innocuous desuetude, a mere name in "Beilstein's Dictionary," together with the thousands of other organic compounds that have been invented and never utilized. But on July 12, 1917, the British holding the line at Ypres were besprinkled with this villainous substance. Its success was so great that the Germans henceforth made it their main reliance and soon the Allies followed suit. In one offensive of ten days the Germans are said to have used a million shells containing 2500 tons of mustard gas. The making of so dangerous a compound on a large scale was one of the most difficult tasks set before the chemists of this and other countries, yet it was successfully solved. The raw materials are chlorine, alcohol and sulfur. The alcohol is passed with steam through a vertical iron tube filled with kaolin and heated. This converts the alcohol into a gas known as ethylene (C_{2}H_{4}). Passing a stream of chlorine gas into a tank of melted sulfur produces sulfur monochloride and this treated with the ethylene makes the "mustard." The final reaction was carried on at the Edgewood Arsenal in seven airtight tanks or "reactors," each having a capacity of 30,000 pounds. The ethylene gas being led into the tank and distributed through the liquid sulfur chloride by porous blocks or fine nozzles, the two chemicals combined to form what is officially named "di-chlor-di-ethyl-sulfide" (ClC_{2}H_{4}SC_{2}H_{4}Cl). This, however, is too big a mouthful, so even the chemists were glad to fall in with the commonalty and call it "mustard gas." The effectiveness of "mustard" depends upon its persistence. It is a stable liquid, evaporating slowly and not easily decomposed. It lingers about trenches and dugouts and impregnates soil and cloth for days. Gas masks do not afford complete protection, for even if they are impenetrable they must be taken off some time and the gas lies in wait for that time. In some cases the masks were worn continuously for twelve hours after the attack, but when they were removed the soldiers were overpowered by the poison. A place may seem to be free from it but when the sun heats up the ground the liquid volatilizes and the vapor soaks through the clothing. As the men become warmed up by work their skin is blistered, especially under the armpits. The mustard acts like steam, producing burns that range from a mere reddening to serious ulcerations, always painful and incapacitating, but if treated promptly in the hospital rarely causing death or permanent scars. The gas attacks the eyes, throat, nose and lungs and may lead to bronchitis or pneumonia. It was found necessary at the front to put all the clothing of the soldiers into the sterilizing ovens every night to remove all traces of mustard. General Johnson and his staff in the 77th Division were poisoned in their dugouts because they tried to alleviate the discomfort of their camp cots by bedding taken from a neighboring village that had been shelled the day before. Of the 925 cases requiring medical attention at the Edgewood Arsenal 674 were due to mustard. During the month of August 3-1/2 per cent. of the mustard plant force were sent to the hospital each day on the average. But the record of the Edgewood Arsenal is a striking demonstration of what can be done in the prevention of industrial accidents by the exercise of scientific prudence. In spite of the fact that from three to eleven thousand men were employed at the plant for the year 1918 and turned out some twenty thousand tons of the most poisonous gases known to man, there were only three fatalities and not a single case of blindness. Besides the four toxic gases previously described, chlorine, phosgene, chlorpicrin and mustard, various other compounds have been and many others might be made. A list of those employed in the present war enumerates thirty, among them compounds of bromine, arsenic and cyanogen that may prove more formidable than any so far used. American chemists kept very mum during the war but occasionally one could not refrain from saying: "If the Kaiser knew what I know he would surrender unconditionally by telegraph." No doubt the science of chemical warfare is in its infancy and every foresighted power has concealed weapons of its own in reserve. One deadly compound, whose identity has not yet been disclosed, is known as "Lewisite," from Professor Lewis of Northwestern, who was manufacturing it at the rate of ten tons a day in the "Mouse Trap" stockade near Cleveland. Throughout the history of warfare the art of defense has kept pace with the art of offense and the courage of man has never failed, no matter to what new danger he was exposed. As each new gas employed by the enemy was detected it became the business of our chemists to discover some method of absorbing or neutralizing it. Porous charcoal, best made from such dense wood as coconut shells, was packed in the respirator box together with layers of such chemicals as will catch the gases to be expected. Charcoal absorbs large quantities of any gas. Soda lime and potassium permanganate and nickel salts were among the neutralizers used. The mask is fitted tightly about the face or over the head with rubber. The nostrils are kept closed with a clip so breathing must be done through the mouth and no air can be inhaled except that passing through the absorbent cylinder. Men within five miles of the front were required to wear the masks slung on their chests so they could be put on within six seconds. A well-made mask with a fresh box afforded almost complete immunity for a time and the soldiers learned within a few days to handle their masks adroitly. So the problem of defense against this new offensive was solved satisfactorily, while no such adequate protection against the older weapons of bayonet and shrapnel has yet been devised. Then the problem of the offense was to catch the opponent with his mask off or to make him take it off. Here the lachrymators and the sternutators, the tear gases and the sneeze gases, came into play. Phenylcarbylamine chloride would make the bravest soldier weep on the battlefield with the abandonment of a Greek hero. Di-phenyl-chloro-arsine would set him sneezing. The Germans alternated these with diabolical ingenuity so as to catch us unawares. Some shells gave off voluminous smoke or a vile stench without doing much harm, but by the time our men got used to these and grew careless about their masks a few shells of some extremely poisonous gas were mixed with them. The ideal gas for belligerent purposes would be odorless, colorless and invisible, toxic even when diluted by a million parts of air, not set on fire or exploded by the detonator of the shell, not decomposed by water, not readily absorbed, stable enough to stand storage for six months and capable of being manufactured by the thousands of tons. No one gas will serve all aims. For instance, phosgene being very volatile and quickly dissipated is thrown into trenches that are soon to be taken while mustard gas being very tenacious could not be employed in such a case for the trenches could not be occupied if they were captured. The extensive use of poison gas in warfare by all the belligerents is a vindication of the American protest at the Hague Conference against its prohibition. At the First Conference of 1899 Captain Mahan argued very sensibly that gas shells were no worse than other projectiles and might indeed prove more merciful and that it was illogical to prohibit a weapon merely because of its novelty. The British delegates voted with the Americans in opposition to the clause "the contracting parties agree to abstain from the use of projectiles the sole object of which is the diffusion of asphyxiating or deleterious gases." But both Great Britain and Germany later agreed to the provision. The use of poison gas by Germany without warning was therefore an act of treachery and a violation of her pledge, but the United States has consistently refused to bind herself to any such restriction. The facts reported by General Amos A. Fries, in command of the overseas branch of the American Chemical Warfare Service, give ample support to the American contention at The Hague: Out of 1000 gas casualties there are from 30 to 40 fatalities, while out of 1000 high explosive casualties the number of fatalities run from 200 to 250. While exact figures are as yet not available concerning the men permanently crippled or blinded by high explosives one has only to witness the debarkation of a shipload of troops to be convinced that the number is very large. On the other hand there is, so far as known at present, not a single case of permanent disability or blindness among our troops due to gas and this in face of the fact that the Germans used relatively large quantities of this material. In the light of these facts the prejudice against the use of gas must gradually give way; for the statement made to the effect that its use is contrary to the principles of humanity will apply with far greater force to the use of high explosives. As a matter of fact, for certain purposes toxic gas is an ideal agent. For example, it is difficult to imagine any agent more effective or more humane that may be used to render an opposing battery ineffective or to protect retreating troops. Captain Mahan's argument at The Hague against the proposed prohibition of poison gas is so cogent and well expressed that it has been quoted in treatises on international law ever since. These reasons were, briefly: 1. That no shell emitting such gases is as yet in practical use or has undergone adequate experiment; consequently, a vote taken now would be taken in ignorance of the facts as to whether the results would be of a decisive character or whether injury in excess of that necessary to attain the end of warfare--the immediate disabling of the enemy--would be inflicted. 2. That the reproach of cruelty and perfidy, addressed against these supposed shells, was equally uttered formerly against firearms and torpedoes, both of which are now employed without scruple. Until we know the effects of such asphyxiating shells, there was no saying whether they would be more or less merciful than missiles now permitted. That it was illogical, and not demonstrably humane, to be tender about asphyxiating men with gas, when all are prepared to admit that it was allowable to blow the bottom out of an ironclad at midnight, throwing four or five hundred into the sea, to be choked by water, with scarcely the remotest chance of escape. As Captain Mahan says, the same objection has been raised at the introduction of each new weapon of war, even though it proved to be no more cruel than the old. The modern rifle ball, swift and small and sterilized by heat, does not make so bad a wound as the ancient sword and spear, but we all remember how gunpowder was regarded by the dandies of Hotspur's time: And it was great pity, so it was, This villainous saltpeter should be digg'd Out of the bowels of the harmless earth Which many a good tall fellow had destroy'd So cowardly; and but for these vile guns He would himself have been a soldier. The real reason for the instinctive aversion manifested against any new arm or mode of attack is that it reveals to us the intrinsic horror of war. We naturally revolt against premeditated homicide, but we have become so accustomed to the sword and latterly to the rifle that they do not shock us as they ought when we think of what they are made for. The Constitution of the United States prohibits the infliction of "cruel and unusual punishments." The two adjectives were apparently used almost synonymously, as though any "unusual" punishment were necessarily "cruel," and so indeed it strikes us. But our ingenious lawyers were able to persuade the courts that electrocution, though unknown to the Fathers and undeniably "unusual," was not unconstitutional. Dumdum bullets are rightfully ruled out because they inflict frightful and often incurable wounds, and the aim of humane warfare is to disable the enemy, not permanently to injure him. [Illustration: From "America's Munitions" THE CHLORPICRIN PLANT AT THE EDGEWOOD ARSENAL From these stills, filled with a mixture of bleaching powder, lime, and picric acid, the poisonous gas, chlorpicrin, distills off. This plant produced 31 tons in one day] [Illustration: Courtesy of the Metal and Thermit Corporation, N.Y. REPAIRING THE BROKEN STERN POST OF THE U.S.S. NORTHERN PACIFIC, THE BIGGEST MARINE WELD IN THE WORLD On the right the fractured stern post is shown. On the left it is being mended by means of thermit. Two crucibles each containing 700 pounds of the thermit mixture are seen on the sides of the vessel. From the bottom of these the melted steel flowed down to fill the fracture] In spite of the opposition of the American and British delegates the First Hague Conference adopted the clause, "The contracting powers agree to abstain from the use of projectiles the [sole] object of which is the diffusion of asphyxiating or deleterious gases." The word "sole" (_unique_) which appears in the original French text of The Hague convention is left out of the official English translation. This is a strange omission considering that the French and British defended their use of explosives which diffuse asphyxiating and deleterious gases on the ground that this was not the "sole" purpose of the bombs but merely an accidental effect of the nitric powder used. The Hague Congress of 1907 placed in its rules for war: "It is expressly forbidden to employ poisons or poisonous weapons." But such attempts to rule out new and more effective means of warfare are likely to prove futile in any serious conflict and the restriction gives the advantage to the most unscrupulous side. We Americans, if ever we give our assent to such an agreement, would of course keep it, but our enemy--whoever he may be in the future--will be, as he always has been, utterly without principle and will not hesitate to employ any weapon against us. Besides, as the Germans held, chemical warfare favors the army that is most intelligent, resourceful and disciplined and the nation that stands highest in science and industry. This advantage, let us hope, will be on our side. CHAPTER XIII PRODUCTS OF THE ELECTRIC FURNACE The control of man over the materials of nature has been vastly enhanced by the recent extension of the range of temperature at his command. When Fahrenheit stuck the bulb of his thermometer into a mixture of snow and salt he thought he had reached the nadir of temperature, so he scratched a mark on the tube where the mercury stood and called it zero. But we know that absolute zero, the total absence of heat, is 459 of Fahrenheit's degrees lower than his zero point. The modern scientist can get close to that lowest limit by making use of the cooling by the expansion principle. He first liquefies air under pressure and then releasing the pressure allows it to boil off. A tube of hydrogen immersed in the liquid air as it evaporates is cooled down until it can be liquefied. Then the boiling hydrogen is used to liquefy helium, and as this boils off it lowers the temperature to within three or four degrees of absolute zero. The early metallurgist had no hotter a fire than he could make by blowing charcoal with a bellows. This was barely enough for the smelting of iron. But by the bringing of two carbon rods together, as in the electric arc light, we can get enough heat to volatilize the carbon at the tips, and this means over 7000 degrees Fahrenheit. By putting a pressure of twenty atmospheres onto the arc light we can raise it to perhaps 14,000 degrees, which is 3000 degrees hotter than the sun. This gives the modern man a working range of about 14,500 degrees, so it is no wonder that he can perform miracles. When a builder wants to make an old house over into a new one he takes it apart brick by brick and stone by stone, then he puts them together in such new fashion as he likes. The electric furnace enables the chemist to take his materials apart in the same way. As the temperature rises the chemical and physical forces that hold a body together gradually weaken. First the solid loosens up and becomes a liquid, then this breaks bonds and becomes a gas. Compounds break up into their elements. The elemental molecules break up into their component atoms and finally these begin to throw off corpuscles of negative electricity eighteen hundred times smaller than the smallest atom. These electrons appear to be the building stones of the universe. No indication of any smaller units has been discovered, although we need not assume that in the electron science has delivered, what has been called, its "ultim-atom." The Greeks called the elemental particles of matter "atoms" because they esteemed them "indivisible," but now in the light of the X-ray we can witness the disintegration of the atom into electrons. All the chemical and physical properties of matter, except perhaps weight, seem to depend upon the number and movement of the negative and positive electrons and by their rearrangement one element may be transformed into another. So the electric furnace, where the highest attainable temperature is combined with the divisive and directive force of the current, is a magical machine for accomplishment of the metamorphoses desired by the creative chemist. A hundred years ago Davy, by dipping the poles of his battery into melted soda lye, saw forming on one of them a shining globule like quicksilver. It was the metal sodium, never before seen by man. Nowadays this process of electrolysis (electric loosening) is carried out daily by the ton at Niagara. The reverse process, electro-synthesis (electric combining), is equally simple and even more important. By passing a strong electric current through a mixture of lime and coke the metal calcium disengages itself from the oxygen of the lime and attaches itself to the carbon. Or, to put it briefly, CaO + 3C --> CaC_{2} + CO lime coke calcium carbon carbide monoxide This reaction is of peculiar importance because it bridges the gulf between the organic and inorganic worlds. It was formerly supposed that the substances found in plants and animals, mostly complex compounds of carbon, hydrogen and oxygen, could only be produced by "vital forces." If this were true it meant that chemistry was limited to the mineral kingdom and to the extraction of such carbon compounds as happened to exist ready formed in the vegetable and animal kingdoms. But fortunately this barrier to human achievement proved purely illusory. The organic field, once man had broken into it, proved easier to work in than the inorganic. But it must be confessed that man is dreadfully clumsy about it yet. He takes a thousand horsepower engine and an electric furnace at several thousand degrees to get carbon into combination with hydrogen while the little green leaf in the sunshine does it quietly without getting hot about it. Evidently man is working as wastefully as when he used a thousand slaves to drag a stone to the pyramid or burned down a house to roast a pig. Not until his laboratory is as cool and calm and comfortable as the forest and the field can the chemist call himself completely successful. But in spite of his clumsiness the chemist is actually making things that he wants and cannot get elsewhere. The calcium carbide that he manufactures from inorganic material serves as the raw material for producing all sorts of organic compounds. The electric furnace was first employed on a large scale by the Cowles Electric Smelting and Aluminum Company at Cleveland in 1885. On the dump were found certain lumps of porous gray stone which, dropped into water, gave off a gas that exploded at touch of a match with a splendid bang and flare. This gas was acetylene, and we can represent the reaction thus: CaC_{2} + 2 H_{2}O --> C_{2}H_{2} + CaO_{2}H_{2} calcium carbide _added_ to water _ gives_ acetylene _and_ slaked lime We are all familiar with this reaction now, for it is acetylene that gives the dazzling light of the automobiles and of the automatic signal buoys of the seacoast. When burned with pure oxygen instead of air it gives the hottest of chemical flames, hotter even than the oxy-hydrogen blowpipe. For although a given weight of hydrogen will give off more heat when it burns than carbon will, yet acetylene will give off more heat than either of its elements or both of them when they are separate. This is because acetylene has stored up heat in its formation instead of giving it off as in most reactions, or to put it in chemical language, acetylene is an endothermic compound. It has required energy to bring the H and the C together, therefore it does not require energy to separate them, but, on the contrary, energy is released when they are separated. That is to say, acetylene is explosive not only when mixed with air as coal gas is but by itself. Under a suitable impulse acetylene will break up into its original carbon and hydrogen with great violence. It explodes with twice as much force without air as ordinary coal gas with air. It forms an explosive compound with copper, so it has to be kept out of contact with brass tubes and stopcocks. But compressed in steel cylinders and dissolved in acetone, it is safe and commonly used for welding and melting. It is a marvelous though not an unusual sight on city streets to see a man with blue glasses on cutting down through a steel rail with an oxy-acetylene blowpipe as easily as a carpenter saws off a board. With such a flame he can carve out a pattern in a steel plate in a way that reminds me of the days when I used to make brackets with a scroll saw out of cigar boxes. The torch will travel through a steel plate an inch or two thick at a rate of six to ten inches a minute. [Illustration: Courtesy of the Carborundum Company, Niagara Falls MAKING ALOXITE IN THE ELECTRIC FURNACES BY FUSING COKE AND BAUXITE In the background are the circular furnaces. In the foreground are the fused masses of the product] [Illustration: Courtesy of the Carborundum Co., Niagara Falls A BLOCK OF CARBORUNDUM CRYSTALS] [Illustration: Courtesy of the Carborundum Co., Niagara Falls MAKING CARBORUNDUM IN THE ELECTRIC FURNACE At the end may be seen the attachments for the wires carrying the electric current and on the side the flames from the burning carbon.] The temperatures attainable with various fuels in the compound blowpipe are said to be: Acetylene with oxygen 7878° F. Hydrogen with oxygen 6785° F. Coal gas with oxygen 6575° F. Gasoline with oxygen 5788° F. If we compare the formula of acetylene, C_{2}H_{2} with that of ethylene, C_{2}H_{4}, or with ethane, C_{2}H_{6}, we see that acetylene could take on two or four more atoms. It is evidently what the chemists call an "unsaturated" compound, one that has not reached its limit of hydrogenation. It is therefore a very active and energetic compound, ready to pick up on the slightest instigation hydrogen or oxygen or chlorine or any other elements that happen to be handy. This is why it is so useful as a starting point for synthetic chemistry. To build up from this simple substance, acetylene, the higher compounds of carbon and oxygen it is necessary to call in the aid of that mysterious agency, the catalyst. Acetylene is not always acted upon by water, as we know, for we see it bubbling up through the water when prepared from the carbide. But if to the water be added a little acid and a mercury salt, the acetylene gas will unite with the water forming a new compound, acetaldehyde. We can show the change most simply in this fashion: C_{2}H_{2} + H_{2}O --> C_{2}H_{4}O acetylene _added to_ water _forms_ acetaldehyde Acetaldehyde is not of much importance in itself, but is useful as a transition. If its vapor mixed with hydrogen is passed over finely divided nickel, serving as a catalyst, the two unite and we have alcohol, according to this reaction: C_{2}H_{4}O + H_{2} --> C_{2}H_{6}O acetaldehyde _added to_ hydrogen _forms_ alcohol Alcohol we are all familiar with--some of us too familiar, but the prohibition laws will correct that. The point to be noted is that the alcohol we have made from such unpromising materials as limestone and coal is exactly the same alcohol as is obtained by the fermentation of fruits and grains by the yeast plant as in wine and beer. It is not a substitute or imitation. It is not the wood spirits (methyl alcohol, CH_{4}O), produced by the destructive distillation of wood, equally serviceable as a solvent or fuel, but undrinkable and poisonous. Now, as we all know, cider and wine when exposed to the air gradually turn into vinegar, that is, by the growth of bacteria the alcohol is oxidized to acetic acid. We can, if we like, dispense with the bacteria and speed up the process by employing a catalyst. Acetaldehyde, which is halfway between alcohol and acid, may also be easily oxidized to acetic acid. The relationship is readily seen by this: C{2}H_{6}O --> CC_{2}H_{4}O --> C_{2}H_{4}O_{3} alcohol acetaldehyde acetic acid Acetic acid, familiar to us in a diluted and flavored form as vinegar, is when concentrated of great value in industry, especially as a solvent. I have already referred to its use in combination with cellulose as a "dope" for varnishing airplane canvas or making non-inflammable film for motion pictures. Its combination with lime, calcium acetate, when heated gives acetone, which, as may be seen from its formula (C_{3}H_{6}O) is closely related to the other compounds we have been considering, but it is neither an alcohol nor an acid. It is extensively employed as a solvent. Acetone is not only useful for dissolving solids but it will under pressure dissolve many times its volume of gaseous acetylene. This is a convenient way of transporting and handling acetylene for lighting or welding. If instead of simply mixing the acetone and acetylene in a solution we combine them chemically we can get isoprene, which is the mother substance of ordinary India rubber. From acetone also is made the "war rubber" of the Germans (methyl rubber), which I have mentioned in a previous chapter. The Germans had been getting about half their supply of acetone from American acetate of lime and this was of course shut off. That which was produced in Germany by the distillation of beech wood was not even enough for the high explosives needed at the front. So the Germans resorted to rotting potatoes--or rather let us say, since it sounds better--to the cultivation of _Bacillus macerans_. This particular bacillus converts the starch of the potato into two-thirds alcohol and one-third acetone. But soon potatoes got too scarce to be used up in this fashion, so the Germans turned to calcium carbide as a source of acetone and before the war ended they had a factory capable of manufacturing 2000 tons of methyl rubber a year. This shows the advantage of having several strings to a bow. The reason why acetylene is such an active and acquisitive thing the chemist explains, or rather expresses, by picturing its structure in this shape: H-C[triple bond]C-H Now the carbon atoms are holding each other's hands because they have nothing else to do. There are no other elements around to hitch on to. But the two carbons of acetylene readily loosen up and keeping the connection between them by a single bond reach out in this fashion with their two disengaged arms and grab whatever alien atoms happen to be in the vicinity: | | H-C-C-H | | Carbon atoms belong to the quadrumani like the monkeys, so they are peculiarly fitted to forming chains and rings. This accounts for the variety and complexity of the carbon compounds. So when acetylene gas mixed with other gases is passed over a catalyst, such as a heated mass of iron ore or clay (hydrates or silicates of iron or aluminum), it forms all sorts of curious combinations. In the presence of steam we may get such simple compounds as acetic acid, acetone and the like. But when three acetylene molecules join to form a ring of six carbon atoms we get compounds of the benzene series such as were described in the chapter on the coal-tar colors. If ammonia is mixed with acetylene we may get rings with the nitrogen atom in place of one of the carbons, like the pyridins and quinolins, pungent bases such as are found in opium and tobacco. Or if hydrogen sulfide is mixed with the acetylene we may get thiophenes, which have sulfur in the ring. So, starting with the simple combination of two atoms of carbon with two of hydrogen, we can get directly by this single process some of the most complicated compounds of the organic world, as well as many others not found in nature. In the development of the electric furnace America played a pioneer part. Provost Smith of the University of Pennsylvania, who is the best authority on the history of chemistry in America, claims for Robert Hare, a Philadelphia chemist born in 1781, the honor of constructing the first electrical furnace. With this crude apparatus and with no greater electromotive force than could be attained from a voltaic pile, he converted charcoal into graphite, volatilized phosphorus from its compounds, isolated metallic calcium and synthesized calcium carbide. It is to Hare also that we owe the invention in 1801 of the oxy-hydrogen blowpipe, which nowadays is used with acetylene as well as hydrogen. With this instrument he was able to fuse strontia and volatilize platinum. But the electrical furnace could not be used on a commercial scale until the dynamo replaced the battery as a source of electricity. The industrial development of the electrical furnace centered about the search for a cheap method of preparing aluminum. This is the metallic base of clay and therefore is common enough. But clay, as we know from its use in making porcelain, is very infusible and difficult to decompose. Sixty years ago aluminum was priced at $140 a pound, but one would have had difficulty in buying such a large quantity as a pound at any price. At international expositions a small bar of it might be seen in a case labeled "silver from clay." Mechanics were anxious to get the new metal, for it was light and untarnishable, but the metallurgists could not furnish it to them at a low enough price. In order to extract it from clay a more active metal, sodium, was essential. But sodium also was rare and expensive. In those days a professor of chemistry used to keep a little stick of it in a bottle under kerosene and once a year he whittled off a piece the size of a pea and threw it into water to show the class how it sizzled and gave off hydrogen. The way to get cheaper aluminum was, it seemed, to get cheaper sodium and Hamilton Young Castner set himself at this problem. He was a Brooklyn boy, a student of Chandler's at Columbia. You can see the bronze tablet in his honor at the entrance of Havemeyer Hall. In 1886 he produced metallic sodium by mixing caustic soda with iron and charcoal in an iron pot and heating in a gas furnace. Before this experiment sodium sold at $2 a pound; after it sodium sold at twenty cents a pound. But although Castner had succeeded in his experiment he was defeated in his object. For while he was perfecting the sodium process for making aluminum the electrolytic process for getting aluminum directly was discovered in Oberlin. So the $250,000 plant of the "Aluminium Company Ltd." that Castner had got erected at Birmingham, England, did not make aluminum at all, but produced sodium for other purposes instead. Castner then turned his attention to the electrolytic method of producing sodium by the use of the power of Niagara Falls, electric power. Here in 1894 he succeeded in separating common salt into its component elements, chlorine and sodium, by passing the electric current through brine and collecting the sodium in the mercury floor of the cell. The sodium by the action of water goes into caustic soda. Nowadays sodium and chlorine and their components are made in enormous quantities by the decomposition of salt. The United States Government in 1918 procured nearly 4,000,000 pounds of chlorine for gas warfare. The discovery of the electrical process of making aluminum that displaced the sodium method was due to Charles M. Hall. He was the son of a Congregational minister and as a boy took a fancy to chemistry through happening upon an old text-book of that science in his father's library. He never knew who the author was, for the cover and title page had been torn off. The obstacle in the way of the electrolytic production of aluminum was, as I have said, because its compounds were so hard to melt that the current could not pass through. In 1886, when Hall was twenty-two, he solved the problem in the laboratory of Oberlin College with no other apparatus than a small crucible, a gasoline burner to heat it with and a galvanic battery to supply the electricity. He found that a Greenland mineral, known as cryolite (a double fluoride of sodium and aluminum), was readily fused and would dissolve alumina (aluminum oxide). When an electric current was passed through the melted mass the metal aluminum would collect at one of the poles. In working out the process and defending his claims Hall used up all his own money, his brother's and his uncle's, but he won out in the end and Judge Taft held that his patent had priority over the French claim of Hérault. On his death, a few years ago, Hall left his large fortune to his Alma Mater, Oberlin. Two other young men from Ohio, Alfred and Eugene Cowles, with whom Hall was for a time associated, wore the first to develop the wide possibilities of the electric furnace on a commercial scale. In 1885 they started the Cowles Electric Smelting and Aluminum Company at Lockport, New York, using Niagara power. The various aluminum bronzes made by absorbing the electrolyzed aluminum in copper attracted immediate attention by their beauty and usefulness in electrical work and later the company turned out other products besides aluminum, such as calcium carbide, phosphorus, and carborundum. They got carborundum as early as 1885 but miscalled it "crystallized silicon," so its introduction was left to E.A. Acheson, who was a graduate of Edison's laboratory. In 1891 he packed clay and charcoal into an iron bowl, connected it to a dynamo and stuck into the mixture an electric light carbon connected to the other pole of the dynamo. When he pulled out the rod he found its end encrusted with glittering crystals of an unknown substance. They were blue and black and iridescent, exceedingly hard and very beautiful. He sold them at first by the carat at a rate that would amount to $560 a pound. They were as well worth buying as diamond dust, but those who purchased them must have regretted it, for much finer crystals were soon on sale at ten cents a pound. The mysterious substance turned out to be a compound of carbon and silicon, the simplest possible compound, one atom of each, CSi. Acheson set up a factory at Niagara, where he made it in ten-ton batches. The furnace consisted simply of a brick box fifteen feet long and seven feet wide and deep, with big carbon electrodes at the ends. Between them was packed a mixture of coke to supply the carbon, sand to supply the silicon, sawdust to make the mass porous and salt to make it fusible. [Illustration: The first American electric furnace, constructed by Robert Hare of Philadelphia. From "Chemistry in America," by Edgar Fahs Smith] The substance thus produced at Niagara Falls is known as "carborundum" south of the American-Canadian boundary and as "crystolon" north of this line, as "carbolon" by another firm, and as "silicon carbide" by chemists the world over. Since it is next to the diamond in hardness it takes off metal faster than emery (aluminum oxide), using less power and wasting less heat in futile fireworks. It is used for grindstones of all sizes, including those the dentist uses on your teeth. It has revolutionized shop-practice, for articles can be ground into shape better and quicker than they can be cut. What is more, the artificial abrasives do not injure the lungs of the operatives like sandstone. The output of artificial abrasives in the United States and Canada for 1917 was: Tons Value Silicon carbide 8,323 $1,074,152 Aluminum oxide 48,463 6,969,387 A new use for carborundum was found during the war when Uncle Sam assumed the rôle of Jove as "cloud-compeller." Acting on carborundum with chlorine--also, you remember, a product of electrical dissolution--the chlorine displaces the carbon, forming silicon tetra-chloride (SiCl_{4}), a colorless liquid resembling chloroform. When this comes in contact with moist air it gives off thick, white fumes, for water decomposes it, giving a white powder (silicon hydroxide) and hydrochloric acid. If ammonia is present the acid will unite with it, giving further white fumes of the salt, ammonium chloride. So a mixture of two parts of silicon chloride with one part of dry ammonia was used in the war to produce smoke-screens for the concealment of the movements of troops, batteries and vessels or put in shells so the outlook could see where they burst and so get the range. Titanium tetra-chloride, a similar substance, proved 50 per cent. better than silicon, but phosphorus--which also we get from the electric furnace--was the most effective mistifier of all. Before the introduction of the artificial abrasives fine grinding was mostly done by emery, which is an impure form of aluminum oxide found in nature. A purer form is made from the mineral bauxite by driving off its combined water. Bauxite is the ore from which is made the pure aluminum oxide used in the electric furnace for the production of metallic aluminum. Formerly we imported a large part of our bauxite from France, but when the war shut off this source we developed our domestic fields in Arkansas, Alabama and Georgia, and these are now producing half a million tons a year. Bauxite simply fused in the electric furnace makes a better abrasive than the natural emery or corundum, and it is sold for this purpose under the name of "aloxite," "alundum," "exolon," "lionite" or "coralox." When the fused bauxite is worked up with a bonding material into crucibles or muffles and baked in a kiln it forms the alundum refractory ware. Since alundum is porous and not attacked by acids it is used for filtering hot and corrosive liquids that would eat up filter-paper. Carborundum or crystolon is also made up into refractory ware for high temperature work. When the fused mass of the carborundum furnace is broken up there is found surrounding the carborundum core a similar substance though not quite so hard and infusible, known as "carborundum sand" or "siloxicon." This is mixed with fireclay and used for furnace linings. Many new forms of refractories have come into use to meet the demands of the new high temperature work. The essentials are that it should not melt or crumble at high heat and should not expand and contract greatly under changes of temperature (low coefficient of thermal expansion). Whether it is desirable that it should heat through readily or slowly (coefficient of thermal conductivity) depends on whether it is wanted as a crucible or as a furnace lining. Lime (calcium oxide) fuses only at the highest heat of the electric furnace, but it breaks down into dust. Magnesia (magnesium oxide) is better and is most extensively employed. For every ton of steel produced five pounds of magnesite is needed. Formerly we imported 90 per cent. of our supply from Austria, but now we get it from California and Washington. In 1913 the American production of magnesite was only 9600 tons. In 1918 it was 225,000. Zirconia (zirconium oxide) is still more refractory and in spite of its greater cost zirkite is coming into use as a lining for electric furnaces. Silicon is next to oxygen the commonest element in the world. It forms a quarter of the earth's crust, yet it is unfamiliar to most of us. That is because it is always found combined with oxygen in the form of silica as quartz crystal or sand. This used to be considered too refractory to be blown but is found to be easily manipulable at the high temperatures now at the command of the glass-blower. So the chemist rejoices in flasks that he can heat red hot in the Bunsen burner and then plunge into ice water without breaking, and the cook can bake and serve in a dish of "pyrex," which is 80 per cent. silica. At the beginning of the twentieth century minute specimens of silicon were sold as laboratory curiosities at the price of $100 an ounce. Two years later it was turned out by the barrelful at Niagara as an accidental by-product and could not find a market at ten cents a pound. Silicon from the electric furnace appears in the form of hard, glittering metallic crystals. An alloy of iron and silicon, ferro-silicon, made by heating a mixture of iron ore, sand and coke in the electrical furnace, is used as a deoxidizing agent in the manufacture of steel. Since silicon has been robbed with difficulty of its oxygen it takes it on again with great avidity. This has been made use of in the making of hydrogen. A mixture of silicon (or of the ferro-silicon alloy containing 90 per cent. of silicon) with soda and slaked lime is inert, compact and can be transported to any point where hydrogen is needed, say at a battle front. Then the "hydrogenite," as the mixture is named, is ignited by a hot iron ball and goes off like thermit with the production of great heat and the evolution of a vast volume of hydrogen gas. Or the ferro-silicon may be simply burned in an atmosphere of steam in a closed tank after ignition with a pinch of gunpowder. The iron and the silicon revert to their oxides while the hydrogen of the water is set free. The French "silikol" method consists in treating silicon with a 40 per cent. solution of soda. Another source of hydrogen originating with the electric furnace is "hydrolith," which consists of calcium hydride. Metallic calcium is prepared from lime in the electric furnace. Then pieces of the calcium are spread out in an oven heated by electricity and a current of dry hydrogen passed through. The gas is absorbed by the metal, forming the hydride (CaH_{2}). This is packed up in cans and when hydrogen is desired it is simply dropped into water, when it gives off the gas just as calcium carbide gives off acetylene. This last reaction was also used in Germany for filling Zeppelins. For calcium carbide is convenient and portable and acetylene, when it is once started, as by an electric shock, decomposes spontaneously by its own internal heat into hydrogen and carbon. The latter is left as a fine, pure lampblack, suitable for printer's ink. Napoleon, who was always on the lookout for new inventions that could be utilized for military purposes, seized immediately upon the balloon as an observation station. Within a few years after the first ascent had been made in Paris Napoleon took balloons and apparatus for generating hydrogen with him on his "archeological expedition" to Egypt in which he hoped to conquer Asia. But the British fleet in the Mediterranean put a stop to this experiment by intercepting the ship, and military aviation waited until the Great War for its full development. This caused a sudden demand for immense quantities of hydrogen and all manner of means was taken to get it. Water is easily decomposed into hydrogen and oxygen by passing an electric current through it. In various electrolytical processes hydrogen has been a wasted by-product since the balloon demand was slight and it was more bother than it was worth to collect and purify the hydrogen. Another way of getting hydrogen in quantity is by passing steam over red-hot coke. This produces the blue water-gas, which contains about 50 per cent. hydrogen, 40 per cent. carbon monoxide and the rest nitrogen and carbon dioxide. The last is removed by running the mixed gases through lime. Then the nitrogen and carbon monoxide are frozen out in an air-liquefying apparatus and the hydrogen escapes to the storage tank. The liquefied carbon monoxide, allowed to regain its gaseous form, is used in an internal combustion engine to run the plant. There are then many ways of producing hydrogen, but it is so light and bulky that it is difficult to get it where it is wanted. The American Government in the war made use of steel cylinders each holding 161 cubic feet of the gas under a pressure of 2000 pounds per square inch. Even the hydrogen used by the troops in France was shipped from America in this form. For field use the ferro-silicon and soda process was adopted. A portable generator of this type was capable of producing 10,000 cubic feet of the gas per hour. The discovery by a Kansas chemist of natural sources of helium may make it possible to free ballooning of its great danger, for helium is non-inflammable and almost as light as hydrogen. Other uses of hydrogen besides ballooning have already been referred to in other chapters. It is combined with nitrogen to form synthetic ammonia. It is combined with oxygen in the oxy-hydrogen blowpipe to produce heat. It is combined with vegetable and animal oils to convert them into solid fats. There is also the possibility of using it as a fuel in the internal combustion engine in place of gasoline, but for this purpose we must find some way of getting hydrogen portable or producible in a compact form. Aluminum, like silicon, sodium and calcium, has been rescued by violence from its attachment to oxygen and like these metals it reverts with readiness to its former affinity. Dr. Goldschmidt made use of this reaction in his thermit process. Powdered aluminum is mixed with iron oxide (rust). If the mixture is heated at any point a furious struggle takes place throughout the whole mass between the iron and the aluminum as to which metal shall get the oxygen, and the aluminum always comes out ahead. The temperature runs up to some 6000 degrees Fahrenheit within thirty seconds and the freed iron, completely liquefied, runs down into the bottom of the crucible, where it may be drawn off by opening a trap door. The newly formed aluminum oxide (alumina) floats as slag on top. The applications of the thermit process are innumerable. If, for instance, it is desired to mend a broken rail or crank shaft without moving it from its place, the two ends are brought together or fixed at the proper distance apart. A crucible filled with the thermit mixture is set up above the joint and the thermit ignited with a priming of aluminum and barium peroxide to start it off. The barium peroxide having a superabundance of oxygen gives it up readily and the aluminum thus encouraged attacks the iron oxide and robs it of its oxygen. As soon as the iron is melted it is run off through the bottom of the crucible and fills the space between the rail ends, being kept from spreading by a mold of refractory material such as magnesite. The two ends of the rail are therefore joined by a section of the same size, shape, substance and strength as themselves. The same process can be used for mending a fracture or supplying a missing fragment of a steel casting of any size, such as a ship's propeller or a cogwheel. [Illustration: TYPES OF GAS MASK USED BY AMERICA, THE ALLIES, AND GERMANY DURING THE WAR In the top row are the American masks, chronologically, from left to right: U.S. Navy mask (obsolete), U.S. Navy mask (final type), U.S. Army box respirator (used throughout the war), U.S.R.F.K. respirator, U.S.A.T. respirator (an all-rubber mask), U.S.K.T. respirator (a sewed fabric mask), and U.S. "Model 1919," ready for production when the armistice was signed. In the middle row, left to right, are: British veil (the original emergency mask used in April, 1915), British P.H. helmet (the next emergency mask), British box respirator (standard British army type), French M2 mask (original type), French Tissot artillery mask, and French A.R.S. mask (latest type). In the front row: the latest German mask, the Russian mask, Italian mask, British motor corps mask, U.S. rear area emergency respirator, and U.S. Connell mask] [Illustration: PUMPING MELTED WHITE PHOSPHORUS INTO HAND GRENADES FILLED WITH WATER--EDGEWOOD ARSENAL] [Illustration: FILLING SHELL WITH "MUSTARD GAS" Empty shells are being placed on small trucks to be run into the filling chamber. The large truck in the foreground contains loaded shell] For smaller work thermit has two rivals, the oxy-acetylene torch and electric welding. The former has been described and the latter is rather out of the range of this volume, although I may mention that in the latter part of 1918 there was launched from a British shipyard the first rivotless steel vessel. In this the steel plates forming the shell, bulkheads and floors are welded instead of being fastened together by rivets. There are three methods of doing this depending upon the thickness of the plates and the sort of strain they are subject to. The plates may be overlapped and tacked together at intervals by pressing the two electrodes on opposite sides of the same point until the spot is sufficiently heated to fuse together the plates here. Or roller electrodes may be drawn slowly along the line of the desired weld, fusing the plates together continuously as they go. Or, thirdly, the plates may be butt-welded by being pushed together edge to edge without overlapping and the electric current being passed from one plate to the other heats up the joint where the conductivity is interrupted. It will be observed that the thermit process is essentially like the ordinary blast furnace process of smelting iron and other metals except that aluminum is used instead of carbon to take the oxygen away from the metal in the ore. This has an advantage in case carbon-free metals are desired and the process is used for producing manganese, tungsten, titanium, molybdenum, vanadium and their allows with iron and copper. During the war thermit found a new and terrible employment, as it was used by the airmen for setting buildings on fire and exploding ammunition dumps. The German incendiary bombs consisted of a perforated steel nose-piece, a tail to keep it falling straight and a cylindrical body which contained a tube of thermit packed around with mineral wax containing potassium perchlorate. The fuse was ignited as the missile was released and the thermit, as it heated up, melted the wax and allowed it to flow out together with the liquid iron through the holes in the nose-piece. The American incendiary bombs were of a still more malignant type. They weighed about forty pounds apiece and were charged with oil emulsion, thermit and metallic sodium. Sodium decomposes water so that if any attempt were made to put out with a hose a fire started by one of these bombs the stream of water would be instantaneously changed into a jet of blazing hydrogen. Besides its use in combining and separating different elements the electric furnace is able to change a single element into its various forms. Carbon, for instance, is found in three very distinct forms: in hard, transparent and colorless crystals as the diamond, in black, opaque, metallic scales as graphite, and in shapeless masses and powder as charcoal, coke, lampblack, and the like. In the intense heat of the electric arc these forms are convertible one into the other according to the conditions. Since the third form is the cheapest the object is to change it into one of the other two. Graphite, plumbago or "blacklead," as it is still sometimes called, is not found in many places and more rarely found pure. The supply was not equal to the demand until Acheson worked out the process of making it by packing powdered anthracite between the electrodes of his furnace. In this way graphite can be cheaply produced in any desired quantity and quality. Since graphite is infusible and incombustible except at exceedingly high temperatures, it is extensively used for crucibles and electrodes. These electrodes are made in all sizes for the various forms of electric lamps and furnaces from rods one-sixteenth of an inch in diameter to bars a foot thick and six feet long. It is graphite mixed with fine clay to give it the desired degree of hardness that forms the filling of our "lead" pencils. Finely ground and flocculent graphite treated with tannin may be held in suspension in liquids and even pass through filter-paper. The mixture with water is sold under the name of "aquadag," with oil as "oildag" and with grease as "gredag," for lubrication. The smooth, slippery scales of graphite in suspension slide over each other easily and keep the bearings from rubbing against each other. The other and more difficult metamorphosis of carbon, the transformation of charcoal into diamond, was successfully accomplished by Moissan in 1894. Henri Moissan was a toxicologist, that is to say, a Professor of Poisoning, in the Paris School of Pharmacy, who took to experimenting with the electric furnace in his leisure hours and did more to demonstrate its possibilities than any other man. With it he isolated fluorine, most active of the elements, and he prepared for the first time in their purity many of the rare metals that have since found industrial employment. He also made the carbides of the various metals, including the now common calcium carbide. Among the problems that he undertook and solved was the manufacture of artificial diamonds. He first made pure charcoal by burning sugar. This was packed with iron in the hollow of a block of lime into which extended from opposite sides the carbon rods connected to the dynamo. When the iron had melted and dissolved all the carbon it could, Moissan dumped it into water or better into melted lead or into a hole in a copper block, for this cooled it most rapidly. After a crust was formed it was left to solidify slowly. The sudden cooling of the iron on the outside subjected the carbon, which was held in solution, to intense pressure and when the bit of iron was dissolved in acid some of the carbon was found to be crystallized as diamond, although most of it was graphite. To be sure, the diamonds were hardly big enough to be seen with the naked eye, but since Moissan's aim was to make diamonds, not big diamonds, he ceased his efforts at this point. To produce large diamonds the carbon would have to be liquefied in considerable quantity and kept in that state while it slowly crystallized. But that could only be accomplished at a temperature and pressure and duration unattainable as yet. Under ordinary atmospheric pressure carbon passes over from the solid to the gaseous phase without passing through the liquid, just as snow on a cold, clear day will evaporate without melting. Probably some one in the future will take up the problem where Moissan dropped it and find out how to make diamonds of any size. But it is not a question that greatly interests either the scientist or the industrialist because there is not much to be learned from it and not much to be made out of it. If the inventor of a process for making cheap diamonds could keep his electric furnace secretly in his cellar and market his diamonds cautiously he might get rich out of it, but he would not dare to turn out very large stones or too many of them, for if a suspicion got around that he was making them the price would fall to almost nothing even if he did sell another one. For the high price of the diamond is purely fictitious. It is in the first place kept up by limiting the output of the natural stone by the combination of dealers and, further, the diamond is valued not for its usefulness or beauty but by its real or supposed rarity. Chesterton says: "All is gold that glitters, for the glitter is the gold." This is not so true of gold, for if gold were as cheap as nickel it would be very valuable, since we should gold-plate our machinery, our ships, our bridges and our roofs. But if diamonds were cheap they would be good for nothing except grindstones and drills. An imitation diamond made of heavy glass (paste) cannot be distinguished from the genuine gem except by an expert. It sparkles about as brilliantly, for its refractive index is nearly as high. The reason why it is not priced so highly is because the natural stone has presumably been obtained through the toil and sweat of hundreds of negroes searching in the blue ground of the Transvaal for many months. It is valued exclusively by its cost. To wear a diamond necklace is the same as hanging a certified check for $100,000 by a string around the neck. Real values are enhanced by reduction in the cost of the price of production. Fictitious values are destroyed by it. Aluminum at twenty-five cents a pound is immensely more valuable to the world than when it is a curiosity in the chemist's cabinet and priced at $160 a pound. So the scope of the electric furnace reaches from the costly but comparatively valueless diamond to the cheap but indispensable steel. As F.J. Tone says, if the automobile manufacturers were deprived of Niagara products, the abrasives, aluminum, acetylene for welding and high-speed tool steel, a factory now turning out five hundred cars a day would be reduced to one hundred. I have here been chiefly concerned with electricity as effecting chemical changes in combining or separating elements, but I must not omit to mention its rapidly extending use as a source of heat, as in the production and casting of steel. In 1908 there were only fifty-five tons of steel produced by the electric furnace in the United States, but by 1918 this had risen to 511,364 tons. And besides ordinary steel the electric furnace has given us alloys of iron with the once "rare metals" that have created a new science of metallurgy. CHAPTER XIV METALS, OLD AND NEW The primitive metallurgist could only make use of such metals as he found free in nature, that is, such as had not been attacked and corroded by the ubiquitous oxygen. These were primarily gold or copper, though possibly some original genius may have happened upon a bit of meteoric iron and pounded it out into a sword. But when man found that the red ocher he had hitherto used only as a cosmetic could be made to yield iron by melting it with charcoal he opened a new era in civilization, though doubtless the ocher artists of that day denounced him as a utilitarian and deplored the decadence of the times. Iron is one of the most timid of metals. It has a great disinclination to be alone. It is also one of the most altruistic of the elements. It likes almost every other element better than itself. It has an especial affection for oxygen, and, since this is in both air and water, and these are everywhere, iron is not long without a mate. The result of this union goes by various names in the mineralogical and chemical worlds, but in common language, which is quite good enough for our purpose, it is called iron rust. [Illustration: By courtesy _Mineral Foote-Notes_. From Agricola's "De Re Metallica 1550." Primitive furnace for smelting iron ore.] Not many of us have ever seen iron, the pure metal, soft, ductile and white like silver. As soon as it is exposed to the air it veils itself with a thin film of rust and becomes black and then red. For that reason there is practically no iron in the world except what man has made. It is rarer than gold, than diamonds; we find in the earth no nuggets or crystals of it the size of the fist as we find of these. But occasionally there fall down upon us out of the clear sky great chunks of it weighing tons. These meteorites are the mavericks of the universe. We do not know where they come from or what sun or planet they belonged to. They are our only visitors from space, and if all the other spheres are like these fragments we know we are alone in the universe. For they contain rustless iron, and where iron does not rust man cannot live, nor can any other animal or any plant. Iron rusts for the same reason that a stone rolls down hill, because it gets rid of its energy that way. All things in the universe are constantly trying to get rid of energy except man, who is always trying to get more of it. Or, on second thought, we see that man is the greatest spendthrift of all, for he wants to expend so much more energy than he has that he borrows from the winds, the streams and the coal in the rocks. He robs minerals and plants of the energy which they have stored up to spend for their own purposes, just as he robs the bee of its honey and the silk worm of its cocoon. Man's chief business is in reversing the processes of nature. That is the way he gets his living. And one of his greatest triumphs was when he discovered how to undo iron rust and get the metal out of it. In the four thousand years since he first did this he has accomplished more than in the millions of years before. Without knowing the value of iron rust man could attain only to the culture of the Aztecs and Incas, the ancient Egyptians and Assyrians. The prosperity of modern states is dependent on the amount of iron rust which they possess and utilize. England, United States, Germany, all nations are competing to see which can dig the most iron rust out of the ground and make out of it railroads, bridges, buildings, machinery, battleships and such other tools and toys and then let them relapse into rust again. Civilization can be measured by the amount of iron rusted per capita, or better, by the amount rescued from rust. But we are devoting so much space to the consideration of the material aspects of iron that we are like to neglect its esthetic and ethical uses. The beauty of nature is very largely dependent upon the fact that iron rust and, in fact, all the common compounds of iron are colored. Few elements can assume so many tints. Look at the paint pot cañons of the Yellowstone. Cheap glass bottles turn out brown, green, blue, yellow or black, according to the amount and kind of iron they contain. We build a house of cream-colored brick, varied with speckled brick and adorned with terra cotta ornaments of red, yellow and green, all due to iron. Iron rusts, therefore it must be painted; but what is there better to paint it with than iron rust itself? It is cheap and durable, for it cannot rust any more than a dead man can die. And what is also of importance, it is a good, strong, clean looking, endurable color. Whenever we take a trip on the railroad and see the miles of cars, the acres of roofing and wall, the towns full of brick buildings, we rejoice that iron rust is red, not white or some leas satisfying color. We do not know why it is so. Zinc and aluminum are metals very much like iron in chemical properties, but all their salts are colorless. Why is it that the most useful of the metals forms the most beautiful compounds? Some say, Providence; some say, chance; some say nothing. But if it had not been so we would have lost most of the beauty of rocks and trees and human beings. For the leaves and the flowers would all be white, and all the men and women would look like walking corpses. Without color in the flower what would the bees and painters do? If all the grass and trees were white, it would be like winter all the year round. If we had white blood in our veins like some of the insects it would be hard lines for our poets. And what would become of our morality if we could not blush? "As for me, I thrill to see The bloom a velvet cheek discloses! Made of dust! I well believe it, So are lilies, so are roses." An etiolated earth would be hardly worth living in. The chlorophyll of the leaves and the hemoglobin of the blood are similar in constitution. Chlorophyll contains magnesium in place of iron but iron is necessary to its formation. We all know how pale a plant gets if its soil is short of iron. It is the iron in the leaves that enables the plants to store up the energy of the sunshine for their own use and ours. It is the iron in our blood that enables us to get the iron out of iron rust and make it into machines to supplement our feeble hands. Iron is for us internally the carrier of energy, just as in the form of a trolley wire or of a third rail it conveys power to the electric car. Withdraw the iron from the blood as indicated by the pallor of the cheeks, and we become weak, faint and finally die. If the amount of iron in the blood gets too small the disease germs that are always attacking us are no longer destroyed, but multiply without check and conquer us. When the iron ceases to work efficiently we are killed by the poison we ourselves generate. Counting the number of iron-bearing corpuscles in the blood is now a common method of determining disease. It might also be useful in moral diagnosis. A microscopical and chemical laboratory attached to the courtroom would give information of more value than some of the evidence now obtained. For the anemic and the florid vices need very different treatment. An excess or a deficiency of iron in the body is liable to result in criminality. A chemical system of morals might be developed on this basis. Among the ferruginous sins would be placed murder, violence and licentiousness. Among the non-ferruginous, cowardice, sloth and lying. The former would be mostly sins of commission, the latter, sins of omission. The virtues could, of course, be similarly classified; the ferruginous virtues would include courage, self-reliance and hopefulness; the non-ferruginous, peaceableness, meekness and chastity. According to this ethical criterion the moral man would be defined as one whose conduct is better than we should expect from the per cent. of iron in his blood. The reason why iron is able to serve this unique purpose of conveying life-giving air to all parts of the body is because it rusts so readily. Oxidation and de-oxidation proceed so quietly that the tenderest cells are fed without injury. The blood changes from red to blue and _vice versa_ with greater ease and rapidity than in the corresponding alternations of social status in a democracy. It is because iron is so rustable that it is so useful. The factories with big scrap-heaps of rusting machinery are making the most money. The pyramids are the most enduring structures raised by the hand of man, but they have not sheltered so many people in their forty centuries as our skyscrapers that are already rusting. We have to carry on this eternal conflict against rust because oxygen is the most ubiquitous of the elements and iron can only escape its ardent embraces by hiding away in the center of the earth. The united elements, known to the chemist as iron oxide and to the outside world as rust, are among the commonest of compounds and their colors, yellow and red like the Spanish flag, are displayed on every mountainside. From the time of Tubal Cain man has ceaselessly labored to divorce these elements and, having once separated them, to keep them apart so that the iron may be retained in his service. But here, as usual, man is fighting against nature and his gains, as always, are only temporary. Sooner or later his vigilance is circumvented and the metal that he has extricated by the fiery furnace returns to its natural affinity. The flint arrowheads, the bronze spearpoints, the gold ornaments, the wooden idols of prehistoric man are still to be seen in our museums, but his earliest steel swords have long since crumbled into dust. Every year the blast furnaces of the world release 72,000,000 tons of iron from its oxides and every year a large part, said to be a quarter of that amount, reverts to its primeval forms. If so, then man after five thousand years of metallurgical industry has barely got three years ahead of nature, and should he cease his efforts for a generation there would be little left to show that man had ever learned to extract iron from its ores. The old question, "What becomes of all the pins?" may be as well asked of rails, pipes and threshing machines. The end of all iron is the same. However many may be its metamorphoses while in the service of man it relapses at last into its original state of oxidation. To save a pound of iron from corrosion is then as much a benefit to the world as to produce another pound from the ore. In fact it is of much greater benefit, for it takes four pounds of coal to produce one pound of steel, so whenever a piece of iron is allowed to oxidize it means that four times as much coal must be oxidized in order to replace it. And the beds of coal will be exhausted before the beds of iron ore. If we are ever to get ahead, if we are to gain any respite from this enormous waste of labor and natural resources, we must find ways of preventing the iron which we have obtained and fashioned into useful tools from being lost through oxidation. Now there is only one way of keeping iron and oxygen from uniting and that is to keep them apart. A very thin dividing wall will serve for the purpose, for instance, a film of oil. But ordinary oil will rub off, so it is better to cover the surface with an oil-like linseed which oxidizes to a hard elastic and adhesive coating. If with linseed oil we mix iron oxide or some other pigment we have a paint that will protect iron perfectly so long as it is unbroken. But let the paint wear off or crack so that air can get at the iron, then rust will form and spread underneath the paint on all sides. The same is true of the porcelain-like enamel with which our kitchen iron ware is nowadays coated. So long as the enamel holds it is all right but once it is broken through at any point it begins to scale off and gets into our food. Obviously it would be better for some purposes if we could coat our iron with another and less easily oxidized metal than with such dissimilar substances as paint or porcelain. Now the nearest relative to iron is nickel, and a layer of this of any desired thickness may be easily deposited by electricity upon any surface however irregular. Nickel takes a bright polish and keeps it well, so nickel plating has become the favorite method of protection for small objects where the expense is not prohibitive. Copper plating is used for fine wires. A sheet of iron dipped in melted tin comes out coated with a thin adhesive layer of the latter metal. Such tinned plate commonly known as "tin" has become the favorite material for pans and cans. But if the tin is scratched the iron beneath rusts more rapidly than if the tin were not there, for an electrolytic action is set up and the iron, being the negative element of the couple, suffers at the expense of the tin. With zinc it is quite the opposite. Zinc is negative toward iron, so when the two are in contact and exposed to the weather the zinc is oxidized first. A zinc plating affords the protection of a Swiss Guard, it holds out as long as possible and when broken it perishes to the last atom before it lets the oxygen get at the iron. The zinc may be applied in four different ways. (1) It may be deposited by electrolysis as in nickel plating, but the zinc coating is more apt to be porous. (2) The sheets or articles may be dipped in a bath of melted zinc. This gives us the familiar "galvanized iron," the most useful and when well done the most effective of rust preventives. Besides these older methods of applying zinc there are now two new ones. (3) One is the Schoop process by which a wire of zinc or other metal is fed into an oxy-hydrogen air blast of such heat and power that it is projected as a spray of minute drops with the speed of bullets and any object subjected to the bombardment of this metallic mist receives a coating as thick as desired. The zinc spray is so fine and cool that it may be received on cloth, lace, or the bare hand. The Schoop metallizing process has recently been improved by the use of the electric current instead of the blowpipe for melting the metal. Two zinc wires connected with any electric system, preferably the direct, are fed into the "pistol." Where the wires meet an electric arc is set up and the melted zinc is sprayed out by a jet of compressed air. (4) In the Sherardizing process the articles are put into a tight drum with zinc dust and heated to 800° F. The zinc at this temperature attacks the iron and forms a series of alloys ranging from pure zinc on the top to pure iron at the bottom of the coating. Even if this cracks in part the iron is more or less protected from corrosion so long as any zinc remains. Aluminum is used similarly in the calorizing process for coating iron, copper or brass. First a surface alloy is formed by heating the metal with aluminum powder. Then the temperature is raised to a high degree so as to cause the aluminum on the surface to diffuse into the metal and afterwards it is again baked in contact with aluminum dust which puts upon it a protective plating of the pure aluminum which does not oxidize. [Illustration: PHOTOMICROGRAPHS SHOWING THE STRUCTURE OF STEEL MADE BY PROFESSOR E.G. MARTIN OF PURDUE UNIVERSITY 1. Cold-worked steel showing ferrite and sorbite (enlarged 500 times) 2. Steel showing pearlite crystals (enlarged 500 times) 3. Structure characteristic of air-cooled steel (enlarged 50 times) 4. The triangular structure characteristic of cast steel showing ferrite and pearlite (enlarged 50 times)] [Illustration: Courtesy of E.G. Mahin THE MICROSCOPIC STRUCTURE OF METALS 1. Malleabilized casting; temper carbon in ferrite (enlarged 50 times) 2. Type metal; lead-antimony alloy in matrix of lead (enlarged 100 times) 3. Gray cast iron; carbon as graphite (enlarged 500 times) 4. Steel composed of cementite (white) and pearlite (black) (enlarged 50 times)] Another way of protecting iron ware from rusting is to rust it. This is a sort of prophylactic method like that adopted by modern medicine where inoculation with a mild culture prevents a serious attack of the disease. The action of air and water on iron forms a series of compounds and mixtures of them. Those that contain least oxygen are hard, black and magnetic like iron itself. Those that have most oxygen are red and yellow powders. By putting on a tight coating of the black oxide we can prevent or hinder the oxidation from going on into the pulverulent stage. This is done in several ways. In the Bower-Barff process the articles to be treated are put into a closed retort and a current of superheated steam passed through for twenty minutes followed by a current of producer gas (carbon monoxide), to reduce any higher oxides that may have been formed. In the Gesner process a current of gasoline vapor is used as the reducing agent. The blueing of watch hands, buckles and the like may be done by dipping them into an oxidizing bath such as melted saltpeter. But in order to afford complete protection the layer of black oxide must be thickened by repeating the process which adds to the time and expense. This causes a slight enlargement and the high temperature often warps the ware so it is not suitable for nicely adjusted parts of machinery and of course tools would lose their temper by the heat. A new method of rust proofing which is free from these disadvantages is the phosphate process invented by Thomas Watts Coslett, an English chemist, in 1907, and developed in America by the Parker Company of Detroit. This consists simply in dipping the sheet iron or articles into a tank filled with a dilute solution of iron phosphate heated nearly to the boiling point by steam pipes. Bubbles of hydrogen stream off rapidly at first, then slower, and at the end of half an hour or longer the action ceases, and the process is complete. What has happened is that the iron has been converted into a basic iron phosphate to a depth depending upon the density of articles processed. Any one who has studied elementary qualitative analysis will remember that when he added ammonia to his "unknown" solution, iron and phosphoric acid, if present, were precipitated together, or in other words, iron phosphate is insoluble except in acids. Therefore a superficial film of such phosphate will protect the iron underneath except from acids. This film is not a coating added on the outside like paint and enamel or tin and nickel plate. It is therefore not apt to scale off and it does not increase the size of the article. No high heat is required as in the Sherardizing and Bower-Barff processes, so steel tools can be treated without losing their temper or edge. The deposit consisting of ferrous and ferric phosphates mixed with black iron oxide may be varied in composition, texture and color. It is ordinarily a dull gray and oiling gives a soft mat black more in accordance with modern taste than the shiny nickel plating that delighted our fathers. Even the military nowadays show more quiet taste than formerly and have abandoned their glittering accoutrements. The phosphate bath is not expensive and can be used continuously for months by adding more of the concentrated solution to keep up the strength and removing the sludge that is precipitated. Besides the iron the solution contains the phosphates of other metals such as calcium or strontium, manganese, molybdenum, or tungsten, according to the particular purpose. Since the phosphating solution does not act on nickel it may be used on articles that have been partly nickel-plated so there may be produced, for instance, a bright raised design against a dull black background. Then, too, the surface left by the Parker process is finely etched so it affords a good attachment for paint or enamel if further protection is needed. Even if the enamel does crack, the iron beneath is not so apt to rust and scale off the coating. These, then, are some of the methods which are now being used to combat our eternal enemy, the rust that doth corrupt. All of them are useful in their several ways. No one of them is best for all purposes. The claim of "rust-proof" is no more to be taken seriously than "fire-proof." We should rather, if we were finical, have to speak of "rust-resisting" coatings as we do of "slow-burning" buildings. Nature is insidious and unceasing in her efforts to bring to ruin the achievements of mankind and we need all the weapons we can find to frustrate her destructive determination. But it is not enough for us to make iron superficially resistant to rust from the atmosphere. We should like also to make it so that it would withstand corrosion by acids, then it could be used in place of the large and expensive platinum or porcelain evaporating pans and similar utensils employed in chemical works. This requirement also has been met in the non-corrosive forms of iron, which have come into use within the last five years. One of these, "tantiron," invented by a British metallurgist, Robert N. Lennox, in 1912, contains 15 per cent. of silicon. Similar products are known as "duriron" and "Buflokast" in America, "metilure" in France, "ileanite" in Italy and "neutraleisen" in Germany. It is a silvery-white close-grained iron, very hard and rather brittle, somewhat like cast iron but with silicon as the main additional ingredient in place of carbon. It is difficult to cut or drill but may be ground into shape by the new abrasives. It is rustproof and is not attacked by sulfuric, nitric or acetic acid, hot or cold, diluted or concentrated. It does not resist so well hydrochloric acid or sulfur dioxide or alkalies. The value of iron lies in its versatility. It is a dozen metals in one. It can be made hard or soft, brittle or malleable, tough or weak, resistant or flexible, elastic or pliant, magnetic or non-magnetic, more or less conductive to electricity, by slight changes of composition or mere differences of treatment. No wonder that the medieval mind ascribed these mysterious transformations to witchcraft. But the modern micrometallurgist, by etching the surface of steel and photographing it, shows it up as composite as a block of granite. He is then able to pick out its component minerals, ferrite, austenite, martensite, pearlite, graphite, cementite, and to show how their abundance, shape and arrangement contribute to the strength or weakness of the specimen. The last of these constituents, cementite, is a definite chemical compound, an iron carbide, Fe_{3}C, containing 6.6 per cent. of carbon, so hard as to scratch glass, very brittle, and imparting these properties to hardened steel and cast iron. With this knowledge at his disposal the iron-maker can work with his eyes open and so regulate his melt as to cause these various constituents to crystallize out as he wants them to. Besides, he is no longer confined to the alloys of iron and carbon. He has ransacked the chemical dictionary to find new elements to add to his alloys, and some of these rarities have proved to possess great practical value. Vanadium, for instance, used to be put into a fine print paragraph in the back of the chemistry book, where the class did not get to it until the term closed. Yet if it had not been for vanadium steel we should have no Ford cars. Tungsten, too, was relegated to the rear, and if the student remembered it at all it was because it bothered him to understand why its symbol should be W instead of T. But the student of today studies his lesson in the light of a tungsten wire and relieves his mind by listening to a phonograph record played with a "tungs-tone" stylus. When I was assistant in chemistry an "analysis" of steel consisted merely in the determination of its percentage of carbon, and I used to take Saturday for it so I could have time enough to complete the combustion. Now the chemists of a steel works' laboratory may have to determine also the tungsten, chromium, vanadium, titanium, nickel, cobalt, phosphorus, molybdenum, manganese, silicon and sulfur, any or all of them, and be spry about it, because if they do not get the report out within fifteen minutes while the steel is melting in the electrical furnace the whole batch of 75 tons may go wrong. I'm glad I quit the laboratory before they got to speeding up chemists so. The quality of the steel depends upon the presence and the relative proportions of these ingredients, and a variation of a tenth of 1 per cent. in certain of them will make a different metal out of it. For instance, the steel becomes stronger and tougher as the proportion of nicked is increased up to about 15 per cent. Raising the percentage to 25 we get an alloy that does not rust or corrode and is non-magnetic, although both its component metals, iron and nickel, are by themselves attracted by the magnet. With 36 per cent. nickel and 5 per cent. manganese we get the alloy known as "invar," because it expands and contracts very little with changes of temperature. A bar of the best form of invar will expand less than one-millionth part of its length for a rise of one degree Centigrade at ordinary atmospheric temperature. For this reason it is used in watches and measuring instruments. The alloy of iron with 46 per cent. nickel is called "platinite" because its rate of expansion and contraction is the same as platinum and glass, and so it can be used to replace the platinum wire passing through the glass of an electric light bulb. A manganese steel of 11 to 14 per cent. is too hard to be machined. It has to be cast or ground into shape and is used for burglar-proof safes and armor plate. Chrome steel is also hard and tough and finds use in files, ball bearings and projectiles. Titanium, which the iron-maker used to regard as his implacable enemy, has been drafted into service as a deoxidizer, increasing the strength and elasticity of the steel. It is reported from France that the addition of three-tenths of 1 per cent. of zirconium to nickel steel has made it more resistant to the German perforating bullets than any steel hitherto known. The new "stainless" cutlery contains 12 to 14 per cent. of chromium. With the introduction of harder steels came the need of tougher tools to work them. Now the virtue of a good tool steel is the same as of a good man. It must be able to get hot without losing its temper. Steel of the old-fashioned sort, as everybody knows, gets its temper by being heated to redness and suddenly cooled by quenching or plunging it into water or oil. But when the point gets heated up again, as it does by friction in a lathe, it softens and loses its cutting edge. So the necessity of keeping the tool cool limited the speed of the machine. But about 1868 a Sheffield metallurgist, Robert F. Mushet, found that a piece of steel he was working with did not require quenching to harden it. He had it analyzed to discover the meaning of this peculiarity and learned that it contained tungsten, a rare metal unrecognized in the metallurgy of that day. Further investigation showed that steel to which tungsten and manganese or chromium had been added was tougher and retained its temper at high temperature better than ordinary carbon steel. Tools made from it could be worked up to a white heat without losing their cutting power. The new tools of this type invented by "Efficiency" Taylor at the Bethlehem Steel Works in the nineties have revolutionized shop practice the world over. A tool of the old sort could not cut at a rate faster than thirty feet a minute without overheating, but the new tungsten tools will plow through steel ten times as fast and can cut away a ton of the material in an hour. By means of these high-speed tools the United States was able to turn out five times the munitions that it could otherwise have done in the same time. On the other hand, if Germany alone had possessed the secret of the modern steels no power could have withstood her. A slight superiority in metallurgy has been the deciding factor in many a battle. Those of my readers who have had the advantages of Sunday school training will recall the case described in I Samuel 13:19-22. By means of these new metals armor plate has been made invulnerable--except to projectiles pointed with similar material. Flying has been made possible through engines weighing no more than two pounds per horse power. The cylinders of combustion engines and the casing of cannon have been made to withstand the unprecedented pressure and corrosive action of the fiery gases evolved within. Castings are made so hard that they cannot be cut--save with tools of the same sort. In the high-speed tools now used 20 or 30 per cent, of the iron is displaced by other ingredients; for example, tungsten from 14 to 25 per cent., chromium from 2 to 7 per cent., vanadium from 1/2 to 1-1/2 per cent., carbon from 6 to 8 per cent., with perhaps cobalt up to 4 per cent. Molybdenum or uranium may replace part of the tungsten. Some of the newer alloys for high-speed tools contain no iron at all. That which bears the poetic name of star-stone, stellite, is composed of chromium, cobalt and tungsten in varying proportions. Stellite keeps a hard cutting edge and gets tougher as it gets hotter. It is very hard and as good for jewelry as platinum except that it is not so expensive. Cooperite, its rival, is an alloy of nickel and zirconium, stronger, lighter and cheaper than stellite. Before the war nearly half of the world's supply of tungsten ore (wolframite) came from Burma. But although Burma had belonged to the British for a hundred years they had not developed its mineral resources and the tungsten trade was monopolized by the Germans. All the ore was shipped to Germany and the British Admiralty was content to buy from the Germans what tungsten was needed for armor plate and heavy guns. When the war broke out the British had the ore supply, but were unable at first to work it because they were not familiar with the processes. Germany, being short of tungsten, had to sneak over a little from Baltimore in the submarine _Deutschland_. In the United States before the war tungsten ore was selling at $6.50 a unit, but by the beginning of 1916 it had jumped to $85 a unit. A unit is 1 per cent. of tungsten trioxide to the ton, that is, twenty pounds. Boulder County, Colorado, and San Bernardino, California, then had mining booms, reminding one of older times. Between May and December, 1918, there was manufactured in the United States more than 45,500,000 pounds of tungsten steel containing some 8,000,000 pounds of tungsten. If tungsten ores were more abundant and the metal more easily manipulated, it would displace steel for many purposes. It is harder than steel or even quartz. It never rusts and is insoluble in acids. Its expansion by heat is one-third that of iron. It is more than twice as heavy as iron and its melting point is twice as high. Its electrical resistance is half that of iron and its tensile strength is a third greater than the strongest steel. It can be worked into wire .0002 of an inch in diameter, almost too thin to be seen, but as strong as copper wire ten times the size. The tungsten wires in the electric lamps are about .03 of an inch in diameter, and they give three times the light for the same consumption of electricity as the old carbon filament. The American manufacturers of the tungsten bulb have very appropriately named their lamp "Mazda" after the light god of the Zoroastrians. To get the tungsten into wire form was a problem that long baffled the inventors of the world, for it was too refractory to be melted in mass and too brittle to be drawn. Dr. W.D. Coolidge succeeded in accomplishing the feat in 1912 by reducing the tungstic acid by hydrogen and molding the metallic powder into a bar by pressure. This is raised to a white heat in the electric furnace, taken out and rolled down, and the process repeated some fifty times, until the wire is small enough so it can be drawn at a red heat through diamond dies of successively smaller apertures. The German method of making the lamp filaments is to squirt a mixture of tungsten powder and thorium oxide through a perforated diamond of the desired diameter. The filament so produced is drawn through a chamber heated to 2500° C. at a velocity of eight feet an hour, which crystallizes the tungsten into a continuous thread. The first metallic filament used in the electric light on a commercial scale was made of tantalum, the metal of Tantalus. In the period 1905-1911 over 100,000,000 tantalus lamps were sold, but tungsten displaced them as soon as that metal could be drawn into wire. A recent rival of tungsten both as a filament for lamps and hardener for steel is molybdenum. One pound of this metal will impart more resiliency to steel than three or four pounds of tungsten. The molybdenum steel, because it does not easily crack, is said to be serviceable for armor-piercing shells, gun linings, air-plane struts, automobile axles and propeller shafts. In combination with its rival as a tungsten-molybdenum alloy it is capable of taking the place of the intolerably expensive platinum, for it resists corrosion when used for spark plugs and tooth plugs. European steel men have taken to molybdenum more than Americans. The salts of this metal can be used in dyeing and photography. Calcium, magnesium and aluminum, common enough in their compounds, have only come into use as metals since the invention of the electric furnace. Now the photographer uses magnesium powder for his flashlight when he wants to take a picture of his friends inside the house, and the aviator uses it when he wants to take a picture of his enemies on the open field. The flares prepared by our Government for the war consist of a sheet iron cylinder, four feet long and six inches thick, containing a stick of magnesium attached to a tightly rolled silk parachute twenty feet in diameter when expanded. The whole weighed 32 pounds. On being dropped from the plane by pressing a button, the rush of air set spinning a pinwheel at the bottom which ignited the magnesium stick and detonated a charge of black powder sufficient to throw off the case and release the parachute. The burning flare gave off a light of 320,000 candle power lasting for ten minutes as the parachute slowly descended. This illuminated the ground on the darkest night sufficiently for the airman to aim his bombs or to take photographs. The addition of 5 or 10 per cent. of magnesium to aluminum gives an alloy (magnalium) that is almost as light as aluminum and almost as strong as steel. An alloy of 90 per cent. aluminum and 10 per cent. calcium is lighter and harder than aluminum and more resistant to corrosion. The latest German airplane, the "Junker," was made entirely of duralumin. Even the wings were formed of corrugated sheets of this alloy instead of the usual doped cotton-cloth. Duralumin is composed of about 85 per cent. of aluminum, 5 per cent. of copper, 5 per cent. of zinc and 2 per cent. of tin. When platinum was first discovered it was so cheap that ingots of it were gilded and sold as gold bricks to unwary purchasers. The Russian Government used it as we use nickel, for making small coins. But this is an exception to the rule that the demand creates the supply. Platinum is really a "rare metal," not merely an unfamiliar one. Nowhere except in the Urals is it found in quantity, and since it seems indispensable in chemical and electrical appliances, the price has continually gone up. Russia collapsed into chaos just when the war work made the heaviest demand for platinum, so the governments had to put a stop to its use for jewelry and photography. The "gold brick" scheme would now have to be reversed, for gold is used as a cheaper metal to "adulterate" platinum. All the members of the platinum family, formerly ignored, were pressed into service, palladium, rhodium, osmium, iridium, and these, alloyed with gold or silver, were employed more or less satisfactorily by the dentist, chemist and electrician as substitutes for the platinum of which they had been deprived. One of these alloys, composed of 20 per cent. palladium and 80 per cent. gold, and bearing the telescoped name of "palau" (palladium au-rum) makes very acceptable crucibles for the laboratory and only costs half as much as platinum. "Rhotanium" is a similar alloy recently introduced. The points of our gold pens are tipped with an osmium-iridium alloy. It is a pity that this family of noble metals is so restricted, for they are unsurpassed in tenacity and incorruptibility. They could be of great service to the world in war and peace. As the "Bad Child" says in his "Book of Beasts": I shoot the hippopotamus with bullets made of platinum, Because if I use leaden ones, his hide is sure to flatten 'em. Along in the latter half of the last century chemists had begun to perceive certain regularities and relationships among the various elements, so they conceived the idea that some sort of a pigeon-hole scheme might be devised in which the elements could be filed away in the order of their atomic weights so that one could see just how a certain element, known or unknown, would behave from merely observing its position in the series. Mendeléef, a Russian chemist, devised the most ingenious of such systems called the "periodic law" and gave proof that there was something in his theory by predicting the properties of three metallic elements, then unknown but for which his arrangement showed three empty pigeon-holes. Sixteen years later all three of these predicted elements had been discovered, one by a Frenchman, one by a German and one by a Scandinavian, and named from patriotic impulse, gallium, germanium and scandium. This was a triumph of scientific prescience as striking as the mathematical proof of the existence of the planet Neptune by Leverrier before it had been found by the telescope. But although Mendeléef's law told "the truth," it gradually became evident that it did not tell "the whole truth and nothing but the truth," as the lawyers put it. As usually happens in the history of science the hypothesis was found not to explain things so simply and completely as was at first assumed. The anomalies in the arrangement did not disappear on closer study, but stuck out more conspicuously. Though Mendeléef had pointed out three missing links, he had failed to make provision for a whole group of elements since discovered, the inert gases of the helium-argon group. As we now know, the scheme was built upon the false assumptions that the elements are immutable and that their atomic weights are invariable. The elements that the chemists had most difficulty in sorting out and identifying were the heavy metals found in the "rare earths." There were about twenty of them so mixed up together and so much alike as to baffle all ordinary means of separating them. For a hundred years chemists worked over them and quarreled over them before they discovered that they had a commercial value. It was a problem as remote from practicality as any that could be conceived. The man in the street did not see why chemists should care whether there were two didymiums any more than why theologians should care whether there were two Isaiahs. But all of a sudden, in 1885, the chemical puzzle became a business proposition. The rare earths became household utensils and it made a big difference with our monthly gas bills whether the ceria and the thoria in the burner mantles were absolutely pure or contained traces of some of the other elements that were so difficult to separate. This sudden change of venue from pure to applied science came about through a Viennese chemist, Dr. Carl Auer, later and in consequence known as Baron Auer von Welsbach. He was trying to sort out the rare earths by means of the spectroscopic method, which consists ordinarily in dipping a platinum wire into a solution of the unknown substance and holding it in a colorless gas flame. As it burns off, each element gives a characteristic color to the flame, which is seen as a series of lines when looked at through the spectroscope. But the flash of the flame from the platinum wire was too brief to be studied, so Dr. Auer hit upon the plan of soaking a thread in the liquid and putting this in the gas jet. The cotton of course burned off at once, but the earths held together and when heated gave off a brilliant white light, very much like the calcium or limelight which is produced by heating a stick of quicklime in the oxy-hydrogen flame. But these rare earths do not require any such intense heat as that, for they will glow in an ordinary gas jet. So the Welsbach mantle burner came into use everywhere and rescued the coal gas business from the destruction threatened by the electric light. It was no longer necessary to enrich the gas with oil to make its flame luminous, for a cheaper fuel gas such as is used for a gas stove will give, with a mantle, a fine white light of much higher candle power than the ordinary gas jet. The mantles are knit in narrow cylinders on machines, cut off at suitable lengths, soaked in a solution of the salts of the rare earths and dried. Artificial silk (viscose) has been found better than cotton thread for the mantles, for it is solid, not hollow, more uniform in quality and continuous instead of being broken up into one-inch fibers. There is a great deal of difference in the quality of these mantles, as every one who has used them knows. Some that give a bright glow at first with the gas-cock only half open will soon break up or grow dull and require more gas to get any kind of a light out of them. Others will last long and grow better to the last. Slight impurities in the earths or the gas will speedily spoil the light. The best results are obtained from a mixture of 99 parts thoria and 1 part ceria. It is the ceria that gives the light, yet a little more of it will lower the luminosity. The non-chemical reader is apt to be confused by the strange names and their varied terminations, but he need not be when he learns that the new metals are given names ending in _-um_, such as sodium, cerium, thorium, and that their oxides (compounds with oxygen, the earths) are given the termination _-a_, like soda, ceria, thoria. So when he sees a name ending in _-um_ let him picture to himself a metal, any metal since they mostly look alike, lead or silver, for example. And when he comes across a name ending in _-a_ he may imagine a white powder like lime. Thorium, for instance, is, as its name implies, a metal named after the thunder god Thor, to whom we dedicate one day in each week, Thursday. Cerium gets its name from the Roman goddess of agriculture by way of the asteroid. The chief sources of the material for the Welsbach burners is monazite, a glittering yellow sand composed of phosphate of cerium with some 5 per cent. of thorium. In 1916 the United States imported 2,500,000 pounds of monazite from Brazil and India, most of which used to go to Germany. In 1895 we got over a million and a half pounds from the Carolinas, but the foreign sand is richer and cheaper. The price of the salts of the rare metals fluctuates wildly. In 1895 thorium nitrate sold at $200 a pound; in 1913 it fell to $2.60, and in 1916 it rose to $8. Since the monazite contains more cerium than thorium and the mantles made from it contain more thorium than cerium, there is a superfluity of cerium. The manufacturers give away a pound of cerium salts with every purchase of a hundred pounds of thorium salts. It annoyed Welsbach to see the cerium residues thrown away and accumulating around his mantle factory, so he set out to find some use for it. He reduced the mixed earths to a metallic form and found that it gave off a shower of sparks when scratched. An alloy of cerium with 30 or 35 per cent. of iron proved the best and was put on the market in the form of automatic lighters. A big business was soon built up in Austria on the basis of this obscure chemical element rescued from the dump-heap. The sale of the cerite lighters in France threatened to upset the finances of the republic, which derived large revenue from its monopoly of match-making, so the French Government imposed a tax upon every man who carried one. American tourists who bought these lighters in Germany used to be much annoyed at being held up on the French frontier and compelled to take out a license. During the war the cerium sparklers were much used in the trenches for lighting cigarettes, but--as those who have seen "The Better 'Ole" will know--they sometimes fail to strike fire. Auer-metal or cerium-iron alloy was used in munitions to ignite hand grenades and to blazon the flight of trailer shells. There are many other pyrophoric (light-producing) alloys, including steel, which our ancestors used with flint before matches and percussion caps were invented. There are more than fifty metals known and not half of them have come into common use, so there is still plenty of room for the expansion of the science of metallurgy. If the reader has not forgotten his arithmetic of permutations he can calculate how many different alloys may be formed by varying the combinations and proportions of these fifty. We have seen how quickly elements formerly known only to chemists--and to some of them known only by name--have become indispensable in our daily life. Any one of those still unutilized may be found to have peculiar properties that fit it for filling a long unfelt want in modern civilization. Who, for instance, will find a use for gallium, the metal of France? It was described in 1869 by Mendeléef in advance of its advent and has been known in person since 1875, but has not yet been set to work. It is such a remarkable metal that it must be good for something. If you saw it in a museum case on a cold day you might take it to be a piece of aluminum, but if the curator let you hold it in your hand--which he won't--it would melt and run over the floor like mercury. The melting point is 87° Fahr. It might be used in thermometers for measuring temperatures above the boiling point of mercury were it not for the peculiar fact that gallium wets glass so it sticks to the side of the tube instead of forming a clear convex curve on top like mercury. Then there is columbium, the American metal. It is strange that an element named after Columbia should prove so impractical. Columbium is a metal closely resembling tantalum and tantalum found a use as electric light filaments. A columbium lamp should appeal to our patriotism. The so-called "rare elements" are really abundant enough considering the earth's crust as a whole, though they are so thinly scattered that they are usually overlooked and hard to extract. But whenever one of them is found valuable it is soon found available. A systematic search generally reveals it somewhere in sufficient quantity to be worked. Who, then, will be the first to discover a use for indium, germanium, terbium, thulium, lanthanum, neodymium, scandium, samarium and others as unknown to us as tungsten was to our fathers? As evidence of the statement that it does not matter how rare an element may be it will come into common use if it is found to be commonly useful, we may refer to radium. A good rich specimen of radium ore, pitchblende, may contain as much, as one part in 4,000,000. Madame Curie, the brilliant Polish Parisian, had to work for years before she could prove to the world that such an element existed and for years afterwards before she could get the metal out. Yet now we can all afford a bit of radium to light up our watch dials in the dark. The amount needed for this is infinitesimal. If it were more it would scorch our skins, for radium is an element in eruption. The atom throws off corpuscles at intervals as a Roman candle throws off blazing balls. Some of these particles, the alpha rays, are atoms of another element, helium, charged with positive electricity and are ejected with a velocity of 18,000 miles a second. Some of them, the beta rays, are negative electrons, only about one seven-thousandth the size of the others, but are ejected with almost the speed of light, 186,000 miles a second. If one of the alpha projectiles strikes a slice of zinc sulfide it makes a splash of light big enough to be seen with a microscope, so we can now follow the flight of a single atom. The luminous watch dials consist of a coating of zinc sulfide under continual bombardment by the radium projectiles. Sir William Crookes invented this radium light apparatus and called it a "spinthariscope," which is Greek for "spark-seer." Evidently if radium is so wasteful of its substance it cannot last forever nor could it have forever existed. The elements then ate not necessarily eternal and immutable, as used to be supposed. They have a natural length of life; they are born and die and propagate, at least some of them do. Radium, for instance, is the offspring of ionium, which is the great-great-grandson of uranium, the heaviest of known elements. Putting this chemical genealogy into biblical language we might say: Uranium lived 5,000,000,000 years and begot Uranium X1, which lived 24.6 days and begot Uranium X2, which lived 69 seconds and begot Uranium 2, which lived 2,000,000 years and begot Ionium, which lived 200,000 years and begot Radium, which lived 1850 years and begot Niton, which lived 3.85 days and begot Radium A, which lived 3 minutes and begot Radium B, which lived 26.8 minutes and begot Radium C, which lived 19.5 minutes and begot Radium D, which lived 12 years and begot Radium E, which lived 5 days and begot Polonium, which lived 136 days and begot Lead. The figures I have given are the times when half the parent substance has gone over into the next generation. It will be seen that the chemist is even more liberal in his allowance of longevity than was Moses with the patriarchs. It appears from the above that half of the radium in any given specimen will be transformed in about 2000 years. Half of what is left will disappear in the next 2000 years, half of that in the next 2000 and so on. The reader can figure out for himself when it will all be gone. He will then have the answer to the old Eleatic conundrum of when Achilles will overtake the tortoise. But we may say that after 100,000 years there would not be left any radium worth mentioning, or in other words practically all the radium now in existence is younger than the human race. The lead that is found in uranium and has presumably descended from uranium, behaves like other lead but is lighter. Its atomic weight is only 206, while ordinary lead weighs 207. It appears then that the same chemical element may have different atomic weights according to its ancestry, while on the other hand different chemical elements may have the same atomic weight. This would have seemed shocking heresy to the chemists of the last century, who prided themselves on the immutability of the elements and did not take into consideration their past life or heredity. The study of these radioactive elements has led to a new atomic theory. I suppose most of us in our youth used to imagine the atom as a little round hard ball, but now it is conceived as a sort of solar system with an electropositive nucleus acting as the sun and negative electrons revolving around it like the planets. The number of free positive electrons in the nucleus varies from one in hydrogen to 92 in uranium. This leaves room for 92 possible elements and of these all but six are more or less certainly known and definitely placed in the scheme. The atom of uranium, weighing 238 times the atom of hydrogen, is the heaviest known and therefore the ultimate limit of the elements, though it is possible that elements may be found beyond it just as the planet Neptune was discovered outside the orbit of Uranus. Considering the position of uranium and its numerous progeny as mentioned above, it is quite appropriate that this element should bear the name of the father of all the gods. In these radioactive elements we have come upon sources of energy such as was never dreamed of in our philosophy. The most striking peculiarity of radium is that it is always a little warmer than its surroundings, no matter how warm these may be. Slowly, spontaneously and continuously, it decomposes and we know no way of hastening or of checking it. Whether it is cooled in liquefied air or heated to its melting point the change goes on just the same. An ounce of radium salt will give out enough heat in one hour to melt an ounce of ice and in the next hour will raise this water to the boiling point, and so on again and again without cessation for years, a fire without fuel, a realization of the philosopher's lamp that the alchemists sought in vain. The total energy so emitted is millions of times greater than that produced by any chemical combination such as the union of oxygen and hydrogen to form water. From the heavy white salt there is continually rising a faint fire-mist like the will-o'-the-wisp over a swamp. This gas is known as the emanation or niton, "the shining one." A pound of niton would give off energy at the rate of 23,000 horsepower; fine stuff to run a steamer, one would think, but we must remember that it does not last. By the sixth day the power would have fallen off by half. Besides, no one would dare to serve as engineer, for the radiation will rot away the flesh of a living man who comes near it, causing gnawing ulcers or curing them. It will not only break down the complex and delicate molecules of organic matter but will attack the atom itself, changing, it is believed, one element into another, again the fulfilment of a dream of the alchemists. And its rays, unseen and unfelt by us, are yet strong enough to penetrate an armorplate and photograph what is behind it. But radium is not the most mysterious of the elements but the least so. It is giving out the secret that the other elements have kept. It suggests to us that all the other elements in proportion to their weight have concealed within them similar stores of energy. Astronomers have long dazzled our imaginations by calculating the horsepower of the world, making us feel cheap in talking about our steam engines and dynamos when a minutest fraction of the waste dynamic energy of the solar system would make us all as rich as millionaires. But the heavenly bodies are too big for us to utilize in this practical fashion. And now the chemists have become as exasperating as the astronomers, for they give us a glimpse of incalculable wealth in the meanest substance. For wealth is measured by the available energy of the world, and if a few ounces of anything would drive an engine or manufacture nitrogenous fertilizer from the air all our troubles would be over. Kipling in his sketch, "With the Night Mail," and Wells in his novel, "The World Set Free," stretched their imaginations in trying to tell us what it would mean to have command of this power, but they are a little hazy in their descriptions of the machinery by which it is utilized. The atom is as much beyond our reach as the moon. We cannot rob its vault of the treasure. READING REFERENCES The foregoing pages will not have achieved their aim unless their readers have become sufficiently interested in the developments of industrial chemistry to desire to pursue the subject further in some of its branches. Assuming such interest has been aroused, I am giving below a few references to books and articles which may serve to set the reader upon the right track for additional information. To follow the rapid progress of applied science it is necessary to read continuously such periodicals as the _Journal of Industrial and Engineering Chemistry_ (New York), _Metallurgical and Chemical Engineering_ (New York), _Journal of the Society of Chemical Industry_ (London), _Chemical Abstracts_ (published by the American Chemical Society, Easton, Pa.), and the various journals devoted to special trades. The reader may need to be reminded that the United States Government publishes for free distribution or at low price annual volumes or special reports dealing with science and industry. Among these may be mentioned "Yearbook of the Department of Agriculture"; "Mineral Resources of the United States," published by the United States Geological Survey in two annual volumes, Vol. I on the metals and Vol. II on the non-metals; the "Annual Report of the Smithsonian Institution," containing selected articles on pure and applied science; the daily "Commerce Reports" and special bulletins of Department of Commerce. Write for lists of publications of these departments. The following books on industrial chemistry in general are recommended for reading and reference: "The Chemistry of Commerce" and "Some Chemical Problems of To-Day" by Robert Kennedy Duncan (Harpers, N.Y.), "Modern Chemistry and Its Wonders" by Martin (Van Nostrand), "Chemical Discovery and Invention in the Twentieth Century" by Sir William A. Tilden (Dutton, N.Y.), "Discoveries and Inventions of the Twentieth Century" by Edward Cressy (Dutton), "Industrial Chemistry" by Allen Rogers (Van Nostrand). "Everyman's Chemistry" by Ellwood Hendrick (Harpers, Modern Science Series) is written in a lively style and assumes no previous knowledge of chemistry from the reader. The chapters on cellulose, gums, sugars and oils are particularly interesting. "Chemistry of Familiar Things" by S.S. Sadtler (Lippincott) is both comprehensive and comprehensible. The following are intended for young readers but are not to be despised by their elders who may wish to start in on an easy up-grade: "Chemistry of Common Things" (Allyn & Bacon, Boston) is a popular high school text-book but differing from most text-books in being readable and attractive. Its descriptions of industrial processes are brief but clear. The "Achievements of Chemical Science" by James C. Philip (Macmillan) is a handy little book, easy reading for pupils. "Introduction to the Study of Science" by W.P. Smith and E.G. Jewett (Macmillan) touches upon chemical topics in a simple way. On the history of commerce and the effect of inventions on society the following titles may be suggested: "Outlines of Industrial History" by E. Cressy (Macmillan); "The Origin of Invention," a study of primitive industry, by O.T. Mason (Scribner); "The Romance of Commerce" by Gordon Selbridge (Lane); "Industrial and Commercial Geography" or "Commerce and Industry" by J. Russell Smith (Holt); "Handbook of Commercial Geography" by G.G. Chisholm (Longmans). The newer theories of chemistry and the constitution of the atom are explained in "The Realities of Modern Science" by John Mills (Macmillan), and "The Electron" by R.A. Millikan (University of Chicago Press), but both require a knowledge of mathematics. The little book on "Matter and Energy" by Frederick Soddy (Holt) is better adapted to the general reader. The most recent text-book is the "Introduction to General Chemistry" by H.N. McCoy and E.M. Terry. (Chicago, 1919.) CHAPTER II The reader who may be interested in following up this subject will find references to all the literature in the summary by Helen R. Hosmer, of the Research Laboratory of the General Electric Company, in the _Journal of Industrial and Engineering Chemistry_, New York, for April, 1917. Bucher's paper may be found in the same journal for March, and the issue for September contains a full report of the action of U.S. Government and a comparison of the various processes. Send fifteen cents to the U.S. Department of Commerce (or to the nearest custom house) for Bulletin No. 52, Special Agents Series on "Utilization of Atmospheric Nitrogen" by T.H. Norton. The Smithsonian Institution of Washington has issued a pamphlet on "Sources of Nitrogen Compounds in the United States." In the 1913 report of the Smithsonian Institution there are two fine articles on this subject: "The Manufacture of Nitrates from the Atmosphere" and "The Distribution of Mankind," which discusses Sir William Crookes' prediction of the exhaustion of wheat land. The D. Van Nostrand Co., New York, publishes a monograph on "Fixation of Atmospheric Nitrogen" by J. Knox, also "TNT and Other Nitrotoluenes" by G.C. Smith. The American Cyanamid Company, New York, gives out some attractive literature on their process. "American Munitions 1917-1918," the report of Benedict Crowell, Director of Munitions, to the Secretary of War, gives a fully illustrated account of the manufacture of arms, explosives and toxic gases. Our war experience in the "Oxidation of Ammonia" is told by C.L. Parsons in _Journal of Industrial and Engineering Chemistry_, June, 1919, and various other articles on the government munition work appeared in the same journal in the first half of 1919. "The Muscle Shoals Nitrate Plant" in _Chemical and Metallurgical Engineering_, January, 1919. CHAPTER III The Department of Agriculture or your congressman will send you literature on the production and use of fertilizers. From your state agricultural experiment station you can procure information as to local needs and products. Consult the articles on potash salts and phosphate rock in the latest volume of "Mineral Resources of the United States," Part II Non-Metals (published free by the U.S. Geological Survey). Also consult the latest Yearbook of the Department of Agriculture. For self-instruction, problems and experiments get "Extension Course in Soils," Bulletin No. 355, U.S. Dept. of Agric. A list of all government publications on "Soil and Fertilizers" is sent free by Superintendent of Documents, Washington. The _Journal of Industrial and Engineering Chemistry_ for July, 1917, publishes an article by W.C. Ebaugh on "Potash and a World Emergency," and various articles on American sources of potash appeared in the same _Journal_ October, 1918, and February, 1918. Bulletin 102, Part 2, of the United States National Museum contains an interpretation of the fertilizer situation in 1917 by J.E. Poque. On new potash deposits in Alsace and elsewhere see _Scientific American Supplement_, September 14, 1918. CHAPTER IV Send ten cents to the Department of Commerce, Washington, for "Dyestuffs for American Textile and Other Industries," by Thomas H. Norton, Special Agents' Series, No. 96. A more technical bulletin by the same author is "Artificial Dyestuffs Used in the United States," Special Agents' Series, No. 121, thirty cents. "Dyestuff Situation in U.S.," Special Agents' Series, No. 111, five cents. "Coal-Tar Products," by H.G. Porter, Technical Paper 89, Bureau of Mines, Department of the Interior, five cents. "Wealth in Waste," by Waldemar Kaempfert, _McClure's_, April, 1917. "The Evolution of Artificial Dyestuffs," by Thomas H. Norton, _Scientific American_, July 21, 1917. "Germany's Commercial Preparedness for Peace," by James Armstrong, _Scientific American_, January 29, 1916. "The Conquest of Commerce" and "American Made," by Edwin E. Slosson in _The Independent_ of September 6 and October 11, 1915. The H. Koppers Company, Pittsburgh, give out an illustrated pamphlet on their "By-Product Coke and Gas Ovens." The addresses delivered during the war on "The Aniline Color, Dyestuff and Chemical Conditions," by I.F. Stone, president of the National Aniline and Chemical Company, have been collected in a volume by the author. For "Dyestuffs as Medicinal Agents" by G. Heyl, see _Color Trade Journal_, vol. 4, p. 73, 1919. "The Chemistry of Synthetic Drugs" by Percy May, and "Color in Relation to Chemical Constitution" by E.R. Watson are published in Longmans' "Monographs on Industrial Chemistry." "Enemy Property in the United States" by A. Mitchell Palmer in _Saturday Evening Post_, July 19, 1919, tells of how Germany monopolized chemical industry. "The Carbonization of Coal" by V.B. Lewis (Van Nostrand, 1912). "Research in the Tar Dye Industry" by B.C. Hesse in _Journal of Industrial and Engineering Chemistry_, September, 1916. Kekulé tells how he discovered the constitution of benzene in the _Berichte der Deutschen chemischen Gesellschaft_, V. XXIII, I, p. 1306. I have quoted it with some other instances of dream discoveries in _The Independent_ of Jan. 26, 1918. Even this innocent scientific vision has not escaped the foul touch of the Freudians. Dr. Alfred Robitsek in "Symbolisches Denken in der chemischen Forschung," _Imago_, V. I, p. 83, has deduced from it that Kekulé was morally guilty of the crime of OEdipus as well as minor misdemeanors. CHAPTER V Read up on the methods of extracting perfumes from flowers in any encyclopedia or in Duncan's "Chemistry of Commerce" or Tilden's "Chemical Discovery in the Twentieth Century" or Rogers' "Industrial Chemistry." The pamphlet containing a synopsis of the lectures by the late Alois von Isakovics on "Synthetic Perfumes and Flavors," published by the Synfleur Scientific Laboratories, Monticello, New York, is immensely interesting. Van Dyk & Co., New York, issue a pamphlet on the composition of oil of rose. Gildemeister's "The Volatile Oils" is excellent on the history of the subject. Walter's "Manual for the Essence Industry" (Wiley) gives methods and recipes. Parry's "Chemistry of Essential Oils and Artificial Perfumes," 1918 edition. "Chemistry and Odoriferous Bodies Since 1914" by G. Satie in _Chemie et Industrie_, vol. II, p. 271, 393. "Odor and Chemical Constitution," _Chemical Abstracts_, 1917, p. 3171 and _Journal of Society for Chemical Industry_, v. 36, p. 942. CHAPTER VI The bulletin on "By-Products of the Lumber Industry" by H.K. Benson (published by Department of Commerce, Washington, 10 cents) contains a description of paper-making and wood distillation. There is a good article on cellulose products by H.S. Mork in _Journal of the Franklin Institute_, September, 1917, and in _Paper_, September 26, 1917. The Government Forest Products Laboratory at Madison, Wisconsin, publishes technical papers on distillation of wood, etc. The Forest Service of the U.S. Department of Agriculture is the chief source of information on forestry. The standard authority is Cross and Bevans' "Cellulose." For the acetates see the eighth volume of Worden's "Technology of the Cellulose Esters." CHAPTER VII The speeches made when Hyatt was awarded the Perkin medal by the American Chemical Society for the discovery of celluloid may be found in the _Journal of the Society of Chemical Industry_ for 1914, p. 225. In 1916 Baekeland received the same medal, and the proceedings are reported in the same _Journal_, v. 35, p. 285. A comprehensive technical paper with bibliography on "Synthetic Resins" by L.V. Redman appeared in the _Journal of Industrial and Engineering Chemistry_, January, 1914. The controversy over patent rights may be followed in the same _Journal_, v. 8 (1915), p. 1171, and v. 9 (1916), p. 207. The "Effects of Heat on Celluloid" have been examined by the Bureau of Standards, Washington (Technological Paper No. 98), abstract in _Scientific American Supplement_, June 29, 1918. For casein see Tague's article in Rogers' "Industrial Chemistry" (Van Nostrand). See also Worden's "Nitrocellulose Industry" and "Technology of the Cellulose Esters" (Van Nostrand); Hodgson's "Celluloid" and Cross and Bevan's "Cellulose." For references to recent research and new patent specifications on artificial plastics, resins, rubber, leather, wood, etc., see the current numbers of _Chemical Abstracts_ (Easton, Pa.) and such journals as the _India Rubber Journal, Paper, Textile World, Leather World_ and _Journal of American Leather Chemical Association._ The General Bakelite Company, New York, the Redmanol Products Company, Chicago, the Condensite Company, Bloomfield, N.J., the Arlington Company, New York (handling pyralin), give out advertising literature regarding their respective products. CHAPTER VIII Sir William Tilden's "Chemical Discovery and Invention in the Twentieth Century" (E.P. Dutton & Co.) contains a readable chapter on rubber with references to his own discovery. The "Wonder Book of Rubber," issued by the B.F. Goodrich Rubber Company, Akron, Ohio, gives an interesting account of their industry. Iles: "Leading American Inventors" (Henry Holt & Co.) contains a life of Goodyear, the discoverer of vulcanization. Potts: "Chemistry of the Rubber Industry, 1912." The Rubber Industry: Report of the International Rubber Congress, 1914. Pond: "Review of Pioneer Work in Rubber Synthesis" in _Journal of the American Chemical Society_, 1914. Bang: "Synthetic Rubber" in _Metallurgical and Chemical Engineering_, May 1, 1917. Castellan: "L'Industrie caoutchoucière," doctor's thesis, University of Paris, 1915. The _India Rubber World_, New York, all numbers, especially "What I Saw in the Philippines," by the Editor, 1917. Pearson: "Production of Guayule Rubber," _Commerce Reports_, 1918, and _India Rubber World_, 1919. "Historical Sketch of Chemistry of Rubber" by S.C. Bradford in _Science Progress_, v. II, p. 1. CHAPTER IX "The Cane Sugar Industry" (Bulletin No. 53, Miscellaneous Series, Department of Commerce, 50 cents) gives agricultural and manufacturing costs in Hawaii, Porto Rico, Louisiana and Cuba. "Sugar and Its Value as Food," by Mary Hinman Abel. (Farmer's Bulletin No. 535, Department of Agriculture, free.) "Production of Sugar in the United States and Foreign Countries," by Perry Elliott. (Department of Agriculture, 10 cents.) "Conditions in the Sugar Market January to October, 1917," a pamphlet published by the American Sugar Refining Company, 117 Wall Street, New York, gives an admirable survey of the present situation as seen by the refiners. "Cuban Cane Sugar," by Robert Wiles, 1916 (Indianapolis: Bobbs-Merrill Co., 75 cents), an attractive little book in simple language. "The World's Cane Sugar Industry, Past and Present," by H.C.P. Geering. "The Story of Sugar," by Prof. G.T. Surface of Yale (Appleton, 1910). A very interesting and reliable book. The "Digestibility of Glucose" is discussed in _Journal of Industrial and Engineering Chemistry_, August, 1917. "Utilization of Beet Molasses" in _Metallurgical and Chemical Engineering_, April 5, 1917. CHAPTER X "Maize," by Edward Alber (Bulletin of the Pan-American Union, January, 1915). "Glucose," by Geo. W. Rolfe _(Scientific American Supplement_, May 15 or November 6, 1915, and in Boger's "Industrial Chemistry"). On making ethyl alcohol from wood, see Bulletin No. 110, Special Agents' Series, Department of Commerce (10 cents), and an article by F.W. Kressmann in _Metallurgical and Chemical Engineering_, July 15, 1916. On the manufacture and uses of industrial alcohol the Department of Agriculture has issued for free distribution Farmer's Bulletin 269 and 424, and Department Bulletin 182. On the "Utilization of Corn Cobs," see _Journal of Industrial and Engineering Chemistry_, Nov., 1918. For John Winthrop's experiment, see the same _Journal_, Jan., 1919. CHAPTER XI President Scherer's "Cotton as a World Power" (Stokes, 1916) is a fascinating volume that combines the history, science and politics of the plant and does not ignore the poetry and legend. In the Yearbook of the Department of Agriculture for 1916 will be found an interesting article by H.S. Bailey on "Some American Vegetable Oils" (sold separate for five cents), also "The Peanut: A Great American Food" by same author in the Yearbook of 1917. "The Soy Bean Industry" is discussed in the same volume. See also: Thompson's "Cottonseed Products and Their Competitors in Northern Europe" (Part I, Cake and Meal; Part II, Edible Oils. Department of Commerce, 10 cents each). "Production and Conservation of Fats and Oils in the United States" (Bulletin No. 769, 1919, U.S. Dept. of Agriculture). "Cottonseed Meal for Feeding Cattle" (U.S. Department of Agriculture, Farmer's Bulletin 655, free). "Cottonseed Industry in Foreign Countries," by T.H. Norton, 1915 (Department of Commerce, 10 cents). "Cottonseed Products" in _Journal of the Society of Chemical Industry_, July 16, 1917, and Baskerville's article in the same journal (1915, vol. 7, p. 277). Dunstan's "Oil Seeds and Feeding Cakes," a volume on British problems since the war. Ellis's "The Hydrogenation of Oils" (Van Nostrand, 1914). Copeland's "The Coconut" (Macmillan). Barrett's "The Philippine Coconut Industry" (Bulletin No. 25, Philippine Bureau of Agriculture). "Coconuts, the Consols of the East" by Smith and Pope (London). "All About Coconuts" by Belfort and Hoyer (London). Numerous articles on copra and other oils appear in _U.S. Commerce Reports_ and _Philippine Journal of Science_. "The World Wide Search for Oils" in _The Americas_ (National City Bank, N.Y.). "Modern Margarine Technology" by W. Clayton in _Journal Society of Chemical Industry_, Dec. 5, 1917; also see _Scientific_ _American Supplement_, Sept. 21, 1918. A court decision on the patent rights of hydrogenation is given in _Journal of Industrial and Engineering Chemistry_ for December, 1917. The standard work on the whole subject is Lewkowitsch's "Chemical Technology of Oils, Fats and Waxes" (3 vols., Macmillan, 1915). CHAPTER XII A full account of the development of the American Warfare Service has been published in the _Journal of Industrial and Engineering Chemistry_ in the monthly issues from January to August, 1919, and an article on the British service in the issue of April, 1918. See also Crowell's Report on "America's Munitions," published by War Department. _Scientific American_, March 29, 1919, contains several articles. A. Russell Bond's "Inventions of the Great War" (Century) contains chapters on poison gas and explosives. Lieutenant Colonel S.J.M. Auld, Chief Gas Officer of Sir Julian Byng's army and a member of the British Military Mission to the United States, has published a volume on "Gas and Flame in Modern Warfare" (George H. Doran Co.). CHAPTER XIII See chapter in Cressy's "Discoveries and Inventions of Twentieth Century." "Oxy-Acetylene Welders," Bulletin No. 11, Federal Board of Vocational Education, Washington, June, 1918, gives practical directions for welding. _Reactions_, a quarterly published by Goldschmidt Thermit Company, N.Y., reports latest achievements of aluminothermics. Provost Smith's "Chemistry in America" (Appleton) tells of the experiments of Robert Hare and other pioneers. "Applications of Electrolysis in Chemical Industry" by A.F. Hall (Longmans). For recent work on artificial diamonds see _Scientific American Supplement_, Dec. 8, 1917, and August 24, 1918. On acetylene see "A Storehouse of Sleeping Energy" by J.M. Morehead in _Scientific American_, January 27, 1917. CHAPTER XIV Spring's "Non-Technical Talks on Iron and Steel" (Stokes) is a model of popular science writing, clear, comprehensive and abundantly illustrated. Tilden's "Chemical Discovery in the Twentieth Century" must here again be referred to. The Encyclopedia Britannica is convenient for reference on the various metals mentioned; see the article on "Lighting" for the Welsbach burner. The annual "Mineral Resources of the United States, Part I," contains articles on the newer metals by Frank W. Hess; see "Tungsten" in the volume for 1914, also Bulletin No. 652, U.S. Geological Survey, by same author. _Foote-Notes_, the house organ of the Foote Mineral Company, Philadelphia, gives information on the rare elements. Interesting advertising literature may be obtained from the Titantium Alloy Manufacturing Company, Niagara Falls, N.Y.; Duriron Castings Company, Dayton, O.; Buffalo Foundry and Machine Company, Buffalo, N.Y., manufacturers of "Buflokast" acid-proof apparatus, and similar concerns. The following additional references may be useful: Stellite alloys in _Jour. Ind. & Eng. Chem._, v. 9, p. 974; Rossi's work on titantium in same journal, Feb., 1918; Welsbach mantles in _Journal Franklin Institute_, v. 14, p. 401, 585; pure alloys in _Trans. Amer. Electro-Chemical Society_, v. 32, p. 269; molybdenum in _Engineering_, 1917, or _Scientific American Supplement_, Oct. 20, 1917; acid-resisting iron in _Sc. Amer. Sup._, May 31, 1919; ferro-alloys in _Jour. Ind. & Eng. Chem._, v. 10, p. 831; influence of vanadium, etc., on iron, in _Met. Chem. Eng._, v. 15, p. 530; tungsten in _Engineering_, v. 104, p. 214. INDEX Abrasives, 249-251 Acetanilid, 87 Acetone, 125, 154, 243, 245 Acetylene, 30, 154, 240-248, 257, 307, 308 Acheson, 249 Air, liquefied, 33 Alcohol, ethyl, 101, 102, 127, 174, 190-194, 242-244, 305 methyl, 101, 102, 127, 191 Aluminum, 31, 246-248, 255, 272, 284 Ammonia, 27, 29, 31, 33, 56, 64, 250 American dye industry, 82 Aniline dyes, 60-92 Antiseptics, 86, 87 Argon, 16 Art and nature, 8, 9, 170, 173 Artificial silk, 116, 118, 119 Aspirin, 84 Atomic theory, 293-296, 299 Aylesworth, 140 Baekeland, 137 Baeyer, Adolf von, 77 Bakelite, 138, 303 Balata, 159 Bauxite, 31 Beet sugar, 165, 169, 305 Benzene formula, 67, 301, 101 Berkeley, 61 Berthelot, 7, 94 Birkeland-Eyde process, 26 Bucher process, 32 Butter, 201, 208 Calcium, 246, 253 Calcium carbide, 30, 339 Camphor, 100, 131 Cane sugar, 164, 167, 177, 180, 305 Carbolic acid, 18, 64, 84, 101, 102, 137 Carborundum, 249-251 Caro and Frank process, 30 Casein, 142 Castner, 246 Catalyst, 28, 204 Celluloid, 128-135, 302 Cellulose, 110-127, 129, 137, 302 Cellulose acetate, 118, 120, 302 Cerium, 288-290 Chemical warfare, 218-235, 307 Chlorin, 224, 226, 250 Chlorophyll, 267 Chlorpicrin, 224, 226 Chromicum, 278, 280 Coal, distillation of, 60, 64, 70, 84, 301 Coal tar colors, 60-92 Cochineal, 79 Coconut oil, 203, 211-215, 306 Collodion, 117, 123, 130 Cologne, eau de, 107 Copra, 203, 211-215, 306 Corn oil, 183, 305 Cotton, 112, 120, 129, 197 Cocain, 88 Condensite, 141 Cordite, 18, 19 Corn products, 181-195, 305 Coslett process, 273 Cottonseed oil, 201 Cowles, 248 Creative chemistry, 7 Crookes, Sir William, 292, 299 Curie, Madame, 292 Cyanamid, 30, 35, 299 Cyanides, 32 Diamond, 259-261, 308 Doyle, Sir Arthur Conan, 221 Drugs, synthetic, 6, 84, 301 Duisberg, 151 Dyestuffs, 60-92 Edison, 84, 141 Ehrlich, 86, 87 Electric furnace, 236-262, 307 Fats, 196-217, 306 Fertilizers, 37, 41, 43, 46, 300 Flavors, synthetic, 93-109 Food, synthetic, 94 Formaldehyde, 136, 142 Fruit flavors, synthetic, 99, 101 Galalith, 142 Gas masks, 223, 226, 230, 231 Gerhardt, 6, 7 Glucose, 137, 184-189, 194, 305 Glycerin, 194, 203 Goldschmidt, 256 Goodyear, 161 Graphite, 258 Guayule, 159, 304 Guncotton, 17, 117, 125, 130 Gunpowder, 14, 15, 22, 234 Gutta percha, 159 Haber process, 27, 28 Hall, C.H., 247 Hare, Robert, 237, 245, 307 Harries, 149 Helium, 236 Hesse, 70, 72, 90 Hofmann, 72, 80 Huxley, 10 Hyatt, 128, 129, 303 Hydrogen, 253-255 Hydrogenation of oils, 202-205, 306 Indigo, 76, 79 Iron, 236, 253, 262-270, 308 Isoprene, 136, 146, 149, 150, 154 Kelp products, 53, 142 Kekulé's dream, 66, 301 Lard substitutes, 209 Lavoisier, 6 Leather substitutes, 124 Leucite, 53 Liebig, 38 Linseed oil, 202, 205, 270 Magnesium, 283 Maize products, 181-196, 305 Manganese, 278 Margarin, 207-212, 307 Mauve, discovery of, 74 Mendeléef, 285, 291 Mercerized cotton, 115 Moissan, 259 Molybdenum, 283, 308 Munition manufacture in U.S., 33, 224, 299, 307 Mushet, 279 Musk, synthetic, 96, 97, 106 Mustard gas, 224, 227-229 Naphthalene, 4, 142, 154 Nature and art, 8-13, 118, 122, 133 Nitrates, Chilean, 22, 24, 30, 36 Nitric acid derivatives, 20 Nitrocellulose, 17, 117 Nitrogen, in explosives, 14, 16, 117, 299 fixation, 24, 25, 29, 299 Nitro-glycerin, 18, 117, 214 Nobel, 18, 117 Oils, 196-217, 306 Oleomargarin, 207-212, 307 Orange blossoms, 99, 100 Osmium, 28 Ostwald, 29, 55 Oxy-hydrogen blowpipe, 246 Paper, 111, 132 Parker process, 273 Peanut oil, 206, 211, 214, 306 Perfumery, Art of, 103-108 Perfumes, synthetic, 93-109, 302 Perkin, W.H., 148 Perkin, Sir William, 72, 80, 102 Pharmaceutical chemistry, 6, 85-88 Phenol, 18, 64, 84, 101, 102, 137 Phonograph records, 84, 141 Phosphates, 56-59 Phosgene, 224, 225 Photographic developers, 88 Picric acid, 18, 84, 85, 226 Platinum, 28, 278, 280, 284, 286 Plastics, synthetic, 128-143 Pneumatic tires, 162 Poisonous gases in warfare, 218-235, 307 Potash, 37, 45-56, 300 Priestley, 150, 160 Purple, royal, 75, 79 Pyralin, 132, 133 Pyrophoric alloys, 290 Pyroxylin, 17, 127, 125, 130 Radium, 291, 295 Rare earths, 286-288, 308 Redmanol, 140 Remsen, Ira, 178 Refractories, 251-252 Resins, synthetic, 135-143 Rose perfume, 93, 96, 97, 99, 105 Rubber, natural, 155-161, 304 synthetic, 136, 145-163, 304 Rumford, Count, 160 Rust, protection from, 262-275 Saccharin, 178, 179 Salicylic acid, 88, 101 Saltpeter, Chilean, 22, 30, 36, 42 Schoop process, 272 Serpek process, 31 Silicon, 249, 253 Smell, sense of, 97, 98, 103, 109 Smith, Provost, 237, 245, 307 Smokeless powder, 15 Sodium, 148, 238, 247 Soil chemistry, 38, 39 Soy bean, 142, 211, 217, 306 Starch, 137, 184, 189, 190 Stassfort salts, 47, 49, 55 Stellites, 280, 308 Sugar, 164-180, 304 Sulfuric acid, 57 Tantalum, 282 Terpenes, 100, 154 Textile industry, 5, 112, 121, 300 Thermit, 256 Thermodynamics, Second law of, 145 Three periods of progress, 3 Tin plating, 271 Tilden, 146, 298 Titanium, 278, 308 TNT, 19, 21, 84, 299 Trinitrotoluol, 19, 21, 84, 299 Tropics, value of, 96, 156, 165, 196, 206, 213, 216 Tungsten, 257, 277, 281, 308 Uranium, 28 Vanadium, 277, 280, 308 Vanillin, 103 Violet perfume, 100 Viscose, 116 Vitamines, 211 Vulcanization, 161 Welding, 256 Welsbach burner, 287-289, 308 Wheat problem, 43, 299 Wood, distillation of, 126, 127 Wood pulp, 112, 120, 303 Ypres, Use of gases at, 221 Zinc plating, 271 _Once a Slosson Reader_ _Always a Slosson Fan_ JUST PUBLISHED CHATS ON SCIENCE By E.E. SLOSSON Author of "Creative Chemistry," etc. Dr. Slosson is nothing short of a prodigy. He is a triple-starred scientist man who can bring down the highest flying scientific fact and tame it so that any of us can live with it and sometimes even love it. He can make a fairy tale out of coal-tar dyes and a laboratory into a joyful playhouse while it continues functioning gloriously as a laboratory. But to readers of "Creative Chemistry" it is wasting time to talk about Dr. Slosson's style. "Chats On Science," which has just been published, is made up of eighty-five brief chapters or sections or periods, each complete in itself, dealing with a gorgeous variety of subjects. They go from Popover Stars to Soda Water, from How Old Is Disease to Einstein in Words of One Syllable. The reader can begin anywhere, but when he begins he will ultimately read the entire series. It is good science and good reading. It contains some of the best writing Dr. Slosson has ever done. The Boston Transcript says: "These 'Chats' are even more fascinating, were that possible, than 'Creative Chemistry.' They are more marvelous than the most marvelous of fairy tales ... Even an adequate review could give little idea of the treasures of modern scientific knowledge 'Chats on Science' contains ... Dr. Slosson has, besides rare scientific knowledge, that gift of the gods--imagination." * * * * * ("Chats on Science" by E.E. Slosson is published by The Century Company, 353 Fourth Avenue, New York City. It is sold for $2.00 at all bookstores, or it may be ordered from the publisher.) FOOTNOTES: [1] I am quoting mostly Unstead's figures from the _Geographical Journal_ of 1913. See also Dickson's "The Distribution of Mankind," in Smithsonian Report, 1913. [2] United States Abstract of Census of Manufactures, 1914, p. 34. [3] United States Department of Agriculture, Bulletin No. 505. 
29734	----	[Illustration: _To face the Title._] EXPERIMENTS AND OBSERVATIONS ON DIFFERENT KINDS OF AIR. [Price 5s. unbound.] Quamobrem, si qua est erga Creatorem humilitas, si qua operum ejus reverentia et magnificatio, si qua charitas in homines, si erga necessitates et ærumnas humanas relevandas studium, si quis amor veritatis in naturalibus, et odium tenebrarum, et intellectus purificandi desiderium; orandi sunt homines iterum atque iterum, ut, missis philosophiis istis volaticis et preposteris, quæ theses hypothesibus anterposuerunt, et experientiam captivam duxerunt, atque de operibus dei triumpharunt, summisse, et cum veneratione quadam, ad volumen creaturarum evolvendum accedant; atque in eo moram faciant, meditentur, et ab opinionibus abluti et mundi, caste et integre versentur.----In interpretatione ejus eruenda nulli operæ parcant, sed strenue procedant, persistant, immoriantur. LORD BACON IN INSTAURATIONE MAGNA. EXPERIMENTS AND OBSERVATIONS ON DIFFERENT KINDS OF AIR. By JOSEPH PRIESTLEY, LL.D. F.R.S. The SECOND EDITION Corrected. Fert animus Causas tantarum expromere rerum; Immensumque aperitur opus. LUCAN LONDON: Printed for J. JOHNSON, No. 72, in St. Paul's Church-Yard. MDCCLXXV. TO THE RIGHT HONOURABLE THE EARL OF SHELBURNE, THIS TREATISE IS WITH THE GREATEST GRATITUDE AND RESPECT, INSCRIBED, BY HIS LORDSHIP's MOST OBLIGED, AND OBEDIENT HUMBLE SERVANT, J. PRIESTLEY. Transcriber's Note: Footnotes have been moved to the end of the chapter. The errata listed at the end of the book have been corrected in the text. In the text, there are places where the apothecary symbols for ounce and dram are used. These are changed to oz. and dr. in the text file. THE PREFACE. One reason for the present publication has been the favourable reception of those of my _Observations on different kinds of air_, which were published in the Philosophical Transactions for the year 1772, and the demand for them by persons who did not chuse, for the sake of those papers only, to purchase the whole volume in which they were contained. Another motive was the _additions_ to my observations on this subject, in consequence of which my papers grew too large for such a publication as the _Philosophical Transactions_. Contrary, therefore, to my intention, expressed Philosophical Transactions, vol. 64. p. 90, but with the approbation of the President, and of my friends in the society, I have determined to send them no more papers for the present on this subject, but to make a separate and immediate publication of all that I have done with respect to it. Besides, considering the attention which, I am informed, is now given to this subject by philosophers in all parts of Europe, and the rapid progress that has already been made, and may be expected to be made in this branch of knowledge, all unnecessary delays in the publication of experiments relating to it are peculiarly unjustifiable. When, for the sake of a little more reputation, men can keep brooding over a new fact, in the discovery of which they might, possibly, have very little real merit, till they think they can astonish the world with a system as complete as it is new, and give mankind a prodigious idea of their judgment and penetration; they are justly punished for their ingratitude to the fountain of all knowledge, and for their want of a genuine love of science and of mankind, in finding their boasted discoveries anticipated, and the field of honest fame pre-occupied, by men, who, from a natural ardour of mind, engage in philosophical pursuits, and with an ingenuous simplicity immediately communicate to others whatever occurs to them in their inquiries. As to myself, I find it absolutely impossible to produce a work on this subject that shall be any thing like _complete_. My first publication I acknowledged to be very imperfect, and the present, I am as ready to acknowledge, is still more so. But, paradoxical as it may seem, this will ever be the case in the progress of natural science, so long as the works of God are, like himself, infinite and inexhaustible. In completing one discovery we never fail to get an imperfect knowledge of others, of which we could have no idea before; so that we cannot solve one doubt without creating several new ones. Travelling on this ground resembles Pope's description of travelling among the Alps, with this difference, that here there is not only _succession_, but an _increase_ of new objects and new difficulties. So pleas'd at first the tow'ring Alps we try, Mount o'er the vales, and seem to tread the sky. Th' eternal snows appear already past, And the first clouds and mountains seem the last, But those attain'd, we tremble to survey The growing labours of the lengthen'd way. Th' increasing prospect tires our wand'ring eyes, Hills peep o'er hills, and Alps on Alps arise. ESSAY ON CRITICISM. Newton, as he had very little knowledge of _air_, so he had few doubts concerning it. Had Dr. Hales, after his various and valuable investigations, given a list of all his _desiderata_, I am confident that he would not have thought of one in ten that had occurred to me at the time of my last publication; and my doubts, queries, and hints for new experiments are very considerably increased, after a series of investigations, which have thrown great light upon many things of which I was not able to give any explanation before. I would observe farther, that a person who means to serve the cause of science effectually, must hazard his own reputation so far as to risk even _mistakes_ in things of less moment. Among a multiplicity of new objects, and new relations, some will necessarily pass without sufficient attention; but if a man be not mistaken in the principal objects of his pursuits, he has no occasion to distress himself about lesser things. In the progress of his inquiries he will generally be able to rectify his own mistakes; or if little and envious souls should take a malignant pleasure in detecting them for him, and endeavouring to expose him, he is not worthy of the name of a philosopher, if he has not strength of mind sufficient to enable him not to be disturbed at it. He who does not foolishly affect to be above the failings of humanity, will not be mortified when it is proved that he is but a man. In this work, as well as in all my other philosophical writings, I have made it a rule not to conceal the _real views_ with which I have made experiments; because though, by following a contrary maxim, I might have acquired a character of greater sagacity, I think that two very good ends are answered by the method that I have adopted. For it both tends to make a narrative of a course of experiments more interesting, and likewise encourages other adventurers in experimental philosophy; shewing them that, by pursuing even false lights, real and important truths may be discovered, and that in seeking one thing we often find another. In some respects, indeed, this method makes the narrative _longer_, but it is by making it less tedious; and in other respects I have written much more concisely than is usual with those who publish accounts of their experiments. In this treatise the reader will often find the result of long processes expressed in a few lines, and of many such in a single paragraph; each of which, if I had, with the usual parade, described it at large (explaining first the _preparation_, then reciting the _experiment_ itself, with the _result_ of it, and lastly making suitable _reflections_) would have made as many sections or chapters, and have swelled my book to a pompous and respectable size. But I have the pleasure to think that those philosophers who have but little time to spare for _reading_, which is always the case with those who _do_ much themselves, will thank me for not keeping them too long from their own pursuits; and that they will find rather more in the volume, than the appearance of it promises. I do not think it at all degrading to the business of experimental philosophy, to compare it, as I often do, to the diversion of _hunting_, where it sometimes happens that those who have beat the ground the most, and are consequently the best acquainted with it, weary themselves without starting any game; when it may fall in the way of a mere passenger; so that there is but little room for boasting in the most successful termination of the chace. The best founded praise is that which is due to the man, who, from a supreme veneration for the God of nature, takes pleasure in contemplating his _works_, and from a love of his fellow-creatures, as the offspring of the same all-wise and benevolent parent, with a grateful sense and perfect enjoyment of the means of happiness of which he is already possessed, seeks, with earnestness, but without murmuring or impatience, that greater _command of the powers of nature_, which can only be obtained by a more extensive and more accurate _knowledge_ of them; and which alone can enable us to avail ourselves of the numerous advantages with which we are surrounded, and contribute to make our common situation more secure and happy. Besides, the man who believes that there is a _governor_ as well as a _maker_ of the world (and there is certainly equal reason to believe both) will acknowledge his providence and favour at least as much in a successful pursuit of _knowledge_, as of _wealth_; which is a sentiment that entirely cuts off all boasting with respect to ourselves, and all envy and jealousy with respect to others; and disposes us mutually to rejoice in every new light that we receive, through whose hands soever it be conveyed to us. I shall pass for an enthusiast with some, but I am perfectly easy under the imputation, because I am happy in those views which subject me to it; but considering the amazing improvements in natural knowledge which have been made within the last century, and the many ages, abounding with men who had no other object but study, in which, however, nothing of this kind was done, there appears to me to be a very particular providence in the concurrence of those circumstances which have produced so great a change; and I cannot help flattering myself that this will be instrumental in bringing about other changes in the state of the world, of much more consequence to the improvement and happiness of it. This rapid progress of knowledge, which, like the progress of a _wave_ of the sea, of _sound_, or of _light_ from the sun, extends itself not this way or that way only, but _in all directions_, will, I doubt not, be the means, under God, of extirpating _all_ error and prejudice, and of putting an end to all undue and usurped authority in the business of _religion_, as well as of _science_; and all the efforts of the interested friends of corrupt establishments of all kinds will be ineffectual for their support in this enlightened age: though, by retarding their downfal, they may make the final ruin of them more complete and glorious. It was ill policy in Leo the Xth to patronize polite literature. He was cherishing an enemy in disguise. And the English hierarchy (if there be any thing unsound in its constitution) has equal reason to tremble even at an air-pump, or an electrical machine. There certainly never was any period in which _natural knowledge_ made such a progress as it has done of late years, and especially in this country; and they who affect to speak with supercilious contempt of the publications of the present age in general, or of the Royal Society in particular, are only those who are themselves engaged in the most trifling of all literary pursuits, who are unacquainted with all real science, and are ignorant of the progress and present state of it.[1] It is true that the rich and the great in this country give less attention to these subjects than, I believe, they were ever known to do, since the time of Lord Bacon, and much less than men of rank and fortune in other countries give to them. But with us this loss is made up by men of leisure, spirit, and ingenuity, in the middle ranks of life, which is a circumstance that promises better for the continuance of this progress in useful knowledge than any noble or royal patronage. With us, politics chiefly engage the attention of those who stand foremost in the community, which, indeed, arises from the _freedom_ and peculiar _excellence_ of our constitution, without which even the spirit of men of letters in general, and of philosophers in particular, who never directly interfere in matters of government, would languish. It is rather to be regretted, however, that, in such a number of nobility and gentry, so very few should have any taste for scientifical pursuits, because, for many valuable purposes of science, _wealth_ gives a decisive advantage. If extensive and lasting _fame_ be at all an object, literary, and especially scientifical pursuits, are preferable to political ones in a variety of respects. The former are as much more favourable for the display of the human faculties than the latter, as the _system of nature_ is superior to any _political system_ upon earth. If extensive _usefulness_ be the object, science has the same advantage over politics. The greatest success in the latter seldom extends farther than one particular country, and one particular age; whereas a successful pursuit of science makes a man the benefactor of all mankind, and of every age. How trifling is the fame of any statesman that this country has ever produced to that of Lord Bacon, of Newton, or of Boyle; and how much greater are our obligations to such men as these, than to any other in the whole _Biographia Britannica_; and every country, in which science has flourished, can furnish instances for similar observations. Here my reader will thank me, and the writer will, I hope, forgive me, if I quote a passage from the postscript of a letter which I happen to have just received from that excellent, and in my opinion, not too enthusiastical philosopher, father Beccaria of Turin. _Mi spiace che il mondo politico ch'è pur tanto passeggero, rubbi il grande Franklin al mondo della natura, che non sa ne cambiare, ne mancare._ In English. "I am sorry that the _political world_, which is so very transitory, should take the great Franklin from the _world of nature_, which can never change, or fail." I own it is with peculiar pleasure that I quote this passage, respecting this truly great man, at a time when some of the infatuated politicians of this country are vainly thinking to build their wretched and destructive projects, on the ruins of his established reputation; a reputation as extensive as the spread of science itself, and of which it is saying very little indeed, to pronounce that it will last and flourish when the names of all his enemies shall be forgotten. I think it proper, upon this occasion, to inform my friends, and the public, that I have, for the present, suspended my design of writing _the history and present state of all the branches of experimental philosophy_. This has arisen not from any dislike of the undertaking, but, in truth, because I see no prospect of being reasonably indemnified for so much labour and expence, notwithstanding the specimens I have already given of that work (in the _history of electricity_, and of the _discoveries relating to vision, light, and colours_) have met with a much more favourable reception from the best judges both at home and abroad, than I expected. Immortality, if I should have any view to it, is not the proper price of such works as these. I propose, however, having given so much attention to the subject of _air_, to write, at my leisure, the history and present state of discoveries relating to it; in which case I shall, as a part of it, reprint this work, with such improvements as shall have occurred to me at that time; and I give this notice of it, that no person who intends to purchase it may have reason (being thus apprised of my intention) to complain of buying the same thing twice. If any person chuse it, he may save his five or six shillings for the present, and wait five or six years longer (if I should live so long) for the opportunity of buying the same thing, probably much enlarged, and at the same time a complete account of all that has been done by others relating to this subject. Though for the plain, and I hope satisfactory reason above mentioned, I shall probably write no other _histories_ of this kind, I shall, as opportunity serves, endeavour to provide _materials_ for such histories, by continuing my experiments, keeping my eyes open to such new appearances as may present themselves, investigating them as far as I shall be able, and never failing to communicate to the public, by some channel or other, the result of my observations. In the publication of this work I have thought that it would be agreeable to my readers to preserve, in some measure, the order of history, and therefore I have not thrown together all that I have observed with respect to each kind of air, but have divided the work into _two parts_; the former containing what was published before, in the Philosophical Transactions, with such observations and corrections as subsequent experience has suggested to me; and I have reserved for the latter part of the work an account of the experiments which I have made since that publication, and after a pretty long interruption in my philosophical pursuits, in the course of the last summer. Besides I am sensible that in the latter part of this work a different arrangement of the subjects will be more convenient, for their mutual illustration. Some persons object to the term _air_, as applied to _acid_, _alkaline_, and even _nitrous air_; but it is certainly very convenient to have a common term by which to denote things which have so many common properties, and those so very striking; all of them agreeing with the air in which we breathe, and with _fixed air_, in _elasticity_, and _transparency_, and in being alike affected by heat or cold; so that to the eye they appear to have no difference at all. With much more reason, as it appears to me, might a person object to the common term _metal_, as applied to things so very different from one another as gold, quicksilver, and lead. Besides, _acid_ and _alkaline_ air do not differ from _common air_ (in any respect that can countenance an objection to their having a common appellation) except in such properties as are common to it with _fixed air_, though in a different degree; viz. that of being imbibed by water. But, indeed, all kinds of air, common air itself not excepted, are capable of being imbibed by water in some degree. Some may think the terms acid and alkaline _vapour_ more proper than acid and alkaline _air_. But the term _vapour_ having always been applied to elastic matters capable of being condensed in the temperature of the atmosphere, especially the vapour of water, it seems harsh to apply it to any elastic substance, which at the same time that it is as transparent as the air we breathe, is no more affected by cold than it is. As my former papers were immediately translated into several foreign languages, I may presume that this treatise, having a better title to it, will be translated also; and, upon this presumption, I cannot help expressing a wish, that it may be done by persons who have a competent knowledge of _subject_, as well as of the _English language_. The mistakes made by some foreigners, have induced me to give this caution. _London, Feb._ _1774._ ADVERTISEMENT. The _weights_ mentioned in the course of this treatise are _Troy_, and what is called _an ounce measure of air_, is the space occupied by an ounce weight of water, which is equal to 480 grains, and is, therefore, almost two _cubic inches_ of water; for one cubic inch weighs 254 grains. FOOTNOTES: [1] See Sir John Pringle's _Discourse on the different kinds of air_, p. 29, which, if it became me to do it, I would recommend to the reader, as containing a just and elegant account of the several discoveries that have been successively made, relating to the subject of this treatise. THE CONTENTS. THE INTRODUCTION. Section I. _A general view of PRECEDING DISCOVERIES relating to AIR_ Page 1 Sect. II. _An Account of the APPARATUS with which the following Experiments were made_ 6 PART I. _Experiments and Observations made in, and before the Year 1772._ 23 Sect. I. _Of FIXED AIR_ 25 Sect. II. _Of AIR in which a CANDLE, or BRIMSTONE, has burned out_ 43 Sect. III. _Of INFLAMMABLE AIR_ 55 Sect. IV. _Of AIR infected with ANIMAL RESPIRATION, or PUTREFACTION_ 70 Sect. V. _Of AIR in which a mixture of BRIMSTONE and FILINGS of IRON has stood_ 105 Sect. VI. _Of NITROUS AIR_ 108 Sect. VII. _Of AIR infected with the FUMES of BURNING CHARCOAL_ 129 Sect. VIII. _Of the effect of the CALCINATION of METALS, and of the EFFLUVIA of PAINT made with WHITE-LEAD and OIL, on AIR_ 133 Sect. IX. _Of MARINE ACID AIR_ 143 Sect. X. _Miscellaneous Observations_ 154 PART II. _Experiments and Observations made in the Year 1773, and the Beginning of 1774._ Sect. I. _Observations on ALKALINE AIR_ 163 Sect. II. _Of COMMON AIR diminished, and made noxious by various processes_ 177 Sect. III. _Of NITROUS AIR_ 203 Sect. IV. _Of MARINE ACID AIR_ 229 Sect. V. _Of INFLAMMABLE AIR_ 242 Sect. VI. _Of FIXED AIR_ 248 Sect. VII. MISCELLANEOUS EXPERIMENTS 252 Sect. VIII. _QUERIES, SPECULATIONS, and HINTS_ 258 THE APPENDIX. Number I. _EXPERIMENTS made by Mr. Hey to prove that there is no OIL of VITRIOL in water impregnated with FIXED AIR_ 288 Number II. _A Letter from Mr. HEY to Dr. PRIESTLEY, concerning the effects of fixed Air applied by way of Clyster_ 292 Number III. _Observations on the MEDICINAL USES of FIXED AIR. By THOMAS PERCIVAL, M. D. Fellow of the ROYAL SOCIETY, and of the SOCIETY of ANTIQUARIES in LONDON_ 300 Number IV. _Extract of a Letter from WILLIAM FALCONER, M. D. of BATH_ 314 Number V. _Extract of a Letter from Mr. WILLIAM BEWLEY, of GREAT MASSINGHAM, NORFOLK_ 317 Num. VI. _A Letter from Dr. FRANKLIN_ 321 Number VII. _Extract of Letter from Mr. HENRY of MANCHESTER_ 323 THE INTRODUCTION. SECTION I. _A general view of PRECEDING DISCOVERIES relating to air._ For the better understanding of the experiments and observations on different kinds of air contained in this treatise, it will be useful to those who are not acquainted with the history of this branch of natural philosophy, to be informed of those facts which had been discovered by others, before I turned my thoughts to the subject; which suggested, and by the help of which I was enabled to pursue, my inquiries. Let it be observed, however, that I do not profess to recite in this place _all_ that had been discovered concerning air, but only those discoveries the knowledge of which is necessary, in order to understand what I have done myself; so that any person who is only acquainted with the general principles of natural philosophy, may be able to read this treatise, and, with proper attention, to understand every part of it. That the air which constitutes the atmosphere in which we live has _weight_, and that it is _elastic_, or consists of a compressible and dilatable fluid, were some of the earliest discoveries that were made after the dawning of philosophy in this western part of the world. That elastic fluids, differing essentially from the air of the atmosphere, but agreeing with it in the properties of weight, elasticity, and transparency, might be generated from solid substances, was discovered by Mr. Boyle, though two remarkable kinds of factitious air, at least the effects of them, had been known long before to all miners. One of these is heavier than common air. It lies at the bottom of pits, extinguishes candles, and kills animals that breathe it, on which account it had obtained the name of the _choke damp_. The other is lighter than common air, taking its place near the roofs of subterraneous places, and because it is liable to take fire, and explode, like gunpowder, it had been called the _fire damp_. The word _damp_ signifies _vapour_ or _exhalation_ in the German and Saxon language. Though the former of these kinds of air had been known to be noxious, the latter I believe had not been discovered to be so, having always been found in its natural state, so much diluted with common air, as to be breathed with safety. Air of the former kind, besides having been discovered in various caverns, particularly the _grotta del Cane_ in Italy, had also been observed on the surface of fermenting liquors, and had been called _gas_ (which is the same with _geist_, or _spirit_) by Van Helmont, and other German chymists; but afterwards it obtained the name of _fixed air_, especially after it had been discovered by Dr. Black of Edinburgh to exist, in a fixed state, in alkaline salts, chalk, and other calcareous substances. This excellent philosopher discovered that it is the presence of the fixed air in these substances that renders them _mild_, and that when they are deprived of it, by the force of fire, or any other process, they are in that state which had been called _caustic_, from their corroding or burning animal and vegetable substances. Fixed air had been discovered by Dr. Macbride of Dublin, after an observation of Sir John Pringle's, which led to it, to be in a considerable degree antiseptic; and since it is extracted in great plenty from fermenting vegetables, he had recommended the use of _wort_ (that is an infusion of malt in water) as what would probably give relief in the sea-scurvy, which is said to be a putrid disease. Dr. Brownrigg had also discovered that the same species of air is contained in great quantities in the water of the Pyrmont spring at Spa in Germany, and in other mineral waters, which have what is called an _acidulous_ taste, and that their peculiar flavour, briskness, and medicinal virtues, are derived from this ingredient. Dr. Hales, without seeming to imagine that there was any material difference between these kinds of air and common air, observed that certain substances and operations _generate_ air, and others _absorb_ it; imagining that the diminution of air was simply a taking away from the common mass, without any alteration in the properties of what remained. His experiments, however, are so numerous, and various, that they are justly esteemed to be the solid foundation of all our knowledge of this subject. Mr. Cavendish had exactly ascertained the specific gravities of fixed and inflammable air, shewing the former of them to be 1-1/2 heavier than common air, and the latter ten times lighter. He also shewed that water would imbibe more than its own bulk of fixed air. Lastly, Mr. Lane discovered that water thus impregnated with fixed air will dissolve a considerable quantity of iron, and thereby become a strong chalybeate. These, I would observe, are by no means all the discoveries concerning air that have been made by the gentlemen whose names I have mentioned, and still less are they all that have been made by others; but they comprise all the previous knowledge of this subject that is necessary to the understanding of this treatise; except a few particulars, which will be mentioned in the course of the work, and which it is, therefore, unnecessary to recite in this place. SECTION II. _An account of the APPARATUS with which the following experiments were made._ Rather than describe at large the manner in which every particular experiment that I shall have occasion to recite was made, which would both be very tedious, and require an unnecessary multiplicity of drawings, I think it more adviseable to give, at one view, an account of all my apparatus and instruments, or at least of every thing that can require a description, and of all the different operations and processes in which I employ them. It will be seen that my apparatus for experiments on air is, in fact, nothing more than the apparatus of Dr. Hales, Dr. Brownrigg, and Mr. Cavendish, diversified, and made a little more simple. Yet notwithstanding the simplicity of this apparatus, and the ease with which all the operations are conducted, I would not have any person, who is altogether without experience, to imagine that he shall be able to select any of the following experiments, and immediately perform it, without difficulty or blundering. It is known to all persons who are conversant in experimental philosophy, that there are many little attentions and precautions necessary to be observed in the conducting of experiments, which cannot well be described in words, but which it is needless to describe, since practice will necessarily suggest them; though, like all other arts in which the hands and fingers are made use of, it is only _much practice_ that can enable a person to go through complex experiments, of this or any other kind, with ease and readiness. For experiments in which air will bear to be confined by water, I first used an oblong trough made of earthen ware, as _a_ fig. 1. about eight inches deep, at one end of which I put thin flat stones, _b. b._ about an inch, or half an inch, under the water, using more or fewer of them according to the quantity of water in the trough. But I have since found it more convenient to use a larger wooden trough, of the same general shape, eleven inches deep, two feet long, and 1-1/2 wide, with a shelf about an inch lower than the top, instead of the flat stones above-mentioned. This trough being larger than the former, I have no occasion to make provision for the water being higher or lower, the bulk of a jar or two not making so great a difference as did before. The several kinds of air I usually keep in _cylindrical jars_, as _c_, _c_, fig. 1, about ten inches long, and 2-1/2 wide, being such as I have generally used for electrical batteries, but I have likewise vessels of very different forms and sizes, adapted to particular experiments. When I want to remove vessels of air from the large trough, I place them in _pots_ or _dishes_, of various sizes, to hold more or less water, according to the time that I have occasion to keep the air, as fig. 2. These I plunge in water, and slide the jars into them; after which they may be taken out together, and be set wherever it shall be most convenient. For the purpose of merely removing a jar of air from one place to another, where it is not to stand longer than a few days, I make use of common _tea-dishes_, which will hold water enough for that time, unless the air be in a state of diminution, by means of any process that is going on in it. If I want to try whether an animal will live in any kind of air, I first put the air into a small vessel, just large enough to give it room to stretch itself; and as I generally make use of _mice_ for this purpose, I have found it very convenient to use the hollow part of a tall beer-glass, _d_ fig. 1, which contains between two and three ounce measures of air. In this vessel a mouse will live twenty minutes, or half an hour. For the purpose of these experiments it is most convenient to catch the mice in small wire traps, out of which it is easy to take them, and holding them by the back of the neck, to pass them through the water into the vessel which contains the air. If I expect that the mouse will live a considerable time, I take care to put into the vessel something on which it may conveniently sit, out of the reach of the water. If the air be good, the mouse will soon be perfectly at its ease, having suffered nothing by its passing through the water. If the air be supposed to be noxious, it will be proper (if the operator be desirous of preserving the mice for farther use) to keep hold of their tails, that they may be withdrawn as soon as they begin to shew signs of uneasiness; but if the air be thoroughly noxious, and the mouse happens to get a full inspiration, it will be impossible to do this before it be absolutely irrecoverable. In order to _keep_ the mice, I put them into receivers open at the top and bottom, standing upon plates of tin perforated with many holes, and covered with other plates of the same kind, held down by sufficient weights, as fig. 3. These receivers stand upon _a frame of wood_, that the fresh air may have an opportunity of getting to the bottoms of them, and circulating through them. In the inside I put a quantity of paper or tow, which must be changed, and the vessel washed and dried, every two or three days. This is most conveniently done by having another receiver, ready cleaned and prepared, into which the mice may be transferred till the other shall be cleaned. Mice must be kept in a pretty exact temperature, for either much heat or much cold kills them presently. The place in which I have generally kept them is a shelf over the kitchen fire-place where, as it is usual in Yorkshire, the fire never goes out; so that the heat varies very little, and I find it to be, at a medium, about 70 degrees of Fahrenheit's thermometer. When they had been made to pass through the water, as they necessarily must be in order to a change of air, they require, and will bear a very considerable degree of heat, to warm and dry them. I found, to my great surprize, in the course of these experiments, that mice will live intirely without water; for though I have kept them for three or four months, and have offered them water several times, they would never taste it; and yet they continued in perfect health and vigour. Two or three of them will live very peaceably together in the same vessel; though I had one instance of a mouse tearing another almost in pieces, and when there was plenty of provisions for both of them. In the same manner in which a mouse is put into a vessel of any kind of air, a _plant_, or any thing else, may be put into it, viz. by passing it through the water; and if the plant be of a kind that will grow in water only, there will be no occasion to set it in a pot of earth, which will otherwise be necessary. There may appear, at first sight, some difficulty in opening the mouth of a phial, containing any substance, solid or liquid, to which water must not be admitted, in a jar of any kind of air, which is an operation that I have sometimes had recourse to; but this I easily effect by means of _a cork cut tapering_, and a strong, wire thrust through it, as in fig. 4, for in this form it will sufficiently fit the mouth of any phial, and by holding the phial in one hand, and the wire in the other, and plunging both my hands into the trough of water, I can easily convey the phial through the water into the jar; which must either be held by an assistant, or be fastened by strings, with its mouth projecting over the shelf. When the phial is thus conveyed into the jar, the cork may easily be removed, and may also be put into it again at pleasure, and conveyed the same way out again. When any thing, as a gallipot, &c. is to be supported at a considerable height within a jar, it is convenient to have such _wire stands_ as are represented fig. 5. They answer better than any other, because they take up but little room, and may be easily bended to any shape or height. If I have occasion to pour air from a vessel with a wide mouth into another with a very narrow one, I am obliged to make use of a funnel, fig. 6, but by this means the operation is exceedingly easy; first filling the vessel into which the air is to be conveyed with water, and holding the mouth of it, together with the funnel, both under water with one hand, while the other is employed in pouring the air; which, ascending through the funnel up into the vessel, makes the water descend, and takes its place. These funnels are best made of glass, because the air being visible through them, the quantity of it may be more easily estimated by the eye. It will be convenient to have several of these funnels of different sizes. In order to expel air from solid substances by means of heat, I sometimes put them into a _gun-barrel_, fig. 7, and filling it up with dry sand, that has been well burned, so that no air can come from it, I lute to the open end the stem of a tobacco pipe, or a small glass tube. Then having put the closed end of the barrel, which contains the materials, into the fire, the generated air, issuing through the tube, may be received in a vessel of quicksilver, with its mouth immersed in a bason of the same, suspended all together in wires, in the manner described in the figure: or any other fluid substance may be used instead of quicksilver. But the most accurate method of procuring air from several substances, by means of heat, is to put them, if they will bear it, into phials full of quicksilver, with the mouths immersed in the same, and then throw the focus of a burning mirror upon them. For this purpose the phials should be made with their bottoms round, and very thin, that they may not be liable to break with a pretty sudden application of heat. If I want to expel air from any liquid, I nearly fill a phial with it, and having a cork perforated, I put through it, and secure with cement, a glass tube, bended in the manner represented at _e_ fig. 1. I then put the phial into a kettle of water, which I set upon the fire and make to boil. The air expelled by the heat, from the liquor contained in the phial, issues through the tube, and is received in the bason of quicksilver, fig. 7. Instead of this suspended bason, I sometimes content myself with tying a flaccid bladder to the end of the tube, in both these processes, that it may receive the newly generated air. In experiments on those kinds of air which are readily imbibed by water, I always make use of quicksilver, in the manner represented fig. 8, in which _a_ is the bason of quicksilver, _b_ a glass vessel containing quicksilver, with its mouth immersed in it, _c_ a phial containing the ingredients from which the air is to be produced; and _d_ is a small recipient, or glass vessel designed to receive and intercept any liquor that may be discharged along with the air, which is to be transmitted free from any moisture into the vessel _b_. If there be no apprehension of moisture, I make use of the glass tube only, without any recipient, in the manner represented _e_ fig. 1. In order to invert the vessel _b_, I first fill it with quicksilver, and then carefully cover the mouth of it with a piece of soft leather; after which it may be turned upside down without any danger of admitting the air, and the leather may be withdrawn when it is plunged in the quicksilver. In order to generate air by the solution of metals, or any process of a similar nature, I put the materials into a phial, prepared in the manner represented at _e_ fig. 1, and put the end of the glass tube under the mouth of any vessel into which I want to convey the air. If heat be necessary I can easily apply to it a candle, or a red hot poker while it hangs in this position. When I have occasion to transfer air from a jar standing in the trough of water to a vessel standing in quicksilver, or in any other situation whatever, I make use of the contrivance represented fig. 9, which consists of a bladder, furnished at one end with a small glass tube bended, and at the other with a cork, perforated so as just to admit the small end of a funnel. When the common air is carefully pressed out of this bladder, and the funnel is thrust tightly into the cork, it may be filled with any kind of air as easily as a glass jar; and then a string being tied above the cork in which the funnel is inserted, and the orifice in the other cork closed, by pressing the bladder against it, it may be carried to any place, and if the tube be carefully wiped, the air may be conveyed quite free from moisture through a body of quicksilver, or any thing else. A little practice will make this very useful manoeuvre perfectly easy and accurate. In order to impregnate fluids with any kind of air, as water with fixed air, I fill a phial with the fluid larger or less as I have occasion (as _a_ fig. 10;) and then inverting it, place it with its mouth downwards, in a bowl _b_, containing a quantity of the same fluid; and having filled the bladder, fig. 9, with the air, I throw as much of it as I think proper into the phial, in the manner described above. To accelerate the impregnation, I lay my hand on the top of the phial, and shake it as much as I think proper. If, without having any air previously generated, I would convey it into the fluid immediately as it arises from the proper materials, I keep the same bladder in connection with a phial _c_ fig. 10, containing the same materials (as chalk, salt of tartar, or pearl ashes in diluted oil of vitriol, for the generation of fixed air) and taking care, lest, in the act of effervescence, any of the materials in the phial _c_ should get into the vessel _a_, to place this phial on a stand lower than that on which the bason was placed, I press out the newly generated air, and make it ascend directly into the fluid. For this purpose, and that I may more conveniently shake the phial _c_, which is necessary in some processes, especially with chalk and oil of vitriol, I sometimes make use of a flexible leathern tube _d_, and sometimes only a glass tube. For if the bladder be of a sufficient length, it will give room for the agitation of the phial; or if not, it is easy to connect two bladders together by means of a perforated cork, to which they may both be fastened. When I want to try whether any kind of air will admit a candle to burn in it, I make use of a cylindrical glass vessel, fig. 11. and a bit of wax candle _a_ fig. 12, fastened to the end of a wire _b_, and turned up, in such a manner as to be let down into the vessel with the flame upwards. The vessel should be kept carefully covered till the moment that the candle is admitted. In this manner I have frequently extinguished a candle more than twenty times successively, in a vessel of this kind, though it is impossible to dip the candle into it without giving the external air an opportunity of mixing with the air in the inside more or less. The candle _c_, at the other end of the wire is very convenient for holding under a jar standing in water, in order to burn as long as the inclosed air can supply it; for the moment that it is extinguished, it may be drawn through the water before any smoke can have mixed with the air. In order to draw air out of a vessel which has its mouth immersed in water, and thereby to raise the water to whatever height may be necessary, it is very convenient to make use of a glass _syphon_, fig. 13, putting one of the legs up into the vessel, and drawing the air out at the other end by the mouth. If the air be of a noxious quality, it may be necessary to have a syringe fastened to the syphon, the manner of which needs no explanation. I have not thought it safe to depend upon a valve at the top of the vessel, which Dr. Hales sometimes made use of. If, however, a very small hole be made at the top of a glass vessel, it may be filled to any height by holding it under water, while the air is issuing out at the hole, which may then be closed with wax or cement. If the generated air will neither be absorbed by water, nor diminish common air, it may be convenient to put part of the materials into a cup, supported by a stand, and the other part into a small glass vessel, placed on the edge of it, as at _f_, fig. 1. Then having, by means of a syphon, drawn the air to at convenient height, the small glass vessel may be easily pushed into the cup, by a wire introduced through the water; or it may be contrived, in a variety of ways, only to discharge the contents of the small vessel into the larger. The distance between the boundary of air and water, before and after the operation, will shew the quantity of the generated air. The effect of processes that _diminish_ air may also be tried by the same apparatus. When I want to admit a particular kind of air to any thing that will not bear wetting, and yet cannot be conveniently put into a phial, and especially if it be in the form of a powder, and must be placed upon a stand (as in those experiments in which the focus of a burning mirror is to be thrown upon it) I first exhaust a receiver, in which it is previously placed; and having a glass tube, bended for the purpose, as in fig. 14, I screw it to the stem of a transfer of the air pump on which the receiver had been exhausted, and introducing it through the water into a jar of that kind of air with which I would fill the receiver, I only turn the cock, and I gain my purpose. In this method, however, unless the pump be very good, and several contrivances, too minute to be particularly described, be made use of a good deal of common air will get into the receiver. When I want to measure the goodness of any kind of air, I put two measures of it into a jar standing in water; and when I have marked upon the glass the exact place of the boundary of air and water, I put to it one measure of nitrous air; and after waiting a proper time, note the quantity of its diminution. If I be comparing two kinds of air that are nearly alike, after mixing them in a large jar, I transfer the mixture into a long glass tube, by which I can lengthen my scale to what degree I please. If the quantity of the air, the goodness of which I want to ascertain, be exceedingly small, so as to be contained in a part of a glass tube, out of which water will not run spontaneously, as _a_ fig. 15; I first measure with a pair of compasses the length of the column of air in the tube, the remaining part being filled with water, and lay it down upon a scale; and then, thrusting a wire of a proper thickness, _b_, into the tube, I contrive, by means of a thin plate of iron, bent to a sharp angle _c_, to draw it out again, when the whole of this little apparatus has been introduced through the water into a jar of nitrous air; and the wire being drawn out, the air from the jar must supply its place. I then measure the length of this column of nitrous air which I have got into the tube, and lay it also down upon the scale, so as to know the exact length of both the columns. After this, holding the tube under water, with a small wire I force the two separate columns of air into contact, and when they have been a sufficient time together, I measure the length of the whole, and compare it with the length of both the columns taken before. A little experience will teach the operator how far to thrust the wire into the tube, in order to admit as much air as he wants and no more. In order to take the electric spark in a quantity of any kind of air, which must be very small, to produce a sensible effect upon it, in a short time, by means of a common machine, I put a piece of wire into the end of a small tube, and fasten it with hot cement, as in fig. 16; and having got the air I want into the tube by means of the apparatus fig. 15, I place it inverted in a bason containing either quicksilver, or any other fluid substance by which I chuse to have the air confined. I then, by the help of the air pump, drive out as much of the air as I think convenient, admitting the quicksilver, &c. to it, as at _a_, and putting a brass ball on the end of the wire, I take the sparks or shocks upon it, and thereby transmit them through the air to the liquor in the tube. To take the electric sparks in any kind of fluid, as oil, &c. I use the same apparatus described above, and having poured into the tube as much of the fluid as I conjecture I can make the electric spark pass through, I fill the rest with quicksilver; and placing it inverted in a bason of quicksilver, I take the sparks as before. If air be generated very fast by this process, I use a tube that is narrow at the top, and grows wider below, as fig. 17, that the quicksilver may not recede too soon beyond the striking distance. Sometimes I have used a different apparatus for this purpose, represented fig. 18. Taking a pretty wide glass tube, hermetically sealed at the upper-end, and open below, at about an inch, or at what distance I think convenient from the top, I get two holes made in it, opposite to each other. Through these I put two wires, and fastening them with warm cement, I fix them at what distance I please from each other. Between these wires I take the sparks, and the bubbles of air rise, as they are formed, to the top of the tube. PART I. _Experiments and Observations made in, and before the year 1772._ In writing upon the subject of _different kinds of air_, I find myself at a loss for proper _terms_, by which to distinguish them, those which have hitherto obtained being by no means sufficiently characteristic, or distinct. The only terms in common use are, _fixed air_, _mephitic_, and _inflammable_. The last, indeed, sufficiently characterizes and distinguishes that kind of air which takes fire, and explodes on the approach of flame; but it might have been termed _fixed_ with as much propriety as that to which Dr. Black and others have given that denomination, since it is originally part of some solid substance, and exists in an unelastic state. All these newly discovered kinds of air may also be called _factitious_; and if, with others, we use the term _fixable_, it is still obvious to remark, that it is applicable to them all; since they are all capable of being imbibed by some substance or other, and consequently of being _fixed_ in them, after they have been in an elastic state. The term _mephitic_ is equally applicable to what is called _fixed air_, to that which is _inflammable_, and to many other kinds; since they are equally noxious, when breathed by animals. Rather, however, than either introduce new terms, or change the signification of old ones, I shall use the term _fixed air_, in the sense in which it is now commonly used, and distinguish the other kinds by their properties, or some other periphrasis. I shall be under a necessity, however, of giving names to those kinds of air, to which no names had been given by others, as _nitrous_, _acid_, and _alkaline_. SECTION I. _Of FIXED AIR._ It was in consequence of living for some time in the neighbourhood of a public brewery, that I was induced to make experiments on fixed air, of which there is always a large body, ready formed, upon the surface of the fermenting liquor, generally about nine inches, or a foot in depth, within which any kind of substance may be very conveniently placed; and though, in these circumstances, the fixed air must be continually mixing with the common air, and is therefore far from being perfectly pure, yet there is a constant fresh supply from the fermenting liquor, and it is pure enough for many purposes. A person, who is quite a stranger to the properties of this kind of air, would be agreeably amused with extinguishing lighted candles, or chips of wood in it, as it lies upon the surface of the fermenting liquor; for the smoke readily unites with this kind of air, probably by means of the water which it contains; so that very little or none of the smoke will escape into the open air, which is incumbent upon it. It is remarkable, that the upper surface of this smoke, floating in the fixed air, is smooth, and well defined; whereas the lower surface is exceedingly ragged, several parts hanging down to a considerable distance within the body of the fixed air, and sometimes in the form of balls, connected to the upper stratum by slender threads, as if they were suspended. The smoke is also apt to form itself into broad flakes, parallel to the surface of the liquor, and at different distances from it, exactly like clouds. These appearances will sometimes continue above an hour, with very little variation. When this fixed air is very strong, the smoke of a small quantity of gunpowder fired in it will be wholly retained by it, no part escaping into the common air. Making an agitation in this air, the surface of it, (which still continues to be exactly defined) is thrown into the form of waves, which it is very amusing to look upon; and if, by this agitation, any of the fixed air be thrown over the side of the vessel, the smoke, which is mixed with it, will fall to the ground, as if it was so much water, the fixed air being heavier than common air. The red part of burning wood was extinguished in this air, but I could not perceive that a red-hot poker was sooner cooled in it. Fixed air does not instantly mix with common air. Indeed if it did, it could not be caught upon the surface of the fermenting liquor. A candle put under a large receiver, and immediately plunged very deep below the surface of the fixed air, will burn some time. But vessels with the smallest orifices, hanging with their mouths downwards in the fixed air, will _in time_ have the common air, which they contain, perfectly mixed with it. When the fermenting liquor is contained in vessels close covered up, the fixed air, on removing the cover, readily affects the common air which is contiguous to it; so that, candles held at a considerable distance above the surface will instantly go out. I have been told by the workmen, that this will sometimes be the case, when the candles are held two feet above the mouth of the vessel. Fixed air unites with the smoke of rosin, sulphur, and other electrical substances, as well as with the vapour of water; and yet, by holding the wire of a charged phial among these fumes, I could not make any electrical atmosphere, which surprized me a good deal, as there was a large body of this smoke, and it was so confined, that it could not escape me. I also held some oil of vitriol in a glass vessel within the fixed air, and by plunging a piece of red-hot glass into it, raised a copious and thick fume. This floated upon the surface of the fixed air like other fumes, and continued as long. Considering the near affinity between water and fixed air, I concluded that if a quantity of water was placed near the yeast of the fermenting liquor, it could not fail to imbibe that air, and thereby acquire the principal properties of Pyrmont, and some other medicinal mineral waters. Accordingly, I found, that when the surface of the water was considerable, it always acquired the pleasant acidulous taste that Pyrmont water has. The readiest way of impregnating water with this virtue, in these circumstances, is to take two vessels, and to keep pouring the water from one into the other, when they are both of them held as near the yeast as possible; for by this means a great quantity of surface is exposed to the air, and the surface is also continually changing. In this manner, I have sometimes, in the space of two or three minutes, made a glass of exceedingly pleasant sparkling water, which could hardly be distinguished from very good Pyrmont, or rather Seltzer water. But the _most effectual_ way of impregnating water with fixed air is to put the vessels which contain the water into glass jars, filled with the purest fixed air made by the solution of chalk in diluted oil of vitriol, standing in quicksilver. In this manner I have, in about two days, made a quantity of water to imbibe more than an equal bulk of fixed air, so that, according to Dr. Brownrigg's experiments, it must have been much stronger than the best imported Pyrmont; for though he made his experiments at the spring-head, he never found that it contained quite so much as half its bulk of this air. If a sufficient quantity of quicksilver cannot be procured, _oil_ may be used with sufficient advantage, for this purpose, as it imbibes the fixed air very slowly. Fixed air may be kept in vessels standing in water for a long time, if they be separated by a partition of oil, about half an inch thick. Pyrmont water made in these circumstances, is little or nothing inferior to that which has stood in quicksilver. The _readiest_ method of preparing this water for use is to agitate it strongly with a large surface exposed to the fixed air. By this means more than an equal bulk of air may be communicated to a large quantity of water in the space of a few minutes. But since agitation promotes the dissipation of fixed air from water, it cannot be made to imbibe so great a quantity in this method as in the former, where more time is taken. Easy directions for impregnating water with fixed air I have published in a small pamphlet, designed originally for the use of seamen in long voyages, on the presumption that it might be of use for preventing or curing the sea scurvy, equally with wort, which was recommended by Dr. Macbride for this purpose, on no other account than its property of generating fixed air, by its fermentation in the stomach. Water thus impregnated with fixed air readily dissolves iron, as Mr. Lane has discovered; so that if a quantity of iron filings be put to it, it presently becomes a strong chalybeate, and of the mildest and most agreeable kind. I have recommended the use of _chalk_ and oil of vitriol as the cheapest, and, upon the whole, the best materials for this purpose. But some persons prefer _pearl ashes_, _pounded marble_, or other calcareous or _alkaline substances_; and perhaps with reason. My own experience has not been sufficient to enable me to decide in this case. Whereas some persons had suspected that a quantity of the oil of vitriol was rendered volatile by this process, I examined it, by all the chemical methods that are in use; but could not find that water thus impregnated contained the least perceivable quantity of that acid. Mr. Hey, indeed, who assisted me in this examination, found that distilled water, impregnated with fixed air, did not mix so readily with soap as the distilled water itself; but this was also the case when the fixed air had passed through a long glass tube filled with alkaline salts, which, it may be supposed, would have imbibed any of the oil of vitriol that might have been contained in that air[2]. Fixed air itself may be said to be of the nature of an acid, though of a weak and peculiar sort.----Mr. Bergman of Upsal, who honoured me with a letter upon the subject, calls it the _aërial acid_, and, among other experiments to prove it to be an acid, he says that it changes the blue juice of tournesole into red. This Mr. Hey found to be true, and he moreover discovered that when water tinged blue with the juice of tournesole, and then red with fixed air, has been exposed to the open air, it recovers its blue colour again. The heat of boiling water will expel all the fixed air, if a phial containing the impregnated water be held in it; but it will often require above half an hour to do it completely. Dr. Percival, who is particularly attentive to every improvement in the medical art, and who has thought so well of this impregnation as to prescribe it in several cases, informs me that it seems to be much stronger, and sparkles more, like the true Pyrmont water, after it has been kept some time. This circumstance, however, shews that, in time, the fixed air is more easily disengaged from the water; and though, in this state, it may affect the taste more sensibly, it cannot be of so much use in the stomach and bowels, as when the air is more firmly retained by the water. By the process described in my pamphlet, fixed air may be readily incorporated with wine, beer, and almost any other liquor whatever; and when beer, wine, or cyder, is become flat or dead (which is the consequence of the escape of the fixed air they contained) they may be revived by this means; but the delicate and agreeable flavour, or acidulous taste, communicated by fixed air, and which is very manifest in water, can hardly be perceived in wine, or any liquors which have much taste of their own. I should think that there can be no doubt, but that water thus impregnated with fixed air must have all the medicinal virtues of genuine Pyrmont or Seltzer water; since these depend upon the fixed air they contain. If the genuine Pyrmont water derives any advantage from its being a natural chalybeate, this may also be obtained by providing a common chalybeate water, and using it in these processes, instead of common water. Having succeeded so well with this artificial Pyrmont water, I imagined that it might be possible to give _ice_ the same virtue, especially as cold is known to promote the absorption of fixed air by water; but in this I found myself quite mistaken. I put several pieces of ice into a quantity of fixed air, confined by quicksilver, but no part of the air was absorbed in two days and two nights; but upon bringing it into a place where the ice melted, the air was absorbed as usual. I then took a quantity of strong artificial Pyrmont water, and putting it into a thin glass phial, I set it in a pot that was filled with snow and salt. This mixture instantly freezing the water that was contiguous to the sides of the glass, the air was discharged plentifully, so that I catched a considerable quantity, in a bladder tied to the mouth of the phial. I also took two quantities of the same Pyrmont water, and placed one of them where it might freeze, keeping the other in a cold place, but where it would not freeze. This retained its acidulous taste, though the phial which contained it was not corked; whereas the other being brought into the same place, where the ice melted very slowly, had at the same time the taste of common water only. That quantity of water which had been frozen by the mixture of snow and salt, was almost as much like snow as ice, such a quantity of air-bubbles were contained in it, by which it was prodigiously increased in bulk. The pressure of the atmosphere assists very considerably in keeping fixed air confined in water; for in an exhausted receiver, Pyrmont water will absolutely boil, by the copious discharge of its air. This is also the reason why beer and ale froth so much _in vacuo_. I do not doubt, therefore, but that, by the help of a condensing engine, water might be much more highly impregnated with the virtues of the Pyrmont spring; and it would not be difficult to contrive a method of doing it. The manner in which I made several experiments to ascertain the absorption of fixed air by different fluid substances, was to put the liquid into a dish, and holding it within the body of the fixed air at the brewery, to set a glass vessel into it, with its mouth inverted. This glass being necessarily filled with the fixed air, the liquor would rise into it when they were both taken into the common air, if the fixed air was absorbed at all. Making use of _ether_ in this manner, there was a constant bubbling from under the glass, occasioned by this fluid easily rising in vapour, so that I could not, in this method, determine whether it imbibed the air or not. I concluded however, that they did incorporate, from a very disagreeable circumstance, which made me desist from making any more experiments of the kind. For all the beer, over which this experiment was made, contracted a peculiar taste; the fixed air impregnated with the ether being, I suppose, again absorbed by the beer. I have also observed, that water which remained a long time within this air has sometimes acquired a very disagreeable taste. At one time it was like tar-water. How this was acquired, I was very desirous of making some experiments to ascertain, but I was discouraged by the fear of injuring the fermenting liquor. It could not come from the fixed air only. Insects and animals which breathe very little are stifled in fixed air, but are not soon quite killed in it. Butterflies and flies of other kinds will generally become torpid, and seemingly dead, after being held a few minutes over the fermenting liquor; but they revive again after being brought into the fresh air. But there are very great varieties with respect to the time in which different kinds of flies will either become torpid in the fixed air, or die in it. A large strong frog was much swelled, and seemed to be nearly dead, after being held about six minutes over the fermenting liquor; but it recovered upon being brought into the common air. A snail treated in the same manner died presently. Fixed air is presently fatal to vegetable life. At least sprigs of mint growing in water, and placed over the fermenting liquor, will often become quite dead in one day, or even in a less space of time; nor do they recover when they are afterwards brought into the common air. I am told, however, that some other plants are much more hardy in this respect. A red rose, fresh gathered, lost its redness, and became of a purple colour, after being held over the fermenting liquor about twenty-four hours; but the tips of each leaf were much more affected than the rest of it. Another red rose turned perfectly white in this situation; but various other flowers of different colours were very little affected. These experiments were not repeated, as I wish they might be done, in pure fixed air, extracted from chalk by means of oil of vitriol. For every purpose, in which it was necessary that the fixed air should be as unmixed as possible, I generally made it by pouring oil of vitriol upon chalk and water, catching it in a bladder fastened to the neck of the phial in which they were contained, taking care to press out all the common air, and also the first, and sometimes the second, produce of fixed air; and also, by agitation, making it as quickly as I possibly could. At other times, I made it pass from the phial in which it was generated through a glass tube, without the intervention of any bladder, which, as I found by experience, will not long make a sufficient separation between several kinds of air and common air. I had once thought that the readiest method of procuring fixed air, and in sufficient purity, would be by the simple process of burning chalk, or pounded lime-stone in a gun-barrel, making it pass through the stem of a tobacco-pipe, or a glass tube carefully luted to the orifice of it. In this manner I found that air is produced in great plenty; but, upon examining it, I found, to my very great surprise, that little more than one half of it was fixed air, capable of being absorbed by water; and that the rest was inflammable, sometimes very weakly, but sometimes pretty highly so. Whence this inflammability proceeds, I am not able to determine, the lime or chalk not being supposed to contain any other than fixed air. I conjecture, however, that it must proceed from the iron, and the separation of it from the calx may be promoted by that small quantity of oil of vitriol, which I am informed is contained in chalk, if not in lime-stone also. But it is an objection to this hypothesis, that the inflammable air produced in this manner burns blue, and not at all like that which is produced from iron, or any other metal, by means of an acid. It also has not the smell of that kind of inflammable air which is produced from mineral substances. Besides, oil of vitriol without water, will not dissolve iron; nor can inflammable air be got from it, unless the acid be considerably diluted; and when I mixed brimstone with the chalk, neither the quality nor the quantity of the air was changed by it. Indeed no air, or permanently elastic vapour, can be got from brimstone, or any oil. Perhaps this inflammable principle may come from some remains of the animals, from which it is thought that all calcareous matter proceeds. In the method in which I generally made the fixed air (and indeed always, unless the contrary be particularly mentioned, viz. by diluted oil of vitriol and chalk) I found by experiment that it was as pure as Mr. Cavendish made it. For after it had patted through a large body of water in small bubbles, still 1/50 or 1/60 part only was not absorbed by water. In order to try this as expeditiously as possible, I kept pouring the air from one glass vessel into another, immersed in a quantity of cold water, in which manner I found by experience, that almost any quantity may be reduced as far as possible in a very short time. But the most expeditious method of making water imbibe any kind of air, is to confine it in a jar; and agitate it strongly, in the manner described in my pamphlet on the impregnation of water with fixed air, and represented fig. 10. At the same time that I was trying the purity of my fixed air, I had the curiosity to endeavour to ascertain whether that part of it which is not miscible in water, be equally diffused through the whole mass; and, for this purpose, I divided a quantity of about a gallon into three parts, the first consisting of that which was uppermost, and the last of that which was the lowest, contiguous to the water; but all these parts were reduced in about an equal proportion, by passing through the water, so that the whole mass had been of an uniform composition. This I have also found to be the case with several kinds of air, which will, not properly incorporate. A mouse will live very well, though a candle will not burn in the residuum of the purest fixed air that I can make; and I once made a very large quantity for the sole purpose of this experiment. This, therefore, seems to be one instance of the generation of genuine common air, though vitiated in some degree. It is also another proof of the residuum of fixed air being, in part at least, common air, that it becomes turbid, and is diminished by the mixture of nitrous air, as will be explained hereafter. That fixed air only wants some addition to make it permanent, and immiscible with water if not in all respects, common air, I have been led to conclude, from several attempts which I once made to mix it with air in which a quantity of iron filings and brimstone, made into a paste with water, had stood; for, in several mixtures of this kind, I imagined that not much more than half of the fixed air could be imbibed by water; but, not being able to repeat the experiment, I conclude that I either deceived myself in it, or that I overlooked some circumstance on which the success of it depended. These experiments, however, whether they were fallacious or otherwise, induced me to try whether any alteration would be made in the constitution of fixed air, by this mixture of iron filings and brimstone. I therefore put a mixture of this kind into a quantity of as pure fixed air as I could make, and confined the whole in quicksilver, lest the water should absorb it before the effects of the mixture could take place. The consequence was, that the fixed air was diminished, and the quicksilver rose in the vessel, till about the fifth part was occupied by it; and, as near as I could judge, the process went on, in all respects, as if the air in the inside had been common air. What is most remarkable, in the result of this experiment, is, that the fixed air, into which this mixture had been put, and which had been in part diminished by it, was in part also rendered insoluble in water by this means. I made this experiment four times, with the greatest care, and observed, that in two of them about one sixth, and in the other two about one fourteenth, of the original quantity, was such as could not be absorbed by water, but continued permanently elastic. Lest I should have made any mistake with respect to the purity of the fixed air, the last time that I made the experiment, I set part of the fixed air, which I made use of, in a separate vessel, and found it to be exceedingly pure, so as to be almost wholly absorbed by water; whereas the other part, to which I had put the mixture, was far from being so. In one of these cases, in which fixed air was made immiscible with water, it appeared to be not very noxious to animals; but in another case, a mouse died in it pretty soon. This difference probably arose from my having inadvertently agitated the air in water rather more in one case than in the other. As the iron is reduced to a calx by this process, I once concluded, that it is phlogiston that fixed air wants, to make it common air; and, for any thing I yet know this may be the case, though I am ignorant of the method of combining them; and when I calcined a quantity of lead in fixed air, in the manner which will be described hereafter, it did not seem to have been less soluble in water than it was before. FOOTNOTES: [2] An account of Mr. Hey's experiments will be found in the Appendix to these papers. SECTION II. _Of AIR in which a CANDLE, or BRIMSTONE, has burned out._ It is well known that flame cannot subsist long without change of air, so that the common air is necessary to it, except in the case of substances, into the composition of which nitre enters, for these will burn _in vacuo_, in fixed air, and even under water, as is evident in some rockets, which are made for this purpose. The quantity of air which even a small flame requires to keep it burning is prodigious. It is generally said, that an ordinary candle _consumes_, as it is called, about a gallon in a minute. Considering this amazing consumption of air, by fires of all kinds, volcanos, &c. it becomes a great object of philosophical inquiry, to ascertain what change is made in the constitution of the air by flame, and to discover what provision there is in nature for remedying the injury which the atmosphere receives by this means. Some of the following experiments will, perhaps, be thought to throw light upon the subject. The diminution of the quantity of air in which a candle, or brimstone, has burned out, is various; But I imagine that, at a medium, it may be about one fifteenth, or one sixteenth of the whole; which is one third as much as by animal or vegetable substances putrefying in it, by the calcination of metals, or by any of the other causes of the complete diminution of air, which will be mentioned hereafter. I have sometimes thought, that flame disposes the common air to deposit the fixed air it contains; for if any lime-water be exposed to it, it immediately becomes turbid. This is the case, when wax candles, tallow candles, chips of wood, spirit of wine, ether, and every other substance which I have yet tried, except brimstone, is burned in a close glass vessel, standing in lime-water. This precipitation of fixed air (if this be the case) may be owing to something emitted from the burning bodies, which has a stronger affinity with the other constituent parts of the atmosphere[3]. If brimstone be burned in the same circumstances, the lime-water continues transparent, but still there may have been the same precipitation of the fixed part of the air; but that, uniting with the lime and the vitriolic acid, it forms a selenetic salt, which is soluble in water. Having evaporated a quantity of water thus impregnated, by burning brimstone a great number of times over it, a whitish powder remained, which had an acid taste; but repeating the experiment with a quicker evaporation, the powder had no acidity, but was very much like chalk. The burning of brimstone but once over a quantity of lime-water, will affect it in such a manner, that breathing into it will not make it turbid, which otherwise it always presently does. Dr. Hales supposed, that by burning brimstone repeatedly in the same quantity of air, the diminution would continue without end. But this I have frequently tried, and not found to be the case. Indeed, when the ignition has been imperfect in the first instance, a second firing of the same substance will increase the effect of the first, &c. but this progress soon ceases. In many cases of the diminution of air, the effect is not immediately apparent, even when it stands in water; for sometimes the bulk of air will not be much reduced, till it has passed several times through a quantity of water, which has thereby a better opportunity of absorbing that part of the air, which had not been perfectly detatched from the rest. I have sometimes found a very great reduction of a mass of air, in consequence of passing but once through cold water. If the air has stood in quicksilver, the diminution is generally inconsiderable, till it has undergone this operation, there not being any substance exposed to the air that could absorb any part of it. I could not find any considerable alteration in the specific gravity of the air, in which candles, or brimstone, had burned out. I am satisfied, however, that it is not heavier than common air, which must have been manifest, if so great a diminution of the quantity had been owing, as Dr. Hales and others supposed, to the elasticity of the whole mass being impaired. After making several trials for this purpose, I concluded that air, thus diminished in bulk, is rather lighter than common air, which favours the supposition of the fixed, or heavier part of the common air, having been precipitated. An animal will live nearly, if not quite as long, in air in which candles have burned out, as in common air. This fact surprized me very greatly, having imagined that what is called the _consumption_ of air by flame, or respiration, to have been of the same nature, and in the same degree; but I have since found, that this fact has been observed by many persons, and even so early as by Mr. Boyle. I have also observed, that air, in which brimstone has burned, is not in the least injurious to animals, after the fumes, which at first make it very cloudy, have intirely subsided. I must, in this place, admonish my reader not to confound the simple _burning of brimstone_, or of matches (_i. e._ bits of wood dipped in it) and the burning of brimstone with a burning mirror, or any _foreign heat_. The effect of the former is nothing more than that of any other _flame_, or _ignited vapour_, which will not burn, unless the air with which it is surrounded be in a very pure state, and which is therefore extinguished when the air begins to be much vitiated. Lighted brimstone, therefore reduces the air to the same state as lighted wood. But the focus of a burning mirror thrown for a sufficient time either upon brimstone, or wood, after it has ceased to burn of its own accord, and has become _charcoal_, will have a much greater effect: of the same kind, diminishing the air to its utmost extent, and making it thoroughly noxious. In fact, as will be seen hereafter, more phlogiston is expelled from these substances in the latter case than in the former. I never, indeed, actually carried this experiment so far with brimstone; but from the diminution of air that I did produce by this means, I concluded that, by continuing the process some time longer, it would have been effected. Having read, in the Memoirs of the Philosophical Society at Turin, vol. I. p. 41. that air in which candles had burned out was perfectly restored, so that other candles would burn in it again as well as ever, after having been exposed to a considerable degree of _cold_, and likewise after having been compressed in bladders, (for the cold had been supposed to have produced this effect by nothing but _condensation_) I repeated those experiments, and did, indeed, find, that when I compressed the air in _bladders_, as the Count de Saluce, who made the observation, had done, the experiment succeeded: but having had sufficient reason to distrust bladders, I compressed the air in a glass vessel standing in water; and then I found, that this process is altogether ineffectual for the purpose. I kept the air compressed much more, and much longer, than the Count had done, but without producing any alteration in it. I also find, that a greater degree of cold than that which he applied, and of longer continuance, did by no means restore this kind of air: for when I had exposed the phials which contained it a whole night, in which the frost was very intense; and also when I kept it surrounded with a mixture of snow and salt, I found it, in all respects, the same as before. It is also advanced, in the same Memoir, p. 41. that _heat_ only, as the reverse of _cold_, renders air unfit for candles burning in it. But I repeated the experiment of the Count for that purpose, without finding any such effect from it. I also remember that, many years ago, I filled an exhausted receiver with air, which had passed through a glass tube made red-hot, and found that a candle would burn in it perfectly well. Also, rarefaction by the air-pump does not injure air in the least degree. Though this experiment failed, I have been so happy, as by accident to have hit upon a method of restoring air, which has been injured by the burning of candles, and to have discovered at least one of the restoratives which nature employs for this purpose. It is _vegetation_. This restoration of vitiated air, I conjecture, is effected by plants imbibing the phlogistic matter with which it is overloaded by the burning of inflammable bodies. But whether there be any foundation for this conjecture or not, the fact is, I think, indisputable. I shall introduce the account of my experiments on this subject, by reciting some of the observations which I made on the growing of plants in confined air, which led to this discovery. One might have imagined that, since common air is necessary to vegetable, as well as to animal life, both plants and animals had affected it in the same manner; and I own I had that expectation, when I first put a sprig of mint into a glass jar, standing inverted in a vessel of water: but when it had continued growing there for some months, I found that the air would neither extinguish a candle, nor was it at all inconvenient to a mouse, which I put into it. The plant was not affected any otherwise than was the necessary consequence of its confined situation; for plants growing in several other kinds of air, were all affected in the very same manner. Every succession of leaves was more diminished in size than the preceding, till, at length, they came to be no bigger than the heads of pretty small pins. The root decayed, and the stalk also, beginning from the root; and yet the plant continued to grow upwards, drawing its nourishment through a black and rotten stem. In the third or fourth set of leaves, long and white hairy filaments grew from the insertion of each leaf and sometimes from the body of the stem, shooting out as far as the vessel in which it grew would permit, which, in my experiments, was about two inches. In this manner a sprig of mint lived, the old plant decaying, and new ones shooting up in its place, but less and less continually, all the summer season. In repeating this experiment, care must be taken to draw away all the dead leaves from about the plant, lest they should putrefy, and affect the air. I have found that a fresh cabbage leaf, put under a glass vessel filled with common air, for the space of one night only, has so affected the air, that a candle would not burn in it the next morning, and yet the leaf had not acquired any smell of putrefaction. Finding that candles would burn very well in air in which plants had grown a long time, and having had some reason to think, that there was something attending vegetation, which restored air that had been injured by respiration, I thought it was possible that the same process might also restore the air that had been injured by the burning of candles. Accordingly, on the 17th of August 1771, I put a sprig of mint into a quantity of air, in which a wax candle had burned out, and found that, on the 27th of the same month, another candle burned perfectly well in it. This experiment I repeated, without the least variation in the event, not less than eight or ten times in the remainder of the summer. Several times I divided the quantity of air in which the candle had burned out, into two parts, and putting the plant into one of them, left the other in the same exposure, contained, also, in a glass vessel immersed in water, but without any plant; and never failed to find, that a candle would burn in the former, but not in the latter. I generally found that five or six days were sufficient to restore this air, when the plant was in its vigour; whereas I have kept this kind of air in glass vessels, immersed in water many months, without being able to perceive that the least alteration had been made in it. I have also tried a great variety of experiments upon it, as by condensing, rarefying, exposing to the light and heat, &c. and throwing into it the effluvia of many different substances, but without any effect. Experiments made in the year 1772, abundantly confirmed my conclusion concerning the restoration of air, in which candles had burned out by plants growing in it. The first of these experiments was made in the month of May; and they were frequently repeated in that and the two following months, without a single failure. For this purpose I used the flames of different substances, though I generally used wax or tallow candles. On the 24th of June the experiment succeeded perfectly well with air in which spirit of wine had burned out, and on the 27th of the same month it succeeded equally well with air in which brimstone matches had burned out, an effect of which I had despaired the preceding year. This restoration of air, I found, depended upon the _vegetating state_ of the plant; for though I kept a great number of the fresh leaves of mint in a small quantity of air in which candles had burned out, and changed them frequently, for a long space of time, I could perceive no melioration in the state of the air. This remarkable effect does not depend upon any thing peculiar to _mint_, which was the plant that I always made use of till July 1772; for on the 16th of that month, I found a quantity of this kind of air to be perfectly restored by sprigs of _balm_, which had grown in it from the 7th of the same month. That this restoration of air was not owing to any _aromatic effluvia_ of these two plants, not only appeared by the _essential oil of mint_ having no sensible effect of this kind; but from the equally complete restoration of this vitiated air by the plant called _groundsel_, which is usually ranked among the weeds, and has an offensive smell. This was the result of an experiment made the 16th of July, when the plant had been growing in the burned air from the 8th of the same month. Besides, the plant which I have found to be the most effectual of any that I have tried for this purpose is _spinach_, which is of quick growth, but will seldom thrive long in water. One jar of burned air was perfectly restored by this plant in four days, and another in two days. This last was observed on the 22d of July. In general, this effect may be presumed to have taken place in much less time than I have mentioned; because I never chose to make a trial of the air, till I was pretty sure, from preceding observations, that the event which I had expected must have taken place, if it would succeed at all; lest, returning back that part of the air on which I made the trial, and which would thereby necessarily receive a small mixture of common air, the experiment might not be judged to be quite fair; though I myself might be sufficiently satisfied with respect to the allowance that was to be made for that small imperfection. FOOTNOTES: [3] The supposition, mentioned in this and other passages of the first part of this publication, viz. that the diminution of common air, by this and other processes is, in part at least, owing to the precipitation of the fixed air from it, the reader will find confirmed by the experiments and observations in the second part. SECTION III. _Of INFLAMMABLE AIR._ I have generally made inflammable air in the manner described by Mr. Cavendish, in the Philosophical Transactions, from iron, zinc, or tin; but chiefly from the two former metals, on account of the process being the least troublesome: but when I extracted it from vegetable or animal substances, or from coals, I put them into a gun-barrel, to the orifice of which I luted a glass tube, or the stem of a tobacco-pipe, and to the end of this I tied a flaccid bladder in order to catch the generated air; or I received the air in a vessel of quicksilver, in the manner represented Fig. 7. There is not, I believe, any vegetable or animal substance whatever, nor any mineral substance, that is inflammable, but what will yield great plenty of inflammable air, when they are treated in this manner, and urged with a strong heat; but, in order to get the most air, the heat must be applied as suddenly, and as vehemently, as possible. For, notwithstanding the same care be taken in luting, and in every other respect, six or even ten times more air may be got by a sudden heat than by a slow one, though the heat that is last applied be as intense as that which was applied suddenly. A bit of dry oak, weighing about twelve grains, will generally yield about a sheep's bladder full of inflammable air with a brisk heat, when it will only give about two or three ounce measures, if the same heat be applied to it very gradually. To what this difference is owing, I cannot tell. Perhaps the phlogiston being extricated more slowly may not be intirely expelled, but form another kind of union with its base; so that charcoal made with a heat slowly applied shall contain more phlogiston than that which is made with a sudden heat. It may be worth while to examine the properties of the charcoal with this view. Inflammable air, when it is made by a quick process, has a very strong and offensive smell, from whatever substance it be generated; but this smell is of three different kinds, according as the air is extracted from mineral, vegetable, or animal substances. The last is exceedingly fetid; and it makes no difference, whether it be extracted from a bone, or even an old and dry tooth, from soft muscular flesh; or any other part of the animal. The burning of any substance occasions the same smell: for the gross fume which arises from them, before they flame, is the inflammable air they contain, which is expelled by heat, and then readily ignited. The smell of inflammable air is the very same, as far as I am able to perceive, from whatever substance of the same kingdom it be extracted. Thus it makes no difference whether it be got from iron, zinc, or tin, from any kind of wood, or, as was observed before, from any part of an animal. If a quantity of inflammable air be contained in a glass vessel standing in water, and have been generated very fast, it will smell even through the water, and this water will also soon become covered with a thin film, assuming all the different colours. If the inflammable air have been generated from iron, this matter will appear to be a red okre, or the earth of iron, as I have found by collecting a considerable quantity of it; and if it have been generated from zinc, it is a whitish substance, which I suppose to be the calx of the metal. It likewise settles to the bottom of the vessel, and when the water is stirred, it has very much the appearance of wool. When water is once impregnated in this manner, it will continue to yield this scum for a considerable time after the air is removed from it. This I have often observed with respect to iron. Inflammable air, made by a violent effervescence, I have observed to be much more inflammable than that which is made by a weak effervescence, whether the water or the oil of vitriol prevailed in the mixture. Also the offensive smell was much stronger in the former case than in the latter. The greater degree of inflammability appeared by the greater number of successive explosions, when a candle was presented to the neck of a phial filled with it.[4] It is possible, however, that this diminution of inflammability may, in some measure, arise from the air continuing so much longer in the bladder when it is made very slowly; though I think the difference is too great for this cause to have produced the whole of it. It may, perhaps, deserve to be tried by a different process, without a bladder. Inflammable air is not thought to be miscible with water, and when kept many months, seems, in general, to be as inflammable as ever. Indeed, when it is extracted from vegetable or animal substances, a part of it will be imbibed by the water in which it stands; but it may be presumed, that in this case, there was a mixture of fixed air extracted from the substance along with it. I have indisputable evidence, however, that inflammable air, standing long in water, has actually lost all its inflammability, and even come to extinguish flame much more than that air in which candles have burned out. After this change it appears to be greatly diminished in quantity, and it still continues to kill animals the moment they are put into it. This very remarkable fact first occurred to my observation on the twenty-fifth of May 1771, when I was examining a quantity of inflammable air, which had been made from zinc, near three years before. Upon this, I immediately set by a common quart-bottle filled with inflammable air from iron, and another equal quantity from zinc; and examining them in the beginning of December following, that from the iron was reduced near one half in quantity, if I be not greatly mistaken; for I found the bottle half full of water, and I am pretty clear that it was full of air when it was set by. That which had been produced from zinc was not altered, and filled the bottle as at first. Another instance of this kind occurred to my observation on the 19th of June 1772, when a quantity of air, half of which had been inflammable air from zinc, and half air in which mice had died, and which had been put together the 30th of July 1771, appeared not to be in the least inflammable, but extinguished flame, as much as any kind of air that I had ever tried. I think that, in all, I have had four instances of inflammable air losing its inflammability, while it stood in water. Though air tainted with putrefaction extinguishes flame, I have not found that animals or vegetables putrefying in inflammable air render it less inflammable. But one quantity of inflammable air, which I had set by in May 1771, along with the others above mentioned, had had some putrid flesh in it; and this air had lost its inflammability, when it was examined at the same time with the other in the December following. The bottle in which this air had been kept, smelled exactly like very strong Harrogate water. I do not think that any person could have distinguished them. I have made plants grow for several months in inflammable air made from zinc, and also from oak; but, though the plants grew pretty well, the air still continued inflammable. The former, indeed, was not so highly inflammable as when it was fresh made, but the latter was quite as much so; and the diminution of inflammability in the former case, I attribute to some other cause than the growth of the plant. No kind of air, on which I have yet made the experiment, will conduct electricity; but the colour of an electric spark is remarkably different in some different kinds of air, which seems to shew that they are not equally good non-conductors. In fixed air, the electric spark is exceedingly white; but in inflammable air it is of a purple, or red colour. Now, since the most vigorous sparks are always the whitest, and, in other cases, when the spark is red, there is reason to think that the electric matter passes with difficulty, and with less rapidity: it is possible that the inflammable air may contain particles which conduct electricity, though very imperfectly; and that the whiteness of the spark in the fixed air, may be owing to its meeting with no conducting particles at all. When an explosion was made in a quantity of inflammable air, it was a little white in the center, but the edges of it were still tinged with a beautiful purple. The degree of whiteness in this case was probably owing to the electric matter rushing with more violence in an explosion than in a common spark. Inflammable air kills animals as suddenly as fixed air, and, as far as can be perceived, in the same manner, throwing them into convulsions, and thereby occasioning present death. I had imagined that, by animals dying in a quantity of inflammable air, it would in time become less noxious; but this did not appear to be the case; for I killed great number of mice in a small quantity of this air; which I kept several months for this purpose, without its being at all sensibly mended; the last, as well as the first mouse, dying the moment it was put into it. I once imagined that, since fixed and inflammable air are the reverse of one another, in several remarkable properties, a mixture of them would make common air; and while I made the mixtures in bladders, I imagined that I had succeeded in my attempt; but I have since found that thin bladders do not sufficiently prevent the air that is contained in them from mixing with the external air. Also corks will not sufficiently confine different kinds of air, unless the phials in which they are confined be set with their mouths downwards, and a little water lie in the necks of them, which, indeed, is equivalent to the air standing in vessels immersed in water. In this manner, however, I have kept different kinds of air for several years. Whatever methods I took to promote the mixture of fixed and inflammable air, they were all ineffectual. I think it my duty, however, to recite the issue of an experiment or two of this kind, in which equal mixtures of these two kinds of air had stood near three years, as they seem to shew that they had in part affected one another, in that long space of time. These mixtures I examined April 27, 1771. One of them had stood in quicksilver, and the other in a corked phial, with a little water in it. On opening the latter in water, the water instantly rushed in, and filled almost half of the phial, and very little more was absorbed afterwards. In this case the water in the phial had probably absorbed a considerable part of the fixed air, so that the inflammable air was exceedingly rarefied; and yet the whole quantity that must have been rendered non-elastic was ten times more than the bulk of the water, and it has not been found that water can contain much more than its own bulk of fixed air. But in other cases I have found the diminution of a quantity of air, and especially of fixed air, to be much greater than I could well account for by any kind of absorption. The phial which had stood immersed in quicksilver had lost very little of its original quantity of air; and being now opened in water, and left there, along with another phial, which was just then filled, as this had been three years before, viz. with air half inflammable and half fixed, I observed that the quantity of both was diminished, by the absorption of the water, in the same proportion. Upon applying a candle to the mouths of the phials which had been kept three years, that which had stood in quicksilver went off at one explosion, exactly as it would have done if there had been a mixture of common air with the inflammable. As a good deal depends upon the apertures of the vessels in which the inflammable air is mixed, I mixed the two kinds of air in equal proportions in the same phial, and after letting the phial stand some days in water, that the fixed air might be absorbed, I applied a candle to it, but it made ten or twelve explosions (stopping the phial after each of them) before the inflammable matter was exhausted. The air which had been confined in the corked phial exploded in the very same manner as an equal and fresh mixture of the two kinds of air in the same phial, the experiment being made as soon as the fixed air was absorbed, as before; so that in this case, the two kinds of air did not seem to have affected one another at all. Considering inflammable air as air united to, or loaded with phlogiston, I exposed to it several substances, which are said to have a near affinity with phlogiston, as oil of vitriol, and spirit of nitre (the former for above a month), but without making any sensible alteration in it. I observed, however, that inflammable air, mixed with the fumes of smoking spirit of nitre, goes off at one explosion, exactly like a mixture of half common and half inflammable air. This I tried several times, by throwing the inflammable air into a phial full of spirit of nitre, with its mouth immersed in a bason containing some of the same spirit, and then applying the flame of a candle to the mouth of the phial, the moment that it was uncovered, after it had been taken out of the bason. This remarkable effect I hastily concluded to have arisen from the inflammable air having been in part deprived of its inflammability, by means of the stronger affinity, which the spirit of nitre had with phlogiston, and therefore I imagined that by letting them stand longer in contact, and especially by agitating them strongly together, I should deprive the air of all its inflammability; but neither of these operations succeeded, for still the air was only exploded at once, as before. And lastly, when I passed a quantity of inflammable air, which had been mixed with the fumes of spirit of nitre, through a body of water, and received it in another vessel, it appeared not to have undergone any change at all, for it went off in several successive explosions, like the purest inflammable air. The effect above-mentioned must, therefore, have been owing to the fumes of the spirit of nitre supplying the place of common air for the purpose of ignition, which is analogous to other experiments with nitre. Having had the curiosity, on the 25th of July 1772, to expose a great variety of different kinds of air to water out of which the air it contained had been boiled, without any particular view; the result was, in several respects, altogether unexpected, and led to a variety of new observations on the properties and affinities of several kinds of air with respect to water. Among the rest three fourths of that which was inflammable was absorbed by the water in about two days, and the remainder was inflammable, but weakly so. Upon this, I began to agitate a quantity of strong inflammable air in a glass jar, standing in a pretty large trough of water, the surface of which was exposed to the common air, and I found that when I had continued the operation about ten minutes, near one fourth of the quantity of air had disappeared; and finding that the remainder made an effervescence with nitrous air, I concluded that it must have become fit for respiration, whereas this kind of air is, at the first, as noxious as any other kind whatever. To ascertain this, I put a mouse into a vessel containing 2-1/2 ounce measures of it, and observed that it lived in it twenty minutes, which is as long as a mouse will generally live in the same quantity of common air. This mouse was even taken out alive, and recovered very well. Still also the air in which it had breathed so long was inflammable, though very weakly so. I have even found it to be so when a mouse has actually died in it. Inflammable air thus diminished by agitation in water, makes but one explosion on the approach of a candle, exactly like a mixture of inflammable air with common air. From this experiment I concluded that, by continuing the same process, I should deprive inflammable air of all its inflammability, and this I found to be the case; for, after a longer agitation, it admitted a candle to burn in it, like common air, only more faintly; and indeed by the test of nitrous air it did not appear to be near so good as common air. Continuing the same process still farther, the air which had been most strongly inflammable a little before, came to extinguish a candle, exactly like air in which a candle had burned out, nor could they be distinguished by the test of nitrous air. I found, by repeated trials, that it was difficult to catch the time in which inflammable air obtained from metals, in coming to extinguish flame, was in the state of common air, so that the transition from the one to the other must be very short. Indeed I think that in many, perhaps in most cases, there may be no proper medium at all, the phlogiston passing at once from that mode of union with its base which constitutes inflammable air, to that which constitutes an air that extinguishes flame, being so much overloaded as to admit of no more. I readily, however, found this middle state in a quantity of inflammable air extracted from oak, which air I had kept a year, and in which a plant had grown, though very poorly, for some part of the time. A quantity of this air, after being agitated in water till it was diminished about one half, admitted a candle to burn in it exceedingly well, and was even hardly to be distinguished from common air by the test of nitrous air. I took some pains to ascertain the quantity of diminution, in fresh made and very highly-inflammable air from iron, at which it ceased to be inflammable, and, upon the whole, I concluded that it was so when it was diminished a little more than one half; for a quantity which was diminished exactly one half had something inflammable in it, but in the slightest degree imaginable. It is not improbable, however, but there may be great differences in the result of this experiment. Finding that water would imbibe inflammable air, I endeavoured to impregnate water with it, by the same process by which I had made water imbibe fixed air; but though I found that distilled water would imbibe about one fourteenth of its bulk of inflammable air, I could not perceive that the taste of it was sensibly altered. FOOTNOTES: [4] To try this, after every explosion, which immediately follows the presenting of the flame, the mouth of the phial should be closed (I generally do it with a finger of the hand in which I hold the phial) for otherwise the inflammable air will continue burning, though invisibly in the day time, till the whole be consumed. SECTION IV. _Of AIR infected with ANIMAL RESPIRATION, or PUTREFACTION._ That candles will burn only a certain time, in a given quantity of air is a fact not better known, than it is that animals can live only a certain time in it; but the cause of the death of the animal is not better known than that of the extinction of flame in the same circumstances; and when once any quantity of air has been rendered noxious by animals breathing in it as long as they could, I do not know that any methods have been discovered of rendering it fit for breathing again. It is evident, however, that there must be some provision in nature for this purpose, as well as for that of rendering the air fit for sustaining flame; for without it the whole mass of the atmosphere would, in time, become unfit for the purpose of animal life; and yet there is no reason to think that it is, at present, at all less fit for respiration than it has ever been. I flatter myself, however, that I have hit upon two of the methods employed by nature for this great purpose. How many others there may be, I cannot tell. When animals die upon being put into air in which other animals have died, after breathing in it as long as they could, it is plain that the cause of their death is not the want of any _pabulum vitæ,_ which has been supposed to be contained in the air, but on account of the air being impregnated with something stimulating to their lungs; for they almost always die in convulsions, and are sometimes affected so suddenly, that they are irrecoverable after a single inspiration, though they be withdrawn immediately, and every method has been taken to bring them to life again. They are affected in the same manner, when they are killed in any other kind of noxious air that I have tried, viz. fixed air, inflammable air, air filled with the fumes of brimstone, infected with putrid matter, in which a mixture of iron filings and brimstone has stood, or in which charcoal has been burned, or metals calcined, or in nitrous air, &c. As it is known that _convulsions_ weaken, and exhaust the vital powers, much more than the most vigorous _voluntary_ action of the muscles, perhaps these universal convulsions may exhaust the whole of what we may call the _vis vitæ_ at once, at least that the lungs may be rendered absolutely incapable of action, till the animal be suffocated, or be irrecoverable for want of respiration. If a mouse (which is an animal that I have commonly made use of for the purpose of these experiments) can stand the first shock of this stimulus, or has been habituated to it by degrees, it will live a considerable time in air in which other mice will die instantaneously. I have frequently found that when a number of mice have been confined in a given quantity of air, less than half the time that they have actually lived in it, a fresh mouse being introduced to them has been instantly thrown into convulsions, and died. It is evident, therefore, that if the experiment of the Black Hole were to be repeated, a man would stand the better chance of surviving it, who should enter at the first, than at the last hour. I have also observed, that young mice will always live much longer than old ones, or than those which are full grown, when they are confined in the same quantity of air. I have sometimes known a young mouse to live six hours in the same circumstances in which an old mouse has not lived one. On these accounts, experiments with mice, and, for the same reason, no doubt, with other animals also, have a considerable degree of uncertainty attending them; and therefore, it is necessary to repeat them frequently, before the result can be absolutely depended upon. But every person of feeling will rejoice with me in the discovery of _nitrous air_, to be mentioned hereafter, which supersedes many experiments with the respiration of animals, being a much more accurate test of the purity of air. The discovery of the provision in nature for restoring air, which has been injured by the respiration of animals, having long appeared to me to be one of the most important problems in natural philosophy, I have tried a great variety of schemes in order to effect it. In these my guide has generally been to consider the influences to which the atmosphere is, in fact, exposed; and, as some of my unsuccessful trials may be of use to those who are disposed to take pains in the farther investigation of this subject, I shall mention the principal of them. The noxious effluvium with which air is loaded by animal respiration, is not absorbed by standing, without agitation; in fresh or salt water. I have kept it many months in fresh water, when, instead of being meliorated, it has seemed to become even more deadly, so as to require more time to restore it, by the methods which will be explained hereafter, than air which has been lately made noxious. I have even spent several hours in pouring this air from one glass vessel into another, in water, sometimes as cold, and sometimes as warm, as my hands could bear it, and have sometimes also wiped the vessels many times, during the course of the experiment, in order to take off that part of the noxious matter, which might adhere to the glass vessels, and which evidently gave them an offensive smell; but all these methods were generally without any sensible effect. The _motion_, also, which the air received in these circumstances, it is very evident, was of no use for this purpose. I had not then thought of the simple, but most effectual method of agitating air in water, by putting it into a tall jar and shaking it with my hand. This kind of air is not restored by being exposed to the _light_, or by any other influence to which it is exposed, when confined in a thin phial, in the open air, for some months. Among other experiments, I tried a great variety of different _effluvia_, which are continually exhaling into the air, especially of those substances which are known to resist putrefaction; but I could not by these means effect any melioration of the noxious quality of this kind of air. Having read, in the memoirs of the Imperial Society, of a plague not affecting a particular village, in which there was a large sulphur-work, I immediately fumigated a quantity of this kind of air; or (which will hereafter appear to be the very same thing) air tainted with putrefaction, with the fumes of burning brimstone, but without any effect. I once imagined, that the _nitrous acid_ in the air might be the general restorative which I was in quest of; and the conjecture was favoured, by finding that candles would burn in air extracted from saltpetre. I therefore spent a good deal of time in attempting, by a burning glass, and other means, to impregnate this noxious air, with some effluvium of saltpetre, and, with the same view, introduced into it the fumes of the smoaking spirit of nitre; but both these methods were altogether ineffectual. In order to try the effect of _heat_, I put a quantity of air, in which mice had died, into a bladder, tied to the end of the stem of a tobacco-pipe, at the other end of which was another bladder, out of which the air was carefully pressed. I then put the middle part of the stem into a chafing-dish of hot coals, strongly urged with a pair of bellows; and, pressing the bladders alternately, I made the air pass several times through the heated part of the pipe. I have also made this kind of air very hot, standing in water before the fire. But neither of these methods were of any use. _Rarefaction_ and _condensation_ by instruments were also tried, but in vain. Thinking it possible that the _earth_ might imbibe the noxious quality of the air, and thence supply the roots of plants with such putrescent matter as is known to be nutritive to them, I kept a quantity of air, in which mice had died, in a phial, one half of which was filled with fine garden-mould; but, though it stood two months in these circumstances, it was not the better for it. I once imagined that, since several kinds of air cannot be long separated from common air, by being confined in bladders, in bottles well corked; or even closed with ground stopples, the affinity between this noxious air and the common air might be so great, that they would mix through a body of water interposed between them; the water continually receiving from the one, and giving to the other, especially as water receives some kind of impregnation from, I believe, every kind of air to which it is contiguous; but I have seen no reason to conclude, that a mixture of any kind of air with the common air can be produced in this manner. I have kept air in which mice have died, air in which candles have burned out, and inflammable air, separated from the common air, by the slightest partition of water that I could well make, so that it might not evaporate in a day or two, if I should happen not to attend to them; but I found no change in them after a month or six weeks. The inflammable air was still inflammable, mice died instantly in the air in which other mice had died before, and candles would not burn where they had burned out before. Since air tainted with animal or vegetable putrefaction is the same thing with air rendered noxious by animal respiration, I shall now recite the observations which I have made upon this kind of air, before I treat of the method of restoring them. That these two kinds of air are, in fact, the same thing, I conclude from their having several remarkable common properties, and from their differing in nothing that I have been able to observe. They equally extinguish flame, they are equally noxious to animals, they are equally, and in the same way, offensive to the smell, and they are restored by the same means. Since air which has passed through the lungs is the same thing with air tainted with animal putrefaction, it is probable that one use of the lungs is to carry off a _putrid effluvium_, without which, perhaps, a living body might putrefy as soon as a dead one. When a mouse putrefies in any given quantity of air, the bulk of it is generally increased for a few days; but in a few days more it begins to shrink up, and in about eight or ten days, if the weather be pretty warm, it will be found to be diminished 1/6, or 1/5 of its bulk. If it do not appear to be diminished after this time, it only requires to be passed through water, and the diminution will not fail to be sensible. I have sometimes known almost the whole diminution to take place, upon once or twice passing through the water. The same is the case with air, in which animals have breathed as long as they could. Also, air in which candles have burned out may almost always be farther reduced by this means. All these processes, as I observed before, seem to dispose the compound mass of air to part with some constituent part belonging to it (which appears to be the _fixed air_ that enters into its constitution) and this being miscible with water, must be brought into contact with it, in order to mix with it to the most advantage, especially when its union with the other constituent principles of the air is but partially broken. I have put mice into vessels which had their mouths immersed in quicksilver, and observed that the air was not much contracted after they were dead or cold; but upon withdrawing the mice, and admitting lime water to the air, it immediately became turbid, and was contracted in its dimensions as usual. I tried the same thing with air tainted with putrefaction, putting a dead mouse to a quantity of common air, in a vessel which had its mouth immersed in quicksilver, and after a week I took the mouse out, drawing it through the quicksilver, and observed that, for some time, there was an apparent increase of the air perhaps about 1/20. After this, it stood two days in the quicksilver, without any sensible alteration; and then admitting water to it, it began to be absorbed, and continued so, till the original quantity was diminished about 1/6. If, instead of common water, I had made use of lime-water in this experiment, I make no doubt but it would have become turbid. If a quantity of lime-water in a phial be put under a glass vessel standing in water, it will not become turbid, and provided the access of the common air be prevented, it will continue lime-water, I do not know how long; but if a mouse be left to putrefy in the vessel, the water will deposit all its lime in a few days. This is owing to the fixed air deposited by the common air, and perhaps also from more fixed air discharged from the putrefying substances in some part of the process of putrefaction. The air that is discharged from putrefying substances seems, in some cases, to be chiefly fixed air, with the addition of some other effluvium, which has the power of diminishing common air. The resemblance between the true putrid effluvium and fixed air in the following experiment, which is as decisive as I can possibly contrive it, appeared to be very great; indeed much greater than I had expected. I put a dead mouse into a tall glass vessel, and having filled the remainder with quicksilver, and set it, inverted, in a pot of quicksilver, I let it stand about two months, in which time the putrid effluvium issuing from the mouse had filled the whole vessel, and part of the dissolved blood, which lodged upon the surface of the quicksilver, began to be thrown out. I then filled another glass vessel, of the same size and shape, with as pure fixed air as I could make, and exposed them both, at the same time, to a quantity of lime-water. In both cases the water grew turbid alike, it rose equally fast in both the vessels, and likewise equally high; so that about the same quantity remained unabsorbed by the water. One of these kinds of air, however, was exceedingly sweet and pleasant, and the other insufferably offensive; one of them also would have made an addition to any quantity of common air, with which it had been mixed, and the other would have diminished it. This, at least, would have been the consequence, if the mouse itself had putrefied in any quantity of common air. It seems to depend, in some measure, upon the _time_, and other circumstances, in the dissolution of animal or vegetable substances, whether they yield the proper putrid effluvium, or fixed, or inflammable air; but the experiments which I have made upon this subject, have not been numerous enough to enable me to decide with certainty concerning those circumstances. Putrid cabbage, green or boiled, infects the air in the very same manner as putrid animal substances. Air thus tainted is equally contracted in its dimensions, it equally extinguishes flame, and is equally noxious to animals; but they affect the air very differently, if the heat that is applied to them be considerable. If beef or mutton, raw or boiled, be placed so near to the fire, that the heat to which it is exposed shall equal, or rather exceed, that of the blood, a considerable quantity of air will be generated in a day or two, about 1/7th of which I have generally found to be absorbed by water, while all the rest was inflammable; but air generated from vegetables, in the same circumstances, will be almost all fixed air, and no part of it inflammable. This I have repeated again and again, the whole process being in quicksilver; so that neither common air nor water, had any access to the substance on which the experiment was made; and the generation of air, or effluvium of any kind, except what might be absorbed by quicksilver, or resorbed by the substance itself, might be distinctly noted. A vegetable substance, after standing a day or two in these circumstances, will yield nearly all the air that can be extracted from it, in that degree of heat; whereas an animal substance will continue to give more air, or effluvium, of some kind or other, with very little alteration, for many weeks. It is remarkable, however, that though a piece of beef or mutton, plunged in quicksilver, and kept in this degree of heat, yield air, the bulk of which is inflammable, and contracts no putrid smell (at least, in a day or two) a mouse treated in the same manner, yields the proper putrid effluvium, as indeed the smell sufficiently indicates. That the putrid effluvium will mix with water seems to be evident from the following experiment. If a mouse be put into a jar full of water, standing with its mouth inverted in another vessel of water, a considerable quantity of elastic matter (and which may, therefore, be called _air_) will soon be generated, unless the weather be so cold as to check all putrefaction. After a short time, the water contracts an extremely fetid and offensive smell, which seems to indicate that the putrid effluvium pervades the water, and affects the neighbouring air; and since, after this, there is often no increase of the air, that seems to be the very substance which is carried off through the water, as fast as it is generated; and the offensive smell is a sufficient proof that it is not fixed air. For this has a very agreeable flavour, whether it be produced by fermentation, or extracted from chalk by oil of vitriol; affecting not only the mouth, but even the nostrils; with a pungency which is peculiarly pleasing to a certain degree, as any person may easily satisfy himself, who will chuse to make the experiment. If the water in which the mouse was immersed, and which is saturated with the putrid air, be changed, the greater part of the putrid air, will, in a day or two, be absorbed, though the mouse continues to yield the putrid effluvium as before; for as soon as this fresh water becomes saturated with it, it begins to be offensive to the smell, and the quantity of the putrid air upon its surface increases as before. I kept a mouse producing putrid air in this manner for the space of several months. Six ounce measures of air not readily absorbed by water, appeared to have been generated from one mouse, which had been putrefying eleven days in confined air, before it was put into a jar which was quite filled with water, for the purpose of this observation. Air thus generated from putrid mice standing in water, without any mixture of common air, extinguishes flame, and is noxious to animals, but not more so than common air only tainted with putrefaction. It is exceedingly difficult and tedious to collect a quantity of this putrid air, not miscible in water, so very great a proportion of what is collected being absorbed by the water in which it is kept; but what that proportion is, I have not endeavoured to ascertain. It is probably the same proportion that that part of fixed air, which is not readily absorbed by water, bears to the rest; and therefore this air, which I at first distinguished by the name of _the putrid effluvium_, is probably the same with fixed air, mixed with the phlogistic matter, which, in this and other processes, diminishes common air. Though a quantity of common air be diminished by any substance putrefying in it, I have not yet found the same effect to be produced by a mixture of putrid air with common air; but, in the manner in which I have hitherto made the experiment, I was obliged to let the putrid air pass through a body of water, which might instantly absorb the phlogistic matter that diminished the common air. Insects of various kinds live perfectly well in air tainted with animal or vegetable putrefaction, when a single inspiration of it would have instantly killed any other animal. I have frequently tried the experiment with flies and butterflies. The _aphides_ also will thrive as well upon plants growing in this kind of air, as in the open air. I have even been frequently obliged to take plants out of the putrid air in which they were growing, on purpose to brush away the swarms of these insects which infected them; and yet so effectually did some of them conceal themselves, and so fast did they multiply, in these circumstances, that I could seldom keep the plants quite clear of them. When air has been freshly and strongly tainted with putrefaction, so as to smell through the water, sprigs of mint have presently died, upon being put into it, their leaves turning black; but if they do not die presently, they thrive in a most surprizing manner. In no other circumstances have I ever seen vegetation so vigorous as in this kind of air, which is immediately fatal to animal life. Though these plants have been crouded in jars filled with this air, every leaf has been full of life; fresh shoots have branched out in various directions, and have grown much faster than other similar plants, growing in the same exposure in common air. This observation led me to conclude, that plants, instead of affecting the air in the same manner with animal respiration, reverse the effects of breathing, and tend to keep the atmosphere sweet and wholesome, when it is become noxious, in consequence of animals either living and breathing, or dying and putrefying in it. In order to ascertain this, I took a quantity of air, made thoroughly noxious, by mice breathing and dying in it, and divided it into two parts; one of which I put into a phial immersed in water; and to the other (which was contained in a glass jar, standing in water) I put a sprig of mint. This was about the beginning of August 1771, and after eight or nine days, I found that a mouse lived perfectly well in that part of the air, in which the sprig of mint had grown, but died the moment it was put into the other part of the same original quantity of air; and which I had kept in the very same exposure, but without any plant growing in it. This experiment I have several times repeated; sometimes using air in which animals had breathed and died, and at other times using air, tainted with vegetable or animal putrefaction; and generally with the same success. Once, I let a mouse live and die in a quantity of air which had been noxious, but which had been restored by this process, and it lived nearly as long as I conjectured it might have done in an equal quantity of fresh air; but this is so exceedingly various, that it is not easy to form any judgment from it; and in this case the symptom of _difficult respiration_ seemed to begin earlier than it would have done in common air. Since the plants that I made use of manifestly grow and thrive in putrid air; since putrid matter is well known to afford proper nourishment for the roots of plants; and since it is likewise certain that they receive nourishment by their leaves as well as by their roots, it seems to be exceedingly probable, that the putrid effluvium is in some measure extracted from the air, by means of the leaves of plants, and therefore that they render the remainder more fit for respiration. Towards the end of the year some experiments of this kind did not answer so well as they had done before, and I had instances of the relapsing of this restored air to its former noxious state. I therefore suspended my judgment concerning the efficacy of plants to restore this kind of noxious air, till I should have an opportunity of repeating my experiments, and giving more attention to them. Accordingly I resumed the experiments in the summer of the year 1772, when I presently had the most indisputable proof of the restoration of putrid air by vegetation; and as the fact is of some importance, and the subsequent variation in the state of this kind of air is a little remarkable, I think it necessary to relate some of the facts pretty circumstantially. The air, on which I made the first experiments, was rendered exceedingly noxious by mice dying in it on the 20th of June. Into a jar nearly filled with one part of this air, I put a sprig of mint, while I kept another part of it in a phial, in the same exposure; and on the 27th of the same month, and not before, I made a trial of them, by introducing a mouse into a glass vessel, containing 2-1/2 ounce measures filled with each kind of air; and I noted the following facts. When the vessel was filled with the air in which the mint had grown, a very large mouse lived five minutes in it, before it began to shew any sign of uneasiness. I then took it out, and found it to be as strong and vigorous as when it was first put in; whereas in that air which had been kept in the phial only, without a plant growing in it, a younger mouse continued not longer than two or three seconds, and was taken out quite dead. It never breathed after, and was immediately motionless. After half an hour, in which time the larger mouse (which I had kept alive, that the experiment might be made on both the kinds of air with the very same animal) would have been sufficiently recruited, supposing it to have received any injury by the former experiment, was put into the same vessel of air; but though it was withdrawn again, after being in it hardly one second, it was recovered with difficulty, not being able to stir from the place for near a minute. After two days, I put the same mouse into an equal quantity of common air, and observed that it continued seven minutes without any sign of uneasiness; and being very uneasy after three minutes longer, I took it out. Upon the whole, I concluded that the restored air wanted about one fourth of being as wholesome as common air. The same thing also appeared when I applied the test of nitrous air. In the seven days, in which the mint was growing in this jar of noxious air, three old shoots had extended themselves about three inches, and several new ones had made their appearance in the same time. Dr. Franklin and Sir John Pringle happened to be with me, when the plant had been three or four days in this state, and took notice of its vigorous vegetation, and remarkably healthy appearance in that confinement. On the 30th of the same month, a mouse lived fourteen minutes, breathing naturally all the time, and without appearing to be much uneasy, till the last two minutes, in the vessel containing two ounce measures and a half of air which had been rendered noxious, by mice breathing in it almost a year before, and which, I had found to be most highly noxious on the 19th of this month, a plant having grown in it, but not exceedingly well, these eleven days; on which account I had deferred making the trial so long. The restored air was affected by a mixture of nitrous air, almost as much as common air. As this putrid air was thus easily restored to a considerable degree of fitness for respiration, by plants growing in it, I was in hopes that by the same means it might in time be so much more perfectly restored, that a candle would burn in it; and for this purpose I kept plants growing in the jars which contained this air till the middle of August following, but did not take sufficient care to pull out all the old and rotten leaves. The plants, however, had grown, and looked so well upon the whole, that I had no doubt but that the air must constantly have been in a mending state; when I was exceedingly surprized to find, on the 24th of that month, that though the air in one of the jars had not grown worse, it was no better; and that the air in the other jar was so much worse than it had been, that a mouse would have died in it in a few seconds. It also made no effervescence with nitrous air, as it had done before. Suspecting that the same plant might be capable of restoring putrid air to a certain degree only, or that plants might have a contrary tendency in some stages of their growth, I withdrew the old plant, and put a fresh one in its place; and found that, after seven days, the air was restored to its former wholesome state. This fact I consider as a very remarkable one, and well deserving of a farther investigation, as it may throw more light upon the principles of vegetation. It is not, however, a single fact; for I had several instances of the same kind in the preceding year; but it seemed so very extraordinary, that air should grow worse by the continuance of the same treatment by which it had grown better, that, whenever I observed it, I concluded that I had not taken sufficient care to satisfy myself of its previous restoration. That plants are capable of perfectly restoring air injured by respiration, may, I think, be inferred with certainty from the perfect restoration, by this means, of air which had passed through my lungs, so that a candle would burn in it again, though it had extinguished flame before, and apart of the same original quantity of air still continued to do so. Of this one instance occurred in the year 1771, a sprig of mint having grown in a jar of this kind of air, from the 25th of July to the 17th of August following; and another trial I made, with the same success, the 7th of July 1772, the plant having grown in it from the 29th of June preceding. In this case also I found that the effect was not owing to any virtue in the leaves of mint; for I kept them constantly changed in a quantity of this kind of air, for a considerable time, without making any sensible alteration in it. These proofs of a partial restoration of air by plants in a state of vegetation, though in a confined and unnatural situation, cannot but render it highly probable, that the injury which is continually done to the atmosphere by the respiration of such a number of animals, and the putrefaction of such masses of both vegetable and animal matter, is, in part at least, repaired by the vegetable creation. And, notwithstanding the prodigious mass of air that is corrupted daily by the above-mentioned causes; yet, if we consider the immense profusion of vegetables upon the face of the earth, growing in places, suited to their nature, and consequently at full liberty to exert all their powers, both inhaling and exhaling, it can hardly be thought, but that it may be a sufficient counterbalance to it, and that the remedy is adequate to the evil. Dr. Franklin, who, as I have already observed, saw some of my plants in a very flourishing state, in highly noxious air, was pleased to express very great satisfaction with the result of the experiments. In his answer to the letter in which I informed him of it, he says, "That the vegetable creation should restore the air which is spoiled by the animal part of it, looks like a rational system, and seems to be of a piece with the rest. Thus fire purifies water all the world over. It purifies it by distillation, when it raises it in vapours, and lets it fall in rain; and farther still by filtration, when, keeping it fluid, it suffers that rain to percolate the earth. We knew before that putrid animal substances were converted into sweet vegetables, when mixed with the earth, and applied as manure; and now, it seems, that the same putrid substances, mixed with the air, have a similar effect. The strong thriving state of your mint in putrid air seems to shew that the air is mended by taking something from it, and not by adding to it." He adds, "I hope this will give some check to the rage of destroying trees that grow near houses, which has accompanied our late improvements in gardening, from an opinion of their being unwholesome. I am certain, from long observation, that there is nothing unhealthy in the air of woods; for we Americans have every where our country habitations in the midst of woods, and no people on earth enjoy better health, or are more prolific." Having rendered inflammable air perfectly innoxious by continued _agitation in a trough of water_, deprived of its air, I concluded that other kinds of noxious air might be restored by the same means; and I presently found that this was the case with putrid air, even of more than a year's standing. I shall observe once for all, that this process has never failed to restore any kind of noxious air on which I have tried it, viz. air injured by respiration or putrefaction, air infected with the fumes of burning charcoal, and of calcined metals, air in which a mixture of iron filings and brimstone, that in which paint made of white lead and oil has stood, or air which has been diminished by a mixture of nitrous air. Of the remarkable effect which this process has on nitrous air itself, an account will be given in its proper place. If this process be made in water deprived of air, either by the air-pump, by boiling, or by distillation, or if fresh rain-water be used, the air will always be diminished by the agitation; and this is certainly the fairest method of making the experiment. If the water be fresh pump-water, there will always be an increase of the air by agitation, the air contained in the water being set loose, and joining that which is in the jar. In this case, also, the air has never failed to be restored; but then it might be suspected that the melioration was produced by the addition of some more wholesome ingredient. As these agitations were made in jars with wide mouths, and in a trough which had a large surface exposed to the common air, I take it for granted that the noxious effluvia, whatever they be, were first imbibed by the water, and thereby transmitted to the common atmosphere. In some cases this was sufficiently indicated by the disagreeable smell which attended the operation. After I had made these experiments, I was informed that an ingenious physician and philosopher had kept a fowl alive twenty-four hours, in a quantity of air in which another fowl of the same size had not been able to live longer than an hour, by contriving to make the air, which it breathed, pass through no very large quantity of acidulated water, the surface of which was not exposed to the common air; and that even when the water was not acidulated, the fowl lived much longer than it could have done, if the air which it breathed had not been drawn through the water. As I should not have concluded that this experiment would have succeeded so well, from any observations that I had made upon the subject, I took a quantity of air in which mice had died, and agitated it very strongly, first in about five times its own quantity of distilled water, in the manner in which I had impregnated water with fixed air; but though the operation was continued a long time, it made no sensible change in the properties of the air. I also repeated the operation with pump-water, but with as little effect. In this case, however, though the air was agitated in a phial, which had a narrow neck, the surface of the water in the bason was considerably large, and exposed to the common atmosphere, which must have tended a little to favour the experiment. In order to judge more precisely of the effect of these different methods of agitating air, I transferred the very noxious air, which I had hot been able to amend in the least degree by the former method, into an open jar, standing in a trough of water; and when I had agitated it till it was diminished about one third, I found it to be better than air in which candles had burned out, as appeared by the test of the nitrous air; and a mouse lived in 2-1/2 ounce measures of it a quarter of an hour, and was not sensibly affected the first ten or twelve minutes. In order to determine whether the addition of any _acid_ to the water, would make it more capable of restoring putrid air, I agitated a quantity of it in a phial containing very strong vinegar; and after that in _aqua fortis_, only half diluted with water; but by neither of these processes was the air at all mended, though the agitation was repeated, at intervals, during a whole day, and it was moreover allowed to stand in that situation all night. Since, however, water in these experiments must have imbibed and retained a certain portion of the noxious effluvia, before they could be transmitted to the external air, I do not think it improbable but that the agitation of the sea and large lakes may be of some use for the purification of the atmosphere, and the putrid matter contained in water may be imbibed by aquatic plants, or be deposited in some other manner. Having found, by several experiments above-mentioned that the proper putrid effluvium is something quite distinct from fixed air, and finding, by the experiments of Dr. Macbride, that fixed air corrects putrefaction; it occured to me, that fixed air, and air tainted with putrefaction, though equally, noxious when separate, might make a wholesome mixture, the one, correcting the other; and I was confirmed in this opinion by, I believe, not less than fifty or sixty instances, in which air, that had been made in the highest degree noxious, by respiration or putrefaction, was so far sweetened, by a mixture of about four times as much fixed air, that afterwards mice lived in it exceedingly well, and in some cases almost as long as in common air. I found it, indeed, to be more difficult to restore _old_ putrid air by this means; but I hardly ever failed to do it, when the two kinds of air had stood a long time together; by which I mean about a fortnight or three weeks. The reason why I do not absolutely conclude that the restoration of air in these cases was the effect of fixed air, is that, when I made a trial of the mixture, I sometimes agitated the two kinds of air pretty strongly together, in a trough of water, or at least passed it several times through water, from one jar to another, that the superfluous fixed air might be absorbed, not suspecting at that time that the agitation could have any other effect. But having since found that very violent, and especially long-continued agitation in water, without any mixture of fixed air, never failed to render any kind of noxious air in some measure fit for respiration (and in one particular instance the mere transferring of the air from one vessel to another through the water, though for a much longer time than I ever used for the mixtures of air, was of considerable use for the same purpose) I began to entertain some doubt of the efficacy of fixed air in this case. In some cases also the mixture of fixed air had by no means so much effect on the putrid air as, from the generality of my observations, I should have expected. I was always aware, indeed, that it might be said, that, the residuum of fixed air not being very noxious, such an addition must contribute to mend the putrid air; but, in order to obviate this objection, I once mixed the residuum of as much fixed air as I had found, by a variety of trials, to be sufficient to restore a given quantity of putrid air, with an equal quantity of that air, without making any sensible melioration of it. Upon the whole, I am inclined to think that this process could hardly have succeeded so well as it did with me, and in so great a number of trials, unless fixed air have some tendency to correct air tainted with respiration or putrefaction; and it is perfectly agreeable to the analogy of Dr. Macbride's discoveries, and may naturally be expected from them, that it should have such an effect. By a mixture of fixed air I have made wholesome the residuum of air generated by putrefaction only, from mice plunged in water. This, one would imagine, _à priori_, to be the most noxious of all kinds of air. For if common air only tainted with putrefaction be so deadly, much more might one expect that air to be so, which was generated from putrefaction only; but it seems to be nothing more than common air (or at least that kind of fixed air which is not absorbed by water) tainted with putrefaction, and therefore requires no other process to sweeten it. In this case, however, we seem to have an instance of the generation of genuine common air, though mixed with something that is foreign to it. Perhaps the residuum of fixed air may be another instance of the same nature, and also the residuum of inflammable air, and of nitrous air, especially nitrous air loaded with phlogiston, after long agitation in water. Fixed air is equally diffused through the whole mass of any quantity of putrid air with which it is mixed: for dividing the mixture into two equal parts, they were reduced in the same proportion by passing through water. But this is also the case with some of the kinds of air which will not incorporate, as inflammable air, and air in which brimstone has burned. If fixed air tend to correct air which has been injured by animal respiration or putrefaction, _lime kilns_, which discharge great quantities of fixed air, may be wholesome in the neighbourhood of populous cities, the atmosphere of which must abound with putrid effluvia. I should think also that physicians might avail themselves of the application of fixed air in many putrid disorders, especially as it may be so easily administered by way of _clyster_, where it would often find its way to much of the putrid matter. Nothing is to be apprehended from the distention of the bowels by this kind of air, since it is so readily absorbed by any fluid or moist substance. Since fixed air is not noxious _per se_, but, like fire, only in excess, I do not think it at all hazardous to attempt to _breathe_ it. It is however easily conveyed into the _stomach_, in natural or artificial Pyrmont water, in briskly-fermenting liquors, or a vegetable diet. It is even possible, that a considerable quantity of fixed air might be imbibed by the absorbing vessels of the skin, if the whole body, except the head, should be suspended over a vessel of strongly-fermenting liquor; and in some putrid disorders this treatment might be very salutary. If the body was exposed quite naked, there would be very little danger from the cold in this situation, and the air having freer access to the skin might produce a greater effect. Being no physician, I run no risk by throwing out these random, and perhaps whimsical proposals.[5] Having communicated my observations on fixed air, and especially my scheme of applying it by way of _clyster_ in putrid disorders, to Mr. Hey, an ingenious surgeon in Leeds a case presently occurred, in which he had an opportunity of giving it a trial; and mentioning it to Dr. Hird and Dr. Crowther, two physicians who attended the patient, they approved the scheme, and it was put in execution; both by applying the fixed air by way of clyster, and at the same time making the patient drink plentifully of liquors strongly impregnated with it. The event was such, that I requested Mr. Hey to draw up a particular account of the case, describing the whole of the treatment, that the public might be satisfied that this new application of fixed air is perfectly safe, and also, have an opportunity of judging how far it had the effect which I expected from it; and as the application is new, and not unpromising, I shall subjoin his letter to me on the subject, by way of _Appendix_ to these papers. When I began my inquires into the properties of different kinds of air, I engaged my friend Dr. Percival to attend to the _medicinal uses_ of them, being sensible that his knowledge of philosophy as well as of medicine would give him a singular advantage for this purpose. The result of his observations I shall also insert in the Appendix. FOOTNOTES: [5] Some time after these papers were first printed, I was pleased to find the same proposal in _Dr. Alexander's Experimental Essays_. SECTION V. _Of AIR in which a mixture of BRIMSTONE and FILINGS of IRON has stood._ Reading in Dr. Hales's account of his experiments, that there was a great diminution of the quantity of air in which _a mixture of powdered brimstone and filings of iron, made into a paste with water_, had stood, I repeated the experiment, and found the diminution greater than I had expected. This diminution of air is made as effectually, and as expeditiously, in quicksilver as in water; and it may be measured with the greatest accuracy, because there is neither any previous expansion or increase of the quantity of air, and because it is some time before this process begins to have any sensible effect. This diminution of air is various; but I have generally found it to be between one fifth and one fourth of the whole. Air thus diminished is not heavier, but rather lighter than common air; and though lime-water does not become turbid when it is exposed to this air, it is probably owing to the formation of a selenitic salt, as was the case with the simple burning of brimstone above-mentioned. That something proceeding from the brimstone strongly affects the water which is confined in the same place with this mixture, is manifest from the very strong smell that it has of the volatile spirit of vitriol. I conclude that the diminution of air by this, process is of the same kind with the diminution of it in the other cases, because when this mixture is put into air which has been previously diminished, either by the burning of candles, by respiration, or putrefaction, though it never fails to diminish it something more, it is, however, no farther than this process alone would have done it. If a fresh mixture be introduced into a quantity of air which had been reduced by a former mixture, it has little or no farther effect. I once observed, that when a mixture of this kind was taken out of a quantity of air in which a candle had before burned out, and in which it had stood for several days, it was quite cold and black, as it always becomes in a confined place; but it presently grew very hot, smoaked copously, and smelled very offensively; and when it was cold, it was brown, like the rust of iron. I once put a mixture of this kind to a quantity of inflammable air, made from iron, by which means it was diminished 1/9 or 1/10 in its bulk; but, as far as I could judge, it was still as inflammable as ever. Another quantity of inflammable air was also reduced in the same proportion, by a mouse putrefying in it; but its inflammability was not seemingly lessened. Air diminished by this mixture of iron filings and brimstone, is exceedingly noxious to animals, and I have not perceived that it grows any better by keeping in water. The smell of it is very pungent and offensive. The quantity of this mixture which I made use of in the preceding experiments, was from two to four ounce measures; but I did not perceive, but that the diminution of the quantity of air (which was generally about twenty ounce measures) was as great with the smallest, as with the largest quantity. How small a quantity is necessary to diminish a given quantity of air to a _maximum_, I have made no experiments to ascertain. As soon as this mixture of iron filings with, brimstone and water, begins to ferment, it also turns black, and begins to swell, and it continues to do so, till it occupies twice as much space as it did at first. The force with which it expands is great; but how great it is I have not endeavoured to determine. When this mixture is immersed in water, it generates no air, though it becomes black, and swells. SECTION VI. _Of NITROUS AIR._ Ever since I first read Dr. Hales's most excellent _Statical Essays_, I was particularly struck with that experiment of his, of which an account is given, VOL. I, p. 224. and VOL. II, p. 280. in which common air, and air generated from the Walton pyrites, by spirit of nitre, made a turbid red mixture, and in which part of the common air was absorbed; but I never expected to have the satisfaction of seeing this remarkable appearance, supposing it to be peculiar to that particular mineral. Happening to mention this subject to the Hon. Mr. Cavendish, when I was in London, in the spring of the year 1772, he said that he did not imagine but that other kinds of pyrites, or the metals might answer as well, and that probably the red appearance of the mixture depended upon the spirit of nitre only. This encouraged me to attend to the subject; and having no pyrites, I began with the solution of the different metals in spirit of nitre, and catching the air which was generated in the solution, I presently found what I wanted, and a good deal more. Beginning with the solution of brass, on the 4th of June 1772, I first found this remarkable species of air, only one effect of which, was casually observed by Dr. Hales; and he gave so little attention to it, and it has been so much unnoticed since his time, that, as far as I know, no name has been given to it. I therefore found myself, contrary to my first resolution, under an absolute necessity of giving a name to this kind of air myself. When I first began to speak and write of it to my friends, I happened to distinguish it by the name of _nitrous air_, because I had procured it by means of spirit of nitre only; and though I cannot say that I altogether like the term, neither myself nor any of my friends, to whom I have applied for the purpose, have been able to hit upon a better; so that I am obliged, after all, to content myself with it. I have found that this kind of air is readily procured from iron, copper, brass, tin, silver, quicksilver, bismuth, and nickel, by the nitrous acid only, and from gold and the regulus of antimony by _aqua regia_. The circumstances attending the solution of each of these metals are various, but hardly worth mentioning, in treating of the properties of the _air_ which they yield; which, from what metal soever it is extracted, has, as far as I have been able to observe, the very same properties. One of the most conspicuous properties of this kind of air is the great diminution of any quantity of common air with which it is mixed, attended with a turbid red, or deep orange colour, and a considerable heat. The _smell_ of it, also, is very strong, and remarkable, but very much resembling that of smoking spirit of nitre. The diminution of a mixture of this and common air is not an equal diminution of both the kinds, which is all that Dr. Hales could observe, but of about one fifth of the common air, and as much of the nitrous air as is necessary to produce that effect; which, as I have found by many trials, is about one half as much as the original quantity of common air. For if one measure of nitrous air be put to two measures of common air, in a few minutes (by which time the effervescence will be over, and the mixture will have recovered its transparency) there will want about one ninth of the original two measures; and if both the kinds of air be very pure, the diminution will still go on slowly, till in a day or two, the whole will be reduced to one fifth less than the original quantity of common air. This farther diminution, by long standing, I had not observed at the time of the first publication of these papers. I hardly know any experiment that is more adapted to amaze and surprize than this is, which exhibits a quantity of air, which, as it were, devours a quantity of another kind of air half as large as itself, and yet is so far from gaining any addition to its bulk, that it is considerably diminished by it. If, after this full saturation of common air with nitrous air, more nitrous air be put to it, it makes an addition equal to its own bulk, without producing the least redness, or any other visible effect. If the smallest quantity of common air be put to any larger quantity of nitrous air, though the two together will not occupy so much space as they did separately, yet the quantity will still be larger than that of the nitrous air only. One ounce measure of common air being put to near twenty ounce measures of nitrous air, made an addition to it of about half an ounce measure. This being a much greater proportion than the diminution of common air, in the former experiment, proves that part of the diminution in the former case is in the nitrous air. Besides, it will presently appear, that nitrous air is subject to a most remarkable diminution; and as common air, in a variety of other cases, suffers a diminution from one fifth to one fourth, I conclude, that in this case also it does not exceed that proportion, and therefore that the remainder of the diminution respects the nitrous air. In order to judge whether the _water_ contributed to the diminution of this mixture of nitrous and common air, I made the whole process several times in quicksilver, using one third of nitrous, and two thirds of common air, as before. In this case the redness continued a very long time, and the diminution was not so great as when the mixtures had been made in water, there remaining one seventh more than the original quantity of common air. This mixture stood all night upon the quicksilver; and the next morning I observed that it was no farther diminished upon the admission of water to it, nor by pouring it several times through the water, and letting it stand in water two days. Another mixture, which had stood about six hours on the quicksilver, was diminished a little more upon the admission of water, but was never less than the original quantity of common air. In another case however, in which the mixture had stood but a very short time in quicksilver, the farther diminution, which took place upon the admission of water, was much more considerable; so that the diminution, upon the whole, was very nearly as great as if the process had been intirely in water. It is evident from these experiments, that the diminution is in part owing to the absorption by the water; but that when the mixture is kept a long time, in a situation in which there is no water to absorb any part of it, it acquires a constitution, by which it is afterwards incapable of being absorbed by water, or rather, there is an addition to the quantity of air by nitrous air produced by the solution of the quicksilver. It will be seen, in the second part of this work, that, in the decomposition of nitrous air by its mixture with common air, there is nothing at hand when the process is made in quicksilver, with which the acid that entered into its composition can readily unite. In order to determine whether the fixed part of common air was deposited in the diminution of it by nitrous air, I inclosed a vessel full of lime-water in the jar in which the process was made, but it occasioned no precipitation of the lime; and when the vessel was taken out, after it had been in that situation a whole day, the lime was easily precipitated by breathing into it as usual. But though the precipitation of the lime was not sensible in this method of making the experiment, it is sufficiently so when the whole process is made in lime-water, as will be seen in the second part of this work; so that we have here another evidence of the deposition of fixed air from common air. I have made no alteration, however, in the preceding paragraph, because it may not be unuseful, as a caution to future experimenters. It is exceedingly remarkable that this effervescence and diminution, occasioned by the mixture of nitrous air, is peculiar to common air, or _air fit for respiration_; and, as far as I can judge, from a great number of observations, is at least very nearly, if not exactly, in proportion to its fitness for this purpose; so that by this means the goodness of air may be distinguished much more accurately than it can be done by putting mice, or any other animals, to breathe in it. This was a most agreeable discovery to me, as I hope it may be an useful one to the public; especially as, from this time, I had no occasion for so large a stock of mice as I had been used to keep for the purpose of these experiments, using them only in those which required to be very decisive; and in these cases I have seldom failed to know beforehand in what manner they would be affected. It is also remarkable that, on whatever account air is unfit for respiration, this same test is equally applicable. Thus there is not the least effervescence between nitrous and fixed air, or inflammable air, or any species of diminished air. Also the degree of diminution being from nothing at all to more than one third of the whole of any quantity of air, we are, by this means, in possession of a prodigiously large _scale_, by which we may distinguish very small degrees of difference in the goodness of air. I have not attended much to this circumstance, having used this test chiefly for greater differences; but, if I did not deceive myself, I have perceived a real difference in the air of my study, after a few persons have been with me in it, and the air on the outside of the house. Also a phial of air having been sent me, from the neighbourhood of York, it appeared not to be so good as the air near Leeds; that is, it was not diminished so much by an equal mixture of nitrous air, every other circumstance being as nearly the same as I could contrive. It may perhaps be possible, but I have not yet attempted it, to distinguish some of the different winds, or the air of different times of the year, &c. &c. by this test. By means of this test I was able to determine what I was before in doubt about, viz. the _kind_ as well as the _degree_ of injury done to air by candles burning in it. I could not tell with certainty, by means of mice, whether it was at all injured with respect to respiration; and yet if nitrous air may be depended upon for furnishing an accurate test, it must be rather more than one third worse than common air, and have been diminished by the same general cause of the other diminutions of air. For when, after many trials, I put one measure of thoroughly putrid and highly noxious air, into the same vessel with two measures of good wholesome air, and into another vessel an equal quantity, viz. three measures of air in which a candle had burned out; and then put equal quantities of nitrous air to each of them, the latter was diminished rather more than the former. It agrees with this observation, that _burned air_ is farther diminished both by putrefaction, and a mixture of iron filings and brimstone; and I therefore take it for granted by every other cause of the diminution of air. It is probable, therefore, that burned air is air so far loaded with phlogiston, as to be able to extinguish a candle, which it may do long before it is fully saturated. Inflammable air with a mixture of nitrous air burns with a green flame. This makes a very pleasing experiment when it is properly conducted. As, for some time, I chiefly made use of _copper_ for the generation of nitrous air, I first ascribed this circumstance to that property of this metal, by which it burns with a green flame; but I was presently satisfied that it must arise from the spirit of nitre, for the effect is the very same from which ever of the metals the nitrous air is extracted, all of which I tried for this purpose, even silver and gold. A mixture of oil of vitriol and spirit of nitre in equal proportions dissolved iron, and the produce was nitrous air; but a less degree of spirit of nitre in the mixture produced air that was inflammable, and which burned with a green flame. It also tinged common air a little red, and diminished it, though not much. The diminution of common air by a mixture of nitrous air, is not so extraordinary as the diminution which nitrous air itself is subject to from a mixture of iron filings and brimstone, made into a paste with water. This mixture, as I have already observed, diminishes common air between one fifth and one fourth, but has no such effect upon any kind of air that has been diminished, and rendered noxious by any other process; but when it is put to a quantity of nitrous air, it diminishes it so much, that no more than one fourth of the original quantity will be left. The effect of this process is generally perceived in five or six hours, about which time the visible effervesence of the mixture begins; and in a very short time it advances so rapidly, that in about an hour almost the whole effect will have taken place. If it be suffered to stand a day or two longer, the air will still be diminished farther, but only a very little farther, in proportion to the first diminution. The glass jar, in which the air and this mixture have been confined, has generally been so much heated in this process, that I have not been able to touch it. Nitrous air thus diminished has not so strong a smell as nitrous air itself, but smells just like common air in which the same mixture has stood; and it is not capable of being diminished any farther, by a fresh mixture of iron and brimstone. Common air saturated with nitrous air is also no farther diminished by this mixture of iron filings and brimstone, though the mixture ferments with great heat, and swells very much in it. Plants die very soon, both in nitrous air, and also in common air saturated with nitrous air, but especially in the former. Neither nitrous air, nor common air saturated with nitrous air, differ in specific gravity from common air. At least, the difference is so small, that I could not be sure there was any; sometimes about three pints of it seeming to be about half a grain heavier, and at other times as much lighter than common air. Having, among other kinds of air, exposed a quantity of nitrous air to water out of which the air had been well boiled, in the experiment to which I have more than once referred (as having been the occasion of several new and important observations) I found that 19/20 of the whole was absorbed. Perceiving, to my great surprize, that so very great a proportion of this kind of air was miscible with water, I immediately began to agitate a considerable quantity of it, in a jar standing in a trough of the same kind of water; and, with about four times as much agitation as fixed air requires, it was so far absorbed by the water, that only about one fifth remained. This remainder extinguished flame, and was noxious to animals. Afterwards I diminished a pretty large quantity of nitrous air to one eighth of its original bulk, and the remainder still retained much of its peculiar smell, and diminished common air a little. A mouse also died in it, but not so suddenly as it would have done in pure nitrous air. In this operation the peculiar smell of nitrous air is very manifest, the water being first impregnated with the air, and then transmitting it to the common atmosphere. This experiment gave me the hint of impregnating water with nitrous air, in the manner in which I had before done it with fixed air; and I presently found that distilled water would imbibe about one tenth of its bulk of this kind of air, and that it acquired a remarkably acid and astringent taste from it. The smell of water thus impregnated is at first peculiarly pungent. I did not chuse to swallow any of it, though, for any thing that I know, it may be perfectly innocent, and perhaps, in some cases, salutary. This kind of air is retained very obstinately by water. In an exhausted receiver a quantity of water thus saturated emitted a whitish fume, such as sometimes issues from bubbles of this air when it is first generated, and also some air-bubbles; but though it was suffered to stand a long time in this situation, it still retained its peculiar taste; but when it had stood all night pretty near the fire, the water was become quite vapid, and had deposited a filmy kind of matter, of which I had often collected a considerable quantity from the trough in which jars containing this air had stood. This I suppose to be a precipitate of the metal, by the solution of which the nitrous air was generated. I have not given so much attention to it as to know, with certainty, in what circumstances this _deposit_ is made, any more than I do the matter deposited from inflammable air above-mentioned; for I cannot get it, at least in any considerable quantity, when I please; whereas I have often found abundance of it, when I did not expect it at all. The nitrous air with which I made the first impregnation of water was extracted from copper; but when I made the impregnation with air from quicksilver, the water had the very same taste, though the matter deposited from it seemed to be of a different kind; for it was whitish, whereas the other had a yellowish tinge. Except the first quantity of this impregnated water, I could never deprive any more that I made of its peculiar taste. I have even let some of it stand more than a week, in phials with their mouths open, and sometimes very near the fire, without producing any alteration in it[6]. Whether any of the spirit of nitre contained in the nitrous air be mixed with the water in this operation, I have not yet endeavoured to determine. This, however, may probably be the case, as the spirit of nitre is, in a considerable degree, volatile[7]. It will perhaps be thought, that the most _useful_, if not the most remarkable, of all the properties of this extraordinary kind of air, is its power of preserving animal substances from putrefaction, and of restoring those that are already putrid, which it possesses in a far greater degree than fixed air. My first observation of this was altogether casual. Having found nitrous air to suffer so great a diminution as I have already mentioned by a mixture of iron filings and brimstone, I was willing to try whether it would be equally diminished by other causes of the diminution of common air, especially by putrefaction; and for this purpose I put a dead mouse into a quantity of it, and placed it near the fire, where the tendency to putrefaction was very great. In this case there was a considerable diminution, viz. from 5-1/4 to 3-1/4; but not so great as I had expected, the antiseptic power of the nitrous air having checked the tendency to putrefaction; for when, after a week, I took the mouse out, I perceived, to my very great surprize, that it had no offensive smell. Upon this I took two other mice, one of them just killed, and the other soft and putrid, and put them both into the same jar of nitrous air, standing in the usual temperature of the weather, in the months of July and August of 1772; and after twenty-five days, having observed that there was little or no change in the quantity of the air, I took the mice out; and, examining them, found them both perfectly sweet, even when cut through in several places. That which had been put into the air when just dead was quite firm; and the flesh of the other, which had been putrid and soft, was still soft, but perfectly sweet. In order to compare the antiseptic power of this kind of air with that of fixed air, I examined a mouse which I had inclosed in a phial full of fixed air, as pure as I could make it, and which I had corked very close; but upon opening this phial in water about a month after, I perceived that a large quantity of putrid effluvium had been generated; for it rushed with violence out of the phial; and the smell that came from it, the moment the cork was taken out, was insufferably offensive. Indeed Dr. Macbride says, that he could only restore very thin pieces of putrid flesh by means of fixed air. Perhaps the antiseptic power of these kinds of air may be in proportion to their acidity. If a little pains were taken with this subject, this remarkable antiseptic power of nitrous air might possibly be applied to various uses, perhaps to the preservation of the more delicate birds, fishes, fruits, &c. mixing it in different proportions with common or fixed air. Of this property of nitrous air anatomists may perhaps avail themselves, as animal substances may by this means be preserved in their natural soft state; but how long it will answer for this purpose, experience only can shew. I calcined lead and tin in the manner hereafter described in a quantity of nitrous air, but with very little sensible effect; which rather surprized me; as, from the result of the experiment with the iron filings and brimstone, I had expected a very great diminution of the nitrous air by this process; the mixture of iron filings and brimstone, and the calcination of metals, having the same effect upon common air, both of them diminishing it in nearly the same proportion. But though I made the metals _fume_ copiously in nitrous air, there might be no real _calcination_, the phlogiston not being separated, and the proper calcination prevented by there being no _fixed_ _air_, which is necessary to the formation of the calx, to unite with it. Nitrous air is procured from all the proper metals by spirit of nitre, except lead, and from all the semi-metals that I have tried, except zinc. For this purpose I have used bismuth and nickel, with spirit of nitre only, and regulus of antimony and platina, with _aqua regia_. I got little or no air from lead by spirit of nitre, and have not yet made any experiments to ascertain the nature of this solution. With zinc I have taken a little pains. Four penny-weights and seventeen grains of zinc dissolved in spirit of nitre, to which as much water was added, yielded about twelve ounce measures of air, which had, in some degree, the properties of nitrous air, making a slight effervescence with common air, and diminishing it about as much as nitrous air, which had been itself diminished one half by washing in water. The smell of them both was also the same; so that I concluded it to be the same thing, that part of the nitrous air, which is imbibed by water, being retained in this solution. In order to discover whether this was the case, I made the solution boil in a sand-heat. Some air came from it in this state, which seemed to be the same thing, with nitrous air diminished about one sixth, or one eighth, by washing in water. When the fluid part was evaporated, there remained a brown fixed substance, which was observed by Mr. Hellot, who describes it, Ac. Par. 1735, M. p. 35. A part of this I threw into a small red-hot crucible; and covering it immediately with a receiver, standing in water, I observed that very dense red fumes rose from it, and filled the receiver. This redness continued about as long as that which is occasioned by a mixture of nitrous and common air; the air was also considerably diminished within the receiver. This substance, therefore, must certainly have contained within it the very same thing, or principle, on which the peculiar properties of nitrous air depend. It is remarkable, however, that though the air within the receiver was diminished about one fifth by this process, it was itself as much affected with a mixture of nitrous air, as common air is, and a candle burned in it very well. This may perhaps be attributed to some effect of the spirit of nitre, in the composition of that brown substance. Nitrous air, I find, will be considerably diminished in its bulk by standing a long time in water, about as much as inflammable air is diminished in the same circumstances. For this purpose I kept for some months a quart-bottle full of each of these kinds of air; but as different quantities of inflammable air vary very much in this respect, it is not improbable but that nitrous air may vary also. From one trial that I made, I conclude that nitrous air may be kept in a bladder much better than most other kinds of air. The air to which I refer was kept about a fortnight in a bladder, through which the peculiar smell of the nitrous air was very sensible for several days. In a day or two the bladder became red, and was much contracted in its dimensions. The air within it had lost very little of its peculiar property of diminishing common air. I did not endeavour to ascertain the exact quantity of nitrous air produced from given quantities, of all the metals which yield it; but the few observations which I did make for this purpose I shall recite in this place: dwt. gr. 6 0 of silver yielded 17-1/2 ounce measures. 5 19 of quicksilver 4-1/2 1 2-1/2 of copper 14-1/2 2 0 of brass 21 0 20 of iron 16 1 5 of bismuth 6 0 12 of nickel 4 FOOTNOTES: [6] I have since found, that nitrous air has never failed to escape from the water, which has been impregnated with it, by long exposure to the open air. [7] This suspicion has been confirmed by the ingenious Mr. Bewley, of Great Massingham in Norfolk, who has discovered that the acid taste of this water is not the necessary consequence of its impregnation with nitrous air, but is the effect of the _acid vapour_, into which part of this air is resolved, when it is decomposed by a mixture with common air. This, it will be seen, exactly agrees with my own observation on the constitution of nitrous air, in the second part of this work. A more particular account of Mr. Bewley's observation will be given in the _Appendix_. SECTION VII. _Of AIR infected with the FUMES of BURNING CHARCOAL._ Air infected with the fumes of burning charcoal is well known to be noxious; and the Honourable Mr. Cavendish favoured me with an account of some experiments of his, in which a quantity of common air was reduced from 180 to 162 ounce measures, by passing through a red-hot iron tube filled with the dust of charcoal. This diminution he ascribed to such a _destruction_ of common air as Dr. Hales imagined to be the consequence of burning. Mr. Cavendish also observed, that there had been a generation of fixed air in this process, but that it was absorbed by sope leys. This experiment I also repeated, with a small variation of circumstances, and with nearly the same result. Afterwards, I endeavoured to ascertain, by what appears to me to be an easier and more certain method, in what manner air is affected with the fumes of charcoal, viz. by suspending bits of charcoal within glass vessels, filled to a certain height with water, and standing inverted in another vessel of water, while I threw the focus of a burning mirror, or lens, upon them. In this manner I diminished a given quantity of air one fifth, which is nearly in the same proportion with other diminutions of air. If, instead of pure water, I used _lime-water_ in this process, it never failed to become turbid by the precipitation of the lime, which could only be occasioned by fixed air, either discharged from the charcoal, or deposited by the common air. At first I concluded that it came from the charcoal; but considering that it is not probable that fixed air, confined in any substance, can bear so great a degree of heat as is necessary to make charcoal, without being wholly expelled; and that in other diminutions of common air, by phlogiston only, there appears to be a deposition of fixed air, I have now no doubt but that, in this case also, it is supplied from the same source. This opinion is the more probable, from there being the same precipitation of lime, in this process, with whatever degree of heat the charcoal had been made. If, however, the charcoal had not been made with a very considerable degree of heat, there never failed to be a permanent addition of inflammable air produced; which agrees with what I observed before, that, in converting dry wood into charcoal, the greatest part is changed into inflammable air. I have sometimes found, that charcoal which was made with the most intense heat of a smith's fire, which vitrified part of a common crucible in which the charcoal was confined, and which had been continued above half an hour, did not diminish the air in which the focus of a burning mirror was thrown upon it; a quantity of inflammable air equal to the diminution of the common air being generated in the process: whereas, at other times, I have not perceived that there was any generation of inflammable air, but a simple diminution of common air, when the charcoal had been made with a much less degree of heat. This subject deserves to be farther investigated. To make the preceding experiment with still more accuracy, I repeated it in quicksilver; when I perceived that there was a small increase of the quantity of air, probably from a generation of inflammable air. Thus it stood without any alteration a whole night, and part of the following day; when lime-water, being admitted to it, it presently became turbid, and, after some time, the whole quantity of air, which was about four ounce measures, was diminished one fifth, as before. In this case, I carefully weighed the piece of charcoal, which was exactly two grains, and could not find that it was sensibly diminished in weight by the operation. Air thus diminished by the fumes of burning charcoal not only extinguishes flame, but is in the highest degree noxious to animals; it makes no effervescence with nitrous air, and is incapable of being diminished any farther by the fumes of more charcoal, by a mixture of iron filings and brimstone, or by any other cause of the diminution of air that I am acquainted with. This observation, which respects all other kinds of diminished air, proves that Dr. Hales was mistaken in his notion of the _absorption_ of air in those circumstances in which he observed it. For he supposed that the remainder was, in all cases, of the same nature with that which had been absorbed, and that the operation of the same cause would not have failed to produce a farther diminution; whereas all my observations shew that air, which has once been fully diminished by any cause whatever, is not only incapable of any farther diminution, either from the same or from any other cause, but that it has likewise acquired _new properties_, most remarkably different from those which it had before, and that they are, in a great measure, the same in all the cases. These circumstances give reason to suspect, that the cause of diminution is, in reality, the same in all the cases. What this cause is, may, perhaps, appear in the next course of observations. SECTION VIII. _Of the effect of the CALCINATION of METALS, and of the EFFLUVIA of PAINT made with WHITE-LEAD and OIL, on AIR._ Having been led to suspect, from the experiments which I had made with charcoal, that the diminution of air in that case, and perhaps in other cases also, was, in some way or other the consequence of its having more than its usual quantity of phlogiston, it occurred to me, that the calcination of metals, which are generally supposed to consist of nothing but a metallic earth united to phlogiston, would tend to ascertain the fact, and be a kind of _experimentum crucis_ in the case. Accordingly, I suspended pieces of lead and tin in given quantities of air, in the same manner as I had before treated the charcoal; and throwing the focus of a burning mirror or lens upon them, so as to make them fume copiously. I presently perceived a diminution of the air. In the first trial that I made, I reduced four ounce measures of air to three, which is the greatest diminution of common air that I had ever observed before, and which I account for, by supposing that, in other cases, there was not only a cause of diminution, but causes of addition also, either of fixed or inflammable air, or some other permanently elastic matter, but that the effect of the calcination of metals being simply the escape of phlogiston, the cause of diminution was alone and uncontrouled. The air, which I had thus diminished by calcination of lead, I transferred into another clean phial, but found that the calcination of more lead in it (or at least the attempt to make a farther calcination) had no farther effect upon it. This air also, like that which had been infected with the fumes of charcoal, was in the highest degree noxious, made no effervescence with nitrous air, was no farther diminished by the mixture of iron filings and brimstone, and was not only rendered innoxious, but also recovered, in a great measure, the other properties of common air, by washing in water. It might be suspected that the noxious quality of air in which _lead_ was calcined, might be owing to some fumes peculiar to that metal; but I found no sensible difference between the properties of this air, and that in which _tin_ was calcined. The _water_ over which metals are calcined acquires a yellowish tinge, and an exceedingly pungent smell and taste, pretty much (as near as I can recollect, for I did not compare them together) like that over which brimstone has been frequently burned. Also a thin and whitish pellicle covered both the surface of the water, and likewise the sides of the phial in which the calcination was made; insomuch that, without frequently agitating the water, it grew so opaque by this constantly accumulating incrustation, that the sun-beams could not be transmitted through it in a quantity sufficient to produce the calcination. I imagined, however, that, even when this air was transferred into a clean phial, the metals were not so easily melted or calcined as they were in fresh air; for the air being once fully saturated with phlogiston, may not so readily admit any more, though it be only to transmit it to the water. I also suspected that metals were not easily melted or calcined in inflammable, fixed, or nitrous air, or any kind of diminished air.[8] None of these kinds of air suffered any change by this operation; nor was there any precipitation of lime, when charcoal was heated in any of these kinds of air standing in lime-water. This furnishes another, and I think a pretty decisive proof, that, in the precipitation of lime by charcoal, the fixed air does not come from the charcoal, but from the common air. Otherwise it is hard to assign a reason, why the same degree of heat (or at least a much greater) should not expel the fixed air from this substance, though surrounded by these different kinds of air, and why the fixed air might not be transmitted through them to the lime-water. Query. May not water impregnated with phlogiston from calcined metals, or by any other method, be of some use in medicine? The effect of this impregnation is exceedingly remarkable; but the principle with which it is impregnated is volatile, and intirely escapes in a day or two, if the surface of the water be exposed to the common atmosphere. It should seem that phlogiston is retained more obstinately by charcoal than it is by lead or tin; for when any given quantity of air is fully saturated with phlogiston from charcoal, no heat that I have yet applied has been able to produce any more effect upon it; whereas, in the same circumstances, lead and tin may still be calcined, at least be made to emit a copious fume, in which some part of the phlogiston may be set loose. The air indeed, can take no more; but the water receives it, and the sides of the phial also receive an addition of incrustation. This is a white powdery substance, and well deserves to be examined. I shall endeavour to do it at my leisure. Lime-water never became turbid by the calcination of metals over it, the calx immediately seizing the precipitated fixed air, in preference to the lime in the water; but the colour, smell, and taste of the water was always changed and the surface of it became covered with a yellow pellicle, as before. When this process was made in quicksilver, the air was diminished only one fifth; and upon water being admitted to it, no more was absorbed; which is an effect similar to that of a mixture of nitrous and common air, which was mentioned before. The preceding experiments on the calcination of metals suggested to me a method of explaining the cause of the mischief which is known to arise from fresh _paint_, made with white-lead (which I suppose is an imperfect calx of lead) and oil. To verify my hypothesis, I first put a small pot full of this kind of paint, and afterwards (which answered much better, by exposing a greater surface of the paint) I daubed several pieces of paper with it, and put them under a receiver, and observed, that in about twenty-four hours, the air was diminished between one fifth and one fourth, for I did not measure it very exactly. This air also was, as I expected to find, in the highest degree noxious; it did not effervesce with nitrous air, it was no farther diminished by a mixture of iron filings and brimstone, and was made wholesome by agitation in water deprived of all air. I think it appears pretty evident, from the preceding experiments on the calcination of metals that air is, some way or other, diminished in consequence of being highly charged with phlogiston; and that agitation in water restores it, by imbibing a great part of the phlogistic matter. That water has a considerable affinity with phlogiston, is evident from the strong impregnation which it receives from it. May not plants also restore air diminished by putrefaction by absorbing part of the phlogiston with which it is loaded? The greater part of a dry plant, as well as of a dry animal substance, consists of inflammable air, or something that is capable of being converted into inflammable air; and it seems to be as probable that this phlogistic matter may have been imbibed by the roots and leaves of plants, and afterwards incorporated into their substance, as that it is altogether produced by the power of vegetation. May not this phlogistic matter be even the most essential part of the food and support of both vegetable and animal bodies? In the experiments with metals, the diminution of air seems to be the consequence of nothing but a saturation with phlogiston; and in all the other cases of the diminution of air, I do not see but that it may be effected by the same means. When a vegetable or animal substance is dissolved by putrefaction, the escape of the phlogistic matter (which, together with all its other constituent parts, is then let loose from it) may be the circumstance that produces the diminution of the air in which it putrefies. It is highly improbable that what remains after an animal body has been thoroughly dissolved by putrefaction, should yield so great a quantity of inflammable air, as the dried animal substance would have done. Of this I have not made an actual trial, though I have often thought of doing it, and still intend to do it; but I think there can be no doubt of the result. Again, iron, by its fermentation with brimstone and water, is evidently reduced to a calx, so that phlogiston must have escaped from it. Phlogiston also must evidently be set loose by the ignition of charcoal, and is not improbably the matter which flies off from paint, composed of white-lead and oil. Lastly, since spirit of nitre is known to have a very remarkable affinity with phlogiston, it is far from being improbable that nitrous air may also produce the same effect by the same means. To this hypothesis it may be objected, that, if diminished air be air saturated with phlogiston, it ought to be inflammable. But this by no means follows; since its inflammability may depend upon some particular _mode of combination_, or degree of affinity, with which we are not acquainted. Besides, inflammable air seems to consist of some other principle, or to have some other constituent part, besides phlogiston and common air, as is probable from that remarkable deposit, which, as I have observed, is made by inflammable air, both from iron and zinc. It is not improbable, however, but that a greater degree of heat may inflame that air which extinguishes a common candle, if it could be conveniently applied. Air that is inflammable, I observe, extinguishes red-hot wood; and indeed inflammable substances can only be those which, in a certain degree of heat, have a less affinity with the phlogiston they contain, than the air, or some other contiguous substance, has with it; so that the phlogiston only quits one substance, with which it was before combined, and enters another, with which it may be combined in a very different manner. This substance, however, whether it be air or any thing else, being now fully saturated with phlogiston, and not being able to take any more, in the same circumstances, must necessarily extinguish fire, and put a stop to the ignition of all other bodies, that is, to the farther escape of phlogiston from them. That plants restore noxious air, by imbibing the phlogiston with which it is loaded, is very agreeable to the conjectures of Dr. Franklin, made many years ago, and expressed in the following extract from the last edition of his Letters, p. 346. "I have been inclined to think that the fluid _fire_, as well as the fluid _air_, is attracted by plants in their growth, and becomes consolidated with the other materials of which they are formed, and makes a great part of their substance; that, when they come to be digested, and to suffer in the vessels a kind of fermentation, part of the fire, as well as part of the air, recovers its fluid active state again, and diffuses itself in the body, digesting and separating it; that the fire so re-produced, by digestion and separation, continually leaving the body, its place is supplied by fresh quantities, arising from the continual separation; that whatever quickens the motion of the fluids in an animal, quickens the separation, and re-produces more of the fire, as exercise; that all the fire emitted by wood, and other combustibles, when burning, existed in them before in a solid state, being only discovered when separating; that some fossils, as sulphur, sea-coal, &c. contain a great deal of solid fire; and that, in short, what escapes and is dissipated in the burning of bodies, besides water and earth, is generally the air and fire, that before made parts of the solid." FOOTNOTES: [8] I conclude from the experiments of M. Lavoisier, which were made with a much better burning lens than I had an opportunity of making use of, that there was no _real calcination_ of the metals, though they were made to _fume_ in inflammable or nitrous air; because he was not able to produce more than a slight degree of calcination in any given quantity of common air. SECTION IX. _Of MARINE ACID AIR._ Being very much struck with the result of an experiment of the Hon. Mr. Cavendish, related Phil. Trans. Vol. LVI. p. 157, by which, though, he says, he was not able to get any inflammable air from copper, by means of spirit of salt, he got a much more remarkable kind of air, viz. one that lost its elasticity by coming into contact with water, I was exceedingly desirous of making myself acquainted with it. On this account, I began with making the experiment in quicksilver, which I never failed to do in any case in which I suspected that air might either be absorbed by water, or be in any other manner affected by it; and by this means I presently got a much more distinct idea of the nature and effects of this curious solution. Having put some copper filings into a small phial, with a quantity of spirit of salt; and making the air (which was generated in great plenty, on the application of heat) ascend into a tall glass vessel full of quicksilver, and standing in quicksilver, the whole produce continued a considerable time without any change of dimensions. I then introduced a small quantity of water to it; when about three fourths of it (the whole being about four ounce measures) presently, but gradually, disappeared, the quicksilver rising in the vessel. I then introduced a considerable quantity of water; but there was no farther diminution of the air, and the remainder I found to be inflammable. Having frequently continued this process a long time after the admission of the water, I was much amused with observing the large bubbles of the newly generated air, which came through the quicksilver, the sudden diminution of them when they came to the water, and the very small bubbles which went through the water. They made, however, a continual, though slow, increase of inflammable air. Fixed air, being admitted to the whole produce of this air from copper, had no sensible effect upon it. Upon the admission of water, a great part of the mixture presently disappeared; another part, which I suppose to have been the fixed air, was absorbed slowly; and in this particular case the very small permanent residuum did not take fire; but it is very possible that it might have done so, if the quantity had been greater. The solution of _lead_ in the marine acid is attended with the very same phænomena as the solution of copper in the same acid; about three fourths of the generated air disappearing on the admission of water; and the remainder being inflammable. The solutions of iron, tin, and zinc, in the marine acid, were all attended with the same phænomena as the solutions of copper and lead, but in a less degree; for in iron one eighth, in tin one sixth, and in zinc one tenth of the generated air disappeared on the admission of water. The remainder of the air from iron, in this case, burned with a green, or very light blue flame. I had always thought it something extraordinary that a species of air should _lose its elasticity_ by the mere _contact_ of any thing, and from the first suspected that it must have been _imbibed_ by the water that was admitted to it; but so very great a quantity of this air disappeared upon the admission of a very small quantity of water, that at first I could not help concluding that appearances favoured the former hypothesis. I found, however, that when I admitted a much smaller quantity of water, confined in a narrow glass tube, a part only of the air disappeared, and that very slowly, and that more of it vanished upon the admission of more water. This observation put it beyond a doubt, that this air was properly _imbibed_ by the water, which, being once fully saturated with it, was not capable of receiving any more. The water thus impregnated tasted very acid, even when it was much diluted with other water, through which the tube containing it was drawn. It even dissolved iron very fast, and generated inflammable air. This last observation, together with another which immediately follows, led me to the discovery of the true nature of this remarkable kind of air. Happening, at one time, to use a good deal of copper and a small quantity of spirit of salt, in the generation of this kind of air, I was surprized to find that air was produced long after, I could not but think that the acid must have been saturated with the metal; and I also found that the proportion of inflammable air to that which was absorbed by the water continually diminished, till, instead of being one fourth of the whole, as I had first observed, it was not so much as one twentieth. Upon this, I concluded that this subtle air did not arise from the copper, but from the spirit of salt; and presently making the experiment with the acid only, without any copper, or metal of any kind, this air was immediately produced in as great plenty as before; so that this remarkable kind of air is, in fact, nothing more than the vapour, or fumes of spirit of salt, which appear to be of such a nature, that they are not liable to be condensed by cold, like the vapour of water, and other fluids, and therefore may be very properly called an _acid air_, or more restrictively, the _marine acid air_. This elastic acid vapour, or acid air, extinguishes flame, and is much heavier than common air; but how much heavier, will not be easy to ascertain. A cylindrical glass vessel, about three fourths of an inch in diameter, and four inches deep, being filled with it, and turned upside down, a lighted candle may be let down into it more than twenty times before it will burn at the bottom. It is pleasing to observe the colour of the flame in this experiment; for both before the candle goes out, and also when it is first lighted again, it burns with a beautiful green, or rather light-blue flame, such as is seen when common salt is thrown into the fire. When this air is all expelled from any quantity of spirit of salt, which is easily perceived by the subsequent vapour being condensed by cold, the remainder is a very weak acid, barely capable of dissolving iron. Being now in the possession of a new subject of experiments, viz. an elastic acid vapour, in the form of a permanent air, easily procured, and effectually confined by glass and quicksilver, with which it did not seem to have any affinity; I immediately began to introduce a variety of substances to it; in order to ascertain its peculiar properties and affinities, and also the properties of those other bodies with respect to it. Beginning with _water_, which, from preceding observations, I knew would imbibe it, and become impregnated with it; I found that 2-1/2 grains of rain-water absorbed three ounce measures of this air, after which it was increased one third in its bulk, and weighed twice as much as before; so that this concentrated vapour seems to be twice as heavy as rain-water: Water impregnated with it makes the strongest spirit of salt that I have seen, dissolving iron with the most rapidity. Consequently, two thirds of the best spirit of salt is nothing more than mere phlegm or water. Iron filings, being admitted to this air, were dissolved by it pretty fast, half of the air disappearing, and the other half becoming inflammable air, not absorbed by water. Putting chalk to it, fixed air was produced. I had not introduced many substances to this air, before I discovered that it had an affinity with _phlogiston_, so that it would deprive other substances of it, and form with it such an union as constitutes inflammable air; which seems to shew, that inflammable air universally consists of the union of some acid vapour with phlogiston. Inflammable air was produced, when to this acid air I put spirit of wine, oil of olives, oil of turpentine, charcoal, phosphorus, bees-wax, and even sulphur. This last observation, I own, surprized me; for, the marine acid being reckoned the weakest of the three mineral acids, I did not think that it had been capable of dislodging the oil of vitriol from this substance; but I found that it had the very same effect both upon alum and nitre; the vitriolic acid in the former case, and the nitrous in the latter, giving place to the stronger vapour of spirit of salt. The rust of iron, and the precipitate of nitrous air made from copper, also imbibed this air very fast, and the little that remained of it was inflammable air; which proves, that these calces contain phlogiston. It seems also to be pretty evident, from this experiment, that the precipitate above mentioned is a real calx of the metal, by the solution of which the nitrous air is generated. As some remarkable circumstances attend the absorption of this acid air, by the substances above-mentioned, I shall briefly mention them. Spirit of wine absorbs this air as readily as water itself, and is increased in bulk by that means. Also, when it is saturated, it dissolves iron with as much rapidity, and still continues inflammable. Oil of olives absorbs this air very slowly, and at the same time, it turns almost black, and becomes glutinous. It is also less miscible with water, and acquires a very disagreeable smell. By continuing upon the surface of the water, it became white, and its offensive smell went off in a few days. Oil of turpentine absorbed this air very fast, turning brown, and almost black. No inflammable air was formed, till I raised more of the acid air than the oil was able to absorb, and let it stand a considerable time; and still the air was but weakly inflammable. The same was the case with the oil of olives, in the last mentioned experiment; and it seems to be probable, that, the longer this acid air had continued in contact with the oil, the more phlogiston it would have extracted from it. It is not wholly improbable, but that, in the intermediate state, before it becomes inflammable air, it may be nearly of the nature of common air. Bees-wax absorbed this air very slowly. About the bigness of a hazel-nut of the wax being put to three ounce measures of the acid air, the air was diminished one half in two days, and, upon the admission of water, half of the remainder also disappeared. This air was strongly inflammable. Charcoal absorbed this air very fast. About one fourth of it was rendered immiscible in water, and was but weakly inflammable. A small bit of _phosphorus_, perhaps about half a grain, smoked, and gave light in the acid air, just as it would have done in common air confined. It was not sensibly wasted after continuing about twelve hours in that state, and the bulk of the air was very little diminished. Water being admitted to it absorbed it as before, except about one fifth of the whole. It was but weakly inflammable. Putting several pieces of _sulphur_ to this air, it was absorbed but slowly. In about twenty-four hours about one fifth of the quantity had disappeared; and water being admitted to the remainder, very little more was absorbed. The remainder was inflammable, and burned with a blue flame. Notwithstanding the affinity which this acid air appears to have with phlogiston, it is not capable of depriving all bodies of it. I found that dry wood, crusts of bread, and raw flesh, very readily imbibed this air, but did not part with any of their phlogiston to it. All these substances turned very brown, after they had been some time exposed to this air, and tasted very strongly of the acid when they were taken out; but the flesh, when washed in water, became very white, and the fibres easily separated from one another, even more than they would have done if it had been boiled or roasted[9]. When I put a piece of _saltpetre_ to this air it was presently surrounded with a white fume, which soon filled the whole vessel, exactly like the fume which bursts from the bubbles of nitrous air, when it is generated by a vigorous fermentation, and such as is seen when nitrous air is mixed with this acid air. In about a minute, the whole quantity of air was absorbed, except a very little, which might be the common air that had lodged upon the surface of the spirit of salt within the phial. A piece of _alum_ exposed to this air turned yellow, absorbed it as fast as the saltpetre had done, and was reduced by it to the form of a powder. Common salt, as might be expected, had no effect whatever on this marine acid air. I had also imagined, that if air diminished by the processes above-mentioned was affected in this manner, in consequence of its being saturated with phlogiston, a mixture of this acid air might imbibe that phlogiston, and render it wholesome again; but I put about one fourth of this air to a quantity of air in which metals had been calcined, without making any sensible alteration in it. I do not, however, infer from this, that air is not diminished by means of phlogiston, since the common air, like some other substances, may hold the phlogiston too fast, to be deprived of it by this acid air. I shall conclude my account of these experiments with observing, that the electric spark is visible in acid air, exactly as it is in common air; and though I kept making this spark a considerable time in a quantity of it, I did not perceive that any sensible alteration was made in it. A little inflammable air was produced, but not more than might have come from the two iron nails which I made use of in taking the sparks. FOOTNOTES: [9] It will be seen, in the second part of this work, that, in some of these processes, I had afterwards more success. SECTION X. MISCELLANEOUS OBSERVATIONS. 1. As many of the preceding observations relate to the _vinous_ and _putrefactive_ fermentations, I had the curiosity to endeavour to ascertain in what manner the air would be affected by the _acetous_ fermentation. For this purpose I inclosed a phial full of small beer in a jar standing in water; and observed that, during the first two or three days, there was an increase of the air in the jar, but from that time it gradually decreased, till at length there appeared to be a diminution of about one tenth of the whole quantity. During this time the whole surface of it was gradually covered with a scum, beautifully corrugated. After this there was an increase of the air till there was more than the original quantity; but this must have been fixed air, not incorporated with the rest of the mass; for, withdrawing the beer, which I found to be sour, after it had stood 18 or 20 days under the jar, and passing the air several times through cold water, the original quantity was diminished about one ninth. In the remainder a candle would not burn, and a mouse would have died presently. The smell of this air was exceedingly pungent, but different from that of the putrid effluvium. A mouse lived perfectly well in this air, thus affected with the acetous fermentation; after it had stood several days mixed with four times the quantity of fixed air. 2. All the kinds of factitious air on which I have yet made the experiment are highly noxious, except that which is extracted from saltpetre, or alum; but in this even a candle burned just as in common air[10]. In one quantity which I got from saltpetre a candle not only burned, but the flame was increased, and something was heard like a hissing, similar to the decrepitation of nitre in an open fire. This experiment was made when the air was fresh made, and while it probably contained some particles of nitre, which would have been deposited afterwards. The air was extracted from these substances by heating them in a gun-barrel, which was much corroded and soon spoiled by the experiment. What effect this circumstance may have had upon the air I have not considered. November 6, 1772, I had the curiosity to examine the state of a quantity of this air which had been extracted from saltpetre above a year, and which at first was perfectly wholesome; when, to my very great surprize, I found that it was become, in the highest degree, noxious. It made no effervescence with nitrous air, and a mouse died the moment it was put into it. I had not, however, washed it in rain-water quite ten minutes (and perhaps less time would have been sufficient) when I found, upon trial, that it was restored to its former perfectly wholesome state. It effervesced with nitrous air as much as the best common air ever does; and even a candle burned in it very well, which I had never before observed of any kind of noxious air meliorated by agitation in water. This series of facts, relating to air extracted from nitre, appear to me to be very extraordinary and important, and, in able hands, may lead to considerable discoveries. 3. There are many substances which impregnate common air in a very remarkable manner, but without making it noxious to animals. Among other things I tried volatile alkaline salts, and camphor; the latter of which I melted with a burning-glass, in air inclosed in a phial. The mouse, which was put into this air, sneezed and coughed very much, especially after it was taken out; but it presently recovered, and did not appear to have been sensibly injured. 4. Having made several experiments with a mixture of iron filings and brimstone, kneaded to a paste with water, I had the curiosity to try what would be the effect of substituting _brass dust_ in the place of the iron filings. The result was, that when this mixture had stood about three weeks, in a given quantity of air, it had turned black, but was not increased in bulk. The air also was neither sensibly increased nor decreased, but the nature of it was changed; for it extinguished flame, it would have killed a mouse presently, and was not restored by fixed air, which had been mixed with it several days. 5. I have frequently mentioned my having, at one time, exposed equal quantities of different kinds of air in jars standing in boiled water. _Common air_ in this experiment was diminished four sevenths, and the remainder extinguished flame. This experiment demonstrates that water does not absorb air equally, but that it decomposes it, taking one part, and leaving the rest. To be quite sure of this fact, I agitated a quantity of common air in boiled water, and when I had reduced it from eleven ounce measures to seven, I found that it extinguished a candle, but a mouse lived in it very well. At another time a candle barely went out when the air was diminished one third, and at other times I have found this effect lake place at other very different degrees of diminution. This difference I attribute to the differences in the state of the water with respect to the air contained in it; for sometimes it had stood longer than at other times before I made use of it. I also used distilled-water, rain-water, and water out of which the air had been pumped, promiscuously with rain water. I even doubt, not but that, in a certain state of the water, there might be no sensible difference in the bulk of the agitated air, and yet at the end of the process it would extinguish a candle, air being supplied from the water in the place of that part of the common air which had been absorbed. It is certainly a little extraordinary that the very same process should so far mend putrid air, as to reduce it to the standard of air in which candles have burned out; and yet that it should so far injure common and wholesome air as to reduce it to about the same standard: but so the fact certainly is. If air extinguish flame in consequence of its being previously saturated with phlogiston, it must, in this case, have been transferred from the water to the air, and it is by no means inconsistent with this hypothesis to suppose, that, if the air be over saturated with phlogiston, the water will imbibe it, till it be reduced to the same proportion that agitation in water would have communicated to it. To a quantity of common air, thus diminished by agitation in water, till it extinguished a candle, I put a plant, but it did not so far restore it as that a candle would burn in it again; which to me appeared not a little extraordinary, as it did not seem to be in a worse state than air in which candles had burned out, and which had never failed to be restored by the same means. I had no better success with a quantity of permanent air which I had collected from my pump-water. Indeed these experiments were begun before I was acquainted with that property of nitrous air, which makes it so accurate a measure of the goodness of other kinds of air; and it might perhaps be rather too late in the year when I made the experiments. Having neglected these two jars of air, the plants died and putrefied in both of them; and then I found the air in them both to be highly noxious, and to make no effervescence with nitrous air. I found that a pint of my pump-water contained about one fourth of an ounce measure of air, one half of which was afterwards absorbed by standing in fresh pump-water. A candle would not burn in this air, but a mouse lived in it very well. Upon the whole, it seemed to be in about the same state as air in which a candle had burned out. 6. I once imagined that, by mere _stagnation_, air might become unfit for respiration, or at least the burning of candles; but if this be the case, and the change be produced gradually, it must require a long time for the purpose. For on the 22d of September 1772, I examined a quantity of common air, which had been kept in a phial, without agitation, from May 1771, and found it to be in no respect worse than fresh air, even by the test of the nitrous air. 7. The crystallization of nitre makes no sensible alteration in the air in which the process is made. For this purpose I dissolved as much nitre as a quantity of hot water would contain, and let it cool under a receiver, standing in water. 8. November 6, 1772, a quantity of inflammable air, which, by long keeping, had come to extinguish flame, I observed to smell very much like common air in which a mixture of iron filings and brimstone had stood. It was not, however, quite so strong, but it was equally noxious. 9. Bismuth and nickel are dissolved in the marine acid with the application of a considerable degree of heat; but little or no air is got from either of them; but, what I thought a little remarkable, both of them smelled very much like Harrowgate water, or liver of sulphur. This smell I have met with several times in the course of my experiments, and in processes very different from one another. FOOTNOTES: [10] Experiments, of which an account will be given in the second part of this work, make it probable, that though a candle burned even _more than well_ in this air, an animal would not have lived in it. At the time of this first publication, however, I had no idea of this being possible in nature. PART II. _Experiments and Observations made in the Year 1773, and the Beginning of 1774._ SECTION I. _Observations on ALKALINE AIR._ After I had made the discovery of the _marine acid air_, which the vapour of spirit of salt may properly enough be called, and had made those experiments upon it, of which I have given an account in the former part of this work, and others which I propose to recite in this part; it occurred to me, that, by a process similar to that by which this _acid_ air is expelled from the spirit of salt, an _alkaline_ air might be expelled from substances containing volatile alkali. Accordingly I procured some volatile spirit of sal ammoniac, and having put it into a thin phial, and heated it with the flame of a candle, I presently found that a great quantity of vapour was discharged from it; and being received in a vessel of quicksilver, standing in a bason of quicksilver, it continued in the form of a transparent and permanent air, not at all condensed by cold; so that I had the same opportunity of making experiments upon it, as I had before on the acid air, being in the same favourable circumstances. With the same ease I also procured this air from _spirit of hartshorn_, and _sal volatile_ either in a fluid or solid form, i. e. from those volatile alkaline salts which are produced by the distillation of sal ammoniac with fixed alkalis. But in this case I soon found that the alkaline air I procured was not pure; for the fixed air, which entered into the composition of my materials, was expelled along with it. Also, uniting again with the alkaline air, in the glass tube through which they were conveyed, they stopped it up, and were often the means of bursting my vessels. While these experiments were new to me, I imagined that I was able to procure this air with peculiar advantage and in the greatest abundance, either from the salts in a dry state, when they were just covered with water, or in a perfectly fluid state; for, upon applying a candle to the phials in which they were contained, there was a most astonishing production of air; but having examined it, I found it to be chiefly fixed air, especially after the first or second produce from the same materials; and removing my apparatus to a trough of water and using the water instead of quicksilver, I found that it was not presently absorbed by it. This, however, appears to be an easy and elegant method of procuring fixed air, from a small quantity of materials, though there must be a mixture of alkaline air along with it; as it is by means of its combination with this principle only, that it is possible, that so much fixed air should be retained in any liquid. Water, at least, we know, cannot be made to contain much more than its own bulk of fixed air. After this disappointment, I confined myself to the use of that volatile spirit of sal ammoniac which is procured by a distillation with slaked lime, which contains no fixed air; and which seems, in a general state, to contain about as much alkaline air, as an equal quantity of spirit of salt contains of the acid air. Wanting, however, to procure this air in greater quantities, and this method being rather expensive, it occurred to me, that alkaline air might, probably, be procured, with the most ease and convenience, from the original materials, mixed in the same proportions that chemists had found by experience to answer the best for the production of the volatile spirit of sal ammoniac. Accordingly I mixed one fourth of pounded sal ammoniac, with three fourths of slaked lime; and filling a phial with the mixture, I presently found it completely answered my purpose. The heat of a candle expelled from this mixture a prodigious quantity of alkaline air; and the same materials (as much as filled an ounce phial) would serve me a considerable time, without changing; especially when, instead of a glass phial, I made use of a small iron tube, which I find much more convenient for the purpose. As water soon begins to rise in this process, it is necessary, if the air is intended to be conveyed perfectly _dry_ into the vessel of quicksilver, to have a small vessel in which this water (which is the common volatile spirit of sal ammoniac) may be received. This small vessel must be interposed between the vessel which contains the materials for the generation of the air, and that in which it is to be received, as _d_ fig. 8. This _alkaline_ air being perfectly analogous to the _acid_ air, I was naturally led to investigate the properties of it in the same manner, and nearly in the same order. From this analogy I concluded, as I presently found to be the fact, that this alkaline air would be readily imbibed by water, and, by its union with it, would form a volatile spirit of sal ammoniac. And as the water, when admitted to the air in this manner, confined by quicksilver, has an opportunity of fully saturating itself with the alkaline vapour, it is made prodigiously stronger than any volatile spirit of sal ammoniac that I have ever seen; and I believe stronger than it can be made in the common way. In order to ascertain what addition, with respect to quantity and weight, water would acquire by being saturated with alkaline air, I put 1-1/4 grains of rain-water into a small glass tube, closed at one end with cement, and open at the other, the column of water measuring 7/10 of an inch; and having introduced it through the quicksilver into a vessel containing alkaline air, observed that it absorbed 7/8 of an ounce measure of the _air_, and had then gained about half a grain in weight, and was increased to 8-1/2 tenths of an inch in length. I did not make a second experiment of this kind, and therefore will not answer for the exactness of these proportions in future trials. What I did sufficiently answered my purpose, in a general view of the subject. When I had, at one time, saturated a quantity of distilled water with alkaline air, so that a good deal of the air remained unabsorbed on the surface of the water, I observed that, as I continued to throw up more air, a considerable proportion of it was imbibed, but not the whole; and when I had let the apparatus stand a day, much more of the air that lay on the surface was imbibed. And after the water would imbibe no more of the _old_ air, it imbibed _new_. This shews that water requires a considerable time to saturate itself with this kind of air, and that part of it more readily unites with water than the rest. The same is also, probably, the case with all the kinds of air with which water can be impregnated. Mr. Cavendish made this observation with respect to fixed air, and I repeated the whole process above-mentioned with acid air, and had precisely the same result. The alkaline water which I procured in this experiment was, beyond comparison, stronger to the smell, than any spirit of sal ammoniac that I had seen. This experiment led me to attempt the making of spirit of sal ammoniac in a larger quantity, by impregnating distilled water with this alkaline air. For this purpose I filled a piece of a gun-barrel with the materials above-mentioned, and luted to the open end of it a small glass tube, one end of which was bent, and put within the mouth of a glass vessel, containing a quantity of distilled water upon quicksilver, standing in a bason of quicksilver, as in fig. 7. In these circumstances the heat of the fire, applied gradually, expelled the alkaline air, which, passing through the tube, and the quicksilver, came at last to the water, which, in time, became fully saturated with it. By this means I got a very strong alkaline liquor, from which I could again expel the alkaline air which I had put into it, whenever it happened to be more convenient to me to get it in that manner. This process may easily be performed in a still larger way; and by this means a liquor of the same nature with the volatile spirit of sal ammoniac, might be made much stronger, and much cheaper, than it is now made. Having satisfied myself with respect to the relation that alkaline air bears to water, I was impatient to find what would be the consequence of mixing this new air with the other kinds with which I was acquainted before, and especially with _acid_ air; having a notion that these two airs, being of opposite natures, might compose a _neutral air_, and perhaps the very same thing with common air. But the moment that these two kinds of air came into contact, a beautiful white cloud was formed, and presently filled the whole vessel in which they were contained. At the same time the quantity of air began to diminish, and, at length, when the cloud was subsided, there appeared to be formed a solid _while salt_, which was found to be the common _sal ammoniac_, or the marine acid united to the volatile alkali. The first quantity that I produced immediately deliquesced, upon being exposed to the common air; but if it was exposed in a very dry and warm place, it almost all evaporated, in a white cloud. I have, however, since, from the same materials, produced the salt above-mentioned in a state not subject to deliquesce or evaporate. This difference, I find, is owing to the proportion of the two kinds of air in the compound. It is only volatile when there is more than a due proportion of either of the constituent parts. In these cases the smell of the salts is extremely pungent, but very different from one another; being manifestly acid, or alkaline, according to the prevalence of each of these airs respectively. _Nitrous air_ admitted to alkaline air likewise occasioned a whitish cloud, and part of the air was absorbed; but it presently grew clear again; leaving only a little dimness on the sides of the vessel. This, however, might be a kind of salt, formed by the union of the two kinds of air. There was no other salt formed that I could perceive. Water being admitted to this mixture of nitrous and alkaline air presently absorbed the latter, and left the former possessed of its peculiar properties. _Fixed air_ admitted to alkaline air formed oblong and slender crystals, which crossed one another, and covered the sides of the vessel in the form of net-work. These crystals must be the same thing with the volatile alkalis which chemists get in a solid form, by the distillation of sal ammoniac with fixed alkaline salts. _Inflammable air_ admitted to alkaline air exhibited no particular appearance. Water, as in the former experiment, absorbed the alkaline air, and left the inflammable air as it was before. It was remarkable, however, that the water which was admitted to them became whitish, and that this white cloud settled, in the form of a white powder, to the bottom of the vessel. Alkaline air mixed with _common air_, and standing together several days, first in quicksilver, and then in water (which absorbed the alkaline air) it did not appear that there was any change produced in the common air: at least it was as much diminished by nitrous air as before. The same was the case with a mixture of acid air and common air. Having mixed air that had been diminished by the fermentation of a mixture of iron filings and brimstone with alkaline air, the water absorbed the latter, but left the former, with respect to the test of nitrous air (and therefore, as I conclude, with respect to all its properties) the same that it was before. _Spirit of wine_ imbibes alkaline air as readily as water, and seems to be as inflammable afterwards as before. Alkaline air contracts no union with _olive oil_. They were in contact almost two days, without any diminution of the air. Oil of turpentine, and essential oil of mint, absorbed a very small quantity of alkaline air, but were not sensibly changed by it. _Ether_, however, imbibed alkaline air pretty freely; but it was afterwards as inflammable as before, and the colour was not changed. It also evaporated as before, but I did not attend to this last circumstance very accurately. _Sulphur_, _nitre_, _common salt_, and _flints_, were put to alkaline air without imbibing any part of it; but _charcoal_, _spunge_, bits of _linen cloth_, and other substances of that nature, seemed to condense this air upon their surfaces; for it began to diminish immediately upon their being put to it; and when they were taken out the alkaline smell they had contracted was so pungent as to be almost intolerable, especially that of the spunge. Perhaps it might be of use to recover persons from swooning. A bit of spunge, about as big as a hazel nut, presently imbibed an ounce measure of alkaline air. A piece of the inspissated juice of _turnsole_ was made very dry and warm, and yet it imbibed a great quantity of the air; by which it contracted a most pungent smell, but the colour of it was not changed. _Alum_ undergoes a very remarkable change by the action of alkaline air. The outward shape and size remain the same, but the internal structure is quite changed, becoming opaque, beautifully white, and, to appearance, in all respects, like alum which had been roasted; and so as not to be at all affected by a degree of heat that would have reduced it to that state by roasting. This effect is produced slowly; and if a piece of alum be taken out of alkaline air before the operation is over, the inside will be transparent, and the outside, to an equal thickness, will be a white crust. I imagine that the alkaline vapour seizes upon the water that enters into the constitution of crude alum, and which would have been expelled by heat. Roasted alum also imbibes alkaline air, and, like the raw alum that has been exposed to it, acquires a taste that is peculiarly disagreeable. _Phosphorus_ gave no light in alkaline air, and made no lasting change in its dimensions. It varied, indeed, a little, being sometimes increased and sometimes diminished, but after a day and a night, it was in the same state as at the first. Water absorbed this air just as if nothing had been put to it. Having put some _spirit of salt_ to alkaline air, the air was presently absorbed, and a little of the white salt above-mentioned was formed. A little remained unabsorbed, and transparent, but upon the admission of common air to it, it instantly became white. _Oil of vitriol_, also formed a white salt with alkaline air, and this did not rise in white fumes. Acid air, as I have observed in my former papers, extinguishes a candle. Alkaline air, on the contrary, I was surprized to find, is slightly inflammable; which, however, seems to confirm the opinion of chemists, that the volatile alkali contains phlogiston. I dipped a lighted candle into a tall cylindrical vessel, filled with alkaline air, when it went out three or four times successively; but at each time the flame was considerably enlarged, by the addition of another flame, of a pale yellow colour; and at the last time this light flame descended from the top of the vessel to the bottom. At another time, upon presenting a lighted candle to the mouth of the same vessel, filled with the same kind of air, the yellowish flame ascended two inches higher than the flame of the candle. The electric spark taken in alkaline air is red, as it is in common inflammable air. Though alkaline air be inflammable, it appeared, by the following experiment, to be heavier than the common inflammable air, as well as to contract no union with it. Into a vessel containing a quantity of inflammable air, I put half as much alkaline air, and then about the same quantity of acid air. These immediately formed a white cloud, but it did not rise within the space that was occupied by the inflammable air; so that this latter had kept its place above the alkaline air, and had not mixed with it. That alkaline air is lighter than acid air is evident from the appearances that attend the mixture, which are indeed very beautiful. When acid air is introduced into a vessel containing alkaline air, the white cloud which they form appears at the bottom only, and ascends gradually. But when the alkaline air is put to the acid, the whole becomes immediately cloudy, quite to the top of the vessel. In the last place, I shall observe that alkaline air, as well as acid, dissolves _ice_ as fast as a hot fire can do it. This was tried when both the kinds of air, and every instrument made use of in the experiment, had been exposed to a pretty intense frost several hours. In both cases, also, the water into which the ice was melted dissolved more ice, to a considerable quantity. SECTION II. _Of COMMON AIR diminished and made noxious by various processes._ It will have been observed that, in the first publication of my papers, I confined myself chiefly to the narration of the new _facts_ which I had discovered, barely mentioning any _hypotheses_ that occurred to me, and never seeming to lay much stress upon them. The reason why I was so much upon my guard in this respect was, left, in consequence of attaching myself to any hypothesis too soon, the success of my future inquiries might be obstructed. But subsequent experiments having thrown great light upon the preceding ones and having confirmed the few conjectures I then advanced, I may now venture to speak of my hypotheses with a little less diffidence. Still, however, I shall be ready to relinquish any notions I may now entertain, if new facts should hereafter appear not to favour them. In a great variety of cases I have observed that there is a remarkable _diminution_ of common, or respirable air, in proportion to which it is always rendered unfit for respiration, indisposed to effervesce with nitrous air, and incapable of farther diminution from any other cause. The circumstances which produce this effect I had then observed to be the burning of candles, the respiration of animals, the putrefaction of vegetables or animal substances, the effervescence of iron filings and brimstone, the calcination of metals, the fumes of charcoal, the effluvia of paint made of white-lead and oil, and a mixture of nitrous air. All these processes, I observed, agree in this one circumstance, and I believe in no other, that the principle which the chemists call _phlogiston_ is set loose; and therefore I concluded that the diminution of the air was, in some way or other, the consequence of the air becoming overcharged with phlogiston,[11] and that water, and growing vegetables, tend to restore this air to a state fit for respiration, by imbibing the superfluous phlogiston. Several experiments which I have since made tend to confirm this supposition. Common air, I find, is diminished, and rendered noxious, by _liver of sulphur_, which the chemists say exhales phlogiston, and nothing else. The diminution in this case was one fifth of the whole, and afterwards, as in other similar cases, it made no effervescence with nitrous air. I found also, after Dr. Hales, that air is diminished by _Homberg's pyrophorus_. The same effect is produced by firing _gunpowder_ in air. This I tried by firing the gunpowder in a receiver half exhausted, by which the air was rather more injured than it would have been by candles burning in it. Air is diminished by a cement made with one half common coarse turpentine and half bees-wax. This was the result of a very casual observation. Having, in an air-pump of Mr. Smeaton's construction, closed that end of the syphon-gage, which is exposed to the outward air, with this cement (which I knew would make it perfectly air-light) instead of sealing it hermetically; I observed that, in a course of time, the quicksilver in that leg kept continually rising, so that the measures I marked upon it were of no use to me; and when I opened that end of the tube, and closed it again, the same consequence always took place. At length, suspecting that this effect must have arisen from the bit of _cement_ diminishing the air to which it was exposed, I covered all the inside of a glass tube with it, and one end of it being quite closed with the cement, I set it perpendicular, with its open end immersed in a bason of quicksilver; and was presently satisfied that my conjecture was well founded: for, in a few days, the quicksilver rose so much within the tube, that the air in the inside appeared to be diminished about one sixth. To change this air I filled the tube with quicksilver, and pouring it out again, I replaced the tube in its former situation; when the air was diminished again, but not so fast as before. The same lining of cement diminished the air a third time. How long it will retain this power I cannot tell. This cement had been made several months before I made this experiment with it. I must observe, however, that another quantity of this kind of cement, made with a finer and more liquid turpentine, had not the power of diminishing air, except in a very small proportion. Also the common red cement has this property in the same small degree. Common air, however, which had been confined in a glass vessel lined with this cement about a month, was so far injured that a candle would not burn in it. In a longer time it would, I doubt not, have become thoroughly noxious. Iron that has been suffered to rust in nitrous air diminishes common air very fast, as I shall have occasion to mention when I give a continuation of my experiments on nitrous air. Lastly, the same effect, I find, is produced by the _electric spark_, though I had no expectation of this event when I made the experiment. This experiment, however, and those which I have made in pursuance of it, has fully confirmed another of my conjectures, which relates to the _manner_ in which air is diminished by being overcharged with phlogiston, viz. the phlogiston having a nearer affinity with some of the constituent parts of the air than the fixed air which enters into the composition of it, in consequence of which the fixed air is precipitated. This I first imagined from perceiving that lime-water became turbid by burning candles over it, p. 44. This was also the case with lime-water confined in air in which an animal substance was putrefying, or in which an animal died, p. 79. and that in which charcoal was burned, p. 81. But, in all these cases, there was a possibility of the fixed air being discharged from the candle, the putrefying substance, the lungs of the animal, or the charcoal. That there is a precipitation of lime when nitrous air is mixed with common air, I had not then observed, but I have since found it to be the case. That there was no precipitation of lime when brimstone was burned, I observed, p. 45. might be owing to the fixed air and the lime uniting with the vitriolic acid, and making a salt, which was soluble in water; which salt I, indeed, discovered by the evaporation of the water. I also observed, p. 46, 105. that diminished air being rather lighter than common air is a circumstance in favour of the fixed, or the heavier part of the common air, having been precipitated. It was upon this idea, together with others similar to it, that I took so much pains to mix fixed air with air diminished by respiration or putrefaction, in order to make it fit for respiration again; and I thought that I had, in general, succeeded to a considerable degree, p. 99, &c. I will add, also, what I did not mention before, that I once endeavoured, but without effect, to preserve mice alive in the same unchanged air, by supplying them with fixed air, when the air in which they were confined began to be injured by their respiration. Without effect, also, I confined for some months, a quantity of quick lime in a given quantity of common air, thinking it might extract the fixed air from it. The experiments which I made with electricity were solely intended to ascertain what has often been attempted, but, as far as I know, had never been fully accomplished, viz. to change the blue colour of liquors, tinged with vegetable juices, red. For this purpose I made use of a glass tube, about one tenth of an inch diameter in the inside, as in fig. 16. In one end of this I cemented a piece of wire _b_, on which I put a brass ball. The lower part from _a_ was filled with water tinged blue, or rather purple, with the juice of turnsole, or archil. This is easily done by an air-pump, the tube being set in a vessel of the tinged water. Things being thus prepared, I perceived that, after I had taken the electric spark, between the wire _b_, and the liquor at _a_, about a minute, the upper part of it began to look red, and in about two minutes it was very manifestly so; and the red part, which was about a quarter of an inch in length, did not readily mix with the rest of the liquor. I observed also, that if the tube lay inclined while I took the sparks, the redness extended twice as far on the lower side as on the upper. The most important, though the least expected observation, however, was that, in proportion as the liquor became red, it advanced nearer to the wire, so that the space of air in which the sparks were taken was diminished; and at length I found that the diminution was about one fifth of the whole space; after which more electrifying produced no sensible effect. To determine whether the cause of the change of colour was in the _air_, or in the _electric matter_, I expanded the air which had been diminished in the tube by means of an air-pump, till it expelled all the liquor, and admitted fresh blue liquor into its place; but after that, electricity produced no sensible effect, either on the air, or on the liquor; so that it was evident that the electric matter had decomposed the air, and had made it deposite something that was of an acid nature. In order to determine whether the _wire_ had contributed any thing to this effect, I used wires of different metals, iron, copper, brass, and silver; but the result was the very same with them all. It was also the same when, by means of a bent glass tube, I made the electric spark without any wire at all, in the following manner. Each leg of the tube, fig. 19. stood in a bason of quicksilver; which, by means of an air-pump, was made to ascend as high as _a, a_, in each leg, while the space between _a_ and _b_ in each contained the blue liquor, and the space between _b_ and _b_ contained common air. Things being thus disposed, I made the electric spark perform the circuit from one leg to the other, passing from the liquor in one leg of the tube to the liquor in the other leg, through the space of air. The effect was, that the liquor, in both the legs, became red, and the space of air between them was contracted, as before. Air thus diminished by electricity makes no effervescence with, and is no farther diminished by a mixture of nitrous air; so that it must have been in the highest degree noxious, exactly like air diminished by any other process. In order to determine what the _acid_ was, which was deposited by the air, and which changed the colour of the blue liquor, I exposed a small quantity of the liquor so changed to the common air, and found that it recovered its blue colour, exactly as water, tinged with the same blue, and impregnated with fixed air, will do. But the following experiment was still more decisive to this purpose. Taking the electric spark upon _lime-water_, instead of the blue liquor, the lime was precipitated as the air diminished. From these experiments it pretty clearly follows, that the electric matter either is, or contains phlogiston; since it does the very same thing that phlogiston does. It is also probable, from these experiments, that the sulphureous smell, which is occasioned by electricity, being very different from that of fixed air, the phlogiston in the electric matter itself may contribute to it. It was now evident that common air diminished by any one of the processes above-mentioned being the same thing, as I have observed, with air diminished by any other of them (since it is not liable to be farther diminished by any other) the loss which it sustains, in all the cases, is, in part, that of the _fixed air_ which entered into its constitution. The fixed air thus precipitated from common air by means of phlogiston unites with lime, if any lime water be ready to receive it, unless there be some other substance at hand, with which it has a greater affinity, as the _calces of metals_. If the whole of the diminution of common air was produced by the deposition of fixed air, it would be easy to ascertain the quantity of fixed air that is contained in any given quantity of common air. But it is evident that the whole of the diminution of common air by phlogiston is not owing to the precipitation of fixed air, because a mixture of nitrous air will make a great diminution in all kinds of air that are fit for respiration, even though they never were common air, and though nothing was used in the process for generating them that can be supposed to yield fixed air. Indeed, it appears, from some of the experiments, that the diminution of some of these kinds of air by nitrous air is so great, and approaches so nearly to the quantity of the diminution of common air by the same process, as to shew that, unless they be very differently affected by phlogiston, very little is to be allowed to the loss of fixed air in the diminution of common air by nitrous air. The kinds of air on which this experiment was made were inflammable air, nitrous air diminished by iron filings and brimstone, and nitrous air itself; all of which are produced by the solution of metals in acids; and also on common air diminished and made noxious, and therefore deprived of its fixed air by phlogistic processes; and they were restored to a great degree of purity by agitation in water, out of which its own air had been carefully boiled. To five parts of inflammable air, which had been agitated in water till it was diminished about one half (at which time part of it fired with a weak explosion) I put one part of nitrous air, which diminished it one eighth of the whole. This was done in lime-water, without any precipitation of lime. To compare this with common air, I mixed the same quantity, viz. five parts of this, and one part of nitrous air: when considerable crust of lime was formed upon the surface of the lime water, though the diminution was very little more than in the former process. It is possible, however, that the common air might have taken more nitrous air before it was fully saturated, so as to begin to receive an addition to its bulk. I agitated in water a quantity of nitrous air phlogisticated with iron filings and brimstone, and found it to be so far restored, that three fourths of an ounce measure of nitrous air being put to two ounce measures of it, made no addition to it. But the most remarkable of these experiments is that which I made with _nitrous air_ itself which I had no idea of the possibility of reducing to a state fit for respiration by any process whatever, at the time of my former publication on this subject. This air, however, itself, without any previous phlogistication, is purified by agitation in water till it is diminished by fresh nitrous air, and to a very considerable degree. In a pretty long time I agitated nitrous air in water, supplying it from time to time with more, as the former quantity diminished, till only one eighteenth of the whole quantity remained; in which state it was so wholesome, that a mouse lived in two ounce measures of it more than ten minutes, without shewing any sign of uneasiness; so that I concluded it must have been about as good as air in which candles had burned out. After agitating it again in water, I put one part of fresh nitrous air to five parts of this air, and it was diminished one ninth part. I then agitated it a third time, and putting more nitrous air to it, it was diminished again in the same proportion, and so a fourth time; so that, by continually repeating the process, it would, I doubt not, have been all absorbed. These processes were made in lime-water, without forming any incrustation on the surface of it. Lastly, I took a quantity of common air, which had been diminished and made noxious by phlogistic processes; and when it had been agitated in water, I found that it was diminished by nitrous air, though not so much as it would have been at the first. After cleansing it a second time, it was diminished again by the same means; and, after that, a third time; and thus there can be no doubt but that, in time, the whole quantity would have disappeared. For I have never found that agitation in water, deprived of its own air, made any addition to a quantity of noxious air; though, _a priori_, it might have been imagined that, as a saturation with phlogiston diminishes air, the extraction of phlogiston would increase the bulk of it. On the contrary, agitation in water always diminished noxious air a little; indeed, if water be deprived of all its own air, it is impossible to agitate any kind of air in it without some loss. Also, when noxious air has been restored by plants, I never perceived that it gained any addition to its bulk by that means. There was no incrustation of the lime-water in the above-mentioned experiment. It is not a little remarkable, that those kinds of air which never had been common air, as inflammable air, phlogisticated nitrous air, and nitrous air itself, when rendered wholesome by agitation in water, should be more diminished by fresh nitrous air, than common air which had been made noxious, and restored by the same process; and yet, from the few trials that I have made, I could not help concluding that this is the case. In this course of experiments I was very near deceiving myself, in consequence of transferring the nitrous air which I made use of in a bladder, in the manner described, p. 15. fig. 9. so as to conclude that there was a precipitation of lime in all the above-mentioned cases, and that even nitrous air itself produced that effect. But after repeated trials, I found that there was no precipitation of lime, except, in the first diminution of common air, when the nitrous air was transferred in a glass vessel. That the calces of metals contain air, of some kind or other, and that this air contributes to the additional weight of the calces, above that of the metals from which they are made, had been observed by Dr. Hales; and Mr. Hartley had informed me, that when red-lead is boiled in linseed oil, there is a prodigious discharge of air before they incorporate. I had likewise found, that no weight is either gained or lost by the calcination of tin in a close glass vessel; but I purposely deferred making any more experiments on the subject, till we should have some weather in which I could make use of a large burning lens, which I had provided for that and other purposes; but, in the mean time, I was led to the discovery in a different manner. Having, by the last-recited experiments, been led to consider the electric matter as phlogiston, or something containing phlogiston, I was endeavouring to revivify the calx of lead with it; when I was surprized to perceive a considerable generation of air. It occurred to me, that possibly this effect might arise from the _heat_ communicated to the red-lead by the electric sparks, and therefore I immediately filled a small phial with the red-lead, and heating it with a candle, I presently expelled from it a quantity of air about four or five times the bulk of the lead, the air being received in a vessel of quicksilver. How much more air it would have yielded, I did not try. Along with the air, a small quantity of _water_ was likewise thrown out; and it immediately occurred to me, that this water and air together must certainly be the cause of the addition of weight in the calx. It still remained to examine what kind of air this was; but admitting water to it, I found that it was imbibed by it, exactly like _fixed air_, which I therefore immediately concluded it must be[12]. After this, I found that Mr. Lavoisier had completely discovered the same thing, though his apparatus being more complex, and less accurate than mine, he concluded that more of the air discharged from the calces of metals was immiscible with water than I found it to be. It appeared to me that I had never obtained fixed air more pure. It being now pretty clearly determined, that common air is made to deposit the fixed air which entered into the constitution of it, by means of phlogiston, in all the cases of diminished air, it will follow, that in the precipitation of lime, by breathing into lime-water the fixed air, which incorporates with lime, comes not from the lungs, but from the common air, decomposed by the phlogiston exhaled from them, and discharged, after having been taken in with the aliment, and having performed its function in the animal system. Thus my conjecture is more confirmed, that the cause of the death of animals in confined air is not owing to the want of any _pabulum vitæ_, which the air had been supposed to contain, but to the want of a discharge of the phlogistic matter, with which the system was loaded; the air, when once saturated with it, being no sufficient _menstruum_ to take it up. The instantaneous death of animals put into air so vitiated, I still think is owing to some _stimulus_, which, by causing immediate, universal and violent convulsions, exhausts the whole of the _vis vitæ_ at once; because, as I have observed, the manner of their death is the very same in all the different kinds of noxious air. To this section on the subject of diminished, and noxious air, or as it might have been called _phlogisticated air_, I shall subjoin a letter which I addressed to Sir John Pringle, on the noxious quality of the effluvia of putrid marshes, and which was read at a meeting of the Royal Society, December 16, 1773. This letter which is printed in the Philosophical Transactions, Vol. 74, p. 90. is immediately followed by another paper, to which I would refer my reader. It was written by Dr. Price, who has so greatly distinguished himself, and done such eminent service to his country, and to mankind, by his calculations relating to the probabilities of human life, and was suggested by his hearing this letter read at the Royal Society. It contains a confirmation of my observations on the noxious effects of stagnant waters by deductions from Mr. Muret's account of the Bills of Mortality for a parish situated among marshes, in the district of Vaud, belonging to the Canton of Bern in Switzerland. To Sir JOHN PRINGLE, Baronet. DEAR SIR, Having pursued my experiments on different kinds of air considerably farther, in several respects, than I had done when I presented the last account of them to the Royal Society; and being encouraged by the favourable notice which the Society has been pleased to take of them, I shall continue my communications on this subject; but, without waiting for the result of a variety of processes, which I have now going on, or of other experiments, which I propose to make, I shall, from time to time, communicate such detached articles, as I shall have given the most attention to, and with respect to which, I shall have been the most successful in my inquiries. Since the publication of my papers, I have read two treatises, written by Dr. Alexander, of Edinburgh, and am exceedingly pleased with the spirit of philosophical inquiry, which they discover. They appear to me to contain many new, curious, and valuable observations; but one of the _conclusions_, which he draws from his experiments, I am satisfied, from my own observations, is ill founded, and from the nature of it, must be dangerous. I mean his maintaining, that there is nothing to be apprehended from the neighbourhood of putrid marshes. I was particularly surprised, to meet with such an opinion as this, in a book inscribed to yourself, who have so clearly explained the great mischief of such a situation, in your excellent treatise _on the diseases of the army_. On this account, I have thought it not improper, to address to you the following observations and experiments, which I think clearly demonstrate the fallacy of Dr. Alexander's reasoning, indisputably establish your doctrine, and indeed justify the apprehensions of all mankind in this case. I think it probable enough, that putrid matter, as Dr. Alexander has endeavoured to prove, will preserve other substances from putrefaction; because, being already saturated with the putrid effluvium, it cannot readily take any more; but Dr. Alexander was not aware, that air thus loaded with putrid effluvium is exceedingly noxious when taken into the lungs. I have lately, however, had an opportunity of fully ascertaining how very noxious such air is. Happening to use at Calne, a much larger trough of water, for the purpose of my experiments, than I had done at Leeds, and not having fresh water so near at hand as I had there, I neglected to change it, till it turned black, and became offensive, but by no means to such a degree, as to deter me from making use of it. In this state of the water, I observed bubbles of air to rise from it, and especially in one place, to which some shelves, that I had in it, directed them; and having set an inverted glass vessel to catch them, in a few days I collected, a considerable quantity of this air, which issued spontaneously from the putrid water; and putting nitrous air to it, I found that no change of colour or diminution ensued, so that it must have been, in the highest degree, noxious. I repeated the same experiment several times afterwards, and always with the same result. After this, I had the curiosity to try how wholesome air would be affected by this water; when, to my real surprise, I found, that after only one minute's agitation in it, a candle would not burn in it; and, after three or four minutes, it was in the same state with the air, which had issued spontaneously from the same water. I also found, that common air, confined in a glass vessel, in _contact_ only with this water, and without any agitation, would not admit a candle to burn in it after two days. These facts certainly demonstrate, that air which either arises from stagnant and putrid water, or which has been for some time in contact with it, must be very unfit for respiration; and yet Dr. Alexander's opinion is rendered so plausible by his experiments, that it is very possible that many persons may be rendered secure, and thoughtless of danger, in a situation in which they must necessarily breathe it. On this account, I have thought it right to make this communication as early as I conveniently could; and as Dr. Alexander appears to be an ingenuous and benevolent man, I doubt not but he will thank me for it. That air issuing from water, or rather from the soft earth, or mud, at the bottom of pits containing water, is not always unwholesome, I have also had an opportunity of ascertaining. Taking a walk, about two years ago, in the neighbourhood of Wakefield, in Yorkshire, I observed bubbles of air to arise, in remarkably great plenty, from a small pool of water, which, upon inquiry, I was informed had been the place, where some persons had been boring the ground, in order to find coal. These bubbles of air having excited my curiosity, I presently returned, with a bason, and other vessels proper for my purpose, and having stirred the mud with a long stick, I soon got about a pint of this air; and, examining it, found it to be good, common air; at least a candle burned in it very well. I had not then discovered the method of ascertaining the goodness of common air, by a mixture of nitrous air. Previous to the trial, I had suspected that this air would have been found to be inflammable. I shall conclude this letter with observing, that I have found a remarkable difference in different kinds of water, with respect to their effect on common air agitated in them, and which I am not yet able to account for. If I agitate common air in the water of a deep well, near my house in Calne, which is hard, but clear and sweet, a candle will not burn in it after three minutes. The same is the case with the rain-water, which I get from the roof of my house. But in distilled water, or the water of a spring-well near the house, I must agitate the air about twenty minutes, before it will be so much injured. It may be worth while, to make farther experiments with respect to this property of water. In consequence of using the rain-water, and the well-water above mentioned, I was very near concluding, contrary to what I have asserted in this treatise, that common air suffers a decomposition by great rarefaction. For when I had collected a considerable quantity of air, which had been rarefied about four hundred times, by an excellent pump made for me by Mr. Smeaton, I always found, that if I filled my receivers with the water above mentioned, though I did it so gradually as to occasion as little agitation as possible, a candle would not burn in the air that remained in them. But when I used distilled water, or fresh spring-water, I undeceived myself. I think myself honoured by the attention, which, from the first, you have given to my experiments, and am, with the greatest respect, Dear Sir, Your most obliged Humble Servant, London, 7 Dec. 1773. J. PRIESTLEY. POSTSCRIPT. I cannot help expressing my surprize, that so clear and intelligible an account, of Mr. SMEATON'S air-pump, should have been before the public so long, as ever since the publication of the forty-seventh volume of the Philosophical Transactions, printed in 1752, and yet that none of our philosophical instrument-makers should use the construction. The superiority of this pump, to any that are made upon the common plan, is, indeed, prodigious. Few of them will rarefy more than 100 times, and, in a general way, not more than 60 or 70 times; whereas this instrument must be in a poor state indeed, if it does not rarefy 200 or 300 times; and when it is in good order, it will go as far as 1000 times, and sometimes even much farther than that; besides, this instrument is worked with much more ease, than a common air-pump, and either exhausts or condenses at pleasure. In short, to a person engaged in philosophical pursuits, this instrument is an invaluable acquisition. I shall have occasion to recite some experiments, which I could not have made, and which, indeed, I should hardly have dared to attempt, if I had not been possessed of such an air-pump as this. It is much to be wished, that some person of spirit in the trade would attempt the construction of an instrument, which would do great credit to himself, as well as be of eminent service to philosophy. FOOTNOTES: [11] On this account, if it was thought convenient to introduce a new term (or rather make a new application of a term already in use among chemists) it might not be amiss to call air that has been diminished, and made noxious by any of the processes above mentioned, or others similar to them, by the common appellation of _phlogisticated air_; and, if it was necessary, the particular process by which it was phlogisticated might be added; as common air phlogisticated by charcoal, air phlogisticated by the calcination of metals, nitrous air phlogisticated with the liver of sulphur, &c. [12] Here it becomes me to ask pardon of that excellent philosopher Father Beccaria of Turin, for conjecturing that the phlogiston, with which he revivified metals, did not come from the electric matter itself, but from what was discharged from other pieces of metal with which he made the experiment. See History of Electricity, p. 277, &c. This _revivification of metals_ by electricity completes the proof of the electric matter being, or containing phlogiston. SECTION III. _Of NITROUS AIR._ Since the publication of my former papers I have given more attention to the subject of nitrous air than to any other species of air; and having been pretty fortunate in my inquiries, I shall be able to lay before my reader a more satisfactory account of the curious phenomena occasioned by it, and also of its nature and constitution, than I could do before, though much still remains to be investigated concerning it, and many new objects of inquiry are started. With a view to discover where the power of nitrous air to diminish common air lay, I evaporated to dryness a quantity of the solution of copper in diluted spirit of nitre; and having procured from it a quantity of a _green precipitate_, I threw the focus of a burning-glass upon it, when it was put into a vessel of quicksilver, standing inverted in a bason of quicksilver. In this manner I procured air from it, which appeared to be, in all respects, nitrous air; so that part of the same principle which had escaped during the solution, in the form of _air_, had likewise been retained in it, and had not left it in the evaporation of the water. With great difficulty I also procured a small quantity of the same kind of air from a solution of _iron_ in spirit of nitre, by the same process. Having, for a different purpose, fired some paper, which had been dipped in a solution of copper in diluted spirit of nitre, in nitrous air, I found there was a considerable addition to the quantity of it; upon which I fired some of the same kind of paper in quicksilver and presently observed that air was produced from it in great plenty. This air, at the first, seemed to have some singular properties, but afterwards I found that it was nothing more than a mixture of nitrous air, from the precipitate of the solution, and of inflammable air, from the paper; but that the former was predominant. In the mixture of this kind of air with common air, in a trough of water which had been putrid, but which at that time seemed to have recovered its former sweetness (for it was not in the least degree offensive to the smell) a phenomenon sometimes occurred, which for a long time exceedingly delighted and puzzled me; but which was afterwards the means of letting me see much farther into the constitution of nitrous air than I had been able to see before. When the diminution of the air was nearly completed, the vessel in which the mixture was made began to be filled with the most beautiful _white fumes_, exactly resembling the precipitation of some white substance in a transparent menstruum, or the falling of very fine snow; except that it was much thicker below than above, as indeed is the case in all chemical precipitations. This appearance continued two or three minutes. At other times I went over the same process, as nearly as possible in the same manner, but without getting this remarkable appearance, and was several times greatly disappointed and chagrined, when I baulked the expectations of my friends, to whom I had described, and meant to have shewn it. This made me give all the attention I possibly could to this experiment, endeavouring to recollect every circumstance, which, though unsuspected at the time, might have contributed to produce this new appearance; and I took a great deal of pains to procure a quantity of this air from the paper above mentioned for the purpose, which, with a small burning lens, and an uncertain sun, is not a little troublesome. But all that I observed for some time was, that I stood the best chance of succeeding when I _warmed_ the vessel in which the mixture was made, and _agitated_ the air during the effervescence. Finding, at length, that, with the same preparation and attentions, I got the same appearance from a mixture of nitrous and common air in the same trough of water, I concluded that it could not depend upon any thing peculiar to the precipitate of the _copper_ contained in the _paper_ from which the air was procured, as I had at first imagined, but upon what was common to it, and pure nitrous air. Afterwards, having, (with a view to observe whether any crystals would be formed by the union of volatile alkali, and nitrous air, similar to those formed by it and fixed air, as described by Mr. Smeth in his _Dissertation on fixed Air_) opened the mouth of a phial which was half filled with a volatile alkaline liquor, in a jar of nitrous air (in the manner described p. 11. fig. 4.) I had an appearance which perfectly explained the preceding. All that part of the phial which was above the liquor, and which contained common air, was filled with beautiful _white clouds_, as if some fine white powder had been instantly thrown into it, and some of these clouds rose within the jar of nitrous air. This appearance continued about a minute, and then intirely disappeared, the air becoming transparent. Withdrawing the phial, and exposing it to the common air, it there also became turbid, and soon after the transparency returned. Introducing it again into the nitrous air, the clouds appeared as before. In this manner the white fumes, and transparency, succeeded each other alternately, as often as I chose to repeat the experiment, and would no doubt have continued till the air in the jar had been thoroughly diluted with common air. These appearances were the same with any substance that contained _volatile alkali_, fluid or solid. When, instead of the small phial, I used a large and tall glass jar, this appearance was truly fine and striking, especially when the water in the trough was very transparent. For I had only to put the smallest drop of a volatile alkaline liquor, or the smallest bit of the solid salt, into the jar, and the moment that the mouth of it was opened in a jar of nitrous air, the white clouds above mentioned began to be formed at the mouth, and presently descended to the bottom, so as to fill the whole, were it ever so large, as with fine snow. In considering this experiment, I soon perceived that this curious appearance must have been occasioned by the mixture of the nitrous and common air, and therefore that the white clouds must be _nitrous ammoniac_, formed by the acid of the nitrous air, set loose in the decomposition of it by common air, while the phlogiston, which must be another constituent part of nitrous air, entering the common air, is the cause of the diminution it suffers in this process; as it is the cause of a similar diminution, in a variety of other processes. I would observe, that it is not peculiar to nitrous air to be a test of the fitness of air for respiration. Any other process by which air is diminished and made noxious answers the same purpose. Liver of sulphur for instance, the calcination of metals, or a mixture of iron filings and brimstone will do just the same thing; but the application of them is not so easy, or elegant, and the effect is not so soon perceived. In fact, it is _phlogiston_ that is the test. If the air be so loaded with this principle that it can take no more, which is seen by its not being diminished in any of the processes above mentioned, it is noxious; and it is wholesome in proportion to the quantity of phlogiston that it is able to take. This, I have no doubt, is the true theory of the diminution of common air by nitrous air, the redness of the appearance being nothing more than the usual colour of the fumes, of spirit of nitre, which is now disengaged from the superabundant phlogiston with which it was combined in the nitrous air, and ready to form another union with any thing that is at hand, and capable of it. With the volatile alkali it forms nitrous ammoniac, water imbibes it like any other acid, even quicksilver is corroded by it; but this action being slow, the redness in this mixture of nitrous and common air continues much longer when the process is made in quicksilver, than when it is made in water, and the diminution, as I have also observed; is by no means so great. I was confirmed in this opinion when I put a bit of volatile alkaline salt into the jar of quicksilver in which I made the mixture of nitrous and common air. In these circumstances, the vessel being previously filled with the alkaline fumes, the acid immediately joined them, formed the white clouds above mentioned, and the diminution proceeded almost as far as when the process was made in water. That it did not proceed quite so far, I attribute chiefly to the small quantity of calx formed by the slight solution of mercury with the acid fumes not being able to absorb all the fixed air that is precipitated from the common air by the phlogiston. In part, also, it may be owing to the small quantify of surface in the quicksilver in the vessels that I made use of; in consequence of which the acid fumes could act upon it only in a slow succession, so that part of them, as well as of the fixed air, had an opportunity of forming another union with the diminished air. This, as I have observed before, was so much the case when the process was made in quicksilver, without any volatile alkali, that when water was admitted to it, after some time, it was not capable of dissolving that union, tho' it would not have taken place if the process had been in water from the first. In diversifying this experiment, I found that it appeared to very great advantage when I suspended a piece of volatile salt in the common air, previous to the admission of nitrous air to it, inclosing it in a bit of gauze, muslin, or a small net of wire. For, presently after the redness of the mixture begins to go off, the white cloud, like snow, begins to descend from the salt, as if a white powder was shaken out of the bag that contains it. This white cloud presently fills the whole vessel, and the appearance will last about five minutes. If the salt be not put to the mixture of these two kinds of air till it has perfectly recovered its transparency, the effervescence being completely over, no white cloud will be formed; and, what is rather more remarkable, there is nothing of this appearance when the salt is put into the nitrous air itself. The reason of this must be, that the acid of the nitrous air has a nearer affinity with its phlogiston than with the volatile alkali; though the phlogiston having a nearer affinity with something in the common air, the acid being thereby set loose, will unite with the alkaline vapour, if it be at hand to unite with it. There is also very little, if any white cloud formed upon holding a piece of the volatile salt within the mouth of a phial containing smoking spirit of nitre. Also when I threw the focus of a burning mirror upon some sal ammoniac in nitrous air, and filled the whole vessel with white fumes which arose from it, they were soon dispersed, and the air was neither diminished nor altered. I was now fully convinced, that the white cloud which I casually observed, in the first of these experiments, was occasioned by the volatile alkali emitted from the water, which was in a slight degree putrid; and that the warming, and agitation of the vessels, had promoted the emission of the putrid, or alkaline effluvium. I could not perceive that the diminution of common air by the mixture of nitrous air was sensibly increased by the presence of the volatile alkali. It is possible, however, that, by assisting the water to take up the acid, something less of it may be incorporated with the remaining diminished air than would otherwise have been; but I did not give much attention to this circumstance. When the phial in which I put the alkaline salts contained any kind of noxious air, the opening of it in nitrous air was not followed by any thing of the appearance above mentioned. This was the case with inflammable air. But when, after agitating the inflammable air in water, I had brought it to a state in which it was diminished a little by the mixture of nitrous air, the cloudy appearance was in the same proportion; so that this appearance seems to be equally a test of the fitness of air for respiration, with the redness which attends the mixture of it with nitrous air only. Having generally fastened the small bag which contained the volatile salt to a piece of brass wire in the preceding experiment, I commonly found the end of it corroded, and covered with a blue substance. Also the salt itself, and sometimes the bag was died blue. But finding that this was not the case when I used an iron wire in the same circumstances, but that it became _red_, I was satisfied that both the metals had been dissolved by the volatile alkali. At first I had a suspicion that the blue might have come from the copper, out of which the nitrous air had been made. But when the nitrous air was made from iron, the appearances were, in all respects, the same. I have observed, in the preceding section, that if nitrous air be mixed with common air in _lime-water_, the surface of the water, where it is contiguous to that mixture, will be covered with an incrustation of lime, shewing that some fixed air had been deposited in the process. It is remarkable, however, as I there also just mentioned, that this is the case when nitrous air alone is put to a vessel of lime-water, after it has been kept in a _bladder_, or only transferred from one vessel to another by a bladder, in the manner described, p. 15. fig. 9. As I had used the same bladder for transferring various kinds of air, and among the rest _fixed air_, I first imagined that this effect might have been occasioned by a mixture of this fixed air with the nitrous air, and therefore took a fresh bladder; but still the effect was the same. To satisfy myself farther, that the bladder had produced this effect, I put one into a jar of nitrous air, and after it had continued there a day and a night, I found that the nitrous air in this jar, though it was transferred in a glass vessel, made lime-water turbid. Whether there was any thing in the preparation of these bladders that occasioned their producing this effect, I cannot tell. They were such as I procure from the apothecaries. The thing seems to deserve farther examination, as there seems, in this case, to be the peculiar effect of fixed air from other causes, or else a production of fixed air from materials that have not been supposed to yield it, at least not in circumstances similar to these. As fixed air united to water dissolves iron, I had the curiosity to try whether fixed air alone would do it; and as nitrous air is of an _acid_ nature, as well as fixed air, I, at the same time, exposed a large surface of iron to both the kinds; first filling two eight ounce phials with nails, and then with quicksilver, and after that displacing the quicksilver in one of the phials by fixed air, and in the other by nitrous air; then inverting them, and leaving them with their mouths immersed in basons of quicksilver. In these circumstances the two phials stood about two months, when no sensible change at all was produced in the fixed air, or in the iron which had been exposed to it, but a most remarkable, and most unexpected change was made in the nitrous air; and in pursuing the experiment, it was transformed into a species of air, with properties which, at the time of my first publication on this subject, I should not have hesitated to pronounce impossible, viz. air in which a candle burns quite naturally and freely, and which is yet in the highest degree noxious to animals, insomuch that they die the moment they are put into it; whereas, in general, animals live with little sensible inconvenience in air in which candles have burned out. Such, however, is nitrous air, after it has been long exposed to a large surface of iron. It is not less extraordinary, that a still longer continuance of nitrous air in these circumstances (but _how long_ depends upon too many, and too minute circumstances to be ascertained with exactness) makes it not only to admit a candle to burn in it, but enables it to burn with an _enlarged flame_, by another flame (extending every where to an equal distance from that of the candle, and often plainly distinguishable from it) adhering to it. Sometimes I have perceived the flame of the candle, in these circumstances, to be twice as large as it is naturally, and sometimes not less than five or six times larger; and yet without any thing like an _explosion_, as in the firing of the weakest inflammable air. Nor is the farther progress in the transmutation of nitrous air, in these circumstances, less remarkable. For when it has been brought to the state last mentioned, the agitation of it in fresh water almost instantly takes off that peculiar kind of inflammability, so that it extinguishes a candle, retaining its noxious quality. It also retains its power of diminishing common air in a very great degree. But this noxious quality, like the noxious quality of all other kinds of air that will bear agitation in water, is taken out of it by this operation, continued about five minutes; in which process it suffers a farther and very considerable diminution. It is then itself diminished by fresh nitrous air, and animals live in it very well, about as well as in air in which candles have burned out. Lastly, One quantity of nitrous air, which had been exposed to iron in quicksilver, from December 18 to January 20, and which happened to stand in water till January 31 (the iron still continuing in the phial) was fired with an explosion, exactly like a weak inflammable air. At the same time another quantity of nitrous air, which had likewise been exposed to iron, standing in quicksilver, till about the same time, and had then stood in water only, without iron, only admitted a candle to burn in it with an enlarged flame, as in the cases above mentioned. But whether the difference I have mentioned in the circumstances of these experiments contributed to this difference in the result, I cannot tell. Nitrous air treated in the manner above mentioned is diminished about one fourth by standing in quicksilver; and water admitted to it will absorb about half the remainder; but if water only, and no quicksilver, be used from the beginning, the nitrous air will be diminished much faster and farther; so that not more than one fourth, one sixth, or one tenth of the original quantity will remain. But I do not know that there is any difference in the constitution of the air which remains in these two cases. The water which has imbibed this nitrous air exposed to iron is remarkably green, also the phial containing it becomes deeply, and, I believe, indelibly tinged with green; and if the water be put into another vessel, it presently deposits a considerable quantity of matter, which when dry appears to be the earth or ochre of iron; from which it is evident, that the acid of the nitrous air dissolves the iron; while the phlogiston, being set loose, diminishes nitrous air, as in the process of the iron filings and brimstone. Upon this hint, instead of using _iron_, I introduced a pot of _liver of sulphur_ into a jar of nitrous air, and presently found, that what I had before done by means of iron in six weeks, or two months, I could do by liver of sulphur (in consequence, no doubt, of its giving its phlogiston more freely) in less than twenty-four hours, especially when the process was kept warm. It is remarkable, however, that if the process with liver of sulphur be suffered to proceed, the nitrous air will be diminished much farther. At one time not more than one twentieth of the original quantity remained, and how much farther it right have been diminished, I cannot tell. In this great diminution, it does not admit a candle to burn in it at all; and I generally found this to be the case whenever the diminution had proceeded beyond three fourths of the original quantity[13]. It is something remarkable, that though the diminution of nitrous air by iron filings and brimstone very much resembles the diminution of it by iron only, or by liver of sulphur, yet the iron filings and brimstone never bring it to such a state as that a candle will burn in it; and also that, after this process, it is never capable of diminishing common air. But when it is considered that these properties are destroyed by agitation in water, this difference in the result of processes, in other respects similar, will appear less extraordinary; and they agree in this, that long agitation in water makes both these kinds of nitrous air equally fit for respiration, being equally diminished by fresh nitrous air. It is possible that there would have been a more exact agreement in the result of these processes, if they had been made in equal degrees of _heat_; but the process with iron was made in the usual temperature of the atmosphere, and that with liver of sulphur generally near a fire. It may clearly, I think, be inferred from these experiments, that all the difference between fresh nitrous air, that state of it in which it is partially inflammable, or wholly so, that in which it again extinguishes candles, and that in which it finally becomes fit for respiration, depends upon some difference in the _mode of the combination_ of its acid with phlogiston, or on the _proportion_ between these two ingredients in its composition; and it is not improbable but that, by a little more attention to these experiments, the whole mystery of this proportion and combination may be explained. I must not omit to observe that there was something peculiar in the result of the first experiment which I made with nitrous air exposed to iron; which was that, without any agitation in water, it was diminished by fresh nitrous air, and that a candle burned in it quite naturally. To what this difference was owing I cannot tell. This air, indeed, had been exposed to the iron a week or two longer than in any of the other cases, but I do not imagine that this circumstance could have produced that difference. When the process is in water with iron, the time in which the diminution is accomplished is exceedingly various; being sometimes completed in a few days, whereas at other times it has required a week or a fortnight. Some kinds of iron also produced this effect much sooner than others, but on what circumstances this difference depends I do not know. What are the varieties in the result of this experiment when it is made in quicksilver I cannot tell, because, on account of its requiring more time, I have not repeated it so often; but I once found that nitrous air was not sensibly changed by having been exposed to iron in quicksilver nine days; whereas in water a very considerable alteration was always made in much less than half that time. It may just deserve to be mentioned, that nitrous air extremely rarified in an air-pump dissolves iron, and is diminished by it as much as when it is in its native state of condensation. It is something remarkable, though I never attended to it particularly before I made these last experiments, and it may tend to throw some light upon them, that when a candle is extinguished, as it never fails to be, in nitrous air, the flame seems to be a little enlarged at its edges, by another bluish flame added to it, just before its extinction. It is proper to observe in this place, that the electric spark taken in nitrous air diminishes it to one fourth of its original quantity, which is about the quantity of its diminution by iron filings and brimstone, and also by liver of sulphur without heat. The air is also brought by electricity to the same state as it is by iron filings and brimstone, not diminishing common air. If the electric spark be taken in it when it is confined by water tinged with archil, it is presently changed from blue to red, and that to a very great degree. When the iron nails or wires, which I have used to diminish nitrous air, had done their office, I laid them aside, not suspecting that they could be of any other philosophical use; but after having lain exposed to the open air almost a fortnight; having, for some other purpose, put some of them into a vessel containing common air, standing inverted, and immersed in water, I was surprized to observe that the air in which they were confined was diminished. The diminution proceeded so fast, that the process was completed in about twenty-four hours; for in that time the air was diminished about one fifth, so that it made no effervescence with nitrous air, and was, therefore, no doubt, highly noxious, like air diminished by any other process. This experiment I have repeated a great number of times, with the same phials, filled with nails or wires that have been suffered to rust in nitrous air, but their power of diminishing common air grows less and less continually. How long it will be before it is quite exhausted I cannot tell. This diminution of air I conclude must arise from the phlogiston, either of the nitrous air or the iron, being some way entangled in the rust, in which the wires were encrusted, and afterwards getting loose from it. To the experiments upon iron filings and brimstone in nitrous air, I must add, that when a pot full of this mixture had absorbed as much as it could of a jar of nitrous air (which is about three fourths of the whole) I put fresh nitrous air to it, and it continued to absorb, till three or four jars full of it disappeared; but the absorption was exceedingly slow at the last. Also when I drew this pot through the water, and admitted fresh nitrous air to it, it absorbed another jar full, and then ceased. But when I scraped off the outer surface of this mixture, which had been so long exposed to the nitrous air, the remainder absorbed more of the air. When I took the top of the mixture which I had scraped off and threw upon it the focus of a burning-glass, the air in which it was confined was diminished, and became quite noxious; yet when I endeavoured to get air from this matter in a jar full of quicksilver, I was able to procure little or nothing. It is not a little remarkable that nitrous air diminished by iron filings and brimstone, which is about one fourth, cannot, by agitation in water, be diminished much farther; whereas pure nitrous air may, by the same process, be diminished to one twentieth of its whole bulk, and perhaps much more. This is similar to the effect of the same mixture, and of phlogiston in other cases, on fixed air; for it so far changes its constitution, that it is afterwards incapable of mixing with water. It is similar also to the effect of phlogiston in acid air, which of itself is almost instantly absorbed by water; but by this addition it is first converted into inflammable air, which does not readily mix with water, and which, by long agitation in water, becomes of another constitution, still less miscible with water. I shall close this section with a few other observations of a miscellaneous nature. Nitrous air is as much diminished both by iron filings, and also by liver of sulphur, when confined in quicksilver, as when it is exposed to water. Distilled water tinged blue with the juice of turnsole becomes red on being impregnated with nitrous air; but by being exposed a week or a fortnight to the common atmosphere, in open and shallow vessels, it recovers its blue colour; though, in that time, the greater part of the water will be evaporated. This shews that in time nitrous air escapes from the water with which it is combined, just as fixed air does, though by no means so readily[14]. Having dissolved silver, copper, and iron in equal quantities of spirit of nitre diluted with water, the quantities of nitrous air produced from them were in the following proportion; from iron 8, from copper 6-1/4, from silver 6. In about the same proportion also it was necessary to mix water with the spirit of nitre in each case, in order to make it dissolve these metals with equal rapidity, silver requiring the least water, and iron the most. Phosphorus gave no light in nitrous air, and did not take away from its power of diminishing common air; only when the redness of the mixture went off, the vessel in which it was made was filled with white fumes, as if there had been some volatile alkali in it. The phosphorus itself was unchanged. There is something remarkable in the effect of nitrous air on _insects_ that are put into it. I observed before that this kind of air is as noxious as any whatever, a mouse dying the moment it is put into it; but frogs and snails (and therefore, probably, other animals whose respiration is not frequent) will bear being exposed to it a considerable time, though they die at length. A frog put into nitrous air struggled much for two or three minutes, and moved now and then for a quarter of an hour, after which it was taken out, but did not recover. _Wasps_ always died the moment they were put into the nitrous air. I could never observe that they made the least motion in it, nor could they be recovered to life afterwards. This was also the case in general with _spiders_, _flies_, and _butterflies_. Sometimes, however, spiders would recover after being exposed about a minute to this kind of air. Considering how fatal nitrous air is to insects, and likewise its great antiseptic power, I conceived that considerable use might be made of it in medicine, especially in the form of _clysters_, in which fixed air had been applied with some success; and in order to try whether the bowels of an animal would bear the injection of it, I contrived, with the help of Mr. Hey, to convey a quantity of it up the anus of a dog. But he gave manifest signs of uneasiness, as long as he retained it, which was a considerable time, though in a few hours afterwards he was as lively as ever, and seemed to have suffered nothing from the operation. Perhaps if nitrous air was diluted either with common air, or fixed air, the bowels might bear it better, and still it might be destructive to _worms_ of all kinds, and be of use to check or correct putrefaction in the intestinal canal, or other parts of the system. I repeat it once more that, being no physician, I run no risk by such proposals as these; and I cannot help flattering myself that, in time, very great medicinal use will be made of the application of these different kinds of air to the animal system. Let ingenious physicians attend to this subject, and endeavour to lay hold of the new _handle_ which is now presented them, before it be seized by rash empiricks; who, by an indiscriminate and injudicious application, often ruin the credit of things and processes which might otherwise make an useful addition to the _materia_ and _ars medica_. In the first publication of my papers, having experienced the remarkable antiseptic power of nitrous air, I proposed an attempt to preserve anatomical preparations, &c. by means of it; but Mr. Hey, who made the trial, found that, after some months, various animal substances were shriveled, and did not preserve their natural forms in this kind of air. FOOTNOTES: [13] The result of several of these experiments I had the pleasure of trying in the presence of the celebrated Mr. De Luc of Geneva, when he was upon a visit to Lord Shelburne in Wiltshire. [14] I have not repeated this experiment with that variation of circumstances which an attention to Mr. Bewley's observation will suggest. SECTION IV. _Of MARINE ACID AIR._ In my former experiments on this species of air I procured it from spirit of salt, but I have since hit upon a much less expensive method of getting it, by having recourse to the process by which the spirit of salt is itself originally made. For this purpose I fill a small phial with common salt, pour upon it a small quantity of concentrated oil of vitriol, and receive the fumes emitted by it in a vessel previously filled with quicksilver, and standing in a bason of quicksilver, in which it appears in the form of a perfectly _transparent air_, being precisely the same thing with that which I had before expelled from the spirit of salt. This method of procuring acid air is the more convenient, as a phial, once prepared in this manner, will suffice, for common experiments, many weeks; especially if a little more oil of vitriol be occasionally put to it. It only requires a little more heat at the last than at the first. Indeed, at the first, the heat of a person's hand will often be sufficient to make it throw out the vapour. In warm weather it will even keep smoking many days without the application of any other heat. On this account, it should be placed where there are no instruments, or any thing of metal, that can be corroded by this acid vapour. It is from dear-bought experience that I give this advice. It may easily be perceived when this phial is throwing out this acid vapour, as it always appears, in the open air, in the form of a light cloud; owing, I suppose, to the acid attracting to itself, and uniting with, the moisture that is in the common atmosphere. By this process I even made a stronger spirit of salt than can be procured in any other way. For having a little water in the vessel which contains the quicksilver, it imbibes the acid vapour, and at length becomes truly saturated with it. Having, in this manner, impregnated pure water with acid air, I could afterwards expel the same air from it, as from common spirit of salt. I observed before that this acid vapour, or air, has a strong affinity with _phlogiston_, so that it decomposes many substances which contain it, and with them forms a permanently inflammable air, no more liable to be imbibed by water than inflammable air procured by any other process, being in fact the very same thing; and that, in some cases, it even dislodges spirit of nitre and oil of vitriol, which in general appear to be stronger acids than itself. I have since observed that, by giving it more time, it will extract phlogiston from substances from which I at first concluded that it was not able to do it, as from dry wood, crusts of bread not burnt, dry flesh, and what is more extraordinary from flints. As there was something peculiar to itself in the process or result of each of these experiments, it may not be improper to mention them distinctly. Pieces of dry _cork wood_ being put to the acid air, a small quantity remained not imbibed by water, and was inflammable. Very dry pieces of _oak_, being exposed to this air a day and a night, after imbibing a considerable quantity of it, produced air which was inflammable indeed, but in the slightest degree imaginable. It seemed to be very nearly in the state of common air. A piece of _ivory_ imbibed the acid vapour very slowly. In a day and a night, however, about half an ounce measure of permanent air was produced, and it was pretty strongly inflammable. The ivory was not discoloured, but was rendered superficially soft, and clammy, tasting very acid. Pieces of _beef_, roasted, and made quite dry, but not burnt, absorbed the acid vapour slowly; and when it had continued in this situation all night, from five ounce measures of the air, half a measure was permanent, and pretty strongly inflammable. This experiment succeeded a second time exactly in the same manner; but when I used pieces of white dry _chicken-flesh_ though I allowed the same time, and in other respects the process seemed to go on in the same manner, I could not perceive that any part of the remaining air was inflammable. Some pieces of a whitish kind of _flint_, being put into a quantity of acid air, imbibed but a very little of it in a day and a night; but of 2-1/2 ounce measures of it, about half a measure remained unabsorbed by water, and this was strongly inflammable, taking fire just like an equal mixture of inflammable and common air. At another time, however, I could not procure any inflammable air by this means, but to what circumstance these different results were owing I cannot tell. That inflammable air is produced from _charcoal_ in acid air I observed before. I have since found that it may likewise be procured from _pit coal_, without being charred. Inflammable air I had also observed to arise from the exposure of spirit of wine, and various _oily_ substances, to the vapour of spirit of salt. I have since made others of a similar nature, and as peculiar circumstances attended some of these experiments, I shall recite them more at large. _Essential oil of mint_ absorbed this air pretty fast, and presently became of a deep brown colour. When it was taken out of this air it was of the consistence of treacle, and sunk in water, smelling differently from what it did before; but still the smell of the mint was predominant. Very little or none of the air was fixed, so as to become inflammable; but more time would probably have produced this effect. _Oil of turpentine_ was also much thickened, and became of a deep brown colour, by being saturated with acid air. _Ether_ absorbed acid air very fast, and became first of a turbid white, and then of a yellow and brown colour. In one night a considerable quantity of permanent air was produced, and it was strongly inflammable. Having, at one time, fully saturated a quantity of ether with acid air, I admitted bubbles of common air to it, through the quicksilver, by which it was confined, and observed that white fumes were made in it, at the entrance of every bubble, for a considerable time. At another time, having fully saturated a small quantity of ether with acid air, and having left the phial in which it was contained nearly full of the air, and inverted, it was by some accident overturned; when, instantly, the whole room was filled with a visible fume, like a white cloud, which had very much the smell of ether, but peculiarly offensive. Opening the door and window of the room, this light cloud filled a long passage, and another room. In the mean time the ether was seemingly all vanished, but some time after the surface of the quicksilver in which the experiment had been made was covered with a liquor that tasted very acid; arising, probably, from the moisture in the atmosphere attracted by the acid vapour with which the ether had been impregnated. This visible cloud I attribute to the union of the moisture in the atmosphere with the compound of the acid air and ether. I have since saturated other quantities of ether with acid air, and found it to be exceedingly volatile, and inflammable. Its exhalation was also visible, but not in so great a degree as in the case above mentioned. _Camphor_ was presently reduced into a fluid state by imbibing acid air, but there seemed to be something of a whitish sediment in it. After continuing two days in this situation I admitted water to it; immediately upon which the camphor resumed its former solid state, and, to appearance, was the very same substance that it had been before; but the taste of it was acid, and a very small part of the air was permanent, and slightly inflammable. The acid air seemed to make no impression upon a piece of Derbyshire _spar_, of a very dark colour, and which, therefore, seemed to contain a good deal of phlogiston. As the acid air has so near an affinity with phlogiston, I expected that the fumes of _liver of sulphur_, which chemists agree to be phlogistic, would have united with it, so as to form inflammable air; but I was disappointed in that expectation. This substance imbibed half of the acid air to which it was introduced: one fourth of the remainder, after standing one day in quicksilver, was imbibed by water, and what was left extinguished a candle. This experiment, however, seems to prove that acid air and phlogiston may form a permanent kind of air that is not inflammable. Perhaps it may be air in such a state as common air loaded with phlogiston, and from which the fixed air has been precipitated. Or rather, it may be the same thing with inflammable air, that has lost its inflammability by long standing in water. It well deserves a farther examination. The following experiments are those in which the _stronger acids_ were made use of, and therefore they may assist us farther to ascertain their affinities with certain substances, with respect to this marine acid in the form of air. I put a quantity of strong concentrated _oil of vitriol_ to acid air, but it was not at all affected by it in a day and a night. In order to try whether it would not have more power in a more condensed state, I compressed it with an additional atmosphere; but upon taking off this pressure, the air expanded again, and appeared to be not at all diminished. I also put a quantity of strong _spirit of nitre_ to it without any sensible effect. We may conclude, therefore, that the marine acid, in this form of air, is not able to dislodge the other acids from their union with water. _Blue vitriol_, which is formed by the union of the vitriolic acid with copper, turned to a dark green the moment that it was put to the acid air, which it absorbed, though slowly. Two pieces, as big as small nuts, absorbed three ounce measures of the air in about half an hour. The green colour was very superficial; for it was easily wiped or washed off. _Green copperas_ turned to a deeper green upon being put into acid air, which it absorbed slowly. _White copperas_ absorbed this air very fast, and was dissolved in it. _Sal ammoniac_, being the union of spirit of salt with volatile alkali, was no more affected with the acid air than, as I have observed before, common salt was. I also introduced to the acid air various other substances, without any particular expectation; and it may be worth while to give an account of the results, that the reader may draw from them such conclusions as he shall think reasonable. _Borax_ absorbed acid air about as fast as blue vitriol, but without any thing else that was observable. Fine white _sugar_ absorbed this air slowly, was thoroughly penetrated with it, became of a deep brown colour, and acquired a smell that was peculiarly pungent. A piece of _quick lime_ being put to about twelve or fourteen ounce measures of acid air, and continuing in that situation about two days, there remained one ounce measure of air that was not absorbed by water, and it was very strongly inflammable, as much so as a mixture of half inflammable and half common air. Very particular care was taken that no common air mixed with the acid air in this process. At another time, from about half the quantity of acid air above mentioned, with much less quick-lime, and in the space of one day, I got half an ounce measure of air that was inflammable in a slight degree only. This experiment proves that some part of the phlogiston which escapes from the fuel, in contact with which the lime is burned, adheres to it. But I am very far from thinking that the causticity of quick-lime is at all owing to this circumstance. I have made a few more experiments on the mixture of acid air with _other kinds of air_, and think that it may be worth while to mention them, though nothing of consequence, at least nothing but negative conclusions, can be drawn from them. A quantity of common air saturated with nitrous air was put to a quantity of acid air, and they continued together all night, without any sensible effect. The quantity of both remained the same, and water being admitted to them, it absorbed all the acid air, and left the other just as before. A mixture of two thirds of air diminished by iron filings and brimstone, and one third acid air, were mixed together, and left to stand four weeks in quicksilver. But when the mixture was examined, water presently imbibed all the acid air, and the diminished air was found to be just the same that it was before. I had imagined that the acid air might have united with the phlogiston with which the diminished air was overcharged, so as to render it wholsome; and I had read an account of the stench arising from putrid bodies being corrected by acid fumes. The remaining experiments, in which the acid air was principally concerned, are of a miscellaneous nature. I put a piece of dry _ice_ to a quantity of acid air (as was observed in the section concerning _alkaline_ air) taking it with a forceps, which, as well as the air itself, and the quicksilver by which it had been confined; had been exposed to the open air for an hour, in a pretty strong frost. The moment it touched the air it was dissolved as fast as it would have been by being thrown into a hot fire, and the air was presently imbibed. Putting fresh pieces of ice to that which was dissolved before, they were also dissolved immediately, and the water thus procured did not freeze again, though it was exposed a whole night, in a very intense frost. Flies and spiders die in acid air, but not so quickly as in nitrous air. This surprized me very much; as I had imagined that nothing could be more speedily fatal to all animal life than this pure acid vapour. As inflammable air, I have observed, fires at one explosion in the vapour of smoking spirit of nitre, just like an equal mixture of inflammable and common air, I thought it was possible that the fume which naturally rises from common spirit of salt might have the same effect, but it had not. For this purpose I treated the spirit of salt, as I had before done the smoking spirit of nitre; first filling a phial with it, then inverting it in a vessel containing a quantity of the same acid; and having thrown the inflammable air into it, and thereby driven out all the acid, turning it with its mouth upwards, and immediately applying a candle to it. Acid air not being so manageable as most of the other kinds of air, I had recourse to the following peculiar method, in order to ascertain its _specific gravity_. Having filled an eight ounce phial with this air, and corked it up, I weighed it very accurately; and then, taking out the cork, I blew very strongly into it with a pair of bellows, that the common air might take place of the acid; and after this I weighed it again, together with the cork, but I could not perceive the least difference in the weight. I conclude, however, from this experiment, that the acid air is heavier than the common air, because the mouth of the phial and the inside of it were evidently moistened by the water which the acid vapour had attracted from the air, which moisture must have added to the weight of the phial. SECTION V. _Of INFLAMMABLE AIR._ It will have appeared from my former experiments, that inflammable air consists chiefly, if not wholly, of the union of an acid vapour with phlogiston; that as much of the phlogiston as contributes to make air inflammable is imbibed by the water in which it is agitated; that in this process it soon becomes fit for respiration, and by the continuance of it comes at length to extinguish flame. These observations, and others which I have made upon this kind of air, have been confirmed by my later experiments, especially those in which I have connected _electrical experiments_ with those on air. The electric spark taken in any kind of _oil_ produces inflammable air, as I was led to observe in the following manner. Having found, as will be mentioned hereafter, that ether doubles the quantity of any kind of air to which it is admitted; and being at that time engaged in a course of experiments to ascertain the effect of the electric matter on all the different kinds of air, I had the curiosity to try what it would do with _common air_, thus increased by means of ether. The very first spark, I observed, increased the quantity of this air very considerably, so that I had very soon six or eight times as much as I began with; and whereas water imbibes all the ether that is put to any kind of air, and leaves it without any visible change, with respect to quantity or quality, this air, on the contrary, was not imbibed by water. It was also very little diminished by the mixture of nitrous air. From whence it was evident, that it had received an addition of some other kind of air, of which it now principally consisted. In order to determine whether this effect was produced by the _wire_, or the _cement_ by which the air was confined (as I thought it possible that phlogiston might be discharged from them) I made the experiment in a glass syphon, fig. 19, and by that means I contrived to make the electric spark pass from quicksilver through the air on which I made the experiment, and the effect was the same as before. At one time there happened to be a bubble of common air, without any ether, in one part of the syphon, and another bubble with ether in another part of it; and it was very amusing to observe how the same electric sparks diminished the former of these bubbles, and increased the latter. It being evident that the _ether_ occasioned the difference that was observable in these two cases, I next proceeded to take the electric spark in a quantity of ether only, without any air whatever; and observed that every spark produced a small bubble; and though, while the sparks were taken in the ether itself, the generation of air was slow, yet when so much air was collected, that the sparks were obliged to pass through it, in order, to come to the ether and the quicksilver on which it rested, the increase was exceedingly rapid; so that, making the experiment in small tubes, as fig. 16, the quicksilver soon receded beyond the striking distance. This air, by passing through water, was diminished to about one third, and was inflammable. One quantity of air produced in this manner from ether I suffered to stand two days in water, and after that I transferred it several times through the water, from one vessel to another, and still found that it was very strongly inflammable; so that I have no doubt of its being genuine inflammable air, like that which is produced from metals by acids, or by any other chemical process. Air produced from ether, mixed both with common and nitrous air, was likewise inflammable; but in the case of the nitrous air, the original quantity bore a very small proportion to the quantity generated. Concluding that the inflammable matter in this air came from the ether, as being of the class of _oils_, I tried other kinds of oil, as _oil of olives_, _oil of turpentine_, and _essential oil of mint_, taking the electric spark in them, without any air to begin with, and found that inflammable air was produced in this manner from them all. The generation of air from oil of turpentine was the quickest, and from the oil of olives the slowest in these three cases. By the same process I got inflammable air from _spirit of wine_, and about as copiously as from the essential oil of mint. This air continued in water a whole night, and when it was transferred into another vessel was strongly inflammable. In all these cases the inflammable matter might be supposed to arise from the inflammable substances on which the experiments were made. But finding that, by the same process I could get inflammable air from the _volatile spirit of sal ammoniac_, I conclude that the phlogiston was in part supplied by the electric matter itself. For though, as I have observed before, the alkaline air which is expelled from the spirit of sal ammoniac be inflammable, it is so in a very slight degree, and can only be perceived to be so when there is a considerable quantity of it. Endeavouring to procure air from a caustic alkaline liquor, accurately made for me by Mr. Lane, and also from spirit of salt, I found that the electric spark could not be made visible in either of them; so that they must be much more perfect conductors of electricity than water, or other fluid substances. This experiment well deserves to be prosecuted. I observed before that inflammable air, by standing long in water, and especially by agitation in water, loses its inflammability; and that in the latter case, after passing through a state in which it makes some approach to common air (just admitting a candle to burn in it) it comes to extinguish a candle. I have since made another observation of this kind, which well deserves to be recited. It relates to the inflammable air generated from oak the 27th of July 1771, of which I have made mention before. This air I have observed to have been but weakly inflammable some months after it was generated, and to have been converted into pretty good or wholesome air by no great degree of agitation in water; but on the 27th of March 1773, I found the remainder of it to be exceedingly good air. A candle burned in it perfectly well, and it was diminished by nitrous air almost as much as common air. I shall conclude this section with a few miscellaneous observations of no great importance. Inflammable air is not changed by being made to pass many times through a red-hot iron tube. It is also no more diminished or changed by the fumes of liver of sulphur, or by the electric spark, than I have before observed it to have been by a mixture of iron filings and brimstone. When the electric spark was taken in it, it was confined by a quantity of water tinged blue with the juice of archil, but the colour remained unchanged. I put two _wasps_ into inflammable air, and let them remain there a considerable time, one of them near an hour. They presently ceased to move, and seemed to be quite dead for about half an hour after they were taken into the open air; but then they came to life again, and presently after seemed to be as well as ever they had been. SECTION VI. _Of FIXED AIR._ The additions I have made to my observations on _fixed air_ are neither numerous nor considerable. The most important of them is a confirmation of my conjecture, that fixed air is capable of forming an union with phlogiston, and thereby becoming a kind of air that is not miscible with water. I had produced this effect before by means of iron filings and brimstone, fermenting in this kind of air; but I have since had a much more decisive and elegant proof of it by _electricity_. For after taking a small electric explosion, for about an hour, in the space of an inch of fixed air, confined in a glass tube one tenth of an inch in diameter, fig. 16, I found that when water was admitted to it, only one fourth of the air was imbibed. Probably the whole of it would have been rendered immiscible in water, if the electrical operation had been continued a sufficient time. This air continued several days in water, and was even agitated in water without any farther diminution. It was not, however, common air, for it was not diminished by nitrous air. By means of iron filings and brimstone I have, since my former experiments, procured a considerable quantity of this kind of air in a method something different from that which I used before. For having placed a pot of this mixture under a receiver, and exhausted it with a pump of Mr. Smeaton's construction, I filled it with fixed air, and then left it plunged under water; so that no common air could have access to it. In this manner, and in about a week, there was, as near as I can recollect, one sixth, or at least one eighth of the whole converted into a permanent air, not imbibed by water. From this experiment I expected that the same effect would have been produced on fixed air by the fumes of _liver of sulphur_; but I was disappointed in that expectation, which surprised me not a little; though this corresponds in some measure, to the effect of phlogiston exhaled from this substance on acid air. Perhaps more time may be requisite for this purpose, for this process was not continued more than a day and a night. Iron filings and brimstone, I have observed, ferment with great heat in nitrous air, and I have since observed that this process is attended with greater heat in fixed air than in common air. Though fixed air incorporated with water dissolves iron, fixed air without water has no such power, as I observed before. I imagined that, if it could have dissolved iron, the phlogiston would have united with the air, and have made it immiscible with water, as in the former instances; but after being confined in a phial full of nails from the 15th of December to the 4th of October following, neither the iron nor the air appeared to have been affected by their mutual contact. Having exposed equal quantities of common and fixed air, in equal and similar cylindrical glass vessels, to equal degrees of heat, by placing them before a fire, and frequently changing their situations, I observed that they were expanded exactly alike, and when removed from the fire they both recovered their former dimensions. Having had some small suspicion that liver of sulphur, besides emitting phlogiston, might also yield some fixed air (which is known to be contained in the salt of tartar from which it is made) I mixed the two ingredients, viz. salt of tartar and brimstone, and putting them into a thin phial, and applying the flame of a candle to it, so as to form the liver of sulphur, I received the air that came from it in this process in a vessel of quicksilver. In this manner I procured a very considerable quantity of fixed air, so that I judged it was all discharged from the tartar. But though it is possible that a small quantity of it may remain in liver of sulphur, when it is made in the most perfect manner, it is not probable that it can be expelled without heat. SECTION VII. MISCELLANEOUS EXPERIMENTS. 1. It is something extraordinary that, though ether, as I found, cannot be made to assume the form of air (the vapour arising from it by heat, being soon condensed by cold, even in quicksilver) yet that a very small quantity of ether put to any kind of air, except the acid, and alkaline, which it imbibes, almost instantly doubles the apparent quantity of it; but upon passing this air through water, it is presently reduced to its original quantity again, with little or no change of quality. I put about the quantity of half a nut-shell full of ether, inclosed in a glass tube, through a body of quicksilver, into an ounce measure of common air, confined by quicksilver; upon which it presently began to expand, till it occupied the space of two ounce measures. It then gradually contracted about one sixth of an ounce measure. Putting more ether to it, it again expanded to two ounce measures; but no more addition of ether would make it expand any farther. Withdrawing the quicksilver, and admitting water to this air, without any agitation, it began to be absorbed; but only about half an ounce measure had disappeared after it had stood an hour in the water. But by once passing it through water the air was reduced to its original dimensions. Being tried by a mixture of nitrous air, it appeared not to be so good as fresh air, though the injury it had received was not considerable. All the phenomena of dilatation and contraction were nearly the same, when, instead of common air, I used nitrous air, fixed air, inflammable air, or any species of phlogisticated common air. The quantity of each of these kinds of air was nearly doubled while they were kept in quicksilver, but fixed air was not so much increased as the rest, and phlogisticated air less; but after passing through the water, they appeared not to have been sensibly changed by the process. 2. Spirit of wine yields no air by means of heat, the vapours being soon condensed by cold, like the vapour of water; yet when, in endeavouring to procure air from it, I made it boil, and catched the air which had rested on the surface of the spirit, and which had been expelled by the heat together with the vapour, in a vessel of quicksilver, and afterwards admitted acid air to it, the vessel was filled with white fumes, as if there had been a mixture of alkaline air along with it. To what this appearance was owing I cannot tell, and indeed I did not examine into it. 3. Having been informed by Dr. Small and Mr. Bolton of Birmingham, that paper dipped in a solution of copper in spirit of nitre would take fire with a moderate heat (a fact which I afterwards found mentioned in the Philosophical Transactions) it occurred to me that this would be very convenient for experiments relating to _ignition_ in different kinds of air; and indeed I found that it was easily fired, either by a burning lens, or the approach of red-hot iron on the outside of the phial in which it was contained, and that any part of it being once fired, the whole was presently reduced to ashes; provided it was previously made thoroughly dry, which, however, it is not very easy to do. With this preparation, I found that this paper burned freely in all kinds of air, but not in _vacuo_, which is also the case with gunpowder; and, as I have in effect observed before, all the kinds of air in which this paper was burned received an addition to their bulk, which consisted partly of nitrous air, from the nitrous precipitate, and partly of inflammable air, from the paper. As some of the circumstances attending the ignition of this paper in some of the kinds of air were a little remarkable, I shall just recite them. Firing this paper in _inflammable_ air, which it did without any ignition of the inflammable air itself, the quantity increased regularly, till the phial in which the process was made was nearly full; but then it began to decrease, till one third of the whole quantity disappeared. A piece of this paper being put to three ounce measures of _acid_ air, a great part of it presently turned yellow, and the air was reduced to one third of the original quantity, at the same time becoming reddish, exactly like common air in a phial containing smoking spirit of nitre. After this, by the approach of hot iron, I set fire to the paper; immediately upon which there was a production of air which more than filled the phial. This air appeared, upon examination, to be very little different from pure nitrous air. I repeated this experiment with the same event. Paper dipped in a solution of mercury, zinc, or iron, in nitrous acid, has, in a small degree, the same property with paper dipped in a solution of copper in the same acid. 4. Gunpowder is also fired in all kinds of air, and, in the quantity in which I tried it, did not make any sensible change in them, except that the common air in which it was fired would not afterwards admit a candle to burn in it. In order to try this experiment I half exhausted a receiver, and then with a burning-glass fired the gunpowder which had been previously put into it. By this means I could fire a greater quantity of gunpowder in a small quantity of air, and avoid the hazard of blowing up, and breaking my receiver. I own that I was rather afraid of firing gunpowder in inflammable air, but there was no reason for my fear; for it exploded quite freely in this air, leaving it, in all respects, just as it was before. In order to make this experiment, and indeed almost all the experiments of firing gunpowder in different kinds of air, I placed the powder upon a convenient stand within my receiver, and having carefully exhausted it by a pump of Mr. Smeaton's construction, I filled the receiver with any kind of air by the apparatus described, p. 19, fig. 14, taking the greatest care that the tubes, &c. which conveyed the air should contain little or no common air. In the experiment with inflammable air a considerable mixture of common air would have been exceedingly hazardous: for, by that assistance, the inflammable air might have exploded in such a manner, as to have been dangerous to the operator. Indeed, I believe I should not have ventured to have made the experiment at all with any other pump besides Mr. Smeaton's. Sometimes, I filled a glass vessel with quicksilver, and introduced the air to it, when it was inverted in a bason of quicksilver. By this means I intirely avoided any mixture of common air; but then it was not easy to convey the gunpowder into it, in the exact quantity that was requisite for my purpose. This, however, was the only method by which I could contrive to fire gunpowder in acid or alkaline air, in which it exploded just as it did in nitrous or fixed air. I burned a considerable quantity of gunpowder in an exhausted receiver (for it is well known that it will not explode in it) but the air I got from it was very inconsiderable, and in these circumstances was necessarily mixed with common air. A candle would not burn in it. SECTION VIII. _QUERIES, SPECULATIONS, and HINTS._ I begin to be apprehensive lest, after being considered as a _dry experimenter_, I should pass, with many of my readers, into the opposite character of a _visionary theorist_. A good deal of theory has been interspersed in the course of this work, but, not content with this, I am now entering upon a long section, which contains nothing else. The conjectures that I have ventured to advance in the body of the work will, I hope, be found to be pretty well supported by facts; but the present section will, I acknowledge, contain many _random thoughts_. I have, however, thrown them together by themselves, that readers of less imagination, and who care not to advance beyond the regions of plain fact, may, if they please, proceed no farther, that their delicacy be not offended. In extenuation of my offence, let it, however, be considered, that _theory_ and _experiment_ necessarily go hand in hand, every process being intended to ascertain some particular _hypothesis_, which, in fact, is only a conjecture concerning the circumstances or the cause of some natural operation; consequently that the boldest and most original experimenters are those, who, giving free scope to their imaginations, admit the combination of the most distant ideas; and that though many of these associations of ideas, will be wild and chimerical, yet that others will have the chance of giving rise to the greatest and most capital discoveries; such as very cautious, timid, sober, and slow-thinking people would never have come at. Sir Isaac Newton himself, notwithstanding the great advantage which he derived from a habit of _patient thinking_, indulged bold and excentric thoughts, of which his Queries at the end of his book of Optics are a sufficient evidence. And a quick conception of distant analogies, which is the great key to unlock the secret of nature, is by no means incompatible with the spirit of _perseverance_, in investigations calculated to ascertain and pursue those analogies. § 1. _Speculations concerning the CONSTITUENT PRINCIPLES of the different kinds of AIR, and the CONSTITUTION and ORIGIN of the ATMOSPHERE, &c._ All the kinds of air that appear to me to be essentially distinct from each other are _fixed air_, _acid_ and _alkaline_; for these, and another principle, called _phlogiston_, which I have not been able to exhibit in the form of _air_, and which has never yet been exhibited by itself in _any form_, seem to constitute all the kinds of air that I am acquainted with. Acid air and phlogiston constitute an air which either extinguishes flame, or is itself inflammable, according, probably, to the quantity of phlogiston combined in it, or the mode of combination. When it extinguishes flame, it is probably so much charged with the phlogistic matter, as to take no more from a burning candle, which must, therefore, necessarily go out in it. When it is inflammable, it is probably so much charged with phlogiston, that the heat communicated by a burning candle makes it immediately separate itself from the other principle with which it was united, in which separation _heat_ is produced, as in other cases of ignition; the action and reaction, which necessarily attends the separation of the constituent principles, exciting probably a vibratory motion in them. Since inflammable, air, by agitation in water, first comes to lose its inflammability, so as to be fit for respiration, and even to admit a candle to burn in it, and then comes to extinguish a candle; it seems probable that water imbibes a great part of this extraordinary charge of phlogiston. And that water _can_ be impregnated with phlogiston, is evident from many of my experiments, especially those in which metals were calcined over it. Water having this affinity with phlogiston, it is probable that it always contains a considerable portion of it; which phlogiston having a stronger affinity with the acid air, which is perhaps the basis of common air, may by long agitation be communicated to it, so as to leave it over saturated, in consequence of which it will extinguish a candle. It is possible, however, that inflammable air and air which extinguishes a candle may differ from one another in the _mode_ of the combination of these two constituent principles, as well as in the proportional quantity of each; and by agitation in water, or long standing, that mode of combination may change. This we know to be the case with other substances, as with _milk_, from which, by standing only, _cream_ is separated; which by agitation becomes _butter_. Also many substances, being at rest, putrefy, and thereby become quite different from what they were before. If this be the case with inflammable air, the water may imbibe either of the constituent parts, whenever any proportion of it is spontaneously separated from the rest; and should this ever be that phlogiston, with which air is but slightly overcharged, as by the burning of a candle, it will be recovered to a state in which a candle may burn in it again. It will be observed, however, that it was only in one instance that I found that strong inflammable air, in its transition to a state in which it extinguishes a candle, would admit a candle to burn in it, and that was very faintly; that then the air was far from being pure, as appeared by the test of nitrous air; and that it was only from a particular quantity of inflammable air which I got from oak, and which had stood a long time in water, that I ever got air which was as pure as common air. Indeed, it is much more easy to account for the passing of inflammable air into a state in which it extinguishes candles, without any intermediate state, in which it will admit a candle to burn in it, than otherwise. This subject requires and deserves farther investigation. It will also be well worth while to examine what difference the agitation of air in natural or artificial _sea-water_ will occasion. Since acid air and phlogiston make inflammable air, and since inflammable air is convertible into air fit for respiration, it seems not to be improbable, that these two ingredients are the only essential principles of common air. For this change is produced by agitation in water only, without the addition of any fixed air, though this kind of air, like various other things of a foreign nature, may be combined with it. Considering also what prodigious quantities of inflammable air are produced by the burning of small pieces of wood or pit-coal, it may not be improbable but that the _volcanos_, with which there are evident traces of almost the whole surface of the earth having been overspread, may have been the origin of our atmosphere, as well as (according to the opinion of some) of all the solid land. The superfluous phlogiston of the air, in the state in which it issues from volcanos, may have been imbibed by the waters of the sea, which it is probable originally covered the surface of the earth, though part of it might have united with the acid vapour exhaled from the sea, and by this union have made a considerable and valuable addition to the common mass of air; and the remainder of this over-charge of phlogiston may have been imbibed by plants as soon as the earth was furnished with them. That an acid vapour is really exhaled from the sea, by the heat of the sun, seems to be evident from the remarkably different states of the atmosphere, in this respect, in hot and cold climates. In Hudson's bay, and also in Russia, it is said, that metals hardly ever rust, whereas they are remarkably liable to rust in Barbadoes, and other islands between the tropics. See Ellis's Voyage, p. 288. This is also the case in places abounding with salt-springs, as Nantwich in Cheshire. That mild air should consist of parts of so very different a nature as an acid vapour and phlogiston, one of which is so exceedingly corrosive, will not appear surprising to a chemist, who considers the very strong affinity which these two principles are known to have with each other, and the exceedingly different properties which substances composed by them possess. This is exemplified in common _sulphur_, which is as mild as air, and may be taken into the stomach with the utmost safety, though nothing can be more destructive than one of its constituent parts, separately taken, viz. oil of vitriol. Common air, therefore, notwithstanding its mildness, may be composed of similar principles, and be a real _sulphur_. That the fixed air which makes part of the atmosphere is not presently imbibed by the waters of the sea, on which it rests, may be owing to the union which this kind of air also appears to be capable of forming with phlogiston. For fixed air is evidently of the nature of an acid; and it appears, in fact, to be capable of being combined with phlogiston, and thereby of constituting a species of air not liable to be imbibed by water. Phlogiston, however, having a stronger affinity with acid air, which I suppose to be the basis of common air, it is not surprising that, uniting with this, in preference to the fixed air, the latter should be precipitated, whenever a quantity of common air is made noxious by an over-charge of phlogiston. The fixed air with which our atmosphere abounds may also be supplied by volcanos, from the vast masses of calcareous matter lodged in the earth, together with inflammable air. Also a part of it may be supplied from the fermentation of vegetables upon the surface of it. At present, as fast as it is precipitated and imbibed by one process, it may be set loose by others. Whether there be, upon, the whole, an increase or a decrease of the general mass of the atmosphere is not easy to conjecture, but I should imagine that it rather increases. It is true that many processes contribute to a great visible diminution of common air, and that when by other processes it is restored to its former wholesomeness, it is not increased in its dimensions; but volcanos and fires still supply vast quantities of air, though in a state not yet fit for respiration; and it will have been seen in my experiments, that vegetable and animal substances, dissolved by putrefaction, not only emit phlogiston, but likewise yield a considerable quantity of permanent elastic air, overloaded indeed with phlogiston, as might be expected, but capable of being purified by those processes in nature by which other noxious air is purified. That particles are continually detaching themselves from the surfaces of all solid bodies, even the metallic ones, and that these particles constitute the most permanent part of the atmosphere, as Sir Isaac Newton supposed, does not appear to me to be at all probable. My readers will have observed, that not only is common air liable to be diminished by a mixture of nitrous air, but likewise air originally produced from inflammable air, and even from nitrous air itself, which never contained any fixed air. From this it may be inferred, that the whole of the diminution of common air by phlogiston is not owing to the precipitation of fixed air, but from a real contraction of its dimensions, in consequence of its union with phlogiston. Perhaps an accurate attention to the specific gravity of air procured from these different materials, and in these different states, may determine this matter, and assist us in investigating the nature of phlogiston. In what _manner_ air is diminished by phlogiston, independent of the precipitation of any of its constituent parts, is not easy to conceive; unless air thus diminished be heavier than air not diminished, which I did not find to be the case. It deserves, however, to be tried with more attention. That phlogiston should communicate absolute _levity_ to the bodies with which it is combined, is a supposition that I am not willing to have recourse to, though it would afford an easy solution of this difficulty. I have likewise observed, that a mouse will live almost as long in inflammable air, when it has been agitated in water, and even before it has been deprived of all its inflammability, as in common air; and yet that in this state it is not, perhaps, so much diminished by nitrous air as common air is. In this case, therefore, the diminution seems to have been occasioned by a contraction of dimensions, and not by a loss of any constituent part; so that the air is really better, that is, more fit for respiration, than, by the test of nitrous air, it would seem to be. If this be the case (for it is not easy to judge with accuracy by experiments with small animals) nitrous air will be an accurate test of the goodness of _common air_ only, that is, air containing a considerable proportion of fixed air. But this is the most valuable purpose for which a test of the goodness of air can be wanted. It will still, indeed, serve for a measure of the goodness of air that does not contain fixed air; but, a smaller degree of diminution in this case, must be admitted to be equivalent to a greater diminution in the other. As I could never, by means of growing vegetables, bring air which had been thoroughly noxious to so pure a state as that a candle would burn in it, it may be suspected that something else besides _vegetation_ is necessary to produce this effect. But it should be considered, that no part of the common atmosphere can ever be in this highly noxious state, or indeed in a state in which a candle will not burn in it; but that even air reduced to this state, either by candles actually burning out in it, or by breathing it, has never failed to be perfectly restored by vegetation, at least so far that candles would burn in it again, and, to all appearance, as well, and as long as ever; so that the growing vegetables, with which the surface of the earth is overspread, may, for any thing that appears to the contrary, be a cause of the purification of the atmosphere sufficiently adequate to the effect. It may likewise be suspected, that since _agitation in water_ injures pure common air, the agitation of the sea may do more harm than good in this respect. But it requires a much more violent and longer continued agitation of air in water than is ever occasioned by the waves of the sea to do the least sensible injury to it. Indeed a light agitation of air in _putrid water_ injures it very materially; but if the water be sweet, this effect is not produced, except by a long and tedious operation, whereas it requires but a very short time, in comparison, to restore a quantity of any of the most noxious kinds of air to a very great degree of wholesomeness by the same process. Dr. Hales found that he could breathe the same air much longer when, in the course of his respiration, it was made to pass through several folds of cloth dipped in vinegar, in a solution of sea-salt, or in salt of tartar, especially the last. Statical Essays, vol. 1. p. 266. The experiment is valuable, and well deserves to be repeated with a greater variety of circumstances. I imagine that the effect was produced by those substances, or by the _water_ which they attracted from the air, imbibing the phlogistic matter discharged from the lungs. Perhaps the phlogiston may unite with the watery part of the atmosphere, in preference to any other part of it, and may by that means be more easily transferred to such salts as imbibe moisture. Sir Isaac Newton defines _flame_ to be _fumus candens_, considering all _smoke_ as being of the same nature, and capable of ignition. But the smoke of common fuel consists of two very different things. That which rises first is mere _water_, loaded with some of the grosser parts of the fuel, and is hardly more capable of becoming red hot than water itself; but the other kind of smoke, which alone is capable of ignition, is properly _inflammable air_, which is also loaded with other heterogeneous matter, so as to appear like a very dense smoke. A lighted candle soon shews them to be essentially different from each other. For one of them instantly takes fire, whereas the other extinguishes a candle. It is remarkable that gunpowder will take fire, and explode in all kinds of air, without distinction, and that other substances which contain _nitre_ will burn freely in those circumstances. Now since nothing can burn, unless there be something at hand to receive the phlogiston, which is set loose in the act of ignition, I do not see how this fact can be accounted for, but by supposing that the acid of nitre, being peculiarly formed to unite with phlogiston, immediately receives it. And if the sulphur, which is thereby formed, be instantly decomposed again, as the chemists in general say, thence comes the explosion of gunpowder, which, however, requires the reaction of some incumbent atmosphere, and without which the materials will only _melt_, and be _dispersed_ without explosion. Nitrous air seems to consist of the nitrous acid vapour united to phlogiston, together, perhaps, with some small portion of the metallic calx; just as inflammable air consists of the vitriolic or marine acid, and the same phlogistic principle. It should seem, however, that phlogiston has a stronger affinity with the marine acid, if that be the basis of common air; for nitrous air being admitted to common air, it is immediately decomposed; probably by the phlogiston joining with the acid principle of the common air, while the fixed air which it contained is precipitated, and the acid of the nitrous air is absorbed by the water in which the mixture is made, or unites with any volatile alkali that happens to be at hand. This, indeed, is hardly agreeable to the hypothesis of most chemists, who suppose that the nitrous acid is stronger than the marine, so as to be capable of dislodging it from any base with which it may be combined; but it agrees with my own experiments on marine acid air, which shew that, in many cases, this _weaker acid_, as it is called, is capable of separating both the vitriolic and the nitrous acids from the phlogiston with which they are combined. On the other hand, the solution of metals in the different acids seems to shew, that the nitrous acid forms a closer union with phlogiston than the other two; because the air which is formed by the nitrous acid is not inflammable, like that which is produced by the oil of vitriol, or the spirit of salt. Also, the same weight of iron does not yield half the quantity of nitrous air that it does of inflammable. The great diminution of nitrous air by phlogiston is not easily accounted for, unless we suppose that its superabundant acid, uniting more intimately with the phlogiston, constitutes a species of _sulphur_ that is not easily perceived or catched; though, in the process with iron, and also in that with liver of sulphur, part of the redundant phlogiston forms such an union with the acid as gives it a kind of inflammability. It appears to me to be very probable, that the spirit of nitre might be exhibited in the form of _air_, if it were possible to find any fluid by which it could be confined; but it unites with quicksilver as well as with water, so that when, by boiling the spirit of nitre, the fumes are driven through the glass tube, fig. 8, they instantly seize upon the quicksilver through which they are to be conveyed, and uniting with it, form a substance that stops up the tube: a circumstance which has more than once exposed me to very disagreeable accidents, in consequence of the bursting of the phials. I do not know any inquiry more promising than the investigation of the properties of _nitre_, the _nitrous acid_, and _nitrous air_. Some of the most wonderful phenomena in nature are connected with them, and the subject seems to be fully within our reach. § 2. _Speculations arising from the consideration of the similarity of the ELECTRIC MATTER and PHLOGISTON._ There is nothing in the history of philosophy more striking than the rapid progress of _electricity_. Nothing ever appeared more trifling than the first effects which were observed of this agent in nature, as the attraction and repulsion of straws, and other light substances. It excited more attention by the flashes of _light_ which it exhibited. We were more seriously alarmed at the electrical _shock_, and the effects of the electrical _battery_; and we were astonished to the highest degree by the discovery of the similarity of electricity with _lightning_, and the _aurora borealis_, with the connexion it seems to have with _water-spouts_, _hurricanes_, and _earthquakes_, and also with the part that is probably assigned to it in the system of _vegetation_, and other the most important processes in nature. Yet, notwithstanding all this, we have been, within a few years, more puzzled than ever with the electricity of the _torpedo_, and of the _anguille temblante_ of Surinam, especially since that most curious discovery of Mr. Walsh's, that the former of these wonderful fishes has the power of giving a proper electrical shock; the electrical matter which proceeds from it performing a real circuit from one part of the animal to the other; while both the fish which performs this experiment and all its apparatus are plunged in water, which is known to be a conducting substance. Perhaps, however, by considering this fact in connexion with a few others, and especially with what I have lately observed concerning the identity of electricity and phlogiston, a little light may be thrown upon this subject, in consequence of which we may be led to consider electricity in a still more important light. Many of my readers, I am aware, will smile at what I am going to advance; but the apprehension of this shall not interrupt my speculations, how chimerical soever they may be thought to be. The facts, the consideration of which I would combine with that of the electricity of the torpedo, are the following. First, The remarkable electricity of the feathers of a paroquet, observed by Mr. Hartmann, an account of which may be seen in Mr. Rozier's Journal for Sept. 1771. p. 69. This bird never drinks, but often washes itself; but the person who attended it having neglected to supply it with water for this purpose, its feathers appeared to be endued with a proper electrical virtue, repelling one another, and retaining their electricity a long time after they were plucked from the body of the bird, just as they would have done if they had received electricity from an excited glass tube. Secondly, The electric matter directed through the body of any muscle forces it to contract. This is known to all persons who attend to what is called the electrical shock; which certainly occasions a proper _convulsion_, but has been more fully illustrated by Father Beccaria. See my _History of Electricity_, p. 402. Lastly, Let it be considered that the proper nourishment of an animal body, from which the source and materials of all muscular motion must be derived, is probably some modification of phlogiston. Nothing will nourish that does not contain phlogiston, and probably in such a state as to be easily separated from it by the animal functions. That the source of muscular motion is phlogiston is still more probable, from the consideration of the well known effects of vinous and spirituous liquors, which consist very much of phlogiston, and which instantly brace and strengthen the whole nervous and muscular system; the phlogiston in this case being, perhaps, more easily extricated, and by a less tedious animal process, than in the usual method of extracting it from mild aliments. Since, however, the mildest aliments do the same thing more slowly and permanently, that spirituous liquors do suddenly and transiently, it seems probable that their operation is ultimately the same. This conjecture is likewise favoured by my observation, that respiration and putrefaction affect common air in the same manner, and in the same manner in which all other processes diminish air and make it noxious, and which agree in nothing but the emission of phlogiston. If this be the case, it should seem that the phlogiston which we take in with our aliment, after having discharged its proper function in the animal system (by which it probably undergoes some unknown alteration) is discharged as _effete_ by the lungs into the great common _menstruum_, the atmosphere. My conjecture suggested (whether supported or not) by these facts, is, that animals have a power of converting phlogiston, from the state in which they receive it in their nutriment, into that state in which it is called the electrical fluid; that the brain, besides its other proper uses, is the great laboratory and repository for this purpose; that by means of the nerves this great principle, thus exalted, is directed into the muscles, and forces them to act, in the same manner as they are forced into action when the electric fluid is thrown into them _ab extra_. I farther suppose, that the generality of animals have no power of throwing this generated electricity any farther than the limits of their own system; but that the _torpedo_, and animals of a similar construction, have likewise the power, by means of an additional apparatus, of throwing it farther, so as to affect other animals, and other substances at a distance from them. In this case, it should seem that the electric matter discharged from the animal system (by which it is probably more exhausted and fatigued than by ordinary muscular motion) would never return to it, at least so as to be capable of being made use of a second time, and yet if the structure of these animals be such as that the electric matter shall dart from one part of them only, while another part is left suddenly deprived of it, it may make a circuit, as in the Leyden phial. As to the _manner_ in which the electric matter makes a muscle contract, I do not pretend to have any conjecture worth mentioning. I only imagine that whatever can make the muscular fibres recede from one another farther than the parts of which they consist, must have this effect. Possibly, the _light_ which is said to proceed from some animals, as from cats and wild beasts, when they are in pursuit of their prey in the night, may not only arise, as it has hitherto been supposed to do, from the friction of their hairs or bristles, &c. but that violent muscular exertion may contribute to it. This may assist them occasionally to catch their prey; as glow-worms, and other insects, are provided with a constant light for that purpose, to the supply of which light their nutriment may also contribute. I would not even say that the light which is said to have proceeded from some human bodies, of a particular temperament, and especially on some extraordinary occasions, may not have been of the electrical kind, that is, produced independently of friction, or with less friction than would have produced it in other persons; as in those cases related by Bartholin in his treatice _De luce animalium_. See particularly what he says concerning Theodore king of the Goths, p. 54, concerning Gonzaga duke of Mantua, p. 57, and Gothofred Antonius, p. 123: But I would not have my readers suppose that I lay much stress upon stories no better authenticated than these. The electric matter in passing through non-conducting substances always emits _light_. This light I have been sometimes inclined to suspect might have been supplied from the substance through which it passes. But I find that after the electric spark has diminished a quantity of air as much as it possibly can, so that it has no more visible effect upon it, the electric light in that air is not at all lessened. It is probable, therefore, that electric light comes from the electric matter itself; and this being a modification of phlogiston, it is probable that _all light_ is a modification of phlogiston also. Indeed, since no other substances besides such as contain phlogiston are capable of ignition, and consequently of becoming luminous, it was on this account pretty evident, prior to these deductions from electrical phenomena, that light and phlogiston are the same thing, in different forms or states. It appears to me that _heat_ has no more proper connexion with phlogiston than it has with water, or any other constituent part of bodies; but that it is a state into which the parts of bodies are thrown by their action and reaction with respect to one another; and probably (as the English philosophers in general have supposed) the heated state of bodies may consist of a subtle vibratory motion of their parts. Since the particles which constitute light are thrown from luminous bodies with such amazing velocity, it is evident that, whatever be the cause of such a projection, the reaction consequent upon it must be considerable. This may be sufficient not only to keep up, but also to increase the vibration of the parts of those bodies in which the phlogiston is not very firmly combined; and the difference between the substances which are called _inflammable_ and others which also contain phlogiston may be this, that in the former the heat, or the vibration occasioned by the emission of their own phlogiston, may be sufficient to occasion the emission of more, till the whole be exhausted; that is, till the body be reduced to ashes. Whereas in bodies which are not inflammable, the heat occasioned by the emission of their own phlogiston may not be sufficient for this purpose, but an additional heat _ab extra_ may be necessary. Some philosophers dislike the term _phlogiston_; but, for my part, I can see no objection to giving that, or any other name, to a _real something_, the presence or absence of which makes so remarkable difference in bodies, as that of _metallic calces_ and _metals_, _oil of vitriol_ and _brimstone_, &c. and which may be transferred from one substance to another, according to certain known laws, that is, in certain definite circumstances. It is certainly hard to conceive how any thing that answers this description can be only a mere _quality_, or mode of bodies, and not _substance_ itself, though incapable of being exhibited alone. At least, there can be no harm in giving this name to any _thing_, or any _circumstance_ that is capable of producing these effects. If it should hereafter appear not to be a substance, we may change our phraseology, if we think proper. On the other hand I dislike the use of the term _fire_, as a constituent principle of natural bodies, because, in consequence of the use that has generally been made of that term, it includes another thing or circumstance, viz. _heat_, and thereby becomes ambiguous, and is in danger of misleading us. When I use the term phlogiston, as a principle in the constitution of bodies, I cannot mislead myself or others, because I use one and the same term to denote only one and the same _unknown cause_ of certain well-known effects. But if I say that _fire_ is a principle in the constitution of bodies, I must, at least, embarrass myself with the distinction of fire _in a state of action_, and fire _inactive_, or quiescent. Besides I think the term phlogiston preferable to that of fire, because it is not in common use, but confined to philosophy; so that the use of it may be more accurately ascertained. Besides, if phlogiston and the electric matter be the same thing, though it cannot be exhibited alone, in a _quiescent state_, it may be exhibited alone under one of its modifications, when it is in _motion_. And if light be also phlogiston, or some modification or subdivision of phlogiston, the same thing is capable of being exhibited alone in this other form also. In my paper on the _conducting power of charcoal_, (See Philosophical Transactions, vol. 60. p. 221) I observed that there is a remarkable resemblance between metals and charcoal; as in both these substances there is an intimate union of phlogiston with an earthy base; and I said that, had there been any phlogiston in _water_, I should have concluded, that there had been no conducting power in nature, but in consequence of an union of this principle with some base; for while metals have phlogiston they conduct electricity, but when they are deprived of it they conduct no longer. Now the affinity which I have observed between phlogiston and water leads me to conclude that water, in its natural state, does contain some portion of phlogiston; and according to the hypothesis just now mentioned they must be intimately united, because water is not inflammable. I think, therefore, that after this state of hesitation and suspence, I may venture to lay it down as a characteristic distinction between conducting and non-conducting substances, that the former contain phlogiston intimately united with some base, and that the latter, if they contain phlogiston at all, retain it more loosely. In what manner this circumstance facilitates the passing of the electric matter through one substance, and obstructs its passage through another, I do not pretend to say. But it is no inconsiderable thing to have advanced but _one step_ nearer to an explanation of so very capital a distinction of natural bodies, as that into conductors and non-conductors of electricity. I beg leave to mention in this place, as favourable to this hypothesis, a most curious discovery made very lately by Mr. Walsh, who being assisted by Mr. De Luc to make a more perfect vacuum in the double or arched barometer, by boiling the quicksilver in the tube, found that the electric spark or shock would no more pass through it, than through a stick of solid glass. He has also noted several circumstances that affect this vacuum in a very extraordinary manner. But supposing that vacuum to be perfect, I do not see how we can avoid inferring from the fact, that some _substance_ is necessary to conduct electricity; and that it is not capable, by its own expansive power, of extending itself into spaces void of all matter, as has generally been supposed, on the idea of there being nothing to obstruct its passage. Indeed if this was the case, I do not see how the electric matter could be retained within the body of the earth, or any of the planets, or solid orbs of any kind. In nature we see it make the most splendid appearance in the upper and thinner regions of the atmosphere, just as it does in a glass tube nearly exhausted; but if it could expand itself beyond that degree of rarity, it would necessarily be diffused into the surrounding vacuum, and continue and be condensed there, at least in a greater proportion than in or near any solid body, as Newton supposed concerning his _ether_. If that mode of vibration which constitutes heat be the means of converting phlogiston from that state in which it makes a part of solid bodies, and eminently contributes to the firmness of their texture into that state in which it diminishes common air; may not that peculiar kind of vibration by which Dr. Hartley supposes the brain to be affected, and by which he endeavours to explain all the phenomena of sensation, ideas, and muscular motion, be the means by which the phlogiston, which is conveyed into the system by nutriment, is converted into that form or modification of it of which the electric fluid consists. These two states of phlogiston may be conceived to resemble, in some measure, the two states of fixed air, viz. elastic, or non-elastic; a solid, or a fluid. THE APPENDIX. In this Appendix I shall present the reader with the communications of several of my friends on the subject of the preceding work. Among them I should with pleasure have inserted some curious experiments, made by Dr. Hulme of Halifax, on the air extracted from Buxton water, and on the impregnation of several fluids, with different kinds of air; but that he informs me he proposes to make a separate publication on the subject. NUMBER I. _EXPERIMENTS made by Mr. Hey to prove that there is no OIL of VITRIOL in water impregnated with FIXED AIR._ It having been suggested, that air arising from a fermenting mixture of chalk and oil of vitriol might carry up with it a small portion of the vitriolic acid, rendered volatile by the act of fermentation; I made the following experiments, in order to discover whether the acidulous taste, which water impregnated with such air affords, was owing to the presence of any acid, or only to the fixed air it had absorbed. EXPERIMENT I. I mixed a tea-spoonful of syrup of violets with an ounce of distilled water, saturated with fixed air procured from chalk by means of the vitriolic acid; but neither upon the first mixture, nor after standing 24 hours, was the colour of the syrup at all changed, except by its simple dilution. EXPERIMENT II. A portion of the same distilled water, unimpregnated with fixed air, was mixed with the syrup in the same proportion: not the least difference in colour could be perceived betwixt this and the above-mentioned mixture. EXPERIMENT III. One drop of oil of vitriol being mixed with a pint of the same distilled water, an ounce of this water was mixed with a tea-spoonful of the syrup. This mixture was very distinguishable in colour from the two former, having a purplish cast, which the others wanted. EXPERIMENT IV. The distilled water impregnated with so small a quantity of vitriolic acid, having a more agreeable taste than when alone, and yet manifesting the presence of an acid by means of the syrup of violets; I subjected it to some other tests of acidity. It formed curds when agitated with soap, lathered with difficulty, and very imperfectly; but not the least ebullition could be discovered upon dropping in spirit of sal ammoniac, or solution of salt of tartar, though I had taken care to render the latter free from causticity by impregnating it with fixed air. EXPERIMENT V. The distilled water saturated with fixed air neither effervesced, nor shewed any clouds, when mixed with the fixed or volatile alkali. EXPERIMENT VI. No curd was formed by pouring this water upon an equal quantity of milk, and boiling them together. EXPERIMENT VII. When agitated with soap, this water produced curds, and lathered with some difficulty; but not so much as the distilled water mixed with vitriolic acid in the very small proportion above-mentioned. The same distilled water without any impregnation of fixed air lathered with soap without the least previous curdling. River-water, and a pleasant pump-water not remarkably hard, were compared with these. The former produced curds before it lathered, but not quite in so great a quantity as the distilled water impregnated with fixed air: the latter caused a stronger curd than any of the others above-mentioned. EXPERIMENT VIII. Apprehending that the fixed air in the distilled water occasioned the coagulation, or separation of the oily part of the soap, only by destroying the causticity of the _lixivium_, and thereby rendering the union less perfect betwixt that and the tallow, and not by the presence of any acid; I impregnated a fresh quantity of the same distilled water with fixed air, which had passed through half a yard of a wide barometer-tube filled with salt of tartar; but this water caused the same curdling with soap as the former had done, and appeared in every respect to be exactly the same. EXPERIMENT IX. Distilled water saturated with fixed air formed a white cloud and precipitation, upon being mixed with a solution of _saccharum saturni_. I found likewise, that fixed air, after passing through the tube filled with alkaline salt, upon being let into a phial containing a solution of the metalic salt in distilled water, caused a perfect separation of the lead, in the form of a white powder; for the water, after this precipitation, shewed no cloudiness upon a fresh mixture of the substances which had before rendered it opaque. NUMBER II. _A Letter from Mr. HEY to Dr. PRIESTLEY, concerning the Effects of fixed Air applied by way of Clyster._ Leeds, Feb. 15th, 1772. Reverend Sir, Having lately experienced the good effects of fixed air in a putrid fever, applied in a manner, I believe not heretofore made use of, I thought it proper to inform you of the agreeable event, as the method of applying this powerful corrector of putrefaction took its rise principally from your observations and experiments on factitious air; and now, at your request, I send the particulars of the case I mentioned to you, as far as concerns the administration of this remedy. January 8, 1772, Mr. Lightbowne, a young gentleman who lives with me, was seized with a fever, which, after continuing about ten days, began to be attended with those symptoms that indicate a putrescent state of the fluids. 18th, His tongue was black in the morning when I first visited him, but the blackness went off in the day-time upon drinking: He had begun to doze much the preceding day, and now he took little notice of those that were about him: His belly was loose, and had been so for some days: his pulse beat 110 strokes in a minute, and was rather low: he was ordered to take twenty-five grains of Peruvian bark with five of tormentil-root in powder every four hours, and to use red wine and water cold as his common drink. 19th, I was called to visit him early in the morning, on account of a bleeding at the nose which had come on: he lost about eight ounces of blood, which was of a loose texture: the hæmorrhage was suppressed, though not without some difficulty, by means of tents made of soft lint, dipped in cold water strongly impregnated with tincture of iron, which were introduced within the nostrils quite through to their posterior apertures; a method which has never yet failed me in like cases. His tongue was now covered with a thick black pellicle, which was not diminished by drinking: his teeth were furred with the same kind of sordid matter, and even the roof of his mouth and sauces were not free from it: his looseness and stupor continued, and he was almost incessantly muttering to himself: he took this day a scruple of the Peruvian bark with ten grains of tormentil every two or three hours: a starch clyster, containing a drachm of the compound powder of bole, without opium, was given morning and evening: a window was set open in his room, though it was a severe frost, and the floor was frequently sprinkled with vinegar. 20th, He continued nearly in the same state: when roused from his dozing, he generally gave a sensible answer to the questions asked him; but he immediately relapsed, and repeated his muttering. His skin was dry, and harsh, but without _petechiæ_. He sometimes voided his urine and _fæces_ into the bed, but generally had sense enough to ask for the bed-pan: as he now nauseated the bark in substance, it was exchanged for Huxham's tincture, of which he took a table spoonful every two hours in a cup full of cold water: he drank sometimes a little of the tincture of roses, but his common liquors were red wine and water, or rice-water and brandy acidulated with elixir of vitriol: before drinking, he was commonly requested to rinse his mouth with water to which a little honey and vinegar had been added. His looseness rather increased, and the stools were watery, black, and foetid: It was judged necessary to moderate this discharge, which seemed to sink him, by mixing a drachm of the _theriaca Andromachi_ with each clyster. 21st. The same putrid symptoms remained, and a _subsultus tendinum_ came on: his stools were more foetid; and so hot, that the nurse assured me she could not apply her hand to the bed-pan, immediately after they were discharged, without feeling pain on this account: The medicine and clysters were repeated. Reflecting upon the disagreeable necessity we seemed to lie under of confining this putrid matter in the intestines, lest the evacuation should destroy the _vis vitæ_ before there was time to correct its bad quality, and overcome its bad effects, by the means we were using; I considered, that, if this putrid ferment could be more immediately corrected, a stop would probably be put to the flux, which seemed to arise from, or at least to be encreased by it; and the _fomes_ of the disease would likewise be in a great measure removed. I thought nothing was so likely to effect this, as the introduction of fixed air into the alimentary canal, which, from the experiments of Dr. Macbride, and those you have made since his publication, appears to be the most powerful corrector of putrefaction hitherto known. I recollected what you had recommended to me as deserving to be tried in putrid diseases, I mean, the injection of this kind of air by way of clyster, and judged that in the present case such a method was clearly indicated. The next morning I mentioned my reflections to Dr. Hird and Dr. Crowther, who kindly attended this young gentleman at my request, and proposed the following method of treatment, which, with their approbation, was immediately entered upon. We first gave him five grains of ipecacuanha, to evacuate in the most easy manner part of the putrid _colluvies_: he was then allowed to drink freely of brisk orange-wine, which contained a good deal of fixed air, yet had not lost its sweetness. The tincture of bark was continued as before; and the water which he drank along with it, was impregnated with fixed air from the atmosphere of a large vat of fermenting wort, in the manner I had learned from you. Instead of the astringent clyster, air alone was injected, collected from a fermenting mixture of chalk and oil of vitriol: he drank a bottle of orange-wine in the course of this day, but refused any other liquor except water and his medicine: two bladders full of air were thrown up in the afternoon. 23d. His stools were less frequent; their heat likewise and peculiar _foetor_ were considerably diminished; his muttering was much abated, and the _subsultus tendinum_ had left him. Finding that part of the air was rejected when given with a bladder in the usual way, I contrived a method of injecting it which was not so liable to this inconvenience. I took the flexible tube of that instrument which is used for throwing up the fume of tobacco, and tied a small bladder to the end of it that is connected with the box made for receiving the tobacco, which I had previously taken off from the tube: I then put some bits of chalk into a six ounce phial until it was half filled; upon these I poured such a quantity of oil of vitriol as I thought capable of saturating the chalk, and immediately tied the bladder, which I had fixed to the tube, round the neck of the phial: the clyster-pipe, which was fastened to the other end of the tube, was introduced into the _anus_ before the oil of vitriol was poured upon the chalk. By this method the air passed gradually into the intestines as it was generated; the rejection of it was in a great measure prevented; and the inconvenience of keeping the patient uncovered during the operation was avoided. 24th, He was so much better, that there seemed to be no necessity for repeating the clysters: the other means were continued. The window of his room was now kept shut. 25th, All the symptoms of putrescency had left him; his tongue and teeth were clean; there remained no unnatural blackness or _foetor_ in his stool, which had now regained their proper consistence; his dozing and muttering were gone off; and the disagreeable odour of his breath and perspiration was no longer perceived. He took nourishment to-day, with pleasure; and, in the afternoon, sat up an hour in his chair. His fever, however, did not immediately leave him; but this we attributed to his having caught cold from being incautiously uncovered, when the window was open, and the weather extremely severe; for a cough, which had troubled him in some degree from the beginning, increased, and he became likewise very hoarse for several days, his pulse, at the same time, growing quicker: but these complaints also went off, and he recovered, without any return of the bad symptoms above-mentioned. I am, Reverend Sir, Your obliged humble Servant, WM. HEY. POSTSCRIPT October 29, 1772. Fevers of the putrid kind have been so rare in this town, and in its neighbourhood, since the commencement of the present year, that I have not had an opportunity of trying again the effects of fixed air, given by way of clyster, in any case exactly similar to Mr. Lightbowne's. I have twice given water saturated with fixed air in a fever of the putrescent kind, and it agreed very well with the patients. To one of them the aërial clysters were administred, on account of a looseness, which attended the fever, though the stools were not black, nor remarkably hot or foetid. These clysters did not remove the looseness, though there was often a greater interval than usual betwixt the evacuations, after the injection of them. The patient never complained of any uneasy distention of the belly from the air thrown up, which, indeed, is not to be wondered at, considering how readily this kind of air is absorbed by aqueous and other fluids, for which sufficient time was given, by the gradual manner of injecting it. Both those patients recovered though the use of fixed air did not produce a crisis before the period at which such fevers usually terminate. They had neither of them the opportunity of drinking such wine as Mr. Lightbowne took, after the use of fixed air was entered upon; and this, probably, was some disadvantage to them. I find the methods of procuring fixed air, and impregnating water with it, which you have published, are preferable to those I made use of in Mr. Lightbowne's case. The flexible tube used for conveying the fume of tobacco into the intestines, I find to be a very convenient instrument in this case, by the method before-mentioned (only adding water to the chalk, before the oil of vitriol is instilled, as you direct) the injection of air may be continued at pleasure, without any other inconvenience to the patient, than what may arise from his continuing in one position during the operation, which scarcely deserves to be mentioned, or from the continuance of the clyster-pipe within the anus, which is but trifling, if it be not shaken much, or pushed against the rectum. When I said in my letter, that fixed air appeared to be the greatest corrector of putrefaction hitherto known, your philosophical researches had not then made you acquainted with that most remarkably antiseptic property of nitrous air. Since you favoured me with a view of some astonishing proofs of this, I have conceived hopes, that this kind of air may likewise be applied medicinally to great advantage. W. H. NUMBER III. _Observations on the MEDICINAL USES of FIXED AIR. By THOMAS PERCIVAL, M. D. Fellow of the ROYAL SOCIETY, and of the SOCIETY of ANTIQUARIES in LONDON._ These Observations on the MEDICINAL USES OF FIXED AIR have been before published in the Second Volume of my Essays; but are here reprinted with considerable additions. They form a part of an experimental inquiry into this interesting and curious branch of Physics; in which the friendship of Dr. Priestley first engaged me, in concert with himself. Manchester, March 16, 1774. In a course of Experiments, which is yet unfinished, I have had frequent opportunities of observing that FIXED AIR may in no inconsiderable quantity be breathed without danger or uneasiness. And it is a confirmation of this conclusion, that at Bath, where the waters copiously exhale this mineral spirit,[15] the bathers inspire it with impunity. At Buxton also, where the Bath is in a close vault, the effects of such _effluvia_, if noxious, must certainly be perceived. Encouraged by these considerations, and still more by the testimony of a very judicious Physician at Stafford, in favour of this powerful antiseptic remedy, I have administered fixed air in a considerable number of cases of the PHTHISIS PULMONALIS, by directing my patients to inspire the steams of an effervescing mixture of chalk and vinegar; or what I have lately preferred, of vinegar and potash. The hectic fever has in several instances been considerably abated, and the matter expectorated has become less offensive, and better digested. I have not yet been so fortunate in any one case, as to effect a cure; although the use of mephitic air has been accompanied with proper internal medicines. But Dr. Withering, the gentleman referred to above, informs me, that he has been more successful. One Phthisical patient under his care has by a similar course intirely recovered; another was rendered much better; and a third, whose case was truly deplorable, seemed to be kept alive by it more than two months. It may be proper to observe that fixed air can only be employed with any prospect of success, in the latter stages of the _phthisis pulmonalis_, when a purulent expectoration takes place. After the rupture and discharge of a VOMICA also, such a remedy promises to be a powerful palliative. Antiseptic fumigations and vapours have been long employed, and much extolled in cases of this kind. I made the following experiment, to determine whether their efficacy, in any degree, depends on the separation of fixed air from their substance. One end of a bent tube was fixed in a phial full of lime-water; the other end in a bottle of the tincture of myrrh. The junctures were carefully luted, and the phial containing the tincture of myrrh was placed in water, heated almost to the boiling point, by the lamp of a tea-kettle. A number of air-bubbles were separated, but probably not of the mephitic kind, for no precipitation ensued in the lime water. This experiment was repeated with the _tinct. tolutanæ, ph. ed._ and with _sp, vinos. camp._ and the result was entirely the same. The medicinal action therefore of the vapours raised from such tinctures, cannot be ascribed to the extrication of fixed air; of which it is probable bodies are deprived by _chemical solution_ as well as by _mixture_. If mephitic air be thus capable of correcting purulent matter in the lungs, we may reasonably infer it will be equally useful when applied externally to foul ULCERS. And experience confirms the conclusion. Even the sanies of a CANCER, when the carrot poultice failed, has been sweetened by it, the pain mitigated, and a better digestion produced. The cases I refer to are now in the Manchester infirmary, under the direction of my friend Mr. White, whose skill as a surgeon, and abilities as a writer are well known to the public. Two months have elapsed since these observations were written,[16] and the same remedy, during that period, has been assiduously applied, but without any further success. The progress of the cancers seems to be checked by the fixed air; but it is to be feared that a cure will not be effected. A palliative remedy, however, in a disease so desperate and loathsome, may be considered as a very valuable acquisition. Perhaps NITROUS AIR might be still more efficacious. This species of factitious air is obtained from all the metals except zinc, by means of the nitrous acid; and Dr. Priestley informs me, that as a sweetener and antiseptic it far surpasses fixed air. He put two mice into a quantity of it, one just killed, the other offensively putrid. After twenty-five days they were both perfectly sweet. In the ULCEROUS SORE THROAT much advantage has been experienced from the vapours of effervescing mixtures drawn into the _fauces_[17]. But this remedy should not supersede the use of other antiseptic applications.[18] A physician[19] who had a very painful APTHOUS ULCER at the point of his tongue, found great relief, when other remedies failed, from the application of fixed air to the part affected. He held his tongue over an effervescing mixture of potash and vinegar; and as the pain was always mitigated, and generally removed by this vaporisation, he repeated it, whenever the anguish arising from the ulcer was more than usually severe. He tried a combination of potash and oil of vitriol well diluted with water; but this proved stimulant and increased his pain; probably owing to some particles of the acid thrown upon the tongue, by the violence of the effervescence. For a paper stained with the purple juice of radishes, when held at an equal distance over two vessels, the one containing potash and vinegar, the other the same alkali and _Spiritus vitrioli tenuis_, was unchanged by the former, but was spotted with red, in various parts, by the latter. In MALIGNANT FEVERS wines abounding with fixed air may be administered, to check the septic ferment, and sweeten the putrid _colluvies_ in the _primæ viæ_. If the laxative quality of such liquors be thought an objection to the use of them, wines of a greater age may be given, impregnated with mephitic air, by a simple but ingenious contrivance of my friend Dr. Priestley.[20] The patient's common drink might also be medicated in the same way. A putrid DIARRH[OE]A frequently occurs in the latter stage of such disorder, and it is a most alarming and dangerous symptom. If the discharge be stopped by astringents, a putrid _fomes_ is retained in the body, which aggravates the delirium and increases the fever. On the contrary, if it be suffered to take its course, the strength of the patient must soon be exhausted, and death unavoidably ensue. The injection of mephitic air into the intestines, under these circumstances, bids fair to be highly serviceable. And a case of this deplorable kind, has lately been communicated to me, in which the vapour of chalk and oil of vitriol conveyed into the body by the machine employed for tobacco clysters, quickly restrained the _diarrhoea_, corrected the heat and foetor of the stools, and in two days removed every symptom of danger[21]. Two similar instances of the salutary effects of mephitic air, thus administered, have occurred also in my own practice, the history of which I shall briefly lay before the reader. May we not presume that the same remedy would be equally useful in the DYSENTERY? The experiment is at least worthy of trial. Mr. W----, aged forty-four years, corpulent, inactive, with a short neck, and addicted to habits of intemperance, was attacked on the 7th of July 1772, with symptoms which seemed to threaten an apoplexy. On the 8th, a bilious looseness succeeded, with a profuse hoemorrhage from the nose. On the 9th, I was called to his assistance. His countenance was bloated, his eyes heavy, his skin hot, and his pulse hard, full, and oppressed. The diarrhoea continued; his stools were bilious and very offensive; and he complained of griping pains in his bowels. He had lost, before I saw him, by the direction of Mr. Hall, a surgeon of eminence in Manchester, eight ounces of blood from the arm, which was of a lax texture; and he had taken a saline mixture every sixth hour. The following draught was prescribed, and a dose of rhubarb directed to be administered at night. Rx. _Aq. Cinnam. ten._ oz. j. _Succ. Limon. recent._ oz. ß. _Salis Nitri gr. xij. Syr. è Succo Limon. dr. j. M. f. Haust._ _4tis horis sumendus._ July 11. The _Diarrhoea_ was more moderate; his griping pains were abated; and he had less stupor and dejection in his countenance. Pulse 90, not so hard or oppressed. As his stools continued to be foetid, the dose of rhubarb was repeated; and instead of simple cinnamon-water, his draughts were prepared with an infusion of columbo root. 12. The _Diarrhoea_ continued; his stools were involuntary; and he discharged in this way a quantity of black, grumous, and foetid blood. Pulse hard and quick; skin hot; tongue covered with a dark fur; abdomen swelled; great stupor. Ten grains of columbo root, and fifteen of the _Gummi rubrum astringens_ were added to each draught. Fixed air, under the form of clysters, was injected every second or third hour; and directions were given to supply the patient plentifully with water, artificially impregnated with mephitic air. A blister was also laid between his shoulders. 13. The Diarrhoea continued, with frequent discharges of blood; but the stools had now lost their foetor. Pulse 120; great flatulence in the bowels, and fulness in the belly. The clysters of fixed air always diminished the tension of the _Abdomen_, abated flatulence, and made the patient more easy and composed for some time after their injection. They were directed to be continued, together with the medicated water. The nitre was omitted, and a scruple of the _Confect. Damocratis_ was given every fourth hour, in an infusion of columbo root. 14. The Diarrhoea was how checked, His other symptoms continued as before. Blisters were applied to the arms; and a drachm and a half of the _Tinctura Serpentariæ_ was added to each draught. 15. His pulse was feeble, quicker and more irregular. He dosed much; talked incoherently; and laboured under a slight degree of _Dyspnæa_. His urine, which had hitherto assumed no remarkable appearance, now became pale. Though he discharged wind very freely, his belly was much swelled, except for a short time after the injection of the air-clysters. The following draughts were then prescribed. Rx _Camphoræ mucilag. G. Arab, solutæ gr. viij. Infus. Rad. Columbo oz. jfs Tinct. Serpent. dr. ij Confect. Card. scruple j Syr. è Cort. Aurant dr. i m. f. Haust. 4tis horis sumendus._ Directions were given to foment his feet frequently with vinegar and warm water. 16. He has had no stools since the 14th. His _Abdomen_ is tense. No change in the other symptoms. The _Tinct. Serpent._ was omitted in his draughts, and an equal quantity of _Tinct. Rhæi Sp._ substituted in its place. In the evening he had a motion to stool, of which he was for the first time so sensible, as to give notice to his attendants. But the discharge, which was considerable and slightly offensive, consisted almost entirely of blood, both in a coagulated and in a liquid state. His medicines were therefore varied as follows: Rx. _Decoct. Cort. Peruv. oz. iss Tinct. Cort. ejusd. dr. ij. Confect. Card. scruple j Gum. Rubr. Astring. gr. xv. Pulv. Alnmin. gr. vij. m. f. Haustus 4tis horis sumendus._ Red Port wine was now given more freely in his medicated water; and his nourishment consisted of sago and salep. In this state, with very little variation, he continued for several days; at one time ostive, and at another discharging small quantities of fæces, mixed with grumous blood. The air-clysters were continued, and the astringents omitted. 20. His urine was now of an amber colour, and deposited a slight sediment. His pulse was more regular, and although still very quick, abated in number ten strokes in a minute. His head was less confused, and his sleep seemed to be refreshing. No blood appeared in his stools, which were frequent, but small in quantity; and his _Abdomen_ was less tense than usual. He was extremely deaf; but gave rational answers to the few questions which were proposed to him; and said he felt no pain. 21. He passed a very restless night; his delirium recurred; his pulse beat 125 strokes in a minute; his urine was of a deep amber colour when first voided; but when cold assumed the appearance of cow's whey. The _Abdomen_ was not very tense, nor had he any further discharge of blood. Directions were given to shave his head, and to wash it with a mixture of vinegar and brandy; the quantity of wine in his drink was diminished; and the frequent use of the pediluvium was enjoined. The air-clysters were discontinued, as his stools were not offensive, and his _Abdomen_ less distended. 22. His pulse was now small, irregular, and beat 130 strokes in a minute. The _Dyspnoea_ was greatly increased; his skin was hot, and bedewed with a clammy moisture; and every symptom seemed to indicate the approach of death. In this state he continued till evening, when he recruited a little. The next day he had several slight convulsions. His urine which was voided plentifully, still put on the appearance of whey when cold. Cordial and antispasmodic draughts, composed of camphor, tincture of castor, and _Sp. vol. aromat._ were now directed; and wine was liberally administered. 24. He rose from his bed, and by the assistance of his attendants walked across the chamber. Soon after he was seized with a violent convulsion, in which he expired. To adduce a case which terminated fatally as a proof of the efficacy of any medicine, recommended to the attention of the public, may perhaps appear singular; but cannot be deemed absurd, when that remedy answered the purposes for which it was intended. For in the instance before us; fixed air was employed, not with an expectation that it would cure the fever, but to obviate the symptoms of putrefaction, and to allay the uneasy irritation in the bowels. The disease was too malignant, the nervous system too violently affected, and the strength of the patient too much exhausted by the discharges of blood which he suffered, to afford hopes of recovery from the use of the most powerful antiseptics. But in the succeeding case the event proved more fortunate. Elizabeth Grundy, aged seventeen, was attacked on the 10th of December 1772, with the usual symptoms of a continued fever. The common method of cure was pursued; but the disease increased, and soon assumed a putrid type. On the 23d I found her in a constant delirium, with a _subsultus tendinum_. Her skin was hot and dry, her tongue black, her thirst immoderate, and her stools frequent, extremely offensive, and for the most part involuntary. Her pulse beat 130 strokes in a minute; she dosed much; and was very deaf. I directed wine to be administered freely; a blister to be applied to her back; the _pediluvium_ to be used several times in the day; and mephitic air to be injected under the form of a clyster every two hours. The next day her stools were less frequent, had lost their foetor, and were no longer discharged involuntarily; her pulse was reduced to 110 strokes in the minute; and her delirium was much abated. Directions were given to repeat the clysters, and to supply the patient liberally with wine. These means were assiduously pursued several days; and the young woman was so recruited by the 28th, that the injections were discontinued. She was now quite rational, and not averse to medicine. A decoction of Peruvian bark was therefore prescribed, by the use of which she speedily recovered her health. I might add a third history of a putrid disease, in which the mephitic air is now under trial, and which affords the strongest proof both of the _antiseptic_, and of the _tonic_ powers of this remedy; but as the issue of the case remains yet undetermined (though it is highly probable, alas! that it will be fatal) I shall relate only a few particulars of it. Master D. a boy of about twelve years of age, endowed with an uncommon capacity, and with the most amiable dispositions, has laboured many months under a hectic fever, the consequence of several tumours in different parts of his body. Two of these tumours were laid open by Mr. White, and a large quantity of purulent matter was discharged from them. The wounds were very properly treated by this skilful surgeon, and every suitable remedy, which my best judgment could suggest, was assiduously administered. But the matter became sanious, of a brown colour, and highly putrid. A _Diarrhoea_ succeeded; the patient's stools were intolerably offensive, and voided without his knowledge. A black fur collected about his teeth; his tongue was covered with _Aphthæ_; and his breath was so foetid, as scarcely to be endured. His strength was almost exhausted; a _subsultus tendinum_ came on; and the final period of his sufferings seemed to be rapidly approaching. As a last, but almost hopeless, effort, I advised the injection of clysters of mephitic air. These soon corrected the foetor of the patient's stools; restrained his _Diarrhoea_; and seemed to recruit his strength and spirits. Within the space of twenty-four hours his wounds assumed a more favourable appearance; the matter discharged from them became of a better colour and consistence; and was no longer so offensive to the smell. The use of this remedy has been continued several days, but is now laid aside. A large tumour is suddenly formed under the right ear; swallowing is rendered difficult and painful; and the patient refuses all food and medicine. Nourishing clysters are directed; but it is to be feared that these will renew the looseness, and that this amiable youth will quickly sink under his disorder[22]. The use of _wort_ from its saccharine quality, and disposition to ferment, has lately been proposed as a remedy for the SEA SCURVY. Water or other liquors, already abounding with fixed air in a separate state, should seem to be better adapted to this purpose; as they will more quickly correct the putrid disposition of the fluids, and at the same time, by their gentle stimulus[23] increase the powers of digestion, and give new strength to the whole system. Dr. Priestley, who suggested both the idea and the means of executing it, has under the sanction of the College of Physicians, proposed the scheme to the Lords of the Admiralty, who have ordered trial to be made of it, on board some of his Majesty's ships of war. Might it not however give additional efficacy to this remedy, if instead of simple water, the infusion of malt were to be employed? I am persuaded such a medicinal drink might be prescribed also with great advantage in SCROPHULOUS COMPLAINTS, when not attended with a hectic fever; and in other disorders in which a general acrimony prevails, and the crasis of the blood is destroyed. Under such circumstances, I have seen _vibices_ which spread over the body, disappear in a few days from the use of wort. A gentleman who is subject to a scorbutic eruption in his face, for which he has used a variety of remedies with no very beneficial effect, has lately applied the fumes of chalk and oil of vitriol to the parts affected. The operation occasions great itching and pricking in the skin, and some degree of drowsiness, but evidently abates the serous discharge, and diminishes the eruption. This patient has several symptoms which indicate a genuine scorbutic DIATHESIS; and it is probable that fixed air, taken internally, would be an useful medicine in this case. The saline draughts of Riverius are supposed to owe their antiemetic effects to the air, which is separated from the salt of wormwood during the act of effervescence. And the tonic powers of many mineral waters seem to depend on this principle. I was lately desired to visit a lady who had most severe convulsive REACHINGS. Various remedies had been administered without effect, before I saw her. She earnestly desired a draught of malt liquor, and was indulged with half a pint of Burton beer in brisk effervescence. The vomitings ceased immediately, and returned no more. Fermenting liquors, it is well known, abound with fixed air. To this, and to the cordial quality of the beer, the favourable effect which it produced, may justly be ascribed. But I shall exceed my design by enlarging further on this subject. What has been advanced it is hoped, will suffice to excite the attention of physicians to a remedy which is capable of being applied to so many important medicinal purposes. NUMBER IV. _Extract of a Letter from WILLIAM FALCONER, M.D. of BATH._ Jan 6, 1774, Reverend Sir, I once observed the same taste you mention (Philosophical Transactions, p. 156. of this Volume, p. 35.) viz. like tar water, in some water that I impregnated with fixed air about three years ago. I did not then know to what to attribute it, but your experiment seems to clear it up. I happened to have spent all my acid for raising effervescence, and to supply its place I used a bottle of dulcified spirit of nitre, which I knew was greatly under-saturated with spirit of wine; from which, as analogous to your observation, I imagine the effect proceeded. As[24] to the coagulation of the blood of animals by fixed Air, I fear it will scarce stand the test of experiment, as I this day gave it, I think, a fair trial, in the following manner. A young healthy man, at 20 years old, received a contusion by a fall, was instantly carried to a neighbouring surgeon, and, at my request, bled in the following manner. I inserted a glass funnel into the neck of a large clear phial about oz. x. contents, and bled him into it to about oz. viii. By these means the blood was exposed to the air as little a time as possible, as it flowed into the bottle as it came from the orifice. As soon as the quantity proposed was drawn, the bottle was carefully corked, and brought to me. It was then quite fluid, nor was there the least separation of its parts. On the surface of this I conveyed several streams of fixed air (having first placed the bottle with the blood in a bowl of water, heated as nearly to the human heat as possible) from the mixture of the vitriolic acid and lixiv. tartar, which I use preferably to other alkalines, as being (as Dr. Cullen observes) in the mildest state, and therefore most likely to generate most air. I shook the phial often, and threw many streams of air on the blood, as I have often practised with success for impregnating water; but could not perceive the smallest signs of coagulation, although it stood in an atmosphere of fixed air 20 minutes or more. I then uncorked the bottles, and poured off about oz. ii to which I added about 6 or 7 gtts of spirit of vitriol, which coagulated it immediately. I set the remainder in a cold place and it coagulated, as near as I could judge, in the same time that blood would have done newly drawn from the vein. P. 82. Perhaps the circumilance of putrid vegetables yielding all fixed and no inflammable air may be the causes of their proving so antiseptic, even when putrid, as appears by Mr. Alexander's Experiments. P. 86. Perhaps the putrid air continually exhaled may be one cause of the luxuriancy of plants growing on dunghills or in very rich soils. P. 146. Your observation that inflammable air consists of the union of some acid vapour with phlogiston, puts me in mind of an old observation of Dr. Cullen, that the oil separated from soap by an acid was much more inflammable than before, resembling essential oil, and soluble in V. sp. I have tried fixed air as an antiseptic taken in by respiration, but with no great success. In one case it seemed to be of service, in two it seemed indifferent, and in one was injurious, by exciting a cough. NUMBER V. _Extract of a Letter from Mr. WILLIAM BEWLEY, of GREAT MASSINGHAM, NORFOLK._ March 23, 1774. Dear Sir, When I first received your paper, I happened to have a process going on for the preparation of _nitrous ether_, without distillation.[25] I had heretofore always taken for granted that the elastic fluid generated in that preparation was _fixed_ air: but on examination I found this combination of the nitrous acid with inflammable spirits, produced an elastic fluid that had the same general properties with the air that you unwillingly, though very properly, in my opinion, term _nitrous_; as I believe it is not to be procured without employing the _nitrous_ acid, either in a simple state, or compounded, as in _aqua regia_. I shall suggest, however, by and by some doubts with respect to it's title to the appellation of _air_. Water impregnated with your nitrous air _certainly_, as you suspected from it's taste, contains the nitrous acid. On saturating a quantity of this water with a fixed alcali, and then evaporating, &c. I have procured two chrystals of nitre. But the principal observations that have occurred to me on the subject of nitrous air are the following. My experiments have been few and made by snatches, under every disadvantage as to apparatus, &c. and with frequent interruptions; and yet I think they are to be depended upon. My first remark is, that nitrous air does not give water a sensibly acid impregnation, unless it comes into contact, or is mixed with a portion of common or atmospherical air: and my second, that nitrous air principally consists of the nitrous acid itself, reduced to the state of a _permanent_ vapour not condensable by cold, like other vapours, but which requires the presence and admixture of common air to restore it to its primitive state of a liquid. I am beholden for this idea, you will perceive, to your own very curious discovery of the true nature of Mr. Cavendish's _marine_ vapour. When I first repeated your experiment of impregnating water with nitrous air, the water, I must own tasted acid; as it did in one, or perhaps two trials afterwards; but, to my great astonishment, in all the following experiments, though some part of the factitious air, or vapour, was visibly absorbed by the water, I could not perceive the latter to have acquired any sensible acidity. I at length found, however, that I could render this same water _very_ acid, by means only of the nitrous air already included in the phial with it. Taking the inverted phial out of the water, I remove my finger from the mouth of it, to admit a little of the common air, and instantly replace my finger. The redness, effervescence, and diminution take place. Again taking off my finger, and instantly replacing it, more common, air rushes in, and the same phenomena recur. The process sometimes requires to be seven or eight times repeated, before the whole of the nitrous _vapour_ (as I shall venture to call it) is condensed into nitrous _acid_, by the successive entrance of fresh parcels of common air after each effervescence; and the water becomes evidently more and more acid after every such fresh admission of the external air, which at length ceases to enter, when the whole of the vapour has been condensed. No agitation of the water is requisite, except a gentle motion, just sufficient to rince the sides of the phial, in order to wash off the condensed vapour. The acidity which you (and I likewise, at first) observed in the water agitated with nitrous air _alone_, I account for thus. On bringing the phial to the mouth, the common air meeting with the nitrous vapour in the neck of the phial, condenses it, and impregnates the water with the acid, in the very act of receiving it upon the tongue. On stopping the mouth of the phial with my tongue for a short time and afterwards withdrawing it a very little, to suffer the common air to rush past it into the phial, the sensation of acidity has been sometimes intolerable: but taking a large gulph of the water at the same time, it has been found very slightly acid.--The following is one of the methods by which I have given water a very strong acid impregnation, by means of a mixture of nitrous and common air. Into a small phial, containing only common air, I force a quantity of nitrous air at random, out of a bladder, and instantly clap my finger on the mouth of the bottle. I then immerse the neck of it into water, a small quantity of which I suffer to enter, which squirts into it with violence; and immediately replacing my finger, remove the phial. The water contained in it is already _very_ acid, and it becomes more and more so (if a sufficient quantity of nitrous air was at first thrown in) on alternately stopping the mouth of the phial, and opening it, as often as fresh air will enter. Since I wrote the above, I have frequently converted a small portion of water in an ounce phial into a weak _Aqua fortis_, by repeated mixtures of common and nitrous air; throwing in alternately the one or the other, according to the circumstances; that is, as long as there was a superabundance of nitrous air, suffering the common air to enter and condense it; and, when that was effected, forcing in more nitrous air from the bladder, to the common air which now predominated in the phial--and so alternately. I have wanted leisure, and conveniences, to carry on this process to its _maximum_, or to execute it in a different and better manner; but from what I have done, I think we may conclude that nitrous air consists principally of the nitrous acid, phlogisticated, or otherwise so modified, by a previous commenstruation with metals, inflammable spirits, &c. as to be reduced into a durably elastic vapour: and that, in order to deprive it of its elasticity, and restore it to its former state, an addition of common air is requisite, and, as I suspect, of water likewise, or some other fluid: as in the course of my few trials, I have not yet been able to condense it in a perfectly dry bottle. NUMBER VI. _A Letter from_ Dr. FRANKLIN. Craven Street, April 10, 1774. Dear Sir, In compliance with your request, I have endeavoured to recollect the circumstances of the American experiments I formerly mentioned to you, of raising a flame on the surface of some waters there. When I passed through New Jersey in 1764, I heard it several times mentioned, that by applying a lighted candle near the surface of some of their rivers, a sudden flame Would catch and spread on the water, continuing to burn for near half a minute. But the accounts I received were so imperfect that I could form no guess at the cause of such an effect, and rather doubted the truth of it. I had no opportunity of seeing the experiment; but calling to see a friend who happened to be just returned home from making it himself, I learned from him the manner of it; which was to choose a shallow place, where the bottom could be reached by a walking-stick, and was muddy; the mud was first to be stirred with the stick, and when a number of small bubbles began to arise from it, the candle was applied. The flame was so sudden and so strong, that it catched his ruffle and spoiled it, as I saw. New-Jersey having many pine-trees in different parts of it, I then imagined that something like a volatile oil of turpentine might be mixed with the waters from a pine-swamp, but this supposition did not quite satisfy me. I mentioned the fact to some philosophical friends on my return to England, but it was not much attended to. I suppose I was thought a little too credulous. In 1765, the Reverend Dr. Chandler received a letter from Dr. Finley, President of the College in that province, relating the same experiment. It was read at the Royal Society, Nov. 21, of that year, but not printed in the Transactions; perhaps because it was thought too strange to be true, and some ridicule might be apprehended if any member should attempt to repeat it in order to ascertain or refute it. The following is a copy of that account. "A worthy gentleman, who lives at a few miles distance, informed me that in a certain small cove of a mill-pond, near his house, he was surprized to see the surface of the water blaze like inflamed spirits. I soon after went to the place, and made the experiment with the same success. The bottom of the creek was muddy, and when stirred up, so as to cause a considerable curl on the surface, and a lighted candle held within two or three inches of it, the whole surface was in a blaze, as instantly as the vapour of warm inflammable spirits, and continued, when strongly agitated, for the space of several seconds. It was at first imagined to be peculiar to that place; but upon trial it was soon found, that such a bottom in other places exhibited the same phenomenon. The discovery was accidentally made by one belonging to the mill." I have tried the experiment twice here in England, but without success. The first was in a slow running water with a muddy bottom. The second in a stagnant water at the bottom of a deep ditch. Being some time employed in stirring this water, I ascribed an intermitting fever, which seized me a few days after, to my breathing too much of that foul air which I stirred up from the bottom, and which I could not avoid while I stooped in endeavouring to kindle it.--The discoveries you have lately made of the manner in which inflammable air is in some cases produced, may throw light on this experiment, and explain its succeeding in some cases, and not in others. With the highest esteem and respect, I am, Dear Sir, Your most obedient humble servant, B. FRANKLIN. NUMBER VII. _Extract of a Letter from_ Mr. HENRY _of_ Manchester. It is with great pleasure I hear of your intended publication _on air_, and I beg leave to communicate to you an experiment or two which I lately made. Dr. Percival had tried, without effect, to dissolve lead in water impregnated with fixed air. I however thought it probable, that the experiment might succeed with nitrous air. Into a quantity of water impregnated with it, I put several pieces of sheet-lead, and suffered them, after agitation, to continue immersed about two hours. A few drops of vol. tincture of sulphur changed the water to a deep orange colour, but not so deep as when the same tincture was added to a glass of the same water, into which one drop of a solution of sugar of lead had been instilled. The precipitates of both in the morning, were exactly of the same kind; and the water in which the lead had been infused all night, being again tried by the same test, gave signs of a still stronger saturnine impregnation--Whether the nitrous air acts as an acid on the lead, or in the same manner that fixed air dissolves iron, I do not pretend to determine. Syrup of violets added to the nitrous water became of a pale red, but on standing about an hour, grew of a turbid brown cast. Though the nitrous acid is not often found, except produced by art, yet as there is a probability that nitre may be formed in the earth in large towns, and indeed fossile nitre has been actually found in such situations, it should be an additional caution against the use of leaden pumps. I tried to dissolve mercury by the same means, but without success. I am, with the most sincere esteem, Dear Sir, Your obliged and obedient servant, THO. HENRY. _FINIS._ FOOTNOTES: [15] See Dr. Falconer's very useful and ingenious treatise on the Bath water, 2d edit. p. 313. [16] May, 1772. [17] Vid. Mr. White's useful treatise on the management of pregnant and lying-in women, p. 279. [18] See the author's observations on the efficacy of external applications in the ulcerous sore throats, Essays medical and experimental, Vol. I. 2d edit. p. 377. [19] The author of these observations. [20] Directions for impregnating water with fixed air, in order to communicate to it the peculiar spirit and virtues of Pyrmont water, and other mineral waters of a similar nature. [21] Referring to the case communicated by Mr. Hey. [22] He languished about a week, and then died. [23] The vegetables which are most efficacious in the cure of the scurvy, possess some degree of a stimulating power. [24] This refers, to an experiment mentioned in the first publication of these papers in the Philosophical Transactions, but omitted in this volume. [25] The first account of this curious process was, I believe, given in the Mem. de l'Ac. de Sc. de Paris for 1742. Though seemingly less volatile than the vitriolic ether, it boils with a much smaller degree of heat. One day last summer, it boiled in the coolest room of my house; as it gave me notice by the explosion attending its driving out the cork. To save the bottle, and to prevent the total loss of the liquor by evaporation, I found myself obliged instantly to carry it down to my cellar. ERRATA. P. 15. l. 13. _for_ it to _read_ to it p. 24. l. 20. ---- has ---- had p. 60. l. 22. ---- inflammable ---- in inflammable p. 84. l. 5. ---- experiments ---- experiment p. 145. l. 16. ---- with ---- of p. 153. l. 1. ---- that is ---- this air p. 199. l. 17. ---- ingenious ---- ingenuous p. 211. l. 23. ---- of ---- , if p. 243. l. 27. ---- diminishing ---- diminished p. 272. l. 21. ---- seem ---- seems p. 301. l. 31. ---- ---- ---- one end p. 303. l. 5. ---- ---- ---- the nitrous p. 304. l. 21. ---- deslrium ---- delirium p. 306. l. 2. ---- recet. ---- recent. p. 308. l. 7. ---- per ---- Peruv. p. 313. l. 27. ---- usual ---- useful p. 300. to 314. passim ---- Diarrhæa ---- Diarrhoea p. 316. l. 11. ---- remains ---- remainder p. 524. l. 15. ---- it ---- iron. A CATALOGUE of BOOKS written by JOSEPH PRIESTLEY, LL.D. 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20848	----	AN ELEMENTARY STUDY OF CHEMISTRY BY WILLIAM McPHERSON, PH.D. PROFESSOR OF CHEMISTRY, OHIO STATE UNIVERSITY AND WILLIAM EDWARDS HENDERSON, PH.D. ASSOCIATE PROFESSOR OF CHEMISTRY, OHIO STATE UNIVERSITY _REVISED EDITION_ GINN & COMPANY BOSTON * NEW YORK * CHICAGO * LONDON COPYRIGHT, 1905, 1906, BY WILLIAM MCPHERSON AND WILLIAM E. HENDERSON ALL RIGHTS RESERVED The Athenæum Press GINN & COMPANY * PROPRIETORS * BOSTON * U.S.A. Transcriber's note: For Text: A word surrounded by a cedilla such as ~this~ signifies that the word is bolded in the text. A word surrounded by underscores like _this_ signifies the word is italics in the text. The italic and bold markup for single italized letters (such as variables in equations) and "foreign" abbreviations are deleted for easier reading. For numbers and equations: Parentheses have been added to clarify fractions. Underscores before bracketed numbers in equations denote a subscript. Superscripts are designated with a caret and brackets, e.g. 11.1^{3} is 11.1 to the third power. Appendix A and B have been moved to the end of the book. Minor typos have been corrected. PREFACE In offering this book to teachers of elementary chemistry the authors lay no claim to any great originality. It has been their aim to prepare a text-book constructed along lines which have become recognized as best suited to an elementary treatment of the subject. At the same time they have made a consistent effort to make the text clear in outline, simple in style and language, conservatively modern in point of view, and thoroughly teachable. The question as to what shall be included in an elementary text on chemistry is perhaps the most perplexing one which an author must answer. While an enthusiastic chemist with a broad understanding of the science is very apt to go beyond the capacity of the elementary student, the authors of this text, after an experience of many years, cannot help believing that the tendency has been rather in the other direction. In many texts no mention at all is made of fundamental laws of chemical action because their complete presentation is quite beyond the comprehension of the student, whereas in many cases it is possible to present the essential features of these laws in a way that will be of real assistance in the understanding of the science. For example, it is a difficult matter to deduce the law of mass action in any very simple way; yet the elementary student can readily comprehend that reactions are reversible, and that the point of equilibrium depends upon, rather simple conditions. The authors believe that it is worth while to present such principles in even an elementary and partial manner because they are of great assistance to the general student, and because they make a foundation upon which the student who continues his studies to more advanced courses can securely build. The authors have no apologies to make for the extent to which they have made use of the theory of electrolytic dissociation. It is inevitable that in any rapidly developing science there will be differences of opinion in regard to the value of certain theories. There can be no question, however, that the outline of the theory of dissociation here presented is in accord with the views of the very great majority of the chemists of the present time. Moreover, its introduction to the extent to which the authors have presented it simplifies rather than increases the difficulties with which the development of the principles of the science is attended. The oxygen standard for atomic weights has been adopted throughout the text. The International Committee, to which is assigned the duty of yearly reporting a revised list of the atomic weights of the elements, has adopted this standard for their report, and there is no longer any authority for the older hydrogen standard. The authors do not believe that the adoption of the oxygen standard introduces any real difficulties in making perfectly clear the methods by which atomic weights are calculated. The problems appended to the various chapters have been chosen with a view not only of fixing the principles developed in the text in the mind of the student, but also of enabling him to answer such questions as arise in his laboratory work. They are, therefore, more or less practical in character. It is not necessary that all of them should be solved, though with few exceptions the lists are not long. The answers to the questions are not directly given in the text as a rule, but can be inferred from the statements made. They therefore require independent thought on the part of the student. With very few exceptions only such experiments are included in the text as cannot be easily carried out by the student. It is expected that these will be performed by the teacher at the lecture table. Directions for laboratory work by the student are published in a separate volume. While the authors believe that the most important function of the elementary text is to develop the principles of the science, they recognize the importance of some discussion of the practical application of these principles to our everyday life. Considerable space is therefore devoted to this phase of chemistry. The teacher should supplement this discussion whenever possible by having the class visit different factories where chemical processes are employed. Although this text is now for the first time offered to teachers of elementary chemistry, it has nevertheless been used by a number of teachers during the past three years. The present edition has been largely rewritten in the light of the criticisms offered, and we desire to express our thanks to the many teachers who have helped us in this respect, especially to Dr. William Lloyd Evans of this laboratory, a teacher of wide experience, for his continued interest and helpfulness. We also very cordially solicit correspondence with teachers who may find difficulties or inaccuracies in the text. The authors wish to make acknowledgments for the photographs and engravings of eminent chemists from which the cuts included in the text were taken; to Messrs. Elliott and Fry, London, England, for that of Ramsay; to The Macmillan Company for those of Davy and Dalton, taken from the Century Science Series; to the L. E. Knott Apparatus Company, Boston, for that of Bunsen. THE AUTHORS OHIO STATE UNIVERSITY COLUMBUS, OHIO CONTENTS CHAPTER PAGE I. INTRODUCTION 1 II. OXYGEN 13 III. HYDROGEN 28 IV. WATER AND HYDROGEN DIOXIDE 40 V. THE ATOMIC THEORY 59 VI. CHEMICAL EQUATIONS AND CALCULATIONS 68 VII. NITROGEN AND THE RARE ELEMENTS IN THE ATMOSPHERE 78 VIII. THE ATMOSPHERE 83 IX. SOLUTIONS 94 X. ACIDS, BASES, AND SALTS; NEUTRALIZATION 106 XI. VALENCE 116 XII. COMPOUNDS OF NITROGEN 122 XIII. REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM 137 XIV. SULPHUR AND ITS COMPOUNDS 143 XV. PERIODIC LAW 165 XVI. THE CHLORINE FAMILY 174 XVII. CARBON AND SOME OF ITS SIMPLER COMPOUNDS 196 XVIII. FLAMES,--ILLUMINANTS 213 XIX. MOLECULAR WEIGHTS, ATOMIC WEIGHTS, FORMULAS 223 XX. THE PHOSPHORUS FAMILY 238 XXI. SILICON, TITANIUM, BORON 257 XXII. THE METALS 267 XXIII. THE ALKALI METALS 274 XXIV. THE ALKALINE-EARTH FAMILY 300 XXV. THE MAGNESIUM FAMILY 316 XXVI. THE ALUMINIUM FAMILY 327 XXVII. THE IRON FAMILY 338 XXVIII. COPPER, MERCURY, AND SILVER 356 XXIX. TIN AND LEAD 370 XXX. MANGANESE AND CHROMIUM 379 XXXI. GOLD AND THE PLATINUM FAMILY 390 XXXII. SOME SIMPLE ORGANIC COMPOUNDS 397 INDEX 421 APPENDIX A Facing back cover APPENDIX B Inside back cover LIST OF FULL-PAGE ILLUSTRATIONS PAGE ANTOINE LAURENT LAVOISIER _Frontispiece_ JOSEPH PRIESTLEY 14 JOHN DALTON 60 WILLIAM RAMSAY 82 DMITRI IVANOVITCH MENDELÉEFF 166 HENRI MOISSAN 176 SIR HUMPHRY DAVY 276 ROBERT WILHELM BUNSEN 298 AN ELEMENTARY STUDY OF CHEMISTRY CHAPTER I INTRODUCTION ~The natural sciences.~ Before we advance very far in the study of nature, it becomes evident that the one large study must be divided into a number of more limited ones for the convenience of the investigator as well as of the student. These more limited studies are called the _natural sciences_. Since the study of nature is divided in this way for mere convenience, and not because there is any division in nature itself, it often happens that the different sciences are very intimately related, and a thorough knowledge of any one of them involves a considerable acquaintance with several others. Thus the botanist must know something about animals as well as about plants; the student of human physiology must know something about physics as well as about the parts of the body. ~Intimate relation of chemistry and physics.~ Physics and chemistry are two sciences related in this close way, and it is not easy to make a precise distinction between them. In a general way it may be said that they are both concerned with inanimate matter rather than with living, and more particularly with the changes which such matter may be made to undergo. These changes must be considered more closely before a definition of the two sciences can be given. ~Physical changes.~ One class of changes is not accompanied by an alteration in the composition of matter. When a lump of coal is broken the pieces do not differ from the original lump save in size. A rod of iron may be broken into pieces; it may be magnetized; it may be heated until it glows; it may be melted. In none of these changes has the composition of the iron been affected. The pieces of iron, the magnetized iron, the glowing iron, the melted iron, are just as truly iron as was the original rod. Sugar may be dissolved in water, but neither the sugar nor the water is changed in composition. The resulting liquid has the sweet taste of sugar; moreover the water may be evaporated by heating and the sugar recovered unchanged. Such changes are called _physical changes_. DEFINITION: _Physical changes are those which do not involve a change in the composition of the matter._ ~Chemical changes.~ Matter may undergo other changes in which its composition is altered. When a lump of coal is burned ashes and invisible gases are formed which are entirely different in composition and properties from the original coal. A rod of iron when exposed to moist air is gradually changed into rust, which is entirely different from the original iron. When sugar is heated a black substance is formed which is neither sweet nor soluble in water. Such changes are evidently quite different from the physical changes just described, for in them new substances are formed in place of the ones undergoing change. Changes of this kind are called _chemical changes_. DEFINITION: _Chemical changes are those which involve a change in the composition of the matter._ ~How to distinguish between physical and chemical changes.~ It is not always easy to tell to which class a given change belongs, and many cases will require careful thought on the part of the student. The test question in all cases is, Has the composition of the substance been changed? Usually this can be answered by a study of the properties of the substance before and after the change, since a change in composition is attended by a change in properties. In some cases, however, only a trained observer can decide the question. ~Changes in physical state.~ One class of physical changes should be noted with especial care, since it is likely to prove misleading. It is a familiar fact that ice is changed into water, and water into steam, by heating. Here we have three different substances,--the solid ice, the liquid water, and the gaseous steam,--the properties of which differ widely. The chemist can readily show, however, that these three bodies have exactly the same composition, being composed of the same substances in the same proportion. Hence the change from one of these substances into another is a physical change. Many other substances may, under suitable conditions, be changed from solids into liquids, or from liquids into gases, without change in composition. Thus butter and wax will melt when heated; alcohol and gasoline will evaporate when exposed to the air. _The three states--solid, liquid, and gas--are called the three physical states of matter._ ~Physical and chemical properties.~ Many properties of a substance can be noted without causing the substance to undergo chemical change, and are therefore called its _physical properties_. Among these are its physical state, color, odor, taste, size, shape, weight. Other properties are only discovered when the substance undergoes chemical change. These are called its _chemical properties_. Thus we find that coal burns in air, gunpowder explodes when ignited, milk sours when exposed to air. ~Definition of physics and chemistry.~ It is now possible to make a general distinction between physics and chemistry. DEFINITION: _Physics is the science which deals with those changes in matter which do not involve a change in composition._ DEFINITION: _Chemistry is the science which deals with those changes in matter which do involve a change in composition._ ~Two factors in all changes.~ In all the changes which matter can undergo, whether physical or chemical, two factors must be taken into account, namely, _energy_ and _matter_. ~Energy.~ It is a familiar fact that certain bodies have the power to do work. Thus water falling from a height upon a water wheel turns the wheel and in this way does the work of the mills. Magnetized iron attracts iron to itself and the motion of the iron as it moves towards the magnet can be made to do work. When coal is burned it causes the engine to move and transports the loaded cars from place to place. When a body has this power to do work it is said to possess energy. ~Law of conservation of energy.~ Careful experiments have shown that when one body parts with its energy the energy is not destroyed but is transferred to another body or system of bodies. Just as energy cannot be destroyed, neither can it be created. If one body gains a certain amount of energy, some other body has lost an equivalent amount. These facts are summed up in the law of conservation of energy which may be stated thus: _While energy can be changed from one form into another, it cannot be created or destroyed._ ~Transformations of energy.~ Although energy can neither be created nor destroyed, it is evident that it may assume many different forms. Thus the falling water may turn the electric generator and produce a current of electricity. The energy lost by the falling water is thus transformed into the energy of the electric current. This in turn may be changed into the energy of motion, as when the current is used for propelling the cars, or into the energy of heat and light, as when it is used for heating and lighting the cars. Again, the energy of coal may be converted into energy of heat and subsequently of motion, as when it is used as a fuel in steam engines. Since the energy possessed by coal only becomes available when the coal is made to undergo a chemical change, it is sometimes called _chemical energy_. It is this form of energy in which we are especially interested in the study of chemistry. ~Matter.~ Matter may be defined as that which occupies space and possesses weight. Like energy, matter may be changed oftentimes from one form into another; and since in these transformations all the other physical properties of a substance save weight are likely to change, the inquiry arises, Does the weight also change? Much careful experimenting has shown that it does not. The weight of the products formed in any change in matter always equals the weight of the substances undergoing change. ~Law of conservation of matter.~ The important truth just stated is frequently referred to as the law of conservation of matter, and this law may be briefly stated thus: _Matter can neither be created nor destroyed, though it can be changed from one form into another._ ~Classification of matter.~ At first sight there appears to be no limit to the varieties of matter of which the world is made. For convenience in study we may classify all these varieties under three heads, namely, _mechanical mixtures_, _chemical compounds_, and _elements_. [Illustration: Fig. 1] ~Mechanical mixtures.~ If equal bulks of common salt and iron filings are thoroughly mixed together, a product is obtained which, judging by its appearance, is a new substance. If it is examined more closely, however, it will be seen to be merely a mixture of the salt and iron, each of which substances retains its own peculiar properties. The mixture tastes just like salt; the iron particles can be seen and their gritty character detected. A magnet rubbed in the mixture draws out the iron just as if the salt were not there. On the other hand, the salt can be separated from the iron quite easily. Thus, if several grams of the mixture are placed in a test tube, and the tube half filled with water and thoroughly shaken, the salt dissolves in the water. The iron particles can then be filtered from the liquid by pouring the entire mixture upon a piece of filter paper folded so as to fit into the interior of a funnel (Fig. 1). The paper retains the solid but allows the clear liquid, known as the _filtrate_, to drain through. The iron particles left upon the filter paper will be found to be identical with the original iron. The salt can be recovered from the filtrate by evaporation of the water. To accomplish this the filtrate is poured into a small evaporating dish and gently heated (Fig. 2) until the water has disappeared, or _evaporated_. The solid left in the dish is identical in every way with the original salt. Both the iron and the salt have thus been recovered in their original condition. It is evident that no new substance has been formed by rubbing the salt and iron together. The product is called a _mechanical mixture_. Such mixtures are very common in nature, almost all minerals, sands, and soils being examples of this class of substances. It is at once apparent that there is no law regulating the composition of a mechanical mixture, and no two mixtures are likely to have exactly the same composition. The ingredients of a mechanical mixture can usually be separated by mechanical means, such as sifting, sorting, magnetic attraction, or by dissolving one constituent and leaving the other unchanged. [Illustration: Fig. 2] DEFINITION: _A mechanical mixture is one in which the constituents retain their original properties, no chemical action having taken place when they were brought together._ ~Chemical compounds.~ If iron filings and powdered sulphur are thoroughly ground together in a mortar, a yellowish-green substance results. It might easily be taken to be a new body; but as in the case of the iron and salt, the ingredients can readily be separated. A magnet draws out the iron. Water does not dissolve the sulphur, but other liquids do, as, for example, the liquid called carbon disulphide. When the mixture is treated with carbon disulphide the iron is left unchanged, and the sulphur can be obtained again, after filtering off the iron, by evaporating the liquid. The substance is, therefore, a mechanical mixture. If now a new portion of the mixture is placed in a dry test tube and carefully heated in the flame of a Bunsen burner, as shown in Fig. 3, a striking change takes place. The mixture begins to glow at some point, the glow rapidly extending throughout the whole mass. If the test tube is now broken and the product examined, it will be found to be a hard, black, brittle substance, in no way recalling the iron or the sulphur. The magnet no longer attracts it; carbon disulphide will not dissolve sulphur from it. It is a new substance with new properties, resulting from the chemical union of iron and sulphur, and is called iron sulphide. Such substances are called _chemical compounds_, and differ from mechanical mixtures in that the substances producing them lose their own characteristic properties. We shall see later that the two also differ in that the composition of a chemical compound never varies. [Illustration: Fig. 3] DEFINITION: _A chemical compound is a substance the constituents of which have lost their own characteristic properties, and which cannot be separated save by a chemical change._ ~Elements.~ It has been seen that iron sulphide is composed of two entirely different substances,--iron and sulphur. The question arises, Do these substances in turn contain other substances, that is, are they also chemical compounds? Chemists have tried in a great many ways to decompose them, but all their efforts have failed. Substances which have resisted all efforts to decompose them into other substances are called _elements_. It is not always easy to prove that a given substance is really an element. Some way as yet untried may be successful in decomposing it into other simpler forms of matter, and the supposed element will then prove to be a compound. Water, lime, and many other familiar compounds were at one time thought to be elements. DEFINITION: _An element is a substance which cannot be separated into simpler substances by any known means._ ~Kinds of matter.~ While matter has been grouped in three classes for the purpose of study, it will be apparent that there are really but two distinct kinds of matter, namely, compounds and elements. A mechanical mixture is not a third distinct kind of matter, but is made up of varying quantities of either compounds or elements or both. ~Alchemy.~ In olden times it was thought that some way could be found to change one element into another, and a great many efforts were made to accomplish this transformation. Most of these efforts were directed toward changing the commoner metals into gold, and many fanciful ways for doing this were described. The chemists of that time were called _alchemists_, and the art which they practiced was called _alchemy_. The alchemists gradually became convinced that the only way common metals could be changed into gold was by the wonderful power of a magic substance which they called the _philosopher's stone_, which would accomplish this transformation by its mere touch and would in addition give perpetual youth to its fortunate possessor. No one has ever found such a stone, and no one has succeeded in changing one metal into another. ~Number of elements.~ The number of substances now considered to be elements is not large--about eighty in all. Many of these are rare, and very few of them make any large fraction of the materials in the earth's crust. Clarke gives the following estimate of the composition of the earth's crust: Oxygen 47.0% Calcium 3.5% Silicon 27.9 Magnesium 2.5 Aluminium 8.1 Sodium 2.7 Iron 4.7 Potassium 2.4 Other elements 1.2% A complete list of the elements is given in the Appendix. In this list the more common of the elements are marked with an asterisk. It is not necessary to study more than a third of the total number of elements to gain a very good knowledge of chemistry. ~Physical state of the elements.~ About ten of the elements are gases at ordinary temperatures. Two--mercury and bromine--are liquids. The others are all solids, though their melting points vary through wide limits, from cæsium which melts at 26° to elements which do not melt save in the intense heat of the electric furnace. ~Occurrence of the elements.~ Comparatively few of the elements occur as uncombined substances in nature, most of them being found in the form of chemical compounds. When an element does occur by itself, as is the case with gold, we say that it occurs in the _free state_ or _native_; when it is combined with other substances in the form of compounds, we say that it occurs in the _combined state_, or _in combination_. In the latter case there is usually little about the compound to suggest that the element is present in it; for we have seen that elements lose their own peculiar properties when they enter into combination with other elements. It would never be suspected, for example, that the reddish, earthy-looking iron ore contains iron. ~Names of elements.~ The names given to the elements have been selected in a great many different ways. (1) Some names are very old and their original meaning is obscure. Such names are iron, gold, and copper. (2) Many names indicate some striking physical property of the element. The name bromine, for example, is derived from a Greek word meaning a stench, referring to the extremely unpleasant odor of the substance. The name iodine comes from a word meaning violet, alluding to the beautiful color of iodine vapor. (3) Some names indicate prominent chemical properties of the elements. Thus, nitrogen means the producer of niter, nitrogen being a constituent of niter or saltpeter. Hydrogen means water former, signifying its presence in water. Argon means lazy or inert, the element being so named because of its inactivity. (4) Other elements are named from countries or localities, as germanium and scandium. ~Symbols.~ In indicating the elements found in compounds it is inconvenient to use such long names, and hence chemists have adopted a system of abbreviations. These abbreviations are known as _symbols_, each element having a distinctive symbol. (1) Sometimes the initial letter of the name will suffice to indicate the element. Thus I stands for iodine, C for carbon. (2) Usually it is necessary to add some other characteristic letter to the symbol, since several names may begin with the same letter. Thus C stands for carbon, Cl for chlorine, Cd for cadmium, Ce for cerium, Cb for columbium. (3) Sometimes the symbol is an abbreviation of the old Latin name. In this way Fe (ferrum) indicates iron, Cu (cuprum), copper, Au (aurum), gold. The symbols are included in the list of elements given in the Appendix. They will become familiar through constant use. ~Chemical affinity the cause of chemical combination.~ The agency which causes substances to combine and which holds them together when combined is called _chemical affinity_. The experiments described in this chapter, however, show that heat is often necessary to bring about chemical action. The distinction between the cause producing chemical action and the circumstances favoring it must be clearly made. Chemical affinity is always the cause of chemical union. Many agencies may make it possible for chemical affinity to act by overcoming circumstances which stand in its way. Among these agencies are heat, light, and electricity. As a rule, solution also promotes action between two substances. Sometimes these agencies may overcome chemical attraction and so occasion the decomposition of a compound. EXERCISES 1. To what class of changes do the following belong? (a) The melting of ice; (b) the souring of milk; (c) the burning of a candle; (d) the explosion of gunpowder; (e) the corrosion of metals. What test question must be applied in each of the above cases? 2. Give two additional examples (a) of chemical changes; (b) of physical changes. 3. Is a chemical change always accompanied by a physical change? Is a physical change always accompanied by a chemical change? 4. Give two or more characteristics of a chemical change. 5. (a) When a given weight of water freezes, does it absorb or evolve heat? (b) When the resulting ice melts, is the total heat change the same or different from that of freezing? 6. Give three examples of each of the following: (a) mechanical mixtures; (b) chemical compounds; (c) elements. 7. Give the derivation of the names of the following elements: thorium, gallium, selenium, uranium. (Consult dictionary.) 8. Give examples of chemical changes which are produced through the agency of heat; of light; of electricity. CHAPTER II OXYGEN ~History.~ The discovery of oxygen is generally attributed to the English chemist Priestley, who in 1774 obtained the element by heating a compound of mercury and oxygen, known as red oxide of mercury. It is probable, however, that the Swedish chemist Scheele had previously obtained it, although an account of his experiments was not published until 1777. The name oxygen signifies acid former. It was given to the element by the French chemist Lavoisier, since he believed that all acids owe their characteristic properties to the presence of oxygen. This view we now know to be incorrect. ~Occurrence.~ Oxygen is by far the most abundant of all the elements. It occurs both in the free and in the combined state. In the free state it occurs in the air, 100 volumes of dry air containing about 21 volumes of oxygen. In the combined state it forms eight ninths of water and nearly one half of the rocks composing the earth's crust. It is also an important constituent of the compounds which compose plant and animal tissues; for example, about 66% by weight of the human body is oxygen. ~Preparation.~ Although oxygen occurs in the free state in the atmosphere, its separation from the nitrogen and other gases with which it is mixed is such a difficult matter that in the laboratory it has been found more convenient to prepare it from its compounds. The most important of the laboratory methods are the following: 1. _Preparation from water._ Water is a compound, consisting of 11.18% hydrogen and 88.82% oxygen. It is easily separated into these constituents by passing an electric current through it under suitable conditions. The process will be described in the chapter on water. While this method of preparation is a simple one, it is not economical. 2. _Preparation from mercuric oxide._ This method is of interest, since it is the one which led to the discovery of oxygen. The oxide, which consists of 7.4% oxygen and 92.6% mercury, is placed in a small, glass test tube and heated. The compound is in this way decomposed into mercury which collects on the sides of the glass tube, forming a silvery mirror, and oxygen which, being a gas, escapes from the tube. The presence of the oxygen is shown by lighting the end of a splint, extinguishing the flame and bringing the glowing coal into the mouth of the tube. The oxygen causes the glowing coal to burst into a flame. In a similar way oxygen may be obtained from its compounds with some of the other elements. Thus manganese dioxide, a black compound of manganese and oxygen, when heated to about 700°, loses one third of its oxygen, while barium dioxide, when heated, loses one half of its oxygen. 3. _Preparation from potassium chlorate (usual laboratory method)._ Potassium chlorate is a white solid which consists of 31.9% potassium, 28.9% chlorine, and 39.2% oxygen. When heated it undergoes a series of changes in which all the oxygen is finally set free, leaving a compound of potassium and chlorine called potassium chloride. The change may be represented as follows: /potassium\ | | (potassium / potassium \ (potassium { chlorine } = { } + oxygen | | chlorate) \ chlorine / chloride) \oxygen / [Illustration: JOSEPH PRIESTLEY (English) (1733-1804) School-teacher, theologian, philosopher, scientist; friend of Benjamin Franklin; discoverer of oxygen; defender of the phlogiston theory; the first to use mercury in a pneumatic trough, by which means he first isolated in gaseous form hydrochloric acid, sulphur dioxide, and ammonia] The evolution of the oxygen begins at about 400°. It has been found, however, that if the potassium chlorate is mixed with about one fourth its weight of manganese dioxide, the oxygen is given off at a much lower temperature. Just how the manganese dioxide brings about this result is not definitely known. The amount of oxygen obtained from a given weight of potassium chlorate is exactly the same whether the manganese dioxide is present or not. So far as can be detected the manganese dioxide undergoes no change. [Illustration: Fig. 4] ~Directions for preparing oxygen.~ The manner of preparing oxygen from potassium chlorate is illustrated in the accompanying diagram (Fig. 4). A mixture consisting of one part of manganese dioxide and four parts of potassium chlorate is placed in the flask A and gently heated. The oxygen is evolved and escapes through the tube B. It is collected by bringing over the end of the tube the mouth of a bottle completely filled with water and inverted in a vessel of water, as shown in the figure. The gas rises in the bottle and displaces the water. In the preparation of large quantities of oxygen, a copper retort (Fig. 5) is often substituted for the glass flask. [Illustration: Fig. 5] In the preparation of oxygen from potassium chlorate and manganese dioxide, the materials used must be pure, otherwise a violent explosion may occur. The purity of the materials is tested by heating a small amount of the mixture in a test tube. ~The collection of gases.~ The method used for collecting oxygen illustrates the general method used for collecting such gases as are insoluble in water or nearly so. The vessel C (Fig. 4), containing the water in which the bottles are inverted, is called a _pneumatic trough._ ~Commercial methods of preparation.~ Oxygen can now be purchased stored under great pressure in strong steel cylinders (Fig. 6). It is prepared either by heating a mixture of potassium chlorate and manganese dioxide, or by separating it from the nitrogen and other gases with which it is mixed in the atmosphere. The methods employed for effecting this separation will be described in subsequent chapters. [Illustration: Fig. 6] ~Physical properties.~ Oxygen is a colorless, odorless, tasteless gas, slightly heavier than air. One liter of it, measured at a temperature of 0° and under a pressure of one atmosphere, weighs 1.4285 g., while under similar conditions one liter of air weighs 1.2923 g. It is but slightly soluble in water. Oxygen, like other gases, may be liquefied by applying very great pressure to the highly cooled gas. When the pressure is removed the liquid oxygen passes again into the gaseous state, since its boiling point under ordinary atmospheric pressure is -182.5°. ~Chemical properties.~ At ordinary temperatures oxygen is not very active chemically. Most substances are either not at all affected by it, or the action is so slow as to escape notice. At higher temperatures, however, it is very active, and unites directly with most of the elements. This activity may be shown by heating various substances until just ignited and then bringing them into vessels of the gas, when they will burn with great brilliancy. Thus a glowing splint introduced into a jar of oxygen bursts into flame. Sulphur burns in the air with a very weak flame and feeble light; in oxygen, however, the flame is increased in size and brightness. Substances which readily burn in air, such as phosphorus, burn in oxygen with dazzling brilliancy. Even substances which burn in air with great difficulty, such as iron, readily burn in oxygen. The burning of a substance in oxygen is due to the rapid combination of the substance or of the elements composing it with the oxygen. Thus, when sulphur burns both the oxygen and sulphur disappear as such and there is formed a compound of the two, which is an invisible gas, having the characteristic odor of burning sulphur. Similarly, phosphorus on burning forms a white solid compound of phosphorus and oxygen, while iron forms a reddish-black compound of iron and oxygen. ~Oxidation.~ The term _oxidation_ is applied to the chemical change which takes place when a substance, or one of its constituent parts, combines with oxygen. This process may take place rapidly, as in the burning of phosphorus, or slowly, as in the oxidation (or rusting) of iron when exposed to the air. It is always accompanied by the liberation of heat. The amount of heat liberated by the oxidation of a definite weight of any given substance is always the same, being entirely independent of the rapidity of the process. If the oxidation takes place slowly, the heat is generated so slowly that it is difficult to detect it. If the oxidation takes place rapidly, however, the heat is generated in such a short interval of time that the substance may become white hot or burst into a flame. ~Combustion; kindling temperature.~ When oxidation takes place so rapidly that the heat generated is sufficient to cause the substance to glow or burst into a flame the process is called _combustion_. In order that any substance may undergo combustion, it is necessary that it should be heated to a certain temperature, known as the _kindling temperature._ This temperature varies widely for different bodies, but is always definite for the same body. Thus the kindling temperature of phosphorus is far lower than that of iron, but is definite for each. When any portion of a substance is heated until it begins to burn the combustion will continue without the further application of heat, provided the heat generated by the process is sufficient to bring other parts of the substance to the kindling temperature. On the other hand, if the heat generated is not sufficient to maintain the kindling temperature, combustion ceases. ~Oxides.~ The compounds formed by the oxidation of any element are called _oxides_. Thus in the combustion of sulphur, phosphorus, and iron, the compounds formed are called respectively oxide of sulphur, oxide of phosphorus, and oxide of iron. In general, then, _an oxide is a compound of oxygen with another element_. A great many substances of this class are known; in fact, the oxides of all the common elements have been prepared, with the exception of those of fluorine and bromine. Some of these are familiar compounds. Water, for example, is an oxide of hydrogen, and lime an oxide of the metal calcium. ~Products of combustion.~ The particular oxides formed by the combustion of any substance are called _products of combustion_ of that substance. Thus oxide of sulphur is the product of the combustion of sulphur; oxide of iron is the product of the combustion of iron. It is evident that the products of the combustion of any substance must weigh more than the original substance, the increase in weight corresponding to the amount of oxygen taken up in the act of combustion. For example, when iron burns the oxide of iron formed weighs more than the original iron. In some cases the products of combustion are invisible gases, so that the substance undergoing combustion is apparently destroyed. Thus, when a candle burns it is consumed, and so far as the eye can judge nothing is formed during combustion. That invisible gases are formed, however, and that the weight of these is greater than the weight of the candle may be shown by the following experiment. [Illustration: Fig. 7] A lamp chimney is filled with sticks of the compound known as sodium hydroxide (caustic soda), and suspended from the beam of the balance, as shown in Fig. 7. A piece of candle is placed on the balance pan so that the wick comes just below the chimney, and the balance is brought to a level by adding weights to the other pan. The candle is then lighted. The products formed pass up through the chimney and are absorbed by the sodium hydroxide. Although the candle burns away, the pan upon which it rests slowly sinks, showing that the combustion is attended by an increase in weight. ~Combustion in air and in oxygen.~ Combustion in air and in oxygen differs only in rapidity, the products formed being exactly the same. That the process should take place less rapidly in the former is readily understood, for the air is only about one fifth oxygen, the remaining four fifths being inert gases. Not only is less oxygen available, but much of the heat is absorbed in raising the temperature of the inert gases surrounding the substance undergoing combustion, and the temperature reached in the combustion is therefore less. ~Phlogiston theory of combustion.~ The French chemist Lavoisier (1743-1794), who gave to oxygen its name was the first to show that combustion is due to union with oxygen. Previous to his time combustion was supposed to be due to the presence of a substance or principle called _phlogiston_. One substance was thought to be more combustible than another because it contained more phlogiston. Coal, for example, was thought to be very rich in phlogiston. The ashes left after combustion would not burn because all the phlogiston had escaped. If the phlogiston could be restored in any way, the substance would then become combustible again. Although this view seems absurd to us in the light of our present knowledge, it formerly had general acceptance. The discovery of oxygen led Lavoisier to investigate the subject, and through his experiments he arrived at the true explanation of combustion. The discovery of oxygen together with the part it plays in combustion is generally regarded as the most important discovery in the history of chemistry. It marked the dawn of a new period in the growth of the science. ~Combustion in the broad sense.~ According to the definition given above, the presence of oxygen is necessary for combustion. The term is sometimes used, however, in a broader sense to designate any chemical change attended by the evolution of heat and light. Thus iron and sulphur, or hydrogen and chlorine under certain conditions, will combine so rapidly that light is evolved, and the action is called a combustion. Whenever combustion takes place in the air, however, the process is one of oxidation. ~Spontaneous combustion.~ The temperature reached in a given chemical action, such as oxidation, depends upon the rate at which the reaction takes place. This rate is usually increased by raising the temperature of the substances taking part in the action. When a slow oxidation takes place under such conditions that the heat generated is not lost by being conducted away, the temperature of the substance undergoing oxidation is raised, and this in turn hastens the rate of oxidation. The rise in temperature may continue in this way until the kindling temperature of the substance is reached, when combustion begins. Combustion occurring in this way is called _spontaneous combustion_. Certain oils, such as the linseed oil used in paints, slowly undergo oxidation at ordinary temperatures, and not infrequently the origin of fires has been traced to the spontaneous combustion of oily rags. The spontaneous combustion of hay has been known to set barns on fire. Heaps of coal have been found to be on fire when spontaneous combustion offered the only possible explanation. ~Importance of oxygen.~ 1. Oxygen is essential to life. Among living organisms only certain minute forms of plant life can exist without it. In the process of respiration the air is taken into the lungs where a certain amount of oxygen is absorbed by the blood. It is then carried to all parts of the body, oxidizing the worn-out tissues and changing them into substances which may readily be eliminated from the body. The heat generated by this oxidation is the source of the heat of the body. The small amount of oxygen which water dissolves from the air supports all the varied forms of aquatic animals. 2. Oxygen is also essential to decay. The process of decay is really a kind of oxidation, but it will only take place in the presence of certain minute forms of life known as bacteria. Just how these assist in the oxidation is not known. By this process the dead products of animal and vegetable life which collect on the surface of the earth are slowly oxidized and so converted into harmless substances. In this way oxygen acts as a great purifying agent. 3. Oxygen is also used in the treatment of certain diseases in which the patient is unable to inhale sufficient air to supply the necessary amount of oxygen. OZONE ~Preparation.~ When electric sparks are passed through oxygen or air a small percentage of the oxygen is converted into a substance called _ozone_, which differs greatly from oxygen in its properties. The same change can also be brought about by certain chemical processes. Thus, if some pieces of phosphorus are placed in a bottle and partially covered with water, the presence of ozone may soon be detected in the air contained in the bottle. The conversion of oxygen into ozone is attended by a change in volume, 3 volumes of oxygen forming 2 volumes of ozone. If the resulting ozone is heated to about 300°, the reverse change takes place, the 2 volumes of ozone being changed back into 3 volumes of oxygen. It is possible that traces of ozone exist in the atmosphere, although its presence there has not been definitely proved, the tests formerly used for its detection having been shown to be unreliable. ~Properties.~ As commonly prepared, ozone is mixed with a large excess of oxygen. It is possible, however, to separate the ozone and thus obtain it in pure form. The gas so obtained has the characteristic odor noticed about electrical machines when in operation. By subjecting it to great pressure and a low temperature, the gas condenses to a bluish liquid, boiling at -119°. When unmixed with other gases ozone is very explosive, changing back into oxygen with the liberation of heat. Its chemical properties are similar to those of oxygen except that it is far more active. Air or oxygen containing a small amount of ozone is now used in place of oxygen in certain manufacturing processes. ~The difference between oxygen and ozone.~ Experiments show that in changing oxygen into ozone no other kind of matter is either added to the oxygen or withdrawn from it. The question arises then, How can we account for the difference in their properties? It must be remembered that in all changes we have to take into account _energy_ as well as _matter_. By changing the amount of energy in a substance we change its properties. That oxygen and ozone contain different amounts of energy may be shown in a number of ways; for example, by the fact that the conversion of ozone into oxygen is attended by the liberation of heat. The passage of the electric sparks through oxygen has in some way changed the energy content of the element and thus it has acquired new properties. _Oxygen and ozone must, therefore, be regarded as identical so far as the kind of matter of which they are composed is concerned. Their different properties are due to their different energy contents._ ~Allotropic states or forms of matter.~ Other elements besides oxygen may exist in more than one form. These different forms of the same element are called _allotropic states_ or _forms_ of the element. These forms differ not only in physical properties but also in their energy contents. Elements often exist in a variety of forms which look quite different. These differences may be due to accidental causes, such as the size or shape of the particles or the way in which the element was prepared. Only such forms, however, as have different energy contents are properly called allotropic forms. MEASUREMENT OF GAS VOLUMES ~Standard conditions.~ It is a well-known fact that the volume occupied by a definite weight of any gas can be altered by changing the temperature of the gas or the pressure to which it is subjected. In measuring the volume of gases it is therefore necessary, for the sake of accuracy, to adopt some standard conditions of temperature and pressure. The conditions agreed upon are (1) a temperature of 0°, and (2) a pressure equal to the average pressure exerted by the atmosphere at the sea level, that is, 1033.3 g. per square centimeter. These conditions of temperature and pressure are known as the _standard conditions_, and when the volume of a gas is given it is understood that the measurement was made under these conditions, unless it is expressly stated otherwise. For example, the weight of a liter of oxygen has been given as 1.4285 g. This means that one liter of oxygen, measured at a temperature of 0° and under a pressure of 1033.3 g. per square centimeter, weighs 1.4285 g. The conditions which prevail in the laboratory are never the standard conditions. It becomes necessary, therefore, to find a way to calculate the volume which a gas will occupy under standard conditions from the volume which it occupies under any other conditions. This may be done in accordance with the following laws. ~Law of Charles.~ This law expresses the effect which a change in the temperature of a gas has upon its volume. It may be stated as follows: _For every degree the temperature of a gas rises above zero the volume of the gas is increased by 1/273 of the volume which it occupies at zero; likewise for every degree the temperature of the gas falls below zero the volume of the gas is decreased by 1/273 of the volume which it occupies at zero, provided in both cases that the pressure to which the gas is subjected remains constant._ If V represents the volume of gas at 0°, then the volume at 1° will be V + 1/273 V; at 2° it will be V + 2/273 V; or, in general, the volume v, at the temperature t, will be expressed by the formula (1) v = V + t/273 V, or (2) v = V(1 + (t/273)). Since 1/273 = 0.00366, the formula may be written (3) v = V(1 + 0.00366t). Since the value of V (volume under standard conditions) is the one usually sought, it is convenient to transpose the equation to the following form: (4) V = v/(1 + 0.00366t). The following problem will serve as an illustration of the application of this equation. The volume of a gas at 20° is 750 cc.; find the volume it will occupy at 0°, the pressure remaining constant. In this case, v = 750 cc. and t = 20. By substituting these values, equation (4) becomes V = 750/(1 + 0.00366 × 20) = 698.9 cc. ~Law of Boyle.~ This law expresses the relation between the volume occupied by a gas and the pressure to which it is subjected. It may be stated as follows: _The volume of a gas is inversely proportional to the pressure under which it is measured, provided the temperature of the gas remains constant._ If V represents the volume when subjected to a pressure P and v represents its volume when the pressure is changed to p, then, in accordance with the above law, V : v :: p : P, or VP = vp. In other words, for a given weight of a gas the product of the numbers representing its volume and the pressure to which it is subjected is a constant. Since the pressure of the atmosphere at any point is indicated by the barometric reading, it is convenient in the solution of the problems to substitute the latter for the pressure measured in grams per square centimeter. The average reading of the barometer at the sea level is 760 mm., which corresponds to a pressure of 1033.3 g. per square centimeter. The following problem will serve as an illustration of the application of Boyle's law. A gas occupies a volume of 500 cc. in a laboratory where the barometric reading is 740 mm. What volume would it occupy if the atmospheric pressure changed so that the reading became 750 mm.? Substituting the values in the equation VP = vp, we have 500 × 740 = v × 750, or v = 493.3 cc. ~Variations in the volume of a gas due to changes both in temperature and pressure.~ Inasmuch as corrections must be made as a rule for both temperature and pressure, it is convenient to combine the equations given above for the corrections for each, so that the two corrections may be made in one operation. The following equation is thus obtained: (5) V_{s} = vp/(760(1 + 0.00366t)), in which V_{s} represents the volume of a gas under standard conditions and v, p, and t the volume, pressure, and temperature respectively at which the gas was actually measured. The following problem will serve to illustrate the application of this equation. A gas having a temperature of 20° occupies a volume of 500 cc. when subjected to a pressure indicated by a barometric reading of 740 mm. What volume would this gas occupy under standard conditions? In this problem v = 500, p = 740, and t = 20. Substituting these values in the above equation, we get V_{s} = (500 × 740)/(760 (1 + 0.00366 × 20)) = 453.6 cc. [Illustration: Fig. 8] ~Variations in the volume of a gas due to the pressure of aqueous vapor.~ In many cases gases are collected over water, as explained under the preparation of oxygen. In such cases there is present in the gas a certain amount of water vapor. This vapor exerts a definite pressure, which acts in opposition to the atmospheric pressure and which therefore must be subtracted from the latter in determining the effective pressure upon the gas. Thus, suppose we wish to determine the pressure to which the gas in tube A (Fig. 8) is subjected. The tube is raised or lowered until the level of the water inside and outside the tube is the same. The atmosphere presses down upon the surface of the water (as indicated by the arrows), thus forcing the water upward within the tube with a pressure equal to the atmospheric pressure. The full force of this upward pressure, however, is not spent in compressing the gas within the tube, for since it is collected over water it contains a certain amount of water vapor. This water vapor exerts a pressure (as indicated by the arrow within the tube) in opposition to the upward pressure. It is plain, therefore, that the effective pressure upon the gas is equal to the atmospheric pressure less the pressure exerted by the aqueous vapor. The pressure exerted by the aqueous vapor increases with the temperature. The figures representing the extent of this pressure (often called the _tension of aqueous vapor_) are given in the Appendix. They express the pressure or tension in millimeters of mercury, just as the atmospheric pressure is expressed in millimeters of mercury. Representing the pressure of the aqueous vapor by a, formula (5) becomes (6) V_{s} = v(p - a)/(760(1 + 0.00366t)). The following problem will serve to illustrate the method of applying the correction for the pressure of the aqueous vapor. The volume of a gas measured over water in a laboratory where the temperature is 20° and the barometric reading is 740 mm. is 500 cc. What volume would this occupy under standard conditions? The pressure exerted by the aqueous vapor at 20° (see table in Appendix) is equal to the pressure exerted by a column of mercury 17.4 mm. in height. Substituting the values of v, t, p, and a in formula (6), we have (6) V_{s} = 500(740 - 17.4)/(760(1 + 0.00366 × 20)) = 442.9 cc. ~Adjustment of tubes before reading gas volumes.~ In measuring the volumes of gases collected in graduated tubes or other receivers, over a liquid as illustrated in Fig. 8, the reading should be taken after raising or lowering the tube containing the gas until the level of the liquid inside and outside the tube is the same; for it is only under these conditions that the upward pressure within the tube is the same as the atmospheric pressure. EXERCISES 1. What is the meaning of the following words? phlogiston, ozone, phosphorus. (Consult dictionary.) 2. Can combustion take place without the emission of light? 3. Is the evolution of light always produced by combustion? 4. (a) What weight of oxygen can be obtained from 100 g. of water? (b) What volume would this occupy under standard conditions? 5. (a) What weight of oxygen can be obtained from 500g. of mercuric oxide? (b) What volume would this occupy under standard conditions? 6. What weight of each of the following compounds is necessary to prepare 50 l. of oxygen? (a) water; (b) mercuric oxide; (c) potassium chlorate. 7. Reduce the following volumes to 0°, the pressure remaining constant: (a) 150 cc. at 10°; (b) 840 cc. at 273°. 8. A certain volume of gas is measured when the temperature is 20°. At what temperature will its volume be doubled? 9. Reduce the following volumes to standard conditions of pressure, the temperature remaining constant: (a) 200 cc. at 740 mm.; (b) 500 l. at 380 mm. 10. What is the weight of 1 l. of oxygen when the pressure is 750 mm. and the temperature 0°? 11. Reduce the following volumes to standard conditions of temperature and pressure: (a) 340 cc. at 12° and 753 mm; (b) 500 cc. at 15° and 740 mm. 12. What weight of potassium chlorate is necessary to prepare 250 l. of oxygen at 20° and 750 mm.? 13. Assuming the cost of potassium chlorate and mercuric oxide to be respectively $0.50 and $1.50 per kilogram, calculate the cost of materials necessary for the preparation of 50 l. of oxygen from each of the above compounds. 14. 100 g. of potassium chlorate and 25 g. of manganese dioxide were heated in the preparation of oxygen. What products were left in the flask, and how much of each was present? CHAPTER III HYDROGEN ~Historical.~ The element hydrogen was first clearly recognized as a distinct substance by the English investigator Cavendish, who in 1766 obtained it in a pure state, and showed it to be different from the other inflammable airs or gases which had long been known. Lavoisier gave it the name hydrogen, signifying water former, since it had been found to be a constituent of water. ~Occurrence.~ In the free state hydrogen is found in the atmosphere, but only in traces. In the combined state it is widely distributed, being a constituent of water as well as of all living organisms, and the products derived from them, such as starch and sugar. About 10% of the human body is hydrogen. Combined with carbon, it forms the substances which constitute petroleum and natural gas. It is an interesting fact that while hydrogen in the free state occurs only in traces on the earth, it occurs in enormous quantities in the gaseous matter surrounding the sun and certain other stars. ~Preparation from water.~ Hydrogen can be prepared from water by several methods, the most important of which are the following. 1. _By the electric current._ As has been indicated in the preparation of oxygen, water is easily separated into its constituents, hydrogen and oxygen, by passing an electric current through it under certain conditions. 2. _By the action of certain metals._ When brought into contact with certain metals under appropriate conditions, water gives up a portion or the whole of its hydrogen, its place being taken by the metal. In the case of a few of the metals this change occurs at ordinary temperatures. Thus, if a bit of sodium is thrown on water, an action is seen to take place at once, sufficient heat being generated to melt the sodium, which runs about on the surface of the water. The change which takes place consists in the displacement of one half of the hydrogen of the water by the sodium, and may be represented as follows: _ _ _ _ | hydrogen | | sodium | sodium + | hydrogen |(water) = | hydrogen |(sodium hydroxide) + hydrogen |_oxygen _| |_oxygen _| The sodium hydroxide formed is a white solid which remains dissolved in the undecomposed water, and may be obtained by evaporating the solution to dryness. The hydrogen is evolved as a gas and may be collected by suitable apparatus. Other metals, such as magnesium and iron, decompose water rapidly, but only at higher temperatures. When steam is passed over hot iron, for example, the iron combines with the oxygen of the steam, thus displacing the hydrogen. Experiments show that the change may be represented as follows: _ _ | hydrogen | _ _ _ _ iron + | hydrogen |(water) = | iron |(iron oxide) + | hydrogen | |_oxygen _| |_oxygen _| |_hydrogen_| The iron oxide formed is a reddish-black compound, identical with that obtained by the combustion of iron in oxygen. ~Directions for preparing hydrogen by the action of steam on iron.~ The apparatus used in the preparation of hydrogen from iron and steam is shown in Fig. 9. A porcelain or iron tube B, about 50 cm. in length and 2 cm. or 3 cm. in diameter, is partially filled with fine iron wire or tacks and connected as shown in the figure. The tube B is heated, slowly at first, until the iron is red-hot. Steam is then conducted through the tube by boiling the water in the flask A. The hot iron combines with the oxygen in the steam, setting free the hydrogen, which is collected over water. The gas which first passes over is mixed with the air previously contained in the flask and tube, and is allowed to escape, _since a mixture of hydrogen with oxygen or air explodes violently when brought in contact with a flame_. It is evident that the flask A must be disconnected from the tube before the heat is withdrawn. That the gas obtained is different from air and oxygen may be shown by holding a bottle of it mouth downward and bringing a lighted splint into it. The hydrogen is ignited and burns with an almost colorless flame. [Illustration Fig. 9] ~Preparation from acids~ (_usual laboratory method_). While hydrogen can be prepared from water, either by the action of the electric current or by the action of certain metals, these methods are not economical and are therefore but little used. In the laboratory hydrogen is generally prepared from compounds known as acids, all of which contain hydrogen. When acids are brought in contact with certain metals, the metals dissolve and set free the hydrogen of the acid. Although this reaction is a quite general one, it has been found most convenient in preparing hydrogen by this method to use either zinc or iron as the metal and either hydrochloric or sulphuric acid as the acid. Hydrochloric acid is a compound consisting of 2.77% hydrogen and 97.23% chlorine, while sulphuric acid consists of 2.05% hydrogen, 32.70% sulphur, and 65.25% oxygen. The changes which take place in the preparation of hydrogen from zinc and sulphuric acid (diluted with water) may be represented as follows: _ _ _ _ | hydrogen |(sulphuric | zinc |(zinc zinc + | sulphur | acid) = | sulphur | sulphate) + hydrogen |_oxygen _| |_oxygen _| In other words, the zinc has taken the place of the hydrogen in sulphuric acid. The resulting compound contains zinc, sulphur, and oxygen, and is known as zinc sulphate. This remains dissolved in the water present in the acid. It may be obtained in the form of a white solid by evaporating the liquid left after the metal has passed into solution. When zinc and hydrochloric acid are used the following changes take place: _ _ _ _ | hydrogen |(hydrochloric | zinc |(zinc zinc + |_chlorine_| acid) = |_chlorine_| chloride) + hydrogen When iron is used the changes which take place are exactly similar to those just given for zinc. [Illustration Fig. 10.] ~Directions for preparing hydrogen from acids.~ The preparation of hydrogen from acids is carried out in the laboratory as follows: The metal is placed in a flask or wide-mouthed bottle A (Fig. 10) and the acid is added slowly through the funnel tube B. The metal dissolves in the acid, while the hydrogen which is liberated escapes through the exit tube C and is collected over water. It is evident that the hydrogen which passes over first is mixed with the air from the bottle A. Hence care must be taken not to bring a flame near the exit tube, since, as has been stated previously, such a mixture explodes with great violence when brought in contact with a flame. ~Precautions.~ Both sulphuric acid and zinc, if impure, are likely to contain small amounts of arsenic. Such materials should not be used in preparing hydrogen, since the arsenic present combines with a portion of the hydrogen to form a very poisonous gas known as arsine. On the other hand, chemically pure sulphuric acid, i.e. sulphuric acid that is entirely free from impurities, will not act upon chemically pure zinc. The reaction may be started, however, by the addition of a few drops of a solution of copper sulphate or platinum tetrachloride. ~Physical properties.~ Hydrogen is similar to oxygen in that it is a colorless, tasteless, odorless gas. It is characterized by its extreme lightness, being the lightest of all known substances. One liter of the gas weighs only 0.08984 g. On comparing this weight with that of an equal volume of oxygen, viz., 1.4285 g., the latter is found to be 15.88 times as heavy as hydrogen. Similarly, air is found to be 14.38 times as heavy as hydrogen. Soap bubbles blown with hydrogen rapidly rise in the air. On account of its lightness it is possible to pour it upward from one bottle into another. Thus, if the bottle A (Fig. 11) is filled with hydrogen, placed mouth downward by the side of bottle _B_, filled with air, and is then gradually inverted under B as indicated in the figure, the hydrogen will flow upward into bottle _B_, displacing the air. Its presence in bottle B may then be shown by bringing a lighted splint to the mouth of the bottle, when the hydrogen will be ignited by the flame. It is evident, from this experiment, that in order to retain the gas in an open bottle the bottle must be placed mouth downward. [Illustration Fig. 11] Hydrogen is far more difficult to liquefy than any other gas, with the exception of helium, a rare element recently found to exist in the atmosphere. The English scientist Dewar, however, in 1898 succeeded not only in obtaining hydrogen in liquid state but also as a solid. Liquid hydrogen is colorless and has a density of only 0.07. Its boiling point under atmospheric pressure is -252°. Under diminished pressure the temperature has been reduced to -262°. The solubility of hydrogen in water is very slight, being still less than that of oxygen. Pure hydrogen produces no injurious results when inhaled. Of course one could not live in an atmosphere of the gas, since oxygen is essential to respiration. ~Chemical properties.~ At ordinary temperatures hydrogen is not an active element. A mixture of hydrogen and chlorine, however, will combine with explosive violence at ordinary temperature if exposed to the sunlight. The union can be brought about also by heating. The product formed in either case is hydrochloric acid. Under suitable conditions hydrogen combines with nitrogen to form ammonia, and with sulphur to form the foul-smelling gas, hydrogen sulphide. The affinity of hydrogen for oxygen is so great that a mixture of hydrogen and oxygen or hydrogen and air explodes with great violence when heated to the kindling temperature (about 612°). Nevertheless under proper conditions hydrogen may be made to burn quietly in either oxygen or air. The resulting hydrogen flame is almost colorless and is very hot. The combustion of the hydrogen is, of course, due to its union with oxygen. The product of the combustion is therefore a compound of hydrogen and oxygen. That this compound is water may be shown easily by experiment. [Illustration Fig. 12] ~Directions for burning hydrogen in air.~ The combustion of hydrogen in air may be carried out safely as follows: The hydrogen is generated in the bottle A (Fig. 12), is dried by conducting it through the tube X, filled with some substance (generally calcium chloride) which has a great attraction for moisture, and escapes through the tube T, the end of which is drawn out to a jet. The hydrogen first liberated mixes with the air contained in the generator. If a flame is brought near the jet before this mixture has all escaped, a violent and very dangerous explosion results, since the entire apparatus is filled with the explosive mixture. On the other hand, if the flame is not applied until all the air has been expelled, the hydrogen is ignited and burns quietly, since only the small amount of it which escapes from the jet can come in contact with the oxygen of the air at any one time. By holding a cold, dry bell jar or bottle over the flame, in the manner shown in the figure, the steam formed by the combustion of the hydrogen is condensed, the water collecting in drops on the sides of the jar. ~Precautions.~ In order to avoid danger it is absolutely necessary to prove that the hydrogen is free from air before igniting it. This can be done by testing small amounts of the escaping gas. A convenient and safe method of doing this is to fill a test tube with the gas by inverting it over the jet. The hydrogen, on account of its lightness, collects in the tube, displacing the air. After holding it over the jet for a few moments in order that it may be filled with the gas, the tube is gently brought, mouth downward, to the flame of a burner placed not nearer than an arm's length from the jet. If the hydrogen is mixed with air a slight explosion occurs, but if pure it burns quietly in the tube. The operation is repeated until the gas burns quietly, when the tube is quickly brought back over the jet for an instant, whereby the escaping hydrogen is ignited by the flame in the tube. [Illustration. Fig. 13] ~A mixture of hydrogen and oxygen is explosive.~ That a mixture of hydrogen and air is explosive may be shown safely as follows: A cork through which passes a short glass tube about 1 cm. in diameter is fitted air-tight into the tubule of a bell jar of 2 l. or 3 l. capacity. (A thick glass bottle with bottom removed may be used.) The tube is closed with a small rubber stopper and the bell jar filled with hydrogen, the gas being collected over water. When entirely filled with the gas the jar is removed from the water and supported by blocks of wood in order to leave the bottom of the jar open, as shown in Fig. 13. The stopper is now removed from the tube in the cork, and the hydrogen, which on account of its lightness escapes from the tube, is at once lighted. As the hydrogen escapes, the air flows in at the bottom of the jar and mixes with the remaining portion of the hydrogen, so that a mixture of the two soon forms, and a loud explosion results. The explosion is not dangerous, since the bottom of the jar is open, thus leaving room for the expansion of the hot gas. Since air is only one fifth oxygen, the remainder being inert gases, it may readily be inferred that a mixture of hydrogen with pure oxygen would be far more explosive than a mixture of hydrogen with air. Such mixtures should not be made except in small quantities and by experienced workers. ~Hydrogen does not support combustion.~ While hydrogen is readily combustible, it is not a supporter of combustion. In other words, substances will not burn in it. This may be shown by bringing a lighted candle supported by a stiff wire into a bottle or cylinder of the pure gas, as shown in Fig. 14. The hydrogen is ignited by the flame of the candle and burns at the mouth of the bottle, where it comes in contact with the oxygen in the air. When the candle is thrust up into the gas, its flame is extinguished on account of the absence of oxygen. If slowly withdrawn, the candle is relighted as it passes through the layer of burning hydrogen. [Illustration: Fig. 14] [Illustration: Fig. 15] ~Reduction.~ On account of its great affinity for oxygen, hydrogen has the power of abstracting it from many of its compounds. Thus, if a stream of hydrogen, dried by passing through the tube B (Fig. 15), filled with calcium chloride, is conducted through the tube C containing some copper oxide, heated to a moderate temperature, the hydrogen abstracts the oxygen from the copper oxide. The change may be represented as follows: hydrogen + {copper} {hydrogen} {oxygen}(copper oxide) = {oxygen }(water) + copper The water formed collects in the cold portions of the tube C near its end. In this experiment the copper oxide is said to undergo reduction. _Reduction may therefore be defined as the process of withdrawing oxygen from a compound._ ~Relation of reduction to oxidation.~ At the same time that the copper oxide is reduced it is clear that the hydrogen is oxidized, for it combines with the oxygen given up by the copper oxide. The two processes are therefore very closely related, and it usually happens that when one substance is oxidized some other substance is reduced. That substance which gives up its oxygen is called an _oxidizing agent_, while the substance which unites with the oxygen is called a _reducing agent_. ~The oxyhydrogen blowpipe.~ This is a form of apparatus used for burning hydrogen in pure oxygen. As has been previously stated, the flame produced by the combustion of hydrogen in the air is very hot. It is evident that if pure oxygen is substituted for air, the temperature reached will be much higher, since there are no inert gases to absorb the heat. The oxyhydrogen blowpipe, used to effect this combination, consists of a small tube placed within a larger one, as shown in Fig. 16. [Illustration: Fig. 16] The hydrogen, stored under pressure, generally in steel cylinders, is first passed through the outer tube and ignited at the open end of the tube. The oxygen from a similar cylinder is then conducted through the inner tube, and mixes with the hydrogen at the end of the tube. In order to produce the maximum heat, the hydrogen and oxygen must be admitted to the blowpipe in the exact proportion in which they combine, viz., 2 volumes of hydrogen to 1 of oxygen, or by weight, 1 part of hydrogen to 7.94 parts of oxygen. The intensity of the heat may be shown by bringing into the flame pieces of metal such as iron wire or zinc. These burn with great brilliancy. Even platinum, having a melting point of 1779°, may be melted by the heat of the flame. While the oxyhydrogen flame is intensely hot, it is almost non-luminous. If directed against some infusible substance like ordinary lime (calcium oxide), the heat is so intense that the lime becomes incandescent and glows with a brilliant light. This is sometimes used as a source of light, under the name of _Drummond_ or _lime light_. [Illustration: Fig. 17] ~The blast lamp.~ A similar form of apparatus is commonly used in the laboratory as a source of heat under the name _blast lamp_ (Fig. 17). This differs from the oxyhydrogen blowpipe only in the size of the tubes. In place of the hydrogen and oxygen the more accessible coal gas and air are respectively used. The former is composed largely of a mixture of free hydrogen and gaseous compounds of carbon and hydrogen. While the temperature of the flame is not so high as that of the oxyhydrogen blowpipe, it nevertheless suffices for most chemical operations carried out in the laboratory. ~Uses of hydrogen.~ On account of its cost, hydrogen is but little used for commercial purposes. It is sometimes used as a material for the inflation of balloons, but usually the much cheaper coal gas is substituted for it. Even hot air is often used when the duration of ascension is very short. It has been used also as a source of heat and light in the oxyhydrogen blowpipe. Where the electric current is available, however, this form of apparatus has been displaced almost entirely by the electric light and electric furnace, which are much more economical and more powerful sources of light and heat. EXERCISES 1. Will a definite weight of iron decompose an unlimited weight of steam? 2. Why is oxygen passed through the inner tube of the oxyhydrogen blowpipe rather than the outer? 3. In Fig. 14, will the flame remain at the mouth of the tube? 4. From Fig. 15, suggest a way for determining experimentally the quantity of water formed in the reaction. 5. Distinguish clearly between the following terms: oxidation, reduction, combustion, and kindling temperature. 6. Is oxidation always accompanied by reduction? 7. What is the source of heat in the lime light? What is the exact use of lime in this instrument? 8. In Fig. 12, why is it necessary to dry the hydrogen by means of the calcium chloride in the tube X? 9. At what pressure would the weight of 1 l. of hydrogen be equal to that of oxygen under standard conditions? 10. (a) What weight of hydrogen can be obtained from 150 g. of sulphuric acid? (b) What volume would this occupy under standard conditions? (c) The density of sulphuric acid is 1.84. What volume would the 150 g. of the acid occupy? 11. How many liters of hydrogen can be obtained from 50 cc. of sulphuric acid having a density of 1.84? 12. Suppose you wish to fill five liter bottles with hydrogen, the gas to be collected over water in your laboratory, how many cubic centimeters of sulphuric acid would be required? CHAPTER IV COMPOUNDS OF HYDROGEN AND OXYGEN; WATER AND HYDROGEN DIOXIDE WATER ~Historical.~ Water was long regarded as an element. In 1781 Cavendish showed that it is formed by the union of hydrogen and oxygen. Being a believer in the phlogiston theory, however, he failed to interpret his results correctly. A few years later Lavoisier repeated Cavendish's experiments and showed that water must be regarded as a compound of hydrogen and oxygen. ~General methods employed for the determination of the composition of a compound.~ The composition of a compound may be determined by either of two general processes these are known as _analysis_ and _synthesis_. 1. _Analysis_ is the process of decomposing a compound into its constituents and determining what these constituents are. The analysis is _qualitative_ when it results in merely determining what elements compose the compound; it is _quantitative_ when the exact percentage of each constituent is determined. Qualitative analysis must therefore precede quantitative analysis, for it must be known what elements, are in a compound before a method can be devised for determining exactly how much of each is present. 2. _Synthesis_ is the process of forming a compound from its constituent parts. It is therefore the reverse of analysis. Like analysis, it may be either qualitative or quantitative. ~Application of these methods to the determination of the composition of water.~ The determination of the composition of water is a matter of great interest not only because of the importance of the compound but also because the methods employed illustrate the general methods of analysis and synthesis. ~Methods based on analysis.~ The methods based on analysis may be either qualitative or quantitative in character. [Illustration: Fig. 18] 1. _Qualitative analysis._ As was stated in the study of oxygen, water may be separated into its component parts by means of the electric current. The form of apparatus ordinarily used for effecting this analysis is shown in Fig. 18. A platinum wire, to the end of which is attached a small piece of platinum foil (about 15 mm. by 25 mm.), is fused through each of the tubes B and D, as shown in the figure. The stopcocks at the ends of these tubes are opened and water, to which has been added about one tenth of its volume of sulphuric acid, is poured into the tube A until the side tubes B and D are completely filled. The stopcocks are then closed. The platinum wires extending into the tubes B and D are now connected with the wires leading from two or three dichromate cells joined in series. The pieces of platinum foil within the tubes thus become the electrodes, and the current flows from one to the other through the acidulated water. As soon as the current passes, bubbles of gas rise from each of the electrodes and collect in the upper part of the tubes. The gas rising from the negative electrode is found to be hydrogen, while that from the positive electrode is oxygen. It will be seen that the volume of the hydrogen is approximately double that of the oxygen. Oxygen is more soluble in water than hydrogen, and a very little of it is also lost by being converted into ozone and other substances. It has been found that when the necessary corrections are made for the error due to these facts, the volume of the hydrogen is exactly double that of the oxygen. Fig. 19 illustrates a simpler form of apparatus, which may be used in place of that shown in Fig. 18. A glass or porcelain dish is partially filled with water to which has been added the proper amount of acid. Two tubes filled with the same liquid are inverted over the electrodes. The gases resulting from the decomposition of the water collect in the tubes. [Illustration: Fig. 19] 2. _Quantitative analysis._ The analysis just described is purely qualitative and simply shows that water contains hydrogen and oxygen. It does not prove the absence of other elements; indeed it does not prove that the hydrogen and oxygen are present in the proportion in which they are liberated by the electric current. The method may be made quantitative, however, by weighing the water decomposed and also the hydrogen and oxygen obtained in its decomposition. If the combined weights of the hydrogen and oxygen exactly equal the weight of the water decomposed, then it would be proved that the water consists of hydrogen and oxygen in the proportion in which they are liberated by the electric current. This experiment is difficult to carry out, however, so that the more accurate methods based on synthesis are used. ~Methods based on synthesis.~ Two steps are necessary to ascertain the exact composition of water by synthesis: (1) to show by qualitative synthesis that water is formed by the union of oxygen with hydrogen; (2) to determine by quantitative synthesis in what proportion the two elements unite to form water. The fact that water is formed by the combination of oxygen with hydrogen was proved in the preceding chapter. The quantitative synthesis may be made as follows: [Illustration: Fig. 20] The combination of the two gases is brought about in a tube called a eudiometer. This is a graduated tube about 60 cm. long and 2 cm. wide, closed at one end (Fig. 20). Near the closed end two platinum wires are fused through the glass, the ends of the wires within the tube being separated by a space of 2 mm or 3 mm. The tube is entirely filled with mercury and inverted in a vessel of the same liquid. Pure hydrogen is passed into the tube until it is about one fourth filled. The volume of the gas is then read off on the scale and reduced to standard conditions. Approximately an equal volume of pure oxygen is then introduced and the volume again read off and reduced to standard conditions. This gives the total volume of the two gases. From this the volume of the oxygen introduced may be determined by subtracting from it the volume of the hydrogen. The combination of the two gases is now brought about by connecting the two platinum wires with an induction coil and passing a spark from one wire to the other. Immediately a slight explosion occurs. The mercury in the tube is at first depressed because of the expansion of the gases due to the heat generated, but at once rebounds, taking the place of the gases which have combined to form water. The volume of the water in the liquid state is so small that it may be disregarded in the calculations. In order that the temperature of the residual gas and the mercury may become uniform, the apparatus is allowed to stand for a few minutes. The volume of the gas is then read off and reduced to standard conditions, so that it may be compared with the volumes of the hydrogen and oxygen originally taken. The residual gas is then tested in order to ascertain whether it is hydrogen or oxygen, experiments having proved that it is never a mixture of the two. From the information thus obtained the composition of the water may be calculated. Thus, suppose the readings were as follows: Volume of hydrogen taken 20.3 cc. Volume of hydrogen and oxygen 38.7 Volume of oxygen 18.4 Volume of gas left after combination has taken place (oxygen) 8.3 The 20.3 cc. of hydrogen have combined with 18.4 cc. minus 8.3 cc. (or 10.1 cc.) of oxygen; or approximately 2 volumes of hydrogen have combined with 1 of oxygen. Since oxygen is 15.88 times as heavy as hydrogen, the proportion by weight in which the two gases combine is 1 part of hydrogen to 7.94 of oxygen. ~Precaution.~ If the two gases are introduced into the eudiometer in the exact proportions in which they combine, after the combination has taken place the liquid will rise and completely fill the tube. Under these conditions, however, the tube is very likely to be broken by the sudden upward rush of the liquid. Hence in performing the experiment care is taken to introduce an excess of one of the gases. ~A more convenient form of eudiometer.~ A form of eudiometer (Fig. 21) different from that shown on page 43 is sometimes used to avoid the calculations necessary in reducing the volumes of the gases to the same conditions of temperature and pressure in order to make comparisons. With this apparatus it is possible to take the readings of the volumes under the same conditions of temperature and pressure, and thus compare them directly. The apparatus (Fig. 21) is filled with mercury and the gases introduced into the tube A. The experiment is carried out as in the preceding one, except that before taking the reading of the gas volumes, mercury is either added to the tube B or withdrawn from it by means of the stopcock C, until it stands at exactly the same height in both tubes. The gas inclosed in tube A is then under atmospheric pressure; and since but a few minutes are required for performing the experiment, the conditions of temperature and pressure may be regarded as constant. Hence the volumes of the hydrogen and oxygen and of the residual gas may be read off from the tube and directly compared. [Illustration: Fig. 21] ~Method used by Berzelius and Dumas.~ The method used by these investigators enables us to determine directly the proportion by weight in which the hydrogen and oxygen combine. Fig. 22 illustrates the apparatus used in making this determination. B is a glass tube containing copper oxide. C and D are glass tubes filled with calcium chloride, a substance which has great affinity for water. The tubes B and C, including their contents, are carefully weighed, and the apparatus connected as shown in the figure. A slow current of pure hydrogen is then passed through A, and that part of the tube B which contains copper oxide is carefully heated. The hydrogen combines with the oxygen present in the copper oxide to form water, which is absorbed by the calcium chloride in tube C. The calcium chloride in tube D prevents any moisture entering tube C from the air. The operation is continued until an appreciable amount of water has been formed. The tubes B and C are then weighed once more. The loss of weight in the tube B will exactly equal the weight of oxygen taken up from the copper oxide in the formation of the water. The gain in weight in the tube C will exactly equal the weight of the water formed. The difference in these weights will of course equal the weight of the hydrogen present in the water formed. [Illustration: Fig. 22] ~Dumas' results.~ The above method for the determination of the composition of water was first used by Berzelius in 1820. The work was repeated in 1843 by Dumas, the average of whose results is as follows: Weight of water formed 236.36 g. Oxygen given up by the copper oxide 210.04 ------ Weight of hydrogen present in water 26.32 According to this experiment the ratio of hydrogen to oxygen in water is therefore 26.32 to 210.04, or as l to 7.98 ~Morley's results.~ The American chemist Morley has recently determined the composition of water, extreme precautions being taken to use pure materials and to eliminate all sources of error. The hydrogen and oxygen which combined, as well as the water formed, were all accurately weighed. According to Morley's results, 1 part of hydrogen by weight combines with 7.94 parts of oxygen to form water. ~Comparison of results obtained.~ From the above discussions it is easy to see that it is by experiment alone that the composition of a compound can be determined. Different methods may lead to slightly different results. The more accurate the method chosen and the greater the skill with which the experiment is carried out, the more accurate will be the results. It is generally conceded by chemists that the results obtained by Morley in reference to the composition of water are the most accurate ones. In accordance with these results, then, _water must be regarded as a compound containing hydrogen and oxygen in the proportion of 1 part by weight of hydrogen to 7.94 parts by weight of oxygen_. ~Relation between the volume of aqueous vapor and the volumes of the hydrogen and oxygen which combine to form it.~ When the quantitative synthesis of water is carried out in the eudiometer as described above, the water vapor formed by the union of the hydrogen and oxygen at once condenses. The volume of the resulting liquid is so small that it may be disregarded in making the calculations. If, however, the experiment is carried out at a temperature of 100° or above, the water-vapor formed is not condensed and it thus becomes possible to compare the volume of the vapor with the volumes of hydrogen and oxygen which combined to form it. This can be accomplished by surrounding the arm A of the eudiometer (Fig. 23) with the tube B through which is passed the vapor obtained by boiling some liquid which has a boiling point above 100°. In this way it has been proved that 2 volumes of hydrogen and 1 volume of oxygen combine to form exactly 2 volumes of water vapor, the volumes all being measured under the same conditions of temperature and pressure. It will be noted that the relation between these volumes may be expressed by whole numbers. The significance of this very important fact will be discussed in a subsequent chapter. [Illustration: Fig. 23] ~Occurrence of water.~ Water not only covers about three fourths of the surface of the earth, and is present in the atmosphere in the form of moisture, but it is also a common constituent of the soil and rocks and of almost every form of animal and vegetable organism. The human body is nearly 70% water. This is derived not only from the water which we drink but also from the food which we eat, most of which contains a large percentage of water. Thus potatoes contain about 78% of water, milk 85%, beef over 50%, apples 84%, tomatoes 94%. ~Impurities in water.~ Chemically pure water contains only hydrogen and oxygen. Such a water never occurs in nature, however, for being a good solvent, it takes up certain substances from the rocks and soil with which it comes in contact. When such waters are evaporated these substances are deposited in the form of a residue. Even rain water, which is the purest form occurring in nature, contains dust particles and gases dissolved from the atmosphere. The foreign matter in water is of two kinds, namely, _mineral_, such as common salt and limestone, and _organic_, that is the products of animal and vegetable life. ~Mineral matter in water.~ The amount and nature of the mineral matter present in different waters vary greatly, depending on the character of the rocks and soil with which the waters come in contact. The more common of the substances present are common salt and compounds of calcium, magnesium, and iron. One liter of the average river water contains about 175 mg. of mineral matter. Water from deep wells naturally contains more mineral matter than river water, generally two or three times as much, while sea water contains as much as 35,000 mg. to the liter. ~Effect of impurities on health.~ The mineral matter in water does not, save in very exceptional cases, render the water injurious to the human system. In fact the presence of a certain amount of such matter is advantageous, supplying the mineral constituents necessary for the formation of the solid tissues of the body. The presence of organic matter, on the other hand, must always be regarded with suspicion. This organic matter may consist not only of the products of animal and vegetable life but also of certain microscopic forms of living organisms which are likely to accompany such products. Contagious diseases are known to be due to the presence in the body of minute living organisms or germs. Each disease is caused by its own particular kind of germ. Through sewage these germs may find their way from persons afflicted with disease into the water supply, and it is principally through the drinking water that certain of these diseases, especially typhoid fever, are spread. It becomes of great importance, therefore, to be able to detect such matter when present in drinking water as well as to devise methods whereby it can be removed or at least rendered harmless. ~Analysis of water.~ The mineral analysis of a water is, as the name suggests, simply the determination of the mineral matter present. Sanitary analysis, on the other hand, is the determination of the organic matter present. The physical properties of a water give no conclusive evidence as to its purity, since a water may be unfit for drinking purposes and yet be perfectly clear and odorless. Neither can any reliance be placed on the simple methods often given for testing the purity of water. Only the trained chemist can carry out such methods of analysis as can be relied upon. [Illustration: Fig. 24] ~Purification of water.~ Three general methods are used for the purification of water, namely, _distillation_, _filtration_, and _boiling_. 1. _Distillation._ The most effective way of purifying natural waters is by the process of distillation. This consists in boiling the water and condensing the steam. Fig. 24 illustrates the process of distillation, as commonly conducted in the laboratory. Ordinary water is poured into the flask A and boiled. The steam is conducted through the condenser B, which consists essentially of a narrow glass tube sealed within a larger one, the space between the two being filled with cold water, which is admitted at C and escapes at D. The inner tube is thus kept cool and the steam in passing through it is condensed. The water formed by the condensation of the steam collects in the receiver E and is known as _distilled_ water. Such water is practically pure, since the impurities are nonvolatile and remain in the flask A. ~Commercial distillation.~ In preparing distilled water on a large scale, the steam is generated in a boiler or other metal container and condensed by passing it through a pipe made of metal, generally tin. This pipe is wound into a spiral and is surrounded by a current of cold water. Distilled water is used by the chemist in almost all of his work. It is also used in the manufacture of artificial ice and for drinking water. ~Fractional distillation.~ In preparing distilled water, it is evident that if the natural water contains some substance which is volatile its vapor will pass over and be condensed with the steam, so that the distillate will not be pure water. Even such mixtures, however, may generally be separated by repeated distillation. Thus, if a mixture of water (boiling point 100°) and alcohol (boiling point 78°) is distilled, the alcohol, having the lower boiling point, tends to distill first, followed by the water. The separation of the two is not perfect, however, but may be made nearly so by repeated distillations. The process of separating a mixture of volatile substances by distillation is known as _fractional distillation_. 2. _Filtration._ The process of distillation practically removes all nonvolatile foreign matter, mineral as well as organic. In purifying water for drinking purposes, however, it is only necessary to eliminate the latter or to render it harmless. This is ordinarily done either by filtration or boiling. In filtration the water is passed through some medium which will retain the organic matter. Ordinary charcoal is a porous substance and will condense within its pores the organic matter in water if brought in contact with it. It is therefore well adapted to the construction of filters. Such filters to be effective must be kept clean, since it is evident that the charcoal is useless after its pores are filled. A more effective type of filter is the Chamberlain-Pasteur filter. In this the water is forced through a porous cylindrical cup, the pores being so minute as to strain out the organic matter. ~City filtration beds.~ For purifying the water supply of cities, large filtration beds are prepared from sand and gravel, and the water is allowed to filter through these. Some of the impurities are strained out by the filter, while others are decomposed by the action of certain kinds of bacteria present in the sand. Fig. 25 shows a cross section of a portion of the filter used in purifying the water supply of Philadelphia. The water filters through the sand and gravel and passes into the porous pipe A, from which it is pumped into the city mains. The filters are covered to prevent the water from freezing in cold weather. [Illustration: Fig. 25] 3. _Boiling._ A simpler and equally efficient method for purifying water for drinking purposes consists in boiling the water. It is the germs in water that render it dangerous to health. These germs are living forms of matter. If the water is boiled, the germs are killed and the water rendered safe. While these germs are destroyed by heat, cold has little effect upon them. Thus Dewar, in working with liquid hydrogen, exposed some of these minute forms of life to the temperature of boiling hydrogen (-252°) without killing them. ~Self-purification of water.~ It has long been known that water contaminated with organic matter tends to purify itself when exposed to the air. This is due to the fact that the water takes up a small amount of oxygen from the air, which gradually oxidizes the organic matter present in the water. While water is undoubtedly purified in this way, the method cannot be relied upon to purify a contaminated water so as to render it safe for drinking purposes. ~Physical properties.~ Pure water is an odorless and tasteless liquid, colorless in thin layers, but having a bluish tinge when observed through a considerable thickness. It solidifies at 0° and boils at 100° under the normal pressure of one atmosphere. If the pressure is increased, the boiling point is raised. When water is cooled it steadily contracts until the temperature of 4° is reached: it then expands. Water is remarkable for its ability to dissolve other substances, and is the best solvent known. Solutions of solids in water are more frequently employed in chemical work than are the solid substances, for chemical action between substances goes on more readily when they are in solution than it does when they are in the solid state. ~Chemical properties.~ Water is a very stable substance, or, in other words, it does not undergo decomposition readily. To decompose it into its elements by heat alone requires a very high temperature; at 2500°, for example, only about 5% of the entire amount is decomposed. Though very stable towards heat, water can be decomposed in other ways, as by the action of the electrical current or by certain metals. ~Heat of formation and heat of decomposition are equal.~ The fact that a very high temperature is necessary to decompose water into hydrogen and oxygen is in accord with the fact that a great deal of heat is evolved by the union of hydrogen and oxygen; for it has been proved that the heat necessary to decompose a compound into its elements (heat of decomposition) is equal to the heat evolved in the formation of a compound from its elements (heat of formation). ~Water of crystallization.~ When a solid is dissolved in water and the resulting solution is allowed to evaporate, the solid separates out, often in the form of crystals. It has been found that the crystals of many compounds, although perfectly dry, give up a definite amount of water when heated, the substance at the same time losing its crystalline form. Such water is called _water of crystallization_. This varies in amount with different compounds, but is perfectly definite for the same compound. Thus, if a perfectly dry crystal of copper sulphate is strongly heated in a tube, water is evolved and condenses on the sides of the tube, the crystal crumbling to a light powder. The weight of the water evolved is always equal to exactly 36.07% of the weight of copper sulphate crystals heated. The water must therefore be in chemical combination with the substance composing the crystal; for if simply mixed with it or adhering to it, not only would the substance appear moist but the amount present would undoubtedly vary. The combination, however, must be a very weak one, since the water is often expelled by even a gentle heat. Indeed, in some cases the water is given up on simple exposure to air. Such compounds are said to be _efflorescent_. Thus a crystal of sodium sulphate (Glauber's salt) on exposure to air crumbles to a fine powder, owing to the escape of its water of crystallization. Other substances have just the opposite property: they absorb moisture when exposed to the air. For example, if a bit of dry calcium chloride is placed in moist air, in the course of a few hours it will have absorbed sufficient moisture to dissolve it. Such substances are said to be _deliquescent_. A deliquescent body serves as a good drying or _desiccating_ agent. We have already employed calcium chloride as an agent for absorbing the moisture from hydrogen. Many substances, as for example quartz, form crystals which contain no water of crystallization. ~Mechanically inclosed water.~ Water of crystallization must be carefully distinguished from water which is mechanically inclosed in a crystal and which can be removed by powdering the crystal and drying. Thus, when crystals of common salt are heated, the water inclosed in the crystal is changed into steam and bursts the crystal with a crackling sound. Such crystals are said to _decrepitate_. That this water is not combined is proved by the fact that the amount present varies and that it has all the properties of water. ~Uses of water.~ The importance of water in its relation to life and commerce is too well known to require comment. Its importance to the chemist has also been pointed out. It remains to call attention to the fact that it is used as a standard in many physical measurements. Thus 0° and 100° on the centigrade scale are respectively the freezing and the boiling points of water under normal pressure. The weight of 1 cc. of water at its point of greatest density is the unit of weight in the metric system, namely, the gram. It is also taken as the unit for the determination of the density of liquids and solids as well as for the measurement of amounts of heat. HYDROGEN DIOXIDE ~Composition.~ As has been shown, 1 part by weight of hydrogen combines with 7.94 parts by weight of oxygen to form water. It is possible, however, to obtain a second compound of hydrogen and oxygen differing from water in composition in that 1 part by weight of hydrogen is combined with 2 × 7.94, or 15.88 parts, of oxygen. This compound is called _hydrogen dioxide_ or _hydrogen peroxide_, the prefixes _di-_ and _per-_ signifying that it contains more oxygen than hydrogen oxide, which is the chemical name for water. ~Preparation.~ Hydrogen dioxide cannot be prepared cheaply by the direct union of hydrogen and oxygen, and indirect methods must therefore be used. It is commonly prepared by the action of a solution of sulphuric acid on barium dioxide. The change which takes place may be indicated as follows: sulphuric acid + barium dioxide = barium sulphate + hydrogen dioxide -------------- -------------- --------------- ---------------- hydrogen barium barium hydrogen sulphur oxygen sulphur oxygen oxygen oxygen In other words, the barium and hydrogen in the two compounds exchange places. By this method a dilute solution of the dioxide in water is obtained. It is possible to separate the dioxide from the water by fractional distillation. This is attended with great difficulties, however, since the pure dioxide is explosive. The distillation is carried on under diminished pressure so as to lower the boiling points as much as possible; otherwise the high temperature would decompose the dioxide. ~Properties.~ Pure hydrogen dioxide is a colorless sirupy liquid having a density of 1.49. Its most characteristic property is the ease with which it decomposes into water and oxygen. One part by weight of hydrogen is capable of holding firmly only 7.94 parts of oxygen. The additional 7.94 parts of oxygen present in hydrogen dioxide are therefore easily evolved, the compound breaking down into water and oxygen. This decomposition is attended by the generation of considerable heat. In dilute solution hydrogen dioxide is fairly stable, although such a solution should be kept in a dark, cool place, since both heat and light aid in the decomposition of the dioxide. ~Uses.~ Solutions of hydrogen dioxide are used largely as oxidizing agents. The solution sold by druggists contains 3% of the dioxide and is used in medicine as an antiseptic. Its use as an antiseptic depends upon its oxidizing properties. EXERCISES 1. Why does the chemist use distilled water in making solutions, rather than filtered water? 2. How could you determine the total amount of solid matter dissolved in a sample of water? 3. How could you determine whether a given sample of water is distilled water? 4. How could the presence of air dissolved in water be detected? 5. How could the amount of water in a food such as bread or potato be determined? 6. Would ice frozen from impure water necessarily be free from disease germs? 7. Suppose that the maximum density of water were at 0° in place of 4°; what effect would this have on the formation of ice on bodies of water? 8. Is it possible for a substance to contain both mechanically inclosed water and water of crystallization? 9. If steam is heated to 2000° and again cooled, has any chemical change taken place in the steam? 10. Why is cold water passed into C instead of D (Fig. 24)? 11. Mention at least two advantages that a metal condenser has over a glass condenser. 12. Draw a diagram of the apparatus used in your laboratory for supplying distilled water. 13. 20 cc. of hydrogen and 7 cc. of oxygen are placed in a eudiometer and the mixture exploded. (a) How many cubic centimeters of aqueous vapor are formed? (b) What gas and how much of it remains in excess? 14. (a) What weight of water can be formed by the combustion of 100 L of hydrogen, measured under standard conditions? (b)What volume of oxygen would be required in (a)? (c)What weight of potassium chlorate is necessary to prepare this amount of oxygen? 15. What weight of oxygen is present in 1 kg. of the ordinary hydrogen dioxide solution? In the decomposition of this weight of the dioxide into water and oxygen, what volume of oxygen (measured under standard conditions) is evolved? CHAPTER V THE ATOMIC THEORY ~Three fundamental laws of matter.~ Before we can gain any very definite idea in regard to the structure of matter, and the way in which different kinds of substances act chemically upon each other, it is necessary to have clearly in view three fundamental laws of matter. These laws have been established by experiment, and any conception which may be formed concerning matter must therefore be in harmony with them. The laws are as follows: ~Law of conservation of matter.~ This law has already been touched upon in the introductory chapter, and needs no further discussion. It will be recalled that it may be stated thus: _Matter can neither be created nor destroyed, though it can be changed from one form into another._ ~Law of definite composition.~ In the earlier days of chemistry there was much discussion as to whether the composition of a given compound is always precisely the same or whether it is subject to some variation. Two Frenchmen, Berthollet and Proust, were the leaders in this discussion, and a great deal of most useful experimenting was done to decide the question. Their experiments, as well as all succeeding ones, have shown that the composition of a pure chemical compound is always exactly the same. Water obtained by melting pure ice, condensing steam, burning hydrogen in oxygen, has always 11.18% hydrogen and 88.82% oxygen in it. Red oxide of mercury, from whatever source it is obtained, contains 92.6% mercury and 7.4% oxygen. This truth is known as _the law of definite composition_, and may be stated thus: _The composition of a chemical compound never varies._ ~Law of multiple proportion.~ It has already been noted, however, that hydrogen and oxygen combine in two different ratios to form water and hydrogen dioxide respectively. It will be observed that this fact does not contradict the law of definite composition, for entirely different substances are formed. These compounds differ from each other in composition, but the composition of each one is always constant. This ability of two elements to unite in more than one ratio is very frequently observed. Carbon and oxygen combine in two different ratios; nitrogen and oxygen combine to form as many as five distinct compounds, each with its own precise composition. In the first decade of the last century John Dalton, an English school-teacher and philosopher, endeavored to find some rule which holds between the ratios in which two given substances combine. His studies brought to light a very simple relation, which the following examples will make clear. In water the hydrogen and oxygen are combined in the ratio of 1 part by weight of hydrogen to 7.94 parts by weight of oxygen. In hydrogen dioxide the 1 part by weight of hydrogen is combined with 15.88 parts by weight of oxygen. The ratio between the amounts of oxygen which combine with the same amount of hydrogen to form water and hydrogen dioxide respectively is therefore 7.94: 15.88, or 1: 2. [Illustration: JOHN DALTON (English) (1766-1844) Developed the atomic theory; made many studies on the properties and the composition of gases. His book entitled "A New System of Chemical Philosophy" had a large influence on the development of chemistry] Similarly, the element iron combines with oxygen to form two oxides, one of which is black and the other red. By analysis it has been shown that the former contains 1 part by weight of iron combined with 0.286 parts by weight of oxygen, while the latter contains 1 part by weight of iron combined with 0.429 parts by weight of oxygen. Here again we find that the amounts of oxygen which combine with the same fixed amount of iron to form the two compounds are in the ratio of small whole numbers, viz., 2:3. Many other examples of this simple relation might be given, since it has been found to hold true in all cases where more than one compound is, formed from the same elements. Dalton's law of multiple proportion states these facts as follows: _When any two elements,_ A _and_ B, _combine to form more than one compound, the amounts of_ B _which unite with any fixed amount of_ A _bear the ratio of small whole numbers to each other_. ~Hypothesis necessary to explain the laws of matter.~ These three generalizations are called _laws_, because they express in concise language truths which are found by careful experiment to hold good in all cases. They do not offer any explanation of the facts, but merely state them. The human mind, however, does not rest content with the mere bare facts, but seeks ever to learn the explanation of the facts. A suggestion which is offered to explain such a set of facts is called an _hypothesis_. The suggestion which Dalton offered to explain the three laws of matter, called the _atomic hypothesis_, was prompted by his view of the constitution of matter, and it involves three distinct assumptions in regard to the nature of matter and chemical action. Dalton could not prove these assumptions to be true, but he saw that if they were true the laws of matter become very easy to understand. ~Dalton's atomic hypothesis.~ The three assumptions which Dalton made in regard to the nature of matter, and which together constitute the atomic hypothesis, are these: 1. All elements are made up of minute, independent particles which Dalton designated as _atoms_. 2. All atoms of the same element have equal masses; those of different elements have different masses; in any change to which an atom is subjected its mass does not change. 3. When two or more elements unite to form a compound, the action consists in the union of a definite small number of atoms of each element to form a small particle of the compound. The smallest particles of a given compound are therefore exactly alike in the number and kinds of atoms which they contain, and larger masses of the substances are simply aggregations of these least particles. ~Molecules and atoms.~ Dalton applied the name atom not only to the minute particles of the elements but also to the least particles of compounds. Later Avogadro, an Italian scientist, pointed out the fact that the two are different, since the smallest particle of an element is a unit, while that of a compound must have at least two units in it. He suggested the name _molecule_ for the least particle of a compound which can exist, retaining the name _atom_ for the smallest particle of an element. In accordance with this distinction, we may define the atom and the molecule as follows: _An atom is the smallest particle of an element which can exist. A molecule is the smallest particle of a compound which can exist._ It will be shown in a subsequent chapter that sometimes two or more atoms of the same element unite with each other to form molecules of the element. While the term atom, therefore, is applicable only to elements, the term molecule is applicable both to elements and compounds. ~The atomic hypothesis and the laws of matter.~ Supposing the atomic hypothesis to be true, let us now see if it is in harmony with the laws of matter. 1. _The atomic hypothesis and the law of conservation of matter._ It is evident that if the atoms never change their masses in any change which they undergo, the total quantity of matter can never change and the law of conservation of matter must follow. 2. _The atomic hypothesis and the law of definite composition._ According to the third supposition, when iron combines with sulphur the union is between definite numbers of the two kinds of atoms. In the simplest case one atom of the one element combines with one atom of the other. If the sulphur and the iron atoms never change their respective masses when they unite to form a molecule of iron sulphide, all iron sulphide molecules will have equal amounts of iron in them and also of sulphur. Consequently any mass made up of iron sulphide molecules will have the same fraction of iron by weight as do the individual iron sulphide molecules. Iron sulphide, from whatever source, will have the same composition, which is in accordance with the law of definite composition. 3. _The atomic hypothesis and the law of multiple proportion._ But this simplest case may not always be the only one. Under other conditions one atom of iron might combine with two of sulphur to form a molecule of a second compound. In such a case the one atom of iron would be in combination with twice the mass of sulphur that is in the first compound, since the sulphur atoms all have equal masses. What is true for one molecule will be true for any number of them; consequently when such quantities of these two compounds are selected as are found to contain the same amount of iron, the one will contain twice as much sulphur as the other. The combination between the atoms may of course take place in other simple ratios. For example, two atoms of one element might combine with three or with five of the other. In all such cases it is clear that the law of multiple proportion must hold true. For on selecting such numbers of the two kinds of molecules as have the same number of the one kind of atoms, the numbers of the other kind of atoms will stand in some simple ratio to each other, and their weights will therefore stand in the same simple ratio. ~Testing the hypothesis.~ Efforts have been made to find compounds which do not conform to these laws, but all such attempts have resulted in failure. If such compounds should be found, the laws would be no longer true, and the hypothesis of Dalton would cease to possess value. When an hypothesis has been tested in every way in which experiment can test it, and is still found to be in harmony with the facts in the case, it is termed a _theory_. We now speak of the atomic theory rather than of the atomic hypothesis. ~Value of a theory.~ The value of a theory is twofold. It aids in the clear understanding of the laws of nature because it gives an intelligent idea as to why these laws should be in operation. A theory also leads to discoveries. It usually happens that in testing a theory much valuable work is done, and many new facts are discovered. Almost any theory in explaining given laws will involve a number of consequences apart from the laws it seeks to explain. Experiment will soon show whether these facts are as the theory predicts they will be. Thus Dalton's atomic theory predicted many properties of gases which experiment has since verified. ~Atomic weights.~ It would be of great advantage in the study of chemistry if we could determine the weights of the different kinds of atoms. It is evident that this cannot be done directly. They are so small that they cannot be seen even with a most powerful microscope. It is calculated that it would take 200,000,000 hydrogen atoms placed side by side to make a row one centimeter long. No balance can weigh such minute objects. It is possible, however, to determine their relative weights,--that is, how much heavier one is than another. _These relative weights of the atoms are spoken of as the atomic weights of the elements._ If elements were able to combine in only one way,--one atom of one with one atom of another,--the problem of determining the atomic weights would be very simple. We should merely have to take some one convenient element as a standard, and find by experiment how much of each other element would combine with a fixed weight of it. The ratios thus found would be the same ratios as those between the atoms of the elements, and thus we should have their relative atomic weights. The law of multiple proportion calls attention to the fact that the atoms combine in other ratios than 1: 1, and there is no direct way of telling which one, if any, of the several compounds in a given case is the one consisting of a single atom of each element. If some way were to be found of telling how much heavier the entire molecule of a compound is than the atom chosen as a standard,--that is, of determining the molecular weights of compounds,--the problem could be solved, though its solution would not be an entirely simple matter. There are ways of determining the molecular weights of compounds, and there are other experiments which throw light directly upon the relative weights of the atoms. These methods cannot be described until the facts upon which they rest have been studied. It will be sufficient for the present to assume that these methods are trustworthy. ~Standard for atomic weights.~ Since the atomic weights are merely relative to some one element chosen as a standard, it is evident that any one of the elements may serve as this standard and that any convenient value may be assigned to its atom. At one time oxygen was taken as this standard, with the value 100, and the atomic weights of the other elements were expressed in terms of this standard. It would seem more rational to take the element of smallest atomic weight as the standard and give it unit value; accordingly hydrogen was taken as the standard with an atomic weight of 1. Very recently, however, this unit has been replaced by oxygen, with an atomic weight of 16. ~Why oxygen is chosen as the standard for atomic weights.~ In the determination of the atomic weight of an element it is necessary to find the weight of the element which combines with a definite weight of another element, preferably the element chosen as the standard. Since oxygen combines with the elements far more readily than does hydrogen to form definite compounds, it is far better adapted for the standard element, and has accordingly replaced hydrogen as the standard. Any definite value might be given to the weight of the oxygen atom. In assigning a value to it, however, it is convenient to choose a whole number, and as small a number as possible without making the atomic weight of any other element less than unity. For these reasons the number 16 has been chosen as the atomic weight of oxygen. This makes the atomic weight of hydrogen equal to 1.008, so that there is but little difference between taking oxygen as 16 and hydrogen as 1 for the unit. The atomic weights of the elements are given in the Appendix. EXERCISES 1. Two compounds were found to have the following compositions: (a) oxygen = 69.53%, nitrogen = 30.47%; (b) oxygen = 53.27%, nitrogen = 46.73%. Show that the law of multiple proportion holds in this case. 2. Two compounds were found to have the following compositions: (a) oxygen = 43.64%, phosphorus = 56.36%; (b) oxygen = 56.35%, phosphorus = 43.65%. Show that the law of multiple proportion holds in this case. 3. Why did Dalton assume that all the atoms of a given element have the same weight? CHAPTER VI CHEMICAL EQUATIONS AND CALCULATIONS ~Formulas.~ Since the molecule of any chemical compound consists of a definite number of atoms, and this number never changes without destroying the identity of the compound, it is very convenient to represent the composition of a compound by indicating the composition of its molecules. This can be done very easily by using the symbols of the atoms to indicate the number and the kind of the atoms which constitute the molecule. HgO will in this way represent mercuric oxide, a molecule of which has been found to contain 1 atom each of mercury and oxygen. H_{2}O will represent water, the molecules of which consist of 1 atom of oxygen and 2 of hydrogen, the subscript figure indicating the number of the atoms of the element whose symbol precedes it. H_{2}SO_{4} will stand for sulphuric acid, the molecules of which contain 2 atoms of hydrogen, 1 of sulphur, and 4 of oxygen. The combination of symbols which represents the molecule of a substance is called its _formula_. ~Equations.~ When a given substance undergoes a chemical change it is possible to represent this change by the use of such symbols and formulas. In a former chapter it was shown that mercuric oxide decomposes when heated to form mercury and oxygen. This may be expressed very briefly in the form of the equation (1) HgO = Hg + O. When water is electrolyzed two new substances, hydrogen and oxygen, are formed from it. This statement in the form of an equation is (2) H_{2}O = 2H + O. The coefficient before the symbol for hydrogen indicates that a single molecule of water yields two atoms of hydrogen on decomposition. In like manner the combination of sulphur with iron is expressed by the equation (3) Fe + S = FeS. The decomposition of potassium chlorate by heat takes place as represented by the equation (4) KClO_{3} = KCl + 3O. ~Reading of equations.~ Since equations are simply a kind of shorthand way of indicating chemical changes which occur under certain conditions, in reading an equation the full statement for which it stands should be given. Equation (1) should be read, "Mercuric oxide when heated gives mercury and oxygen"; equation (2) is equivalent to the statement, "When electrolyzed, water produces hydrogen and oxygen"; equation (3), "When heated together iron and sulphur unite to form iron sulphide"; equation (4), "Potassium chlorate when heated yields potassium chloride and oxygen." ~Knowledge required for writing equations.~ In order to write such equations correctly, a considerable amount of exact knowledge is required. Thus, in equation (1) the fact that red oxide of mercury has the composition represented by the formula HgO, that it is decomposed by heat, that in this decomposition mercury and oxygen are formed and no other products,--all these facts must be ascertained by exact experiment before the equation can be written. An equation expressing these facts will then have much value. Having obtained an equation describing the conduct of mercuric oxide on being heated, it will not do to assume that other oxides will behave in like manner. Iron oxide (FeO) resembles mercuric oxide in many respects, but it undergoes no change at all when heated. Manganese dioxide, the black substance used in the preparation of oxygen, has the formula MnO_{2}. When this substance is heated oxygen is set free, but the metal manganese is not liberated; instead, a different oxide of manganese containing less oxygen is produced. The equation representing the reaction is 3MnO_{2} = Mn_{3}O_{4} + 2O. ~Classes of reactions.~ When a chemical change takes place in a substance the substance is said to undergo a reaction. Although a great many different reactions will be met in the study of chemistry, they may all be grouped under the following heads. 1. _Addition._ This is the simplest kind of chemical action. It consists in the union of two or more substances to produce a new substance. The combination of iron with sulphur is an example: Fe + S = FeS. 2. _Decomposition._ This is the reverse of addition, the substance undergoing reaction being parted into its constituents. The decomposition of mercuric oxide is an example: HgO = Hg + O. 3. _Substitution._ It is sometimes possible for an element in the free state to act upon a compound in such a way that it takes the place of one of the elements of the compound, liberating it in turn. In the study of the element hydrogen it was pointed out that hydrogen is most conveniently prepared by the action of sulphuric or hydrochloric acid upon zinc. When sulphuric acid is used a substance called zinc sulphate, having the composition represented by the formula ZnSO_{4}, is formed together with hydrogen. The equation is Zn + H_{2}SO_{4} = ZnSO_{4} + 2H. When hydrochloric acid is used zinc chloride and hydrogen are the products of reaction: Zn + 2HCl = ZnCl_{2} + 2H. When iron is used in place of zinc the equation is Fe + H_{2}SO_{4} = FeSO_{4} + 2H. These reactions are quite similar, as is apparent from an examination of the equations. In each case 1 atom of the metal replaces 2 atoms of hydrogen in the acid, and the hydrogen escapes as a gas. When an element in the free state, such as the zinc in the equations just given, takes the place of some one element in a compound, setting it free from chemical combination, the act is called _substitution_. Other reactions illustrating substitution are the action of sodium on water, Na + H_{2}O = NaOH + H; and the action of heated iron upon water, 3Fe + 4H_{2}O = Fe_{3}O_{4} + 8H. 4. _Double decomposition._ When barium dioxide (BaO_{2}) is treated with sulphuric acid two compounds are formed, namely, hydrogen dioxide (H_{2}O_{2}) and barium sulphate (BaSO_{4}). The equation is BaO_{2} + H_{2}SO_{4} = BaSO_{4} + H_{2}O_{2}. In this reaction it will be seen that the two elements barium and hydrogen simply exchange places. Such a reaction is called a _double decomposition_. We shall meet with many examples of this kind of chemical reactions. ~Chemical equations are quantitative.~ The use of symbols and formulas in expressing chemical changes has another great advantage. Thus, according to the equation H_{2}O = 2H + O, 1 molecule of water is decomposed into 2 atoms of hydrogen and 1 atom of oxygen. But, as we have seen, the relative weights of the atoms are known, that of hydrogen being 1.008, while that of oxygen is 16. The molecule of water, being composed of 2 atoms of hydrogen and 1 atom of oxygen, must therefore weigh relatively 2.016 + 16, or 18.016. The amount of hydrogen in this molecule must be 2.016/18.016, or 11.18% of the whole, while the amount of oxygen must be 16/18.018, or 88.82% of the whole. Now, since any definite quantity of water is simply the sum of a great many molecules of water, it is plain that the fractions representing the relative amounts of hydrogen and oxygen present in a molecule must likewise express the relative amounts of hydrogen and oxygen present in any quantity of water. Thus, for example, in 20 g. of water there are 2.016/18.016 × 20, or 2.238 g. of hydrogen, and 16/18.016 × 20, or 17.762 g. of oxygen. These results in reference to the composition of water of course agree exactly with the facts obtained by the experiments described in the chapter on water, for it is because of those experiments that the values 1.008 and 16 are given to hydrogen and oxygen respectively. It is often easier to make calculations of this kind in the form of a proportion rather than by fractions. Since the molecule of water and the two atoms of hydrogen which it contains have the ratio by weight of 18.016: 2.016, any mass of water has the same ratio between its total weight and the weight of the hydrogen in it. Hence, to find the number of grams (x) of hydrogen in 20 g. of water, we have the proportion 18.016 : 2.016 :: 20 g. : x (grams of hydrogen). Solving for x, we get 2.238 for the number of grams of hydrogen. Similarly, to find the amount (x) of oxygen present in the 20 g. of water, we have the proportion 18.016 : 16 :: 20 : x from which we find that x = 17.762 g. Again, suppose we wish to find what weight of oxygen can be obtained from 15 g. of mercuric oxide. The equation representing the decomposition of mercuric oxide is HgO = Hg + O. The relative weights of the mercury and oxygen atoms are respectively 200 and 16. The relative weight of the mercuric oxide molecule must therefore be the sum of these, or 216. The molecule of mercuric oxide and the atom of oxygen which it contains have the ratio 216: 16. This same ratio must therefore hold between the weight of any given quantity of mercuric oxide and that of the oxygen which it contains. Hence, to find the weight of oxygen in 15 g. of mercuric oxide, we have the proportion 216 : 16 :: 15 : x (grams of oxygen). On the other hand, suppose we wish to prepare, say, 20 g. of oxygen. The problem is to find out what weight of mercuric oxide will yield 20 g. of oxygen. The following proportion evidently holds 216 : 16 :: x (grams of mercuric oxide) : 20; from which we get x = 270. In the preparation of hydrogen by the action of sulphuric acid upon zinc, according to the equation, Zn + H_{2}SO_{4} = ZnSO_{4} + 2 H, suppose that 50 g. of zinc are available; let it be required to calculate the weight of hydrogen which can be obtained. It will be seen that 1 atom of zinc will liberate 2 atoms of hydrogen. The ratio by weight of a zinc to an hydrogen atom is 65.4: 1.008; of 1 zinc atom to 2 hydrogen atoms, 65.4: 2.016. Zinc and hydrogen will be related in this reaction in this same ratio, however many atoms of zinc are concerned. Consequently in the proportion 65.4 : 2.016 :: 50 : x, x will be the weight of hydrogen set free by 50 g. of zinc. The weight of zinc sulphate produced at the same time can be found from the proportion 65.4 : 161.46 :: 50 : x; where 161.46 is the molecular weight of the zinc sulphate, and x the weight of zinc sulphate formed. In like manner, the weight of sulphuric acid used up can be calculated from the proportion 65.4 : 98.076 :: 50 : x. These simple calculations are possible because the symbols and formulas in the equations represent the relative weights of the substances concerned in a chemical reaction. When once the relative weights of the atoms have been determined, and it has been agreed to allow the symbols to stand for these relative weights, an equation or formula making use of the symbols becomes a statement of a definite numerical fact, and calculations can be based on it. ~Chemical equations not algebraic.~ Although chemical equations are quantitative, it must be clearly understood that they are not algebraic. A glance at the equations 7 + 4 = 11, 8 + 5 = 9 + 4 will show at once that they are true. The equations HgO = Hg + O, FeO = Fe + O are equally true in an algebraic sense, but experiment shows that only the first is true chemically, for iron oxide (FeO) cannot be directly decomposed into iron and oxygen. Only such equations as have been found by careful experiment to express a real chemical transformation, true both for the kinds of substances as well as for the weights, have any value. _Chemical formulas and equations, therefore, are a concise way of representing qualitatively and quantitatively facts which have been found by experiment to be true in reference to the composition of substances and the changes which they undergo._ ~Formulas representing water of crystallization.~ An examination of substances containing water of crystallization has shown that in every case the water is present in such proportion by weight as can readily be represented by a formula. For example, copper sulphate (CuSO_{4}) and water combine in the ratio of 1 molecule of the sulphate to 5 of water; calcium sulphate (CaSO_{4}) and water combine in the ratio 1: 2 to form gypsum. These facts are expressed by writing the formulas for the two substances with a period between them. Thus the formula for crystallized copper sulphate is CuSO_{4}·5H_{2}O; that of gypsum is CaSO_{4}·2H_{2}O. ~Heat of reaction.~ Attention has frequently been directed to the fact that chemical changes are usually accompanied by heat changes. In general it has been found that in every chemical action heat is either absorbed or given off. By adopting a suitable unit for the measurement of heat, the heat change during a chemical reaction can be expressed in the equation for the reaction. Heat cannot be measured by the use of a thermometer alone, since the thermometer measures the intensity of heat, not its quantity. The easiest way to measure a quantity of heat is to note how warm it will make a definite amount of a given substance chosen as a standard. Water has been chosen as the standard, and the unit of heat is called a _calorie. A calorie is defined as the amount of heat required to raise the temperature of one gram of water one degree._ By means of this unit it is easy to indicate the heat changes in a given chemical reaction. The equation 2H + O = H_{2}O + 68,300 cal. means that when 2.016 g. of hydrogen combine with 16 g. of oxygen, 18.016 g. of water are formed and 68,300 cal. are set free. C + 2S = CS_{2} - 19,000 cal. means that an expenditure of 19,000 cal. is required to cause 12 g. of carbon to unite with 64.12 g. of sulphur to form 76.12 g. of carbon disulphide. In these equations it will be noted that the symbols stand for as many grams of the substance as there are units in the weights of the atoms represented by the symbols. This is always understood to be the case in equations where the heat of reaction is given. ~Conditions of a chemical action are not indicated by equations.~ Equations do not tell the conditions under which a reaction will take place. The equation HgO = Hg + O does not tell us that it is necessary to keep the mercuric oxide at a high temperature in order that the decomposition may go on. The equation Zn + 2HCl = ZnCl_{2} + 2H in no way indicates the fact that the hydrochloric acid must be dissolved in water before it will act upon the zinc. From the equation H + Cl = HCl it would not be suspected that the two gases hydrogen and chlorine will unite instantly in the sunlight, but will stand mixed in the dark a long time without change. It will therefore be necessary to pay much attention to the details of the conditions under which a given reaction occurs, as well as to the expression of the reaction in the form of an equation. EXERCISES 1. Calculate the percentage composition of the following substances: (a) mercuric oxide; (b) potassium chlorate; (c) hydrochloric acid; (d) sulphuric acid. Compare the results obtained with the compositions as given in Chapters II and III. 2. Determine the percentage of copper, sulphur, oxygen, and water in copper sulphate crystals. What weight of water can be obtained from 150 g. of this substance? 3. What weight of zinc can be dissolved in 10 g. of sulphuric acid? How much zinc sulphate will be formed? 4. How many liters of hydrogen measured under standard conditions can be obtained from the action of 8 g. of iron on 10 g. of sulphuric acid? How much iron sulphate (FeSO_{4}) will be formed? 5. 10 g. of zinc were used in the preparation of hydrogen; what weight of iron will be required to prepare an equal volume? 6. How many grams of barium dioxide will be required to prepare 1 kg. of common hydrogen dioxide solution? What weight of barium sulphate will be formed at the same time? 7. What weight of the compound Mn_{3}O_{4} will be formed by strongly heating 25 g. of manganese dioxide? What volume of oxygen will be given off at the same time, measured under standard conditions? 8. (a) What is the weight of 100 l. of hydrogen measured in a laboratory in which the temperature is 20° and pressure 750 mm.? (b) What weight of sulphuric acid is necessary to prepare this amount of hydrogen? (c) The density of sulphuric acid is 1.84. Express the acid required in (b) in cubic centimeters. 9. What weight of potassium chlorate is necessary to furnish sufficient oxygen to fill four 200 cc. bottles in your laboratory (the gas to be collected over water)? CHAPTER VII NITROGEN AND THE RARE ELEMENTS: ARGON, HELIUM, NEON, KRYPTON, XENON ~Historical.~ Nitrogen was discovered by the English chemist Rutherford in 1772. A little later Scheele showed it to be a constituent of air, and Lavoisier gave it the name _azote_, signifying that it would not support life. The name _nitrogen_ was afterwards given it because of its presence in saltpeter or niter. The term azote and symbol Az are still retained by the French chemists. ~Occurrence.~ Air is composed principally of oxygen and nitrogen in the free state, about 78 parts by volume out of every 100 parts being nitrogen. Nitrogen also occurs in nature in the form of potassium nitrate (KNO_{3})--commonly called saltpeter or niter--as well as in sodium nitrate (NaNO_{3}). Nitrogen is also an essential constituent of all living organisms; for example, the human body contains about 2.4% of nitrogen. ~Preparation from air.~ Nitrogen can be prepared from air by the action of some substance which will combine with the oxygen, leaving the nitrogen free. Such a substance must be chosen, however, as will combine with the oxygen to form a product which is not a gas, and which can be readily separated from the nitrogen. The substances most commonly used for this purpose are phosphorus and copper. 1. _By the action of phosphorus._ The method used for the preparation of nitrogen by the action of phosphorus is as follows: The phosphorus is placed in a little porcelain dish, supported on a cork and floated on water (Fig. 26). It is then ignited by contact with a hot wire, and immediately a bell jar or bottle is brought over it so as to confine a portion of the air. The phosphorus combines with the oxygen to form an oxide of phosphorus, known as phosphorus pentoxide. This is a white solid which floats about in the bell jar, but in a short time it is all absorbed by the water, leaving the nitrogen. The withdrawal of the oxygen is indicated by the rising of the water in the bell jar. [Illustration: Fig. 26] 2. _By the action of copper._ The oxygen present in the air may also be removed by passing air slowly through a heated tube containing copper. The copper combines with the oxygen to form copper oxide, which is a solid. The nitrogen passes on and may be collected over water. ~Nitrogen obtained from air is not pure.~ Inasmuch as air, in addition to oxygen and nitrogen, contains small amounts of other gases, and since the phosphorus as well as the copper removes only the oxygen, it is evident that the nitrogen obtained by these methods is never quite pure. About 1% of the product is composed of other gases, from which it is very difficult to separate the nitrogen. The impure nitrogen so obtained may, however, be used for a study of most of the properties of nitrogen, since these are not materially affected by the presence of the other gases. ~Preparation from compounds of nitrogen.~ Pure nitrogen may be obtained from certain compounds of the element. Thus, if heat is applied to the compound ammonium nitrite (NH_{4}NO_{2}), the change represented in the following equation takes place: NH_{4}NO_{2} = 2H_{2}O + 2N. ~Physical properties.~ Nitrogen is similar to oxygen and hydrogen in that it is a colorless, odorless, and tasteless gas. One liter of nitrogen weighs 1.2501 g. It is almost insoluble in water. It can be obtained in the form of a colorless liquid having a boiling point of -195° at ordinary pressure. At -214° it solidifies. ~Chemical properties.~ Nitrogen is characterized by its inertness. It is neither combustible nor a supporter of combustion. At ordinary temperatures it will not combine directly with any of the elements except under rare conditions. At higher temperatures it combines with magnesium, lithium, titanium, and a number of other elements. The compounds formed are called _nitrides_, just as compounds of an element with oxygen are called _oxides_. When it is mixed with oxygen and subjected to the action of electric sparks, the two gases slowly combine forming oxides of nitrogen. A mixture of nitrogen and hydrogen when treated similarly forms ammonia, a gaseous compound of nitrogen and hydrogen. Since we are constantly inhaling nitrogen, it is evident that it is not poisonous. Nevertheless life would be impossible in an atmosphere of pure nitrogen on account of the exclusion of the necessary oxygen. ~Argon, helium, neon, krypton, xenon.~ These are all rare elements occurring in the air in very small quantities. Argon, discovered in 1894, was the first one obtained. Lord Rayleigh, an English scientist, while engaged in determining the exact weights of various gases, observed that the nitrogen obtained from the air is slightly heavier than pure nitrogen obtained from its compounds. After repeating his experiments many times, always with the same results, Rayleigh finally concluded that the nitrogen which he had obtained from the air was not pure, but was mixed with a small amount of some unknown gas, the density of which is greater than that of nitrogen. Acting on this assumption, Rayleigh, together with the English chemist Ramsay, attempted to separate the nitrogen from the unknown gas. Knowing that nitrogen would combine with magnesium, they passed the nitrogen obtained from the air and freed from all known substances through tubes containing magnesium heated to the necessary temperature. After repeating this operation, they finally succeeded in obtaining from the atmospheric nitrogen a small volume of gas which would not combine with magnesium and hence could not be nitrogen. This proved to be a new element, to which they gave the name _argon_. As predicted, this new element was found to be heavier than nitrogen, its density as compared with hydrogen as a standard being approximately 20, that of nitrogen being only 14. About 1% of the atmospheric nitrogen proved to be argon. The new element is characterized by having no affinity for other elements. Even under the most favorable conditions it has not been made to combine with any other element. On this account it was given the name argon, signifying lazy or idle. Like nitrogen, it is colorless, odorless, and tasteless. It has been liquefied and solidified. Its boiling point is -187°. Helium was first found in the gases expelled from certain minerals by heating. Through the agency of the spectroscope it had been known to exist in the sun long before its presence on the earth had been demonstrated,--a fact suggested by the name helium, signifying the sun. Its existence in traces in the atmosphere has also been proven. It was first liquefied by Onnes in July, 1908. Its boiling point, namely -269°, is the lowest temperature yet reached. The remaining elements of this group--neon, krypton, and xenon--have been obtained from liquid air. When liquid air is allowed to boil, the constituents which are the most difficult to liquefy, and which therefore have the lowest boiling points, vaporize first, followed by the others in the order of their boiling points. It is possible in this way to make at least a partial separation of the air into its constituents, and Ramsay thus succeeded in obtaining from liquid air not only the known constituents, including argon and helium, but also the new elements, neon, krypton, and xenon. These elements, as well as helium, all proved to be similar to argon in that they are without chemical activity, apparently forming no compounds whatever. The percentages present in the air are very small. The names, neon, krypton, xenon, signify respectively, new, hidden, stranger. EXERCISES 1. How could you distinguish between oxygen, hydrogen, and nitrogen? 2. Calculate the relative weights of nitrogen and oxygen; of nitrogen and hydrogen. 3. In the preparation of nitrogen from the air, how would hydrogen do as a substance for the removal of the oxygen? 4. What weight of nitrogen can be obtained from 10 l. of air measured under the conditions of temperature and pressure which prevail in your laboratory? 5. How many grams of ammonium nitrite are necessary in the preparation of 20 l. of nitrogen measured over water under the conditions of temperature and pressure which prevail in your laboratory? 6. If 10 l. of air, measured under standard conditions, is passed over 100 g. of hot copper, how much will the copper gain in weight? [Illustration: WILLIAM RAMSAY (Scotch) (1855-) Has made many studies in the physical properties of substances; discovered helium; together with Lord Rayleigh and others he discovered argon, krypton, xenon, and neon; has contributed largely to the knowledge of radio-active substances, showing that radium gradually gives rise to helium; professor at University College, London] CHAPTER VIII THE ATMOSPHERE ~Atmosphere and air.~ The term _atmosphere_ is applied to the gaseous envelope surrounding the earth. The term _air_ is generally applied to a limited portion of this envelope, although the two words are often used interchangeably. Many references have already been made to the composition and properties of the atmosphere. These statements must now be collected and discussed somewhat more in detail. ~Air formerly regarded as an element.~ Like water, air was at first regarded as elementary in character. Near the close of the eighteenth century Scheele, Priestley, and Lavoisier showed by their experiments that it is a mixture of at least two gases,--those which we now call oxygen and nitrogen. By burning substances in an inclosed volume of air and noting the contraction in volume due to the removal of the oxygen, they were able to determine with some accuracy the relative volumes of oxygen and nitrogen present in the air. ~The constituents of the atmosphere.~ The constituents of the atmosphere may be divided into two general groups: those which are essential to life and those which are not essential. 1. _Constituents essential to life._ In addition to oxygen and nitrogen at least two other substances, namely, carbon dioxide and water vapor, must be present in the atmosphere in order that life may exist. The former of these is a gaseous compound of carbon and oxygen having the formula CO_{2}. Its properties will be discussed in detail in the chapter on the compounds of carbon. Its presence in the air may be shown by causing the air to bubble through a solution of calcium hydroxide (Ca(OH)_{2}), commonly called lime water. The carbon dioxide combines with the calcium hydroxide in accordance with the following equation: Ca(OH)_{2} + CO_{2} = CaCO_{3} + H_{2}O. The resulting calcium carbonate (CaCO_{3}) is insoluble in water and separates in the form of a white powder, which causes the solution to appear milky. The presence of water vapor is readily shown by its condensation on cold objects as well as by the fact that a bit of calcium chloride when exposed to the air becomes moist, and may even dissolve in the water absorbed from the air. 2. _Constituents not essential to life._ In addition to the essential constituents, the air contains small percentages of various other gases, the presence of which so far as is known is not essential to life. This list includes the rare elements, argon, helium, neon, krypton, and xenon; also hydrogen, ammonia, hydrogen dioxide, and probably ozone. Certain minute forms of life (germs) are also present, the decay of organic matter being due to their presence. ~Function of each of the essential constituents.~ (1) The oxygen directly supports life through respiration. (2) The nitrogen, on account of its inactivity, serves to dilute the oxygen, and while contrary to the older views, it is possible that life might continue to exist in the absence of the atmospheric nitrogen, yet the conditions of life would be entirely changed. Moreover, nitrogen is an essential constituent of all animal and plant life. It was formerly supposed that neither animals nor plants could assimilate the free nitrogen, but it has been shown recently that the plants of at least one natural order, the Leguminosæ, to which belong the beans, peas, and clover, have the power of directly assimilating the free nitrogen from the atmosphere. This is accomplished through the agency of groups of bacteria, which form colonies in little tubercles on the roots of the plants. These bacteria probably assist in the absorption of nitrogen by changing the free nitrogen into compounds which can be assimilated by the plant. Fig. 27 shows the tubercles on the roots of a variety of bean. (3) The presence of water vapor in the air is necessary to prevent excessive evaporation from both plants and animals. (4) Carbon dioxide is an essential plant food. [Illustration: Fig. 27] ~The quantitative analysis of air.~ A number of different methods have been devised for the determination of the percentages of the constituents present in the atmosphere. Among these are the following. 1. _Determination of oxygen._ (1) The oxygen is withdrawn from a measured volume of air inclosed in a tube, by means of phosphorus. To make the determination, a graduated tube is filled with water and inverted in a vessel of water. Air is introduced into the tube until it is partially filled with the gas. The volume of the inclosed air is carefully noted and reduced to standard conditions. A small piece of phosphorus is attached to a wire and brought within the tube as shown in Fig. 28. After a few hours the oxygen in the inclosed air will have combined with the phosphorus, the water rising to take its place. The phosphorus is removed and the volume is again noted and reduced to standard conditions. The contraction in the volume of the air is equal to the volume of oxygen absorbed. [Illustration: Fig. 28] (2) The oxygen may also be estimated by passing a measured volume of air through a tube containing copper heated to a high temperature. The oxygen in the air combines with the copper to form copper oxide (CuO). Hence the increase in the weight of the copper equals the weight of the oxygen in the volume of air taken. (3) A more accurate method is the following. A eudiometer tube is filled with mercury and inverted in a vessel of the same liquid. A convenient amount of air is then introduced into the tube and its volume accurately noted. There is then introduced more than sufficient hydrogen to combine with the oxygen present in the inclosed air, and the volume is again accurately noted. The mixture is then exploded by an electric spark, and the volume is once more taken. By subtracting this volume from the total volume of the air and hydrogen there is obtained the contraction in volume due to the union of the oxygen and hydrogen. The volume occupied by the water formed by the union of the two gases is so small that it may be disregarded in the calculation. Since oxygen and hydrogen combine in the ratio 1: 2 by volume, it is evident that the contraction in volume due to the combination is equal to the volume occupied by the oxygen in the air contained in the tube, plus twice this volume of hydrogen. In other words, one third of the total contraction is equal to the volume occupied by the oxygen in the inclosed air. The following example will make this clear: Volume of air in tube 50.0 cc. Volume after introducing hydrogen 80.0 Volume after combination of oxygen and hydrogen 48.5 Contraction in volume due to combination (80 cc.-48.5 cc.) 31.5 Volume of oxygen in 50 cc. of air (1/3 of 31.5) 10.5 All these methods agree in showing that 100 volumes of dry air contain approximately 21 volumes of oxygen. 2. _Determination of nitrogen._ If the gas left after the removal of oxygen from a portion of air is passed over heated magnesium, the nitrogen is withdrawn, argon and the other rare elements being left. It may thus be shown that of the 79 volumes of gas left after the removal of the oxygen from 100 volumes of air, approximately 78 are nitrogen and 0.93 argon. The other elements are present in such small quantities that they may be neglected. 3. _Determination of carbon dioxide._ The percentage of carbon dioxide in any given volume of air may be determined by passing the air over calcium hydroxide or some other compound which will combine with the carbon dioxide. The increase in the weight of the hydroxide equals the weight of the carbon dioxide absorbed. The amount present in the open normal air is from 3 to 4 parts by volume in 10,000 volumes of air, or about 0.04%. 4. _Determination of water vapor._ The water vapor present in a given volume of air may be determined by passing the air over calcium chloride (or some other compound which has a strong affinity for water), and noting the increase in the weight of the chloride. The amount present varies not only with the locality, but there is a wide variation from day to day in the same locality because of the winds and changes in temperature. ~Processes affecting the composition of the air.~ The most important of these processes are the following. 1. _Respiration._ In the process of respiration some of the oxygen in the inhaled air is absorbed by the blood and carried to all parts of the body, where it combines with the carbon of the worn-out tissues. The products of oxidation are carried back to the lungs and exhaled in the form of carbon dioxide. The amount exhaled by an adult averages about 20 l. per hour. Hence in a poorly ventilated room occupied by a number of people the amount of carbon dioxide rapidly increases. While this gas is not poisonous unless present in large amounts, nevertheless air containing more than 15 parts in 10,000 is not fit for respiration. 2. _Combustion._ All of the ordinary forms of fuel contain large percentages of carbon. On burning, this carbon combines with oxygen in the air, forming carbon dioxide. Combustion and respiration, therefore, tend to diminish the amount of oxygen in the air and to increase the amount of carbon dioxide. 3. _Action of plants._ Plants have the power, when in the sunlight, of absorbing carbon dioxide from the air, retaining the carbon and returning at least a portion of the oxygen to the air. It will be observed that these changes are just the opposite of those brought about by the processes of respiration and combustion. ~Poisonous effect of exhaled air.~ The differences in the percentages of oxygen, carbon dioxide, and moisture present in inhaled air and exhaled air are shown in the following analyses. INHALED AIR EXHALED AIR Oxygen 21.00% 16.00% Carbon dioxide 0.04 4.38 Moisture variable saturated The foul odor of respired air is due to the presence of a certain amount of organic matter. It is possible that this organic matter rather than the carbon dioxide is responsible for the injurious effects which follow the respiration of impure air. The extent of such organic impurities present may be judged, however, by the amount of carbon dioxide present, since the two are exhaled together. ~The cycle of carbon in nature.~ Under the influence of sunlight, the carbon dioxide absorbed from the air by plants reacts with water and small amounts of other substances absorbed from the soil to form complex compounds of carbon which constitute the essential part of the plant tissue. This reaction is attended by the evolution of oxygen, which is restored to the air. The compounds resulting from these changes are much richer in their energy content than are the substances from which they are formed; hence a certain amount of energy must have been absorbed in their formation. The source of this energy is the sun's rays. If the plant is burned, the changes which took place in the formation of the compounds present are largely reversed. The carbon and hydrogen present combine with oxygen taken from the air to form carbon dioxide and water, while the energy absorbed from the sun's rays is liberated in the form of energy of heat. If, on the other hand, the plant is used as food, the compounds present are used in building up the tissues of the body. When this tissue breaks down, the changes which it undergoes are very similar to those which take place when the plant is burned. The carbon and hydrogen combine with the inhaled oxygen to form carbon dioxide and water, which are exhaled. The energy possessed by the complex substances is liberated partly in the form of energy of heat, which maintains the heat of the body, and partly in the various forms of muscular energy. The carbon originally absorbed from the air by the plant in the form of carbon dioxide is thus restored to the air and is ready to repeat the cycle of changes. ~The composition of the air is constant.~ Notwithstanding the changes constantly taking place which tend to alter the composition of the air, the results of a great many analyses of air collected in the open fields show that the percentages of oxygen and nitrogen as well as of carbon dioxide are very nearly constant. Indeed, so constant are the percentages of oxygen and nitrogen that the question has arisen, whether these two elements are not combined in the air, forming a definite chemical compound. That the two are not combined but are simply mixed together can be shown in a number of ways, among which are the following. 1. When air dissolves in water it has been found that the ratio of oxygen to nitrogen in the dissolved air is no longer 21: 78, but more nearly 35: 65. If it were a chemical compound, the ratio of oxygen to nitrogen would not be changed by solution in water. 2. A chemical compound in the form of a liquid has a definite boiling point. Water, for example, boils at 100°. Moreover the steam which is thus formed has the same composition as the water. The boiling point of liquid air, on the other hand, gradually rises as the liquid boils, the nitrogen escaping first followed by the oxygen. If the two were combined, they would pass off together in the ratio in which they are found in the air. ~Why the air has a constant composition.~ If air is a mixture and changes are constantly taking place which tend to modify its composition, how, then, do we account for the constancy of composition which the analyses reveal? This is explained by several facts. (1) The changes which are caused by the processes of combustion and respiration, on the one hand, and the action of plants, on the other, tend to equalize each other. (2) The winds keep the air in constant motion and so prevent local changes. (3) The volume of the air is so vast and the changes which occur are so small compared with the total amount of air that they cannot be readily detected. (4) Finally it must be noted that only air collected in the open fields shows this constancy in composition. The air in a poorly ventilated room occupied by a number of people rapidly changes in composition. ~The properties of the air.~ Inasmuch as air is composed principally of a mixture of oxygen and nitrogen, which elements have already been discussed, its properties may be inferred largely from those of the two gases. One liter weighs 1.2923 g. It is thus 14.38 times as heavy as hydrogen. At the sea level it exerts an average pressure sufficient to sustain a column of mercury 760 mm. in height. This is taken as the standard pressure in determining the volumes of gases as well as the boiling points of liquids. Water may be made to boil at any temperature between 0° and considerably above 100° by simply varying the pressure. It is only when the pressure upon it is equal to the normal pressure of the atmosphere at the sea level, as indicated by a barometric reading of 760 mm., that it boils at 100°. ~Preparation of liquid air.~ Attention has been called to the fact that both oxygen and nitrogen can be obtained in the liquid state by strongly cooling the gases and applying great pressure to them. Since air is largely a mixture of these two gases, it can be liquefied by the same methods. The methods for liquefying air have been simplified greatly in that the low temperature required is obtained by allowing a portion of the compressed air to expand. The expansion of a gas is always attended by the absorption of heat. In liquefying air the apparatus is so constructed that the heat absorbed is withdrawn from air already under great pressure. This process is continued until the temperature is lowered to the point of liquefaction. [Illustration: Fig. 29] ~The Dewar bulb.~ It is not possible to preserve air in the liquid state in a closed vessel, on account of the enormous pressure exerted by it in its tendency to pass into the gaseous state. It may however be preserved for some hours or even days before it will completely evaporate, by simply placing it in an open vessel surrounded by a nonconducting material. The most efficient vessel for this purpose is the _Dewar bulb_ shown in Fig. 29. The air is withdrawn from the space between the two walls, thus making it nonconducting. ~Properties and uses of liquid air.~ When first prepared, liquid air is cloudy because of the presence of particles of solid carbon dioxide. These may be filtered off, leaving a liquid of slightly bluish color. It begins to boil at about -190°, the nitrogen passing off first, gradually followed by the oxygen, the last portions being nearly pure oxygen. To a certain extent oxygen is now prepared in this way for commercial purposes. The extremely low temperature of liquid air may be inferred from the fact that mercury when cooled by it is frozen to a mass so hard that it may be used for driving nails. Liquid air is used in the preparation of oxygen and as a cooling agent in the study of the properties of matter at low temperatures. It has thus been found that elements at extremely low temperatures largely lose their chemical activity. EXERCISES 1. When oxygen and nitrogen are mixed in the proportion in which they exist in the atmosphere, heat is neither evolved nor absorbed by the process. What important point does this suggest? 2. What essential constituent of the air is found in larger amount in manufacturing districts than in the open country? 3. Can you suggest any reason why the growth of clover in a field improves the soil? 4. Why are the inner walls of a Dewar bulb sometimes coated with a film of silver? 5. To what is the blue color of liquid air due? Does this color increase in intensity on standing? 6. When ice is placed in a vessel containing liquid air, the latter boils violently. Explain. 7. Taking the volumes of the oxygen and nitrogen in 100 volumes of air as 21 and 78 respectively, calculate the percentages of these elements present by weight. 8. Would combustion be more intense in liquid air than in the gaseous substance? 9. A tube containing calcium chloride was found to weigh 30.1293 g. A volume of air which weighed 15.2134 g. was passed through, after which the weight of the tube was found to be 30.3405 g. What was the percentage amount of moisture present in the air? 10. 10 l. of air measured at 20° and 740 mm. passed through lime water caused the precipitation of 0.0102 g. of CaCO_{3}. Find the number of volumes of carbon dioxide in 10,000 volumes of the air. CHAPTER IX SOLUTIONS ~Definitions.~ When a substance disappears in a liquid in such a way as to thoroughly mix with it and to be lost to sight as an individual body, the resulting liquid is called a _solution_. The liquid in which the substance dissolves is called the _solvent_, while the dissolved substance is called the _solute_. ~Classes of solutions.~ Matter in any one of its physical states may dissolve in a liquid, so that we may have solutions of gases, of liquids, and of solids. Solutions of liquids in liquids are not often mentioned in the following pages, but the other two classes will become very familiar in the course of our study, and deserve special attention. SOLUTION OF GASES IN LIQUIDS [Illustration: Fig. 30] It has already been stated that oxygen, hydrogen, and nitrogen are slightly soluble in water. Accurate study has led to the conclusion that all gases are soluble to some extent not only in water but in many other liquids. The amount of a gas which will dissolve in a liquid depends upon a number of conditions, and these can best be understood by supposing a vessel B (Fig. 30), to be filled with the gas and inverted over the liquid. Under these circumstances the gas cannot escape or become mixed with another gas. ~Circumstances affecting the solubility of gases.~ A number of circumstances affect the solubility of a gas in a liquid. 1. _Nature of the gas._ Other conditions being equal, each gas has its own peculiar solubility, just as it has its own special taste or odor. The solubility of gases varies between wide limits, as will be seen from the following table, but as a rule a given volume of a liquid will not dissolve more than two or three times its own volume of a gas. _Solubility of Gases in Water_ 1 l. of water at 760 mm. pressure and at 0° will dissolve: Ammonia 1148.00 l. Hydrochloric acid 503.00 Sulphur dioxide 79.79 Carbon dioxide 1.80 Oxygen 41.14 cc. Hydrogen 21.15 Nitrogen 20.03 In the case of very soluble gases, such as the first three in the table, it is probable that chemical combination between the liquid and the gas takes place. 2. _Nature of the liquid._ The character of the liquid has much influence upon the solubility of a gas. Water, alcohol, and ether have each its own peculiar solvent power. From the solubility of a gas in water, no prediction can be made as to its solubility in other liquids. 3. _Influence of pressure._ It has been found that the weight of gas which dissolves in a given case is proportional to the pressure exerted upon the gas. If the pressure is doubled, the weight of gas going into solution is doubled; if the pressure is diminished to one half of its original value, half of the dissolved gas will escape. Under high pressure, large quantities of gas can be dissolved in a liquid, and when the pressure is removed the gas escapes, causing the liquid to foam or _effervesce_. 4. _Influence of temperature._ In general, the lower the temperature of the liquid, the larger the quantity of gas which it can dissolve. 1000 volumes of water at 0° will dissolve 41.14 volumes of oxygen; at 50°, 18.37 volumes; at 100° none at all. While most gases can be expelled from a liquid by boiling the solution, some cannot. For example, it is not possible to expel hydrochloric acid gas completely from its solution by boiling. SOLUTION OF SOLIDS IN LIQUIDS This is the most familiar class of solutions, since in the laboratory substances are much more frequently used in the form of solutions than in the solid state. ~Circumstances affecting the solubility of a solid.~ The solubility of a solid in a liquid depends upon several factors. 1. _Nature of the solid._ Other conditions being the same, solids vary greatly in their solubility in liquids. This is illustrated in the following table: _Table of Solubility of Solids at 18°_ 100 cc. of water will dissolve: Calcium chloride 71.0 g. Sodium chloride 35.9 Potassium nitrate 29.1 Copper sulphate 21.4 Calcium sulphate 0.207 No solids are absolutely insoluble, but the amount dissolved may be so small as to be of no significance for most purposes. Thus barium sulphate, one of the most insoluble of common substances, dissolves in water to the extent of 1 part in 400,000. 2. _Nature of the solvent._ Liquids vary much in their power to dissolve solids. Some are said to be good solvents, since they dissolve a great variety of substances and considerable quantities of them. Others have small solvent power, dissolving few substances, and those to a slight extent only. Broadly speaking, water is the most general solvent, and alcohol is perhaps second in solvent power. 3. _Temperature._ The weight of a solid which a given liquid can dissolve varies with the temperature. Usually it increases rapidly as the temperature rises, so that the boiling liquid dissolves several times the weight which the cold liquid will dissolve. In some instances, as in the case of common salt dissolved in water, the temperature has little influence upon the solubility, and a few solids are more soluble in cold water than in hot. The following examples will serve as illustrations: _Table of Solubility at 0° and at 100°_ 100 cc. of water will dissolve: At 0° At 100° Calcium chloride 49.6 g. 155.0 g. Sodium chloride 35.7 39.8 Potassium nitrate 13.3 247.0 Copper sulphate 15.5 73.5 Calcium sulphate 0.205 0.217 Calcium hydroxide 0.173 0.079 ~Saturated solutions.~ A liquid will not dissolve an unlimited quantity of a solid. On adding the solid to the liquid in small portions at a time, it will be found that a point is reached at which the liquid will not dissolve more of the solid at that temperature. The solid and the solution remain in contact with each other unchanged. This condition may be described by saying that they are in equilibrium with each other. A solution is said to be _saturated_ when it remains unchanged in concentration in contact with some of the solid. The weight of the solid which will completely saturate a definite volume of a liquid at a given temperature is called the _solubility_ of the substance at that temperature. ~Supersaturated solutions.~ When a solution, saturated at a given temperature, is allowed to cool it sometimes happens that no solid crystallizes out. This is very likely to occur when the vessel used is perfectly smooth and the solution is not disturbed in any way. Such a solution is said to be _supersaturated_. That this condition is unstable can be shown by adding a crystal of the solid to the solution. All of the solid in excess of the quantity required to saturate the solution at this temperature will at once crystallize out, leaving the solution saturated. Supersaturation may also be overcome in many cases by vigorously shaking or stirring the solution. ~General physical properties of solutions.~ A few general statements may be made in reference to the physical properties of solutions. 1. _Distribution of the solid in the liquid._ A solid, when dissolved, tends to distribute itself uniformly through the liquid, so that every part of the solution has the same concentration. The process goes on very slowly unless hastened by stirring or shaking the solution. Thus, if a few crystals of a highly colored substance such as copper sulphate are placed in the bottom of a tall vessel full of water, it will take weeks for the solution to become uniformly colored. 2. _Boiling points of solutions._ The boiling point of a liquid is raised by the presence of a substance dissolved in it. In general the extent to which the boiling point of a solvent is raised by a given substance is proportional to the concentration of the solution, that is, to the weight of the substance dissolved in a definite weight of the solvent. 3. _Freezing points of solutions._ A solution freezes at a lower temperature than the pure solvent. The lowering of the freezing point obeys the same law which holds for the raising of the boiling point: the extent of lowering is proportional to the weight of dissolved substance, that is, to the concentration of the solution. ~Electrolysis of solutions.~ Pure water does not appreciably conduct the electric current. If, however, certain substances such as common salt are dissolved in the water, the resulting solutions are found to be conductors of electricity. Such solutions are called _electrolytes_. When the current passes through an electrolyte some chemical change always takes place. This change is called _electrolysis_. [Illustration: Fig. 31] The general method used in the electrolysis of a solution is illustrated in Fig. 31. The vessel D contains the electrolyte. Two plates or rods, A and B, made of suitable material, are connected with the wires from a battery (or dynamo) and dipped into the electrolyte, as shown in the figure. These plates or rods are called _electrodes_. The electrode connected with the zinc plate of the battery is the negative electrode or _cathode_, while that connected with the carbon plate is the positive electrode or _anode_. ~Theory of electrolytic dissociation.~ The facts which have just been described in connection with solutions, together with many others, have led chemists to adopt a theory of solutions called _the theory of electrolytic dissociation_. The main assumptions in this theory are the following. 1. _Formation of ions._ Many compounds when dissolved in water undergo an important change. A portion of their molecules fall apart, or _dissociate_, into two or more parts, called _ions_. Thus sodium nitrate (NaNO_{3}) dissociates into the ions Na and NO_{3}; sodium chloride, into the ions Na and Cl. These ions are free to move about in the solution independently of each other like independent molecules, and for this reason were given the name ion, which signifies a wanderer. 2. _The electrical charge of ions._ Each ion carries a heavy electrical charge, and in this respect differs from an atom or molecule. It is evident that the sodium in the form of an ion must differ in some important way from ordinary sodium, for sodium ions, formed from sodium nitrate, give no visible evidence of their presence in water, whereas metallic sodium at once decomposes the water. The electrical charge, therefore, greatly modifies the usual chemical properties of the element. 3. _The positive charges equal the negative charges._ The ions formed by the dissociation of any molecule are of two kinds. One kind is charged with positive electricity and the other with negative electricity; moreover the sum of all the positive charges is always equal to the sum of all the negative charges. The solution as a whole is therefore electrically neutral. If we represent dissociation by the usual chemical equations, with the electrical charges indicated by + and - signs following the symbols, the dissociation of sodium chloride molecules is represented thus: NaCl --> Na^{+}, Cl^{-}. The positive charge on each sodium ion exactly equals the negative charge on each chlorine ion. Sodium sulphate dissociates, as shown in the equation Na_{2}SO_{4} --> 2Na^{+}, SO_{4}^{--}. Here the positive charge on the two sodium ions equals the double negative charge on the SO_{4} ion. 4. _Not all compounds dissociate._ Only those compounds dissociate whose solutions form electrolytes. Thus salt dissociates when dissolved in water, the resulting solution being an electrolyte. Sugar, on the other hand, does not dissociate and its solution is not a conductor of the electric current. 5. _Extent of dissociation differs in different liquids._ While compounds most readily undergo dissociation in water, yet dissociation often occurs to a limited extent when solution takes place in liquids other than water. In the discussion of solutions it will be understood that the solvent is water unless otherwise noted. ~The theory of electrolytic dissociation and the properties of solutions.~ In order to be of value, this theory must give a reasonable explanation of the properties of solutions. Let us now see if the theory is in harmony with certain of these properties. ~The theory of electrolytic dissociation and the boiling and freezing points of solutions.~ We have seen that the boiling point of a solution of a substance is raised in proportion to the concentration of the dissolved substance. This is but another way of saying that the change in the boiling point of the solution is proportional to the number of molecules of the dissolved substance present in the solution. It has been found, however, that in the case of electrolytes the boiling point is raised more than it should be to conform to this law. If the solute dissociates into ions, the reason for this becomes clear. Each ion has the same effect on the boiling point as a molecule, and since their number is greater than the number of molecules from which they were formed, the effect on the boiling point is abnormally great. In a similar way, the theory furnishes an explanation of the abnormal lowering of the freezing point of electrolytes. ~The theory of electrolytic dissociation and electrolysis.~ The changes taking place during electrolysis harmonize very completely with the theory of dissociation. This will become clear from a study of the following examples. [Illustration: Fig. 32] 1. _Electrolysis of sodium chloride._ Fig. 32 represents a vessel in which the electrolyte is a solution of sodium chloride (NaCl). According to the dissociation theory the molecules of sodium chloride dissociate into the ions Na^{+} and Cl^{-}. The Na^{+} ions are attracted to the cathode owing to its large negative charge. On coming into contact with the cathode, the Na^{+} ions give up their positive charge and are then ordinary sodium atoms. They immediately decompose the water according to the equation Na + H_{2}O = NaOH + H, and hydrogen is evolved about the cathode. The chlorine ions on being discharged at the anode in similar manner may either be given off as chlorine gas, or may attack the water, as represented in the equation 2Cl + H_{2}O = 2HCl + O. 2. _Electrolysis of water._ The reason for the addition of sulphuric acid to water in the preparation of oxygen and hydrogen by electrolysis will now be clear. Water itself is not an electrolyte to an appreciable extent; that is, it does not form enough ions to carry a current. Sulphuric acid dissolved in water is an electrolyte, and dissociates into the ions 2 H^{+} and SO_{4}^{--}. In the process of electrolysis of the solution, the hydrogen ions travel to the cathode, and on being discharged escape as hydrogen gas. The SO_{4} ions, when discharged at the anode, act upon water, setting free oxygen and once more forming sulphuric acid: SO_{4} + H_{2}O = H_{2}SO_{4} + O. The sulphuric acid can again dissociate and the process repeat itself as long as any water is left. Hence the hydrogen and oxygen set free in the electrolysis of water really come directly from the acid but indirectly from the water. 3. _Electrolysis of sodium sulphate._ In a similar way, sodium sulphate (Na_{2}SO_{4}), when in solution, gives the ions 2 Na^{+} and SO_{4}^{--}. On being discharged, the sodium atoms decompose water about the cathode, as in the case of sodium chloride, while the SO_{4} ions when discharged at the anode decompose the water, as represented in the equation SO_{4} + H_{2}O = H_{2}SO_{4} + O [Illustration: Fig. 33] That new substances are formed at the cathode and anode may be shown in the following way. A U-tube, such as is represented in Fig. 33, is partially filled with a solution of sodium sulphate, and the liquid in one arm is colored with red litmus, that in the other with blue litmus. An electrode placed in the red solution is made to serve as cathode, while one in the blue solution is made the anode. On allowing the current to pass, the blue solution turns red, while the red solution turns blue. These are exactly the changes which would take place if sodium hydroxide and sulphuric acid were to be set free at the electrodes, as required by the theory. ~The properties of electrolytes depend upon the ions present.~ When a substance capable of dissociating into ions is dissolved in water, the properties of the solution will depend upon two factors: (1) the ions formed from the substance; (2) the undissociated molecules. Since the ions are usually more active chemically than the molecules, most of the chemical properties of an electrolyte are due to the ions rather than to the molecules. The solutions of any two substances which give the same ion will have certain properties in common. Thus all solutions containing the copper ion (Cu^{++}) are blue, unless the color is modified by the presence of ions or molecules having some other color. EXERCISES 1. Distinguish clearly between the following terms: electrolysis, electrolyte, electrolytic dissociation, ions, solute, solvent, solution, saturated solution, and supersaturated solution. 2. Why does the water from some natural springs effervesce? 3. (a) Why does not the water of the ocean freeze? (b) Why will ice and salt produce a lower temperature than ice alone? 4. Why does shaking or stirring make a solid dissolve more rapidly in a liquid? 5. By experiment it was found that a certain volume of water was saturated at 100° with 114 g. of potassium nitrate. On cooling to 0° a portion of the substance crystallized. (a) How many grams of the substance remained in solution? (b) What was the strength of the solution at 18°? (c) How much water had been used in the experiment? 6. (a) 10 g. of common salt were dissolved in water and the solution evaporated to dryness; what weight of solid was left? (b) 10 g. of zinc were dissolved in hydrochloric acid and the solution evaporated to dryness; what weight of solid was left? 7. Account for the fact that sugar sometimes deposits from molasses, even when no evaporation has taken place. 8. (a) From the standpoint of the theory of electrolytic dissociation, write the simple equation for a dilute solution of copper sulphate (CuSO_{4}); this solution is blue. (b) In the same manner, write one for sodium sulphate; this solution is colorless. (c) How would you account for the color of the copper sulphate solution? 9. (a) As in the preceding exercise, write a simple equation for a dilute solution of copper chloride (CuCl_{2}); this solution is blue. (b) In the same manner, write one for sodium chloride; this solution is colorless. To what is the blue color due? 10. What component is present in concentrated sulphuric acid that is almost wanting in very dilute sulphuric acid? 11. Why will vegetables cook faster when boiled in strong salt water than when boiled in pure water? 12. How do you explain the foaming of soda water? CHAPTER X ACIDS, BASES, AND SALTS; NEUTRALIZATION ~Acids, bases, and salts.~ The three classes of compounds known respectively as acids, bases, and salts include the great majority of the compounds with which we shall have to deal. It is important, therefore, for us to consider each of these classes in a systematic way. The individual members belonging to each class will be discussed in detail in the appropriate places, but a few representatives of each class will be described in this chapter with special reference to the common properties in accordance with which they are classified. ~The familiar acids.~ _Hydrochloric acid_ is a gas composed of hydrogen and chlorine, and has the formula HCl. The substance is very soluble in water, and it is this solution which is usually called hydrochloric acid. _Nitric acid_ is a liquid composed of hydrogen, nitrogen, and oxygen, having the formula HNO_{3}. As sold commercially it is mixed with about 32% of water. _Sulphuric acid_, whose composition is represented by the formula H_{2}SO_{4}, is an oily liquid nearly twice as heavy as water, and is commonly called _oil of vitriol_. ~Characteristics of acids.~ (1) All acids contain hydrogen. (2) When dissolved in water the molecules of the acid dissociate into two kinds of ions. One of these is always hydrogen and is the cation (+), while the other consists of the remainder of the molecule and is the anion (-). (3) The solution tastes sour. (4) It has the power to change the color of certain substances called _indicators_. Thus blue litmus is changed to red, and yellow methyl orange is changed to red. Since all acids produce hydrogen cations, while the anions of each are different, the properties which all acids have in common when in solution, such as taste and action on indicators, must be attributed to the hydrogen ions. DEFINITION: _An acid is a substance which produces hydrogen ions when dissolved in water or other dissociating liquids._ ~Undissociated acids.~ When acids are perfectly free from water, or are dissolved in liquids like benzene which do not have the power of dissociating them into ions, they should have no real acid properties. This is found to be the case. Under these circumstances they do not affect the color of indicators or have any of the properties characteristic of acids. The familiar bases. The bases most used in the laboratory are sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH)_{2}). These are white solids, soluble in water, the latter sparingly so. Some bases are very difficultly soluble in water. The very soluble ones with most pronounced basic properties are sometimes called the _alkalis_. ~Characteristics of bases.~ (1) All bases contain hydrogen and oxygen. (2) When dissolved in water the molecules of the base dissociate into two kinds of ions. One of these is always composed of oxygen and hydrogen and is the anion. It has the formula OH and is called the _hydroxyl ion_. The remainder of the molecule, which usually consists of a single atom, is the cation. (3) The solution of a base has a soapy feel and a brackish taste. (4) It reverses the color change produced in indicators by acids, turning red litmus blue, and red methyl orange yellow. Since all bases produce hydroxyl anions, while the cations of each are different, the properties which all bases have in common when in solution must be due to the hydroxyl ions. DEFINITION: _A base is a substance which produces hydroxyl ions when dissolved in water or other dissociating liquids._ ~Undissociated bases.~ Bases, in the absence of water or when dissolved in liquids which do not dissociate them, should have none of the properties characteristic of this class of substances. This has been found to be the case. For example, they have no effect upon indicators under these circumstances. ~Neutralization.~ When an acid and a base are brought together in solution in proper proportion, the characteristic properties of each disappear. The solution tastes neither sour nor brackish; it has no effect upon indicators. There can therefore be neither hydrogen nor hydroxyl ions present in the solution. A study of reactions of this kind has shown that the hydrogen ions of the acid combine with the hydroxyl ions of the base to form molecules of water, water being a substance which is not appreciably dissociated into ions. This action of an acid on a base is called _neutralization_. The following equations express the neutralization of the three acids by three bases, water being formed in each case. Na^{+}, OH^{-} + H^{+}, Cl^{-} = Na^{+}, Cl^{-} + H_{2}O. K^{+}, OH^{-} + H^{+}, NO_{3}^{-} = K^{+}, NO_{3}^{-} + H_{2}O. Ca^{++}, (OH)_{2}^{--} + H_{2}^{++}, SO_{4}^{--} = Ca^{++}, SO_{4}^{--} + 2H_{2}O. DEFINITION: _Neutralization consists in the union of the hydrogen ion of an acid with the hydroxyl ion of a base to form water._ ~Salts.~ It will be noticed that in neutralization the anion of the acid and the cation of the base are not changed. If, however, the water is expelled by evaporation, these two ions slowly unite, and when the water becomes saturated with the substance so produced, it separates in the form of a solid called a _salt_. DEFINITION: _A salt is a substance formed by the union of the anion of an acid with the cation of a base._ ~Characteristics of salts.~ (1) From the definition of a salt it will be seen that there is no element or group of elements which characterize salts. (2) Salts as a class have no peculiar taste. (3) In the absence of all other substances they are without action on indicators. (4) When dissolved in water they form two kinds of ions. ~Heat of neutralization.~ If neutralization is due to the union of hydrogen ions with hydroxyl ions, and nothing more, it follows that when a given weight of water is formed in neutralization, the heat set free should always be the same, no matter from what acid and base the two kinds of ions have been supplied. Careful experiments have shown that this is the case, provided no other reactions take place at the same time. When 18g. of water are formed in neutralization, 13,700 cal. of heat are set free. This is represented in the equations Na^{+}, OH^{-} + H^{+}, Cl^{-} = Na^{+}, Cl^{-} + H_{2}O + 13,700 cal. K^{+}, OH^{-} + H^{+}, NO_{3}^{-} = K^{+}, NO_{3}^{-} + H_{2}O + 13,700 cal. Ca^{++}, (OH)_{2}^{--} + H_{2}^{++}, SO_{4}^{--} = Ca^{++}, SO_{4}^{--} + 2H_{2}O + 2 × 13,700 cal. ~Neutralization a quantitative act.~ Since neutralization is a definite chemical act, each acid will require a perfectly definite weight of each base for its neutralization. For example, a given weight of sulphuric acid will always require a definite weight of sodium hydroxide, in accordance with the equation H_{2}, SO_{4} + 2Na, OH = Na_{2}, SO_{4} + 2H_{2}O. ~Determination of the ratio in neutralization.~ The quantities of acid and base required in neutralization may be determined in the following way. Dilute solutions of the two substances are prepared, the sulphuric acid being placed in one of the burettes (Fig. 34) and the sodium hydroxide in the other. The levels of the two liquids are then brought to the zero marks of the burettes by means of the stopcocks. A measured volume of the acid is drawn off into a beaker, a few drops of litmus solution added, and the sodium hydroxide is run in drop by drop until the red litmus just turns blue. The volume of the sodium hydroxide consumed is then noted. If the concentrations of the two solutions are known, it is easy to calculate what weight of sodium hydroxide is required to neutralize a given weight of sulphuric acid. By evaporating the neutralized solution to dryness, the weight of the sodium sulphate formed can be determined directly. Experiment shows that the weights are always in accordance with the equation in the preceding paragraph. [Illustration: Fig. 34] ~Extent of dissociation.~ The question will naturally arise, When an acid, base, or salt dissolves in water, do all the molecules dissociate into ions, or only a part of them? The experiments by which this question can be answered cannot be described here. It has been found, however, that only a fraction of the molecules dissociate. The percentage which will dissociate in a given case depends upon several conditions, the chief of which are: (1) The concentration of the solution. In concentrated solutions only a very small percentage of dissociation occurs. As the solution is diluted the percentage increases, and in very dilute solutions it may be very large, though it is never complete in any ordinary solution. (2) The nature of the dissolved compound. At equal concentrations substances differ much among themselves in the percentage of dissociation. The great majority of salts are about equally dissociated. Acids and bases, on the contrary, show great differences. Some are freely dissociated, while others are dissociated to but a slight extent. ~Strength of acids and bases.~ Since acid and basic properties are due to hydrogen and hydroxyl ions respectively, the acid or base which will produce the greatest percentage of these ions at a given concentration must be regarded as the strongest representative of its class. The acids and bases described in the foregoing paragraphs are all quite strong. In 10% solutions they are dissociated to about 50%, and this is also approximately the extent to which most salts are dissociated at this same concentration. ~Partial neutralization.~ 1. _Basic salts._ The chemical action between an acid and a base is not always as complete as has been represented in the foregoing paragraphs. For example, if the base magnesium hydroxide (Mg(OH)_{2}) and hydrochloric acid (HCl) are brought together in the ratio of an equal number of molecules of each, there will be only half enough hydrogen ions for the hydroxyl ions present. Mg, (OH)_{2} + H, Cl = Mg, OH, Cl + H_{2}O. Magnesium, hydroxyl, and chlorine ions are left at the close of the reaction, and under the proper conditions unite to form molecules of the compound Mg(OH)Cl. This compound, when dissolved, can form hydroxyl ions and therefore possesses basic properties; it can also form the ions of a salt (Mg and Cl), and has properties characteristic of salts. Substances of this kind are called _basic salts._ DEFINITION: _A basic salt is a substance which can give the ions both of a base and of a salt when dissolved in water._ 2. _Acid salts._ In a similar way, when sulphuric acid and sodium hydroxide are brought together in the ratio of equal numbers of the molecules of each, it is possible to have a reaction expressed by the equation Na, OH + H_{2}, SO_{4} = Na, H, SO_{4} + H_{2}O. The ions remaining after all the hydroxyl ions have been used up are those of an acid (H) and those of a salt (Na and SO_{4}). These unite to form the substance NaHSO_{4}, and as the solution becomes saturated with this substance through evaporation, it separates in the form of crystals. In solution this substance can give hydrogen ions, and therefore possesses acid properties; it can also give the ions characteristic of a salt. It is therefore called an _acid salt_. DEFINITION: _An acid salt is one which can give the ions of an acid and of a salt when in solution._ 3. _Normal salts._ Salts which are the products of complete neutralization, such as Na_{2}SO_{4}, and which in solution can give neither hydrogen nor hydroxyl ions, but only the ions of a salt, are called _normal salts_ to distinguish them from acid and basic salts. ~Methods of expressing reactions between compounds in solution.~ Chemical equations representing reactions between substances in solution may represent the details of the reaction, or they may simply indicate the final products formed. In the latter case the formation of ions is not indicated. Thus, if we wish to call attention to the details of the reaction between sodium hydroxide and hydrochloric acid in solution, the equation is written as follows: Na^{+}, OH^{-} + H^{+}, Cl^{-} = Na^{+}, Cl^{-} + H_{2}O. On the other hand, if we wish simply to represent the final products formed, the following is used. NaOH + HCl = NaCl + H_{2}O. Both of these methods will therefore be used: ~Radicals.~ It has been emphasized that the hydroxyl group (OH) always forms the anion of a base, while the group NO_{3} forms the anion of nitric acid and sodium nitrate; the group SO_{4}, the anion of sulphuric acid and calcium sulphate. A group of elements which in this way constitutes a part of a molecule, acting as a unit in a chemical change, or forming ions in solution, is called a _radical_. Some of these radicals have been given special names, the names signifying the elements present in the radical. Thus we have the hydroxyl radical (OH) and the nitrate radical (NO_{3}). DEFINITION: _A radical is a group of elements forming part of a molecule, and acting as a unit in chemical reactions._ ~Names of acids, bases, and salts.~ Since acids, bases, and salts are so intimately related to each other, it is very advantageous to give names to the three classes in accordance with some fixed system. The system universally adopted is as follows: ~Naming of bases.~ All bases are called _hydroxides_. They are distinguished from each other by prefixing the name of the element which is in combination with the hydroxyl group. Examples: sodium hydroxide (NaOH); calcium hydroxide (Ca(OH)_{2}); copper hydroxide (Cu(OH)_{2}). ~Naming of acids.~ The method of naming acids depends upon whether the acid consists of two elements or three. 1. _Binary acids._ Acids containing only one element in addition to hydrogen are called _binary acids_. They are given names consisting of the prefix _hydro-_, the name of the second element present, and the termination _-ic_. Examples: hydrochloric acid (HCl); hydrosulphuric acid (H_{2}S). 2. _Ternary acids._ In addition to the two elements present in binary acids, the great majority of acids also contain oxygen. They therefore consist of three elements and are called _ternary acids_. It usually happens that the same three elements can unite in different proportions to make several different acids. The most familiar one of these is given a name ending in the suffix _-ic_, while the one with less oxygen is given a similar name, but ending in the suffix _-ous_. Examples: nitric acid (HNO_{3}); nitrous acid (HNO_{2}). In cases where more than two acids are known, use is made of prefixes in addition to the two suffixes _-ic_ and _-ous_. Thus the prefix _per-_ signifies an acid still richer in oxygen; the prefix _hypo-_ signifies one with less oxygen. ~Naming of salts.~ A salt derived from a binary acid is given a name consisting of the names of the two elements composing it, with the termination _-ide_. Example: sodium chloride (NaCl). All other binary compounds are named in the same way. A salt of a ternary acid is named in accordance with the acid from which it is derived. A ternary acid with the termination _-ic_ gives a salt with the name ending in _-ate_, while an acid with termination _-ous_ gives a salt with the name ending in _-ite_. The following table will make the application of these principles clear: ACIDS SYMBOL SALTS SYMBOL Hydrochloric HCl Sodium chloride NaCl Hypochlorous HClO Sodium hypochlorite NaClO Chlorous HClO_{2} Sodium chlorite NaClO_{2} Chloric HClO_{3} Sodium chlorate NaClO_{3} Perchloric HClO_{4} Sodium perchlorate NaClO_{4} EXERCISES 1. 25 cc. of a solution containing 40 g. of sodium hydroxide per liter was found to neutralize 25 cc. of a solution of hydrochloric acid. What was the strength of the acid solution? 2. After neutralizing a solution of sodium hydroxide with nitric acid, there remained after evaporation 100 g. of sodium nitrate. How much of each substance had been used? 3. A solution contains 18 g. of hydrochloric acid per 100 cc. It required 25 cc. of this solution to neutralize 30 cc. of a solution of sodium hydroxide. What was the strength of the sodium hydroxide solution in parts per hundred? 4. When perfectly dry sulphuric acid is treated with perfectly dry sodium hydroxide, no chemical change takes place. Explain. 5. When cold, concentrated sulphuric acid is added to zinc, no change takes place. Recall the action of dilute sulphuric acid on the same metal. How do you account for the difference? 6. A solution of hydrochloric acid in benzene does not conduct the electric current. When this solution is treated with zinc, will hydrogen be evolved? Explain. 7. (a) Write equation for preparation of hydrogen from zinc and dilute sulphuric acid. (b) Rewrite the same equation from the standpoint of the theory of electrolytic dissociation, (c) Subtract the common SO_{4} ion from both members of the equation, (d) From the resulting equation, explain in what the preparation of hydrogen consists when examined from the standpoint of this theory. 8. In the same manner as in the preceding exercise, explain in what the action of sodium on water to give hydrogen consists. CHAPTER XI VALENCE ~Definition of valence.~ A study of the formulas of various binary compounds shows that the elements differ between themselves in the number of atoms of other elements which they are able to hold in combination. This is illustrated in the formulas HCl, H_{2}O, H_{3}N, H_{4}C. (hydrochloric acid) (water) (ammonia) (marsh gas) It will be noticed that while one atom of chlorine combines with one atom of hydrogen, an atom of oxygen combines with two, an atom of nitrogen with three, one of carbon with four. The number which expresses this combining ratio between atoms is a definite property of each element and is called its _valence_. DEFINITION: _The valence of an element is that property which determines the number of the atoms of another element which its atom can hold in combination._ ~Valence a numerical property.~ Valence is therefore merely a numerical relation and does not convey any information in regard to the intensity of the affinity between atoms. Judging by the heat liberated in their union, oxygen has a far stronger affinity for hydrogen than does nitrogen, but an atom of oxygen can combine with two atoms only of hydrogen, while an atom of nitrogen can combine with three. ~Measure of valence.~ In expressing the valence of an element we must select some standard for comparison, just as in the measurement of any other numerical quantity. It has been found that an atom of hydrogen is never able to hold in combination more than one atom of any other element. Hydrogen is therefore taken as the standard, and other elements are compared with it in determining their valence. A number of other elements are like hydrogen in being able to combine with at most one atom of other elements, and such elements are called _univalent_. Among these are chlorine, iodine, and sodium. Elements such as oxygen, calcium, and zinc, which can combine with two atoms of hydrogen or other univalent elements, are said to be _divalent_. Similarly, we have _trivalent, tetravalent, pentavalent_ elements. None have a valence of more than 8. ~Indirect measure of valence.~ Many elements, especially among the metals, do not readily form compounds with hydrogen, and their valence is not easy to determine by direct comparison with the standard element. These elements, however, combine with other univalent elements, such as chlorine, and their valence can be determined from the compounds so formed. ~Variable valence.~ Many elements are able to exert different valences under differing circumstances. Thus we have the compounds Cu_{2}O and CuO, CO and CO_{2}, FeCl_{2} and FeCl_{3}. It is not always possible to assign a fixed valence to an element. Nevertheless each element tends to exert some normal valence, and the compounds in which it has a valence different from this are apt to be unstable and easily changed into compounds in which the valence of the element is normal. The valences of the various elements will become familiar as the elements are studied in detail. ~Valence and combining ratios.~ When elements combine to form compounds, the ratio in which they combine will be determined by their valences. In those compounds which consist of two elements directly combined, the union is between such numbers of the two atoms as have equal valences. Elements of the same valence will therefore combine atom for atom. Designating the valence of the atoms by Roman numerals placed above their symbols, we have the formulas II II II III III IV IV HCl, ZnO, BN, CSi. A divalent element, on the other hand, will combine with two atoms of a univalent element. Thus we have II II II II ZnCl_{2} and H_{2}O (the numerals above each symbol representing the sum of the valences of the atoms of the element present). A trivalent atom will combine with three atoms of a univalent element, as in the compound III III H_{3}N. If a trivalent element combines with a divalent element, the union will be between two atoms of the trivalent element and three of the divalent element, since these numbers are the smallest which have equal valences. Thus the oxide of the trivalent metal aluminium has the formula Al_{2}O_{3}. Finally one atom of a tetravalent element such as carbon will combine with four atoms of a univalent element, as in the compound CH_{4}, or with two atoms of a divalent element, as in the compound CO_{2}. We have no knowledge as to why elements differ in their combining power, and there is no way to determine their valences save by experiment. ~Valence and the structure of compounds.~ Compounds will be met from time to time which are apparent exceptions to the general statements just made in regard to valence. Thus, from the formula for hydrogen dioxide (H_{2}O_{2}), it might be supposed that the oxygen is univalent; yet it is certainly divalent in water (H_{2}O). That it may also be divalent in H_{2}O_{2} may be made clear as follows: The unit valence of each element may be represented graphically by a line attached to its symbol. Univalent hydrogen and divalent oxygen will then have the symbols H- and -O-. When atoms combine, each unit valence of one atom combines with a unit valence of another atom. Thus the composition of water may be expressed by the formula H-O-H, which is meant to show that each of the unit valences of oxygen is satisfied with the unit valence of a single hydrogen atom. The chemical conduct of hydrogen dioxide leads to the conclusion that the two oxygen atoms of its molecule are in direct combination with each other, and in addition each is in combination with a hydrogen atom. This may be expressed by the formula H-O-O-H. The oxygen in the compound is therefore divalent, just as it is in water. It will thus be seen that the structure of a compound must be known before the valences of the atoms making up the compound can be definitely decided upon. Such formulas as H-O-H and H-O-O-H are known as _structural formulas_, because they are intended to show what is known in regard to the arrangement of the atoms in the molecules. ~Valence and the replacing power of atoms.~ Just as elements having the same valence combine with each other atom for atom, so if they replace each other in a chemical reaction they will do so in the same ratio. This is seen in the following equations, in which a univalent hydrogen atom is replaced by a univalent sodium atom: NaOH + HCl = NaCl + H_{2}O. 2NaOH + H_{2}SO_{4} = Na_{2}SO_{4} + 2H_{2}O. Na + H_{2}O = NaOH + H. Similarly, one atom of divalent calcium will replace two atoms of univalent hydrogen or one of divalent zinc: Ca(OH)_{2} + 2 HCl = CaCl_{2} + 2H_{2}O. CaCl_{2} + ZnSO_{4} = CaSO_{4} + ZnCl_{2}. In like manner, one atom of a trivalent element will replace three of a univalent element, or two atoms will replace three atoms of a divalent element. ~Valence and its applications to formulas of salts.~ While the true nature of valence is not understood and many questions connected with the subject remain unanswered, yet many of the main facts are of much help to the student. Thus the formula of a salt, differs from that of the acid from which it is derived in that the hydrogen of the acid has been replaced by a metal. If, then, it is known that a given metal forms a normal salt with a certain acid, the formula of the salt can at once be determined if the valence of the metal is known. Since sodium is univalent, the sodium salts of the acids HCl and H_{2}SO_{4} will be respectively NaCl and Na_{2}SO_{4}. One atom of divalent zinc will replace 2 hydrogen atoms, so that the corresponding zinc salts will be ZnCl_{2} and ZnSO_{4}. The formula for aluminium sulphate is somewhat more difficult to determine. Aluminium is trivalent, and the simplest ratio in which the aluminium atom can replace the hydrogen in sulphuric acid is 2 atoms of aluminium (6 valences) to 3 molecules of sulphuric acid (6 hydrogen atoms). The formula of the sulphate will then be Al_{2}(SO_{4})_{3}. ~Valence and its application to equation writing.~ It will be readily seen that a knowledge of valence is also of very great assistance in writing the equations for reactions of double decomposition. Thus, in the general reaction between an acid and a base, the essential action is between the univalent hydrogen ion and the univalent hydroxyl ion. The base and the acid must always be taken in such proportions as to secure an equal number of each of these ions. Thus, in the reaction between ferric hydroxide (Fe(OH)_{3}) and sulphuric acid (H_{2}SO_{4}), it will be necessary to take 2 molecules of the former and 3 of the latter in order to have an equal number of the two ions, namely, 6. The equation will then be 2Fe(OH)_{3} + 3H_{2}SO_{4} = Fe_{2}(SO_{4})_{3} + 6H_{2}O. Under certain conditions the salts Al_{2}(SO_{4})_{3} and CaCl_{2} undergo double decomposition, the two metals, aluminium and calcium, exchanging places. The simplest ratio of exchange in this case is 2 atoms of aluminium (6 valences) and 3 atoms of calcium (6 valences). The reaction will therefore take place between 1 molecule of Al_{2}(SO_{4})_{3} and 3 of CaCl_{2}, and the equation is as follows: Al_{2}(SO_{4})_{3} + 3 CaCl_{2} = 3CaSO_{4} + 2AlCl_{3}. EXERCISES 1. Sodium, calcium, and aluminium have valences of 1, 2, and 3 respectively; write the formulas of their chlorides, sulphates, and phosphates (phosphoric acid = H_{3}PO_{4}), on the supposition that they form salts having the normal composition. 2. Iron forms one series of salts in which it has a valence of 2, and another series in which it has a valence of 3; write the formulas for the two chlorides of iron, also for the two sulphates, on the supposition that these have the normal composition. 3. Write the equation representing the neutralization of each of the following bases by each of the acids whose formulas are given: NaOH HCl Ba(OH)_{2} H_{2}SO_{4} Al(OH)_{3} H_{3}PO_{4} 4. Silver acts as a univalent element and calcium as a divalent element in the formation of their respective nitrates and chlorides. (a) Write the formula for silver nitrate; for calcium chloride. (b) When solutions of these two salts are mixed, the two metals, silver and calcium, exchange places; write the equation for the reaction. _5._ Antimony acts as a trivalent element in the formation of a chloride. (a) What is the formula for antimony chloride? (b) When hydrosulphuric acid (H_{2}S) is passed into a solution of this chloride the hydrogen and antimony exchange places; write the equation for the reaction. 6. Lead has a valence of 2 and iron of 3 in the compounds known respectively as lead nitrate and ferric sulphate. (a) Write the formulas for these two compounds. (b) When their solutions are mixed the two metals exchange places; write the equation for the reaction. CHAPTER XII COMPOUNDS OF NITROGEN ~Occurrence.~ As has been stated in a former chapter, nitrogen constitutes a large fraction of the atmosphere. The compounds of nitrogen, however, cannot readily be obtained from this source, since at any ordinary temperature nitrogen is able to combine directly with very few of the elements. In certain forms of combination nitrogen occurs in the soil from which it is taken up by plants and built into complex substances composed chiefly of carbon, hydrogen, oxygen, and nitrogen. Animals feeding on these plants assimilate the nitrogenous matter, so that this element is an essential constituent of both plants and animals. ~Decomposition of organic matter by bacteria.~ When living matter dies and undergoes decay complicated chemical reactions take place, one result of which is that the nitrogen of the organic matter is set free either as the element nitrogen, or in the form of simple compounds, such as ammonia (NH_{3}) or oxides of nitrogen. Experiment has shown that all such processes of decay are due to the action of different kinds of bacteria, each particular kind effecting a different change. ~Decomposition of organic matter by heat.~ When organic matter is strongly heated decomposition into simpler substances takes place in much the same way as in the case of bacterial decomposition. Coal is a complex substance of vegetable origin, consisting largely of carbon, but also containing hydrogen, oxygen, and nitrogen. When this is heated in a closed vessel so that air is excluded, about one seventh of the nitrogen is converted into ammonia, and this is the chief source from which ammonia and its compounds are obtained. COMPOUNDS OF NITROGEN WITH HYDROGEN ~Ammonia~ (NH_{3}). Several compounds consisting exclusively of nitrogen and hydrogen are known, but only one, ammonia, need be considered here. ~Preparation of ammonia.~ Ammonia is prepared in the laboratory by a different method from the one which is used commercially. 1. _Laboratory method._ In the laboratory ammonia is prepared from ammonium chloride, a compound having the formula NH_{4}Cl, and obtained in the manufacture of coal gas. As will be shown later in the chapter, the group NH_{4} in this compound acts as a univalent radical and is known as _ammonium_. When ammonium chloride is warmed with sodium hydroxide, the ammonium and sodium change places, the reaction being expressed in the following equation. NH_{4}Cl + NaOH = NaCl + NH_{4}OH. The ammonium hydroxide (NH_{4}OH) so formed is unstable and breaks down into water and ammonia. NH_{4}OH = NH_{3} + H_{2}O. Calcium hydroxide (Ca(OH)_{2}) is frequently used in place of the more expensive sodium hydroxide, the equations being 2NH_{4}Cl + Ca(OH)_{2} = CaCl_{2} + 2NH_{4}OH, 2NH_{4}OH = 2H_{2}O + 2NH_{3}. In the preparation, the ammonium chloride and calcium hydroxide are mixed together and placed in a flask arranged as shown in Fig. 35. The mixture is gently warmed, when ammonia is evolved as a gas and is collected by displacement of air. [Illustration: Fig. 35] 2. _Commercial method._ Nearly all the ammonia of commerce comes from the gasworks. Ordinary illuminating gas is made by distilling coal, as will be explained later, and among the products of this distillation a solution of ammonia in water is obtained. This solution, known as _gas liquor_, contains not only ammonia but other soluble substances. Most of these combine chemically with lime, while ammonia does not; if then lime is added to the gas liquor and the liquor is heated, the ammonia is driven out from the mixture. It may be dissolved again in pure, cold water, forming _aqua ammonia_, or the ammonia water of commerce. ~Preparation from hydrogen and nitrogen.~ When electric sparks are passed for some time through a mixture of hydrogen and nitrogen, a small percentage of the two elements in the mixture is changed into ammonia. The action soon ceases, however, for the reason that ammonia is decomposed by the electric discharge. The reaction expressed in the equation N + 3H = NH_{3} can therefore go in either direction depending upon the relative quantities of the substances present. This recalls the similar change from oxygen into ozone, which soon ceases because the ozone is in turn decomposed into oxygen. ~Physical properties.~ Under ordinary conditions ammonia is a gas whose density is 0.59. It is therefore little more than half as heavy as air. It is easily condensed into a colorless liquid, and can now be purchased in liquid form in steel cylinders. The gas is colorless and has a strong, suffocating odor. It is extremely soluble in water, 1 l. of water at 0° and 760 mm. pressure dissolving 1148 l. of the gas. In dissolving this large volume of gas the water expands considerably, so that the density of the solution is less than that of water, the strongest solutions having a density of 0.88. ~Chemical properties.~ Ammonia will not support combustion, nor will it burn under ordinary conditions. In an atmosphere of oxygen it burns with a feeble, yellowish flame. When quite dry it is not a very active substance, but when moist it combines with a great many substances, particularly with acids. ~Uses.~ It has been stated that ammonia can be condensed to a liquid by the application of pressure. If the pressure is removed from the liquid so obtained, it rapidly passes again into the gaseous state and in so doing absorbs a large amount of heat. Advantage is taken of this fact in the preparation of artificial ice. Large quantities of ammonia are also used in the preparation of ammonium compounds. ~The manufacture of artificial ice.~ Fig. 36 illustrates the method of preparing artificial ice. The ammonia gas is liquefied in the pipes X by means of the pump Y. The heat generated is absorbed by water flowing over the pipes. The pipes lead into a large brine tank, a cross section of which is shown in the figure. Into the brine (concentrated solution of common salt) contained in this tank are dipped the vessels A, B, C, filled with pure water. The pressure is removed from the liquid ammonia as it passes into the pipes immersed in the brine, and the heat absorbed by the rapid evaporation of the liquid lowers the temperature of the brine below zero. The water in A, B, C is thereby frozen into cakes of ice. The gaseous ammonia resulting from the evaporation of the liquid ammonia is again condensed, so that the process is continuous. [Illustration Fig. 36] ~Ammonium hydroxide~ (NH_{4}OH). The solution of ammonia in water is found to have strong basic properties and therefore contains hydroxyl ions. It turns red litmus blue; it has a soapy feel; it neutralizes acids, forming salts with them. It seems probable, therefore, that when ammonia dissolves in water it combines chemically with it according to the equation NH_{3} + H_{2}O = NH_{4}OH, and that it is the substance NH_{4}OH, called ammonium hydroxide, which has the basic properties, dissociating into the ions NH_{4} and OH. Ammonium hydroxide has never been obtained in a pure state. At every attempt to isolate it the substance breaks up into water and ammonia,-- NH_{4}OH = NH_{3} + H_{2}O. ~The ammonium radical.~ The radical NH_{4} plays the part of a metal in many chemical reactions and is called ammonium. The ending _-ium_ is given to the name to indicate the metallic properties of the substance, since the names of the metals in general have that ending. The salts formed by the action of the base ammonium hydroxide on acids are called ammonium salts. Thus, with hydrochloric acid, ammonium chloride is formed in accordance with the equation NH_{4}OH + HCl = NH_{4}Cl + H_{2}O. Similarly, with nitric acid, ammonium nitrate (NH_{4}NO_{3}) is formed, and with sulphuric acid, ammonium sulphate ((NH_{4})_{2}S0_{4}). It will be noticed that in the neutralization of ammonium hydroxide by acids the group NH_{4} replaces one hydrogen atom of the acid, just as sodium does. The group therefore acts as a univalent metal. ~Combination of nitrogen with hydrogen by volume.~ Under suitable conditions ammonia can be decomposed into nitrogen and hydrogen by passing electric sparks through the gas. Accurate measurement has shown that when ammonia is decomposed, two volumes of the gas yield one volume of nitrogen and three volumes of hydrogen. Consequently, if the two elements were to combine directly, one volume of nitrogen would combine with three volumes of hydrogen to form two volumes of ammonia. Here, as in the formation of steam from hydrogen and oxygen, small whole numbers serve to indicate the relation between the volumes of combining gases and that of the gaseous product. COMPOUNDS OF NITROGEN WITH OXYGEN AND HYDROGEN In addition to ammonium hydroxide, nitrogen forms several compounds with hydrogen and oxygen, of which nitric acid (HNO_{3}) and nitrous acid (HNO_{2}) are the most familiar. ~Nitric acid~ (HNO_{3}). Nitric acid is not found to any extent in nature, but some of its salts, especially sodium nitrate (NaNO_{3}) and potassium nitrate (KNO_{3}) are found in large quantities. From these salts nitric acid can be obtained. [Illustration Fig. 37] ~Preparation of nitric acid.~ When sodium nitrate is treated with concentrated cold sulphuric acid, no chemical action seems to take place. If, however, the mixture is heated in a retort, nitric acid is given off as a vapor and may be easily condensed to a liquid by passing the vapor into a tube surrounded by cold water, as shown in Fig. 37. An examination of the liquid left in the retort shows that it contains sodium acid sulphate (NaHSO_{4}), so that the reaction may be represented by the equation NaNO_{3} + H_{2}SO_{4} = NaHSO_{4} + HNO_{3}. If a smaller quantity of sulphuric acid is taken and the mixture is heated to a high temperature, normal sodium sulphate is formed: 2NaNO_{3} + H_{2}SO_{4} = Na_{2}SO_{4} + 2HNO_{3}. In this case, however, the higher temperature required decomposes a part of the nitric acid. ~The commercial preparation of nitric acid.~ Fig. 38 illustrates a form of apparatus used in the preparation of nitric acid on a large scale. Sodium nitrate and sulphuric acid are heated in the iron retort A. The resulting acid vapors pass in the direction indicated by the arrows, and are condensed in the glass tubes B, which are covered with cloth kept cool by streams of water. These tubes are inclined so that the liquid resulting from the condensation of the vapors runs back into C and is drawn off into large vessels (D). [Illustration Fig. 38] ~Physical properties of nitric acid.~ Pure nitric acid is a colorless liquid, which boils at about 86° and has a density of 1.56. The concentrated acid of commerce contains about 68% of the acid, the remainder being water. Such a mixture has a density of 1.4. The concentrated acid fumes somewhat in moist air, and has a sharp choking odor. ~Chemical properties.~ The most important chemical properties of nitric acid are the following. 1. _Acid properties._ As the name indicates, this substance is an acid, and has all the properties of that class of substances. It changes blue litmus red and has a sour taste in dilute solutions. It forms hydrogen ions in solution and neutralizes bases forming salts. It also acts upon the oxides of most metals, forming a salt and water. It is one of the strongest acids. 2. _Decomposition on heating._ When boiled, or exposed for some time to sunlight, it suffers a partial decomposition according to the equation 2HNO_{3} = H_{2}O + 2NO_{2} + O. The substance NO_{2}, called nitrogen peroxide, is a brownish gas, which is readily soluble in water and in nitric acid. It therefore dissolves in the undecomposed acid, and imparts a yellowish or reddish color to it. Concentrated nitric acid highly charged with this substance is called _fuming nitric acid_. 3. _Oxidizing action._ According to its formula, nitric acid contains a large percentage of oxygen, and the reaction just mentioned shows that the compound is not a very stable one, easily undergoing decomposition. These properties should make it a good oxidizing agent, and we find that this is the case. Under ordinary circumstances, when acting as an oxidizing agent, it is decomposed according to the equation 2HNO_{3} = H_{2}O + 2NO + 3O. The oxygen is taken up by the substance oxidized, and not set free, as is indicated in the equation. Thus, if carbon is oxidized by nitric acid, the oxygen combines with carbon, forming carbon dioxide (CO_{2}): C + 2O = CO_{2}. 4. _Action on metals._ We have seen that when an acid acts upon a metal hydrogen is set free. Accordingly, when nitric acid acts upon a metal, such as copper, we should expect the reaction to take place which is expressed in the equation Cu + 2HNO_{3} = Cu(NO_{3})_{2} + 2H. This reaction does take place, but the hydrogen set free is immediately oxidized to water by another portion of the nitric acid according to the equation HNO_{3} + 3H = 2H_{2}O + NO. As these two equations are written, two atoms of hydrogen are given off in the first equation, while three are used up in the second. In order that the hydrogen may be equal in the two equations, we must multiply the first by 3 and the second by 2. We shall then have 3Cu + 6HNO_{3} = 3Cu(NO_{3})_{2} + 6H, 2HNO_{3} + 6H = 4H_{2}O + 2NO. The two equations may now be combined into one by adding the quantities on each side of the equality sign, canceling the hydrogen which is given off in the one reaction and used up in the other. We shall then have the equation 3Cu + 8HNO_{3} = 3Cu(NO_{3})_{2} + 2NO + 4H_{2}O. A number of other reactions may take place when nitric acid acts upon metals, resulting in the formation of other oxides of nitrogen, free nitrogen, or even ammonia. The reaction just given is, however, the usual one. ~Importance of steps in a reaction.~ This complete equation has the advantage of making it possible to calculate very easily the proportions in which the various substances enter into the reaction or are formed in it. It is unsatisfactory in that it does not give full information about the way in which the reaction takes place. For example, it does not suggest that hydrogen is at first formed, and subsequently transformed into water. It is always much more important to remember the steps in a chemical reaction than to remember the equation expressing the complete action; for if these steps in the reaction are understood, the complete equation is easily obtained in the manner just described. ~Salts of nitric acid,--nitrates.~ The salts of nitric acid are called nitrates. Many of these salts will be described in the study of the metals. They are all soluble in water, and when heated to a high temperature undergo decomposition. In a few cases a nitrate on being heated evolves oxygen, forming a nitrite: NaNO_{3} = NaNO_{2} + O. In other cases the decomposition goes further, and the metal is left as oxide: Cu(NO_{3})_{2} = CuO + 2NO_{2} + O. ~Nitrous acid~ (HNO_{2}). It is an easy matter to obtain sodium nitrite (NaNO_{2}), as the reaction given on the previous page indicates. Instead of merely heating the nitrate, it is better to heat it together with a mild reducing agent, such as lead, when the reaction takes place which is expressed by the equation NaNO_{3} + Pb = PbO + NaNO_{2}. When sodium nitrite is treated with an acid, such as sulphuric acid, it is decomposed and nitrous acid is set free: NaNO_{2} + H_{2}SO_{4} = NaHSO_{4} + HNO_{2}. The acid is very unstable, however, and decomposes readily into water and nitrogen trioxide (N_{2}O_{3}): 2HNO_{2} = H_{2}O + N_{2}O_{3}. Dilute solutions of the acid, however, can be obtained. COMPOUNDS OF NITROGEN WITH OXYGEN Nitrogen combines with oxygen to form five different oxides. The formulas and names of these are as follows: N_{2}O nitrous oxide. NO nitric oxide. NO_{2} nitrogen peroxide. N_{2}O_{3} nitrogen trioxide, or nitrous anhydride. N_{2}O_{5} nitrogen pentoxide, or nitric anhydride. These will now be briefly discussed. ~Nitrous oxide~ (_laughing gas_) (N_{2}O). Ammonium nitrate, like all nitrates, undergoes decomposition when heated; and owing to the fact that it contains no metal, but does contain both oxygen and hydrogen, the reaction is a peculiar one. It is represented by the equation NH_{4}NO_{3} = 2H_{2}O + N_{2}O. The oxide of nitrogen so formed is called nitrous oxide or laughing gas. It is a colorless gas having a slight odor. It is somewhat soluble in water, and in solution has a slightly sweetish taste. It is easily converted into a liquid and can be purchased in this form. When inhaled it produces a kind of hysteria (hence the name "laughing gas"), and even unconsciousness and insensibility to pain if taken in large amounts. It has long been used as an anæsthetic for minor surgical operations, such as those of dentistry, but owing to its unpleasant after effects it is not so much in use now as formerly. Chemically, nitrous oxide is remarkable for the fact that it is a very energetic oxidizing agent. Substances such as carbon, sulphur, iron, and phosphorus burn in it almost as brilliantly as in oxygen, forming oxides and setting free nitrogen. Evidently the oxygen in nitrous oxide cannot be held in very firm combination by the nitrogen. [Illustration Fig. 39] ~Nitric oxide~ (NO). We have seen that when nitric acid acts upon metals, such as copper, the reaction represented by the following equation takes place: 3Cu + 8HNO_{3} = 3Cu(NO_{3})_{3} + 2NO + 4H_{2}O. Nitric oxide is most conveniently prepared in this way. The metal is placed in the flask A (Fig. 39) and the acid added slowly through the funnel tube B. The gas escapes through C and is collected over water. Pure nitric oxide is a colorless gas, slightly heavier than air, and is practically insoluble in water. It is a difficult gas to liquefy. Unlike nitrous oxide, nitric oxide does not part with its oxygen easily, and burning substances introduced into this gas are usually extinguished. A few substances like phosphorus, which have a very strong affinity for oxygen and which are burning energetically in the air, will continue to burn in an atmosphere of nitric oxide. In this case the nitric oxide loses all of its oxygen and the nitrogen is set free as gas. ~Action of nitric oxide with oxygen.~ When nitric oxide comes into contact with oxygen or with the air, it at once combines with the oxygen even at ordinary temperatures, forming a reddish-yellow gas of the formula NO_{2}, which is called nitrogen peroxide. This action is not energetic enough to produce a flame, though considerable heat is set free. ~Nitrogen peroxide~ (NO_{2}). This gas, as we have just seen, is formed by allowing nitric oxide to come into contact with oxygen. It can also be made by heating certain nitrates, such as lead nitrate: Pb(NO_{3})_{2} = PbO + 2NO_{2} + O. It is a reddish-yellow gas of unpleasant odor, which is quite poisonous when inhaled. It is heavier than air and is easily condensed to a liquid. It dissolves in water, but this solution is not a mere physical solution; the nitrogen peroxide is decomposed, forming a mixture of nitric and nitrous acids: 2NO_{2} + H_{2}O = HNO_{2} + HNO_{3}. Nitrogen peroxide will not combine with more oxygen; it will, however, give up a part of its oxygen to burning substances, acting as an oxidizing agent: NO_{2} = NO + O. ~Acid anhydrides.~ The oxides N_{2}O_{3} (nitrogen trioxide) and N_{2}O_{5} (nitrogen pentoxide) are rarely prepared and need not be separately described. They bear a very interesting relation to the acids of nitrogen. When dissolved in water they combine with the water, forming acids: N_{2}O_{3} + H_{2}O = 2HNO_{2}, N_{2}O_{5} + H_{2}O = 2HNO_{3}. On the other hand, nitrous acid very easily decomposes, yielding water and nitrogen trioxide, and by suitable means nitric acid likewise may be decomposed into water and nitrogen pentoxide: 2HNO_{2} = H_{2}O + N_{2}O_{3}, 2HNO_{3} = H_{2}O + N_{2}O_{5}. In view of the close relation between these oxides and the corresponding acids, they are called _anhydrides_ of the acids, N_{2}O_{3} being nitrous anhydride and N_{2}O_{5} nitric anhydride. DEFINITION: _Any oxide which will combine with water to form an acid, or which together with water is formed by the decomposition of an acid, is called an anhydride of that acid._ EXERCISES 1. Perfectly dry ammonia does not affect litmus paper. Explain. 2. Can ammonia be dried by passing the gas through concentrated sulphuric acid? Explain. 3. Ammonium hydroxide is a weak base, i.e. it is not highly dissociated. When it is neutralized by strong acids the heat of reaction is less than when strong bases are so neutralized. Suggest some possible cause for this. 4. Why is brine used in the manufacture of artificial ice? 5. Discuss the energy changes which take place in the manufacture of artificial ice. 6. What weight of ammonium chloride is necessary to furnish enough ammonia to saturate 1 l. of water at 0° and 760 mm.? 7. What weight of sodium nitrate is necessary to prepare 100 cc. of commercial nitric acid? What weight of potassium nitrate is necessary to furnish the same weight of acid? 8. 100 l. of nitrogen peroxide were dissolved in water and neutralized with sodium hydroxide. What substances were formed and how much of each?(1 l. nitrogen peroxide weighs 2.05 grams.) 9. How many liters of nitrous oxide, measured under standard conditions, can be prepared from 10 g. of ammonium nitrate? 10. What weight of copper is necessary to prepare 50 l. of nitric oxide under standard conditions? 11. (a) Calculate the percentage composition of the oxides of nitrogen. (b) What important law does this series of substances illustrate? 12. Write the equations representing the reactions between ammonium hydroxide, and sulphuric acid and nitric acid respectively, in accordance with the theory of electrolytic dissociation. 13. In the same way, write the equations representing the reactions between nitric acid and each of the following bases: NaOH, KOH, NH_{4}OH, Ca(OH)_{2}. CHAPTER XIII REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM ~Reversible reactions.~ The reactions so far considered have been represented as continuing, when once started, until one or the other substance taking part in the reaction has been used up. In some reactions this is not the case. For example, we have seen that when steam is passed over hot iron the reaction is represented by the equation 3Fe + 4H_{2}O = Fe_{3}O_{4} + 8H. On the other hand, when hydrogen is passed over hot iron oxide the reverse reaction takes place: Fe_{3}O_{4} +8H = 3Fe + 4H_{2}O. The reaction can therefore go in either direction, depending upon the conditions of the experiment. Such a reaction is called a _reversible reaction_. It is represented by an equation with double arrows in place of the equality sign, thus: 3Fe + 4H_{2}O <--> Fe_{3}O_{4} + 8H. In a similar way, the equation N + 3H <--> NH_{3} expresses the fact that under some conditions nitrogen may unite with hydrogen to form ammonia, while under other conditions ammonia decomposes into nitrogen and hydrogen. The conversion of oxygen into ozone is also reversible and may be represented thus: oxygen <--> ozone. ~Chemical equilibrium.~ Reversible reactions do not usually go on to completion in one direction unless the conditions under which the reaction takes place are very carefully chosen. Thus, if iron and steam are confined in a heated tube, the steam acts upon the iron, producing iron oxide and hydrogen. But these substances in turn act upon each other to form iron and steam once more. When these two opposite reactions go on at such rates that the weight of the iron changed into iron oxide is just balanced by the weight of the iron oxide changed into iron, there will be no further change in the relative weights of the four substances present in the tube. The reaction is then said to have reached an equilibrium. ~Factors which determine the point of equilibrium.~ There are two factors which have a great deal of influence in determining the point at which a given reaction will reach equilibrium. 1. _Influence of the chemical nature of the substances._ If two reversible reactions of the same general kind are selected, it has been found that the point of equilibrium is different in the two cases. For example, in the reactions represented by the equations 3Fe + 4H_{2}O <--> Fe_{3}O_{4} + 8H, Zn + H_{2}O <--> ZnO + 2H, the equilibrium will be reached when very different quantities of the iron and zinc have been changed into oxides. The individual chemical properties of the iron and zinc have therefore marked influence upon the point at which equilibrium will be reached. 2. _Influence of relative mass._ If the tube in which the reaction 3Fe + 4H_{2}O <--> Fe_{3}O_{4} + 8H has come to an equilibrium is opened and more steam is admitted, an additional quantity of the iron will be changed into iron oxide. If more hydrogen is admitted, some of the oxide will be reduced to metal. The point of equilibrium is therefore dependent upon the relative masses of the substances taking part in the reaction. When one of the substances is a solid, however, its mass has little influence, since it is only the extent of its surface which can affect the reaction. ~Conditions under which reversible reactions are complete.~ If, when the equilibrium between iron and steam has been reached, the tube is opened and a current of steam is passed in, the hydrogen is swept away as fast as it is formed. The opposing reaction of hydrogen upon iron oxide must therefore cease, and the action of steam on the iron will go on until all of the iron has been transformed into iron oxide. On the other hand, if a current of hydrogen is admitted into the tube, the steam will be swept away by the hydrogen, and all of the iron oxide will be reduced to iron. _A reversible reaction can therefore be completed in either direction when one of the products of the reaction is removed as fast as it is formed._ ~Equilibrium in solution.~ When reactions take place in solution in water the same general principles hold good. The matter is not so simple, however, as in the case just described, owing to the fact that many of the reactions in solution are due to the presence of ions. The substances most commonly employed in solution are acids, bases, or salts, and all of these undergo dissociation. Any equilibrium which may be reached in solutions of these substances must take place between the various ions formed, on the one hand, and the undissociated molecules, on the other. Thus, when nitric acid is dissolved in water, equilibrium is reached in accordance with the equation H^{+} + NO_{3}^{-} <--> HNO_{3}. ~Conditions under which reversible reactions in solution are complete.~ The equilibrium between substances in solution may be disturbed and the reaction caused to go on in one direction to completion in either of three ways. 1. _A gas may be formed which escapes from the solution._ When sodium nitrate and sulphuric acid are brought together in solution all four ions, Na^{+}, NO_{3}^{-}, H^{+}, SO_{4}^{--}, are formed. These ions are free to rearrange themselves in various combinations. For example, the H^{+} and the NO_{3}^{-} ions will reach the equilibrium H^{+} + NO_{3}^{-} <--> HNO_{3}. If the experiment is performed with very little water present, as is the case in the preparation of nitric acid, the equilibrium will be reached when most of the H^{+} and the NO_{3}^{-} ions have combined to form undissociated HNO_{3}. Finally, if the mixture is now heated above the boiling point of nitric acid, the acid distills away as fast as it is formed. More and more H^{+} and NO_{3}^{-} ions will then combine, and the process will continue until one or the other of them has all been removed from the solution. The substance remaining is sodium acid sulphate (NaHSO_{4}), and the reaction can therefore be expressed by the equation NaNO_{3} + H_{2}SO_{4} = NaHSO_{4} + HNO_{3}. 2. _An insoluble solid may be formed._ When hydrochloric acid (HCl) and silver nitrate (AgNO_{3}) are brought together in solution the following ions will be present: H^{+}, Cl^{-}, Ag^{+}, NO_{3}^{-}. The ions Ag^{+} and Cl^{-} will then set up the equilibrium Ag^{+} + Cl^{-} <--> AgCl. But silver chloride (AgCl) is almost completely insoluble in water, and as soon as a very little of it has formed the solution becomes supersaturated, and the excess of the salt precipitates. More silver and chlorine ions then unite, and this continues until practically all of the silver or the chlorine ions have been removed from the solution. We then say that the following reaction is complete: AgNO_{3} + HCl = AgCl + HNO_{3}. 3. _Two different ions may form undissociated molecules._ In the neutralization of sodium hydroxide by hydrochloric acid the ions H^{+} and OH^{-} come to the equilibrium H^{+} + OH^{-} <--> H_{2}O. But since water is almost entirely undissociated, equilibrium can only be reached when there are very few hydroxyl or hydrogen ions present. Consequently the two ions keep uniting until one or the other of them is practically removed from the solution. When this occurs the neutralization expressed in the following equation is complete: NaOH + HCl = H_{2}O + NaCl. ~Preparation of acids.~ The principle of reversible reactions finds practical application in the preparation of most of the common acids. An acid is usually prepared by treating the most common of its salts with some other acid of high boiling point. The mixture is then heated until the lower boiling acid desired distills out. Owing to its high boiling point (338°), sulphuric acid is usually employed for this purpose, most other acids boiling below that temperature. EXERCISES 1. What would take place when solutions of silver nitrate and sodium chloride are brought together? What other chlorides would act in the same way? 2. Is the reaction expressed by the equation NH_{3} + H_{2}O = NH_{4}OH reversible? If so, state the conditions under which it will go in each direction. 3. Is the reaction expressed by the equation 2H + O = H_{2}O reversible? If so, state the conditions under which it will go in each direction. 4. Suggest a method for the preparation of hydrochloric acid. CHAPTER XIV SULPHUR AND ITS COMPOUNDS ~Occurrence.~ The element sulphur has been known from the earliest times, since it is widely distributed in nature and occurs in large quantities in the uncombined form, especially in the neighborhood of volcanoes. Sicily has long been famous for its sulphur mines, and smaller deposits are found in Italy, Iceland, Mexico, and especially in Louisiana, where it is mined extensively. In combination, sulphur occurs abundantly in the form of sulphides and sulphates. In smaller amounts it is found in a great variety of minerals, and it is a constituent of many animal and vegetable substances. ~Extraction of sulphur.~ Sulphur is prepared from the native substance, the separation of crude sulphur from the rock and earthy materials with which it is mixed being a very simple process. The ore from the mines is merely heated until the sulphur melts and drains away from the earthy impurities. The crude sulphur obtained in this way is distilled in a retort-shaped vessel made of iron, the exit tube of which opens into a cooling chamber of brickwork. When the sulphur vapor first enters the cooling chamber it condenses as a fine crystalline powder called _flowers of sulphur_. As the condensing chamber becomes warm, the sulphur collects as a liquid in it, and is drawn off into cylindrical molds, the product being called _roll sulphur_ or _brimstone_. ~Physical properties.~ Roll sulphur is a pale yellow, crystalline solid, without marked taste and with but a faint odor. It is insoluble in water, but is freely soluble in a few liquids, notably in carbon disulphide. Roll sulphur melts at 114.8°. Just above the melting point it forms a rather thin, straw-colored liquid. As the temperature is raised, this liquid turns darker in color and becomes thicker, until at about 235° it is almost black and is so thick that the vessel containing it can be inverted without danger of the liquid running out. At higher temperatures it becomes thin once more, and boils at 448°, forming a yellowish vapor. On cooling the same changes take place in reverse order. ~Varieties of sulphur.~ Sulphur is known in two general forms, crystalline and amorphous. Each of these forms exists in definite modifications. ~Crystalline sulphur.~ Sulphur occurs in two crystalline forms, namely, rhombic sulphur and monoclinic sulphur. 1. _Rhombic sulphur._ When sulphur crystallizes from its solution in carbon disulphide it separates in crystals which have the same color and melting point as roll sulphur, and are rhombic in shape. Roll sulphur is made up of minute rhombic crystals. 2. _Monoclinic sulphur._ When melted sulphur is allowed to cool until a part of the liquid has solidified, and the remaining liquid is then poured off, it is found that the solid sulphur remaining in the vessel has assumed the form of fine needle-shaped crystals. These differ much in appearance from the rhombic crystals obtained by crystallizing sulphur from its solution in carbon disulphide. The needle-shaped form is called _monoclinic sulphur_. The two varieties differ also in density and in melting point, the monoclinic sulphur melting at 120°. Monoclinic and rhombic sulphur remain unchanged in contact with each other at 96°. Above this temperature the rhombic changes into monoclinic; at lower temperatures the monoclinic changes into rhombic. The temperature 96° is therefore called the transition point of sulphur. Heat is set free when monoclinic sulphur changes into rhombic. ~Amorphous sulphur.~ Two varieties of amorphous sulphur can be readily obtained. These are white sulphur and plastic sulphur. 1. _White sulphur._ Flowers of sulphur, the preparation of which has been described, consists of a mixture of rhombic crystals and amorphous particles. When treated with carbon disulphide, the crystals dissolve, leaving the amorphous particles as a white residue. 2. _Plastic sulphur._ When boiling sulphur is poured into cold water it assumes a gummy, doughlike form, which is quite elastic. This can be seen in a very striking manner by distilling sulphur from a small, short-necked retort, such as is represented in Fig. 40, and allowing the liquid to run directly into water. In a few days it becomes quite brittle and passes over into ordinary rhombic sulphur. [Illustration Fig. 40] ~Chemical properties of sulphur.~ When sulphur is heated to its kindling temperature in oxygen or in the air it burns with a pale blue flame, forming sulphur dioxide (SO_{2}). Small quantities of sulphur trioxide (SO_{3}) may also be formed in the combustion of sulphur. Most metals when heated with sulphur combine directly with it, forming metallic sulphides. In some cases the action is so energetic that the mass becomes incandescent, as has been seen in the case of iron uniting with sulphur. This property recalls the action of oxygen upon metals, and in general the metals which combine readily with oxygen are apt to combine quite readily with sulphur. ~Uses of sulphur.~ Large quantities of sulphur are used as a germicide in vineyards, also in the manufacture of gunpowder, matches, vulcanized rubber, and sulphuric acid. COMPOUNDS OF SULPHUR WITH HYDROGEN ~Hydrosulphuric acid~ (H_{2}S). This substance is a gas having the composition expressed by the formula H_{2}S and is commonly called hydrogen sulphide. It is found in the vapors issuing from volcanoes, and in solution in the so-called sulphur waters of many springs. It is formed when organic matter containing sulphur undergoes decay, just as ammonia is formed under similar circumstances from nitrogenous matter. ~Preparation.~ Hydrosulphuric acid is prepared in the laboratory by treating a sulphide with an acid. Iron sulphide (FeS) is usually employed: FeS + 2HCl = FeCl_{2} + H_{2}S. A convenient apparatus is shown in Fig. 41. A few lumps of iron sulphide are placed in the bottle A, and dilute acid is added in small quantities at a time through the funnel tube B, the gas escaping through the tube C. [Illustration: Fig. 41] ~Explanation of the reaction.~ Iron sulphide is a salt of hydrosulphuric acid, and this reaction is therefore similar to the one which takes place when sulphuric acid acts upon a nitrate. In both cases a salt and an acid are brought together, and there is a tendency for the reaction to go on until a state of equilibrium is reached. This equilibrium is constantly disturbed by the escape of the gaseous acid set free, so that the reaction goes on until all of the original salt has been decomposed. The two reactions differ in that the first one is complete at ordinary temperatures, while in the case of sulphuric acid acting upon sodium nitrate, the reacting substances must be heated so as to secure a temperature at which nitric acid is a gas. ~Physical properties.~ Hydrosulphuric acid is a colorless gas, having a weak, disagreeable taste and an exceedingly offensive odor. It is rather sparingly soluble in water at ordinary temperatures, about three volumes dissolving in one of water. In boiling water it is not soluble at all. In pure form it acts as a violent poison, and even when diluted largely with air produces headache, dizziness, and nausea. It is a little heavier than air, having a density of 1.18. ~Chemical properties.~ The most important chemical properties of hydrosulphuric acid are the following: 1. _Acid properties._ Hydrosulphuric acid is a weak acid. In solution in water it turns blue litmus red and neutralizes bases, forming salts called _sulphides_. 2. _Action on oxygen._ The elements composing hydrosulphuric acid have each a strong affinity for oxygen, and are not held together very firmly. Consequently the gas burns readily in oxygen or the air, according to the equation H_{2}S + 3O = H_{2}O + SO_{2}. When there is not enough oxygen for both the sulphur and the hydrogen, the latter element combines with the oxygen and the sulphur is set free: H_{2}S + O = H_{2}O + S. 3. _Reducing action._ Owing to the ease with which hydrosulphuric acid decomposes and the strong affinity of both sulphur and hydrogen for oxygen, the substance is a strong reducing agent, taking oxygen away from many substances which contain it. 4. _Action on metals._ Hydrosulphuric acid acts towards metals in a way very similar to water. Thus, when it is passed over heated iron in a tube, the reaction is represented by the equation 3Fe + 4H_{2}S = Fe_{3}S_{4} + 8H. Water in the form of steam, under similar circumstances, acts according to the equation 3Fe + 4H_{2}O = Fe_{3}O_{4} + 8H. ~Salts of hydrosulphuric acid,--sulphides.~ The salts of hydrosulphuric acid, called sulphides, form an important class of salts. Many of them are found abundantly in nature, and some of them are important ores. They will be frequently mentioned in connection with the metals. Most of the sulphides are insoluble in water, and some of them are insoluble in acids. Consequently, when hydrosulphuric acid is passed into a solution of a salt, it often happens that a sulphide is precipitated. With copper chloride the equation is CuCl_{2} + H_{2}S = CuS + 2HCl. Because of the fact that some metals are precipitated in this way as sulphides while others are not, hydrosulphuric acid is extensively used in the separation of the metals in the laboratory. ~Explanation of the reaction.~ When hydrosulphuric acid and copper chloride are brought together in solution, both copper and sulphur ions are present, and these will come to an equilibrium, as represented in the equation Cu^{+} + S^{-} <--> CuS. Since copper sulphide is almost insoluble in water, as soon as a very small quantity has formed the solution becomes supersaturated, and the excess keeps precipitating until nearly all the copper or sulphur ions have been removed from the solution. With some other ions, such as iron, the sulphide formed does not saturate the solution, and no precipitate results. OXIDES OF SULPHUR Sulphur forms two well-known compounds with oxygen: sulphur dioxide (SO_{2}), sometimes called sulphurous anhydride; and sulphur trioxide (SO_{3}), frequently called sulphuric anhydride. ~Sulphur dioxide~ (SO_{2}). Sulphur dioxide occurs in nature in the gases issuing from volcanoes, and in solution in the water of many springs. It is likely to be found wherever sulphur compounds are undergoing oxidation. ~Preparation.~ Three general ways may be mentioned for the preparation of sulphur dioxide: 1. _By the combustion of sulphur._ Sulphur dioxide is readily formed by the combustion of sulphur in oxygen or the air: S + 2O = SO_{2}. It is also formed when substances containing sulphur are burned: ZnS + 3O = ZnO + SO_{2}. 2. _By the reduction of sulphuric acid._ When concentrated sulphuric acid is heated with certain metals, such as copper, part of the acid is changed into copper sulphate, and part is reduced to sulphurous acid. The latter then decomposes into sulphur dioxide and water, the complete equation being Cu + 2H_{2}SO_{4} = CuSO_{4} + SO_{2} + 2H_{2}O. 3. _By the action of an acid on a sulphite._ Sulphites are salts of sulphurous acid (H_{2}SO_{3}). When a sulphite is treated with an acid, sulphurous acid is set free, and being very unstable, decomposes into water and sulphur dioxide. These reactions are expressed in the equations Na_{2}SO_{3} + 2HCl = 2NaCl + H_{2}SO_{3}, H_{2}SO_{3} = H_{2}O + SO_{2}. ~Explanation of the reaction.~ In this case we have two reversible reactions depending on each other. In the first reaction, (1) Na_{2}SO_{3} + 2HCl <--> 2NaCl + H_{2}SO_{3}, we should expect an equilibrium to result, for none of the four substances in the equation are insoluble or volatile when water is present to hold them in solution. But the quantity of the H_{2}SO_{3} is constantly diminishing, owing to the fact that it decomposes, as represented in the equation (2) H_{2}SO_{3} <--> H_{2}O + SO_{2}, and the sulphur dioxide, being a gas, escapes. No equilibrium can therefore result, since the quantity of the sulphurous acid is constantly being diminished because of the escape of sulphur dioxide. ~Physical properties.~ Sulphur dioxide is a colorless gas, which at ordinary temperatures is 2.2 times as heavy as air. It has a peculiar, irritating odor. The gas is very soluble in water, one volume of water dissolving eighty of the gas under standard conditions. It is easily condensed to a colorless liquid, and can be purchased in this condition stored in strong bottles, such as the one represented in Fig. 42. [Illustration: Fig. 42] ~Chemical properties.~ Sulphur dioxide has a marked tendency to combine with other substances, and is therefore an active substance chemically. It combines with oxygen gas, but not very easily. It can, however, take oxygen away from some other substances, and is therefore a good reducing agent. Its most marked chemical property is its ability to combine with water to form sulphurous acid (H_{2}SO_{3}). ~Sulphurous acid~ (H_{2}SO_{3}). When sulphur dioxide dissolves in water it combines chemically with it to form sulphurous acid, an unstable substance having the formula H_{3}SO_{3}. It is impossible to prepare this acid in pure form, as it breaks down very easily into water and sulphur dioxide. The reaction is therefore reversible, and is expressed by the equation H_{2}O + SO_{2} <--> H_{2}SO_{3}. Solutions of the acid in water have a number of interesting properties. 1. _Acid properties._ The solution has all the properties typical of an acid. When neutralized by bases, sulphurous acid yields a series of salts called _sulphites_. 2. _Reducing properties._ Solutions of sulphurous acid act as good reducing agents. This is due to the fact that sulphurous acid has the power of taking up oxygen from the air, or from substances rich in oxygen, and is changed by this reaction into sulphuric acid: H_{2}SO_{3} + O = H_{2}SO_{4}, H_{2}SO_{3} + H_{2}O_{2} = H_{2}S0_{4} + H_{2}O. 3. _Bleaching properties._ Sulphurous acid has strong bleaching properties, acting upon many colored substances in such a way as to destroy their color. It is on this account used to bleach paper, straw goods, and even such foods as canned corn. 4. _Antiseptic properties._ Sulphurous acid has marked antiseptic properties, and on this account has the power of arresting fermentation. It is therefore used as a preservative. ~Salts of sulphurous acid,--sulphites.~ The sulphites, like sulphurous acid, have the power of taking up oxygen very readily, and are good reducing agents. On account of this tendency, commercial sulphites are often contaminated with sulphates. A great deal of sodium sulphite is used in the bleaching industry, and as a reagent for softening paper pulp. ~Sulphur trioxide~ (SO_{3}). When sulphur dioxide and oxygen are heated together at a rather high temperature, a small amount of sulphur trioxide (SO_{3}) is formed, but the reaction is slow and incomplete. If, however, the heating takes place in the presence of very fine platinum dust, the reaction is rapid and nearly complete. [Illustration: Fig. 43] ~ Experimental preparation of sulphur trioxide.~ The experiment can be performed by the use of the apparatus shown in Fig. 43, the fine platinum being secured by moistening asbestos fiber with a solution of platinum chloride and igniting it in a flame. The fiber, covered with fine platinum, is placed in a tube of hard glass, which is then heated with a burner to about 350°, while sulphur dioxide and air are passed into the tube. Union takes place at once, and the strongly fuming sulphur trioxide escapes from the jet at the end of the tube, and may be condensed by surrounding the receiving tube with a freezing mixture. ~Properties of sulphur trioxide.~ Sulphur trioxide is a colorless liquid, which solidifies at about 15° and boils at 46°. A trace of moisture causes it to solidify into a mass of silky white crystals, somewhat resembling asbestos fiber in appearance. In contact with the air it fumes strongly, and when thrown upon water it dissolves with a hissing sound and the liberation of a great deal of heat. The product of this reaction is sulphuric acid, so that sulphur trioxide is the anhydride of that acid: SO_{3} + H_{2}O = H_{2}SO_{4}. ~Catalysis.~ It has been found that many chemical reactions, such as the union of sulphur dioxide with oxygen, are much influenced by the presence of substances which do not themselves seem to take a part in the reaction, and are left apparently unchanged after it has ceased. These reactions go on very slowly under ordinary circumstances, but are greatly hastened by the presence of the foreign substance. Substances which hasten very slow reactions in this way are said to act as catalytic agents or _catalyzers_, and the action is called _catalysis_. Just how the action is brought about is not well understood. DEFINITION: _A catalyzer is a substance which changes the velocity of a reaction, but does not change its products._ ~Examples of Catalysis.~ We have already had several instances of such action. Oxygen and hydrogen combine with each other at ordinary temperatures in the presence of platinum powder, while if no catalytic agent is present they do not combine in appreciable quantities until a rather high temperature is reached. Potassium chlorate, when heated with manganese dioxide, gives up its oxygen at a much lower temperature than when heated alone. Hydrogen dioxide decomposes very rapidly when powdered manganese dioxide is sifted into its concentrated solution. On the other hand, the catalytic agent sometimes retards chemical action. For example, a solution of hydrogen dioxide decomposes more slowly when it contains a little phosphoric acid than when perfectly pure. For this reason commercial hydrogen dioxide always contains phosphoric acid. Many reactions are brought about by the catalytic action of traces of water. For example, phosphorus will not burn in oxygen in the absence of all moisture. Hydrochloric acid will not unite with ammonia if the reagents are perfectly dry. It is probable that many of the chemical transformations in physiological processes, such as digestion, are assisted by certain substances acting as catalytic agents. The principle of catalysis is therefore very important. ~Sulphuric acid~ (_oil of vitriol_) (H_{2}SO_{4}). Sulphuric acid is one of the most important of all manufactured chemicals. Not only is it one of the most common reagents in the laboratory, but enormous quantities of it are used in many of the industries, especially in the refining of petroleum, the manufacture of nitroglycerin, sodium carbonate, and fertilizers. ~Manufacture of sulphuric acid.~ 1. _Contact process_. The reactions taking place in this process are represented by the following equations: SO_{2} + O = SO_{3}, SO_{3} + H_{2}O = H_{2}SO_{4}. To bring about the first of these reactions rapidly, a catalyzer is employed, and the process is carried out in the following way: Large iron tubes are packed with some porous material, such as calcium and magnesium sulphates, which contains a suitable catalytic substance scattered through it. The catalyzers most used are platinum powder, vanadium oxide, and iron oxide. Purified sulphur dioxide and air are passed through the tubes, which are kept at a temperature of about 350°. Sulphur trioxide is formed, and as it issues from the tube it is absorbed in water or dilute sulphuric acid. The process is continued until all the water in the absorbing vessel has been changed into sulphuric acid, so that a very concentrated acid is made in this way. An excess of the trioxide may dissolve in the strong sulphuric acid, forming what is known as _fuming sulphuric acid_. 2. _Chamber process._ The method of manufacture exclusively employed until recent years, and still in very extensive use, is much more complicated. The reactions are quite involved, but the conversion of water, sulphur dioxide, and oxygen into sulphuric acid is accomplished by the catalytic action of oxides of nitrogen. The reactions are brought about in large lead-lined chambers, into which oxides of nitrogen, sulphur dioxide, steam, and air are introduced in suitable proportions. ~Reactions of the chamber process.~ In a very general way, the various reactions which take place in the lead chambers may be expressed in two equations. In the first reaction sulphur dioxide, nitrogen peroxide, steam, and oxygen unite, as shown in the equation (1) 2SO_{2} + 2NO_{2} + H_{2}O + O = 2SO_{2} (OH) (NO_{2}). The product formed in this reaction is called nitrosulphuric acid or "chamber crystals." It actually separates on the walls of the chambers when the process is not working properly. Under normal conditions, it is decomposed as fast as it is formed by the action of excess of steam, as shown in the equation (2) 2SO_{2} (OH) (NO_{2}) + H_{2}O + O = 2H_{2}SO_{4} + 2NO_{2}. The nitrogen dioxide formed in this reaction can now enter into combination with a new quantity of sulphur dioxide, steam, and oxygen, and the series of reactions go on indefinitely. Many other reactions occur, but these two illustrate the principle of the process. The relation between sulphuric acid and nitrosulphuric acid can be seen by comparing their structural formulas: O= -OH O= -OH S S O= -OH O= -NO_{2} The latter may be regarded as derived from the former by the substitution of the nitro group (NO_{2}) for the hydroxyl group (OH). [Illustration: Fig. 44] ~The sulphuric acid plant.~ Fig. 44 illustrates the simpler parts of a plant used in the manufacture of sulphuric acid by the chamber process. Sulphur or some sulphide, as FeS_{2}, is burned in furnace A. The resulting sulphur dioxide, together with air and some nitrogen peroxide, are conducted into the large chambers, the capacity of each chamber being about 75,000 cu. ft. Steam is also admitted into these chambers at different points. These compounds react to form sulphuric acid, according to the equations given above. The nitrogen left after the withdrawal of the oxygen from the admitted air escapes through the Gay-Lussac tower X. In order to prevent the escape of the oxides of nitrogen regenerated in the reaction, the tower is filled with lumps of coke, over which trickles concentrated sulphuric acid admitted from Y. The nitrogen peroxide dissolves in the acid and the resulting solution collects in H. This is pumped into E, where it is mixed with dilute acid and allowed to trickle down through the chamber D (Glover tower), which is filled with some acid-resisting rock. Here the nitrogen peroxide is expelled from the solution by the action of the hot gases entering from A, and together with them enters the first chamber again. The acid from which the nitrogen peroxide is expelled collects in F. Theoretically, a small amount of nitrogen peroxide would suffice to prepare an unlimited amount of sulphuric acid; practically, some of it escapes, and this is replaced by small amounts admitted at B. The sulphuric acid so formed, together with the excess of condensed steam, collect upon the floor of the chambers in the form of a liquid containing from 62% to 70% of sulphuric acid. The product is called _chamber acid_ and is quite impure; but for many purposes, such as the manufacture of fertilizers, it needs no further treatment. It can be concentrated by boiling it in vessels made of iron or platinum, which resist the action of the acid, nearly all the water boiling off. Pure concentrated acid can be made best by the contact process, while the chamber process is cheaper for the dilute impure acid. ~Physical properties.~ Sulphuric acid is a colorless, oily liquid, nearly twice as heavy as water. The ordinary concentrated acid contains about 2% of water, has a density of 1.84, and boils at 338°. It is sometimes called _oil of vitriol_, since it was formerly made by distilling a substance called _green vitriol_. ~Chemical properties.~ Sulphuric acid possesses chemical properties which make it one of the most important of chemical substances. 1. _Action as an acid._ In dilute solution sulphuric acid acts as any other acid, forming salts with oxides and hydroxides. 2. _Action as an oxidizing agent._ Sulphuric acid contains a large percentage of oxygen and is, like nitric acid, a very good oxidizing agent. When the concentrated acid is heated with sulphur, carbon, and many other substances, oxidation takes place, the sulphuric acid decomposing according to the equation H_{2}SO_{4} = H_{2}SO_{3} + O. 3. _Action on metals._ In dilute solution sulphuric acid acts upon many metals, such as zinc, forming a sulphate and liberating hydrogen. When the concentrated acid is employed the hydrogen set free is oxidized by a new portion of the acid, with the liberation of sulphur dioxide. With copper the reactions are expressed by the equations (1) Cu + H_{2}SO_{4} = CuSO_{4} + 2H, (2) H_{2}SO_{4} + 2H = H_{2}SO_{3} + H_{2}O, (3) H_{2}SO_{3} = H_{2}O + SO_{2}. By combining these equations the following one is obtained: Cu + 2H_{2}SO_{4} = CuSO_{4} + SO_{2} + 2H_{2}O. 4. _Action on salts._ We have repeatedly seen that an acid of high boiling point heated with the salt of some acid of lower boiling point will drive out the low boiling acid. The boiling point of sulphuric acid (338°) is higher than that of almost any common acid; hence it is used largely in the preparation of other acids. 5. _Action on water._ Concentrated sulphuric acid has a very great affinity for water, and is therefore an effective dehydrating agent. Gases which have no chemical action upon sulphuric acid can be freed from water vapor by bubbling them through the strong acid. When the acid is diluted with water much heat is set free, and care must be taken to keep the liquid thoroughly stirred during the mixing, and to pour the acid into the water,--never the reverse. Not only can sulphuric acid absorb water, but it will often withdraw the elements hydrogen and oxygen from a compound containing them, decomposing the compound, and combining with the water so formed. For this reason most organic substances, such as sugar, wood, cotton, and woolen fiber, and even flesh, all of which contain much oxygen and hydrogen in addition to carbon, are charred or burned by the action of the concentrated acid. ~Salts of sulphuric acid,--sulphates.~ The sulphates form a very important class of salts, and many of them have commercial uses. Copperas (iron sulphate), blue vitriol (copper sulphate), and Epsom salt (magnesium sulphate) serve as examples. Many sulphates are important minerals, prominent among these being gypsum (calcium sulphate) and barytes (barium sulphate). ~Thiosulphuric acid~ (H_{2}S_{2}O_{3}); ~Thiosulphates.~ Many other acids of sulphur containing oxygen are known, but none of them are of great importance. Most of them cannot be prepared in a pure state, and are known only through their salts. The most important of these is thiosulphuric acid. When sodium sulphite is boiled with sulphur the two substances combine, forming a salt which has the composition represented in the formula Na_{2}S_{2}O_{3}: Na_{2}SO_{3} + S = Na_{2}S_{2}O_{3}. The substance is called sodium thiosulphate, and is a salt of the easily decomposed acid H_{2}S_{2}O_{3}, called thiosulphuric acid. This reaction is quite similar to the action of oxygen upon sulphites: Na_{2}SO_{3} + O = Na_{2}SO_{4}. More commonly the salt is called sodium hyposulphite, or merely "hypo." It is a white solid and is extensively used in photography, in the bleaching industry, and as a disinfectant. ~Monobasic and dibasic acids.~ Such acids as hydrochloric and nitric acids, which have only one replaceable hydrogen atom in the molecule, or in other words yield one hydrogen ion in solution, are called monobasic acids. Acids yielding two hydrogen ions in solution are called dibasic acids. Similarly, we may have tribasic and tetrabasic acids. The three acids of sulphur are dibasic acids. It is therefore possible for each of them to form both normal and acid salts. The acid salts can be made in two ways: the acid may be treated with only half enough base to neutralize it,-- NaOH + H_{2}SO_{4} = NaHSO_{4} + H_{2}O; or a normal salt may be treated with the free acid,-- Na_{2}SO_{4} + H_{2}SO_{4} = 2NaHSO_{4}. Acid sulphites and sulphides may be made in the same ways. ~Carbon disulphide~ (CS_{2}). When sulphur vapor is passed over highly heated carbon the two elements combine, forming carbon disulphide (CS_{2}), just as oxygen and carbon unite to form carbon dioxide (CO_{2}). The substance is a heavy, colorless liquid, possessing, when pure, a pleasant ethereal odor. On standing for some time, especially when exposed to sunlight, it undergoes a slight decomposition and acquires a most disagreeable, rancid odor. It has the property of dissolving many substances, such as gums, resins, and waxes, which are insoluble in most liquids, and it is extensively used as a solvent for such substances. It is also used as an insecticide. It boils at a low temperature (46°), and its vapor is very inflammable, burning in the air to form carbon dioxide and sulphur dioxide, according to the equation CS_{2} + 6O = CO_{2} + 2SO_{2}. [Illustration: Fig. 45] ~Commercial preparation of carbon disulphide.~ In the preparation of carbon disulphide an electrical furnace is employed, such as is represented in Fig. 45. The furnace is packed with carbon C, and this is fed in through the hoppers B, as fast as that which is present in the hearth of the furnace is used up. Sulphur is introduced at A, and at the lower ends of the tubes it is melted by the heat of the furnace and flows into the hearth as a liquid. An electrical current is passed through the carbon and melted sulphur from the electrodes E, heating the charge. The vapors of carbon disulphide pass up through the furnace and escape at D, from which they pass to a suitable condensing apparatus. ~Comparison of sulphur and oxygen.~ A comparison of the formulas and the chemical properties of corresponding compounds of oxygen and sulphur brings to light many striking similarities. The conduct of hydrosulphuric acid and water toward many substances has been seen to be very similar; the oxides and sulphides of the metals have analogous formulas and undergo many parallel reactions. Carbon dioxide and disulphide are prepared in similar ways and undergo many analogous reactions. It is clear, therefore, that these two elements are far more closely related to each other than to any of the other elements so far studied. ~Selenium and tellurium.~ These two very uncommon elements are still more closely related to sulphur than is oxygen. They occur in comparatively small quantities and are usually found associated with sulphur and sulphides, either as the free elements or more commonly in combination with metals. They form compounds with hydrogen of the formulas H_{2}Se and H_{2}Te; these bodies are gases with properties very similar to those of H_{2}S. They also form oxides and oxygen acids which resemble the corresponding sulphur compounds. The elements even have allotropic forms corresponding very closely to those of sulphur. Tellurium is sometimes found in combination with gold and copper, and occasions some difficulties in the refining of these metals. The elements have very few practical applications. ~Crystallography.~ In order to understand the difference between the two kinds of sulphur crystals, it is necessary to know something about crystals in general and the forms which they may assume. An examination of a large number of crystals has shown that although they may differ much in geometric form, they can all be considered as modifications of a few simple plans. The best way to understand the relation of one crystal to another is to look upon every crystal as having its faces and angles arranged in definite fashion about certain imaginary lines drawn through the crystal. These lines are called axes, and bear much the same relation to a crystal as do the axis and parallels of latitude and longitude to the earth and a geographical study of it. All crystals can be referred to one of six simple plans or systems, which have their axes as shown in the following drawings. The names and characteristics of these systems are as follows: 1. Isometric or regular system (Fig. 46). Three equal axes, all at right angles. [Illustration: Fig. 46] 2. Tetragonal system (Fig. 47). Two equal axes and one of different length, all at right angles to each other. [Illustration: Fig. 47] 3. Orthorhombic system (Fig. 48). Three unequal axes, all at right angles to each other. [Illustration: Fig. 48] 4. Monoclinic system (Fig. 49). Two axes at right angles, and a third at right angles to one of these, but inclined to the other. [Illustration: Fig. 49] 5. Triclinic system (Fig. 50). Three axes, all inclined to each other. [Illustration: Fig. 50] 6. Hexagonal system (Fig. 51). Three equal axes in the same plane intersecting at angles of 60°, and a fourth at right angles to all of these. [Illustration: Fig. 51] Every crystal can be imagined to have its faces and angles arranged in a definite way around one of these systems of axes. A cube, for instance, is referred to Plan 1, an axis ending in the center of each face; while in a regular octohedron an axis ends in each solid angle. These forms are shown in Fig. 46. It will be seen that both of these figures belong to the same system, though they are very different in appearance. In the same way, many geometric forms may be derived from each of the systems, and the light lines about the axes in the drawings show two of the simplest forms of each of the systems. In general a given substance always crystallizes in the same system, and two corresponding faces of each crystal of it always make the same angle with each other. A few substances, of which sulphur is an example, crystallize in two different systems, and the crystals differ in such physical properties as melting point and density. Such substances are said to be _dimorphous_. EXERCISES 1. (a) Would the same amount of heat be generated by the combustion of 1 g. of each of the allotropic modifications of sulphur? (b) Would the same amount of sulphur dioxide be formed in each case? 2. Is the equation for the preparation of hydrosulphuric acid a reversible one? As ordinarily carried out, does the reaction complete itself? 3. Suppose that hydrosulphuric acid were a liquid, would it be necessary to modify the method of preparation? 4. Can sulphuric acid be used to dry hydrosulphuric acid? Give reason for answer. 5. Does dry hydrosulphuric acid react with litmus paper? State reason for answer. 6. How many grams of iron sulphide are necessary to prepare 100 l. of hydrosulphuric acid when the laboratory conditions are 17° and 740 mm. pressure? 7. Suppose that the hydrogen in 1 l. of hydrosulphuric acid were liberated; what volume would it occupy, the gases being measured under the same conditions? 8. Write the equations representing the reaction between hydrosulphuric acid and sodium hydroxide and ammonium hydroxide respectively. 9. Show that the preparation of sulphur dioxide from a sulphite is similar in principle to the preparation of hydrogen sulphide. 10. (a) Does dry sulphur dioxide react with litmus paper? (b) How can it be shown that a solution of sulphur dioxide in water acts like an acid? 11. (a) Calculate the percentage composition of sulphurous anhydride and sulphuric anhydride. (b) Show how these two substances are in harmony with the law of multiple proportion. 12. How many pounds of sulphur would be necessary in the preparation of 100 lb. of 98% sulphuric acid? 13. What weight of sulphur dioxide is necessary in the preparation of 1 kg. of sodium sulphite? 14. What weight of copper sulphate crystals can be obtained by dissolving 1 kg. of copper in sulphuric acid and crystallizing the product from water? 15. Write the names and formulas of the oxides and oxygen acids of selenium and tellurium. 16. In the commercial preparation of carbon disulphide, what is the function of the electric current? 17. If the Gay-Lussac tower were omitted from the sulphuric acid factory, what effect would this have on the cost of production of sulphuric acid? CHAPTER XV PERIODIC LAW A number of the elements have now been studied somewhat closely. The first three of these, oxygen, hydrogen, and nitrogen, while having some physical properties in common with each other, have almost no point of similarity as regards their chemical conduct. On the other hand, oxygen and sulphur, while quite different physically, have much in common in their chemical properties. About eighty elements are now known. If all of these should have properties as diverse as do oxygen, hydrogen, and nitrogen, the study of chemistry would plainly be a very difficult and complicated one. If, however, the elements can be classified in groups, the members of which have very similar properties, the study will be very much simplified. ~Earlier classification of the elements.~ Even at an early period efforts were made to discover some natural principle in accordance with which the elements could be classified. Two of these classifications may be mentioned here. 1. _Classification into metals and non-metals._ The classification into metals and non-metals most naturally suggested itself. This grouping was based largely on physical properties, the metals being heavy, lustrous, malleable, ductile, and good conductors of heat and electricity. Elements possessing these properties are usually base-forming in character, and the ability to form bases came to be regarded as a characteristic property of the metals. The non-metals possessed physical properties which were the reverse of those of the metals, and were acid-forming in character. Not much was gained by this classification, and it was very imperfect. Some metals, such as potassium, are very light; some non-metals, such as iodine, have a high luster; some elements can form either an acid or a base. 2. _Classification into triad families._ In 1825 Döbereiner observed that an interesting relation exists between the atomic weights of chemically similar elements. To illustrate, lithium, sodium, and potassium resemble each other very closely, and the atomic weight of sodium is almost exactly an arithmetical mean between those of the other two: (7.03 + 39.15)/2 = 23.09. In many chemical and physical properties sodium is midway between the other two. A number of triad families were found, but among eighty elements, whose atomic weights range all the way from 1 to 240, such agreements might be mere chance. Moreover many elements did not appear to belong to such families. ~Periodic division.~ In 1869 the Russian chemist Mendeléeff devised an arrangement of the elements based on their atomic weights, which has proved to be of great service in the comparative study of the elements. A few months later the German, Lothar Meyer, independently suggested the same ideas. This arrangement brought to light a great generalization, now known as the _periodic law_. An exact statement of the law will be given after the method of arranging the elements has been described. [Illustration: DMITRI IVANOVITCH MENDELÉEFF (Russian) (1834-1907) Author of the periodic law; made many investigations on the physical constants of elements and compounds; wrote an important book entitled "Principles of Chemistry"; university professor and government official] ~Arrangement of the periodic table.~ The arrangement suggested by Mendeléeff, modified somewhat by more recent investigations, is as follows: Beginning with lithium, which has an atomic weight of 7, the elements are arranged in a horizontal row in the order of their atomic weights, thus: ~Li (7.03), Be (9.1), B (11), C (12), N (14.04), O (16), F (19).~ These seven elements all differ markedly from each other. The eighth element, sodium, is very similar to lithium. It is placed just under lithium, and a new row follows: ~Na(23.05), Mg (24.36), Al (27.1), Si (28.4), P (31), S (32.06), Cl(35.45).~ When the fifteenth element, potassium, is reached, it is placed under sodium, to which it is very similar, and serves to begin a third row: ~K (39.15), Ca (40.1), Sc (44.1,) Ti (48.1), V (51.2), Cr (52.1), Mn(55).~ Not only is there a strong similarity between lithium, sodium, and potassium, which have been placed in a vertical row because of this resemblance, but the elements in the other vertical rows exhibit much of the same kind of similarity among themselves, and evidently form little natural groups. The three elements following manganese, namely, iron, nickel, and cobalt, have atomic weights near together, and are very similar chemically. They do not strongly resemble any of the elements so far considered, and are accordingly placed in a group by themselves, following manganese. A new row is begun with copper, which somewhat resembles the elements of the first vertical column. Following the fifth and seventh rows are groups of three closely related elements, so that the completed arrangement has the appearance represented in the table on page 168. THE PERIODIC ARRANGEMENT OF THE ELEMENTS --------+-----------+-----------+-----------+-----------+-----------+ Periods | GROUP | GROUP | GROUP | GROUP | GROUP | | 0 | I | II | III | IV | |A B|A B|A B|A B|A B| --------+-----------+-----------+-----------+-----------+-----------+ 1 |H==1.008 | | | | | 2 |He=4 |Li=7.03 |Be=9.1 |B=11 |C=12 | --------+-----------+-----------+-----------+-----------+-----------+ 3 | Ne=20|Na=23.05 | Mg=24.36| AL=27.1| Si=28.4| --------+-----------+-----------+-----------+-----------+-----------+ 4 |A=39.9 |K=39.15 |Ca=40.1 |Sc=44.1 |Ti=48.1 | | | | | | | | | | | | | --------+-----------+-----------+-----------+-----------+-----------+ 5 | | Cu=63.6| Zn=65.4| Ga=70| Ge=72.5| --------+-----------+-----------+-----------+-----------+-----------+ 6 |Kr=81.8 |Rb=85.5 |Sr=87.6 |Y=89 |Zr=90.6 | | | | | | | | | | | | | --------+-----------+-----------+-----------+-----------+-----------+ 7 | | Ag=107.93| Cd=112.4| In=115| Sn=119| --------+-----------+-----------+-----------+-----------+-----------+ 8 |X=128 |Cs=132.9 |Ba=137.4 |La=138.9 |Ce=Yb* | | | | | |140.25-173 | | | | | | | --------+-----------+-----------+-----------+-----------+-----------+ 9 | Au=197.2| Hg=200| Tl=204.1| Pb=206.9| Bi=208.5| --------+-----------+-----------+-----------+-----------+-----------+ 10 | | |Ra=225 | |Th=232.5 | --------+-----------+-----------+-----------+-----------+-----------+ | | R_{2}O | RO |R_{2}O_{3} | RO_{2} | | | RH | RH_{2} | RH_{3} | RH_{4} | --------+-----------+-----------+-----------+-----------+-----------+ ==================part 2============== --------+-----------+-----------+-----------+-----------+ Periods | GROUP | GROUP | GROUP | GROUP | | V | VI | VII | VIII | |A B|A B|A B| | --------+-----------+-----------+-----------+-----------+ 1 | | | | | 2 |N=14.04 |O=16 |F=19 | | --------+-----------+-----------+-----------+-----------+ 3 | P=31| S=32.06| Cl=35.45| | --------+-----------+-----------+-----------+-----------+ 4 |V=51.2 |Cr=52.1 |Mn=55 |Fe=55.9 | | | | |Ni=58.7 | | | | |Co=59 | --------+-----------+-----------+-----------+-----------+ 5 | As=75| Se=79.2| Br=79.96| | --------+-----------+-----------+-----------+-----------+ 6 |Cb=94 |Mo=96 | |Ru=101.7 | | | | |Rh=103 | | | | |Pd=106.5 | --------+-----------+-----------+-----------+-----------+ 7 | Sb=120.2| Te=127.6| I=126.97| | --------+-----------+-----------+-----------+-----------+ 8 |Ta=183 |W=184 | |Os=191 | | | | |Ir=193 | | | | |Pt=194.8 | --------+-----------+-----------+-----------+-----------+ 9 | | | | | --------+-----------+-----------+-----------+-----------+ 10 | U=238.5 | | | | --------+-----------+-----------+-----------+-----------+ | R_{2}O_{5}| RO_{3} | R_{2}O_{7}| RO_{4} | | RH_{3} | RH_{2} | RH | | --------+-----------+-----------+-----------+-----------+ [* This includes a number of elements whose atomic weights lie between 140 and 173, but which have not been accurately studied, and so their proper arrangement is uncertain.] ~Place of the atmospheric elements.~ When argon was discovered it was seen at once that there was no place in the table for an element of atomic weight approximately 40. When the other inactive elements were found, however, it became apparent that they form a group just preceding Group 1. They are accordingly arranged in this way in Group 0 (see table on opposite page). A study of this table brings to light certain very striking facts. ~Properties of elements vary with atomic weights.~ There is evidently a close relation between the properties of an element and its atomic weight. Lithium, at the beginning of the first group, is a very strong base-forming element, with pronounced metallic properties. Beryllium, following lithium, is less strongly base-forming, while boron has some base-forming and some acid-forming properties. In carbon all base-forming properties have disappeared, and the acid-forming properties are more marked than in boron. These become still more emphasized as we pass through nitrogen and oxygen, until on reaching fluorine we have one of the strongest acid-forming elements. The properties of these seven elements therefore vary regularly with their atomic weights, or, in mathematical language, are regular functions of them. ~Periodic law.~ The properties of the first seven elements vary _continuously_--that is steadily--away from base-forming and toward acid-forming properties. If lithium had the smallest atomic weight of any of the elements, and fluorine the greatest, so that in passing from one to the other we had included all the elements, we could say that the properties of elements are continuous functions of their atomic weights. But fluorine is an element of small atomic weight, and the one following it, sodium, breaks the regular order, for in it reappear all the characteristic properties of lithium. Magnesium, following sodium, bears much the same relation to beryllium that sodium does to lithium, and the properties of the elements in the second row vary much as they do in the first row until potassium is reached, when another repetition begins. The properties of the elements do not vary continuously, therefore, with atomic weights, but at regular intervals there is a repetition, or _period_. This generalization is known as the _periodic law_, and may be stated thus: _The properties of elements are periodic functions of their atomic weights._ ~The two families in a group.~ While all the elements in a given vertical column bear a general resemblance to each other, it has been noticed that those belonging to periods having even numbers are very strikingly similar to each other. They are placed at the left side of the group columns. In like manner, the elements belonging to the odd periods are very similar and are arranged at the right side of the group columns. Thus calcium, strontium, and barium are very much alike; so, too, are magnesium, zinc, and cadmium. The resemblance between calcium and magnesium, or strontium and zinc, is much less marked. This method of arrangement therefore divides each group into two families, each containing four or five members, between which there is a great similarity. ~Family resemblances.~ Let us now inquire more closely in what respects the elements of a family resemble each other. 1. _Valence._ In general the valence of the elements in a family is the same, and the formulas of their compounds are therefore similar. If we know that the formula of sodium chloride is NaCl, it is pretty certain that the formula of potassium chloride will be KCl--not KCl_{2} or KCl_{3}. The general formulas R_{2}O, RO, etc., placed below the columns show the formulas of the oxides of the elements in the column provided they form oxides. In like manner the formulas RH, RH_{2}, etc., show the composition of the compounds formed with hydrogen or chlorine. 2. _Chemical properties._ The chemical properties of the members of a family are quite similar. If one member is a metal, the others usually are; if one is a non-metal, so, too, are the others. The families in the first two columns consist of metals, while the elements found in the last two columns form acids. There is in addition a certain regularity in properties of the elements in each family. If the element at the head of the family is a strong acid-forming element, this property is likely to diminish gradually, as we pass to the members of the family with higher atomic weights. Thus phosphorus is strongly acid-forming, arsenic less so, antimony still less so, while bismuth has almost no acid-forming properties. We shall meet with many illustrations of this fact. 3. _Physical properties._ In the same way, the physical properties of the members of a family are in general somewhat similar, and show a regular gradation as we pass from element to element in the family. Thus the densities of the members of the magnesium family are Mg = 1.75, Zn = 7.00, Cd = 8.67, Hg = 13.6. Their melting points are Mg = 750°, Zn = 420°, Cd = 320°, Hg = -39.5°. ~Value of the periodic law.~ The periodic law has proved of much value in the development of the science of chemistry. 1. _It simplifies study._ It is at once evident that such regularities very much simplify the study of chemistry. A thorough study of one element of a family makes the study of the other members a much easier task, since so many of the properties and chemical reactions of the elements are similar. Thus, having studied the element sulphur in some detail, it is not necessary to study selenium and tellurium so closely, for most of their properties can be predicted from the relation which they sustain to sulphur. 2. _It predicts new elements._ When the periodic law was first formulated there were a number of vacant places in the table which evidently belonged to elements at that time unknown. From their position in the table, Mendeléeff predicted with great precision the properties of the elements which he felt sure would one day be discovered to fill these places. Three of them, scandium, germanium, and gallium, were found within fifteen years, and their properties agreed in a remarkable way with the predictions of Mendeléeff. There are still some vacant places in the table, especially among the heavier elements. 3. _It corrects errors._ The physical constants of many of the elements did not at first agree with those demanded by the periodic law, and a further study of many such cases showed that errors had been made. The law has therefore done much service in indicating probable error. ~Imperfections of the law.~ There still remain a good many features which must be regarded as imperfections in the law. Most conspicuous is the fact that the element hydrogen has no place in the table. In some of the groups elements appear in one of the families, while all of their properties show that they belong in the other. Thus sodium belongs with lithium and not with copper; fluorine belongs with chlorine and not with manganese. There are two instances where the elements must be transposed in order to make them fit into their proper group. According to their atomic weights, tellurium should follow iodine, and argon should follow potassium. Their properties show in each case that this order must be reversed. The table separates some elements altogether which, in many respects have closely agreeing properties. Iron, chromium, and manganese are all in different groups, although they are similar in many respects. The system is therefore to be regarded as but a partial and imperfect expression of some very important and fundamental relation between the substances which we know as elements, the exact nature of this relation being as yet not completely clear to us. EXERCISES 1. Suppose that an element were discovered that filled the blank in Group O, Period 5; what properties would it probably have? 2. Suppose that an element were discovered that filled the blank in Group VI, Period 9, family B; what properties would it have? 3. Sulphur and oxygen both belong in Group VI, although in different families; in what respects are the two similar? CHAPTER XVI THE CHLORINE FAMILY ================================================================== | | | | | ATOMIC | MELTING | BOILING | COLOR AND STATE | WEIGHT | POINT | POINT | ______________|________|_________|_________|______________________ | | | | Fluorine (F) | 19.00 | -223° | -187° | Pale yellowish gas. Chlorine (Cl) | 35.45 | -102° | -33.6° | Greenish-yellow gas. Bromine (Br) | 79.96 | -7° | 59° | Red liquid. Iodine (I) | 126.97 | 107° | 175° | Purplish-black solid. ================================================================== ~The family.~ The four elements named in the above table form a strongly marked family of elements and illustrate very clearly the way in which the members of a family in a periodic group resemble each other, as well as the character of the differences which we may expect to find between the individual members. 1. _Occurrence._ These elements do not occur in nature in the free state. The compounds of the last three elements of the family are found extensively in sea water, and on this account the name _halogens_, signifying "producers of sea salt," is sometimes applied to the family. 2. _Properties._ As will be seen by reference to the table, the melting points and boiling points of the elements of the family increase with their atomic weights. A somewhat similar gradation is noted in their color and state. One atom of each of the elements combines with one atom of hydrogen to form acids, which are gases very soluble in water. The affinity of the elements for hydrogen is in the inverse order of their atomic weights, fluorine having the strongest affinity and iodine the weakest. Only chlorine and iodine form oxides, and those of the former element are very unstable. The elements of the group are univalent in their compounds with hydrogen and the metals. FLUORINE ~Occurrence.~ The element fluorine occurs in nature most abundantly as the mineral fluorspar (CaF_{2}), as cryolite (Na_{3}AlF_{6}), and in the complex mineral apatite (3 Ca_{3}(PO_{4})_{2}·CaF_{2}). ~Preparation.~ All attempts to isolate the element resulted in failure until recent years. Methods similar to those which succeed in the preparation of the other elements of the family cannot be used; for as soon as the fluorine is liberated it combines with the materials of which the apparatus is made or with the hydrogen of the water which is always present. The preparation of fluorine was finally accomplished by the French chemist Moissan by the electrolysis of hydrofluoric acid. Perfectly dry hydrofluoric acid (HF) was condensed to a liquid and placed in a U-shaped tube made of platinum (or copper), which was furnished with electrodes and delivery tubes, as shown in Fig. 52. This liquid is not an electrolyte, but becomes such when potassium fluoride is dissolved in it. When this solution was electrolyzed hydrogen was set free at the cathode and fluorine at the anode. [Illustration: Fig. 52] ~Properties.~ Fluorine is a gas of slightly yellowish color, and can be condensed to a liquid boiling at -187° under atmospheric pressure. It solidifies at -223°. It is extremely active chemically, being the most active of all the elements at ordinary temperatures. It combines with all the common elements save oxygen, very often with incandescence and the liberation of much heat. It has a strong affinity for hydrogen and is able to withdraw it from its compounds with other elements. Because of its great activity it is extremely poisonous. Fluorine does not form any oxides, neither does it form any oxygen acids, in which respects it differs from the other members of the family. ~Hydrofluoric acid~ (HF). Hydrofluoric acid is readily obtained from fluorspar by the action of concentrated sulphuric acid. The equation is CaF_{2} + H_{2}SO_{4} = CaSO_{4} + 2HF. In its physical properties it resembles the binary acids of the other elements of this family, being, however, more easily condensed to a liquid. The anhydrous acid boils at 19° and can therefore be prepared at ordinary pressures. It is soluble in all proportions in water, and a concentrated solution--about 50%--is prepared for the market. Its fumes are exceedingly irritating to the respiratory organs, and several chemists have lost their lives by accidentally breathing them. [Illustration: HENRI MOISSAN (French) (1853-1907) Famous for his work with the electric furnace at high temperatures; prepared artificial diamonds, together with many new binary compounds such as carbides, silicides, borides, and nitrides; isolated fluorine and studied its properties and its compounds very thoroughly] ~Chemical properties.~ Hydrofluoric acid, like other strong acids, readily acts on bases and metallic oxides and forms the corresponding fluorides. It also dissolves certain metals such as silver and copper. It acts very vigorously upon organic matter, a single drop of the concentrated acid making a sore on the skin which is very painful and slow in healing. Its most characteristic property is its action upon silicon dioxide (SiO_{2}), with which it forms water and the gas silicon tetrafluoride (SiF_{4}), as shown in the equation SiO_{2} + 4HF = SiF_{4} + 2H_{2}O. Glass consists of certain compounds of silicon, which are likewise acted on by the acid so that it cannot be kept in glass bottles. It is preserved in flasks made of wax or gutta-percha. ~Etching.~ Advantage is taken of this reaction in etching designs upon glass. The glass vessel is painted over with a protective paint upon which the acid will not act, the parts which it is desired to make opaque being left unprotected. A mixture of fluorspar and sulphuric acid is then painted over the vessel and after a few minutes the vessel is washed clean. Wherever the hydrofluoric acid comes in contact with the glass it acts upon it, destroying its luster and making it opaque, so that the exposed design will be etched upon the clear glass. Frosted glass globes are often made in this way. The etching may also be effected by covering the glass with a thin layer of paraffin, cutting the design through the wax and then exposing the glass to the fumes of the acid. ~Salts of hydrofluoric acid,--fluorides.~ A number of the fluorides are known, but only one of them, calcium fluoride (CaF_{2}), is of importance. This is the well-known mineral fluorspar. CHLORINE ~Historical.~ While studying the action of hydrochloric acid upon the mineral pyrolusite, in 1774, Scheele obtained a yellowish, gaseous substance to which he gave a name in keeping with the phlogiston theory then current. Later it was supposed to be a compound containing oxygen. In 1810, however, the English chemist Sir Humphry Davy proved it to be an element and named it chlorine. ~Occurrence.~ Chlorine does not occur free in nature, but its compounds are widely distributed. For the most part it occurs in combination with the metals in the form of chlorides, those of sodium, potassium, and magnesium being most abundant. Nearly all salt water contains these substances, particularly sodium chloride, and very large salt beds consisting of chlorides are found in many parts of the world. ~Preparation.~ Two general methods of preparing chlorine may be mentioned, namely, the laboratory method and the electrolytic method. 1. _Laboratory method._ In the laboratory chlorine is made by warming the mineral pyrolusite (manganese dioxide, MnO_{2}) with concentrated hydrochloric acid. The first reaction, which seems to be similar to the action of acids upon oxides in general, is expressed in the equation MnO_{2} + 4HCl = MnCl_{4} + 2H_{2}O. The manganese compound so formed is very unstable, however, and breaks clown according to the equation MnCl_{4} = MnCl_{2} + 2Cl. Instead of using hydrochloric acid in the preparation of chlorine it will serve just as well to use a mixture of sodium chloride and sulphuric acid, since these two react to form hydrochloric acid. The following equations will then express the changes: (1) 2NaCl + H_{2}SO_{4} = Na_{2}SO_{4} + 2HCl. (2) MnO_{2} + 4 HCl = MnCl_{2} + 2Cl + 2H_{2}O. (3) MnCl_{2} + H_{2}SO_{4} = MnSO_{4} + 2HCl. Combining these equations, the following equation expressing the complete reaction is obtained: 2NaCl + MnO_{2} + 2H_{2}SO_{4} = MnSO_{4} + Na_{2}SO_{4} + 2H_{2}O + 2Cl. Since the hydrochloric acid liberated in the third equation is free to act upon manganese dioxide, it will be seen that all of the chlorine originally present in the sodium chloride is set free. The manganese dioxide and the hydrochloric acid are brought together in a flask, as represented in Fig. 53, and a gentle heat is applied. The rate of evolution of the gas is regulated by the amount of heat applied, and the gas is collected by displacement of air. As the equations show, only half of the chlorine present in the hydrochloric acid is liberated. [Illustration: Fig. 53] 2. _Electrolytic method._ Under the discussion of electrolysis (p. 102) it was shown that when a solution of sodium chloride is electrolyzed chlorine is evolved at the anode, while the sodium set free at the cathode reacts with the water to form hydrogen, which is evolved, and sodium hydroxide, which remains in solution. A great deal of the chlorine required in the chemical industries is now made in this way in connection with the manufacture of sodium hydroxide. ~Physical properties.~ Chlorine is a greenish-yellow gas, which has a peculiar suffocating odor and produces a very violent effect upon the throat and lungs. Even when inhaled in small quantities it often produces all the symptoms of a hard cold, and in larger quantities may have serious and even fatal action. It is quite heavy (density = 2.45) and can therefore be collected by displacement of air. One volume of water under ordinary conditions dissolves about three volumes of chlorine. The gas is readily liquefied, a pressure of six atmospheres serving to liquefy it at 0°. It forms a yellowish liquid which solidifies at -102°. ~Chemical properties.~ At ordinary temperatures chlorine is far more active chemically than any of the elements we have so far considered, with the exception of fluorine; indeed, it is one of the most active of all elements. 1. _Action on metals._ A great many metals combine directly with chlorine, especially when hot. A strip of copper foil heated in a burner flame and then dropped into chlorine burns with incandescence. Sodium burns brilliantly when heated strongly in slightly moist chlorine. Gold and silver are quickly tarnished by the gas. 2. _Action on non-metals._ Chlorine has likewise a strong affinity for many of the non-metals. Thus phosphorus burns in a current of the gas, while antimony and arsenic in the form of a fine powder at once burst into flame when dropped into jars of the gas. The products formed in all cases where chlorine combines with another element are called _chlorides_. 3. _Action on hydrogen._ Chlorine has a strong affinity for hydrogen, uniting with it to form hydrochloric acid. A jet of hydrogen burning in the air continues to burn when introduced into a jar of chlorine, giving a somewhat luminous flame. A mixture of the two gases explodes violently when a spark is passed through it or when it is exposed to bright sunlight. In the latter case it is the light and not the heat which starts the action. 4. _Action on substances containing hydrogen._ Not only will chlorine combine directly with free hydrogen but it will often abstract the element from its compounds. Thus, when chlorine is passed into a solution containing hydrosulphuric acid, sulphur is precipitated and Hydrochloric acid formed. The reaction is shown by the following equation: H_{2}S + 2Cl = 2HCl + S. With ammonia the action is similar: NH_{3} + 3Cl = 3HCl + N. The same tendency is very strikingly seen in the action of chlorine upon turpentine. The latter substance is largely made up of compounds having the composition represented by the formula C_{10}H_{16}. When a strip of paper moistened with warm turpentine is placed in a jar of chlorine dense fumes of hydrochloric acid appear and a black deposit of carbon is formed. Even water, which is a very stable compound, can be decomposed by chlorine, the oxygen being liberated. This may be shown in the following way: [Illustration: Fig. 54] If a long tube of rather large diameter is filled with a strong solution of chlorine in water and inverted in a vessel of the same solution, as shown in Fig. 54, and the apparatus is placed in bright sunlight, very soon bubbles of a gas will be observed to rise through the solution and collect in the tube. An examination of this gas will show that it is oxygen. It is liberated from water in accordance with the following equation: H_{2}O + 2Cl = 2HCl + O. 5. _Action on color substances,--bleaching action._ If strips of brightly colored cloth or some highly colored flowers are placed in quite dry chlorine, no marked change in color is noticed as a rule. If, however, the cloth and flowers are first moistened, the color rapidly disappears, that is, the objects are bleached. Evidently the moisture as well as the chlorine is concerned in the action, and a study of the case shows that the chlorine has combined with the hydrogen of the water. The oxygen set free oxidizes the color substance, converting it into a colorless compound. It is evident from this explanation that chlorine will only bleach those substances which are changed into colorless compounds by oxidation. 6. _Action as a disinfectant._ Chlorine has also marked germicidal properties, and the free element, as well as compounds from which it is easily liberated, are used as disinfectants. ~Nascent state.~ It will be noticed that oxygen when set free from water by chlorine is able to do what ordinary oxygen cannot do, for both the cloth and the flowers are unchanged in the air which contains oxygen. It is generally true that the activity of an element is greatest at the instant of liberation from its compounds. To express this fact elements at the instant of liberation are said to be in the _nascent state_. It is nascent oxygen which does the bleaching. ~Hydrochloric acid~ (_muriatic acid_) (HCl). The preparation of hydrochloric acid may be discussed under two general heads: 1. _Laboratory preparation._ The product formed by the burning of hydrogen in chlorine is the gas hydrochloric acid. This substance is much more easily obtained, however, by treating common salt (sodium chloride) with sulphuric acid. The following equation shows the reaction: 2NaCl + H_{2}SO_{4} = Na_{2}SO_{4} + 2HCl. The dry salt is placed in a flask furnished with a funnel tube and an exit tube, the sulphuric acid is added, and the flask gently warmed. The hydrochloric acid gas is rapidly given off and can be collected by displacement of air. The same apparatus can be used as was employed in the preparation of chlorine (Fig. 53). When a _solution_ of salt is treated with sulphuric acid there is no very marked action. The hydrochloric acid formed is very soluble in water, and so does not escape from the solution; hence a state of equilibrium is soon reached between the four substances represented in the equation. When _concentrated_ sulphuric acid, in which hydrochloric acid is not soluble, is poured upon dry salt the reaction is complete. 2. _Commercial preparation._ Commercially, hydrochloric acid is prepared in connection with the manufacture of sodium sulphate, the reaction being the same as that just given. The reaction is carried out in a furnace, and the hydrochloric acid as it escapes in the form of gas is passed into water in which it dissolves, the solution forming the hydrochloric acid of commerce. When the materials are pure a colorless solution is obtained. The most concentrated solution has a density of 1.2 and contains 40% HCl. The commercial acid, often called _muriatic acid_, is usually colored yellow by impurities. ~Composition of hydrochloric acid.~ When a solution of hydrochloric acid is electrolyzed in an apparatus similar to the one in which water was electrolyzed (Fig. 18), chlorine collects at the anode and hydrogen at the cathode. At first the chlorine dissolves in the water, but soon the water in the one tube becomes saturated with it, and if the stopcocks are left open until this is the case, and are then closed, it will be seen that the two gases are set free in equal volumes. When measured volumes of the two gases are caused to unite it is found that one volume of hydrogen combines with one of chlorine. Other experiments show that the volume of hydrochloric acid formed is just equal to the sum of the volumes of hydrogen and chlorine. Therefore one volume of hydrogen combines with one volume of chlorine to form two volumes of hydrochloric acid gas. Since chlorine is 35.18 times as heavy as hydrogen, it follows that one part of hydrogen by weight combines with 35.18 parts of chlorine to form 36.18 parts of hydrochloric acid. ~Physical properties.~ Hydrochloric acid is a colorless gas which has an irritating effect when inhaled, and possesses a sour, biting taste, but no marked odor. It is heavier than air (density = 1.26) and is very soluble in water. Under standard conditions 1 volume of water dissolves about 500 volumes of the gas. On warming such a solution the gas escapes, until at the boiling point the solution contains about 20% by weight of HCl. Further boiling will not drive out any more acid, but the solution will distill with unchanged concentration. A more dilute solution than this will lose water on boiling until it has reached the same concentration, 20%, and will then distill unchanged. Under high pressure the gas can be liquefied, 28 atmospheres being required at 0°. Under these conditions it forms a colorless liquid which is not very active chemically. It boils at -80° and solidifies at -113°. The solution of the gas in water is used almost entirely in the place of the gas itself, since it is not only far more convenient but also more active. ~Chemical properties.~ The most important chemical properties of hydrochloric acid are the following: 1. _Action as an acid._ In aqueous solution hydrochloric acid has very strong acid properties; indeed, it is one of the strongest acids. It acts upon oxides and hydroxides, converting them into salts: NaOH + HCl = NaCl + H_{2}O, CuO + 2HCl = CuCl_{2} + H_{2}O. It acts upon many metals, forming chlorides and liberating hydrogen: Zn + 2HCl = ZnCl_{2} + 2H, Al + 3HCl = AlCl_{3} + 3H. Unlike nitric and sulphuric acids it has no oxidizing action, so that when it acts on metals hydrogen is always given off. 2. _Relation to combustion._ Hydrochloric acid gas is not readily decomposed, and is therefore neither combustible nor a supporter of combustion. 3. _Action on oxidizing agents._ Although hydrochloric acid is incombustible, it can be oxidized under some circumstances, in which case the hydrogen combines with oxygen, while the chlorine is set free. Thus, when a solution of hydrochloric acid acts upon manganese dioxide part of the chlorine is set free: MnO_{2} + 4HCl = MnCl_{2} + 2H_{2}O + 2Cl. ~Aqua regia.~ It has been seen that when nitric acid acts as an oxidizing agent it usually decomposes, as represented in the equation 2HNO_{3} = H_{2}O + 2NO + 3O. The oxygen so set free may act on hydrochloric acid: 6HCl + 3O = 3H_{2}O + 6Cl. The complete equation therefore is 2HNO_{3} + 6HCl = 4H_{2}O + 2NO + 6Cl. When concentrated nitric and hydrochloric acids are mixed this reaction goes on slowly, chlorine and some other substances not represented in the equation being formed. The mixture is known as _aqua regia_ and is commonly prepared by adding one volume of nitric acid to three volumes of hydrochloric acid. It acts more powerfully upon metals and other substances than either of the acids separately, and owes its strength not to acid properties but to the action of the nascent chlorine which it liberates. Consequently, when it acts upon metals such as gold it converts them into chlorides, and the reaction can be represented by such equations as Au + 3Cl = AuCl_{3}. ~Salts of hydrochloric acid,--chlorides.~ The chlorides of all the metals are known and many of them are very important compounds. Some of them are found in nature, and all can be prepared by the general method of preparing salts. Silver chloride, lead chloride, and mercurous chloride are insoluble in water and acids, and can be prepared by adding hydrochloric acid to solutions of compounds of the respective elements. While the chlorides have formulas similar to the fluorides, their properties are often quite different. This is seen in the solubility of the salts. Those metals whose chlorides are insoluble form soluble fluorides, while many of the metals which form soluble chlorides form insoluble fluorides. ~Compounds of chlorine with oxygen and hydrogen.~ Chlorine combines with oxygen and hydrogen to form four different acids. They are all quite unstable, and most of them cannot be prepared in pure form; their salts can easily be made, however, and some of them will be met with in the study of the metals. The formulas and names of these acids are as follows: HClO hypochlorous acid. HClO_{2} chlorous acid. HClO_{3} chloric acid. HClO_{4} perchloric acid. ~Oxides of chlorine.~ Two oxides are known, having the formulas Cl_{2}O and ClO_{2}. They decompose very easily and are good oxidizing agents. BROMINE ~Historical.~ Bromine was discovered in 1826 by the French chemist Ballard, who isolated it from sea salt. He named it bromine (stench) because of its unbearable fumes. ~Occurrence.~ Bromine occurs almost entirely in the form of bromides, especially as sodium bromide and magnesium bromide, which are found in many salt springs and salt deposits. The Stassfurt deposits in Germany and the salt waters of Ohio and Michigan are especially rich in bromides. ~Preparation of bromine.~ The laboratory method of preparing bromine is essentially different from the commercial method. [Illustration Fig. 55] 1. _Laboratory method._ As in the case of chlorine, bromine can be prepared by the action of hydrobromic acid (HBr) on manganese dioxide. Since hydrobromic acid is not an article of commerce, a mixture of sulphuric acid and a bromide is commonly substituted for it. The materials are placed in a retort arranged as shown in Fig. 55. The end of the retort just touches the surface of the water in the test tube. On heating, the bromine distills over and is collected in the cold receiver. The equation is 2NaBr + 2H_{2}SO_{4} + MnO_{2} = Na_{2}SO_{4} + MnSO_{4} + 2H_{2}O + 2Br. 2. _Commercial method._ Bromine is prepared commercially from the waters of salt wells which are especially rich in bromides. On passing a current of electricity through such waters the bromine is first liberated. Any chlorine liberated, however, will assist in the reaction, since free chlorine decomposes bromides, as shown in the equation NaBr + Cl = NaCl + Br. When the water containing the bromine is heated, the liberated bromine distills over into the receiver. ~Physical properties.~ Bromine is a dark red liquid about three times as heavy as water. Its vapor has a very offensive odor and is most irritating to the eyes and throat. The liquid boils at 59° and solidifies at -7°; but even at ordinary temperatures it evaporates rapidly, forming a reddish-brown gas very similar to nitrogen peroxide in appearance. Bromine is somewhat soluble in water, 100 volumes of water under ordinary conditions dissolving 1 volume of the liquid. It is readily soluble in carbon disulphide, forming a yellow solution. ~Chemical properties and uses.~ In chemical action bromine is very similar to chlorine. It combines directly with many of the same elements with which chlorine unites, but with less energy. It combines with hydrogen and takes away the latter element from some of its compounds, but not so readily as does chlorine. Its bleaching properties are also less marked. Bromine finds many uses in the manufacture of organic drugs and dyestuffs and in the preparation of bromides. ~Hydrobromic acid (HBr).~ When sulphuric acid acts upon a bromide hydrobromic acid is set free: 2NaBr + H_{2}SO_{4} = Na_{2}SO_{4} + 2HBr. At the same time some bromine is set free, as may be seen from the red fumes which appear, and from the odor. The explanation of this is found in the fact that hydrobromic acid is much less stable than hydrochloric acid, and is therefore more easily oxidized. Concentrated sulphuric acid is a good oxidizing agent, and oxidizes a part of the hydrobromic acid, liberating bromine: H_{2}SO_{4} + 2HBr = 2H_{2}O + SO_{2} + 2Br. ~Preparation of pure hydrobromic acid.~ A convenient way to make pure hydrobromic acid is by the action of bromine upon moist red phosphorus. This can be done with the apparatus shown in Fig. 56. Bromine is put into the dropping funnel A, and red phosphorus, together with enough water to cover it, is placed in the flask B. By means of the stopcock the bromine is allowed to flow drop by drop into the flask, the reaction taking place without the application of heat. The equations are (1) P + 3Br = PBr_{3}, (2) PBr_{3} + 3H_{2}O = P(OH)_{3} + 3HBr. [Illustration Fig. 56] The U-tube C contains glass beads which have been moistened with water and rubbed in red phosphorus. Any bromine escaping action in the flask acts upon the phosphorus in the U-tube. The hydrobromic acid is collected in the same way as hydrochloric acid. ~Properties.~ Hydrobromic acid very strikingly resembles hydrochloric acid in physical and chemical properties. It is a colorless, strongly fuming gas, heavier than hydrochloric acid and, like it, is very soluble in water. Under standard conditions 1 volume of water dissolves 610 volumes of the gas. Chemically, the chief point in which it differs from hydrochloric acid is in the fact that it is much more easily oxidized, so that bromine is more readily set free from it than chlorine is from hydrochloric acid. ~Salts of hydrobromic acid,--bromides.~ The bromides are very similar to the chlorides in their properties. Chlorine acts upon both bromides and free hydrobromic acid, liberating bromine from them: KBr + Cl = KCl + Br, HBr + Cl = HCl + Br. Silver bromide is extensively used in photography, and the bromides of sodium and potassium are used as drugs. ~Oxygen compounds.~ No oxides of bromine are surely known, and bromine does not form so many oxygen acids as chlorine does. Salts of hypobromous acid (HBrO) and bromic acid (HBrO_{3}) are known. IODINE ~Historical.~ Iodine was discovered in 1812 by Courtois in the ashes of certain sea plants. Its presence was revealed by its beautiful violet vapor, and this suggested the name iodine (from the Greek for violet appearance). ~Occurrence.~ In the combined state iodine occurs in very small quantities in sea water, from which it is absorbed by certain sea plants, so that it is found in their ashes. It occurs along with bromine in salt springs and beds, and is also found in Chili saltpeter. ~Preparation.~ Iodine may be prepared in a number of ways, the principal methods being the following: 1. _Laboratory method._ Iodine can readily be prepared in the laboratory from an iodide by the method used in preparing bromine, except that sodium iodide is substituted for sodium bromide. It can also be made by passing chlorine into a solution of an iodide. [Illustration: Fig. 57] 2. _Commercial method._ Commercially iodine was formerly prepared from seaweed (kelp), but is now obtained almost entirely from the deposits of Chili saltpeter. The crude saltpeter is dissolved in water and the solution evaporated until the saltpeter crystallizes. The remaining liquors, known as the "mother liquors," contain sodium iodate (NaIO_{3}), in which form the iodine is present in the saltpeter. The chemical reaction by which the iodine is liberated from this compound is a complicated one, depending on the fact that sulphurous acid acts upon iodic acid, setting iodine free. This reaction is shown as follows: 2HIO_{3} + 5H_{2}SO_{3} = 5H_{2}SO_{4} + H_{2}O + 2I. ~Purification of iodine.~ Iodine can be purified very conveniently in the following way. The crude iodine is placed in an evaporating dish E (Fig. 57), and the dish is set upon the sand bath S. The iodine is covered with the inverted funnel F, and the sand bath is gently heated with a Bunsen burner. As the dish becomes warm the iodine rapidly evaporates and condenses again on the cold surface of the funnel in shining crystals. This process, in which a solid is converted into a vapor and is again condensed into a solid without passing through the liquid state, is called _sublimation_. ~Physical properties.~ Iodine is a purplish-black, shining, heavy solid which crystallizes in brilliant plates. Even at ordinary temperatures it gives off a beautiful violet vapor, which increases in amount as heat is applied. It melts at 107° and boils at 175°. It is slightly soluble in water, but readily dissolves in alcohol, forming a brown solution (tincture of iodine), and in carbon disulphide, forming a violet solution. The element has a strong, unpleasant odor, though by no means as irritating as that of chlorine and bromine. ~Chemical properties.~ Chemically iodine is quite similar to chlorine and bromine, but is still less active than bromine. It combines directly with many elements at ordinary temperatures. At elevated temperatures it combines with hydrogen, but the reaction is reversible and the compound formed is quite easily decomposed. Both chlorine and bromine displace it from its salts: KI + Br = KBr + I, KI + Cl = KCl + I. When even minute traces of iodine are added to thin starch paste a very intense blue color develops, and this reaction forms a delicate test for iodine. Iodine is extensively used in medicine, especially in the form of a tincture. It is also largely used in the preparation of dyes and organic drugs, iodoform, a substance used as an antiseptic, has the formula CHI_{3}. ~Hydriodic acid (HI).~ This acid cannot be prepared in pure condition by the action of sulphuric acid upon an iodide, since the hydriodic acid set free is oxidized by the sulphuric acid just as in the case of hydrobromic acid, but to a much greater extent. It can be prepared in exactly the same way as hydrobromic acid, iodine being substituted for bromine. It can also be prepared by passing hydrosulphuric acid into water in which iodine is suspended. The equation is H_{2}S + 2I = 2HI + S. The hydriodic acid formed in this way dissolves in the water. ~Properties and uses.~ Hydriodic acid resembles the corresponding acids of chlorine and bromine in physical properties, being a strongly fuming, colorless gas, readily soluble in water. Under standard conditions 1 volume of water dissolves about 460 volumes of the gas. It is, however, more unstable than either hydrochloric or hydrobromic acids, and on exposure to the air it gradually decomposes in accordance with the equation 2HI + O = H_{2}O + 2I. Owing to the slight affinity between iodine and hydrogen the acid easily gives up its hydrogen and is therefore a strong reducing agent. This is seen in its action on sulphuric acid. The salts of hydriodic acid, the iodides, are, in general, similar to the chlorides and bromides. Potassium iodide (KI) is the most familiar of the iodides and is largely used in medicine. ~Oxygen compounds.~ Iodine has a much greater affinity for oxygen than has either chlorine or bromine. When heated with nitric acid it forms a stable oxide (I_{2}O_{5}). Salts of iodic acid (HIO_{3}) and periodic acid (HIO_{4}) are easily prepared, and the free acids are much more stable than the corresponding acids of the other members of this family. GAY-LUSSAC'S LAW OF VOLUMES In the discussion of the composition of hydrochloric acid it was stated that one volume of hydrogen combines with one volume of chlorine to form two volumes of hydrochloric acid. With bromine and iodine similar combining ratios hold good. These facts recall the simple volume relations already noted in the study of the composition of steam and ammonia. These relations may be represented graphically in the following way: +---+ +----+ +------+ +------+ | H | + | Cl | = | H Cl | + | H Cl | +---+ +----+ +------+ +------+ +---+ +---+ +---+ +--------+ +--------+ | H | | H | + | O | = | H_{2}O | + | H_{2}O | +---+ +---+ +---+ +--------+ +--------+ +---+ +---+ +---+ +---+ +--------+ +--------+ | H | | H | | H | + | N | = | NH_{3} | + | NH_{3} | +---+ +---+ +---+ +---+ +--------+ +--------+ In the early part of the past century Gay-Lussac, a distinguished French chemist, studied the volume relations of many combining gases, and concluded that similar relations always hold. His observations are summed up in the following law: _When two gases combine chemically there is always a simple ratio between their volumes, and between the volume of either one of them and that of the product, provided it is a gas._ By a simple ratio is meant of course the ratio of small whole numbers, as 1 : 2, 2 : 3. EXERCISES 1. How do we account for the fact that liquid hydrofluoric acid is not an electrolyte? 2. Why does sulphuric acid liberate hydrofluoric acid from its salts? 3. In the preparation of chlorine, what advantages are there in treating manganese dioxide with a mixture of sodium chloride and sulphuric acid rather than with hydrochloric acid? 4. Why must chlorine water be kept in the dark? 5. What is the derivation of the word nascent? 6. What substances studied are used as bleaching agents? To what is the bleaching action due in each case? 7. What substances studied are used as disinfecting agents? 8. What is meant by the statement that hydrochloric acid is one of the strongest acids? 9. What is the meaning of the phrase _aqua regia_? 10. Cl_{2}O is the anhydride of what acid? 11. A solution of hydriodic acid on standing turns brown. How is this accounted for? 12. How can bromine vapor and nitrogen peroxide be distinguished from each other? 13. Write the equations for the reaction taking place when hydriodic acid is prepared from iodine, phosphorus, and water. 14. From their behavior toward sulphuric acid, to what class of agents do hydrobromic and hydriodic acids belong? 15. Give the derivation of the names of the elements of the chlorine family. 16. Write the names and formulas for the binary acids of the group in the order of the stability of the acids. 17. What is formed when a metal dissolves in each of the following? nitric acid; dilute sulphuric acid; concentrated sulphuric acid; hydrochloric acid; aqua regia. 18. How could you distinguish between a chloride, a bromide, and an iodide? 19. What weight of sodium chloride is necessary to prepare sufficient hydrochloric acid to saturate 1 l. of water under standard conditions? 20. On decomposition 100 l. of hydrochloric acid would yield how many liters of hydrogen and chlorine respectively, the gases being measured under the same conditions? Are your results in accord with the experimental facts? CHAPTER XVII CARBON AND SOME OF ITS SIMPLER COMPOUNDS ~The family.~ Carbon stands at the head of a family of elements in the fourth group in the periodic table. The resemblances between the elements of this family, while quite marked, are not so striking as in the case of the elements of the chlorine family. With the exception of carbon, these elements are comparatively rare, and need not be taken up in detail in this chapter. Titanium will be referred to again in connection with silicon which it very closely resembles. ~Occurrence.~ Carbon is found in nature in the uncombined state in several forms. The diamond is practically pure carbon, while graphite and coal are largely carbon, but contain small amounts of other substances. Its natural compounds are exceedingly numerous and occur as gases, liquids, and solids. Carbon dioxide is its most familiar gaseous compound. Natural gas and petroleum are largely compounds of carbon with hydrogen. The carbonates, especially calcium carbonate, constitute great strata of rocks, and are found in almost every locality. All living organisms, both plant and animal, contain a large percentage of this element, and the number of its compounds which go to make up all the vast variety of animate nature is almost limitless. Over one hundred thousand definite compounds containing carbon have been prepared. In the free state carbon occurs in three allotropic forms, two of which are crystalline and one amorphous. ~Crystalline carbon.~ Crystalline carbon occurs in two forms,--diamond and graphite. 1. _Diamond._ Diamonds are found in considerable quantities in several localities, especially in South Africa, the East Indies, and Brazil. The crystals belong to the regular system, but the natural stones do not show this very clearly. When found they are usually covered with a rough coating which is removed in the process of cutting. Diamond cutting is carried on most extensively in Holland. The density of the diamond is 3.5, and, though brittle, it is one of the hardest of substances. Black diamonds, as well as broken and imperfect stones which are valueless as gems, are used for grinding hard substances. Few chemical reagents have any action on the diamond, but when heated in oxygen or the air it blackens and burns, forming carbon dioxide. Lavoisier first showed that carbon dioxide is formed by the combustion of the diamond; and Sir Humphry Davy in 1814 showed that this is the only product of combustion, and that the diamond is pure carbon. ~The diamond as a gem.~ The pure diamond is perfectly transparent and colorless, but many are tinted a variety of colors by traces of foreign substances. Usually the colorless ones are the most highly prized, although in some instances the color adds to the value; thus the famous Hope diamond is a beautiful blue. Light passing through a diamond is very much refracted, and to this fact the stone owes its brilliancy and sparkle. ~Artificial preparation of diamonds.~ Many attempts have been made to produce diamonds artificially, but for a long time these always ended in failure, graphite and not diamonds being the product obtained. The French chemist Moissan, in his extended study of chemistry at high temperatures, finally succeeded (1893) in making some small ones. He accomplished this by dissolving carbon in boiling iron and plunging the crucible containing the mixture into water, as shown in Fig. 58. Under these conditions the carbon crystallized in the iron in the form of the diamond. The diamonds were then obtained by dissolving away the iron in hydrochloric acid. [Illustration: Fig. 58] 2. _Graphite._ This form of carbon is found in large quantities, especially in Ceylon, Siberia, and in some localities of the United States and Canada. It is a shining black substance, very soft and greasy to the touch. Its density is about 2.15. It varies somewhat in properties according to the locality in which it is found, and is more easily attacked by reagents than is the diamond. It is also manufactured by heating carbon with a small amount of iron (3%) in an electric furnace. It is used in the manufacture of lead pencils and crucibles, as a lubricant, and as a protective covering for iron in the form of a polish or a paint. ~Amorphous carbon.~ Although there are many varieties of amorphous carbon known, they are not true allotropic modifications. They differ merely in their degree of purity, their fineness of division, and in their mode of preparation. These substances are of the greatest importance, owing to their many uses in the arts and industries. As they occur in nature, or are made artificially, they are nearly all impure carbon, the impurity depending on the particular substance in question. 1. _Pure carbon._ Pure amorphous carbon is best prepared by charring sugar. This is a substance consisting of carbon, hydrogen, and oxygen, the latter two elements being present in the ratio of one oxygen atom to two of hydrogen. When sugar is strongly heated the oxygen and hydrogen are driven off in the form of water and pure carbon is left behind. Prepared in this way it is a soft, lustrous, very bulky, black powder. 2. _Coal and coke._ Coals of various kinds were probably formed from vast accumulations of vegetable matter in former ages, which became covered over with earthy material and were thus protected from rapid decay. Under various natural agencies the organic matter was slowly changed into coal. In anthracite these changes have gone the farthest, and this variety of coal is nearly pure carbon. Soft or bituminous coals contain considerable organic matter besides carbon and mineral substances. When heated strongly out of contact with air the organic matter is decomposed and the resulting volatile matter is driven off in the form of gases and vapors, and only the mineral matter and carbon remain behind. The gaseous product is chiefly illuminating gas and the solid residue is _coke_. Some of the coke is found as a dense cake on the sides and roof of the retort. This is called retort carbon and is quite pure. 3. _Charcoal._ This is prepared from wood in the same way that coke is made from coal. When the process is carried on in retorts the products expelled by the heat are saved. Among these are many valuable substances such as wood alcohol and acetic acid. Where timber is abundant the process is carried out in a wasteful way, by merely covering piles of wood with sod and setting the wood on fire. Some wood burns and the heat from this decomposes the wood not burned, forming charcoal from it. The charcoal, of course, contains the mineral part of the wood from which it is formed. 4. _Bone black._ This is sometimes called animal charcoal, and is made by charring bones and animal refuse. The organic part of the materials is thus decomposed and carbon is left in a very finely divided state, scattered through the mineral part which consists largely of calcium phosphate. For some uses this mineral part is removed by treatment with hydrochloric acid and prolonged washing. 5. _Lampblack._ Lampblack and soot are products of imperfect combustion of oil and coal, and are deposited from a smoky flame on a cold surface. The carbon in this form is very finely divided and usually contains various oily materials. ~Properties.~ While the various forms of carbon differ in many properties, especially in color and hardness, yet they are all odorless, tasteless solids, insoluble in water and characterized by their stability towards heat. Only in the intense heat of the electric arc does carbon volatilize, passing directly from the solid state into a vapor. Owing to this fact the inside surface of an incandescent light bulb after being used for some time becomes coated with a dark film of carbon. It is not acted on at ordinary temperatures by most reagents, but at a higher temperature it combines directly with many of the elements, forming compounds called _carbides_. When heated in the presence of sufficient oxygen it burns, forming carbon dioxide. ~Uses of carbon.~ The chief use of amorphous carbon is for fuel to furnish heat and power for all the uses of civilization. An enormous quantity of carbon in the form of the purer coals, coke, and charcoal is used as a reducing agent in the manufacture of the various metals, especially in the metallurgy of iron. Most of the metals are found in nature as oxides, or in forms which can readily be converted into oxides. When these oxides are heated with carbon the oxygen is abstracted, leaving the metal. Retort carbon and coke are used to make electric light carbons and battery plates, while lampblack is used for indelible inks, printer's ink, and black varnishes. Bone black and charcoal have the property of absorbing large volumes of certain gases, as well as smaller amounts of organic matter; hence they are used in filters to remove noxious gases and objectionable colors and odors from water. Bone black is used extensively in the sugar refineries to remove coloring matter from the impure sugars. ~Chemistry of carbon compounds.~ Carbon is remarkable for the very large number of compounds which it forms with the other elements, especially with oxygen and hydrogen. Compounds containing carbon are more numerous than all others put together, and the chemistry of these substances presents peculiarities not met with in the study of other substances. For these reasons the systematic study of carbon compounds, or of _organic chemistry_ as it is usually called, must be deferred until the student has gained some knowledge of the chemistry of other elements. An acquaintance with a few of the most familiar carbon compounds is, however, essential for the understanding of the general principles of chemistry. ~Compounds of carbon with hydrogen,--the hydrocarbons.~ Carbon unites with hydrogen to form a very large number of compounds called _hydrocarbons_. Petroleum and natural gas are essentially mixtures of a great variety of these hydrocarbons. Many others are found in living plants, and still others are produced by the decay of organic matter in the absence of air. Only two of them, methane and acetylene, will be discussed here. ~Methane~ (_marsh gas_) (CH_{4}). This is one of the most important of these hydrocarbons, and constitutes about nine tenths of natural gas. As its name suggests, it is formed in marshes by the decay of vegetable matter under water, and bubbles of the gas are often seen to rise when the dead leaves on the bottom of pools are stirred. It also collects in mines, and, when mixed with air, is called _fire damp_ by the miners because of its great inflammability, damp being an old name for a gas. It is formed when organic matter, such as coal or wood, is heated in closed vessels, and is therefore a principal constituent of coal gas. ~Preparation.~ Methane is prepared in the laboratory by heating sodium or calcium acetate with soda-lime. Equal weights of fused sodium acetate and soda-lime are thoroughly dried, then mixed and placed in a good-sized, hard-glass test tube fitted with a one-holed stopper and delivery tube. The mixture is gradually heated, and when the air has been displaced from the tube the gas is collected in bottles by displacement of water. Soda-lime is a mixture of sodium and calcium hydroxides. Regarding it as sodium hydroxide alone, the equation is NaC_{2}H_{3}O_{2} + NaOH = Na_{2}CO_{3} + CH_{4}. ~Properties.~ Methane is a colorless, odorless gas whose density is 0.55. It is difficult to liquefy, boiling at -155° under standard pressure, and is almost insoluble in water. It burns with a pale blue flame, liberating much heat, and when mixed with oxygen is very explosive. ~Davy's safety lamp.~ In 1815 Sir Humphry Davy invented a lamp for the use of miners, to prevent the dreadful mine explosions then common, due to methane mixed with air. The invention consisted in surrounding the upper part of the common miner's lamp with a mantle of wire gauze and the lower part with glass (Fig. 59). It has been seen that two gases will not combine until raised to their kindling temperature, and if while combining they are cooled below this point, the combination ceases. A flame will not pass through a wire gauze because the metal, being a good conductor of heat, takes away so much heat from the flame that the gases are cooled below the kindling temperature. When a lamp so protected is brought into an explosive mixture the gases inside the wire mantle burn in a series of little explosions, giving warning to the miner that the air is unsafe. [Illustration: Fig. 59] ~Acetylene~ (C_{2}H_{2}). This is a colorless gas usually having a disagreeable odor due to impurities. It is now made in large quantities from calcium carbide (CaC_{2}). This substance is formed when coal and lime are heated together in an electric furnace. When treated with water the carbide is decomposed, yielding acetylene: CaC_{2} + 2H_{2}O = C_{2}H_{2} + Ca(OH)_{2}. Under ordinary conditions the gas burns with a very smoky flame; in burners constructed so as to secure a large amount of oxygen it burns with a very brilliant white light, and hence is used as an illuminant. ~Laboratory preparation.~ The gas can be prepared readily in a generator such as is shown in Fig. 60. The inner tube contains fragments of calcium carbide, while the outer one is filled with water. As long as the stopcock is closed the water cannot rise in the inner tube. When the stopcock is open the water rises, and, coming into contact with the carbide in the inner tube, generates acetylene. This escapes through the stopcock, and after the air has been expelled may be lighted as it issues from the burner. [Illustration: Fig. 60] Carbon forms two oxides, namely, carbon dioxide (CO_{2}) and carbon monoxide (CO). ~Carbon dioxide~ (CO_{2}). Carbon dioxide is present in the air to the extent of about 3 parts in 10,000, and this apparently small amount is of fundamental importance in nature. In some localities it escapes from the earth in great quantities, and many spring waters carry large amounts of it in solution. When these highly charged spring waters reach the surface of the earth, and the pressure on them is removed, the carbon dioxide escapes with effervescence. It is a product of the oxidation of all organic matter, and is therefore formed in fires as well as in the process of decay. It is thrown off from the lungs of all animals in respiration, and is a product of many fermentation processes such as vinegar making and brewing. Combined with metallic oxides it forms vast deposits of carbonates in nature. ~Preparation.~ In the laboratory carbon dioxide is always prepared by the action of an acid upon a carbonate, usually calcium carbonate, the apparatus shown in Fig. 39 serving the purpose very well. This reaction might be expected to produce carbonic acid, thus: CaCO_{3} + 2HCl = CaCl_{2} + H_{2}CO_{3}. Carbonic acid is very unstable, however, and decomposes into its anhydride, CO_{2}, and water, thus: H_{2}CO_{3} = H_{2}O + CO_{2}. The complete reaction is represented by the equation CaCO_{3} + 2HCl = CaCl_{2} + CO_{2} + H_{2}O. ~Physical properties.~ Carbon dioxide is a colorless, practically odorless gas whose density is 1.5. Its weight may be inferred from the fact that it can be siphoned, or poured like water, from one vessel downward into another. At 15° and under ordinary pressure it dissolves in its own volume of water and imparts a somewhat biting, pungent taste to it. It is easily condensed, and is now prepared commercially in this form by pumping the gas into steel cylinders (see Fig. 6) which are kept cold during the process. When the liquid is permitted to escape into the air part of it instantly evaporates, and in so doing absorbs so much heat that another portion is solidified, the solid form strikingly resembling snow in appearance. This snow is very cold and mercury can easily be frozen with it. ~Solid carbon dioxide.~ Cylinders of liquid carbon dioxide are inexpensive, and should be available in every school. To demonstrate the properties of solid carbon dioxide, the cylinder should be placed across the table and supported in such a way that the stopcock end is several inches lower than the other end. A loose bag is made by holding the corners of a handkerchief around the neck of the stopcock, and the cock is then turned on so that the gas rushes out in large quantities. Very quickly a considerable quantity of the snow collects in the handkerchief. To freeze mercury, press a piece of filter paper into a small evaporating dish and pour the mercury upon it. Coil a flat spiral upon the end of a wire, and dip the spiral into the mercury. Place a quantity of solid carbon dioxide upon the mercury and pour 10 cc.-15 cc. of ether over it. In a minute or two the mercury will solidify and may be removed from the dish by the wire serving as a handle. The filter paper is to prevent the mercury from sticking to the dish; the ether dissolves the solid carbon dioxide and promotes its rapid conversion into gas. ~Chemical properties.~ Carbon dioxide is incombustible, since it is, like water, a product of combustion. It does not support combustion, as does nitrogen peroxide, because the oxygen in it is held in very firm chemical union with the carbon. Very strong reducing agents, such as highly heated carbon, can take away half of its oxygen: CO_{2} + C = 2CO. ~Uses.~ The relation of carbon dioxide to plant life has been discussed in a previous chapter. Water highly charged with carbon dioxide is used for making soda water and similar beverages. Since it is a non-supporter of combustion and can be generated readily, carbon dioxide is also used as a fire extinguisher. Some of the portable fire extinguishers are simply devices for generating large amounts of the gas. It is not necessary that all the oxygen should be kept away from the fire in order to smother it. A burning candle is extinguished in air which contains only 2.5% of carbon dioxide. ~Carbonic acid~ (H_{2}CO_{3}). Like most of the oxides of the non-metallic elements, carbon dioxide is an acid anhydride. It combines with water to form an acid of the formula H_{2}CO_{3}, called carbonic acid: H_{2}O + CO_{2} = H_{2}CO_{3}. The acid is, however, very unstable and cannot be isolated. Only a very small amount of it is actually formed when carbon dioxide is passed into water, as is evident from the small solubility of the gas. If, however, a base is present in the water, salts of carbonic acid are formed, and these are quite stable: 2NaOH + H_{2}O + CO_{2} = Na_{2}CO_{3} + 2H_{2}O. ~Action of carbon dioxide on bases.~ This conduct is explained by the principles of reversible reactions. The equation H_{2}O +CO_{2} <--> H_{2}CO_{3} is a reversible equation, and the extent to which the reaction progresses depends upon the relative concentrations of each of the three factors in it. Equilibrium is ordinarily reached when very little H_{2}CO_{3} is formed. If a base is present in the water to combine with the H_{2}CO_{3} as fast as it is formed, all of the CO_{2} is converted into H_{2}CO_{3}, and thence into a carbonate. ~Salts of carbonic acid,--carbonates.~ The carbonates form a very important class of salts. They are found in large quantities in nature, and are often used in chemical processes. Only the carbonates of sodium, potassium, and ammonium are soluble, and these can be made by the action of carbon dioxide on solutions of the bases, as has just been explained. The insoluble carbonates are formed as precipitates when soluble salts are treated with a solution of a soluble carbonate. Thus the insoluble calcium carbonate can be made by bringing together solutions of calcium chloride and sodium carbonate: CaCl_{2} + Na_{2}CO_{3} = CaCO_{3} + 2NaCl. Most of the carbonates are decomposed by heat, yielding an oxide of the metal and carbon dioxide. Thus lime (calcium oxide) is made by strongly heating calcium carbonate: CaCO_{3} = CaO + CO_{2}. ~Acid carbonates.~ Like all acids containing two acid hydrogen atoms, carbonic acid can form both normal and acid salts. The acid carbonates are made by treating a normal carbonate with an excess of carbonic acid. With few exceptions they are very unstable, heat decomposing them even when in solution. ~Action of carbon dioxide on calcium hydroxide.~ If carbon dioxide is passed into clear lime water, calcium carbonate is at first precipitated: H_{2}O + CO_{2} = H_{2}CO_{3}, Ca(OH)_{2} + H_{2}CO_{3} = CaCO_{3} + 2H_{2}O. Advantage is taken of this reaction in testing for the presence of carbon dioxide, as already explained in the chapter on the atmosphere. If the current of carbon dioxide is continued, the precipitate soon dissolves, because the excess of carbonic acid forms calcium acid carbonate which is soluble: CaCO_{3} + H_{2}CO_{3} = Ca(HCO_{3})_{2}. If now the solution is heated, the acid carbonate is decomposed and calcium carbonate once more precipitated: Ca(HCO_{3})_{2} = CaCO_{3} + H_{2}CO_{3}. ~Carbon monoxide (CO).~ Carbon monoxide can be made in a number of ways, the most important of which are the three following: 1. _By the partial oxidation of carbon._ If a slow current of air is conducted over highly heated carbon, the monoxide is formed, thus: C + O = CO It is therefore often formed in stoves when the air draught is insufficient. Water gas, which contains large amounts of carbon monoxide, is made by partially oxidizing carbon with steam: C + H_{2}O = CO + 2H. 2. _By the partial reduction of carbon dioxide._ When carbon dioxide is conducted over highly heated carbon it is reduced to carbon monoxide by the excess of carbon: CO_{2} + C = 2CO. When coal is burning in a stove or grate carbon dioxide is at first formed in the free supply of air, but as the hot gas rises through the glowing coal it is reduced to carbon monoxide. When the carbon monoxide reaches the free air above the coal it takes up oxygen to form carbon dioxide, burning with the blue flame so familiar above a bed of coals, especially in the case of hard coals. 3. _By the decomposition of oxalic acid._ In the laboratory carbon monoxide is usually prepared by the action of concentrated sulphuric acid upon oxalic acid. The latter substance has the formula C_{2}H_{2}O_{4}. The sulphuric acid, owing to its affinity for water, decomposes the oxalic acid, as represented in the equation C_{2}H_{2}O_{4} + (H_{2}SO_{4}) = (H_{2}SO_{4}) + H_{2}O + CO_{2} + CO. ~Properties.~ Carbon monoxide is a light, colorless, almost odorless gas, very difficult to liquefy. Chemically it is very active, combining directly with a great many substances. It has a great affinity for oxygen and is therefore combustible and a good reducing agent. Thus, if carbon monoxide is passed over hot copper oxide, the copper is reduced to the metallic state: CuO + CO = Cu + CO_{2}. When inhaled it combines with the red coloring matter of the blood and in this way prevents the absorption of oxygen, so that even a small quantity of the gas may prove fatal. [Illustration: Fig. 61] ~The reducing power of carbon monoxide.~ Fig. 61 illustrates a method of showing the reducing power of carbon monoxide. The gas is generated by gently heating 7 or 8 g. of oxalic acid with 25 cc. of concentrated sulphuric acid in a 200 cc. flask A. The bottle B contains a solution of sodium hydroxide, which removes the carbon dioxide formed along with the monoxide. C contains a solution of calcium hydroxide to show that the carbon dioxide is completely removed. E is a hard-glass tube containing 1 or 2 g. of copper oxide, which is heated by a burner. The black copper oxide is reduced to reddish metallic copper by the carbon monoxide, which is thereby changed to carbon dioxide. The presence of the carbon dioxide is shown by the precipitate in the calcium hydroxide solution in D. Any unchanged carbon monoxide is collected over water in F. ~Carbon disulphide~ (CS_{2}). Just as carbon combines with oxygen to form carbon dioxide, so it combines with sulphur to form carbon disulphide (CS_{2}). This compound has been described in the chapter on sulphur. ~Hydrocyanic acid~ (_prussic acid_)(HCN). Under the proper conditions carbon unites with nitrogen and hydrogen to form the acid HCN, called hydrocyanic acid. It is a weak, volatile acid, and is therefore easily prepared by treating its salts with sulphuric acid: KCN + H_{2}SO_{4} = KHSO_{4} + HCN. It is most familiar as a gas, though it condenses to a colorless liquid boiling at 26°. It has a peculiar odor, suggesting bitter almonds, and is extremely poisonous either when inhaled or when taken into the stomach. A single drop may cause death. It dissolves readily in water, its solution being commonly called prussic acid. The salts of hydrocyanic acid are called _cyanides_, the cyanides of sodium and potassium being the best known. These are white solids and are extremely poisonous. ~Solutions of potassium cyanide are alkaline.~ A solution of potassium cyanide turns red litmus blue, and must therefore contain hydroxyl ions. The presence of these ions is accounted for in the following way. Although water is so little dissociated into its ions H^{+} and OH^{-} that for most purposes we may neglect the dissociation, it is nevertheless measurably dissociated. Hydrocyanic acid is one of the weakest of acids, and dissociates to an extremely slight extent. When a cyanide such as potassium cyanide dissolves it freely dissociates, and the CN^{-} ions must come to an equilibrium with the H^{+} ions derived from the water: H^{+} + CN^{-} <--> HCN. The result of this equilibrium is that quite a number of H^{+} ions from the water are converted into undissociated HCN molecules. But for every H^{+} ion so removed an OH^{-} ion remains free, and this will give the solution alkaline properties. EXERCISES 1. How can you prove that the composition of the different allotropic forms of carbon is the same? 2. Are lampblack and bone black allotropic forms of carbon? Will equal amounts of heat be liberated in the combustion of 1 g. of each? 3. How could you judge of the relative purity of different forms of carbon? 4. Apart from its color, why should carbon be useful in the preparation of inks and paints? 5. Could asbestos fibers be used to replace the wire in a safety lamp? 6. Why do most acids decompose carbonates? 7. What effect would doubling the pressure have upon the solubility of carbon dioxide in water? 8. What compound would be formed by passing carbon dioxide into a solution of ammonium hydroxide? Write the equation. 9. Write equations for the preparation of K_{2}CO_{3}; of BaCO_{3}; of MgCO_{3}. 10. In what respects are carbonic and sulphurous acids similar? 11. Give three reasons why the reaction which takes place when a solution of calcium acid carbonate is heated, completes itself. 12. How could you distinguish between carbonates and sulphites? 13. How could you distinguish between oxygen, hydrogen, nitrogen, nitrous oxide, and carbon dioxide? 14. Could a solution of sodium hydroxide be substituted for the solution of calcium hydroxide in testing for carbon dioxide? 15. What weight of sodium hydroxide is necessary to neutralize the carbonic acid formed by the action of hydrochloric acid on 100 g. of calcium carbonate? 16. What weight of calcium carbonate would be necessary to prepare sufficient carbon dioxide to saturate 10 l. of water at 15° and under ordinary pressure? 17. On the supposition that calcium carbide costs 12 cents a kilogram, what would be the cost of an amount sufficient to generate 100 l. of acetylene measured at 20° and 740 mm.? 18. How would the volume of a definite amount of carbon monoxide compare with the volume of carbon dioxide formed by its combustion, the measurements being made under the same conditions? CHAPTER XVIII FLAMES,--ILLUMINANTS ~Conditions necessary for flames.~ It has been seen that when two substances unite chemically, with the production of light and heat, the act of union is called combustion. When one of the substances undergoing combustion remains solid at the temperature occasioned by the combustion, light may be given off, but there is no flame. Thus iron wire burning in oxygen throws off a shower of sparks and is brilliantly incandescent, but no flame is seen. When, however, both of the substances are gases or vapors at the temperature reached in the combustion, the act of union is accompanied by a flame. ~Flames from burning liquids or solids.~ Many substances which are liquids or solids at ordinary temperatures burn with a flame because the heat of combustion vaporizes them slowly, and the flame is due to the union of this vapor with the gas supporting the combustion. ~Supporter of combustion.~ That gas which surrounds the flame and constitutes the atmosphere in which the combustion occurs is said to support the combustion. The other gas which issues into this atmosphere is said to be the combustible gas. Thus, in the ordinary combustion of coal gas in the air the coal gas is said to be combustible, while the air is regarded as the supporter of combustion. These terms are entirely relative, however, for a jet of air issuing into an atmosphere of coal gas will burn when ignited, the coal gas supporting the combustion. Ordinarily, when we say that a gas is combustible we mean that it is combustible in an atmosphere of air. [Illustration: Fig. 62] ~Either gas may be the supporter of combustion.~ That the terms _combustible_ and _supporter of combustion_ are merely relative may be shown in the following way: A lamp chimney A is fitted with a cork and glass tubes, as shown in Fig. 62. The tube C should have a diameter of from 12 to 15 mm. A thin sheet of asbestos in which is cut a circular opening about 2 cm. in diameter is placed over the top of the chimney. The opening in the asbestos is closed with the palm of the hand, and gas is admitted to the chimney through the tube B. The air in the chimney is soon expelled through the tube C, and the gas itself is then lighted at the lower end of this tube. The hand is now removed from the opening in the asbestos, when the flame at the end of the tube at once rises and appears at the end within the chimney, as shown in the figure. The excess of coal gas now escapes from the opening in the asbestos and may be lighted. The flame at the top of the asbestos board is due to the combustion of coal gas in air, while the flame within the chimney is due to the combustion of air in coal gas, the air being drawn up through the tube by the escaping gas. ~Appearance of flames.~ The flame caused by the union of hydrogen and oxygen is almost colorless and invisible. Chlorine and hydrogen combine with a pale violet flame, carbon monoxide burns in oxygen with a blue flame, while ammonia burns with a deep yellow flame. The color and appearance of flames are therefore often quite characteristic of the particular combustion which occasions them. ~Structure of flames.~ When the gas undergoing combustion issues from a round opening into an atmosphere of the gas supporting combustion, as is the case with the burning Bunsen burner (Fig. 63), the flame is generally conical in outline. It consists of several distinct cones, one within the other, the boundary between them being marked by differences of color or luminosity. In the simplest flame, of which hydrogen burning in oxygen is a good example, these cones are two in number,--an inner one, formed by unburned gas, and an outer one, usually more or less luminous, consisting of the combining gases. This outer one is in turn surrounded by a third envelope of the products of combustion; this envelope is sometimes invisible, as in the present case, but is sometimes faintly luminous. The lower part of the inner cone of the flame is quite cool and consists of unburned gas. Toward the top of the inner cone the gas has become heated to a high temperature by the burning envelope surrounding it. On reaching the supporter of combustion on the outside it is far above its kindling temperature, and combustion follows with the evolution of much heat. The region of combustion just outside the inner cone is therefore the hottest part of the flame. [Illustration: Fig. 63] ~Oxidizing and reducing flames.~ Since the tip of the outside cone consists of very hot products of combustion mixed with oxygen from the air, a substance capable of oxidation placed in this part of the flame becomes very hot and is easily oxidized. The oxygen with which it combines comes, of course, from the atmosphere, and not from the products of combustion. This outer tip of the flame is called the _oxidizing flame_. At the tip of the inner cone the conditions are quite different. This region consists of a highly heated combustible gas, which has not yet reached a supply of oxygen. If a substance rich in oxygen, such as a metallic oxide, is placed in this region of the flame, the heated gases combine with its oxygen and the substance is reduced. This part of the flame is called the _reducing flame_. These flames are used in testing certain substances, especially minerals. For this purpose they are produced by blowing into a small luminous Bunsen flame from one side through a blowpipe. This is a tube of the shape shown in Fig. 64. The flame is directed in any desired way and has the oxidizing and reducing regions very clearly marked (Fig. 65). It is non-luminous from the same causes which render the open Bunsen burner flame non-luminous, the gases from the lungs serving to furnish oxygen and to dilute the combustible gas. [Illustration: Fig. 64] [Illustration: Fig. 65] ~Luminosity of flames.~ The luminosity of flames is due to a number of distinct causes, and may therefore be increased or diminished in several ways. 1. _Presence of solid matter._ The most obvious of these causes is the presence in the flame of incandescent solid matter. Thus chalk dust sifted into a non-luminous flame renders it luminous. When hydrocarbons form a part of the combustible gas, as they do in nearly all illuminating gases and oils, some carbon is usually set free in the process of combustion. This is made very hot by the flame and becomes incandescent, giving out light. In a well-regulated flame it is afterward burned up, but when the supply of oxygen is insufficient it escapes from the flame as lampblack or soot. That it is temporarily present in a well-burning luminous flame may be demonstrated by holding a cold object, such as a small evaporating dish, in the flame for a few seconds. This cold object cools the carbon below its kindling temperature, and it is deposited on the object as soot. 2. _Pressure._ A second factor in the luminosity of flames is the pressure under which the gases are burning. Under increased pressure there is more matter in a given volume of a gas, and the chemical action is more energetic than when the gases are rarefied. Consequently there is more heat and light. A candle burning on a high mountain gives less light than when it burns at the sea level. If the gas is diluted with a non-combustible gas, the effect is the same as if it is rarefied, for under these conditions there is less combustible gas in a given volume. 3. _Temperature._ The luminosity also depends upon the temperature attained in the combustion. In general the hotter the flame the greater the luminosity; hence cooling the gases before combustion diminishes the luminosity of the flame they will make, because it diminishes the temperature attained in the combustion. Thus the luminosity of the Bunsen flame is largely diminished by the air drawn up with the gas. This is due in part to the fact that the burning gas is diluted and cooled by the air drawn in. The oxygen thus introduced into the flame also causes the combustion of the hot particles of carbon which would otherwise tend to make the flame luminous. ~Illuminating and fuel gases.~ A number of mixtures of combustible gases, consisting largely of carbon compounds and hydrogen, find extensive use for the production of light and heat. The three chief varieties are coal gas, water gas, and natural gas. The use of acetylene gas has already been referred to. ~Coal gas.~ Coal gas is made by heating bituminous coal in large retorts out of contact with the air. Soft or bituminous coal contains, in addition to large amounts of carbon, considerable quantities of compounds of hydrogen, oxygen, nitrogen, and sulphur. When distilled the nitrogen is liberated partly in the form of ammonia and cyanides and partly as free nitrogen gas; the sulphur is converted into hydrogen sulphide, carbon disulphide, and oxides of sulphur; the oxygen into water and oxides of carbon. The remaining hydrogen is set free partly as hydrogen and partly in combination with carbon in the form of hydrocarbons. The most important of these is methane, with smaller quantities of many others, some of which are liquids or solids at ordinary temperatures. The great bulk of the carbon remains behind as coke and retort carbon. ~The manufacture of coal gas.~ In the manufacture of coal gas it is necessary to separate from the volatile constituents formed by the heating of the coal all those substances which are either solid or liquid at ordinary temperature, since these would clog the gas pipes. Certain gaseous constituents, such as hydrogen sulphide and ammonia, must also be removed. The method used to accomplish this is shown in Fig. 66. The coal is heated in air-tight retorts illustrated by A. The volatile products escape through the pipe X and bubble into the tarry liquid in the large pipe B, known as the _hydraulic main_, which runs at right angles to the retorts. Here is deposited the greater portion of the solid and liquid products, forming a tarry mass known as _coal tar_. Much of the ammonia also remains dissolved in this liquid. The partially purified gas then passes into the pipes C, which serve to cool it and further remove the solid and liquid matter. The gas then passes into D, which is filled with coke over which a jet of water is sprayed. The water still further cools the gas and at the same time partially removes such gaseous products as hydrogen sulphide and ammonia, which are soluble in water. In E the gas passes over some material such as lime, which removes the last portions of the sulphur compounds as well as much of the carbon dioxide present. From E the gas passes into the large gas holder F, from which it is distributed through pipes to the places where it is burned. [Illustration: Fig. 66] One ton of good gas coal yields approximately 10,000 cu. ft. of gas, 1400 lb. of coke, 120 lb. of tar, and 20 gal. of ammoniacal liquor. Not only is the ammonia obtained in the manufacture of the gas of great importance, but the coal tar also serves as the source of many very useful substances, as will be explained in Chapter XXXII. ~Water gas.~ Water gas is essentially a mixture of carbon monoxide and hydrogen. It is made by passing steam over very hot anthracite coal, when the reaction shown in the following equation takes place: C + H_{2}O = CO + 2H. When required merely to produce heat the gas is at once ready for use. When made for illuminating purposes it must be enriched, that is, illuminants must be added, since both carbon monoxide and hydrogen burn with non-luminous flames. This is accomplished by passing it into heaters containing highly heated petroleum oils. The gas takes up hydrocarbon gases formed in the decomposition of the petroleum oils, which make it burn with a luminous flame. Water gas is very effective as a fuel, since both carbon monoxide and hydrogen burn with very hot flames. It has little odor and is very poisonous. Its use is therefore attended with some risk, since leaks in pipes are very likely to escape notice. ~Natural gas.~ This substance, so abundant in many localities, varies much in composition, but is composed principally of methane. When used for lighting purposes it is usually burned in a burner resembling an open Bunsen, the illumination being furnished by an incandescent mantle. This is the case in the familiar Welsbach burner. Contrary to statements frequently made, natural gas contains no free hydrogen. TABLE SHOWING COMPOSITION OF GASES =====================+================+========+========+========== | PENNSYLVANIA | COAL | WATER | ENRICHED | NATURAL | GAS | GAS | WATER | GAS | | | GAS ---------------------+----------------+--------+--------+---------- Hydrogen | | 41.3 | 52.88 | 30.00 Methane | 90.64 | 43.6 | 2.16 | 24.00 Illuminants | | 3.9 | | 12.05 Carbon monoxide | | 6.4 | 36.80 | 29.00 Carbon dioxide | 0.30 | 2.0 | 3.47 | 0.30 Nitrogen | 9.06 | 1.2 | 4.69 | 2.50 Oxygen | | 0.3 | | 1.50 Hydrocarbon vapors | | 1.5 | | 1.50 =====================+================+========+========+========== These are analyses of actual samples, and may be taken as about the average for the various kinds of gases. Any one of these may vary considerably. The nitrogen and oxygen in most cases is due to a slight admixture of air which is difficult to exclude entirely in the manufacture and handling of gases. ~Fuels.~ A variety of substances are used as fuels, the most important of them being wood, coal, and the various gases mentioned above. Wood consists mainly of compounds of carbon, hydrogen, and oxygen. The composition of coal and the fuel gases has been given. Since these fuels are composed principally of carbon and hydrogen or their compounds, the chief products of combustion are carbon dioxide and water. The practice of heating rooms with portable gas or oil stoves with no provision for removing the products of combustion is to be condemned, since the carbon dioxide is generated in sufficient quantities to render the air unfit for breathing. Rooms so heated also become very damp from the large amount of water vapor formed in the combustion, and which in cold weather condenses on the window glass, causing the glass to "sweat." Both coal and wood contain a certain amount of mineral substances which constitute the ashes. ~The electric furnace.~ In recent years electric furnaces have come into wide use in operations requiring a very high temperature. Temperatures as high as 3500° can be easily reached, whereas the hottest oxyhydrogen flame is not much above 2000°. These furnaces are constructed on one of two general principles. [Illustration: Fig. 67] 1. _Arc furnaces._ In the one type the source of heat is an electric arc formed between carbon electrodes separated a little from each other, as shown in Fig. 67. The substance to be heated is placed in a vessel, usually a graphite crucible, just below the arc. The electrodes and crucible are surrounded by materials which fuse with great difficulty, such as magnesium oxide, the walls of the furnace being so shaped as to reflect the heat downwards upon the contents of the crucible. [Illustration: Fig. 68] 2. _Resistance furnaces._ In the other type of furnace the heat is generated by the resistance offered to the current in its passage through the furnace. In its simplest form it may be represented by Fig. 68. The furnace is merely a rectangular box built up of loose bricks. The electrodes E, each consisting of a bundle of carbon rods, are introduced through the sides of the furnace. The materials to be heated, C, are filled into the furnace up to the electrodes, and a layer of broken coke is arranged so as to extend from one electrode to the other. More of the charge is then placed on top of the coke. In passing through the broken coke the electrical current encounters great resistance. This generates great heat, and the charge surrounding the coke is brought to a very high temperature. The advantage of this type of furnace is that the temperature can be regulated to any desired intensity. EXERCISES 1. Why does charcoal usually burn with no flame? How do you account for the flame sometimes observed when it burns? 2. How do you account for the fact that a candle burns with a flame? 3. What two properties must the mantle used in the Welsbach lamp possess? 4. (a) In what respects does the use of the Welsbach mantle resemble that of lime in the calcium light? (b) If the mantle were made of carbon, would it serve the same purpose? 5. Would anthracite coal be suitable for the manufacture of coal gas? 6. How could you prove the formation of carbon dioxide and water in the combustion of illuminating gases? 7. Suggest a probable way in which natural gas has been formed. 8. Coal frequently contains a sulphide of iron. (a) What two sulphur compounds are likely to be formed when gas is made from such coal? (b) Suggest some suitable method for the removal of these compounds. 9. Why does the use of the bellows on the blacksmith's forge cause a more intense heat? 10. What volume of oxygen is necessary to burn 100 l. of marsh gas and what volume of carbon dioxide would be formed, all of the gases being measured under standard conditions? 11. Suppose a cubic meter of Pennsylvania natural gas, measured under standard conditions, were to be burned. How much water by weight would result? CHAPTER XIX MOLECULAR WEIGHTS, ATOMIC WEIGHTS, FORMULAS ~Introduction.~ In the chapter on The Atomic Theory, it was shown that if it were true that two elements uniting to form a compound always combined in the ratio of one atom of one element to one atom of the other element, it would be a very easy matter to decide upon figures which would represent the relative weights of the different atoms. It would only be necessary to select some one element as a standard and determine the weight of every element which combines with a definite weight (say 1 g.) of the standard element. The figures so obtained would evidently represent the relative weights of the atoms. But the law of multiple proportion at once reminds us that two elements may unite in several proportions; and there is no simple way to determine the number of atoms present in the molecule of any compound. Consequently the problem of deciding upon the relative atomic weights is not an easy one. To the solution of this problem we must now turn. ~Dalton's method of determining atomic weights.~ When Dalton first advanced the atomic theory he attempted to solve this problem by very simple methods. He thought that when only one compound of two elements is known it is reasonable to suppose that it contains one atom of each element. He therefore gave the formula HO to water, and HN to ammonia. When more than two compounds were known he assumed that the most familiar or the most stable one had the simple formula. He then determined the atomic weight as explained above. The results he obtained were contradictory and very far from satisfactory, and it was soon seen that some other method, resting on much more scientific grounds, must be found to decide what compounds, if any, have a single atom of each element present. ~Determination of atomic weights.~ Three distinct steps are involved in the determination of the atomic weight of an element: (1) determination of the equivalent, (2) determination of molecular weights of its compounds, and (3) deduction of the exact atomic weight from the equivalent and molecular weights. ~1. Determination of the equivalent.~ By the equivalent of an element is meant the weight of the element which will combine with a fixed weight of some other element chosen as a standard. It has already been explained that oxygen has been selected as the standard element for atomic weights, with a weight of 16. This same standard will serve very well as a standard for equivalents. _The equivalent of an element is the weight of the element which will combine with 16 g. of oxygen._ Thus 16 g. of oxygen combines with 16.03 g. of sulphur, 65.4 g. of zinc, 215.86 g. of silver, 70.9 g. of chlorine. These figures, therefore, represent the equivalent weights of these elements. ~Relation of atomic weights to equivalents.~ According to the atomic theory combination always takes place between whole numbers of atoms. Thus one atom unites with one other, or with two or three; or two atoms may unite with three, or three with five, and so on. When oxygen combines with zinc the combination must be between definite numbers of the two kinds of atoms. Experiment shows that these two elements combine in the ratio of 16 g. of oxygen to 65.4 g. of zinc. If one atom of oxygen combines with one atom of zinc, then this ratio must be the ratio between the weights of the two atoms. If one atom of oxygen combines with two atoms of zinc, then the ratio between the weights of the two atoms will be 16: 32.7. If two atoms of oxygen combine with one atom of zinc, the ratio by weight between the two atoms will be 8: 65.4. It is evident, therefore, that the real atomic weight of an element must be some multiple or submultiple of the equivalent; in other words, the equivalent multiplied by 1/2, 1, 2, or 3 will give the atomic weight. ~Combining weights.~ A very interesting relation holds good between the equivalents of the various elements. We have just seen that the figures 16.03, 65.4, 215.86, and 70.9 are the equivalents respectively of sulphur, zinc, silver, and chlorine. These same figures represent the ratios by weight in which these elements combine among themselves. Thus 215.86 g. of silver combine with 70.9 g. of chlorine and with 2 × 16.03 g. of sulphur. 65.4 g. of zinc combine with 70.9 g. of chlorine and 2 × 16.03 g. of sulphur. By taking the equivalent or some multiple of it a value can be obtained for each element which will represent its combining value, and for this reason is called its _combining weight_. It is important to notice that the fact that a combining weight can be obtained for each element is not a part of a theory, but is the direct result of experiment. ~Elements with more than one equivalent.~ It will be remembered that oxygen combines with hydrogen in two ratios. In one case 16 g. of oxygen combine with 2.016 g. of hydrogen to form water; in the other 16 g. of oxygen combine with 1.008 g. of hydrogen to form hydrogen dioxide. The equivalents of hydrogen are therefore 2.016 and 1.008. Barium combines with oxygen in two proportions: in barium oxide the proportion is 16 g. of oxygen to 137.4 g. of barium; in barium dioxide the proportion is 16 g. of oxygen to 68.7 g. of barium. In each case one equivalent is a simple multiple of the other, so the fact that there may be two equivalents does not add to the uncertainty. All we knew before was that the true atomic weight is some multiple of the equivalent. ~2. The determination of molecular weights.~ To decide the question as to which multiple of the equivalent correctly represents the atomic weight of an element, it has been found necessary to devise a method of determining the molecular weights of compounds containing the element in question. Since the molecular weight of a compound is merely the sum of the weights of all the atoms present in it, it would seem to be impossible to determine the molecular weight of a compound without first knowing the atomic weights of the constituent atoms, and how many atoms of each element are present in the molecule. But certain facts have been discovered which suggest a way in which this can be done. ~Avogadro's hypothesis.~ We have seen that the laws of Boyle, Charles, and Gay-Lussac apply to all gases irrespective of their chemical character. This would lead to the inference that the structure of gases must be quite simple, and that it is much the same in all gases. In 1811 Avogadro, an Italian physicist, suggested that if we assume all gases under the same conditions of temperature and pressure to have the same number of molecules in a given volume, we shall have a probable explanation of the simplicity of the gas laws. It is difficult to prove the truth of this hypothesis by a simple experiment, but there are so many facts known which are in complete harmony with this suggestion that there is little doubt that it expresses the truth. Avogadro's hypothesis may be stated thus: _Equal volumes of all gases under the same conditions of temperature and pressure contain the same number of molecules._ ~Avogadro's hypothesis and molecular weights.~ Assuming that Avogadro's hypothesis is correct, we have a very simple means for deciding upon the relative weights of molecules; for if equal volumes of two gases contain the same number of molecules, the weights of the two volumes must be in the same ratio as the weights of the individual molecules which they contain. If we adopt some one gas as a standard, we can express the weights of all other gases as compared with this one, and the same figures will express the relative weights of the molecules of which the gases are composed. ~Oxygen as the standard.~ It is important that the same standard should be adopted for the determination of molecular weights as has been decided upon for atomic weights and equivalents, so that the three values may be in harmony with each other. Accordingly it is best to adopt oxygen as the standard element with which to compare the molecular weights of other gases, being careful to keep the oxygen atom equal to 16. ~The oxygen molecule contains two atoms.~ One point must not be overlooked, however. We desire to have our unit, the oxygen _atom_, equal to 16. The method of comparing the weights of gases just suggested compares the molecules of the gases with the _molecule_ of oxygen. Is the molecule and the atom of oxygen the same thing? This question is answered by the following considerations. We have seen that when steam is formed by the union of oxygen and hydrogen, two volumes of hydrogen combine with one volume of oxygen to form two volumes of steam. Let us suppose that the one volume of oxygen contains 100 molecules; then the two volumes of steam must, according to Avogadro's hypothesis, contain 200 molecules. But each of these 200 molecules must contain at least one atom of oxygen, or 200 in all, and these 200 atoms came from 100 molecules of oxygen. It follows that each molecule of oxygen must contain at least two atoms of oxygen. Evidently this reasoning merely shows that there are _at least_ two atoms in the oxygen molecule. There may be more than that, but as there is no evidence to this effect, we assume that the molecule contains two atoms only. It is evident that if we wish to retain the value 16 for the atom of oxygen we must take twice this value, or 32, for the value of the oxygen molecule, when using it as a standard for molecular weights. ~Determination of the molecular weights of gases from their weights compared with oxygen.~ Assuming the molecular weight of oxygen to be 32, Avogadro's hypothesis gives us a ready means for determining the molecular weight of any other gas, for all that is required is to know its weight compared with that of an equal volume of oxygen. For example, 1 l. of chlorine is found by experiment to weigh 2.216 times as much as 1 l. of oxygen. The molecular weight of chlorine must therefore be 2.216 × 32, or 70.91. If, instead of comparing the relative weights of 1 l. of the two gases, we select such a volume of oxygen as will weigh 32 g., or the weight in grams corresponding to the molecular weight of the gas, the calculation is much simplified. It has been found that 32 g. of oxygen, under standard conditions, measure 22.4 l. This same volume of hydrogen weighs 2.019 g.; of chlorine 70.9 g.; of hydrochloric acid 36.458 g. The weights of these equal volumes must be proportional to their molecular weights, and since the weight of the oxygen is the same as the value of its molecular weight, so too will the weights of the 22.4 l. of the other gases be equal to the value of their molecular weights. As a summary we can then make the following statement: _The molecular weight of any gas may be determined by calculating the weight of 22.4 l. of the gas, measured under standard conditions._ ~Determination of molecular weights from density of gases.~ In an actual experiment it is easier to determine the density of a gas than the weight of a definite volume of it. The density of a gas is usually defined as its weight compared with that of an equal volume of air. Having determined the density of a gas, its weight compared with oxygen may be determined by multiplying its density by the ratio between the weights of air and oxygen. This ratio is 0.9046. To compare it with our standard for atomic weights we must further multiply it by 32, since the standard is 1/32 the weight of oxygen molecules. The steps then are these: 1. Determine the density of the gas (its weight compared with air). 2. Multiply by 0.9046 to make the comparison with oxygen molecules. 3. Multiply by 32 to make the comparison with the unit for atomic weights. We have, then, the formula: molecular weight = density × 0.9046 × 32; or, still more briefly, M. = D. × 28.9. The value found by this method for the determination of molecular weights will of course agree with those found by calculating the weight of 22.4 l. of the gas, since both methods depend on the same principles. [Illustration: Fig. 69] ~Determination of densities of gases.~ The relative weights of equal volumes of two gases can be easily determined. The following is one of the methods used. A small flask, such as is shown in Fig. 69, is filled with one of the gases, and after the temperature and pressure have been noted the flask is sealed up and weighed. The tip of the sealed end is then broken off, the flask filled with the second gas, and its weight determined. If the weight of the empty flask is subtracted from these two weighings, the relative weights of the gases is readily found. ~3. Deduction of atomic weights from molecular weights and equivalents.~ We have now seen how the equivalent of an element and the molecular weight of compounds containing the element can be obtained. Let us see how it is possible to decide which multiple of the equivalent really is the true atomic weight. As an example, let us suppose that the equivalent of nitrogen has been found to be 7.02 and that it is desired to obtain its atomic weight. The next step is to obtain the molecular weights of a large number of compounds containing nitrogen. The following will serve: ==================+============+=============+================+============== | | APPROXIMATE | PERCENTAGE OF | PART OF | DENSITY BY | MOLECULAR | NITROGEN BY | MOLECULAR | EXPERIMENT | WEIGHT | EXPERIMENT | WEIGHT DUE | | (D. × 28.9) | | TO NITROGEN ------------------+------------+-------------+----------------+-------------- Nitrogen gas | 0.9671 | 27.95 | 100.00 | 27.95 Nitrous oxide | 1.527 | 44.13 | 63.70 | 27.11 Nitric oxide | 1.0384 | 30.00 | 46.74 | 14.02 Nitrogen peroxide | 1.580 | 45.66 | 30.49 | 13.90 Ammonia | 0.591 | 17.05 | 82.28 | 14.03 Nitric acid | 2.180 | 63.06 | 22.27 | 14.03 Hydrocyanic acid | 0.930 | 26.87 | 51.90 | 13.94 ==================+============+=============+================+============== ~Method of calculation.~ The densities of the various gases in the first column of this table are determined by experiment, and are fairly accurate but not entirely so. By multiplying these densities by 28.9 the molecular weights of the compounds as given in the second column are obtained. By chemical analysis it is possible to determine the percentage composition of these substances, and the percentages of nitrogen in them as determined by analysis are given in the third column. If each of these molecular weights is multiplied in turn by the percentage of nitrogen in the compound, the product will be the weight of the nitrogen in the molecular weight of the compound. This will be the sum of the weights of the nitrogen atoms in the molecule. These values are given in the fourth column in the table. If a large number of compounds containing nitrogen are studied in this way, it is probable that there will be included in the list at least one substance whose molecule contains a single nitrogen atom. In this case the number in the fourth column will be the approximate atomic weight of nitrogen. On comparing the values for nitrogen in the table it will be seen that a number which is approximately 14 is the smallest, and that the others are multiples of this. These compounds of higher value, therefore, contain more than one nitrogen atom in the molecule. ~Accurate determination of atomic weights.~ Molecular weights cannot be determined very accurately, and consequently the part in them due to nitrogen is a little uncertain, as will be seen in the table. All we can tell by this method is that the true weight is very near 14. The equivalent can however be determined very accurately, and we have seen that it is some multiple or submultiple of the true atomic weight. Since molecular-weight determinations have shown that in the case of nitrogen the atomic weight is near 14, and we have found the equivalent to be 7.02, it is evident that the true atomic weight is twice the equivalent, or 7.02 × 2 = 14.04. ~Summary.~ These, then, are the steps necessary to establish the atomic weight of an element. 1. Determine the equivalent accurately by analysis. 2. Determine the molecular weight of a large number of compounds of the element, and by analysis the part of the molecular weight due to the element. The smallest number so obtained will be approximately the atomic weight. 3. Multiply the equivalent by the small whole number (usually 1, 2, or 3), which will make a number very close to the approximate atomic weight. The figure so obtained will be the true atomic weight. ~Molecular weights of the elements.~ It will be noticed that the molecular weight of nitrogen obtained by multiplying its density by 28.9 is 28.08. Yet the atomic weight of nitrogen as deduced from a study of its gaseous compounds is 14.04. The simplest explanation that can be given for this is that the gaseous nitrogen is made up of molecules, each of which contains two atoms. In this respect it resembles oxygen; for we have seen that an entirely different line of reasoning leads us to believe that the molecule of oxygen contains two atoms. When we wish to indicate molecules of these gases the symbols N_{2} and O_{2} should be used. When we desire to merely show the weights taking part in a reaction this is not necessary. The vapor densities of many of the elements show that, like oxygen and nitrogen, their molecules consist of two atoms. In other cases, particularly among the metals, the molecule and the atom are identical. Still other elements have four atoms in their molecules. While oxygen contains two atoms in its molecules, a study of ozone has led to the conclusion that it has three. The formation of ozone from oxygen can therefore be represented by the equation 3O_{2} = 2O_{3}. ~Other methods of determining molecular weights.~ It will be noticed that Avogadro's law gives us a method by which we can determine the relative weights of the molecules of two gases because it enables us to tell when we are dealing with an equal number of the two kinds of molecules. If by any other means we can get this information, we can make use of the knowledge so gained to determine the molecular weights of the two substances. ~Raoult's laws.~ Two laws have been discovered which give us just such information. They are known as Raoult's laws, and can be stated as follows: 1. _When weights of substances which are proportional to their molecular weights are dissolved in the same weight of solvent, the rise of the boiling point is the same in each case._ 2. _When weights of substances which are proportional to their molecular weights are dissolved in the same weight of solvent, the lowering of the freezing point is the same in each case._ By taking advantage of these laws it is possible to determine when two solutions contain the same number of molecules of two dissolved substances, and consequently the relative molecular weights of the two substances. ~Law of Dulong and Petit.~ In 1819 Dulong and Petit discovered a very interesting relation between the atomic weight of an element and its specific heat, which holds true for elements in the solid state. If equal weights of two solids, say, lead and silver, are heated through the same range of temperature, as from 10° to 20°, it is found that very different amounts of heat are required. The amount of heat required to change the temperature of a solid or a liquid by a definite amount compared with the amount required to change the temperature of an equal weight of water by the same amount is called its specific heat. Dulong and Petit discovered the following law: _The specific heat of an element in the solid form multiplied by its atomic weight is approximately equal to the constant 6.25._ That is, at. wt. × sp. ht. = 6.25. Consequently, 6.25 at. wt. = -------- sp. ht. This law is not very accurate, but it is often possible by means of it to decide upon what multiple of the equivalent is the real atomic weight. Thus the specific heat of iron is found by experiment to be 0.112, and its equivalent is 27.95. 6.25 ÷ 0.112 = 55.8. We see, therefore, that the atomic weight is twice the equivalent, or 55.9. ~How formulas are determined.~ It will be well in connection with molecular weights to consider how the formula of a compound is decided upon, for the two subjects are very closely associated. Some examples will make clear the method followed. The molecular weight of a substance containing hydrogen and chlorine was 36.4. By analysis 36.4 parts of the substance was found to contain 1 part of hydrogen and 35.4 parts of chlorine. As these are the simple atomic weights of the two elements, the formula of the compound must be HCl. A substance consisting of oxygen and hydrogen was found to have a molecular weight of 34. Analysis showed that in 34 parts of the substance there were 2 parts of hydrogen and 32 parts of oxygen. Dividing these figures by the atomic weights of the two elements, we get 2 ÷ 1 = 2 for H; 32 ÷ 16 = 2 for O. The formula is therefore H_{2}O_{2}. A substance containing 2.04% H, 32.6% S, and 65.3% O was found to have a molecular weight of 98. In these 98 parts of the substance there are 98 × 2.04% = 2 parts of H, 98 × 32.6% = 32 parts of S, and 98 × 65.3% = 64 parts of O. If the molecule weighs 98, the hydrogen atoms present must together weigh 2, the sulphur atoms 32, and the oxygen atoms 64. Dividing these figures by the respective atomic weights of the three elements, we have, for H, 2 ÷ 1 = 2 atoms; for S, 32 ÷ 32 = 1 atom; for O, 64 ÷ 16 = 4 atoms. Hence the formula is H_{2}SO_{4}. We have, then, this general procedure: Find the percentage composition of the substance and also its molecular weight. Multiply the molecular weight successively by the percentage of each element present, to find the amount of the element in the molecular weight of the compound. The figures so obtained will be the respective parts of the molecular weight due to the several atoms. Divide by the atomic weights of the respective elements, and the quotient will be the number of atoms present. ~Avogadro's hypothesis and chemical calculations.~ This law simplifies many chemical calculations. 1. _Application to volume relations in gaseous reactions._ Since equal volumes of gases contain an equal number of molecules, it follows that when an equal number of gaseous molecules of two or more gases take part in a reaction, the reaction will involve equal volumes of the gases. In the equation C_{2}H_{2}O_{4} = H_{2}O + CO_{2} + CO, since 1 molecule of each of the gases CO_{2} and CO is set free from each molecule of oxalic acid, the two substances must always be set free in equal volumes. Acetylene burns in accordance with the equation 2C_{2}H_{2} + 5O_{2} = 4CO_{2} + 2H_{2}O. Hence 2 volumes of acetylene will react with 5 volumes of oxygen to form 4 volumes of carbon dioxide and 2 volumes of steam. That the volume relations may be correct a gaseous element must be given its molecular formula. Thus oxygen must be written O_{2} and not 2O. 2. _Application to weights of gases._ It will be recalled that the molecular weight of a gas is determined by ascertaining the weight of 22.4 l. of the gas. This weight in grams is called the _gram-molecular weight_ of a gas. If the molecular weight of any gas is known, the weight of a liter of the gas under standard conditions may be determined by dividing its gram-molecular weight by 22.4. Thus the gram-molecular weight of a hydrochloric acid gas is 36.458. A liter of the gas will therefore weigh 36.458 ÷ 22.4 = 1.627 g. EXERCISES 1. From the following data calculate the atomic weight of sulphur. The equivalent, as obtained by an analysis of sulphur dioxide, is 16.03. The densities and compositions of a number of compounds containing sulphur are as follows: NAME DENSITY COMPOSITION BY PERCENTAGE Hydrosulphuric acid 1.1791 S = 94.11 H = 5.89 Sulphur dioxide 2.222 S = 50.05 O = 49.95 Sulphur trioxide 2.74 S = 40.05 O = 59.95 Sulphur chloride 4.70 S = 47.48 Cl = 52.52 Sulphuryl chloride 4.64 S = 23.75 Cl = 52.53 O = 23.70 Carbon disulphide 2.68 S = 84.24 C = 15.76 2. Calculate the formulas for compounds of the following compositions: MOLECULAR WEIGHT (1) S = 39.07% O = 58.49% H = 2.44% 81.0 (2) Ca = 29.40 S = 23.56 O = 47.04 136.2 (3) K = 38.67 N = 13.88 O = 47.45 101.2 3. The molecular weight of ammonia is 17.06; of sulphur dioxide is 64.06; of chlorine is 70.9. From the molecular weight calculate the weight of 1 l. of each of these gases. Compare your results with the table on the back cover of the book. 4. From the molecular weight of the same gases calculate the density of each, referred to air as a standard. 5. A mixture of 50 cc. of carbon monoxide and 50 cc. of oxygen was exploded in a eudiometer, (a) What gases remained in the tube after the explosion? (b) What was the volume of each? 6. In what proportion must acetylene and oxygen be mixed to produce the greatest explosion? 7. Solve Problem 18, Chapter XVII, without using molecular weights. Compare your results. 8. Solve Problem 10, Chapter XVIII, without using molecular weights. Compare your results. 9. The specific heat of aluminium is 0.214; of lead is 0.031. From these specific heats calculate the atomic weights of each of the elements. CHAPTER XX THE PHOSPHORUS FAMILY ================================================== | | ATOMIC | | MELTING | SYMBOL | WEIGHT | DENSITY | POINT -----------+--------+---------+---------+--------- Phosphorus | P | 31.0 | 1.8 | 43.3° Arsenic | As | 75.0 | 5.73 | --- Antimony | Sb | 120.2 | 6.7 | 432° Bismuth | Bi | 208.5 | 9.8 | 270° ================================================== ~The family.~ The elements constituting this family belong in the same group with nitrogen and therefore resemble it in a general way. They exhibit a regular gradation of physical properties, as is shown in the above table. The same general gradation is also found in their chemical properties, phosphorus being an acid-forming element, while bismuth is essentially a metal. The other two elements are intermediate in properties. ~Compounds.~ In general the elements of the family form compounds having similar composition, as is shown in the following table: PH_{3} PCl_{3} PCl_{5} P_{2}O_{3} P_{2}O_{5} AsH_{3} AsCl_{3} AsCl_{5} As_{2}O_{3} As_{2}O_{5} SbH_{3} SbCl_{3} SbCl_{5} Sb_{2}O_{3} Sb_{2}O_{5} .... BiCl_{3} BiCl_{5} Bi_{2}O_{3} Bi_{2}O_{5} In the case of phosphorus, arsenic, and antimony the oxides are acid anhydrides. Salts of at least four acids of each of these three elements are known, the free acid in some instances being unstable. The relation of these acids to the corresponding anhydrides may be illustrated as follows, phosphorus being taken as an example: P_{2}O_{3} + 3H_{2}O = 2H_{3}PO_{3} (phosphorous acid). P_{2}O_{5} + 3H_{2}O = 2H_{3}PO_{4} (phosphoric acid). P_{2}O_{5} + 2H_{2}O = H_{4}P_{2}O_{7} (pyrophosphoric acid). P_{2}O_{5} + H_{2}O = 2HPO_{3} (metaphosphoric acid). PHOSPHORUS ~History.~ The element phosphorus was discovered by the alchemist Brand, of Hamburg, in 1669, while searching for the philosopher's stone. Owing to its peculiar properties and the secrecy which was maintained about its preparation, it remained a very rare and costly substance until the demand for it in the manufacture of matches brought about its production on a large scale. ~Occurrence.~ Owing to its great chemical activity phosphorus never occurs free in nature. In the form of phosphates it is very abundant and widely distributed. _Phosphorite_ and _sombrerite_ are mineral forms of calcium phosphate, while _apatite_ consists of calcium phosphate together with calcium fluoride or chloride. These minerals form very large deposits and are extensively mined for use as fertilizers. Calcium phosphate is a constituent of all fertile soil, having been supplied to the soil by the disintegration of rocks containing it. It is the chief mineral constituent of bones of animals, and bone ash is therefore nearly pure calcium phosphate. ~Preparation.~ Phosphorus is now manufactured from bone ash or a pure mineral phosphate by heating the phosphate with sand and carbon in an electric furnace. The materials are fed in at M (Fig. 70) by the feed screw F. The phosphorus vapor escapes at P and is condensed under water, while the calcium silicate is tapped off as a liquid at S. The phosphorus obtained in this way is quite impure, and is purified by distillation. [Illustration: Fig. 70] ~Explanation of the reaction.~ To understand the reaction which occurs, it must be remembered that a volatile acid anhydride is expelled from its salts when heated with an anhydride which is not volatile. Thus, when sodium carbonate and silicon dioxide are heated together the following reaction takes place: Na_{2}CO_{3} + SiO_{2} = Na_{2}SiO_{3} + CO_{2}. Silicon dioxide is a less volatile anhydride than phosphoric anhydride (P_{2}O_{5}), and when strongly heated with a phosphate the phosphoric anhydride is driven out, thus: Ca_{3}(PO_{4})_{2} + 3SiO_{2} = 3CaSiO_{3} + P_{2}O_{5}. If carbon is added before the heat is applied, the P_{2}O_{5} is reduced to phosphorus at the same time, according to the equation P_{2}O_{5} + 5C = 2P + 5CO. ~Physical properties.~ The purified phosphorus is a pale yellowish, translucent, waxy solid which melts at 43.3° and boils at 269°. It can therefore be cast into any convenient form under warm water, and is usually sold in the market in the form of sticks. It is quite soft and can be easily cut with a knife, but this must always be done while the element is covered with water, since it is extremely inflammable, and the friction of the knife blade is almost sure to set it on fire if cut in the air. It is not soluble in water, but is freely soluble in some other liquids, notably in carbon disulphide. Its density is 1.8. ~Chemical properties.~ Exposed to the air phosphorus slowly combines with oxygen, and in so doing emits a pale light, or phosphorescence, which can be seen only in a dark place. The heat of the room may easily raise the temperature to the kindling point of phosphorus, when it burns with a sputtering flame, giving off dense fumes of oxide of phosphorus. It burns with dazzling brilliancy in oxygen, and combines directly with many other elements, especially with sulphur and the halogens. On account of its great affinity for oxygen it is always preserved under water. Phosphorus is very poisonous, from 0.2 to 0.3 gram being a fatal dose. Ground up with flour and water or similar substances, it is often used as a poison for rats and other vermin. ~Precaution.~ The heat of the body is sufficient to raise phosphorus above its kindling temperature, and for this reason it should always be handled with forceps and never with the bare fingers. Burns occasioned by it are very painful and slow in healing. ~Red phosphorus.~ On standing, yellow phosphorus gradually undergoes a remarkable change, being converted into a dark red powder which has a density of 2.1. It no longer takes fire easily, neither does it dissolve in carbon disulphide. It is not poisonous and, in fact, seems to be an entirely different substance. The velocity of this change increases with rise in temperature, and the red phosphorus is therefore prepared by heating the yellow just below the boiling point (250°-300°). When distilled and quickly condensed the red form changes back to the yellow. This is in accordance with the general rule that when a substance capable of existing in several allotropic forms is condensed from a gas or crystallized from the liquid state, the more unstable variety forms first, and this then passes into the more stable forms. ~Matches.~ The chief use of phosphorus is in the manufacture of matches. Common matches are made by first dipping the match sticks into some inflammable substance, such as melted paraffin, and afterward into a paste consisting of (1) phosphorus, (2) some oxidizing substance, such as manganese dioxide or potassium chlorate, and (3) a binding material, usually some kind of glue. On friction the phosphorus is ignited, the combustion being sustained by the oxidizing agent and communicated to the wood by the burning paraffin. In sulphur matches the paraffin is replaced by sulphur. In safety matches _red_ phosphorus, an oxidizing agent, and some gritty material such as emery is placed on the side of the box, while the match tip is provided as before with an oxidizing agent and an easily oxidized substance, usually antimony sulphide. The match cannot be ignited easily by friction, save on the prepared surface. ~Compounds of phosphorus with hydrogen.~ Phosphorus forms several compounds with hydrogen, the best known of which is phosphine (PH_{3}) analogous to ammonia (NH_{3}). ~Preparation of phosphine.~ Phosphine is usually made by heating phosphorus with a strong solution of potassium hydroxide, the reaction being a complicated one. [Illustration: Fig. 71] The experiment can be conveniently made in the apparatus shown in Fig. 71. A strong solution of potassium hydroxide together with several small bits of phosphorus are placed in the flask A, and a current of coal gas is passed into the flask through the tube B until all the air has been displaced. The gas is then turned off and the flask is heated. Phosphine is formed in small quantities and escapes through the delivery tube, the exit of which is just covered by the water in the vessel C. Each bubble of the gas as it escapes into the air takes fire, and the product of combustion (P_{2}O_{5}) forms beautiful small rings, which float unbroken for a considerable time in quiet air. The pure phosphine does not take fire spontaneously. When prepared as directed above, impurities are present which impart this property. ~Properties.~ Phosphine is a gas of unpleasant odor and is exceedingly poisonous. Like ammonia it forms salts with the halogen acids. Thus we have phosphonium chloride (PH_{4}Cl) analogous to ammonium chloride (NH_{4}Cl). The phosphonium salts are of but little importance. ~Oxides of phosphorus.~ Phosphorus forms two well-known oxides,--the trioxide (P_{2}O_{3}) and the pentoxide (P_{2}O_{5}), sometimes called phosphoric anhydride. When phosphorus burns in an insufficient supply of air the product is partially the trioxide; in oxygen or an excess of air the pentoxide is formed. The pentoxide is much the better known of the two. It is a snow-white, voluminous powder whose most marked property is its great attraction for water. It has no chemical action upon most gases, so that they can be very thoroughly dried by allowing them to pass through properly arranged vessels containing phosphorus pentoxide. ~Acids of phosphorus.~ The important acids of phosphorus are the following: H_{3}PO_{3} phosphorous acid. H_{3}PO_{4} phosphoric acid. H_{4}P_{2}O_{7} pyrophosphoric acid. HPO_{3} metaphosphoric acid. These may be regarded as combinations of the oxides of phosphorus with water according to the equations given in the discussion of the characteristics of the family. 1. _Phosphorous acid_ (H_{3}PO_{3}). Neither the acid nor its salts are at all frequently met with in chemical operations. It can be easily obtained, however, in the form of transparent crystals when phosphorus trichloride is treated with water and the resulting solution is evaporated: PCl_{3} + 3H_{2}O = H_{3}PO_{3} + 3HCl. Its most interesting property is its tendency to take up oxygen and pass over into phosphoric acid. 2. _Orthophosphoric acid (phosphoric acid)_ (H_{3}PO_{4}). This acid can be obtained by dissolving phosphorus pentoxide in boiling water, as represented in the equation P_{2}O_{5} + 3H_{2}O = 2H_{3}PO_{4}. It is usually made by treating calcium phosphate with concentrated sulphuric acid. The calcium sulphate produced in the reaction is nearly insoluble, and can be filtered off, leaving the phosphoric acid in solution. Very pure acid is made by oxidizing phosphorus with nitric acid. It forms large colorless crystals which are exceedingly soluble in water. Being a tribasic acid, it forms acid as well as normal salts. Thus the following compounds of sodium are known: NaH_{2}PO_{4} monosodium hydrogen phosphate. Na_{2}HPO_{4} disodium hydrogen phosphate. Na_{3}PO_{4} normal sodium phosphate. These salts are sometimes called respectively primary, secondary, and tertiary phosphates. They may be prepared by bringing together phosphoric acid and appropriate quantities of sodium hydroxide. Phosphoric acid also forms mixed salts, that is, salts containing two different metals. The most familiar compound of this kind is microcosmic salt, which has the formula Na(NH_{4})HPO_{4}. _Orthophosphates._ The orthophosphates form an important class of salts. The normal salts are nearly all insoluble and many of them occur in nature. The secondary phosphates are as a rule insoluble, while most of the primary salts are soluble. 3. _Pyrophosphoric acid_ (H_{4}P_{2}O_{7}). On heating orthophosphoric acid to about 225° pyrophosphoric acid is formed in accordance with the following equation: 2H_{3}PO_{4} = H_{4}P_{2}O_{7} + H_{2}O. It is a white crystalline solid. Its salts can be prepared by heating a secondary phosphate: 2Na_{2}HPO_{4} = Na_{4}P_{2}O_{7} + H_{2}O. 4. _Metaphosphoric acid (glacial phosphoric acid)_ (HPO_{3}). This acid is formed when orthophosphoric acid is heated above 400°: H_{3}PO_{4} = HPO_{3} + H_{2}O. It is also formed when phosphorus pentoxide is treated with cold water: P_{2}O_{5} + H_{2}O = 2HPO_{3}. It is a white crystalline solid, and is so stable towards heat that it can be fused and even volatilized without decomposition. On cooling from the fused state it forms a glassy solid, and on this account is often called glacial phosphoric acid. It possesses the property of dissolving small quantities of metallic oxides, with the formation of compounds which, in the case of certain metals, have characteristic colors. It is therefore used in the detection of these metals. While the secondary phosphates, on heating, give salts of pyrophosphoric acid, the primary phosphates yield salts of metaphosphoric acid. The equations representing these reactions are as follows: 2Na_{2}HPO_{4} = Na_{4}P_{3}O_{7} + H_{2}O, NaH_{2}PO_{4} = NaPO_{3} + H_{2}O. ~Fertilizers.~ When crops are produced year after year on the same field certain constituents of the soil essential to plant growth are removed, and the soil becomes impoverished and unproductive. To make the land once more fertile these constituents must be replaced. The calcium phosphate of the mineral deposits or of bone ash serves well as a material for restoring phosphorus to soils exhausted of that essential element; but a more soluble substance, which the plants can more readily assimilate, is desirable. It is better, therefore, to convert the insoluble calcium phosphate into the soluble primary phosphate before it is applied as fertilizer. It will be seen by reference to the formulas for the orthophosphates (see page 244) that in a primary phosphate only one hydrogen atom of phosphoric acid is replaced by a metal. Since the calcium atom always replaces two hydrogen atoms, it might be thought that there could be no primary calcium phosphate; but if the calcium atom replaces one hydrogen atom from each of two molecules of phosphoric acid, the salt Ca(H_{2}PO_{4})_{2} will result, and this is a primary phosphate. It can be made by treatment of the normal phosphate with the necessary amount of sulphuric acid, calcium sulphate being formed at the same time, thus: Ca_{3}(PO_{4})_{2} + 2H_{2}SO_{4} = Ca(H_{2}PO_{4})_{2} + 2CaSO_{4}. The resulting mixture is a powder, which is sold as a fertilizer under the name of "superphosphate of lime." ARSENIC ~Occurrence.~ Arsenic occurs in considerable quantities in nature as the native element, as the sulphides realgar (As_{2}S_{2}) and orpiment (As_{2}S_{3}), as oxide (As_{2}O_{3}), and as a constituent of many metallic sulphides, such as arsenopyrite (FeAsS). ~Preparation.~ The element is prepared by purifying the native arsenic, or by heating the arsenopyrite in iron tubes, out of contact with air, when the reaction expressed by the following equation occurs: FeAsS = FeS + As. The arsenic, being volatile, condenses in chambers connected with the heated tubes. It is also made from the oxide by reduction with carbon: 2As_{2}O_{3} + 3C = 4As + 3CO_{2}. ~Properties.~ Arsenic is a steel-gray, metallic-looking substance of density 5.73. Though resembling metals in appearance, it is quite brittle, being easily powdered in a mortar. When strongly heated it sublimes, that is, it passes into a vapor without melting, and condenses again to a crystalline solid when the vapor is cooled. Like phosphorus it can be obtained in several allotropic forms. It alloys readily with some of the metals, and finds its chief use as an alloy with lead, which is used for making shot, the alloy being harder than pure lead. When heated on charcoal with the blowpipe it is converted into an oxide which volatilizes, leaving the charcoal unstained by any oxide coating. It burns readily in chlorine gas, forming arsenic trichloride,-- As + 3Cl = AsCl_{3}. Unlike most of its compounds, the element itself is not poisonous. ~Arsine~ (AsH_{3}). When any compound containing arsenic is brought into the presence of nascent hydrogen, arsine (AsH_{3}), corresponding to phosphine and ammonia, is formed. The reaction when oxide of arsenic is so treated is As_{2}O_{3} + 12H = 2AsH_{3} + 3H_{2}O. Arsine is a gas with a peculiar garlic-like odor, and is intensely poisonous. A single bubble of pure gas has been known to prove fatal. It is an unstable compound, decomposing into its elements when heated to a moderate temperature. It is combustible, burning with a pale bluish-white flame to form arsenic trioxide and water when air is in excess: 2AsH_{3} + 6O = As_{2}O_{3} + 3H_{2}O. When the supply of air is deficient water and metallic arsenic are formed: 2AsH_{3} + 3O = 3H_{2}O + 2As. These reactions make the detection of even minute quantities of arsenic a very easy problem. [Illustration: Fig. 72] ~Marsh's test for arsenic.~ The method devised by Marsh for detecting arsenic is most frequently used, the apparatus being shown in Fig. 72. Hydrogen is generated in the flask A by the action of dilute sulphuric acid on zinc, is dried by passing over calcium chloride in the tube B, and after passing through the hard-glass tube C is ignited at the jet D. If a substance containing arsenic is now introduced into the generator A, the arsenic is converted into arsine by the action of the nascent hydrogen, and passes to the jet along with the hydrogen. If the tube C is strongly heated at some point near the middle, the arsine is decomposed while passing this point and the arsenic is deposited just beyond the heated point in the form of a shining, brownish-black mirror. If the tube is not heated, the arsine burns along with the hydrogen at the jet. Under these conditions a small porcelain dish crowded down into the flame is blackened by a spot of metallic arsenic, for the arsine is decomposed by the heat of the flame, and the arsenic, cooled below its kindling temperature by the cold porcelain, deposits upon it as a black spot. Antimony conducts itself in the same way as arsenic, but the antimony deposit is more sooty in appearance. The two can also be distinguished by the fact that sodium hypochlorite (NaClO) dissolves the arsenic deposit, but not that formed by antimony. ~Oxides of arsenic.~ Arsenic forms two oxides, As_{2}O_{3} and As_{2}O_{5}, corresponding to those of phosphorus. Of these arsenious oxide, or arsenic trioxide (As_{2}O_{3}), is much better known, and is the substance usually called white arsenic, or merely arsenic. It is found as a mineral, but is usually obtained as a by-product in burning pyrite in the sulphuric-acid industry. The pyrite has a small amount of arsenopyrite in it, and when this is burned arsenious oxide is formed as a vapor together with sulphur dioxide: 2FeAsS + 10O = Fe_{2}O_{3} + As_{2}O_{3} + 2SO_{2}. The arsenious oxide is condensed in appropriate chambers. It is a rather heavy substance, obtained either as a crystalline powder or as large, vitreous lumps, resembling lumps of porcelain in appearance. It is very poisonous, from 0.2 to 0.3 g. being a fatal dose. It is frequently given as a poison, since it is nearly tasteless and does not act very rapidly. This slow action is due to the fact that it is not very soluble, and hence is absorbed slowly by the system. Arsenious oxide is also used as a chemical reagent in glass making and in the dye industry. ~Acids of arsenic.~ Like the corresponding oxides of phosphorus, the oxides of arsenic are acid anhydrides. In solution they combine with bases to form salts, corresponding to the salts of the acids of phosphorus. Thus we have salts of the following acids: H_{3}AsO_{3} arsenious acid. H_{3}AsO_{4} orthoarsenic acid. H_{4}As_{2}O_{3} pyroarsenic acid. HAsO_{3} metarsenic acid. Several other acids of arsenic are also known. Not all of these can be obtained as free acids, since they tend to lose water and form the oxides. Thus, instead of obtaining arsenious acid (H_{3}AsO_{3}), the oxide As_{2}O_{3} is obtained: 2H_{3}AsO_{3} = As_{2}O_{3} + 3H_{2}O. Salts of all the acids are known, however, and some of them have commercial value. Most of them are insoluble, and some of the copper salts, which are green, are used as pigments. Paris green, which has a complicated formula, is a well-known insecticide. ~Antidote for arsenical poisoning.~ The most efficient antidote for arsenic poisoning is ferric hydroxide. It is prepared as needed, according to the equation Fe_{2}(SO_{4})_{3} + 3Mg(OH)_{2} = 2Fe(OH)_{3} + 3MgSO_{4}. ~Sulphides of arsenic.~ When hydrogen sulphide is passed into an acidified solution containing an arsenic compound the arsenic is precipitated as a bright yellow sulphide, thus: 2H_{3}AsO_{3} + 3H_{2}S = As_{2}S_{3} + 6H_{2}O, 2H_{3}AsO_{4} + 5H_{2}S = As_{2}S_{5} + 8H_{2}O. In this respect arsenic resembles the metallic elements, many of which produce sulphides under similar conditions. The sulphides of arsenic, both those produced artificially and those found in nature, are used as yellow pigments. ANTIMONY ~Occurrence.~ Antimony occurs in nature chiefly as the sulphide (Sb_{2}S_{3}), called stibnite, though it is also found as oxide and as a constituent of many complex minerals. ~Preparation.~ Antimony is prepared from the sulphide in a very simple manner. The sulphide is melted with scrap iron in a furnace, when the iron combines with the sulphur to form a slag, or liquid layer of melted iron sulphide, while the heavier liquid, antimony, settles to the bottom and is drawn off from time to time. The reaction involved is represented by the equation Sb_{2}S_{3} + 3Fe = 2Sb + 3FeS. ~Physical properties.~ Antimony is a bluish-white, metallic-looking substance whose density is 6.7. It is highly crystalline, hard, and very brittle. It has a rather low melting point (432°) and expands very noticeably on solidifying. ~Chemical properties.~ In chemical properties antimony resembles arsenic in many particulars. It forms the oxides Sb_{2}O_{3} and Sb_{2}O_{5}, and in addition Sb_{2}O_{4}. It combines with the halogen elements with great energy, burning brilliantly in chlorine to form antimony trichloride (SbCl_{3}). When heated on charcoal with the blowpipe it is oxidized and forms a coating of antimony oxide on the charcoal which has a characteristic bluish-white color. ~Stibine~ (SbH_{3}). The gas stibine (SbH_{3}) is formed under conditions which are very similar to those which produce arsine, and it closely resembles the latter compound, though it is still less stable. It is very poisonous. ~Acids of antimony.~ The oxides Sb_{2}O_{3} and Sb_{2}O_{5} are weak acid anhydrides and are capable of forming two series of acids corresponding in formulas to the acids of phosphorus and arsenic. They are much weaker, however, and are of little practical importance. ~Sulphides of antimony.~ Antimony resembles arsenic in that hydrogen sulphide precipitates it as a sulphide when conducted into an acidified solution containing an antimony compound: 2SbCl_{3} + 3H_{2}S = Sb_{2}S_{3} + 6HCl, 2SbCl_{5} + 5H_{2}S = Sb_{2}S_{5} + 10HCl. The two sulphides of antimony are called the trisulphide and the pentasulphide respectively. When prepared in this way they are orange-colored substances, though the mineral stibnite is black. ~Metallic properties of antimony.~ The physical properties of the element are those of a metal, and the fact that its sulphide is precipitated by hydrogen sulphide shows that it acts like a metal in a chemical way. Many other reactions show that antimony has more of the properties of a metal than of a non-metal. The compound Sb(OH)_{3}, corresponding to arsenious acid, while able to act as a weak acid is also able to act as a weak base with strong acids. For example, when treated with concentrated hydrochloric acid antimony chloride is formed: Sb(OH)_{3} + 3HCl = SbCl_{3} + 3H_{2}O. A number of elements act in this same way, their hydroxides under some conditions being weak acids and under others weak bases. ALLOYS Some metals when melted together thoroughly intermix, and on cooling form a homogeneous, metallic-appearing substance called an _alloy_. Not all metals will mix in this way, and in some cases definite chemical compounds are formed and separate out as the mixture solidifies, thus destroying the uniform quality of the alloy. In general the melting point of the alloy is below the average of the melting points of its constituents, and it is often lower than any one of them. Antimony forms alloys with many of the metals, and its chief commercial use is for such purposes. It imparts to its alloys high density, rather low melting point, and the property of expanding on solidification. Such an alloy is especially useful in type founding, where fine lines are to be reproduced on a cast. Type metal consists of antimony, lead, and tin. Babbitt metal, used for journal bearings in machinery, contains the same metals in a different proportion together with a small percentage of copper. BISMUTH ~Occurrence.~ Bismuth is usually found in the uncombined form in nature. It also occurs as oxide and sulphide. Most of the bismuth of commerce comes from Saxony, and from Mexico and Colorado, but it is not an abundant element. ~Preparation.~ It is prepared by merely heating the ore containing the native bismuth and allowing the melted metal to run out into suitable vessels. Other ores are converted into oxides and reduced by heating with carbon. ~Physical properties.~ Bismuth is a heavy, crystalline, brittle metal nearly the color of silver, but with a slightly rosy tint which distinguishes it from other metals. It melts at a low temperature (270°) and has a density of 9.8. It is not acted upon by the air at ordinary temperatures. ~Chemical properties.~ When heated with the blowpipe on charcoal, bismuth gives a coating of the oxide Bi_{2}O_{3}. This has a yellowish-brown color which easily distinguishes it from the oxides formed by other metals. It combines very readily with the halogen elements, powdered bismuth burning readily in chlorine. It is not very easily acted upon by hydrochloric acid, but nitric and sulphuric acids act upon it in the same way that they do upon copper. ~Uses.~ Bismuth finds its chief use as a constituent of alloys, particularly in those of low melting point. Some of these melt in hot water. For example, Wood's metal, consisting of bismuth, lead, tin, and cadmium, melts at 60.5°. ~Compounds of bismuth.~ Unlike the other elements of this group, bismuth has almost no acid properties. Its chief oxide, Bi_{2}O_{3}, is basic in its properties. It dissolves in strong acids and forms salts of bismuth: Bi_{2}O_{3} + 6HCl = 2BiCl_{3} + 3H_{2}O, Bi_{2}O_{3} + 6HNO_{3} = 2Bi(NO_{3})_{3} + 3H_{2}O. The nitrate and chloride of bismuth can be obtained as well-formed colorless crystals. When treated with water the salts are decomposed in the manner explained in the following paragraph. HYDROLYSIS Many salts such as those of antimony and bismuth form solutions which are somewhat acid in reaction, and must therefore contain hydrogen ions. This is accounted for by the same principle suggested to explain the fact that solutions of potassium cyanide are alkaline in reaction (p. 210). Water forms an appreciable number of hydrogen and hydroxyl ions, and very weak bases such as bismuth hydroxide are dissociated to but a very slight extent. When Bi^{+++} ions from bismuth chloride, which dissociates very readily, are brought in contact with the OH^{-} ions from water, the two come to the equilibrium expressed in the equation Bi^{+++} + 3OH^{-} <--> Bi(OH)_{3}. For every hydroxyl ion removed from the solution in this way a hydrogen ion is left free, and the solution becomes acid in reaction. Reactions of this kind and that described under potassium cyanide are called _hydrolysis_. DEFINITION: _Hydrolysis is the action of water upon a salt to form an acid and a base, one of which is very slightly dissociated._ ~Conditions favoring hydrolysis.~ While hydrolysis is primarily due to the slight extent to which either the acid or the base formed is dissociated, several other factors have an influence upon the extent to which it will take place. 1. _Influence of mass._ Since hydrolysis is a reversible reaction, the relative masses of the reacting substances influence the point at which equilibrium will be reached. In the equilibrium BiCl_{3} + 3H_{2}O <--> Bi(OH)_{3} + 3HCl the addition of more water will result in the formation of more bismuth hydroxide and hydrochloric acid. The addition of more hydrochloric acid will convert some of the bismuth hydroxide into bismuth chloride. 2. _Formation of insoluble substances._ When one of the products of hydrolysis is nearly insoluble in water the solution will become saturated with it as soon as a very little has been formed. All in excess of this will precipitate, and the reaction will go on until the acid set free increases sufficiently to bring about an equilibrium. Thus a considerable amount of bismuth and antimony hydroxides are precipitated when water is added to the chlorides of these elements. The greater the dilution the more hydroxide precipitates. The addition of hydrochloric acid in considerable quantity will, however, redissolve the precipitate. ~Partial hydrolysis.~ In many cases the hydrolysis of a salt is only partial, resulting in the formation of basic salts instead of the free base. Most of these basic salts are insoluble in water, which accounts for their ready formation. Thus bismuth chloride may hydrolyze by successive steps, as shown in the equations BiCl_{3} + H_{2}O = Bi(OH)Cl_{2} + HCl, BiCl_{3} + 2H_{2}O = Bi(OH)_{2}Cl + 2HCl, BiCl_{3} + 3H_{2}O = Bi(OH)_{3} + 3HCl. The basic salt so formed may also lose water, as shown in the equation Bi(OH)_{2}Cl = BiOCl + H_{2}O. The salt represented in the last equation is sometimes called bismuth oxychloride, or bismuthyl chloride. The corresponding nitrate, BiONO_{3}, is largely used in medicine under the name of subnitrate of bismuth. In these two compounds the group of atoms, BiO, acts as a univalent metallic radical and is called _bismuthyl_. Similar basic salts are formed by the hydrolysis of antimony salts. EXERCISES 1. Name all the elements so far studied which possess allotropic forms. 2. What compounds would you expect phosphorus to form with bromine and iodine? Write the equations showing the action of water on these compounds. 3. In the preparation of phosphine, why is coal gas passed into the flask? What other gases would serve the same purpose? 4. Give the formula for the salt which phosphine forms with hydriodic acid. Give the name of the compound. 5. Could phosphoric acid be substituted for sulphuric acid in the preparation of the common acids? 6. Write the equations for the preparation of the three sodium salts of orthophosphoric acid. 7. Why does a solution of disodium hydrogen phosphate react alkaline? 8. On the supposition that bone ash is pure calcium phosphate, what weight of it would be required in the preparation of 1 kg. of phosphorus? 9. If arsenopyrite is heated in a current of air, what products are formed? 10. (a) Write equations for the complete combustion of hydrosulphuric acid, methane, and arsine. (b) In what respects are the reactions similar? 11. Write the equations for all the reactions involved in Marsh's test for arsenic. 12. Write the names and formulas for the acids of antimony. 13. Write the equations showing the hydrolysis of antimony trichloride; of bismuth nitrate. 14. In what respects does nitrogen resemble the members of the phosphorus family? CHAPTER XXI SILICON, TITANIUM, BORON ================================================================= | | | | | | SYMBOL | ATOMIC | DENSITY | CHLORIDES | OXIDES | | WEIGHT | | | ____________|________|________|_________|___________|____________ | | | | | Silicon | Si | 28.4 | 2.35 | SiCl_{4} | SiO_{2} Titanium | Ti | 48.1 | 3.5 | TiCl_{4} | TiO_{2} Boron | B | 11.0 | 2.45 | BCl_{3} | B_{2}O_{3} ================================================================= ~General.~ Each of the three elements, silicon, titanium, and boron, belongs to a separate periodic family, but they occur near together in the periodic grouping and are very similar in both physical and chemical properties. Since the other elements in their families are either so rare that they cannot be studied in detail, or are best understood in connection with other elements, it is convenient to consider these three together at this point. The three elements are very difficult to obtain in the free state, owing to their strong attraction for other elements. They can be prepared by the action of aluminium or magnesium on their oxides and in impure state by reduction with carbon in an electric furnace. They are very hard and melt only at the highest temperatures. At ordinary temperatures they are not attacked by oxygen, but when strongly heated they burn with great brilliancy. Silicon and boron are not attacked by acids under ordinary conditions; titanium is easily dissolved by them. SILICON ~Occurrence.~ Next to oxygen silicon is the most abundant element. It does not occur free in nature, but its compounds are very abundant and of the greatest importance. It occurs almost entirely in combination with oxygen as silicon dioxide (SiO_{2}), often called silica, or with oxygen and various metals in the form of salts of silicic acids, or silicates. These compounds form a large fraction of the earth's crust. Most plants absorb small amounts of silica from the soil, and it is also found in minute quantities in animal organisms. ~Preparation.~ The element is most easily prepared by reducing pure powdered quartz with magnesium powder: SiO_{2} + 2Mg = 2MgO + Si. ~Properties.~ As would be expected from its place in the periodic table, silicon resembles carbon in many respects. It can be obtained in several allotropic forms, corresponding to those of carbon. The crystallized form is very hard, and is inactive toward reagents. The amorphous variety has, in general, properties more similar to charcoal. ~Compounds of silicon with hydrogen and the halogens.~ Silicon hydride (SiH_{4}) corresponds in formula to methane (CH_{4}), but its properties are more like those of phosphine (PH_{3}). It is a very inflammable gas of disagreeable odor, and, as ordinarily prepared, takes fire spontaneously on account of the presence of impurities. Silicon combines with the elements of the chlorine family to form such compounds as SiCl_{4} and SiF_{4}. Of these silicon fluoride is the most familiar and interesting. As stated in the discussion of fluorine, it is formed when hydrofluoric acid acts upon silicon dioxide or a silicate. With silica the reaction is thus expressed: SiO_{2} + 4HF = SiF_{4} + 2H_{2}O. It is a very volatile, invisible, poisonous gas. In contact with water it is partially decomposed, as shown in the equation SiF_{4} + 4H_{2}O = 4HF + Si(OH)_{4}. The hydrofluoric acid so formed combines with an additional amount of silicon fluoride, forming the complex fluosilicic acid (H_{2}SiF_{6}), thus: 2HF + SiF_{4} = H_{2}SiF_{6}. ~Silicides.~ As the name indicates, silicides are binary compounds consisting of silicon and some other element. They are very stable at high temperatures, and are usually made by heating the appropriate substances in an electric furnace. The most important one is _carborundum_, which is a silicide of carbon of the formula CSi. It is made by heating coke and sand, which is a form of silicon dioxide, in an electric furnace, the process being extensively carried on at Niagara Falls. The following equation represents the reaction SiO_{2} + 3C = CSi + 2CO. The substance so prepared consists of beautiful purplish-black crystals, which are very hard. Carborundum is used as an abrasive, that is, as a material for grinding and polishing very hard substances. Ferrosilicon is a silicide of iron alloyed with an excess of iron, which finds extensive use in the manufacture of certain kinds of steel. ~Manufacture of carborundum.~ The mixture of materials is heated in a large resistance furnace for about thirty-six hours. After the reaction is completed there is left a core of graphite G. Surrounding this core is a layer of crystallized carborundum C, about 16 in. thick. Outside this is a shell of amorphous carborundum A. The remaining materials M are unchanged and are used for a new charge. [Illustration: Fig. 73] ~Silicon dioxide~ (_silica_) (SiO_{2}). This substance is found in a great variety of forms in nature, both in the amorphous and in the crystalline condition. In the form of quartz it is found in beautifully formed six-sided prisms, sometimes of great size. When pure it is perfectly transparent and colorless. Some colored varieties are given special names, as amethyst (violet), rose quartz (pale pink), smoky or milky quartz (colored and opaque). Other varieties of silicon dioxide, some of which also contain water, are chalcedony, onyx, jasper, opal, agate, and flint. Sand and sandstone are largely silicon dioxide. ~Properties.~ As obtained by chemical processes silicon dioxide is an amorphous white powder. In the crystallized state it is very hard and has a density of 2.6. It is insoluble in water and in most chemical reagents, and requires the hottest oxyhydrogen flame for fusion. Acids, excepting hydrofluoric acid, have little action on it, and it requires the most energetic reducing agents to deprive it of oxygen. It is the anhydride of an acid, and consequently it dissolves in fused alkalis to form silicates. Being nonvolatile, it will drive out most other anhydrides when heated to a high temperature with their salts, especially when the silicates so formed are fusible. The following equations illustrate this property: Na_{2}CO_{3} + SiO_{2} = Na_{2}SiO_{3} + CO_{2}, Na_{2}SO_{4} + SiO_{2} = Na_{2}SiO_{3} + SO_{3}. ~Silicic acids.~ Silicon forms two simple acids, orthosilicic acid (H_{4}SiO_{4}) and metasilicic acid (H_{2}SiO_{3}). Orthosilicic acid is formed as a jelly-like mass when orthosilicates are treated with strong acids such as hydrochloric. On attempting to dry this acid it loses water, passing into metasilicic or common silicic acid: H_{4}SiO_{4} = H_{2}SiO_{3} + H_{2}O. Metasilicic acid when heated breaks up into silica and water, thus: H_{2}SiO_{3} = H_{2}O + SiO_{2}. ~Salts of silicic acids,--silicates.~ A number of salts of the orthosilicic and metasilicic acids occur in nature. Thus mica (KAlSiO_{4}) is a salt of orthosilicic acid. ~Polysilicic acids.~ Silicon has the power to form a great many complex acids which may be regarded as derived from the union of several molecules of the orthosilicic acid, with the loss of water. Thus we have 3H_{4}SiO_{4} = H_{4}Si_{3}O_{8} + 4H_{2}O. These acids cannot be prepared in the pure state, but their salts form many of the crystalline rocks in nature. Feldspar, for example, has the formula KAlSi_{3}O_{8}, and is a mixed salt of the acid H_{4}Si_{3}O_{8}, whose formation is represented in the equation above. Kaolin has the formula Al_{2}Si_{2}O_{7}·2H_{2}O. Many other examples will be met in the study of the metals. ~Glass.~ When sodium and calcium silicates, together with silicon dioxide, are heated to a very high temperature, the mixture slowly fuses to a transparent liquid, which on cooling passes into the solid called glass. Instead of starting with sodium and calcium silicates it is more convenient and economical to heat sodium carbonate (or sulphate) and lime with an excess of clean sand, the silicates being formed during the heating: Na_{2}CO_{3} + SiO_{2} = Na_{2}SiO_{3} + CO_{2}, CaO + SiO_{2} = CaSiO_{3}. [Illustration: Fig. 74] The mixture is heated below the fusing point for some time, so that the escaping carbon dioxide may not spatter the hot liquid; the heat is then increased and the mixture kept in a state of fusion until all gases formed in the reaction have escaped. _Molding and blowing of glass._ The way in which the melted mixture is handled in the glass factory depends upon the character of the article to be made. Many articles, such as bottles, are made by blowing the plastic glass into hollow molds of the desired shape. The mold is first opened, as shown in Fig. 74. A lump of plastic glass A on the hollow rod B is lowered into the mold, which is then closed by the handles C. By blowing into the tube the glass is blown into the shape of the mold. The mold is then opened and the bottle lifted out. The neck of the bottle must be cut off at the proper place and the sharp edges rounded off in a flame. Other objects, such as lamp chimneys, are made by getting a lump of plastic glass on the end of a hollow iron rod and blowing it into the desired shape without the help of a mold, great skill being required in the manipulation of the glass. Window glass is made by blowing large hollow cylinders about 6 ft. long and 1-1/2 ft. in diameter. These are cut longitudinally, and are then placed in an oven and heated until they soften, when they are flattened out into plates (Fig. 75). Plate glass is cast into flat slabs, which are then ground and polished to perfectly plane surfaces. _Varieties of glass._ The ingredients mentioned above make a soft, easily fusible glass. If potassium carbonate is substituted for the sodium carbonate, the glass is much harder and less easily fused; increasing the amount of sand has somewhat the same effect. Potassium glass is largely used in making chemical glassware, since it resists the action of reagents better than the softer sodium glass. If lead oxide is substituted for the whole or a part of the lime, the glass is very soft, but has a high index of refraction and is valuable for making optical instruments and artificial jewels. [Illustration: Fig. 75] _Coloring of glass._ Various substances fused along with the glass mixture give characteristic colors. The amber color of common bottles is due to iron compounds in the glass; in other cases iron colors the glass green. Cobalt compounds color it deep blue; those of manganese give it an amethyst tint and uranium compounds impart a peculiar yellowish green color. Since iron is nearly always present in the ingredients, glass is usually slightly yellow. This color can be removed by adding the proper amount of manganese dioxide, for the amethyst color of manganese and the yellow of iron together produce white light. _Nature of glass._ Glass is not a definite chemical compound and its composition varies between wide limits. Fused glass is really a solution of various silicates, such as those of calcium and lead, in fused sodium or potassium silicate. A certain amount of silicon dioxide is also present. This solution is then allowed to solidify under such conditions of cooling that the dissolved substances do not separate from the solvent. The compounds which are used to color the glass are sometimes converted into silicates, which then dissolve in the glass, giving it a uniform color. In other cases, as in the milky glasses which resemble porcelain in appearance, the color or opaqueness is due to the finely divided color material evenly distributed throughout the glass, but not dissolved in it. Milky glass is made by mixing calcium fluoride, tin oxide, or some other insoluble substance in the melted glass. Copper or gold in metallic form scattered through glass gives it shades of red. TITANIUM Titanium is a very widely distributed element in nature, being found in almost all soils, in many rocks, and even in plant and animal tissues. It is not very abundant in any one locality, and it possesses little commercial value save in connection with the iron industry. Its most common ore is rutile (TiO_{2}), which resembles silica in many respects. In both physical and chemical properties titanium resembles silicon, though it is somewhat more metallic in character. This resemblance is most marked in the acids of titanium. It not only forms metatitanic and orthotitanic acids but a great variety of polytitanic acids as well. BORON ~Occurrence.~ Boron is never found free in nature. It occurs as boric acid (H_{3}BO_{3}), and in salts of polyboric acids, which usually have very complicated formulas. ~Preparation and properties.~ Boron can be prepared from its oxide by reduction with magnesium, exactly as in the case of silicon. It resembles silicon very strikingly in its properties. It occurs in several allotropic forms, is very hard when crystallized, and is rather inactive toward reagents. It forms a hydride, BH_{3}, and combines directly with the elements of the chlorine family. Boron fluoride (BF_{3}) is very similar to silicon fluoride in its mode of formation and chemical properties. ~Boric oxide~ (B_{2}O_{3}). Boron forms one well-known oxide, B_{2}O_{3}, called boric anhydride. It is formed as a glassy mass by heating boric acid to a high temperature. It absorbs water very readily, uniting with it to form boric acid again: B_{2}O_{3} + 3H_{2}O = 2H_{3}BO_{3}. In this respect it differs from silicon dioxide, which will not combine directly with water. ~Boric acid~ (H_{3}BO_{3}). This is found in nature in considerable quantities and forms one of the chief sources of boron compounds. It is found dissolved in the water of hot springs in some localities, particularly in Italy. Being volatile with steam, the vapor which escapes from these springs has some boric acid in it. It is easily obtained from these sources by condensation and evaporation, the necessary heat being supplied by other hot springs. Boric acid crystallizes in pearly flakes, which are greasy to the touch. In the laboratory it is easily prepared by treating a strong, hot solution of borax with sulphuric acid. Boric acid being sparingly soluble in water crystallizes out on cooling: Na_{2}B_{4}O_{7} + 5H_{2}O + H_{2}SO_{4} = Na_{2}SO_{4} + 4H_{3}BO_{3}. The substance is a mild antiseptic, and on this account is often used in medicine and as a preservative for canned foods and milk. ~Metaboric and polyboric acids.~ When boric acid is gently heated it is converted into metaboric acid (HBO_{2}): H_{3}BO_{3} = HBO_{2} + H_{2}O. On heating metaboric acid to a somewhat higher temperature tetraboric acid (H_{2}B_{4}O_{7}) is formed: 4HBO_{2} = H_{2}B_{4}O_{7} + H_{2}O. Many other complex acids of boron are known. ~Borax.~ Borax is the sodium salt of tetraboric acid, having the formula Na_{2}B_{4}O_{7}·10 H_{2}O. It is found in some arid countries, as southern California and Tibet, but is now made commercially from the mineral colemanite, which is the calcium salt of a complex boric acid. When this is treated with a solution of sodium carbonate, calcium carbonate is precipitated and borax crystallizes from the solution. When heated borax at first swells up greatly, owing to the expulsion of the water of crystallization, and then melts to a clear glass. This glass has the property of easily dissolving many metallic oxides, and on this account borax is used as a flux in soldering, for the purpose of removing from the metallic surfaces to be soldered the film of oxide with which they are likely to be covered. These oxides often give a characteristic color to the clear borax glass, and borax beads are therefore often used in testing for the presence of metals, instead of the metaphosphoric acid bead already described. The reason that metallic oxides dissolve in borax is that borax contains an excess of acid anhydride, as can be more easily seen if its formula is written 2NaBO_{2} + B_{2}O_{3}. The metallic oxide combines with this excess of acid anhydride, forming a mixed salt of metaboric acid. Borax is extensively used as a constituent of enamels and glazes for both metal ware and pottery. It is also used as a flux in soldering and brazing, and in domestic ways it serves as a mild alkali, as a preservative for meats, and in a great variety of less important applications. EXERCISES 1. Account for the fact that a solution of borax in water is alkaline. 2. What weight of water of crystallization does 1 kg. of borax contain? 3. When a concentrated solution of borax acts on silver nitrate a borate of silver is formed. If the solution of borax is dilute, however, an hydroxide of silver forms. Account for this difference in behavior. CHAPTER XXII THE METALS ~The metals.~ The elements which remain to be considered are known collectively as the metals. They are also called the base-forming elements, since their hydroxides are bases. A metal may therefore be defined as an element whose hydroxide is a base. When a base dissolves in water the hydroxyl groups form the anions, while the metallic element forms the cations. From this standpoint a metal can be defined as an element capable of forming simple cations in solution. The distinction between a metal and a non-metal is not a very sharp one, since the hydroxides of a number of elements act as bases under some conditions and as acids under others. We have seen that antimony is an element of this kind. ~Occurrence of metals in nature.~ A few of the metals are found in nature in the free state. Among these are gold, platinum, and frequently copper. They are usually found combined with other elements in the form of oxides or salts of various acids. Silicates, carbonates, sulphides, and sulphates are the most abundant salts. All inorganic substances occurring in nature, whether they contain a metal or not, are called _minerals_. Those minerals from which a useful substance can be extracted are called _ores_ of the substance. These two terms are most frequently used in connection with the metals. ~Extraction of metals,--metallurgy.~ The process of extracting a metal from its ores is called the metallurgy of the metal. The metallurgy of each metal presents peculiarities of its own, but there are several methods of general application which are very frequently employed. 1. _Reduction of an oxide with carbon._ Many of the metals occur in nature in the form of oxides. When these oxides are heated to a high temperature with carbon the oxygen combines with it and the metal is set free. Iron, for example, occurs largely in the form of the oxide Fe_{2}O_{3}. When this is heated with carbon the reaction expressed in the following equation takes place: Fe_{2}O_{3} + 3 C = 2 Fe + 3 CO. Many ores other than oxides may be changed into oxides which can then be reduced by carbon. The conversion of such ores into oxides is generally accomplished by heating, and this process is called _roasting_. Many carbonates and hydroxides decompose directly into the oxide on heating. Sulphides, on the other hand, must be heated in a current of air, the oxygen of the air entering into the reaction. The following equations will serve to illustrate these changes in the case of the ores of iron: FeCO_{3} = FeO + CO_{2}, 2Fe(OH)_{3} = Fe_{2}O_{3} + 3H_{2}O, 2FeS_{2} + 11O = Fe_{2}O_{3} + 4SO_{2}. 2. _Reduction of an oxide with aluminium._ Not all oxides, however, can be reduced by carbon. In such cases aluminium may be used. Thus chromium may be obtained in accordance with the following equation: Cr_{2}O_{3} + 2 Al = 2 Cr + Al_{2}O_{3}. This method is a comparatively new one, having been brought into use by the German chemist Goldschmidt; hence it is sometimes called the Goldschmidt method. 3. _Electrolysis._ In recent years increasing use is being made of the electric current in the preparation of metals. In some cases the separation of the metal from its compounds is accomplished by passing the current through a solution of a suitable salt of the metal, the metal usually being deposited upon the cathode. In other cases the current is passed through a fused salt of the metal, the chloride being best adapted to this purpose. ~Electro-chemical industries.~ Most of the electro-chemical industries of the country are carried on where water power is abundant, since this furnishes the cheapest means for the generation of electrical energy. Niagara Falls is the most important locality in this country for such industries, and many different electro-chemical products are manufactured there. Some industries depend upon electrolytic processes, while in others the electrical energy is used merely as a source of heat in electric furnaces. ~Preparation of compounds of the metals.~ Since the compounds of the metals are so numerous and varied in character, there are many ways of preparing them. In many cases the properties of the substance to be prepared, or the material available for its preparation, suggest a rather unusual way. There are, however, a number of general principles which are constantly applied in the preparation of the compounds of the metals, and a clear understanding of them will save much time and effort in remembering the details in any given case. The most important of these general methods for the preparation of compounds are the following: 1. _By direct union of two elements._ This is usually accomplished by heating the two elements together. Thus the sulphides, chlorides, and oxides of a metal can generally be obtained in this way. The following equations serve as examples of this method: Fe + S = FeS, Mg + O = MgO, Cu + 2Cl = CuCl_{2}. 2. _By the decomposition of a compound._ This decomposition may be brought about either by heat alone or by the combined action of heat and a reducing agent. Thus when the nitrate of a metal is heated the oxide of the metal is usually obtained. Copper nitrate, for example, decomposes as follows: Cu(NO_{3})_{2} = CuO + 2NO_{2} + O. Similarly the carbonates of the metals yield oxides, thus: CaCO_{3} = CaO + CO_{2}. Most of the hydroxides form an oxide and water when heated: 2Al(OH)_{3} = Al_{2}O_{3} + 3H_{2}O. When heated with carbon, sulphates are reduced to sulphides, thus: BaSO_{4} + 2C = BaS + 2CO_{2}. 3. _Methods based on equilibrium in solution._ In the preparation of compounds the first requisite is that the reactions chosen shall be of such a kind as will go on to completion. In the chapter on chemical equilibrium it was shown that reactions in solution may become complete in either of three ways: (1) a gas may be formed which escapes from solution; (2) an insoluble solid may be formed which precipitates; (3) two different ions may combine to form undissociated molecules. By the judicious selection of materials these principles may be applied to the preparation of a great variety of compounds, and illustrations of such methods will very frequently be found in the subsequent pages. 4. _By fusion methods._ It sometimes happens that substances which are insoluble in water and in acids, and which cannot therefore be brought into double decomposition in the usual way, are soluble in other liquids, and when dissolved in them can be decomposed and converted into other desired compounds. Thus barium sulphate is not soluble in water, and sulphuric acid, being less volatile than most other acids, cannot easily be driven out from this salt When brought into contact with melted sodium carbonate, however, it dissolves in it, and since barium carbonate is insoluble in melted sodium carbonate, double decomposition takes place: Na_{2}CO_{3} + BaSO_{4} = BaCO_{3} + Na_{2}SO_{4}. On dissolving the cooled mixture in water the sodium sulphate formed in the reaction, together with any excess of sodium carbonate which may be present, dissolves. The barium carbonate can then be filtered off and converted into any desired salt by the processes already described. 5. _By the action of metals on salts of other metals._ When a strip of zinc is placed in a solution of a copper salt the copper is precipitated and an equivalent quantity of zinc passes into solution: Zn + CuSO_{4} = Cu + ZnSO_{4}. In like manner copper will precipitate silver from its salts: Cu + Ag_{2}SO_{4} = 2Ag + CuSO_{4}. It is possible to tabulate the metals in such a way that any one of them in the table will precipitate any one following it from its salts. The following is a list of some of the commoner metals arranged in this way: Zinc Iron Tin Lead Copper Bismuth Mercury Silver Gold According to this table copper will precipitate bismuth, mercury, silver, or gold from their salts, and will in turn be precipitated by zinc, iron, tin, or lead. Advantage is taken of this principle in the purification of some of the metals, and occasionally in the preparation of metals and their compounds. ~Important insoluble compounds.~ Since precipitates play so important a part in the reactions which substances undergo, as well as in the preparation of many chemical compounds, it is important to know what substances are insoluble. Knowing this, we can in many cases predict reactions under certain conditions, and are assisted in devising ways to prepare desired compounds. While there is no general rule which will enable one to foretell the solubility of any given compound, nevertheless a few general statements can be made which will be of much assistance. 1. _Hydroxides._ All hydroxides are insoluble save those of ammonium, sodium, potassium, calcium, barium, and strontium. 2. _Nitrates._ All nitrates are soluble in water. 3. _Chlorides._ All chlorides are soluble save silver and mercurous chlorides. (Lead chloride is but slightly soluble.) 4. _Sulphates._ All sulphates are soluble save those of barium, strontium, and lead. (Sulphates of silver and calcium are only moderately soluble.) 5. _Sulphides._ All sulphides are insoluble save those of ammonium, sodium, and potassium. The sulphides of calcium, barium, strontium, and magnesium are insoluble in water, but are changed by hydrolysis into acid sulphides which are soluble. On this account they cannot be prepared by precipitation. 6. _Carbonates, phosphates, and silicates._ All normal carbonates, phosphates, and silicates are insoluble save those of ammonium, sodium and potassium. EXERCISES 1. Write equations representing four different ways for preparing Cu(NO_{3})_{2}. 2. Write equations representing six different ways for preparing ZnSO_{4}. 3. Write equations for two reactions to illustrate each of the three ways in which reactions in solutions may become complete. 4. Give one or more methods for preparing each of the following compounds: CaCl_{2}, PbCl_{2}, BaSO_{4}, CaCO_{3}, (NH_{4})_{2}S, Ag_{2}S, PbO, Cu(OH)_{2} (for solubilities, see last paragraph of chapter). State in each case the general principle involved in the method of preparation chosen. CHAPTER XXIII THE ALKALI METALS ================================================================= | | | | | | SYMBOL | ATOMIC | DENSITY | MELTING | FIRST PREPARED | | WEIGHT | | POINT | __________|________|________|_________|_________|________________ | | | | | Lithium | Li | 7.03 | 0.59 | 186.° | Davy 1820 Sodium | Na | 23.05 | 0.97 | 97.6° | " 1807 Potassium | K | 39.15 | 0.87 | 62.5° | " 1807 Rubidium | Rb | 85.5 | 1.52 | 38.5° | Bunsen 1861 Cæsium | Cs | 132.9 | 1.88 | 26.5° | " 1860 ================================================================= ~The family.~ The metals listed in the above table constitute the even family in Group I in the periodic arrangement of the elements, and therefore form a natural family. The name alkali metals is commonly applied to the family for the reason that the hydroxides of the most familiar members of the family, namely sodium and potassium, have long been called alkalis. 1. _Occurrence._ While none of these metals occur free in nature, their compounds are very widely distributed, being especially abundant in sea and mineral waters, in salt beds, and in many rocks. Only sodium and potassium occur in abundance, the others being rarely found in any considerable quantity. 2. _Preparation._ The metals are most conveniently prepared by the electrolysis of their fused hydroxides or chlorides, though it is possible to prepare them by reducing their oxides or carbonates with carbon. 3. _Properties._ They are soft, light metals, having low melting points and small densities, as is indicated in the table. Their melting points vary inversely with their atomic weights, while their densities (sodium excepted) vary directly with these. The pure metals have a silvery luster but tarnish at once when exposed to the air, owing to the formation of a film of oxide upon the surface of the metal. They are therefore preserved in some liquid, such as coal oil, which contains no oxygen. Because of their strong affinity for oxygen they decompose water with great ease, forming hydroxides and liberating hydrogen in accordance with the equation M + H_{2}O = MOH + H, where M stands for any one of these metals. These hydroxides are white solids; they are readily soluble in water and possess very strong basic properties. These bases are nearly equal in strength, that is, they all dissociate in water to about the same extent. 4. _Compounds._ The alkali metals almost always act as univalent elements in the formation of compounds, the composition of which can be represented by such formulas as MH, MCl, MNO_{3}, M_{2}SO_{4}, M_{3}PO_{4}. These compounds, when dissolved in water, dissociate in such a way as to form simple, univalent metallic ions which are colorless. With the exception of lithium these metals form very few insoluble compounds, so that it is not often that precipitates containing them are obtained. Only sodium and potassium will be studied in detail, since the other metals of the family are of relatively small importance. The compounds of sodium and potassium are so similar in properties that they can be used interchangeably for most purposes. Other things being equal, the sodium compounds are prepared in preference to those of potassium, since they are cheaper. When a given sodium compound is deliquescent, or is so soluble that it is difficult to purify, the corresponding potassium compound is prepared in its stead, provided its properties are more desirable in these respects. SODIUM ~Occurrence in nature.~ Large deposits of sodium chloride have been found in various parts of the world, and the water of the ocean and of many lakes and springs contains notable quantities of it. The element also occurs as a constituent of many rocks and is therefore present in the soil formed by their disintegration. The mineral cryolite (Na_{3}AlF_{6}) is an important substance, and the nitrate, carbonate, and borate also occur in nature. ~Preparation.~ In 1807 Sir Humphry Davy succeeded in preparing very small quantities of metallic sodium by the electrolysis of the fused hydroxide. On account of the cost of electrical energy it was for many years found more economical to prepare it by reducing the carbonate with carbon in accordance with the following equation: Na_{2}CO_{3} + 2C = 2Na + 3CO. The cost of generating the electric current has been diminished to such an extent, however, that it is now more economical to prepare sodium by Davy's original method, namely, by the electrolysis of the fused hydroxide or chloride. When the chloride is used the process is difficult to manage, owing to the higher temperature required to keep the electrolyte fused, and because of the corroding action of the fused chloride upon the containing vessel. [Illustration: SIR HUMPHRY DAVY (English) (1778-1829) Isolated sodium, lithium, potassium, barium, strontium, and calcium by means of electrolysis; demonstrated the elementary nature of chlorine; invented the safety lamp; discovered the stupefying effects of nitrous oxide] ~Technical preparation.~ The sodium hydroxide is melted in a cylindrical iron vessel (Fig. 76) through the bottom of which rises the cathode K. The anodes A, several in number, are suspended around the cathode from above. A cylindrical vessel C floats in the fused alkali directly over the cathode, and under this cap the sodium and hydrogen liberated at the cathode collect. The hydrogen escapes by lifting the cover, and the sodium, protected from the air by the hydrogen, is skimmed or drained off from time to time. Oxygen is set free upon the anode and escapes into the air through the openings O without coming into contact with the sodium or hydrogen. This process is carried on extensively at Niagara Falls. [Illustration: Fig. 76] ~Properties.~ Sodium is a silver-white metal about as heavy as water, and so soft that it can be molded easily by the fingers or pressed into wire. It is very active chemically, combining with most of the non-metallic elements, such as oxygen and chlorine, with great energy. It will often withdraw these elements from combination with other elements, and is thus able to decompose water and the oxides and chlorides of many metals. ~Sodium peroxide~ (NaO). Since sodium is a univalent element we should expect it to form an oxide of the formula Na_{2}O. While such an oxide can be prepared, the peroxide (NaO) is much better known. It is a yellowish-white powder made by burning sodium in air. Its chief use is as an oxidizing agent. When heated with oxidizable substances it gives up a part of its oxygen, as shown in the equation 2NaO = Na_{2}O + O. Water decomposes it in accordance with the equation 2NaO + 2H_{2}O = 2NaOH + H_{2}O_{2}. Acids act readily upon it, forming a sodium salt and hydrogen peroxide: 2NaO + 2HCl = 2NaCl + H_{2}O_{2}. In these last two reactions the hydrogen dioxide formed may decompose into water and oxygen if the temperature is allowed to rise: H_{2}O_{2} = H_{2}O + O. ~Peroxides.~ It will be remembered that barium dioxide (BaO_{2}) yields hydrogen dioxide when treated with acids, and that manganese dioxide gives up oxygen when heated with sulphuric acid. Oxides which yield either hydrogen dioxide or oxygen when treated with water or an acid are called peroxides. ~Sodium hydroxide~ (_caustic soda_) (NaOH). 1. _Preparation._ Sodium hydroxide is prepared commercially by several processes. (a) In the older process, still in extensive use, sodium carbonate is treated with calcium hydroxide suspended in water. Calcium carbonate is precipitated according to the equation Na_{2}CO_{3} + Ca(OH)_{2} = CaCO_{3} + 2NaOH. The dilute solution of sodium hydroxide, filtered from the calcium carbonate, is evaporated to a paste and is then poured into molds to solidify. It is sold in the form of slender sticks. (b) The newer methods depend upon the electrolysis of sodium chloride. In the Castner process a solution of salt is electrolyzed, the reaction being expressed as follows: NaCl + H_{2}O = NaOH + H + Cl. The chlorine escapes as a gas, and by an ingenious mechanical device the sodium hydroxide is prevented from mixing with the salt in the solution. In the Acker process the electrolyte is _fused_ sodium chloride. The chlorine is evolved as a gas at the anode, while the sodium alloys with the melted lead which forms the cathode. When this alloy is treated with water the following reaction takes place: Na + H_{2}O = NaOH + H. [Illustration: Fig. 77] ~Technical process.~ A sketch of an Acker furnace is represented in Fig. 77. The furnace is an irregularly shaped cast-iron box, divided into three compartments, A, B, and C. Compartment A is lined with magnesia brick. Compartments B and C are filled with melted lead, which also covers the bottom of A to a depth of about an inch. Above this layer in A is fused salt, into which dip carbon anodes D. The metallic box and melted lead is the cathode. When the furnace is in operation chlorine is evolved at the anodes, and is drawn away through a pipe (not represented) to the bleaching-powder chambers. Sodium is set free at the surface of the melted lead in A, and at once alloys with it. Through the pipe E a powerful jet of steam is driven through the lead in B upwards into the narrow tube F. This forces the lead alloy up through the tube and over into the chamber G. In this process the steam is decomposed by the sodium in the alloy, forming melted sodium hydroxide and hydrogen. The melted lead and sodium hydroxide separate into two layers in G, and the sodium hydroxide, being on top, overflows into tanks from which it is drawn off and packed in metallic drums. The lead is returned to the other compartments of the furnace by a pipe leading from H to I. Compartment C serves merely as a reservoir for excess of melted lead. 2. _Properties._ Sodium hydroxide is a white, crystalline, brittle substance which rapidly absorbs water and carbon dioxide from the air. As the name (caustic soda) indicates, it is a very corrosive substance, having a disintegrating action on most animal and vegetable tissues. It is a strong base. It is used in a great many chemical industries, and under the name of lye is employed to a small extent as a cleansing agent for household purposes. ~Sodium chloride~ (_common salt_) (NaCl). 1. _Preparation._ Sodium chloride, or common salt, is very widely distributed in nature. Thick strata, evidently deposited at one time by the evaporation of salt water, are found in many places. In the United States the most important localities for salt are New York, Michigan, Ohio, and Kansas. Sometimes the salt is mined, especially if it is in the pure form called rock salt. More frequently a strong brine is pumped from deep wells sunk into the salt deposit, and is then evaporated in large pans until the salt crystallizes out. The crystals are in the form of small cubes and contain no water of crystallization; some water is, however, held in cavities in the crystals and causes the salt to decrepitate when heated. 2. _Uses._ Since salt is so abundant in nature it forms the starting point in the preparation of all compounds containing either sodium or chlorine. This includes many substances of the highest importance to civilization, such as soap, glass, hydrochloric acid, soda, and bleaching powder. Enormous quantities of salt are therefore produced each year. Small quantities are essential to the life of man and animals. Pure salt does not absorb moisture; the fact that ordinary salt becomes moist in air is not due to a property of the salt, but to impurities commonly occurring in it, especially calcium and magnesium chlorides. ~Sodium sulphate~ (_Glauber's salt_) (Na_{2}SO_{4}·10H_{2}O). This salt is prepared by the action of sulphuric acid upon sodium chloride, hydrochloric acid being formed at the same time: 2NaCl + H_{2}SO_{4} = Na_{2}SO_{4} + 2HCl. Some sodium sulphate is prepared by the reaction represented in the equation MgSO_{4} + 2NaCl = Na_{2}SO_{4} + MgCl_{2}. The magnesium sulphate required for this reaction is obtained in large quantities in the manufacture of potassium chloride, and being of little value for any other purpose is used in this way. The reaction depends upon the fact that sodium sulphate is the least soluble of any of the four factors in the equation, and therefore crystallizes out when hot, saturated solutions of magnesium sulphate and sodium chloride are mixed together and the resulting mixture cooled. Sodium sulphate forms large efflorescent crystals. The salt is extensively used in the manufacture of sodium carbonate and glass. Small quantities are used in medicine. ~Sodium sulphite~ (Na_{2}SO_{3}·7H_{2}O). Sodium sulphite is prepared by the action of sulphur dioxide upon solutions of sodium hydroxide, the reaction being analogous to the action of carbon dioxide upon sodium hydroxide. Like the carbonate, the sulphite is readily decomposed by acids: Na_{2}SO_{3} + 2HCl = 2NaCl + H_{2}O + SO_{2}. Because of this reaction sodium sulphite is used as a convenient source of sulphur dioxide. It is also used as a disinfectant and a preservative. ~Sodium thiosulphate~ (_hyposulphite of soda or "hypo"_) (Na_{2}S_{2}O_{3}·5H_{2}O). This salt, commonly called sodium hyposulphite, or merely hypo, is made by boiling a solution of sodium sulphite with sulphur: Na_{2}SO_{3} + S = Na_{2}S_{2}O_{3}. It is used in photography and in the bleaching industry, to absorb the excess of chlorine which is left upon the bleached fabrics. ~Thio compounds.~ The prefix "thio" means sulphur. It is used to designate substances which may be regarded as derived from oxygen compounds by replacing the whole or a part of their oxygen with sulphur. The thiosulphates may be regarded as sulphates in which one atom of oxygen has been replaced by an atom of sulphur. This may be seen by comparing the formula Na_{2}SO_{4} (sodium sulphate) with the formula Na_{2}S_{2}O_{3} (sodium thiosulphate). ~Sodium carbonate~ (_sal soda_)(Na_{2}CO_{3}·10H_{2}O). There are two different methods now employed in the manufacture of this important substance. 1. _Le Blanc process._ This older process involves several distinct reactions, as shown in the following equations. (a) Sodium chloride is first converted into sodium sulphate: 2NaCl + H_{2}SO_{4} = Na_{2}SO_{4} + 2HCl. (b) The sodium sulphate is next reduced to sulphide by heating it with carbon: Na_{2}SO_{4} + 2C = Na_{2}S + 2CO_{2}. (c) The sodium sulphide is then heated with calcium carbonate, when double decomposition takes place: Na_{2}S + CaCO_{3} = CaS + Na_{2}CO_{3}. ~Technical preparation of sodium carbonate.~ In a manufacturing plant the last two reactions take place in one process. Sodium sulphate, coal, and powdered limestone are heated together to a rather high temperature. The coal reduces the sulphate to sulphide, which in turn reacts upon the calcium carbonate. Some limestone is decomposed by the heat, forming calcium oxide. When treated with water the calcium oxide is changed into hydroxide, and this prevents the water from decomposing the insoluble calcium sulphide. The crude product of the process is a hard black cake called black ash. On digesting this mass with water the sodium carbonate passes into solution. The pure carbonate is obtained by evaporation of this solution, crystallizing from it in crystals of the formula Na_{2}CO_{3}·10H_{2}O. Since over 60% of this salt is water, the crystals are sometimes heated until it is driven off. The product is called calcined soda, and is, of course, more valuable than the crystallized salt. 2. _Solvay process._ This more modern process depends upon the reactions represented in the equations NaCl + NH_{4}HCO_{3} = NaHCO_{3} + NH_{4}Cl, 2NaHCO_{3} = Na_{2}CO_{3} + H_{2}O + CO_{2}. The reason the first reaction takes place is that sodium hydrogen carbonate is sparingly soluble in water, while the other compounds are freely soluble. When strong solutions of sodium chloride and of ammonium hydrogen carbonate are brought together the sparingly soluble sodium hydrogen carbonate is precipitated. This is converted into the normal carbonate by heating, the reaction being represented in the second equation. ~Technical preparation.~ In the Solvay process a very concentrated solution of salt is first saturated with ammonia gas, and a current of carbon dioxide is then conducted into the solution. In this way ammonium hydrogen carbonate is formed: NH_{3} + H_{2}O + CO_{2} = NH_{4}HCO_{3}. This enters into double decomposition with the salt, as shown in the first equation under the Solvay process. After the sodium hydrogen carbonate has been precipitated the mother liquors containing ammonium chloride are treated with lime: 2NH_{4}Cl + CaO = CaCl_{2} + 2 NH_{3} + H_{2}O. The lime is obtained by burning limestone: CaCO_{3} = CaO + CO_{2}. The ammonia and carbon dioxide evolved in the latter two reactions are used in the preparation of an additional quantity of ammonium hydrogen carbonate. It will thus be seen that there is no loss of ammonia. The only materials permanently used up are calcium carbonate and salt, while the only waste product is calcium chloride. ~Historical.~ In former times sodium carbonate was made by burning seaweeds and extracting the carbonate from their ash. On this account the salt was called _soda ash_, and the name is still in common use. During the French Revolution this supply was cut off, and in behalf of the French government Le Blanc made a study of methods of preparing the carbonate directly from salt. As a result he devised the method which bears his name, and which was used exclusively for many years. It has been replaced to a large extent by the Solvay process, which has the advantage that the materials used are inexpensive, and that the ammonium hydrogen carbonate used can be regenerated from the products formed in the process. Much expense is also saved in fuel, and the sodium hydrogen carbonate, which is the first product of the process, has itself many commercial uses. The Le Blanc process is still used, however, since the hydrochloric acid generated is of value. ~By-products.~ The substances obtained in a given process, aside from the main product, are called the by-products. The success of many processes depends upon the value of the by-products formed. Thus hydrochloric acid, a by-product in the Le Blanc process, is valuable enough to make the process pay, even though sodium carbonate can be made cheaper in other ways. ~Properties of sodium carbonate.~ Sodium carbonate forms large crystals of the formula Na_{2}CO_{3} · 10 H_{2}O. It has a mild alkaline reaction and is used for laundry purposes under the name of washing soda. Mere mention of the fact that it is used in the manufacture of glass, soap, and many chemical reagents will indicate its importance in the industries. It is one of the few soluble carbonates. ~Sodium hydrogen carbonate~ (_bicarbonate of soda_) (NaHCO_{3}). This salt, commonly called bicarbonate of soda, or baking soda, is made by the Solvay process, as explained above, or by passing carbon dioxide into strong solutions of sodium carbonate: Na_{2}CO_{3} + H_{2}O + CO_{2} = 2NaHCO_{3}. The bicarbonate, being sparingly soluble, crystallizes out. A mixture of the bicarbonate with some substance (the compound known as cream of tartar is generally used) which slowly reacts with it, liberating carbon dioxide, is used largely in baking. The carbon dioxide generated forces its way through the dough, thus making it porous and light. ~Sodium nitrate~ (_Chili saltpeter_) (NaNO_{3}). This substance is found in nature in arid regions in a number of places, where it has been formed apparently by the decay of organic substances in the presence of air and sodium salts. The largest deposits are in Chili, and most of the nitrate of commerce comes from that country. Smaller deposits occur in California and Nevada. The commercial salt is prepared by dissolving the crude nitrate in water, allowing the insoluble earthy materials to settle, and evaporating the clear solution so obtained to crystallization. The soluble impurities remain for the most part in the mother liquors. Since this salt is the only nitrate found extensively in nature, it is the material from which other nitrates as well as nitric acid are prepared. It is used in enormous quantities in the manufacture of sulphuric acid and potassium nitrate, and as a fertilizer. ~Sodium phosphate~ (Na_{2}HPO_{4}·12H_{2}O). Since phosphoric acid has three replaceable hydrogen atoms, three sodium phosphates are possible,--two acid salts and one normal. All three can be made without difficulty, but disodium phosphate is the only one which is largely used, and is the salt which is commonly called sodium phosphate. It is made by the action of phosphoric acid on sodium carbonate: Na_{2}CO_{3} + H_{3}PO_{4} = Na_{2}HPO_{4} + CO_{2} + H_{2}O. It is interesting as being one of the few phosphates which are soluble in water, and is the salt commonly used when a soluble phosphate is needed. ~Normal sodium phosphate~ (Na_{3}PO_{4}). Although this is a normal salt its solution has a strongly alkaline reaction. This is due to the fact that the salt hydrolyzes in solution into sodium hydroxide and disodium phosphate, as represented in the equation Na_{3}PO_{4} + H_{2}O = Na_{2}HPO_{4} + NaOH. Sodium hydroxide is strongly alkaline, while disodium phosphate is nearly neutral in reaction. The solution as a whole is therefore alkaline. The salt is prepared by adding a large excess of sodium hydroxide to a solution of disodium phosphate and evaporating to crystallization. The excess of the sodium hydroxide reverses the reaction of hydrolysis and the normal salt crystallizes out. ~Sodium tetraborate ~(_borax_) (Na_{2}B_{4}O_{7}·10H_{2}O). The properties of this important compound have been discussed under the head of boron. POTASSIUM ~Occurrence in nature.~ Potassium is a constituent of many common rocks and minerals, and is therefore a rather abundant element, though not so abundant as sodium. Feldspar, which occurs both by itself and as a constituent of granite, contains considerable potassium. The element is a constituent of all clay and of mica and also occurs in very large deposits at Stassfurt, Germany, in the form of the chloride and sulphate, associated with compounds of sodium and magnesium. In small quantities it is found as nitrate and in many other forms. The natural decomposition of rocks containing potassium gives rise to various compounds of the element in all fertile soils. Its soluble compounds are absorbed by growing plants and built up into complex vegetable substances; when these are burned the potassium remains in the ash in the form of the carbonate. Crude carbonate obtained from wood ashes was formerly the chief source of potassium compounds; they are now mostly prepared from the salts of the Stassfurt deposits. ~Stassfurt salts.~ These salts form very extensive deposits in middle and north Germany, the most noted locality for working them being at Stassfurt. The deposits are very thick and rest upon an enormous layer of common salt. They are in the form of a series of strata, each consisting largely of a single mineral salt. A cross section of these deposits is shown in Fig. 78. While these strata are salts from a chemical standpoint, they are as solid and hard as many kinds of stone, and are mined as stone or coal would be. Since the strata differ in general appearance, each can be mined separately, and the various minerals can be worked up by methods adapted to each particular case. The chief minerals of commercial importance in these deposits are the following: Sylvine KCl. Anhydrite CaSO_{4}. Carnallite KCl·MgCl_{2}·6H_{2}O. Kainite K_{2}SO_{4}·MgSO_{4}·MgCl_{2}·6H_{2}O. Polyhalite K_{2}SO_{4}·MgSO_{4}·2CaSO_{4}·2H_{2}O. Kieserite MgSO_{4}·H_{2}O. Schönite K_{2}SO_{4}·MgSO_{4}·6H_{2}O. ~Preparation and properties.~ The metal is prepared by the same method used in the preparation of sodium. In most respects it is very similar to sodium, the chief difference being that it is even more energetic in its action upon other substances. The freshly cut, bright surface instantly becomes dim through oxidation by the air. It decomposes water very vigorously, the heat of reaction being sufficient to ignite the hydrogen evolved. It is somewhat lighter than sodium and is preserved under gasoline. [Illustration: Fig. 78] ~Potassium hydroxide~ (_caustic potash_) (KOH). Potassium hydroxide is prepared by methods exactly similar to those used in the preparation of sodium hydroxide, which compound it closely resembles in both physical and chemical properties. It is not used to any very great extent, being replaced by the cheaper sodium hydroxide. ~Action of the halogen elements on potassium hydroxide.~ When any one of the three halogen elements--chlorine, bromine, and iodine--is added to a solution of potassium hydroxide a reaction takes place, the nature of which depends upon the conditions of the experiment. Thus, when chlorine is passed into a cold dilute solution of potassium hydroxide the reaction expressed by the following equation takes place: (1) 2KOH + 2Cl = KCl + KClO + H_{2}O. If the solution of hydroxide is concentrated and hot, on the other hand, the potassium hypochlorite formed according to equation (1) breaks down as fast as formed: (2) 3KClO = KClO_{3} + 2KCl. Equation (1), after being multiplied by 3, may be combined with equation (2), giving the following: (3) 6KOH + 6Cl = 5KCl + KClO_{3} + 3H_{2}O. This represents in a single equation the action of chlorine on hot, concentrated solutions of potassium hydroxide. By means of these reactions one can prepare potassium chloride, potassium hypochlorite, and potassium chlorate. By substituting bromine or iodine for chlorine the corresponding compounds of these elements are obtained. Some of these compounds can be obtained in cheaper ways. If the halogen element is added to a solution of sodium hydroxide or calcium hydroxide, the reaction which takes place is exactly similar to that which takes place with potassium hydroxide. It is possible, therefore, to prepare in this way the sodium and calcium compounds corresponding to the potassium compounds given above. ~Potassium chloride~ (KCl). This salt occurs in nature in sea water, in the mineral sylvine, and, combined with magnesium chloride, as carnallite (KCl·MgCl_{2}·6H_{2}O). It is prepared from carnallite by saturating boiling water with the mineral and allowing the solution to cool. The mineral decomposes while in solution, and the potassium chloride crystallizes out on cooling, while the very soluble magnesium chloride remains in solution. The salt is very similar to sodium chloride both in physical and chemical properties. It is used in the preparation of nearly all other potassium salts, and, together with potassium sulphate, is used as a fertilizer. ~Potassium bromide~ (KBr). When bromine is added to a hot concentrated solution of potassium hydroxide there is formed a mixture of potassium bromide and potassium bromate in accordance with the reactions already discussed. There is no special use for the bromate, so the solution is evaporated to dryness, and the residue, consisting of a mixture of the bromate and bromide, is strongly heated. This changes the bromate to bromide, as follows: KBrO_{3} = KBr +3O. The bromide is then crystallized from water, forming large colorless crystals. It is used in medicine and in photography. ~Potassium iodide~ (KI). Potassium iodide may be made by exactly the same method as has just been described for the bromide, substituting iodine for bromine. It is more frequently made as follows. Iron filings are treated with iodine, forming the compound Fe_{3}I_{8}; on boiling this substance with potassium carbonate the reaction represented in the following equation occurs: Fe_{3}I_{8} + 4K_{2}CO_{3} = Fe_{3}O_{4} + 8KI + 4CO_{2}. Potassium iodide finds its chief use in medicine. ~Potassium chlorate~ (KClO_{3}). This salt, as has just been explained, can be made by the action of chlorine on strong potassium hydroxide solutions. The chief use of potassium chlorate is as an oxidizing agent in the manufacture of matches, fireworks, and explosives; it is also used in the preparation of oxygen and in medicine. ~Commercial preparation.~ By referring to the reaction between chlorine and hot concentrated solutions of potassium hydroxide, it will be seen that only one molecule of potassium chlorate is formed from six molecules of potassium hydroxide. Partly because of this poor yield and partly because the potassium hydroxide is rather expensive, this process is not an economical one for the preparation of potassium chlorate. The commercial method is the following. Chlorine is passed into hot solutions of calcium hydroxide, a compound which is very cheap. The resulting calcium chloride and chlorate are both very soluble. To the solution of these salts potassium chloride is added, and as the solution cools the sparingly soluble potassium chlorate crystallizes out: Ca(ClO_{3})_{2} + 2KCl = 2KClO_{3} + CaCl_{2}. Electro-chemical processes are also used. ~Potassium nitrate~ (_saltpeter_) (KNO_{3}). This salt was formerly made by allowing animal refuse to decompose in the open air in the presence of wood ashes or earthy materials containing potassium. Under these conditions the nitrogen in the organic matter is in part converted into potassium nitrate, which was obtained by extracting the mass with water and evaporating to crystallization. This crude and slow process is now almost entirely replaced by a manufacturing process in which the potassium salt is made from Chili saltpeter: NaNO_{3} + KCl = NaCl + KNO_{3}. This process has been made possible by the discovery of the Chili niter beds and the potassium chloride of the Stassfurt deposits. The reaction depends for its success upon the apparently insignificant fact that sodium chloride is almost equally soluble in cold and hot water. All four factors in the equation are rather soluble in cold water, but in hot water sodium chloride is far less soluble than the other three. When hot saturated solutions of sodium nitrate and potassium chloride are brought together, sodium chloride precipitates and can be filtered off, leaving potassium nitrate in solution, together with some sodium chloride. On cooling, potassium nitrate crystallizes out, leaving small amounts of the other salts in solution. Potassium nitrate is a colorless salt which forms very large crystals. It is stable in the air, and when heated is a good oxidizing agent, giving up oxygen quite readily. Its chief use is in the manufacture of gunpowder. ~Gunpowder.~ The object sought for in the preparation of gunpowder is to secure a solid substance which will remain unchanged under ordinary conditions, but which will explode readily when ignited, evolving a large volume of gas. When a mixture of carbon and potassium nitrate is ignited a great deal of gas is formed, as will be seen from the equation 2KNO_{3} + 3C = CO_{2} + CO + N_{2} + K_{2}CO_{3}. By adding sulphur to the mixture the volume of gas formed in the explosion is considerably increased: 2KNO_{3} + 3C + S = 3CO_{2} + N_{2} + K_{2}S. Gunpowder is simply a mechanical mixture of these three substances in the proportion required for the above reaction. While the equation represents the principal reaction, other reactions also take place. The gases formed in the explosion, when measured under standard conditions, occupy about two hundred and eighty times the volume of the original powder. Potassium sulphide (K_{2}S) is a solid substance, and it is largely due to it that gunpowder gives off smoke and soot when it explodes. Smokeless powder consists of organic substances which, on explosion, give only colorless gases, and hence produce no smoke. Sodium nitrate is cheaper than potassium nitrate, but it is not adapted to the manufacture of the best grades of powder, since it is somewhat deliquescent and does not give up its oxygen so readily as does potassium nitrate. It is used, however, in the cheaper grades of powder, such as are employed for blasting. ~Potassium cyanide~ (KCN). When animal matter containing nitrogen is heated with iron and potassium carbonate, complicated changes occur which result in the formation of a substance commonly called yellow prussiate of potash, which has the formula K_{4}FeC_{6}N_{6}. When this substance is heated with potassium, potassium cyanide is formed: K_{4}FeC_{6}N_{6} + 2 K = 6KCN + Fe. Since sodium is much cheaper than potassium it is often used in place of it: K_{4}FeC_{6}N_{6} + 2Na = 4KCN + 2NaCN + Fe. The mixture of cyanides so resulting serves most of the purposes of the pure salt. It is used very extensively in several metallurgical processes, particularly in the extraction of gold. Potassium cyanide is a white solid characterized by its poisonous properties, and must be used with extreme caution. ~Potassium carbonate~ (_potash_) (K_{2}CO_{3}). This compound occurs in wood ashes in small quantities. It cannot be prepared by the Solvay process, since the acid carbonate is quite soluble in water, but is made by the Le Blanc process. Its chief use is in the manufacture of other potassium salts. ~Other salts of potassium.~ Among the other salts of potassium frequently met with are the sulphate (K_{2}SO_{4}), the acid carbonate (KHCO_{3}), the acid sulphate (KHSO_{4}), and the acid sulphite (KHSO_{3}). These are all white solids. LITHIUM, RUBIDIUM, CÆSIUM Of the three remaining elements of the family--lithium, rubidium, and cæsium--lithium is by far the most common, the other two being very rare. Lithium chloride and carbonate are not infrequently found in natural mineral waters, and as these substances are supposed to increase the medicinal value of the water, they are very often added to artificial mineral waters in small quantities. COMPOUNDS OF AMMONIUM ~General.~ As explained in a previous chapter, when ammonia is passed into water the two compounds combine to form the base NH_{4}OH, known as ammonium hydroxide. When this base is neutralized with acids there are formed the corresponding salts, known as the ammonium salts. Since the ammonium group is univalent, ammonium salts resemble those of the alkali metals in formulas; they also resemble the latter salts very much in their chemical properties, and may be conveniently described in connection with them. Among the ammonium salts the chloride, sulphate, carbonate, and sulphide are the most familiar. ~Ammonium chloride~ (_sal ammoniac_) (NH_{4}Cl). This substance is obtained by neutralizing ammonium hydroxide with hydrochloric acid. It is a colorless substance crystallizing in fine needles, and, like most ammonium salts, is very soluble in water. When placed in a tube and heated strongly it decomposes into hydrochloric acid and ammonia. When these gases reach a cooler portion of the tube they at once recombine, and the resulting ammonium chloride is deposited on the sides of the tube. In this way the salt can be separated from nonvolatile impurities. Ammonium chloride is sometimes used in preparation of ammonia; it is also used in making dry batteries and in the laboratory as a chemical reagent. ~Ammonium sulphate~ ((NH_{4})_{2}SO_{4}). This salt resembles the chloride very closely, and, being cheaper, is used in place of it when possible. It is used in large quantity as a fertilizer, the nitrogen which it contains being a very valuable food for plants. ~Ammonium carbonate~ ((NH_{4})_{2}CO_{3}). This salt, as well as the acid carbonate (NH_{4}HCO_{3}), is used as a chemical reagent. They are colorless solids, freely soluble in water. The normal carbonate is made by heating ammonium chloride with powdered limestone (calcium carbonate), the ammonium carbonate being obtained as a sublimate in compact hard masses: 2NH_{4}Cl + CaCO_{3} = (NH_{4})_{2}CO_{3} + CaCl_{2}. The salt always smells of ammonia, since it slowly decomposes, as shown in the equation (NH_{4})_{2}CO_{3} = NH_{4}HCO_{3} + NH_{3}. The acid carbonate, or bicarbonate, is prepared by saturating a solution of ammonium hydroxide with carbon dioxide: NH_{4}OH + CO_{2} = NH_{4}HCO_{3}. It is a well-crystallized stable substance. ~Ammonium sulphide~ ((NH_{4})_{2}S). Ammonium sulphide is prepared by the action of hydrosulphuric acid upon ammonium hydroxide: 2NH_{4}OH + H_{2}S = (NH_{4})_{2}S + 2H_{2}O. If the action is allowed to continue until no more hydrosulphuric acid is absorbed, the product is the acid sulphide, sometimes called the hydrosulphide: NH_{4}OH + H_{2}S = NH_{4}HS + H_{2}O. If equal amounts of ammonium hydroxide and ammonium acid sulphide are brought together, the normal sulphide is formed: NH_{4}OH + NH_{4}HS = (NH_{4})_{2}S + H_{2}O It has been obtained in the solid state, but only with great difficulty. As used in the laboratory it is always in the form of a solution. It is much used in the process of chemical analysis because it is a soluble sulphide and easily prepared. On exposure to the air ammonium sulphide slowly decomposes, being converted into ammonia, water, and sulphur: (NH_{4})_{2}S + O = 2NH_{3} + H_{2}O + S. As fast as the sulphur is liberated it combines with the unchanged sulphide to form several different ammonium sulphides in which there are from two to five sulphur atoms in the molecule, thus: (NH_{4})_{2}S_{2}, (NH_{4})_{2}S_{3}, (NH_{4})_{2}S_{5}. These sulphides in turn decompose by further action of oxygen, so that the final products of the reaction are those given in the equation. A solution of these compounds is yellow and is sometimes called _yellow ammonium sulphide_. FLAME REACTION--SPECTROSCOPE When compounds of either sodium or potassium are brought into the non-luminous flame of a Bunsen burner the flame becomes colored. Sodium compounds color it intensely yellow, while those of potassium color it pale violet. When only one of these elements is present it is easy to identify it by this simple test, but when both are present the intense color of the sodium flame entirely conceals the pale tint characteristic of potassium compounds. It is possible to detect the potassium flame in such cases, however, in the following way. When light is allowed to shine through a very small hole or slit in some kind of a screen, such as a piece of metal, upon a triangular prism of glass, the light is bent or refracted out of its course instead of passing straight through the glass. It thus comes out of the prism at some angle to the line at which it entered. Yellow light is bent more than red, and violet more than yellow. When light made up of the yellow of sodium and the violet of potassium shines through a slit upon such a prism, the yellow and the violet lights come out at somewhat different angles, and so two colored lines of light--a yellow line and a violet line--are seen on looking into the prism in the proper direction. The instrument used for separating the rays of light in this way is called a _spectroscope_ (Fig. 79). The material to be tested is placed on a platinum wire and held in the colorless Bunsen flame. The resulting light passes through the slit in the end of tube B, and then through B to the prism. The resulting lines of light are seen by looking into the tube A, which contains a magnifying lens. Most elements give more than one image of the slit, each having a different color, and the series of colored lines due to an element is called its spectrum. [Illustration: Fig. 79] The spectra of the known elements have been carefully studied, and any element which imparts a characteristic color to a flame, or has a spectrum of its own, can be identified even when other elements are present. Through the spectroscopic examination of certain minerals a number of elements have been discovered by the observation of lines which did not belong to any known element. A study of the substance then brought to light the new element. Rubidium and cæsium were discovered in this way, rubidium having bright red lines and cæsium a very intense blue line. Lithium colors the flame deep red, and has a bright red line in its spectrum. EXERCISES 1. What is an alkali? Can a metal itself be an alkali? 2. Write equations showing how the following changes may be brought about, giving the general principle involved in each change: NaCl --> Na_{2}SO_{3}, Na_{2}SO_{3} --> NaCl, NaCl --> NaBr, Na_{2}SO_{4} --> NaNO_{3}, NaNO_{3} --> NaHCO_{3}. 3. What carbonates are soluble? 4. State the conditions under which the reaction represented by the following equation can be made to go in either direction: Na_{2}CO_{3} + H_{2}O + CO_{2} <--> 2 NaHCO_{3}. 5. Account for the fact that solutions of sodium carbonate and potassium carbonate are alkaline. 6. What non-metallic element is obtained from the deposits of Chili saltpeter? 7. Supposing concentrated hydrochloric acid (den. = 1.2) to be worth six cents a pound, what is the value of the acid generated in the preparation of 1 ton of sodium carbonate by the Le Blanc process? 8. What weight of sodium carbonate crystals will 1 kg. of the anhydrous salt yield? 9. Write equations for the preparation of potassium hydroxide by three different methods. 10. What would take place if a bit of potassium hydroxide were left exposed to the air? 11. Write the equations for the reactions between sodium hydroxide and bromine; between potassium hydroxide and iodine. 12. Write equations for the preparation of potassium sulphate; of potassium acid carbonate. 13. What weight of carnallite would be necessary in the preparation of 1 ton of potassium carbonate? 14. Write the equations showing how ammonium chloride, ammonium sulphate, ammonium carbonate, and ammonium nitrate may be prepared from ammonium hydroxide. 15. Write an equation to represent the reaction involved in the preparation of ammonia from ammonium chloride. 16. What substances already studied are prepared from the following compounds? ammonium chloride; ammonium nitrate; ammonium nitrite; sodium nitrate; sodium chloride. 17. How could you prove that the water in crystals of common salt is not water of crystallization? 18. How could you distinguish between potassium chloride and potassium iodide? between sodium chloride and ammonium chloride? between sodium nitrate and potassium nitrate? [Illustration: ROBERT WILHELM BUNSEN (German) (1811-1899) Invented many lecture-room and laboratory appliances (Bunsen burner); invented the spectroscope and with it discovered rubidium and cæsium; greatly perfected methods of electrolysis, inventing a new battery; made many investigations among metallic and organic substances] CHAPTER XXIV THE ALKALINE-EARTH FAMILY =========================================================================== | | | | | | | | | MILLIGRAMS SOL- | | | | | UBLE IN 1 L. | | | | | OF WATER AT 18° | | SYMBOL | ATOMIC | DENSITY |__________________| CARBONATE | | WEIGHT | | | | DECOMPOSES | | | | SULPHATE| HYDROX-| | | | | | IDE | __________|________|________|_________|_________|________|_________________ | | | | | | Calcium | Ca | 40.1 | 1.54 | 2070.00 | 1670. | At dull red heat Strontium | Sr | 87.6 | 2.50 | 170.00 | 7460. | At white heat Barium | Ba | 137.4 | 3.75 | 2.29 | 36300. | Scarcely at all =========================================================================== ~The family.~ The alkaline-earth family consists of the very abundant element calcium and the much rarer elements strontium and barium. They are called the alkaline-earth metals because their properties are between those of the alkali metals and the earth metals. The earth metals will be discussed in a later chapter. The family is also frequently called the calcium family. 1. _Occurrence._ These elements do not occur free in nature. Their most abundant compounds are the carbonates and sulphates; calcium also occurs in large quantities as the phosphate and silicate. 2. _Preparation._ The metals were first prepared by Davy in 1808 by electrolysis. This method has again come into use in recent years. Strontium and barium have as yet been obtained only in small quantities and in the impure state, and many of their physical properties, such as their densities and melting points, are therefore imperfectly known. 3. _Properties._ The three metals resemble each other very closely. They are silvery-white in color and are about as hard as lead. Their densities increase with their atomic weights, as is shown in the table on opposite page. Like the alkali metals they have a strong affinity for oxygen, tarnishing in the air through oxidation. They decompose water at ordinary temperatures, forming hydroxides and liberating hydrogen. When ignited in the air they burn with brilliancy, forming oxides of the general formula MO. These oxides readily combine with water, according to the equation MO + H_{2}O = M(OH)_{2}. Each of the elements has a characteristic spectrum, and the presence of the metals can easily be detected by the spectroscope. 4. _Compounds._ The elements are divalent in almost all of their compounds, and these compounds in solution give simple, divalent, colorless ions. The corresponding salts of the three elements are very similar to each other and show a regular variation in properties in passing from calcium to strontium and from strontium to barium. This is seen in the solubility of the sulphate and hydroxide, and in the ease of decomposition of the carbonates, as given in the table. Unlike the alkali metals, their normal carbonates and phosphates are insoluble in water. CALCIUM ~Occurrence.~ The compounds of calcium are very abundant in nature, so that the total amount of calcium in the earth's crust is very large. A great many different compounds containing the clement are known, the most important of which are the following: Calcite (marble) CaCO_{3}. Phosphorite Ca_{3}(PO_{4})_{2}. Fluorspar CaF_{2}. Wollastonite CaSiO_{3}. Gypsum CaSO_{4}·2H_{2}O. Anhydrite CaSO_{4}. ~Preparation.~ Calcium is now prepared by the electrolysis of the melted chloride, the metal depositing in solid condition on the cathode. It is a gray metal, considerably heavier and harder than sodium. It acts upon water, forming calcium hydroxide and hydrogen, but the action does not evolve sufficient heat to melt the metal. It promises to become a useful substance, though no commercial applications for it have as yet been found. ~Calcium oxide~ (_lime, quicklime_) (CaO). Lime is prepared by strongly heating calcium carbonate (limestone) in large furnaces called kilns: CaCO_{3} = CaO + CO_{2}. When pure, lime is a white amorphous substance. Heated intensely, as in the oxyhydrogen flame, it gives a brilliant light called the lime light. Although it is a very difficultly fusible substance, yet in the electric furnace it can be made to melt and even boil. Water acts upon lime with the evolution of a great deal of heat,--hence the name quicklime, or live lime,--the process being called slaking. The equation is CaO + H_{2}O = Ca(OH)_{2}. Lime readily absorbs moisture from the air, and is used to dry moist gases, especially ammonia, which cannot be dried by the usual desiccating agents. It also absorbs carbon dioxide, forming the carbonate CaO + CO_{2} = CaCO_{3}. Lime exposed to air is therefore gradually converted into hydroxide and carbonate, and will no longer slake with water. It is then said to be air-slaked. ~Limekilns.~ The older kiln, still in common use, consists of a large cylindrical stack in which the limestone is loosely packed. A fire is built at the base of the stack, and when the burning is complete it is allowed to die out and the lime is removed from the kiln. The newer kilns are constructed as shown in Fig. 80. A number of fire boxes are built around the lower part of the kiln, one of which is shown at B. The fire is built on the grate F and the hot products of combustion are drawn up through the stack, decomposing the limestone. The kiln is charged at C, and sometimes fuel is added with the limestone to cause combustion throughout the contents of the kiln. The burned lime is raked out through openings in the bottom of the stack, one of which is shown at _D._ The advantage of this kind of a kiln over the older form is that the process is continuous, limestone being charged in at the top as fast as the lime is removed at the bottom. [Illustration: Fig. 80] ~Calcium hydroxide ~ (_slaked lime_) (Ca(OH)_{2}). Pure calcium hydroxide is a light white powder. It is sparingly soluble in water, forming a solution called _limewater_, which is often used in medicine as a mild alkali. Chemically, calcium hydroxide is a moderately strong base, though not so strong as sodium hydroxide. Owing to its cheapness it is much used in the industries whenever an alkali is desired. A number of its uses have already been mentioned. It is used in the preparation of ammonia, bleaching powder, and potassium hydroxide. It is also used to remove carbon dioxide and sulphur compounds from coal gas, to remove the hair from hides in the tanneries (this recalls the caustic or corrosive properties of sodium hydroxide), and for making mortar. ~Mortar~ is a mixture of calcium hydroxide and sand. When it is exposed to the air or spread upon porous materials moisture is removed from it partly by absorption in the porous materials and partly by evaporation, and the mortar becomes firm, or _sets_. At the same time carbon dioxide is slowly absorbed from the air, forming hard calcium carbonate: Ca(OH)_{2} + CO_{2} = CaCO_{3} + H_{2}O. By this combined action the mortar becomes very hard and adheres firmly to the surface upon which it is spread. The sand serves to give body to the mortar and makes it porous, so that the change into carbonate can take place throughout the mass. It also prevents too much shrinkage. ~Cement.~ When limestone to which clay and sand have been added in certain proportions is burned until it is partly fused (some natural marl is already of about the right composition), and the clinker so produced is ground to powder, the product is called cement. When this material is moistened it sets to a hard stone-like mass which retains its hardness even when exposed to the continued action of water. It can be used for under-water work, such as bridge piers, where mortar would quickly soften. Several varieties of cement are made, the best known of which is Portland cement. ~Growing importance of cement.~ Cement is rapidly coming into use for a great variety of purposes. It is often used in place of mortar in the construction of brick buildings. Mixed with crushed stone and sand it forms concrete which is used in foundation work. It is also used in making artificial stone, terra-cotta trimmings for buildings, artificial stone walks and floors, and the like. It is being used more and more for making many articles which were formerly made of wood or stone, and the entire walls of buildings are sometimes made of cement blocks or of concrete. ~Calcium carbonate~ (CaCO_{3}). This substance is found in a great many natural forms to which various names have been given. They may be classified under three heads: 1. _Amorphous carbonate._ This includes those forms which are not markedly crystalline. Limestone is the most familiar of these and is a grayish rock usually found in hard stratified masses. Whole mountain ranges are sometimes made up of this material. It is always impure, usually containing magnesium carbonate, clay, silica, iron and aluminium compounds, and frequently fossil remains. Marl is a mixture of limestone and clay. Pearls, chalk, coral, and shells are largely calcium carbonate. 2. _Hexagonal carbonate._ Calcium carbonate crystallizes in the form of rhomb-shaped crystals which belong to the hexagonal system. When very pure and transparent the substance is called Iceland spar. Calcite is a similar form, but somewhat opaque or clouded. Mexican onyx is a massive variety, streaked or banded with colors due to impurities. Marble when pure is made up of minute calcite crystals. Stalactites and stalagmites are icicle-like forms sometimes found in caves. 3. _Rhombic carbonate._ Calcium carbonate sometimes crystallizes in needle-shaped crystals belonging to the rhombic system. This is the unstable form and tends to go over into the other variety. Aragonite is the most familiar example of this form. ~Preparation and uses of calcium carbonate.~ In the laboratory pure calcium carbonate can be prepared by treating a soluble calcium salt with a soluble carbonate: Na_{2}CO_{3} + CaCl_{2} = CaCO_{3} + 2NaCl. When prepared in this way it is a soft white powder often called precipitated chalk, and is much used as a polishing powder. It is insoluble in water, but dissolves in water saturated with carbon dioxide, owing to the formation of the acid calcium carbonate which is slightly soluble: CaCO_{3} + H_{2}CO_{3} = Ca(HCO_{3})_{2}. The natural varieties of calcium carbonate find many uses, such as in the preparation of lime and carbon dioxide; in metallurgical operations, especially in the blast furnaces; in the manufacture of soda, glass, and crayon (which, in addition to chalk, usually contains clay and calcium sulphate); for building stone and ballast for roads. ~Calcium chloride~ (CaCl_{2}). This salt occurs in considerable quantity in sea water. It is obtained as a by-product in many technical processes, as in the Solvay soda process. When crystallized from its saturated solutions it forms colorless needles of the composition CaCl_{2}·6H_{2}O. By evaporating a solution to dryness and heating to a moderate temperature calcium chloride is obtained anhydrous as a white porous mass. In this condition it absorbs water with great energy and is a valuable drying agent. ~Bleaching powder~ (CaOCl_{2}). When chlorine acts upon a solution of calcium hydroxide the reaction is similar to that which occurs between chlorine and potassium hydroxide: 2 Ca(OH)_{2} + 4 Cl = CaCl_{2} + Ca(ClO)_{2} + 2 H_{2}O. If, however, chlorine is conducted over calcium hydroxide in the form of a dry powder, it is absorbed and a substance is formed which appears to have the composition represented in the formula CaOCl_{2}. This substance is called bleaching powder, or hypochlorite of lime. It is probably the calcium salt of both hydrochloric and hypochlorous acids, so that its structure is represented by the formula /ClO Ca \Cl. In solution this substance acts exactly like a mixture of calcium chloride (CaCl_{2}) and calcium hypochlorite (Ca(ClO)_{2}), since it dissociates to form the ions Ca^{++}, Cl^{-}, and ClO^{-}. Bleaching powder undergoes a number of reactions which make it an important substance. 1. When treated with an acid it evolves chlorine: /ClO Ca + H_{2}SO_{4} = CaSO_{4} + HCl + HClO, \Cl HCl + HClO = H_{2}O + 2Cl. This reaction can be employed in the preparation of chlorine, or the nascent chlorine may be used as a bleaching agent. 2. It is slowly decomposed by the carbon dioxide of the air, yielding calcium carbonate and chlorine: CaOCl_{2} + CO_{2} = CaCO_{3} + 2Cl. Owing to this slow action the substance is a good disinfectant. 3. When its solution is boiled the substance breaks down into calcium chloride and chlorate: 6CaOCl_{2} = 5CaCl_{2} + Ca(ClO_{3})_{2}. This reaction is used in the preparation of potassium chlorate. ~Calcium fluoride~ (_fluorspar_) (CaF_{2}). Fluorspar has already been mentioned as the chief natural compound of fluorine. It is found in large quantities in a number of localities, and is often crystallized in perfect cubes of a light green or amethyst color. It can be melted easily in a furnace, and is sometimes used in the fused condition in metallurgical operations to protect a metal from the action of the air during its reduction. It is used as the chief source of fluorine compounds, especially hydrofluoric acid. ~Calcium sulphate~ (_gypsum_) (CaSO_{4}·2H_{2}O). This abundant substance occurs in very perfectly formed crystals or in massive deposits. It is often found in solution in natural waters and in the sea water. Salts deposited from sea water are therefore likely to contain this substance (see Stassfurt salts). It is very sparingly soluble in water, and is thrown down as a fine white precipitate when any considerable amounts of a calcium salt and a soluble sulphate (or sulphuric acid) are brought together in solution. Its chief use is in the manufacture of plaster of Paris and of hollow tiles for fireproof walls. Such material is called _gypsite_. It is also used as a fertilizer. Calcium sulphate, like the carbonate, occurs in many forms in nature. Gypsum is a name given to all common varieties. Granular or massive specimens are called alabaster, while all those which are well crystallized are called selenite. Satin spar is still another variety often seen in mineral collections. ~Plaster of Paris.~ When gypsum is heated to about 115° it loses a portion of its water of crystallization in accordance with the equation 2(CaSO_{4}·2H_{2}O) = 2CaSO_{4}·H_{2}O + 2H_{2}O. The product is a fine white powder called _plaster of Paris_. On being moistened it again takes up this water, and in so doing first forms a plastic mass, which soon becomes very firm and hard and regains its crystalline structure. These properties make it very valuable as a material for forming casts and stucco work, for cementing glass to metals, and for other similar purposes. If overheated so that all water is driven off, the process of taking up water is so slow that the material is worthless. Such material is said to be dead burned. Plaster of Paris is very extensively used as the finishing coat for plastered walls. ~Hard water.~ Waters containing compounds of calcium and magnesium in solution are called hard waters because they feel harsh to the touch. The hardness of water may be of two kinds,--(1) temporary hardness and (2) permanent hardness. 1. _Temporary hardness._ We have seen that when water charged with carbon dioxide comes in contact with limestone a certain amount of the latter dissolves, owing to the formation of the soluble acid carbonate of calcium. The hardness of such waters is said to be temporary, since it may be removed by boiling. The heat changes the acid carbonate into the insoluble normal carbonate which then precipitates, rendering the water soft: Ca(HCO_{3})_{2} = CaCO_{3} + H_{2}O + CO_{2}. Such waters may also be softened by the addition of sufficient lime or calcium hydroxide to convert the acid carbonate of calcium into the normal carbonate. The equation representing the reaction is Ca(HCO_{3})_{2} + Ca(OH)_{2} = 2CaCO_{3} + 2H_{2}O. 2. _Permanent hardness._ The hardness of water may also be due to the presence of calcium and magnesium sulphates or chlorides. Boiling the water does not affect these salts; hence such waters are said to have permanent hardness. They may be softened, however, by the addition of sodium carbonate, which precipitates the calcium and magnesium as insoluble carbonates: CaSO_{4} + Na_{2}CO_{3} = CaCO_{3} + Na_{2}SO_{4}. This process is sometimes called "breaking" the water. ~Commercial methods for softening water.~ The average water of a city supply contains not only the acid carbonates of calcium and magnesium but also the sulphates and chlorides of these metals, together with other salts in smaller quantities. Such waters are softened on a commercial scale by the addition of the proper quantities of calcium hydroxide and sodium carbonate. The calcium hydroxide is added first to precipitate all the acid carbonates. After a short time the sodium carbonate is added to precipitate the other soluble salts of calcium and magnesium, together with any excess of calcium hydroxide which may have been added. The quantity of calcium hydroxide and sodium carbonate required is calculated from a chemical analysis of the water. It will be noticed that the water softened in this way will contain sodium sulphate and chloride, but the presence of these salts is not objectionable. ~Calcium carbide~ (CaC_{2}). This substance is made by heating well-dried coke and lime in an electrical furnace. The equation is CaO + 3C = CaC_{2} + CO. The pure carbide is a colorless, transparent, crystalline substance. In contact with water it is decomposed with the evolution of pure acetylene gas, having a pleasant ethereal odor. The commercial article is a dull gray porous substance which contains many impurities. The acetylene prepared from this substance has a very characteristic odor due to impurities, the chief of these being phosphine. It is used in considerable quantities as a source of acetylene gas for illuminating purposes. ~Technical preparation.~ Fig. 81 represents a recent type of a carbide furnace. The base of the furnace is provided with a large block of carbon A, which serves as one of the electrodes. The other electrodes B, several in number, are arranged horizontally at some distance above this. A mixture of coal and lime is fed into the furnace through the trap top C, and in the lower part of the furnace this mixture becomes intensely heated, forming liquid carbide. This is drawn off through the taphole D. The carbon monoxide formed in the reaction escapes through the pipes E and is led back into the furnace. The pipes F supply air, so that the monoxide burns as it reënters the furnace and assists in heating the charge. The carbon dioxide so formed, together with the nitrogen entering as air, escape at G. An alternating current is used. [Illustration: Fig. 81] ~Calcium phosphate~ (Ca_{3}(PO_{4})_{2}). This important substance occurs abundantly in nature as a constituent of apatite (3Ca_{3}(PO_{4})_{2}·CaF_{2}), in phosphate rock, and as the chief mineral constituent of bones. Bone ash is therefore nearly pure calcium phosphate. It is a white powder, insoluble in water, although it readily dissolves in acids, being decomposed by them and converted into soluble acid phosphates, as explained in connection with the acids of phosphorus. STRONTIUM ~Occurrence.~ Strontium occurs sparingly in nature, usually as strontianite (SrCO_{3}) and as celestite (SrSO_{4}). Both minerals form beautiful colorless crystals, though celestite is sometimes colored a faint blue. Only a few of the compounds of strontium have any commercial applications. ~Strontium hydroxide~ (Sr(OH)_{2}·8H_{2}O). The method of preparation of strontium hydroxide is analogous to that of calcium hydroxide. The substance has the property of forming an insoluble compound with sugar, which can easily be separated again into its constituents. It is therefore sometimes used in the sugar refineries to extract sugar from impure mother liquors from which the sugar will not crystallize. ~Strontium nitrate~ (Sr(NO_{3})_{2}·4H_{2}O). This salt is prepared by treating the native carbonate with nitric acid. When ignited with combustible materials it imparts a brilliant crimson color to the flame, and because of this property it is used in the manufacture of red lights. BARIUM Barium is somewhat more abundant than strontium, occurring in nature largely as barytes, or heavy spar (BaSO_{4}), and witherite (BaCO_{3}). Like strontium, it closely resembles calcium both in the properties of the metal and in the compounds which it forms. ~Oxides of barium.~ Barium oxide (BaO) can be obtained by strongly heating the nitrate: Ba(NO_{3})_{2} = BaO + 2NO_{2} + O. Heated to a low red heat in the air, the oxide combines with oxygen, forming the peroxide (BaO_{2}). If the temperature is raised still higher, or the pressure is reduced, oxygen is given off and the oxide is once more formed. The reaction BaO_{2} <--> BaO + O is reversible and has been used as a means of separating oxygen from the air. Treated with acids, barium peroxide yields hydrogen peroxide: BaO_{2} + 2HCl = BaCl_{2} + H_{2}O_{2}. ~Barium chloride~ (BaCl_{2}·2H_{2}O). Barium chloride is a white well-crystallized substance which is easily prepared from the native carbonate. It is largely used in the laboratory as a reagent to detect the presence of sulphuric acid or soluble sulphates. ~Barium sulphate~ _(barytes)_ (BaSO_{4}). Barium sulphate occurs in nature in the form of heavy white crystals. It is precipitated as a crystalline powder when a barium salt is added to a solution of a sulphate or sulphuric acid: BaCl_{2} + H_{2}SO_{4} = BaSO_{4} + 2HCl. This precipitate is used, as are also the finely ground native sulphate and carbonate, as a pigment in paints. On account of its low cost it is sometimes used as an adulterant of white lead, which is also a heavy white substance. Barium compounds color the flame green, and the nitrate (Ba(NO_{3})_{2}) is used in the manufacture of green lights. Soluble barium compounds are poisonous. RADIUM ~Historical.~ In 1896 the French scientist Becquerel observed that the mineral pitchblende possesses certain remarkable properties. It affects photographic plates even in complete darkness, and discharges a gold-leaf electroscope when brought close to it. In 1898 Madam Curie made a careful study of pitchblende to see if these properties belong to it or to some unknown substance contained in it. She succeeded in extracting from it a very small quantity of a substance containing a new element which she named radium. In 1910 Madam Curie succeeded in obtaining radium itself by the electrolysis of radium chloride. It is a silver-white metal melting at about 700°. It blackens in the air, forming a nitride, and decomposes water. Its atomic weight is about 226.5. ~Properties.~ Compounds of radium affect a photographic plate or electroscope even through layers of paper or sheets of metal. They also bring about chemical changes in substances placed near them. Investigation of these strange properties has suggested that the radium atoms are unstable and undergo a decomposition. As a result of this decomposition very minute bodies, to which the name corpuscles has been given, are projected from the radium atom with exceedingly great velocity. It is to these corpuscles that the strange properties of radium are due. It seems probable that the gas helium is in some way formed during the decomposition of radium. Two or three other elements, particularly uranium and thorium, have been found to possess many of the properties of radium in smaller degree. ~Radium and the atomic theory.~ If these views in regard to radium should prove to be well founded, it will be necessary to modify in some respects the conception of the atom as developed in a former chapter. The atom would have to be regarded as a compound unit made up of several parts. In a few cases, as in radium and uranium, it would appear that this unit is unstable and undergoes transformation into more stable combinations. This modification would not, in any essential way, be at variance with the atomic theory as propounded by Dalton. EXERCISES 1. What properties have the alkaline-earth metals in common with the alkali metals? In what respects do they differ? 2. Write the equation for the reaction between calcium carbide and water. 3. For what is calcium chlorate used? 4. Could limestone be completely decomposed if heated in a closed vessel? 5. Caves often occur in limestone. Account for their formation. 6. What is the significance of the term fluorspar? (Consult dictionary.) 7. Could calcium chloride be used in place of barium chloride in testing for sulphates? 8. What weight of water is necessary to slake the lime obtained from 1 ton of pure calcium carbonate? 9. What weight of gypsum is necessary in the preparation of 1 ton of plaster of Paris? 10. Write equations to represent the reactions involved in the preparation of strontium hydroxide and strontium nitrate from strontianite. 11. Write equations to represent the reactions involved in the preparation of barium chloride from heavy spar. 12. Could barium hydroxide be used in place of calcium hydroxide in testing for carbon dioxide? CHAPTER XXV THE MAGNESIUM FAMILY =========================================================================== |SYMBOL |ATOMIC |DENSITY |MELTING |BOILING | OXIDE | |WEIGHT | | POINT | POINT | --------------------------------------------------------------------------- Magnesium | Mg | 24.36 | 1.75 | 750° | 920° | MgO Zinc | Zn | 65.4 | 7.00 | 420° | 950° | ZnO Cadmium | Cd |112.4 | 8.67 | 320° | 778° | CdO =========================================================================== ~The family.~ In the magnesium family are included the four elements: magnesium, zinc, cadmium, and mercury. Between the first three of these metals there is a close family resemblance, such as has been traced between the members of the two preceding families. Mercury in some respects is more similar to copper and will be studied in connection with that metal. 1. _Properties._ When heated to a high temperature in the air each of these metals combines with oxygen to form an oxide of the general formula MO, in which M represents the metal. Magnesium decomposes boiling water slowly, while zinc and cadmium have but little action on it. 2. _Compounds._ The members of this group are divalent in nearly all their compounds, so that the formulas of their salts resemble those of the alkaline-earth metals. Like the alkaline-earth metals, their carbonates and phosphates are insoluble in water. Their sulphates, however, are readily soluble. Unlike both the alkali and alkaline-earth metals, their hydroxides are nearly insoluble in water. Most of their compounds dissociate in such a way as to give a simple, colorless, metallic ion. MAGNESIUM ~Occurrence.~ Magnesium is a very abundant element in nature, ranking a little below calcium in this respect. Like calcium, it is a constituent of many rocks and also occurs in the form of soluble salts. ~Preparation.~ The metal magnesium, like most metals whose oxides are difficult to reduce with carbon, was formerly prepared by heating the anhydrous chloride with sodium: MgCl_{2} + 2Na = 2NaCl + Mg. It is now made by electrolysis, but instead of using as the electrolyte the melted anhydrous chloride, which is difficult to obtain, the natural mineral carnallite is used. This is melted in an iron pot which also serves as the cathode in the electrolysis. A rod of carbon dipping into the melted salt serves as the anode. The apparatus is very similar to the one employed in the preparation of sodium. ~Properties.~ Magnesium is a rather tough silvery-white metal of small density. Air does not act rapidly upon it, but a thin film of oxide forms upon its surface, dimming its bright luster. The common acids dissolve it with the formation of the corresponding salts. It can be ignited readily and in burning liberates much heat and gives a brilliant white light. This light is very rich in the rays which affect photographic plates, and the metal in the form of fine powder is extensively used in the production of flash lights and for white lights in pyrotechnic displays. ~Magnesium oxide~ (_magnesia_) (MgO). Magnesium oxide, sometimes called magnesia or magnesia usta, resembles lime in many respects. It is much more easily formed than lime and can be made in the same way,--by igniting the carbonate. It is a white powder, very soft and light, and is unchanged by heat even at very high temperatures. For this reason it is used in the manufacture of crucibles, for lining furnaces, and for other purposes where a refractory substance is needed. It combines with water to form magnesium hydroxide, but much more slowly and with the production of much less heat than in the case of calcium oxide. ~Magnesium hydroxide~ (Mg(OH)_{2}). The hydroxide formed in this way is very slightly soluble in water, but enough dissolves to give the water an alkaline reaction. Magnesium hydroxide is therefore a fairly strong base. It is an amorphous white substance. Neither magnesia nor magnesium salts have a very marked effect upon the system; and for this reason magnesia is a very suitable antidote for poisoning by strong acids, since any excess introduced into the system will have no injurious effect. ~Magnesium cement.~ A paste of magnesium hydroxide and water slowly absorbs carbon dioxide from the air and becomes very hard. The hardness of the product is increased by the presence of a considerable amount of magnesium chloride in the paste. The hydroxide, with or without the chloride, is used in the preparation of cements for some purposes. ~Magnesium carbonate~ (MgCO_{3}). Magnesium carbonate is a very abundant mineral. It occurs in a number of localities as magnesite, which is usually amorphous, but sometimes forms pure crystals resembling calcite. More commonly it is found associated with calcium carbonate. The mineral dolomite has the composition CaCO_{3}·MgCO_{3}. Limestone containing smaller amounts of magnesium carbonate is known as dolomitic limestone. Dolomite is one of the most common rocks, forming whole mountain masses. It is harder and less readily attacked by acids than limestone. It is valuable as a building stone and as ballast for roadbeds and foundations. Like calcium carbonate, magnesium carbonate is insoluble in water, though easily dissolved by acids. ~Basic carbonate of magnesium.~ We should expect to find magnesium carbonate precipitated when a soluble magnesium salt and a soluble carbonate are brought together: Na_{2}CO_{3} + MgCl_{2} = MgCO_{3} + 2NaCl. Instead of this, some carbon dioxide escapes and the product is found to be a basic carbonate. The most common basic carbonate of magnesium has the formula 4MgCO_{3}·Mg(OH)_{2}, and is sometimes called magnesia alba. This compound is formed by the partial hydrolysis of the normal carbonate at first precipitated: 5MgCO_{3} + 2H_{2}O = 4MgCO_{3}·Mg(OH)_{2} + H_{2}CO_{3}. ~Magnesium chloride~ (MgCl_{2}·6H_{2}O). Magnesium chloride is found in many natural waters and in many salt deposits (see Stassfurt salts). It is obtained as a by-product in the manufacture of potassium chloride from carnallite. As there is no very important use for it, large quantities annually go to waste. When heated to drive off the water of crystallization the chloride is decomposed as shown in the equation MgCl_{2}·6H_{2}O = MgO + 2HCl + 5H_{2}O. Owing to the abundance of magnesium chloride, this reaction is being used to some extent in the preparation of both magnesium oxide and hydrochloric acid. ~Boiler scale.~ When water which contains certain salts in solution is evaporated in steam boilers, a hard insoluble material called _scale_ deposits in the boiler. The formation of this scale may be due to several distinct causes. 1. _To the deposit of calcium sulphate._ This salt, while sparingly soluble in cold water, is almost completely insoluble in superheated water. Consequently it is precipitated when water containing it is heated in a boiler. 2. _To decomposition of acid carbonates._ As we have seen, calcium and magnesium acid carbonates are decomposed on heating, forming insoluble normal carbonates: Ca(HCO_{3})_{2} = CaCO_{3} + H_{2}O + CO_{2}. 3. _To hydrolysis of magnesium salts._ Magnesium chloride, and to some extent magnesium sulphate, undergo hydrolysis when superheated in solution, and the magnesium hydroxide, being sparingly soluble, precipitates: MgCl_{2} + 2H_{2}O <--> Mg(OH)_{2} + 2HCl. This scale adheres tightly to the boiler in compact layers and, being a non-conductor of heat, causes much waste of fuel. It is very difficult to remove, owing to its hardness and resistance to reagents. Thick scale sometimes cracks, and the water coming in contact with the overheated iron occasions an explosion. Moreover, the acids set free in the hydrolysis of the magnesium salts attack the iron tubes and rapidly corrode them. These causes combine to make the formation of scale a matter which occasions much trouble in cases where hard water is used in steam boilers. Water containing such salts should be softened, therefore, before being used in boilers. ~Magnesium sulphate~ (_Epsom salt_) (MgSO_{4}·7H_{2}O). Like the chloride, magnesium sulphate is found rather commonly in springs and in salt deposits. A very large deposit of the almost pure salt has been found in Wyoming. Its name was given to it because of its abundant occurrence in the waters of the Epsom springs in England. Magnesium sulphate has many uses in the industries. It is used to a small extent in the preparation of sodium and potassium sulphates, as a coating for cotton cloth, in the dye industry, in tanning, and in the manufacture of paints and laundry soaps. To some extent it is used in medicine. ~Magnesium silicates.~ Many silicates containing magnesium are known and some of them are important substances. Serpentine, asbestos, talc, and meerschaum are examples of such substances. ZINC ~Occurrence.~ Zinc never occurs free in nature. Its compounds have been found in many different countries, but it is not a constituent of common rocks and minerals, and its occurrence is rather local and confined to definite deposits or pockets. It occurs chiefly in the following ores: Sphalerite (zinc blende) ZnS. Zincite ZnO. Smithsonite ZnCO_{3}. Willemite Zn_{2}SiO_{4}. Franklinite ZnO·Fe_{2}O_{3}. One fourth of the world's output of zinc comes from the United States, Missouri being the largest producer. ~Metallurgy.~ The ores employed in the preparation of zinc are chiefly the sulphide, oxide, and carbonate. They are first roasted in the air, by which process they are changed into oxide: ZnCO_{3} = ZnO + CO_{2}, ZnS + 3O = ZnO + SO_{2}. The oxide is then mixed with coal dust, and the mixture is heated in earthenware muffles or retorts, natural gas being used as fuel in many cases. The oxide is reduced by this means to the metallic state, and the zinc, being volatile at the high temperature reached, distills and is collected in suitable receivers. At first the zinc collects in the form of fine powder, called zinc dust or flowers of zinc, recalling the formation under similar conditions of flowers of sulphur. Later, when the whole apparatus has become warm, the zinc condenses to a liquid in the receiver, from which it is drawn off into molds. Commercial zinc often contains a number of impurities, especially carbon, arsenic, and iron. ~Physical properties.~ Pure zinc is a rather heavy bluish-white metal with a high luster. It melts at about 420°, and if heated much above this temperature in the air takes fire and burns with a very bright bluish flame. It boils at about 950° and can therefore be purified by distillation. Many of the physical properties of zinc are much influenced by the temperature and previous treatment of the metal. When cast into ingots from the liquid state it becomes at ordinary temperatures quite hard, brittle, and highly crystalline. At 150° it is malleable and can be rolled into thin sheets; at higher temperatures it again becomes very brittle. When once rolled into sheets it retains its softness and malleability at ordinary temperatures. When melted and poured into water it forms thin brittle flakes, and in this condition is called granulated or mossy zinc. ~Chemical properties.~ Zinc is tarnished superficially by moist air, but beyond this is not affected by it. It does not decompose even boiling water. When the metal is quite pure, sulphuric and hydrochloric acids have scarcely any action upon it; when, however, it contains small amounts of other metals such as magnesium or arsenic, or when it is merely in contact with metallic platinum, brisk action takes place and hydrogen is evolved. For this reason, when pure zinc is used in the preparation of hydrogen a few drops of platinum chloride are often added to the solution to assist the chemical action. Nitric acid dissolves the metal readily, with the formation of zinc nitrate and various reduction products of nitric acid. The strong alkalis act upon zinc and liberate hydrogen: Zn + 2KOH = Zn(OK)_{2} + 2H. The product of this reaction, potassium zincate, is a salt of zinc hydroxide, which is thus seen to have acid properties, though it usually acts as a base. ~Uses of zinc.~ The metal has many familiar uses. Rolled into sheets, it is used as a lining for vessels which are to contain water. As a thin film upon the surface of iron (galvanized iron) it protects the iron from rust. Iron is usually galvanized by dipping it into a bath of melted zinc, but electrical methods are also employed. Zinc plates are used in many forms of electrical batteries. In the laboratory zinc is used in the preparation of hydrogen, and in the form of zinc dust as a reducing agent. One of the largest uses of zinc is in the manufacture of alloys. Brass, an alloy of zinc and copper, is the most important of these; German silver, consisting of copper, zinc, and nickel, has many uses; various bronzes, coin metals, and bearing metals also contain zinc. Its ability to alloy with silver finds application in the separation of silver from lead (see silver). ~Compounds of zinc.~ In general, the compounds of zinc are similar in formula and appearance to those of magnesium, but in other properties they often differ markedly. A number of them have value in commercial ways. ~Zinc oxide~ (_zinc white_) (ZnO). Zinc oxide occurs in impure form in nature, being colored red by manganese and iron compounds. It can be prepared just like magnesium oxide, but is more often made by burning the metal. Zinc oxide is a pure white powder which becomes yellow on heating and regains its white color when cold. It is much used as a white pigment in paints, under the name of zinc white, and has the advantage over white lead in that it is not changed in color by sulphur compounds, while lead turns black. It is also used in the manufacture of rubber goods. ~Commercial preparation of zinc oxide.~ Commercially it is often made from franklinite in the following way. The franklinite is mixed with coal and heated to a high temperature in a furnace, by which process the zinc is set free and converted into vapor. As the vapor leaves the furnace through a conduit it meets a current of air and takes fire in it, forming zinc oxide. The oxide passes on and is filtered from the air through canvas bags, which allow the air to pass but retain the oxide. It is thus made by burning the metal, though the metal is not actually isolated in the process. ~Soluble salts.~ The soluble salts of zinc can be made by dissolving the metal or the oxide in the appropriate acid. They are all somewhat poisonous. The sulphate and chloride are the most familiar. ~Zinc sulphate~ (_white vitriol_) (ZnSO_{4}·7H_{2}O). This salt is readily crystallized from strong solutions in transparent colorless crystals. It is prepared commercially by careful roasting of the sulphide: ZnS + 4O = ZnSO_{4}. ~Zinc chloride~ (ZnCl_{2}·H_{2}O). When a solution of zinc chloride is slowly evaporated a salt of the composition ZnCl_{2}·H_{2}O crystallizes out. If the water is completely expelled by heat and the residue distilled, the anhydrous chloride is obtained and may be cast into sticks or broken into lumps. In this distillation, just as in heating magnesium chloride, some of the chloride is decomposed: ZnCl_{2}·H_{2}O = ZnO + 2HCl. The anhydrous chloride has a great affinity for water, and is used as a dehydrating agent. It is also a germicide, and wood which is to be exposed to conditions which favor decay, as, for example, railroad ties, is often soaked in solutions of this salt. ~Insoluble compounds.~ The insoluble compounds of zinc can be prepared by precipitation. The most important are the sulphide, carbonate, and hydroxide. ~Zinc sulphide~ (ZnS). This substance occurs as the mineral sphalerite, and is one of the most valued ores of zinc. Very large deposits occur in southwestern Missouri. The natural mineral is found in large crystals or masses, resembling resin in color and luster. When prepared by precipitation the sulphide is white. CADMIUM ~The element.~ This element occurs in small quantities in some zinc ores. In the course of the metallurgy of zinc the cadmium compounds undergo chemical changes quite similar to those of the zinc compounds, and the cadmium distills along with the zinc. Being more volatile, it comes over with the first of the zinc and is prepared from the first portions of the distillate by special methods of purification. The element very closely resembles zinc in most respects. Some of its alloys are characterized by having low melting points. ~Compounds of cadmium.~ Among the compounds of cadmium may be mentioned the chloride (CdCl_{2}·2H_{2}O), the sulphate (3CdSO_{4}·8H_{2}O), and the nitrate (Cd(NO_{3})_{2}·4H_{2}O). These are white solids soluble in water. The sulphide (CdS) is a bright yellow substance which is insoluble in water and in dilute acids. It is valuable as a pigment in fine paints. EXERCISES 1. What properties have the metals of the magnesium family in common with the alkali metals; with the alkaline-earth metals? 2. Compare the action of the metals of the magnesium group on water with that of the other metals studied. 3. What metals already studied are prepared by electrolysis? 4. Write the equations representing the reactions between magnesium and hydrochloric acid; between magnesium and dilute sulphuric acid. 5. What property of magnesium was taken advantage of in the isolation of argon? 6. With phosphoric acid magnesium forms salts similar to those of calcium. Write the names and formulas of the corresponding magnesium salts. 7. How could you distinguish between magnesium chloride and magnesium sulphate? between Glauber's salts and Epsom salts? 8. What weight of carnallite is necessary in the preparation of 500 g. of magnesium? 9. Account for the fact that paints made of zinc oxide are not colored by hydrosulphuric acid. 10. What hydroxide studied, other than zinc hydroxide, has both acid and basic properties? 11. Write equations showing how the following compounds of zinc may be obtained from metallic zinc: the oxide, chloride, nitrate, carbonate, sulphate, sulphide, hydroxide. CHAPTER XXVI THE ALUMINIUM FAMILY ~The family.~ The element aluminium is the most abundant member of the group of elements known as the aluminium family; indeed, the other members of the family--gallium, indium, and thallium--are of such rare occurrence that they need not be separately described. The elements of the family are ordinarily trivalent, so that the formulas for their compounds differ from those of the elements so far studied. Their hydroxides are practically insoluble in water and are very weak bases; indeed, the bases are so weak that their salts are often hydrolyzed into free base and free acid in solution. The salts formed from these bases usually contain water of crystallization, which cannot be driven off without decomposing them more or less. The trivalent metals, which in addition to aluminium include also iron and chromium, are sometimes called the _earth metals_. The name refers to the earthy appearance of the oxides of these metals, and to the fact that many earths, soils, and rocks are composed in part of these substances. ALUMINIUM ~Occurrence.~ Aluminium never occurs in the free state in nature, owing to its great affinity for oxygen. In combined form, as oxides, silicates, and a few other salts, it is both abundant and widely distributed, being an essential constituent of all soils and of most rocks excepting limestone and sandstone. Cryolite (Na_{3}AlF_{6}), found in Greenland, and bauxite, which is an aluminium hydroxide usually mixed with some iron hydroxide, are important minerals. It is estimated that aluminium composes about 8% of the earth's crust. In the industries the metal is called aluminum, but its chemical name is aluminium. [Illustration: Fig. 82] ~Preparation.~ Aluminium was first prepared by Wöhler, in 1827, by heating anhydrous aluminium chloride with potassium: AlCl_{3} + 3K = 3KCl + Al. This method was tried after it was found impossible to reduce the oxide of aluminium with carbon. The metal possessed such interesting properties and promised to be so useful that many efforts were made to devise a cheap way of preparing it. The method which has proved most successful consists in the electrolysis of the oxide dissolved in melted cryolite. ~Metallurgy.~ An iron box A (Fig. 82) about eight feet long and six feet wide is connected with a powerful generator in such a way as to serve as the cathode upon which the aluminium is deposited. Three or four rows of carbon rods B dip into the box and serve as the anodes. The box is partially filled with cryolite and the current is turned on, generating enough heat to melt the cryolite. Aluminium oxide is then added, and under the influence of the electric current it decomposes into aluminium and oxygen. The temperature is maintained above the melting point of aluminium, and the liquid metal, being heavier than cryolite, sinks to the bottom of the vessel, from which it is tapped off from time to time through the tap hole C. The oxygen in part escapes as gas, and in part combines with the carbon of the anode, the combustion being very brilliant. The process is carried on at Niagara Falls. The largest expense in the process, apart from the cost of electrical energy, is the preparation of aluminium oxide free from other oxides, for most of the oxide found in nature is too impure to serve without refining. Bauxite is the principal ore used as a source of the aluminium because it is converted into pure oxide without great difficulty. Since common clay is a silicate of aluminium and is everywhere abundant, it might be expected that this would be utilized in the preparation of aluminium. It is, however, very difficult to extract the aluminium from a silicate, and no practical method has been found which will accomplish this. ~Physical properties.~ Aluminium is a tin-white metal which melts at 640° and is very light, having a density of 2.68. It is stiff and strong, and with frequent annealing can be rolled into thin foil. It is a good conductor of heat and electricity, though not so good as copper for a given cross section of wire. ~Chemical properties.~ Aluminium is not perceptibly acted on by boiling water, and moist air merely dims its luster. Further action is prevented in each case by the formation of an extremely thin film of oxide upon the surface of the metal. It combines directly with chlorine, and when heated in oxygen burns with great energy and the liberation of much heat. It is therefore a good reducing agent. Hydrochloric acid acts upon it, forming aluminium chloride: nitric acid and dilute sulphuric acid have almost no action on it, but hot, concentrated sulphuric acid acts upon it in the same way as upon copper: 2Al + 6H_{2}SO_{4} = Al_{2}(SO_{4})_{3} + 6H_{2}O + 3SO_{2}. Alkalis readily attack the metal, liberating hydrogen, as in the case of zinc: Al + 3KOH = Al(OK)_{3} + 3H. Salt solutions, such as sea water, corrode the metal rapidly. It alloys readily with other metals. ~Uses of aluminium.~ These properties suggest many uses for the metal. Its lightness, strength, and permanence make it well adapted for many construction purposes. These same properties have led to its extensive use in the manufacture of cooking utensils. The fact that it is easily corroded by salt solutions is, however, a disadvantage. Owing to its small resistance to electrical currents, it is replacing copper to some extent in electrical construction, especially for trolley and power wires. Some of its alloys have very valuable properties, and a considerable part of the aluminium manufactured is used for this purpose. Aluminium bronze, consisting of about 90% copper and 10% aluminium, has a pure golden color, is strong and malleable, is easily cast, and is permanent in the air. Considerable amounts of aluminium steel are also made. ~Goldschmidt reduction process.~ Aluminium is frequently employed as a powerful reducing agent, many metallic oxides which resist reduction by carbon being readily reduced by it. The aluminium in the form of a fine powder is mixed with the metallic oxide, together with some substance such as fluorspar to act as a flux. The mixture is ignited, and the aluminium unites with the oxygen of the metallic oxide, liberating the metal. This collects in a fused condition under the flux. An enormous quantity of heat is liberated in this reaction, and a temperature as high as 3500° can be reached. The heat of the reaction is turned to practical account in welding car rails, steel castings, and in similar operations where an intense local heat is required. A mixture of aluminium with various metallic oxides, ready prepared for such purposes, is sold under the name of _thermite_. [Illustration: Fig. 83] ~Preparation of chromium by the Goldschmidt method.~ A mixture of chromium oxide and aluminium powder is placed in a Hessian crucible (A, Fig. 83), and on top of it is placed a small heap B of a mixture of sodium peroxide and aluminium, into which is stuck a piece of magnesium ribbon C. Powdered fluorspar D is placed around the sodium peroxide, after which the crucible is set on a pan of sand and the magnesium ribbon ignited. When the flame reaches the sodium peroxide mixture combustion of the aluminium begins with almost explosive violence, so that great care must be taken in the experiment. The heat of this combustion starts the reaction in the chromium oxide mixture, and the oxide is reduced to metallic chromium. When the crucible has cooled a button of chromium will be found in the bottom. ~Aluminium oxide~ (Al_{2}O_{3}). This substance occurs in several forms in nature. The relatively pure crystals are called corundum, while emery is a variety colored dark gray or black, usually with iron compounds. In transparent crystals, tinted different colors by traces of impurities, it forms such precious stones as the sapphire, oriental ruby, topaz, and amethyst. All these varieties are very hard, falling little short of the diamond in this respect. Chemically pure aluminium oxide can be made by igniting the hydroxide, when it forms an amorphous white powder: 2Al(OH)_{3} = Al_{2}O_{3} + 3H_{2}O. The natural varieties, corundum and emery, are used for cutting and grinding purposes; the purest forms, together with the artificially prepared oxide, are largely used in the preparation of aluminium. ~Aluminium hydroxide~ (Al(OH)_{3}). The hydroxide occurs in nature as the mineral hydrargyllite, and in a partially dehydrated form called bauxite. It can be prepared by adding ammonium hydroxide to any soluble aluminium salt, forming a semi-transparent precipitate which is insoluble in water but very hard to filter. It dissolves in most acids to form soluble salts, and in the strong bases to form aluminates, as indicated in the equations Al(OH)_{3} + 3HCl = AlCl_{3} + 3H_{2}O, Al(OH)_{3} + 3NaOH = Al(ONa)_{3} + 3H_{2}O. It may act, therefore, either as a weak base or as a weak acid, its action depending upon the character of the substances with which it is in contact. When heated gently the hydroxide loses part of its hydrogen and oxygen according to the equation Al(OH)_{3} = AlO·OH + H_{2}O. This substance, the formula of which is frequently written HAlO_{2}, is a more pronounced acid than is the hydroxide, and its salts are frequently formed when aluminium compounds are fused with alkalis. The magnesium salt Mg(AlO_{2})_{2} is called spinel, and many other of its salts, called aluminates, are found in nature. When heated strongly the hydroxide is changed into oxide, which will not again take up water on being moistened. ~Mordants and dyeing.~ Aluminium hydroxide has the peculiar property of combining with many soluble coloring materials and forming insoluble products with them. On this account it is often used as a filter to remove objectionable colors from water. This property also leads to its wide use in the dye industry. Many dyes will not adhere to natural fibers such as cotton and wool, that is, will not "dye fast." If, however, the cloth to be dyed is soaked in a solution of aluminium compounds and then treated with ammonia, the aluminium salts which have soaked into the fiber will be converted into the hydroxide, which, being insoluble, remains in the body of it. If the fiber is now dipped into a solution of the dye, the aluminium hydroxide combines with the color material and fastens, or "fixes," it upon the fiber. A substance which serves this purpose is called a _mordant_, and aluminium salts, particularly the acetate, are used in this way. ~Aluminium chloride~ (AlCl_{3}·6 H_{2}O). This substance is prepared by dissolving the hydroxide in hydrochloric acid and evaporating to crystallization. When heated it is converted into the oxide, resembling magnesium in this respect: 2(AlCl_{3}·6 H_{2}O) = Al_{2}O_{3} + 6HCl + 9H_{2}O. The anhydrous chloride, which has some important uses, is made by heating aluminium turnings in a current of chlorine. ~Alums.~ Aluminium sulphate can be prepared by the action of sulphuric acid upon aluminium hydroxide. It has the property of combining with the sulphates of the alkali metals to form compounds called _alums_. Thus, with potassium sulphate the reaction is expressed by the equation K_{2}SO_{4} + Al_{2}(SO_{4})_{3} + 24H_{2}O = 2(KAl(SO_{4})_{2}·12H_{2}O). Under similar conditions ammonium sulphate yields ammonium alum: (NH_{4})_{2}SO_{4} + Al_{2}(SO_{4})_{3} + 24H_{2}O = 2(NH_{4}Al(SO_{4})_{2}·12H_{2}O). Other trivalent sulphates besides aluminium sulphate can form similar compounds with the alkali sulphates, and these compounds are also called alums, though they contain no aluminium. They all crystallize in octahedra and contain twelve molecules of water of crystallization. The alums most frequently prepared are the following: Potassium alum KAl(SO_{4})_{2}·12H_{2}O. Ammonium alum NH_{4}Al(SO_{4})_{2}·12H_{2}O. Ammonium iron alum NH_{4}Fe(SO_{4})_{2}·12H_{2}O. Potassium chrome alum KCr(SO_{4})_{2}·12H_{2}O. An alum may therefore be regarded as a compound derived from two molecules of sulphuric acid, in which one hydrogen atom has been displaced by the univalent alkali atom, and the other three hydrogen atoms by an atom of one of the trivalent metals, such as aluminium, iron, or chromium. Very large, well-formed crystals of an alum can be prepared by suspending a small crystal by a thread in a saturated solution of the alum, as shown in Fig. 84. The small crystal slowly grows and assumes a very perfect form. [Illustration: Fig. 84] ~Other salts of aluminium.~ While aluminium hydroxide forms fairly stable salts with strong acids, it is such a weak base that its salts with weak acids are readily hydrolyzed. Thus, when an aluminium salt and a soluble carbonate are brought together in solution we should expect to have aluminium carbonate precipitated according to the equation 3Na_{2}CO_{3} + 2AlCl_{3} = Al_{2}(CO_{3})_{3} + 6NaCl. But if it is formed at all, it instantly begins to hydrolyze, the products of the hydrolysis being aluminium hydroxide and carbonic acid, Al_{2}(CO_{3})_{3} + 6H_{2}O = 2Al(OH)_{3} + 3H_{2}CO_{3}. Similarly a soluble sulphide, instead of precipitating aluminium sulphide (Al_{2}S_{3}), precipitates aluminium hydroxide; for hydrogen sulphide is such a weak acid that the aluminium sulphide at first formed hydrolyzes at once, forming aluminium hydroxide and hydrogen sulphide: 3Na_{2}S + 2AlCl_{3} + 6H_{2}O = 2Al(OH)_{3} + 6NaCl + 3H_{2}S. ~Alum baking powders.~ It is because of the hydrolysis of aluminium carbonate that alum is used as a constituent of some baking powders. The alum baking powders consist of a mixture of alum and sodium hydrogen carbonate. When water is added the two compounds react together, forming aluminium carbonate, which hydrolyzes into aluminium hydroxide and carbonic acid. The carbon dioxide from the latter escapes through the dough and in so doing raises it into a porous condition, which is the end sought in the use of a baking powder. ~Aluminium silicates.~ One of the most common constituents of rocks is feldspar (KAlSi_{3}O_{8}), a mixed salt of potassium and aluminium with the polysilicic acid (H_{4}Si_{3}O_{8}). Under the influence of moisture, carbon dioxide, and changes of temperature this substance is constantly being broken down into soluble potassium compounds and hydrated aluminium silicate. This compound has the formula Al_{2}Si_{2}O_{7}·2H_{2}O. In relatively pure condition it is called kaolin; in the impure state, mixed with sand and other substances, it forms common clay. Mica is another very abundant mineral, having varying composition, but being essentially of the formula KAlSiO_{4}. Serpentine, talc, asbestos, and meerschaum are important complex silicates of aluminium and magnesium, and granite is a mechanical mixture of quartz, feldspar, and mica. ~Ceramic industries.~ Many articles of greatest practical importance, ranging from the roughest brick and tile to the finest porcelain and chinaware, are made from some form of kaolin, or clay. No very precise classification of such ware can be made, as the products vary greatly in properties, depending upon the materials used and the treatment during manufacture. Porcelain is made from the purest kaolin, to which must be added some less pure, plastic kaolin, since the pure substance is not sufficiently plastic. There is also added some more fusible substance, such as feldspar, gypsum, or lime, together with some pure quartz. The constituents must be ground very fine, and when thoroughly mixed and moistened must make a plastic mass which can be molded into any desired form. The article molded from such materials is then burned. In this process the article is slowly heated to a point at which it begins to soften and almost fuse, and then it is allowed to cool slowly. At this stage, a very thin vessel will be translucent and have an almost glassy fracture; if, however, it is somewhat thicker, or has not been heated quite so high, it will still be porous, and partly on this account and partly to improve its appearance it is usually glazed. Glazing is accomplished by spreading upon the object a thin layer of a more fusible mixture of the same materials as compose the body of the object itself, and again heating until the glaze melts to a transparent glassy coating upon the surface of the vessel. In some cases fusible mixtures of quite different composition from that used in fashioning the vessel may be used as a glaze. Oxides of lead, zinc, and barium are often used in this way. When less carefully selected materials are used, or quite thick vessels are made, various grades of stoneware are produced. The inferior grades are glazed by throwing a quantity of common salt into the kiln towards the end of the first firing. In the form of vapor the salt attacks the surface of the baked ware and forms an easily fusible sodium silicate upon it, which constitutes a glaze. Vitrified bricks, made from clay or ground shale, are burned until the materials begin to fuse superficially, forming their own glaze. Other forms of brick and tile are not glazed at all, but are left porous. The red color of ordinary brick and earthenware is due to an oxide of iron formed in the burning process. The decorations upon china are sometimes painted upon the baked ware and then glazed over, and sometimes painted upon the glaze and burned in by a third firing. Care must be taken to use such pigments as are not affected by a high heat and do not react chemically with the constituents of the baked ware or the glaze. EXERCISES 1. What metals and compounds studied are prepared by electrolysis? 2. Write the equation for the reaction between aluminium and hydrochloric acid; between aluminium and sulphuric acid (in two steps). 3. What hydroxides other than aluminium hydroxide have both acid and basic properties? 4. Write equations showing the methods used for preparing aluminium hydroxide and sulphate. 5. Write the general formula of an alum, representing an atom of an alkali metal by X and an atom of a trivalent metal by Y. 6. What is meant by the term polysilicic acid, as used in the discussion of aluminium silicates? 7. Compare the properties of the hydroxides of the different groups of metals so far studied. 8. In what respects does aluminium oxide differ from calcium oxide in properties? 9. Supposing bauxite to be 90% aluminium hydroxide, what weight of it is necessary for the preparation of 100 kg. of aluminium? CHAPTER XXVII THE IRON FAMILY =================================================================== | | | | | | | | | APPROXIMATE | | SYMBOL | ATOMIC | DENSITY | MELTING | OXIDES | | WEIGHT | | POINT | ________|________|________|_________|_____________|________________ | | | | | Iron | Fe | 55.9 | 7.93 | 1800° | FeO, Fe_{2}O_{3} Cobalt | Co | 59.0 | 8.55 | 1800° | CoO, Co_{2}O_{3} Nickel | Ni | 58.7 | 8.9 | 1600° | NiO, Ni_{2}O_{3} =================================================================== ~The family.~ The elements iron, cobalt, and nickel form a group in the eighth column of the periodic table. The atomic weights of the three are very close together, and there is not the same gradual gradation in the properties of the three elements that is noticed in the families in which the atomic weights differ considerably in magnitude. The elements are very similar in properties, the similarity being so great in the case of nickel and cobalt that it is difficult to separate them by chemical analysis. The elements occur in nature chiefly as oxides and sulphides, though they have been found in very small quantities in the native state, usually in meteorites. Their sulphides, carbonates, and phosphates are insoluble in water, the other common salts being soluble. Their salts are usually highly colored, those of iron being yellow or light green as a rule, those of nickel darker green, while cobalt salts are usually rose colored. The metals are obtained by reducing the oxides with carbon. IRON ~Occurrence.~ The element iron has long been known, since its ores are very abundant and it is not difficult to prepare the metal from them in fairly pure condition. It occurs in nature in many forms of combination,--in large deposits as oxides, sulphides, and carbonates, and in smaller quantities in a great variety of minerals. Indeed, very few rocks or soils are free from small amounts of iron, and it is assimilated by plants and animals playing an important part in life processes. ~Metallurgy.~ It will be convenient to treat of the metallurgy of iron under two heads,--Materials Used and Process. ~Materials used.~ Four distinct materials are used in the metallurgy of iron: 1. _Iron ore._ The ores most frequently used in the metallurgy of iron are the following: Hematite Fe_{2}O_{3}. Magnetite Fe_{3}O_{4}. Siderite FeCO_{3}. Limonite 2Fe_{2}O_{2}·3H_{2}O. These ores always contain impurities, such as silica, sulphides, and earthy materials. All ores, with the exception of the oxides, are first roasted to expel any water and carbon dioxide present and to convert any sulphide into oxide. 2. _Carbon._ Carbon in some form is necessary both as a fuel and as a reducing agent. In former times wood charcoal was used to supply the carbon, but now anthracite coal or coke is almost universally used. 3. _Hot air._ To maintain the high temperature required for the reduction of iron a very active combustion of fuel is necessary. This is secured by forcing a strong blast of hot air into the lower part of the furnace during the reduction process. 4. _Flux._ (a) _Purpose of the flux._ All the materials which enter the furnace must leave it again either in the form of gases or as liquids. The iron is drawn off as the liquid metal after its reduction. To secure the removal of the earthy matter charged into the furnace along with the ore, materials are added to the charge which will, at the high temperature of the furnace, combine with the impurities in the ore, forming a liquid. The material added for this purpose is called the _flux_; the liquid produced from the flux and the ore is called _slag_. (b) _Function of the slag._ While the main purpose of adding flux to the charge is to remove from the furnace in the form of liquid slag the impurities originally present in the ore, the slag thus produced serves several other functions. It keeps the contents of the furnace in a state of fusion, thus preventing clogging, and makes it possible for the small globules of iron to run together with greater ease into one large liquid mass. (c) _Character of the slag._ The slag is really a kind of readily fusible glass, being essentially a calcium-aluminium silicate. The ore usually contains silica and some aluminium compounds, so that limestone (which also contains some silica and aluminium) is added to furnish the calcium required for the slag. If the ore and the limestone do not contain a sufficient amount of silica and aluminium for the formation of the slag, these ingredients are added in the form of sand and feldspar. In the formation of slag from these materials the ore is freed from the silica and aluminium which it contained. [Illustration: Fig. 85] ~Process.~ The reduction of iron is carried out in large towers called blast furnaces. The blast furnace (Fig. 85) is usually about 80 ft. high and 20 ft. in internal diameter at its widest part, narrowing somewhat both toward the top and toward the bottom. The walls are built of steel and lined with fire-brick. The base is provided with a number of pipes T, called tuyers, through which hot air can be forced into the furnace. The tuyers are supplied from a large pipe S, which circles the furnace as a girdle. The base has also an opening M, through which the liquid metal can be drawn off from time to time, and a second opening P, somewhat above the first, through which the excess of slag overflows. The top is closed by a movable trap C and C, called the cone, and through this the materials to be used are introduced. The gases produced by the combustion of the fuel and the reduction of the ore, together with the nitrogen of the air forced in through the tuyers, escape through pipes D, called downcomer pipes, which leave the furnace near the top. These gases are very hot and contain combustible substances, principally carbon monoxide; they are therefore utilized as fuel for the engines and also to heat the blast admitted through the tuyers. The lower part of the furnace is often furnished with a water jacket. This consists of a series of pipes W built into the walls, through which water can be circulated to reduce their temperature. Charges consisting of coke (or anthracite coal), ore, and flux in proper proportions are introduced into the furnace at intervals through the trap top. The coke burns fiercely in the hot-air blast, giving an intense heat and forming carbon monoxide. The ore, working down in the furnace as the coke burns, becomes very hot, and by the combined reducing action of the carbon and carbon monoxide is finally reduced to metal and collects as a liquid in the bottom of the furnace, the slag floating on the molten iron. After a considerable amount of the iron has collected the slag is drawn off through the opening P. The molten iron is then drawn off into large ladles and taken to the converters for the manufacture of steel, or it is run out into sand molds, forming the bars or ingots called "pigs." The process is a continuous one, and when once started it is kept in operation for months or even years without interruption. It seems probable that the first product of combustion of the carbon, at the point where the tuyers enter the furnace, is carbon dioxide. This is at once reduced to carbon monoxide by the intensely heated carbon present, so that no carbon dioxide can be found at that point. For practical purposes, therefore, we may consider that carbon monoxide is the first product of combustion. ~Varieties of iron.~ The iron of commerce is never pure, but contains varying amounts of other elements, such as carbon, silicon, phosphorus, sulphur, and manganese. These elements may either be alloyed with the iron or may be combined with it in the form of definite chemical compounds. In some instances, as in the case of graphite, the mixture may be merely mechanical. The properties of iron are very much modified by the presence of these elements and by the form of the combination between them and the iron; the way in which the metal is treated during its preparation has also a marked influence on its properties. Owing to these facts many kinds of iron are recognized in commerce, the chief varieties being cast iron, wrought iron, and steel. ~Cast iron.~ The product of the blast furnace, prepared as just described, is called cast iron. It varies considerably in composition, usually containing from 90 to 95% iron, the remainder being largely carbon and silicon with smaller amounts of phosphorus and sulphur. When the melted metal from the blast furnace is allowed to cool rapidly most of the carbon remains in chemical combination with the iron, and the product is called white cast iron. If the cooling goes on slowly, the carbon partially separates as flakes of graphite which remain scattered through the metal. This product is softer and darker in color and is called gray cast iron. ~Properties of cast iron.~ Cast iron is hard, brittle, and rather easily melted (melting point about 1100°). It cannot be welded or forged into shape, but is easily cast in sand molds. It is strong and rigid but not elastic. It is used for making castings and in the manufacture of other kinds of iron. Cast iron, which contains the metal manganese up to the extent of 20%, together with about 3% carbon, is called spiegel iron; when more than this amount of manganese is present the product is called ferromanganese. The ferromanganese may contain as much as 80% manganese. These varieties of cast iron are much used in the manufacture of steel. ~Wrought iron.~ Wrought iron is made by burning out from cast iron most of the carbon, silicon, phosphorus, and sulphur which it contains. The process is called _puddling_, and is carried out in a furnace constructed as represented in Fig. 86. The floor of the furnace F is somewhat concave and is made of iron covered with a layer of iron oxide. A long flame produced by burning fuel upon the grate G is directed downward upon the materials placed upon the floor, and the draught is maintained by the stack S. A is the ash box and T a trap to catch the solid particles carried into the stack by the draught. Upon the floor of the furnace is placed the charge of cast iron, together with a small amount of material to make a slag. The iron is soon melted by the flame directed upon it, and the sulphur, phosphorus, and silicon are oxidized by the iron oxide, forming oxides which are anhydrides of acids. These combine with the flux, which is basic in character, or with the iron oxide, to form a slag. The carbon is also oxidized and escapes as carbon dioxide. As the iron is freed from other elements it becomes pasty, owing to the higher melting point of the purer iron, and in this condition forms small lumps which are raked together into a larger one. The large lump is then removed from the furnace and rolled or hammered into bars, the slag; being squeezed out in this process. The product has a stranded or fibrous structure. _The product of a puddling furnace is called wrought iron._ [Illustration: Fig. 86] ~Properties of wrought iron.~ Wrought iron is nearly pure iron, usually containing about 0.3% of other substances, chiefly carbon. It is tough, malleable, and fibrous in structure. It is easily bent and is not elastic, so it will not sustain pressure as well as cast iron. It can be drawn out into wire of great tensile strength, and can also be rolled into thin sheets (sheet iron). It melts at a high temperature (about 1600°) and is therefore forged into shape rather than cast. If melted, it would lose its fibrous structure and be changed into a low carbon steel. ~Steel.~ Steel, like wrought iron, is made by burning out from cast iron a part of the carbon, silicon, phosphorus, and sulphur which it contains; but the process is carried out in a very different way, and usually, though not always, more carbon is found in steel than in wrought iron. A number of processes are in use, but nearly all the steel of commerce is made by one of the two following methods. [Illustration: Fig. 87] 1. _Bessemer process._ This process, invented about 1860, is by far the most important. It is carried out in great egg-shaped crucibles called converters (Fig. 87), each one of which will hold as much as 15 tons of steel. The converter is built of steel and lined with silica. It is mounted on trunnions T, so that it can be tipped over on its side for filling and emptying. One of the trunnions is hollow and a pipe P connects it with an air chamber A, which forms a false bottom to the converter. The true bottom is perforated, so that air can be forced in by an air blast admitted through the trunnion and the air chamber. White-hot, liquid cast iron from a blast furnace is run into the converter through its open necklike top O, the converter being tipped over to receive it; the air blast is then turned on and the converter rotated to a nearly vertical position. The elements in the iron are rapidly oxidized, the silicon first and then the carbon. The heat liberated in the oxidation, largely due to the combustion of silicon, keeps the iron in a molten condition. When the carbon is practically all burned out cast iron or spiegel iron, containing a known percentage of carbon, is added and allowed to mix thoroughly with the fluid. The steel is then run into molds, and the ingots so formed are hammered or rolled into rails or other forms. By this process any desired percentage of carbon can be added to the steel. Low carbon steel, which does not differ much from wrought iron in composition, is now made in this way and is replacing the more expensive wrought iron for many purposes. ~The basic lining process.~ When the cast iron contains phosphorus and sulphur in appreciable quantities, the lining of the converter is made of dolomite. The silicon and carbon burn, followed by the phosphorus and sulphur, and the anhydrides of acids so formed combine with the basic oxides of the lining, forming a slag. This is known as the basic lining process. 2. _Open-hearth process._ In this process a furnace very similar to a puddling furnace is used, but it is lined with silica or dolomite instead of iron oxide. A charge consisting in part of old scrap iron of any kind and in part of cast iron is melted in the furnace by a gas flame. The silicon and carbon are slowly burned away, and when a test shows that the desired percentage of carbon is present the steel is run out of the furnace. _Steel may therefore be defined as the product of the Bessemer or open-hearth processes._ ~Properties of steel.~ Bessemer and open-hearth steel usually contain only a few tenths of a per cent of carbon, less than 0.1% silicon, and a very much smaller quantity of phosphorus and sulphur. Any considerable amount of the latter elements makes the steel brittle, the sulphur affecting it when hot, and the phosphorus when cold. This kind of steel is used for structural purposes, for rails, and for nearly all large steel articles. It is hard, malleable, ductile, and melts at a lower temperature than wrought iron. It can be forged into shape, rolled into sheets, or cast in molds. ~Relation of the three varieties of iron.~ It will be seen that wrought iron is usually very nearly pure iron, while steel contains an appreciable amount of alloy material, chiefly carbon, and cast iron still more of the same substances. It is impossible, however, to assign a given sample of iron to one of these three classes on the basis of its chemical composition alone. A low carbon steel, for example, may contain less carbon than a given sample of wrought iron. The real distinction between the three is the process by which they are made. The product of the blast furnace is cast iron; that of the puddling furnace is wrought iron; that of the Bessemer and open-hearth methods is steel. ~Tool steel.~ Steel designed for use in the manufacture of edged tools and similar articles should be relatively free from silicon and phosphorus, but should contain from 0.5 to 1.5% carbon. The percentage of carbon should be regulated by the exact use to which the steel is to be put. Steel of this character is usually made in small lots from either Bessemer or open-hearth steel in the following way. A charge of melted steel is placed in a large crucible and the calculated quantity of pure carbon is added. The carbon dissolves in the steel, and when the solution is complete the metal is poured out of the crucible. This is sometimes called crucible steel. ~Tempering of steel.~ Steel containing from 0.5 to 1.5% carbon is characterized by the property of "taking temper." When the hot steel is suddenly cooled by plunging it into water or oil it becomes very hard and brittle. On carefully reheating this hard form it gradually becomes less brittle and softer, so that by regulating the temperature to which steel is reheated in tempering almost any condition of temper demanded for a given purpose, such as for making springs or cutting tools, can be obtained. ~Steel alloys.~ It has been found that small quantities of a number of different elements when alloyed with steel very much improve its quality for certain purposes, each element having a somewhat different effect. Among the elements most used in this connection are manganese, silicon, chromium, nickel, tungsten, and molybdenum. The usual method for adding these elements to the steel is to first prepare a very rich alloy of iron with the element to be added, and then add enough of this alloy to a large quantity of the steel to bring it to the desired composition. A rich alloy of iron with manganese or silicon can be prepared directly in a blast furnace, and is called ferromanganese or ferrosilicon. Similar alloys of iron with the other elements mentioned are made in an electric furnace by reducing the mixed oxides with carbon. ~Pure iron.~ Perfectly pure iron is rarely prepared and is not adapted to commercial uses. It can be made by reducing pure oxide of iron in a current of hydrogen at a high temperature. Prepared in this way it forms a black powder; when melted it forms a tin-white metal which is less fusible and more malleable than wrought iron. It is easily acted upon by moist air. ~Compounds of iron.~ Iron differs from the metals so far studied in that it is able to form two series of compounds in which the iron has two different valences. In the one series the iron is divalent and forms compounds which in formulas and many chemical properties are similar to the corresponding zinc compounds. It can also act as a trivalent metal, and in this condition forms salts similar to those of aluminium. Those compounds in which the iron is divalent are known as _ferrous_ compounds, while those in which it is trivalent are known as _ferric_. ~Oxides of iron.~ Iron forms several oxides. Ferrous oxide (FeO) is not found in nature, but can be prepared artificially in the form of a black powder which easily takes up oxygen, forming ferric oxide: 2FeO + O = Fe_{2}O_{3}. Ferric oxide is the most abundant ore of iron and occurs in great deposits, especially in the Lake Superior region. It is found in many mineral varieties which vary in density and color, the most abundant being hematite, which ranges in color from red to nearly black. When prepared by chemical processes it forms a red powder which is used as a paint pigment (Venetian red) and as a polishing powder (rouge). Magnetite has the formula Fe_{3}O_{4} and is a combination of FeO and Fe_{2}O_{3}. It is a very valuable ore, but is less abundant than hematite. It is sometimes called magnetic oxide of iron, or lodestone, since it is a natural magnet. ~Ferrous salts.~ These salts are obtained by dissolving iron in the appropriate acid, or, when insoluble, by precipitation. They are usually light green in color and crystallize well. In chemical reactions they are quite similar to the salts of magnesium and zinc, but differ from them in one important respect, namely, that they are easily changed into compounds in which the metal is trivalent. Thus ferrous chloride treated with chlorine or aqua regia is changed into ferric chloride: FeCl_{2} + Cl = FeCl_{3}. Ferrous hydroxide exposed to moist air is rapidly changed into ferric hydroxide: 2Fe(OH)_{2} + H_{2}O + O = 2Fe(OH)_{3}. ~Ferrous sulphate~ _(copperas, green vitriol)_ (FeSO_{4}·7H_{2}O). Ferrous sulphate is the most familiar ferrous compound. It is prepared commercially as a by-product in the steel-plate mills. Steel plates are cleaned by the action of dilute sulphuric acid upon them, and in the process some of the iron dissolves. The liquors are concentrated and the green vitriol separates from them. ~Ferrous sulphide~ (FeS). Ferrous sulphide is sometimes found in nature as a golden-yellow crystalline mineral. It is formed as a black precipitate when a soluble sulphide and an iron salt are brought together in solution: FeSO_{4} + Na_{2}S = FeS + Na_{2}SO_{4}. It can also be made as a heavy dark-brown solid by fusing together the requisite quantities of sulphur and iron. It is obtained as a by-product in the metallurgy of lead: PbS + Fe = FeS + Pb. It is used in the laboratory in the preparation of hydrosulphuric acid: FeS + 2HCl = FeCl_{2} + H_{2}S. ~Iron disulphide~ _(pyrites)_ (FeS_{2}). This substance bears the same relation to ferrous sulphide that hydrogen dioxide does to water. It occurs abundantly in nature in the form of brass-yellow cubical crystals and in compact masses. Sometimes the name "fool's gold" is applied to it from its superficial resemblance to the precious metal. It is used in very large quantities as a source of sulphur dioxide in the manufacture of sulphuric acid, since it burns readily in the air, forming ferric oxide and sulphur dioxide: 2FeS_{2} + 11O = Fe_{2}O_{3} + 4SO_{2}. ~Ferrous carbonate~ (FeCO_{3}). This compound occurs in nature as siderite, and is a valuable ore. It will dissolve to some extent in water containing carbon dioxide, just as will calcium carbonate, and waters containing it are called chalybeate waters. These chalybeate waters are supposed to possess certain medicinal virtues and form an important class of mineral waters. ~Ferric salts.~ Ferric salts are usually obtained by treating an acidified solution of a ferrous salt with an oxidizing agent: 2FeCl_{2} + 2HCl + O = 2FeCl_{3} + H_{2}O, 2FeSO_{4} + H_{2}SO_{4} + O = Fe_{2}(SO_{4})_{3} + H_{2}O. They are usually yellow or violet in color, are quite soluble, and as a rule do not crystallize well. Heated with water in the absence of free acid, they hydrolyze even more readily than the salts of aluminium. The most familiar ferric salts are the chloride and the sulphate. ~Ferric chloride~ (FeCl_{3}). This salt can be obtained most conveniently by dissolving iron in hydrochloric acid and then passing chlorine into the solution: Fe + 2HCl = FeCl_{2} + 2H, FeCl_{2} + Cl = FeCl_{3}. When the pure salt is heated with water it is partly hydrolyzed: FeCl_{3} + 3 H_{2}O <--> Fe(OH)_{3} + 3HCl. This is a reversible reaction, however, and hydrolysis can therefore be prevented by first adding a considerable amount of the soluble product of the reaction, namely, hydrochloric acid. ~Ferric sulphate~ (Fe_{2}(SO_{4})_{3}). This compound can be made by treating an acid solution of green vitriol with an oxidizing agent. It is difficult to crystallize and hard to obtain in pure condition. When an alkali sulphate in proper quantity is added to ferric sulphate in solution an iron alum is formed, and is easily obtained in large crystals. The best known iron alums have the formulas KFe(SO_{4})_{2}·12H_{2}O and NH_{4}Fe(SO_{4})_{2}·12H_{2}O. They are commonly used when a pure ferric salt is required. ~Ferric hydroxide~ (Fe(OH)_{3}). When solutions of ferric salts are treated with ammonium hydroxide, ferric hydroxide is formed as a rusty-red precipitate, insoluble in water. ~Iron cyanides.~ A large number of complex cyanides containing iron are known, the most important being potassium ferrocyanide, or yellow prussiate of potash (K_{4}FeC_{6}N_{6}), and potassium ferricyanide, or red prussiate of potash (K_{3}FeC_{6}N_{6}). These compounds are the potassium salts of the complex acids of the formulas H_{4}FeC_{6}N_{6} and H_{3}FeC_{6}N_{6}. ~Oxidation of ferrous salts.~ It has just been seen that when a ferrous salt is treated with an oxidizing agent in the presence of a free acid a ferric salt is formed: 2FeSO_{4} + H_{2}SO_{4} + O = Fe_{2}(SO_{4})_{3} + H_{2}O. In this reaction oxygen is used up, and the valence of the iron is changed from 2 to 3. The same equation may be written 2Fe^{++}, 2SO_{4}^{--} + 2H^{+}, SO_{4}^{--} + O = 2Fe^{+++}, 3SO_{4}^{--} + H_{2}O. Hydrogen ions have been oxidized to water, while the charge of each iron ion has been increased from 2 to 3. In a similar way the conversion of ferrous chloride into ferric chloride may be written Fe^{++}, 2Cl^{-} + Cl = Fe^{+++}, + 3Cl^{-}. Here again the valence of the iron and the charge on the iron ion has been increased from 2 to 3, though no oxygen has entered into the reaction. As a rule, however, changes of this kind are brought about by the use of an oxidizing agent, and are called oxidations. The term "oxidation" is applied to all reactions in which the valence of the metal of a compound is increased, or, in other words, to all reactions in which the charge of a cation is increased. ~Reduction of ferric salts.~ The changes which take place when a ferric salt is converted into a ferrous salt are the reverse of the ones just described. This is seen in the equation FeCl_{3} + H = FeCl_{2} + HCl In this reaction the valence of the iron has been changed from 3 to 2. The same equation may be written Fe^{+++}, 3Cl_{-} + H = Fe^{++}, + H^{+} + 3Cl_{-} It will be seen that the charge of the iron ions has been diminished from 3 to 2. Since these changes are the reverse of the oxidation changes just considered, they are called reduction reactions. The term "reduction" is applied to all processes in which the valence of the metal of a compound is diminished, or, in other words, to all processes in which the charge on the cations is diminished. NICKEL AND COBALT These elements occur sparingly in nature, usually combined with arsenic or with arsenic and sulphur. Both elements have been found in the free state in meteorites. Like iron they form two series of compounds, but the salts corresponding to the ferrous salts are the most common, the ones corresponding to the ferric salts being difficult to obtain. Thus we have the chlorides NiCl_{2}·6H_{2}O and CoCl_{2}·6H_{2}O; the sulphates NiSO_{4}·7H_{2}O and CoSO_{4}·7H_{2}O; the nitrates Ni(NO_{3})_{2}·6H_{2}O and Co(NO_{3})_{2}·6H_{2}O. Nickel is largely used as an alloy with other metals. Alloyed with copper it forms coin metal from which five-cent pieces are made, with copper and zinc it forms German silver, and when added to steel in small quantities nickel steel is formed which is much superior to common steel for certain purposes. When deposited by electrolysis upon the surface of other metals such as iron, it forms a covering which will take a high polish and protects the metal from rust, nickel not being acted upon by moist air. Salts of nickel are usually green. Compounds of cobalt fused with glass give it an intensely blue color. In powdered form such glass is sometimes used as a pigment called smalt. Cobalt salts, which contain water of crystallization, are usually cherry red in color; when dehydrated they become blue. EXERCISES 1. In the manufacture of cast iron, why is the air heated before being forced into the furnace? 2. Write the equations showing how each of the following compounds of iron could be obtained from the metal itself: ferrous chloride, ferrous hydroxide, ferrous sulphate, ferrous sulphide, ferrous carbonate, ferric chloride, ferric sulphate, ferric hydroxide. 3. Account for the fact that a solution of sodium carbonate, when added to a solution of a ferric salt, precipitates an hydroxide and not a carbonate. 4. Calculate the percentage of iron in each of the common iron ores. 5. One ton of steel prepared by the Bessemer process is found by analysis to contain 0.2% carbon. What is the minimum weight of carbon which must be added in order that the steel may be made to take a temper? CHAPTER XXVIII COPPER, MERCURY, AND SILVER ================================================================== | | | | | | | | | | FORMULAS OF OXIDES | SYMBOL | ATOMIC | DENSITY | MELTING |___________________ | | WEIGHT | | POINT | | | | | | | "ous" | "ic" ________|________|________|_________|_________|__________|________ | | | | | | Copper | Cu | 63.6 | 8.89 | 1084° | Cu_{2}O | CuO Mercury | Hg | 200.00 | 13.596 | -39.5° | Hg_{2}O | HgO Silver | Ag | 107.93 | 10.5 | 960° | Ag_{2}O | AgO ================================================================== ~The family.~ By referring to the periodic arrangement of the elements (page 168), it will be seen that mercury is not included in the same family with copper and silver. Since the metallurgy of the three elements is so similar, however, and since they resemble each other so closely in chemical properties, it is convenient to class them together for study. 1. _Occurrence._ The three elements occur in nature to some extent in the free state, but are usually found as sulphides. Their ores are easy to reduce. 2. _Properties._ They are heavy metals of high luster and are especially good conductors of heat and electricity. They are not very active chemically. Neither hydrochloric nor dilute sulphuric acid has any appreciable action upon them. Concentrated sulphuric acid attacks all three, forming metallic sulphates and evolving sulphur dioxide, while nitric acid, both dilute and concentrated, converts them into nitrates with the evolution of oxides of nitrogen. 3. _Two series of salts._ Copper and mercury form oxides of the types M_{2}O and MO, as well as two series of salts. In one series the metals are univalent and the salts have formulas like those of the sodium salts. They are called cuprous and mercurous salts. In the other series the metals are divalent and resemble magnesium salts in formulas. These are called cupric and mercuric salts. Silver forms only one series of salts, being always a univalent metal. COPPER ~Occurrence.~ The element copper has been used for various purposes since the earliest days of history. It is often found in the metallic state in nature, large masses of it occurring pure in the Lake Superior region and in other places to a smaller extent. The most valuable ores are the following: Cuprite Cu_{2}O. Chalcocite Cu_{2}S. Chalcopyrite CuFeS_{2}. Bornite Cu_{3}FeS_{3}. Malachite CuCO_{3}·Cu(OH)_{2}. Azurite 2CuCO_{3}·Cu(OH)_{2}. ~Metallurgy of copper.~ Ores containing little or no sulphur are easy to reduce. They are first crushed and the earthy impurities washed away. The concentrated ore is then mixed with carbon and heated in a furnace, metallic copper resulting from the reduction of the copper oxide by the hot carbon. ~Metallurgy of sulphide ores.~ Much of the copper of commerce is made from chalcopyrite and bornite, and these ores are more difficult to work. They are first roasted in the air, by which treatment much of the sulphur is burned to sulphur dioxide. The roasted ore is then melted in a small blast furnace or in an open one like a puddling furnace. In melting, part of the iron combines with silica to form a slag of iron silicate. The product, called crude matte, contains about 50% copper together with sulphur and iron. Further purification is commonly carried on by a process very similar to the Bessemer process for steel. The converter is lined with silica, and a charge of matte from the melting furnace, together with sand, is introduced, and air is blown into the mass. By this means the sulphur is practically all burned out by the air, and the remaining iron combines with silica and goes off as slag. The copper is poured out of the converter and molded into anode plates for refining. ~Refining of copper.~ Impure copper is purified by electrolysis. A large plate of it, serving as an anode, is suspended in a tank facing a thin plate of pure copper, which is the cathode. The tank is filled with a solution of copper sulphate and sulphuric acid to serve as the electrolyte. A current from a dynamo passes from the anode to the cathode, and the copper, dissolving from the anode, is deposited upon the cathode in pure form, while the impurities collect on the bottom of the tank. Electrolytic copper is one of the purest of commercial metals and is very nearly pure copper. ~Recovery of gold and silver.~ Gold and silver are often present in small quantities in copper ores, and in electrolytic refining these metals collect in the muddy deposit on the bottom of the tank. The mud is carefully worked over from time to time and the precious metals extracted from it. A surprising amount of gold and silver is obtained in this way. ~Properties of copper.~ Copper is a rather heavy metal of density 8.9, and has a characteristic reddish color. It is rather soft and is very malleable, ductile, and flexible, yet tough and strong; it melts at 1084°. As a conductor of heat and electrical energy it is second only to silver. Hydrochloric acid, dilute sulphuric acid, and fused alkalis are almost without action upon it; nitric acid and hot, concentrated sulphuric acid, however, readily dissolve it. In moist air it slowly becomes covered with a thin layer of green basic carbonate; heated in the air it is easily oxidized to black copper oxide (CuO). ~Uses.~ Copper is extensively used for electrical purposes, for roofs and cornices, for sheathing the bottom of ships, and for making alloys. In the following table the composition of some of these alloys is indicated: COMPOSITION OF ALLOYS OF COPPER IN PERCENTAGES Aluminium bronze copper (90 to 97%), aluminium (3 to 10%). Brass copper (63 to 73%), zinc (27 to 37%). Bronze copper (70 to 95%), zinc (1 to 25%), tin (1 to 18%). German silver copper (56 to 60%), zinc (20%), nickel (20 to 25%). Gold coin copper (10%), gold (90%). Gun metal copper (90%), tin (10%). Nickel coin copper (75%), nickel (25%) Silver coin copper (10%), silver (90%). ~Electrotyping.~ Matter is often printed from electrotype plates which are prepared as follows. The matter is set up in type and wax is firmly pressed down upon the face of it until a clear impression is obtained. The impressed side of the wax is coated with graphite and the impression is made the cathode in an electrolytic cell containing a copper salt in solution. When connected with a current the copper is deposited as a thin sheet upon the letters in wax, and when detached is a perfect copy of the type, the under part of the letters being hollow. The sheet is strengthened by pouring on the under surface a suitable amount of molten metal (commercial lead is used). The sheet so strengthened is then used in printing. ~Two series of copper compounds.~ Copper, like iron, forms two series of compounds: in the cuprous compounds it is univalent; in the cupric it is divalent. The cupric salts are much the more common of the two, since the cuprous salts pass readily into cupric by oxidation. ~Cuprous compounds.~ The most important cuprous compound is the oxide (Cu_{2}O), which occurs in nature as ruby copper or cuprite. It is a bright red substance and can easily be prepared by heating copper to a high temperature in a limited supply of air. It is used for imparting a ruby color to glass. By treating cuprous oxide with different acids a number of cuprous salts can be made. Many of these are insoluble in water, the chloride (CuCl) being the best known. When suspended in dilute hydrochloric acid it is changed into cupric chloride, the oxygen taking part in the reaction being absorbed from the air: 2CuCl + 2HCl + O = 2CuCl_{2} + H_{2}O. ~Cupric compounds.~ Cupric salts are easily made by dissolving cupric oxide in acids, or, when insoluble, by precipitation. Most of them are blue or green in color, and the soluble ones crystallize well. Since they are so much more familiar than the cuprous salts, they are frequently called merely copper salts. ~Cupric oxide~ (CuO). This is a black insoluble substance obtained by heating copper in excess of air, or by igniting the hydroxide or nitrate. It is used as an oxidizing agent. ~Cupric hydroxide~ (Cu(OH)_{2}). The hydroxide prepared by treating a solution of a copper salt with sodium hydroxide is a light blue insoluble substance which easily loses water and changes into the oxide. Heat applied to the liquid containing the hydroxide suspended in it serves to bring about the reaction represented by the equation Cu(OH)_{2} = CuO + H_{2}O. ~Cupric sulphate~ (_blue vitriol_) (CuSO_{4}·5H_{2}O). This substance, called blue vitriol or bluestone, is obtained as a by-product in a number of processes and is produced in very large quantities. It forms large blue crystals, which lose water when heated and crumble to a white powder. The salt finds many uses, especially in electrotyping and in making electrical batteries. ~Cupric sulphide~ (CuS). The insoluble black sulphide (CuS) is easily prepared by the action of hydrosulphuric acid upon a solution of a copper salt: CuSO_{4} + H_{2}S = CuS + H_{2}SO_{4}. It is insoluble in water and dilute acids. MERCURY ~Occurrence.~ Mercury occurs in nature chiefly as the sulphide (HgS) called cinnabar, and in globules of metal inclosed in the cinnabar. The mercury mines of Spain have long been famous, California being the next largest producer. ~Metallurgy.~ Mercury is a volatile metal which has but little affinity for oxygen. Sulphur, on the other hand, readily combines with oxygen. These facts make the metallurgy of mercury very simple. The crushed ore, mixed with a small amount of carbon to reduce any oxide or sulphate that might be formed, is roasted in a current of air. The sulphur burns to sulphur dioxide, while the mercury is converted into vapor and is condensed in a series of condensing vessels. The metal is purified by distillation. ~Properties.~ Mercury is a heavy silvery liquid with a density of 13.596. It boils at 357° and solidifies at -39.5°. Small quantities of many metals dissolve in it, forming liquid alloys, while with larger quantities it forms solid alloys. The alloys of mercury are called amalgams. Toward acids mercury conducts itself very much like copper; it is easily attacked by nitric and hot, concentrated sulphuric acids, while cold sulphuric and hydrochloric acids have no effect on it. ~Uses.~ Mercury is extensively used in the construction of scientific instruments, such as the thermometer and barometer, and as a liquid over which to collect gases which are soluble in water. The readiness with which it alloys with silver and gold makes it very useful in the extraction of these elements. ~Compounds of mercury.~ Like copper, mercury forms two series of compounds: the mercurous, of which mercurous chloride (HgCl) is an example; and the mercuric, represented by mercuric chloride (HgCl_{2}). ~Mercuric oxide~ (HgO). Mercuric oxide can be obtained either as a brick-red or as a yellow substance. When mercuric nitrate is heated carefully the red modification is formed in accordance with the equation Hg(NO_{3})_{2} = HgO + 2NO_{2} + O. The yellow modification is prepared by adding a solution of a mercuric salt to a solution of sodium or potassium hydroxide: Hg(NO_{3})_{2} + 2NaOH = 2NaNO_{3} + Hg(OH)_{2}, Hg(OH)_{2} = HgO + H_{2}O. When heated the oxide darkens until it becomes almost black; at a higher temperature it decomposes into mercury and oxygen. It was by this reaction that oxygen was discovered. ~Mercurous chloride~ (_calomel_) (HgCl). Being insoluble, mercurous chloride is precipitated as a white solid when a soluble chloride is added to a solution of mercurous nitrate: HgNO_{3} + NaCl = HgCl + NaNO_{3}. Commercially it is manufactured by heating a mixture of mercuric chloride and mercury. When exposed to the light it slowly changes into mercuric chloride and mercury: 2HgCl = HgCl_{2} + Hg. It is therefore protected from the light by the use of colored bottles. It is used in medicine. Most mercurous salts are insoluble in water, the principal soluble one being the nitrate, which is made by the action of cold, dilute nitric acid on mercury. ~Mercuric chloride~ (_corrosive sublimate_) (HgCl_{2}). This substance can be made by dissolving mercuric oxide in hydrochloric acid. On a commercial scale it is made by subliming a mixture of common salt and mercuric sulphate: 2NaCl + HgSO_{4} = HgCl_{2} + Na_{2}SO_{4}. The mercuric chloride, being readily volatile, vaporizes and is condensed again in cool vessels. Like mercurous chloride it is a white solid, but differs from it in that it is soluble in water. It is extremely poisonous and in dilute solutions is used as an antiseptic in dressing wounds. ~Mercuric sulphide~ (HgS). As cinnabar this substance forms the chief native compound of mercury, occurring in red crystalline masses. By passing hydrosulphuric acid into a solution of a mercuric salt it is precipitated as a black powder, insoluble in water and acids. By other means it can be prepared as a brilliant red powder known as vermilion, which is used as a pigment in fine paints. ~The iodides of mercury.~ If a solution of potassium iodide is added to solutions of a mercurous and a mercuric salt respectively, the corresponding iodides are precipitated. Mercuric iodide is the more important of the two, and as prepared above is a red powder which changes to yellow on heating to 150°. The yellow form on cooling changes back again to the red form, or may be made to do so by rubbing it with a knife blade or some other hard object. SILVER ~Occurrence.~ Silver is found in small quantities in the uncombined state; usually, however, it occurs in combination with sulphur, either as the sulphide (Ag_{2}S) or as a small constituent of other sulphides, especially those of lead and copper. It is also found alloyed with gold. ~Metallurgy.~ _Parkes's process._ Silver is usually smelted in connection with lead. The ores are worked over together, as described under lead, and the lead and silver obtained as an alloy, the silver being present in small quantity. The alloy is melted and metallic zinc is stirred in. Zinc will alloy with silver but not with lead, and it is found that the silver leaves the lead and, in the form of an alloy with zinc, forms as a crust upon the lead and is skimmed off. This crust, which, of course, contains lead adhering to it, is partially melted and the most of the lead drained off. The zinc is removed by distillation, and the residue is melted on an open hearth in a current of air; by this means the zinc and lead remaining with the silver are changed into oxides and the silver remains behind unaltered. ~Amalgamation process.~ In some localities the old amalgamation process is used. The silver ore is treated with common salt and ferrous compounds, which process converts the silver first into chloride and then into metallic silver. Mercury is then added and thoroughly mixed with the mass, forming an amalgam with the silver. After some days the earthy materials are washed away and the heavier amalgam is recovered. The mercury is distilled off and the silver left in impure form. ~Refining silver.~ The silver obtained by either of the above processes may still contain copper, gold, and iron, and is refined by "parting" with sulphuric acid. The metal is heated with strong sulphuric acid which dissolves the silver, copper, and iron present, but not the gold. In the solution of silver sulphate so obtained copper plates are suspended, upon which the pure silver precipitates, the copper going into solution as sulphate, as shown in the equation Ag_{2}SO_{4} + Cu = 2Ag + CuSO_{4}. The solution obtained as a by-product in this process furnishes most of the blue vitriol of commerce. Silver is also refined by electrolytic methods similar to those used in refining copper. ~Properties of silver.~ Silver is a heavy, rather soft, white metal, very ductile and malleable and capable of taking a high polish. It surpasses all other metals as a conductor of heat and electricity, but is too costly to find extensive use for such purposes. It melts at a little lower temperature than copper (961°). It alloys readily with other heavy metals, and when it is to be used for coinage a small amount of copper--from 8 to 10%--is nearly always melted with it to give it hardness. It is not acted upon by water or air, but is quickly tarnished when in contact with sulphur compounds, turning quite black in time. Hydrochloric acid and fused alkalis do not act upon it, but nitric acid and hot, concentrated sulphuric acid dissolve it with ease. [Illustration: Fig. 88] ~Electroplating.~ Since silver is not acted upon by water or air, and has a pleasing appearance, it is used to coat various articles made of cheaper metals. Such articles are said to be silver plated. The process by which this is done is called electroplating. It is carried on as follows: The object to be plated (such as a spoon) is attached to a wire and dipped into a solution of a silver salt. Electrical connection is made in such a way that the article to be plated serves as the cathode, while the anode is made up of one or more plates of silver (Fig. 88, A). When a current is passed through the electrolyte silver dissolves from the anode plate and deposits on the cathode in the form of a closely adhering layer. By making the proper change in the electrolyte and anode plate objects may be plated with gold and other metals. ~Compounds of silver.~ Silver forms two oxides but only one series of salts, namely, the one which corresponds to the mercurous and cuprous series. ~Silver nitrate~ (_lunar caustic_) (AgNO_{3}). This salt is easily prepared by dissolving silver in nitric acid and evaporating the resulting solution. It crystallizes in flat plates, and when heated carefully can be melted without decomposition. When cast into sticks it is called lunar caustic, for it has a very corrosive action on flesh, and is sometimes used in surgery to burn away abnormal growths. The alchemists designated the metals by the names of the heavenly bodies. The moon (luna) was the symbol for silver; hence the name "lunar caustic." ~Silver sulphide~ (Ag_{2}S). This occurs in nature and constitutes one of the principal ores of silver. It can be obtained in the form of a black solid by passing hydrosulphuric acid through a solution of silver nitrate. ~Compounds of silver with the halogens.~ The chloride, bromide, and iodide of silver are insoluble in water and acids, and are therefore precipitated by bringing together a soluble halogen salt with silver nitrate: AgNO_{3} + KCl = AgCl + KNO_{3}. They are remarkable for the fact that they are very sensitive to the action of light, undergoing a change of color and chemical composition when exposed to sunlight, especially if in contact with organic matter such as gelatin. ~Photography.~ The art of photography is based on the fact that the halogen compounds of silver are affected by the light, particularly in the presence of organic matter. From a chemical standpoint the processes involved may be described under two heads: (1) the preparation of the negative; (2) the preparation of the print. 1. _Preparation of the negative._ The plate used in the preparation of the negative is made by spreading a thin layer of gelatin, in which silver bromide is suspended (silver iodide is sometimes added also), over a glass plate or celluloid film and allowing it to dry. When the plate so prepared is placed in a camera and the image of some object is focused upon it, the silver salt undergoes a change which is proportional at each point to the intensity of the light falling upon it. In this way an image of the object photographed is produced upon the plate, which is, however, invisible and is therefore called "latent." It can be made visible by the process of developing. To develop the image the exposed plate is immersed in a solution of some reducing agent called the developer. The developer reduces that portion of the silver salt which has been affected by the light, depositing it in the form of black metallic silver which closely adheres to the plate. The unaffected silver salt, upon which the developer has no action, must now be removed from the plate. This is done by immersing the plate in a solution of sodium thiosulphate (hypo). After the silver salt has been dissolved off, the plate is washed with water and dried. The plate so prepared is called the negative because it is a picture of the object photographed, with the lights exactly reversed. This is called fixing the negative. 2. _Preparation of the print._ The print is made from paper which is prepared in the same way as the negative plate. The negative is placed upon this paper and exposed to the light in such a way that the light must pass through the negative before striking the paper. If the paper is coated with silver chloride, a visible image is produced, in which case a developer is not needed. The proofs are made in this way. In order to make them permanent the unchanged silver chloride must be dissolved off with sodium thiosulphate. The print is then toned by dipping it into a solution of gold or platinum salts. The silver on the print passes into solution, while the gold or platinum takes its place. These metals give a characteristic color or tone to the print, the gold making it reddish brown, while the platinum gives it a steel-gray tone. If a silver bromide paper is used in making the print, a latent image is produced which must be developed as in the case of the negative itself. The silver bromide is much more sensitive than the chloride, so that the printing can be done in artificial light. Since the darkest places on the negative cut off the most light, it is evident that the lights of the print will be the reverse of those of the negative, and will therefore correspond to those of the object photographed. The print is therefore called the positive. EXERCISES 1. Account for the fact that copper has been used for so long a time. 2. Write equations for the action of concentrated sulphuric and nitric acids upon the metals of this family. 3. How would you account for the fact that normal copper sulphate is slightly acid to litmus? 4. Contrast the action of heat on cupric nitrate and mercuric nitrate. 5. State reasons why mercury is adapted for use in thermometers and barometers. 6. How could you distinguish between mercurous chloride and mercuric chloride? 7. Write equations for the preparation of mercuric and mercurous iodides. 8. How would you account for the fact that solutions of the different salts of a metal usually have the same color? 9. Crude silver usually contains iron and lead. What would become of these metals in refining by parting with sulphuric acid? 10. In the amalgamation process for extracting silver, how does ferrous chloride convert silver chloride into silver? Write equation. Why is the silver sulphide first changed into silver chloride? 11. What impurities would you expect to find in the copper sulphate prepared from the refining of silver? 12. How could you prepare pure silver chloride from a silver coin? 13. Mercuric nitrate and silver nitrate are both white solids soluble in water. How could you distinguish between them? 14. Account for the fact that sulphur waters turn a silver coin black; also for the fact that a silver spoon is blackened by foods (eggs, for example) containing sulphur. 15. When a solution of silver nitrate is added to a solution of potassium chlorate no precipitate forms. How do you account for the fact that a precipitate of silver chloride is not formed? CHAPTER XXIX TIN AND LEAD ==================================================================== | | | | | | SYMBOL | ATOMIC | DENSITY | MELTING | COMMON OXIDES | | WEIGHT | | POINT | _____|________|________|_________|_________|________________________ | | | | | Tin | Sn | 119.0 | 7.35 | 235° | SnO SnO_{2} Lead | Pb | 206.9 | 11.38 | 327° | PbO Pb_{3}O_{4} PbO_{2} ==================================================================== ~The family.~ Tin and lead, together with silicon and germanium, form a family in Group IV of the periodic table. Silicon has been discussed along with the non-metals, while germanium, on account of its rarity, needs only to be mentioned. The other family of Group IV includes carbon, already described, and a number of rare elements. TIN ~Occurrence.~ Tin is found in nature chiefly as the oxide (SnO_{2}), called cassiterite or tinstone. The most famous mines are those of Cornwall in England, and of the Malay Peninsula and East India Islands; in small amounts tinstone is found in many other localities. ~Metallurgy.~ The metallurgy of tin is very simple. The ore, separated as far as possible from earthy materials, is mixed with carbon and heated in a furnace, the reduction taking place readily. The equation is SnO_{2} + C = Sn + CO_{2}. The metal is often purified by carefully heating it until it is partly melted; the pure tin melts first and can be drained away from the impurities. ~Properties.~ Pure tin, called block tin, is a soft white metal with a silver-like appearance and luster; it melts readily (235°) and is somewhat lighter than copper, having a density of 7.3. It is quite malleable and can be rolled out into very thin sheets, forming tin foil; most tin foil, however, contains a good deal of lead. Under ordinary conditions it is quite unchanged by air or moisture, but at a high temperature it burns in air, forming the oxide SnO_{2}. Dilute acids have no effect upon it, but concentrated acids attack it readily. Concentrated hydrochloric acid changes it into the chloride Sn + 2HCl = SnCl_{2} + 2H. With sulphuric acid tin sulphate and sulphur dioxide are formed: Sn + 2H_{2}SO_{4} = SnSO_{4} + SO_{2} + 2H_{2}O Concentrated nitric acid oxidizes it, forming a white insoluble compound of the formula H_{2}SnO_{3}, called metastannic acid: 3Sn + 4HNO_{3} + H_{2}O = 3H_{2}SnO_{3} + 4NO. ~Uses of tin.~ A great deal of tin is made into tin plate by dipping thin steel sheets into the melted metal. Owing to the way in which tin resists the action of air and dilute acids, tin plate is used in many ways, such as in roofing, and in the manufacture of tin cans, cooking vessels, and similar articles. Many useful alloys contain tin, some of which have been mentioned in connection with copper. When tin is alloyed with other metals of low melting point, soft, easily melted alloys are formed which are used for friction bearings in machinery; tin, antimony, lead, and bismuth are the chief constituents of these alloys. Pewter and soft solder are alloys of tin and lead. ~Compounds of tin.~ Tin forms two series of compounds: the stannous, in which the tin is divalent, illustrated in the compounds SnO, SnS, SnCl_{2}; the stannic, in which it is tetravalent as shown in the compounds SnO_{2}, SnS_{2}. There is also an acid, H_{2}SnO_{3}, called stannic acid, which forms a series of salts called stannates. While this acid has the same composition as metastannic acid, the two are quite different in their chemical properties. This difference is probably due to the different arrangement of the atoms in the molecules of the two substances. Only a few compounds of tin need be mentioned. ~Stannic oxide~ (SnO_{2}). Stannic oxide is of interest, since it is the chief compound of tin found in nature. It is sometimes found in good-sized crystals, but as prepared in the laboratory is a white powder. When fused with potassium hydroxide it forms potassium stannate, acting very much like silicon dioxide: SnO_{2} + 2KOH = K_{2}SnO_{3} + H_{2}O. ~Chlorides of tin.~ Stannous chloride is prepared by dissolving tin in concentrated hydrochloric acid and evaporating the solution to crystallization. The crystals which are obtained have the composition SnCl_{2}·2H_{2}O, and are known as tin crystals. By treating a solution of stannous chloride with aqua regia, stannic chloride is formed: SnCl_{2} + 2Cl = SnCl_{4}. The salt which crystallizes from such a solution has the composition SnCl_{4}·5H_{2}O, and is known commercially as oxymuriate of tin. If metallic tin is heated in a current of dry chlorine, the anhydrous chloride (SnCl_{4}) is obtained as a heavy colorless liquid which fumes strongly on exposure to air. The ease with which stannous chloride takes up chlorine to form stannic chloride makes it a good reducing agent in many reactions, changing the higher chlorides of metals to lower ones. Thus mercuric chloride is changed into mercurous chloride: SnCl_{2} + 2HgCl_{2} = SnCl_{4} + 2HgCl. If the stannous chloride is in excess, the reaction may go further, producing metallic mercury: SnCl_{2} + 2HgCl = SnCl_{4} + 2Hg. Ferric chloride is in like manner reduced to ferrous chloride: SnCl_{3} + 2FeCl_{3} = SnCl_{4} + 2FeCl_{2}. The chlorides of tin, as well as the alkali stannates, are much used as mordants in dyeing processes. The hydroxides of tin and free stannic acid, which are easily liberated from these compounds, possess in very marked degree the power of fixing dyes upon fibers, as explained under aluminium. LEAD ~Occurrence.~ Lead is found in nature chiefly as the sulphide (PbS), called galena; to a much smaller extent it occurs as carbonate, sulphate, chromate, and in a few other forms. Practically all the lead of commerce is made from galena, two general methods of metallurgy being in use. ~Metallurgy.~ 1. The sulphide is melted with scrap iron, when iron sulphide and metallic lead are formed; the liquid lead, being the heavier, sinks to the bottom of the vessel and can be drawn off: PbS + Fe = Pb + FeS. 2. The sulphide is roasted in the air until a part of it has been changed into oxide and sulphate. The air is then shut off and the heating continued, the reactions indicated in the following equations taking place: 2PbO + PbS = 3Pb + SO_{2}, PbSO_{4} + PbS = 2Pb + 2SO_{2}. The lead so prepared usually contains small amounts of silver, arsenic, antimony, copper, and other metals. The silver is removed by Parkes's method, as described under silver, and the other metals in various ways. The lead of commerce is one of the purest commercial metals, containing as a rule only a few tenths per cent of impurities. ~Properties.~ Lead is a heavy metal (den. = 11.33) which has a brilliant silvery luster on a freshly cut surface, but which soon tarnishes to a dull blue-gray color. It is soft, easily fused (melting at 327°), and quite malleable, but has little toughness or strength. It is not acted upon to any great extent by the oxygen of the air under ordinary conditions, but is changed into oxide at a high temperature. With the exception of hydrochloric and sulphuric acids, most acids, even very weak ones, act upon it, forming soluble lead salts. Hot, concentrated hydrochloric and sulphuric acids also attack it to a slight extent. ~Uses.~ Lead is employed in the manufacture of lead pipes and in large storage batteries. In the form of sheet lead it is used in lining the chambers of sulphuric acid works and in the preparation of paint pigments. Some alloys of lead, such as solder and pewter (lead and tin), shot (lead and arsenic), and soft bearing metals, are widely used. Type metal consists of lead, antimony, and sometimes tin. Compounds of lead form several important pigments. ~Compounds of lead.~ In nearly all its compounds lead has a valence of 2, but a few corresponding to stannic compounds have a valence of 4. ~Lead oxides.~ Lead forms a number of oxides, the most important of which are litharge, red lead or minium, and lead peroxide. 1. _Litharge_ (PbO). This oxide forms when lead is oxidized at a rather low temperature, and is obtained as a by-product in silver refining. It is a pale yellow powder, and has a number of commercial uses. It is easily soluble in nitric acid: PbO + 2HNO_{3} = Pb(NO_{3})_{2} + H_{2}O. 2. _Red lead, or minium_ (Pb_{3}O_{4}). Minium is prepared by heating lead (or litharge) to a high temperature in the air. It is a heavy powder of a beautiful red color, and is much used as a pigment. 3. _Lead peroxide_ (PbO_{2}). This is left as a residue when minium is heated with nitric acid: Pb_{3}O_{4} + 4HNO_{3} = 2Pb(NO_{3})_{2} + PbO_{2} + 2H_{2}O. It is a brown powder which easily gives up a part of its oxygen and, like manganese dioxide and barium dioxide, is a good oxidizing agent. ~Soluble salts of lead.~ The soluble salts of lead can be made by dissolving (Pb(C_{2}H_{3}O_{2})_{2}·3H_{2}O), litharge in acids. Lead acetate called sugar of lead, and lead nitrate (Pb(NO_{3})_{2}) are the most familiar examples. They are while crystalline solids and are poisonous in character. ~Insoluble salts of lead; lead carbonate.~ While the normal carbonate of lead (PbCO_{3}) is found to some extent, in nature and can be prepared in the laboratory, basic carbonates of varying composition are much more easy to obtain. One of the simplest of these has the composition 2PbCO_{3}·Pb(OH)_{2}. A mixture of such carbonates is called white lead. This is prepared on a large scale as a paint pigment and as a body for paints which are to be colored with other substances. ~White lead.~ White lead is an amorphous white substance which, when mixed with oil, has great covering power, that is, it spreads out in an even waxy film, free from streaks and lumps, and covers the entire surface upon which it is spread. Its disadvantage as a pigment lies in the fact that it gradually blackens when exposed to sulphur compounds, which are often present in the air, forming black lead sulphide (PbS). ~Technical preparation of white lead.~ Different methods are used in the preparation of white lead, but the old one known as the Dutch process is still the principal one employed. In this process, earthenware pots about ten inches high and of the shape shown in Fig. 89 are used. In the bottom A is placed a 3% solution of acetic acid (vinegar answers the purpose very well). The space above this is filled with thin, perforated, circular pieces of lead, supported by the flange B of the pot. These pots are placed close together on a bed of tan bark on the floor of a room known as the corroding room. They are covered over with boards, upon which tan bark is placed, and another row of pots is placed on this. In this way the room is filled. The white lead is formed by the fumes of the acetic acid, together with the carbon dioxide set free in the fermentation of the tan bark acting on the lead. About three months are required to complete the process. [Illustration 1: Fig. 89] ~Lead sulphide~ (PbS). In nature this compound occurs in highly crystalline condition, the crystals having much the same luster as pure lead. It is readily prepared in the laboratory as a black precipitate, by the action of hydrosulphuric acid upon soluble lead salts: Pb(NO_{3})_{2} + H_{2}S = PbS + 2HNO_{3}. It is insoluble both in water and in dilute acids. ~Other insoluble salts.~ Lead chromate (PbCrO_{4}) is a yellow substance produced by the action of a soluble lead salt upon a soluble chromate, thus: K_{2}CrO_{4} + Pb(NO_{3})_{2} = PbCrO_{4} + 2 KNO_{3}. It is used as a yellow pigment. Lead sulphate (PbSO_{4}) is a white substance sometimes found in nature and easily prepared by precipitation. Lead chloride (PbCl_{2}) is likewise a white substance nearly insoluble in cold water, but readily soluble in boiling water. ~Thorium and cerium.~ These elements are found in a few rare minerals, especially in the monazite sand of the Carolinas and Brazil. The oxides of these elements are used in the preparation of the Welsbach mantles for gas lights, because of the intense light given out when a mixture of the oxides is heated. These mantles contain the oxides of cerium and thorium in the ratio of about 1% of the former to 99% of the latter. Compounds of thorium, like those of radium, are found to possess radio-activity, but in a less degree. EXERCISES 1. How could you detect lead if present in tin foil? 2. Stannous chloride reduces gold chloride (AuCl_{3}) to gold. Give equation. 3. What are the products of hydrolysis when stannic chloride is used as a mordant? 4. How could you detect arsenic, antimony, or copper in lead? 5. Why is lead so extensively used for making water pipes? 6. What sulphates other than lead are insoluble? 7. Could lead nitrate be used in place of barium chloride in testing for sulphates? 8. How much lead peroxide could be obtained from 1 kg. of minium? 9. The purity of white lead is usually determined by observing the volume of carbon dioxide given off when it is treated with an acid. What acid should be used? On the supposition that it has the formula 2PbCO_{3}·Pb(OH)_{2}, how nearly pure was a sample if 1 g. gave 30 cc. of carbon dioxide at 20° and 750 mm.? 10. Silicon belongs in the same family with tin and lead. In what respects are these elements similar? 11. What weight of tin could be obtained by the reduction of 1 ton of cassiterite? 12. What reaction would you expect to take place when lead peroxide is treated with hydrochloric acid? 13. White lead is often adulterated with barytes. Suggest a method for detecting it, if present, in a given example of white lead. CHAPTER XXX MANGANESE AND CHROMIUM ==================================================================== | | | | | | SYMBOL | ATOMIC | DENSITY | MELTING | FORMULAS OF ACIDS | | WEIGHT | | POINT | __________|________|________|_________|_________|___________________ | | | | | Manganese | Mn | 55.0 | 8.01 | 1900° | H_{2}MnO_{4} and | | | | | HMnO_{4} Chromium | Cr | 52.1 | 7.3 | 3000° | H_{2}CrO_{4} and | | | | | H_{2}Cr_{2}O_{7} ==================================================================== ~General.~ Manganese and chromium, while belonging to different families, have so many features in common in their chemical conduct that they may be studied together with advantage. They differ from most of the elements so far studied in that they can act either as acid-forming or base-forming elements. As base-forming elements each of the metals forms two series of salts. In the one series, designated by the suffix "ous," the metal is divalent; in the other series, designated by the suffix "ic," the metal is trivalent. Only the manganous and the chromic salts, however, are of importance. The acids in which these elements play the part of a non-metal are unstable, but their salts are usually stable, and some of them are important compounds. MANGANESE ~Occurrence.~ Manganese is found in nature chiefly as the dioxide MnO_{2}, called pyrolusite. In smaller amounts it occurs as the oxides Mn_{2}O_{3} and Mn_{3}O_{4}, and as the carbonate MnCO_{3}. Some iron ores also contain manganese. ~Preparation and properties.~ The element is difficult to prepare in pure condition and has no commercial applications. It can be prepared, however, by reducing the oxide with aluminium powder or by the use of the electric furnace, with carbon as the reducing agent. The metal somewhat resembles iron in appearance, but is harder, less fusible, and more readily acted upon by air and moisture. Acids readily dissolve it, forming manganous salts. ~Oxides of manganese.~ The following oxides of manganese are known: MnO, Mn_{2}O_{3}, Mn_{3}O_{4}, MnO_{2}, and Mn_{2}O_{7}. Only one of these, the dioxide, needs special mention. ~Manganese dioxide~ (_pyrolusite_) (MnO_{2}). This substance is the most abundant manganese compound found in nature, and is the ore from which all other compounds of manganese are made. It is a hard, brittle, black substance which is valuable as an oxidizing agent. It will be recalled that it is used in the preparation of chlorine and oxygen, in decolorizing glass which contains iron, and in the manufacture of ferromanganese. ~Compounds containing manganese as a base-forming element.~ As has been stated previously, manganese forms two series of salts. The most important of these salts, all of which belong to the manganous series, are the following: Manganous chloride MnCl_{2}·4H_{2}O. Manganous sulphide MnS. Manganous sulphate MnSO_{4}·4H_{2}O. Manganous carbonate MnCO_{3}. Manganous hydroxide Mn(OH)_{2}. The chloride and sulphate may be prepared by heating the dioxide with hydrochloric and sulphuric acids respectively: MnO_{2} + 4HCl = MnCl_{2} + 2H_{2}O + 2Cl, MnO_{2} + H_{2}SO_{4} = MnSO_{4} + H_{2}O + O. The sulphide, carbonate, and hydroxide, being insoluble, may be prepared from a solution of the chloride or sulphate by precipitation with the appropriate reagents. Most of the manganous salts are rose colored. They not only have formulas similar to the ferrous salts, but resemble them in many of their chemical properties. ~Compounds containing manganese as an acid-forming element.~ Manganese forms two unstable acids, namely, manganic acid and permanganic acid. While these acids are of little interest, some of their salts, especially the permanganates, are important compounds. ~Manganic acid and manganates.~ When manganese dioxide is fused with an alkali and an oxidizing agent a green compound is formed. The equation, when caustic potash is used, is as follows: MnO_{2} + 2KOH + O = K_{2}MnO_{4} + H_{2}O. The green compound (K_{2}MnO_{4}) is called potassium manganate, and is a salt of the unstable manganic acid (H_{2}MnO_{4}). The manganates are all very unstable. ~Permanganic acid and the permanganates.~ When carbon dioxide is passed through a solution of a manganate a part of the manganese is changed into manganese dioxide, while the remainder forms a salt of the unstable acid HMnO_{4}, called permanganic acid. The equation is 3K_{2}MnO_{4} + 2CO_{2} = MnO_{2} + 2KMnO_{4} + 2K_{2}CO_{3}. Potassium permanganate (KMnO_{4}) crystallizes in purple-black needles and is very soluble in water, forming an intensely purple solution. All other permanganates, as well as permanganic acid itself, give solutions of the same color. ~Oxidizing properties of the permanganates.~ The permanganates are remarkable for their strong oxidizing properties. When used as an oxidizing agent the permanganate is itself reduced, the exact character of the products formed from it depending upon whether the oxidation takes place (1) in an alkaline or neutral solution, or (2) in an acid solution. 1. _Oxidation in alkaline or neutral solution._ When the solution is either alkaline or neutral the potassium and the manganese of the permanganate are both converted into hydroxides, as shown in the equation 2KMnO_{4} + 5H_{2}O = 2Mn(OH)_{4} + 2KOH + 3O. 2. _Oxidation in acid solution._ When free acid such as sulphuric is present, the potassium and the manganese are both changed into salts of the acid: 2KMnO_{4} + 3H_{2}SO_{4} = K_{2}SO_{4} + 2MnSO_{4} + 3H_{2}O + 5O. Under ordinary conditions, however, neither one of these reactions takes place except in the presence of a third substance which is capable of oxidation. The oxygen is not given off in the free state, as the equations show, but is used up in effecting oxidation. Potassium permanganate is particularly valuable as an oxidizing agent not only because it acts readily either in acid or in alkaline solution, but also because the reaction takes place so easily that often it is not even necessary to heat the solution to secure action. The substance finds many uses in the laboratory, especially in analytical work. It is also used as an antiseptic as well as a disinfectant. CHROMIUM ~Occurrence.~ The ore from which all chromium compounds are made is chromite, or chrome iron ore (FeCr_{2}O_{4}). This is found most abundantly in New Caledonia and Turkey. The element also occurs in small quantities in many other minerals, especially in crocoisite (PbCrO_{4}), in which mineral it was first discovered. ~Preparation.~ Chromium, like manganese, is very hard to reduce from its ores, owing to its great affinity for oxygen. It can, however, be made by the same methods which have proved successful with manganese. Considerable quantities of an alloy of chromium with iron, called ferrochromium, are now produced for the steel industry. ~Properties.~ Chromium is a very hard metal of about the same density as iron. It is one of the most infusible of the metals, requiring a temperature little short of 3000° for fusion. At ordinary temperatures air has little action on it; at higher temperatures, however, it burns brilliantly. Nitric acid has no action on it, but hydrochloric and dilute sulphuric acids dissolve it, liberating hydrogen. ~Compounds containing chromium as a base-forming element.~ While chromium forms two series of salts, chromous salts are difficult to prepare and are of little importance. The most important of the chromic series are the following: Chromic hydroxide Cr(OH)_{3}. Chromic chloride CrCl_{3}·6H_{2}O. Chromic sulphate Cr_{2}(SO_{4})_{3}. Chrome alums ~Chromic hydroxide~ (Cr(OH)_{3}). This substance, being insoluble, can be obtained by precipitating a solution of the chloride or sulphate with a soluble hydroxide. It is a greenish substance which, like aluminium hydroxide, dissolves in alkalis, forming soluble salts. ~Dehydration of chromium hydroxide.~ When heated gently chromic hydroxide loses a part of its oxygen and hydrogen, forming the substance CrO·OH, which, like the corresponding aluminium compound, has more pronounced acid properties than the hydroxide. It forms a series of salts very similar to the spinels; chromite is the ferrous salt of this acid, having the formula Fe(CrO_{2})_{2}. When heated to a higher temperature chromic hydroxide is completely dehydrated, forming the trioxide Cr_{2}O_{3}. This resembles the corresponding oxides of aluminium and iron in many respects. It is a bright green powder, and when ignited strongly becomes almost insoluble in acids, as is also the case with aluminium oxide. ~Chromic sulphate~ (Cr_{2}(SO_{4})_{3}). This compound is a violet-colored solid which dissolves in water, forming a solution of the same color. This solution, however, turns green on heating, owing to the formation of basic salts. Chromic sulphate, like ferric and aluminium sulphates, unites with the sulphates of the alkali metals to form alums, of which the best known are potassium chrome alum (KCr(SO_{4})_{2}·12H_{2}O) and ammonium chrome alum (NH_{4}Cr(SO_{4})_{2}·12H_{2}O). These form beautiful dark purple crystals and have some practical uses in the tanning industry and in photography. A number of the salts of chromium are also used in the dyeing industry, for they hydrolyze like aluminium salts and the hydroxide forms a good mordant. ~Hydrolysis of chromium salts.~ When ammonium sulphide is added to a solution of a chromium salt, such as the sulphate, chromium hydroxide precipitates instead of the sulphide. This is due to the fact that chromic sulphide, like aluminium sulphide, hydrolyzes in the presence of water, forming chromic hydroxide and hydrosulphuric acid. Similarly, a soluble carbonate precipitates a basic carbonate of chromium. ~Compounds containing chromium as an acid-forming element.~ Like manganese, chromium forms two unstable acids, namely, chromic acid and dichromic acid. Their salts, the chromates and dichromates, are important compounds. ~Chromates.~ When a chromium compound is fused with an alkali and an oxidizing agent a chromate is produced. When potassium hydroxide is used as the alkali the equation is 2Cr(OH)_{3} + 4KOH + 3O = 2K_{2}CrO_{4} + 5H_{2}O. This reaction recalls the formation of a manganate under similar conditions. ~Properties of chromates.~ The chromates are salts of the unstable chromic acid (H_{2}CrO_{4}), and as a rule are yellow in color. Lead chromate (PbCrO_{4}) is the well-known pigment chrome yellow. Most of the chromates are insoluble and can therefore be prepared by precipitation. Thus, when a solution of potassium chromate is added to solutions of lead nitrate and barium nitrate respectively, the reactions expressed by the following equations occur: Pb(NO_{3})_{2} + K_{2}CrO_{4} = PbCrO_{4} + 2KNO_{3}, Ba(NO_{3})_{2} + K_{2}CrO_{4} = BaCrO_{4} + 2KNO_{3}. The chromates of lead and barium separate as yellow precipitates. The presence of either of these two metals can be detected by taking advantage of these reactions. ~Dichromates.~ When potassium chromate is treated with an acid the potassium salt of the unstable dichromic acid (H_{2}Cr_{2}O_{7}) is formed: 2K_{2}CrO_{4} + H_{2}SO_{4} = K_{2}Cr_{2}O_{7} + K_{2}SO_{4} + H_{2}O. The relation between the chromates and dichromates is the same as that between the phosphates and the pyrophosphates. Potassium dichromate might therefore be called potassium pyrochromate. ~Potassium dichromate~ (K_{2}Cr_{2}O_{7}). This is the best known dichromate, and is the most familiar chromium compound. It forms large crystals of a brilliant red color, and is rather sparingly soluble in water. When treated with potassium hydroxide it is converted into the chromate K_{2}Cr_{2}O_{7} + 2KOH = 2K_{2}CrO_{4} + H_{2}O. When added to a solution of lead or barium salt the corresponding chromates (not dichromates) are precipitated. With barium nitrate the equation is 2Ba(NO_{3})_{2} + K_{2}Cr_{2}O_{7} + H_{2}O = 2BaCrO_{4} + 2KNO_{3} + 2HNO_{3}. Potassium dichromate finds use in many industries as an oxidizing agent, especially in the preparation of organic substances, such as the dye alizarin, and in the construction of several varieties of electric batteries. ~Sodium chromates.~ The reason why the potassium salt rather than the sodium compound is used is that sodium chromate and dichromate are so soluble that it is hard to prepare them pure. This difficulty is being overcome now, and the sodium compounds are replacing the corresponding potassium salts. This is of advantage, since a sodium salt is cheaper than a potassium salt, so far as raw materials go. ~Oxidizing action of chromates and dichromates.~ When a dilute solution of a chromate or dichromate is acidified with an acid, such as sulphuric acid, no reaction apparently takes place. However, if there is present a third substance capable of oxidation, the chromium compound gives up a portion of its oxygen to this substance. Since the chromate changes into a dichromate in the presence of an acid, it will be sufficient to study the action of the dichromates alone. The reaction takes place in two steps. Thus, when a solution of ferrous sulphate is added to a solution of potassium dichromate acidified with sulphuric acid, the reaction is expressed by the following equations: (1) K_{2}Cr_{2}O_{7} + 4H_{2}SO_{4} = K_{2}SO_{4} + Cr_{2}(SO_{4})_{3} + 4H_{2}O + 3O, (2) 6FeSO_{4} + 3H_{2}SO_{4} + 3O = 3Fe_{2}(SO_{4})_{3} + 3H_{2}O. The dichromate decomposes in very much the same way as a permanganate does, the potassium and chromium being both changed into salts in which they play the part of metals, while part of the oxygen of the dichromate is liberated. By combining equations (1) and (2), the following is obtained: K_{2}Cr_{2}O_{7} + 7H_{2}SO_{4} + 6FeSO_{4} = K_{2}SO_{4} + Cr_{2}(SO_{4})_{3} + 3Fe_{2}(SO_{4})_{3} + 7H_{2}0. This reaction is often employed in the estimation of iron in iron ores. ~Potassium chrome alum.~ It will be noticed that the oxidizing action of potassium dichromate leaves potassium sulphate and chromium sulphate as the products of the reaction. On evaporating the solution these substances crystallize out as potassium chrome alum, which substance is produced as a by-product in the industries using potassium dichromate for oxidizing purposes. ~Chromic anhydride~ (CrO_{3}). When concentrated sulphuric acid is added to a strong solution of potassium dichromate, and the liquid allowed to stand, deep red needle-shaped crystals appear which have the formula CrO_{3}.This oxide of chromium is called chromic anhydride, since it combines readily with water to form chromic acid: CrO_{3} + H_{2}O = H_{2}CrO_{4}. It is therefore analogous to sulphur trioxide which forms sulphuric acid in a similar way: SO_{3} + H_{2}O = H_{2}SO_{4}. Chromic anhydride is a very strong oxidizing agent, giving up oxygen and forming chromic oxide: 2CrO_{3} = Cr_{2}O_{3} + 3O. ~Rare elements of the family.~ Molybdenum, tungsten, and uranium are three rather rare elements belonging in the same family with chromium, and form many compounds which are similar in formulas to the corresponding compounds of chromium. They can play the part of metals and also form acids resembling chromic acid in formula. Thus we have molybdic acid (H_{2}MoO_{4}), the ammonium salt of which is (NH_{4})_{2}MoO_{4}. This salt has the property of combining with phosphoric acid to form a very complex substance which is insoluble in nitric acid. On this account molybdic acid is often used in the estimation of the phosphoric acid present in a substance. Like chromium, the metals are difficult to prepare in pure condition. Alloys with iron can be prepared by reducing the mixed oxides with carbon in an electric furnace; these alloys are used to some extent in preparing special kinds of steel. EXERCISES 1. How does pyrolusite effect the decolorizing of glass containing iron? 2. Write the equations for the preparation of manganous chloride, carbonate, and hydroxide. 3. Write the equations representing the reactions which take place when ferrous sulphate is oxidized to ferric sulphate by potassium permanganate in the presence of sulphuric acid. 4. In the presence of sulphuric acid, oxalic acid is oxidized by potassium permanganate according to the equation C_{2}H_{2}O_{4} + O = 2CO_{2} + H_{2}O. Write the complete equation. 5. 10 g. of iron were dissolved in sulphuric acid and oxidized to ferric sulphate by potassium permanganate. What weight of the permanganate was required? 6. What weight of ferrochromium containing 40% chromium must be added to a ton of steel to produce an alloy containing 1% of chromium? 7. Write the equation representing the action of ammonium sulphide upon chromium sulphate. 8. Potassium chromate oxidizes hydrochloric acid, forming chlorine. Write the complete equation. 9. Give the action of sulphuric acid on potassium dichromate (a) in the presence of a large amount of water; (b) in the presence of a small amount of water. CHAPTER XXXI GOLD AND THE PLATINUM FAMILY ============================================================================== | | | | | | | | ATOMIC | | HIGHEST | HIGHEST | MELTING | SYMBOL | WEIGHT | DENSITY | OXIDE | CHLORIDE | POINT __________|________|________|_________|_________ |__________|_____________ | | | | | | Ruthenium | Ru | 101.7 | 12.26 | RuO_{4} | RuCl_{4} | Electric arc Rhodium | Rh | 103. | 12.1 | RhO_{2} | RhCl_{2} | Electric arc Palladium | Pd | 106.5 | 11.8 | PdO_{2} | PdCl_{4} | 1500° Iridium | Ir | 193. | 22.42 | IrO_{2} | IrCl_{4} | 1950° Osmium | Os | 191. | 22.47 | OsO_{4} | OsCl_{4} | Electric arc Platinum | Pt | 194.8 | 21.50 | PtO_{2} | PtCl_{4} | 1779° Gold | Au | 197.2 | 19.30 | Au_{2}O_{3} | AuCl_{3} | 1064° ============================================================================== ~The family.~ Following iron, nickel, and cobalt in the eighth column of the periodic table are two groups of three elements each. The metals of the first of these groups--ruthenium, rhodium, and palladium--have atomic weights near 100 and densities near 12. The metals of the other group--iridium, osmium, and platinum--have atomic weights near 200 and densities near 21. These six rare elements have very similar physical properties and resemble each other chemically not only in the type of compounds which they form but also in the great variety of them. They occur closely associated in nature, usually as alloys of platinum in the form of irregular metallic grains in sand and gravel. Platinum is by far the most abundant of the six. Although the periodic classification assigns gold to the silver-copper group, its physical as well as many of its chemical properties much more closely resemble those of the platinum metals, and it can he conveniently considered along with them. The four elements gold, platinum, osmium, and iridium are the heaviest substances known, being about twice as heavy as lead. PLATINUM ~Occurrence.~ About 90% of the platinum of commerce comes from Russia, small amounts being produced in California, Brazil, and Australia. ~Preparation.~ Native platinum is usually alloyed with gold and the platinum metals. To separate the platinum the alloy is dissolved in aqua regia, which converts the platinum into chloroplatinic acid (H_{2}PtCl_{6}). Ammonium chloride is then added, which precipitates the platinum as insoluble ammonium chloroplatinate: H_{2}PtCl_{6} + 2NH_{4}Cl = (NH_{4})_{2}PtCl_{6} + 2HCl. Some iridium is also precipitated as a similar compound. On ignition the double chloride is decomposed, leaving the platinum as a spongy metallic mass, which is melted in an electric furnace and rolled or hammered into the desired shape. ~Physical properties.~ Platinum is a grayish-white metal of high luster, and is very malleable and ductile. It melts in the oxyhydrogen blowpipe and in the electric furnace; it is harder than gold and is a good conductor of electricity. In finely divided form it has the ability to absorb or occlude gases, especially oxygen and hydrogen. These gases, when occluded, are in a very active condition resembling the nascent state, and can combine with each other at ordinary temperatures. A jet of hydrogen or coal gas directed upon spongy platinum is at once ignited. ~Platinum as a catalytic agent.~ Platinum is remarkable for its property of acting as a catalytic agent in a large number of chemical reactions, and mention has been made of this use of the metal in connection with the manufacture of sulphuric acid. When desired for this purpose some porous or fibrous substance, such as asbestos, is soaked in a solution of platinic chloride and then ignited. The platinum compound is decomposed and the platinum deposited in very finely divided form. Asbestos prepared in this way is called platinized asbestos. The catalytic action seems to be in part connected with the property of absorbing gases and rendering them nascent. Some other metals possess this same power, notably palladium, which is remarkable for its ability to absorb hydrogen. ~Chemical properties.~ Platinum is a very inactive element chemically, and is not attacked by any of the common acids. Aqua regia slowly dissolves it, forming platinic chloride (PtCl_{4}), which in turn unites with the hydrochloric acid present in the aqua regia, forming the compound chloroplatinic acid (H_{2}PtCl_{6}). Platinum is attacked by fused alkalis. It combines at higher temperatures with carbon and phosphorus and alloys with many metals. It is readily attacked by chlorine but not by oxidizing agents. ~Applications.~ Platinum is very valuable as a material for the manufacture of chemical utensils which are required to stand a high temperature or the action of strong reagents. Platinum crucibles, dishes, forceps, electrodes, and similar articles are indispensable in the chemical laboratory. In the industries it is used for such purposes as the manufacture of pans for evaporating sulphuric acid, wires for sealing through incandescent light bulbs, and for making a great variety of instruments. Unfortunately the supply of the metal is very limited, and the cost is steadily advancing, so that it is now more valuable than gold. ~Compounds.~ Platinum forms two series of salts of which platinous chloride (PtCl_{2}) and platinic chloride (PtCl_{4}) are examples. Platinates are also known. While a great variety of compounds of platinum have been made, the substance is chiefly employed in the metallic state. ~Platinic chloride (PtCl_{4}).~ Platinic chloride is an orange-colored, soluble compound made by heating chloroplatinic acid in a current of chlorine. If hydrochloric acid is added to a solution of the substance, the two combine, forming chloroplatinic acid (H_{2}PtCl_{6}): 2HCl + PtCl_{4} = H_{2}PtCl_{6}. The potassium and ammonium salts of this acid are nearly insoluble in water and alcohol. The acid is therefore used as a reagent to precipitate potassium in analytical work. With potassium chloride the equation is 2KCl + H_{2}PtCl_{6} = K_{2}PtCl_{6} + 2HCl. ~Other metals of the family.~ The other members of the family have few applications. Iridium is used in the form of a platinum alloy, since the alloy is much harder than pure platinum and is even less fusible. This alloy is sometimes used to point gold pens. Osmium tetroxide (OsO_{4}) is a very volatile liquid and is used under the name of osmic acid as a stain for sections in microscopy. GOLD ~Occurrence.~ Gold has been found in many localities, the most famous being South Africa, Australia, Russia, and the United States. In this country it is found in Alaska and in nearly half of the states of the union, notably in California, Colorado, and Nevada. It is usually found in the native condition, frequently alloyed with silver; in combination it is sometimes found as telluride (AuTe_{2}), and in a few other compounds. ~Mining.~ Native gold occurs in the form of small grains or larger nuggets in the sands of old rivers, or imbedded in quartz veins in rocks. In the first case it is obtained in crude form by placer mining. The sand containing the gold is shaken or stirred in troughs of running waters called sluices. This sweeps away the sand but allows the heavier gold to sink to the bottom of the sluice. Sometimes the sand containing the gold is washed away from its natural location into the sluices by powerful streams of water delivered under pressure from pipes. This is called hydraulic mining. In vein mining the gold-bearing quartz is mined from the veins, stamped into fine powder in stamping mills, and the gold extracted by one of the processes to be described. ~Extraction.~ 1. _Amalgamation process._ In the amalgamation process the powder containing the gold is washed over a series of copper plates whose surfaces have been amalgamated with mercury. The gold sticks to the mercury or alloys with it, and after a time the gold and mercury are scraped off and the mixture is distilled. The mercury distills off and the gold is left in the retort ready for refining. 2. _Chlorination process._ When gold occurs along with metallic sulphides it is often extracted by chlorination. The ore is first roasted, and is then moistened and treated with chlorine. This dissolves the gold but not the metallic oxides: Au + 3Cl = AuCl_{3}. The gold chloride, being soluble, is extracted from the mixture with water, and the gold is precipitated from the solution, usually by adding ferrous sulphate: AuCl_{3} + 3FeSO_{4} = Au + FeCl_{3} + Fe_{2}(SO_{4})_{3}. 3. _Cyanide process._ This process depends upon the fact that gold is soluble in a solution of potassium cyanide in the presence of the oxygen of the air. The powder from the stamping mills is treated with a very dilute potassium cyanide solution which extracts the gold: 2Au + 4KCN + H_{2}O + O = 2KOH + 2KAu(CN)_{2}. From this solution the gold can be obtained by electrolysis or by precipitation with metallic zinc: 2KAu(CN)_{2} + Zn = K_{2}Zn(CN)_{4} + 2Au. ~Refining of gold.~ Gold is refined by three general methods: 1. _Electrolysis._ When gold is dissolved in a solution of potassium cyanide, and the solution electrolyzed, the gold is deposited in very pure condition on the cathode. 2. _Cupellation._ When the gold is alloyed with easily oxidizable metals, such as copper or lead, it may be refined by cupellation. The alloy is fused with an oxidizing flame on a shallow hearth made of bone ash, which substance has the property of absorbing metallic oxides but not the gold. Any silver which may be present remains alloyed with the gold. 3. _Parting with sulphuric acid._ Gold may be separated from silver, as well as from many other metals, by heating the alloy with concentrated sulphuric acid. This dissolves the silver, while the gold is not attacked. ~Physical properties.~ Gold is a very heavy bright yellow metal, exceedingly malleable and ductile, and a good conductor of electricity. It is quite soft and is usually alloyed with copper or silver to give it the hardness required for most practical uses. The degree of fineness is expressed in terms of carats, pure gold being twenty-four carats; the gold used for jewelry is usually eighteen carats, eighteen parts being gold and six parts copper or silver. Gold coinage is 90% gold and 10% copper. ~Chemical properties.~ Gold is not attacked by any one of the common acids; aqua regia easily dissolves it, forming gold chloride (AuCl_{3}), which in turn combines with hydrochloric acid to form chlorauric acid (HAuCl_{4}). Fused alkalis also attack it. Most oxidizing agents are without action upon it, and in general it is not an active element. ~Compounds.~ The compounds of gold, though numerous and varied in character, are of comparatively little importance and need not be described in detail. The element forms two series of salts in which it acts as a metal: in the aurous series the gold is univalent, the chloride having the formula AuCl; in the auric series it is trivalent, auric chloride having the formula AuCl_{3}. Gold also acts as an acid-forming element, forming such compounds as potassium aurate (KAuO_{2}). Its compounds are very easily decomposed, however, metallic gold separating from them. EXERCISES 1. From the method of preparation of platinum, what metal is likely to be alloyed with it? 2. The "platinum chloride" of the laboratory is made by dissolving platinum in aqua regia. What is the compound? 3. How would you expect potassium aurate and platinate to be formed? What precautions would this suggest in the use of platinum vessels? 4. Why must gold ores be roasted in the chlorination process? CHAPTER XXXII SOME SIMPLE ORGANIC COMPOUNDS ~Division of chemistry into organic and inorganic.~ Chemistry is usually divided into two great divisions,--organic and inorganic. The original significance of these terms was entirely different from the meaning which they have at the present time. 1. _Original significance._ The division into organic and inorganic was originally made because it was believed that those substances which constitute the essential parts of living organisms were built up under the influence of the life force of the organism. Such substances, therefore, should be regarded as different from those compounds prepared in the laboratory or formed from the inorganic or mineral constituents of the earth. In accordance with this view organic chemistry included those substances formed by living organisms. Inorganic chemistry, on the other hand, included all substances formed from the mineral portions of the earth. In 1828 the German chemist Wöhler prepared urea, a typical organic compound, from inorganic materials. The synthesis of other so-called organic compounds followed, and at present it is known that the same chemical laws apply to all substances whether formed in the living organism or prepared in the laboratory from inorganic constituents. The terms "organic" and "inorganic" have therefore lost their original significance. 2. _Present significance._ The great majority of the compounds found in living organisms contain carbon, and the term "organic chemistry," as used at present, includes not only these compounds but all compounds of carbon. _Organic chemistry_ has become, therefore, _the chemistry of the compounds of carbon_, all other substances being treated under the head of inorganic chemistry. This separation of the compounds of carbon into a group by themselves is made almost necessary by their great number, over one hundred thousand having been recorded. For convenience some of the simpler carbon compounds, such as the oxides and the carbonates, are usually discussed in inorganic chemistry. ~The grouping of compounds in classes.~ The study of organic chemistry is much simplified by the fact that the large number of bodies included in this field may be grouped in classes of similar compounds. It thus becomes possible to study the properties of each class as a whole, in much the same way as we study a group of elements. The most important of these classes are the _hydrocarbons_, the _alcohols_, the _aldehydes_, the _acids_, the _ethereal salts_, the _ethers_, the _ketones_, the _organic bases_, and the _carbohydrates_. A few members of each of these classes will now be discussed briefly. THE HYDROCARBONS Carbon and hydrogen combine to form a large number of compounds. These compounds are known collectively as the _hydrocarbons_. They may be divided into a number of groups or series, each being named from its first member. Some of the groups are as follows: METHANE SERIES CH_{4} methane C_{2}H_{6} ethane C_{3}H_{8} propane C_{4}H_{10} butane C_{5}H_{12} pentane C_{6}H_{14} hexane C_{7}H_{16} heptane C_{8}H_{18} octane ETHYLENE SERIES C_{2}H_{4} ethylene C_{3}H_{6} propylene C_{4}H_{8} butylene BENZENE SERIES C_{6}H_{6} benzene C_{7}H_{8} toluene C_{8}H_{10} xylene ACETYLENE SERIES C_{2}H_{2} acetylene C_{3}H_{4} allylene Only the lower members (that is, those which contain a small number of carbon atoms) of the above groups are given. The methane series is the most extensive, all of the compounds up to C_{24}H_{50} being known. It will be noticed that the successive members of each of the above series differ by the group of atoms (CH_{2}). Such a series is called an _homologous series_. In general, it may be stated that the members of an homologous series show a regular gradation in most physical properties and are similar in chemical properties. Thus in the methane group the first four members are gases at ordinary temperatures; those containing from five to sixteen carbon atoms are liquids, the boiling points of which increase with the number of carbon atoms present. Those containing more than sixteen carbon atoms are solids. ~Sources of the hydrocarbons.~ There are two chief sources of the hydrocarbons, namely, (1) crude petroleum and (2) coal tar. 1. _Crude petroleum._ This is a liquid pumped from wells driven into the earth in certain localities. Pennsylvania, Ohio, Kansas, California, and Texas are the chief oil-producing regions in the United States. The crude petroleum consists largely of liquid hydrocarbons in which are dissolved both gaseous and solid hydrocarbons. Before being used it must be refined. In this process the petroleum is run into large iron stills and subjected to fractional distillation. The various hydrocarbons distill over in the general order of their boiling points. The distillates which collect between certain limits of temperature are kept separate and serve for different uses; they are further purified, generally by washing with sulphuric acid, then with an alkali, and finally with water. Among the products obtained from crude petroleum in this way are the naphthas, including benzine and gasoline, kerosene or coal oil, lubricating oils, vaseline, and paraffin. None of these products are definite chemical compounds, but each consists of a mixture of hydrocarbons, the boiling points of which lie within certain limits. 2. _Coal tar._ This product is obtained in the manufacture of coal gas, as already explained. It is a complex mixture and is refined by the same general method used in refining crude petroleum. The principal hydrocarbons obtained from the coal tar are benzene, toluene, naphthalene, and anthracene. In addition to the hydrocarbons, coal tar contains many other compounds, such as carbolic acid and aniline. ~Properties of the hydrocarbons.~ The lower members of the first two series of hydrocarbons mentioned are all gases; the succeeding members are liquids. In some series, as the methane series, the higher members are solids. The preparation and properties of methane and acetylene have been discussed in a previous chapter. Ethylene is present in small quantities in coal gas and may be obtained in the laboratory by treating alcohol (C_{2}H_{6}O) with sulphuric acid: C_{2}H_{6}O = C_{2}H_{4} + H_{2}O. Benzene, the first member of the benzene series, is a liquid boiling at 80°. The hydrocarbons serve as the materials from which a large number of compounds can be prepared; indeed, it has been proposed to call organic chemistry _the chemistry of the hydrocarbon derivatives_. ~Substitution products of the hydrocarbons.~ As a rule, at least a part of the hydrogen in any hydrocarbon can be displaced by an equivalent amount of certain elements or groups of elements. Thus the compounds CH_{3}Cl, CH_{2}Cl_{2}, CHCl_{3}, CCl_{4} can be obtained from methane by treatment with chlorine. Such compounds are called _substitution products_. ~Chloroform~ (CHCl_{3}). This can be made by treating methane with chlorine, as just indicated, although a much easier method consists in treating alcohol or acetone (which see) with bleaching powder. Chloroform is a heavy liquid having a pleasant odor and a sweetish taste. It is largely used as a solvent and as an anæsthetic in surgery. ~Iodoform~ (CHI_{3}). This is a yellow crystalline solid obtained by treating alcohol with iodine and an alkali. It has a characteristic odor and is used as an antiseptic. ALCOHOLS When such a compound as CH_{3}Cl is treated with silver hydroxide the reaction expressed by the following equation takes place: CH_{3}Cl + AgOH = CH_{3}OH + AgCl. Similarly C_{2}H_{5}Cl will give C_{2}H_{5}OH and AgCl. The compounds CH_{3}OH and C_{2}H_{5}OH so obtained belong to the class of substances known as _alcohols_. From their formulas it will be seen that they may be regarded as derived from hydrocarbons by substituting the hydroxyl group (OH) for hydrogen. Thus the alcohol CH_{3}OH may be regarded as derived from methane (CH_{4}) by substituting the group OH for one atom of hydrogen. A great many alcohols are known, and, like the hydrocarbons, they may be grouped into series. The relation between the first three members of the methane series and the corresponding alcohols is shown in the following table: CH_{4} (methane) CH_{3}OH (methyl alcohol). C_{2}H_{6} (ethane) C_{2}H_{5}OH (ethyl alcohol). C_{3}H_{8} (propane) C_{3}H_{7}OH (propyl alcohol). ~Methyl alcohol~ (_wood alcohol_) (CH_{3}OH). When wood is placed in an air-tight retort and heated, a number of compounds are evolved, the most important of which are the three liquids, methyl alcohol, acetic acid, and acetone. Methyl alcohol is obtained entirely from this source, and on this account is commonly called _wood alcohol_. It is a colorless liquid which has a density of 0.79 and boils at 67°. It burns with an almost colorless flame and is sometimes used for heating purposes, in place of the more expensive ethyl alcohol. It is a good solvent for organic substances and is used especially as a solvent in the manufacture of varnishes. It is very poisonous. ~Ethyl alcohol~ (_common alcohol_) (C_{2}H_{5}OH). 1. _Preparation._ This compound may be prepared from glucose (C_{6}H_{12}O_{6}), a sugar easily obtained from starch. If some baker's yeast is added to a solution of glucose and the temperature is maintained at about 30°, bubbles of gas are soon evolved, showing that a change is taking place. The yeast contains a large number of minute organized bodies, which are really forms of plant life. The plant grows in the glucose solution, and in so doing secretes a substance known as _zymase_, which breaks down the glucose in accordance with the following equation: C_{6}H_{12}O_{6} = 2C_{2}H_{5}OH + 2CO_{2}. ~Laboratory preparation of alcohol.~ The formation of alcohol and carbon dioxide from glucose may be shown as follows: About 100 g. of glucose are dissolved in a liter of water in flask A (Fig. 90). This flask is connected with the bottle B, which is partially filled with limewater. The tube C contains solid sodium hydroxide. A little baker's yeast is now added to the solution in flask A, and the apparatus is connected, as shown in the figure. If the temperature is maintained at about 30°, the reaction soon begins. The bubbles of gas escape through the limewater in B. A precipitate of calcium carbonate soon forms in the limewater, showing the presence of carbon dioxide. The sodium hydroxide in tube C prevents the carbon dioxide in the air from acting on the limewater. The alcohol remains in the flask A and may be separated by fractional distillation. [Illustration: Fig. 90] 2. _Properties._ Ethyl alcohol is a colorless liquid with a pleasant odor. It has a density of 0.78 and boils at 78°. It resembles methyl alcohol in its general properties. It is sometimes used as a source of heat, since its flame is very hot and does not deposit carbon, as the flame from oil does. When taken into the system in small quantities it causes intoxication; in larger quantities it acts as a poison. The intoxicating properties of such liquors as beer, wine, and whisky are due to the alcohol present. Beer contains from 2 to 5% of alcohol, wine from 5 to 20%, and whisky about 50%. The ordinary alcohol of the druggist contains 94% of alcohol and 6% of water. When this is boiled with lime and then distilled nearly all the water is removed, the distillate being called _absolute alcohol_. ~Commercial preparation of alcohol.~ Alcohol is prepared commercially from starch obtained from corn or potatoes. The starch is first converted into a sugar known as maltose, by the action of _malt_, a substance prepared by moistening barley with water, allowing it to germinate, and then drying it. There is present in the malt a substance known as diastase, which has the property of changing starch into maltose. This sugar, like glucose, breaks down into alcohol and carbon dioxide in the presence of yeast. The resulting alcohol is separated by fractional distillation. ~Denatured alcohol.~ The 94% alcohol is prepared at present at a cost of about 35 cents per gallon, which is about half the cost of the preparation of methyl alcohol. The government, however, imposes a tax on all ethyl alcohol which amounts to $2.08 per gallon on the 94% product. This increases its cost to such an extent that it is not economical to use it for many purposes for which it is adapted, such as a solvent in the preparation of paints and varnishes and as a material for the preparation of many important organic compounds. By an act of Congress in 1906, the tax was removed from _denatured_ alcohol, that is alcohol mixed with some substance which renders it unfit for the purposes of a beverage but will not impair its use for manufacturing purposes. Some of the European countries have similar laws. The substances ordinarily used to denature alcohol are wood alcohol and pyridine, the latter compound having a very offensive odor. ~Fermentation.~ The reaction which takes place in the preparation of ethyl alcohol belongs to the class of changes known under the general name of fermentation. Thus we say that the yeast causes the glucose to ferment, and the process is known as alcoholic fermentation. There are many kinds of fermentations, and each is thought to be due to the presence of a definite substance known as an _enzyme_, which acts by catalysis. In many cases, as in alcoholic fermentation, the change is brought about by the action of minute forms of life. These probably secrete the enzymes which cause the fermentation to take place. Thus the yeast plant is supposed to bring about alcoholic fermentation by secreting the enzyme known as zymase. ~Glycerin~ (C_{3}H_{5}(OH)_{3}). This compound may be regarded as derived from propane (C_{3}H_{8}) by displacing three atoms of hydrogen by three hydroxyl groups, and must therefore be regarded as an alcohol. It is formed in the manufacture of soaps, as will be explained later. It is an oily, colorless liquid having a sweetish taste. It is used in medicine and in the manufacture of the explosives nitroglycerin and dynamite. ALDEHYDES When alcohols are treated with certain oxidizing agents two hydrogen atoms are removed from each molecule of the alcohol. The resulting compounds are known as aldehydes. The relation of the aldehydes derived from methyl and ethyl alcohol to the alcohols themselves may be shown as follows: Alcohols {CH_{3}OH Corresponding aldehydes {CH_{2}O {C_{2}H_{5}OH {C_{2}H_{4}O The first of these (CH_{2}O) is a gas known as formaldehyde. Its aqueous solution is largely used as an antiseptic and disinfectant under the name of _formalin_. Acetaldehyde (C_{2}H_{4}O) is a liquid boiling at 21°. ACIDS Like the other classes of organic compounds, the organic acids may be arranged in homologous series. One of the most important of these series is the _fatty-acid series_, the name having been given to it because the derivatives of certain of its members are constituents of the fats. Some of the most important members of the series are given in the following table. They are all monobasic, and this fact is expressed in the formulas by separating the replaceable hydrogen atom from the rest of the molecule: H·CHO_{2} formic acid, a liquid boiling at 100°. H·C_{2}H_{3}O acetic acid, a liquid boiling at 118°. H·C_{3}H_{5}O_{2} propionic acid, a liquid boiling at 140°. H·C_{4}H_{7}O_{2} butyric acid, a liquid boiling at 163°. H·C_{16}H_{31}O_{2} palmitic acid, a solid melting at 62°. H·C_{18}H_{35}O_{2} stearic acid, a solid melting at 69°. ~Formic acid~ (H·CHO_{2}). The name "formic" is derived from the Latin _formica_, signifying ant. This name was given to the acid because it was formerly obtained from a certain kind of ants. It is a colorless liquid and occurs in many plants such as the stinging nettles. The inflammation caused by the sting of the bee is due to formic acid. ~Acetic acid~ (H·C_{2}H_{3}O_{2}). Acetic acid is the acid present in vinegar, the sour taste being due to it. It can be prepared by either of the following methods. 1. _Acetic fermentation._ This consists in the change of alcohol into acetic acid through the agency of a minute organism commonly called mother of vinegar. The change is represented by the following equation: C_{2}H_{5}OH + 2O = HC_{2}H_{3}O_{2} + H_{2}O. The various kinds of vinegars are all made by this process. In the manufacture of cider vinegar the sugar present in the cider first undergoes alcoholic fermentation; the resulting alcohol then undergoes acetic fermentation. The amount of acetic acid present in vinegars varies from 3 to 6%. 2. _From the distillation of wood._ The liquid obtained by heating wood in the absence of air contains a large amount of acetic acid, and this can be separated readily in a pure state. This is the most economical method for the preparation of the concentrated acid. Acetic acid is a colorless liquid and has a strong pungent odor. Many of its salts are well-known compounds. Lead acetate (Pb(C_{2}H_{3}O_{2})_{2}) is the ordinary _sugar of lead_. Sodium acetate (NaC_{2}H_{3}O_{2}) is a white solid largely used in making chemical analyses. Copper acetate (Cu(C_{2}H_{3}O_{2})_{2}) is a blue solid. When copper is acted upon by acetic acid in the presence of air a green basic acetate of copper is formed. This is commonly known as verdigris. All acetates are soluble in water. ~Butyric acid~ (H·C_{4}H_{7}O_{2}). Derivatives of butyric acid are present in butter and impart to it its characteristic flavor. ~Palmitic and stearic acids.~ Ordinary fats consist principally of derivatives of palmitic and stearic acids. When the fats are heated with sodium hydroxide the sodium salts of these acids are formed. If hydrochloric acid is added to a solution of the sodium salts, the free palmitic and stearic acids are precipitated. They are white solids, insoluble in water. Stearic acid is often used in making candles. ~Acids belonging to other series.~ In addition to members of the fatty-acid series, mention may be made of the following well-known acids. ~Oxalic acid~ (H_{2}C_{2}O_{4}). This is a white solid which occurs in nature in many plants, such as the sorrels. Its ammonium salt ((NH_{4})_{2}C_{2}O_{4}) is used as a reagent for the detection of calcium. When added to a solution of a calcium compound the white, insoluble calcium oxalate (CaC_{2}O_{4}) precipitates. ~Tartaric acid~ (H_{2}·C_{4}H_{4}O_{6}). This compound occurs either in a free state or in the form of its salts in many fruits. The potassium acid salt (KHC_{4}H_{4}O_{6}) occurs in the juice of grapes. When the juice ferments in the manufacture of wine, this salt, being insoluble in alcohol, separates out on the sides of the cask and in this form is known as argol. This is more or less colored by the coloring matter of the grape. When purified it forms a white solid and is sold under the name of cream of tartar. The following are also well-known salts of tartaric acid: potassium sodium tartrate (Rochelle salt) (KNaC_{4}H_{4}O_{6}), potassium antimonyl tartrate (tartar emetic) (KSbOC_{4}H_{4}O_{6}). ~Cream of tartar baking powders.~ The so-called cream of tartar baking powders consist of a mixture of cream of tartar, bicarbonate of soda, and some starch or flour. When water is added to this mixture the cream of tartar slowly acts upon the soda present liberating carbon dioxide in accordance with the following equation: KHC_{4}H_{4}O_{6} + NaHCO_{3} = KNaC_{4}H_{4}O_{6} + H_{2}O + CO_{2}. The carbon dioxide evolved escapes through the dough, thus making it light and porous. ~Citric acid~ (H_{3}·C_{6}H_{5}O_{7}). This acid occurs in many fruits, especially in lemons. It is a white solid, soluble in water, and is often used as a substitute for lemons in making lemonade. ~Lactic acid~ (H·C_{3}H_{5}O_{3}). This is a liquid which is formed in the souring of milk. ~Oleic acid~ (H·C_{18}H_{33}O_{2}). The derivatives of this acid constitute the principal part of many oils and liquid fats. The acid itself is an oily liquid. ETHEREAL SALTS When acids are brought in contact with alcohols under certain conditions a reaction takes place similar to that which takes place between acids and bases. The following equations will serve as illustrations: KOH + HNO_{3} = KNO_{3} + H_{2}O, CH_{3}OH + HNO_{3} = CH_{3}NO_{3} + H_{2}O. The resulting compounds of which methyl nitrate (CH_{3}NO_{3}) may be taken as the type belong to the class known as _ethereal salts_, the name having been given them because some of them possess pleasant ethereal odors. It will be seen that the ethereal salts differ from ordinary salts in that they contain a hydrocarbon radical, such as CH_{3}, C_{2}H_{5}, C_{3}H_{5}, in place of a metal. ~The nitrates of glycerin~ (_nitroglycerin_). Nitric acid reacts with glycerin in the same way that it reacts with a base containing three hydroxyl groups such as Fe(OH)_{3}: Fe(OH)_{3} + 3HNO_{3} = Fe(NO_{3})_{3} + 3H_{2}O, C_{3}H_{5}(OH)_{3} + 3HNO_{3} = C_{3}H_{5}(NO_{3})_{3} + 3H_{2}O. The resulting nitrate (C_{3}H_{5}(NO_{3})_{3}) is the main constituent of _nitroglycerin_, a slightly yellowish oil characterized by its explosive properties. Dynamite consists of porous earth which has absorbed nitroglycerin, and its strength depends on the amount present. It is used much more largely than nitroglycerin itself, since it does not explode so readily by concussion and hence can be transported with safety. ~The fats.~ These are largely mixtures of the ethereal salts known respectively as olein, palmitin, and stearin. These salts may be regarded as derived from oleic, palmitic, and stearic acids respectively, by replacing the hydrogen of the acid with the glycerin radical C_{3}H_{5}. Since this radical is trivalent and oleic, palmitic, and stearic acids contain only one replaceable hydrogen atom to the molecule, it is evident that three molecules of each acid must enter into each molecule of the ethereal salt. The formulas for the acids and the ethereal salts derived from each are as follows: HC_{18}H_{33}O_{2} (oleic acid) C_{8}H_{6}(C_{18}H_{33}O_{2})_{3}, (olein) HC_{16}H_{31}O_{2} (palmitic acid) C_{3}H_{5}(C_{16}H_{31}0_{2})_{3} (palmitin) HC_{18}H_{35}O_{2} (stearic acid) C_{3}H_{5}(C_{18}H_{35}O_{2})_{3} (stearin) Olein is a liquid and is the main constituent of liquid fats. Palmitin and stearin are solids. ~Butter fat and oleomargarine.~ Butter fat consists principally of olein, palmitin, and stearin. The flavor of the fat is due to the presence of a small amount of butyrin, which is an ethereal salt of butyric acid. Oleomargarine differs from butter mainly in the fact that a smaller amount of butyrin is present. It is made from the fats obtained from cattle and hogs. This fat is churned up with milk, or a small amount of butter is added, in order to furnish sufficient butyrin to impart the butter flavor. ~Saponification.~ When an ethereal salt is heated with an alkali a reaction expressed by the following equation takes place: C_{2}H_{5}NO_{3} + KOH = C_{2}H_{5}OH + KNO_{3}. This process is known as _saponification_, since it is the one which takes place in the manufacture of soaps. The ordinary soaps are made by heating fats with a solution of sodium hydroxide. The reactions involved may be illustrated by the following equation representing the reaction between palmitin and sodium hydroxide: C_{3}H_{5}(C_{16}H_{31}O_{2})_{3} + 3 NaOH = 3 NaC_{16}H_{31}O_{2} + C_{3}H_{5}(OH)_{3}. In accordance with this equation the ethereal salts in the fats are converted into glycerin and the sodium salts of the corresponding acids. The sodium salts are separated and constitute the soaps. These salts are soluble in water. When added to water containing calcium salts the insoluble calcium palmitate and stearate are precipitated. Magnesium salts act in a similar way. It is because of these facts that soap is used up by hard waters. ETHERS When ethyl alcohol is heated to 140° with sulphuric acid the reaction expressed by the following equation takes place: 2C_{2}H_{5}OH = (C_{2}H_{5})_{2}O + H_{2}O. The resulting compound, (C_{2}H_{5})_{2}O, is ordinary ether and is the most important member of the class of compounds called _ethers_. Ordinarily ether is a light, very inflammable liquid boiling at 35°. It is used as a solvent for organic substances and as an anæsthetic in surgical operations. KETONES The most common member of this group is acetone (C_{3}H_{6}O), a colorless liquid obtained when wood is heated in the absence of air. It is used in the preparation of other organic compounds, especially chloroform. ORGANIC BASES This group includes a number of compounds, all of which contain nitrogen as well as carbon. They are characterized by combining directly with acids to form salts, and in this respect they resemble ammonia. They may, indeed, be regarded as derived from ammonia by displacing a part or all of the hydrogen present in ammonia by hydrocarbon radicals. Among the simplest of these compounds may be mentioned methylamine (CH_{3}NH_{2}) and ethylamine (C_{2}H_{5}NH_{2}). These two compounds are gases and are formed in the distillation of wood and bones. Pyridine (C_{5}H_{6}N) and quinoline (C_{9}H_{7}N) are liquids present in small amounts in coal tar, and also in the liquid obtained by the distillation of bones. Most of the compounds now classified under the general name of _alkaloids_ (which see) also belong to this group. CARBOHYDRATES The term "carbohydrate" is applied to a class of compounds which includes the sugars, starch, and allied bodies These compounds contain carbon, hydrogen, and oxygen the last two elements generally being present in the proportion in which they combine to form water. The most important members of this class are the following: Cane sugar C_{12}H_{22}O_{11}. Milk sugar C_{12}H_{22}O_{11}. Dextrose C_{6}H_{12}O_{6}. Levulose C_{6}H_{12}O_{6}. Cellulose C_{6}H_{10}O_{5}. Starch C_{6}H_{10}0_{5}. ~Cane sugar~ (C_{12}H_{22}O_{11}). This is the well-known substance commonly called sugar. It occurs in many plants especially in the sugar cane and sugar beet. It was formerly obtained almost entirely from the sugar cane, but at present the greatest amount of it comes from the sugar beet. The juice from the cane or beet contains the sugar in solution along with many impurities. These impurities are removed, and the resulting solution is then evaporated until the sugar crystallizes out. The evaporation is conducted in closed vessels from which the air is partially exhausted. In this way the boiling point of the solution is lowered and the charring of the sugar is prevented. It is impossible to remove all the sugar from the solution. In preparing sugar from sugar cane the liquors left after separating as much of it as possible from the juice of the cane constitute ordinary molasses. Maple sugar is made by the evaporation of the sap obtained from a species of the maple tree. Its sweetness is due to the presence of cane sugar, other products present in the maple sap imparting the distinctive flavor. When a solution of cane sugar is heated with hydrochloric or other dilute mineral acid, two compounds, dextrose and levulose, are formed in accordance with the following equation: C_{12}H_{22}O_{11} + H_{2}O = C_{6}H_{12}O_{6} + C_{6}H_{12}O_{6}. This same change is brought about by the action of an enzyme present in the yeast plant. When yeast is added to a solution of cane sugar fermentation is set up. The cane sugar, however, does not ferment directly: the enzyme in the yeast first transforms the sugar into dextrose and levulose, and these sugars then undergo alcoholic fermentation. When heated to 160° cane sugar melts; if the temperature is increased to about 215°, a partial decomposition takes place and a brown substance known as caramel forms. This is used largely as a coloring matter. ~Milk sugar~ (C_{12}H_{22}O_{11}). This sugar is present in the milk of all mammals. The average composition of cow's milk is as follows: Water 87.17% Casein (nitrogenous matter) 3.56 Butter fat 3.64 Milk sugar 4.88 Mineral matter 0.75 When _rennin_, an enzyme obtained from the stomach of calves, is added to milk, the casein separates and is used in the manufacture of cheese. The remaining liquid contains the milk sugar which separates on evaporation; it resembles cane sugar in appearance but is not so sweet or soluble. The souring of milk is due to the fact that the milk sugar present undergoes _lactic fermentation_ in accordance with the equation C_{12}H_{22}O_{11} + H_{2}O = 4C_{3}H_{6}O_{3}. The lactic acid formed causes the separation of the casein, thus giving the well-known appearance of sour milk. ~Isomeric compounds.~ It will be observed that cane sugar and milk sugar have the same formulas. Their difference in properties is due to the different arrangement of the atoms in the molecule. Such compounds are said to be isomeric. Dextrose and levulose are also isomeric. ~Dextrose~ (_grape sugar, glucose_) (C_{6}H_{12}O_{6}). This sugar is present in many fruits and is commonly called grape sugar because of its presence in grape juice. It can be obtained by heating cane sugar with dilute acids, as explained above; also by heating starch with dilute acids, the change being as follows: C_{6}H_{10}6_{5} + H_{2}O = C_{6}H_{12}O_{6}. Pure dextrose is a white crystalline solid, readily soluble in water, and is not so sweet as cane sugar. In the presence of yeast it undergoes alcoholic fermentation. It is prepared from starch in large quantities, and being less expensive than cane sugar, is used as a substitute for it in the manufacture of jellies, jams, molasses, candy, and other sweets. The product commonly sold under the name of _glucose_ contains about 45% of dextrose. ~Levulose~ _(fruit sugar)_(C_{6}H_{12}O_{6}). This sugar is a white solid which occurs along with dextrose in fruits and honey. It undergoes alcoholic fermentation in the presence of yeast. ~Cellulose~ (C_{6}H_{10}O_{5}). This forms the basis of all woody fibers. Cotton and linen are nearly pure cellulose. It is insoluble in water, alcohol, and dilute acids. Sulphuric acid slowly converts it into dextrose. Nitric acid forms nitrates similar to nitroglycerin in composition and explosive properties. These nitrates are variously known as nitrocellulose, pyroxylin, and gun cotton. When exploded they yield only colorless gases; hence they are used especially in the manufacture of smokeless gunpowder. _Collodion_ is a solution of nitrocellulose in a mixture of alcohol and ether. _Celluloid_ is a mixture of nitrocellulose and camphor. _Paper_ consists mainly of cellulose, the finer grades being made from linen and cotton rags, and the cheaper grades from straw and wood. ~Starch~ (C_{6}H_{10}O_{5}). This is by far the most abundant carbohydrate found in nature, being present especially in seeds and tubers. In the United States it is obtained chiefly from corn, nearly 80% of which is starch. In Europe it is obtained principally from the potato. It consists of minute granules and is practically insoluble in cold water. These granules differ somewhat in appearance, according to the source of the starch, so that it is often possible to determine from what plant the starch was obtained. When heated with water the granules burst and the starch partially dissolves. Dilute acids, as well as certain enzymes, convert it into dextrose or similar sugars. When seeds germinate the starch present is converted into soluble sugars, which are used as food for the growing plant. ~Chemical changes in bread making.~ The average composition of wheat flour is as follows: Water. 13.8% Protein (nitrogenous matter) 7.9 Fats 1.4 Starch 76.4 Mineral matter 0.5 In making bread the flour is mixed with water and yeast, and the resulting dough set aside in a warm place for a few hours. The yeast first converts a portion of the starch into dextrose or a similar sugar, which then undergoes alcoholic fermentation. The carbon dioxide formed escapes through the dough, making it light and porous. The yeast plant thrives best at about 30°; hence the necessity for having the dough in a warm place. If the temperature rises above 50°, the vitality of the yeast is destroyed and fermentation ceases. In baking the bread, the heat expels the alcohol and also expands the bubbles of carbon dioxide caught in the dough, thus increasing its lightness. SOME DERIVATIVES OF BENZENE Attention has been called to the complex nature of coal tar. Among the compounds present are the hydrocarbons, benzene, toluene, naphthalene, and anthracene. These compounds are not only useful in themselves but serve for the preparation of many other important compounds known under the general name of coal-tar products. ~Nitrobenzene~ (_oil of myrbane_) (C_{6}H_{5}NO_{2}). When benzene is treated with nitric acid a reaction takes place which is expressed by the following equation: C_{6}H_{6} + HNO_{3} = C_{6}H_{5}NO_{2} + H_{2}O. The product C_{6}H_{5}NO_{2} is called nitrobenzene. It is a slightly yellowish poisonous liquid, with a characteristic odor. Its main use is in the manufacture of aniline. ~Aniline~ (C_{6}H_{5}NH_{2}). When nitrobenzene is heated with iron and hydrochloric acid the hydrogen evolved by the action of the iron upon the acid reduces the nitrobenzene in accordance with the following equation: C_{6}H_{5}NO_{2} + 6H = C_{6}H_{5}NH_{2} + 2H_{2}O. The resulting compound is known as aniline, a liquid boiling at 182°. When first prepared it is colorless, but darkens on standing. Large quantities of it are used in the manufacture of the _aniline or coal-tar dyes_, which include many important compounds. ~Carbolic acid~ (C_{6}H_{5}OH). This compound, sometimes known as _phenol_, occurs in coal tar, and is also prepared from benzene. It forms colorless crystals which are very soluble in water. It is strongly corrosive and very poisonous. ~Naphthalene and anthracene.~ These are hydrocarbons occurring along with benzene in coal tar. They are white solids, insoluble in water. The well-known _moth balls_ are made of naphthalene. Large quantities of naphthalene are used in the preparation of _indigo_, a dye formerly obtained from the indigo plant, but now largely prepared by laboratory methods. Similarly anthracene is used in the preparation of the dye _alizarin_, which was formerly obtained from the madder root. THE ALKALOIDS This term is applied to a group of compounds found in many plants and trees. They all contain nitrogen, and most of them are characterized by their power to combine with acids to form salts. This property is indicated by the name alkaloids, which signifies alkali-like. The salts are soluble in water, and on this account are more largely used than the free alkaloids, which are insoluble in water. Many of the alkaloids are used in medicine, some of the more important ones being given below. ~Quinine.~ This alkaloid occurs along with a number of others in the bark of certain trees which grow in districts in South America and also in Java and other tropical islands. It is a white solid, and its sulphate is used in medicine in the treatment of fevers. ~Morphine.~ When incisions are made in the unripe capsules of one of the varieties of the poppy plant, a milky juice exudes which soon thickens. This is removed and partially dried. The resulting substance is the ordinary _opium_ which contains a number of alkaloids, the principal one being morphine. This alkaloid is a white solid and is of great service in medicine. Among the other alkaloids may be mentioned the following: _Nicotine_, a very poisonous liquid, the salts of which occur in the leaves of the tobacco plant; _cocaine_, a crystalline solid present in coca leaves and used in medicine as a local anæsthetic; _atropine_, a solid present in the berry of the deadly nightshade, and used in the treatment of diseases of the eye; _strychnine_, a white, intensely poisonous solid present in the seeds of the members of the _Strychnos_ family. INDEX Acetaldehyde 405 Acetic acid 406 Acetone 411 Acetylene 203 series 399 Acids 106 binary 113 characteristics 106 definition 107 dibasic 159 familiar 106 monobasic 159 nomenclature 113 organic 405 preparation 141 strength 111 ternary 113 undissociated 107 Acker furnace, 279 Agate 260 Air 83 a mechanical mixture 89 carbon dioxide in 87 changes in composition 87 liquid 91 nitrogen in 87 oxygen in 85 poisonous effects of exhaled 88 properties 90 quantitative analysis of 85 regarded as an element 83 standard for density 229 water vapor in 87 Alabaster 308 Alchemists 9 Alchemy 9 Alcohol, common 402 denatured 404 ethyl 402 methyl 402 wood 402 Alcohols 401 Aldehydes 405 Alizarin 418 Alkali 107, 274 family 274 Alkaline-earth family 300 Alkaloids 418 Allotropic forms 22 Alloys 252 Alum 333 ammonium 334 ammonium chrome 384 ammonium iron 352 baking powders 335 potassium 333 potassium chrome 384 potassium iron 352 Aluminates 332 Aluminium 327 bronze 330, 359 chloride 333 family 327 hydroxide 332 metallurgy 328 occurrence 327 oxide 331 preparation 328 properties 329 silicates 335 uses 330 Amalgam 362 Amethyst 260, 331 Ammonia 123 composition 127 preparation 123 properties 124 uses 125 Ammonium 126 acid carbonate 295 carbonate 295 chloride 294 compounds 294 Ammonium hydrosulphide 296 hydroxide 126 molybdate 388 oxalate 407 sulphate 295 sulphide 295 sulphide, yellow 296 Analysis 40 Anhydride 135 carbonic 206 chromic 387 nitric 135 nitrous 135 phosphoric 243 sulphuric 153 Anhydrite 288 Aniline 417 Anion 106 Anode 99 Anthracene 418 Antimony 250 acids 251 alloys 253 chloride 252 metallic properties 252 occurrence 251 oxides 251 preparation 251 properties 251 sulphides 251 Apatite 175, 239, 311 Aqua ammonia 124 Aqua regia 185 Aqueous tension 25 Argon 80 Arsenic 246 acids 250 antidote 250 Marsh's test 248 occurrence 246 oxides 249 preparation 246 properties 247 sulphides 250 white 249 Arsenopyrites 246 Arsine 247 Asbestos 321, 336 Atmosphere 83 constituents 83 function of constituents 84 Atomic hypothesis 61 theory 59 and laws of matter 63 and radium 314 weights, 65 accurate determination 231 and general properties 167 and specific heats 233 calculation of 231 Dalton's method 223 direct determination 233 from molecular weights 230 relation to equivalent 224 standard for 66 steps in determining 224 Atoms 62 size 65 Atropine 419 Aurates 396 Avogadro's hypothesis 226 and chemical calculations 235 and molecular weights 227 Azote 78 Azurite 357 Babbitt metal 253 Bacteria 85 decomposition of organic matter by 122 nitrifying 85 Baking powders 285, 408 alum 335 soda 285 Barium 312 chloride 313 nitrate 313 oxides 312 sulphate 313 Barytes 312 Bases 107 characteristics 107 definition 108 familiar 107 nomenclature 113 organic 412 strength 113 undissociated 108 Basic lining process 346 Bauxite 332 Beer 404 Benzene 417 derivatives 417 series 399 Benzine 400 Bessemer process 345 Bismuth 253 basic salts 255 chloride 253 nitrate 253 occurrence 253 oxides 254 preparation 253 salts, hydrolysis of 254 subnitrate 256 uses 253 Bismuthyl chloride 256 Blast furnace 341 lamp 38 Bleaching powder 306 Bleaching by chlorine 181 by sulphurous acid 152 Boiler scale 320 Bone ash 311 Bone black 200 Borax 265 bead 266 Bornite 357 Boron 257, 264 acids 265 fluoride 264 hydride 264 occurrence 264 oxides 264 preparation 264 properties 264 Brass 323 Bread making 416 Bromides 190 Bromine 187 occurrence 187 oxygen compounds 190 preparation 187 properties 188 Bronze 359 aluminium 330, 359 Butter fat 410 Butyric acid 407 By-product 284 Cadmium 325 compounds 326 Cæsium 294 Calamine 321 Calcite 305 Calcium 301 carbide 203, 310 carbonate 305 chloride 306 fluoride 308 hydroxide 303 occurrence 301 oxide 302 phosphate 246, 311 preparation 302 sulphate 308 Calomel 363 Calorie 76 Caramel 414 Carbohydrates 413 Carbolic acid 417 Carbon 196 allotropic forms 196 amorphous 198 compounds 196 crystalline forms 197 cycle in nature 88 dioxide 204 and bases 206 and plant life 88 in air 87 occurrence 204 preparation 204 properties 204 solid 204 disulphide 160, 210 family 196 hydrogen compounds 201 monoxide 208 occurrence 196 oxides 203 properties 200 pure 198 retort 199 uses 200 Carbonates 207 acid 207 Carbonic acid 206 Carborundum 259 Carnallite 288 Casein 414 Cassiterite 370 Catalysis 153 Catalyzers 153 Cathode 99 Cation 106 Caustic potash 288 soda 278 Celestite 312 Celluloid 415 Cellulose 415 Cement 304 Ceramic industries 336 Cerium 377 Chalcedony 260 Chalcocite 357 Chalcopyrite 357 Chalk 305 Chamber acid 157 Changes, physical and chemical 2 Charcoal 199 Chemical affinity 12 changes 2 compounds 7 equilibrium 128 properties 3 Chemistry, definition 4 Chili saltpeter 191, 285 Chinaware 336 Chloric acid 187 Chlorides 186 Chlorine 177 bleaching action 181 chemical properties 180 family 174 historical 177 occurrence 178 oxides 187 oxygen acids 187 preparation 178 properties 179 Chloroform 401 Chloroplatinic acid 393 Chlorous acid 187 Chromates 385 Chrome alum 384 Chromic acid 388 anhydride 387 chloride 383 hydroxide 383 sulphate 384 sulphide 384 Chromite 383 Chromium 383 a base-forming element 383 an acid-forming element 385 occurrence 383 Cinnabar 363 Citric acid 408 Clay 336 Coal 199 gas 217 products 400 tar 218 Cobalt 354 compounds 354 Cocaine 419 Coke 199 Collodion 415 Colemanite 265 Combining weights 225 Combustion 17 broad sense 20 in air 19 phlogiston theory 19 products 18 spontaneous 20 supporters 213 Compounds, chemical 7 isomeric 414 of metals, preparation 265 structure of 118 Conservation of energy 4 of matter 5 Contact process 154 Converter, Bessemer 345 Copper 357 acetate 407 alloys of 359 family 356 hydroxide 360 metallurgy 357 occurrence 357 ores 357 oxide 360 properties 358 refining 358 sulphate 361 sulphide 361 uses 359 Copperas 350 Coral 305 Corrosive sublimate 363 Corundum 331 Cream of tartar 408 Crocoisite 383 Cryolite 175, 328 Crystallization 98 water of 54, 75 Crystallography 161 Crystals 161 axes of 161 systems 162 Cupric compounds 360 Cuprite 360 Cuprous compounds 360 chloride 360 oxide 360 Cyanides 210 solutions are alkaline 210 Dalton's atomic hypothesis 61 Decay 21 Decomposition of organic matter 122 Decrepitation 55 Deliquescence 55 Density of gases 230 Desiccating agents 55 Developers 367 Dewar bulb 91 Dextrose 414 Diamond 197 Dichromates 385 Dichromic acid 385 Dimorphous substances 163 Dissociation 99 and boiling point 101 and freezing point 101 equations of 112 extent of 113 Distillation 50 Dogtooth spar 306 Dolomite 319 Double decomposition 71 Drummond light 38 Dyeing 333 Dynamite 409 Earth metals 327 Efflorescence 54 Electric furnace 221 Electro-chemical industries 269 Electrode 99 Electrolysis 99 of sodium chloride 102 of sodium sulphate 103 of water 41, 102 Electrolytes 99 Electrolytic dissociation 99 Electroplating 366 Electrotyping 359 Elements, definition 8 atomic weights 232 earlier classification 165 names 11 natural groups 165 number of 9 occurrence 10 periodic division 166 physical state 10 symbols of 11 Emery 331 Energy 4 and plant life 89 chemical 5 conservation of 4 transformation of 5 Enzyme 405 Epsom salts 320 Equations 68 are quantitative 72 knowledge requisite for 69 not algebraic 74 reading of 69 Equilibrium 138 chemical 138 in solution 139 point of 138 Equivalent 224 determination of 224 elements with more than one 225 relation to atomic weight 224 Etching 177 Ether 411 Ethereal salts 409 Ethers 411 Ethylamine 412 Ethylene series 399 Eudiometer 43 Evaporation 11 Families in periodic groups 170 triads 165 Family resemblances 170 Fats 409 Fatty acid series 405 Feldspar 261, 335 Fermentation 404 acetic 406 alcoholic 404, 405 lactic 414 Ferric chloride 352 hydroxide 352 salts 351 reduction 353 sulphate 352 Ferrochromium, 383 Ferromanganese 343 Ferrosilicon 259 Ferrous carbonate 351 salts 350 oxidation of 353 sulphate 350 sulphide 350 Fertilizers 245 Filtration 6, 51 beds 52 Fire damp 202 Flames 213 appearance 214 blowpipe 216 Bunsen 214 conditions for 213 hydrogen 34 luminosity 216 oxidizing 214 oxyhydrogen 37 reactions 296 reducing 214 structure 214 Flash lights 317 Flint 260 Fluorides 177 Fluorine 175 Fluorspar 175, 308 Fluosilicic acid 259 Flux 340 Fool's gold 351 Formaldehyde 405 Formalin 405 Formic acid 406 Formulas 68 how determined 234 structural 119 Fractional distillation 51 Franklinite 321 Fuels 220 Furnace, arc 221 electric 221 resistance 221 Fusion methods 271 Galena 373 Gallium 327 Galvanized iron 323 Gas, collection of 15 coal 217 fuel 217 illuminating 217 measurement of 23 natural 219 purification of 218 water 219 Gases, table 220 Gasoline 400 German silver 323, 359 Germanium 370 Germs, effect of cold on 53 in air 84 in water 52 Glass 262 coloring of 263 etching of 177 molding of 263 nature of 263 varieties 263 Glauber's salt 281 Glazing 336 Glucose 414 Glycerin 405 nitrates of 409 Gold 393 alloys 396 chloride 396 coin 359 extraction of 394 in copper 358 mining 394 occurrence 393 properties 396 refining of 395 telluride 394 Goldschmidt method 269, 330 Gram-molecular weight 236 Granite 336 Graphite 198 Gun cotton 415 metal 359 powder 292 Gypsite 308 Gypsum 308 Halogens 174 Hard water 309 Heat of reaction 75 Helium 80, 314 Hematite 339, 349 Homologous series 398 Hydriodic acid 193 Hydrobromic acid 189 Hydrocarbons 201, 398 properties 400 series 398 substitution products 401 Hydrochloric acid 182 composition 183 oxidation of 185 preparation 182 properties 184 salts 186 Hydrocyanic acid 210 Hydrofluoric acid 176 etching by 177 salts of 177 Hydrogen 28 dioxide 56 explosive with oxygen 35 occurrence 28 preparation from acids 30 preparation from water 28 properties 32 standard for atomic weights 66 standard for molecular weights 227 sulphide 146 uses 38 Hydrolysis 254 conditions affecting 255 partial 255 Hydrosulphuric acid 146 Hydroxyl radical 112 Hypochlorous acid 187 Hypothesis 61 Avogadro's 226 Dalton's 61 Ice manufacture 125 Iceland spar 305 Indigo 418 Indium 327 Insoluble compounds 272 Iodic acid 194 Iodides 193 Iodine 190 oxygen compounds 193 preparation 191 properties 192 tincture 192 Iodoform 192, 401 Ions 100 and electrolytes 104 Iridium 393 Iron 339 alum 352 cast 343 compounds 349 cyanides 352 disulphide 351 family 338 metallurgy 339 occurrence 339 ores 339 oxides 349 pure 348 varieties 342, 347 wrought 343 Jasper 260 Kainite 288 Kaolin 261, 335 Kerosene 400 Ketones 411 Kieserite 288 Kindling temperature 17 Krypton 80 Lactic acid 408 Lampblack 200 Laughing gas 132 Law, definition 61 of Boyle 24 of Charles 23 of combining volumes 194 of conservation of energy 4 of conservation of matter 5, 59 of definite composition 59 of Dulong and Petit 233 of Gay-Lussac 194 of multiple proportion 60 of Raoult 233 periodic 169 Lead 373 acetate 375, 407 alloys 375 basic carbonate 376 carbonate 376 chloride 377 chromate 377 insoluble compounds 376 metallurgy 373 nitrate 375 occurrence 373 oxides 375 peroxide 375 properties 374 red 375 soluble salts 375 sugar of 375 sulphate 377 sulphide 377 white 376 Le Blanc soda process 282 Levulose 415 Lime 302 air-slaked 303 hypochlorite 307 kilns 303 slaked 303 Lime light 38 Limestone 305 Limewater 303 Limonite 339 Litharge 375 Lithium 294 Luminosity of flames 216 Lunar caustic 366 Magnesia 318 alba 319 usta 318 Magnesite 318 Magnesium 317 basic carbonate 319 carbonate 318 cement 318 chloride 319 family 316 hydroxide 318 oxide 318 silicates 321 sulphate 320 Magnetite 339, 349 Malachite 357 Manganates 381 Manganese 379 a base-forming element 380 an acid-forming element 381 in glass 263 occurrence 379 oxides 380 Manganic acid 381 Manganous salts 380 Marble 305 Marl 305 Marsh gas 202 Matches 242 Matte 358 Matter, classification 6 conservation 5 definition 5 kinds 9 Measurement of gases 23 Mechanical mixtures 6 Meerschaum 321, 336 Mercuric chloride 363 iodide 364 oxide 14, 362 sulphide 363 Mercurous chloride 363 Mercury 361 iodides 364 metallurgy 361 occurrence 361 oxides 362 uses 362 Metaboric acid 265 Metallurgy 268 Metals 165, 267 action on salts 271 definition 267 extraction 268 occurrence 267 preparation of compounds 269 reduction from ores 268 Metaphosphoric acid 245 Metarsenic acid 250 Metasilicic acid 261 Metastannic acid 371 Methane 202, 399 Methylamine 412 Mexican onyx 305 Mica 261, 336 Microcosmic salt 244 Milk 414 Minerals 267 Minium 375 Mixed salts 244 Molasses 413 Molecular weights 226 boiling-point method 233 compared with oxygen 228 determination 226 freezing-point method 233 oxygen standard 227 of elements 232 vapor-density method 229 Molecule 62 Molybdenum 388 Molybdic acid 388 Monazite sand 377 Mordants 333 Morphine 418 Mortar 304 Moth balls 418 Muriatic acid 182 Naphthalene 418 Naphthas 400 Nascent state 182 Natural gas 219 sciences 1 Neon 80 Neutralization 108 a definite act 109 definition 109 heat of 109 partial 111 Niagara Falls 269, 329 Nickel 354 coin 359 compounds 354 plating 354 Nicotine 419 Nitrates 131 Nitric acid, 128 action on metals 130 decomposition 129 oxidizing action 130 preparation 128, 140 properties 129 salts 131 Nitric oxide 133 Nitrites 132 Nitrobenzene 417 Nitrocellulose 415 Nitrogen 78 compounds 122 in air 87 occurrence 78, 122 oxides 132 preparation 78 properties 80 Nitroglycerin 409 Nitrosulphuric acid 155 Nitrous acid 132 oxide 132 Non-metals 165 Oil of myrbane 417 of vitriol 154 Oleic acid 408 Olein 409 Oleomargarine 410 Onyx 260 Opal 260 Open-hearth process 346 Opium 418 Ores 267 Organic bases 412 chemistry 201, 397 matter, decomposition 122 Orpiment 246 Orthoarsenic acid 250 Orthophosphates 244 Orthophosphoric acid 244 Orthosilicic acid 261 Osmic acid 393 Osmium 393 tetroxide 393 Oxalic acid 407 Oxidation 17, 353 definition 18 Oxidizing agent 37 Oxygen 13 and ozone 22 commercial preparation 16 history 13 importance 21 in air estimation, 85 in air function, 84 occurrence 13 preparation 13 properties 16 standard for atomic weights 66 two atoms in molecule 227 Oxyhydrogen blowpipe 37 Ozone 21, 137 Palladium 390 Palmitic acid 407 Palmitin 409 Paraffin 400 Paris green 250 Parkes's method for silver 364 Pearls 305 Perchloric acid 187 Periodic acid 194 Periodic division 166 groups 167 law 169 law, imperfections 172 law, value 171 table 168 table, arrangement 166 Permanent hardness 310 Permanganates 381 Permanganic acid 381 Peroxides 278 Petroleum 399 Pewter 372 Phenol 417 Philosopher's stone 9 Phlogiston 19 Phosphates 245 Phosphine 242 Phosphonium compounds 243 Phosphoric acid 244 Phosphorite 239 Phosphorous acid 244 Phosphorus 239 acids 243 family 238 hydrogen compounds 242 occurrence 239 oxides 243 preparation 239 properties 240 red 241 yellow 240 Photography 367 Physical changes 2 properties 3 properties and periodic groups 171 state 3 Physics 1, 4 Pitchblende 314 Plaster of Paris 308 Platinic chloride 393 Platinized asbestos 391 Platinous chloride 393 Platinum 391 a catalytic agent 152, 392 Pneumatic trough 16 Polyboric acid 265 Polyhalite 288 Polysilicic acids 261 Porcelain 336 Portland cement 304 Potash 293 Potassium 287 acid carbonate 294 acid sulphate 294 acid sulphite 294 alum, aluminium 334 alum, chrome 384 alum, iron 352 and plant life 287 aurate 396 bromide 290 carbonate 293 chlorate 291 chloride 290 chromate 385 cyanide 293 dichromate 386 ferricyanide 352 ferrocyanide 352 hydroxide 288 hydroxide, action of halogens 289 hypochlorite 289 iodide 290 manganate 381 nitrate 291 occurrence 287 permanganate 381 preparation 288 sulphate 294 Precipitated chalk 306 Precipitation 140 Properties, chemical 3 physical 3 Prussic acid 210 Puddling 343 furnace 344 Pyridine 412 Pyrites 351 Pyrolusite 380 Pyrophosphoric acid 245 Quantitative equations 72 Quartz 260 Quicklime 302 Quinine 418 Quinoline 412 Radical 112 Radium 313 Reaction, classes 70 addition 70 completed 139 heat of 75 of decomposition 70 of double decomposition 71 of substitution 70 reversible 137 steps in 131 Realgar 246 Red lead 375 phosphorus 241 Reducing agent 37 Reduction 36, 354 Rennin 414 Resemblances, family 170 Respiration 87 Rhodium 390 Rochelle salts 408 Rouge 349 Rubidium 294 Ruby 331 Ruthenium 390 Rutile 264 Safety lamp 202 Sal ammoniac 294 soda 282 Salt 280 Saltpeter 291 Chili 285 Salts, 109 acid, 112 Salts basic 111 binary 114 characteristics 109 definition 109 insoluble 272 mixed 244 nomenclature 113 normal 112 preparation by precipitation 270 Sand 260 Sandstone 260 Saponification 410 Sapphire 331 Satinspar 308 Scale 320 Schönite 288 Selenite 308 Selenium 161 Serpentine 320, 336 Shot 247, 375 Siderite 339 Silica 260 Silicates 261 Silicic acids 261 Silicides 259 Silicon 258 acids 261 dioxide 260 fluoride 258 hydride 258 Silver 364 amalgamation process 364 bromide 367 chloride 367 coin 359 German 359 in copper ores 358 iodide 367 metallurgy 364 nitrate 366 oxide 366 parting of 365 refining 365 sulphide 366 Slag 340 Smalt 355 Smithsonite 321 Smokeless powder 293 Soaps 410 Soda ash 284 Soda lime 202 Sodium 276 acetate 407 bicarbonate 285 carbonate 282 carbonate, historical 284 chloride 280 chromates 386 hydrogen carbonate 285 hydroxide 278 hyposulphite 282 iodate 191 nitrate 285 occurrence 276 peroxide 277 phosphates 286 preparation 276 properties 277 sulphate 281 sulphite 281 tetraborate 287 thiosulphate 282 Solder 372, 375 Solubility of gases 95 of solids 96 Solution 94 and chemical action 53 boiling point 98 classes 94 distribution of solids in 98 electrolysis of 99 freezing point 99 of gases in liquids 94 of solids in liquids 96 properties 98 saturated 97 supersaturated 98 Solvay soda process 283 Sombrerite 239 Spectroscope 296 Sphalerite 325 Spiegel iron 343 Spinel 332 Spontaneous combustion 20 Stalactites 305 Stalagmites 305 Standard conditions 23 Stannates 372 Stannic acid 372 chloride 372 oxide 372 Stannous chloride 372 Starch 415 Stassfurt salts 287 Stearic acid 407 Stearin 409 Steel 345 alloys 348 properties 347 tempering of 348 tool 347 Stibine 251 Stibnite 250 Stoneware 336 Strontianite 312 Strontium 312 hydroxide 312 nitrate 312 Structural formulas 119 Structure of compounds 119 Strychnine 419 Substitution 70 Sugars 412 cane 412 fruit 415 grape 414 milk 414 Sulphates 159 Sulphides 148 Sulphites 152 action of acids on 150 Sulphur 143 allotropic forms 144 chemical properties 145 comparison with oxygen 161 dioxide 149 preparation 149 properties 150 extraction 143 flowers of 143 occurrence 143 oxides 149 physical properties 144 trioxide 152 uses 146 varieties 144 Sulphuric acid 154 action as an acid 157 action on metals 157 action on organic matter 158 action on salts 158 action on water 158 fuming 155 manufacture 154 oxidizing action 157 plant 156 properties 157 salts 159 Sulphuric anhydride 153 Sulphurous acid 151 Superphosphate of lime 246 Sylvine 288 Symbols 11 Synthesis 40 Table, alkali metals 274 alkaline-earth metals 300 alloys of copper 359 aqueous tension Appendix B atomic weights Appendix A chlorine family 174 composition of earth's crust 10 composition of fuel gases 220 constants of elements Appendix B copper family 356 elements Appendix A gold and platinum metals 390 hydrocarbons 399 magnesium family 316 manganese and chromium 379 periodic arrangement 168 phosphorus family 238 silicon family 257 solubility of gases in water 95 solubility of salts 96 solubility of salts at different temperatures 97 tin and lead 370 weights of gases Appendix B Talc 321, 336 Tartar emetic 408 Tartaric acid 408 Tellurium 161 Temporary hardness 309 Ternary acids 113 salts 114 Tetraboric acid 265 Thallium 327 Theory, atomic 61 definition 64 value of 64 Thermite 331 Thio compounds 282 Thiosulphates 159 Thiosulphuric acid 159 Thorium 377 Tin 370 block 371 compounds 372 crystals 372 family 370 foil 371 metallurgy 370 plate 371 properties 371 uses 371 Titanium 257, 264 Topaz 331 Triad families 166 Tungsten 388 Type metal 253, 375 Uranium 388 Valence 116 a numerical property 116 and combining ratios 118 and equations 120 and formulas 120 and periodic groups 162 and structure 118 definition 116 indirectly determined 117 measure of 117 variable 117 Vaseline 400 Venetian red 349 Verdigris 407 Vermilion 363 Vinegar 406 Vitriol, blue 361 green 350 oil of 154 white 324 Volume and aqueous tension 25 and pressure 24 and temperature 23 of combining gases 194 Water 40 a compound 40 and disease 49 catalytic action of 154 chalybeate 351 chemical properties 53 composition 47 composition by volume 44 composition by weight 47 dissociation of 210 distillation of 50 electrolysis of 41, 103 filtration of 51 gas 219 hard 309 historical 40 impurities in 48 in air 87 mineral 49 occurrence 48 of crystallization 54, 75 physical properties 53 purification of 50 qualitative analysis 41 quantitative analysis 42 river 49 sanitary analysis 50 self-purification 53 softening of 310 standard substance 55 synthesis 43 uses of 55 Weights, atomic 65 Welsbach mantles 219, 377 Whisky 404 Wine 404 Witherite 312 Wood alcohol 402 distillation 402 Wood's metal 254 Xenon 80 Yeast 403 Zinc 321 alloys of 323 blende 321 chloride 325 flowers of 322 metallurgy 321 occurrence 321 oxide 324 sulphate 324 sulphide 325 white 324 Zymase, 403 ANNOUNCEMENTS AN ELEMENTARY STUDY OF CHEMISTRY By WILLIAM McPHERSON, Professor of Chemistry in Ohio State University, and WILLIAM E. HENDERSON, Associate Professor of Chemistry in Ohio State University. 12mo. Cloth. 434 pages. Illustrated. List price, $1.25; mailing price, $1.40 This book is the outgrowth of many years of experience in the teaching of elementary chemistry. In its preparation the authors have steadfastly kept in mind the limitations of the student to whom chemistry is a new science. They have endeavored to present the subject in a clear, well-graded way, passing in a natural and logical manner from principles which are readily understood to those which are more difficult to grasp. The language is simple and as free as possible from unusual and technical phrases. Those which are unavoidable are carefully defined. The outline is made very plain, and the paragraphing is designed to be of real assistance to the student in his reading. The book is in no way radical, either in the subject-matter selected or in the method of treatment. At the same time it is in thorough harmony with the most recent developments in chemistry, both in respect to theory and discovery. Great care has been taken in the theoretical portions to make the treatment simple and well within the reach of the ability of an elementary student. The most recent discoveries have been touched upon where they come within the scope of an elementary text. Especial attention has been given to the practical applications of chemistry, and to the description of the manufacturing processes in use at the present time. EXERCISES IN CHEMISTRY. By WILLIAM McPHERSON and WILLIAM E. HENDERSON. (_In press._) GINN & COMPANY PUBLISHERS A FIRST COURSE IN PHYSICS By ROBERT A. MILLIKAN, Associate Professor of Physics, and HENRY G. GALE, Assistant Professor of Physics in The University of Chicago 12mo, cloth, 488 pages, illustrated, $1.25 A LABORATORY COURSE IN PHYSICS _FOR SECONDARY SCHOOLS_ By ROBERT A. MILLIKAN and HENRY G. GALE 12mo, flexible cloth, 134 pages, illustrated, 40 cents This one-year course in physics has grown out of the experience of the authors in developing the work in physics at the School of Education of The University of Chicago, and in dealing with the physics instruction in affiliated high schools and academies. The book is a simple, objective presentation of the subject as opposed to a formal and mathematical one. It is intended for the third-year high-school pupils and is therefore adapted in style and method of treatment to the needs of students between the ages of fifteen and eighteen. It especially emphasizes the historical and practical aspects of the subject and connects the study very intimately with facts of daily observation and experience. The authors have made a careful distinction between the class of experiments which are essentially laboratory problems and those which belong more properly to the classroom and the lecture table. The former are grouped into a Laboratory Manual which is designed for use in connection with the text. The two books are not, however, organically connected, each being complete in itself. All the experiments included in the work have been carefully chosen with reference to their usefulness as effective classroom demonstrations. GINN AND COMPANY PUBLISHERS APPENDIX A LIST OF THE ELEMENTS, THEIR SYMBOLS, AND ATOMIC WEIGHTS The more important elements are marked with an asterisk O = 16 *Antimony Sb 120.2 *Argon A 39.9 *Arsenic As 75.0 *Barium Ba 137.4 Beryllium Be 9.1 *Bismuth Bi 208.5 *Boron B 11.0 *Bromine Br 79.96 *Cadmium Cd 112.4 Cæsium Cs 132.9 *Calcium Ca 40.1 *Carbon C 12.00 Cerium Ce 140.25 *Chlorine Cl 35.45 *Chromium Cr 52.1 *Cobalt Co 59.0 Columbium Cb 94.0 *Copper Cu 63.6 Erbium Er 166.0 *Fluorine F 19.0 Gadolinium Gd 156.0 Gallium Ga 70.0 Germanium Ge 72.5 *Gold Au 197.2 Helium He 4.0 *Hydrogen H 1.008 Indium In 115.0 *Iodine I 126.97 Iridium Ir 193.0 *Iron Fe 55.9 Krypton Kr 81.8 Lanthanum La 138.9 *Lead Pb 206.9 Lithium Li 7.03 *Magnesium Mg 24.36 *Manganese Mn 55.0 *Mercury Hg 200.0 Molybdenum Mo 96.0 Neodymium Nd 143.6 Neon Ne 20.0 *Nickel Ni 58.7 *Nitrogen N 14.04 Osmium Os 191.0 *Oxygen O 16.00 Palladium Pd 106.5 *Phosphorus P 31.0 *Platinum Pt 194.8 *Potassium K 39.15 Praseodymium Pr 140.5 Radium Ra 225.0 Rhodium Rh 103.0 Rubidium Rb 85.5 Ruthenium Ru 101.7 Samarium Sm 150.3 Scandium Sc 44.1 Selenium Se 79.2 *Silicon Si 28.4 *Silver Ag 107.93 *Sodium Na 23.05 *Strontium Sr 87.6 *Sulphur S 32.06 Tantalum Ta 183.0 Tellurium Te 127.6 Terbium Tb 160.0 Thallium Tl 204.1 Thorium Th 232.5 Thulium Tm 171.0 *Tin Sn 119.0 Titanium Ti 48.1 Tungsten W 184.0 Uranium U 238.5 Vanadium V 51.2 Xenon Xe 128.0 Ytterbium Yb 173.0 Yttrium Yt 89.0 *Zinc Zn 65.4 Zirconium Zr 90.6 APPENDIX B Tension of Aqueous Vapor expressed in Millimeters of Mercury TEMPERATURE PRESSURE 16 13.5 17 14.4 18 15.3 19 16.3 20 17.4 21 18.5 22 19.6 23 20.9 24 22.2 25 23.5 Weight of 1 Liter of Various Gases measured under Standard Conditions Acetylene 1.1614 Air 1.2923 Ammonia 0.7617 Carbon dioxide 1.9641 Carbon monoxide 1.2499 Chlorine 3.1650 Hydrocyanic acid 1.2036 Hydrochloric acid 1.6275 Hydrogen 0.08984 Hydrosulphuric acid 1.5211 Methane 0.7157 Nitric oxide 1.3410 Nitrogen 1.2501 Nitrous oxide 1.9677 Oxygen 1.4285 Sulphur dioxide 2.8596 Densities and Melting Points of Some Common Elements DENSITY MELTING POINT Aluminium 2.68 640 Antimony 6.70 432 Arsenic 5.73 -- Barium 3.75 -- Bismuth 9.80 270 Boron 2.45 -- Cadmium 8.67 320 Cæsium 1.88 26.5 Calcium 1.54 -- Carbon, Diamond 3.50 -- " Graphite 2.15 -- " Charcoal 1.80 -- Chromium 7.30 3000 Cobalt 8.55 1800 Copper 8.89 1084 Gold 19.30 1064 Iridium 22.42 1950 Iron 7.93 1800 Lead 11.38 327 Lithium 0.59 186 Magnesium 1.75 750 Manganese 8.01 1900 Mercury 13.596 -39.5 Nickel 8.9 1600 Osmium 22.47 -- Palladium 11.80 1500 Phosphorus 1.80 45 Platinum 21.50 1779 Potassium 0.87 62.5 Rhodium 12.10 -- Rubidium 1.52 38.5 Ruthenium 12.26 -- Silicon 2.35 -- Silver 10.5 960 Sodium 0.97 97.6 Strontium 2.50 -- Sulphur 2.00 114.8 Tin 7.35 235 Titanium 3.50 -- Zinc 7.00 420 
33466	----	THE SOCIAL GANGSTER THE CRAIG KENNEDY SERIES BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER HARPER & BROTHERS PUBLISHERS NEW YORK AND LONDON Copyright, 1916, by HARPER & BROTHERS Printed in the United States of America [Illustration: JUST BEFORE WE WERE OFF A TELEGRAM CAME TO HER, WHICH SHE READ AND HASTILY STUFFED INTO A POCKET OF HER RIDING HABIT] CONTENTS I. THE SOCIAL GANGSTER II. THE CABARET ROUGE III. THE FOX HUNT IV. THE TANGO THIEF V. THE "THÉ DANSANT" VI. THE SERUM DIAGNOSIS VII. THE DIAMOND QUEEN VIII. THE ANESTHETIC VAPORIZER IX. THE TWILIGHT SLEEP X. THE SIXTH SENSE XI. THE INFERNAL MACHINES XII. THE SUBMARINE BELL XIII. THE SUPER-TOXIN XIV. THE SECRET AGENTS XV. THE GERM OF ANTHRAX XVI. THE SLEEPMAKER XVII. THE INTER-URBAN HANDICAP XVIII. THE TOXIN OF FATIGUE XIX. THE X-RAY DETECTIVE XX. THE MECHANICAL CONNOISSEUR XXI. THE RADIOGRAPH WITNESS XXII. THE ABSOLUTE ZERO XXIII. THE VACUUM BOTTLE XXIV. THE SOLAR PLEXUS XXV. THE DEMON ENGINE XXVI. THE ELECTROLYSIS CLEW XXVII. THE PERPETUAL MOTION MACHINE XXVIII. THE CANCER HOUSE XXIX. THE QUACK DOCTORS XXX. THE FILTERABLE VIRUS XXXI. THE VOODOO MYSTERY XXXII. THE FLUORISCINE TEST XXXIII. THE RESPIRATION CALORIMETER XXXIV. THE EVIL EYE XXXV. THE BURIED TREASURE XXXVI. THE WEED OF MADNESS THE SOCIAL GANGSTER CHAPTER I THE SOCIAL GANGSTER "I'm so worried over Gloria, Professor Kennedy, that I hardly know what I'm doing." Mrs. Bradford Brackett was one of those stunning women of baffling age of whom there seem to be so many nowadays. One would scarcely have believed that she could be old enough to have a daughter who would worry her very much. Her voice trembled and almost broke as she proceeded with her story, and, looking closer, I saw that, at least now, her face showed marks of anxiety that told on her more than would have been the case some years before. At the mention of the name of Gloria Brackett, I saw that Craig was extremely interested, though he did not betray it to Mrs. Brackett. Already, with my nose for news I had scented a much bigger story than any that had been printed. For the Bracketts had lately been more or less in the news of the day. Choking back a little suppressed sob in her throat, Mrs. Brackett took from a delicate gold mesh bag and laid on the desk before Kennedy a small clipping from the "Lost and Found" advertisements in the _Star_. It read: "REWARD of $10,000 and absolutely no questions asked for the return of a diamond necklace of seventy-one stones which disappeared from a house at Willys Hills, Long Island, last Saturday or Sunday. "LA RUE & CO., Jewelers, "---- Fifth Avenue." I recognized the advertisement as one that had occasioned a great deal of comment on the _Star_, due to its peculiar nature. It had been a great mystery, perhaps much more so than if the advertisement had been worded and signed in the usual way. I knew also that the advertisement had created a great furore of excitement and gossip at the fashionable North Shore Hunt Club of which Bradford Brackett was Master of Fox Hounds. "At first," explained Mrs. Brackett nervously, "La Rue & Co. were able to keep the secret. They even refused to let the police take up the case. But as public interest in the advertisement increased at last the secret leaked out--at least that part of it which connected our name with the loss. That, however, seemed only to whet curiosity. It left everybody wondering what was back of it all. That's what we've been trying to avoid--that sort of publicity." She paused a moment, but Kennedy said nothing, evidently thinking that the best safety valve for her overwrought feelings would be to let her tell her story in her own way. "Why, you know," she resumed rapidly, to hide her agitation, "the most ridiculous things have been said. Some people have even said that we lost nothing at all, that it was all a clever attempt at notoriety, to get our names in the papers. Some have said it was a plan to collect the burglary insurance. But we are wealthy. They didn't stop to think how inconceivable that was. We have nothing to lose, even if the necklace is never heard of again." For the moment her indignation had got the better of her worry. Most opinions, I recalled, had been finally that the disappearance was mixed up with some family affairs. At any rate, here was to be the real story at last. I dissembled my interest. Mrs. Brackett's indignation was quickly succeeded by the more poignant feelings that had brought her to Kennedy. "You see," she continued, now almost sobbing, "it is really all, I fear, my own fault. I didn't realize that Gloria was growing so fast and so far out of my life. I've let her be brought up by governesses and servants. I've sent her to the best schools I could find. I thought it was all right. But now, too late, I realize that it is all wrong. I haven't kept close enough to her." She was rattling on in this disjointed manner, getting more and more excited, but still Kennedy made no effort to lead the conversation. "I didn't think Gloria was more than a child. But--why, Mr. Kennedy, she's been going, I find, to these afternoon dances in the city and out at a place not far from Willys Hills." "What sort of places?" prompted Kennedy. "The Cabaret Rouge," answered Mrs. Brackett, flashing at us a look of defiance that really masked fear of public opinion. I knew of the place. It had an extremely unsavory reputation. In fact there were two places of the same name, one in the city and the other out on Long Island. Mrs. Brackett must have seen Kennedy and me exchange a look askance at the name. "Oh, it's not a question of morals, alone," she hastened. "After all, sometimes common sense and foolishness are fair equivalents for right and wrong." Kennedy looked up quickly, genuinely surprised at this bit of worldly wisdom. "When women do stupid, dangerous things, trouble follows," she persisted, adding, "if not at once, a bit later. This is a case of it." One could not help feeling sorry for the woman and what she had to face. "I had hoped, oh, so dearly," she went on a moment later, "that Gloria would marry a young man who, I know, is devoted to her, an Italian of fine family, Signor Franconi--you must have heard of him--the inventor of a new system of wireless transmission of pictures. But with such a scandal--how can we expect it? Do you know him?" "Not personally, though I have heard of him," returned Kennedy briefly. Both Craig and myself had been interested in reports of his invention, which he called the "Franconi Telephote," by which he claimed to be able to telegraph either over wires or by wireless light and dark points so rapidly and in such a manner as to deceive the eye and produce at the receiving end what amounted to a continuous reproduction of a picture at the transmitting end. At least, in spite of his society leanings, Franconi was no mere dilettante inventor. "But--the necklace," suggested Craig, after a moment, for the first time interrupting the rather rambling trend of Mrs. Brackett's story, "what has this all to do with the necklace?" She looked at him almost despairingly. "I don't really care for a thousand such necklaces," she cried. "It is my daughter--her good name--her--her safety!" Suddenly she had become almost hysterical as she thought of the real purpose of her visit, which she had not yet been able to bring herself to disclose even to Kennedy. Finally, with an effort, she managed to control herself and go on. "You see," she said in a low tone, almost as if she were confessing some fault of her own, "Gloria has been frequenting these--_recherché_ places, without my knowledge, and there she has become intimate with some of the fastest of the fast set. "You ask about the necklace. I don't know, I must admit. Has some one of her friends taken advantage of her to learn our habits and get into the house and get it? Or, have they put her up to getting it?" The last query was wrung from her as if by main force. She could not even breathe it without a shudder. "When the necklace was stolen," she added tremulously, "it must have been an inside job, as you detectives call it. Mr. Brackett and I were away at the time at a week-end party. We supposed Gloria was visiting some friends in the city. But since then we have learned that she motored out with some of her dance-crazed acquaintances to the Cabaret Rouge, not far from Willys Hills. It must have been taken then--by some of them." The recital to comparative strangers, even though they were to be trusted to right the wrong, was more than she could bear. Mrs. Brackett was now genuinely in tears, her shoulders trembling under the emotion, as she bowed her head. Her despair and self-accusation would really have moved anyone, much less were needed to enlist Kennedy. He said nothing, but his look of encouragement seemed to nerve her up again to go on. She forced back her feelings heroically. "We put the advertisement that way because--well, now you understand why," she resumed; then anticipating our question, added, "But there has been no response." I knew from her tone that even to herself she would not admit that Gloria might have been guilty. Yet subconsciously it must have been in her mind and she knew it was in ours. Her voice broke again. "Mr. Brackett has repeatedly ordered Gloria to give up her fast acquaintances. But she defies him. Even to my pleadings she has turned a deaf ear." It was most pathetic to watch the workings of the mother's face as she was forced to say this of her daughter. All thought of the necklace was lost, now. "I--I want my daughter back," she almost wailed. "Who are these rapid youngsters?" asked Craig gently. "I don't know all of them," she replied. "There is young Rittenhouse Smith; he is one. The Rittenhouse Smiths, you know, are a very fine family. But young 'Ritter,' as the younger set call him, is wild. They've had to cut his allowance two or three times, I believe. Another of them is Rhinelander Brown. I don't think the Browns have much money, but it is a good family. Oh," she added with a faint attempt at a smile, "I'm not the only mother who has heart-aches. But the worst of it is that there are some professionals with whom they go--a dancer, Rex Du Mond, and a woman named Bernice Bentley. I don't know any more of them, but I presume there is a regular organization of these social gangsters." "Did Signor Franconi--ever go with them?" asked Craig. "Oh, mercy, no," she hastened. "And they can't seem to break the gang up," ruminated Craig, evidently liking her characterization of the group. She sighed deeply and wiped away another tear. "I've done what I could with Gloria. I've cut her allowance--but it has done no good. I'm losing my hold on her altogether. You--you will help me--I mean, help Gloria?" she asked eagerly, leaning forward in an appeal which must have cost her a great deal, so common is the repression of such feelings in women of her type. "Gladly," returned Kennedy heartily. "I will do anything in my power." Proud though she was, Mrs. Brackett could scarcely murmur her thanks. "Where can I see Gloria?" asked Kennedy finally. She shook her head. "I can't say. If you want to, you may see her tomorrow, though, at the drag hunt of the club. My husband says he is not going to take Gloria's actions without a protest. So he has peremptorily ordered her to attend the meet of the Hunt Club. We thought it would get her away, at least for a time, from her associates, though I must say I can't be sure that she will obey." I thought I understood, partly at least. Bradford Brackett's election as M. F. H. had been a crowning distinction in his social career and he did not propose to have Gloria's escapades spoil the meet for him. Perhaps he thought this as good an occasion as any to use his power to force her back into the circle to which she rightfully belonged. Mrs. Brackett had risen. "How can I ever thank you?" she exclaimed, extending her hand impulsively. "I know nothing has been changed--yet. But already I feel better." "I shall do what I can; depend on me," reiterated Kennedy modestly. "If I can do nothing before, I shall be out at the Hunt Club tomorrow--perhaps I shall be there anyhow." "This is a most peculiar situation," I remarked a few minutes later, as Mrs. Brackett was whisked away from the laboratory door in her motor. "Indeed it is," returned Kennedy, pacing up and down, his face wrinkled with thought. "I don't know whether I feel more like a detective or a spiritual adviser." He pulled out his watch. "Half-past four," he considered. "I'd like to have a look at that Cabaret Rouge here in town." CHAPTER II THE CABARET ROUGE It was a perfect autumn afternoon, one of those days when one who is normal feels the call to get out of doors and enjoy what is left of the fine weather before the onset of winter. We strode along in the bracing air until at last we turned into Broadway at the upper end of what might be called "Automobile Row." Motor cars and taxicabs were buzzing along in an endless stream, most of them filled with women, gowned and bonneted in the latest mode. Before the garish entrance of the Cabaret Rouge they seemed to pile up and discharge their feminine cargoes. We entered and were quickly engulfed in the tide of eager pleasure seekers. A handsome and judicious tip to the head waiter secured us a table at the far end of a sort of mezzanine gallery, from which we could look down over a railing at the various groups at the little white tables below. There we sat, careful to spend the necessary money to entitle us to stay, for to the average New Yorker the test seems to be not so much what one is getting for it as how much money is spent when out for a "good time." Smooth and glittering on the surface, like its little polished dancing floor in the middle of the squares of tables downstairs, the Cabaret Rouge, one could see, had treacherous undercurrents unsuspected until an insight such as we had just had revealed them. The very atmosphere seemed vibrant with laughter and music. A string band played sharp, staccato, highly accentuated music, a band of negroes as in many of the showy and high-priced places where a keen sense of rhythm was wanted. All around us women were smoking cigarettes. Everywhere they were sipping expensive drinks. Instinctively one felt the undertow in the very atmosphere. I wondered who they were and where they all came from, these expensively dressed, apparently refined though perhaps only veneered girls, whirling about with the pleasantest looking young men who expertly guided them through the mazes of the fox-trot and the canter waltz and a dozen other steps I knew not of. This was one of New York's latest and most approved devices to beguile the languid afternoons of ladies of leisure. "There she is," pointed out Kennedy finally. "I recognize her from the pictures I've seen." I followed the direction of his eyes. The music had started and out on the floor twisting in and out among the crowded couples was one pair that seemed to attract more attention than the rest. They had come from a gay party seated in a little leather cozy corner like several about the room, evidently reserved for them, for the cozy corners seemed to be much in demand. Gloria was well named. She was a striking girl, not much over nineteen surely, tall, lissome, precisely the figure that the modern dances must have been especially designed to set off. I watched her attentively. In fact I could scarcely believe the impression I was gaining of her. Already one could actually see on her marks of dissipation. One does not readily think of a girl as sowing her wild oats. Yet they often do. This is one of the strange anomalies of the new freedom of woman. A few years ago such a place would have been neither so decent nor attractive. Now it was superficially both. To it went those who never would have dared overstep the strictly conventional in the evil days when the reformer was not abroad in the land. I watched Gloria narrowly. Clearly here was an example of a girl attracted by the glamor of the life and flattery of its satellites. What the end of it all might be I preferred not to guess. Craig was looking about at the variegated crowd. Suddenly he jogged my elbow. There, just around the turn of the railing of the gallery, sat a young man, dark of hair and eyes, of a rather distinguished foreign appearance, his face set in a scowl as he looked down on the heads of the dancers. One could have followed the tortuous course of Gloria and her partner by his eyes, which the man never took off her, even following her back to the table in the corner when the encore of the dance was finished. The young man's face at least was familiar to me, though I had not met him. It was Signor Franconi, quietly watching Gloria and her gay party. After a few moments, Craig rose, paid his check, and moved over to the table where Franconi was sitting alone. He introduced himself and Franconi, with easy politeness, invited us to join him. I studied the man's face attentively. Signor Franconi was still young, in spite of the honors that had been showered on him for his many inventions. I had wondered before why such a man would be interested in a girl of Gloria's evident type. But as I studied him I fancied I understood. To his serious mind it was just the butterfly type that offered the greatest relief. An intellectual woman would have been merely carrying into another sphere the problems with which he was more than capable of wrestling. But there was no line of approval in his fine face of the butterfly and candle-singeing process that was going on here. I must say I heartily liked him. "What are you working on now?" asked Kennedy as a preliminary step to drawing him out against the time when we might become better acquainted and put the conversation on a firmer basis. "A system of wireless transmission of pictures," he returned mechanically. "I think I have vastly improved the system of Dr. Korn. You are familiar with it, I presume?" Kennedy nodded. "I have seen it work," he said simply. That telephotograph apparatus, I remembered, depended on the ability of the element selenium to vary the strength of an electric current passing through it in proportion to the brightness with which the selenium is illuminated. "That system," he resumed, speaking as though his mind was not on the subject particularly just now, "produces positive pictures at one end of the apparatus by the successive transmission of many small parts separately. I have harnessed the alternating current in a brand-new way, I think. Instead of prolonging the operation, I do it all at once, projecting the image on a sheet of tiny selenium cells. My work is done. Now the thing to do is to convince the world of that." "Then you have the telephote in actual operation?" asked Kennedy. "Yes," he replied. "I have a little station down on the shore of the south side of the island." He handed us a card on which he wrote the address at South Side Beach. "That will admit you there at any time, if I should not be about. I am testing it out there--have several instruments on transatlantic liners. We think it may be of use in war--sending plans, photographs of spies--and such things." He stopped suddenly. The music had started again and Gloria was again out on the dancing floor. It was evident that at this very important time in his career Franconi's mind was on other things. "Everyone seems to become easily acquainted with everyone else here," remarked Craig, bending over the rail. "I suppose one cannot dance without partners," returned Franconi absently. We continued to watch the dancers. I knew enough of these young fellows, merely by their looks, to see that most of them were essential replicas of one type. Certainly most of them could have qualified as social gangsters, without scruples, without visible means of support, without character or credit, but not without a certain vicious kind of ambition. They seemed to have an unlimited capacity for dancing, freak foods, joy rides, and clothes. Clothes were to them what a jimmy is to a burglar. Their English coats were so tight that one wondered how they bent and swayed without bursting. Smart clothes and smart manners such as they affected were very fascinating to some women. "Who are they all, do you suppose?" I queried. "All sorts and conditions," returned Kennedy. "Wall Street fellows whose pocketbooks have been thinned by dull times on the Exchange; actors out of engagements, law clerks, some of them even college students. They seem to be a new class. I don't think of any other way they could pick up a living more easily than by this polite parasitism. None of them have any money. They don't get anything from the owner of the cabaret, of course, except perhaps the right to sign checks for a limited amount in the hope that they may attract new business. It's grafting, pure and simple. The women are their dupes; they pay the bills--and even now and then something for 'private lessons' in dancing in a 'studio.'" Franconi was dividing his attention between what Kennedy was saying and watching Gloria and her partner, who seemed to be a leader of the type I have just described, tall and spare as must be the successful dancing men of today. "There's a fellow named Du Mond," he put in. "Who is he?" asked Craig, as though we had never heard of him. "To borrow one of your Americanisms," returned Franconi, "I think he's the man who puts the 'tang' in tango. From what I hear, though, I think he borrows the 'fox' from fox-trot and plucks the feathers from the 'lame duck.'" Kennedy smiled, but immediately became interested in a tall blonde girl who had been talking to Du Mond just before the dancing began. I noticed that she was not dancing, but stood in the background most of the time giving a subtle look of appraisal to the men who sat at tables and the girls who also sat alone. Now and then she would move from one table to another with that easy, graceful glide which showed she had been a dancer from girlhood. Always after such an excursion we saw other couples who had been watching in lonely wistfulness, now made happy by a chance to join the throng. "Who is that woman?" I asked. "I believe her name is Bernice Bentley," replied Franconi. "She's the--well, they call her the official hostess--a sort of introducer. That's the reason why, as you observed, there is no lack of friendliness and partners. She just arranges introductions, very tactfully, of course, for she's experienced." I regarded her with astonishment. I had never dreamed that such a thing was possible, even in cosmopolitan New York. What could these women be thinking of? Some of them looked more than capable of taking care of themselves, but there must be many, like Gloria, who were not. What did they know of the men, except their clothes and steps? "Soft shoe workers, tango touts," muttered Kennedy under his breath. As we watched we saw a slender, rather refined-looking girl come in and sit quietly at a table in the rear. I wondered what the official introducer would do about her and waited. Sure enough, it was not long before Miss Bentley appeared with one of the dancing men in tow. To my surprise the "hostess" was coldly turned down. What it was that happened I did not know, but it was evident that a change had taken place. Unobtrusively Bernice Bentley seemed to catch the roving eye of Du Mond while he was dancing and direct it toward the little table. I saw his face flush suddenly and a moment later he managed to work Gloria about to the opposite side of the dancing floor and, though the music had not stopped, on some pretext or other to join the party in the corner again. Gloria did not want to stop dancing, but it seemed as if Du Mond exercised some sort of influence over her, for she did just as he wished. Was she really afraid of him? Who was the little woman who had been like a skeleton at a feast? Almost before we knew it, it seemed that the little party had tired of the Cabaret Rouge. Of course we could hear nothing, but it seemed as if Du Mond were proposing something and had carried his point. At any rate the waiter was sent on a mysterious excursion and the party made as though they were preparing to leave. Little had been said by either Franconi or ourselves, but it was by a sort of instinct that we, too, paid our check and moved down to the coat room ahead of them. In an angle we waited, until Gloria and her party appeared. Du Mond was not with them. We looked out of the door. Before the cabaret stood a smart hired limousine which was evidently Gloria's. She would not have dared use her own motor on such an excursion. They drove off without seeing us and a moment later Du Mond and Bernice Bentley appeared. "Thank you for the tip," I heard him whisper. "I thought the best thing was to get them away without me. I'll catch them in a taxi later. You're off at seven? Ritter will call for you? Then we'll wait and all go out together. It's safer out there." Just what it all meant I could not say, but it interested me to know that young Ritter Smith and Bernice Bentley seemed on such good terms. Evidently the gay party were transferring the scene of their gayety to the country place of the Cabaret Rouge. But why? We parted at the door with Franconi, who repeated his invitation to visit his shop down at the beach. I started to follow Franconi out, but Kennedy drew me back. "Why did you suppose I let them go?" he explained under his breath, as we retreated to the angle again. "I wanted to watch that little woman who came in alone." We had not long to wait. Scarcely had Du Mond disappeared when she came out and stood in the entrance while a boy summoned a taxicab for her. Kennedy improved the opportunity by calling another for us and by the time she was ready to drive off we were able to follow her. She drove to the Prince Henry Hotel, where she dismissed the machine and entered. We did the same. "By the way," asked Kennedy casually, sauntering up to the desk after she had stopped to get her keys and a letter, "can you tell me who that woman was?" The clerk ran his finger down the names on the register. At last he paused and turned the book around to us. His finger indicated: "Mrs. Katherine Du Mond, Chicago." Kennedy and I looked at each other in amazement. Du Mond was married and his wife was in town. She had not made a scene. She had merely watched. What could have been more evident than that she was seeking evidence and such evidence could only have been for a court of law in a divorce suit? The possibilities which the situation opened up for Gloria seemed frightful. We left the hotel and Kennedy hurried down Broadway, turning off at the office of a young detective, Chase, whom he used often on matters of pure routine for which he had no time. "Chase," he instructed, when we were seated in the office, "you recall that advertisement of the lost necklace in the _Star_ by La Rue & Co.?" The young man nodded. Everyone knew it. "Well," resumed Kennedy, "I want you to search the pawnshops, particularly those of the Tenderloin, for any trace you can find of it. Let me know, if it is only a rumor." There was nothing more that we could do that night, though Kennedy found out over the telephone, by a ruse, that, as he suspected, the country place of the Cabaret Rouge was the objective of the gay party which we had seen. CHAPTER III THE FOX HUNT The next day was that of the hunt and we motored out to the North Shore Hunt Club. It was a splendid day and the ride was just enough to put an edge on the meet that was to follow. We pulled up at last before the rambling colonial building which the Hunt Club boasted as its home. Mrs. Brackett was waiting for us already with horses from the Brackett stables. "I'm so glad you came," she greeted us aside. "Gloria is here--under protest. That young man over there, talking to her, is Ritter Smith. 'Rhine' Brown, as they call him, was about a moment ago--oh, yes, there he is, coming over on that chestnut mare to talk to them. I wanted you to see them here. After the hunt, if you care to, I think you might go over to the Cabaret Rouge out here. You might find out something." She was evidently quite proud of her handsome daughter and that anything should come up to smirch her name cut her deeply. The Hunt Club was a swagger organization, even in these degenerate days when farmers will not tolerate broken fences and trampled crops, and when democratic ideas interfere sadly with the follies of the rich. In a cap with a big peak, a scarlet hunting coat and white breeches with top boots, Brackett himself made a striking figure of M. F. H. There were thirty or forty in the field, the men in silk hats. For the most part one could not see that the men treated Gloria much differently. But it was evident that the women did. In fact the coldness even extended to her mother, who would literally have been frozen out if it had not been for her quasi-official position. I could see now that it was also a fight for Mrs. Brackett's social life. As we watched Gloria, we could see that Franconi was hovering around, unsuccessfully trying to get an opportunity to say a word to her alone. Just before we were off a telegram came to her, which she read and hastily stuffed into a pocket of her riding habit. But that was all that happened and I fell to studying the various types of human nature, from the beginner who rode very hard and very badly and made himself generally odious to the M. F. H., to the old seasoned hunter who talked of the old days of real foxes and how he used to know all the short cuts to the coverts. It was a keen, crisp day. Already a man had been over the field pulling along the ground a little bag of aniseed, and now the hunt was about to start. Noses down, sterns feathering zigzag over the ground, sniffing earth and leaves and grass, the hounds were brought up. One seemed to get a good whiff of the trail and lifted his head with a half yelp, half whine, high pitched, frenzied, never-to-be-forgotten. Others joined in the music. "Gone away!" sounded a huntsman as if there were a real fox. We were off after them. Drag hounds, however, for the most part run mute and very fast, so that that picturesque feature was missing. But the light soil and rail fences of Long Island were ideal for drag hunting. Nor was it so easy as it seemed to follow. Also there was the spice of danger, risk to the hunters, the horses and the dogs. We went for four or five miles. Then there was a check for the stragglers to come up. Some had fresh mounts, and all of us were glad of the breathing space while the M. F. H. "held" the hounds. While we waited we saw that Mrs. Brackett was riding about quickly, as if something were on her mind. A moment she stopped to speak to her husband, then galloped over to us. Her face was almost white. "Gloria hasn't come up with the rest!" she exclaimed breathlessly. Already Brackett had told those about him and all was confusion. It was only a moment when the members of the hunt were scouring the country over which we had passed, with something really definite to find. Kennedy did not pause. "Come on, Walter," he shouted, striking out down the road, with me hard after him. We pulled up before a road-house of remarkable quaintness and luxury of appointment, one of the hundreds about New York which the automobile has recreated. Before it swung the weathered sign: Cabaret Rouge. To our hurried inquiries the manager admitted that Du Mond had been there, but alone, and had left, also alone. Gloria had not come there. A moment later sounds of hoofs on the hard road interrupted us and Ritter Smith dashed up. "Just overtook a farmer down the road," he panted. "Says he saw an automobile waiting at the stone bridge and later it passed him with a girl and a man in it. He couldn't recognize them. The top was up and they went so fast." Together we retraced the way to the stone bridge. Sure enough, there on the side of the road were marks where a car had pulled up. The grass about was trampled and as we searched Kennedy reached down and picked up something white. At least it had been white. But now it was spotted with fresh blood, as though someone had tried to stop a nose-bleed. He looked at it more closely. In the corner was embroidered a little "G." Evidently there had been a struggle and a car had whizzed off. Gloria was gone. But with whom? Had the message which we had seen her read at the start been from Du Mond? Was the plan to elope and so avoid his wife? Then why the struggle? Absolutely nothing more developed from the search. An alarm was at once sent out and the police all over the country notified. There was nothing to do now but wait. Mrs. Brackett was frantic. But it was not now the scandal that worried her. It was Gloria's safety. That night, in the laboratory, Kennedy took the handkerchief and with the blood on it made a most peculiar test before a strange-looking little instrument. It seemed to consist of a little cylinder of glass immersed in water kept at the temperature of the body. Between two minute wire pincers or serres, in the cylinder, was a very small piece of some tissue. To the lower serre was attached a thread. The upper one was attached to a sort of lever ending in a pen that moved over a ruled card. "Every emotion," remarked Kennedy as he watched the movement of the pen in fine zigzag lines over the card, "produces its physiological effect. Fear, rage, pain, hunger are primitive experiences, the most powerful that determine the actions of man. I suppose you have heard of the recent studies of Dr. Walter Cannon of Harvard of the group of remarkable alterations in bodily economy under emotion?" I nodded and Kennedy resumed. "On the surface one may see the effect of blood vessels contracting, in pallor; one may see cold sweat, or the saliva stop when the tongue cleaves to the roof of the mouth, or one may see the pupils dilate, hairs raise, respiration become quick, or the beating of the heart, or trembling of the muscles, notably the lips. But one cannot see such evidences of emotion if he is not present at the time. How can we reconstruct them?" He paused a moment, then resumed. "There are organs hidden deep in the body which do not reveal so easily the emotions. But the effect often outlasts the actual emotion. There are special methods by which one can study the feelings. That is what I have been doing here." "But how can you?" I queried. "There is what is called the sympathetic nervous system," he explained. "Above the kidney there are also glands called the suprarenal which excrete a substance known as adrenin. In extraordinarily small amounts adrenin affects this sympathetic system. In emotions of various kinds a reflex action is sent to the suprarenal glands which causes a pouring into the blood of adrenin. "On the handkerchief of Gloria Brackett I obtained plenty of comparatively fresh blood. Here in this machine I have between these two pincers a minute segment of rabbit intestine." He withdrew the solution from the cylinder with a pipette, then introduced some more of the dissolved blood from the handkerchief. The first effect was a strong contraction of the rabbit intestine, then in a minute or so the contractions became fairly even with the base line on the card. "Such tissue," he remarked, "is noticeably affected by even one part in over a million of adrenin. See. Here, by the writing lever, the rhythmical contractions are recorded. Such a strip of tissue will live for hours, will contract and relax beautifully with a regular rhythm which, as you see, can be graphically recorded. This is my adrenin test." Carefully he withdrew the ruled paper with its tracings. "It's a very simple test after all," he said, laying beside this tracing another which he had made previously. "There you see the difference between what I may call 'quiet blood' and 'excited blood.'" I looked at the two sets of tracings. Though they were markedly different, I did not, of course, understand what they meant. "What do they show to an expert?" I asked, perplexed. "Fear," he answered laconically. "Gloria Brackett did not go voluntarily. She did not elope. She was forced to go!" "Attacked and carried off?" I queried. "I did not say that," he replied. "Perhaps our original theory that her nose was bleeding may be correct. It might have started in the excitement, the anger and fear at what happened, whatever it was. Certainly the amount of adrenin in her blood shows that she was laboring under strong enough emotion." Our telephone rang insistently and Kennedy answered it. As he talked, although I could hear only one side of the conversation, I knew that the message was from Chase and that he had found something important about the missing necklace. "What was it?" I asked eagerly as he hung up the receiver. "Chase has traced the necklace," he reported; "that is, he has discovered the separate stones, unset, pawned in several shops. The tickets were issued to a girl whose description exactly fits Gloria Brackett." I could only stare at him. What we had all feared had actually taken place. Gloria must have taken the necklace herself. Though we had feared it and tried to discount it, nevertheless the certainty came as a shock. "Why should she have taken it?" I considered. "For many possible reasons," returned Kennedy. "You saw the life she was leading. Her own income probably went to keeping those harpies going. Besides, her mother had cut her allowance. She may have needed money very badly." "Perhaps they had run her into debt," I agreed, though the thought was disagreeable. "How about that other little woman we saw?" suggested Kennedy. "You remember how Gloria seemed to stand in fear of Du Mond? Who knows but that he made her get it to save her reputation? A girl in Gloria's position might do many foolish things. But to be named as co-respondent, that would be fatal." There was not much comfort to be had by either alternative, and we sat for a moment regarding each other in silence. Suddenly the door opened. Mrs. Brackett entered. Never have I seen a greater contrast in so short a time than that between the striking society matron who first called on us and the broken woman now before us. She was a pathetic figure as Kennedy placed an easy chair for her. "Why, what's the matter?" asked Kennedy. "Have you heard anything new?" She did not answer directly, but silently handed him a yellow slip of paper. On a telegraph blank were written simply the words, "Don't try to follow me. I've gone to be a war nurse. When I make good I will let you know. Gloria." We looked at each other in blank amazement. That was hardly an easy way to trace her. How could one ever find out now where she was, in the present state of affairs abroad, even supposing it were not a ruse to cover up something? Somehow I felt that the message did not tell the story. Where was Du Mond? Had he fled, too,--perhaps forced her to go with him when Mrs. Du Mond appeared? The message did not explain the struggle and the fear. "Oh, Mr. Kennedy," pleaded Mrs. Brackett, all thought of her former pride gone, as she actually held out her hands imploringly and almost fell on her knees, "can't you find her--can't you _do_ something?" "Have you a photograph of Gloria?" he asked hurriedly. "Yes," she cried eagerly, reaching into her mesh bag and drawing one out. "I carry it with me always. Why?" "Come," exclaimed Kennedy, seizing it. "It occurs to me that it is now or never that this device of Franconi's must prove that it is some good. If she really went, she wasted no time. There's just a bare chance that the telephote has been placed on some of these vessels that are carrying munitions abroad. Franconi says that he has developed it for its war value." As fast as Mrs. Brackett's chauffeur could drive us, we motored down to South Side Beach and sought out the little workshop directly on the ocean where Franconi had told us that we should always be welcome. He was not there, but an assistant was. Kennedy showed him the card that Franconi had given us. "Show me how the machine works," he asked, while Mrs. Brackett and I waited aside, scarcely able to curb our impatience. "Well," began the assistant, "this is a screen of very minute and sensitive selenium cells. I don't know how to describe the process better than to say that the tones of sound, the human voice, have hundreds of gradations which are transmitted, as you know, by wireless, now. Gradations of light, which are all that are necessary to produce the illusion of a picture, are far simpler than those of sound. Here, in this projector--" "That is the transmitting part of the apparatus?" interrupted Kennedy brusquely. "That holder?" "Yes. You see there are hundreds of alternating conductors and insulators, all synchronized with hundreds of similar receivers at the--" "Let me see you try this photograph," interrupted Kennedy again, handing over the picture of Gloria which Mrs. Brackett had given him. "Signor Franconi told me he had the telephote on several outgoing liners. Let me see if you can transmit it. Is there any way of sending a wireless message from this place?" The assistant had shoved the photograph into the holder from which each section was projected on the selenium cell screen. "I have a fairly powerful plant here," he replied. Quickly Kennedy wrote out a message, briefly describing the reason why the picture was transmitted and asking that any station on shipboard that received it would have a careful search made of the passengers for any young woman, no matter what name was assumed, who might resemble the photograph. Though nothing could be expected immediately at best, it was at least some satisfaction to know that through the invisible air waves, wirelessly, the only means now of identifying Gloria was being flashed far and wide to all the big ships within a day's distance or less on which Franconi had established his system as a test. The telephote had finished its work. Now there was nothing to do but wait. It was a slender thread on which hung the hope of success. While we waited, Mrs. Brackett was eating her heart out with anxiety. Kennedy took the occasion to call up the New York police on long distance. They had no clew to Gloria. Nor had they been able to find a trace of Du Mond. Mrs. Du Mond also had disappeared. At the Cabaret Rouge, Bernice Bentley had been held and put through a third degree, without disclosing a thing, if indeed she knew anything. I wondered whether, at such a crisis, Du Mond, too, might not have taken the opportunity to flee the country. We had almost given up hope, when suddenly a little buzzer on the telephote warned the operator that something was coming over it. "The _Monfalcone_," he remarked, interpreting the source of the impulses. "We gathered breathlessly about the complicated instrument as, on a receiving screen composed of innumerable pencils of light polarized and acting on a set of mirrors, each corresponding to the cells of the selenium screen and tuned to them, as it were, a thin film or veil seemed gradually to clear up, as the telephote slowly got itself into equilibrium at both ends of the air line. Gradually the face of a girl appeared. "Gloria!" gasped Mrs. Brackett in a tone that sounded as if ten years had been added to her life. "Wait," cautioned the operator. "There is a written message to follow." On the same screen now came in letters that Mrs. Brackett in her joy recognized the message: "I couldn't help it. I was blackmailed into taking the necklace. Even at the hunt I received another demand. I did not mean to go, but I was carried off by force before I could pay the second demand. Now I'm glad of it. Forgive us. Gloria." "Us?" repeated Mrs. Brackett, not comprehending. "Look--another picture," pointed Kennedy. We bent over as the face of a man seemed to dissolve more clearly in place of the writing. "Thank God!" exclaimed Mrs. Brackett fervently, reading the face by a sort of intuition before it cleared enough for us to recognize. "He has saved her from herself!" It was Franconi! Slowly it faded and in its place appeared another written message. "Recalled to Italy for war service. I took her with me by force. It was the only way. Civil ceremony in New York yesterday. Religious will follow at Rome." CHAPTER IV THE TANGO THIEF "My husband has such a jealous disposition. He will never believe the truth--never!" Agatha Seabury moved nervously in the deep easy chair beside Kennedy's desk, leaning forward, uncomfortably, the tense lines marring the beauty of her fine features. Kennedy tilted his desk chair back in order to study her face. "You say you have never written a line to the fellow nor he to you?" he asked. "Not a line, not a scrap,--until I received that typewritten letter about which I just told you," she repeated vehemently, meeting his penetrating gaze without flinching. "Why, Professor Kennedy, as heaven is my witness, I have never done a wrong thing--except to meet him now and then at afternoon dances." I felt that the nerve-racked society woman before us must be either telling the truth or else that she was one of the cleverest actresses I had ever seen. "Have you the letter here?" asked Craig quickly. Mrs. Seabury reached into her neat leather party case and pulled out a carefully folded sheet of note paper. It was all typewritten, down to the very signature itself. Evidently the blackmailer had taken every precaution to protect himself, for even if the typewriting could be studied and identified, it would be next to impossible to get at the writer through it and locate the machine on which it was written among the thousands in the city. Kennedy studied the letter carefully, then, with a low exclamation, handed it over to me, nodding to Mrs. Seabury that it was all right for me to see it. "No ordinary fellow, I'm afraid," he commented musingly, adding, "this thief of reputations." I read, beginning with the insolent familiarity of "Dear Agatha." "I hope you will pardon me for writing to you," the letter continued, "but I find that I am in a rather difficult position financially. As you know, in the present disorganized state of the stock market, investments which in normal times are good are now almost valueless. Still, I must protect those I already have without sacrificing them. "It is therefore necessary that I raise fifty thousand dollars before the end of the week, and I know of no one to appeal to but you--who have shared so many pleasant stolen hours with me. "Of course, I understand all that you have told me about Mr. Seabury and his violent nature. Still, I feel sure that one of your wealth and standing in the community can find a way to avoid all trouble from that quarter. Naturally, I should prefer to take every precaution to prevent the fact of our intimacy from coming to Mr. Seabury's knowledge. But I am really desperate and feel that you alone can help me. "Hoping to hear from you soon, I am, "Your old tango friend, "H. MORGAN SHERBURNE." I fairly gasped at the thinly veiled threat of exposure at the end of the note from this artistic blackmailer. She was watching our faces anxiously as we read. "Oh," she cried wildly, glancing from one to the other of us, strangers to whom in her despair she had been forced to bare the secrets of her proud heart, "he's so clever about it, too. I--I didn't know what to do. I had only my jewels. I thought of all the schemes I had ever read, of pawning them, of having paste replicas made, of trying to collect the burglary insurance, of--" "But you didn't do anything like that, did you?" interrupted Craig hastily. "No, no," she cried. "I thought if I did, then it wouldn't be long before this Sherburne would be back again for more. Oh," she almost wailed, dabbing at the genuine tears with her dainty lace handkerchief while her shoulders trembled with a repressed convulsive sob, "I--I am utterly wretched--crushed." "The scoundrel!" I muttered. Kennedy shook his head at me slowly. "Calling names won't help matters now," he remarked tersely. Then in an encouraging tone he added, "You have done just the right thing, Mrs. Seabury, in not starting to pay the blackmail. The secret of the success of these fellows is that their victims prefer losing jewelry and money to going to the police and having a lot of unpleasant notoriety." "Yes, I know that," she agreed hastily, "but--my husband! If he hears, he will believe the worst, and--I--I really love and respect Judson--though," she added, "he might have seen that I liked dancing and--innocent amusements of the sort still. I am not an old woman." I could not help wondering if the whole truth were told in her rather plaintive remark, or whether she was overplaying what was really a minor complaint. Judson Seabury, I knew from hearsay, was a man of middle age to whom, as to so many, business and the making of money had loomed as large as life itself. Competitors had even accused him of being ruthless when he was convinced that he was right, and I could well imagine that Mrs. Seabury was right in her judgment of the nature of the man if he became convinced for any reason that someone had crossed his path in his relations with his wife. "Where did you usually--er--meet Sherburne?" asked Craig, casually guiding the conversation. "Why--at the Vanderveer--always," she replied. "Would you mind meeting him there again this afternoon so that I could see him?" asked Kennedy. "Perhaps it would be best, anyhow, to let him think that you are going to do as he demands, so that we can gain a little time." She looked up, startled. "Yes--I can do that--but don't you think it is risky? Do you think there is any way I can get free from him? Suppose he makes a new demand. What shall I do? Oh, Professor Kennedy, you do not, you cannot know what I am going through--how I hate and fear him." "Mrs. Seabury," reassured Craig earnestly, "I'll take up your case. Clever as the man is, there must be some way to get at him." Sherburne must have exercised a sort of fascination over her, for the look of relief that crossed her face as Kennedy promised to aid her was almost painful. As often before, I could scarcely envy Kennedy in his ready assumption of another's problems that seemed so baffling. It meant little, perhaps, to us whether we succeeded. But to her it meant happiness, perhaps honor itself. It was as though she were catching at a life line in the swirling current of events that had engulfed her. She hesitated no longer. "I'll be there--I'll meet him--at four," she murmured, as she rose and made a hurried departure. For some time after she had gone, Kennedy sat considering what she had told us. As for myself, I cannot say that I was thoroughly satisfied that she had told all. It was not to be expected. "How do you figure that woman out?" I queried at length. Kennedy looked at me keenly from under knitted brows. "You mean, do I believe her story--of her relations with this fellow, Sherbourne?" he returned, thoughtfully. "Exactly," I assented, "and what she said about her regard for her husband, too." Kennedy did not reply for a few minutes. Evidently the same question had been in his own mind and he had not reasoned out the answer. Before he could reply the door buzzer sounded and the colored boy from the lower hall handed a card to Craig, with an apology about the house telephone switchboard being out of order. As Kennedy laid the card on the table before us, with a curt "Show the gentleman in," to the boy, I looked at it in blank amazement. It read, "Judson Seabury." Before I could utter a word of comment on the strange coincidence, the husband was sitting in the same chair in which his wife had sat less than half an hour before. Judson Seabury was a rather distinguished looking man of the solid, business type. Merely to meet his steel gray eye was enough to tell one that this man would brook no rivalry in anything he undertook. I foresaw trouble, even though I could not define its nature. Craig twirled the card in his fingers, as if to refresh his mind on a name otherwise unfamiliar. I was wondering whether Seabury might not have trailed his wife to our office and have come to demand an explanation. It was with some relief that I found he had not. "Professor Kennedy," he began nervously, hitching his chair closer, without further introduction, in the manner of a man who was accustomed to having his own way in any matter he undertook, "I am in a most peculiar situation." Seabury paused a moment, Kennedy nodded acquiescence, and the man suddenly blurted out, "I--I don't know whether I'm being slowly poisoned or not!" The revelation was startling enough in itself, but doubly so after the interview that had just preceded. I covered my own surprise by a quick glance at Craig. His face was impassive as he narrowly searched Seabury's. I knew, though, that back of his assumed calm, Craig was doing some rapid thinking about the ethics of listening to both parties in the case. However, he said nothing. Indeed, Seabury, once started, hurried on, scarcely giving him a chance to interrupt. "I may as well tell you," he proceeded, with the air of a man who for the first time is relieving his mind of something that has been weighing heavily on him, "that for some time I have not been exactly--er--easy in my mind about the actions of my wife." Evidently he had arrived at the conclusion to tell what worried him, and must say it, for he continued immediately: "It's not that I actually know anything about any indiscretions on Agatha's part, but,--well, there have been little things--hints that she was going frequently to _thés dansants_, and that sort of thing, you know. Lately, too, I have seen a change in her manner toward me, I fancy. Sometimes I think she seems to avoid me, especially during the last few days. Then again, as this morning, she seems to be--er--too solicitous." He passed his hand over his forehead, as if to clear it. For once he did not seem to be the self-confident man who had at first entered our apartment. I noticed that he had a peculiar look, a feeble state of the body which he was at times at pains to conceal, a look which the doctors call, I believe, cachectic. "I mean," he added hastily, as if it might as well be said first as last, "that she seems to be much concerned about my health, my food--" "Just what is it that you actually know, not what you fear?" interrupted Kennedy, perhaps a little brusquely, at last having seen a chance to insert a word edgewise into the flow of Seabury's troubles, real or imaginary. Seabury paused a moment, then resumed with a description of his health, which, to tell the truth, was by no means reassuring. "Well," he answered slowly, "I suffer a good deal from such terrible dyspepsia, Professor Kennedy. My stomach and digestion are all upset--bad health and growing weakness--pain, discomfort--vomiting after meals, even bleeding. I've tried all sorts of cures, but still I can feel that I am still losing health and strength, and, so far, at least, the doctors don't seem to be doing me much good. I have begun to wonder whether it is a case for the doctors, after all. Why, the whole thing is getting on my nerves so that I'm almost afraid to eat," he concluded. "You have eaten nothing today, then, I am to understand?" asked Craig when Seabury had finished with his minute and puzzling account of his troubles. "Not even breakfast this morning," he replied. "Mrs. Seabury urged me to eat, but--I--I couldn't." "Good!" exclaimed Kennedy, much to our surprise. "That will make it just so much easier to use a test I have in mind to determine whether there is anything in your suspicions." He had risen and gone over to a cabinet. "Would you mind baring your arm a moment?" he asked Seabury. With a sharp little instrument, carefully sterilized, Craig pricked a vein in the man's arm. Slowly a few drops of darkened venous blood welled out. A moment later Kennedy caught them in a sterile test tube and sealed the tube. Before our second visitor could start again in retailing his suspicions which now seemed definitely, in his own mind at least, directed in some way against Mrs. Seabury, Kennedy skillfully closed the interview. "I feel sure that the test I shall make will tell me positively, soon, whether your fears are well grounded or not, Mr. Seabury," he concluded briefly, as he accompanied the man out into the hall to shake hands farewell with him at the elevator door. "I'll let you know as soon as anything develops, but until we have something tangible there is no use wasting our energies." CHAPTER V THE "THE DANSANT" I felt, however, that Seabury accepted this conclusion reluctantly, in fact with a sort of mental reservation not to cease activity himself. The remainder of the forenoon, and for some time during the early afternoon, Craig plunged into one of his periods of intense work and abstraction at the laboratory. It was, indeed, a most unusual and delicate test which he was making. For one thing, I noticed that he had, in a sterilizer, some peculiar granular tissue that had been sent to him from a hospital. This tissue he was very careful to cleanse of blood and then by repeated boilings prepare for whatever use he had in mind. As for myself, I could only stand aside and watch his preparations in silence. Among the many peculiar pieces of apparatus which he had, I recall one that consisted of a glass cylinder with a siphon tube running into it halfway up the outside. Inside was another, smaller cylinder. All about him as he proceeded were glass containers, capillary pipettes, test tubes, Bunsen burners, and dialyzers of porous parchment paper whose wrappers described them as "permeable for peptones, but not for albumins." Carefully set aside was the blood which he had drawn from Seabury's veins, allowed to stand till the serum separated out from the clot. Next he pipetted it into a centrifuge tube and centrifuged it at high speed, some sixteen thousand revolutions, until the serum was perfectly clear, with no trace of a reddish tint, nor even cloudy. After that he drew off the serum into a little tube, covered it with a layer of a substance called toluol from another sterile pipette, and finally placed it in an incubator at a temperature of about ninety-eight. It was well along toward four o'clock when he paused as if some mental alarm clock had awakened him to another part of the plan of action he had laid out. "Walter," he remarked, hastily doffing his stained old laboratory coat, "I think we'd better drop around to the Vanderveer." Curious as I had been at the preparations he was making in the laboratory, I was still glad at even the suggestion of something that my less learned mind could understand and it was not many seconds before we were on our way. Through the lobby of the famous new hostelry we slowly lounged along, then down a passage into the tea room, where, in the center of a circle of quaint little wicker chairs and tables, was a glossy dancing floor. Kennedy selected a table not in the circle, but around an "L," inconspicuously located so that we could watch the dancing without ourselves being watched. At one end of the room an excellent orchestra was playing. I gazed about, fascinated. At the dancing tea was represented, apparently, much wealth--women whose throats and fingers glittered with gold and gems, men whose very air exuded prosperity--or at least its veneer. About it all was the glamor of the _risqué_. One felt a sort of compromising familiarity in this breaking down of old social restraints through the insidious influence of the tea room, with its accompaniments of music and dancing. "I suppose," remarked Craig after we had for some time settled ourselves and watched the brilliant scene, "that, like many others, Walter, you have often wondered whether these modern dances are actually as stimulating as they seem." I shrugged my shoulders non-committally. "Well, there is what psychologists might call a real dance neurosis," he went on, contemplatively, toying with a glass. "In fact few persons can withstand the physical effect of the peculiar rhythm, the close contact, and the sinuous movements--at least where, so to speak, the surroundings are suggestive and the dance becomes less restrained and more sensuous, as it does often in circumstances like these, often among strangers." The music had started again and one after another couples seemed to float past in unhesitating hesitation--dowager and débutante, dandy and doddering octogenarian. "Why," he exclaimed, looking out at the whirling kaleidoscope, "here in the most advanced epoch, people of culture and intelligence frankly say they are 'wild' for something primitive." "Still," I objected, "dancing even in the wild, stimulating emotional manner you see here need not be merely an incitement to love, need it? May it not be a normal gratification of the love instinct--eroticism translated into rhythm? Perhaps it may represent sex, but not necessarily badly." Kennedy nodded. "Undoubtedly the effect of the dances is in direct ratio to the sexual temperament of the dancer," he admitted. He paused and again watched the whirl. "Does Mrs. Seabury herself understand it?" he mused, only half speaking to me. "I'm sure that this Sherburne is clever enough to do so, at any rate." A hearty round of applause came from the dancers as the music ceased. None left the floor, however, but remained waiting for the encore eagerly, scarcely changing the positions in which they had stopped. "To my mind," Kennedy resumed, with the music, "several things seem significant. Many people have noticed that after marriage women generally lose much of their ardor for dancing. I feel that it is an unsafe matter on which to generalize, but--well--Mrs. Seabury seems not to have lost it." "Then," I inquired quickly, "you imply that--she is not really as much in love with her husband as she would have us think--or, perhaps, herself believes?" "Not quite that," he replied doubtfully. "But I am wondering whether there is such a factor that must be considered." Before I could answer Kennedy touched my arm. Instinctively I followed the direction of his eye and saw Mrs. Seabury step out on the floor across from us. Without a word from Craig, I realized that the man with her must be Sherburne, our "tango thief." Fashionably dressed, affable, seemingly superficially, at least, well educated, tall, graceful, with easy manners, I could not help seeing at a glance that he was one of the most erotic dancers on the little floor. As they passed near us, Mrs. Seabury caught Kennedy's eye in momentary recognition. Her face, flushed with the dance, colored perhaps a shade deeper, but not noticeably to her partner, who was devoting himself wholly and skillfully to leading her in a manner that one could see called forth frequent comment from others, less favored. As they sat down after this dance and the encore, Craig motioned to the waiter at our table and whispered to him. A few moments later, a man whom I had seen around the hotel on my infrequent visits, but did not know, slipped quietly into a seat beside Kennedy, even deeper in the shadow of the recess in which we were sitting. "Walter, I'd like to have you meet Mr. Dunn, the house detective," whispered Kennedy under his breath. The usual interchange of remarks followed, during which Dunn was evidently waiting for Kennedy to reveal the real purpose of our visit. "By the way, Dunn," remarked Craig at length, "who is that fellow--over there with the woman in blue--the fellow with the heavy braided coat?" Dunn craned his neck cautiously, then shrugged his shoulders. "I've seen him here with her before," he remarked. "I don't know him, though. Why?" Briefly Kennedy sketched such facts of a supposedly hypothetical case as would be likely to secure an opinion from the house man. Dunn narrowed his eyes thoughtfully. "That's rather a ticklish situation, Kennedy," Dunn remarked when Craig had stated the case, omitting all reference to Seabury's name as well as his suspicions. "Of course," he went on, "I know we've got to protect the name of the hotel. And I know we can't have men meeting our women patrons, doing a gavotte or two--and then fox-trotting them into blackmail." Dunn stroked his chin thoughtfully. "You see, we can do a great deal to suppress card sharps, agents for fake mining stocks, passers of worthless checks, and confidence men of that sort. But it is not so simple to thwart the vultures who prey on the gullibility and passions of the so-called idle rich." "There must be something you can do to get it on this fellow, though," persisted Craig. "Well," considered the house man, "we have what might be called our hotel secret service--several men and women operating entirely apart from the hotel force of detectives who, like myself, are too well known to clever crooks. Nobody knows them, except myself. There's one--that girl over there dancing with that middle-aged man who has mail sent here but doesn't live here. Could they be of use?" "Just the thing," exclaimed Craig enthusiastically. "Can't you have her get acquainted--just as a precaution--with that man? His name, by the way, I understand is Sherburne." "I'll do it," agreed Dunn, rising unostentatiously. Just then I happened to glance across the floor and over the heads of those seated at the tables at a door opposite us. It was my turn hastily to seize Kennedy's elbow. "Good God!" I exclaimed involuntarily. There, in the further doorway of the tea room, stood Judson Seabury himself! Without a word, Craig rose and quickly crossed the dancing floor, stopping before Mrs. Seabury's table. Instead of waiting to be introduced, he sat down deliberately, as though he had been there all the time and had just gone out of the room and come back. He did it all so quickly that he was able in a perfectly natural way to turn and see that Seabury himself had been watching and now was advancing slowly, picking his way among the crowded tables. From around my corner I saw Craig whisper a word or two to Mrs. Seabury, then rise and meet Seabury less than halfway from the door by which he had been standing. The tension of the situation was too much for Mrs. Seabury. Confounded and bewildered, she fled precipitately, passing within a few feet of my table. Her face was positively ghastly. As for Sherburne, he merely sat a moment and surveyed the irate husband with calm and studied insolence at a safe distance. Then he, too, rose and turned deliberately on his heel. Curious to know how Craig would meet the dilemma, I watched eagerly and was surprised to see Seabury, after a moment's whispered talk, turn and leave the tea room by the same door through which he had entered. "What did you do?" I asked, as Craig rejoined me a few moments later. "What did you say? My hat's off to you," I added in admiration. "Told him I had trailed her here with one of my operatives, but was convinced there was nothing wrong, after all," he returned. "You mean," I asked as the result of Craig's quick thinking dawned on me, "that you told him Sherburne was _your_ operative?" Kennedy nodded. "I want to see him, now, if I can," he said simply. CHAPTER VI THE SERUM DIAGNOSIS We paid our check and Kennedy and I sauntered in the direction Sherburne had taken, finding him ultimately in the cafe, alone. Without further introduction Kennedy approached him. "So--you are a detective?" sneered Sherburne superciliously, elevating his eyebrows just the fraction of an inch. "Not exactly," parried Kennedy, seating himself beside Sherburne. Then in a tone as if he were willing to get down, without further preliminary, to business, seemingly negotiating, he asked: "Mr. Sherburne, may I ask just what it is on which you base your claim on Mrs. Seabury? Is it merely meeting her here? If that is so you must know that it amounts to nothing--now." The two men faced each other, each taking the other's measure. "Nothing?" coolly retorted Sherburne. "Perhaps not--in itself. But--suppose--I--had--" He said the words slowly, as he fumbled in his fob pocket, then cut them short as he found what he was looking for. Safely, in the palm of his hand, he displayed a latch-key, momentarily, then with a taunting smile dropped it back again into the fob pocket. "Perhaps she gave it to me--perhaps I was a welcome visitor in her apartment," he insinuated. "How would she relish having that told to Mr. Seabury--backed up by the possession of the key?" I could not help feeling that for the moment Kennedy was checkmated. Sherburne was playing a desperate game and apparently held the key, however he got it, as a trump card. "Thank you," was all that Kennedy said, as he rose. "I wanted to know how far you could go. Perhaps we can meet you halfway." Sherburne smiled cynically. "All the way," he said quietly, as we left the cafe. In silence Kennedy left the hotel and jumped into a cab, directing the driver to the laboratory, where he had asked Mrs. Seabury to wait for him. We found her there, still much agitated. Hastily Craig explained to her how he had saved the situation, but her mind was too occupied over something else to pay much attention. "I--I can't blame you, Professor Kennedy," she cried, choking down a sob in her voice, "but I have just discovered--he has told me that it is even worse than I had anticipated." We were both following her closely, the incident of the latch-key still fresh in mind. "Some time ago," she hurried on, "I missed my latch-key. I thought nothing of it at the time--thought perhaps I had mislaid it. But today he told me--just after the dance, even while I was making him think I would pay him the money, because--because I liked him--he told me he had it. The brute! He must have picked my handbag!" Her eyes were blazing now with indignation. Yet as she looked at us both, evidently the recollection of what had just happened came flooding over her mind, and she dropped her head in her hands in helpless dismay at the new development. Craig pulled out his watch hastily. "It is about six, Mrs. Seabury," he reassured. "Can you be here at, say, eight?" "I will be here," she murmured pliantly, realizing her own helplessness. She had scarcely closed the door when Craig seized the telephone, and hurriedly tried to locate Seabury himself. "Apparently no trace of him yet," he fumed, as he hung up the receiver. "The first problem is how to get that key." Instantly I thought of Dunn's secret service girl. Kennedy shook his head doubtfully. "I'm afraid there is no time for that," he answered. "But will you attend to that end of the affair for me, Walter? I have just a little more work here at the laboratory before I am ready. I don't care how you do it, but I want you to convey to Sherburne the welcome news that Mrs. Seabury is prepared to give in, in any way he may see fit, if he will call her up here at eight o'clock." Kennedy had already plunged back among his beakers and test tubes, and with these slender instructions I sallied forth in my quest of Sherburne. I had little difficulty in locating him and delivering my message, which he received with a satisfaction that invited assault and battery and mayhem. However, I managed to restrain myself and rejoin Craig in the laboratory, shortly after seven o'clock. I had scarcely had time to assure Kennedy of the success of my mission, when we were surprised to see the door open and Seabury himself appear. His face was actually haggard. Whether or not he had believed the hastily concocted story of Kennedy at the Vanderveer, his mind had not ceased to work on the other fears that had prompted his coming to us in the first place. "I've been trying to locate you all over," greeted Craig. Seabury heaved a sigh and passed his hand, with its familiar motion, over his forehead. "I thought perhaps you might be able to find out something from this stuff," he answered, unwrapping a package which he was carrying. "Some samples of the food I've been getting. If you don't find anything in this, I've others I want tested." As I looked at the man's drawn face, I wondered whether in fact there might be something in his fears. On the surface, the thing did indeed seem to place Agatha Seabury in a bad light. At the sight of the key in Sherburne's possession I had grasped at the straw that he might have conceived some diabolical plan to get rid of Seabury for purposes of his own. But then, I reasoned, would he have been so free in showing the key if he had realized that it might cast suspicion on himself? I was forced to ask myself again whether she might, in her hysterical fear of exposure by the adroit blackmailer, have really attempted to poison her husband. It was a desperate situation. But Kennedy was apparently ready to meet it, though he seemed to take no great interest in the food samples Seabury had just brought. Instead he seemed to rely wholly on the tests he had already begun with the peculiar tissue I had seen him boiling and the blood serum derived from Seabury himself. Without a word he took three tubes from the incubator, in which I had seen him place them some time before, and, as they stood in a rack, indicated them lightly with his finger. "I think I can clear part of this mystery up immediately," he began, speaking more to himself than to Seabury and myself. "Here I have a tested dialyzer in which has been placed a half cubic centimeter of pure clear serum. Here is another dialyzer with the same amount of serum, but no tissue, such as Mr. Jameson has seen me place in this first one. Here is still another with the tissue in distilled water, but no blood serum. I have placed all the dialyzers in tubes of distilled water and all are covered with a substance known as toluol and corked to keep them from contamination." Kennedy held up before us the three tubes and Seabury gazed on them with a sort of fascination, scarcely believing that in them in some way might be contained the verdict on the momentous problem that troubled his mind and might perhaps mean life or death to him. Carefully Kennedy took from each tube a few cubic centimeters of the dialyzate and into each he poured a little liquid from a tiny vial which I noticed was labelled "Ninhydrin." "This," he explained as he set down the vial, "is a substance which gives a colorless solution with water, but when mixed with albumins, peptones, or amino-acids becomes violet on boiling. Tube number three must remain colorless. Number two may be violet. Number one may approximate number two or be more deeply colored. If one and two are about the same I call my test negative. But if one is more deeply colored than two, then it is positive. The other tube is the control." Impatiently we waited as the three tubes simmered over the heat. What would they show? Seabury's eyes were glued on them, his hand trembling in the presence of some unknown danger. Slowly the liquid in the second tube turned to violet. But more rapidly and more deeply appeared the violet in number one. The test was positive. "What is it?" gasped Seabury hoarsely, leaning over close. "This," exclaimed Kennedy, "is the famous Abderhalden test--serum-diagnosis--discovered by Professor Emile Abderhalden of Halle. It rests on the fact that when a foreign substance comes into the blood, the blood reacts, with the formation of a protective ferment produced as a result of physiologic and pathologic conditions. "For instance," he went on, "a certain albumin always produces a certain ferment. Presence in the blood stream of blood-foreign substances calls forth a ferment that will digest them and split them into molecules. The forces of nature form and mobilize directly in the blood serum. "Let me get this clearly. Albumin cannot pass through the pores of an animal membrane, since the individual molecules are too large. If, however, the albumin is broken up by a ferment-action, then the molecules become small enough to pass through." Seabury was listening like a man on whom a stunning blow was about to descend. "Thus we can tell," proceeded Kennedy, "whether there is such a ferment in blood serum as would be produced by a certain condition, for when the ferment is there blood from the individual possessing it will digest a similar proteid in a dialyzing thimble kept at body temperature. "Why," cried Kennedy, swept along by the wonder of the thing, "this test opens up a vista of alluring and extensive possibilities. The human organism actually diagnoses its own illnesses automatically. It is infinitely more exact, more rapid, and more certain than all that human art can attain. Each organ contains special ferments in its cells in the most subtle way attuned to the molecular condition of the particular cell substance and with complete indifference to other cells. "Don't you see? It diagnoses at the very first stage. You take a small quantity of blood, derive the serum, then introduce a piece of tissue such as you wish to find out whether it is diseased or not. The thing is of overwhelming importance. One can discover a condition even before the organ itself shows it outwardly. It means a new epoch in medicine. As for me, I call it the new 'police service' of the organism--working with perfect, scientific accuracy." "Wh-what do you find?" reiterated Seabury. "I have made tests for about everything I can suspect," returned Kennedy, taking the tubes and pouring the liquid from number two into number one until they were equalized in color, thus testing them, while we watched every action closely. "You see," he digressed, "to get the two the same shade I have to dilute the first by the second. Now, the dialyzers are not permeable to albumin. Therefore the violet color indicates that the blood serum in this case contains ferments which the body is making to split up some foreign substance in the blood, such as I suspected and obtained from the hospital. The test is positive. Mr. Seabury, how long have you felt as you say that you do?" "Several weeks," the man returned weakly. "That is fortunate," cried Kennedy, "fortunate that it has not been several months." He paused, then added the startling statement, "Mr. Seabury, I can find no evidence here of poison. As a matter of fact, the wonderful Abderhalden test shows me that you have one of the most common forms of internal disease that occur for the most part in persons at or after middle life, about the age of fifty, more common in men than in women--a disease which taken in time, as it has been revealed by this wonderful test, may be cured and you may be saved--an incipient cancer of the stomach." Kennedy paused a moment and listened. I fancied I heard someone in the hall. But he went on, "The person whom you suspect of poisoning you--" There came a suppressed scream from the door, as it was flung open and Agatha Seabury stood there, staring with fixed, set eyes at Kennedy, then at her husband. Mechanically I looked at my watch. It was precisely eight. Kennedy had evidently prolonged the test for a purpose. "The person whom you suspected," he repeated firmly, "is innocent!" A moment Agatha stood there, then as the thing dawned on her, she uttered one cry, "Judson!" She reeled as Kennedy with a quick step or two caught her. Seabury himself seemed dazed. "And I have--" he ejaculated, then stopped. Kennedy raised his hand. "Just a moment, please," he interrupted, as he placed Mrs. Seabury in a chair, then glanced hastily at his watch. She saw the motion and seemed suddenly to realize that it was nearing the time for Sherburne to call up. With a mighty effort she seemed to grip herself. She had just been shocked to know that she was charged unjustly. But had she been cleared from one peril only to fall a victim to another--the one she already feared? Was Sherburne to escape, after all, and ruin her? The telephone tinkled insistently. Kennedy seized the receiver. "Who is it?" we heard him ask. "Mr. Sherburne--oh yes." Mrs. Seabury paled at the name. I saw her shoot a covert glance at her husband, and was relieved to see that his face betrayed as yet no recognition of the name. She turned and listened to Kennedy, straining her ears to catch every syllable and interpret every scrap of the one-sided conversation. Quickly Craig had jammed the receiver down on a little metal base which we had not noticed near the instrument. Three prongs reaching upward from the base engaged the receiver tightly, fitting closely about it. Then he took up a watch-case receiver to listen through, in place of the regular receiver. "Sherburne, you say?" he repeated. "H. Morgan Sherburne?" Apparently the voice at the other end of the wire replied rather peevishly, for Kennedy endeavored to smooth over the delay. We waited impatiently as he reiterated the name. Why was he so careful about it? The moments were speeding fast and Mrs. Seabury found the suspense terrific. "Must pay--we'll never get anything on you?" Craig repeated after a few moments further parley. "Very well. I am commissioned to meet you there in ten minutes and settle the thing up on those terms," he concluded as he clapped the regular receiver back on its hook with a hasty good-by and faced us triumphantly. "The deuce I won't get anything. I've got it!" he exclaimed. Judson Seabury was too stunned by the revelation that he had a cancer to follow clearly the maze of events. "That," cried Kennedy, rising quickly, "is what is known as the telescribe--a new invention of Edison that records on a specially prepared phonograph cylinder all that is said--both ways--over a telephone wire. Come!" Ten minutes later, in a cab that had been waiting at the door, we pulled up at the Vanderveer. Without a word, leaving Judson Seabury and his wife in the waiting cab, Craig sprang out, followed by me, as he signaled. There was Sherburne, brazen and insolent, in the cafe as we entered, from a rear door, and came upon him before he knew it, our friend, Dunn, whom we had met in the lobby, hovering concealed outside, ready to come to our assistance. In a moment Kennedy was at Sherburne's elbow, pinching it in the manner familiar to international crooks. "Will you tell me what your precise business is in this hotel?" shot out Craig before Sherburne could recover from his surprise. Sherburne flushed and flared--then became pale with rage. "None of your damned insolence!" he ground out, then paused, cutting the next remark short as he gritted, "What do you mean? Shall I send a wax impression of that key--" Kennedy had quickly flashed the cylinder of the telescribe before his eyes and instinctively Sherburne seemed to realize that with all his care in using typewriters and telephones, some kind of record of his extortion had been obtained. For a moment he crumpled up. Then Kennedy seized him by the elbow, dragging him toward a side door opposite that at which our cab was standing. "I mean," he muttered, "that I have the goods on you at last and you'll get the limit for blackmail through this little wax cylinder if you so much as show your face in New York again. I don't care where you go, but it must be by the first train. Understand?" A moment later we returned to the cab, where it had pulled up in the shadow, away from the carriage entrance. "You--you'll forgive me--for my--unjust suspicions--Agatha?" we heard a voice from the depths of the cab say. Kennedy pulled me back in time not to interrupt a muffled "Yes." Craig coughed. As he reached a hand in through the cab door to bid good-night to the reunited couple, I saw Mrs. Seabury start, then turn and drop into her handbag the key which Kennedy had extracted from Sherburne's pocket in the _mêlée_ and now conveyed back to her in the handshake. CHAPTER VII THE DIAMOND QUEEN "Meet _Sylvania_ Quarantine midnight. Strange death Rawaruska. Retain you in interest steamship company. Thompson, Purser." Kennedy had torn open the envelope of a wireless message that had come from somewhere out in the Atlantic and had just been delivered to him at dinner one evening. He read it quickly and tossed it over to me. "Rawaruska," I repeated. "Do you suppose that means the clever little Russian dancer who was in the 'Revue' last year?" "There could hardly be two of that unusual name who would be referred to so familiarly," returned Craig. "Curious that we've had nothing in the wireless news about it." "Perhaps it has been delayed," I suggested. "Let me ring up the _Star_. They may have something now." A few minutes later I rejoined Craig at the table. A report had just been received that Rawaruska had been discovered, late the night before, unconscious in her room on the _Sylvania_. The ship's surgeon had been summoned, but before he was able to do anything for her she died. That was all the report said. It was meager, but it served to excite our interest. Renée Rawaruska, I knew, was a popular little Russian dancer abroad who had come to America the season previous and had made a big hit on Broadway. Beautiful, strange, fiery, she incarnated the mysterious Slav. I knew her to be one of those Russian dancers before whose performances Parisian audiences had gone wild with admiration, one who had carried her art beyond anything known in other countries, fascinating, subtle. Hastily over the telephone Kennedy made arrangements to go down to Quarantine on a revenue tug that was leaving to meet the _Sylvania_. It was a weird trip through the choppy winter seas of the upper bay and the Narrows, in the dark, with the wind cold and bleak. The tug had scarcely cast off from the Battery, where we met it, when a man, who had been watching us from a crevice of his turned-up ulster collar, quietly edged over. "You are Professor Kennedy, the detective?" he began, more as if asserting it than asking the question. Craig eyed him a moment, but said nothing. "I understand," he went on, not waiting for a reply, "that you are interested in the case of that little Russian actress, Rawaruska?" Still Kennedy said nothing. "My name is Wade--of the Customs Service," pursued the man, nothing abashed. Sticking his head forward between the corners of his high collar he added, in a lowered voice, "You have heard, I suppose, of the great amber diamond, 'The Invincible'?" Kennedy nodded and I thought hurriedly of all the big stones I had ever heard--the Pitt, the Orloff, the Koh-i-noor, the Star of the South, the Cullinan, and others. "The Invincible, you know," he added, "is the largest amber diamond in the world, almost the size of the famous Cullinan, over three hundred carats. It was found in the dry diggings of the Vaal River, a few miles from Kimberley. The dry diggings are independent of the De Beers combine, of course. Well, its owner has always been in the position of Mark Twain's man with the million-dollar bank-note who found it too large to cash. No one knows just what an amber diamond of that size is really worth. This one is almost perfect, resembles the huge top of a decanter stopper. It's a beautiful orange color and has been estimated at--well, as high as close to a quarter of a million, though, as I said, that is all guesswork." "Yes?" remarked Kennedy, more for politeness than anything else. Wade leaned over closer. "The Invincible," he whispered, shielding his lips from the keen, biting gale, "was last known to belong to the De Guerres, of Antwerp. One of my special agents abroad has cabled me to look out for it. He thinks there is reason to believe it will be smuggled into America for safe keeping during the troubles in Belgium." It seemed to make no difference to the customs man that Kennedy did not exactly welcome him with open arms. "The De Guerres are well-known dealers in diamonds, one of the leading houses in the 'city of diamonds,' as Antwerp has been called. One of the De Guerres is on the _Sylvania_, the junior partner--" he paused, then added,--"the husband, I believe, of Rawaruska. I thought perhaps you might be willing to try to help me." "I should be glad to," replied Kennedy tersely, pondering what the officer had told us. Nothing more was said on the trip and at last we came to the _Sylvania_, lying grim and dark of hull off the little cluster of Quarantine buildings, with myriads of twinkling lights on her, far above but scarcely relieving the blackness of the leviathan form. Thompson, the purser, a quiet, unexcitable Englishman, met us as we came over the side, and for the moment we lost sight of our new-found friend, Wade. "Perhaps you didn't know it," informed Thompson as we made our way through the ship, "but Rawaruska was married--had been for some time." "Who was her husband?" queried Kennedy, seeking confirmation of what we had already heard. "Armand De Guerre, a Belgian, of Antwerp," was the reply, "one of the partners in a famous old diamond-cutting firm of that city." Kennedy looked at the purser keenly for a moment, then asked, "Were they traveling together?" "Oh, yes,--that is, he had engaged a room, but you know how crowded the boats are with refugees fleeing to America from the war. He gave up his room, or rather his share of it, to a woman, a professional saleswoman, well known, I believe, in Antwerp as well as the Rue de la Paix in Paris and Maiden Lane and Fifth Avenue of your city, a Miss Hoffman--Elsa Hoffman. She shared the room with Rawaruska, while De Guerre took his chances in the steerage." As we walked down one of the main corridors we noticed ahead of us a seemingly very nervous and excited gentleman engaged apparently in a heated conversation with another. "Monsieur De Guerre," whispered Thompson as we approached. The two seemed to be just on the point of parting, as we neared them, and, I think, our approach hastened them. I could not hear what one of them said, but I heard De Guerre almost hiss, as he turned on his heel, "Well, sir, you were the last one seen with her alive." A moment later the purser introduced us to De Guerre. There was something about him which I can hardly express on paper, a sort of hypnotic fascination. I felt instinctively that such a man would wield a powerful influence over some women. Was it in his eyes, or was it merely his ardent foreign grace? "You _must_ find out the truth," he cried eagerly. "Already they are saying that it was suicide. But I cannot believe it. It cannot be. No,--she was murdered!" Kennedy ventured no opinion, but now, more than ever, hastened to signify to the purser that he wanted to look over the ground as quickly as possible before the ship docked. Rawaruska, we found, had occupied Room 186, on the port side of one of the lower decks. Kennedy seemed to be keenly interested, as we approached the room in which the body still lay, awaiting arrival at the pier a few hours later. The stateroom, apparently, ran to the very skin of the vessel and the ports opened directly on the water, not upon an outside deck, as with the rooms above it. It was an outside room at the end of a sort of cross alleyway, and it was impossible that anyone could have reached it except through the corridors. Attached to it was a little bath and directly across from the bath, on the other side, was another small room which was occupied by her maid, Cecilie, a French girl. In the main bedroom was a double bed, a couch, a wardrobe, and a small, thin-legged writing or dressing table. On the white bed lay the now cold and marble figure of the once vivacious little dancer who had enchanted thousands in life--petite, brunette, voluptuous. Rawaruska was beautiful, even in death. Her finely chiseled features, lacking that heaviness which often characterizes European women, were, however, terribly drawn and her perfect complexion on which she had prided herself was now all mottled and bluish. As Kennedy examined the body, I could not help observing that there seemed to be every evidence that the girl had been asphyxiated in some strange manner. Had it been by a deft touch on a nerve of her beautiful, soft neck that had constricted the throat and cut off her breath? I had heard of such things. Or had it been asphyxiation due to a poison that had paralyzed the chest muscles? The purser, as soon as we came aboard, had summoned the ship's surgeon, and we had scarcely arrived at Rawaruska's room when he joined us. He was one of those solid, reliable doctors, not brilliant, but one in whom you might place great confidence, a Dr. Sanderson, educated in Edinburgh, and long a follower of the sea. "Was there any evidence of a struggle?" asked Kennedy. "No, none whatever," replied the doctor. "No peculiar odor, no receptacle of any kind near her that might have held poison?" "No, nothing that could have been used to hold poison or a drug." Kennedy was regarding the face of the little dancer attentively. "Most extraordinary," he remarked slowly, "that congested look she has." "Yes," agreed Dr. Sanderson, "her face was flushed and blue when I got to her--cyanotic, I should say. There seemed to be a great dryness of her throat and the muscles of her throat were paretic. Her pupils were dilated, too, and her pulse was rapid, as if from a greatly increased blood pressure." "Was she conscious?" asked Kennedy, almost reverently turning over her rigid body and looking at the back of her neck and the upper spine. "Did she recognize anything, say anything?" "She seemed to be in a state of amnesia," replied Sanderson slowly. "Evidently if she had seen anything she had forgotten or wouldn't tell," he added cautiously. "Who found her?" asked Craig. "How was she discovered?" "Why, Miss Hoffman found her," replied the purser quickly. "She called one of the stewards. She had been sitting in the library reading until quite late and Rawaruska had retired early, for she was not a good sailor, they tell me. It must have been nearly midnight when De Guerre and a friend, pausing at the library door on their way from the smoking room, saw Miss Hoffman, and all three stopped in the Ritz restaurant for a bite to eat. "De Guerre walked down the corridor with Miss Hoffman afterwards," he continued, "and left her as she went into the room with his wife. Perhaps a minute later--long enough anyway so that he had reached the other end of the corridor--she screamed. She had turned on the light and had found Rawaruska lying half across the bed, unconscious. Miss Hoffman called to the steward to summon Dr. Preston, but he came to me first, instead." "Dr. Preston?" repeated Kennedy. "Yes, a young American physician, the friend who had been with De Guerre in the smoking room part of the evening, and later made up the party in the restaurant," vouchsafed Sanderson. "The man De Guerre was talking to as we came down the hall," put in Thompson. "H'm," mused Kennedy, evidently thinking of the remark we had overheard. "I've talked with him now and then myself," admitted Sanderson; "a bright fellow who has been studying abroad and after many adventures succeeded in getting across the border into Holland and thence to England. He managed to squeeze into the steerage of the _Sylvania_, though, of course, like De Guerre, he was classed as a first-cabin passenger. He had become very friendly with Rawaruska and her party while they were waiting for bookings in London." Thompson leaned over. "The steward in the corridor tells me," he said in a low tone, "that early in the evening Dr. Preston and Rawaruska were on the promenade deck together." I tried vaguely to piece together the scraps of information which we had gleaned. Kennedy, however, said nothing, but was now leaning over the body of the little dancer, looking at the upper region of her spine attentively. Quietly, from a group of three or four little red marks on her back he squeezed out several drops of liquid, absorbing them on a piece of sterile gauze. A moment later, De Guerre, who had quietly slipped away during the examination, as if unable to bear the sight of the tragedy, returned, and with him was a young woman. "Miss Elsa Hoffman," he introduced. Elsa Hoffman was of a fascinating type, tall, finely gowned, of superb poise, physically perfect. One could not help admiring her deep blue eyes and blonde radiance. Indeed, I felt that one must rely much on her attractions in pursuit of her business of selling gems to wealthy men and women. Still, in spite of her evident poise, the tragedy seemed to have oppressed and unnerved her. She did not seem to be able to add much to the scanty stock of facts we had, even after repeating the story of her discovery of Rawaruska, which was substantially as the purser had already told it. "I--I think perhaps Mr. Kennedy ought to question Cecilie," she suggested finally, turning toward De Guerre, who nodded his assent. A sudden movement in the passageway followed, and the door opened quietly. A man entered, a youngish fellow of fine physique and attractive face. I recognized him immediately as Dr. Preston. His apparently usually debonair manner was visibly subdued by the presence of death. Evidently he had just heard that someone was investigating the tragedy and had hastened to be present. Both De Guerre and Elsa nodded to him, a trifle coldly. Only a moment did he pause to look at the drawn face on the pillow, then stood apart, ill at ease until Kennedy had finished his minute examination. As Kennedy moved away from the bed, Dr. Preston contrived to place himself near him and apart from the rest. "Mr. Kennedy," he began in a husky undertone, "they tell me you have been engaged to investigate this--this awful affair." Kennedy assented. "If there is anything I can do to help you," Preston added anxiously, "I hope you will command me. In fact," he added as Kennedy nodded while Preston glanced covertly at De Guerre and Miss Hoffman, "I hope you'll get at the truth." "Thank you," responded Kennedy, meeting his eye squarely this time; "I shall be glad to call on you if occasion arises." I watched Preston closely, not quite making out just what he was driving at, nor the reason for the strained relations that now seemed to exist among the former friends. Still following Kennedy's every motion, Preston retired to the position of a more than interested spectator. CHAPTER VIII THE ANESTHETIC VAPORIZER Craig had completed a hasty search of the room, with its little dressing table, two trunks, and a cabinet. Everything seemed to have been kept in a most neat and orderly manner by the attentive Cecilie, who was apparently a model servant. The little white bathroom was equally immaculate, and Kennedy passed next to an examination of the little room of the French maid. Cecilie was a pretty, dark little being, with snapping black eyes, the type of winsome French maid that one would naturally have expected Rawaruska, with her artist's love of the beautiful, to have picked out to serve her dainty self. As I ran my eye over the group that was now intently watching Kennedy at work, I fancied I caught Elsa Hoffman eyeing Cecilie sharply, and I am sure that once at least those black eyes snapped back a wireless message of defiance at the penetrating eyes of blue. I could feel instinctively the atmosphere of hostility between the two women. "The door was not locked, you say?" repeated Craig, following up one of the first of his own questions to Cecilie, which had resulted in unearthing this new fact. "Non, monsieur," replied Cecilie in accented English which was charming. "Mam'selle--we all called her that, her stage name,--used to leave it open in case of fire or accident. She had a terrible fear of drowning. You know there have been some awful wrecks lately, and she was, oh, so nervous." "But her valuables?" prompted Craig quickly, watching the effect of his question. "All in the ship's safe, in care of the purser," replied Cecilie. "So were Miss Hoffman's." "Yes," corroborated Thompson, "and, besides, the corridors and passageways are well patrolled by stewards at all times." The search of Cecilie's room, which was smaller and more scantily furnished, took only a few minutes. A suppressed exclamation from Craig served to divert my attention from the study of those around me to the study of Kennedy himself, and what he had discovered. Hidden away in the back of a drawer in a small chiffonier, he had come across several articles that aroused interest if they did not whet the blade of suspicion. "_Mon Dieu!_" exclaimed the maid as Kennedy suppressed a smile of gratification at the outcome of the search. "But that is not mine!" Kennedy drew out from the back of the drawer, where it had been tucked, a little silken bag. He opened it. On the surface it seemed that the bag was empty. But as he brought it cautiously closer to his face to peer in, I could see that just a whiff of its contents was enough. "What have you there?" I asked Kennedy, careful that no one else could overhear us. "Cayenne pepper, snuff, and some other chemical," sneezed Craig. "Very effective to throw into the face of anyone," he commented, closing quickly the bag by its loose drawing strings, "that is, if you merely want to blind him and put him out temporarily." I did not pay much attention to the protests of the maid, nor the look of triumph that crossed the face of Elsa Hoffman and surprise exhibited by Dr. Preston. For Kennedy had picked up from the same drawer a little toilet vaporizer, too, and was examining it minutely. As he held it up, I could see, or rather I fancied that it was empty. He pressed the bulb lightly, then seemed to start back quickly. "What's that?" I queried, mystified at his actions. "Something the French secret service spies call the 'bad perfume,'" he returned frankly, "an anesthetic so incredibly rapid and violent that the spies, usually women, who use it wear a filter veil over their own mouths and noses to protect themselves." The whole thing was so queer that I could only wonder what might be the explanation. Cecilie was protesting volubly, now in fair English, now in liquid French, that she knew absolutely nothing of the articles. I wondered whether Rawaruska herself might not have placed them there. Might she not have been a spy, one of those clever little dancers who had wormed themselves by their graceful agility into the good graces of some of the world's leading men and made Russia a recognized diplomatic power? Something like the same idea must have been suggested to Dr. Sanderson, who was standing next me, for he bent over and remarked to me in an undertone, with a significant glance at what Kennedy had discovered, "I suppose you realize that the position of the Russian government has undergone a marked change since the Russian dancers have won international popularity?" I had not thought much about it before, but now that he mentioned it, I could not help a nod of assent. "Why, I have heard," he continued with the air of a man who is imparting a big piece of information, "that the beautiful young women of the imperial ballet mingle in the society of the capitals of the world, make friends with politicians, social leaders, high officials, and exert a great influence in favor of their own country wherever they go. No doubt," he added, "they sometimes convey valuable information to the Foreign Office which could not be obtained in any other way." I was not paying much attention to him, but still the doctor rattled on in an undertone, "Some of these dancers are past masters in the art of intrigue. Do you suppose Rawaruska and the rest have had the task set for them to win back the public opinion of your country, which departed from its traditional policy of friendliness during the Japanese war?" I made no answer. I was engrossed in considering the primary question. Could it have been a suicide, after all? Surely she had removed the evidences of it much better than in any other case I had ever seen. Or, had there been a "triangle," perhaps a quadrangle here? I could not persuade myself that De Guerre cared greatly for his wife, except perhaps to be jealous of anyone else having her. He was too attentive to Elsa Hoffman, and she, in turn, was not of the type to care much for anyone. As for Dr. Preston, although he seemed to have had a friendship for Rawaruska, I could not exactly fit him into the scheme of things. We proceeded up the bay on the _Sylvania_, but were able to discover nothing further that night. As we left the ship at the dock in the morning we ran across Wade, who was quietly directing a dozen or so of his men. "Any trace yet of the Invincible?" asked Craig, stopping in an unostentatious corner. The customs man shook his head gravely. "Not yet," he replied. "But I'm not discouraged. If we miss it here in the customs inspection it will be sure to turn up later. There's a shady jeweler on Fifth Avenue, Margot, who knows these Antwerp people pretty well. I have a man working there, a diamond cutter, and other agents in the trade. Oh, I'll hear about it soon enough, if it is here. Only I'd like to have done something spectacular, something that would count for me at Washington. Have you found out anything?" Briefly Kennedy told him some of the scattered facts we had discovered, just enough to satisfy him without taking him into our confidence. "I'm going to be busy in the laboratory, Walter," remarked Kennedy as our taxicab extricated itself from the ruck of the river-front streets. "I don't know that there is anything that you can do--except--well, yes. I wish you'd try to keep an eye on some of these people--that maid, Cecilie, especially." We had learned that De Guerre was to stop at the Vanderveer and, later in the morning, I dropped into the hotel and glanced over the register. De Guerre was registered there and Cecilie had a little room, also, pending the disposal he would make of her. Miss Hoffman had rooms of her own, which she had evidently re-engaged, with a family in a residential street not far from the hotel. The clerk told me that De Guerre was out, but that the maid had returned after having been out alone, for a short time, also. The lobby of the Vanderveer was fairly crowded with people by this time, and I found no difficulty in keeping in the background and still seeing pretty much everything that went on. It was rather tame, however, and I was still debating whether I should not do something active, when I happened to glance up and catch sight of a familiar face. It was Dr. Preston making inquiries for someone of the room clerk. I dodged back of a pillar and waited, covering myself with an early morning war extra that repeated the news of the night before. A few moments later, Preston, who had received an answer from whomever he was calling, edged his way toward one of the deserted little reception rooms near a side carriage entrance. Carefully, I trailed him. It was some minutes before I could make up my mind to risk passing the door of the little parlor and being discovered, but I was growing impatient. As I glanced in I was astonished to see him talking earnestly to Cecilie. I did not dare stop, for fear one or the other might look up, but I could see that Preston was eagerly questioning her. Her face was averted from me and I could not read even her expression. The passageway was deserted, and if I paused I would inevitably attract attention. So I kept on, turning instinctively in the labyrinth and coming back to the lobby, where I found a position near the telephone booths which gave me a concealed view at least of the door of the parlor around an angle. I waited. Perhaps five minutes passed. Then Cecilie and Dr. Preston suddenly emerged from the reception room. Evidently the maid was anxious to get away, perhaps afraid to be seen with him. With a word, she almost ran down the corridor in the direction of the rear elevators, and Preston, with a queer look on his face, came slowly toward me. Instinctively I drew back into a telephone booth; then it occurred to me that if I emerged just as he passed he would not be likely to suspect anything, and I might have a chance to study him. I did so, and was quite amused at the look of surprise on his face as I greeted him. Still, I do not think he thought I was shadowing him. We paused for a moment on the street, after a conventional exchange of remarks about the tragedy to poor little Rawaruska. "That Miss Hoffman seems to be a very capable woman," I remarked, by way of dragging the conversation into channels into which it seemed unlikely to drift naturally. "Y-yes," he agreed, as I caught a sidelong glance from the corner of his eye. "I believe she has had a rather checkered career. I understand that she was a nurse, a trained nurse, once." There was something about the remark that impressed me. It was made deliberately, I fancied. What his purpose was, I could not fathom, but I felt that in the instant while he had hesitated he had debated and made up his mind to say it. My face betraying nothing to his searching glance, he pulled hastily at his watch. "I'm going downtown on the subway--to clear up some of the muss that this European business has got me in with my bankers," he said quickly. "I'd be glad to have you call on me at any time at the Charlton, just up the avenue a bit. Good-day, sir. I'm glad to have met you. Drop in on me." He was gone, scarcely waiting for me to reply, leaving me to wonder what was the cause of his strange actions. Mechanically I looked at my own watch and decided that I had left Craig undisturbed long enough. CHAPTER IX THE TWILIGHT SLEEP As I entered the laboratory I saw before him a peculiar, telescope-like instrument, at one end of which, in a jar of oxygen, something was burning with a brilliant, penetrating flame. He paused in his work and I hastened to tell him of the peculiar experience I had had in the forenoon. But he said nothing, even at the significant actions of Dr. Preston. "How about those things you found in the maid's room?" I asked at length. "Do they explain Rawaruska's death?" "The trouble with them," he replied, thoughtfully shaking his head, "is that the effects of such things last only for a short time. They might have been used at first--but there was something used afterward." "Something afterward?" I repeated, keenly interested, and fingering the telescope-like arrangement curiously. "What's this?" "One of the new quartz lens spectroscopes used by Dr. Dobbie of the English Government laboratories," he answered briefly. "I think chemists, police officials, coroners and physicians are going to find it most valuable. You see, by throwing the ultra-violet part of the spectrum from a source of light as I obtain from the sparking of iron in oxygen through the lenses of a quartz spectroscope, the lines of many dangerous drugs, especially of the alkaloids, can be distinctly and quickly located in the spectrum. Each drug produces a characteristic kind of line. We use a quartz lens because glass cuts off the ultra-violet rays. Why, even the most minute particle of poison can be detected in this revolutionary fashion." He had resumed squinting through the spectroscope. "Well," I asked, "do you find anything there?" He had evidently been using the piece of gauze on which he had preserved the liquid from the peculiar little marks on Rawaruska's spine. "Narcophin," he muttered, still squinting. "Narcophin?" I repeated. "What is that?" "A derivative of opium--morphine. There's another poison here, too," he added. "What is it?" "Scopolamine," he answered tersely, "scopolamine hydrobromide." "Why," I exclaimed, "that is the drug they use in this new 'twilight sleep,' as they call it." "Exactly," he replied, "the _dämmerschlaf_. I suspected something of the kind when I saw those little punctures on her back. Some people show a marked susceptibility to it; others just the reverse. Evidently she was one of those who go under it quietly and quickly." I looked at Kennedy in amazement. "You can see," he went on, catching the expression on my face, "if it could be used for medical science, it could also be used for crime. That's the way I reasoned, the way someone else must have reasoned." He paused, then went on. "Someone thought out this plan of using narcophin and scopolamine to cause the twilight sleep, to keep Rawaruska just on the borderland of unconsciousness, destroying her memory and producing forgetfulness. That is the _dämmerschlaf_; perception is retained but memory lost. You are acquainted with the test? They show an object to a patient and ask her if she sees it. Say, half an hour later, it is shown again. If she remembers it, it is a sign that a new injection is necessary. "Only in this case the criminal went too far, disregarded the danger of the thing. Scopolamine in too great a quantity causes death by paralysis of respiration--a paralysis, by the way, against which artificial respiration and all means of stimulating are ineffective because of the rigidity of the muscles. And so, you see, in this case Rawaruska died." I could not help thinking of Preston, the young doctor who had been studying in Germany. More than likely he had heard of and had investigated the Frieberg "twilight sleep" treatment. We had made some progress, even though we did not know why or by whom the drugs had been administered. Wade, of the Customs Service, had, as I have said, told us that he had several secret agents about in the trade, constantly picking up bits of information that might interest the Treasury Department. It did not surprise Kennedy, therefore, late in the forenoon, to have Wade call up and tell him that among the early callers at Margot's, the jeweler, was the maid Cecilie. "That was where she must have been before I reached the Vanderveer," I exclaimed. Kennedy nodded. "But why did she go there?" he asked. "And why was she talking with Preston?" Inasmuch as I couldn't answer the questions I didn't try, but waited while Craig reasoned out some method of attack on them. "Since it's known that we're working on the case of Rawaruska," he ruminated half an hour later over an untasted lunch, "we might just as well take the risk of seeing Margot himself. Let's go down and look his shop over." So in the middle of the afternoon, when Fifth Avenue was crowded with shoppers, we paused before Margot's window, looking over the entrancing display of precious stones gleaming out from the rich black velvet background, and then sauntered in, like any other customers. Kennedy engaged the salesman in talk about necklaces and lavallieres, always leading the conversation around to the largest stones that he saw, and dwelling particularly on those that were colored. As I listened, trying to throw in a word now and then that would not sound absolutely foolish, I was impressed by a feeling that Margot's, even though it was such a fashionable place, was what might be called only a high-class shyster's. In fact, I recalled having heard that Margot had engineered several rather questionable transactions in gems. "I'm much interested in orange stones," remarked Kennedy, casually turning up a flawless white diamond and discarding it as if it did not interest him. "Once when I was abroad I saw the famous Invincible, and a handsomer gem than it is I never hope to see." The clerk, ever obliging, replaced the tray before us in the safe and retired toward the back of the shop. "He suspects nothing, at least," whispered Kennedy. A moment later he returned. "I'm sorry," he reported, "but we haven't any such stones in the house. But I believe we expect some in a few days. If you could--" "I shall remember it; thank you," interrupted Kennedy brusquely, as I caught a momentary gleam of satisfaction in his eye. "That's most fortunate. I'll be in again. Thank you." We turned toward the door. In an instant it flashed over me that perhaps they were recutting the big Invincible. "Just a moment, please, gentlemen," interrupted a voice behind us. A short, stocky man had come up behind us. "I thought you did not look like purchasers, nor yet like crooks," he said defiantly. "Did I hear you refer to the Invincible?" It was Margot himself, who had been hovering about behind us. Kennedy said nothing. "Yes," he went on, "I am cutting a large diamond, but it is not like the Invincible. It is much handsomer--one that was discovered right here in this country in the new diamond fields of Arkansas. The diamond itself is already sold. And you would nevair guess the buyer, oh, nevair!" "No?" queried Kennedy. "Nevair!" reiterated Margot. "It could not be delivered to a woman who was once the maid of Rawaruska, the Russian dancer?" Craig asked abruptly. Margot shot a quick and suspicious glance at us. "Then you are, as I suspected, a detectif?" he cried. Kennedy eyed him sharply without admitting the heinous charge. Margot returned his look and I felt that of all sayings that about a dishonest man not being able to look you in the eye was itself the least credible. He laughed daringly. "Well, perhaps you are right," he said. "But whoever it is, he is lucky to have bought a stone like it so cheaply!" The man was baffling. I could not figure it out. Had Margot been simply a high-class "fence" for the disposal and convenient reappearance of stolen goods? We returned uptown to our apartment to find that in the meantime Wade had called up again. Kennedy got him on the wire. It seemed that shortly after we left Margot's Cecilie had called again and had gone off with a small, carefully wrapped package. "A strange case," pondered Kennedy, as he hung up the receiver. "First there is a murder that looks like a suicide, then the sale of a diamond that looks like a fake." He paused a moment. "They have worked quickly to cover it up; we must work with equal quickness if we are to uncover them." With almost lightning rapidity he had seized the telephone again and had our old friend First Deputy O'Connor on the wire. Briefly he explained the case, and arranged for the necessary arrests that would bring the principal actors in the little drama to the laboratory that night. Then he fell to work on a little delicate electrical instrument consisting, outwardly at least, of a dial with a pointer and several little carbon handles attached to wires, as well as a switchboard. I know that Kennedy did not relish having his hand forced in this manner, but nevertheless he was equal to the emergency and when, after dinner, those whom O'Connor had rounded up began to appear at the laboratory, no one would ever have imagined that he had not the entire case on the very tip of his tongue, almost bursting forth an accusation. De Guerre had complied with the police order by sending Cecilie alone in a cab, and later he drove up with Miss Hoffman. Dr. Preston came in shortly afterward, shooting a keen glance at Cecilie, and avoiding more than a nod to De Guerre. Margot himself was the last to arrive, protesting volubly. Wade, of course, was already there. "I really must beg your pardon," began Kennedy, as he ignored the querulousness of Margot, the late arrival, adding significantly, "that is, of all of you except one, for monopolizing the evening." Whatever might have been in their minds to say, no one ventured a word. Kennedy's tone when he said, "Of all of you except one," was too tense and serious. It demanded attention, and he got it. "I am going to put to you first a hypothetical case," he continued quietly. "Let us say that the De Guerres of Antwerp decided to smuggle a great jewel into America for safe keeping, perhaps for sale, during the troublous times in their own country. "Now, any man would know," he went on, "that he had a pretty slim chance when it came to smuggling in a diamond. Besides, everyone knew that the De Guerres owned this particular stone, of which I shall speak later. But a woman? Smuggling is second nature to some women." Quickly he ran over the strange facts that had been unearthed regarding the death of the dainty Russian dancer. "You were right, Monsieur De Guerre," he concluded, turning to the diamond merchant; "it was no suicide. Your wife was killed--unintentionally, it is true,--but killed in an attempt to steal a great diamond from her while she was smuggling it." De Guerre made no answer, save a hasty glance at Wade that did not carry with it an admission of smuggling. "You mean to say, then, Mr. Kennedy," Margot demanded, "that while Rawaruska was smuggling in the big diamond of which you speak someone heard of it and deliberately _murdered_ her?" "Not too fast," cautioned Craig. "Think again before you use those words, 'deliberately murdered.' If it had been murder that was intended, how much more surely it might have been accomplished by more brutal methods--or by more scientific. No, murder was never deliberately intended." He stopped, as if to emphasize the point, then slowly began to distribute to each of us one of the carbon handles I had seen him adjusting to the peculiar little electrical instrument. "Let me reconstruct the case," he hurried on, giving a final twist or two to the instrument itself, now placed before him on a table, with its dial face away from us. "Rawaruska had retired for the night. Where had she placed the diamond? It would probably take a long search to find it. Well, the twilight sleep was chosen because it was supposed to be a safe and sure means to the end. Even if she retained some degree of consciousness, she would forget what happened. That is partly the reason for the treatment, anyhow,--the loss of memory. "Someone believed this was a safe and sure anesthetic. First perhaps a whiff of the secret service 'bad perfume' to insure that she would not cry out--then an injection of narcophin and scopolamine--another--and the twilight sleep. A few minutes, and Rawaruska was unconscious. "Then came the search. Perhaps she was restless. Another injection settled that. At last the great diamond was found. But the twilight sleep meant not forgetfulness but death to Rawaruska!" Craig paused. It was almost as if one could see the word picture of the scene as he painted it. "What was to be done? The diamond must be recut--anything to hide its identity, at once, and at any cost. And Margot? The story of the Arkansas diamond and the sale is a blind. The case is perfect!" Kennedy raised his eyes for the first time from the study of the little electrical machine before him, and caught the eye of Cecilie, holding it, unwilling. "Did you ever hear of the great diamond, the Invincible?" Kennedy smashed out. I felt that it might not have been exactly chivalrous, but it was necessary. Cecilie's breast, which had showed a wildly beating heart as Kennedy told of how her mistress had died, was calmer now. Her air of surprise at the mention of the diamond was perfect. Elsa Hoffman was gazing at her, too, in tense interest. De Guerre was outwardly cool, Margot openly cynical, Preston leaning forward in ill-suppressed excitement. For a moment Kennedy paused again, as if allowing all to collect themselves before he took them by assault. "I have lately been studying," he remarked casually, "the experiments of Dr. Von Pfungen of Vienna showing the protective resistance of the human skin against an electric current. Normally, this resistance averages from seventy to eighty thousand ohms. In the morning, owing to the accumulation of waste products, the resistance may mount to almost double. In persons suffering from nervous anxiety, it decreases to five thousand and even down to a thousand ohms in cases of hysteria. Von Pfungen has also measured a human being's emotional feelings by the electric current. I have a copy of his instrument here. There is one person who sits gripping the carbon electric handle connected with this galvanometer who, to begin with, had a resistance of over sixty thousand. But when I began to tell of how Rawaruska met her death, of the hypothetical case I have built up by my observations and experiments here in this very laboratory, the needle of the galvanometer started to oscillate downward. It went down until it reached thirty-eight thousand at the mention of murder. When I said the case was perfect, it had got as low as under twenty thousand, swinging lower and lower as the person saw hope depart!" Kennedy was no longer paying any attention to the little instrument. As I followed him, I became more and more impatient. What was it he had discovered? Who was it? "Preston," cried Kennedy, suddenly wheeling on the young doctor, "through your regard--honorable, I am sure--for Rawaruska you have let yourself be drawn into doing a little amateur detective work. Let me warn you. Instead of clearing up the case, you merely laid yourself open to suspicion. Fortunately the galvanometer absolves you. You should have known that Cecilie was only a tool. De Guerre, your black wallet, that all diamond dealers carry--thank you, Wade--that's it." Kennedy had turned from Preston to Cecilie, then to De Guerre so suddenly that no one was prepared for the signal he gave to the customs officer. Wade had covered the surprised dealer and was now emptying out the contents of the wallet. There, on the table, gleaming in the light of the laboratory, lay a wonderful brilliant, some three hundred carats--perfect in its blazing crystalline orange beauty. There it lay, a jewel which might charm and arouse the cupidity of two hemispheres. It shone like a thing of life. Yet back of its orange fire lay a black tragedy. Margot was on his feet instantly. "That is not the--" "Just a moment, Mr. Margot," interrupted Kennedy. "I think Mr. Wade will be able to show that it is the Invincible when he matches up the parts that have been hurriedly cut from--from the wonderful Arkansas diamond," Craig added sarcastically. "Miss Hoffman, Dr. Preston tells us that before you were a diamond saleswoman you had been a trained nurse!" The look Elsa Hoffman flashed, as her calm exterior refused to conceal her emotions longer, was venomous. Kennedy was the calmest one of us all as he tapped the little galvanometer significantly with his index finger. "De Guerre," he exclaimed, leaning forward slightly, "you and your lover, Elsa Hoffman, planned cunningly to rob your own brothers. But, instead of robbers merely," he ground out, "you are murderers!" CHAPTER X THE SIXTH SENSE "I suppose you have read in the papers of the mysterious burning of our country house at Oceanhurst, on the south shore of Long Island?" It had been about the middle of the afternoon that a huge automobile of the latest design drew up at Kennedy's laboratory and a stylishly dressed woman, accompanied by a very attentive young man, alighted. They had entered and the man, with a deep bow, presented two cards bearing the names of the Count and Countess Alessandro Rovigno. Julia Rovigno, I knew, was the daughter of Roger Gaskell, the retired banker. She had recently married Count Rovigno, a young foreigner whose family had large shipping interests in America and at Trieste in the Adriatic. "Yes, indeed, I have read about it," nodded Craig. "You see," she hurried on a little nervously, "it was a wedding present to us from my father." "Giulia," put in the young man quickly, giving her name an accent that was not, however, quite Italian, "thinks the fire was started by an incendiary." Rovigno was a tall, rather boyish-looking man of thirty-two or thirty-three, with light brown hair, light brown beard and mustache. His eyes and forehead spoke of intelligence, but I had never heard that he cared much about practical business affairs. In fact, to American society Rovigno was known chiefly as one of the most daring of motor-boat enthusiasts. "It may have been the work of an incendiary," he continued thoughtfully, "or it may not. I don't know. But there has been an epidemic of fires among the large houses out on Long Island lately." I nodded to Kennedy, for I had myself compiled a list for the _Star_, which showed that considerably over a million dollars' worth of show places had been destroyed. "At any rate," added the Countess, "we are burned out, and are staying in town now--at my father's house. I wish you would come around there. Perhaps father can help you. He knows all about the country out that way, for his own place isn't a quarter of a mile away." "I shall be glad to drop around, if I can be of any assistance," agreed Kennedy as the young couple left us. The Rovignos had scarcely gone when a woman appeared at the laboratory door. She was well dressed, pretty, but looked pale and haggard. "My name is Mrs. Bettina Petzka," she began, singling out Kennedy. "You do not know me, but my husband, Nikola, was one of the first students you taught, Professor." "Yes, yes, I recall him very well," replied Craig. "He was a brilliant student, too--very promising. What can I do for you?" "Why, Professor Kennedy," she cried, no longer able to control her feelings, "he has suddenly disappeared." "What line of work had he taken up?" asked Craig, interested. "He was a wireless operator--had been employed on a liner that runs to the Adriatic from New York. But he was out of work. Someone has told me that he thought he saw Nikola in Hoboken around the docks where a number of the liners that go to blockaded ports are laid up waiting the end of the war." She paused. "I see," remarked Kennedy, pursing up his lips thoughtfully. "Your husband was not a reservist of any of the countries at war, was he?" "No--he was first of all a scientist. I don't think he had any interest in the war--at least he never talked much about it." "I know," persisted Craig, "but had he taken out his naturalization papers here?" "He had applied for them." "When did he disappear?" "I haven't seen him for two nights," she sobbed. It flashed over me that it was now two nights since the fire that had burned Rovigno's house, although there was no reason for connecting the events, at least yet. The young woman was plainly wild with anxiety. "Oh, can't you help me find Nikola?" she pleaded. "I'll try my best," reassured Kennedy, taking down on a card her address and bowing her out. It was late in the afternoon before we had an opportunity to call at the Gaskell town house where the Rovignos were staying. The Count was not at home, but the Countess welcomed us and led us directly into a large library. "I'd like to have you meet my father," she introduced. "Father, this is Professor Kennedy, whom Alex and I have engaged to look into the burning of our house." Old Roger Gaskell received us, I thought, with a curious mixture of restraint and eagerness. "I hope you'll excuse me?" asked the Countess a moment later. "I really must dress for dinner. But I think I've told you all I can. I wanted you to talk to my father." "I've heard of the epidemic of fires from my friend Mr. Jameson here, on the _Star_," remarked Kennedy when we were alone. "Some, I understand, have attributed the fires to incendiaries, others have said they were the work of disgruntled servants, others of an architect or contractor who hasn't shared in the work and thinks he may later. I've even heard it said that an insurance man may be responsible--hoping to get new business, you know." Gaskell looked at us keenly. Then he rose and approached us, raising his finger as though cautioning silence. "Do you know," he whispered so faintly that it was almost lost, "sometimes I think there is a plot against me?" "Against _you_?" whispered back Kennedy. "Why, what do you mean?" "I can't tell you--here," he replied. "But, I believe there are detectaphones hidden about this house!" "Have you searched?" asked Kennedy keenly. "Yes, but I've found nothing. I've gone over all the furniture and such things. Still, they might be inside the walls, mightn't they?" Kennedy nodded. "Could you discover them if they were?" asked Gaskell. "I think I could," replied Craig confidently. "Then there's another peculiar thing," resumed Gaskell, a little more freely, yet still whispering. "I suppose you know that I have a country estate not far from my daughter?" He paused. "Of course I know," he went on, watching Kennedy's face, "that sparks are sometimes struck by horses' shoes when they hit stones. But the shoes of my horses, for instance, out there lately have been giving forth sparks even in the stable. My groom called my attention to it, and I saw it myself." He continued looking searchingly at Kennedy. "You are a scientist," he said at length. "Can you tell me why?" Kennedy was thinking deeply. "I can't, offhand," he replied frankly. "But I should like to have a chance to investigate." "There may be some connection with the fire," hinted Gaskell anxiously as he accompanied us to the door. At our own apartment, when we returned, we found our friend, Burke, of the Secret Service, waiting for us. "Just had a hurry call to come to New York," he explained, "and thought I'd like to drop in on you first." "What's the trouble?" asked Kennedy. "Why, there's been a mysterious yacht lurking about the mouth of the harbor for several days and they want to look into it." "Whose yacht do they think it is?" "They don't know, but it is said to resemble one that belongs to a man named Gaskell." "Gaskell?" repeated Craig, turning suddenly. "Yes,--the _Furious_--a fast, floating palace--one of these new power yachts, run by a gas engine--built for speed. Why, do you know anything about it?" Kennedy said nothing. "The revenue cutter _Uncas_ has been assigned to me," went on Burke. "If you have nothing better to do, I'd like to have you give me a hand in the case. You might find it a little different from the ordinary run." "I shall be glad to go with you," replied Craig cordially. "Only, just now I've got a particular case of my own. I'll see you tomorrow at the Customs House, though, if I can." "Good!" exclaimed Burke. "I don't think either of you, particularly Jameson, will regret it. It promises to be a good story." Burke had scarcely left us when Kennedy decided on his next move. We went directly over to the Long Island Railroad station and caught the next train out to Oceanhurst, not a long run from the city. Thus, early in the evening, Kennedy was able to begin, under cover, his investigation of the neighborhood of the Rovigno and Gaskell houses. We entered the Gaskell estate and looked it over as we made our way toward the stable to find the groom. Out on the bay we could see the _Furious_ at anchor. Nearer in shore were a couple of Count Rovigno's speedy racing motor-boats. Along the shore, we saw a basin for yachts, capable even of holding the _Furious_. The groom proved to be a rather dull-witted fellow, and left us pretty much to our own devices. "Ya-as--sparks--I saw 'em," he drawled in answer to Kennedy's question. "So did Mr. Gaskell. Naw--I don't know nawthin' about 'em." He had lumbered out into another part of the stable when I heard a low exclamation from Craig, of "Look, Walter!" I did look in amazement. There were indeed little sparks, in fact a small burst of them in all directions, where there were metal surfaces in close proximity to one another. Kennedy had brought along with him a strange instrument and he was now looking attentively at it. "What is that?" I asked. "The bolometer," he replied, "invented by Professor Langley." "And what does it do?" "Detects waves," he replied, "rays that are invisible to the eye. For instance, just now it tells me that shooting through the darkness are invisible waves, perhaps infra-red rays." He paused, and I looked at him inquiringly. "You know," he explained, "the infra-red rays are closer to the heat rays than those of the upper end of the spectrum and beyond, the ultra-violet rays, with which we have already had some experience." Kennedy continued to look at his bolometer. "Yes," he remarked thoughtfully, half to himself, "somewhere around here there is a generator of infra-red rays and a projector of those rays. It reminds me of those so-called F-rays of Ulivi--or at least of a very powerful wireless." I was startled at the speculations that his words conjured up in my mind. Was the "evil eye" of superstition a scientific fact? Was there a baneful beam that could be directed at will--one that could not be seen or felt until it worked its havoc? Was there a power that steel walls could not hold, which, in fact, was the more surely transmitted by them? Somehow, the fact of the strange disappearance of Petzka, the wireless operator, kept bobbing up in my mind. I could not help wondering whether, perhaps, he had found this strange power and was using it for some nefarious purpose. Could it have been Petzka who was responsible for the fires? But, why? I could not figure it out. Early the next morning we called at the Gaskell town house again. Kennedy had brought with him a small piece of apparatus which seemed to consist of two sets of coils placed on ends of a magnet bar. To them was attached a long flexible wire which he screwed into an electric light bulb socket. Then he placed a peculiar telephone-like apparatus, attached to the other end, to his ears. He adjusted the magnets and carried the thing carefully about the room. At one point he stopped and moved the thing vertically up along the wall, from floor to ceiling. "That's a gas pipe," he said simply. "What's the instrument?" I asked. "A new apparatus for finding pipes electrically, which I think can be just as well applied to finding other things concealed in walls under plaster and paper." He paused to adjust the thing. "The electrical method," he went on, "is a special application of well-known induction balance principles. You see one set of coils receives an alternating or vibrating current. The other is connected with this telephone. First I established a balance so that there was no sound in the telephone." He moved the thing about. "Now, when the device comes near metal-piping, for example, or a wire, the balance is disturbed and I hear a sound. That was the gas pipe. It is easy to find its exact location. Hulloa--" He paused again in a corner, back of Gaskell's desk and appeared to be listening intently. A moment later he was ruthlessly breaking through the plaster of the beautifully decorated wall. Sure enough, in there was a detectaphone, concealed only a fraction of an inch beneath the paper, with wires leading down inside the partition in the direction of the cellar. CHAPTER XI THE INFERNAL MACHINES He ripped the little mechanical eavesdropper out, wires and all, but he did not disconnect the wires, yet. We traced it out, and down into the cellar the wires led, directly, and then across, through a small opening in the foundations into the next cellar of an apartment house, ending in a bin or storeroom. In itself the thing, so far, gave no clew as to who was using it or the purpose for which it had been installed. But it was strange. "Someone _was_ evidently trying to get something from you, Mr. Gaskell," remarked Craig pointedly, after we returned to the Gaskell library. "Why do you suppose he went to all that trouble?" Gaskell shrugged his shoulders and averted his eyes. "I've heard of a yacht outside New York harbor," added Craig casually. "A yacht?" "Yes," he said nonchalantly, "the _Furious_." Gaskell met Kennedy's eye and looked at him as though Craig had some occult power of divination. Then he moved over closer to us. "Is that detectaphone thing out of business now?" he asked, hoarsely. "Yes." "Absolutely?" "Absolutely." Gaskell leaned over. "Then I don't mind telling you, Professor Kennedy," he said in a low tone, "that I am letting a friend of mine from London use that yacht to supply some allied warships on the Atlantic with news, supplies and ammunition, such as can be carried." Kennedy looked at him keenly, but for some moments did not answer. I knew he was debating on how he might properly dove-tail this with Burke's case, ethically. "Someone is trying to find out from eavesdropping just what your plans are, then," remarked Craig thoughtfully, with a significant tap on the detectaphone. A moment later he turned his back to us and knelt down. He seemed to be wrapping the detectaphone up in a small package which he put in his pocket and closing the hole in the wall as best he could where he had ripped the paper. "All I ask of you," concluded Gaskell, as we left a few minutes later, "is to keep your hands off that phase of things. Find the incendiary--yes; but this other matter that you have forced out of me--well--hands off!" On our way downtown to keep the appointment Kennedy had made with Burke the night before, he stopped at the laboratory to get a heavy parcel which he carried along. We found Burke waiting for us, impatiently, at the Customs House. "We've just discovered that the liners over at Hoboken have had steam up for a couple of days," he said excitedly. "Evidently they are waiting to make a break for the ocean--perhaps in concert with a sortie of the fleets over in Europe." "H-m," mused Kennedy, looking fixedly at Burke, "that complicates matters, doesn't it? We must preserve American neutrality." He thought a moment. "I should like to go aboard the revenue cutter. May I?" "Surely," agreed Burke. A few moments later we were on the _Uncas_, Kennedy and Burke in earnest conversation in low tones which I did not overhear. Evidently Craig was telling him just enough of what he had himself discovered so as to enlist Burke's services. The captain in charge of the _Uncas_ joined the conversation a few moments later, and then Kennedy took the heavy package down below. For some time he was at work in one of the forward tanks that was full of water, attaching the thing, whatever it was, in such a way that it seemed to form part of the skin of the ship. Another brief talk with Burke and the captain followed, and then the three returned to the deck. "Oh, by the way," remarked Burke, as he and Kennedy came back to me, "I forgot to tell you that I have had some of my men working on the case and one of them has just learned that a fellow named Petzka, one of the best wireless operators,--a Hungarian or something--has been engaged to go on that yacht." "Petzka?" I repeated involuntarily. "Yes," said Burke, in surprise, "do you know anything about him?" I turned to Kennedy. "Not much," replied Craig. "But you can find out about him, I think, through his wife. He used to be one of my students. Here's her address. She's very anxious to hear from him. I'm sure that if you have any news she will be only too glad to receive it." Burke took the address and a little while later we went ashore. I was not surprised when Kennedy proposed, as the next move, to revisit the cellar in the apartment next to Gaskell's house. But I was surprised at what he said, after we had reached the place. All along I had supposed that he was planning to wait there in hope of catching the person who had installed the detectaphone. That, of course, was a possibility, still. But in reality he had another purpose, also. We had scarcely secreted ourselves in the cellar storeroom, which was in a dark corner where one might remain unobserved even if the janitor entered the cellar, provided he did not search that part, when Kennedy took the receiving headpiece of the detectaphone and placed it over his head, quite as if nothing had happened. "What's the use of that?" I queried. "You ripped the transmitter out up above." He smiled quietly. "While my back was turned toward you, so that you couldn't see," he said, "I slipped the thing back again, only down further where Gaskell wouldn't be likely to find it, even if he looked. I don't know whether he was frank with us, so I thought I'd try the eavesdropping game myself, in place of the man who put this thing in in the first place, whoever he was." We took turns listening, but could hear not a sound. Nor did anyone come into the cellar. So a good part of the afternoon passed, apparently fruitless. My patience was thoroughly exhausted when, suddenly, a motion from Craig revived my flagging interest. I waited impatiently for him to tell me what it was that he heard. "What was it?" I asked finally as he pulled the receivers off his head and stood for a moment, considering. "At first I heard the sound of voices," he answered quickly. "One was the voice of a woman, which I recognized. It was the Countess. The other was the Count. "'Giulia,' I heard him say, as they entered the room, 'I don't see why you should want to go. It's dangerous. And besides, it's none of our business if your father lets his yacht be used for such a purpose.' "'But I want to go, Alex,' she said. 'I will go. I'm a good sailor. It's father's yacht. He won't care.' "'But what's the use?' he expostulated. 'Besides--think of the danger. If it was our business, it might be different.' "'I should think you'd want to go.' "'Not I. I can get all the excitement I want in a motor-boat race without risking my precious neck pulling the chestnuts out of the fire for someone else.' "'Well, I want the adventure,' she persisted, petulantly. "'But, Giulia, if you go tonight, think of the risk--' "That was the last I heard as they left the room, still arguing. Evidently, someone is going to pull off something tonight." It did not take Kennedy long to make up his mind what to do next. He left the cellar hurriedly and in the laboratory hastily fixed up a second heavy and bulky package similar to that which he had taken down to the revenue cutter earlier in the day, making it into two parcels so as to distribute the burden between us. That night we journeyed out to Oceanhurst again. Avoiding the regular road, we made our way from the station to the Gaskell place by a roundabout path and it was quite dark by the time we got there. As we approached the basin we saw that there were several men about. They appeared to be on guard, but since Oceanhurst at that season of the year was pretty deserted and the Gaskell estate was out of the town, they were not especially vigilant. Dark and grim, with only one light showing weakly, lay the yacht, having been run into the basin, now. A hawser had been stretched across the mouth of the basin. Outside was a little tender, while a searchlight was playing over the water all the time. Evidently whatever interference was feared was expected from the water rather than from the land. We slunk into the shadow of a row of bath-houses, in order to get our bearings. On the opposite side from the road that led down from the house, it was not so likely that anyone would suspect that interlopers were hiding there. Still, they were not neglecting that side of the basin, at least in a perfunctory sort of way. Kennedy drew me back into the shadow, deeper, at the sound of footsteps on the boardwalk leading in front of the bath-houses. From our hiding place we could now hear two voices, apparently of sailors. "Do you know the new wireless operator who goes with us tonight?" asked one. "No. They've been very careful of him. I guess they were afraid that someone might get wise. But there couldn't very well be any leak, there. One of those Englishmen has been with him every minute since he was engaged." "They say he's pretty good. Who is he?" "A Servian, he says, and his name sounds as if it might be so." The voices trailed off. It was only a scrap of conversation, but Kennedy had not missed a word of it. "That means Petzka," he nodded to me. "What is he--a Hungarian or a Servian?" I asked quickly. Kennedy had craned his neck out beyond the corner of the bath-houses and was looking at the _Furious_ in the basin. "Come on, Walter," he whispered, not taking time to answer my question. "Those fellows have gone. There's no one at all on this side of the basin and I just saw the men on deck go up the gangplank to the boat-house. They can't do any more than put us off, anyhow." He had watched his chance well. As quickly as we could, burdened down by our two heavy packages, we managed to slip across the boardwalk to the piling that formed that side of the basin. The _Furious_ had swung over with the tide nearer our side than the other. It was a daring leap, but he made it as lightly as a cat, landing on the deck. I passed over the packages to him and followed. Kennedy scarcely paused to glance about. He had chosen a moment when no one was looking, and, bending down under the weight of the packages we dodged back of a cabin. A dim light shining into the hold told us that no one was there and we dived down. It was the work of a moment to secrete ourselves in the blank darkness behind a pile of boxes, aft. A noise startled us. Someone was coming down the steep, ladder-like stairs. A moment later we heard another noise. There were two of them, moving about among the boxes. From our hiding place we could overhear them talking in hoarse whispers, but could not see them. "Where did you put them?" asked a voice. "In every package of explosives and in as many of the boxes of canned goods as I had time. There wasn't much opportunity except while the stuff was in the boat-house." I looked at Kennedy, wild-eyed. Was there treachery in the crew? He was leaning forward as much as our cramped quarters would permit, so as not to miss a word. "All right," said the other voice. "No one suspects?" "No. But the Secret Service has been pretty busy. They suspect something--but not this." "Good. You are sure that you can detonate them when the time comes?" "Positive. Everything is working fine. I've done my part of it. Changing wireless operators gave me just the chance I wanted." "All right. I guess I'll go now." "Remember the signal. As soon as the things are detonated I will get off, some way, by wireless the S O S--as if it came from the fleet, you understand?" "Yes--that will be the signal for the dash. Good luck--I'm going ashore now." As they passed up the ladder, I could no longer restrain myself. "Craig," I cried, "this is devilish!" I thought I saw it all now. In the cases of goods on the _Furious_ were some terrible infernal machines which had been hidden, to be detonated by these deadly rays of wireless. Kennedy was busy, working quickly putting together the parts he had taken from the two packages we had carried. As I watched him, I realized that the burning of the Rovigno house was not the action of an incendiary, after all. It had been done by these deadly rays, probably by mere accident. As nearly as I could make it out, there was a counterplot against the _Furious_. Somewhere was an infernal workshop, possibly hedged about by doors of steel which ordinary force would find hard to penetrate, but from which, any moment, this super-criminal might send out his deadly power. The more I considered it, while Kennedy worked, the more uncanny it seemed. This man had rendered the mere possession of explosives more dangerous to the possessor than to the enemy. Archimedes had been outdone! The problem before us now was not only the preservation of American neutrality, but the actual safety of life. Through the open hatch I could now hear voices on the deck. One was that of a woman, which I recognized quickly. It was Julia Rovigno. "I'll be just as quiet as a mouse," she was saying. "I'll stay in the cabin--I won't be in the way." I could not hear the man's voice in reply, but it did not sound like Rovigno's. It was rather like Gaskell's. Still, we had heard enough to know that Julia Rovigno was on the yacht, had insisted on going on the expedition for the excitement of the thing, just as we had heard over the detectaphone. "Hadn't we better warn her?" I asked Craig, who had paused in his work at the sound of voices. Before he could answer we were plunged in sudden darkness. Someone had switched out the light that had been shining down through the hatchway. Before we knew it the opening to the hatchway had been closed. CHAPTER XII THE SUBMARINE BELL Kennedy groped about for a light, stumbling over boxes and bags. "For heaven's sake, Craig," I entreated. "Be careful. Those packages are full of the devilish things!" He said nothing. At least we had a little more freedom to move and I managed to find my way over to a little round porthole and open it. As I looked out, I almost fainted at the realization. The _Furious_ was under way! We were locked in the hold--virtual prisoners--our only company those dastardly infernal machines, whose very nature we did not know! Helplessly I gazed around me. There seemed to be only this one porthole, open, looking out over the dark and turbulent water, which slipped ominously past as we gained speed. Why had Kennedy not foreseen this risk? I glanced at him. He had found an electric light, connected with the yacht's dynamo, and, before turning it on, closed and covered the port so that it threw no reflection out. Far from being disconcerted, on the contrary, he seemed rather pleased than otherwise at the unexpected turn of events. As I looked at our scant and cramped quarters I could see absolutely no way of getting word to anyone off the _Furious_ who might help us. What he was working on I did not know, but if it was some sort of wireless, even if we were able to send a message, what hope was there that it would get past the delicate wireless detector which this criminal must have somewhere near for tapping messages that were being flashed through the air? Had we not heard him say that the signal was to be an S O S sent, as it were, from the fleet far out on the ocean? I could well have believed that Kennedy could rig up some means of communication. But, if the possessor of this terrible infra-red ray, or wireless wave, secret should learn that we, too, knew it, the only result that he would accomplish would be to insure our destruction immediately. It was a foggy night and a drizzle had set in. The _Furious_ could not under such circumstances make such good speed as she was accustomed to make. Fortunately, also, the waves were not running high. Craig had taken a desperate chance. How would he meet it? I watched him at work, fascinated by our peril. Finishing as quickly as he could, he put out our sole electric light, unscrewed the bulb and attached to the socket a wire which he had connected with the instrument over which he had spent so many precious moments. Through the little porthole he cast a peculiar disk, heavy, such as I had seen him place so carefully aboard the _Uncas_. It sank in the water with a splash and trailed along beside the yacht, held by a wire, submerged, perhaps, ten or twelve feet. He made a final inspection of the thing as well as he could by the light of a match, then pressed a key which seemed to close a circuit. I could feel a dull, metallic vibration, as it were. "What are you doing?" I asked, looking curiously also at an arrangement, like a microphone, which he had placed over his ears. "It works!" he cried excitedly. "What works?" I reiterated. "This Fessenden oscillator," he explained. "It's a system for the employment of sound for submarine signals. I don't know whether you realize it, but great advance has been made recently since it was suggested to use water instead of air as the medium for transmitting signals. I can't stop to explain this apparatus just now, but it is composed of a ring magnet, a copper tube which lies in an air gap of a magnetic field, and a stationary central armature. The magnetic field is much stronger than that in the ordinary dynamo. "The copper tube, which has an alternating current induced in it, is attached to solid disks of steel which in turn are attached to a steel diaphragm an inch thick. In the _Uncas_ I had a chance to make that diaphragm practically a part of the side of the ship. Here I have had to hang it overboard, with a large water-tight diaphragm attached to the oscillator." I listened eagerly, even if I were not an electrical engineer. "The same oscillator," he went on, "is used for sending and receiving, for, like the ordinary electric motor it is also capable of acting as a generator, and a very efficient one, too. All I have to do is to throw a switch in one direction when I want to telegraph or telephone under water, and in the other direction when I want to listen in." I could scarcely credit what I heard. Craig had circumvented even the spectacular wireless. He was actually talking through water. Craig had virtually endowed himself with a sixth sense! I watched him spellbound. Would he succeed in whatever it was that he was planning? I waited anxiously. "There's the answer!" he exclaimed in sudden exultation. "Burke is on the _Uncas_. He tells me that he went to see Mrs. Petzka and she is with him--insisted on going, when she heard that her husband had been engaged by the _Furious_." He waited a moment. "You see, Walter," he resumed, "what I am doing is to send out signals by which the _Uncas_ can locate and follow us. She is fast, but, thank heaven, this yacht has to go slow tonight. Sound travels in water at a velocity of about four thousand feet a second. For instance, I find that I get an echo in about one-twentieth of a second. That is the reflected sound wave from the bottom, and indicates that we are in water of about one hundred feet depth. Then I get another echo in something over two seconds. That is the waves reflected from the _Uncas_, which has been hovering about, waiting for something to happen. They can't be much more than a mile and a half away, now. I had expected to signal them from the shore, a dock or something of the sort, using this oscillator to get around that fellow's wireless. But we're much better off on the boat." I looked at him in amazement. "Surrounded by all this junk that may blow us to kingdom come any second?" I demanded. "Burke says steam is still up on all the ships tied up in the harbor so that they can make a dash for it. They are evidently waiting for that S O S signal." "That's all right," I said in desperation, "But suppose they blow us up, first?" "Blow us up first?" he repeated. "Why, don't you understand? It is not the _Furious_ that they are after. The whole war fleet that is hanging around in this part of the Atlantic is to be blown up in mid-ocean, as part of the plan to aid the escape of the interned ships in New York." "Oh," I breathed, with a sigh of relief, "that's it, is it?" "Yes. We'll get in bad all around if we can't stop it--Burke with the Secret Service and ourselves with Gaskell, who doesn't dream that his yacht is being used for the exact opposite of the purpose for which he thinks he has lent it--to say nothing of the mess that our government will have to face for letting these precious schemers play ducks and drakes with our neutrality." We waited eagerly, Kennedy sending out and receiving the submarine signals, and I peering out anxiously into the almost impenetrable fog. Suddenly, apparently from nowhere in the shifting mist, lights seemed to loom up. Instead of stopping, however, the _Furious_ put on a sudden burst of reckless speed. The _Uncas_ was no match for her at that game. Would she escape finally, after all? A sharp report rang out. The _Uncas_ had sent a shot across our bows, so dangerously close that it snapped one of the cables that held the mast. The vibration of our engine slowed, and ceased, and we lay, idly wallowing in the waves as the revenue cutter, bearing our friend Burke and help, came up. A couple of boats put out from the cutter and in almost no time we could hear the tread of feet and the exchange of harsh words as the government officers swarmed up the ladder to our deck. It was only a moment later that the hatch was broken open and we heard the welcome brogue of Burke, calling, "Kennedy--are you and Jameson all right?" "Right here," sang out Craig, detaching the oscillator and replacing the electric bulb, which he lighted. The commotion on deck was too great for anyone to make much of finding us, two stowaways. The Countess was surprised, however, and, I felt, rather glad to see us at a time when we might, possibly exert some influence in her favor if matters came to a more serious pass. There was scarcely time for a word. Burke's men were working quickly. They had entered the hold, after a word from Kennedy, and far out into the ocean they were casting the boxes and bags overboard, one at a time, as fast as they could. They worked feverishly, as Burke spurred them on, and I must say that it was with the utmost relief that I saw the things thrown over. The boxes sank, but rose again and floated, bobbing up and down, at least some of them, perhaps a third above water and two-thirds below. It was not for several minutes that I noticed that with those who had come aboard the _Furious_ from the cutter stood Bettina Petzka. A moment later she caught sight of Kennedy. "Where is my husband?" she demanded, running to him. Kennedy had no chance to reply. Suddenly a series of flashes shattered the darkness. A terrific roar seemed to rise from the very ocean, while a rain of sparks lighted up great spurts of water and then fell back, to perish in the dark waves. The _Furious_ trembled from end to end. We looked, startled, at each other. But we were all safe. The things had been detonated in the water. "Only the fact that he would have blown himself up prevented him from blowing up the yacht and all the evidence against him, now that we have discovered his plot," cried Burke, excitedly, dashing down the deck. Recovered scarcely from our surprise at the explosion and the queer actions of the Secret Service man, we rushed after him as best we could, Craig leading. He led the way to the little wireless room. The door was bolted on the inside, but we managed soon to burst it open. I shall never forget the surprise which greeted us. In a chair, bound and gagged, as though he had been overcome only after a struggle, sat Petzka. Mrs. Petzka threw herself frantically on him, tearing at the stout cords that held him. "Nikola--what is the matter?" she cried. "What has happened?" Through his gag, which she had loosened a bit, he made a peculiar, gurgling noise. As nearly as I could make out, he was struggling to say, "He came in--surprised me--seized me--locked the door." Julia Rovigno stood rooted to the spot--utterly speechless. There, surrounded by electric batteries, condensers, projectors, regulators, resonators, reflectors, voltmeters, and ammeters, queer apparatus which he had smuggled secretly on the _Furious_, before a strange sort of device, with a wireless headgear still over his ears, stood the owner of at least two of the liners of the belligerents which were to have made the dash for the ocean after he had succeeded by his new wireless ray device in removing the hostile fleet--Count Rovigno himself. CHAPTER XIII THE SUPER-TOXIN "I've got to make good in this Delaney case, Kennedy," appealed our old friend, Dr. Leslie, the coroner, one evening when he had dropped unexpectedly into the laboratory, looking particularly fagged and discouraged. "You know," he added, "they've been investigating my office--and now, here comes a case which, I must confess, completely baffles us again." "Delaney," mused Craig. "Let me see. That's the rich Texas rancher who has been blazing a trail through the white lights of Broadway--with that Baroness Von Dorf and----" "And other war brokers," interrupted Leslie. "War brokers?" queried Craig. "Yes. That's what they call them. They're a new class--people with something to sell to or with commissions to buy for belligerent governments. In Delaney's case it was fifty thousand or so head of cattle and horses, controlled by a syndicate of which he was the promoter. That's why he came to New York, you know,--to sell them at a high price to any European power. The syndicate stands to make a small fortune." "I understand," nodded Kennedy, interested. "Just as though there wasn't mystery enough about Delaney's sudden death," Leslie hurried on, "here's a letter that came to him today--too late." Kennedy took the note Leslie handed him. It was postmarked "Washington," and read: DEAR DALEY: I intended writing to you sooner but haven't felt well enough since I came here. The strangest thing about it is that the doctors I have consulted seem to be unable to tell me definitely what is the matter. I can tell you I have been badly frightened. I seemed to have a lot of little boils on my face and new ones kept coming. I felt weak and chilly and had headaches that almost drove me crazy. Perhaps the thing, whatever it is, has made me insane, but I cannot help wondering whether there may not be something back of it all. Do you suppose someone could have poisoned me, hoping to ruin my beauty, on which, to a great measure, depends my success in my mission to America during the war? Since I came here I have been wondering, too, how you are. If there should be anything in my suspicions, perhaps it would be safest for you to leave New York. There is nothing more I can say, but if you feel the least bit unwell, do not disregard this warning. If you will meet me here, we can arrange the deal with those I represent at almost any price you name. Try hard to get here. As ever, LOUISE. Craig looked up quickly. "Have you communicated with the Baroness?" he asked. Dr. Leslie leaned forward in his chair. "The fact is," he replied slowly, "the woman who calls herself the Baroness Von Dorf has suddenly disappeared, even in Washington. We can find no trace of her whatever. Indeed, the embassy down there does not even admit that she is a war buyer. Oh, the newspapers haven't got the whole Delaney story--yet. But when they do get it"--he paused and glanced significantly at me--"there's going to be _some_ sensation." I recalled now that there had been an air of mystery surrounding the sudden death of Daley Delaney the day before. At least one of the papers had called it "the purple death"--whatever that might mean. I had thought it due to the wild career of the ranchman, perhaps a plain case of apoplexy, around which the bright young reporters had woven a slender thread of romance. Kennedy, however, thought otherwise. "The purple death," he ruminated, turning the case over in his mind. "Have you any idea what the papers mean by that?" "Why, it's one of the most grewsome things you ever heard of," went on Leslie eagerly, encouraged. "In some incomprehensible way the hand of fate seems to have suddenly descended on the whole Delaney entourage. First his Japanese servant fell a victim to this 'purple death,' as they call it. "He had scarcely been removed to a hospital where, after fighting a brave fight, he succumbed to the unknown peril, when the butler was stricken. Delaney himself packed up, to leave, in panic, when suddenly, apparently without warning, the purple death carried him off. In three days three of them have died suddenly. Then came this letter from the Baroness. It set me thinking. Perhaps it _was_ poison--I don't know." Craig read the letter of the Baroness again. "Most interesting," he exclaimed energetically as Dr. Leslie finished. "I shall be only too glad to help you if I can. Could you take us up to Delaney's rooms? Is the body still there?" "No, it has been removed to a private undertaking establishment and the apartment is guarded by police. We can stop at the undertaker's on the way over to the apartment." There could be no doubt that Leslie was considerably relieved to think that Craig would consent to take the case. As for Kennedy, I could see that the affair aroused his interest to the keenest point. "Was anyone associated with Delaney in the syndicate here?" inquired Craig as we settled ourselves in Dr. Leslie's car. "Yes," answered the coroner, hurrying us along, "another member of the syndicate was his friend, Dr. Harris Haynes." "Who is he?" asked Kennedy. "Haynes has been a veterinary, but found that there was more money in the cattle business than in practicing his profession. The needs of European war seemed to offer just the opportunity they needed to reap a quick fortune." "I've heard," nodded Craig, "that conditions abroad have led to a great influx of adventurers with other people's money." "Yes. According to all accounts, Delaney and Haynes have been leading a rather rapid existence since they came to New York. It's quite right. The city is full of queer and mysterious characters, both men and women, who profess to be agents for various foreign governments, often unnamed. Delaney and Haynes have met about all of this curious army, I suppose." "I see," prompted Craig. "Among them, I take it, was this stunning woman who calls herself the Baroness Louise Von Dorf. How friendly were they?" "Well, she spent a great deal of time, when she was in the city, up at the apartment Delaney had rented." Leslie and Kennedy exchanged a significant glance. "Who is she?" asked Craig. "Do you know?" "No one seems to know. Yet she is always plentifully supplied with money and they tell me she talks glibly of those whose 'influence' she can command in Washington." "But she has disappeared," mused Kennedy. "Were there any others?" "Haynes hasn't been proof against their wiles," answered the coroner. "I have found out that he was introduced by one of the 'war brokers' to a Madame Daphne Dupres." "And she?" Leslie shook his head. "I don't know anything about her, except that she lives at the Hotel St. Quentin--the same place, by the way, where Haynes makes his headquarters." Our car pulled up at the private morgue of the burial company to which Delaney's body had been taken. We entered, and Kennedy wasted no time in making a careful examination of the remains of the unfortunate victim. "I couldn't make anything out of it, even after an autopsy," confessed Dr. Leslie. "It seemed as though it were something that had been conveyed by the blood all over the body, something that blocked the capillaries and caused innumerable hemorrhages into organs and tissues, and especially nerve centers." The body seemed to be discolored and variegated in color, with here and there little marks of boils or vesicles. "It looks like something that has depleted the red corpuscles of oxygen," continued Leslie, noticing that Kennedy had drawn off a little of the body fluids, evidently for future study. "As nearly as I could make out there had been a cyanosis in a marked degree. He had all the appearance of having been asphyxiated." "Which seems to have been enough to suggest to some imaginative mind the 'purple death,'" remarked Kennedy dryly. Still, I could not help noticing that it was really no exaggeration to call it the purple death. One of the morgue attendants had called Dr. Leslie aside and a moment later he rejoined us. "They tell me Haynes has been here," he reported. "I left word that any visitors were to be carefully watched." "Strange," muttered Kennedy, absorbing Dr. Leslie's latest information and then looking back at the body, puzzled. "Very strange. Let us go up to the apartment right away." Kennedy stowed the little tube in which he had placed the body fluid safely in his pocket and led the way out again to our waiting car. Delaney had picked out a fashionable neighborhood in which to live. As we entered the bronze grilled door and rode up in the elevator, Kennedy handed each of us a cigar and lighted one himself. I lighted up, too, thinking that perhaps there might be some virtue in tobacco to ward off the unseen perils into which we were going. The wealthy ranchman, evidently, on his arrival in New York had rented an apartment, furnished, from a lawyer, Ashby Ames, who had gone south on account of his health. We entered and found that it was a very attractive place that Ames had fitted up. At one side of a library or drawing-room opened out a little glass sun-parlor or conservatory on a balcony. Into it a dining-room opened also. In fact, the living rooms of the whole suite could be thrown into one, with this sun-parlor as a center. Everything about the apartment was quite up-to-date, also. For instance, I noticed that the little conservatory was lighted brilliantly by a mercury vapor tube that ran around it in a huge rectangle of light. Dr. Leslie and the police had already ransacked the place and there did not seem to be much likelihood that anything could have escaped them. Still, Kennedy began a searching examination after his own methods, while we waited, gazing at him curiously. By the frown on his forehead I gathered that he was not meeting with much encouragement, when, suddenly, he withdrew the cigar from his mouth, looked at it critically, puffed again, then moved his lips and tongue as if trying to taste something. Mechanically I did the same. The cigar had a peculiar flavor. I should have flung it away if Kennedy himself had not given it to me. It was not mere imagination, either. Surely there had been none of that sweetishness about the fragrant Havana when I lighted it on the way up. "What is the matter?" I asked. "There's cyanogen in this room," Craig remarked keenly, still tasting, as he stood near the sun-parlor. "Cyanogen?" I repeated. "Yes, there are artificial aids to the senses that make them much keener than nature has done for us. For instance, if air contains the merest traces of the deadly cyanogen gas--prussic acid, you know--cigar smoke acquires a peculiar taste which furnishes an efficient alarm signal." Dr. Leslie's face brightened as Kennedy proceeded. "That is something like my idea," he exclaimed. "I have thought all along that it looked very much like a poisoning case. In fact, the very first impression I had was that it might have been due to a cyanide--or at least some gas like cyanogen." Kennedy said nothing, and the coroner proceeded. "And the body looked cyanotic, too, you recall. But the autopsy revealed nothing further. I have even examined the food, as far as I can, but I can't find anything wrong with it." There was a noise at the door, outside in the hall, and Dr. Leslie opened it. "Dr. Haynes," he introduced, a moment later. Haynes was a large man, good-looking, even striking, with a self-assertive manner. We shook hands, and taking our cue from Craig, waited for him to speak. "It's very strange what could have carried Delaney off so suddenly," ventured Haynes a moment later. "I've been trying to figure it out myself. But I must admit that so far it has completely stumped me." He was pacing up and down the room and I watched him more or less suspiciously. Somehow I could not get the idea out of my head that he had been listening to us outside. Now and then, I fancied, he shot a glance at us, as if he were watching us. "They tell me at the burial company that you were there today," put in Dr. Leslie, his eyes fixed on Haynes' face. Haynes met his gaze squarely, without flinching. "Yes. I got thinking over what the papers said about the 'purple death,' and I thought perhaps I might have overlooked something. But there wasn't--" The telephone rang. Haynes seized the receiver before any of the rest of us could get to it. "That must be for me," he said with a brusque apology. "Why--yes, I am here. Dr. Leslie and Professor Kennedy are up here. No--we haven't discovered anything new. Yes--I shall keep the appointment. Good-by." The conversation had been short, but, to me at least, it seemed that he had contrived to convey a warning without seeming to do so. CHAPTER XIV THE SECRET AGENTS Dr. Leslie looked at Haynes searchingly. "Who was it?" he asked. "Madame Dupres?" Haynes did not hesitate. "Yes," he nodded. "I had an appointment with her and told her that if I was late it would probably be that I had stopped here." The answer came so readily that I must confess that I was suspicious of it. "Did Madame Dupres know the Baroness Von Dorf?" asked Craig quickly. "Yes, indeed," returned Haynes, then stopped suddenly. "But they didn't travel in the same circle, did they?" asked Dr. Leslie, with the air of the cross-examiner who wished to place on record a fact that might later prove damaging. "Not exactly," answered Haynes, with some hesitation. "You knew her, of course?" added Craig. Haynes nodded. "I wonder if you could locate the Baroness," pursued Kennedy. Haynes seemed to express no surprise at the obvious implication that she was missing. "I have no objection to trying," he answered simply; then, with a glance at his watch, he reached for his hat and stick and excused himself. "I'm afraid I must go. If I can be of any assistance," he added, "don't hesitate to call on me. Delaney and I were pretty closely associated in this deal and I feel that nothing is too much to ask of me if it is possible to clear up the mystery of his death, if there is any." He departed as quickly as he had come. "I wonder what he dropped in for?" I remarked. "Whatever it was, he didn't get it," returned Leslie. "I'm not so sure of that," I said, remembering the brief telephone conversation with Madame Dupres. Kennedy did not appear to be bothering much about the question one way or the other. He had let his cigar go out during Haynes' visit, but now that we were alone again he continued his minute search of the premises. He opened a closet which evidently contained nothing but household utensils and was about to shut the door when an idea occurred to him. A moment later he pulled from the mystic depths an electric vacuum cleaner and dragged it over to the sun-parlor. Without a word we watched him as he ran it over the floor and walls, even over the wicker stands on which the plants stood, and then over the floor coverings and furniture of the other rooms that opened into the conservatory. What he was after I could not imagine, but I knew it was useless to ask him until he had found it or had some reason for telling it. Carefully he removed the dust and dirt from the machine and wrapped it up tightly in a package. We parted from Dr. Leslie at the door of the apartment, promising to keep in touch with him and let him know the moment anything happened. At the first telegraph office Kennedy entered and sent off a long message to our friend Burke of the Secret Service in Washington, asking him to locate the Baroness, if possible, in that city, and to give any information he might have about either Haynes or Madame Dupres. "It's still early in the evening," remarked Kennedy as we left the telegraph office. "Suppose we drop around to the St. Quentin. Perhaps we may run into our friends there." The St. Quentin was a favorite resort of foreigners in New York, and I, at least, entered prepared to suspect everyone. "Not all these mysterious-looking men and women," laughed Kennedy, noticing me as we walked through the lobby, "are secret agents of foreign governments." "Still they look as if they might give you the 'high sign,'" I replied, "particularly if you flashed a bankroll." "I don't doubt it," he agreed, his eye roving over the throng. "I suspect that Scotland Yard and the Palais de Justice might be quite pleased to see some faces here rather than on the other side of the Atlantic." He drew me into an angle and for some moments we studied the passing crowd of diplomats and near-diplomats. A moment later I saw Kennedy bow and, following the direction of his eyes, looked up to a sort of mezzanine gallery. There were Haynes and a most attractive woman, talking earnestly. "Madame Dupres," Craig whispered to me, aside. She was tall, slender, gowned in the most modish manner, and had a foreign way about her that would have fascinated one even more cosmopolitan than a Texas veterinary. Now and then someone would stop and chat with them and it seemed that they were on very good terms, at least with a certain group at the St. Quentin. Kennedy moved out further into the lobby where he was more noticeable; then, with a sudden resolution, mounted the steps to the mezzanine floor and approached Haynes. "Let me introduce Professor Kennedy, Madame Dupres," presented Haynes. Kennedy bowed. Whatever one's opinion of madame, he was forced to admit that she was clever. It was evident, also, that she and Haynes were on very intimate terms, also. "I hope that you will be able to clear up the mystery that the newspapers have found in Mr. Delaney's death," she remarked. "Mr. Haynes has told me that he met you tonight with Dr. Leslie. By the way, has he told you his own theory?" she asked. "We shall do our best," replied Kennedy, meeting her eye in as impersonal a manner as it was possible, for it is always difficult to dissociate a beautiful woman from a case like this and judge her not as a beautiful woman but on the merits of the case. "No, Mr. Haynes has not told me his theory--yet." "I'm very glad to have met you," she added, extending her daintily gloved hand to Kennedy, "and you may be sure that if there is any way in which I can be of service I shall expect you to call on me. Just now I hope you will excuse me. I have some letters to get off--and I will leave you men to discuss Mr. Haynes' theory without being hampered by a mere woman. Never mind, Harris," she added as Haynes made as if to escort her to the ladies' writing room. As Madame Dupres passed down the steps there was no denying that she made a splendid impression. Haynes watched her with a glance that was almost ravenous. There could be no doubt of her influence over him. As she passed through the lobby she paused at the telegraph desk a moment, then went into the writing room. "Yes, I think I have an explanation," began Haynes, when she was out of sight. "I've been trying to figure out what could have killed Delaney. Of course I can only guess, but I don't think it is such a bad guess." "What is it?" asked Craig. "You remember the mercury vapor light?" Kennedy nodded. "Mercury vapor lights of that sort are a pretty good source of ultra-violet rays sometimes," went on Haynes. "Well, doubtless you know that various plants belonging to different families produce free prussic acid. They are really cyanogenetic plants. Light and the assimilation processes depending on light exert a favorable influence on cyanogenesis. For instance, a mixture of citric acid with a much smaller amount of potassium nitrite and a trace of bicarbonate of iron, if exposed to light, will generate hydrocyanic acid. That, I believe, is what actually happens in some plant tissues. Animals rarely touch such plants. I believe that such a process might be aided rather than retarded by ultra-violet rays. What do you think of it?" Craig was following Dr. Haynes keenly. As for me, I was astounded by his frankness. I recalled what Kennedy had already said up in Delaney's apartment, and watched his face covertly. "Your explanation is plausible," was all that Craig said. "By the way, have you found out anything about the Baroness?" "Not a word, yet," replied Haynes unhesitatingly. "She seems to be out of town." "And madame--has she any idea where she is?" Haynes shook his head. "You may rest assured," replied Haynes in a tone that was meant to carry conviction, "that if we can find out we shall be only too happy to do so--ourselves." There was nothing to be gained by further inquiry here, and I could imagine that Kennedy was burning with anxiety to get at work on his own line of inquiry at the laboratory. After a few minutes of conversation we excused ourselves and left the hotel. Craig's air of abstraction was not such as to invite further questioning, and I left him an hour or so later in the laboratory surrounded by his microscopes, slides, and innumerable test-tubes which he had prepared for some exceedingly minute investigation in which his exact soul delighted. How late he worked I do not know, for I did not hear him come into our apartment. But he was up very early, in fact woke me up stirring around the living room. I had scarcely completed dressing, while he scanned the morning papers in a vain hope that some stray news item might shed some light on the mystery in which we were now involved, when the whirr of our door buzzer announced that we had an unusually early caller. Kennedy opened the door and admitted a stranger. He was one of those well-groomed middle-aged men whose appearance denotes with what care they seek by every means to retain youth that is fast passing. I could imagine him calmly calculating even his vices. "My name is Ames--Ashby Ames," he introduced. "Dr. Leslie, the coroner, has suggested that I see you." Ames looked as if he had been traveling all night and had not had a chance to freshen himself up in his haste. "I've just heard about that trouble down at my apartment," he continued, "and, though I had planned a trip for my health to the southern resorts, I thought it best for me to come right back to New York. It's a beastly mess." He had thrown his hat vindictively on the table, though his manner to us was rather that of one seeking advice. "Why," he stormed, "this affair is the limit! I rent my apartment to an apparently reputable person. And what do I find? It is not even a mere scandal. It is worse. The place is closed and guarded--quarantined, as it were. I can't get back into my own rooms!" Kennedy smiled. "I can't blame you for feeling vexed, Mr. Ames," he soothed, "but I'm sure I don't know what I can do for you more than I am doing. We are making every effort to clear the thing up--and I have been on the case, you must remember, less than twelve hours." "Oh, I've no criticism of you," rejoined Ames, somewhat mollified. "I didn't come here to criticise. I came only because I thought you might like to know that I was back in town, and because Dr. Leslie mentioned your name. No, indeed--no criticism. Only," he added, "now that my vacation is spoiled and I am back in town, there is going to be some action--that's all." "It can't come too swiftly for me," encouraged Craig. "I'm going to jump right into this beastly row," pursued Ames aggressively. "This morning I'm going to look these people up. They tell me that Baroness has been spending a good deal of time at my place. Pine business--eh? She's disappeared. But I'll get after that Haynes and the Madame Dupres they tell me about--and I'll let you know if I find out anything." He had not given Kennedy a chance to say anything, and in fact Kennedy did not seem to want to say anything yet. "Just thought I'd drop in," concluded Ames, who hadn't taken a chair, but now extended his hand to us; "I think I'll drop into a Turkish bath and freshen up a bit. Keep in touch with me." We shook hands and Ames departed, bustling out as he had bustled in. Kennedy looked at me and laughed as the door closed. "If we have many more people co-operating with us," he exclaimed, "we may resign and let this case solve itself." "I don't think that is likely," I replied. "Not unless we hear from Burke," he agreed. "There is plenty for me to do in the laboratory--but I do wish Burke would wire." The morning passed, and still there was no word from Burke. "I think we might drop around to the St. Quentin for lunch," suggested Kennedy in the forenoon. "We might pick up some news there." We had scarcely entered when we met Haynes pacing up and down the lobby furiously. "What's the matter?" inquired Craig, eyeing him searchingly. "Why," he replied nervously, sticking his thumbs into his waistcoat pockets and then plunging them into his trousers pockets as if it was with the utmost difficulty he controlled those unruly members from doing violence to somebody, "that fellow Ames from whom Delaney hired the apartment had just returned suddenly to town. I saw him talking to Madame Dupres in the hotel parlor. She seemed a bit nervous, so I went in to speak to her. But she said everything was all right and that she'd meet me out here in a few minutes. It's quarter of an hour now. I think he's threatening her with something." Haynes was evidently worried. I wondered whether he was afraid that Ames might worm from her some secret common to the two, for I did not doubt that Ames was a clever and subtle attorney and capable of obtaining a great deal of information by his kind of kid-glove third degree. "I should like to see both of them," decided Craig quickly. Before Haynes could say anything more, he strode into the hotel parlor. Haynes and I followed a short distance behind. There was an air of tense, suppressed excitement in the group, but of all of us, I felt that Madame Dupres was the coolest. "I see you've lost no time in getting busy," nodded Craig to Ames. "No," he replied easily. "This is certainly a very interesting situation which madame here has just outlined to me." Haynes came up just in time to catch the last words. "I say, Ames," he almost roared, "you may be a clever lawyer, but you must remember that you are also expected to be a gentleman. There are limits to questioning a woman when she has not the advantage of having a friend to advise her." For a moment I thought there was going to be a fight, but Kennedy moved unobtrusively between the two men. As for Madame Dupres, I felt that really she was a match for both of them. Instead of getting mad, however, Ames merely laughed. "Why, Haynes," he said quietly, "I don't think you ought to complain. I understand that you, now representing Delaney's Texas syndicate, have already signed the final contract for the deal with those whom Madame Dupres represents and have received a certified check from them as a first payment to bind the bargain." Haynes turned almost livid, then recovering himself, glanced at Madame Dupres. "Why, Harris, I didn't think there was any secrecy about it now," she said, seeing the change in him. "If there is, I'm sorry." "There isn't," replied Haynes, quickly recovering his composure. "Only I just didn't like to see a lawyer, an outsider, quizzing you, that's all." Jealousy was stamped in every line of Haynes' face. Ames said nothing, but it was impossible to escape the look of gratification which he shot at Kennedy as he brought out the startling new development. Madame Dupres was clever enough to see that no good could come of prolonging an interview for which now there was an excuse to break up. "Take me in to lunch, Harris," she said, slipping her arm familiarly into his. "Good-morning, gentlemen." Somehow I felt that she would have liked to add, "And if you see the Baroness, tell her I have beaten her to it." Ames watched them depart with an air of cynical satisfaction, paused a moment, then in turn excused himself from us. What did it mean? What was behind all this intrigue. Was it merely to get this cattle contract, big as that was? We lunched together at the St. Quentin, and it was evident that Madame Dupres was doing her best to smooth over the ruffled feelings of her lover. Luncheon over, Kennedy plunged with redoubled energy into his laboratory investigation. He said little, but I could tell from his manner that he had found something that was very fascinating to him. CHAPTER XV THE GERM OF ANTHRAX It was not until the middle of the afternoon that there came a sudden, brief message from the Secret Service in Washington: Mr. Craig Kennedy, New York. I have located the Baroness Von Dorf in a private sanitarium here and will have her in New York tonight by eight o'clock. BURKE. "In a private sanitarium--will have her in New York tonight," reread Craig, studying the message. "Then it wouldn't seem that there could be much the matter with her." For a few moments he paced the laboratory floor, alternately studying the boards and the yellow telegram. At last, his face seemed to light up as if he had reasoned something out to his satisfaction. Quickly he reached for the telephone and called Dr. Leslie. "I shall have the Baroness here tonight at eight, Leslie," I heard him say. "Don't tell a soul about it. But I'd like to have you make all the arrangements to secure the attendance of Haynes, Ames, and Madame Dupres here just a bit ahead of that time." There was nothing that I could do to aid Craig more in the hours that remained than to efface myself, and I did it in the most effectual way I could think of, compatible with my interest in the case. I rode down to Dr. Leslie's office and dined hurriedly with him. The only new information I gleaned was that Haynes had visited him during the afternoon and had outlined his theory of cyanogen, which certainly seemed to me to fit in quite readily with the facts. When we reached the laboratory, early, Kennedy was still absorbed in studying his microscope. He said nothing, but apparently had gained an air of confidence which he lacked the night before. The Baroness had not yet arrived, but a few minutes after us came Ashby Ames, still complaining about the closing of his apartment and the inconvenience the whole affair had put him to. Haynes arrived and Ames cut short his tirade, glancing resentfully at the veterinary as though in some way he were responsible for his troubles. Madame Dupres arrived shortly, and I could not help noticing that Haynes was patently jealous of even the nod of recognition she gave to Ames. "I don't think I need say that this is one of the most baffling cases that we have ever had," began Kennedy, with a glance at Dr. Leslie. "It certainly is," chimed in the coroner, as though he had been appealed to for corroboration. "In the first place," resumed Kennedy, "I discovered in the air up there in Delaney's room just a trace of cyanogen." Haynes nodded approvingly, glancing from one to the other of us. "But," added Craig, as if he had built up a house of cards merely to demolish it, "I don't think that cyanogen was the cause of Delaney's death--although it furnished the clew." "What could it have been, then?" demanded Haynes, his face clouding. Kennedy looked at him calmly. "You've heard of anthrax?" he asked simply. "Y-yes," replied Haynes, meeting his eye fixedly. "Murrain--the cattle disease." "That is so deadly to human beings sometimes," added Craig. "Well, I've found something very much like anthrax germs in the sweepings that I took up with the vacuum cleaner up there." Dr. Leslie was listening intently. "I can't see how it could have been anthrax," he put in, slowly shaking his head. "Why, Kennedy, the symptoms were entirely different." "No, this was a poisoning of some kind," added Dr. Haynes. "Dr. Leslie himself tells me that you found traces of cyanogen in the air--and you have just said so, too." Kennedy indicated the microscope. "Take a look at that slide under the lens," he said simply. I was nearest and as he evidently meant each of us to look, I did so. Under the high-power lens I could see some little roundish dots moving slowly through the field. Haynes looked next. "But, Professor Kennedy," he objected, almost as soon as he had time for a good look, "the bacilli of anthrax have normally the form of straight bars strung together in a row." "Yes, rod bacilli," added Dr. Leslie, also looking. "Like long rows of hyphens, slender cylindric, non-motile chains joined end to end." We looked at Craig inquiringly. "Like that," he indicated, substituting another slide. We looked again. The field had somewhat the appearance of an exaggerated war map with dark units of supposed troops. "That's it," nodded Haynes. Kennedy removed the slide. "Those are some anthrax germs I obtained here in the city from a pathologist," he said, turning a switch that threw on in a lamp a peculiar, purplish light. "This is a machine for the propagation of ultra-violet rays." He placed the second slide, with its germs of anthrax, in the light, allowing it to play over the slide. "Now look," he said. We did. Something had evidently happened. The chains were broken and smaller units were moving. "If anthrax germs are exposed for a few seconds, even, to ultra-violet light, they change more or less," Kennedy proceeded. "These new forms are not stable. They quickly change back again into their original form." For about ten minutes we sat in silence while the weird light played as if with ghostly fingers on the deadly invisible peril on the little glass microscope slide. "But if the action of the ultra-violet rays is continued," went on Craig, "the microbe changes into a coccus, and then into a filiform bacillus. This form is stable. And the germ is changed in other respects than mere shape. It has entirely new characteristics. It is a true mutation. It produces a disease entirely different from that of the anthrax bacillus from which it is derived. I have tried it on a guinea pig--and it has died in forty-eight hours." Startled as I was by this remarkable discovery, I yet had time to watch Haynes. He had not taken his eyes off Kennedy once since he began to speak. "In anthrax," continued Craig, "an autopsy reveals an enormous serous swelling, about the point of inoculation, with a large gathering of microbes which are formed in the blood and spleen. Death seems to be due to septic poisoning. But this new microbe--super-toxicus, I think it might well be named--produces no swelling and scarcely any microbes are to be found in the blood. "The lungs are inflamed, with innumerable small abscesses. That is the internal form of the disease from breathing in the spores of these microbes. It has an external form, also, but that is by no means so deadly. One would say that death from the internal form of the disease was due to poisoning. The toxin of this microbe produces a sort of asphyxiation, cutting off and eating up the supply of oxygen. "Such a condition is called cyanosis. That is why in Delaney it had the appearance of cyanogen poisoning. The effect was the same. But the trace of cyanogen in the air was merely a coincidence, Haynes. It wasn't cyanogen that killed. But it was something quite as deadly--and far harder to trace--a new germ!" We listened, fascinated. "A French scientist, a woman, Madame Victor Henri, a student at the Pasteur Institute in Paris, has shown that a new microbe can actually be created from anthrax germs by the use of ultra-violet rays. It is not like anthrax, but may be quite as deadly, perhaps more so. "This discovery," he added earnestly, "proves for the first time that a living organism can be changed suddenly and artificially into an organism of a new and entirely different species. One can scarcely appreciate the importance of it. If the germs of different diseases can be transformed, the germ of one being changed into the germ of another, it will be a first step toward finding a way to change deadly germs into others that will be quite innocuous." Kennedy paused impressively to let the horror of the thing impress itself on our minds. "But this criminal has been working for evil purposes in the wrong direction--creating a disease in order to cover up his tracks!" One could almost feel the net closing. "Delaney has fallen a victim to a new germ of which someone learned in Paris," Craig raced on, inexorably, "a germ that would never, in all probability, be discovered by American doctors, a germ that poisoned safely, surely, and swiftly by its deadly super-toxin." A few moments before there had been a noise of a car outside the laboratory window, but in the excitement of Craig's startling revelation we had paid no attention. A hasty tap at the door interrupted him. Before he could open it a very beautiful woman burst in, followed by a thick-set Irishman. It was the Baroness Von Dorf and our friend Burke. For a moment the two women fairly glared at each other. "I've heard what Professor Kennedy just said," cried the Baroness, her eyes snapping fire. "Fortunately, I had to go to Washington and was able to protect myself by seeming to disappear. If I had stayed in New York another day, there is no telling what might have happened to me. Probably I should have got this disease internally instead of externally. As it was, I thought it would come near ruining my beauty." Burke tossed a yellow slip of paper on the table near Kennedy. "That is something one of our special agents found and brought me today," he exclaimed. Kennedy picked it up and read it, while Burke faced us. The Secret Service man fixed his eyes on Madame Dupres. "As for you, my dear lady," he challenged, "how do you happen to be in New York with one of the greatest international crooks that ever troubled the police of five continents?" "I--in New York?" she shrugged coolly. "Monte Carlo, Paris, Vienna, London--all were dead. I had to come here to make a living." The Baroness drew herself up as if to speak. "You scoundrel--you will give my apartment a bad name with your dirty cattle plague--will you!" ground out a voice harshly at my side. I turned quickly. Ames had clutched Haynes by the throat. We were all on our feet in a moment, but there was no need of separating them. The veterinary was more than a match for the hot-headed little lawyer. "Someone," shot out Kennedy, wheeling quickly, "figured that the cattle deal could be brought about quite naturally if Delaney were dead and the Baroness out of the way. Later he could reap the profit and carry off Madame Dupres into the bargain. And if anything were ever discovered, what more natural than to throw the suspicion on a veterinary who was supposed to know all about anthrax?" Just then a half circle of nickled steel gleamed momentarily in Kennedy's hands. I recognized it as a pair of the new handcuffs that uncoiled automatically, gripping at a mere touch. I saw it all in a flash, as I picked up the paper that Burke had tossed to Kennedy. It was a telegram, and read: A. A., The New Stratfield, Washington. Return immediately. Coroner has Craig Kennedy on case. D. D. "It was a devilish scheme," snapped Kennedy, as the handcuffs circled the fake lawyer's wrists, "but it didn't work, Ames." CHAPTER XVI THE SLEEPMAKER "Perhaps race-horses may be a little out of your line, Mr. Kennedy, but I think you will find the case sufficiently interesting to warrant you in taking it up." Our visitor was a young man, one of the most carefully groomed and correctly dressed I have ever met. His card told us that we were honored by a visit from Montague Broadhurst, a noted society whip, who had lavished many thousands of dollars on his racing-stable out on Long Island. "You see," he went on hurriedly, "there have been a good many strange things that have happened to my horses lately." He paused a moment, then continued: "They have been losing consistently. Take my favorite, Lady Lee, for instance." "Do you think they have been doped?" asked Kennedy quickly, eager to get down to the point at issue, for I had never known Craig to be interested in racing. "I don't know," replied the young millionaire, drawing his eyelids together reflectively. "I've had the best veterinary in the country to look my stable over, and even he can't seem to find a thing that's wrong." "Perhaps a visit out there might show us something," cut in Kennedy, as though he were rather favorably impressed, after all, by the novelty of the case. Broadhurst's face brightened. "Then you will take it up--you are interested?" he queried, adding, "My car is outside." "I'm interested in anything that promises a new experience," returned Craig, "and I think this affair may be of that sort." Broadhurst's stable was out on central Long Island, not far from the pretty and fashionable town of Northbury. As we passed down the main street, I could see that Broadhurst was easily the most popular of the wealthy residents of the neighborhood. In fact, the Broadhurst racing stables were a sort of local industry, one of the show-places of Northbury. As we swung out again into the country, we could see ahead of us some stable-boys working out several fine thoroughbreds on Broadhurst's private track, while a group of grooms and rubbers watched them. The stable itself was a circular affair of frame, painted dark red, which contrasted sharply with the green of the early summer trees. Broadhurst's car pulled up before a large office and lounging-room at one end, above which Murchie, his manager and trainer, had his suite of rooms. The office into which Broadhurst led us was decidedly "horsey." About the place were handsomely mounted saddles, bridles, and whips, more for exhibition than for use. In velvet-lined cases were scores of glittering bits. All the appointments were brass-mounted. Sporting prints, trophies, and Mission easy chairs made the room most attractive. Before a desk sat Murchie. As I looked at him, I thought that he had a cruel expression about his eyes, a predatory mouth and chin. He rose quickly at the sight of Broadhurst. "Murchie, I would like to have you meet my friends, Mr. Kennedy and Mr. Jameson," introduced Broadhurst. "They are very much interested in horses, and I want you to show them about the place and let them see everything." We chatted a moment, and then went out to look at the horses. In the center of the circular group of stalls was a lawn. The stalls of the racers in training were large box stalls. "You have certainly trained a great horse in Lady Lee," remarked Kennedy casually, as we made our way around the ring of stalls. Murchie looked up at him quickly. "Until the last few races, I thought so," he replied, stopping before the stall of the famous racer and opening the door. Lady Lee was a splendid three-year-old bay, a quivering, sensitive, high-strung animal. Murchie looked at her a moment, then at us. "A horse, you know," he said reflectively, "is just as ambitious to win a race as you are to win success, but must have hard training. I keep horses in training eight or nine months out of the year. I get them into shape in the early spring and am very careful what they eat. If they get a vacation, they may eat green foods, carrots, and grass in open field; but when we prepare them for the ring or a race, they must have grain, bran, and soft foods. They must have careful grooming to put the coats in first-class condition, must be kept exquisitely clean, with the best ventilation." "How about exercise?" asked Kennedy. "Well," replied Murchie, "I work out horses according to age, with the distance for fast work gradually increased." Our trip through the wonderful stable over, we returned to the office, Murchie walking ahead with Broadhurst. As we reached the door, Broadhurst turned to us. "I hope you will pardon me," he said, "but there is some business up at the house that I must attend to." "Oh, Mr. Broadhurst," interjected Murchie, "before you go back to town, I want to talk over with you some of the changes that ought to be made about the boys here, as well as their food and quarters." "All right," returned Broadhurst; "jump into the car and ride with me. We can talk on the way, and you can come right back. I'll pick you gentlemen up later." Kennedy nodded, quick to perceive the cue that Broadhurst had given him to watch the stables without Murchie watching us. We sat down in the office, and I looked about at the superb fittings. "Do you think it is possible for an owner to make a financial success of racing without betting?" I asked Kennedy. "Possible, but highly improbable," returned Craig. "I believe they consider that they have an excellent year whenever they clear expenses. I don't know about Broadhurst, but I believe that a good many owners don't bet on their horses. They have seen the glaring crookedness of the thing, especially if they have happened to be officers of jockey clubs or stewards of various race-meets. Personally, I should think a man of Broadhurst's stamp would not permit himself to be made a victim of the leeches of the turf--although he may wager a bit, just to give zest to the race. American racing has often been called a purely gambling affair, and I think, before we get through, that we shall see the reason for much of the public opposition to it." Just then a small man entered the office, and, seeing us, asked for Mr. Murchie. His face was pinched and thin. He wore the latest cut of clothes, but was so very slight that his garments hung loosely on him. One could well imagine that he had tried all sorts of schemes to keep himself down toward the hundred-and-ten-or-twelve-pound mark. He was the very type of jockey. He introduced himself to us as Danny McGee, and I recognized at once the famous twenty-five-thousand-dollar-a-year rider, who had so often successfully defended the Broadhurst colors. "Mr. Murchie has gone up to the house," replied Kennedy to his inquiry. McGee looked us over a minute. "Friends of his?" he asked, in a confidential tone. Kennedy smiled. "Of Mr. Broadhurst's," he said quietly. There was a noticeable change in McGee's manner. "Just out here to look the stable over," went on Kennedy; "a wonderful place." "Yes; we think so," assented McGee. "It seems strange," ventured Kennedy, "that, with all this care, Lady Lee should not be keeping up to her record." McGee glanced at us keenly. "I don't understand it myself," he said. "I suppose lots of people must think it is the fault of the jockey, but I have certainly earned my salary lately with that filly. I don't know what's the matter. I've done the best I can, but in spite of it there's something wrong." He spoke with an air of genuine worry, and, although I tried hard, I must confess that I found it impossible to fathom him. "The filly," he added, "has her regular work-out and the regular feed, and yet she seems to be all tired out most of the time. Even the veterinaries can't seem to find out what's the matter." An awkward silence followed, during which both Kennedy and myself endeavored to conceal our ignorance of horses by saying nothing about them. Finally McGee rose and excused himself, saying that he would be back soon. There were still a few minutes before Murchie would be likely to return. Without saying a word, Kennedy rose and opened the door which led into the stable. Across the lawn in the center we could see a man's figure rapidly retreating through the main entrance, and, somehow or other, I felt that at the sound of the opening of our door he hastened his pace. Kennedy walked quickly around the circle of box stalls until he came again to Lady Lee. He entered the stall and looked the famous racer over carefully. I was wondering what, if anything, he expected to find, when, almost before I knew it, I saw him jab a little hypodermic needle into her neck and withdraw a few drops of blood. Lady Lee reared and snorted, but Kennedy managed to quiet her. He returned the hypodermic, with these few drops of blood, carefully into its case again, and we made our way back to the office. A few minutes later, the drone of Broadhurst's car told us that Murchie had returned. We resumed the talk about horses, upstairs in Murchie's own apartment, which consisted of living-rooms, a library, and bath. It was a luxuriously appointed place, in keeping with the tastes of its occupant. We sat down in the library. I was quite interested in looking about me. For one thing, Murchie's idea of art seemed to be a curious blending of horse and woman. There were pictures of all the string of Broadhurst winners, interspersed with Venuses and actresses. On a little table I noticed, at length, a colored photograph in an oval gilt frame. It was of a very beautiful girl. She was something over medium height, with a fine figure, golden hair, and deep-blue eyes. Somehow, I recalled that I had seen that face before, and when I caught Kennedy looking at it from time to time, I was certain of it. Suddenly it flashed over me that the picture had been published in the _Star_. It was Cecilie Safford. I remembered having read of Murchie's escapades, one of which was his elopement with a pretty young stenographer whom he had met at the horse show a couple of years before. The talk ran along about horses still, but I noticed that Kennedy was even more interested in Murchie's pictures, now, than in his conversation. In the place of honor, over the mantel, hung a portrait, in an artistic panel, of a slender girl with dark hair and hazel eyes, with a soft, swanlike throat and neck, and a somewhat imperious manner of carrying her head. I followed Craig's glance across the room. There, in a frame upon the wall in a corner, hung an enlargement of a group photograph. It was of a middle-aged woman, a little boy, and a little girl. Then I remembered the whole story. At the time of his elopement, Murchie had a wife living. Since then he had been divorced. Although he had promised to marry Cecilie when the divorce was obtained, he was now engaged to marry a wealthy girl, Amélie Guernsey. Broadhurst returned shortly for us, and we made another tour of the stable, on the outside, including the quarters of the innumerable employees. Finally, at a hint from Kennedy that we had seen enough for the present, Broadhurst motored back to the city with us. CHAPTER XVII THE INTER-URBAN HANDICAP That night, instead of going to the laboratory, we walked down Broadway until we came to a hotel much frequented by the sporting fraternity. We entered the restaurant, which was one of the most brilliant in the white-light region, took a seat at a table, and Kennedy proceeded to ingratiate himself with the waiter, and, finally, with the head waiter. At last, I saw why Kennedy was apparently wasting so much time over dinner. "Do you happen to know that girl, Cecilie Safford, that Broadhurst's trainer, Murchie, eloped with?" he asked. The head waiter nodded. "I used to know her," he replied. "She used to come in here a good deal, but you won't find her in the Broadway places any more these days. She's more likely to be over on Eighth Avenue." He mentioned the name of a cabaret saloon. Kennedy paid the check and again we started out. We finally entered a place, down in a basement, and once more Kennedy began to quiz the waiter. This time he had no trouble. Across the room, the waiter pointed to a girl, seated with a young fellow at a round table. I could scarcely believe what I saw. The face had the same features as that of the photograph in the oval gilt frame in Murchie's apartment, but it was not the same face. As I studied her, I could imagine her story without even hearing it. The months of waiting for Murchie to marry her and his callous refusal had been her ruin. Cecilie had learned to drink, and from that had gone to drugs. Her mirror must have told her that she was not the same girl who had eloped with Murchie. Her figure had lost its slim, beautiful lines. Her features were bloated. Her eyes were smaller, and her lips were heavy. Her fresh color had disappeared. She had a gray, pasty look. All she had--her beauty--had vanished. Murchie had been divorced, and was about to marry--but not Cecilie. It was to a young and lovely girl, with such a face of innocence as Cecilie had when Murchie had first dictated a letter to her in the office at the horse show, and had fascinated her with his glittering talk of wealth and ease. The news of his engagement had driven her frantic. Curiously enough, the young fellow with her did not seem to be dissipated in the least. There was, on the contrary, an earnestness about him that one was rather sorry to see in such a place. In fact, he was a clean-cut young man, evidently more of a student than a sport. He reminded me of some one I had seen before. I was getting rather interested in an underworld cabaret when, suddenly, Kennedy grasped my arm. At the same moment, a shot was fired. We jumped to our feet in time to see a young tough, with a slouch like that of the rubbers and grooms at Broadhurst's. The fellow who had been seated with Cecilie was struggling with him for the possession of a pistol, which had been discharged harmlessly. Evidently the tough had been threatening him with it. The waiters crowded around them, and the general _mêlée_ about Cecilie's table was at its height when a policeman came dashing in on the run. The arrest of the gunman and his opponent, as well as of Cecilie as a witness, seemed imminent. Kennedy moved forward slowly, working his way through the crowd, nearer to the table. Instead of interfering, however, he stooped down and picked up something from the floor. "Let's get out of this as quickly as possible, Walter," he whispered, turning to me. When we reached the street, he stopped under an arc-light, and I saw him dive down into his pocket and pull out a little glass vial. He looked at it curiously. "I saw her take it out of her pocketbook and throw it into a corner as soon as the policeman came in," he explained. "What do you think it is?" I asked. "Dope? That's what they all do if they get a chance when they are pinched--throw it away." "Perhaps," answered Kennedy. "But it's worth studying to see what drug she is really using." Late as it was, Craig insisted on going directly to the laboratory to plunge into work. First, he took the little hypodermic needle with which he had drawn several drops of blood from the race-horse, and emptied the contents into a test tube. Finding that I was probably of more use at home in our apartment asleep than bothering Kennedy in the laboratory, I said good-night. But when I awoke in the morning, I found that Kennedy had not been in bed at all. It was as I expected. He had worked all night, and, as I entered the laboratory, I saw him engaged in checking up two series of tests which he had been making. "Have you found anything yet?" I asked. He pointed to a corner where he kept a couple of guinea-pigs. They were sound asleep, rolled up in little fluffy balls of down. Ordinarily, in the morning, I found the little fellows very frisky. "Yes," he said; "I think I have found something. I have injected just a drop of blood from Lady Lee into one of them, and I think he's good for a long sleep." "But how about the other one?" I asked. "That's what puzzles me," ruminated Kennedy. "Do you remember that bottle I picked up last night? I haven't finished the analysis of the blood or of the contents of the bottle, but they seem to contain at least some of the same substances. Among the things I find are monopotassium phosphate and sarcolactic acid, with just a trace of carbon dioxide. I injected some of the liquid from the bottle into the other fellow, and you see what the effect is--the same in both cases." The telephone bell rang excitedly. "Is there a Mr. Kennedy there?" asked Long Distance, adding, without waiting for an answer, "Hold the wire, please." I handed the receiver to Kennedy. The conversation was short, and as he hung up the receiver, Craig turned to me. "It was Broadhurst at the Idlewild Hotel," he said quickly. "Today is the day of the great Interurban Handicap at Belmore Park with stakes of twenty-five thousand dollars. Usually they take the horse over to the track at least a week or two before the race, but as Broadhurst's stable is so near, he didn't do it--hoping he might keep a better watch over Lady Lee. But she's no better. If the horse is being tampered with, he wants to know who is doing it and how." Kennedy paused a moment, then went over to a cabinet and took from it a bottle and a very large-sized hypodermic. We must have been among the first on the field at Belmore Park that day. Lady Lee had been sent over there after we left Northbury the day before, under the care of Murchie and McGee, and had been stabled in the quarters on the track which had been assigned to Broadhurst. With Broadhurst, who was waiting for us, we lounged across the field in the direction of the stables. There was no doubt about it, Lady Lee was not in prime condition. It was not that there was anything markedly wrong, but to the trained observer the famous race-horse seemed to lack just a trifle of the _élan_ which meant a win. While Murchie and the jockey were talking outside to Broadhurst, Kennedy slipped into the stall to look at the racer. "Stand over by that side of the door, Walter," he muttered. "I'll be through in just a minute. I want you to act as a cover." Quickly he jabbed the hypodermic into the horse and pressed down the plunger. Lady Lee reared and snorted as she had done before when he extracted the blood, and instantly Murchie and McGee were crowding past me. But the instant had been long enough for Kennedy. He had dropped the hypodermic into his pocket and was endeavoring to soothe the horse. "I guess she's not very much used to strangers," he remarked coolly. No one thought any more of it, apparently. A few minutes later, Broadhurst rejoined Kennedy and myself. I could see that his face showed plainly he was greatly worried. "I don't understand it," he kept repeating. "And what is worse, the news seems to have leaked out that Lady Lee isn't fit. The odds are going up." Kennedy looked at him fixedly a moment. "If you want to win this race, Mr. Broadhurst," he remarked in a low tone, "I should advise you to watch Lady Lee every minute from now until the start." "What do you mean?" whispered Broadhurst hoarsely. "I can't say yet--only watch." While Broadhurst and Kennedy hovered about the stall on one pretext or another, watching both Murchie and McGee as they directed the rubbers and others who were preparing for the race, I watched the trainer and the jockey minutely. They certainly did nothing, at least now, to excite suspicion. But might not the harm have already been done? Was it too late? When the bell sounded the paddock call, McGee led the racer out of the stall and to the paddock. Presently the field, Lady Lee at the fore, walked past the grandstand and cantered slowly down the course to the starting-post. Meanwhile, following Broadhurst, we had already made our way over to the club-house enclosure. It was not like the old days when there was money everywhere, thousands of dollars in plain sight, in the cash-boxes of the bookmakers, when men rushed wildly about with handfuls of bills of large denomination and bets were made with frequent rapidity. And yet there was still a certain maelstrom of the betting-ring left; but the bookmakers had to carry everything in their heads instead of setting it down on paper. I knew the system, and knew that, in spite of the apparent ease with which it seemed possible to beat it, welshing was almost unheard of. The grandstand was crowded, although it was quite a different crowd from that at race meets of former times and on other tracks. Belmore Park lay within motoring distance of the greatest aggregation of wealth and fashion in the country. It was a wonderful throng. The gay dresses of the women mingled kaleidoscopically with the more somber clothing of the men. Every eye in that sea of moving humanity seemed to be riveted on Lady Lee and her rider. It was a pretty good example of how swiftly inside news at the race-track may become public property. Ill news, on this occasion, seemed to have traveled apace. Field-glasses were leveled at the horse which should have been the favorite, and one could tell, by the buzz of conversation, that this race was the great event of the season. As the jockeys maneuvered for position, one could almost feel that some wonderful feats of memory were being performed by the bookmakers. The odds, during the morning, had gradually lengthened against Lady Lee. Like all thoroughbreds, Lady Lee had a most delicate organism, and the good rider, in such a case, was the one who understood his mount. McGee had, in the past at least, that reputation. He had reached pretty near the top of his profession by knowing how to deal with horses of all types. All this and more I had picked up from the gossip of the track. The barrier was sprung and the flag dropped. They were off! The grandstand rose in a body. For a moment, it seemed to me that McGee had lost his nerve. Alertness at the post is an important factor. He had not got away from the barrier ahead of the field. Another rider, too, had got the rail, and hence the shortest route. I wondered whether, after all, that had been the trouble all along, for nothing can win or lose a race quicker or better than those little failures of the jockey himself. Lady Lee, I had heard it said, was one of those horses that do not require urging, but go to the front naturally. Just now, it did not seem that she was beaten, but that she lacked just the power to lead the field. Did McGee figure that the horses ahead of him were setting such a fast clip that they would drop back to him before the race was over? Cleverly, however, he avoided being pocketed, as those ahead of and beside him tried to close in and make him pull up. Around they went until the horses looked to the naked eye like toys strung on wires. Only the tension of the crowd made one feel that this was no play; it was deadly serious sport. On they sped, watched in a lull of deathly stillness. Surely, I felt, this was indeed a great sight--this acid test of the nerves of men and animals pitted against one another. They were coming into the stretch now! Suddenly, it seemed that, by some telepathic connection, both the horse and the rider caught the electric tension which swayed us in the club-house enclosure. I myself was carried away by the frenzied spirit of the race. Broadhurst was leaning forward, oblivious of everything else in the world, straining his eyes through a field-glass. Murchie was watching the race with a supercilious air, which I knew was clearly assumed. On they came! I could not help wondering whether McGee had not really planned to throw the race. Would he, perhaps at the last moment, lose his nerve? Lady Lee suddenly shot through the field. A mighty shout rose from the entire grandstand. It was over in a matter of seconds. She had finished first by a half-length! She had won the classic and the rich stakes. Pandemonium seemed to reign in the club-house inclosure. Broadhurst slapped Murchie over the back with a blow of congratulation that almost felled him. As for McGee, they nearly carried him off the field on their shoulders. Only Kennedy seemed to be calm. The race had been won--but had the problem been solved? Broadhurst seemed to have forgotten all about his previous appeal to Kennedy in the unexpected joy of winning. We paused awhile to watch the frantic crowd, and once, I recall, I caught sight of a stunning, dark-haired woman grasping Murchie's both hands in an ecstasy of joy. Instantly I recognized Amélie Guernsey. As Kennedy and I motored back to the city alone, he was silent most of the way. Only once did he make a remark. "The Belmore Inn," he said, as we passed a rather cheap road-house some distance from the track. "That's where I heard one of the rubbers say the former Mrs. Murchie was living." That night, Craig plunged back again into work in the laboratory, and I, having nothing else to do, wrote a feature story of the great race for the _Star_. Kennedy made up for the rest he had lost and the strain of the day by a long sleep; but early in the morning the telephone bell rang insistently. Kennedy bounded out of bed to answer it. I could gather nothing from the monosyllables which he uttered, except that the matter under discussion was profoundly serious. Finally, he jammed down the receiver. "Good God, Walter," he exclaimed, "Murchie's been murdered!" CHAPTER XVIII THE TOXIN OF FATIGUE He gave me no time for questions, and I had no ability to reconstruct my own theory of the case as we hustled into our clothes to catch the early morning train. "Broadhurst is at the Idlewild Hotel," Kennedy said, as we left the apartment, "and I think we can make it quicker by railway than by motor." The turfman met us at the station. "Tell me just what happened," asked Kennedy. "No one seems to understand just what it was," Broadhurst explained, "but, as nearly as I remember, Murchie was the lion of the Idlewild grillroom all the evening. He had 'come back.' Once, I recall, he was paged, and the boy told him someone was waiting outside. He went out, and returned, considerably flushed and excited. "'By George,' he said, 'a man never raises his head above the crowd but that there's somebody there to take a crack at it! There must have been some crank outside, for before I could get a look in the dark, I was seized. I managed to get away. I got a little scratch with a knife or a pin, though,' he said, dabbing at a cut on his neck." "What then?" prompted Kennedy. "None of us paid much attention to it," resumed Broadhurst, "until just as another toast was proposed to Lady Lee and someone suggested that Murchie respond to it, we turned to find him huddled up in his chair, absolutely unconscious. The house physician could find nothing wrong apparently--in fact, said it was entirely a case of heart failure. I don't think any of us would question his opinion if it had not been for Murchie's peculiar actions when he came back to the room that time." Murchie's body had been removed to the local undertaking establishment. As Broadhurst drove up there and we entered, Kennedy seemed interested only in the little jab and a sort of swelling upon the neck of the dead man. Quickly he made a little incision beside it, and about ten or a dozen drops of what looked like blood-serum oozed out on a piece of gauze which Craig held. As we turned to leave the undertaker's, a striking, dark-haired girl, with the color gone from her cheeks, hurried past us and fell on her knees beside Murchie's body. It was the woman who had congratulated him the day before, the woman of the panel--Amélie Guernsey. I had not noticed, up to this point, another woman who was standing apart in the crowd, but now I happened to catch her eye. It was the woman whose picture with the two children hung in Murchie's apartment. Kennedy drew me back into the crowd, and there we watched the strange tragedy of the wife that was and the wife that was to have been. Craig hurried back to the city after that, and, as we pushed our way up the ramp from the station, he looked hastily at his watch. "Walter," he said, "I want you to locate Cecilie Safford and let me know at the laboratory the moment you find her. And perhaps it would be well to start at the police station." It seemed to me as though the girl whom we had found so easily the evening before had now utterly disappeared. At the police station she had not been held, but had given an address which had proved fictitious. At the cabaret saloon no one had seen her since the incident of the fight. As I left the place, I ran into Donovan, of the Tenderloin squad, and put the case to him. He merely laughed. "Of course I could find her any time I wanted to," he said. "I knew that was a fake address." He gave me the real address, and I hurried to the nearest telephone to call up Craig. "Have Donovan bring her over here as soon as he can find her," he called back. When I arrived at the laboratory, I found Kennedy engrossed in his tests. "Have you found anything definite?" I asked anxiously. He nodded, but would say nothing. "I've telephoned Broadhurst," he remarked, a moment later. "You remember that the former Mrs. Murchie was at Belmore Inn. I have asked him to stop and get her on the way down here in the car with McGee, and to get Amélie Guernsey at the Idlewild, too." He continued to work. "And, oh yes," he added: "I have asked Inspector O'Connor to take up another line, too." It was a strange gathering that assembled that forenoon. Donovan arrived soon after I did, and with him, sure enough, was Cecilie Safford. A few moments later Broadhurst's car swung up to the door, and Broadhurst entered, accompanied by Amélie Guernsey. McGee followed, with the former Mrs. Murchie. "I don't want another job like that," whispered Broadhurst to Kennedy. "I'm nearly frozen. Neither of those women has spoken a word since we started." "You can hardly blame them," returned Kennedy. Mrs. Murchie was still a handsome woman. She now carried herself with an air of assumed dignity. Amélie Guernsey had regained her color in the excitement of the ride and was, if anything, more beautiful than ever. But, as Broadhurst intimated, one could almost feel the frigidity of the atmosphere as the three women who had played such dramatic parts in Murchie's life sat there, trying to watch and, at the same time, avoid each other's gaze. The suspense was relieved when O'Connor came in in a department car. With him were the young man who had been seated with Cecilie at the table the night of the fight and also the gunman. "The magistrate in the night court settled the case that night," informed O'Connor, under his breath, laying down two slips of paper before Kennedy, "but I have their pedigrees. That fellow's name is Ronald Mawson," he said, pointing to Cecilie's companion, then indicating the gunman, "That's Frank Giani--Frank the Wop." I watched Mawson and Cecilie closely, but could discover nothing. They scarcely looked at each other. McGee, however, glared at both Mawson and the gunman, though none of them said a word. "They used to be out there as stable-boys at Broadhurst's," I heard O'Connor continue, in a whisper. "I think they had a run-in and were fired. Each says the other got him in wrong." A moment later Kennedy began: "When you came to my laboratory the other day, Mr. Broadhurst," he said, "you remarked that perhaps this case might be a little out of my line, but that I might find it sufficiently interesting. I can assure you that I have not only found it interesting, but astounding. I have seldom had the privilege of unraveling a mystery which was so cleverly rigged and in which there are so many cross-currents of human passion." "Then you think Lady Lee was doped?" asked Broadhurst. "Doped?" interjected McGee quickly. "Why, Mr. Broadhurst, you remember what the veterinary said. He couldn't find any signs of heroin or any other dope they use." "That's the devilish ingenuity of it all," shot out Kennedy suddenly, holding up a little beaker in which there was some colorless fluid. "I am merely going to show you now what can be done by the use of one of the latest discoveries of physiological chemistry." He took a syringe and, drawing back the plunger, filled it with the liquid. With a slight jab of cocaine to make the little operation absolutely painless, he injected the fluid into the livelier of our two guinea-pigs. "While you and Murchie were absent the first day that I went out to your stable, I succeeded in drawing off some of the blood of Lady Lee," Craig resumed, talking to Broadhurst. "Here, in my laboratory, I have studied it. Lady Lee, that day, had had no more than the ordinary amount of exercise, yet she was completely fagged." By this time the little guinea-pig had become more and more listless and was now curled up in a corner sound asleep. "I have had to work very hurriedly this morning," Craig continued, "but it has only been covering ground over which I have already gone. I was already studying a peculiar toxin. And from the fluid I obtained from Murchie's body, I have been able to calculate that a deadly dose of that same powerful poison killed him." Kennedy plunged directly from this startling revelation into his proof. "Perhaps you have heard of the famous German scientist, Weichardt, of Berlin," he resumed, "and his remarkable investigations into the toxin of fatigue. Scientists define fatigue as the more or less complete loss of the power of muscles to respond to stimulation due to their normal activity. An interval of rest is usually enough to bring about their return to some degree of power. But for complete return to normal condition, a long interval may be necessary. "As the result of chemical changes which occur in a muscle from contraction, certain substances are formed which depress or inhibit the power of contraction. Extracts made from the fatigued muscles of one frog, for instance, when injected into the circulation of another frog bring on an appearance of fatigue in the latter. Extracts from unfatigued muscles give no such results. More than that, the production of this toxin of fatigue by the exercise of one set of muscles, such as those of the legs in walking, greatly diminishes the amount of work obtainable from other unused muscles, such as those of the arms." Kennedy went on, looking at the sleeping guinea-pig rather than at us: "Weichardt has isolated from fatigued muscles a true toxin of a chemical and physical nature, like the bacterial toxins, which, when introduced into the blood, gives rise to the phenomena of fatigue. This is the toxin of fatigue--kenotoxin. Those who have studied the subject have found at least three fatigue substances--free sarcolactic acid, carbon dioxide, and monopotassium phosphate, which is so powerful that, after the injection of one-fifteenth of a gram, the poisoned muscle shows signs of fatigue and is scarcely able to lift a weight easily lifted in normal conditions. Other fatigue products may be discovered; but, if present in large quantity or in small quantity for a long time, each of the substances I have named will cause depression or fatigue of muscles. "Further than that," continued Kennedy, "the depressing influence of these substances on what is known as striated muscle--heart muscle--is well known. The physician at the Idlewild might very well have mistaken the cause of the relaxation of Murchie's heart. For German investigators have also found that the toxin of fatigue, when injected into the circulation of a fresh animal, may not only bring on fatigue but may even cause death--as it did finally here." Kennedy paused. "Lady Lee," he said, looking from one to the other of his audience keenly, "Lady Lee was the first victim of the fiendish cunning of this--" A shrill voice interrupted. "But Lady Lee won the race!" It was McGee, the jockey. Kennedy looked at him a moment, then tapped another beaker on the table before him. "Weichardt has also obtained, by the usual methods," he replied, "an antitoxin with the power of neutralizing the fatigue properties of the toxin. You thought Lady Lee was not friendly with strangers that morning at the track. She was not, when the stranger jabbed a needle into her neck and pumped an extra large dose of the antitoxin of fatigue into her just in time to neutralize, before the race, the long series of injections of fatigue toxin." Kennedy was now traveling rapidly toward the point which he had in view. He drew from his pocket the little bottle which he had picked up that night in the cabaret saloon. "One word more," he said, as he held up the bottle and faced Cecilie Safford, who was now trembling like a leaf ready to fall: "If one with shattered nerves were unable to sleep, can you imagine what would be a most ideal sedative--especially if to take almost any other drug would be merely to substitute that habit for another?" He waited a moment, then answered his own question. "Naturally," he proceeded, "it might be, theoretically at least, a small dose of those products of fatigue by which nature herself brings on sleep. I am not going into the theory of the thing. The fact that you had such a thing is all that interests me." I watched the girl's eyes as they were riveted on Kennedy. She seemed to be fascinated, horrified. "This bottle contains a weak solution of the toxin of fatigue," persisted Kennedy. I thought she would break down, but, by a mighty effort, she kept her composure and said nothing. "Someone was trying to discredit and ruin Murchie by making the horses he trained lose races--somebody whose life and happiness Murchie himself had already ruined. "That person," pursued Kennedy relentlessly, "was defeated in the attempt to discredit Murchie when, by my injection of the antitoxin, Lady Lee finally did win. In that person's mind, Murchie, not the horse, had won. "The wild excitement over Murchie's vindication drove that person to desperation. There was only one more road to revenge. It was to wait until Murchie himself could be easily overpowered, when an overwhelming dose of this fatigue toxin could be shot into him--the weapon that had failed on the horses turned on himself. Besides, no one--not even the most expert physician or chemist--would ever suspect that Murchie's death was not natural." "That--that bottle is mine--mine!" shouted a wild voice interrupting. "I took it--I used it--I--" "Just a moment, Miss Safford," entreated Kennedy. "That person," he rapped out sharply, picking up the pedigrees O'Connor had handed him, "that person gave the toxin to a poor dope fiend as a sleeping-potion in one strength, gave it to Lady Lee in still another strength, and to Murchie in its most fatal strength. It was the poor and unknown pharmacist described in this pedigree whose dream of happiness Murchie shattered when he captivated Cecilie Safford--her deserted lover, Ronald Mawson." CHAPTER XIX THE X-RAY DETECTIVE "I want to consult you, Professor Kennedy, about a most baffling case of sudden death under suspicious circumstances. Blythe is my name--Dr. Blythe." Our visitor spoke deliberately, without the least perturbation of manner, yet one could see that he was a physician who only as a last resort would appeal to outside aid. "What is the case, Doctor?" queried Craig. The Doctor cleared his throat. "It is of a very pretty young art student, Rhoda Fleming, who returned to New York from France shortly after the outbreak of the war and opened a studio in the New Studio Apartments on Park Avenue, not far from my office," began Dr. Blythe, pausing as if to set down accurately every feature of the "case history" of a patient. "Yes," prompted Craig. "About a week ago," the Doctor resumed, "I was called to attend Miss Fleming. I think the call came from her maid, Leila, but I am not sure. She had suddenly been taken ill about an hour after dinner. She was cyanotic, had a rapid pulse, and nausea. By means of stimulants I succeeded in bringing her around, however, and she recovered. It looked like acute gastritis. "But last night, at about the same time, I was called again to see the same girl. She was in an even more serious condition, with all the former symptoms magnified, unconscious, and suffering severe pains in the abdominal region. Her temperature was 103. Apparently there had been too great a delay, for she died in spite of everything I could do without regaining consciousness." Kennedy regarded the Doctor's face pointedly. "Did the necropsy show that she was--er--" "No," interrupted the Doctor, catching his glance. "She was not about to become a mother. And I doubt the suicide theory, too." He paused and then after a moment's consideration, added deliberately, "When she recovered from the first attack she seemed to have a horror of death and could offer no explanation of her sudden illness." "But what other reason could there have been for her condition?" persisted Kennedy, determined to glean all he could of the Doctor's personal impressions. Dr. Blythe hesitated again, as if considering a point in medical ethics, then suddenly seemed to allow himself to grow confidential. "I'm very much interested in art myself, Professor," he explained. "I suppose you have heard of the famous 'Fête du Printemps,' by Watteau?" Kennedy nodded vaguely. "The original, you know," Dr. Blythe went on hurriedly, "hung in the château of the Comtesse de la Fontaine in the Forest of Compiegne, and was immensely valuable--oh--worth probably a hundred thousand dollars or more." A moment later Dr. Blythe leaned over with ill-suppressed excitement. "After I brought her around the first time she confided to me that it had been entrusted to her by the Comtesse for safe-keeping during the war, that she had taken it first to London, but fearing it would not be safe even there, had brought it to New York." "H'm," mused Kennedy, "that is indeed strange. What's your theory, then,--foul play?" Dr. Blythe looked from Kennedy to me, then said slowly, "Yes--but we can't find a trace of poison. Dr. Leslie--the Coroner--I believe you know him--and I can find nothing, in fact. It is most incomprehensible." I noticed that Kennedy was watching Dr. Blythe rather keenly and, somehow, I fell to trying to fathom both his story and himself, without, I confess, any result. "I should like to look her apartment over," remarked Craig with alacrity, needing no second invitation to take up a mystery that already promised many surprises. The New Studio Apartments were in a huge twelve-story ornate Renaissance affair on upper Park Avenue, an example of the rapidly increasing co-operative idea which the impractical artistic temperament has proved soundly practical. It was really a studio building, too, designed for those artists who preferred luxury and convenience to the more romantic atmosphere of the "Alley"--which is the way the initiated refer to the mews back of Washington Square, known as Macdougal's Alley, famous in fact and fiction. Rhoda Fleming's was a most attractively arranged suite, with a large studio commanding the north light and having a ceiling twice as high as the ordinary room, which allowed of the other rooms being, as it were, on two floors, since their ceilings were of ordinary height. On every side, as we entered, we could see works of art in tasteful profusion. Since the removal of the body of the beautiful but unfortunate young art student, no one had been left there, except the maid, Leila. Leila was herself a very pretty girl, one of those who need neither fine clothes nor expensive jewels to attract attention. In fact she had neither. I noticed that she was neatly and tastefully dressed, however, and wore a plain gold band on the ring finger of her left hand. She seemed to be heartbroken over the death of her mistress, but how much of it was genuine, I could not say, though I am frank to admit that even before I saw her I had determined that she was worth watching. "Show me just how you discovered Miss Fleming," asked Kennedy of Dr. Blythe, getting down to work immediately. "Why," he replied, "when I got here she was lying half across that divan, as if she had fallen there, fainting. Each time a little table had been set for a light dinner and the dinner had been eaten. The remains were on the table. And," Blythe added significantly, "each time there was a place set for another person. That person was gone." Kennedy had turned inquiringly to Leila. "I was engaged only for the day," she answered modestly. "Evenings when Mademoiselle had a little party she would often pay me extra to come back again and clean up. She liked to prepare little chafing-dish dinners--but disliked the cleaning." Dr. Blythe nodded significantly, as though that accounted for the reason why it had seemed to be Leila who had called him in both times. Kennedy and I had found the little pantry closet in the kitchenette where the maid kept the few housekeeping utensils. He took a hasty inventory of the slender stock, among which, for some reason, I noted a bottle of a well-known brand of meat sauce, one of those dark-colored appetizers, with a heavy, burnt-grain odor. Craig's next move was to ransack the little escritoire in the corner of the studio room itself. That was the work of but a few moments and resulted in his finding a packet of letters in the single drawer. He glanced over them hastily. Several of an intimately personal nature were signed, "Arnold Faber." Faber, I knew, was a young art collector, very wealthy and something more than a mere dilettante. Other letters were of business dealings with well-known Fifth Avenue art galleries of Pierre Jacot & Cie., quite natural in view of Miss Fleming's long residence in France. The letters had scarcely been replaced when the door of the studio opened and I caught sight of a tastefully gowned young woman, quite apparently a foreigner acclimated to New York. "Oh, I beg pardon," she apologized. "I heard voices and thought perhaps it was some of Rhoda's relatives from the West and that I could do something." "Good-evening, Miss Tourville," greeted Dr. Blythe, who was evidently well-known to this colony of artists. A moment later he introduced us, "This, by the way, is Miss Rita Tourville, an intimate friend of Miss Fleming, who has the studio above." We bowed, exchanged the conventional remarks that such a tragedy made necessary, and Rita Tourville excused herself. Somehow or other, however, I could not resist the impression that she had come in purposely to see what was going on. On our way out, after promising Dr. Blythe to meet him later in the night at the office of the Coroner, Kennedy, instead of going directly to the street, descended to the basement of the apartment and sought the janitor, who lived there. "I'd like very much to see the rubbish that has come down from Miss Fleming's apartment," he asked, slipping into the janitor's hand a large silver coin. "It's all mixed up with rubbish from all the apartments on that side of the house," replied the janitor, indicating a bulging burlap bag. "Miss Tourville's, also?" queries Craig. The janitor nodded assent. Kennedy surely obtained his money's worth of junk as the janitor spread the contents of the bag on the cellar floor. With his walking stick he pawed over it minutely, now and then stooping to examine something more or less carefully. He had gone through somewhat more than half of the rubbish that had come from the apartments when he came upon what looked like the broken remains of a little one-ounce dark-colored, labelless bottle. Kennedy picked it up and sniffed at it. He said nothing, but I saw his brow knit with thought. A moment later he wrapped it in a piece of tissue paper, thanked the janitor, and we mounted the cellar steps to the street. "I think I'll try to see Faber tonight," he remarked as we walked down the avenue. "It will do no harm at any rate." Fortunately, we found the young millionaire art connoisseur at home, in a big house which he had inherited from his father, on Madison Avenue, in the Murray Hill section. "The death of Miss Fleming has completely upset me," he confessed after we had introduced ourselves without telling too much. "You see, I was quite well acquainted with her." Kennedy said nothing, but I could feel that he was longing to ask questions leading up to whether Faber had been the mysterious diner in the Fleming Studio the night before. "I suppose you are acquainted with Watteau's 'Fête du Printemps'?" shot out Craig, after a few inconsequential questions, watching Faber's face furtively. "Indeed I am," replied the young man, apparently not disconcerted in the least. The fact was that he seemed quite willing, even eager to discuss the painting. I could not make it out, unless it might be that any subject was less painful than the sudden death of Miss Fleming. "Yes," he continued voluntarily, "I suppose you know it represents a group of dancers. The central figure of the group, as everyone believes, is reputed to be the passionate and jealous Madame de Montespan, whom the beautiful Madame de Maintenon replaced in the affections of Louis XIV. "Why, no one thinks of Watteau, with his delightful daintiness and many graceful figures on such masterfully disposed backgrounds as a portrait painter. But the Fête shows, I have always contended, that he drew on many real faces for his characters. Yes, he could paint portraits, too, wonderfully minute and exact little miniatures." Faber had risen as he discoursed. "I have a copy of it," he added, leading the way into his own private gallery, while Craig and I followed him without comment. We gazed long and intently at the face of the central figure. Small though it was, it was a study in itself, a puzzle, distracting, enigmatical. There was a hard, cruel sensuousness about the beautiful mouth which the painter seemed to have captured and fixed beneath the very oils. Masked cleverly in the painted penetrating dark eyes was a sort of cunning which, combined with the ravishing curves of the cheeks and chin, transfixed the observer. Something in the face reminded me of a face I had once seen. It was not exactly Rita's face, but it had a certain quality that recalled it. I fancied that there was in both the living and the painted face a jealousy that would brook no rivalry, that would dare all for the object of its love. Faber saw that we had caught the spirit of the portrait, and seemed highly gratified. "What crimes a man might commit under the spell of a woman like that!" exclaimed Craig, noticing his gratification. "By the way, do you know that Miss Fleming was said to have had the original--and that it is gone?" Faber looked from one to the other of us without moving a muscle of his face. "Why, yes," he replied steadily. I could not make out whether he had expected and been prepared for the question or not. At any rate he added, half serious, half smiling, "Even for her portrait someone was ready to risk even life and honor to kidnap her!" Evidently in his ardor he personified the picture, felt that the thief must have been moved by what the psychologists call "an imperative idea" for the mere possession of such a treasure. "Still," Craig remarked dryly, "the wanderings of the lost Duchess by Gainsborough for a quarter of a century stuffed into a tin tube, to say nothing of the final sordid ending of the capture of Mona Lisa, might argue a devotion among art thieves a bit short of infatuation. I think we'll find this lady, too, to be held for ransom, not for love." Faber said nothing. He was evidently waiting for Kennedy to proceed. "I may photograph your copy of the Fête?" queried Craig finally, "so as to use it in identifying the real one?" "Surely," replied the collector. "I have no objection. If I should happen to be out when you came, I'll leave word with my man to let you go ahead." Just then the telephone rang and Faber reached for it before we could thank him and say good-night. "Hello--oh, Miss Tourville, how do you do? Why--er--yes--yes, I'm listening." They chatted for several minutes, Faber answering mostly in monosyllables. Perhaps it was my imagination, but I thought the conversation, at least at his end of the line, constrained. As he hung up the receiver, I fancied, too, that Faber seemed to look on us with a sort of suspicion. What was his connection with Rita, I wondered? What had Rita told him? A moment later we had said good-by and had gained the street, Kennedy still making no comment on the case. "There's nothing more that we can do tonight," remarked Craig, looking at his watch finally as we walked along. "Let us go over to the City Laboratory and see Dr. Leslie, as I promised Blythe." CHAPTER XX THE MECHANICAL CONNOISSEUR Dr. Leslie, the Coroner, was an old friend of ours with whom we had co-operated in several cases. When we reached his office we found Dr. Blythe there already, waiting for us. "Have you found anything yet?" asked Dr. Blythe with what I felt was just a trace of professional pique at the fact that neither physician had been able to shed any light on the case so far. "I can't say--yet," responded Craig, not noticing Blythe's manner, as from the piece of tissue paper in which he had wrapped them he produced the broken bits of bottle. Carefully he washed off the jagged pieces, as though perhaps some of the liquid the bottle had contained might have adhered to the glass. "I suppose you have animals here for experiment?" he asked of Leslie. The Coroner nodded. "Chickens?" asked Craig with a broad smile at the double meaning. "A Leghorn rooster," returned Dr. Leslie with a laugh. "Good--bring him on," replied Craig briskly. Quickly Kennedy shot a small quantity of the liquid he had obtained by washing the bits of glass into the veins of the white Leghorn. Then he released the rooster, flapping about. In a corner chanticleer stood, preening his feathers and restoring his ruffled dignity, while we compared opinions. "Look!" exclaimed Kennedy a few minutes later, when we had almost forgotten the rooster. His bright red comb was now whitish. As we watched, a moment later it turned dark blue. Otherwise, however, he seemed unaffected. "What is it?" I asked in amazement, turning to Craig. "Ergot, I think," he replied tersely. "At least that is one test for its presence." "Ergot!" repeated Dr. Leslie, reaching for a book on a shelf above him. Turning the pages hurriedly, he read, "There has been no experience in the separation of the constituents of ergot from the organs of the body. An attempt might be made by the Dragendorff process, but success is doubtful." "Dragendorff found it so, at any rate," put in Dr. Blythe positively. Running his fingers over the backs of the other books, Dr. Leslie selected another. "It is practically impossible," he read, "to separate ergot from the tissues so as to identify it." "Absolutely," asserted Dr. Blythe quickly. I looked from one physician to the other. Was this the "safe" poison at last? Kennedy said nothing and I fell to wondering why, too, Dr. Blythe was so positive. Was it merely to vindicate his professional pride at the failure he and the Coroner had had so far with the case? "I suppose you have no objection to my taking some of this sample of the contents of the organs of her body, have you?" asked Craig at length of Dr. Leslie. "None in the world," replied the Coroner. Kennedy poured out some of the liquid into a bottle, corked it carefully, and we stood for a few moments longer chatting over the developments, or rather lack of developments of the case. It was late when we returned to our apartment, but the following morning Kennedy was up long before I was. I knew enough of him, however, to know that I would find him at his laboratory breakfastless, and my deduction was correct. It was not until the forenoon that Craig had completed the work he had set himself to do as he puzzled over something in the interminable litter of tubes and jars, bottles and beakers, reagents, solutions, and precipitates. "I'm going to drop in at Jacot's," he announced finally, laying off his threadbare and acid-stained coat and pulling on the clothes more fitted for civilization. Having no objection, but quite the contrary, I hastened to accompany him. Jacot's was a well-known shop. It opened on Fifth Avenue, just a few feet below the sidewalk, and Jacot himself was a slim Frenchman, well preserved, faultlessly dressed. "I am the agent of Mr. Morehouse, the Western mine-owner and connoisseur," introduced Kennedy, as we entered the shop. "May I look around?" "Certainement,--avec plaisir, M'sieur," welcomed the suave dealer, with both hands interlocked. "In what is Mr. Morehouse most interested? In pictures? In furniture? In--" "In almost anything that is rare and beautiful," confided Craig, looking Jacot squarely in the eye and adding, "and not particular about the price if he wants a thing, either. But I--I am particular--about one thing." Jacot looked up inquiringly. "A rebate," Kennedy went on insinuatingly, "a commission on the bill--you understand? The price is immaterial, but not my--er--commission. Comprenez-vous?" "Parfaitement," smiled the little Frenchman. "I can arrange all that. Trust me." We spent an hour, perhaps, wandering up and down the long aisles of the store, admiring, half purchasing, absorbing facts about this, that and the other thing that might captivate the fictitious Mr. Morehouse. Not satisfied with what was displayed so temptingly in the front of the store, Kennedy wandered back of a partition apparently in search of some more choice treasures, before Jacot could stop him. He turned over a painting that had been placed with its face toward the wall, as if for protection. I recognized the subject with a start. It was Watteau's Fête! "Wonderful!" exclaimed Kennedy in well-feigned ecstasy, just as Jacot came up. "Ah, but, M'sieur," interposed the art dealer, "that is only a copy--and not for sale." "I believe my friend, Mr. Faber, has a copy," ventured Craig. "By a Miss Fleming?" asked Jacot quickly, apparently all interest now. Kennedy shrugged his shoulders. Was Jacot hinting at something known in the trade? "Might I photograph some of the things here to show Mr. Morehouse?" asked Craig a moment later. "I see several things in which I think he might be interested." "Surely," answered Jacot, then, after consideration, in which his beady eye seemed to size up Kennedy, he added, sotto voce, craftily, "Would Mr. Morehouse be--er--interested in Watteau's Fête?" My heart almost stopped beating. Were we really on the right track at last? Jacot leaned over confidentially to Kennedy and added, "Why not sell as an original, not this, but another copy--a--a--what you call it?--a fake?" I understood. Kennedy, having invited crooked dealing by his remark about the rake-off, was being approached about another crooked deal. "A fake Watteau?" he asked, appearing to meet Jacot halfway. Jacot nodded. "Why not? You know the same Botticelli belongs to collectors in Philadelphia and Boston; that is, each has a picture and if one is genuine the other must be a fake. Possibly the artist painted the same picture twice. Why, M'sieur, there are Rubens, Hals, Van Dycks, Rembrandts galore in this country that hang also at the same time abroad." Jacot smiled. "Did you never hear of a picture with a dual personality?" Kennedy seemed to consider the idea. "I'll think it over," he remarked finally, as we prepared to leave, "and let you know when I come back to snap some of the things for my principal." "Well--of all brazen crooks!" I sputtered when we had gained Fifth Avenue. Kennedy shook his head. "We can't be sure of anything in this game. Does it occur to you that he might perhaps think he was playing us for suckers, after all?" My mind worked rapidly. "And that that picture of Faber's is the real original, after all?" I asked. "You mean that somehow a copy by Miss Fleming has come really to Jacot with instructions to palm it off on some gullible buyer?" "Frankly, Walter," he said, as we walked along, "I don't know what to think. You know even the greatest experts sometimes disagree over questions like this. Well, Walter, art is long and time is fleeting. If we are ever to settle where that real Watteau is, we shall have to resort to science, I think." That afternoon after a trip up to the laboratory, where Craig secured a peculiar and cumbersome photographic outfit, we at last found ourselves around at Faber's private gallery. Faber was out, but, true to his promise, he had left word with his man, who admitted us. Kennedy set to work immediately, before the painting, placing an instrument which certainly was not like a regular camera. I was further astonished, moreover, when Craig set up something back of the canvas, which he moved away from the wall. As nearly as I could make it out it consisted of a glass bulb of curious shape. A moment later he attached the bulb to a wire that connected with a little rheostat or resistance coil and thence, in turn, to an electric-light socket. He switched on the electric current and the apparatus behind the picture began to sputter. I could not see very well what it was, but it looked as if the bulb was suffused with a peculiar, yellowish-green light, divided into two hemispheres of different shades. The pungent odor of ozone from the electric discharge filled the room. While Kennedy was working, I had noticed a little leather party box lying on a table, as though it had been forgotten. It was not just the thing one would expect in Faber's rooms and I looked at it more closely. On it were the initials "R. T." Had Rita Tourville visited him? Craig had scarcely finished and was packing up his apparatus when we heard a noise outside. A second later, Faber himself entered, with Rita, evidently looking for something. "Oh, yes, Rita,--here it is. Why, Kennedy--how are you? Did you get your photograph?" Kennedy replied that he had, and thanked him. It was easy to see Rita's pleasure at being with the young connoisseur, but at the sight of Craig I fancied for a moment that I saw a flash of that passionate resentment which had caused me to find a resemblance between the expression of her face and that of De Montespan in the painting, a hint at what she would do or dare to protect the object of her affections. We departed shortly, leaving Rita and Faber deep in the discussion of some art topic. It was not until late in the afternoon that we were able to revisit Jacot's. He received us cordially, but Craig, by a whispered word or two, was able to postpone the answer to the clever proposal which might have been a trap prepared for us. Craig, with a regular camera which he had brought also, set to work snapping pictures and objects of art with reckless profusion, moving them about to get a better light and otherwise consuming time. At last came the opportunity he had been awaiting, when Jacot had a customer in the front of the store. Quickly he set up the peculiar apparatus which he had used at Faber's before the copy of the Watteau in the rear of the shop, switched on the electricity, and amid the suppressed sputtering duplicated the work I had seen him do before. As he was packing the apparatus up, I happened to glance toward the front of the store. There were Leila and Jacot in earnest conversation. I whispered to Kennedy, and, a moment later, she caught sight of me, appeared not to recognize me, and left. Jacot sauntered back to us, I thought, concealing his haste. Before he could speak, Kennedy asked, "Who was that woman?" He had finished packing up the apparatus and even if Jacot had heard something that caused him to change his mind, it was now too late to stop Kennedy. "Why," hastened Jacot, apparently frank, "that is the maid of the Miss Fleming, the artist who has just died. She has come to me to see whether I can get her a position with another artist." "I thought I recognized her," remarked Kennedy. "I remember when I saw her once before that she had on a wedding ring. Doesn't her husband support her?" Jacot shrugged his shoulders. "She is looking for another position--that is all I know," he said simply. Kennedy picked up his apparatus. "You will think over my proposition?" asked Jacot, as we left. "And let you know in a day or two," nodded Kennedy. As we walked up Fifth Avenue, I confess to have felt all at sea. Who had the real masterpiece? Was it Faber, or Jacot, or was it someone else? If Rita had warned Faber against us, and Leila had warned Jacot, which had copy and which original? Or were they both copies and had the original been hidden? Had it been stolen for money or had some fiend with a knowledge of this mysterious ergot stolen it simply for love of art, stopping not even at murder to get it? CHAPTER XXI THE RADIOGRAPH WITNESS It was apparent that quick action was necessary if the mystery was ever to be solved. Kennedy evidently thought so, too, for he did not wait even until he returned to his laboratory to set in motion, through our old friend, Commissioner O'Connor, the machinery that would result in warrants to compel the attendance at the laboratory of all those interested in the case. Then he called up Dr. Leslie and finally Dr. Blythe himself. Back again in the laboratory, Kennedy employed the time in developing some plates of the pictures he had taken, and by early evening, after a brief study of them, his manner indicated that he was ready. Dr. Leslie, whom he had asked to come a little before the rest, arrived early, and a few moments later Dr. Blythe, very much excited by the message he had received. "Have you found anything?" he asked eagerly. "I've been trying all sorts of tests myself, and I can't prove the presence of a thing--not a thing." "Not ergot?" asked Kennedy quietly. "No," he cried, "you can't prove anything--you can't prove that she was poisoned by ergot." Dr. Leslie looked helplessly at Kennedy, but said nothing. "Not until recently, perhaps, could I have proved anything," returned Kennedy calmly. "Evidently you didn't know, Dr. Blythe, that the first successful isolation of an alkaloid of ergot from the organs in a case of acute ergotism had been made by two Pittsburgh scientists. True, up to the present toxicologists had to rely on the physical properties of this fungus of rye for its identification. That may have made it seem like a safe poison to someone. But I have succeeded in isolating ergotinin from the sample of the contents of the organs of the poor girl." Without pausing, he picked up a beaker. "Here I have the residue left from an acid solution of an extract of the organs, treated with chloroform. It is, as you see, crystalline." In his other hand he held up another beaker. "Next I got the residue obtained by extraction of the acid aqueous liquid with ether. That, too, is crystalline." Kennedy displayed something in the shape of long needles, the sides of which were not quite parallel and the ends replaced by a pair of faces. Quickly he dissolved some of the crystals in sulphuric acid. Then he added another chemical from a bottle labeled ferro chlorid. The liquid, as we bent over it, changed quickly to a brilliant orange, then a crimson, next a green, and finally became a deep blue. "What he has derived from the body responds to all the chemical tests for ergotinin itself," remarked Dr. Leslie, looking quickly across at Dr. Blythe. Dr. Blythe said nothing. I smelt of the stuff. Odors with me, as, I suppose, with other people, have a psychological effect, calling up scenes associated with them. This odor recalled something. I strove to recollect what it was. At last it came with a rush. "The meat sauce!" I exclaimed involuntarily. "Exactly," replied Kennedy. "I have obtained that bottle. There was ergot in it, cleverly concealed by the natural smell and taste of the sauce. But who put it there? Who had the knowledge that would suggest using such a poison? Who had the motive? Who had been dining with her that fatal evening?" Kennedy had no chance to answer his questions, even if he had intended to do so. The door of the laboratory opened and Rita Tourville, in charge of one of O'Connor's men, who looked as if he might have enjoyed it better if the lady had not been so angry, entered. Evidently O'Connor had timed the arrival closely to what Craig had asked, for scarcely a moment later Faber came whirling up in one of his own cars. Not a word passed between him and Rita, yet I felt sure that they had some understanding of each other. Leila arrived shortly, and it was noticeable that Rita avoided her, though for what reason I could not guess. Finally came Jacot, blustering, but, having made the officer the safety-valve of his mercurial feelings, quickly subsiding before us. Dr. Blythe appeared amazed at the quickness with which Kennedy moved now. "In ordinary times," began Kennedy, noting as he spoke the outward attitude of our guests toward each other, "the world would have stood aghast at the disappearance of such a masterpiece as the Fête by Watteau. It would have ranked with the theft of Gainesborough's Duchess of Devonshire, Da Vinci's Mona Lisa, the brown-skinned Madonna of the Mexican convent, Millet's Goose-girl, and the Shepherd and Flock, the portrait of Saskia by Rembrandt, and other stolen masterpieces. "But today the vicissitudes of works of art in war time pass almost unnoticed. Still there is a fascination exercised over the human mind by works of art and other objects of historic interest, the more so because the taking of art treasures seems to have become epidemic in northern Europe." He laid down what looked more like two rough sketches than photographs, yet they were photographs, though the relative brightness of color in photographs was quite different. Outlines were displaced, also. Ugly spots and bands marred the general effect. They were peculiar. "They are X-ray images or radiographs of two oil paintings, both claimed to be copies of Watteau's famous Fête," explained Kennedy, picking up one of them. "In a radiograph of the body," he continued, "the difference of brightness that distinguishes the heart from the lungs, bones from flesh, is due to the different densities of tissues. In these pictures the same effect is produced by the different densities of the pigments, especially of their principal and heaviest elements." He paused and laid down a chart. "For anyone who doubts what I am about to prove, I have made a scale of oil colors arranged in accordance to their transparency to Roentgen rays by applying standard pigments to canvas in patches of equal thickness. "I think you can see what I am driving at. For instance, a design drawn in a heavy pigment will show through a layer of a less dense pigment, under the influence of the X-ray--just as bones show through flesh. In other words, an ordinary photograph reproduces only the surface of a painting. A radiograph represents all the pigments underneath, also producing effects in proportion to their densities. "Let me show you the practical result of all this in studying such radiographs, as worked out by a German student. I have made several very interesting and conclusive discoveries which these radiographs I have taken illustrate." He paused a moment, for the sake of emphasis. "You will notice," he resumed carefully, "the lace frill above the bodice on the figure of Madame de Montespan, in this radiograph. In the painting the frill is sharply defined and can be clearly distinguished from the bodice. But look at this radiograph. It appears tattered. It overflows the bodice. "That led me to suspect that the bodice was widened as an afterthought--perhaps to diminish the area of white. That is the reason why the white shows through the bodice in the radiograph. But in this other one the bodice and the frill are substantially as they must be in the original." Again he paused, as if taking up a new point. "This radiograph,--number one, I may call it--shows a broad light band on the right hand of the figure, of which not a trace is to be found either in the other radiograph or the painting itself. It represents the first rough sketch of an arm and hand. "Again, in this first radiograph the ring and little fingers are close together and a sixth finger appears between the index and middle fingers. From that I infer that the hand hung limp with the fingers nearly in contact in the first sketch and that the fingers were afterward separated. But in this second radiograph the arm, hand and fingers are perfect." It was fascinating to listen to Kennedy as he delved down into the invisible beneath the very oils and dug out their hidden mystery. "Take the head and shoulder," he continued. "Radiograph number one clearly shows flaking of the painting which has been painted over to conceal it. Ordinary light reveals no trace, either, of a long crack on the shoulder which evidently was filled with a thick mass of pigment containing too little white lead to obliterate the crack in the radiograph. White spots above the ear, in the radiograph, probably indicate an excess of white lead used in retouching. At any rate, radiograph number two contains no such defects." Kennedy paused before drawing the conclusion. "The radiograph of an original picture reveals changes made by the artist in the course of his work. The counterfeiter, like other copyists, reproduces as accurately as possible the final result. That is all he can see. He makes errors and corrections, but of a different kind. There are no serious changes. "So, a radiograph of even a part of a picture shows the layers of pigment that are hidden from the eye and the changes made during the composition of the work. One can easily distinguish the genuine from the spurious copies, for it is absolutely impossible for an imitator to make a copy that will stand the X-ray test. "You see," he went on enthusiastically, "the most striking feature of these radiographs is their revelation of details of the first sketch, which have been altered in the finished picture. We actually obtain an insight into the methods of an artist--" he paused, adding--"who has been dead for centuries." It was wonderful what Kennedy was getting out of those, to us, blurred and indistinct skiagraphs. I studied the faces before me. None seemed to indicate any disposition to break down. Kennedy saw it, too, and evidently determined to go to the bitter end in hammering out the truth of the mystery. "One moment more, please," he resumed. "The radiograph shows even more than that. It shows the possibility of detecting a signature that has been painted over, in order to disarm suspicion. The detection is easier in proportion to the density of the pigment used for the signature and the lack of density of the superposed coat." He had laid the radiographs on the table before him, with a finger on the corner of each, as he faced us. "At the bottom of each of the paintings in question," he shot out, leaning forward, "you will find nothing in the way of a signature. But here, in radiograph number two, for instance, barely discernible, are the words, "R. Fleming," quite invisible to the eye, but visible to the X-ray. These words have been painted over. Why? Was it to prevent anyone from thinking that the owner had ever had any connection with Rhoda Fleming?" I was following Kennedy, but not so closely that I missed a fearful glance of Rita from Faber to Jacot. What it meant, I did not know. The others were too intent on Kennedy's exposure to notice. I wondered whether someone had sought to conceal the fact that he had a copy of the famous Watteau, made by Miss Fleming? "Look at the bottom of the other radiograph, number one, further toward the left," pursued Kennedy resistlessly. "There you will discover traces of an 'A' and a 'W,' which do not appear on the painting. Between these two are marks which can also be deciphered by the X-ray--'Antoine Watteau.' Perhaps it was painted over lightly so that an original could be smuggled in as a copy. More likely it was done so that a thief and murderer could not be traced." As Kennedy's voice rang out, more and more accusatory, Rita Tourville became more and more uncontrollably nervous. "It was suggested," modulated Kennedy, playing with his little audience as a cat might with a mouse, "that someone murdered Rhoda Fleming with the little-understood poison, ergot, because of an infatuation for the picture itself. But the modern crook has an eye for pictures, just as for other valuables. The spread of the taste for art has taught these fellows that such things as old masters are worth money, and they will even murder now to get them. No, that radiograph which I have labeled number one is not a copy. It is of the genuine old master--the real Watteau. "Someone, closely associated with Miss Fleming, had found out that she had the original. That person, in order to get it, went even so far as to--" Rita Tourville jumped up, wildly, facing Craig and crying out, "No, no--his _is_ the copy--the copy by Miss Fleming. It was I who told him to paint over the signature. It was I who called him away--both nights--on a pretext--when he was dining with her--alone--called him because--I--I loved him and I knew--" Faber was on his feet beside her in a moment, his face plainly showing his feelings toward her. As he laid his hand on her arm to restrain her, she turned and caught a penetrating glance from Jacot's hypnotic eye. Slowly she collapsed into her chair, covering her face with her hands, sobbing. For a moment a look of intense scorn and hatred blazed in Leila's face, then was checked. Craig waved the radiograph of the real Watteau as he emphasized his last words. "In spite of Rita Tourville's unexpected love for Faber, winning him from your victim, and with the aid of your wife, Leila, in the rôle of maid, the third member of your unique gang of art thieves, you are convicted infallibly by my X-ray detective," thundered Craig as he pointed his finger at the now cowering Jacot. CHAPTER XXII THE ABSOLUTE ZERO "Isn't there some way you can save him, Professor Kennedy? You _must_ come out to Briar Lake." When a handsome woman like Mrs. Fraser Ferris pleads, she is irresistible. Not only that, but the story which she had not trusted either to a message or a messenger was deeply interesting, for, already, it had set agog the fashionable country house colony. Mrs. Ferris had come to us not as the social leader now, but as a mother. Only the night before her son, young Fraser, had been arrested by the local authorities at Briar Lake on the charge of homicide. I had read the meager dispatch in the morning papers and had wondered what the whole story might be. "You see, Professor Kennedy," she began in an agitated voice as soon as she arrived at the laboratory and introduced herself to us, "day before yesterday, Fraser was boxing at the Country Club with another young man, Irving Evans." Kennedy nodded. Both of them were well known. Ferris had been the All-America tackle on the University football team a couple of years previous and Evans was a crack pitcher several years before. "Irving," she continued, adding, "of course I call him Irving, for his mother and I were schoolgirls together--Irving, I believe, fell unconscious during the bout. I'm telling you just what Fraser told me. "The other men in the Club gymnasium at the time carried him into the locker-room and there they all did what they could to revive him. They succeeded finally, but when he regained consciousness he complained of a burning sensation in his stomach, or, rather, as Fraser says, just below the point where his ribs come together. They say, too, that there was a red spot on his skin, about the size of a half-dollar. "Finally," she continued with a sigh, "the other men took Irving home--but he lapsed into a half-comatose condition. He never got better. He--he died the next day--yesterday." It was evidently a great effort for Mrs. Ferris to talk of the affair which had involved her son, but she had made up her mind to face the necessity and was going through it bravely. "Of course," she resumed a moment later, "the death of Irving Evans caused a great deal of talking. It was natural in a community like Briar Lake. But I don't think anything would have been thought about it, out of the way, if the afternoon after his death--yesterday--the body of one of the Club's stewards, Benson, had not been found jammed into a trunk. Apparently, it had been dumped off an automobile in one of the most lonely sections of the country. "In fact," she went on, "it was the sort of thing that might have taken place, one would say, in the dark alleys of a big city. But in a country resort like Briar Lake, the very uncommonness of such a case called added attention to it." "I understand," agreed Craig, "but why did they suspect your son?" "That's the ridiculous part of it, at least to me," hastened the mother to her son's defense. "Both Irving and my son, as you know, were former University athletic stars, and, as in all country clubs, I suppose, that meant popularity. Irving was engaged to Anita Allison. Anita is one of the most beautiful and popular girls in the younger set, a splendid golfer, charming and clever, the life of the Club at the dances and teas." Mrs. Ferris paused as though she would convey to us just the social status of everyone concerned. "Of course," she threw in parenthetically, "you know the Allisons are reputed to be quite well off. When old Mr. Allison died, Anita's brother, Dean, several years older than herself, inherited the brokerage business of his father and, according to the will, assumed the guardianship of his younger sister." She seemed to be considering something, then suddenly to make up her mind to tell it. "I suppose everyone knows it," she resumed, "and you ought to know it, too. Fraser was--er--one of Anita's unsuccessful suitors. In fact, Anita had been sought by nearly all of the most eligible young fellows of the Club. I don't think there were many who had not at some time or other offered her his whole heart as well as his fortune. "I didn't encourage Fraser--or try to discourage him. But I could see that it lay between Fraser and Irving." "And the rather strange circumstances of the death of Evans, as well as of the steward, occasioned a good deal of gossip, I suppose," chimed in Kennedy. "Yes. Somehow, people began to whisper that it was revenge or hate or jealousy that had prompted the blow,--that perhaps the steward, Benson, who was very popular with the young men, knew or had seen something that made him dangerous. "Anyhow, gossip grew until it seemed that, in some way which no one has ever said definitely, a deliberate attempt was made on Irving Evans's life, and finally the local authorities, rather glad to take up a scandal in the Club set, took action and arrested my Fraser--under a charge of homicide." She blurted the words out fiercely and defiantly, but it was all assumed. Underneath, one could see the woman fighting loyally with every weapon for her son, keenly alive to the disgrace that even the breath of scandal unrefuted might bring to his name. "How about the other admirers?" asked Craig quickly. "That's another queer thing," she replied eagerly. "You see, they have all suddenly become very busy and have made perfect alibis. But there was Allan Wyndham--he's a friend of the Allisons,--why shouldn't they suspect him? In fact, there was quite a group of young fellows closely associated with Dean Allison in speculation. Irving Evans was one. But," she added, with a glance at Kennedy as if she realized that it was like catching at a straw, "with Fraser, of course,--there is that blow. We can't deny that." "What does Miss Allison think?" queried Craig. "Oh, I believe Anita is all broken up by the tragedy to her fiancé. She was at the Club at the time--in the tea room. No one dared to tell her until Irving had been taken home. Then her brother, who was in the gymnasium when the thing happened and had been one of those to carry Irving into the locker-room, was naturally chosen by the rest, after they had done all they could to revive Irving, to break the news as gently as he could to his sister. She took it calmly. But I think it would have been better if she had given way to her real feelings. They say she has secluded herself in the Allison house and won't see a soul." Kennedy's brow puckered in thought. "You can't imagine what a terrible shock this thing has been to me," pleaded Mrs. Ferris. "Oh, the horror of it all! You _must_ come out to Briar Lake with me!" There was, naturally, no doubt of the poignancy of her feelings as she looked from Kennedy to myself, imploringly. As for Craig, he did not need to betray the sympathy he felt not only for the young man who had been arrested and his mother, but for the poor girl whose life might be blasted by the tragedy and the unhappy victim who had been snatched away so suddenly almost on the very eve of happiness. It was not half an hour later, that, with a very grateful mother, we were on our way out to Briar Lake in Mrs. Ferris's touring car. As we whirled along past the city limits, Kennedy leaned back on the cushions and for some minutes seemed absorbed in thought. "Of course it is possible," he remarked at length, noticing that both Mrs. Ferris and I were watching him nervously, "that Miss Allison may know something that will throw some light on the affair. But it may be of an entirely private nature. I don't know how we'll get her to talk, but we must--if she knows anything. I'd like to stop at the Allison house, first." "Very well," agreed Mrs. Ferris, leaning forward and directing the chauffeur to turn off before we reached Briar Lake on the main road. We sped along and I could not help feeling that the young man who was driving the car was quite as eager as anyone else to bring help to his young master. The Allison house proved to be a roomy, old-fashioned place on a rise of ground just this side of Briar Lake, for the Allisons had been among the first to acquire estates at the exclusive colony. Mrs. Ferris remained in the car, while Kennedy and I went in to introduce ourselves. We found the young society girl evidently now in full possession of her nerves. She was slender, fair, with deep blue eyes, not merely pretty, but with a face that showed character. Anita Allison had been seated in the library, and, as we entered, I could see that she had hastily shoved some papers, at which she had been looking, into a drawer of the desk. "Miss Allison," began Kennedy, "this is a most unfortunate affair and I must beg your pardon--" "Yes," she interrupted, "I understand. As if I didn't feel badly enough--oh--they have to make it all so much harder to bear by arresting Fraser--and then all this notoriety,--it is awful." I confess that I had not expected that we would see her so easily. Yet I felt that there was some constraint in her manner, in spite of that. "I want to speak frankly with you, Miss Allison," went on Craig gently. "Is there anything about the matter--of a personal nature--that you haven't told? I want to appeal to you. Remember, there is another life at stake, now." She looked at us searchingly. Did she suspect that we knew something or was she herself seeking information? "No, no," she cried. "There isn't a thing--not a thing that I know that I haven't told--nothing." Kennedy said nothing himself, but watched her, apparently assuming that she would go on. "Oh," she cried, "if I could only _do_ something--anything. It might get my mind off it all. But I--I can't even cry!" Plainly there was little except a sort of mental vivisection of her grief to be gained from her yet--even if she suspected something, of which I was not entirely sure. We excused ourselves and left her, sunk deeply into a leather chair, her face buried in her hands, but not weeping. "Is Mr. Allison at home?" inquired Craig as we passed out through the hall, meeting the butler at the door. "No, sir," he replied. "He went to New York this morning, sir, and said he'd be at the Club later this afternoon." We climbed into the car and Kennedy looked at his watch. "It's getting well along in the afternoon," he remarked. "I think I'll go over to the Club. We may find Allison there now." As we turned out into the main road our driver had to swerve for a car which turned off, coming from the city, as we had come a few minutes before. He looked around at it blackly, as it went up the road to the Allison house, for he had had to stall his own engine to avoid a collision. There was no one in the other car but a driver with a visored hat. "Whose car was that?" asked Craig quickly. "Allan Wyndham's," answered our driver, starting his engine. "H'm," mused Craig. "Wyndham must have sent her a message from town. Too bad we hurried so to get up here." At last, as we turned a bend in the main road, the broad chimneys, white columns and wide balustrades of the Briar Lake Country Club loomed in sight. The Country Club was a most pretentious building, yet, unlike many such clubs, had a very hospitable air in spite of its aristocratic and handsome appearance. There was something very inviting about its wide sweep of roof and ample piazzas, some enclosed in glass, as we approached by the broad graveled driveway that swung in from the highway between the gentle curves of green lawns whose expanse was broken by the tall pines through which we caught a glimpse of the hills. It was indeed a beautiful country. We entered a wide hall and came to the reception room crowded with luxurious armchairs and cozy corners. In a glass case stood the usual trophies. Grouped about a huge deep fire was a knot of people, and here and there others were talking earnestly. One could feel that this was one of those social institutions not to be in which argued that one was decidedly out of things. I could almost visualize the close scrutiny that new applicants would undergo, not so much as men among men, but through the eyes of the women folk, dissecting the wives and daughters of the family. Founded originally because of the interest of the older members in horses and the hunt, the Club had now extended its activities to polo and motors, golf, tennis, squash, with a fine old English bowling green and ample shooting traps. I could not blame Mrs. Ferris for not wishing to enter the Club just yet. She had left us at the door, promising to send the car back for our disposal. CHAPTER XXIII THE VACUUM BOTTLE Fortunately, Dean Allison was at the Club, as we hoped, having just arrived by the train that left New York at the close of the banking day. Someone told us, however, that Wyndham had probably decided to remain in town over night. Allison was perhaps a little older than I had imagined, rather a grave young man who seemed to take his club responsibilities on the Council very seriously. "I'd like to talk to you about this Evans case," began Craig when we had been introduced. "Glad to tell you all I know," he responded cordially. "It isn't much, I'm afraid. It's terrible--terrible. We don't know what to think. My sister is all broken up by it, poor girl." He led the way over to a corner, in a sort of bow window, and we sat down on the hard leather cushions. "No, there isn't much I can say," he resumed. "You see, one of the recreations of the younger set at the Club is boxing--that's about all there was to it--not the amateurish thing one usually sees, but real scientific boxing. "Fraser had adopted the so-called Fitzsimmons shift--you know, the right foot forward, while the left hand shoots out from somewhere near the hip, plunging at close range into the pit of the stomach." Allison rose to illustrate it. "Irving, on the other hand, had been advocating the Jeffries crouch as the only safeguard to meet it,--like that." He threw himself into position and went on, "The bout had been arranged, accordingly, and it was _some_ bout, too. Most of us here are fond of boxing to keep fit. "Well, at last Fraser got under his guard, I suppose you'd call it. He landed. For an instant, Irving stood up straight, his hands helplessly extended. Most of us thought he was fooling and Fraser jumped back, laughing at the way his contention had worked out. Then, slowly, struggling as if against the inevitable, Irving bent forward and toppled over on his face. "That's where we woke up. We rushed forward and picked him up, apparently unconscious, and carried him to the locker-room. There was a good deal of excitement. Someone telephoned for a doctor, but couldn't seem to find one at home." "Did you see anything peculiar take place in the locker-room?" asked Kennedy, following keenly. "Anything peculiar?" "Yes--anyone near him, perhaps--another blow--while he was unconscious." "No--and I think I would have seen anything that was out of the way. I was there almost all the time--until someone told me my sister was upstairs and suggested that I was the best one to break the news to her." "I'd like to look over the gymnasium and locker-room," suggested Craig. Dean Allison led the way downstairs quickly. Craig did not spend more than a minute in the gymnasium, but the locker-room he examined carefully. It was a long room. Each locker bore the name of its owner and he hastily ran his eye over them, getting their location. I don't know that even he had, yet, any idea that he would find anything, but it was just his habit to go over the ground of a tragedy, in hope of picking up some clew. He looked over the floor very carefully, now and then bending down as if to discover spots. Once he paused a moment, then continued his measured tread down the long row of lockers until he came to a door at the other end of the room. We went out and Kennedy looked about closely. "Oh,--about Benson, the steward," he said, looking up quickly and stroking his chin as if an idea had occurred to him. "Is there anyone here who might know something about him--his habits, associates,--that sort of thing?" "Why--yes," considered Allison slowly, "the chef might know. Wait, I'll call him." As Allison disappeared in the direction of what was evidently the kitchen, we stood outside by the door, waiting. Kennedy's eye traveled back and forth about us and finally fell on a row of rubbish barrels a few feet away. He moved over to them. He had half turned away, retracing his steps back to me thoughtfully, when his eye must have been attracted by something gleaming. He turned back and poked at it with his stick. Peeping from the rubbish was a dented thermos bottle, the lining of which was cracked and broken. He was about to turn away again when his eye fell on something else. It was the top of the bottle, the little metal cap that screws over it, or rather it was what was left of the cap. "That's strange," he muttered to himself, picking it up. The cap, which might have been used as a cup, was broken in the most peculiar manner, in spite of the fact that it was metal. If it had been of glass I should have said that someone had dropped it. Kennedy frowned and dropped the pieces into his pocket, turning to wait for Allison to return with the chef. "I can't seem to find him," reported Allison a moment later. "But he'll be here soon. He'll have to be--or lose his job. How would after dinner do? I'll have him and all the other employés, then." "Good!" agreed Kennedy. "That will give me time to go into the town first and get back." "I'd be glad to have you dine with me," invited Allison. "Thank you," smiled Kennedy. "I'm afraid I won't have time for dining tonight. I'll be back after dinner, though." Mrs. Ferris's car had returned and Craig's next step was to go on into the town of Briar Lake. On the way he decided first to stop at the Evans house, which took us only a little bit out of our way. There he made a minute examination of the body of the young man. Irving Evans had been a handsome fellow and the tragedy of his death had been a sad blow to his family. However, I shall not dwell on that, as it is no part of my story. Kennedy was eager to see the red spot in the pit of the stomach of the dead man of which everyone had spoken. He looked at it closely, as I did also, although I could make nothing of it. Evans had complained of a burning, stinging sensation, during his moments of consciousness and the mark had had a flushed, angry look. It seemed as though a sort of crust had formed over it, which now was ashen white. Craig did not spend as long as I had anticipated at the Evans house, but, although he said nothing, I could tell by the expression of his face that he was satisfied with the conclusions which he drew from the examination. Yet I could not see that the combination of circumstances looked much better for Fraser Ferris. We went on now to the town and there we had no trouble in meeting the authorities and getting them to talk. In fact, they seemed quite eager to justify themselves. As we passed down the main street, Mrs. Ferris's chauffeur mentioned the fact that a local physician, Dr. Welch, was also the Coroner of the county. Kennedy asked him to stop at the doctor's office, and we entered. "A most unfortunate occurrence," prefaced the doctor as we seated ourselves. "You assume, then, that it was the blow that killed Evans?" asked Kennedy pointedly. The doctor looked at him a moment. "Of course--why not?" he demanded argumentatively, as though we had come all the way from the city for the sole purpose of impugning his medical integrity. "I suppose you know the classical case of the young man who was coming out of the theater, when some of the party began indulging in rather boisterous horse play? One bent another quietly over his arm and tapped him a sharp blow with the disengaged hand on the stretched abdomen. The blow fell right over the solar plexus and, to the surprise of everyone, the young man died." The Coroner had risen and was pacing the room slowly. "I could cite innumerable cases. Everyone understands that a blow may be fatal because of shock to the solar plexus. In such a case no post-mortem trace might be found and the blow could even be a light one. "For instance, in a fight a blow might be struck and the recipient fall dead. If the medical examiner should find nothing on holding the autopsy which would have caused sudden death, he can testify that a shock to the solar plexus will cause death and that the post-mortem examination will give no evidence to support or disprove the statement. The absolute absence, however, of any reason or of injury to the other organs will add weight to his testimony, evidence of the blow being present." "And you think this was such a case?" asked Kennedy, with just a trace of a challenge in his tone. "Certainly," replied the Coroner. "Certainly. We know that a blow was struck--in all probability hard enough to affect the solar plexus." It was evident, in his mind at least, that young Ferris was guilty and Kennedy rose to go, refraining from antagonizing him by further questions. We next visited the county court house, which was not far from the doctor's office. There, the sheriff, a young man, met us and seemed willing to talk over the evidence which so far had been unearthed in the case. In his office was a trunk, a cheap brown affair, in which the body of the unfortunate steward, Benson, had been found. "Quite likely the trunk had been carried to the spot in a car and thrown off," the sheriff explained. "A couple of boys happened to find it. They told of their find and one of the constables opened the trunk, then called us up here. In the trunk was the body of a man, crouched, the head forced back between the knees." "I'd like to see Benson's body," remarked Kennedy. "Very well, I'll go with you," returned the sheriff. "It's at the undertaker's--our only local morgue." As we walked slowly up the street, the sheriff went on, just to show that country as well as city detectives knew a thing or two. "There are just two things in which this differs from the ordinary barrel or trunk murder you read about." "What are they?" encouraged Craig. "Well, we know the victim. There wasn't any difficulty about identifying him. We know it wasn't really a Black Hand crime, although everything seems to have been done to make it look like one, and the body was left in the most lonely part of the country. "And then the trunk. We have traced it easily to the Club House. It was Benson's own trunk--had been up in his own room, which was locked." "His own trunk?" repeated Craig, suddenly becoming interested. "How could anyone take it out, without being seen? Didn't anyone hear anything?" "No. Apparently not. None of the other servants seem to have heard a thing. I don't know how it could have been got out, especially as his door was locked and we found the keys on him. But--well, it was. That's all." We had reached the undertaker's. The body of Benson was horribly mangled about the head and chest, particularly the mouth. It seemed as if a great hole had been torn in him, and he must have died instantly. Kennedy examined the grewsome remains most carefully. What had done it, I wondered? Could the man have been drugged, perhaps, and then shot? "Maybe it was a dum-dum bullet," I suggested, "one of those that mushrooms out and produces such frightful wounds." "But assuming it entered the front, there is no exit in the back," the sheriff put in quickly, "and no bullet has been found." "Well, if he wasn't shot," I persisted, "it must have been a blow, and it seems impossible that a blow could have produced such an effect." The sheriff said nothing, evidently preferring to gain with silence a reputation for superior wisdom. Kennedy had nothing better than silence to offer, either, though he continued for a long time examining the wounds on the body. Our last visit in town was to Fraser Ferris himself, to whom the sheriff agreed to conduct us. Ferris was confined in the grim, dark, stone, vine-clad county jail. We had scarcely entered the forbidding door of the place when we heard a step behind us. We turned to see Mrs. Ferris again. She seemed very much excited, and together we four, with a keeper, mounted the steps. As she caught sight of her son, behind the bars, she seemed to gasp, then nerve herself up to face the ordeal of seeing a Ferris in such a place. "Fraser," she cried, running forward. He was tall, sunburned, and looked like a good sportsman, a clean-cut fellow. It was hard to think of him as a murderer, especially after the affecting meeting of the mother and son. "Do you know what I've just heard?" she asked at length, then scarcely pausing for a word of encouragement from him, she went on. "Why, they say that Benson was in town early that evening, drinking heavily and that that might account--" "There--there you are," he cried earnestly. "I don't know what happened. But why should I do anything to him? Perhaps someone waylaid him. That's plausible." "Of course," warned Kennedy a few minutes later, "you know that anything you say may be used against you. But--" "I _will_ talk," interrupted the young man passionately, "although my lawyer tells me not to. Why, it's all so silly. As for Irving Evans, I can't see how I could have hit him hard enough, while, as for poor Benson,--well, that's even sillier yet. How should I know anything of that? Besides, they were all at the Club late that night, all except me, talking over the--the accident. Why don't they suspect Wyndham? He was there. Why don't they suspect--some of the others?" Mrs. Ferris was trying to keep a brave face and her son was more eager to encourage her than to do anything else. "Keep up a good heart, Mother," he called, as we finally left, after his thanking Kennedy most heartily. "They haven't indicted me yet, and the grand jury won't meet for a couple of weeks. Lots of things may turn up before then." It was evident that, next to the disgrace of the arrest, his mother feared even more the shame of an indictment and trial, even though it might end in an acquittal. Yet so far we had found no one, as far as I knew, who had been able to give us a fact that contradicted the deductions of the authorities in the case. CHAPTER XXIV THE SOLAR PLEXUS It was after the dinner hour that we found ourselves at the Country Club again. Wyndham had not come back from the city, but Allison was there and had gathered together all the Club help so that Kennedy might question them. He did question them down in the locker-room, I thought perhaps for the moral effect. The chef, whom I had suspected of knowing something, was there, but proved to be unenlightening. In fact, no one seemed to have anything to contribute. Quite the contrary. They could not even suggest a way in which the trunk might have been taken from the steward's room. "That's not very difficult," smiled Kennedy, as one after another the servants asserted that it would be impossible to get it around the turns in the stairs without making a noise. "Where was Benson's room?" The chef led the way to the door, that by which we had gone out before when we had seen the rubbish barrels. "Up there," he pointed, "on the third floor." There was no fire escape, nor were there any outside balconies, and I wondered how Craig would account for it. "Someone might have lowered the trunk from the window by a rope, might they not?" he asked simply. "Yes," returned the chef, unconvinced. "But his door was locked and he had his keys in his pocket. How about that?" "It doesn't follow that he was killed in his room, does it?" asked Craig. "In fact it is altogether impossible that he could have been. Suppose he was killed outside. Might not someone have taken the keys from his pocket, gone up to the room without making any noise and let the trunk down here by a rope? Then if he had dropped the rope, locked the door, and returned the keys to Benson's pockets--how about that?" It was so simple and feasible that no one could deny it. Yet I could not see that it furthered us in solving the greater mystery. We went up to the steward's room and searched his belongings, without finding anything that merited even that expenditure of time. However, Craig was confident now, although he did not say much, and by a late train we returned to the city in preference to using Mrs. Ferris's car. All the next day, Kennedy was engaged, either in his laboratory or on an errand that took him downtown during most of the middle of the day. When he returned, I could tell by the look on his face that his quest, whatever it had been, had been successful. "I found Wyndham--had a long talk with him," was all he would say in answer to my questions, before he went back to whatever he was studying at the laboratory. I had made some inquiries myself in the meantime, especially about Wyndham. As nearly as I could make out, the young men at Briar Lake were afflicted with a disease which is very prevalent--the desire to get rich quick. In that respect Fraser Ferris was no better than the rest. Nor was Irving Evans. Allan Wyndham had been a plunger almost from boyhood, and only the tight rein that his conservative father held over him had checked him. Sometimes the young men succeeded, and that had served only to whet their appetites for more easy money. But more often they had failed. In most cases, it seemed, Dean Allison's firm had been the brokers through whom they dealt, particularly Wyndham. In fact, with more time on my hands during the day than I knew what to do with, in the absence of Kennedy I had evolved several very pretty little theories of the case which involved the recouping of dissipated fortunes by marriage with the popular young heiress. It was late in the afternoon that the telephone rang, and, as Craig was busy, I answered it. "Oh, Mr. Jameson," I heard Mrs. Ferris's voice calling over long distance from Briar Lake anxiously, "is Mr. Kennedy there? Please let me speak to him." I hastened to hand over the receiver to Kennedy and waited impatiently until he finished. "A special grand jury has been empanelled for ten o'clock tomorrow morning," he said as he turned from the wire and faced me, "and unless we can do something immediately, they are sure to find an indictment." Kennedy scowled and shook his head. "It looks to me as if someone were mighty anxious to railroad young Ferris along," he remarked, hurrying across to the laboratory table, where he had been at work, and flinging off his stained smock. "Well, are you ready for them?" I asked. "Yes," he replied quickly. "Call up and find out about the trains to Briar Lake, Walter." I found that we could easily get a train that would have us at the Country Club not later than eight o'clock, and as I turned to tell Kennedy, I saw him carefully packing into a case a peculiar shaped flask which he had been using in some of his experiments. Outside it had a felt jacket, and as we hurried over to the station Kennedy carried it carefully in the case by a handle. The ride out to Briar Lake seemed interminable, but it was better than going up in a car at night, and Mrs. Ferris met us anxiously at the station. Thus, early in the evening, in the little reception room of the Country Club, there gathered a large party, not the largest it had seen, but certainly the most interested. In fact no one, except young Ferris, had any legitimate reason for staying away. "Dead men tell no tales," remarked Kennedy sententiously, as he faced us, having whispered to me that he wanted me to take a position near the door and stay there, no matter what happened. "But," he added, "science opens their mute mouths. Science has become the greatest detective in the world. "Once upon a time, it is true, many a murderer was acquitted and perhaps many an innocent man hanged because of appearances. But today the assassin has to reckon with the chemist, the physicist, the X-ray expert, and a host of others. They start on his track and force him to face damning, dispassionate scientific facts. "And," he went on, raising his voice a trifle, "science, with equal zeal, brings facts to clear an innocent man protesting his innocence, but condemned by circumstantial evidence." For a moment he paused, and when he began again it was evident that he was going straight to the point at issue in the case. "Various theories have been confidently proposed in this unfortunate affair which resulted in the death of Irving Evans," he proceeded. "One thing I want clear at the start. The fact is, and I am not running counter to it, that we have what might very well be called two brains. One is in the head, does the thinking. The other is a sort of abdominal brain, controls nutrition and a host of other functions, automatically. It is the solar plexus--the epigastric, sympathetic nervous system. "It is true that the knot of life is situated at the base of the cranial brain. One jab of a needle and it might be quickly extinguished. Yet derangement of the so-called abdominal brain destroys life as effectually, though perhaps not so quickly. A shock to the abdominal brain of young Evans has been administered--in a most remarkable manner." I could see Mrs. Ferris watching him with staring eyes, for Kennedy was doing just what many a lawyer does--stating first the bad side of one's case, and seeming to establish the contention of the opposite side. "It was an unfortunate blow," he admitted, "perhaps even dangerous. But it was not deadly. What happened downstairs in the gymnasium must be taken into account with what happened afterwards in the locker and both considered in the light of the death of the steward, Benson, later. "The mark on the stomach of Irving Evans was due to something else than the blow. Everyone has noticed that. It was a peculiar mark and no mere blow could have produced it. "Weird in conception, horribly cunning in its execution was this attempt at murder," he added, taking from the case the peculiar flask which I had seen him pack up. He held it up so that we could see. It was evidently composed of two flasks, one inside the other, the outer encased in felt, as I had seen, the inner coated with quicksilver and a space between the two. Inside was a peculiar liquid which had a bluish tinge, but was odorless. From the surface a thin vapor seemed to rise. It was not corked, but from the neck he pulled out a light cotton stopper. As he agitated the liquid slightly, it had the appearance of boiling. He turned over the bottle and spilled some of it on the floor. It evaporated instantly, like water on a hot stove. Then he took from his pocket a small tin cup and poured out into it some of the liquid, letting it stand a few moments, smoking. He poured back the liquid into the flask and dropped the cup on the hardwood floor. It shattered as if it had been composed of glass. One of the men in the front row moved forward to pick up the pieces. "Just a minute," interfered Kennedy. "If you think anything of your fingers, let that be. In the rubbish, just outside the locker-room, yesterday, I discovered the remains of a thermos bottle and of a metal cup like this which I have dropped on the floor. I have examined the cup, or rather the pieces. "These two murders were committed by one of the least known agencies--freezing, by liquid air." I could hear a gasp from the auditors and I knew that someone's heart must be icy at the discovery of the portentous secret. "I have some liquid air in this Dewar flask," continued Kennedy. "That is what liquid air is usually kept in. But it may be kept in an ordinary thermos bottle quite well, also. "If I should drop just a minute bit on my hand, it would probably boil away without hurting me, for it evaporates so quickly that it forms a layer or film of air which prevents contact of the terribly cold liquid air and the skin. I might thrust my finger in it for a few seconds and it would not hurt me. But if I kept it there my finger would become brittle and actually break off, so terrible is the cold of one hundred and ninety degrees below zero, Centigrade. It produces an instantaneous frost bite, numbing so quickly that it often is hardly felt. Placed on the surface of flesh this way, it changes it to a pearly-white, solid surface. The thawing, however, is intensely painful, giving first a burning sensation, then a stinging, flushed feeling, exactly as Irving Evans described what he felt. The part affected swells and a crust forms which it takes weeks to heal, supposing the part affected is small. "Someone, in that locker-room," continued Craig, "placed a piece of cotton soaked in liquid air on the stomach of the unconscious boy. Instantly, before anyone noticed it, it froze through to the solar plexus. Ultimately that was bound to kill him. And who would bear the blame? Why, Fraser Ferris, of course. The accident in the bout afforded an opportunity to use the stuff which the criminal in his wildest dreams could not have bettered." "How about Benson, the steward?" spoke up a voice. We turned. It was the Coroner, loath even yet to give up the official theory. "That was a pure accident," returned Kennedy. "The club, as you know, is a temperance club. But the members, or at least some of them, keep drinks in their lockers. The steward, Benson, knew this. It has been shown that Benson had been in town that evening, had imbibed considerably. "He had observed one of the members of the club take from his locker something which he thought was to revive young Evans. What more natural, then, than for him to visit that locker when he returned from town, open it? "He found a thermos bottle. Instead of the regular cork, it had a light cotton stopper. In his muddled state, the steward did not stop to think--even if he had, he would have seen no reason for carefully corking something that was not designed to keep in a thermos bottle. "But instead of whiskey, the bottle contained what had not yet evaporated of the liquid air. You may not know it, but liquid air can be easily preserved in open vessels with a stopper which allows the passage of the evaporated air. However paradoxical it may seem, it cannot be kept in closed vessels, for enormous pressures are at once brought into play. "Benson opened the bottle and poured out some of the contents in the metal cup-cap of the bottle. He raised it to his lips--swallowed it--or that much of it that did not paralyze him. It expanded, boiled, exploded--producing the ghastly wound by almost literally blowing him up. "The owner of the liquid air, who must have had it there waiting a chance to use it, was probably waiting up in the club rooms now, for a chance to get rid of it as evidence. He must have heard a noise down in the locker-room. What if he had been observed and someone were down there investigating? "He hurried down there. To his horror, in the darkness, he found Benson, already dead, the locker open, the thermos bottle broken and the cup smashed. "It was a terrible clew. He must get that body away from the locker-room. He could throw the bottle out; no one could suspect anything when the air had evaporated, as it soon would, now. But the body--that was different. The method he employed in getting rid of the body, I think you all must already know." I had been watching Wyndham's face keenly. As Craig proceeded, I fancied that I saw in it a look of startled surprise. "_Was_ it one of Anita Allison's many admirers who did this thing?" Craig asked suddenly. I turned from Wyndham to Craig, wondering. What did he mean? Everyone had accepted that theory of the case so far. No one had questioned it. But, with his words, it suddenly dawned on me that it was by no means the only theory. Before Craig could go on, there came a startled cry from one of the ladies. "Oh--he did it--he did it!" Anita Allison had fainted. Dean Allison was at his sister's side in a moment. "Here--let me get her out into the fresh air," he cried. Wyndham had started up at the words and the two men were facing each other over the girl who had already discovered the secret, but had kept it locked in her breast. "Walter--lock that door," rang out Craig's voice mercilessly. I backed up, my whole weight against it, and turned the key. "I know the gossip of Wall Street now," shot out Kennedy hurriedly, facing the crowd who were all on their feet. "Today I have visited a number of speculative young gentlemen of Briar Lake, including Mr. Wyndham. "The truth is that Miss Allison's fortune was gone--dissipated in an unsuccessful bear raid on the market in which others have shared--and lost. "If she had married, it meant an accounting and surrendering of her full control of her fortune. You have done this dastardly crime, Dean Allison, to keep your sister in ignorance of the loss and to save your own miserable reputation!" CHAPTER XXV THE DEMON ENGINE "Perpetual motion sounds foolish, I'll admit. But, Professor Kennedy, this Creighton self-acting motor does things I can't explain." Craig looked perplexed as he gazed from Adele Laidlaw, his young and very pretty client, to me. We had heard a great deal about the young lady, one of the wealthiest heiresses of the country. She paused a moment and looked at us, evidently thinking of the many schemes which people had devised to get her money away from her. "Really," she went on, "I haven't a friend to whom I can go, except Mr. Tresham--no one on whom I can rely for advice in a case of this kind." Several times, I recollected, there had been rumors that she was engaged to Leslie Tresham, who had been the lawyer for her father before his death. The rumors had always been denied, however, though I am sure it was not Tresham's fault. "You see," she continued, as Craig still said nothing, "father was of a mechanical turn of mind; in fact so was the whole family, and I suppose I have inherited it. I'm just crazy over cars and boats. Anyhow, I was introduced to Mr. Creighton and he seemed so earnest and his work was so interesting that I bought a little of his stock. Now he needs more money to perfect his motor. Perhaps the thing is all right, but,--well, what do I really know about it?" One could not help feeling a great deal of sympathy for her. She was not the type of woman who would be easily misled, yet I could imagine that she must constantly be on her guard against schemers of every sort lurking to take advantage of every whim. "H'm," mused Kennedy, with a smile, eyeing our visitor keenly. "I've been consulted on about everything from pickpockets to the fountain of youth. Now it's perpetual motion. I must say, Miss Laidlaw, your case has a decided scientific interest for me, anyhow, as well as personal. I'd like to look at this wonderful machine, if you can arrange it." "I can do that," she answered confidently with a glance of thanks to Kennedy for his help. "May I use your telephone?" She had to wait some time for an answer to her call, but finally she got Creighton on the wire. "He had just come in," she said, hanging up the receiver. "He'll be there if we come down right away." Adele Laidlaw drove us downtown in her own high-powered car, which, true to her mechanical instincts, she handled herself. She drove it very well, too. In fact, I felt safer than with Kennedy, who, like many drivers, was inclined to take chances when he was at the wheel himself and could see what he was up against, though he balked severely when anyone else did it. "How did you become interested in this perpetual motion machine, Miss Laidlaw?" he asked as we threaded our way through the dense traffic. "Well, I suppose everyone knows that I'm interested in engines," she replied, as we waited for the signal from a policeman at a cross-street. "I've spent a good deal on them in speed-boats and in racing cars, too. An acquaintance, a friend of Mr. Creighton's, a Mrs. Barry,--Mr. Tresham knows her,--thought perhaps I might use the motor somehow and told me of it. I went down to see it and--I must confess that it fascinated me." I had not yet quite got myself accustomed to a girl who was interested in such things, though, in these days, I must confess, saw no reason why she should not be. Kennedy was dividing his attention between the admirable manner in which she handled the car and her very expressive face. Was it really, I wondered, that Creighton, more than his motor, has fascinated her? She drew up before the Consolidated Bank Building, a modern steel and concrete structure in the uptown business section. "The laboratory is next door," she said, as she let the car slide ahead a few feet more. "Mr. Tresham's office is in the Bank Building. I've had to go there so often since father died that I stopped through force of habit, I suppose." Mindful of Kennedy's admiration for Freud, his theory of forgetting occurred to me. Was there any significance in the mistake? Had the unconscious blunder betrayed something which perhaps she herself consciously did not realize? Was it Tresham, after all, whom she really admired and wanted to see? Creighton's workshop was in an old two-story brick building, evidently awaiting only the development of the neighborhood before it was torn down. Meanwhile the two buildings were in marked contrast. Which of them typified Creighton? Was he hopelessly out of date, or really ahead of his time? I must confess to having had a lively curiosity to meet the inventor. The entrance to the laboratory from the street was through a large door into a room in which was a carpenter's bench. On one side were some powerful winches and a large assortment of tools. In the back of the room a big door led to another room on the ground floor to the rear. "Mr. Creighton's is upstairs," remarked Miss Laidlaw, turning past the locked door and going up a worn flight of steps. "Whose shop is that?" asked Kennedy, indicating the door. "I don't know who rents these rooms down here," she replied. Up the stairway we went to the second floor. On the top landing stood some old machinery. In a little room on one side was a big desk, as well as books, instruments, and drawings of all sorts. Opposite this room was another little room, with many bits of expensive machinery on shelves and tables. Back of these two, and up a step, was a large room, the full width of the building, the workshop of the inventor, into which she led us. "I've brought a couple of friends of mine who may be interested in the vibrodyne motor," Miss Laidlaw introduced us. "Very pleased to meet you, gentlemen," Creighton returned. "Before we get through, I think you'll agree with me that you never dreamed of anything more wonderful than this motor of mine." He was a large, powerfully built man, with a huge head, square jaw with heavy side whiskers, and eyes that moved restlessly under a shock of iron-gray hair. Whether it was the actual size of his head or his bushy hair, one got the impression that his cranium housed a superabundant supply of brains. Every action was nervous and quick. Even his speech was rapid, as though his ideas outstripped his tongue. He impressed one as absorbed in this thing which he said frankly had been his life study, every nerve strained to make it succeed and convince people. "Just what is this force you call vibrodyne?" asked Craig, gazing about at the curious litter of paraphernalia in the shop. "Of course, I'm willing to admit," began Creighton quickly, in the tone of a man who was used to showing his machine to skeptical strangers but must be allowed to explain it in his own way, "that never before by any mechanical, electrical, thermal, or other means has a self-moving motor been made." He paused apparently to let us grasp the significance of what he was about to say. "But, is it impossible, as some of the old scientists have proved to their own satisfaction it must be?" he went on, warming up to his subject. "May there not be molecular, atomic, even ionic forces of which we have not dreamed? You have only to go back a few years and study radioactivity, for instance, to see how ideas may change. "Today," he added emphatically, "the conservation of energy, in the old sense at least, has been overthrown. Gentlemen, all the old laws must be modified by my discovery of vibrodyne. I loose new new forces--I create energy!" I watched him narrowly as he proposed and rapidly answered his own questions. He was talking quite as much for Miss Laidlaw's benefit, I thought, as ours. In fact, it was evident that her interest in the machine and in himself pleased him greatly. I knew already that though the search after perpetual motion through centuries had brought failure, still it captivated a certain type of inventive mind. I knew also that, just as the exact squaring of the circle and the transmutation of metals brought out some great mathematical discoveries and much of modern chemistry, so perpetual motion had brought out the greatest of all generalizations of physics--the conservation of energy. Yet here was a man who questioned the infallibility of that generalization. Actually taking the ultra-modern view that matter is a form of energy, he was asserting that energy in some way might be created or destroyed, at least transformed in a manner that no one had ever understood before. To him, radioactivity which had overthrown or amplified many of the old ideas was only a beginning. "Here is the machine," he pointed out at last, still talking, leading us proudly across the littered floor of his laboratory. It seemed, at first glance, to consist of a circular iron frame, about a foot and a half in diameter, firmly bolted to the floor. "I have it fastened down because, as you will see, it develops such a tremendous power," explained the inventor, adding, as he pointed above it, "That is all the power is developed from, too." On a shelf was a Daniell battery of four cells. In the porous cup was bichromate of potash and in the outer vessel dilute sulphuric acid. "Let me show you how I get two and a half horsepower out of three ounces of zinc for nine hours," went on Creighton proudly. "As you doubtless know, the usual thing is one horsepower per pound of zinc per hour. Ultimately, I expect to perfect the process until I get a thousand horsepower from an ounce in this vibrodyne motor." He started the engine by attaching the wires from the comparatively weak Daniell cells. Slowly it began to move, gaining speed, until finally the very floor shook from the great power and the rapidity of the motion. It seemed incredible that the small current from the battery should develop such apparent power and I looked at Kennedy in amazement. "There's a carelessly--or purposely--ill-balanced flywheel, I suspect," whispered Craig to me surreptitiously. "Yes, but the power," I persisted. He shook his head. Evidently he was not convinced, but had no theory, yet. Adele Laidlaw looked at Craig questioningly, as though to read what he thought of it. Before her he betrayed nothing. Now and then she would look earnestly at Creighton. It was evident that she admired him very much, yet there seemed to be something about him that she did not quite understand. Just then the telephone rang. Creighton stopped his machine and left us for a moment to answer the call, while the engine slowed down and came to rest. Quickly Kennedy pulled out his watch and pried the crystal off the face. He walked over to a basin and filled the crystal with a few drops of water. Then he set it down on the table. I looked at it closely. As nearly as I could make out, there seemed to be a slight agitation on the surface of the thin film of water in the glass. Craig smiled quietly to himself and flicked the water into the sink, returning the crystal to his watch. I did not understand just what it was that Craig was after, but I felt sure that there was some kind of vibration that he had discovered. Meanwhile, we could hear Creighton telephoning and I noticed that Miss Laidlaw was alertly listening, too. "Why, no," I heard him answer monosyllabically but in a tone that was carefully modulated, "not alone. Let me call you up--soon." The conversation ended almost as abruptly as it had begun. Somehow, it seemed evident to me that Creighton had been talking to a woman. Though he apparently had not wanted to say anything before us, he could not disguise the fact. From his quick, nervous manner with us, I had concluded that no mere man could have commanded so deferential a tone from him. A moment later he rejoined us, resuming his praises of his motor. By this time I had come to recognize that he was a master in the manipulation of fantastic terms, which I, at least, did not understand. Therein, perhaps, lay their potency, though I doubt whether Kennedy himself knew what Creighton meant when he talked of "polar sympathy," "inter-atomic ether," "molecular disintegration," and "orbitic chaos." I saw that Adele Laidlaw was watching Creighton narrowly now. Was it on account of the telephone call? Who had it been? Perhaps, it occurred to me, it was Mrs. Barry. Was Creighton afraid of arousing the jealousy of Adele Laidlaw? There seemed to be nothing more of importance that Craig could learn at present and we soon bade Creighton good-by, leaving with Miss Laidlaw. I noticed that he locked the door after us as we went out. "I'd like to meet this Mrs. Barry," remarked Craig as we passed out of the building. He said it evidently to see just how Miss Laidlaw would take it. "I think I can arrange that," replied Adele Laidlaw colorlessly. "I'll ask her to visit me this afternoon. You can call casually." We accompanied her to her car, promising to report as soon as possible if we discovered anything new. "I'm going in to call on Tresham," remarked Craig, turning into the Bank Building. CHAPTER XXVI THE ELECTROLYSIS CLEW As Kennedy walked through the corridor of the building, he paused and bent down, as though examining the wall. I looked, too. There was a crack in the concrete, in the side wall toward the Creighton laboratory. "Do you suppose vibration caused it?" I asked, remembering his watch crystal test. Craig shook his head. "The vibrations in a building can be shown by a watch glass full of water. You saw the surface of the liquid with its minute waves. There's vibration, all right, but that is not the cause of such cracks as these." He stood for a moment regarding the crack attentively. On the floor on which we were was the Consolidated Bank itself. Beneath us were the Consolidated Safety Deposit vaults. "What did cause them, then?" I asked, mystified. "Apparently escaping currents of electricity are causing electrolysis of the Bank Building," he replied, his face wrinkled in thought. "Electrolysis?" I repeated mechanically. "Yes. I suppose you know how stray or vagrant currents affect steel and concrete?" I shook my head in the negative. "Well," he explained as we stood there, "I believe that in one government test at least it was shown that when an electric current of high voltage passes from steel to concrete, the latter is cracked and broken. Often a mechanical pressure as great as four or five thousand pounds a square inch is exerted and there is rapid destruction due to the heating effect of the current." I expressed my surprise at what he had discovered. "The danger is easily overestimated," he hastened to add. "But in this case I think it is real, though probably it is a special and extreme condition. Still it is special and extreme conditions which we are in the habit of encountering in our cases, Walter. That is what we must be looking out for. In this instance the destruction due to electrolysis is most likely caused by the oxidation of the iron anode. The oxides which are formed are twice as great in volume as the iron was originally and the resulting pressure is what causes the concrete to break. I think we shall find that this condition will bear strict watching." For a moment Kennedy stopped at the little office of the superintendent of the building, in the rear. "I was just wondering whether you had noticed those cracks in the walls down the corridor," remarked Kennedy after a brief introduction. The superintendent looked at him suspiciously. Evidently he feared we had some ulterior motive, perhaps represented some rival building and might try to scare away his tenants. "Oh, that's nothing," he said confidently. "Just the building settling a bit--easily fixed." "The safety vault company haven't complained?" persisted Kennedy, determined to get something out of the agent. "No indeed," he returned confidently. "I guess they've got troubles of their own--real ones." "How's that?" asked Craig, falling in with the man's evident desire to change the subject. "Why, I believe their alarm system's out of order," he replied. "Some of the fine wires in it burnt out, I think. Defective wiring, I guess. Oh, they've had it patched up, changed about a little,--it's all right now, they say. But they've had a deuce of a time with the alarm ringing at all sorts of hours, and not a trace of trouble." I looked quickly at Craig. Though the superintendent thought he had been very clever in changing the topic of conversation, he had unwittingly furnished us with another clew. I could not ask Craig before him and I forgot to do so later, but, to me at least, it seemed as if this might be due to induction from the stray currents. "No one here seems to have suspected the Creighton motor, anyhow," commented Craig to me, as we thanked the superintendent and walked across to the elevators. We rode up to Tresham's office, which was on the third floor, on the side of the building toward Creighton's laboratory. In fact one of the windows opened almost on the roof of the brick building next door. We found Tresham in his office and he received us affably, I thought. "Miss Laidlaw told me she was going to consult you," he remarked as we introduced ourselves. "I'm glad she did so." Tresham was a large, well-built fellow, apparently athletically inclined, clean shaven with dark hair that was getting very thin. He seemed quite at ease as he talked with us, yet I could tell that he was weighing us all the time, as lawyers will do. "What do you think of Creighton's motor?" opened Kennedy. "You've seen it, I suppose?" "Oh, yes," he replied quickly and jerkily. "Since Miss Laidlaw became interested he's been in here to have me look over his application for a patent. You know, I used to be a patent lawyer for a number of years until I decided to branch out into general practice. Legally Creighton seems to be sound enough. Of course, you know, the patent office won't grant a patent on a machine such as he claims without a rigid demonstration. He needs money, he says, for that. If his idea is sound, I don't see any reason why he shouldn't get a basic patent." Tresham paused. I was conscious that he was furtively watching the face of Kennedy as though he hoped to learn as much from him as Craig did on his part. "It's the mechanical end of it that I don't understand," continued Tresham, after a pause. "Creighton claims to have discovered a new force which he calls vibrodyne. I think it is just as well that Miss Laidlaw has decided to consult a scientist about it before she puts any more money into the thing. I can't say I approve of her interest in it--though, of course, I know next to nothing about it, except from the legal standpoint." "Who is that Mrs. Barry of whom Miss Laidlaw spoke?" asked Kennedy a moment later. "I believe she is a friend of Creighton's. Somehow she got acquainted with Miss Laidlaw and introduced her to him." "You know her?" queried Craig casually. "Oh, yes," came the frank reply. "She has been in to see me, too; first to interest me in the motor, and then to consult me about various legal points in connection with it." I felt sure that Tresham was more than just a bit jealous of his pretty client. Certainly his tone was intended to convey the impression that he wished she would leave her affairs in his hands entirely. "You don't know anything more about her--where she came from--her connections?" added Craig. "Hardly more than you do," asserted Tresham. "I've only seen the woman a few times. In fact I should be glad to know more about her--and about Creighton, too. I hope that if you find out anything you'll let me know so that I can protect Miss Laidlaw's interests." "I shall do so," promised Kennedy, rising. "I'll do the same," agreed Tresham, extending his hand. "I see no reason why we shouldn't work together for--my client." There was no mistaking the fact that Tresham would have liked to be able to say something more intimate than "client." Perhaps he might have been nearer to it if her interest in him had not been diverted by this wonderful motor. At any rate I fancied he had little love for Creighton. Yet, when I reflected afterward, it seemed like a wide gulf that must separate a comparatively impecunious lawyer from a wealthy girl like Adele Laidlaw. Kennedy was not through with his effort to learn something by a thorough investigation of the neighborhood yet. For some time after we left Tresham's office, he stood in the doorway of the Bank Building, looking about as though he hated to leave without establishing some vantage point from which to watch what was going on in Creighton's laboratory. "Of course I can't very well get into the safety vault under the bank," he mused. "I wish I could." He walked past Creighton's without seeing anything happen. The next building was a similar two-story brick affair. A sign on it read, "Studios and Offices For Rent." An idea seemed to be suggested to him by the sign. He wheeled and entered the place. Inquiry brought out a caretaker who showed us several rooms unoccupied, among them one vacant on the first floor. Kennedy looked it over carefully, as though considering whether it was just the place he wanted, but ended, as I knew he intended, in hiring it. "I can't move my stuff in for a couple of days," he told the caretaker. "Meanwhile, I may have the key, I suppose?" He had paid a good deposit and the key was readily forthcoming. The hiring of the ground floor room accomplished without exciting suspicion, Kennedy and I made a hasty trip up to his own laboratory, where he took a small box from a cabinet and hurried back to the taxicab which had brought us uptown. Back again in the bare room which he had acquired, Craig set to work immediately installing a peculiar instrument which he took from the package. It seemed to consist of two rods much like electric light carbons, fixed horizontally in a wooden support with a spindle-shaped bit of carbon between the two ends of the rods. Wires were connected with binding screws at the free ends of the carbon rods. First Craig made a connection with an electric light socket from which he removed the bulb, cutting in a rheostat. Then he attached the free wires from the carbons to a sort of telephone headgear and switched on the current. "What is it?" I asked curiously. "A geophone," he replied simply. "And what is a geophone?" I inquired. "Literally an earth-phone," he explained. "It is really the simplest form of telephone, applied to the earth. You saw what it was. Any high school student of physics can make one, even with two or three dry batteries in circuit." "But what does it do?" I asked. "It is really designed to detect earth vibrations. All that is necessary is to set the carbon stick arrangement, which is the transmitter of this telephone, on the floor, place myself at the other end and listen. A trained ear can readily detect rumblings. Really it is doing in a different and often better way what the seismograph does. This instrument is so sensitive that it will record the slamming of a cellar door across the street. No one can go up those stairs next door without letting me know it, no matter how cautious he is about it." Craig stood there some minutes holding the thing over his ears and listening intently. "The vibrodyne machine isn't running," he remarked finally after repeated adjustments of the geophone. "But someone is in that little room under Creighton's workshop. I suspected that something was down there after that watch crystal test of mine. Now I know it. I wonder what the man is doing?" There was no excuse yet, however, for breaking into the room on the other side of the wall and under Creighton's. Kennedy went out and watched. Though we waited some time nobody came out. He went back to our own room in the rear of the first floor. Though we both listened some time, neither of us could now hear a sound through the geophone except those made by passing trolleys and street vehicles. Inquiry about the neighborhood did not develop who was the tenant or what was his business. In fact the results were just the reverse. No one seemed to know even the business conducted there. The room back of the locked door which Miss Laidlaw had passed was shrouded in mystery. Nothing at all of any value was being recorded by the geophone when Kennedy glanced quickly at his watch. "If we are to see Miss Laidlaw and meet that Mrs. Barry, we had better be on our way," he remarked hurriedly. Miss Laidlaw was living in a handsome apartment on Central Park, West. We entered and gave our cards to the man at the door of her suite, who bowed us into a little reception room. We entered and waited. Suddenly we were aware that someone in the next room, a library, was talking. Whether we would or not we could not help overhearing what was said. Apparently two women were there, and they were not taking care how loud they spoke. "Then you object to my even knowing Mr. Creighton?" asked one of the voices, pausing evidently for a reply which the other did not choose to make. "I suppose if it was Mr. Tresham you'd object, too." There was something "catty" and taunting about the voice. It was a hard voice, the voice of a woman who had seen much, and felt fully capable of taking care of herself in more. "You can't make up your mind which one you care for most, then? Is that it?" pursued the same voice. "Well, I'll be a sport. I'll leave you Creighton--if you can keep him." "I want neither," broke in a voice which I recognized at once as Adele Laidlaw's. She spoke with a suppressed emotion which plainly indicated that she did want one of them. Just then the butler entered with our cards. We heard no more. A moment later we were ushered into the library. Mrs. Barry was a trim, well-groomed woman whose age was deceptive. I felt that no matter what one might think of Miss Laidlaw, here was a woman whose very looks seemed to warn one to be on his guard. She was a woman of the world, confident in her own ability to take care of herself. Adele was flushed and excited, as we entered, though she was making a desperate effort to act as though nothing had happened. "My friend, Professor Kennedy, and Mr. Jameson," she introduced us simply, making no pretense to conceal our identity. Mrs. Barry was, in addition to her other accomplishments, a good actress. "I've heard a great deal about you, Professor," she said, extending her hand, but not taking her eyes off Craig's face. Kennedy met her gaze directly. What did she mean? Had she accepted Miss Laidlaw's invitation to call in order to look us over, knowing that we had come to do the same? "Mr. Creighton tells me that you have been to see his new motor," she ventured, even before any of us could open the subject. She seemed to enjoy making the remark for the specific purpose of rousing Miss Laidlaw. It succeeded amply, also. The implication that Creighton took her into his confidence was sufficient to cause Adele Laidlaw to shoot an angry glance at her. Mrs. Barry had no objection to sticking a knife in and turning it around. "Of course I don't know as much about such things as Miss Laidlaw," she purred, "but Mr. Tresham tells me that there may be some trouble with the patent office about allowing the patent. From all I have heard there's a fortune in that motor for someone. Wonderful, isn't it?" Even the mention of Tresham's name in the studied familiarity of her tone seemed to increase the scarcely latent hostility between the two women. Kennedy, so far, had said nothing, content merely to observe. "It appears to be wonderful," was all he said, guardedly. Mrs. Barry eyed him sharply and Miss Laidlaw appeared to be ill at ease. Evidently she wanted to believe in Creighton and his motor, yet her natural caution forbade her. The entrance of Kennedy into the case seemed to have proved a disturbing factor between the two women, to have brought matters to a head. We chatted for a few minutes, Kennedy deftly refusing to commit himself on anything, Mrs. Barry seeking to lead him into expressing some opinion, and endeavoring to conceal her exasperation as he avoided doing so. At last Kennedy glanced at his watch, which reminded him of a mythical appointment, sufficient to terminate the visit. "I'm very glad to have met you," he bowed to Mrs. Barry, as she, too, rose to go, while he preserved the fiction of merely having dropped in to see Miss Laidlaw. He turned to her. "I should be delighted to have both you and Mr. Tresham drop in at my laboratory some time, Miss Laidlaw." Miss Laidlaw caught his eye and read in it that this was his way, under the circumstances, of asking her to keep in touch with him. "I shall do so," she promised. We parted from Mrs. Barry at the door of her taxicab. "A very baffling woman," I remarked a moment later. "Do you suppose she is as intimate with Creighton as she implies?" Kennedy shook his head. "It isn't that that interests me most, just now," he replied. "What I can't figure out is Adele Laidlaw's attitude toward both Creighton and Tresham. She seems to resent Mrs. Barry's intimacy with either." "Yes," I agreed. "Sometimes I have thought she really cared for both--at least, that she was unable to make up her mind which she cared for most. Offhand, I should have thought that she was the sort who wouldn't think a man worth caring much for." Kennedy shook his head. "Given a woman, Walter," he said thoughtfully, "whose own and ancestral training has been a course of suppression, where she has been taught and drilled that exhibitions of emotion and passion are disgraceful, as I suspect Miss Laidlaw's parents have believed, and you have a woman whose primitive instincts have been stored and strengthened. The instincts are there, nevertheless, far back in the subconscious mind. I don't think Adele Laidlaw knows it herself, but there is something about both those men which fascinates her and she can't make up her mind which fascinates her most. Perhaps they have the same qualities." "But Mrs. Barry," I interrupted. "Surely she must know." "I think she does," he returned. "I think she knows more than we suspect." I looked at him quickly, not quite making out the significance of the remark, but he said no more. For the present, at least, he left Adele Laidlaw quite as much an enigma as ever. "I wish that you would make inquiries about regarding Mrs. Barry," he said finally as we reached the subway. "I'm going down again to the little room we hired and watch. You'll find me at the laboratory later tonight." CHAPTER XXVII THE PERPETUAL MOTION MACHINE I tried my best, but there was very little that I could find out about Mrs. Barry. No one seemed to know where she came from, and even "Mr. Barry" seemed shrouded in obscurity. I was convinced, however, that she was an adventuress. One thing, however, I did turn up. She had called on Tresham at his office a number of times, usually late in the afternoon, and he had taken her to dinner and to the theater. Apparently he knew her a great deal better than he had been willing to admit to us. I was not surprised, for, like a good many men of his class, Tresham was better known in the white light district than one might suspect. Mrs. Barry had all the marks of being good company on such an excursion. On the way uptown, I stopped off in the neighborhood of Longacre Square in the hope of picking up some more gossip at one or another of the clubs. Tresham was a member of several, though as near as I could find out, used them more for business than social reasons. On Broadway it was different, however. There he was known as a liberal spender and lover of night life. Like many others he now and then accumulated quite large bills. I wondered whether Mrs. Barry had not found out and taken advantage of his weakness. It was, as I have said, comparatively little that I had been able to discover, yet when I met Kennedy again, later in the evening, at his laboratory, he listened eagerly to what I had to report. "Did anything happen downtown?" I asked when I had finished. "Nothing much," he returned. "Of course, listening over the geophone, I couldn't watch the Bank Building, too. There's something very queer about Creighton. I could hear him at work in the room upstairs until quite late, making a lot of noise. If I don't find out anything more definite soon, I shall have to adopt some other measures." "You didn't do anything more about that electrolysis clew?" I queried. "Nothing," he replied briefly, "except that I inquired of the electric light company and found out that Creighton, or someone in his building, was using a good deal of power." "That looks bad," I ventured, remembering the claims made for the engine and the comparatively weak batteries that were said to run it. Kennedy nodded acquiescence, but said nothing more. We walked over in silence to our apartment on the Heights and far into the night Craig sat there, shading his eyes with his hand, apparently studying out the peculiar features of the case and planning some new angle of approach at it tomorrow. We were surprised the next day to receive an early visit from Miss Laidlaw at the laboratory. She drove up before the Chemistry Building, very much excited, as though her news would not bear repeating even over the telephone. "What do you think?" she exclaimed, bursting in on us. "Mr. Creighton has disappeared!" "Disappeared?" repeated Kennedy. "How did you find it out?" "Mr. Tresham just telephoned me from his office," she hurried on. "He was going into the Bank Building when he saw a wagon drive off from the place next door. He thought it was strange and instead of going on up to his own office he walked into Creighton's. When he tried to get in, the place was locked. There's a sign on it, too, 'For Rent,' he says." "That's strange," considered Kennedy. "I suppose he didn't notice what kind of wagon it was?" "Yes, he said it looked like a junk wagon--full of stuff." I looked from Miss Laidlaw to Kennedy. Plainly our entrance into the case had been the signal for the flitting of Creighton. Quickly he reached for the telephone. "You know Mrs. Barry's number?" he asked. "Yes, it's the Prince Edward Hotel." He called up, but the conversation was over in a moment. "She didn't return to the hotel last night," he announced as he hung up the receiver. "She's in this thing, too," exclaimed Adele Laidlaw. "Can you go down with me now and meet Mr. Tresham? I promised I would." Though she repressed her feelings, as usual, I could see that Adele Laidlaw was furious. Was it because Creighton had gone off with her money, or was it pique because Mrs. Barry had, perhaps, won him? At any rate, someone was going to feel the fury of her scorn. We motored down quickly in Miss Laidlaw's car and met Tresham, who was standing in front of the Bank Building waiting for us. "It just happened that I came down early this morning," he explained, "or I shouldn't have noticed anything out of the way. The junk wagon was just driving away as I came up. It seemed to be in such a hurry that it attracted my attention." It was the first time we had seen Tresham and Miss Laidlaw together and I was interested to see how they would act. There was no mistaking his attitude toward her and Adele was much more cordial to him than I had expected. "While I was waiting I got a key from the agent," he explained. "But I didn't want to go in until you came." Tresham opened the door and led the way upstairs, Miss Laidlaw following closely. As we entered Creighton's shop, everything seemed to be in the greatest disorder. Prints and books were scattered about, the tools were lying about wherever they happened to have been left, all the models were smashed or missing and a heap of papers in the fireplace showed where many plans, letters and other documents had been burned. We hurried into the big room. Sure enough, the demon motor itself was gone! Creighton had unbolted it from the floor and some holes in the boards had been plugged up. The room below was still locked and the windows were covered with opaque paper on the inside. "What do you suppose he has done with the motor?" asked Adele. "The only clew is a junk dealer whom we don't know," I replied, as Kennedy said nothing. We looked about the place thoroughly, but could find nothing else. Creighton seemed to have made a clean getaway in the early hours. "I wish I could stay and help you," remarked Tresham at length. "But I must be in court at ten. If there's anything I can do, though, call on me." "I'm going to find that engine if I have to visit every junk dealer in New York," declared Miss Laidlaw soon after Tresham left. "That's about all we can do, yet, I guess," remarked Kennedy, evidently not much worried about the disappearance of the inventor. Together we three closed up the workshop and started out with a list from a trade publication giving all those who dealt in scrap iron and old metal. In fact we spent most of the day going from one to another of the junk shops. I never knew that there were so many dealers in waste. They seemed to be all over the city and in nearly every section. It was a tremendous job, but we mapped it out so that we worked our way from one section to another. We had got as far as the Harlem River when we entered one place and looked about while we waited for someone in charge to appear. I heard a low exclamation from Kennedy, and turned to look in the direction he indicated. There, in a wagon from which the horse had been unhitched, was the heavy base of the engine into which so many dollars had been turned--sold as so much scrap! Kennedy examined it quickly, while I questioned a man who appeared from behind a shed in the rear. It was useless. He could give no clew that we already could not guess. He had just bought it from a man who seemed anxious to get rid of it. His description of the man tallied with Creighton. But that was all. It gave us no chance to trace him. "Look," exclaimed Kennedy eagerly, bending closer over the motor. "This is one of the neatest perpetual motion frauds I ever heard of." He had turned the heavy base of the motor upward. One glance left me with little wonder why Creighton had so carefully bolted the machine to the floor. In the base were two rectangular apertures to allow a belt to run over a concealed pulley on the main shaft of the machine in the case. Evidently, when the circuit from the Daniell cells was closed, the pulley, somehow, was thrown into gear. It was loose and the machine began to revolve slowly at first, then faster and with great show of power. The pounding, as Kennedy had surmised, was due to the flywheel not well balanced. "Well," I remarked, "now that we have found it, I don't see that it does us much good." "Only that we understand it," returned Craig. "I left that geophone down there in the room next door which I hired. I think, if Miss Laidlaw will take us down there, I'd like to get it." He spoke with a sort of easy confidence which I knew was hard to be assumed in the face of what looked like defeat. Had Craig deliberately let Creighton have a chance to get away, in order that he might convict himself? In silence, with Miss Laidlaw at the wheel, we went downtown again to the room which Craig had hired next to Creighton's workshop. As we approached it, he leaned over to Miss Laidlaw. "Stop around the corner," he asked. "Let's go in quietly." We entered our bare little room and Kennedy set to work as though to detach the geophone, while I explained it to our client. "What's the matter?" she interrupted in the middle of my explanation, indicating Kennedy. He had paused and had placed the receivers to his ears. By his expression I knew that the instrument was registering something. "Someone is in the lower room of the shop next door," he answered, facing us quickly. "If we hurry, we'll have him cornered." Miss Laidlaw and I went out and around in front, while Craig dashed through a back door to cut off retreat that way. "What's that? Hurry!" exclaimed Miss Laidlaw. Plainly there was a muffled scream of a woman as we entered the street door. I hurried forward. It was the work of only a few seconds to batter down the locked door in the room under Creighton's old workshop, and as the door gave way, I heard the sound of shattered glass from the rear which told that Kennedy had heard the scream, too, and had gained an entrance. Inside I could make out in the half-light a man and a woman. The woman was running toward me, as if for help. "Mrs. Barry!" gasped Adele Laidlaw. "He got me here--to kill me!" she cried hysterically. "I am the only one who knows the truth--it was the last day--tonight he would have had the money--and I would have been out of the way. But I'll expose him--I'll ruin him. See--he came in from the roof--" A blinding flash of light greeted us, followed by a scream from Adele Laidlaw, as she ran past us and dropped on her knees beside a body that had fallen with a thud in the flame before a yawning hole in the side wall. Mrs. Barry ran past me, back again, at almost the same moment. It was a strange sight--these two women glaring at each other over the prostrate figure of the man. "Here's the real demon engine," panted Craig, coming up from the back and pointing to an electric motor as well as other apparatus consisting of several series of coils. "The perpetual motion machine was just a fake. It was merely a cover to an attempt to break into the bank vaults by electrolysis of the steel and concrete. Creighton was a dummy, a fiction--to take the blame and disappear when the robbery was discovered." "Creighton," I repeated, looking at the man on the floor, "a dummy?" "Oh--he's dead!" wailed Adele Laidlaw. "He's dead!" "Electrocuted by his own machine rather than face disgrace and disbarment," cut in Craig. "No wonder she was in doubt which of the two men fascinated her most." I moved forward and bent over the contorted form of the lawyer, Tresham, who was wearing the whiskers and iron gray wig of his alter-ego, Creighton. CHAPTER XXVIII THE CANCER HOUSE "You've heard of such things as cancer houses, I suppose, Professor Kennedy?" It was early in the morning and Craig's client, Myra Moreton, as she introduced herself, had been waiting at the laboratory door in a state of great agitation as we came up. Just because her beautiful face was pale and haggard with worry, she was a pathetic figure, as she stood there, dressed in deep mourning, the tears standing in her eyes merely because we were a little later than usual. "Well," she hurried on as she dropped into a chair, "that is what they are calling that big house of ours at Norwood--a cancer house, if there is such a thing." Clearly, Myra Moreton was a victim of nervous prostration. She had asked the question with a hectic eagerness, yet had not waited for an answer. "Oh," she exclaimed, "you do not, you cannot know what it means to have something like this constantly hanging over you. Think of it--five of us have died in less than five years. It haunts me. Who next. That is all I can think about. Who next?" Her first agitation had been succeeded by a calmness of despair, almost of fatalism, which was worse for her than letting loose her pent-up emotions. I had heard of cases of people in whom there was no record of hereditary predisposition to cancer, people apparently in perfect health, who had moved into houses where cancer patients had lived and died and had themselves developed the disease. Though I had, of course, never even remotely experienced such a feeling as she described, I could well fancy what it must be to her. Kennedy watched her sympathetically. "But why do you come to me?" he asked gently. "Don't you think a cancer specialist would be more likely to help you?" "A specialist?" she repeated with a peculiar hopelessness. "Professor Kennedy, five years ago, when my Uncle Frank was attacked by cancer, father was so foolish as to persuade him to consult a specialist whose advertisement he saw in the papers, a Dr. Adam Loeb on Forty-second Street here in New York. Specialist! Oh, I'm worried sick every time I have a sore or anything like this on my neck or anywhere else." She had worked herself from her unnatural calm almost into a state of hysterics as she displayed a little sore on her delicate white throat. "That?" reassured Kennedy. "Oh, that may be nothing but a little boil. But this Dr. Loeb--he must be a quack. No doctor who advertises--" "Perhaps," she interrupted. "That is what Dr. Goode out at Norwood tells me. But father has faith in him, even has him at the house sometimes. I cannot bear the sight of him. Since I first saw him my uncle, his wife, another aunt, my cousin have died, and then, last week, my--my mother." Her voice broke, but with a great effort she managed to get herself together. "Now I--I fear that my father may go next. Perhaps it will strike me--or my brother, Lionel--who can tell? Think of it--the whole family wiped out by this terrible thing. Can it be natural, I ask myself? Is there not something back of it?" "Who is this Dr. Loeb?" asked Kennedy, more for the purpose of aiding her in giving vent to her feelings than anything else. "He is a New York doctor," she reiterated. "I believe he claims to have a sure cure for cancer, by the use of radium and such means. My father has absolute confidence in him--visits him at his office and, as I told you, even has him at Norwood. In fact they are quite friendly. So was Lionel until lately." "What happened to shake your brother's faith?" asked Craig. "Nothing, I imagine, except that Lionel began thinking it over after someone told him about cancer houses. You must admit yourself that it is--at least strange. I wish you could see Lionel. He knows more about it than I do. Or Dr. Goode. I think he has made some kind of test. He could tell you much better than I can all the strange history. But they don't agree--Lionel and Gail. Oh--it is more than I can stand. What shall I--" She had fainted. In an instant I was at her side, helping Kennedy bring her around. "There, there," soothed Kennedy several minutes later as her deep eyes looked at him appealingly. "Perhaps, after all, there may be something I can do. If I should go out to Norwood with you as soon as you feel better, wouldn't that be all right?" "Oh--will you?" she cried, overjoyed. "If you would--how could I ever thank you? I feel better. No--don't stop me. I've been living on nerve. I can do more. Please--let me telephone Lionel that we are coming." Kennedy humored her, although I knew he had several important investigations going on at the time. It was scarcely an hour before we were on the train and in the early forenoon we were met by her brother at the station in a light car. Through the beautiful streets of the quaint old Connecticut town we rode until at last we stopped before a great stone house which had been the Moreton mansion for several generations. It was a double house, a gloomy sort of place, surrounded by fir trees, damp and suggestive of decay. I could not help feeling that if ever there were a house about which I could associate the story which Myra had poured forth, this was it. Somehow, to me at least, it had all the mystery of being haunted. Darius Moreton, her father, happened to be at home to lunch when we arrived. He was a man past middle age. Like his father and grandfather, he was a manufacturer of optical goods and had increased the business very well. But, like many successful business men, he was one of those who are very positive, with whom one cannot argue. Myra introduced Kennedy as interested in cause and treatment of cancer, and especially in the tracing down of a definite case of a "cancer house." "No," he shook his head grimly, "I'm afraid it is heredity. My friend, Dr. Loeb, is the only one who understands it. I have the most absolute confidence in him." He said it in a way that seemed to discourage all argument. Kennedy did not antagonize him by disagreeing, but turned to Lionel, who was a rather interesting type of young man. Son of Darius Moreton by his first wife, Lionel had gone to the scientific school as had his father and, graduating, had taken up the business of the Moreton family as a matter of course. Myra seemed overcome by the journey to the city to see Kennedy and, after a light luncheon, Lionel undertook to talk to us and show us through the house. It was depressing, almost ghastly, to think of the slow succession of tragedies which these walls had witnessed. "This is a most unusual case," commented Craig thoughtfully as Lionel went over briefly the family history. "If it can be authenticated that this is a cancer house, I am sure the medical profession will be interested, for they seem to be divided into two camps on the question." "Authenticated?" hastened Lionel. "Well, take the record. First there was my Uncle Frank, who was father's partner in the factory. He died just about five years ago at the age of fifty-one. That same year his wife, my Aunt Julia, died. She was just forty-eight. Then my other aunt, Fanny, father's sister, died of cancer of the throat. She was rather older, fifty-four. Not quite two years afterward my cousin, George, son of Uncle Frank, died. He was several years younger than I, twenty-nine. Finally my step-mother died, last week. She was forty-nine. So, I suppose we may be pardoned if, somehow, in spite of the fact, as you say, that many believe that the disease is not contagious or infectious or whatever you call it, we believe that it lurks in the house. Myra and I would get out tomorrow, only father insists that there is nothing in it, says it is all heredity. I don't know but that that's worse. That means that there is no escape." We had come down the wide staircase into the library, where we joined Myra, who was resting on a chaise-longue. "I should like very much to have a talk with Dr. Goode," suggested Craig. "By all means," agreed Myra eagerly. "I'll go over to his office with you. It is only next door." "Then I'll wait here," said Lionel, rather curtly, I thought. I fancied that there was a coolness that amounted to a latent hostility between Lionel and Dr. Goode, and I wondered about it. Across the sparse lawn that struggled up under the deep shade of the trees stood a smaller, less pretentious house of a much more modern type. That was where Dr. Goode lived. We crossed with Myra through a break in the hedge between the two houses. As we were about to pass between the two grounds, Kennedy's foot kicked something that seemed to have rolled down from some rubbish on the boundary line of the two properties, piled up evidently waiting to be carted away. Craig stooped casually and picked the object up. It was a queer V-shaped little porcelain cone. He gave it a hasty look, then dropped it into his pocket. Dr. Goode, into whose office Myra led us, was a youngish man, smooth-shaven, the type of the new generation of doctors. He had come to Norwood several years before and had struggled up to a very fair practice. "Miss Moreton tells me," began Kennedy after we had been introduced, "that there is a theory that theirs is one of these so-called cancer houses." The doctor looked at us keenly. "Yes," he nodded, "I have heard that theory expressed--and others, too. Of course, I haven't had a chance to verify it. But I may say that, privately, I am hardly prepared to accept it, yet, as a case of cancer house." He was very guarded in his choice of words, but did not succeed in covering up the fact that he had a theory of his own. I was watching both the young doctor and Myra. She had entered his office in a way that suggested that she was something more than a patient. As I watched them, it did not take one of very keen perception to discover that they were on very intimate terms indeed and thought very highly of each other. A glance at the solitaire on Myra's finger convinced me. They were engaged. "You don't believe it, then?" asked Craig quickly. The young man hesitated and shrugged his shoulders. "You have a theory of your own?" persisted Craig, determined to get an answer. "I don't know whether I have or not," he replied non-committally. "Is it that you think it possible to produce cancer artificially and purposely?" shot out Craig. Dr. Goode considered. I wondered whether he had any suspicions of which he would not speak because of professional ethics. Kennedy had fixed his eyes on him sharply and the doctor seemed uneasy under the scrutiny. "I've heard of cases," he ventured finally, "where X-rays and radium have caused cancerous growths. You know several of the experimenters have lost their lives in that way--martyrs to science." I could not help, somehow or other, thinking of Dr. Loeb. Did Dr. Goode refer indirectly to him? Loeb certainly was no martyr to science. He might be a charlatan. But was he a scientific villain? "That may all be true," pursued Craig relentlessly, evidently bound to draw the young man out. "But it is, after all, a question of fact, not of opinion." Myra was looking at him eagerly now and the doctor saw that she expected him to speak. It was more pressure than he could resist. "I have long suspected something of the sort," he remarked in a low, forced tone. "I've had samples of the blood of the Moretons examined. In fact I have found that their blood affects the photographic plate through a layer of black paper. You know red blood cells and serum have a distinct power of reducing photo-silver on plates when exposed to certain radiations. In other words, I have found that their blood is, apparently, radioactive!" Myra looked at him aghast. It was evidently the first time he had said anything about this new suspicion, even to her. The very idea was shocking. Could it be that someone was using these new forces with devilish ingenuity? "If that's the case, who would be the most likely person to do such a thing?" shot out Craig. "I wouldn't like to say," he returned, dodging, though we were all thinking of Dr. Loeb. "But the motive?" demanded Craig. "What motive would there be?" "Darius Moreton is very intimate with a certain person," he returned enigmatically. "It is even reported in town that he has left that person a large sum of money in his will in payment for his services, if you call them so, to the family." He had evidently not intended to say so much and, although Craig tried in every way, he could not get the doctor to amplify what he had hinted at. We returned to the Moreton house, Kennedy apparently much impressed by what Dr. Goode had said. "If you will permit me," he asked, "I should like to have a few drops of blood from each of you." "Goode tried that," remarked old Mr. Moreton. "I don't know that anything came of it. Still, I am not going to refuse, if Myra and Lionel agree." Craig had already taken from his pocket a small case containing a hypodermic and some little glass tubes. There seemed to be no valid objection and from each of them he drew off a small quantity of blood. As he worked, I thought I saw what he had in mind. Could there be, I wondered, an X-ray outfit or perhaps radium concealed about the living rooms of the house? First of all, it was necessary to verify Dr. Goode's observations. We chatted a few moments, then took leave of Myra Moreton. "Keep up your courage," whispered Craig with a look that told her that he had seen the conflict between loyalty to her father and to her lover. Lionel drove us back to the station in the car alone. Nothing of importance was said by any of us until we had almost reached the station. "I can see," he said finally, "that you don't feel sure that it is a cancer house." Kennedy said nothing. "Well," he pursued, "I don't know anything about it, of course. But I do know this much--those doctors are making a good thing out of father and the rest of us." The car had pulled up. "I've got no use for Loeb," the young man went on. "Still, I'd rather not that we had trouble with him. I'll tell you," he added in a burst of confidence, "he has a little girl who works for him, his secretary, Miss Golder. She comes from Norwood. I should hate to have anything happen to queer her. People used to think Goode was engaged to her before he took that office next to us and got ambitious. Father placed her with Dr. Loeb. If it's necessary to do anything with him, I wish you'd think whether she couldn't be kept out of it in some way." "I'll try to do it," agreed Craig, as we shook hands and climbed on the early afternoon train back to the city. CHAPTER XXIX THE QUACK DOCTORS Kennedy's first move was to go downtown to the old building opposite the City Hall and visit the post-office inspectors. "I've heard of the government's campaign against the medical quacks who are using the mails," he introduced when we at last found the proper inspector. "I wonder whether you know a Dr. Adam Loeb?" "Loeb?" repeated the inspector, O'Hanlon, who was in charge of the investigation which was then in progress. "Of course we know Loeb--a very slippery customer, too, with just enough science at his command to make the case against him difficult. "I suppose," went on O'Hanlon, "you know that in Europe the popular furore about radium and its applications appeared earlier than it did here. But now we have great numbers of dishonest and fake radium cure establishments. Usually they have neither radium nor knowledge. They promise a cure, but they can't even palliate the trouble. Loeb has some radium, I guess, but that's about all." "I think I'd like to visit the 'doctor' and his 'medical museum,'" ventured Kennedy when O'Hanlon had finished describing the case to us. "Very well," agreed O'Hanlon. "Our cases against the quacks are just about completed. I've heard a great deal about you, Mr. Kennedy. I think I may trust you." The inspector paused. "Tomorrow," he added, looking at us significantly, "we have planned a simultaneous raid of all of them in the city. However, there's no objection to your seeing Dr. Loeb, if you'll be careful to give no hint that something is about to be pulled off. I'm sure any new evidence we may get against him will be quite welcome." "I'd like to see him in action before the raid," hastened Craig. "Well, I think the best way, then, for you to get at him," advised the inspector, "would be to adopt the method my investigators use with these fakers. I mean for one or the other of you to pose as a prospective patient. Only don't let him treat you too much with any of those electrical things of his." Craig glanced over at me whimsically. "Oh," I said good-humoredly, "I'll be the goat, if that's what you're going to ask me." Craig laughed. "Come in tomorrow," called the inspector as we left. "I'd like to hear what happens and I may be able to add something to what you find out." We found Dr. Loeb established in a palatial suite of offices in an ultra-modern office building. Outside was what he called his "medical museum." It was a grewsome collection of wax figures and colored charts well calculated to prepare one for the worst. At the end of the room was a huge sign bearing his name and the words, "Positive Cure for Cancer Without Cautery or the Knife." There were no cappers or steerers about the place, though I have no doubt he had them working for him outside to bring in business. Instead, we were met by a very pretty, fluffy-haired girl, evidently the doctor's secretary. She, I gathered, was the Miss Golder whom Lionel had mentioned. In fact, I felt that she was really much above the level of such a position. Loeb's office was elaborately equipped. There were static machines, electric coils, high frequency appliances, X-ray outfits, galvanic and faradic cabinets, electric light reflectors of high power, light bath cabinets, electric vibrators, high pressure nebulizers and ozonizers--everything, as Craig expressed it later, to impress the patient that Loeb could cure any disease the flesh was heir to. I know that it impressed me. The doctor himself was a pompous man of middle age, with a very formidable beard and a deep voice that forbade contradiction. "I've come to you on the recommendation of a patient of yours," began Craig, adding hastily, "not for myself, but for my friend here, whom I'm afraid isn't very well." The doctor eyed me through his gold-rimmed spectacles. Already I began to feel shaky. "Who recommended you?" he asked casually. "My friend, Mr. Darius Moreton of Norwood. I suppose you remember him?" "Oh, very well, very well. A most peculiar case, that of the Moretons. I have succeeded in prolonging their lives beyond what anyone else could have done. But I fear that they haven't all followed my treatment. You know, you must put yourself entirely in my hands, and there is a young doctor out there, I believe, whom they have also. That isn't fair to me. I wonder whether you are acquainted with my methods of treatment?" Kennedy shook his head negatively. "Miss Golder," the doctor called, as the fluffy-haired secretary responded quickly, "will you give these gentlemen some of my booklets on the Loeb Method." Miss Golder took from a cabinet several handsomely printed pamphlets extolling the skill and success of Dr. Loeb. Like everything else about him, no expense had been spared to impress the reader. As Miss Golder left the office, Dr. Loeb began a rapid examination of me, using an X-ray machine. I am sure that if I had not received a surreptitious encouraging nod from Craig now and then, I should have been ready to croak or cash in, according to whichever Dr. Loeb suggested--probably the latter, for I could not help thinking that a great deal of time was spent in mentally X-raying my pocketbook. When he finished, the doctor shook his head gravely. Of course I was threatened. But the thing was only incipient. Still, if it were not attended to immediately it was only a question of a short time when I might be as badly, as the wax figures and charts outside. I had fortunately come just in time to be saved. "I think that with the electrical treatment we can get rid of that malignant growth in a month," he promised, fixing a price for the treatment which I thought was pretty high, considering the brief time he had actually spent on me, and the slight cost of electric light and power. I paid him ten dollars on deposit, and after a final consultation we left the doctor's office. I was to return for a treatment in a couple of days. We turned out of the entrance of the office building just as scores of employés were hurrying home. As we reached the door, I felt Kennedy grasp my arm. I swung around. There, in an angle of the corridor, I caught sight of a familiar figure. Dr. Goode was standing, evidently waiting for someone to come out. There were several elevators and the crowd of discharging passengers was thick. He had been so intent on looking for someone he expected, apparently, that he had missed us. Kennedy drew me on into the doorway of the building next door, from which we could observe everyone who went in and out of the skyscraper in which Dr. Loeb had his offices. "I wonder what he's down here for," scowled Kennedy. "Perhaps he's doing some detective work of his own," I suggested. "Lionel Moreton said that Miss Golder and he used to be intimate," ruminated Kennedy. "I wonder if he's waiting for her?" We did not have long to wait. It was only a few minutes when Kennedy's surmise proved correct. Miss Golder and Dr. Goode came out, and turned in the direction of the railroad station for Norwood. He was eagerly questioning her about something, perhaps, I imagined, our visit to Dr. Loeb. What did it mean? There was no use and it was too risky to follow them. Kennedy turned and we made our way uptown to the laboratory, where he plunged at once into an examination of the blood specimens he had taken from the Moretons and of the peculiar porcelain cone which he had picked up in the rubbish pile between the two houses. Having emptied the specimens of blood in several little shallow glass receptacles which he covered with black paper and some very sensitive films, he turned his attention to the cone. I noted that he was very particular in his examination of it, apparently being very careful to separate whatever it was he was looking for on the inside and the outside surfaces. "That," he explained to me at length as he worked, "is what is known as a Berkefeld filter, a little porous cup, made of porcelain. The minute meshes of this filter catch and hold bacteria as if in the meshes of a microscopic sieve, just like an ordinary water filter. It is so fine that it holds back even the tiny bacillus fluorescens liquefaciens which are used to test it. These bacilli measure only from a half to one and one-and-a-half micromillimeters in diameter. In other words 130,000 germs of half a micromillimeter would be necessary to make an inch." "What has it been used for?" I ventured. "I can't say, yet," he returned, and I did not pursue the inquiry, knowing Kennedy's aversion to being questioned when he was not yet sure of his facts. It was the next day when the post-office inspectors, the police and others who had been co-operating had settled on the raid not only of Dr. Loeb's but of all the medical quacks who were fleecing the credulous of the city out of hundreds of thousands of dollars a year by one of the most cruel swindles that have ever been devised. For the time, Kennedy dropped his investigations in the laboratory and we went down to O'Hanlon's office, where a thick batch of warrants, just signed, had been received. Quickly O'Hanlon disposed his forces so that in all parts of the town they might swoop down at once and gather in the medical harpies. Dr. Loeb's stood first on the list of those which O'Hanlon decided to handle himself. "By the way," mentioned O'Hanlon as we hurried uptown to be ready in time, "I had a letter from Darius Moreton this morning threatening me with all kinds of trouble unless we let up on Dr. Loeb. It's pretty hard to keep a big investigation like this secret, but I think we've planned a little surprise for this morning." With the post-office inspector we climbed into a patrol wagon with a detail of police who were to make a general round-up of the places on Forty-second Street. As the wagon backed up to the curb in front of the building in which Loeb's office was, the policemen hopped out and hurried into the building before a crowd could collect. Unceremoniously they rushed through the outer office, headed by O'Hanlon. Quickly though the raid was executed, it could not be done without some warning commotion. As we entered the front door of the office, we could just catch a glimpse of a man retreating through a back door. There was something familiar about his back, and Kennedy and I started after him. But we were too late. He had fled without even waiting for his hat, which lay on Miss Golder's desk, and had disappeared down a back stairway which had been left unguarded. "Confound it," muttered O'Hanlon, as we returned, "Loeb hasn't been here today. Who was that?" "I don't know," replied Craig, picking up the hat, underneath which lay a package. He opened the package. Inside were half a dozen Berkefeld filters, those peculiar porcelain cones such as we had found out at Norwood. Quickly Craig ran his eye over the mass of papers on Miss Golder's desk. He picked up an appointment book and turned the pages rapidly. There were several entries that seemed to interest him. I bent over. Among other names entered during the past few days I made out both "Moreton" and "Dr. Goode." I recalled the letter which O'Hanlon had received from Moreton. Had he or someone else got wind of the raids and tipped off Dr. Loeb? Above the hubbub of the raid I could hear O'Hanlon putting poor little Miss Golder through a third degree. "Who was it that went out?" he shouted into her face. "You might as well tell. If you don't it'll go hard with you." But, like all women who have been taken into these get-rich-quick swindles, she was loyal to a fault. "I don't know," she sobbed, dabbing at her eyes with a bit of a lace handkerchief. Nor could all of O'Hanlon's bulldozing get another admission out of her except that it was a "stranger." She protested and wept. But she even rode off in the patrol wagon with the rest of the employés unmoved. Whom was she shielding? All we had was the secretary, a couple of cappers, and half a dozen patients, regular and prospective, who had been waiting in the office. We had a wagon-load of evidence, including letters and circulars, apparatus of all kinds, medicines, and pills. But there was nothing more. Craig did not seem especially interested in the mass of stuff which the police had seized. In fact the only thing that seemed to interest him was the man who had disappeared. We had his hat and the package of filters. Craig picked up the hat and examined it. "It's a soft hat and consequently doesn't tell us very much about the shape of his head," he remarked. Then his face brightened. "But he couldn't have left anything much better," he remarked complacently, as he went over to one of the little wall cabinets which the towel service companies place over wash-basins in offices. He took from it a comb and brush and wrapped them up carefully. I looked at the hat also. There was no name in it, not even the usual initials. What did Craig mean? Other raids in various parts of the city proved far more successful than the one in which we had participated and O'Hanlon quickly forgot his chagrin in the reports that soon came piling in. As for ourselves we had no further interest except in the disposition of this case, and Craig decided shortly to go back to work again in the laboratory among his test-tubes, slides, and microscopes. "I will leave you to follow the cases against the quacks, particularly Dr. Loeb and Miss Golder, Walter," he said. "By the way, you saw me take that hair brush. I wish I had a collection of them. In some way you must get me a hair brush from Dr. Goode. You'll have to take a trip out to Norwood. And while you are there, get the brushes from Darius Moreton and Lionel. I don't know how you'll get Goode's, but Myra will help you with the others, I'm sure." He turned to his work and was soon absorbed in some microscopic studies, leaving me no chance to question him about his strange commission. CHAPTER XXX THE FILTERABLE VIRUS I was surprised to run into O'Hanlon himself in the train out to Norwood. The failure to get Dr. Loeb troubled him and he had reasoned that if Darius Moreton took the trouble to write a letter about his friend he might possibly know more of his whereabouts than he professed. We discussed the case nearly the whole journey, agreeing to separate just before we reached the station in order not to be seen together. It took me longer to carry out Kennedy's request than I had expected. I found Myra at home alone, very much excited. "Someone called me up from New York this morning," she said, "and asked whether father and Lionel were at home. I thought they were at the factory, but when I called there, the foreman told me they hadn't been there. And Dr. Goode is out, too--hasn't seen any of his patients today. Oh, Mr. Jameson, what does it all mean? Where have they gone?" I was a poor one to comfort her, for I had no idea myself. Still, I did my best, and incidentally secured the brushes, though I must confess I had to commit a little second-story work to get into Dr. Goode's. It seemed heartless to leave the poor girl all alone, but I knew that Kennedy was waiting anxiously for me. I promised to make inquiries all over about her father, Lionel, and Dr. Goode, and, I think, the mere fact that someone showed an interest in her cheered her up, especially when I told her Kennedy was working hard on the case. As I waited for the train that was to take me back to the city, the train from New York pulled in. Imagine my surprise when I saw Miss Golder step off nervously and hurry up the main street. I watched her, debating what to do, whether to let Kennedy wait and follow her, or not. "Someone, they don't know who, bailed her out," I heard a voice whisper in my ear. I turned quickly. It was O'Hanlon. "She put up cash bail," he added under his breath. "No one knows where she got it. I'm waiting until she turns that corner--then I'm going to shadow her. I can't seem to find anyone in this town just now. Perhaps she knows where Loeb is." "If you get on the trail, will you wire me?" I asked. "Here's my train now." O'Hanlon promised, and as I swung on the step I caught a last glimpse of him sauntering casually in the direction Miss Golder had taken. I handed Kennedy the brushes I had obtained, but he gave me no opportunity to satisfy my curiosity. Instead, he started me out again to keep in touch with the progress made in the cases of the quacks, particularly the search for Dr. Loeb, which seemed to interest him quite as much as the bailing out of Miss Golder. It was after dinner and I was preparing to follow the cases on into the night court, if necessary, when one of O'Hanlon's assistants hurried up to me. "We've just had a wire from Mr. O'Hanlon," he cried excitedly, handing me a telegram. I read: "Loeb captured Norwood. Darius Moreton hiding him in vacant house outside town. Advise Kennedy." I dashed for the nearest telephone and called up Craig. "Fine, Walter," he shouted back. "I am ready. Meet me at the station and wire O'Hanlon to wait there for us." We made the journey to Norwood as impatiently as any two passengers on the accommodation at that hour of night, Craig carrying his evidence in the case in a little leather hand satchel. Already, out at the old house, O'Hanlon had gathered the Moreton family, Dr. Goode, who had turned up with the rest, Dr. Loeb, and Miss Golder. Myra Moreton was even more agitated than she had been when I left her during the afternoon. In fact the secrecy maintained by both her family and Dr. Goode, to say nothing of the presence of Dr. Loeb in the house under arrest, had all but broken her down. She greeted Kennedy almost as though he had been a life-long friend. "I want you to look after Miss Moreton, Walter," he said in a low tone as we three stood in the hall. "And you, Miss Moreton, I want to trust me when I tell you I am going to bring you safely out of this thing. Be a brave girl," he encouraged, taking her hand. "Remember that Mr. Jameson and I are here solely in your interest." "I know it," she murmured, her lip trembling. "I will try." A moment later we entered the Moreton library. Dr. Loeb was glaring impartially at everybody. I am sure that if he had been able to get at any of his formidable electrical apparatus he would have made short work of us "without cautery or knife." Darius Moreton was indignant, Lionel supercilious, Dr. Goode silent. Kennedy lost no time in getting down to the business that had brought him out to Norwood, for this was not exactly a sociable gathering. "Of course," he began, laying his leather case on the table and unlocking, but not opening it, "references to cancer houses abound in medical literature, but I think I am safe in saying that nothing has been conclusively proved in favor either of the believers or the skeptics. At least, it may be said to be an open question, with the weight of opinion against it. Such physicians as Sir Thomas Oliver have said that the evidence in favor is too strong to be ignored. Others, equally brilliant, have shown why it should be ignored. "In the absence of better proof--or rather in the presence of other facts--perhaps, in this case, it would be better to see whether there is not some other theory that may fit the facts better." "Dr. Goode thought that the cancers might have been caused artificially by X-rays or radium," I ventured. Craig shook his head. "I have taken a piece of filter paper saturated with a solution of potassium iodide, starch paste, and ferrosulphate and laid it over a sample of blood, not four millimeters away. The whole I have kept in the dark. "Now, we know that blood gives off peroxide of hydrogen. Peroxide of hydrogen is capable of attacking photographic plates. The paper can be permeated by a gas. No, that was not a case of photo-activity observed by Dr. Goode. It was the emission of gas from the blood that affected the plates." "But suppose that is the case," objected Dr. Goode hastily. "There are the deaths from cancer. How do you explain them? It is not a cancer house, you say. Is it mere chance?" "Anyone may be pardoned for believing that cancer houses or even cancer districts exist," reiterated Craig. "Indeed some observations seem to show it, as I have said, though the opponents of the theory claim to have found other causes. Here, as you hint, five people, living in close association, have died in five years." He paused and drew from the satchel the little porcelain cone which he had picked up between the Moreton and Goode houses. "I have here," he resumed, "what is known as a Berkefeld filter. Its meshes let through none of the germs that we can see with a microscope. It is bacteria-proof. Only something smaller than these things can pass through it, something that we cannot see, a clear watery fluid. That something in this case is a filterable virus." Kennedy paused again, then went on, "Although the filterable viruses have only recently come to attention, it is known that they are of very diverse character. Here we have opened up the world of the infinitely little--the universe that lies beyond the range of the microscope. The study of these tiny particles is now one of the greatest objects in scientific medicine. "Are they living? It seems so, for a very little of the virus gives rise to growths from which many others start. It may, of course, be chemical, but it looks as if it were organic, since it resists cold, although not heat, and can be destroyed by phenol, toluol, and other antiseptics. Perhaps the virus may be visible, but not by any means yet known. Still, we do know that these things which no eye can see may cause some of the commonest diseases." Kennedy paused. As usual he had his little audience following him breathlessly. Even Dr. Loeb forgot to glower. "In recent experiments with cancer in chickens," continued Craig, "tumor material ground fine and treated in various ways has been filtered through these filters. Cancers have been caused by this agent which has passed through the filter. "On the inside of the filter which I picked up back of this very house, near the boundary of Dr. Goode's, I have found the giant cells of cancer. On the outside was something which I have been able to develop into a virus, these micro-organisms that belong to the ultra-invisible. I do not pretend to know just how this bacteriological dwarf has been used. But I know enough to say that someone has, without doubt, been using some sort of filterable virus to induce cancers, just as the experimenters at the Rockefeller Institute have done with animals. "Naturally, in the Moreton family, this person found a fertile soil. Perhaps he waited until he saw what looked like a favorable wound, or traumatism. It is well-known that cancer often can be traced to a wound. Perhaps he introduced this virus surreptitiously into a cut, now and then. For, experiments show that the virus is strikingly dependent for its action on the derangement of the tissues with which it is brought in contact. "This person must have had a high percentage of failures in his attempts to inoculate the virus successfully. But by persistence and taking advantage of every predisposition afforded by nature, he succeeded. At any rate, this person must have been intimately acquainted with the family, must have had some motive for seeking their deaths,--for instance the family fortune. "It makes no difference whether the victims might have had cancer sooner or later, anyway. Even if that were so, this cold-blooded villain was at least hastening the development, if not actually causing the frightful and fatal disease." Myra Moreton shuddered, and looked at Dr. Goode anxiously as Kennedy proceeded. He seemed about to interrupt, but managed to check himself. Craig reached over and picked out from the satchel the hat which we had found on a desk at the office of the cancer quack. "In the raid of Dr. Loeb's," he explained, changing tone, "a man disappeared. I have here a soft hat which he left behind in his hurry to escape, as well as some of the filters he was carrying." He turned the hat inside out. "You will see," Craig pointed out, "that on the felt of the inside there are numerous hairs, from the head of the wearer." I leaned forward, breathlessly. I began to see the part I had played in building up his case. "Human hair," he remarked, "differs greatly. Under the microscope one may study the oval-shaped medulla, the long pointed cortex, and the flat cuticle cells of an individual hair. The pigment in the cortex can be studied also. "I have taken some of the hairs from the inside of this hat, examined, photographed, and measured them. I have compared them with a color scale perfected by the late Alphonse Bertillon. In fact, in France quite a science has been built up about hair by the so-called 'pilologists.' The German scientific criminalists have written minute treaties on the hair and astounding results have been obtained by them in detection. "I have been able to secure samples of the hair of everyone in this case and I have studied them also. These hairs in the hat which was left over the package of filters have furnished me with a slender but no less damning clew to a veritable monster." One could have heard a pin drop, as if Kennedy were a judge pronouncing a death sentence. "Dr. Loeb is guilty of being one of the most heartless of quacks, it is true," Kennedy's voice rang out tensely, as he faced us. "But the slow murders, one by one, bringing the family estate nearer and nearer--they were done by one who hoped to throw the blame on Dr. Loeb, by the man whose hair I have here--Lionel Moreton." CHAPTER XXXI THE VOODOO MYSTERY "Everybody's crazy, Kennedy. The whole world is going mad!" Our old friend, Burke, of the Secret Service, scowled at the innocent objects in Craig's laboratory as he mopped his broad forehead. "And the Secret Service is as bad as the rest," he went on, still scowling and not waiting for any comment from us. "Why, what with these European spies and agitators, strikers and dynamiters, we're nearly dippy. Here, in less than a week I've been shifted off war cases to Mexico and now to Hayti. I don't mean that I've been away, of course,--oh, no. You don't have to go to them. They come to us. Confound it, New York is full of plots and counterplots. I tell you, Kennedy, the whole world is crazy." Craig listened with sympathy mixed with amusement. "Can I help you out?" he asked. "If you don't I'll be dippy, too," returned Burke with a whimsical grimace. "What's the trouble with Hayti, then?" encouraged Kennedy seriously. "Trouble enough," answered Burke. "Why, here's that Caribbean liner, _Haytien_, just in from Port au Prince. She's full of refugees--government supporters and revolutionists--you never saw such a menagerie since the ark." I watched Burke keenly as he cut loose with his often picturesque language. Somehow, it seemed rather fascinating to have the opera bouffe side of the Black Republic presented to us. At least it was different from anything we had had lately--and perhaps not at all opera bouffe, either. Kennedy, at least, did not seem to think so, for although he was very busy at the time, seemed prepared to lay aside his work to aid Burke. "You haven't heard about it yet," continued the Secret Service man, "but on the _Haytien_ was a man--black of course--Guillaume Leon. He was a friend of the United States--at least so he called himself, I believe--wanted a new revolution down there, more American marines landed to bolster up a new government that would clean things up, a new deal all around." Burke paused, then added by way of explanation of his own attitude in the matter, "That may be all right, perhaps,--may be just what they need down there, but we can't let people come here and plot revolutions like that right in New York. They're sore enough at us without our letting them think in Latin America that we're taking a hand in their troubles." "Quite right," agreed Kennedy. "About Leon." "Yes, Leon," resumed Burke, getting back to the subject. "Well, I was told by the Chief of the Service to look out for this fellow. And I did. I thought it would make a good beginning to go down the bay on a revenue tug to meet the _Haytien_ at Quarantine. But, by Jingo, no sooner was I over the side of the ship than what do you suppose I ran up against?" He did not pause long enough to give us a guess, but shot out dramatically, "Leon was dead--yes, dead!" Kennedy and I had been interested up to this point. Now we were eager to have him go on. "He died on the voyage up," continued Burke, "just after passing the Gulf Stream, suddenly and from no apparent cause. At least the ship's surgeon couldn't find any cause and neither could they down at Quarantine. So after some time they let the ship proceed up the bay and placed the whole thing in the hands of the Secret Service." "Is there anyone you suspect?" I asked. "Suspect?" repeated Burke. "I suspect them all. The _Haytien_ was full of niggers--as superstitious as they make 'em. The ship's surgeon tells me that after the body of Leon was discovered there was such a scene as he had never witnessed. It was more like bedlam than a group of human beings. Some were for putting the body over into the sea immediately. Others threatened murder if it was done. Most of them didn't know what it was they wanted. Then, there was a woman there. She seemed to be nearly crazy--" There came a knock at the laboratory door. "If you'll just go into the next room with Walter," said Craig to Burke, "I'll see you in a few minutes. Sit down, make yourself at home." I went in with him and Burke dropped into a chair beside my typewriter. The laboratory door opened. From where we were sitting we could see in a mirror on the opposite wall that it was a girl, dark of skin, perhaps a mulatto, but extremely beautiful, with great brown eyes and just a trace of kinkiness in her black hair. But it was the worried, almost haunted, look on her face that attracted one's attention most. I happened to glance at Burke to see whether he had noticed it. I thought his eyes would pop out of his head. Just then Kennedy walked across the laboratory and closed our door. "What's the matter?" I whispered. But before Burke could reply, a draught opened the door just a bit. He placed his finger on his lips. We could not close the door, and we sat there in our corner unintentional but no less interested eavesdroppers. "Mademoiselle Collette Aux Cayes is my name," she began, with a strangely French accent which we could just understand. "I've heard of you, Professor Kennedy, as a great detective." "I should be glad to do what I can for you," he returned. "But you mustn't expect too much. You seem to be in some great trouble." "Trouble--yes," she replied excitedly. "My name isn't really Aux Cayes. That is the name of my guardian, a friend of my father's. Both my father and mother are dead--killed by a mob during an uprising several years ago. I was in Paris at the time, being educated in a convent, or I suppose I should have been killed, too." She seemed to take it as a matter of course, from which I concluded that she had been sent to Paris when she was very young and did not remember her parents very well. "At last the time came for me to go back to Hayti," she resumed. "There is nothing that would interest you about that--except that after I got back, in Port au Prince, I met a young lawyer--Guillaume Leon." She hesitated and looked at Craig as though trying to read whether he had ever heard the name before, but Kennedy betrayed nothing. There was more than that in her tone, though. It was evident that Leon had been more than a friend to her. "Hayti has been so upset during the past months," she went on, "that my guardian decided to go to New York, and of course I was taken along with him. It happened that on the ship--the _Haytien_--Monsieur Leon went also. It was very nice until--" She came to a full stop. Kennedy encouraged her gently, knowing what she was going to tell. "One night, after we had been out some time," she resumed unexpectedly, "I could not sleep and I went out on the deck to walk and watch the moonlight. As I walked softly up and down, I heard voices, two men, in the shadow of one of the cabins. They were talking and now and then I could catch a word. It was about Guillaume. I heard them say that he was plotting another revolution, that that was the reason he was going to New York--not because he wanted to be on the boat with me. There was something about money, too, although I couldn't get it very clearly. It had to do with an American banking house, Forsythe & Co., I think,--money that was to be paid to Guillaume to start an uprising. I think they must have heard me, for I couldn't hear any more and they moved off down the deck, so that I couldn't recognize them. You see, I am not a revolutionist. My guardian belongs to the old order." She stopped again, as though in doubt just how to go on. "Anyhow," she continued finally, "I determined to tell Guillaume. It would have made it harder for us--but it was he, not his politics, I loved." She was almost crying as she blurted out, "But it was only the next day that he was found dead in his stateroom. I never saw him alive after I overheard that talk." It was some moments before she had calmed herself so that she could go on. "You know our people, Professor Kennedy," she resumed, choking back her sobs. "Some said his dead body was like Jonah, and ought to be thrown off to the sea. Then others didn't even want to have it touched, said that it ought to be embalmed. And others didn't want that, either." "What do you mean? Who were they?" "Oh, there was one man,--Castine," she replied, hesitating over the name, as though afraid even to mention it. "He wanted it thrown overboard?" prompted Craig. "N--no, he didn't want that, either," she replied. "He urged them not to touch it--just to leave it alone." She was very much frightened, evidently at her own temerity in coming to Craig and saying so much. Yet something seemed to impel her to go on. "Oh, Professor Kennedy," she exclaimed in a sudden burst of renewed feeling, "don't you understand? I--I loved him--even after I found out about the money and what he intended to do with it. I could not see his dear body thrown in the ocean." She shivered all over at the thought, and it was some time before she said anything more. But Kennedy let her do as she pleased, as he often did when deep emotion was wringing the secrets from people's hearts. "He is dead!" she sobbed wildly. "Was he poisoned? Oh, can't you find out? Can't you help me?" Suddenly her voice in wild appeal sank almost to a hoarse whisper. "You must not let anybody know that I came to you," she implored. "Why not?" "Oh--I--I am just afraid--that's all." There was real fear in her tone and face now, fear for herself. "Where is the body?" asked Kennedy, to get her mind off whatever hung like an incubus over it. "Down on the _Haytien_, at the pier, over in Brooklyn, still," she replied. "They kept us all interned there. But my guardian had enough influence to get off for a time and while he is arranging for quarters for our stay after we are released, I slipped away to see you." "You must go back to the boat?" "Oh, yes. We agreed to go back." "Then I shall be down immediately," Craig promised. "If you will go ahead, I will see you there. Perhaps, at first you had better not recognize me. I will contrive some way to meet you. Then they will not know." "Thank you," she murmured, as she rose to go, now in doubt whether she had done the best thing to come to Craig, now glad that she had some outside assistance in which she could trust. He accompanied her to the door, bidding her keep up her courage, then closed it, waiting until her footsteps down the hall had died away. Then he opened our door and caught sight of Burke's face. "That's strange, Burke," he began, before he realized what the expression on his face meant. "There's a woman--what? You don't mean to tell me that you knew her?" "Why, yes," hastened Burke. "There was a rich old planter, Henri Aux Cayes, aboard, too. She's his ward, Mademoiselle Collette." "That's right," nodded Craig in surprise. "She's the woman I was telling you about. She may be a little dark, but she's a beauty, all right. I heard what she said. No wonder she was so frantic, then." "What do you know of the bankers, Forsythe & Co.?" asked Craig. "Forsythe & Co.?" considered Burke. "Well, not much, perhaps. But for a long time, I believe, they've been the bankers and promoters of defunct Caribbean islands, reaping a rich harvest out of the troubles of those decrepit governments, playing one against the other." "H-m," mused Kennedy. "Can you go over to Brooklyn with me now?" "Of course," agreed Burke, brightening up. "That was what I hoped you'd do." Kennedy and I were just about to leave the laboratory with Burke when an idea seemed to occur to Craig. He excused himself and went back to a cabinet where I saw him place a little vial and a hypodermic needle in his vest pocket. CHAPTER XXXII THE FLUORISCINE TEST Our trip over to the other borough was uneventful except for the toilsome time we had to get to the docks where South and Central American ships were moored. We boarded the _Haytien_ at last and Burke led us along the deck toward a cabin. I looked about curiously. There seemed to be the greatest air of suppressed excitement. Everyone was talking, in French, too, which seemed strange to me in people of their color. Yet everything seemed to be in whispers as if they were in fear. We entered the cabin after our guide. There in the dim light lay the body of Leon in a bunk. There were several people in the room, already, among them the beautiful Mademoiselle Collette. She pretended not to recognize Kennedy until we were introduced, but I fancied I saw her start at finding him in company with Burke. Yet she did not exhibit anything more than surprise, which was quite natural. Burke turned the sheet down from the face of the figure in the bunk. Leon had been a fine-looking specimen of his race, with good features, strong, and well groomed. Kennedy bent over and examined the body carefully. "A very strange case," remarked the ship's surgeon, whom Burke beckoned over a moment later. "Quite," agreed Craig absently, as he drew the vial and the hypodermic from his pocket, dipped the needle in and shot a dose of the stuff into the side of the body. "I can't find out that there is any definite cause of death," resumed the surgeon. Before Craig could reply someone else entered the darkened cabin. We turned and saw Collette run over to him and take his hand. "My guardian, Monsieur Aux Cayes," she introduced, then turned to him with a voluble explanation of something in French. Aux Cayes was a rather distinguished looking Haytian, darker than Collette, but evidently of the better class and one who commanded respect among the natives. "It is quite extraordinary," he said with a marked accent, taking up the surgeon's remark. "As for these people--" he threw out his hands in a deprecating gesture--"one cannot blame them for being perplexed when your doctors disagree." Kennedy had covered up Leon's face again and Collette was crying softly. "Don't, my dear child," soothed Aux Cayes, patting her shoulder gently. "Please, try to calm thyself." It was evident that he adored his beautiful ward and would have done anything to relieve her grief. Kennedy evidently thought it best to leave the two together, as Aux Cayes continued to talk to her in diminutives and familiar phrases from the French. "Were there any other people on the boat who might be worth watching?" he asked as we rejoined Burke, who was looking about at the gaping crowd. Burke indicated a group. "Well, there was an old man, Castine, and the woman he calls his wife," he replied. "They were the ones who really kept the rest from throwing the body overboard." "Oh, yes," assented Kennedy. "She told me about them. Are they here now?" Burke moved over to the group and beckoned someone aside toward us. Castine was an old man with gray hair, and a beard which gave him quite an appearance of wisdom, besides being a matter of distinction among those who were beardless. With him was Madame Castine, much younger and not unattractive for a negress. "You knew Monsieur Leon well?" asked Kennedy. "We knew him in Port au Prince, like everybody," replied Castine, without committing himself to undue familiarity. "Do you know of any enemies of his on the boat?" cut in Burke. "You were present when they were demanding that his body be thrown over, were you not? Who was foremost in that?" Castine shrugged his shoulders in a deprecatory manner. "I do not speak English very well," he replied. "It was only those who fear the dead." There was evidently nothing to be gained by trying on him any of Burke's third degree methods. He had always that refuge that he did not understand very well. I turned and saw that Collette and Aux Cayes had come out of the cabin to the deck together, he holding her arm while she dabbed the tears away from her wonderful eyes. At the sight of us talking to Castine and the other woman, she seemed to catch her breath. She did not speak to us, but I saw the two women exchange a glance of appraisal, and I determined that "Madame" Castine was at least worth observing. By the attitude of the group from which we had drawn them, Castine, it seemed, exercised some kind of influence over all, rich and poor, revolutionist and government supporter. The appearance of Collette occasioned a buzz of conversation and glances, and it was only a moment before she retreated into the cabin again. Apparently she did not wish to lose anything, as long as Kennedy and Burke were about. Kennedy did not seem to be so much interested in quizzing Castine just yet, now that he had seen him, as he was in passing the time profitably for a few minutes. He looked at his watch, snapped it back into his pocket, and walked deliberately into the cabin again. There he drew back the cover over Leon's face, bent over it, raised the lids of the eyes, and gazed into them. Collette, who had been standing near him, watching every motion, drew back with an exclamation of horror and surprise. "The voodoo sign is on him!" she cried. "It must be that!" Almost in panic she fled, dragging her guardian with her. I, too, looked. The man's eyes were actually green, now. What did it mean? "Burke," remarked Kennedy decisively, "I shall take the responsibility of having the body transferred to my laboratory where I can observe it. I'll leave you to attend to the formalities with the coroner. Then I want you to get in touch with Forsythe & Co. Watch them without letting them know you are doing so--and watch their visitors, particularly." A private ambulance was called and, with much wagging of heads and tongues, the body of Leon was carried on a stretcher, covered by a sheet, down the gangplank and placed in it. We followed closely in a taxicab, across the bridge and uptown. For some days, I may say, Kennedy had been at work in his laboratory in a little anteroom, where he was installing some new apparatus for which he had received an appropriation from the trustees of the University. It was a very complicated affair, one part of which seemed to be a veritable room within the room. Into this chamber, as it were, he now directed the men to carry Leon's body and lay it on a sort of bed or pallet that was let down from the side wall of the compartment. I had been quite mystified by the apparatus which Kennedy had set up, but had had no opportunity to discuss it with him and he had been so busy installing it that he had not taken time, often, for meals. In fact, the only way I knew that he had finished was that when Burke had called he had seemed interested in the call. Outside the small chamber I have spoken of, in the room itself, were several large pieces of machinery, huge cylinders with wheels and belts, run by electric motors. No sooner had the body been placed in the little chamber and the door carefully closed than Kennedy threw a switch, setting the apparatus in motion. "How could Leon have been killed?" I asked, as he rejoined me in the outside laboratory. "What did Collette mean by her frightened cry of the 'voodoo sign'?" The incident had made a marked impression on me and I had been unable quite to arrive at any sensible explanation. "Of course, you know that voodoo means literally anything that inspires fear," remarked Kennedy after a moment's thought. "The god of voodoo is the snake. I cannot say now what it was that she feared. But to see the eyeballs turn green is uncanny, isn't it?" "I should say so," I agreed. "But is that all?" He shook his head. "No, I don't believe it is. Hayti is the hotbed of voodoo worship. The cult has inaugurated a sort of priesthood--often a priest and a priestess, called 'papaloi' and 'mammaloi'--papa and mamma, probably with a corruption of the French word, 'roi,' king. They are, as it were, heads of the community, father and mother, king and queen. Some of the leading men of the communities in the islands of the Caribbean are secret voodoists and leaders. Just what is going on under the surface in this case, I cannot even hazard a guess. But there is some deviltry afoot." Just then the telephone rang and Craig answered it. "It was from Burke," he said as he hung up the receiver. "Confidential agents of his have been about. No one from the ship seems to have been down to see Forsythe, but Forsythe has had people over at the ship. Burke says someone is sending off great bunches of messages to Hayti--he thinks the powerful wireless apparatus of the _Haytien_ is being used." For a moment Kennedy stood in the center of the laboratory, thinking. Then he appeared to make up his mind to something. "Has that taxicab gone?" he asked, opening a cabinet from which he took several packages. I looked out of the window. The ambulance had gone back, but the driver of the car had evidently waited to call up his office for instructions. I beckoned to him, and together Kennedy and I placed the packages in the car. Thus we were able quickly to get back again to the wharf where the _Haytien_ was berthed. Instead of going aboard again, however, Kennedy stopped just outside, where he was not observed and got out of the car, dismissing it. In the office of the steamship company, he sought one of the employés and handed him a card, explaining that we were aiding Burke in the case. The result of the parley was that Kennedy succeeded in getting to the roof of the covered pier on the opposite side from that where the ship lay. There he set to work on a strange apparatus, wires from which ran up to a flag pole on which he was constructing what looked like a hastily improvised wireless aerial. That part arranged, Kennedy followed his wires down again and took them in by a window to a sort of lumber-room back of the office. Outside everyone was too busy to watch what we were doing there and Craig could work uninterrupted. "What are you doing?" I asked. "Installing a wireless plant?" "Not quite," he smiled quietly. "This is a home-made wireless photo-recording set. Of course, wireless aerials of amateurs don't hum any more since war has caused the strict censorship of all wireless. But there is no reason why one can't receive messages, even if they can't be sent by everybody. "This is a fairly easy and inexpensive means by which automatic records can be taken. It involves no delicate instruments and the principal part of it can be made in a few hours from materials that I have in my laboratory. The basis is the capillary electrometer." "Sounds very simple," I volunteered, trying not to be sarcastic. "Well, here it is," he indicated, touching what looked like an ordinary soft glass tube of perhaps a quarter of an inch diameter, bent U-shaped, with one limb shorter than the other. "It is filled nearly to the top of the shorter limb with chemically pure mercury," he went on. "On the top of it, I have poured a little twenty per cent sulphuric acid. Dipping into the acid is a small piece of capillary tube drawn out to a very fine point at the lower end." He filled the little tube with mercury also. "The point of this," he observed, "is fine enough to prevent the mercury running through of its own weight--about as fine as a hair." He dipped the point and held it in the sulphuric acid and blew through the capillary tube. When the mercury bubbled through the point in minute drops, he stopped blowing. It drew back for a short distance by capillary attraction and the acid followed it up. "You can see that connections are made to the mercury in the arm and the tube by short pieces of platinum wire," he continued. "It isn't necessary to go into the theory of the instrument. But the most minute difference of potential between the two masses of mercury will cause the fine point at the junction of the liquids to move up and down. "Connected to the aerial and the earth, with a crystal detector in series, it is only a matter of applying an ordinary photo-recording drum, and the machine is made." He had been setting up a light-tight box, inside of which was a little electric lamp. Opposite was a drum covered with bromide paper. He started the clockwork going and after a few moments' careful observation, we went away, and left the thing, trusting that no one was the wiser. Nothing further occurred that day, except for frequent reports from Burke, who told us how his men were getting on in their shadowing of Forsythe & Co. Apparently, the death of Leon had put a stop to revolutionary plots, or at least had caused the plotters to change their methods radically. The time was shortening, too, during which Burke could keep the passengers of the _Haytien_ under such close surveillance, and it was finally decided that on the next morning they should be released, while all those suspected were to be shadowed separately by Secret Service agents, in the hope that once free they would commit some overt act that might lead to a clew. CHAPTER XXXIII THE RESPIRATION CALORIMETER It was early the next morning, about half an hour after the time set for the release of the passengers, that our laboratory door was flung open and Collette Aux Cayes rushed in, wildly excited. "What's the matter?" asked Kennedy anxiously. "Someone has been trying to keep me on the boat," she panted. "And all the way over here a man has been following me." Kennedy looked at her a minute calmly. We could understand why she might have been shadowed, though it must have been a bungling job of Burke's operative. But who could have wanted her kept on the boat? "I don't know," she replied, in answer to Kennedy's question. "But somehow I was the only one not told that we could go. And when I did go, one of the Secret Service men stopped me." "Are you sure it was a Secret Service man?" "He said he was." "Yes, but if he had been, he would not have done that, nor let you get away, if he had. Can't you imagine anyone who might want you detained longer?" She looked at us, half frightened. "N--not unless it is that man--or the woman with him," she replied, clasping her hands. "You mean Castine?" "Yes," she replied, avoiding the use of his name. "Ever since you had the body removed, he has been in great fear. I have heard him ask fifty times, 'Where have they taken him?' and 'Is he to be embalmed?'" "That's strange," remarked Kennedy. "Why that anxiety from him? I remember that it was he who wanted the body left alone. Is it for fear that we might discover something which might be covered up?" Kennedy disappeared into the anteroom and I heard him making a great fuss as he regulated the various pieces of machinery that surrounded the little chamber. Some minutes later, he emerged. "Meet us here in an hour," he directed Collette, "with your guardian." Quickly Craig telephoned for a tank of oxygen to be sent over to the laboratory, then got Burke on the wire and asked him to meet us down at the dock. We arrived first and Craig hurried into the lumber-room, where fortunately he found everything undisturbed. He tore off the strip of paper from the drum and held it up. On it was a series of marks, which looked like dots and dashes, of a peculiar kind, along a sort of base line. Carefully he ran his eye over the strip. Then he shoved it into his pocket in great excitement. "Hello," greeted Burke, as he came up puffing from the hurried trip over from the Customs House, where his office was. "What's doing now?" "A great deal, I think," returned Kennedy. "Can you locate Castine and that woman and come up to the laboratory--right away?" "I can put my finger on them in five minutes and be there in half an hour," he returned, not pausing to inquire further, for, like me, Burke had learned that Kennedy could not be hurried in any of his revelations. Together, Craig and I returned to the laboratory to find that Collette Aux Cayes was already there with her guardian, as solicitous as ever for her comfort and breathing fire and slaughter against the miscreants who had tried to detain her, without his knowledge. Some minutes later Castine and "Madame" Castine arrived. At sight of Collette she seemed both defiant and restless, as though sensing trouble, I thought. Few words were spoken now by anyone, as Burke and I completed the party. "Will you be so kind as to step into the little anteroom with me?" invited Craig, holding open the door for us. We entered and he followed; then, as he led the way, stopped before a little glass window in the compartment which I have described. Collette was next to me. I could feel the tenseness of her senses as she gazed through the window at the body on the shelf-like pallet inside. "What is this thing?" asked Aux Cayes, as Collette drew back, and he caught her by the arm. For the moment Kennedy said nothing, but opened a carefully sealed door and slid the pallet out, unhinging it, while I saw Castine trembling and actually turning ashen about the lips. "This," Kennedy replied at length, "is what is known as a respiration calorimeter, which I have had constructed after the ideas of Professors Atwater and Benedict of Wesleyan, with some improvements of my own. It is used, as you may know, in studying food values, both by the government and by other investigators. A man could live in that room for ten or twelve days. My idea, however, was to make use of it for other things than that for which it was intended." He took a few steps over to the complicated apparatus which had so mystified me, now at rest, as he turned a switch on opening the carefully sealed door. "It is what is known as a closed circuit calorimeter," he went on. "For instance, through this tube air leaves the chamber. Here is a blower. At this point, the water in the air is absorbed by sulphuric acid. Next the carbon dioxide is absorbed by soda lime. Here a little oxygen is introduced to keep the composition normal and at this point the air is returned to the chamber." He traced the circuit as he spoke, then paused and remarked, "Thus, you see, it is possible to measure the carbon dioxide and the other respiration products. As for heat, the walls are constructed so that the gain or loss of heat in the chamber is prevented. Heat cannot escape in any other way than that provided for carrying it off and measuring it. Any heat is collected by this stream of water which keeps the temperature constant and in that way we can measure any energy that is given off. The walls are of concentric shells of copper and zinc with two of wood, between which is 'dead air,' an effective heat insulator. In other words," he concluded, "it is like a huge thermos bottle." It was all very weird and fascinating. But what he could have been doing with a dead body, I could not imagine. Was there some subtle, unknown poison which had hitherto baffled science, but which now he was about to reveal to us? He seemed to be in no hurry to overcome the psychological effect his words had on his auditors, for as he picked up and glanced at a number of sheets of figures, he went on: "In the case of live persons, there is a food aperture here, a little window with air locks arranged for the passage of food and drink. That large window through which you looked admits light. There is also a telephone. Everything is arranged so that all that enters, no matter how minute, is weighed and measured. The same is true of all that leaves. Nothing is too small to take into account." He shook the sheaf of papers before us. "Here I have some records which have been made by myself, and, in my absence, by one of my students. In them the most surprising thing that I have discovered is that in the body of Leon metabolism seems still to be going on." I listened to him in utter amazement, wondering toward what his argument was tending. "I got my first clew from an injection of fluoriscine," he resumed. "You know there are many people who have a horror of being buried alive. It is a favorite theme of the creepy-creep writers. As you know, the heart may stop beating, but that does not necessarily mean that the person is dead. There are on record innumerable cases where the use of stimulants has started again the beating of a heart that has stopped. "Still, burial alive is hardly likely among civilized people, for the simple reason that the practice of embalming makes death practically certain. At once, when I heard that there had been objections to the embalming of this body, I began to wonder why they had been made. "Then it occurred to me that one certain proof of death was the absolute cessation of circulation. You may not know, but scientists have devised this fluoriscine test to take advantage of that. I injected about ten grains. If there is any circulation, there should be an emerald green discoloration of the cornea of the eye. If not, the eye should remain perfectly white. "I tried the test. The green eye-ball gave me a hint. Then I decided to make sure with a respiration calorimeter that would measure whatever heat, what breath, no matter how minute they were." Collette gave a start as she began to realize vaguely what Craig was driving at. "It was not the voodoo sign, Mademoiselle," he said, turning to her. "It was a sign, however, of something that suggested at once to me the connection of voodoo practices." There was something so uncanny about it that my own heart almost skipped beating, while Burke, by my other side, muttered something which was not meant to be profane. Collette was now trembling violently and I took her arm so that if she should faint she would not fall either on my side or on that of her guardian, who seemed himself on the verge of keeling over. Castine was mumbling. Only his wife seemed to retain her defiance. "The skill of the voodoo priests in the concoction of strange draughts from the native herbs of Hayti is well known," Kennedy began again. "There are among them fast and slow poisons, poisons that will kill almost instantly and others that are guaged in strength to accumulate and resemble wasting away and slow death. "I know that in all such communities today no one will admit that there is such a thing still as the human sacrifice, 'the lamb without horns.' But there is on record a case where a servant was supposed to have died. The master ordered the burial, and it took place. But the grave was robbed. Later the victim was resuscitated and sacrificed. "Most uncanny of the poisons is that which will cause the victim to pass into an unconscious condition so profound that it may easily be mistaken for death. It is almost cataleptic. Such is the case here. My respiration calorimeter shows that from that body there are still coming the products of respiration, that there is still heat in it. It must have been that peculiar poison of the voodoo priests that was used." Racing on now, not giving any of us a chance even to think of the weird thing, except to shudder instinctively, Kennedy drew from his pocket and slapped down on a table the photographic records that had been taken by his home-made wireless recording apparatus. "From Mr. Burke," he said, as he did so, "I received the hint that many messages were being transmitted by wireless, secretly perhaps, from the _Haytien_. I wanted to read those messages that were being flashed so quietly and secretly through the air. How could it be done? I managed to install down at the dock an apparatus known as the capillary electrometer. By the use of this almost unimaginably delicate instrument I was able to drag down literally out of the air the secrets that seemed so well hidden from all except those for whom they were intended. Listen." He took the roll of paper from the drum and ran his finger along it hastily, translating to himself the Morse code as he passed from one point to another. "Here," cried Craig excitedly. "'Leon out of way for time safely. Revolution suppressed before Forsythe can make other arrangements. Conspiracy frustrated.' Just a moment. Here's another. 'Have engaged bridal suite at Hotel La Coste. Communicate with me there after tomorrow.'" Still holding the wireless record, Kennedy swung about to Burke and myself. "Burke, stand over by the door," he shouted. "Walter--that tank of oxygen, please." I dragged over the heavy tank which he had ordered as he adjusted a sort of pulmotor breathing apparatus over Leon. Then I dropped back to my place beside Collette, as the oxygen hissed out. Castine was now on his knees, his aged arms outstretched. "Before God, Mr. Kennedy--I didn't do it. I didn't give Leon the poison!" Kennedy, however, engrossed in what he was doing, paid no attention to the appeal. Suddenly I saw what might have been a faint tremor of an eyelid on the pallid body before us. I felt Collette spring forward from my side. "He lives! He lives!" she cried, falling on her knees before the still cataleptic form. "Guillaume!" There was just a faint movement of the lips, as though as the man came back from another world he would have called, "Collette!" "Seize that man--it is his name signed to the wireless messages!" shouted Kennedy, extending his accusing forefinger at Aux Cayes, who had plotted so devilishly to use his voodoo knowledge both to suppress the revolution and at the same time to win his beautiful ward for himself from her real lover. CHAPTER XXXIV THE EVIL EYE "You don't know the woman who is causing the trouble. You haven't seen her eyes. But--Madre de Dios!--my father is a changed man. Sometimes I think he is--what you call--mad!" Our visitor spoke in a hurried, nervous tone, with a marked foreign accent which was not at all unpleasing. She was a young woman, unmistakably beautiful, of the dark Spanish type and apparently a South American. "I am Señorita Inez de Mendoza of Lima, Peru," she introduced herself, as she leaned forward in her chair in a high state of overwrought excitement. "We have been in this country only a short time--my father and I, with his partner in a mining venture, Mr. Lockwood. Since the hot weather came we have been staying at the Beach Inn at Atlantic Beach." She paused a moment and hesitated, as though in this strange land of the north she had no idea of which way to turn for help. "Perhaps I should have gone to see a doctor about him," she considered, doubtfully; then her emotions got the better of her and she went on passionately, "but, Mr. Kennedy it is not a case for a doctor. It is a case for a detective--for someone who is more than a detective." She spoke pleadingly now, in a soft musical voice that was far more pleasing to the ear than that of the usual Spanish-American. I had heard that the women of Lima were famed for their beauty and melodious voices. Señorita Mendoza surely upheld their reputation. There was an appealing look in her soft brown eyes and her thin, delicate lips trembled as she hurried on with her strange story. "I never saw my father in such a state before," she murmured. "All he talks about is the 'big fish'--whatever that may mean--and the curse of Mansiche. At times his eyes are staring wide open. Sometimes I think he has a violent fever. He is excited--and seems to be wasting away. He seems to see strange visions and hear voices. Yet I think he is worse when he is quiet in a dark room alone than when he is down in the lobby of the hotel in the midst of the crowd." A sudden flash of fire seemed to light up her dark eyes. "There is a woman at the hotel, too," she went on, "a woman from Truxillo, Señora de Moche. Ever since she has been there my father has been growing worse and worse." "Who is this Señora de Moche?" asked Kennedy, studying the Señorita as if she were under a lens. "A Peruvian of an old Indian family," she replied. "She has come to New York with her son, Alfonso, who is studying at the University here. I knew him in Peru," she added, as if by way of confession, "when he was a student at the University of Lima." There was something in both her tone and her manner that would lead one to believe that she bore no enmity toward the son--indeed quite the contrary--whatever might be her feelings toward the mother of de Moche. Kennedy reached for our university catalogue and found the name, Alfonso de Moche, a post-graduate student in the School of Engineering, and therefore not in any of Kennedy's own courses. I could see that Craig was growing more and more interested. "And you think," he queried, "that in some way this woman is connected with the strange change that has taken place in your father?" "I don't know," she temporized, but the tone of her answer was sufficient to convey the impression that in her heart she did suspect something, she knew not what. "It's not a long run to Atlantic Beach," considered Kennedy. "I have one or two things that I must finish up first, however." "Then you will come down tonight?" she asked, as Kennedy rose and took the little white silk gloved hand which she extended. "Tonight surely," answered Craig, holding the door for her to pass out. "Well," I said, when we were alone, "what is it--a romance or a crime?" "Both, I think," he replied abstractedly, taking up the experiment which the visit had interrupted. "I think," he remarked late in the afternoon, as he threw off his acid-stained smock, "that I will go over to the University library before it closes and refresh my mind on some of those old Peruvian antiquities and traditions. The big fish or _peje grande_, as I remember it, was the name given by the natives to one of the greatest buried treasures about the time of Pizarro's conquest. If I remember correctly, Mansiche was the great cacique, or something of that sort--the ruler in northern Peru at that time. He is said to have left a curse on any native who ever divulged the whereabouts of the treasure and the curse was also to fall on any Spaniard who might discover it." For more than an hour Kennedy delved into the archeological lore in the library. Then he rejoined me at the laboratory and after a hasty bite of dinner we hurried down to the station. That evening we stepped off the train at Atlantic Beach to make our way to the Beach Inn. The resort was just springing into night life, as the millions of incandescent lights flooded it with a radiance which we could see reflected in the sky long before our train arrived. There was something intoxicating about the combination of the bracing salt air and the gay throngs seeking pleasure. Instead of taking the hotel 'bus, Kennedy decided to stroll to the inn along the boardwalk. We were just about to turn into the miniature park which separated the inn from the walk when we noticed a wheel chair coming in our direction. In it were a young man and a woman of well-preserved middle age. They had evidently been enjoying the ocean breeze after dinner, and the sound of music had drawn them back to the hotel. We entered the lobby of the inn just as the first number of the evening concert by the orchestra was finishing. Kennedy stood at the desk for a moment while Señorita Mendoza was being paged, and ran his eye over the brilliant scene. In a minute the boy returned and led us through the maze of wicker chairs to an alcove just off the hall which later in the evening would be turned into a ballroom. On a wide settee, the Señorita was talking with animation to a tall, clean-cut young man in evening clothes, whose face bore the tan of a sun much stronger than that at Atlantic Beach. He was unmistakably of the type of American soldier of fortune. In a deep rocker before them sat a heavy-set man whose piercing black eyes beetled forth from under bushy eyebrows. He was rather distinguished looking, and his close-cropped hair and mustache set him off as a man of affairs and consequence in his own country. As we approached, Señorita Mendoza rose quickly. I wondered how she was going to get over the awkward situation of introducing us, for surely she did not intend to let her father know that she was employing a detective. She did it most cleverly, with a significant look at Kennedy which he understood. "Good-evening. I am delighted to see you," she greeted. Then, turning to her father, she introduced Craig. "This is Professor Kennedy," she explained, "whom I met at the reception of the Hispano-American Society. You remember I told you he was so much interested in our Peruvian ruins." Don Luis's eyes seemed fairly to glitter with excitement. They were prominent eyes, staring, and I could not help studying them. "Then, Señor Kennedy," he exclaimed, "you know of our ruins of Chan-Chan, of Chima--those wonderful places--and have heard the legend of the _peje grande_?" His eyes, by that time, were almost starting from their sockets, and I noticed that the pupils were dilated almost to the size of the iris. "We must sit down," he went on, "and talk about Peru." The soldier of fortune also had risen as we approached. In her soft musical voice, the Señorita now interrupted her father. "Professor Kennedy, let me introduce you to Mr. Lockwood, my father's partner in a mining project which brings us to New York." As Kennedy and I shook hands with the young mining engineer, I felt that Lockwood was something more to her than a mere partner in her father's mining venture. We drew up chairs and joined the circle. Kennedy said something about mining and the very word "mine" seemed to excite Señor Mendoza still further. "Your American financiers have lost millions in mining in Peru," he exclaimed excitedly, taking out a beautifully chased gold cigarette case, "but we are going to make more millions than they ever dreamed of, because we are simply going to mine for the products of centuries of labor already done, for the great treasure of Truxillo." He opened the cigarette case and handed it about. The cigarettes seemed to be his own special brand. We lighted up and puffed away for a moment. There was a peculiar taste about them, however, which I did not like. In fact, I think that the Latin-American cigarettes do not seem to appeal to an American very much, anyhow. As we talked, I noticed that Kennedy evidently shared my own tastes, for he allowed his cigarette to go out, and after a puff or two I did the same. For the sake of my own comfort I drew out one of my own cigarettes as soon as I could do so politely. "We are not the only ones who have sought the _peje grande_," resumed Mendoza eagerly, "but we are the only ones who are seeking it in the right place, and," he added, leaning over with a whisper, "I am the only one who has the concession, the monopoly, from the government to seek in what we know to be the right place. Others have found the little fish. We shall find the big fish." He had raised his voice from the whisper and I caught the Señorita looking anxiously at Kennedy, as much as to say, "You see? His mind is full of only one subject." Señor Mendoza's eyes had wandered from us and he seemed all of a sudden to grow wild. "We shall find it," he cried, "no matter what obstacles man or devil put in our way. It is ours--for a simple piece of engineering--ours! The curse of Mansiche--pouf!" He snapped his fingers almost defiantly as he said it in a high-pitched voice. There was an air of bravado about it and I could not help feeling that perhaps in his heart he was not so sure of himself as he would have others think. It was as though some diabolical force had taken possession of his brain and he fought it off. Kennedy quickly followed the staring glance of Mendoza. Out on the broad veranda, by an open window a few yards from us, sat the woman of the wheel chair. The young man who accompanied her had his back toward us for the moment, but she was looking fixedly in our direction, paying no attention apparently to the music. She was a large woman, with dark hair, and contrasting full red lips. Her face, in marked contradiction to her Parisian costume and refined manners, had a slight copper swarthiness about it. But it was her eyes that arrested and held one's attention. Whether it was in the eyes themselves or in the way that she used them, there could be no mistake about the hypnotic power that their owner wielded. She saw us looking at her, but it made no difference. Not for an instant did she allow our gaze to distract her in the projection of their weird power straight at Don Luis himself. Don Luis, on his part, seemed fascinated. He rose, and, for a moment, I thought that he was going over to speak to her, as if drawn by that intangible attraction which Poe has so cleverly expressed in his "Imp of the Perverse." Instead, in the midst of the number which the orchestra was playing, he turned and, as though by a superhuman effort, moved away among the guests out into the brighter lights and gayety of the lobby. I glanced up in time to see the anxious look on the Señorita's face change momentarily into a flash of hatred toward the woman in the window. The young man turned just about that time, and there was no mistaking the ardent glance he directed toward the fair Peruvian. I fancied that her face softened a bit, too. She resumed her normal composure as she said to Lockwood, "You will excuse me, I know. Father is tired of the music. I think I will take him for a turn down the boardwalk. If you can join us in our rooms in an hour or so, may we see you!" she asked, with another significant glance at Kennedy. Craig had barely time to reply that we should be delighted before she was gone. Evidently she did not dare let her father get very far out of her sight. We sat for a few moments smoking and chatting with Lockwood. "What is the curse of Mansiche?" asked Kennedy at length. "Oh, I don't know," returned Lockwood, impatiently flicking the ashes from his cigar, as though such stories had no interest for the practical mind of an engineer. "Some old superstition. I don't know much about the story; but I do know that there is treasure in that great old Chimu mound near Truxillo, and that Don Luis has got us the government concession to bore into it, if we can only raise the capital to carry it out." Kennedy showed no disposition to leave the academic and become interested in the thing from the financial standpoint, and the conversation dragged. "I beg pardon," apologized Lockwood at length, "but I have some very important letters that I must get off before the mail closes. I'll see you, I presume, when the Señorita and Don Luis come back?" Kennedy nodded. In fact, I think he was rather glad of the opportunity to look things over unhampered. CHAPTER XXXV THE BURIED TREASURE Señora de Moche--for I had no doubt now that this was the Peruvian Indian woman of whom Señorita Inez had spoken--seemed to lose interest in us and in the concert the moment Don Luis went out. Her son also seemed restive. He was a good-looking fellow, with high forehead, nose slightly aquiline, chin and mouth firm, in fact the whole face refined and intellectual, though tinged with melancholy. We strolled down the wide veranda, and as we passed the woman and her son I was conscious of that strange feeling (which psychologists tell us, however, has no foundation) of being stared at from behind. Kennedy turned suddenly and again we passed, just in time to catch in a low tone from the young man, "Yes, I have seen him at the University. Everyone knows that he--" The rest was lost. It was quite evident now that they thought we were interested in them. There was, then, no use in our watching them further. Indeed, when we turned again, we found that the Señora and Alfonso had risen, gone through the long, open window inside, and were making their way slowly to the elevator. The door of the elevator had scarcely closed when Kennedy turned on his heel and quickly made his way back to the alcove where we had been sitting. Lying about on the ash tray on a little wicker table were several of Mendoza's half-burned cigarettes. We sat down a moment and, after a hasty glance around, Craig gathered them up and folded them in a piece of paper. Leisurely Kennedy strolled over to the desk, and, as guests in a summer hotel will do, looked over the register. The Mendozas, father and daughter, were registered in rooms 810 and 812, a suite on the eighth floor. Lockwood was across the hall in 811. Turning the pages, Kennedy paused, then nudged me. Señora de Moche and Señor Alfonso de Moche were on the same floor in 839 and 841, just around an "L" in the hall. The two parties must meet frequently not only downstairs in the inn, but in the corridors and elevators. Kennedy said nothing, but glanced at his watch. We had nearly three-quarters of an hour to wait yet until our pretty client returned. "There's no use in wasting time or in trying to conceal our identity," he said finally, drawing a card from his pocket and handing it to the clerk. "Señora de Moche, please." Much to my surprise, the Señora telephoned down that she would see us in her own sitting-room, and I followed Kennedy into the elevator. Alfonso was out and the Señora was alone. "I hope that you will pardon me," began Craig with an elaborate explanation, "but I have become interested in an opportunity to invest in a Peruvian venture and they tell me at the office that you are a Peruvian. I thought that perhaps you could advise me." She looked at us keenly. I fancied that she detected the subterfuge, yet she did not try to avoid us. On closer view, her eyes were really remarkable--those of a woman endowed with an abundance of health and energy--eyes that were full of what the old phrenologists used to call amativeness, denoting a nature capable of intense passion, whether of love or hate. Yet I confess that I could not find anything especially abnormal about them, as I had about Mendoza's. "I suppose you mean that scheme of Señor Mendoza and his friend, Mr. Lockwood," she returned, speaking rapidly. "Let me tell you about it. You may know that the Chimu tribes in the north were the wealthiest at the time of the coming of the Spaniards. Well, they had a custom of burying with their dead all their movable property. Sometimes a common grave or _huaca_ was given to many. That would become a cache of treasure. "Back in the seventeenth century," she continued, leaning forward eagerly as she talked, "a Spaniard opened a Chimu _huaca_ and found gold that is said to have been worth a million dollars. An Indian told him of it. After he had shown him the treasure, the Indian told the Spaniard that he had given him only the little fish, the _peje chica_, but that some day he would give him the big fish, the _peje grande_. "The Indian died," she went on solemnly, flashing at Craig a glance from her wonderful eyes. "He was poisoned by the other members of his tribe." She paused, then flashed, "That is my tribe, my family." She paused a moment. "The big fish is still a secret--or at least it was until they got it from my brother, to whom the tradition had been intrusted. They drove him crazy--until he talked. Then, after he had told the secret, and lost his mind, he threw himself one day into Lake Titicaca." She stopped dramatically in her passionate out-pouring of the tragedies that had followed the hidden treasure. "I cannot tell you more than you probably already know," she resumed, watching our faces intently. "You know, I suppose, that the treasure is believed to be in a large mound, a tumulus I think you call it, visible from our town of Truxillo. Many people have tried to open it, but the mass of sand pours down on them and they have been discouraged. But Señor Mendoza believes that he knows just where to bore and Mr. Lockwood has a plan for a well-timbered tunnel which can be driven at the right point." She said it with a sort of quiet assurance that conveyed the impression without her saying it that the venture was somehow doomed to failure, that these desecrators were merely toying with fate. All through her remarks one could feel that she suspected Mendoza of having been responsible for the downfall and tragedy of her brother, who had betrayed the age-old secret. Her eyes assumed a far-away, dreamy look as she went on. "You must know that we Peruvians have been so educated that we never explore ruins for hidden treasure--not even if we have the knowledge of engineering to do so." Apparently she was thinking of her son and his studies at the University. One could follow her thoughts as they flitted from him to the beautiful girl with whom she had seen us. "We are a peculiar race," she proceeded. "We seldom intermarry with other races. We are as proud as Señor Mendoza, as proud of our unmixed lineage as your 'belted earls.'" She said it with a quiet dignity quite in contrast with the nervous, hasty manner of Don Luis. There was no doubt that the race feeling cut deep. Kennedy had been following her closely and I could see that the cross currents of superstition, avarice and race hatred in the case presented a tangle that challenged him. "Thank you," he murmured, rising. "You have told me quite enough to make me think seriously before I join in any such undertaking." She smiled enigmatically and we bowed ourselves out. "A most baffling woman," was Craig's only comment as we rode down again in the elevator to wait for the return of Don Luis and the Señorita. Scarcely had their chair set them down at the inn than Alfonso seemed to appear from nowhere. He had evidently been waiting in the shadow of the porch for them. We stood aside and watched the little drama. For a few minutes the Señorita talked with him. One did not need to be told that she had a deep regard for the young man. She wanted to see him, yet she did not want to see him. Don Luis, on the contrary, seemed to become quite restive and impatient again and to wish to cut the conversation short. It was self-evident that Alfonso was deeply in love with Inez. I wondered whether, after all, the trouble was that the proud old Castilian Don Luis would never consent to the marriage of his daughter to one of Indian blood? Was he afraid of a love forbidden by race prejudice? In any event, one could easily imagine the feelings of Alphonso toward Lockwood, whom he saw carrying off the prize under his very eyes. As for his mother, we had seen that the Peruvians of her caste were a proud old race. Her son was the apple of her eye. Who were these to scorn her race, her family? It was a little more than an hour after our first meeting when the party, including Lockwood, who had finished his letters, gathered again up in the rooms of the Mendozas. It was a delightful evening, even in spite of the tension on which we were. We chatted about everything from archeology to Wall Street, until I could well imagine how anyone possessed of an imagination susceptible to the influence of mystery and tradition would succumb to the glittering charm of the magic words, _peje chica_, and feel all the gold hunter's enthusiasm when brought into the atmosphere of the _peje grande_. Visions of hidden treasure seemed to throw a glamour over everything. Kennedy and the Señorita had moved over to a window, where they were gazing out on the fairyland of Atlantic Beach spread out before them, while Lockwood and Don Luis were eagerly quizzing me on the possibilities of newspaper publicity. "Oh, Professor Kennedy," I heard her say under her breath, "sometimes I fear that it is the _mal de ojo_--the evil eye." I did not catch Craig's answer, but I did catch time and again narrowly observing Don Luis. Our host was smoking furiously now, and his eyes had even more than before that peculiar, staring look. By the way his veins stood out I could see that Mendoza's heart action must be rapid. He was talking more and more wildly as he grew more excited. Even Lockwood noticed it and, I thought, frowned. Slowly the conviction was forced on me. The man was mad--raving mad! "Really, I must get back to the city tonight," I overheard Craig say to the Señorita as finally he turned from the window toward us. Her face clouded, but she said nothing. "If you could arrange to have us dine with you tomorrow night up here, however," he added quickly in a whisper, "I think I might be prepared to take some action." "By all means," she replied eagerly, as though catching at anything that promised aid. On the late train back, I half dozed, wondering what had caused Mendoza's evident madness. Was it a sort of auto-hypnotism? There was, I knew, a form of illusion known as ophthalmophobia--fear of the eye. It ranged from mere aversion at being gazed at, all the way to the subjective development of real physical illness out of otherwise trifling ailments. If not that, what object could there be for anyone to cause such a condition? Might it be for the purpose of robbery? Or might it be for revenge? Back in the laboratory, Kennedy pulled out from a cabinet a peculiar apparatus. It seemed to consist of a sort of triangular prism set with its edge vertically on a rigid platform attached to a massive stand. Next he lighted one of the cigarette stubs which he had carried away so carefully. The smoke curled up between a powerful light and the peculiar instrument, while Craig peered through a lens, manipulating the thing with exhaustless patience and skill. Finally he beckoned me over and I looked through, too. On a sort of fine grating all I could see was a number of strange lines. "That," he explained in answer to my unspoken question as I continued to gaze, "is one of the latest forms of the spectroscope, known as the interferometer, with delicately ruled gratings in which power to resolve the straight close lines in the spectrum is carried to the limit of possibility. A small watch is delicate, but it bears no comparison to the delicacy of these detraction spectroscopes. "Every substance, you know, is, when radiating light, characterized by what at first appears to be almost a haphazard set of spectral lines without relation to one another. But they are related by mathematical laws and the apparent haphazard character is only the result of our lack of knowledge of how to interpret the results." He resumed his place at the eye-piece to check over his results. "Walter," he said finally with a twinkle of the eye, "I wish you'd go out and find me a cat." "A cat?" I repeated. "Yes--a cat--felis domesticus, if it sounds better that way, a plain ordinary cat." I jammed on my hat and, late as it was, sallied forth on this apparently ridiculous mission. Several belated passers-by and a policeman watched me as though I were a house-breaker and I felt like a fool, but at last by perseverance and tact I managed to capture a fairly good specimen of the species and transported it in my arms to the laboratory without an undue number of scratches. CHAPTER XXXVI THE WEED OF MADNESS In my absence Craig had set to work on a peculiar apparatus, as though he were distilling something from several of the other cigarette stubs. I placed the cat in a basket and watched Craig until finally he seemed to be rewarded for his patient labors. It was well along toward morning when he obtained in a test-tube a few drops of a colorless, almost odorless liquid. I watched him curiously as he picked the cat out of the basket and held it gently in his arms. With a dropper he sucked up a bit of the liquid from the test-tube. Then he let a small drop fall into the eye of the cat. The cat blinked a moment and I bent over to observe it more closely. The cat's eye seemed to enlarge, even under the light, as if it were the proverbial cat's eye under a bed. What did it mean? Was there such a thing as the drug of the evil eye? "What have you found?" I queried. "Something very much like the so-called 'weed of madness,' I think," he replied slowly. "The weed of madness?" I repeated. "Yes, something like that Mexican toloache and the Hindu datura which you must have heard about," he continued. "You know the jimson weed--the Jamestown weed? It grows almost everywhere in the world, but most thrivingly in the tropics. They are all related in some way, I believe. The jimson weed on the Pacific coast of the Andes has large white flowers which exhale a faint, repulsive odor. It is a harmless looking plant with its thick tangle of leaves, a coarse green growth, with trumpet-shaped flowers. But, to one who knows its properties, it is quite too dangerously convenient. "I think those cigarettes have been doped," he went on positively. "It isn't toloache that was used. I think it must be some particularly virulent variety of the jimson weed. Perhaps it is in the preparation of the thing. The seeds of the stramonium, which is the same thing, contain a higher percentage of poison than the leaves and flowers. Perhaps they were used. I can't say." He took a drop of the liquid he had isolated and added a drop of nitric acid. Then he evaporated it by gentle heat and it left a residue which was slightly yellow. Next he took from the shelf over his table a bottle marked alcoholic solution, potassium hydrate, and let a drop fall on it. Instantly the residue became a beautiful purple, turning rapidly to violet, then to dark red and finally disappeared. "Stramonium all right," he nodded with satisfaction. "That was known as Vitali's test. Yes, there was stramonium in those cigarettes--datura stramonium--perhaps a trace of hyocyamino. They are all, like atropine, mydriatic alkaloids, so-called from the effect on the eye. One one-hundred-thousandth of a grain will affect the cat's eye. You saw how it acted. It is more active than even atropine. Better yet, you remember how Don Luis's eyes looked." "How about the Señora?" I put in. "Oh," he answered quickly, "her pupils were normal enough. Didn't you notice that? This concentrated poison which has been used in Mendoza's cigarettes does not kill, at least not outright. It is worse. Slowly it accumulates in the system. It acts on the brain. Of all the dangers to be met with in superstitious countries, these mydriatic alkaloids are among the worst. They offer a chance for crimes of the most fiendish nature--worse than the gun or the stiletto, and with little fear of detection. It is the production of insanity!" Horrible though the idea was I could not doubt it in the face of Craig's investigations and what I had already seen. In fact, it was necessary for me only to recall the peculiar sensations I myself had experienced after smoking merely a few puffs of one of Mendoza's cigarettes in order to be convinced of the possible effect of the insidious poison contained in the many that he smoked. It was almost dawn before Craig and I left the laboratory after his discovery of the manner of the stramonium poisoning. I was thoroughly tired, though not so much so that my dreams were not haunted by a succession of baleful eyes peering at me from the darkness. I slept late, but Kennedy was about early at the laboratory, verifying his experiments and checking over his results, carefully endeavoring to isolate any other of the closely related mydriatic alkaloids that might be contained in the noxious fumes of the poisoned tobacco. Though he was already convinced of what was going on, I knew that he considered it a matter of considerable medico-legal importance to be exact, for if the affair ever came to the stage of securing an indictment, the charge could be sustained only by specific proof. Early in the forenoon Kennedy left me alone in the laboratory and made a trip downtown, where he visited a South American tobacco dealer and placed a rush order for a couple of hundred cigarettes, duplicating in shape and quality those which Señor Mendoza doza preferred, except, however, the deadly drug which was in those he was smoking. I had some writing to do and was busily engaged at my typewriter when I suddenly became conscious of that feeling of being watched. Perhaps I had heard a footstep outside and did not remember it, but at any rate I had the feeling. I stopped tapping the keys suddenly and wheeled about in my chair just in time to catch a glimpse of a face dodging back from the window. I don't think that I would be prepared to swear just who it was, but there was just enough that was familiar about the fleeting glimpse of the eyes to make me feel uncomfortable. I ran to the door, but it was too late. The intruder had disappeared. Still, the more I thought about it, the more determined I was to verify my suspicions, if possible. I put on my hat and walked over to the registrar's office. Sure enough, Alfonso de Moche was registered in the summer school as well as in the regular course. I was now fully convinced that it was he who had been watching us. Not satisfied, I determined to make further inquiries about the young man. He had been at the University that morning, I learned from one of his professors, and that convinced me more than ever that he had employed at least a part of the time in spying on us. As I had expected, the professor told me that he was an excellent student, though very quiet and reserved. His mind seemed to run along the line of engineering and mining, especially, and I could not help drawing the conclusion that perhaps he, too, was infected by the furore for treasure hunting, in spite of his Indian ancestry. Nothing further occurred, however, during the day to excite suspicion and Craig listened with interest, though without comment, when I related what had happened. He divided his time during the rest of the day between some experimental work of his own and fits of deep reverie in which he was evidently trying to piece together the broken strands of the strange story in which we were now concerned. The package of cigarettes which he had ordered was delivered late in the afternoon. Kennedy had already wrapped up a small package of a powder and filled a small atomizer with some liquid. Stowing these things away in his pockets as best he could, with a little vial which he shoved into his waistcoat pocket, he announced that he was ready at last to take an early train to Atlantic Beach. We dined that night, as Craig had requested, with the Mendozas and Lockwood up in the sitting-room of Don Luis's suite. It was a delightfully situated room, overlooking the boardwalk and the ocean, and the fresh wind that was wafted in from the water made it quite the equal of a roof garden. Dinner had been ordered but not served, when Craig maneuvered to get a few minutes alone with Inez. Although I could not hear, I gathered that he was outlining at least a part of his plans to her and seeking her co-operation. She seemed to understand and approve, and I really believe that the dinner was the first in a long time that the distracted girl had really enjoyed. While we were waiting for it, I suddenly became aware that she had contrived to leave Kennedy and myself alone in the sitting-room for a moment. It was evidently part of Craig's plan. Instantly he opened a large case in which Mendoza kept cigarettes and hastily substituted for those in it an equal number of the cigarettes which he had had made. The dinner itself was more like a family party than a formal dinner, for Kennedy, when he wanted to do so, had a way of ingratiating himself and leading the conversation so that everyone was at his ease. Everything progressed smoothly until we came to the coffee. The Señorita poured, and as she raised the coffee pot Kennedy called our attention to a long line of colliers just on the edge of the horizon, slowly making their way up the coast. I was sitting next to the Señorita, not particularly interested in colliers at that moment. From a fold in her dress I saw her hastily draw a little vial and pour a bit of yellowish, syrupy liquid into the cup which she was preparing for her father. I could not help looking at her quickly. She saw me, then raised her finger to her lips with an explanatory glance at Kennedy, who was keeping the others interested in colliers. Instantly I recognized the little vial that Kennedy had shoved into his vest pocket. More coffee and innumerable cigarettes followed. I did my best to aid in the conversation, but my real interest was centered in Don Luis himself, whom I could not help watching closely. Was it a fact or was it merely imagination? He seemed quite different. The pupils of his eyes did not seem to be quite so dilated as they had been the night before. Even his heart action appeared to be more normal. I think the Señorita noticed it, too. Dinner over and darkness cutting off the magnificent sweep of ocean view, Inez suggested that we go down to the concert, as had been their custom. It was the first time that Kennedy had not seemed to fall in with any of her suggestions, but I knew that that, too, must be part of his preconcerted plan. "If you will pardon us," he excused, "Mr. Jameson and I have some friends over at Stillson Hall whom we have promised to run in to see. I think this would be a good opportunity. We'll rejoin you--in the alcove where we were last night, if possible." No one objected. In fact I think Lockwood was rather glad to have a chance to talk to Inez, for Kennedy had monopolized a great deal of her attention. We left them at the elevator, but instead of leaving the Inn Kennedy edged his way around into the shadow of a doorway where we could watch. Fortunately the Señorita managed to get the same settee in the corner which we had occupied the night before. A moment later I caught a glimpse of a familiar face at the long window opening on the veranda. Señora de Moche and her son had drawn up chairs, just outside. They had not seen us and, as far as we knew, had no reason to suspect that we were about. As we watched the two groups, I could not fail to note that the change in Don Luis was really marked. There was none of the wildness in his conversation, as there had been. Once he even met the keen eye of the Señora, but it did not seem to have the effect it had had on the previous occasion. "What was it you had the Señorita drop into his coffee?" I asked Craig under my breath. "You saw that?" he smiled. "It was pilocarpine, jaborandi, a plant found largely in Brazil, one of the antidotes for stramonium poisoning. It doesn't work with everyone. But it seems to have done so with Mendoza. Besides, the caffeine in the coffee probably aided the pilocarpine. Did you notice how it contracted his pupils almost back to normal again?" Kennedy did not take his eyes off the two groups as he talked. "I've got at the case from a brand-new angle, I think," he added. "Unless I am mistaken, when the criminal sees Don Luis getting better, it will mean another attempt to substitute more cigarettes doped with that drug." Satisfied so far with the play he was staging, Kennedy moved over to the hotel desk, and after a quiet conference with the head clerk, found out that the room next to the suite of the Mendozas was empty. The clerk gave him several keys and with a last look at the Señora and her son, to see whether they were getting restive, I followed Craig into the elevator and we rode up to the eighth floor again. The halls were deserted now and we entered the room next to the Mendozas without being observed. It was a simple matter after that to open a rather heavy door that communicated between the two suites. Instead of switching on the light, Kennedy first looked about carefully until he was assured that no one was there. Quickly he sprinkled on the floor from the hall door to the table on which the case of cigarettes lay some of the powder which I had seen him wrap up in the laboratory before we left. Then with the atomizer he sprayed over it something that had a pungent, familiar odor, walking backwards from the hall door as he did so. "Don't you want more light?" I asked, starting to cross to a window to raise a shade to let the moonlight stream in. "Don't walk on it, Walter," he whispered, pushing me back. "First I sprinkled some powdered iodine and then ammonia enough to moisten it. It evaporates quickly, leaving what I call my anti-burglar powder." He had finished his work and now the evening wind was blowing away the slight fumes that had risen. For a few moments he left the door into the next room open to clear away the odor, then quietly closed it, but did not lock it. In the darkness we settled ourselves now for a vigil that was to last we knew not how long. Neither of us spoke as we half crouched in the shadow of the next room, listening. Slowly the time passed. Would anyone take advantage of the opportunity to tamper with that box of cigarettes on Mendoza's table? Who was it who had conceived and executed this devilish plot? What was the purpose back of it all? Once or twice we heard the elevator door clang and waited expectantly, but nothing happened. I began to wonder whether if someone had a pass-key to the Mendoza suite we could hear them enter. The outside hall was thickly carpeted and deadened every footfall if one exercised only reasonable caution. "Don't you think we might leave the door ajar a little?" I suggested anxiously. "Sh!" was Kennedy's only comment in the negative. I glanced now and then at my watch and was surprised to see how early it was. The minutes were surely leaden-footed. In the darkness and silence I fell to reviewing the weird succession of events which had filled the past two days. I am not by nature superstitious, but in the darkness I could well imagine a staring succession of eyes, beginning with the dilated pupils of Don Luis and always ending with those remarkable piercing black eyes of the Indian woman with the melancholy-visaged son. Suddenly I heard in the next room what sounded like a series of little explosions, as though someone were treading on match-heads. "My burglar powder," muttered Craig in a hoarse whisper. "Every step, even those of a mouse running across, sets it off!" He rose quickly and threw open the door into the Mendoza suite. I sprang through after him. There, in the shadows, I saw a dark form, starting back in retreat. But it was too late. In the dim light of the little explosions, I caught a glimpse of a face--the face of the person who had been craftily working on the superstition of Don Luis, now that his influence had got from the government the precious concession, working with the dread drug to drive him insane and thus capture both Mendoza's share of the fortune as well as his daughter, well knowing that suspicion would rest on the jealous Indian woman with the wonderful eyes whose brother had already been driven insane and whose son Inez Mendoza really loved better than himself--the soldier of fortune, Lockwood. 
30775	----	ELEMENTS OF CHEMISTRY, IN A NEW SYSTEMATIC ORDER, CONTAINING ALL THE MODERN DISCOVERIES. ILLUSTRATED WITH THIRTEEN COPPERPLATES. BY MR LAVOISIER, Member of the Academy of Sciences, Royal Society of Medicine, and Agricultural Society of Paris, of the Royal Society of London, and Philosophical Societies of Orleans, Bologna, Basil, Philadelphia, Haerlem, Manchester, &c. &c. TRANSLATED FROM THE FRENCH, BY ROBERT KERR, F.R. & A.SS.E. Member of the Royal College of Surgeons, and Surgeon to the Orphan Hospital of Edinburgh. EDINBURGH: PRINTED FOR WILLIAM CREECH, AND SOLD IN LONDON BY G. G. AND J. J. ROBINSONS. MDCCXC. ************************************************************************ Transcriber's note: Tables needed to be split to fit space constraints. Minor typos have been corrected and footnotes moved to the end of the chapters. The italic markup for single italized letters (such as variables in equations) and weight abbreviations are deleted for easier reading. ************************************************************************ ADVERTISEMENT OF THE TRANSLATOR. The very high character of Mr Lavoisier as a chemical philosopher, and the great revolution which, in the opinion of many excellent chemists, he has effected in the theory of chemistry, has long made it much desired to have a connected account of his discoveries, and of the new theory he has founded upon the modern experiments written by himself. This is now accomplished by the publication of his Elements of Chemistry; therefore no excuse can be at all necessary for giving the following work to the public in an English dress; and the only hesitation of the Translator is with regard to his own abilities for the task. He is most ready to confess, that his knowledge of the composition of language fit for publication is far inferior to his attachment to the subject, and to his desire of appearing decently before the judgment of the world. He has earnestly endeavoured to give the meaning of the Author with the most scrupulous fidelity, having paid infinitely greater attention to accuracy of translation than to elegance of stile. This last indeed, had he even, by proper labour, been capable of attaining, he has been obliged, for very obvious reasons, to neglect, far more than accorded with his wishes. The French copy did not reach his hands before the middle of September; and it was judged necessary by the Publisher that the Translation should be ready by the commencement of the University Session at the end of October. He at first intended to have changed all the weights and measures used by Mr Lavoisier into their correspondent English denominations, but, upon trial, the task was found infinitely too great for the time allowed; and to have executed this part of the work inaccurately, must have been both useless and misleading to the reader. All that has been attempted in this way is adding, between brackets ( ), the degrees of Fahrenheit's scale corresponding with those of Reaumeur's thermometer, which is used by the Author. Rules are added, however, in the Appendix, for converting the French weights and measures into English, by which means the reader may at any time calculate such quantities as occur, when desirous of comparing Mr Lavoisier's experiments with those of British authors. By an oversight, the first part of the translation went to press without any distinction being preserved between charcoal and its simple elementary part, which enters into chemical combinations, especially with oxygen or the acidifying principle, forming carbonic acid. This pure element, which exists in great plenty in well made charcoal, is named by Mr Lavoisier _carbone_, and ought to have been so in the translation; but the attentive reader can very easily rectify the mistake. There is an error in Plate XI. which the engraver copied strictly from the original, and which was not discovered until the plate was worked off at press, when that part of the Elements which treats of the apparatus there represented came to be translated. The two tubes 21. and 24. by which the gas is conveyed into the bottles of alkaline solution 22. 25. should have been made to dip into the liquor, while the other tubes 23. and 26. which carry off the gas, ought to have been cut off some way above the surface of the liquor in the bottles. A few explanatory notes are added; and indeed, from the perspicuity of the Author, very few were found necessary. In a very small number of places, the liberty has been taken of throwing to the bottom of the page, in notes, some parenthetical expressions, only relative to the subject, which, in their original place, tended to confuse the sense. These, and the original notes of the Author, are distinguished by the letter A, and to the few which the Translator has ventured to add, the letter E is subjoined. Mr Lavoisier has added, in an Appendix, several very useful Tables for facilitating the calculations now necessary in the advanced state of modern chemistry, wherein the most scrupulous accuracy is required. It is proper to give some account of these, and of the reasons for omitting several of them. No. I. of the French Appendix is a Table for converting ounces, gros, and grains, into the decimal fractions of the French pound; and No. II. for reducing these decimal fractions again into the vulgar subdivisions. No. III. contains the number of French cubical inches and decimals which correspond to a determinate weight of water. The Translator would most readily have converted these Tables into English weights and measures; but the necessary calculations must have occupied a great deal more time than could have been spared in the period limited for publication. They are therefore omitted, as altogether useless, in their present state, to the British chemist. No. IV. is a Table for converting lines or twelfth parts of the inch, and twelfth parts of lines, into decimal fractions, chiefly for the purpose of making the necessary corrections upon the quantities of gasses according to their barometrical pressure. This can hardly be at all useful or necessary, as the barometers used in Britain are graduated in decimal fractions of the inch, but, being referred to by the Author in the text, it has been retained, and is No. I. of the Appendix to this Translation. No. V. Is a Table for converting the observed heights of water within the jars used in pneumato-chemical experiments into correspondent heights of mercury for correcting the volume of gasses. This, in Mr Lavoisier's Work, is expressed for the water in lines, and for the mercury in decimals of the inch, and consequently, for the reasons given respecting the Fourth Table, must have been of no use. The Translator has therefore calculated a Table for this correction, in which the water is expressed in decimals, as well as the mercury. This Table is No. II. of the English Appendix. No. VI. contains the number of French cubical inches and decimals contained in the corresponding ounce-measures used in the experiments of our celebrated countryman Dr Priestley. This Table, which forms No. III. of the English Appendix, is retained, with the addition of a column, in which the corresponding English cubical inches and decimals are expressed. No. VII. Is a Table of the weights of a cubical foot and inch, French measure, of the different gasses expressed in French ounces, gros, grains, and decimals. This, which forms No. VI. of the English Appendix, has been, with considerable labour, calculated into English weight and measure. No. VIII. Gives the specific gravities of a great number of bodies, with columns, containing the weights of a cubical foot and inch, French measure, of all the substances. The specific gravities of this Table, which is No. VII. of the English Appendix, are retained, but the additional columns, as useless to the British philosopher, are omitted; and to have converted these into English denominations must have required very long and painful calculations. Rules are subjoined, in the Appendix to this translation, for converting all the weights and measures used by Mr Lavoisier into corresponding English denominations; and the Translator is proud to acknowledge his obligation to the learned Professor of Natural Philosophy in the University of Edinburgh, who kindly supplied him with the necessary information for this purpose. A Table is likewise added, No. IV. of the English Appendix, for converting the degrees of Reaumeur's scale used by Mr Lavoisier into the corresponding degrees of Fahrenheit, which is universally employed in Britain[1]. This Translation is sent into the world with the utmost diffidence, tempered, however, with this consolation, that, though it must fall greatly short of the elegance, or even propriety of language, which every writer ought to endeavour to attain, it cannot fail of advancing the interests of true chemical science, by disseminating the accurate mode of analysis adopted by its justly celebrated Author. Should the public call for a second edition, every care shall be taken to correct the forced imperfections of the present translation, and to improve the work by valuable additional matter from other authors of reputation in the several subjects treated of. EDINBURGH, } Oct. 23. 1789. } FOOTNOTES: [1] The Translator has since been enabled, by the kind assistance of the gentleman above alluded to, to give Tables, of the same nature with those of Mr Lavoisier, for facilitating the calculations of the results of chemical experiments. PREFACE OF THE AUTHOR. When I began the following Work, my only object was to extend and explain more fully the Memoir which I read at the public meeting of the Academy of Sciences in the month of April 1787, on the necessity of reforming and completing the Nomenclature of Chemistry. While engaged in this employment, I perceived, better than I had ever done before, the justice of the following maxims of the Abbé de Condillac, in his System of Logic, and some other of his works. "We think only through the medium of words.--Languages are true analytical methods.--Algebra, which is adapted to its purpose in every species of expression, in the most simple, most exact, and best manner possible, is at the same time a language and an analytical method.--The art of reasoning is nothing more than a language well arranged." Thus, while I thought myself employed only in forming a Nomenclature, and while I proposed to myself nothing more than to improve the chemical language, my work transformed itself by degrees, without my being able to prevent it, into a treatise upon the Elements of Chemistry. The impossibility of separating the nomenclature of a science from the science itself, is owing to this, that every branch of physical science must consist of three things; the series of facts which are the objects of the science, the ideas which represent these facts, and the words by which these ideas are expressed. Like three impressions of the same seal, the word ought to produce the idea, and the idea to be a picture of the fact. And, as ideas are preserved and communicated by means of words, it necessarily follows that we cannot improve the language of any science without at the same time improving the science itself; neither can we, on the other hand, improve a science, without improving the language or nomenclature which belongs to it. However certain the facts of any science may be, and, however just the ideas we may have formed of these facts, we can only communicate false impressions to others, while we want words by which these may be properly expressed. To those who will consider it with attention, the first part of this treatise will afford frequent proofs of the truth of the above observations. But as, in the conduct of my work, I have been obliged to observe an order of arrangement essentially differing from what has been adopted in any other chemical work yet published, it is proper that I should explain the motives which have led me to do so. It is a maxim universally admitted in geometry, and indeed in every branch of knowledge, that, in the progress of investigation, we should proceed from known facts to what is unknown. In early infancy, our ideas spring from our wants; the sensation of want excites the idea of the object by which it is to be gratified. In this manner, from a series of sensations, observations, and analyses, a successive train of ideas arises, so linked together, that an attentive observer may trace back to a certain point the order and connection of the whole sum of human knowledge. When we begin the study of any science, we are in a situation, respecting that science, similar to that of children; and the course by which we have to advance is precisely the same which Nature follows in the formation of their ideas. In a child, the idea is merely an effect produced by a sensation; and, in the same manner, in commencing the study of a physical science, we ought to form no idea but what is a necessary consequence, and immediate effect, of an experiment or observation. Besides, he that enters upon the career of science, is in a less advantageous situation than a child who is acquiring his first ideas. To the child, Nature gives various means of rectifying any mistakes he may commit respecting the salutary or hurtful qualities of the objects which surround him. On every occasion his judgments are corrected by experience; want and pain are the necessary consequences arising from false judgment; gratification and pleasure are produced by judging aright. Under such masters, we cannot fail to become well informed; and we soon learn to reason justly, when want and pain are the necessary consequences of a contrary conduct. In the study and practice of the sciences it is quite different; the false judgments we form neither affect our existence nor our welfare; and we are not forced by any physical necessity to correct them. Imagination, on the contrary, which is ever wandering beyond the bounds of truth, joined to self-love and that self-confidence we are so apt to indulge, prompt us to draw conclusions which are not immediately derived from facts; so that we become in some measure interested in deceiving ourselves. Hence it is by no means to be wondered, that, in the science of physics in general, men have often made suppositions, instead of forming conclusions. These suppositions, handed down from one age to another, acquire additional weight from the authorities by which they are supported, till at last they are received, even by men of genius, as fundamental truths. The only method of preventing such errors from taking place, and of correcting them when formed, is to restrain and simplify our reasoning as much as possible. This depends entirely upon ourselves, and the neglect of it is the only source of our mistakes. We must trust to nothing but facts: These are presented to us by Nature, and cannot deceive. We ought, in every instance, to submit our reasoning to the test of experiment, and never to search for truth but by the natural road of experiment and observation. Thus mathematicians obtain the solution of a problem by the mere arrangement of data, and by reducing their reasoning to such simple steps, to conclusions so very obvious, as never to lose sight of the evidence which guides them. Thoroughly convinced of these truths, I have imposed upon myself, as a law, never to advance but from what is known to what is unknown; never to form any conclusion which is not an immediate consequence necessarily flowing from observation and experiment; and always to arrange the facts, and the conclusions which are drawn from them, in such an order as shall render it most easy for beginners in the study of chemistry thoroughly to understand them. Hence I have been obliged to depart from the usual order of courses of lectures and of treatises upon chemistry, which always assume the first principles of the science, as known, when the pupil or the reader should never be supposed to know them till they have been explained in subsequent lessons. In almost every instance, these begin by treating of the elements of matter, and by explaining the table of affinities, without considering, that, in so doing, they must bring the principal phenomena of chemistry into view at the very outset: They make use of terms which have not been defined, and suppose the science to be understood by the very persons they are only beginning to teach. It ought likewise to be considered, that very little of chemistry can be learned in a first course, which is hardly sufficient to make the language of the science familiar to the ears, or the apparatus familiar to the eyes. It is almost impossible to become a chemist in less than three or four years of constant application. These inconveniencies are occasioned not so much by the nature of the subject, as by the method of teaching it; and, to avoid them, I was chiefly induced to adopt a new arrangement of chemistry, which appeared to me more consonant to the order of Nature. I acknowledge, however, that in thus endeavouring to avoid difficulties of one kind, I have found myself involved in others of a different species, some of which I have not been able to remove; but I am persuaded, that such as remain do not arise from the nature of the order I have adopted, but are rather consequences of the imperfection under which chemistry still labours. This science still has many chasms, which interrupt the series of facts, and often render it extremely difficult to reconcile them with each other: It has not, like the elements of geometry, the advantage of being a complete science, the parts of which are all closely connected together: Its actual progress, however, is so rapid, and the facts, under the modern doctrine, have assumed so happy an arrangement, that we have ground to hope, even in our own times, to see it approach near to the highest state of perfection of which it is susceptible. The rigorous law from which I have never deviated, of forming no conclusions which are not fully warranted by experiment, and of never supplying the absence of facts, has prevented me from comprehending in this work the branch of chemistry which treats of affinities, although it is perhaps the best calculated of any part of chemistry for being reduced into a completely systematic body. Messrs Geoffroy, Gellert, Bergman, Scheele, De Morveau, Kirwan, and many others, have collected a number of particular facts upon this subject, which only wait for a proper arrangement; but the principal data are still wanting, or, at least, those we have are either not sufficiently defined, or not sufficiently proved, to become the foundation upon which to build so very important a branch of chemistry. This science of affinities, or elective attractions, holds the same place with regard to the other branches of chemistry, as the higher or transcendental geometry does with respect to the simpler and elementary part; and I thought it improper to involve those simple and plain elements, which I flatter myself the greatest part of my readers will easily understand, in the obscurities and difficulties which still attend that other very useful and necessary branch of chemical science. Perhaps a sentiment of self-love may, without my perceiving it, have given additional force to these reflections. Mr de Morveau is at present engaged in publishing the article _Affinity_ in the Methodical Encyclopædia; and I had more reasons than one to decline entering upon a work in which he is employed. It will, no doubt, be a matter of surprise, that in a treatise upon the elements of chemistry, there should be no chapter on the constituent and elementary parts of matter; but I shall take occasion, in this place, to remark, that the fondness for reducing all the bodies in nature to three or four elements, proceeds from a prejudice which has descended to us from the Greek Philosophers. The notion of four elements, which, by the variety of their proportions, compose all the known substances in nature, is a mere hypothesis, assumed long before the first principles of experimental philosophy or of chemistry had any existence. In those days, without possessing facts, they framed systems; while we, who have collected facts, seem determined to reject them, when they do not agree with our prejudices. The authority of these fathers of human philosophy still carry great weight, and there is reason to fear that it will even bear hard upon generations yet to come. It is very remarkable, that, notwithstanding of the number of philosophical chemists who have supported the doctrine of the four elements, there is not one who has not been led by the evidence of facts to admit a greater number of elements into their theory. The first chemists that wrote after the revival of letters, considered sulphur and salt as elementary substances entering into the composition of a great number of substances; hence, instead of four, they admitted the existence of six elements. Beccher assumes the existence of three kinds of earth, from the combination of which, in different proportions, he supposed all the varieties of metallic substances to be produced. Stahl gave a new modification to this system; and succeeding chemists have taken the liberty to make or to imagine changes and additions of a similar nature. All these chemists were carried along by the influence of the genius of the age in which they lived, which contented itself with assertions without proofs; or, at least, often admitted as proofs the slighted degrees of probability, unsupported by that strictly rigorous analysis required by modern philosophy. All that can be said upon the number and nature of elements is, in my opinion, confined to discussions entirely of a metaphysical nature. The subject only furnishes us with indefinite problems, which may be solved in a thousand different ways, not one of which, in all probability, is consistent with nature. I shall therefore only add upon this subject, that if, by the term _elements_, we mean to express those simple and indivisible atoms of which matter is composed, it is extremely probable we know nothing at all about them; but, if we apply the term _elements_, or _principles of bodies_, to express our idea of the last point which analysis is capable of reaching, we must admit, as elements, all the substances into which we are capable, by any means, to reduce bodies by decomposition. Not that we are entitled to affirm, that these substances we consider as simple may not be compounded of two, or even of a greater number of principles; but, since these principles cannot be separated, or rather since we have not hitherto discovered the means of separating them, they act with regard to us as simple substances, and we ought never to suppose them compounded until experiment and observation has proved them to be so. The foregoing reflections upon the progress of chemical ideas naturally apply to the words by which these ideas are to be expressed. Guided by the work which, in the year 1787, Messrs de Morveau, Berthollet, de Fourcroy, and I composed upon the Nomenclature of Chemistry, I have endeavoured, as much as possible, to denominate simple bodies by simple terms, and I was naturally led to name these first. It will be recollected, that we were obliged to retain that name of any substance by which it had been long known in the world, and that in two cases only we took the liberty of making alterations; first, in the case of those which were but newly discovered, and had not yet obtained names, or at least which had been known but for a short time, and the names of which had not yet received the sanction of the public; and, secondly, when the names which had been adopted, whether by the ancients or the moderns, appeared to us to express evidently false ideas, when they confounded the substances, to which they were applied, with others possessed of different, or perhaps opposite qualities. We made no scruple, in this case, of substituting other names in their room, and the greatest number of these were borrowed from the Greek language. We endeavoured to frame them in such a manner as to express the most general and the most characteristic quality of the substances; and this was attended with the additional advantage both of assisting the memory of beginners, who find it difficult to remember a new word which has no meaning, and of accustoming them early to admit no word without connecting with it some determinate idea. To those bodies which are formed by the union of several simple substances we gave new names, compounded in such a manner as the nature of the substances directed; but, as the number of double combinations is already very considerable, the only method by which we could avoid confusion, was to divide them into classes. In the natural order of ideas, the name of the class or genus is that which expresses a quality common to a great number of individuals: The name of the species, on the contrary, expresses a quality peculiar to certain individuals only. These distinctions are not, as some may imagine, merely metaphysical, but are established by Nature. "A child," says the Abbé de Condillac, "is taught to give the name _tree_ to the first one which is pointed out to him. The next one he sees presents the same idea, and he gives it the same name. This he does likewise to a third and a fourth, till at last the word _tree_, which he first applied to an individual, comes to be employed by him as the name of a class or a genus, an abstract idea, which comprehends all trees in general. But, when he learns that all trees serve not the same purpose, that they do not all produce the same kind of fruit, he will soon learn to distinguish them by specific and particular names." This is the logic of all the sciences, and is naturally applied to chemistry. The acids, for example, are compounded of two substances, of the order of those which we consider as simple; the one constitutes acidity, and is common to all acids, and, from this substance, the name of the class or the genus ought to be taken; the other is peculiar to each acid, and distinguishes it from the rest, and from this substance is to be taken the name of the species. But, in the greatest number of acids, the two constituent elements, the acidifying principle, and that which it acidifies, may exist in different proportions, constituting all the possible points of equilibrium or of saturation. This is the case in the sulphuric and the sulphurous acids; and these two states of the same acid we have marked by varying the termination of the specific name. Metallic substances which have been exposed to the joint action of the air and of fire, lose their metallic lustre, increase in weight, and assume an earthy appearance. In this state, like the acids, they are compounded of a principle which is common to all, and one which is peculiar to each. In the same way, therefore, we have thought proper to class them under a generic name, derived from the common principle; for which purpose, we adopted the term _oxyd_; and we distinguish them from each other by the particular name of the metal to which each belongs. Combustible substances, which in acids and metallic oxyds are a specific and particular principle, are capable of becoming, in their turn, common principles of a great number of substances. The sulphurous combinations have been long the only known ones in this kind. Now, however, we know, from the experiments of Messrs Vandermonde, Monge, and Berthollet, that charcoal may be combined with iron, and perhaps with several other metals; and that, from this combination, according to the proportions, may be produced steel, plumbago, &c. We know likewise, from the experiments of M. Pelletier, that phosphorus may be combined with a great number of metallic substances. These different combinations we have classed under generic names taken from the common substance, with a termination which marks this analogy, specifying them by another name taken from that substance which is proper to each. The nomenclature of bodies compounded of three simple substances was attended with still greater difficulty, not only on account of their number, but, particularly, because we cannot express the nature of their constituent principles without employing more compound names. In the bodies which form this class, such as the neutral salts, for instance, we had to consider, 1st, The acidifying principle, which is common to them all; 2d, The acidifiable principle which constitutes their peculiar acid; 3d, The saline, earthy, or metallic basis, which determines the particular species of salt. Here we derived the name of each class of salts from the name of the acidifiable principle common to all the individuals of that class; and distinguished each species by the name of the saline, earthy, or metallic basis, which is peculiar to it. A salt, though compounded of the same three principles, may, nevertheless, by the mere difference of their proportion, be in three different states. The nomenclature we have adopted would have been defective, had it not expressed these different states; and this we attained chiefly by changes of termination uniformly applied to the same state of the different salts. In short, we have advanced so far, that from the name alone may be instantly found what the combustible substance is which enters into any combination; whether that combustible substance be combined with the acidifying principle, and in what proportion; what is the state of the acid; with what basis it is united; whether the saturation be exact, or whether the acid or the basis be in excess. It may be easily supposed that it was not possible to attain all these different objects without departing, in some instances, from established custom, and adopting terms which at first sight will appear uncouth and barbarous. But we considered that the ear is soon habituated to new words, especially when they are connected with a general and rational system. The names, besides, which were formerly employed, such as _powder of algaroth_, _salt of alembroth_, _pompholix_, _phagadenic water_, _turbith mineral_, _colcathar_, and many others, were neither less barbarous nor less uncommon. It required a great deal of practice, and no small degree of memory, to recollect the substances to which they were applied, much more to recollect the genus of combination to which they belonged. The names of _oil of tartar per deliquium_, _oil of vitriol_, _butter of arsenic and of antimony_, _flowers of zinc_, &c. were still more improper, because they suggested false ideas: For, in the whole mineral kingdom, and particularly in the metallic class, there exists no such thing as butters, oils, or flowers; and, in short, the substances to which they give these fallacious names, are nothing less than rank poisons. When we published our essay on the nomenclature of chemistry, we were reproached for having changed the language which was spoken by our masters, which they distinguished by their authority, and handed down to us. But those who reproach us on this account, have forgotten that it was Bergman and Macquer themselves who urged us to make this reformation. In a letter which the learned Professor of Upsal, M. Bergman, wrote, a short time before he died, to M. de Morveau, he bids him _spare no improper names; those who are learned, will always be learned, and those who are ignorant will thus learn sooner_. There is an objection to the work which I am going to present to the public, which is perhaps better founded, that I have given no account of the opinion of those who have gone before me; that I have stated only my own opinion, without examining that of others. By this I have been prevented from doing that justice to my associates, and more especially to foreign chemists, which I wished to render them. But I beseech the reader to consider, that, if I had filled an elementary work with a multitude of quotations; if I had allowed myself to enter into long dissertations on the history of the science, and the works of those who have studied it, I must have lost sight of the true object I had in view, and produced a work, the reading of which must have been extremely tiresome to beginners. It is not to the history of the science, or of the human mind, that we are to attend in an elementary treatise: Our only aim ought to be ease and perspicuity, and with the utmost care to keep every thing out of view which might draw aside the attention of the student; it is a road which we should be continually rendering more smooth, and from which we should endeavour to remove every obstacle which can occasion delay. The sciences, from their own nature, present a sufficient number of difficulties, though we add not those which are foreign to them. But, besides this, chemists will easily perceive, that, in the first part of my work, I make very little use of any experiments but those which were made by myself: If at any time I have adopted, without acknowledgment, the experiments or the opinions of M. Berthollet, M. Fourcroy, M. de la Place, M. Monge, or, in general, of any of those whose principles are the same with my own, it is owing to this circumstance, that frequent intercourse, and the habit of communicating our ideas, our observations, and our way of thinking to each other, has established between us a sort of community of opinions, in which it is often difficult for every one to know his own. The remarks I have made on the order which I thought myself obliged to follow in the arrangement of proofs and ideas, are to be applied only to the first part of this work. It is the only one which contains the general sum of the doctrine I have adopted, and to which I wished to give a form completely elementary. The second part is composed chiefly of tables of the nomenclature of the neutral salts. To these I have only added general explanations, the object of which was to point out the most simple processes for obtaining the different kinds of known acids. This part contains nothing which I can call my own, and presents only a very short abridgment of the results of these processes, extracted from the works of different authors. In the third part, I have given a description, in detail, of all the operations connected with modern chemistry. I have long thought that a work of this kind was much wanted, and I am convinced it will not be without use. The method of performing experiments, and particularly those of modern chemistry, is not so generally known as it ought to be; and had I, in the different memoirs which I have presented to the Academy, been more particular in the detail of the manipulations of my experiments, it is probable I should have made myself better understood, and the science might have made a more rapid progress. The order of the different matters contained in this third part appeared to me to be almost arbitrary; and the only one I have observed was to class together, in each of the chapters of which it is composed, those operations which are most connected with one another. I need hardly mention that this part could not be borrowed from any other work, and that, in the principal articles it contains, I could not derive assistance from any thing but the experiments which I have made myself. I shall conclude this preface by transcribing, literally, some observations of the Abbé de Condillac, which I think describe, with a good deal of truth, the state of chemistry at a period not far distant from our own. These observations were made on a different subject; but they will not, on this account, have less force, if the application of them be thought just. 'Instead of applying observation to the things we wished to know, we have chosen rather to imagine them. Advancing from one ill founded supposition to another, we have at last bewildered ourselves amidst a multitude of errors. These errors becoming prejudices, are, of course, adopted as principles, and we thus bewilder ourselves more and more. The method, too, by which we conduct our reasonings is as absurd; we abuse words which we do not understand, and call this the art of reasoning. When matters have been brought this length, when errors have been thus accumulated, there is but one remedy by which order can be restored to the faculty of thinking; this is, to forget all that we have learned, to trace back our ideas to their source, to follow the train in which they rise, and, as my Lord Bacon says, to frame the human understanding anew. 'This remedy becomes the more difficult in proportion as we think ourselves more learned. Might it not be thought that works which treated of the sciences with the utmost perspicuity, with great precision and order, must be understood by every body? The fact is, those who have never studied any thing will understand them better than those who have studied a great deal, and especially than those who have written a great deal.' At the end of the fifth chapter, the Abbé de Condillac adds: 'But, after all, the sciences have made progress, because philosophers have applied themselves with more attention to observe, and have communicated to their language that precision and accuracy which they have employed in their observations: In correcting their language they reason better.' CONTENTS. PART FIRST. Of the Formation and Decomposition of Aëriform Fluids,--of the Combustion of Simple Bodies, and the Formation of Acids, Page 1 CHAP. I.--Of the Combinations of Caloric, and the Formation of Elastic Aëriform Fluids or Gasses, ibid. CHAP. II.--General Views relative to the Formation and Composition of our Atmosphere, 26 CHAP. III.--Analysis of Atmospheric Air, and its Division into two Elastic Fluids; one fit for Respiration, the other incapable of being respired, 32 CHAP. IV.--Nomenclature of the several constituent Parts of Atmospheric Air, 48 CHAP. V.--Of the Decomposition of Oxygen Gas by Sulphur, Phosphorus, and Charcoal, and of the Formation of Acids in general, 54 CHAP. VI.--Of the Nomenclature of Acids in general, and particularly of those drawn from Nitre and Sea Salt, 66 CHAP. VII.--Of the Decomposition of Oxygen Gas by means of Metals, and the Formation of Metallic Oxyds, 78 CHAP. VIII.--Of the Radical Principle of Water, and of its Decomposition by Charcoal and Iron, 83 CHAP. IX.--Of the Quantities of Caloric disengaged from different Species of Combustion, 97 Combustion of Phosphorus, 100 SECT. I.--Combustion of Charcoal, 101 SECT. II.--Combustion of Hydrogen Gas, 102 SECT. III.--Formation of Nitric Acid, 102 SECT. IV.--Combustion of Wax, 105 SECT. V.--Combustion of Olive Oil, 106 CHAP. X.--Of the Combustion of Combustible Substances with each other, 109 CHAP. XI.--Observations upon Oxyds and Acids with several Bases, and upon the Composition of Animal and Vegetable Substances, 115 CHAP. XII.--Of the Decomposition of Vegetable and Animal Substances by the Action of Fire, 123 CHAP. XIII.--Of the Decomposition of Vegetable Oxyds by the Vinous Fermentation, 129 CHAP. XIV.--Of the Putrefactive Fermentation, 141 CHAP. XV.--Of the Acetous Fermentation, 146 CHAP. XVI.--Of the Formation of Neutral Salts, and of their Bases, 149 SECT. I.--Of Potash, 151 SECT. II.--Of Soda, 155 SECT. III.--Of Ammoniac, 156 SECT. IV.--Of Lime, Magnesia, Barytes, and Argill, 157 SECT. V.--Of Metallic Bodies, 159 CHAP. XVII.--Continuation of the Observations upon Salifiable Bases, and the Formation of Neutral Salts, 161 PART II. Of the Combinations of Acids with Salifiable Bases, and of the Formation of Neutral Salts, 175 INTRODUCTION, ibid. TABLE of Simple Substances, 175 SECT. I.--Observations upon simple Substances, 176 TABLE of Compound Oxydable and Acidifiable Bases, 179 SECT. II.--Observations upon Compound Radicals, 180 SECT. III.--Observations upon the Combinations of Light and Caloric with different Substances, 182 TABLE of the Combinations of Oxygen with the Simple Substances, to face 185 SECT. IV.--Observations upon these Combinations, 185 TABLE of the Combinations of Oxygen with Compound Radicals, 190 SECT. V.--Observations upon these Combinations, 191 TABLE of the Combinations of Azote with the Simple Substances, 194 SECT VI.--Observations upon these Combinations of Azote, 195 TABLE of the Combinations of Hydrogen with Simple Substances, 198 SECT. VII.--Observations upon Hydrogen, and its Combinations, 199 TABLE of the Binary Combinations of Sulphur with the Simple Substances, 202 SECT. VIII.--Observations upon Sulphur, and its Combinations, 203 TABLE of the Combinations of Phosphorus with Simple Substances, 204 SECT. IX.--Observations upon Phosphorus and its Combinations, 205 TABLE of the Binary Combinations of Charcoal, 207 SECT. X.--Observations upon Charcoal, and its Combinations, 208 SECT. XI.--Observations upon the Muriatic, Fluoric, and Boracic Radicals, and their Combinations, 209 SECT. XII.--Observations upon the Combinations of Metals with each other, 219 TABLE of the Combinations of Azote, in the State of Nitrous Acid, with the Salifiable Bases, 212 TABLE of the Combinations of Azote, in the State of Nitric Acid, with the Salifiable Bases, 213 SECT. XIII.--Observations upon Nitrous and Nitric Acids, and their Combinations with Salifiable Bases, 214 TABLE of the Combinations of Sulphuric Acid with the Salifiable Bases, 218 SECT. XIV.--Observations upon Sulphuric Acid, and its Combinations, 219 TABLE of the Combinations of Sulphurous Acid, 222 SECT. XV.--Observations upon Sulphurous Acid, and its Combinations with Salifiable Bases, 223 TABLE of the Combinations of Phosphorous and Phosphoric Acids, 225 SECT. XVI.--Observations upon Phosphorous and Phosphoric Acids, and their Combinations with Salifiable Bases, 226 TABLE of the Combinations of Carbonic Acid, 228 SECT. XVII.--Observations upon Carbonic Acid, and its Combinations with Salifiable Bases, 229 TABLE of the Combinations of Muriatic Acid, 231 TABLE of the Combinations of Oxygenated Muriatic Acid, 232 SECT. XVIII.--Observations upon Muriatic and Oxygenated Muriatic Acid, and their Combinations with Salifiable Bases, 233 TABLE of the Combinations of Nitro-Muriatic Acid, 236 SECT. XIX.--Observations upon Nitro-muriatic Acid, and its Combinations with Salifiable Bases, 237 TABLE of the Combinations of Fluoric Acid, 239 SECT. XX.--Observations upon Fluoric Acid, and its Combinations with Salifiable Bases, 240 TABLE of the Combinations of Boracic Acid, 242 SECT. XXI.--Observations upon Boracic Acid, and its Combinations with Salifiable Bases, 243 TABLE of the Combinations of Arseniac Acid, 246 SECT. XXII.--Observations upon Arseniac Acid, and its Combinations with Salifiable Bases, 247 SECT. XXIII.--Observations upon Molibdic Acid, and its Combinations with Salifiable Bases, 249 SECT. XXIV.--Observations upon Tungstic Acid, and its Combinations with Salifiable Bases, and a Table of these in the order of their Affinity, 251 TABLE of the Combinations of Tartarous Acid, 253 SECT. XXV.--Observations upon Tartarous Acid, and its Combinations with Salifiable Bases, 254 SECT. XXVI.--Observations upon Mallic Acid, and its Combinations with Salifiable Bases, 256 TABLE of the Combinations of Citric Acid, 258 SECT. XXVII.--Observations upon Citric Acid, and its Combinations with Salifiable Bases, 259 TABLE of the Combinations of Pyro-lignous Acid, 260 SECT. XXVIII.--Observations upon Pyro-lignous Acid, and its Combinations with Salifiable Bases, 261 SECT. XXIX.--Observations upon Pyro-tartarous Acid, and its Combinations with Salifiable Bases, ibid. TABLE of the Combinations of Pyro-mucous Acid, 263 SECT. XXX.--Observations upon Pyro-mucous Acid, and its Combinations with Salifiable Bases, 264 TABLE of the Combinations of Oxalic Acid, 265 SECT. XXXI.--Observations upon Oxalic Acid, and its Combinations with Salifiable Bases, 266 TABLE of the Combinations of Acetous Acid, to face 267 SECT. XXXII.--Observations upon Acetous Acid, and its Combinations with the Salifiable Bases, 267 TABLE of the Combinations of Acetic Acid, 271 SECT. XXXIII.--Observations upon Acetic Acid, and its Combinations with Salifiable Bases, 272 TABLE of the Combinations of Succinic Acid, 273 SECT. XXXIV.--Observations upon Succinic Acid, and its Combinations with Salifiable Bases, 274 SECT. XXXV.--Observations upon Benzoic Acid, and its Combinations with Salifiable Bases, 275 SECT. XXXVI.--Observations upon Camphoric Acid, and its Combinations with Salifiable Bases, 276 SECT. XXXVII.--Observations upon Gallic Acid, and its Combinations with Salifiable Bases, 277 SECT. XXXVIII.--Observations upon Lactic Acid, and its Combinations with Salifiable Bases, 278 TABLE of the Combinations of Saccholactic Acid, 280 SECT. XXXIX.--Observations upon Saccholactic Acid, and its Combination with Salifiable Bases, 281 TABLE of the Combinations of Formic Acid, 282 SECT. XL.--Observations upon Formic Acid, and its Combinations with the Salifiable Bases, 283 SECT. XLI.--Observations upon the Bombic Acid, and its Combinations with the Salifiable Bases, 284 TABLE of the Combinations of the Sebacic Acid, 285 SECT. XLII.--Observations upon the Sebacic Acid, and its Combinations with the Salifiable Bases, 286 SECT. XLIII.--Observations upon the Lithic Acid, and its Combinations with the Salifiable Bases, 287 TABLE of the Combinations of the Prussic Acid, 288 SECT. XLIV.--Observations upon the Prussic Acid, and its Combinations with the Salifiable Bases, 289 PART III. Description of the Instruments and Operations of Chemistry, 291 INTRODUCTION, 291 CHAP. I.--Of the Instruments necessary for determining the Absolute and Specific Gravities of Solid and Liquid Bodies, 295 CHAP. II.--Of Gazometry, or the Measurement of the Weight and Volume of Aëriform Substances, 304 SECT. I.--Of the Pneumato-chemical Apparatus, ibid. SECT. II.--Of the Gazometer, 308 SECT. III.--Some other methods for Measuring the Volume of Gasses, 319 SECT. IV.--Of the method of Separating the different Gasses from each other, 323 SECT. V.--Of the necessary Corrections of the Volume of Gasses, according to the Pressure of the Atmosphere, 328 SECT. VI.--Of the Correction relative to the Degrees of the Thermometer, 335 SECT. VII.--Example for Calculating the Corrections relative to the Variations of Pressure and Temperature, 337 SECT. VIII.--Method of determining the Weight of the different Gasses, 340 CHAP. III.--Description of the Calorimeter, or Apparatus for measuring Caloric, 343 CHAP. IV.--Of the Mechanical Operations for Division of Bodies, 357 SECT. I.--Of Trituration, Levigation, and Pulverization, ibid. SECT. II.--Of Sifting and Washing Powdered Substances, 361 SECT. III.--Of Filtration, 363 SECT. IV.--Of Decantation, 365 CHAP. V.--Of Chemical means for Separating the Particles of Bodies from each other without Decomposition, and for Uniting them again, 367 SECT. I.--Of the Solution of Salts, 368 SECT. II.--Of Lixiviation, 373 SECT. III.--Of Evaporation, 375 SECT. IV.--Of Cristallization, 379 SECT. V.--Of Simple Distillation, 384 SECT. VI.--Of Sublimation, 388 CHAP. VI.--Of Pneumato-chemical Distillations, Metallic Dissolutions, and some other operations which require very complicated instruments, 390 SECT. I.--Of Compound and Pneumato-chemical Distillations, ibid. SECT. II.--Of Metallic Dissolutions, 398 SECT. III.--Apparatus necessary in Experiments upon Vinous and Putrefactive Fermentations, 401 SECT. IV.--Apparatus for the Decomposition of Water, 404 CHAP. VII.--Of the Composition and Use of Lutes, 407 CHAP. VIII.--Of Operations upon Combustion and Deflagration, 414 SECT. I.--Of Combustion in general, ibid. SECT. II.--Of the Combustion of Phosphorus, 418 SECT. III.--Of the Combustion of Charcoal, 422 SECT. IV.--Of the Combustion of Oils, 426 SECT. V.--Of the Combustion of Alkohol, 433 SECT. VI.--Of the Combustion of Ether, 435 SECT. VII.--Of the Combustion of Hydrogen Gas, and the Formation of Water, 437 SECT. VIII.--Of the Oxydation of Metals, 441 CHAP. IX.--Of Deflagration, 452 CHAP. X.--Of the Instruments necessary for Operating upon Bodies in very high Temperatures, 460 SECT. I.--Of Fusion, ibid. SECT. II.--Of Furnaces, 462 SECT. III.--Of increasing the Action of Fire, by using Oxygen Gas instead of Atmospheric Air, 474 APPENDIX. No. I.--TABLE for Converting Lines, or Twelfth Parts of an Inch, and Fractions of Lines, into Decimal Fractions of the Inch, 481 No. II.--TABLE for Converting the Observed Heighth of Water in the Jars of the Pneumato-Chemical Apparatus, expressed in Inches and Decimals, into Corresponding Heighths of Mercury, 482 No. III.--TABLE for Converting the Ounce Measures used by Dr Priestley into French and English Cubical Inches, 483 No. IV.--TABLE for Reducing the Degrees of Reaumeur's Thermometer into its corresponding Degrees of Fahrenheit's Scale, 484 No. V.--ADDITIONAL.--RULES for Converting French Weights and Measures into correspondent English Denominations, 485 No. VI.--TABLE of the Weights of the different Gasses, at 28 French inches, or 29.84 English inches barometrical pressure, and at 10° (54.5°) of temperature, expressed in English measure and English Troy weight, 490 No. VII.--TABLES of the Specific Gravities of different bodies, 491 No. VIII.--ADDITIONAL.--RULES for Calculating the Absolute Gravity in English Troy Weight of a Cubic Foot and Inch, English Measure, of any Substance whose Specific Gravity is known, 505 No. IX.--TABLES for Converting Ounces, Drams, and Grains, Troy, into Decimals of the Troy Pound of 12 Ounces, and for Converting Decimals of the Pound Troy into Ounces, &c. 508 No. X.--TABLE of the English Cubical Inches and Decimals corresponding to a determinate Troy Weight of Distilled Water at the Temperature of 55°, calculated from Everard's experiment, 511 ELEMENTS OF CHEMISTRY. PART I. Of the Formation and Decomposition of Aëriform Fluids--of the Combustion of Simple Bodies--and the Formation of Acids. CHAP. I. _Of the Combinations of Caloric, and the Formation of Elastic Aëriform Fluids._ That every body, whether solid or fluid, is augmented in all its dimensions by any increase of its sensible heat, was long ago fully established as a physical axiom, or universal proposition, by the celebrated Boerhaave. Such facts as have been adduced for controverting the generality of this principle offer only fallacious results, or, at least, such as are so complicated with foreign circumstances as to mislead the judgment: But, when we separately consider the effects, so as to deduce each from the cause to which they separately belong, it is easy to perceive that the separation of particles by heat is a constant and general law of nature. When we have heated a solid body to a certain degree, and have thereby caused its particles to separate from each other, if we allow the body to cool, its particles again approach each other in the same proportion in which they were separated by the increased temperature; the body returns through the same degrees of expansion which it before extended through; and, if it be brought back to the same temperature from which we set out at the commencement of the experiment, it recovers exactly the same dimensions which it formerly occupied. But, as we are still very far from being able to arrive at the degree of absolute cold, or deprivation of all heat, being unacquainted with any degree of coldness which we cannot suppose capable of still farther augmentation, it follows, that we are still incapable of causing the ultimate particles of bodies to approach each other as near as is possible; and, consequently, that the particles of all bodies do not touch each other in any state hitherto known, which, tho' a very singular conclusion, is yet impossible to be denied. It is supposed, that, since the particles of bodies are thus continually impelled by heat to separate from each other, they would have no connection between themselves; and, of consequence, that there could be no solidity in nature, unless they were held together by some other power which tends to unite them, and, so to speak, to chain them together; which power, whatever be its cause, or manner of operation, we name Attraction. Thus the particles of all bodies may be considered as subjected to the action of two opposite powers, the one repulsive, the other attractive, between which they remain in equilibrio. So long as the attractive force remains stronger, the body must continue in a state of solidity; but if, on the contrary, heat has so far removed these particles from each other, as to place them beyond the sphere of attraction, they lose the adhesion they before had with each other, and the body ceases to be solid. Water gives us a regular and constant example of these facts; whilst below Zero[2] of the French thermometer, or 32° of Fahrenheit, it remains solid, and is called ice. Above that degree of temperature, its particles being no longer held together by reciprocal attraction, it becomes liquid; and, when we raise its temperature above 80°, (212°) its particles, giving way to the repulsion caused by the heat, assume the state of vapour or gas, and the water is changed into an aëriform fluid. The same may be affirmed of all bodies in nature: They are either solid or liquid, or in the state of elastic aëriform vapour, according to the proportion which takes place between the attractive force inherent in their particles, and the repulsive power of the heat acting upon these; or, what amounts to the same thing, in proportion to the degree of heat to which they are exposed. It is difficult to comprehend these phenomena, without admitting them as the effects of a real and material substance, or very subtile fluid, which, insinuating itself between the particles of bodies, separates them from each other; and, even allowing the existence of this fluid to be hypothetical, we shall see in the sequel, that it explains the phenomena of nature in a very satisfactory manner. This substance, whatever it is, being the cause of heat, or, in other words, the sensation which we call _warmth_ being caused by the accumulation of this substance, we cannot, in strict language, distinguish it by the term _heat_; because the same name would then very improperly express both cause and effect. For this reason, in the memoir which I published in 1777[3], I gave it the names of _igneous fluid_ and _matter of heat_. And, since that time, in the work[4] published by Mr de Morveau, Mr Berthollet, Mr de Fourcroy, and myself, upon the reformation of chemical nomenclature, we thought it necessary to banish all periphrastic expressions, which both lengthen physical language, and render it more tedious and less distinct, and which even frequently does not convey sufficiently just ideas of the subject intended. Wherefore, we have distinguished the cause of heat, or that exquisitely elastic fluid which produces it, by the term of _caloric_. Besides, that this expression fulfils our object in the system which we have adopted, it possesses this farther advantage, that it accords with every species of opinion, since, strictly speaking, we are not obliged to suppose this to be a real substance; it being sufficient, as will more clearly appear in the sequel of this work, that it be considered as the repulsive cause, whatever that may be, which separates the particles of matter from each other; so that we are still at liberty to investigate its effects in an abstract and mathematical manner. In the present state of our knowledge, we are unable to determine whether light be a modification of caloric, or if caloric be, on the contrary, a modification of light. This, however, is indisputable, that, in a system where only decided facts are admissible, and where we avoid, as far as possible, to suppose any thing to be that is not really known to exist, we ought provisionally to distinguish, by distinct terms, such things as are known to produce different effects. We therefore distinguish light from caloric; though we do not therefore deny that these have certain qualities in common, and that, in certain circumstances, they combine with other bodies almost in the same manner, and produce, in part, the same effects. What I have already said may suffice to determine the idea affixed to the word _caloric_; but there remains a more difficult attempt, which is, to give a just conception of the manner in which caloric acts upon other bodies. Since this subtile matter penetrates through the pores of all known substances; since there are no vessels through which it cannot escape, and, consequently, as there are none which are capable of retaining it, we can only come at the knowledge of its properties by effects which are fleeting, and difficultly ascertainable. It is in these things which we neither see nor feel, that it is especially necessary to guard against the extravagancy of our imagination, which forever inclines to step beyond the bounds of truth, and is very difficultly restrained within the narrow line of facts. We have already seen, that the same body becomes solid, or fluid, or aëriform, according to the quantity of caloric by which it is penetrated; or, to speak more strictly, according as the repulsive force exerted by the caloric is equal to, stronger, or weaker, than the attraction of the particles of the body it acts upon. But, if these two powers only existed, bodies would become liquid at an indivisible degree of the thermometer, and would almost instantaneously pass from the solid state of aggregation to that of aëriform elasticity. Thus water, for instance, at the very moment when it ceases to be ice, would begin to boil, and would be transformed into an aëriform fluid, having its particles scattered indefinitely through the surrounding space. That this does not happen, must depend upon the action of some third power. The pressure of the atmosphere prevents this separation, and causes the water to remain in the liquid state till it be raised to 80° of temperature (212°) above zero of the French thermometer, the quantity of caloric which it receives in the lowest temperature being insufficient to overcome the pressure of the atmosphere. Whence it appears that, without this atmospheric pressure, we should not have any permanent liquid, and should only be able to see bodies in that state of existence in the very instant of melting, as the smallest additional caloric would instantly separate their particles, and dissipate them through the surrounding medium. Besides, without this atmospheric pressure, we should not even have any aëriform fluids, strictly speaking, because the moment the force of attraction is overcome by the repulsive power of the caloric, the particles would separate themselves indefinitely, having nothing to give limits to their expansion, unless their own gravity might collect them together, so as to form an atmosphere. Simple reflection upon the most common experiments is sufficient to evince the truth of these positions. They are more particularly proved by the following experiment, which I published in the Memoirs of the French Academy for 1777, p. 426. Having filled with sulphuric ether[5] a small narrow glass vessel, A, (Plate VII. Fig. 17.), standing upon its stalk P, the vessel, which is from twelve to fifteen lines diameter, is to be covered by a wet bladder, tied round its neck with several turns of strong thread; for greater security, fix a second bladder over the first. The vessel should be filled in such a manner with the ether, as not to leave the smallest portion of air between the liquor and the bladder. It is now to be placed under the recipient BCD of an air-pump, of which the upper part B ought to be fitted with a leathern lid, through which passes a wire EF, having its point F very sharp; and in the same receiver there ought to be placed the barometer GH. The whole being thus disposed, let the recipient be exhausted, and then, by pushing down the wire EF, we make a hole in the bladder. Immediately the ether begins to boil with great violence, and is changed into an elastic aëriform fluid, which fills the receiver. If the quantity of ether be sufficient to leave a few drops in the phial after the evaporation is finished, the elastic fluid produced will sustain the mercury in the barometer attached to the air-pump, at eight or ten inches in winter, and from twenty to twenty-five in summer[6]. To render this experiment more complete, we may introduce a small thermometer into the phial A, containing the ether, which will descend considerably during the evaporation. The only effect produced in this experiment is, the taking away the weight of the atmosphere, which, in its ordinary state, presses on the surface of the ether; and the effects resulting from this removal evidently prove, that, in the ordinary temperature of the earth, ether would always exist in an aëriform state, but for the pressure of the atmosphere, and that the passing of the ether from the liquid to the aëriform state is accompanied by a considerable lessening of heat; because, during the evaporation, a part of the caloric, which was before in a free state, or at least in equilibrio in the surrounding bodies, combines with the ether, and causes it to assume the aëriform state. The same experiment succeeds with all evaporable fluids, such as alkohol, water, and even mercury; with this difference, that the atmosphere formed in the receiver by alkohol only supports the attached barometer about one inch in winter, and about four or five inches in summer; that formed by water, in the same situation, raises the mercury only a few lines, and that by quicksilver but a few fractions of a line. There is therefore less fluid evaporated from alkohol than from ether, less from water than from alkohol, and still less from mercury than from either; consequently there is less caloric employed, and less cold produced, which quadrates exactly with the results of these experiments. Another species of experiment proves very evidently that the aëriform state is a modification of bodies dependent on the degree of temperature, and on the pressure which these bodies undergo. In a Memoir read by Mr de la Place and me to the Academy in 1777, which has not been printed, we have shown, that, when ether is subjected to a pressure equal to twenty-eight inches of the barometer, or about the medium pressure of the atmosphere, it boils at the temperature of about 32° (104°), or 33° (106.25°), of the thermometer. Mr de Luc, who has made similar experiments with spirit of wine, finds it boils at 67° (182.75°). And all the world knows that water boils at 80° (212°). Now, boiling being only the evaporation of a liquid, or the moment of its passing from the fluid to the aëriform state, it is evident that, if we keep ether continually at the temperature of 33° (106.25°), and under the common pressure of the atmosphere, we shall have it always in an elastic aëriform state; and that the same thing will happen with alkohol when above 67° (182.75°), and with water when above 80° (212°); all which are perfectly conformable to the following experiment[7]. I filled a large vessel ABCD (Plate VII. Fig. 16.) with water, at 35° (110.75°), or 36° (113°); I suppose the vessel transparent, that we may see what takes place in the experiment; and we can easily hold the hands in water at that temperature without inconvenience. Into it I plunged some narrow necked bottles F, G, which were filled with the water, after which they were turned up, so as to rest on their mouths on the bottom of the vessel. Having next put some ether into a very small matrass, with its neck a b c, twice bent as in the Plate, I plunged this matrass into the water, so as to have its neck inserted into the mouth of one of the bottles F. Immediately upon feeling the effects of the heat communicated to it by the water in the vessel ABCD it began to boil; and the caloric entering into combination with it, changed it into elastic aëriform fluid, with which I filled several bottles successively, F, G, &c. This is not the place to enter upon the examination of the nature and properties of this aëriform fluid, which is extremely inflammable; but, confining myself to the object at present in view, without anticipating circumstances, which I am not to suppose the reader to know, I shall only observe, that the ether, from this experiment, is almost only capable of existing in the aëriform state in our world; for, if the weight of our atmosphere was only equal to between 20 and 24 inches of the barometer, instead of 28 inches, we should never be able to obtain ether in the liquid state, at least in summer; and the formation of ether would consequently be impossible upon mountains of a moderate degree of elevation, as it would be converted into gas immediately upon being produced, unless we employed recipients of extraordinary strength, together with refrigeration and compression. And, lastly, the temperature of the blood being nearly that at which ether passes from the liquid to the aëriform state, it must evaporate in the primae viae, and consequently it is very probable the medical properties of this fluid depend chiefly upon its mechanical effect. These experiments succeed better with nitrous ether, because it evaporates in a lower temperature than sulphuric ether. It is more difficult to obtain alkohol in the aëriform state; because, as it requires 67° (182.75°) to reduce it to vapour, the water of the bath must be almost boiling, and consequently it is impossible to plunge the hands into it at that temperature. It is evident that, if water were used in the foregoing experiment, it would be changed into gas, when exposed to a temperature superior to that at which it boils. Although thoroughly convinced of this, Mr de la Place and myself judged it necessary to confirm it by the following direct experiment. We filled a glass jar A, (Plate VII. Fig. 5.) with mercury, and placed it with its mouth downwards in a dish B, likewise filled with mercury, and having introduced about two gross of water into the jar, which rose to the top of the mercury at CD; we then plunged the whole apparatus into an iron boiler EFGH, full of boiling sea-water of the temperature of 85° (123.25°), placed upon the furnace GHIK. Immediately upon the water over the mercury attaining the temperature of 80° (212°), it began to boil; and, instead of only filling the small space ACD, it was converted into an aëriform fluid, which filled the whole jar; the mercury even descended below the surface of that in the dish B; and the jar must have been overturned, if it had not been very thick and heavy, and fixed to the dish by means of iron-wire. Immediately after withdrawing the apparatus from the boiler, the vapour in the jar began to condense, and the mercury rose to its former station; but it returned again to the aëriform state a few seconds after replacing the apparatus in the boiler. We have thus a certain number of substances, which are convertible into elastic aëriform fluids by degrees of temperature, not much superior to that of our atmosphere. We shall afterwards find that there are several others which undergo the same change in similar circumstances, such as muriatic or marine acid, ammoniac or volatile alkali, the carbonic acid or fixed air, the sulphurous acid, &c. All of these are permanently elastic in or about the mean temperature of the atmosphere, and under its common pressure. All these facts, which could be easily multiplied if necessary, give me full right to assume, as a general principle, that almost every body in nature is susceptible of three several states of existence, solid, liquid, and aëriform, and that these three states of existence depend upon the quantity of caloric combined with the body. Henceforwards I shall express these elastic aëriform fluids by the generic term _gas_; and in each species of gas I shall distinguish between the caloric, which in some measure serves the purpose of a solvent, and the substance, which in combination with the caloric, forms the base of the gas. To these bases of the different gases, which are hitherto but little known, we have been obliged to assign names; these I shall point out in Chap. IV. of this work, when I have previously given an account of the phenomena attendant upon the heating and cooling of bodies, and when I have established precise ideas concerning the composition of our atmosphere. We have already shown, that the particles of every substance in nature exist in a certain state of equilibrium, between that attraction which tends to unite and keep the particles together, and the effects of the caloric which tends to separate them. Hence the caloric not only surrounds the particles of all bodies on every side, but fills up every interval which the particles of bodies leave between each other. We may form an idea of this, by supposing a vessel filled with small spherical leaden bullets, into which a quantity of fine sand is poured, which, insinuating into the intervals between the bullets, will fill up every void. The balls, in this comparison, are to the sand which surrounds them exactly in the same situation as the particles of bodies are with respect to the caloric; with this difference only, that the balls are supposed to touch each other, whereas the particles of bodies are not in contact, being retained at a small distance from each other, by the caloric. If, instead of spherical balls, we substitute solid bodies of a hexahedral, octohedral, or any other regular figure, the capacity of the intervals between them will be lessened, and consequently will no longer contain the same quantity of sand. The same thing takes place, with respect to natural bodies; the intervals left between their particles are not of equal capacity, but vary in consequence of the different figures and magnitude of their particles, and of the distance at which these particles are maintained, according to the existing proportion between their inherent attraction, and the repulsive force exerted upon them by the caloric. In this manner we must understand the following expression, introduced by the English philosophers, who have given us the first precise ideas upon this subject; _the capacity of bodies for containing the matter of heat_. As comparisons with sensible objects are of great use in assisting us to form distinct notions of abstract ideas, we shall endeavour to illustrate this, by instancing the phenomena which take place between water and bodies which are wetted and penetrated by it, with a few reflections. If we immerge equal pieces of different kinds of wood, suppose cubes of one foot each, into water, the fluid gradually insinuates itself into their pores, and the pieces of wood are augmented both in weight and magnitude: But each species of wood will imbibe a different quantity of water; the lighter and more porous woods will admit a larger, the compact and closer grained will admit of a lesser quantity; for the proportional quantities of water imbibed by the pieces will depend upon the nature of the constituent particles of the wood, and upon the greater or lesser affinity subsisting between them and water. Very resinous wood, for instance, though it may be at the same time very porous, will admit but little water. We may therefore say, that the different kinds of wood possess different capacities for receiving water; we may even determine, by means of the augmentation of their weights, what quantity of water they have actually absorbed; but, as we are ignorant how much water they contained, previous to immersion, we cannot determine the absolute quantity they contain, after being taken out of the water. The same circumstances undoubtedly take place, with bodies that are immersed in caloric; taking into consideration, however, that water is an incompressible fluid, whereas caloric is, on the contrary, endowed with very great elasticity; or, in other words, the particles of caloric have a great tendency to separate from each other, when forced by any other power to approach; this difference must of necessity occasion very considerable diversities in the results of experiments made upon these two substances. Having established these clear and simple propositions, it will be very easy to explain the ideas which ought to be affixed to the following expressions, which are by no means synonimous, but possess each a strict and determinate meaning, as in the following definitions: _Free caloric_, is that which is not combined in any manner with any other body. But, as we live in a system to which caloric has a very strong adhesion, it follows that we are never able to obtain it in the state of absolute freedom. _Combined caloric_, is that which is fixed in bodies by affinity or elective attraction, so as to form part of the substance of the body, even part of its solidity. By the expression _specific caloric_ of bodies, we understand the respective quantities of caloric requisite for raising a number of bodies of the same weight to an equal degree of temperature. This proportional quantity of caloric depends upon the distance between the constituent particles of bodies, and their greater or lesser degrees of cohesion; and this distance, or rather the space or void resulting from it, is, as I have already observed, called the _capacity of bodies for containing caloric_. _Heat_, considered as a sensation, or, in other words, sensible heat, is only the effect produced upon our sentient organs, by the motion or passage of caloric, disengaged from the surrounding bodies. In general, we receive impressions only in consequence of motion, and we might establish it as an axiom, _That_, WITHOUT MOTION, THERE IS NO SENSATION. This general principle applies very accurately to the sensations of heat and cold: When we touch a cold body, the caloric which always tends to become in equilibrio in all bodies, passes from our hand into the body we touch, which gives us the feeling or sensation of cold. The direct contrary happens, when we touch a warm body, the caloric then passing from the body into our hand, produces the sensation of heat. If the hand and the body touched be of the same temperature, or very nearly so, we receive no impression, either of heat or cold, because there is no motion or passage of caloric; and thus no sensation can take place, without some correspondent motion to occasion it. When the thermometer rises, it shows, that free caloric is entering into the surrounding bodies: The thermometer, which is one of these, receives its share in proportion to its mass, and to the capacity which it possesses for containing caloric. The change therefore which takes place upon the thermometer, only announces a change of place of the caloric in those bodies, of which the thermometer forms one part; it only indicates the portion of caloric received, without being a measure of the whole quantity disengaged, displaced, or absorbed. The most simple and most exact method for determining this latter point, is that described by Mr de la Place, in the Memoirs of the Academy, No. 1780, p. 364; a summary explanation of which will be found towards the conclusion of this work. This method consists in placing a body, or a combination of bodies, from which caloric is disengaging, in the midst of a hollow sphere of ice; and the quantity of ice melted becomes an exact measure of the quantity of caloric disengaged. It is possible, by means of the apparatus which we have caused to be constructed upon this plan, to determine, not as has been pretended, the capacity of bodies for containing heat, but the ratio of the increase or diminution of capacity produced by determinate degrees of temperature. It is easy with the same apparatus, by means of divers combinations of experiments, to determine the quantity of caloric requisite for converting solid substances into liquids, and liquids into elastic aëriform fluids; and, _vice versa_, what quantity of caloric escapes from elastic vapours in changing to liquids, and what quantity escapes from liquids during their conversion into solids. Perhaps, when experiments have been made with sufficient accuracy, we may one day be able to determine the proportional quantity of caloric, necessary for producing the several species of gasses. I shall hereafter, in a separate chapter, give an account of the principal results of such experiments as have been made upon this head. It remains, before finishing this article, to say a few words relative to the cause of the elasticity of gasses, and of fluids in the state of vapour. It is by no means difficult to perceive that this elasticity depends upon that of caloric, which seems to be the most eminently elastic body in nature. Nothing is more readily conceived, than that one body should become elastic by entering into combination with another body possessed of that quality. We must allow that this is only an explanation of elasticity, by an assumption of elasticity, and that we thus only remove the difficulty one step farther, and that the nature of elasticity, and the reason for caloric being elastic, remains still unexplained. Elasticity in the abstract is nothing more than that quality of the particles of bodies by which they recede from each other when forced together. This tendency in the particles of caloric to separate, takes place even at considerable distances. We shall be satisfied of this, when we consider that air is susceptible of undergoing great compression, which supposes that its particles were previously very distant from each other; for the power of approaching together certainly supposes a previous distance, at least equal to the degree of approach. Consequently, those particles of the air, which are already considerably distant from each other, tend to separate still farther. In fact, if we produce Boyle's vacuum in a large receiver, the very last portion of air which remains spreads itself uniformly through the whole capacity of the vessel, however large, fills it completely throughout, and presses every where against its sides: We cannot, however, explain this effect, without supposing that the particles make an effort to separate themselves on every side, and we are quite ignorant at what distance, or what degree of rarefaction, this effort ceases to act. Here, therefore, exists a true repulsion between the particles of elastic fluids; at least, circumstances take place exactly as if such a repulsion actually existed; and we have very good right to conclude, that the particles of caloric mutually repel each other. When we are once permitted to suppose this repelling force, the _rationale_ of the formation of gasses, or aëriform fluids, becomes perfectly simple; tho' we must, at the same time, allow, that it is extremely difficult to form an accurate conception of this repulsive force acting upon very minute particles placed at great distances from each other. It is, perhaps, more natural to suppose, that the particles of caloric have a stronger mutual attraction than those of any other substance, and that these latter particles are forced asunder in consequence of this superior attraction between the particles of the caloric, which forces them between the particles of other bodies, that they may be able to reunite with each other. We have somewhat analogous to this idea in the phenomena which occur when a dry sponge is dipt into water: The sponge swells; its particles separate from each other; and all its intervals are filled up by the water. It is evident, that the sponge, in the act of swelling, has acquired a greater capacity for containing water than it had when dry. But we cannot certainly maintain, that the introduction of water between the particles of the sponge has endowed them with a repulsive power, which tends to separate them from each other; on the contrary, the whole phenomena are produced by means of attractive powers; and these are, _first_, The gravity of the water, and the power which it exerts on every side, in common with all other fluids; _2dly_, The force of attraction which takes place between the particles of the water, causing them to unite together; _3dly_, The mutual attraction of the particles of the sponge with each other; and, _lastly_, The reciprocal attraction which exists between the particles of the sponge and those of the water. It is easy to understand, that the explanation of this fact depends upon properly appreciating the intensity of, and connection between, these several powers. It is probable, that the separation of the particles of bodies, occasioned by caloric, depends in a similar manner upon a certain combination of different attractive powers, which, in conformity with the imperfection of our knowledge, we endeavour to express by saying, that caloric communicates a power of repulsion to the particles of bodies. FOOTNOTES: [2] Whenever the degree of heat occurs in this work, it is stated by the author according to Reaumur's scale. The degrees within brackets are the correspondent degrees of Fahrenheit's scale, added by the translator. E. [3] Collections of the French Academy of Sciences for that year, p. 420. [4] Chemical Nomenclature. [5] As I shall afterwards give a definition, and explain the properties of the liquor called _ether_, I shall only premise here, that it is a very volatile inflammable liquor, having a considerably smaller specific gravity than water, or even spirit of wine.--A. [6] It would have been more satisfactory if the Author had specified the degrees of the thermometer at which these heights of the mercury in the barometer are produced. [7] Vide Memoirs of the French Academy, anno 1780, p. 335.--A. CHAP. II. _General Views relative to the Formation and Composition of our Atmosphere._ These views which I have taken of the formation of elastic aëriform fluids or gasses, throw great light upon the original formation of the atmospheres of the planets, and particularly that of our earth. We readily conceive, that it must necessarily consist of a mixture of the following substances: _First_, Of all bodies that are susceptible of evaporation, or, more strictly speaking, which are capable of retaining the state of aëriform elasticity in the temperature of our atmosphere, and under a pressure equal to that of a column of twenty-eight inches of quicksilver in the barometer; and, _secondly_, Of all substances, whether liquid or solid, which are capable of being dissolved by this mixture of different gasses. The better to determine our ideas relating to this subject, which has not hitherto been sufficiently considered, let us, for a moment, conceive what change would take place in the various substances which compose our earth, if its temperature were suddenly altered. If, for instance, we were suddenly transported into the region of the planet Mercury, where probably the common temperature is much superior to that of boiling water, the water of the earth, and all the other fluids which are susceptible of the gasseous state, at a temperature near to that of boiling water, even quicksilver itself, would become rarified; and all these substances would be changed into permanent aëriform fluids or gasses, which would become part of the new atmosphere. These new species of airs or gasses would mix with those already existing, and certain reciprocal decompositions and new combinations would take place, until such time as all the elective attractions or affinities subsisting amongst all these new and old gasseous substances had operated fully; after which, the elementary principles composing these gasses, being saturated, would remain at rest. We must attend to this, however, that, even in the above hypothetical situation, certain bounds would occur to the evaporation of these substances, produced by that very evaporation itself; for as, in proportion to the increase of elastic fluids, the pressure of the atmosphere would be augmented, as every degree of pressure tends, in some measure, to prevent evaporation, and as even the most evaporable fluids can resist the operation of a very high temperature without evaporating, if prevented by a proportionally stronger compression, water and all other liquids being able to sustain a red heat in Papin's digester; we must admit, that the new atmosphere would at last arrive at such a degree of weight, that the water which had not hitherto evaporated would cease to boil, and, of consequence, would remain liquid; so that, even upon this supposition, as in all others of the same nature, the increasing gravity of the atmosphere would find certain limits which it could not exceed. We might even extend these reflections greatly farther, and examine what change might be produced in such situations upon stones, salts, and the greater part of the fusible substances which compose the mass of our earth. These would be softened, fused, and changed into fluids, &c.: But these speculations carry me from my object, to which I hasten to return. By a contrary supposition to the one we have been forming, if the earth were suddenly transported into a very cold region, the water which at present composes our seas, rivers, and springs, and probably the greater number of the fluids we are acquainted with, would be converted into solid mountains and hard rocks, at first diaphanous and homogeneous, like rock crystal, but which, in time, becoming mixed with foreign and heterogeneous substances, would become opake stones of various colours. In this case, the air, or at least some part of the aëriform fluids which now compose the mass of our atmosphere, would doubtless lose its elasticity for want of a sufficient temperature to retain them in that state: They would return to the liquid state of existence, and new liquids would be formed, of whose properties we cannot, at present, form the most distant idea. These two opposite suppositions give a distinct proof of the following corollaries: _First_, That _solidity_, _liquidity_, and _aëriform elasticity_, are only three different states of existence of the same matter, or three particular modifications which almost all substances are susceptible of assuming successively, and which solely depend upon the degree of temperature to which they are exposed; or, in other words, upon the quantity of caloric with which they are penetrated[8]. _2dly_, That it is extremely probable that air is a fluid naturally existing in a state of vapour; or, as we may better express it, that our atmosphere is a compound of all the fluids which are susceptible of the vaporous or permanently elastic state, in the usual temperature, and under the common pressure. _3dly_, That it is not impossible we may discover, in our atmosphere, certain substances naturally very compact, even metals themselves; as a metallic substance, for instance, only a little more volatile than mercury, might exist in that situation. Amongst the fluids with which we are acquainted, some, as water and alkohol, are susceptible of mixing with each other in all proportions; whereas others, on the contrary, as quicksilver, water, and oil, can only form a momentary union; and, after being mixed together, separate and arrange themselves according to their specific gravities. The same thing ought to, or at least may, take place in the atmosphere. It is possible, and even extremely probable, that, both at the first creation, and every day, gasses are formed, which are difficultly miscible with atmospheric air, and are continually separating from it. If these gasses be specifically lighter than the general atmospheric mass, they must, of course, gather in the higher regions, and form strata that float upon the common air. The phenomena which accompany igneous meteors induce me to believe, that there exists in the upper parts of our atmosphere a stratum of inflammable fluid in contact with those strata of air which produce the phenomena of the aurora borealis and other fiery meteors.--I mean hereafter to pursue this subject in a separate treatise. FOOTNOTES: [8] The degree of pressure which they undergo must be taken into account. E. CHAP. III. _Analysis of Atmospheric Air, and its Division into two Elastic Fluids; the one fit for Respiration, the other incapable of being respired._ From what has been premised, it follows, that our atmosphere is composed of a mixture of every substance capable of retaining the gasseous or aëriform state in the common temperature, and under the usual pressure which it experiences. These fluids constitute a mass, in some measure homogeneous, extending from the surface of the earth to the greatest height hitherto attained, of which the density continually decreases in the inverse ratio of the superincumbent weight. But, as I have before observed, it is possible that this first stratum is surmounted by several others consisting of very different fluids. Our business, in this place, is to endeavour to determine, by experiments, the nature of the elastic fluids which compose the inferior stratum of air which we inhabit. Modern chemistry has made great advances in this research; and it will appear by the following details that the analysis of atmospherical air has been more rigorously determined than that of any other substance of the class. Chemistry affords two general methods of determining the constituent principles of bodies, the method of analysis, and that of synthesis. When, for instance, by combining water with alkohol, we form the species of liquor called, in commercial language, brandy or spirit of wine, we certainly have a right to conclude, that brandy, or spirit of wine, is composed of alkohol combined with water. We can produce the same result by the analytical method; and in general it ought to be considered as a principle in chemical science, never to rest satisfied without both these species of proofs. We have this advantage in the analysis of atmospherical air, being able both to decompound it, and to form it a new in the most satisfactory manner. I shall, however, at present confine myself to recount such experiments as are most conclusive upon this head; and I may consider most of these as my own, having either first invented them, or having repeated those of others, with the intention of analysing atmospherical air, in perfectly new points of view. I took a matrass (A, fig. 14. plate II.) of about 36 cubical inches capacity, having a long neck B C D E, of six or seven lines internal diameter, and having bent the neck as in Plate IV. Fig. 2. so as to allow of its being placed in the furnace M M N N, in such a manner that the extremity of its neck E might be inserted under a bell-glass F G, placed in a trough of quicksilver R R S S; I introduced four ounces of pure mercury into the matrass, and, by means of a syphon, exhausted the air in the receiver F G, so as to raise the quicksilver to L L, and I carefully marked the height at which it stood by pasting on a slip of paper. Having accurately noted the height of the thermometer and barometer, I lighted a fire in the furnace M M N N, which I kept up almost continually during twelve days, so as to keep the quicksilver always almost at its boiling point. Nothing remarkable took place during the first day: The Mercury, though not boiling, was continually evaporating, and covered the interior surface of the vessels with small drops, at first very minute, which gradually augmenting to a sufficient size, fell back into the mass at the bottom of the vessel. On the second day, small red particles began to appear on the surface of the mercury, which, during the four or five following days, gradually increased in size and number; after which they ceased to increase in either respect. At the end of twelve days, seeing that the calcination of the mercury did not at all increase, I extinguished the fire, and allowed the vessels to cool. The bulk of air in the body and neck of the matrass, and in the bell-glass, reduced to a medium of 28 inches of the barometer and 10° (54.5°) of the thermometer, at the commencement of the experiment was about 50 cubical inches. At the end of the experiment the remaining air, reduced to the same medium pressure and temperature, was only between 42 and 43 cubical inches; consequently it had lost about 1/6 of its bulk. Afterwards, having collected all the red particles, formed during the experiment, from the running mercury in which they floated, I found these to amount to 45 grains. I was obliged to repeat this experiment several times, as it is difficult in one experiment both to preserve the whole air upon which we operate, and to collect the whole of the red particles, or calx of mercury, which is formed during the calcination. It will often happen in the sequel, that I shall, in this manner, give in one detail the results of two or three experiments of the same nature. The air which remained after the calcination of the mercury in this experiment, and which was reduced to 5/6 of its former bulk, was no longer fit either for respiration or for combustion; animals being introduced into it were suffocated in a few seconds, and when a taper was plunged into it, it was extinguished as if it had been immersed into water. In the next place, I took the 45 grains of red matter formed during this experiment, which I put into a small glass retort, having a proper apparatus for receiving such liquid, or gasseous product, as might be extracted: Having applied a fire to the retort in a furnace, I observed that, in proportion as the red matter became heated, the intensity of its colour augmented. When the retort was almost red hot, the red matter began gradually to decrease in bulk, and in a few minutes after it disappeared altogether; at the same time 41-1/2 grains of running mercury were collected in the recipient, and 7 or 8 cubical inches of elastic fluid, greatly more capable of supporting both respiration and combustion than atmospherical air, were collected in the bell-glass. A part of this air being put into a glass tube of about an inch diameter, showed the following properties: A taper burned in it with a dazzling splendour, and charcoal, instead of consuming quietly as it does in common air, burnt with a flame, attended with a decrepitating noise, like phosphorus, and threw out such a brilliant light that the eyes could hardly endure it. This species of air was discovered almost at the same time by Mr Priestley, Mr Scheele, and myself. Mr Priestley gave it the name of _dephlogisticated air_, Mr Scheele called it _empyreal air_. At first I named it _highly respirable air_, to which has since been substituted the term of _vital air_. We shall presently see what we ought to think of these denominations. In reflecting upon the circumstances of this experiment, we readily perceive, that the mercury, during its calcination, absorbs the salubrious and respirable part of the air, or, to speak more strictly, the base of this respirable part; that the remaining air is a species of mephitis, incapable of supporting combustion or respiration; and consequently that atmospheric air is composed of two elastic fluids of different and opposite qualities. As a proof of this important truth, if we recombine these two elastic fluids, which we have separately obtained in the above experiment, viz. the 42 cubical inches of mephitis, with the 8 cubical inches of respirable air, we reproduce an air precisely similar to that of the atmosphere, and possessing nearly the same power of supporting combustion and respiration, and of contributing to the calcination of metals. Although this experiment furnishes us with a very simple means of obtaining the two principal elastic fluids which compose our atmosphere, separate from each other, yet it does not give us an exact idea of the proportion in which these two enter into its composition: For the attraction of mercury to the respirable part of the air, or rather to its base, is not sufficiently strong to overcome all the circumstances which oppose this union. These obstacles are the mutual adhesion of the two constituent parts of the atmosphere for each other, and the elective attraction which unites the base of vital air with caloric; in consequence of these, when the calcination ends, or is at least carried as far as is possible, in a determinate quantity of atmospheric air, there still remains a portion of respirable air united to the mephitis, which the mercury cannot separate. I shall afterwards show, that, at least in our climate, the atmospheric air is composed of respirable and mephitic airs, in the proportion of 27 and 73; and I shall then discuss the causes of the uncertainty which still exists with respect to the exactness of that proportion. Since, during the calcination of mercury, air is decomposed, and the base of its respirable part is fixed and combined with the mercury, it follows, from the principles already established, that caloric and light must be disengaged during the process: But the two following causes prevent us from being sensible of this taking place: As the calcination lasts during several days, the disengagement of caloric and light, spread out in a considerable space of time, becomes extremely small for each particular moment of that time, so as not to be perceptible; and, in the next place, the operation being carried on by means of fire in a furnace, the heat produced by the calcination itself becomes confounded with that proceeding from the furnace. I might add the respirable part of the air, or rather its base, in entering into combination with the mercury, does not part with all the caloric which it contained, but still retains a part of it after forming the new compound; but the discussion of this point, and its proofs from experiment, do not belong to this part of our subject. It is, however, easy to render this disengagement of caloric and light evident to the senses, by causing the decomposition of air to take place in a more rapid manner. And for this purpose, iron is excellently adapted, as it possesses a much stronger affinity for the base of respirable air than mercury. The elegant experiment of Mr Ingenhouz, upon the combustion of iron, is well known. Take a piece of fine iron wire, twisted into a spiral, (BC, Plate IV. Fig. 17.) fix one of its extremities B into the cork A, adapted to the neck of the bottle DEFG, and fix to the other extremity of the wire C, a small morsel of tinder. Matters being thus prepared, fill the bottle DEFG with air deprived of its mephitic part; then light the tinder, and introduce it quickly with the wire upon which it is fixed, into the bottle which you stop up with the cork A, as is shown in the figure (17 Plate IV.) The instant the tinder comes into contact with the vital air it begins to burn with great intensity; and, communicating the inflammation to the iron-wire, it too takes fire, and burns rapidly, throwing out brilliant sparks, which fall to the bottom of the vessel in rounded globules, which become black in cooling, but retain a degree of metallic splendour. The iron thus burnt is more brittle even than glass, and is easily reduced into powder, and is still attractable by the magnet, though not so powerfully as it was before combustion. As Mr Ingenhouz has neither examined the change produced on iron, nor upon the air by this operation, I have repeated the experiment under different circumstances, in an apparatus adapted to answer my particular views, as follows. Having filled a bell-glass (A, Plate IV. Fig. 3.) of about six pints measure, with pure air, or the highly respirable part of air, I transported this jar by means of a very flat vessel, into a quicksilver bath in the bason BC, and I took care to render the surface of the mercury perfectly dry both within and without the jar with blotting paper. I then provided a small capsule of china-ware D, very flat and open, in which I placed some small pieces of iron, turned spirally, and arranged in such a way as seemed most favourable for the combustion being communicated to every part. To the end of one of these pieces of iron was fixed a small morsel of tinder, to which was added about the sixteenth part of a grain of phosphorus, and, by raising the bell-glass a little, the china capsule, with its contents, were introduced into the pure air. I know that, by this means, some common air must mix with the pure air in the glass; but this, when it is done dexterously, is so very trifling, as not to injure the success of the experiment. This being done, a part of the air is sucked out from the bell-glass, by means of a syphon GHI, so as to raise the mercury within the glass to EF; and, to prevent the mercury from getting into the syphon, a small piece of paper is twisted round its extremity. In sucking out the air, if the motion of the lungs only be used, we cannot make the mercury rise above an inch or an inch and a half; but, by properly using the muscles of the mouth, we can, without difficulty, cause it to rise six or seven inches. I next took an iron wire, (MN, Plate IV. Fig. 16.) properly bent for the purpose, and making it red hot in the fire, passed it through the mercury into the receiver, and brought it in contact with the small piece of phosphorus attached to the tinder. The phosphorus instantly takes fire, which communicates to the tinder, and from that to the iron. When the pieces have been properly arranged, the whole iron burns, even to the last particle, throwing out a white brilliant light similar to that of Chinese fireworks. The great heat produced by this combustion melts the iron into round globules of different sizes, most of which fall into the China cup; but some are thrown out of it, and swim upon the surface of the mercury. At the beginning of the combustion, there is a slight augmentation in the volume of the air in the bell-glass, from the dilatation caused by the heat; but, presently afterwards, a rapid diminution of the air takes place, and the mercury rises in the glass; insomuch that, when the quantity of iron is sufficient, and the air operated upon is very pure, almost the whole air employed is absorbed. It is proper to remark in this place, that, unless in making experiments for the purpose of discovery, it is better to be contented with burning a moderate quantity of iron; for, when this experiment is pushed too far, so as to absorb much of the air, the cup D, which floats upon the quicksilver, approaches too near the bottom of the bell-glass; and the great heat produced, which is followed by a very sudden cooling, occasioned by the contact of the cold mercury, is apt to break the glass. In which case, the sudden fall of the column of mercury, which happens the moment the least flaw is produced in the glass, causes such a wave, as throws a great part of the quicksilver from the bason. To avoid this inconvenience, and to ensure success to the experiment, one gross and a half of iron is sufficient to burn in a bell-glass, which holds about eight pints of air. The glass ought likewise to be strong, that it may be able to bear the weight of the column of mercury which it has to support. By this experiment, it is not possible to determine, at one time, both the additional weight acquired by the iron, and the changes which have taken place in the air. If it is wished to ascertain what additional weight has been gained by the iron, and the proportion between that and the air absorbed, we must carefully mark upon the bell-glass, with a diamond, the height of the mercury, both before and after the experiment[9]. After this, the syphon (GH, Pl. IV. fig. 3.) guarded, as before, with a bit of paper, to prevent its filling with mercury, is to be introduced under the bell-glass, having the thumb placed upon the extremity, G, of the syphon, to regulate the passage of the air; and by this means the air is gradually admitted, so as to let the mercury fall to its level. This being done, the bell-glass is to be carefully removed, the globules of melted iron contained in the cup, and those which have been scattered about, and swim upon the mercury, are to be accurately collected, and the whole is to be weighed. The iron will be found in that state called _martial ethiops_ by the old chemists, possessing a degree of metallic brilliancy, very friable, and readily reducible into powder, under the hammer, or with a pestle and mortar. If the experiment has succeeded well, from 100 grains of iron will be obtained 135 or 136 grains of ethiops, which is an augmentation of 35 per cent. If all the attention has been paid to this experiment which it deserves, the air will be found diminished in weight exactly equal to what the iron has gained. Having therefore burnt 100 grains of iron, which has acquired an additional weight of 35 grains, the diminution of air will be found exactly 70 cubical inches; and it will be found, in the sequel, that the weight of vital air is pretty nearly half a grain for each cubical inch; so that, in effect, the augmentation of weight in the one exactly coincides with the loss of it in the other. I shall observe here, once for all, that, in every experiment of this kind, the pressure and temperature of the air, both before and after the experiment, must be reduced, by calculation, to a common standard of 10° (54.5°) of the thermometer, and 28 inches of the barometer. Towards the end of this work, the manner of performing this very necessary reduction will be found accurately detailed. If it be required to examine the nature of the air which remains after this experiment, we must operate in a somewhat different manner. After the combustion is finished, and the vessels have cooled, we first take out the cup, and the burnt iron, by introducing the hand through the quicksilver, under the bell-glass; we next introduce some solution of potash, or caustic alkali, or of the sulphuret of potash, or such other substance as is judged proper for examining their action upon the residuum of air. I shall, in the sequel, give an account of these methods of analysing air, when I have explained the nature of these different substances, which are only here in a manner accidentally mentioned. After this examination, so much water must be let into the glass as will displace the quicksilver, and then, by means of a shallow dish placed below the bell-glass, it is to be removed into the common water pneumato-chemical apparatus, where the air remaining may be examined at large, and with great facility. When very soft and very pure iron has been employed in this experiment, and, if the combustion has been performed in the purest respirable or vital air, free from all admixture of the noxious or mephitic part, the air which remains after the combustion will be found as pure as it was before; but it is difficult to find iron entirely free from a small portion of charry matter, which is chiefly abundant in steel. It is likewise exceedingly difficult to procure the pure air perfectly free from some admixture of mephitis, with which it is almost always contaminated; but this species of noxious air does not, in the smallest degree, disturb the result of the experiment, as it is always found at the end exactly in the same proportion as at the beginning. I mentioned before, that we have two ways of determining the constituent parts of atmospheric air, the method of analysis, and that by synthesis. The calcination of mercury has furnished us with an example of each of these methods, since, after having robbed the respirable part of its base, by means of the mercury, we have restored it, so as to recompose an air precisely similar to that of the atmosphere. But we can equally accomplish this synthetic composition of atmospheric air, by borrowing the materials of which it is composed from different kingdoms of nature. We shall see hereafter that, when animal substances are dissolved in the nitric acid, a great quantity of gas is disengaged, which extinguishes light, and is unfit for animal respiration, being exactly similar to the noxious or mephitic part of atmospheric air. And, if we take 73 parts, by weight, of this elastic fluid, and mix it with 27 parts of highly respirable air, procured from calcined mercury, we will form an elastic fluid precisely similar to atmospheric air in all its properties. There are many other methods of separating the respirable from the noxious part of the atmospheric air, which cannot be taken notice of in this part, without anticipating information, which properly belongs to the subsequent chapters. The experiments already adduced may suffice for an elementary treatise; and, in matters of this nature, the choice of our evidences is of far greater consequence than their number. I shall close this article, by pointing out the property which atmospheric air, and all the known gasses, possess of dissolving water, which is of great consequence to be attended to in all experiments of this nature. Mr Saussure found, by experiment, that a cubical foot of atmospheric air is capable of holding 12 grains of water in solution: Other gasses, as the carbonic acid, appear capable of dissolving a greater quantity; but experiments are still wanting by which to determine their several proportions. This water, held in solution by gasses, gives rise to particular phenomena in many experiments, which require great attention, and which has frequently proved the source of great errors to chemists in determining the results of their experiments. FOOTNOTES: [9] It will likewise be necessary to take care that the air contained in the glass, both before and after the experiment, be reduced to a common temperature and pressure, otherwise the results of the following calculations will be fallacious.--E. CHAP. IV. _Nomenclature of the several Constituent Parts of Atmospheric Air._ Hitherto I have been obliged to make use of circumlocution, to express the nature of the several substances which constitute our atmosphere, having provisionally used the terms of _respirable_ and _noxious_, or _non-respirable parts of the air_. But the investigations I mean to undertake require a more direct mode of expression; and, having now endeavoured to give simple and distinct ideas of the different substances which enter into the composition of the atmosphere, I shall henceforth express these ideas by words equally simple. The temperature of our earth being very near to that at which water becomes solid, and reciprocally changes from solid to fluid, and as this phenomenon takes place frequently under our observation, it has very naturally followed, that, in the languages of at least every climate subjected to any degree of winter, a term has been used for signifying water in the state of solidity, when deprived of its caloric. The same, however, has not been found necessary with respect to water reduced to the state of vapour by an additional dose of caloric; since those persons who do not make a particular study of objects of this kind, are still ignorant that water, when in a temperature only a little above the boiling heat, is changed into an elastic aëriform fluid, susceptible, like all other gasses, of being received and contained in vessels, and preserving its gasseous form so long as it remains at the temperature of 80° (212°), and under a pressure not exceeding 28 inches of the mercurial barometer. As this phenomenon has not been generally observed, no language has used a particular term for expressing water in this state[10]; and the same thing occurs with all fluids, and all substances, which do not evaporate in the common temperature, and under the usual pressure of our atmosphere. For similar reasons, names have not been given to the liquid or concrete states of most of the aëriform fluids: These were not known to arise from the combination of caloric with certain bases; and, as they had not been seen either in the liquid or solid states, their existence, under these forms, was even unknown to natural philosophers. We have not pretended to make any alteration upon such terms as are sanctified by ancient custom; and, therefore, continue to use the words _water_ and _ice_ in their common acceptation: We likewise retain the word _air_, to express that collection of elastic fluids which composes our atmosphere; but we have not thought it necessary to preserve the same respect for modern terms, adopted by latter philosophers, having considered ourselves as at liberty to reject such as appeared liable to occasion erroneous ideas of the substances they are meant to express, and either to substitute new terms, or to employ the old ones, after modifying them in such a manner as to convey more determinate ideas. New words have been drawn, chiefly from the Greek language, in such a manner as to make their etymology convey some idea of what was meant to be represented; and these we have always endeavoured to make short, and of such a nature as to be changeable into adjectives and verbs. Following these principles, we have, after Mr Macquer's example, retained the term _gas_, employed by Vanhelmont, having arranged the numerous class of elastic aëriform fluids under that name, excepting only atmospheric air. _Gas_, therefore, in our nomenclature, becomes a generic term, expressing the fullest degree of saturation in any body with caloric; being, in fact, a term expressive of a mode of existence. To distinguish each species of gas, we employ a second term from the name of the base, which, saturated with caloric, forms each particular gas. Thus, we name water combined to saturation with caloric, so as to form an elastic fluid, _aqueous gas_; ether, combined in the same manner, _etherial gas_; the combination of alkohol with caloric, becomes _alkoholic gas_; and, following the same principles, we have _muriatic acid gas_, _ammoniacal gas_, and so on of every substance susceptible of being combined with caloric, in such a manner as to assume the gasseous or elastic aëriform state. We have already seen, that the atmospheric air is composed of two gasses, or aëriform fluids, one of which is capable, by respiration, of contributing to animal life, and in which metals are calcinable, and combustible bodies may burn; the other, on the contrary, is endowed with directly opposite qualities; it cannot be breathed by animals, neither will it admit of the combustion of inflammable bodies, nor of the calcination of metals. We have given to the base of the former, or respirable portion of the air, the name of _oxygen_, from [Greek: oxys] _acidum_, and [Greek: geinomas], _gignor_; because, in reality, one of the most general properties of this base is to form acids, by combining with many different substances. The union of this base with caloric we term _oxygen gas_, which is the same with what was formerly called _pure_, or _vital air_. The weight of this gas, at the temperature of 10° (54.50), and under a pressure equal to 28 inches of the barometer, is half a grain for each cubical inch, or one ounce and a half to each cubical foot. The chemical properties of the noxious portion of atmospheric air being hitherto but little known, we have been satisfied to derive the name of its base from its known quality of killing such animals as are forced to breathe it, giving it the name of _azote_, from the Greek privitive particle [Greek: a] and [Greek: xaê], vita; hence the name of the noxious part of atmospheric air is _azotic gas_; the weight of which, in the same temperature, and under the same pressure, is 1 oz. 2 gros and 48 grs. to the cubical foot, or 0.4444 of a grain to the cubical inch. We cannot deny that this name appears somewhat extraordinary; but this must be the case with all new terms, which cannot be expected to become familiar until they have been some time in use. We long endeavoured to find a more proper designation without success; it was at first proposed to call it _alkaligen gas_, as, from the experiments of Mr Berthollet, it appears to enter into the composition of ammoniac, or volatile alkali; but then, we have as yet no proof of its making one of the constituent elements of the other alkalies; beside, it is proved to compose a part of the nitric acid, which gives as good reason to have called it _nitrigen_. For these reasons, finding it necessary to reject any name upon systematic principles, we have considered that we run no risk of mistake in adopting the terms of _azote_, and _azotic gas_, which only express a matter of fact, or that property which it possesses, of depriving such animals as breathe it of their lives. I should anticipate subjects more properly reserved for the subsequent chapters, were I in this place to enter upon the nomenclature of the several species of gasses: It is sufficient, in this part of the work, to establish the principles upon which their denominations are founded. The principal merit of the nomenclature we have adopted is, that, when once the simple elementary substance is distinguished by an appropriate term, the names of all its compounds derive readily, and necessarily, from this first denomination. FOOTNOTES: [10] In English, the word _steam_ is exclusively appropriated to water in the state of vapour. E. CHAP. V. _Of the Decomposition of Oxygen Gas by Sulphur, Phosphorus, and Charcoal--and of the Formation of Acids in general._ In performing experiments, it is a necessary principle, which ought never to be deviated from, that they be simplified as much as possible, and that every circumstance capable of rendering their results complicated be carefully removed. Wherefore, in the experiments which form the object of this chapter, we have never employed atmospheric air, which is not a simple substance. It is true, that the azotic gas, which forms a part of its mixture, appears to be merely passive during combustion and calcination; but, besides that it retards these operations very considerably, we are not certain but it may even alter their results in some circumstances; for which reason, I have thought it necessary to remove even this possible cause of doubt, by only making use of pure oxygen gas in the following experiments, which show the effects produced by combustion in that gas; and I shall advert to such differences as take place in the results of these, when the oxygen gas, or pure vital air, is mixed, in different proportions, with azotic gas. Having filled a bell-glass (A. Pl. iv. fig. 3), of between five and six pints measure, with oxygen gas, I removed it from the water trough, where it was filled, into the quicksilver bath, by means of a shallow glass dish slipped underneath, and having dried the mercury, I introduced 61-1/4 grains of Kunkel's phosphorus in two little China cups, like that represented at D, fig. 3. under the glass A; and that I might set fire to each of the portions of phosphorus separately, and to prevent the one from catching fire from the other, one of the dishes was covered with a piece of flat glass. I next raised the quicksilver in the bell-glass up to E F, by sucking out a sufficient portion of the gas by means of the syphon G H I. After this, by means of the crooked iron wire (fig. 16.), made red hot, I set fire to the two portions of phosphorus successively, first burning that portion which was not covered with the piece of glass. The combustion was extremely rapid, attended with a very brilliant flame, and considerable disengagement of light and heat. In consequence of the great heat induced, the gas was at first much dilated, but soon after the mercury returned to its level, and a considerable absorption of gas took place; at the same time, the whole inside of the glass became covered with white light flakes of concrete phosphoric acid. At the beginning of the experiment, the quantity of oxygen gas, reduced, as above directed, to a common standard, amounted to 162 cubical inches; and, after the combustion was finished, only 23-1/4 cubical inches, likewise reduced to the standard, remained; so that the quantity of oxygen gas absorbed during the combustion was 138-3/4 cubical inches, equal to 69.375 grains. A part of the phosphorus remained unconsumed in the bottom of the cups, which being washed on purpose to separate the acid, weighed about 16-1/4 grains; so that about 45 grains of phosphorus had been burned: But, as it is hardly possible to avoid an error of one or two grains, I leave the quantity so far qualified. Hence, as nearly 45 grains of phosphorus had, in this experiment, united with 69.375 grains of oxygen, and as no gravitating matter could have escaped through the glass, we have a right to conclude, that the weight of the substance resulting from the combustion in form of white flakes, must equal that of the phosphorus and oxygen employed, which amounts to 114.375 grains. And we shall presently find, that these flakes consisted entirely of a solid or concrete acid. When we reduce these weights to hundredth parts, it will be found, that 100 parts of phosphorus require 154 parts of oxygen for saturation, and that this combination will produce 254 parts of concrete phosphoric acid, in form of white fleecy flakes. This experiment proves, in the most convincing manner, that, at a certain degree of temperature, oxygen possesses a stronger elective attraction, or affinity, for phosphorus than for caloric; that, in consequence of this, the phosphorus attracts the base of oxygen gas from the caloric, which, being set free, spreads itself over the surrounding bodies. But, though this experiment be so far perfectly conclusive, it is not sufficiently rigorous, as, in the apparatus described, it is impossible to ascertain the weight of the flakes of concrete acid which are formed; we can therefore only determine this by calculating the weights of oxygen and phosphorus employed; but as, in physics, and in chemistry, it is not allowable to suppose what is capable of being ascertained by direct experiment, I thought it necessary to rep at this experiment, as follows, upon a larger scale, and by means of a different apparatus. I took a large glass baloon (A. Pl. iv. fig. 4.) with an opening three inches diameter, to which was fitted a crystal stopper ground with emery, and pierced with two holes for the tubes yyy, xxx. Before shutting the baloon with its stopper, I introduced the support BC, surmounted by the china cup D, containing 150 grs. of phosphorus; the stopper was then fitted to the opening of the baloon, luted with fat lute, and covered with slips of linen spread with quick-lime and white of eggs: When the lute was perfectly dry, the weight of the whole apparatus was determined to within a grain, or a grain and a half. I next exhausted the baloon, by means of an air pump applied to the tube XXX, and then introduced oxygen gas by means of the tube yyy, having a stop cock adapted to it. This kind of experiment is most readily and most exactly performed by means of the hydro-pneumatic machine described by Mr Meusnier and me in the Memoirs of the Academy for 1782, pag. 466. and explained in the latter part of this work, with several important additions and corrections since made to it by Mr Meusnier. With this instrument we can readily ascertain, in the most exact manner, both the quantity of oxygen gas introduced into the baloon, and the quantity consumed during the course of the experiment. When all things were properly disposed, I set fire to the phosphorus with a burning glass. The combustion was extremely rapid, accompanied with a bright flame, and much heat; as the operation went on, large quantities of white flakes attached themselves to the inner surface of the baloon, so that at last it was rendered quite opake. The quantity of these flakes at last became so abundant, that, although fresh oxygen gas was continually supplied, which ought to have supported the combustion, yet the phosphorus was soon extinguished. Having allowed the apparatus to cool completely, I first ascertained the quantity of oxygen gas employed, and weighed the baloon accurately, before it was opened. I next washed, dried, and weighed the small quantity of phosphorus remaining in the cup, on purpose to determine the whole quantity of phosphorus consumed in the experiment; this residuum of the phosphorus was of a yellow ochrey colour. It is evident, that by these several precautions, I could easily determine, 1st, the weight of the phosphorus consumed; 2d, the weight of the flakes produced by the combustion; and, 3d, the weight of the oxygen which had combined with the phosphorus. This experiment gave very nearly the same results with the former, as it proved that the phosphorus, during its combustion, had absorbed a little more than one and a half its weight of oxygen; and I learned with more certainty, that the weight of the new substance, produced in the experiment, exactly equalled the sum of the weights of the phosphorus consumed, and oxygen absorbed, which indeed was easily determinable _a priori_. If the oxygen gas employed be pure, the residuum after combustion is as pure as the gas employed; this proves that nothing escapes from the phosphorus, capable of altering the purity of the oxygen gas, and that the only action of the phosphorus is to separate the oxygen from the caloric, with which it was before united. I mentioned above, that when any combustible body is burnt in a hollow sphere of ice, or in an apparatus properly constructed upon that principle, the quantity of ice melted during the combustion is an exact measure of the quantity of caloric disengaged. Upon this head, the memoir given by M. de la Place and me, Aº. 1780, p. 355, may be consulted. Having submitted the combustion of phosphorus to this trial, we found that one pound of phosphorus melted a little more than 100 pounds of ice during its combustion. The combustion of phosphorus succeeds equally well in atmospheric air as in oxygen gas, with this difference, that the combustion is vastly slower, being retarded by the large proportion of azotic gas mixed with the oxygen gas, and that only about one-fifth part of the air employed is absorbed, because as the oxygen gas only is absorbed, the proportion of the azotic gas becomes so great toward the close of the experiment, as to put an end to the combustion. I have already shown, that phosphorus is changed by combustion into an extremely light, white, flakey matter; and its properties are entirely altered by this transformation: From being insoluble in water, it becomes not only soluble, but so greedy of moisture, as to attract the humidity of the air with astonishing rapidity; by this means it is converted into a liquid, considerably more dense, and of more specific gravity than water. In the state of phosphorus before combustion, it had scarcely any sensible taste, by its union with oxygen it acquires an extremely sharp and sour taste: in a word, from one of the class of combustible bodies, it is changed into an incombustible substance, and becomes one of those bodies called acids. This property of a combustible substance to be converted into an acid, by the addition of oxygen, we shall presently find belongs to a great number of bodies: Wherefore, strict logic requires that we should adopt a common term for indicating all these operations which produce analogous results; this is the true way to simplify the study of science, as it would be quite impossible to bear all its specifical details in the memory, if they were not classically arranged. For this reason, we shall distinguish this conversion of phosphorus into an acid, by its union with oxygen, and in general every combination of oxygen with a combustible substance, by the term of _oxygenation_: from which I shall adopt the verb to _oxygenate_, and of consequence shall say, that in _oxygenating_ phosphorus we convert it into an acid. Sulphur is likewise a combustible body, or, in other words, it is a body which possesses the power of decomposing oxygen gas, by attracting the oxygen from the caloric with which it was combined. This can very easily be proved, by means of experiments quite similar to those we have given with phosphorus; but it is necessary to premise, that in these operations with sulphur, the same accuracy of result is not to be expected as with phosphorus; because the acid which is formed by the combustion of sulphur is difficultly condensible, and because sulphur burns with more difficulty, and is soluble in the different gasses. But I can safely assert, from my own experiments, that sulphur in burning absorbs oxygen gas; that the resulting acid is considerably heavier than the sulphur burnt; that its weight is equal to the sum of the weights of the sulphur which has been burnt, and of the oxygen absorbed; and, lastly that this acid is weighty, incombustible, and miscible with water in all proportions: The only uncertainty remaining upon this head, is with regard to the proportions of sulphur and of oxygen which enter into the composition of the acid. Charcoal, which, from all our present knowledge regarding it, must be considered as a simple combustible body, has likewise the property of decomposing oxygen gas, by absorbing its base from the caloric: But the acid resulting from this combustion does not condense in the common temperature; under the pressure of our atmosphere, it remains in the state of gas, and requires a large proportion of water to combine with or be dissolved in. This acid has, however, all the known properties of other acids, though in a weaker degree, and combines, like them, with all the bases which are susceptible of forming neutral salts. The combustion of charcoal in oxygen gas, may be effected like that of phosphorus in the bell-glass, (A. Pl. IV. fig. 3.) placed over mercury: but, as the heat of red hot iron is not sufficient to set fire to the charcoal, we must add a small morsel of tinder, with a minute particle of phosphorus, in the same manner as directed in the experiment for the combustion of iron. A detailed account of this experiment will be found in the memoirs of the academy for 1781, p. 448. By that experiment it appears, that 28 parts by weight of charcoal require 72 parts of oxygen for saturation, and that the aëriform acid produced is precisely equal in weight to the sum of the weights of the charcoal and oxygen gas employed. This aëriform acid was called fixed or fixable air by the chemists who first discovered it; they did not then know whether it was air resembling that of the atmosphere, or some other elastic fluid, vitiated and corrupted by combustion; but since it is now ascertained to be an acid, formed like all others by the oxygenation of its peculiar base, it is obvious that the name of fixed air is quite ineligible[11]. By burning charcoal in the apparatus mentioned p. 60, Mr de la Place and I found that one lib. of charcoal melted 96 libs. 6 oz. of ice; that, during the combustion, 2 libs. 9 oz. 1 gros. 10 grs. of oxygen were absorbed, and that 3 libs. 9 oz. 1 gros. 10 grs. of acid gas were formed. This gas weighs 0.695 parts of a grain for each cubical inch, in the common standard temperature and pressure mentioned above, so that 34,242 cubical inches of acid gas are produced by the combustion of one pound of charcoal. I might multiply these experiments, and show by a numerous succession of facts, that all acids are formed by the combustion of certain substances; but I am prevented from doing so in place, by the plan which I have laid down, of proceeding only from facts already ascertained, to such as are unknown, and of drawing my examples only from circumstances already explained. In the mean time, however, the three examples above cited may suffice for giving a clear and accurate conception of the manner in which acids are formed. By these it may be clearly seen, that oxygen is an element common to them all, which constitutes their acidity; and that they differ from each other, according to the nature of the oxygenated or acidified substance. We must therefore, in every acid, carefully distinguish between the acidifiable, base, which Mr de Morveau calls the radical, and the acidifiing principle or oxygen. FOOTNOTES: [11] It may be proper to remark, though here omitted by the author, that, in conformity with the general principles of the new nomenclature, this acid is by Mr Lavoisier and his coleagues called the carbonic acid, and when in the aëriform state carbonic acid gas. E. CHAP. VI. _Of the Nomenclature of Acids in general, and particularly of those drawn from Nitre and Sea-Salt._ It becomes extremely easy, from the principles laid down in the preceding chapter, to establish a systematic nomenclature for the acids: The word _acid_, being used as a generic term, each acid falls to be distinguished in language, as in nature, by the name of its base or radical. Thus, we give the generic name of acids to the products of the combustion or oxygenation of phosphorus, of sulphur, and of charcoal; and these products are respectively named, the _phosphoric acid_, the _sulphuric acid_, and the _carbonic acid_. There is however, a remarkable circumstance in the oxygenation of combustible bodies, and of a part of such bodies as are convertible into acids, that they are susceptible of different degrees of saturation with oxygen, and that the resulting acids, though formed by the union of the same elements, are possessed of different properties, depending upon that difference of proportion. Of this, the phosphoric acid, and more especially the sulphuric, furnishes us with examples. When sulphur is combined with a small proportion of oxygen, it forms, in this first or lower degree of oxygenation, a volatile acid, having a penetrating odour, and possessed of very particular qualities. By a larger proportion of oxygen, it is changed into a fixed, heavy acid, without any odour, and which, by combination with other bodies, gives products quite different from those furnished by the former. In this instance, the principles of our nomenclature seem to fail; and it seems difficult to derive such terms from the name of the acidifiable base, as shall distinctly express these two degrees of saturation, or oxygenation, without circumlocution. By reflection, however, upon the subject, or perhaps rather from the necessity of the case, we have thought it allowable to express these varieties in the oxygenation of the acids, by simply varying the termination of their specific names. The volatile acid produced from sulphur was anciently known to Stahl under the name of _sulphurous_ acid[12]. We have preserved that term for this acid from sulphur under-saturated with oxygen; and distinguish the other, or completely saturated or oxygenated acid, by the name of _sulphuric_ acid. We shall therefore say, in this new chemical language, that sulphur, in combining with oxygen, is susceptible of two degrees of saturation; that the first, or lesser degree, constitutes sulphurous acid, which is volatile and penetrating; whilst the second, or higher degree of saturation, produces sulphuric acid, which is fixed and inodorous. We shall adopt this difference of termination for all the acids which assume several degrees of saturation. Hence we have a phosphorous and a phosphoric acid, an acetous and an acetic acid; and so on, for others in similar circumstances. This part of chemical science would have been extremely simple, and the nomenclature of the acids would not have been at all perplexed, as it is now in the old nomenclature, if the base or radical of each acid had been known when the acid itself was discovered. Thus, for instance, phosphorus being a known substance before the discovery of its acid, this latter was rightly distinguished by a term drawn from the name of its acidifiable base. But when, on the contrary, an acid happened to be discovered before its base, or rather, when the acidifiable base from which it was formed remained unknown, names were adopted for the two, which have not the smallest connection; and thus, not only the memory became burthened with useless appellations, but even the minds of students, nay even of experienced chemists, became filled with false ideas, which time and reflection alone is capable of eradicating. We may give an instance of this confusion with respect to the acid sulphur: The former chemists having procured this acid from the vitriol of iron, gave it the name of the vitriolic acid from the name of the substance which produced it; and they were then ignorant that the acid procured from sulphur by combustion was exactly the same. The same thing happened with the aëriform acid formerly called _fixed air_; it not being known that this acid was the result of combining charcoal with oxygen, a variety of denominations have been given to it, not one of which conveys just ideas of its nature or origin. We have found it extremely easy to correct and modify the ancient language with respect to these acids proceeding from known bases, having converted the name of _vitriolic acid_ into that of _sulphuric_, and the name of _fixed air_ into that of _carbonic acid_; but it is impossible to follow this plan with the acids whose bases are still unknown; with these we have been obliged to use a contrary plan, and, instead of forming the name of the acid from that of its base, have been forced to denominate the unknown base from the name of the known acid, as happens in the case of the acid which is procured from sea salt. To disengage this acid from the alkaline base with which it is combined, we have only to pour sulphuric acid upon sea-salt, immediately a brisk effervescence takes place, white vapours arise, of a very penetrating odour, and, by only gently heating the mixture, all the acid is driven off. As, in the common temperature and pressure of our atmosphere, this acid is naturally in the state of gas, we must use particular precautions for retaining it in proper vessels. For small experiments, the most simple and most commodious apparatus consists of a small retort G, (Pl. V. Fig. 5.), into which the sea-salt is introduced, well dried[13], we then pour on some concentrated sulphuric acid, and immediately introduce the beak of the retort under little jars or bell-glasses A, (same Plate and Fig.), previously filled with quicksilver. In proportion as the acid gas is disengaged, it passes into the jar, and gets to the top of the quicksilver, which it displaces. When the disengagement of the gas slackens, a gentle heat is applied to the retort, and gradually increased till nothing more passes over. This acid gas has a very strong affinity with water, which absorbs an enormous quantity of it, as is proved by introducing a very thin layer of water into the glass which contains the gas; for, in an instant, the whole acid gas disappears, and combines with the water. This latter circumstance is taken advantage of in laboratories and manufactures, on purpose to obtain the acid of sea-salt in a liquid form; and for this purpose the apparatus (Pl. IV. Fig. 1.) is employed. It consists, 1st, of a tubulated retort A, into which the sea-salt, and after it the sulphuric acid, are introduced through the opening H; 2d, of the baloon or recipient c, b, intended for containing the small quantity of liquid which passes over during the process; and, 3d, of a set of bottles, with two mouths, L, L, L, L, half filled with water, intended for absorbing the gas disengaged by the distillation. This apparatus will be more amply described in the latter part of this work. Although we have not yet been able, either to compose or to decompound this acid of sea-salt, we cannot have the smallest doubt that it, like all other acids, is composed by the union of oxygen with an acidifiable base. We have therefore called this unknown substance the _muriatic base_, or _muriatic radical_, deriving this name, after the example of Mr Bergman and Mr de Morveau, from the Latin word _muria_, which was anciently used to signify sea-salt. Thus, without being able exactly to determine the component parts of _muriatic acid_, we design, by that term, a volatile acid, which retains the form of gas in the common temperature and pressure of our atmosphere, which combines with great facility, and in great quantity, with water, and whose acidifiable base adheres so very intimately with oxygen, that no method has hitherto been devised for separating them. If ever this acidifiable base of the muriatic acid is discovered to be a known substance, though now unknown in that capacity, it will be requisite to change its present denomination for one analogous with that of its base. In common with sulphuric acid, and several other acids, the muriatic is capable of different degrees of oxygenation; but the excess of oxygen produces quite contrary effects upon it from what the same circumstance produces upon the acid of sulphur. The lower degree of oxygenation converts sulphur into a volatile gasseous acid, which only mixes in small proportions with water, whilst a higher oxygenation forms an acid possessing much stronger acid properties, which is very fixed and cannot remain in the state of gas but in a very high temperature, which has no smell, and which mixes in large proportion with water. With muriatic acid, the direct reverse takes place; an additional saturation with oxygen renders it more volatile, of a more penetrating odour, less miscible with water, and diminishes its acid properties. We were at first inclined to have denominated these two degrees of saturation in the same manner as we had done with the acid of sulphur, calling the less oxygenated _muriatous acid_, and that which is more saturated with oxygen _muriatic acid_: But, as this latter gives very particular results in its combinations, and as nothing analogous to it is yet known in chemistry, we have left the name of muriatic acid to the less saturated, and give the latter the more compounded appellation of _oxygenated muriatic acid_. Although the base or radical of the acid which is extracted from nitre or saltpetre be better known, we have judged proper only to modify its name in the same manner with that of the muriatic acid. It is drawn from nitre, by the intervention of sulphuric acid, by a process similar to that described for extracting the muriatic acid, and by means of the same apparatus (Pl. IV. Fig. 1.). In proportion as the acid passes over, it is in part condensed in the baloon or recipient, and the rest is absorbed by the water contained in the bottles L,L,L,L; the water becomes first green, then blue, and at last yellow, in proportion to the concentration of the acid. During this operation, a large quantity of oxygen gas, mixed with a small proportion of azotic gas, is disengaged. This acid, like all others, is composed of oxygen, united to an acidifiable base, and is even the first acid in which the existence of oxygen was well ascertained. Its two constituent elements are but weakly united, and are easily separated, by presenting any substance with which oxygen has a stronger affinity than with the acidifiable base peculiar to this acid. By some experiments of this kind, it was first discovered that azote, or the base of mephitis or azotic gas, constituted its acidifiable base or radical; and consequently that the acid of nitre was really an azotic acid, having azote for its base, combined with oxygen. For these reasons, that we might be consistent with our principles, it appeared necessary, either to call the acid by the name of _azotic_, or to name the base _nitric radical_; but from either of these we were dissuaded, by the following considerations. In the _first_ place, it seemed difficult to change the name of nitre or saltpetre, which has been universally adopted in society, in manufactures, and in chemistry; and, on the other hand, azote having been discovered by Mr Berthollet to be the base of volatile alkali, or ammoniac, as well as of this acid, we thought it improper to call it nitric radical. We have therefore continued the term of azote to the base of that part of atmospheric air which is likewise the nitric and ammoniacal radical; and we have named the acid of nitre, in its lower and higher degrees of oxygenation, _nitrous acid_ in the former, and _nitric acid_ in the latter state; thus preserving its former appellation properly modified. Several very respectable chemists have disapproved of this deference for the old terms, and wished us to have persevered in perfecting a new chemical language, without paying any respect for ancient usage; so that, by thus steering a kind of middle course, we have exposed ourselves to the censures of one sect of chemists, and to the expostulations of the opposite party. The acid of nitre is susceptible of assuming a great number of separate states, depending upon its degree of oxygenation, or upon the proportions in which azote and oxygen enter into its composition. By a first or lowest degree of oxygenation, it forms a particular species of gas, which we shall continue to name _nitrous gas_; this is composed nearly of two parts, by weight, of oxygen combined with one part of azote; and in this state it is not miscible with water. In this gas, the azote is by no means saturated with oxygen, but, on the contrary, has still a very great affinity for that element, and even attracts it from atmospheric air, immediately upon getting into contact with it. This combination of nitrous gas with atmospheric air has even become one of the methods for determining the quantity of oxygen contained in air, and consequently for ascertaining its degree of salubrity. This addition of oxygen converts the nitrous gas into a powerful acid, which has a strong affinity with water, and which is itself susceptible of various additional degrees of oxygenation. When the proportions of oxygen and azote is below three parts, by weight, of the former, to one of the latter, the acid is red coloured, and emits copious fumes. In this state, by the application of a gentle heat, it gives out nitrous gas; and we term it, in this degree of oxygenation, _nitrous acid_. When four parts, by weight, of oxygen, are combined with one part of azote, the acid is clear and colourless, more fixed in the fire than the nitrous acid, has less odour, and its constituent elements are more firmly united. This species of acid, in conformity with our principles of nomenclature, is called _nitric acid_. Thus, nitric acid is the acid of nitre, surcharged with oxygen; nitrous acid is the acid of nitre surcharged with azote; or, what is the same thing, with nitrous gas; and this latter is azote not sufficiently saturated with oxygen to possess the properties of an acid. To this degree of oxygenation, we have afterwards, in the course of this work, given the generical name of _oxyd_[14]. FOOTNOTES: [12] The term formerly used by the English chemists for this acid was written _sulphureous_; but we have thought proper to spell it as above, that it may better conform with the similar terminations of nitrous, carbonous, &c. to be used hereafter. In general, we have used the English terminations _ic_ and _ous_ to translate the terms of the Author which end with _ique_ and _cux_, with hardly any other alterations.--E. [13] For this purpose, the operation called _decrepitation_ is used, which consists in subjecting it to nearly a red heat, in a proper vessel, so as to evaporate all its water of crystallization.--E. [14] In strict conformity with the principles of the new nomenclature, but which the Author has given his reasons for deviating from in this instance, the following ought to have been the terms for azote, in its several degrees of oxygenation: Azote, azotic gas, (azote combined with caloric), azotic oxyd gas, nitrous acid, and nitric acid.--E. CHAP. VII. _Of the Decomposition of Oxygen Gas by means of Metals, and the Formation of Metallic Oxyds._ Oxygen has a stronger affinity with metals heated to a certain degree than with caloric; in consequence of which, all metallic bodies, excepting gold, silver, and platina, have the property of decomposing oxygen gas, by attracting its base from the caloric with which it was combined. We have already shown in what manner this decomposition takes place, by means of mercury and iron; having observed, that, in the case of the first, it must be considered as a kind of gradual combustion, whilst, in the latter, the combustion is extremely rapid, and attended with a brilliant flame. The use of the heat employed in these operations is to separate the particles of the metal from each other, and to diminish their attraction of cohesion or aggregation, or, what is the same thing, their mutual attraction for each other. The absolute weight of metallic substances is augmented in proportion to the quantity of oxygen they absorb; they, at the same time, lose their metallic splendour, and are reduced into an earthy pulverulent matter. In this state metals must not be considered as entirely saturated with oxygen, because their action upon this element is counterbalanced by the power of affinity between it and caloric. During the calcination of metals, the oxygen is therefore acted upon by two separate and opposite powers, that of its attraction for caloric, and that exerted by the metal, and only tends to unite with the latter in consequence of the excess of the latter over the former, which is, in general, very inconsiderable. Wherefore, when metallic substances are oxygenated in atmospheric air, or in oxygen gas, they are not converted into acids like sulphur, phosphorus, and charcoal, but are only changed into intermediate substances, which, though approaching to the nature of salts, have not acquired all the saline properties. The old chemists have affixed the name of _calx_ not only to metals in this state, but to every body which has been long exposed to the action of fire without being melted. They have converted this word _calx_ into a generical term, under which they confound calcareous earth, which, from a neutral salt, which it really was before calcination, has been changed by fire into an earthy alkali, by _losing_ half of its weight, with metals which, by the same means, have joined themselves to a new substance, whose quantity often _exceeds_ half their weight, and by which they have been changed almost into the nature of acids. This mode of classifying substances of so very opposite natures, under the same generic name, would have been quite contrary to our principles of nomenclature, especially as, by retaining the above term for this state of metallic substances, we must have conveyed very false ideas of its nature. We have, therefore, laid aside the expression _metallic calx_ altogether, and have substituted in its place the term _oxyd_, from the Greek word [Greek: oxys]. By this may be seen, that the language we have adopted is both copious and expressive. The first or lowest degree of oxygenation in bodies, converts them into _oxyds_; a second degree of additional oxygenation constitutes the class of acids, of which the specific names, drawn from their particular bases, terminate in _ous_, as the _nitrous_ and _sulphurous_ acids; the third degree of oxygenation changes these into the species of acids distinguished by the termination in ic, as the _nitric_ and _sulphuric_ acids; and, lastly, we can express a fourth, or highest degree of oxygenation, by adding the word _oxygenated_ to the name of the acid, as has been already done with the _oxygenated muriatic_ acid. We have not confined the term _oxyd_ to expressing the combinations of metals with oxygen, but have extended it to signify that first degree of oxygenation in all bodies, which, without converting them into acids, causes them to approach to the nature of salts. Thus, we give the name of _oxyd of sulphur_ to that soft substance into which sulphur is converted by incipient combustion; and we call the yellow matter left by phosphorus, after combustion, by the name of _oxyd of phosphorus_. In the same manner, nitrous gas, which is azote in its first degree of oxygenation, is the _oxyd of azote_. We have likewise oxyds in great numbers from the vegetable and animal kingdoms; and I shall show, in the sequel, that this new language throws great light upon all the operations of art and nature. We have already observed, that almost all the metallic oxyds have peculiar and permanent colours. These vary not only in the different species of metals, but even according to the various degrees of oxygenation in the same metal. Hence we are under the necessity of adding two epithets to each oxyd, one of which indicates the metal _oxydated_[15], while the other indicates the peculiar colour of the oxyd. Thus, we have the black oxyd of iron, the red oxyd of iron, and the yellow oxyd of iron; which expressions respectively answer to the old unmeaning terms of martial ethiops, colcothar, and rust of iron, or ochre. We have likewise the gray, yellow, and red oxyds of lead, which answer to the equally false or insignificant terms, ashes of lead, massicot, and minium. These denominations sometimes become rather long, especially when we mean to indicate whether the metal has been oxydated in the air, by detonation with nitre, or by means of acids; but then they always convey just and accurate ideas of the corresponding object which we wish to express by their use. All this will be rendered perfectly clear and distinct by means of the tables which are added to this work. FOOTNOTES: [15] Here we see the word oxyd converted into the verb _to oxydate_, _oxydated_, _oxydating_, after the same manner with the derivation of the verb _to oxygenate_, _oxygenated_, _oxygenating_, from the word _oxygen_. I am not clear of the absolute necessity of this second verb here first introduced, but think, in a work of this nature, that it is the duty of the translator to neglect every other consideration for the sake of strict fidelity to the ideas of his author.--E. CHAP. VIII. _Of the Radical Principle of Water, and of its Decomposition by Charcoal and Iron._ Until very lately, water has always been thought a simple substance, insomuch that the older chemists considered it as an element. Such it undoubtedly was to them, as they were unable to decompose it; or, at least, since the decomposition which took place daily before their eyes was entirely unnoticed. But we mean to prove, that water is by no means a simple or elementary substance. I shall not here pretend to give the history of this recent, and hitherto contested discovery, which is detailed in the Memoirs of the Academy for 1781, but shall only bring forwards the principal proofs of the decomposition and composition of water; and, I may venture to say, that these will be convincing to such as consider them impartially. _Experiment First._ Having fixed the glass tube EF, (Pl. vii. fig. 11.) of from 8 to 12 lines diameter, across a furnace, with a small inclination from E to F, lute the superior extremity E to the glass retort A, containing a determinate quantity of distilled water, and to the inferior extremity F, the worm SS fixed into the neck of the doubly tubulated bottle H, which has the bent tube KK adapted to one of its openings, in such a manner as to convey such aëriform fluids or gasses as may be disengaged, during the experiment, into a proper apparatus for determining their quantity and nature. To render the success of this experiment certain, it is necessary that the tube EF be made of well annealed and difficultly fusible glass, and that it be coated with a lute composed of clay mixed with powdered stone-ware; besides which, it must be supported about its middle by means of an iron bar passed through the furnace, lest it should soften and bend during the experiment. A tube of China-ware, or porcellain, would answer better than one of glass for this experiment, were it not difficult to procure one so entirely free from pores as to prevent the passage of air or of vapours. When things are thus arranged, a fire is lighted in the furnace EFCD, which is supported of such a strength as to keep the tube EF red hot, but not to make it melt; and, at the same time, such a fire is kept up in the furnace VVXX, as to keep the water in the retort A continually boiling. In proportion as the water in the retort A is evaporated, it fills the tube EF, and drives out the air it contained by the tube KK; the aqueous gas formed by evaporation is condensed by cooling in the worm SS, and falls, drop by drop, into the tubulated bottle H. Having continued this operation until all the water be evaporated from the retort, and having carefully emptied all the vessels employed, we find that a quantity of water has passed over into the bottle H, exactly equal to what was before contained in the retort A, without any disengagement of gas whatsoever: So that this experiment turns out to be a simple distillation; and the result would have been exactly the same, if the water had been run from one vessel into the other, through the tube EF, without having undergone the intermediate incandescence. _Experiment Second._ The apparatus being disposed, as in the former experiment, 28 grs. of charcoal, broken into moderately small parts, and which has previously been exposed for a long time to a red heat in close vessels, are introduced into the tube EF. Every thing else is managed as in the preceding experiment. The water contained in the retort A is distilled, as in the former experiment, and, being condensed in the worm, falls into the bottle H; but, at the same time, a considerable quantity of gas is disengaged, which, escaping by the tube KK, is received in a convenient apparatus for that purpose. After the operation is finished, we find nothing but a few atoms of ashes remaining in the tube EF; the 28 grs. of charcoal having entirely disappeared. When the disengaged gasses are carefully examined, they are sound to weigh 113.7 grs.[16]; these are of two kinds, viz. 144 cubical inches of carbonic acid gas, weighing 100 grs. and 380 cubical inches of a very light gas, weighing only 13.7 grs. which takes fire when in contact with air, by the approach of a lighted body; and, when the water which has passed over into the bottle H is carefully examined, it is found to have lost 85.7 grs. of its weight. Thus, in this experiment, 85.7 grs. of water, joined to 28 grs. of charcoal, have combined in such a way as to form 100 grs. of carbonic acid, and 13.7 grs. of a particular gas capable of being burnt. I have already shown, that 100 grs. of carbonic acid gas consists of 72 grs. of oxygen, combined with 28 grs. of charcoal; hence the 28 grs. of charcoal placed in the glass tube have acquired 72 grs. of oxygen from the water; and it follows, that 85.7 grs. of water are composed of 72 grs. of oxygen, combined with 13.7 grs. of a gas susceptible of combustion. We shall see presently that this gas cannot possibly have been disengaged from the charcoal, and must, consequently, have been produced from the water. I have suppressed some circumstances in the above account of this experiment, which would only have complicated and obscured its results in the minds of the reader. For instance, the inflammable gas dissolves a very small part of the charcoal, by which means its weight is somewhat augmented, and that of the carbonic gas proportionally diminished. Altho' the alteration produced by this circumstance is very inconsiderable; yet I have thought it necessary to determine its effects by rigid calculation, and to report, as above, the results of the experiment in its simplified state, as if this circumstance had not happened. At any rate, should any doubts remain respecting the consequences I have drawn from this experiment, they will be fully dissipated by the following experiments, which I am going to adduce in support of my opinion. _Experiment Third._ The apparatus being disposed exactly as in the former experiment, with this difference, that instead of the 28 grs. of charcoal, the tube EF is filled with 274 grs. of soft iron in thin plates, rolled up spirally. The tube is made red hot by means of its furnace, and the water in the retort A is kept constantly boiling till it be all evaporated, and has passed through the tube EF, so as to be condensed in the bottle H. No carbonic acid gas is disengaged in this experiment, instead of which we obtain 416 cubical inches, or 15 grs. of inflammable gas, thirteen times lighter than atmospheric air. By examining the water which has been distilled, it is found to have lost 100 grs. and the 274 grs. of iron confined in the tube are found to have acquired 85 grs. additional weight, and its magnitude is considerably augmented. The iron is now hardly at all attractable by the magnet; it dissolves in acids without effervescence; and, in short, it is converted into a black oxyd, precisely similar to that which has been burnt in oxygen gas. In this experiment we have a true _oxydation_ of iron, by means of water, exactly similar to that produced in air by the assistance of heat. One hundred grains of water having been decomposed, 85 grs. of oxygen have combined with the iron, so as to convert it into the state of black oxyd, and 15 grs. of a peculiar inflammable gas are disengaged: From all this it clearly follows, that water is composed of oxygen combined with the base of an inflammable gas, in the respective proportions of 85 parts, by weight of the former, to 15 parts of the latter. Thus water, besides the oxygen, which is one of its elements in common with many other substances, contains another element as its constituent base or radical, and for which we must find an appropriate term. None that we could think of seemed better adapted than the word _hydrogen_, which signifies the _generative principle of water_, from [Greek: ydor] _aqua_, and [Greek: geinomas] _gignor_[17]. We call the combination of this element with caloric _hydrogen gas_; and the term hydrogen expresses the base of that gas, or the radical of water. This experiment furnishes us with a new combustible body, or, in other words, a body which has so much affinity with oxygen as to draw it from its connection with caloric, and to decompose air or oxygen gas. This combustible body has itself so great affinity with caloric, that, unless when engaged in a combination with some other body, it always subsists in the aëriform or gasseous state, in the usual temperature and pressure of our atmosphere. In this state of gas it is about 1/13 of the weight of an equal bulk of atmospheric air; it is not absorbed by water, though it is capable of holding a small quantity of that fluid in solution, and it is incapable of being used for respiration. As the property this gas possesses, in common with all other combustible bodies, is nothing more than the power of decomposing air, and carrying off its oxygen from the caloric with which it was combined, it is easily understood that it cannot burn, unless in contact with air or oxygen gas. Hence, when we set fire to a bottle full of this gas, it burns gently, first at the neck of the bottle, and then in the inside of it, in proportion as the external air gets in: This combustion is slow and successive, and only takes place at the surface of contact between the two gasses. It is quite different when the two gasses are mixed before they are set on fire: If, for instance, after having introduced one part of oxygen gas into a narrow mouthed bottle, we fill it up with two parts of hydrogen gas, and bring a lighted taper, or other burning body, to the mouth of the bottle, the combustion of the two gasses takes place instantaneously with a violent explosion. This experiment ought only to be made in a bottle of very strong green glass, holding not more than a pint, and wrapped round with twine, otherwise the operator will be exposed to great danger from the rupture of the bottle, of which the fragments will be thrown about with great force. If all that has been related above, concerning the decomposition of water, be exactly conformable to truth;--if, as I have endeavoured to prove, that substance be really composed of hydrogen, as its proper constituent element, combined with oxygen, it ought to follow, that, by reuniting these two elements together, we should recompose water; and that this actually happens may be judged of by the following experiment. _Experiment Fourth._ I took a large cristal baloon, A, Pl. iv. fig. 5. holding about 30 pints, having a large opening, to which was cemented the plate of copper BC, pierced with four holes, in which four tubes terminate. The first tube, H h, is intended to be adapted to an air pump, by which the baloon is to be exhausted of its air. The second tube gg, communicates, by its extremity MM, with a reservoir of oxygen gas, with which the baloon is to be filled. The third tube d D d', communicates, by its extremity d NN, with a reservoir of hydrogen gas. The extremity d' of this tube terminates in a capillary opening, through which the hydrogen gas contained in the reservoir is forced, with a moderate degree of quickness, by the pressure of one or two inches of water. The fourth tube contains a metallic wire GL, having a knob at its extremity L, intended for giving an electrical spark from L to d', on purpose to set fire to the hydrogen gas: This wire is moveable in the tube, that we may be able to separate the knob L from the extremity d' of the tube D d'. The three tubes d D d', gg, and H h, are all provided with stop-cocks. That the hydrogen gas and oxygen gas may be as much as possible deprived of water, they are made to pass, in their way to the baloon A, through the tubes MM, NN, of about an inch diameter, and filled with salts, which, from their deliquescent nature, greedily attract the moisture of the air: Such are the acetite of potash, and the muriat or nitrat of lime[18]. These salts must only be reduced to a coarse powder, lest they run into lumps, and prevent the gasses from geting through their interstices. We must be provided before hand with a sufficient quantity of oxygen gas, carefully purified from all admixture of carbonic acid, by long contact with a solution of potash[19]. We must likewise have a double quantity of hydrogen gas, carefully purified in the same manner by long contact with a solution of potash in water. The best way of obtaining this gas free from mixture is, by decomposing water with very pure soft iron, as directed in Exp. 3. of this chapter. Having adjusted every thing properly, as above directed, the tube H h is adapted to an air-pump, and the baloon A is exhausted of its air. We next admit the oxygen gas so as to fill the baloon, and then, by means of pressure, as is before mentioned, force a small stream of hydrogen gas through its tube D d', which we immediately set on fire by an electric spark. By means of the above described apparatus, we can continue the mutual combustion of these two gasses for a long time, as we have the power of supplying them to the baloon from their reservoirs, in proportion as they are consumed. I have in another place[20] given a description of the apparatus used in this experiment, and have explained the manner of ascertaining the quantities of the gasses consumed with the most scrupulous exactitude. In proportion to the advancement of the combustion, there is a deposition of water upon the inner surface of the baloon or matrass A: The water gradually increases in quantity, and, gathering into large drops, runs down to the bottom of the vessel. It is easy to ascertain the quantity of water collected, by weighing the baloon both before and after the experiment. Thus we have a twofold verification of our experiment, by ascertaining both the quantities of the gasses employed, and of the water formed by their combustion: These two quantities must be equal to each other. By an operation of this kind, Mr Meusnier and I ascertained that it required 85 parts, by weight, of oxygen, united to 15 parts of hydrogen, to compose 100 parts of water. This experiment, which has not hitherto been published, was made in presence of a numerous committee from the Royal Academy. We exerted the most scrupulous attention to its accuracy; and have reason to believe that the above propositions cannot vary a two hundredth part from absolute truth. From these experiments, both analytical and synthetic, we may now affirm that we have ascertained, with as much certainty as is possible in physical or chemical subjects, that water is not a simple elementary substance, but is composed of two elements, oxygen and hydrogen; which elements, when existing separately, have so strong affinity for caloric, as only to subsist under the form of gas in the common temperature and pressure of our atmosphere. This decomposition and recomposition of water is perpetually operating before our eyes, in the temperature of the atmosphere, by means of compound elective attraction. We shall presently see that the phenomena attendant upon vinous fermentation, putrefaction, and even vegetation, are produced, at least in a certain degree, by decomposition of water. It is very extraordinary that this fact should have hitherto been overlooked by natural philosophers and chemists: Indeed, it strongly proves, that, in chemistry, as in moral philosophy, it is extremely difficult to overcome prejudices imbibed in early education, and to search for truth in any other road than the one we have been accustomed to follow. I shall finish this chapter by an experiment much less demonstrative than those already related, but which has appeared to make more impression than any other upon the minds of many people. When 16 ounces of alkohol are burnt in an apparatus[21] properly adapted for collecting all the water disengaged during the combustion, we obtain from 17 to 18 ounces of water. As no substance can furnish a product larger than its original bulk, it follows, that something else has united with the alkohol during its combustion; and I have already shown that this must be oxygen, or the base of air. Thus alkohol contains hydrogen, which is one of the elements of water; and the atmospheric air contains oxygen, which is the other element necessary to the composition of water. This experiment is a new proof that water is a compound substance. FOOTNOTES: [16] In the latter part of this work will be found a particular account of the processes necessary for separating the different kinds of gasses, and for determining their quantities.--A. [17] This expression Hydrogen has been very severely criticised by some, who pretend that it signifies engendered by water, and not that which engenders water. The experiments related in this chapter prove, that, when water is decomposed, hydrogen is produced, and that, when hydrogen is combined with oxygen, water is produced: So that we may say, with equal truth, that water is produced from hydrogen, or hydrogen is produced from water.--A. [18] See the nature of these salts in the second part of this book.--A. [19] By potash is here meant, pure or caustic alkali, deprived of carbonic acid by means of quick-lime: In general, we may observe here, that all the alkalies and earths must invariably be considered as in their pure or caustic state, unless otherwise expressed.--E. The method of obtaining this pure alkali of potash will be given in the sequel.--A. [20] See the third part of this work.--A. [21] See an account of this apparatus in the third part of this work.--A. CHAP. IX. _Of the quantities of Caloric disengaged from different species of Combustion._ We have already mentioned, that, when any body is burnt in the center of a hollow sphere of ice and supplied with air at the temperature of zero (32°), the quantity of ice melted from the inside of the sphere becomes a measure of the relative quantities of caloric disengaged. Mr de la Place and I gave a description of the apparatus employed for this kind of experiment in the Memoirs of the Academy for 1780, p. 355; and a description and plate of the same apparatus will be found in the third part of this work. With this apparatus, phosphorus, charcoal, and hydrogen gas, gave the following results: One pound of phosphorus melted 100 libs. of ice. One pound of charcoal melted 96 libs. 8 oz. One pound of hydrogen gas melted 295 libs. 9 oz. 3-1/2 gros. As a concrete acid is formed by the combustion of phosphorus, it is probable that very little caloric remains in the acid, and, consequently, that the above experiment gives us very nearly the whole quantity of caloric contained in the oxygen gas. Even if we suppose the phosphoric acid to contain a good deal of caloric, yet, as the phosphorus must have contained nearly an equal quantity before combustion, the error must be very small, as it will only consist of the difference between what was contained in the phosphorus before, and in the phosphoric acid after combustion. I have already shown in Chap. V. that one pound of phosphorus absorbs one pound eight ounces of oxygen during combustion; and since, by the same operation, 100 lib. of ice are melted, it follows, that the quantity of caloric contained in one pound of oxygen gas is capable of melting 66 libs. 10 oz. 5 gros 24 grs. of ice. One pound of charcoal during combustion melts only 96 libs. 8 oz. of ice, whilst it absorbs 2 libs. 9 oz. 1 gros 10 grs. of oxygen. By the experiment with phosphorus, this quantity of oxygen gas ought to disengage a quantity of caloric sufficient to melt 171 libs. 6 oz. 5 gros of ice; consequently, during this experiment, a quantity of caloric, sufficient to melt 74 libs. 14 oz. 5 gros of ice disappears. Carbonic acid is not, like phosphoric acid, in a concrete state after combustion but in the state of gas, and requires to be united with caloric to enable it to subsist in that state; the quantity of caloric missing in the last experiment is evidently employed for that purpose. When we divide that quantity by the weight of carbonic acid, formed by the combustion of one pound of charcoal, we find that the quantity of caloric necessary for changing one pound of carbonic acid from the concrete to the gasseous state, would be capable of melting 20 libs. 15 oz. 5 gros of ice. We may make a similar calculation with the combustion of hydrogen gas and the consequent formation of water. During the combustion of one pound of hydrogen gas, 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas are absorbed, and 295 libs. 9 oz. 3-1/2 gros of ice are melted. But 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas, in changing from the aëriform to the solid state, loses, according to the experiment with phosphorus, enough of caloric to have melted 377 libs. 12 oz. 3 gros of ice. There is only disengaged, from the same quantity of oxygen, during its combustion with hydrogen gas, as much caloric as melts 295 libs. 2 oz. 3-1/2 gros; wherefore there remains in the water at Zero (32°), formed, during this experiment, as much caloric as would melt 82 libs. 9 oz. 7-1/2 gros of ice. Hence, as 6 libs. 10 oz. 5 gros 24 grs. of water are formed from the combustion of one pound of hydrogen gas with 5 libs. 10 oz. 5 gros 24 grs. of oxygen, it follows that, in each pound of water, at the temperature of Zero, (32°), there exists as much caloric as would melt 12 libs. 5 oz. 2 gros 48 grs. of ice, without taking into account the quantity originally contained in the hydrogen gas, which we have been obliged to omit, for want of data to calculate its quantity. From this it appears that water, even in the state of ice, contains a considerable quantity of caloric, and that oxygen, in entering into that combination, retains likewise a good proportion. From these experiments, we may assume the following results as sufficiently established. _Combustion of Phosphorus._ From the combustion of phosphorus, as related in the foregoing experiments, it appears, that one pound of phosphorus requires 1 lib. 8 oz. of oxygen gas for its combustion, and that 2 libs. 8 oz. of concrete phosphoric acid are produced. The quantity of caloric disengaged by the combustion of one pound of phosphorus, expressed by the number of pounds of ice melted during that operation, is 100.00000. The quantity disengaged from each pound of oxygen, during the combustion of phosphorus, expressed in the same manner, is 66.66667. The quantity disengaged during the formation of one pound of phosphoric acid, 40.00000. The quantity remaining in each pound of phosphoric acid, 0.00000(A). [Note A: We here suppose the phosphoric acid not to contain any caloric, which is not strictly true; but, as I have before observed, the quantity it really contains is probably very small, and we have not given it a value, for want of a sufficient data to go upon.--A.] _Combustion of Charcoal._ In the combustion of one pound of charcoal, 2 libs. 9 oz. 1 gros 10 grs. of oxygen gas are absorbed, and 3 libs. 9 oz. 1 gros 10 grs. of carbonic acid gas are formed. Caloric, disengaged daring the combustion of one pound of charcoal, 96.50000(A). Caloric disengaged during the combustion of charcoal, from each pound of oxygen gas absorbed, 37.52823. Caloric disengaged during the formation of one pound of carbonic acid gas, 27.02024. Caloric retained by each pound of oxygen after the combustion, 29.13844. Caloric necessary for supporting one pound of carbonic acid in the state of gas, 20.97960. [Note A: All these relative quantities of caloric are expressed by the number of pounds of ice, and decimal parts, melted during the several operations.--E.] _Combustion of Hydrogen Gas._ In the combustion of one pound of hydrogen gas, 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas are absorbed, and 6 libs. 10 oz. 5 gros 24 grs. of water are formed. Caloric from each lib. of hydrogen gas, 295.58950. Caloric from each lib. of oxygen gas, 52.16280. Caloric disengaged during the formation of each pound of water, 44.33840. Caloric retained by each lib. of oxygen after combustion with hydrogen, 14.50386. Caloric retained by each lib. of water at the temperature of Zero (32°), 12.32823. _Of the Formation of Nitric Acid._ When we combine nitrous gas with oxygen gas, so as to form nitric or nitrous acid a degree of heat is produced, which is much less considerable than what is evolved during the other combinations of oxygen; whence it follows that oxygen, when it becomes fixed in nitric acid, retains a great part of the heat which it possessed in the state of gas. It is certainly possible to determine the quantity of caloric which is disengaged during the combination of these two gasses, and consequently to determine what quantity remains after the combination takes place. The first of these quantities might be ascertained, by making the combination of the two gasses in an apparatus surrounded by ice; but, as the quantity of caloric disengaged is very inconsiderable, it would be necessary to operate upon a large quantity of the two gasses in a very troublesome and complicated apparatus. By this consideration, Mr de la Place and I have hitherto been prevented from making the attempt. In the mean time, the place of such an experiment may be supplied by calculations, the results of which cannot be very far from truth. Mr de la Place and I deflagrated a convenient quantity of nitre and charcoal in an ice apparatus, and found that twelve pounds of ice were melted by the deflagration of one pound of nitre. We shall see, in the sequel, that one pound of nitre is composed, as under, of Potash 7 oz. 6 gros 51.84 grs. = 4515.84 grs. Dry acid 8 1 21.16 = 4700.16. The above quantity of dry acid is composed of Oxygen 6 oz. 3 gros 66.34 grs. = 3738.34 grs. Azote 1 5 25.82 = 961.82. By this we find that, during the above deflagration, 2 gros 1-1/3 gr. of charcoal have suffered combustion, alongst with 3738.34 grs. or 6 oz. 3 gros 66.34 grs. of oxygen. Hence, since 12 libs. of ice were melted during the combustion, it follows, that one pound of oxygen burnt in the same manner would have melted 29.58320 libs. of ice. To which the quantity of caloric, retained by a pound of oxygen after combining with charcoal to form carbonic acid gas, being added, which was already ascertained to be capable of melting 29.13844 libs. of ice, we have for the total quantity of caloric remaining in a pound of oxygen, when combined with nitrous gas in the nitric acid 58.72164; which is the number of pounds of ice the caloric remaining in the oxygen in that state is capable of melting. We have before seen that, in the state of oxygen gas, it contained at least 66.66667; wherefore it follows that, in combining with azote to form nitric acid, it only loses 7.94502. Farther experiments upon this subject are necessary to ascertain how far the results of this calculation may agree with direct fact. This enormous quantity of caloric retained by oxygen in its combination into nitric acid, explains the cause of the great disengagement of caloric during the deflagrations of nitre; or, more strictly speaking, upon all occasions of the decomposition of nitric acid. _Of the Combustion of Wax._ Having examined several cases of simple combustion, I mean now to give a few examples of a more complex nature. One pound of wax-taper being allowed to burn slowly in an ice apparatus, melted 133 libs. 2 oz. 5-1/3 gros of ice. According to my experiments in the Memoirs of the Academy for 1784, p. 606, one pound of wax-taper consists of 13 oz. 1 gros 23 grs. of charcoal, and 2 oz. 6 gros 49 grs. of hydrogen. By the foregoing experiments, the above quantity of charcoal ought to melt 79.39390 libs. of ice; and the hydrogen should melt 52.37605 --------- In all 131.76995 libs. Thus, we see the quantity of caloric disengaged from a burning taper, is pretty exactly conformable to what was obtained by burning separately a quantity of charcoal and hydrogen equal to what enters into its composition. These experiments with the taper were several times repeated, so that I have reason to believe them accurate. _Combustion of Olive Oil._ We included a burning lamp, containing a determinate quantity of olive-oil, in the ordinary apparatus, and, when the experiment was finished, we ascertained exactly the quantities of oil consumed, and of ice melted; the result was, that, during the combustion of one pound of olive-oil, 148 libs. 14 oz. 1 gros of ice were melted. By my experiments in the Memoirs of the Academy for 1784, and of which the following Chapter contains an abstract, it appears that one pound of olive-oil consists of 12 oz. 5 gros 5 grs. of charcoal, and 3 oz. 2 gros 67 grs. of hydrogen. By the foregoing experiments, that quantity of charcoal should melt 76.18723 libs. of ice, and the quantity of hydrogen in a pound of the oil should melt 62.15053 libs. The sum of these two gives 138.33776 libs. of ice, which the two constituent elements of the oil would have melted, had they separately suffered combustion, whereas the oil really melted 148.88330 libs. which gives an excess of 10.54554 in the result of the experiment above the calculated result, from data furnished by former experiments. This difference, which is by no means very considerable, may arise from errors which are unavoidable in experiments of this nature, or it may be owing to the composition of oil not being as yet exactly ascertained. It proves, however, that there is a great agreement between the results of our experiments, respecting the combination of caloric, and those which regard its disengagement. The following desiderata still remain to be determined, viz. What quantity of caloric is retained by oxygen, after combining with metals, so as to convert them into oxyds; What quantity is contained by hydrogen, in its different states of existence; and to ascertain, with more precision than is hitherto attained, how much caloric is disengaged during the formation of water, as there still remain considerable doubts with respect to our present determination of this point, which can only be removed by farther experiments. We are at present occupied with this inquiry; and, when once these several points are well ascertained, which we hope they will soon be, we shall probably be under the necessity of making considerable corrections upon most of the results of the experiments and calculations in this Chapter. I did not, however, consider this as a sufficient reason for withholding so much as is already known from such as may be inclined to labour upon the same subject. It is difficult, in our endeavours to discover the principles of a new science, to avoid beginning by guess-work; and it is rarely possible to arrive at perfection from the first setting out. CHAP. X. _Of the Combination of Combustible Substances with each other._ As combustible substances in general have a great affinity for oxygen, they ought likewise to attract, or tend to combine with each other; _quae sunt eadem uni tertio, sunt eadem inter se_; and the axiom is found to be true. Almost all the metals, for instance, are capable of uniting with each other, and forming what are called _alloys_[22], in common language. Most of these, like all combinations, are susceptible of several degrees of saturation; the greater number of these alloys are more brittle than the pure metals of which they are composed, especially when the metals alloyed together are considerably different in their degrees of fusibility. To this difference in fusibility, part of the phenomena attendant upon _alloyage_ are owing, particularly the property of iron, called by workmen _hotshort_. This kind of iron must be considered as an alloy, or mixture of pure iron, which is almost infusible, with a small portion of some other metal which fuses in a much lower degree of heat. So long as this alloy remains cold, and both metals are in the solid state, the mixture is malleable; but, if heated to a sufficient degree to liquify the more fusible metal, the particles of the liquid metal, which are interposed between the particles of the metal remaining solid, must destroy their continuity, and occasion the alloy to become brittle. The alloys of mercury, with the other metals, have usually been called _amalgams_, and we see no inconvenience from continuing the use of that term. Sulphur, phosphorus, and charcoal, readily unite with metals. Combinations of sulphur with metals are usually named _pyrites_. Their combinations with phosphorus and charcoal are either not yet named, or have received new names only of late; so that we have not scrupled to change them according to our principles. The combinations of metal and sulphur we call _sulphurets_, those with phosphorus _phosphurets_, and those formed with charcoal _carburets_. These denominations are extended to all the combinations into which the above three substances enter, without being previously oxygenated. Thus, the combination of sulphur with potash, or fixed vegetable alkali, is called _sulphuret of potash_; that which it forms with ammoniac, or volatile alkali, is termed _sulphuret of ammoniac_. Hydrogen is likewise capable of combining with many combustible substances. In the state of gas, it dissolves charcoal, sulphur, phosphorus, and several metals; we distinguish these combinations by the terms, _carbonated hydrogen gas_, _sulphurated hydrogen gas_, and _phosphorated hydrogen gas_. The sulphurated hydrogen gas was called _hepatic air_ by former chemists, or _foetid air from sulphur_, by Mr Scheele. The virtues of several mineral waters, and the foetid smell of animal excrements, chiefly arise from the presence of this gas. The phosphorated hydrogen gas is remarkable for the property, discovered by Mr Gengembre, of taking fire spontaneously upon getting into contact with atmospheric air, or, what is better, with oxygen gas. This gas has a strong flavour, resembling that of putrid fish; and it is very probable that the phosphorescent quality of fish, in the state of putrefaction, arises from the escape of this species of gas. When hydrogen and charcoal are combined together, without the intervention of caloric, to bring the hydrogen into the state of gas, they form oil, which is either fixed or volatile, according to the proportions of hydrogen and charcoal in its composition. The chief difference between fixed or fat oils drawn from vegetables by expression, and volatile or essential oils, is, that the former contains an excess of charcoal, which is separated when the oils are heated above the degree of boiling water; whereas the volatile oils, containing a just proportion of these two constituent ingredients, are not liable to be decomposed by that heat, but, uniting with caloric into the gasseous state, pass over in distillation unchanged. In the Memoirs of the Academy for 1784, p. 593. I gave an account of my experiments upon the composition of oil and alkohol, by the union of hydrogen with charcoal, and of their combination with oxygen. By these experiments, it appears that fixed oils combine with oxygen during combustion, and are thereby converted into water and carbonic acid. By means of calculation applied to the products of these experiments, we find that fixed oil is composed of 21 parts, by weight, of hydrogen combined with 79 parts of charcoal. Perhaps the solid substances of an oily nature, such as wax, contain a proportion of oxygen, to which they owe their state of solidity. I am at present engaged in a series of experiments, which I hope will throw great light upon this subject. It is worthy of being examined, whether hydrogen in its concrete state, uncombined with caloric, be susceptible of combination with sulphur, phosphorus, and the metals. There is nothing that we know of, which, _a priori_, should render these combinations impossible; for combustible bodies being in general susceptible of combination with each other, there is no evident reason for hydrogen being an exception to the rule: However, no direct experiment as yet establishes either the possibility or impossibility of this union. Iron and zinc are the most likely, of all the metals, for entering into combination with hydrogen; but, as these have the property of decomposing water, and as it is very difficult to get entirely free from moisture in chemical experiments, it is hardly possible to determine whether the small portions of hydrogen gas, obtained in certain experiments with these metals, were previously combined with the metal in the state of solid hydrogen, or if they were produced by the decomposition of a minute quantity of water. The more care we take to prevent the presence of water in these experiments, the less is the quantity of hydrogen gas procured; and, when very accurate precautions are employed, even that quantity becomes hardly sensible. However this inquiry may turn out respecting the power of combustible bodies, as sulphur, phosphorus, and metals, to absorb hydrogen, we are certain that they only absorb a very small portion; and that this combination, instead of being essential to their constitution, can only be considered as a foreign substance, which contaminates their purity. It is the province of the advocates[23] for this system to prove, by decisive experiments, the real existence of this combined hydrogen, which they have hitherto only done by conjectures founded upon suppositions. FOOTNOTES: [22] This term _alloy_, which we have from the language of the arts, serves exceedingly well for distinguishing all the combinations or intimate unions of metals with each other, and is adopted in our new nomenclature for that purpose.--A. [23] By these are meant the supporters of the phlogistic theory, who at present consider hydrogen, or the base of inflammable air, as the phlogiston of the celebrated Stahl.--E. CHAP. XI. _Observations upon Oxyds and Acids with several Bases--and upon the Composition of Animal and Vegetable Substances._ We have, in Chap. V. and VIII. examined the products resulting from the combustion of the four simple combustible substances, sulphur, phosphorus, charcoal, and hydrogen: We have shown, in Chap. X that the simple combustible substances are capable of combining with each other into compound combustible substances, and have observed that oils in general, and particularly the fixed vegetable oils, belong to this class, being composed of hydrogen and charcoal. It remains, in this chapter, to treat of the oxygenation of these compound combustible substances, and to show that there exist acids and oxyds having double and triple bases. Nature furnishes us with numerous examples of this kind of combinations, by means of which, chiefly, she is enabled to produce a vast variety of compounds from a very limited number of elements, or simple substances. It was long ago well known, that, when muriatic and nitric acids were mixed together, a compound acid was formed, having properties quite distinct from those of either of the acids taken separately. This acid was called _aqua regia_, from its most celebrated property of dissolving gold, called _king of metals_ by the alchymists. Mr Berthollet has distinctly proved that the peculiar properties of this acid arise from the combined action of its two acidifiable bases; and for this reason we have judged it necessary to distinguish it by an appropriate name: That of _nitro-muriatic_ acid appears extremely applicable, from its expressing the nature of the two substances which enter into its composition. This phenomenon of a double base in one acid, which had formerly been observed only in the nitro-muriatic acid, occurs continually in the vegetable kingdom, in which a simple acid, or one possessed of a single acidifiable base, is very rarely found. Almost all the acids procurable from this kingdom have bases composed of charcoal and hydrogen, or of charcoal, hydrogen, and phosphorus, combined with more or less oxygen. All these bases, whether double or triple, are likewise formed into oxyds, having less oxygen than is necessary to give them the properties of acids. The acids and oxyds from the animal kingdom are still more compound, as their bases generally consist of a combination of charcoal, phosphorus, hydrogen, and azote. As it is but of late that I have acquired any clear and distinct notions of these substances, I shall not, in this place, enlarge much upon the subject, which I mean to treat of very fully in some memoirs I am preparing to lay before the Academy. Most of my experiments are already performed; but, to be able to give exact reports of the resulting quantities, it is necessary that they be carefully repeated, and increased in number: Wherefore, I shall only give a short enumeration of the vegetable and animal acids and oxyds, and terminate this article by a few reflections upon the composition of vegetable and animal bodies. Sugar, mucus, under which term we include the different kinds of gums, and starch, are vegetable oxyds, having hydrogen and charcoal combined, in different proportions, as their radicals or bases, and united with oxygen, so as to bring them to the state of oxyds. From the state of oxyds they are capable of being changed into acids by the addition of a fresh quantity of oxygen; and, according to the degrees of oxygenation, and the proportion of hydrogen and charcoal in their bases, they form the several kinds of vegetable acids. It would be easy to apply the principles of our nomenclature to give names to these vegetable acids and oxyds, by using the names of the two substances which compose their bases: They would thus become hydro-carbonous acids and oxyds: In this method we might indicate which of their elements existed in excess, without circumlocution, after the manner used by Mr Rouelle for naming vegetable extracts: He calls these extracto-resinous when the extractive matter prevails in their composition, and resino-extractive when they contain a larger proportion of resinous matter. Upon that plan, and by varying the terminations according to the formerly established rules of our nomenclature, we have the following denominations: Hydro-carbonous, hydro-carbonic; carbono-hydrous, and carbono-hydric oxyds. And for the acids: Hydro-carbonous, hydro carbonic, oxygenated hydro-carbonic; carbono-hydrous, carbono-hydric, and oxygenated carbono-hydric. It is probable that the above terms would suffice for indicating all the varieties in nature, and that, in proportion as the vegetable acids become well understood, they will naturally arrange themselves under these denominations. But, though we know the elements of which these are composed, we are as yet ignorant of the proportions of these ingredients, and are still far from being able to class them in the above methodical manner; wherefore, we have determined to retain the ancient names provisionally. I am somewhat farther advanced in this inquiry than at the time of publishing our conjunct essay upon chemical nomenclature; yet it would be improper to draw decided consequences from experiments not yet sufficiently precise: Though I acknowledge that this part of chemistry still remains in some degree obscure, I must express my expectations of its being very soon elucidated. I am still more forcibly necessitated to follow the same plan in naming the acids, which have three or four elements combined in their bases; of these we have a considerable number from the animal kingdom, and some even from vegetable substances. Azote, for instance, joined to hydrogen and charcoal, form the base or radical of the Prussic acid; we have reason to believe that the same happens with the base of the Gallic acid; and almost all the animal acids have their bases composed of azote, phosphorus, hydrogen, and charcoal. Were we to endeavour to express at once all these four component parts of the bases, our nomenclature would undoubtedly be methodical; it would have the property of being clear and determinate; but this assemblage of Greek and Latin substantives and adjectives, which are not yet universally admitted by chemists, would have the appearance of a barbarous language, difficult both to pronounce and to be remembered. Besides, this part of chemistry being still far from that accuracy it must arrive to, the perfection of the science ought certainly to precede that of its language; and we must still, for some time, retain the old names for the animal oxyds and acids. We have only ventured to make a few slight modifications of these names, by changing the termination into _ous_, when we have reason to suppose the base to be in excess, and into _ic_, when we suspect the oxygen predominates. The following are all the vegetable acids hitherto known: 1. Acetous acid. 2. Acetic acid. 3. Oxalic acid. 4. Tartarous acid. 5. Pyro-tartarous acid. 6. Citric acid. 7. Malic acid. 8. Pyro-mucous acid. 9. Pyro-lignous acid. 10. Gallic acid. 11. Benzoic acid. 12. Camphoric acid. 13. Succinic acid. Though all these acids, as has been already said, are chiefly, and almost entirely, composed of hydrogen, charcoal, and oxygen, yet, properly speaking, they contain neither water carbonic acid nor oil, but only the elements necessary for forming these substances. The power of affinity reciprocally exerted by the hydrogen, charcoal, and oxygen, in these acids, is in a state of equilibrium only capable of existing in the ordinary temperature of the atmosphere; for, when they are heated but a very little above the temperature of boiling water, this equilibrium is destroyed, part of the oxygen and hydrogen unite, and form water; part of the charcoal and hydrogen combine into oil; part of the charcoal and oxygen unite to form carbonic acid; and, lastly, there generally remains a small portion of charcoal, which, being in excess with respect to the other ingredients, is left free. I mean to explain this subject somewhat farther in the succeeding chapter. The oxyds of the animal kingdom are hitherto less known than those from the vegetable kingdom, and their number is as yet not at all determined. The red part of the blood, lymph, and most of the secretions, are true oxyds, under which point of view it is very important to consider them. We are only acquainted with six animal acids, several of which, it is probable, approach very near each other in their nature, or, at least, differ only in a scarcely sensible degree. I do not include the phosphoric acid amongst these, because it is found in all the kingdoms of nature. They are, 1. Lactic acid. 2. Saccholactic acid. 3. Bombic acid. 4. Formic acid. 5. Sebacic acid. 6. Prussic acid. The connection between the constituent elements of the animal oxyds and acids is not more permanent than in those from the vegetable kingdom, as a small increase of temperature is sufficient to overturn it. I hope to render this subject more distinct than has been done hitherto in the following chapter. CHAP. XII. _Of the Decomposition of Vegetable and Animal Substances by the Action of Fire._ Before we can thoroughly comprehend what takes place during the decomposition of vegetable substances by fire, we must take into consideration the nature of the elements which enter into their composition, and the different affinities which the particles of these elements exert upon each other, and the affinity which caloric possesses with them. The true constituent elements of vegetables are hydrogen, oxygen, and charcoal: These are common to all vegetables, and no vegetable can exist without them: Such other substances as exist in particular vegetables are only essential to the composition of those in which they are found, and do not belong to vegetables in general. Of these elements, hydrogen and oxygen have a strong tendency to unite with caloric, and be converted into gas, whilst charcoal is a fixed element, having but little affinity with caloric. On the other hand, oxygen, which, in the usual temperature, tends nearly equally to unite with hydrogen and with charcoal, has a much stronger affinity with charcoal when at the red heat[24], and then unites with it to form carbonic acid. Although we are far from being able to appreciate all these powers of affinity, or to express their proportional energy by numbers, we are certain, that, however variable they may be when considered in relation to the quantity of caloric with which they are combined, they are all nearly in equilibrium in the usual temperature of the atmosphere; hence vegetables neither contain oil[25], water, nor carbonic acid, tho' they contain all the elements of these substances. The hydrogen is neither combined with the oxygen nor with the charcoal, and reciprocally; the particles of these three substances form a triple combination, which remains in equilibrium whilst undisturbed by caloric but a very slight increase of temperature is sufficient to overturn this structure of combination. If the increased temperature to which the vegetable is exposed does not exceed the heat of boiling water, one part of the hydrogen combines with the oxygen, and forms water, the rest of the hydrogen combines with a part of the charcoal, and forms volatile oil, whilst the remainder of the charcoal, being set free from its combination with the other elements, remains fixed in the bottom of the distilling vessel. When, on the contrary, we employ a red heat, no water is formed, or, at least, any that may have been produced by the first application of the heat is decomposed, the oxygen having a greater affinity with the charcoal at this degree of heat, combines with it to form carbonic acid, and the hydrogen being left free from combination with the other elements, unites with caloric, and escapes in the state of hydrogen gas. In this high temperature, either no oil is formed, or, if any was produced during the lower temperature at the beginning of the experiment, it is decomposed by the action of the red heat. Thus the decomposition of vegetable matter, under a high temperature, is produced by the action of double and triple affinities; while the charcoal attracts the oxygen, on purpose to form carbonic acid, the caloric attracts the hydrogen, and converts it into hydrogen gas. The distillation of every species of vegetable substance confirms the truth of this theory, if we can give that name to a simple relation of facts. When sugar is submitted to distillation, so long as we only employ a heat but a little below that of boiling water, it only loses its water of cristallization, it still remains sugar, and retains all its properties; but, immediately upon raising the heat only a little above that degree, it becomes blackened, a part of the charcoal separates from the combination, water slightly acidulated passes over accompanied by a little oil, and the charcoal which remains in the retort is nearly a third part of the original weight of the sugar. The operation of affinities which take place during the decomposition, by fire, of vegetables which contain azote, such as the cruciferous plants, and of those containing phosphorus, is more complicated; but, as these substances only enter into the composition of vegetables in very small quantities, they only, apparently, produce slight changes upon the products of distillation; the phosphorus seems to combine with the charcoal, and, acquiring fixity from that union, remains behind in the retort, while the azote, combining with a part of the hydrogen, forms ammoniac, or volatile alkali. Animal substances, being composed nearly of the same elements with cruciferous plants, give the same products in distillation, with this difference, that, as they contain a greater quantity of hydrogen and azote, they produce more oil and more ammoniac. I shall only produce one fact as a proof of the exactness with which this theory explains all the phenomena which occur during the distillation of animal substances, which is the rectification and total decomposition of volatile animal oil, commonly known by the name of Dippel's oil. When these oils are procured by a first distillation in a naked fire they are brown, from containing a little charcoal almost in a free state; but they become quite colourless by rectification. Even in this state the charcoal in their composition has so slight a connection with the other elements as to separate by mere exposure to the air. If we put a quantity of this animal oil, well rectified, and consequently clear, limpid, and transparent, into a bell-glass filled with oxygen gas over mercury, in a short time the gas is much diminished, being absorbed by the oil, the oxygen combining with the hydrogen of the oil forms water, which sinks to the bottom, at the same time the charcoal which was combined with the hydrogen being set free, manifests itself by rendering the oil black. Hence the only way of preserving these oils colourless and transparent, is by keeping them in bottles perfectly full and accurately corked, to hinder the contact of air, which always discolours them. Successive rectifications of this oil furnish another phenomenon confirming our theory. In each distillation a small quantity of charcoal remains in the retort, and a little water is formed by the union of the oxygen contained in the air of the distilling vessels with the hydrogen of the oil. As this takes place in each successive distillation, if we make use of large vessels and a considerable degree of heat, we at last decompose the whole of the oil, and change it entirely into water and charcoal. When we use small vessels, and especially when we employ a slow fire, or degree of heat little above that of boiling water, the total decomposition of these oils, by repeated distillation, is greatly more tedious, and more difficultly accomplished. I shall give a particular detail to the Academy, in a separate memoir, of all my experiments upon the decomposition of oil; but what I have related above may suffice to give just ideas of the composition of animal and vegetable substances, and of their decomposition by the action of fire. FOOTNOTES: [24] Though this term, red heat, does not indicate any absolutely determinate degree of temperature, I shall use it sometimes to express a temperature considerably above that of boiling water.--A. [25] I must be understood here to speak of vegetables reduced to a perfectly dry state; and, with respect to oil, I do not mean that which is procured by expression either in the cold, or in a temperature not exceeding that of boiling water; I only allude to the empyreumatic oil procured by distillation with a naked fire, in a heat superior to the temperature of boiling water; which is the only oil declared to be produced by the operation of fire. What I have published upon this subject in the Memoirs of the Academy for 1786 may be consulted.--A. CHAP. XIII. _Of the Decomposition of Vegetable Oxyds by the Vinous Fermentation._ The manner in which wine, cyder, mead, and all the liquors formed by the spiritous fermentation, are produced, is well known to every one. The juice of grapes or of apples being expressed, and the latter being diluted with water, they are put into large vats, which are kept in a temperature of at least 10° (54.5°) of the thermometer. A rapid intestine motion, or fermentation, very soon takes place, numerous globules of gas form in the liquid and burst at the surface; when the fermentation is at its height, the quantity of gas disengaged is so great as to make the liquor appear as if boiling violently over a fire. When this gas is carefully gathered, it is found to be carbonic acid perfectly pure, and free from admixture with any other species of air or gas whatever. When the fermentation is completed, the juice of grapes is changed from being sweet, and full of sugar, into a vinous liquor which no longer contains any sugar, and from which we procure, by distillation, an inflammable liquor, known in commerce under the name of Spirit of Wine. As this liquor is produced by the fermentation of any saccharine matter whatever diluted with water, it must have been contrary to the principles of our nomenclature to call it spirit of wine rather than spirit of cyder, or of fermented sugar; wherefore, we have adopted a more general term, and the Arabic word _alkohol_ seems extremely proper for the purpose. This operation is one of the most extraordinary in chemistry: We must examine whence proceed the disengaged carbonic acid and the inflammable liquor produced, and in what manner a sweet vegetable oxyd becomes thus converted into two such opposite substances, whereof one is combustible, and the other eminently the contrary. To solve these two questions, it is necessary to be previously acquainted with the analysis of the fermentable substance, and of the products of the fermentation. We may lay it down as an incontestible axiom, that, in all the operations of art and nature, nothing is created; an equal quantity of matter exists both before and after the experiment; the quality and quantity of the elements remain precisely the same; and nothing takes place beyond changes and modifications in the combination of these elements. Upon this principle the whole art of performing chemical experiments depends: We must always suppose an exact equality between the elements of the body examined and those of the products of its analysis. Hence, since from must of grapes we procure alkohol and carbonic acid, I have an undoubted right to suppose that must consists of carbonic acid and alkohol. From these premises, we have two methods of ascertaining what passes during vinous fermentation, by determining the nature of, and the elements which compose, the fermentable substances, or by accurately examining the produces resulting from fermentation; and it is evident that the knowledge of either of these must lead to accurate conclusions concerning the nature and composition of the other. From these considerations, it became necessary accurately to determine the constituent elements of the fermentable substances; and, for this purpose, I did not make use of the compound juices of fruits, the rigorous analysis of which is perhaps impossible, but made choice of sugar, which is easily analysed, and the nature of which I have already explained. This substance is a true vegetable oxyd with two bases, composed of hydrogen and charcoal brought to the state of an oxyd, by a certain proportion of oxygen; and these three elements are combined in such a way, that a very slight force is sufficient to destroy the equilibrium of their connection. By a long train of experiments, made in various ways, and often repeated, I ascertained that the proportion in which these ingredients exist in sugar, are nearly eight parts of hydrogen, 64 parts of oxygen, and 28 parts of charcoal, all by weight, forming 100 parts of sugar. Sugar must be mixed with about four times its weight of water, to render it susceptible of fermentation; and even then the equilibrium of its elements would remain undisturbed, without the assistance of some substance, to give a commencement to the fermentation. This is accomplished by means of a little yeast from beer; and, when the fermentation is once excited, it continues of itself until completed. I shall, in another place, give an account of the effects of yeast, and other ferments, upon fermentable substances. I have usually employed 10 libs. of yeast, in the state of paste, for each 100 libs. of sugar, with as much water as is four times the weight of the sugar. I shall give the results of my experiments exactly as they were obtained, preserving even the fractions produced by calculation. TABLE I. _Materials of Fermentation._ libs. oz. gros grs. Water 400 0 0 0 Sugar 100 0 0 0 Yeast in paste, 10 libs. { Water 7 3 6 44 composed of { Dry yeast 2 12 1 28 ---------------------- Total 510 TABLE II. _Constituent Elements of the Materials of Fermentation._ libs. oz. gros grs. 407 libs. 3 oz. 6 gros 44 grs. { Hydrogen 61 1 2 71.40 of water, composed of { Oxygen 346 2 3 44.60 { Hydrogen 8 0 0 0 100 libs. sugar, composed of { Oxygen 64 0 0 0 { Charcoal 28 0 0 0 { Hydrogen 0 4 5 9.30 2 libs. 12 oz. 1 gros 28 grs. of { Oxygen 1 10 2 28.76 dry yeast, composed of { Charcoal 0 12 4 59 { Azote 0 0 5 2.94 ----------------------- Total weight 510 0 0 0 TABLE III. _Recapitulation of these Elements._ libs. oz. gros grs. Oxygen: of the water 340 0 0 0 } of the water } libs. oz. gros grs. in the yeast 6 2 3 44.60 } 411 12 6 1.36 of the sugar 64 0 0 0 } of the dry yeast 1 10 2 28.76 } Hydrogen: of the water 60 0 0 0 } of the water } in the yeast 1 1 2 71.40 } 69 6 0 8.70 of the sugar 8 0 0 0 } of the dry yeast 0 4 5 9.30 } Charcoal: of the sugar 28 0 0 0 } of the yeast 0 12 4 59.00 } 28 12 4 59.00 Azote of the yeast - - - - } 0 0 5 2.94 -------------------------- In all 510 0 0 0 Having thus accurately determined the nature and quantity of the constituent elements of the materials submitted to fermentation, we have next to examine the products resulting from that process. For this purpose, I placed the above 510 libs. of fermentable liquor in a proper[26] apparatus, by means of which I could accurately determine the quantity and quality of gas disengaged during the fermentation, and could even weigh every one of the products separately, at any period of the process I judged proper. An hour or two after the substances are mixed together, especially if they are kept in a temperature of from 15° (65.75°) to 18° (72.5°) of the thermometer, the first marks of fermentation commence; the liquor turns thick and frothy, little globules of air are disengaged, which rise and burst at the surface; the quantity of these globules quickly increases, and there is a rapid and abundant production of very pure carbonic acid, accompanied with a scum, which is the yeast separating from the mixture. After some days, less or more according to the degree of heat, the intestine motion and disengagement of gas diminish; but these do not cease entirely, nor is the fermentation completed for a considerable time. During the process, 35 libs. 5 oz. 4 gros 19 grs. of dry carbonic acid are disengaged, which carry alongst with them 13 libs. 14 oz. 5 gros of water. There remains in the vessel 460 libs. 11 oz. 6 gros 53 grs. of vinous liquor, slightly acidulous. This is at first muddy, but clears of itself, and deposits a portion of yeast. When we separately analise all these substances, which is effected by very troublesome processes, we have the results as given in the following Tables. This process, with all the subordinate calculations and analyses, will be detailed at large in the Memoirs of the Academy. TABLE IV. _Product of Fermentation._ libs. oz. gros grs. 35 libs. 5 oz. 4 gros 19 grs. { Oxygen 25 7 1 34 of carbonic acid, composed of { Charcoal 9 14 2 57 408 libs. 15 oz. 5 gros 14 grs. { Oxygen 347 10 0 59 of water, composed of { Hydrogen 61 5 4 27 { Oxygen, combined { with hydrogen 31 6 1 64 { Hydrogen, combined 57 libs. 11 oz. 1 gros 58 grs. { with oxygen 5 8 5 3 of dry alkohol, composed of { Hydrogen, combined { with charcoal 4 0 5 0 { Charcoal, combined { with hydrogen 16 11 5 63 2 libs. 8 oz. of dry acetous { Hydrogen 0 2 4 0 acid, composed of { Oxygen 1 11 4 0 { Charcoal 0 10 0 0 4 libs. 1 oz. 4 gros 3 grs. { Hydrogen 0 5 1 67 of residuum of sugar, { Oxygen 2 9 7 27 composed of { Charcoal 1 2 2 53 { Hydrogen 0 2 2 41 1 lib. 6 oz. 0 gros 5 grs. { Oxygen 0 13 1 14 of dry yeast, composed of { Charcoal 0 6 2 30 { Azote 0 0 2 37 --- ----------------- 510 libs. Total 510 0 0 0 TABLE V. _Recapitulation of the Products._ ---------------------------------------------------------------------------- libs. oz. gros grs. 409 libs. 10 oz. 0 gros 54 grs. { Water 347 10 0 59 of oxygen contained in the { Carbonic acid 25 7 1 34 { Alkohol 31 6 1 64 { Acetous acid 1 11 4 0 { Residuum of sugar 2 9 7 27 { Yeast 0 13 1 14 28 libs. 12 oz. 5 gros 59 grs. { Carbonic acid 9 14 2 57 of charcoal contained { Alkohol 16 11 5 63 in the { Acetous acid 0 10 0 0 { Residuum of sugar 1 2 2 53 { Yeast 0 6 2 30 { Water 61 5 4 27 71 libs. 8 oz. 6 gros 66 grs. { Water of the alkohol 5 8 5 3 of hydrogen contained { Combined with the in the { charcoal of the alko. 4 0 5 0 { Acetous acid 0 2 4 0 { Residuum of sugar 0 5 1 67 { Yeast 0 2 2 41 2 gros 37 grs. of azote in the yeast 0 0 2 37 --- --------------- 510 libs. Total 510 0 0 0 In these results, I have been exact, even to grains; not that it is possible, in experiments of this nature, to carry our accuracy so far, but as the experiments were made only with a few pounds of sugar, and as, for the sake of comparison, I reduced the results of the actual experiments to the quintal or imaginary hundred pounds, I thought it necessary to leave the fractional parts precisely as produced by calculation. When we consider the results presented by these tables with attention, it is easy to discover exactly what occurs during fermentation. In the first place, out of the 100 libs. of sugar employed, 4 libs. 1 oz. 4 gros 3 grs. remain, without having suffered decomposition; so that, in reality, we have only operated upon 95 libs. 14 oz. 3 gros 69 grs. of sugar; that is to say, upon 61 libs. 6 oz. 45 grs. of oxygen, 7 libs. 10 oz. 6 gros 6 grs. of hydrogen, and 26 libs. 13 oz. 5 gros 19 grs. of charcoal. By comparing these quantities, we find that they are fully sufficient for forming the whole of the alkohol, carbonic acid and acetous acid produced by the fermentation. It is not, therefore, necessary to suppose that any water has been decomposed during the experiment, unless it be pretended that the oxygen and hydrogen exist in the sugar in that state. On the contrary, I have already made it evident that hydrogen, oxygen and charcoal, the three constituent elements of vegetables, remain in a state of equilibrium or mutual union with each other which subsists so long as this union remains undisturbed by increased temperature, or by some new compound attraction; and that then only these elements combine, two and two together, to form water and carbonic acid. The effects of the vinous fermentation upon sugar is thus reduced to the mere separation of its elements into two portions; one part is oxygenated at the expence of the other, so as to form carbonic acid, whilst the other part, being deoxygenated in favour of the former, is converted into the combustible substance alkohol; therefore, if it were possible to reunite alkohol and carbonic acid together, we ought to form sugar. It is evident that the charcoal and hydrogen in the alkohol do not exist in the state of oil, they are combined with a portion of oxygen, which renders them miscible with water; wherefore these three substances, oxygen, hydrogen, and charcoal, exist here likewise in a species of equilibrium or reciprocal combination; and in fact, when they are made to pass through a red hot tube of glass or porcelain, this union or equilibrium is destroyed, the elements become combined, two and two, and water and carbonic acid are formed. I had formally advanced, in my first Memoirs upon the formation of water, that it was decomposed in a great number of chemical experiments, and particularly during the vinous fermentation. I then supposed that water existed ready formed in sugar, though I am now convinced that sugar only contains the elements proper for composing it. It may be readily conceived, that it must have cost me a good deal to abandon my first notions, but by several years reflection, and after a great number of experiments and observations upon vegetable substances, I have fixed my ideas as above. I shall finish what I have to say upon vinous fermentation, by observing, that it furnishes us with the means of analysing sugar and every vegetable fermentable matter. We may consider the substances submitted to fermentation, and the products resulting from that operation, as forming an algebraic equation; and, by successively supposing each of the elements in this equation unknown, we can calculate their values in succession, and thus verify our experiments by calculation, and our calculation by experiment reciprocally. I have often successfully employed this method for correcting the first results of my experiments, and to direct me in the proper road for repeating them to advantage. I have explained myself at large upon this subject, in a Memoir upon vinous fermentation already presented to the Academy, and which will speedily be published. FOOTNOTES: [26] The above apparatus is described in the Third Part.--A. CHAP. XIV. _Of the Putrefactive Fermentation._ The phenomena of putrefaction are caused, like those of vinous fermentation, by the operation of very complicated affinities. The constituent elements of the bodies submitted to this process cease to continue in equilibrium in the threefold combination, and form themselves anew into binary combinations[27], or compounds, consisting of two elements only; but these are entirely different from the results produced by the vinous fermentation. Instead of one part of the hydrogen remaining united with part of the water and charcoal to form alkohol, as in the vinous fermentation, the whole of the hydrogen is dissipated, during putrefaction, in the form of hydrogen gas, whilst, at the same time, the oxygen and charcoal, uniting with caloric, escape in the form of carbonic acid gas; so that, when the whole process is finished, especially if the materials have been mixed with a sufficient quantity of water, nothing remains but the earth of the vegetable mixed with a small portion of charcoal and iron. Thus putrefaction is nothing more than a complete analysis of vegetable substance, during which the whole of the constituent elements is disengaged in form of gas, except the earth, which remains in the state of mould[28]. Such is the result of putrefaction when the substances submitted to it contain only oxygen, hydrogen, charcoal and a little earth. But this case is rare, and these substances putrify imperfectly and with difficulty, and require a considerable time to complete their putrefaction. It is otherwise with substances containing azote, which indeed exists in all animal matters, and even in a considerable number of vegetable substances. This additional element is remarkably favourable to putrefaction; and for this reason animal matter is mixed with vegetable, when the putrefaction of these is wished to be hastened. The whole art of forming composts and dunghills, for the purposes of agriculture, consists in the proper application of this admixture. The addition of azote to the materials of putrefaction not only accelerates the process, that element likewise combines with part of the hydrogen, and forms a new substance called _volatile alkali_ or _ammoniac_. The results obtained by analysing animal matters, by different processes, leave no room for doubt with regard to the constituent elements of ammoniac; whenever the azote has been previously separated from these substances, no ammoniac is produced; and in all cases they furnish ammoniac only in proportion to the azote they contain. This composition of ammoniac is likewise fully proved by Mr Berthollet, in the Memoirs of the Academy for 1785, p. 316. where he gives a variety of analytical processes by which ammoniac is decomposed, and its two elements, azote and hydrogen, procured separately. I already mentioned in Chap. X. that almost all combustible bodies were capable of combining with each other; hydrogen gas possesses this quality in an eminent degree, it dissolves charcoal, sulphur, and phosphorus, producing the compounds named _carbonated hydrogen gas_, _sulphurated hydrogen gas_, and _phosphorated hydrogen gas_. The two latter of these gasses have a peculiarly disagreeable flavour; the sulphurated hydrogen gas has a strong resemblance to the smell of rotten eggs, and the phosphorated smells exactly like putrid fish. Ammoniac has likewise a peculiar odour, not less penetrating, or less disagreeable, than these other gasses. From the mixture of these different flavours proceeds the fetor which accompanies the putrefaction of animal substances. Sometimes ammoniac predominates, which is easily perceived by its sharpness upon the eyes; sometimes, as in feculent matters, the sulphurated gas is most prevalent; and sometimes, as in putrid herrings, the phosphorated hydrogen gas is most abundant. I long supposed that nothing could derange or interrupt the course of putrefaction; but Mr Fourcroy and Mr Thouret have observed some peculiar phenomena in dead bodies, buried at a certain depth, and preserved to a certain degree, from contact with air; having found the muscular flesh frequently converted into true animal fat. This must have arisen from the disengagement of the azote, naturally contained in the animal substance, by some unknown cause, leaving only the hydrogen and charcoal remaining, which are the elements proper for producing fat or oil. This observation upon the possibility of converting animal substances into fat may some time or other lead to discoveries of great importance to society. The faeces of animals, and other excrementitious matters, are chiefly composed of charcoal and hydrogen, and approach considerably to the nature of oil, of which they furnish a considerable quantity by distillation with a naked fire; but the intolerable foetor which accompanies all the products of these substances prevents our expecting that, at least for a long time, they can be rendered useful in any other way than as manures. I have only given conjectural approximations in this Chapter upon the composition of animal substances, which is hitherto but imperfectly understood. We know that they are composed of hydrogen, charcoal, azote, phosphorus, and sulphur, all of which, in a state of quintuple combination, are brought to the state of oxyd by a larger or smaller quantity of oxygen. We are, however, still unacquainted with the proportions in which these substances are combined, and must leave it to time to complete this part of chemical analysis, as it has already done with several others. FOOTNOTES: [27] Binary combinations are such as consist of two simple elements combined together. Ternary, and quaternary, consist of three and four elements.--E. [28] In the Third Part will be given the description of an apparatus proper for being used in experiments of this kind.--A. CHAP. XV. _Of the Acetous Fermentation._ The acetous fermentation is nothing more than the acidification or oxygenation of wine[29], produced in the open air by means of the absorption of oxygen. The resulting acid is the acetous acid, commonly called Vinegar, which is composed of hydrogen and charcoal united together in proportions not yet ascertained, and changed into the acid state by oxygen. As vinegar is an acid, we might conclude from analogy that it contains oxygen, but this is put beyond doubt by direct experiments: In the first place, we cannot change wine into vinegar without the contact of air containing oxygen; secondly, this process is accompanied by a diminution of the volume of the air in which it is carried on from the absorption of its oxygen; and, thirdly, wine may be changed into vinegar by any other means of oxygenation. Independent of the proofs which these facts furnish of the acetous acid being produced by the oxygenation of wine, an experiment made by Mr Chaptal, Professor of Chemistry at Montpellier, gives us a distinct view of what takes place in this process. He impregnated water with about its own bulk of carbonic acid from fermenting beer, and placed this water in a cellar in vessels communicating with the air, and in a short time the whole was converted into acetous acid. The carbonic acid gas procured from beer vats in fermentation is not perfectly pure, but contains a small quantity of alkohol in solution, wherefore water impregnated with it contains all the materials necessary for forming the acetous acid. The alkohol furnishes hydrogen and one portion of charcoal, the carbonic acid furnishes oxygen and the rest of the charcoal, and the air of the atmosphere furnishes the rest of the oxygen necessary for changing the mixture into acetous acid. From this observation it follows, that nothing but hydrogen is wanting to convert carbonic acid into acetous acid; or more generally, that, by means of hydrogen, and according to the degree of oxygenation, carbonic acid may be changed into all the vegetable acids; and, on the contrary, that, by depriving any of the vegetable acids of their hydrogen, they may be converted into carbonic acid. Although the principal facts relating to the acetous acid are well known, yet numerical exactitude is still wanting, till furnished by more exact experiments than any hitherto performed; wherefore I shall not enlarge any farther upon the subject. It is sufficiently shown by what has been said, that the constitution of all the vegetable acids and oxyds is exactly conformable to the formation of vinegar; but farther experiments are necessary to teach us the proportion of the constituent elements in all these acids and oxyds. We may easily perceive, however, that this part of chemistry, like all the rest of its divisions, makes rapid progress towards perfection, and that it is already rendered greatly more simple than was formerly believed. FOOTNOTES: [29] The word Wine, in this chapter, is used to signify the liquor produced by the vinous fermentation, whatever vegetable substance may have been used for obtaining it.--E. CHAP. XVI. _Of the Formation of Neutral Salts, and of their different Bases._ We have just seen that all the oxyds and acids from the animal and vegetable kingdoms are formed by means of a small number of simple elements, or at least of such as have not hitherto been susceptible of decomposition, by means of combination with oxygen; these are azote, sulphur, phosphorus, charcoal, hydrogen, and the muriatic radical[30]. We may justly admire the simplicity of the means employed by nature to multiply qualities and forms, whether by combining three or four acidifiable bases in different proportions, or by altering the dose of oxygen employed for oxydating or acidifying them. We shall find the means no less simple and diversified, and as abundantly productive of forms and qualities, in the order of bodies we are now about to treat of. Acidifiable substances, by combining with oxygen, and their consequent conversion into acids, acquire great susceptibility of farther combination; they become capable of uniting with earthy and metallic bodies, by which means neutral salts are formed. Acids may therefore be considered as true _salifying_ principles, and the substances with which they unite to form neutral salts may be called _salifiable_ bases: The nature of the union which these two principles form with each other is meant as the subject of the present chapter. This view of the acids prevents me from considering them as salts, though they are possessed of many of the principal properties of saline bodies, as solubility in water, &c. I have already observed that they are the result of a first order of combination, being composed of two simple elements, or at least of elements which act as if they were simple, and we may therefore rank them, to use the language of Stahl, in the order of _mixts_. The neutral salts, on the contrary, are of a secondary order of combination, being formed by the union of two _mixts_ with each other, and may therefore be termed _compounds_. Hence I shall not arrange the alkalies[31] or earths in the class of salts, to which I allot only such as are composed of an oxygenated substance united to a base. I have already enlarged sufficiently upon the formation of acids in the preceding chapter, and shall not add any thing farther upon that subject; but having as yet given no account of the salifiable bases which are capable of uniting with them to form neutral salts, I mean, in this chapter, to give an account of the nature and origin of each of these bases. These are potash, soda, ammoniac, lime, magnesia, barytes, argill[32], and all the metallic bodies. § 1. _Of Potash._ We have already shown, that, when a vegetable substance is submitted to the action of fire in distilling vessels, its component elements, oxygen, hydrogen, and charcoal, which formed a threefold combination in a state of equilibrium, unite, two and two, in obedience to affinities which act conformable to the degree of heat employed. Thus, at the first application of the fire, whenever the heat produced exceeds the temperature of boiling water, part of the oxygen and hydrogen unite to form water; soon after the rest of the hydrogen, and part of the charcoal, combine into oil; and, lastly, when the fire is pushed to the red heat, the oil and water, which had been formed in the early part of the process, become again decomposed, the oxygen and charcoal unite to form carbonic acid, a large quantity of hydrogen gas is set free, and nothing but charcoal remains in the retort. A great part of these phenomena occur during the combustion of vegetables in the open air; but, in this case, the presence of the air introduces three new substances, the oxygen and azote of the air and caloric, of which two at least produce considerable changes in the results of the operation. In proportion as the hydrogen of the vegetable, or that which results from the decomposition of the water, is forced out in the form of hydrogen gas by the progress of the fire, it is set on fire immediately upon getting in contact with the air, water is again formed, and the greater part of the caloric of the two gasses becoming free produces flame. When all the hydrogen gas is driven out, burnt, and again reduced to water, the remaining charcoal continues to burn, but without flame; it is formed into carbonic acid, which carries off a portion of caloric sufficient to give it the gasseous form; the rest of the caloric, from the oxygen of the air, being set free, produces the heat and light observed during the combustion of charcoal. The whole vegetable is thus reduced into water and carbonic acid, and nothing remains but a small portion of gray earthy matter called ashes, being the only really fixed principles which enter into the constitution of vegetables. The earth, or rather ashes, which seldom exceeds a twentieth part of the weight of the vegetable, contains a substance of a particular nature, known under the name of fixed vegetable alkali, or potash. To obtain it, water is poured upon the ashes, which dissolves the potash, and leaves the ashes which are insoluble; by afterwards evaporating the water, we obtain the potash in a white concrete form: It is very fixed even in a very high degree of heat. I do not mean here to describe the art of preparing potash, or the method of procuring it in a state of purity, but have entered upon the above detail that I might not use any word not previously explained. The potash obtained by this process is always less or more saturated with carbonic acid, which is easily accounted for: As the potash does not form, or at least is not set free, but in proportion as the charcoal of the vegetable is converted into carbonic acid by the addition of oxygen, either from the air or the water, it follows, that each particle of potash, at the instant of its formation, or at least of its liberation, is in contact with a particle of carbonic acid, and, as there is a considerable affinity between these two substances, they naturally combine together. Although the carbonic acid has less affinity with potash than any other acid, yet it is difficult to separate the last portions from it. The most usual method of accomplishing this is to dissolve the potash in water; to this solution add two or three times its weight of quick-lime, then filtrate the liquor and evaporate it in close vessels; the saline substance left by the evaporation is potash almost entirely deprived of carbonic acid. In this state it is soluble in an equal weight of water, and even attracts the moisture of the air with great avidity; by this property it furnishes us with an excellent means of rendering air or gas dry by exposing them to its action. In this state it is soluble in alkohol, though not when combined with carbonic acid; and Mr Berthollet employs this property as a method of procuring potash in the state of perfect purity. All vegetables yield less or more of potash in consequence of combustion, but it is furnished in various degrees of purity by different vegetables; usually, indeed, from all of them it is mixed with different salts from which it is easily separable. We can hardly entertain a doubt that the ashes, or earth which is left by vegetables in combustion, pre-existed in them before they were burnt, forming what may be called the skeleton, or osseous part of the vegetable. But it is quite otherwise with potash; this substance has never yet been procured from vegetables but by means of processes or intermedia capable of furnishing oxygen and azote, such as combustion, or by means of nitric acid; so that it is not yet demonstrated that potash may not be a produce from these operations. I have begun a series of experiments upon this object, and hope soon to be able to give an account of their results. § 2. _Of Soda._ Soda, like potash, is an alkali procured by lixiviation from the ashes of burnt plants, but only from those which grow upon the sea-side, and especially from the herb _kali_, whence is derived the name _alkali_, given to this substance by the Arabians. It has some properties in common with potash, and others which are entirely different: In general, these two substances have peculiar characters in their saline combinations which are proper to each, and consequently distinguish them from each other; thus soda, which, as obtained from marine plants, is usually entirely saturated with carbonic acid, does not attract the humidity of the atmosphere like potash, but, on the contrary, desiccates, its cristals effloresce, and are converted into a white powder having all the properties of soda, which it really is, having only lost its water of cristallization. Hitherto we are not better acquainted with the constituent elements of soda than with those of potash, being equally uncertain whether it previously existed ready formed in the vegetable or is a combination of elements effected by combustion. Analogy leads us to suspect that azote is a constituent element of all the alkalies, as is the case with ammoniac; but we have only slight presumptions, unconfirmed by any decisive experiments, respecting the composition of potash and soda. § 3. _Of Ammoniac._ We have, however, very accurate knowledge of the composition of ammoniac, or volatile alkali, as it is called by the old chemists. Mr Berthollet, in the Memoirs of the Academy for 1784, p. 316. has proved by analysis, that 1000 parts of this substance consist of about 807 parts of azote combined with 193 parts of hydrogen. Ammoniac is chiefly procurable from animal substances by distillation, during which process the azote and hydrogen necessary to its formation unite in proper proportions; it is not, however, procured pure by this process, being mixed with oil and water, and mostly saturated with carbonic acid. To separate these substances it is first combined with an acid, the muriatic for instance, and then disengaged from that combination by the addition of lime or potash. When ammoniac is thus produced in its greatest degree of purity it can only exist under the gasseous form, at least in the usual temperature of the atmosphere, it has an excessively penetrating smell, is absorbed in large quantities by water, especially if cold and assisted by compression. Water thus saturated with ammoniac has usually been termed volatile alkaline fluor; we shall call it either simply ammoniac, or liquid ammoniac, and ammoniacal gas when it exists in the aëriform state. § 4. _Of Lime, Magnesia, Barytes, and Argill._ The composition of these four earths is totally unknown, and, until by new discoveries their constituent elements are ascertained, we are certainly authorised to consider them as simple bodies. Art has no share in the production of these earths, as they are all procured ready formed from nature; but, as they have all, especially the three first, great tendency to combination, they are never found pure. Lime is usually saturated with carbonic acid in the state of chalk, calcarious spars, most of the marbles, &c.; sometimes with sulphuric acid, as in gypsum and plaster stones; at other times with fluoric acid forming vitreous or fluor spars; and, lastly, it is found in the waters of the sea, and of saline springs, combined with muriatic acid. Of all the salifiable bases it is the most universally spread through nature. Magnesia is found in mineral waters, for the most part combined with sulphuric acid; it is likewise abundant in sea-water, united with muriatic acid; and it exists in a great number of stones of different kinds. Barytes is much less common than the three preceding earths; it is found in the mineral kingdom, combined with sulphuric acid, forming heavy spars, and sometimes, though rarely, united to carbonic acid. Argill, or the base of alum, having less tendency to combination than the other earths, is often found in the state of argill, uncombined with any acid. It is chiefly procurable from clays, of which, properly speaking, it is the base, or chief ingredient. § 5. _Of Metallic Bodies._ The metals, except gold, and sometimes silver, are rarely found in the mineral kingdom in their metallic state, being usually less or more saturated with oxygen, or combined with sulphur, arsenic, sulphuric acid, muriatic acid, carbonic acid, or phosphoric acid. Metallurgy, or the docimastic art, teaches the means of separating them from these foreign matters; and for this purpose we refer to such chemical books as treat upon these operations. We are probably only acquainted as yet with a part of the metallic substances existing in nature, as all those which have a stronger affinity to oxygen, than charcoal possesses, are incapable of being reduced to the metallic state, and, consequently, being only presented to our observation under the form of oxyds, are confounded with earths. It is extremely probable that barytes, which we have just now arranged with earths, is in this situation; for in many experiments it exhibits properties nearly approaching to those of metallic bodies. It is even possible that all the substances we call earths may be only metallic oxyds, irreducible by any hitherto known process. Those metallic bodies we are at present acquainted with, and which we can reduce to the metallic or reguline state, are the following seventeen: 1. Arsenic. 2. Molybdena. 3. Tungstein. 4. Manganese. 5. Nickel. 6. Cobalt. 7. Bismuth. 8. Antimony. 9. Zinc. 10. Iron. 11. Tin. 12. Lead. 13. Copper. 14. Mercury. 15. Silver. 16. Platina. 17. Gold. I only mean to consider these as salifiable bases, without entering at all upon the consideration of their properties in the arts, and for the uses of society. In these points of view each metal would require a complete treatise, which would lead me far beyond the bounds I have prescribed for this work. FOOTNOTES: [30] I have not ventured to omit this element, as here enumerated with the other principles of animal and vegetable substances, though it is not at all taken notice of in the preceding chapters as entering into the composition of these bodies.--E. [31] Perhaps my thus rejecting the alkalies from the class of salts may be considered as a capital defect in the method I have adopted, and I am ready to admit the charge; but this inconvenience is compensated by so many advantages, that I could not think it of sufficient consequence to make me alter my plan.--A. [32] Called Alumine by Mr Lavoisier; but as Argill has been in a manner naturalized to the language for this substance by Mr Kirwan, I have ventured to use it in preference.--E. CHAP. XVII. _Continuation of the Observations upon Salifiable Bases, and the Formation of Neutral Salts._ It is necessary to remark, that earths and alkalies unite with acids to form neutral salts without the intervention of any medium, whereas metallic substances are incapable of forming this combination without being previously less or more oxygenated; strictly speaking, therefore, metals are not soluble in acids, but only metallic oxyds. Hence, when we put a metal into an acid for solution, it is necessary, in the first place, that it become oxygenated, either by attracting oxygen from the acid or from the water; or, in other words, that a metal cannot be dissolved in an acid unless the oxygen, either of the acid, or of the water mixed with it, has a stronger affinity to the metal than to the hydrogen or the acidifiable base; or, what amounts to the same thing, that no metallic solution can take place without a previous decomposition of the water, or the acid in which it is made. The explanation of the principal phenomena of metallic solution depends entirely upon this simple observation, which was overlooked even by the illustrious Bergman. The first and most striking of these is the effervescence, or, to speak less equivocally, the disengagement of gas which takes place during the solution; in the solutions made in nitric acid this effervescence is produced by the disengagement of nitrous gas; in solutions with sulphuric acid it is either sulphurous acid gas or hydrogen gas, according as the oxydation of the metal happens to be made at the expence of the sulphuric acid or of the water. As both nitric acid and water are composed of elements which, when separate, can only exist in the gasseous form, at least in the common temperature of the atmosphere, it is evident that, whenever either of these is deprived of its oxygen, the remaining element must instantly expand and assume the state of gas; the effervescence is occasioned by this sudden conversion from the liquid to the gasseous state. The same decomposition, and consequent formation of gas, takes place when solutions of metals are made in sulphuric acid: In general, especially by the humid way, metals do not attract all the oxygen it contains; they therefore reduce it, not into sulphur, but into sulphurous acid, and as this acid can only exist as gas in the usual temperature, it is disengaged, and occasions effervescence. The second phenomenon is, that, when the metals have been previously oxydated, they all dissolve in acids without effervescence: This is easily explained; because, not having now any occasion for combining with oxygen, they neither decompose the acid nor the water by which, in the former case, the effervescence is occasioned. A third phenomenon, which requires particular consideration, is, that none of the metals produce effervescence by solution in oxygenated muriatic acid. During this process the metal, in the first place, carries off the excess of oxygen from the oxygenated muriatic acid, by which it becomes oxydated, and reduces the acid to the state of ordinary muriatic acid. In this case there is no production of gas, not that the muriatic acid does not tend to exist in the gasseous state in the common temperature, which it does equally with the acids formerly mentioned, but because this acid, which otherwise would expand into gas, finds more water combined with the oxygenated muriatic acid than is necessary to retain it in the liquid form; hence it does not disengage like the sulphurous acid, but remains, and quietly dissolves and combines with the metallic oxyd previously formed from its superabundant oxygen. The fourth phenomenon is, that metals are absolutely insoluble in such acids as have their bases joined to oxygen by a stronger affinity than these metals are capable of exerting upon that acidifying principle. Hence silver, mercury, and lead, in their metallic states, are insoluble in muriatic acid, but, when previously oxydated, they become readily soluble without effervescence. From these phenomena it appears that oxygen is the bond of union between metals and acids; and from this we are led to suppose that oxygen is contained in all substances which have a strong affinity with acids: Hence it is very probable the four eminently salifiable earths contain oxygen, and their capability of uniting with acids is produced by the intermediation of that element. What I have formerly noticed relative to these earths is considerably strengthened by the above considerations, viz. that they may very possibly be metallic oxyds, with which oxygen has a stronger affinity than with charcoal, and consequently not reducible by any known means. All the acids hitherto known are enumerated in the following table, the first column of which contains the names of the acids according to the new nomenclature, and in the second column are placed the bases or radicals of these acids, with observations. _Names of the Acids._ _Names of the Bases, with Observations._ 1. Sulphurous }Sulphur. 2. Sulphuric } 3. Phosphorous }Phosphorus. 4. Phosphoric } 5. Muriatic }Muriatic radical or base, hitherto unknown. 6. Oxygenated muriatic } 7. Nitrous } 8. Nitric }Azote. 9. Oxygenated nitric } 10. Carbonic Charcoal }The bases or radicals of all these acids 11. Acetous }seem to be formed by a combination 12. Acetic }of charcoal and hydrogen; 13. Oxalic }and the only difference seems to be 14. Tartarous }owing to the different proportions in 15. Pyro-tartarous }which these elements combine to form 16. Citric }their bases, and to the different doses 17. Malic }of oxygen in their acidification. A 18. Pyro-lignous }connected series of accurate experiments 19. Pyro-mucous }is still wanted upon this subject. 20. Gallic }Our knowledge of the bases of 21. Prussic }these acids is hitherto imperfect; we 22. Benzoic }only know that they contain hydrogen 23. Succinic }and charcoal as principal elements, 24. Camphoric }and that the prussic acid contains 25. Lactic }azote. 26. Saccholactic } 27. Bombic }The base of these and all acids 28. Formic }procured from animal substances seems 29. Sebacic }to consist of charcoal, hydrogen, }phosphorous, and azote. 30. Boracic }The bases of these two are hitherto 31. Fluoric }entirely unknown. 32. Antimonic Antimony. 33. Argentic Silver. 34. Arseniac(A) Arsenic. 35. Bismuthic Bismuth. 36. Cobaltic Cobalt. 37. Cupric Copper. 38. Stannic Tin. 39. Ferric Iron. 40. Manganic Manganese. 41. Mercuric(B) Mercury. 42. Molybdic Molybdena. 43. Nickolic Nickel. 44. Auric Gold. 45. Platinic Platina. 46. Plumbic Lead. 47. Tungstic Tungstein. 48. Zincic Zinc. [Note A: This term swerves a little from the rule in making the name of this acid terminate in _ac_ instead of _ic_. The base and acid are distinguished in French by _arsenic_ and _arsenique_; but, having chosen the English termination _ic_ to translate the French _ique_, I was obliged to use this small deviation.--E.] [Note B: Mr Lavoisier has hydrargirique; but mercurius being used for the base or metal, the name of the acid, as above, is equally regular, and less harsh.--E.] In this list, which contains 48 acids, I have enumerated 17 metallic acids hitherto very imperfectly known, but upon which Mr Berthollet is about to publish a very important work. It cannot be pretended that all the acids which exist in nature, or rather all the acidifiable bases, are yet discovered; but, on the other hand, there are considerable grounds for supposing that a more accurate investigation than has hitherto been attempted will diminish the number of the vegetable acids, by showing that several of these, at present considered as distinct acids, are only modifications of others. All that can be done in the present state of our knowledge is, to give a view of chemistry as it really is, and to establish fundamental principles, by which such bodies as may be discovered in future may receive names, in conformity with one uniform system. The known salifiable bases, or substances capable of being converted into neutral salts by union with acids, amount to 24; viz. 3 alkalies, 4 earths, and 17 metallic substances; so that, in the present state of chemical knowledge, the whole possible number of neutral salts amounts to 1152[33]. This number is upon the supposition that the metallic acids are capable of dissolving other metals, which is a new branch of chemistry not hitherto investigated, upon which depends all the metallic combinations named _vitreous_. There is reason to believe that many of these supposable saline combinations are not capable of being formed, which must greatly reduce the real number of neutral salts producible by nature and art. Even if we suppose the real number to amount only to five or six hundred species of possible neutral salts, it is evident that, were we to distinguish them, after the manner of the ancients, either by the names of their first discoverers, or by terms derived from the substances from which they are procured, we should at last have such a confusion of arbitrary designations, as no memory could possibly retain. This method might be tolerable in the early ages of chemistry, or even till within these twenty years, when only about thirty species of salts were known; but, in the present times, when the number is augmenting daily, when every new acid gives us 24 or 48 new salts, according as it is capable of one or two degrees of oxygenation, a new method is certainly necessary. The method we have adopted, drawn from the nomenclature of the acids, is perfectly analogical, and, following nature in the simplicity of her operations, gives a natural and easy nomenclature applicable to every possible neutral salt. In giving names to the different acids, we express the common property by the generical term _acid_, and distinguish each species by the name of its peculiar acidifiable base. Hence the acids formed by the oxygenation of sulphur, phosphorus, charcoal, &c. are called _sulphuric acid_, _phosphoric acid_, _carbonic acid_, &c. We thought it likewise proper to indicate the different degrees of saturation with oxygen, by different terminations of the same specific names. Hence we distinguish between sulphurous and sulphuric, and between phosphorous and phosphoric acids, &c. By applying these principles to the nomenclature of neutral salts, we give a common term to all the neutral salts arising from the combination of one acid, and distinguish the species by adding the name of the salifiable base. Thus, all the neutral salts having sulphuric acid in their composition are named _sulphats_; those formed by the phosphoric acid, _phosphats_, &c. The species being distinguished by the names of the salifiable bases gives us _sulphat of potash_, _sulphat of soda_, _sulphat of ammoniac_, _sulphat of lime_, _sulphat of iron_, &c. As we are acquainted with 24 salifiable bases, alkaline, earthy, and metallic, we have consequently 24 sulphats, as many phosphats, and so on through all the acids. Sulphur is, however, susceptible of two degrees of oxygenation, the first of which produces sulphurous, and the second, sulphuric acid; and, as the neutral salts produced by these two acids, have different properties, and are in fact different salts, it becomes necessary to distinguish these by peculiar terminations; we have therefore distinguished the neutral salts formed by the acids in the first or lesser degree of oxygenation, by changing the termination _at_ into _ite_, as _sulphites_, _phosphites_[34], &c. Thus, oxygenated or acidified sulphur, in its two degrees of oxygenation is capable of forming 48 neutral salts, 24 of which are sulphites, and as many sulphats; which is likewise the case with all the acids capable of two degrees of oxygenation[35]. It were both tiresome and unnecessary to follow these denominations through all the varieties of their possible application; it is enough to have given the method of naming the various salts, which, when once well understood, is easily applied to every possible combination. The name of the combustible and acidifiable body being once known, the names of the acid it is capable of forming, and of all the neutral combinations the acid is susceptible of entering into, are most readily remembered. Such as require a more complete illustration of the methods in which the new nomenclature is applied will, in the Second Part of this book, find Tables which contain a full enumeration of all the neutral salts, and, in general, all the possible chemical combinations, so far as is consistent with the present state of our knowledge. To these I shall subjoin short explanations, containing the best and most simple means of procuring the different species of acids, and some account of the general properties of the neutral salts they produce. I shall not deny, that, to render this work more complete, it would have been necessary to add particular observations upon each species of salt, its solubility in water and alkohol, the proportions of acid and of salifiable base in its composition, the quantity of its water of cristallization, the different degrees of saturation it is susceptible of, and, finally, the degree of force or affinity with which the acid adheres to the base. This immense work has been already begun by Messrs Bergman, Morveau, Kirwan, and other celebrated chemists, but is hitherto only in a moderate state of advancement, even the principles upon which it is founded are not perhaps sufficiently accurate. These numerous details would have swelled this elementary treatise to much too great a size; besides that, to have gathered the necessary materials, and to have completed all the series of experiments requisite, must have retarded the publication of this book for many years. This is a vast field for employing the zeal and abilities of young chemists, whom I would advise to endeavour rather to do well than to do much, and to ascertain, in the first place, the composition of the acids, before entering upon that of the neutral salts. Every edifice which is intended to resist the ravages of time should be built upon a sure foundation; and, in the present state of chemistry, to attempt discoveries by experiments, either not perfectly exact, or not sufficiently rigorous, will serve only to interrupt its progress, instead of contributing to its advancement. FOOTNOTES: [33] This number excludes all triple salts, or such as contain more than one salifiable base, all the salts whose bases are over or under saturated with acid, and those formed by the nitro-muriatic acid.--E. [34] As all the specific names of the acids in the new nomenclature are adjectives, they would have applied severally to the various salifiable bases, without the invention of other terms, with perfect distinctness. Thus, _sulphurous potash_, and _sulphuric potash_, are equally distinct as _sulphite of potash_, and _sulphat of potash_; and have the advantage of being more easily retained in the memory, because more naturally arising from the acids themselves, than the arbitrary terminations adopted by Mr Lavoisier.--E. [35] There is yet a third degree of oxygenation of acids, as the oxygenated muriatic and oxygenated nitric acids. The terms applicable to the neutral salts resulting from the union of these acids with salifiable bases is supplied by the Author in the Second Part of this Work. These are formed by prefixing the word _oxygenated_ to the name of the salt produced by the second degree of oxygenation. Thus, _oxygenated_ muriat of potash, _oxygenated_ nitrat of soda, &c.--E. PART II. Of the Combination of Acids with Salifiable Bases, and of the Formation of Neutral Salts. INTRODUCTION. If I had strictly followed the plan I at first laid down for the conduct of this work, I would have confined myself, in the Tables and accompanying observations which compose this Second Part, to short definitions of the several known acids, and abridged accounts of the processes by which they are obtainable, with a mere nomenclature or enumeration of the neutral salts which result from the combination of these acids with the various salifiable bases. But I afterwards found that the addition of similar Tables of all the simple substances which enter into the composition of the acids and oxyds, together with the various possible combinations of these elements, would add greatly to the utility of this work, without being any great increase to its size. These additions, which are all contained in the twelve first sections of this Part, and the Tables annexed to these, form a kind of recapitulation of the first fifteen Chapters of the First Part: The rest of the Tables and Sections contain all the saline combinations. It must be very apparent that, in this Part of the Work, I have borrowed greatly from what has been already published by Mr de Morveau in the First Volume of the _Encyclopedie par ordre des Matières_. I could hardly have discovered a better source of information, especially when the difficulty of consulting books in foreign languages is considered. I make this general acknowledgment on purpose to save the trouble of references to Mr de Morveau's work in the course of the following part of mine. TABLE OF SIMPLE SUBSTANCES. Simple substances belonging to all the kingdoms of nature, which may be considered as the elements of bodies. _New Names._ _Correspondent old Names._ Light Light. Caloric {Heat. {Principle or element of heat. {Fire. Igneous fluid. {Matter of fire and of heat. Oxygen {Dephlogisticated air. {Empyreal air. {Vital air, or {Base of vital air. Azote {Phlogisticated air or gas. {Mephitis, or its base. Hydrogen {Inflammable air or gas, {or the base of inflammable air. Oxydable and Acidifiable simple Substance not Metallic. _New Names._ _Correspondent old names._ Sulphur } Phosphorous }The same names. Charcoal } Muriatic radical } Fluoric radical }Still unknown. Boracic radical } Oxydable and Acidifiable simple Metallic Bodies _New Names._ _Correspondent Old Names._ Antimony } { Antimony. Arsenic } { Arsenic. Bismuth } { Bismuth. Cobalt } { Cobalt. Copper } { Copper. Gold } { Gold. Iron } { Iron. Lead } Regulus of { Lead. Manganese } { Manganese. Mercury } { Mercury. Molybdena } { Molybdena. Nickel } { Nickel. Platina } { Platina. Silver } { Silver. Tin } { Tin. Tungstein } { Tungstein. Zinc } { Zinc. Salifiable simple Earthy Substances. _New Names._ _Correspondent old Names._ Lime {Chalk, calcareous earth. {Quicklime. Magnesia {Magnesia, base of Epsom salt. {Calcined or caustic magnesia. Barytes Barytes, or heavy earth. Argill Clay, earth of alum. Silex Siliceous or vitrifiable earth. SECT. I.--_Observations upon the Table of Simple Substances._ The principle object of chemical experiments is to decompose natural bodies, so as separately to examine the different substances which enter into their composition. By consulting chemical systems, it will be found that this science of chemical analysis has made rapid progress in our own times. Formerly oil and salt were considered as elements of bodies, whereas later observation and experiment have shown that all salts, instead of being simple, are composed of an acid united to a base. The bounds of analysis have been greatly enlarged by modern discoveries[36]; the acids are shown to be composed of oxygen, as an acidifying principle common to all, united in each to a particular base. I have proved what Mr Haffenfratz had before advanced, that these radicals of the acids are not all simple elements, many of them being, like the oily principle, composed of hydrogen and charcoal. Even the bases of neutral salts have been proved by Mr Berthollet to be compounds, as he has shown that ammoniac is composed of azote and hydrogen. Thus, as chemistry advances towards perfection, by dividing and subdividing, it is impossible to say where it is to end; and these things we at present suppose simple may soon be found quite otherwise. All we dare venture to affirm of any substance is, that it must be considered as simple in the present state of our knowledge, and so far as chemical analysis has hitherto been able to show. We may even presume that the earths must soon cease to be considered as simple bodies; they are the only bodies of the salifiable class which have no tendency to unite with oxygen; and I am much inclined to believe that this proceeds from their being already saturated with that element. If so, they will fall to be considered as compounds consisting of simple substances, perhaps metallic, oxydated to a certain degree. This is only hazarded as a conjecture; and I trust the reader will take care not to confound what I have related as truths, fixed on the firm basis of observation and experiment, with mere hypothetical conjectures. The fixed alkalies, potash, and soda, are omitted in the foregoing Table, because they are evidently compound substances, though we are ignorant as yet what are the elements they are composed of. TABLE _of compound oxydable and acidifiable bases._ _Names of the radicals._ Oxydable or acidifiable { Nitro-muriatic radical or base, from the mineral { base of the acid formerly kingdom. { called aqua regia. { Tartarous radical or base. { Malic. } { Citric. } { Pyro-lignous. } Oxydable or acidifiable { Pyro-mucous. } hydro-carbonous or { Pyro-tartarous. } carbono-hydrous radicals { Oxalic. } from the vegetable { Acetous. } kingdom. { Succinic. } Radicals { Benzoic. } { Camphoric. } { Gallic. } } Oxydable or acidifiable { Lactic. } radicals from the animal { Saccholactic. } kingdom, which { Formic. } mostly contain azote, { Bombic. } and frequently phosphorus. { Sebacic. } { Lithic. } { Prussic. } _Note._--The radicals from the vegetable kingdom are converted by a first degree of oxygenation into vegetable oxyds, such as sugar, starch, and gum or mucus: Those of the animal kingdom by the same means form animal oxyds, as lymph, &c.--A. SECT. II.--_Observations upon the Table of Compound Radicals._ The older chemists being unacquainted with the composition of acids, and not suspecting them to be formed by a peculiar radical or base for each, united to an acidifying principle or element common to all, could not consequently give any name to substances of which they had not the most distant idea. We had therefore to invent a new nomenclature for this subject, though we were at the same time sensible that this nomenclature must be susceptible of great modification when the nature of the compound radicals shall be better understood[37]. The compound oxydable and acidifiable radicals from the vegetable and animal kingdoms, enumerated in the foregoing table, are not hitherto reducible to systematic nomenclature, because their exact analysis is as yet unknown. We only know in general, by some experiments of my own, and some made by Mr Hassenfratz, that most of the vegetable acids, such as the tartarous, oxalic, citric, malic, acetous, pyro-tartarous, and pyromucous, have radicals composed of hydrogen and charcoal, combined in such a way as to form single bases, and that these acids only differ from each other by the proportions in which these two substances enter into the composition of their bases, and by the degree of oxygenation which these bases have received. We know farther, chiefly from the experiments of Mr Berthollet, that the radicals from the animal kingdom, and even some of those from vegetables, are of a more compound nature, and, besides hydrogen and charcoal, that they often contain azote, and sometimes phosphorus; but we are not hitherto possessed of sufficiently accurate experiments for calculating the proportions of these several substances. We are therefore forced, in the manner of the older chemists, still to name these acids after the substances from which they are procured. There can be little doubt that these names will be laid aside when our knowledge of these substances becomes more accurate and extensive; the terms _hydro-carbonous_, _hydro-carbonic_, _carbono-hydrous_, and _carbono hydric_[38], will then become substituted for those we now employ, which will then only remain as testimonies of the imperfect state in which this part of chemistry was transmitted to us by our predecessors. It is evident that the oils, being composed of hydrogen and charcoal combined, are true carbono-hydrous or hydro-carbonous radicals; and, indeed, by adding oxygen, they are convertible into vegetable oxyds and acids, according to their degrees of oxygenation. We cannot, however, affirm that oils enter in their entire state into the composition of vegetable oxyds and acids; it is possible that they previously lose a part either of their hydrogen or charcoal, and that the remaining ingredients no longer exist in the proportions necessary to constitute oils. We still require farther experiments to elucidate these points. Properly speaking, we are only acquainted with one compound radical from the mineral kingdom, the nitro-muriatic, which is formed by the combination of azote with the muriatic radical. The other compound mineral acids have been much less attended to, from their producing less striking phenomena. SECT. III.--_Observations upon the Combinations of Light and Caloric with different Substances._ I have not constructed any table of the combinations of light and caloric with the various simple and compound substances, because our conceptions of the nature of these combinations are not hitherto sufficiently accurate. We know, in general, that all bodies in nature are imbued, surrounded, and penetrated in every way with caloric, which fills up every interval left between their particles; that, in certain cases, caloric becomes fixed in bodies, so as to constitute a part even of their solid substance, though it more frequently acts upon them with a repulsive force, from which, or from its accumulation in bodies to a greater or lesser degree, the transformation of solids into fluids, and of fluids to aëriform elasticity, is entirely owing. We have employed the generic name _gas_ to indicate this aëriform state of bodies produced by a sufficient accumulation of caloric; so that, when we wish to express the aëriform state of muriatic acid, carbonic acid, hydrogen, water, alkohol, &c. we do it by adding the word _gas_ to their names; thus muriatic acid gas, carbonic acid gas, hydrogen gas, aqueous gas, alkoholic gas, &c. The combinations of light, and its mode of acting upon different bodies, is still less known. By the experiments of Mr Berthollet, it appears to have great affinity with oxygen, is susceptible of combining with it, and contributes alongst with caloric to change it into the state of gas. Experiments upon vegetation give reason to believe that light combines with certain parts of vegetables, and that the green of their leaves, and the various colours of their flowers, is chiefly owing to this combination. This much is certain, that plants which grow in darkness are perfectly white, languid, and unhealthy, and that to make them recover vigour, and to acquire their natural colours, the direct influence of light is absolutely necessary. Somewhat similar takes place even upon animals: Mankind degenerate to a certain degree when employed in sedentary manufactures, or from living in crowded houses, or in the narrow lanes of large cities; whereas they improve in their nature and constitution in most of the country labours which are carried on in the open air. Organization, sensation, spontaneous motion, and all the operations of life, only exist at the surface of the earth, and in places exposed to the influence of light. Without it nature itself would be lifeless and inanimate. By means of light, the benevolence of the Deity hath filled the surface of the earth with organization, sensation, and intelligence. The fable of Promotheus might perhaps be considered as giving a hint of this philosophical truth, which had even presented itself to the knowledge of the ancients. I have intentionally avoided any disquisitions relative to organized bodies in this work, for which reason the phenomena of respiration, sanguification, and animal heat, are not considered; but I hope, at some future time, to be able to elucidate these curious subjects. [Trancriber's note: The following table is presented in four sections to comply with 75 character line limitation.] TABLE of the binary Combinations of Oxygen with simple Substances ------------+----------------+-----------------------------------------+ |Names of |First degree of oxygenation. | |the simple +--------------------+--------------------+ |substances. |New Names. |Ancient Names. | +----------------+--------------------+--------------------+ {Caloric |Oxygen gas {Vital or | { | {dephlogisticated | { | {air | { | { | {Hydrogen. |Water(A). | | { | | | {Azote {Nitrous oxyd, or }Nitrous gas or air | { {base of nitrous gas } | { | | | {Charcoal {Oxyd of charcoal, or}Unknown | Combinations{ {carbonic oxyd } | of oxygen { | | | with {Sulphur |Oxyd of sulphur |Soft sulphur | simple { | | | non-metallic{Phosphorus |Oxyd of phosphorus {Residuum from the } substances. { | {combustion of } { | {phosphorus } { | | | {Muriatic radical}Muriatic oxyd |Unknown | { | | | {Fluoric radical }Fluoric oxyd |Unknown | { | | | {Boracic radical }Boracic oxyd |Unknown | ------------------------------------------------------------------------ {Antimony |Grey oxyd of |Grey calx of | { |antimony |antimony | { | | | {Silver |Oxyd of silver |Calx of silver | { | | | {Arsenic |Grey oxyd of arsenic|Grey calx of arsenic| { | | | {Bismuth |Grey oxyd of bismuth|Grey calx of bismuth| { | | | { | | | {Cobalt |Grey oxyd of cobalt |Grey calx of cobalt | { | | | {Copper |Brown oxyd of copper|Brown calx of copper{ { | | { {Tin |Grey oxyd of tin |Grey calx of tin | { | | | {Iron |Black oxyd of iron |Martial ethiops { Combinations{ | | | of oxygen {Manganese |Black oxyd of |Black calx of | with the { |manganese |manganese | simple { | | | metallic {Mercury |Black oxyd of |Ethiops mineral(B) { substances. { |mercury | { { | | | {Molybdena |Oxyd of molybdena |Calx of molybdena | { | | | {Nickel |Oxyd of nickel |Calx of nickel | { | | | {Gold |Yellow oxyd of gold |Yellow calx of gold | { | | | {Platina |Yellow oxyd of |Yellow calx of | { |platina |platina | { | | | {Lead |Grey oxyd of lead |Grey calx of lead { { | | { {Tungstein |Oxyd of Tungstein |Calx of Tungstein { { | | | {Zinc |Grey oxyd of zinc |Grey calx of zinc | ------------+----------------+--------------------+--------------------+ ------------+----------------+-----------------------------------------+ |Names of |Second degree of oxygenation. | |the simple +--------------------+--------------------+ |substances. |New Names. |Ancient Names. | +----------------+--------------------+--------------------+ {Caloric | | | { | | | {Hydrogen. | | | { | | | {Azote {Nitrous acid |Smoaking nitrous | { { |acid | { | | | {Charcoal {Carbonous acid |Unknown | Combinations{ { | | of oxygen {Sulphur |Sulphurous acid |Sulphureous acid | with simple { | | | non-metallic{Phosphorus |Phosphorous acid {Volatile acid of } substances. { | {phosphorus } { | | | {Muriatic radical}Muriatous acid |Unknown | { | | | {Fluoric radical }Fluorous acid |Unknown | { | | | {Boracic radical }Boracous acid |Unknown | ------------------------------------------------------------------------ {Antimony |White oxyd of {White calx of } { |antimony {antimony } { | {diaphoretic antimony} { | | | {Silver | | | { | | | {Arsenic |White oxyd of |White calx of | { |arsenic |arsenic | { | | | {Bismuth |White oxyd of |White calx of | { |bismuth |bismuth | { | | | {Cobalt | | | { | | | {Copper |Blue and green oxyds}Blue and green | { |of copper }calces of copper | { | | | {Tin |White oxyd of tin {White calx of tin, } { | {or putty of tin } { | | | {Iron |Yellow and red oxyds}Ochre and rust of | { |of iron }iron | Combinations{ | | | of oxygen {Manganese |White oxyd of |White calx of | with the { |manganese |manganese | simple { | | | metallic {Mercury |Yellow and red oxyds{Turbith mineral, } substances. { |of mercury {red precipitate, } { | {calcinated mercury, } { | {precipitate per se } { | | | {Molybdena | | | { | | | {Nickel | | | { | | | {Gold |Red oxyd of gold {Red calx of gold, } { | {purple precipitate } { | |of cassius | { | | | {Platina | | | { | | | {Lead |Yellow and red oxyds}Massicot and minium | { |of lead } | { | | | {Tungstein | | | { | | | {Zinc |White oxyd of zinc {White calx of zinc, } { | {pompholix } ------------+----------------+--------------------+--------------------+ ------------+----------------+-----------------------------------------+ |Names of |Third degree of oxygenation. | |the simple +--------------------+--------------------+ |substances. |New Names. |Ancient Names. | +----------------+--------------------+--------------------+ {Caloric | | | { | | | {Hydrogen. | | | { | | | {Azote {Nitric acid {Pale, or not } { { {smoaking nitrous } { | {acid | { | | | Combinations{Charcoal {Carbonic acid |Fixed air | of oxygen { | | | with {Sulphur |Sulphuric acid |Vitriolic acid | simple { | | | non-metallic{Phosphorus |Phosphoric acid |Phosphoric acid | substances. { | | | {Muriatic radical}Muriatic acid |Marine acid | { | | | {Fluoric radical }Fluoric acid |Unknown till lately | { | | | {Boracic radical }Boracic acid {Homberg's sedative | { } {salt | ------------------------------------------------------------------------ {Antimony |Antimonic acid | | { | | | {Silver |Argentic acid | | { | | | {Arsenic |Arseniac acid |Acid of arsenic | { | | | {Bismuth |Bismuthic acid | | { | | | {Cobalt |Cobaltic acid | | { | | | {Copper |Cupric acid | | { | | | {Tin |Stannic acid | | { | | | {Iron |Ferric acid | | Combinations{ | | | of oxygen {Manganese |Manganesic acid | | with the { | | | simple { | | | metallic {Mercury |Mercuric acid | | substances. { | | | {Molybdena |Molybdic acid |Acid of molybdena { { | | | {Nickel |Nickelic acid | | { | | | {Gold |Auric acid | | { | | | {Platina |Platinic acid | | { | | | {Lead |Plumbic acid | | { | | | {Tungstein |Tungstic acid |Acid of Tungstein { { | | | {Zinc |Zincic acid | | ------------+----------------+--------------------+--------------------+ ------------+----------------+------------------------------------------+ |Names of |Fourth degree of oxygenation. | |the simple +---------------------+--------------------+ |substances. |New Names. |Ancient Names. | +----------------+---------------------+--------------------+ {Caloric | | | { | | | {Hydrogen. | | | { | | | {Azote {Oxygenated nitric |Unknown | { {acid | | { | | | {Charcoal {Oxygenated carbonic |Unknown | Combinations{ {acid | | of oxygen { | | | with {Sulphur |Oxygenated sulphuric |Unknown | simple { |acid | | non-metallic{Phosphorus |Oxygenated phosphoric|Unknown | substances. { |acid | | { | | | {Muriatic radical}Oxygenated muriatic {Dephlogisticated | { |acid |marine acid | { | | | {Fluoric radical } | | { | | | {Boracic radical } | | { } | | ------------------------------------------------------------------------ {Antimony | | | { | | | {Silver | | | { | | | {Arsenic |Oxygenated arseniac |Unknown | { |acid | | { | | | {Bismuth | | | { | | | {Cobalt | | | { | | | {Copper | | | { | | | {Tin | | | { | | | {Iron | | | { | | | Combinations{ | | | of oxygen {Manganese | | | with the { | | | simple { | | | metallic {Mercury | | | substances. { | | | {Molybdena |Oxygenated molybdic |Unknown | { |acid | | {Nickel | | | { | | | {Gold | | | { | | | {Platina | | | { | | | {Lead | | | { | | | {Tungstein |Oxygenated Tungstic }Unknown | { |acid | | { | | | {Zinc | | | ------------+----------------+---------------------+--------------------+ [Note A: Only one degree of oxygenation of hydrogen is hitherto known.--A.] [Note B: Ethiops mineral is the sulphuret of mercury; this should have been called black precipitate of mercury.--E.] SECT. IV.--_Observations upon the Combinations of Oxygen with the simple Substances._ Oxygen forms almost a third of the mass of our atmosphere, and is consequently one of the most plentiful substances in nature. All the animals and vegetables live and grow in this immense magazine of oxygen gas, and from it we procure the greatest part of what we employ in experiments. So great is the reciprocal affinity between this element and other substances, that we cannot procure it disengaged from all combination. In the atmosphere it is united with caloric, in the state of oxygen gas, and this again is mixed with about two thirds of its weight of azotic gas. Several conditions are requisite to enable a body to become oxygenated, or to permit oxygen to enter into combination with it. In the first place, it is necessary that the particles of the body to be oxygenated shall have less reciprocal attraction with each other than they have for the oxygen, which otherwise cannot possibly combine with them. Nature, in this case, may be assisted by art, as we have it in our power to diminish the attraction of the particles of bodies almost at will by heating them, or, in other words, by introducing caloric into the interstices between their particles; and, as the attraction of these particles for each other is diminished in the inverse ratio of their distance, it is evident that there must be a certain point of distance of particles when the affinity they possess with each other becomes less than that they have for oxygen, and at which oxygenation must necessarily take place if oxygen be present. We can readily conceive that the degree of heat at which this phenomenon begins must be different in different bodies. Hence, on purpose to oxygenate most bodies, especially the greater part of the simple substances, it is only necessary to expose them to the influence of the air of the atmosphere in a convenient degree of temperature. With respect to lead, mercury, and tin, this needs be but little higher than the medium temperature of the earth; but it requires a more considerable degree of heat to oxygenate iron, copper, &c. by the dry way, or when this operation is not assisted by moisture. Sometimes oxygenation takes place with great rapidity, and is accompanied by great sensible heat, light, and flame; such is the combustion of phosphorus in atmospheric air, and of iron in oxygen gas. That of sulphur is less rapid; and the oxygenation of lead, tin, and most of the metals, takes place vastly slower, and consequently the disengagement of caloric, and more especially of light, is hardly sensible. Some substances have so strong an affinity with oxygen, and combine with it in such low degrees of temperature, that we cannot procure them in their unoxygenated state; such is the muriatic acid, which has not hitherto been decomposed by art, perhaps even not by nature, and which consequently has only been found in the state of acid. It is probable that many other substances of the mineral kingdom are necessarily oxygenated in the common temperature of the atmosphere, and that being already saturated with oxygen, prevents their farther action upon that element. There are other means of oxygenating simple substances besides exposure to air in a certain degree of temperature, such as by placing them in contact with metals combined with oxygen, and which have little affinity with that element. The red oxyd of mercury is one of the best substances for this purpose, especially with bodies which do not combine with that metal. In this oxyd the oxygen is united with very little force to the metal, and can be driven out by a degree of heat only sufficient to make glass red hot; wherefore such bodies as are capable of uniting with oxygen are readily oxygenated, by means of being mixed with red oxyd of mercury, and moderately heated. The same effect may be, to a certain degree, produced by means of the black oxyd of manganese, the red oxyd of lead, the oxyds of silver, and by most of the metallic oxyds, if we only take care to choose such as have less affinity with oxygen than the bodies they are meant to oxygenate. All the metallic reductions and revivifications belong to this class of operations, being nothing more than oxygenations of charcoal, by means of the several metallic oxyds. The charcoal combines with the oxygen and with caloric, and escapes in form of carbonic acid gas, while the metal remains pure and revivified, or deprived of the oxygen which before combined with it in the form of oxyd. All combustible substances may likewise be oxygenated by means of mixing them with nitrat of potash or of soda, or with oxygenated muriat of potash, and subjecting the mixture to a certain degree of heat; the oxygen, in this case, quits the nitrat or the muriat, and combines with the combustible body. This species of oxygenation requires to be performed with extreme caution, and only with very small quantities; because, as the oxygen enters into the composition of nitrats, and more especially of oxygenated muriats, combined with almost as much caloric as is necessary for converting it into oxygen gas, this immense quantity of caloric becomes suddenly free the instant of the combination of the oxygen with the combustible body, and produces such violent explosions as are perfectly irresistible. By the humid way we can oxygenate most combustible bodies, and convert most of the oxyds of the three kingdoms of nature into acids. For this purpose we chiefly employ the nitric acid, which has a very slight hold of oxygen, and quits it readily to a great number of bodies by the assistance of a gentle heat. The oxygenated muriatic acid may be used for several operations of this kind, but not in them all. I give the name of _binary_ to the combinations of oxygen with the simple substances, because in these only two elements are combined. When three substances are united in one combination I call it _ternary_, and _quaternary_ when the combination consists of four substances united. TABLE _of the combinations of Oxygen with the compound radicals._ _Names of the radicals._ _Names of the resulting acids._ _New nomenclature._ _Old nomenclature._ Nitro muriatic} Nitro muriatic acid Aqua regia. radical } (A) Tartaric Tartarous acid Unknown till lately. Malic Malic acid Ditto. Citric Citric acid Acid of lemons. Pyro-lignous Pyro-lignous acid Empyreumatic acid of wood. Pyro-mucous Pyro-mucous acid Empyr. acid of sugar. Pyro-tartarous Pyro-tartarous acid Empyr. acid of tartar. Oxalic Oxalic acid Acid of sorel. Acetic {Acetous acid Vinegar, or acid of vinegar. {Acetic acid Radical vinegar. Succinic Succinic acid Volatile salt of amber. Benzoic Benzotic acid Flowers of benzoin. Camphoric Camphoric acid Unknown till lately. Gallic Gallic acid {The astringent principle {of vegetables. (B) Lactic Lactic acid Acid of sour whey. Saccholactic Saccholactic acid Unknown till lately. Formic Formic acid Acid of ants. Bombic Bombic acid Unknown till lately. Sebacic Sebacic acid Ditto. Lithic Lithic acid Urinary calculus. Prussic Prussic acid Colouring matter of Prussian blue. [Note A: These radicals by a first degree of oxygenation form vegetable oxyds, as sugar, starch, mucus, &c.--A.] [Note B: These radicals by a first degree of oxygenation form the animal oxyds, as lymph, red part of the blood, animal secretions, &c.--A.] SECT. V.--_Observations upon the Combinations of Oxygen with the Compound Radicals._ I published a new theory of the nature and formation of acids in the Memoirs of the Academy for 1776, p. 671. and 1778, p. 535. in which I concluded, that the number of acids must be greatly larger than was till then supposed. Since that time, a new field of inquiry has been opened to chemists; and, instead of five or six acids which were then known, near thirty new acids have been discovered, by which means the number of known neutral salts have been increased in the same proportion. The nature of the acidifiable bases, or radicals of the acids, and the degrees of oxygenation they are susceptible of, still remain to be inquired into. I have already shown, that almost all the oxydable and acidifiable radicals from the mineral kingdom are simple, and that, on the contrary, there hardly exists any radical in the vegetable, and more especially in the animal kingdom, but is composed of at least two substances, hydrogen and charcoal, and that azote and phosphorus are frequently united to these, by which we have compound radicals of two, three, and four bases or simple elements united. From these observations, it appears that the vegetable and animal oxyds and acids may differ from each other in three several ways: 1st, According to the number of simple acidifiable elements of which their radicals are composed: 2dly, According to the proportions in which these are combined together: And, 3dly, According to their different degrees of oxygenation: Which circumstances are more than sufficient to explain the great variety which nature produces in these substances. It is not at all surprising, after this, that most of the vegetable acids are convertible into each other, nothing more being requisite than to change the proportions of the hydrogen and charcoal in their composition, and to oxygenate them in a greater or lesser degree. This has been done by Mr Crell in some very ingenious experiments, which have been verified and extended by Mr Hassenfratz. From these it appears, that charcoal and hydrogen, by a first oxygenation, produce tartarous acid, oxalic acid by a second degree, and acetous or acetic acid by a third, or higher oxygenation; only, that charcoal seems to exist in a rather smaller proportion in the acetous and acetic acids. The citric and malic acids differ little from the preceding acids. Ought we then to conclude that the oils are the radicals of the vegetable and animal acids? I have already expressed my doubts upon this subject: 1st, Although the oils appear to be formed of nothing but hydrogen and charcoal, we do not know if these are in the precise proportion necessary for constituting the radicals of the acids: 2dly, Since oxygen enters into the composition of these acids equally with hydrogen and charcoal, there is no more reason for supposing them to be composed of oil rather than of water or of carbonic acid. It is true that they contain the materials necessary for all these combinations, but then these do not take place in the common temperature of the atmosphere; all the three elements remain combined in a state of equilibrium, which is readily destroyed by a temperature only a little above that of boiling water[39]. TABLE _of the Binary Combinations of Azote with the Simple Substances._ _Simple Substances._ _Results of the Combinations._ _New Nomenclature._ _Old Nomenclature._ Caloric Azotic gas Phlogisticated air, or Mephitis. Hydrogen Ammoniac Volatile alkali. {Nitrous oxyd Base of Nitrous gas. {Nitrous acid Smoaking nitrous acid. Oxygen {Nitric acid Pale nitrous acid. {Oxygenated nitric acid Unknown. {This combination is hitherto unknown; should it {ever be discovered, it will be called, according to Charcoal {the principles of our nomenclature, Azuret of {Charcoal. Charcoal dissolves in azotic gas, and {forms carbonated azotic gas. Phosphorus. Azuret of phosphorus. Still unknown. {Azuret of sulphur. Still unknown. We know Sulphur {that sulphur dissolves in azotic gas, forming {sulphurated azotic gas. {Azote combines with charcoal and hydrogen, and Compound {sometimes with phosphorus, in the compound radicals {oxydable and acidifiable bases, and is generally {contained in the radicals of the animal acids. {Such combinations are hitherto unknown; if ever Metallic {discovered, they will form metallic azurets, as substances {azuret of gold, of silver, &c. Lime { Magnesia { Barytes {Entirely unknown. If ever discovered, they will Argill {form azuret of lime, azuret of magnesia, &c. Potash { Soda { SECT. VI.--_Observations upon the Combinations of Azote with the Simple Substances._ Azote is one of the most abundant elements; combined with caloric it forms azotic gas, or mephitis, which composes nearly two thirds of the atmosphere. This element is always in the state of gas in the ordinary pressure and temperature, and no degree of compression or of cold has been hitherto capable of reducing it either to a solid or liquid form. This is likewise one of the essential constituent elements of animal bodies, in which it is combined with charcoal and hydrogen, and sometimes with phosphorus; these are united together by a certain portion of oxygen, by which they are formed into oxyds or acids according to the degree of oxygenation. Hence the animal substances may be varied, in the same way with vegetables, in three different manners: 1st, According to the number of elements which enter into the composition of the base or radical: 2dly, According to the proportions of these elements: 3dly, According to the degree of oxygenation. When combined with oxygen, azote forms the nitrous and nitric oxyds and acids; when with hydrogen, ammoniac is produced. Its combinations with the other simple elements are very little known; to these we give the name of Azurets, preserving the termination in _uret_ for all nonoxygenated compounds. It is extremely probable that all the alkaline substances may hereafter be found to belong to this genus of azurets. The azotic gas may be procured from atmospheric air, by absorbing the oxygen gas which is mixed with it by means of a solution of sulphuret of potash, or sulphuret of lime. It requires twelve or fifteen days to complete this process, during which time the surface in contact must be frequently renewed by agitation, and by breaking the pellicle which forms on the top of the solution. It may likewise be procured by dissolving animal substances in dilute nitric acid very little heated. In this operation, the azote is disengaged in form of gas, which we receive under bell glasses filled with water in the pneumato-chemical apparatus. We may procure this gas by deflagrating nitre with charcoal, or any other combustible substance; when with charcoal, the azotic gas is mixed with carbonic acid gas, which may be absorbed by a solution of caustic alkali, or by lime water, after which the azotic gas remains pure. We can procure it in a fourth manner from combinations of ammoniac with metallic oxyds, as pointed out by Mr de Fourcroy: The hydrogen of the ammoniac combines with the oxygen of the oxyd, and forms water, whilst the azote being left free escapes in form of gas. The combinations of azote were but lately discovered: Mr Cavendish first observed it in nitrous gas and acid, and Mr Berthollet in ammoniac and the prussic acid. As no evidence of its decomposition has hitherto appeared, we are fully entitled to consider azote as a simple elementary substance. TABLE _of the Binary Combinations of Hydrogen with Simple Substances._ _Simple_ _Resulting Compounds._ _Substances._ _New Nomenclature._ _Old Names._ Caloric Hydrogen gas Inflammable air. Azote Ammoniac Volatile Alkali. Oxygen Water Water. Sulphur {Hydruret of sulphur, or } {sulphuret of hydrogen } Hitherto unknown (A). Phosphorus {Hydruret of phosphorus, or } {phosphuret of hydrogen } Charcoal {Hydro-carbonous, or } Not known till lately. {carbono-hydrous radicals(B)} Metallic {Metallic hydrurets(C), as } Hitherto unknown. substances, {hydruret of iron, &c. } as iron, &c. { } [Note A: These combinations take place in the state of gas, and form, respectively, sulphurated and phosphorated oxygen gas--A.] [Note B: This combination of hydrogen with charcoal includes the fixed and volatile oils, and forms the radicals of a considerable part of the vegetable and animal oxyds and acids. When it takes place in the state of gas it forms carbonated hydrogen gas.--A.] [Note C: None of these combinations are known, and it is probable that they cannot exist, at least in the usual temperature of the atmosphere, owing to the great affinity of hydrogen for caloric.--A.] SECT. VII.--_Observations upon Hydrogen, and its Combinations with Simple Substances._ Hydrogen, as its name expresses, is one of the constituent elements of water, of which it forms fifteen hundredth parts by weight, combined with eighty-five hundredth parts of oxygen. This substance, the properties and even existence of which was unknown till lately, is very plentifully distributed in nature, and acts a very considerable part in the processes of the animal and vegetable kingdoms. As it possesses so great affinity with caloric as only to exist in the state of gas, it is consequently impossible to procure it in the concrete or liquid state, independent of combination. To procure hydrogen, or rather hydrogen gas, we have only to subject water to the action of a substance with which oxygen has greater affinity than it has to hydrogen; by this means the hydrogen is set free, and, by uniting with caloric, assumes the form of hydrogen gas. Red hot iron is usually employed for this purpose: The iron, during the process, becomes oxydated, and is changed into a substance resembling the iron ore from the island of Elba. In this state of oxyd it is much less attractible by the magnet, and dissolves in acids without effervescence. Charcoal, in a red heat, has the same power of decomposing water, by attracting the oxygen from its combination with hydrogen. In this process carbonic acid gas is formed, and mixes with the hydrogen gas, but is easily separated by means of water or alkalies, which absorb the carbonic acid, and leave the hydrogen gas pure. We may likewise obtain hydrogen gas by dissolving iron or zinc in dilute sulphuric acid. These two metals decompose water very slowly, and with great difficulty, when alone, but do it with great ease and rapidity when assisted by sulphuric acid; the hydrogen unites with caloric during the process, and is disengaged in form of hydrogen gas, while the oxygen of the water unites with the metal in the form of oxyd, which is immediately dissolved in the acid, forming a sulphat of iron or of zinc. Some very distinguished chemists consider hydrogen as the _phlogiston_ of Stahl; and as that celebrated chemist admitted the existence of phlogiston in sulphur, charcoal, metals, &c. they are of course obliged to suppose that hydrogen exists in all these substances, though they cannot prove their supposition; even if they could, it would not avail much, since this disengagement of hydrogen is quite insufficient to explain the phenomena of calcination and combustion. We must always recur to the examination of this question, "Are the heat and light, which are disengaged during the different species of combustion, furnished by the burning body, or by the oxygen which combines in all these operations?" And certainly the supposition of hydrogen being disengaged throws no light whatever upon this question. Besides, it belongs to those who make suppositions to prove them; and, doubtless, a doctrine which without any supposition explains the phenomena as well, and as naturally, as theirs does by supposition, has at least the advantage of greater simplicity[40]. TABLE _of the Binary Combinations of Sulphur with Simple Substances._ _Simple_ _Resulting Compounds._ _Substances._ _New Nomenclature._ _Old Nomenclature._ Caloric Sulphuric gas { Oxyd of sulphur Soft sulphur. Oxygen { Sulphurous acid Sulphureous acid. { Sulphuric acid Vitriolic acid. Hydrogen Sulphuret of hydrogen } Azote azote } Unknown Combinations. Phosphorus phosphorus } Charcoal charcoal } Antimony antimony Crude antimony. Silver silver Arsenic arsenic Orpiment, realgar. Bismuth bismuth Cobalt cobalt Copper copper Copper pyrites. Tin tin Iron iron Iron pyrites. Manganese manganese Mercury mercury Ethiops mineral, cinnabar. Molybdena molybdena Nickel nickel Gold gold Platina platina Lead lead Galena. Tungstein tungstein Zinc zinc Blende. { Alkaline liver of sulphur Potash potash { with fixed vegetable alkali. { Alkaline liver of sulphur Soda soda { with fixed mineral { alkali. { Volatile liver of sulphur, Ammoniac ammoniac { smoaking liquor { of Boyle. Lime lime Calcareous liver of sulphur. Magnesia magnesia Magnesian liver of sulphur. Barytes barytes Barytic liver of sulphur. Argill argill Yet unknown. SECT. VIII.--_Observations on Sulphur, and its Combinations._ Sulphur is a combustible substance, having a very great tendency to combination; it is naturally in a solid state in the ordinary temperature, and requires a heat somewhat higher than boiling water to make it liquify. Sulphur is formed by nature in a considerable degree of purity in the neighbourhood of volcanos; we find it likewise, chiefly in the state of sulphuric acid, combined with argill in aluminous schistus, with lime in gypsum, &c. From these combinations it may be procured in the state of sulphur, by carrying off its oxygen by means of charcoal in a red heat; carbonic acid is formed, and escapes in the state of gas; the sulphur remains combined with the clay, lime, &c. in the state of sulphuret, which is decomposed by acids; the acid unites with the earth into a neutral salt, and the sulphur is precipitated. TABLE _of the Binary Combinations of Phosphorus with the Simple Substances._ _Simple Substances._ _Resulting Compounds._ Caloric Phosphoric gas. { Oxyd of phosphorus. Oxygen { Phosphorous acid. { Phosphoric acid. Hydrogen Phosphuret of hydrogen. Azote Phosphuret of azote. Sulphur Phosphuret of Sulphur. Charcoal Phosphuret of charcoal. Metallic substances Phosphuret of metals(A). Potash } Soda } Ammoniac } Phosphuret of Potash, Lime } Soda, &c.(B) Barytes } Magnesia } Argill } [Note A: Of all these combinations of phosphorus with metals, that with iron only is hitherto known, forming the substance formerly called Siderite; neither is it yet ascertained whether, in this combination, the phosphorus be oxygenated or not.--A.] [Note B: These combinations of phosphorus with the alkalies and earths are not yet known; and, from the experiments of Mr Gengembre, they appear to be impossible--A.] SECT. IX.--_Observations upon Phosphorus, and its Combinations._ Phosphorus is a simple combustible substance, which was unknown to chemists till 1667, when it was discovered by Brandt, who kept the process secret; soon after Kunkel found out Brandt's method of preparation, and made it public. It has been ever since known by the name of Kunkel's phosphorus. It was for a long time procured only from urine; and, though Homberg gave an account of the process in the Memoirs of the Academy for 1692, all the philosophers of Europe were supplied with it from England. It was first made in France in 1737, before a committee of the Academy at the Royal Garden. At present it is procured in a more commodious and more oeconomical manner from animal bones, which are real calcareous phosphats, according to the process of Messrs Gahn, Scheele, Rouelle, &c. The bones of adult animals being calcined to whiteness, are pounded, and passed through a fine silk sieve; pour upon the fine powder a quantity of dilute sulphuric acid, less than is sufficient for dissolving the whole. This acid unites with the calcareous earth of the bones into a sulphat of lime, and the phosphoric acid remains free in the liquor. The liquid is decanted off, and the residuum washed with boiling water; this water which has been used to wash out the adhering acid is joined with what was before decanted off, and the whole is gradually evaporated; the dissolved sulphat of lime cristallizes in form of silky threads, which are removed, and by continuing the evaporation we procure the phosphoric acid under the appearance of a white pellucid glass. When this is powdered, and mixed with one third its weight of charcoal, we procure very pure phosphorus by sublimation. The phosphoric acid, as procured by the above process, is never so pure as that obtained by oxygenating pure phosphorus either by combustion or by means of nitric acid; wherefore this latter should always be employed in experiments of research. Phosphorus is found in almost all animal substances, and in some plants which give a kind of animal analysis. In all these it is usually combined with charcoal, hydrogen, and azote, forming very compound radicals, which are, for the most part, in the state of oxyds by a first degree of union with oxygen. The discovery of Mr Hassenfratz, of phosphorus being contained in charcoal, gives reason to suspect that it is more common in the vegetable kingdom than has generally been supposed: It is certain, that, by proper processes, it may be procured from every individual of some of the families of plants. As no experiment has hitherto given reason to suspect that phosphorus is a compound body, I have arranged it with the simple or elementary substances. It takes fire at the temperature of 32° (104°) of the thermometer. TABLE _of the Binary Combinations of Charcoal._ _Simple_ _Substances._ _Resulting Compounds._ { Oxyd of charcoal Unknown. Oxygen { Carbonic acid Fixed air, chalky acid. Sulphur Carburet of sulphur } Phosphorus Carburet of phosphorus } Unknown. Azote Carburet of azote } { Carbono-hydrous radical Hydrogen { Fixed and volatile oils { Of these only the carburets of Metallic substances Carburets of metals { iron and zinc are known, and { were formerly called Plumbago. Alkalies and earths Carburet of potash, &c. Unknown. SECT. X.--_Observations upon Charcoal, and its Combinations with Simple Substances._ As charcoal has not been hitherto decomposed, it must, in the present state of our knowledge, be considered as a simple substance. By modern experiments it appears to exist ready formed in vegetables; and I have already remarked, that, in these, it is combined with hydrogen, sometimes with azote and phosphorus, forming compound radicals, which may be changed into oxyds or acids according to their degree of oxygenation. To obtain the charcoal contained in vegetable or animal substances, we subject them to the action of fire, at first moderate, and afterwards very strong, on purpose to drive off the last portions of water, which adhere very obstinately to the charcoal. For chemical purposes, this is usually done in retorts of stone-ware or porcellain, into which the wood, or other matter, is introduced, and then placed in a reverberatory furnace, raised gradually to its greatest heat: The heat volatilizes, or changes into gas, all the parts of the body susceptible of combining with caloric into that form, and the charcoal, being more fixed in its nature, remains in the retort combined with a little earth and some fixed salts. In the business of charring wood, this is done by a less expensive process. The wood is disposed in heaps, and covered with earth, so as to prevent the access of any more air than is absolutely necessary for supporting the fire, which is kept up till all the water and oil is driven off, after which the fire is extinguished by shutting up all the air-holes. We may analyse charcoal either by combustion in air, or rather in oxygen gas, or by means of nitric acid. In either case we convert it into carbonic acid, and sometimes a little potash and some neutral salts remain. This analysis has hitherto been but little attended to by chemists; and we are not even certain if potash exists in charcoal before combustion, or whether it be formed by means of some unknown combination during that process. SECT. XI.--_Observations upon the Muriatic, Fluoric, and Boracic Radicals, and their Combinations._ As the combinations of these substances, either with each other, or with the other combustible bodies, are hitherto entirely unknown, we have not attempted to form any table for their nomenclature. We only know that these radicals are susceptible of oxygenation, and of forming the muriatic, fluoric, and boracic acids, and that in the acid state they enter into a number of combinations, to be afterwards detailed. Chemistry has hitherto been unable to disoxygenate any of them, so as to produce them in a simple state. For this purpose, some substance must be employed to which oxygen has a stronger affinity than to their radicals, either by means of single affinity, or by double elective attraction. All that is known relative to the origin of the radicals of these acids will be mentioned in the sections set apart for considering their combinations with the salifiable bases. SECT. XII.--_Observations upon the Combinations of Metals with each other._ Before closing our account of the simple or elementary substances, it might be supposed necessary to give a table of alloys or combinations of metals with each other; but, as such a table would be both exceedingly voluminous and very unsatisfactory, without going into a series of experiments not yet attempted, I have thought it adviseable to omit it altogether. All that is necessary to be mentioned is, that these alloys should be named according to the metal in largest proportion in the mixture or combination; thus the term _alloy of gold and silver_, or gold alloyed with silver, indicates that gold is the predominating metal. Metallic alloys, like all other combinations, have a point of saturation. It would even appear, from the experiments of Mr de la Briche, that they have two perfectly distinct degrees of saturation. TABLE _of the Combinations of Azote in the state of Nitrous Acid with the Salifiable Bases, arranged according to the affinities of these Bases with the Acid_. _Names of the bases._ _Names of the neutral salts._ _New nomenclature._ _Notes._ Barytes Nitrite of barytes. { Potash potash. { These salts are only Soda soda. { known of late, and Lime lime. { have received no particular Magnesia magnesia. { name in the old Ammoniac ammoniac. { nomenclature. Argill argill. { { As metals dissolve both in nitrous and Oxyd of zinc zinc. { nitric acids, metallic salts must of iron iron. { consequence be formed having manganese manganese. { different degrees of oxygenation. cobalt cobalt. { Those wherein the metal is nickel nickel. { least oxygenated must be lead lead. { called Nitrites, when more so, tin tin. { Nitrats; but the limits of this copper copper. { distinction are difficultly bismuth bismuth. { ascertainable. The older antimony antimony. { chemists were not acquainted arsenic arsenic. { with any of these salts. mercury mercury. { silver { It is extremely probable that gold, silver gold { and platina only form nitrats, and cannot subsist platina { in the state of nitrites. TABLE _of the Combinations of Azote, completely saturated with Oxygen, in the state of Nitric Acid, with the Salifiable Bases, in the order of the affinity with the Acid_. _Bases._ _Names of the resulting neutral salts._ _New nomenclature._ _Old nomenclature._ Barytes Nitrat of barytes Nitre, with a base of heavy earth. Potash potash Nitre, saltpetre. Nitre with base of potash. Soda soda { Quadrangular nitre. Nitre with base of { mineral alkali. { Calcareous nitre. Nitre with Lime lime { calcareous base. Mother water { of nitre, or saltpetre. Magnesia magnesia Magnesian nitre. Nitre with base of magnesia. Ammoniac ammoniac Ammoniacal nitre. { Nitrous alum. Argillaceous nitre. Nitre Argill argill { with base of earth of alum. Oxyd of zinc zinc Nitre of zinc. iron iron Nitre of iron. Martial nitre. Nitrated iron. manganese manganese Nitre of manganese. cobalt cobalt Nitre of cobalt. nickel nickel Nitre of nickel. lead lead Saturnine nitre. Nitre of lead. tin tin Nitre of tin. copper copper Nitre of copper or of Venus. bismuth bismuth Nitre of bismuth. antimony antimony Nitre of antimony. arsenic arsenic Arsenical nitre. mercury mercury Mercurial nitre. silver silver Nitre of silver or luna. Lunar caustic. gold gold Nitre of gold. platina platina Nitre of platina. SECT. XIII.--_Observations upon the Nitrous and Nitric Acids, and their Combinations._ The nitrous and nitric acids are procured from a neutral salt long known in the arts under the name of _saltpetre_. This salt is extracted by lixiviation from the rubbish of old buildings, from the earth of cellars, stables, or barns, and in general of all inhabited places. In these earths the nitric acid is usually combined with lime and magnesia, sometimes with potash, and rarely with argill. As all these salts, excepting the nitrat of potash, attract the moisture of the air, and consequently would be difficultly preserved, advantage is taken, in the manufactures of saltpetre and the royal refining house, of the greater affinity of the nitric acid to potash than these other bases, by which means the lime, magnesia, and argill, are precipitated, and all these nitrats are reduced to the nitrat of potash or saltpetre[41]. The nitric acid is procured from this salt by distillation, from three parts of pure saltpetre decomposed by one part of concentrated sulphuric acid, in a retort with Woulfe's apparatus, (Pl. IV. fig. 1.) having its bottles half filled with water, and all its joints carefully luted. The nitrous acid passes over in form of red vapours surcharged with nitrous gas, or, in other words, not saturated with oxygen. Part of the acid condenses in the recipient in form of a dark orange red liquid, while the rest combines with the water in the bottles. During the distillation, a large quantity of oxygen gas escapes, owing to the greater affinity of oxygen to caloric, in a high temperature, than to nitrous acid, though in the usual temperature of the atmosphere this affinity is reversed. It is from the disengagement of oxygen that the nitric acid of the neutral salt is in this operation converted into nitrous acid. It is brought back to the state of nitric acid by heating over a gentle fire, which drives off the superabundant nitrous gas, and leaves the nitric acid much diluted with water. Nitric acid is procurable in a more concentrated state, and with much less loss, by mixing very dry clay with saltpetre. This mixture is put into an earthern retort, and distilled with a strong fire. The clay combines with the potash, for which it has great affinity, and the nitric acid passes over, slightly impregnated with nitrous gas. This is easily disengaged by heating the acid gently in a retort, a small quantity of nitrous gas passes over into the recipient, and very pure concentrated nitric acid remains in the retort. We have already seen that azote is the nitric radical. If to 20-1/2 parts, by weight, of azote 43-1/2 parts of oxygen be added, 64 parts of nitrous gas are formed; and, if to this we join 36 additional parts of oxygen, 100 parts of nitric acid result from the combination. Intermediate quantities of oxygen between these two extremes of oxygenation produce different species of nitrous acid, or, in other words, nitric acid less or more impregnated with nitrous gas. I ascertained the above proportions by means of decomposition; and, though I cannot answer for their absolute accuracy, they cannot be far removed from truth. Mr Cavendish, who first showed by synthetic experiments that azote is the base of nitric acid, gives the proportions of azote a little larger than I have done; but, as it is not improbable that he produced the nitrous acid and not the nitric, that circumstance explains in some degree the difference in the results of our experiments. As, in all experiments of a philosophical nature, the utmost possible degree of accuracy is required, we must procure the nitric acid for experimental purposes, from nitre which has been previously purified from all foreign matter. If, after distillation, any sulphuric acid is suspected in the nitric acid, it is easily separated by dropping in a little nitrat of barytes, so long as any precipitation takes place; the sulphuric acid, from its greater affinity, attracts the barytes, and forms with it an insoluble neutral salt, which falls to the bottom. It may be purified in the same manner from muriatic acid, by dropping in a little nitrat of silver so long as any precipitation of muriat of silver is produced. When these two precipitations are finished, distill off about seven-eighths of the acid by a gentle heat, and what comes over is in the most perfect degree of purity. The nitric acid is one of the most prone to combination, and is at the same time very easily decomposed. Almost all the simple substances, with the exception of gold, silver, and platina, rob it less or more of its oxygen; some of them even decompose it altogether. It was very anciently known, and its combinations have been more studied by chemists than those of any other acid. These combinations were named _nitres_ by Messrs Macquer and Beaumé; but we have changed their names to nitrats and nitrites, according as they are formed by nitric or by nitrous acid, and have added the specific name of each particular base, to distinguish the several combinations from each other. TABLE _of the Combinations of Sulphuric Acid with the Salifiable Bases, in the order of affinity._ _Names of the bases._ _Resulting compounds._ _New nomenclature._ _Old nomenclature._ Barytes Sulphat of barytes Heavy spar. Vitriol of heavy earth. Potash potash {Vitriolated tartar. Sal { de duobus. Arcanum { duplicatam. Soda soda Glauber's salt. Lime lime Selenite, gypsum, calcareous vitriol. Magnesia magnesia Epsom salt, sedlitz salt, magnesian vitriol. Ammoniac ammoniac Glauber's secret sal ammoniac. Argill argill Alum. Oxyd of zinc zinc {White vitriol, goslar { vitriol, white coperas, { vitriol of zinc. iron iron {Green coperas, green { vitriol, martial vitriol, { vitriol of iron. manganese manganese Vitriol of manganese. cobalt cobalt Vitriol of cobalt. nickel nickel Vitriol of nickel. lead lead Vitriol of lead. tin tin Vitriol of tin. copper copper {Blue coperas, blue vitriol, { Roman vitriol, { vitriol of copper. bismuth bismuth Vitriol of bismuth. antimony antimony Vitriol of antimony. arsenic arsenic Vitriol of arsenic. mercury mercury Vitriol of mercury. silver silver Vitriol of silver. gold gold Vitriol of gold. platina platina Vitriol of platina. SECT. XIV.--_Observations upon Sulphuric Acid and its Combinations._ For a long time this acid was procured by distillation from sulphat of iron, in which sulphuric acid and oxyd of iron are combined, according to the process described by Basil Valentine in the fifteenth century; but, in modern times, it is procured more oeconomically by the combustion of sulphur in proper vessels. Both to facilitate the combustion, and to assist the oxygenation of the sulphur, a little powdered saltpetre, nitrat of potash, is mixed with it; the nitre is decomposed, and gives out its oxygen to the sulphur, which contributes to its conversion into acid. Notwithstanding this addition, the sulphur will only continue to burn in close vessels for a limited time; the combination ceases, because the oxygen is exhausted, and the air of the vessels reduced almost to pure azotic gas, and because the acid itself remains long in the state of vapour, and hinders the progress of combustion. In the manufactories for making sulphuric acid in the large way, the mixture of nitre and sulphur is burnt in large close built chambers lined with lead, having a little water at the bottom for facilitating the condensation of the vapours. Afterwards, by distillation in large retorts with a gentle heat, the water passes over, slightly impregnated with acid, and the sulphuric acid remains behind in a concentrated state. It is then pellucid, without any flavour, and nearly double the weight of an equal bulk of water. This process would be greatly facilitated, and the combustion much prolonged, by introducing fresh air into the chambers, by means of several pairs of bellows directed towards the flame of the sulphur, and by allowing the nitrous gas to escape through long serpentine canals, in contact with water, to absorb any sulphuric or sulphurous acid gas it might contain. By one experiment, Mr Berthollet found that 69 parts of sulphur in combustion, united with 31 parts of oxygen, to form 100 parts of sulphuric acid; and, by another experiment, made in a different manner, he calculates that 100 parts of sulphuric acid consists of 72 parts sulphur, combined with 28 parts of oxygen, all by weight. This acid, in common with every other, can only dissolve metals when they have been previously oxydated; but most of the metals are capable of decomposing a part of the acid, so as to carry off a sufficient quantity of oxygen, to render themselves soluble in the part of the acid which remains undecomposed. This happens with silver, mercury, iron, and zinc, in boiling concentrated sulphuric acid; they become first oxydated by decomposing part of the acid, and then dissolve in the other part; but they do not sufficiently disoxygenate the decomposed part of the acid to reconvert it into sulphur; it is only reduced to the state of sulphurous acid, which, being volatilised by the heat, flies off in form of sulphurous acid gas. Silver, mercury, and all the other metals except iron and zinc, are insoluble in diluted sulphuric acid, because they have not sufficient affinity with oxygen to draw it off from its combination either with the sulphur, the sulphurous acid, or the hydrogen; but iron and zinc, being assisted by the action of the acid, decompose the water, and become oxydated at its expence, without the help of heat. TABLE _of the Combinations of the Sulphurous Acid with the Salifiable Bases, in the order of affinity._ _Names of the Bases._ _Names of the Neutral Salts._ Barytes Sulphite of barytes. Potash potash. Soda soda. Lime lime. Magnesia magnesia. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. tin tin. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. mercury mercury. silver silver. gold gold. platina platina. _Note._--The only one of these salts known to the old chemists was the sulphite of potash, under the name of _Stahl's sulphureous salt_. So that, before our new nomenclature, these compounds must have been named _Stahl's sulphureous salt_, having base of fixed vegetable alkali, and so of the rest. In this Table we have followed Bergman's order of affinity of the sulphuric acid, which is the same in regard to the earths and alkalies, but it is not certain if the order be the same for the metallic oxyds.--A. SECT. XV.--_Observations upon Sulphurous Acid, and its Combinations._ The sulphurous acid is formed by the union of oxygen with sulphur by a lesser degree of oxygenation than the sulphuric acid. It is procurable either by burning sulphur slowly, or by distilling sulphuric acid from silver, antimony, lead, mercury, or charcoal; by which operation a part of the oxygen quits the acid, and unites to these oxydable bases, and the acid passes over in the sulphurous state of oxygenation. This acid, in the common pressure and temperature of the air, can only exist in form of gas; but it appears, from the experiments of Mr Clouet, that, in a very low temperature, it condenses, and becomes fluid. Water absorbs a great deal more of this gas than of carbonic acid gas, but much less than it does of muriatic acid gas. That the metals cannot be dissolved in acids without being previously oxydated, or by procuring oxygen, for that purpose, from the acids during solution, is a general and well established fact, which I have perhaps repeated too often. Hence, as sulphurous acid is already deprived of great part of the oxygen necessary for forming the sulphuric acid, it is more disposed to recover oxygen, than to furnish it to the greatest part of the metals; and, for this reason, it cannot dissolve them, unless previously oxydated by other means. From the same principle it is that the metallic oxyds dissolve without effervescence, and with great facility, in sulphurous acid. This acid, like the muriatic, has even the property of dissolving metallic oxyds surcharged with oxygen, and consequently insoluble in sulphuric acid, and in this way forms true sulphats. Hence we might be led to conclude that there are no metallic sulphites, were it not that the phenomena which accompany the solution of iron, mercury, and some other metals, convince us that these metallic substances are susceptible of two degrees of oxydation, during their solution in acids. Hence the neutral salt in which the metal is least oxydated must be named _sulphite_, and that in which it is fully oxydated must be called _sulphat_. It is yet unknown whether this distinction is applicable to any of the metallic sulphats, except those of iron and mercury. TABLE _of the Combinations of Phosphorous and Phosphoric Acids, with the Salifiable Bases, in the Order of Affinity._ _Names of the_ _Names of the Neutral Salts formed by_ _Bases._ _Phosphorous Acid,_ _Phosphoric Acid._ Phosphites of(B) Phosphats of(C) Lime lime lime. Barytes barytes barytes. Magnesia magnesia magnesia. Potash potash potash. Soda soda soda. Ammoniac ammoniac ammoniac. Argill argill argill. Oxyds of(A) zinc zinc zinc. iron iron iron. manganese manganese manganese. cobalt cobalt cobalt. nickel nickel nickel. lead lead lead. tin tin tin. copper copper copper. bismuth bismuth bismuth. antimony antimony antimony. arsenic arsenic arsenic. mercury mercury mercury. silver silver silver. gold gold gold. platina platina platina. [Note A: The existence of metallic phosphites supposes that metals are susceptible of solution in phosphoric acid at different degrees of oxygenation, which is not yet ascertained.--A.] [Note B: All the phosphites were unknown till lately, and consequently have not hitherto received names.--A.] [Note C: The greater part of the phosphats were only discovered of late, and have not yet been named.--A.] SECT. XVI.--_Observations upon Phosphorous and Phosphoric Acids, and their Combinations._ Under the article Phosphorus, Part II. Sect. X. we have already given a history of the discovery of that singular substance, with some observations upon the mode of its existence in vegetable and animal bodies. The best method of obtaining this acid in a state of purity is by burning well purified phosphorus under bell-glasses, moistened on the inside with distilled water; during combustion it absorbs twice and a half its weight of oxygen; so that 100 parts of phosphoric acid is composed of 28-1/2 parts of phosphorus united to 71-1/2 parts of oxygen. This acid may be obtained concrete, in form of white flakes, which greedily attract the moisture of the air, by burning phosphorus in a dry glass over mercury. To obtain phosphorous acid, which is phosphorus less oxygenated than in the state of phosphoric acid, the phosphorus must be burnt by a very slow spontaneous combustion over a glass-funnel leading into a crystal phial; after a few days, the phosphorus is found oxygenated, and the phosphorous acid, in proportion as it forms, has attracted moisture from the air, and dropped into the phial. The phosphorous acid is readily changed into phosphoric acid by exposure for a long time to the free air; it absorbs oxygen from the air, and becomes fully oxygenated. As phosphorus has a sufficient affinity for oxygen to attract it from the nitric and muriatic acids, we may form phosphoric acid, by means of these acids, in a very simple and cheap manner. Fill a tubulated receiver, half full of concentrated nitric acid, and heat it gently, then throw in small pieces of phosphorus through the tube, these are dissolved with effervescence and red fumes of nitrous gas fly off; add phosphorus so long as it will dissolve, and then increase the fire under the retort to drive off the last particles of nitric acid; phosphoric acid, partly fluid and partly concrete, remains in the retort. TABLE _of the Combinations of Carbonic Acid, with the Salifiable Bases, in the Order of Affinity._ _Names of_ _Resulting Neutral Salts._ _Bases_ _New Nomenclature._ _Old Nomenclature._ Barytes Carbonates of barytes(A) Aërated or effervescent heavy earth. Lime lime {Chalk, calcareous spar, { Aërated calcareous earth. Potash potash {Effervescing or aërated fixe { vegetable alkali, mephitis of { potash. Soda soda {Aërated or effervescing fixed mineral { alkali, mephitic soda. Magnesia magnesia {Aërated, effervescing, mild, or { mephitic magnesia. Ammoniac ammoniac {Aërated, effervescing, mild, or { mephitic volatile alkali. Argill argill {Aërated or effervescing argillaceous { earth, or earth of alum. Oxyds of zinc zinc Zinc spar, mephitic or aërated zinc. iron iron Sparry iron-ore, mephitic or aërated iron. manganese manganese Aërated manganese. cobalt cobalt Aërated cobalt. nickel nickel Aërated nickel. lead lead Sparry lead-ore, or aërated lead. tin tin Aërated tin. copper copper Aërated copper. bismuth bismuth Aërated bismuth. antimony antimony Aërated antimony. arsenic arsenic Aërated arsenic. mercury mercury Aërated mercury. silver silver Aërated silver. gold gold Aërated gold. platina platina Aërated platina. [Note A: As these salts have only been understood of late, they have not, properly speaking, any old names. Mr Morveau, in the First Volume of the Encyclopedia, calls them _Mephites_; Mr Bergman gives them the name of _aërated_; and Mr de Fourcroy, who calls the carbonic acid _chalky acid_, gives them the name of _chalks_.--A] SECT. XVII.--_Observations upon Carbonic Acid, and its Combinations._ Of all the known acids, the carbonic is the most abundant in nature; it exists ready formed in chalk, marble, and all the calcareous stones, in which it is neutralized by a particular earth called _lime_. To disengage it from this combination, nothing more is requisite than to add some sulphuric acid, or any other which has a stronger affinity for lime; a brisk effervescence ensues, which is produced by the disengagement of the carbonic acid which assumes the state of gas immediately upon being set free. This gas, incapable of being condensed into the solid or liquid form by any degree of cold or of pressure hitherto known, unites to about its own bulk of water, and thereby forms a very weak acid. It may likewise be obtained in great abundance from saccharine matter in fermentation, but is then contaminated by a small portion of alkohol which it holds in solution. As charcoal is the radical of this acid, we may form it artificially, by burning charcoal in oxygen gas, or by combining charcoal and metallic oxyds in proper proportions; the oxygen of the oxyd combines with the charcoal, forming carbonic acid gas, and the metal being left free, recovers its metallic or reguline form. We are indebted for our first knowledge of this acid to Dr Black, before whose time its property of remaining always in the state of gas had made it to elude the researches of chemistry. It would be a most valuable discovery to society, if we could decompose this gas by any cheap process, as by that means we might obtain, for economical purposes, the immense store of charcoal contained in calcareous earths, marbles, limestones, &c. This cannot be effected by single affinity, because, to decompose the carbonic acid, it requires a substance as combustible as charcoal itself, so that we should only make an exchange of one combustible body for another not more valuable; but it may possibly be accomplished by double affinity, since this process is so readily performed by Nature, during vegetation, from the most common materials. TABLE _of the Combinations of Muriatic Acid, with the Salifiable Bases, in the Order of Affinity._ _Names of the_ _Resulting Neutral Salts._ _bases._ _New nomenclature._ _Old nomenclature._ Barytes. Muriat of {Sea-salt, having base of barytes { heavy earth. Potash potash {Febrifuge salt of Sylvius: { Muriated vegetable fixed { alkali. Soda soda Sea-salt. Lime lime Muriated lime. Oil of lime. Magnesia magnesia {Marine Epsom salt. Muriated magnesia. Ammoniac ammoniac Sal ammoniac. Argill argill {Muriated alum, sea-salt { with base of earth of alum. Oxyd of zinc zinc Sea-salt of, or muriatic zinc. iron iron Salt of iron, Martial sea-salt. manganese manganese Sea-salt of manganese. cobalt cobalt Sea-salt of cobalt. nickel nickel Sea-salt of nickel. lead lead Horny-lead. Plumbum corneum. tin smoaking of tin Smoaking liquor of Libavius. solid of tin Solid butter of tin. copper copper Sea-salt of copper. bismuth bismuth Sea-salt of bismuth. antimony antimony Sea-salt of antimony. arsenic arsenic Sea-salt of arsenic. {sweet of mercury {Sweet sublimate of mercury, { { calomel, aquila alba. mercury { { {corrosive of {Corrosive sublimate of { mercury { mercury. silver silver Horny silver, argentum corneum, luna cornea. gold gold Sea-salt of gold. platina platina Sea-salt of platina. TABLE _Of the Combinations of Oxygenated Muriatic Acid, with the Salifiable Bases, in the Order of Affinity._ _Names of the Neutral Salts by_ _Names of the Bases._ _the new Nomenclature._ Oxygenated muriat of Barytes barytes. Potash potash. Soda soda. Lime lime. Magnesia magnesia. Argill argill. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. tin tin. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. mercury mercury. silver silver. gold gold. platina platina. This order of salts, entirely unknown to the ancient chemists, was discovered in 1786 by Mr Berthollet.--A. SECT. XIX.--_Observations upon Muriatic and Oxygenated Muriatic Acids, and their Combinations._ Muriatic acid is very abundant in the mineral kingdom naturally combined with different salifiable bases, especially with soda, lime, and magnesia. In sea-water, and the water of several lakes, it is combined with these three bases, and in mines of rock-salt it is chiefly united to soda. This acid does not appear to have been hitherto decomposed in any chemical experiment; so that we have no idea whatever of the nature of its radical, and only conclude, from analogy with the other acids, that it contains oxygen as its acidifying principle. Mr Berthollet suspects the radical to be of a metallic nature; but, as Nature appears to form this acid daily, in inhabited places, by combining miasmata with aëriform fluids, this must necessarily suppose a metallic gas to exist in the atmosphere, which is certainly not impossible, but cannot be admitted without proof. The muriatic acid has only a moderate adherence to the salifiable bases, and can readily be driven from its combination with these by sulphuric acid. Other acids, as the nitric, for instance, may answer the same purpose; but nitric acid being volatile, would mix, during distillation, with the muriatic. About one part of sulphuric acid is sufficient to decompose two parts of decrepitated sea-salt. This operation is performed in a tubulated retort, having Woulfe's apparatus, (Pl. IV. Fig. 1.), adapted to it. When all the junctures are properly lured, the sea-salt is put into the retort through the tube, the sulphuric acid is poured on, and the opening immediately closed with its ground crystal stopper. As the muriatic acid can only subsist in the gaseous form in the ordinary temperature, we could not condense it without the presence of water. Hence the use of the water with which the bottles in Woulfe's apparatus are half filled; the muriatic acid gas, driven off from the sea-salt in the retort, combines with the water, and forms what the old chemists called _smoaking spirit of salt_, or _Glauber's spirit of sea-salt_, which we now name _muriatic acid_. The acid obtained by the above process is still capable of combining with a farther dose of oxygen, by being distilled from the oxyds of manganese, lead, or mercury, and the resulting acid, which we name _oxygenated muriatic acid_, can only, like the former, exist in the gasseous form, and is absorbed, in a much smaller quantity by water. When the impregnation of water with this gas is pushed beyond a certain point, the superabundant acid precipitates to the bottom of the vessels in a concrete form. Mr Berthollet has shown that this acid is capable of combining with a great number of the salifiable bases; the neutral salts which result from this union are susceptible of deflagrating with charcoal, and many of the metallic substances; these deflagrations are very violent and dangerous, owing to the great quantity of caloric which the oxygen carries alongst with it into the composition of oxygenated muriatic acid. TABLE _of the Combinations of Nitro-muriatic Acid with the Salifiable Bases, in the Order of Affinity, so far as is known._ _Names of the Bases._ _Names of the Neutral Salts._ Argill Nitro-muriat of argill. Ammoniac ammoniac. Oxyd of antimony antimony. silver silver. arsenic arsenic. Barytes barytes. Oxyd of bismuth bismuth. Lime lime. Oxyd of cobalt cobalt. copper copper. tin tin. iron iron. Magnesia magnesia. Oxyd of manganese manganese. mercury mercury. molybdena molybdena. nickel nickel. gold gold. platina platina. lead lead. Potash potash. Soda soda. Oxyd of tungstein tungstein. zinc zinc. _Note._--Most of these combinations, especially those with the earths and alkalies, have been little examined, and we are yet to learn whether they form a mixed salt in which the compound radical remains combined, or if the two acids separate, to form two distinct neutral salts.--A. SECT. XX.--_Observations upon the Nitro-Muriatic Acid, and its Combinations._ The nitro-muriatic acid, formerly called _aqua regia_, is formed by a mixture of nitric and muriatic acids; the radicals of these two acids combine together, and form a compound base, from which an acid is produced, having properties peculiar to itself, and distinct from those of all other acids, especially the property of dissolving gold and platina. In dissolutions of metals in this acid, as in all other acids, the metals are first oxydated by attracting a part of the oxygen from the compound radical. This occasions a disengagement of a particular species of gas not hitherto described, which may be called _nitro-muriatic gas_; it has a very disagreeable smell, and is fatal to animal life when respired; it attacks iron, and causes it to rust; it is absorbed in considerable quantity by water, which thereby acquires some slight characters of acidity. I had occasion to make these remarks during a course of experiments upon platina, in which I dissolved a considerable quantity of that metal in nitro-muriatic acid. I at first suspected that, in the mixture of nitric and muriatic acids, the latter attracted a part of the oxygen from the former, and became converted into oxygenated muriatic acid, which gave it the property of dissolving gold; but several facts remain inexplicable upon this supposition. Were it so, we must be able to disengage nitrous gas by heating this acid, which however does not sensibly happen. From these considerations, I am led to adopt the opinion of Mr Berthollet, and to consider nitro-muriatic acid as a single acid, with a compound base or radical. TABLE _of the Combinations of Fluoric Acid, with the Salifiable Bases, in the Order of Affinity._ _Names of the Bases._ _Names of the Neutral Salts._ Lime Fluat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. mercury mercury. silver silver. gold gold. platina platina. And by the dry way, Argill Fluat of argill. _Note._--These combinations were entirely unknown to the old chemists, and consequently have no names in the old nomenclature.--A. SECT. XXI.--_Observations upon the Fluoric Acid, and its Combinations._ Fluoric exists ready formed by Nature in the fluoric spars[42], combined with calcareous earth, so as to form an insoluble neutral salt. To obtain it disengaged from that combination, fluor spar, or fluat of lime, is put into a leaden retort, with a proper quantity of sulphuric acid, a recipient likewise of lead, half full of water, is adapted, and fire is applied to the retort. The sulphuric acid, from its greater affinity, expels the fluoric acid which passes over and is absorbed by the water in the receiver. As fluoric acid is naturally in the gasseous form in the ordinary temperature, we can receive it in a pneumato-chemical apparatus over mercury. We are obliged to employ metallic vessels in this process, because fluoric acid dissolves glass and silicious earth, and even renders these bodies volatile, carrying them over with itself in distillation in the gasseous form. We are indebted to Mr Margraff for our first acquaintance with this acid, though, as he could never procure it free from combination with a considerable quantity of silicious earth, he was ignorant of its being an acid sui generis. The Duke de Liancourt, under the name of Mr Boulanger, considerably increased our knowledge of its properties; and Mr Scheele seems to have exhausted the subject. The only thing remaining is to endeavour to discover the nature of the fluoric radical, of which we cannot hitherto form any ideas, as the acid does not appear to have been decomposed in any experiment. It is only by means of compound affinity that experiments ought to be made with this view, with any probability of success. TABLE _of the Combinations of Boracic Acid, with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Lime Borat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Oxyd of zinc zinc. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. mercury mercury. Argill argill. _Note._--Most of these combinations were neither known nor named by the old chemists. The boracic acid was formerly called _sedative salt_, and its compounds _borax_, with base of fixed vegetable alkali, &c.--A. SECT. XXII.--_Observations upon Boracic Add and its Combinations._ This is a concrete acid, extracted from a salt procured from India called _borax_ or _tincall_. Although borax has been very long employed in the arts, we have as yet very imperfect knowledge of its origin, and of the methods by which it is extracted and purified; there is reason to believe it to be a native salt, found in the earth in certain parts of the east, and in the water of some lakes. The whole trade of borax is in the hands of the Dutch, who have been exclusively possessed of the art of purifying it till very lately, that Messrs L'Eguillier of Paris have rivalled them in the manufacture; but the process still remains a secret to the world. By chemical analysis we learn that borax is a neutral salt with excess of base, consisting of soda, partly saturated with a peculiar acid long called _Homberg's sedative salt_, now _the boracic acid_. This acid is found in an uncombined state in the waters of certain lakes. That of Cherchiais in Italy contains 94-1/2 grains in each pint of water. To obtain boracic acid, dissolve some borax in boiling water, filtrate the solution, and add sulphuric acid, or any other having greater affinity to soda than the boracic acid; this latter acid is separated, and is procured in a crystalline form by cooling. This acid was long considered as being formed during the process by which it is obtained, and was consequently supposed to differ according to the nature of the acid employed in separating it from the soda; but it is now universally acknowledged that it is identically the same acid, in whatever way procured, provided it be properly purified from mixture of other acids, by warning, and by repeated solution and cristallization. It is soluble both in water and alkohol, and has the property of communicating a green colour to the flame of that spirit. This circumstance led to a suspicion of its containing copper, which is not confirmed by any decisive experiment. On the contrary, if it contain any of that metal, it must only be considered as an accidental mixture. It combines with the salifiable bases in the humid way; and though, in this manner, it is incapable of dissolving any of the metals directly, this combination is readily affected by compound affinity. The Table presents its combinations in the order of affinity in the humid way; but there is a considerable change in the order when we operate via sicca; for, in that case, argill, though the last in our list, must be placed immediately after soda. The boracic radical is hitherto unknown; no experiments having as yet been able to decompose the acid; We conclude, from analogy with the other acids, that oxygen exists in its composition as the acidifying principle. TABLE _of the Combinations of Arseniac Acid, with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Lime Arseniat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. bismuth bismuth. mercury mercury. antimony antimony. silver silver. gold gold. platina platina. Argill argill. _Note._--This order of salts was entirely unknown to the antient chemists. Mr Macquer, in 1746, discovered the combinations of arseniac acid with potash and soda, to which he gave the name of _arsenical neutral salts_.--A. SECT. XXIII.--_Observations upon Arseniac Acid, and its Combinations._ In the Collections of the Academy for 1746, Mr Macquer shows that, when a mixture of white oxyd of arsenic and nitre are subjected to the action of a strong fire, a neutral salt is obtained, which he calls _neutral salt of arsenic_. At that time, the cause of this singular phenomenon, in which a metal acts the part of an acid, was quite unknown; but more modern experiments teach that, during this process, the arsenic becomes oxygenated, by carrying off the oxygen of the nitric acid; it is thus converted into a real acid, and combines with the potash. There are other methods now known for oxygenating arsenic, and obtaining its acid free from combination. The most simple and most effectual of these is as follows: Dissolve white oxyd of arsenic in three parts, by weight, of muriatic acid; to this solution, in a boiling state, add two parts of nitric acid, and evaporate to dryness. In this process the nitric acid is decomposed, its oxygen unites with the oxyd of arsenic, and converts it into an acid, and the nitrous radical flies off in the state of nitrous gas; whilst the muriatic acid is converted by the heat into muriatic acid gas, and may be collected in proper vessels. The arseniac acid is entirely freed from the other acids employed during the process by heating it in a crucible till it begins to grow red; what remains is pure concrete arseniac acid. Mr Scheele's process, which was repeated with great success by Mr Morveau, in the laboratory at Dijon, is as follows: Distil muriatic acid from the black oxyd of manganese, this converts it into oxygenated muriatic acid, by carrying off the oxygen from the manganese, receive this in a recipient containing white oxyd of arsenic, covered by a little distilled water; the arsenic decomposes the oxygenated muriatic acid, by carrying off its supersaturation of oxygen, the arsenic is converted into arseniac acid, and the oxygenated muriatic acid is brought back to the state of common muriatic acid. The two acids are separated by distillation, with a gentle heat increased towards the end of the operation, the muriatic acid passes over, and the arseniac acid remains behind in a white concrete form. The arseniac acid is considerably less volatile than white oxyd of arsenic; it often contains white oxyd of arsenic in solution, owing to its not being sufficiently oxygenated; this is prevented by continuing to add nitrous acid, as in the former process, till no more nitrous gas is produced. From all these observations I would give the following definition of arseniac acid. It is a white concrete metallic acid, formed by the combination of arsenic with oxygen, fixed in a red heat, soluble in water, and capable of combining with many of the salifiable bases. SECT. XXIV.--_Observations upon Molybdic Acid, and its Combinations with Acidifiable Bases[43]._ Molybdena is a particular metallic body, capable of being oxygenated, so far as to become a true concrete acid[44]. For this purpose, one part ore of molybdena, which is a natural sulphuret of that metal, is put into a retort, with five or six parts nitric acid, diluted with a quarter of its weight of water, and heat is applied to the retort; the oxygen of the nitric acid acts both upon the molybdena and the sulphur, converting the one into molybdic, and the other into sulphuric acid; pour on fresh quantities of nitric acid so long as any red fumes of nitrous gas escape; the molydbena is then oxygenated as far as is possible, and is found at the bottom of the retort in a pulverulent form, resembling chalk. It must be washed in warm water, to separate any adhering particles of sulphuric acid; and, as it is hardly soluble, we lose very little of it in this operation. All its combinations with salifiable bases were unknown to the ancient chemists. TABLE _of the Combinations of Tungstic Acid with the Salifiable Bases._ _Bases._ _Neutral Salts._ Lime Tungstat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Argill argill. Oxyd of antimony(A), &c. antimony(B), &c. [Note A: The combinations with metallic oxyds were set down by Mr Lavoisier in alphabetical order; their order of affinity being unknown, I have omitted them, as serving no purpose.--E.] [Note B: All these salts were unknown to the ancient chemists.--A.] SECT. XXV.--_Observations upon Tungstic Acid, and its Combinations._ Tungstein is a particular metal, the ore of which has frequently been confounded with that of tin. The specific gravity of this ore is to water as 6 to 1; in its form of cristallization it resembles the garnet, and varies in colour from a pearl-white to yellow and reddish; it is found in several parts of Saxony and Bohemia. The mineral called _Wolfram_, which is frequent in the mines of Cornwal, is likewise an ore of this metal. In all these ores the metal is oxydated; and, in some of them, it appears even to be oxygenated to the state of acid, being combined with lime into a true tungstat of lime. To obtain the acid free, mix one part of ore of tungstein with four parts of carbonat of potash, and melt the mixture in a crucible, then powder and pour on twelve parts of boiling water, add nitric acid, and the tungstic acid precipitates in a concrete form. Afterwards, to insure the complete oxygenation of the metal, add more nitric acid, and evaporate to dryness, repeating this operation so long as red fumes of nitrous gas are produced. To procure tungstic acid perfectly pure, the fusion of the ore with carbonat of potash must be made in a crucible of platina, otherwise the earth of the common crucibles will mix with the products, and adulterate the acid. TABLE _of the Combinations of Tartarous Acid, with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Lime Tartarite of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. tin tin. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. silver silver. mercury mercury. gold gold. platina platina. SECT. XXVI.--_Observations upon Tartarous Acid, and its Combinations._ Tartar, or the concretion which fixes to the inside of vessels in which the fermentation of wine is completed, is a well known salt, composed of a peculiar acid, united in considerable excess to potash. Mr Scheele first pointed out the method of obtaining this acid pure. Having observed that it has a greater affinity to lime than to potash, he directs us to proceed in the following manner. Dissolve purified tartar in boiling water, and add a sufficient quantity of lime till the acid be completely saturated. The tartarite of lime which is formed, being almost insoluble in cold water, falls to the bottom, and is separated from the solution of potash by decantation; it is afterwards washed in cold water, and dried; then pour on some sulphuric acid, diluted with eight or nine parts of water, digest for twelve hours in a gentle heat, frequently stirring the mixture; the sulphuric acid combines with the lime, and the tartarous acid is left free. A small quantity of gas, not hitherto examined, is disengaged during this process. At the end of twelve hours, having decanted off the clear liquor, wash the sulphat of lime in cold water, which add to the decanted liquor, then evaporate the whole, and the tartarous acid is obtained in a concrete form. Two pounds of purified tartar, by means of from eight to ten ounces of sulphuric acid, yield about eleven ounces of tartarous acid. As the combustible radical exists in excess, or as the acid from tartar is not fully saturated with oxygen, we call it _tartarous acid_, and the neutral salts formed by its combinations with salifiable bases _tartarites_. The base of the tartarous acid is a carbono-hydrous or hydro-carbonous radical, less oxygenated than in the oxalic acid; and it would appear, from the experiments of Mr Hassenfratz, that azote enters into the composition of the tartarous radical, even in considerable quantity. By oxygenating the tartarous acid, it is convertible into oxalic, malic, and acetous acids; but it is probable the proportions of hydrogen and charcoal in the radical are changed during these conversions, and that the difference between these acids does not alone consist in the different degrees of oxygenation. The tartarous acid is susceptible of two degrees of saturation in its combinations with the fixed alkalies; by one of these a salt is formed with excess of acid, improperly called _cream of tartar_, which in our new nomenclature is named _acidulous tartarite of potash_; by a second or equal degree of saturation a perfectly neutral salt is formed, formerly called _vegetable salt_, which we name _tartarite of potash_. With soda this acid forms tartarite of soda, formerly called _sal de Seignette_, or _sal polychrest of Rochell_. SECT. XXVII.--_Observations upon Malic Acid, and its Combinations with the Salifiable Bases[45]._ The malic acid exists ready formed in the sour juice of ripe and unripe apples, and many other fruits, and is obtained as follows: Saturate the juice of apples with potash or soda, and add a proper proportion of acetite of lead dissolved in water; a double decomposition takes place, the malic acid combines with the oxyd of lead and precipitates, being almost insoluble, and the acetite of potash or soda remains in the liquor. The malat of lead being separated by decantation, is washed with cold water, and some dilute sulphuric acid is added; this unites with the lead into an insoluble sulphat, and the malic acid remains free in the liquor. This acid, which is found mixed with citric and tartarous acid in a great number of fruits, is a kind of medium between oxalic and acetous acids being more oxygenated than the former, and less so than the latter. From this circumstance, Mr Hermbstadt calls it _imperfect vinegar_; but it differs likewise from acetous acid, by having rather more charcoal, and less hydrogen, in the composition of its radical. When an acid much diluted has been used in the foregoing process, the liquor contains oxalic as well as malic acid, and probably a little tartarous, these are separated by mixing lime-water with the acids, oxalat, tartarite, and malat of lime are produced; the two former, being insoluble, are precipitated, and the malat of lime remains dissolved; from this the pure malic acid is separated by the acetite of lead, and afterwards by sulphuric acid, as directed above. TABLE _of the Combinations of Citric Acid, with the Salifiable Bases, in the Order of Affinity(A)._ _Bases._ _Neutral Salts._ Barytes Citrat of barytes. Lime lime. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. cobalt cobalt. copper copper. arsenic arsenic. mercury mercury. antimony antimony. silver silver. gold gold. platina platina. Argill argill. [Note A: These combinations were unknown to the ancient chemists. The order of affinity of the salifiable bases with this acid was determined by Mr Bergman and by Mr de Breney of the Dijon Academy.--A.] SECT. XXVIII.--_Observations upon Citric Acid, and its Combinations._ The citric acid is procured by expression from lemons, and is found in the juices of many other fruits mixed with malic acid. To obtain it pure and concentrated, it is first allowed to depurate from the mucous part of the fruit by long rest in a cool cellar, and is afterwards concentrated by exposing it to the temperature of 4 or 5 degrees below Zero, from 21° to 23° of Fahrenheit, the water is frozen, and the acid remains liquid, reduced to about an eighth part of its original bulk. A lower degree of cold would occasion the acid to be engaged amongst the ice, and render it difficultly separable. This process was pointed out by Mr Georgius. It is more easily obtained by saturating the lemon-juice with lime, so as to form a citrat of lime, which is insoluble in water; wash this salt, and pour on a proper quantity of sulphuric acid; this forms a sulphat of lime, which precipitates and leaves the citric acid free in the liquor. TABLE _of the Combinations of Pyro-lignous Acid with the Salifiable Bases, in the Order of Affinity(A)._ _Bases._ _Neutral Salts._ Lime Pyro-mucite of lime. Barytes barytes. Potash potash. Soda soda. Magnesia magnesia. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. mercury mercury. antimony antimony. silver silver. gold gold. platina platina. Argill argill. [Note A: The above affinities were determined by Messrs de Morveau and EloI Boursier de Clervaux. These combinations were entirely unknown till lately.--A.] SECT. XXIX.--_Observations upon Pyro-lignous Acid, and its Combinations._ The ancient chemists observed that most of the woods, especially the more heavy and compact ones, gave out a particular acid spirit, by distillation, in a naked fire; but, before Mr Goetling, who gives an account of his experiments upon this subject in Crell's Chemical Journal for 1779, no one had ever made any inquiry into its nature and properties. This acid appears to be the same, whatever be the wood it is procured from. When first distilled, it is of a brown colour, and considerably impregnated with charcoal and oil; it is purified from these by a second distillation. The pyro-lignous radical is chiefly composed of hydrogen and charcoal. SECT. XXX.--_Observations upon Pyro-tartarous Acid, and its Combinations with the Salifiable Bases[46]._ The name of _Pyro-tartarous acid_ is given to a dilute empyreumatic acid obtained from purified acidulous tartarite of potash by distillation in a naked fire. To obtain it, let a retort be half filled with powdered tartar, adapt a tubulated recipient, having a bent tube communicating with a bell-glass in a pneumato-chemical apparatus; by gradually raising the fire under the retort, we obtain the pyro-tartarous acid mixed with oil, which is separated by means of a funnel. A vast quantity of carbonic acid gas is disengaged during the distillation. The acid obtained by the above process is much contaminated with oil, which ought to be separated from it. Some authors advise to do this by a second distillation; but the Dijon academicians inform us, that this is attended with great danger from explosions which take place during the process. TABLE _of the Combinations of Pyro-mucous Acid, with the Salifiable Bases, in the Order of Affinity(A)._ _Bases._ _Neutral Salts._ Potash Pyro-mucite of potash. Soda soda. Barytes barytes. Lime lime. Magnesia magnesia. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. antimony antimony. [Note A: All these combinations were unknown to the ancient chemists.--A.] SECT. XXXI.--_Observations upon Pyro-mucous Acid, and its Combinations._ This acid is obtained by distillation in a naked fire from sugar, and all the saccharine bodies; and, as these substances swell greatly in the fire, it is necessary to leave seven-eighths of the retort empty. It is of a yellow colour, verging to red, and leaves a mark upon the skin, which will not remove but alongst with the epidermis. It may be procured less coloured, by means of a second distillation, and is concentrated by freezing, as is directed for the citric acid. It is chiefly composed of water and oil slightly oxygenated, and is convertible into oxalic and malic acids by farther oxygenation with the nitric acid. It has been pretended that a large quantity of gas is disengaged during the distillation of this acid, which is not the case if it be conducted slowly, by means of moderate heat. TABLE _of the Combinations of the Oxalic Acid, with the Salifiable Bases, in the Order of Affinity(A)._ _Bases._ _Neutral Salts._ Lime Oxalat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. mercury mercury. silver silver. gold gold. platina platina. [Note A: All unknown to the ancient chemists.--A.] SECT. XXXII.--_Observations upon Oxalic Acid, and its Combinations._ The oxalic acid is mostly prepared in Switzerland and Germany from the expressed juice of sorrel, from which it cristallizes by being left long at rest; in this state it is partly saturated with potash, forming a true acidulous oxalat of potash, or salt with excess of acid. To obtain it pure, it must be formed artificially by oxygenating sugar, which seems to be the true oxalic radical. Upon one part of sugar pour six or eight parts of nitric acid, and apply a gentle heat; a considerable effervescence takes place, and a great quantity of nitrous gas is disengaged; the nitric acid is decomposed, and its oxygen unites to the sugar: By allowing the liquor to stand at rest, cristals of pure oxalic acid are formed, which must be dried upon blotting paper, to separate any remaining portions of nitric acid; and, to ensure the purity of the acid, dissolve the cristals in distilled water, and cristallize them afresh. +---------------+------------------+--------------------------------------- | _Bases._ | _Neutral salts._ |_Names of the resulting neutral salts_ | | | |_according to the old nomenclature._ | |---------------+------------------+---------------------------------------+ |Barytes |Acetite of barytes{Unknown to the ancients. Discovered by | | | {Mr de Morveau, who calls it _barotic | | | {acéte_. | | | | | |Potash | ---- potash {Secret terra foliata tartari of Muller.| | | {Arcanum tartari of Basil Valentin and | | | {Paracelsus. Purgative magistery of | | | {tartar of Schroëder. Essential salt of | | | {wine of Zwelfer. Regenerated tartar of | | | {Tachenius. Diuretic salt of Sylvius | | | {and Wilson. | | | | | |Soda | ---- soda {Foliated earth with base of mineral | | | {alkali. Mineral or crystallisable | | | {foliated earth. Mineral acetous salt. | | | | | |Lime | ---- lime {Salt of chalk, coral, or crabs eyes; | | | {mentioned by Hartman. | | | | | |Magnesia | ---- magnesia |First mentioned by Mr Wenzel. | | | | | |Ammoniac | ---- ammoniac {Spiritus Mindereri. | | | {Ammoniacal acetous salt. | | | | | |Oxyd of zinc | ---- zinc {Known to Glauber, Schwedemberg, | | | {Respour, Pott, de Lassone, and Wenzel, | | | {but not named. | | | | | | ---- manganese| ---- manganese |Unknown to the ancients. | | | | | | ---- iron | ---- iron {Martial vinegar. Described by Monnet, | | | {Wenzel, and the Duke d'Ayen. | | | | | | ---- lead | ---- lead {Sugar, vinegar, and salt of lead or | | | {Saturn. | | | | | | ---- tin | ---- tin {Known to Lemery, Margraff, Monnet, | | | {Weslendorf, and Wenzel, but not named. | | | | | | ---- cobalt | ---- cobalt |Sympathetic ink of Mr Cadet. | | | | | | ---- copper | ---- copper {Verdigris, crystals of verditer, | | | {verditer, distilled verdigris, crystals| | | {of Venus or of copper. | | | | | | ---- nickel | ---- nickel |Unknown to the ancients. | | | | | | ---- arsenic | ---- arsenic {Arsenico-acetous fuming liquor, | | | {liquid phosphorus of Mr Cadet. | | | | | | ---- bismuth | ---- bismuth {Sugar of bismuth of Mr Geoffroi. Known | | | {to Gellert, Pott, Weslendorf, Bergman, | | | {and de Morveau. | | | | | | ---- mercury | ---- mercury {Mercurial foliated earth, Keyser's | | | {famous antivenereal remedy. Mentioned | | | {by Gebaver in 1748; known to Helot, | | | {Margraff, Baumé, Bergman, and | | | {de Morveau. | | | | | | ---- antimony | ---- antimony |Unknown. | | | | | | ---- silver | ---- silver {Described by Margraff, Monnet, and | | | {Wenzel; unknown to the ancients. | | | | | | ---- gold | ---- gold {Little known, mentioned by Schroëder | | | {and Juncker. | | | | | | ---- platina | ---- platina |Unknown. | | | | | |Argill | ---- argill |According to Mr Wenzel, vinegar | | | |dissolves only a very small proportion | | | |of argill. | +---------------+------------------+---------------------------------------+ From the liquor remaining after the first cristallization of the oxalic acid we may obtain malic acid by refrigeration: This acid is more oxygenated than the oxalic; and, by a further oxygenation, the sugar is convertible into acetous acid, or vinegar. The oxalic acid, combined with a small quantity of soda or potash, has the property, like the tartarous acid, of entering into a number of combinations without suffering decomposition: These combinations form triple salts, or neutral salts with double bases, which ought to have proper names. The salt of sorrel, which is potash having oxalic acid combined in excess, is named acidulous oxalat of potash in our new nomenclature. The acid procured from sorrel has been known to chemists for more than a century, being mentioned by Mr Duclos in the Memoirs of the Academy for 1688, and was pretty accurately described by Boerhaave; but Mr Scheele first showed that it contained potash, and demonstrated its identity with the acid formed by the oxygenation of sugar. SECT. XXXIII.--_Observations upon Acetous Acid, and its Combinations._ This acid is composed of charcoal and hydrogen united together, and brought to the state of an acid by the addition of oxygen; it is consequently formed by the same elements with the tartarous oxalic, citric, malic acids, and others, but the elements exist in different proportions in each of these; and it would appear that the acetous acid is in a higher state of oxygenation than these other acids. I have some reason to believe that the acetous radical contains a small portion of azote; and, as this element is not contained in the radicals of any vegetable acid except the tartarous, this circumstance is one of the causes of difference. The acetous acid, or vinegar, is produced by exposing wine to a gentle heat, with the addition of some ferment: This is usually the ley, or mother, which has separated from other vinegar during fermentation, or some similar matter. The spiritous part of the wine, which consists of charcoal and hydrogen, is oxygenated, and converted into vinegar: This operation can only take place with free access of air, and is always attended by a diminution of the air employed in consequence of the absorption of oxygen; wherefore, it ought always to be carried on in vessels only half filled with the vinous liquor submitted to the acetous fermentation. The acid formed during this process is very volatile, is mixed with a large proportion of water, and with many foreign substances; and, to obtain it pure, it is distilled in stone or glass vessels by a gentle fire. The acid which passes over in distillation is somewhat changed by the process, and is not exactly of the same nature with what remains in the alembic, but seems less oxygenated: This circumstance has not been formerly observed by chemists. Distillation is not sufficient for depriving this acid of all its unnecessary water; and, for this purpose, the best way is by exposing it to a degree of cold from 4° to 6° below the freezing point, from 19° to 23° of Fahrenheit; by this means the aqueous part becomes frozen, and leaves the acid in a liquid state, and considerably concentrated. In the usual temperature of the air, this acid can only exist in the gasseous form, and can only be retained by combination with a large proportion of water. There are other chemical processes for obtaining the acetous acid, which consist in oxygenating the tartarous, oxalic, or malic acids, by means of nitric acid; but there is reason to believe the proportions of the elements of the radical are changed during this process. Mr Hassenfratz is at present engaged in repeating the experiments by which these conversions are said to be produced. The combinations of acetous acid with the various salifiable bases are very readily formed; but most of the resulting neutral salts are not cristallizable, whereas those produced by the tartarous and oxalic acids are, in general, hardly soluble. Tartarite and oxalat of lime are not soluble in any sensible degree: The malats are a medium between the oxalats and acetites, with respect to solubility, and the malic acid is in the middle degree of saturation between the oxalic and acetous acids. With this, as with all the acids, the metals require to be oxydated previous to solution. The ancient chemists knew hardly any of the salts formed by the combinations of acetous acid with the salifiable bases, except the acetites of potash, soda, ammoniac, copper, and lead. Mr Cadet discovered the acetite of arsenic[47]; Mr Wenzel, the Dijon academicians Mr de Lassone, and Mr Proust, made us acquainted with the properties of the other acetites. From the property which acetite of potash possesses, of giving out ammoniac in distillation, there is some reason to suppose, that, besides charcoal and hydrogen, the acetous radical contains a small proportion of azote, though it is not impossible but the above production of ammoniac may be occasioned by the decomposition of the potash. TABLE _of the Combinations of Acetic Acid with the Salifiable Bases, in the order of affinity._ _Bases._ _Neutral Salts._ Barytes Acetat of barytes. Potash potash. Soda soda. Lime lime. Magnesia magnesia. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. mercury mercury. antimony antimony. silver silver. gold gold. platina platina. Argill argill. _Note._--All these salts were unknown to the ancients; and even those chemists who are most versant in modern discoveries, are yet at a lose whether the greater part of the salts produced by the oxygenated acetic radical belong properly to the class of acetites, or to that of acetats.--A. SECT. XXXIV.--_Observations upon Acetic Acid, and its Combinations._ We have given to radical vinegar the name of acetic acid, from supposing that it consists of the same radical with that of the acetous acid, but more highly saturated with oxygen. According to this idea, acetic acid is the highest degree of oxygenation of which the hydro-carbonous radical is susceptible; but, although this circumstance be extremely probable, it requires to be confirmed by farther, and more decisive experiments, before it be adopted as an absolute chemical truth. We procure this acid as follows: Upon three parts acetite of potash or of copper, pour one part of concentrated sulphuric acid, and, by distillation, a very highly concentrated vinegar is obtained, which we call acetic acid, formerly named radical vinegar. It is not hitherto rigorously proved that this acid is more highly oxygenated than the acetous acid, nor that the difference between them may not consist in a different proportion between the elements of the radical or base. TABLE _of the Combinations of Succinic Acid with the Salifiable Bases, in the order of Affinity._ _Bases._ _Neutral Salts._ Barytes Succinat of barytes. Lime lime. Potash potash. Soda soda. Ammoniac ammoniac. Magnesia magnesia. Argill argill. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. tin tin. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. mercury mercury. silver silver. gold gold. platina platina. _Note._--All the succinats were unknown to the ancient chemists.--A. SECT. XXXV.--_Observations upon Succinic Acid, and its Combinations._ The succinic acid is drawn from amber by sublimation in a gentle heat, and rises in a concrete form into the neck of the subliming vessel. The operation must not be pushed too far, or by too strong a fire, otherwise the oil of the amber rises alongst with the acid. The salt is dried upon blotting paper, and purified by repeated solution and crystallization. This acid is soluble in twenty-four times its weight of cold water, and in a much smaller quantity of hot water. It possesses the qualities of an acid in a very small degree, and only affects the blue vegetable colours very slightly. The affinities of this acid, with the salifiable bases, are taken from Mr de Morveau, who is the first chemist that has endeavoured to ascertain them. SECT. XXXVI.--_Observations upon Benzoic Acid, and its Combinations with Salifiable Bases[48]._ This acid was known to the ancient chemists under the name of Flowers of Benjamin, or of Benzoin, and was procured, by sublimation, from the gum or resin called Benzoin: The means of procuring it, _via humida_, was discovered by Mr Geoffroy, and perfected by Mr Scheele. Upon benzoin, reduced to powder, pour strong lime-water, having rather an excess of lime; keep the mixture continually stirring, and, after half an hour's digestion, pour off the liquor, and use fresh portions of lime-water in the same manner, so long as there is any appearance of neutralization. Join all the decanted liquors, and evaporate, as far as possible, without occasioning cristallization, and, when the liquor is cold, drop in muriatic acid till no more precipitate is formed. By the former part of the process a benzoat of lime is formed, and, by the latter, the muriatic acid combines with the lime, forming muriat of lime, which remains dissolved, while the benzoic acid, being insoluble, precipitates in a concrete state. SECT. XXXVII.--_Observations upon Camphoric Acid, and its Combinations with Salifiable Bases[49]._ Camphor is a concrete essential oil, obtained, by sublimation, from a species of laurus which grows in China and Japan. By distilling nitric acid eight times from camphor, Mr Kosegarten converted it into an acid analogous to the oxalic; but, as it differs from that acid in some circumstances, we have thought necessary to give it a particular name, till its nature be more completely ascertained by farther experiment. As camphor is a carbono-hydrous or hydro-carbonous radical, it is easily conceived, that, by oxygenation, it should form oxalic, malic, and several other vegetable acids: This conjecture is rendered not improbable by the experiments of Mr Kosegarten; and the principal phenomena exhibited in the combinations of camphoric acid with the salifiable bases, being very similar to those of the oxalic and malic acids, lead me to believe that it consists of a mixture of these two acids. SECT. XXXVIII.--_Observations upon Gallic Acid, and its Combinations with Salifiable Bases[50]._ The Gallic acid, formerly called Principle of Astringency, is obtained from gall nuts, either by infusion or decoction with water, or by distillation with a very gentle heat. This acid has only been attended to within these few years. The Committee of the Dijon Academy have followed it through all its combinations, and give the best account of it hitherto produced. Its acid properties are very weak; it reddens the tincture of turnsol, decomposes sulphurets, and unites to all the metals when they have been previously dissolved in some other acid. Iron, by this combination, is precipitated of a very deep blue or violet colour. The radical of this acid, if it deserves the name of one, is hitherto entirely unknown; it is contained in oak willow, marsh iris, the strawberry, nymphea, Peruvian bark, the flowers and bark of pomgranate, and in many other woods and barks. SECT. XXXIX.--_Observations upon Lactic Acid, and its Combinations with Salifiable Bases[51]._ The only accurate knowledge we have of this acid is from the works of Mr Scheele. It is contained in whey, united to a small quantity of earth, and is obtained as follows: Reduce whey to one eighth part of its bulk by evaporation, and filtrate, to separate all its cheesy matter; then add as much lime as is necessary to combine with the acid; the lime is afterwards disengaged by the addition of oxalic acid, which combines with it into an insoluble neutral salt. When the oxalat of lime has been separated by decantation, evaporate the remaining liquor to the consistence of honey; the lactic acid is dissolved by alkohol, which does not unite with the sugar of milk and other foreign matters; these are separated by filtration from the alkohol and acid; and the alkohol being evaporated, or distilled off, leaves the lactic acid behind. This acid unites with all the salifiable bases forming salts which do not cristallize; and it seems considerably to resemble the acetous acid. TABLE _of the Combinations of Saccholactic Acid with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Lime Saccholat of lime. Barytes barytes. Magnesia magnesia. Potash potash. Soda soda. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. mercury mercury. antimony antimony. silver silver. _Note._--All these were unknown to the ancient chemists.--A. SECT. XL.--_Observations upon Saccholactic Acid, and its Combinations._ A species of sugar may be extracted, by evaporation, from whey, which has long been known in pharmacy, and which has a considerable resemblance to that procured from sugar canes. This saccharine matter, like ordinary sugar, may be oxygenated by means of nitric acid: For this purpose, several portions of nitric acid are distilled from it; the remaining liquid is evaporated, and set to cristallize, by which means cristals of oxalic acid are procured; at the same time a very fine white powder precipitates, which is the saccholactic acid discovered by Scheele. It is susceptible of combining with the alkalies, ammoniac, the earths, and even with the metals: Its action upon the latter is hitherto but little known, except that, with them, it forms difficultly soluble salts. The order of affinity in the table is taken from Bergman. TABLE _of the Combinations of Formic Acid, with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Barytes Formiat of barytes. Potash potash. Soda soda. Lime lime. Magnesia magnesia. Ammoniac ammoniac. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. bismuth bismuth. silver silver. Argill argill. _Note._--All unknown to the ancient chemists.--A. SECT. XLI.--_Observations upon Formic Acid, and its Combinations._ This acid was first obtained by distillation from ants, in the last century, by Samuel Fisher. The subject was treated of by Margraff in 1749, and by Messrs Ardwisson and Ochrn of Leipsic in 1777. The formic acid is drawn from a large species of red ants, _formica rufa, Lin._ which form large ant hills in woody places. It is procured, either by distilling the ants with a gentle heat in a glass retort or an alembic; or, after having washed the ants in cold water, and dried them upon a cloth, by pouring on boiling water, which dissolves the acid; or the acid may be procured by gentle expression from the insects, in which case it is stronger than in any of the former ways. To obtain it pure, we must rectify, by means of distillation, which separates it from the uncombined oily and charry matter; and it may be concentrated by freezing, in the manner recommended for treating the acetous acid. SECT. XLII.--_Observations upon Bombic Acid, and its Combinations with Acidifiable Bases[52]._ The juices of the silk worm seem to assume an acid quality when that insect changes from a larva to a chrysalis. At the moment of its escape from the latter to the butterfly form, it emits a reddish liquor which reddens blue paper, and which was first attentively observed by Mr Chaussier of the Dijon academy, who obtains the acid by infusing silk worm chrysalids in alkohol, which dissolves their acid without being charged with any of the gummy parts of the insect; and, by evaporating the alkohol, the acid remains tollerably pure. The properties and affinities of this acid are not hitherto ascertained with any precision; and we have reason to believe that analogous acids may be procured from other insects. The radical of this acid is probably, like that of the other acids from the animal kingdom, composed of charcoal, hydrogen, and azote, with the addition, perhaps, of phosphorus. TABLE _of the Combinations of Sebacic Acid, with the Salifiable Bases, in the Order of Affinity._ _Bases._ _Neutral Salts._ Barytes Sebat of barytes. Potash potash. Soda soda. Lime lime. Magnesia magnesia. Ammoniac ammoniac. Argill argill. Oxyd of zinc zinc. manganese manganese. iron iron. lead lead. tin tin. cobalt cobalt. copper copper. nickel nickel. arsenic arsenic. bismuth bismuth. mercury mercury. antimony antimony. silver silver. _Note._--All these were unknown to the ancient chemists.--A. SECT. XLIII.--_Observations upon Sebacid Acid, and its Combinations._ To obtain the sebacic acid, let some suet be melted in a skillet over the fire, alongst with some quick-lime in fine powder, and constantly stirred, raising the fire towards the end of the operation, and taking care to avoid the vapours, which are very offensive. By this process the sebacic acid unites with the lime into a sebat of lime, which is difficultly soluble in water; it is, however, separated from the fatty matters with which it is mixed by solution in a large quantity of boiling water. From this the neutral salt is separated by evaporation; and, to render it pure, is calcined, redissolved, and again cristallized. After this we pour on a proper quantity of sulphuric acid, and the sebacic acid passes over by distillation. SECT. XLIV.--_Observations upon the Lithic Acid, and its Combinations with the Salifiable Bases[53]._ From the later experiments of Bergman and Scheele, the urinary calculus appears to be a species of salt with an earthy basis; it is slightly acidulous, and requires a large quantity of water for solution, three grains being scarcely soluble in a thousand grains of boiling water, and the greater part again cristallizes when cold. To this concrete acid, which Mr de Morveau calls Lithiasic Acid, we give the name of Lithic Acid, the nature and properties of which are hitherto very little known. There is some appearance that it is an acidulous neutral salt, or acid combined in excess with a salifiable base; and I have reason to believe that it really is an acidulous phosphat of lime; if so, it must be excluded from the class of peculiar acids. TABLE _of the Combinations of the Prussic Acid with the Salifiable Bases, in the order of affinity._ _Bases._ _Neutral Salts._ Potash Prussiat of potash. Soda soda. Ammoniac ammoniac. Lime lime. Barytes barytes. Magnesia magnesia. Oxyd of zinc zinc. iron iron. manganese manganese. cobalt cobalt. nickel nickel. lead lead. tin tin. copper copper. bismuth bismuth. antimony antimony. arsenic arsenic. silver silver. mercury mercury. gold gold. platina platina. _Note._---All these were unknown to former chemists.--A. _Observations upon the Prussic Acid, and its Combinations._ As the experiments which have been made hitherto upon this acid seem still to leave a considerable degree of uncertainty with regard to its nature, I shall not enlarge upon its properties, and the means of procuring it pure and dissengaged from combination. It combines with iron, to which it communicates a blue colour, and is equally susceptible of entering into combination with most of the other metals, which are precipitated from it by the alkalies, ammoniac, and lime, in consequence of greater affinity. The Prussic radical, from the experiments of Scheele, and especially from those of Mr Berthollet, seems composed of charcoal and azote; hence it is an acid with a double base. The phosphorus which has been found combined with it appears, from the experiments of Mr Hassenfratz, to be only accidental. Although this acid combines with alkalies, earths, and metals, in the same way with other acids, it possesses only some of the properties we have been in use to attribute to acids, and it may consequently be improperly ranked here in the class of acids; but, as I have already observed, it is difficult to form a decided opinion upon the nature of this substance until the subject has been farther elucidated by a greater number of experiments. FOOTNOTES: [36] See Memoirs of the Academy for 1776, p. 671. and for 1778, p. 535,--A. [37] See Part I. Chap. XI. upon this subject.--A. [38] See Part I. Chap. XI. upon the application of these names according to the proportions of the two ingredients.--A [39] See Part I. Chap. XII. upon this subject.--A. [40] Those who wish to see what has been said upon this great chemical question by Messrs de Morveau, Berthollet, De Fourcroy, and myself, may consult our translation of Mr Kirwan's Essay upon Phlogiston.--A. [41] Saltpetre is likewise procured in large quantities by lixiviating the natural soil in some parts of Bengal, and of the Russian Ukrain.--E. [42] Commonly called _Derbyshire spars_.--E. [43] I have not added the Table of these combinations, as the order of their affinity is entirely unknown; they are called _molybdats of argil_, _antimony_, _potash_, &c.--E. [44] This acid was discovered by Mr Scheele, to whom chemistry is indebted for the discovery of several other acids.--A. [45] I have omitted the Table, as the order of affinity is unknown, and is given by Mr Lavoisier only in alphabetical order. All the combinations of malic acid with salifiable bases, which are named _malats_, were unknown to the ancient chemists.--E. [46] The order of affinity of the salifiable bases with this acid is hitherto unknown. Mr Lavoisier, from its similarity to pyro-lignous acid, supposes the order to be the same in both; but, as this is not ascertained by experiment, the table is omitted. All these combinations, called _Pyro-tartarites_, were unknown till lately--E. [47] Savans Etrangers, Vol. III. [48] These combinations are called Benzoats of Lime, Potash, Zinc, &c.; but, as the order of affinity is unknown, the alphabetical table is omitted, as unnecessary.--E. [49] These combinations, which were all unknown to the ancients, are called Camphorats. The table is omitted, as being only in alphabetical order.--E. [50] These combinations, which are called Gallats, were all unknown to the ancients; and the order of their affinity is not hitherto established.--A. [51] These combinations are called Lactats; they were all unknown to the ancient chemists, and their affinities have not yet been ascertained.--A. [52] These combinations named Bombats were unknown to the ancient chemists; and the affinities of the salifiable bases with the bombic acid are hitherto undetermined.--A. [53] All the combinations of this acid, should it finally turn out to be one, were unknown to the ancient chemists, and its affinities with the salifiable bases have not been hitherto determined.--A. PART III. Description of the Instruments and Operations of Chemistry. INTRODUCTION. In the two former parts of this work I designedly avoided being particular in describing the manual operations of chemistry, because I had found from experience, that, in a work appropriated to reasoning, minute descriptions of processes and of plates interrupt the chain of ideas, and render the attention necessary both difficult and tedious to the reader. On the other hand, if I had confined myself to the summary descriptions hitherto given, beginners could have only acquired very vague conceptions of practical chemistry from my work, and must have wanted both confidence and interest in operations they could neither repeat nor thoroughly comprehend. This want could not have been supplied from books; for, besides that there are not any which describe the modern instruments and experiments sufficiently at large, any work that could have been consulted would have presented these things under a very different order of arrangement, and in a different chemical language, which must greatly tend to injure the main object of my performance. Influenced by these motives, I determined to reserve, for a third part of my work, a summary description of all the instruments and manipulations relative to elementary chemistry. I considered it as better placed at the end, rather than at the beginning of the book, because I must have been obliged to suppose the reader acquainted with circumstances which a beginner cannot know, and must therefore have read the elementary part to become acquainted with. The whole of this third part may therefore be considered as resembling the explanations of plates which are usually placed at the end of academic memoirs, that they may not interrupt the connection of the text by lengthened description. Though I have taken great pains to render this part clear and methodical, and have not omitted any essential instrument or apparatus, I am far from pretending by it to set aside the necessity of attendance upon lectures and laboratories, for such as wish to acquire accurate knowledge of the science of chemistry. These should familiarise themselves to the employment of apparatus, and to the performance of experiments by actual experience. _Nihil est in intellectu quod non prius fuerit in sensu_, the motto which the celebrated Rouelle caused to be painted in large characters in a conspicuous part of his laboratory, is an important truth never to be lost sight of either by teachers or students of chemistry. Chemical operations may be naturally divided into several classes, according to the purposes they are intended for performing. Some may be considered as purely mechanical, such as the determination of the weight and bulk of bodies, trituration, levigation, searching, washing, filtration, &c. Others may be considered as real chemical operations, because they are performed by means of chemical powers and agents; such are solution, fusion, &c. Some of these are intended for separating the elements of bodies from each other, some for reuniting these elements together; and some, as combustion, produce both these effects during the same process. Without rigorously endeavouring to follow the above method, I mean to give a detail of the chemical operations in such order of arrangement as seemed best calculated for conveying instruction. I shall be more particular in describing the apparatus connected with modern chemistry, because these are hitherto little known by men who have devoted much of their time to chemistry, and even by many professors of the science. CHAP. I. _Of the Instruments necessary for determining the Absolute and Specific Gravities of Solid and Liquid Bodies._ The best method hitherto known for determining the quantities of substances submitted to chemical experiment, or resulting from them, is by means of an accurately constructed beam and scales, with properly regulated weights, which well known operation is called _weighing_. The denomination and quantity of the weights used as an unit or standard for this purpose are extremely arbitrary, and vary not only in different kingdoms, but even in different provinces of the same kingdom, and in different cities of the same province. This variation is of infinite consequence to be well understood in commerce and in the arts; but, in chemistry, it is of no moment what particular denomination of weight be employed, provided the results of experiments be expressed in convenient fractions of the same denomination. For this purpose, until all the weights used in society be reduced to the same standard, it will be sufficient for chemists in different parts to use the common pound of their own country as the unit or standard, and to express all its fractional parts in decimals, instead of the arbitrary divisions now in use. By this means the chemists of all countries will be thoroughly understood by each other, as, although the absolute weights of the ingredients and products cannot be known, they will readily, and without calculation, be able to determine the relative proportions of these to each other with the utmost accuracy; so that in this way we shall be possessed of an universal language for this part of chemistry. With this view I have long projected to have the pound divided into decimal fractions, and I have of late succeeded through the assistance of Mr Fourche balance-maker at Paris, who has executed it for me with great accuracy and judgment. I recommend to all who carry on experiments to procure similar divisions of the pound, which they will find both easy and simple in its application, with a very small knowledge of decimal fractions[54]. As the usefulness and accuracy of chemistry depends entirely upon the determination of the weights of the ingredients and products both before and after experiments, too much precision cannot be employed in this part of the subject; and, for this purpose, we must be provided with good instruments. As we are often obliged, in chemical processes, to ascertain, within a grain or less, the tare or weight of large and heavy instruments, we must have beams made with peculiar niceness by accurate workmen, and these must always be kept apart from the laboratory in some place where the vapours of acids, or other corrosive liquors, cannot have access, otherwise the steel will rust, and the accuracy of the balance be destroyed. I have three sets, of different sizes, made by Mr Fontin with the utmost nicety, and, excepting those made by Mr Ramsden of London, I do not think any can compare with them for precision and sensibility. The largest of these is about three feet long in the beam for large weights, up to fifteen or twenty pounds; the second, for weights of eighteen or twenty ounces, is exact to a tenth part of a grain; and the smallest, calculated only for weighing about one gros, is sensibly affected by the five hundredth part of a grain. Besides these nicer balances, which are only used for experiments of research, we must have others of less value for the ordinary purposes of the laboratory. A large iron balance, capable of weighing forty or fifty pounds within half a dram, one of a middle size, which may ascertain eight or ten pounds, within ten or twelve grains, and a small one, by which about a pound may be determined, within one grain. We must likewise be provided with weights divided into their several fractions, both vulgar and decimal, with the utmost nicety, and verified by means of repeated and accurate trials in the nicest scales; and it requires some experience, and to be accurately acquainted with the different weights, to be able to use them properly. The best way of precisely ascertaining the weight of any particular substance is to weigh it twice, once with the decimal divisions of the pound, and another time with the common subdivisions or vulgar fractions, and, by comparing these, we attain the utmost accuracy. By the specific gravity of any substance is understood the quotient of its absolute weight divided by its magnitude, or, what is the same, the weight of a determinate bulk of any body. The weight of a determinate magnitude of water has been generally assumed as unity for this purpose; and we express the specific gravity of gold, sulphuric acid, &c. by saying, that gold is nineteen times, and sulphuric acid twice the weight of water, and so of other bodies. It is the more convenient to assume water as unity in specific gravities, that those substances whose specific gravity we wish to determine, are most commonly weighed in water for that purpose. Thus, if we wish to determine the specific gravity of gold flattened under the hammer, and supposing the piece of gold to weigh 8 oz. 4 gros 2-1/2 grs. in the air[55], it is suspended by means of a fine metallic wire under the scale of a hydrostatic balance, so as to be entirely immersed in water, and again weighed. The piece of gold in Mr Brisson's experiment lost by this means 3 gros 37 grs.; and, as it is evident that the weight lost by a body weighed in water is precisely equal to the weight of the water displaced, or to that of an equal volume of water, we may conclude, that, in equal magnitudes, gold weighs 4893-1/2 grs. and water 253 grs. which, reduced to unity, gives 1.0000 as the specific gravity of water, and 19.3617 for that of gold. We may operate in the same manner with all solid substances. We have rarely any occasion, in chemistry, to determine the specific gravity of solid bodies, unless when operating upon alloys or metallic glasses; but we have very frequent necessity to ascertain that of fluids, as it is often the only means of judging of their purity or degree of concentration. This object may be very fully accomplished with the hydrostatic balance, by weighing a solid body; such, for example, as a little ball of rock cristal suspended by a very fine gold wire, first in the air, and afterwards in the fluid whose specific gravity we wish to discover. The weight lost by the cristal, when weighed in the liquor, is equal to that of an equal bulk of the liquid. By repeating this operation successively in water and different fluids, we can very readily ascertain, by a simple and easy calculation, the relative specific gravities of these fluids, either with respect to each other or to water. This method is not, however, sufficiently exact, or, at least, is rather troublesome, from its extreme delicacy, when used for liquids differing but little in specific gravity from water; such, for instance, as mineral waters, or any other water containing very small portions of salt in solution. In some operations of this nature, which have not hitherto been made public, I employed an instrument of great sensibility for this purpose with great advantage. It consists of a hollow cylinder, A b c f, Pl. vii. fig. 6. of brass, or rather of silver, loaded at its bottom, b c f, with tin, as represented swimming in a jug of water, l m n o. To the upper part of the cylinder is attached a stalk of silver wire, not more than three fourths of a line diameter, surmounted by a little cup d, intended for containing weights; upon the stalk a mark is made at g, the use of which we shall presently explain. This cylinder may be made of any size; but, to be accurate, ought at least to displace four pounds of water. The weight of tin with which this instrument is loaded ought to be such as will make it remain almost in equilibrium in distilled water, and should not require more than half a dram, or a dram at most, to make it sink to g. We must first determine, with great precision, the exact weight of the instrument, and the number of additional grains requisite for making it sink, in distilled water of a determinate temperature, to the mark: We then perform the same experiment upon all the fluids of which we wish to ascertain the specific gravity, and, by means of calculation, reduce the observed differences to a common standard of cubic feet, pints or pounds, or of decimal fractions, comparing them with water. This method, joined to experiments with certain reagents[56], is one of the best for determining the quality of waters, and is even capable of pointing out differences which escape the most accurate chemical analysis. I shall, at some future period, give an account of a very extensive set of experiments which I have made upon this subject. These metallic hydrometers are only to be used for determining the specific gravities of such waters as contain only neutral salts or alkaline substances; and they may be constructed with different degrees of ballast for alkohol and other spiritous liquors. When the specific gravities of acid liquors are to be ascertained, we must use a glass hydrometer, as represented Pl. vii. fig. 14[57]. This consists of a hollow cylinder of glass, a b c f, hermetically sealed at its lower end, and drawn out at the upper into a capillary tube a, ending in the little cup or bason d. This instrument is ballasted with more or less mercury, at the bottom of the cylinder introduced through the tube, in proportion to the weight of the liquor intended to be examined: We may introduce a small graduated slip of paper into the tube a d; and, though these degrees do not exactly correspond to the fractions of grains in the different liquors, they may be rendered very useful in calculation. What is said in this chapter may suffice, without farther enlargement, for indicating the means of ascertaining the absolute and specific gravities of solids and fluids, as the necessary instruments are generally known, and may easily be procured: But, as the instruments I have used for measuring the gasses are not any where described, I shall give a more detailed account of these in the following chapter. FOOTNOTES: [54] Mr Lavoisier gives, in this part of his work, very accurate directions for reducing the common subdivisions of the French pound into decimal fractions, and _vice versa_, by means of tables subjoined to this 3d part. As these instructions, and the table, would be useless to the British chemist, from the difference between the subdivisions of the French and Troy pounds, I have omitted them, but have subjoined in the appendix accurate rules for converting the one into the other.--E. [55] Vide Mr Brisson's Essay upon Specific Gravity, p. 5.--A. [56] For the use of these reagents see Bergman's excellent treatise upon the analysis of mineral waters, in his Chemical and Physical Essays.--E. [57] Three or four years ago, I have seen similar glass hydrometers, made for Dr Black by B. Knie, a very ingenious artist of this city.--E. CHAP. II. _Of Gazometry, or the Measurement of the Weight and Volume of Aëriform Substances._ SECT. I. _Description of the Pneumato-chemical Apparatus._ The French chemists have of late applied the name of _pneumato-chemical apparatus_ to the very simple and ingenious contrivance, invented by Dr Priestley, which is now indispensibly necessary to every laboratory. This consists of a wooden trough, of larger or smaller dimensions as is thought convenient, lined with plate-lead or tinned copper, as represented in perspective, Pl. V. In Fig. 1. the same trough or cistern is supposed to have two of its sides cut away, to show its interior construction more distinctly. In this apparatus, we distinguish between the shelf ABCD Fig. 1. and 2. and the bottom or body of the cistern FGHI Fig. 2. The jars or bell-glasses are filled with water in this deep part, and, being turned with their mouths downwards, are afterwards set upon the shelf ABCD, as shown Plate X. Fig. 1. F. The upper parts of the sides of the cistern above the level of the shelf are called the _rim_ or _borders_. The cistern ought to be filled with water, so as to stand at least an inch and a half deep upon the shelf, and it should be of such dimensions as to admit of at least one foot of water in every direction in the well. This size is sufficient for ordinary occasions; but it is often convenient, and even necessary, to have more room; I would therefore advise such as intend to employ themselves usefully in chemical experiments, to have this apparatus made of considerable magnitude, where their place of operating will allow. The well of my principal cistern holds four cubical feet of water, and its shelf has a surface of fourteen square feet; yet, in spite of this size, which I at first thought immoderate, I am often straitened for room. In laboratories, where a considerable number of experiments are performed, it is necessary to have several lesser cisterns, besides the large one, which may be called the _general magazine_; and even some portable ones, which may be moved when necessary, near a furnace, or wherever they may be wanted. There are likewise some operations which dirty the water of the apparatus, and therefore require to be carried on in cisterns by themselves. It were doubtless considerably cheaper to use cisterns, or iron-bound tubs, of wood simply dove-tailed, instead of being lined with lead or copper; and in my first experiments I used them made in that way; but I soon discovered their inconvenience. If the water be not always kept at the same level, such of the dovetails as are left dry shrink, and, when more water is added, it escapes through the joints, and runs out. We employ cristal jars or bell glasses, Pl. V. Fig. 9. A. for containing the gasses in this apparatus; and, for transporting these, when full of gas, from one cistern to another, or for keeping them in reserve when the cistern is too full, we make use of a flat dish BC, surrounded by a standing up rim or border, with two handles DE for carrying it by. After several trials of different materials, I have found marble the best substance for constructing the mercurial pneumato-chemical apparatus, as it is perfectly impenetrable by mercury, and is not liable, like wood, to separate at the junctures, or to allow the mercury to escape through chinks; neither does it run the risk of breaking, like glass, stone-ware, or porcelain. Take a block of marble BCDE, Plate V. Fig. 3. and 4. about two feet long, 15 or 18 inches broad, and ten inches thick, and cause it to be hollowed out as at m n Fig. 5. about four inches deep, as a reservoir for the mercury; and, to be able more conveniently to fill the jars, cut the gutter T V, Fig. 3. 4. and 5. at least four inches deeper; and, as this trench may sometimes prove troublesome, it is made capable of being covered at pleasure by thin boards, which slip into the grooves x y, Fig. 5. I have two marble cisterns upon this construction, of different sizes, by which I can always employ one of them as a reservoir of mercury, which it preserves with more safety than any other vessel, being neither subject to overturn, nor to any other accident. We operate with mercury in this apparatus exactly as with water in the one before described; but the bell-glasses must be of smaller diameter, and much stronger; or we may use glass tubes, having their mouths widened, as in Fig. 7.; these are called _eudiometers_ by the glass-men who sell them. One of the bell-glasses is represented Fig. 5. A. standing in its place, and what is called a jar is engraved Fig. 6. The mercurial pneumato-chemical apparatus is necessary in all experiments wherein the disengaged gasses are capable of being absorbed by water, as is frequently the case, especially in all combinations, excepting those of metals, in fermentation, &c. SECT. II. _Of the Gazometer._ I give the name of _gazometer_ to an instrument which I invented, and caused construct, for the purpose of a kind of bellows, which might furnish an uniform and continued stream of oxygen gas in experiments of fusion. Mr Meusnier and I have since made very considerable corrections and additions, having converted it into what may be called an _universal instrument_, without which it is hardly possible to perform most of the very exact experiments. The name we have given the instrument indicates its intention for measuring the volume or quantity of gas submitted to it for examination. It consists of a strong iron beam, DE, Pl. VIII. Fig. 1. three feet long, having at each end, D and E, a segment of a circle, likewise strongly constructed of iron, and very firmly joined. Instead of being poised as in ordinary balances, this beam rests, by means of a cylindrical axis of polished steel, F, Fig. 9. upon two large moveable brass friction-wheels, by which the resistance to its motion from friction is considerably diminished, being converted into friction of the second order. As an additional precaution, the parts of these wheels which support the axis of the beam are covered with plates of polished rock-cristal. The whole of this machinery is fixed to the top of the solid column of wood BC, Fig. 1. To one extremity D of the beam, a scale P for holding weights is suspended by a flat chain, which applies to the curvature of the arc nDo, in a groove made for the purpose. To the other extremity E of the beam is applied another flat chain, i k m, so constructed, as to be incapable of lengthening or shortening, by being less or more charged with weight; to this chain, an iron trivet, with three branches, a i, c i, and h i, is strongly fixed at i, and these branches support a large inverted jar A, of hammered copper, of about 18 inches diameter, and 20 inches deep. The whole of this machine is represented in perspective, Pl. VIII. Fig. 1. and Pl. IX. Fig. 2. and 4. give perpendicular sections, which show its interior structure. Round the bottom of the jar, on its outside, is fixed (Pl. IX. Fig. 2.) a border divided into compartments 1, 2, 3, 4, &c. intended to receive leaden weights separately represented 1, 2, 3, Fig. 3. These are intended for increasing the weight of the jar when a considerable pressure is requisite, as will be afterwards explained, though such necessity seldom occurs. The cylindrical jar A is entirely open below, de, Pl. IX. Fig. 4.; but is closed above with a copper lid, a b c, open at b f, and capable of being shut by the cock g. This lid, as may be seen by inspecting the figures, is placed a few inches within the top of the jar to prevent the jar from being ever entirely immersed in the water, and covered over. Were I to have this instrument made over again, I should cause the lid to be considerably more flattened, so as to be almost level. This jar or reservoir of air is contained in the cylindrical copper vessel, LMNO, Pl. VIII. Fig. 1. filled with water. In the middle of the cylindrical vessel LMNO, Pl. IX. Fig. 4. are placed two tubes st, xy, which are made to approach each other at their upper extremities t y; these are made of such a length as to rise a little above the upper edge LM of the vessel LMNO, and when the jar abcde touches the bottom NO, their upper ends enter about half an inch into the conical hollow b, leading to the stop-cock g. The bottom of the vessel LMNO is represented Pl. IX. Fig. 3. in the middle of which a small hollow semispherical cap is soldered, which may be considered as the broad end of a funnel reversed; the two tubes st, xy, Fig. 4. are adapted to this cap at s and x, and by this means communicate with the tubes mm, nn, oo, pp, Fig. 3. which are fixed horizontally upon the bottom of the vessel, and all of which terminate in, and are united by, the spherical cap sx. Three of these tubes are continued out of the vessel, as in Pl. VIII. Fig. 1. The first marked in that figure 1, 2, 3, is inserted at its extremity 3, by means of an intermediate stop-cock 4, to the jar V. which stands upon the shelf of a small pneumato-chemical apparatus GHIK, the inside of which is shown Pl. IX. Fig. 1. The second tube is applied against the outside of the vessel LMNO from 6 to 7, is continued at 8, 9, 10, and at 11 is engaged below the jar V. The former of these tubes is intended for conveying gas into the machine, and the latter for conducting small quantities for trials under jars. The gas is made either to flow into or out of the machine, according to the degree of pressure it receives; and this pressure is varied at pleasure, by loading the scale P less or more, by means of weights. When gas is to be introduced into the machine, the pressure is taken off, or even rendered negative; but, when gas is to be expelled, a pressure is made with such degree of force as is found necessary. The third tube 12, 13, 14, 15, is intended for conveying air or gas to any necessary place or apparatus for combustions, combinations, or any other experiment in which it is required. To explain the use of the fourth tube, I must enter into some discussions. Suppose the vessel LMNO, Pl. VIII. Fig. 1. full of water, and the jar A partly filled with gas, and partly with water; it is evident that the weights in the bason P may be so adjusted, as to occasion an exact equilibrium between the weight of the bason and of the jar, so that the external air shall not tend to enter into the jar, nor the gas to escape from it; and in this case the water will stand exactly at the same level both within and without the jar. On the contrary, if the weight in the bason P be diminished, the jar will then press downwards from its own gravity, and the water will stand lower within the jar than it does without; in this case, the included air or gas will suffer a degree of compression above that experienced by the external air, exactly proportioned to the weight of a column of water, equal to the difference of the external and internal surfaces of the water. From these reflections, Mr Meusnier contrived a method of determining the exact degree of pressure to which the gas contained in the jar is at any time exposed. For this purpose, he employs a double glass syphon 19, 20, 21, 22, 23, firmly cemented at 19 and 23. The extremity 19 of this syphon communicates freely with the water in the external vessel of the machine, and the extremity 23 communicates with the fourth tube at the bottom of the cylindrical vessel, and consequently, by means of the perpendicular tube st, Pl. IX. Fig. 4. with the air contained in the jar. He likewise cements, at 16, Pl. VIII. Fig. 1. another glass tube 16, 17, 18, which communicates at 16 with the water in the exterior vessel LMNO, and, at its upper end 18, is open to the external air. By these several contrivances, it is evident that the water must stand in the tube 16, 17, 18, at the same level with that in the cistern LMNO; and, on the contrary, that, in the branch 19, 20, 21, it must stand higher or lower, according as the air in the jar is subjected to a greater or lesser pressure than the external air. To ascertain these differences, a brass scale divided into inches and lines is fixed between these two tubes. It is readily conceived that, as air, and all other elastic fluids, must increase in weight by compression, it is necessary to know their degree of condensation to be enabled to calculate their quantities, and to convert the measure of their volumes into correspondent weights; and this object is intended to be fulfilled by the contrivance now described. But, to determine the specific gravity of air or of gasses, and to ascertain their weight in a known volume, it is necessary to know their temperature, as well as the degree of pressure under which they subsist; and this is accomplished by means of a small thermometer, strongly cemented into a brass collet, which screws into the lid of the jar A. This thermometer is represented separately, Pl. VIII. Fig. 10. and in its place 24, 25, Fig. 1. and Pl. IX. Fig. 4. The bulb is in the inside of the jar A, and its graduated stalk rises on the outside of the lid. The practice of gazometry would still have laboured under great difficulties, without farther precautions than those above described. When the jar A sinks in the water of the cistern LMNO, it must lose a weight equal to that of the water which it displaces; and consequently the compression which it makes upon the contained air or gas must be proportionally diminished. Hence the gas furnished, during experiments from the machine, will not have the same density towards the end that it had at the beginning, as its specific gravity is continually diminishing. This difference may, it is true, be determined by calculation; but this would have occasioned such mathematical investigations as must have rendered the use of this apparatus both troublesome and difficult. Mr Meusnier has remedied this inconvenience by the following contrivance. A square rod of iron, 26, 27, Pl. VIII. Fig. 1. is raised perpendicular to the middle of the beam DE. This rod passes through a hollow box of brass 28, which opens, and may be filled with lead; and this box is made to slide alongst the rod, by means of a toothed pinion playing in a rack, so as to raise or lower the box, and to fix it at such places as is judged proper. When the lever or beam DE stands horizontal, this box gravitates to neither side; but, when the jar A sinks into the cistern LMNO, so as to make the beam incline to that side, it is evident the loaded box 28, which then passes beyond the center of suspension, must gravitate to the side of the jar, and augment its pressure upon the included air. This is increased in proportion as the box is raised towards 27, because the same weight exerts a greater power in proportion to the length of the lever by which it acts. Hence, by moving the box 28 alongst the rod 26, 27, we can augment or diminish the correction it is intended to make upon the pressure of the jar; and both experience and calculation show that this may be made to compensate very exactly for the loss of weight in the jar at all degrees of pressure. I have not hitherto explained the most important part of the use of this machine, which is the manner of employing it for ascertaining the quantities of the air or gas furnished during experiments. To determine this with the most rigorous precision, and likewise the quantity supplied to the machine from experiments, we fixed to the arc which terminates the arm of the beam E, Pl. VIII. Fig. 1. the brass sector l m, divided into degrees and half degrees, which consequently moves in common with the beam; and the lowering of this end of the beam is measured by the fixed index 29, 30, which has a Nonius giving hundredth parts of a degree at its extremity 30. The whole particulars of the different parts of the above described machine are represented in Plate VIII. as follow. Fig. 2. Is the flat chain invented by Mr Vaucanson, and employed for suspending the scale or bason P, Fig. 1; but, as this lengthens or shortens according as it is more or less loaded, it would not have answered for suspending the jar A, Fig. 1. Fig. 5. Is the chain i k m, which in Fig. 1. sustains the jar A. This is entirely formed of plates of polished iron interlaced into each other, and held together by iron pins. This chain does not lengthen in any sensible degree, by any weight it is capable of supporting. Fig. 6. The trivet, or three branched stirrup, by which the jar A is hung to the balance, with the screw by which it is fixed in an accurately vertical position. Fig. 3. The iron rod 26, 27, which is fixed perpendicular to the center of the beam, with its box 28. Fig. 7. & 8. The friction-wheels, with the plates of rock-cristal Z, as points of contact by which the friction of the axis of the lever of the balance is avoided. Fig. 4. The piece of metal which supports the axis of the friction-wheels. Fig. 9. The middle of the lever or beam, with the axis upon which it moves. Fig. 10. The thermometer for determining the temperature of the air or gas contained in the jar. When this gazometer is to be used, the cistern or external vessel, LMNO, Pl. VIII. Fig. 1. is to be filled with water to a determinate height, which should be the same in all experiments. The level of the water should be taken when the beam of the balance stands horizontal; this level, when the jar is at the bottom of the cistern, is increased by all the water which it displaces, and is diminished in proportion as the jar rises to its highest elevation. We next endeavour, by repeated trials, to discover at what elevation the box 28 must be fixed, to render the pressure equal in all situations of the beam. I should have said nearly, because this correction is not absolutely rigorous; and differences of a quarter, or even of half a line, are not of any consequence. This height of the box 28 is not the same for every degree of pressure, but varies according as this is of one, two, three, or more inches. All these should be registered with great order and precision. We next take a bottle which holds eight or ten pints, the capacity of which is very accurately determined by weighing the water it is capable of containing. This bottle is turned bottom upwards, full of water, in the cistern of the pneumato chemical apparatus GHIK, Fig. 1. and is set on its mouth upon the shelf of the apparatus, instead of the glass jar V, having the extremity 11 of the tube 7, 8, 9, 10, 11, inserted into its mouth. The machine is fixed at zero of pressure, and the degree marked by the index 30 upon the sector m l is accurately observed; then, by opening the stop-cock 8, and pressing a little upon the jar A, as much air is forced into the bottle as fills it entirely. The degree marked by the index upon the sector is now observed, and we calculate what number of cubical inches correspond to each degree. We then fill a second and third bottle, and so on, in the same manner, with the same precautions, and even repeat the operation several times with bottles of different sizes, till at last, by accurate attention, we ascertain the exact gage or capacity of the jar A, in all its parts; but it is better to have it formed at first accurately cylindrical, by which we avoid these calculations and estimates. The instrument I have been describing was constructed with great accuracy and uncommon skill by Mr Meignie junior, engineer and physical instrument-maker. It is a most valuable instrument, from the great number of purposes to which it is applicable; and, indeed, there are many experiments which are almost impossible to be performed without it. It becomes expensive, because, in many experiments, such as the formation of water and of nitric acid, it is absolutely necessary to employ two of the same machines. In the present advanced state of chemistry, very expensive and complicated instruments are become indispensibly necessary for ascertaining the analysis and synthesis of bodies with the requisite precision as to quantity and proportion; it is certainly proper to endeavour to simplify these, and to render them less costly; but this ought by no means to be attempted at the expence of their conveniency of application, and much less of their accuracy. SECT. III. _Some other methods of measuring the volume of Gasses._ The gazometer described in the foregoing section is too costly and too complicated for being generally used in laboratories for measuring the gasses, and is not even applicable to every circumstance of this kind. In numerous series of experiments, more simple and more readily applicable methods must be employed. For this purpose I shall describe the means I used before I was in possession of a gazometer, and which I still use in preference to it in the ordinary course of my experiments. Suppose that, after an experiment, there is a residuum of gas, neither absorbable by alkali nor water, contained in the upper part of the jar AEF, Pl. IV. Fig. 3. standing on the shelf of a pneumato-chemical apparatus, of which we wish to ascertain the quantity, we must first mark the height to which the mercury or water rises in the jar with great exactness, by means of slips of paper pasted in several parts round the jar. If we have been operating in mercury, we begin by displacing the mercury from the jar, by introducing water in its stead. This is readily done by filling a bottle quite full of water; having stopped it with your finger, turn it up, and introduce its mouth below the edge of the jar; then, turning down its body again, the mercury, by its gravity, falls into the bottle, and the water rises in the jar, and takes the place occupied by the mercury. When this is accomplished, pour so much water into the cistern ABCD as will stand about an inch over the surface of the mercury; then pass the dish BC, Pl. V. Fig. 9. under the jar, and carry it to the water cistern, Fig. 1. and 2. We here exchange the gas into another jar, which has been previously graduated in the manner to be afterwards described; and we thus judge of the quantity or volume of the gas by means of the degrees which it occupies in the graduated jar. There is another method of determining the volume of gas, which may either be substituted in place of the one above described, or may be usefully employed as a correction or proof of that method. After the air or gas is exchanged from the first jar, marked with slips of paper, into the graduated jar, turn up the mouth of the marked jar, and fill it with water exactly to the marks EF, Pl. IV. Fig. 3. and by weighing the water we determine the volume of the air or gas it contained, allowing one cubical foot, or 1728 cubical inches, of water for each 70 pounds, French weight. The manner of graduating jars for this purpose is very easy, and we ought to be provided with several of different sizes, and even several of each size, in case of accidents. Take a tall, narrow, and strong glass jar, and, having filled it with water in the cistern, Pl. V. Fig. 1. place it upon the shelf ABCD; we ought always to use the same place for this operation, that the level of the shelf may be always exactly similar, by which almost the only error to which this process is liable will be avoided. Then take a narrow mouthed phial which holds exactly 6 oz. 3 gros 61 grs. of water, which corresponds to 10 cubical inches. If you have not one exactly of this dimension, choose one a little larger, and diminish its capacity to the size requisite, by dropping in a little melted wax and rosin. This bottle serves the purpose of a standard for gaging the jars. Make the air contained in this bottle pass into the jar, and mark exactly the place to which the water has descended; add another measure of air, and again mark the place of the water, and so on, till all the water be displaced. It is of great consequence that, during the course of this operation, the bottle and jar be kept at the same temperature with the water in the cistern; and, for this reason, we must avoid keeping the hands upon either as much as possible; or, if we suspect they have been heated, we must cool them by means of the water in the cistern. The height of the barometer and thermometer during this experiment is of no consequence. When the marks have been thus ascertained upon the jar for every ten cubical inches, we engrave a scale upon one of its sides, by means of a diamond pencil. Glass tubes are graduated in the same manner for using in the mercurial apparatus, only they must be divided into cubical inches, and tenths of a cubical inch. The bottle used for gaging these must hold 8 oz. 6 gros 25 grs. of mercury, which exactly corresponds to a cubical inch of that metal. The method of determining the volume of air or gas, by means of a graduated jar, has the advantage of not requiring any correction for the difference of height between the surface of the water within the jar, and in the cistern; but it requires corrections with respect to the height of the barometer and thermometer. But, when we ascertain the volume of air by weighing the water which the jar is capable of containing, up to the marks EF, it is necessary to make a farther correction, for the difference between the surface of the water in the cistern, and the height to which it rises within the jar. This will be explained in the fifth section of this chapter. SECT. IV. _Of the method of Separating the different Gasses from each other._ As experiments often produce two, three, or more species of gas, it is necessary to be able to separate these from each other, that we may ascertain the quantity and species of each. Suppose that under the jar A, Pl. IV. Fig. 3. is contained a quantity of different gasses mixed together, and standing over mercury, we begin by marking with slips of paper, as before directed, the height at which the mercury stands within the glass; then introduce about a cubical inch of water into the jar, which will swim over the surface of the mercury: If the mixture of gas contains any muriatic or sulphurous acid gas, a rapid and considerable absorption will instantly take place, from the strong tendency these two gasses have, especially the former, to combine with, or be absorbed by water. If the water only produces a slight absorption of gas hardly equal to its own bulk, we conclude, that the mixture neither contains muriatic acid, sulphuric acid, or ammoniacal gas, but that it contains carbonic acid gas, of which water only absorbs about its own bulk. To ascertain this conjecture, introduce some solution of caustic alkali, and the carbonic acid gas will be gradually absorbed in the course of a few hours; it combines with the caustic alkali or potash, and the remaining gas is left almost perfectly free from any sensible residuum of carbonic acid gas. After each experiment of this kind, we must carefully mark the height at which the mercury stands within the jar, by slips of paper pasted on, and varnished over when dry, that they may not be washed off when placed in the water apparatus. It is likewise necessary to register the difference between the surface of the mercury in the cistern and that in the jar, and the height of the barometer and thermometer, at the end of each experiment. When all the gas or gasses absorbable by water and potash are absorbed, water is admitted into the jar to displace the mercury; and, as is described in the preceding section, the mercury in the cistern is to be covered by one or two inches of water. After this, the jar is to be transported by means of the flat dish BC, Pl. V. Fig. 9. into the water apparatus; and the quantity of gas remaining is to be ascertained by changing it into a graduated jar. After this, small trials of it are to be made by experiments in little jars, to ascertain nearly the nature of the gas in question. For instance, into a small jar full of the gas, Fig. 8. Pl. V. a lighted taper is introduced; if the taper is not immediately extinguished, we conclude the gas to contain oxygen gas; and, in proportion to the brightness of the flame, we may judge if it contain less or more oxygen gas than atmospheric air contains. If, on the contrary, the taper be instantly extinguished, we have strong reason to presume that the residuum is chiefly composed of azotic gas. If, upon the approach of the taper, the gas takes fire and burns quietly at the surface with a white flame, we conclude it to be pure hydrogen gas; if this flame is blue, we judge it consists of carbonated hydrogen gas; and, if it takes fire with a sudden deflagration, that it is a mixture of oxygen and hydrogen gas. If, again, upon mixing a portion of the residuum with oxygen gas, red fumes are produced, we conclude that it contains nitrous gas. These preliminary trials give some general knowledge of the properties of the gas, and nature of the mixture, but are not sufficient to determine the proportions and quantities of the several gasses of which it is composed. For this purpose all the methods of analysis must be employed; and, to direct these properly, it is of great use to have a previous approximation by the above methods. Suppose, for instance, we know that the residuum consists of oxygen and azotic gas mixed together, put a determinate quantity, 100 parts, into a graduated tube of ten or twelve lines diameter, introduce a solution of sulphuret of potash in contact with the gas, and leave them together for some days; the sulphuret absorbs the whole oxygen gas, and leaves the azotic gas pure. If it is known to contain hydrogen gas, a determinate quantity is introduced into Volta's eudiometer alongst with a known proportion of hydrogen gas; these are deflagrated together by means of the electrical spark; fresh portions of oxygen gas are successively added, till no farther deflagration takes place, and till the greatest possible diminution is produced. By this process water is formed, which is immediately absorbed by the water of the apparatus; but, if the hydrogen gas contain charcoal, carbonic acid is formed at the same time, which is not absorbed so quickly; the quantity of this is readily ascertained by assisting its absorption, by means of agitation. If the residuum contains nitrous gas, by adding oxygen gas, with which it combines into nitric acid, we can very nearly ascertain its quantity, from the diminution produced by this mixture. I confine myself to these general examples, which are sufficient to give an idea of this kind of operations; a whole volume would not serve to explain every possible case. It is necessary to become familiar with the analysis of gasses by long experience; we must even acknowledge that they mostly possess such powerful affinities to each other, that we are not always certain of having separated them completely. In these cases, we must vary our experiments in every possible point of view, add new agents to the combination, and keep out others, and continue our trials, till we are certain of the truth and exactitude of our conclusions. SECT. V. _Of the necessary corrections upon the volume of the Gasses, according to the pressure of the Atmosphere._ All elastic fluids are compressible or condensible in proportion to the weight with which they are loaded. Perhaps this law, which is ascertained by general experience, may suffer some irregularity when these fluids are under a degree of condensation almost sufficient to reduce them to the liquid state, or when either in a state of extreme rarefaction or condensation; but we seldom approach either of these limits with most of the gasses which we submit to our experiments. I understand this proposition of gasses being compressible, in proportion to their superincumbent weights, as follows: A barometer, which is an instrument generally known, is, properly speaking, a species of syphon, ABCD, Pl. XII. Fig. 16. whose leg AB is filled with mercury, whilst the leg CD is full of air. If we suppose the branch CD indefinitely continued till it equals the height of our atmosphere, we can readily conceive that the barometer is, in reality, a sort of balance, in which a column of mercury stands in equilibrium with a column of air of the same weight. But it is unnecessary to prolongate the branch CD to such a height, as it is evident that the barometer being immersed in air, the column of mercury AB will be equally in equilibrium with a column of air of the same diameter, though the leg CD be cut off at C, and the part CD be taken away altogether. The medium height of mercury in equilibrium with the weight of a column of air, from the highest part of the atmosphere to the surface of the earth is about twenty-eight French inches in the lower parts of the city of Paris; or, in other words, the air at the surface of the earth at Paris is usually pressed upon by a weight equal to that of a column of mercury twenty-eight inches in height. I must be understood in this way in the several parts of this publication when talking of the different gasses, as, for instance, when the cubical foot of oxygen gas is said to weigh 1 oz. 4 gros, under 28 inches pressure. The height of this column of mercury, supported by the pressure of the air, diminishes in proportion as we are elevated above the surface of the earth, or rather above the level of the sea, because the mercury can only form an equilibrium with the column of air which is above it, and is not in the smallest degree affected by the air which is below its level. In what ratio does the mercury in the barometer descend in proportion to its elevation? or, what is the same thing, according to what law or ratio do the several strata of the atmosphere decrease in density? This question, which has exercised the ingenuity of natural philosophers during last century, is considerably elucidated by the following experiment. If we take the glass syphon ABCDE, Pl. XII. Fig. 17. shut at E, and open at A, and introduce a few drops of mercury, so as to intercept the communication of air between the leg AB and the leg BE, it is evident that the air contained in BCDE is pressed upon, in common with the whole surrounding air, by a weight or column of air equal to 28 inches of mercury. But, if we pour 28 inches of mercury into the leg AB, it is plain the air in the branch BCDE will now be pressed upon by a weight equal to twice 28 inches of mercury, or twice the weight of the atmosphere; and experience shows, that, in this case, the included air, instead of filling the tube from B to E, only occupies from C to E, or exactly one half of the space it filled before. If to this first column of mercury we add two other portions of 28 inches each, in the branch AB, the air in the branch BCDE will be pressed upon by four times the weight of the atmosphere, or four times the weight of 28 inches of mercury, and it will then only fill the space from D to E, or exactly one quarter of the space it occupied at the commencement of the experiment. From these experiments, which may be infinitely varied, has been deduced as a general law of nature, which seems applicable to all permanently elastic fluids, that they diminish in volume in proportion to the weights with which they are pressed upon; or, in other words, "_the volume of all elastic fluids is in the inverse ratio of the weight by which they are compressed_." The experiments which have been made for measuring the heights of mountains by means of the barometer, confirm the truth of these deductions; and, even supposing them in some degree inaccurate, these differences are so extremely small, that they may be reckoned as nullities in chemical experiments. When this law of the compression of elastic fluids is once well understood, it becomes easily applicable to the corrections necessary in pneumato chemical experiments upon the volume of gas, in relation to its pressure. These corrections are of two kinds, the one relative to the variations of the barometer, and the other for the column of water or mercury contained in the jars. I shall endeavour to explain these by examples, beginning with the most simple case. Suppose that 100 cubical inches of oxygen gas are obtained at 10° (54.5°) of the thermometer, and at 28 inches 6 lines of the barometer, it is required to know what volume the 100 cubical inches of gas would occupy, under the pressure of 28 inches[58], and what is the exact weight of the 100 inches of oxygen gas? Let the unknown volume, or the number of inches this gas would occupy at 28 inches of the barometer, be expressed by x; and, since the volumes are in the inverse ratio of their superincumbent weights, we have the following statement: 100 cubical inches is to x inversely as 28.5 inches of pressure is to 28.0 inches; or directly 28 : 28.5 :: 100 : x = 101.786--cubical inches, at 28 inches barometrical pressure; that is to say, the same gas or air which at 28.5 inches of the barometer occupies 100 cubical inches of volume, will occupy 101.786 cubical inches when the barometer is at 28 inches. It is equally easy to calculate the weight of this gas, occupying 100 cubical inches, under 28.5 inches of barometrical pressure; for, as it corresponds to 101.786 cubical inches at the pressure of 28, and as, at this pressure, and at 10° (54.5°) of temperature, each cubical inch of oxygen gas weighs half a grain, it follows, that 100 cubical inches, under 28.5 barometrical pressure, must weigh 50.893 grains. This conclusion might have been formed more directly, as, since the volume of elastic fluids is in the inverse ratio of their compression, their weights must be in the direct ratio of the same compression: Hence, since 100 cubical inches weigh 50 grains, under the pressure of 28 inches, we have the following statement to determine the weight of 100 cubical inches of the same gas as 28.5 barometrical pressure, 28 : 50 :: 28.5 : x, the unknown quantity, = 50.893. The following case is more complicated: Suppose the jar A, Pl. XII. Fig. 18. to contain a quantity of gas in its upper part ACD, the rest of the jar below CD being full of mercury, and the whole standing in the mercurial bason or reservoir GHIK, filled with mercury up to EF, and that the difference between the surface CD of the mercury in the jar, and EF, that in the cistern, is six inches, while the barometer stands at 27.5 inches. It is evident from these data, that the air contained in ACD is pressed upon by the weight of the atmosphere, diminished by the weight of the column of mercury CE, or by 27.5 - 6 = 21.5 inches of barometrical pressure. This air is therefore less compressed than the atmosphere at the mean height of the barometer, and consequently occupies more space than it would occupy at the mean pressure, the difference being exactly proportional to the difference between the compressing weights. If, then, upon measuring the space ACD, it is found to be 120 cubical inches, it must be reduced to the volume which it would occupy under the mean pressure of 28 inches. This is done by the following statement: 120 : x, the unknown volume, :: 21.5 : 28 inversely; this gives x = 120 × 21.5 / 28 = 92.143 cubical inches. In these calculations we may either reduce the height of the mercury in the barometer, and the difference of level in the jar and bason, into lines or decimal fractions of the inch; but I prefer the latter, as it is more readily calculated. As, in these operations, which frequently recur, it is of great use to have means of abbreviation, I have given a table in the appendix for reducing lines and fractions of lines into decimal fractions of the inch. In experiments performed in the water-apparatus, we must make similar corrections to procure rigorously exact results, by taking into account, and making allowances for the difference of height of the water within the jar above the surface of the water in the cistern. But, as the pressure of the atmosphere is expressed in inches and lines of the mercurial barometer, and, as homogeneous quantities only can be calculated together, we must reduce the observed inches and lines of water into correspondent heights of the mercury. I have given a table in the appendix for this conversion, upon the supposition that mercury is 13.5681 times heavier than water. SECT. VI. _Of Corrections relative to the Degrees of the Thermometer._ In ascertaining the weight of gasses, besides reducing them to a mean of barometrical pressure, as directed in the preceding section, we must likewise reduce them to a standard thermometrical temperature; because, all elastic fluids being expanded by heat, and condensed by cold, their weight in any determinate volume is thereby liable to considerable alterations. As the temperature of 10° (54.5°) is a medium between the heat of summer and the cold of winter, being the temperature of subterraneous places, and that which is most easily approached to at all seasons, I have chosen that degree as a mean to which I reduce air or gas in this species of calculation. Mr de Luc found that atmospheric air was increased 1/215 part of its bulk, by each degree of a mercurial thermometer, divided into 81 degrees, between the freezing and boiling points; this gives 1/211 part for each degree of Reaumur's thermometer, which is divided into 80 degrees between these two points. The experiments of Mr Monge seem to make this dilatation less for hydrogen gas, which he thinks is only dilated 1/180. We have not any exact experiments hitherto published respecting the ratio of dilatation of the other gasses; but, from the trials which have been made, their dilatation seems to differ little from that of atmospheric air. Hence I may take for granted, till farther experiments give us better information upon this subject, that atmospherical air is dilated 1/210 part, and hydrogen gas 1/190 part for each degree of the thermometer; but, as there is still great uncertainty upon this point, we ought always to operate in a temperature as near as possible to the standard of 10°, (54.5°) by this means any errors in correcting the weight or volume of gasses by reducing them to the common standard, will become of little moment. The calculation for this correction is extremely easy. Divide the observed volume of air by 210, and multiply the quotient by the degrees of temperature above or below 10° (54.5°). This correction is negative when the actual temperature is above the standard, and positive when below. By the use of logarithmical tables this calculation is much facilitated[59]. SECT. VII. _Example for calculating the Corrections relative to the Variations of Pressure and Temperature._ CASE. In the jar A, Pl. IV. Fig. 3. standing in a water apparatus, is contained 353 cubical inches of air; the surface of the water within the jar at EF is 4-1/2 inches above the water in the cistern, the barometer is at 27 inches 9-1/2 lines, and the thermometer at 15° (65.75°). Having burnt a quantity of phosphorus in the air, by which concrete phosphoric acid is produced, the air after the combustion occupies 295 cubical inches, the water within the jar stands 7 inches above that in the cistern, the barometer is at 27 inches 9-1/4 lines, and the thermometer at 16° (68°). It is required from these data to determine the actual volume of air before and after combustion, and the quantity absorbed during the process. _Calculation before Combustion._ The air in the jar before combustion was 353 cubical inches, but it was only under a barometrical pressure of 27 inches 9-1/2 lines; which, reduced to decimal fractions by Tab. I. of the Appendix, gives 27.79167 inches; and from this we must deduct the difference of 4-1/2 inches of water, which, by Tab. II. corresponds to 0.33166 inches of the barometer; hence the real pressure of the air in the jar is 27.46001. As the volume of elastic fluids diminish in the inverse ratio of the compressing weights, we have the following statement to reduce the 353 inches to the volume the air would occupy at 28 inches barometrical pressure. 353 : x, the unknown volume, :: 27.46001 : 28. Hence, x = 353 × 27.46001 / 28 = 346.192 cubical inches, which is the volume the same quantity of air would have occupied at 28 inches of the barometer. The 210th part of this corrected volume is 1.65, which, for the five degrees of temperature above the standard gives 8.255 cubical inches; and, as this correction is subtractive, the real corrected volume of the air before combustion is 337.942 inches. _Calculation after Combustion._ By a similar calculation upon the volume of air after combustion, we find its barometrical pressure 27.77083 - 0.51593 = 27.25490. Hence, to have the volume of air under the pressure of 28 inches, 295 : x :: 27.77083 : 28 inversely; or, x = 295 x 27.25490 / 28 = 287.150. The 210th part of this corrected volume is 1.368, which, multiplied by 6 degrees of thermometrical difference, gives the subtractive correction for temperature 8.208, leaving the actual corrected volume of air after combustion 278.942 inches. _Result._ The corrected volume before combustion 337.942 Ditto remaining after combustion 278.942 -------- Volume absorbed during combustion 59.000. SECT. VIII. _Method of determining the Absolute Gravity of the different Gasses._ Take a large balloon A, Pl. V. Fig. 10. capable of holding 17 or 18 pints, or about half a cubical foot, having the brass cap bcde strongly cemented to its neck, and to which the tube and stop-cock f g is fixed by a tight screw. This apparatus is connected by the double screw represented separately at Fig. 12. to the jar BCD, Fig. 10. which must be some pints larger in dimensions than the balloon. This jar is open at top, and is furnished with the brass cap h i, and stop-cock l m. One of these slop-cocks is represented separately at Fig. 11. We first determine the exact capacity of the balloon by filling it with water, and weighing it both full and empty. When emptied of water, it is dried with a cloth introduced through its neck d e, and the last remains of moisture are removed by exhausting it once or twice in an air-pump. When the weight of any gas is to be ascertained, this apparatus is used as follows: Fix the balloon A to the plate of an air-pump by means of the screw of the stop-cock f g, which is left open; the balloon is to be exhausted as completely as possible, observing carefully the degree of exhaustion by means of the barometer attached to the air-pump. When the vacuum is formed, the stop-cock f g is shut, and the weight of the balloon determined with the most scrupulous exactitude. It is then fixed to the jar BCD, which we suppose placed in water in the shelf of the pneumato chemical apparatus Fig. 1.; the jar is to be filled with the gas we mean to weigh, and then, by opening the stop-cocks f g and l m, the gas ascends into the balloon, whilst the water of the cistern rises at the same time into the jar. To avoid very troublesome corrections, it is necessary, during this first part of the operation, to sink the jar in the cistern till the surfaces of the water within the jar and without exactly correspond. The stop-cocks are again shut, and the balloon being unscrewed from its connection with the jar, is to be carefully weighed; the difference between this weight and that of the exhausted balloon is the precise weight of the air or gas contained in the balloon. Multiply this weight by 1728, the number of cubical inches in a cubical foot, and divide the product by the number of cubical inches contained in the balloon, the quotient is the weight of a cubical foot of the gas or air submitted to experiment. Exact account must be kept of the barometrical height and temperature of the thermometer during the above experiment; and from these the resulting weight of a cubical foot is easily corrected to the standard of 28 inches and 10°, as directed in the preceding section. The small portion of air remaining in the balloon after forming the vacuum must likewise be attended to, which is easily determined by the barometer attached to the air-pump. If that barometer, for instance, remains at the hundredth part of the height it stood at before the vacuum was formed, we conclude that one hundredth part of the air originally contained remained in the balloon, and consequently that only 99/100 of gas was introduced from the jar into the balloon. FOOTNOTES: [58] According to the proportion of 114 to 107, given between the French and English foot, 28 inches of the French barometer are equal to 29.83 inches of the English. Directions will be found in the appendix for converting all the French weights and measures used in this work into corresponding English denominations.--E. [59] When Fahrenheit's thermometer is employed, the dilatation by each degree must be smaller, in the proportion of 1 to 2.25, because each degree of Reaumur's scale contains 2.25 degrees of Fahrenheit; hence we must divide by 472.5, and finish the rest of the calculation as above.--E. CHAP. III. _Description of the Calorimeter, or Apparatus for measuring Caloric._ The calorimeter, or apparatus for measuring the relative quantities of heat contained in bodies, was described by Mr de la Place and me in the Memoirs of the Academy for 1780, p. 355. and from that Essay the materials of this chapter are extracted. If, after having cooled any body to the freezing point, it be exposed in an atmosphere of 25° (88.25°), the body will gradually become heated, from the surface inwards, till at last it acquire the same temperature with the surrounding air. But, if a piece of ice be placed in the same situation, the circumstances are quite different; it does not approach in the smallest degree towards the temperature of the circumambient air, but remains constantly at Zero (32°), or the temperature of melting ice, till the last portion of ice be completely melted. This phenomenon is readily explained; as, to melt ice, or reduce it to water, it requires to be combined with a certain portion of caloric; the whole caloric attracted from the surrounding bodies, is arrested or fixed at the surface or external layer of ice which it is employed to dissolve, and combines with it to form water; the next quantity of caloric combines with the second layer to dissolve it into water, and so on successively till the whole ice be dissolved or converted into water by combination with caloric, the very last atom still remaining at its former temperature, because the caloric has never penetrated so far as long as any intermediate ice remained to melt. Upon these principles, if we conceive a hollow sphere of ice at the temperature of Zero (32°) placed in an atmosphere 10° (54.5°), and containing a substance at any degree of temperature above freezing, it follows, 1st, That the heat of the external atmosphere cannot penetrate into the internal hollow of the sphere of ice; 2dly, That the heat of the body placed in the hollow of the sphere cannot penetrate outwards beyond it, but will be stopped at the internal surface, and continually employed to melt successive layers of ice, until the temperature of the body be reduced to Zero (32°), by having all its superabundant caloric above that temperature carried off by the ice. If the whole water, formed within the sphere of ice during the reduction of the temperature of the included body to Zero, be carefully collected, the weight of the water will be exactly proportional to the quantity of caloric lost by the body in passing from its original temperature to that of melting ice; for it is evident that a double quantity of caloric would have melted twice the quantity of ice; hence the quantity of ice melted is a very exact measure of the quantity of caloric employed to produce that effect, and consequently of the quantity lost by the only substance that could possibly have supplied it. I have made this supposition of what would take place in a hollow sphere of ice, for the purpose of more readily explaining the method used in this species of experiment, which was first conceived by Mr de la Place. It would be difficult to procure such spheres of ices and inconvenient to make use of them when got; but, by means of the following apparatus, we have remedied that defect. I acknowledge the name of Calorimeter, which I have given it, as derived partly from Greek and partly from Latin, is in some degree open to criticism; but, in matters of science, a slight deviation from strict etymology, for the sake of giving distinctness of idea, is excusable; and I could not derive the name entirely from Greek without approaching too near to the names of known instruments employed for other purposes. The calorimeter is represented in Pl. VI. It is shown in perspective at Fig. 1. and its interior structure is engraved in Fig. 2. and 3.; the former being a horizontal, and the latter a perpendicular section. Its capacity or cavity is divided into three parts, which, for better distinction, I shall name the interior, middle, and external cavities. The interior cavity f f f f, Fig. 4. into which the substances submitted to experiment are put, is composed of a grating or cage of iron wire, supported by several iron bars; its opening or mouth LM, is covered by the lid HG, of the same materials. The middle cavity b b b b, Fig. 2. and 3. is intended to contain the ice which surrounds the interior cavity, and which is to be melted by the caloric of the substance employed in the experiment. The ice is supported by the grate m m at the bottom of the cavity, under which is placed the sieve n n. These two are represented separately in Fig. 5. and 6. In proportion as the ice contained in the middle cavity is melted, by the caloric disengaged from the body placed in the interior cavity, the water runs through the grate and sieve, and falls through the conical funnel c c d, Fig. 3. and tube x y, into the receiver F, Fig. 1. This water may be retained or let out at pleasure, by means of the stop-cock u. The external cavity a a a a, Fig. 2. and 3. is filled with ice, to prevent any effect upon the ice in the middle cavity from the heat of the surrounding air, and the water produced from it is carried off through the pipe ST, which shuts by means of the stop-cock r. The whole machine is covered by the lid FF, Fig. 7. made of tin painted with oil colour, to prevent rust. When this machine is to be employed, the middle cavity b b b b, Fig. 2. and 3., the lid GH, Fig. 4. of the interior cavity, the external cavity a a a a, Fig. 2. and 3. and the general lid FF, Fig. 7. are all filled with pounded ice, well rammed, so that no void spaces remain, and the ice of the middle cavity is allowed to drain. The machine is then opened, and the substance submitted to experiment being placed in the interior cavity, it is instantly closed. After waiting till the included body is completely cooled to the freezing point, and the whole melted ice has drained from the middle cavity, the water collected in the vessel F, Fig. 1. is accurately weighed. The weight of the water produced during the experiment is an exact measure of the caloric disengaged during the cooling of the included body, as this substance is evidently in a similar situation with the one formerly mentioned as included in a hollow sphere of ice; the whole caloric disengaged is stopped by the ice in the middle cavity, and that ice is preserved from being affected by any other heat by means of the ice contained in the general lid, Fig. 7. and in the external cavity. Experiments of this kind last from fifteen to twenty hours; they are sometimes accelerated by covering up the substance in the interior cavity with well drained ice, which hastens its cooling. The substances to be operated upon are placed in the thin iron bucket, Fig. 8. the cover of which has an opening fitted with a cork, into which a small thermometer is fixed. When we use acids, or other fluids capable of injuring the metal of the instruments, they are contained in the matras, Fig. 10. which has a similar thermometer in a cork fitted to its mouth, and which stands in the interior cavity upon the small cylindrical support RS, Fig. 10. It is absolutely requisite that there be no communication between the external and middle cavities of the calorimeter, otherwise the ice melted by the influence of the surrounding air, in the external cavity, would mix with the water produced from the ice of the middle cavity, which would no longer be a measure of the caloric lost by the substance submitted to experiment. When the temperature of the atmosphere is only a few degrees above the freezing point, its heat can hardly reach the middle cavity, being arrested by the ice of the cover, Fig. 7. and of the external cavity; but, if the temperature of the air be under the degree of freezing, it might cool the ice contained in the middle cavity, by causing the ice in the external cavity to fall, in the first place, below zero (32°). It is therefore essential that this experiment be carried on in a temperature somewhat above freezing: Hence, in time of frost, the calorimeter must be kept in an apartment carefully heated. It is likewise necessary that the ice employed be not under zero (32°); for which purpose it must be pounded, and spread out thin for some time, in a place of a higher temperature. The ice of the interior cavity always retains a certain quantity of water adhering to its surface, which may be supposed to belong to the result of the experiment; but as, at the beginning of each experiment, the ice is already saturated with as much water as it can contain, if any of the water produced by the caloric should remain attached to the ice, it is evident, that very nearly an equal quantity of what adhered to it before the experiment must have run down into the vessel F in its stead; for the inner surface of the ice in the middle cavity is very little changed during the experiment. By any contrivance that could be devised, we could not prevent the access of the external air into the interior cavity when the atmosphere was 9° or 10° (52° or 54°) above zero. The air confined in the cavity being in that case specifically heavier than the external air, escapes downwards through the pipe x y, Fig. 3, and is replaced by the warmer external air, which, giving out its caloric to the ice, becomes heavier, and sinks in its turn; thus a current of air is formed through the machine, which is the more rapid in proportion as the external air exceeds the internal in temperature. This current of warm air must melt a part of the ice, and injure the accuracy of the experiment: We may, in a great degree, guard against this source of error by keeping the stop-cock u continually shut; but it is better to operate only when the temperature of the external air does not exceed 3°, or at most 4°, (39° to 41°); for we have observed, that, in this case, the melting of the interior ice by the atmospheric air is perfectly insensible; so that we may answer for the accuracy of our experiments upon the specific heat of bodies to a fortieth part. We have caused make two of the above described machines; one, which is intended for such experiments as do not require the interior air to be renewed, is precisely formed according to the description here given; the other, which answers for experiments upon combustion, respiration, &c. in which fresh quantities of air are indispensibly necessary, differs from the former in having two small tubes in the two lids, by which a current of atmospheric air may be blown into the interior cavity of the machine. It is extremely easy, with this apparatus, to determine the phenomena which occur in operations where caloric is either disengaged or absorbed. If we wish, for instance, to ascertain the quantity of caloric which is disengaged from a solid body in cooling a certain number of degrees, let its temperature be raised to 80° (212°); it is then placed in the interior cavity f f f f, Fig. 2. and 3. of the calorimeter, and allowed to remain till we are certain that its temperature is reduced to zero (32°); the water produced by melting the ice during its cooling is collected, and carefully weighed; and this weight, divided by the volume of the body submitted to experiment, multiplied into the degrees of temperature which it had above zero at the commencement of the experiment, gives the proportion of what the English philosophers call specific heat. Fluids are contained in proper vessels, whose specific heat has been previously ascertained, and operated upon in the machine in the same manner as directed for solids, taking care to deduct, from the quantity of water melted during the experiment, the proportion which belongs to the containing vessel. If the quantity of caloric disengaged during the combination of different substances is to be determined, these substances are to be previously reduced to the freezing degree by keeping them a sufficient time surrounded with pounded ice; the mixture is then to be made in the inner cavity of the calorimeter, in a proper vessel likewise reduced to zero (32°); and they are kept inclosed till the temperature of the combination has returned to the same degree: The quantity of water produced is a measure of the caloric disengaged during the combination. To determine the quantity of caloric disengaged during combustion, and during animal respiration, the combustible bodies are burnt, or the animals are made to breathe in the interior cavity, and the water produced is carefully collected. Guinea pigs, which resist the effects of cold extremely well, are well adapted for this experiment. As the continual renewal of air is absolutely necessary in such experiments, we blow fresh air into the interior cavity of the calorimeter by means of a pipe destined for that purpose, and allow it to escape through another pipe of the same kind; and that the heat of this air may not produce errors in the results of the experiments, the tube which conveys it into the machine is made to pass through pounded ice, that it may be reduced to zero (32°) before it arrives at the calorimeter. The air which escapes must likewise be made to pass through a tube surrounded with ice, included in the interior cavity of the machine, and the water which is produced must make a part of what is collected, because the caloric disengaged from this air is part of the product of the experiment. It is somewhat more difficult to determine the specific caloric contained in the different gasses, on account of their small degree of density; for, if they are only placed in the calorimeter in vessels like other fluids, the quantity of ice melted is so small, that the result of the experiment becomes at best very uncertain. For this species of experiment we have contrived to make the air pass through two metallic worms, or spiral tubes; one of these, through which the air passes, and becomes heated in its way to the calorimeter, is contained in a vessel full of boiling water, and the other, through which the air circulates within the calorimeter to disengage its caloric, is placed in the interior cavity, f f f f, of that machine. By means of a small thermometer placed at one end of the second worm, the temperature of the air, as it enters the calorimeter, is determined, and its temperature in getting out of the interior cavity is found by another thermometer placed at the other end of the worm. By this contrivance we are enabled to ascertain the quantity of ice melted by determinate quantities of air or gas, while losing a certain number of degrees of temperature, and, consequently, to determine their several degrees of specific caloric. The same apparatus, with some particular precautions, may be employed to ascertain the quantity of caloric disengaged by the condensation of the vapours of different liquids. The various experiments which may be made with the calorimeter do not afford absolute conclusions, but only give us the measure of relative quantities; we have therefore to fix a unit, or standard point, from whence to form a scale of the several results. The quantity of caloric necessary to melt a pound of ice has been chosen as this unit; and, as it requires a pound of water of the temperature of 60° (167°) to melt a pound of ice, the quantity of caloric expressed by our unit or standard point is what raises a pound of water from zero (32°) to 60° (167°). When this unit is once determined, we have only to express the quantities of caloric disengaged from different bodies by cooling a certain number of degrees, in analogous values: The following is an easy mode of calculation for this purpose, applied to one of our earliest experiments. We took 7 lib. 11 oz. 2 gros 36 grs. of plate-iron, cut into narrow slips, and rolled up, or expressing the quantity in decimals, 7.7070319. These, being heated in a bath of boiling water to about 78° (207.5°), were quickly introduced into the interior cavity of the calorimeter: At the end of eleven hours, when the whole quantity of water melted from the ice had thoroughly drained off, we found that 1.109795 pounds of ice were melted. Hence, the caloric disengaged from the iron by cooling 78° (175.5°) having melted 1.109795 pounds of ice, how much would have been melted by cooling 60° (135°)? This question gives the following statement in direct proportion, 78 : 1.109795 :: 60 : x = 0.85369. Dividing this quantity by the weight of the whole iron employed, viz. 7.7070319, the quotient 0.110770 is the quantity of ice which would have been melted by one pound of iron whilst cooling through 60° (135°) of temperature. Fluid substances, such as sulphuric and nitric acids, &c. are contained in a matras, Pl. VI. Fig. 9. having a thermometer adapted to the cork, with its bulb immersed in the liquid. The matras is placed in a bath of boiling water, and when, from the thermometer, we judge the liquid is raised to a proper temperature, the matras is placed in the calorimeter. The calculation of the products, to determine the specific caloric of these fluids, is made as above directed, taking care to deduct from the water obtained the quantity which would have been produced by the matras alone, which must be ascertained by a previous experiment. The table of the results obtained by these experiments is omitted, because not yet sufficiently complete, different circumstances having occasioned the series to be interrupted; it is not, however, lost sight of; and we are less or more employed upon the subject every winter. CHAP. IV. _Of Mechanical Operations for Division of Bodies._ SECT. I. _Of Trituration, Levigation, and Pulverization._ These are, properly speaking, only preliminary mechanical operations for dividing and separating the particles of bodies, and reducing them into very fine powder. These operations can never reduce substances into their primary, or elementary and ultimate particles; they do not even destroy the aggregation of bodies; for every particle, after the most accurate trituration, forms a small whole, resembling the original mass from which it was divided. The real chemical operations, on the contrary, such as solution, destroy the aggregation of bodies, and separate their constituent and integrant particles from each other. Brittle substances are reduced to powder by means of pestles and mortars. These are of brass or iron, Pl. I. Fig. 1.; of marble or granite, Fig. 2.; of lignum vitae, Fig. 3.; of glass, Fig. 4.; of agate, Fig. 5.; or of porcellain, Fig. 6. The pestles for each of these are represented in the plate, immediately below the mortars to which they respectively belong, and are made of hammered iron or brass, of wood, glass, porcellain, marble, granite, or agate, according to the nature of the substances they are intended to triturate. In every laboratory, it is requisite to have an assortment of these utensils, of various sizes and kinds: Those of porcellain and glass can only be used for rubbing substances to powder, by a dexterous use of the pestle round the sides of the mortar, as it would be easily broken by reiterated blows of the pestle. The bottom of mortars ought to be in the form of a hollow sphere, and their sides should have such a degree of inclination as to make the substances they contain fall back to the bottom when the pestle is lifted, but not so perpendicular as to collect them too much together, otherwise too large a quantity would get below the pestle, and prevent its operation. For this reason, likewise, too large a quantity of the substance to be powdered ought not to be put into the mortar at one time; and we must from time to time get rid of the particles already reduced to powder, by means of sieves to be afterwards described. The most usual method of levigation is by means of a flat table ABCD, Pl. 1. Fig. 7. of porphyry, or other stone of similar hardness, upon which the substance to be reduced to powder is spread, and is then bruised and rubbed by a muller M, of the same hard materials, the bottom of which is made a small portion of a large sphere; and, as the muller tends continually to drive the substances towards the sides of the table, a thin flexible knife, or spatula of iron, horn, wood, or ivory, is used for bringing them back to the middle of the stone. In large works, this operation is performed by means of large rollers of hard stone, which turn upon each other, either horizontally, in the way of corn-mills, or by one vertical roller turning upon a flat stone. In the above operations, it is often requisite to moisten the substances a little, to prevent the fine powder from flying off. There are many bodies which cannot be reduced to powder by any of the foregoing methods; such are fibrous substances, as woods; such as are tough and elastic, as the horns of animals, elastic gum, &c. and the malleable metals which flatten under the pestle, instead of being reduced to powder. For reducing the woods to powder, rasps, as Pl. I. Fig. 8. are employed; files of a finer kind are used for horn, and still finer, Pl. 1. Fig. 9. and 10. for metals. Some of the metals, though not brittle enough to powder under the pestle, are too soft to be filed, as they clog the file, and prevent its operation. Zinc is one of these, but it may be powdered when hot in a heated iron mortar, or it may be rendered brittle, by alloying it with a small quantity of mercury. One or other of these methods is used by fire-work makers for producing a blue flame by means of zinc. Metals may be reduced into grains, by pouring them when melted into water, which serves very well when they are not wanted in fine powder. Fruits, potatoes, &c. of a pulpy and fibrous nature may be reduced to pulp by means of the grater, Pl. 1. Fig. 11. The choice of the different substances of which these instruments are made is a matter of importance; brass or copper are unfit for operations upon substances to be used as food or in pharmacy; and marble or metallic instruments must not be used for acid substances; hence mortars of very hard wood, and those of porcelain, granite, or glass, are of great utility in many operations. SECT. II. _Of Sifting and Washing Powdered Substances._ None of the mechanical operations employed for reducing bodies to powder is capable of producing it of an equal degree of fineness throughout; the powder obtained by the longest and most accurate trituration being still an assemblage of particles of various sizes. The coarser of these are removed, so as only to leave the finer and more homogeneous particles by means of sieves, Pl. I. Fig. 12. 13. 14. 15. of different finenesses, adapted to the particular purposes they are intended for; all the powdered matter which is larger than the intestices of the sieve remains behind, and is again submitted to the pestle, while the finer pass through. The sieve Fig. 12. is made of hair-cloth, or of silk gauze; and the one represented Fig. 13. is of parchment pierced with round holes of a proper size; this latter is employed in the manufacture of gun-powder. When very subtile or valuable materials are to be sifted, which are easily dispersed, or when the finer parts of the powder may be hurtful, a compound sieve, Fig. 15. is made use of, which consists of the sieve ABCD, with a lid EF, and receiver GH; these three parts are represented as joined together for use, Fig. 14. There is a method of procuring powders of an uniform fineness, considerably more accurate than the sieve; but it can only be used with such substances as are not acted upon by water. The powdered substance is mixed and agitated with water, or other convenient fluid; the liquor is allowed to settle for a few moments, and is then decanted off; the coarsest powder remains at the bottom of the vessel, and the finer passes over with the liquid. By repeated decantations in this manner, various sediments are obtained of different degrees of fineness; the last sediment, or that which remains longed suspended in the liquor, being the finest. This process may likewise be used with advantage for separating substances of different degrees of specific gravity, though of the same fineness; this last is chiefly employed in mining, for separating the heavier metallic ores from the lighter earthy matters with which they are mixed. In chemical laboratories, pans and jugs of glass or earthen ware are employed for this operation; sometimes, for decanting the liquor without disturbing the sediment, the glass syphon ABCHI, Pl. II. Fig. 11. is used, which may be supported by means of the perforated board DE, at the proper depth in the vessel FG, to draw off all the liquor required into the receiver LM. The principles and application of this useful instrument are so well known as to need no explanation. SECT. III. _Of Filtration._ A filtre is a species of very fine sieve, which is permeable to the particles of fluids, but through which the particles of the finest powdered solids are incapable of passing; hence its use in separating fine powders from suspension in fluids. In pharmacy, very close and fine woollen cloths are chiefly used for this operation; these are commonly formed in a conical shape, Pl. II. Fig. 2. which has the advantage of uniting all the liquor which drains through into a point A, where it may be readily collected in a narrow mouthed vessel. In large pharmaceutical laboratories, this filtring bag is streached upon a wooden stand, Pl. II. Fig. 1. For the purposes of chemistry, as it is requisite to have the filtres perfectly clean, unsized paper is substituted instead of cloth or flannel; through this substance, no solid body, however finely it be powdered, can penetrate, and fluids percolate through it with the greatest readiness. As paper breaks easily when wet, various methods of supporting it are used according to circumstances. When a large quantity of fluid is to be filtrated, the paper is supported by the frame of wood, Pl. II. Fig. 3. ABCD, having a piece of coarse cloth stretched over it, by means of iron-hooks. This cloth must be well cleaned each time it is used, or even new cloth must be employed, if there is reason to suspect its being impregnated with any thing which can injure the subsequent operations. In ordinary operations, where moderate quantities of fluid are to be filtrated, different kinds of glass funnels are used for supporting the paper, as represented Pl. II. Fig. 5. 6. and 7. When several filtrations must be carried on at once, the board or shelf AB, Fig. 9. supported upon stands C and D, and pierced with round holes, is very convenient for containing the funnels. Some liquors are so thick and clammy, as not to be able to penetrate through paper without some previous preparation, such as clarification by means of white of eggs, which being mixed with the liquor, coagulates when brought to boil, and, entangling the greater part of the impurities of the liquor, rises with them to the surface in the state of scum. Spiritous liquors may be clarified in the same manner by means of isinglass dissolved in water, which coagulates by the action of the alkohol without the assistance of heat. As most of the acids are produced by distillation, and are consequently clear, we have rarely any occasion to filtrate them; but if, at any time, concentrated acids require this operation, it is impossible to employ paper, which would be corroded and destroyed by the acid. For this purpose, pounded glass, or rather quartz or rock-cristal, broke in pieces and grossly powdered, answers very well; a few of the larger pieces are put in the neck of the funnel; these are covered with the smaller pieces, the finer powder is placed over all, and the acid is poured on at top. For the ordinary purposes of society, river-water is frequently filtrated by means of clean washed sand, to separate its impurities. SECT. IV. _Of Decantation._ This operation is often substituted instead of filtration for separating solid particles which are diffused through liquors. These are allowed to settle in conical vessels, ABCDE, Pl. II. Fig. 10. the diffused matters gradually subside, and the clear fluid is gently poured off. If the sediment be extremely light, and apt to mix again with the fluid by the slightest motion, the syphon, Fig. 11. is used, instead of decantation, for drawing off the clear fluid. In experiments, where the weight of the precipitate must be rigorously ascertained, decantation is preferable to filtration, providing the precipitate be several times washed in a considerable proportion of water. The weight of the precipitate may indeed be ascertained, by carefully weighing the filtre before and after the operation; but, when the quantity of precipitate is small, the different proportions of moisture retained by the paper, in a greater or lesser degree of exsiccation, may prove a material source of error, which ought carefully to be guarded against. CHAP. V. _Of Chemical Means for separating the Particles of Bodies from each other; without Decomposition, and for uniting them again._ I have already shown that there are two methods of dividing the particles of bodies, the _mechanical_ and _chemical_. The former only separates a solid mass into a great number of smaller masses; and for these purposes various species of forces are employed, according to circumstances, such as the strength of man or of animals, the weight of water applied through the means of hydraulic engines, the expansive power of steam, the force of the wind, &c. By all these mechanical powers, we can never reduce substances into powder beyond a certain degree of fineness; and the smallest particle produced in this way, though it seems very minute to our organs, is still in fact a mountain, when compared with the ultimate elementary particles of the pulverized substance. The chemical agents, on the contrary, divide bodies into their primitive particles. If, for instance, a neutral salt be acted upon by these, it is divided, as far as is possible, without ceasing to be a neutral salt. In this Chapter, I mean to give examples of this kind of division of bodies, to which I shall add some account of the relative operations. SECT. I. _Of the Solution of Salts._ In chemical language, the terms of _solution_ and _dissolution_ have long been confounded, and have very improperly been indiscriminately employed for expressing both the division of the particles of a salt in a fluid, such as water, and the division of a metal in an acid. A few reflections upon the effects of these two operations will suffice to show that they ought not to be confounded together. In the solution of salts, the saline particles are only separated from each other, whilst neither the salt nor the water are at all decomposed; we are able to recover both the one and the other in the same quantity as before the operation. The same thing takes place in the solution of resins in alkohol. During metallic dissolutions, on the contrary, a decomposition, either of the acid, or of the water which dilutes it, always takes place; the metal combines with oxygen, and is changed into an oxyd, and a gasseous substance is disengaged; so that in reality none of the substances employed remain, after the operation, in the same state they were in before. This article is entirely confined to the consideration of solution. To understand properly what takes place during the solution of salts, it is necessary to know, that, in most of these operations, two distinct effects are complicated together, viz. solution by water, and solution by caloric; and, as the explanation of most of the phenomena of solution depends upon the distinction of these two circumstances, I shall enlarge a little upon their nature. Nitrat of potash, usually called nitre or saltpetre, contains very little water of cristallization, perhaps even none at all; yet this salt liquifies in a degree of heat very little superior to that of boiling water. This liquifaction cannot therefore be produced by means of the water of cristallization, but in consequence of the salt being very fusible in its nature, and from its passing from the solid to the liquid state of aggregation, when but a little raised above the temperature of boiling water. All salts are in this manner susceptible of being liquified by caloric, but in higher or lower degrees of temperature. Some of these, as the acetites of potash and soda, liquify with a very moderate heat, whilst others, as sulphat of potash, lime, &c. require the strongest fires we are capable of producing. This liquifaction of salts by caloric produces exactly the same phenomena with the melting of ice; it is accomplished in each salt by a determinate degree of heat, which remains invariably the same during the whole time of the liquifaction. Caloric is employed, and becomes fixed during the melting of the salt, and is, on the contrary, disengaged when the salt coagulates. These are general phenomena which universally occur during the passage of every species of substance from the solid to the fluid state of aggregation, and from fluid to solid. These phenomena arising from solution by caloric are always less or more conjoined with those which take place during solutions in water. We cannot pour water upon a salt, on purpose to dissolve it, without employing a compound solvent, both water and caloric; hence we may distinguish several different cases of solution, according to the nature and mode of existence of each salt. If, for instance, a salt be difficultly soluble in water, and readily so by caloric, it evidently follows, that this salt will be difficultly soluble in cold water, and considerably in hot water; such is nitrat of potash, and more especially oxygenated muriat of potash. If another salt be little soluble both in water and caloric, the difference of its solubility in cold and warm water will be very inconsiderable; sulphat of lime is of this kind. From these considerations, it follows, that there is a necessary relation between the following circumstances; the solubility of a salt in cold water, its solubility in boiling water, and the degree of temperature at which the same salt liquifies by caloric, unassisted by water; and that the difference of solubility in hot and cold water is so much greater in proportion to its ready solution in caloric, or in proportion to its susceptibility of liquifying in a low degree of temperature. The above is a general view of solution; but, for want of particular facts, and sufficiently exact experiments, it is still nothing more than an approximation towards a particular theory. The means of compleating this part of chemical science is extremely simple; we have only to ascertain how much of each salt is dissolved by a certain quantity of water at different degrees of temperature; and as, by the experiments published by Mr de la Place and me, the quantity of caloric contained in a pound of water at each degree of the thermometer is accurately known, it will be very easy to determine, by simple experiments, the proportion of water and caloric required for solution by each salt, what quantity of caloric is absorbed by each at the moment of liquifaction, and how much is disengaged at the moment of cristallization. Hence the reason why salts are more rapidly soluble in hot than in cold water is perfectly evident. In all solutions of salts caloric is employed; when that is furnished intermediately from the surrounding bodies, it can only arrive slowly to the salt; whereas this is greatly accelerated when the requisite caloric exists ready combined with the water of solution. In general, the specific gravity of water is augmented by holding salts in solution; but there are some exceptions to the rule. Some time hence, the quantities of radical, of oxygen, and of base, which constitute each neutral salt, the quantity of water and caloric necessary for solution, the increased specific gravity communicated to water, and the figure of the elementary particles of the cristals, will all be accurately known. From these all the circumstances and phenomena of cristallization will be explained, and by these means this part of chemistry will be compleated. Mr Seguin has formed the plan of a thorough investigation of this kind, which he is extremely capable of executing. The solution of salts in water requires no particular apparatus; small glass phials of different sizes, Pl. II. Fig. 16. and 17. pans of earthern ware, A, Fig. 1. and 2. long-necked matrasses, Fig. 14. and pans or basons of copper or of silver, Fig. 13. and 15. answer very well for these operations. SECT. II. _Of Lixiviation._ This is an operation used in chemistry and manufactures for separating substances which are soluble in water from such as are insoluble. The large vat or tub, Pl. II. Fig. 12. having a hole D near its bottom, containing a wooden spiget and fosset or metallic stop-cock DE, is generally used for this purpose. A thin stratum of straw is placed at the bottom of the tub; over this, the substance to be lixiviated is laid and covered by a cloth, then hot or cold water, according to the degree of solubility of the saline matter, is poured on. When the water is supposed to have dissolved all the saline parts, it is let off by the stop-cock; and, as some of the water charged with salt necessarily adheres to the straw and insoluble matters, several fresh quantities of water are poured on. The straw serves to secure a proper passage for the water, and may be compared to the straws or glass rods used in filtrating, to keep the paper from touching the sides of the funnel. The cloth which is laid over the matters under lixiviation prevents the water from making a hollow in these substances where it is poured on, through which it might escape without acting upon the whole mass. This operation is less or more imitated in chemical experiments; but as in these, especially with analytical views, greater exactness is required, particular precautions must be employed, so as not to leave any saline or soluble part in the residuum. More water must be employed than in ordinary lixiviations, and the substances ought to be previously stirred up in the water before the clear liquor is drawn off, otherwise the whole mass might not be equally lixiviated, and some parts might even escape altogether from the action of the water. We must likewise employ fresh portions of water in considerable quantity, until it comes off entirely free from salt, which we may ascertain by means of the hydrometer formerly described. In experiments with small quantities, this operation is conveniently performed in jugs or matrasses of glass, and by filtrating the liquor through paper in a glass funnel. When the substance is in larger quantity, it may be lixiviated in a kettle of boiling water, and filtrated through paper supported by cloth in the wooden frame, Pl. II. Fig. 3. and 4.; and in operations in the large way, the tub already mentioned must be used. SECT. III. _Of Evaporation._ This operation is used for separating two substances from each other, of which one at least must be fluid, and whose degrees of volatility are considerably different. By this means we obtain a salt, which has been dissolved in water, in its concrete form; the water, by heating, becomes combined with caloric, which renders it volatile, while the particles of the salt being brought nearer to each other, and within the sphere of their mutual attraction, unite into the solid state. As it was long thought that the air had great influence upon the quantity of fluid evaporated, it will be proper to point out the errors which this opinion has produced. There certainly is a constant slow evaporation from fluids exposed to the free air; and, though this species of evaporation may be considered in some degree as a solution in air, yet caloric has considerable influence in producing it, as is evident from the refrigeration which always accompanies this process; hence we may consider this gradual evaporation as a compound solution made partly in air, and partly in caloric. But the evaporation which takes place from a fluid kept continually boiling, is quite different in its nature, and in it the evaporation produced by the action of the air is exceedingly inconsiderable in comparison with that which is occasioned by caloric. This latter species may be termed _vaporization_ rather than _evaporation_. This process is not accelerated in proportion to the extent of evaporating surface, but in proportion to the quantities of caloric which combine with the fluid. Too free a current of cold air is often hurtful to this process, as it tends to carry off caloric from the water, and consequently retards its conversion into vapour. Hence there is no inconvenience produced by covering, in a certain degree, the vessels in which liquids are evaporated by continual boiling, provided the covering body be of such a nature as does not strongly draw off the caloric, or, to use an expression of Dr Franklin's, provided it be a bad conductor of heat. In this case, the vapours escape through such opening as is left, and at least as much is evaporated, frequently more than when free access is allowed to the external air. As during evaporation the fluid carried off by caloric is entirely lost, being sacrificed for the sake of the fixed substances with which it was combined, this process is only employed where the fluid is of small value, as water, for instance. But, when the fluid is of more consequence, we have recourse to distillation, in which process we preserve both the fixed substance and the volatile fluid. The vessels employed for evaporation are basons or pans of copper, silver, or lead, Pl. II. Fig. 13. and 15. or capsules of glass, porcellain, or stone ware, Pl. II. A, Fig. 1. and 2. Pl. III. Fig. 3 and 4. The best utensils for this purpose are made of the bottoms of glass retorts and matrasses, as their equal thinness renders them more fit than any other kind of glass vessel for bearing a brisk fire and sudden alterations of heat and cold without breaking. As the method of cutting these glass vessels is no where described in books, I shall here give a description of it, that they may be made by chemists for themselves out of spoiled retorts, matrasses, and recipients, at a much cheaper rate than any which can be procured from glass manufacturers. The instrument, Pl. III. Fig. 5. consisting of an iron ring AC, fixed to the rod AB, having a wooden handle D, is employed as follows: Make the ring red hot in the fire, and put it upon the matrass G, Fig. 6. which is to be cut; when the glass is sufficiently heated, throw on a little cold water, and it will generally break exactly at the circular line heated by the ring. Small flasks or phials of thin glass are exceeding good vessels for evaporating small quantities of fluid; they are very cheap, and stand the fire remarkably. One or more of these may be placed upon a second grate above the furnace, Pl. III. Fig. 2. where they will only experience a gentle heat. By this means a great number of experiments may be carried on at one time. A glass retort, placed in a sand bath, and covered with a dome of baked earth, Pl. III. Fig. 1. answers pretty well for evaporations; but in this way it is always considerably slower, and is even liable to accidents; as the sand heats unequally, and the glass cannot dilate in the same unequal manner, the retort is very liable to break. Sometimes the sand serves exactly the office of the iron ring formerly mentioned; for, if a single drop of vapour, condensed into liquid, happens to fall upon the heated part of the vessel, it breaks circularly at that place. When a very intense fire is necessary, earthen crucibles may be used; but we generally use the word _evaporation_ to express what is produced by the temperature of boiling water, or not much higher. SECT. IV. _Of Cristallization._ In this process the integrant parts of a solid body, separated from each other by the intervention of a fluid, are made to exert the mutual attraction of aggregation, so as to coalesce and reproduce a solid mass. When the particles of a body are only separated by caloric, and the substance is thereby retained in the liquid state, all that is necessary for making it cristallize, is to remove a part of the caloric which is lodged between its particles, or, in other words, to cool it. If this refrigeration be slow, and the body be at the same time left at rest, its particles assume a regular arrangement, and cristallization, properly so called, takes place; but, if the refrigeration is made rapidly, or if the liquor be agitated at the moment of its passage to the concrete state, the cristallization is irregular and confused. The same phenomena occur with watery solutions, or rather in those made partly in water, and partly by caloric. So long as there remains a sufficiency of water and caloric to keep the particles of the body asunder beyond the sphere of their mutual attraction, the salt remains in the fluid state; but, whenever either caloric or water is not present in sufficient quantity, and the attraction of the particles for each other becomes superior to the power which keeps them asunder, the salt recovers its concrete form, and the cristals produced are the more regular in proportion as the evaporation has been slower and more tranquilly performed. All the phenomena we formerly mentioned as taking place during the solution of salts, occur in a contrary sense during their cristallization. Caloric is disengaged at the instant of their assuming the solid state, which furnishes an additional proof of salt being held in solution by the compound action of water and caloric. Hence, to cause salts to cristallize which readily liquify by means of caloric, it is not sufficient to carry off the water which held them in solution, but the caloric united to them must likewise be removed. Nitrat of potash, oxygenated muriat of potash, alum, sulphat of soda, &c. are examples of this circumstance, as, to make these salts cristallize, refrigeration must be added to evaporation. Such salts, on the contrary, as require little caloric for being kept in solution, and which, from that circumstance, are nearly equally soluble in cold and warm water, are cristallizable by simply carrying off the water which holds them in solution, and even recover their solid state in boiling water; such are sulphat of lime, muriat of potash and of soda, and several others. The art of refining saltpetre depends upon these properties of salts, and upon their different degrees of solubility in hot and cold water. This salt, as produced in the manufactories by the first operation, is composed of many different salts; some are deliquescent, and not susceptible of being cristallized, such as the nitrat and muriat of lime; others are almost equally soluble in hot and cold water, as the muriats of potash and of soda; and, lastly, the saltpetre, or nitrat of potash, is greatly more soluble in hot than it is in cold water. The operation is begun, by pouring upon this mixture of salts as much water as will hold even the least soluble, the muriats of soda and of potash, in solution; so long as it is hot, this quantity readily dissolves all the saltpetre, but, upon cooling, the greater part of this salt cristallizes, leaving about a sixth part remaining dissolved, and mixed with the nitrat of lime and the two muriats. The nitre obtained by this process is still somewhat impregnated with other salts, because it has been cristallized from water in which these abound: It is completely purified from these by a second solution in a small quantity of boiling water, and second cristallization. The water remaining after these cristallizations of nitre is still loaded with a mixture of saltpetre, and other salts; by farther evaporation, crude saltpetre, or rough-petre, as the workmen call it, is procured from it, and this is purified by two fresh solutions and cristallizations. The deliquescent earthy salts which do not contain the nitric acid are rejected in this manufacture; but those which consist of that acid neutralized by an earthy base are dissolved in water, the earth is precipitated by means of potash, and allowed to subside; the clear liquor is then decanted, evaporated, and allowed to cristallize. The above management for refining saltpetre may serve as a general rule for separating salts from each other which happen to be mixed together. The nature of each must be considered, the proportion in which each dissolves in given quantities of water, and the different solubility of each in hot and cold water. If to these we add the property which some salts possess, of being soluble in alkohol, or in a mixture of alkohol and water, we have many resources for separating salts from each other by means of cristallization, though it must be allowed that it is extremely difficult to render this separation perfectly complete. The vessels used for cristallization are pans of earthen ware, A, Pl. II. Fig. 1. and 2. and large flat dishes, Pl. III. Fig. 7. When a saline solution is to be exposed to a slow evaporation in the heat of the atmosphere, with free access of air, vessels of some depth, Pl. III. Fig. 3. must be employed, that there may be a considerable body of liquid; by this means the cristals produced are of considerable size, and remarkably regular in their figure. Every species of salt cristallizes in a peculiar form, and even each salt varies in the form of its cristals according to circumstances, which take place during cristallization. We must not from thence conclude that the saline particles of each species are indeterminate in their figures: The primative particles of all bodies, especially of salts, are perfectly constant in their specific forms; but the cristals which form in our experiments are composed of congeries of minute particles, which, though perfectly equal in size and shape, may assume very dissimilar arrangements, and consequently produce a vast variety of regular forms, which have not the smallest apparent resemblance to each other, nor to the original cristal. This subject has been very ably treated by the Abbé Haüy, in several memoirs presented to the Academy, and in his work upon the structure of cristals: It is only necessary to extend generally to the class of salts the principles he has particularly applied to some cristalized stones. SECT. V. _Of Simple Distillation._ As distillation has two distinct objects to accomplish, it is divisible into simple and compound; and, in this section, I mean to confine myself entirely to the former. When two bodies, of which one is more volatile than the other, or has more affinity to caloric, are submitted to distillation, our intention is to separate them from each other: The more volatile substance assumes the form of gas, and is afterwards condensed by refrigeration in proper vessels. In this case distillation, like evaporation, becomes a species of mechanical operation, which separates two substances from each other without decomposing or altering the nature of either. In evaporation, our only object is to preserve the fixed body, without paying any regard to the volatile matter; whereas, in distillation, our principal attention is generally paid to the volatile substance, unless when we intend to preserve both the one and the other. Hence, simple distillation is nothing more than evaporation produced in close vessels. The most simple distilling vessel is a species of bottle or matrass, A, Pl. III. Fig. 8. which has been bent from its original form BC to BD, and which is then called a retort; when used, it is placed either in a reverberatory furnace, Pl. XIII. Fig. 2. or in a sand bath under a dome of baked earth, Pl. III. Fig. 1. To receive and condense the products, we adapt a recipient, E, Pl. III. Fig. 9. which is luted to the retort. Sometimes, more especially in pharmaceutical operations, the glass or stone ware cucurbit, A, with its capital B, Pl. III. Fig. 12, or the glass alembic and capital, Fig. 13. of one piece, is employed. This latter is managed by means of a tubulated opening T, fitted with a ground stopper of cristal; the capital, both of the cucurbit and alembic, has a furrow or trench, r r, intended for conveying the condensed liquor into the beak RS, by which it runs out. As, in almost all distillations, expansive vapours are produced, which might burst the vessels employed, we are under the necessity of having a small hole, T, Fig. 9. in the balloon or recipient, through which these may find vent; hence, in this way of distilling, all the products which are permanently aëriform are entirely lost, and even such as difficultly lose that state have not sufficient space to condense in the balloon: This apparatus is not, therefore, proper for experiments of investigation, and can only be admitted in the ordinary operations of the laboratory or in pharmacy. In the article appropriated for compound distillation, I shall explain the various methods which have been contrived for preserving the whole products from bodies in this process. As glass or earthen vessels are very brittle, and do not readily bear sudden alterations of heat and cold, every well regulated laboratory ought to have one or more alembics of metal for distilling water, spiritous liquors, essential oils, &c. This apparatus consists of a cucurbit and capital of tinned copper or brass, Pl. III. Fig. 15. and 16. which, when judged proper, may be placed in the water bath, D, Fig. 17. In distillations, especially of spiritous liquors, the capital must be furnished with a refrigetory, SS, Fig. 16. kept continually filled with cold water; when the water becomes heated, it is let off by the stop-cock, R, and renewed with a fresh supply of cold water. As the fluid distilled is converted into gas by means of caloric furnished by the fire of the furnace, it is evident that it could not condense, and, consequently, that no distillation, properly speaking, could take place, unless it is made to deposit in the capital all the caloric it received in the cucurbit; with this view, the sides of the capital must always be preserved at a lower temperature than is necessary for keeping the distilling substance in the state of gas, and the water in the refrigetory is intended for this purpose. Water is converted into gas by the temperature of 80° (212°), alkohol by 67° (182.75°), ether by 32° (104°); hence these substances cannot be distilled, or, rather, they will fly off in the state of gas, unless the temperature of the refrigetory be kept under these respective degrees. In the distillation of spiritous, and other expansive liquors, the above described refrigetory is not sufficient for condensing all the vapours which arise; in this case, therefore, instead of receiving the distilled liquor immediately from the beak, TU, of the capital into a recipient, a worm is interposed between them. This instrument is represented Pl. III. Fig. 18. contained in a worm tub of tinned copper, it consists of a metallic tube bent into a considerable number of spiral revolutions. The vessel which contains the worm is kept full of cold water, which is renewed as it grows warm. This contrivance is employed in all distilleries of spirits, without the intervention of a capital and refrigetory, properly so called. The one represented in the plate is furnished with two worms, one of them being particularly appropriated to distillations of odoriferous substances. In some simple distillations it is necessary to interpose an adopter between the retort and receiver, as shown Pl. III. Fig, 11. This may serve two different purposes, either to separate two products of different degrees of volatility, or to remove the receiver to a greater distance from the furnace, that it may be less heated. But these, and several other more complicated instruments of ancient contrivance, are far from producing the accuracy requisite in modern chemistry, as will be readily perceived when I come to treat of compound distillation. SECT. VI. _Of Sublimation._ This term is applied to the distillation of substances which condense in a concrete or solid form, such as the sublimation of sulphur, and of muriat of ammoniac, or sal ammoniac. These operations may be conveniently performed in the ordinary distilling vessels already described, though, in the sublimation of sulphur, a species of vessels, named Alludels, have been usually employed. These are vessels of stone or porcelain ware, which adjust to each other over a cucurbit containing the sulphur to be sublimed. One of the best subliming vessels, for substances which are not very volatile, is a flask, or phial of glass, sunk about two thirds into a sand bath; but in this way we are apt to lose a part of the products. When these are wished to be entirely preserved, we must have recourse to the pneumato-chemical distilling apparatus, to be described in the following chapter. CHAP. VI. _Of Pneumato-chemical Distillations, Metallic Dissolutions, and some other operations which require very complicated instruments._ SECT. I. _Of Compound and Pneumato-chemical Distillations._ In the preceding chapter, I have only treated of distillation as a simple operation, by which two substances, differing in degrees of volatility, may be separated from each other; but distillation often actually decomposes the substances submitted to its action, and becomes one of the most complicated operations in chemistry. In every distillation, the substance distilled must be brought to the state of gas, in the cucurbit or retort, by combination with caloric: In simple distillation, this caloric is given out in the refrigeratory or in the worm, and the substance again recovers its liquid or solid form, but the substances submitted to compound distillation are absolutely decompounded; one part, as for instance the charcoal they contain, remains fixed in the retort, and all the rest of the elements are reduced to gasses of different kinds. Some of these are susceptible of being condensed, and of recovering their solid or liquid forms, whilst others are permanently aëriform; one part of these are absorbable by water, some by the alkalies, and others are not susceptible of being absorbed at all. An ordinary distilling apparatus, such as has been described in the preceding chapter, is quite insufficient for retaining or for separating these diversified products, and we are obliged to have recourse, for this purpose, to methods of a more complicated nature. The apparatus I am about to describe is calculated for the most complicated distillations, and may be simplified according to circumstances. It consists of a tubulated glass retort A, Pl. IV. Fig. 1. having its beak fitted to a tubulated balloon or recipient BC; to the upper orifice D of the balloon a bent tube DEfg is adjusted, which, at its other extremity g, is plunged into the liquor contained in the bottle L, with three necks xxx. Three other similar bottles are connected with this first one, by means of three similar bent tubes disposed in the same manner; and the farthest neck of the last bottle is connected with a jar in a pneumato-chemical apparatus, by means of a bent tube[60]. A determinate weight of distilled water is usually put into the first bottle, and the other three have each a solution of caustic potash in water. The weight of all these bottles, and of the water and alkaline solution they contain, must be accurately ascertained. Every thing being thus disposed, the junctures between the retort and recipient, and of the tube D of the latter, must be luted with fat lute, covered over with slips of linen, spread with lime and white of egg; all the other junctures are to be secured by a lute made of wax and rosin melted together. When all these dispositions are completed, and when, by means of heat applied to the retort A, the substance it contains becomes decomposed, it is evident that the least volatile products must condense or sublime in the beak or neck of the retort itself, where most of the concrete substances will fix themselves. The more volatile substances, as the lighter oils, ammoniac, and several others, will condense in the recipient GC, whilst the gasses, which are not susceptible of condensation by cold, will pass on by the tubes, and boil up through the liquors in the several bottles. Such as are absorbable by water will remain in the first bottle, and those which caustic alkali can absorb will remain in the others; whilst such gasses as are not susceptible of absorption, either by water or alkalies, will escape by the tube RM, at the end of which they may be received into jars in a pneumato-chemical apparatus. The charcoal and fixed earth, &c. which form the substance or residuum, anciently called _caput mortuum_, remain behind in the retort. In this manner of operating, we have always a very material proof of the accuracy of the analysis, as the whole weights of the products taken together, after the process is finished, must be exactly equal to the weight of the original substance submitted to distillation. Hence, for instance, if we have operated upon eight ounces of starch or gum arabic, the weight of the charry residuum in the retort, together with that of all the products gathered in its neck and the balloon, and of all the gas received into the jars by the tube RM added to the additional weight acquired by the bottles, must, when taken together, be exactly eight ounces. If the product be less or more, it proceeds from error, and the experiment must be repeated until a satisfactory result be procured, which ought not to differ more than six or eight grains in the pound from the weight of the substance submitted to experiment. In experiments of this kind, I for a long time met with an almost insurmountable difficulty, which must at last have obliged me to desist altogether, but for a very simple method of avoiding it, pointed out to me by Mr Hassenfratz. The smallest diminution in the heat of the furnace, and many other circumstances inseparable from this kind of experiments, cause frequent reabsorptions of gas; the water in the cistern of the pneumato-chemical apparatus rushes into the last bottle through the tube RM, the same circumstance happens from one bottle into another, and the fluid is often forced even into the recipient C. This accident is prevented by using bottles having three necks, as represented in the plate, into one of which, in each bottle, a capillary glass-tube St, st, st, st, is adapted, so as to have its lower extremity t immersed in the liquor. If any absorption takes place, either in the retort, or in any of the bottles, a sufficient quantity of external air enters, by means of these tubes, to fill up the void; and we get rid of the inconvenience at the price of having a small mixture of common air with the products of the experiment, which is thereby prevented from failing altogether. Though these tubes admit the external air, they cannot permit any of the gasseous substances to escape, as they are always shut below by the water of the bottles. It is evident that, in the course of experiments with this apparatus, the liquor of the bottles must rise in these tubes in proportion to the pressure sustained by the gas or air contained in the bottles; and this pressure is determined by the height and gravity of the column of fluid contained in all the subsequent bottles. If we suppose that each bottle contains three inches of fluid, and that there are three inches of water in the cistern of the connected apparatus above the orifice of the tube RM, and allowing the gravity of the fluids to be only equal to that of water, it follows that the air in the first bottle must sustain a pressure equal to twelve inches of water; the water must therefore rise twelve inches in the tube S, connected with the first bottle, nine inches in that belonging to the second, six inches in the third, and three in the last; wherefore these tubes must be made somewhat more than twelve, nine, six, and three inches long respectively, allowance being made for oscillatory motions, which often take place in the liquids. It is sometimes necessary to introduce a similar tube between the retort and recipient; and, as the tube is not immersed in fluid at its lower extremity, until some has collected in the progress of the distillation, its upper end must be shut at first with a little lute, so as to be opened according to necessity, or after there is sufficient liquid in the recipient to secure its lower extremity. This apparatus cannot be used in very accurate experiments, when the substances intended to be operated upon have a very rapid action upon each other, or when one of them can only be introduced in small successive portions, as in such as produce violent effervescence when mixed together. In such cases, we employ a tubulated retort A, Pl. VII. Fig. 1. into which one of the substances is introduced, preferring always the solid body, if any such is to be treated, we then lute to the opening of the retort a bent tube BCDA, terminating at its upper extremity B in a funnel, and at its other end A in a capillary opening. The fluid material of the experiment is poured into the retort by means of this funnel, which must be made of such a length, from B to C, that the column of liquid introduced may counterbalance the resistance produced by the liquors contained in all the bottles, Pl. IV. Fig. 1. Those who have not been accustomed to use the above described distilling apparatus may perhaps be startled at the great number of openings which require luting, and the time necessary for making all the previous preparations in experiments of this kind. It is very true that, if we take into account all the necessary weighings of materials and products, both before and after the experiments, these preparatory and succeeding steps require much more time and attention than the experiment itself. But, when the experiment succeeds properly, we are well rewarded for all the time and trouble bestowed, as by one process carried on in this accurate manner much more just and extensive knowledge is acquired of the nature of the vegetable or animal substance thus submitted to investigation, than by many weeks assiduous labour in the ordinary method of proceeding. When in want of bottles with three orifices, those with two may be used; it is even possible to introduce all the three tubes at one opening, so as to employ ordinary wide-mouthed bottles, provided the opening be sufficiently large. In this case we must carefully fit the bottles with corks very accurately cut, and boiled in a mixture of oil, wax, and turpentine. These corks are pierced with the necessary holes for receiving the tubes by means of a round file, as in Pl. IV. Fig. 8. SECT. II. _Of Metallic Dissolutions._ I have already pointed out the difference between solution of salts in water and metallic dissolutions. The former requires no particular vessels, whereas the latter requires very complicated vessels of late invention, that we may not lose any of the products of the experiment, and may thereby procure truly conclusive results of the phenomena which occur. The metals, in general, dissolve in acids with effervescence, which is only a motion excited in the solvent by the disengagement of a great number of bubbles of air or aëriform fluid, which proceed from the surface of the metal, and break at the surface of the liquid. Mr Cavendish and Dr Priestley were the first inventors of a proper apparatus for collecting these elastic fluids. That of Dr Priestley is extremely simple, and consists of a bottle A, Pl. VII. Fig. 2. with its cork B, through which passes the bent glass tube BC, which is engaged under a jar filled with water in the pneumato-chemical apparatus, or simply in a bason full of water. The metal is first introduced into the bottle, the acid is then poured over it, and the bottle is instantly closed with its cork and tube, as represented in the plate. But this apparatus has its inconveniencies. When the acid is much concentrated, or the metal much divided, the effervescence begins before we have time to cork the bottle properly, and some gas escapes, by which we are prevented from ascertaining the quantity disengaged with rigorous exactness. In the next place, when we are obliged to employ heat, or when heat is produced by the process, a part of the acid distills, and mixes with the water of the pneumato-chemical apparatus, by which means we are deceived in our calculation of the quantity of acid decomposed. Besides these, the water in the cistern of the apparatus absorbs all the gas produced which is susceptible of absorption, and renders it impossible to collect these without loss. To remedy these inconveniencies, I at first used a bottle with two necks, Pl. VII. Fig. 3. into one of which the glass funnel BC is luted so as to prevent any air escaping; a glass rod DE is fitted with emery to the funnel, so as to serve the purpose of a stopper. When it is used, the matter to be dissolved is first introduced into the bottle, and the acid is then permitted to pass in as slowly as we please, by raising the glass rod gently as often as is necessary until saturation is produced. Another method has been since employed, which serves the same purpose, and is preferable to the last described in some instances. This consists in adapting to one of the mouths of the bottle A, Pl. VII. Fig. 4. a bent tube DEFG, having a capillary opening at D, and ending in a funnel at G. This tube is securely luted to the mouth C of the bottle. When any liquid is poured into the funnel, it falls down to F; and, if a sufficient quantity be added, it passes by the curvature E, and falls slowly into the bottle, so long as fresh liquor is supplied at the funnel. The liquor can never be forced out of the tube, and no gas can escape through it, because the weight of the liquid serves the purpose of an accurate cork. To prevent any distillation of acid, especially in dissolutions accompanied with heat, this tube is adapted to the retort A, Pl. VII. Fig. 1. and a small tubulated recipient, M, is applied, in which any liquor which may distill is condensed. On purpose to separate any gas that is absorbable by water, we add the double necked bottle L, half filled with a solution of caustic potash; the alkali absorbs any carbonic acid gas, and usually only one or two other gasses pass into the jar of the connected pneumato-chemical apparatus through the tube NO. In the first chapter of this third part we have directed how these are to be separated and examined. If one bottle of alkaline solution be not thought sufficient, two, three, or more, may be added. SECT. III. _Apparatus necessary in Experiments upon Vinous and Putrefactive Fermentations._ For these operations a peculiar apparatus, especially intended for this kind of experiment, is requisite. The one I am about to describe is finally adopted, as the best calculated for the purpose, after numerous corrections and improvements. It consists of a large matrass, A, Pl. X. fig. 1. holding about twelve pints, with a cap of brass a b, strongly cemented to its mouth, and into which is screwed a bent tube c d, furnished with a stop-cock e. To this tube is joined the glass recipient B, having three openings, one of which communicates with the bottle C, placed below it. To the posterior opening of this recipient is fitted a glass tube g h i, cemented at g and i to collets of brass, and intended to contain a very deliquescent concrete neutral salt, such as nitrat or muriat of lime, acetite of potash, &c. This tube communicates with two bottles D and E, filled to x and y with a solution of caustic potash. All the parts of this machine are joined together by accurate screws, and the touching parts have greased leather interposed, to prevent any passage of air. Each piece is likewise furnished with two stop-cocks, by which its two extremities may be closed, so that we can weigh each separately at any period of the operation. The fermentable matter, such as sugar, with a proper quantity of yeast, and diluted with water, is put into the matrass. Sometimes, when the fermentation is too rapid, a considerable quantity of froth is produced, which not only fills the neck of the matrass, but passes into the recipient, and from thence runs down into the bottle C. On purpose to collect this scum and must, and to prevent it from reaching the tube filled with deliquescent salts, the recipient and connected bottle are made of considerable capacity. In the vinous fermentation, only carbonic acid gas is disengaged, carrying with it a small proportion of water in solution. A great part of this water is deposited in passing through the tube g h i, which is filled with a deliquescent salt in gross powder, and the quantity is ascertained by the augmentation of the weight of the salt. The carbonic acid gas bubbles up through the alkaline solution in the bottle D, to which it is conveyed by the tube k l m. Any small portion which may not be absorbed by this first bottle is secured by the solution in the second bottle E, so that nothing, in general, passes into the jar F, except the common air contained in the vessels at the commencement of the experiment. The same apparatus answers extremely well for experiments upon the putrefactive fermentation; but, in this case, a considerable quantity of hydrogen gas is disengaged through the tube q r s t u, by which it is conveyed into the jar F; and, as this disengagement is very rapid, especially in summer, the jar must be frequently changed. These putrefactive fermentations require constant attendance from the above circumstance, whereas the vinous fermentation hardly needs any. By means of this apparatus we can ascertain, with great precision, the weights of the substances submitted to fermentation, and of the liquid and aëriform products which are disengaged. What has been already said in Part I. Chap. XIII. upon the products of the vinous fermentation, may be consulted. SECT. IV. _Apparatus for the Decomposition of Water._ Having already given an account, in the first part of this work, of the experiments relative to the decomposition of water, I shall avoid any unnecessary repetitions, and only give a few summary observations upon the subject in this section. The principal substances which have the power of decomposing water are iron and charcoal; for which purpose, they require to be made red hot, otherwise the water is only reduced into vapours, and condenses afterwards by refrigeration, without sustaining the smallest alteration. In a red heat, on the contrary, iron or charcoal carry off the oxygen from its union with hydrogen; in the first case, black oxyd of iron is produced, and the hydrogen is disengaged pure in form of gas; in the other case, carbonic acid gas is formed, which disengages, mixed with the hydrogen gas; and this latter is commonly carbonated, or holds charcoal in solution. A musket barrel, without its breach pin, answers exceedingly well for the decomposition of water, by means of iron, and one should be chosen of considerable length, and pretty strong. When too short, so as to run the risk of heating the lute too much, a tube of copper is to be strongly soldered to one end. The barrel is placed in a long furnace, CDEF, Pl. VII. Fig. 11. so as to have a few degrees of inclination from E to F; a glass retort A, is luted to the upper extremity E, which contains water, and is placed upon the furnace VVXX. The lower extremity F is luted to a worm SS, which is connected with the tubulated bottle H, in which any water distilled without decomposition, during the operation, collects, and the disengaged gas is carried by the tube KK to jars in a pneumato-chemical apparatus. Instead of the retort a funnel may be employed, having its lower part shut by a stop-cock, through which the water is allowed to drop gradually into the gun-barrel. Immediately upon getting into contact with the heated part of the iron, the water is converted into steam, and the experiment proceeds in the same manner as if it were furnished in vapours from the retort. In the experiment made by Mr Meusnier and me before a committee of the Academy, we used every precaution to obtain the greatest possible precision in the result of our experiment, having even exhausted all the vessels employed before we began, so that the hydrogen gas obtained might be free from any mixture of azotic gas. The results of that experiment will hereafter be given at large in a particular memoir. In numerous experiments, we are obliged to use tubes of glass, porcelain, or copper, instead of gun-barrels; but glass has the disadvantage of being easily melted and flattened, if the heat be in the smallest degree raised too high; and porcelain is mostly full of small minute pores, through which the gas escapes, especially when compressed by a column of water. For these reasons I procured a tube of brass, which Mr de la Briche got cast and bored out of the solid for me at Strasburg, under his own inspection. This tube is extremely convenient for decomposing alkohol, which resolves into charcoal, carbonic acid gas, and hydrogen gas; it may likewise be used with the same advantage for decomposing water by means of charcoal, and in a great number of experiments of this nature. FOOTNOTES: [60] The representation of this apparatus, Pl. IV. Fig. 1. will convey a much better idea of its disposition than can possibly be given by the most laboured description.--E. CHAP. VII. _Of the Composition and Application of Lutes._ The necessity of properly securing the junctures of chemical vessels to prevent the escape of any of the products of experiments, must be sufficiently apparent; for this purpose lutes are employed, which ought to be of such a nature as to be equally impenetrable to the most subtile substances, as glass itself, through which only caloric can escape. This first object of lutes is very well accomplished by bees wax, melted with about an eighth part of turpentine. This lute is very easily managed, sticks very closely to glass, and is very difficultly penetrable; it may be rendered more consistent, and less or more hard or pliable, by adding different kinds of resinous matters. Though this species of lute answers extremely well for retaining gasses and vapours, there are many chemical experiments which produce considerable heat, by which this lute becomes liquified, and consequently the expansive vapours must very readily force through and escape. For such cases, the following fat lute is the best hitherto discovered, though not without its disadvantages, which shall be pointed out. Take very pure and dry unbaked clay, reduced to a very fine powder, put this into a brass mortar, and beat it for several hours with a heavy iron pestle, dropping in slowly some boiled lintseed oil; this is oil which has been oxygenated, and has acquired a drying quality, by being boiled with litharge. This lute is more tenacious, and applies better, if amber varnish be used instead of the above oil. To make this varnish, melt some yellow amber in an iron laddle, by which operation it loses a part of its succinic acid, and essential oil, and mix it with lintseed oil. Though the lute prepared with this varnish is better than that made with boiled oil, yet, as its additional expence is hardly compensated by its superior quality, it is seldom used. The above fat lute is capable of sustaining a very violent degree of heat, is impenetrable by acids and spiritous liquors, and adheres exceedingly well to metals, stone ware, or glass, providing they have been previously rendered perfectly dry. But if, unfortunately, any of the liquor in the course of an experiment gets through, either between the glass and the lute, or between the layers of the lute itself, so as to moisten the part, it is extremely difficult to close the opening. This is the chief inconvenience which attends the use of fat lute, and perhaps the only one it is subject to. As it is apt to soften by heat, we must surround all the junctures with slips of wet bladder applied over the luting, and fixed on by pack-thread tied round both above and below the joint; the bladder, and consequently the lute below, must be farther secured by a number of turns of pack-thread all over it. By these precautions, we are free from every danger of accident; and the junctures secured in this manner may be considered, in experiments, as hermetically sealed. It frequently happens that the figure of the junctures prevents the application of ligatures, which is the case with the three-necked bottles formerly described; and it even requires great address to apply the twine without shaking the apparatus; so that, where a number of junctures require luting, we are apt to displace several while securing one. In these cases, we may substitute slips of linen, spread with white of egg and lime mixed together, instead of the wet bladder. These are applied while still moist, and very speedily dry and acquire considerable hardness. Strong glue dissolved in water may answer instead of white of egg. These fillets are usefully applied likewise over junctures luted together with wax and rosin. Before applying a lute, all the junctures of the vessels must be accurately and firmly fitted to each other, so as not to admit of being moved. If the beak of a retort is to be luted to the neck of a recipient, they ought to fit pretty accurately; otherwise we must fix them, by introducing short pieces of soft wood or of cork. If the disproportion between the two be very considerable, we must employ a cork which fits the neck of the recipient, having a circular hole of proper dimensions to admit the beak of the retort. The same precaution is necessary in adapting bent tubes to the necks of bottles in the apparatus represented Pl. IV. Fig. 1. and others of a similar nature. Each mouth of each bottle must be fitted with a cork, having a hole made with a round file of a proper size for containing the tube. And, when one mouth is intended to admit two or more tubes, which frequently happens when we have not a sufficient number of bottles with two or three necks, we must use a cork with two or three holes, Pl. IV. Fig. 8. When the whole apparatus is thus solidly joined, so that no part can play upon another, we begin to lute. The lute is softened by kneading and rolling it between the fingers, with the assistance of heat, if necessary. It is rolled into little cylindrical pieces, and applied to the junctures, taking great care to make it apply close, and adhere firmly, in every part; a second roll is applied over the first, so as to pass it on each side, and so on till each juncture be sufficiently covered; after this, the slips of bladder, or of linen, as above directed, must be carefully applied over all. Though this operation may appear extremely simple, yet it requires peculiar delicacy and management; great care must be taken not to disturb one juncture whilst luting another, and more especially when applying the fillets and ligatures. Before beginning any experiment, the closeness of the luting ought always to be previously tried, either by slightly heating the retort A, Pl. IV. Fig. 1, or by blowing in a little air by some of the perpendicular tubes S s s s; the alteration of pressure causes a change in the level of the liquid in these tubes. If the apparatus be accurately luted, this alteration of level will be permanent; whereas, if there be the smallest, opening in any of the junctures, the liquid will very soon recover its former level. It must always be remembered, that the whole success of experiments in modern chemistry depends upon the exactness of this operation, which therefore requires the utmost patience, and most attentive accuracy. It would be of infinite service to enable chemists, especially those who are engaged in pneumatic processes, to dispense with the use of lutes, or at least to diminish the number necessary in complicated instruments. I once thought of having my apparatus constructed so as to unite in all its parts by fitting with emery, in the way of bottles with cristal stoppers; but the execution of this plan was extremely difficult. I have since thought it preferable to substitute columns of a few lines of mercury in place of lutes, and have got an apparatus constructed upon this principle, which appears capable of very convenient application in a great number of circumstances. It consists of a double necked bottle A, Pl. XII. Fig. 12.; the interior neck bc communicates with the inside of the bottle, and the exterior neck or rim de leaves an interval between the two necks, forming a deep gutter intended to contain the mercury. The cap or lid of glass B enters this gutter, and is properly fitted to it, having notches in its lower edge for the passage of the tubes which convey the gas. These tubes, instead of entering directly into the bottles as in the ordinary apparatus, have a double bend for making them enter the gutter, as represented in Fig. 13. and for making them fit the notches of the cap B; they rise again from the gutter to enter the inside of the bottle over the border of the inner mouth. When the tubes are disposed in their proper places, and the cap firmly fitted on, the gutter is filled with mercury, by which means the bottle is completely excluded from any communication, excepting through the tubes. This apparatus may be very convenient in many operations in which the substances employed have no action upon Mercury. Pl. XII. Fig. 14. represents an apparatus upon this principle properly fitted together. Mr Seguin, to whose active and intelligent assistance I have been very frequently much indebted, has bespoken for me, at the glass-houses, some retorts hermetically united to their recipients, by which luting will be altogether unnecessary. CHAP. VIII. _Of Operations upon Combustion and Deflagration._ SECT. I. _Of Combustion in general._ Combustion, according to what has been already said in the First Part of this Work, is the decomposition of oxygen gas produced by a combustible body. The oxygen which forms the base of this gas is absorbed by, and enters into, combination with the burning body, while the caloric and light are set free. Every combustion, therefore, necessarily supposes oxygenation; whereas, on the contrary, every oxygenation does not necessarily imply concomitant combustion; because combustion, properly so called, cannot take place without disengagement of caloric and light. Before combustion can take place, it is necessary that the base of oxygen gas should have greater affinity to the combustible body than it has to caloric; and this elective attraction, to use Bergman's expression, can only take place at a certain degree of temperature, which is different for each combustible substance; hence the necessity of giving a first motion or beginning to every combustion by the approach of a heated body. This necessity of heating any body we mean to burn depends upon certain considerations, which have not hitherto been attended to by any natural philosopher, for which reason I shall enlarge a little upon the subject in this place. Nature is at present in a state of equilibrium, which cannot have been attained until all the spontaneous combustions or oxygenations possible in the ordinary degrees of temperature had taken place. Hence, no new combustions or oxygenations can happen without destroying this equilibrium, and raising the combustible substances to a superior degree of temperature. To illustrate this abstract view of the matter by example: Let us suppose the usual temperature of the earth a little changed, and that it is raised only to the degree of boiling water; it is evident, that, in this case, phosphorus, which is combustible in a considerably lower degree of temperature, would no longer exist in nature in its pure and simple state, but would always be procured in its acid or oxygenated state, and its radical would become one of the substances unknown to chemistry. By gradually increasing the temperature of the earth the same circumstance would successively happen to all the bodies capable of combustion; and, at last, every possible combustion having taken place, there would no longer exist any combustible body whatever, as every substance susceptible of that operation would be oxygenated, and consequently incombustible. There cannot therefore exist, so far as relates to us, any combustible body, except such as are incombustible in the ordinary temperatures of the earth; or, what is the same thing, in other words, that it is essential to the nature of every combustible body not to possess the property of combustion, unless heated, or raised to the degree of temperature at which its combustion naturally takes place. When this degree is once produced, combustion commences, and the caloric which is disengaged by the decomposition of the oxygen gas keeps up the temperature necessary for continuing combustion. When this is not the case, that is, when the disengaged caloric is insufficient for keeping up the necessary temperature, the combustion ceases: This circumstance is expressed in common language by saying, that a body burns ill, or with difficulty. Although combustion possesses some circumstances in common with distillation, especially with the compound kind of that operation, they differ in a very material point. In distillation there is a separation of one part of the elements of the substance from each other, and a combination of these, in a new order, occasioned by the affinities which take place in the increased temperature produced during distillation: This likewise happens in combustion, but with this farther circumstance, that a new element, not originally in the body, is brought into action; oxygen is added to the substance submitted to the operation, and caloric is disengaged. The necessity of employing oxygen in the state of gas in all experiments with combustion, and the rigorous determination of the quantities employed, render this kind of operations peculiarly troublesome. As almost all the products of combustion are disengaged in the state of gas, it is still more difficult to retain them than even those furnished during compound distillation; hence this precaution was entirely neglected by the ancient chemists; and this set of experiments exclusively belong to modern chemistry. Having thus pointed out, in a general way, the objects to be had in view in experiments upon combustion, I proceed, in the following sections of this chapter, to describe the different instruments I have used with this view. The following arrangement is formed, not upon the nature of the combustible bodies, but upon that of the instruments necessary for combustion. SECT. II. _Of the Combustion of Phosphorus._ In these combustions we begin by filling a jar, capable at least of holding six pints, with oxygen gas in the water apparatus, Pl. V. Fig. 1.; when it is perfectly full, so that the gas begins to flow out below, the jar, A, is carried to the mercury apparatus, Pl. IV. Fig. 3. We then dry the surface of the mercury, both within and without the jar, by means of blotting-paper, taking care to keep the paper for some time entirely immersed in the mercury before it is introduced under the jar, lest we let in any common air, which sticks very obstinately to the surface of the paper. The body to be submitted to combustion, being first very accurately weighed in nice scales, is placed in a small flat shallow dish, D, of iron or porcelain; this is covered by the larger cup P, which serves the office of a diving bell, and the whole is passed through the mercury into the jar, after which the larger cup is retired. The difficulty of passing the materials of combustion in this manner through the mercury may be avoided by raising one of the sides of the jar, A, for a moment, and slipping in the little cup, D, with the combustible body as quickly as possible. In this manner of operating, a small quantity of common air gets into the jar, but it is so very inconsiderable as not to injure either the progress or accuracy of the experiment in any sensible degree. When the cup, D, is introduced under the jar, we suck out a part of the oxygen gas, so as to raise the mercury to EF, as formerly directed, Part I. Chap. V. otherwise, when the combustible body is set on fire, the gas becoming dilated would be in part forced out, and we should no longer be able to make any accurate calculation of the quantities before and after the experiment. A very convenient mode of drawing out the air is by means of an air-pump syringe adapted to the syphon, GHI, by which the mercury may be raised to any degree under twenty-eight inches. Very inflammable bodies, as phosphorus, are set on fire by means of the crooked iron wire, MN, Pl. IV. Fig. 16. made red hot, and passed quickly through the mercury. Such as are less easily set on fire have a small portion of tinder, upon which a minute particle of phosphorus is fixed, laid upon them before using the red hot iron. In the first moment of combustion the air, being heated, rarifies, and the mercury descends; but when, as in combustions of phosphorus and iron, no elastic fluid is formed, absorption becomes presently very sensible, and the mercury rises high into the jar. Great attention must be used not to burn too large a quantity of any substance in a given quantity of gas, otherwise, towards the end of the experiment, the cup would approach so near the top of the jar as to endanger breaking it by the great heat produced, and the sudden refrigeration from the cold mercury. For the methods of measuring the volume of the gasses, and for correcting the measures according to the heighth of the barometer and thermometer, &c. see Chap. II. Sect. V. and VI. of this part. The above process answers very well for burning all the concrete substances, and even for the fixed oils: These last are burnt in lamps under the jar, and are readily set on fire by means of tinder, phosphorus, and hot iron. But it is dangerous for substances susceptible of evaporating in a moderate heat, such as ether, alkohol, and the essential oils; these substances dissolve in considerable quantity in oxygen gas; and, when set on fire, a dangerous and sudden explosion takes place, which carries up the jar to a great height, and dashes it in a thousand pieces. From two such explosions some of the members of the Academy and myself escaped very narrowly. Besides, though this manner of operating is sufficient for determining pretty accurately the quantity of oxygen gas absorbed, and of carbonic acid produced, as water is likewise formed in all experiments upon vegetable and animal matters which contain an excess of hydrogen, this apparatus can neither collect it nor determine its quantity. The experiment with phosphorus is even incomplete in this way, as it is impossible to demonstrate that the weight of the phosphoric acid produced is equal to the sum of the weights of the phosphorus burnt and oxygen gas absorbed during the process. I have been therefore obliged to vary the instruments according to circumstances, and to employ several of different kinds, which I shall describe in their order, beginning with that used for burning phosphorus. Take a large balloon, A, Pl. IV. Fig. 4. of cristal or white glass, with an opening, EF, about two inches and a half, or three inches, diameter, to which a cap of brass is accurately fitted with emery, and which has two holes for the passage of the tubes xxx, yyy. Before shutting the balloon with its cover, place within it the stand, BC, supporting the cup of porcelain, D, which contains the phosphorus. Then lute on the cap with fat lute, and allow it to dry for some days, and weigh the whole accurately; after this exhaust the balloon by means of an air-pump connected with the tube xxx, and fill it with oxygen gas by the tube yyy, from the gazometer, Pl. VIII. Fig. 1. described Chap. II. Sect II. of this part. The phosphorus is then set on fire by means of a burning-glass, and is allowed to burn till the cloud of concrete phosphoric acid stops the combustion, oxygen gas being continually supplied from the gazometer. When the apparatus has cooled, it is weighed and unluted; the tare of the instrument being allowed, the weight is that of the phosphoric acid contained. It is proper, for greater accuracy, to examine the air or gas contained in the balloon after combustion, as it may happen to be somewhat heavier or lighter than common air; and this difference of weight must be taken into account in the calculations upon the results of the experiment. SECT. III. _Of the Combustion of Charcoal._ The apparatus I have employed for this process consists of a small conical furnace of hammered copper, represented in perspective, Pl. XII. Fig. 9. and internally displayed Fig. 11. It is divided into the furnace, ABC, where the charcoal is burnt, the grate, d e, and the ash-hole, F; the tube, GH, in the middle of the dome of the furnace serves to introduce the charcoal, and as a chimney for carrying off the air which has served for combustion. Through the tube, l m n, which communicates with the gazometer, the hydrogen gas, or air, intended for supporting the combustion, is conveyed into the ash-hole, F, whence it is forced, by the application of pressure to the gazometer, to pass through the grate, d e, and to blow upon the burning charcoal placed immediately above. Oxygen gas, which forms 28/100 of atmospheric air, is changed into carbonic acid gas during combustion with charcoal, whilst the azotic gas of the air is not altered at all. Hence, after the combustion of charcoal in atmospheric air, a mixture of carbonic acid gas and azotic gas must remain; to allow this mixture to pass off, the tube, o p, is adapted to the chimney, GH, by means of a screw at G, and conveys the gas into bottles half filled with solution of caustic potash. The carbonic acid gas is absorbed by the alkali, and the azotic gas is conveyed into a second gazometer, where its quantity is ascertained. The weight of the furnace, ABC, is first accurately determined, then introduce the tube RS, of known weight, by the chimney, GH, till its lower end S, rests upon the grate, d e, which it occupies entirely; in the next place, fill the furnace with charcoal, and weigh the whole again, to know the exact quantity of charcoal submitted to experiment. The furnace is now put in its place, the tube, l m n, is screwed to that which communicates with the gazometer, and the tube, o p, to that which communicates with the bottles of alkaline solution. Every thing being in readiness, the stop-cock of the gazometer is opened, a small piece of burning charcoal is thrown into the tube, RS, which is instantly withdrawn, and the tube, o p, is screwed to the chimney, GH. The little piece of charcoal falls upon the grate, and in this manner gets below the whole charcoal, and is kept on fire by the stream of air from the gazometer. To be certain that the combustion is begun, and goes on properly, the tube, q r s, is fixed to the furnace, having a piece of glass cemented to its upper extremity, s, through which we can see if the charcoal be on fire. I neglected to observe above, that the furnace, and its appendages, are plunged in water in the cistern, TVXY, Fig. 11. Pl. XII. to which ice may be added to moderate the heat, if necessary; though the heat is by no means very considerable, as there is no air but what comes from the gazometer, and no more of the charcoal burns at one time than what is immediately over the grate. As one piece of charcoal is consumed another falls down into its place, in consequence of the declivity of the sides of the furnace; this gets into the stream of air from the grate, d e, and is burnt; and so on, successively, till the whole charcoal is consumed. The air which has served the purpose of the combustion passes through the mass of charcoal, and is forced by the pressure of the gazometer to escape through the tube, o p, and to pass through the bottles of alkaline solution. This experiment furnishes all the necessary data for a complete analysis of atmospheric air and of charcoal. We know the weight of charcoal consumed; the gazometer gives us the measure of the air employed; the quantity and quality of gas remaining after combustion may be determined, as it is received, either in another gazometer, or in jars, in a pneumato-chemical apparatus; the weight of ashes remaining in the ash-hole is readily ascertained; and, finally, the additional weight acquired by the bottles of alkaline solution gives the exact quantity of carbonic acid formed during the process. By this experiment we may likewise determine, with sufficient accuracy, the proportions in which charcoal and oxygen enter into the composition of carbonic acid. In a future memoir I shall give an account to the Academy of a series of experiments I have undertaken, with this instrument, upon all the vegetable and animal charcoals. By some very slight alterations, this machine may be made to answer for observing the principal phenomena of respiration. SECT. IV. _Of the Combustion of Oils._ Oils are more compound in their nature than charcoal, being formed by the combination of at least two elements, charcoal and hydrogen; of course, after their combustion in common air, water, carbonic acid gas, and azotic gas, remain. Hence the apparatus employed for their combustion requires to be adapted for collecting these three products, and is consequently more complicated than the charcoal furnace. The apparatus I employ for this purpose is composed of a large jar or pitcher A, Pl. XII. Fig. 4. surrounded at its upper edge by a rim of iron properly cemented at DE, and receding from the jar at BC, so as to leave a furrow or gutter xx, between it and the outside of the jar, somewhat more than two inches deep. The cover or lid of the jar, Fig. 5. is likewise surrounded by an iron rim f g, which adjusts into the gutter xx, Fig. 4. which being filled with mercury, has the effect of closing the jar hermetically in an instant, without using any lute; and, as the gutter will hold about two inches of mercury, the air in the jar may be made to sustain the pressure of more than two feet of water, without danger of its escaping. The lid has four holes, T h i k, for the passage of an equal number of tubes. The opening T is furnished with a leather box, through which passes the rod, Fig. 3. intended for raising and lowering the wick of the lamp, as will be afterwards directed. The three other holes are intended for the passage of three several tubes, one of which conveys the oil to the lamp, a second conveys air for keeping up the combustion, and the third carries off the air, after it has served for combustion. The lamp in which the oil is burnt is represented Fig. 2; a is the reservoir of oil, having a funnel by which it is filled; b c d e f g h is a syphon which conveys the oil to the lamp 11; 7, 8, 9, 10, is the tube which conveys the air for combustion from the gazometer to the same lamp. The tube b c is formed externally, at its lower end b, into a male screw, which turns in a female screw in the lid of the reservoir of oil a; so that, by turning the reservoir one way or the other, it is made to rise or fall, by which the oil is kept at the necessary level. When the syphon is to be filled, and the communication formed between the reservoir of oil and the lamp, the stop-cock c is shut, and that at e opened, oil is poured in by the opening f at the top of the syphon, till it rises within three or four lines of the upper edge of the lamp, the stop-cock k is then shut, and that at c opened; the oil is then poured in at f, till the branch b c d of the syphon is filled, and then the stop-cock e is closed. The two branches of the syphon being now completely filled, a communication is fully established between the reservoir and the lamp. In Pl. XII. Fig. 1. all the parts of the lamp 11, Fig. 2. are represented magnified, to show them distinctly. The tube i k carries the oil from the reservoir to the cavity a a a a, which contains the wick; the tube 9, 10, brings the air from the gazometer for keeping up the combustion; this air spreads through the cavity d d d d, and, by means of the passages c c c c and b b b b, is distributed on each side of the wick, after the principles of the lamps constructed by Argand, Quinquet, and Lange. To render the whole of this complicated apparatus more easily understood, and that its description may make all others of the same kind more readily followed, it is represented, completely connected together for use, in Pl. XI. The gazometer P furnishes air for the combustion by the tube and stop-cock 1, 2; the tube 2, 3, communicates with a second gazometer, which is filled whilst the first one is emptying during the process, that there may be no interruption to the combustion; 4, 5, is a tube of glass filled with deliquescent salts, for drying the air as much as possible in its passage; and the weight of this tube and its contained salts, at the beginning of the experiment, being known, it is easy to determine the quantity of water absorbed by them from the air. From this deliquescent tube the air is conducted through the pipe 5, 6, 7, 8, 9, 10, to the lamp 11, where it spreads on both sides of the wick, as before described, and feeds the flame. One part of this air, which serves to keep up the combustion of the oil, forms carbonic acid gas and water, by oxygenating its elements. Part of this water condenses upon the sides of the pitcher A, and another part is held in solution in the air by means of caloric furnished by the combustion. This air is forced by the compression of the gazometer to pass through the tube 12, 13, 14, 15, into the bottle 16, and the worm 17, 18, where the water is fully condensed from the refrigeration of the air; and, if any water still remains in solution, it is absorbed by deliquescent salts contained in the tube 19, 20. All these precautions are solely intended for collecting and determining the quantity of water formed during the experiment; the carbonic acid and azotic gas remains to be ascertained. The former is absorbed by caustic alkaline solution in the bottles 22 and 25. I have only represented two of these in the figure, but nine at least are requisite; and the last of the series may be half filled with lime-water, which is the most certain reagent for indicating the presence of carbonic acid; if the lime-water is not rendered turbid, we may be certain that no sensible quantity of that acid remains in the air. The rest of the air which has served for combustion, and which chiefly consists of azotic gas, though still mixed with a considerable portion of oxygen gas, which has escaped unchanged from the combustion, is carried through a third tube 28, 29, of deliquescent salts, to deprive it of any moisture it may have acquired in the bottles of alkaline solution and lime-water, and from thence by the tube 29, 30, into a gazometer, where its quantity is ascertained. Small essays are then taken from it, which are exposed to a solution of sulphuret of potash, to ascertain the proportions of oxygen and azotic gas it contains. In the combustion of oils the wick becomes charred at last, and obstructs the rise of the oil; besides, if we raise the wick above a certain height, more oil rises through its capillary tubes than the stream of air is capable of consuming, and smoke is produced. Hence it is necessary to be able to lengthen or shorten the wick without opening the apparatus; this is accomplished by means of the rod 31, 32, 33, 34, which passes through a leather-box, and is connected with the support of the wick; and that the motion of this rod, and consequently of the wick, may be regulated with the utmost smoothness and facility; it is moved at pleasure by a pinnion which plays in a toothed rack. The rod, with its appendages, are represented Pl. XII. Fig. 3. It appeared to me, that the combustion would be assisted by surrounding the flame of the lamp with a small glass jar open at both ends, as represented in its place in Pl. XI. I shall not enter into a more detailed description of the construction of this apparatus, which is still capable of being altered and modified in many respects, but shall only add, that when it is to be used in experiment, the lamp and reservoir with the contained oil must be accurately weighed, after which it is placed as before directed, and lighted; having then formed the connection between the air in the gazometer and the lamp, the external jar A, Pl. XI. is fixed over all, and secured by means of the board BC and two rods of iron which connect this board with the lid, and are screwed to it. A small quantity of oil is burnt while the jar is adjusting to the lid, and the product of that combustion is lost; there is likewise a small portion of air from the gazometer lost at the same time. Both of these are of very inconsiderable consequence in extensive experiments, and they are even capable of being valued in our calculation of the results. In a particular memoir, I shall give an account to the Academy of the difficulties inseparable from this kind of experiments: These are so insurmountable and troublesome, that I have not hitherto been able to obtain any rigorous determination of the quantities of the products. I have sufficient proof, however, that the fixed oils are entirely resolved during combustion into water and carbonic acid gas, and consequently that they are composed of hydrogen and charcoal; but I have no certain knowledge respecting the proportions of these ingredients. SECT. V. _Of the Combustion of Alkohol._ The combustion of alkohol may be very readily performed in the apparatus already described for the combustion of charcoal and phosphorus. A lamp filled with alkohol is placed under the jar A, Pl. IV. Fig. 3. a small morsel of phosphorus is placed upon the wick of the lamp, which is set on fire by means of the hot iron, as before directed. This process is, however, liable to considerable inconveniency; it is dangerous to make use of oxygen gas at the beginning of the experiment for fear of deflagration, which is even liable to happen when common air is employed. An instance of this had very near proved fatal to myself, in presence of some members of the Academy. Instead of preparing the experiment, as usual, at the time it was to be performed, I had disposed every thing in order the evening before; the atmospheric air of the jar had thereby sufficient time to dissolve a good deal of the alkohol; and this evaporation had even been considerably promoted by the height of the column of mercury, which I had raised to EF, Pl. IV. Fig. 3. The moment I attempted to set the little morsel of phosphorus on fire by means of the red hot iron, a violent explosion took place, which threw the jar with great violence against the floor of the laboratory, and dashed it in a thousand pieces. Hence we can only operate upon very small quantities, such as ten or twelve grains of alkohol, in this manner; and the errors which may be committed in experiments upon such small quantities prevents our placing any confidence in their results. I endeavoured to prolong the combustion, in the experiments contained in the Memoirs of the Academy for 1784, p. 593. by lighting the alkohol first in common air, and furnishing oxygen gas afterwards to the jar, in proportion as it consumed; but the carbonic acid gas produced by the process became a great hinderance to the combustion, the more so that alkohol is but difficultly combustible, especially in worse than common air; so that even in this way very small quantities only could be burnt. Perhaps this combustion might succeed better in the oil apparatus, Pl. XI.; but I have not hitherto ventured to try it. The jar A in which the combustion is performed is near 1400 cubical inches in dimension; and, were an explosion to take place in such a vessel, its consequences would be very terrible, and very difficult to guard against. I have not, however, despaired of making the attempt. From all these difficulties, I have been hitherto obliged to confine myself to experiments upon very small quantities of alkohol, or at least to combustions made in open vessels, such as that represented in Pl. IX. Fig. 5. which will be described in Section VII. of this chapter. If I am ever able to remove these difficulties, I shall resume this investigation. SECT. VI. _Of the Combustion of Ether._ Tho' the combustion of ether in close vessels does not present the same difficulties as that of alkohol, yet it involves some of a different kind, not more easily overcome, and which still prevent the progress of my experiments. I endeavoured to profit by the property which ether possesses of dissolving in atmospheric air, and rendering it inflammable without explosion. For this purpose, I constructed the reservoir of ether a b c d, Plate XII. Fig. 8. to which air is brought from the gazometer by the tube 1, 2, 3, 4. This air spreads, in the first place, in the double lid ac of the reservoir, from which it passes through seven tubes ef, gh, ik, &c. which descend to the bottom of the ether, and it is forced by the pressure of the gazometer to boil up through the ether in the reservoir. We may replace the ether in this first reservoir, in proportion as it is dissolved and carried off by the air, by means of the supplementary reservoir E, connected by a brass tube fifteen or eighteen inches long, and shut by a stop-cock. This length of the connecting tube is to enable the descending ether to overcome the resistance occasioned by the pressure of the air from the gazometer. The air, thus loaded with vapours of ether, is conducted by the tube 5, 6, 7, 8, 9, to the jar A, into which it is allowed to escape through a capillary opening, at the extremity of which it is set on fire. The air, when it has served the purpose of combustion, passes through the bottle 16, Pl. XI. the worm 17, 18, and the deliquescent tube 19, 20, after which it passes through the alkaline bottles; in these its carbonic acid gas is absorbed, the water formed during the experiment having been previously deposited in the former parts of the apparatus. When I caused construct this apparatus, I supposed that the combination of atmospheric air and ether formed in the reservoir a b c d, Pl. XII. Fig. 8. was in proper proportion for supporting combustion; but in this I was mistaken; for there is a very considerable quantity of excess of ether; so that an additional quantity of atmospheric air is necessary to enable it to burn fully. Hence a lamp constructed upon these principles will burn in common air, which furnishes the quantity of oxygen necessary for combustion, but will not burn in close vessels in which the air is not renewed. From this circumstance, my ether lamp went out soon after being lighted and shut up in the jar A, Pl. XII. Fig. 8. To remedy this defect, I endeavoured to bring atmospheric air to the lamp by the lateral tube 10, 11, 12, 13, 14, 15, which I distributed circularly round the flame; but the flame is so exceedingly rare, that it is blown out by the gentlest possible stream of air, so that I have not hitherto succeeded in burning ether. I do not, however, despair of being able to accomplish it by means of some changes I am about to have made upon this apparatus. SECT. VII. _Of the Combustion of Hydrogen Gas, and the Formation of Water._ In the formation of water, two substances, hydrogen and oxygen, which are both in the aëriform state before combustion, are transformed into liquid or water by the operation. This experiment would be very easy, and would require very simple instruments, if it were possible to procure the two gasses perfectly pure, so that they might burn without any residuum. We might, in that case, operate in very small vessels, and, by continually furnishing the two gasses in proper proportions, might continue the combustion indefinitely. But, hitherto, chemists have only employed oxygen gas, mixed with azotic gas; from which circumstance, they have only been able to keep up the combustion of hydrogen gas for a very limited time in close vessels, because, as the residuum of azotic gas is continually increasing, the air becomes at last so much contaminated, that the flame weakens and goes out. This inconvenience is so much the greater in proportion as the oxygen gas employed is less pure. From this circumstance, we must either be satisfied with operating upon small quantities, or must exhaust the vessels at intervals, to get rid of the residuum of azotic gas; but, in this case, a portion of the water formed during the experiment is evaporated by the exhaustion; and the resulting error is the more dangerous to the accuracy of the process, that we have no certain means of valuing it. These considerations make me desirous to repeat the principal experiments of pneumatic chemistry with oxygen gas entirely free from any admixture of azotic gas; and this may be procured from oxygenated muriat of potash. The oxygen gas extracted from this salt does not appear to contain azote, unless accidentally, so that, by proper precautions, it may be obtained perfectly pure. In the mean time, the apparatus employed by Mr Meusnier and me for the combustion of hydrogen gas, which is described in the experiment for recomposition of water, Part I. Chap. VIII. and need not be here repeated, will answer the purpose; when pure gasses are procured, this apparatus will require no alterations, except that the capacity of the vessels may then be diminished. See Pl. IV. Fig. 5. The combustion, when once begun, continues for a considerable time, but weakens gradually, in proportion as the quantity of azotic gas remaining from the combustion increases, till at last the azotic gas is in such over proportion that the combustion can no longer be supported, and the flame goes out. This spontaneous extinction must be prevented, because, as the hydrogen gas is pressed upon in its reservoir, by an inch and a half of water, whilst the oxygen gas suffers a pressure only of three lines, a mixture of the two would take place in the balloon, which would at last be forced by the superior pressure into the reservoir of oxygen gas. Wherefore the combustion must be stopped, by shutting the stop-cock of the tube dDd whenever the flame grows very feeble; for which purpose it must be attentively watched. There is another apparatus for combustion, which, though we cannot with it perform experiments with the same scrupulous exactness as with the preceding instruments, gives very striking results that are extremely proper to be shewn in courses of philosophical chemistry. It consists of a worm EF, Pl. IX. Fig. 5. contained in a metallic cooller ABCD. To the upper part of this worm E, the chimney GH is fixed, which is composed of two tubes, the inner of which is a continuation of the worm, and the outer one is a case of tin-plate, which surrounds it at about an inch distance, and the interval is filled up with sand. At the inferior extremity K of the inner tube, a glass tube is fixed, to which we adopt the Argand lamp LM for burning alkohol, &c. Things being thus disposed, and the lamp being filled with a determinate quantity of alkohol, it is set on fire; the water which is formed during the combustion rises in the chimney KE, and being condensed in the worm, runs out at its extremity F into the bottle P. The double tube of the chimney, filled with sand in the interstice, is to prevent the tube from cooling in its upper part, and condensing the water; otherwise, it would fall back in the tube, and we should not be able to ascertain its quantity, and besides it might fall in drops upon the wick, and extinguish the flame. The intention of this construction, is to keep the chimney always hot, and the worm always cool, that the water may be preserved in the state of vapour whilst rising, and may be condensed immediately upon getting into the descending part of the apparatus. By this instrument, which was contrived by Mr Meusnier, and which is described by me in the Memoirs of the Academy for 1784, p. 593. we may, with attention to keep the worm always cold, collect nearly seventeen ounces of water from the combustion of sixteen ounces of alkohol. SECT. VIII. _Of the Oxydation of Metals._ The term _oxydation_ or _calcination_ is chiefly used to signify the process by which metals exposed to a certain degree of heat are converted into oxyds, by absorbing oxygen from the air. This combination takes place in consequence of oxygen possessing a greater affinity to metals, at a certain temperature, than to caloric, which becomes disengaged in its free state; but, as this disengagement, when made in common air, is slow and progressive, it is scarcely evident to the senses. It is quite otherwise, however, when oxydation takes place in oxygen gas; for, being produced with much greater rapidity, it is generally accompanied with heat and light, so as evidently to show that metallic substances are real combustible bodies. All the metals have not the same degree of affinity to oxygen. Gold, silver, and platina, for instance, are incapable of taking it away from its combination with caloric, even in the greatest known heat; whereas the other metals absorb it in a larger or smaller quantity, until the affinities of the metal to oxygen, and of the latter to caloric, are in exact equilibrium. Indeed, this state of equilibrium of affinities may be assumed as a general law of nature in all combinations. In all operations of this nature, the oxydation of metals is accelerated by giving free access to the air; it is sometimes much assisted by joining the action of a bellows, which directs a stream of air over the surface of the metal. This process becomes greatly more rapid if a stream of oxygen gas be used, which is readily done by means of the gazometer formerly described. The metal, in this case, throws out a brilliant flame, and the oxydation is very quickly accomplished; but this method can only be used in very confined experiments, on account of the expence of procuring oxygen gas. In the essay of ores, and in all the common operations of the laboratory, the calcination or oxydation of metals is usually performed in a dish of baked clay, Pl. IV. Fig. 6. commonly called a _roasting test_, placed in a strong furnace. The substances to be oxydated are frequently stirred, on purpose to present fresh surfaces to the air. Whenever this operation is performed upon a metal which is not volatile, and from which nothing flies off into the surrounding air during the process, the metal acquires additional weight; but the cause of this increased weight during oxydation could never have been discovered by means of experiments performed in free air; and it is only since these operations have been performed in close vessels, and in determinate quantities of air, that any just conjectures have been formed concerning the cause of this phenomenon. The first method for this purpose is due to Dr Priestley, who exposes the metal to be calcined in a porcelain cup N, Pl. IV. Fig. 11. placed upon the stand IK, under a jar A, in the bason BCDE, full of water; the water is made to rise up to GH, by sucking out the air with a syphon, and the focus of a burning glass is made to fall upon the metal. In a few minutes the oxydation takes place, a part of the oxygen contained in the air combines with the metal, and a proportional diminution of the volume of air is produced; what remains is nothing more than azotic gas, still however mixed with a small quantity of oxygen gas. I have given an account of a series of experiments made with this apparatus in my Physical and Chemical Essays, first published in 1773. Mercury may be used instead of water in this experiment, whereby the results are rendered still more conclusive. Another process for this purpose was invented by Mr Boyle, and of which I gave an account in the Memoirs of the Academy for 1774, p. 351. The metal is introduced into a retort, Pl. III. Fig. 20. the beak of which is hermetically sealed; the metal is then oxydated by means of heat applied with great precaution. The weight of the vessel, and its contained substances, is not at all changed by this process, until the extremity of the neck of the retort is broken; but, when that is done, the external air rushes in with a hissing noise. This operation is attended with danger, unless a part of the air is driven out of the retort, by means of heat, before it is hermetically sealed, as otherwise the retort would be apt to burst by the dilation of the air when placed in the furnace. The quantity of air driven out may be received under a jar in the pneumato-chemical apparatus, by which its quantity, and that of the air remaining in the retort, is ascertained. I have not multiplied my experiments upon oxydation of metals so much as I could have wished; neither have I obtained satisfactory results with any metal except tin. It is much to be wished that some person would undertake a series of experiments upon oxydation of metals in the several gasses; the subject is important, and would fully repay any trouble which this kind of experiment might occasion. As all the oxyds of mercury are capable of revivifying without addition, and restore the oxygen gas they had before absorbed, this seemed to be the most proper metal for becoming the subject of conclusive experiments upon oxydation. I formerly endeavoured to accomplish the oxydation of mercury in close vessels, by filling a retort, containing a small quantity of mercury, with oxygen gas, and adapting a bladder half full of the same gas to its beak; See Pl. IV. Fig. 12. Afterwards, by heating the mercury in the retort for a very long time, I succeeded in oxydating a very small portion, so as to form a little red oxyd floating upon the surface of the running mercury; but the quantity was so small, that the smallest error committed in the determination of the quantities of oxygen gas before and after the operation must have thrown very great uncertainty upon the results of the experiment. I was, besides, dissatisfied with this process, and not without cause, lest any air might have escaped through the pores of the bladder, more especially as it becomes shrivelled by the heat of the furnace, unless covered over with cloths kept constantly wet. This experiment is performed with more certainty in the apparatus described in the Memoirs of the Academy for 1775, p. 580. This consists of a retort, A, Pl. IV. Fig. 2. having a crooked glass tube BCDE of ten or twelve lines internal diameter, melted on to its beak, and which is engaged under the bell glass FG, standing with its mouth downwards, in a bason filled with water or mercury. The retort is placed upon the bars of the furnace MMNN, Pl. IV. Fig. 2. or in a sand bath, and by means of this apparatus we may, in the course of several days, oxydate a small quantity of mercury in common air; the red oxyd floats upon the surface, from which it may be collected and revivified, so as to compare the quantity of oxygen gas obtained in revivification with the absorption which took place during oxydation. This kind of experiment can only be performed upon a small scale, so that no very certain conclusions can be drawn from them[61]. The combustion of iron in oxygen gas being a true oxydation of that metal, ought to be mentioned in this place. The apparatus employed by Mr Ingenhousz for this operation is represented in Pl. IV. Fig. 17.; but, having already described it sufficiently in Chap. III. I shall refer the reader to what is said of it in that place. Iron may likewise be oxydated by combustion in vessels filled with oxygen gas, in the way already directed for phosphorus and charcoal. This apparatus is represented Pl. IV. Fig. 3. and described in the fifth chapter of the first part of this work. We learn from Mr Ingenhousz, that all the metals, except gold, silver, and mercury, may be burnt or oxydated in the same manner, by reducing them into very fine wire, or very thin plates cut into narrow slips; these are twisted round with iron-wire, which communicates the property of burning to the other metals. Mercury is even difficultly oxydated in free air. In chemical laboratories, this process is usually carried on in a matrass A, Pl. IV. Fig. having a very flat body, and a very long neck BC, which vessel is commonly called _Boyle's bell_. A quantity of mercury is introduced sufficient to cover the bottom, and it is placed in a sand-bath, which keeps up a constant heat approaching to that of boiling mercury. By continuing this operation with five or six similar matrasses during several months, and renewing the mercury from time to time, a few ounces of red oxyd are at last obtained. The great slowness and inconvenience of this apparatus arises from the air not being sufficiently renewed; but if, on the other hand, too free a circulation were given to the external air, it would carry off the mercury in solution in the state of vapour, so that in a few days none would remain in the vessel. As, of all the experiments upon the oxydation of metals, those with mercury are the most conclusive, it were much to be wished that a simple apparatus could be contrived by which this oxydation and its results might be demonstrated in public courses of chemistry. This might, in my opinion, be accomplished by methods similar to those I have already described for the combustion of charcoal and the oils; but, from other pursuits, I have not been able hitherto to resume this kind of experiment. The oxyd of mercury revives without addition, by being heated to a slightly red heat. In this degree of temperature, oxygen has greater affinity to caloric than to mercury, and forms oxygen gas. This is always mixed with a small portion of azotic gas, which indicates that the mercury absorbs a small portion of this latter gas during oxydation. It almost always contains a little carbonic acid gas, which must undoubtedly be attributed to the foulnesses of the oxyd; these are charred by the heat, and convert a part of the oxygen gas into carbonic acid. If chemists were reduced to the necessity of procuring all the oxygen gas employed in their experiments from mercury oxydated by heat without addition, or, as it is called, _calcined_ or _precipitated_ per se, the excessive dearness of that preparation would render experiments, even upon a moderate scale, quite impracticable. But mercury may likewise be oxydated by means of nitric acid; and in this way we procure a red oxyd, even more pure than that produced by calcination. I have sometimes prepared this oxyd by dissolving mercury in nitric acid, evaporating to dryness, and calcining the salt, either in a retort, or in capsules formed of pieces of broken matrasses and retorts, in the manner formerly described; but I have never succeeded in making it equally beautiful with what is sold by the druggists, and which is, I believe, brought from Holland. In choosing this, we ought to prefer what is in solid lumps composed of soft adhering scales, as when in powder it is sometimes adulterated with red oxyd of lead. To obtain oxygen gas from the red oxyd of mercury, I usually employ a porcelain retort, having a long glass tube adapted to its beak, which is engaged under jars in the water pneumato-chemical apparatus, and I place a bottle in the water, at the end of the tube, for receiving the mercury, in proportion as it revives and distils over. As the oxygen gas never appears till the retort becomes red, it seems to prove the principle established by Mr Berthollet, that an obscure heat can never form oxygen gas, and that light is one of its constituent elements. We must reject the first portion of gas which comes over, as being mixed with common air, from what was contained in the retort at the beginning of the experiment; but, even with this precaution, the oxygen gas procured is usually contaminated with a tenth part of azotic gas, and with a very small portion of carbonic acid gas. This latter is readily got rid of, by making the gas pass through a solution of caustic alkali; but we know of no method for separating the azotic gas; its proportions may however be ascertained, by leaving a known quantity of the oxygen gas contaminated with it for a fortnight, in contact with sulphuret of soda or potash, which absorbs the oxygen gas so as to convert the sulphur into sulphuric acid, and leaves the azotic gas remaining pure. We may likewise procure oxygen gas from black oxyd of manganese or nitrat of potash, by exposing them to a red heat in the apparatus already described for operating upon red oxyd of mercury; only, as it requires such a heat as is at least capable of softening glass, we must employ retorts of stone or of porcelain. But the purest and best oxygen gas is what is disengaged from oxygenated muriat of potash by simple heat. This operation is performed in a glass retort, and the gas obtained is perfectly pure, provided that the first portions, which are mixed with the common air of the vessels, be rejected. FOOTNOTES: [61] See an account of this experiment, Part. I. Chap. iii.--A. CHAP. IX. _Of Deflagration._ I have already shown, Part I. Chap. IX. that oxygen does not always part with the whole of the caloric it contained in the state of gas when it enters into combination with other bodies. It carries almost the whole of its caloric alongst with it in entering into the combinations which form nitric acid and oxygenated muriatic acid; so that in nitrats, and more especially in oxygenated muriats, the oxygen is, in a certain degree, in the state of oxygen gas, condensed, and reduced to the smallest volume it is capable of occupying. In these combinations, the caloric exerts a constant action upon the oxygen to bring it back to the state of gas; hence the oxygen adheres but very slightly, and the smallest additional force is capable of setting it free; and, when such force is applied, it often recovers the state of gas instantaneously. This rapid passage from the solid to the aëriform state is called detonation, or fulmination, because it is usually accompanied with noise and explosion. Deflagrations are commonly produced by means of combinations of charcoal either with nitre or oxygenated muriat of potash; sometimes, to assist the inflammation, sulphur is added; and, upon the just proportion of these ingredients, and the proper manipulation of the mixture, depends the art of making gun-powder. As oxygen is changed, by deflagration with charcoal, into carbonic acid, instead of oxygen gas, carbonic acid gas is disengaged, at least when the mixture has been made in just proportions. In deflagration with nitre, azotic gas is likewise disengaged, because azote is one of the constituent elements of nitric acid. The sudden and instantaneous disengagement and expansion of these gasses is not, however, sufficient for explaining all the phenomena of deflagration; because, if this were the sole operating power, gun powder would always be so much the stronger in proportion as the quantity of gas disengaged in a given time was the more considerable, which does not always accord with experiment. I have tried some kinds which produced almost double the effect of ordinary gun powder, although they gave out a sixth part less of gas during deflagration. It would appear that the quantity of caloric disengaged at the moment of detonation contributes considerably to the expansive effects produced; for, although caloric penetrates freely through the pores of every body in nature, it can only do so progressively, and in a given time; hence, when the quantity disengaged at once is too large to get through the pores of the surrounding bodies, it must necessarily act in the same way with ordinary elastic fluids, and overturn every thing that opposes its passage. This must, at least in part, take place when gun-powder is set on fire in a cannon; as, although the metal is permeable to caloric, the quantity disengaged at once is too large to find its way through the pores of the metal, it must therefore make an effort to escape on every side; and, as the resistance all around, excepting towards the muzzle, is too great to be overcome, this effort is employed for expelling the bullet. The caloric produces a second effect, by means of the repulsive force exerted between its particles; it causes the gasses, disengaged at the moment of deflagration, to expand with a degree of force proportioned to the temperature produced. It is very probable that water is decomposed during the deflagration of gun-powder, and that part of the oxygen furnished to the nascent carbonic acid gas is produced from it. If so, a considerable quantity of hydrogen gas must be disengaged in the instant of deflagration, which expands, and contributes to the force of the explosion. It may readily be conceived how greatly this circumstance must increase the effect of powder, if we consider that a pint of hydrogen gas weighs only one grain and two thirds; hence a very small quantity in weight must occupy a very large space, and it must exert a prodigious expansive force in passing from the liquid to the aëriform state of existence. In the last place, as a portion of undecomposed water is reduced to vapour during the deflagration of gun-powder, and as water, in the state of gas, occupies seventeen or eighteen hundred times more space than in its liquid state, this circumstance must likewise contribute largely to the explosive force of the powder. I have already made a considerable series of experiments upon the nature of the elastic fluids disengaged during the deflagration of nitre with charcoal and sulphur; and have made some, likewise, with the oxygenated muriat of potash. This method of investigation leads to tollerably accurate conclusions with respect to the constituent elements of these salts. Some of the principal results of these experiments, and of the consequences drawn from them respecting the analysis of nitric acid, are reported in the collection of memoirs presented to the Academy by foreign philosophers, vol. xi. p. 625. Since then I have procured more convenient instruments, and I intend to repeat these experiments upon a larger scale, by which I shall procure more accurate precision in their results; the following, however, is the process I have hitherto employed. I would very earnestly advise such as intend to repeat some of these experiments, to be very much upon their guard in operating upon any mixture which contains nitre, charcoal, and sulphur, and more especially with those in which oxygenated muriat of potash is mixed with these two materials. I make use of pistol barrels, about six inches long, and of five or six lines diameter, having the touch-hole spiked up with an iron nail strongly driven in, and broken in the hole, and a little tin-smith's solder run in to prevent any possible issue for the air. These are charged with a mixture of known quantities of nitre and charcoal, or any other mixture capable of deflagration, reduced to an impalpable powder, and formed into a paste with a moderate quantity of water. Every portion of the materials introduced must be rammed down with a rammer nearly of the same caliber with the barrel, four or five lines at the muzzle must be left empty, and about two inches of quick match are added at the end of the charge. The only difficulty in this experiment, especially when sulphur is contained in the mixture, is to discover the proper degree of moistening; for, if the paste be too much wetted, it will not take fire, and if too dry, the deflagration is apt to become too rapid, and even dangerous. When the experiment is not intended to be rigorously exact, we set fire to the match, and, when it is just about to communicate with the charge, we plunge the pistol below a large bell-glass full of water, in the pneumato chemical apparatus. The deflagration begins, and continues in the water, and gas is disengaged with less or more rapidity, in proportion as the mixture is more or less dry. So long as the deflagration continues, the muzzle of the pistol must be kept somewhat inclined downwards, to prevent the water from getting into its barrel. In this manner I have sometimes collected the gas produced from the deflagration of an ounce and half, or two ounces, of nitre. In this manner of operating it is impossible to determine the quantity of carbonic acid gas disengaged, because a part of it is absorbed by the water while passing through it; but, when the carbonic acid is absorbed, the azotic gas remains; and, if it be agitated for a few minutes in caustic alkaline solution, we obtain it pure, and can easily determine its volume and weight. We may even, in this way, acquire a tollerably exact knowledge of the quantity of carbonic acid by repeating the experiment a great many times, and varying the proportions of charcoal, till we find the exact quantity requisite to deflagrate the whole nitre employed. Hence, by means of the weight of charcoal employed, we determine the weight of oxygen necessary for saturation, and deduce the quantity of oxygen contained in a given weight of nitre. I have used another process, by which the results of this experiment are considerably more accurate, which consists in receiving the disengaged gasses in bell-glasses filled with mercury. The mercurial apparatus I employ is large enough to contain jars of from twelve to fifteen pints in capacity, which are not very readily managed when full of mercury, and even require to be filled by a particular method. When the jar is placed in the cistern of mercury, a glass syphon is introduced, connected with a small air-pump, by means of which the air is exhausted, and the mercury rises so as to fill the jar. After this, the gas of the deflagration is made to pass into the jar in the same manner as directed when water is employed. I must again repeat, that this species of experiment requires to be performed with the greatest possible precautions. I have sometimes seen, when the disengagement of gas proceeded with too great rapidity, jars filled with more than an hundred and fifty pounds of mercury driven off by the force of the explosion, and broken to pieces, while the mercury was scattered about in great quantities. When the experiment has succeeded, and the gas is collected under the jar, its quantity in general, and the nature and quantities of the several species of gasses of which the mixture is composed, are accurately ascertained by the methods already pointed out in the second chapter of this part of my work. I have been prevented from putting the last hand to the experiments I had begun upon deflagration, from their connection with the objects I am at present engaged in; and I am in hopes they will throw considerable light upon the operations belonging to the manufacture of gun-powder. CHAP. X. _Of the Instruments necessary for Operating upon Bodies in very high Temperatures._ SECT. I. _Of Fusion._ We have already seen, that, by aqueous solution, in which the particles of bodies are separated from each other, neither the solvent nor the body held in solution are at all decomposed; so that, whenever the cause of separation ceases, the particles reunite, and the saline substance recovers precisely the same appearance and properties it possessed before solution. Real solutions are produced by fire, or by introducing and accumulating a great quantity of caloric between the particles of bodies; and this species of solution in caloric is usually called _fusion_. This operation is commonly performed in vessels called crucibles, which must necessarily be less fusible than the bodies they are intended to contain. Hence, in all ages, chemists have been extremely solicitous to procure crucibles of very refractory materials, or such as are capable of resisting a very high degree of heat. The best are made of very pure clay or of porcelain earth; whereas such as are made of clay mixed with calcareous or silicious earth are very fusible. All the crucibles made in the neighbourhood of Paris are of this kind, and consequently unfit for most chemical experiments. The Hessian crucibles are tolerably good; but the best are made of Limoges earth, which seems absolutely infusible. We have, in France, a great many clays very fit for making crucibles; such, for instance, is the kind used for making melting pots at the glass-manufactory of St Gobin. Crucibles are made of various forms, according to the operations they are intended to perform. Several of the most common kinds are represented Pl. VII. Fig. 7. 8. 9. and 10. the one represented at Fig. 9. is almost shut at its mouth. Though fusion may often take place without changing the nature of the fused body, this operation is frequently employed as a chemical means of decomposing and recompounding bodies. In this way all the metals are extracted from their ores; and, by this process, they are revivified, moulded, and alloyed with each other. By this process sand and alkali are combined to form glass, and by it likewise pastes, or coloured stones, enamels, &c. are formed. The action of violent fire was much more frequently employed by the ancient chemists than it is in modern experiments. Since greater precision has been employed in philosophical researches, the _humid_ has been preferred to the _dry_ method of process, and fusion is seldom had recourse to until all the other means of analysis have failed. SECT. II. _Of Furnaces._ These are instruments of most universal use in chemistry; and, as the success of a great number of experiments depends upon their being well or ill constructed, it is of great importance that a laboratory be well provided in this respect. A furnace is a kind of hollow cylindrical tower, sometimes widened above, Pl. XIII. Fig. 1. ABCD, which must have at least two lateral openings; one in its upper part F, which is the door of the fire-place, and one below, G, leading to the ash-hole. Between these the furnace is divided by a horizontal grate, intended for supporting the fewel, the situation of which is marked in the figure by the line HI. Though this be the least complicated of all the chemical furnaces, yet it is applicable to a great number of purposes. By it lead, tin, bismuth, and, in general, every substance which does not require a very strong fire, may be melted in crucibles; it will serve for metallic oxydations, for evaporatory vessels, and for sand-baths, as in Pl. III. Fig. 1. and 2. To render it proper for these purposes, several notches, m m m m, Pl. XIII. Fig. 1. are made in its upper edge, as otherwise any pan which might be placed over the fire would stop the passage of the air, and prevent the fewel from burning. This furnace can only produce a moderate degree of heat, because the quantity of charcoal it is capable of consuming is limited by the quantity of air which is allowed to pass through the opening G of the ash-hole. Its power might be considerably augmented by enlarging this opening, but then the great stream of air which is convenient for some operations might be hurtful in others; wherefore we must have furnaces of different forms, constructed for different purposes, in our laboratories: There ought especially to be several of the kind now described of different sizes. The reverberatory furnace, Pl. XIII. Fig. 2. is perhaps more necessary. This, like the common furnace, is composed of the ash-hole HIKL, the fire-place KLMN, the laboratory MNOP, and the dome RRSS, with its funnel or chimney TTVV; and to this last several additional tubes may be adapted, according to the nature of the different experiments. The retort A is placed in the division called the laboratory, and supported by two bars of iron which run across the furnace, and its beak comes out at a round hole in the side of the furnace, one half of which is cut in the piece called the laboratory, and the other in the dome. In most of the ready made reverberatory furnaces which are sold by the potters at Paris, the openings both above and below are too small: These do not allow a sufficient volume of air to pass through; hence, as the quantity of charcoal consumed, or, what is much the same thing, the quantity of caloric disengaged, is nearly in proportion to the quantity of air which passes through the furnace, these furnaces do not produce a sufficient effect in a great number of experiments. To remedy this defect, there ought to be two openings GG to the ash-hole; one of these is shut up when only a moderate fire is required; and both are kept open when the strongest power of the furnace is to be exerted. The opening of the dome SS ought likewise to be considerably larger than is usually made. It is of great importance not to employ retorts of too large size in proportion to the furnace, as a sufficient space ought always to be allowed for the passage of the air between the sides of the furnace and the vessel. The retort A in the figure is too small for the size of the furnace, yet I find it more easy to point out the error than to correct it. The intention of the dome is to oblige the flame and heat to surround and strike back or reverberate upon every part of the retort, whence the furnace gets the name of reverberatory. Without this circumstance the retort would only be heated in its bottom, the vapours raised from the contained substance would condense in the upper part, and a continual cohabitation would take place without any thing passing over into the receiver, but, by means of the dome, the retort is equally heated in every part, and the vapours being forced out, can only condense in the neck of the retort, or in the recipient. To prevent the bottom of the retort from being either heated or coolled too suddenly, it is sometimes placed in a small sand-bath of baked clay, standing upon the cross bars of the furnace. Likewise, in many operations, the retorts are coated over with lutes, some of which are intended to preserve them from the too sudden influence of heat or of cold, while others are for sustaining the glass, or forming a kind of second retort, which supports the glass one during operations wherein the strength of the fire might soften it. The former is made of brick-clay with a little cow's hair beat up alongst with it, into a paste or mortar, and spread over the glass or stone retorts. The latter is made of pure clay and pounded stone-ware mixed together, and used in the same manner. This dries and hardens by the fire, so as to form a true supplementary retort capable of retaining the materials, if the glass retort below should crack or soften. But, in experiments which are intended for collecting gasses, this lute, being porous, is of no manner of use. In a great many experiments wherein very violent fire is not required, the reverberatory furnace may be used as a melting one, by leaving out the piece called the laboratory, and placing the dome immediately upon the fire-place, as represented Pl. XIII. Fig. 3. The furnace represented in Fig. 4. is very convenient for fusions; it is composed of the fire-place and ash-hole ABD, without a door, and having a hole E, which receives the muzzle of a pair of bellows strongly luted on, and the dome ABGH, which ought to be rather lower than is represented in the figure. This furnace is not capable of producing a very strong heat, but is sufficient for ordinary operations, and may be readily moved to any part of the laboratory where it is wanted. Though these particular furnaces are very convenient, every laboratory must be provided with a forge furnace, having a good pair of bellows, or, what is more necessary, a powerful melting furnace. I shall describe the one I use, with the principles upon which it is constructed. The air circulates in a furnace in consequence of being heated in its passage through the burning coals; it dilates, and, becoming lighter than the surrounding air, is forced to rise upwards by the pressure of the lateral columns of air, and is replaced by fresh air from all sides, especially from below. This circulation of air even takes place when coals are burnt in a common chaffing dish; but we can readily conceive, that, in a furnace open on all sides, the mass of air which passes, all other circumstances being equal, cannot be so great as when it is obliged to pass through a furnace in the shape of a hollow tower, like most of the chemical furnaces, and consequently, that the combustion must be more rapid in a furnace of this latter construction. Suppose, for instance, the furnace ABCDEF open above, and filled with burning coals, the force with which the air passes through the coals will be in proportion to the difference between the specific gravity of two columns equal to AC, the one of cold air without, and the other of heated air within the furnace. There must be some heated air above the opening AB, and the superior levity of this ought likewise to be taken into consideration; but, as this portion is continually coolled and carried off by the external air, it cannot produce any great effect. But, if we add to this furnace a large hollow tube GHAB of the same diameter, which preserves the air which has been heated by the burning coals from being coolled and dispersed by the surrounding air, the difference of specific gravity which causes the circulation will then be between two columns equal to GC. Hence, if GC be three times the length of AC, the circulation will have treble force. This is upon the supposition that the air in GHCD is as much heated as what is contained in ABCD, which is not strictly the case, because the heat must decrease between AB and GH; but, as the air in GHAB is much warmer than the external air, it follows, that the addition of the tube must increase the rapidity of the stream of air, that a larger quantity must pass through the coals, and consequently that a greater degree of combustion must take place. We must not, however, conclude from these principles, that the length of this tube ought to be indefinitely prolonged; for, since the heat of the air gradually diminishes in passing from AB to GH, even from the contact of the sides of the tube, if the tube were prolonged to a certain degree, we would at last come to a point where the specific gravity of the included air would be equal to the air without; and, in this case, as the cool air would no longer tend to rise upwards, it would become a gravitating mass, resisting the ascension of the air below. Besides, as this air, which has served for combustion, is necessarily mixed with carbonic acid gas, which is considerably heavier than common air, if the tube were made long enough, the air might at last approach so near to the temperature of the external air as even to gravitate downwards; hence we must conclude, that the length of the tube added to a furnace must have some limit beyond which it weakens, instead of strengthening the force of the fire. From these reflections it follows, that the first foot of tube added to a furnace produces more effect than the sixth, and the sixth more than the tenth; but we have no data to ascertain at what height we ought to stop. This limit of useful addition is so much the farther in proportion as the materials of the tube are weaker conductors of heat, because the air will thereby be so much less coolled; hence baked earth is much to be preferred to plate iron. It would be even of consequence to make the tube double, and to fill the interval with rammed charcoal, which is one of the worst conductors of heat known; by this the refrigeration of the air will be retarded, and the rapidity of the stream of air consequently increased; and, by this means, the tube may be made so much the longer. As the fire-place is the hottest part of a furnace, and the part where the air is most dilated in its passage, this part ought to be made with a considerable widening or belly. This is the more necessary, as it is intended to contain the charcoal and crucible, as well as for the passage of the air which supports, or rather produces the combustion; hence we only allow the interstices between the coals for the passage of the air. From these principles my melting furnace is constructed, which I believe is at least equal in power to any hitherto made, though I by no means pretend that it possesses the greatest possible intensity that can be produced in chemical furnaces. The augmentation of the volume of air produced during its passage through a melting furnace not being hitherto ascertained from experiment, we are still unacquainted with the proportions which should exist between the inferior and superior apertures, and the absolute size of which these openings should be made is still less understood; hence data are wanting by which to proceed upon principle, and we can only accomplish the end in view by repeated trials. This furnace, which, according to the above stated rules, is in form of an eliptical spheroid, is represented Pl. XIII. Fig. 6. ABCD; it is cut off at the two ends by two plains, which pass, perpendicular to the axis, through the foci of the elipse. From this shape it is capable of containing a considerable quantity of charcoal, while it leaves sufficient space in the intervals for the passage of the air. That no obstacle may oppose the free access of external air, it is perfectly open below, after the model of Mr Macquer's melting furnace, and stands upon an iron tripod. The grate is made of flat bars set on edge, and with considerable interstices. To the upper part is added a chimney, or tube, of baked earth, ABFG, about eighteen feet long, and almost half the diameter of the furnace. Though this furnace produces a greater heat than any hitherto employed by chemists, it is still susceptible of being considerably increased in power by the means already mentioned, the principal of which is to render the tube as bad a conductor of heat as possible, by making it double, and filling the interval with rammed charcoal. When it is required to know if lead contains any mixture of gold or silver, it is heated in a strong fire in capsules of calcined bones, which are called cuppels. The lead is oxydated, becomes vitrified, and sinks into the substance of the cuppel, while the gold or silver, being incapable of oxydation, remain pure. As lead will not oxydate without free access of air, this operation cannot be performed in a crucible placed in the middle of the burning coals of a furnace, because the internal air, being mostly already reduced by the combustion into azotic and carbonic acid gas, is no longer fit for the oxydation of metals. It was therefore necessary to contrive a particular apparatus, in which the metal should be at the same time exposed to the influence of violent heat, and defended from contact with air rendered incombustible by its passage through burning coals. The furnace intended for answering this double purpose is called the cuppelling or essay furnace. It is usually made of a square form, as represented Pl. XIII. Fig. 8. and 10. having an ash-hole AABB, a fire-place BBCC, a laboratory CCDD, and a dome DDEE. The muffle or small oven of baked earth GH, Fig. 9. being placed in the laboratory of the furnace upon cross bars of iron, is adjusted to the opening GG, and luted with clay softened in water. The cuppels are placed in this oven or muffle, and charcoal is conveyed into the furnace through the openings of the dome and fire-place. The external air enters through the openings of the ash-hole for supporting the combustion, and escapes by the superior opening or chimney at EE; and air is admitted through the door of the muffle GG for oxydating the contained metal. Very little reflection is sufficient to discover the erroneous principles upon which this furnace is constructed. When the opening GG is shut, the oxydation is produced slowly, and with difficulty, for want of air to carry it on; and, when this hole is open, the stream of cold air which is then admitted fixes the metal, and obstructs the process. These inconveniencies may be easily remedied, by constructing the muffle and furnace in such a manner that a stream of fresh external air should always play upon the surface of the metal, and this air should be made to pass through a pipe of clay kept continually red hot by the fire of the furnace. By this means the inside of the muffle will never be coolled, and processes will be finished in a few minutes, which at present require a considerable space of time. Mr Sage remedies these inconveniencies in a different manner; he places the cuppel containing lead, alloyed with gold or silver, amongst the charcoal of an ordinary furnace, and covered by a small porcelain muffle; when the whole is sufficiently heated, he directs the blast of a common pair of hand-bellows upon the surface of the metal, and completes the cuppellation in this way with great ease and exactness. SECT. III. _Of increasing the Action of Fire, by using Oxygen Gas instead of Atmospheric Air._ By means of large burning glasses, such as those of Tchirnausen and Mr de Trudaine, a degree of heat is obtained somewhat greater than has hitherto been produced in chemical furnaces, or even in the ovens of furnaces used for baking hard porcelain. But these instruments are extremely expensive, and do not even produce heat sufficient to melt crude platina; so that their advantages are by no means sufficient to compensate for the difficulty of procuring, and even of using them. Concave mirrors produce somewhat more effect than burning glasses of the same diameter, as is proved by the experiments of Messrs Macquer and Beaumé with the speculum of the Abbé Bouriot; but, as the direction of the reflected rays is necessarily from below upwards, the substance to be operated upon must be placed in the air without any support, which renders most chemical experiments impossible to be performed with this instrument. For these reasons, I first endeavoured to employ oxygen gas for combustion, by filling large bladders with it, and making it pass through a tube capable of being shut by a stop-cock; and in this way I succeeded in causing it to support the combustion of lighted charcoal. The intensity of the heat produced, even in my first attempt, was so great as readily to melt a small quantity of crude platina. To the success of this attempt is owing the idea of the gazometer, described p. 308. _et seq._ which I substituted instead of the bladders; and, as we can give the oxygen gas any necessary degree of pressure, we can with this instrument keep up a continued stream, and give it even a very considerable force. The only apparatus necessary for experiments of this kind consists of a small table ABCD, Pl. XII. Fig. 15, with a hole F, through which passes a tube of copper or silver, ending in a very small opening at G, and capable of being opened or shut by the stop-cock H. This tube is continued below the table at l m n o, and is connected with the interior cavity of the gazometer. When we mean to operate, a hole of a few lines deep must be made with a chizel in a piece of charcoal, into which the substance to be treated is laid; the charcoal is set on fire by means of a candle and blow-pipe, after which it is exposed to a rapid stream of oxygen gas from the extremity G of the tube FG. This manner of operating can only be used with such bodies as can be placed, without inconvenience, in contact with charcoal, such as metals, simple earths, &c. But, for bodies whose elements have affinity to charcoal, and which are consequently decomposed by that substance, such as sulphats, phosphats, and most of the neutral salts, metallic glasses, enamels, &c. we must use a lamp, and make the stream of oxygen gas pass through its flame. For this purpose, we use the elbowed blow-pipe ST, instead of the bent one FG, employed with charcoal. The heat produced in this second manner is by no means so intense as in the former way, and is very difficultly made to melt platina. In this manner of operating with the lamp, the substances are placed in cuppels of calcined bones, or little cups of porcelain, or even in metallic dishes. If these last are sufficiently large, they do not melt, because, metals being good conductors of heat, the caloric spreads rapidly through the whole mass, so that none of its parts are very much heated. In the Memoirs of the Academy for 1782, p. 476. and for 1783, p. 573. the series of experiments I have made with this apparatus may be seen at large. The following are some of the principal results. 1. Rock cristal, or pure silicious earth, is infusible, but becomes capable of being softened or fused when mixed with other substances. 2. Lime, magnesia, and barytes, are infusible, either when alone, or when combined together; but, especially lime, they assist the fusion of every other body. 3. Argill, or pure base of alum, is completely fusible _per se_ into a very hard opake vitreous substance, which scratches glass like the precious stones. 4. All the compound earths and stones are readily fused into a brownish glass. 5. All the saline substances, even fixed alkali, are volatilized in a few seconds. 6. Gold, silver, and probably platina, are slowly volatilized without any particular phenomenon. 7. All other metallic substances, except mercury, become oxydated, though placed upon charcoal, and burn with different coloured flames, and at last dissipate altogether. 8. The metallic oxyds likewise all burn with flames. This seems to form a distinctive character for these substances, and even leads me to believe, as was suspected by Bergman, that barytes is a metallic oxyd, though we have not hitherto been able to obtain the metal in its pure or reguline state. 9. Some of the precious stones, as rubies, are capable of being softened and soldered together, without injuring their colour, or even diminishing their weights. The hyacinth, tho' almost equally fixed with the ruby, loses its colour very readily. The Saxon and Brasilian topaz, and the Brasilian ruby, lose their colour very quickly, and lose about a fifth of their weight, leaving a white earth, resembling white quartz, or unglazed china. The emerald, chrysolite, and garnet, are almost instantly melted into an opake and coloured glass. 10. The diamond presents a property peculiar to itself; it burns in the same manner with combustible bodies, and is entirely dissipated. There is yet another manner of employing oxygen gas for considerably increasing the force of fire, by using it to blow a furnace. Mr Achard first conceived this idea; but the process he employed, by which he thought to dephlogisticate, as it is called, atmospheric air, or to deprive it of azotic gas, is absolutely unsatisfactory. I propose to construct a very simple furnace, for this purpose, of very refractory earth, similar to the one represented Pl. XIII. Fig. 4. but smaller in all its dimensions. It is to have two openings, as at E, through one of which the nozle of a pair of bellows is to pass, by which the heat is to be raised as high as possible with common air; after which, the stream of common air from the bellows being suddenly stopt, oxygen gas is to be admitted by a tube, at the other opening, communicating with a gazometer having the pressure of four or five inches of water. I can in this manner unite the oxygen gas from several gazometers, so as to make eight or nine cubical feet of gas pass through the furnace; and in this way I expect to produce a heat greatly more intense than any hitherto known. The upper orifice of the furnace must be carefully made of considerable dimensions, that the caloric produced may have free issue, lest the too sudden expansion of that highly elastic fluid should produce a dangerous explosion. FINIS. APPENDIX. No. I. TABLE _for Converting Lines, or Twelfth Parts of an Inch, and Fractions of Lines, into Decimal Fractions of the Inch._ Twelfth Parts Decimal Decimal of a Line. Fractions. Lines. Fractions. 1 0.00694 1 0.08333 2 0.01389 2 0.16667 3 0.02083 3 0.25000 4 0.02778 4 0.33333 5 0.03472 5 0.41667 6 0.04167 6 0.50000 7 0.04861 7 0.58333 8 0.05556 8 0.66667 9 0.06250 9 0.75000 10 0.06944 10 0.83333 11 0.07639 11 0.91667 12 0.08333 12 1.00000 No. II. TABLE _for Converting the Observed Heighths of Water in the Jars of the Pneumato-Chemical Apparatus, expressed in Inches and Decimals, into Corresponding Heighths of Mercury._ Water. Mercury. Water. Mercury. .1 .00737 4. .29480 .2 .01474 5. .36851 .3 .02201 6. .44221 .4 .02948 7. .51591 .5 .03685 8. .58961 .6 .04422 9. .66332 .7 .05159 10. .73702 .8 .05896 11. .81072 .9 .06633 12. .88442 1. .07370 13. .96812 2. .14740 14. 1.04182 3. .22010 15. 1.11525 No. III. TABLE _for Converting the Ounce Measures used by Dr Priestly into French and English Cubical Inches._ Ounce French cubical English cubical measures. inches. inches. 1 1.567 1.898 2 3.134 3.796 3 4.701 5.694 4 6.268 7.592 5 7.835 9.490 6 9.402 11.388 7 10.969 13.286 8 12.536 15.184 9 14.103 17.082 10 15.670 18.980 20 31.340 37.960 30 47.010 56.940 40 62.680 75.920 50 78.350 94.900 60 94.020 113.880 70 109.690 132.860 80 125.360 151.840 90 141.030 170.820 100 156.700 189.800 1000 1567.000 1898.000 No. IV. ADDITIONAL. TABLE _for Reducing the Degrees of Reaumeur's Thermometer into its corresponding Degrees of Fahrenheit's Scale._ R. F. R. F. R. F. R. F. 0 = 32 21 = 79.25 41 = 124.25 61 = 169.25 1 = 34.25 22 = 81.5 42 = 126.5 62 = 171.5 2 = 36.5 23 = 83.75 43 = 128.75 63 = 173.75 3 = 38.75 24 = 86 44 = 131 64 = 176. 4 = 41 25 = 88.25 45 = 133.25 65 = 178.25 5 = 43.25 26 = 90.5 46 = 135.5 66 = 180.5 6 = 45.5 27 = 92.75 47 = 137.75 67 = 182.75 7 = 47.75 28 = 95 48 = 140 68 = 185 8 = 50 29 = 97.25 49 = 142.25 69 = 187.25 9 = 52.25 30 = 99.5 50 = 144.5 70 = 189.5 10 = 54.5 31 = 101.75 51 = 146.75 71 = 191.75 11 = 56.75 32 = 104 52 = 149 72 = 194. 12 = 59 33 = 106.25 53 = 151.25 73 = 196.25 13 = 61.25 34 = 108.5 54 = 153.5 74 = 198.5 14 = 63.5 35 = 110.75 55 = 155.75 75 = 200.75 15 = 65.75 36 = 113 56 = 158 76 = 203 16 = 68 37 = 115.25 57 = 160.25 77 = 205.25 17 = 70.25 38 = 117.5 58 = 162.5 78 = 207.5 18 = 72.5 39 = 119.75 59 = 164.75 79 = 209.75 19 = 74.75 40 = 122 60 = 167 80 = 212 20 = 77 _Note_--Any degree, either higher or lower, than what is contained in the above Table, may be at any time converted, by remembering that one degree of Reaumeur's scale is equal to 2.25° of Fahrenheit; or it may be done without the Table by the following formula, R × 9 / 4 + 32 = F; that is, multiply the degree of Reaumeur by 9, divide the product by 4, to the quotient add 32, and the sum is the degree of Fahrenheit.--E. No. V. ADDITIONAL. RULES _for converting French Weights and Measures into correspondent English Denominations[62]._ § 1. _Weights._ The Paris pound, poids de mark of Charlemagne, contains 9216 Paris grains; it is divided into 16 ounces, each ounce into 8 gros, and each gros into 72 grains. It is equal to 7561 English Troy grains. The English Troy pound of 12 ounces contains 5760 English Troy grains, and is equal to 7021 Paris grains. The English averdupois pound of 16 ounces contains 7000 English Troy grains, and is equal to 8538 Paris grains. To reduce Paris grs. to English Troy } grs. divide by } 1.2189 To reduce English Troy grs. to Paris } grs. multiply by } To reduce Paris ounces to English } Troy, divide by } To reduce English Troy ounces to } 1.015734 Paris, multiply by } Or the conversion may be made by means of the following Tables. I. _To reduce French to English Troy Weight._ The Paris pound = 7561 } The ounce = 472.5625 } English. The gros = 59.0703 } Troy. The grain = .8194 } Grains. II. _To Reduce English Troy to Paris Weight._ The English Troy pound } = 7021. } of 12 ounces } } The Troy ounce = 585.0830 } The dram of 60 grs. = 73.1353 } Paris The penny weight, or } = 29.2540 } grains. denier, of 24 grs. } } The scruple, of 20 grs. = 24.3784 } III. _To Reduce English Averdupois to Paris Weight._ The averdupois pound of } } 16 ounces, or 7000 } = 8538. } Paris Troy grains. } } grains. The ounce = 533.6250 } § 2. _Long and Cubical Measures._ To reduce Paris feet or inches into } English, multiply by } 1.065977 English feet or inches into Paris, } divide by } To reduce Paris cubic feet or inches } to English, multiply by } English cubic feet or inches to Paris, } 1.211278 divide by } Or by means of the following tables: IV. _To Reduce Paris Long Measure to English._ The Paris royal foot of } } 12 inches } = 12.7977 } English The inch = 1.0659 } The line, or 1/12 of an inch = .0888 } inches. The 1/12 of a line = .0074 } V. _To Reduce English Long Measure to French._ The English foot = 11.2596 } The inch = .9383 } The 1/8 of an inch = .1173 } Paris inches. The 1/10 = .0938 } The line, or 1/12 = .0782 } VI. _To Reduce French Cube Measure to English._ The Paris } English { } cube foot = 1.211278 } cubical { 2093.088384 } The cubic } feet, { } inches. inch = .000700 } or { 1.211278 } VII. _To Reduce English Cube Measure to French._ The English cube foot, } or 1728 cubical inches } = 1427.4864 } French The cubical inch = .8260 } cubical The cube tenth = .0008 } inches. § 3. _Measure of Capacity._ The Paris pint contains 58.145[63] English cubical inches, and the English wine pint contains 28.85 cubical inches; or, the Paris pint contains 2.01508 English pints, and the English pint contains .49617 Paris pints; hence, To reduce the Paris pint to the English, } multiply by } 2.01508. To reduce the English pint to the } Paris, divide by } No. VI. TABLE _of the Weights of the different Gasses, at 28 French inches, or 29.84 English inches barometrical pressure, and at 10° (54.5°) of temperature, expressed in English measure and English Troy weight._ Names of the Gasses. Weight of a Weight of a cubical inch. cubical foot. (A) qrs. oz. dr. qrs. Atmospheric air .32112 1 1 15 Azotic gas .30064 1 0 39.5 Oxygen gas .34211 1 1 51 Hydrogen gas .02394 0 0 41.26 Carbonic acid gas .44108 1 4 41 (B) Nitrous gas .37000 1 2 39 Ammoniacal gas .18515 0 5 19.73 Sulphurous acid gas .71580 2 4 38 [Note A: These five were ascertained by Mr Lavoisier himself.--E.] [Note B: The last three are inserted by Mr Lavoisier upon the authority of Mr Kirwan.--E.] No. VII. _Tables_ _of the Specific Gravities of different bodies._ § 1. _Metallic Substances._ GOLD. Pure gold of 24 carats melted but not hammered 19.2581 The same hammered 19.3617 Gold of the Parisian standard, 22 carats fine, not hammered(A) 17.4863 The same hammered 17.5894 Gold of the standard of French coin, 21-22/32 carats fine, not hammered 17.4022 The same coined 17.6474 Gold of the French trinket standard, 20 carats fine, not hammered 15.7090 The same hammered 15.7746 [Note A: The same with Sterling.] SILVER. Pure or virgin silver, 24 deniers, not hammered 10.4743 The same hammered 10.5107 Silver of the Paris standard, 11 deniers 10 grains fine, not hammered(B) 10.1752 The same hammered 10.3765 Silver, standard of French coin, 10 deniers 21 grains fine, not hammered 10.0476 The same coined 10.4077 [Note B: This is 10 grs. finer than Sterling.] PLATINA. Crude platina in grains 15.6017 The same, after being treated with muriatic acid 16.7521 Purified platina, not hammered 19.5000 The same hammered 20.3366 The same drawn into wire 21.0417 The same passed through rollers 22.0690 COPPER AND BRASS. Copper, not hammered 7.7880 The same wire drawn 8.8785 Brass, not hammered 8.3958 The same wire drawn 8.5441 IRON AND STEEL. Cast iron 7.2070 Bar iron, either screwed or not 7.7880 Steel neither tempered nor screwed 7.8331 Steel screwed but not tempered 7.8404 Steel tempered and screwed 7.8180 Steel tempered and not screwed 7.8163 TIN. Pure tin from Cornwall melted and not screwed 7.2914 The same screwed 7.2994 Malacca tin, not screwed 7.2963 The same screwed 7.3065 Molten lead 11.3523 Molten zinc 7.1908 Molten bismuth 9.8227 Molten cobalt 7.8119 Molten arsenic 5.7633 Molten nickel 7.8070 Molten antimony 6.7021 Crude antimony 4.0643 Glass of antimony 4.9464 Molybdena 4.7385 Tungstein 6.0665 Mercury 13.5681 § 2. _Precious Stones._ White Oriental diamond 3.5212 Rose-coloured Oriental ditto 3.5310 Oriental ruby 4.2833 Spinell ditto 3.7600 Ballas ditto 3.6458 Brasillian ditto 3.5311 Oriental topas 4.0106 Ditto Pistachio ditto 4.0615 Brasillian ditto 3.5365 Saxon topas 3.5640 Ditto white ditto 3.5535 Oriental saphir 3.9941 Ditto white ditto 3.9911 Saphir of Puy 4.0769 Ditto of Brasil 3.1307 Girasol 4.0000 Ceylon jargon 4.4161 Hyacinth 3.6873 Vermillion 4.2299 Bohemian garnet 4.1888 Dodecahedral ditto 4.0627 Syrian ditto 4.0000 Volcanic ditto, with 24 sides 2.4684 Peruvian emerald 2.7755 Crysolite of the jewellers 2.7821 Ditto of Brasil 2.6923 Beryl, or Oriental aqua marine 3.5489 Occidental aqua marine 2.7227 § 3. _Silicious Stones._ Pure rock cristal of Madagascar 2.6530 Ditto of Brasil 2.6526 Ditto of Europe, or gelatinous 2.6548 Cristallized quartz 2.6546 Amorphous ditto 2.6471 Oriental agate 2.5901 Agate onyx 2.6375 Transparent calcedony 2.6640 Carnelian 2.6137 Sardonyx 2.6025 Prase 2.5805 Onyx pebble 2.6644 Pebble of Rennes 2.6538 White jade 2.9502 Green jade 2.9660 Red jasper 2.6612 Brown ditto 2.6911 Yellow ditto 2.7101 Violet ditto 2.7111 Gray ditto 2.7640 Jasponyx 2.8160 Black prismatic hexahedral schorl 3.3852 Black spary ditto 3.3852 Black amorphous schorl, called antique basaltes 2.9225 Paving stone 2.4158 Grind stone 2.1429 Cutler's stone 2.1113 Fountainbleau stone 2.5616 Scyth stone of Auvergne 2.5638 Ditto of Lorrain 2.5298 Mill stone 2.4835 White flint 2.5941 Blackish ditto 2.5817 § 4. _Various Stones, &c._ Opake green Italian serpentine, or gabro of the Florentines 2.4295 Coarse Briancon chalk 2.7274 Spanish chalk 2.7902 Foliated lapis ollaris of Dauphiny 2.7687 Ditto ditto from Sweden 2.8531 Muscovy talc 2.7917 Black mica 2.9004 Common schistus or slate 2.6718 New slate 2.8535 White rasor hone 2.8763 Black and white hone 3.1311 Rhombic or Iceland cristal 2.7151 Pyramidal calcareous spar 2.7141 Oriental or white antique alabaster 2.7302 Green Campan marble 2.7417 Red Campan marble 2.7242 White Carara marble 2.7168 White Parian marble 2.8376 Various kinds of calcareous stones } from 1.3864 used in France for building. } to 2.3902 Heavy spar 4.4300 White fluor 3.1555 Red ditto 3.1911 Green ditto 3.1817 Blue ditto 3.1688 Violet ditto 3.1757 Red scintilant zeolite from Edelfors 2.4868 White scintilant zeolite 2.0739 Cristallized zeolite 2.0833 Black pitch stone 2.0499 Yellow pitch stone 2.0860 Red ditto 2.6695 Blackish ditto 2.3191 Red porphyry 2.7651 Ditto of Dauphiny 2.7033 Green serpentine 2.8960 Black ditto of Dauphiny, called variolite 2.9339 Green ditto from Dauphiny 2.9883 Ophites 2.9722 Granitello 3.0626 Red Egyptian granite 2.6541 Beautiful red granite 2.7609 Granite of Girardmas 2.7163 Pumice stone .9145 Lapis obsidianus 2.3480 Pierre de Volvic 2.3205 Touch stone 2.4153 Basaltes from Giants Causeway 2.8642 Ditto prismatic from Auvergne 2.4153 Glass gall 2.8548 Bottle glass 2.7325 Green glass 2.6423 White glass 2.8922 St Gobin cristal 2.4882 Flint glass 3.3293 Borax glass 2.6070 Seves porcelain 2.1457 Limoges ditto 2.3410 China ditto 2.3847 Native sulphur 2.0332 Melted sulphur 1.9907 Hard peat 1.3290 Ambergrease .9263 Yellow transparent amber 1.0780 § 5. _Liquids._ Distilled water 1.0000 Rain water 1.0000 Filtered water of the Seine 1.00015 Arcueil water 1.00046 Avray water 1.00043 Sea water 1.0263 Water of the Dead Sea 1.2403 Burgundy wine .9915 Bourdeaux ditto .9939 Malmsey Madeira 1.0382 Red beer 1.0338 White ditto 1.0231 Cyder 1.0181 Highly rectified alkohol .8293 Common spirits of wine .8371 Alkohol 15 pts. water 1 part. .8527 14 2 .8674 13 3 .8815 12 4 .8947 11 5 .9075 10 6 .9199 9 7 .9317 8 8 .9427 7 9 .9519 6 10 .9594 5 11 .9674 4 12 .9733 3 13 .9791 2 14 .9852 1 15 .9919 Sulphuric ether .7394 Nitric ether .9088 Muriatic ether .7298 Acetic ether .8664 Sulphuric acid 1.8409 Nitric ditto 1.2715 Muriatic ditto 1.1940 Red acetous ditto 1.0251 White acetous ditto 1.0135 Distilled ditto ditto 1.0095 Acetic ditto 1.0626 Formic ditto .9942 Solution of caustic ammoniac, or volatil alkali fluor .8970 Essential or volatile oil of turpentine .8697 Liquid turpentine .9910 Volatile oil of lavender .8938 Volatile oil of cloves 1.0363 Volatile oil of cinnamon 1.0439 Oil of olives .9153 Oil of sweet almonds .9170 Lintseed oil .9403 Oil of poppy seed .9288 Oil of beech mast .9176 Whale oil .9233 Womans milk 1.0203 Mares milk 1.0346 Ass milk 1.0355 Goats milk 1.0341 Ewe milk 1.0409 Cows milk 1.0324 Cow whey 1.0193 Human urine 1.0106 § 6. _Resins and Gums_ Common yellow or white rosin 1.0727 Arcanson 1.0857 Galipot(A) 1.0819 Baras(A) 1.0441 Sandarac 1.0920 Mastic 1.0742 Storax 1.1098 Opake copal 1.1398 Transparent ditto 1.0452 Madagascar ditto 1.0600 Chinese ditto 1.0628 Elemi 1.0182 Oriental anime 1.0284 Occidental ditto 1.0426 Labdanum 1.1862 Ditto _in tortis_ 2.4933 Resin of guaiac 1.2289 Ditto of jallap 1.2185 Dragons blood 1.2045 Gum lac 1.1390 Tacamahaca 1.0463 Benzoin 1.0924 Alouchi(B) 1.0604 Caragna(C) 1.1244 Elastic gum .9335 Camphor .9887 Gum ammoniac 1.2071 Sagapenum 1.2008 Ivy gum(D) 1.2948 Gamboge 1.2216 Euphorbium 1.1244 Olibanum 1.1732 Myrrh 1.3600 Bdellium 1.3717 Aleppo Scamony 1.2354 Smyrna ditto 1.2743 Galbanum 1.2120 Assafoetida 1.3275 Sarcocolla 1.2684 Opoponax 1.6226 Cherry tree gum 1.4817 Gum Arabic 1.4523 Tragacanth 1.3161 Basora gum 1.4346 Acajou gum(E) 1.4456 Monbain gum(F) 1.4206 Inspissated juice of liquorice 1.7228 ---- Acacia 1.5153 ---- Areca 1.4573 Terra Japonica 1.3980 Hepatic aloes 1.3586 Socotrine aloes 1.3795 Inspissated juice of St John's wort 1.5263 Opium 1.3366 Indigo .7690 Arnotto .5956 Yellow wax .9648 White ditto .9686 Ouarouchi ditto(G) .8970 Cacao butter .8916 Spermaceti .9433 Beef fat .9232 Veal fat .9342 Mutton fat .9235 Tallow .9419 Hoggs fat .9368 Lard .9478 Butter .9423 [Note A: Resinous juices extracted in France from the Pine. _Vide Bomare's Dict._] [Note B: Odoriferous gum from the tree which produces the Cortex Winteranus. _Bomare._] [Note C: Resin of the tree called in Mexico Caragna, or Tree of Madness. _Ibid._] [Note D: Extracted in Persia and the warm countries from Hedera terrestris.--_Bomare._] [Note E: From a Brasilian tree of this name.--_Ibid._] [Note F: From a tree of this name.--_Ibid._] [Note G: The produce of the Tallow Tree of Guayana. _Vide Bomare's Dict._] § 7. _Woods._ Heart of oak 60 years old 1.1700 Cork .2400 Elm trunk .6710 Ash ditto .8450 Beech .8520 Alder .8000 Maple .7550 Walnut .6710 Willow .5850 Linden .6040 Male fir .5500 Female ditto .4980 Poplar .3830 White Spanish ditto .5294 Apple tree .7930 Pear tree .6610 Quince tree .7050 Medlar .9440 Plumb tree .7850 Olive wood .9270 Cherry tree .7150 Filbert tree .6000 French box .9120 Dutch ditto 1.3280 Dutch yew .7880 Spanish ditto .8070 Spanish cypress .6440 American cedar .5608 Pomgranate tree 1.3540 Spanish mulberry tree .8970 Lignum vitae 1.3330 Orange tree .7050 _Note_--The numbers in the above Table, if the Decimal point be carried three figures farther to the right hand, nearly express the absolute weight of an English cube foot of each substance in averdupois ounces. See No. VIII. of the Appendix.--E. No. VIII. ADDITIONAL. RULES _for Calculating the Absolute Gravity in English Troy Weight of a Cubic Foot and Inch, English Measure, of any Substance whose Specific Gravity is known[64]._ In 1696, Mr Everard, balance-maker to the Exchequer, weighed before the Commissioners of the House of Commons 2145.6 cubical inches, by the Exchequer standard foot, of distilled water, at the temperature of 55° of Fahrenheit, and found it to weigh 1131 oz. 14 dts. Troy, of the Exchequer standard. The beam turned with 6 grs. when loaded with 30 pounds in each scale. Hence, supposing the pound averdupois to weigh 7000 grs. Troy, a cubic foot of water weighs 62-1/2 pounds averdupois, or 1000 ounces averdupois, wanting 106 grains Troy. And hence, if the specific gravity of water be called 1000, the proportional specific gravities of all other bodies will nearly express the number of averdupois ounces in a cubic foot. Or more accurately, supposing the specific gravity of water expressed by 1. and of all other bodies in proportional numbers, as the cubic foot of water weighs, at the above temperature, exactly 437489.4 grains Troy, and the cubic inch of water 253.175 grains, the absolute weight of a cubical foot or inch of any body in Troy grains may be found by multiplying their specific gravity by either of the above numbers respectively. By Everard's experiment, and the proportions of the English and French foot, as established by the Royal Society and French Academy of Sciences, the following numbers are ascertained. Paris grains in a Paris cube foot of water = 645511 English grains in a Paris cube foot of water = 529922 Paris grains in an English cube foot of water = 533247 English grains in an English cube foot of water = 437489.4 English grains in an English cube inch of water = 253.175 By an experiment of Picard with the measure and weight of the Chatelet, the Paris cube foot of water contains of Paris grains = 641326 By one of Du Hamel, made with great care = 641376 By Homberg = 641666 These show some uncertainty in measures or in weights; but the above computation from Everard's experiment may be relied on, because the comparison of the foot of England with that of France was made by the joint labours of the Royal Society of London and the French Academy of Sciences: It agrees likewise very nearly with the weight assigned by Mr Lavoisier, 70 Paris pounds to the cubical foot of water. No. IX. TABLES _for Converting Ounces, Drams, and Grains, Troy, into Decimals of the Troy Pound of 12 Ounces, and for Converting Decimals of the Pound Troy into Ounces, &c._ I. _For Grains._ Grains = Pound. 1 .0001736 2 .0003472 3 .0005208 4 .0006944 5 .0008681 6 .0010417 7 .0012153 8 .0013889 9 .0015625 10 .0017361 20 .0034722 30 .0052083 40 .0069444 50 .0086806 60 .0104167 70 .0121528 80 .0138889 90 .0156250 100 .0173611 200 .0374222 300 .0520833 400 .0694444 500 .0868055 600 .1041666 700 .1215277 800 .1388888 900 .1562499 1000 .1736110 2000 .3472220 3000 .5208330 4000 .6944440 5000 .8680550 6000 1.0418660 7000 1.2152770 8000 1.3888880 9000 1.5624990 II. _For Drams._ Drams = Pound. 1 .0104167 2 .0208333 3 .0312500 4 .0416667 5 .0520833 6 .0625000 7 .0729167 8 .0833333 III. _For Ounces._ Ounces = Pounds. 1 .0833333 2 .1666667 3 .2500000 4 .3333333 5 .4166667 6 .5000000 7 .5833333 8 .6666667 9 .7500000 10 .8333333 11 .9166667 12 1.0000000 IV. _Decimals of the Pound into Ounces, &c._ _Tenth parts._ lib. = oz. dr. gr. 0.1 1 1 36 0.2 2 3 12 0.3 3 4 48 0.4 4 6 24 0.5 6 0 0 0.6 7 1 36 0.7 8 3 12 0.8 9 4 48 0.9 10 6 24 _Hundredth parts._ 0.01 0 0 57.6 0.02 0 1 55.2 0.03 0 2 52.8 0.04 0 3 50.4 0.05 0 4 48.0 0.06 0 5 45.6 0.07 0 6 43.2 0.08 0 7 40.8 0.09 0 3 38.4 _Thousandths._ 0.001 0 0 5.76 0.002 0 0 11.52 0.003 0 0 17.28 0.004 0 0 23.04 0.005 0 0 28.80 lib. = grs. 0.006 34.56 0.007 40.32 0.008 46.08 0.009 51.84 _Ten thousandth parts._ 0.0001 0.576 0.0002 1.152 0.0003 1.728 0.0004 2.304 0.0005 2.880 0.0006 3.456 0.0007 4.032 0.0008 4.608 0.0009 5.184 _Hundred thousandth parts._ 0.00001 0.052 0.00002 0.115 0.00003 0.173 0.00004 0.230 0.00005 0.288 0.00006 0.346 0.00007 0.403 0.00008 0.461 0.00009 0.518 No. X. TABLE _of the English Cubical Inches and Decimals corresponding to a determinate Troy Weight of Distilled Water at the Temperature of 55°, calculated from Everard's experiment._ _For Grains._ Grs. Cubical inches. 1 = .0039 2 .0078 3 .0118 4 .0157 5 .0197 6 .0236 7 .0275 8 .0315 9 .0354 10 .0394 20 .0788 30 .1182 40 .1577 50 .1971 _For Drams._ Drams. Cubical inches. 1 = .2365 2 .4731 3 .7094 4 .9463 5 1.1829 6 1.4195 7 1.6561 _For Ounces._ Oz. Cubical inches. 1 = 1.8927 2 3.7855 3 5.6782 4 7.5710 5 9.4631 6 11.3565 7 13.2493 8 15.1420 9 17.0748 10 18.9276 11 20.8204 _For Pounds._ Libs. Cubical inches. 1 = 22.7131 2 45.4263 3 68.1394 4 90.8525 5 113.5657 6 136.2788 7 158.9919 8 181.7051 9 204.4183 10 227.1314 50 1135.6574 100 2271.3148 1000 22713.1488 FOOTNOTES: [62] For the materials of this Article the Translator is indebted to Professor Robertson. [63] It is said, _Belidor Archit. Hydrog._ to contain 31 oz. 64 grs. of water, which makes it 58.075 English inches; but, as there is considerable uncertainty in the determinations of the weight of the French cubical measure of water, owing to the uncertainty of the standards made use of, it is better to abide by Mr Everard's measure, which was with the Exchequer standards, and by the proportions of the English and French foot, as established by the French Academy and Royal Society. [64] The whole of this and the following article was communicated to the Translator by Professor Robinson.--E. _THE PLATES_ [Illustration: _Plate I_] [Illustration: _Plate I (continued)_] [Illustration: _Plate II_] [Illustration: _Plate II (continued)_] [Illustration: _Plate III_] [Illustration: _Plate III (continued)_] [Illustration: _Plate IV_] [Illustration: _Plate IV (continued)_] [Illustration: _Plate V_] [Illustration: _Plate V (continued)_] [Illustration: _Plate VI_] [Illustration: _Plate VI (continued)_] [Illustration: _Plate VII_] [Illustration: _Plate VII (continued)_] [Illustration: _Plate VIII_] [Illustration: _Plate VIII (continued)_] [Illustration: _Plate IX_] [Illustration: _Plate IX (continued)_] [Illustration: _Plate X_] [Illustration: _Plate X (continued)_] [Illustration: _Plate XI_] [Illustration: _Plate XI (continued)_] [Illustration: _Plate XII_] [Illustration: _Plate XII (continued)_] [Illustration: _Plate XII (continued)_] [Illustration: _Plate XII (continued)_] [Illustration: _Plate XII (continued)_] [Illustration: _Plate XIII_] [Illustration: _Plate XIII (continued)_] THE END. 
34457	----	Note: Project Gutenberg also has an HTML version of this file which includes the original illustrations. See 34457-h.htm or 34457-h.zip: (http://www.gutenberg.org/files/34457/34457-h/34457-h.htm) or (http://www.gutenberg.org/files/34457/34457-h.zip) Transcriber's note: Page numbers enclosed by curly braces (example: {25}) have been incorporated to facilitate the use of the Table of Contents. In chemical formulas an underscore is used to indicate that the following number enclosed by curly braces is a subscript. For example, the formula of water is indicated by H_{2}O. A carat character followed by a number enclosed by curly braces indicate an exponent. For example, ten raised to the minus 7th power is indicated by 10^{-7}. A few typographical errors have been corrected and are listed at the end of the text. THE PHASE RULE AND ITS APPLICATIONS by ALEX. FINDLAY, M.A., PH.D., D.SC. * * * * * TEXT-BOOKS OF PHYSICAL CHEMISTRY. EDITED BY SIR WILLIAM RAMSAY, K.C.B., F.R.S., D.SC. * * * * * STOICHIOMETRY. By SYDNEY YOUNG, D.Sc., F.R.S., Professor of Chemistry in the University of Dublin; together with an INTRODUCTION TO THE STUDY OF PHYSICAL CHEMISTRY by Sir WILLIAM RAMSAY, K.C.B., F.R.S., Editor of the Series. Crown 8vo. 7s. 6d. AN INTRODUCTION TO THE STUDY OF PHYSICAL CHEMISTRY. Being a General Introduction to the Series by Sir WILLIAM RAMSAY, K.C.B., F.R.S., D.Sc. Crown 8vo. 1s. net. CHEMICAL STATICS AND DYNAMICS, including THE THEORIES OF CHEMICAL CHANGE, CATALYSIS AND EXPLOSIONS. BY J. W. MELLOR, D.Sc. (N.Z.), B.Sc. (Vict.) Crown 8vo. 7s. 6d. THE PHASE RULE AND ITS APPLICATIONS. By ALEX. FINDLAY, M.A., Ph.D., D.Sc., Lecturer and Demonstrator in Chemistry, University of Birmingham. With 134 Figures in the Text. Crown 8vo. 5s. SPECTROSCOPY. By E. C. C. BALY, F.I.C., Lecturer on Spectroscopy and Assistant Professor of Chemistry, University College, London. With 163 Illustrations. Crown 8vo. 10s. 6d. THERMOCHEMISTRY. By JULIUS THOMSEN, Emeritus Professor of Chemistry in the University of Copenhagen. Translated by KATHARINE A. BURKE, B.Sc. (Lond.), Assistant in the Department of Chemistry, University College, London. Crown 8vo. 9s. ELECTRO-CHEMISTRY. PART I.--GENERAL THEORY. By R. A. LEHFELDT, D.Sc., Professor of Physics at the East London Technical College. Including a Chapter on the Relation of Chemical Constitution to Conductivity, by T. S. MOORE, B.A., B.Sc., Lecturer in the University of Birmingham. Crown 8vo. 5s. PART II.--APPLICATIONS TO ELECTROLYSIS, PRIMARY AND SECONDARY BATTERIES, etc. By N. T. M. WILSMORE, D.Sc. [_In the press._ STEREOCHEMISTRY. By A. W. STEWART, D.Sc., Carnegie Research Fellow, Lecturer on Stereochemistry in University College, London. With 87 Illustrations. Crown 8vo. 10s. 6d. RELATIONS BETWEEN CHEMICAL CONSTITUTION AND PHYSICAL PROPERTIES. By SAMUEL SMILES, D.Sc. [_In preparation._ THERMODYNAMICS. By F. G. DONNAN, M.A., Ph.D. [_In preparation._ ACTINOCHEMISTRY. By C. E. K. MEES, D.Sc., and S. E. SHEPPARD, D.Sc. [_In preparation._ PRACTICAL SPECTROGRAPHIC ANALYSIS. By J. H. POLLOK, D.Sc. [_In preparation._ LONGMANS, GREEN, AND CO. 39 PATERNOSTER ROW, LONDON NEW YORK, BOMBAY, AND CALCUTTA * * * * * THE PHASE RULE AND ITS APPLICATIONS BY ALEX. FINDLAY, M.A., PH.D., D.SC. Lecturer on Physical Chemistry, University of Birmingham With One Hundred and Thirty-Four Figures in the Text Third Impression Longmans, Green, and Co. 39 Paternoster Row, London New York, Bombay, and Calcutta 1908 All rights reserved DEDICATED TO FRANCIS ROBERT JAPP, LL.D., F.R.S. PROFESSOR OF CHEMISTRY, UNIVERSITY OF ABERDEEN, IN GRATITUDE FOR EARLY TRAINING AND ADVICE {vii} PREFACE TO THE SECOND EDITION. During the two years which have elapsed since the first edition of this book appeared, the study of chemical equilibria has been prosecuted with considerable activity, and valuable additions have been made to our knowledge in several departments of this subject. In view of the scope of the present work, it has been, of course, impossible to incorporate all that has been done; but several new sections have been inserted, notably those on the study of basic salts; the interpretation of cooling curves, and the determination of the composition of solid phases without analysis; the equilibria between iron, carbon monoxide, and carbon dioxide, which are of importance in connection with the processes occurring in the blast furnace; and the Phase Rule study of the ammonia-soda process. I have also incorporated a short section on the reciprocal salt-pair barium carbonate--potassium sulphate, which had been written for the German edition of this book by the late Professor W. Meyerhoffer. The section on the iron-carbon alloys, which in the first edition was somewhat unsatisfactory, has been rewritten. A. F. _September, 1906._ {viii} PREFACE Although we are indebted to the late Professor Willard Gibbs for the first enunciation of the Phase Rule, it was not till 1887 that its practical applicability to the study of Chemical Equilibria was made apparent. In that year Roozeboom disclosed the great generalization, which for upwards of ten years had remained hidden and unknown save to a very few, by stripping from it the garb of abstract Mathematics in which it had been clothed by its first discoverer. The Phase Rule was thus made generally accessible; and its adoption by Roozeboom as the basis of classification of the different cases of chemical equilibrium then known established its value, not only as a means of co-ordinating the large number of isolated cases of equilibrium and of giving a deeper insight into the relationships existing between the different systems, but also as a guide in the investigation of unknown systems. While the revelation of the principle embedded in the Phase Rule is primarily due to Roozeboom, it should not be forgotten that, some years previously, van't Hoff, in ignorance of the work of Willard Gibbs, had enunciated his "law of the incompatibility of condensed systems," which in some respects coincides with the Phase Rule; and it is only owing to the more general applicability of the latter that the very {ix} important generalization of van't Hoff has been somewhat lost sight of. The exposition of the Phase Rule and its applications given in the following pages has been made entirely non-mathematical, the desire having been to explain as clearly as possible the principles underlying the Phase Rule, and to illustrate their application to the classification and investigation of equilibria, by means of a number of cases actually studied. While it has been sought to make the treatment sufficiently elementary to be understood by the student just commencing the study of chemical equilibria, an attempt has been made to advance his knowledge to such a stage as to enable him to study with profit the larger works on the subject, and to follow with intelligence the course of investigation in this department of Physical Chemistry. It is also hoped that the volume may be of use, not only to the student of Physical Chemistry, or of the other branches of that science, but also to the student of Metallurgy and of Geology, for whom an acquaintance with at least the principles of the Phase Rule is becoming increasingly important. In writing the following account of the Phase Rule, it is scarcely necessary to say that I have been greatly indebted to the larger works on Chemical Equilibria by Ostwald ("Lehrbuch"), Roozeboom ("Die Heterogenen Gleichgewichte"), and Bancroft ("The Phase Rule"); and in the case of the first-named, to the inspiration also of personal teaching. My indebtedness to these and other authors I have indicated in the following pages. In conclusion, I would express my thanks to Sir William Ramsay, whose guidance and counsel have been constantly {x} at my disposal; and to my colleagues, Dr. T. Slater Price and Dr. A. McKenzie, for their friendly criticism and advice. To Messrs. J. N. Friend, M.Sc., and W. E. S. Turner, B.Sc., I am also indebted for their assistance in reading the proof-sheets. A. F. _November, 1903._ {xi} CONTENTS PAGE CHAPTER I INTRODUCTION 1 General, I. Homogeneous and heterogeneous equilibrium, 5. Real and apparent equilibrium, 5. CHAPTER II THE PHASE RULE 7 Phases, 8. Components, 10. Degree of freedom. Variability of a system, 14. The Phase Rule, 16. Classification of systems according to the Phase Rule, 17. Deduction of the Phase Rule, 18. CHAPTER III TYPICAL SYSTEMS OF ONE COMPONENT 21 A. _Water._ Equilibrium between liquid and vapour. Vaporization curve, 21. Upper limit of vaporization curve, 23. Sublimation curve of ice, 24. Equilibrium between ice and water. Curve of fusion, 25. Equilibrium between ice, water, and vapour. The triple point, 27. Bivariant systems of water, 29. Supercooled water. Metastable state, 30. Other systems of the substance water, 32. B. _Sulphur_, 33. Polymorphism, 33. Sulphur, 34. Triple point--Rhombic and monoclinic sulphur and vapour. Transition point, 34. Condensed systems, 36. Suspended transformation, 37. Transition curve--Rhombic and monoclinic sulphur, 37. Triple point--Monoclinic sulphur, liquid, and vapour. Melting point of monoclinic sulphur, 38. Triple point--Rhombic and monoclinic sulphur and liquid, 38. Triple point--Rhombic sulphur, liquid, and vapour. Metastable triple point, 38. Fusion curve of rhombic sulphur, 39. Bivariant systems, 39. C. _Tin_, 41. Transition point, 41. {xii} Enantiotropy and monotropy, 44. D. _Phosphorus_, 46. Enantiotropy combined with monotropy, 51. E. _Liquid Crystals_, 51. Phenomena observed, 51. Nature of liquid crystals, 52. Equilibrium relations in the case of liquid crystals, 53. CHAPTER IV GENERAL SUMMARY 55 Triple point, 55. Theorems of van't Hoff and of Le Chatelier, 57. Changes at the triple point, 58. Triple point solid--solid--vapour, 62. Sublimation and vaporization curves, 63. Fusion curve--Transition curve, 66. Suspended transformation. Metastable equilibria, 69. Velocity of transformation, 70. Law of successive reactions, 73. CHAPTER V SYSTEMS OF TWO COMPONENTS--PHENOMENA OF DISSOCIATION 76 Different systems of two components, 77. PHENOMENA OF DISSOCIATION. Bivariant systems, 79. Univariant systems, 80. Ammonia compounds of metal chlorides, 82. Salts with water of crystallization, 85. Efflorescence, 86. Indefiniteness of the vapour pressure of a hydrate, 87. Suspended transformation, 89. Range of existence of hydrates, 90. Constancy of vapour pressure and the formation of compounds, 90. Measurement of the vapour pressure of hydrates, 91. CHAPTER VI SOLUTIONS 92 Definition, 92. SOLUTIONS OF GASES IN LIQUIDS, 93. SOLUTIONS OF LIQUIDS IN LIQUIDS, 95. Partial or limited miscibility, 96. Phenol and water, 97. Methylethylketone and water, 100. Triethylamine and water, 101. General form of concentration-temperature curve, 101. Pressure-concentration diagram, 102. Complete miscibility, 104. Pressure-concentration diagram, 104. CHAPTER VII SOLUTIONS OF SOLIDS IN LIQUIDS, ONLY ONE OF THE COMPONENTS BEING VOLATILE 106 General, 106. The saturated solution, 108. Form of the solubility curve, 108. A. ANHYDROUS SALT AND WATER. {xiii} The solubility curve, 111. Suspended transformation and supersaturation, 113. Solubility curve at higher temperatures, 114. (1) _Complete miscibility of the fused components._ Ice as solid phase, 116. Cryohydrates, 117. Changes at the quadruple point, 119. Freezing mixtures, 120. (2) _Partial miscibility of the fused components._ Supersaturation, 124. Pressure-temperature diagram, 126. Vapour pressure of solid--solution--vapour, 126. Other univariant systems, 127. Bivariant systems, 129. Deliquescence, 130. Separation of salt on evaporation, 130. General summary, 131. CHAPTER VIII SOLUTIONS OF SOLIDS IN LIQUIDS, ONLY ONE OF THE COMPONENTS BEING VOLATILE 133 B. HYDRATED SALT AND WATER, (1) _The compounds formed do not have a definite melting point._ Concentration-temperature diagram, 133. Sodium sulphate and water, 134. Suspended transformation, 137. Dehydration by means of anhydrous sodium sulphate, 138. Pressure-temperature diagram, 138. (2) _The compounds formed have a definite melting point._ Solubility curve of calcium chloride hexahydrate, 145. Pressure-temperature diagram, 149. The indifferent point, 150. The hydrates of ferric chloride, 151. Suspended transformation, 155. Evaporation of solutions at constant temperature, 155. Inevaporable solutions, 157. Illustration, 158. CHAPTER IX EQUILIBRIA BETWEEN TWO VOLATILE COMPONENTS 161 General, 161. Iodine and chlorine, 161. Concentration-temperature diagram, 162. Pressure-temperature diagram, 165. Bivariant systems, 167. Sulphur dioxide and water, 169. Pressure-temperature diagram, 170. Bivariant systems, 173. CHAPTER X SOLID SOLUTIONS. MIXED CRYSTALS 175 General, 175. Solution of gases in solids, 176. Palladium and hydrogen, 178. Solutions of solids in solids. Mixed crystals, 180. Formation of mixed crystals of isomorphous substances, 182. I. The two components can form an unbroken series of mixed crystals. (_a_) _The freezing points of all mixtures lie between the freezing points of the pure components._ Examples, 183. Melting-point curve, 183. (_b_) _The freezing-point curve passes through a maximum._ Example, 186. (_c_) _The freezing-point curve passes through a minimum._ Example, 188. Fractional {xiv} crystallization of mixed crystals, 188. II. The two components do not form a continuous series of mixed crystals. (_a_) _The freezing-point curve exhibits a transition point_, 190. Example, 190. (_b_) _The freezing-point curve exhibits a eutectic point_, 191. Examples, 192. Changes in mixed crystals with the temperature, 192. CHAPTER XI EQUILIBRIUM BETWEEN DYNAMIC ISOMERIDES 195 Temperature-concentration diagram, 196. Transformation of the unstable into the stable form, 201. Examples, 203. _Benzaldoximes_, 203. _Acetaldehyde and paraldehyde_, 204. CHAPTER XII SUMMARY.--APPLICATION OF THE PHASE RULE TO THE STUDY OF SYSTEMS OF TWO COMPONENTS 207 Summary of the different systems of two components, 208. (1) _Organic compounds_, 212. (2) _Optically active substances_, 213. Examples, 216. Transformations, 217. (3) _Alloys_, 220. Iron--carbon alloys, 223. Determination of the composition of compounds without analysis, 228. Formation of minerals, 232. CHAPTER XIII SYSTEMS OF THREE COMPONENTS 234 General, 234. Graphic representation, 235. CHAPTER XIV SOLUTIONS OF LIQUIDS IN LIQUIDS 240 1. _The three components form only one pair of partially miscible liquids_, 240. Retrograde solubility, 245. The influence of temperature, 247. 2. _The three components can form two pairs of partially miscible liquids_, 249. 3. _The three components form three pairs of partially miscible liquids_, 251. CHAPTER XV PRESENCE OF SOLID PHASES 253 A. The ternary eutectic point, 253. Formation of compounds, 255. B. Equilibria at higher temperatures. Formation of double salts, 258. Transition point, 258. Vapour pressure. {xv} Quintuple point, 261. Solubility curves at the transition point, 264. Decomposition of the double salt by water, 267. Transition interval, 270. Summary, 271. CHAPTER XVI ISOTHERMAL CURVES AND THE SPACE MODEL 272 Non-formation of double salts, 272. Formation of double salt, 273. Transition interval, 277. Isothermal evaporation, 278. Crystallization of double salt from solutions containing excess of one component, 280. Formation of mixed crystals, 281. Application to the characterization of racemates, 282. _Representation in space._ Space model for carnallite, 284. Summary and numerical data, 287. Ferric chloride--hydrogen chloride--water, 290. Ternary systems, 291. The isothermal curves, 294. Basic Salts, 296. Bi_{2}O_{3}--N_{2}O_{5}--H_{2}O, 298. Basic mercury salts, 301. Indirect determination of the composition of the solid phase, 302. CHAPTER XVII ABSENCE OF LIQUID PHASE 305 Iron, carbon monoxide, carbon dioxide, 305. CHAPTER XVIII SYSTEMS OF FOUR COMPONENTS 312 Reciprocal salt-pairs. Choice of components, 313. Transition point, 314. Formation of double salts, 315. Transition interval, 315. Graphic representation, 316. Example, 317. Ammonia-soda process, 320. Preparation of barium nitrite, 327. Barium carbonate and potassium sulphate, 328. APPENDIX EXPERIMENTAL DETERMINATION OF THE TRANSITION POINT 331 I. The dilatometric method, 331. II. Measurement of the vapour pressure, 334. III. Solubility measurements, 335. IV. Thermometric method, 337. V. Optical method, 338. VI. Electrical methods, 338. NAME INDEX 341 SUBJECT INDEX 345 * * * * * {1} THE PHASE RULE CHAPTER I INTRODUCTION General.--Before proceeding to the more systematic treatment of the Phase Rule, it may, perhaps, be not amiss to give first a brief forecast of the nature of the subject we are about to study, in order that we may gain some idea of what the Phase Rule is, of the kind of problem which it enables us to solve, and of the scope of its application. It has long been known that if water is placed in a closed, exhausted space, vapour is given off and a certain pressure is created in the enclosing vessel. Thus, when water is placed in the Torricellian vacuum of the barometer, the mercury is depressed, and the amount of depression increases as the temperature is raised. But, although the pressure of the vapour increases as the temperature rises, its value at any given temperature is constant, no matter whether the amount of water present or the volume of the vapour is great or small; if the pressure on the vapour is altered while the temperature is maintained constant, either the water or the vapour will ultimately disappear; the former by evaporation, the latter by condensation. At any given temperature within certain limits, therefore, water and vapour can exist permanently in contact with one another--or, as it is said, be in equilibrium with one another--only when the pressure has a certain definite value. The same law of constancy of vapour pressure at a given {2} temperature, quite irrespective of the volumes of liquid and vapour,[1] holds good also in the case of alcohol, ether, benzene, and other pure liquids. It is, therefore, not unnatural to ask the question, Does it hold good for all liquids? Is it valid, for example, in the case of solutions? We can find the answer to these questions by studying the behaviour of a solution--say, a solution of common salt in water--when placed in the Torricellian vacuum. In this case, also, it is observed that the pressure of the vapour increases as the temperature is raised, but the pressure is no longer independent of the volume; as the volume increases, the pressure slowly diminishes. If, however, solid salt is present in contact with the solution, then the pressure again becomes constant at constant temperature, even when the volume of the vapour is altered. As we see, therefore, solutions do not behave in the same way as pure liquids. Moreover, on lowering the temperature of water, a point is reached at which ice begins to separate out; and if heat be now added to the system or withdrawn from it, no change will take place in the temperature or vapour pressure of the latter until either the ice or the water has disappeared.[2] Ice, water, and vapour, therefore, can be in equilibrium with one another only at one definite temperature and one definite pressure. In the case of a solution of common salt, however, we may have ice in contact with the solution at different temperatures and pressures. Further, it is possible to have a solution in equilibrium not only with anhydrous salt (NaCl), but also with the hydrated salt (NaCl, 2H_{2}O), as well as with ice, and the question, therefore, arises: Is it possible to state in a general manner the conditions under which such different systems can exist in equilibrium; or to obtain some insight {3} into the relations which exist between pure liquids and solutions? As we shall learn, the Phase Rule enables us to give an answer to this question. The preceding examples belong to the class of so-called "physical" equilibria, or equilibria depending on changes in the physical state. More than a hundred years ago, however, it was shown by Wenzel and Berthollet that "chemical" equilibria can also exist; that chemical reactions do not always take place completely in one direction as indicated by the usual chemical equation, but that before the reacting substances are all used up the reaction ceases, and there is a condition of equilibrium between the reacting substances and the products of reaction. As an example of this, there may be taken the process of lime-burning, which depends on the fact that when calcium carbonate is heated, carbon dioxide is given off and quicklime is produced. If the carbonate is heated in a closed vessel it will be found, however, not to undergo entire decomposition. When the pressure of the carbon dioxide reaches a certain value (which is found to depend on the temperature), decomposition ceases, and calcium carbonate exists side by side with calcium oxide and carbon dioxide. Moreover, at any given temperature the pressure is constant and independent of the amount of carbonate or oxide present, or of the volume of the gas; _nor does the addition of either of the products of dissociation, carbon dioxide or calcium oxide, cause any change in the equilibrium_. Here, then, we see that, although there are three different substances present, and although the equilibrium is no longer due to physical, but to chemical change, it nevertheless obeys the same law as the vapour pressure of a pure volatile liquid, such as water. It might be supposed, now, that this behaviour would be shown by other dissociating substances, _e.g._ ammonium chloride. When this substance is heated it dissociates into ammonia and hydrogen chloride, and at any given temperature the pressure of these gases is constant,[3] and is independent of the amounts of solid and gas present. So far, therefore, ammonium chloride behaves like calcium carbonate. If, however, one of the {4} products of dissociation be added to the system, it is found that the pressure is no longer constant at a given temperature, but varies with the amount of gas, ammonia or hydrogen chloride, which is added. In the case of certain dissociating substances, therefore, addition of one of the products of dissociation alters the equilibrium, while in other cases it does not. With the help of the Phase Rule, however, a general interpretation of this difference of behaviour can be given--an interpretation which can be applied not only to the two cases cited, but to all cases of dissociation. Again, it is well known that sulphur exists in two different crystalline forms, octahedral and prismatic, each of which melts at a different temperature. The problem here is, therefore, more complicated than in the case of ice, for there is now a possibility not only of one solid form, but of two different forms of the same substance existing in contact with liquid. What are the conditions under which these two forms can exist in contact with liquid, either singly or together, and under what conditions can the two solid forms exist together without the presence of liquid sulphur? To these questions an answer can also be given with the help of the Phase Rule. These cases are, however, comparatively simple; but when we come, for instance, to study the conditions under which solutions are formed, and especially when we inquire into the solubility relations of salts capable of forming, perhaps, a series of crystalline hydrates; and when we seek to determine the conditions under which these different forms can exist in contact with the solution, the problem becomes more complicated, and the necessity of some general guide to the elucidation of the behaviour of these different systems becomes more urgent. It is, now, to the study of such physical and chemical equilibria as those above-mentioned that the Phase Rule finds application; to the study, also, of the conditions regulating, for example, the formation of alloys from mixtures of the fused metals, or of the various salts of the Stassfurt deposits; the behaviour of iron and carbon in the formation of steel and the {5} separation of different minerals from a fused rock-mass.[4] With the help of the Phase Rule we can group together into classes the large number of different isolated cases of systems in equilibrium; with its aid we are able to state, in a general manner at least, the conditions under which a system can be in equilibrium, and by its means we can gain some insight into the relations existing between different kinds of systems. Homogeneous and Heterogeneous Equilibrium.--Before passing to the consideration of this generalization, it will be well to first make mention of certain restrictions which must be placed on its treatment, and also of the limitations to which it is subject. If a system is uniform throughout its whole extent, and possesses in every part identical physical properties and chemical composition, it is called _homogeneous_. Such is, for example, a solution of sodium chloride in water. An equilibrium occurring in such a homogeneous system (such as the equilibrium occurring in the formation of an ester in alcoholic solution) is called _homogeneous equilibrium_. If, however, the system consists of parts which have different physical properties, perhaps also different chemical properties, and which are marked off and separated from one another by bounding surfaces, the system is said to be _heterogeneous_. Such a system is formed by ice, water, and vapour, in which the three portions, each in itself homogeneous, can be mechanically separated from one another. When equilibrium exists between different, physically distinct parts, it is known as _heterogeneous equilibrium_. It is, now, with heterogeneous equilibria, with the conditions under which a heterogeneous system can exist, that we shall deal here. Further, we shall not take into account changes of equilibrium due to the action of electrical, magnetic, or capillary forces, or of gravity; but shall discuss only those which are due to changes of pressure, temperature, and volume (or concentration). Real and Apparent Equilibrium.--In discussing equilibria, also, a distinction must be drawn between real and {6} apparent equilibria. In the former case there is a state of rest which undergoes continuous change with change of the conditions (_e.g._ change of temperature or of pressure), and for which the chief criterion is that _the same condition of equilibrium is reached from whichever side it is approached_. Thus in the case of a solution, if the temperature is maintained constant, the same concentration will be obtained, no matter whether we start with an unsaturated solution to which we add more solid, or with a supersaturated solution from which we allow solid to crystallize out; or, in the case of water in contact with vapour, the same vapour pressure will be obtained, no matter whether we heat the water up to the given temperature or cool it down from a higher temperature. In this case, water and vapour are in _real_ equilibrium. On the other hand, water in contact with hydrogen and oxygen at the ordinary temperature is a case only of _apparent_ equilibrium; on changing the pressure and temperature continuously within certain limits there is no continuous change observed in the relative amounts of the two gases. On heating beyond these limits there is a sudden and not a continuous change, and the system no longer regains its former condition on being cooled to the ordinary temperature. In all such cases the system may be regarded as undergoing change and as tending towards a state of true or real equilibrium, but with such slowness that no change is observed. Although the case of water in contact with hydrogen and oxygen is an extreme one, it must be borne in mind that the condition of true equilibrium may not be reached instantaneously or even with measurable velocity, and in all cases it is necessary to be on one's guard against mistaking apparent (or false) for real (or true) equilibrium. The importance of this will be fully illustrated in the sequel. * * * * * {7} CHAPTER II THE PHASE RULE Although the fact that chemical reactions do not take place completely in one direction, but proceed only to a certain point and there make a halt, was known in the last quarter of the eighteenth century (Wenzel, 1777; Berthollet, 1799); and although the opening and subsequent decades of the following century brought many further examples of such equilibria to our knowledge, it was not until the last quarter of the nineteenth century that a theorem, general in its application and with foundations weakened by no hypothetical assumptions as to the nature or constitution of matter, was put forward by Willard Gibbs;[5] a generalization which serves at once as a golden rule by which the condition of equilibrium of a system can be tested, and as a guide to the similarities and dissimilarities existing in different systems. Before that time, certainly, attempts had been made to bring the different known cases of equilibria--chemical and physical--under general laws. From the very first, both Wenzel[6] and Berthollet[7] recognized the influence exercised by the _mass_ of the substances on the equilibrium of the system. It was reserved, however, for Guldberg and Waage, by their more general statement and mathematical treatment of the Law of Mass Action,[8] to inaugurate the period of quantitative study of equilibria. The law which these investigators enunciated {8} served satisfactorily to summarize the conditions of equilibrium in many cases both of homogeneous and, with the help of certain assumptions and additions, of heterogeneous equilibrium. By reason, however, of the fact that it was developed on the basis of the kinetic and molecular theories, and involved, therefore, certain hypothetical assumptions as to the nature and condition of the substances taking part in the equilibrium, the law of mass action failed, as it necessarily must, when applied to those systems in which neither the number of different molecular aggregates nor the degree of their molecular complexity was known. Ten years after the law of mass action was propounded by Guldberg and Waage, Willard Gibbs,[9] Professor of Physics in Yale University, showed how, in a perfectly general manner, free from all hypothetical assumptions as to the molecular condition of the participating substances, all cases of equilibrium could be surveyed and grouped into classes, and how similarities in the behaviour of apparently different kinds of systems, and differences in apparently similar systems, could be explained. As the basis of his theory of equilibria, Gibbs adopted the laws of thermodynamics,[10] a method of treatment which had first been employed by Horstmann.[11] In deducing the law of equilibrium, Gibbs regarded a system as possessing only three independently variable factors[12]--temperature, pressure, and the concentration of the components of the system--and he enunciated the general theorem now usually known as the _Phase Rule_, by which he defined the conditions of equilibrium as a relationship between the number of what are called the phases and the components of the system. Phases.--Before proceeding farther we shall first consider what exactly is meant by the terms _phase_ and _component_. We have already seen (p. 5) that a heterogeneous system is made {9} up of different portions, each in itself homogeneous, but marked off in space and separated from the other portions by bounding surfaces. These homogeneous, physically distinct and mechanically separable portions are called _phases_. Thus ice, water, and vapour, are three phases of the same chemical substance--water. A phase, however, whilst it must be physically and chemically homogeneous, need not necessarily be chemically simple. Thus, a gaseous mixture or a solution may form a phase; but a heterogeneous mixture of solid substances constitutes as many phases as there are substances present. Thus when calcium carbonate dissociates under the influence of heat, calcium oxide and carbon dioxide are formed. There are then _two_ solid phases present, viz. calcium carbonate and oxide, and one gas phase, carbon dioxide. The _number of phases_ which can exist side by side may vary greatly in different systems. In all cases, however, there can be but one gas or vapour phase on the account of the fact that all gases are miscible with one another in all proportions. In the case of liquid and solid phases the number is indefinite, since the above property does not apply to them. The number of phases which can be formed by any given substance or group of substances also differs greatly, and in general increases with the number of participating substances. Even in the case of a single substance, however, the number may be considerable; in the case of sulphur, for example, at least eight different solid phases are known (_v._ Chap. III.). It is of importance to bear in mind that equilibrium is _independent of the amounts_ of the phases present.[13] Thus it is a familiar fact that the pressure of a vapour in contact with a {10} liquid (_i.e._ the pressure of the saturated vapour) is unaffected by the amounts, whether relative or absolute, of the liquid and vapour; also the amount of a substance dissolved by a liquid is independent of the amount of solid in contact with the solution. It is true that deviations from this general law occur when the amount of liquid or the size of the solid particles is reduced beyond a certain point,[14] owing to the influence of surface energy; but we have already (p. 5) excluded such cases from consideration. Components.--Although the conception of phases is one which is readily understood, somewhat greater difficulty is experienced when we come to consider what is meant by the term _component_; for the components of a system are not synonymous with the chemical elements or compounds present, _i.e._ with the _constituents_ of the system, although both elements and compounds may be components. By the latter term there are meant only those constituents the concentration of which can undergo _independent_ variation in the different phases, and it is only with these that we are concerned here.[15] To understand the meaning of this term we shall consider briefly some cases with which the reader will be familiar, and at the outset it must be emphasized that the Phase Rule is concerned merely with those constituents which take part in the state of real equilibrium (p. 5); for it is only to the final state, not to the processes by which that state is reached, that the Phase Rule applies. Consider now the case of the system water--vapour or ice--water--vapour. The number of constituents taking part in the equilibrium here is only one, viz. the chemical substance, water. Hydrogen and oxygen, the constituents of water, are not to be regarded as components, because, in the first place, they are {11} not present in the system in a state of real equilibrium (p. 6); in the second place, they are combined in definite proportions to form water, and their amounts, therefore, cannot be varied independently. A variation in the amount of hydrogen necessitates a definite variation in the amount of oxygen. In the case, already referred to, in which hydrogen and oxygen are present along with water at the ordinary temperature, we are not dealing with a condition of true equilibrium. If, however, the temperature is raised to a certain point, a state of true equilibrium between hydrogen, oxygen, and water-vapour will be possible. In this case hydrogen and oxygen will be components, because now they do take part in the equilibrium; also, they need no longer be present in definite proportions, but excess of one or the other may be added. Of course, if the restriction be arbitrarily made that the free hydrogen and oxygen shall be present always and only in the proportions in which they are combined to form water, there will be, as before, only one component, water. From this, then, we see that a change in the conditions of the experiment (in the present case a rise of temperature) may necessitate a change in the number of the components. It is, however, only in the case of systems of more than one component that any difficulty will be found; for only in this case will a choice of components be possible. Take, for instance, the dissociation of calcium carbonate into calcium oxide and carbon dioxide. At each temperature, as we have seen, there is a definite state of equilibrium. When equilibrium has been established, there are three different substances present--calcium carbonate, calcium oxide, and carbon dioxide; and these are the constituents of the system between which equilibrium exists. Now, although these constituents take part in the equilibrium, they are not all to be regarded as components, for they are not mutually independent. On the contrary, the different phases are related to one another, and if two of these are taken, the composition of the third is defined by the equation CaCO_{3} = CaO + CO_{2} {12} Now, in deciding the number of components in any given system, not only must the constituents chosen be capable of independent variation, but a further restriction is imposed, and we obtain the following rule: _As the components of a system there are to be chosen the_ smallest number _of independently variable constituents by means of which the composition of each phase participating in the state of equilibrium can be expressed in the form of a chemical equation._ Applying this rule to the case under consideration, we see that of the three constituents present when the system is in a state of equilibrium, only two, as already stated, are independently variable. It will further be seen that in order to express the composition of each phase present, two of these constituents are necessary. The system is, therefore, one of _two components_, or a system of the second order. When, now, we proceed to the actual choice of components, it is evident that any two of the constituents can be selected. Thus, if we choose as components CaCO_{3} and CaO, the composition of each phase can be expressed by the following equations:-- CaCO_{3} = CaCO_{3} + 0CaO CaO = CaO + 0CaCO_{3} CO_{2} = CaCO_{3} - CaO As we see, then, both zero and negative quantities of the components have been introduced; and similar expressions would be obtained if CaCO_{3} and CO_{2} were chosen as components. The matter can, however, be simplified and the use of negative quantities avoided if CaO and CO_{2} are chosen; and it is, therefore, customary to select these as the components. While it is possible in the case of systems of the second order to choose the two components in such a way that the composition of each phase can be expressed by positive quantities of these, such a choice is not always possible when dealing with systems of a higher order (containing three or four components). From the example which has just been discussed, it might {13} appear as if the choice of the components was rather arbitrary. On examining the point, however, it will be seen that the arbitrariness affects only the _nature_, not the _number_, of the components; a choice could be made with respect to which, not to how many, constituents were to be regarded as components. As we shall see presently, however, it is only the number, not the nature of the components that is of importance. After the discussion of the conditions which the substances chosen as components must satisfy, another method may be given by which the number of components present in a system can be determined. Suppose a system consisting of several phases in equilibrium, and the composition of each phase determined by analysis. If each phase present, regarded as a whole, has the same composition, the system contains only one component, or is of the first order. If two phases must be mixed in suitable quantities in order that the composition of a third phase may be obtained, the system is one of two components or of the second order; and if three phases are necessary to give the composition of a fourth coexisting phase, the system is one of three components, or of the third order.[16] Although the examples to be considered in the sequel will afford sufficient illustration of the application of the rules given above, one case may perhaps be discussed to show the application of the method just given for determining the number of components. Consider the system consisting of Glauber's salt in equilibrium with solution and vapour. If these three phases are analyzed, the composition of the solid will be expressed by Na_{2}SO_{4}, 10H_{2}O; that of the solution by Na_{2}SO_{4} + _x_H_{2}O, while the vapour phase will be H_{2}O. The system evidently cannot be a one-component system, for the phases have not all the same composition. By varying the amounts of two phases, however (_e.g._ Na_{2}SO_{4}, 10H_{2}O and H_{2}O), the composition of the third phase--the solution--can be obtained. The system is, therefore, one of _two components_. But sodium sulphate can also exist in the anhydrous form and as the hydrate Na_{2}SO_{4}, 7H_{2}O. In these cases there may {14} be chosen as components Na_{2}SO_{4} and H_{2}O, and Na_{2}SO_{4}, 7H_{2}O and H_{2}O respectively. In both cases, therefore, there are two components. But the two systems (Na_{2}SO_{4}, 10H_{2}O--H_{2}O, and Na_{2}SO_{4}, 7H_{2}O--H_{2}O) can be regarded as special cases of the system Na_{2}SO_{4}--H_{2}O, and these two components will apply to all systems made up of sodium sulphate and water, no matter whether the solid phase is anhydrous salt or one of the hydrates. In all three cases, of course, the _number_ of components is the same; but by choosing Na_{2}SO_{4} and H_{2}O as components, the possible occurrence of negative quantities of components in expressing the composition of the phases is avoided; and, further, these components apply over a much larger range of experimental conditions. Again, therefore, we see that, although the number of the components of a system is definite, a certain amount of liberty is allowed in the choice of the substances; and we also see that the choice will be influenced by the conditions of experiment. Summing up, now, we may say-- (1) The components are to be chosen from among the constituents which are present when the system is in a state of true equilibrium, and which take part in that equilibrium. (2) As components are to be chosen the _smallest number_ of such constituents necessary to express the composition of each phase participating in the equilibrium, zero and negative quantities of the components being permissible. (3) In any given system the _number_ of the components is definite, but may alter with alteration of the conditions of experiment. A certain freedom of choice, however, is allowed in the (qualitative, not quantitative) selection of the components, the choice being influenced by considerations of simplicity, suitability, or generality of application.[17] Degree of Freedom. Variability of a System.--It is well known that in dealing with a certain mass of gas or vapour, _e.g._ water vapour, if only one of the independently variable factors--temperature, pressure, and concentration (or volume)--is fixed, the state of the gas or vapour is undefined; while occupying the same volume (the concentration, therefore, remaining {15} unchanged), the temperature and the pressure may be altered; at a given temperature, a gas can exist under different pressures and occupy different volumes, and under any given pressure the temperature and volume may vary. If, however, two of the factors are arbitrarily fixed, then the third factor can only have a certain definite value; at any given values of temperature and pressure a given mass of gas can occupy only a definite volume. Suppose, however, that the system consists of water in contact with vapour. The condition of the system then becomes perfectly defined on arbitrarily giving one of the variables a certain value. If the temperature is fixed, the pressure under which water and water vapour can coexist is also determined; and conversely, if a definite pressure is chosen, the temperature is also defined. Water and vapour can coexist under a given pressure only at a definite temperature. Finally, let the water and vapour be cooled down until ice begins to separate out. So soon as the third phase, ice, appears, the state of the system as regards temperature and pressure of the vapour is perfectly defined, and none of the variables can be arbitrarily changed without causing the disappearance of one of the phases, ice, water, or vapour. We see, therefore, that in the case of some systems two, in other cases, only one of the independent variables (temperature, pressure, concentration) can be altered without destroying the nature of the system; while in other systems, again, these variables have all fixed and definite values. We shall therefore define the number of degrees of freedom[18] of a system as the _number of the variable factors, temperature, pressure, and concentration of the components, which must be arbitrarily fixed in order that the condition of the system may be perfectly defined_. From what has been said, therefore, we shall describe a gas or vapour as having two degrees of freedom; the system water--vapour as having only one; and the system ice--water--vapour as having no degrees of freedom. We may also speak of the {16} _variability_ or _variance_ of a system, and describe a system as being invariant, univariant, bivariant, multivariant,[19] according as the number of degrees of freedom is nought, one, two, or more than two. A knowledge of its variability is, therefore, of essential importance in studying the condition and behaviour of a system, and it is the great merit of the Phase Rule that _the state of a system is defined entirely by the relation existing between the number of the components and the phases present_, no account being taken of the molecular complexity of the participating substances, nor any assumption made with regard to the constitution of matter. It is, further, as we see, quite immaterial whether we are dealing with "physical" or "chemical" equilibrium; in principle, indeed, no distinction need be drawn between the two classes, although it is nevertheless often convenient to make use of the terms, in spite of a certain amount of indefiniteness which attaches to them--an indefiniteness, indeed, which attaches equally to the terms "physical" and "chemical" process.[20] The Phase Rule.--The Phase Rule of Gibbs, which defines the condition of equilibrium by the relation between the number of coexisting phases and the components, may be stated as follows: A system consisting of n components can exist in _n_ + 2 phases only when the temperature, pressure, and concentration have fixed and definite values; if there are _n_ components in _n_ + 1 phases, equilibrium can exist while one of the factors varies, and if there are only _n_ phases, two of the varying factors may be arbitrarily fixed. This rule, the application of which, it is hoped, will become clear in the sequel, may be very concisely and conveniently summarized in the form of the equation-- P + F = C + 2, or F = C + 2 - P where P denotes the number of the phases, F the degrees of freedom, and C the number of components. From the second form of the equation it can be readily seen that the greater the number of the phases, the fewer are the degrees of freedom. With increase in the number of the phases, therefore, the {17} condition of the system becomes more and more defined, or less and less variable. Classification of Systems according to the Phase Rule.--We have already learned in the introductory chapter that systems which are apparently quite different in character may behave in a very similar manner. Thus it was stated that the laws which govern the equilibrium between water and its vapour are quite analogous to those which are obeyed by the dissociation of calcium carbonate into carbon dioxide and calcium oxide; in each case a certain temperature is associated with a definite pressure, no matter what the relative or absolute amounts of the respective substances are. And other examples were given of systems which were apparently similar in character, but which nevertheless behaved in a different manner. The relations between the various systems, however, become perfectly clear and intelligible in the light of the Phase Rule. In the case first mentioned, that of water in equilibrium with its vapour, we have one component--water--present in two phases, _i.e._ in two physically distinct forms, viz. liquid and vapour. According to the Phase Rule, therefore, since C = 1, and P = 2, the degree of freedom F is equal to 1 + 2 - 2 = 1; the system possesses one degree of freedom, as has already been stated. But in the case of the second system mentioned above there are two components, viz. calcium oxide and carbon dioxide (p. 12), and three phases, viz. two solid phases, CaO and CaCO_{3}, and the gaseous phase, CO_{2}. The number of degrees of freedom of the system, therefore, is 2 + 2 - 3 = 1; this system, therefore, also possesses one degree of freedom. We can now understand why these two systems behave in a similar manner; both are univariant, or possess only one degree of freedom. We shall therefore expect a similar behaviour in the case of all univariant systems, no matter how dissimilar the systems may outwardly appear. Similarly, all bivariant systems will exhibit analogous behaviour; and generally, systems possessing the same degree of freedom will show a like behaviour. In accordance with the Phase Rule, therefore, we may classify the different systems which may be found into invariant, univariant, bivariant, multivariant, {18} according to the relation which obtains between the number of the components and the number of coexisting phases; and we shall expect that in each case the members of any particular group will exhibit a uniform behaviour. By this means we are enabled to obtain an insight into the general behaviour of any system, so soon as we have determined the number of the components and the number of the coexisting phases. The adoption of the Phase Rule for the purposes of classification has been of great importance in studying changes in the equilibrium existing between different substances; for not only does it render possible the grouping together of a large number of isolated phenomena, but the guidance it affords has led to the discovery of new substances, has given the clue to the conditions under which these substances can exist, and has led to the recognition of otherwise unobserved resemblances existing between different systems. Deduction of the Phase Rule.--In the preceding pages we have restricted ourselves to the statement of the Phase Rule, without giving any indication of how it has been deduced. At the close of this chapter, therefore, the mathematical deduction of the generalization will be given, but in brief outline only, the reader being referred to works on Thermodynamics for a fuller treatment of the subject.[21] All forms of energy can be resolved into two factors, the _capacity_ factor and the _intensity_ factor; but for the production of equilibrium, only the intensity factor is of importance. Thus, if two bodies having the same temperature are brought in contact with each other, they will be in equilibrium as regards heat energy, no matter what may be the amounts of heat (capacity factor) contained in either, because the intensity factor--the temperature--is the same. But if the temperature of the two bodies is different, _i.e._ if the intensity factor of heat energy is different, the two bodies will no longer be in equilibrium; but heat will pass from the hotter to the colder until both have the same temperature. As with heat energy, so with chemical energy. If we have a substance existing in two different states, or in two different {19} phases of a system, equilibrium can occur only when the intensity factor of chemical energy is the same. This intensity factor may be called the _chemical potential_; and we can therefore say that a system will be in equilibrium when the chemical potential of each component is the same in all the phases in which the component occurs. Thus, for example, ice, water, and vapour have, at the triple point, the same chemical potential. The potential of a component in any phase depends not only on the composition of the phase, but also on the temperature and the pressure (or volume). If, therefore, we have a system of C components existing in P phases, then, in order to fix the composition of unit mass of each phase, it is necessary to know the masses of (C - 1) components in each of the phases. As regards the composition, therefore, each phase possesses (C - 1) variables. Since there are P phases, it follows that, as regards composition, the whole system possesses P(C - 1) variables. Besides these there are, however, two other variables, viz. temperature and pressure, so that altogether a system of C components in P phases possesses P(C - 1) + 2 variables. In order to define the state of the system completely, it will be necessary to have as many equations as there are variables. If, therefore, there are fewer equations than there are variables, then, according to the deficiency in the number of the equations, one or more of the variables will have an undefined value; and values must be assigned to these variables before the system is entirely defined. The number of these undefined values gives us the variability or the degree of freedom of the system. The equations by which the system is to be defined are obtained from the relationship between the potential of a component and the composition of the phase, the temperature and the pressure. Further, as has already been stated, equilibrium occurs when the potential of each component is the same in the different phases in which it is present. If, therefore, we choose as standard one of the phases in which all the components occur, then in any other phase in equilibrium with {20} it, the potential of each component must be the same as in the standard phase. For each phase in equilibrium with the standard phase, therefore, there will be a definite equation of state for each component in the phase; so that, if there are P phases, we obtain for each component (P - 1) equations; and for C components, therefore, we obtain C(P - 1) equations. But we have seen above that there are P(C - 1) + 2 variables, and as we have only C(P - 1) equations, there must be P(C - 1) + 2 - C(P - 1) = C + 2 - P variables undefined. That is to say, the degree of freedom (F) of a system consisting of C components in P phases is-- F = C + 2 - P * * * * * {21} CHAPTER III TYPICAL SYSTEMS OF ONE COMPONENT A. _Water._ For the sake of rendering the Phase Rule more readily intelligible, and at the same time also for the purpose of obtaining examples by which we may illustrate the general behaviour of systems, we shall in this chapter examine in detail the behaviour of several well-known systems consisting of only one component. The most familiar examples of equilibria in a one-component system are those furnished by the three phases of water, viz. ice, water, water vapour. The system consists of one component, because all three phases have the same chemical composition, represented by the formula H_{2}O. As the criterion of equilibrium we shall choose a definite pressure, and shall study the variation of the pressure with the temperature; and for the purpose of representing the relationships which we obtain we shall employ a temperature-pressure diagram, in which the temperatures are measured as abscissæ and the pressures as ordinates. In such a diagram invariant systems will be represented by points; univariant systems by lines, and bivariant systems by areas. Equilibrium between Liquid and Vapour. Vaporization Curve.--Consider in the first place the conditions for the coexistence of liquid and vapour. According to the Phase Rule (p. 16), a system consisting of one component in two phases has one degree of freedom, or is univariant. We should therefore expect that it will be possible for liquid water to coexist with water vapour at different values of temperature and {22} pressure, but that if we arbitrarily fix one of the variable factors, pressure, temperature, or volume (in the case of a given mass of substance), the state of the system will then be defined. If we fix, say, the temperature, then the pressure will have a definite value; or if we adopt a certain pressure, the liquid and vapour can coexist only at a certain definite temperature. Each temperature, therefore, will correspond to a definite pressure; and if in our diagram we join by a continuous line all the points indicating the values of the pressure corresponding to the different temperatures, we shall obtain a curve (Fig. 1) representing the variation of the pressure with the temperature. This is the curve of vapour pressure, or the _vaporization curve_ of water. [Illustration: FIG. 1.] Now, the results of experiment are quite in agreement with the requirements of the Phase Rule, and at any given temperature the system water--vapour can exist in equilibrium only under a definite pressure. The vapour pressure of water at different temperatures has been subjected to careful measurement by Magnus,[22] Regnault,[23] Ramsay and Young,[24] Juhlin,[25] Thiesen and Scheel,[26] and others. In the following table the values of the vapour pressure from -10° to +100° are those calculated from the measurements of Regnault, corrected by the measurements of Wiebe and Thiesen and Scheel;[27] those from 120° to 270° were determined {23} by Ramsay and Young, while the values of the critical pressure and temperature are those determined by Battelli.[28] VAPOUR PRESSURE OF WATER. -------------+-----------------+--------------+-------------------- | | | Temperature. | Pressure in cm. | Temperature. | Pressure in cm. | mercury. | | mercury. -------------+-----------------+--------------+-------------------- | | | -10° | 0.213 | 120° | 148.4 0° | 0.458[29] | 130° | 201.9 +20° | 1.752 | 150° | 356.8 40° | 5.516 | 200° | 1162.5 60° | 14.932 | 250° | 2973.4 80° | 35.54 | 270° | 4110.1 100° | 76.00 | 364.3° | 14790.4 (194.6 atm.) | | (critical | (critical pressure). | | temperature) | -------------+-----------------+--------------+-------------------- The pressure is, of course, independent of the relative or absolute volumes of the liquid and vapour; on increasing the volume at constant temperature, a certain amount of the liquid will pass into vapour, and the pressure will regain its former value. If, however, the pressure be permanently maintained at a value different from that corresponding to the temperature employed, then either all the liquid will pass into vapour, or all the vapour will pass into liquid, and we shall have either vapour alone or liquid alone. Upper Limit of Vaporization Curve.--On continuing to add heat to water contained in a closed vessel, the pressure of the vapour will gradually increase. Since with increase of pressure the density of the vapour must increase, and since with rise of temperature the density of the liquid must decrease, a point will be reached at which the density of liquid and vapour become identical; the system ceases to be heterogeneous, and passes into one homogeneous phase. The temperature at which this occurs is called the _critical temperature_. To this temperature there will, of course, correspond a certain definite pressure, called the _critical pressure_. The curve representing the {24} equilibrium between liquid and vapour must, therefore, end abruptly at the critical point. At temperatures above this point no pressure, however great, can cause the formation of the liquid phase; at temperatures above the critical point the vapour becomes a gas. In the case of water, the critical temperature is 364.3°, and the critical pressure 194.6 atm.; at the point representing these conditions the vapour-pressure curve of water must cease. Sublimation Curve of Ice.--Vapour is given off not only by liquid water, but also by solid water, or ice. That this is so is familiar to every one through the fact that ice or snow, even at temperatures below the melting point, gradually disappears in the form of vapour. Even at temperatures considerably lower than 0°, the vapour pressure of ice, although small, is quite appreciable; and it is possible, therefore, to have ice and vapour coexisting in equilibrium. When we inquire into the conditions under which such a system can exist, we see again that we are dealing with a univariant system--one component existing in two phases--and that, therefore, just as in the case of the system water and vapour, there will be for each temperature a certain definite pressure of the vapour, and this pressure will be independent of the relative or absolute amounts of the solid or vapour present, and will depend solely on the temperature. Further, just as in the case of the vapour pressure of water, the condition of equilibrium between ice and water vapour will be represented by a line or curve showing the change of pressure with the temperature. Such a curve, representing the conditions of equilibrium between a solid and its vapour, is called a _sublimation curve_. At temperatures represented by any point on this curve, the solid (ice) will sublime or pass into vapour without previously fusing. Since ice melts at 0° (_vide infra_), the sublimation curve must end at that temperature. The following are the values of the vapour pressure of ice between 0° and -50°.[30] {25} VAPOUR PRESSURE OF ICE. --------------------------------------------------------------- Temperature. | Pressure in mm. | Temperature. | Pressure in mm. | mercury. | | mercury. -------------+-----------------+--------------+---------------- -50° | 0.050 | -8° | 2.379 -40° | 0.121 | -6° | 2.821 -30° | 0.312 | -4° | 3.334 -20° | 0.806 | -2° | 3.925 -15° | 1.279 | 0° | 4.602 -10° | 1.999 | | ---------------------------------------------------------------- Equilibrium between Ice and Water. Curve of Fusion.--There is still another univariant system of the one component water, the existence of which, at definite values of temperature and pressure, the Phase Rule allows us to predict. This is the system solid--liquid. Ice on being heated to a certain temperature melts and passes into the liquid state; and since this system solid--liquid is univariant, there will be for each temperature a certain definite pressure at which ice and water can coexist or be in equilibrium, independently of the amounts of the two phases present. Since now the temperature at which the solid phase is in equilibrium with the liquid phase is known as the melting point or point of fusion of the solid, the curve representing the temperatures and pressures at which the solid and liquid are in equilibrium will represent the change of the melting point with the pressure. Such a curve is called the _curve of fusion_, or the melting-point curve. It was not until the middle of the nineteenth century that this connection between the pressure and the melting point, or the change of the melting point with the pressure, was observed. The first to recognize the existence of such a relationship was James Thomson,[31] who in 1849 showed that from theoretical considerations such a relationship must exist, and predicted that in the case of ice the melting point would be lowered by pressure. This prediction was fully confirmed by his brother, W. Thomson[32] (Lord Kelvin), who found that under a pressure {26} of 8.1 atm. the melting point of ice was -0.059°; under a pressure of 16.8 atm. the melting point was -0.129°. The experiments which were first made in this connection were more of a qualitative nature, but in recent years careful measurements of the influence of pressure on the melting point of ice have been made more especially by Tammann,[33] and the results obtained by him are given in the following table and represented graphically in Fig. 2. FUSION PRESSURE OF ICE. --------------------------------------------------------------------- | Pressure in kilogms. per | Change of melting point for Temperature. | sq. cm.[34] | an increase of pressure of | | 1 kilogm. per sq. cm. --------------------------------------------------------------------- -0° | 1 | -2.5° | 336 | 0.0074° -5° | 615 | 0.0090° -7.5° | 890 | 0.0091° -10.0° | 1155 | 0.0094° -12.5° | 1410 | 0.0100° -15.0° | 1625 | 0.0116° -17.5° | 1835 | 0.0119° -20.0° | 2042 | 0.0121° -22.1° | 2200 | 0.0133° --------------------------------------------------------------------- From the numbers in the table and from the figure we see that as the pressure is increased the melting point of ice is lowered; but we also observe that a very large change of pressure is required in order to produce a very small change in the melting point. The curve, therefore, is very steep. Increase of pressure by one atmosphere lowers the melting point by only 0.0076°,[35] or an increase of pressure of 135 atm. is required to produce a lowering of the melting point of 1°. We see further that the fusion curve bends slightly as the pressure is increased, which signifies that the variation of {27} the melting point with the pressure changes; at -15°, when the pressure is 1625 kilogm. per sq. cm., increase of pressure by 1 kilogm. per sq. cm. lowers the melting point by 0.012°. This curvature of the fusion curve we shall later (Chap. IV.) see to be an almost universal phenomenon. [Illustration: FIG. 2.] [Illustration: FIG. 3.] Equilibrium between Ice, Water, and Vapour. The Triple Point.--On examining the vapour-pressure curves of ice and water (Fig. 3), we see that at a temperature of about 0° and under a pressure of about 4.6 mm. mercury, the two curves cut. At this point liquid water and solid ice are each in equilibrium with vapour at the same pressure. Since this is so, they must, of course, be in equilibrium {28} with one another, as experiment also shows. At this point, therefore, ice, water, and vapour can be in equilibrium, and as there are three phases present, the point is called a _triple point_.[36] The triple point, however, does not lie exactly at 0° C., for this temperature is defined as the melting point of ice under atmospheric pressure. At the triple point, however, the pressure is equal to the vapour pressure of ice and water, and this pressure, as we see from the tables on pp. 21 and 23, is very nearly 4.6 mm., or almost 1 atm. less than in the previous case. Now, we have just seen that a change of pressure of 1 atm. corresponds to a change of the melting point of 0.0076°; the melting point of ice, therefore, when under the pressure of its own vapour, will be very nearly +0.0076°, and the pressure of the vapour will be very slightly greater than 4.579 mm., which is the pressure at 0° (p. 21). The difference is, however, slight, and may be neglected here. At the temperature, then, of +0.0076°, and under a pressure of 4.6 mm. of mercury, ice, water, and vapour will be in equilibrium; the point in our diagram representing this particular temperature and pressure is, therefore, the triple point of the system ice--water--vapour. Since at the triple point we have three phases of one component, the system at this point is invariant--it possesses no degrees of freedom. If the temperature is changed, the system will undergo alteration in such a way that one of the phases will disappear, and a univariant system will result; if heat be added, ice will melt, and we shall have left water and vapour; if heat be abstracted, water will freeze, and we shall have left ice and vapour; if, when the temperature is altered, the pressure is kept constant, then we shall ultimately obtain only one phase (see Chap. IV.). The triple point is not only the point of intersection of the vaporization and sublimation curves, but it is also the end-point of the fusion curve. The fusion curve, as we have seen, is the curve of equilibrium between ice and water; and since at the triple point ice and water are each in equilibrium with {29} vapour of the same pressure, they must, of course, also be in equilibrium with one another. [Illustration: FIG. 4.] Bivariant Systems of Water.--If we examine Fig. 4, we see that the curves OA, OB, OC, which represent diagrammatically the conditions under which water and vapour, ice and vapour, and water and ice are in equilibrium, form the boundaries of three "fields," or areas, I., II., III. These areas, now, represent the conditions for the existence of the single phases, solid, liquid, and vapour respectively. At temperatures and pressures represented by any point in the field I., solid only can exist as a stable phase. Since we have here one component in only one phase, the system is bivariant, and at any given temperature, therefore, ice can exist under a series of pressures; and under any given pressure, at a series of temperatures, these pressures and temperatures being limited only by the curves OB, OC. Similarly also with the areas II. and III. We see, further, that the different areas are the regions of stability of the phase common to the two curves by which the area is enclosed.[37] Thus, the phase common to the two systems {30} represented by BO (ice and vapour), and OA (water and vapour) is the vapour phase; and the area BOA is therefore the area of the vapour phase. Similarly, BOC is the area of the ice phase, and COA the area of the water phase. Supercooled Water. Metastable State.--When heated under the ordinary atmospheric pressure, ice melts when the temperature reaches 0°, and it has so far not been found possible to raise the temperature of ice above this point without liquefaction taking place. On the other hand, it has long been known that water can be cooled below zero without solidification occurring. This was first discovered in 1724 by Fahrenheit,[38] who found that water could be exposed to a temperature of -9.4° without solidifying; so soon, however, as a small particle of ice was brought in contact with the water, crystallization commenced. Superfused or supercooled water--_i.e._ water cooled below 0°--is unstable only in respect of the solid phase; so long as the presence of the solid phase is carefully avoided, the water can be kept for any length of time without solidifying, and the system supercooled water and vapour behaves in every way like a stable system. A system, now, which in itself is stable, and which becomes instable only in contact with a particular phase, is said to be _metastable_, and the region throughout which this condition exists is called the metastable region. Supercooled water, therefore, is in a metastable condition. If the supercooling be carried below a certain temperature, solidification takes place spontaneously without the addition of the solid phase; the system then ceases to be metastable, and becomes _instable_. Not only has water been cooled to temperatures considerably below the melting point of ice, but the vapour pressure of the supercooled water has been measured. It is of interest and importance, now, to see what relationship exists between the vapour pressure of ice and that of supercooled water at the same temperature. This relationship is clearly shown by the numbers in the following table,[39] and is represented in Fig. 3, {31} p. 27., and diagrammatically in Fig. 4, the vapour pressures of supercooled water being represented by the curve OA', which is the unbroken continuation of AO. VAPOUR PRESSURE OF ICE AND OF SUPERCOOLED WATER. --------------------------------------------------------------------- | Pressure in mm. mercury. ------------------------------------------------------ Temperature. | | | | Water. | Ice. | Difference. --------------------------------------------------------------------- 0° | 4.618 | 4.602 | 0.016[40] -2° | 3.995 | 3.925 | 0.070 -4° | 3.450 | 3.334 | 0.116 -8° | 2.558 | 2.379 | 0.179 -10° | 2.197 | 1.999 | 0.198 -15° | 1.492 | 1.279 | 0.213 -20° | 1.005 | 0.806 | 0.199 --------------------------------------------------------------------- At all temperatures below 0° (more correctly +0.0076°), at which temperature water and ice have the same vapour pressure, the vapour pressure of supercooled water is _greater_ than that of ice at the same temperature. From the relative positions of the curves OB and OA (Fig. 4) we see that at all temperatures above 0°, the (metastable) sublimation curve of ice, if it could be obtained, would be higher than the vaporization curve of water. This shows, therefore, that at 0° a "break" must occur in the curve of states, and that in the neighbourhood of this break the curve above that point must ascend less rapidly than the curve below the break. Since, however, the differences in the vapour pressures of supercooled water and of ice are very small, the change in the direction of the vapour-pressure curve on passing from ice to water was at first not observed, and Regnault regarded the sublimation curve as passing continuously into {32} the vaporization curve. The existence of a break was, however, shown by James Thomson[41] and by Kirchhoff[42] to be demanded by thermo-dynamical considerations, and the prediction of theory was afterwards realized experimentally by Ramsay and Young in their determinations of the vapour pressure of water and ice, as well as in the case of other substances.[43] From what has just been said, we can readily understand why ice and water cannot exist in equilibrium below 0°. For, suppose we have ice and water in the same closed space, but not in contact with one another, then since the vapour pressure of the supercooled water is higher than that of ice, the vapour of the former must be supersaturated in contact with the latter; vapour must, therefore, condense on the ice; and in this way there will be a slow distillation from the water to the ice, until at last all the water will have disappeared, and only ice and vapour remain.[44] Other Systems of the Substance Water.--We have thus far discussed only those systems which are constituted by the three phases--ice, water, and water vapour. It has, however, been recently found that at a low temperature and under a high pressure ordinary ice can pass into two other crystalline varieties, called by Tammann[45] ice II. and ice III., ordinary ice being ice I. According to the Phase Rule, now, since each of these solid forms constitutes a separate phase (p. 9), it will be possible to have the following (and more) systems of water, in addition to those already studied, viz. water, ice I., ice II.; water, ice I., ice III.; water, ice II., ice III., forming invariant systems and existing in equilibrium only at a definite triple point; further, water, ice II.; water, ice III.; ice I., ice II.; ice I., ice III.; ice II., ice III., forming univariant systems, existing, therefore, at definite corresponding values of {33} temperature and pressure; and lastly, the bivariant systems, ice II. and ice III. Several of these systems have been investigated by Tammann. The triple point for water, ice I., ice III., lies at -22°, and a pressure of 2200 kilogms. per sq. cm. (2130 atm.), as indicated in Fig. 2, p. 27.[46] In contrast with the behaviour of ordinary ice, the temperature of equilibrium in the case of water--ice II., and water--ice III., is _raised_ by increase of pressure. B. _Sulphur._ Polymorphism.--Reference has just been made to the fact that ice can exist not only in the ordinary form, but in at least two other crystalline varieties. This phenomenon, the existence of a substance in two or more different crystalline forms, is called _polymorphism_. Polymorphism was first observed by Mitscherlich[47] in the case of sodium phosphate, and later in the case of sulphur. To these two cases others were soon added, at first of inorganic, and later of organic substances, so that polymorphism is now recognized as of very frequent occurrence indeed.[48] These various forms of a substance differ not only in crystalline shape, but also in melting point, specific gravity, and other physical properties. In the liquid state, however, the differences do not exist. According to our definition of phases (p. 9), each of these polymorphic forms constitutes a separate phase of the particular substance. As is readily apparent, the number of possible systems formed of one component may be considerably increased when that component is capable of existing in different crystalline forms. We have, therefore, to inquire what are the conditions under which different polymorphic forms can coexist, either alone or in presence of the liquid and vapour phase. For the purpose of illustrating the general behaviour of such systems, we shall study the systems formed by the different crystalline forms of sulphur, tin, and benzophenone. {34} Sulphur exists in two well-known crystalline forms--rhombic, or octahedral, and monoclinic, or prismatic sulphur. Of these, the former melts at 114.5°; the latter at 120°.[49] Further, at the ordinary temperature, rhombic sulphur can exist unchanged, whereas, on being heated to temperatures somewhat below the melting point, it passes into the prismatic variety. On the other hand, at temperatures above 96°, prismatic sulphur can remain unchanged, whereas at the ordinary temperature it passes slowly into the rhombic form. If, now, we examine the case of sulphur with the help of the Phase Rule, we see that the following systems are theoretically possible:-- I. _Bivariant Systems: One component in one phase._ (_a_) Rhombic sulphur. (_b_) Monoclinic sulphur. (_c_) Sulphur vapour. (_d_) Liquid sulphur. II. _Univariant Systems: One component in two phases._ (_a_) Rhombic sulphur and vapour. (_b_) Monoclinic sulphur and vapour. (_c_) Rhombic sulphur and liquid. (_d_) Monoclinic sulphur and liquid. (_e_) Rhombic and monoclinic sulphur. (_f_) Liquid and vapour. III. _Invariant Systems: One component in three phases._ (_a_) Rhombic and monoclinic sulphur and vapour. (_b_) Rhombic sulphur, liquid and vapour. (_c_) Monoclinic sulphur, liquid and vapour. (_d_) Rhombic and monoclinic sulphur and liquid. [Illustration: FIG. 5.] Triple Point--Rhombic and Monoclinic Sulphur and Vapour. Transition Point.--In the case of ice, water and vapour, we saw that at the triple point the vapour pressures of ice and water are equal; below this point, ice is stable; above this point, water is stable. We saw, further, that below 0° the vapour pressure of the stable system is lower than that of the metastable, and therefore that at the triple point there is a break in the vapour pressure curve of such a kind that above {35} the triple point the vapour-pressure curve ascends more slowly than below it. Now, although the vapour pressure of solid sulphur has not been determined, we can nevertheless consider that it does possess a certain, even if very small, vapour pressure,[50] and that at the temperature at which the vapour pressures of rhombic and monoclinic sulphur become equal, we can have these two solid forms existing in equilibrium with the vapour. Below that point only one form, that with the lower vapour pressure, will be stable; above that point only the other form will be stable. On passing through the triple point, therefore, there will be a change of the one form into the other. This point is represented in our diagram (Fig. 5) by the point O, the two curves AO and OB representing diagrammatically the vapour pressures of rhombic and monoclinic sulphur respectively. If the vapour phase is absent and the system maintained under a constant pressure, _e.g._ {36} atmospheric pressure, there will also be a definite temperature at which the two solid forms are in equilibrium, and on passing through which complete and reversible transformation of one form into the other occurs. This temperature, which refers to equilibrium in absence of the vapour phase, is known as the _transition temperature_ or _inversion temperature_. Were we dependent on measurements of pressure and temperature, the determination of the transition point might be a matter of great difficulty. When we consider, however, that the other physical properties of the solid phases, _e.g._ the density, undergo an abrupt change on passing through the transition point, owing to the transformation of one form into the other, then any method by which this abrupt change in the physical properties can be detected may be employed for determining the transition point. A considerable number of such methods have been devised, and a description of the most important of these is given in the Appendix. In the case of sulphur, the transition point of rhombic into monoclinic sulphur was found by Reicher[51] to lie at 95.5°. Below this temperature the octahedral, above it the monoclinic, is the stable form. Condensed Systems.--We have already seen that in the change of the melting point of water with the pressure, a very great increase of the latter was necessary in order to produce a comparatively small change in the temperature of equilibrium. This is a characteristic of all systems from which the vapour phase is absent, and which are composed only of solid and liquid phases. Such systems are called _condensed systems_,[52] and in determining the temperature of equilibrium of such systems, practically the same point will be obtained whether the measurements are carried out under atmospheric pressure or under the pressure of the vapour of the solid or liquid phases. The transition point, therefore, as determined in open vessels at atmospheric pressure, will differ only by a very slight amount from the triple point, or point at which the two solid or liquid phases are in equilibrium under the pressure of their vapour. {37} The determination of the transition point is thereby greatly simplified. Suspended Transformation.--In many respects the transition point of two solid phases is analogous to the melting point of a solid, or point at which the solid passes into a liquid. In both cases the change of phase is associated with a definite temperature and pressure in such a way that below the point the one phase, above the point the other phase, is stable. The transition point, however, differs in so far from a point of fusion, that while it is possible to supercool a liquid, no definite case is known where the solid has been heated above the triple point without passing into the liquid state. Transformation, therefore, is suspended only on one side of the melting point. In the case of two solid phases, however, the transition point can be overstepped in both directions, so that each phase can be obtained in the metastable condition. In the case of supercooled water, further, we saw that the introduction of the stable, solid phase caused the speedy transformation of the metastable to the stable condition of equilibrium; but in the case of two solid phases the change from the metastable to the stable modification may occur with great slowness, even in presence of the stable form. This tardiness with which the stable condition of equilibrium is reached greatly increases in many cases the difficulty of accurately determining the transition point. The phenomena of suspended transformation will, however, receive a fuller discussion later (p. 68). Transition Curve--Rhombic and Monoclinic Sulphur.--Just as we found the melting point of ice to vary with the pressure, so also do we find that change of pressure causes an alteration in the transition point. In the case of the transition point of rhombic into monoclinic sulphur, increase of pressure by 1 atm. raises the transition point by 0.04°-0.05°.[53] The transition curve, or curve representing the change of the transition point with pressure, will therefore slope to the right away from the pressure axis. This is curve OC (Fig. 5). {38} Triple Point--Monoclinic Sulphur, Liquid, and Vapour. Melting Point of Monoclinic Sulphur.--Above 95.5°, monoclinic sulphur is, as we have seen, the stable form. On being heated to 120°, under atmospheric pressure, it melts. This temperature is, therefore, the point of equilibrium between monoclinic sulphur and liquid sulphur under atmospheric pressure. Since we are dealing with a condensed system, this temperature may be regarded as very nearly that at which the solid and liquid are in equilibrium with their vapour, _i.e._ the triple point, solid (monoclinic)--liquid--vapour. This point is represented in the diagram by B. Triple Point--Rhombic and Monoclinic Sulphur and Liquid.--In contrast with that of ice, the fusion point of monoclinic sulphur is _raised_ by increase of pressure, and the fusion curve, therefore, slopes to the right. The transition curve of rhombic and monoclinic sulphur, as we have seen, also slopes to the right, and more so than the fusion curve of monoclinic sulphur. There will, therefore, be a certain pressure and temperature at which the two curves will cut. This point lies at 151°, and a pressure of 1320 kilogm. per sq. cm., or about 1288 atm.[54] It, therefore, forms another triple point, the existence of which had been predicted by Roozeboom,[55] at which rhombic and monoclinic sulphur are in equilibrium with liquid sulphur. It is represented in our diagram by the point C. _Beyond this point monoclinic sulphur ceases to exist in a stable condition._ At temperatures and pressures above this triple point, rhombic sulphur will be the stable modification, and this fact is of mineralogical interest, because it explains the occurrence in nature of well-formed rhombic crystals. Under ordinary conditions, prismatic sulphur separates out on cooling fused sulphur, but at temperatures above 151° and under pressures greater than 1288 atm., the rhombic form would be produced.[56] Triple Point--Rhombic Sulphur, Liquid, and Vapour. Metastable Triple Point.--On account of the slowness with {39} which transformation of one form into the other takes place on passing the transition point, it has been found possible to heat rhombic sulphur up to its melting point (114.5°). At this temperature, not only is rhombic sulphur in a metastable condition, but the liquid is also metastable, its vapour pressure being greater than that of solid monoclinic sulphur. This point is represented in our diagram by the point b. From the relative positions of the metastable melting point of rhombic sulphur and the stable melting point of monoclinic sulphur at 120°, we see that, of the two forms, the metastable form has the lower melting point. This, of course, is valid only for the relative stability in the neighbourhood of the melting point; for we have already learned that at lower temperatures rhombic sulphur is the stable, monoclinic sulphur the metastable (or unstable) form. Fusion Curve of Rhombic Sulphur.--Like any other melting point, that of rhombic sulphur will be displaced by increase of pressure; increase of pressure raises the melting point, and we can therefore obtain a metastable fusion curve representing the conditions under which rhombic sulphur is in equilibrium with liquid sulphur. This metastable fusion curve must pass through the triple point for rhombic sulphur--monoclinic sulphur--liquid sulphur, and on passing this point it becomes a stable fusion curve. The continuation of this curve, therefore, above 151° forms the stable fusion curve of rhombic sulphur (curve CD). These curves have been investigated at high pressures by Tammann, and the results are represented according to scale in Fig. 6,[57] _a_ being the curve for monoclinic sulphur and liquid; _b_, that for rhombic sulphur and liquid; and _c_, that for rhombic and monoclinic sulphur. Bivariant Systems.--Just as in the case of the diagram of states of water, the areas in Fig. 5 represent the conditions for the stable existence of the single phases: rhombic sulphur in the area to the left of AOCD; monoclinic sulphur in the area OBC; liquid sulphur in the area EBCD; sulphur vapour below the curves AOBE. As can be seen from the diagram, {40} the existence of monoclinic sulphur is limited on all sides, its area being bounded by the curves OB, OC, BC. At any point outside this area, monoclinic sulphur can exist only in a metastable condition. [Illustration: FIG. 6.] Other crystalline forms of sulphur have been obtained,[58] so that the existence of other systems of the one-component sulphur besides those already described is possible. Reference will be made to these later (p. 51). {41} C. _Tin._ Another substance capable of existing in more than one crystalline form, is the metal tin, and although the general behaviour, so far as studied, is analogous to that of sulphur, a short account of the two varieties of tin may be given here, not only on account of their metallurgical interest, but also on account of the importance which the phenomena possess for the employment of this metal in everyday life. After a winter of extreme severity in Russia (1867-1868), the somewhat unpleasant discovery was made that a number of blocks of tin, which had been stored in the Customs House at St. Petersburg, had undergone disintegration and crumbled to a grey powder.[59] That tin undergoes change on exposure to extreme cold was known, however, before that time, even as far back as the time of Aristotle, who spoke of the tin as "melting."[60] Ludicrous as that term may now appear, Aristotle nevertheless unconsciously employed a strikingly accurate analogy, for the conditions under which ordinary white tin passes into the grey modification are, in many ways, quite analogous to those under which a substance passes from the solid to the liquid state. The knowledge of this was, however, beyond the wisdom of the Greek philosopher. For many years there existed considerable confusion both as to the conditions under which the transformation of white tin into its allotropic modification occurs, and to the reason of the change. Under the guidance of the Phase Rule, however, the confusion which obtained has been cleared away, and the "mysterious" behaviour of tin brought into accord with other phenomena of transformation.[61] Transition Point.--Just as in the case of sulphur, so also in the case of tin, there is a transition point above which the {42} one form, ordinary white tin, and below which the other form, grey tin, is the stable variety. In the case of this metal, the transition point was found by Cohen and van Eyk, who employed both the dilatometric and the electrical methods (Appendix) to be 20°. Below this temperature, grey tin is the stable form. But, as we have seen in the case of sulphur, the change of the metastable into the stable solid phase occurs with considerable slowness, and this behaviour is found also in the case of tin. Were it not so, we should not be able to use this metal for the many purposes to which it is applied in everyday life; for, with the exception of a comparatively small number of days in the year, the temperature of our climate is below 20°, and _white tin is, therefore, at the ordinary temperature, in a metastable condition_. The change, however, into the stable form at the ordinary temperature, although slow, nevertheless takes place, as is shown by the partial or entire conversion of articles of tin which have lain buried for several hundreds of years. On lowering the temperature, the velocity with which the transformation of the tin occurs is increased, and Cohen and van Eyk found that the temperature of maximum velocity is about -50°. Contact with the stable form will, of course, facilitate the transformation. The change of white tin into grey takes place also with increased velocity in presence of a solution of tin ammonium chloride (pink salt), which is able to dissolve small quantities of tin. In presence of such a solution also, it was found that the temperature at which the velocity of transformation was greatest was raised to 0°. At this temperature, white tin in contact with a solution of tin ammonium chloride, and the grey modification, undergoes transformation to an appreciable extent in the course of a few days. Fig. 7 is a photograph of a piece of white tin undergoing transformation into the grey variety.[62] The bright surface of the tin becomes covered with a number of warty masses, formed of the less dense grey form, and the number and size of these continue to grow until the whole of the white tin has passed {43} into a grey powder. On account of the appearance which is here seen, this transformation of tin has been called by Cohen the "tin plague." [Illustration: FIG. 7.] {44} Enantiotropy and Monotropy.--In the case of sulphur and tin, we have met with two substances existing in polymorphic forms, and we have also learned that these forms exhibit a definite transition point at which their relative stability is reversed. Each form, therefore, possesses a definite range of stable existence, and is capable of undergoing transformation into the other, at temperatures above or below that of the transition point. Another class of dimorphous substances is, however, met with as, for instance, in the case of the well-known compounds iodine monochloride and benzophenone. Each crystalline form has its own melting point, the dimorphous forms of iodine monochloride melting at 13.9° and 27.2°,[63] and those of benzophenone at 26° and 48°.[64] This class of substance differs from that which we have already studied (_e.g._ sulphur and tin), in that at all temperatures up to the melting point, only one of the forms is stable, the other being metastable. There is, therefore, no transition point, and transformation of the crystalline forms can be observed _only in one direction_. These two classes of phenomena are distinguished by the names _enantiotropy_ and _monotropy_; enantiotropic substances being such that the change of one form into the other is a reversible process (_e.g._ rhombic sulphur into monoclinic, and monoclinic sulphur into rhombic), and monotropic substances, those in which the transformation of the crystalline forms is irreversible. [Illustration: FIG. 8.] [Illustration: FIG. 9.] These differences in the behaviour can be explained very well in many cases by supposing that in the case of enantiotropic substances the transition point lies below the melting point, while in the case of monotropic substances, it lies above the melting point.[65] These conditions would be represented by the Figs. 8 and 9. In these two figures, O_{3} is the transition point, O_{1} and O_{2} the melting points of the metastable and stable forms {45} respectively. From Fig. 9 we see that the crystalline form I. at all temperatures up to its melting point is metastable with respect to the form II. In such cases the transition point could be reached only at higher pressures. Although, as already stated, this explanation suffices for many cases, it does not prove that in all cases of monotropy the transition point is above the melting point of the two forms. It is also quite possible that the transition point may lie below the melting points;[66] in this case we have what is known as _pseudomonotropy_. It is possible that graphite and diamond,[67] perhaps also the two forms of phosphorus, stand in the relation of pseudomonotropy (_v._ p. 49). The disposition of the curves in Figs. 8 and 9 also explains the phenomenon sometimes met with, especially in organic chemistry, that the substance first melts, then solidifies, and remelts at a higher temperature. On again determining the melting point after re-solidification, only the higher melting point is obtained. The explanation of such a behaviour is, that if the determination of the melting point is carried out rapidly, the point O_{1}, the melting point of the metastable solid form, may be realized. At this temperature, however, the liquid is metastable with respect to the stable solid form, and if the temperature is {46} not allowed to rise above the melting point of the latter, the liquid may solidify. The stable solid modification thus obtained will melt only at a higher temperature. D. _Phosphorus._ An interesting case of a monotropic dimorphous substance is found in phosphorus, which occurs in two crystalline forms; white phosphorus belonging to the regular system, and red phosphorus belonging to the hexagonal system. From determinations of the vapour pressures of liquid white phosphorus, and of solid red phosphorus,[68] it was found that the vapour pressure of red phosphorus was considerably lower than that of liquid white phosphorus at the same temperature, the values obtained being given in the following table. VAPOUR PRESSURES OF WHITE AND RED PHOSPHORUS. ------------------------------------------------------------------------- Vapour pressure of liquid white phosphorus. | Vapour pressure of red | phosphorus. -------------------------------------------------+----------------------- Temperature.| Pressure | Temperature.| Pressure | Temperature.| Pressure | in cm. | | in atm. | | in atm. ------------+----------+-------------+-----------+-------------+--------- 165° | 12 | 360° | 3.2 | 360° | 0.1 180° | 20.4 | 440° | 7.5 | 440° | 1.75 200° | 26.6 | 494° | 18.0 | 487° | 6.8 219° | 35.9 | 503° | 21.9 | 510° | 10.8 230° | 51.4 | 511° | 26.2 | 531° | 16.0 290° | 76.0 | -- | -- | 550° | 31.0 -- | -- | -- | -- | 577° | 56.0 ------------------------------------------------------------------------- These values are also represented graphically in Fig. 10. [Illustration: FIG. 10.] At all temperatures above about 260°, transformation of the white into the red modification takes place with appreciable velocity, and this velocity increases as the temperature is raised. Even at lower temperatures, _e.g._ at the ordinary temperature, the velocity of transformation is increased under the influence {47} of light,[69] or by the presence of certain substances, _e.g._ iodine,[70] just as the velocity of transformation of white tin into the grey modification was increased by the presence of a solution of tin ammonium chloride (p. 40). At the ordinary temperature, therefore, white phosphorus must be considered as the less stable (metastable) form, for although it can exist in contact with red phosphorus for a long period, its vapour pressure, as we have seen, is greater than that of the red modification, and also, its solubility in different solvents is greater[71] than that of the red modification; as we shall find later, the solubility of the metastable form is always greater than that of the stable. The relationships which are met with in the case of phosphorus can be best represented by the diagram, Fig. 11.[72] In this figure, BO_{1} represents the conditions of equilibrium of the univariant system red phosphorus and vapour, which ends at O_{1}, the melting point of red phosphorus. By heating in capillary tubes of hard glass, Chapman[73] found that red phosphorus melts at the melting point of potassium iodide, _i.e._ about 630°,[74] but the pressure at this temperature is unknown. At O_{1}, then, we have the triple point, red phosphorus, liquid, and vapour, and starting from it, we should have the {48} vaporization curve of liquid phosphorus, O_{1}A, and the fusion curve of red phosphorus, O_{1}F. Although these have not been determined, the latter curve must, from theoretical considerations (_v._ p. 58), slope slightly to the right; _i.e._ increase of pressure raises the melting point of red phosphorus. [Illustration: FIG. 11.] When white phosphorus is heated to 44°, it melts. At this point, therefore, we shall have another triple point, white phosphorus--liquid--vapour; the pressure at this point has been calculated to be 3 mm.[75] This point is the intersection of three curves, viz. sublimation curve, vaporization curve, and the fusion curve of white phosphorus. The fusion curve, O_{2}E, has been determined by Tammann[76] and by G. A. Hulett,[77] and it was found that increase of pressure by 1 atm. raises the melting point by 0.029°. The sublimation curve of white phosphorus has not yet been determined. As can be seen from the table of vapour pressures (p. 46), the vapour pressure of white phosphorus has been determined up to 500°; at temperatures above this, however, the velocity with which transformation into red phosphorus takes place is so great as to render the determination of the vapour pressure {49} at higher temperatures impossible. Since, however, the difference between white phosphorus and red phosphorus disappears in the liquid state, the vapour pressure curve of white phosphorus must pass through the point O_{1}, the melting point of red phosphorus, and must be continuous with the curve O_{1}A, the vapour pressure curve of liquid phosphorus (_vide infra_). Since, as Fig. 10 shows, the vapour pressure curve of white phosphorus ascends very rapidly at higher temperatures, the "break" between BO_{1} and O_{1}A must be very slight. As compared with monotropic substances like benzophenone, phosphorus exhibits the peculiarity that transformation of the metastable into the stable modification takes place with great slowness; and further, the time required for the production of equilibrium between red phosphorus and phosphorus vapour is great compared with that required for establishing the same equilibrium in the case of white phosphorus. This behaviour can be best explained by the assumption that change in the molecular complexity (polymerization) occurs in the conversion of white into red phosphorus, and when red phosphorus passes into vapour (depolymerization).[78] This is borne out by the fact that measurements of the vapour density of phosphorus vapour at temperatures of 500° and more, show it to have the molecular weight represented by P_{4},[79] and the same molecular weight has been found for phosphorus in solution.[80] On the other hand, it has recently been shown by R. Schenck,[81] that the molecular weight of red phosphorus is at least P_{8}, and very possibly higher. In the case of phosphorus, therefore, it is more than possible that we are dealing, not simply with two polymorphic {50} forms of the same substance, but with polymeric forms, and that there is no transition point at temperatures above the absolute zero, unless we assume the molecular complexity of the two forms to become the same. The curve for red phosphorus would therefore lie below that of white phosphorus, for the vapour pressure of the polymeric form, if produced from the simpler form with evolution of heat, must be lower than that of the latter. A transition point would, of course, become possible if the sign of the heat effect in the transformation of the one modification into the other should change. If, further, the liquid which is produced by the fusion of red phosphorus at 630° under high pressure also exists in a polymeric form, greater than P_{4}, then the metastable vaporization curve of white phosphorus would not pass through the melting point of red phosphorus, as was assumed above.[82] We have already seen in the case of water (p. 31) that the vapour pressure of supercooled water is greater than that of ice, and that therefore it is possible, theoretically at least, by a process of distillation, to transfer the water from one end of a closed tube to the other, and to there condense it as ice. On account of the very small difference between the vapour pressure of supercooled water and ice, this distillation process has not been experimentally realized. In the case of phosphorus, however, where the difference in the vapour pressures is comparatively great, it has been found possible to distil white phosphorus from one part of a closed tube to another, and to there condense it as red phosphorus; and since the vapour pressure of red phosphorus at 350° is less than the vapour pressure of white phosphorus at 200°, it is possible to carry out the distillation from a _colder_ part of the tube to a _hotter_, by having white phosphorus at the former and red phosphorus at the latter. Such a process of distillation has been carried out by Troost and Hautefeuille between 324° and 350°.[83] Relationships similar to those found in the case of phosphorus are also met with in the case of cyanogen and {51} paracyanogen, which have been studied by Chappuis,[84] Troost and Hautefeuille,[85] and Dewar,[86] and also in the case of other organic substances. Enantiotropy combined with Monotropy.--Not only can polymorphic substances exhibit enantiotropy or monotropy, but, if the substance is capable of existing in more than two crystalline forms, both relationships may be found, so that some of the forms may be enantiotropic to one another, while the other forms exhibit only monotropy. This behaviour is seen in the case of sulphur, which can exist in as many as eight different crystalline varieties. Of these only monoclinic and rhombic sulphur exhibit the relationship of enantiotropy, _i.e._ they possess a definite transition point, while the other forms are all metastable with respect to rhombic and monoclinic sulphur, and remain so up to the melting point; that is to say, they are monotropic modifications.[87] E. _Liquid Crystals._ Phenomena observed.--In 1888 it was discovered by Reinitzer[88] that the two substances, cholesteryl acetate and cholesteryl benzoate, possess the peculiar property of melting sharply at a definite temperature to milky liquids; and that the latter, on being further heated, suddenly become clear, also at a definite temperature. Other substances, more especially _p_-azoxyanisole and _p_-azoxyphenetole, were, later, found to possess the same property of having apparently a double melting point.[89] On cooling the clear liquids, the reverse series of changes occurred. The turbid liquids which were thus obtained were found to possess not only the usual properties of liquids (such as the {52} property of flowing and of assuming a perfectly spherical shape when suspended in a liquid of the same density), but also those properties which had hitherto been observed only in the case of solid crystalline substances, viz. the property of double refraction and of giving interference colours when examined by polarized light; the turbid liquids are _anisotropic_. To such liquids, the optical properties of which were discovered by O. Lehmann,[90] the name _liquid crystals_, or crystalline liquids, was given. Nature of Liquid Crystals.--During the past ten years the question as to the nature of liquid crystals has been discussed by a number of investigators, several of whom have contended strongly against the idea of the term "liquid" being applied to the crystalline condition; and various attempts have been made to prove that the turbid liquids are in reality heterogeneous and are to be classed along with emulsions.[91] This view was no doubt largely suggested by the fact that the anisotropic liquids were turbid, whereas the "solid" crystals were clear. Lehmann found, however, that, when examined under the microscope, the "simple" liquid crystals were also clear,[92] the apparent turbidity being due to the aggregation of a number of differently oriented crystals, in the same way as a piece of marble does not appear transparent although composed of transparent crystals.[93] Further, no proof of the heterogeneity of liquid crystals has yet been obtained, but rather all chemical and physical investigations indicate that they are homogeneous.[94] No separation {53} of a solid substance from the milky, anisotropic liquids has been effected; the anisotropic liquid is in some cases less viscous than the isotropic liquid formed at a higher temperature; and the temperature of liquefaction is constant, and is affected by pressure and admixture with foreign substances exactly as in the case of a pure substance.[95] [Illustration: FIG. 12.] Equilibrium Relations in the Case of Liquid Crystals.--Since, now, we have seen that we are dealing here with substances in two crystalline forms (which we may call the solid and liquid[96] crystalline form), which possess a definite transition point, at which, transformation of the one form into the other occurs in both directions, we can represent the conditions of equilibrium by a diagram in all respects similar to that employed in the case of other enantiotropic substances, _e.g._ sulphur (p. 35). {54} In Fig. 12 there is given a diagrammatic representation of the relationships found in the case of _p_-azoxyanisole.[97] Although the vapour pressure of the substance in the solid, or liquid state, has not been determined, it will be understood from what we have already learned, that the curves AO, OB, BC, representing the vapour pressure of solid crystals, liquid crystals, isotropic liquid, must have the relative positions shown in the diagram. Point O, the transition point of the solid into the liquid crystals, lies at 118.27°, and the change of the transition point with the pressure is +0.032° pro 1 atm. The transition curve OE slopes, therefore, slightly to the right. The point B, the melting point of the liquid crystals, lies at 135.85°, and the melting point is raised 0.0485° pro 1 atm. The curve BD, therefore, also slopes to the right, and more so than the transition curve. In this respect azoxyanisole is different from sulphur. The areas bounded by the curves represent the conditions for the stable existence of the four single phases, solid crystals, liquid crystals, isotropic liquid and vapour. The most important substances hitherto found to form liquid crystals are[98]:-- ----------------------------------+------------+-------- | | Substance. | Transition | Melting | point. | point. ----------------------------------+------------+-------- | | Cholesteryl benzoate | 145.5° | 178.5° Azoxyanisole | 118.3° | 135.9° Azoxyphenetole | 134.5° | 168.1° Condensation product from | | benzaldehyde and benzidine | 234° | 260° Azine of _p_-oxyethylbenzaldehyde | 172° | 196° Condensation product from | | _p_-tolylaldehyde and benzidine | 231° | -- _p_-Methoxycinnamic acid | 169° | 185° ----------------------------------+------------+-------- * * * * * {55} CHAPTER IV GENERAL SUMMARY In the preceding pages we have learned how the principles of the Phase Rule can be applied to the elucidation of various systems consisting of one component. In the present chapter it is proposed to give a short summary of the relationships we have met with, and also to discuss more generally how the Phase Rule applies to other one-component systems. On account of the fact that beginners are sometimes inclined to expect too much of the Phase Rule; to expect, for example, that it will inform them as to the exact behaviour of a substance, it may here be emphasized that the Phase Rule is a general rule; it informs us only as to the general conditions of equilibrium, and leaves the determination of the definite, numerical data to experiment. Triple Point.--We have already (p. 28) defined a triple point in a one-component system, as being that pressure and temperature at which three phases coexist in equilibrium; it represents, therefore, an invariant system (p. 16). At the triple point also, three curves cut, viz. the curves representing the conditions of equilibrium of the three univariant systems formed by the combination of the three phases in pairs. The most common triple point of a one-component system is, of course, the triple point, solid, liquid, vapour (S-L-V), but other triple points[99] are also possible when, as in the case of {56} sulphur or benzophenone, polymorphic forms occur. Whether or not all the triple points can be experimentally realized will, of course, depend on circumstances. We shall, in the first place, consider only the triple point S-L-V. As to the general arrangement of the three univariant curves around the triple point, the following rules may be given. (1) The prolongation of each of the curves beyond the triple point must lie between the other two curves. (2) The middle position at one and the same temperature in the neighbourhood of the triple point is taken by that curve (or its metastable prolongation) which represents the two phases of most widely differing specific volume.[100] That is to say, if a line of constant temperature is drawn immediately above or below the triple point so as to cut the three curves--two stable curves and the metastable prolongation of the third--the position of the curves at that temperature will be such that the middle position is occupied by that curve (or its metastable prolongation) which represents the two phases of most widely differing specific volume. Now, although these rules admit of a considerable variety of possible arrangements of curves around the triple point,[101] only two of these have been experimentally obtained in the case of the triple point solid--liquid--vapour. At present, therefore, we shall consider only these two cases (Figs. 13 and 14). [Illustration: FIG. 13.] [Illustration: FIG. 14.] An examination of these two figures shows that they satisfy the rules laid down. Each of the curves on being prolonged passes between the other two curves. In the case of substances of the first type (Fig. 13), the specific volume of the solid is greater than that of the liquid (the substance contracts on fusion); the difference of specific volume will, therefore, be greatest between liquid and vapour. The curve, therefore, for liquid and vapour (or its prolongation) must lie between the other two curves; this is seen from the figure to be the case. Similarly, the rule is satisfied by the arrangement of curves in Fig. 14, where the difference of specific volumes is {57} greatest between the solid and vapour. In this case the curve S-V occupies the intermediate position. As we see, the two figures differ from one another only in that the fusion curve OC in one case slopes to the right away from the pressure axis, thus indicating that the melting point is raised by increase of pressure; in the other case, to the left, indicating a lowering of the melting point with the pressure. These conditions are found exemplified in the case of sulphur and ice (pp. 29 and 35). We see further from the two figures, that O in Fig. 13 gives the highest temperature at which the solid can exist, for the curve for solid--liquid slopes back to regions of lower temperature; in Fig. 14, O gives the lowest temperature at which the liquid phase can exist as stable phase.[102] Theorems of van't Hoff and of Le Chatelier.--So far we have studied only the conditions under which various systems exist in equilibrium; and we now pass to a consideration of the changes which take place in a system when the external conditions of temperature and pressure are altered. For all such changes there exist two theorems, based on the laws of thermodynamics, by means of which the alterations in a system can be qualitatively predicted.[103] The first of these, usually {58} known as van't Hoff's _law of movable equilibrium_,[104] states: When the temperature of a system in equilibrium is raised, that reaction takes place which is accompanied by absorption of heat; and, conversely, when the temperature is lowered, that reaction occurs which is accompanied by an evolution of heat. The second of the two theorems refers to the effect of change of pressure, and states:[105] When the pressure on a system in equilibrium is increased, that reaction takes place which is accompanied by a diminution of volume; and when the pressure is diminished, a reaction ensues which is accompanied by an increase of volume. The demonstration of the universal applicability of these two theorems is due chiefly to Le Chatelier, who showed that they may be regarded as consequences of the general law of action and reaction. For this reason they are generally regarded as special cases of the more general law, known as the _theorem of Le Chatelier_, which may be stated in the words of Ostwald, as follows:[106] _If a system in equilibrium is subjected to a constraint by which the equilibrium is shifted, a reaction takes place which opposes the constraint, _i.e._ one by which its effect is partially destroyed._ This theorem of Le Chatelier is of very great importance, for it applies to all systems and changes of the condition of equilibrium, whether physical or chemical; to vaporization and fusion; to solution and chemical action. In all cases, whenever changes in the external condition of a system in equilibrium are produced, processes also occur within the system which tend to counteract the effect of the external changes. _Changes at the Triple Point._--If now we apply this theorem to equilibria at the triple point S-L-V, and ask what changes will occur in such a system when the external conditions of pressure and temperature are altered, the general answer to the question will be: So long as the three phases are present, no {59} change in the temperature or pressure of the system can occur, but _only changes in the relative amounts of the phases_; that is to say, the effect on the system of change in the external conditions is opposed by the reactions or changes which take place within the system (according to the theorems of van't Hoff and Le Chatelier). We now proceed to discuss what these changes are, and shall consider first the effect of alteration of the temperature at constant volume and constant pressure, and then the effect of alteration of the pressure both when the temperature remains constant and when it varies. When the volume is kept constant, the effect of the addition of heat to a system at the triple point S-L-V differs somewhat according as there is an increase or diminution of volume when the solid passes into the liquid state. In the former and most general case (Fig. 14), addition of heat will cause a certain amount of the solid phase to melt, whereby the heat which is added becomes latent; the temperature of the system therefore does not rise. Since, however, the melting of the solid is accompanied by an increase of volume, whereby an increase of pressure would result, a certain portion of the vapour must condense to liquid, in order that the pressure may remain constant. The total effect of addition of heat, therefore, is to cause both solid and vapour to pass into liquid, _i.e._ there occurs the change S + V --> L. It will, therefore, depend on the relative quantities of solid and vapour, which will disappear first. If the solid disappears first, then we shall pass to the system L-V; if vapour disappears first, we shall obtain the system S-L. Withdrawal of heat causes the reverse change, L --> S + V; at all temperatures below the triple point the liquid is unstable or metastable (p. 30). When fusion is accompanied by a diminution of volume (_e.g._ ice, Fig. 13), then, since the melting of the solid phase would decrease the total volume, _i.e._ would lower the pressure, a certain quantity of the solid must also pass into vapour in order that the pressure may be maintained constant. On addition of heat, therefore, there occurs the reaction S --> L + V; withdrawal of heat causes the reverse change L + V --> S. Above the temperature of the triple point the {60} solid cannot exist; below the triple point both systems, S-L and S-V, can exist, and it will therefore depend on the relative amounts of liquid and vapour which of these two systems is obtained on withdrawing heat from the system at constant volume. The same changes in the phases occur when heat is added or withdrawn at constant pressure, so long as the three phases are present. Continued addition of heat, however, at constant pressure will ultimately cause the formation of the bivariant system vapour alone; continued withdrawal of heat will ultimately cause the formation of solid alone. This will be readily understood from Fig. 15. The dotted line D'OD is a line of constant pressure; on adding heat, the system passes along the line OD into the region of vapour; on heat being withdrawn, the system passes along OD' into the area of solid. [Illustration: FIG. 15.] Similar changes are produced when the volume of the system is altered. Alteration of volume may take place either while transference of heat to or from the system is cut off (adiabatic change), or while such transference may occur (isothermal change). In the latter case, the temperature of the system will remain constant; in the former case, since at the triple point the pressure must be constant so long as the three phases are present, increase of volume must be compensated by the evaporation of liquid. This, however, would cause the temperature to fall (since communication of heat from the outside is supposed to be cut off), and a portion of the liquid must therefore freeze. In this way the latent heat of evaporation is counterbalanced by the latent heat of fusion. As the result of increase of volume, therefore, the process occurs L --> S + V. Diminution of volume, without transference of heat, will bring about the opposite change, S + V --> L. In the former case there is ultimately obtained the univariant system S-V; in the latter case there will be {61} obtained either S-L or L-V according as the vapour or solid phase disappears first. This argument holds good for both types of triple point shown in Figs. 13 and 14 (p. 57). A glance at these figures will show that increase of volume (diminution of pressure) will lead ultimately to the system S-V, for at pressures lower than that of the triple point, the liquid phase cannot exist. Decrease of volume (increase of pressure), on the other hand, will lead either to the system S-L or L-V, because these systems can exist at pressures higher than that of the triple point. If the vapour phase disappears and we pass to the curve S-L, continued diminution of volume will be accompanied by a fall in temperature in the case of systems of the first type (Fig. 13), and by a rise in temperature in the case of systems of the second type (Fig. 14). [Illustration: FIG. 16.] [Illustration: FIG. 17.] Lastly, if the temperature is maintained constant, _i.e._ if heat can pass into or out of the system, then on changing the volume the same changes in the phases will take place as described above until one of the phases has disappeared. Continued increase of volume (decrease of pressure) will then cause the disappearance of a second phase, the system passing along the dotted line OE' (Figs. 16, 17), so that ultimately there remains only the vapour phase. Conversely, diminution of volume (increase of pressure) will ultimately lead either to solid (Fig. 16) or to liquid alone (Fig. 17), the system passing along the dotted line OE. {62} In discussing the alterations which may take place at the triple point with change of temperature and pressure, we have considered only the triple point S-L-V. The same reasoning, however, applies, _mutatis mutandis_, to all other triple points, so that if the specific volumes of the phases are known, and the sign of the heat effects which accompany the transformation of one phase into the other, it is possible to predict (by means of the theorem of Le Chatelier) the changes which will be produced in the system by alteration of the pressure and temperature. In all cases of transformation at the triple point, it should be noted that all _three phases are involved in the change_,[107] and not two only; the fact that in the case, say, of the transformation from solid to liquid, or liquid to solid, at the melting point with change of temperature, only these two phases appear to be affected, is due to there generally being a large excess of the vapour phase present and to the prior disappearance therefore of the solid or liquid phase. In the case of triple points at which two solid phases are in equilibrium with liquid, other arrangements of the curves around the triple point are found. It is, however, unnecessary to give a general treatment of these here, since the principles which have been applied to the triple point S-L-V can also be applied to the other triple points.[108] Triple Point Solid--Solid--Vapour.--The triple point solid--solid--vapour is one which is of considerable importance. Examples of such a triple point have already been given in sulphur and tin, and a list of other substances capable of yielding two solid phases is given below. The triple point S-S-V is not precisely the same as the transition point, but is very nearly so. The transition point is the temperature at which the relative stability of the two solid phases undergoes change, when the vapour phase is absent and the pressure is 1 atm.; whereas at the triple point the pressure is that of the system itself. The transition point, therefore, bears the same relation to the triple point S-S-V as the melting point to the triple point S-L-V. {63} In the following table is given a list of the most important polymorphous substances, and the temperatures of the transition point.[109] ------------------------------------+------------- | Substance. | Transition | temperature. ------------------------------------+------------- | Ammonium nitrate-- | [beta]-rhombic --> [alpha]-rhombic | 35° [alpha]-rhombic --> rhombohedral | 83° Rhombohedral --> regular | 125° Mercuric iodide | 126° Potassium nitrate | 129° Silver iodide | 145° Silver nitrate | 160° Sulphur | 95.5° Tetrabrommethane | 46.8° Thallium nitrate-- | Rhombic --> rhombohedral | 80° Rhombohedral --> regular | 142.5° Thallium picrate | 46° Tin | 20° ------------------------------------+------------- Sublimation and Vaporization Curves.--We have already seen, in the case of ice and liquid water, that the vapour pressure increases as the temperature rises, the increase of pressure per degree being greater the higher the temperature. The sublimation and vaporization curves, therefore, are not straight lines, but are bent, the convex side of the curve being towards the temperature axis in the ordinary _pt_-diagram. In the case of sulphur and of tin, we assumed vapour to be given off by the solid substance, although the pressure of the vapour has not hitherto been measured. The assumption, however, is entirely justified, not only on theoretical grounds, but also because the existence of a vapour pressure has been observed in the case of many solid substances at temperatures much below the melting point,[110] and in some cases, _e.g._ camphor,[111] the vapour pressure is considerable. {64} As the result of a large number of determinations, it has been found that all vapour pressure curves have the same general form alluded to above. Attempts have also been made to obtain a general expression for the quantitative changes in the vapour pressure with change of temperature, but without success. Nevertheless, the _qualitative_ changes, or the general direction of the curves, can be predicted by means of the theorem of Le Chatelier. As we have already learned (p. 16), the Phase Rule takes no account of the molecular complexity of the substances participating in an equilibrium. A dissociating substance, therefore, in contact with its vaporous products of dissociation (_e.g._ ammonium chloride in contact with ammonia and hydrogen chloride), will likewise constitute a univariant system of one component, provided the composition of the vapour phase as a whole is the same as that of the solid or liquid phase (p. 13). For all such substances, therefore, the conditions of equilibrium will be represented by a curve of the same general form as the vapour pressure curve of a non-dissociating substance.[112] The same behaviour is also found in the case of substances which polymerize on passing into the solid or liquid state (_e.g._ red phosphorus). Where such changes in the molecular state occur, however, the time required for equilibrium to be established is, as a rule, greater than when the molecular state is the same in both phases. From an examination of Figs. 13 and 14, it will be easy to predict the effect of change of pressure and temperature on the univariant systems S-V or L-V. If the volume is kept constant, addition of heat will cause an increase of pressure, the system S-V moving along the curve AO until at the triple point the liquid phase is formed, and the system L-V moving along the curve OB; so long as two phases are present, the condition of the system must be represented by these two curves. Conversely, withdrawal of heat will cause condensation of vapour, and therefore diminution of pressure; the system will therefore move along the vaporization or sublimation curve to lower temperatures and pressures, so long as the system remains univariant. {65} If transference of heat to or from the system is prevented, increase of volume (diminution of pressure) will cause the system L-V to pass along the curve BO; liquid will pass into vapour and the temperature will fall.[113] At O solid may appear, and the temperature of the system will then remain constant until the liquid phase has disappeared (p. 57); the system will then follow the curve OA until the solid phase disappears, and we are ultimately left with vapour. On the other hand, diminution of volume (increase of pressure) will cause condensation of vapour, and the system S-V will pass along the curve AO to higher temperatures and pressures; at O the solid will melt, and the system will ultimately pass to the curve OB or to OC (p. 57). Addition or withdrawal of heat at constant pressure, and increase or diminution of the pressure at constant temperature, will cause the system to pass along lines parallel to the temperature and the pressure axis respectively; the working out of these changes may be left to the reader, guided by what has been said on pp. 60 and 61. The sublimation curve of all substances, so far as yet found, has its upper limit at the melting point (triple point), although the possibility of the existence of a superheated solid is not excluded. The lower limit is, theoretically at least, at the absolute zero, provided no new phase, _e.g._ a different crystalline modification, is formed. If the sublimation pressure of a substance is greater than the atmospheric pressure at any temperature below the point of fusion, then the substance will _sublime without melting_ when heated in an open vessel; and fusion will be possible only at a pressure higher than the atmospheric. This is found, for example, in the case of red phosphorus (p. 47). If, however, the sublimation pressure of a substance at its triple point S-L-V is less than one atmosphere, then the substance will melt when heated in an open vessel. In the case of the vaporization curve, the upper limit lies at the critical point where the liquid ceases to exist;[114] the {66} lower limit is determined by the range of the metastable state of the supercooled liquid. The interpolation and extrapolation of vapour-pressure curves is rendered very easy by means of a relationship which Ramsay and Young[115] found to exist between the vapour-pressure curves of different substances. It was observed that in the case of closely related substances, the ratio of the absolute temperatures corresponding to equal vapour pressures is constant, _i.e._ T_{1}/T'_{1} = T_{2}/T'_{2}. When the two substances are not closely related, it was found that the relationship could be expressed by the equation T_{1}/T'_{1} = T_{2}/T'_{2} + _c_(_t_' - _t_) where _c_ is a constant having a small positive or negative value, and _t_' and _t_ are the temperatures at which one of the substances has the two values of the vapour pressure in question. By means of this equation, if the vapour-pressure curve of one substance is known, the vapour-pressure curve of any other substance can be calculated from the values at any two temperatures of the vapour pressure of that substance. Fusion Curve--Transition Curve.--The fusion curve represents the conditions of equilibrium between the solid and liquid phase; it shows the change of the melting point of a substance with change of pressure. As shown in Figs. 13 and 14, the fusion curve is inclined either towards the pressure axis or away from it; that is, increase of pressure can either lower or raise the melting point. It is easy to predict in a qualitative manner the different effect of pressure on the melting point in the two cases mentioned, if we consider the matter in the light of the theorem of Le Chatelier (p. 58). Water, on passing into ice, expands; therefore, if the pressure on the system ice--water be increased, a reaction will take place which is accompanied by a diminution in volume, _i.e._ the ice will melt. Consequently, a lower temperature will be required in order to counteract the effect of increase of pressure; or, in other words, the melting point will {67} be lowered by pressure.[116] In the second case, the passage of the liquid to the solid state is accompanied by a diminution of volume; the effect of increase of pressure will therefore be the reverse of that in the previous case. If the value of the heat of fusion and the alteration of volume accompanying the change of state are known, it is possible to calculate _quantitatively_ the effect of pressure.[117] We have already seen (p. 25) that the effect of pressure on the melting point of a substance was predicted as the result of theoretical considerations, and was first proved experimentally in the case of ice. Soon after, Bunsen[118] showed that the melting point of other substances is also affected by pressure; and in more recent years, ample experimental proof of the change of the melting point with the pressure has been obtained. The change of the melting point is, however, small; as a rule, increase of pressure by 1 atm. changes the melting point by about 0.03°, but in the case of water the change is much less (0.0076°), and in the case of camphor much more (0.13°). In other words, if we take the mean case, an increase of pressure of more than 30 atm. is required to produce a change in the melting point of 1°. Investigations which were made of the influence of pressure on the melting-point, showed that up to pressures of several hundred atmospheres the fusion curve is a straight line.[119] Tammann[120] has, however, found that on increasing the pressure the fusion curve no longer remains straight, but bends towards the pressure axis, so that, on sufficiently increasing the pressure, a maximum temperature might at length be reached. This maximum has, so far, however, not been attained, although the melting point curves of various substances have been studied up to pressures of 4500 atm. This is to be accounted for partly {68} by the fact that the probable maximum temperature in the case of most substances lies at very great pressures, and also by the fact that other solid phases make their appearance, as, for example, in the case of ice (p. 32). As to the upper limit of the fusion curve, the view has been expressed[121] that just as in the case of liquid and vapour, so also in the case of solid and liquid, there exists a critical point at which the solid and the liquid phase become identical. Experimental evidence, however, does not appear to favour this view.[122] The _transition point_, like the melting point, is also influenced by the pressure, and in this case also it is found that pressure may either raise or lower the transition point, so that the transition curve may be inclined either away from or towards the pressure axis. The direction of the transition curve can also be predicted if the change of volume accompanying the passage of one form into the other is known. In the case of sulphur, we saw that the transition point is raised by increase of pressure; in the case of the transition of rhombohedral into [alpha]-rhombic form of ammonium nitrate, however, the transition point is lowered by pressure, as shown by the following table.[123] -------------+---------- | Temperature. | Pressure. -------------+---------- | 85.85° | 1 atm. 84.38° | 100 " 83.03° | 200 " 82.29° | 250 " -------------+---------- So far as investigations have been carried out, it appears that in most cases the transition curve is practically a straight line. It has, however, been found in the case of Glauber's salt, that with increase of pressure the transition curve passes through a point of maximum temperature, and exhibits, therefore, a form similar to that assumed by Tammann for the fusion curve.[124] {69} Suspended Transformation. Metastable Equilibria.--Hitherto we have considered only systems in stable equilibrium. We have, however, already seen, in the case of water, that on cooling the liquid down to the triple point, solidification did not necessarily take place, although the conditions were such as to allow of its formation. Similarly, we saw that rhombic sulphur can be heated above the transition point, and monoclinic sulphur can be obtained at temperatures below the transition point, although in both cases transformation into a more stable form is possible; the system becomes metastable. The same reluctance to form a new phase is observed also in the phenomena of superheating of liquids, and in the "hanging" of mercury in barometers, in which case the vapour phase is not formed. In general, then, we may say that _a new phase will not necessarily be formed immediately the system passes into such a condition that the existence of that phase is possible_; but rather, instead of the system undergoing transformation so as to pass into the most stable condition under the existing pressure and temperature, this transformation will be "suspended" or delayed, and the system will become metastable. Only in the case of the formation of the liquid from the solid phase, in a one-component system, has this reluctance to form a new phase not been observed. _To ensure the formation of the new phase, it is necessary to have that phase present._ The presence of the solid phase will prevent the supercooling of the liquid; and the presence of the vapour phase will prevent the superheating of the liquid. However, even in the presence of the more stable phase, transformation of the metastable phase occurs with very varying velocity; in some cases so quickly as to appear almost instantaneous; while in other cases, the change takes place so slowly as to require hundreds of years for its achievement. It is this slow rate of transformation that renders the existence of metastable forms possible, when in contact with the more stable phase. Thus, for example, although calcite is the most stable form of calcium carbonate at the ordinary temperature,[125] the less stable {70} modification, aragonite, nevertheless exists under the ordinary conditions in an apparently very stable state. As to the amount of the new phase required to bring about the transformation of the metastable phase, quantitative measurements have been carried out only in the case of the initiation of crystallization in a supercooled liquid.[126] As the result of these investigations, it was found that, in the case of superfused salol, the very small amount of 1 � 10^{-7} gm. of the solid phase was sufficient to induce crystallization. Crystallization of a supercooled liquid, however, can be initiated only by a "nucleus" of the same substance in the solid state, or, as has also been found, by a nucleus of an isomorphous solid phase; it is not brought about by the presence of any chance solid. Velocity of Transformation.--Attention has already been drawn to the sluggishness with which reciprocal transformation of the polymorphic forms of a substance may occur. In the case of tin, for example, it was found that the white modification, although apparently possessing permanence, is in reality in a metastable state, under the ordinary conditions of temperature and pressure. This great degree of stability is due to the tardiness with which transformation into the grey form occurs. What was found in the case of tin, is met with also in the case of all transformations in the solid state, but the velocity of the change is less in some cases than in others, and appears to decrease with increase of the valency of the element.[127] To this fact van't Hoff attributes the great permanence of many really unstable (or metastable) carbon compounds. Reference has been made to the fact that the velocity of transformation can be accelerated by various means. One of the most important of these is the employment of a liquid which has a solvent action on the solid phases. Just as we have seen that at any given temperature the less stable form has the higher vapour pressure, but that at the transition point the vapour pressure of both forms becomes identical, so also it can be proved theoretically, and be shown experimentally, that {71} at a given temperature the solubility of the less stable form is greater than that of the more stable, but that at the transition point the solubility of the two forms becomes identical.[128] If, then, the two solid phases are brought into contact with a solvent, the less stable phase will dissolve more abundantly than the more stable; the solution will therefore become supersaturated with respect to the latter, which will be deposited. A gradual change of the less stable form, therefore, takes place through the medium of the solvent. In this way the more rapid conversion of white tin into grey in presence of a solution of tin ammonium chloride (p. 42) is to be explained. Although, as a rule, solvents accelerate the transformation of one solid phase into the other, they may also have a retarding influence on the velocity of transformation, as was found by Reinders in the case of mercuric iodide.[129] The velocity of inversion, also, is variously affected by different solvents, and in some cases, at least, it appears to be slower the more viscous the solvent;[130] indeed, Kastle and Reed state that yellow crystals of mercuric iodide, which, ordinarily, change with considerable velocity into the red modification, have been preserved for more than a year under vaseline. Temperature, also, has a very considerable influence on the velocity of transformation. The higher the temperature, and the farther it is removed from the equilibrium point (transition point), the greater is the velocity of change. Above the transition point, these two factors act in the same direction, and the velocity of transformation will therefore go on increasing indefinitely the higher the temperature is raised. Below the transition point, however, the two factors act in opposite directions, and the more the temperature is lowered, the more is the effect of removal from the equilibrium point counteracted. A point will therefore be reached at which the velocity is a maximum. Reduction of the temperature {72} below this point causes a rapid falling off in the velocity of change. The point of maximum velocity, however, is not definite, but may be altered by various causes. Thus, Cohen found that in the case of tin, the point of maximum velocity was altered if the metal had already undergone transformation; and also by the presence of different liquids.[131] Lastly, the presence of small quantities of different substances--catalytic agents or catalyzers--has a great influence on the velocity of transformation. Thus, _e.g._, the conversion of white to red phosphorus is accelerated by the presence of iodine (p. 47). Greater attention, however, has been paid to the study of the velocity of crystallization of a supercooled liquid, the first experiments in this direction having been made by Gernez[132] on the velocity of crystallization of phosphorus and sulphur. Since that time, the velocity of crystallization of other supercooled liquids has been investigated; such as acetic acid and phenol by Moore;[133] supercooled water by Tumlirz;[134] and a number of organic substances by Tammann,[135] Friedländer and Tammann,[136] and by Bogojawlenski.[137] In measuring the velocity of crystallization, the supercooled liquids were contained in narrow glass tubes, and the time required for the crystallization to advance along a certain length of the tube was determined, the velocity being expressed in millimetres per minute. The results which have so far been obtained may be summarized as follows. For any given degree of supercooling of a substance, the velocity of crystallization is constant. As the degree of supercooling increases, the velocity of crystallization also increases, until a certain point is reached at which the velocity is a maximum, which has a definite characteristic value for each substance. This maximum velocity remains constant over a certain range of {73} temperature; thereafter, the velocity diminishes fairly rapidly, and, with sufficient supercooling, may become zero. The liquid then passes into a glassy mass, which will remain (practically) permanent even in contact with the crystalline solid. In ordinary glass we have a familiar example of a liquid which has been cooled to a temperature at which crystallization takes place with very great slowness. If, however, glass is heated, a temperature is reached, much below the melting point of the glass, at which crystallization occurs with appreciable velocity, and we observe the phenomenon of devitrification.[138] When the velocity of crystallization is studied at temperatures above the maximum point, it is found that the velocity is diminished by the addition of foreign substances; and in many cases, indeed, it has been found that the diminution is the same for equimolecular quantities of different substances. It would hence appear possible to utilize this behaviour as a method for determining molecular weights.[139] The rule is, however, by no means a universal one. Thus it has been found by F. Dreyer,[140] in studying the velocity of crystallization of formanilide, that the diminution in the velocity produced by equivalent amounts of different substances is not the same, but that the foreign substances exercise a specific influence. Further, von Pickardt's rule does not hold when the foreign substance forms mixed crystals (Chap. X.) with the crystallizing substance.[141] Law of Successive Reactions.--When sulphur vapour is cooled at the ordinary temperature, it first of all condenses to drops of liquid, which solidify in an amorphous form, and only after some time undergo crystallization; or, when phosphorus vapour is condensed, white phosphorus is first formed, and not the more stable form--red phosphorus. It has also been observed that even at the ordinary temperature (therefore much below the transition point) sulphur may crystallize out from solution in benzene, alcohol, carbon disulphide, and other {74} solvents, in the prismatic form, the less stable prismatic crystals then undergoing transformation into the rhombic form;[142] a similar behaviour has also been observed in the transformation of the monotropic crystalline forms of sulphur.[143] Many other examples might be given. In organic chemistry, for instance, it is often found that when a substance is thrown out of solution, it is first deposited as a liquid, which passes later into the more stable crystalline form. In analysis, also, rapid precipitation from concentrated solution often causes the separation of a less stable and more soluble amorphous form. On account of the great frequency with which the prior formation of the less stable form occurs, Ostwald[144] has put forward the _law of successive reactions_, which states that when a system passes from a less stable condition it does not pass directly into the most stable of the possible states; but into the next more stable, and so step by step into the most stable. This law explains the formation of the metastable forms of monotropic substances, which would otherwise not be obtainable. Although it is not always possible to observe the formation of the least stable form, it should be remembered that that may quite conceivably be due to the great velocity of transformation of the less stable into the more stable form. From what we have learned about the velocity of transformation of metastable phases, we can understand that rapid cooling to a low temperature will tend to preserve the less stable form; and, on account of the influence of temperature in increasing the velocity of change, it can be seen that the formation of the less stable form will be more difficult to observe in superheated than in supercooled systems. The factors, however, which affect the readiness with which {75} the less stable modification is produced, appear to be rather various.[145] Although a number of at least apparent exceptions to Ostwald's law have been found, it may nevertheless be accepted as a very useful generalization which sums up very frequently observed phenomena. * * * * * {76} CHAPTER V SYSTEMS OF TWO COMPONENTS--PHENOMENA OF DISSOCIATION In the preceding pages we have studied the behaviour of systems consisting of only one component, or systems in which all the phases, whether solid, liquid, or vapour, had the same chemical composition (p. 13). In some cases, as, for example, in the case of phosphorus and sulphur, the component was an elementary substance; in other cases, however, _e.g._ water, the component was a compound. The systems which we now proceed to study are characterized by the fact that the different phases have no longer all the same chemical composition, and cannot, therefore, according to definition, be considered as one-component systems. In most cases, little or no difficulty will be experienced in deciding as to the _number_ of the components, if the rules given on pp. 12 and 13 are borne in mind. If the composition of all the phases, each regarded as a whole, is the same, the system is to be regarded as of the first order, or a one-component system; if the composition of the different phases varies, the system must contain more than one component. If, in order to _express_ the composition of all the phases present when the system is in equilibrium, two of the constituents participating in the equilibrium are necessary and sufficient, the system is one of two components. Which two of the possible substances are to be regarded as components will, however, be to a certain extent a matter of arbitrary choice. The principles affecting the choice of components will best be learned by a study of the examples to be discussed in the sequel. {77} Different Systems of Two Components.--Applying the Phase Rule P + F = C + 2 to systems of two components, we see that in order that the system may be invariant, there must be four phases in equilibrium together; two components in three phases constitute a univariant, two components in two phases a bivariant system. In the case of systems of one component, the highest degree of variability found was two (one component in one phase); but, as is evident from the formula, there is a higher degree of freedom possible in the case of two-component systems. Two components existing in only one phase constitute a tervariant system, or a system with three degrees of freedom. In addition to the pressure and temperature, therefore, a third variable factor must be chosen, and as such there is taken the _concentration of the components_. In systems of two components, therefore, not only may there be change of pressure and temperature, as in the case of one-component systems, but the concentration of the components in the different phases may also alter; a variation which did not require to be considered in the case of one-component systems. [Illustration: FIG. 18.] Since a two-component system may undergo three possible {78} independent variations, we should require for the graphic representation of all the possible conditions of equilibrium a system of three co-ordinates in space, three axes being chosen, say, at right angles to one another, and representing the three variables--pressure, temperature, and concentration of components (Fig. 18). A curve (_e.g._ AB) in the plane containing the pressure and temperature axes would then represent the change of pressure with the temperature, the concentration remaining unaltered (_pt_-diagram); one in the plane containing the pressure and concentration axes (_e.g._ AF or DF), the change of pressure with the concentration, the temperature remaining constant (_pc_-diagram), while in the plane containing the concentration and the temperature axes, the simultaneous change of these two factors at constant pressure would be represented (_tc_-diagram). If the points on these three curves are joined together, a surface, ABDE, will be formed, and any line on that surface (_e.g._ FG, or GH, or GI) would represent the simultaneous variation of the three factors--pressure, temperature, concentration. Although we shall at a later point make some use of these solid figures, we shall for the present employ the more readily intelligible plane diagram. The number of different systems which can be formed from two components, as well as the number of the different phenomena which can there be observed, is much greater than in the case of one component. In the case of no two substances, however, have all the possible relationships been studied; so that for the purpose of gaining an insight into the very varied behaviour of two-component systems, a number of different examples will be discussed, each of which will serve to give a picture of some of the relationships. Although the strict classification of the different systems according to the Phase Rule would be based on the variability of the systems, the study of the many different phenomena, and the correlation of the comparatively large number of different systems, will probably be rendered easiest by grouping these different phenomena into classes, each of these classes being studied with the help of one or more typical examples. The order of treatment adopted here is, of course, quite arbitrary; {79} but has been selected from considerations of simplicity and clearness. PHENOMENA OF DISSOCIATION. Bivariant Systems.--As the first examples of the equilibria between a substance and its products of dissociation, we shall consider very briefly those cases in which there is one solid phase in equilibrium with vapour. Reference has already been made to such systems in the case of ammonium chloride. On being heated, ammonium chloride dissociates into ammonia and hydrogen chloride. Since, however, in that case the vapour phase has the same total composition as the solid phase, viz. NH_{3} + HCl = NH_{4}Cl, the system consists of only one component existing in two phases; it is therefore univariant, and to each temperature there will correspond a definite vapour pressure (dissociation pressure).[146] If, however, excess of one of the products of dissociation be added, the system becomes one of two components. In the first place, analysis of each of the two phases yields as the composition of each, solid: NH_{4}Cl (= NH_{3} + HCl); vapour: _m_NH_{3} + _n_HCl. Obviously the smallest number of substances by which the composition of the two phases can be expressed is two; that is, the number of components is two. What, then, are the components? The choice lies between NH_{3} + HCl, NH_{4}Cl + NH_{3}, and NH_{4}Cl + HCl; for the three substances, ammonium chloride, ammonia, hydrogen chloride, are the only ones taking part in the equilibrium of the system. Of these three pairs of components, we should obviously choose as the most simple NH_{3} and HCl, for we can then represent the composition of the two phases as the _sum_ of the two components. If one of the other two possible pairs of components be chosen, we should have to introduce negative quantities of one of the components, in order to represent the composition of the vapour phase. Although it must be allowed that the introduction of negative quantities of a component in such cases is quite permissible, still it will be {80} better to adopt the simpler and more direct choice, whereby the composition of each of the phases is represented as a sum of two components in varying proportions (p. 12). If, therefore, we have a solid substance, such as ammonium chloride, which dissociates on volatilization, and if the products of dissociation are added in varying amounts to the system, we shall have, in the sense of the Phase Rule, a _two-component system existing in two phases_. Such a system will possess two degrees of freedom. At any given temperature, not only the pressure, but also the composition, of the vapour-phase, _i.e._ the concentration of the components, can vary. Only after one of these independent variables, pressure or composition, has been arbitrarily fixed does the system become univariant, and exhibit a definite, constant pressure at a given temperature. Now, although the Phase Rule informs us that at a given temperature change of composition of the vapour phase will be accompanied by change of pressure, it does not cast any light on the relation between these two variables. This relationship, however, can be calculated theoretically by means of the Law of Mass Action.[147] From this we learn that in the case of a substance which dissociates into equivalent quantities of two gases, the product of the partial pressures of the gases is constant at a given temperature. This has been proved experimentally in the case of ammonium hydrosulphide, ammonium cyanide, phosphonium bromide, and other substances.[148] Univariant Systems.--In order that a system of two components shall possess only one degree of freedom, three phases must be present. Of such systems, there are seven possible, viz. S-S-S, S-S-L, S-S-V, L-L-L, S-L-L, L-L-V, S-L-V; S denoting solid, L liquid, and V vapour. In the present chapter we shall consider only the systems S-S-V, _i.e._ those systems in which there are two solid phases and a vapour phase present. {81} As an example of this, we may first consider the well-known case of the dissociation of calcium carbonate. This substance on being heated dissociates into calcium oxide, or quick-lime, and carbon dioxide, as shown by the equation CaCO_{3} <--> CaO + CO_{2}. In accordance with our definition (p. 9), we have here two solid phases, the carbonate and the quick-lime, and one vapour phase; the system is therefore univariant. To each temperature, therefore, there will correspond a certain, definite maximum pressure of carbon dioxide (dissociation pressure), and this will follow the same law as the vapour pressure of a pure liquid (p. 21). More particularly, it will be independent of the relative or absolute amounts of the two solid phases, and of the volume of the vapour phase. If the temperature is maintained constant, increase of volume will cause the dissociation of a further amount of the carbonate until the pressure again reaches its maximum value corresponding to the given temperature. Diminution of volume, on the other hand, will bring about the combination of a certain quantity of the carbon dioxide with the calcium oxide until the pressure again reaches its original value. The dissociation pressure of calcium carbonate was first studied by Debray,[149] but more exact measurements have been made by Le Chatelier,[150] who found the following corresponding values of temperature and pressure:-- -------------+------------------------- | Temperature. | Pressure in cm. mercury. -------------+------------------------- | 547° | 2.7 610° | 4.6 625° | 5.6 740° | 25.5 745° | 28.9 810° | 67.8 812° | 76.3 865° | 133.3 -------------+------------------------- From this table we see that it is only at a temperature of about 812° that the pressure of the carbon dioxide becomes equal to atmospheric pressure. In a vessel open to {82} the air, therefore, the complete decomposition of the calcium carbonate would not take place below this temperature by the mere heating of the carbonate. If, however, the carbon dioxide is removed as quickly as it is formed, say by a current of air, then the entire decomposition can be made to take place at a much lower temperature. For the dissociation equilibrium of the carbonate depends only on the partial pressure of the carbon dioxide, and if this is kept small, then the decomposition can proceed, even at a temperature below that at which the pressure of the carbon dioxide is less than atmospheric pressure. Ammonia Compounds of Metal Chlorides.--Ammonia possesses the property of combining with various substances, chiefly the halides of metals, to form compounds which again yield up the ammonia on being heated. Thus, for example, on passing ammonia over silver chloride, absorption of the gas takes place with formation of the substances AgCl,3NH_{3} and 2AgCl,3NH_{3}, according to the conditions of the experiment. These were the first known substances belonging to this class, and were employed by Faraday in his experiments on the liquefaction of ammonia. Similar compounds have also been obtained by the action of ammonia on silver bromide, iodide, cyanide, and nitrate; and with the halogen compounds of calcium, zinc, and magnesium, as well as with other salts. The behaviour of the ammonia compounds of silver chloride is typical for the compounds of this class, and may be briefly considered here. It was found by Isambert[151] that at temperatures below 15°, silver chloride combined with ammonia to form the compound AgCl,3NH_{3}, while at temperatures above 20° the compound 2AgCl,3NH_{3} was produced. On heating these substances, ammonia was evolved, and the pressure of this gas was found in the case of both compounds to be constant at a given temperature, but was greater in the case of the former than in the case of the latter substance; the pressure, further, was independent of the amount decomposed. The behaviour of these two substances is, therefore, exactly analogous to that shown by calcium carbonate, and the explanation is also similar. {83} Regarded from the point of view of the Phase Rule, we see that we are here dealing with two components, AgCl and NH_{3}. On being heated, the compounds decompose according to the equations:-- 2(AgCl,3NH_{3}) <--> 2AgCl,3NH_{3} + 3NH_{3}. 2AgCl,3NH_{3} <--> 2AgCl + 3NH_{3}. There are, therefore, three phases, viz. AgCl,3NH_{3}; 2AgCl,3NH_{3}, and NH_{3}, in the one case; and 2AgCl,3NH_{3}; AgCl, and NH_{3} in the other. These two systems are therefore univariant, and to each temperature there must correspond a definite pressure of dissociation, quite irrespective of the amounts of the phases present. Similarly, if, at constant temperature, the volume is increased (or if the ammonia which is evolved is pumped off), the pressure will remain constant so long as two solid phases, AgCl,3NH_{3} and 2AgCl,3NH_{3}, are present, _i.e._ until the compound richer in ammonia is completely decomposed, when there will be a sudden fall in the pressure to the value corresponding to the system 2AgCl,3NH_{3}--AgCl--NH_{3}. The pressure will again remain constant at constant temperature, until all the ammonia has been pumped off, when there will again be a sudden fall in the pressure to that of the system formed by solid silver chloride in contact with its vapour. The reverse changes take place when the pressure of the ammonia is gradually increased. If the volume is continuously diminished, the pressure will first increase until it has reached a certain value; the compound 2AgCl,3NH_{3} can then be formed, and the pressure will now remain constant until all the silver chloride has disappeared. The pressure will again rise, until it has reached the value at which the compound AgCl,3NH_{3} can be formed, when it will again remain constant until the complete disappearance of the lower compound. _There is no gradual change of pressure_ on passing from one system to another; but the changes are abrupt, as is demanded by the Phase Rule, and as experiment has conclusively proved.[152] The dissociation pressures of the two compounds of silver {84} chloride and ammonia, as determined by Isambert,[153] are given in the following table:-- -------------------------+------------------------- | AgCl,3NH_{3}. | 2AgCl,3NH_{3}. -------------+-----------+--------------+---------- | | | Temperature. | Pressure. | Temperature. | Pressure. -------------+-----------+--------------+---------- | | | 0° | 29.3 cm. | 20.0° | 9.3 cm. 10.6° | 50.5 " | 31.0° | 12.5 " 17.5° | 65.5 " | 47.0° | 26.8 " 24.0° | 93.7 " | 58.5° | 52.8 " 28.0° | 135.5 " | 69.0° | 78.6 " 34.2° | 171.3 " | 71.5° | 94.6 " 48.5° | 241.4 " | 77.5° | 119.8 " 51.5° | 413.2 " | 83.5° | 159.3 " 54.0° | 464.1 " | 86.1° | 181.3 " | | 88.5° | 201.3 " -------------+-----------+--------------+---------- The conditions for the formation of these two compounds, by passing ammonia over silver chloride, to which reference has already been made, will be readily understood from the above tables. In the case of the triammonia mono-chloride, the dissociation pressure becomes equal to atmospheric pressure at a temperature of about 20°; above this temperature, therefore, it cannot be formed by the action of ammonia at atmospheric pressure on silver chloride. The triammonia dichloride can, however, be formed, for its dissociation pressure at this temperature amounts to only 9 cm., and becomes equal to the atmospheric pressure only at a temperature of about 68°; and this temperature, therefore, constitutes the limit above which no combination can take place between silver chloride and ammonia under atmospheric pressure. Attention may be here drawn to the fact, to which reference will also be made later, that _two_ solid phases are necessary in order that the dissociation pressure at a given temperature shall be definite; _and for the exact definition of this pressure it is necessary to know, not merely what is the substance undergoing dissociation, but also what is the solid product of dissociation formed_. For the definition of the equilibrium, the latter is as important as the former. We shall presently find proof of this in the case {85} of an analogous class of phenomena, viz. the dissociation of salt hydrates. Salts with Water of Crystallization.--In the case of the dehydration of crystalline salts containing water of crystallization, we meet with phenomena which are in all respects similar to those just studied. A salt hydrate on being heated dissociates into a lower hydrate (or anhydrous salt) and water vapour. Since we are dealing with two components--salt and water[154]--in three phases, viz. hydrate _a_, hydrate _b_ (or anhydrous salt), and vapour, the system is univariant, and to each temperature there will correspond a certain, definite vapour pressure (the dissociation pressure), which will be independent of the relative or absolute amounts of the phases, _i.e._ of the amount of hydrate which has already undergone dissociation or dehydration. [Illustration: FIG. 19.] The constancy of the dissociation pressure had been proved experimentally by several investigators[155] a number of years before the theoretical basis for its necessity had been given. In the case of salts capable of forming more than one hydrate, we should obtain a series of dissociation curves (_pt_-curves), as in the case of the different hydrates of copper sulphate. In Fig. 19 there are represented diagrammatically the vapour-pressure curves of the following univariant systems of copper sulphate and water:-- Curve OA: CuSO_{4},5H_{2}O <--> CuSO_{4},3H_{2}O + 2H_{2}O. Curve OB: CuSO_{4},3H_{2}O <--> CuSO_{4},H_{2}O + 2H_{2}O. Curve OC: CuSO_{4},H_{2}O <--> CuSO_{4} + H_{2}O. Let us now follow the changes which take place on {86} increasing the pressure of the aqueous vapour in contact with anhydrous copper sulphate, the temperature being meanwhile maintained constant. If, starting from the point D, we slowly add water vapour to the system, the pressure will gradually rise, without formation of hydrate taking place; for at pressures below the curve OC only the anhydrous salt can exist. At E, however, the hydrate CuSO_{4},H_{2}O will be formed, and as there are now three phases present, viz. CuSO_{4}, CuSO_{4},H_{2}O, and vapour, the system becomes _univariant_; and since the temperature is constant, the pressure must also be constant. Continued addition of vapour will result merely in an increase in the amount of the hydrate, and a decrease in the amount of the anhydrous salt. When the latter has entirely disappeared, _i.e._ has passed into hydrated salt, the system again becomes _bivariant_, and passes along the line EF; the pressure gradually increases, therefore, until at F the hydrate 3H_{2}O is formed, and the system again becomes univariant; the three phases present are CuSO_{4},H_{2}O, CuSO_{4},3H_{2}O, vapour. The pressure will remain constant, therefore, until the hydrate 1H_{2}O has disappeared, when it will again increase till G is reached; here the hydrate 5H_{2}O is formed, and the pressure once more remains constant until the complete disappearance of the hydrate 3H_{2}O has taken place. Conversely, on dehydrating CuSO_{4},5H_{2}O at constant temperature, we should find that the pressure would maintain the value corresponding to the dissociation pressure of the system CuSO_{4},5H_{2}O--CuSO_{4},3H_{2}O--vapour, until all the hydrate 5H_{2}O had disappeared; further removal of water would then cause the pressure to fall _abruptly_ to the pressure of the system CuSO_{4},3H_{2}O--CuSO_{4},H_{2}O--vapour, at which value it would again remain constant until the tri-hydrate had passed into the monohydrate, when a further sudden diminution of the pressure would occur. This behaviour is represented diagrammatically in Fig. 20, the values of the pressure being those at 50°. Efflorescence.--From Fig. 19 we are enabled to predict the conditions under which a given hydrated salt will effloresce when exposed to the air. We have just learned that copper {87} sulphate pentahydrate, for example, will not be formed unless the pressure of the aqueous vapour reaches a certain value; and that conversely, if the vapour pressure falls below the dissociation pressure of the pentahydrate, this salt will undergo dehydration. From this, then, it is evident that a crystalline salt hydrate will effloresce when exposed to the air, if the partial pressure of the water vapour in the air is lower than the dissociation pressure of the hydrate. At the ordinary temperature the dissociation pressure of copper sulphate is less than the pressure of water vapour in the air, and therefore copper sulphate does not effloresce. In the case of sodium sulphate decahydrate, however, the dissociation pressure is greater than the normal vapour pressure in a room, and this salt therefore effloresces. [Illustration: FIG. 20.] Indefiniteness of the Vapour Pressure of a Hydrate.--Reference has already been made (p. 84), in the case of the ammonia compounds of the metal chlorides, to the importance of the solid product of dissociation for the definition of the dissociation pressure. Similarly also in the case of a hydrated salt. A salt hydrate in contact with vapour constitutes only a bivariant system, and can exist therefore at different values of temperature and pressure of vapour, as is seen from the diagram, Fig. 19. Anhydrous copper sulphate can exist in contact with water vapour at all values of temperature and pressure lying in the field below the curve OC; and the hydrate CuSO_{4},H_{2}O can exist in contact with vapour at all values of temperature and pressure in the field BOC. Similarly, each of the other hydrates can exist in contact with vapour at different values of temperature and pressure. From the Phase Rule, however, we learn that, in order that at a given temperature the pressure of a two-component system {88} may be constant, there must be three phases present. Strictly, therefore, we can speak only of the vapour pressure of a _system_; and since, in the cases under discussion, the hydrates dissociate into a solid and a vapour, any statement as to the vapour pressure of a hydrate has a definite meaning _only when the second solid phase produced by the dissociation is given_. The everyday custom of speaking of the vapour pressure of a hydrated salt acquires a meaning only through the assumption, tacitly made, that the second solid phase, or the solid produced by the dehydration of the hydrate, is the _next lower_ hydrate, where more hydrates than one exist. That a hydrate always dissociates in such a way that the next lower hydrate is formed is, however, by no means certain; indeed, cases have been met with where apparently the anhydrous salt, and not the lower hydrate (the existence of which was possible), was produced by the dissociation of the higher hydrate.[156] That a salt hydrate can exhibit different vapour pressures according to the solid product of dissociation, can not only be proved theoretically, but it has also been shown experimentally to be a fact. Thus CaCl_{2},6H_{2}O can dissociate into water vapour and either of two lower hydrates, each containing four molecules of water of crystallization, and designated respectively as CaCl_{2},4H_{2}O[alpha], and CaCl_{2},4H_{2}O[beta]. Roozeboom[157] has shown that the vapour pressure which is obtained differs according to which of these two hydrates is formed, as can be seen from the following figures:-- -------------+---------------------------------------------------------- | Pressure of System. Temperature. +-----------------------------+---------------------------- | CaCl_{2},6H_{2}O; CaCl_{2}, | CaCl_{2},6H_{2}O; CaCl_{2}, | 4H_{2}O[alpha]; vapour. | 4H_{2}O[beta]; vapour. -------------+-----------------------------+---------------------------- -15° | 0.027 cm. | 0.022 cm. 0 | 0.092 " | 0.076 " +10 | 0.192 " | 0.162 " 20 | 0.378 " | 0.315 " 25 | 0.508 " | 0.432 " 29.2 | -- | 0.567 " 29.8 | 0.680 " | -- -------------+-----------------------------+--------------------------- {89} By reason of the non-recognition of the importance of the solid dissociation product for the definition of the dissociation pressure of a salt hydrate, many of the older determinations lose much of their value. Suspended Transformation.--Just as in systems of one component we found that a new phase was not necessarily formed when the conditions for its existence were established, so also we find that even when the vapour pressure is lowered below the dissociation pressure of a system, dissociation does not necessarily occur. This is well known in the case of Glauber's salt, first observed by Faraday. Undamaged crystals of Na_{2}SO_{4},10H_{2}O could be kept unchanged in the open air, although the vapour pressure of the system Na_{2}SO_{4},10H_{2}O--Na_{2}SO_{4}--vapour is greater than the ordinary pressure of aqueous vapour in the air. That is to say, the possibility of the formation of the new phase Na_{2}SO_{4} was given; nevertheless this new phase did not appear, and the system therefore became metastable, or unstable with respect to the anhydrous salt. When, however, a trace of the new phase--the anhydrous salt--was brought in contact with the hydrate, transformation occurred; the hydrate effloresced. The possibility of suspended transformation or the non-formation of the new phases must also be granted in the case where the vapour pressure is raised above that corresponding to the system hydrate--anhydrous salt (or lower hydrate)--vapour; in this case the formation of the higher hydrate becomes a possibility, but not a certainty. Although there is no example of this known in the case of hydrated salts, the suspension of the transformation has been observed in the case of the compounds of ammonia with the metal chlorides (p. 82). Horstmann,[158] for example, found that the pressure of ammonia in contact with 2AgCl,3NH_{3} could be raised to a value higher than the dissociation pressure of AgCl,3NH_{3} without this compound being formed. We see, therefore, that even when the existence of the higher compound in contact with the lower became possible, the higher compound was not immediately formed. Range of Existence of Hydrates.--In Fig. 19 the vapour {90} pressure curves of the different hydrates of copper sulphate are represented as maintaining their relative positions throughout the whole range of temperatures. But this is not necessarily the case. It is possible that at some temperature the vapour pressure curve of a lower hydrate may cut that of a higher hydrate. At temperatures above the point of intersection, the lower hydrate would have a higher vapour pressure than the higher hydrate, and would therefore be metastable with respect to the latter. The range of stable existence of the lower hydrate would therefore end at the point of intersection. This appears to be the case with the two hydrates of sodium sulphate, to which reference will be made later.[159] Constancy of Vapour Pressure and the Formation of Compounds.--We have seen in the case of the salt hydrates that the continued addition of the vapour phase to the system caused an increase in the pressure until at a definite value of the pressure a hydrate is formed; the pressure then becomes constant, and remains so, until one of the solid phases has disappeared. Conversely, on withdrawing the vapour phase, the pressure remained constant so long as any of the dissociating compound was present, independently of the degree of the decomposition (p. 86). This behaviour, now, has been employed for the purpose of determining whether or not definite chemical compounds are formed. Should compounds be formed between the vapour phase and the solid, then, on continued addition or withdrawal of the vapour phase, it will be found that the vapour pressure remains constant for a certain time, and will then suddenly assume a new value, at which it will again remain constant. By this method, Ramsay[160] found that no definite hydrates were formed in the case of ferric and aluminium oxides, but that two are formed in the case of lead oxide, viz. 2PbO,H_{2}O and 3PbO,H_{2}O. The method has also been applied to the investigation of the so-called palladium hydride,[161] and the results obtained appear to show that no compound is formed. Reference will, however, be made to this case later (Chap. X.). {91} Measurement of the Vapour Pressure of Hydrates.--For the purpose of measuring the small pressures exerted by the vapour of salt hydrates, use is very generally made of a differential manometer called the _Bremer-Frowein tensimeter_.[162] This apparatus has the form shown in Fig. 21. It consists of a U-tube, the limbs of which are bent close together, and placed in front of a millimetre scale. The bend of the tube is filled with oil or other suitable liquid, _e.g._ bromonaphthalene. If it is desired to measure the dissociation pressure of, say, a salt hydrate, concentrated sulphuric acid is placed in the flask _e_, and a quantity of the hydrate, well dried and powdered,[163] in the bulb d. The necks of the bulbs _d_ and _e_ are then sealed off. Since, as we have learned, suspended transformation may occur, it is advisable to first partially dehydrate the salt, in order to ensure the presence of the second solid product of dissociation; the value of the dissociation pressure being independent of the degree of dissociation of the hydrate (p. 86). The small bulbs _d_ and _e_ having been filled, the apparatus is placed on its side, so as to allow the liquid to run from the bend of the tube into the bulbs _a_ and _b_; it is then exhausted through _f_ by means of a mercury pump, and sealed off. The apparatus is now placed in a perpendicular position in a thermostat, and kept at constant temperature until equilibrium is established. Since the vapour pressure on the side containing the sulphuric acid may be regarded as zero, the difference in level of the two surfaces of liquid in the U-tube gives directly the dissociation pressure of the hydrate in terms of the particular liquid employed; if the density of the latter is known, the pressure can then be calculated to cm. of mercury. [Illustration: FIG. 21.] * * * * * {92} CHAPTER VI SOLUTIONS Definition.--In all the cases which have been considered in the preceding pages, the different phases--with the exception of the vapour phase--consisted of a single substance of definite composition, or were definite chemical individuals.[164] But this invariability of the composition is by no means imposed by the Phase Rule; on the contrary, we shall find in the examples which we now proceed to study, that the participation of phases of variable composition in the equilibrium of a system is in no way excluded. To such phases of variable composition there is applied the term _solution_. A solution, therefore, is to be defined as _a homogeneous mixture, the composition of which can undergo continuous variation within certain limits_; the limits, namely, of its existence.[165] From this definition we see that the term solution is not restricted to any particular physical state of substances, but includes within its range not only the liquid, but also the gaseous and solid states. We may therefore have solutions of gases in liquids, and of gases in solids; of liquids in liquids or in solids; of solids in liquids, or of solids in solids. Solutions of gases in gases are, of course, also possible; since, however, gas solutions never give rise to more than one phase, their {93} treatment does not come within the scope of the Phase Rule, which deals with heterogeneous equilibria. It should also be emphasized that the definition of solution given above, neither creates nor recognizes any distinction between solvent and dissolved substance (solute); and, indeed, a too persistent use of these terms and the attempt to permanently label the one or other of two components as the solvent or the solute, can only obscure the true relationships and aggravate the difficulty of their interpretation. In all cases it should be remembered that we are dealing with equilibria between two components (we confine our attention in the first instance to such), the solution being constituted of these components in variable and varying amounts. The change from the case where the one component is in great excess (ordinarily called the solvent) to that in which the other component predominates, may be quite gradual, so that it is difficult or impossible to say at what point the one component ceases to be the solvent and becomes the solute. The adoption of this standpoint need not, however, preclude one from employing the conventional terms solvent and solute in ordinary language, especially when reference is made only to some particular condition of equilibrium of the system, when the concentration of the two components in the solution is widely different. SOLUTIONS OF GASES IN LIQUIDS. As the first class of solutions to which we shall turn our attention, there may be chosen the solutions of gases in liquids, or the equilibria between a liquid and a gas. These equilibria really constitute a part of the equilibria to be studied more fully in Chapter VIII.; but since the two-phase systems formed by the solutions of gases in liquids are among the best-known of the two-component systems, a short section may be here allotted to their treatment. When a gas is passed into a liquid, absorption takes place to a greater or less extent, and a point is at length reached when the liquid absorbs no more of the gas; a condition of equilibrium is attained, and the liquid is said to be saturated {94} with the gas. In the light of the Phase Rule, now, such a system is bivariant (two components in two phases); and two of the variable factors, pressure, temperature, and concentration of the components, must therefore be chosen in order that the condition of the system may be defined. If the concentration and the temperature are fixed, then the pressure is also defined; or under given conditions of temperature and pressure, the concentration of the gas in the solution must have a definite value. If, however, the temperature alone is fixed, the concentration and the pressure can alter; a fact so well known that it does not require to be further insisted on. As to the way in which the solubility of a gas in a liquid varies with the pressure, the Phase Rule of course does not state; but guidance on this point is again yielded by the theorem of van't Hoff and Le Chatelier. Since the absorption of a gas is in all cases accompanied by a diminution of the total volume, this process must take place with increase of pressure. This, indeed, is stated in a quantitative manner in the law of Henry, according to which the amount of a gas absorbed is proportional to the pressure. But this law must be modified in the case of gases which are very readily absorbed; the _direction of change_ of concentration with the pressure will, however, still be in accordance with the theorem of Le Chatelier. If, on the other hand, the pressure is fixed, then the concentration will vary with the temperature; and since the absorption of gases is in all cases accompanied by the evolution of heat, the solubility is found, in accordance with the theorem of Le Chatelier, to diminish with rise of temperature. In considering the changes of pressure accompanying changes of concentration and temperature, a distinction must be drawn between the total pressure and the partial pressure of the dissolved gas, in cases where the solvent is volatile. In these cases, the law of Henry applies not to the total pressure of the vapour, but only to the partial pressure of the dissolved gas. {95} SOLUTIONS OF LIQUIDS IN LIQUIDS. When mercury and water are brought together, the two liquids remain side by side without mixing. Strictly speaking, mercury undoubtedly dissolves to a certain extent in the water, and water no doubt dissolves, although to a less extent, in the mercury; the amount of substance passing into solution is, however, so minute, that it may, for all practical purposes, be left out of account, so long as the temperature does not rise much above the ordinary.[166] On the other hand, if alcohol and water be brought together, complete miscibility takes place, and one homogeneous solution is obtained. Whether water be added in increasing quantities to pure alcohol, or pure alcohol be added in increasing amount to water, at no point, at no degree of concentration, is a system obtained containing more than one liquid phase. At the ordinary temperature, water and alcohol can form only two phases, liquid and vapour. If, however, water be added to ether, or if ether be added to water, solution will not occur to an indefinite extent; but a point will be reached when the water or the ether will no longer dissolve more of the other component, and a further addition of water on the one hand, or ether on the other, will cause the formation of two liquid layers, one containing excess of water, the other excess of ether. We shall, therefore, expect to find all grades of miscibility, from almost perfect immiscibility to perfect miscibility, or miscibility in all proportions. In cases of perfect immiscibility, the components do not affect one another, and the system therefore remains unchanged. Such cases do not call for treatment here. We have to concern ourselves here only with the second and third cases, viz. with cases of complete and of partial miscibility. There is no essential difference between the two classes, for, as we shall see, {96} the one passes into the other with change of temperature. The formal separation into two groups is based on the miscibility relations at ordinary temperatures. Partial or Limited Miscibility.--In accordance with the Phase Rule, a pure liquid in contact with its vapour constitutes a univariant system. If, however, a small quantity of a second substance is added, which is capable of dissolving in the first, a bivariant system will be obtained; for there are now two components and, as before, only two phases--the homogeneous liquid solution and the vapour. At constant temperature, therefore, both the composition of the solution and the pressure of the vapour can undergo change; or, if the composition of the solution remains unchanged, the pressure and the temperature can alter. If the second (liquid) component is added in increasing amount, the liquid will at first remain homogeneous, and its composition and pressure will undergo a continuous change; when, however, the concentration has reached a definite value, solution no longer takes place; two liquid phases are produced. Since there are now three phases present, two liquids and vapour, the system is univariant; at a given temperature, therefore, the concentration of the components in the two liquid phases, as well as the vapour pressure, must have definite values. Addition of one of the components, therefore, cannot alter the concentrations or the pressure, but can only cause a change in the relative amounts of the phases. The two liquid phases can be regarded, the one as a solution of the component I. in component II., the other as a solution of component II. in component I. If the pressure is maintained constant, then to each temperature there will correspond a definite concentration of the components in the two liquid phases; and addition of excess of one will merely alter the relative amounts of the two solutions. As the temperature changes, the composition of the two solutions will change, and there will therefore be obtained two solubility curves, one showing the solubility of component I. in component II., the other showing the solubility of component II. in component I. Since heat may be either evolved or absorbed when one liquid dissolves in another, the solubility may diminish or increase {97} with rise of temperature. The two solutions which at a given temperature correspond to one another are known as _conjugate solutions_. The solubility relations of partially miscible liquids have been studied by Guthrie,[167] and more especially by Alexejeff[168] and by Rothmund.[169] A considerable variety of curves have been obtained, and we shall therefore discuss only a few of the different cases which may be taken as typical of the rest. Phenol and Water.--When phenol is added to water at the ordinary temperature, solution takes place, and a homogeneous liquid is produced. When, however, the concentration of the phenol in the solution has risen to about 8 per cent., phenol ceases to be dissolved; and a further addition of it causes the formation of a second liquid phase, which consists of excess of phenol and a small quantity of water. In ordinary language it may be called a solution of water in phenol. If now the temperature is raised, this second liquid phase will disappear, and a further amount of phenol must be added in order to produce a separation of the liquid into two layers. In this way, by increasing the amount of phenol and noting the temperature at which the two layers disappear, the so-called solubility curve of phenol in water can be obtained. By noting the change of the solubility with the temperature in this manner, it is found that at all temperatures below 68.4°, the addition of more than a certain amount of phenol causes the formation of two layers; at temperatures above this, however, two layers cannot be formed, no matter how much phenol is added. At temperatures above 68.4°, therefore, water and phenol are miscible in all proportions. On the other hand, if water is added to phenol at the ordinary temperature, a liquid is produced which consists chiefly of phenol, and on increasing the amount of water beyond a certain point, two layers are formed. On raising the temperature these two layers disappear, and a homogeneous solution is again obtained. The phenomena are exactly analogous to those already described. Since, now, in the second {98} case the concentration of the phenol in the solution gradually decreases, while in the former case it gradually increases, a point must at length be reached at which the composition of the two solutions becomes the same. On mixing the two solutions, therefore, one homogeneous liquid will be obtained. But the point at which two phases become identical is called a critical point, so that, in accordance with this definition, the temperature at which the two solutions of phenol and water become identical may be called the _critical solution temperature_, and the concentration at this point may be called the _critical concentration_. [Illustration: FIG. 22.] From what has been said above, it will be seen that at any temperature below the critical solution temperature, two conjugate solutions containing water and phenol in different concentration can exist together, one containing excess of water, the other excess of phenol. The following table gives the composition of the two layers, and the values are represented graphically in Fig. 22.[170] PHENOL AND WATER. C_{1} is the percentage amount of phenol in the first layer. C_{2} " " " second layer. -------------+--------+-------- Temperature. | C_{1}.| C_{2}. -------------+--------+-------- 20° | 8.5 | 72.2 30° | 8.7 | 69.9 40° | 9.7 | 66.8 50° | 12.0 | 62.7 55° | 14.2 | 60.0 60° | 17.5 | 56.2 65° | 22.7 | 49.7 68.4° | 36.1 | 36.1 -------------+--------+-------- {99} The critical solution temperature for phenol and water is 68.4°, the critical concentration 36.1 per cent. of phenol. At all temperatures above 68.4°, only homogeneous solutions of phenol and water can be obtained; water and phenol are then miscible in all proportions. At the critical solution point the system exists in only two phases--liquid and vapour. It ought, therefore, to possess two degrees of freedom. The restriction is, however, imposed that the composition of the two liquid phases, coexisting at a point infinitely near to the critical point, becomes the same, and this disposes of one of the degrees of freedom. The system is therefore univariant; and at a given temperature the pressure will have a definite value. Conversely, if the pressure is fixed (as is the case when the system is under the pressure of its own vapour), then the temperature will also be fixed; that is, the critical solution temperature has a definite value depending only on the substances. If the vapour phase is omitted, the temperature will alter with the pressure; in this case, however, as in the case of other condensed systems, the effect of pressure is slight. From Fig. 22 it is easy to predict the effect of bringing together water and phenol in any given quantities at any temperature. Start with a solution of phenol and water having the composition represented by the point _x_. If to this solution phenol is added at constant temperature, it will dissolve, and the composition of the solution will gradually change, as shown by the dotted line _xy_. When, however, the concentration has reached the value represented by the point _y_, two liquid layers will be formed, the one solution having the composition represented by _y_, the other that represented by _y'_. The system is now univariant, and on further addition of phenol, the composition of the two liquid phases will remain unchanged, but their relative amounts will alter. The phase richer in phenol will increase in amount; that richer in water will decrease, and ultimately disappear, and there will remain the solution _y'_. Continued addition of phenol will then lead to the point _x'_, there being now only one liquid phase present. Since the critical solution point represents the highest temperature at which two liquid phases consisting of phenol and {100} water can exist together, these two substances can be brought together in any amount whatever at temperatures higher than 68.4°, without the formation of two layers. It will therefore be possible to pass from a system represented by _x_ to one represented by _x'_, without at any time two liquid phases appearing. Starting with _x_, the temperature is first raised above the critical solution temperature; phenol is then added until the concentration reaches the point _x__{2}. On allowing the temperature to fall, the system will then pass into the condition represented by _x'_. [Illustration: FIG. 23.] Methylethylketone and Water.--In the case just described, the solubility of each component in the other increased continuously with the temperature. There are, however, cases where a maximum or minimum of solubility is found, _e.g._ methylethylketone and water. The curve which represents the equilibria between these two substances is given in Fig. 23, the concentration values being contained in the following table:[171]-- METHYLETHYLKETONE AND WATER. --------------+-----------------+----------------- Temperature. | C_{1} per cent. | C_{2} per cent. --------------+-----------------+----------------- -10° | 34.5 | 89.7 +10° | 26.1 | 90.0 30° | 21.9 | 89.9 50° | 17.5 | 89.0 70° | 16.2 | 85.7 90° | 16.1 | 84.8 110° | 17.7 | 80.0 130° | 21.8 | 71.9 140° | 26.0 | 64.0 151.8° | 44.2 | 44.2 --------------+-----------------+----------------- {101} These numbers and Fig. 23 show clearly the occurrence of a minimum in the solubility of the ketone in water, and also a minimum (at about 10°) in the solubility of water in methylethylketone. Minima of solubility have also been found in other cases. [Illustration: FIG. 24.] Triethylamine and Water.--Although in most of the cases studied the solubility of one liquid in another increases with rise of temperature, this is not so in all cases. Thus, at temperatures below 18°, triethylamine and water mix together in all proportions; but, on raising the temperature, the homogeneous solution becomes turbid and separates into two layers. In this case, therefore, the critical solution temperature is found in the direction of lower temperature, not in the direction of higher.[172] This behaviour is clearly shown by the graphic representation in Fig. 24, and also by the numbers in the following table:-- TRIETHYLAMINE AND WATER. -------------+-----------------+---------------- Temperature. | C_{1} per cent. | C_{2} per cent. -------------+-----------------+---------------- 70° | 1.6 | -- 50° | 2.9 | -- 30° | 5.6 | 96 25° | 7.3 | 95.5 20° | 15.5 | 73 ±18.5° | ±30 | ±30 -------------+-----------------+---------------- General Form of Concentration-Temperature Curve.--From the preceding figures it will be seen that the general {102} form of the solubility curve is somewhat parabolic in shape; in the case of triethylamine and water, the closed end of the curve is very flat. Since for all liquids there is a point (critical point) at which the liquid and gaseous states become identical, and since all gases are miscible in all proportions, it follows that there must be some temperature at which the liquids become perfectly miscible. In the case of triethylamine and water, which has just been considered, there must therefore be an upper critical solution temperature, so that the complete solubility relations would be represented by a closed curve of an ellipsoidal aspect. An example of such a curve is furnished by nicotine and water. At temperatures below 60° and above 210°, nicotine and water mix in all proportions.[173] Although it is possible that this is the general form of the curve for all pairs of liquids, there are as yet insufficient data to prove it. With regard to the closed end of the curve it may be said that it is continuous; the critical solution point is not the intersection of two curves, for such a break in the continuity of the curve could occur only if there were some discontinuity in one of the phases. No such discontinuity exists. The curve is, therefore, not to be considered as two solubility curves cutting at a point; it is a curve of equilibrium between two components, and so long as the phases undergo continuous change, the curve representing the equilibrium must also be continuous. As has already been emphasized, a distinction between solvent and solute is merely conventional (p. 93). Pressure-Concentration Diagram.--In considering the pressure-concentration diagram of a system of two liquid components, a distinction must be drawn between the total pressure of the system and the partial pressures of the components. On studying the total pressure of a system, it is found that two cases can be obtained.[174] So long as there is only one liquid phase, the system is bivariant. The pressure therefore can change with the concentration and the temperature. If the temperature is maintained {103} constant, the pressure will vary only with the concentration, and this variation can therefore be represented by a curve. If, however, two liquid phases are formed, the system becomes univariant: and if one of the variables, say the temperature, is arbitrarily fixed, the system no longer possesses any degree of freedom. _When two liquid phases are formed, therefore, the concentrations and the vapour pressure have definite values, which are maintained so long as the two liquid phases are present_; the temperature being supposed constant. In Fig. 25 is given a diagrammatic representation of the two kinds of pressure-concentration curves which have so far been obtained. In the one case, the vapour pressure of the invariant system (at constant temperature) lies higher than the vapour pressure of either of the pure components; a phenomenon which is very generally found in the case of partially miscible liquids, _e.g._ ether and water.[175] Accordingly, by the addition of water to ether, or of ether to water, there is an increase in the _total_ vapour pressure of the system. [Illustration: FIG. 25.] With regard to the second type, the vapour pressure of the systems with two liquid phases lies between that of the two single components. An example of this is found in sulphur dioxide and water.[176] On adding sulphur dioxide to water there is an increase of the total vapour pressure; but on adding water to liquid sulphur dioxide, the total vapour pressure is diminished. The case that the vapour pressure of the system with two {104} liquid phases is _less_ than that of each of the components is not possible. With regard to the _partial pressure_ of the components, the behaviour is more uniform. The partial pressure of one component is in all cases lowered by the addition of the other component, the diminution being approximately proportional to the amount added. If two liquid phases are present, the partial pressure of the components, as well as the total pressure, is constant, and is the same for both phases. That is to say, in the case of the two liquids, saturated solution of water in ether, and of ether in water, the partial pressure of the ether in the vapour in contact with the one solution is the same as that in the vapour over the other solution.[177] Complete Miscibility.--Although the phenomena of complete miscibility are here treated under a separate heading, it must not be thought that there is any essential difference between those cases where the liquids exhibit limited miscibility and those in which only one homogeneous solution is formed. As has been already pointed out, the solubility relations alter with the temperature; and liquids which at one temperature can dissolve in one another only to a limited extent, are found at some other temperature to possess the property of complete miscibility. Conversely, we may expect that liquids which at one temperature, say at the ordinary temperature, are miscible in all proportions, will be found at some other temperature to be only partially miscible. Thus, for example, it was found by Guthrie that ethyl alcohol and carbon disulphide, which are miscible in all proportions at the ordinary temperature, possess only limited miscibility at temperatures below -14.4°.[178] Nevertheless, it is doubtful if the critical solution temperature is in all cases experimentally realizable. Pressure-Concentration Diagram.--Since, in the cases of complete miscibility of two liquid components, there are never more than two phases present, the system must always be bivariant; and two of the variables pressure, temperature or concentration of the components, must be arbitrarily chosen {105} before the system becomes defined. For this reason the Phase Rule affords only a slight guidance in the study of such equilibria; and we shall therefore not enter in detail into the behaviour of these homogeneous mixtures. All that the Phase Rule can tell us in connection with these solutions, is that at constant temperature the vapour pressure of the solution varies with the composition of the liquid phase; and if the composition of the liquid phase remains unchanged, the pressure also must remain unchanged. This constancy of composition is exhibited not only by pure liquids, but also by liquid solutions in all cases where the vapour pressure of the solution reaches a maximum or minimum value. This is the case, for example, with mixtures of constant boiling point.[179] * * * * * {106} CHAPTER VII SOLUTIONS OF SOLIDS IN LIQUIDS, ONLY ONE OF THE COMPONENTS BEING VOLATILE General.--When a solid is brought into contact with a liquid in which it can dissolve, a certain amount of it passes into solution; and the process continues until the concentration reaches a definite value independent of the amount of solid present. A condition of equilibrium is established between the solid and the solution; the solution becomes _saturated_. Since the number of components is two, and the number of phases three, viz. solid, liquid solution, vapour, the system is univariant. If, therefore, one of the factors, pressure, temperature, or concentration of the components (in the solution[180]), is arbitrarily fixed, the state of the system becomes perfectly defined. Thus, at any given temperature, the vapour pressure of the system and the concentration of the components have a definite value. If the temperature is altered, the vapour pressure and also, in general, the concentration will undergo change. Likewise, if the pressure varies, while the system is isolated so that no heat can pass between it and its surroundings, the concentration and the temperature must also undergo variation until they attain values corresponding to the particular pressure. That the temperature has an influence, sometimes a very considerable influence, on the amount of substance passing into solution, is sufficiently well known; the effect of pressure, although less apparent, is no less certain. If at any given temperature the volume of the vapour phase is diminished, {107} vapour will condense to liquid, in order that the pressure may remain constant, and so much of the solid will pass into solution that the concentration may remain unchanged; for, so long as the three phases are present, the state of the system cannot alter. If, however, one of the phases, _e.g._ the vapour phase, disappears, the system becomes bivariant; at any given temperature, therefore, there may be different values of concentration and pressure. The direction in which change of concentration will occur with change of pressure can be predicted by means of the theorem of Le Chatelier, if it is known whether solution is accompanied by increase or diminution of the total volume. If diminution of the total volume of the system occurs on solution, increase of pressure will increase the solubility; in the reverse case, increase of pressure will diminish the solubility. This conclusion has also been verified by experiment, as is shown by the following figures.[181] --------------------------------------------------------------- |Change of | Solubility (at 18°) (grams salt |volume by | in 1 gram of solution). |dissolving 1 gm.|--------------------------- Salt. |of salt in the | | |saturated | Pressure | Pressure |solution. | = 1 atm. | = 500 atm. ------------------+----------------+----------+---------------- Sodium chloride | -0.07 | 0.264 | 0.270 Ammonium chloride | +0.10 | 0.272 | 0.258 Alum | -0.067 | 0.115 | 0.142 | | |(_p_ = 400 atm.) ------------------------------------------------------------- As can be seen, a large increase of the pressure brings about a no more than appreciable alteration of the solubility; a result which is due, as in the case of the alteration of the fusion point with the pressure, to the small change in volume accompanying solution or increase of pressure. For all practical purposes, therefore, the solubility as determined under atmospheric pressure may be taken as equal to the true {108} solubility, that is, the solubility when the system is under the pressure of its own vapour. The Saturated Solution.--From what has been said above, it will be seen that the condition of saturation of a solution can be defined only with respect to a certain solid phase; if no solid is present, the system is undefined, for it then consists of only two phases, and is therefore bivariant. Under such circumstances not only can there be at one given temperature solutions of different concentration, all containing less of one of the components than when that component is present in the solid form, but there can also exist solutions containing more of that component than corresponds to the equilibrium when the solid is present. In the former case the solutions are _unsaturated_, in the latter case they are _supersaturated with respect to a certain solid phase_; in themselves, the solutions are stable, and are neither unsaturated nor supersaturated. Further, if the solid substance can exist in different allotropic modifications, the particular form of the substance which is in equilibrium with the solution must be known, in order that the statement of the solubility may be definite; for each form has its own solubility, and, as we shall see presently, the less stable form has the greater solubility (cf. p. 47). In all determinations of the solubility, therefore, not only must the concentration of the components in the solution be determined, but equal importance should be attached to the characterisation of the solid phase present. In this connection, also, one other point may be emphasised. For the production of the equilibrium between a solid and a liquid, time is necessary, and this time not only varies with the state of division of the solid and the efficiency of the stirring, but is also dependent on the nature of the substance.[182] Considerable care must therefore be taken that sufficient time is allowed for equilibrium to be established. Such care is more especially needful when changes may occur in the solid phase, and neglect of it has greatly diminished the value of many of the older determinations of solubility. Form of the Solubility Curve.--The solubility curve--that {109} is, the curve representing the change of concentration of the components in the solution with the temperature--differs markedly from the curve of vapour pressure (p. 63), in that it possesses no general form, but may vary in the most diverse manner. Not only may the curve have an almost straight and horizontal course, or slope or curve upwards at varying angles; but it may even slope downwards, corresponding to a decrease in the solubility with rise of temperature; may exhibit maxima or minima of solubility, or may, as in the case of some hydrated salts, pass through a point of maximum temperature. In the latter case the salt may possess two values of solubility at the same temperature. We shall consider these cases in the following chapter. [Illustration: FIG. 26.] The great variety of form shown by solubility curves is at once apparent from Fig. 26, in which the solubility curves of various substances (not, however, drawn to scale) are reproduced.[183] Varied as is the form of the solubility curve, its _direction_, nevertheless, can be predicted by means of the theorem of van't Hoff and Le Chatelier; for in accordance with that theorem (p. 57) increase of solubility with the temperature must occur in those cases where the process of solution is accompanied by an _absorption_ of heat; and a decrease in the solubility with rise of temperature will be found in cases where solution occurs with _evolution_ of heat. Where there is no heat effect accompanying solution, {110} change of temperature will be without influence on the solubility; and if the sign of the heat of solution changes, the direction of the solubility curve must also change, _i.e._ must show a maximum or minimum point. This has in all cases been verified by experiment.[184] In applying the theorem of Le Chatelier to the course of the solubility curve, it should be noted that by heat of solution there is meant, not the heat effect produced on dissolving the salt in a large amount of solvent (which is the usual signification of the expression), but the heat which is absorbed or evolved when the salt is dissolved in the almost saturated solution (the so-called last heat of solution). Not only does the heat effect in the two cases have a different value, but it may even have a different sign. A striking example of this is afforded by cupric chloride, as the following figures show:[185]-- ----------------------------------------------------------- Number of gram-molecules of | CuCl_{2}, 2H_{2}O dissolved in 198 | Heat effect. gram-molecules of water. | -----------------------------------+----------------------- 1 | +37 K 2.02 | +66 " 4.15 | +105 " 7.07 | +117 " 9.95 | +117 " 11 | +91 " 18.8 | -10 " 19.6 | -31 " 24.75 | -198 " ------------------------------------------------------------ In the above table the positive sign indicates evolution of heat, the negative sign, absorption of heat; and the values of the heat effect are expressed in centuple calories. Judging from the heat effect produced on dissolving cupric chloride in a large bulk of water, we should predict that the solubility of that salt would diminish with rise of temperature; as a matter of fact, it increases. This is in accordance with the fact that {111} the last heat of solution is _negative_ (as expressed above), _i.e._ solution of the salt in the almost saturated solution is accompanied by absorption of heat. We are led to expect this from the fact that the heat of solution changes sign from positive to negative as the concentration increases; experiment also showed it to be the case. Despite its many forms, it should be particularly noted that the solubility curve of any substance is _continuous_, so long as the solid phase, or solid substance in contact with the solution, remains unchanged. If any "break" or discontinuous change in the direction of the curve occurs, it is a sign that the _solid phase has undergone alteration_. Conversely, if it is known that a change takes place in the solid phase, a break in the solubility curve can be predicted. We shall presently meet with examples of this.[186] A.--ANHYDROUS SALT AND WATER. The Solubility Curve.--In studying the equilibria in those systems of two components in which the liquid phase is a solution or phase of varying composition, we shall in the present chapter limit the discussion to those cases where no compounds are formed, but where the components crystallise out in the pure state. Since some of the best-known examples of such systems are yielded by the solutions of anhydrous salts in water, we shall first of all briefly consider some of the results which have been obtained with them. For the most part the solubility curves have been studied only at temperatures lying between 0° and 100°, the solid phase in contact with the solution being the anhydrous salt. For the representation of these equilibria, the concentration-temperature {112} diagram is employed, the concentration being expressed as the number of grams of the salt dissolved in 100 grams of water, or as the number of gram-molecules of salt in 100 gram-molecules of water. The curves thus obtained exhibit the different forms to which reference has already been made. So long as the salt remains unchanged the curve will be continuous, but if the salt alters its form, then the solubility curve will show a break. [Illustration: FIG. 27.] Now, we have already seen in Chapter III. that certain substances are capable of existing in various crystalline forms, and these forms are so related to one another that at a given temperature the relative stability of each pair of polymorphic forms undergoes change. Since each crystalline variety of a substance must have its own solubility, there must be a break in the solubility curve at the temperature of transition of the two enantiotropic forms. At this point the two solubility curves must cut, for since the two forms are in equilibrium with respect to their vapour, they must also be in equilibrium with respect to their solutions. From the table on p. 63 it is seen that potassium nitrate, ammonium nitrate, silver nitrate, thallium nitrate, thallium picrate, are capable of existing in two or more different enantiotropic crystalline forms, the range of stability of these forms being limited by definite temperatures (transition temperature). Since the transition point is not altered by a solvent (provided the latter is not absorbed by the solid phase), we should find on studying the solubility of these substances in water that the solubility curve would exhibit a change in direction at the temperature of transition. As a matter of fact this has been verified, more especially in the case of ammonium nitrate[187] {113} and thallium picrate.[188] The following table contains the values of the solubility of ammonium nitrate obtained by Müller and Kaufmann, the solubility being expressed in gram-molecules NH_{4}NO_{3} in 100 gram-molecules of water. In Fig. 27 these results are represented graphically. The equilibrium point was approached both from the side of unsaturation and of supersaturation, and the condition of equilibrium was controlled by determinations of the density of the solution. SOLUBILITY OF AMMONIUM NITRATE. ------------------------------------------------------------ Temperature. | Solubility. | Temperature. | Solubility. --------------+-------------+--------------+---------------- 12.2° | 34.50 | 32.7° | 57.90 20.2° | 43.30 | 34.0° | 58.89 25.05° | 48.19 | 35.0° | 59.80 28.0° | 51.86 | 36.0° | 61.00 30.0° | 54.40 | 37.5° | 62.90 30.2° | 54.61 | 38.0° | 63.60 31.9° | 57.20 | 39.0° | 65.09 32.1° | 57.60 | 40.0° | 66.80 ------------------------------------------------------------ From the graphic representation of the solubility given in Fig. 27, there is seen to be a distinct change in the direction of the curve at a temperature of 32°; and this break in the curve corresponds to the transition of the [beta]-rhombic into the [alpha]-rhombic form of ammonium nitrate (p. 63). Suspended Transformation and Supersaturation.--As has already been learned, the transformation of the one crystalline form into the other does not necessarily take place immediately the transition point has been passed; and it has therefore been found possible in a number of cases to follow the solubility curve of a given crystalline form beyond the point at which it ceases to be the most stable modification. Now, it will be readily seen from Fig. 27 that if the two solubility curves be prolonged beyond the point of intersection, the solubility of the less stable form is greater than that of the more stable. A solution, therefore, which is saturated with respect to the less stable form, _i.e._ which is in equilibrium with that form, is _supersaturated with respect to the more stable modification_. If, {114} therefore, a small quantity of the more stable form is introduced into the solution, the latter must deposit such an amount of the more stable form that the concentration of the solution corresponds to the solubility of the stable form at the particular temperature. Since, however, the solution is now _unsaturated_ with respect to the less stable variety, the latter, if present, must pass into solution; and the two processes, deposition of the stable and solution of the metastable form, must go on until the latter form has entirely disappeared and a saturated solution of the stable form is obtained. There will thus be a conversion, through the medium of the solvent, of the less stable into the more stable modification. This behaviour is of practical importance in the determination of transition points (_v._ Appendix). From the above discussion it will be seen how important is the statement of the solid phase for the definition of saturation and supersaturation.[189] Solubility Curve at Higher Temperatures.--On passing to the consideration of the solubility curves at higher temperatures, two chief cases must be distinguished. (1) The two components in the fused state can mix in all proportions. (2) The two components in the fused state cannot mix in all proportions. 1. _Complete Miscibility of the Fused Components._ [Illustration: FIG. 28.] The best example of this which has been studied, so far as anhydrous salts and water are concerned, is that of silver nitrate and water. The solubility of this salt at temperatures {115} above 100° has been studied chiefly by Etard[190] and by Tilden and Shenstone.[191] The values obtained by Etard are given in the following table, and represented graphically in Fig. 28. SOLUBILITY OF SILVER NITRATE. --------------------------------------------------- Temperature. |Parts of dry salt in 100 parts | of solution. --------------------+------------------------------ -7° | 46.2 -1° | 52.1 +5° | 56.3 10° | 61.2 20° | 67.8 40.5° | 76.8 73° | 84.0 135° | 92.8 182° | 96.9 --------------------------------------------------- In this figure the composition of the solution is expressed in parts of silver nitrate in 100 parts by weight of the solution, so that 100 per cent. represents pure silver nitrate. As can be seen, the solubility increases with the temperature. At a temperature of about 160° there should be a break in the curve due to change of crystalline form (p. 63). Such a change in the direction of the solubility curve, however, does not in any way alter the essential nature of the relationships discussed here, and may for the present be left out of account. On following the solubility curve of silver nitrate to higher temperatures, therefore, the concentration of silver nitrate in the solution gradually increases, until at last, at a temperature of 208°,[192] the melting point of pure silver nitrate is reached, and the concentration of the water has become zero. The curve throughout its whole extent represents the equilibrium between silver nitrate, solution, and vapour. Conversely, starting with pure silver nitrate in contact with the fused salt, addition of water will lower the melting point, _i.e._ will lower the temperature at which the solid salt can exist in contact with the liquid; {116} and the depression will be all the greater the larger the amount of water added. As the concentration of the water in the liquid phase is increased, therefore, the system will pass back along the curve from higher to lower temperatures, and from greater to smaller concentrations of silver nitrate in the liquid phase. The curve in Fig. 28 may, therefore, be regarded either as the solubility curve of silver nitrate in water, or as the freezing point curve for silver nitrate in contact with a solution consisting of that salt and water. As the temperature of the saturated solution falls, silver nitrate is deposited, and on lowering the temperature sufficiently a point will at last be reached at which ice also begins to separate out. Since there are now four phases co-existing, viz. silver nitrate, ice, solution, vapour, the system is invariant, and the point is a _quadruple point_. This quadruple point, therefore, forms the lower limit of the solubility curve of silver nitrate. Below this point the solution becomes metastable. Ice as Solid Phase.--Ice melts or is in equilibrium with water at a temperature of 0°. The melting point, will, however, be lowered by the solution of silver nitrate in the water; and the greater the concentration of the salt in the solution the greater will be the depression of the temperature of equilibrium. On continuing the addition of silver nitrate, a point will at length be reached at which the salt is no longer dissolved, but remains in the solid form along with the ice. We again obtain, therefore, the invariant system ice--salt--solution--vapour. The temperature at which this invariant system can exist has been found by Middelberg[193] to be -7.3°, the solution at this point containing 47.1 per cent. of silver nitrate. The same general behaviour will be found in the case of all other systems of two components belonging to this class; that is, in the case of systems from which the components crystallise out in the pure state, and in which the fused components are miscible in all proportions. In all such cases, therefore, the solubility curves (curves of equilibrium) can be represented diagrammatically as in Fig. 29. In this figure OA represents the solubility curve of the salt, and OB the freezing {117} point curve of ice. O is the quadruple point at which the invariant system exists, and may be regarded as the point of intersection of the solubility curve with the freezing-point curve. Since this point is fixed, the condition of the system as regards temperature, vapour pressure, and concentration of the components (or composition of the solution), is perfectly definite. From the way, also, in which the condition is attained, it is evident that the quadruple point is the lowest temperature that can be obtained with mixtures of the two components in presence of vapour. It is known as the _cryohydric point_, or, generally, the _eutectic point_.[194] [Illustration: FIG. 29.] Cryohydrates.[195]--On cooling a solution of common salt in water to a temperature of -3°, Guthrie observed that the hydrate NaCl,2H_{2}O separated out. This salt continued to be deposited until at a temperature of -22° opaque crystals made their appearance, and the liquid passed into the solid state without change of temperature. A similar behaviour was found by Guthrie in the case of a large number of other salts, a temperature below that of the melting point of ice being reached at which on continued withdrawal of heat, the solution solidified at a constant temperature. When the system had attained this minimum temperature, it was found that the composition of the solid and the liquid phases was the same, and remained unchanged throughout the period of solidification. This is shown by the following figures, which give the composition of different samples of the solid phase deposited from the solution at constant temperature.[196] {118} --------------------------------- No. | Temperature of | NaCl. | solidification. | Per cent. ----|-----------------|---------- 1 | -21° to -22° | 23.72 2 | -22° | 23.66 3 | -22° | 23.73 4 | -23° | 23.82 5 | -23° | 23.34 6 | -23° | 23.35 --------------------------------- Mean 23.6 --------------------------------- Conversely, a mixture of ice and salt containing 23.6 per cent. of sodium chloride will melt at a definite and constant temperature, and exhibit, therefore, a behaviour supposed to be characteristic of a pure chemical compound. This, then, combined with the fact that the solid which was deposited was crystalline, and that the same constant temperature was attained, no matter with what proportions of water and salt one started, led Guthrie to the belief that the solids which thus separated at constant temperature were definite chemical compounds, to which he gave the general name _cryohydrate_. A large number of such cryohydrates were prepared and analysed by Guthrie, and a few of these are given in the following table, together with the temperature of the cryohydric point:[197]-- CRYOHYDRATES. ------------------------------------------------------------------ Salt. | Cryohydric point. | Percentage of anhydrous | | salt in the cryohydrate. ------------------------------------------------------------------ Sodium bromide | -24° | 41.33 Sodium chloride | -22° | 23.60 Potassium iodide | -22° | 52.07 Sodium nitrate | -17.5° | 40.80 Ammonium sulphate | -17° | 41.70 Ammonium chloride | -15° | 19.27 Sodium iodide | -15° | 59.45 Potassium bromide | -13° | 32.15 Potassium chloride | -11.4° | 20.03 Magnesium sulphate | -5° | 21.86 Potassium nitrate | -2.6° | 11.20 Sodium sulphate | -0.7° | 4.55 ------------------------------------------------------------------ {119} The chemical individuality of these cryohydrates was, however, called in question by Pfaundler,[198] and disproved by Offer,[199] who showed that in spite of the constancy of the melting point, the cryohydrates had the properties, not of definite chemical compounds, but of mixtures; the arguments given being that the heat of solution and the specific volume are the same for the cryohydrate as for a mixture of ice and salt of the same composition; and it was further shown that the cryohydrate had not a definite crystalline form, but separated out as an opaque mass containing the two components in close juxtaposition. The heterogeneous nature of cryohydrates can also be shown by a microscopical examination. At the cryohydric point, therefore, we are not dealing with a single solid phase, but with two solid phases, ice and salt; the cryohydric point, therefore, as already stated, is a quadruple point and represents an invariant system. Although on cooling a solution to the cryohydric point, separation of ice may occur, it will not necessarily take place; the system may become metastable. Similarly, separation of salt may not take place immediately the cryohydric point is reached. It will, therefore, be possible to follow the curves BO and AO beyond the quadruple point,[200] which is thereby clearly seen to be the point of intersection of the solubility curve of the salt and the freezing-point curve of ice. At this point, also, the curves of the univariant systems ice--salt--vapour and ice--salt--solution intersect. Changes at the Quadruple Point.--Since the invariant system ice--salt--solution--vapour can exist only at a definite temperature, addition or withdrawal of heat must cause the disappearance of one of the phases, whereby the system will become univariant. So long as all four phases are present the temperature, pressure, and concentration of the components in the solution must remain constant. When, therefore, heat is added to or withdrawn from the system, mutually compensatory changes will take place within the system whereby the {120} condition of the latter is preserved. These changes can in all cases be foreseen with the help of the theorem of van't Hoff and Le Chatelier; and, after what was said in Chap. IV., need only be briefly referred to here. In the first place, addition of heat will cause ice to melt, and the concentration of the solution will be thereby altered; salt must therefore dissolve until the original concentration is reached, and the heat of fusion of ice will be counteracted by the heat of solution of the salt. Changes of volume of the solid and liquid phases must also be taken into account; an alteration in the volume of these phases being compensated by condensation or evaporation. All four phases will therefore be involved in the change, and the final state of the system will be dependent on the amounts of the different phases present; the ultimate result of addition or withdrawal of heat or of change of pressure at the quadruple point will be one of the four univariant systems: ice--solution--vapour; salt--solution--vapour; ice--salt--vapour; ice--salt--solution. If the vapour phase disappear, there will be left the univariant system ice--salt--solution, and the temperature at which this system can exist will alter with the pressure. Since in this case the influence of pressure is comparatively slight, the temperature of the quadruple point will differ only slightly from that of the cryohydric point as determined under atmospheric pressure. Freezing Mixtures.--Not only will the composition of a univariant system undergo change when the temperature is varied, but, conversely, if the _composition_ of the system is caused to change, corresponding changes of temperature must ensue. Thus, if ice is added to the univariant system salt--solution--vapour, the ice must melt and the temperature fall; and if sufficient ice is added, the temperature of the cryohydric point must be at length reached, for it is only at this temperature that the four phases ice--salt--solution--vapour can coexist. Or, on the other hand, if salt is added to the system ice--solution--vapour, the concentration of the solution will increase, ice must melt, and the temperature must thereby fall; and this process also will go on until the cryohydric point is reached. In both cases ice melts and there is a change in the {121} composition of the solution; in the former case, salt will be deposited[201] because the solubility diminishes as the temperature falls; in the latter, salt will pass into solution. This process may be accompanied either by an evolution or, more generally, by absorption of heat; in the former case the effect of the addition of ice will be partially counteracted; in the latter case it will be augmented. These principles are made use of in the preparation of _freezing mixtures_. The lowest temperature which can be reached by means of these (under atmospheric pressure) is the cryohydric point. This temperature-minimum is, however, not always attained in the preparation of a freezing mixture, and that for various reasons. The chief of these are radiation and the heat absorbed in cooling the solution produced. The lower the temperature falls, the more rapid does the radiation become; and the rate at which the temperature sinks decreases as the amount of solution increases. Both these factors counteract the effect of the latent heat of fusion and the heat of solution, so that a point is reached (which may lie considerably above the cryohydric point) at which the two opposing influences balance. The absorption of heat by the solution can be diminished by allowing the solution to drain off as fast as it is produced; and the effect of radiation can be partially annulled by increasing the rate of cooling. This can be done by the more intimate mixing of the components. Since, under atmospheric pressure, the temperature of the cryohydric point is constant, the cryohydrates are very valuable for the production of baths of constant low temperature. 2. _Partial Miscibility of the Fused Components._ On passing to the study of the second class of systems of two components belonging to this group, namely, those in which the fused components are not miscible in all proportions, we find that the relationships are not quite so simple as {122} in the case of silver nitrate and water. In the latter case, only one liquid phase was possible; in the cases now to be studied, two liquid phases can be formed, and there is a marked discontinuity in the solubility curve on passing from the cryohydric point to the melting point of the second (non-volatile) component. Paratoluidine dissolves in water, and the solubility increases as the temperature rises.[202] At 44.2°, however, paratoluidine in contact with water melts, and two liquid phases are formed, viz. a solution of water in fused paratoluidine and a solution of fused paratoluidine in water. We have, therefore, the phenomenon of _melting under the solvent_. This melting point will, of course, be lower than the melting point of the pure substance, because the solid is now in contact with a solution, and, as we have already seen, addition of a foreign substance lowers the melting point. Such cases of melting under the solvent are by no means rare, and a review of the relationships met with may, therefore, be undertaken here. As an example, there may be chosen the equilibrium between succinic nitrile, C_{2}H_{4}(CN)_{2} and water, which has been fully studied by Schreinemakers.[203] [Illustration: FIG. 30.] If to the system ice--water at 0° succinic nitrile is added, the temperature will fall; and continued addition of the nitrile will lead at last to the cryohydric point _b_ (Fig. 30), at which solid nitrile, ice, solution, and vapour can coexist. The temperature of the cryohydric point is -1.2°, and the composition of the solution is 1.29 mol. of nitrile in 100 mol. of solution. From _a_ to _b_ the solid phase in contact with the solution is ice. {123} If the temperature be now raised so as to cause the disappearance of the ice, and the addition of nitrile be continued, the concentration of the nitrile in the solution will increase as represented by the curve _bc_. At the point _c_ (18.5°), when the concentration of the nitrile in the solution has increased to 2.5 molecules per cent., the nitrile melts and two liquid phases are formed; the concentration of the nitrile in these two phases is given by the points _c_ and _c'_. As there are now four phases present, viz. solid nitrile, solution of fused nitrile in water, solution of water in fused nitrile, and vapour, the system is _invariant_. Since at this point the concentration, temperature, and pressure are completely defined, addition or withdrawal of heat can only cause a change in the relative amounts of the phases, _but no variation of the concentrations_ of the respective phases. As a matter of fact, continued addition of nitrile and addition of heat will cause an increase in the amount of the liquid phase containing excess of nitrile (_i.e._ the solution of water in fused nitrile), whereas the other liquid phase, the solution of fused nitrile in water, will gradually disappear. When it has completely disappeared, the system will be represented by the point _c'_, where the molecular concentration of nitrile is now 75 per cent., and again becomes univariant, the three phases being solid nitrile, liquid phase containing excess of nitrile, and vapour; and as the amount of the water is diminished the temperature of equilibrium rises, until at 54° the melting point of the pure nitrile is reached. Return now to the point c. At this point there exists the invariant system solid nitrile, two liquid phases, vapour. If heat be added, the solid nitrile will disappear, and there will be left the univariant system, consisting of two liquid phases and vapour.[204] Such a system will exhibit relationships similar to those already studied in the previous chapter. As the temperature rises, the mutual solubility of the two fused components becomes greater, until at _d_ (55.5°) the critical solution temperature is reached, and the fused components become miscible in all proportions. At all temperatures and concentrations lying to the right {124} of the curve _abcdc'e_ there can be only one liquid phase; in the field _cdc'_ there are two liquid phases. From the figure it will be easy to see what will be the result of bringing together succinic nitrile and water at different temperatures and in different amounts. Since _b_ is the lowest temperature at which liquid can exist in stable equilibrium with solid, ice and succinic nitrile can be mixed in any proportions at temperatures below _b_ without undergoing change. Between _b_ and _c_ succinic nitrile will be dissolved until the concentration reaches the value on the curve _bc_, corresponding to the given temperature. On adding the nitrile to water at temperatures between _c_ and _d_, it will dissolve until a concentration lying on the curve _cd_ is attained; at this point two liquid phases will be formed, and further addition of nitrile will cause the one liquid phase (that containing excess of nitrile) to increase, while the other liquid phase will decrease, until it finally disappears and there is only one liquid phase left, that containing excess of nitrile. This can dissolve further quantities of the nitrile, and the concentration will increase until the curve _c'e_ is reached, when the concentration will remain unchanged, and addition of solid will merely increase the amount of the solid phase. If a solution represented by any point in the field lying below the curve _bcd_ is heated to a temperature above _d_, the critical solution temperature, then the concentration of the nitrile can be increased to any desired amount without at any time two liquid phases making their appearance; the system can then be cooled down to a temperature represented by any point between the curves _dc'e_. In this way it is possible to pass continuously from a solution containing excess of one component to solutions containing excess of the other, as represented by the dotted line _xxxx_ (_v._ p. 100). At no point is there formation of two liquid phases. Supersaturation.--Just as suspended transformation is rarely met with in the passage from the solid to the liquid state, so also it is found in the case of the melting of substances under the solvent that suspended fusion does not occur; but that when the temperature of the invariant point is reached at which, therefore, the formation of two liquid layers is possible, {125} these two liquid layers, as a matter of fact, make their appearance. Suspended transformation can, however, take place from the side of the liquid phase, just as water or other liquid can be cooled below the normal freezing point without solidification occurring. The question, therefore, arises as to the relative solubilities of the solid and the supercooled liquid at the same temperature. [Illustration: FIG. 31.] The answer to this question can at once be given from what we have already learned (p. 113), if we recollect that at temperatures below the point of fusion under the solvent, the solid form, at temperatures above that point, the liquid form, is the more stable; at this temperature, therefore, the relative stability of the solid and liquid forms changes. Since, as we have already seen, the less stable form has the greater solubility, it follows that the supercooled liquid, being the less stable form, must have the greater solubility. This was first proved experimentally by Alexejeff[205] in the case of benzoic acid and water, the solubility curves for which are given in Fig. 31. As can be seen from the figure, the prolongation of the curve for liquid--liquid, which represents the solubility of the supercooled liquid benzoic acid, lies above that for the solubility of the {126} solid benzoic acid in water; the solution saturated with respect to the supercooled liquid is therefore supersaturated with respect to the solid form. A similar behaviour has been found in the case of other substances.[206] Pressure-Temperature Diagram.--Having considered the changes which occur in the concentration of the components in a solution with the temperature, we may conclude the discussion of the equilibrium between a salt and water by studying the variation of the vapour pressure. Since in systems of two components the two phases, solution and vapour, constitute a bivariant system, the vapour pressure is undefined, and may have different values at the same temperature, depending on the concentration. In order that there may be for each temperature a definite corresponding pressure of the vapour, a third phase must be present. This condition is satisfied by the system solid--liquid (solution)--vapour; that is, by the saturated solution (p. 108). In the case of a saturated solution, therefore, the pressure of the vapour at any given temperature is constant. Vapour Pressure of Solid--Solution--Vapour.--It has long been known that the addition of a non-volatile solid to a liquid in which it is soluble lowers the vapour pressure of the solvent; and the diminution of the pressure is approximately proportional to the amount of substance dissolved (Law of Babo). The vapour-pressure curve, therefore, of a solution of a salt in water must lie below that for pure water. Further, in the case of a pure liquid, the vaporization curve is a function only of the temperature (p. 63), whereas, in the case of a solution, the pressure varies both with the temperature and the _concentration_. These two factors, however, act in opposite directions; for although the vapour pressure in all cases increases as the temperature rises, increase of concentration, as we have seen, lowers the vapour pressure. Again, since the concentration itself varies with the temperature, two cases have to be considered, viz. where the concentration increases with rise of {127} temperature, and where the concentration diminishes with rise of temperature. The relations which are found here will be best understood with the help of Fig. 32.[207] In this figure, OB represents the sublimation curve of ice, and BC the vaporization curve of water; the curve for the solution must lie below this, and must cut the sublimation curve of ice at some temperature below the melting point. The point of intersection A is the cryohydric point. If the solubility increases with rise of temperature, the increase of the vapour pressure due to the latter will be partially annulled. Since at first the effect of increase of temperature more than counteracts the depressing action of increase of concentration, the vapour pressure will increase on raising the temperature above the cryohydric point. If the elevation of temperature is continued, however, to the melting point of the salt, the effect of increasing concentration makes itself more and more felt, so that the vapour-pressure curve of the solution falls more and more below that of the pure liquid, and the pressure will ultimately become equal to that of the pure salt; that is to say, practically equal to zero. The curve will therefore be of the general form AMF shown in Fig. 32. If the solubility should diminish with rise of temperature, the two factors, temperature and concentration, will act in the same direction, and the vapour-pressure curve will rise relatively more rapid than that of the pure liquid; since, however, the pure salt is ultimately obtained, the vapour-pressure curve must in this case also finally approach the value zero. [Illustration: FIG. 32.] Other Univariant Systems.--Besides the univariant system {128} salt--solution--vapour already considered, three others are possible, viz. ice--solution--vapour, ice--salt--solution, and ice--salt--vapour. The fusion point of a substance is lowered, as we have seen, by the addition of a foreign substance, and the depression is all the greater the larger the quantity of substance added. The vapour pressure of the water, also, is lowered by the solution in it of other substances, so that the vapour pressure of the system ice--solution--vapour must decrease as the temperature falls from the fusion point of ice to the cryohydric point. This curve is represented by BA (Fig. 32), and is coincident with the sublimation curve of ice. This, at first sight, strange fact will be readily understood when we consider that since ice and solution are together in equilibrium with the same vapour, they must have the same vapour pressure. For suppose at any given temperature equilibrium to have been established in the system ice--solution--vapour, removal of the ice will not alter this equilibrium. Suppose, now, the ice and the solution placed under a bell-jar so that they have a common vapour, but are not themselves in contact; then, if they do not have the same vapour pressure, distillation must take place and the solution will become more dilute or more concentrated. Since, at the completion of this process, the ice and solution are now in equilibrium when they are not in contact, they must also be in equilibrium when they are in contact (p. 32). But if distillation has taken place the concentration of the solution must have altered, so that the ice will now be in equilibrium with a solution of a different concentration from before. But according to the Phase Rule ice cannot at one and the same temperature be in equilibrium with two solutions of different concentration, for the system ice--solution--vapour is univariant, and at any given temperature, therefore, not only the pressure but also the _concentration of the components in the solution must be constant_. Distillation could not, therefore, take place from the ice to the solution or _vice versâ_; that is to say, the solution and the ice must have the same vapour pressure--the sublimation pressure of ice. The reason of the coincidence is the non-volatility of the salt: had {129} the salt a measurable vapour pressure itself, the sublimation curve of ice and the curve for ice--solution--vapour would no longer fall together. The curve AO represents the pressures of the system ice--salt--vapour. This curve will also be coincident with the sublimation curve of ice, on account of the non-volatility of the salt. The equilibria of the fourth univariant system ice--salt--solution are represented by AE. Since this is a condensed system, the effect of a small change of temperature will be to cause a large change of pressure, as in the case of the fusion point of a pure substance. The direction of this curve will depend on whether there is an increase or diminution of volume on solidification; but the effect in any given case can be predicted with the help of the theorem of Le Chatelier. Since the cryohydric point is a quadruple point in a two-component system, it represents an invariant system. The condition of the system is, therefore, completely defined; the four phases, ice, salt, solution, vapour, can co-exist only when the temperature, pressure, and concentration of the solution have constant and definite values. Addition or withdrawal of heat, therefore, can cause no alteration of the condition of the system except a variation of the relative amounts of the phases. Addition of heat at constant volume will ultimately lead to the system salt--solution--vapour or the system ice--solution--vapour, according as ice or salt disappears first. This is readily apparent from the diagram (Fig. 32), for the systems ice--salt--solution and ice--salt--vapour can exist only at temperatures below the cryohydric point (provided the curve for ice--salt--solution slopes towards the pressure axis). Bivariant Systems.--Besides the univariant systems already discussed, various bivariant systems are possible, the conditions for the existence of which are represented by the different areas of Fig. 32. They are as follows:-- _Area._ _System._ OAMF Salt--vapour. CBAMF Solution--vapour; salt--solution. EABD Salt--solution; ice--solution. EAO Ice--salt. {130} Deliquescence.--As is evident from Fig. 32, salt can exist in contact with water vapour at pressures under those represented by OAMF. If, however, the pressure of the vapour is increased until it reaches a value lying on this curve at temperatures above the cryohydric point, solution will be formed; for the curve AMF represents the equilibria between salt--solution--vapour. From this, therefore, it is clear that if the pressure of the aqueous vapour in the atmosphere is greater than that of the saturated solution of a salt, that salt will, on being placed in the air, form a solution; it will _deliquesce_. Separation of Salt on Evaporation.--With the help of Fig. 32 it is possible to state in a general manner whether or not salt will be deposited when a solution is evaporated under a constant pressure.[208] The curve AMF (Fig. 32) is the vapour-pressure curve of the saturated solutions of the salt, _i.e._ it represents, as we have seen, the maximum vapour pressure at which salt can exist in contact with solution and vapour. The dotted line _aa_ represents atmospheric pressure. If, now, an unsaturated solution, the composition of which is represented by the point _x_, is heated in an open vessel, the temperature will rise, and the vapour pressure of the solution will increase. The system will, therefore, pass along a line represented diagrammatically by _xx'_. At the point _x'_ the vapour pressure of the system becomes equal to 1 atm.; and as the vessel is open to the air, the pressure cannot further rise; the solution boils. If the heating is continued, water passes off, the concentration increases, and the boiling point rises. The system will therefore pass along the line _x'm_, until at the point _m_ solid salt separates out (provided supersaturation is excluded). The system is now univariant, and continued heating will no longer cause an alteration of the concentration; as water passes off, solid salt will be deposited, and the solution will evaporate to dryness. If, however, the atmospheric pressure is represented not by _aa_ but by _bb_, then, as Fig. 32 shows, the maximum vapour {131} pressure of the system salt--solution--vapour never reaches the pressure of 1 atm. Further, since the curve _bb_ lies in the area of the bivariant system solution--vapour there can at no point be a separation of the solid form; for the system solid--solution--vapour can exist only along the curve AMF. On evaporating the solution of a salt in an open vessel, therefore, salt can be deposited only if at some temperature the pressure of the saturated solution is equal to the atmospheric pressure. This is found to be the case with most salts. In the case of aqueous solutions of sodium and potassium hydroxide, however, the vapour pressure of the saturated solution never reaches the value of 1 atm., and on evaporating these solutions, therefore, in an open vessel, there is no separation of the solid. Only a homogeneous fused mass is obtained. If, however, the evaporation be carried out under a pressure which is lower than the maximum pressure of the saturated solution, separation of the solid substance will be possible. General Summary.--The systems which have been discussed in the present chapter contained water as one of their components, and an anhydrous salt as the other. It will, however, be clear that the relationships which were found in the case of these will be found also in other cases where it is a question of the equilibria between two components, which crystallize out in the pure state, and only one of which possesses a measurable vapour pressure. A similar behaviour will, for example, be found in the case of many pairs of organic substances; and in all cases the equilibria will be represented by a diagram of the general appearance of Fig. 29 or Fig. 30. That is to say: Starting from the fusion point of component I., the system will pass, by progressive addition of component II., to regions of lower temperature, until at last the cryohydric or eutectic point is reached. On further addition of component II., the system will pass to regions of higher temperature, the solid phase now being component II. If the fused components are miscible with one another in all proportions a continuous curve will be obtained leading up to the point of fusion of component II. Slight changes of direction, it is true, due to changes in the crystalline form, may be found along this curve, {132} but throughout its whole course there will be but one liquid phase. If, on the other hand, the fused components are not miscible in all proportions, then the second curve will exhibit a marked discontinuity, and two liquid phases will make their appearance. * * * * * {133} CHAPTER VIII SOLUTIONS OF SOLIDS IN LIQUIDS, ONLY ONE OF THE COMPONENTS BEING VOLATILE B.--HYDRATED SALT AND WATER. In the preceding chapter we discussed the behaviour of systems formed of two components, only one of which was volatile, in those cases where the two components separated from solution in the pure state. In the present chapter we shall consider those systems in which combination between the components can occur with the formation of definite compounds; such as are found in the case of crystalline salt hydrates. Since a not inconsiderable amount of study has been devoted to the systems formed by hydrated salts and water, systems which are of great chemical interest and importance, the behaviour of these will first call for discussion in some detail, and it will be found later that the relationships which exist in such systems appear also in a large number of other two-component systems. The systems belonging to this group may be divided into two classes according as the compounds formed possess a definite melting point, _i.e._ form a liquid phase of the same composition, or do not do so. We shall consider the latter first. 1. _The Compounds formed do not have a Definite Melting Point._ Concentration-Temperature Diagram.--In the case of salts which can form crystalline hydrates, the temperature-concentration diagram, representing the equilibria of the {134} different possible systems, must necessarily be somewhat more complicated than where no such combination of the components occurs. For, as has already been pointed out, each substance has its own solubility curve; and there will therefore be as many solubility curves as there are solid phases possible, _the curve for each particular solid phase being continuous so long as it remains unchanged in contact with the solution_. As an example of the relationships met with in such cases, we shall first of all consider the systems formed of sodium sulphate and water. [Illustration: FIG. 33.] Sodium Sulphate and Water.--At the ordinary temperatures, sodium sulphate crystallises from water with ten molecules of water of crystallisation, forming Glauber's salt. On determining the solubility of this salt in water, it is found that the solubility increases as the temperature rises, the values of the solubility, represented graphically by the curve AC (Fig. 33), being given in the following table.[209] The numbers denote grams of sodium sulphate, calculated as anhydrous salt, dissolved by 100 grams of water. SOLUBILITY OF Na_{2}SO_{4},10H_{2}O. -------------------------- Temperature. | Solubility. -------------------------- 0° | 5.02 10° | 9.00 15° | 13.20 18° | 16.80 20° | 19.40 25° | 28.00 30° | 40.00 33° | 50.76 34° | 55.00 -------------------------- {135} On continuing the investigation at higher temperatures, it was found that the solubility no longer increased, but _decreased with rise of temperature_. At the same time, it was observed that the solid phase was now different from that in contact with the solution at temperatures below 33°; for whereas in the latter case the solid phase was sodium sulphate decahydrate, at temperatures above 33° the solid phase was the anhydrous salt. The course of the solubility curve of anhydrous sodium sulphate is shown by BD, and the values of the solubility are given in the following table:--[210] SOLUBILITY OF ANHYDROUS SODIUM SULPHATE. -------------------------- Temperature. | Solubility. -------------------------- 18° | 53.25 20° | 52.76 25° | 51.53 30° | 50.37 33° | 49.71 34° | 49.53 36° | 49.27 40.15° | 48.78 50.40° | 46.82 -------------------------- As is evident from the figure, the solubility curve which is obtained when anhydrous sodium sulphate is present as the solid phase, cuts the curve representing the solubility of the decahydrate, at a temperature of about 33°. If a solution of sodium sulphate which has been saturated at a temperature of about 34° be cooled down to a temperature below 17°, while care is taken that the solution is protected against access of particles of Glauber's salt, crystals of a second hydrate of sodium sulphate, having the composition Na_{2}SO_{4},7H_{2}O, separate out. On determining the composition of the solutions in equilibrium with this hydrate at different temperatures, the following values were obtained, these values being represented by the curve FE (Fig. 33):-- {136} SOLUBILITY OF Na_{2}SO_{4},7H_{2}O. -------------------------- Temperature. | Solubility. -------------------------- 0° | 19.62 10° | 30.49 15° | 37.43 18° | 41.63 20° | 44.73 25° | 52.94 26° | 54.97 -------------------------- Since, as has already been stated, each solid substance has its own solubility curve, there are three separate curves to be considered in the case of sodium sulphate and water. Where two curves cut, the solution must be saturated with respect to two solid phases; at the point B, therefore, the point of intersection of the solubility curve of anhydrous sodium sulphate with that of the decahydrate, the solution must be saturated with respect to these two solid substances. But a system of two components existing in four phases, anhydrous salt--hydrated salt--solution--vapour, is invariant; and this invariability will remain even if only three phases are present, provided that one of the factors, pressure, temperature, or concentration of components retains a constant value. This is the case when solubilities are determined in open vessels; the pressure is then equal to atmospheric pressure. Under these circumstances, then, the system, anhydrous sodium sulphate--decahydrate--solution, will possess no degree of freedom, and can exist, therefore, only at one definite temperature and when the solution has a certain definite composition. The temperature of this point is 32.482° on a mercury thermometer, or 32.379° on the hydrogen thermometer.[211] {137} Suspended Transformation.--Although it is possible for the anhydrous salt to make its appearance at the temperature of the quadruple point, it will not necessarily do so; and it is therefore possible to follow the solubility curve of sodium sulphate decahydrate to a higher temperature. Since, however, the solubility of the decahydrate at temperatures above the quadruple point is greater than that of the anhydrous salt, the solution which is _saturated_ with respect to the former will be _supersaturated_ with respect to the latter. On bringing a small quantity of the anhydrous salt in contact with the solution, therefore, anhydrous salt will be deposited; and all the hydrated salt present will ultimately undergo conversion into the anhydrous salt, through the medium of the solution. In this case, as in all cases, the solid phase, which is the most stable at the temperature of the experiment, has at that temperature the least solubility. Similarly, the solubility curve of anhydrous sodium sulphate has been followed to temperatures below 32.5°. Below this temperature, however, the solubility of this salt is greater than that of the decahydrate, and the saturated solution of the anhydrous salt will therefore be supersaturated for the decahydrate, and will deposit this salt if a "nucleus" is added to the solution. From this we see that at temperatures above 32.5° the anhydrous salt is the stable form, while the decahydrate is unstable (or metastable); at temperatures below 32.5° the decahydrate is stable. This temperature, therefore, is the _transition temperature_ for decahydrate and anhydrous salt. From Fig. 33 we see further that the solubility curve of the anhydrous salt (which at all temperatures below 32.5° is metastable) is cut by the solubility curve of the heptahydrate; and this point of intersection (at a temperature of 24.2°) must be the _transition point_ for heptahydrate and anhydrous salt. Since at all temperatures the solubility of the heptahydrate is greater than that of the decahydrate, the former hydrate must be metastable with respect to the latter; so that throughout its whole course the solubility curve of the heptahydrate {138} represents only metastable equilibria. Sodium sulphate, therefore, forms only one stable hydrate, the decahydrate. The solubility relations of sodium sulphate illustrate very clearly the importance of the solid phase for the definition of saturation and supersaturation. Since the solubility curve of the anhydrous salt has been followed backwards to a temperature of about 18°, it is readily seen, from Fig. 33, that at a temperature of, say, 20° three different _saturated_ solutions of sodium sulphate are possible, according as the anhydrous salt, the heptahydrate or the decahydrate, is present as the solid phase. Two of these solutions, however, would be metastable and _supersaturated with respect to the decahydrate_. Further, the behaviour of sodium sulphate and water furnishes a very good example of the fact that a "break" in the solubility curve occurs when, and only when, the solid phase undergoes change. So long as the decahydrate, for example, remained unaltered in contact with the solution, the solubility curve was continuous; but when the anhydrous salt appeared in the solid phase, a distinct change in the direction of the solubility curve was observed. Dehydration by Means of Anhydrous Sodium Sulphate.--The change in the relative stability of sodium sulphate decahydrate and anhydrous salt in presence of water at a temperature of 32.5° explains why the latter salt cannot be employed for dehydration purposes at temperatures above the transition point. The dehydrating action of the anhydrous salt depends on the formation of the decahydrate; but since at temperatures above 33° the latter is unstable, and cannot be formed in presence of the anhydrous salt, this salt cannot, of course, effect a dehydration above that temperature. Pressure-Temperature Diagram.--The consideration of the pressure-temperature relations of the two components, sodium sulphate and water, must include not only the vapour pressure of the saturated solutions, but also that of the crystalline hydrates. The vapour pressures of salt hydrates have already been treated in a general manner (Chap. V.), so that it is only necessary here to point out the connection between the two classes of systems. {139} In most cases the vapour pressure of a salt hydrate, _i.e._ the vapour pressure of the system hydrate--anhydrous salt (or lower hydrate)--vapour, is at all temperatures lower than that of the system anhydrous salt (or lower hydrate)--solution--vapour. This, however, is not a necessity; and cases are known where the vapour pressure of the former system is, under certain circumstances, equal to or higher than that of the latter. An example of this is found in sodium sulphate decahydrate. On heating Na_{2}SO_{4},10H_{2}O, a point is reached at which the dissociation pressure into anhydrous salt and water vapour becomes equal to the vapour pressure of the saturated solution of the anhydrous salt, as is apparent from the following measurements;[212] the differences in pressure being expressed in millimetres of a particular oil. Temperature: 29.0° 30.83° 31.79° 32.09° 32.35° 32.6° Difference of pressure: 23.8 10.8 5.6 3.6 1.6 0 At 32.6°, therefore, the vapour pressures of the two systems Na_{2}SO_{4},10H_{2}O--Na_{2}SO_{4}--vapour Na_{2}SO_{4}--solution--vapour are equal; at this temperature the four phases, Na_{2}SO_{4},10H_{2}O; Na_{2}SO_{4}; solution; vapour, can coexist. From this it is evident that when sodium sulphate decahydrate is heated to 32.6°, the two new phases anhydrous salt and solution will be formed (suspended transformation being supposed excluded), and the hydrate will appear to undergo _partial fusion_; and during the process of "melting" the vapour pressure and temperature will remain constant.[213] This is, however, not a true but a so-called _incongruent_ melting point; for the composition of the liquid phase is not the same as that of the solid. As has already been pointed out (p. 137), we are dealing here with the _transition point_ of the decahydrate and anhydrous salt, _i.e._ with the reaction Na_{2}SO_{4},10H_{2}O <--> Na_{2}SO_{4} + 10H_{2}O. Since at the point of partial fusion of the decahydrate four {140} phases can coexist, the point is a quadruple point in a two-component system, and the system at this point is therefore invariant. The temperature of this point is therefore perfectly definite, and on this account the proposal has been made to adopt this as a fixed point in thermometry.[214] The temperature is, of course, practically the same as that at which the two solubility curves intersect (p. 112). If, however, the vapour phase disappears, the system becomes univariant, and the equilibrium temperature undergoes change with change of pressure. The transition curve has been determined by Tammann,[215] and shown to pass through a point of maximum temperature. [Illustration: FIG. 34.] The vapour pressure of the different systems of sodium sulphate and water can best be studied with the help of the diagram in Fig. 34.[216] The curve ABCD represents the vapour-pressure curve of the saturated solution of anhydrous sodium sulphate. GC is the pressure curve of decahydrate + anhydrous salt, which, as we have seen, cuts the curve ABCD at the transition temperature, 32.6°. Since at this point the solution is saturated with respect to both the anhydrous salt and the decahydrate, the vapour-pressure curve of the saturated solution of the latter must also pass through the point C.[217] As at temperatures below this point the solubility of the decahydrate is less than that of the anhydrous salt, the vapour pressure of the solution will, in accordance with Babo's law (p. 126), be higher than that of the solution of the anhydrous salt; which was also found experimentally to be the case (curve HC). {141} In connection with the vapour pressure of the saturated solutions of the anhydrous salt and the decahydrate, attention must be drawn to a conspicuous deviation from what was found to hold in the case of one-component systems in which a vapour phase was present (p. 31). There, it was seen that the vapour pressure of the more stable system was always _lower_ than that of the less stable; in the present case, however, we find that this is no longer so. We have already learned that at temperatures below 32.5° the system decahydrate--solution--vapour is more stable than the system anhydrous salt--solution--vapour; but the vapour pressure of the latter system is, as has just been stated, lower than that of the former. At temperatures above the transition point the vapour pressure of the saturated solution of the decahydrate will be lower than that of the saturated solution of the anhydrous salt. This behaviour depends on the fact that the less stable form is the more soluble, and that the diminution of the vapour pressure increases with the amount of salt dissolved. With regard to sodium sulphate heptahydrate the same considerations will hold as in the case of the decahydrate. Since at 24° the four phases heptahydrate, anhydrous salt, solution, vapour can coexist, the vapour-pressure curves of the systems hydrate--anhydrous salt--vapour (curve EB) and hydrate--solution--vapour (curve FB) must cut the pressure curve of the saturated solution of the anhydrous salt at the above temperature, as represented in Fig. 34 by the point B. This constitutes, therefore, a second quadruple point, which is, however, metastable. From the diagram it is also evident that the dissociation pressure of the heptahydrate is higher than that of the decahydrate, although it contains less water of crystallization. The system heptahydrate--anhydrous salt--vapour must be metastable with respect to the system decahydrate--anhydrous salt--vapour, and will pass into the latter.[218] Whether or not there is a temperature at which the vapour-pressure curves of the two systems intersect, and below which the heptahydrate becomes the more stable form, is not known. {142} In the case of sodium sulphate there is only one stable hydrate. Other salts are known which exhibit a similar behaviour; and we shall therefore expect that the solubility relationships will be represented by a diagram similar to that for sodium sulphate. A considerable number of such cases have, indeed, been found,[219] and in some cases there is more than one metastable hydrate. This is found, for example, in the case of nickel iodate,[220] the solubility curves for which are given in Fig. 35. As can be seen from the figure, suspended transformation occurs, the solubility curves having in some cases been followed to a considerable distance beyond the transition point. One of the most brilliant examples, however, of suspended transformation in the case of salt hydrates, and the sluggish transition from the less stable to the more stable form, is found in the case of the hydrates of calcium chromate.[221] [Illustration: FIG. 35.] In the preceding cases, the dissociation-pressure curve of the hydrated salt cuts the vapour-pressure curve of the saturated {143} solution of the anhydrous salt. It can, however, happen that the dissociation-pressure curve of one hydrate cuts the solubility curve, not of the anhydrous salt, but of a lower hydrate; in this case there will be more than one stable hydrate, each having a stable solubility curve; and these curves will intersect at the temperature of the transition point. Various examples of this behaviour are known, and we choose for illustration the solubility relationships of barium acetate and its hydrates[222] (Fig. 36). [Illustration: FIG. 36.] At temperatures above 0°, barium acetate can form two stable hydrates, a trihydrate and a monohydrate. The solubility of the trihydrate increases very rapidly with rise of temperature, and has been determined up to 26.1°. At temperatures above 24.7°, however, the trihydrate is metastable with respect to the monohydrate; for at this temperature the solubility curve of the latter hydrate cuts that of the former. This is, therefore, the transition temperature for the trihydrate and monohydrate. The solubility curve of the monohydrate succeeds that of the trihydrate, and exhibits a conspicuous point of minimum solubility at about 30°. Below 24.7° the {144} monohydrate is the less stable hydrate, but its solubility has been determined to a temperature of 22°. At 41° the solubility curve of the monohydrate intersects that of the anhydrous salt, and this is therefore the transition temperature for the monohydrate and anhydrous salt. Above this temperature the anhydrous salt is the stable solid phase. Its solubility curve also passes through a minimum. The diagram of solubilities of barium acetate not only illustrates the way in which the solubility curves of the different stable hydrates of a salt succeed one another, but it has also an interest and importance from another point of view. In Fig. 36 there is also shown a faintly drawn curve which is continuous throughout its whole course. This curve represents the solubility of barium acetate as determined by Krasnicki.[223] Since, however, three different solid phases can exist under the conditions of experiment, it is evident, from what has already been stated (p. 111), that the different equilibria between barium acetate and water could not be represented by one _continuous_ curve. Another point which these experiments illustrate and which it is of the highest importance to bear in mind is, that in making determinations of the solubility of salts which are capable of forming hydrates, it is not only necessary to determine the composition of the solution, but _it is of equal importance to determine the composition of the solid phase in contact with it_. In view of the fact, also, that the solution equilibrium is in many cases established with comparative slowness, it is necessary to confirm the point of equilibrium, either by approaching it from higher as well as from lower temperatures, or by actually determining the rate with which the condition of equilibrium is attained. This can be accomplished by actual weighing of the dissolved salt or by determinations of the density of the solution, as well as by other methods. {145} 2. _The Compounds formed have a Definite Melting Point._ In the cases which have just been considered we saw that the salt hydrates on being heated did not undergo complete fusion, but that a solid was deposited consisting of a lower hydrate or of the anhydrous salt. It has, however, been long known that certain crystalline salt hydrates (_e.g._ sodium thiosulphate, Na_{2}S_{2}O_{3},5H_{2}O, sodium acetate, NaC_{2}H_{3}O_{2},3H_{2}O) melt completely in their water of crystallization, and yield a liquid of the _same composition_ as the crystalline salt. In the case of sodium thiosulphate pentahydrate the temperature of liquefaction is 56°; in the case of sodium acetate trihydrate, 58°. These two salts, therefore, have a definite melting point. For the purpose of studying the behaviour of such salt hydrates, we shall choose not the cases which have just been mentioned, but two others which have been more fully studied, viz. the hydrates of calcium chloride and of ferric chloride. Solubility Curve of Calcium Chloride Hexahydrate.[224]--Although calcium chloride forms several hydrates, each of which possesses its own solubility, it is nevertheless the solubility curve of the hexahydrate which will chiefly interest us at present, and we shall therefore first discuss that curve by itself. [Illustration: FIG. 37.] The solubility of this salt has been determined from the cryohydric point, which lies at about -55°, up to the melting point of the salt.[225] The solubility increases with rise of temperature, as is shown by the figures in the following table, and by the (diagrammatic) curve AB in Fig. 37. In the table, the numbers under the heading "solubility" denote the number of grams of CaCl_{2} dissolved in 100 grams {146} of water; those under the heading "composition," the number of gram-molecules of water in the solution to one gram-molecule of CaCl_{2}. SOLUBILITY OF CALCIUM CHLORIDE HEXAHYDRATE. ----------------------------------------- Temperature. | Solubility. | Composition. ----------------------------------------- -55° | 42.5 | 14.5 -25° | 50.0 | 12.3 -10° | 55.0 | 11.2 0° | 59.5 | 10.37 10° | 65.0 | 9.49 20° | 74.5 | 8.28 25° | 82.0 | 7.52 28.5° | 90.5 | 6.81 29.5° | 95.5 | 6.46 30.2° | 102.7 | 6.00 29.6° | 109.0 | 5.70 29.2° | 112.8 | 5.41 ----------------------------------------- So far as the first portion of the curve is concerned, it resembles the most general type of solubility curve. In the present case the solubility is so great and increases so rapidly with rise of temperature, that a point is reached at which the water of crystallization of the salt is sufficient for its complete solution. This temperature is 30.2°; and since the composition of the solution is the same as that of the solid salt, viz. 1 mol. of CaCl_{2} to 6 mols. of water, this temperature must be the melting point of the hexahydrate. At this point the hydrate will fuse or the solution will solidify without change of temperature and without change of composition. Such a melting point is called a _congruent_ melting point. But the solubility curve of calcium chloride hexahydrate differs markedly from the other solubility curves hitherto considered in that it possesses a _retroflex portion_, represented in the figure by BC. As is evident from the figure, therefore, calcium chloride hexahydrate exhibits the peculiar and, as it was at first thought, impossible behaviour that it can be in equilibrium at one and the same temperature with two different solutions, one of which contains more, the other less, water than the solid hydrate; for it must be remembered that {147} throughout the whole course of the curve ABC the solid phase present in equilibrium with the solution is the hexahydrate. Such a behaviour, however, on the part of calcium chloride hexahydrate will appear less strange if one reflects that the melting point of the hydrate will, like the melting point of other substances, be lowered by the addition of a second substance. If, therefore, water is added to the hydrate at its melting point, the temperature at which the solid hydrate will be in equilibrium with the liquid phase (solution) will be lowered; or if, on the other hand, anhydrous calcium chloride is added to the hydrate at its melting point (or what is the same thing, if water is removed from the solution), the temperature at which the hydrate will be in equilibrium with the liquid will also be lowered; _i.e._ the hydrate will melt at a lower temperature. In the former case we have the hydrate in equilibrium with a solution containing more water, in the latter case with a solution containing less water than is contained in the hydrate itself. It has already been stated (p. 109) that the solubility curve (in general, the equilibrium curve) is continuous so long as the solid phase remains unchanged; and we shall therefore expect that the curve ABC will be continuous. Formerly, however, it was considered by some that the curve was not continuous, but that the melting point is the point of intersection of two curves, a solubility curve and a fusion curve. Although the earlier solubility determinations were insufficient to decide this point conclusively, more recent investigation has proved beyond doubt that the curve is continuous and exhibits no break.[226] {148} Although in taking up the discussion of the equilibria between calcium chloride and water, it was desired especially to call attention to the form of the solubility curve in the case of salt hydrates possessing a definite melting point, nevertheless, for the sake of completeness, brief mention may be made of the other systems which these two components can form. [Illustration: FIG. 38.] Besides the hexahydrate, the solubility curve of which has already been described, calcium chloride can also crystallize in two different forms, each of which contains four molecules {149} of water of crystallization; these are distinguished as [alpha]-tetrahydrate, and [beta]-tetrahydrate. Two other hydrates are also known, viz. a dihydrate and a monohydrate. The solubility curves of these different hydrates are given in Fig. 38. On following the solubility curve of the hexahydrate from the ordinary temperature upwards, it is seen that at a temperature of 29.8° represented by the point H, it cuts the solubility curve of the [alpha]-tetrahydrate. This point is therefore a quadruple point at which the four phases hexahydrate, [alpha]-tetrahydrate, solution, and vapour can coexist. It is also the transition point for these two hydrates. Since, at temperatures above 29.8°, the [alpha]-tetrahydrate is the stable form, it is evident from the data given before (p. 146), as also from Fig. 38, that the portion of the solubility curve of the hexahydrate lying above this temperature represents _metastable_ equilibria. The realization of the metastable melting point of the hexahydrate is, therefore, due to suspended transformation. At the transition point, 29.8°, the solubility of the hexahydrate and [alpha]-tetrahydrate is 100.6 parts of CaCl_{2} in 100 parts of water. The retroflex portion of the solubility curve of the hexahydrate extends to only 1° below the melting point of the hydrate. At 29.2° crystals of a new hydrate, [beta]-tetrahydrate, separate out, and the solution, which now contains 112.8 parts of CaCl_{2} to 100 parts of water, is saturated with respect to the two hydrates. Throughout its whole extent the solubility curve EDF of the [beta]-tetrahydrate represents metastable equilibria. The upper limit of the solubility curve of [beta]-tetrahydrate is reached at 38.4° (F), the point of intersection with the curve for the dihydrate. Above 29.8° the stable hydrate is the [alpha]-tetrahydrate; and its solubility curve extends to 45.3° (K), at which temperature it cuts the solubility curve of the dihydrate. The curve of the latter hydrate extends to 175.5° (L), and is then succeeded by the curve for the monohydrate. The solubility curve of the anhydrous salt does not begin until a temperature of about 260°. The whole diagram, therefore, shows a succession of stable hydrates, a metastable hydrate, a metastable melting point and retroflex solubility curve. {150} Pressure-Temperature Diagram.--The complete study of the equilibria between the two components calcium chloride and water would require the discussion of the vapour pressure of the different systems, and its variation with the temperature. For our present purpose, however, such a discussion would not be of great value, and will therefore be omitted here; in general, the same relationships would be found as in the case of sodium sulphate (p. 138), except that the rounded portion of the solubility curve of the hexahydrate would be represented by a similar rounded portion in the pressure curve.[227] As in the case of sodium sulphate, the transition points of the different hydrates would be indicated by breaks in the curve of pressures. Finally, mention may again be made of the difference of the pressure of dissociation of the hexahydrate according as it becomes dehydrated to the [alpha]- or the [beta]-tetrahydrate (p. 88). The Indifferent Point.--We have already seen that at 30.2° calcium chloride hexahydrate melts congruently, and that, provided the pressure is maintained constant, addition or withdrawal of heat will cause the complete liquefaction or solidification, without the temperature of the system undergoing change. This behaviour, therefore, is similar to, but is not quite the same as the fusion of a simple substance such as ice; and the difference is due to the fact that in the case of the hexahydrate the emission of vapour by the liquid phase causes an alteration in the composition of the latter, owing to the non-volatility of the calcium chloride; whereas in the case of ice this is, of course, not so. Consider, however, for the present that the vapour phase is absent, and that we are dealing with the two-phase system solid--solution. Then, since there are two components, the system is bivariant. For any given value of the pressure, therefore, we should expect that the system could exist at different temperatures; which, indeed, is the case. It has, however, already been noted that when the composition of the liquid phase becomes the same as that of the solid, the system then behaves as a _univariant_ system; for, at a given pressure, the system solid--solution can exist only at _one_ temperature, change of temperature producing complete transformation in {151} one or other direction. _The variability of the system has therefore been diminished._ This behaviour will perhaps be more clearly understood when one reflects that since the composition of the two phases is the same, the system may be regarded as being formed of _one component_, just as the system NH_{4}Cl <--> NH_{3} + HCl was regarded as being composed of one component when the vapour had the same total composition as the solid (p. 13). One component in two phases, however, constitutes a univariant system, and we can therefore see that calcium chloride hexahydrate in contact with solution of the same composition will constitute a univariant system. The temperature of equilibrium will, however, vary with the pressure;[228] if the latter is constant, the temperature will also be constant. A point such as has just been referred to, which represents the special behaviour of a system of two (or more) components, in which the composition of two phases becomes identical, is known as an _indifferent point_,[229] and it has been shown[230] that at a given pressure the temperature in the indifferent point is the _maximum_ or _minimum_ temperature possible at the particular pressure[231] (cf. critical solution temperature). At such a point a system loses one degree of freedom, or behaves like a system of the next lower order. The Hydrates of Ferric Chloride.--A better illustration of the formation of compounds possessing a definite melting point, and of the existence of retroflex solubility curves, is afforded by the hydrates of ferric chloride, which not only possess definite points of fusion, but these melting points are stable. A very brief description of the relations met with will suffice.[232] {152} Ferric chloride can form no less than four stable hydrates, viz. Fe_{2}Cl_{6},12H_{2}O, Fe_{2}Cl_{6},7H_{2}O, Fe_{2}Cl_{6},5H_{2}O, and Fe_{2}Cl_{6},4H_{2}O, and each of these hydrates possesses a definite, stable melting point. On analogy with the behaviour of calcium chloride, therefore, we shall expect that the solubility curves of these different hydrates will exhibit a series of _temperature maxima_; the points of maximum temperature representing systems in which the composition of the solid and liquid phases is the same. A graphical representation of the solubility relations is given in Fig. 39, and the composition of the different saturated solutions which can be formed is given in the following tables, the composition being expressed in molecules of Fe_{2}Cl_{6} to 100 molecules of water. The figures printed in thick type refer to transition and melting points. [Illustration: FIG. 39.] {153} COMPOSITION OF THE SATURATED SOLUTIONS OF FERRIC CHLORIDE AND ITS HYDRATES. (_The name placed at the head of each table is the solid phase._) ICE. --------------------------- Temperature. | Composition. --------------------------- ±-55° | ±2.75 -40° | 2.37 -27.5° | 1.90 -20.5° | 1.64 -10° | 1.00 0° | 0 --------------------------- Fe_{2}Cl_{6},12H_{2}O. --------------------------- Temperature. | Composition. --------------------------- -55° | ±2.75 -41° | 2.81 -27° | 2.98 0° | 4.13 10° | 4.54 20° | 5.10 30° | 5.93 35° | 6.78 36.5° | 7.93 37° | 8.33 36° | 9.29 33° | 10.45 30° | 11.20 27·4° | 12.15 20° | 12.83 10° | 13.20 8° | 13.70 --------------------------- Fe_{2}Cl_{6},7H_{2}O. --------------------------- Temperature. | Composition. --------------------------- 20° | 11.35 27·4° | 12.15 32° | 13.55 32.5° | 14.29 30° | 15.12 25° | 15.54 --------------------------- Fe_{2}Cl_{6},5H_{2}O. --------------------------- Temperature. | Composition. --------------------------- 20° | 11.35 12° | 12.87 20° | 13.95 27° | 14.85 30° | 15.12 35° | 15.64 50° | 17.50 55° | 19.15 56° | 20.00 55° | 20.32 --------------------------- Fe_{2}Cl_{6},4H_{2}O --------------------------- Temperature. | Composition. --------------------------- 20° | 11.35 50° | 19.96 55° | 20.32 60° | 20.70 69° | 21.53 72.5° | 23.35 73.5° | 25.00 72.5° | 26.15 70° | 27.90 66° | 29.20 --------------------------- Fe_{2}Cl_{6} (ANHYDROUS). --------------------------- Temperature. | Composition. --------------------------- 20° | 11.35 66° | 29.20 70° | 29.42 75° | 28.92 80° | 29.20 100° | 29.75 --------------------------- The lowest portion of the curve, AB, represents the equilibria between ice and solutions containing ferric chloride. It represents, in other words, the lowering of the fusion point of ice by addition of ferric chloride. At the point B (-55°), the cryohydric point (p. 117) is reached, at which the solution is in equilibrium with ice and ferric chloride dodecahydrate. As {154} has already been shown, such a point represents an invariant system; and the liquid phase will, therefore, solidify to a mixture of ice and hydrate without change of temperature. If heat is added, ice will melt and the system will pass to the curve BCDN, which is the solubility curve of the dodecahydrate. At C (37°), the point of maximum temperature, the hydrate melts completely. The retroflex portion of this curve can be followed backwards to a temperature of 8°, but below 27.4° (D), the solutions are supersaturated with respect to the heptahydrate; point D is the eutectic point for dodecahydrate and heptahydrate. The curve DEF is the solubility curve of the heptahydrate, E being the melting point, 32.5°. On further increasing the quantity of ferric chloride, the temperature of equilibrium is lowered until at F (30°) another eutectic point is reached, at which the heptahydrate and pentahydrate can co-exist with solution. Then follow the solubility curves for the pentahydrate, the tetrahydrate, and the anhydrous salt; G (56°) is the melting point of the former hydrate, J (73.5°) the melting point of the latter. H and K, the points at which the curves intersect, represent eutectic points; the temperature of the former is 55°, that of the latter 66°. The dotted portions of the curves represent metastable equilibria. As is seen from the diagram, a remarkable series of solubility curves is obtained, each passing through a point of maximum temperature, the whole series of curves forming an undulating "festoon." To the right of the series of curves the diagram represents unsaturated solutions; to the left, supersaturated. If an unsaturated solution, the composition of which is represented by a point in the field to the right of the solubility curves, is cooled down, the result obtained will differ according as the composition of the solution is the same as that of a cryohydric point, or of a melting point, or has an intermediate value. Thus, if a solution represented by _x__{1} is cooled down, the composition will remain unchanged as indicated by the horizontal dotted line, until the point D is reached. At this point, dodecahydrate and heptahydrate will separate out, and the liquid will ultimately solidify completely to a mixture or "conglomerate" of these two hydrates; the temperature of {155} the system remaining constant until complete solidification has taken place. If, on the other hand, a solution of the composition _x__{3} is cooled down, ferric chloride dodecahydrate will be formed when the temperature has fallen to that represented by C, and the solution will completely solidify, without alteration of temperature, with formation of this hydrate. In both these cases, therefore, a point is reached at which complete solidification occurs without change of temperature. Somewhat different, however, is the result when the solution has an intermediate composition, as represented by _x__{2} or _x__{4}. In the former case the dodecahydrate will first of all separate out, but on further withdrawal of heat the temperature will fall, the solution will become relatively richer in ferric chloride, owing to separation of the hydrate, and ultimately the eutectic point D will be reached, at which complete solidification will occur. Similarly with the second solution. Ferric chloride dodecahydrate will first be formed, and the temperature will gradually fall, the composition of the solution following the curve CB until the cryohydric point B is reached, when the whole will solidify to a conglomerate of ice and dodecahydrate. Suspended Transformation.--Not only can the upper branch of the solubility curve of the dodecahydrate be followed backwards to a temperature of 8°, or about 19° below the temperature of transition to the heptahydrate; but suspended transformation has also been observed in the case of the heptahydrate and the pentahydrate. To such an extent is this the case that the solubility curve of the latter hydrate has been followed downwards to its point of intersection with the curve for the dodecahydrate. This point of intersection, represented in Fig. 39 by M, lies at a temperature of about 15°; and at this temperature, therefore, it is possible for the two solid phases dodecahydrate and pentahydrate to coexist, so that M is a eutectic point for the dodecahydrate and the pentahydrate. It is, however, a metastable eutectic point, for it lies in the region of supersaturation with respect to the heptahydrate; and it can be realized only because of the fact that the latter hydrate is not readily formed. Evaporation of Solutions at Constant Temperature.--On {156} evaporating dilute solutions of ferric chloride at constant temperature, a remarkable series of changes is observed, which, however, will be understood with the help of Fig. 40. Suppose an unsaturated solution, the composition of which is represented by the point _x__{1}, is evaporated at a temperature of about 17° - 18°. As water passes off, the composition of the solution will follow the dotted line of constant temperature, until at the point where it cuts the curve BC the solid hydrate Fe_{2}Cl_{6},12H_{2}O separates out. As water continues to be removed, the hydrate must be deposited (in order that the solution shall remain saturated), until finally the solution dries up to the hydrate. As dehydration proceeds, the heptahydrate can be formed, and the dodecahydrate will finally pass into the heptahydrate; and this, in turn, into the pentahydrate. [Illustration: FIG. 40.] But the heptahydrate is not always formed by the dehydration of the dodecahydrate, and the behaviour on evaporation is therefore somewhat perplexing at first sight. After the solution has dried to the dodecahydrate, as explained above, further removal of water causes liquefaction, and the system is now represented by the point of intersection at _a_; at this point the solid hydrate is in equilibrium with a solution containing relatively more ferric chloride. If, therefore, evaporation is continued, the solid hydrate must _pass into solution_ in order that the composition of the latter may remain unchanged, so that ultimately a liquid will again be obtained. A very slight further dehydration will bring the solution into the state represented by _b_, at which the pentahydrate is formed, and the solution will at last disappear and leave this hydrate alone. Without the information to be obtained from the curves in Figs. 39 and 40, the phenomena which would be observed on carrying out the evaporation at a temperature of about 31 - 32° {157} would be still more bewildering. The composition of the different solutions formed will be represented by the perpendicular line _x__{2}12345. Evaporation will first cause the separation of the dodecahydrate, and then total disappearance of the liquid phase. Then liquefaction will occur, and the system will now be represented by the point 2, in which condition it will remain until the solid hydrate has disappeared. Following this there will be deposition of the heptahydrate (point 3), with subsequent disappearance of the liquid phase. Further dehydration will again cause liquefaction, when the concentration of the solution will be represented by the point 4; the heptahydrate will ultimately disappear, and then will ensue the deposition of the pentahydrate, and complete solidification will result. On evaporating a solution, therefore, of the composition _x__{2}, the following series of phenomena will be observed: solidification to dodecahydrate; liquefaction; solidification to heptahydrate; liquefaction; solidification to pentahydrate.[233] Although ferric chloride and water form the largest and best-studied series of hydrates possessing definite melting points, examples of similar hydrates are not few in number; and more careful investigation is constantly adding to the list.[234] In all these cases the solubility curve will show a point of maximum temperature, at which the hydrate melts, and will end, above and below, in a cryohydric point. Conversely, if such a curve is found in a system of two components, we can argue that a definite compound of the components possessing a definite melting point is formed. Inevaporable Solutions.--If a saturated solution in contact with two hydrates, or with a hydrate and anhydrous salt is heated, the temperature and composition of the solution will, of course, remain unchanged so long as the two solid phases are present, for such a system is invariant. In addition to this, however, the _quantity_ of the solution will also remain unchanged, the water which evaporates being supplied by the higher hydrate. The same phenomenon is also observed in the case of cryohydric points when ice is a solid phase; so long as the latter is present, evaporation will be accompanied {158} by fusion of the ice, and the quantity of solution will remain constant. Such solutions are called _inevaporable_.[235] [Illustration: FIG. 41.] Illustration.--In order to illustrate the application of the principles of the Phase Rule to the study of systems formed by a volatile and a non-volatile component, a brief description may be given of the behaviour of sulphur dioxide and potassium iodide, which has formed the subject of a recent investigation. After it had been found[236] that liquid sulphur dioxide has the property of dissolving potassium iodide, and that the solutions thus obtained present certain peculiarities of behaviour, the question arose as to whether or not compounds are formed between the sulphur dioxide and the potassium iodide, and if so, what these compounds are. To find an answer to this question, Walden and Centnerszwer[237] made a complete investigation of the solubility curves (equilibrium curves) of these two components, the investigation extending from the freezing point to the critical point of sulphur dioxide. For convenience of reference, the results which they obtained are represented diagrammatically in Fig. 41. The freezing point (A) of pure sulphur dioxide was found to be -72.7°. Addition of potassium iodide lowered the freezing point, but the maximum depression obtained was very small, and was reached when the concentration of the potassium iodide in the solution was only 0.336 mols. per cent. Beyond this point, an increase in the concentration of the iodide was accompanied by an elevation of the freezing point, the change of the freezing point with the concentration being represented by the curve BC. The solid {159} which separated from the solutions represented by BC was a bright _yellow_ crystalline substance. At the point C (-23.4°) a temperature-maximum was reached; and as the concentration of the potassium iodide was continuously increased, the temperature of equilibrium first fell and then slowly rose, until at +0.26° (E) a second temperature-maximum was registered. On passing the point D, the solid which was deposited from the solution was a _red_ crystalline substance. On withdrawing sulphur dioxide from the system, the solution became turbid, and the temperature remained constant. The investigation was not pursued farther at this point, the attention being then directed to the equilibria at higher temperatures. When a solution of potassium iodide in liquid sulphur dioxide containing 1.49 per cent. of potassium iodide was heated, solid (potassium iodide) was deposited at a temperature of 96.4°. Solutions containing more than about 3 per cent. of the iodide separated, on being heated, into two layers, and the temperature at which the liquid became heterogeneous fell as the concentration was increased; a temperature-minimum being obtained with solutions containing 12 per cent. of potassium iodide. On the other hand, solutions containing 30.9 per cent. of the iodide, on being heated, deposited potassium iodide; while a solution containing 24.5 per cent. of the salt first separated into two layers at 89.3°, and then, on cooling, solid was deposited and one of the liquid layers disappeared. Such are, in brief, the results of experiment; their interpretation in the light of the Phase Rule is the following:-- The curve AB is the freezing-point curve of solid sulphur dioxide in contact with solutions of potassium iodide. BCD is the solubility curve of the yellow crystalline solid which is deposited from the solutions. C, the temperature-maximum, is the melting point of this _yellow_ solid, and the composition of the latter must be the same as that of the solution at this point (p. 145), which was found to be that represented by the formula KI,14SO_{2}. B is therefore the eutectic point, at which solid sulphur dioxide and the compound KI,14SO_{2} can exist together in equilibrium with solution and vapour. The curve DE is the solubility curve of the _red_ crystalline solid, and the {160} point E, at which the composition of solution and solid is the same, is the melting point of the solid. The composition of this substance was found to be KI,4SO_{2}.[238] D is, therefore, the eutectic point at which the compounds KI,14SO_{2} and KI,4SO_{2} can coexist in equilibrium with solution and vapour. The curve DE does not exhibit a retroflex portion; on the contrary, on attempting to obtain more concentrated solutions in equilibrium with the compound KI,4SO_{2}, a new solid phase (probably potassium iodide) was formed. Since at this point there are four phases in equilibrium, viz. the compound KI,4SO_{2}, potassium iodide, solution, and vapour, the system is invariant. E is, therefore, the _transition point_ for KI,4SO_{2} and KI. Passing to higher temperatures, FG is the solubility curve of potassium iodide in sulphur dioxide; at G two liquid phases are formed, and the system therefore becomes invariant (cf. p. 121). The curve GHK is the solubility curve for two partially miscible liquids; and since complete miscibility occurs on _lowering_ the temperature, the curve is similar to that obtained with triethylamine and water (p. 101). K is also an invariant point at which potassium iodide is in equilibrium with two liquid phases and vapour. The complete investigation of the equilibria between sulphur dioxide and potassium iodide, therefore, shows that these two components form the compounds KI,14SO_{2} and KI,4SO_{2}; and that when solutions having a concentration between those represented by the points G and K are heated, separation into two layers occurs. The temperatures and concentrations of the different characteristic points are as follows:-- ------------------------------------------------------------- | | Composition of Point. | Temperature. | the solution | | per cent. KI. ------------------------------------------------------------- A (m.p. of SO_{2}) | -72.7° | -- B (eutectic point) | -- | 0.86 C (m.p. of KI,14SO_{2}) | -23.4° | 17.63 E (m.p. of KI,4SO_{2}) | +0.26° | 39.33 G (KI + two liquid phases) | (about) 88° | 24.0 H (critical solution point) | 77.3° | 12 K (KI + two liquid phases) | (about) 88° | 2.7 ------------------------------------------------------------- * * * * * {161} CHAPTER IX EQUILIBRIA BETWEEN TWO VOLATILE COMPONENTS General.--In the two preceding chapters certain restrictions were imposed on the discussion of the equilibria between two components; but in the present chapter the restriction that only one of the components is volatile will be allowed to fall, and the general behaviour of two volatile[239] components, each of which is capable of forming a liquid solution with the other, will be studied. As we shall see, however, the removal of the previous restriction produces no alteration in the general aspect of the equilibrium curves for concentration and temperature, but changes to some extent the appearance of the pressure-temperature diagram. The latter would become still more complicated if account were taken not only of the total pressure but also of the partial pressures of the two components in the vapour phase; this complication, however, will not be introduced in the present discussion.[240] In this chapter we shall consider the systems formed by the two components iodine and chlorine, and sulphur dioxide and water. Iodine and Chlorine.--The different systems furnished by iodine and chlorine, rendered classical by the studies of Stortenbeker,[241] form a very complete example of equilibria in a two-component system. We shall first of all consider the {162} relations between concentration and temperature, with the help of the accompanying diagram, Fig. 42. [Illustration: FIG. 42.] Concentration-Temperature Diagram.--In this diagram the temperatures are taken as the abscissæ, and the composition of the solution, expressed in atoms of chlorine to one atom of iodine,[242] is represented by the ordinates. In the diagram, A represents the melting point of pure iodine, 114°. If chlorine is added to the system, a solution of chlorine in liquid iodine is obtained, and the temperature at which solid iodine is in equilibrium with the liquid solution will be all the lower the greater the concentration of the chlorine. We therefore obtain the curve ABF, which represents the composition of the solution {163} with which solid iodine is in equilibrium at different temperatures. This curve can be followed down to 0°, but at temperatures below 7.9° (B) it represents metastable equilibria. At B iodine monochloride can be formed, and if present the system becomes invariant; B is therefore a quadruple point at which the four phases, iodine, iodine monochloride, solution, and vapour, can coexist. Continued withdrawal of heat at this point will therefore lead to the complete solidification of the solution to a mixture or conglomerate of iodine and iodine monochloride, while the temperature remains constant during the process. B is the eutectic point for iodine and iodine monochloride. Just as we found in the case of aqueous salt solutions that at temperatures above the cryohydric or eutectic point, two different solutions could exist, one in equilibrium with ice, the other in equilibrium with the salt (or salt hydrate), so in the case of iodine and chlorine there can be two solutions above the eutectic point B, one containing a lower proportion of chlorine in equilibrium with iodine, the other containing a higher proportion of chlorine in equilibrium with iodine monochloride. The composition of the latter solution is represented by the curve BCD. As the concentration of chlorine is increased, the temperature at which there is equilibrium between iodine monochloride and solution rises until a point is reached at which the composition of the solution is the same as that of the solid. At this point (C), iodine monochloride melts. Addition of one of the components will lower the temperature of fusion, and a continuous curve,[243] exhibiting a retroflex portion as in the case of CaCl_{2},6H_{2}O, will be obtained. At temperatures below its melting point, therefore, iodine monochloride can be in equilibrium with two different solutions. The upper portion of this curve, CD, can be followed downwards to a temperature of 22.7°. At this temperature iodine trichloride can separate out, and a second quadruple {164} point (D) is obtained. This is the eutectic point for iodine monochloride and iodine trichloride. By addition of heat and increase in the amount of chlorine, the iodine monochloride disappears, and the system passes along the curve DE, which represents the composition of the solutions in equilibrium with solid iodine trichloride. The concentration of chlorine in the solution increases as the temperature is raised, until at the point E, where the solution has the same composition as the solid, the maximum temperature is reached; the iodine trichloride melts. On increasing still further the concentration of chlorine in the solution, the temperature of equilibrium falls, and a continuous curve, similar to that for the monochloride, is obtained. The upper branch of this curve has been followed down to a temperature of 30°, the solution at this point containing 99.6 per cent. of chlorine.[244] The very rounded form of the curve is due to the trichloride being largely dissociated in the liquid state. One curve still remains to be considered. As has already been mentioned, iodine monochloride can exist in two crystalline forms, only one of which, however, is stable at temperatures below the melting point; the two forms are _monotropic_ (p. 44). The stable form which melts at 27.2°, is called the [alpha]-form, while the less stable variety, melting at 13.9°, is known as the [beta]-form. If, now, the presence of [alpha]-ICl is excluded, it is possible to obtain the [beta]-form, and to study the conditions of equilibrium between it and solutions of iodine and chlorine, from the eutectic point F to the melting point G. As the [beta]-ICl becomes less stable in presence of excess of chlorine, it has not been possible to study the retroflex portion of the curve represented by the dotted continuation of FG. The following table gives some of the numerical data from which Fig. 42 was constructed.[245] {165} IODINE AND CHLORINE. I. _Invariant systems._ ------------------------------------------------------------------------- | | Phases present. Temper-| Pressure.+--------------------+-----------------+-------------- ature. | | Solid. | Liquid. | Vapour. --------+----------+--------------------+-----------------+-------------- 7.9° | 11 mm. | I_{2},[alpha]-ICl | I[wavy]Cl_{0.66}| I + Cl_{0.92} 0.9° | -- | I_{2},[beta]-ICl | I[wavy]Cl_{0.72}| -- 22.7° | 42 mm. | [alpha]-ICl,ICl_{3}| I[wavy]Cl_{1.19}| I + Cl_{1.75} [-102° | <1 atm. | ICl_{3},Cl_{2} | I[wavy]Cl_{m} | I + Cl_{n}] --------+----------+--------------------+-----------------+-------------- II. _Melting points._ A. Iodine,[246] 114.15° (pressure 89.8 mm.). C. [alpha]-Iodine monochloride, 27.2° (pressure 37 mm.). E. Iodine trichloride, 101° (pressure 16 atm.). G. [beta]-Iodine monochloride, 13.9°. Since the vapour pressure at the melting point of iodine trichloride amounts to 16 atm., the experiments must of course be carried out in closed vessels. At 63.7° the vapour pressure of the system trichloride--solution--vapour is equal to 1 atm. Pressure-Temperature Diagram.--In this diagram there are represented the values of the vapour pressure of the saturated solutions of chlorine and iodine. To give a complete picture of the relations between pressure, temperature, and concentration, a solid model would be required, with three axes at right angles to one another along which could be measured the values of pressure, temperature, and concentration of the components in the solution. Instead of this, however, there may be employed the accompanying projection figure[247] (Fig. 43), the lower portion of which shows the projection of the equilibrium curve on the surface containing the concentration and temperature axes, while the upper portion is the projection on the plane containing the pressure and temperature axes. The lower portion is therefore a concentration-temperature diagram; {166} the upper portion, a pressure-temperature diagram. The corresponding points of the two diagrams are joined by dotted lines. [Illustration: FIG. 43.] Corresponding to the point C, the melting point of pure iodine, there is the point C_{1}, which represents the vapour pressure of iodine at its melting point. At this point three curves cut: 1, the sublimation curve of iodine; 2, the vaporization curve of fused iodine; 3, C_{1}B_{1}, the vapour-pressure curve of the saturated solutions in equilibrium with solid iodine. Starting, therefore, with the system solid iodine--liquid iodine, addition of chlorine will cause the temperature of equilibrium to fall continuously, while the vapour pressure will first increase, pass through a maximum and then fall continuously {167} until the eutectic point, B (B_{1}), is reached.[248] At this point the system is invariant, and the pressure will therefore remain constant until all the iodine has disappeared. As the concentration of the chlorine increases in the manner represented by the curve B_f_H, the pressure of the vapour also increases as represented by the curve B_{1}_f__{1}H_{1}. At H_{1}, the eutectic point for iodine monochloride and iodine trichloride, the pressure again remains constant until all the monochloride has disappeared. As the concentration of the solution passes along the curve HF, the pressure of the vapour increases as represented by the curve H_{1}F_{1}; F_{1} represents the pressure of the vapour at the melting point of iodine trichloride. If the concentration of the chlorine in the solution is continuously increased from this point, the vapour pressure first increases and then decreases, until the eutectic point for iodine trichloride and solid chlorine is reached (D_{1}). Curves Cl_{2} solid and Cl_{2} liquid represent the sublimation and vaporization curves of chlorine, the melting point of chlorine being -102°. Although complete measurements of the vapour pressure of the different systems of pure iodine to pure chlorine have not been made, the experimental data are nevertheless sufficient to allow of the general form of the curves being indicated with certainty. Bivariant Systems.--To these, only a brief reference need be made. Since there are two components, two phases will form a bivariant system. The fields in which these systems can exist are shown in Fig. 43 and Fig. 44, which is a more diagrammatic representation of a portion of Fig. 43. I. Iodine--vapour. II. Solution--vapour. III. Iodine trichloride--vapour. IV. Iodine monochloride--vapour. [Illustration: FIG. 44.] The conditions for the existence of these systems will probably be best understood from Fig. 44. Since the curve B'A' {168} represents the pressures under which the system iodine--solution--vapour can exist, increase of volume (diminution of pressure) will cause the volatilization of the solution, and the system iodine--vapour will remain. If, therefore, we start with a system represented by _a_, diminution of pressure at constant temperature will lead to the condition represented by _x_. On the other hand, increase of pressure at _a_ will lead to the condensation of a portion of the vapour phase. Since, now, the concentration of chlorine in the vapour is greater than in the solution, condensation of vapour would increase the concentration of chlorine in the solution; a certain amount of iodine must therefore pass into solution in order that the composition of the latter shall remain unchanged.[249] If, therefore, the volume of vapour be sufficiently great, continued diminution of volume will ultimately lead to the disappearance of all the iodine, and there will remain only solution and vapour (field II.). As the diminution of volume is continued, the vapour pressure and the concentration of the chlorine in the solution will increase, until when the pressure has reached the value _b_, iodine monochloride can separate out. The system, therefore, again becomes univariant, and at constant temperature the pressure and composition of the phases must remain unchanged. Diminution of volume will therefore not effect an increase of pressure, but a condensation of the vapour; and since this is richer in chlorine than the {169} solution, solid iodine monochloride must separate out in order that the concentration of the solution remain unchanged.[250] As the result, therefore, we obtain the bivariant system iodine monochloride--vapour. A detailed discussion of the effect of a continued increase of pressure will not be necessary. From what has already been said and with the help of Fig. 44, it will readily be understood that this will lead successively to the univariant system (_c_), iodine monochloride--solution--vapour; the bivariant system solution--vapour (field II.); the univariant system (_d_), iodine trichloride--solution--vapour; and the bivariant system _x'_, iodine trichloride--vapour. If the temperature of the experiment is above the melting point of the monochloride, then the systems in which this compound occurs will not be formed. Sulphur Dioxide and Water.--In the case just studied we have seen that the components can combine to form definite compounds possessing stable melting points. The curves of equilibrium, therefore, resemble in their general aspect those of calcium chloride and water, or of ferric chloride and water. In the case of sulphur dioxide and water, however, the melting point of the compound formed cannot be realized, because transition to another system occurs; retroflex concentration-temperature curves are therefore not found here, but the curves exhibit breaks or sudden changes in direction at the transition points, as in the case of the systems formed by sodium sulphate and water. The case of sulphur dioxide and water is also of interest from the fact that two liquid phases can be formed. The phases which occur are--Solid: ice, sulphur dioxide hydrate, SO_{2},7H_{2}O. Liquid: two solutions, the one containing excess of sulphur dioxide, the other excess of water, and represented by the symbols SO_{2} [wavy] _x_H_{2}O (solution I.), and H_{2}O [wavy] _y_SO_{2} (solution II.). Vapour: a mixture of sulphur dioxide and water vapour in varying proportions. Since there are two components, sulphur dioxide and water, the number of {170} possible systems is considerable. Only the following, however, have been studied:-- I. _Invariant Systems: Four co-existing phases._ (_a_) Ice, hydrate, solution, vapour. (_b_) Hydrate, solution I., solution II., vapour. II. _Univariant Systems: Three co-existing phases._ (_a_) Hydrate, solution I., vapour. (_b_) Hydrate, solution II., vapour. (_c_) Solution I., solution II., vapour. (_d_) Hydrate, solution I., solution II. (_e_) Hydrate, ice, vapour. (_f_) Ice, solution II., vapour. (_g_) Ice, hydrate, solution II. III. _Bivariant Systems: Two co-existing phases._ (_a_) Hydrate, solution I. (_b_) Hydrate, solution II. (_c_) Hydrate, vapour. (_d_) Hydrate, ice. (_e_) Solution I., solution II. (_f_) Solution I., vapour. (_g_) Solution I., ice. (_h_) Solution II., vapour. (_i_) Solution II., ice. (_j_) Ice, vapour. [Illustration: FIG. 45.] Pressure-Temperature Diagram.[251]--If sulphur dioxide is passed into water at 0°, a solution will be formed and the temperature at which ice can exist in equilibrium with this solution will fall more and more as the concentration of the sulphur dioxide increases. At -2.6°, however, a cryohydric point is reached at which solid hydrate separates out, and the system becomes invariant. The curve AB (Fig. 45) therefore represents the pressure of the system ice--solution II.--vapour, and B represents the temperature and pressure at which the invariant system ice--hydrate--solution II.--vapour can exist. At this point the temperature is -2.6°, and the pressure 21.1 cm. If heat is withdrawn from this system, the solution will ultimately {171} solidify to a mixture of ice and hydrate, and there will be obtained the univariant system ice--hydrate--vapour. The vapour pressure of this system has been determined down to a temperature of -9.5°, at which temperature the pressure amounts to 15 cm. The pressures for this system are represented by the curve BC. If at the point B the volume is diminished, the pressure must remain constant, but the relative amounts of the different phases will undergo change. If suitable quantities of these are present, diminution of volume will ultimately lead to the total condensation of the vapour phase, and there will remain the univariant system ice--hydrate--solution. The temperature of equilibrium of this system will alter with the pressure, but, as in the case of the melting point of a simple substance, great differences of pressure will cause only comparatively small changes in the temperature of equilibrium. The change of the cryohydric point with the pressure is represented by the line BE; the actual values have not been determined, but the curve must slope towards the pressure axis because fusion is accompanied by diminution of volume, as in the case of pure ice. {172} A fourth univariant system can be formed at B. This is the system hydrate--solution II.--vapour. The conditions for the existence of this system are represented by the curve BF, which may therefore be regarded as the vapour-pressure curve of the saturated solution of sulphur dioxide heptahydrate in water. Unlike the curve for iodine trichloride--solution--vapour, this curve cannot be followed to the melting point of the hydrate. Before this point is reached, a second liquid phase appears, and an invariant system consisting of hydrate--solution I.--solution II.--vapour is formed. We have here, therefore, the phenomenon of melting under the solution as in the case of succinic nitrile and water (p. 122). This point is represented in the diagram by F; the temperature at this point is 12.1°, and the pressure 177.3 cm. The range of stable existence of the hydrate is therefore from -2.6° to 12.1°; nevertheless, the curve FB has been followed down to a temperature of -6°, at which point ice formed spontaneously. So long as the four phases hydrate, two liquid phases, and vapour are present, the condition of the system is perfectly defined. By altering the conditions, however, one of the phases can be made to disappear, and a univariant system will then be obtained. Thus, if the vapour phase is made to disappear, the univariant system solution I.--solution II.--hydrate, will be left, and the temperature at which this system is in equilibrium will vary with the pressure. This is represented by the curve FI; under a pressure of 225 atm. the temperature of equilibrium is 17.1°. Increase of pressure, therefore, raises the temperature at which the three phases can coexist. Again, addition of heat to the invariant system at F will cause the disappearance of the solid phase, and there will be formed the univariant system solution I.--solution II.--vapour. In the case of this system the vapour pressure increases as the temperature rises, as represented by the curve FG. Such a system is analogous to the case of ether and water, or other two partially miscible liquids (p. 103). As the temperature changes, the composition of the two liquid phases will undergo change; but this system has not been studied fully. The fourth curve, which ends at the quadruple point F, is {173} that representing the vapour pressure of the system hydrate--solution I.--vapour (FH). This curve has been followed to a temperature of 0°, the pressure at this point being 113 cm. The metastable prolongation of GF has also been determined. Although, theoretically, this curve must lie below FH, it was found that the difference in the pressure for the two curves was within the error of experiment. Bivariant Systems.--The different bivariant systems, consisting of two phases, which can exist within the range of temperature and pressure included in Fig. 45, were given on p. 170. The conditions under which these systems can exist are represented by the areas in the diagram, and the fields of the different bivariant systems are indicated by letters, corresponding to the letters on p. 170. Just as in the case of one-component systems (p. 29), we found that the field lying between any two curves gave the conditions of existence of that phase which was common to the two curves, so also in the case of two-component systems, a bivariant two-phase system occurs in the field enclosed[252] by the two curves to which the two phases are common. As can be seen, the same bivariant system can occur in more than one field. As is evident from Fig. 45, three different bivariant systems are capable of existing in the area HFI; which of these will be obtained will depend on the relative masses of the different phases in the univariant or invariant system. Thus, starting with a system represented by a point on the curve HF, diminution of volume at constant temperature will cause the condensation of a portion of the vapour, which is rich in sulphur dioxide; since this would increase the concentration of sulphur dioxide in the solution, it must be counteracted by the passage of a portion of the hydrate (which is relatively poor in sulphur dioxide) into the solution. If, therefore, the amount of hydrate present is relatively very small, the final result of the compression will be the production of the system _f_, solution I.--vapour. On the other hand, if the vapour is present in relatively small amount, it will be the first phase to disappear, {174} and the bivariant system _a_, hydrate--solution I., will be obtained. Finally, if we start with the invariant system at F, compression will cause the condensation of vapour, while the composition of the two solutions will remain unchanged. When all the vapour has disappeared, the univariant system hydrate--solution I.--solution II. will be left. If, now, the pressure is still further increased, while the temperature is kept below 12°, more and more hydrate must be formed at the expense of the two liquid phases (because 12° is the lower limit for the coexistence of the two liquid phases), and if the amount of the solution I. (containing excess of sulphur dioxide) is relatively small, it will disappear before solution II., and there will be obtained the bivariant system hydrate--solution II. (bivariant system _b_). In a similar manner, account can be taken of the formation of the other bivariant systems. A behaviour similar to that of sulphur dioxide and water is shown by chlorine and water and by bromine and water, although these have not been so fully studied.[253] In the case of hydrogen bromide and water, and of hydrogen chloride and water, a hydrate, viz. HBr,2H_{2}O and HCl,2H_{2}O, is formed which possesses a definite melting point, as in the case of iodine trichloride. In these cases, therefore, a retroflex curve is obtained. Further, just as in the case of the chlorides of iodine the upper branch of the retroflex curve ended in a eutectic point, so also in the case of the hydrate HBr,2H_{2}O the upper branch of the curve ends in a eutectic point at which the system dihydrate--monohydrate--solution--vapour can exist. Before the melting point of the monohydrate is reached, two liquid phases are formed, as in the case of sulphur dioxide and water. * * * * * {175} CHAPTER X SOLID SOLUTIONS. MIXED CRYSTALS General.--With the conception of gaseous and liquid solutions, every one is familiar. Gases can mix in all proportions to form homogeneous solutions. Gases can dissolve in or be "absorbed" by liquids; and solids, also, when brought in contact with liquids, "pass into solution" and yield a homogeneous liquid phase. On the other hand, the conception of a _solid solution_ is one which in many cases is found more difficult to appreciate; and the existence and behaviour of solid solutions, in spite of their not uncommon occurrence and importance, are in general comparatively little known. The reason of this is to be found, to some extent, no doubt, in the fact that the term "solid solution" was introduced at a comparatively recent date,[254] but it is probably also due in some measure to a somewhat hazy comprehension of the definition of the term "solution" itself. As has already been said (p. 92), a solution is a homogeneous phase, the composition of which can vary continuously within certain limits; the definition involves, therefore, no condition as to the physical state of the substances. Accordingly, solid solutions are homogeneous solid phases, the composition of which can undergo continuous variation within certain limits. Just as we saw that the range of variation of composition is more limited in the case of liquids than in the case of gases, so also we find that the limits of miscibility are in general still more restricted in the case of solids. Examples of complete miscibility are, however, not unknown even in the case of solid substances. Solid solutions have long been known, although, of course, {176} they were not defined as such. Thus, the phenomena of "occlusion" of gases by metals and other substances (occlusion of hydrogen by palladium; occlusion of hydrogen by iron) are due to the formation of solid solutions. The same is probably also true of the phenomena of "adsorption," as in the removal of organic colouring matter by charcoal, although, in this case, surface tension no doubt plays a considerable part.[255] As examples of the solution of gases in solids there may be cited (in addition to the phenomena of occlusion already mentioned), the hydrated silicates and the zeolites. During dehydration these crystalline substances remain clear and transparent, and the pressure of the water vapour which they emit varies with the degree of hydration or the concentration of water in the mineral.[256] As examples of the solution of solids in solids we have the cementation of iron by charcoal, the formation of glass, and the crystallization together of isomorphous substances. Although we have here spoken of the glasses as "solid solutions," it should be mentioned that the term "solid" is used in its popular sense. Strictly speaking, the glasses are to be regarded as supercooled liquids (see also p. 53, footnote). In discussing the equilibria in systems containing a solid solution, it is of essential importance to remember that a solid solution constitutes only _one_ phase, a phase of varying composition, as in the case of liquid solutions. Solution of Gases in Solids.--Comparatively little work has been done in this connection, the investigations being limited chiefly to the phenomena of occlusion or adsorption of gases by charcoal.[257] We shall, therefore, indicate only briefly {177} and in a general manner, the behaviour which the Phase Rule enables us to foresee.[258] In dealing with the systems formed by the two phases gas--solid, three chief cases call for mention:-- I. _The gas is not absorbed by the solid, but when the pressure reaches a certain value, combination of the two components can result._ [Illustration: Fig. 46.] The graphic representation of such a system is shown in Fig. 46, the ordinates being the pressures of the gas, and the abscissæ the concentrations of the gaseous component in the solid phase. Since there is no formation of a solid solution, the concentration of gas in the solid phase remains zero until the pressure has increased to the point A. At this point combination can take place. There will now be three phases present, viz. solid component, compound, and vapour. The system is therefore univariant, and if the temperature is maintained constant, the vapour pressure will be constant, irrespective of the amount of compound formed, _i.e._ irrespective of the relative amounts of gas and solid. This is indicated by the line AB. When the solid component has entirely disappeared, the system ceases to be univariant, and if no absorption occurs, the pressure will increase again, as shown by BC. If a second compound can be formed, then a second _pc_-line will be obtained, similar to the preceding. To this group belong the salt hydrates (Chap. VII.). II. _The gas may be absorbed and may also form a compound._ If absorption of gas occurs with formation of a solid solution, then, as the system consists of two phases, solution--vapour, it is bivariant. At constant temperature, therefore, the pressure will still vary with the concentration of the gaseous component in the solid phase. This is represented by the curve AB in Fig. 47. When, however, the pressure has reached a certain value, combination can take place; and since there are now three phases present, the system is {178} univariant, and at constant temperature the pressure is constant, as shown by the line BC. III. _Absorption of gas occurs, but at a certain concentration the solid solution can separate into two immiscible solid solutions._ We have seen, in Chapter VI., that two liquids can form two immiscible solutions, and the same has also been found true of solid solutions, as we shall presently learn more fully. If, now, two immiscible solutions are formed, then the system will become univariant, and at constant temperature the _pc_-curve will be a straight line, as in the case of the formation of a compound (cf. p. 86). The behaviour of this system will, therefore, also be represented diagrammatically by Fig. 47. [Illustration: FIG. 47.] _Palladium and Hydrogen._--The phenomenon of the absorption of hydrogen by palladium, to which Graham gave the name "occlusion," is one that has claimed the attention of several investigators. Although Graham was not of opinion that a compound is formed, but rather that the gas undergoes very great condensation, acts as a quasi-metal (to which he gave the name hydrogenium), and forms a homogeneous alloy with the palladium, later investigations, especially those of Troost and Hautefeuille,[259] pointed to the formation of a definite chemical compound, having the formula Pd_{2}H. This conclusion has, however, not been confirmed by subsequent investigation.[260] Roozeboom and Hoitsema[261] sought to arrive at a final decision as to the nature of the phenomenon by an investigation of the equilibrium between hydrogen and palladium on the basis of the Phase Rule classification given above. If a compound is formed, diminution of volume would cause no increase of pressure, but only an increase in the amount of the compound. As this is the only case of gas absorption which has been {179} accurately studied from this point of view, a brief account of the results obtained will be given here, although these are not so clear and free from ambiguity as one would desire. The scientists just mentioned investigated the variation of the pressure of hydrogen with the amount absorbed by the metal at different temperatures, and a few of their results, typical of all, are represented graphically in Fig. 48; the curves indicating the variation of the gas pressure with the concentration of the hydrogen in the palladium at the temperatures 120°, 170°, and 200°. As can be seen, the curve consists of three parts, an ascending portion which passes gradually and continuously into an almost horizontal but slightly ascending middle part, which in turn passes without break into a second rapidly ascending curve. This, as Fig. 48 indicates, is the general form of the curve; but the length of the middle portion varies with the temperature, being shorter at higher than at lower temperatures. [Illustration: FIG. 48.] What is the interpretation to be put on these curves? With regard to the two end portions, these represent bivariant, two-phase systems, consisting of a solid solution and gas. They correspond, therefore, to curve AB in Fig. 47. If the middle portion were horizontal, it would indicate either the formation of a compound or of two immiscible solid solutions. If a compound Pd_{2}H were formed, then the middle portion would at all temperatures end at the same value of the concentration, viz. that corresponding to 0.5 atoms of hydrogen to 1 atom of palladium. As the figure shows, however, this is not the case; the higher the temperature, the lower is the concentration at which the middle passes into the terminal portion of the curve. {180} Such a behaviour would, however, agree with the assumption of the formation of two solid solutions, the "miscibility" of which increases with the temperature, as in the case of the liquid solutions of phenol and water (p. 97). Nevertheless, although the assumption of the formation of two solid solutions is more satisfactory than that of the formation of a compound, it does not entirely explain the facts. If two solid solutions are formed, the pressure curve should be horizontal, but this is not the case; and the deviation from the horizontal does not appear to be due to impurities either in the gas or in the metal, but is apparently a peculiarity of the system. Further, the gradual instead of abrupt passage of the three portions of the curve into one another remains unexplained. Hoitsema has expressed the opinion that the occlusion of hydrogen by palladium is a process of continuous absorption, the peculiar form of the curve--the flat middle portion--being possibly due to a condensation of the gas, even at temperatures far above the critical temperature of liquid hydrogen. While, therefore, the occlusion of hydrogen by palladium still presents some unexplained phenomena, the behaviour found by Hoitsema would appear to disprove conclusively the formation of a definite chemical compound.[262] SOLUTION OF SOLIDS IN SOLIDS. MIXED CRYSTALS. The introduction by van't Hoff of the term "solid solution" resulted from the discovery of a number of deviations from the Raoult-van't Hoff law for the depression of the freezing point by dissolved substances. In all cases, the depression was too small; in some instances, indeed, the freezing point may be raised. To explain these irregularities, van't Hoff assumed that the dissolved substance crystallized out along with the solid solvent; and he showed how this would account for the {181} deviations from the law of the depression of the freezing point, which had been developed on the assumption that only the pure solvent crystallized out from the solution.[263] The "mixed crystals" which were thus obtained, and which van't Hoff called dilute solid solutions, showed great resemblance in their behaviour to ordinary liquid solutions, and obeyed the laws applicable to these. These laws, however, can no longer be applied in the case of the concentrated solid solutions formed by the crystallization together of isomorphous substances, and known as isomorphous mixtures. Indeed, it has been contended[264] that these isomorphous mixtures should not be considered as solid solutions at all, although no sharp line of demarcation can be drawn between the two classes. The differences, however, in the behaviour of the two groups are of a quantitative rather than a qualitative nature; and since we are concerned at present only with the qualitative behaviour, we shall make no distinction between the crystalline solid solutions and the isomorphous mixtures, but shall study the behaviour of the two classes under the head of "mixed crystals." Mixed crystals can be formed either by sublimation[265] or from a liquid phase; and in the latter case the mixed crystals can be deposited either from solution in a common solvent or from a mixture of the fused components. In this method of formation, which alone will be discussed in the present chapter, we are dealing with the fusion curves of two substances, where, however, the liquid solution is in equilibrium not with one of the pure components, but with a solid solution or mixed crystal. The simple scheme (Fig. 29, p. 117) which was obtained in the case of two components which crystallize out in the pure state, is no longer sufficient in the case of the formation of mixed crystals. With the help of the Phase Rule, however, the different possible systems can be classified; and examples of the different cases predicted by the Phase Rule have also been obtained by experiment. {182} We shall now consider briefly the formation of mixed crystals by isomorphous substances; the consideration of the formation of mixed crystals of isodimorphous substances will, on account of the complexity of the relationships, not be undertaken here.[266] _Formation of Mixed Crystals of Isomorphous Substances._ For the purpose of representing the relationships found here we shall employ a temperature-concentration diagram,[267] in which the ordinates represent the temperature and the abscissæ the concentration of the components. Since there are two solutions, the liquid and the solid, and since the concentration of the components in these two phases is not, in general, the same, two curves will be required for each system, one relating to the liquid phase, the other relating to the solid. The temperature at which solid begins to be deposited from the liquid solution will be called the _freezing point_ of the mixture, and the temperature at which the solid solution just begins to liquefy will be called the _melting point_ of the solid solution. The temperature-concentration curve for the liquid phase will therefore be the freezing-point curve; that for the solid solution, the melting-point curve. The latter will be represented by a dotted line.[268] {183} I.--THE TWO COMPONENTS CAN FORM AN UNBROKEN SERIES OF MIXED CRYSTALS. Since, as has already been pointed out (p. 176), a mixed crystal (solid solution) constitutes only one phase, it is evident that if the two components are miscible with one another in all proportions in the solid state, there can never be more than one solid phase present, viz. the solid solution or mixed crystal. If the components are completely miscible in the solid state, they will also be completely miscible in the liquid state, and there can therefore be only one liquid phase. The system can at no point become invariant, because there can never be more than three phases present. When, therefore, the two components form a continuous series of mixed crystals, the equilibrium curve must also be continuous. Of these systems three types are found. [Illustration: FIG. 49.] (_a_) _The freezing points of all mixtures lie between the freezing points of the pure components_ (Curve I., Fig. 49). Examples.--This type of curve is represented by the mixed crystals of naphthalene and [beta]-naphthol.[269] The addition of [beta]-naphthol to naphthalene raises the freezing point of the latter, and the rise is directly proportional to the amount of naphthol added. The freezing point curve is therefore a straight line joining the melting points of the two components. This behaviour, however, is rather exceptional, the freezing-point curve lying generally above, sometimes also below, the straight line joining the melting points of the pure components. Thus the freezing-point curve of mixtures of [alpha]-monochlorocinnamic aldehyde and [alpha]-monobromocinnamic aldehyde[270] lies above the {184} straight line joining the melting points of the pure components (31.22° and 69.56°), as is evident from the following table:-- ---------------------------------------------------------------------- Molecules of bromo- | | cinnamic aldehyde in | Freezing point. | Deviation from straight 100 mols. of mixture. | | line. ---------------------------------------------------------------------- 0.00 | 31.22° | -- 10.48 | 37.28° | 2.04° 21.91 | 43.12° | 3.50° 30.07 | 46.80° | 4.05° 45.04 | 52.94° | 4.45° 62.16 | 58.82° | 3.77° 82.98 | 65.07° | 2.03° 93.50 | 67.91° | 0.84° 100.00 | 69.56° | -- ---------------------------------------------------------------------- Melting-point Curve.--This curve, like the freezing-point curve, must also be continuous, and the melting points of the different solid solutions will lie between the melting points of the pure components. This is represented by the dotted line in Fig. 49, I. The relative position of the two curves, which can be deduced with the help of thermodynamics and also by experimental determination, is found in all cases to be in accordance with the following rule: At any given temperature, _the concentration of that component by the addition of which the freezing point is depressed, is greater in the liquid than in the solid phase_; or, conversely, _the concentration of that component by the addition of which the freezing point is raised, is greater in the solid than in the liquid phase_. An illustration of this rule is afforded by the two substances chloro- and bromo-cinnamic aldehyde already mentioned. As can be seen from the above table, the addition of chlorocinnamic aldehyde lowers the melting point of the bromo-compound. In accordance with the rule, therefore, the concentration of the chloro-compound in the liquid phase must be greater than in the solid phase; and this was found experimentally. At a temperature of 49.44°, the liquid contained 58.52 per cent., the solid only 52.57 per cent. of the chlorocinnamic aldehyde. From this it will also be clear that on cooling a fused mixture of two substances capable of forming mixed crystals, {185} the temperature of solidification will not remain constant during the separation of the solid; nor, on the other hand, will the temperature of liquefaction of the solid solution be constant. Thus, for example, if a liquid solution of two components, A and B, having the composition represented by the point _x_ (Fig. 50), is allowed to cool, the system will pass along the line _xx'_. At the temperature of the point _a_, mixed crystals will be deposited, the composition of which will be that represented by b. As the temperature continues to fall, more and more solid will be deposited; and since the solid phase is relatively rich in the component B, the liquid will become relatively poorer in this. The composition of the liquid solution will therefore pass along the curve _ad_, the composition of the solid solution at the same time passing along the curve _bc_; at the point _c_ the liquid will solidify completely.[271] [Illustration: FIG. 50.] Conversely, if mixed crystals of the composition and at the temperature _x'_ are heated, liquefaction will begin at the temperature _c_, yielding a liquid of the composition d. On continuing to add heat, the temperature of the mass will rise, more of the solid will melt, and the composition of the two phases will change as represented by the curves _da_ and _cb_. When the temperature has risen to _a_, complete liquefaction will have occurred. The process of solidification or of liquefaction is therefore extended over a temperature interval _ac_. Even when the freezing-point curve is a straight line joining {186} the melting points of the pure components, the melting-point curve will not necessarily coincide with the freezing-point curve, although it may approach very near to it; complete coincidence can take place only when the melting points of the two components are identical. An example of this will be given later (Chap. XII.). (_b_) _The freezing-point curve passes through a maximum_ (Curve II., Fig. 49). [Illustration: FIG. 51.] This curve exhibits the greatest degree of contrast to the freezing-point curve which is obtained when the pure components crystallize out. For, since the curve passes through a maximum, it is evident that the freezing point of each of the components must be _raised_ by the addition of the other component. Example.--Very few cases belonging to this type are known. The best example is found in the freezing-point curve of mixtures of _d_- and _l_-carvoxime[272] (C_{10}H_{14}N.OH). The freezing points and melting points of the different mixtures of _d_- and _l_-carvoxime are given in the following table, and represented graphically in Fig. 51:-- ---------------+----------------+-----------------+----------------- Per cent. of | Per cent. of | Freezing point. | Melting point. _d_-carvoxime. | _l_-carvoxime. | | ---------------+----------------+-----------------+----------------- 100 | 0 | 72.0° | 72.0° 99 | 1 | 72.4° | -- 98 | 2 | 73.0° | -- 95 | 5 | 75.4° | 73.0° 90 | 10 | 79.0° | 75.0° 80 | 20 | 84.6° | 80.0° 70 | 30 | 88.2° | 85.0° 60 | 40 | 90.4° | -- 50 | 50 | 91.4° | 91.4° 25 | 75 | 86.4° | 82.0° 8 | 92 | 77.4° | -- 1 | 99 | 72.4° | -- 0 | 100 | 72.0° | 72.0° ---------------+----------------+-----------------+----------------- {187} In this figure, the melting-point curve, _i.e._ the temperature-concentration curve for the mixed crystals, is represented by the lower curve. Since the addition of the lævo-form to the dextro-form raises the melting point of the latter, the concentration of the lævo-form (on the right-hand branch of the curve) must, in accordance with the rule given, be greater in the solid phase than in the liquid. Similarly, since addition of the dextro-form raises the melting point of the lævo-form, the solid phase (on the left-hand branch of the curve) must be richer in dextro- than in lævo-carvoxime. At the maximum point, the melting-point and freezing-point curves touch; at this point, therefore, the composition of the solid and liquid phases must be identical. It is evident, therefore, that at the maximum point the liquid will solidify, or the solid will liquefy completely without change of temperature; and, accordingly, mixed crystals of the composition represented by the maximum point will exhibit a definite melting point, and will in this respect behave like a simple substance. (_c_) _The freezing-point curve passes through a minimum_ (Curve III., Fig. 49). In this case, as in the case of those systems where the pure components are deposited, a minimum freezing point is obtained. In the latter case, however, there are two freezing-point curves which intersect at a eutectic point; in the case where mixed crystals are formed there is only one continuous curve. On one side of the minimum point the liquid phase contains relatively more, on the other side relatively less, of the one component than does the solid phase; while at the minimum point the composition of the two phases is the same. At this point, therefore, complete solidification or complete liquefaction will occur without change of temperature, and the mixed crystals will accordingly exhibit a definite melting point. [Illustration: FIG. 52.] {188} Example.--As an example of this there may be taken the mixed crystals of mercuric bromide and iodide.[273] Mercuric bromide melts at 236.5°, and mercuric iodide at 255.4°. The mixed crystal of definite constant melting point (minimum point) contains 59 mols. per cent. of mercuric bromide, the melting point being 216.1°. The numerical data are contained in the following table, and represented graphically in Fig. 52:-- ----------------------------------------------------- Mols. per cent. of | | HgBr_{2}. | Freezing point. | Melting point. ----------------------------------------------------- 100 | 236.5° | 236° 90 | 228.8° | 226° 80 | 222.2° | 219° 70 | 217.8° | 217° 65 | 216.6° | 216° 60 | 216.1° | 215.5° 55 | 216.3° | 216° 50 | 217.3° | 216° 40 | 221.1° | 218° 30 | 227.8° | 223° 20 | 236.2° | 231° 10 | 245.5° | 242° 0 | 255.4° | 254° ----------------------------------------------------- [Illustration: FIG. 53.] Fractional Crystallization of Mixed Crystals.--With the help of the diagrams already given it will be possible to predict what will be the result of the fractional crystallization of a fused mixture of two substances which can form mixed crystals. Suppose, for example, a fused mixture of the composition _x_ (Fig. 53) is cooled down; then, as we have already seen, when the temperature has fallen to _a_, mixed crystals of composition, _b_, are deposited. If the temperature is allowed to fall {189} to _x'_, and the solid then separated from the liquid, the mixed crystals so obtained will have the composition represented by e. If, now, the mixed crystals _e_ are completely fused and the fused mass allowed to cool, separation of solid will occur when the temperature has fallen to the point _f_. The mixed crystals which are deposited have now the composition represented by _g_, i.e. _they are richer in B than the original mixed crystals_. By repeating this process, the composition of the successive crops of mixed crystals which are obtained approximates more and more to that of the pure component B, while, on the other hand, the composition of the liquid phase produced tends to that of pure A. By a systematic and methodical repetition of the process of fractional crystallization, therefore, a _practically_ complete separation of the components can be effected; a perfect separation is theoretically impossible. From this it will be readily understood that in the case of substances the freezing point of which passes through a maximum, fractional crystallization will ultimately lead to mixed crystals having the composition of the maximum point, while the liquid phase will more and more assume the composition of either pure A or pure B, according as the initial composition was on the A side or the B side of the maximum point. In those cases, however, where the curves exhibit a minimum, the solid phase which separates out will ultimately be one of the pure components, while a liquid phase will finally be obtained which has the composition of the minimum point. II.--THE TWO COMPONENTS DO NOT FORM A CONTINUOUS SERIES OF MIXED CRYSTALS. This case corresponds to that of the partial miscibility of liquids. The solid component A can "dissolve" the component B until the concentration of the latter in the mixed crystal has reached a certain value. Addition of a further amount of B will not alter the composition of the mixed crystal, but there will be formed a second solid phase consisting {190} of a solution of A in B. At this point the four phases, mixed crystals containing excess of A, mixed crystals containing excess of B, liquid solution, vapour, can coexist; this will therefore be an invariant point. The temperature-concentration curves will therefore no longer be continuous, but will exhibit a break or discontinuity at the point at which the invariant system is formed. (_a_) _The freezing-point curve exhibits a transition point_ (Curve I., Fig. 54). As is evident from the figure, addition of B raises the melting point of A, and, in accordance with the rule previously given, the concentration of B in the mixed crystals will be greater than in the solution. This is represented in the figure by the dotted curve AD. On the other hand, addition of A lowers the melting point of B, and the two curves BC and BE are obtained for the liquid and solid phases respectively. At the temperature of the line CDE the liquid solution of the composition represented by C is in equilibrium with the two different mixed crystals represented by D and E. At this temperature, therefore, the _tc_-curve for the solid phase exhibits a discontinuity; and, since the solid phase undergoes change at this point, the freezing-point curve must show a break (p. 111). [Illustration: FIG. 54.] Example.--Curves of the form given in Fig. 54 I. have been found experimentally in the case of silver nitrate and sodium nitrate.[274] The following table contains the numerical data, which are also represented graphically in Fig. 55:-- {191} ----------------------------------------------------- Molecules NaNO_{3} | Freezing point. | Melting point. per cent. | | ----------------------------------------------------- 0 | 208.6° | 208.6° 8 | 211.4° | 210° 15.06 | 215° | 212° 19.46 | 217.2° | 214.8° 21.9 | 222° | 215° 26 | 228.4° | 216.5° 29.7 | 234.8° | 217.5° 36.2 | 244.4° | 217.5° 47.3 | 259.4° | 237.6° 58.9 | 272° | 257° 72 | 284° | 274° 100 | 308° | 308° ----------------------------------------------------- The temperature of the transition point is 217.5°; at this point the liquid contains 19.5, and the two conjugate solid solutions 26 and 38 molecules of sodium nitrate per cent. respectively. [Illustration: FIG. 55.] [Illustration: FIG. 56.] (_b_) _The freezing-point curve exhibits a eutectic point_ (Curve II., Fig. 54). {192} In this case the freezing point of each of the components is lowered by the addition of the other, until at last a point is reached at which the liquid solution solidifies to a mixture or conglomerate of two mixed crystals. Examples.--Curves belonging to this class have been obtained in the case of potassium and thallium nitrates[275] and of naphthalene and monochloracetic acid.[276] The data for the latter are given in the following table and represented in Fig. 56:-- ------------------------------------------------------------------------- | Liquid solution. | Solid solution. ------------------------------------------------------------ Temperature. | | | | | Per cent. | Per cent. | Per cent. | Per cent. | naphthalene. | acid. | naphthalene. | acid. ------------------------------------------------------------------------- 62° | -- | 100 | -- | 100 60° | 4.0 | 96.0 | 1.7 | 98.3 55° | 21.0 | 79.0 | 2.1 | 97.9 53.5° | 29.4 | 70.0 | -- | -- 55° | 31.3 | 68.7 | 59.6 | 40.4 60° | 42.4 | 57.6 | 80.3 | 19.7 65° | 53.3 | 46.7 | 89.2 | 10.8 70° | 69.7 | 2.3 | 95.4 | 4.6 75° | 84.4 | 15.6 | 96.6 | 3.4 79.9° | 100 | -- | 100 | -- ------------------------------------------------------------------------- At the eutectic point the liquid solution is in equilibrium with two different mixed crystals the composition of which is represented by D and E respectively. If, therefore, a fused mixture containing the two components A and B in the proportions represented by C is cooled down, it will, when the temperature has reached the point C, solidify completely to a _conglomerate_ of mixed crystals, D and E. [Illustration: FIG. 57.] [Illustration: FIG. 58.] Changes in Mixed Crystals with the Temperature.--In the case of the different types of systems represented in Fig. 49, a homogeneous liquid solution of the two components will exist at temperatures above the freezing-point curve, a homogeneous mixed crystal at temperatures below the melting-point curve, while at any point between the freezing-point and melting-point {193} curves the mixture will separate into a solid phase and a liquid phase. In the case, however, of the two types shown in Fig. 54 the relationships are somewhat more complicated. As before, the area above the freezing-point curve gives the conditions under which homogeneous liquid solutions can exist; but below the melting-point curve two different mixed crystals can coexist. This will be best understood from Figs. 57 and 58. D and E represent, as we have seen, the composition of two mixed crystals which are in equilibrium with the liquid solution at the temperature of the point C. These two mixed crystals represent, in the one case, a saturated solution of B in A (point D), and the other a saturated solution of A in B (point E). Just as we saw that the mutual solubility of two liquids varied with the temperature, so also in the case of two solids; as the temperature alters, the solubility of the two solid components in one another will change. This alteration is indicated diagrammatically in Figs. 57 and 58 by the dotted curve similar to the solubility curves for two mutually soluble liquids (p. 101). Suppose, now, that a mixed crystal of the composition _x_ is cooled down, it will remain unchanged until, when the temperature has fallen to _t'_, the homogeneous mixed crystal breaks up into a conglomerate of two mixed crystals the composition of {194} which is represented by _x'_ and _x"_ respectively. From this, then, it can be seen that in the case of substances which form two solid solutions, the mixed crystals which are desposited from the liquid fused mass need not remain unchanged in the solid state, but may at some lower temperature lose their homogeneity. This fact is of considerable importance for the formation of alloys.[277] A good example of this will soon be met with in the case of the iron and carbon alloys. The alloys of copper and tin also furnish examples of the great changes which may take place in the alloy between the temperature at which it separates out from the fused mass and the ordinary temperature. Thus, for example, one of the alloys of copper and tin which separates out from the liquid as a solid solution breaks up, on cooling, into the compound Cu_{3}Sn and liquid:[278] a striking example of a solid substance partially liquefying on being cooled. * * * * * {195} CHAPTER XI EQUILIBRIUM BETWEEN DYNAMIC ISOMERIDES It has long been known that certain substances, _e.g._ acetoacetic ester, are capable when in solution or in the fused state, of reacting as if they possessed two different constitutions; and in order to explain this behaviour the view was advanced (by Laar) that in such cases a hydrogen atom oscillated between two positions in the molecule, being at one time attached to oxygen, at another time to carbon, as represented by the formula-- CH_{3}.C--CH.CO_{2}C_{2}H_{5} . ^ . | O<-H When the hydrogen is in one position, the substance will act as an hydroxy-compound; with hydrogen in the other position, as a ketone. Substances possessing this double function are called _tautomeric_. Doubt, however, arose as to the validity of the above explanation, and this doubt was confirmed by the isolation of the two isomerides in the solid state, and also by the fact that the velocity of change of the one isomeride into the other could in some cases be quantitatively measured. These and other observations then led to the view, in harmony with the laws of chemical dynamics, that tautomeric substances in the dissolved or fused state represent a _mixture_ of two isomeric forms, and that equilibrium is established not by _intra_- but by _inter_-molecular change, as expressed by the equation-- CH_{3}.CO.CH_{2}.CO_{2}C_{2}H_{5} <--> CH_{3}.C(OH):CH.CO_{2}C_{2}H_{5} {196} In the solid state, the one or other of the isomerides represents the stable form; but in the liquid state (solution or fusion) the stable condition is an equilibrium between the two forms. A similar behaviour is also found in the case of other isomeric substances where the isomerism is due to difference of structure, _i.e._ structure isomerism (_e.g._ in the case of the oximes C_{6}H_{5}.C.H C_{6}H_{5}.C.H || and || ), N.OH HO.N or to difference in configuration, _i.e._ stereoisomerism (_e.g._ optically active substances), or to polymerism (_e.g._ acetaldehyde and paraldehyde). In all such cases, although the different solid forms correspond to a single definite constitution, in the liquid state a condition of equilibrium between the two modifications is established. As a general name for these different classes of substances, the term "dynamic isomerides" has been introduced; and the different kinds of isomerism are classed together under the title "dynamic isomerism."[279] By reason of the importance of these phenomena in the study more especially of Organic Chemistry, a brief account of the equilibrium relations exhibited by systems composed of dynamic isomerides may be given here.[280] In studying the fusion and solidification of those substances which exhibit the relationships of dynamic isomerism, the phenomena observed will vary somewhat according as the reversible transformation of the one form into the other takes place with measurable velocity at temperatures in the neighbourhood of the melting points, or only at some higher temperature. If the transformation is very rapid, the system will behave like a one-component system, but if the isomeric change is comparatively slow, the behaviour will be that of a two-component system. Temperature-Concentration Diagram.--The relationships which are met with here will be most readily understood with {197} the help of Fig. 59. Suppose, in the first instance, that isomeric transformation does not take place at the temperature of the melting point, then the freezing point curve will have the simple form ACB; the formation of compounds being for the present excluded. This is the simplest type of curve, and gives the composition of the solutions in equilibrium with the one modification ([alpha] modification) at different temperatures (curve AC); and of the solutions in equilibrium with the other modification ([beta] modification) at different temperatures (curve BC). C is the eutectic point at which the two solid isomerides can exist side by side in contact with the solution. [Illustration: FIG. 59.] Now, suppose that isomeric transformation takes place with measurable velocity. If the pure [alpha]-modification is heated to a temperature _t'_ above its melting point, and the liquid maintained at that temperature until equilibrium has been established, a certain amount of the [beta]-form will be present in the liquid, the composition of which will be represented by the point _x'_. The same condition of equilibrium will also be reached by starting with pure [beta]. Similarly, if the temperature of the liquid is maintained at the temperature _t"_, equilibrium will be reached, we shall suppose, when the solution has the composition _x"_. The curve DE, therefore, which passes through all the different values of _x_ corresponding to different values of _t_, will represent the change of equilibrium with the temperature. It will slope to the right (as in the figure) if the transformation of [alpha] into [beta] is accompanied by absorption of heat; to the left if the transformation is accompanied by evolution of heat, in accordance with van't Hoff's Law of movable equilibrium. If transformation occurs without heat effect, the equilibrium will be independent of the {198} temperature, and the equilibrium curve DE will therefore be perpendicular and parallel to the temperature axis. We must now find the meaning of the point D. Suppose the pure [alpha]- or pure [beta]-form heated to the temperature _t'_, and the temperature maintained constant until the liquid has the composition _x'_ corresponding to the equilibrium at that temperature. If the temperature is now allowed to fall sufficiently slowly so that the condition of equilibrium is continually readjusted as the temperature changes, the composition of the solution will gradually alter as represented by the curve _x'_D. Since D is on the freezing point curve of pure [alpha], this form will be deposited on cooling; and since D is also on the equilibrium curve of the liquid, D is the only point at which solid can exist in stable equilibrium with the liquid phase. (The vapour phase may be omitted from consideration, as we shall suppose the experiments carried out in open vessels.) All systems consisting of the two hylotropic[281] isomeric substances [alpha] and [beta] will, therefore, ultimately freeze at the point D, which is called the "natural" freezing point[282] of the system; provided, of course, that sufficient time is allowed for equilibrium to be established. From this it is apparent that _the stable modification at temperatures in the neighbourhood of the melting point is that which is in equilibrium with the liquid phase at the natural freezing point_. From what has been said, it will be easy to predict what will be the behaviour of the system under different conditions. If pure [alpha] is heated, a temperature will be reached at which it will melt, but this melting point will be sharp only if the velocity of isomeric transformation is comparatively slow; _i.e._ slow in comparison with the determination of the melting point. If the substance be maintained in the fused condition for some time, a certain amount of the [beta] modification will be formed, and on lowering the temperature the pure [alpha] form will be deposited, not at the temperature of the melting point, but at some lower temperature depending on the concentration of the [beta] modification in the liquid phase. If isomeric transformation {199} takes place slowly in comparison with the rate at which deposition of the solid occurs, the liquid will become increasingly rich in the [beta] modification, and the freezing point will, therefore, sink continuously. At the eutectic point, however, the [beta] modification will also be deposited, and the temperature will remain constant until all has become solid. If, on the other hand, the velocity of transformation is sufficiently rapid, then as quickly as the [alpha] modification is deposited, the equilibrium between the two isomeric forms in the liquid phase will continuously readjust itself, and the end-point of solidification will be the natural freezing point. Similarly, starting with the pure [beta] modification, the freezing point after fusion will gradually fall owing to the formation of the [alpha] modification; and the composition of the liquid phase will pass along the curve BC. If, now, the rate of cooling is not too great, or if the velocity of isomeric transformation is sufficiently rapid, complete solidification will not occur at the eutectic point; for at this temperature solid and liquid are not in stable equilibrium with one another. On the contrary, a further quantity of the [beta] modification will undergo isomeric change, the liquid phase will become richer in the [alpha] form, and the freezing point will _rise_; the solid phase in contact with the liquid being now the [alpha] modification. The freezing point will continue to rise until the point D is reached, at which complete solidification will take place without further change of temperature. The diagram also allows us to predict what will be the result of rapidly cooling a fused mixture of the two isomerides. Suppose that either the [alpha] or the [beta] modification has been maintained in the fused state at the temperature _t'_ sufficiently long for equilibrium to be established. The composition of the liquid phase will be represented by _x'_. If the liquid is now _rapidly_ cooled, the composition will remain unchanged as represented by the dotted line _x'_G. At the temperature of the point G solid [alpha] modification will be deposited. If the cooling is not carried below the point G, so as to cause complete solidification, the freezing point will be found to rise with time, owing to the conversion of some of the [beta] form into the [alpha] form {200} in the liquid phase; and this will continue until the composition of the liquid has reached the point D. From what has just been said, it can also be seen that if the freezing point curves can be obtained by actual determination of the freezing points of different synthetic mixtures of the two isomerides, it will be possible to determine the condition of equilibrium in the fused state at any given temperature without having recourse to analysis. All that is necessary is to rapidly cool the fused mass, after equilibrium has been established, and find the freezing point at which solid is deposited; that is, find the point at which the line of constant temperature cuts the freezing point curve. The composition corresponding to this temperature gives the composition of the equilibrium mixture at the given temperature. It will be evident, from what has gone before, that the degree of completeness with which the different curves can be realised will depend on the velocity with which isomeric change takes place, and on the rapidity with which the determinations of the freezing point can be carried out. As the two extremes we have, on the one hand, practically instantaneous transformation, and on the other, practically infinite slowness of transformation. In the former case, only one melting and freezing point will be found, viz. the natural freezing point; in the latter case, the two isomerides will behave as two perfectly independent components, and the equilibrium curve DE will not be realised. The diagram which is obtained when isomeric transformation does not occur within measurable time at the temperature of the melting point is somewhat different from that already given in Fig. 59. In this case, the two freezing point curves AC and BC (Fig. 60) can be readily realized, as no isomeric change occurs in the liquid phase. Suppose, however, that at a higher temperature, _t'_, reversible isomeric transformation can take place, the composition of the liquid phase will alter until at the point _x'_ a condition of equilibrium is reached; and the composition of the liquid at higher temperatures will be represented by the curve _x'_F. Below the temperature _t'_ the position of the equilibrium curve is hypothetical; but as the temperature {201} falls the velocity of transformation diminishes, and at last becomes _practically_ zero. The equilibrium curve can therefore be regarded as dividing into two branches _x'_G and _x'_H. At temperatures between G and _t'_ the [alpha] modification can undergo isomeric change leading to a point on the curve G_x'_; and the [beta] modification can undergo change leading to a point on the curve H_x'_. The same condition of equilibrium is therefore not reached from each side, and we are therefore dealing not with true but with false equilibrium (p. 5). Below the temperatures G and H, isomeric transformation does not occur in measurable time. We shall not, however, enter into a detailed discussion of the equilibria in such systems, more especially as they are not systems in true equilibrium, and as the temperature at which true equilibrium can be established with appreciable velocity alters under the influence of catalytic agents.[283] Examples of such systems will no doubt be found in the case of optically active substances, where both isomerides are apparently quite stable at the melting point. In the case of such substances, also, the action of catalytic agents in producing isomeric transformation (racemisation) is well known. [Illustration: FIG. 60.] Transformation of the Unstable into the Stable Form.--As has already been stated, the stable modification in the neighbourhood of the melting point is that one which is in equilibrium with the liquid phase at the natural freezing point. In the case of polymorphic substances, we have seen (p. 39) that that form which is stable in the neighbourhood of the melting point melts at the higher temperature. That was a {202} consequence of the fact that the two polymorphic forms on melting gave identical liquid phases. In the present case, however, the above rule does not apply, for the simple reason that the liquid phase obtained by the fusion of the one modification is not identical with that obtained by the fusion of the other. In the case of isomeric substances, therefore, the form of lower melting point _may_ be the more stable; and where this behaviour is found it is a sign that the two forms are isomeric (or polymeric) and not polymorphic.[284] An example of this is found in the case of the isomeric benzaldoximes (p. 203). Since in Fig. 59 the [alpha] modification has been represented as the stable form, the transformation of the [beta] into the [alpha] form will be possible at all temperatures down to the transition point. At temperatures below the eutectic point, transformation will occur without formation of a liquid phase; but at temperatures above the eutectic point liquefaction can take place. This will be more readily understood by drawing a line of constant temperature, HK, at some point between C and B. Then if the [beta] modification is maintained for a sufficiently long time at that temperature, a certain amount of the [alpha] modification will be formed; and when the composition of the mixture has reached the point H, fusion will occur. If the temperature is maintained constant, isomeric transformation will continue to take place in the liquid phase until the equilibrium point for that temperature is reached. If this temperature is higher than the natural melting point, the mixture will remain liquid all the time; but if it is below the natural melting point, then the [alpha] modification will be deposited when the system reaches the condition represented by the point on the curve AC corresponding to the particular temperature. As isomeric transformation continues, the freezing point of the system will rise until it reaches the natural freezing point D. Similarly, if the [alpha] modification is maintained at a temperature above that of the point D, liquefaction will ultimately occur, and the system will again reach the final state represented by D.[285] {203} Examples.--_Benzaldoximes._ The relationships which have just been discussed from the theoretical point of view will be rendered clearer by a brief description of cases which have been experimentally investigated. The first we shall consider is that of the two isomeric benzaldoximes:[286]-- C_{6}H_{5}.C.H C_{6}H_{5}.C.H || || HO.N N.OH Benzantialdoxime Benzsynaldoxime ([alpha]-modification). ([beta]-modification). Fig. 61 gives a graphic representation of the results obtained. The melting point of the [alpha] modification is 34-35°; the melting point of the unstable [beta]-modification being 130°. The freezing curves AC and BC were obtained by determining the freezing points of different mixtures of known composition, and the numbers so obtained are given in the following table. {204} ---------------------------------------------------- Grams of the [alpha] modification | in 100 gm. of mixture. | Freezing point. ----------------------------------+----------------- 26.2 | 101° 49.2 | 79° 73.7 | 46° 91.7 | 26.2° 95.0 | 28.6° 96.0 | 30.0° ---------------------------------------------------- [Illustration: FIG. 61.] The eutectic point C was found to lie at 25-26°, and the natural freezing point D was found to be 27.7°. The equilibrium curve DE was determined by heating the liquid mixtures at different temperatures until equilibrium was attained, and then rapidly cooling the liquid. In all cases the freezing point was practically that of the point D. From this it is seen that the equilibrium curve must be a straight line parallel to the temperature axis; and, therefore, isomeric transformation in the case of the two benzaldoximes is not accompanied by any heat effect (p. 197). This behaviour has also been found in the case of acetaldoxime.[287] The isomeric benzaldoximes are also of interest from the fact that the stable modification has the _lower_ melting point (_v._ p. 202). _Acetaldehyde and Paraldehyde._--As a second example of the equilibria between two isomerides, we shall take the two isomeric (polymeric) forms of acetaldehyde, which have recently been exhaustively studied.[288] {205} In the case of these two substances the reaction 3CH_{3}.CHO <--> (CH_{3}.CHO)_{3} takes place at the ordinary temperature with very great slowness. For this reason it is possible to determine the freezing point curves of acetaldehyde and paraldehyde. The three chief points on these curves, represented graphically in Fig. 62, are:-- m.p. of acetaldehyde - 118.45° m.p. of paraldehyde + 12.55° eutectic point - 119.9° [Illustration: FIG. 62.] In order to determine the position of the natural melting point, it was necessary, on account of the slowness of transformation, to employ a catalytic agent in order to increase the velocity with which the equilibrium was established. A drop of concentrated sulphuric acid served the purpose. In presence of a trace of this substance, isomeric transformation very speedily occurs, and leads to the condition of equilibrium. Starting in the one case with fused paraldehyde, and in the other case with acetaldehyde, the same freezing point, viz. 6.75°, was obtained, the solid phase being paraldehyde. This temperature, 6.75°, is therefore the natural freezing point, and paraldehyde, the solid in equilibrium with the liquid phase at this point, is the stable form. With regard to the change of equilibrium with the temperature, it was found that whereas the liquid phase contained 11.7 molecules per cent. of acetaldehyde at the natural freezing point, the liquid at the temperature of 41.6° contains 46.6 molecules per cent. of acetaldehyde. As the temperature {206} rises, therefore, there is increased formation of acetaldehyde, or a decreasing amount of polymerisation. This is in harmony with the fact that the polymerisation of acetaldehyde is accompanied by evolution of heat. While speaking of these isomerides, it may be mentioned that at the temperature 41.6° the equilibrium mixture has a vapour pressure equal to the atmospheric pressure. At this temperature, therefore, the equilibrium mixture (obtained quickly with the help of a trace of sulphuric acid) boils.[289] * * * * * {207} CHAPTER XII SUMMARY.--APPLICATION OF THE PHASE RULE TO THE STUDY OF SYSTEMS OF TWO COMPONENTS In this concluding chapter on two-component systems, it is proposed to indicate briefly how the Phase Rule has been applied to the elucidation of a number of problems connected with the equilibria between two components, and how it has been employed for the interpretation of the data obtained by experiment. It is hoped that the practical value of the Phase Rule may thereby become more apparent, and its application to other cases be rendered easier. The interest and importance of investigations into the conditions of equilibrium between two substances, lie in the determination not only of the conditions for the stable existence of the participating substances, but also of whether or not chemical action takes place between these two components; and if combination occurs, in the determination of the nature of the compounds formed and the range of their existence. In all such investigations, the Phase Rule becomes of conspicuous value on account of the fact that its principles afford, as it were, a touchstone by which the character of the system can be determined, and that from the form of the equilibrium curves obtained, conclusions can be drawn as to the nature of the interaction between the two substances. In order to exemplify the application of the principles of the Phase Rule more fully than has already been done, illustrations will be drawn from investigations on the interaction of organic compounds; on the equilibria between optically active compounds; and on alloys. {208} Summary of the Different Systems of Two Components.--Before passing to the consideration of the application of the Phase Rule to the investigation of particular problems, it will be well to collect together the different types of equilibrium curves with which we are already acquainted; to compare them with one another, in order that we may then employ these characteristic curves for the interpretation of the curves obtained as the result of experiment. In investigating the equilibria between two components, three chief classes of curves will be obtained according as-- I. No combination takes place between the two components. II. The components can form definite compounds. III. The components separate out in the form of mixed crystals. The different types of curves which are obtained in these three cases are represented in Figs. 63, 64, 65. These different diagrams represent the whole series of equilibria, from the melting point of the one component (A) to that of the other component (B). The curves represent, in all cases, the composition of the solution, or phase of variable composition; the temperature being measured along one axis, and the composition along the other. We shall now recapitulate very briefly the characteristics of the different curves. [Illustration: FIG. 63.] If no compound is formed between the two components, {209} the general form of the equilibrium curve will be that of curve I. or II., Fig. 63. Type I. is the simplest form of curve found, and consists, as the diagram shows, of only two branches, AC and BC, meeting at the point C, _which lies below the melting point of either component_. The solid phase which is in equilibrium with the solutions AC is pure A; that in equilibrium with BC, pure B. C is the eutectic point. Although at the eutectic point the solution solidifies entirely without change of temperature, the solid which is deposited is not a homogeneous solid phase, but a mixture, or conglomerate of the two components. _The eutectic point, therefore, represents the melting or freezing point, not of a compound, but of a mixture_ (p. 119). Curve II., Fig. 63, is obtained when two liquid phases are formed. C is an eutectic point, D and F are transition points at which there can co-exist the four phases--solid, two liquid phases, vapour. DEF represents the change in the composition of the two liquid phases with rise of temperature; the curve might also have the reversed form with the critical solution point below the transition points D and F. [Illustration: FIG. 64.] In the second class of systems (Fig. 64), that in which combination between the components occurs, there are again two types according as the compound formed has a definite melting point (_i.e._ can exist in equilibrium with a solution of the same composition), or undergoes only partial fusion; that is, exhibits a transition point. If a compound possessing a definite melting point is formed, the equilibrium curve will have the general form shown by curve I., Fig. 64. A, B, and D are the melting points of pure A, pure B, and of the compound A_{x}B_{y} respectively. AC {210} is the freezing point curve of A in presence of B; BE that of B in presence of A; and DC and DE the freezing point curves of the compound in presence of a solution containing excess of one of the components. C and E are eutectic points at which mixtures of A and A_{x}B_{y}, or B and A_{x}B_{y} can co-exist in contact with solution. The curve CDE may be large or small, and the melting point of the compound, D, may lie above or below that of each of the components, or may have an intermediate position. If more than one compound can be formed, a series of curves similar to CDE will be obtained (_cf._ p. 152). On the other hand, if the compound undergoes transition to another solid phase at a temperature below its melting point, a curve of the form II., Fig. 64, will be found. This corresponds to the case where a compound can exist only in contact with solutions containing excess of one of the components. The metastable continuation of the equilibrium curve for the compound is indicated by the dotted line, the summit of which would be the melting point of the compound. Before this temperature is reached, however, the solid compound ceases to be able to exist in contact with solution, and transition to a different solid phase occurs at the point E (_cf._ p. 134). This point, therefore, represents the limit of the existence of the compound AB. If a series of compounds can be formed none of which possess a definite melting point, then a series of curves will be obtained which do not exhibit a temperature-maximum, and there will be only one eutectic point. The limits of existence of each compound will be marked by a break in the curve (_cf._ p. 143). [Illustration: FIG. 65.] Turning, lastly, to the third class of systems, in which formation of mixed crystals can occur, five different types of curves can be obtained, as shown in Fig. 65. With regard to the first three types, curves I., II., and III., {211} these differ entirely from those of the previous classes, in that they are continuous; they exhibit no eutectic point, and no transition point. Curve II. bears some resemblance to the melting-point curve of a compound (_e.g._ CDE, Fig. 64, I.), but differs markedly from it in not ending in eutectic points. Further, in the case of the formation of a compound, the composition of the solid phase remains unchanged throughout the whole curve between the eutectic points; whereas, when mixed crystals are produced, the composition of the solid phase varies with the composition of the liquid solution. On passing through the maximum, the relative proportions of A and B in the solid and the liquid phase undergo change; on the one side of the maximum, the solid phase contains relatively more A, and on the other side of the maximum, relatively more B than the liquid phase. Lastly, when mixed crystals are formed, the temperature at which complete solidification occurs changes as the composition of the solution changes, whereas in the case of the formation of compounds, the temperature of complete solidification for all solutions is a eutectic point. The third type of curve, Fig. 65, can be distinguished in a similar manner from the ordinary eutectic curve, Fig. 63, I., to which it bears a certain resemblance. Whereas in the case of the latter, the eutectic point is the temperature of complete solidification of all solutions, the point of minimum temperature in the case of the formation of mixed crystals, is the solidification point only of solutions having one particular composition; that, namely, of the minimum point. For all other solutions, the temperature of complete solidification is different. Whereas, also, in the case of the simple eutectic curve, the solid which separates out from the solutions represented by either curve remains the same throughout the whole extent of that curve, the composition of the mixed crystal varies with variation of the composition of the liquid phase, and the relative proportions of the two components in the solid and the liquid phase are reversed on passing through the minimum.[290] In a similar manner, type IV., Fig. 65, can be distinguished from type II., Fig. 64, by the fact that it does not exhibit a {212} eutectic point, and that the composition of the solid phase undergoes continuous variation with variation of the liquid phase on either side of the transition point. Lastly, type V., which does exhibit a eutectic point, differs from the eutectic curve of Fig. 63, in that the eutectic point does not constitute the point of complete solidification for all solutions, and that the composition of the solid phase varies with the composition of the liquid phase. Such, then, are the chief general types of equilibrium curves for two-components; they are the pattern curves with which other curves, experimentally determined, can be compared; and from the comparison it will be possible to draw conclusions as to the nature of the equilibria between the two components under investigation. 1. _Organic Compounds._ [Illustration: FIG. 66.] The principles of the Phase Rule have been applied to the investigation of the equilibria between organic compounds, and Figs. 66-69 reproduce some of the results which have been obtained.[291] {213} Fig. 66, the freezing point curve (curve of equilibrium) for _o_-nitrophenol and _p_-toluidine, shows a curve of the simplest type[292] (type I., Fig. 63), in which two branches meet at an eutectic point. The solid phase in equilibrium with solutions represented by the left-hand branch of the curve was _o_-nitrophenol (m.p. 44.1°); that in equilibrium with the solutions represented by the right-hand branch, was _p_-toluidine (m.p. 43.3°). At the eutectic point (15.6°), these two solid phases could co-exist with the liquid phase. This equilibrium curve, therefore, shows that _o_-nitrophenol and _p_-toluidine do not combine with one another. In connection with this curve, attention may be called to the interesting fact that although the solid produced by cooling the liquid phase at the eutectic point has a composition approximating to that of a compound of equimolecular proportions of the phenol and toluidine, and a constant melting point, it is nevertheless a _mixture_. Although, as a rule, the constituents of the eutectic mixture are not present in simple molecular proportions, there is no reason why they should not be so; and it is therefore necessary to beware of assuming the formation of compounds in such cases.[293] Fig. 67, on the other hand, indicates with perfect certainty the formation of a compound between phenol and [alpha]-naphthylamine.[294] (_Cf._ curve I., Fig. 64.) Phenol freezes at 40.4°, but the addition of [alpha]-naphthylamine lowers the freezing point as represented by the curve AC. At C (16.0°) the compound C_{6}H_{5}OH,C_{10}H_{7}NH_{2} is formed, and the system becomes invariant. On increasing the amount of the amine, the temperature of equilibrium rises, the solid phase now being the compound. At D, the curve passes through a maximum (28.8°), at which the solid and liquid phases have the same composition. This is the melting point of the compound. Further addition of the amine lowers the temperature of equilibrium, until at E solid [alpha]-naphthylamine separates out, and a second eutectic point (24.0°) is obtained. BE is the {214} freezing-point curve of [alpha]-naphthylamine in presence of phenol, the freezing point of the pure amine being 48.3°. On account of the great sluggishness with which the compound of phenol and [alpha]-naphthylamine crystallizes, it was found possible to follow the freezing point curves of phenol and the amine to temperatures considerably below the eutectic points, as shown by the curves CF and EG. [Illustration: FIG. 67.] Phenol can also combine with _p_-toluidine in equimolecular proportions; and this compound is of interest, from the fact that it exists in two crystalline forms melting at 28.5° and 30°. Each of these forms now must have its own equilibrium curve, and it was found that the intermediate portion of the freezing point curve was duplicated, as shown in Fig. 68.[295] {215} [Illustration: FIG. 68.] [Illustration: FIG. 69.] {216} Lastly, a curve is given, Fig. 69,[296] which corresponds with curve II., Fig. 64. Picric acid and benzene can form a compound, which, however, can exist only in contact with solutions _containing excess of benzene_. When the temperature is raised, a point (K) is reached at which the compound melts with separation of solid picric acid. The point, K, is, therefore, a _transition point_; analysis, however, showed that the composition of the solution at this point is very nearly that of the compound C_{6}H_{2}(NO_{2})_{3}OH,C_{6}H_{6}, so that the melting point of the compound can almost be reached. The fusion of the compound of benzene and picric acid with separation of the latter is analogous to the (partial) fusion of Glauber's salt with separation of anhydrous sodium sulphate. 2. _Optically Active Substances._ The question as to whether a resolvable inactive body is a mixture of the two oppositely active constituents (a _dl_-mixture), or a racemic compound, is one which has given rise to considerable discussion during the past decade; and several investigators have endeavoured to establish general rules by which the question could be decided. In the case of inactive liquids it is a matter of great difficulty to arrive at a certain conclusion as to whether one is dealing with a mixture or a compound, for in this case the usual physical methods give but a dubious answer; and although the existence of a racemate in the liquid state (in the case of conine) has been asserted,[297] most chemists incline to the belief that such a thing is improbable. Even in the case of crystalline substances, where the differences between the various forms is greater, it was not always easy to discriminate between the _dl_-mixture and the racemic compound. The occurrence of hemihedral faces was considered by Pasteur to be a sufficient criterion for an optically active substance. It has, however, been found that hemihedry in crystals, although a frequent accompaniment of {217} optical activity, is by no means a necessary or constant expression of this property. Other rules, also, which were given, although in some cases reliable, were in other cases insufficient; and all were in so far unsatisfactory that they lacked a theoretical basis. With the help of the Phase Rule, however, it is possible from a study of the solubility or fusion curves of the optically active and inactive substances, to decide the nature of the inactive substance, at least under certain conditions. On account of the interest and importance which these compounds possess, a brief description of the application of the Phase Rule to the study of such substances will be given here;[298] the two optical antipodes being regarded as the two components. In the present chapter we shall consider only the fusion curves, the solubility curves being discussed in the next section on three-component systems. The rules which are hereby obtained, have reference only to the nature of the inactive substance in the neighbourhood of the melting points. I. _The inactive substance is a _dl_-mixture._ In this case the fusion curves will have the simple form shown in type I, Fig. 63. A and B are the melting points of the two optical isomerides, and C the eutectic point at which the inactive mixture consisting of equal amounts of d- and l-form melts. Owing to the similar effect of the one form on the freezing point of the other, the figure is symmetrical. No example of this simple case has been investigated. II. _The two components form a racemic compound._ In this case there will be three melting point curves as in Fig. 64, type I. In this case also the figure must be symmetrical. Examples.--As examples of this, may be taken dimethyl tartrate and mandelic acid, the freezing point curves of which are given in Figs. 70 and 71.[299] As can be seen, the curve for the racemic tartrate occupies a large part of the diagram, {218} while that for racemic mandelic acid is much smaller. In the case of dimethyldiacetyl tartrate, this middle portion is still less. [Illustration: FIG. 70.] [Illustration: FIG. 71.] [Illustration: FIG. 72.] Active dimethyl tartrate melts at 43.3°; racemic dimethyl tartrate at 89.4°. Active mandelic acid melts at 132.8°; the racemic acid at 118.0°. In the one case, therefore, the racemic compound has a higher, in the other a lower melting point than the active forms. {219} In the case of partially racemic compounds (_i.e._ the compound of a racemate with an optically active substance) the type of curve will be the same, but the figure will no longer be symmetrical. Such a curve has been found in the case of the l-menthyl esters of d- and l-mandelic acid (Fig. 72).[300] The freezing point of l-menthyl d-mandelate is 97.2°, of l-menthyl l-mandelate 77.6°, and of l-menthyl r-mandelate 83.7.° It will be observed that the summit of the curve for the partially racemic mandelate is very flat, indicating that the compound is largely dissociated into its components at the temperature of fusion. III. _The inactive substance is a pseudo-racemic mixed crystal._ In cases where the active components can form mixed crystals, the freezing-point curve will exhibit one of the forms given in Fig. 65. The inactive mixed crystal containing 50 per cent. of the dextro and laevo compound, is known as a pseudo-racemic mixed crystal.[301] So far, only curves of the types I. and II. have been obtained. Examples.--The two active camphor oximes are of interest from the fact that they form a continuous series of mixed crystals, _all of which have the same melting point_. The curve which is obtained in this case is, therefore, a straight line joining the melting points of the pure active components; the melting point of the active isomerides and of the whole series of mixed crystals being 118.8°. [Illustration: FIG. 73.] In the case of the carvoximes mixed crystals are also formed, but the equilibrium curve in this case exhibits a maximum (Fig. 73). At this maximum point the composition of the solid and of the liquid solution is the same. Since the curve must be symmetrical, this maximum point must occur in the case of the solution containing 50 per cent. {220} of each component, which will therefore be inactive. Further, this inactive mixed crystal will melt and solidify at the same temperature, and behave, therefore, like a chemical compound (p. 187). The melting point of the active compounds is 72°; that of the inactive pseudo-racemic mixed crystal is 91.4°· Transformations.--As has already been remarked, the conclusions which can be drawn from the fusion curves regarding the nature of the inactive substances formed hold only for temperatures in the neighbourhood of the melting points. At temperatures below the melting point transformation may occur; _e.g._ a racemate may break up into a _dl_-mixture, or a pseudo-racemic mixed crystal may form a racemic compound. We shall at a later point meet with examples of a racemic compound changing into a _dl_-mixture at a definite transition point; and the pseudo-racemic mixed crystal of camphoroxime is an example of the second transformation. Although at temperatures in the neighbourhood of the melting point the two active camphoroximes form only mixed crystals but no compound, a racemic compound is formed at temperatures below 103°. At this temperature the inactive pseudo-racemic mixed crystal changes into a racemic compound; and in the case of the other mixed crystals transformation to racemate and (excess of) active component also occurs, although at a lower temperature than in the case of the inactive mixed crystal. Although this behaviour is one of considerable importance, this brief reference to it must suffice here.[302] 3. _Alloys._ One of the most important classes of substances in the study of which the Phase Rule has been of very considerable importance, is that formed by the mixtures or compounds of metals with one another known as alloys. Although in the investigation of the nature of these bodies various methods are employed, one of the most important is the determination of the character of the freezing-point curve; for from the form of this, valuable information can, as we have already learned, be {221} obtained regarding the nature of the solid substances which separate out from the molten mixture. Although it is impossible here to discuss fully the experimental results and the oftentimes very complicated relationships which the study of the alloys has brought to light, a brief reference to these bodies will be advisable on account both of the scientific interest and of the industrial importance attaching to them.[303] We have already seen that there are three chief types of freezing-point curves in systems of two components, viz. those obtained when (1) the pure components crystallize out from the molten mass; (2) the components form one or more compounds; (3) the components form mixed crystals. In the case of the metals, representatives of these three classes are also found. 1. _The components separate out in the pure state._ In this case the freezing-point curve is of the simple type, Fig. 63, I. Such curves have been obtained in the case of a number of pairs of metals, _e.g._ zinc--cadmium, zinc--aluminium, copper--silver (Heycock and Neville), tin--zinc, bismuth--lead (Gautier), and in other cases. From molten mixtures represented by one branch of the freezing-point curve one of the metals will be deposited; while from mixtures represented by the other branch, the other metal will separate out. At the eutectic point the molten mass will solidify to a _heterogeneous mixture_ of the two metals, forming what is known as the _eutectic alloy_. Such an alloy, therefore, will melt at a definite temperature lower than the melting point of either of the pure metals. {222} In the following table are given the temperature and the composition of the liquid at the eutectic point, for three pairs of metals:-- ------------------------------------------------------------------- | Temperature. | Composition of liquid. ------------------------------------------------------------------- Zinc--cadmium | 264.5° | 73.5 atoms per cent. of cadmium. Zinc--aluminium | 380.5° | 11 " " aluminium. Copper--silver | 778° | 40 " " copper. ------------------------------------------------------------------- The melting points of the pure metals are, zinc, 419°; cadmium, 322°; silver, 960°; copper, 1081°; aluminium, 650°. 2. _The two metals can form one or more compounds._ In this case there will be obtained not only the freezing-point curves of the pure metals, but each compound formed will have its own freezing-point curve, exhibiting a point of maximum temperature, and ending on either side in an eutectic point. The simplest curve of this type will be obtained when only one compound is formed, as is the case with mercury and thallium.[304] This curve is represented in Fig. 74, where the summit of the intermediate curve corresponds with a composition TlHg_{2}. Similar curves are also given by nickel and tin, by aluminium and silver, and by other metals, the formation of definite compounds between these pairs of metals being thereby indicated.[305] [Illustration: FIG. 74.] {223} A curve belonging to the same type, but more complicated, is obtained with gold and aluminium;[306] in this case, several compounds are formed, some of which have a definite melting point, while others exhibit only a transition point. The chief compound is AuAl_{2}, which has practically the same melting point as pure gold. 3. _The two metals form mixed crystals (solid solutions)._ The simplest case in which the metals crystallize out together is found in silver and gold.[307] The freezing-point curve in this case is an almost straight line joining the freezing points of the pure metals (_cf._ curve I., Fig. 65, p. 210). These two metals, therefore, can form an unbroken series of mixed crystals. In some cases, however, the two metals do not form an unbroken series of mixed crystals. In the case of zinc and silver,[308] for example, the addition of silver _raises_ the freezing point of the mixture, until a transition point is reached. This corresponds with curve IV., Fig. 65. Silver and copper, and gold and copper, on the other hand, do not form unbroken series of mixed crystals, but the freezing-point curve exhibits an eutectic point, as in curve V., Fig. 65. Not only may there be these three different types of curves, but there may also be combinations of these. Thus the two metals may not only form compounds, but one of the metals may not separate out in the pure state at all, but form mixed crystals. In this case the freezing point may rise (as in the case of silver and zinc), and one of the eutectic points will be absent. Iron-Carbon Alloys.--Of all the different binary alloys, probably the most important are those formed by iron and carbon: alloys consisting not of two metals, but of a metal and a non-metal. On account of the importance of these alloys, an attempt will be made to describe in brief some of the most important relationships met with. Before proceeding to discuss the applications of the Phase Rule to the study of the iron-carbon alloys, however, the main {224} facts with which we have to deal may be stated very briefly. With regard to the metal itself, it is known to exist in three different allotropic modifications, called [alpha]-, [beta]-, and [gamma]-ferrite respectively. Like the two modifications of sulphur and of tin, these different forms exhibit transition points at which the relative stability of the forms changes. Thus the transition point for [alpha]- and [beta]-ferrite is about 780°; and below this temperature the [alpha]- form, above it the [beta]- form is stable. For [beta]- and [gamma]-ferrite, the transition point is about 870°, the [gamma]- form being the stable modification above this temperature. The different modifications of iron also possess different properties. Thus, [alpha]-ferrite is magnetic, but does not possess the power of dissolving carbon; [beta]-ferrite is non-magnetic, and likewise does not dissolve carbon; [gamma]-ferrite is also non-magnetic, but possesses the power of dissolving carbon, and of thus giving rise to solid solutions of carbon in iron. Various alloys of iron and carbon, also, have to be distinguished. First of all, there is _hard steel_, which contains varying amounts of carbon up to 2 per cent. Microscopic examination shows that these mixtures are all homogeneous; and they are therefore to be regarded as solid solutions of carbon in iron ([gamma]-ferrite). To these solutions the name _martensite_ has been given. _Pearlite_ contains about 0.8 per cent. of carbon, and, on microscopic examination, is found to be a heterogeneous mixture. If heated above 670°, pearlite becomes homogeneous, and forms martensite. Lastly, there is a definite compound of iron and carbon, iron carbide or _cementite_, having the formula Fe_{3}C. A short description may now be given of the application of the Phase Rule to the two-component system iron--carbon; and of the diagram showing how the different systems are related, and with the help of which the behaviour of the different mixtures under given conditions can be predicted. Although, with regard to the main features of this diagram, the different areas to be mapped and the position of the frontier lines, there is general agreement; a final decision has not yet been reached with regard to the interpretation to be put on all the curves. [Illustration: FIG. 75.] The chief relationships met with in the case of the {225} iron-carbon alloys are represented graphically in Fig. 75.[309] The curve AC is the freezing-point curve for iron,[310] BC the unknown freezing-point curve for graphite. C is an eutectic point. Suppose, now, that we start with a mixture of iron and carbon, represented by the point _x_. On lowering the temperature, a point, _y_, will be reached at which solid begins to separate out. This solid phase, however, is not pure iron, but a solid solution of carbon in iron, having the composition represented by _y'_ (cf. p. 185). As the temperature continues to fall, the {226} composition of the liquid phase changes in the direction of _y_C, while the composition of the solid which separates out changes in the direction _y'_D; and, finally, when the composition of the molten mass is that of the point C (4.3 per cent. of carbon), the whole mass solidifies to a heterogeneous mixture of two solid solutions, one of which is represented by D (containing 2 per cent. of carbon), while the other will consist practically of pure graphite, and is not shown in the figure. The temperature of the eutectic point is 1130°. Even below the solidification point, however, changes can take place. As has been said, the solid phase which finally separates out from the molten mass is a solid solution represented by the point D; and the curve DE represents the change in the composition of this solid solution with the temperature. As indicated in the figure, DE forms a part of a curve representing the mutual solubility of graphite in iron and iron in graphite; the latter solutions, however, not being shown, as they would lie far outside the diagram. As the temperature falls below 1130°, more and more graphite separates out, until at E, when the temperature is 1000°, the solid solution contains only 1.8 per cent. of carbon. At this temperature cementite also begins to be formed, so that as the temperature continues to fall, separation of cementite (represented by the line E'F') occurs, and the composition of the solid solution undergoes alteration, as represented by the curve EF. Below the temperature of the point F (670°) the martensite becomes heterogeneous, and forms pearlite. From the above description, therefore, it follows that if we start with a molten mixture of iron and carbon, the composition of which is represented by any point between D and C (from 2 to 4.3 per cent. of carbon), we shall obtain, on cooling the mass, first of all solid solutions, the composition of which will be represented by points on the line AD; that then, after the mass has completely solidified at 1130°, further cooling will lead to a separation of graphite and a change in the composition of the martensite (from 2 to 1.8 per cent. of carbon). On cooling below 1000°, however, the martensite and graphite will give rise to cementite and solid solutions {227} containing less carbon than before, until, at temperatures below 670°, we are left with a mixture of pearlite and cementite. We have already said that iron consists in three allotropic modifications, the regions of stability of which are separated by definite transition points. The transition point for [alpha]- and [beta]-ferrite (780°) is represented in Fig. 75 by the point H; and the transition point for [beta]- and [gamma]-ferrite (870°) by the point I. Since neither the [alpha]- nor the [beta]-ferrite dissolves carbon, the transition point will be unaffected by addition of carbon, and we therefore obtain the horizontal transition curve HG. In the case of the [beta]- and [gamma]-ferrite, however, the latter dissolves carbon, and the transition point is consequently affected by the amount of carbon present. This is shown by the line IG. If a martensite containing less carbon than that represented by the point G is cooled down from a temperature of, say, 900°, then when the temperature has fallen to that, represented by a point on the curve IG, [beta]-ferrite will separate out, and, as the temperature falls, the composition of the solid solution will alter as represented by IG. On passing below the temperature of HG, the [beta]-ferrite will be converted into [alpha]-ferrite, and, as the temperature falls, the latter will separate out more and more, while the composition of the solid solution alters in the direction GF. On passing to still lower temperatures, the solid solution at F (0.8 per cent. of carbon) breaks up into pearlite. If the percentage of carbon in the original solid solution was between that represented by the points G and F, then, on cooling down, no [beta]-ferrite, but only [alpha]-ferrite would separate out. We see, therefore, that when martensite is allowed to cool _slowly_, it yields a heterogeneous mixture either of ferrite and pearlite (when the original mixture contained up to 0.8 per cent. of carbon), or pearlite and cementite (when the original mixture contained between 0.8 and 2 per cent. of carbon). These heterogeneous mixtures constitute soft steels, or, when the carbon content is low, wrought iron. The case, however, is different if the solid solution of carbon in iron is _rapidly_ cooled (quenched) from a temperature above the curve IGFE to a temperature below this {228} curve. In this case, the rapid cooling does not allow time for the various changes which have been described to take place; so that the homogeneous solid solution, on being rapidly cooled, remains homogeneous. In this way hard steel is obtained. By varying the rapidity of cooling, as is done in the tempering of steel, varying degrees of hardness can be obtained. The interpretation of the curves given above is that due essentially to Roozeboom, who concluded from the experimental data that at temperatures below 1000° the stable systems are martensite and cementite, or ferrite and cementite, graphite being labile. It has, however, been pointed out, more especially by E. Heyn,[311] that this is not in harmony with the facts of metallurgy, which show that graphite is undoubtedly formed on slow cooling, and more especially when small quantities of silicon are present in the iron.[312] While, therefore, the relationships represented by Fig. 75 are obtained under certain conditions (especially when manganese is present), Heyn considers that all the curves in that figure, except ACB, represent _metastable_ systems--systems, therefore, akin to supercooled liquids. Rapid cooling will favour the production of the metastable systems containing cementite, and therefore give rise to relationships represented by Fig. 75; whereas slow cooling will lead to the stable system ferrite and graphite. Presence of silicon tends to prevent, presence of manganese tends to assist, the production of the metastable systems. Although this view put forward by Heyn has not been conclusively proved, it must be said that there is much evidence in its favour. Further investigation is, however, required before a final decision as to the interpretation of the curves can be reached. Determination of the Composition of Compounds, without Analysis.--Since the equilibrium between a solid and a liquid phase depends not only on the composition of the liquid (solution) but also on that of the solid, it is necessary {229} to determine the composition of the latter. In some cases this is easily effected by separating the solid from the liquid phase and analyzing it. In other cases, however, this method is inapplicable, or is accompanied by difficulties, due either to the fact that the solid phase undergoes decomposition (_e.g._ when it contains a volatile constituent), or to the difficulty of completely separating the mother liquor; as, for example, in the case of alloys. In all such cases, therefore, recourse must be had to other methods. In the first place, synthetic methods may be employed.[313] In this case we start with a solution of the two components, to which a third substance is added, which, however, does not enter into the solid phase.[314] We will assume that the initial solution contains _x_ gm. of A and _y_ gm. of B to 1 gm. of C. After the solution has been cooled down to such a temperature that solid substance separates out, a portion of the liquid phase is removed with a pipette and analyzed. If, now, the composition of the solution is such that there are _x'_ gm. of A and _y'_ gm. of B to 1 gm. of C., then the composition of the solid phase is _x_ - _x'_ gm. of A and _y_ - _y'_ gm. of B. When _x_ = _x'_, the solid phase is pure B; when _y_ = _y'_, the solid phase is pure A. We have assumed here that there is only one solid phase present, containing A and B. To make sure that the solid phase is not a solid solution in which A and B are present in the same ratio as in the liquid solution, a second determination of the composition must be made, with different initial and end concentrations. If the solid phase is a solid solution, the composition will now be found different from that found previously. The composition of the solid phase can, however, be determined in another manner, viz. by studying the fusion curve and the curve of cooling. From the form of the fusion curve alone, it is possible to decide whether the two components {230} form a compound or not; and if the compounds which may be formed have a definite melting point, the position of the latter gives at once the composition of the compounds (cf. p. 231). This method, however, cannot be applied when the compounds undergo decomposition before the melting point is reached. In such cases, however, the form of the cooling curve enables one to decide the composition of the solid phase.[315] If a solution is allowed to cool slowly, and the temperature noted at definite times, the graphic representation of the rate of cooling will give a continuous curve; _e.g._ _ab_ in Fig. 76. So soon, however, as a solid phase begins to be formed, the rate of cooling alters abruptly, and the cooling curve then exhibits a break, or change in direction (point _b_). When the eutectic point is reached, the temperature remains constant, until all the liquid has solidified. This is represented by the line _cd_. When complete solidification has occurred, the fall of temperature again becomes uniform (_de_). [Illustration: FIG. 76.] [Illustration: FIG. 77.] [Illustration: FIG. 78.] The length of time during which the temperature remains constant at the point _c_, depends, of course, on the eutectic solution. If, therefore, we take equal amounts of solution having a different initial composition, the period of constant temperature in the cooling curve will evidently be greatest in the case of the solution having the composition of the eutectic point; and the period will become less and less as we increase the amount of one of the components. The relationship between initial composition of solution and the duration of constant temperature at the eutectic point is represented by the curve _a'c'b'_ (Fig. 77). When a compound possessing a definite melting point is formed, it behaves as a pure substance. If, therefore, the initial composition of the {231} solution is the same as that of the compound, no eutectic solution will be obtained; and therefore no line of constant temperature, such as _cd_ (Fig. 76). In such a case, if we represent graphically the relation between the initial composition of the solution and the duration of constant temperature, a diagram is obtained such as shown in Fig. 78. The two maxima on the time-composition curve represent eutectic points, and the minima, _a'_, _b'_, _e'_, pure substances. The position of _e'_ gives the composition of the compound. When a series of compounds is formed, then for each compound a minimum is found on the time-composition curve. [Illustration: FIG. 79.] If the compound formed has no definite melting point, the diagram obtained is like that shown in Fig. 79. If we start with a solution, the composition of which is represented by a point between _d_ and _b_, then, on cooling, _b_ will separate out first, and the temperature will fall until the point _d_ is reached. The temperature then remains constant until the component _b_, which has separated out, is converted into the compound. After this the temperature again falls, until it again remains constant at the eutectic point c. In the case of the first halt, the period of constant temperature is greatest when the initial composition of the solution is the same as that of the compound; and it becomes shorter and shorter with {232} increase in the amount of either component. In this way we obtain the time-composition curve _b'e"d'_, of which the maximum point _e"_ gives the composition of the compound. On the other hand, the period of constant temperature for the eutectic point _c_ is greatest in the case of solutions having the same initial _composition_ as that corresponding with the eutectic point; and it decreases the more the initial composition approaches that of the pure component _a_ or the component e. In this way we obtain the time-composition curve _a'c'e'_. Here also the point _e'_ represents the composition of the compound. We see, therefore, that from the graphic representation of the freezing-point curve, and from the duration of the temperature-arrests on the cooling curve, for solutions of different initial composition, it is possible, without having recourse to analysis, to decide what solid phases are formed, and what is their composition. Formation of Minerals.--Important and interesting as is the application of the Phase Rule to the study of alloys, its application to the study of the conditions regulating the formation of minerals is no less so; and although we do not propose to consider different cases in detail here, still attention must be drawn to certain points connected with this interesting subject. In the first place, it will be evident from what has already been said, that that mineral which first crystallizes out from a molten magma is not necessarily the one with the highest melting point. The _composition_ of the fused mass must be taken into account. When the system consists of two components which do not form a compound, one or other of these will separate out in a pure state, according as the composition of the molten mass lies on one or other side of the eutectic composition; and the separation of the one component will continue until the composition of the eutectic point is reached. Further cooling will then lead to the simultaneous separation of the two components. If, however, the two components form a stable compound (_e.g._ orthoclase, from a fused mixture of silica and potassium aluminate), then the freezing-point curve will resemble that {233} shown in Fig. 64; _i.e._ there will be a middle curve possessing a dystectic point, and ending on either side at a eutectic point. This curve would represent the conditions under which orthoclase is in equilibrium with the molten magma. If the initial composition of the magma is represented by a point between the two eutectic points, orthoclase will separate first. The composition of the magma will thereby change, and the mass will finally solidify to a mixture of orthoclase and silica, or orthoclase and potassium aluminate, according to the initial composition. What has just been said holds, however, only for stable equilibria, and it must not be forgotten that complications can arise owing to suspended transformation (when, for example, the magma is rapidly cooled) and the production of metastable equilibria. These conditions occur very frequently in nature. The study of the formation of minerals from the point of view of the Phase Rule is still in its initial stages, but the results which have already been obtained give promise of a rich harvest in the future.[316] * * * * * {234} CHAPTER XIII SYSTEMS OF THREE COMPONENTS General.--It has already been made evident that an increase in the number of the components from one to two gives rise to a considerable increase in the possible number of systems, and introduces not a few complications into the equilibrium relations of these. No less is this the case when the number of components increases from two to three; and although examples of all the possible types of systems of three components have not been investigated, nor, indeed, any one type fully, nevertheless, among the systems which have been studied experimentally, cases occur which not only possess a high scientific interest, but are also of great industrial importance. On account not only of the number, but more especially of the complexity of the systems constituted of three components, no attempt will be made to give a full account, or, indeed, even a survey of all the cases which have been subjected to a more or less complete experimental investigation; on the contrary, only a few of the more important classes will be selected, and the most important points in connection with the behaviour of these described. On applying the Phase Rule P + F = C + 2 to the systems of three components, we see that in order that the system shall be invariant, no fewer than five phases must be present together, and an invariant system will therefore exist at a _quintuple_ point. Since the number of liquid phases can never exceed the number of the components, and since there can be only one vapour phase, it is evident that in this case, {235} as in others, there must always be at least one solid phase present at the quintuple point. As the number of phases diminishes, the variability of the system can increase from one to four, so that in the last case the condition of the system will not be completely defined until not only the temperature and the total pressure of the system, but also the concentrations of two of the components have been fixed. Or, instead of the concentrations, the partial pressures of the components may also be taken as independent variables. Graphic Representation.--Hitherto the concentrations of the components have been represented by means of rectangular co-ordinates, although the numerical relationships have been expressed in two different ways. In the one case, the concentration of the one component was expressed in terms of a fixed amount of the other component. Thus, the solubility of a salt was expressed by the number of grams of salt dissolved by 100 grams of water or other solvent; and the numbers so obtained were measured along one of the co-ordinates. The second co-ordinate was then employed to indicate the change of another independent variable, _e.g._ temperature. In the other case, the combined weights of the two components A and B were put equal to unity, and the concentration of the one expressed as a fraction of the whole amount. This method allows of the representation of the complete series of concentrations, from pure A to pure B, and was employed, for example, in the graphic representation of the freezing point curves. Even in the case of three components rectangular co-ordinates can also be employed, and, indeed, are the most convenient in those cases where the behaviour of two of the components to one another is very different from their behaviour to the third component; as, for example, in the case of two salts and water. In these cases, the composition of the system can be represented by measuring the amounts of each of the two components in a given weight of the third, along two co-ordinates at right angles to one another; and the change of the system with the temperature can then be represented by a third axis at right angles to the first two. In those cases, {236} however, where the three components behave in much the same manner towards one another, the rectangular co-ordinates are not at all suitable, and instead of these a _triangular diagram_ is employed. Various methods have been proposed for the graphic representation of systems of three components by means of a triangle, but only two of these have been employed to any considerable extent; and a short description of these two methods will therefore suffice.[317] [Illustration: FIG. 80.] In the method proposed by Gibbs an equilateral triangle of unit height is used (Fig 80).[318] The quantities of the different components are expressed as fractional parts of the whole, and the sum of their concentrations is therefore equal to unity, and can be represented by the height of the triangle. The corners {237} of the triangle represent the pure substances A, B, and C respectively. A point on one of the sides of the triangle will give the composition of a mixture in which only two components are present, while a point within the triangle will represent the composition of a ternary mixture. Since every point within the triangle has the property that the sum of the perpendiculars from that point on the sides of the triangle is equal to unity (the height of the triangle), it is evident that the composition of a ternary mixture can be represented by fixing a point within the triangle such that the lengths of the _perpendiculars_ from the point to the sides of the triangle are equal respectively to the fractional amounts of the three components present; the fractional amount of A, B, or C being represented by the perpendicular distance from the side of the triangle _opposite_ the corners A, B, and C respectively. The location of this point is simplified by dividing the normals from each of the corners on the opposite side into ten or one hundred parts, and drawing through these divisions lines at right angles to the normal and parallel to the side of the triangle. A network of rhombohedra is thus obtained, and the position of any point can be read off in practically the same manner as in the case of rectangular co-ordinates. Thus the point P in Fig. 80 represents a ternary mixture of the composition A = 0.5, B = 0.3, C = 0.2; the perpendiculars P_a_, P_b_, and P_c_ being equal respectively to 0.5, 0.2, and 0.3 of the height of the triangle. Another method of representation, due to Roozeboom, consists in employing an equilateral triangle, the length of whose _side_ is made equal to unity, or one hundred; the sum of the fractional or percentage amounts of the three components being represented therefore by a side of the triangle. In this case the composition of a ternary mixture is obtained by determining, not the _perpendicular_ distance of a point P from the three sides of the triangle, but the distance in a direction _parallel_ to the sides of the triangle (Fig. 81). Conversely, in order to represent a mixture consisting of _a_, _b_, and _c_ parts of the components A, B, and C respectively, one side of the triangle, say AB, is first of all divided into ten or one {238} hundred parts; a portion, B_x_ = _a_, is then measured off, and represents the amount of A present. Similarly, a portion, A_x'_ = _b_, is measured off and represents the fractional amount of B, while the remainder, _xx'_ = _c_, represents the amount of C. From _x_ and _x'_ lines are drawn parallel to the sides of the triangle, and the point of intersection, P, represents the composition of the ternary mixture of given composition; for, as is evident from the figure, the distance of the point P from the three sides of the triangle, when measured in directions _parallel_ to the sides, is equal to _a_, _b_, and _c_ respectively. From the division marks on the side AB, it is seen that the point P in this figure also represents a mixture of 0.5 parts of A, 0.2 parts of B, and 0.3 parts of C. This gives exactly the same result as the previous method. The employment of a right-angled isosceles triangle has also been suggested,[319] but is not in general use. [Illustration: FIG. 81.] In employing the triangular diagram, it will be of use to note a property of the equilateral triangle. A line drawn from one corner of the triangle to the opposite side, represents the composition of all mixtures in which the _relative_ amounts of two of the components remain unchanged. Thus, as Fig. 82 shows, if the component C is added to a mixture x, in which A and B are present in the proportions of _a_ : _b_, a mixture _x'_, which is thereby obtained, also contains A and B in the ratio _a_ : b. For the two triangles AC_x_ and BC_x_ are similar to the two triangles HC_x'_ and KC_x'_; and, {239} therefore, A_x_ : B_x_ = H_x'_ : K_x'_. But A_x_ = D_x_ and B_x_ = E_x_; further H_x'_ = F_x'_ and K_x'_ = G_x'_. Therefore, D_x_ : E_x_ = F_x'_ : G_x'_ = _b_ : a. At all points on the line C_x_, therefore, the ratio of A to B is the same. [Illustration: FIG. 82.] [Illustration: FIG. 83.] If it is desired to represent at the same time the change of another independent variable, _e.g._ temperature, this can be done by measuring the latter along axes drawn perpendicular to the corners of the triangle. In this way a right prism (Fig. 83) is obtained, and each section of this cut parallel to the base represents therefore an _isothermal surface_. * * * * * {240} CHAPTER XIV SOLUTIONS OF LIQUIDS IN LIQUIDS We have already seen (p. 95) that when two liquids are brought together, they may mix in all proportions and form one homogeneous liquid phase; or, only partial miscibility may occur, and two phases be formed consisting of two mutually saturated solutions. In the latter case, the concentration of the components in either phase and also the vapour pressure of the system had, at a given temperature, perfectly definite values. In the case of three liquid components, a similar behaviour may be found, although complete miscibility of three components with the formation of only one liquid phase is of much rarer occurrence than in the case of two components. When only partial miscibility occurs, various cases are met with according as the three components form one, two, or three pairs of partially miscible liquids. Further, when two of the components are only partially miscible, the addition of the third may cause either an increase or a diminution in the mutual solubility of these. An increase in the mutual solubility is generally found when the third component dissolves readily in each of the other two; but when the third component dissolves only sparingly in the other two, its addition diminishes the mutual solubility of the latter. We shall consider here only a few examples illustrating the three chief cases which can occur, viz. (1) A and B, and also B and C are miscible in all proportions, while A and C are only partially miscible. (2) A and B are miscible in all proportions, but A and C and B and C are only partially miscible. (3) A and B, B and C, and A and C are only partially miscible. A, B, and C here represent the three components. 1.--_The three components form only one pair of partially miscible liquids._ {241} An example of this is found in the three substances: chloroform, water, and acetic acid.[320] Chloroform and acetic acid, and water and acetic acid, are miscible with one another in all proportions, but chloroform and water are only partially miscible with one another. If, therefore, chloroform is shaken with a larger quantity of water than it can dissolve, two layers will be formed consisting one of a saturated solution of water in chloroform, the other of a saturated solution of chloroform in water. The composition of these two solutions at a temperature of about 18°, will be represented by the points _a_ and _b_ in Fig. 84; _a_ representing a solution of the composition: chloroform, 99 per cent.; water, 1 per cent.; and _b_ a solution of the composition: chloroform, 0.8 per cent.; water, 99.2 per cent. When acetic acid is added, it distributes itself between the two liquid layers, and two conjugate _ternary_ solutions, consisting of chloroform, water, and acetic acid are thereby produced which are in equilibrium with one another, and the composition of which will be represented by two points inside the triangle. In this way a series of pairs of ternary solutions will be obtained by the addition of acetic acid to the mixture of chloroform and water. By this addition, also, not only do the two liquid phases become increasingly rich in acetic acid, but the mutual solubility of the chloroform and water increases; so that the layer _a_ becomes relatively richer in water, and layer _b_ relatively richer in chloroform. This is seen from the following table, which gives the percentage composition of different conjugate ternary solutions at 18°. ------------------------------------------------------------------------- Heavier layer. | Lighter layer. ------------------------------------------------------------------------- Chloroform. | Water. | Acetic acid. | Chloroform. | Water. | Acetic acid. ------------------------------------------------------------------------- 99.01 | 0.99 | 0 | 0.84 | 99.16 | 0 91.85 | 1.38 | 6.77 | 1.21 | 73.69 | 25.10 80.00 | 2.28 | 17.72 | 7.30 | 48.58 | 44.12 70.13 | 4.12 | 25.75 | 15.11 | 34.71 | 50.18 67.15 | 5.20 | 27.65 | 18.33 | 31.11 | 50.56 59.99 | 7.93 | 32.08 | 25.20 | 25.39 | 49.41 55.81 | 9.58 | 34.61 | 28.85 | 23.28 | 47.87 ------------------------------------------------------------------------- {242} By the continued addition of acetic acid, the composition of the successive conjugate solutions in equilibrium with one another becomes, as the table shows, more nearly the same, and a point is at length reached at which the two solutions become identical. This will therefore be a _critical point_ (p. 98). Increased addition of acetic acid beyond this point will lead to a single homogeneous solution. These relationships are represented graphically by the curve _a_K_b_, Fig. 84. The points on the branch _a_K represent the composition of the solutions relatively rich in chloroform (heavier layer), those on the curve _b_K the composition of solutions relatively rich in water (lighter layer); and the points on these two branches representing conjugate solutions are joined together by "tie-lines." Thus, the points _a'b'_ represent conjugate solutions, and the line _a'b'_ is a tie-line. [Illustration: FIG. 84.] Since, now, acetic acid when added to a heterogeneous mixture of chloroform and water does not enter in equal amounts into the two layers, but in amounts depending on its coefficient of distribution between chloroform and water,[321] the {243} tie-lines will not be parallel to AB, but will be inclined at an angle. As the solutions become more nearly the same, the tie-lines diminish in length, and at last, when the conjugate solutions become identical, shrink to a point. For the reason that the tie-lines are, in general, not parallel to the side of the triangle, the critical point at which the tie-line vanishes will not be at the summit of the curve, but somewhere below this, as represented by the point K. The curve _a_K_b_, further, forms the boundary between the heterogeneous and homogeneous systems. A mixture of chloroform, water, and acetic acid represented by any point outside the curve _a_K_b_, will form only one homogeneous phase; while any mixture represented by a point within the curve, will separate into two layers having the composition represented by the ends of the tie-line passing through that point. Thus, a mixture of the total composition _x_, will separate into two layers having the composition _a'_ and _b'_ respectively. Since three components existing in three phases (two liquid and a vapour phase) constitute a bivariant system, the final result, _i.e._ the composition of the two layers and the total vapour pressure, will not depend merely on the temperature, as in the case of two-component systems (p. 102), but also on the composition of the mixture with which we start. At constant temperature, however, all mixtures, the composition of which is represented by a point on one and the same tie-line, will separate into the same two liquid phases, although the relative _amounts_ of the two phases will vary. If we omit the vapour phase, the condition of the system will depend on the pressure as well as on the temperature and composition of the initial mixture. By keeping the pressure constant, _e.g._ at atmospheric pressure (by working with open vessels), the system again becomes bivariant. We see, therefore, that the position of the curve _a_K_b_, or, in other words, the composition of the different conjugate ternary solutions, will vary with the temperature, and only with the temperature, if we assume either constancy of pressure or the presence of the vapour phase. Since at the critical point the condition is imposed that the two liquid phases become identical, one degree of freedom is thereby {244} lost, and therefore only one degree of freedom remains. The critical point, therefore, depends on the temperature, and only on the temperature; always on the assumption, of course, that the pressure is constant, or that a vapour phase is present. Fig. 84, therefore, represents an isothermal (p. 239). It is of importance to note that the composition of the different ternary solutions obtained by the addition of acetic acid to a heterogeneous mixture of chloroform and water, will depend not only on the amount of acetic acid added, but also on the relative amounts of chloroform and water at the commencement. Suppose, for example, that we start with chloroform and water in the proportions represented by the point _c'_ (Fig. 84). On mixing these, two liquid layers having the composition _a_ and _b_ respectively will be formed. Since by the addition of acetic acid the relative amounts of these two substances in the system as a whole cannot undergo alteration, the total composition of the different ternary systems which will be obtained must be represented by a point on the line C_c'_ (p. 238). Thus, for example, by the addition of acetic acid a system may be obtained, the total composition of which is represented by the point _c"_. Such a system, however, will separate into two conjugate ternary solutions, the composition of which will be represented by the ends of the tie-line passing through the point _c"_. So long as the total composition of the system lies below the point S, _i.e._ the point of intersection of the line C_c'_ with the boundary curve, two liquid layers will be formed; while all systems having a total composition represented by a point on the line C_c'_, above S, will form only one homogeneous solution. From the figure, also, it is evident that as the amount of acetic acid is increased, the relative amounts of the two liquid layers formed differ more and more until at S a limiting position is reached, when the amount of the one liquid layer dwindles to nought, and only one solution remains. The same reasoning can be carried through for different initial amounts of chloroform and water, but it would be fruitless to discuss all the different systems which can be obtained. The reason for the preceding discussion was to show that {245} although the addition of acetic acid to a mixture of chloroform and water will, in all cases, lead ultimately to a limiting system, beyond which homogeneity occurs, that point is not necessarily the critical point. On the contrary, in order that addition of acetic acid shall lead to the critical mixture, it is necessary to start with a binary mixture of chloroform and water in the proportions represented by the point _c'_. In this case, addition of acetic acid will give rise to a series of conjugate ternary solutions, the composition of which will gradually approach to one another, and at last become identical. From the foregoing it will be evident that the amount of acetic acid required to produce a homogenous solution, will depend on the relative amounts of chloroform and water from which we start, and can be ascertained by joining the corner C with the point on the line AB representing the total composition of the initial binary system. The point where this line intersects the boundary curve _a_K_b_ will indicate the minimum amount of acetic acid which, under these particular conditions, is necessary to give one homogeneous solution. Retrograde Solubility.--As a consequence of the fact that acetic acid distributes itself unequally between chloroform and water, and the critical point K, therefore, does not lie at the summit of the curve, it is possible to start with a homogeneous solution in which the percentage amount of acetic acid is greater than at the critical point, and to pass from this first to a heterogenous and then again to a homogenous system merely by altering the relative amounts of chloroform and water. This phenomenon, to which the term _retrograde solubility_ is applied, will be observed not only in the case of chloroform, water, and acetic acid, but in all other systems in which the critical point lies below the highest point of the boundary curve for heterogeneous systems. This will be seen from the diagram, Fig. 85. Starting with the homogeneous system represented by _x_, in which, therefore, the concentration of C is greater than in the critical mixture (K), if the relative amounts of A and B are altered in the direction _xx'_, while the amount of C is maintained constant, the system will become heterogeneous when the composition reaches the point _y_, and will remain {246} heterogeneous with changing composition until the point _y'_ is passed, when it will again become homogeneous. If the relative concentration of C is increased above that represented by the line SS, this phenomenon will, of course, no longer be observed. [Illustration: FIG. 85.] Relationships similar to those described for chloroform, water, and acetic acid are also found in the case of a number of other trios, _e.g._ ether, water, and alcohol; chloroform, water, and alcohol.[322] They have also been observed in the case of a considerable number of molten metals.[323] Thus, molten lead and silver, as well as molten zinc and silver, mix in all proportions; but molten lead and zinc are only partially miscible with one another. When melted together, therefore, the last two metals will separate into two liquid layers, one rich in lead, the other rich in zinc. If silver is now added, and the temperature maintained above the freezing point of the mixture, the silver passes for the most part, in accordance with the law of distribution, into the upper layer, which is rich in zinc; silver being more soluble in molten zinc than in molten lead. This is clearly shown by the following figures:--[324] {247} -------------------------------------------------- Heavier alloy. | Lighter alloy. -------------------------------------------------- Percentage amount of | Percentage amount of Silver. | Lead. | Zinc. | Silver. | Lead. | Zinc. -------------------------------------------------- 1.25 | 96.69 | 2.06 | 38.91 | 3.12 | 57.97 1.71 | 96.43 | 1.86 | 45.01 | 3.37 | 51.62 5.55 | 93.16 | 1.29 | 54.93 | 4.21 | 40.86 -------------------------------------------------- The numbers in the same horizontal row give the composition of the conjugate alloys, and it is evident that the upper layer consists almost entirely of silver and zinc. On allowing the mixture to cool slightly, the upper layer solidifies first, and can be separated from the still molten lead layer. It is on this behaviour of silver towards a mixture of molten lead and zinc that the Parkes's method for the desilverization of lead depends.[325] If aluminium is also added, a still larger proportion of silver passes into the lighter layer, and the desilverization of the lead is more complete.[326] [Illustration: FIG. 86.] [Illustration: FIG. 87.] The Influence of Temperature.--As has already been said, a ternary system existing in three phases possesses two degrees of freedom; and the state of the system is therefore dependent not only on the relative concentration of the components, but also on the temperature. As the temperature changes, therefore, the boundary curve of the heterogeneous system will also alter; and in order to represent this alteration we shall make use of the right prism, in which the temperature is measured upwards. In this way the boundary curve passes into a boundary surface (called a dineric surface), as shown in Fig. 86. In this figure the curve _akb_ is the isothermal for the ternary system; the curve _a_K_b_ shows the change in the _binary_ system AB with the temperature, with {248} a critical point at K. This curve has the same meaning as those given in Chapter VI. The curve _k_K is a critical curve joining together the critical points of the different isothermals. In such a case as is shown in Fig. 86, there does not exist any real critical temperature for the ternary system, for as the temperature is raised, the amount of C in the "critical" solution becomes less and less, and at K only two components, A and B, are present. In the case, however, represented in Fig. 87, a real ternary critical point is found. In this figure _ak'b_ is an isothermal, _ak"_ is the curve for the binary system, and K is the ternary critical point. All points outside the helmet-shaped boundary surface represent homogeneous ternary solutions, while all points within the surface belong to heterogeneous systems. Above the temperature of the point K, the three components are miscible in all proportions. An example of a ternary system yielding such a boundary surface is that consisting of phenol, water, and acetone.[327] In this case the critical temperature K is 92°, and the composition at this ternary critical point is-- Water 59 per cent. Acetone 12 " Phenol 29 " [Illustration: FIG. 88.] The difference between the two classes of systems just mentioned, is seen very clearly by a glance at the Figs. 88 and 89, which show the projection of the isothermals on the base of the prism. In Fig. 88, the projections yield paraboloid curves, the two branches of which are cut by one side of the triangle; and the critical point is represented by a point on {249} this side. In the second case (Fig. 89), however, the projections of the isothermals form ellipsoidal curves surrounding the supreme critical point, which now lies _inside the triangle_. At lower temperatures, these isothermal boundary curves are cut by a side of the triangle; at the critical temperature, _k"_, of the binary system AB, the boundary curve _touches_ the side AB, while at still higher temperatures the boundary curve comes to lie entirely within the triangle. At any given temperature, therefore, between the critical point of the binary system (_k"_), and the supreme critical point of the ternary system (K), each pair of the three components are miscible with one another in all proportions; for the region of heterogeneous systems is now bounded by a closed curve lying entirely within the triangle. Outside this curve only homogeneous systems are found. Binary mixtures, therefore, represented by any point on one of the sides of the triangle must be homogeneous, for they all lie outside the boundary curve for heterogeneous states. [Illustration: FIG. 89.] 2. _The three components can form two pairs of partially miscible liquids._ In the case of the three components water, alcohol, and succinic nitrile, water and alcohol are miscible in all proportions, but not so water and succinic nitrile, or alcohol and succinic nitrile. [Illustration: FIG. 90.] [Illustration: FIG. 91.] As we have already seen (p. 122), water and succinic nitrile can form two liquid layers between the temperatures 18.5° and 55.5°; while alcohol and nitrile can form two liquid layers between 13° and 31°. If, then, between these two temperature limits, alcohol is added to a heterogeneous mixture of water and nitrile, or water is added to a mixture of alcohol and nitrile, two heterogeneous ternary systems will be formed, {250} and two boundary curves will be obtained in the triangular diagram, as shown in Fig. 90.[328] On changing the temperature, the boundary curves will also undergo alteration, in a manner similar to that just discussed. As the temperature falls, the two curves will spread out more and more into the centre of the triangle, and might at last meet one another; while at still lower temperatures we may imagine the curves still further expanding so that the two heterogeneous regions flow into one another and form a _band_ on the triangular diagram (Fig. 91). This, certainly, has not been realized in the case of the three components mentioned, because at a temperature higher than that at which the two heterogeneous regions could fuse together, solid separates out. [Illustration: FIG. 92.] The gradual expansion of a paraboloid into a band-like area of heterogeneous ternary systems, has, however, been observed in the case of water, phenol, and aniline.[329] In Fig. 92 are shown three isothermals, viz. those for 148°, 95°, and 50°. At 148°, water and aniline form two layers having the composition-- Water, 83.5 per cent. } { water, 20 per cent. } and { Aniline, 16.5 " } { aniline, 80 " {251} and the critical point _k'_ has the composition-- Water, 65; phenol, 13.2; aniline, 21.8 per cent. At 95°, the composition of the two binary solutions is-- Water, 93 per cent. } { water 8 per cent. } and { Aniline, 7 " } { aniline, 92 " while the point _k"_ has the composition Water, 69.9; phenol, 26.6; aniline, 3.5 per cent. At 50°, the region of heterogeneous states now forms a band, and the two layers formed by water and aniline have the composition-- Water, 96.5 per cent. } { water, 5.5 per cent. } and { Aniline, 3.5 " } { aniline, 94.5 " while the two layers formed by water and phenol have the composition-- Water, 89 per cent.} { water, 38 per cent. } and { Phenol, 11 " } { phenol, 62 " All mixtures of water, phenol, and aniline, therefore, the composition of which is represented by any point within the band _abcd_, will form two ternary solutions; while if the composition is represented by a point outside the band, only one homogeneous solution will be produced. 3. _The three components form three pairs of partially miscible liquids._ [Illustration: FIG. 93.] The third chief case which can occur is that no two of the components are completely miscible with one another. In this case, therefore, we shall obtain three paraboloid boundary curves, as shown in Fig. 93. If, now, we imagine these three curves to expand in towards the centre of the triangle, as might happen, for example, by lowering the temperature, a point will {252} be reached at which the curves partly overlap, and we shall get the appearance shown in Fig. 94. The points _a_, _b_, and _c_ represent the points where the three curves cut, and the triangle _abc_ is a region where the curves overlap. From this diagram we can see that any mixture having a composition represented by a point in one of the clear spaces at the corners of the larger triangle, will form a homogeneous solution; if the composition corresponds to any point lying in one of the quadrilateral regions _x__{1}, _x__{2} or _x__{3}, two ternary solutions will be formed; while, if the composition is represented by any point in the inner triangle, separation into three layers will occur. [Illustration: FIG. 94.] Since in the clear regions at the corners of the triangle we have three components in two phases, liquid and vapour, the systems have three degrees of freedom. At constant temperature, therefore, the condition of the system is not defined until the concentrations of two of the components are fixed. A system belonging to one of the quadrilateral spaces has, as we have seen, two degrees of freedom; besides the temperature, one concentration must be fixed. Lastly, a system the composition of which falls within the inner triangle _abc_, will form three layers, and will therefore possess only one degree of freedom. If the temperature is fixed, the composition of the three layers is also determined, viz. that of the points _a_, _b_, and _c_ respectively; and a change in the composition of the original mixture can lead only to a difference in the relative amounts of the three layers, not to a difference in their composition. An example of a system which can form three liquid phases is found in water, ether, and succinic nitrile.[330] * * * * * {253} CHAPTER XV PRESENCE OF SOLID PHASES A. The Ternary Eutectic Point.--In passing to the consideration of those ternary systems in which one or more solid phases can exist together with one liquid phase, we shall first discuss not the solubility curves, as in the case of two-component systems, but the simpler relationships met with at the freezing point. That is, we shall first of all examine the freezing point curves of ternary systems. [Illustration: FIG. 95.] Since it is necessary to take into account not only the changing composition of the liquid phase, but also the variation of the temperature, we shall employ the right prism for the graphic representation of the systems, as shown in Fig. 95. A, B, and C in this figure, therefore, denote the melting points of the pure components. If we start with the component A at its melting point, and add B, which is capable of dissolving in liquid A, the freezing point of A will be lowered; and, similarly, the freezing point of B by addition of A. In this way we get the freezing point curve A_k__{1}B for the binary system; _k__{1}; being an eutectic point. This curve will of course lie in the plane formed by one face of the prism. In a similar manner we obtain the freezing point curves A_k__{2}C and B_k__{3}C. These curves give the composition of the binary liquid phases in equilibrium {254} with one of the pure components, or at the eutectic points, with a mixture of two solid components. If, now, to the system represented say by the point _k__{1}, a small quantity of the third component, C, is added, the temperature at which the two solid phases A and B can exist in equilibrium with the liquid phase is lowered; and this depression of the eutectic point is all the greater the larger the addition of C. In this way we obtain the curve _k__{1}K, which slopes inwards and downwards, and indicates the varying composition of the ternary liquid phase with which a mixture of solid A and B are in equilibrium. Similarly, the curves _k__{2}K and _k__{3}K are the corresponding eutectic curves for A and C, and B and C in equilibrium with ternary solutions. At the point K, the three solid components are in equilibrium with the liquid phase; and this point, therefore, represents _the lowest temperature attainable with the three components given_. Each of the ternary eutectic curves, as they may be called, is produced by the intersection of two surfaces, while at the ternary eutectic point, three surfaces, viz. A_k__{1}K_k__{2}, B_k__{1}K_k__{3}, and C_k__{1}K_k__{3} intersect. Any point on one of these surfaces represents a ternary solution in equilibrium with only one component in the solid state; the lines or curves of intersection of these represent equilibria with two solid phases, while at the point K, the ternary eutectic point, there are three solid phases in equilibrium with a liquid and a vapour phase. The surfaces just mentioned represent bivariant systems. One component in the solid state can exist in equilibrium with a ternary liquid phase under varying conditions of temperature and concentration of the components in the solution; and before the state of the system is defined, these two variables, temperature and composition of the liquid phase, must be fixed. On the other hand, the curves formed by the intersection of these planes represent univariant systems; at a given temperature two solid phases can exist in equilibrium with a ternary solution, only when the latter has a definite composition. Lastly, the ternary eutectic point, K, represents an invariant system; three solid phases can exist in equilibrium with a ternary solution, only when the latter has one fixed composition and when the temperature has a definite value. This eutectic point, therefore, {255} has a perfectly definite position, depending only on the nature of the three components. Instead of employing the prism, the change in the composition of the ternary solutions can also be indicated by means of the _projections_ of the curves _k__{1}K, _k__{2}K, and _k__{3}K on the base of the prism, the particular temperature being written beside the different eutectic points and curves. This is shown in Fig. 96. [Illustration: FIG. 96.] The numbers which are given in this diagram refer to the eutectic points for the system bismuth--lead--tin, the data for which are as follows:--[331] -------------------------------------------------------------------- Melting point of | Percentage composition of | Temperature of binary pure metal. | binary eutectic mixture. | eutectic point. -------------------------------------------------------------------- | Bi Pb Sn | Bismuth, 268° | 55 45 -- | Bi--Pb, 127° Lead, 325° | 58 -- 42 | Bi--Sn, 133° Tin, 232° | -- 37 63 | Pb--Sn, 182° -------------------------------------------------------------------- -------------------------------------------------- Percentage composition of | Temperature of ternary ternary eutectic mixture. | eutectic point. -------------------------------------------------- Bi Pb Sn | 52 32 16 | 96° -------------------------------------------------- Formation of Compounds.--In the case just discussed, the components crystallized out from solution in the pure state. If, however, combination can take place between two of the components, the relationships will be somewhat different; the curves which are obtained in such a case being represented in Fig. 97. From the figure, we see that the two components B {256} and C form a compound, and the freezing point curve of the binary system has therefore the form shown in Fig. 64 (p. 209). Further, there are two _ternary_ eutectic points, K_{1} and K_{2}, the solid phases present being A, B, and compound, and A, C, and compound respectively. [Illustration: FIG. 97.] The particular point, now, to which it is desired to draw attention is this. Suppose the ternary eutectic curves projected on a plane parallel to the face of the prism containing B and C, _i.e._ suppose the concentrations of the two components B and C, between which interaction can occur, expressed in terms of a constant amount of the third component A,[332] curves will then be obtained which are in every respect analogous to the freezing point curves of binary systems. Thus, suppose the eutectic curves _k__{1}K and _k__{2}K in Fig. 95 projected on the face BC of the prism, then evidently a curve will be obtained consisting of two branches meeting in an eutectic point. On the other hand, the projection of the ternary eutectic curves in Fig. 97 on the face BC of the prism, will give a curve consisting of three portions, as shown by the outline _k__{1}K_{1}K_{2}_k__{2} in Fig. 97. Various examples of this have been studied, and the following table contains some of the data for the system ethylene bromide (A), picric acid (B), and [beta]-naphthol (C), obtained by Bruni.[333] {257} ------------------------------------------------------------------------- | Temperature | Solid phases present. ------------------------------------------------------------------------- Point _k__{1} | 9.41° | Ethylene bromide, picric acid. Curve _k__{1}K_{1} | -- | " " Point K_{1} | 9.32° | Ethylene bromide, picric acid, and | | [beta]-naphthol picrate. Curve K_{1}D'K_{2} | -- | Ethylene bromide, | | [beta]-naphthol picrate. Point D' | 9.75° | " " " " Point K_{2} | 8.89° | " " [beta]-naphthol, | | and picrate. Curve K_{2}_k__{2} | -- | " " [beta]-naphthol. Point _k__{2} | 9.04° | " " " ------------------------------------------------------------------------- From what has been said, it will be apparent that if the ternary eutectic curve of a three-component system (in which one of the components is present in constant amount) is determined, it will be possible to state, from the form of curve obtained, whether or not the two components present in varying amount crystallize out pure or combine with one another to form a compound. It may be left to the reader to work out the curves for the other possible systems; but it will be apparent, that the projections of the ternary eutectic curves in the manner given will yield a series of curves alike in all points to the binary curves given in Figs. 63-65, pp. 208-210. Since, from the method of investigation, the temperatures of the eutectic curves will depend on the melting point of the third component (A), it is possible, by employing substances with widely differing melting points, to investigate the interaction of the two components (_e.g._ two optical antipodes) B and C over a range of temperature; and thus determine the range of stability of the compound, if one is formed. Since, in some cases, two substances which at one temperature form mixed crystals combine at another temperature to form a definite compound, the relationships which have just been described can be employed, and indeed, have been employed, to determine the temperature at which this change occurs.[334] By means of this method, Adriani found that below 103° _i_-camphoroxime exists as a racemic compound, while above {258} that temperature it occurs as a racemic mixed crystal[335] (_cf._ p. 219). B. Equilibria at Higher Temperatures. Formation of Double Salts.--After having studied the relationships which are found in the neighbourhood of the freezing points of the components, we now pass to the discussion of the equilibria which are met with at higher temperatures. In this connection we shall confine the discussion entirely to the systems formed of two salts and water, dealing more particularly with those cases in which the water is present in relatively large amount and acts as solvent. Further, in studying these systems, one restriction must be made, viz. that the single salts are salts either of the same base or of the same acid; or are, in other words, capable of yielding a common ion in solution. Such a restriction is necessary, because otherwise the system would be one not of three but of four components.[336] Transition Point.--As is very well known, there exist a number of hydrated salts which, on being heated, undergo apparent partial fusion; and in Chapter V. the behaviour of such hydrates was more fully studied in the light of the Phase Rule. Glauber's salt, or sodium sulphate decahydrate, for example, on being heated to a temperature of about 32.5°, partially liquefies, owing to the fact that the water of crystallization is split off and anhydrous sodium sulphate formed, as shown by the equation-- Na_{2}SO_{4},10H_{2}O = Na_{2}SO_{4} + 10H_{2}O The temperature of 32.5°, it was learned, constituted a _transition point_ for the decahydrate and anhydrous salt plus water; decomposition of the hydrated salt occurring above this temperature, combination of the anhydrous salt and water below it. Analogous phenomena are met with in systems constituted of two salts and water in which the formation of double salts can take place. Thus, for example, if _d_-sodium potassium {259} tartrate is heated to above 55°, apparent partial fusion occurs, and the two single salts, _d_-sodium tartrate and _d_-potassium tartrate, are deposited, the change which occurs being represented by the equation-- 4NaKC_{4}O_{6}H_{4},4H_{2}O = 2Na_{2}C_{4}O_{6}H_{4},2H_{2}O + 2K_{2}C_{4}O_{6}H_{4},½H_{2}O + 11H_{2}O On the other hand, if sodium and potassium tartrates are mixed with water in the proportions shown on the right side of the equation, the system will remain partially liquid so long as the temperature is maintained above 55° (in a closed vessel to prevent loss of water), but on allowing the temperature to fall below this point, complete solidification will ensue, owing to the formation of the hydrated double salt. Below 55°, therefore, the hydrated double salt is the stable system, while above this temperature the two single salts plus saturated solution are stable.[337] A similar behaviour is found in the case of the double salt copper dipotassium chloride (CuCl_{2},2KCl,2H_{2}O or CuK_{2}Cl_{4},2H_{2}O).[338] When this salt is heated to 92°, partial liquefaction occurs, and the original blue plate-shaped crystals give place to brown crystalline needles and white cubes; while on allowing the temperature to fall, re-formation of the blue double salt ensues. The temperature 92° is, therefore, a transition point at which the reversible reaction-- CuK_{2}Cl_{4},2H_{2}O <--> CuKCl_{3} + KCl + 2H_{2}O takes place. The decomposition of sodium potassium tartrate, or of copper dipotassium chloride, differs in so far from that of Glauber's salt that _two_ new solid phases are formed; and in the case of copper dipotassium chloride, one of the decomposition products is itself a double salt. In the two examples of double salt decomposition which have just been mentioned, sufficient water was yielded to cause a partial liquefaction; but other cases are known where this is not so. Thus, when copper calcium acetate is heated to a {260} temperature of 75°, although decomposition of the double salt into the two single salts occurs as represented by the equation[339]-- CuCa(C_{2}H_{3}O_{2})_{4},8H_{2}O = Cu(C_{2}H_{3}O_{2})_{2},H_{2}O + Ca(C_{2}H_{3}O_{2})_{2},H_{2}O + 6H_{2}O the amount of water split off is insufficient to give the appearance of partial fusion, and, therefore, only a change in the crystals is observed. The preceding examples, in which decomposition of the double salt was effected by a rise of temperature, were chosen for first consideration as being more analogous to the case of Glauber's salt; but not a few examples are known where the reverse change takes place, formation of the double salt occurring _above_ the transition point, and decomposition into the constituent salts below it. Instances of this behaviour are found in the case of the formation of astracanite from sodium and magnesium sulphates, and of sodium ammonium racemate from the two sodium ammonium tartrates, to which reference will be made later. Between these various systems, however, there is no essential difference; and whether decomposition or formation of the double salt occurs at temperatures above the transition point, will of course depend on the heat of change at that point. For, in accordance with van't Hoff's law of movable equilibrium (p. 58), that change will take place at the higher temperature which is accompanied by an absorption of heat. If, therefore, the formation of the double salt from the single salts is accompanied by an absorption of heat, the double salt will be formed from the single salts on raising the temperature; but if the reverse is the case, then the double salt on being heated will decompose into the constituent salts.[340] In those cases, now, which have so far been studied, the change at the transition point is accompanied by a taking up or a splitting off of water; and _in such cases the general rule can be given, that if the water of crystallization of the two constituent {261} salts together is greater than that of the double salt, the latter will be produced from the former on raising the temperature_ (_e.g._ astracanite from sodium and magnesium sulphates); _but if the double salt contains more water of crystallization than the two single salts, increase of temperature will effect the decomposition of the double salt_. When we seek for the connection between this rule and the law of van't Hoff, it is found in the fact that the heat effect involved in the hydration or dehydration of the salts is much greater than that of the other changes which occur, and determines, therefore, the sign of the total heat effect.[341] Vapour Pressure. Quintuple Point.--In the case of Glauber's salt, we saw that at a certain temperature the vapour pressure curve of the hydrated salt cut that of the saturated solution of anhydrous sodium sulphate. That point, it will be remembered, was a quadruple point at which the four phases sodium sulphate decahydrate, anhydrous sodium sulphate, solution, and vapour, could co-exist; and was also the point of intersection of the curves for four univariant systems. In the case of the formation of double salts, similar relationships are met with; and also certain differences, due to the fact that we are now dealing with systems of three components. Two cases will be chosen here for brief description, one in which formation, the other in which decomposition of the double salt occurs with rise of temperature. On heating a mixture of sodium sulphate decahydrate and magnesium sulphate heptahydrate, it is found that at 22° partial liquefaction occurs with formation of astracanite. At this temperature, therefore, there can coexist the five phases-- Na_{2}SO_{4},10H_{2}O; MgSO_{4},7H_{2}O; Na_{2}Mg(SO_{4})_{2},4H_{2}O; solution; vapour. This constitutes, therefore, a _quintuple point_; and since there are three components present in five phases, the system is invariant. This point, also, will be the point of intersection of curves for five univariant systems, which, in this case, must each be composed of four phases. These systems are-- {262} I. Na_{2}SO_{4},10H_{2}O; MgSO_{4},7H_{2}O; Na_{2}Mg(SO_{4})_{2},4H_{2}O; vapour. II. Na_{2}SO_{4},10H_{2}O; MgSO_{4},7H_{2}O; solution; vapour. III. MgSO_{4},7H_{2}O; Na_{2}Mg(SO_{4})_{2},4H_{2}O; solution; vapour. IV. Na_{2}SO_{4},10H_{2}O; Na_{2}Mg(SO_{4})_{2},4H_{2}O; solution; vapour. V. Na_{2}SO_{4},10H_{2}O; MgSO_{4},7H_{2}O; Na_{2}Mg(SO_{4})_{2},4H_{2}O; solution. [Illustration: FIG. 98.] On representing the vapour pressures of these different systems graphically, a diagram is obtained such as is shown in Fig. 98,[342] the curves being numbered in accordance with the above list. When the system I. is heated, the vapour pressure increases until at the quintuple point the liquid phase (solution) is formed, and it will then depend on the relative amounts of the different phases whether on further heating there is formed system III., IV., or V. If either of the first two is produced, we shall obtain the vapour pressure of the solutions saturated with respect to both double salt and one of the single salts; while if the vapour phase disappears, there will be obtained the pressure of the condensed systems formed of double salt, two single salts and solution. This curve, therefore, indicates the _change of the transition point with pressure_; and since in the ordinary determinations of the transition point in open vessels, we are in reality dealing with condensed systems under the pressure of 1 atm., it will be evident that the transition point does not accurately coincide with the quintuple point (at which the system is under the pressure of its own vapour). As in the case of other condensed systems, however, pressure has only a slight influence on the temperature of the transition point. Whether or not pressure raises or lowers the transition point will depend on whether transformation is accompanied by an increase or {263} diminution of volume (theorem of Le Chatelier, p. 58). In the case of the formation of astracanite, expansion occurs, and the transition point will therefore be raised by increase of pressure. Although measurements have not been made in the case of this system, the existence of such a curve has been experimentally verified in the case of copper and calcium acetates and water (v. _infra_).[343] [Illustration: FIG. 99.] The vapour pressure diagram in the case of copper calcium acetate and water (Fig. 99), is almost the reverse of that already discussed. In this case, the double salt decomposes on heating, and the decomposition is accompanied by a contraction. Curve I. is the vapour pressure curve for double salt, two single salts (p. 260), and vapour; curves II. and III. give the vapour pressures of solutions saturated with respect to double salt and one of the single salts; curve IV. is the curve of pressures for the solutions saturated with respect to the two single salts; while curve V. again represents the change of the transition point with pressure. On examining this diagram, it is seen that whereas {264} astracanite could exist both above and below the quintuple point, copper calcium acetate can exist only _below_ the quintuple point. This behaviour is found only in those cases in which the double salt is decomposed by rise of temperature, and where the decomposition is accompanied by a diminution of volume.[344] As already mentioned, the decomposition of copper calcium acetate into the single salts and saturated solution is accompanied by a contraction, and it was therefore to be expected that increase of pressure would _lower_ the transition point. This expectation of theory was confirmed by experiment, for van't Hoff and Spring found that although the transition point under atmospheric pressure is about 75°, decomposition of the double salt took place even at the ordinary temperature when the pressure was increased to 6000 atm.[345] Solubility Curves at the Transition Point.--At the transition point, as has already been shown, the double salt and the two constituent salts can exist in equilibrium with the same solution. The transition point, therefore, must be the point of intersection of two solubility curves; the solubility curve of the double salt and the solubility curve of the mixtures of the two constituent salts. It should be noted here that we are not dealing with the solubility curves of the single salts separately, for since the systems are composed of three components, a single solid phase can, at a given temperature, be in equilibrium with solutions of different composition, and two solid phases in contact with solution (and vapour) are therefore necessary to give an univariant system. The same applies, of course, to the solubility of the double salt; for a double salt also constitutes a single phase, and can therefore exist in equilibrium with solutions of varying composition. If, however, we make the restriction (which we do for the present) that the double salt is not decomposed by water, then the solution will contain the constituent salts in the same relative proportions as they are contained in the double salt, and the system may therefore be regarded as one of _two_ components, viz. double salt and water. In this case one solid phase is sufficient, with solution and {265} vapour, to give an univariant system; and at a given temperature, therefore, the solubility will have a perfectly definite value. Since in almost all cases the solubility is determined in open vessels, we shall in the following discussion consider that the vapour phase is absent, and that the system is under a constant pressure, that of the atmosphere. With this restriction, therefore, four phases will constitute an invariant system, three phases an univariant, and two phases a bivariant system. It has already been learned that in the case of sodium sulphate and water, the solubility curve of the salt undergoes a sudden change in direction at the transition point, and that this is accompanied by a change in the solid phase in equilibrium with the solution. The same behaviour is also found in the case of double salts. To illustrate this, we shall briefly discuss the solubility relations of a few double salts, beginning with one of the simplest cases, that of the formation of rubidium racemate from rubidium _d_- and _l_-tartrates. The solubilities are represented diagrammatically in Fig. 100, the numerical data being contained in the following table, in which the solubility is expressed as the number of gram-molecules Rb_{2}C_{4}H_{4}O_{6} in 100 gm.-molecules of water.[346] --------------------------------------------------------------- Temperature. | Solubility of tartrate | Solubility of racemate. | mixture. | --------------------------------------------------------------- 25° | 13.03 | 10.91 35° | -- | 12.63 40.4° | -- | 13.48 40.7° | 13.46 | -- 54° | 13.83 | -- --------------------------------------------------------------- In Fig. 100 the curve AB represents the solubility of the racemate, while A'BC represents the solubility of the mixed tartrates. Below the transition point, therefore, the solubility of the racemate is less than that of the mixed tartrates. The solution, saturated with respect to the latter, will be supersaturated with respect to the racemate; and if a nucleus of this is present, racemate will be deposited, and the mixed tartrates, if present in equimolecular amounts, will ultimately {266} entirely disappear, and only racemate will be left as solid phase. The solution will then have the composition represented by a point on the curve AB. Conversely, above the transition point, the saturated solution of the racemate would be supersaturated with respect to the two tartrates, and transformation into the latter would ensue. If, therefore, a solution of equimolecular proportions of rubidium _d_- and _l_-tartrates is allowed to evaporate at a temperature above 40°, a mixture of the two tartrates will be deposited; while at temperatures below 40° the racemate will separate out. [Illustration: FIG. 100.] Similar relationships are met with in the case of sodium ammonium _d_- and _l_-tartrate and sodium ammonium racemate; but in this case the racemate is the stable form in contact with solution above the transition point (27°).[347] Below the transition point, therefore, the solubility curve of the mixed tartrates will lie below the solubility curve of the racemate. Below the transition point, therefore, sodium ammonium racemate will break up in contact with solution into a mixture of sodium ammonium _d_- and _l_-tartrates. At a higher temperature, 35°, sodium ammonium racemate undergoes decomposition into sodium racemate and ammonium racemate.[348] The behaviour of sodium ammonium racemate is of interest from the fact that it was the first racemic substance to be resolved into its optically active forms by a process of crystallization. On neutralizing a solution of racemic tartaric acid, half with soda and half with ammonia, and allowing the solution to evaporate, Pasteur[349] obtained a mixture of sodium ammonium {267} _d_- and _l_-tartrates. Since Pasteur was unaware of the existence of a transition point, the success of his experiment was due to the happy chance that he allowed the solution to evaporate at a temperature below 27°; for had he employed a temperature above this, separation of the racemate into the two enantiomorphous forms would not have occurred. For this reason the attempt of Staedel to perform the same resolution met only with failure.[350] Decomposition of the Double Salt by Water.--In the two cases just described, the solubility relationships at the transition point are of a simpler character than in the case of most double salts. If, at a temperature above the transition point, a mixture of rubidium _d_- and _l_-tartrates in equimolecular proportions is brought in contact with water a solution will be obtained, which is saturated with respect to both enantiomorphous forms; and since the solubility of the two optical antipodes is identical, and the effect of one on the solubility of the other also the same, the solution will contain equimolecular amounts of the _d_- and _l_-salt. If, now, the solution is cooled down in contact with the solid salts to just below the transition point, it becomes supersaturated with respect to the racemate, and this will be deposited. The solution thereby becomes unsaturated with respect to the mixture of the active salts, and these must therefore pass into solution. As the latter are equally soluble, equal amounts of each will dissolve, and a further quantity of the racemate will be deposited. These processes of solution and deposition will continue until the single tartrates have completely disappeared, and only racemate is left as solid phase. As a consequence of the identical solubility of the two tartrates, therefore, no excess of either form will be left on passing through the transition point. From this it will be evident that the racemate can exist as single solid phase in contact with its saturated solution at the transition point; or, in other words, the racemate is not decomposed by water at the transition point. The same behaviour will evidently be exhibited by sodium ammonium racemate at 27°, for the two enantiomorphous sodium ammonium tartrates have also identical solubility. {268} Very different, however, is the behaviour of, say, astracanite, or of the majority of double salts; for the solubility of the constituent salts is now no longer the same. If, for example, excess of a mixture of sodium sulphate and magnesium sulphate, in equimolecular proportions, is brought in contact with water below the transition point (22°), more magnesium sulphate than sodium sulphate will dissolve, the solubility of these two salts in a common solution being given by the following figures, which express number of molecules of the salt in 100 molecules of water.[351] COMPOSITION OF SOLUTIONS SATURATED WITH RESPECT TO Na_{2}SO_{4},10H_{2}O AND MgSO_{4},7H_{2}O. ---------------------------------------- Temperature. | Na_{2}SO_{4}. | MgSO_{4}. ---------------------------------------- 18.5° | 2.16 | 4.57 24.5° | 3.43 | 4.68 ---------------------------------------- At the transition point, then, it is evident that the solution contains more magnesium sulphate than sodium sulphate: and this must still be the case when astracanite, which contains sodium sulphate and magnesium sulphate in equimolecular proportions, separates out. If, therefore, the temperature is raised slightly above the transition point, magnesium sulphate and sodium sulphate will pass into solution, the former, however, in larger quantities than the latter, and astracanite will be deposited; and this will go on until all the magnesium sulphate has disappeared, and a mixture of astracanite and sodium sulphate decahydrate is left as solid phases. Since there are now three phases present, the system is univariant (by reason of the restriction previously made that the vapour phase is absent), and at a given temperature the solution will have a definite composition; as given in the following table:-- COMPOSITION OF SOLUTIONS SATURATED WITH RESPECT TO Na_{2}Mg(SO_{4})_{2},4H_{2}O AND Na_{2}SO_{4},10H_{2}O. ---------------------------------------- Temperature. | Na_{2}SO_{4}. | MgSO_{4}. ---------------------------------------- 22° | 2.95 | 4.70 24.5° | 3.45 | 3.62 ---------------------------------------- {269} From the above figures, therefore, it will be seen that at a temperature just above the transition point a solution in contact with the two solid phases, astracanite and Glauber's salt, contains a relatively smaller amount of sodium sulphate than a pure solution of astracanite would; for in this case there would be equal molecular amounts of Na_{2}SO_{4} and MgSO_{4}. A solution which is saturated with respect to astracanite alone, will contain more sodium sulphate than the solution saturated with respect to astracanite plus Glauber's salt, and the latter will therefore be deposited. From this, therefore, it is clear that if astracanite is brought in contact with water at about the transition point, it will undergo decomposition with separation of Glauber's salt (supersaturation being excluded). [Illustration: FIG. 101.] This will perhaps be made clearer by considering Fig. 101. In this diagram the ordinates represent the ratio of sodium sulphate to magnesium sulphate in the solutions, and the abscissæ represent the temperatures. The line AB represents solutions saturated with respect to a mixture of the single salts (p. 268); BC refers to solutions in equilibrium with astracanite and magnesium sulphate; while BX represents the composition of solutions in contact with the solid phases astracanite and Glauber's salt. The values of the solubility are contained in the following table, and in that on p. 268, and are, as before, expressed in gm.-molecules of salt in 100 gm.-molecules of water.[352] {270} ------------------------------------------------------------------------- | Astracanite | Astracanite Temperature. | + sodium sulphate. | + magnesium sulphate. |----------------------------|------------------------------ | Na_{2}SO_{4}. | MgSO_{4}. | Na_{2}SO_{4}. | MgSO_{4}. ------------------------------------------------------------------------- 18.5° | -- | -- | 3.41 | 4.27 22° | 2.95 | 4.70 | 2.85 | 4.63 24.5° | 3.45 | 3.62 | 2.68 | 4.76 30° | 4.58 | 2.91 | 2.30 | 5.31 35° | 4.30 | 2.76 | 1.73 | 5.88 ------------------------------------------------------------------------- At the transition point the ratio of sodium sulphate to magnesium sulphate is approximately 1 : 1.6. In the case of solutions saturated with respect to both astracanite and Glauber's salt, the relative amount of sodium sulphate increases as the temperature rises, while in the solutions saturated for astracanite and magnesium sulphate, the ratio of sodium sulphate to magnesium sulphate decreases. If, now, we consider only the temperatures above the transition point, we see from the figure that solutions represented by points above the line BX contain relatively more sodium sulphate than solutions in contact with astracanite and Glauber's salt; and solutions lying below the line BC contain relatively more magnesium sulphate than solutions saturated with this salt and astracanite. These solutions will therefore not be stable, but will deposit in the one case, astracanite and Glauber's salt, and in the other case, astracanite and magnesium sulphate, until a point on BX or BC is reached. All solutions, however, lying to the right of CBX, will be _unsaturated_ with respect to these two pairs of salts, and only the solutions represented by the line XY (and which contain equimolecular amounts of sodium and magnesium sulphates) will be saturated with respect to the pure double salt. Transition Interval.--Fig. 101 will also render intelligible a point of great importance in connection with astracanite, and of double salts generally. At temperatures between those represented by the points B and X, the double salt when brought in contact with water will be decomposed with separation of sodium sulphate. Above the temperature of the point {271} X, however, the solution of the pure double salt is stable, because it can still take up a little of either of the components. At temperatures, then, above that at which the solution in contact with the double salt and the less soluble single salt, contains the single salts in the ratio in which they are present in the double salt, solution of the latter will take place without decomposition. _The range of temperature between that at which double salt can begin to be formed (the transition point) and that at which it ceases to be decomposed by water is called the transition interval._[353] If the two single salts have identical solubility at the transition point, the transition interval diminishes to nought. In those cases where the double salt is the stable form below the transition point, the transition interval will extend downwards to a lower temperature. Fig. 101 will then have the reverse form. Summary.--With regard to double salts we have learned that their formation from and their decomposition into the single salts, is connected with a definite temperature, the _transition temperature_. At this transition temperature two vapour pressure curves cut, viz. a curve of dehydration of a mixture of the single salts and the solubility curve of the double salt; or the dehydration curve of the double salt and the solubility curve of the mixed single salts. The solubility curves, also, of these two systems intersect at the transition point, but although the formation of the double salt commences at the transition point, complete stability in contact with water may not be attained till some temperature above (or below) that point. _Only when the temperature is beyond the transition interval, will a double salt dissolve in water without decomposition (_e.g._ the alums)._ * * * * * {272} CHAPTER XVI ISOTHERMAL CURVES AND THE SPACE MODEL In the preceding chapter we considered the changes in the solubility of double salts and of mixtures of their constituent salts with the temperature; noting, more especially, the relationships between the two systems at the transition point. It is now proposed to conclude the study of the three-component systems by discussing very briefly the solubility relations at constant temperature, or the isothermal solubility curves. In this way fresh light will be thrown on the change in the solubility of one component by the addition of another component, and also on the conditions of formation and stable existence of double salts in solution. With the help of these isothermal curves, also, the phenomena of crystallization at constant temperature--phenomena which have not only a scientific interest but also an important bearing on the industrial preparation of double salts--will be more clearly understood.[354] A brief description will also be given of the method of representing the variation of the concentration of the two salts in the solution with the temperature. Non-formation of Double Salts.--In Fig. 102 are shown the solubility curves of two salts, A and B, which at the given temperature do not form a double salt.[355] The ordinates represent the amount of A, the abscissæ the amount of B in a _constant amount_ of the third component, the solvent. The {273} point A, therefore, represents the solubility of the salt A at the given temperature; and similarly, point B represents the solubility of B. Since we are dealing with a three-component system, one solid phase in contact with solution will constitute a bivariant system (in the absence of the vapour phase and under a constant pressure). At any given temperature, therefore, the concentration of the solution in equilibrium with the solid can undergo change. If, now, to a pure solution of A a small quantity of B is added, the solubility of A will in general be altered; as a rule it is diminished, but sometimes it is increased.[356] The curve AC represents the varying composition of the solution in equilibrium with the solid component A. Similarly, the curve BC represents the composition of the solutions in contact with pure B as solid phase. At the point, C, where these two curves intersect, there are two solid phases, viz. pure A and pure B, in equilibrium with solution, and the system becomes invariant. At this point the solution is saturated with respect to both A and B, and at a given temperature must have a perfectly definite composition. To take an example, if we suppose A to represent sodium sulphate decahydrate, and B, magnesium sulphate heptahydrate, and the temperature to be 18.5° (_i.e._ below the transition point), the point C would represent a solution containing 2.16 gm.-molecules Na_{2}SO_{4} and 4.57 gm.-molecules MgSO_{4} per 100 gm.-molecules of water (p. 268). The curve ACB is the boundary curve for saturated solutions; solutions lying outside this curve are supersaturated, those lying within the area ACBO, are unsaturated. [Illustration: FIG. 102.] [Illustration: FIG. 103.] [Illustration: FIG. 104.] Formation of Double Salt.--We have already learned in the preceding chapter that if the temperature is outside[357] the {274} transition interval, it is possible to prepare a pure saturated solution of the double salt. If, now, we suppose the double salt to contain the two constituent salts in equimolecular proportions, its saturated solution must be represented by a point lying on the line which bisects the angle AOB; _e.g._ point D, Fig. 103. But a double salt constitutes only a single phase, and can exist, therefore, in contact with solutions of varying concentration, as represented by EDF. Let us compare, now, the relations between the solubility curve for the double salt, and those for the two constituent salts. We shall suppose that the double salt is formed from the single salts when the temperature is raised above a certain point (as in the formation of astracanite). At a temperature below the transition point, as we have already seen, the solubility of the double salt is greater than that of a mixture of the single salts. The curve EDF, therefore, must lie above the point C, in the region representing solutions supersaturated with respect to the single salts (Fig. 104). Such a solution, however, would be metastable, and on being brought in contact with the single salts would deposit these and yield a solution represented by the point C. At this particular temperature, therefore, the isothermal solubility curve will consist of only two branches. [Illustration: FIG. 105.] Suppose, now, that the temperature is that of the transition point. At this point, the double salt can exist together with the single salts in contact with solution. The solubility curve {275} of the double salt must, therefore, pass through the point C, as shown in Fig. 105. From this figure, now, it is seen that a solution saturated with respect to double salt alone (point D), is supersaturated with respect to the component A. If, then, at the temperature of the transition point, excess of the double salt is brought in contact with water,[358] and if supersaturation is excluded, _the double salt will undergo decomposition and the component A will be deposited_. The relative concentration of the component B in the solution will, therefore, increase, and the composition of the solution will be thereby altered in the direction DC. When the solution has the composition of C, the single salt ceases to be deposited, for at this point the solution is saturated for both double and single salt; and the system becomes invariant. This diagram explains very clearly the phenomenon of the decomposition of a double salt at the transition point. As is evident, this decomposition will occur when the solution which is saturated at the temperature of the transition point, with respect to the two single salts (point C), does not contain these salts in the same ratio in which they are present in the double salt. If point C lay on the dotted line bisecting the right angle, then the pure saturated solution of the double salt would not be supersaturated with respect to either of the single salts, and the double salt would, therefore, not be decomposed by water. As has already been mentioned, this behaviour is found in the case of optically active isomerides, the solubilities of which are identical. At the transition point, therefore, the isothermal curve also consists of two branches; but the point of intersection of the two branches now represents a solution which is saturated not {276} only with respect to the single salts, but also for the double salt in presence of the single salts. We have just seen that by a change of temperature the two solubility curves, that for the two single salts and that for the double salt, were made to approach one another (_cf._ Figs. 104 and 105). In the previous chapter, however, we found that on passing the transition point to the region of stability for the double salt, the solution which is saturated for a mixture of the two constituent salts, is supersaturated for the double salt. In this case, therefore, point C must lie above the solubility curve of the pure double salt (Fig. 106), and a solution of the composition C, if brought in contact with double salt, will deposit the latter. If the single salts were also present, then as the double salt separated out, the single salts would pass into solution, because so long as the two single salts are present, the composition of the solution must remain unaltered. If one of the single salts disappear before the other, there will be left double salt plus A or double salt plus B, according to which was in excess; and the composition of the solution will be either that represented by D (saturated for double salt plus A), or that of the point F (saturated for double salt plus B). [Illustration: FIG. 106.] In connection with the isothermal represented in Fig. 106, it should be noted that at this particular temperature a solution saturated with respect to the pure double salt is no longer supersaturated for one of the single salts (point D); so that at the temperature of this isothermal the double salt is not decomposed by water. At this temperature, further, the boundary curve consists of three branches AD, DF, and FB, which give the composition of the solutions in equilibrium with pure A, double salt, and pure B respectively; while the points D and F represent solutions saturated for double salt plus A and double salt plus B. On continuing to alter the temperature in the same direction {277} as before, the relative shifting of the solubility curves becomes more marked, as shown in Fig. 107. At the temperature of this isothermal, the solution saturated for the double salt now lies in a region of distinct unsaturation with respect to the single salts; and the double salt can now exist as solid phase in contact with solutions containing both relatively more of A (curve ED), and relatively more of B (curve DF), than is contained in the double salt itself. [Illustration: FIG. 107.] Transition Interval.--From what has been said, and from an examination of the isothermal diagrams, Figs. 104-107, it will be seen that by a variation of the temperature we can pass from a condition where the double salt is quite incapable of existing in contact with solution (supersaturation being excluded), to a condition where the existence of the double salt in presence of solution becomes possible; only in the presence, however, of one of the single salts (_transition point_, Fig. 105). A further change of temperature leads to a condition where the stable existence of the pure double salt in contact with solution just becomes possible (Fig. 106); and from this point onwards, pure saturated solutions of the double salt can be obtained (Fig. 107). _At any temperature, therefore, between that represented by Fig. 105, and that represented by Fig. 106, the double salt undergoes partial decomposition, with deposition of one of the constituent salts._ The temperature range between the transition point and the temperature at which a stable saturated solution of the pure double salt just begins to be possible, is known as the _transition interval_ (p. 270). As the figures show, the transition interval is limited on the one side by the transition temperature, and on the other by the temperature at which the solution saturated for double salt and the less soluble of the single salts, contains the component salts in the same ratio as they are present in the double salt. The greater the difference in the solubility of the single salts, the larger will be the transition interval. {278} Isothermal Evaporation.--The isothermal solubility curves are of great importance for obtaining an insight into the behaviour of a solution when subjected to isothermal evaporation. To simplify the discussion of the relationships found here, we shall still suppose that the double salt contains the single salts in equimolecular proportions; and we shall, in the first instance, suppose that the unsaturated solution with which we commence, also contains the single salts in the same ratio. The composition of the solution must, therefore, be represented by some point lying on the line OD, the bisectrix of the right angle. From what has been said, it is evident that when the formation of a double salt can occur, three temperature intervals can be distinguished, viz. the single-salt interval, the transition interval, and the double-salt interval.[359] When the temperature lies in the first interval, evaporation leads first of all to the crystallization of one of the single salts, and then to the separation of both the single salts together. In the second temperature interval, evaporation again leads, in the first place, to the deposition of one of the single salts, and afterwards to the crystallization of the double salt. In the third temperature interval, only the double salt crystallizes out. This will become clearer from what follows. [Illustration: FIG. 108.] [Illustration: FIG. 109.] If an unsaturated solution of the two single salts in equimolecular proportion (_e.g._ point _x_, Fig. 108) is evaporated at a temperature at which the formation of double salt is impossible, the component A, the solubility curve of which is {279} cut by the line OD, will first separate out; the solution will thereby become richer in B. On continued evaporation, more A will be deposited, and the composition of the solution will change until it attains the composition represented by the point C, when both A and B will be deposited, and the composition of the solution will remain unchanged. The result of evaporation will therefore be a mixture of the two components. If the formation of double salt is possible, but if the temperature lies within the transition interval, the relations will be represented by a diagram like Fig. 109. Isothermal evaporation of the solution X will lead to the deposition of the component A, and the composition of the solution will alter in the direction DE; at the latter point the double salt will be formed, and the composition of the solution will remain unchanged so long as the two solid phases are present. As can be seen from the diagram, however, the solution in E contains less of component A than is contained in the double salt. Deposition of the double salt at E, therefore, would lead to a relative decrease in the concentration of A in the solution, and to counterbalance this, _the salt which separated out at the commencement must redissolve_. Since the salts were originally present in equimolecular proportions, the final result of evaporation will be the pure double salt. If when the solution has reached the point E the salt A which had separated out is removed, double salt only will be left as solid phase. At a given temperature, however, a single solid phase can exist in equilibrium with solutions of different composition. If, therefore, isothermal evaporation is continued after the removal of the salt A, double salt will be deposited, and the composition of the solution will change in the direction EF. At the point F the salt B will separate out, and on evaporation both double salt and the salt B will be deposited. In the former case (when the salt A disappears on evaporation) we are dealing with an _incongruently saturated solution_; but in the latter case, where both solid phases continue to be deposited, the solution is said to be _congruently saturated_.[360] A "congruently saturated solution" is one from which the {280} solid phases are continuously deposited during isothermal evaporation to dryness, whereas in the case of "incongruently saturated solutions," at least one of the solid phases disappears during the process of evaporation. [Illustration: FIG. 110.] Lastly, if the temperature lies outside the transition interval, isothermal evaporation of an unsaturated solution of the composition X (Fig. 110) will lead to the deposition of pure double salt from beginning to end. If a solution of the composition Y is evaporated, the component A will first be deposited and the composition of the solution will alter in the direction of E, at which point double salt will separate out. Since the solution at this point contains relatively more of A than is present in the double salt, both the double salt and the single salt A will be deposited on continued evaporation, in order that the composition of the solution shall remain unchanged. In the case of solution Z, first component B and afterwards the double salt will be deposited. The result will, therefore, be a mixture of double salt and the salt B (congruently saturated solutions), It may be stated here that the same relationships as have been explained above for double salts are also found in the resolution of racemic compounds by means of optically active substances (third method of Pasteur). In this case the single salts are doubly active substances (_e.g._ strychnine-_d_-tartrate and strychnine-_l_-tartrate), and the double salt is a partially racemic compound.[361] Crystallization of Double Salt from Solutions containing Excess of One Component.--One more case of isothermal crystallization may be discussed. It is well known that a double salt which is decomposed by pure water can nevertheless be obtained pure by crystallization from a solution containing excess of one of the single salts (_e.g._ in the case of carnallite). Since the double salt is partially decomposed by water, the temperature of the experiment must be within the transition {281} interval, and the relations will, therefore, be represented by a diagram like Fig. 109. If, now, instead of starting with an unsaturated solution containing the single salts in equimolecular proportions, we commence with one in which excess of one of the salts is present, as represented by the point Y, isothermal evaporation will cause the composition to alter in the direction YD', the relative amounts of the single salts remaining the same throughout. When the composition of the solution reaches the point D', pure double salt will be deposited. The separation of double salt will, however, cause a relative decrease in the concentration of the salt A, and the composition of the solution will, therefore, alter in the direction D'F. If the evaporation is discontinued before the solution has attained the composition F, only double salt will have separated out. Even within the transition interval, therefore, pure double salt can be obtained by crystallization, provided the original solution has a composition represented by a point lying between the two lines OE and OF. Since, as already shown, the composition of the solution alters on evaporation in the direction EF, it will be best to employ a solution having a composition near to the line OE. Formation of Mixed Crystals.--If the two single salts A and B do not crystallize out pure from solution, but form an unbroken series of mixed crystals, it is evident that an invariant system cannot be produced. The solubility curve will therefore be continuous from A to B; the liquid solutions of varying composition being in equilibrium with solid solutions also of varying composition. If, however, the series of mixed crystals is not continuous, there will be a break in the solubility curve at which two solid solutions of different composition will be in equilibrium with liquid solution. This, of course, will constitute an invariant system, and the point will correspond to the point C in Fig. 108. A full discussion of these systems would, however, lead us too far, and the above indication of the behaviour must suffice.[362] {282} Application to the Characterization of Racemates.--The form of the isothermal solubility curves is also of great value for determining whether an inactive substance is a racemic compound or a conglomerate of equal proportions of the optical antipodes.[363] As has already been pointed out, the formation of racemic compounds from the two enantiomorphous isomerides, is analogous to the formation of double salts. The isothermal solubility curves, also, have a similar form. In the case of the latter, indeed, the relationships are simplified by the fact that the two enantiomorphous forms have identical solubility, and the solubility curves are therefore symmetrical to the line bisecting the angle of the co-ordinates. Further, with the exception of the partially racemic compounds to be mentioned later, there is no transition interval. In Fig. 111, are given diagrammatically two isothermal solubility curves for optically active substances. From what has been said in the immediately preceding pages, the figure ought really to explain itself. The upper isothermal _acb_ represents the solubility relations when the formation of a racemic compound is excluded, as, _e.g._ in the case of rubidium _d_- and _l_-tartrates above the transition point (p. 265). The solution at the point _c_ is, of course, inactive, and _is unaffected by addition of either the _d_- or _l_- form_. The lower isothermal, on the other hand, would be obtained at a temperature at which the racemic compound could be formed. The curve _a'e_ is the solubility curve for the _l_- form; _b'f_, that for the _d_- form; and _edf_, that for the racemic compound in presence of solutions of varying concentration. The point _d_ corresponds to saturation for the pure racemic compound. [Illustration: FIG. 111.] From these curves now, it will be evident that it will be possible, in any given case, to decide whether or not an inactive body is a mixture or a racemic compound. For this purpose, {283} two solubility determinations are made, first with the inactive material alone (in excess), and then with the inactive material plus excess of one of the optically active forms. If we are dealing with a mixture, the two solutions thus obtained will be identical; both will have the composition corresponding to the point _c_, and will be inactive. If, however, the inactive material is a racemic compound, then two different solutions will be obtained; namely, an inactive solution corresponding to the point _d_ (Fig. 111), and an _active_ solution corresponding either to _e_ or to _f_, according to which enantiomorphous form was added. _Partially racemic compounds._[364] In this case we are no longer dealing with enantiomorphous forms, and the solubility of the two oppositely active isomerides is no longer the same. The symmetry of the solubility curves therefore disappears, and a figure is obtained which is identical in its general form with that found in the case of ordinary double salts (Fig. 112). In this case there is a transition interval. [Illustration: FIG. 112.] The curves _acb_ belong to a temperature at which the partially racemic compound cannot be formed; _a'dfb'_, to the temperature at which the compound just begins to be stable in contact with water, and _a"ed'f'b"_ belongs to a temperature at which the partially racemic compound is quite stable in contact with water. Suppose now solubility determinations, made in the first case with the original material alone, and then with the original body plus each of the two compounds, formed from the enantiomorphous substances separately, then if the original body was a mixture, identical solutions will be obtained in all three cases (point _c_); if it was a partially racemic compound, three different solutions (_e_, _d'_, and _f'_) will be obtained if the temperature was outside the transition interval, and two solutions, _d_ and _f_, if the temperature belonged to the transition interval. {284} _Representation in Space._ Space Model for Carnallite.--Interesting and important as the isothermal solubility curves are, they are insufficient for the purpose of obtaining a clear insight into the complete behaviour of the systems of two salts and water. A short description will, therefore, be given here of the representation in space of the solubility relations of potassium and magnesium chlorides, and of the double salt which they form, carnallite.[365] [Illustration: FIG. 113.] Fig. 113 is a diagrammatic sketch of the model for carnallite looked at sideways from above. Along the X-axis is measured the concentration of magnesium chloride in the {285} solution; along the Y-axis, the concentration of potassium chloride; while along the T-axis is measured the temperature. The three axes are at right angles to one another. The XT-plane, therefore, contains the solubility curve of magnesium chloride; the YT-plane, the solubility curve of potassium chloride, and in the space between the two planes, there are represented the composition of solutions containing both magnesium and potassium chlorides. Any _surface_ between the two planes will represent the various solutions in equilibrium with only one solid phase, and will therefore indicate the area or field of existence of bivariant ternary systems. A _line_ or _curve_ formed by the intersection of two surfaces will represent solutions in equilibrium with two solid phases (viz. those belonging to the intersecting surfaces), and will show the conditions for the existence of univariant systems. Lastly, _points_ formed by the intersection of three surfaces will represent invariant systems, in which a solution can exist in equilibrium with three solid phases (viz. those belonging to the three surfaces). We shall first consider the solubility relations of the single salts. The complete equilibrium curve for magnesium chloride and water is represented in Fig. 113 by the series of curves ABF_{1} G_{1} H_{1} J_{1} L_{1} N_{1}. AB is the freezing-point curve of ice in contact with solutions containing magnesium chloride, and B is the cryohydric point at which the solid phases ice and MgCl_{2},12H_{2}O can co-exist with solution. BFG is the solubility curve of magnesium chloride dodecahydrate. This curve shows a point of maximum temperature at F_{1}, and a retroflex portion F_{1}G_{1}. The curve is therefore of the form exhibited by calcium chloride hexahydrate, or the hydrates of ferric chloride (Chapter VIII.). G_{1} is a transition point at which the solid phase changes from dodecahydrate to octahydrate, the solubility of which is represented by the curve G_{1}H_{1}. At H_{1} the octahydrate gives place to the hexahydrate, which is the solid phase in equilibrium with the solutions represented by the curve H_{1}J_{1}. J_{1} and L_{1} are also transition points at which the solid phase undergoes change, in the former case from hexahydrate to tetrahydrate; and in the latter case, {286} from tetrahydrate to dihydrate. The complete curve of equilibrium for magnesium chloride and water is, therefore, somewhat complicated, and is a good example of the solubility curves obtained with salts capable of forming several hydrates. The solubility curve of potassium chloride is of the simplest form, consisting only of the two branches AC, the freezing-point curve of ice, and CO, the solubility curve of the salt. C is the cryohydric point. This point and the two curves lie in the YT-plane. On passing to the ternary systems, the composition of the solutions must be represented by points or curves situated _between_ the two planes. We shall now turn to the consideration of these. BD and CD are ternary eutectic curves (p. 284). They give the composition of solutions in equilibrium with ice and magnesium chloride dodecahydrate (BD), and with ice and potassium chloride (CD). D is a _ternary cryohydric point_. If the temperature is raised and the ice allowed to disappear, we shall pass to the solubility curve for MgCl_{2},12H_{2}O + KCl (curve DE). At E carnallite is formed and the potassium chloride disappears; EFG is then the solubility curve for MgCl_{2},12H_{2}O + carnallite (KMgCl_{3},6H_{2}O). This curve also shows a point of maximum temperature (F) and a retroflex portion. GH and HJ represent the solubility curves of carnallite + MgCl_{2},8H_{2}O and carnallite + MgCl_{2},6H_{2}O, G and H being transition points. JK is the solubility curve for carnallite + MgCl_{2},4H_{2}O. At the point K we have the _highest temperature at which carnallite can exist with magnesium chloride in contact with solution_. Above this temperature decomposition takes place and potassium chloride separates out. If at the point E, at which the two single salts and the double salt are present, excess of potassium chloride is added, the magnesium chloride will all disappear owing to the formation of carnallite, and there will be left carnallite and potassium chloride. The solubility curve for a mixture of these two salts is represented by EMK; a simple curve exhibiting, however, a temperature maximum at M. This maximum point corresponds with the fact that dry carnallite melts at this temperature with separation of potassium chloride. _At all temperatures {287} above this point, the formation of double salt is impossible_. The retroflex portion of the curve represents solutions in equilibrium with carnallite and potassium chloride, but in which the ratio MgCl_{2} : KCl is greater than in the double salt. Throughout its whole course, _the curve EMK represents solutions in which the ratio of MgCl_{2} : KCl is greater than in the double salt_. As this is a point of some importance, it will be well, perhaps, to make it clearer by giving one of the isothermal curves, _e.g._ the curve for 10°, which is represented diagrammatically in Fig. 114. E and F here represent solutions saturated for carnallite plus magnesium chloride hydrate, and for carnallite plus potassium chloride. As is evident, the point F lies above the line representing equimolecular proportions of the salts (OD). [Illustration: FIG. 114.] Summary and Numerical Data.--We may now sum up the different systems which can be formed, and give the numerical data from which the model is constructed.[366] I. _Bivariant Systems._ -------------------------------------- Solid phase. | Area of existence. -------------------------------------- Ice | ABDC KCl | CDEMKLNO Carnallite | EFGHJKM MgCl_{2},12H_{2}O | BF_{1}G_{1}GFED MgCl_{2},8H_{2}O | G_{1}H_{1}HG MgCl_{2},6H_{2}O | H_{1}I_{1}IH MgCl_{2},4H_{2}O | I_{1}L_{1}LKI MgCl_{2},2H_{2}O | L_{1}N_{1}NL -------------------------------------- II. _Univariant Systems._--The different univariant systems have already been described. The course of the curves will be sufficiently indicated if the temperature and composition of the solutions for the different invariant systems are given. {288} III.--_Invariant Systems--Binary and Ternary._ ------------------------------------------------------------------------- | | | Composition of solution. Point. | Solid Phases. | Temper- | Gram-molecules of salt | | ature. | per 1000 gram-mol. water. ------------------------------------------------------------------------- A | Ice | 0° | -- | | | B | Ice; MgCl_{2},12H_{2}O | -33.6° | 49.2 MgCl_{2} | | | C | Ice; KCl | -11.1° | 59.4 KCl | | | D |{ Ice; MgCl_{2},12H_{2}O; }| -34.3° | 43 MgCl_{2}; 3 KCl |{ KCl }| | | | | E |{ MgCl_{2},12H_{2}O; KCl; }| -21° | 66.1 MgCl_{2}; 4.9 KCl |{ carnallite }| | | | | F_{1} | MgCl_{2},12H_{2}O | -16.4° | 83.33 MgCl_{2} | | | F |{ MgCl_{2},12H_{2}O; }| -16.6° |{ Almost same as F_{1}; |{ carnallite }| |{ contains small amount | | |{ of KCl | | | G_{1} |{ MgCl_{2},12H_{2}O; }| -16.8° | 87.5 MgCl_{2} |{ MgCl_{2},8H_{2}O }| | | | | G |{ MgCl_{2},12H_{2}O; }| -16.9° |{ Almost same as G_{1}, |{ MgCl_{2},8H_{2}O; }| |{ but contains small |{ carnallite }| |{ quantity of KCl | | | H_{1} |{ MgCl_{2},8H_{2}O; }| -3.4° | 99 MgCl_{2} |{ MgCl_{2},6H_{2}O }| | | | | H |{ MgCl_{2},8H_{2}O; }|ca. -3.4° |{ Almost same as H_{1}, |{ MgCl_{2},6H_{2}O; }| |{ but contains small |{ carnallite }| |{ amount of KCl | | | J_{1} |{ MgCl_{2},6H_{2}O; }| 116.67° | 161.8 MgCl_{2} |{ MgCl_{2},4H_{2}O }| | | | | J |{ MgCl_{2},6H_{2}O; }| 115.7° | 162 MgCl_{2}; 4 KCl |{ MgCl_{2},4H_{2}O; }| | |{ carnallite }| | | | | K |{ MgCl_{2},4H_{2}O; KCl; }| 152.5° | 200 MgCl_{2}; 24 KCl |{ carnallite }| | | | | L_{1} |{ MgCl_{2},4H_{2}O; }| 181° | 238.1 MgCl_{2} |{ MgCl_{2},2H_{2}O }| | | | | L |{ MgCl_{2},4H_{2}O; }| 176° | 240 MgCl_{2}; 41 KCl |{ MgCl_{2},2H_{2}O; KCl }| | | | | M | Carnallite; KCl | 167.5° | 166.7 MgCl_{2}; 41.7 KCl | | | [N_{1} | MgCl_{2},2H_{2}O | 186° | ca. 241 MgCl_{2}] | | | N | MgCl_{2},2H_{2}O; KCl | 186° | 240 MgCl_{2}; 63 KCl | | | [O | KCl | 186° | 195.6 KCl] ------------------------------------------------------------------------- With the help of the data in the preceding table and of the solid model it will be possible to state in any given case what will be the behaviour of a system composed of magnesium chloride, potassium chloride and water. One or two different cases will be very briefly described; and the reader should have no difficulty in working out the behaviour under other conditions with the help of the model and the numerical data just given. {289} In the first place it may be again noted that at a temperature above 167.5° (point M) carnallite cannot exist. If, therefore, a solution of magnesium and potassium chlorides is evaporated at a temperature above this point, the result will be a mixture of potassium chloride and either magnesium chloride tetrahydrate or magnesium chloride dihydrate, according as the temperature is below or above 176°. The isothermal curve here consists of only two branches. Further, reference has already been made to the fact that all points of the carnallite area correspond to solutions in equilibrium with carnallite, but in which the ratio of MgCl_{2} to KCl is greater than in the double salt. A solution which is saturated with respect to double salt alone will be supersaturated with respect to potassium chloride. At all temperatures, therefore, carnallite is decomposed by water with separation of potassium chloride; hence all solutions obtained by adding excess of carnallite to water will lie on the curve EM. _A pure saturated solution of carnallite cannot be obtained._ If an unsaturated solution of the two salts in equimolecular amounts is evaporated, potassium chloride will first be deposited, because the plane bisecting the right angle formed by the X and Y axes cuts the area for that salt. Deposition of potassium chloride will lead to a relative increase in the concentration of magnesium chloride in the solution; and on continued evaporation a point (on the curve EM) will be reached at which carnallite will separate out. So long as the two solid phases are present, the composition of the solution must remain unchanged. Since the separation of carnallite causes a decrease in the relative concentration of the potassium chloride in the solution, the portion of this salt which was deposited at the commencement must _redissolve_, and carnallite will be left on evaporating to dryness. (_Incongruently saturated solution._) Although carnallite is decomposed by pure water, it will be possible to crystallize it from a solution having a composition represented by any point in the carnallite area. Since during the separation of the double salt the relative amount of magnesium chloride increases, it is most advantageous to {290} commence with a solution the composition of which is represented by a point lying just above the curve EM (cf. p. 281). From the above description of the behaviour of carnallite in solution, the processes usually employed for obtaining potassium chloride will be readily intelligible.[367] Ferric Chloride--Hydrogen Chloride--Water.--In the case of another system of three components which we shall now describe, the relationships are considerably more complicated than in those already discussed. They deserve discussion, however, on account of the fact that they exhibit a number of new phenomena. In the system formed by the three components, ferric chloride, hydrogen chloride, and water, not only can various compounds of ferric chloride and water (p. 152), and of hydrogen chloride and water be formed, each of which possesses a definite melting point, but various ternary compounds are also known. Thus we have the following solid phases:-- 2FeCl_{3},12H_{2}O HCl,3H_{2}O 2FeCl_{3},2HCl,12H_{2}O 2FeCl_{3},7H_{2}O HCl,2H_{2}O 2FeCl_{3},2HCl,8H_{2}O 2FeCl_{3},5H_{2}O HCl,H_{2}O 2FeCl_{3},2HCl,4H_{2}O 2FeCl_{3},4H_{2}O FeCl_{3} From this it will be readily understood that the complete study of the conditions of temperature and concentration under which solutions can exist, either with one solid phase or with two or three solid phases, are exceedingly complicated; and, as a matter of fact, only a few of the possible equilibria have been investigated. We shall attempt here only a brief description of the most important of these.[368] If we again employ rectangular co-ordinates for the graphic {291} representation of the results, we have the two planes XOT and YOT (Fig. 115): the concentration of ferric chloride being measured along the X-axis, the concentration of hydrogen chloride along the Y-axis, and the temperature along the T-axis. The curve ABCDEFGHJK is, therefore, the solubility curve of ferric chloride in water (p. 152), and the curve A'B'C'D'E'F' the solubility curve of hydrogen chloride and its hydrates. B' and D' are the melting points of the hydrates HCl,3H_{2}O and HCl,2H_{2}O. In the space between these two planes are represented those systems in which all three components are present. As already stated, only a few of the possible ternary systems have been investigated, and these are represented in Fig. 116. The figure shows the model resting on the XOT-plane, so that the lower edge represents the solubility curve of ferric chloride, the concentration increasing from right to left. The concentration of hydrogen chloride is measured upwards, and the temperature forwards. The further end of the model represents the isothermal surface for -30°. The surface of the model on the left does not correspond with the plane YOT in Fig. 115, but with a parallel plane which cuts the concentration axis for ferric chloride at a point representing 65 gm.-molecules FeCl_{3} in 100 gm.-molecules of water. The upper surface corresponds with a plane parallel to the axis XOT, at a distance corresponding with the concentration of 50 gm.-molecules HCl in 100 gm.-molecules of water. [Illustration: FIG. 115.] Ternary Systems.--We pass over the binary system FeCl_{3}--H_{2}O, which has already been discussed (p. 152), and the similar system HCl--H_{2}O (see Fig. 115), and turn to the discussion of some of the ternary systems represented by {292} points on the surface of the model between the planes XOT and YOT. As in the case of carnallite, a plane represents the conditions of concentration of solution and temperature under which a ternary solution can be in equilibrium with a _single_ solid phase (bivariant systems), a line represents the conditions for the coexistence of a solution with two solid phases (univariant systems), and a point the conditions for equilibrium with three solid phases (invariant systems). [Illustration: FIG. 116.] In the case of a binary system, in which 2FeCl_{3},12H_{2}O is in equilibrium with a solution of the same composition, addition of hydrogen chloride must evidently lower the temperature at which equilibrium can exist; and the same holds, of course, {293} for all other binary solutions in equilibrium with this solid phase. In this way we obtain the surface I., which represents the temperatures and concentrations of solutions in which 2FeCl_{3},12H_{2}O can be in equilibrium with a ternary solution containing ferric chloride, hydrogen chloride, and water. This surface is analogous to the curved surface K_{1}K_{2}_k__{4}_k__{3} in Fig. 97 (p. 256). Similarly, the surfaces II., III., IV., and V. represent the conditions for equilibrium between the solid phases 2FeCl_{3},7H_{2}O; 2FeCl_{3},5H_{2}O; 2FeCl_{3},4H_{2}O; FeCl_{3} and ternary solutions respectively. The lines CL, EM, GN, and IO on the model represent univariant systems in which a ternary solution is in equilibrium with two solid phases, viz. with those represented by the adjoining fields. These lines correspond with the ternary eutectic curves _k__{3}K_{1} and _k__{4}K_{2} in Fig. 97. Besides the surfaces already mentioned, there are still three others, VI., VII., and VIII., which also represent the conditions for equilibrium between one solid phase and a ternary solution; but in these cases, the solid phase is not a binary compound or an anhydrous salt, but a ternary compound containing all three components. The solid phases which are in equilibrium with the ternary solutions represented by the surfaces VI., VII., and VIII., are 2FeCl_{3},2HCl,4H_{2}O; 2FeCl_{3},2HCl,8H_{2}O; and 2FeCl_{3},2HCl,12H_{2}O respectively. The model for FeCl_{3}--HCl--H_{2}O exhibits certain other peculiarities not found in the case of MgCl_{2}--KCl--H_{2}O. On examining the model more closely, it is found that the field of the ternary compound 2FeCl_{3},2HCl,8H_{2}O (VII.) resembles the surface of a sugar cone, and has a projecting point, the end of which corresponds with a higher temperature than does any other point of the surface. At the point of maximum temperature the composition of the liquid phase is the same as that of the solid. This point, therefore, represents the melting point of the double salt of the above composition. The curves representing univariant systems are of two kinds. In the one case, the two solid phases present are both binary compounds; or one is a binary compound and the other is one of the components. In the other case, either one or both solid phases are ternary compounds. Curves belonging {294} to the former class (so-called _border curves_) start from binary eutectic points, and their course is always towards lower temperatures, _e.g._ CL, EM, GN, IO. Curves belonging to the latter class (so-called _medial curves_) would, in a triangular diagram, lie entirely within the triangle. Such curves are YV, WV, VL, LM, MV, NS, ST, SO, OZ. These curves do not always run from higher to lower temperatures, but may even exhibit a point of maximum temperature. Such maxima are found, for example, at U (Fig. 116), and also on the curves ST and LV. Finally, whereas all the other ternary univariant curves run in valleys between the adjoining surfaces, we find at the point X a similar appearance to that found in the case of carnallite, as the univariant curve here rises above the surrounding surface. The point X, therefore, does not correspond with a eutectic point, but with a transition point. At this point the ternary compound 2FeCl_{3},2HCl,12H_{2}O melts with separation of 2FeCl_{3},12H_{2}O, just as carnallite melts at 168° with separation of potassium chloride. The Isothermal Curves.--A deeper insight into the behaviour of the system FeCl_{3}--HCl--H_{2}O is obtained from a study of the isothermal curves, the complete series of which, so far as they have been studied, is given in Fig. 117.[369] In this figure the lightly drawn curves represent isothermal solubility curves, the particular temperature being printed beside the curve.[370] The dark lines give the composition of the univariant systems at different temperatures. The point of intersection of a dark with a light curve gives the composition of the univariant solution at the temperature represented by the light curve; and the point of intersection of two dark lines gives the composition of the invariant solution in equilibrium with three solid phases. The dotted lines represent metastable systems, and the points P, Q, and R represent solutions of {295} the composition of the ternary salts, 2FeCl_{3},2HCl,4H_{2}O; 2FeCl_{3},2HCl,8H_{2}O; and 2FeCl_{3},2HCl,12H_{2}O. [Illustration: FIG. 117.] The farther end of the model (Fig. 116) corresponds, as already mentioned, to the temperature -30°, so that the outline evidently represents the isothermal curve for that temperature. Fig. 117 does not show this. We can, however, follow the isothermal for -20°, which is the extreme curve on the right in Fig. 117. Point A represents the solubility of 2FeCl_{3},12H_{2}O in water. If hydrogen chloride is added, the concentration of ferric chloride in the solution first decreases and then increases, until at point 34 the ternary double salt 2FeCl_{3},2HCl,12H_{2}O is formed. If the addition of hydrogen chloride is continued, the ferric chloride disappears ultimately, and only the ternary double salt remains. This salt can coexist with solutions of the composition represented by the curve which passes through the points 173, 174, 175. At the last-mentioned point, the ternary salt with 8H_{2}O is formed. The composition of the solutions with which this salt is in equilibrium at -20° is represented by the curve which passes through a point of maximal concentration with respect to HCl, and cuts the curve SN at the point 112, at which the solution is in equilibrium with the two solid phases 2FeCl_{3},4H_{2}O and 2FeCl_{3},2HCl,8H_{2}O. The succeeding portion of the isotherm represents the solubility curve at -20° of 2FeCl_{3},4H_{2}O, which cuts the dark line OS at point 113, at which the solution is in equilibrium with the two solid phases 2FeCl_{3},4H_{2}O and 2FeCl_{3},2HCl,4H_{2}O. Thereafter comes the solubility curve of the latter compound. The other isothermal curves can be followed in a similar manner. If the temperature is raised, the region of existence of the ternary double salts becomes smaller and smaller, and at temperatures above 30° the ternary salts with 12H_{2}O and 8H_{2}O are no longer capable of existing. If the temperature is raised above 46°, only the binary compounds of ferric chloride and water and the anhydrous salt can exist as solid phases. The isothermal curve for 0° represents the solubility curve for 2FeCl_{3},12H_{2}O; 2FeCl_{3},7H_{2}O; 2FeCl_{3},5H_{2}O; and 2FeCl_{3},4H_{2}O. {296} Finally, in the case of the system FeCl_{3}--HCl--H_{2}O, we find _closed_ isothermal curves. Since, as already stated, the salt 2FeCl_{3},2HCl,8H_{2}O has a definite melting point, the temperature of which is therefore higher than that at which this compound is in equilibrium with solutions of other composition, it follows that the line of intersection of an isothermal plane corresponding with a temperature immediately below the melting point of the salt with the cone-shaped surface of its region of existence, will form a closed curve. This is shown by the isotherm for -4.5°, which surrounds the point Q, the melting point of the ternary salt. The following table gives some of the numerical data from which the curves and the model have been constructed:-- ------------------------------------------------------------------------- | | | Composition of the sol- | | | ution in gm.-mols. salt Point. | Solid phases. | Temper- | to 100 gm.-mols. water. | | ature. |------------------------ | | | HCl | FeCl_{3} ------------------------------------------------------------------------- A | 2FeCl_{3},12H_{2}O | -20° | -- | 6.56 | | | | C |{ 2FeCl_{3},12H_{2}O; }| 27.4° | -- | 24.30 |{ 2FeCl_{3},7H_{2}O }| | | | | | | E |{ 2FeCl_{3},7H_{2}O; }| 30° | -- | 30.24 |{ 2FeCl_{3},5H_{2}O }| | | | | | | G |{ 2FeCl_{3},5H_{2}O; }| 55° | -- | 40.64 |{ 2FeCl_{3},4H_{2}O }| | | | | | | J | 2FeCl_{3},4H_{2}O; FeCl_{3} | 66° | -- | 58.40 | | | | |{ 2FeCl_{3},12H_{2}O; }| | | L |{ 2FeCl_{3},7H_{2}O; }| -7.5° | 19.22 | 23.72 |{ 2FeCl_{3},2HCl,8H_{2}O }| | | | | | | |{ 2FeCl_{3},7H_{2}O; }| | | M |{ 2FeCl_{3},5H_{2}O; }| -7.3° | 23.08 | 28.55 |{ 2FeCl_{3},2HCl,8H_{2}O }| | | | | | | |{ 2FeCl_{3},5H_{2}O; }| | | N |{ 2FeCl_{3},4H_{2}O; }| -16° | 28.40 | 31.89 |{ 2FeCl_{3},2HCl,8H_{2}O }| | | | | | | |{ 2FeCl_{3},4H_{2}O; }| | | S |{ 2FeCl_{3},2HCl,8H_{2}O; }| -27.5° | 32.33 | 34.21 |{ 2FeCl_{3},2HCl,4H_{2}O }| | | | | | | |{ 2FeCl_{3},4H_{2}O; }| | | O |{ FeCl_{3}; }| 29° | 33.71 | 49.84 |{ 2FeCl_{3},2HCl,4H_{2}O }| | | | | | | U |{ 2FeCl_{3},7H_{2}O; }| -4.5° | 20.66 | 25.74 |{ 2FeCl_{3},2HCl,8H_{2}O }| | | | | | | |{ 2FeCl_{3},12H_{2}O; }| | | V |{ 2FeCl_{3},2HCl,12H_{2}O; }| -13° | 22.40 | 18.00 |{ 2FeCl_{3},2HCl,8H_{2}O }| | | | | | | X |{ 2FeCl_{3},12H_{2}O; }| -12.5° | 22.14 | 16.69 |{ 2FeCl_{3},2HCl,12H_{2}O }| | | | | | | Q | 2FeCl_{3},2HCl,8H_{2}O | -3° (melting point) ------------------------------------------------------------------------- Basic Salts.--Another class of systems in the study of {297} which the Phase Rule has performed exceptional service, is that of the basic salts. In many cases it is impossible, by the ordinary methods of analysis, to decide whether one is dealing with a definite chemical individual or with a mixture. The question whether a solid phase is a chemical individual can, however, be answered, in most cases, with the help of the principles which we have already learnt. Let us consider, for example, the formation of basic salts from bismuth nitrate, and water. In this case we can choose as components Bi_{2}O_{3}, N_{2}O_{5}, and H_{2}O; since all the systems consist of these in varying amounts. If we are dealing with a condition of equilibrium at constant temperature between liquid and solid phases, three cases can be distinguished,[371] viz.-- 1. The solutions in different experiments have the same composition, but the composition of the precipitate alters. In this case there must be two solid phases. 2. The solutions in different experiments can have varying composition, while the composition of the precipitate remains unchanged. In this case only one solid phase exists, a definite compound. 3. The composition both of the solution and of the precipitate varies. In this case the solid phase is a solid solution or a mixed crystal. In order, therefore, to decide what is the nature of a precipitate produced by the hydrolysis of a normal salt, it is only necessary to ascertain whether and how the composition of the precipitate alters with alteration in the composition of the solution. If the composition of the solution is represented by abscissæ, and the composition of the precipitate by ordinates, the form of the curves obtained would enable us to answer our question; for vertical lines would indicate the presence of two solid phases (1st case), horizontal lines the presence of only one solid phase (2nd case), and slanting lines the presence of mixed crystals (3rd case). This method of representation cannot, however, be carried out in most cases. It is, however, {298} generally possible to find one pair or several pairs of components, the _relative amounts_ of which in the solution or in the precipitate undergo change when, and only when, the composition of the solution or of the precipitate changes. Thus, in the case of bismuth, nitrate, and water, we can represent the ratio of Bi_{2}O_{3} : N_{2}O_{5} in the precipitate as ordinates, and N_{2}O_{5} : H_{2}O in the solution as abscissæ. A horizontal line then indicates a single solid phase, and a vertical line two solid phases. An example of this is given in Fig. 118.[372] [Illustration: FIG. 118.] Bi_{2}O_{3}--N_{2}O_{5}--H_{2}O.--Although various systems have been studied in which there is formation of basic salts,[373] we shall content ourselves here with the description of some of the conditions for the formation of basic salts of bismuth nitrate, and for their equilibrium in contact with solutions.[374] Three normal salts of bismuth oxide and nitric acid are known, viz. Bi_{2}O_{3},3N_{2}O_{5},10H_{2}O(S_{10}); Bi_{2}O_{3},3N_{2}O_{5},4H_{2}O(S_{4}); and Bi_{2}O_{3},3N_{2}O_{5},3H_{2}O(S_{3}). Besides these normal salts, there are the following basic salts:-- {299} Bi_{2}O_{3},N_{2}O_{5},2H_{2}O (represented by B_{1-1-2}) Bi_{2}O_{3},N_{2}O_{5},H_{2}O ( " " B_{1-1-1}) 6Bi_{2}O_{3},5N_{2}O_{5},9H_{2}O ( " " B_{6-5-9}) 2Bi_{2}O_{3},N_{2}O_{5},H_{2}O ( " " B_{2-1-1}) Probably some others also exist. The problem now is to find the conditions under which these different normal and basic salts can be in equilibrium with solutions of varying concentration of the three components. Having determined the equilibrium conditions for the different salts, it is then possible to construct a model similar to that for MgCl_{2}--KCl--H_{2}O or for FeCl_{3}--HCl--H_{2}O, from which it will be possible to determine the limits of stability of the different salts, and to predict what will occur when we bring the salts in contact with solutions of nitric acid of different concentrations and at different temperatures. For our present purpose it is sufficient to pick out only some of the equilibria which have been studied, and which are represented in the model (Fig. 119). In this case use has been made of the triangular method of representation, so that the surface of the model lies within the prism. [Illustration: FIG. 119.] This model shows the three surfaces, A, B, and C, which represent the conditions for the stable existence of the salts B_{1-1-1}, S_{10}, and S_{3} in contact with solution at different {300} temperatures. The front surface of the model represents the temperature 9°, and the farther end the temperature 75.5°. The dotted curve represents the isotherm for 20°. The prominences between the surfaces represent, of course, solutions which are saturated in respect of two solid phases. Thus, for example, _pabc_ represents solutions in equilibrium with B_{1-1-1} and S_{10}; and the ridge _qdc_, solutions in equilibrium with S_{10} and S_{3}. The point _b_, which lies at 75.5°, is the point of maximum temperature for S_{10}. If the temperature is raised above this point, S_{10} decomposes into the basic salt B_{1-1-1} and solution. This point is therefore analogous to the point M in the carnallite model, at which this salt decomposes into potassium chloride and solution (p. 284); or to the point at which the salt 2FeCl_{3},2HCl,12H_{2}O decomposes into 2FeCl_{3},12H_{2}O and solution (p. 294). The curve _pab_ has been followed to the temperature of 72° (point _c_). The end of the model is incomplete, but it is probable that in the neighbourhood of the point _c_ there exists a quintuple point at which the basic salt B_{1-2-2} appears. In the neighbourhood of _e_ also there probably exists another quintuple point at which S_{4} is formed. These systems have, however, not been studied. The following tables give some of the numerical data:-- ISOTHERM FOR 20°. ---------------------------------------------------------------------- | Composition of the solution. Gram-mols. | in 1000 gm.-mols. of water. Solid phase. |---------------------------------------- | Bi_{2}O_{3} | N_{2}O_{5} -----------------------------|-----------------|---------------------- B_{1-1-1} | 10.50 | 38.65 -- | 27.20 | 83.84 B_{1-1-1}; S_{10} | 30.15 | 97.97 S_{10} | 29.70 | 96.57 -- | 19.65 | 98.76 -- | 10.51 | 162.58 -- | 33.51 | 355.87 S_{10}; S_{3} | 51.00 | 403.0 S_{3} | 14.35 | 492.0 -- | 7.45 | 592.9 ---------------------------------------------------------------------- SYSTEMS IN EQUILIBRIUM WITH B_{1-1-1} AND S_{10} (CURVE _pabc_). ------------------------------------------------------------ | Composition of the solution. Gram-mols. | in 1000 gm.-mols. of water. Temperature. |---------------------------------------- | Bi_{2}O_{3} | N_{2}O_{5} -------------------|---------------|------------------------ 9° | 26.7 | 88.2 20° (point _a_) | 30.15 | 97.97 30° | 33.6 | 112.3 50° | 41.8 | 148.4 65° | 57.21 | 190.8 75.5° (point _b_) | 87.9 | 288.4 72° (point _c_) | 96.0 | 327.0 ------------------------------------------------------------ SYSTEMS IN EQUILIBRIUM WITH S_{10} AND S_{3} (CURVE _qde_). -------------------------------------------------------- | Composition of the solution. Gram-mols. | in 1000 gm.-mols. of water. Temperature. |----------------------------------------- | Bi_{2}O_{3} | N_{2}O_{5} --------------|---------------|------------------------- 11.5° | 44.5 | 396 20° | 51.0 | 405.4 50° | 66.5 | 444.2 65° | 80.0 | 454.4 -------------------------------------------------------- Basic Mercury Salts.--The Phase Rule has also been applied by A. J. Cox[375] in an investigation of the basic salts of mercury, the result of which has been to show that, of the salts mentioned in text-books, quite a number are incorrectly stated to be chemical compounds or chemical individuals (p. 92). The investigation, which was carried out essentially in the manner described above, included the salts mentioned in the following table; and of the basic salts said to be derived from them, only those mentioned really exist. In the following table, the numbers in the second column give the minimum values of the concentration of the acid, expressed in equivalent normality, necessary for the existence of the {301} corresponding salts in contact with solution at the temperature given in the third column:-- ------------------------------------------------------------- Salt. | Normality of | Temperature. | acid. | ------------------------------------------------------------- HgCrO_{4} | 1.41 | 50° 3HgO.CrO_{3} | 2.6 � 10^{-4} | 50° | | Hg(NO_{3})_{2}.H_{2}O | 18.72 | 25° 3HgO.N_{2}O_{5} | 0.159 | 25° | | HgSO_{4} | 6.87 | 25° 3HgO.SO_{3} | 1.3 � 10^{-3} | 25° | | HgF_{2} | 1.14 | 25° | | HgNO_{3}.H_{2}O | 2.95 | 25° 5Hg_{2}O.3N_{2}O_{5}.2H_{2}O | ca. 0.293 | 25° 2Hg_{2}O.N_{2}O_{5}(?) | 0.110 | 25° 3Hg_{2}O.N_{2}O_{5}.2H_{2}O(?) | 1.7 � 10^{-3} | 25° | | Hg_{2}SO_{4} | 4.2 � 10^{-3} | 25° 2Hg_{2}O.SO_{3}.H_{2}O | 5.6 � 10^{-4} | 25° ------------------------------------------------------------- Mercuric fluoride does not form any basic salt. Since two succeeding members of a series can coexist only in contact with a solution of definite concentration, we can prepare acid solutions of definite concentration by bringing an excess of two such salts in contact with water. Indirect Determination of the Composition of the Solid Phase.--It has already been shown (p. 228) how the composition of the solid phase in a system of two components can be determined without analysis, and we shall now describe how this can be done in a system of three components.[376] We shall assume that we are dealing with the aqueous solution of two salts which can give rise to a double salt, in which case we can represent the solubility relations in a system of rectangular co-ordinates. In this case we should obtain, as before (Fig. 120), the isotherm _adcb_, if we express the {302} composition of the solution in gram-molecules of A or of B to 100 gram-molecules of water. [Illustration: FIG. 120.] Let us suppose, now, that the double salt is in equilibrium with the solution at a definite temperature, and that the composition of the solution is represented by the point e. The greater part of the solution is now separated from the solid phase, and the latter, _together with the adhering mother liquor_, is analyzed. The composition (expressed, as before, in gram-molecules of A and B to 100 gram molecules of water) will be represented by a point (_e.g._ _f_) on the line _e_S, where S represents the composition of the double salt. That this is so will be evident when one considers that the composition of the whole mass must lie between the composition of the solution and that of the double salt, no matter what the relative amounts of the solid phase and the mother liquor. If, in a similar manner, we analyze a solution of a different composition in equilibrium with the same double salt (not necessarily at the same temperature as before), and also the mixture of solid phase and solution, we shall obtain two other points, as, for example, _g_ and _h_, and the line joining these must likewise pass through S. The method of finding the {303} composition of an unknown double salt consists, therefore, in finding, in the manner just described, the position of two lines such as _ef_ and _gh_. The point of intersection of these lines then gives the composition of the double salt. If the double salt is anhydrous, the point S lies at infinity, and the lines _ef_ and _gh_ are parallel to each other. The same result is arrived at by means of the triangular method of representation.[377] If we start with the three components in known amounts, and represent the initial composition of the whole by a point in the triangle, and then ascertain the final composition of the solution in equilibrium with the solid phase at a definite temperature, the line joining the points representing the initial and end concentration passes through the point representing the composition of the solid phase. If two determinations are made with solutions having different initial and final concentrations in equilibrium with the same solid phase, then the point of intersection of the two lines so obtained gives the composition of the solid phase. * * * * * {304} CHAPTER XVII ABSENCE OF A LIQUID PHASE In the preceding chapters dealing with equilibria in three-component systems, our attention was directed only to those cases in which liquid solutions formed one or more phases. Mention must, however, be made of certain systems which contain no liquid phase, and in which only solids and gases are in equilibrium. Since, in all cases, there can be but one gas phase, four solid phases will be necessary in order to form an invariant system. When only three solid phases are present, the system is univariant; and when only two solid phases coexist with gas, it is bivariant. If, however, we make the restriction that the gas pressure is constant, we diminish the variability by one. On account of their great industrial importance, we shall describe briefly some of the systems belonging to this class. Iron, Carbon Monoxide, Carbon Dioxide.--Some of the most important systems of three components in which equilibrium exists between solid and gas phases are those formed by the three components--iron, carbon monoxide, and carbon dioxide--and they are of importance especially for the study of the processes occurring in the blast furnace. If carbon monoxide is passed over reduced iron powder at a temperature of about 600°, the iron is oxidized and the carbon monoxide reduced with separation of carbon in accordance with the equation Fe + CO = FeO + C This reaction is succeeded by the two reactions FeO + CO = Fe + CO_{2} CO_{2} + C = 2CO {305} [Illustration: FIG. 121.] The former of these reactions is not complete, but leads to a definite equilibrium. The result of the different reactions is therefore an equilibrium between the three solid phases, carbon, iron, and ferrous oxide, and the gas phase consisting of carbon monoxide and dioxide. We have here four phases; and if the total pressure is maintained constant, equilibrium can occur only at a definite temperature. Since, under certain conditions, we can also have the reaction Fe_{3}O_{4} + CO = 3FeO + CO_{2} {306} a second series of equilibria can be obtained of a character similar to the former. These various equilibria have been investigated by Baur and Glaessner,[378] and the following is a short account of the results of their work. Mixtures of the solid phases in equilibrium with carbon monoxide and dioxide were heated in a porcelain tube at a definite temperature until equilibrium was produced, and the gas was then pumped off and analyzed. The results which were obtained are given in the following tables, and represented graphically in Fig. 121. SOLID PHASES: Fe_{3}O_{4}; FeO. ----------------------------------------------------------------- | | Duration of | | Percentage of No. | Tube filled | the experiment | Temperature. | | with | in hours. | | CO_{2} | CO ----------------------------------------------------------------- 1 | CO | 14 | 600° | 59.3 | 40.7 2 | CO | 15 | 590° | 54.7 | 45.3 3 | CO_{2} | 16 | 590° | 64.6 | 35.4 4 | CO | 24 | 590° | 58.4 | 41.6 5 | CO | 22 | 730° | 67.7 | 32.3 6 | CO_{2} | 22 | 730° | 86.1 | 31.9 7 | CO | 22 | 750° | 68.4 | 31.6 8 | CO_{2} | 22 | 610° | 64.9 | 35.1 9 | CO | 23 | 420° | 56.0 | 44.0 10 | CO | 47 | 350° | 65.6 | 34.4 11 | CO_{2} | 46 | 350° | 72.8 | 27.2 12 | CO | 53 | 350° | 64.0 | 36.0 13 | CO | 18 | 570° | 53.4 | 46.6 14 | CO | 19 | 680° | 60.5 | 39.5 15 | CO_{2} | 24 | 540° | 55.5 | 44.5 16 | CO | 21 | 630° | 57.5 | 42.5 17 | CO_{2} | 17 | 690° | 65.5 | 34.5 18 | CO_{2} | 17 | 670° | 67.0 | 33.0 19 | CO_{2} | 24 | 410° | 58.5 | 41.5 20 | CO | 24 | 490° | 51.7 | 48.8 21 | CO_{2} | 23 | 590° | 54.4 | 45.6 22 | CO_{2} | 4 | 950° | 77.0 | 23.0 23 | CO_{2} | 15 | 850° | 73.4 | 26.6 24 | CO | 8 | 800° | 71.2 | 28.8 25 | CO_{2} | 24 | 540° | 56.7 | 43.3 ----------------------------------------------------------------- {307} SOLID PHASES: FeO; Fe. ------+-------------+-------------+--------------+--------------- | | Duration of | | Percentage of No. | Tube filled | experiment | Temperature. | | with | in hours. | | CO_{2} | CO ------+-------------+-------------+--------------+--------+------ I. | CO | 15 | 800° | 35.2 | 64.8 II. | CO | 18 | 530° | 29.1 | 70.9 III. | CO | 13 | 880° | 30.2 | 69.6 IV. | CO_{2} | 24 | 870° | 32.3 | 67.7 V. | CO | 18 | 760° | 36.9 | 63.1 VI. | CO_{2} | 16 | 820° | 34.7 | 65.3 VII. | CO_{2} | 18 | 730° | 41.1 | 58.9 VIII. | CO | 18 | 630° | 34.9 | 65.1 IX. | CO_{2} | 17 | 630° | 61.6 | 58.4 X. | CO | 18 | 540° | 25.0 | 75.0 XI. | CO_{2} | 25 | 540° | 36.5 | 63.5 ------+-------------+-------------+--------------+--------+------ As is evident from the above tables and from the curves in Fig. 121, the curve of equilibrium in the case of the reaction Fe_{3}O_{4} + CO = 3FeO + CO_{2} exhibits a maximum for the ratio CO : CO_{2}, at 490°, while, for the reaction FeO + CO = Fe + CO_{2} this ratio has a minimum value at 680°. From these curves can be derived the conditions under which the different solid phases can exist in contact with gas. Thus, for example, at a temperature of 690°, FeO and Fe_{3}O_{4} can coexist with a mixture of 65.5 per cent. of CO_{2} and 34.5 per cent. of CO. If the partial pressure of CO_{2} is increased, there occurs the reaction 3FeO + CO_{2} = Fe_{3}O_{4} + CO and if carbon dioxide is added in sufficient amount, the ferrous oxide finally disappears completely. If, on the other hand, the partial pressure of CO is increased, there occurs the reaction Fe_{3}O_{4} + CO = 3FeO + CO_{2} and all the ferric oxide can be made to disappear. We see, therefore, that Fe_{3}O_{4} can only exist at temperatures and in {308} contact with mixtures of carbon monoxide and dioxide, represented by the area which lies below the under curve in Fig. 121. Similarly, the region of existence of FeO is that represented by the area between the two curves; while metallic iron can exist under the conditions of temperature and composition of gas phase represented by the area above the upper curve in Fig. 121. If, therefore, ferric oxide or metallic iron is heated for a sufficiently long time at temperatures above 700° (to the right of the dotted line; _vide infra_), complete transformation to ferrous oxide finally occurs. In another series of equilibria which can be obtained, carbon is one of the solid phases. In Fig. 121 the equilibria between carbon, carbon monoxide, and carbon dioxide under pressures of one and of a quarter atmosphere, are represented by dotted lines.[379] If we consider only the dotted line on the right, representing the equilibria under atmospheric pressure, we see that the points in which the dotted line cuts the other two curves must represent systems in which carbon monoxide and carbon dioxide are in equilibrium with FeO + Fe_{3}O_{4} + C, on the one hand, and with Fe + FeO + C on the other. These systems can only exist at one definite temperature, if we make the restriction that the pressure is maintained constant (atmospheric pressure). Starting, therefore, with the equilibrium FeO + Fe_{3}O_{4} + CO + CO_{2} at a temperature of about 670°, and then add carbon to the system, the reaction C + CO_{2} = 2CO will occur, because the concentration of CO_{2} is greater than what corresponds with the system FeO + Fe_{3}O_{4} + C in equilibrium with carbon monoxide and dioxide. In consequence of this reaction, the equilibrium between FeO + Fe_{3}O_{4} and the gas phase is disturbed, and the change in the composition of the gas phase is opposed by the reaction Fe_{3}O_{4} + CO = 3FeO + CO_{2}, which continues until either all the carbon {309} or all the ferric oxide is used up. If the ferric oxide first disappears, the equilibrium corresponds with a point on the dotted line in the middle area of Fig. 121, which represents equilibria between FeO + C as solid phases, and a mixture of carbon monoxide and dioxide as gas phase. If the temperature is higher than 685°, at which temperature the curve for C--CO--CO_{2} cuts that for Fe--FeO--CO--CO_{2}; then, when all the ferric oxide has disappeared, the concentration of CO_{2} is still too great for the coexistence of FeO and C. Consequently, there occurs the reaction C + CO_{2} = 2CO, and the composition of the gas phase alters until a point on the upper curve is reached. A further increase in the concentration of CO is opposed by the reaction FeO + CO = Fe + CO_{2}, and the pressure remains constant until all the ferrous oxide is reduced and only iron and carbon remain in equilibrium with gas. If the quantities of the substances have been rightly chosen, we ultimately reach a point on the dotted curve in the upper part of Fig. 121. Fig. 121 shows us, also, what are the conditions under which the reduction of ferric to ferrous oxide by carbon can occur. Let us suppose, for example, that we start with a mixture of carbon monoxide and dioxide at about 600° (the lowest point on the dotted line), and maintain the total pressure constant and equal to one atmosphere. If the temperature is increased, the concentration of the carbon dioxide will diminish, owing to the reaction C + CO_{2} = 2CO, but the ferric oxide will undergo no change until the temperature reaches 647°, the point of intersection of the dotted curve with the curve for FeO and Fe_{3}O_{4}. At this point further increase in the concentration of carbon monoxide is opposed by the reduction of ferric oxide in accordance with the equation Fe_{3}O_{4} + CO = 3FeO + CO_{2}. The pressure, therefore, remains constant until all the ferric oxide has disappeared. If the temperature is still further raised, we again obtain a univariant system, FeO + C, in equilibrium with gas (univariant because the total pressure is constant); and if the temperature is raised the composition of the gas must undergo change. This is effected by the reaction C + CO_{2} = 2CO. When the {310} temperature rises to 685°, at which the dotted curve cuts the curve for Fe--FeO, further change is prevented by the reaction FeO + CO = Fe + CO_{2}. When all the ferrous oxide is used up, we obtain the system Fe + C in equilibrium with gas. If the temperature is now raised, the composition of the gas undergoes change, as shown by the dotted line. The two temperatures, 647° and 685°, give, evidently, the limits within which ferric or ferrous oxide can be reduced directly by carbon. It is further evident that at any temperature to the right of the dotted line, carbon is unstable in presence of iron or its oxides; while at temperatures lower than those represented by the dotted line, it is stable. In the blast furnace, therefore, separation of carbon can occur only at lower temperatures, and the carbon must disappear on raising the temperature. Finally, it may be remarked that the equilibrium curves show that ferrous oxide is most easily reduced at 680°, since the concentration of the carbon monoxide required at this temperature is a minimum. On the other hand, ferric oxide is reduced with greatest difficulty at 490°, since at this temperature the requisite concentration of carbon monoxide is a maximum. Other equilibria between solid and gas phases are: Equilibrium between iron, ferric oxide, water vapour, and hydrogen,[380] and the equilibria between carbon, carbon monoxide, carbon dioxide, water vapour, and hydrogen,[381] which is of importance for the manufacture of water gas. * * * * * {311} CHAPTER XVIII SYSTEMS OF FOUR COMPONENTS In the systems which have so far been studied, we have met with cases where two or three components could enter into combination; but in no case did we find double decomposition occurring. The reason of this is that in the systems previously studied, in which double decomposition might have been possible, namely in those systems in which two salts acted as components, the restriction was imposed that either the basic or the acid constituent of these salts must be the same; a restriction imposed, indeed, for the very purpose of excluding double decomposition. Now, however, we shall allow this restriction to fall, thereby extending the range of study. Hitherto, in connection with four-component systems, the attention has been directed solely to the study of aqueous solutions of salts, and more especially of the salts which occur in sea-water, _i.e._ chiefly, the sulphates and chlorides of magnesium, potassium, and sodium. The importance of these investigations will be recognized when one recollects that by the evaporation of sea-water there have been formed the enormous salt-beds at Stassfurt, which constitute at present the chief source of the sulphates and chlorides of magnesium and potassium. The investigations, therefore, are not only of great geological interest as tending to elucidate the conditions under which these salt-beds have been formed, but are of no less importance for the industrial working of the deposits. It is, however, not the intention to enter here into any detailed description of the different systems which have so far been studied, and of the sometimes very complex relationships {312} met with, but merely to refer briefly to some points of more general import in connection with these systems.[382] Reciprocal Salt-Pairs. Choice of Components.--When two salts undergo double decomposition, the interaction can be expressed by an equation such as NH_{4}Cl + NaNO_{3} = NaCl + NH_{4}NO_{3} Since one pair of salts--NaCl + NH_{4}NO_{3}--is formed from the other pair--NH_{4}Cl + NaNO_{3}--by double decomposition, the two pairs of salts are known as _reciprocal salt-pairs_.[383] It is with systems in which the component salts form reciprocal salt-pairs that we have to deal here. It must be noted, however, that the four salts formed by two reciprocal salt-pairs do not constitute a system of four, but only of _three_ components. This will be understood if it is recalled that only so many constituents are taken as components as are necessary to _express_ the composition of all the phases present (p. 12). It will be seen, now, that the composition of each of the four salts which can be present together can be expressed in terms of three of them. Thus, for example, in the case of NH_{4}Cl, NaNO_{3}, NH_{4}NO_{3}, NaCl, we can express the composition of NH_{4}Cl by NH_{4}NO_{3} + NaCl - NaNO_{3}; or of NaNO_{3} by NH_{4}NO_{3} + NaCl - NH_{4}Cl. In all these cases it will be seen that negative quantities of one of the components must be employed; but that we have seen to be quite permissible (p. 12). The number of components is, therefore, three; but any three of the four salts can be chosen. Since, then, two reciprocal salt-pairs constitute only three {313} components or independently variable constituents, another component is necessary in order to obtain a four-component system. As such, we shall choose water. Transition Point.--In the case of the formation of double salts from two single salts, we saw that there was a point--the _quintuple point_--at which five phases could coexist. This point we also saw to be a transition point, on one side of which the double salt, on the other side the two single salts in contact with solution, were found to be the stable system. A similar behaviour is found in the case of reciprocal salt-pairs. The four-component system, two reciprocal salt-pairs and water, can give rise to an invariant system in which the six phases, four salts, solution, vapour, can coexist; the temperature at which this is possible constitutes a _sextuple point_. Now, this sextuple point is also a transition point, on the one side of which the one salt-pair, on the other side the reciprocal salt-pair, is stable in contact with solution. The sextuple point is the point of intersection of the curves of six univariant systems, viz. four solubility curves with three solid phases each, a vapour-pressure curve for the system: two reciprocal salt-pairs--vapour; and a transition curve for the condensed system: two reciprocal salt-pairs--solution. If we omit the vapour phase and work under atmospheric pressure (in open vessels), we find that the transition point is the point of intersection of four solubility curves. Just as in the case of three-component systems we saw that the presence of one of the single salts along with the double salt was necessary in order to give a univariant system, so in the four-component systems the presence of a third salt is necessary as solid phase along with one of the salt-pairs. In the case of the reciprocal salt-pairs mentioned above, the transition point would be the point of intersection of the solubility curves of the systems with the following groups of salts as solid phases: Below the transition point: NH_{4}Cl + NaNO_{3} + NaCl; NH_{4}Cl + NaNO_{3} + NH_{4}NO_{3}; above the transition point: NaCl + NH_{4}NO_{3} + NaNO_{3}; NaCl + NH_{4}NO_{3} + NH_{4}Cl. From this we see that the two salts NH_{4}Cl and NaNO_{3} would be able to exist together with solution below the transition point, but not above it. This transition point has not been determined. {314} Formation of Double Salts.--In all cases of four-component systems so far studied, the transition points have not been points at which one salt-pair passed into its reciprocal, but at which a double salt was formed. Thus, at 4.4° Glauber's salt and potassium chloride form glaserite and sodium chloride, according to the equation 2Na_{2}SO_{4},10H_{2}O + 3KCl = K_{3}Na(SO_{4})_{2} + 3NaCl + 20H_{2}O Above the transition point, therefore, there would be K_{3}Na(SO_{4})_{2}, NaCl and KCl; and it may be considered that at a higher temperature the double salt would interact with the potassium chloride according to the equation K_{3}Na(SO_{4})_{2} + KCl = 2K_{2}SO_{4} + NaCl thus giving the reciprocal of the original salt-pair. This point has, however, not been experimentally realized.[384] Transition Interval.--A double salt, we learned (p. 277), when brought in contact with water at the transition point undergoes partial decomposition with separation of one of the constituent salts; and only after a certain range of temperature (transition interval) has been passed, can a pure saturated solution be obtained. A similar behaviour is also found in the case of reciprocal salt-pairs. If one of the salt-pairs is brought in contact with water at the transition point, interaction will occur and one of the salts of the reciprocal salt-pair will be deposited; and this will be the case throughout a certain range of temperature, after which it will be possible to prepare a solution saturated only for the one salt-pair. In the case of ammonium chloride and sodium nitrate the lower limit of the transition interval is 5.5°, so that above this temperature and up to that of the transition point (unknown), ammonium chloride and sodium nitrate in contact with water would give rise to a third salt by double decomposition, in this case to sodium chloride.[385] {315} Graphic Representation.--For the graphic representation of systems of four components, four axes may be chosen intersecting at a point like the edges of a regular octahedron (Fig. 122).[386] Along these different axes the equivalent molecular amounts of the different salts are measured. [Illustration: FIG. 122.] [Illustration: FIG. 123.] To represent a given system consisting of _x_B, _y_C, and _z_D in a given amount of water (where B, C, and D represent equivalent molecular amounts of the salts), measure off on OB and OC lengths equal to _x_ and _y_ respectively. The point of intersection _a_ (Fig. 122) represents a solution containing _x_B and _y_C (_ab_ = _x_; _ac_ = _y_). From _a_ a line _a_P is drawn parallel to OD and equal to _z_. P then represents the solution of the above composition. It is usual, however, not to employ the three-dimensional figure, but its horizontal and vertical projections. Fig. 122, if projected on the base of the octahedron, would yield a diagram such as is shown in Fig. 123. The projection of the edges of the octahedron form two axes at right angles and give rise to four quadrants similar to those employed for the representation of ternary solutions (p. 273). Here, the point _a_ represents a ternary solution saturated with respect to B and C; and _a_P, quaternary solutions in equilibrium with the same two salts as solid phases. Such a diagram represents the conditions of equilibrium only for one definite temperature, and corresponds, therefore, to the isothermal diagrams for ternary systems (p. 273). In such a diagram, since the temperature and {316} pressure are constant (vessels open to the air), a surface will represent a solution in equilibrium with only one solid phase; a line, a solution with two solid phases, and a point, one in equilibrium with three solid phases. [Illustration: FIG. 124.] Example.--As an example of the complete isothermal diagram, there may be given one representing the equilibria in the system composed of water and the reciprocal salt-pair sodium sulphate--potassium chloride for the temperature 0° (Fig. 124).[387] The amounts of the different salts are measured along the four axes, and the composition of the solution is {317} expressed in equivalent gram-molecules per 1000 gram-molecules of water.[388] The outline of this figure represents four ternary solutions in which the component salts have a common acid or basic constituent; viz. sodium chloride--sodium sulphate, sodium sulphate--potassium sulphate, potassium sulphate--potassium chloride, potassium chloride--sodium chloride. These four sets of curves are therefore similar to those discussed in the previous chapter. In the case of sodium and potassium sulphate, a double salt, _glaserite_ [K_{3}Na(SO_{4})_{2}] is formed. Whether glaserite is really a definite compound or not is still a matter of doubt, since isomorphic mixtures of Na_{2}SO_{4} and K_{2}SO_{4} have been obtained. According to van't Hoff and Barscholl,[389] glaserite is an isomorphous mixture; but Gossner[390] considers it to be a definite compound having the formula K_{3}Na(SO_{4})_{2}. Points VIII. and IX. represent solutions saturated with respect to glaserite and sodium sulphate, and glaserite and potassium sulphate respectively. The lines which pass inwards from these boundary curves represent solutions containing three salts, but in contact with only two solid phases; and the points where three lines meet, or where three fields meet, represent solutions in equilibrium with three solid phases; with the phases, namely, belonging to the three concurrent fields. If it is desired to represent a solution containing the salts say in the proportions, 51Na_{2}Cl_{2}, 9.5K_{2}Cl_{2}, 3.5K_{2}SO_{4}, the difficulty is met with that two of the salts, sodium chloride and potassium sulphate, lie on opposite axes. To overcome this difficulty the difference 51 - 3.5 = 47.5 is taken and measured off along the sodium chloride axis; and the solution is therefore represented by the point 47.5Na_{2}Cl_{2}, 9.5K_{2}Cl_{2}. In order, therefore, to find the amount of potassium sulphate present {318} from such a diagram, it is necessary to know the total number of salt molecules in the solution. When this is known, it is only necessary to subtract from it the sum of the molecules of sodium and potassium chloride, and the result is equal to twice the number of potassium sulphate molecules. Thus, in the above example, the total number of salt molecules is 64. The number of molecules of sodium and potassium chloride is 57; 64 - 57 = 7, and therefore the number of potassium sulphate molecules is 3.5. Another method of representation employed is to indicate the amounts of only two of the salts in a plane diagram, and to measure off the total number of molecules along a vertical axis. In this way a solid model is obtained. The numerical data from which Fig. 124 was constructed are contained in the following table, which gives the composition of the different solutions at 0°:--[391] ---------------------------------------- | | | | Point. | Solid phases. | | | ---------------------------------------- I. | NaCl | | | II. | KCl | | | III. | Na_{2}SO_{4},10H_{2}O | | | IV. | K_{2}SO_{4} | | | V. | NaCl; KCl | | | VI. | NaCl; Na_{2}SO_{4},10H_{2}O | | | VII. | KCl; K_{2}SO_{4} | | | VIII. |{ Glaserite; }| |{ Na_{2}SO_{4},10H_{2}O }| | | IX. | Glaserite; K_{2}SO_{4} | | | X. |{ Na_{2}SO_{4},10H_{2}O; KCl; }| |{ NaCl }| | | XI. |{ Na_{2}SO_{4},10H_{2}O; KCl; }| |{ glaserite }| | | XII. | K_{2}SO_{4}; KCl; glaserite | ---------------------------------------- [Transcriber's note: table continued below...] ------------------------------------------------------------------------- Composition of solution in gram-mols. | Total per 1000 gram-mols. water. | number -------------------------------------------------------------| of salt Na_{2}Cl_{2}. | K_{2}Cl_{2}. | Na_{2}SO_{4}. | K_{2}SO_{4}. | molecules. ------------------------------------------------------------------------- 55 | -- | -- | -- | 55 | | | | -- | 34.5 | -- | -- | 34.5 | | | | -- | -- | 6 | -- | 6 | | | | -- | -- | -- | 9 | 9 | | | | 46.5 | 12.5 | -- | -- | 59 | | | | 47.5 | -- | 8 | -- | 55.5 | | | | -- | 34.5 | -- | 1 | 35.5 | | | | -- | -- | 10 | 10 | 20 | | | | | | | | -- | -- | 7.5 | 10 | 17.5 | | | | 51 | 9.5 | -- | 3.5 | 64 | | | | | | | | 40.5 | 13 | -- | 3.5 | 57 | | | | | | | | 18 | 23 | -- | 3 | 44 ------------------------------------------------------------------------- From the aspect of these diagrams the conditions under which the salts can coexist can be read at a glance. Thus, {319} for example, Fig. 124 shows that at 0° Glauber's salt and potassium chloride can exist together with solution; namely, in contact with solutions having the composition X--XI. This temperature must therefore be below the transition point of this salt-pair (p. 314). On raising the temperature to 4.4°, it is found that the curve VIII.--XI. moves so that the point XI. coincides with point X. At this point, therefore, there will be _four_ concurrent fields, viz. Glauber's salt, potassium chloride, glaserite, and sodium chloride. But these four salts can coexist with solution only at the transition point; so that 4.4° is the transition temperature of the salt-pair: Glauber's salt--potassium chloride. At higher temperatures the line VIII.--XI. moves still further to the left, so that the field for Glauber's salt becomes entirely separated from the field for potassium chloride. This shows that at temperatures above the transition point the salt-pair Glauber's salt--potassium chloride cannot coexist in presence of solution. [Illustration: FIG. 125.] If it is only desired to indicate the mutual relationships of the different components and the conditions for their coexistence (_paragenesis_), a simpler diagram than Fig. 124 can be employed. Thus if the boundary curves of Fig. 124 are so drawn that they cut one another at right angles, a figure such as Fig. 125 is obtained, the Roman numerals here corresponding with those in Fig. 124. Ammonia-Soda Process.--One of the most important applications of the Phase Rule to systems of four components with reciprocal salt-pairs has recently been made by Fedotieff[392] in his investigations of the conditions for the formation of sodium carbonate by the so-called ammonia-soda (Solvay) {320} process.[393] This process consists, as is well known, in passing carbon dioxide through a solution of common salt saturated with ammonia. Whatever differences of detail there may be in the process as carried out in different manufactories, the reaction which forms the basis of the process is that represented by the equation NaCl + NH_{4}HCO_{3} = NaHCO_{3} + NH_{4}Cl We are dealing here, therefore, with reciprocal salt-pairs, the behaviour of which has just been discussed in the preceding pages. The present case is, however, simpler than that of the salt-pair Na_{2}SO_{4}.10H_{2}O + KCl, inasmuch as under the conditions of experiment neither hydrates nor double salts are formed. Since the study of the reaction is rendered more difficult on account of the fact that ammonium bicarbonate in solution, when under atmospheric pressure, undergoes decomposition at temperatures above 15°, this temperature was the one chosen for the detailed investigation of the conditions of equilibrium. Since, further, it has been shown by Bodländer[394] that the bicarbonates possess a definite solubility only when the pressure of carbon dioxide in the solution has a definite value, the measurements were carried out in solutions saturated with this gas. This, however, does not constitute another component, because we have made the restriction that the sum of the partial pressures of carbon dioxide and water vapour is equal to 1 atmosphere. The concentration of the carbon dioxide is, therefore, not independently variable (p. 10). [Illustration: FIG. 126.] In order to obtain the data necessary for a discussion of the conditions of soda formation by the ammonia-soda process, solubility determinations with the four salts, NaCl, NH_{4}Cl, NH_{4}HCO_{3}, and NaHCO_{3} were made, first with the single salts and then {321} with the salts in pairs. The results obtained are represented graphically in Fig. 126, which is an isothermal diagram similar to that given by Fig. 124. The points I., II., III., IV., represent the composition of solutions in equilibrium with two solid salts. We have, however, seen (p. 314) that the transition point, when the experiment is carried out under constant pressure (atmospheric pressure), is the point of intersection of four solubility curves, each of which represents the composition of solutions in equilibrium with three salts, viz. one of the reciprocal salt-pairs along with a third salt. Since, now, it was found that the stable salt-pair at temperatures between 0° and 30° is sodium bicarbonate and ammonium chloride, determinations were made of the composition of solutions in equilibrium with NaHCO_{3} + NH_{4}Cl + NH_{4}HCO_{3} and with NaHCO_{3} + NH_{4}Cl + NaCl as solid phases. Under the {322} conditions of experiment (temperature = 15°) sodium chloride and ammonium bicarbonate cannot coexist in contact with solution. These determinations gave the data necessary for the construction of the complete isothermal diagram (Fig. 127). The most important of these data are given in the following table (temperature, 15°):-- ------------------------------------------------------------------------- | | Composition of the solution in gram-molecules | | to 1000 gram-molecules Point. | Solid phases. | of water. | |---------------------------------------------- | | NaHCO_{3} | NaCl | NH_{4}HCO_{3} | NH_{4}Cl ------------------------------------------------------------------------- -- | NaHCO_{3} | 1.08 | -- | -- | -- -- | NaCl | -- | 6.12 | -- | -- -- | NH_{4}HCO_{3} | -- | -- | 2.36 | -- -- | NH_{4}Cl | -- | -- | -- | 6.64 I. | NaHCO_{3}; NaCl | 0.12 | 6.06 | -- | -- II. | NaCl; NH_{4}Cl | -- | 4.55 | -- | 3.72 III. | NH_{4}Cl; | -- | -- | 0.81 | 6.40 | NH_{4}HCO_{3} | | | | IV. | NaHCO_{3}; | 0.71 | -- | 2.16 | -- | NH_{4}HCO_{3} | | | | P_{1} | NaHCO_{3}; | 0.93 | 0.51 | -- | 6.28 | NH_{4}HCO_{3}; | | | | | NH_{4}Cl | | | | P_{2} | NaHCO_{3}; | 0.18 | 4.44 | -- | 3.73 | NaCl; NH_{4}Cl | | | | ------------------------------------------------------------------------- With reference to the solution represented by the point P_{1}, it may be remarked that it is an incongruently saturated solution (p. 279). If sodium chloride is added to this solution, the composition of the latter undergoes change; and if a sufficient amount of the salt is added, the solution P_{2} is obtained. Turning now to the practical application of the data so obtained, consider first what is the influence of concentration on the yield of soda. Since the reaction consists essentially in a double decomposition between sodium chloride and ammonium bicarbonate, then, after the deposition of the sodium bicarbonate, we obtain a solution containing sodium chloride, ammonium chloride, and sodium bicarbonate. In order to ascertain to what extent the sodium chloride has been converted into solid sodium bicarbonate, it is necessary to examine the composition of the solution which is obtained {323} with definite amounts of sodium chloride and ammonium bicarbonate. [Illustration: FIG. 127.] Consider, in the first place, the solutions represented by the curve P_{2}P_{1}. With the help of this curve we can state the conditions under which a solution, saturated for ammonium chloride, is obtained, after deposition of sodium bicarbonate. In the following table the composition of the solutions is given which are obtained with different initial amounts of sodium chloride and ammonium bicarbonate. The last two columns give the percentage amount of the sodium used, which is deposited as solid sodium bicarbonate (U_{Na}); and likewise the percentage amount of ammonium bicarbonate which is usefully converted into sodium bicarbonate, that is to say, the amount of the radical HCO_{3} deposited (U_{NH_{4}}):-- {324} ------+---------------------+ |Initial composition | |of the solutions: | |grams of salt to 1000| Point.|grams of water. | +------+--------------+ | NaCl | NH_{4}HCO_{3}| ------+------+--------------+ P_{2} | 479 | 295 | -- | 448 | 360 | -- | 417 | 431 | P_{1} | 397 | 496 | ------+------+--------------+ [Transcriber's note: table continued below...] +----------------------------------+---------+---------- | | | |Composition of solutions obtained:| | |gram-equivalents per 1000 grams |U_{Na} |U_{NH_{4}} |of water. |per cent.|per cent. +----------+------+------+---------+ | | HCO_{3} | Cl | Na | NH_{4} | | +----------+------+------+---------+---------+---------- | 0.18 | 8.17 | 4.62 | 3.73 | 43.4 | 95.1 | 0.31 | 7.65 | 3.39 | 4.56 | 55.7 | 93.4 | 0.51 | 7.13 | 2.19 | 5.45 | 69.2 | 90.5 | 0.92 | 6.79 | 1.44 | 6.28 | 78.8 | 85.1 +----------+------+------+---------+---------+---------- This table shows that the greater the excess of sodium chloride, the greater is the percentage utilization of ammonia (Point P_{2}); and the more the amount of sodium chloride decreases, the greater is the percentage amount of sodium chloride converted into bicarbonate. In the latter case, however, the percentage utilization of the ammonium bicarbonate decreases; that is to say, less sodium bicarbonate is deposited, or more of it remains in solution. Consider, in the same manner, the relations for solutions represented by the curve P_{2}IV, which gives the composition of solutions saturated with respect to sodium bicarbonate and ammonium bicarbonate. In this case we obtain the following results:-- ------+---------------------+ |Initial composition | |of the solutions: | |grams of salt to 1000| Point.|grams of water. | +------+--------------+ | NaCl | NH_{4}HCO_{3}| ------+------+--------------+ P_{1} | 397 | 496 | -- | 351 | 446 | -- | 316 | 412 | -- | 294 | 389 | -- | 234 | 327 | ------+------+--------------+ [Transcriber's note: table continued below...] +----------------------------------+------+---------- | | | |Composition of solutions obtained:| | |in gram-equivalents per 1000 grams|U_{Na}|U_{NH_{4}} |of water. | | +----------+------+------+---------+ | | HCO_{3} | Cl | Na | NH_{4} | | +----------+------+------+---------+------+---------- | 0.92 | 6.79 | 1.44 | 6.28 | 78.8 | 85.1 | 0.99 | 6.00 | 1.34 | 5.65 | 77.7 | 82.5 | 1.07 | 5.41 | 1.27 | 5.21 | 76.4 | 79.5 | 1.12 | 5.03 | 1.23 | 4.92 | 75.5 | 75.1 | 1.30 | 4.00 | 1.16 | 4.14 | 71.0 | 68.6 +----------+------+------+---------+------+---------- As is evident from this table, diminution in the relative amount of sodium chloride exercises only a slight influence {325} on the utilization of this salt, but is accompanied by a rapid diminution of the effective transformation of the ammonium bicarbonate. So far as the efficient conversion of the sodium is concerned, we see that it reaches its maximum at the point P_{1}, and that it decreases both with increase and with decrease of the relative amount of sodium chloride employed; and faster, indeed, in the former than in the latter case. On the other hand, the effective transformation of the ammonium bicarbonate reaches its maximum at the point P_{2}, and diminishes with increase in the relative amount of ammonium bicarbonate employed. Since sodium chloride is, in comparison with ammonia--even when this is regenerated--a cheap material, it is evidently more advantageous to work with solutions which are relatively rich in sodium chloride (solutions represented by the curve P_{1}P_{2}). This fact has also been established empirically. When, as is the case in industrial practice, we are dealing with solutions which are saturated not for two salts but only for sodium bicarbonate, it is evident that we have then to do with solutions the composition of which is represented by points in the area P_{1}P_{2}I,IV. Since in the commercial manufacture, the aim must be to obtain as complete a utilization of the materials as possible, the solutions employed industrially must lie in the neighbourhood of the curves P_{2}P_{1}IV, as is indicated by the shaded portion in Fig. 127. The best results, from the manufacturer's standpoint, will be obtained, as already stated, when the composition of the solutions approaches that given by a point on the curve P_{2}P_{1}. Considered from the chemical standpoint, the results of the experiments lead to the conclusion that the Solvay process, _i.e._ passage of carbon dioxide through a solution of sodium chloride saturated with ammonia, is not so good as the newer method of Schlösing, which consists in bringing together sodium chloride and ammonium bicarbonate with water.[395] {326} Preparation of Barium Nitrite.--Mention may also be made here of the preparation of barium nitrite by double decomposition of barium chloride and sodium nitrite.[396] The reaction with which we are dealing here is represented by the equation BaCl_{2} + 2NaNO_{2} = 2NaCl + Ba(NO_{2})_{2} It was found that at the ordinary temperature NaCl and Ba(NO_{2})_{2} form the stable salt-pair. If, therefore, barium chloride and sodium nitrite are brought together with an amount of water insufficient for complete solution, transformation to the stable salt-pair occurs, and sodium chloride and barium nitrite are deposited. When, however, a stable salt-pair is in its transition interval (p. 315), a third salt--in this case barium chloride--will be deposited, as we have already learned. On bringing barium chloride and sodium nitrite together with water, therefore, three solid phases are obtained, viz. BaCl_{2}, NaCl, Ba(NO_{2})_{2}. These three phases, together with solution and vapour, constitute a univariant system, so that at each temperature the composition of the solution must be constant. Witt and Ludwig found that the presence of solid barium chloride can be prevented by adding an excess of sodium nitrite, as can be readily foreseen from what has been said. Since the solution in presence of the three solid phases must have a definite composition at a definite temperature, the addition of sodium nitrite to the solution must have, as its consequence, the solution of an equivalent amount of barium chloride, and the deposition of an equivalent amount of sodium chloride and barium nitrite. By sufficient addition of sodium nitrite, the complete disappearance of the solid barium chloride can be effected, and there will remain only the stable salt-pair sodium chloride and barium nitrite. As was pointed out by Meyerhoffer, however, the disappearance of the barium chloride is effected, not by a change in the {327} composition of the solution, but by the necessity for the composition of the solution remaining constant. [Illustration: FIG. 128.] Barium Carbonate and Potassium Sulphate.--As has been found by Meyerhoffer,[397] these two salts form the stable pair, not only at the ordinary temperature, but also at the melting point. For the ordinary temperatures this was proved in the following manner: A solution with the solid phases K_{2}SO_{4} and K_{2}CO_{3}.2H_{2}O in excess can only coexist in contact either with BaCO_{3} or with BaSO_{4}, since, evidently, in one of the two groups the stable system must be present. Two solutions were prepared, each with excess of K_{2}SO_{4} + K_{2}CO_{3}.2H_{2}O, {328} and to one was added BaCO_{3} and to the other BaSO_{4}. After stirring for a few days, the barium sulphate was completely transformed to BaCO_{3}, whereas the barium carbonate remained unchanged. Consequently, BaCO_{3} + K_{2}SO_{4} + K_{2}CO_{3}.2H_{2}O is stable, and, therefore, so also is BaCO_{3} + K_{2}SO_{4}. That BaCO_{3} + K_{2}SO_{4} is the stable pair also at the melting point was proved by a special analytical method which allows of the detection of K_{2}CO_{3} in a mixture of the four solid salts. This analysis showed that a mixture of BaCO_{3} + K_{2}SO_{4}, after being fused and allowed to solidify, contains only small amounts of K_{2}CO_{3}; and this is due entirely to the fact that BaCO_{3} + K_{2}SO_{4} on fusion deposits a little BaSO_{4}, thereby giving rise at the same time to the separation of an equivalent amount of K_{2}CO_{3}. The different solubilities are shown in Fig. 128. In this diagram the solubility of the two barium salts has been neglected. A is the solubility of K_{2}CO_{3}.2H_{2}O; addition of BaCO_{3} does not alter this. B is the solubility of K_{2}CO_{3}.2H_{2}O + K_{2}SO_{4} + BaCO_{3}. A and B almost coincide, since the potassium sulphate is very slightly soluble in the concentrated solution of potassium carbonate. D gives the concentration of the solution in equilibrium with K_{2}SO_{4} + BaSO_{4}. The most interesting point is C. This solution is obtained by adding a small quantity of water to BaCO_{3} + K_{2}SO_{4}, whereupon, being in the transition interval, BaSO_{4} separates out and an equivalent amount of K_{2}CO_{3} goes into solution. C is the end point of the curve CO, which is called the Guldberg-Waage curve, because these investigators determined several points on it. In their experiments, Guldberg and Waage found the ratio K_{2}CO_{3} : K_{2}SO_{4} in solution to be constant and equal to 4. This result is, however, not exact, for the curve CO is not a straight line, as it should be if the above ratio were constant; but it is concave to the abscissa axis, and more so at lower than at higher temperatures. The following table refers to the temperature of 25°. The Roman numbers in the first column refer to the points in Fig. 128. The numbers in the column [Sigma]_k__{2} give the amount, {329} in gram-molecules, of K_{2}CO_{3} + K_{2}SO_{4} contained in 1000 gram-molecules of water:-- SOLUBILITY DETERMINATIONS AT 25°. -----+-------------------------------------+-----------------------+ | | 100 gms. of the | | | solution contain, | No. | Solid phases. | in grams, | | | | | | |K_{2}CO_{3}|K_{2}SO_{4}| -----+-------------------------------------+-----------+-----------+ I. | K_{2}CO_{3}.2H_{2}O + BaCO_{3} | 53.2 | -- | | | | | II. |{ K_{2}CO_{3}.2H_{2}O + K_{2}SO_{4} }| 53.0 | 0.023 | |{ + BaCO_{3} }| | | | | | | III.}| K_{2}SO_{4} + BaCO_{3} | { 28.5 | 0.886 | IV. }| | { 22.1 | 1.72 | | | | | V. | BaCO_{3} + K_{2}SO_{4} + BaSO_{4} | 17.81 | 2.485 | | | | | VI. }| K_{2}SO_{4} + BaSO_{4} | { 12.6 | 3.92 | VII.}| | { 5.85 | 6.76 | | | | | VIII.| K_{2}SO_{4} | -- | 10.76 | | | | | IX. }| BaCO_{3} + BaSO_{4} | { 7.35 | 0.602 | X. }| | { 2.85 | 0.173 | -----+-------------------------------------+-----------+-----------+ [Transcriber's note: table continued below...] -----+-----------------------+-----------------+----------- | 1000 moles | | | of water contain, | | K_{2}CO_{3} No. | in moles, |[Sigma]_k__{2} | ----------- | | | | K_{2}SO_{4} |K_{2}CO_{3}|K_{2}SO_{4}| | -----+-----------+-----------+-----------------+----------- I. | 147.9 | -- | -- | -- | | | | II. | 147.8 | 0.051 | -- | -- | | | | | | | | III.}| 52.58 | 1.296 | -- | -- IV. }| 37.79 | 2.333 | -- | -- | | | | V. | 29.11 | 3.220 | 32.32 | 9.03 | | | | VI. }| 19.66 | 4.853 | -- | -- VII.}| 8.724 | 7.995 | -- | -- | | | | VIII.| -- | 12.47 | -- | -- | | | | IX. }| 10.43 | 0.676 | 11.11 | 15.0 X. }| 3.828 | 0.184 | 4.0 | 21.0 -----+-----------+-----------+-----------------+----------- The Guldberg-Waage curve at 100° was also determined, and it was found that the ratio K_{2}CO_{3}: K_{2}SO_{4} is also not constant, although the variations are not so great as at 25°. GULDBERG-WAAGE CURVE AT 100°. ----------------------+-----------------------+-----------------+------- |100 moles of water | | K2CO3 Solid phases. |contain, in moles, | [Sigma]_k__{2} | ----- | | | | K2SO4 |K_{2}CO_{3}|K_{2}SO_{4}| | ----------------------+-----------+-----------+-----------------+------- BaCO_{3} + K_{2}SO_{4}| 23.9 | 12.65 | 35.65 | 1.82 + BaSO_{4} | | | | BaCO_{3} + BaSO_{4} | 6.28 | 2.02 | 8.3 | 3.1 " " | 3.17 | 0.851 | 4.025 | 3.7 ----------------------+-----------+-----------+-----------------+------- * * * * * {330} APPENDIX EXPERIMENTAL DETERMINATION OF THE TRANSITION POINT For the purpose of determining the transition temperature, a number of methods have been employed, and the most important of these will be briefly described here. In any given case it is sometimes possible to employ more than one method, but all are not equally suitable, and the values of the transition point obtained by the different methods are not always identical. Indeed, a difference of several degrees in the value found may quite well occur.[398] In each case, therefore, some care must be taken to select the method most suitable for the purpose. I. The Dilatometric Method.--Since, in the majority of cases, transformation at the transition point is accompanied by an appreciable change of volume, it is only necessary to ascertain the temperature at which this change of volume occurs, in order to determine the transition point. For this purpose the _dilatometer_ is employed, an apparatus which consists of a bulb with capillary tube attached, and which constitutes a sort of large thermometer (Fig. 129). Some of the substance to be examined is passed into the bulb A through the tube B, which is then sealed off. The rest of the bulb and a small portion of the capillary tube is then filled with some liquid, which, of course, must be without chemical action on the substance under investigation. A liquid, however, may be employed which dissolves the substance, for, as we have seen (p. 70), the transformation at the transition point is, as a rule, accelerated by the presence of a solvent. On the other hand, the liquid must not dissolve in the substance under examination, for the temperature of transformation would be thereby altered. {331} In using the dilatometer, two methods of procedure may be followed. According to the first method, the dilatometer containing the form stable at lower temperatures is placed in a thermostat, maintained at a constant temperature, until it has taken the temperature of the bath. The height of the meniscus is then read on a millimetre scale attached to the capillary. The temperature of the thermostat is then raised degree by degree, and the height of the meniscus at each point ascertained. If, now, no change takes place in the solid, the expansion will be practically uniform, or the rise in the level of the meniscus per degree of temperature will be practically the same at the different temperatures, as represented diagrammatically by the line AB in Fig. 130. On passing through the transition point, however, there will be a more or less sudden increase in the rise of the meniscus per degree (line BC) if the specific volume of the form stable at higher temperatures is greater than that of the original modification; thereafter, the expansion will again be uniform (line CD). Similarly, on cooling, contraction will at first be uniform and then at the transition point there will be a relatively large diminution of volume. [Illustration: FIG. 129.] [Illustration: FIG. 130.] If, now, transformation occurred immediately the transition point was reached, the sudden expansion and contraction would take place at the same temperature. It is, however, generally found that there is a lag, and that with rising temperature the relatively large expansion does not take place until a temperature somewhat higher than the transition point; and with falling temperature the contraction occurs at a temperature somewhat below the transition point. This is represented in Fig. 130 by the lines BC and EF. The amount of lag will vary from case to case, and will {332} also depend on the length of time during which the dilatometer is maintained at constant temperature. As an example, there may be given the results obtained in the determination of the transition point at which sodium sulphate and magnesium sulphate form astracanite (p. 268).[399] The dilatometer was charged with a mixture of the two sulphates. -------------------------------------------------------- Temperature. | Level of oil in capillary. | Rise per 1°. -------------------------------------------------------- 15.6° | 134 | 16.6° | 141 | 7 17.6° | 148 | 7 18.6° | 154 | 6 19.6° | 161 | 7 20.6° | 168 | 7 21.6° | 241 | 73 22.6° | 243 | 2 23.6° | 251 | 8 24.6° | 259 | 8 -------------------------------------------------------- The transition point, therefore, lies about 21.6° (p. 268). The second method of manipulation depends on the fact that, while above or below the transition point transformation of one form into the other can take place, at the transition point the two forms undergo no change. The bulb of the dilatometer is, therefore, charged with a mixture of the stable and metastable forms and a suitable liquid, and is then immersed in a bath at constant temperature. After the temperature of the bath has been acquired, readings of the height of the meniscus are made from time to time to ascertain whether expansion or contraction occurs. If expansion is found, the temperature of the thermostat is altered until a temperature is obtained at which a gradual contraction takes place. The transition point must then lie between these two temperatures; and by repeating the determinations it will be possible to reduce the difference between the temperatures at which expansion and contraction take place to, say, 1°, and to fix the temperature of the transition point, therefore, to within half a degree. By this method the transition point, for example, of sulphur was found to be 95.6° under a pressure of 4 atm.[400] The following are the figures obtained by Reicher, who used a mixture {333} of 1 part of carbon disulphide (solvent for sulphur) and 5 parts of turpentine as the measuring liquid. TEMPERATURE 95.1°. ----------------------------------- Time in minutes. | Level of liquid. ----------------------------------- 5 | 343.5 30 | 340.5 55 | 335.75 65 | 333 ----------------------------------- TEMPERATURE 96.1°. ----------------------------------- Time in minutes. | Level of liquid. ----------------------------------- 5 | 342.75 30 | 354.75 55 | 360.5 60 | 361.5 ----------------------------------- TEMPERATURE 95.6°. ----------------------------------- Time in minutes. | Level of liquid. ----------------------------------- 5 | 368.75 100 | 368 110 | 368.75 ----------------------------------- At a temperature of 95.1° there is a contraction, _i.e._ monoclinic sulphur passes into the rhombic, the specific volume of the former being greater than that of the latter. At 96.1°, however, there is expansion, showing that at this temperature rhombic sulphur passes into monoclinic; while at 95.6° there is neither expansion nor contraction. This is, therefore, the transition temperature; and since the dilatometer was sealed up to prevent evaporation of the liquid, the pressure within it was 4 atm. II. Measurement of the Vapour Pressure.--In the preceding pages it has been seen repeatedly that the vapour pressures of the two systems undergoing reciprocal transformation become identical at the transition point (more strictly, at the triple or {334} multiple point), and the latter can therefore be determined by ascertaining the temperature at which this identity of vapour pressure is established. The apparatus usually employed for this purpose is the Bremer-Frowein tensimeter (p. 91). Although this method has not as yet been applied to systems of one component, it has been used to a considerable extent in the case of systems containing water or other volatile component. An example of this has already been given in Glauber's salt (p. 139). III. Solubility Measurements.--The temperature of the transition point can also be fixed by means of solubility measurements, for at that point the solubility of the two systems becomes identical. Reference has already been made to several cases in which this method was employed, _e.g._ ammonium nitrate (p. 112), Glauber's salt (p. 134), astracanite and sodium and magnesium sulphates (p. 268). The determinations of the solubility can be carried out in various ways. One of the simplest methods, which also gives sufficiently accurate results when the temperature is not high or when the solvent is not very volatile, can be carried out in the following manner. The solid substance is finely powdered (in order to accelerate the process of solution), and placed in sufficient quantity along with the solvent in a tube carefully closed by a glass stopper; the latter is protected by a rubber cap, such as a rubber finger-stall. The tube is then rotated in a thermostat, the temperature of which does not vary more than one or two tenths of a degree, until saturation is produced. The solution is withdrawn by means of a pipette to which a small glass tube, filled with cotton wool to act as a filter, is attached. The solution is then run into a weighing bottle, and weighed; after which the amount of solid in solution is determined in a suitable manner. For more accurate determinations of the solubility, especially when the solvent is appreciably volatile at the temperature of experiment, other methods are preferable. In Fig. 131 is shown the apparatus employed by H. Goldschmidt,[401] and used to a considerable extent in the laboratory of van't Hoff. This consists essentially of three parts: _a_, a tube in which the solvent and salt are placed; this is closed at the foot by an india-rubber stopper. Through this stopper there passes the bent tube _cb_, which connects the tube _a_ with the weighing-tube d. At _c_ there is a plug of cotton wool. Tube _e_ is open to the air. The wider portion of the tube _cb_, which passes through the rubber stopper in _a_, can be closed by a plug {335} attached to a glass rod _ff_, which passes up through a hollow Witt stirrer, _g_. After being fitted together, the whole apparatus is immersed in the thermostat. After the solution has become saturated, the stopper of the bent tube is raised by means of the rod _ff_ and a suction-pump attached to the end of e. The solution is thereby drawn into the weighing-tube _d_, the undissolved salt being retained by the plug at c. The apparatus is then removed from the thermostat, tube _d_ detached and immediately closed by a ground stopper. It is then carefully dried and weighed. [Illustration: FIG. 131.] Another form of solubility vessel, due to Meyerhoffer and Saunders, is shown in Fig. 132.[402] This consists of a single tube, and the stirring is effected by means of a glass screw. [Illustration: FIG. 132.] The progress of the solution towards saturation can be very well tested by determining the density of the solution from time to {336} time. This is most conveniently carried out by means of the pipette shown in Fig. 133.[403] With this pipette the solution can not only be removed for weighing, but the volume can be determined at the same time. It consists of the wide tube _a_, to which the graduated capillary _b_, furnished with a cap _c_, is attached. To the lower end of the pipette the tube _e_, with plug of cotton wool, can be fixed. After the pipette has been filled by sucking at the end of _b_, the stop-cock _d_ is closed and the cap _c_ placed on the capillary. The apparatus can then be weighed, and the volume of the solution be ascertained by means of the graduations. As has already been insisted, particular care must be paid to the characterization of the solid in contact with the solution. [Illustration: FIG. 133.] IV. Thermometric Method.--If a substance is heated, its temperature will gradually rise until the melting point is reached, and the temperature will then remain constant until all the solid has passed into liquid. Similarly, if a substance which can undergo transformation is heated, the temperature will rise until the transition point is reached, and will then remain constant until complete transformation has taken place. This method, it will be remembered, was employed by Richards for the determination of the transition point of sodium sulphate decahydrate (p. 136). The following figures give the results obtained by Meyerhoffer in the case of the transformation:-- CuK_{2}Cl_{4},2H_{2}O <--> CuKCl_{3} + KCl + 2H_{2}O the temperature being noted from minute to minute: 95°, 93°, 91.8°, 91.7°, 92°, 92.3°, 92.4°, 92.2°, 92.2°, 92°, 90.5°, 89°, and then a rapid fall in the temperature. From this we see that the transition point is about 92.2°. It is also evident that a slight supercooling took place (91.7°), owing to a delay in the transformation, but that then the temperature rose to the transition point. This is analogous to the supercooling of a liquid. A similar halt in the temperature would be observed on passing from lower to higher temperatures; but owing to a lag in the transformation, the same temperature is not always obtained. {337} V. Optical Method.--The transition point can sometimes be determined by noting the temperature at which some alteration in the appearance of the substance occurs, such as a change of colour or of the crystalline form. Thus mercuric iodide changes colour from red to yellow, and the blue quadratic crystals of copper calcium acetate change, on passing the transition point, into green rhombs of copper acetate and white needles of calcium acetate (p. 260). Or again, changes in the double refraction of the crystals may be also employed to ascertain the temperature of the transition point. These changes are best observed by means of a microscope. For the purpose of regulating the temperature of the substance a small copper air-bath is employed.[404] VI. Electrical Methods.--Electrical methods for the determination of the transition point are of two kinds, based on measurements of conductivity or of electromotive force. Both methods are restricted in their application, but where applicable give very exact results. The former method, which has been employed in several cases, need not be described here. The second method, however, is of considerable interest and importance, and calls for special reference.[405] If two pieces, say, of zinc, connected together by a conducting wire, are placed in a solution of a zinc salt, _e.g._ zinc sulphate, the potential of the two electrodes will be the same, and no current will be produced in the connecting wire. If, however, the zinc electrodes are immersed in two solutions of _different_ concentration contained in separate vessels, but placed in connection with one another by means of a bent tube filled with a conducting solution, the potentials at the electrodes will no longer be the same, and a current will now flow through the connecting wire. The direction of this current _in the cell_ will be from the weaker to the more concentrated solution. The greater the difference in the concentration of the solutions with respect to zinc, the greater will be the difference of the potential at the two electrodes, or the greater will be the E.M.F. of the cell. When the concentration of the two solutions becomes the same, the E.M.F. will become zero, and no current will pass. It will be understood now how this method can be made use of {338} for determining the transition point of a salt, when we bear in mind that at the transition point the solubility of the two forms becomes identical. Thus, for example, the transition point of zinc sulphate heptahydrate into hexahydrate could be determined in the following manner. Tube A (Fig. 134) contains, say, a saturated solution of the heptahydrate along with some of the solid salt; tube B, a saturated solution of the hexahydrate along with the solid salt. The tube C is a connecting tube bent downwards so as to prevent the mixing of the solutions by convection currents. ZZ are two zinc electrodes immersed in the solution; the cell is placed in a thermostat and the zinc electrodes connected with a galvanometer. Since, now, at temperatures below the transition point the solubility of the hexahydrate (the metastable form) is greater than that of the heptahydrate, a current will be produced, flowing in the cell from heptahydrate to hexahydrate. As the temperature is raised towards the transition point, the solubilities of the two hydrates also approach, and the current produced will therefore become weaker, because the E.M.F. of the cell becomes less; and when the transition point is attained, the E.M.F. becomes zero, and the current ceases. If the temperature is raised above this, the solubility of the heptahydrate becomes greater than that of the hexahydrate, and a current will again be produced, but in the opposite direction. By noting the temperature, therefore, at which the current ceases, or the E.M.F. becomes zero, the transition temperature can be ascertained.[406] [Illustration: FIG. 134.] In the case just described, the electrodes consisted of the same metal as was contained in the salt. But in some cases, _e.g._ sodium sulphate, electrodes of the metal contained in the salt cannot be employed. Nevertheless, the above electrical method can be used {339} even in those cases, if a suitable non-polarizable mercury electrode is employed.[407] Although, as we saw, no current was produced when two pieces of zinc were immersed in the same solution of zinc salt, a current will be obtained if two different metals, or even two different modifications of the same metal, are employed. Thus an E.M.F. will be established when electrodes of grey and of white tin are immersed in the same solution of zinc salt, but at the transition point this E.M.F. will become zero. By this method Cohen determined the transition point of grey and white tin (p. 42). * * * * * {340} NAME INDEX A Abegg, 52 Adriani, 186, 217, 220 Alexejeff, 97, 125 Allan, 298 Allen, L. E., 109 Allen, R. W., 63 Ampolla, 213 Andreä, 109 Aristotle, 41 Armstrong, E. F., 313 Armstrong, H. E., 196 Arzruni, 33 Aten, 147, 163 Auerbach, 326 B Babo, 126 Bancroft, 102, 104, 161, 176, 196, 202, 229, 246, 260, 261, 272, 281, 302 Barnes, 331, 339 Barschall, 318 Barus, 67 Battelli, 23 Baur, 233, 307 Beckmann, 49 Bell, 229 Berthollet, 7 Bodländer, 181, 247, 311, 321 Bogojawlenski, 72 Boudouard, 309, 311 Braun, 107 Brauns, 40, 51, 74 Bredig, 52 Bremer, 91 Brodie, 34, 47 Bruner, 126 Bruni, 181, 182, 256, 257 Bunsen, 67 C Cady, 192 Calvert, 130 Cameron, 203 Carnelley, 47 Carpenter, 225 Carveth, 204, 255 Centnerszwer, 158 Chapman, 47 Chappuis, 51, 176 Charpy, 255 Churchill, 140 Coehn, 52 Cohen, 41, 72, 136, 139, 140 Cooke, 331, 339 Cox, 301 D Dawson, 263 Debray, 74, 81, 139 Deville, 49, 74 Dewar, 26, 51, 178 Dietz, 157 {341} Doelter, 233 Donnan, 8, 18 Dreyer, 73 Duhem, 56, 151 Dutoit, 204 E Etard, 115, 135 F Fahrenheit, 30 Faraday, 82, 89 Fath, 204 Fedotieff, 315, 320 Findlay, 111, 204, 206, 219 Foote, 69 Friedländer, 72 Fritsche, 41 Frowein, 91 Füchtbauer, 75 Fyffe, 143 G Gattermann, 51, 52 Gautier, 222, 223 Gay-Lussac, 135 Gernez, 72 Gibbs, 7, 8, 151, 236 Glaessner, 307 Goldschmidt, E., 41 Goldschmidt, H., 335 Goldschmidt, V., 32 Goossens, 26 Gossner, 318 Graham, 178 Guertler, 73 Guldberg, 7 Guthrie, 97, 104, 117, 118, 119, 233 H Haber, 311 Hahn, 309, 311 Hallock, 35 Hammerl, 145 Hautefeuille, 46, 49, 50, 51, 178 Heller, 311 Henry, 94 Herold, 321 Hertz, 49 Heycock, 194, 221, 223 Heyn, 225, 228 Hickmans, 219 Hiorns, 228 Hissink, 115, 190 Hoitsema, 14, 90, 177, 178, 298 Hollmann, 204 Holsboer, 110 Horstmann, 8, 83, 89 Hudson, 102 Hulett, 10, 48, 52, 54, 67, 109 I Isaac, 114 Isambert, 80, 82, 84 J Jaffé, 74, 114 Joulin, 176 Juhlin, 23, 24, 30 von Jüptner, 225 K Kastle, 71 Kaufler, 49 Kaufmann, 112 Kayser, 176 Keeling, 225 Kelvin, 25 Kenrick, 263, 297 Kipping, 219 Kirchhoff, 32 Knorr, 203 de Kock, 53, 182, 194 Konowaloff, 102, 103, 104 Krasnicki, 144 Kremann, 147, 212 Kuenen, 105 Kultascheff, 233 {342} Kuriloff, 216 Kurnakoff, 221, 222, 230 Küster, 72, 181, 183 L Laar, 195 Labenburg, 216 Lattey, 101 Le Chatelier, 58, 81, 233 Lehfeldt, 338, 340 Lehmann, 33, 52, 53 Lidbury, 147 Loewel, 134, 135 Loewenherz, 134, 316 Lowry, 196, 198 Ludwig, 327 Lumsden, 80, 109, 110 Lussana, 68 Luther, 22 M Mack, 67 Magnus, 22 Mathews, 221 Mellor, 80 Meusser, 142 Meyer, J., 71 Meyer, V., 47 Meyerhoffer, 158, 233, 259, 268, 271, 278, 279, 280, 284, 313, 315, 317, 319, 327, 328, 336, 337 Middelberg, 116 Miers, 114 Miller, 297 Mitscherlich, 33, 49 Mond, 178 Moore, 72 Moss, 66 Müller, 112, 265 Mylius, 109, 142, 157 N Naumann, 49 Neville, 194, 221, 223 O Offer, 119 Ostwald, 8, 10, 13, 16, 22, 44, 58, 68, 70, 74, 85, 88, 92, 102, 110, 117, 125, 127, 130, 141, 198 P Padoa, 73, 181 Parsons, 298 Pasteur, 266 Paternò, 213 Payen, 74 Pedler, 47 Pfaundler, 119 Philip, 213, 214 von Pickardt, 73 Planck, 68 Pope, 219 Poynting, 68 Preuner, 311 Puschin, 222 Q Quincke, 52 R Rabe, 113 Ramsay, 3, 22, 23, 24, 30, 32, 63, 64, 66, 79, 90, 165, 178 Raoult, 180 Reed, 71 Regnault, 22 Reicher, 36, 37, 110, 260, 333 Reinders, 71, 185, 188 Reinitzer, 51, 52 Richards, 136, 140 Riddle, 47 Riecke, 48, 55 Roberts-Austen, 63, 194, 221, 223, 225 Roloff, 117 Roozeboom, 10, 38, 45, 47, 49, 50, 51, 54, 56, 57, 62, 63, 68, 88, 103, 126, 145, 147, 150, 151, 157, 162, 170, 174, 178, 182, 196, 201, 211, 217, 220, 225, 236, 238, 262, 264, 269, 272, 273, 281, 282, 290, 331 {343} Rose, 223 Rotarski, 52 Rothmund, 97, 98, 100 Rutten, 298 S Saposchnikoff, 212 Saunders, 313, 317, 319, 336, 337 Saurel, 151 Schaum, 49, 75 Scheel, 22, 23, 30 Schenck, 49, 52, 54, 311 Schneider, 52 Schönbeck, 75 Schreinemakers, 122, 126, 246, 248, 250, 252, 290, 302 Schrötter, 46 Schukowsky, 52 Schwarz, 331 Seitz, 52 Shenstone, 109, 115, 135 Shepherd, 221, 255 Shields, 178 Skirrow, 130 Spring, 63 von Stackelberg, 107, 110 Staedel, 267 Stansfield, 194, 221 Stokes, 236 Stortenbeker, 44, 147, 161, 164, 281 T Taber, 229 Tammann, 26, 32, 33, 37, 38, 39, 48, 52, 65, 67, 68, 72, 73, 140, 151, 176, 221, 230 Thiesen, 22, 23, 30 Thomson, J., 25, 28, 32 Thomson, W., 25 Tilden, 109, 115, 135 Trevor, 16 Troost, 46, 49, 50, 51 Tumlirz, 72 V Van Bemmelen, 180 Van Deventer, 110, 139, 266, 267, 333 Van Eyk, 41, 63, 192, 338 Van't Hoff, 36, 38, 58, 70, 90, 92, 108, 127, 139, 140, 165, 175, 225, 258, 260, 263, 265, 266, 267, 272, 284, 290, 313, 318, 333, 340 Van Leeuwen, 259 Van Wyk, 185 Vogt, 5, 233 W Waage, 7 Wald, 92 Walden, 158 Walker, 80, 105, 122, 126, 143 Wegscheider, 10, 49, 202 Wells, 136 Wenzel, 7 Wiebe, 22 Witt, 327 Wright, 241, 246, 247 von Wrochem, 109, 142 Y Young, 3, 22, 23, 24, 30, 32, 63, 64, 66, 79, 105, 165 Z Zacharias, 180 Zawidski, 63 Zenghelis, 35 Zimmermann, 311 Zincke, 44 Ziz, 141 * * * * * {344} SUBJECT INDEX A Acetaldehyde and paraldehyde, 204 Acetic acid, chloroform, water, 241 Acetone, phenol, water, 248 Adsorption, 176 Alcohol, chloroform, water, 246 ----, ether, water, 246 Alloys, equilibrium curves of, 221 ---- of copper and tin, liquefaction of, by cooling, 194 ---- of iron and carbon, 223 ---- of thallium and mercury, 222 ----, ternary, 246 Ammonia compounds of metal chlorides, 82 Ammonia silver chlorides, 82 ---- ---- ----, dissociation pressures of, 84 Ammonia-soda process, 320 Ammonium chloride, dissociation of, 3, 79 ---- cyanide, dissociation of, 80 ---- hydrosulphide, dissociation of, 80 ---- nitrate, solubility of, 113 Aniline, phenol, water, 250 Astracanite, 260, 261, 268, 274 B Babo, law of, 126 Barium acetate, solubility of, 143 Barium carbonate and potassium sulphate, 328 ---- nitrite, preparation of, 327 Basic salts, 296 Benzaldoximes, 203 Benzene and picric acid, 216 Bismuth, effect of pressure on the melting point of, 67 ----, lead, tin, 255 ---- nitrates, basic, 298 Bivariant systems, 16 Bromocinnamic aldehyde and chlorocinnamic aldehyde, 183 C Calcium carbonate, dissociation of, 3, 11, 81 ---- chloride hexahydrate, solubility of, 146 ---- ----, solubility of hydrates of, 148 ---- ----, vapour-pressure of hydrates of, 88 Camphor oximes, 219, 257 Carnallite, 284 Carvoximes, 186, 219 Cementite, 224 Chlorine and iodine, 161 Chlorocinnamic aldehyde and bromocinnamic aldehyde, 183 Chloroform, acetic acid, water, 241 ----, alcohol, water, 246 {345} Classification of systems, 17 Component, 8, 10, 12 ----, systems of one, 21, 55 Components, choice of, 12, 13, 14, 76, 313 ----, determination of number of, 13 ----, systems of four, 312 ----, ---- of three, 234 ----, ---- of two, 76, 207 ----, variation in number of, 11, 14 Composition, determination of, without analysis, 228, 302 Concentration-temperature curve for two liquids, 101 Condensed systems, 36 Constituent, 10 Cooling curve, 230 Copper calcium acetate, 260 ---- chloride, heat of solution of, 110 ---- dipotassium chloride, 259 ---- sulphate, 85 Critical concentration, 98, 242 ---- pressure of water, 23 ---- solution temperature, 98 ---- temperature of water, 23 Cryohydrates, 117, 118 Cryohydric point, 117 ---- ----, changes at the, 119 ---- ---- for silver nitrate and ice, 116 Crystals, liquid, 51 ----, ----, equilibria of, 53 ----, ----, list of, 54 ----, ----, nature of, 52 ----, mixed, 180 Crystallization, velocity of, 72, 74 ----, spontaneous, 114 D Deliquescence, 130 Devitrification, 73 Diethylamine and water, solubility of, 101 Dilatometer, determination of transition points by, 331 Dineric surface, 247 Dissociation equilibrium, effect of addition of dissociation products on, 4 ---- of ammonia compounds of metal chlorides, 82, 84 ---- of ammonium chloride, 3, 79 ---- ---- cyanide, 80 ---- ---- hydrosulphide, 80 ---- of calcium carbonate, 3, 81 ---- of compounds, degree of, 147 ---- of phosphonium bromide, 80 ---- of salt hydrates, 85 ----, phenomena of, 79 Dissociation pressure, 81 Distillation of supercooled liquid to solid, 32, 50 Double salt interval, 278 ---- salts, crystallization from solution, 280 ---- ----, decomposition by water, 267 ---- ----, formation of, 258, 273, 315 E Efflorescence, 86 Electrical methods of determining transition points, 338 Enantiotropy, 44, 51 Equilibria, Gibbs's theory of, 8 ----, metastable, 69 Equilibrium apparent (false), 5, 6 ---- between ice and solution, 116 ---- between ice and water, 25 ---- between ice, water, vapour, 27 ---- between water and vapour, 21 ----, chemical, 3, 16 ----, heterogeneous, 5 ----, homogeneous, 5 ----, independence of, on amounts of phases, 9 ----, law of movable, 58 {346} ----, physical, 3, 16 ---- real (true), 5, 6 Ether, alcohol, water, 246 ----, succinic nitrile, water, 252 Ethylene bromide, picric acid, [beta]-naphthol, 256 Eutectic mixtures, 117, 191, 209, 255, 257 ---- point, 117, 209, 213, 253 F Ferric chloride, evaporation of solutions of, 155 ---- ----, hydrates of, 151, 153 ---- ----, hydrogen chloride and water, systems of, 290 Ferrite, modifications of, 224 Freedom, degree of, 14 Freezing mixtures, 120 ---- point, natural, 198 Fusion curve, 66 ---- ---- of ice, 25 ---- of ice, influence of pressure on, 26 ----, partial, 139 G Glaserite, 315, 317 Glasses, 176 Glauber's salt, 13, 134 ---- ----, transition curve of, 68, 140 Graphic representation in space, 77, 284 H Hydrates, range of existence of, 89 ---- chloride and water, 174 Hydrogen bromide and water, 174 Hylotropic substances, 198 I Ice I., 32 ---- II., 32 ---- III., 32 ----, equilibrium between water and, 25 ----, influence of pressure on melting point of, 25, 26 ----, sublimation curve of, 24 ----, vapour pressure of, 25, 31 Indifferent point, 150 Individual, chemical, 92 Inversion temperature, 36 Iodine and chlorine, 161 Iron--carbon alloys, 223 ----, carbon monoxide and carbon dioxide, 305 Isomerides, dynamic, 195, 196 ----, ----, equilibrium between, 195, 196 ----, ----, equilibrium point of, 198 ----, transformation of unstable into stable, 201 Isomerism, dynamic, 196 Isothermal evaporation, 278 ---- solubility curves, 272 L Lead, bismuth, tin, 255 ----, desilverization of, 247 ----, silver, zinc, 246 Le Chatelier, theorem of, 57 Lime, burning of, 3 Liquidus curve, 182 M Mandelic acid, 217 Martensite, 224 Mass action, law of, 7 Melting point, influence of pressure on, 66 {347} ---- ----, congruent, 146 ---- ----, incongruent, 139 ---- under the solvent, 122 Menthyl mandelates, 219 Mercuric bromide and iodide, 188 Mercury salts, basic, 301 Metastable equilibria, 69 ---- region, 30 ---- state, 30 Methylethyl ketone and water, 100 Minerals, formation of, 232 Miscibility of liquids, complete, 95, 104, 114 ---- ----, partial, 95, 96, 121 Mixed crystals, 180, 281 ---- ----, changes in, with temperature, 192 ---- ----, examples of, 183, 186, 187, 190, 192, 219, 223 ---- ----, formation of, 181, 182 ---- ----, fractional crystallization of, 188 ---- ----, freezing points of, 182 ---- ----, melting points of, 182, 184 ---- ----, pseudoracemic, 219 Mixtures, isomorphous, 181 ---- of constant boiling point, 105 ---- of constant melting point, 117, 186, 187, 192, 209, 255, 257 Monotropy, 44, 51 Multivariant systems, 16 N Naphthalene and monochloracetic acid, 192 ---- and [beta]-naphthol, mixed crystals of, 183 [beta]-Naphthol, ethylene bromide, picric acid, 256 [alpha]-Naphthylamine and phenol, 213 Nickel iodate, solubility of, 142 _o_-Nitrophenol and _p_-toluidine, 213 O Occlusion of gases, 176 Optical method of determining transition points, 338 Optically active substances, freezing-point curves of, 216 Order of a system, 13 Organic compounds, application of Phase Rule to, 212 P Palladium and hydrogen, 90, 178 Paragenesis, 320 Paraldehyde and acetaldehyde, 204 Partial pressures of two components, 102 Pearlite, 224 Phase, 8 ---- Rule, 8, 16 ---- ----, deduction of, 18 ---- ----, scope of, 1 Phases, formation of new, 69 ----, number of, 9 Phenol, acetone, water, 248 ----, aniline, water, 250 ---- and [alpha]-naphthylamine, 213 ---- and _p_-toluidine, 214 ---- and water, solubility of, 97 Phosphonium bromide, dissociation of, 80 ---- chloride, 65 Phosphorus, 46 ----, distillation of white to red, 50 ----, melting point of red, 47 ----, ---- ---- of white, 48 ----, solubility of white and red, 47 ----, vapour pressure of white and red, 46 Picric acid and benzene, 216 ---- ----, ethylene bromide, and [beta]-naphthol, 256 Polymorphic forms, solubility of, 112 {348} ---- substances, list of, 63 Polymorphism, 33 Potassium nitrate and thallium nitrate, 192 Potential, chemical, 19 Pressure-concentration diagram for two liquids, 102 Pressure-temperature diagram for solutions, 126 Pseudomonotropy, 45 Pseudo-racemic mixed crystals, 21 Pyridine and methyl iodide, 147 Pyrometer, registering, 230 Q Quadruple point, 116 Quintuple point, 234, 261 R Racemates, characterization of, 217, 282 Reactions, law of successive, 73 Reciprocal salt-pairs, 313 ---- ----, transition point of, 314 Rubidium tartrates, 265 S Salt hydrates, 85 ---- ----, indefiniteness of vapour pressure of, 87 ---- ---- with definite melting point, 145 Separation of salt on evaporation, 130 Silicates, hydrated, 176 Silver, lead, zinc, 246 Silver nitrate, solubility of, 114 ---- ---- and sodium nitrate, 190 Single salt interval, 278 Sodium ammonium tartrates, 266 ---- nitrate and silver nitrate, 190 ---- sulphate and water, equilibria between, 134 Sodium sulphate and water, vapour pressures of, 138, 140 ---- ----, anhydrous, dehydration by, 138 ---- ----, solubility of, 135 ---- ---- decahydrate, solubility of, 134 ---- ---- ----, transition point of, 136, 139 ---- ---- heptahydrate, solubility of, 136 ---- ---- ----, transition point of, 137 Solidus curve, 182 Solubility curve at higher temperatures, 114 ---- ----, form of, 108 ---- ---- of anhydrous salts, 111 ---- ----, retroflex, 146, 151, 162 ---- curves, interpolation and extrapolation of, 111 ---- ---- of three component systems, 264 ----, determination of transition points by, 335 ----, influence of pressure on, 107 ----, ---- of subdivision on, 10 ----, ---- of temperature on, 109 ---- of metastable forms, 47, 112, 137 Solubility of polymorphic forms, 112 ---- of salt hydrates, 133, 145 ---- of supercooled liquids, 125 ----, retrograde, 245 Solute, 93 Solution, definition of, 92 ----, heat of, 109, 110 ----, saturated, 106, 108 ----, supersaturated, 108 ---- temperature, critical, 98 ----, unsaturated, 108 Solutions, bivariant systems, 129 ----, congruently saturated, 279 ---- conjugate, 97, 241 {349} ----, incongruently saturated, 279, 289 ----, inevaporable, 157 ---- of gases in liquids, 93 ---- ---- in solids, 176 ---- of liquids in liquids (binary), 95 ---- ---- ---- (ternary), 240 ---- ----, influence of temperature on, 247 ---- of solids in liquids, 106 ---- ---- in solids, 180 ----, solid, 175, 180 ----, univariant systems, 127 Space model for carnallite, 284 Stability limit, 202 Steel, formation of, 223 Sublimation curve, 63 ---- ---- of ice, 24 ---- without fusion, 65 Succinic nitrile and water, 122 ---- ether, water, 252 Sulphur, 33, 34 ---- dioxide and water, 169 ---- ---- and potassium iodide, 158 ----, transition point of rhombic and monoclinic, 36 Supersaturation, 113, 114, 124 ----, limits of, 114 Systems, condensed, 36 ---- of one component, 21 ---- of two components, 76, 77, 207 T Tachydrite, influence of pressure on the transition point of, 263 Tartrate, dimethyl, 217 ----, sodium potassium, 259 Tautomeric substances, 195 Tensimeter, 91 Thallium nitrate and potassium nitrate, 192 Theorem of van't Hoff and Le Chatelier, 57 Thermometric determination of transition point, 337 Tin, 41 ----, lead, bismuth, 255 ---- plague, 43 ----, transition point of white and grey, 41 _p_-Toluidine and _o_-nitrophenol, 213 ---- and phenol, 214 Transformation of optically active substances, 220 ----, suspended, 37, 69, 89, 113, 137, 155 ----, velocity of, 70 Transition curve, 66 ---- ---- of Glauber's salt, 68, 140 ---- ---- of rhombic and monoclinic sulphur, 37 ---- interval, 270, 277, 315 ---- point, 34 ---- ---- for double salts, 258 ---- ----, influence of pressure on the, 68 ---- points, as fixed points in thermometry, 140 ---- ----, methods of determining, 331 ---- ---- of polymorphic substances, 63 Triangle, graphic representation by, 235 Triethylamine and water, 101 Triple point, 27, 55 ---- ----, arrangement of curves round, 56 ---- ----, changes at, 58 ---- ----, ice, water, vapour, 27 ---- ----, ice II., ice III., and water, 33 ---- ----, metastable, 38 ---- ----, monoclinic sulphur, liquid, vapour, 38 ---- ----, monoclinic and rhombic sulphur, liquid, 38 ---- ----, monoclinic and rhombic sulphur, vapour, 34 {350} ---- ----, red phosphorus, liquid, vapour, 47 ---- ----, rhombic sulphur, liquid, vapour, 38 ---- ---- solid, solid, vapour, 62 ---- ----, white phosphorus, liquid, vapour, 48 U Univariant systems, 16 V Van't Hoff, theorem of, 57 Vaporization curve, 63 ---- ----, interpolation and extrapolation of, 66 ---- ---- of water, 21, 23 Vapour pressure, constancy of, and formation of compounds, 90 ---- ----, dependence of, on solid phase, 88 ---- ----, influence of surface tension on, 2 ---- ---- in three-component systems, 261 ---- ----, measurement of, 91, 334 ---- ---- of calcium chloride solutions, 150 ---- ---- of ice, 25, 31 ---- ---- of small drops, 10 ---- ---- of sodium sulphate and water, 138 Vapour pressure of solid, solution, vapour, 126 ---- ---- of water, 21, 31 Variability of a system, 14, 16 Variance of a system, 16 Volatile components, two, 161 W Water, 21 ----, acetic acid, chloroform, 241 ----, acetone, phenol, 248 ----, alcohol, ether, 246 ----, ----, chloroform, 246 ----, aniline, phenol, 250 ----, bivariant systems of, 29 ----, critical pressure of, 23 ----, critical temperature of, 23 ----, equilibrium between ice and, 25 ----, ---- between vapour and, 21 ----, ether, succinic nitrile, 252 ----, supercooled, 30 ----, ----, vapour pressure of, 31 ----, vaporization curve of, 21 ----, vapour pressure of, 23 Z Zeolites, 176 Zinc, lead, silver, 246 ---- chloride in water, solubility of, 157 THE END PRINTED BY WILLIAM CLOWES AND SONS, LIMITED, LONDON AND BECCLES. * * * * * NOTES [1] Except when the volume of the liquid becomes exceedingly small, in which case the surface tension exerts an influence on the vapour pressure. [2] For reasons which will appear later (Chap. IV.), the volume of the vapour is supposed to be large in comparison with that of the solid and liquid. [3] Ramsay and Young, _Phil. Trans._, 1886, 177. 87. [4] See, more especially, Vogt, _Die Silikatschmelzlösungen_. (Christiania, 1903, 1904.) [5] _Trans. Connecticut Acad._, 1874-1878. [6] Lehre von der chemischen Verwandtschaft der Körper, 1777. [7] See Ostwald's _Klassiker_, No. 74. [8] Etudes sur les affinités chimiques, 1867; Ostwald's _Klassiker_, No. 104. [9] Died April, 1903. [10] For a mathematical treatment of the Phase Rule the reader is referred to the volume in this series on Thermodynamics, by F. G. Donnan. [11] Liebig's _Annalen_, 1873, 170, 192; Ostwald, _Lehrbuch_, II. 2. 111. [12] The action of gravity and other forces being excluded (see p. 5). [13] It may seem as if this were a contradiction to what was said on p. 4 as to the effect of the addition of ammonia or hydrogen chloride to the system constituted by solid ammonium chloride in contact with its products of dissociation. There is, however, no contradiction, because in the case of ammonium chloride the gaseous phase consists of ammonia and hydrogen chloride in equal proportions, and in adding ammonia or hydrogen chloride alone we are not adding the gaseous phase, but only a constituent of it. Addition of ammonia and hydrogen chloride together in the proportions in which they are combined to form ammonium chloride would cause no change in the equilibrium. [14] The vapour pressure of water in small drops is greater than that of water in mass, and the solubility of a solid is greater when in a state of fine subdivision than when in large pieces (_cf._ Hulett, _Zeitschr. physikal. Chem._, 1901, 37. 385). [15] See Ostwald, _Lehrbuch_, II. 2. 476, 934; Roozeboom, _Zeitschr. physikal. Chem._, 1894, 15. 150; _Heterogene Gleichgewichte_, I. p. 16; Wegscheider, _Zeitschr. physikal. Chem._, 1903, 43. 89. [16] Ostwald, _Lehrbuch_, II. 2. 478. [17] See also Hoitsema, _Zeitschr. physikal. Chem._ 1895, 17. 651. [18] The term "degree of freedom" employed here must not be confused with the same term used to denote the various movements of a gas molecule according to the kinetic theory. [19] Trevor, _Jour. Physical Chem._, 1902, 6. 136. [20] Ostwald, _Principles of Inorganic Chemistry_, translated by A. Findlay, 2nd edit., p. 7. (Macmillan, 1904.) [21] See the volume in this series on _Thermodynamics_ by F. G. Donnan. [22] _Pogg. Annalen_, 1844, 61. 225. [23] _Mémoires de l'Acad._, 26. 751. [24] _Phil. Trans._ 1884, 175. 461; 1892, A, 183. 107. [25] _Bihang Svenska Akad. Handl._ 1891, 17. I. 1. [26] Abh_andl. physikal.-tech. Reichsanstalt_, 1900, 3. 71. [27] Ostwald-Luther, _Physiko-chemische Messungen_, 2nd edit., p. 156. [28] _Annales chim. et phys._, 1892 [6], 26. 425. [29] The vapour pressure of water at 0° has recently been very accurately determined by Thiesen and Scheel (_loc. cit._), and found to be 4.579 ± 0.001 mm. of mercury (at 0°), or equal to 0.006025 atm. [30] Juhlin, _Bihang Svenska Akad. Handl._, 1891, 17. I. 58. See also Ramsay and Young, _loc. cit._ [31] _Trans. Roy. Soc. Edin._, 1849, 16. 575. [32] _Proc. Roy. Soc. Edin._, 1850, 2, 267. [33] _Annalen der Physik_, 1899 [3], 68. 564; 1900 [4], 2. 1, 424. See also Dewar, _Proc. Roy. Soc._, 1880, 30. 533. [34] The pressure of 1 atmosphere is equal to 1.033 kilogm. per sq. cm.; or the pressure of 1 kilogm. per sq. cm. is equal to 0.968 atm. [35] Tammann, _loc. cit._, 1900, 2. 1, 424; cf. Goossens, _Arch. néerland_, 1886, 20. 449. [36] J. Thomson, _Proc. Roy. Soc._, 1874, 22. 28. [37] A field is "enclosed" by two curves when these cut at an angle less than two right angles. It may be useful to remember that an invariant system is represented by a _point_, a univariant system by a _line_, and a bivariant system by an _area_. [38] _Phil. Trans._, 1724, 39. 78. [39] Juhlin, _loc. cit._, p. 61; cf. Ramsay and Young, _loc. cit._: Thiesen and Scheel, _loc. cit._ [40] This small difference is due to experimental errors in the determination of the vapour pressures; a differential method betrayed no difference between the vapour pressure of ice and of water at 0°. [41] _Phil. Mag._, 1874 [4], 47. 447; _Proc. Roy. Soc._, 1873, 22. 27. [42] _Pogg. Annalen_, 1858, 103, 206. [43] See _Phil. Trans._, 1884, 175, 461. [44] This phenomenon of distillation from the supercooled liquid to the solid has been very clearly observed in the case of furfuraldoxime (V. Goldschmidt, _Zeitschr. f. Krystallographie_, 1897, 28. 169). [45] _Annalen der Physik_, 1900 [4], 2. 1, 424. [46] A similar triple point has been determined by Tammann in the case of phenol (_Annalen der Physik_, 1902 [4], 9. 249). [47] _Annales chim. et phys._, 1821, 19. 414. [48] Lehmann, _Molekularphysik_, I. 153.; Arzruni, _Physikalische Chemie der Krystalle_. (Graham-Otto, _Lehrbuch der Chemie_, I. 3.) [49] Brodie, _Proc. Roy. Soc._, 1855, 7. 24. [50] That solid sulphur does possess a certain vapour pressure has been shown by Hallock, who observed the formation at the ordinary temperature of copper sulphide in a tube containing copper and sulphur (_Amer. Jour. Sci._, 1889 [3], 37. 405). See also Zenghelis, _Zeitschr. physikal. Chem._, 1904, 50. 219. [51] _Zeitschr. für Krystallographie_, 1884, 8. 593. [52] Van't Hoff, _Studies on Chemical Dynamics_, p. 163. [53] Reicher, _loc. cit._ See also Tammann, _Annalen der Physik_, 1899 [3], 68. 663. [54] Tammann, _Annalen der Physik_, 1899 [3], 68. 633. [55] Rec. Trav. _Chim. Pays-Bas_, 1887, 6. 314. [56] Cf. van't Hoff, _Lectures on Physical Chemistry_, I., p. 27 (Arnold). [57] _Annalen der Physik_, 1899 [3], 68. 663. [58] Brauns, _Jahrbuch für Mineralogie_, 1899-1901, 13. Beilage, p. 39. [59] Fritsche, _Ber._, 1869, 2. 112, 540. [60] _De mirabilibus Auscultationibus_, Cap. 51 (_v._ Cohen, _Zeitschr. physikal. Chem._, 1901, 36. 513). [61] E. Cohen and C. van Eyk, _Zeitschr. physikal. Chem._, 1899, 30. 601; Cohen, _ibid._, 1900, 33. 59; 35. 588; 1901, 36. 513; Cohen and E. Goldschmidt, _ibid._, 1904, 50. 225. [62] _Zeitschr. physikal. Chem._, 1900, 33, 58. [63] Stortenbeker, _Zeitschr. physikal. Chem._, 1889, 3. 11; _Rec. Trav. Chim. Pays-Bas_, 1888, 7. 152. [64] Zincke, _Ber._, 1871, 4. 576. [65] Ostwald, _Zeitschr. physikal. Chem._, 1897, 22. 313. [66] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 177. [67] Roozeboom, _ibid._, p. 179. [68] Schrötter, _Pogg. Annalen_, 1850, 81. 276; Troost and Hautefeuille, _Annales de Chim. et Phys._ 1874 [5], 2. 153; _Ann. Scient. �cole Norm._ 1868 [2], II. 266. [69] Pedler, _Trans. Chem. Soc._, 1890, 57. 599. [70] Brodie, _Trans. Chem. Soc._, 1853, 5, 289. [71] This is a familiar fact in the case of the solubility in carbon disulphide. [72] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 170. [73] _Trans. Chem. Soc._, 1899, 57. 734. [74] Carnelley, _Trans. Chem. Soc._, 1876, 29. 489; 1878, 33. 275. V. Meyer and Riddle, _Ber._, 1893, 26. 2443. [75] Riecke, _Zeitschr. physikal. Chem._, 1890, 6. 411. [76] _Annalen der Physik._, 1898 [3], 66. 492. [77] _Zeitschr. physikal. Chem._, 1899, 28. 666. [78] See Naumann, _Ber._, 1872, 4. 646; Troost and Hautefeuille, _Compt. rend._, 1868, 66. 795; 1868, 67. 1345; Roozeboom, _Das Heterogene Gleichgewicht_, I. pp. 62, 171. [79] Mitscherlich, _Lieb. Annalen_, 1834, 12. 137; Deville and Troost, _Compt. rend._, 1863, 56. 891. [80] Beckmann, _Zeitschr. physikal. Chem._, 1890, 5. 79; Hertz, _ibid._, 6. 358. [81] _Ber._, 1902, 35. 351. _Cf._ also, K. Schaum, _Annalen der Chem._, 1898, 300. 221; R. Wegscheider and Kaufler, _Sitzungsber. kaiserl. Akad. Wissensch. in Wien_, 1901, 110, II. 606. [82] See also Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 177. [83] _Annales de Chim. et Phys._, 1874 [5], 2. 154. [84] _Compt. rend._, 1887, 104. 1505. [85] _Compt. rend._, 1868, 66. 795. [86] _Phil. Mag._, 1884 [5], 18. 210. See also Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 177. [87] Brauns, _Neues Jahrbuch für Mineralogie_, 1900, 13. Beilage-Band, p. 39; Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 181. [88] _Monatshefte_, 1888, 9. 435. [89] Gattermann, _Ber._, 1890, 53. 1738. [90] _Zeitschr. physikal. Chem._, 1889, 4. 468; _Annalen der Physik_, 1900 [4], 2. 649. [91] Quincke, _Annalen der Physik_, 1894 [3], 53. 613; Tammann, _Annalen der Physik_, 1901 [4], 4. 524; 1902, 8. 103; Rotarski, _ibid._, 4. 528. [92] _Annalen der Physik_, 1900 [4], 2. 649. [93] _Annalen der Physik_, 1902 [4], 8. 911. [94] See, more especially, O. Lehmann, _Annalen der Physik_, 1900 [4], 2. 649; Reinitzer, _Sitzungsber. kaiserl. Akad. zu Wien._, 1888, 94. (2), 719; 97. (1), 167; Gattermann, _loc. cit._; Schenck, _Zeitschr. physikal. Chem._, 1897, 23. 703; 1898, 25. 337; 27. 170; 1899, 28. 280; Schenck and Schneider, _ibid._, 1899, 29. 546; Abegg and Seitz, _ibid._, 1899, 29. 491; Hulett, _ibid._, 1899, 28. 629; Coehn, _Zeitschr. Elektrochem._, 1904, 10. 856: Bredig and Schukowsky, _ibid._, 3419. For a full account of the subject, the reader is referred to the work by Lehmann, _Flüssige Kristalle_ (Engelmann, 1904), or the smaller monograph by Schenck, _Kristallinische Flüssigkeiten und flüssige Kristalle_ (Engelmann, 1905). [95] A. C. de Kock, _Zeitschr. physikal. Chem._, 1904, 48. 129. [96] On account of the fact that all grades of rigidity have been realized between the ordinary solid and the liquid state, in the case both of crystalline and amorphous substances, it has been proposed to abandon the terms "solid" and "liquid," and to class bodies as "crystalline" or "amorphous," the passage from the one condition to the other being discontinuous; crystalline bodies possess a certain regular orientation of their molecules and a directive force, while in amorphous bodies these are wanting (see Lehmann, _Annalen der Physik_, 1900 [4], 2. 696). [97] Hulett, _loc. cit._ [98] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 144. See also Schenck, _Kristallinische Flüssigkeiten und flüssige Kristalle_, p. 8 (Engelmann, 1904). [99] The possible number of triple points in a one-component system is given by the expression (_n_(_n_ - 1)(_n_ - 2))/1.2.3, where _n_ is the number of phases (Riecke, _Zeitschr. physikal. Chem._, 1890, 6, 411). The number of triple points, therefore, increases very rapidly as the number of possible phases increases. [100] Duhem, _Zeitschr. physikal. Chem._, 1891, 8. 371. _Cf._ Roozeboom, _Das Heterogene Gleichgewicht_, p. 94 ff. [101] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 99. [102] Roozeboom, _Zeitschr. physikal. Chem._, 1888, 2. 474. [103] These changes can be predicted quantitatively by means of the thermodynamic equation, _dp_/_dt_ = Q/(T(_v_{2}_ - _v_{1}_)), provided the specific volumes of the phases are known, and the heat effect which accompanies the transformation of one phase into the other. [104] _Studies on Chemical Dynamics_, translated by Ewan, p. 218. [105] Le Chatelier, _Compt. rend._, 1884, 99. 786. [106] See _Principles of Inorganic Chemistry_, translated by Findlay, 2nd edit., p. 133. (Macmillan, 1904.) [107] Roozeboom, _Zeitschr. physikal. Chem._, 1888, 2. 474. [108] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 189. [109] Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 125. See also Zawidski, _Zeitschr. physikal. Chem._, 1904, 47. 727; van Eyk, _ibid._, 1905, 51. 720. [110] Roberts-Austen, _Proc. Roy. Soc._, 63. 454; Spring, _Zeitschr. physikal. Chem._, 1894, 15. 65. See also p. 35. [111] Ramsay and Young, _Phil. Trans._, 1884, 175. 461; Allen, _Trans. Chem. Soc._, 1900, 77. 413. [112] Ramsay and Young, _Phil. Trans._ 1886, 177. 87. [113] This is exemplified in the well-known experiment with the cryophorus. [114] Tammann has, however, found that the fusion curve (solid in contact with liquid) of phosphonium chloride can be followed up to temperatures above the critical point (_Arch. néer._, 1901 [2], 6. 244). [115] _Phil. Mag._, 1886, 21. 33. See also S. A. Moss, _Physical Review_, 1903, 16. 356. [116] This is found also in the case of bismuth. See Tammann, _Zeitschr. anorgan. Chem._, 1904, 40. 54. [117] See p. 57, footnote. [118] _Pogg. Annalen_, 1850, 81. 562. [119] Barus, _Amer. Jour. Sci._, 1892, 42. 125; Mack, _Compt. rend._, 1898, 127. 361; Hulett, _Zeitschr. physikal. Chem._, 1899, 38. 629. [120] _Annalen der Physik_, 1899 [3], 68. 553, 629; 1900 [4], 1. 275; 2. 1; 3. 161. See also Tammann, _Kristallisieren und Schmelzen_ (Leipzig, 1903). [121] Ostwald, _Lehrbuch_, II. 2. 373; Poynting, _Phil. Mag._, 1881 [5], 12. 2; Planck, _Wied. Annalen_, 1882, 15. 446. [122] Bakhuis Roozeboom, _Das Heterogene Gleichgewicht_, I. p. 91. [123] Lussana, _Il nuovo Cimento_, 1895 [4], 1. 105. [124] Tammann, _Zeitschr. physikal. Chem._, 1903, 46. 818. [125] Foote, _Zeitschr. physikal. Chem._, 1900, 33. 740. [126] Ostwald, _Zeitschr. physikal. Chem._, 1897, 22. 289. [127] Van't Hoff, _Arch, néer._, 1901, 6. 471. [128] See, for example, the determinations of the solubility of rhombic and monoclinic sulphur, by J. Meyer, _Zeitschr. anorg. Chem._, 1902, 33. 140. [129] _Zeitschr. physikal. Chem._, 1899, 32. 506. [130] Kastle and Reed, _Amer. Chem. Jour._, 1902, 27. 209. [131] _Zeitschr. physikal. Chem._, 1900, 35. 581. [132] _Compt. rend._, 1882, 95. 1278; 1884, 97. 1298, 1366, 1433. [133] _Zeitschr. physikal. Chem._, 1893, 12. 545. [134] _Sitzungsber. Wiener Akad._, 1894, 103. IIa. 226. [135] _Zeitschr. physikal. Chem._, 23-29. See also Küster, _ibid._, 25-28. [136] _Zeitschr. physikal. Chem._, 1897, 24. 152. [137] _Ibid._, 1898, 27. 585. [138] See W. Guertler, _Zeitschr. anorgan. Chem._, 1904, 40. 268; Tammann, _Zeitschr. Elektrochem._, 1904, 10. 532. [139] E. von Pickardt, _Zeitschr. physikal. Chem._, 1902, 42. 17. [140] _Zeitschr. physikal. Chem._, 1904, 48. 467. [141] M. Padoa, _Accad. Lincei, Atti_, 1904, 13. 329. [142] Deville, _Compt. rend._, 1852, 34. 561; Payen, _ibid._, 1852, 34. 508; Debray, _ibid._, 1858, 46. 576. It has also been found by Jaffé (_Zeitschr. physikal. Chem._, 1903, 43. 465) that when spontaneous crystallization from solution occurs, the less stable form always separates first when purification has been carried sufficiently far. [143] Brauns, _Neues Jahrbuch für Mineralogie_, 1899, 13. (Beilage Band) 84. [144] _Lehrbuch_, II. 2. 445. See also _Principles of Inorganic Chemistry_, 2nd edit., p. 210 ff. [145] Schaum and Schönbeck, _Annalen der Physik_, 1902 [4], 8. 652. See also Chr. Füchtbauer, _Zeitschr. physikal. Chem._, 1904, 48. 549. [146] Ramsay and Young, _Phil. Trans._, 1886, 177. 87. [147] See volume in this series on _Chemical Dynamics_, by Dr. J. W. Mellor. [148] Isambert, _Compt. rend._, 1881, 92. 919; 1882, 94. 958; 1883, 96. 643. Walker and Lumsden, _Jour. Chem. Soc._, 1897, 71. 428. [149] _Compt. rend._, 1867, 64. 603. [150] _Compt. rend._, 1883, 102. 1243. [151] _Compt. rend._, 1868, 66, 1259. [152] Horstmann, _Ber._, 1876, 9. 749. [153] _Loc. cit._ [154] For the reasons for choosing anhydrous salt and water instead of salt hydrate and water as components, see p. 14. [155] See Ostwald, _Lehrbuch_, II. 2. 527. [156] Ostwald, _Lehrbuch_, II. 2. 538. [157] _Zeitschr. physikal. Chem._, 1889, 4. 43. [158] _Ber._, 1876, 9. 749. [159] See, for example, van't Hoff, _Lectures on Theoretical and Physical Chemistry_, I. p. 62 (Arnold). [160] _Jour. Chem. Soc._, 1877, 32. 395. [161] Hoitsema, _Zeitschr. physikal. Chem._, 1895, 17. 1. [162] _Zeitschr. physikal. Chem._, 1887, 1. 5; 1895, 17. 52. [163] It is important to powder the salt, since otherwise the dehydration of the hydrate and the production of equilibrium occurs with comparatively great tardiness. [164] A chemical individual is a substance which persists as a phase of constant composition when the conditions of temperature, pressure, and composition of the other phases present, undergo continuous alteration within certain limits--the limits of existence of the substance (Wald, _Zeitschr. physikal. Chem._, 1897, 24. 648). [165] Van't Hoff, _Zeitschr. physikal. Chem._, 1890, 5. 323; Ostwald, _Lehrbuch_, I. 606. [166] That mercury does dissolve in water can be argued from analogy, say, with mercury and bromonaphthalene. At the ordinary temperature these two liquids appear to be quite insoluble in one another, but at a temperature of 280° the mercury dissolves in appreciable quantity; for on heating a tube containing bromonaphthalene over mercury the latter sublimes _through_ the liquid bromonaphthalene and condenses on the upper surface of the tube. [167] _Phil. Mag._, 1884, [5], 18. 22; 495. [168] _Wied. Annalen_, 1886, 28. 305. [169] _Zeitschr. physikal. Chem._, 1898, 26. 433. [170] Rothmund, _loc. cit._ [171] Rothmund, _loc. cit._ [172] A similar behaviour is found in the case of diethylamine and water (R. T. Lattey, _Phil. Mag._, 1905, [6], 10, 397). [173] C. S. Hudson, _Zeitschr. physikal. Chem._, 1904, 47. 113. [174] Konowaloff, _Wied. Annalen_, 1881, 14. 219. Ostwald, _Lehrbuch_, II. 2. 687. Bancroft, _Phase Rule_, p. 96. [175] Konowaloff, _loc. cit._ [176] Roozeboom, _Zeitschr. physikal. Chem._, 1891, 8. 526; _Rec. Trav. Chim. Pays-Bas_, 1884, 3. 38. [177] Konowaloff, _loc. cit._ Cf. Bancroft, _Phase Rule_, p. 100. [178] _Phil. Mag._, 1884 [5], 18. 503. [179] See, for example, Walker, _Introduction to Physical Chemistry_, 3rd edit., p. 86 (Macmillan, 1903). Consult also Young, _Fractional Distillation_ (Macmillan, 1903), or Kuenen, _Verdampfung und Verflüssigung von Gemischen_ (Barth, 1906), where the subject is fully treated. [180] Since this is the only phase of variable composition present. [181] E. von Stackelberg, _Zeitschr. physikal. Chem._, 1896, 20. 337. If the change of volume which accompanies solution, and the heat effect are known, the quantitative change of the solubility with the pressure can be calculated (Braun, _Zeitschr. physikal. Chem._, 1887, 1. 259). [182] Van't Hoff, _Arch. néerland._ 1901 [2], 6. 471. [183] Tilden and Shenstone, _Phil. Trans._ 1884, 175. 23; Hulett and Allen, _Jour. Amer. Chem. Soc._ 1902, 24. 667; Andreä, _Jour. prak. Chem._ 137. 474; Lumsden, _Jour. Chem. Soc._, 1902, 81. 350; Mylius and v. Wrochem, _Ber._ 1900, 33. 3689. [184] E. von Stackelberg, _Zeitschr. physikal. Chem._ 1896, 20. 159; 1898, 26. 533; Lumsden, _Jour. Chem. Soc._, 1902, 81. 350; Holsboer, _Zeitschr. physikal. Chem._, 1902, 39. 691. [185] Reicher and van Deventer, _Zeitschr. physikal. Chem._ 1890, 5. 559; cf. Ostwald, _Lehrbuch_, II. 2. 803. [186] It has been shown that the formula of Ramsay and Young (p. 66) can be applied (with certain restrictions) to the interpolation and extrapolation of the solubility curve of a substance provided two (or three) points on the curve are known. In this case T, T_{1}, etc., refer to the temperatures at which the two substances--one the solubility curve of which is known, the other the solubility curve of which is to be calculated--have equal solubilities, instead of, as in the previous case, equal vapour pressures. (Findlay, _Proc. Roy. Soc._, 1902, 69. 471; _Zeitschr. physikal. Chem._, 1903, 42. 110.) [187] W. Müller and P. Kaufmann, _Zeitschr. physikal. Chem._ 1903, 42. 497. [188] W. O. Rabe, _Zeitschr. physikal. Chem._, 1901, 38. 175. [189] With regard to the limits of supersaturation and the spontaneous crystallization of the solute from supersaturated solutions, see Jaffé, _Zeitschr. physikal. Chem._, 1903, 43. 565, and the very interesting paper by Miers and Isaac, _Trans. Chem. Soc._, 1906, 89. 413. [190] _Annales chim. phys._, 1894 [7], 2. 524. [191] _Phil. Trans._, 1884, 175. 23. [192] Hissink, _Zeitschr. physikal. Chem._, 1900, 32. 543. [193] _Zeitschr. physikal. Chem._, 1903, 43. 313. [194] Guthrie, _Phil. Mag._, 1875, [4], 49. 1; 1884, [5], 17. 462. [195] See Roloff, _Zeitschr. physikal. Chem._, 1895, 17. 325; Guthrie, _loc. cit._ [196] Guthrie, _Phil. Mag._, _loc. cit._ Cf. Ostwald, _Lehrbuch_, II. 2. 843. [197] Guthrie, _Phil. Mag._, 1875 [4], 49. 269. [198] _Ber._, 1877, 20. 2223. [199] _Silz-Ber. Wien. Akad._, 1880, 81. II. 1058. [200] Guthrie, _Phil. Mag._, 1875 [4], 49. 206. [201] If in the neighbourhood of the cryohydric point solution should be accompanied by an evolution of heat, then as the solubility would in that case increase with fall of temperature, salt would pass into solution. [202] Walker, _Zeitschr. physikal. Chem._, 1890, 5. 193. [203] _Zeitschr. physikal. Chem._, 1897, 23. 418. [204] Provided the solid nitrile is not present in too great excess. [205] _Wied. Annalen_, 1886, 28. 328. Cf. Ostwald, _Lehrbuch_, II. 2. 872. [206] Walker, _Zeitschr. physikal. Chem._, 1890, 5. 193. Schreinemakers, _ibid._, 1897, 23. 417. Roozeboom, _Rec. trav. chim. Pays-Bays_, 1889, 8. 257. Bruner, _Zeitschr. physikal. Chem._, 1897, 23. 542. [207] Van't Hoff, _Lectures on Theoretical Chemistry_, I. p. 42. Ostwald, _Lehrbuch_, II. 2. 824. [208] Ostwald, _Principles of Inorganic Chemistry_, translated by A. Findlay, 2nd edit., p. 453 (Macmillan, 1904); Skirrow and Calvert, _Zeitschr. physikal. Chem._, 1901, 37. 217. [209] _Vide_ Loewel, _Annales chim. phys._, 1857 [3], 49. 32. Cf. Löwenherz, _Zeitschr. physikal. Chem._, 1895, 18. 82. [210] Loewel, _loc. cit._ Gay-Lussac, _Annales chim. phys._, 1819, 11. 296. For the solubility at higher temperatures, see Tilden and Shenstone, _Phil. Trans._, 1884, 175. 23. �tard, _Annales chim. phys._, 1894 [7], 2. 548. [211] Richards, _Zeitschr. physikal. Chem._, 1898, 26. 690; Richards and Wells, _ibid._, 1903, 43. 465. This temperature is not quite the same as that of the _quadruple point_ anhydrous salt--hydrated salt--solution--vapour, because the latter is the temperature at which the system is under the pressure of its own vapour. Since, however, the influence of pressure on the solubility is very slight (p. 107), the position of the two points will not be greatly different. The quadruple point was found by Cohen (_Zeitschr. physikal. Chem._, 1894, 14. 90) to be 32.6° and 30.8 mm. of mercury. [212] Van't Hoff and van Deventer, _Zeitschr. physikal. Chem._, 1887, 1. 185. Cf. Cohen, _ibid._, 1894, 14. 88. [213] Debray, _Compt. rend._, 1868, 66. 194. [214] Richards, _Zeitschr. physikal. Chem._, 1898, 26. 690. A number of other salt hydrates, having transition-points ranging from 20° to 78°, which might be used for the same purpose, have been given by Richards and Churchill, _ibid._, 1899, 28. 313. [215] _Zeitschr. physikal. Chem._, 1903, 46. 818. [216] Van't Hoff, _Lectures on Physical Chemistry_, I. p. 67. [217] Cohen, _Zeitschr. physikal. Chem._, 1894, 14. 90. [218] Ziz, _Schweigger's Journal_, 1815, 15. 166. See Ostwald, _Lehrbuch_, II. 2. 717. [219] See, for example, the solubility determinations published in _Wissenschaftliche Abhandl. der physikalisch-technischen Reichsanstalt_, Vol. III., or in the _Berichte_, for the years 1897-1901. [220] Meusser, _Ber._, 1901, 34. 2440. [221] Mylius and von Wrochem, _Ber._, 1900, 33. 3693. [222] Walker and Fyffe, _Jour. Chem. Soc._, 1903, 83. 180. [223] _Monatshefte_, 1887, 8. 601. [224] The equilibria between calcium chloride and water have been most completely studied by Roozeboom (_Zeitschr. physikal. Chem._, 1889, 4. 31). [225] Hammerl, _Sitzungsber. Wien. Akad._, 2^{te} Abteil, 1878, 78. 59. Roozeboom, _Zeitschr. physikal. Chem._, 1889, 4. 31. [226] Lidbury, _Zeitschr. physikal. Chem._, 1902, 39. 453. The curvature at the melting point is all the greater the more the compound is dissociated into its components in the liquid state. If the compound is _completely undissociated_, even in the vapour phase, the two branches of the curve will _intersect_, (_e.g._ pyridine and methyl iodide; Aten, _Versl. Konink. Akad. Wetensch. Amsterdam_, 1905, 13. 462). The smaller the degree of dissociation, therefore, the sharper will be the bend. (See Stortenbeker, _Zeitschr. physikal. Chem._, 1892, 10. 194.) From the extent of flattening of the curve, it is also possible, with some degree of approximation, to calculate the degree of dissociation of the substance in the fused state. (See Roozeboom and Aten, _Zeitschr. physikal. Chem._, 1905, 53. 463; Kremann, _Zeitschr. Elektrochem._, 1906, 12. 259.) [227] See Roozeboom, _Zeitschr. physikal. Chem._, 1889, 4. 31. [228] Tammann, _Wied. Annalen_, 1899, 68. 577. [229] Duhem, _Journ. Physical Chem._, 1898, 2. 31. [230] Gibbs, _Trans. Conn. Acad._, 3. 155; Saurel, _Journ. Phys. Chem._, 1901, 5. 35. [231] In the case of the fusion of a compound of two components with formation of a liquid phase of the same composition, the temperature is a maximum; in the case of liquid mixtures of constant boiling-point, the temperature may be a minimum (p. 105). [232] Roozeboom, _Zeitschr. physikal. Chem._, 1892, 10. 477. The formula of ferric chloride has been doubled, in order to avoid fractions in the expression of the water of crystallization. [233] Roozeboom, _Zeitschr. physikal. Chem._, 1892, 10. 477. [234] A similar series of hydrates is formed by zinc chloride and water (Dietz and Mylius, _Zeitschr. anorg. Chem._, 1905, 44. 209). [235] Meyerhoffer, _Ber._, 1897, 30. 1810. [236] Walden, _Ber._, 1899, 32. 2863. [237] _Zeitschr. physikal. Chem._, 1903, 42. 432. [238] This composition was also confirmed by measurements of the vapour pressure (cf. p. 90). [239] Since all substances are no doubt volatile to a certain extent at some temperature, it is to be understood here that the substances are appreciably volatile at the temperature of the experiment. [240] For a general discussion of the partial pressures in a system of two components, see Bancroft, _Journ. Physical Chem._, 1899, 3. 1. [241] _Zeitschr. physikal. Chem._, 1889, 3. 11; _Rec. trav. chim. Pays-Bas_, 1888, 7. 152. [242] The composition of a solution is represented symbolically by placing a double wavy line between the symbols of the components, and indicating the number of atoms present in the ordinary manner: thus, I [wavy] Cl_{_x_} represents a solution containing _x_ atoms of chlorine to one atom of iodine (Roozeboom, _Zeitschr. physikal. Chem._, 1888, 2. 450). [243] Since iodine monochloride in the liquid state is only very slightly dissociated, the bend at C is very sharp (see p. 147, footnote). See also the investigation of the system pyridine and methyl iodide (Aten, _Versl. Konink. Akad. Wetensch. Amsterdam_, 1905, 13. 462). [244] This upper branch of the curve is not shown in the figure, as the ordinate corresponding to 30° would be very great. [245] Stortenbeker, _Zeitschr. physikal. Chem._, 1889, 3. 22. [246] Ramsay and Young, _Journ. Chem. Soc._, 1886, 49. 458. [247] Van't Hoff, _Lectures on Physical Chemistry_, I. p. 77 (Arnold). [248] This is different from what we found in the case of non-volatile solutes (p. 126). In the present case, the _partial pressure_ of the iodine in the vapour will be lowered by addition of chlorine, but the _total pressure_ is increased. [249] The diminution of volume is supposed to be carried out at constant temperature. The pressure and the composition of the phases must, therefore, remain unchanged, and only the relative amounts of these can undergo alteration. [250] At point _b_ the ratio of chlorine to iodine in the solution is less than in the monochloride, so that by the separation of this the excess of chlorine yielded by the condensation of the vapour is removed. [251] Roozeboom, _Rec. trav. chim. Pays-Bas_, 1884, 3. 29; 1885, 4. 65; _Zeitschr. physikal. Chem._, 1888, 2. 450. [252] Two curves "enclose" a field when they form with one another an angle less than two right angles. [253] Roozeboom, _Zeitschr. physikal. Chem._, _loc. cit._ [254] Van't Hoff, _Zeitschr. physikal. Chem._, 1890, 5. 323. [255] Bancroft has proposed to restrict the term "occlusion" to the formation of solid solutions, and to apply "adsorption" only to effects which are primarily due to surface tension. Such a distinction, however, would probably be very difficult to carry through, for although adsorption may, in large measure, be due to surface tension, the behaviour of adsorbed substances is similar to that of substances existing in solid solutions. [256] Tammann, _Wied. Annalen_, 1897, 63. 16; _Zeitschr. physikal. Chem._, 1898, 27. 323. [257] See, for example, Chappuis, _Wied. Annalen_, 1881, 12. 161; Joulin, _Annal. chim. phys._, 1881, [5], 22. 398; Kayser, _Wied. Annalen_, 1881, 12. 526. [258] Hoitsema, _Zeitschr. physikal. Chem._, 1895, 17. 1. [259] _Annales chim. phys._, 1874, [5], 2. 279. [260] Hoitsema, _Zeitschr. physikal. Chem._, 1895, 17. 1; Dewar, _Phil. Mag._, 1874, [4], 47, 324, 342; Mond, Ramsay and Shields, _Proc. Royal Soc._, 1897, 62. 290. [261] _Loc. cit._ [262] It is noteworthy that the form of curve obtained for hydrogen and palladium bears a striking resemblance to that for the dehydration of colloids containing absorbed water, _e.g._ silicic acid (_vide_ van Bemmelen, _Zeitschr. anorg. Chem._, 1897-1900. Cf. Zacharias, _Zeitschr. physikal. Chem._, 1902, 39. 480). [263] _Zeitschr. physikal. Chem._, 1890, 5. 322. [264] Küster, _Zeitschr. physikal. Chem._, 1895, 17. 367. Bodländer, _Neues Jahrbuch f. Mineralogie_, 1898-99, Beilage Band, 12. 92. [265] Bruni and Padoa, _Atti Accad. Lincei_, 1902 [5], 11. 1; 565. [266] Roozeboom, _Zeitschr. physikal. Chem._, 1899, 30. 385; Bruni, _Rend. Accad. Lincei_, 1898, 2. 138, 347. For a general account of "solid solutions" the reader is referred to Bruni, "_Ueber feste Lösungen_" (Ahrens'sche Sammlung), and to Bodländer, _loc. cit._ For the formation and transformation of liquid mixed crystals, see A. C. de Kock, _Zeitschr. physikal. Chem._, 1904, 48. 129. [267] In discussing the various systems which may be obtained here, Roozeboom (_loc. cit._) made use of the variation of the thermodynamic potential (p. 29) with the concentration. In spite of the advantages which such a treatment affords, the temperature-concentration diagram has been adopted as being more readily understood and as more suitable for an elementary discussion of the subject. [268] These curves are also called the "liquidus" and the "solidus" curve respectively. [269] Küster, _Zeitschr. physikal. Chem._, 1895, 17. 360. [270] Küster, _ibid._, 1891, 8. 589. [271] It should be remarked that the behaviour described here will hold strictly only when the solid mixed crystals undergo change sufficiently rapidly to be always in equilibrium with the liquid. This, however, is not always the case (see Reinders, _Zeitschr. physikal. Chem._, 1900, 32. 494; van Wyk, _Zeitschr. anorg. Chem._, 1905, 48. 25), and complete solidification will not in this case take place at the temperature corresponding with the line _dc_ in Fig. 50, but only at a lower temperature. [272] Adriani, _Zeitschr. physikal. Chem._, 1900, 33. 469. [273] Reinders, _Zeitschr. physikal. Chem._, 1900, 32. 494. [274] Hissink, _Zeitschr. physikal. Chem._, 1900, 32. 542. [275] Van Eyk, _Zeitschr. physikal. Chem._, 1899, 30. 430. [276] Cady, _Journ. Physical. Chem._, 1899, 3. 127. [277] See Roberts-Austen and Stansfield, _Rapports du congrès international de physique_, 1900, I. 363. [278] Heycock and Neville, _Proc. Roy. Soc._, 1903, 71. 409. For the partial liquefaction of mixed crystals on cooling, see also A. C. de Kock (_Zeitschr. physikal. Chem._, 1904, 48. 129). [279] Armstrong, _Watt's Dictionary of Chemistry_ (Morley and Muir), III., p. 88. See also Lowry, _Jour. Chem. Soc._, 1899, 75. 211. [280] See Bancroft, _Journ. Physical Chem._, 1898, 2. 143; Roozeboom, _Zeitschr. physikal. Chem._, 1899, 28. 288. [281] Hylotropic substances are such as can undergo transformation into other substances of the same composition (Ostwald, _Lehrbuch_, II. 2. 298). [282] Also called Equilibrium Point (Lowry). [283] For a discussion of these systems, see Roozeboom, _Zeitschr. physikal. Chem._, _loc. cit_. [284] See Bancroft, _loc. cit._, p. 147; Wegscheider, _Sitzungsber. Wiener Akad._, 1902, 110. 908. [285] Reference may be made here to the term "stability limit," introduced by Knorr (_Annalen_, 1896, 293. 88) to indicate that temperature above which liquefaction and isomeric change takes place. As employed by Knorr and others, the term does not appear to have a very precise meaning, since it is used to denote, not the temperature at which these changes can occur, but the temperature at which the change is rapid (vide _Annalen_, 1896, 293. 91; 1899, 306. 334); and the introduction of an indefinite velocity of change renders the temperature of the stability limit also somewhat indefinite. The definiteness of the term is also not a little diminished by the fact that the "limit" can be altered by means of catalytic agents. Since, as we have seen, the stable modification can always undergo isomeric change and liquefy at temperatures above the natural freezing point, but not below that point; and, further, the less stable modification can undergo isomeric transformation and liquefy at temperatures above the eutectic point, but will not liquefy at temperatures below that; it seems to the author that it would be more precise to identify these two points--the natural freezing point and the eutectic point--which are not altered by catalytic agents, with the "stability limits" of the stable and unstable modification respectively. A perfectly definite meaning would thereby be given to the term. In the case of those substances which do not undergo appreciable isomeric change at the temperature of the melting point, the stability limits would be the points G and H, Fig. 60. [286] Cameron, _Journ. Physical Chem._, 1898, 2. 409. [287] Carveth, _Journ. Phys. Chem._, 1898, 2. 159. See also Dutoit and Fath, _Journ. chim. phys_., 1903, 1. 358; Findlay, _Trans. Chem. Soc._, 1904, 85. 403. [288] Hollmann, _Zeitschr. physikal. Chem._, 1903, 43. 129. [289] For other examples of the application of the Phase Rule to isomeric substances, see _Journ. Physical Chem._, vols. 2. _et seq._; Findlay, _Trans. Chem. Soc._, 1904, 85. 403. [290] See Roozeboom, _Zeitschr. physikal. Chem._, 1899, 30. 410. [291] See also Saposchnikoff, _Zeitschr. physikal. Chem._, 49. 688; Kremann, _Monatshefte_, 1904, 25. 1215, 1271, 1311. [292] J. C. Philip, _Journ. Chem. Soc._, 1903, 83. 821. [293] _Cf._ also Paterno and Ampolla, _Gazzetta chim. ital._, 1897, 27. 481. [294] Philip, _loc. cit._, p. 826. [295] Philip, _loc. cit._, p. 829. Compare curves for iodine monochloride, Fig. 42, p. 162. [296] Kuriloff, _Zeitschr. physikal. Chem._, 1897, 23. 676. [297] Ladenburg, _Ber._, 1895, 28. 163; 1991. [298] Roozeboom, _Zeitschr. physikal. Chem._, 1899, 28. 494; Adriani, _ibid._, 1900, 33. 453. [299] Adriani, _Zeitschr. physikal. Chem._, 1900, 33. 453. [300] A. Findlay and Miss E. Hickmans. [301] Kipping and Pope, _Journ. Chem. Soc._, 1897, 71. 993. [302] See Roozeboom, _Zeitschr. physikal. Chem._, 1899, 28. 512; Adriani, _ibid._, 1900, 33. 473; 1901, 36. 168. [303] In this connection reference should be made more especially to the paper by Roberts-Austen and Stansfield, "Sur la constitution des alliages métalliques," in the _Rapports du congrès international de physique_, 1900, I. 363; J. A. Mathews, _Journ. of the Franklin Inst._, 1902; Gautier, _Compt. rend._, 1896, 123. 109; Roberts-Austen, "Reports of the Alloys Research Committee," in _Journ. Inst. Mechan. Engineers_, from 1891 to 1904; and the papers by Heycock and Neville, published in the _Journ. Chem. Soc._, and the _Trans. Roy. Soc._ since 1897; also Neville, _Reports of the British Association_, 1900, p. 131. Reference must also be made to the important metallographic investigations by Tammann and his pupils, and of Kurnakoff (_Zeitschr. anorgan. Chem._, vol. 40 and onwards), and also to those of Shepherd, _Journ. Physical Chem._, 8. A bibliography of the alloys is given in _Zeitschr. anorgan. Chem._, 1903, 35. 249. [304] Kurnakoff and Puschin, _Zeitschr. anorgan. Chem._, 1902, 30. 104. [305] Gautier, _Bull. Soc. d'Encouragement_, 1896 [5], 1. 1312. [306] Heycock and Neville, _Phil. Trans._, 1900, 194. 201. [307] Gautier, _loc. cit._ See also Roberts-Austen and Rose, _Proc. Roy. Soc._, 1903, 71. 161. [308] Heycock and Neville, _Journ. Chem. Soc._, 1897, 71. 414. [309] See Roberts-Austen, _Introduction to Metallurgy_, 5th edit., p. 102; Bakhuis Roozeboom, _Journ. Iron and Steel Inst._, 1900, II. 311; _Zeitschr. physikal. Chem._, 1900, 34. 437; von Jüptner, _Siderology_, p. 223 (translation by C. Salter); van't Hoff, _Zinn, Gips, und Stahl_, p. 24, or _Acht Vorträge über physikalische Chemie_, p. 37. Further, Roozeboom, _Zeitschr. Elektrochem._, 1904, 10. 489; E. Heyn, _ibid._, p. 491; Carpenter and Keeling, _Journ. Iron and Steel Inst._, 1904, 65. 224. [310] The melting point of pure iron is given by Carpenter and Keeling (_Journ. Iron and Steel Inst._, 1904, 65. 224) as 1505°. [311] _Zeitschr. für Elektrochem._, 1904, 10. 491. [312] See also Hiorns, _Journ. Soc. Chem. Ind._, 1906, 25. 50. [313] Bancroft, _Jour. Physical Chem._, 1902, 6. 178; Bell and Taber, _ibid._, 1906, 10. 120. [314] The method to be followed when the third component enters into the solid phase will be explained later. [315] Tammann, _Zeitschr. anorg. Chem._, 1903, 37. 303; 1905, 45. 24. Reference may be made here to the registering pyrometer of Kurnakoff, _Zeitschr. anorg. Chem._, 1904, 42. 184. [316] In this connection, see Doelter, _Physikalisch-chemisch Mineralogie_ (Barth, 1901); Meyerhoffer, _Zeitschr. f. Kristallographie_, 1902, 36. 593; Guthrie, _Phil. Mag._, 1884 [5], 17. 479; Le Chatelier, _Compt. rend._, 1900, 130. 85; and especially E. Baur, _Zeitschr. physikal. Chem._, 1903, 42. 567; J. H. L. Vogt, _Zeitschr. Elektrochem._, 1903, 9. 852, and _Die Silikatschmelzlösungen_, Parts I. and II. (Christiania, 1903, 1904). See also N. V. Kultascheff, _Zeitschr. anorg. Chem._, 1903, 35. 187. [317] G. G. Stokes, _Proc. Roy. Soc._, 1891, 49. 174; Gibbs, _Trans. Conn. Acad._, 1876, 3. 176; Roozeboom, _Zeitschr. physikal. Chem._, 1894, 15. 147. [318] This figure has been taken from Ostwald's _Lehrbuch_, II. 2. 984. [319] Roozeboom, _Zeitschr. physikal. Chem._, 1893, 12. 369. [320] C. R. A. Wright, _Proc. Roy. Soc._, 1891, 49. 174; 1892, 50. 375. [321] The distribution coefficient will not remain constant because, apart from other reasons, the mutual solubility of chloroform and water is altered by the addition of the acid. [322] Bancroft, _Physical Review_, 1895, 3. 21; Schreinemakers, _Zeitschr. physikal. Chem._, 1897, 23. 652, and subsequent volumes. [323] C. R. A. Wright, _Proc. Roy. Soc._, 1889-1893. [324] C. R. A. Wright, _Proc. Roy. Soc._, 1892, 50. 390. [325] Bodländer, _Berg- und Hüttenmänn. Ztg._, 1897, 56. 331. [326] C. R. A. Wright, _Proc. Roy. Soc._, _loc. cit._ [327] Schreinemakers, _Zeitschr. physikal. Chem._, 1900, 33. 78. [328] Schreinemakers, _Zeitschr. physikal. Chem._, 1898, 27. 95. [329] Schreinemakers, _Zeitschr. physikal. Chem._, 1899, 29. 577. [330] Schreinemakers, _Zeitschr. physikal. Chem._, 1898, 25. 543. [331] Charpy, _Compt. rend._, 1898, 126. 1569. Compare the curves for the system KNO_{3}--NaNO_{3}--LiNO_{3} (H. R. Carveth, _Journ. Physical Chem._, 1898, 2. 209). Also alloys of Pb--Sn--Bi (E. S. Shepherd, _Journ. Physical Chem._, 1902, 6. 527). [332] It should be remembered that in the triangular diagram a _line_ parallel to one of the sides indicates, at a given temperature, a constant amount of the component represented by the opposite corner of the triangle; and, hence, points in a _plane_, parallel to one face of a right prism, will indicate for different temperatures, variation in the amounts of two components, but constancy in the amount of the third. [333] _Gazzetta chim. ital._, 1898, 28. II. 520. [334] Bruni, _Gazzetta chim. ital._, 1898, 28. II. 508; 1900, 30. I. 35. [335] _Zeitschr. physikal. Chem._, 1900, 36. 168. [336] For a discussion of these systems, see van't Hoff, _Bildung und Spaltung von Doppelsalzen_ (Leipzig, 1897). [337] Van Leeuwen, _Zeitschr. physikal. Chem._, 1897, 23. 35. [338] Meyerhoffer, _Zeitschr. physikal. Chem._, 1889, 3. 336; 1890, 5. 97. [339] Reicher, _Zeitschr. physikal. Chem._, 1887, 1. 220. [340] For other examples of the formation and decomposition of double salts at a transition point, the reader is referred to the work by van't Hoff, already cited, on the _Bildung und Spaltung von Doppelsalzen_; or to Bancroft, _Phase Rule_, p. 180. [341] Bancroft, _Phase Rule_, p. 183. [342] Roozeboom, _Zeitschr. physikal. Chem._, 1888, 2. 514. [343] The influence of pressure on the transition point in the case of tachydrite has been determined by van't Hoff, Kenrick, and Dawson (_Zeitschr. physikal. Chem._, 1901, 39. 27, 34; van't Hoff, _Zur Bildung der ozeanischen Salzablagerungen_, I. p. 66--Brunswick, 1905). This salt is formed from magnesium chloride and calcium chloride at 22°, in accordance with the equation-- 2MgCl_{2}.6H_{2}O + CaCl_{2}.6H_{2}O = Mg_{2}CaCl_{6}.12H_{2}O + 6H_{2}O Increase of pressure raises the transition point, because the formation of tachydrite is accompanied by increase of volume; the elevation being 0.016° for an increase of pressure of 1 atm. The number calculated from the theoretical formula (p. 57) is 0.013° for 1 atm. If one calculates the influence of the pressure of sea-water on the temperature of formation of tachydrite (which is of interest on account of the natural occurrence of this salt), it is found that a depth of water of 1500 metres, exerting a pressure of 180 atm., would alter the temperature of formation of tachydrite by only 3°. The effect is, therefore, comparatively unimportant. [344] Roozeboom, _Zeitschr. physical. Chem._, 1887, 1. 227. [345] _Zeitschr. physical. Chem._, 1887, 1. 227. [346] Van't Hoff and Müller, _Ber._, 1898, 31. 2206. [347] Van't Hoff and van Deventer, _Zeitschr. physikal. Chem._, 1887, 1. 165. [348] For a full discussion of the solubility relations of sodium ammonium racemate, see van't Hoff, _Bildung und Spaltung von Doppelsalzen_, p. 81. [349] _Annales chim. phys._, 1848 [3], 24. 442. [350] See Van't Hoff and van Deventer, _Zeitschr. phys. Chem._, 1887, 1. 165. [351] Meyerhoffer, _Zeitschr. physikal. Chem._, 1890, 5. 121. [352] Roozeboom, _Zeitschr. physikal. Chem._, 1888, 2. 518. [353] Meyerhoffer, _Zeitschr. physikal. Chem._, 1890, 5. 109. On the importance of the transition interval in the case of optically active substances, see Meyerhoffer, _Ber._, 1904, 37. 2604. [354] In connection with this chapter, see, more especially, van't Hoff, _Bildung und Spaltung von Doppelsalzen_, p. 3, _ff._; Roozeboom, _Zeitschr. physikal Chem._, 1892, 10. 158; Bancroft, _Phase Rule_, p. 201; 209. [355] The same restriction must be made here as was imposed in the preceding chapter, namely, that the two salts in solution give a common ion. [356] For example, addition of ammonium chloride to solutions of ferric chloride (Roozeboom, _Zeitschr. physikal. Chem._, 1892, 10. 149). [357] It must, of course, be understood that the temperature is on that side of the transition point on which the double salt is stable. [358] Excess of the double salt must be taken, because otherwise an unsaturated solution might be formed, and this would, of course, not deposit any salt. [359] Meyerhoffer, _Ber._, 1904, 37. 2605. [360] Meyerhoffer, _Ber._, 1897, 30. 1809. [361] Meyerhoffer, _Ber._, 1904, 37. 2604. [362] Bancroft, _Phase Rule_, p. 203; Roozeboom, _Zeitschr. physikal. Chem._, 1891, 8. 504, 531; Stortenbeker, _ibid._, 1895, 17. 643; 1897, 22. 60; 1900, 34. 108. [363] Roozeboom, _Zeitschr. phys. Chem._, 1899, 28. 494; _Ber._, 1899, 32. 537. [364] As, for instance, strychnine racemate, a compound of racemic acid with the _optically active_ strychnine. This would be resolved into strychnine _d_-tartrate and strychnine _l_-tartrate, which are not enantiomorphous forms. [365] Van't Hoff and Meyerhoffer, _Zeitschr. physikal Chem._, 1898, 27. 75; 1899, 30. 86. Fig. 113 is taken from the latter paper. [366] Solid models constructed of plaster of Paris can be obtained from Max Kaehler and Martini, Berlin. [367] Instead of the present method of obtaining potassium chloride by decomposing carnallite with water, advantage might be taken of the fact that carnallite when heated to 168° undergoes decomposition with separation of three-fourths of the potassium chloride (van't Hoff, _Acht Vorträge über physikalische Chemie_, 1902, p. 32). [368] Roozeboom and Schreinemakers, _Zeitschr. physikal. Chem._, 1894, 15. 588. [369] These curves represent only portions of the isotherms, since the systems in which a ternary solution is in equilibrium with solid hydrogen chloride or a hydrate, have not been investigated. [370] The numbers printed beside the points on the curves refer to the number of the experiment in the original paper. [371] Lash, Miller and Kenrick, _Journ. Physical. Chem._, 1903, 7. 259; Allan, _Amer. Chem. Journ._, 1901, 25. 307. [372] Allan, _Amer. Chem. Journ._, 1901, 25. 307. [373] Hoitsema, _Zeitschr. physikal. Chem._, 1895, 17. 651; Allan, _loc. cit._ [374] Rutten, _Zeitschr. anorgan. Chem._, 1902, 30. 342. Compare the system BeO--SO_{3}--H_{2}O; Parsons, _Zeitschr. anorgan. Chem._, 1904, 42. 250. [375] _Zeitschr. anorgan. Chem._, 1904, 40. 146. [376] Schreinemakers, _Zeitschr. physikal. Chem._, 1893, 11. 76; Bancroft, _Journ. Physical Chem._, 1902, 6. 179. [377] _Zeitschr. anorgan. Chem._, 1904, 40. 148. [378] _Zeitschr. physikal. Chem._, 1903, 43. 354. [379] These equilibria were obtained by Boudouard, _Annales chim. phys._, 1901 [7], 24. 5. See also Hahn, _Zeitschr. physikal. Chem._, 1903, 42. 705; 44. 513. [380] G. Preuner, _Zeitschr. physikal. Chem._, 1903, 47. 385. [381] See Hahn, _Zeitschr. physikal. Chem._, 1903, 42. 705; 44. 513; Boudouard, _Bull. Soc. chim._, [3], 25. 484; Bodländer, _Zeitschr. f. Elektrochem._, 1902, 8. 833; R. Schenck and Zimmermann, _Ber._, 1903, 36. 1231, 3663; Schenck and Heller, _ibid._, 1905, 38. 2132; _Zeitschr. f. Elektrochem._, 1903, 9. 691; Haber, _Thermodynamik technischer Gasreaktionen_, p. 293 (Munich, 1903). [382] A very useful summary of the investigations carried out by van't Hoff and his pupils on the formation of the Stassfurt salt-beds is given by E. F. Armstrong, in the _Reports of the British Association for 1901_, p. 262. See also van't Hoff, _Zur Bildung der ozeanischen Salzablagerungen_ (Brunswick, 1905). [383] See especially Meyerhoffer, _Silzungsber. Wien. Akad._, 1895, 104. II. _b_, 840; Meyerhoffer and Saunders, _Zeitschr. physikal. Chem._, 1899, 28. 453; 31. 370. The investigation of the equilibria between reciprocal salt-pairs alone (three-component systems) is of great importance for the artificial preparations of minerals, as also in analytical chemistry for the proper understanding of the methods of conversion of insoluble systems into soluble by fusion (see Meyerhoffer, _Zeitschr. physikal. Chem._, 1901, 38. 307). [384] See Meyerhoffer, _Zeitschr. physikal. Chem._, 1899, 28. 459. [385] Compare the reciprocal salt-pair NaCl--NH_{4}HCO_{3} (p. 321). In this case the upper limit of the transition interval was found by extrapolation of the solubility curve for NaHCO_{3} + NH_{4}Cl + NH_{4}HCO_{3} and NaHCO_{3} + NH_{4}Cl + NaCl to be 32° (Fedotieff, _Zeitschr. phys. Chem._, 1904, 49. 179). [386] Löwenherz, _Zeitschr. physikal. Chem._, 1894, 13. 464. [387] Meyerhoffer and Saunders, _Zeitschr. physikal. Chem._, 1899, 28. 479. [388] As the quantities of the salts are expressed in _equivalent_ gram-molecules, the molecule of sodium and potassium chloride must be doubled in order to be equivalent to sodium sulphate and potassium sulphate. [389] _Sitz-Ber. der kgl. preuss. Akad. der Wiss._, 1903, p. 359. Van't Hoff, _Zur Bildung der ozeanischen Salzablagerungen_, I. p. 34 (Brunswick, 1905). [390] _Zeitschr. für Kristallographie_, 1904, 39. 155. [391] Meyerhoffer and Saunders, _Zeitschr. physikal. Chem._, 1899, 28. 479. [392] _Zeitschr. physikal. Chem._, 1904, 49. 162. [393] Another commercial process, in the study of which good service is done by the Phase Rule, is the caustification of the alkali salts (G. Bodländer, _Zeitschr. für Elektrochem._, 1905, 11. 186; J. Herold, _ibid._, 418). [394] _Zeitschr. physikal. Chem._, 1900, 35. 32. [395] Mention may also be made here of the equilibria between magnesium carbonate and potassium carbonate, although these do not form a reciprocal salt-pair (Auerbach, _Zeitschr. für Elektrochem._, 1904, 10. 161). [396] O. N. Witt and K. Ludwig, _Ber._, 1903, 36. 4384; Meyerhoffer, _ibid._, 1904, 37. 261, 1116. [397] _Zeitschr. physikal. Chem._, 1905, 53. 513. Compare also, _ibid._, 1903, 38. 307. [398] See Schwarz, _Beiträge zur Kenntnis der umkehrbaren Umwandlungen polymorpher Korper_ (Göttingen, 1892); or, Roozeboom, _Heterogen. Gleichgewicht_, I. p. 125. Also Barnes and Cooke, _Journ. Physical Chem._, 1902, 6. 172. [399] Van't Hoff and van Deventer, _Zeitschr. physikal. Chem._, 1887, 1. 173. [400] Reicher, _Zeitschr. für Krystallographie_, 1884, 8. 593. [401] _Zeitschr. physikal. Chem._, 1895, 17. 153. [402] _Zeitschr. physikal. Chem._, 1899, 28. 464. [403] Meyerhoffer and Saunders, _ibid._, p. 466. [404] See Van Eyk, _Zeitschr. physikal. Chem._, 1899, 30. 446. [405] See in this connection the volume in this series on _Electro-chemistry_, by Dr. R. A. Lehfeldt. [406] Barnes and Cooke, _Journ. Physical Chem._, 1902, 6. 172. [407] For a description and explanation of these, the reader should consult the volume in this series by Dr. Lehfeldt on _Electro-chemistry_; and van't Hoff, _Bildung und Spaltung von Doppelsalzen_, p. 48 _ff._ * * * * * Changes made to the printed original. Pages 30-31. "Fig. 3, p. 27.": 'p. 25." in original. So also page 33, "Fig. 2, p. 27". Page 57. "pp. 29 and 35": 'pp. 25 and 38" in original. Page 65. "p. 57.": 'p. 60" in original (twice). Page 166. "there is the point C_{1}": C' in original. Page 225. "C is an eutectic point": 'eutetic' in original. Page 228. "Although this view put forward by Heyn": 'Athough' in original. Page 232. "the period of constant temperature for the eutectic point c": 'the eutectic point e' in original. Page 249. "two liquid layers between 13° and 31°": 'betwen' in original. Page 257. Tables entries 4 and 7. "naphthol": 'napthol' in original. Page 287. "from which the model is constructed": 'he model' in original. 
37682	----	[Transcriber's Note: A few typographical errors have been corrected. Details are given at the end of the text.] HEADS OF LECTURES ON A COURSE OF EXPERIMENTAL PHILOSOPHY, PARTICULARLY INCLUDING CHEMISTRY, DELIVERED AT THE NEW COLLEGE IN HACKNEY. _By JOSEPH PRIESTLEY, LL.D. F.R.S._ AC. IMP. PETROP. R. PARIS. HOLM. TAURIN. AUREL. MED. PARIS. HARLEM. CANTAB. AMERIC. ET PHILAD. SOC. QUI DOCET DISCIT.--WM. LILLY LONDON: PRINTED FOR J. JOHNSON, NO. 72, ST. PAUL'S CHURCH-YARD. 1794. THE PREFACE. Situated, as I happily am, in the neighbourhood of the _New College at Hackney_, an institution that does honour to the Dissenters, an institution open to all persons without distinction[1], and connected as I am by friendship with the tutors, I was glad to give it every assistance in my power; and therefore undertook to read the _Lectures on History and General Policy_ which I had composed when I was tutor at Warrington, and also to give another course on the subject of _Experimental Philosophy_. With this view I drew up the following _Heads of Lectures_; and, to save the students the trouble of transcribing them, they are now printed. To other persons they may serve as a compendious view of the most important discoveries relating to the subject. [Footnote 1: One gentleman of the Roman Catholic persuasion, and several of the Church of England, are now in the College.] As it was found most convenient, with respect to the other business of the college, to confine this course to one lecture in a week, I contrived to bring within that compass as much of the subject of experimental philosophy as I well could, and especially to include the whole of what is called _chemistry_, to which so much attention is now given, and which presents so many new fields of philosophical investigation. Besides that the plan of the young gentlemen's studies would not admit of it, I think it most advisable not to trouble beginners with more than a large outline of any branch of science. By this means they are not fatigued by too long an attention to any one subject, a greater variety of articles may be brought before them, and in future life they may pursue any of them as much farther as their inclination may dispose, and their ability and opportunity shall enable, them to do it. I do not give any account of the _experiments_ introduced into the several lectures. They will be sufficiently indicated by the subjects of them. They were as many as I could conveniently make within the time; and where the experiments themselves could not be made, I usually exhibited both the different substances employed in them, and those that were the result of them. As these lectures were calculated for the use of the students at the New College, I prefix an _Address to them_, the same in substance with that which I delivered to them at the close of the session of 1791. In it may be seen a specimen of the language we hold to them on the subject of _politics_, which with reasonable men will serve as an answer to the many calumnies that have been thrown out against us, as disaffected to the government of this country. Such institutions will, indeed, always be objects of hatred and dread to _bigots_ and the advocates for _arbitrary power_, but the pride of a truly _free country_. I therefore conclude with my earnest prayer (the accomplishment of which the present state of the College does not allow us to doubt) ESTO PERPETUA. THE DEDICATION. TO THE STUDENTS AT THE NEW COLLEGE IN HACKNEY. My young Friends, Having drawn up the following _Heads of Lectures_ for your use, I take the liberty thus publickly to dedicate them to you; and as I earnestly wish for your improvement and happiness in all respects, excuse me if I take the farther liberty of making a few observations, and giving you some advice, of a more general nature, adapted to your age and circumstances. As you will soon leave this place of education, and enter upon your several professions and employments, I hope your conduct will demonstrate to the world the solid advantages of this institution, and that the great expence attending it, and the best attention of the managers, have not been bestowed in vain. Many liberal friends of science, of virtue, and of religion, have contributed to procure you the advantages which you enjoy. They have spared no pains to provide able and careful tutors, and you have had every other advantage for the prosecution of your studies that they could procure you, unclogged by any subscription to articles of faith, or obligation of any other kind, besides such as they have deemed necessary for your own good, and to give the institution its greatest effect. This is an advantage you could not have found elsewhere, at least in this country. And in every seminary of education much more depends upon opportunity for study, free from any obstruction, and undue bias, than upon the ability of tutors; though there is an additional advantage when they are able men, and eminent in the branches of science which they undertake to teach. But this is by no means so essential as many other circumstances. Whatever be the qualifications of your tutors, your improvement must chiefly depend upon yourselves. They cannot _think_ or _labour_ for you. They can only put you in the best way of thinking and labouring for yourselves. If, therefore, you get knowledge, you must acquire it by your own industry. You must form all conclusions, and all maxims, for yourselves, from premises and _data_ collected, and considered by yourselves. And it is the great object of this institution to remove every bias the mind can lie under, and give the greatest scope to true freedom of thinking and inquiry. And provided you be intelligent and virtuous men, and good citizens, it will be no cause of regret to the friends of this institution, if, with respect to _religion_, or _politics_, you adopt systems of principles, and maxims of conduct, very different from theirs. Give me leave, now that I am addressing you as _young men_, and young _students_, to suggest a caution on a subject, of the importance of which it is hardly possible that you should be sufficiently aware, because it is only impressed by that _experience_ which you have not yet had. I mean that degree of vanity which generally accompanies the acquirements that diligent persons of your age make in places of liberal education, and the contempt they are too apt to entertain for those who have not made the same proficiency with themselves. And I assure you, that in the observations I shall make on this subject, I have no view whatever to any thing that I have observed, or heard, of any of you in particular. But I have been in your situation myself, and I know the importance of these observations to students in general. You are now at an age in which young persons usually make the most sensible advances in knowledge, and in which the understanding appears to ripen the most rapid manner. You are able to say every year, every month, and almost every day, what particular advances you have made, and how much you know more than you did before. And being taught, and accustomed, to express your thoughts in writing, you find yourselves qualified to do this in a manner of which you had no idea, or expectation, but a little time ago. You also perfectly remember what you have so recently learned, and many respects may be more particular and exact than even your tutors themselves. The almost unavoidable effect of this is a high idea of your own powers and attainments, and too often a proportionable contempt of those who, not having had equal advantages, cannot do what you are easily capable of. A certain degree of vanity is, therefore, excusable in young persons; and, indeed, it is by means of it that they are excited to exert themselves in a manner that they would not otherwise have done. But be careful that this temper be not indulged to excess, for it will then be found to have serious ill consequences; the least of which is the precluding future improvement, from being already satisfied with yourselves, and conscious of a sufficient superiority over others. The foundation of this self-conceit, on account of literary attainments, will be found to be extremely weak. In fact, we learn more before the period to which you are now arrived, and I hope you will continue to learn more after it, without its being so much noticed; and the _ability_ that is discovered in the acquirements which are the subjects of this vanity is not greater than appears on other occasions. Only they are not so conspicuous. What we all learn in the first three years of our lives, is much more extraordinary in its nature than all that we acquire afterwards. I mean the perfect use of our limbs, and the elements of speech. What we learn in a month in that early period of life, could not, if we were brought up in the ignorance of it, be learned in a year at any subsequent period. But these acquirements being universal, and what the circumstances in which we are all necessarily in compel us to learn, it does not appear extraordinary in any particular individual. Also, the proficiency that boys make at a grammar school, in which, in general, the dead languages only are taught (a knowledge of which is commonly the result of severe application) is too common to be the cause of much self-conceit. But the advances that are made at places of liberal education are both less common, and of a more conspicuous nature. You will also find, if you continue your application to study, that it is only the elements of science that you can acquire here, and that if you live many years, they will bear but a small proportion to your future acquirements. But those future acquirements, in consequence of their bearing a less proportion to your whole stock of knowledge, will not be so conspicuous. Thus, though all the buildings that in one year are added to such a city as London would make a pretty large country town, they bear so small a proportion to what was built before, that they are not much noticed; whereas, had half the quantity of building been erected in a place where no house had existed before, it would have been a memorable event in the history of the country. Also, as in old cities many buildings will fall to decay, while new ones are added; you must expect to forget much of what you now know. No man can give equal attention to every object; and as we advance in life, we, in general, only learn new things at the expence of the old ones. But then they are the more valuable articles of knowledge, the more general and leading principles, which remain with us; while the more useless ones, things to which we give less attention because we find them to be of less use, disappear. Yet it is no uncommon thing for ingenious students to despise old scholars who are not so ready in the _minutiæ_ of literature, though they may have forgotten more than those youths ever knew, and may retain what they cannot acquire without forgetting as much. Another observation proper to lessen the conceit of literary men, is, that genius is not confined to _them_, but is equally great, though not equally conspicuous, in every other line of life, and especially in manufactures and the arts. Here, however, discoveries equal, with respect to _sagacity_, to those of Newton, contribute little to posthumous fame, because the discoverers are not writers. But the greatest branch of intellectual excellence with respect to which every other is nothing, and which, from its nature, can never be foundation of any self-conceit, is _virtue_, or right dispositions of mind, leading to right conduct in life. Proper sentiments, and just affections of mind, arise from just, and often comprehensive, views of things, past, present, and to come. And if the real greatness of any thought, or action, be estimated by the number of elements that constitute it, and its remoteness from the dictates of sense and natural appetite, a virtuous and pious man will appear to be a much more dignified character, more proper to be viewed with admiration and esteem, than the greatest scholar; discovering, in fact, greater comprehension and force of mind. I mean, however, that virtue which is the result of reflection, of discipline, and much voluntary exertion, which, though operating with equal promptness and facility, is as much superior to mere _innocence_, and what is commonly called _good nature_, as motions secondarily automative are to those that are primarily so; a comparison which you who have studied _Hartley's Theory of the Mind_ will see the force of. These considerations I take the liberty to suggest, as being proper to lessen that vanity which is so incident to those who distinguish themselves in the fields of literature, and which, operating like the acquisition of riches, or power, or any possession that is _rare_ among men, instead of enlarging, may tend to contract the mind, by confining its attention to itself. Beginning with a generous emulation, it proceeds to envy and jealousy, and ends in actual hatred and malignity, against which you cannot, surely, be too strongly put upon your guard; this being the greatest depravity to which human nature is subject, and which yet, like any other vice, may be in full possession of the mind, without the person himself knowing, or suspecting it; unless he give more attention to his feelings than most persons do. If no man ever thought himself to be avaricious, or cruel, can it be expected that any person should ever discover that he is too self-conceited? Better, however, infinitely better, were it to rank with the merest dunces, than have the conceit and malignity (produced originally from conceit) of some who have distinguished themselves the most as linguists, critics, and poets. Even the study of nature, though, from its vast extent, it is less apt to produce this baneful effect, is not always a sufficient guard against it. This is an affecting and an alarming consideration. But in the intellectual, as in the civil and commercial world, we gain nothing but at the risk of some loss; and in this case the possible gain is worth the risk of even this great loss. For when literary, and scientific excellence coincide with that which is of a moral nature, it adds unspeakably to the value of a character. Ingenuity coupled with modesty, and great genius with benevolence and true piety, constitute the perfection of human character, and is what we should ever have in view. And a course of education in which both these objects are equally attended to, is the only one that deserves to be called _liberal_: but such as, I hope, you have found this to be. Give me leave further to observe to you, that the time that you spend in a place of liberal education is of more importance to you than you can be at present aware of. Whatever be the sphere of life for which you are destined, the probability is, that you will hereafter have but little leisure for reading and studying, compared to what you have now. Besides, general maxims of all kinds, such as are the foundation of all our future conduct, in morals, religion, or politics, are generally formed at your time of life. From this period expect no great change in your opinions, or conduct; because now it is that you give particular attention to the forming your opinions on all subjects of importance; so that very little that is materially new to you can be expected to occur to you in future life, and almost every thing that you would choose to read will only tend to confirm you in the general principles that you will now adopt. There are, no doubt, exceptions to this, as well as every other general observation; but it is wisdom to suppose, and to act upon the supposition, that we are constituted as the generality of mankind are, and that we shall feel, and act, as they do. Since, then, so much depends on the leading principles and maxims which you will now adopt, be it your care to form just and good ones, and let no authority of tutors, or others, have any undue influence over you. In all cases think and judge for yourselves, and especially on all subjects of importance, and with as much attention as you can give to them. It may not be amiss, in the present state of things, to say something respecting another subject, which now commands universal attention. You cannot but be apprised, that many persons entertain a prejudice against this College, on account of the republican, and, as they choose to call them, the licentious, principles of government, which are supposed to be taught here. Show, then, by your general conversation, and conduct, that you are the friends of peace and good order; and that, whatever may be your opinions with respect to the best form of government for people who have no previous prejudices or habits, you will do every thing in your power for the preservation of that form of it which the generality of your countrymen approve, and under which you live, which is all that can be reasonably expected of any subject. As it is not necessary that every good son should think his parent the wisest and best man in the world, but it is thought sufficient if the son pay due respect and obedience to his parent; so neither is it to be expected that every man should be of opinion that the form of government under which he happens to be born is the best of all possible forms of government. It is enough that he submit to it, and that he make no attempt to bring about any change, except by fair reasoning, and endeavouring to convince his countrymen, that it is in their power to better their condition in that respect, as well as in any other. Think, therefore, speak, and write, with the greatest freedom on the subject of government, particular or general, as well as on any other that may come before you. It can only be avowed tyranny that would prevent this. But at the same time submit yourselves, and promote submission in others, to that form of government which you find to be most approved, in this country, which at present unquestionably is that by _King, Lords, and Commons_. As to _religion_, we may, surely, be allowed to think and act entirely for ourselves; in all cases obeying God and conscience rather than man. But let us be thankful for the degree of liberty that we are allowed, though it be not all that we are justly entitled to; and let us not use any other means than reason and argument in order to better our condition. By this peaceable and steady conduct we shall at length convince those who will hear reason, that we are entitled to greater consideration; and doubt not but whatever is _true_ and _right_, will finally prevail, and be universally established. That any of your tutors, or any of the friends of this institution, wish to promote reformation, in church or state, by any other means than those of reason, and argument, is a _calumny_, utterly void of foundation, or probability. But your conduct, dispersed as you will soon be in different parts of the country, will be the best means of refuting it. Let us leave the method of proceeding by _riot_ and _tumult_ to those persons to whose schemes such proceedings are congenial. Truth stands in no need of such support, and will always triumph when assailed by such weapons. In return, then, for the advantages which you have enjoyed in this institution, do it this service; and in recommending it, I trust you are doing substantial service to the cause of liberty and truth; and conferring a most important benefit on your country, and on mankind. CONTENTS. LECTURE I. _The Introduction_ 1 LECTURE II. _Of the Properties of all Matter_ 9 _Of Aeriform Substances_ 13 LECTURE III. _Of Atmospherical Air_ 15 LECTURE IV. _Of Dephlogisticated Air_ 18 _Of Phlogisticated Air_ 20 LECTURE V. _Of Inflammable Air_ 21 LECTURE VI. _Of Nitrous Air_ 23 LECTURE VII. _Of Fixed Air_ 27 _Of Hepatic Air_ 29 _Of Phosphoric Air_ 30 LECTURE VIII. _Of Dephlogisticated Marine Acid Air_ 31 _Of Phlogisticated Marine Acid Air_ 32 LECTURE IX. _Of Vitriolic Acid Air_ 34 _Of Fluor Acid Air_ 36 LECTURE X. _Of Alkaline Air_ 37 _Miscellaneous Observations relating to Air_ 38 LECTURE XI. _Of Liquid Substances; and first of Water_ 41 LECTURE XII. _Of the Nitrous Acid_ 45 LECTURE XIII. _Of the Vitriolic Acid_ 49 _Of the Marine Acid_ 52 LECTURE XIV. _Of the Vegetable Acids, and others of a less perfect nature_ 54 LECTURE XV. _Of the Phosphoric Acid_ 59 LECTURE XVI. _Of Alkalis_ 62 LECTURE XVII. _Of Liquid Inflammable Substances_ 66 _Of Æther_ 68 LECTURE XVIII. _Of Oil_ 70 LECTURE XIX. _Of Solid Substances_ 76 _Of Calcareous Earth_ 77 _Of Siliceous Earth_ 79 LECTURE XX. _Of Argillaceous Earth_ 81 _Of Terra Ponderosa_ 82 _Of Magnesia_ 83 LECTURE XXI. _Of Ores_ 84 _Of Gold_ 87 LECTURE XXII. _Of Silver_ 90 _Of Platina_ 92 LECTURE XXIII. _Of Mercury_ 94 LECTURE XXIV. _Of Lead_ 99 _Of Copper_ 101 LECTURE XXV. _Of Iron_ 105 LECTURE XXVI. _Of Tin_ 109 _Of the Semi-metals_ 113 LECTURE XXVII. _Of Nickel_ 115 _Of Arsenic_ 116 _Of Cobalt_ 118 _Of Zinc_ 119 LECTURE XXVIII. _Of Antimony_ 121 _Of Manganese_ 123 _Of Wolfram_ 124 _Of Molybdena_ 125 _Of Solid Combustible Substances_ 126 LECTURE XXIX. _Of the Doctrine of Phlogiston and the Composition of Water_ 127 LECTURE XXX. _Of Heat_ 135 LECTURE XXXI. _Of Animal Heat_ 145 LECTURE XXXII. _Of Light_ 148 LECTURE XXXIII. _Of Magnetism_ 155 LECTURE XXXIV. _Of Electricity_ 162 LECTURE XXXV. _The same Subject continued_ 170 LECTURE XXXVI. _The same Subject continued_ 177 LECTURES ON EXPERIMENTAL PHILOSOPHY. LECTURE I. _The Introduction._ The object of experimental philosophy is the knowledge of nature in general, or more strictly, that of the properties of natural substances, and of the changes of those properties in different circumstances. This knowledge can only be attained by _experiment_, or _observation_; as that clay is capable of becoming hard by means of fire, and thereby being made into bricks, and that by the same means lime-stone can be converted into quick-lime, and by the addition of water and sand, make mortar. It is by observation also that we discover that stones and other heavy bodies fall to the ground, and that a magnet will attract iron. In other words, experimental philosophy is an investigation of the wisdom of God in the works and _the laws of nature_, so that it is one of the greatest objects to the mind of man, and opens a field of inquiry which has no bounds; every advance we make suggesting new doubts and subjects of farther inquiry. The uniformity we discover in the properties of natural substances enables us to lay down general rules, or principles, which, being invariable, we call the laws of nature; and by our knowledge of these laws we are able to predict, and at our own pleasure to produce, particular results, and this is the source of all the powers of man. It is the direction we acquire of the powers of nature; so that, as Lord Bacon observed, _knowledge is power_. All arts and manufactures are derived from science. Thus the doctrine of _mechanics_ is an application of the law of gravitation. Every thing we are capable of doing by means of the steam-engine is derived from our knowledge of the properties of water in steam; all the great effects of gunpowder we owe to our knowledge of the composition, and chemical properties, of that substance. Every new appearance in nature is preceded by some new circumstance, and to this, or rather to something always attending it, we say that the appearance is _owing_. This circumstance we therefore call the _cause_, and the new appearance the _effect_ of that cause. Thus we say that the union of phlogiston to a particular kind of earth is the cause of its becoming a metal. It is one of the principal rules of philosophizing to admit no more causes than are necessary to account for the effects. Thus, if the power of gravity, by which heavy bodies fall to the earth, be sufficient to retain the planets in their orbits, we are authorized to reject the _Cartesian Vortices_. In other words, we must make no more general propositions than are necessary to comprehend all the particulars contained in them. Thus, after having observed that iron consists of a particular kind of earth united to phlogiston, and that it is soluble in acids; and that the same is true of all other metallic substances, we say, universally, that all metals consist of a peculiar earth and phlogiston, and that they are all soluble in some acid. Of the circumstances which occasion a change in the properties of bodies, some are the addition of what are properly called _substances_, or things that are the objects of our senses, being _visible_, _tangible_, or having _weight_, &c. Thus the addition of an acid changes an alkali into a neutral salt. But other changes are occasioned either by a change of texture in the substance itself, or the addition of something that is not the object of any of our senses. Thus, a piece of steel becomes a magnet by the touch of another magnet, and a drop of glass acquires the property of flying asunder by a small fracture, in consequence of falling when red hot into cold water. Such also, in the opinion of some, is the difference between hot and cold substances. Till the nature of the cause be ascertained, it is convenient to make use of the term _principle_, as including both of the above-mentioned causes of the change of properties in bodies. Thus, whatever be the real cause of gravity, or of inflammability, we may speak of the _principle of gravity_, or of _inflammability_; whether, with Newton, we suppose gravity to be occasioned by a fluid pervading the whole universe, which he termed _æther_, and whether inflammability be caused by the presence of a real substance called phlogiston, or not. In this manner we use the letters _x_ and _y_ to denote unknown quantities in algebra. When changes are made in substances by the addition of other substances, they make what is called a _chemical union_; and in this case the properties of the compound cannot with any certainty be deduced from those of the component parts, but must be ascertained by fresh experiments. Thus, from the specific gravities, or the degrees of fusibility, of two metals, those of the compound cannot be predicted. Neither water nor acid of vitriol will separately dissolve iron, so as to produce inflammable air, but both together will do it. However, the properties of similar compounds are similar to one another. Thus, all metals dissolved in acids are precipitated by mild alkalis. This chemical union of two substances we ascribe to a certain _elective attraction_, or _affinity_ that subsists between them, in consequence of which they unite with one another whenever a proper opportunity offers, in preference to those substances to which they were before united. Thus the vitriolic acid, having a stronger affinity with the vegetable alkali which is the basis of nitre, will unite with that alkali, and with it form another compound, called _vitriolated tartar_, while the acid of nitre, being detached from its base, is collected separately. When two substances compose one liquid, and a third, which has a stronger affinity with either of the two parts than they have with each other, is added to them, it will unite with that part, and take its place in the solution, while the other will in many cases be precipitated, and may be collected. Thus the earth of alum is precipitated from a solution of alum by salt of tartar. This is the case of _simple affinity_. When both the substances are compounds, the component parts of which have a weaker affinity with each other than they have with those of the other compound, two new combinations are formed, and this is called a case of _double affinity_. Thus when phlogisticated alkali is poured into a solution of green vitriol, the acid of the vitriol unites with the alkali, while the phlogiston joining the calx of iron makes Prussian blue. All nature lying open to our investigation, we must consider the different parts in some order. But it is not very material which we adopt, because, begin where we will, the properties of the substances we first treat of will be connected with those which must be particularly considered afterwards, the changes in one substance being occasioned by its union with another. It will be impossible, for example, to explain the properties of metals without considering the _acids_, because by their union with acids very important changes are made in their properties. There have been three principal methods of arranging natural substances. One is according to the _three kingdoms_, as they are called, into which they have been distributed, viz. the _mineral_, the _vegetable_, and the _animal_. Another is according to the _elements_ which enter into their composition, and a third according to the _form_ in which they are usually found, viz. _aerial_, _fluid_, or _solid_. Upon the whole this last appears to me to be the most convenient, especially as it is easy to intermix general observations concerning the other divisions when they are particularly wanted. As there will be frequent occasion to speak of the component and elementary parts of all substances, I shall here observe, that, according to the latest observations, the following appear to be the elements which compose all natural substances, viz. _dephlogisticated air_, or the _acidifying principle_; _phlogiston_, or the _alkaline principle_; the different _earths_, and the principles of _heat_, _light_, and _electricity_. Besides these, there are the following principles which have not been proved to be substances, viz. _attraction_, _repulsion_, and _magnetism_. By the help of these principles we are able, according to the present state of natural knowledge, to explain all the appearances that have yet occurred to us. LECTURE II. _Of the Properties of all Matter._ Before I consider the properties of particular substances, it will be proper to mention those which are common to them all. But I shall first observe, that the term _substance_ has no proper idea annexed to it, but is merely a convenience in speech; since we cannot speak of the properties of substances, such as _hard_, _round_, _coloured_, &c. &c. (which circumstances alone affect our senses, and thereby give proper ideas) without saying that they inhere in, or belong to, some _thing_, _substance_, or _substratum_. The terms _being_ and _person_ are also in the same predicament. One property of all substances is _extension_, since they all occupy some portion of space. The incapacity of any substance to change its place has been termed, though improperly, the _vis inertiæ_ of matter. It is sufficient to say, that neither this, nor any other effect can be produced without a cause. _Infinite divisibility_ is a necessary property of all extended substance; and from this circumstance it will follow, that the smallest quantity of solid matter may be made to fill the largest space, and yet none of the pores shall exceed the smallest given magnitude; and consequently, that, for any thing we know to the contrary, all the bodies in the universe may be comprized in the smallest space. Another property usually ascribed to all matter is _impenetrability_, or the necessary exclusion of any substance from the place occupied by another. But the only proof of impenetrability is the _resistance_ that we find to our endeavours to put one substance into the place of another; and it is demonstrated by experiments, that this resistance is not occasioned by the actual contact of the substances, but by a power of repulsion acting at a real distance from their surfaces. It requires a considerable force to bring two solid substances into as near contact as the particles of the same substance; and that _these_ are not in actual contact is evident, from their being capable of being brought nearer by cold; and this is most remarkable with respect to the heaviest, that is, the densest, of all substances, viz. the metals. A more positive argument for the penetrability of matter is, that the particles of light, after entering the densest transparent substance, do not appear to meet with any obstruction to their progress till they come to the opposite side. The powers of _attraction_ and _repulsion_ seem to be common to all matter, and the component parts of all substances are kept in their places by the due balance of those opposite powers. If, by any means, the particles of any substance be removed beyond their sphere of mutual attraction, they repel one another, as those of water when it becomes steam. Of the different kinds of attraction, that of _gravitation_ seems to extend to the greatest possible distance; but that which keeps together the parts of the same substance, thence called the _attraction of cohesion_, and the different kinds of chemical attractions, called _affinities_, only act at a small distance. Of the causes of these attractions we are entirely ignorant. _Of Aeriform Substances._ Aeriform substances, of which the air that we breathe is one, though invisible, are real substances, as appears by their excluding other substances. That the air has _weight_ appears by actually weighing a vessel before and after it is exhausted of air by means of an air-pump (an instrument contrived for that purpose) by its bursting a bladder, and various other experiments. Air, being a fluid, presses in all directions, as in the experiment of the fountain in _vacuo_, and others. The weight of the air is the cause of the suspension of mercury in a barometer, and of the action of pumps. The weight of atmospherical air is to that of water in the proportion of about 1 to 800, so as to press with the weight of about fourteen pounds on every square inch of surface. Air, being an elastic fluid, is capable of occupying more or less space according to the pressure which it sustains, as appears by a bladder partially filled with air being expanded when the air is drawn from a receiver in which it is put, by means of the air-pump, and compressed in the condensing engine, an instrument the reverse of the air-pump. Air is necessary to the conveyance of sound, to the existence of flame, and to animal life. LECTURE III. _Of Atmospherical Air._ The first species of air that offers itself to our consideration is that of the atmosphere, which appears to consist of a mixture of two kinds of air, of different and opposite qualities, viz., dephlogisticated and phlogisticated, in the proportion of about one third of the former to two thirds of the latter. It is by means of the former of these two ingredients that it is capable of supporting flame and animal life. This composition of atmospherical air is proved by several substances absorbing the dephlogisticated air, and leaving the phlogisticated. All these processes have been termed _phlogistic_, because the effect is not produced but by substances supposed to contain phlogiston in a volatile state; and by the affinity between phlogiston and the dephlogisticated part of the air, the one is separated from the other. Of these processes are the calcination of metals, a mixture of iron-filings and sulphur, liver of sulphur, the burning of phosphorus, and the effluvia of flowers. In some cases, however, it is not so clear that any thing is emitted from the substance that produces this effect; for water deprived of all air will absorb the dephlogisticated part of the atmospherical in preference to the phlogisticated part. As the purity of atmospherical air, or its fitness for respiration, depends upon the proportion of the dephlogisticated air that it contains, any of the above-mentioned processes will suffice to determine it. The more any given quantity of air is diminished by any of them, the purer it was before the diminution. But this effect is produced the most quickly by a mixture of nitrous air, or firing inflammable air in it, being almost instantaneous. In order to measure the purity of air, it is convenient to take more of the nitrous or inflammable air than is necessary to saturate the dephlogisticated air it contains. Equal quantities of each best answer the purpose. Supposing a given quantity of atmospherical air to be mixed with an equal quantity of nitrous air, and the residuum to be 1.1 measure, the proportion of dephlogisticated and phlogisticated air in it may be found by the following arithmetical operation, it being here taken for granted that one measure of pure dephlogisticated air will saturate two measures of pure nitrous air. 2.0 viz. one of each. 1.1 the residuum. ----- 3)0.9 the quantity that has disappeared. 0.3 the dephlogisticated air contained in the measure of the air examined. And this substracted from 1 leaves .7 for the proportion of phlogisticated air in it. LECTURE IV. _Of Dephlogisticated Air._ Dephlogisticated air, which is one of the component parts of atmospherical air, is a principal element in the composition of acids, and may be extracted by means of heat from many substances which contain them, especially the nitrous and vitriolic; as from nitre, red precipitate, the vitriols, and turbith mineral, and also from these two acids themselves, exposed to a red heat in an earthen tube. This kind of air is also contained in several substances which had attracted it from the atmosphere, as from precipitate _per se_, _minium_, & _manganese_. Dephlogisticated air is likewise produced by the action of light upon green vegetables; and this seems to be the chief means employed by nature to preserve the purity of the atmosphere. It is this ingredient in atmospheric air that enables it to support combustion and animal life. By means of it the most intense heat may be produced, and in the purest of it animals will live nearly five times as long as in an equal quantity of atmospherical air. In respiration, part of this air, passing the membrane of the lungs, unites with the blood, and imparts to it its florid colour, while the remainder, uniting with phlogiston exhaled from the venous blood, forms fixed air. It is dephlogisticated air combined with water that enables fishes to live in it. Dephlogisticated air is something heavier than atmospherical air, and the purity of it measured by mixing with it two equal quantities of nitrous or inflammable air, deducing the residuum after the diminution from the three measures employed, and dividing the remainder by 3, as in the process for common air. _Of Phlogisticated Air._ The other ingredient in the composition of atmospherical air is phlogisticated air. It is procured by extracting the dephlogisticated part of the common air, as by the calcination of metals, &c. &c. by dissolving animal substances in nitrous acid, and also by the union of phlogiston with nitrous air, as by heating iron in it, and by a mixture of iron-filings and sulphur. Phlogisticated air extinguishes a candle, is entirely unfit for respiration, and is something lighter than common air. It is not capable of decomposition, except by exploding it together with a superabundance of dephlogisticated air, and a quantity of inflammable air, or by taking the electric spark repeatedly in a mixture of it and dephlogisticated air. In these cases nitrous acid is formed. LECTURE V. _Of Inflammable Air._ Inflammable air is procured from all combustible substances by means of heat and water, and from several of the metals, especially iron, zink, and tin, by the vitriolic and marine acids. From oils and spirit of wine it is procured by the electric spark. By the same means also alkaline air is converted into it. That which is procured from metals, especially by steam, is the purest and the lightest, about ten times lighter than common air; in consequence of which, if a sufficient quantity be confined in a light covering, it is possible to make it carry up heavy weights. When it is procured from animal or vegetable substances, it is of a heavier kind, and burns with a lambent flame, of various colours, according to the circumstances. Calces of metals heated in inflammable air are revived, and the air absorbed; and since all the metals are revived in the same inflammable air, the principle of metallization, or _phlogiston_, appears to be the same in them all. Pure inflammable air seems to consist of phlogiston and water, and the lambent kinds to be the same thing, with the addition of some oily vapour diffused through it. LECTURE VI. _Of Nitrous Air._ Nitrous air is procured by dissolving most of the metals, especially iron, mercury, and copper, in the nitrous acid; but that from mercury seems to be the purest. Nitrous air produced from copper contains a mixture of phlogisticated air. Some nitrous air is also obtained from the solution of all vegetable substances in nitrous acid; whereas animal substances in the same process yield chiefly phlogisticated air: but in both these cases there is a mixture of fixed air. This species of air is likewise produced by impregnating water with nitrous vapour. This process continues to have this effect after the water becomes blue, but ceases when it turns green; there not then, probably, being a sufficient proportion of water. Nitrous air is likewise produced by volatile alkali passing over red hot manganese, or green vitriol, when they are yielding dephlogisticated air. This shews that dephlogisticated air is one ingredient in the composition of nitrous air, and the same thing appears by pyrophorus burning in it. On the contrary, when nitrous air is made to pass over red-hot iron, volatile alkali is produced. Nitrous air is completely decomposed by a mixture of about half its bulk of dephlogisticated air, and the produce is nitrous acid. And as nitrous acid is likewise formed by the union of inflammable and dephlogisticated air, one principal ingredient in nitrous air must be common to it and inflammable air, or phlogiston. This air is likewise decomposed by dephlogisticated nitrous acid, which by this means becomes phlogisticated. It is also decomposed by a solution of green vitriol, which by this means becomes black, and when exposed to the air, or heated, emits nitrous air, and recovers its former colour. These decompositions of nitrous air seem to be effected by depriving it of phlogiston, and thereby reducing it to the phlogisticated air originally contained in it. This kind of air is diminished to about one fourth of its bulk by a mixture of iron filings and brimstone, or by heating iron in it, or calcining other metals in it, when the remainder is phlogisticated air. All that iron gets in this process is an addition of weight, which appears to be water, but it loses its phlogiston, so that nitrous air seems to contain more phlogiston, and less water than phlogisticated air. Nitrous air and dephlogisticated air will act upon one another through a bladder, but in this case there remains about one-fourth of the bulk of nitrous air, and that is phlogisticated air; so that in this case there seems to be a conversion of nitrous air into phlogisticated air without any addition of phlogiston. Nitrous air is decomposed by pyrophorus, and by agitation in olive oil, which becomes coagulated by the process. It is also absorbed by spirit of turpentine, by ether, by spirit of wine, and alkaline liquors. It is imbibed by charcoal, and both that air which is afterwards expelled from it by heat, and that which remains unabsorbed, is phlogisticated air. Nitrous air resists putrefaction, but is diminished by the animal substances exposed to it to about a fourth of its bulk, and becomes phlogisticated air. It is likewise fatal to plants, and particularly to insects. When nitrous air is long exposed to iron, it is diminished and brought into a state in which a candle will burn in it, though no animal can breathe it. But this peculiar modification of nitrous air, called _dephlogisticated nitrous air_, is produced with the greatest certainty by dissolving iron in spirit of nitre saturated with copper, impregnating water with this air, and then expelling it from the water by heat. If bits of earthen ware be heated in this dephlogisticated nitrous air, a great proportion of it becomes permanent air, not miscible with water, and nearly as pure as common air, so that the principle of _heat_ seems to be wanting to constitute it permanent air. LECTURE VII. _Of Fixed Air._ Having considered the properties of those kinds of air which are not readily absorbed by water, and therefore may be confined by it, I proceed to those which _are_ absorbed by it, and which require to be confined by mercury. There are two kinds, however, in a middle state between these, being absorbed by water, but not very readily; a considerable time, or agitation, being necessary for that purpose. The first of these is _fixed air_. This kind of air is obtained in the purest state by dissolving marble, lime-stone, and other kinds of mild calcareous earth in any acid. It is also obtained by the burning, or the putrefaction, of both animal and vegetable substances, but with a mixture of both phlogisticated and inflammable air. Fixed air is also produced by heating together iron filings and red precipitate; the former of which would alone yield inflammable air, and the latter dephlogisticated. Fixed air is therefore a combination of these two kinds of air. Another fact which proves the same thing is, that if charcoal of copper be heated in dephlogisticated air, almost the whole of it will be converted into fixed air. On the same principle fixed air is produced when iron, and other inflammable substances, are burned in dephlogisticated air, and also when minium, and other substances containing dephlogisticated air, are heated in inflammable air. That water is an essential part of fixed air is proved by an experiment upon _terra ponderosa aerata_, which yields fixed air when it is dissolved in an acid, but not by mere heat. If steam, however, be admitted to it in that state, it will yield as much fixed air as when it is dissolved in an acid. Water absorbs something more than its own bulk of fixed air, and then becomes a proper acid. Iron dissolved in this water makes it a proper chalybeate; as without iron it is of the same nature with Pyrmont or Seltzer water, which by this means may be made artificially. Ice will not imbibe this air, and therefore freezing expels it from water. Fixed air extinguishes flame, and is fatal to animals breathing in it. Also water impregnated with this air is fatal to fishes, and highly injurious to plants. But water thus impregnated will prevent, in a great measure, the putrefaction of animal substances. Fixed air thrown into the intestines, by way of glyster, has been found to give relief in some cases of putrid disease. _Of Hepatic Air._ Another species of air absorbed by water, but not instantly, is termed _hepatic air_, being produced by the solution of liver of sulphur, or of sulphurated iron, in vitriolic or marine acid. Water imbibes about twice its bulk of this kind of air, and it is then the same thing with the sulphureous waters of Harrowgate. _Of Phosphoric Air._ Phosphoric air is produced by the solution of phosphorus in caustic fixed alkali. If this air be confined by mercury, it will take fire on being admitted to atmospheric, and much more to dephlogisticated air. After agitation in water it loses this property, and the residuum is merely inflammable air, with no great diminution of its bulk. This kind of air, therefore, probably consists of phosphorus dissolved in inflammable air; though it cannot be made by melting it in inflammable air. LECTURE VIII. _Of Dephlogisticated Marine Acid Air._ This species of air is produced by heating spirit of salt with manganese; or more readily, by pouring acid of vitriol on a mixture of salt and manganese, in the proportion of about 16 of the former to 6 of the latter. In this case the acid of vitriol decomposes the salt, and the marine acid, disengaged in the form of air, takes dephlogisticated air from the manganese; so that this species of air seems to consist of marine acid vapour, and dephlogisticated air. This species of air has a peculiarly pungent smell, and is absorbed by water as readily as fixed air. The water takes about twice its bulk of it; and thereby acquires a yellowish tinge. Both this air, and the water impregnated with it, discharges vegetable colours from linen or cotton, and is thereby useful in bleaching. This air when cold coagulates into a yellowish substance. It dissolves mercury, and with it forms _corrosive sublimate_. _Of Phlogisticated Marine Acid Air._ Besides the preceding kinds of air which are slowly absorbed by water, there are others which are absorbed by it very rapidly, so that they cannot be confined but by mercury. Of this kind is _phlogisticated marine acid air_, procured by the acid of vitriol and common salt; the former seizing upon the alkaline basis of the latter, and thereby expelling the marine acid in the form of air. It is called _phlogisticated_ to distinguish it from _dephlogisticated marine acid air_, which seems to be the same thing, with the addition of dephlogisticated air. Phlogisticated marine acid air is heavier than common air. It extinguishes a candle with a blue flame. It dissolves many substances containing phlogiston, as iron, dry flesh, &c. and thereby forms a little inflammable air. Water absorbs 360 times its bulk of this air, and is then the strongest spirit of salt. It absorbs one-sixth more than its bulk of alkaline air, and with it forms the common sal ammoniac. Its affinity to water enables it to dissolve ice, and to deprive borax, nitre, and other saline substances, of the water that enters into their composition. LECTURE IX. _Of Vitriolic Acid Air._ Vitriolic acid air is procured by heating in hot acid of vitriol almost any substance containing phlogiston, especially the metals which are soluble in that acid, as copper, mercury, &c. This kind of air is heavier than common air, and extinguishes a candle, but without any particular colour of its flame. It will not dislodge the nitrous or marine acids from any substance containing them. By its affinity to water it deprives borax of it. One measure of this air saturates two of alkaline air, and with it forms the vitriolic ammoniac. Water imbibes between 30 and 40 times its bulk of this air, and retains it when frozen. Water thus impregnated dissolves some metals, and thereby yields inflammable air. If this water be confined in a glass tube, together with common air, and be exposed to a long continued heat, it forms real sulphur, the dephlogisticated part of the common air being imbibed, and forming real vitriolic acid, which uniting with the phlogiston in the air, forms the sulphur. Also this air mixed with atmospheric air will, without heat, imbibe some part of it, and thereby become the common acid of vitriol; so that water impregnated with vitriolic acid air, commonly called _sulphureous_, or _phlogisticated acid of vitriol_, wants dephlogisticated air to make it the common acid of of vitriol. This kind of air is imbibed by oils, which thereby change their colour; whale oil becoming red, olive oil of an orange colour, and spirit of turpentine of the colour of amber. If this air be confined in a glass tube by mercury, and the electric spark be taken in it, a black tinge will be given to the glass contiguous to the spark, and this black substance appears to be mercury super-phlogisticated; since by exposure to air it becomes running mercury: so that the vapour of mercury must be diffused through every part of this air, to the distance of at least several feet from the surface of the mercury. _Of Fluor Acid Air._ Fluor acid air is procured by dissolving the earthy substance called _fluor_ in vitriolic acid. This kind of air extinguishes a candle, and, like vitriolic acid air, one measure of it saturates two of alkaline air. It is peculiar to this kind of air to dissolve glass when it is hot. It seems to consist of a peculiar acid vapour united to the stony substance of the fluor; for water being admitted to it absorbs the acid vapour, and the stony substance is deposited. By this means it exhibits an amusing appearance, whether water be admitted to a glass jar previously filled with that air, or the bubbles of air be admitted, as they are formed, to a quantity of water resting on mercury. LECTURE X. _Of Alkaline Air._ Alkaline air is produced by means of heat from caustic volatile alkali, and also from a mixture of sal-ammoniac and slaked lime, in the proportion of about one-fourth of the former to three-fourths of the latter. In this case the marine acid in the sal-ammoniac unites with the calcareous earth, and the volatile alkali (probably with the assistance of the water) takes the form of air. This species of air is heavier than inflammable air, but lighter than any of the acid airs. Like them, however, it dissolves ice, and deprives alum, and some other saline substances, of the water which they contain. United with fixed air, it makes the concrete volatile alkali; with marine acid air, the common sal-ammoniac; and with water, the caustic volatile alkali. The electric spark, or a red heat, converts alkaline air into three times its bulk of inflammable air; and the calces of metals are revived in alkaline, as well as in inflammable air; but there remains about one-fourth of its bulk of phlogisticated air. These facts shew that alkaline air consists chiefly of phlogiston. _Miscellaneous Observations relating to Air._ The _nitrous_ acid may be exhibited in the form of air, as well as the vitriolic, the marine, and the fluor acids. But it cannot be confined even by mercury, which it instantly dissolves. It may, however, in some measure, be confined in a dry glass vessel, from which it will in a great measure expel the common air. This nitrous acid air is that red vapour, which is produced by the rapid solution of bismuth, and some other metals in the nitrous acid. But the vegetable acid cannot be exhibited in the form of air. It is only capable of being converted into vapour, like water: and in the common temperature of our atmosphere, returns to a state of fluidity. Different kinds of air which have no affinity to each other, when once mixed together will not separate, notwithstanding any difference of specific gravity. Such is the case of a mixture of inflammable and dephlogisticated air, and even of inflammable and fixed air. Without this property also, the phlogisticated air, which constitutes the greatest part of our atmosphere, being specifically lighter than dephlogisticated air, of which the other part of it consists, would separate from it, and ascend into the higher regions of the atmosphere. Inflammable air, however, will not mix with acid or alkaline air. Different kinds of air are expanded differently by the same degrees of heat; dephlogisticated air the least, and alkaline air the most. If any fluid, as water, spirit of wine, or even mercury, be heated in a porous earthen vessel, surrounded by any kind of air, the vapour of the fluid will pass through the vessel _one_ way, while the air passes the _other_; and when the operation ceases, with respect to the _one_, it likewise ceases with respect to the _other_. LECTURE XI. _Of Liquid Substances_; AND FIRST OF _WATER_. Having considered all the substances that are usually found in the form of _air_, I come to those that are generally in a _fluid_ form, beginning with _water_, which is the principal, if not the only cause of fluidity to all the other substances that I shall place in this class. Pure water is a liquid substance, transparent, without colour, taste, or smell; and with different degrees of heat and cold may be made to assume the three forms of a solid, of a fluid, and of air. Below 32° of Fahrenheit it is ice, and above 212° it is vapour; so that in an atmosphere below 32° it never could have been known to be any thing else than a peculiar kind of stone, and above 212° a peculiar species of air. In passing from the state of a solid to that of a liquid, water absorbs a great quantity of the principle, or matter, of _heat_, which remains in it in a _latent_ state; and in passing from a state of fluid to that of vapour, it absorbs much more; and this heat is found when the processes are reversed. It has been observed, that when water becomes vapour, it takes the form of small globules, hollow within, so as to be specifically lighter than air. The degree of heat at which water is converted into vapour depends upon the pressure of the atmosphere; so that in vacuo, or on the top of a high mountain, it boils with little heat; and when compressed, as in Papin's digester, or in the bottom of a deep pit, it requires much heat. In the former case the restoring of the pressure will instantly put a stop to the boiling, and in the latter case the removing of the pressure will instantly convert the heated water into vapour. The ease with which water is converted into vapour by heat, has given a great power to mechanicians, either by employing the natural pressure of the atmosphere, when steam is condensed under a moveable pistern, in an iron cylinder, which was the principle of the old fire-engine, or by employing the elastic power of steam to produce the same effect, which is the principle of Mr. Watt's steam engine. Water was long thought to be incompressible by any external force, but Mr. Canton has shewn that even the pressure of the atmosphere will condense it very sensibly. We do not know any external force equal to that by which water is expanded when it is converted into ice, or into vapour. For though the particles of water approach nearer by cold, yet when it crystallizes, the particles arrange themselves in a particular manner, with interstices between them; so that, on the whole, it takes up more room than before. Water has an affinity to, and combines with, almost all natural substances, aerial, fluid, or solid; but most intimately with acids, alkalies, calcareous earth, and that calx of iron which is called _finery cinder_, from which the strongest heat will not expel it. It has been supposed by some, that by frequent distillation, and also by agitation, water may be converted into a kind of earth; but this does not appear to be the case. It has also of late been thought, that water is resolvable into dephlogisticated and inflammable air; but the experiments which have been alleged to prove this do not satisfy me; so that, for any thing that appeared till very lately, water might be considered as a simple element. By means of heat, however, it seems to be resolvable into such air as that of which the atmosphere consists, viz. dephlogisticated and phlogisticated, only with a greater proportion of the former. Water, with respect to specific gravity and temperature, has generally been made the standard to all other substances; its freezing and boiling points being the limits by means of which thermometers are graduated. Other substances have also been compared with water, as a standard, with respect to the capacity of receiving heat, and retaining it in a latent state, as will be shewn when we consider the subject of heat. LECTURE XII. _Of the Nitrous Acid._ Under the head of _liquids_ I shall consider _acids_ and _alkalis_, though some of them may be exhibited in the form of air, and others in a solid form. These two chemical principles are formed to unite with one another, and then they constitute what is called a _neutral salt_. Both acids and alkalis are distinguishable by their taste. Another test, and more accurate, is, that acids change the blue juices of vegetables red, and alkalis turn the syrup of violets green. Acids are generally distinguished according to the three kingdoms to which they belong, viz. _mineral_, _vegetable_, and _animal_. The mineral acids are three, the _nitrous_, the _vitriolic_, and the _marine_. The nitrous acid is formed by the union of the purest inflammable air, or the purest nitrous air, with dephlogisticated air. But it is usually procured from nitre by means of the vitriolic acid, which, seizing its base, expels the nitrous acid in a liquid form. On this account this acid is said to be weaker than the vitriolic. If the nitrous acid be made to pass through a red-hot earthen tube, it will be decomposed, and the greatest part of it be converted into dephlogisticated air. Like all other acids, the nitrous acid has a strong affinity to water; but it is not capable of so much concentration as the vitriolic. It is generally of an orange or yellow colour; but heat will expel this colour in the form of a red vapour, which is the same acid in the form of air, and loaded with phlogiston; and therefore when it is colourless it is said to be dephlogisticated. But the colourless vapour exposed to heat, or to light, will become coloured again; and the liquid acid imbibing this coloured vapour, becomes coloured as before. This acid tinges the skin of a yellow colour, which does not disappear till the epidermis be changed. The nitrous acid unites with phlogiston, alkalis, metallic substances, and calcareous earth. By means of its affinity with phlogiston it occasions that rapid accension called _detonation_, when any salt containing this acid, especially nitre, is applied to hot charcoal, or when charcoal is put to hot nitre. In fact, the charcoal burns so rapidly by means of the dephlogisticated air supplied by the nitre. A mixture of sulphur assists the accension of these substances, and makes gunpowder, in the explosion of which much nitrous or phlogisticated air is suddenly produced, and expanded by the heat. The application of this force, both to useful and destructive purposes, is well known. If, instead of nitre, a salt made with dephlogisticated marine acid be made use of, the explosion is more easily produced, and is much more violent. Friction will do this as well as heat. Nitre also enters into the composition of _pulvis fulminans_, viz. three parts nitre, two of dry alkali, and one of sulphur. This composition melts, and yields a blue flame, before it explodes. By means of the affinity of the nitrous acid to _oil_, another substance containing phlogiston, it is capable of producing not only a great heat, but even a sudden flame, especially when mixed with a little vitriolic acid. Nitrous acid dissolves all metallic substances except gold and platina, and in the solution nitrous air is produced. The particular kinds of saline substances formed by the union of the nitrous acid with the several metals and earths may be seen in tables constructed for the purpose. They are all deliquescent. LECTURE XIII. _Of the Vitriolic Acid._ The vitriolic acid, so called because it was originally procured from _vitriol_, is now generally procured from sulphur; the dephlogisticated part of the air uniting with it in the act of burning. That dephlogisticated air is essential to this acid is evident from the decomposition of it; for if the vapour of it be made to pass through a red-hot earthen tube, a great quantity of dephlogisticated air is procured. This acid has a strong affinity to water, with which it unites with much heat; and it is capable of greater concentration, or of being made specifically heavier, than any other acid. When pure, it is entirely free from colour and smell, owing, probably, to its being free from phlogiston, which is inseparable from the nitrous or marine acids. The vitriolic acid will dislodge the nitrous, or marine, or any other acid, from their earthy or metallic bases; from which property it is called the strongest of all the acids. By means of the superior affinity of the vitriolic acid to earths, and especially to _terra ponderosa_, the smallest quantity of it in water may be discovered by a solution of this earth in the marine acid. In this acid the terra ponderosa is held in perfect solution; but with the vitriolic acid it forms a substance that is insoluble in water, and therefore it instantly appears in the form of a white cloud. Perhaps chiefly from the strong affinity which this acid has with water, _pyrophorus_, consisting of a mixture of alum and several substances containing phlogiston, takes fire spontaneously on exposure to the air. It is commonly made of three parts of alum and one of brown sugar, or of two parts alum, one of salt of tartar, and one of charcoal. They must be heated till they have for some time emitted a vapour that burns with a blue flame. The saline substances produced by the union of this acid with the several earths and metals, are best exhibited in tables constructed for the purpose. When united to three of the metals, viz. iron, copper, and zinc, they are called _vitriols_, green, blue, and white. And all the substances which this acid unites with crystallize, and do not deliquesce. This acid unites with oil, and the mixture is always black. When any substance containing phlogiston is heated in the vitriolic acid, another species of the acid, called _sulphureous_, is formed, of a pungent smell. In reality, it is water impregnated with vitriolic acid air. It makes, however, a distinct species of acid, and is dislodged from its base by most of the others. _Of the Marine Acid._ The marine acid is procured from common salt by the vitriolic acid, which unites with its base, the fossil alkali. This acid is generally of a straw-colour; but this is owing to an impregnation with some earthy matter, most of which it readily dissolves, especially the metallic ones. It is less capable of concentration than the vitriolic or nitrous acids, perhaps from a more intimate union of phlogiston with it. No heat can extract from it any dephlogisticated air. Though this is denominated a weaker acid than the nitrous, yet it will take silver, lead, or mercury, from their union with the nitrous acid. Upon this principle, a solution of these metals in the nitrous acid will readily discover whether any water contains the marine acid, the latter uniting with the metal dissolved in the former, and forming with it, if it be silver, a _luna cornea_; which being a substance insoluble in water, discovers itself by a cloudy appearance. The union of the marine acid with earths forms salts that easily deliquesce, but with the metals such as are capable of crystallization; and so also is that formed by the union of this acid to terra ponderosa. Neither this acid nor the nitrous will dissolve gold or platina; but a mixture of them, called _aqua regia_, will do it. The marine acid has a strong affinity to dephlogisticated air, and will take it from manganese and other substances; and with this union it becomes a different acid, called _dephlogisticated marine acid_, being water impregnated with dephlogisticated marine acid air, described above. LECTURE XIV. _Of the Vegetable Acids, and others of a less perfect nature._ The principal of the vegetable acids are the _acetous_ and the _tartareous_. The acetous acid is the produce of a peculiar fermentation of vegetable substances, succeeding the _vinous_, in which ardent spirit it is procured, and succeeded by the _putrefactive_, in which volatile alkali is generated. Thus wine is converted into vinegar. Crude vinegar, however, contains some ingredient from the vegetable substances from which it was procured: but distillation separates them, and makes the vinegar colourless; though some of the acid is lost in the process. The acetous acid is concentrated by frost, which does not affect the proper acid, but only the water with which it is united. It may likewise be concentrated by being first combined with alkalies, earths, or metals, and then dislodged by a stronger acid, or by mere heat. Thus the acetous acid, combined with vegetable alkali, forms a substance that is called the _foliated earth of tartar_; and it may be expelled from it by the vitriolic acid. When combined with copper it makes _verdigris_; and from this union heat alone will expel it in a concentrated state. The acetous acid thus concentrated is called _radical vinegar_. Still, however, it is weaker than any of the preceding mineral acids. Several vegetables, as lemons, sorrel, and unripe fruit, contain acids, ready formed by nature, mixed with some of the essential oil of the plants, which gives them their peculiar flavours. All these acids have peculiar properties; but it is not necessary to note them in this very general view of the subject. Like vinegar, these acids may be concentrated by frost, and also by a combination with other substances, and then expelled by a stronger acid. The _acid of tartar_ is very similar to that of vinegar. Tartar, from which it is procured, is a substance deposited on the inside of wine-casks, though it is also found ready formed in several vegetables. It consists of the vegetable alkali and this peculiar acid. When refined from its impurities, it is called _crystals_, or _cream of tartar_. The acid is procured by mixing the tartar with chalk, or lime, which imbibes the superfluous acid, and this is expelled by the acid of vitriol. Or it may be procured by boiling the tartar with five or six times its weight of water, and then putting the acid of vitriol to it. This unites with the vegetable alkali, and forms vitriolated tartar; and the pure acid of tartar may be procured in crystals, by evaporation and filtration, equal in weight to half the cream of tartar. This acid of tartar is more soluble in water than the cream of tartar. This acid, united to the mineral alkali, makes _Rochelle salt_. Every kind of wood, when distilled, or burned, yields a peculiar acid; and it is the vapour of this acid that is so offensive to the eyes in the smoke of wood. A peculiar acid is obtained from most vegetable substances, especially the farinaceous ones, and from sugar, by distillation with the nitrous acid. This seizes upon the substance with which the acid was united, and especially the phlogiston adhering to it, and then the peculiar _acid of sugar_ crystallizes. Thus with three parts of sugar, and thirty of nitrous acid, one part of the proper acid of sugar may be obtained. By the same process an acid may be procured from camphor. The _bark of oak_, and some other vegetable substances, especially nut-galls, contain a substance which has obtained the name of _the astringent principle_; the peculiar property of which is, that it precipitates solutions of iron in the form of a black powder, and in this manner _ink_ is made. But by solution in water and evaporation, crystals, which are a proper _acid of galls_, may be obtained. _Amber_ is a hard semitransparent substance, chiefly found in Prussia, either dug out of the earth, or thrown up by the sea. It is chiefly remarkable for its electrical property; but by distillation in close vessels there sublimes from it a concreted acid, soluble in 24 times its weight of cold water. Amber seems to be of vegetable origin, and to consist of an oil united to this peculiar acid. The acids I shall mention next are of a mineral origin; but being of a less perfect nature as acids, I shall only just note them here. _Borax_ is a substance chiefly found in a crystallized state in some lakes in the East Indies. It consists of the mineral alkali and a peculiar acid, which may be separated, and exhibited in white flakes, by putting acid of vitriol to a solution of it in water. This acid has been called _sedative salt_, from its supposed uses in medicine. It is an acid that requires fifty times its weight of water to dissolve it. Several other mineral substances, as _arsenic_, _molybdena_, _tungsten_, and _wolfram_, in consequence of being treated as the preceding vegetables ones, have been lately found to yield peculiar acids. They are also produced in a concrete state, and require a considerable proportion of water to make them liquid; but as the water in which they are dissolved turns the juice of litmus red, and as they also unite with alkalis, they have all the necessary characteristics of acids. LECTURE XV. _Of the Phosphoric Acid._ The most important acid of _animal_ origin, though it has lately been found in some mineral substances, is the _phosphoric_. Phosphorus itself is a remarkable substance, much resembling sulphur, but much more inflammable. It has been procured chiefly, till of late, from urine, but now more generally from _bones_, by means of the vitriolic acid, which unites with the calcareous earth of which bones consist, and sets at liberty the phosphoric acid, or the base of that acid, with which it was naturally combined. The acid thus procured, mixed with charcoal, and exposed to a strong heat, makes phosphorus. This substance burns with a lambent flame in the common temperature of our atmosphere, but with a strong and vivid flame if it be exposed to the open air when moderately warm. In burning it unites with the dephlogisticated air of the atmosphere, and in this manner the purest phosphoric acid is produced. This acid is also procured in great purity by means of the nitrous or vitriolic acids, especially the former, which readily combines with the phlogiston of the phosphorus, and thus leaves the acid pure. In this process phlogisticated air is produced. This acid is perfectly colourless, and when exposed to heat loses all its water, and becomes a glassy substance, not liable to be dissipated by fire, and readily uniting with earths. United to the mineral alkali, it forms a neutral salt, lately introduced into medicine. United to the mineral and vegetable alkalis naturally contained in urine, it has obtained the name of _microcosmic salt_, frequently used as a flux for mineral substances with a blow-pipe. Besides the phosphoric, there are other acids of an animal origin; as that of _milk_, that of _sugar of milk_, that of the _animal calculus_, and that of _fat_. The acid of milk is the sour whey contained in butter-milk, which, by a tedious chemical process, may be obtained pure from any foreign substance. The sugar of milk is procured by evaporating the whey to dryness, then dissolving it in water, clarifying it with whites of eggs, and evaporating it to the consistence of honey. In this state white crystals of the acid of sugar of milk will be obtained. By distilling these crystals with nitrous acid, other crystals of the proper _acid of sugar of milk_ will be obtained, similar to those of the acid of sugar. If the human calculus be distilled, it yields a volatile alkali, and something sublimes from it which has a sourish taste, and therefore called the _acid of the calculus_. It is probably some modification of the phosphoric acid. Animal fat yields an acid by distillation, or by first combining it with quick-lime, and then separating it by the vitriolic acid. Siliceous earth is corroded by this acid. LECTURE XVI. _Of Alkalis._ The class of substances that seems particularly formed by nature to unite with acids, and thereby form _neutral salts_, are the _alkalis_. They have all a peculiar acrid taste, not easily defined. They change the blue juices of vegetables green, or purple, and in common with acids have an affinity with water, so as to be capable of being exhibited in a liquid form; though when this water is expelled by heat, some of them will assume a solid form. Alkalis are of two kinds; the _fixed_, which have no smell, and the _volatile_ which have a pungent one. The fixed alkalis are of _vegetable_ or _mineral_ origin. When in a solid form, they both melt with a moderate heat, and uniting with earthy substances, make _glass_. With an intense heat they are volatilized. Vegetable alkali is procured by burning plants, and lixiviating the ashes; a purer kind by the burning of tartar, hence called _salt of tartar_; but the purest of all is got by the deflagration of nitre; the charcoal uniting with the acid as it assumes the form of dephlogisticated air, and the alkali being left behind. Mineral alkali is found in ashes of sea-weed. It is likewise the basis of sea-salt; from which it is separated by several processes, but especially by the calx of lead, which has a stronger affinity with the marine acid with which it is found combined. Alkalis united with fixed air are said to be _mild_, and when deprived of it _caustic_, from their readiness to unite with, and thereby _corrode_, vegetable and animal substances. To render them caustic, they are deprived of their fixed air by quick-lime; and in this state they unite with oils, and make _soap_. Alkalis have a stronger affinity with acids than metals have with them; so that they will precipitate them from their solutions in acid menstruums. The vegetable fixed alkali has a strong attraction to water, with which it will become saturated in the common state of our atmosphere, when it is said to _deliquesce_; and having the appearance of _oil_, the salt of tartar is thus said to become _oil of tartar per deliquium_. On the other hand, the mineral, or fossil alkali, is apt to lose its water in a dry atmosphere, and then it is said to _effloresce_. In this state it is often found on old walls. Volatile alkali is procured by burning animal substances; in Egypt (from whence, as contained in _sal ammoniac_, we till of late imported it) from camel's dung; but now from bones, by distillation. To the liquor thus procured they add vitriolic acid, or substances which contain it. This acid unites with the alkali, and common salt being put to it, a double affinity takes place. The vitriolic acid uniting with the mineral alkali of the salt, makes _Glauber salt_, and the marine acid uniting with the volatile alkali, makes _sal ammoniac_. Slaked lime added to this, unites with the marine acid of the ammoniac, and sets loose the volatile alkali in the form of _alkaline air_, which combining with water, makes the liquid caustic volatile alkali. If chalk (containing calcareous earth united with fixed air) be mixed with the sal ammoniac, heat will make the calcareous earth unite with the marine acid, while the fixed air of the chalk will unite with the volatile alkali, and assume a solid form, being the _sal volatile_ of the apothecaries. LECTURE XVII. _Of Liquid Inflammable Substances._ Of liquid inflammable substances the principal is _spirit of wine_, sometimes called _ardent spirit_, and, when highly rectified, _alcohol_. It is obtained from vegetable substances by their going through the vinous fermentation. It is considerably lighter than water, colourless, and transparent, has a peculiar smell and taste, and the property of inebriating. Ardent spirit seems to consist of a peculiar combination of phlogiston and water; for when the vapour of it is made to pass through a red-hot earthen tube, it is resolved into water and inflammable air. It is highly inflammable, and burns without smoke, or leaving any residuum; and in the act of burning its phlogiston so unites with dephlogisticated air as to make fixed air. Ardent spirit mixes readily with water in all proportions, and also with essential oils, and balsams or resins, which are the same thing inspissated. By its affinity with essential oils, ardent spirit extracts them froth aromatic plants; and these liquors have obtained the name of _tinctures_. When the tinctures are distilled, the more volatile parts of the essential oils, which come over in distillation, have acquired the name of _waters_; as _Lavender water_, _Rosemary water_, &c. and what remains in the still is called the _extract_ of the plant. If the tinctures be diluted with much water, the resinous part of the plant will be obtained pure, and separated from the extractive part, which will remain dissolved in the water, while the resin separates from it. Spirit of wine will not dissolve the gummy parts of vegetables; and by this means the gummy substances may be separated from their solutions in water, the spirit uniting with the water only. On the other hand, if resins be dissolved in spirit of wine, the affusion of water will separate them. By means of the affinity of spirit of wine with water, it will seize upon the water in which several salts are dissolved, and thus produce an instant crystallization of them. Salt of tartar has a greater affinity to water than spirit of wine, and by extracting water from it, will assist in concentrating it; but the best method of rendering spirit wine free from water is distillation, the ardent spirit rising before the water. Spirit of wine mixed with the vitriolic and other mineral acids, renders them milder, and thereby more proper for certain medicinal uses. This is called _dulcifying_ them. Spirit of wine is a powerful antiseptic, and is therefore of use to preserve vegetable and animal substances from putrefaction. _Of Æther._ If spirit of wine be distilled with almost any of the acids, the produce is a liquor which has obtained the name of _Æther_, from its extreme lightness and volatility, being much lighter, and more volatile, than any other fluid that we are acquainted with. It is highly inflammable, but the burning of it is accompanied with smoke, and some soot; and on this account it is a medium between spirit of wine and oil, the acid having taken from the spirit of wine part of the water that was essential to it, at the same time that it communicated something of its acid peculiarly modified; since æthers have different properties according to the acids by which they are made; as the _vitriolic_, the _nitrous_, the _marine_, and the _acetous_. No æther, however, can be made from the marine acid till it has been in some measure dephlogisticated; from which it may be inferred, that dephlogisticated air is necessary to the composition of æther. Vitriolic æther is the most common, in consequence of the process by which it is made being the easiest. Æther does not mix with water in all proportions, like spirit of wine, but ten parts of water will take up one of æther. It easily mixes with all oils. It is something remarkable, that though æther will not dissolve gold, it will take from aqua regia the gold that has been previously dissolved in it. By the quick evaporation of æther a considerable degree of cold may be procured; and on this principle it has sometimes been applied to relieve the head-ach and other pains. LECTURE XVIII. _Of Oil._ Oil is a liquid inflammable substance, of great tenacity, disposed to pour in a stream rather than in drops. It is little, if at all, soluble in water. It burns with smoke and soot, and leaves a residuum of a coaly substance. It consists of acid and water combined with phlogiston. All oil is the produce of the vegetable or animal kingdom, no proper mineral substance containing any of it. By distillation oil is in part decomposed, and by this means the thicker kinds of oil are rendered thinner and more volatile, the acid, to which their consistence is chiefly owing, being lost in the process. By repeated distillation it is supposed that all oils may be brought almost to the state of æther, and even of ardent spirit. Acids act powerfully upon oils, but very differently, according to the nature of each. Alkalies also combine with oils, and the less thin and volatile they are, the more easily are they soluble in alkalies. The union of alkali and oil makes _soap_. All oil dissolves sulphur, and with it makes what is called a _balsam_. Oils also dissolve metallic substances, but most sensibly copper and lead. United with the calx of lead, it is used in painting. Oil not readily mixing with water, it will diffuse itself over its surface, and, notwithstanding its tenacity, it will do this very rapidly, and to a great extent; and then it has the extraordinary effect of preventing the action of the wind upon the water, so as to prevent the forming of waves. If a quantity of oil and water be put into a glass vessel and swung, the surface of the water below the oil will be seen to change with respect to the vessel, but not that of the oil. If spirit of wine be put upon them, that will be at rest, and both the lower fluids in motion. Vegetable oil is of two kinds, the _soft_, or _mild_, which has little or no taste or smell, and the _essential_ oil, which is thin, and retains the smell and taste of the plant from which it was extracted. Mild or sweet oil is expressed from the grains or kernels of vegetables, and requires a considerable degree of heat to convert it into vapour, in which state alone it is capable of being inflamed. _Essential oil_ is volatile in the heat of boiling water, and is generally obtained by means of distillation from the most odoriferous sorts of plants; but is sometimes found in their vesicles, as in the rind of an orange. The strong taste of this kind of oil arises from the disengaged acid which abounds in it; and by this means it is soluble in spirit of wine, which sweet oil is not; but it loses much of this property by repeated distillations. By long exposure to the air it loses its more volatile parts, and thereby approaches to the nature of a resin. This volatile odoriferous principle has been called the _spiritus rector_ of the plant. The essential oils of different plants differ much in their specific gravity, and also in the manner by which they are affected by cold, some being heavier and others lighter than water, and some being more difficultly, and others more easily, congealed. Though the differences with respect to _weight_ and _consistency_ in these oils is probably owing to the state of the acid that is combined with them, these two properties are wholly independent of each other; some essential oils being very thin and yet heavy, and others thick and yet light. Essential oils are used in perfumes, and also in medicine, acting powerfully the nervous system. Essential oils are very apt to be adulterated. If it be with sweet oil, it may be discovered by evaporation on white paper, or by a solution in spirit of wine, which will not act upon the sweet oil. If spirit of wine be mixed with it, it will be discovered by a milky appearance upon putting water to it, which uniting with the spirit, will leave the oil much divided. If oil of turpentine, which is the cheapest of essential oils, be mixed with any of the more valuable kinds, it will be discovered by evaporation; a strong smell of turpentine being left on the paper, or cloth, upon which the evaporation was made. Animal oil, like the vegetable, is of two kinds; the first _butter_, or _fat_, which is easily congealed, owing to the quantity of acid that is intimately combined with it. It resembles the sweet oil of vegetables in having no smell or taste. The other kind of animal oil is extracted by distillation from the flesh, the tendons, the bones, and horns, &c. of animals. It differs essentially from the other kind of animal oil, by containing an alkali instead of an acid. By repeated distillation it becomes highly attenuated and volatile; and in this state it is called the _oil of Dippel_, the discoverer of it. All oil exposed to much heat is in part decomposed, and acquires a disagreeable smell; and in this state it is said to be _empyreumatic_: but this property is lost by repeated distillations. Besides the vegetable and animal oils above described, there is a fossil oil called _bitumen_, the several kinds of which differ much in colour and consistence; the most liquid is called _petroleum_, from being found in the cavities of rocks, and the more solid kinds are _amber_, _jet_, _asphaltum_, and _pit-coal_. When distilled, the principal component parts of all these substances are an oil and an acid. But all fossil oil is probably of vegetable or animal origin, from masses of vegetables or animals long buried in the earth. Their differences from resins and other oily matters are probably owing to _time_; the combinations of mineral acids and oils so nearly resembling bitumens, the principal difference being their insolubility in spirit of wine. That the most solid of these, as amber, has been formerly in a liquid state, is evident, from insects and other substances being frequently found in them; and pit-coal has been often found with both the internal texture and external appearance of wood; so that strata of pit-coal have probably been beds of peat in some former state of the earth. LECTURE XIX. _Of Solid Substances._ All solid substances are capable of becoming fluid by heat, and most of them may thereby be reduced into a state of vapour, or air; and in passing from a fluid into a solid state their component parts assume a particular mode of arrangement, called _crystallization_, which differs according to the nature of the substance; so that all solids, especially if they be suffered to concrete slowly, may be called _crystals_. Exclusive of _salts_, which have been considered already, as formed by the union of acids and alkalis, solids in general have obtained the names of _earths_, or _stones_, which differ only in their texture; and they are distinguished into those that are _metallizable_, or those that are not; the former being called _ores_, and the latter simply _earths_; the principal of which are the _calcareous_, _siliceous_, _argillaceous_, _magnesia_, _terra ponderosa_, and a few others which have been discovered lately, but have not been much examined. _Of Calcareous Earth._ Calcareous earth is found in the shells of fishes, the bones of animals, chalk, lime-stone, marble, and gypsum: but all calcareous earth is supposed to be of animal origin; and beds of chalk, lime-stone, or marble, are thought to have been beds of shells formed in the sea, in some pristine state of the earth. The calcareous earth which is found in shells, lime-stone, and marble, is combined with fixed air, discovered by effervescing with acids. To obtain it perfectly pure, the earth must be pounded and washed with water, in order to free it from any saline substance which may be contained in it, then dissolved in distilled vinegar, and precipitated by mild alkalies. Lime-stone exposed to heat loses about half its weight, in fixed air and water, and the remainder, called _quick-lime_, attracts water very powerfully, and their union is attended with much heat, after which it dissolves into a fine powder called _slaked lime_. If it be left exposed to the atmosphere, it will of itself, by gradually imbibing moisture, fall into the state of powder. Water dissolves about one seven hundredth part of its weight of quick-lime, and is then called _lime-water_. Exposed to the air, a crust will be formed on its surface, which is found to consist of calcareous earth and fixed air. Lime and water mixed with sand make _mortar_, by which means different stones may be made to cohere as one mass, which is the most valuable use of this kind of earth. Calcareous earth, united with vitriolic acid, makes _gypsum_; and this substance pounded and exposed to heat, parts with its water, and is then called _plaister of Paris_. In this state, by imbibing water again, it becomes a firm substance, and thus is useful in making moulds, &c. The earth of animal bones is calcareous united to the phosphoric acid. _Of Siliceous Earth._ Siliceous earth seems to be formed by nature from chalk, perhaps by the introduction of some unknown acid, which the vitriolic acid is not able to dislodge. It abounds in most substances which are hard enough to strike fire with steel, as _flint_, _rock crystal_, and most _precious stones_. It is not acted upon by any acid except the fluor and phosphoric, but especially the former: but it is soluble in alkalies; and being then dissolved in water, makes _liquor silicum_, from which the purest siliceous earth may be precipitated by acids. For this purpose about four times the weight of alkali must be made use of. With about equal weights of alkali and siliceous sand is made _glass_, of so great use in admitting light and excluding the weather from our houses, as well as for making various useful utensils. To make glass perfectly colourless, and at the same time more dense, commonly called _flint glass_, manufacturers use a certain proportion of calx of lead and manganese. Siliceous earth is not affected by the strongest heat, except by means of a burning lens, or dephlogisticated air. LECTURE XX. _Of Argillaceous Earth._ Argillaceous earth is found in _clay_, _schistus_, or _slate_, and in _mica_; but the purest is that which is precipitated from a solution of alum by alkalies; for alum consists of the union of vitriolic acid and argillaceous earth. This species of earth is ductile with water; it then hardens and contracts by heat, so as to be of the greatest use in forming _bricks_, or stones of any required form or size. By means of the property of clay to contract in the fire, Mr. Wedgwood has constructed an excellent thermometer to measure the degrees of extreme heat. The ductility of clay seems to depend upon some acid, probably the vitriolic, adhering to it; for it loses that property when it is burned into a brick, but recovers it when it has been again dissolved in an acid. _Of Terra Ponderosa._ _Terra ponderosa_, or _marmor metallicum_, is generally found in two states, viz. united to vitriolic acid, when it is called _calk_, or to fixed air, when it is called _terra ponderosa aerata_. To obtain it pure from its union with the vitriolic acid, it must be melted with about twice its weight of fixed alkali; which unites with the acid, and forming a saline substance, may be washed out of it. In this state it contains water, and therefore, when exposed to heat, will yield fixed air; whereas the terra ponderosa aerata will not yield fixed air by heat only, but when steam is made to pass over it when red hot. This proves that water is essential to the composition of fixed air. This stone is distinguishable by its great specific gravity, being four times as heavy as water; but though in this it resembles an _ore_, it has not been found to be metallizable. _Of Magnesia._ This species of earth is found in _steatites_, or _soap rock_, _Spanish chalk_, _asbestus_, and _Muscovy talck_; but the purest is got by dissolving _Epsom salts_ (which consists of this earth united to the vitriolic acid) and precipitating it by a mild alkali. In this state it becomes united to fixed air, which may be expelled by heat. It is then _calcined_, or _caustic_, but differs from quick-lime by not being soluble in water. _Asbestus_, which contains much of this kind of earth, is remarkable for not being destructible by heat, though it is sometimes found in flexible fibres, so as to be capable of being woven into cloth. _Muscovy talck_ is remarkable for the thin and transparent flakes into which it is divisible, and thereby capable of various uses. There are some other distinct species of earth, particularly one brought from Botany Bay, and another called _Stontiate_, from the place where it was found in Scotland; but they have not as yet been much examined. All stones formed by nature are compounded, and to distinguish them from one another, and ascertain the parts of which they consist, is the subject of _lithology_, a very extensive branch of knowledge. All the simple earths are nearly, if not absolutely, _infusible_; but when they are mixed they may all be fused. LECTURE XXI. _Of Ores_. Metallizable earths, commonly called _ores_, when united to phlogiston, make the metals, distinguishable for their specific gravity, their opacity, shining appearance, and fusibility. All the proper metals are _malleable_, and those which are not so are called _semi-metals_. The metals again are subdivided into the _perfect_ and _imperfect_. The former, which are _gold_, _silver_, and _platina_, suffer no change by fusion, or the longest continued heat: whereas heat calcines or dissipates the phlogiston of the imperfect metals, which are _mercury_, _lead_, _copper_, _iron_, and _tin_, so that they return to the state of earth; and this earth is always heavier than the metal, though of less specific gravity, having received an addition of weight from water or air: but these earths, or ores, being exposed to heat in contact with substances containing phlogiston, again become metals, and are then said to be _revived_. The semi-metals are _bismuth_, _zinc_, _nickel_, regulus of _arsenic_, of _cobalt_, of _antimony_, of _manganese_, of _wolfram_, and of _molybdena_. All metallic substances are crystallizable, and each in a peculiar form, which is discovered by leaving a hole in the bottom of the crucible in which they are melted, and drawing out the stopper, when the mass is beginning to lose its fluidity. Some of the metals will not unite to others when hot, and others of them will; and such as will unite with others are called _solders_. Thus tin is a solder for lead, and brass, gold, or silver, for iron. Ores are never found in regular strata, like the different kinds of earth; but in places which have formerly been cavities, running in all directions, with respect to the regular strata, and commonly called _veins_. Many of the ores in their natural state are said to be _mineralized_ with arsenic or sulphur, those substances being intimately united with the metallic earths. In order to convert the ores into metals, some of them are first reduced to powder, to wash out the earthy or saline particles. They are then kept in a red heat, which the workmen call _roasting_, in order to drive away the arsenic, or sulphur, which are volatile; and in the last place they are fused in contact with charcoal, or other substances containing phlogiston; and to promote the fusion, lime-stone is frequently mixed with them. When the operation is completed, the unmetallic parts are converted into glass, or _scoria_, which lies on the surface, whereas the metal is found at the bottom. To discover the quantity of metal in a small piece of ore is called _assaying_. When metals are fused together, the specific gravity, fusibility, and other properties are changed, and in such a manner as could not be discovered from the properties of the constituent parts. _Of Gold._ Gold is the heaviest of all metallic bodies except platina. It appears yellow or reddish by reflected light, but green or blue by transmitted light, when it is reduced to thin plates. Though gold undergoes no change in a common furnace, or burning lens, it may, in part, at least, be calcined by the electric shock. Gold has the greatest _ductility_, and in wires of equal diameters, it has the greatest _tenacity_, of all the metals. One grain of it may be made to cover 56 square inches; some gold leaf being less than a 200,000th part of an inch thick; and when it is made to cover a silver wire, the gold upon it may not be more than one twelfth part of the thickness of the gold leaf. This metal is soluble in aqua regia; and being precipitated by a volatile alkali, makes a powder called _aurum fulminans_, which is one fourth heavier than the gold, and explodes with great violence in a heat something greater than that of boiling water. Tin precipitates gold in the form of a purple powder, called the _powder of Cassius_, from the inventor of it, and is used in enamels, or the glassy coating which is given to metals by heat. Gold unites with most of the metals, especially with mercury, and these mixtures are called _amalgams_. In gilding, the amalgam is applied to the surface of the metal to be gilded, and the mercury is driven off by heat, leaving the gold attached to the surface. Gold mixed with iron, makes it harder, for the purpose of cutting instruments. To separate gold from the imperfect metals, such as copper, &c. it is mixed with lead, and then exposed to a strong heat, which calcines the lead, and with it the imperfect metals, leaving the gold pure. This process is called _cupellation_, from being performed in a small crucible called a _cupell_. When the gold is mixed with silver, three parts more of silver are put to it, and then the silver is dissolved by nitrous acid, leaving the gold pure. This process is called _quartation_, from the gold being one fourth part of the mass. The fineness of gold is generally estimated by dividing the gold into twenty-four parts, called _carats_. The phrase twenty-three carats fine means that the mass contains twenty-three parts out of twenty-four of pure gold, the remainder being _alloy_, of some baser metal. The fineness of gold may in some measure be discovered by the colour it leaves upon a _touch-stone_, or fine-grained basaltes. Gold is generally found nearly pure, but mixed with earth, or diffused in fine grains through stones. LECTURE XXII. _Of Silver._ Silver is the whitest of all the metals, very ductile, but less so than gold; the thinnest leaves of it being one third thicker than those of gold. It is not calcined in the heat of a common furnace, but partially so by repeated fusion, or a strong burning lens. Sulphureous fumes unite with silver, and tinge it black. The nitrous acid dissolves it, and will hold more than half its weight of it in solution. When fully saturated, this solution deposits crystals, which are called _lunar nitre_, or _nitre of silver_. When these crystals are melted, and the water they contain driven off, a black substance, called _lapis infernalis_, or _lunar caustic_, is formed. This is used as a cautery in surgery. A strong heat will decompose this lunar nitre, and recover the silver. Though the nitrous acid dissolves silver the most readily, the marine acid will deprive the nitrous of it, and form a substance called _luna cornea_, because, when it is melted and cold, it becomes a transparent mass something resembling _horn_. From this luna cornea the purest silver may be obtained. The vitriolic acid will likewise deprive the nitrous of the silver contained in it, and form a white powder, not easily soluble in water. A fulminating silver may be made by the following process: the silver must first be dissolved in pale nitrous acid, then precipitated by lime-water, dried, and exposed to the air three days. It must then be washed in caustic volatile alkali, after which the fluid must be decanted, and the black powder left to dry in the air. The slightest friction will cause this powder to fulminate. It is said, that even a drop of water falling upon it will produce this effect; so that it ought to be made only in very small quantities, and managed with the greatest caution. Most of the metals precipitate silver. That by mercury may be made to assume the form of a tree, called _arbor Dianæ_. Silver is found native in Peru; and the ores frequently contain sulphur, or arsenic, or both. _Of Platina._ Platina is a metal lately discovered in the gold mines of Mexico, where it is found in small particles, never exceeding the size of a pea, mixed with ferruginous sand and quartz. The strongest fire will not melt these grains, though it will make them cohere; but they may be melted by a burning lens, or a blow-pipe supplied with dephlogisticated air. Pure platina is the heaviest body in nature, its specific gravity exceeding twenty-two. It is very malleable, though considerably harder than gold or silver, and has the property of welding in common with iron. This metal is not affected by exposure to the air, or by any simple acid, though concentrated and hot; but it is dissolved by dephlogisticated marine acid, and by aqua regia, in which a little nitrous air is procured. The solution is brown, and when diluted yellow. This liquor is very corrosive, and tinges animal substances of a blackish brown colour. Platina is precipitated from a solution in aqua regia by sal-ammoniac, as gold is by martial vitriol. Iron is precipitated from this solution by the Prussian alkali. Also most of the metals precipitate platina, but not in its metallic state. Arsenic facilitates the solution of platina; and by melting it with equal parts of arsenic and vegetable alkali, and then reducing the mass to a powder, it may be made to take any form; and a strong heat will dissipate the arsenic and the alkali, leaving the platina in the shape required, not fusible by any heat in a common furnace. Platina does not readily combine with gold or silver, and it resists the action of mercury as much as iron; but it mixes well with lead, making it less ductile, and even brittle, according to the proportion of the platina. With copper it forms a compound which takes a beautiful polish, not liable to tarnish, and is therefore used with advantage for mirrors of reflecting telescopes. It unites easily with tin, and also with bismuth, antimony, and zinc. LECTURE XXIII. _Of Mercury._ Mercury is the most fusible of all the metals, not becoming solid but in 40° below 0 in Fahrenheit's thermometer. It is then malleable. It is heavier than any other metal except gold or platina. It is volatile in a temperature much lower than that of boiling water, and in vacuo in the common temperature of the atmosphere; and at six hundred it boils. In a degree of heat in which it would rise easily in vapour, mercury imbibes pure air, and becomes a red calx, called _precipitate per se_. At a greater degree of heat it parts with that air, and is running mercury again. Mercury is not perceptibly altered by exposure to the air. Mercury is acted upon by the vitriolic acid when hot. In this process vitriolic acid air is procured, and the mercury is converted into a white substance, which being dipped in water becomes yellow, called _turbith mineral_, one third heavier than the mercury from which it was made. By heat this substance parts with its pure air, and becomes running mercury; but if the process be made in a clean earthen vessel, there will remain a portion of _red calx_, which cannot be reduced by any degree of heat, except in contact with some substance containing phlogiston. If this be done with a burning lens, in inflammable air, much of the air will be absorbed. Mercury is dissolved most readily in the nitrous acid, when the purest nitrous air is procured; and there remains a substance which is first yellow, and by continuance red, called _red precipitate_. In a greater degree of heat the dephlogisticated air will be recovered, and the mercury be revived; but the substance yields nitrous air after it becomes solid, and till it changes from yellow to red. The precipitates of mercury from acids by means of alkalies possess the property of exploding, when they are exposed to a gradual heat in an iron spoon, after having been triturated with one sixth of their weight of the flowers of sulphur. The residuum consists of a violet-coloured powder, which, by sublimation, is converted into cinnabar. It seems, therefore, as if the sulphur combined suddenly with the mercury, and expelled the dephlogisticated air in an elastic state. The marine acid seizes upon mercury dissolved in nitrous acid, and if the acid be dephlogisticated, the precipitate is _corrosive sublimate_; but with common marine acid, it is called _calomel_, or _mercurius dulcis_. This preparation is generally made in the dry way, by triturating equal parts of mercury, common salt and vitriol, and exposing the whole to a moderate heat; when the corrosive sublimate rises, and adheres to the upper part of the glass vessel in which the process is made. Mercury combines readily with sulphur by trituration, and with it forms a black powder called _Ethiops mineral_. A more intimate combination of mercury and sulphur is made by means of fire. This is called _cinnabar_, about one third of which is sulphur. Vermillion is cinnabar reduced to powder. Mercury readily unites with oil, and with it forms a deep black or blue compound, used in medicine. It readily combines with most of the metals, and when it is used in a sufficient quantity to make them soft, the mixture is called an _amalgam_. It combines most readily with gold, silver, lead, tin, bismuth, and zinc. Looking-glasses are covered on the back with an amalgam of mercury and tin. When mercury is united with lead or other metals, it is rendered less brilliant and less fluid; but agitation in pure air converts the impure metal into a calx, together with much of the mercury, in the form of a black powder. Heat recovers the pure air, and the mercury, leaving the calx of the impure metal. Much mercury is found native in a slaty kind of earth, or in masses of clay or stone; but the greatest quantity is found combined with sulphur in _native cinnabar_. LECTURE XXIV. _Of Lead._ Lead is a metal of a bluish tinge, of no great tenacity, but very considerable specific gravity, being heavier than silver. It melts long before it is red hot, and is then calcined, if it be in contact with respirable air. When boiling it emits fumes, and calcines very rapidly. It may be granulated by being poured into a wooden box, and agitated. During congelation it is brittle, so that the parts will separate by the stroke of a hammer; and by this means the form of its crystals may be discovered. In the progress of calcination it first becomes a dusky grey powder, then yellow, when it is called _massicot_; then, by imbibing pure air, it becomes red, and is called _minium_, or _red lead_. In a greater degree of heat it becomes massicot again, having parted with its pure air. If the heat be too great, and applied rapidly, it becomes a flaky substance, called _litharge_; and with more heat it becomes a _glass_, which readily unites with metallic calces and earths, and is a principal ingredient in the manufacture of _flint glass_, giving it its peculiar density and refractive power. Though lead soon tarnishes, the imperfect calx thus made does not separate from the rest of the metal, and therefore protects it from any farther action of the air, by which means it is very useful for the covering of houses, and other similar purposes. All acids act upon lead, and form with it different saline substances. _White-lead_ consists of its union with vinegar and pure air. Also dissolved in vinegar, and crystallized, it becomes _sugar of lead_, which, like all the other preparations of this metal, is a deadly poison. Oils dissolve the calces of lead, which, by this means, is the basis of paints, plaisters, &c. By means of heat litharge decomposes common salt, the lead uniting with the marine acid, and forming a yellow substance, used in painting, and by this means the fossil alkali is separated. Lead unites with most metals, though not with iron. Two parts of lead and one of tin make a _solder_, which melts with less heat than either of the metals separately; but a composition of eight parts of bismuth, five of lead, and three of tin, makes a metal which melts in boiling water. This metal will be dissolved by water if it contain any saline matter, and the drinking of it occasions a peculiar kind of cholic. Lead is sometimes found native, but generally minerally mineralized with sulphur or arsenic, and often mixed with a small quantity of silver. _Of Copper._ Copper is a metal of a reddish or brownish colour, considerably sonorous, and very malleable. At a heat far below ignition, the surface, of copper becomes covered with a range of prismatic colours, the commencement of its calcination; and with more heat a black scale is formed, which easily separates from the metal, and in a strong heat it melts, and burns with a bluish green flame. Copper rusts by exposure to the air; but the partially-calcined surface adheres to the metal, as in the case of lead, and thus preserves it from farther corrosion. Copper dissolved in the vitriolic acid forms crystals of a blot colour, called _blue copperas_. From this solution it is precipitated by iron, which by this means becomes coated with copper. The nitrous acid dissolves copper with most rapidity, producing nitrous air. If the solution be distilled, almost all the acid will be retained in the residuum, which is white; but more heat will expel the acid, chiefly in the form of dephlogisticated air, and the remainder will be a black substance, consisting of the pure calx of copper. The vegetable acids dissolve copper as well as the mineral ones, which makes the use of this metal for culinary purposes in some cases dangerous. To prevent this they give it a coat of tin. The solution of copper in the vegetable acid is called _verdigris_. Alkalies dissolve copper as well as acids. With the volatile alkali a blue liquor is formed, but in some cases it becomes colourless. All the circumstances of this change of colour have not yet been examined. Both oil and sulphur will dissolve copper, and with the latter it forms a blackish grey compound, used by dyers. Copper readily unites with melted tin, at a temperature much lower than that which is necessary to melt the copper; by which means copper vessels are easily covered with a coating of tin. A mixture of copper and tin, called _bronze_, the specific gravity of which is greater than that of the medium of the two metals, is used in casting statues, cannon, and bells; and in a certain proportion this mixture is excellent for the purpose of mirrors of reflecting telescopes, receiving a fine polish, and not being apt to tarnish. Copper and arsenic make a brittle compound called _tombach_; and with zinc it makes the useful compound commonly called _brass_, in which zinc is about one third of its weight. Copper is sometimes found native; but commonly mixed with sulphur, in ores of a red, green, or blue colour. Copper being an earlier discovery than that of iron, was formerly used for weapons and the shoeing of horses; and the ancients had a method, with which we are not well acquainted, of giving it a considerable degree of hardness, so that a sword made of it might have a pretty good edge. LECTURE XXV. _Of Iron._ Iron is a metal of a bluish colour, of the greatest hardness, the most variable in its properties, and the most useful of all the metals; so that without it it is hardly possible for any people to make great advances in arts and civilization. This metal readily parts with its phlogiston, so as to be very subject to calcine, or rust, by exposure to the air. The same is evident by the colours which appear on its surface when exposed to heat, and also when it is struck with flint; the particles that fly from it being iron partially calcined. In consequence of its readily parting with its phlogiston, it is capable of burning, like wood or other fuel, in pure air. Iron and platina have the property of _welding_ when very hot, so that two pieces may be joined without any solder. When iron is heated in contact with steam, part of the water takes the place of the phlogiston, while the rest unites with it, and makes inflammable air. By this means the iron acquires one third more weight, and becomes what is called _finery cinder_. This substance, heated in inflammable air, imbibes it, parts with its water, and becomes perfect iron again. If the iron be heated in pure air, it also imbibes the water, of which that air chiefly consists, and also a portion of the peculiar element of the pure air. The solution of iron in spirit of vitriol produces _green copperas_; which being calcined, becomes a red substance, called _colcothar_. The precipitate of iron, by an infusion of galls, is the colouring matter in _ink_, which is kept suspended by means of gum. The precipitate from the same solution by phlogisticated alkali, is _Prussian blue_. Water saturated with fixed air dissolves iron, and makes a pleasant chalybeat. The calx of iron gives a green colour to glass. Iron readily combines with sulphur. When they are found combined by nature, the substance is called _pyrites_. The union of phosphoric acid with iron makes it brittle when cold, commonly called _cold short_; and the union of arsenic makes it brittle when hot, thence called _red short_. Iron unites with gold, silver, and platina, and plunged in a white heat into mercury, it becomes coated with it; and if the process be frequently repeated, it will become brittle, which shews that there is some mutual action between them. Iron readily unites with tin; and by dipping thin plates of iron into melted tin, they get a complete coating of it, and make the _tinned plates_ in common use. When crude iron comes from the smelting furnace it is brittle; and when it is white within, it is extremely hard; but when it has a black grain, owing to its having more phlogiston, it is softer, and may be filed and bored. Cast iron becomes _malleable_ by being exposed to a blast of air when nearly melting; the consequence of which is a discharge of inflammable air, and the separation of a liquid substance, which, when concreted, is called _finery cinder_. The iron generally loses one fourth of its weight in the process. Crude iron contains much _plumbago_, and the access of pure air probably assists in discharging it, by converting it into air, chiefly inflammable. Malleable iron, exposed to a red heat in contact with charcoal, called _cementation_, converts it into _steel_, which has the properties of becoming much harder than iron, and very elastic, by being first made very hot, and then suddenly cooled, by plunging it in cold water. By first making it very hard, and then giving different degrees of heat, and cooling it in those different degrees, it is capable of a great variety of _tempers_, proper for different uses. Of the degrees of heat workmen judge by the change of colour on its surface. Steel, like crude iron, is capable of being melted without losing its properties. It is then called _cast steel_, and is of a more uniform texture. Iron acquires some little weight by being converted into steel; and when dissolved in acid, it yields more plumbago. Steel has something less specific gravity than iron. If the cementation be continued too long, the steel acquires a darkish fracture, it is more fusible, and incapable of welding. Steel heated in contact with earthy matters, is reduced to iron. Iron is the only substance capable of _magnetism_; and hardened steel alone is capable of retaining magnetism. The loadstone is an ore of iron. LECTURE XXVI. _Of Tin._ Tin is a metal of a slightly yellowish cast, though harder than lead, very malleable, but of no great tenacity; so that wires cannot be made of it. It easily extends under the hammer, and plates of it, called _tinfoil_, are made only one thousandth part of an inch thick, and might be made as thin again. Tin has less specific gravity than any other metal. It melts long before ignition, at 410 of Fahrenheit, and by the continuance of heat is slowly converted into a white powder, which is the chief ingredient in _putty_, used in polishing, &c. Like lead, it is brittle when heated little short of fusion, and may be reduced into grains by agitation as it passes from a fluid to a solid state. The calx of tin resists fusion more than that of any other metal, which makes it useful in making an opaque white enamel. Tin loses its bright surface when exposed to the air, but is not properly subject to rust; so that it is useful in protecting iron and other metals from the effects of the atmosphere. Concentrated vitriolic acid, assisted by heat, dissolves half its weight of tin, and yields vitriolic acid air. With more water it yields inflammable air. During the solution the phlogiston of the tin uniting with the acid, forms sulphur, which makes it turbid. By long standing, or the addition of water, the calx of tin is precipitated from the solution. The nitrous acid dissolves tin very rapidly without heat, and yields but little nitrous air. With marine acid this metal yields inflammable air. With aqua regia it assumes the form of a gelatinous substance used by dyers to heighten the colour of some red tinctures, so as to produce a bright scarlet in dying wool. A transparent liquor, which emits very copious fumes, called, from the inventor, _the smoking liquor of Libavius_, is made by distilling equal parts of amalgam of tin and mercury with corrosive sublimate, triturated together. A colourless liquor comes over first, and then a thick white fume, which condenses into the transparent liquor above mentioned. Mr. Adet has shewn, that this liquor bears the same relation to the common solution of tin, that corrosive sublimate does to calomel, and has given an ingenious solution of many of its properties. Tin detonates with nitre; and if the crystals made by the solution of copper in the nitrous acid be inclosed in tinfoil, nitrous fumes will be emitted, and the whole will become red hot. Also if five times its weight of sulphur be added to melted tin, a black brittle compound, which readily takes fire, will be formed. Another combination of tin, sulphur, and mercury, makes a light yellow substance called _aurum musivum_ used in painting. Tin is the principal ingredient in the composition of _pewter_, the other ingredients being lead, zinc, bismuth, and copper; each pewterer having his peculiar receipt. It is also used in coating copper and iron plates, and in silvering looking-glasses, besides being cast into a variety of forms, when it is called _block tin_. Tin is sometimes found native, but is generally mineralized with sulphur and arsenic. The latter is thought to be always contained in tin, and to be the cause of the crackling noise made by bending plates of it. _Of the Semi-metals._ Bismuth is a semi-metal of a yellowish or reddish cast, but little subject to change in the air; harder than lead, but easily broken, and reducible to powder. When broken it exhibits large shining facets, in a variety of positions. Thin pieces of it are considerably sonorous. Bismuth melts at about 460° of Fahrenheit. With more heat it ignites, and burns with a slight blue flame, while a yellowish calx, called _flowers of bismuth_, is produced. With more heat it becomes a greenish glass. In a strong heat, and in close vessels, this metal sublimes. Vitriolic acid, even concentrated and boiling, has but little effect upon bismuth; but the nitrous acid acts upon it with the greatest rapidity and violence, producing much nitrous air, mixed with phlogisticated nitrous vapour. From the solution of bismuth in this acid, a white substance, called _magistery of bismuth_, is precipitated by the affusion of water. This has been used as a paint for the skin but has been thought to injure it. The marine acid does not readily act upon bismuth; but when concentrated, it forms with it a saline combination, which does not easily crystallize, but may be sublimed in the form of a soft fusible salt, called _butter of bismuth_. Bismuth unites with most metallic substances, and in general renders them more fusible. When calcined with the imperfect metals, it unites with them, and has the same effect as lead in cupellation. Bismuth is used in the composition of pewter, in printers' types, and other metallic mixtures. This metal is sometimes found native, but more commonly mineralized with sulphur. LECTURE XXVII. _Of Nickel._ Nickel is a semi-metal of a reddish cast, of great hardness, and always magnetical; on which account it is supposed to contain iron, though chemists have not yet been able to separate them. The purest nickel was so infusible as not to run into a mass in the strongest heat of a smith's forge; but then it was in some degree malleable. Concentrated acid of vitriol only corrodes nickel. Alkalies precipitate it from its solution in the nitrous acid, and dissolve the precipitate. It readily unites with sulphur. Nickel is found either native or mineralized with several other metals, especially with copper, when it is called _kupfer nickel_, or _false copper_, being of a reddish or copper colour. This semi-metal has not yet been applied to any use. _Of Arsenic._ What is commonly called _arsenic_ is the calx of a semi-metal called the _regulus of arsenic_. It is a white and brittle substance, expelled from the ores of several metals by heat. It is then refined by a second sublimation, and melted into the masses in which it is commonly sold. This calx is soluble in about eighty times its weight of cold water, or in fifteen times its weight of boiling water. It acts in many respects like an acid, as it decomposes nitre by distillation, when the nitrous acid flies off, and the _arsenical salt of Macquer_ remains behind. When the calx of arsenic is distilled with sulphur, the vitriolic acid flies off, and a substance of a yellow colour, called _orpiment_, is produced. This appears to consist of sulphur and the regulus of arsenic; part of the sulphur receiving pure air from the calx, to which it communicates phlogiston; and thus the sulphur becomes converted into vitriolic acid, while the arsenical calx is reduced, and combines with the rest of the sulphur. The combination of sulphur and arsenic, by melting them together, is of a red colour, known by the name of _realgal_, or _realgar_. It is less volatile than orpiment. The solution of fixed alkali dissolves the calx of arsenic, and by means of heat a brown tenacious mass is produced, and having also a disagreeable smell, it is called _liver of arsenic_. The regulus of arsenic is of a yellow colour, subject to tarnish or grow black, by exposure to the air, very brittle, and of a laminated texture. In close vessels it wholly sublimes, but burns with a small flame in pure air. Vitriolic acid has little action upon this semi-metal, except when hot; but the nitrous acid acts readily upon it, and likewise dissolves the calx, as does boiling marine acid, though it affects it very little when cold. Most of the metals unite with the regulus of arsenic. Dephlogisticated marine acid converts the calx of arsenic into _arsenical acid_ by giving it pure air. The acid of arsenic acts more or less upon all metals, but the phenomena do not appear to be of much importance. The calx of acid is used in a variety of the arts, especially in the manufactory of glass. Orpiment and realgar are used as pigments. Some attempts have been made to introduce it into medicine, but being dangerous, the experiments should be made with caution. _Of Cobalt._ Cobalt is a semi-metal of a grey or steel colour, of a close-grained fracture, more difficult of fusion than copper, not easily calcined. It soon tarnishes in the air, but water has no effect upon it. Cobalt, dissolved in _aqua regia_, makes an excellent sympathetic ink, appearing green when held to the fire, and disappearing when cold, unless it has been heated too much, when it burns the paper. The calx of cobalt is of a deep blue colour, which, when fused, makes the blue glass called _smalt_. The ore of cobalt, called _zaffre_, is found in several parts of Europe, but chiefly in Saxony. As it is commonly sold, it contains twice or thrice its weight of powder of flints. The smalt is usually composed of one part of calcined cobalt, fused with two parts of powder of flint and one of pot-ash. The chief use of cobalt is for making smalt; but the powder and the blue-stone used by laundresses is a preparation made by the Dutch of a coarse kind of smalt. _Of Zinc._ Zinc is a semi-metal of a bluish cast, brighter than lead, and so far malleable as not to be broken by a hammer, though it cannot be much extended. When broken by bending, it appears to consist of cubical grains. If it be heated nearly to melting, it will be sufficiently brittle to be pulverized. It melts long before ignition, and when it is red hot, it burns with a dazzling white flame, and is calcined with such rapidity, that its calx flies up in the form of white flowers, called _flowers of zinc_, or _philosophical wool_. In a stronger heat they become a clear yellow glass. Heated in close vessels, this metal rises without decomposition, being the most volatile of all the metals except the regulus of _arsenic_. Zinc dissolved in diluted vitriolic acid, yields much inflammable air, and has a residuum, which appears to be plumbago, and the liquor forms crystals, called _white copperas_. This metals also yields inflammable air when dissolved in the marine acid. Dissolved in the nitrous acid, it yields dephlogisticated nitrous air, with very little proper nitrous air. The ore of zinc, called _calamine_, is generally of a white colour; and the chief use of it is to unite it with copper, with which it makes brass and other gold-coloured mixtures of metals. The calx and the salts of this metal are occasionally used in medicine. LECTURE XXVIII. _Of Antimony._ The regulus of antimony is of a silvery white colour, of a scaly texture, very brittle, and melts soon after ignition. By continuance of heat it calcines in white fumes, called _argentine flowers of antimony_, which melt into a hyacinthine glass. In close vessels it rises without decomposition. Its calx is soluble in water, like that of arsenic. This metal tarnishes, but does not properly rust, by exposure to the air. This metal is soluble in aqua regia. It detonates with nitre, and what remains of equal parts of nitre and regulus of antimony after detonation, in a hot crucible, is called _diaphoretic antimony_. The water used in this preparation contains a portion of the calx suspended by the alkali, and being precipitated by an acid, is called _ceruse of antimony_. When regulus of antimony is pulverized and mixed with twice its weight of corrosive sublimate (which is attended with heat) and then distilled with a gentle fire, a thick fluid comes over, which is congealed in the receiver, or in the neck of the retort, and is called _butter of antimony_. The residuum consists of revived mercury, with some regulus and calx of antimony. When this butter of antimony is thrown into pure water, there is a white precipitate, called _powder of algaroth_, a violent emetic. Nitrous acid dissolves the butter of antimony; and when an equal weight of nitrous acid has been three times distilled to dryness from butter of antimony, the residuum, after ignition, is called _bezoar mineral_, and seems to be little more than a calx of the metal. Crude antimony, which has been much used in the experiments of alchemists, is a combination of sulphur and regulus of antimony. Heat melts it, and finally converts it into glass, of a dark red colour, called _liver of antimony_. If antimony be melted or boiled with a fixed alkali, a precipitate is made by cooling, called _kermes mineral_, formerly used in medicine. The antimonial preparations that are now most in use are _antimonial wine_ and _tartar emetic_. The wine is made by infusing pulverized glass of antimony in Spanish wine some days, and filtering the clear fluid through paper. The emetic tartar, or antimonial tartar, is a saline substance, composed of acid of tartar, vegetable alkali, and antimony partially calcined. The preparation may be seen in the Dispensaries. The regulus of antimony is used in the form of pills, which purge more or less in proportion to the acid they meet with; and as they undergo little or no change in passing through the body, they are called _perpetual pills_. _Of Manganese._ Manganese is a hard, black mineral, very ponderous, and the regulus of it is a semi-metal of a dull white colour when broken, but soon grows dark by exposure to the air. It is hard and brittle, though not pulverizable, rough in its fracture, and of very difficult fusion. Its calces are white when imperfect, but black, or dark green, when perfect. The white calx is soluble in acids. When broken in pieces, it falls into powder by a spontaneous calcination, and this powder is magnetical, though the mass was not possessed of that property. The black calx of manganese is altogether insoluble in acids. It contains much dephlogisticated air. The calx of manganese is used in making glass; the glass destroying the colour of that of the other materials, and thereby making the whole mass transparent. This semi-metal mixes with most of the metals in fusion, but not with mercury. There is another ore of manganese, called _black woad_, which inflames spontaneously when mixed with oil. _Of Wolfram._ Wolfram is a mineral of a brownish or black colour, found in the tin mines of Cornwall, of a radiated or foliated texture, shining almost like a metal. It contains much of the calx of manganese, and iron; but when the substance is pulverized, these are easily dissolved, and the calx of wolfram is found to be yellow. This calx turns blue by exposure to light; and an hundred grains of it heated with charcoal will yield sixty grains of a peculiar metal, in small particles, which, when broken, look like steel. It is soluble in the vitriolic or marine acids, and reduced to a yellow calx by nitrous acid or aqua regia. _Of Molybdena._ Molybdena is a substance which much resembles plumbago; but its texture is scaly, and not easily pulverized, on account of a degree of flexibility which its laminæ possess. With extreme heat, and mixed with charcoal, it yields small particles of a metal that is grey, brittle, and extremely infusible; and uniting with several of the metals, it forms with them brittle or friable compounds. By heat it is converted into a white calx. _Of Solid Combustible Substances._ There yet remains a class of solid substances, of the _combustible_ kind, but most of them have been already considered under the form of the fluids, from which they are originally formed, as _bitumen_, _pit-coal_, and _amber_; or under the principal ingredients of which they are composed, as _sulphur_ and _plumbago_. There only remains to be mentioned the _diamond_, which is of a nature quite different from that of the other precious stones, the principal ingredient in which is siliceous earth, which renders them not liable to be much affected by heat. On the contrary, the diamond is a combustible substance; for in a degree of heat somewhat greater than that which will melt silver, it burns with a slight flame, diminishes common air, and leaves a soot behind. Also, if diamond powder be triturated with vitriolic acid, it turns it black, which is another proof of its containing phlogiston. The diamond is valued on account of its extreme hardness, the exquisite polish it is capable of, and its extraordinary refractive power; for light falling on its interior surface with an angle of incidence greater than 24½ will be wholly reflected, whereas in glass it requires an angle of 41 degrees. LECTURE XXIX. _Of the Doctrine of Phlogiston and the Composition of Water._ It was supposed to be a great discovery of Mr. Stahl, that all inflammable substances, as well as metals, contain a principle, or substance, to which he gave the name of phlogiston, and that the addition or deprivation of this substance makes some of the most remarkable changes in bodies, especially that the union of a metallic calx and this substance makes a metal; and that combustion consists in the separation of phlogiston from the substances that contain it. That it is the same principle, or substance, that enters into all inflammable substances, and metals, is evident, from its being disengaged from any of them, and entering into the composition of any of the others. Thus the phlogiston of charcoal or inflammable air becomes the phlogiston of any of the metals, when the calx is heated in contact with either of them. On the contrary, Mr. Lavoisier and most of the French chemists, are of opinion, that there is no such principle, or substance, as phlogiston; that metals and other inflammable bodies are simple substances, which have an affinity to pure air; and that combustion consists not in the separation of any thing from the inflammable substance, but in the union of pure air with it. They moreover say, that water is not, as has been commonly supposed, a simple substance, but that it consists of two elements, viz. pure air, or _oxygene_, and another, to which they give the name of _hydrogene_, which, with the principle of _heat_, called by them _calorique_, is inflammable air. The principal fact adduced by them to prove that metals do not lose any thing when they become calces, but only gain something, is, that mercury becomes a calx, called _precipitate per se_, by imbibing pure air, and that it becomes running mercury again by parting with it. This is acknowledged: but it is almost the only case of any calx being revived without the help of some known phlogistic substance; and in this particular case it is not absurd to suppose, that the mercury, in becoming precipitate per se, may retain all its phlogiston, as well as imbibe pure air, and therefore be revived by simply parting with that air. In many other cases the same metal, in different states, contains more or less phlogiston, as cast iron, malleable iron, and steel. Also there is a calx of mercury made by the acid of vitriol, which cannot be revived without the help of inflammable air, or some other substance supposed to contain phlogiston: and that the inflammable air is really imbibed in these processes, is evident, from its wholly disappearing, and nothing being left in the vessel in which the process is made beside the metal that is revived by it. If precipitate per se be revived in inflammable air, the air will be imbibed, so that running mercury may contain more or less phlogiston. The antiphlogistians also say, that the diminution of atmospherical air by the burning of phosphorus is a proof of their theory; the pure air being imbibed by that substance, and nothing emitted from it. But there is the same proof of phosphorus containing phlogiston, that there is of dry flesh containing it; since the produce of the solution of it in nitrous acid, and its effect upon the acid, are the same, viz. the production of phlogisticated air, and the phlogistication of the acid. Their proof that water is decomposed, is, that in sending steam over hot iron, inflammable air (which they suppose to be one constituent part of it) is procured; while the other part, viz. the oxygene, unites with the iron, and adds to its weight. But it is replied, that the inflammable air may be well supposed to be the phlogiston of the iron, united to part of the water, as its base, while the remainder of the water is imbibed by the calx; and that it is mere water, and not pure air, or oxygene, that is retained in the iron, is evident, from nothing but pure water being recovered when this calx of iron is revived in inflammable air, in which case the inflammable air wholly disappears, taking the place of the water, by which it had been expelled. In answer to this it is said, that the pure air expelled from the calx uniting with the inflammable air in the vessel, recomposes the water found after this process. But in every other case in which any substance containing pure air is heated in inflammable air, though the inflammable air be in part imbibed, some _fixed air_ is produced, and this fixed air is composed of the pure air in the substance and part of the inflammable air in the vessel. Thus, if _minium_, which contains pure air, and _massicot_, which contains none, be heated in inflammable air, in both the cases lead will be revived by the absorption of inflammable air; but in the former case only, and not in the latter, will fixed air be produced. The calx of iron, therefore, having the same effect with massicot, when treated in the same manner, appears to contain no more pure air than massicot does. Besides this explanation of the facts on which the new theory is founded, which shews it to be unnecessary, the old hypothesis being sufficient for the purpose, some facts are alledged, as inconsistent with the new doctrine. If the calx of iron made by water, and charcoal made by the greatest degree of heat, be mixed together, a great quantity of inflammable air will be produced; though, according to the new theory, neither of these substances contained any water, which they maintain to be the only origin of it. But this fact is easily explained upon the doctrine of phlogiston; the water in this calx uniting with the phlogiston of the charcoal, and then forming inflammable air; and it is the same kind of inflammable air that is made from charcoal and water. Also the union of inflammable and pure air, when they are fired together by means of the electric spark, produces not pure water, as, according to the new theory, it ought to do, but _nitrous acid_. To this it has been objected, that the acid thus produced came from the decomposition of phlogisticated air, a small portion of which was at first contained in the mixture of the two kinds of air. But when every particle of phlogisticated air is excluded, the strongest acid is procured. They find, indeed, that by the slow burning of inflammable air in pure air, they get pure water. But then it appears, that whenever this is the case, there is a production of phlogisticated air, which contains the necessary element of nitrous acid; and this is always the case when there is a little surplus of the inflammable air that is fired along with the pure air, as the acid is always procured when there is a redundancy of pure air. That much water should be procured by the decomposition of these kinds of air, is easily accounted for, by supposing that water, or steam, is the basis of these, as well as of all other kinds of air. Since air something better than that of the atmosphere is constantly produced from water by converting it into vapour, and also by removing the pressure of the atmosphere, and these processes do not appear to have any limits; it seems probable, that _water_ united to the principle of _heat_; constitutes atmospherical air; and if so, it must consist of the elements of both dephlogisticated and phlogisticated air; which is a supposition very different from that of the French chemists. LECTURE XXX. _Of Heat._ Heat is an affection of bodies well known by the sensation that it excites. It is produced by friction or compression, as by the striking of flint against steel, and the hammering of iron, by the reflection or refraction of light, and by the combustion of inflammable substances. It has been long disputed, whether the cause of heat be properly a _substance_, or some particular affection of the particles that compose the substance that is heated. But be it a substance, or a principle of any other kind, it is capable of being transferred from one body to another, and the communication of it is attended with the following circumstances. All substances are expanded by heat, but some in a greater degree than others; as metals more than earthy substances, and charcoal more than wood. Also some receive and transmit heat through their substance more readily than others; metals more so than earths, and of the metals, copper more readily than iron. Instruments contrived to ascertain the expansion of substances by heat, are called _pyrometers_, and are of various constructions. As a standard to measure the degrees of heat, mercury is in general preferable to any other substance, on account of its readily receiving, and communicating, heat through its whole mass. _Thermometers_, therefore, or instruments to measure the degrees of heat, are generally constructed of it, though, as it is subject to become solid in a great degree of cold, ardent spirit, which will not freeze at all, is more proper in that particular case. The graduation of thermometers is arbitrary. In that of Fahrenheit, which is chiefly used in England, the freezing point of water is 32°, and the boiling point 212°. In that of Reaumur, which is chiefly used abroad, the freezing point of water is 0, and the boiling point 80. To measure the degrees of heat above ignition, Mr. Wedgwood has happily contrived to use pieces of clay, which contract in the fire; and he has also been able to find the coincidence of the degrees in mercurial thermometers with those of his own. To measure the degrees of heat and cold during a person's absence, Lord George Cavendish contrived an instrument, in which a small bason received the mercury, that was raised higher than the place for which it was regulated by heat or cold, without a power of returning. But Mr. Six has lately hit upon a better method, viz. introducing into the tube of his thermometer a small piece of iron, which is raised by the ascent of the mercury, and prevented from descending by a small spring; but which may be brought back to its former place by a magnet acting through the glass. Heat, like light, is propagated in right lines; and what is more remarkable, cold observes the same laws. For if the substance emitting heat without light, as iron below ignition, be placed in the focus of a burning mirror, a thermometer in the focus of a similar mirror, placed parallel to it, though at a considerable distance, will be heated by it, and if a piece of ice be placed there, the mercury will fall. Heat assists the solvent power of almost all menstrua; so that many substances will unite in a certain degree of heat, which will form no union at all without it, as dephlogisticated and inflammable air. If substances be of the same kind, they will receive heat from one another, in proportion to their masses. Thus, if a quantity of water heated to 40° be mixed with another equal quantity of water heated to 20°, the whole mass will be heated to 30°. But if the substances be of different kinds, they will receive heat from each other in different proportions, according to their _capacity_ (as it is called) of receiving heat. Thus, if a pint of mercury of the temperature of 136 be mixed with a pint of water of the temperature of 50, the temperature of the two after mixture will not be a medium between those two numbers, viz. 93, but 76; consequently the mercury was cooled 60°, while the water was heated only 26; so that 26 degrees of heat in water correspond to 60 in mercury. But mercury is about 13 times specifically heavier than water, so that an equal weight of mercury would contain only one thirtieth part of this heat; and dividing 26 by 13, the quotient is 2. If _weight_, therefore, be considered, the heat discovered by water should be reckoned as 2 instead of 60; and consequently when water receives 2 degrees of heat, an equal weight of mercury will receive 60°; and dividing both the numbers by 2, if the heat of water be 1, that of the mercury will be 30. Or since they receive equal degrees of heat, whether they discover it or not (and the less they discover, the more they retain in a latent state) a pound of mercury contains no more than one thirtieth part of the heat actually existing in a pound of water of the same temperature. Water, therefore, is said to have a greater capacity for receiving and retaining heat, without discovering it, than mercury, in the proportion of 30 to 1, if weight be considered, or of 60 to 26, that is of 30 to 13; if _bulk_ be the standard, though, according to some, it is as 3 to 2. The capacity of receiving heat in the substance is greatest in a state of vapour, and least in that of a solid; so that when ice is converted into water, heat is absorbed, and more still when it is converted into vapour; and on the contrary, when vapour is converted into water, it gives out the heat which it had imbibed, and when it becomes ice it gives out still more. If equal quantities of ice and water be exposed to heat at the temperature of 32°, the ice will only become water, without receiving any additional sensible heat; but an equal quantity of water in the same situation would be raised to 178°, so that 146 degrees of heat will be imbibed, and remain in latent in the water, in consequence of its passing from a state of ice: and heat communicated by a given weight of vapour will raise an equal weight of a nonevaporable substance, of the same capacity with water, 943 degrees; so that much more heat is latent in steam, than in the water from which it was formed. This doctrine of latent heat explains a great variety of phænomena in nature; as that of cooling bodies by evaporation, the vapour of water, or any other fluid substance, absorbing and carrying off the heat they had before. Water, perfectly at rest, will fall considerably below the freezing point, and yet continue fluid: but on the slightest agitation, the congelation of the whole, or part of it, takes place instantly, and if the whole be not solid, it will instantly rise to 32°, the freezing point. From whatever cause, some motion seems necessary to the commencement of congelation, at least in a moderate temperature; but whenever any part of the water becomes solid, it gives out some of the heat it had before, and that heat which was before latent becoming sensible, and being diffused through the whole mass, raises its temperature. On the same principle, when water heated higher than the boiling point in a digester is suddenly permitted to escape in the form of steam, the remainder is instantly reduced to the common boiling point, the heat above that point being carried off in a latent state by the steam. Had it not been for this wise provision in nature, the whole of any quantity of water would, in all cases of freezing, have become solid at once; and also the whole of any quantity that was heated to the point of boiling, would have been converted into steam at once; circumstances which would have been extremely inconvenient, and often fatal. This doctrine also explains the effect of freezing mixtures, as that of salt and snow. These solid substances, on being mixed, become fluid, and that fluid absorbing much heat, deprives all the neighbouring bodies of part of what they had. But if the temperature at which the mixture is made be as low as that to which this mixture would have brought it, it has no effect, and in a lower temperature this new fluid would become solid; for that mixture has only a certain determinate capacity for heat, and if the neighbouring bodies have less heat, they will take from it. It has been observed, that the comparative heat of bodies containing phlogiston is increased by calcination or combustion; so that the calx of iron has a greater capacity for heat, and therefore contains more latent heat, than the metal. In general it is not found, that the same substances have their capacity for receiving heat increased by an increase of temperature; but this is said to be the case with a mixture of ardent spirit and water, and also that of spirit of vitriol and water. Since all substances contain a greater or less quantity of heat, and in consequence of being deprived of it become colder and colder, it is a question of some curiosity to determine the extent to which this can go, or at what degree in the scale of a thermometer any substance would be absolutely cold, or deprived of all heat; and an attempt has been made to solve this problem in the following manner. Comparing the capacity of water with that of ice, by means of a third substance, viz. mercury, it has been found, that if that of ice be 9°, that of water is 10°; so that water in becoming ice gives out one tenth part of its whole quantity of heat. But it has been shown, that ice in becoming water absorbs 146 degrees of heat. This, therefore, being one tenth part of the whole heat of water, it must have contained 1460 degrees; so that taking 32 degrees, which is the freezing point, from that number, the point of absolute cold will be 1426 below 0 of Fahrenheit's scale. By a computation, made by means of the heat of inflammable and dephlogisticated air, at the temperature of 50, Dr. Crawford finds, that it contains nearly 1550 degrees of heat; so that the point of absolute cold will be 1500 below 0. But more experiments are wanted to solve this curious problem to entire satisfaction. LECTURE XXXI. _Of Animal Heat._ Since all animals, and especially those that have red blood, are much hotter than the medium in which they live, the source of this heat has become the subject of much investigation; and as the most probable theory is that of Dr. Crawford, I shall give a short detail of the reasons on which it is founded. Having, with the most scrupulous attention, ascertained the _latent_, or, as he calls it, the _absolute_ heat of blood, and also that of the aliments of which it is composed, he finds that it contains more than could have been derived from _them_. Also finding that the absolute heat of arterial blood exceeds that of venous blood, in the proportion of 11½ to 10, he concludes that it derives its heat from the air respired in the lungs, and that it parts with this _latent_ heat, so that it becomes sensible, in the course of its circulation, in which it becomes loaded with phlogiston, which it communicates to the air in the lungs. That this heat is furnished by the _air_, he proves, by finding, that that which we inspire contains more heat than that which we expire, or than the aqueous humor which we expire along with it, in a very considerable proportion; so that if the heat contained in the pure air did not become latent in the blood, it would raise its temperature higher than that of red-hot iron. And again, if the venous blood, in being converted into arterial blood, did not receive a supply of latent heat from the air, its temperature would fall from 96 to 104 below 0 in Fahrenheit's thermometer. That the heat procured by combustion has the same source, viz. the dephlogisticated air that is decomposed in the process, is generally allowed; and Dr. Crawford finds, that when equal portions of air are altered by the respiration of a Guinea pig, or by the burning of charcoal, the quantity of heat communicated by the two processes is nearly equal. The following facts are also alleged in favour of his theory. Whereas animals which have much red blood, and respire much, have the power of keeping themselves in a temperature considerably higher than that of the surrounding atmosphere, other animals, as _frogs_ and _serpents_, are nearly of the same temperature with it; and those animals which have the largest respiratory organs, as birds, are the warmest; also the degree of heat is in some measure proportionable to the quantity of air that is respired in a given time, as in violent exercise. It has been observed, that animals in a medium hotter than the blood have a power of preserving themselves in the same temperature. In this case the heat is probably carried off by perspiration, while the blood ceases to receive, or give out, any heat; and Dr. Crawford finds, that when an animal is placed in a warm medium the colour of the venous blood approaches nearer to that of the arterial than when it is placed in a colder medium; and also, that it phlogisticates the air less than in the former case; so that in these circumstances respiration has not the same effect that it has in a colder temperature, in giving the body an additional quantity of heat; which is an excellent provision in nature, as the heat is not wanted, but, on the contrary, would prove inconvenient. LECTURE XXXII. _Of Light._ Another most important agent in nature, and one that has a near connexion with heat, is _light_, being emitted by all bodies in a state of ignition, and especially by the sun, the great source of light and of heat to this habitable world. Whether light consists of particles of matter (which is most probable) or be the undulation of a peculiar fluid, filling all space, it is emitted from all luminous bodies in right lines. Falling upon other bodies, part of the light is _reflected_ at an angle equal to that of its incidence, though not by impinging on the reflecting surface, but by a power acting at a small distance from it. But another part of the light enters the body, and is _refracted_ or bent _towards_, or _from_, the perpendicular to the surface of the new medium, if the incidence be oblique to it. In general, rays of light falling obliquely on any medium are bent as if they were attracted by it, when it has a greater density, or contains more of the inflammable principle, than the medium through which it was transmitted to it. More of the rays are reflected when they fall upon a body with a small degree of obliquity to its surface, and more of them are transmitted, or enter the body, when their incidence is nearer to a perpendicular. The velocity with which light is emitted or reflected is the same, and so great that it passes from the sun to the earth in about eight minutes and twelve seconds. Rays of light emitted or reflected from a body entering the pupil of the eye, are so refracted by the humours of it, as to be united at the surface of the retina, and so make images of the objects, by means of which they are visible to us; and the magnifying power of telescopes or microscopes depends upon contriving, by means of reflections or refractions, that pencils of rays issuing from every point of any object shall first diverge, and then converge, as they would have done from a much larger object, or from one placed much nearer to the eye. When a beam of light is bent out of its course by refraction, all the rays of which it consists are not equally refracted, but some of them more and others less; and the colour which they are disposed to exhibit is connected invariably with the degree of their refrangibility; the red-coloured rays being the least, and the violet the most refrangible, and the rest being more or less so in proportion to their nearness to these, which are the extremes, in the following order, violet, indigo, blue, green, yellow, orange, red. These colours, when separated as much possible, are still contiguous; and all the shades of each colour have likewise their separate and invariable degrees of refrangibility. When separated as distinctly as possible, they divide the whole space between them exactly as a musical chord is divided in order to found the several notes and half notes of an octave. These differently-coloured rays of light are also separated in passing through the transparent medium of air and water, in consequence of which the sky appears blue and the sea green, these rays being returned, while the red ones proceed to a greater distance. By this means also objects at the bottom of the sea appear to divers red, and so do all objects enlightened by an evening sun. The mixture of all the differently-coloured rays, in the proportions in which they cover the coloured image above mentioned, makes a _white_, and the absence of all light is _blackness_. By means of the different refrangibility of light, the colours of the rainbow may be explained. The distance to which the differently-coloured rays are separated from each other is not in proportion to the mean refractive power of the medium, but depends upon the peculiar constitution of the substance by which they are refracted. The _dispersing power_ of glass, into the composition of which _lead_ enters, is great in proportion to the mean refraction; and it is proportionally little in that glass in which there is much alkaline salt. The construction of _achromatic telescopes_ depends upon this principle. Not only have different rays of light these different properties with respect to bodies, so as to be more or less refracted, or dispersed, by them, but different sides of the same rays seem to have different properties, for they are differently affected on entering a piece of _island crystal_. With the same degree of incidence; part of the pencil of rays, consisting of all the colours, proceeds in one direction, and the rest in a different one; so that objects seen through a piece of this substance appear double. At the surface of all bodies rays of light are promiscuously reflected, or transmitted. But if the next surface be very near to it, the rays of one colour chiefly are reflected, and the rest transmitted, and these places occur alternately for rays of each of the colours in passing from the thinnest to the thickest parts of the medium; so that several series, or orders, of colours will be visible on the surface of the same thin transparent body. On this principle coloured rings appear between a plane and a convex lens, in a little oil on the surface of water, and in bubbles made with soap and water. When rays of light pass near to any body, so as to come within the sphere of its attraction and repulsion, an _inflection_ takes place; all the kinds of rays being bent _towards_, or _from_, the body, and these powers affecting some rays more than others, they are by this means also separated from each other, so that coloured streaks appear both within the shadow, and the outside of it, the red rays being inflected at the greatest distance from the body. Part of the light which enters bodies is retained within them, and proceeds no farther; but so loosely in some kinds of bodies, that a small degree of heat is sufficient to expel it again, so as to make the body visible in the dark: but the more heat is applied, the sooner is all the light expelled. This is a strong argument for the materiality of light. _Bolognian phosphorus_ is a substance which has this property; but a composition made by Mr. Canton, of calcined oyster-shells and sulphur, in a much greater degree. However, white paper, and most substances, except the metals, are possessed of this property in a small degree. Some bodies, especially phosphorus, and animal substances tending to putrefaction, emit light without being sensibly hot. The _colours_ of vegetables, and likewise their _taste_ and _smell_, depend upon light. It is also by means of light falling on the leaves and other green parts of plants, that they emit dephlogisticated air, which preserves the atmosphere fit for respiration. It is light that imparts colour to the skins of men, by means of the fluid immediately under them. This is the cause of _tanning_, of the _copper colour_ of the North Americans, and the _black_ of the Negroes. Light also gives colour to several other substances, especially the solutions of mercury in acids. LECTURE XXXIII. _Of Magnetism._ Magnetism is a property peculiar to iron, or some ores of it. The earth itself, owing probably to the iron ores contained in it, has the same property. But though all iron is acted upon by magnetism, _steel_ only is capable of having the power communicated to it. Every magnet has two poles, denominated _north_ and _south_, each of which attracts the other, and repels that of the same kind with itself. If a magnet be cut into two parts, between the two poles, it will make two magnets, the parts that were contiguous becoming opposite poles. Though the poles of a magnet are denominated _north_ and _south_, they do not constantly, and in all parts of the earth, point due north or south, but in most places to the east or west of them, and with a considerable variation in a course of time. Also a magnet exactly balanced at its center will have a declination from an horizontal position of about 70 degrees. The former is called the _variation_, and the latter the _dipping_ of the magnetic needle. A straight bar of iron which has been long fixed in a vertical position, will become a magnet, the lower end becoming a north pole, and the upper end a south one; for if it be suspended horizontally, the lower end will point towards the north, and the upper end towards the south. Also any bar of iron, not magnetical, held in a vertical position, will become a temporary magnet, the lower end becoming a north pole, and the upper end a south one; and a few strokes of a hammer will fix the poles for a short time, though the position of the ends be changed. Magnetism may likewise be given to a bar of iron by placing it firmly in the position of the dipping-needle, and rubbing it hard one way with a polished steel instrument. Iron will also become magnetical by ignition and quenching it in water in the position of the dipping-needle. Magnetism acts, without any diminution of its force, through any medium; and iron not magnetical will have that power while it is in connexion with a magnet, or rather the power of the magnet is extended through the iron. Steel filings gently thrown upon a magnet, adhere to it in a curious manner; and the filings, acquiring magnetism by the contact, adhere together, and form a number of small magnets, which arrange themselves according to the attraction of the poles of the original magnet. This experiment is made to the most advantage upon a piece of pasteboard, or paper, placed over the magnet. Magnetism is communicated by the friction, or the near position, of a magnet to a piece of steel of a size less than it. For this reason a combination of magnetical bars will have a greater effect than a single one; and in the following manner, beginning without any magnetism at all, the greatest quantity may be procured. Six bars of steel may be rendered slightly magnetical by fixing each of them successively to an upright poker, and stroking it several times from the bottom to the top with the lower end of an old pair of tongs. If then four of these bars be joined, the magnetism of the remaining two will be much increased by a proper method of rubbing with them; and by changing their places, joining the strongest, and acting upon the weakest, they may all be made as magnetical as they are capable of being. The strength of a natural magnet may be increased by covering its polar extremities with steel. This is called the _arming_ of the loadstone. To account for the variation of the needle, Dr. Halley supposed the earth to consist of two parts, an external _shell_ and an internal _nucleus_, detached, and having a revolution distinct from it; and that the action of the poles of the shell and of the nucleus would explain all the varieties in the position of the needle. But others think that the cause of the magnetism of the earth is not _within_, but _without_ itself. One reason for this opinion is, that a magnet is liable to be affected by a strong aurora borealis; and another is, that the variation of the needle proceeds in such manner as supposes that the motion of the nucleus must be quicker than that of the shell of the earth; whereas, since it is most natural to suppose that motion was communicated to the nucleus by the shell, it would be slower. Some idea of the quantity and the progress of the variation of the needle may be formed from the following facts.--At the Cape of Good Hope, when it was discovered by the Portuguese, in 1486, there was no variation, the needle there pointing due north; in 1622 it was about 2 degrees westward, in 1675 it was 8° W. in 1700 about 11° W. in 1756 about 18° W. and in 1774 about 21½° W. In London, in 1580, the variation was 11 degrees 15 seconds E.; in 1622 it was 6° E. in 1634 it was 4 deg. 5 min. E. in 1657 it was nothing at all; in 1672 it was 2 deg. 30 min. W. in 1692 it was 6 deg. W. in 1753 it was about 16 W. and at present it is about 21 W. The longitude may in some places be found by the variation of the needle; and Mr. Churchman, of America, having given much attention to the subject, comparing the observations of others, and many of his own, thinks that he has found a method of determining the longitude to a great degree of certainty, in most cases, by this means. He says there are two magnetic poles of the earth, one to the north and the other to the south, at different distances from the poles of the earth, and revolving in different times; and from the combined influence of these two poles he deduces rules for the position of the needle in all places of the earth, and at all times, past, present, or to come. The north magnetic pole, he says, makes a complete revolution in 426 years, 77 days, 9 hours, and the south pole in about 5459 years. In the beginning of the year 1777 the north magnetic pole was in 76 deg. 4 min. north latitude; and in longitude from Greenwich 140 deg. east; and the south was in 72 deg. south latitude, and 140 deg. east from Greenwich. LECTURE XXXIV. _Of Electricity._ Electricity is a property belonging to, or capable of being communicated to, all substances whatever; and whereas by some of them it is transmitted with great ease, and by others with much difficulty, they have been divided into two classes, and denominated _conductors_ or _non-conductors_ of electricity. Also the latter receiving this power by friction, and other means, are termed _electrics_, and the former _non-electrics_. Metals of all kinds, and water, are conductors, though in very different degrees; so also is charcoal. All other substances, and also a perfect vacuum, are non-conductors of electricity. But many of these substances, when they are made very hot, as glass, resin, baked wood, and perhaps all the rest on which the experiment can be made in this state, are conductors. It is the property of all kinds of electrics, when they are rubbed by bodies different from themselves, to attract light substances of all kinds, to exhibit an appearance of _light_, attended with a particular _sound_, on the approach of any conductor; and if the nostrils are presented, they are affected with a _smell_ like that of phosphorus. This attraction is most easily explained by supposing that electricity is produced by a fluid exceedingly elastic, or repulsive of itself, and attracted by all other substances. An electric exhibiting the appearances above mentioned, is said to be _excited_, and some of them, particularly the _tourmaline_, are excited by heating and cooling, as well as by friction. It appears, however, that excitation consists in the mere transferring of electricity from one substance to another, and that the great source of electricity is in the earth. On this account it is necessary to the considerable excitation of any electric, that the substance against which it is rubbed (hence termed _the rubber_) have a communication with the earth, by means of conductors; for if the rubber be _insulated_, that is cut off from all communication with the earth by means of electrics, the friction has but little effect. When insulated bodies have been attracted by, and brought into contact with, an excited electric, they begin to be repelled by it, and also to repel one another; nor will they be attracted again till they have been brought into contact with some conductor communicating with the earth; but after this they will be attracted as at first. If conductors be _insulated_, electric powers may be communicated to them by the approach of excited electrics, or the contact of other electrified bodies. They will then attract light bodies, and give sparks, &c. like the excited electrics themselves. When electricity is strongly communicated to insulated animal bodies, the pulse is quickened, and perspiration increased; and if they receive, or part with, their electricity on a sudden, a painful sensation is felt at the place of communication. But what is more extraordinary, is, that the influence of the brain and nerves upon the muscles seems to be of an electric nature. This is one of the last and most important of all philosophical discoveries. I shall, therefore, give the result of all the observations that have hitherto been made on the subject, in a _series of propositions_, drawn up by an intelligent friend, who has given much more attention to it than I have done. 1. The nerve of the limb of an animal being laid bare, and surrounded with a piece of sheet lead, or of tinfoil, if a communication be formed between the nerve thus armed and any of the neighbouring muscles, by means of a piece of zinc, strong contractions will be produced in the limb. 2. If a portion of the nerve which has been laid bare be armed as above, contractions will be produced as powerfully, by forming the communication between the armed and bare part of the nerve, as between the armed part and muscle. 3. A similar effect is produced by arming a nerve and simply touching the armed part of the nerve with the metallic conductor. 4. Contractions will take place if a muscle be armed, and a communication be formed by means of the conductor between it and a neighbouring nerve. The same effect will be produced if the communication be formed between the armed muscle and another muscle, which is contiguous to it. 5. Contractions may be produced in the limb of an animal by bringing the pieces of metal into contact with each other at some distance from the limb, provided the latter make part of a line of communication between the two metallic conductors. The experiment which proves this is made in the following manner. The amputated limb of an animal being placed upon a table, let the operator hold with one hand the principal nerve, previously laid bare, and in the other let him hold a piece of zinc; let a small plate of lead or silver be then laid upon the table, at some distance from the limb, and a communication be formed, by means of water, between the limb and the part of the table where the metal is lying. If the operator touch the piece of silver with the zinc, contractions will be produced in the limb the moment that the metals come into contact with each other. The same effect will be produced if the two pieces of metal be previously placed in contact, and the operator touch one of them with his finger. This fact was discovered by Mr. William Cruikshank. 6. Contractions can be produced in the amputated leg of a frog, by putting it into water, and bringing the two metals into contact with each other at a small distance from the limb. 7. The influence which has passed through, and excited contractions in, one limb, may be made to pass through, and excite contractions in, another limb. In performing this experiment it is necessary to attend to the following circumstances: let two amputated limbs of a frog be taken; let one of them be laid upon a table, and its foot be folded in a piece of silver; let a person lift up the nerve of this limb with a silver probe, and another person hold in his hand a piece of zinc, with which he is to touch the silver including the foot; let the person holding the zinc in one hand catch with the other the nerve of the second limb, and he who touches the nerve of the first limb is to hold in his other hand the foot of the second; let the zinc now be applied to the silver including the foot of the first limb, and contractions will immediately be excited in both limbs. 8. The heart is the only involuntary muscle in which contractions can be excited by these experiments. 9. Contractions are produced more strongly, the farther the coating is placed from the origin of the nerve. 10. Animals which were almost dead have been found to be considerably revived by exciting this influence. 11. When these experiments are repeated upon an animal that has been killed by opium, or by the electric shock, very slight contractions are produced; and no contractions whatever will take place in an animal that has been killed by corrosive sublimate, or that has been starved to death. 12. Zinc appears to be the best exciter when applied to gold, silver, molybdena, steel, or copper. The latter metals, however, excite but feeble contractions when applied to each other. Next to zinc, in contact with these metals, tin and lead, and silver and lead, appear to be the most powerful exciters. At least two kinds of fishes, the _torpedo_ and the _electrical eel_, have a voluntary power of giving so strong a shock to the water in which they swim, as to affect fishes and other animals which come near them; and by a conducing communication between different parts of these fishes, an electric shock may be given exactly like that of the Leyden phial, which will be described hereafter; and if the communication be interrupted, a flash of electric light will be perceived. The growth of vegetables is also quickened by electricity. LECTURE XXXV. _The same Subject continued._ No electric can be excited without producing electric appearances in the body with which it is excited, provided that body be insulated; for this insulated rubber will attract light bodies, give sparks, and make a snapping noise, upon the approach of a conductor, as well as the excited electric. If an insulated conductor be pointed, or if a pointed conductor, communicating with the earth, be held pretty near it, little or no electric appearance will be exhibited, only a light will appear at each of the points during the act of excitation, and a current of air will be sensible from off them both. The effect of pointed bodies is best explained on the supposition of the electric matter in one body repelling that in another; and consequently the electricity belonging to a body with a large surface making a greater resistance to the entrance of foreign electricity than that belonging to a smaller. These two electricities, viz. that of the excited electric, and that of the rubber, though similar to, are the reverse of, one another. A body attracted by the one will be repelled by the other, and they will attract, and in all respects act upon, one another more sensibly than upon other bodies; so that two pieces of glass or silk possessed of contrary electricities will cohere firmly together, and require a considerable force to separate them. These two electricities having been first discovered by producing one of them from glass, and the other from amber, sealing-wax, sulphur, rosin, &c. first obtained the names of _vitreous_ and _resinous_ electricity; and it being afterwards imagined that one of them was a redundancy, and the other a deficiency, of a supposed electric fluid, the former has obtained the name of _positive_, and the latter that of _negative_, electricity; and these terms are now principally in use. Positive and negative electricity may be distinguished from each other by the manner in which they appear at the points of bodies. From a pointed body electrified positively, there issues a stream of light, divided into denser streams, at the extremities; whereas, when the point is electrified negatively, the light is more minutely divided, and diffused equally. The former of these is called a _brush_, and the latter a _star_. If a conductor not insulated be brought within the atmosphere (that is the sphere of action) of any electrified body, it acquires the electricity opposite to that of the electrified body, and the nearer it is brought, the stronger opposite electricity does it acquire, till the one receive a spark from the other, and then the electricity of both will be discharged. The electric substance which separates the two conductors possessing these two opposite kinds of electricity, is said to be _charged_. Plates of glass are the most convenient for this purpose, and the thinner the plate the greater is the charge it is capable of holding. The conductors contiguous to each side of the glass are called their _coating_. Agreeably to the above-mentioned general principle, it is necessary that one side of the charged glass have a communication with the rubber, while the other receives the electricity from the conductor, or with the conductor, while the other receives from the rubber. It follows also, that the two sides of the plate thus charged are always possessed of the two opposite electricities; that side which communicates with the excited electric having the electricity of the electric, and that which communicates with the rubber, that of the rubber. There is, consequently, a very eager attraction between these two electricities with which the different sides of the plate are charged, and when a proper communication is made by means of conductors, a flash of electric light, attended with a report (which is greater or less in proportion to the quantity of electricity communicated to them, and the goodness of the conductors) is perceived between them, and the electricity of both sides is thereby discharged. The substance of the glass itself in, or upon, which these electricities exist, is impervious to electricity, and does not permit them to unite; but if they be very strong, and the plate of glass very thin, they will force a passage through the glass. This, however, always breaks the glass, and renders it incapable of another charge. The flash of light, together with the explosion between the two opposite sides of a charged electric, is generally called the _electric shock_, on account of the disagreeable sensation it gives any animal whose body is made use of to form the communication been them. The electric shock is always found to perform the circuit from one side of the charged glass to the other by the shortest passage through the best conductors. Common communicated electricity also observes the same rule in its transmission from one body to another. It has not been found, that the electric shock takes up any sensible space of time in being transmitted to the greatest distances. The electric shock, as also the common electric spark, displaces the air through which it passes; and if its passage from conductor to conductor be interrupted by non-conductors of a moderate thickness, it will rend and tear them in its passage, in such a manner as to exhibit the appearance of a sudden expansion of the air about the center of the shock. If the electric circuit be interrupted, the electric matter, during the discharge, will pass to any other body that lies near its path, and instantly return. This may be called the _lateral explosion_. The effect of this lateral explosion through a brass chain, when the quantity of electricity is very great, will be the discolouring and partial burning of the paper on which it lies. If a great quantity of electricity be accumulated, as in a _battery_, the explosion will pass over the surfaces of imperfect conductors without entering them, and the effect will be a strong _concussion_ of the substance. Also the electric matter thus accumulated and condensed will, by its repulsion, form _concentric circles_, which will appear by melting the surface of a flat piece of metal on which the explosion is received. If an electric shock, or strong spark, be made to pass through, or over, the belly of a muscle, it forces it to contract, as in a convulsion. If a strong shock be sent through a small animal body, it will often deprive it instantly of life. When the electric shock is very strong, it will give polarity to magnetic needles, and sometimes it reverses their poles. Great shocks, by which animals are killed, are said to hasten putrefaction. Electricity and lightning are in all respects the same thing; since every effect of lightning may be imitated by electricity, and every experiment in electricity may be made with lightning, brought down from the clouds by means of insulated pointed rods of metal. LECTURE XXXVI. _The same Subject continued._ Three curious and important instruments, which are among the latest improvements in electricity, deserve a particular explanation, and in all of them the effect depends upon the general principles mentioned above, viz. that bodies placed within the influence, or, as it is usually termed, within the atmosphere, of an electrified body, are affected by a contrary electricity, and that these two electricities mutually attract each other. These instruments are the _electrophorus_, the _condenser_ of electricity, and the _doubler_ of it. The electrophorus consists of an insulated conducting plate applied to an insulated electric. If the latter have any electricity communicated to it, for example the negative, the positive electricity of the former will be attracted by it, and consequently the plate will be capable of receiving electricity from any body communicating with the earth; being, in this situation, capable of containing more electricity than its natural quantity. Consequently, when it is removed from the lower plate, and the whole of its electricity equally diffused through it, it will appear to have a redundance, and therefore will give a spark to any body communicating with the earth. Being then replaced upon the electric, and touched by any body communicating with the earth, it will be again affected as before, and give a spark on being raised; and this process may be continued at pleasure, the electrophorus supplying the place of any other electrical machine. If the conducting plate of the electrophorus be applied to a piece of dry wood, marble, or any other substance through which electricity can pass but very slowly, or if the insulated conducting plate be covered with a piece of thin silk, which will make some resistance to the passage of electricity, and it be then applied to another plate communicating with the earth; and if, in either of these cases, a body with a large surface possessed of a weak electricity be applied to the conducting plate, the weak electricity not being able to overcome the obstruction presented to it, so as to be communicated to the other plate, will affect it with the contrary electricity, and this reacting on the first plate, will condense its electricity on that part of the plate to which it is contiguous; in consequence of which its capacity of receiving electricity will be increased; so that on the separation of the two plates, that electricity which was before condensed, being equally diffused through the whole plate, will have a greater intensity than it had before, attracting light bodies, or even giving a spark, when the body from which it received its electricity was incapable of it. For though it contained a great quantity of electricity, it was diffused through so large a space that its intensity was very small. This instrument is therefore called a _condenser of electricity_. If an insulated plate of metal possessing the smallest degree of electricity be presented very near to another plate communicating with the earth, it will affect this plate with the opposite electricity; and this being, in the same manner, applied to a third plate, will put it into the same state with the first. If then these two plates be joined, and the first plate be presented to either of them, its own electricity being attracted by that of the plate presented, that of the other will be drawn into it, so that its quantity will be doubled. The same process being repeated, will again double the electricity of this plate, till, from being quite insensible to the most exquisite electrometer, it will become very conspicuous, or even give sparks. This instrument is therefore called a _doubler of electricity_, of excellent use in ascertaining the quality of atmospherical electricity when ever so small. If this instrument be so constructed that these three plates can be successively presented to one another by the revolution of one of them on an axis, it is called the _revolving doubler_; and in this form it is most convenient for use. THE END. Transcriber's Note: Details of corrections |Position |Original |Correction | | | | | |Lecture I, first paragraph |limestone |lime-stone | |Lecture I, last paragraph |_attraction_ |_attraction_, | |Lecture III, first paragraph |viz |viz. | |Lecture III, last paragraph |1. |1 | |Lecture XVII, penultimate paragraph |dissoved |dissolved | |Lecture XIX, "Of Calcareous Earth" |hundreth |hundredth | |Lecture XXVI, "Of Semi-metals" |ignates |ignites | |Lecture XXVIII, first paragraph |animony |antimony | 
38246	----	Note: Project Gutenberg also has an HTML version of this file which includes the original illustrations. See 38246-h.htm or 38246-h.zip: (http://www.gutenberg.org/files/38246/38246-h/38246-h.htm) or (http://www.gutenberg.org/files/38246/38246-h.zip) HEROES OF SCIENCE. Chemists by M. M. PATTISON MUIR, M.A., F.R.S.E., Fellow, and Prælector in Chemistry, of Gonville and Caius College, Cambridge. Published under the Direction of the Committee of General Literature and Education Appointed by the Society for Promoting Christian Knowledge. London: Society for Promoting Christian Knowledge, Northumberland Avenue, Charing Cross; 43, Queen Victoria Street, E.C.; 26, St. George's Place, Hyde Park Corner, S.W. Brighton: 135, North Street. New York: E. & J. B. Young & Co. 1883. "The discoveries of great men never leave us; they are immortal; they contain those eternal truths which survive the shock of empires, outlive the struggles of rival creeds, and witness the decay of successive religions."--BUCKLE. "He who studies Nature has continually the exquisite pleasure of discerning or half discerning and divining laws; regularities glimmer through an appearance of confusion, analogies between phenomena of a different order suggest themselves and set the imagination in motion; the mind is haunted with the sense of a vast unity not yet discoverable or nameable. There is food for contemplation which never runs short; you gaze at an object which is always growing clearer, and yet always, in the very act of growing clearer, presenting new mysteries."--THE AUTHOR OF "ECCE HOMO." "Je länger ich lebe, desto mehr verlern' ich das Gelernte, nämlich die Systeme."--JEAN PAUL RICHTER. PREFACE. I have endeavoured in this book to keep to the lines laid down for me by the Publication Committee of the Society, viz. "to exhibit, by selected biographies, the progress of chemistry from the beginning of the inductive method until the present time." The progress of chemistry has been made the central theme; around this I have tried to group short accounts of the lives of those who have most assisted this progress by their labours. This method of treatment, if properly conducted, exhibits the advances made in science as intimately connected with the lives and characters of those who studied it, and also impresses on the reader the continuity of the progress of natural knowledge. The lives of a few chemists have been written; of others there are, however, only scanty notices to be found. The materials for this book have been collected chiefly from the following works:-- Kopp's "Geschichte der Chemie." Thomson's "History of Chemistry." Ladenburg's "Entwickelungsgeschichte der Chemie." Wurtz's "History of the Atomic Theory." Watts's "Dictionary of Chemistry." Whewell's "History of the Inductive Sciences." Rodwell's "Birth of Chemistry;" "Inquiry into the Hermetic Mystery and Alchemy" (London, 1850); "Popular Treatises on Science written during the Middle Ages," edited for the Historical Society of Science by Thomas Wright, M.A. (London, 1841); "Ripley Reviv'd; or, An Exposition upon Sir George Ripley's Hermetico-Poetical Works," by Eirenæus Philalethes (London, 1678); "Tripus Aureus, hoc est Tres Tractates Chymici Selectissimi" (Frankfurt, 1618). "Alchemy;" article in "Encyclopædia Britannica." Boyle's "Sceptical Chymist." "Biographie Universelle;" for notices of Berzelius and Lavoisier. "English Cyclopædia;" for notices of Black, Berzelius and Lavoisier. Black's "Lectures," with Memoir: edited by Dr. Robinson. Priestley's "Memoirs:" written partly by himself. Priestley's works on "Air," etc. Lavoisier's "Oeuvres." Dalton's "Life," by Dr. Henry; "Life," by Dr. R. Angus Smith; "New System of Chemical Philosophy." Davy's "Collected Works;" with Life, by his brother; "Life," by Dr. Paris. Berzelius's "Lehrbuch," and various dissertations. Wöhler's "Jugenderinnerungen eines Chemikers." Graham's "Collected Memoirs." Sketch of Graham's life, in Chemical Society's Journal. "Life-Work of Liebig," by A. W. Hofmann. "Dumas," by A. W. Hofmann. Various dissertations by Liebig and Dumas in _Annalen_, and elsewhere. My warmest thanks are due to my friend, Mr. Francis Rye, for the great assistance he has given me in correcting the proof-sheets. M. M. PATTISON MUIR. CAMBRIDGE, _April, 1883_. CONTENTS. PAGE INTRODUCTORY 1 CHAPTER I. ALCHEMY: AND THE DAWN OF CHEMISTRY. Beginnings of natural knowledge--Chemistry in the Middle Ages--Alchemy--The phlogistic theory 5 CHAPTER II. ESTABLISHMENT OF CHEMISTRY AS A SCIENCE--PERIOD OF BLACK, PRIESTLEY AND LAVOISIER. Introduction of accurate measurements into chemistry--Black's researches on alkalis and on fixed air--His conception of heat--Priestley's experiments on airs--His discovery of oxygen--Lavoisier, the founder of the science of chemistry--He clearly establishes a connection between composition and properties of bodies 30 CHAPTER III. ESTABLISHMENT OF GENERAL PRINCIPLES OF CHEMICAL SCIENCE--PERIOD OF DALTON. Dalton's training in physical science--He revives and renders quantitative the atomic theory--The term "atom" is applied by him to elements and compounds alike--His rules for chemical synthesis 106 CHAPTER IV. ESTABLISHMENT OF GENERAL PRINCIPLES OF CHEMICAL SCIENCE (_continued_)--PERIOD OF DAVY AND BERZELIUS. Electro-chemistry--The dualistic theory developed by Berzelius--Davy's work on acids, alkalis, and salts--He proves chlorine to be an element--His discovery of the safety-lamp 155 CHAPTER V. THE WORK OF GRAHAM. Graham traces the movements of molecules--He distinguishes between colloids and cystalloids--Dialysis 232 CHAPTER VI. RISE AND PROGRESS OF ORGANIC CHEMISTRY--PERIOD OF LIEBIG AND DUMAS. The barrier between inorganic and organic chemistry begins to be broken down--Wöhler prepares urea--Dumas opposes the dualistic system of Berzelius--Liebig's conception of compound radicles--His work in animal and agricultural chemistry 252 CHAPTER VII. MODERN CHEMISTRY. The relations between composition and properties of bodies are developed and rendered more definite--Physical methods are more largely made use of in chemistry--Spectroscopic analysis 294 CHAPTER VIII. SUMMARY AND CONCLUSION 316 HEROES OF SCIENCE. INTRODUCTORY. As we trace the development of any branch of natural knowledge we find that there has been a gradual progress from vague and fanciful to accurate and definite views of Nature. We find that as man's conceptions of natural phenomena become more accurate they also for a time become more limited, but that this limitation is necessary in order that facts may be correctly classified, and so there may be laid the basis for generalizations which, being definite, shall also be capable of expansion. At first Nature is strange; she is full of wonderful and fearful appearances. Man is overwhelmed by the sudden and apparently irregular outbreaks of storms, by the capricious freaks of thunder and lightning, by the awful and unannounced devastations of the volcano or the earthquake; he believes himself to be surrounded by an invisible array of beings more powerful than himself, but, like himself, changeable in their moods and easily provoked to anger. After a time he begins to find that it is possible to trace points of connection between some of the appearances which had so overpowered or perplexed him. The huntsman observes that certain kinds of plants always grow where the game which he pursues is chiefly to be found; from the appearance of the sky at morning and evening the fisherman is able to tell whether there will follow weather suitable for him to set out in his fishing-boat; the tiller of the ground begins to feel sure that if he sow the seed in the well-dug soil and water it in proper seasons he will certainly reap the harvest in due time. And thus man comes to believe that natural events follow each other in a fixed order; there arises a conscious reference on his part of certain effects to certain definite causes. Accurate knowledge has begun. As knowledge of natural appearances advances there comes a time when men devote themselves chiefly to a careful study of some one class of facts; they try to consider that part of Nature with which they are mostly concerned as separate from all other parts of Nature. Thus the various branches of natural knowledge begin to have each a distinct existence. These branches get more and more subdivided, each division is more accurately studied, and so a great number of facts is accumulated in many classes. Then we usually find that a master mind arises, who shows the connection which exists between the different parts of each division of natural knowledge, who takes a wide, far-reaching view of the whole range of the province of knowledge which he studies, and who, at the same time, is able to hold in his vision all the important details of each branch of which that province is composed. And thus we again get wide views of Nature. But these are very different from the vague, dim and hesitating notions in which natural knowledge had its beginnings. In this later time men see that Nature is both simple and complex; that she is more wonderful than their fathers dreamed, but that through all the complexity there runs a definite purpose; that the apparently separate facts are bound together by definite laws, and that to discover this purpose and these laws is possible for man. As we trace this progress in the various branches of natural knowledge we are struck with the fact that each important advance is generally accomplished by one or two leading men; we find that it becomes possible to group the history of each period round a few central figures; and we also learn that the character of the work done by each of these men of note is dependent on the nature and training of the individual man. It will be my endeavour in the following pages to give an account of the advance of chemical science, grouping the facts in each stage of progress round the figures of one or two men who were prominent in that period. For the purposes of this book it will be necessary that I should sketch only the most important periods in the story of chemical progress, and that in each of these I should fill in the prominent points alone. I shall therefore select three periods in the progress of this science, and try to give an account of the main work done in each of these. And the periods will be:-- I. The period wherein, chiefly by the work of Black, Priestley and Lavoisier, the aim of chemical science was defined and the essential characters of the phenomena to be studied were clearly stated. II. The period during which, chiefly by the labours of Dalton, Berzelius and Davy, the great central propositions of the science were laid down and were developed into a definite theory. As belonging in great extent to this period, although chronologically later, I shall also consider the work of Graham. III. The period when, chiefly owing to advances made in organic chemistry, broader and more far-reaching systems of classification were introduced, and the propositions laid down in the preceding period were modified and strengthened. The workers in this period were very numerous; I shall chiefly consider these two--Liebig and Dumas. I shall conclude with a brief sketch of some of the important advances of chemical science in more recent times, and a summary of the characteristics of each of the three periods. CHAPTER I. ALCHEMY: AND THE DAWN OF CHEMISTRY. Early chemistry was not a science. The ancient chemists dealt chiefly with what we should now call chemical manufactures; they made glass, cleaned leather, dyed cloth purple and other colours, extracted metals from their ores, and made alloys of metals. No well-founded explanations of these processes could be expected either from men who simply used the recipes of their predecessors, or from philosophers who studied natural science, not by the help of accurate experiments, but by the unaided light of their own minds. At somewhat later times chemistry assumed a very important place in the general schemes propounded by philosophers. Change is vividly impressed on all man's surroundings: the endeavour to find some resting-place amidst the chaos of circumstances, some unchanging substance beneath the ever-changing appearances of things, has always held a prominent place with those who study the phenomena of the world which surrounds them. In the third and fourth centuries of our era much attention was given to the art which professed to explain the changes of Nature. Religion, philosophy, and what we should now call natural science, were at that time closely intermingled; the scheme of things which then, and for several centuries after that time, exerted a powerful influence over the minds of many thinkers was largely based on the conception of a fundamental unity underlying and regulating the observed dissimilarities of the universe. Thus, in the _Emerald Table of Hermes_, which was held in much repute in the Middle Ages, we read-- "True, without error, certain and most true: that which is above is as that which is below, and that which is below is as that which is above, for performing the miracles of the _One Thing_; and as all things were from one, by the mediation of one, so all things arose from this one thing by adaptation: the father of it is the Sun, the mother of it is the Moon, the wind carried it in its belly, the nurse of it is the Earth. This is the father of all perfection, the consummation of the whole world." And again, in a later writing we have laid down the basis of the art of alchemy in the proposition that "there abides in nature a certain pure matter, which, being discovered and brought by art to perfection, converts to itself proportionally all imperfect bodies that it touches." To discover this fundamental principle, this _One Thing_, became the object of all research. Earth and the heavens were supposed to be bound together by the all-pervading presence of the One Thing; he who should attain to a knowledge of this precious essence would possess all wisdom. To the vision of those who pursued the quest for the One Thing the whole universe was filled by one ever-working spirit, concealed now by this, now by that veil of sense, ever escaping identification in any concrete form, yet certainly capable of being apprehended by the diligent searcher. Analogy was the chief guide in this search. If it were granted that all natural appearances were manifestations of the activity of one essential principle, then the vaguest and most far-fetched analogies between the phenomena of nature might, if properly followed up, lead to the apprehension of this hidden but everywhere present essence. The history of alchemy teaches, in the most striking manner, the dangers which beset this method of pursuing the study of Nature; this history teaches us that analogies, unless founded on carefully and accurately determined facts, are generally utterly misleading in natural science. Let us consider the nature of the experimental evidence which an alchemist of the fourth or fifth century could produce in favour of his statement that transmutation of one kind of matter into another is of constant occurrence in Nature. The alchemist heated a quantity of water in an open glass vessel; the water slowly disappeared, and when it was all gone there remained in the vessel a small quantity of a white earthy solid substance. What could this experiment teach save that water was changed into earth and air? The alchemist then plunged a piece of red-hot iron into water placed under a bell-shaped glass vessel; some of the water seemed to be changed into air, and a candle, when brought into the bell, caused the air therein to take fire. Therefore, concluded the experimenter, water is proved to be changeable into fire. A piece of lead was then strongly heated in the air; it lost its lustre and became changed into a reddish-white powder, very unlike lead in its properties; this powder was then heated in a convenient vessel with a little wheat, whereupon the lead was again produced. Therefore, said the alchemist, lead is destroyed by fire, but it can be reproduced from its ashes by the help of heat and a few grains of corn. The experimenter would now proceed to heat a quantity of a mineral containing lead in an open vessel made of pulverized bones; the lead slowly disappeared, and at the close of the experiment a button of silver remained. Might he not triumphantly assert that he had transmuted lead into silver? In order that the doctrine of the transmutation of metals might rest on yet surer evidence, the alchemist placed a piece of copper in spirits of nitre (nitric acid); the metal disappeared; into the green liquid thus produced he then placed a piece of iron; the copper again made its appearance, while the iron was removed. He might now well say that if lead was thus demonstrably changed into silver, and copper into iron, it was, to say the least, extremely probable that any metal might be changed into any other provided the proper means for producing the change could be discovered. But the experimental alchemist had a yet stranger transmutation wherewith to convince the most sceptical. He poured mercury in a fine stream on to melted sulphur; at once the mercury and the sulphur disappeared, and in their place was found a solid substance black as the raven's wing. He then heated this black substance in a closed vessel, when it also disappeared, and in its place there was found, deposited on the cooler part of the vessel, a brilliantly red-coloured solid. This experiment taught lessons alike to the alchemist, the philosopher, and the moralist of these times. The alchemist learned that to change one kind of matter into another was an easy task: the philosopher learned that the prevalence of change or transmutation is one of the laws of Nature: and the moralist learned that evil is not wholly evil, but contains also some germs of good; for was not the raven-black substance emblematical of the evil, and the red-coloured matter of the good principle of things?[1] On such experimental evidence as this the building of alchemy was reared. A close relationship was believed to prevail through the whole phenomena of Nature. What more natural then than to regard the changes which occur among the forms of matter on this earth as intimately connected with the changes which occur among the heavenly bodies? Man has ever been overawed by the majesty of the stars; yet he has not failed to notice that the movements of these bodies are apparently capricious. The moon has always been to him a type of mutability; only in the sun has he seemed to find a settled resting-point. Now, when we remember that in the alchemical scheme of things the material earth and material heavens, the intellectual, the moral, and the spiritual world were regarded as one great whole, the parts of which were continuously acting and reacting on each other, we cannot wonder that the alchemist should regard special phenomena which he observed in his laboratory, or special forms of matter which he examined, as being more directly than other phenomena or other forms of matter, under the influence of the heavenly bodies. This connection became gradually more apparent to the student of alchemy, until at last it was fixed in the language and the symbols which he employed. Thus the sun (Sol) was represented by a circle, which likewise became the symbol for gold, as being the most perfect metal. The moon (Luna) was ever changing; she was represented by a half-circle, which also symbolized the pale metal silver. Copper and iron were regarded as belonging to the same class of metals as gold, but their less perfect nature was denoted by the sign + or ^. Tin and lead belonged to the lunar class, but like copper they were supposed to be imperfect metals. Mercury was at once solar and lunar in its properties. These suppositions were summed up in such alchemical symbols as are represented below-- [Illustration: Sol. Gold.] [Illustration: Luna. Silver.] [Illustration: Venus. Copper.] [Illustration: Mars. Iron.] [Illustration: Jupiter. Tin.] [Illustration: Saturn. Lead.] [Illustration: Mercury. Quicksilver.] Many of the alchemical names remain to the present time; thus in pharmacy the name "lunar caustic" is applied to silver nitrate, and the symptoms indicative of lead-poisoning are grouped together under the designation of "saturnine cholic." But as the times advanced the older and nobler conception of alchemy became degraded. If it be true, the later alchemists urged, that all things suffer change, but that a changeless essence or principle underlies all changing things, and that the presence of more or less of this essence confers on each form of matter its special properties, it follows that he who can possess himself of this principle will be able to transmute any metal into any other; he will be able to change any metal into gold. Now, as the possession of gold has always carried with it the means of living luxuriously, it is easy to understand how, when this practical aspect of alchemy had taken firm root in men's minds, the pursuit of the art became for all, except a few lofty and noble spirits, synonymous with the pursuit of wealth. So that we shall not, I think, much err if we describe the chemistry of the later Middle Ages as an effort to accumulate facts on which might be founded the art of making gold. In one respect this was an advance. In the early days of alchemy there had been too much trusting to the mental powers for the manufacture of natural facts: chemists now actually worked in laboratories; and very hard did many of these alchemists work. Paracelsus says of the alchemists, "They are not given to idleness, nor go in a proud habit, or plush and velvet garments, often showing their rings upon their fingers, or wearing swords with silver hilts by their sides, or fine and gay gloves upon their hands; but diligently follow their labours, sweating whole days and nights by their furnaces. They do not spend their time abroad for recreation, but take delight in their laboratory. They put their fingers amongst coals, into clay and filth, not into gold rings. They are sooty and black like smiths and miners, and do not pride themselves upon clean and beautiful faces." By thus "taking delight in their laboratories" the later alchemists gathered together many facts; but their work centred round one idea, viz. that metals might all be changed into gold, and this idea was the result rather of intellectual guessing than of reasoning on established facts of Nature. One of the most famous alchemists of the Middle Ages was born at Einsiedeln, in Switzerland, in 1493. His name, when paraphrased into Greek, became Paracelsus. This man, some of whose remarks have just been quoted, acquired great fame as a medical practitioner, and also as a lecturer on medicine: he travelled throughout the greater part of Europe, and is supposed to have been taught the use of several new medicines by the Arabian physicians whom he met in Spain. With an over-weening sense of his own powers, with an ardent and intemperate disposition, revolting against all authority in medicine or science, Paracelsus yet did a good work in calling men to the study of Nature as the only means whereby natural science could be advanced. "Alchemy has but one aim and object," Paracelsus taught: "to extract the quintessence of things, and to prepare arcana and elixirs which may serve to restore to man the health and soundness he has lost." He taught that the visible universe is but an outer shell or covering, that there is a spirit ever at work underneath this veil of phenomena; but that all is not active: "to separate the active function (the spirit) of this outside shell from the passive" was, he said, the proper province of alchemy. Paracelsus strongly insisted on the importance of the changes which occur when a substance burns, and in doing this he prepared the way for Stahl and the phlogistic chemists. However we may admire the general conceptions underlying the work of the earlier alchemists, we must admit that the method of study which they adopted could lead to very few results of lasting value; and I think we may add that, however humble the speculations of these older thinkers might appear, this humility was for the most part only apparent. These men were encompassed (as we are) by unexplained appearances: they were every moment reminded that man is not "the measure of all things;" and by not peering too anxiously into the mysteries around them, by drawing vague conclusions from partially examined appearances, they seemed at once to admit their own powerlessness and the greatness of Nature. But I think we shall find, as we proceed with our story, that this is not the true kind of reverence, and that he is the really humble student of Nature who refuses to overlook any fact, however small, because he feels the tremendous significance of every part of the world of wonders which it is his business and his happiness to explore. As examples of the kind of explanation given by alchemists of those aspects of Nature which they professed to study, I give two quotations from translations of the writings of Basil Valentine and Paracelsus, who flourished in the first half of the fifteenth and sixteenth centuries respectively. "Think most diligently about this; often bear in mind, observe and comprehend that all minerals and metals together, in the same time, and after the same fashion, and of one and the same principal matter, are produced and generated. That matter is no other than a mere vapour, which is extracted from the elementary earth by the superior stars, or by a sidereal distillation of the macrocosm; which sidereal hot infusion, with an airy sulphureous property, descending upon inferiors, so acts and operates as that there is implanted, spiritually and invisibly, a certain power and virtue in those metals and minerals; which fume, moreover, resolves in the earth into a certain water wherefrom all metals are thenceforth generated and ripened to their perfection, and thence proceeds this or that metal or mineral, according as one of the three principles acquires dominion and they have much or little of sulphur and salt, or an unequal mixture of these; whence some metals are fixed, that is, constant or stable; and some are volatile and easily changeable, as is seen in gold, silver, copper, iron, tin and lead." "The life of metals is a secret fatness; of salts, the spirit of aqua fortis; of pearls, their splendour; of marcasites and antimony, a tingeing metalline spirit; of arsenics, a mineral and coagulated poison. The life of all men is nothing else but an astral balsam, a balsamic impression, and a celestial invisible fire, an included air, and a tingeing spirit of salt. I cannot name it more plainly, although it is set out by many names." When the alchemists gave directions for making the stone which was to turn all it touched into gold, they couched them in such strange and symbolical language as this: "After our serpent has been bound by her chain, penetrated with the blood of our green dragon, and driven nine or ten times through the combustible fire into the elementary air, if you do not find her to be exceeding furious and extremely penetrating, it is a sign that you do not hit our subject, the notion of the homogenea, or their proportion; if this furious serpent does not come over in a cloud and turn into our virgin milk, or argentine water, not corrosive at all and yet insensibly and invisibly devouring everything that comes near it, it is plainly to be seen that you err in the notion of our universal menstruum." Or, again, what could any reasonable man make of this? "In the green lion's bed the sun and moon are born; they are married and beget a king. The king feeds on the lion's blood, which is the king's father and mother, who are at the same time his brother and sister. I fear I betray the secret, which I promised my master to conceal in dark speech from any one who knows not how to rule the philosopher's fire." Concerning the same lion, another learned author says that "though called a lion, it is not an animal substance, but for its transcendant force, and the rawness of its origin, it is called the green lion." But he adds in a moment of confidence: "This horrid beast has so many names, that unless God direct the searcher it is impossible to distinguish him." And once more. "Take our two serpents, which are to be found everywhere on the face of the earth: tie them in a love-knot and shut them up in the Arabian _caraha_. This is the first labour; but the next is more difficult. Thou must encamp against them with the fire of nature, and be sure thou dost bring thy line round about. Circle them in and stop all avenues that they find no relief. Continue this siege patiently, and they turn into an ugly venomous black toad, which will be transformed to a horrible devouring dragon, creeping and weltering in the bottom of her cave without wings. Touch her not by any means, for there is not on earth such a vehement transcending poison. As thou hast begun so proceed, and this dragon will turn into a swan. Henceforth I will show thee how to fortify thy fire till the phoenix appear: it is a red bird of a most deep colour, with a shining fiery hue. Feed this bird with the fire of his father and the ether of his mother: for the first is meat and the second is drink, and without this last he attains not to his full glory. Be sure to understand this secret," etc., etc. The alchemists spoke of twelve gates through which he who would attain to the palace of true art must pass: these twelve gates were to be unlocked by twelve keys, descriptions of which, couched in strange and symbolical language, were given in alchemical treatises. Thus in "Ripley reviv'd"[2] we read that Canon Ripley, of Bridlington, who lived in the time of Edward IV., sang thus of the first gate, which was "Calcination:"-- "The battle's fought, the conquest won, The Lyon dead reviv'd; The eagle's dead which did him slay, And both of sense depriv'd. The showers cease, the dews which fell For six weeks do not rise; The ugly toad that did so swell With swelling bursts and dies." And of the third gate, or "Conjunction," we find the Canon saying-- "He was a king, yet dead as dead could be; His sister a queen, Who when her brother she did breathless see, The like was never seen, She cryes Until her eyes With over-weeping were waxed dim-- So long till her tears Reach'd up to her ears: The queen sunk, but the king did swim." In some books these gates and keys are symbolically represented in drawings, _e.g._ in a pamphlet by Paracelsus, called "Tripus Aureus, hoc est Tres Tractates chymici selectissimi." (Frankfurt, 1618.) It is evident that a method of studying Nature which resulted in such dim and hazy explanations as these was eminently fitted to produce many who pretended to possess secrets by the use of which they could bring about startling results beyond the power of ordinary men; and, at the same time, the almost universal acceptance of such statements as those I have quoted implied the existence in men generally of a wondrous readiness to believe anything and everything. Granted that a man by "sweating whole days and nights by his furnaces" can acquire knowledge which gives him great power over his fellows, it necessarily follows that many will be found ready to undergo these days and nights of toil. And when we find that this supposed knowledge is hidden under a mask of strange and mystical signs and language, we may confidently assert that there will be many who learn to repeat these strange terms and use these mystical signs without attempting to penetrate to the truths which lie behind--without, indeed, believing that the mystical machinery which they use has any real meaning at all. We find, as a matter of fact, that the age of the alchemists produced many deceivers, who, by mumbling incantations and performing a few tricks, which any common conjuror would now despise, were able to make crowds of men believe that they possessed a supernatural power to control natural actions, and, under this belief, to make them part with their money and their substance. One respectable physician of the Hague, who entertained a peripatetic alchemist, complains that the man entered his "best-furnished room without wiping his shoes, although they were full of snow and dirt." However, the physician was rewarded, as the stranger gave him, "out of his philosophical commiseration, as much as a turnip seed in size" of the much-wished-for stone of wisdom. That the alchemist of popular belief was a man who used a jargon of strange and high-sounding words, that he might the better deceive those whom he pretended to help, is evident from the literature of the sixteenth and seventeenth centuries. In the play of the "Alchymist" Ben Jonson draws the character of Subtle as that of a complete scoundrel, whose aim is to get money from the pockets of those who are stupid enough to trust him, and who never hesitates to use the basest means for this end. From the speeches of Subtle we may learn the kind of jargon employed by the men who pretended that they could cure diseases and change all baser metals into gold. "_Subtle._ Name the vexations and the martyrizations of metals in the work. _Face._ Sir, putrefaction, Solution, ablution, sublimation, Cohobation, calcination, ceration, and Fixation. _Sub._ And when comes vivification? _Face._ After mortification. _Sub._ What's cohobation? _Face._ 'Tis the pouring on Your aqua regis, and then drawing him off, To the trine circle of the seven spheres. * * * * * _Sub._ And what's your mercury? _Face._ A very fugitive; he will be gone, sir. _Sub._ How know you him? _Pace._ By his viscosity, His oleosity, and his suscitability." Even in the fourteenth century, Chaucer (in the "Canon's Yeoman's Tale") depicts the alchemist as a mere cunning knave. A priest is prevailed on to give the alchemist money, and is told that he will be shown the change of base metal into gold. The alchemist busies himself with preparations, and sends the priest to fetch coals. "And whil he besy was, this feendly wrecche, This false chanoun (the foule feende him fecche) Out of his bosom took a bechen cole In which ful subtilly was maad an hole, And therein put was of silver lymayle An unce, and stopped was withoute fayle The hole with wex, to keep the lymayle in. And understondith, that this false gyn Was not maad there, but it was maad before." This "false gyn" having been put in the crucible and burned with the rest of the ingredients, duly let out its "silver lymayle" (filings), which appeared in the shape of a small button of silver, and so accomplished the "false chanoun's" end of deceiving his victim. The alchemists accumulated many facts: they gained not a little knowledge concerning the appearances of Nature, but they were dominated by a single idea. Living in the midst of an extremely complex order of things, surrounded by a strange and apparently capricious succession of phenomena, they were convinced that the human intelligence, directed and aided by the teachings of the Church, would guide them through the labyrinth. And so they entered on the study of Nature with preconceived notions and foregone conclusions: enthusiastic and determined to know although many of them were, they nevertheless failed because they refused to tread the only path which leads to true advances in natural science--the path of unprejudiced accurate experiment, and of careful reasoning on experimentally determined facts. And even when they had become convinced that their aims were visionary, they could not break free from the vicious system which bound them. "... I am broken and trained To my old habits: they are part of me. I know, and none so well, my darling ends Are proved impossible: no less, no less, Even now what humours me, fond fool, as when Their faint ghosts sit with me and flatter me, And send me back content to my dull round."[3] One of the most commonly occurring and most noticeable changes in the properties of matter is that which proceeds when a piece of wood, or a candle, or a quantity of oil burns. The solid wood, or candle, or the liquid oil slowly disappears, and this disappearance is attended with the visible formation of flame. Even the heavy fixed metals, tin or lead, may be caused to burn; light is produced, a part of the metal seems to disappear, and a white (or reddish) solid, very different from the original metal, remains. The process of burning presents all those peculiarities which are fitted to strike an observer of the changes of Nature; that is, which are fitted to strike a chemist--for chemistry has always been recognized as having for its object to explain the changes which matter undergoes. The chemists of the seventeenth and eighteenth centuries were chiefly occupied in trying to explain this process of burning or combustion. Van Helmont (1577-1644), who was a physician and chemist of Brussels, clearly distinguished between common air and other "airs" or gases produced in different ways. Robert Hooke (1635-1703), one of the original Fellows of the Royal Society, in the "Micographia, or Philosophical Description of Minute Bodies," published in 1665, concluded from the results of numerous experiments that there exists in common air a peculiar kind of gas, similar to, or perhaps identical with the gas or air which is got by heating saltpetre; and he further supposed that when a solid burns, it is dissolved by (or we should now say, it is converted into a gas by combining with) this peculiar constituent of the air. John Mayow (1645-1679), a physician of Oxford, experimented on the basis of facts established by Hooke. He showed that when a substance, _e.g._ a candle, burns in air, the volume of air is thereby lessened. To that portion of the air which had _dissolved_ the burned substance he gave the name of _nitre-air_, and he argued that this air exists in condensed form in nitre, because sulphur burns when heated with nitre in absence of common air. Mayow added the most important fact--a fact which was forgotten by many later experimenters--that the solid substance obtained by burning a metal in air weighs more than the metal itself did before burning. He explained this increase in weight by saying that the burning metal absorbs particles of "nitre-air" from the atmosphere. Thus Hooke and Mayow had really established the fact that common air consists of more than one definite kind of matter--in other words, that common air is not an element; but until recent times the term "element" or "elementary principle" was used without any definite meaning. When we say that the ancients and the alchemists recognized four elements--earth, air, fire, and water--we do not attach to the word "element" the same definite meaning as when we now say, "Iron is an element." From earth, air, fire and water other substances were obtained; or it might be possible to resolve other substances into one or more of these four. But even to such a word as "substance" or "matter" no very definite meaning could be attached. Although, therefore, the facts set forth by Hooke and Mayow might now justify the assertion that air is not an element, they did not, in the year 1670, necessarily convey this meaning to men's minds. The distinction between element and compound was much more clearly laid down by the Hon. Robert Boyle (1627-1691), whose chemical work was wonderfully accurate and thorough, and whose writings are characterized by acute scientific reasoning. We shall again return to these terms "element" and "compound." But the visible and striking phenomenon in most processes of burning is the production of light and sometimes of flame. The importance of the fact that the burned substance (when a solid) weighs more than the unburned substance was overshadowed by the apparent importance of the outward part of the process, which could scarcely be passed over by any observer. There appears to be an outrush of _something_ from the burning substance. There _is_ an outrush of something, said Becher and Stahl, and this something is the "principle of fire." The principle of fire, they said, is of a very subtle nature; its particles, which are always in very rapid motion, can penetrate any substance, however dense. When metals burn--the argument continued--they lose this principle of fire; when the burned metal--or _calx_ as it was usually called--is heated with charcoal it regains this "principle," and so the metal is re-formed from the calx. Thus arose the famous theory of _phlogiston_ (from Greek, = "burned"), which served as a central nucleus round which all chemical facts were grouped for nearly a hundred years. John Joachim Becher was born at Speyer in 1635, and died in 1682; in his chemical works, the most important of which is the "Physica Subterranea," he retained the alchemical notion that the metals are composed of three "principles"--the nitrifiable, the combustible, and the mercurial--and taught that during calcination the combustible and mercurial principles are expelled, while the nitrifiable remains in the calx. George Ernest Stahl--born at Anspach in 1660, and died at Berlin in 1734--had regard chiefly to the principles which escape during the calcination of metals, and simplifying, and at the same rendering more definite the idea of Becher, he conceived and enunciated the theory of phlogiston. But if _something_ (name it "phlogiston" or call it by any other name you please) is lost by a metal when the metal is burned, how is it that the loss of this thing is attended with an increase in the weight of the matter which loses it? Either the theory of phlogiston must be abandoned, or the properties of the _thing_ called phlogiston must be very different from those of any known kind of matter. Stahl replied, phlogiston is a "principle of levity;" the presence of phlogiston in a substance causes that substance to weigh less than it did before it received this phlogiston. In criticizing this strange statement, we must remember that in the middle of the seventeenth century philosophers in general were not firmly convinced of the truth that the essential character of matter is that it possesses weight, nor of the truth that it is impossible to destroy or to create any quantity of matter however small. It was not until the experimental work of Lavoisier became generally known that chemists were convinced of these truths. Nevertheless, the opponents of the Stahlian doctrine were justified in asking for further explanations--in demanding that some other facts analogous to this supposed fact, viz. that a substance can weigh less than nothing, should be experimentally established. The phlogistic theory however maintained its ground; we shall find that it had a distinct element of truth in it, but we shall also find that it did harm to scientific advance. This theory was a wide and sweeping generalization from a few facts; it certainly gave a central idea around which some facts might be grouped, and it was not very difficult, by slightly cutting down here and slightly adding there, to bring many new discoveries within the general theory. We now know that in order to explain the process of combustion much more accurate knowledge was required than the chemists of the seventeenth century possessed; but we ought to be thankful to these chemists, and notably to Stahl, that they did not hesitate to found a generalization on the knowledge they had. Almost everything propounded in natural science has been modified as man's knowledge of nature has become wider and more accurate; but it is because the scientific student of nature uses the generalizations of to-day as stepping-stones to the better theories of to-morrow, that science grows "from more to more." Looking at the state of chemistry about the middle of the eighteenth century, we find that the experiments, and especially the measurements, of Hooke and Mayow had laid a firm basis of fact concerning the process of combustion, but that the phlogistic theory, which appeared to contradict these facts, was supreme; that the existence of airs, or gases, different from common air was established, but that the properties of these airs were very slightly and very inaccurately known; that Boyle had distinguished element from compound and had given definite meanings to these terms, but that nevertheless the older and vaguer expression, "elementary principle," was generally used; and lastly, that very few measurements of the masses of the different kinds of matter taking part in chemical changes had yet been made. FOOTNOTES: [1] I have borrowed these illustrations of the alchemical, experimental method from M. Hoefer's "Histoire de la Chimie," quoted in the "Encyclopædia Brittanica," art. "Alchemy." [2] "Ripley reviv'd: or an exposition upon Sir George Ripley's Hermetico-poetical works," by Eirenæus Philalethes. London, 1678. [3] Browning's "Paracelsus." CHAPTER II. ESTABLISHMENT OF CHEMISTRY AS A SCIENCE--PERIOD OF BLACK, PRIESTLEY AND LAVOISIER. _Joseph Black_, 1728-1799. _Joseph, Priestley_, 1733-1804. _Antoine Laurent Lavoisier_, 1743-1794. During this period of advance, which may be broadly stated as comprising the last half of the eighteenth century, the aim and scope of chemical science were clearly indicated by the labours of Black, Priestley and Lavoisier. The work of these men dealt chiefly with the process of combustion. Black and Priestley finally proved the existence of airs or gases different from common air, and Lavoisier applied these discoveries to give a clear explanation of what happens when a substance burns. * * * * * JOSEPH BLACK was born near Bordeaux in the year 1728. His father was of Scottish family, but a native of Belfast; his mother was the daughter of Mr. Gordon, of Hilhead in Aberdeenshire. We are told by Dr. Robison, in his preface to Black's Lectures, that John Black, the father of Joseph, was a man "of most amiable manners, candid and liberal in his sentiments, and of no common information." At the age of twelve Black was sent home to a school at Belfast; after spending six years there he went to the University of Glasgow in the year 1746. Little is known of his progress at school or at the university, but judging from his father's letters, which his son preserved, he seems to have devoted himself to study. While at Glasgow he was attracted to the pursuit of physical science, and chose medicine as a profession. Becoming a pupil of Dr. Cullen, he was much impressed with the importance of chemical knowledge to the student of medicine. Dr. Cullen appears to have been one of the first to take large and philosophical views of the scope of chemical science, and to attempt to raise chemistry from the rank of a useful art to that of a branch of natural philosophy. Such a man must have been attracted by the young student, whose work was already at once accurate in detail and wide in general scope. In the notes of work kept by Black at this time are displayed those qualities of methodical arrangement, perseverance and thoroughness which are so prominent in his published investigations and lectures. In one place we find, says his biographer, many disjointed facts and records of diverse observations, but the next time he refers to the same subjects we generally have analogous facts noted and some conclusions drawn--we have the beginnings of knowledge. Having once entered on an investigation Black works it out steadily until he gets definite results. His earlier notes are concerned chiefly with heat and cold; about 1752 he begins to make references to the subject of "fixed air." About 1750 Black went to Edinburgh University to complete his medical studies, and here he was again fortunate in finding a really scientific student occupying the chair of natural philosophy. The attention of medical men was directed at this time to the action of limewater as a remedy for stone in the bladder. All the medicines which were of any avail in mitigating the pain attendant on this disease more or less resembled the "caustic ley of the soap-boilers" (or as we should now call it caustic potash or soda). These caustic medicines were mostly prepared by the action of quicklime on some other substance, and quicklime was generally supposed to derive its caustic, or corrosive properties from the fire which was used in changing ordinary limestone into quicklime. When quicklime was heated with "fixed alkalis" (_i.e._ with potassium or sodium carbonate), it changed these substances into caustic bodies which had a corrosive action on animal matter; hence it was concluded that the quicklime had derived a "power"--or some said had derived "igneous matter"--from the fire, and had communicated this to the fixed alkalis, which thereby acquired the property of corroding animal matter. Black thought that he might be able to lay hold of this "igneous matter" supposed to be taken by the limestone from the fire; but he found that limestone loses weight when changed into quicklime. He then dissolved limestone (or chalk) in spirits of salt (hydrochloric acid), and compared the loss of weight undergone by the chalk in this process with the loss suffered by an equal quantity of chalk when strongly heated. This investigation led Black to a fuller study of the action of heat on chalk and on "mild magnesia" (or as we now say, magnesium carbonate). In order that his experiments might be complete and his conclusions well established, he delayed taking the degree of Doctor of Medicine for three years. He graduated as M. D. in 1755, and presented his thesis on "Magnesia Alba, Quicklime and other Alkaline Substances," which contained the results of what is probably the first accurately quantitative examination of a chemical action which we possess. Black prepared mild magnesia (magnesium carbonate) by boiling together solutions of Epsom salts (magnesium sulphate) and fixed alkali (potassium carbonate). He showed that when mild magnesia is heated-- 1. It is much decreased in bulk. 2. It loses weight (twelve parts become five, according to Black). 3. It does not precipitate lime from solutions of that substance in acids (Black had already shown that mild magnesia does precipitate lime). He then strongly heated a weighed quantity of mild magnesia in a retort connected with a receiver; a few drops of water were obtained in the receiver, but the magnesia lost six or seven times as much weight as the weight of the water produced. Black then recalls the experiments of Hales, wherein airs other than common air had been prepared, and concludes that the loss of weight noticed when mild magnesia is calcined is probably due to expulsion, by the heat, of some kind of air. Dissolving some of his mild magnesia in acid he noticed that effervescence occurred, and from this he concluded that the same air which, according to his hypothesis, is expelled by heat, is also driven out from the mild magnesia by the action of acid. He then proceeded to test this hypothesis. One hundred and twenty grains of mild magnesia were strongly calcined; the calcined matter, amounting to seventy grains, was dissolved in dilute oil of vitriol, and this solution was mixed with common fixed alkali (potassium carbonate). The solid which was thus produced was collected, washed and weighed; it amounted to a trifle less than one hundred and twenty grains, and possessed all the properties--detailed by Black--of the original mild magnesia. But this is exactly the result which ought to have occurred according to his hypothesis. The next step in the investigation was to collect the peculiar air which Black had proved to be evolved during the calcination of mild magnesia. To this substance he gave the name of "fixed air," because it was fixed or held by magnesia. Black established the existence of this air in the expired breath of animals, and also showed that it was present in the air evolved during vinous fermentation. He demonstrated several of its properties; among these, the fact that animals die when placed in this air. An air with similar properties was obtained by calcining chalk. Black held that the chemical changes which occur when chalk is calcined are exactly analogous to those which he had proved to take place when magnesia is strongly heated. Chalk ought therefore to lose weight when calcined; the residue ought to neutralize an acid without evolution of any gas, and the quantity of acid thus neutralized ought to be the same as would be neutralized by the uncalcined chalk; lastly, it ought to be possible to recover the uncalcined chalk by adding a fixed alkali to a solution of the calcined chalk or quicklime. The actual results which Black obtained were as follows:-- One hundred and twenty grains of chalk were dissolved in dilute muriatic (hydrochloric) acid; 421 grains of the acid were needed to neutralize the chalk, and 48 grains of fixed air were evolved. One hundred and twenty grains of the same specimen of chalk were strongly calcined, and then dissolved in dilute muriatic acid; 414 grains of the acid were required to neutralize the calcined chalk. The difference between 421 and 414 is very slight; considering the state of practical chemistry at Black's time, we may well agree with him that he was justified in the conclusion that equal weights of calcined and of uncalcined chalk neutralize the same amount of acid. One hundred and twenty grains of the same specimen of chalk were again strongly heated; the calcined chalk, amounting to 68 grains, was digested with a solution of fixed alkali in water. The substance thus obtained, when washed and dried, weighed 118 grains, and had all the properties of ordinary chalk. Therefore, said Black, it is possible to recover the whole of the chalk originally present before calcination, by adding a fixed alkali to the calcined chalk or quicklime. At this time it was known that water dissolves quicklime, but it was generally held that only about one-fourth (or perhaps a little more) of any specimen of quicklime could be dissolved by water, however much water was employed. Black's researches had led him to regard quicklime as a homogeneous chemical compound; he concluded that as water undoubtedly dissolves quicklime to some extent, any specimen of this substance, provided it be pure, must be wholly soluble in water. Carefully conducted experiments proved that Black's conclusion was correct. Black had thus proved that quicklime is a definite substance, with certain fixed properties which characterize it and mark it off from all other substances; that by absorbing, or combining with another definite substance (fixed air), quicklime is changed into a third substance, namely chalk, which is also characterized by properties as definite and marked as those of quicklime or fixed air. Black, quite as much as the alchemists, recognized the fact that change is continually proceeding in Nature; but he clearly established the all-important conclusion that these natural changes proceed in definite order, and that it is possible by careful experiment and just reasoning to acquire a knowledge of this order. He began the great work of showing that, as in other branches of natural science, so also in chemistry, which is pre-eminently the study of the changes of Nature, "the only distinct meaning of that word" (natural) "is _stated_, _fixed_, or _settled_" (Butler's "Analogy," published 1736). This research by Black is a model of what scientific work ought to be. He begins with a few observations of some natural phenomenon; these he supplements by careful experiments, and thus establishes a sure basis of fact; he then builds on this basis a general hypothesis, which he proceeds to test by deducing from it certain necessary conclusions, and proving, or disproving, these by an appeal to Nature. This is the scientific method; it is common sense made accurate. Very shortly after the publication of the thesis on magnesia and quicklime, a vacancy occurred in the chemical chair in Glasgow University, and Black was appointed Professor of Anatomy and Lecturer on Chemistry. As he did not feel fully qualified to lecture on anatomy, he made an arrangement to exchange subjects with the Professor of Medicine, and from this time he delivered lectures on chemistry and on "The Institutes of Medicine." Black devoted a great deal of care and time to the teaching duties of his chair. His chemical experimental researches were not much advanced after this time; but he delivered courses of lectures in which new light was thrown on the whole range of chemical science. In the years between 1759 and 1763 Black examined the phenomena of heat and cold, and gave an explanation, founded on accurate experiments, of the thermal changes which accompany the melting of solids and the vaporization of liquids. If pieces of wood, lead and ice be taken by the hand from a box in which they have been kept cold, the wood feels cold to the touch, the lead feels colder than the wood, and the ice feels colder than the lead; hence it was concluded that the hand receives cold from the wood, more cold from the lead, and most cold from the ice. Black however showed that the wood really takes away heat from the hand, but that as the wood soon gets warmed, the process stops before long; that the lead, not being so quickly warmed as the wood, takes away more heat from the hand than the wood does, and that the ice takes away more heat than either wood or lead. Black thought that the heat which is taken by melting ice from a warm body remains in the water which is produced; as soon as winter came he proceeded to test this supposition by comparing the times required to melt one pound of ice and to raise the temperature of one pound of water through one degree, the source of heat being the same in each case. He also compared the time required to lower the temperature of one pound of water through one degree with that required to freeze one pound of ice-cold water. He found that in order to melt one pound of ice without raising its temperature, as much heat had to be added to the ice as sufficed to raise the temperature of one pound of water through about 140 degrees of Fahrenheit's thermometer. But this heat which has been added to the ice to convert it into water is not indicated by the thermometer. Black called this "_latent heat_." The experimental data and the complete theory of latent heat were contained in a paper read by Black to a private society which met in the University of Glasgow, on April 23, 1762; but it appears that Black was accustomed to teach the theory in his ordinary lectures before this date. The theory of latent heat ought also to explain the phenomena noticed when liquid water is changed into steam. Black applied his theory generally to this change, but did not fully work out the details and actually measure the quantity of heat which is absorbed by water at the boiling point before it is wholly converted into steam at the same temperature, until some years later when he had the assistance of his pupil and friend James Watt. Taking a survey of the phenomena of Nature, Black insisted on the importance of these experimentally established facts--that before ice melts it must absorb a large quantity of heat, and before water is vaporized it must absorb another large quantity of heat, which amounts of heat are restored to surrounding substances when water vapour again becomes liquid water and when liquid water is congealed to ice. He allows his imagination to picture the effects of these properties of water in modifying and ameliorating the climates of tropical and of Northern countries. In his lectures he says, "Here we can also trace another magnificent train of changes which are nicely accommodated to the wants of the inhabitants of this globe. In the equatorial regions, the oppressive heat of the sun is prevented from a destructive accumulation by copious evaporation. The waters, stored with their vaporific heat, are then carried aloft into the atmosphere till the rarest of the vapour reaches the very cold regions of the air, which immediately forms a small portion of it into a fleecy cloud. This also further tempers the scorching heat by its opacity, performing the acceptable office of a screen. From thence the clouds are carried to the inland countries, to form the sources in the mountains which are to supply the numberless streams that water the fields. And by the steady operation of causes, which are tolerably uniform, the greater part of the vapours passes on to the circumpolar regions, there to descend in rains and dews; and by this beneficent conversion into rain by the cold of those regions, each particle of steam gives up the heat which was latent in it. This is immediately diffused, and softens the rigour of those less comfortable climates." In the year 1766 Black was appointed Professor of Chemistry in the University of Edinburgh, in which position he remained till his death in 1799. During these thirty-three years he devoted himself chiefly to teaching and to encouraging the advance of chemical science. He was especially careful in the preparation of his elementary lectures, being persuaded that it was of the utmost importance that his pupils should be well grounded in the principles of chemistry. His health had never been robust, and as he grew old he was obliged to use great care in his diet; his simple and methodical character and habits made it easy for him to live on the plainest food, and to take meals and exercise at stated times and in fixed quantities. Black's life closed, as was fitting, in a quiet and honoured old age. He had many friends, but lived pretty much alone--he was never married. On the 26th of November 1799, "being at table with his usual fare, some bread, a few prunes and a measured quantity of milk diluted with water, and having the cup in his hand when the last stroke of his pulse was to be given, he had set it down on his knees, which were joined together, and kept it steady with his hand, in the manner of a person perfectly at ease; and in this attitude he expired, without spilling a drop, and without a writhe in his countenance, as if an experiment had been required to show to his friends the facility with which he departed." Black was characterized by "moderation and sobriety of thought;" he had a great sense of the fitness of things--of what is called by the older writers "propriety." But he was by no means a dull companion; he enjoyed general society, and was able to bear a part in any kind of conversation. A thorough student of Nature, he none the less did not wish to devote his whole time to laboratory work or to the labours of study; indeed he seems to have preferred the society of well-cultivated men and women to that of specialists in his own or other branches of natural science. But with his true scientific peers he doubtless appeared at his best. Among his more intimate friends were the famous political economist Adam Smith, and the no less celebrated philosopher David Hume. Dr. Hutton, one of the earliest workers in geology, was a particular friend of Black; his friendship with James Watt began when Watt was a student in his class, and continued during his life. With such men as his friends, and engaged in the study of Nature--that boundless subject which one can never know to the full, but which one can always know a little more year by year--Black's life could not but be happy. His example and his teaching animated his students; he was what a university professor ought to be, a student among students, but yet a teacher among pupils. His work gained for him a place in the first rank of men of science; his clearness of mind, his moderation, his gentleness, his readiness to accept the views of others provided these views were well established on a basis of experimentally determined facts, fitted him to be the centre of a circle of scientific students who looked on him as at once their teacher and their friend. As a lecturer Black was eminently successful. He endeavoured to make all his lectures plain and intelligible; he enlivened them by many experiments designed simply to illustrate the special point which he had in view. He abhorred ostentatious display and trickiness in a teacher. Black was strongly opposed to the use of hypotheses in science. Dr. Robison (the editor of his lectures) tells that when a student in Edinburgh he met Black, who became interested in him from hearing him speak somewhat enthusiastically in favour of one of the lecturers in the university. Black impressed on him the necessity of steady experimental work in natural science, gave him a copy of Newton's "Optics" as a model after which scientific work ought to be conducted, and advised him "to reject, even without examination, any hypothetical explanation, as a mere waste of time and ingenuity." But, when we examine Black's own work, we see that by "hypothetical explanations" he meant vague guesses. He himself made free use of scientific (_i.e._ of exact) hypotheses; indeed the history of science tells us that without hypotheses advance is impossible. Black taught by his own researches that science is not an array of facts, but that the object of the student of Nature is to explain facts. But the method generally in vogue before the time of Black was to gather together a few facts, or what seemed to be facts, and on these to raise a vast superstructure of "vain imaginings." Naturalists had scarcely yet learned that Nature is very complex, and that guessing and reasoning on guesses, with here and there an observation added, was not the method by which progress was to be made in learning the lessons written in this complex book of Nature. In place of this loose and slipshod method Black insisted that the student must endeavour to form a clear mental image of every phenomenon which he studied. Such an image could be obtained only by beginning with detailed observation and experiment. From a number of definite mental images the student must put together a picture of the whole natural phenomenon under examination; perceiving that something was wanted here, or that the picture was overcrowded there, he must again go to Nature and gain fresh facts, or sometimes prove that what had been accepted as facts had no real existence, and so at length he would arrive at a true representation of the whole process. So anxious was Black to define clearly what he knew and professed to teach, that he preferred to call his lectures "On the Effects of Heat and Mixtures," rather than to announce them as "A Systematic Course on Chemistry." His introductory lecture on "Heat in General" is very admirable; the following quotation will serve to show the clearness of his style and the methodical but yet eminently suggestive manner of his teaching:-- _"Of Heat in General._ "That this extensive subject may be treated in a profitable manner, I propose-- "First. To ascertain what I mean by the word _heat_ in these lectures. "Secondly. To explain the meaning of the term _cold_, and ascertain the real difference between heat and cold. "Thirdly. To mention some of the attempts which have been made to discover the nature of heat, or to form an idea of what may be the immediate cause of it. "Fourthly and lastly. I shall begin to describe sensible effects produced by heat on the bodies to which it is communicated. "Any person who reflects on the ideas which we annex to the word _heat_ will perceive that this word is used for two meanings, or to express two different things. It either means a sensation excited in our organs, or a certain quality, affection, or condition of the bodies around us, by which they excite in us that sensation. The word is used in the first sense when we say, we feel heat; in the second, when we say, there is heat in the fire or in a hot stone. There cannot be a sensation of heat in the fire, or in the hot stone, but the matter of the fire, or of the stone, is in a state or condition by which it excites in us the sensation of heat. "Now, in beginning to treat of heat and its effects, I propose to use the word in this second sense only; or as expressing that state, condition, or quality of matter by which it excites in us the sensation of heat. This idea of heat will be modified a little and extended as we proceed, but the meaning of the word will continue at bottom the same, and the reason of the modification will be easily perceived." Black's manner of dealing with the phenomenon of combustion illustrates the clearness of the conceptions which he formed of natural phenomena, and shows moreover the thoroughly unbiased nature of his mind. As soon as he had convinced himself that the balance of evidence was in favour of the new (antiphlogistic) theory, he gave up those doctrines in which he had been trained, and accepted the teaching of the French chemists; but he did not--as some with less well-balanced minds might do--regard the new theory as a final statement, but rather as one stage nearer the complete explanation which future experiments and future reasoning would serve to establish. In his lectures on combustion Black first of all establishes the facts, that when a body is burned it is changed into a kind (or kinds) of matter which is no longer inflammable; that the presence of air is needed for combustion to proceed; that the substance must be heated "to a certain degree" before combustion or inflammation begins; that this degree of heat (or we should now say this degree of temperature) differs for each combustible substance; that the supply of air must be renewed if the burning is to continue; and that the process of burning produces a change in the quality of the air supplied to the burning body. He then states the phlogistic interpretation of these phenomena: that combustion is caused by the outrush from the burning body of a something called the _principle of fire_, or _phlogiston_. Black then proceeds to demonstrate certain other facts:--When the substances produced by burning phosphorus or sulphur are heated with carbon (charcoal) the original phosphorus or sulphur is reproduced. This reproduction is due, according to the phlogistic chemists, to the giving back, by carbon, of the phlogiston which had escaped during the burning. Hence carbon contains much phlogiston. But as a similar reproduction of phosphorus or sulphur, from the substances obtained by burning these bodies, can be accomplished by the use of substances other than carbon, it is evident that these other substances also contain much phlogiston, and, moreover, that the phlogiston contained in all these substances is one and the same _principle_. What then, he asks, is this "principle" which can so escape, and be so restored by the action of various substances? He then proceeds as follows:-- "But when we inquire further, and endeavour to learn what notion was formed of the nature of this principle, and what qualities it was supposed to have in its separate state, we find this part of the subject very obscure and unsatisfactory, and the opinions very unsettled. "The elder chemists, and the alchemists, considered sulphur as the universal inflammable principle, or at least they chose to call the inflammable part of all bodies, that are more or less inflammable, by the name of their sulphur.... The famous German chemist Becher was, I believe, the first who rejected the notion of sulphur being the principle of inflammability in bodies.... His notion of the nature of the pure principle of inflammability was afterwards more fully explained and supported by Professor Stahl, who, agreeably to the doctrine of Becher, represented the principle of inflammability as a dry substance, or of an earthy nature, the particles of which were exquisitely subtile, and were much disposed to be agitated and set in motion with inconceivable velocity.... The opinion of Becher and Stahl concerning this _terra secunda_, or _terra inflammabilis_, or _phlogiston_, was that the atoms of it are, more than all others, disposed to be affected with an excessively swift whirling motion (_motus vorticillaris_). The particles of other elementary substances are likewise liable to be affected with the same sort of motion, but not so liable as those of _terra secunda_; and when the particles of any body are agitated with this sort of motion, the body exhibits the phenomena of heat, or ignition, or inflammation according to the violence and rapidity of the motion.... Becher and Stahl, therefore, did not suppose that heat depended on the abundance of a peculiar matter, such as the matter of heat or fire is now supposed to be, but on a peculiar motion of the particles of matter.... "This very crude opinion of the earthy nature of the principle of inflammability appears to have been deduced from a quality of many of the inflammable substances, by which they resist the action of water as a solvent. The greater number of the earthy substances are little, or not at all, soluble in water.... And when Becher and Stahl found those compounds, which they supposed contained phlogiston in the largest quantity, to be insoluble in water, although the other matter, with which the phlogiston was supposed to be united, was, in its separate state, exceedingly soluble in that fluid, they concluded that _a dry nature, or an incapability to be combined with water_, was an eminent quality of their phlogiston; and this was what they meant by calling it an earth or earthy substance.... But these authors supposed, at the same time, that the particles of this dry and earthy phlogiston were much disposed to be excessively agitated with a whirling motion; which whirling motion, exerted in all directions from the bodies in which phlogiston is contained, produced the phenomena of inflammation. This appears to have been the notion formed by Becher and Stahl, concerning the nature of the principle of inflammability, or the phlogiston; a notion which seems the least entitled to the name of explanation of anything we can think of. I presume that few persons can form any clear conception of this whirling motion, or, if they can, are able to explain to themselves how it produces, or can produce, anything like the phenomena of heat or fire." Black then gives a clear account of the experiments of Priestley and Lavoisier (see pp. 58, 59, and 87-89), which established the presence, in common air, of a peculiar kind of gas which is especially concerned in the processes of combustion; he emphasizes the fact that a substance increases in weight when it is burned; and he gives a simple and clear statement of that explanation of combustion which is now accepted by all, and which does not require that the existence of any principle of fire should be assumed. It is important to note that Black clearly connects the _physical_ fact that heat is absorbed, or evolved, by a substance during combustion, with the _chemical_ changes which are brought about in the properties of the substance burned. He concludes with an admirable contrast between the phlogistic theory and the theory of Lavoisier, which shows how wide, and at the same time how definite, his conceptions were. Black never speaks contemptuously of a theory which he opposes. "According to this theory" (_i.e._ the theory of Lavoisier), "the inflammable bodies, sulphur for example, or phosphorus, are simple substances. The acid into which they are changed by inflammation is a compound. The chemists, on the contrary" (_i.e._ the followers of Stahl), "consider the inflammable bodies as compounds, and the uninflammable matter as more simple. In the common theory the heat and light are supposed to emanate from, or to be furnished by, the burning body. But, in Mr. Lavoisier's theory, both are held to be furnished by the air, of which they are held to be constituent parts, or ingredients, while in its state of fire-supporting air." Black was not a brilliant discoverer, but an eminently sound and at the same time imaginative worker; whatever he did he did well, but he did not exhaust any field of inquiry. Many of the facts established by him have served as the basis of important work done by those who came after him. The number of new facts added by Black to the data of chemistry was not large; but by his lectures--which are original dissertations of the highest value--he did splendid service in advancing the science of chemistry. Black possessed that which has generally distinguished great men of science, a marked honesty of character; and to this he added comprehensiveness of mental vision: he saw beyond the limits of the facts which formed the foundations of chemical science in his day. He was not a fact-collector, but a philosopher. * * * * * JOSEPH PRIESTLEY, the son of Jonas Priestley, "a maker and dresser of woollen cloth," was born at Fieldhead, near Leeds, in the year 1733. His mother, who was the daughter of a farmer near Wakefield, died when he was seven years old. From that time he was brought up by a sister of his father, who was possessed of considerable private means. Priestley's surroundings in his young days were decidedly religious, and evidently gave a tone to his whole after life. We shall find that Priestley's work as a man of science can scarcely be separated from his theological and metaphysical work. His cast of mind was decidedly metaphysical; he was altogether different from Black, who, as we have seen, was a typical student of natural phenomena. The house of Priestley's aunt was a resort for all the Dissenting ministers of that part of the county. She herself was strictly Calvinistic in her theological views, but not wholly illiberal. Priestley's early schooling was chiefly devoted to learning languages; he acquired a fair knowledge of Latin, a little Greek, and somewhat later he learned the elements of Hebrew. At one time he thought of going into trade, and therefore, as he tells us in his "Memoirs," he acquired some knowledge of French, Italian and High Dutch. With the help of a friend, a Dissenting minister, he learned something of geometry, mathematics and natural philosophy, and also got some smattering of the Chaldee and Syriac tongues. At the age of nineteen Priestley went to an "academy" at Daventry. The intellectual atmosphere here seems to have been suitable to the rapid development of Priestley's mind. Great freedom of discussion was allowed; even during the teachers' lectures the students were permitted "to ask whatever questions and to make whatever remarks" they pleased; and they did it, Priestley says, "with the greatest, but without any offensive, freedom." The students were required to read and to give an account of the more important arguments for and against the questions discussed in the teachers' lectures. Theological disputations appear to have been the favourite topics on which the students exercised their ingenuity among themselves. Priestley tells us that he "saw reason to embrace what is generally called the heterodox side of almost every question." Leaving this academy, Priestley went, in 1755, as assistant to the Dissenting minister at Needham, in Suffolk. Here he remained for three years, living on a salary of about £30 a year, and getting more and more into bad odour because of his peculiar theological views. From Needham he moved to Nantwich, in Cheshire, where he was more comfortable, and, having plenty of work to do, he had little time for abstruse speculations. School work engaged most of his time at Nantwich; he also began to collect a few scientific instruments, such as an electrical machine and an air-pump. These he taught his scholars to use and to keep in good order. He gave lectures on natural phenomena, and encouraged his scholars to make experiments and sometimes to exhibit their experiments before their parents and friends. He thus extended the reputation of his school and implanted in his scholars a love of natural knowledge. In the year 1761 Priestley removed to Warrington, to act as tutor in a newly established academy, where he taught languages--a somewhat wide subject, as it included lectures on "The Theory of Languages," on "Oratory and Criticism," and on "The History, Laws, and Constitution of England." He says, "It was my province to teach elocution, and also logic and Hebrew. The first of these I retained, but after a year or two I exchanged the two last articles with Dr. Aikin for the civil law, and one year I gave a course of lectures on anatomy." During his stay at Warrington, which lasted until 1767, Priestley married a daughter of Mr. Isaac Wilkinson, an ironmaster of Wrexham, in Wales. He describes his wife as "a woman of an excellent understanding much improved by reading, of great fortitude and strength of mind, and of a temper in the highest degree affectionate and generous, feeling strongly for others and little for herself, also greatly excelling in everything relating to household affairs." About this time Priestley met Dr. Franklin more than once in London. His conversation seems to have incited Priestley to a further study of natural philosophy. He began to examine electrical phenomena, and this led to his writing and publishing a "History of Electricity," in the course of which he found it necessary to make new experiments. The publication of the results of these experiments brought him more into notice among scientific men, and led to his election as a Fellow of the Royal Society, and to his obtaining the degree of LL.D. from the University of Edinburgh. In the year 1767 Priestley removed to Leeds, where he spent six years as minister of Millhill Chapel. He was able to give freer expression to his theological views in Leeds than could be done in smaller places, such as Needham and Nantwich. During this time he wrote and published many theological and metaphysical treatises. But, what is of more importance to us, he happened to live near a brewery. Now, the accidental circumstances, as we call them, of Priestley's life were frequently of the greatest importance in their effects on his scientific work. Black had established the existence and leading properties of fixed air about twelve or thirteen years before the time when Priestley came to live near the brewery in Leeds. He had shown that this fixed air is produced during alcoholic fermentation. Priestley knowing this used to collect the fixed air which came off from the vats in the neighbouring brewery, and amuse himself with observing its properties. But removing from this part of the town his supplies of fixed air were stopped. As however he had become interested in working with airs, he began to make fixed air for himself from chalk, and in order to collect this air he devised a very simple piece of apparatus which has played a most important part in the later development of the chemistry of gases, or pneumatic chemistry. Priestley's _pneumatic trough_ is at this day to be found in every laboratory; it is extremely simple and extremely perfect. A dish of glass, or earthenware, or wood is partly filled with water; a shelf runs across the dish at a little distance beneath the surface of the water; a wide-mouthed bottle is filled with water and placed, mouth downwards, over a hole in this shelf. The gas which is to be collected in this bottle is generated in a suitable vessel, from which a piece of glass or metal tubing passes under the shelf and stops just where the hole is made. The gas which comes from the apparatus bubbles up into the bottle, drives out the water, and fills the bottle. When the bottle is full of gas, it is moved to one side along the shelf, and another bottle filled with water is put in its place. As the mouth of each bottle is under water there is no connection between the gas inside and the air outside the bottle; the gas may therefore be kept in the bottle until the experimenter wants it. (See Fig. 1. which is reduced from the cut in Priestley's "Air.") [Illustration: Fig. 1.] Priestley tells us that at this time he knew very little chemistry, but he thinks that this was a good thing, else he might not have been led to make so many new discoveries as he did afterwards make. Experimenting with fixed air, he found that water could be caused to dissolve some of the gas. In 1772 he published a pamphlet on the method of impregnating water with fixed air; this solution of fixed air in water was employed medicinally, and from this time we date the manufacture of artificial mineral waters. The next six years of Priestley's life (1773-1779) are very important in the history of chemistry; it was during these years that much of his best work on various airs was performed. During this time he lived as a kind of literary companion (nominally as librarian) with the Earl of Shelburne (afterwards Marquis of Lansdowne.) His wife and family--he had now three children--lived at Calne, in Wiltshire, near Lord Shelburne's seat of Bowood. Priestley spent most of the summer months with his family, and the greater part of each winter with Lord Shelburne at his London residence; during this time he also travelled in Holland and Germany, and visited Paris in 1774. In a paper published in November 1772, Priestley says that he examined a specimen of air which he had extracted from saltpetre above a year before this date. This air "had by some means or other become noxious, but," he supposed, "had been restored to its former wholesome state, so as to effervesce with nitrous air" (in modern language, to combine with nitric oxide) "and to admit a candle to burn in it, in consequence of agitation with water." He tells us, in his "Observations on Air" (1779), that at this time he was altogether in the dark as to the nature of this air obtained from saltpetre. In August 1774, he was amusing himself by observing the action of heat on various substances--"without any particular view," he says, "except that of extracting air from a variety of substances by means of a burning lens in quicksilver, which was then a new process with me, and which I was very proud of"--when he obtained from _red precipitate_ (oxide of mercury) an air in which a candle burned with a "remarkably vigorous flame." The production of this peculiar air "surprised me more than I can well express;" "I was utterly at a loss how to account for it." At first he thought that the specimen of _red precipitate_ from which the air had been obtained was not a proper preparation, but getting fresh specimens of this salt, he found that they all yielded the same kind of air. Having satisfied himself by experiment that this peculiar air had "all the properties of common air, only in much greater perfection," he gave to it the name of _dephlogisticated air_. Later experiments taught him that the same air might be obtained from red lead, from manganese oxide, etc., by the action of heat, and from various other salts by the action of acids. Priestley evidently regards the new "dephlogisticated air" simply as very pure ordinary air; indeed, he seems to look on all airs, or gases, as easily changeable one into the other. He always interprets his experimental results by the help of the theory of phlogiston. One would indeed think from Priestley's papers that the existence of this substance phlogiston was an unquestioned and unquestionable fact. Thus, he says in the preface to his "Experiments on Air:" "If any opinion in all the modern doctrine concerning air be well founded, it is certainly this, that nitrous air is highly charged with phlogiston, and that from this quality only it renders pure air noxious.... If I have completely ascertained anything at all relating to air it is this." Priestley thought that "very pure air" would take away phlogiston from some metals without the help of heat or any acid, and thus cause these metals to rust. He therefore placed some clean iron nails in _dephlogisticated air_ standing over mercury; after three months he noticed that about one-tenth of the air in the vessel had disappeared, and he concluded, although no rust appeared, that the dephlogisticated air had as a fact withdrawn phlogiston from the iron nails. This is the kind of reasoning which Black described to his pupils as "mere waste of time and ingenuity." The experiment with the nails was made in 1779; at this time, therefore, Priestley had no conception as to what his _dephlogisticated air_ really was. Trying a great many experiments, and finding that the new air was obtained by the action of acids on earthy substances, Priestley was inclined to regard this air, and if this then all other airs, as made up of an acid (or acids) and an earthy substance. We now know how completely erroneous this conclusion was, but we must remember that in Priestley's time chemical substances were generally regarded as of no very definite or fixed composition; that almost any substance, it was supposed, might be changed into almost any other; that no clear meaning was attached to the word "element;" and that few, if any, careful measurements of the quantities of different kinds of matter taking part in chemical actions had yet been made. But at the same time we cannot forget that the books of Hooke and Mayow had been published years before this time, and that twenty years before Priestley began his work on airs, Black had published his exact, scientific investigation on fixed air. Although we may agree with Priestley that, had he made himself acquainted with what others had done before he began his own experiments, he might not have made so many new discoveries as he did, yet one cannot but think that his discoveries, although fewer, would have been more accurate. We are told by Priestley that, when he was in Paris in 1774, he exhibited the method of obtaining dephlogisticated air from _red precipitate_ to Lavoisier and other French chemists. We shall see hereafter what important results to science followed from this visit to Lavoisier. Let us shortly review Priestley's answer to the question, "What happens when a substance burns in air?" Beginning to make chemical experiments when he had no knowledge of chemistry, and being an extremely rapid worker and thinker, he naturally adopted the prevalent theory, and as naturally interpreted the facts which he discovered in accordance with this theory. When a substance burns, phlogiston, it was said, rushes out of it. But why does rapid burning only take place in air? Because, said Priestley, air has a great affinity for phlogiston, and draws it out of the burning substance. What then becomes of this phlogiston? we next inquire. The answer is, obviously it remains in the air around the burning body, and this is proved by the fact that this air soon becomes incapable of supporting the process of burning, it becomes phlogisticated. Now, if phlogisticated air cannot support combustion, the greater the quantity of phlogiston in air, the less will it support burning; but we know that if a substance is burnt in a closed tube containing air, the air which remains when the burning is quite finished at once extinguishes a lighted candle. Priestley also proved that an air can be obtained by heating _red precipitate_, characterized by its power of supporting combustion with great vigour. What is this but common air completely deprived of phlogiston? It is dephlogisticated air. Now, if common air draws phlogiston out of substances, surely this dephlogisticated air will even more readily do the same. That it really does this Priestley thought he had proved by his experiment with clean iron nails (see p. 60). Water was regarded as a substance which, like air, readily combined with phlogiston; but Priestley thought that a candle burned less vigorously in dephlogisticated air which had been shaken with water than in the same air before this treatment; hence he concluded that phlogiston had been taken from the water. After Cavendish had discovered (or rather rediscovered) hydrogen, and had established the fact that this air is extremely inflammable, most chemists began to regard this gas as pure or nearly pure phlogiston, or, at least, as a substance very highly charged with phlogiston. "Now," said Priestley, "when a metal burns phlogiston rushes out of it; if I restore this phlogiston to the metallic calx, I shall convert it back into the metal." He then showed by experiment that when calx of iron is heated with hydrogen, the hydrogen disappears and the metal iron is produced. He seemed, therefore, to have a large experimental basis for his answer to the question, "What happens when a substance burns?" But at a later time it was proved that iron was also produced by heating the calx of iron with carbon. The antiphlogistic chemists regarded fixed air as composed of carbon and dephlogisticated air; the phlogisteans said it was a substance highly charged with phlogiston. The antiphlogistic school said that calx of iron is composed of iron and dephlogisticated air; the phlogisteans said it was iron deprived of its phlogiston. Here was surely an opportunity for a crucial experiment: when calx of iron is heated with carbon, and iron is produced, there must either be a production of fixed air (which is a non-inflammable gas, and forms a white solid substance when brought into contact with limewater), or there must be an outrush of phlogiston from the carbon. The experiment was tried: a gas was produced which had no action on limewater and which was very inflammable; what could this be but phlogiston, already recognized by this very property of extreme inflammability? Thus the phlogisteans appeared to triumph. But if we examine these experiments made by Priestley with the light thrown on them by subsequent research, we find that they bear the interpretation which he put on them only because they were not accurate; thus, two gases are inflammable, but it by no means follows that these gases are one and the same. We must have more accurate knowledge of the properties of these gases. The air around a burning body, such as iron, after a time loses the power of supporting combustion; but this is merely a qualitative fact. Accurately to trace the change in the properties of this air, it is absolutely necessary that exact measurements should be made; when this is done, we find that the volume of air diminishes during the combustion, that the burning body gains weight, and that this gain in weight is just equal to the loss in weight undergone by the air. When the inflammable gas produced by heating calx of iron with carbon was carefully and _quantitatively_ analyzed, it was found to consist of carbon and oxygen (dephlogisticated air), but to contain these substances in a proportion different from that in which they existed in fixed air. It was a new kind of air or gas; it was _not_ hydrogen. This account of Priestley's experiments and conclusions regarding combustion shows how easy it is in natural science to interpret experimental results, especially when these results are not very accurate, in accordance with a favourite theory; and it also illustrates one of the lessons so emphatically taught by all scientific study, viz. the necessity of suspending one's judgment until accurate measurements have been made, and the great wisdom of then judging cautiously. About 1779 Priestley left Lord Shelburne, and went as minister of a chapel to Birmingham, where he remained until 1791. During his stay in Birmingham, Priestley had a considerable amount of pecuniary help from his friends. He had from Lord Shelburne, according to an agreement made when he entered his service, an annuity of £150 a year for life; some of his friends raised a sum of money annually for him, in order that he might be able to prosecute his researches without the necessity of taking pupils. During the ten years or so after he settled in Birmingham, Priestley did a great deal of chemical work, and made many discoveries, almost entirely in the field of pneumatic chemistry. Besides the discovery of dephlogisticated air (or oxygen) which has been already described, Priestley discovered and gave some account of the properties of _nitrous air_ (nitric acid), _vitriolic acid air_ (sulphur dioxide), _muriatic acid air_ (hydrochloric acid), and _alkaline air_ (ammonia), etc. In the course of his researches on the last-named air he showed, that when a succession of electric sparks is passed through this gas a great increase in the volume of the gas occurs. This fact was further examined at a later time by Berthollet, who, by measuring the increase in volume undergone by a measured quantity of ammonia gas, and determining the nature of the gases produced by the passage of the electric sparks, proved that ammonia is a compound of hydrogen and nitrogen, and that three volumes of the former gas combine with one volume of the latter to produce two volumes of ammonia gas. Priestley's experiments on "inflammable air"--or hydrogen--are important and interesting. The existence of this substance as a definite kind of air had been proved by the accurate researches of Cavendish in 1766. Priestley drew attention to many actions in which this inflammable air is produced, chiefly to those which take place between acids and metals. He showed that inflammable air is not decomposed by electric sparks; but he thought that it was decomposed by long-continued heating in closed tubes made of lead-glass. Priestley regarded inflammable air as an air containing much phlogiston. He found that tubes of lead-glass, filled with this air, were blackened when strongly heated for a long time, and he explained this by saying that the lead in the glass had a great affinity for phlogiston, and drew it out of the inflammable air. When inflammable air burns in a closed vessel containing common air, the latter after a time loses its property of supporting combustion. Priestley gave what appeared to be a fairly good explanation of this fact, when he said that the inflammable air parted with phlogiston, which, becoming mixed with the ordinary air in the vessel, rendered it unable to support the burning of a candle. He gave a few measurements in support of this explanation; but we now know that the method of analysis which he employed was quite untrustworthy. Thinking that by measuring the extent to which the _phlogistication_ (we would now say the _deoxidation_) of common air was carried by mixing measured quantities of common and inflammable airs and exploding this mixture, he might be able to determine the amount of phlogiston in a given volume of inflammable air, he mixed the two airs in glass tubes, through the sides of which he had cemented two pieces of wire, sealed the tubes, and exploded the mixture by passing electric sparks from wire to wire. The residual air now contained, according to Priestley, more phlogiston, and therefore relatively less dephlogisticated air than before the explosion. He made various measurements of the quantities of dephlogisticated air in the tubes, but without getting any constant results. He noticed that after the explosions the insides of the tubes were covered with moisture. At a later time he exploded a mixture of dephlogisticated and inflammable airs (oxygen and hydrogen) in a copper globe, and recorded the fact that after the explosion the globe contained a little water. Priestley was here apparently on the eve of a great discovery. "In looking for one thing," says Priestley, "I have generally found another, and sometimes a thing of much more value than that which I was in quest of." Had he performed the experiment of exploding dephlogisticated and inflammable airs with more care, and had he made sure that the airs used were quite dry before the explosion, he would probably have found a thing of indeed much more value than that of which he was in quest; he would probably have discovered the compound nature of water--a discovery which was made by Cavendish three or four years after these experiments described by Priestley. Some very curious observations were made by Priestley regarding the colour of the gas obtained by heating "spirit of nitre" (_i.e._ nitric acid). He showed that a yellow gas or air is obtained by heating colourless liquid spirit of nitre in a sealed glass tube, and that as the heating is continued the colour of the gas gets darker, until it is finally very dark orange red. These experiments have found an explanation only in quite recent times. Another discovery made by Priestley while in Birmingham, viz. that an acid is formed when electric sparks are passed through ordinary air for some time, led, in the hands of Cavendish--an experimenter who was as careful and deliberate as Priestley was rapid and careless--to the demonstration of the composition of nitric acid. Many observations were made by Priestley on the effects of various airs on growing plants and living animals; indeed, one of his customary methods of testing different airs was to put a mouse into each and watch the effects of the air on its breathing. He grew sprigs of mint in common air, in dephlogisticated air (oxygen), and in phlogisticated air (nitrogen, but probably not pure); the sprig in the last-named air grew best, while that in the dephlogisticated air soon appeared sickly. He also showed that air which has been rendered "noxious" by the burning of a candle in it, or by respiration or putrefaction, could be restored to its original state by the action of growing plants. He thought that the air was in the first instance rendered noxious by being impregnated with phlogiston, and that the plant restored the air by removing this phlogiston. Thus Priestley distinctly showed that (to use his own words) "it is very probable that the injury which is continually done to the atmosphere by the respiration of such a number of animals as breathe it, and the putrefaction of such vast masses, both of vegetable and animal substances, exposed to it, is, in part at least, repaired by the vegetable creation." But from want of quantitative experiments he failed to give any just explanation of the process whereby this "reparation" is accomplished. During his stay in Birmingham, Priestley was busily engaged, as was his wont during life, in writing metaphysical and theological treatises and pamphlets. At this time the minds of men in England were much excited by the events of the French Revolution, then being enacted before them. Priestley and some of his friends were known to sympathize with the French people in this great struggle, as they had been on the side of the Americans in the War of Independence. Priestley's political opinions had, in fact, always been more advanced than the average opinion of his age; by some he was regarded as a dangerous character. But if we read what he lays down as a fundamental proposition in the "Essay on the First Principles of Civil Government" (1768), we cannot surely find anything very startling. "It must be understood, whether it be expressed or not, that all people live in society for their mutual advantage; so that the good and happiness of the members, that is the majority of the members of any state, is the great standard by which everything relating to that state must be finally determined. And though it may be supposed that a body of people may be bound by a voluntary resignation of all their rights to a single person, or to a few, it can never be supposed that the resignation is obligatory on their posterity, because it is manifestly contrary to the good of the whole that it should be so." Priestley proposed many political reforms, but he was decidedly of opinion that these ought to be brought about gradually. He was in favour of abolishing all religious State establishments, and was a declared enemy to the Church of England. His controversies with the clergy of Birmingham helped to stir up a section of public opinion against him, and to bring about the condemnation of his writings in many parts of the country; he was also unfortunate in making an enemy of Mr. Burke, who spoke against him and his writings in the House of Commons. In the year 1791, the day of the anniversary of the taking of the Bastille was celebrated by some of Priestley's friends in Birmingham. On that day a senseless mob, raising the cry of "Church and King," caused a riot in the town. Finding that they were not checked by those in authority, they after a time attacked and burned Dr. Priestley's meeting-house, and then destroyed his dwelling-house, and the houses of several other Dissenters in the town. One of his sons barely escaped with his life. He himself found it necessary to leave Birmingham for London, as he considered his life to be in danger. Many of his manuscripts, his library, and much of his apparatus were destroyed, and his house was burned. A congregation at Hackney had the courage at this time to invite Priestley to become their minister. Here he remained for about three years, ministering to the congregation, and pursuing his chemical and other experiments with the help of apparatus and books which had been supplied by his friends, and by the expenditure of part of the sum, too small to cover his losses, given him by Government in consideration of the damage done to his property in the riots at Birmingham. But finding himself more and more isolated and lonely, especially after the departure of his three sons to America, which occurred during these years, he at last resolved to follow them, and spend the remainder of his days in the New World. Although Priestley had been very badly treated by a considerable section of the English people, yet he left his native country "without any resentment or ill will." "When the time for reflection," he says, "shall come, my countrymen will, I am confident, do me more justice." He left England in 1795, and settled at Northumberland, in Pennsylvania, about a hundred and thirty miles north-west of Philadelphia. By the help of his friends in England he was enabled to build a house and establish a laboratory and a library; an income was also secured sufficient to maintain him in moderate comfort. The chair of chemistry in the University of Philadelphia was offered to him, and he was also invited to the charge of a Unitarian chapel in New York; but he preferred to remain quietly at work in his laboratory and library, rather than again to enter into the noisy battle of life. In America he published several writings. Of his chemical discoveries made after leaving England, the most important was that an inflammable gas is obtained by heating metallic calces with carbon. The production of this gas was regarded by Priestley as an indisputable proof of the justness of the theory of phlogiston (see pp. 63, 64). His health began to give way about 1801; gradually his strength declined, and in February 1804, the end came quietly and peacefully. A list of the books and pamphlets published by Priestley on theological, metaphysical, philological, historical, educational and scientific subjects would fill several pages of this book. His industry was immense. To accomplish the vast amount of work which he did required the most careful outlay of time. In his "Memoirs," partly written by himself, he tells us that he inherited from his parents "a happy temperament of body and mind;" his father especially was always in good spirits, and "could have been happy in a workhouse." His paternal ancestors had, as a race, been healthy and long-lived. He was not himself robust as a youth, yet he was always able to study: "I have never found myself," he says, "less disposed or less qualified for mental exertion of any kind at one time of the day more than another; but all seasons have been equal to me, early or late, before dinner or after." His peculiar evenness of disposition enabled him quickly to recover from the effects of any unpleasant occurrence; indeed, he assures us that "the most perfect satisfaction" often came a day or two after "an event that afflicted me the most, and without any change having taken place in the state of things." Another circumstance which tended to make life easy to him was his fixed resolution, that in any controversy in which he might be engaged, he would frankly acknowledge every mistake he perceived himself to have fallen into. Priestley's scientific work is marked by rapidity of execution. The different parts do not hang together well; we are presented with a brilliant series of discoveries, but we do not see the connecting strings of thought. We are not then astonished when he tells us that sometimes he forgot that he had made this or that experiment, and repeated what he had done weeks before. He says that he could not work in a hurry, and that he was therefore always methodical; but he adds that he sometimes blamed himself for "doing to-day what had better have been put off until to-morrow." Many of his most startling discoveries were the results of chance operations, "not of themes worked out and applied." He was led to the discovery of oxygen, he says, by a succession of extraordinary accidents. But that he was able to take advantage of the chance observations, and from these to advance to definite facts, constitutes the essential difference between him and ordinary plodding investigators. Although he rarely, if ever, saw all the bearings of his own discoveries, although none of his experiments was accurately worked out to its conclusion, yet he did see, rapidly and as it appeared almost at one glance, something of their meanings, and this something was enough to urge him on to fresh experimental work. Although we now condemn Priestley's theories as quite erroneous, yet we must admire his undaunted devotion to experiment. He was a true student of science in one essential point, viz. Nature was for him the first and the last court of appeal. He theorized and speculated much, he experimented rapidly and not accurately, but he was ever appealing to natural facts; and in doing this he could not but lay some foundation which should remain. The facts discovered by him are amongst the very corner-stones on which the building of chemical science was afterwards raised. So enthusiastic was Priestley in the prosecution of his experiments, that when he began, he tells us, "I spent all the money I could possibly raise, carried on by my ardour in philosophical investigation, and entirely regardless of consequences, except so far as never to contract any debts." He seems all through his life to have been perfectly free from anxiety about money affairs. Priestley's manner of work shows how kindly and genial he was. He trained himself to talk and think and write with his family by the fireside; "nothing but reading aloud, or speaking without interruption," was an obstruction to his work. Priestley was just the man who was wanted in the early days of chemical science. By the vast number, variety and novelty of his experimental results, he astonished scientific men--he forcibly drew attention to the science in which he laboured so hard; by the brilliancy of some of his experiments he obliged chemists to admit that a new field of research was opened before them, and the instruments for the prosecution of this research were placed in their hands; and even by the unsatisfactoriness of his reasoning he drew attention to the difficulties and contradictions of the theories which then prevailed in chemistry. That the work of Priestley should bear full fruit it was necessary that a greater than he should interpret it, and should render definite that which Priestley had but vaguely shown to exist. The man who did this, and who in doing it really established chemistry as a science, was Lavoisier. But before considering the work of Lavoisier, I should like to point out that many of the physical characters of common air had been clearly established in the later years of the seventeenth century by the Honourable Robert Boyle. In the "Sceptical Chymist," published in 1661, Mr. Boyle had established the fact that air is a material substance possessed of weight, that this air presses on the surface of all things, and that by removing part of the air in an enclosed space the pressure within that space is diminished. He had demonstrated that the boiling point of water is dependent on the pressure of the air on the surface of the water. Having boiled some water "a pretty while, that by the heat it might be freed from the latitant air," he placed the vessel containing the hot water within the receiver of an arrangement which he had invented for sucking air out of an enclosed space; as soon as he began to suck out air from this receiver, the water boiled "as if it had stood over a very quick fire.... Once, when the air had been drawn out, the liquor did, upon a single exsuction, boil so long with prodigiously vast bubbles, that the effervescence lasted almost as long as was requisite for the rehearsing of a _Pater noster_." Boyle had gone further than the qualitative fact that the volume of an enclosed quantity of air alters with changes in the pressure to which that air is subjected; he had shown by simple and accurate experiments that "the volume varies inversely as the pressure." He had established the generalization of so much importance in physical science now known as _Boyle's law_. The work of the Honourable Henry Cavendish will be considered in some detail in the book on "The Physicists" belonging to this series, but I must here briefly allude to the results of his experiments on air published in the _Philosophical Transactions_ for 1784 and 1785. Cavendish held the ordinary view that when a metal burns in air, the air is thereby phlogisticated; but why is it, he asked, that the volume of air is decreased by this process? It was very generally said that fixed air was produced during the calcination of metals, and was absorbed by the calx. But Cavendish instituted a series of experiments which proved that no fixed air could be obtained from metallic calces. In 1766 inflammable air (hydrogen) was discovered by Cavendish; he now proved that when this air is exploded with dephlogisticated air (oxygen), water is produced. He showed that when these two airs are mixed in about the proportion of two volumes of hydrogen to one volume of oxygen, the greater part, if not the whole of the airs is condensed into water by the action of the electric spark. He then proceeded to prove by experiments that when common air is exploded with inflammable air water is likewise produced, and phlogisticated air (_i.e._ nitrogen) remains. Priestley and Cavendish had thus distinctly established the existence of three kinds of air, viz. dephlogisticated air, phlogisticated air, and inflammable air. Cavendish had shown that when the last named is exploded with common air water is produced (which is composed of dephlogisticated and inflammable airs), and phlogisticated air remains. Common air had thus been proved to consist of these two--phlogisticated and dephlogisticated airs (nitrogen and oxygen). Applying these results to the phenomenon of the calcination of metals, Cavendish gave reasons for thinking that the metals act towards common air in a manner analogous to that in which inflammable air acts--that they withdraw dephlogisticated and leave phlogisticated air; but, as he was a supporter of the phlogistic theory, he rather preferred to say that the burning metals withdraw dephlogisticated air and phlogisticate that which remains; in other words, while admitting that a metal in the process of burning gains dephlogisticated air, he still thought that the metal also loses _something_; viz. phlogiston. That Cavendish in 1783-84 had proved air to consist of two distinct gases, and water to be produced by the union of two gases, must be remembered as we proceed with the story of the discoveries of Lavoisier. * * * * * ANTOINE LAURENT LAVOISIER, born in Paris in 1743, was the son of a wealthy merchant, who, judging from his friendship with many of the men of science of that day, was probably of a scientific bent of mind, and who certainly showed that he was a man of sense by giving his son the best education which he could obtain. After studying in the Mazarin College, Lavoisier entered on a course of training in physical, astronomical, botanical and chemical science. The effects of this training in the accurate methods of physics are apparent in the chemical researches of Lavoisier. At the age of twenty-one Lavoisier wrote a memoir which gained the prize offered by the French Government for the best and most economical method of lighting the streets of a large city. While making experiments, the results of which were detailed in this paper, Lavoisier lived for six weeks in rooms lighted only by artificial light, in order that his eyesight might become accustomed to small differences in the intensities of light from various sources. When he was twenty-five years old Lavoisier was elected a member of the Academy of Sciences. During the next six years (1768-1774) he published various papers, some on chemical, some on geological, and some on mathematical subjects. Indeed at this time, although an ardent cultivator of natural science, he appears to have been undecided as to which branch of science he should devote his strength. The accuracy and thoroughness of Lavoisier's work, and the acuteness of his reasoning powers, are admirably illustrated in two papers, published in the Memoirs of the Academy for 1770, on the alleged conversion of water into earth. When water is boiled for a long time in a glass vessel a considerable quantity of white siliceous earth is found in the vessel. This apparent conversion or transmutation of water into earthy matter was quite in keeping with the doctrines which had been handed down from the times of the alchemists; the experiment was generally regarded as conclusively proving the possibility of changing water into earth. Lavoisier found that after heating water for a hundred and one days in a closed _and weighed_ glass vessel, there was no change in the total weight of the vessel and its contents; when he poured out the water and evaporated it to dryness, he obtained 20.4 grains of solid earthy matter; but he also found, what had been before overlooked, that the glass vessel had lost weight. The actual loss amounted to 17.4 grains. The difference between this and the weight of the earthy matter in the water, viz. three grains, was set down (and as we now know justly set down) by Lavoisier to errors of experiment. Lavoisier therefore concluded that water, when boiled, is not changed into earth, but that a portion of the earthy matter of which glass is composed is dissolved by the water. This conclusion was afterwards confirmed by the Swedish chemist _Scheele_, who proved that the composition of the earthy matter found in the water is identical with that of some of the constituents of glass. By this experiment Lavoisier proved the old alchemical notion of transmutation to be erroneous; he showed that water is not transmuted into earth, but that each of these substances is possessed of definite properties which belong to it and to it only. He established the all-important generalization--which subsequent research has more amply confirmed, until it is to-day accepted as the very foundation of every branch of physical science--that in no process of change is there any alteration in the total mass of matter taking part in that change. The glass vessel in which Lavoisier boiled water for so many days lost weight; but the matter lost by the glass was found dissolved in the water. We know that this generalization holds good in all chemical changes. Solid sulphur may be converted into liquid oil of vitriol, but it is only by the sulphur combining with other kinds of matter; the weight of oil of vitriol produced is always exactly equal to the sum of the weights of the sulphur, hydrogen and oxygen which have combined to form it. The colourless gases, hydrogen and oxygen, combine, and the limpid liquid water is the result; but the weight of the water produced is equal to the sum of the weights of hydrogen and oxygen which combined together. It is impossible to overrate the importance of the principle of the _conservation of mass_, first definitely established by Lavoisier. Some time about the year 1770 Lavoisier turned his attention seriously to chemical phenomena. In 1774 he published a volume entitled "Essays Physical and Chemical," wherein he gave an historical account of all that had been done on the subject of airs from the time of Paracelsus to the year 1774, and added an account of his own experiments, in which he had established the facts that a metal in burning absorbs air, and that when the metallic calx is reduced to metal by heating with charcoal, an air is produced of the same nature as the fixed air of Dr. Black. In November 1772 Lavoisier deposited a sealed note in the hands of the Secretary to the Academy of Sciences. This note was opened on the 1st of May 1773, and found to run as follows[4]:-- "About eight days ago I discovered that sulphur in burning, far from losing, augments in weight; that is to say, that from one pound of sulphur much more than one pound of vitriolic acid is obtained, without reckoning the humidity of the air. Phosphorus presents the same phenomenon. This augmentation of weight arises from a great quantity of air which becomes fixed during the combustion, and which combines with the vapours. "This discovery, confirmed by experiments which I regard as decisive, led me to think that what is observed in the combustion of sulphur and phosphorus might likewise take place with respect to all the bodies which augment in weight by combustion and calcination; and I was persuaded that the augmentation of weight in the calces of metals proceeded from the same cause. The experiment fully confirmed my conjectures. "I operated the reduction of litharge in closed vessels with Hale's apparatus, and I observed that at the moment of the passage of the calx into the metallic state, there was a disengagement of air in considerable quantity, and that this air formed a volume at least one thousand times greater than that of the litharge employed. "As this discovery appears to me one of the most interesting which has been made since Stahl, I thought it expedient to secure to myself the property, by depositing the present note in the hands of the Secretary of the Academy, to remain secret till the period when I shall publish my experiments. "LAVOISIER. "Paris, 11th November 1772." In his paper "On the Calcination of Tin in Closed Vessels, and on the Cause of Increase of Weight acquired by the Metal during this Process" (published in 1774), we see and admire Lavoisier's manner of working. A weighed quantity (about half a pound) of tin was heated to melting in a glass retort, the beak of which was drawn out to a very small opening; the air within the retort having expanded, the opening was closed by melting the glass before the blowpipe. The weight of retort and tin was now noted; the tin was again heated to its melting point, and kept at this temperature as long as the process of calcination appeared to proceed; the retort and its contents were then allowed to cool and again weighed. No change was caused by the heating process in the total weight of the whole apparatus. The end of the retort beak was now broken off; air rushed in with a hissing sound. The retort and contents were again weighed, and the increase over the weight at the moment of sealing the retort was noted. The calcined tin in the retort was now collected and weighed. It was found that the increase in the weight of the tin was equal to the weight of the air which rushed into the retort. Hence Lavoisier concluded that the calcination of tin was accompanied by an absorption of air, and that the difference between the weights of the tin and the calx of tin was equal to the weight of air absorbed; but he states that probably only a part of the air had combined with the tin, and that hence air is not a simple substance, but is composed of two or more constituents. Between the date of this publication and that of Lavoisier's next paper on combustion we know that Priestley visited Paris. In his last work, "The Doctrine of Phlogiston established" (published in 1800), Priestley says, "Having made the discovery of dephlogisticated air some time before I was in Paris in 1774, I mentioned it at the table of Mr. Lavoisier, when most of the philosophical people in the city were present; saying that it was a kind of air in which a candle burned much better than in common air, but I had not then given it any name. At this all the company, and Mr. and Mrs. Lavoisier as much as any, expressed great surprise. I told them that I had got it from _precipitatum per se_, and also from _red lead_." In 1775 Lavoisier's paper, "On the Nature of the Principle which combines with the Metals during their Calcination, and which augments their Weight," was read before the Academy. The preparation and properties of an air obtained, in November 1774, from _red precipitate_ are described, but Priestley's name is not mentioned. It seems probable, however, that Lavoisier learned the existence and the mode of preparation of this air from Priestley;[5] but we have seen that even in 1779 Priestley was quite in the dark as to the true nature of the air discovered by him (p. 60). In papers published in the next three or four years Lavoisier gradually defined and more thoroughly explained the phenomenon of combustion. He burned phosphorus in a confined volume of air, and found that about one-fourth of the air disappeared, that the residual portion of air was unable to support combustion or to sustain animal life, that the phosphorus was converted into a white substance deposited on the sides of the vessel in which the experiment was performed, and that for each grain of phosphorus used about two and a half grains of this white solid were obtained. He further described the properties of the substance produced by burning phosphorus, gave it the name of _phosphoric acid_, and described some of the substances formed by combining it with various bases. The burning of candles in air was about this time studied by Lavoisier. He regarded his experiments as proving that the air which remained after burning a candle, and in which animal life could not be sustained, was really present before the burning; that common air consisted of about one-fourth part of dephlogisticated air and three-fourths of _azotic air_ (_i.e._ air incapable of sustaining life); and that the burning candle simply combined with, and so removed the former of these, and at the same time produced more or less fixed air. In his treatise on chemistry Lavoisier describes more fully his proof that the calcination of a metal consists in the removal, by the metal, of dephlogisticated air (or oxygen) from the atmosphere, and that the metallic calx is simply a compound of metal and oxygen. The experiments are strictly quantitative and are thoroughly conclusive. He placed four ounces of pure mercury in a glass balloon, the neck of which dipped beneath the surface of mercury in a glass dish, and then passed a little way up into a jar containing fifty cubic inches of air, and standing in the mercury in the dish. There was thus free communication between the air in the balloon and that in the glass jar, but no communication between the air inside and that outside the whole apparatus. The mercury in the balloon was heated nearly to its boiling point for twelve days, during which time red-coloured specks gradually formed on the surface of the metal; at the end of this time it was found that the air in the glass jar measured between forty-two and forty-three cubic inches. The red specks when collected amounted to forty-five grains; they were heated in a very small retort connected with a graduated glass cylinder containing mercury. Between seven and eight cubic inches of pure dephlogisticated air (oxygen) were obtained in this cylinder, and forty-one and a half grains of metallic mercury remained when the decomposition of the red substance was completed. The conclusion drawn by Lavoisier from these experiments was that mercury, when heated nearly to boiling in contact with air, withdraws oxygen from the air and combines with this gas to form _red precipitate_, and that when the red precipitate which has been thus formed is strongly heated, it parts with the whole of its oxygen, and is changed back again into metallic mercury. Lavoisier had now (1777-78) proved that the calces of mercury, tin and lead are compounds of these metals with oxygen; and that the oxygen is obtained from the atmosphere when the metal burns. But the phlogistic chemistry was not yet overthrown. We have seen that the upholders of phlogiston believed that in the inflammable air of Cavendish they had at last succeeded in obtaining the long-sought-for phlogiston. Now they triumphantly asked, Why, when metals dissolve in diluted vitriolic or muriatic acid with evolution of inflammable air, are calces of these metals produced? And they answered as triumphantly, Because these metals lose phlogiston by this process, and we know that a calx is a metal deprived of its phlogiston. Lavoisier contented himself with observing that a metallic calx always weighed more than the metal from which it was produced; and that as inflammable air, although much lighter than common air, was distinctly possessed of weight, it was not possible that a metallic calx could be metal deprived of inflammable air. He had given a simple explanation of the process of calcination, and had proved, by accurate experiments, that this explanation was certainly true in some cases. Although all the known facts about solution of metals in acids could not as yet be brought within his explanation, yet none of these facts was absolutely contradictory of that explanation. He was content to wait for further knowledge. And to gain this further knowledge he set about devising and performing new experiments. The upholders of the theory of phlogiston laid considerable stress on the fact that metals are produced by heating metallic calces in inflammable air; the air is absorbed, they said, and so the metal is reproduced. It was obviously of the utmost importance that Lavoisier should learn more about this inflammable air, and especially that he should know exactly what happened when this air was burned. He therefore prepared to burn a large quantity of inflammable air, arranging the experiment so that he should be able to collect and examine the product of this burning, whatever should be the nature of that product. But at this time the news was brought to Paris that Cavendish had obtained water by burning mixtures of inflammable and dephlogisticated airs. This must have been a most exciting announcement to Lavoisier; he saw how much depended on the accuracy of this statement, and as a true student of Nature, he at once set about to prove or disprove it. On the 24th of June 1783, in the presence of the King and several notabilities (including Sir Charles Blagden, Secretary of the Royal Society, who had told Lavoisier of the experiments of Cavendish), Lavoisier and Laplace burned inflammable and dephlogisticated airs, and obtained water. As the result of these experiments they determined that one volume of dephlogisticated air combines with 1.91 volumes of inflammable air to form water. A little later Lavoisier completed the proof of the composition of water by showing that when steam is passed through a tube containing iron filings kept red hot, inflammable air is evolved and calx of iron remains in the tube. Lavoisier could now explain the conversion of a metallic calx into metal by the action of inflammable air; this air decomposes the calx--that is, the metallic oxide--combines with its oxygen to form water, and so the metal is produced. When a metal is dissolved in diluted vitriolic or muriatic acid a calx is formed, because, according to Lavoisier, the water present is decomposed by the metal, inflammable air is evolved, and the dephlogisticated air of the water combines with the metal forming a calx, which then dissolves in the acid. Lavoisier now studied the properties of the compounds produced by burning phosphorus, sulphur and carbon in dephlogisticated air. He found that solutions of these compounds in water had a more or less sour taste and turned certain blue colouring matters red; but these were the properties regarded as especially belonging to acids. These products of combustion in dephlogisticated air were therefore acids; but as phosphorus, carbon and sulphur were not themselves acids, the acid character of the substances obtained by burning these bodies in dephlogisticated air must be due to the presence in them of this air. Hence Lavoisier concluded that this air is the substance the presence of which in a compound confers acid properties on that compound. This view of the action of dephlogisticated air he perpetuated in the name "oxygen" (from Greek, = _acid-producer_), which he gave to dephlogisticated air, and by which name this gas has ever since been known. Priestley was of opinion that the atmosphere is rendered noxious by the breathing of animals, because it is thereby much phlogisticated, and he thought that his experiments rendered it very probable that plants are able to purify this noxious air by taking away phlogiston from it (see p. 69). But Lavoisier was now able to give a much more definite account of the effects on the atmosphere of animal and vegetable life. He had already shown that ordinary air contains oxygen and azote (nitrogen), and that the former is alone concerned in the process of combustion. He was now able to show that animals during respiration draw in air into their lungs: that a portion of the oxygen is there combined with carbon to form carbonic acid gas (as the fixed air of Black was now generally called), which is again expired along with unaltered azote. Respiration was thus proved to be a process chemically analogous to that of calcination. Thus, about the year 1784-85, the theory of phlogiston appeared to be quite overthrown. The arguments of its upholders, after this time, were not founded on facts; they consisted of fanciful interpretations of crudely performed experiments. Cavendish was the only opponent to be dreaded by the supporters of the new chemistry. But we have seen that although Cavendish retained the language of the phlogistic theory (see pp. 78, 79) as in his opinion equally applicable to the facts of combustion with that of the new or Lavoisierian theory, he nevertheless practically admitted the essential point of the latter, viz. that calces are compounds of metal and oxygen (or dephlogisticated air). Although Cavendish was the first to show that water is produced when the two gases hydrogen and oxygen are exploded together, it would yet appear that he did not fully grasp the fact that water is a compound of these two gases; it was left to Lavoisier to give a clear statement of this all-important fact, and thus to remove the last prop from under the now tottering, but once stately edifice built by Stahl and his successors. The explanation given by Lavoisier of combustion was to a great extent based on a conception of element and compound very different from that of the older chemists. In the "Sceptical Chymist" (1661) Boyle had argued strongly against the doctrine of the four "elementary principles," earth, air, fire and water, as held by the "vulgar chymists." The existence of these principles, or some of them, in every compound substance was firmly held by most chemists in Boyle's time. They argued thus: when a piece of green wood bums, the existence in the wood of the principle of fire is made evident by the flame, of the principle of air by the smoke which ascends, of that of water by the hissing and boiling sound, and of the principle of earth by the ashes which remain when the burning is finished.[6] Boyle combated the inference that because a flame is visible round the burning wood, and a light air or smoke ascends from it, _therefore_ these principles were contained in the wood before combustion began. He tried to prove by experiments that one substance may be obtained from another in which the first substance did not already exist; thus, he heated water for a year in a closed glass vessel, and obtained solid particles heavier than, and as he supposed formed from, the water. We have already learned the true interpretation of this experiment from the work of Lavoisier. Boyle grew various vegetables in water only, and thought that he had thus changed water into solid vegetable matter. He tells travellers' tales of the growth of pieces of iron and other metals in the earth or while kept in underground cellars. We now know how erroneous in most points this reasoning was, but we must admit that Boyle established one point most satisfactorily, viz. that because earth, or air, or fire, or water is obtained by heating or otherwise decomposing a substance, it does not necessarily follow that the earth, or air, or fire, or water existed as such in the original substance. He overthrew the doctrine of elementary principles held by the "vulgar chymists." Defining elements as "certain primitive and simple bodies which, not being made of any other bodies, or of one another, are the ingredients of which all those called perfectly mixt bodies are immediately compounded, and into which they are ultimately resolved," Boyle admitted the _possible_ existence, but thought that the facts known at his time did not warrant the assertion of the _certain_ existence, of such "elements." The work of Hooke and Mayow on combustion tended to strengthen this definition of "element" given by Boyle. Black, as we have seen, clearly proved that certain chemical substances were possessed of definite and unvarying composition and properties; and Lavoisier, indirectly by his explanation of combustion, and directly in his "Treatise on Chemistry", laid down the definition of "element" which is now universally adopted. An element is a substance from which no simpler forms of matter--that is, no forms of matter each weighing less than the original substance--have _as yet_ been obtained. In the decade 1774-1784 chemical science was thus established on a sure foundation by Lavoisier. Like most great builders, whether of physical or mental structures, he used the materials gathered by those who came before him, but the merit of arranging these materials into a well-laid foundation, on which the future building might firmly rest, is due to him alone. The value of Lavoisier's work now began to be recognized by his fellow-chemists in France. In 1785 Berthollet, one of the most rising of the younger French chemists, declared himself a convert to the views of Lavoisier on combustion. Fourcroy, another member of the Academy, soon followed the example of Berthollet. Fourcroy, knowing the weakness of his countrymen, saw that if the new views could be made to appear as especially the views of Frenchmen, the victory would be won; he therefore gave to the theory of Lavoisier the name "_La chimie Française_". Although this name was obviously unfair to Lavoisier, it nevertheless caused the antiphlogistic theory to be identified with the French chemists, and succeeded in impressing the French public generally with the idea that to hold to the old theory was to be a traitor to the glory of one's country. M. de Morveau, who held a prominent place both in politics and science, was invited to Paris, and before long was persuaded to embrace the new theory. This conversion--for "the whole matter was managed as if it had been a political intrigue rather than a philosophical inquiry"--was of great importance to Lavoisier and his friends. M. de Morveau was editor of the chemical part of the "Encyclopédie Méthodique;" in that part of this work which had appeared before 1784 De Morveau had skilfully opposed the opinions of Lavoisier, but in the second part of the work he introduced an advertisement announcing the change in his opinions on the subject of combustion, and giving his reasons for this change. The importance of having a definite language in every science is apparent at each step of advance. Lavoisier found great difficulty in making his opinions clear because he was obliged to use a language which had been introduced by the phlogistic chemists, and which bore the impress of that theory on most of its terms. About the years 1785-1787, Lavoisier, Berthollet, Fourcroy and De Morveau drew up a new system of chemical nomenclature. The fundamental principles of that system have remained as those of every nomenclature since proposed. They are briefly these:-- An element is a substance from which no form of matter simpler than itself has as yet been obtained. Every substance is to be regarded as an element until it is proved to be otherwise. The name of every compound is to tell of what elements the substance is composed, and it is to express as far as possible the relative amounts of the elements which go to form the compound. Thus the compounds of oxygen with any other element were called oxides, _e.g._ iron oxide, mercury oxide, tin oxide, etc. When two oxides of iron came to be known, one containing more oxygen relatively to the amount of iron present than the other, that with the greater quantity of oxygen was called iron peroxide, and that with the smaller quantity iron protoxide. We now generally prefer to use the name of the element other than oxygen in adjectival form, and to indicate the relatively smaller or greater quantity of oxygen present by modifications in the termination of this adjective. Thus iron protoxide is now generally known as ferr_ous_ oxide, and iron peroxide as ferr_ic_ oxide. But the principles laid down by the four French chemists in 1785-1787 remain as the groundwork of our present system of nomenclature. The antiphlogistic theory was soon adopted by all French chemists of note. We have already seen that Black, with his usual candour and openness to conviction, adopted and taught this theory, and we are assured by Dr. Thomas Thomson that when he attended Black's classes, nine years after the publication of the French system of nomenclature, that system was in general use among the chemical students of the university. The older theory was naturally upheld by the countrymen of the distinguished Stahl after it had been given up in France. In the year 1792 Klaproth, who was then Professor of Chemistry in Berlin, proposed to the Berlin Academy of Sciences to repeat the more important experiments on which the Lavoisierian theory rested, before the Academy. His offer was accepted, and from that time most of the Berlin chemists declared themselves in favour of the new theory. By the close of last century the teaching of Lavoisier regarding combustion found almost universal assent among chemists. But this teaching carried with it, as necessary parts, the fundamental distinction between element and compound; the denial of the existence of "principles" or "essences;" the recognition of the study of actually occurring reactions between substances as the basis on which all true chemical knowledge was to be built; and the full acknowledgment of the fact that matter is neither created nor destroyed, but only changed as to its form, in any chemical reaction. Of Lavoisier's other work I can only mention the paper on "Specific Heats" contributed by Laplace and Lavoisier to the Memoirs of the Academy for 1780. In this paper is described the ice calorimeter, whereby the amount of heat given out by a substance in cooling from one definite temperature to another is determined, by measuring the amount of ice converted into water by the heated substance in cooling through the stated interval of temperature. The specific heats of various substances, _e.g._ iron, glass, mercury, quicklime, etc., were determined by the help of this instrument. As we read the record of work done by Lavoisier during the years between 1774 and 1794--work which must have involved a great amount of concentrated thought as well as the expenditure of much time--we find it hard to realize that the most tremendous political and social revolution which the modern world has seen was raging around him during this time. In the earlier days of the French Revolution, and in the time immediately preceding that movement, many minds had been stirred to see the importance of the study of Nature; but it was impossible that natural science should continue to flourish when the tyrant Robespierre had begun the Reign of Terror. The roll of those who perished during this time contains no more illustrious name than that of Antoine Laurent Lavoisier. In the year 1794 Lavoisier, who had for some time acted as a _fermier-général_ under the Government, was accused of mixing with the tobacco "water and other ingredients hurtful to the health of the citizens." On this pretext he and some of his colleagues were condemned to death. For some days Lavoisier found a hiding-place among his friends, but hearing that his colleagues had been arrested, he delivered himself up to the authorities, only asking that the death sentence should not be executed until he had completed the research in which he was engaged; "not" that he was "unwilling to part with life," but because he thought the results would be "for the good of humanity." "The Republic has no need of chemists; the course of justice cannot be suspended," was the reply. On the 8th of May 1794, the guillotine did its work; and in his fifty-first year Lavoisier "joined the majority." To the honour of the Academy of which he was so illustrious a member it is recorded that a deputation of his fellow-workers in science, braving the wrath of Robespierre, penetrated to the dungeons of the prison and placed a wreath on the grave of their comrade. * * * * * The period of the infancy of chemical science which I have now briefly described is broadly contemporaneous with the second half of the eighteenth century. At this time the minds of men were greatly stirred. Opinions and beliefs consecrated by the assent of generations of men were questioned or denied; the pretensions of civil and ecclesiastical authorities were withstood; assertions however strongly made, and by whatever authority supported, were met by demands for reasons. In France this revolt against mere authority was especially marked. Led by the great thinker Voltaire, the French philosophers attacked the generally accepted views in moral, theological and historical matters. A little later they began to turn with eager attention and hope to the facts of external Nature. Physical science was cultivated with wonderful vigour and with surprising success. In the sciences of heat and light we have at this time the all-important works of Fourier, Prévost and Fresnel; in geology and natural history we have Buffon and Cuvier; the name of Bichat marks the beginning of biological science, and chemistry takes rank as a science only from the time of Lavoisier. From the philosophers an interest in natural science spread through the mass of the people. About the year 1870 the lecture-rooms of the great teachers of chemistry, astronomy, electricity, and even anatomy were crowded with ladies and gentlemen of fashion in the French capital. A similar state of matters was noticeable in this country. Dr. Black's lecture theatre was filled by an audience which comprised many young men of good position. To know something of chemistry became an essential part of the training of all who desired to be liberally educated. The secrets of Nature were now rapidly explored; astonishing advances were made, and as a matter of course much opposition was raised. In this active, inquiring atmosphere the young science of chemistry grew towards maturity. Priestley, ever seeking for new facts, announcing discovery after discovery, attacking popular belief in most matters, yet satisfied to interpret his scientific discoveries in terms of the hypothesis with which he was most familiar, was the pioneer of the advancing science. He may be compared to the advance-guard sent forward by the explorers of a new country with orders to clear a way for the main body: his work was not to level the rough parts of the way, or to fill in the miry places with well-laid metal, but rather rapidly to make a road as far into the heart of the country as possible. And we have seen how well he did the work. In his discovery of various kinds of airs, notably of oxygen, he laid the basis of the great generalizations of Lavoisier, and, what was perhaps of even more importance, he introduced a new method into chemistry. He showed the existence of a new and unexplored region. Before his time, Hooke and Mayow had proved the existence of more than one kind of air, but the chemistry of gases arose with the discoveries of Priestley. Although Black's chief research, on fixed air and on latent heat, was completed fifteen or twenty years before Priestley's discovery of oxygen, yet the kind of work done by Black, and its influence on chemical science, mark him as coming after Priestley in order of development. We have seen that the work of Black was characterized by thoroughness and suggestiveness. The largeness of scope, the breadth of view, of this great philosopher are best illustrated in his discourses on heat; he there leads us with him in his survey of the domain of Nature, and although he tells us that hypotheses are a "mere waste of time," we find that it is by the strength of his imagination that he commands assent. But he never allows the imagination to degenerate into fanciful guesses; he vigorously tests the fundamental facts of his theory, and then he uses the imagination in developing the necessary consequences of these facts. To Black we owe not only the first rigorously accurate chemical investigation, but also the establishment of just ideas concerning the nature of heat. But Lavoisier came before us as a greater than either Priestley or Black. To great accuracy and great breadth of view he added wonderful power of generalizing; with these, aided by marked mental activity and, on the whole, favourable external circumstances, he was able finally to overthrow the loose opinions regarding combustion and elementary principles which prevailed before his time, and so to establish chemistry as one of the natural sciences. At the close of the first period of advance we find that the sphere of chemistry has been defined; that the object of the science has been laid down, as being to find an explanation of the remarkable changes noticed in the properties of bodies; that as a first step towards the wished-for explanation, all material substances have been divided by the chemist into elements and compounds; that an element has been defined as any kind of matter from a given weight of which no simpler forms of matter--that is, no kinds of matter each weighing less than the original matter--have as yet been obtained; that the great principle of the indestructibility of matter has been established, viz. that however the properties of matter may be altered, yet the total mass (or quantity) remains unchanged; and lastly, we find that an explanation of one important class of chemical changes--those changes which occur when substances burn--has been found. And we have also learned that the method by which these results were obtained was this--to go to Nature, to observe and experiment accurately, to consider carefully the results of these experiments, and so to form a general hypothesis; by the use of the mental powers, and notably by the use of the imagination, to develop the necessary deductions from this hypothesis; and finally, to try these deductions by again inquiring from Nature "whether these things were so." Before the time which we have been considering the paths of chemical science had scarcely yet been trodden. Each discovery was full of promise, each advance displayed the possibility of further progress; the atmosphere was filled as with "a mighty rushing wind" ready to sweep away the old order of things. The age was an age of doubt and of freedom from the trammels of authority; it was a time eminently suited for making advances in natural knowledge. In the unceasing activity of Priestley and Lavoisier we may trace the influence of the restlessness of the age; but in the quietness and strength of the best work of these men, and notably in the work of Black; in the calmness with which Priestley bore his misfortunes at Birmingham; in the noble words of Lavoisier, "I am not unwilling to part with life, but I ask time to finish my experiments, because the results will, I believe, be for the good of humanity"--we see the truth of the assertion made by one who was himself a faithful student of Nature-- "Nature never did betray The heart that loved her." FOOTNOTES: [4] The translation is taken from Thomson's "History of Chemistry." [5] Nevertheless, in other places Lavoisier most readily acknowledges the merits of Priestley. [6] A similar method of reasoning was employed so far back as the tenth century: thus, in an Anglo-Saxon "Manual of Astronomy" we read, "There is no corporeal thing which has not in it the four elements, that is, air and fire, earth and water.... Take a stick and rub it on something, it becomes hot directly with the fire which lurks in it; burn one end, then goeth the moisture out at the other end with the smoke." CHAPTER III. ESTABLISHMENT OF GENERAL PRINCIPLES OF CHEMICAL SCIENCE--PERIOD OF DALTON. _John Dalton_, 1766-1844. The progress of chemical knowledge became so rapid in the early years of the present century, that although I have in this chapter called the time immediately succeeding that of Lavoisier "the period of John Dalton," and although I shall attempt to describe the advances made by this philosopher without considering those of his contemporaries Davy and Berzelius, yet I must insist on the facts that this arrangement is made purely for the sake of convenience, and that many of the discoveries of Davy, Berzelius and others came in order of time before, or followed close upon the publication of Dalton's atomic theory. Nevertheless, as the work of these men belongs in its essence to the modern period, and as the promulgation of the atomic theory by Dalton marks the beginning of this period, it seems better that we should have a clear conception of what was done by this chemist before proceeding to consider the advances made by his contemporaries and successors. * * * * * JOHN DALTON, the second of three children of Joseph and Deborah Dalton, was born at Eaglesfield, a village near Cockermouth, in Cumberland, on the 5th of September 1766. One of the first meeting-houses established by the Society of Friends is to be found in Eaglesfield. The Dalton family had been settled for several generations on a small copyhold estate in this village. The first of them to join the Friends was the grandfather of John Dalton; his descendants remained faithful adherents of this society. Dalton attended the village schools of Eaglesfield and the neighbourhood until he was eleven years old, by which time, in addition to learning reading, writing and arithmetic, he had "gone through a course of mensuration, surveying, navigation, etc." At the age of ten his taste for measurements and calculations began to be remarked by those around him; this taste was encouraged by Mr. Robinson, a relative of Dalton, who recognizing the indomitable perseverance of the boy appears to have taken some care about this time in directing his mathematical studies. At the early age of twelve Dalton affixed to the door of his father's house a large sheet of paper whereon he announced that he had opened a school for youth of both sexes; also that "paper, pens and ink" were sold within. The boy-teacher had little authority over his pupils, who challenged their master to fight in the graveyard, and broke the windows of the room into which they had been locked till their tasks should be learned. When he was fifteen years old Dalton removed to Kendal, where he continued for eleven or twelve years, at first as assistant-master, and then, along with his elder brother Jonathan, as principal of a boarding school for boys. It was announced by the brothers that in this school "youth will be carefully instructed in English, Latin, Greek and French; also writing, arithmetic, merchants' accounts and the mathematics." The school was not very successful. Both brothers were hard, inflexible, and ungainly in their habits, and neither was fitted to become a successful teacher of boys: of the two, John had the gentler disposition, and was preferred by the boys; "besides, his mind was so occupied by mathematics that their faults escaped his notice." During this time Dalton employed his leisure in learning Latin, Greek and French, and in pursuing his studies in mathematics and natural philosophy. He became a frequent contributor to the _Gentlemen's Diary_, a paper which received problems of various kinds--chiefly mathematical--and presented prizes for their successful solution. Besides setting and answering mathematical problems in this journal, and also in the _Ladies' Diary_, Dalton sometimes ventured into the wider fields of mental phenomena. It seems strange to read that, even at the age of twenty-six, Dalton should occupy his leisure time composing answers to such queries as these:-- "Whether, to a generous mind, is the conferring or receiving an obligation, the greater pleasure?" "Is it possible for a person of sensibility and virtue, who has once felt the passion of love in the fullest extent that the human heart is capable of receiving it (being by death or some other circumstance for ever deprived of the object of its wishes), ever to feel an equal passion for any other object?" In his answer to the second of these queries, Dalton carefully framed two hypotheses, and as carefully drew conclusions from each. The question in the _Diary_ was by "Mira;" if "Mira" were a "rapturous maiden" she would not derive much comfort from the cold and mathematical answer by "Mr. John Dalton of Kendal." At Kendal Dalton made the acquaintance of Mr. Gough, who was about eight years older than Dalton, and had been blind from the age of two. Mr. Gough, we are assured by Dalton, was "a perfect master of the Latin, Greek and French tongues;" he understood "well all the different branches of mathematics;" there was "no branch of natural philosophy but what he was well acquainted with;" he knew "by the touch, taste and smell, almost every plant within twenty miles of Kendal." To the friendship of this remarkable man Dalton owed much; with his help he acquired a fair knowledge of the classical languages, and he it was who set Dalton the example of keeping a regular record of weather observations. On the 24th of March 1787 Dalton made his first entry in a book which he entitled "Observations on the Weather, etc.;" the last entry in this book he made fifty-seven years later on the evening preceding his death. The importance of Dalton's meteorological observations, as leading him to the conception of the atomic theory, will be noticed as we proceed. In the year 1793 Dalton, who was now twenty-seven years of age, was invited to Manchester to become tutor in the mathematical and natural philosophy department of a college recently established by influential Dissenters in that town. Eighty pounds for the session of ten months was guaranteed him; and he was provided with "rooms and commons" in the college at a charge of £27 10_s._ per session. He held this appointment for six years, when he retired, and continuing to live in Manchester devoted himself to researches in natural philosophy, gaining a living by giving private lessons in mathematics and physical science at a charge of 2_s._ 6_d._ per hour, or 1_s._ 6_d._ each if more than two pupils attended at the same time. Dalton was elected a Fellow of the Literary and Philosophical Society of Manchester in the year 1794; and from the time of his retiring from the tutorship of Manchester New College till the close of his life he spent a great part of his time in a room in the society's house in George Street, in studying and teaching. The fifty years thus spent are marked by few outward events. The history of Dalton's life from this time is the history of the development of his intellect, and the record of his scientific discoveries. On one occasion during Dalton's stay at Kendal, as he was about to make a visit to his native village, he bethought himself that the present of a pair of silken hose would be acceptable to his mother. He accordingly purchased a pair marked "newest fashion;" but his mother's remark, "Thou hast brought me a pair of grand hose, John; but what made thee fancy so light a colour? I can never show myself at meeting in them," rather disconcerted him, as to his eyes the hose were of the orthodox drab colour. His mother insisted that the stockings were "as red as a cherry." John's brother upheld the "drab" side of the dispute; so the neighbours were called in, and gave their decision that the hose were "varra fine stuff, but uncommon scarlety." From this time Dalton made observations on the peculiarities of his own vision and that of others, and in his first paper read before the Literary and Philosophical Society in 1794, he described these peculiarities. He says, "Since the year 1790 the occasional study of botany obliged me to attend more to colour than before. With respect to colours that were white, yellow, or green, I readily assented to the appropriate term; blue, purple, pink and crimson appeared rather less distinguishable, being, according to my idea, all referable to blue. I have often seriously asked a person whether a flower was blue or pink, but was generally considered to be in jest." Dalton's colour-blindness was amusingly illustrated at a later time, when having been created D.C.L. by the University of Oxford he continued to wear the red robes of his degree for some days; and when his attention was drawn to the somewhat strange phenomenon, even in a university town, of an elderly gentleman in the dress of a Quaker perambulating the town day after day in a scarlet robe, he remarked that to him the gown appeared to be of the same colour as the green trees. Dalton's work during the next six or eight years dealt chiefly with problems suggested by his meteorological observations; he published a volume on "Meteorological Observations and Essays," chiefly occupied with descriptions of the instruments employed, more especially of the thermometer and barometer, and an instrument for determining the dew-point of air. By this time he had established the existence of a connection of some kind between magnetism and the aurora, and had thus laid the foundations of a most important branch of meteorology. In 1799, in a note to a paper on rain and dew, he begins his work on aqueous vapour in the atmosphere by proving that water vapour exists as such in the air. This paper is quickly followed by another on the conducting power of water for heat. A very important paper was published in 1801, on the "Constitution of Mixed Gases, etc.," wherein Dalton asserted that the total pressure of a mixture of two gases on the walls of the containing vessel is equal to the sum of the pressures of each gas; in other words, that if one gas is removed the pressure now exerted by the remaining gas is exactly the same as was exerted by that gas in the original mixture. In a paper published much later (1826), when his views and experiments on this subject were matured, he writes: "It appears to me as completely demonstrated as any physical principle, that whenever two or more ... gases or vapours ... are put together, either into a limited or unlimited space, they will finally be arranged each as if it occupied the whole space, and the others were not present; the nature of the fluids and gravitation being the only efficacious agents." This conclusion was followed out and extended in a paper published in 1803, on the absorption of gases by water and other liquids, wherein he states that the amount of each gas _mechanically dissolved_ by a liquid from a mixture of gases depends only on the quantity of _that_ gas in the mixture, the other gases exerting no influence in this respect. Dalton now considered the variation in the pressures of various gases caused by increasing or decreasing temperature, and then proceeded to discuss the relations which exist between the volumes of gases and the temperature at which these volumes are measured. He concluded that "all elastic fluids" under the same pressure expand equally by heat: and he adds the very important remark, "It seems, therefore, that general laws respecting the absolute quantity and the nature of heat are more likely to be derived from the study of elastic fluids than of other substances"--a remark the profound truth of which has been emphasized by each step in the advances made in our conception of the nature of heat since the time of Dalton. In these papers on the "Constitution of Mixed Gases" Dalton also describes and illustrates a method whereby the actual amount of water vapour in a given bulk of atmospheric air may be found from a knowledge of the dew-point of that air, that is, the temperature at which the deposition of water in the liquid form begins. The introduction of this method for finding the humidity of air marks an important advance in the history of meteorology. In this series of papers published within the first three years of the present century Dalton evidently had before his mind's eye a picture of a gas as a quantity of matter built up of small but independent particles; he constantly speaks of pressures between the small particles of elastic fluids, of these particles as repelling each other, etc. In his "New System" he says, "A vessel full of any pure elastic fluid presents to the imagination a picture like one full of small shot." It is very important to notice that Dalton makes use of this conception of small particles to explain purely physical experiments and operations. Although we know that during these years he was thinking much of "chemical combinations," yet we find that it was his observations on the weather which led him to the conception--a purely physical conception--of each chemically distinct gas as being built up of a vast number of small, equally heavy particles. A consideration of these papers by Dalton on the constitution of mixed gases shows us the method which he pursued in his investigations. "The progress of philosophical knowledge," he says, "is advanced by the discovery of new and important facts; but much more when these facts lead to the establishment of general laws." Dalton always strove to attain to general laws. The facts which he describes are frequently inaccurate; he was singularly deficient in manipulation, and he cannot claim a high place as a careful experimenter. He was however able to draw general conclusions of wide applicability. He seems sometimes to have stated a generalization in definite form before he had obtained any experimental verification of it. In the year 1802 Dalton conducted an examination of air from various localities, and concluded that one hundred volumes of air are composed of twenty-one volumes of oxygen and seventy-nine volumes of nitrogen. This appears to have been his first piece of purely chemical work. But in the next year he again returns to physical phenomena. In the paper already referred to, on the absorption of gases by water and other liquids, published in this year, he had stated that "All gases that enter into water and other liquids by means of pressure, and are wholly disengaged again by the removal of that pressure, are _mechanically_ mixed with the liquid, and not _chemically_ combined with it." But if this be so, why, he asked, does not water mechanically dissolve the same bulk of every kind of gas? The answer which he gives to this question is found at the close of the paper; to the student of chemistry it is very important:-- "This question I have duly considered, and though I am not yet able to satisfy myself completely, I am nearly persuaded that the circumstance depends upon the weight and number of the ultimate particles of the several gases, those whose particles are lightest and single being least absorbable, and the others more, accordingly as they increase in weight and complexity. An inquiry into the relative weights of the ultimate particles of bodies is a subject, as far as I know, entirely new. I have lately been prosecuting this inquiry with remarkable success. The principle cannot be entered upon in this paper; but I shall just subjoin the results, as far as they appear to be ascertained by my experiments." Then follows a "_Table of the relative weights of the ultimate particles of gaseous and other bodies._" The following numbers, among others, are given:-- Hydrogen 1 Sulphur 14·4 Oxygen 5·5 Alcohol 15·1 Azote 4·2 Nitrous oxide 13·7 Phosphorus 7·2 Ether 9·6 Here is the beginning of the atomic theory; and yet Dalton's strictly chemical experimental work lies in the future. The scope of the theory is defined in that sentence--"_An inquiry into the relative weights of the ultimate particles of bodies._" His paper on mixed gases is illustrated by a plate,[7] which shows how vividly Dalton at this time pictured to himself a quantity of gas as composed of many little particles, and how clearly he recognized the necessity of regarding all the particles of each elementary gas as alike, but as differing from those of every other elementary gas. In 1804 Dalton was invited to deliver a course of lectures in the Royal Institution of London, on heat, mixed gases and similar subjects. In these lectures he expounded his views on the constitution of gases, on absorption of gases by liquids, etc. These views drew much attention in this and other countries. "They are busy with them," he writes in 1804, "at London, Edinburgh, Paris and in various parts of Germany, some maintaining one side and some another. The truth will surely out at last." [Illustration: Fig. 2] Dalton's love of numerical calculations is noticeable in a trivial circumstance which he mentions in a letter from London to his brother. He tried to count the number of coaches which he met in going to the Friends' morning meeting: this he assures his brother he "effected with tolerable precision. The number was one hundred and four." During vacation time Dalton usually made a walking excursion in the Lake district. He was extremely fond of mountain scenery, but generally combined the pursuit of science with that of pleasure; he carried his meteorological instruments with him, determined the dew-point at various altitudes, and measured mountain heights by the aid of his barometer. Sometimes however he refused to have anything to do with science. A companion in one of these excursions says that he was "like a schoolboy enjoying a holiday, mocking the cuckoos, putting up and chasing the hares, stopping from time to time to point out some beautiful view, or loitering to chat with passing pedestrians." This side of Dalton's nature was not often apparent. In him the quiet, hard-working student generally appeared prominently marked; but on the half-holiday which he allowed himself on each Thursday afternoon, in order to enjoy the society of a few friends and to engage in his favourite amusement of a game at bowls, he laid aside something of the quietness, regularity and decorum which usually characterized him. "When it came to his turn to bowl he threw his whole soul into the game,... and it was not a little amusing to spectators to see him running after the ball across the green, stooping down as if talking to it, and waving his hands from one side to the other exactly as he wished the line of the ball to be, and manifesting the most intense interest in its coming near to the point at which he aimed." From the year 1803-4 Dalton becomes more and more a worker in chemistry. The establishment of the atomic theory now engaged most of his time and attention. The results of his investigation of "the primary laws which seem to obtain in regard to heat and to chemical combinations" appeared in his "New System of Chemical Philosophy," Part I. of which, "On Heat, on the Constitution of Bodies and on Chemical Synthesis," was published in 1808. We have now arrived at the time when Dalton's inquiry into the "relative weights of the ultimate particles of bodies" was in his opinion sufficiently advanced for presentation to the scientific world; but I think we shall do better to postpone our consideration of this great inquiry until we have completed our review of the chief events in the life of Dalton, other than this the greatest event of all. Dalton did not look for rewards--he desired only the just fame of one who sought for natural truths; but after the publication of the "New System" rewards began to come to him. In 1817 he was elected a corresponding member of the French Academy of Sciences. In 1822, when his fame as a philosophical chemist was fully established, Dalton visited Paris. This visit gave him great pleasure. He was constantly in the society of the great men who then so nobly represented the dignity of natural science in France; Laplace, Cuvier, Biot, Arago, Gay-Lussac, Milne-Edwards and others were his friends. For some time after this visit he was more vivacious and communicative than usual, and we are told by one who lived in the same house as he, "We frequently bantered him with having become half a Frenchman." Dalton especially valued the friendship of Clementine Cuvier, daughter of the great naturalist, with whom he became acquainted during his visit to Paris. All through life he greatly delighted in the society of cultivated women, and his warmest friendships were with gentlewomen. At one time, shortly after going to Manchester, he was much taken by a widow lady who combined great personal charms with considerable mental culture. "During my _captivity_," he writes to a friend, "which lasted about a week, I lost my appetite, and had other symptoms of _bondage_ about me, as incoherent discourse, etc., but have now happily regained my freedom." The society of men who like himself were actively engaged in the investigation of natural science was also a source of much pleasure to Dalton. Such men used to visit him in Manchester, so that in the house of the Rev. Mr. Johns, in whose family he lived, "there were found from time to time some of the greatest philosophers in Europe." Dalton was elected a Fellow of the Royal Society in 1822, and four years later he became the first recipient of one of the Royal Medals, then founded by the King (George IV.). In 1830 he was elected one of the eight foreign Associates of the French Academy, an honour which is generally regarded as the highest that can be bestowed on any man of science. Dalton was one of the original members of the British Association for the Advancement of Science, and he attended most of the meetings from the first held in York in 1831 to that held in Manchester two years before his death. At the Oxford meeting of 1832 he was created D.C.L. by the University, and two years later the University of Edinburgh honoured herself by enrolling his name on the list of her doctors of law. About this time some of Dalton's scientific friends, who considered his work of great national importance, endeavoured to obtain a pension for him from the civil list. At the meeting of the British Association held at Cambridge in 1833, the president, Professor Sedgwick, was able to announce that "His Majesty, willing to manifest his attachment to science, and his regard for a character like that of Dr. Dalton, had graciously conferred on him, out of the funds of the civil list, a substantial mark of his royal favour." The "substantial mark of royal favour," the announcement of which Dalton received "with his customary quietness and simplicity of manner," consisted of a pension of £150 _per annum_, which was increased three years later to £300. The second part of Volume I. of his "New System" was published by Dalton in 1810, and the second volume of the same work in 1827. In 1844 a paper by him was read before the British Association, in which he announced some important discoveries with regard to the water in crystallizable salts, and thus brought a new class of facts within the range of the atomic theory. He was seized with paralysis in 1837, but recovered to a great extent; a second attack in 1844 however completely prostrated him. On the 16th of July in that year he made the last entry in his book of "Observations on the Weather"--"_Little rain_;" next morning he became insensible and quietly passed away. * * * * * It is as the founder of the chemical atomic theory that Dalton must ever be remembered by all students of physical and chemical science. To the Greek philosophers Leucippus and Democritus (flourished about 440-400 B.C.) we owe the conception that "The bodies which we see and handle, which we can set in motion or leave at rest, which we can break in pieces and destroy, are composed of smaller bodies, which we cannot see or handle, which are always in motion, and which can neither be stopped, nor broken in pieces, nor in any way destroyed or deprived of the least of their properties" (Clerk Maxwell). The heavier among these small indivisible bodies or atoms were regarded as always moving downwards. By collisions between these and the lighter ascending atoms lateral movements arose. By virtue of the natural law (as they said) that things of like weight and shape must come to the same place, the atoms of the various elements came together; thus larger masses of matter were formed; these again coalesced, and so finally worlds came into existence. This doctrine was extended by Epicurus (340-270 B.C.), whose teaching is preserved for us in the poem of Lucretius (95-52 B.C.), "De Rerum Natura;" he ascribed to the atoms the power of deviating from a straight line in their descending motion. On this hypothesis Epicurus built a general theory to explain all material and spiritual phenomena. The ceaseless change and decay in everything around them was doubtless one of the causes which led men to this conception of atoms as indivisible, indestructible substances which could never wear out and could never be changed. But even here rest could not be found; the mind was obliged to regard these atoms as always in motion. The dance of the dust-motes in the sunbeam was to Lucretius the result of the more complex motion whereby the atoms which compose that dust are agitated. In his dream as told by Tennyson-- "A void was made in Nature: all her bonds Cracked: and I saw the flaring atom-streams And torrents of her myriad universe, Ruining along the illimitable inane, Fly on to clash together again, and make Another and another frame of things For ever." The central quest of the physicist, from the days of Democritus to the present time, has been to explain the conception of "atom"--to develop more clearly the observed properties of the things which are seen and which may be handled as dependent on the properties of those things which cannot be seen, but which yet exist. For two thousand years he has been trying to penetrate beneath the ever-changing appearances of Nature, and to find some surer resting-place whence he may survey these shifting pictures as they pass before his mental vision. The older atomists thought to find this resting-place, not in the atoms themselves, but in the wide spaces which they supposed to exist between the worlds:-- "The lucid interspace of world and world Where never creeps a cloud, or moves a wind, Nor ever falls the least white star of snow, Nor ever lowest roll of thunder moans, Nor sound of human sorrow mounts to mar Their sacred everlasting calm." To the modern student of science the idea of absolute rest appears unthinkable; but in the most recent outcome of the atomic theory--in the vortex atoms of Helmholtz and Thomson--he thinks he perceives the very "foundation stones of the material universe." Newton conceived the atom as a "solid, massy, hard, impenetrable, movable particle." To the mind of D. Bernoulli the pressure exerted by a gas on the walls of a vessel enclosing it was due to the constant bombardment of the walls by the atoms of which the gas consisted. Atomic motion was the leading idea in the explanation of heat given by Rumford and Davy, and now universally accepted; and, as we have seen, Dalton was himself accustomed to regard all "elastic fluids" (_i.e._ gases) as consisting of vast numbers of atoms. But in the year 1802 or so, Dalton thought that by the study of chemical combinations it would be possible to determine the relative weights of atoms. Assume that any elementary gas is composed of small, indivisible, equally heavy parts; assume that the weight of an atom of one element is different from that of the atom of any other element; and, lastly, assume that when elements combine the atom of the compound so produced is built up of the atoms of the various elements. Make these assumptions, and it follows that the relative weights of two or more elements which combine together must represent the relative weights of the atoms of these elements. We know that the fixity of composition of chemical compounds had been established before this time, largely by the labours of Black and Lavoisier. Fixity of composition had however been called in question by Berthollet, who held that elements combine together in very varying quantities; that, in fact, in place of there being two or three, or a few definite compounds of, say, iron and oxygen, there exists a graduated series of such bodies; and that the amount of iron which combines with oxygen depends chiefly on such physical conditions as the temperature, the pressure, etc., under which the chemical action occurs. But by the date of the publication of the first part of Dalton's "New System," the long dispute between Berthollet and Proust regarding fixity of composition of compounds had nearly closed in favour of the latter chemist, who strongly upheld the affirmative side of the argument. But if Dalton's assumptions are correct, it is evident that when two elements form more than one compound, the quantity of element A in one of these must be a simple multiple of the quantity in the other of these compounds; because there must be a greater number of atoms of element A in the atom of one compound than in that of the other compound, and an elementary atom is assumed to be indivisible. Hence it follows that if one element be taken as a standard, it must be possible to affix to any other element a certain number which shall express the smallest quantity of that element which combines with one part by weight of the standard element; and this number shall also represent how many times the atom of the given element is heavier than the atom of the standard element, the weight of which has been taken to be _one_. If this element forms two compounds with the standard element, the amount of this element in the second compound must be expressed by a simple multiple of the number assigned to this element, because it is not possible, according to the fundamental assumptions of the theory, to form a compound by the combination of fractions of elementary atoms. By pondering on the facts regarding chemical combinations which had been established by various workers previous to the year 1802, Dalton had apparently come to such conclusions as those now indicated. In his paper on the properties of the gases constituting the atmosphere, read to the Manchester Society on November 12, 1802, he stated that one hundred measures of common air would combine with thirty-six measures of "nitrous gas" in a narrow tube to produce an oxide of nitrogen, but with seventy-two measures of the same gas in a wide vessel to produce another oxide of nitrogen. These facts, he says, "clearly point out the theory of the process: the elements of oxygen may combine with a certain portion of nitrous gas, or with twice that portion, but with no intermediate quantity." In the concluding paragraph of his paper on absorption of gases by liquids, read on October 21, 1803, we found (see p. 116) that he had got so far in his inquiry into the "relative weights of the ultimate particles of bodies" as to give a table of twenty-one such weights. About this time Dalton made analyses of two gaseous compounds of carbon--olefiant gas and carburetted hydrogen or marsh-gas. He found that both are compounds of carbon and hydrogen; that in one 4.3 parts by weight of carbon are combined with one part by weight of hydrogen, and in the other the same amount (4.3) of carbon is combined with two parts by weight of hydrogen.[8] This was a striking confirmation of his views regarding combination in multiple proportions, which views followed as a necessary deduction from the atomic hypothesis. From this time he continued to develop and extend this hypothesis, and in the year 1808 he published his "New System of Chemical Philosophy." The first detailed account of the atomic theory was however given to the chemical world the year before Dalton's book appeared. During a conversation with Dalton in the autumn of 1804 Dr. Thomas Thomson learned the fundamental points of the new theory, and in the third edition of his "System of Chemistry," published in 1807, he gave an account of Dalton's views regarding the composition of bodies. In the same year a paper by Thomson appeared in the _Philosophical Transactions_, wherein it was experimentally proved that oxalic acid combines with strontia to form two distinct compounds, one of which contains twice as much oxalic acid as the other, the amount of strontia being the same in both. Analyses of the oxalates of potash, published about the same time by Wollaston, afforded another illustration of the _law of multiple proportions_, and drew the attention of chemists to Dalton's theory. But the new theory was opposed by several very eminent chemists, notably by Sir Humphry Davy. In the autumn of 1807 Wollaston, Thomson and Davy were present at the dinner of the Royal Society Club, at the Crown and Anchor, in the Strand. After dinner, these three chemists discussed the new theory for an hour and a half, Wollaston and Thomson trying to convince Davy of the truth of Dalton's theory; but "so far from being convinced, he went away, if possible, more prejudiced against it than ever." Soon after this Wollaston succeeded in convincing Mr. Davis Gilbert (afterwards President of the Royal Society) of the justness of the atomic theory, and he in turn so placed the facts and the reasoning before Davy, that from this time he became a supporter of the new theory. In order that the atomic theory should be fruitful of results, it was now necessary that the values of the atomic weights of many elements should be carefully determined. Let us consider what knowledge must be acquired before the value to be assigned to the atomic weight of an element can be found. Hydrogen was the element chosen as a standard by Dalton. He assumed that the atom of hydrogen weighs 1; the atomic weight of any other element is therefore a number which tells how many times the atom of that element is heavier than the atom of hydrogen. Thus, when Dalton said the atomic weight of oxygen is 8, he meant that the atom of oxygen is eight times heavier than that of hydrogen. How was this number obtained? Accurate analyses of water show that in this liquid one part by weight of hydrogen is combined with eight parts by weight of oxygen; but (it is said) as the atom of hydrogen weighs 1, the atom of oxygen must weigh 8. In drawing this conclusion it is assumed that the atom, or smallest particle, of water is built up of one atom of hydrogen and one atom of oxygen. Let it be assumed that the atom of water contains two atoms of hydrogen and one of oxygen, then the latter atom must weigh sixteen times as much as each atom of hydrogen; let it be assumed that three atoms of hydrogen combine with one atom of oxygen to form an atom of water, then the weight of the oxygen atom must be twenty-four times that of the hydrogen atom. Any one of these assumptions will equally satisfy the figures obtained by analyzing water (1: 8 = 2: 16 = 3: 24). Now, had we any method whereby we could determine how many times an atom of water is heavier than an atom of hydrogen we should be able to determine which of the foregoing assumptions is correct, and therefore to determine the atomic weight of oxygen. Hence, before the atomic weight of an element can be determined, there must be found some method for determining the atomic weights of compounds of that element. Unless this can be done the atomic theory is of little avail in chemistry. I conceive it to be one of the signal merits of Dalton that he so clearly lays down rules, the best which could be devised at his time, for determining the atomic weights of compounds, or, what is the same thing, for determining the number of elementary atoms in one atom of any compound. In his "New System" he says that he wishes to show the importance of ascertaining "the relative weights of the ultimate particles both of simple and compound bodies, the number of simple elementary particles which constitute one compound particle, and the number of less compound particles which enter into the formation of one more compound particle." Considering compounds of two elements, he divides these into binary, ternary, quaternary, etc., according as the compound atom contains two, three, four, etc., atoms of the elements. He then proceeds thus-- "The following general rules may be adopted as guides in all our investigations respecting chemical synthesis:-- "1st. When only one combination of two bodies can be obtained, it must be presumed to be a _binary_ one, unless some cause appear to the contrary. "2nd. When two combinations are observed, they must be presumed to be a _binary_ and a _ternary_. "3rd. When three combinations are obtained, we may expect one to be _binary_ and the other two _ternary_. "4th. When four combinations are observed, we should expect one _binary_, two _ternary_, and one _quaternary_," etc. Only one compound of hydrogen and oxygen was then known; hence it was presumed to be a binary compound, _i.e._ a compound the smallest particle of which consisted of one atom of hydrogen and one atom of oxygen; and hence, from the data already given on page 130, it followed that the atomic weight of oxygen was 8. Two compounds of carbon and oxygen were known, each containing six parts by weight of carbon, in one case united with eight, and in the other case with sixteen parts by weight of oxygen. From Dalton's rules one of these was a binary, and the other a ternary compound; but as the atomic weight of oxygen had already been determined to be 8, that compound of carbon and oxygen containing eight of oxygen combined with six of carbon was decided to be binary, and that containing sixteen of oxygen (_i.e._ two atoms) to be ternary; and hence the atomic weight of carbon was determined to be 6. In the second part of the "New System" Dalton, guided by these rules, determined experimentally the atomic weights of a great many substances; but this was not the kind of work suited to Dalton's genius. His analytical determinations were generally inaccurate; nevertheless, he clearly showed how the values of the atomic weights of elements ought to be established, and he obtained results sufficiently accurate to confirm his general theory. To make accurate determinations of the relative weights of elementary atoms was one of the tasks reserved for the great Swedish chemist Berzelius (see pp. 162-170). When we examine Dalton's rules we must confess that they appear somewhat arbitrary. He does not give reasons for his assertion that "when only one combination of two bodies can be obtained, it must be presumed to be a binary one." Why may it not be ternary or quaternary? Why must the atom of water be built up of one atom of hydrogen combined with one atom of oxygen? Or, when two compounds are known containing the same pair of elements, why must one be binary and the other ternary? Or, even assuming that this _must_ be justified by facts, does it follow that Dalton's interpretation of the atomic structure of the two oxides of carbon is necessarily correct? These oxides contain 6 of carbon + 8 of oxygen, and 6 of carbon + 16 of oxygen, respectively. Take the second, 6: 16 = 3: 8; assume this to be a binary compound of one atom of oxygen (weighing 8) with one atom of carbon (weighing 3), then the other will be a ternary compound containing one atom of oxygen (8) and two atoms of carbon (6). Hence it appears that Dalton's rules were too arbitrary, and that they were insufficient to determine with certainty the atomic weights of some of the elements. Nevertheless, without some such rules as those of Dalton, no great advances could have been made in applying the atomic theory to the facts of chemical combination; and Dalton's rules were undoubtedly founded on wide considerations. In the appendix to Volume II. of his "New System" he expressly states that before the number of atoms of two elements present in the atom of a compound can be determined, it is necessary that many combinations should be examined, not only of these elements with each other, but also of each of these with other elements; and he tells us that to gather together facts bearing on this general question of chemical synthesis was the object of his work from the time of the promulgation of the atomic theory. When we find that Dalton applied the term "atom" to the small particles of compound bodies, we at once see that by atom he could not always mean "that which cannot be cut;" he simply meant the smallest particle of a substance which exhibits the properties of that substance. A mass of water vapour was conceived by Dalton as "like a mass of small shot." Each shot exhibited the characteristic chemical properties of water vapour; it differed from the large quantity of vapour only in mass; but if one of these little pieces of shot were divided--as Dalton, of course, knew it could be divided--smaller pieces of matter would be produced. But these would no longer be water; they would be new kinds of matter. They are called oxygen and hydrogen. As aids towards gaining a clear conception of the "atom" of a compound as a definite building, Dalton made diagrammatic representations of the hypothetical structures of some of these atoms: the following plate is copied from the "New System:"--A represents an atom of alum; B, an atom of nitrate of alumina; C, of barium chloride; D, of barium nitrate; E, of calcium chloride; F calcium nitrate; G, of calcium sulphate; H, potassium carbonate; I, of potash; and K, an atom of soda. [Illustration: Fig. 3.] But I think if we consider this application of the term "atom" to elements and compounds alike, we shall see objections to it. When an atom of a compound is divided the smaller particles so produced are each very different in chemical properties from the atom which has just been divided. We may, if we choose, assume that the atom of an element could in like manner be divided, and that the products of this division would be different from the elementary atoms; but such a division of an elementary atom has not as a matter of fact been yet accomplished, unless we class among elements substances such as potash and soda, which for many years were universally regarded as elements, and rightly so regarded because they had not been decomposed. In Dalton's nomenclature then, the term "atom" is applied alike to a small particle with definite properties known to be divisible into smaller particles, each with properties different from those of the undivided particle, and to a small particle which, so far as our knowledge goes, cannot be divided into any particle smaller than or different from itself. Nevertheless, if the atomic theory was to be victorious, it was necessary that it should be applied to elements and compounds alike. Until a clear conception should be obtained, and expressed in accurate language, of the differences in structure of the ultimate particles of compounds and of elements, it was perhaps better to apply the term "atom" to both alike. These two difficulties--(1) the difficulty of attaching to the term "atom" a precise meaning applicable to elements and compounds alike, and (2) the difficulty of determining the number of elementary atoms in the atom of a given compound, and hence of determining the relative weights of elementary atoms themselves--were for many years stumbling-blocks in the path of the upholders of the Daltonian theory. The very great difficulty of clearly comprehending the full meaning of Dalton's proposed theory becomes apparent when we learn that within three years from the publication of Part I. of the "New System," facts were made known by the French chemist Gay-Lussac, and the true interpretation of these facts was announced by the Italian chemist Avogadro, which facts and interpretation were sufficient to clear away both the difficulties I have just mentioned; but that nevertheless it is only within the last ten or fifteen years that the true meaning of the facts established by Gay-Lussac and the interpretation given by Avogadro have been generally recognized. In 1809 Gay-Lussac, in a memoir on the combination of gaseous bodies, proved that gases combine chemically in simple proportions by volume, and that the volume of the product always bears a simple relation to the volumes of the combining gases. Thus, he showed that two volumes of hydrogen combine with one volume of oxygen to form two volumes of water vapour; that one volume of nitrogen combines with three volumes of hydrogen to form two volumes of ammonia gas, and so on. Now, as elements combine atom with atom, the weights of these combining volumes of elements must represent the relative weights of the atoms of the same elements. In 1811 Avogadro distinguished between the ultimate particles of compounds and elements. Let a gaseous element, A, combine with another gaseous element, B, to form a gaseous compound, C; then Avogadro supposed that the little particles of A and the little particles of B (Dalton's atoms) split up, each into two or more smaller particles, and that these smaller particles then combine together to form particles of the compound C. The smaller particles produced by splitting a Daltonian elementary atom were regarded by Avogadro as all identical in properties, but these very small particles could not exist uncombined either with each other or with very small particles of some other element. When the atom of a compound is decomposed, Avogadro pictured this atom as splitting into smaller particles of two or three or more different kinds, according as the compound had contained two or three or different elements. To Avogadro's mental vision an elementary gas appeared as built up of a great many little particles, each exhibiting in miniature all the properties of the gas. The gas might be heated, or cooled, or otherwise physically altered, but each of the little particles remained intact; the moment however that this gas was mixed with another on which it could chemically react, these little particles split into smaller parts, but as the smaller parts so produced could not exist in this state, they seized hold of the corresponding very small parts of the other gas, and thus a particle of a compound gas was produced. A compound gas was pictured by Avogadro as also built up of small particles, each exhibiting in miniature the properties of the gas, and each remaining undecomposed when the gas was subjected only to physical actions; but when the gas was chemically decomposed, each little particle split, but the very small parts thus produced, being each a particle of an elementary substance, continued to exist, and could be recognized by the known properties of that element. To the smallest particle of any substance (elementary or compound) which exhibits the properties of that substance, and which cannot be split into parts without destroying these properties, we now give the name of _molecule_. A molecule is itself a structure. It is built up of parts; each of these parts we now call an _atom_. The molecule of a compound is, of course, composed of the atoms of the elements which form that compound. The molecule may contain two or three or more unlike atoms. The molecule of an element is composed of the atoms of that element, and all of these atoms are supposed to be alike. We cannot get hold of elementary atoms and examine them, but we have a large mass of evidence in favour of the view which regards the molecule of an element as composed of parts each weighing less than the molecule itself. The student of physics or chemistry now believes that, were a very small quantity of a gas (say ammonia) or a drop of a liquid (say water) magnified to something like the size of the earth, he should see before him a vast heap of particles of ammonia or of water, each exhibiting all the properties by the possession of which he now distinguishes ammonia or water from all other kinds of matter. He believes that he should see these particles in motion, each moving rapidly from place to place, sometimes knocking against another, sometimes traversing a considerable space without coming into collision with any other. But the student tries to penetrate yet further into the nature of things. To the vision of the chemist these particles of almost inconceivable minuteness are themselves built up of smaller particles. As there is an architecture of masses, so is there an architecture of molecules. Hydrogen and oxygen are mixed; the chemist sees the molecules of each in their never-ceasing dance moving here and there among the molecules of the other, yet each molecule retaining its identity; an electric spark is passed through the mixture, and almost instantaneously he sees each hydrogen molecule split into two parts, and each oxygen molecule split into two parts, and then he sees these parts of molecules, these atoms, combine, a pair of hydrogen atoms with an atom of oxygen, to form compound molecules of water. Avogadro's hypothesis gave the chemist a definition of "molecule;" it also gave him a definition of "atom." It is evident that, however many atoms of a given element there may be in this or in that compound molecule, no compound of this element can exist containing less than a single atom of the element in question; therefore an atom of an element is the smallest quantity of that element in the molecule of any compound thereof. And so we have come back to the original hypothesis of Dalton; but we have extended and modified that hypothesis--we have distinguished two orders of small particles, the molecule (of a compound or of an element) and the atom (of an element). The combination of two or more elements is now regarded as being preceded by the decomposition of the molecules of these elements into atoms. We have defined molecule and we have defined atom, but before we can determine the relative weights of elementary atoms we must have a means of determining the relative weights of compound molecules. The old difficulty still stares us in the face--how can we find the number of elementary atoms in the molecule of a given compound? The same naturalist who enriched chemical science by the discovery of the molecule as distinct from the atom, placed in the hands of chemists the instrument for determining the relative weights of molecules, and thus also the relative weights of atoms. The great generalization, usually known as _Avogadro's law_, runs thus: "_Equal volumes of gases measured at the same temperature and under the same pressure contain equal numbers of molecules._" Gay-Lussac had concluded that "equal volumes of gases contain equal numbers of atoms;" but this conclusion was rejected, and rightly rejected by Dalton, who however at the same time refused to admit that there is a simple relation between the combining volumes of elements. The generalization of Avogadro has however stood the test of experiment, and is now accepted as one of the fundamental "laws" of chemical science. Like the atomic theory itself, Avogadro's law is an outcome of physical work and of physical reasoning. Of late years the great naturalists, Clausius, Helmholtz, Joule, Rankine, Clerk Maxwell and Thomson have developed the physical theory of molecules, and have shown that Avogadro's law may be deduced as a necessary consequence from a few simple physical assumptions. This law has thus been raised, from being a purely empirical generalization, to the rank of a deduction from a wide, yet simple physical theory. Now, if "equal volumes of gases contain equal numbers of molecules," it follows that the ratio of the densities of any two gases must also be the ratio of the weights of the molecules which constitute these gases. Thus, a given volume of water vapour weighs nine times more than an equal volume of hydrogen; therefore the molecule of gaseous water is nine times heavier than the molecule of hydrogen. One has therefore only to adopt a standard of reference for molecular weights, and Avogadro's law gives the means of determining the number of times any gaseous molecule is heavier than that of the standard molecule. But consider the combination of a gaseous element with hydrogen; let us take the case of hydrogen and chlorine, which unite to form gaseous hydrochloric acid, and let us determine the volumes of the uniting elements and the volume of the product. Here is a statement of the results: one volume of hydrogen combines with one volume of chlorine to form two volumes of hydrochloric acid. Assume any number of molecules we please in the one volume of hydrogen--say ten--there must be, by Avogadro's law, also ten molecules in the one volume of chlorine; but inasmuch as the volume of hydrochloric acid produced is double that of either the hydrogen or the chlorine which combined to form it, it follows, by the same law, that twenty molecules of hydrochloric acid have been formed by the union of ten molecules of hydrogen with ten molecules of chlorine. The necessary conclusion is that each hydrogen molecule and each chlorine molecule has split into two parts, and that each half-molecule (or atom) of hydrogen has combined with one half-molecule (or atom) of chlorine, to produce one compound molecule of hydrochloric acid. Therefore we conclude that the hydrogen molecule is composed of two atoms, and that the chlorine molecule is also composed of two atoms; and as hydrogen is to be our standard element, we say that if the atom of hydrogen weighs one, the molecule of the same element weighs two. It is now easy to find the _molecular weight_ of any gas; it is only necessary to find how many times heavier the given gas is than hydrogen, the weight of the latter being taken as 2. Thus, oxygen is sixteen times heavier than hydrogen, but 1: 16 = 2: 32, therefore the molecule of oxygen is thirty-two times heavier than the molecule of hydrogen. Ammonia is eight and a half times heavier than hydrogen, but 1: 8-1/2 = 2: 17, therefore the molecule of ammonia is seventeen times heavier than the molecule of hydrogen. This is what we more concisely express by saying "the molecular weight of oxygen is 32," or "the molecular weight of ammonia is 17," etc., etc. Now, we wish to determine the _atomic weight_ of oxygen; that is, we wish to find how many times the oxygen atom is heavier than the atom of hydrogen. We make use of Avogadro's law and of the definition of "atom" which has been deduced from it (see p. 142). We know that eight parts by weight of oxygen combine with one part by weight of hydrogen to form water; but we do not know whether the molecule of water contains one atom of each element, or two atoms of hydrogen and one atom of oxygen, or some other combination of these atoms (see p. 131). But by vaporizing water and weighing the gas so produced, we find that water vapour is nine times heavier than hydrogen: now, 1: 9 = 2: 18, therefore the molecular weight of water gas is 18. Analysis tells us that eighteen parts by weight of water gas contain sixteen parts of oxygen and two parts of hydrogen; that is to say, we now know that in the molecule of water gas there are two atoms of hydrogen combined with sixteen parts by weight of oxygen. We now proceed to analyze and determine the molecular weights of as many gaseous compounds of oxygen as we can obtain. The outcome of all is that we have as yet failed to obtain any such compound in the molecule of which there are less than sixteen parts by weight of oxygen. In some of these molecules there are sixteen, in some thirty-two, in some forty-eight, in some sixty-four parts by weight of oxygen, but in none is there less than sixteen parts by weight of this element. Therefore we conclude that the atomic weight of oxygen is 16, because this is the smallest amount, referred to hydrogen taken as 1, which has hitherto been found in the molecule of any compound of oxygen. The whole of the work done since the publication of Dalton's "New System" has emphasized the importance of that chemist's remark, that no safe conclusion can be drawn as to the value of the atomic weight of an element except from a consideration of many compounds of that with other elements. But in Avogadro's law we have a far more accurate and trustworthy method for determining the molecular weights of compounds than any which Dalton was able to devise by his study of chemical combinations. We have thus got a clearer conception of "atom" than was generally possessed by chemists in the days of Dalton, and this we have gained by introducing the further conception of "molecule" as that of a quantity of matter different from, and yet similar to, the atom. The task now before us will for the most part consist in tracing the further development of the fundamental conception of Dalton, the conception, viz., of each chemical substance as built up of small parts possessing all the properties, other than the mass, of the whole; and--what we also owe to Dalton--the application of this conception to explain the facts of chemical combination. * * * * * The circumstances of Dalton's early life obliged him to trust largely to his own efforts for acquiring knowledge; and his determination not to accept facts at second hand but to acquire them for himself, is very marked throughout the whole of his life. In the preface to the second part of the "New System" he says, "Having been in my progress so often misled by taking for granted the results of others, I have determined to write as little as possible but what I can attest by my own experience." We should not expect such a man as this to make any great use of books; one of his friends tells us that he heard him declare on a public occasion that he could carry his library on his back, and yet had not read half of the books which comprised it. The love of investigation which characterized Dalton when young would naturally be increased by this course of intellectual life. How strong this desire to examine everything for himself became, is amusingly illustrated by a story told by his medical adviser, Dr. Ransome. Once when Dalton was suffering from catarrh Dr. Ransome had prescribed a James's powder, and finding his patient much better next day, he congratulated himself and Dalton on the good effects of the medicine. "I do not well see how that can be," said Dalton, "as I kept the powder until I could have an opportunity of analyzing it." As Dalton grew older he became more than ever disinclined to place much trust in the results obtained by other naturalists, even when these men were acknowledged to be superior to himself in manipulative and experimental skill. Thus, as we have already learned, he could not be brought to allow the truth of Gay-Lussac's experimentally established law regarding gaseous combinations; he preferred to attribute Gay-Lussac's results to errors of experiment. "The truth is, I believe, that gases do not unite in equal or exact measures in any one instance; when they appear to do so it is owing to the inaccuracy of our experiments." That Dalton did not rank high as an experimenter is evident from the many mistakes in matters of fact which are to be found in the second part of his "New System." A marked example of his inaccuracy in purely experimental work is to be found in the supposed proof given by him that charcoal, after being heated to redness, does not absorb gases. He strongly heated a quantity of charcoal, pulverized it, and placed it in a Florence flask, which was connected by means of a stopcock with a bladder filled with carbonic acid: after a week he found that the flask and its contents had not sensibly increased in weight, and he concluded that no carbonic acid had been absorbed by the charcoal. But no trustworthy result could be obtained from an experiment in which the charcoal, having been deprived of air by heating, was again allowed to absorb air by being pulverized in an open vessel, and was then placed in a flask filled with air, communication between the carbonic acid and the external air being prevented merely by a piece of bladder, a material which is easily permeated by gases. Dalton used a method which can only lead to notable results in natural science when employed by a really great thinker; he acquired a few facts, and then thought out the meaning of these. Almost at the beginning of each investigation he tried to get hold of some definite generalization, and _then_ he proceeded to amass special facts. The object which he kept before himself in his experimental work was to establish or to disprove this or that hypothesis. Every experiment was conducted with a clearly conceived aim. He was even willing to allow a large margin for errors of experiment if he could thereby bring the results within the scope of his hypothesis. That the _law of multiple proportions_ is simply a generalization of facts, and may be stated apart from the atomic theory, is now generally admitted. But in Dalton's mind this law seems to have arisen rather as a deduction from the theory of atoms than to have been gained as a generalization from experiments. He certainly always stated this law in the language of the atomic theory. In one of his walking excursions he explained his theory to a friend, and after expounding his views regarding atomic combinations, he said that the examples which he had given showed the necessary existence of the principle of multiple proportions: "Thou knowest it must be so, for no man can split an atom." We have seen that carburetted hydrogen was one of the compounds on the results of the analysis of which he built his atomic theory; yet we find him saying of the constitution of this compound that "no correct notion seems to have been formed till the atomic theory was introduced and applied in the investigation." When Dalton was meditating on the laws of chemical combination, a French chemist, M. Proust, published analyses of metallic oxides, which proved that when a metal forms two oxides the amount of metal in each is a fixed quantity--that there is a sudden jump, as it were, from one oxide to another. We are sometimes told that from these experiments Proust would have recognized the law of multiple proportions had his analyses only been more accurate; but we know that Dalton's analyses were very inaccurate, and yet he not only recognized the law of multiple proportions, but propounded and established the atomic theory. Something more than a correct system of keeping books and balancing accounts is wanted in natural science. Dalton's experimental results would be the despair of a systematic analyst, but from these Dalton's genius evolved that splendid theory which has done so much to advance the exact investigation of natural phenomena. Probably no greater contrast could be found between methods of work, both leading to the establishment of scientific (that is, accurate and precise) results, than that which exists between the method of Dalton and the method pursued by Priestley. Priestley commenced his experiments with no particular aim in view; sometimes he wanted to amuse himself, sometimes he thought he might light upon a discovery of importance, sometimes his curiosity incited him to experiment. When he got facts he made no profound generalizations; he was content to interpret his results by the help of the prevailing theory of his time. But each new fact only spurred him on to make fresh incursions into the fields of Nature. Dalton thought much and deeply; his experimentally established facts were to him symbols of unseen powers. He used facts as Hobbes says the wise man uses words: they were his counters only, not his money. When we ask how it was that Dalton acquired his great power of penetrating beneath the surface of things and finding general laws, we must attribute this power in part to the training which he gave himself in physical science. It was from a consideration of physical facts that he gained the conception of ultimate particles of definite weight. His method was essentially dynamical; that is, he pictured a gas as a mass of little particles, each of which acted on and was acted on by, other particles. The particles were not thrown together anyhow; definite forces existed between them. Each elementary or compound gas was pictured as a system of little particles, and the properties of that gas were regarded as dependent on the nature and arrangement of these particles. Such a conception as this could only be gained by a careful and profound thinker versed in the methods of physical and mathematical science. Thus we see that although Dalton appeared to gain his great chemical results by a method which we are not generally inclined to regard as the method of natural science, yet it was by virtue of his careful training in a branch of knowledge which deals with facts, as well as in that science which deduces particular conclusions from general principles, that he was able to introduce his fruitful conceptions into the science of chemistry. To me it appears that Dalton was pre-eminently distinguished by the possession of imagination. He formed clear mental images of the phenomena which he studied, and these images he was able to combine and modify so that there resulted a new image containing in itself all the essential parts of each separate picture which he had previously formed. From his intense devotion to the pursuit of science the development of Dalton's general character appears to have been somewhat dwarfed. Although he possessed imagination, it was the imagination of a naturalist rather than that of a man of broad culture. Perhaps it was a want of broad sympathies which made him trust so implicitly in his own work and so readily distrust the work of others, and which moreover led him astray in so many of his purely experimental investigations. * * * * * Dalton began his chemical work about six years after the death of Lavoisier. Unlike that great philosopher he cared nothing for political life. The friends in whose family he spent the greater part of his life in Manchester were never able to tell whether he was Whig or Tory. Unlike Priestley he was content to let metaphysical and theological speculation alone. In his quiet devotion to study he more resembled Black, and in his method, which was more deductive than that usually employed in chemistry, he also resembled the Edinburgh professor. Trained from his earliest days to depend on himself, nurtured in the creedless creed of the Friends, he entered on his life's work with few prejudices, if without much profound knowledge of what had been done before him. By the power of his insight into Nature and the concentration of his thought, he drew aside the curtain which hung between the seen and the unseen; and while Herschel, sweeping the heavens with his telescope and night by night bringing new worlds within the sphere of knowledge, was overpowering men's minds by new conceptions of the infinitely great, John Dalton, with like imaginative power, was examining the architecture of the ultimate particles of matter, and revealing the existence of law and order in the domain of the infinitely small. FOOTNOTES: [7] See Fig. 2, which is copied from the original in the "New System of Chemical Philosophy," and illustrates Dalton's conception of a quantity of carbonic acid gas, each atom built up of one atom of carbon and two of oxygen; of nitrous oxide gas, each atom composed of one atom of nitrogen and one of oxygen; and of hydrogen gas, constituted of single atoms. [8] More accurate analysis has shown that there are six parts of carbon united respectively with one and with two parts by weight of hydrogen in these compounds. CHAPTER IV. ESTABLISHMENT OF GENERAL PRINCIPLES OF CHEMICAL SCIENCE (_continued_)--PERIOD OF DAVY AND BERZELIUS. _Humphry Davy_, 1778-1829. _Johann Jacob Berzelius_, 1779-1848. We may roughly date the period of chemical advance during which the connections between chemistry and other branches of natural knowledge were recognized and studied, as beginning with the first year of this century, and as continuing to our own day. The elaboration of the atomic theory was busily carried on during the second and third decades of this century; to this the labour of the Swedish chemist Berzelius largely contributed. That there exist many points of close connection between chemical and electrical science was also demonstrated by the labours of the same chemist, and by the brilliant and impressive discoveries of Sir Humphry Davy. A system of classification of chemical elements and compounds was established by the same great naturalists, and many inroads were made into the domain of the chemistry of bodies of animal and vegetable origin. The work of Berzelius and Davy, characterized as it is by thoroughness, clearness and definiteness, belongs essentially to the modern era of chemical advance; but I think we shall better preserve the continuity of our story if we devote a chapter to a consideration of the work of these two renowned naturalists before entering on our review of the time immediately preceding the present, as typical workers in which time I have chosen Liebig and Dumas. In the last chapter we found that the foundations of the atomic theory had been laid, and the theory itself had been applied to general problems of chemical synthesis, by Dalton. In giving, in that chapter, a short sketch of the modern molecular theory, and in trying to explain the meaning of the term "molecule" as contrasted with "atom," I necessarily carried the reader forward to a time considerably later than the first decade of this century. We must now retrace our steps; and in perusing the account of the work of Berzelius and Davy given in the present chapter, the reader must endeavour to have in his mind a conception of atom analogous to the mental picture formed by Dalton (see pp. 135, 136); he must regard the term as applicable to element and compound alike; he must remember that the work of which he reads is the work of those who are striving towards a clear conception of the atom, and who are gradually rising to a recognition of the existence of more than one order of small particles, by the regular putting together of which masses of matter are constituted. No materials, so far as I am aware, exist from which a life of Berzelius can be constructed. I must therefore content myself with giving a mere enumeration of the more salient points in his life. Of his chemical work abundant details are fortunately to be found in his own "Lehrbuch," and in the works and papers of himself and his contemporaries. * * * * * JOHANN JACOB BERZELIUS was the son of the schoolmaster of Wäfersunda, a village near Linköping, in East Gothland, Sweden. He was born in August 1779--he was born, that is, a few years after Priestley's discovery of oxygen; at the time when Lavoisier had nearly completed his theory of combustion; when Dalton was endeavouring to keep the unruly youth of Eaglesfield in subjection; and when Black, having established the existence of fixed air and the theory of latent heat, was the central figure in the band of students who were enlarging our knowledge of Nature in the Scottish capital. Being left an orphan at the age of nine, the young Berzelius was brought up by his grandfather, who appears to have been a man of education and sense. After attending school at Linköping, he entered the University of Upsala as a student of medicine. Here he soon began to show a taste for chemistry. It would appear that few or no experiments were then introduced into his lectures by the Professor of Chemistry at Upsala; little encouragement was given to pursue chemical experiments, and so Berzelius had to trust to his own labours for gaining an acquaintance with practical chemistry. Having thus made considerable progress in chemistry, and being on a visit to the mineral baths of Medevi, he seized the opportunity to make a very thorough analysis of the waters of this place, which were renowned in Sweden for their curative properties. The publication of this analysis marks the first appearance of Berzelius as an author. He graduated as M.B. in 1801, and a year or two later presented his dissertation, entitled "The Action of Galvanism on Organic Bodies," as a thesis for the degree of Doctor of Medicine. This thesis, like that of Black, published about half a century earlier, marks an important stage in the history of chemistry. These and other publications made the young doctor famous; he was called to Stockholm to be extraordinary (or assistant) Professor of Chemistry in the medical school of that capital. Sometimes practising medicine in order to add to his limited income, but for the most part engaged in chemical research, he remained in Stockholm for nearly fifty years, during most of which time the laboratory of Berzelius in the Swedish capital was regarded as one of the magnetic poles of the chemical world. To this point came many of the great chemists who afterwards enriched the science by their discoveries. Wöhler, H. and G. Rose, Magnus, Gmelin, Mitscherlich and others all studied with Berzelius. He visited England and France, and was on terms of intimacy and in correspondence with Davy, Dalton, Gay-Lussac, Berthollet and the other men who at that period shed so much lustre on English and French science. It is said that Berzelius was so much pleased with the lectures of Dr. Marcet at Guy's Hospital, that on his return from his visit to England in 1812, he introduced much more liveliness and many more experimental illustrations into his own lectures. At the age of thirty-one, Berzelius was chosen President of the Stockholm Academy of Sciences; a few years later he was elected a Foreign Fellow of the Royal Society, which society bestowed on him the Copley Medal in 1836. He was raised to the rank of a baron by the King of Sweden, being allowed as a special privilege to retain his own name. In the year 1832 Berzelius resigned his professorship, and in the same year he married. During the remainder of his life, he continued to receive honours of all kinds, but he never for a moment forsook the paths of science. After the death of Davy, in 1829, he was recognized as the leading European chemist of his age; but, although firm in his own theoretical views, he was ready to test these views by appealing to Nature. The very persistency with which he clung to a conception established on some solid experimental basis insured that new light would be thrown on that conception by the researches of those chemists who opposed him. Probably no chemist has added to the science so many carefully determined facts as Berzelius; he was always at work in the laboratory, and always worked with the greatest care. Yet the appliances at his command were what we should now call poor, meagre, and utterly inadequate. Professor Wöhler of Göttingen, who in the fulness of days and honours has so lately gone from amongst us, recently gave an account of his visit to Berzelius in the year 1823. Wöhler had taken his degree as Doctor of Medicine at Heidelberg, and being anxious to prosecute the study of chemistry he was advised by his friends to spend a winter in the laboratory of the Swedish professor. Having written to Berzelius and learned that he was willing to allow him working room in his laboratory, the young student set out for Stockholm. After a journey to Lübeck and a few days' passage in a small sailing-vessel, he arrived in the Swedish capital. Knocking at the door of the house pointed out as that of Berzelius, he tells us that his heart beat hard as the door was opened by a tall man of florid complexion. "It was Berzelius himself," he exclaims. Scarcely believing that he was in the very room where so many famous discoveries had been made, he entered the laboratory. No water, no gas, no draught-places, no ovens were to be seen; a couple of plain tables, a blowpipe, a few shelves with bottles, a little simple apparatus, and a large water-barrel whereat Anna, the ancient cook of the establishment, washed the laboratory dishes, completed the furnishings of this room, famous throughout Europe for the work which had been done in it. In the kitchen which adjoined, and where Anna cooked, was a small furnace and a sand bath for heating purposes. In this room many great discoveries were made. Among these we may note the separation of the element columbium in 1815, and of selenion in 1818; the discovery of the new earth thoria in 1828; the elucidation of the properties of yttrium and cerium about 1820, of uranium in 1823, and of the platinum metals in 1828; the accurate determination of the atomic weights of the greater number of the elements; the discovery of "sulphur salts" in 1826-27, and the proof that silica is an acid, and that most of the "stony" minerals are compounds of this acid with various bases. But we shall better learn the value of some of these discoveries by taking a general review of the contributions to chemical science of the man who spent most of his life at work in that room in Stockholm. The German chemist Richter, in the first or second year of this century, had drawn attention to the fact that when two neutral compounds, such as nitrate of potash and chloride of lime, react chemically, the substances produced by this reaction are also neutral. All the potash combined with nitric acid in one salt changes places with all the lime combined with muriatic acid in the other salt; therefore, said Richter, these different quantities of potash and lime are neutralized by the same quantity of nitric acid; and, hence, these amounts of potash and lime are chemically _equivalent_, because these are the amounts which perform the same reaction, viz. neutralization of a fixed quantity of acid. If then careful analyses were made of a number of such neutral compounds as those named, the _equivalents_ of all the commoner "bases" and "acids"[9] might be calculated. Richter's own determinations of the equivalents of acids and bases were not very accurate, but Berzelius was impressed with the importance of this work. The year before the appearance of Dalton's "New System" (_i.e._ in 1807), he began to prepare and carefully analyze series of neutral salts. As the work was proceeding he became acquainted with the theory of Dalton, and at once saw its extreme importance. For some time Berzelius continued to work on the lines laid down by Dalton, and to accumulate data from which the atomic weights of elements might be calculated; but he soon perceived--as the founder of the theory had perceived from the very outset--that the fundamental conception of each atom of an element as being a distinct mass of matter weighing more or less than the atom of every other element, and of each atom of a compound as being built up of the atoms of the elements which compose that compound,--Berzelius, I say, perceived that these conceptions must remain fruitless unless means were found for determining the number of elementary atoms in each compound atom. We have already learned the rules framed by the founder of the atomic theory for his guidance in attempting to solve this problem. Berzelius thought those rules insufficient and arbitrary; he therefore laid down two general rules, on the lines of which he prosecuted his researches into chemical synthesis. "One atom of one element combines with one, two, three, or more atoms of another element." This is practically the same as Dalton's definitions of binary, ternary, etc., compounds (p. 132). "Two atoms of one element combine with three and five atoms of another element." Berzelius here recognizes the existence of compound atoms of a more complex structure than any of those recognized by Dalton. Berzelius further extended the conception of atom by applying it to groups of elements formed, according to him, by the combination of various compound atoms. To his mind every compound atom appeared as built up of two parts; each of these parts might be an elementary atom, or might be itself built up of several elementary atoms, yet in the Berzelian theory each acted as a definite whole. So far as the building up of the complex atom went, each of the two parts into which this atom could be divided acted as if it were a simple atom. If we suppose a patch of two shades of red colour to be laid on a smooth surface, and alongside of this a patch of two shades of yellow colour, and if we suppose the whole mass of colour to be viewed from a distance such that one patch appears uniformly red and the other uniformly yellow, we shall have a rough illustration of the Berzelian compound atom. To the observer the whole mass of colour appears to consist of two distinct patches of contrasted colours; but let him approach nearer, and he perceives that what appeared to be a uniform surface of red or yellow really consists of two patches of unlike shades of red or of yellow. The whole mass of colour represents the compound atom; broadly it consists of two parts--the red colour represents one of the constituent atoms, the yellow colour represents the other constituent atom; but on closer examination the red atom, so to speak--and likewise the yellow atom--is found to consist of parts which are less unlike each other than the whole red atom is unlike the whole yellow atom. We shall have to consider in more detail the reasoning whereby Berzelius arrived at this conception of every compound atom as a _dual_ structure (see pp. 209-212). At present I wish to notice this conception as lying at the root of most of the work which he did in extending and applying the Daltonian theory. I wish to insist on the fact that the atomic theory could not advance without methods being found for determining the number of elementary atoms in a compound atom, without clear conceptions being gained of every compound atom as a structure, and without at least attempts being made to learn the laws in accordance with which that structure was built. Before the atomic weight of oxygen could be determined it was necessary that the number of oxygen and of hydrogen atoms in the atom of water should be known; otherwise all that could be stated was, the atomic weight of oxygen is a simple multiple of 8. Berzelius did much to advance chemical science by the introduction and application of a few simple rules whereby he determined the number of elementary atoms in various compound atoms. But as the science advanced, and as more facts came to be known, the Berzelian rules were found to be too narrow and too arbitrary; chemists sought for some surer and more generally applicable method than that which Berzelius had introduced, and the imperious demand for this method at last forced them to recognize the importance of the great generalization of the Italian naturalist Avogadro, which they had possessed since the year 1811, but the meaning of which they had so long failed to understand. Berzelius made one great step in the direction of recognizing Avogadro's distinction between atom and molecule when he accepted Gay-Lussac's generalization that "equal volumes of gases contain equal numbers of atoms:" but he refused to apply this to other than elementary gases. The weights of the volumes of elementary gases which combined were, for Berzelius, also the weights of the atoms of these elements. Thus, let the weight of one volume of hydrogen be called 1, then two volumes of hydrogen, weighing 2, combine with one volume of oxygen, weighing 16, to form two volumes of water vapour; therefore, said Berzelius, the atom of water consists of two atoms of hydrogen and one atom of oxygen, and the atom of the latter element is sixteen times heavier than the atom of the former. Three volumes of hydrogen, weighing 3, combine with one volume of nitrogen, weighing 14, to form two volumes of ammonia; therefore, said Berzelius, the atom of ammonia consists of three atoms of hydrogen combined with one atom of nitrogen, and the nitrogen atom is fourteen times heavier than the atom of hydrogen. While Berzelius was applying these rules to the determination of the atomic weights of the elements, and was conducting the most important series of analyses known in the annals of the science, two great physico-chemical discoveries were announced. In the year 1818 the "_law of isomorphism_" was stated by Mitscherlich: "Compounds the atoms of which contain equal numbers of elementary atoms, similarly arranged, have the same crystalline form." As thus stated, the law of isomorphism affirms that if two compounds crystallize in the same form, the atoms of these compounds are built up of the same number of elementary atoms--however different may be the nature of the elements in the compounds--and that these elementary atoms are similarly arranged. This statement was soon found to be too absolute, and was accordingly modified; but to go into the history of the law of isomorphism would lead us too far from the great main path of chemical advance, the course of which we are seeking to trace. Berzelius at once accepted Mitscherlich's law, as an aid in his researches on atomic weights. The help to be derived from this law may be illustrated thus: let us assume that two compounds have been obtained exhibiting identity of crystalline form; let it be further assumed that the number of elementary atoms in the atom of one of these compounds is known; it follows, by the law of isomorphism, that the number of elementary atoms in the atom of the other is known also. Let the two compounds be _sulphate of potash_ and _chromate of potash_; let it be assumed that the atom of the first named is known to consist of two atoms of potassium, one atom of sulphur, and four atoms of oxygen; and that the second substance is known to be a compound of the elements potassium, chromium and oxygen; then the atom of the second compound contains, by Mitscherlich's law, two atoms of potassium, one atom of chromium and four atoms of oxygen: hence the relative weight of the atom of chromate of potash can be determined, and hence the relative weight of the atom of chromium can also be determined. A year after the announcement of Mitscherlich's law, the following generalization was stated to hold good, by two French naturalists, Dulong and Petit:--"The atoms of all solid elements have the same capacity for heat." If the amount of heat required to raise the temperature of one grain of water through one degree be called _one unit of heat_, then the capacity for heat of any body other than water is the number of units of heat required to raise the temperature of one grain of that substance through one degree. Each chemical substance, elementary and compound, has its own capacity for heat; but, instead of comparing the capacities for heat of equal weights, Dulong and Petit compared the capacities for heat of weights representing the weights of the atoms of various elements. Thus, equal amounts of heat are required to raise, through the same interval of temperature, fifty-six grains of iron, one hundred and eight grains of silver, and sixty-three and a half grains of copper; but the weights of the atoms of these three elements are in the proportion of 56:108:63-1/2. Dulong and Petit based their generalization on measurements of the capacities for heat of thirteen elements; further research has shown that their statement most probably holds good for all the solid elements. Here then was a most important instrument put into the hands of the chemist. It is only necessary that the atomic weight of one solid element should be certainly known, and that the amount of heat required to raise through one degree the number of grains of that element expressed by its atomic weight should also be known; then the number which expresses the weight, in grains, of any other solid element which is raised through one degree by the same amount of heat, likewise expresses the relative weight of the atom of that element. Thus, suppose that the atomic weight of silver is known to be 108, and suppose that six units of heat are required to raise the temperature of one hundred and eight grains of this metal through one degree; then suppose it is found by experiment that six units of heat suffice to raise the temperature of two hundred and ten grains of bismuth through one degree, it follows--according to the law of Dulong and Petit--that 210 is the atomic weight of bismuth. The modified generalization of Gay-Lussac--"Equal volumes of _elementary_ gases contain equal numbers of atoms;" the laws of "isomorphism" and of "atomic heat;" and the two empirical rules stated on p. 163;--these were the guides used by Berzelius in interpreting the analytical results which he and his pupils obtained in that memorable series of researches, whereby the conceptions of Dalton were shown to be applicable to a wide range of chemical phenomena. The fixity of composition of chemical compounds has now been established; a definite meaning has been given to the term "element;" the conception of "atom" has been gained, but much remains to be done in the way of rendering this conception precise; and fairly good, but not altogether satisfactory methods have been introduced by which the relative weights of the atoms of elements and compounds may be determined. At this time chemists are busy preparing and describing new compounds, and many new elements are also being discovered; the need of classification begins to be felt more and more. In the days of Berzelius and Davy strenuous efforts were made to obtain some generalizations by the application of which the many known elements and compounds might be divided into groups. It was felt that a classification might be founded on the composition of compounds, or perhaps on the properties of the same compounds. These two general principles served as guides in most of the researches then instituted; answers were sought to these two questions: Of what elements is this compound composed? and, What can this compound do; how does it react towards other bodies? Lavoisier, as we know, regarded oxygen as the characteristic element of all _acids_. This term _acid_ implies the possession, by all the substances denoted by it, of some common property; let us shortly trace the history of this word in chemistry. Vinegar was known to the Greeks and Romans, and the names which they gave this substance tell us that sourness was to them its characteristic property. They knew that vinegar effervesced when brought into contact with chalky earths, and that it was able to dissolve many substances--witness the story of Cleopatra's draught of the pearl dissolved in vinegar. Other substances possessed of these properties--for instance oil of vitriol and spirits of salt--as they became known, were classed along with vinegar; but no attempts were made to clearly define the properties of these bodies till comparatively recent times. The characteristics of an acid substance enumerated by Boyle are--solvent power, which is exerted unequally on different bodies; power of turning many vegetable blues to red, and of restoring many vegetable colours which had been destroyed by alkalis; power of precipitating solid sulphur from solutions of this substance in alkalis, and the power of acting on alkalis to produce substances without the properties of either acid or alkali. But what, one may ask, is an alkali, of which mention is so often made by Boyle? From very early times it had been noticed that the ashes which remained when certain plants were burned, and the liquid obtained by dissolving those ashes in water, had great cleansing powers; that they removed oily matter, fat and dirt from cloth and other fabrics. The fact that an aqueous solution of these ashes affects the coloured parts of many plants was also noticed in early times. As progress was made in chemical knowledge observers began to contrast the properties of this plant-ash with the properties of acids. The former had no marked taste, the latter were always very sour; the former turned some vegetable reds to blue, the latter turned the blues to red; a solution of plant-ash had no great solvent action on ordinary mineral matter, whereas this matter was generally dissolved by an acid. In the time of the alchemists, who were always seeking for the principles or essences of things, these properties of acids were attributed to _a principle of acidity_, while the properties of plant-ash and substances resembling plant-ash were attributed to a _principle of alkalinity_ (from Arabic _alkali_, or _the ash_). In the seventeenth century the distinction between acid and alkali was made the basis of a system of chemical medicine. The two principles of acidity and alkalinity were regarded as engaged in an active and never-ending warfare. Every disease was traced to an undue preponderance of one or other of these principles; to keep these unruly principles in quietness became the aim of the physician, and of course it was necessary that the physician should be a chemist, in order that he might know the nature and habits of the principles which gave him so much trouble. Up to this time the term "alkali" had been applied to almost any substance having the properties which I have just enumerated; but this group of substances was divided by Van Helmont and his successors into _fixed alkali_ and _volatile alkali_, and fixed alkali was further subdivided into _mineral alkali_ (what we now call soda) and _vegetable alkali_ (potash). About the same time acids were likewise divided into three groups; _vegetable_, _animal_, and _mineral acids_. To the properties by which alkali was distinguished, viz. cleansing power and action on vegetable colouring matters, Stahl (the founder of the phlogistic theory) added that of combining with acids. When an acid (that is, a sour-tasting substance which dissolves most earthy matters and turns vegetable blues to red) is added to an alkali (that is, a substance which feels soap-like to the touch, which does not dissolve many earthy matters, and which turns many vegetable reds to blue) the properties of both acid and alkali disappear, and a new substance is produced which is not characterized by the properties of either constituent. The new substance, as a rule, is without action on earthy matters or on vegetable colours; it is not sour, nor is it soapy to the touch like alkali; it is _neutral_. It is _a salt_. But, although Stahl stated that an alkali is a substance which combines with an acid, it was not until a century later that these three--alkali, acid, salt--were clearly distinguished. But the knowledge that a certain group of bodies are sour and dissolve minerals, etc., and that a certain other group of bodies are nearly tasteless and do not dissolve minerals, etc., was evidently a knowledge of only the outlying properties of the bodies; it simply enabled a term to be applied to a group of bodies, which term had a definite connotation. _Why_ are acids acid, and _why_ are alkalis alkaline? Acids are acid, said Becher (latter part of seventeenth century), because they all contain the same principle, viz. the primordial acid. This primordial acid is more or less mixed with earthy matter in all actual acids; it is very pure in spirits of salt. Alkalis are alkaline, said Basil Valentine (beginning of the sixteenth century), because they contain a special kind of matter, "the matter of fire." According to other chemists (_e.g._ J. F. Meyer, 1764), acids owe their acidity to the presence of a sharp or biting principle got from fire. Acids, alkalis and salts _all_ contain, according to Stahl (beginning of the eighteenth century), more or less _primordial acid_. The more of this a substance contains, the more acid it is; the less of this it contains, the more alkaline it is. All these attempted explanations recognize that similar properties are to be traced to similarity of composition; but the assertion of the existence of a "primordial acid," or of "the matter of fire," although undoubtedly a step in advance, was not sufficiently definite (unless it was supplemented by a distinct account of the properties of these principles) to be accepted when chemical knowledge became accurate. The same general consideration, founded on a large accumulation of facts, viz. that similarity of properties is due to similarity of composition, guided Lavoisier in his work on acids. He found the "primordial acid" of Stahl, and the "biting principle" of Meyer, in the element oxygen. I have already (p. 91) shortly traced the reasoning whereby Lavoisier arrived at the conclusion that oxygen is _the acid-producer_; here I would insist on the difference between his method and that of Basil Valentine, Stahl and the older chemists. _They_ carried into the domain of natural science conceptions obtained from, and essentially belonging to the domain of metaphysical or extra-physical speculation; _he_ said that oxygen is the acidifier, because all the compounds of this element which he actually examined were possessed of the properties included under the name acid. We know that Lavoisier's conclusion was erroneous, that it was not founded on a sufficiently broad basis of facts. The conception of an acidifying principle, although that principle was identified with a known element, was still tainted with the vices of the alchemical school. We shall see immediately how much harm was done by the assertion of Lavoisier, "All acids contain oxygen." In Chapter II. (pp. 32-37) we traced the progress of knowledge regarding alkalis from the time when the properties of these bodies were said to be due to the existence in them of "matter of fire," to the time when Black had clearly distinguished and defined caustic alkali and carbonated alkali. The truly philosophical character, and at the same time the want of enthusiasm, of Black become apparent if we contrast his work on alkali with that of Lavoisier on acid. Black did not hamper the advance of chemistry by finding a "principle of alkalinity;" but neither did he give a full explanation of the fact that certain bodies are alkaline while others are not. He set himself the problem of accurately determining the differences in composition between burnt (or caustic) and unburnt (or mild) alkali, and he solved the problem most successfully. He showed that the properties of mild alkalis differ from those of caustic alkalis, because the composition of the former differs from that of the latter; and he showed exactly wherein this difference of composition consists, viz. in the possession or non-possession of fixed air. Strange we may say that this discovery did not induce Black to prosecute the study of caustic alkalis: surely he would have anticipated Davy, and have been known as the discoverer of potassium and sodium. In the time of Stahl the name "salt" was applied, as we have learned, to the substance produced by the union of an acid with an alkali; but the same word was used by the alchemists with an altogether different signification. Originally applied to the solid matter obtained by boiling down sea-water, and then extended to include all substances which, like this solid matter, are very easily dissolved by water and can be recovered by boiling down this solution, "salt" was, in the sixteenth and seventeenth centuries, the name given to one of the hypothetical principles or elements. Many kinds of matter were known to be easily dissolved by water; the common possession of these properties was sought to be accounted for by saying that all these substances contained the same principle, namely, _the principle of salt_. I have already tried to indicate the reasoning whereby Boyle did so much to overthrow this conception of salt. He also extended our knowledge of special substances which are now classed as salts. The chemists who came after Boyle gradually reverted to the older meaning of the term "salt," adopting as the characteristics of all substances placed in this class, ready solubility in water, fusibility, or sometimes volatility, and the possession of a taste more or less like that of sea-salt. Substances which resembled salts in general appearance, but were insoluble in water, and very fixed in the fire, were called "earths"; and, as was generally done in those days, the existence of a primordial earth was assumed, more or less of which was supposed to be present in actual earths. This recognition of the possibility of more or less of the primordial earth being present in actually occurring earths, of course necessitated the existence of various kinds of earth. The earths were gradually distinguished from each other; lime was recognized as a substance distinct from baryta, baryta as distinct from alumina, etc. Stahl taught that one essential property of an earth was fusibility by fire, with production of a substance more or less like glass. This property was possessed in a remarkable degree by quartz or silica. Hence silica was regarded as the typical earth, until Berzelius, in 1815, proved it to be an acid. But the earths resembled alkalis, inasmuch as they too combined with, and so neutralized, acids. There is an alkali hidden in every earth, said some chemists. An alkali is an earth refined by the presence of acid and combustible matter, said others. Earths thus came to be included in the term "alkali," when that term was used in its widest acceptation. But a little later it was found that some of the earths were thrown down in the solid form from their solutions in acids by the addition of alkalis; this led to a threefold division, thus-- Earths <----> Alkaline earths <----> Alkalis Insoluble Somewhat soluble Very soluble in in water. in water. water. The distinction at first drawn between "earth" and "alkali" was too absolute; the intermediate group of "alkaline earths" served to bridge over the gap between the extreme groups. "In Nature," says Wordsworth, "everything is distinct, but nothing defined into absolute independent singleness." At this stage of advance, then, an earth is regarded as differing from an alkali in being insoluble, or nearly insoluble in water; in not being soapy to the touch, and not turning vegetable reds to blue: but as resembling an alkali, in that it combines with and neutralizes an acid; and the product of this neutralization, whether accomplished by an alkali or by an earth, is called a salt. To the earth or alkali, as being the foundation on which the salt is built, by the addition of acid, the name of _base_ was given by Rouelle in 1744. But running through every conception which was formed of these substances--acid, alkali, earth, salt--we find a tendency, sometimes forcibly marked, sometimes feebly indicated, but always present, to consider salt as a term of much wider acceptation than any of the others. An acid and an alkali, or an acid and an earth, combine to form a salt; but the salt could not have been thus produced unless the acid, the alkali and the earth had contained in themselves some properties which, when combined, form the properties of the salt. The acid, the alkali, the earth, each is, in a sense, a salt. The perfect salt is produced by the coalescence of the saltness of the acid with the saltness of the alkali. This conception finds full utterance in the names, once in common use, of _sal acidum_ for acid, _sal alkali_ for alkali, and _sal salsum_ or _sal neutrum_ for salt. All are salts; at one extreme comes that salt which is marked by properties called acid properties, at the other extreme comes the salt distinguished by alkaline properties, and between these, and formed by the union of these, comes the middle or neutral salt. It is thus that the nomenclature of chemistry marks the advances made in the science. "What's in a name?" To the historical student of science, almost everything. We shall find how different is the meaning attached in modern chemistry to these terms, _acid salt_, _alkaline salt_, _neutral salt_, from that which our predecessors gave to their _sal acidum_, _sal alkali_, and _sal neutrum_. We must note the appearance of the term _vitriol_, applied to the solid salt-like bodies obtained from acids and characterized by a glassy lustre. By the middle of last century the vitriols were recognized as all derived from, or compounded of, sulphuric acid (oil of vitriol) and metals; this led to a subdivision of the large class of neutral salts into (1) metallic salts produced by the action of sulphuric acid on metals, and (2) neutral salts produced by the action of earths or alkalis on acids generally. To Rouelle, a predecessor of Lavoisier, who died four years before the discovery of oxygen, we owe many accurate and suggestive remarks and experiments bearing on the term "salt." I have already mentioned that it was he who applied the word "base" to the alkali or earth, or it might be metal, from which, by the action of acid, a salt is built up. He also ceased to speak of an acid as _sal acidum_, or of an alkali as _sal alkali_, and applied the term "salt" exclusively to those substances which are produced by the action of acids on bases. When the product of such an action was neutral--that is, had no sour taste, no soapy feeling to the touch, no action on vegetable colours, and no action on acids or bases--he called that product _a neutral salt_; when the product still exhibited some of the properties of acid, _e.g._ sourness of taste, he called it _an acid salt_; and when the product continued to exhibit some of the properties of alkali, _e.g._ turned vegetable reds to blue, he called it _an alkaline salt_. Rouelle also proved experimentally that an acid salt contains more acid--relatively to the same amount of base--than a neutral salt, and that an alkaline salt contains more base--relatively to the same amount of acid--than a neutral salt; and he proved that this excess of acid, or of base, is chemically united to the rest of the salt--is, in other words, an essential part of the salt, from which it cannot be removed without changing the properties of the whole. But we have not as yet got to know why certain qualities connoted by the term "acid" can be affirmed to belong to a group of bodies, why certain other, "alkaline," properties belong to another group, nor why a third group can be distinguished from both of these by the possession of properties which we sum up in the term "earthy." Surely there must be some peculiarity in the composition of these substances, common to all, by virtue of which all are acid. The atom of an acid is surely composed of certain elements which are never found in the atom of an alkali or an earth; or perhaps the difference lies in the number, rather than in the nature of the elements in the acid atoms, or even in the arrangement of the elementary atoms in the compound atom of acid, of alkali, and of earth. I think that our knowledge of salt is now more complete than our knowledge of either acid, alkali, or earth. We know that a salt is formed by the union of an acid and an alkali or earth; if, then, we get to know the composition of acids and bases (_i.e._ alkalis and earths), we shall be well on the way towards knowing the composition of salts. And now we must resume our story where we left it at p. 176. Lavoisier had recognized oxygen as the acidifier; Black had proved that a caustic alkali does not contain carbonic acid. Up to this time metallic calces, and for the most part alkalis and earths also, had been regarded as elementary substances. Lavoisier however proved calces to be compounds of metals and oxygen; but as some of those calces had all the properties which characterized earths, it seemed probable that all earths are metallic oxides, and if all earths, most likely all alkalis also. Many attempts were made to decompose earths and alkalis, and to obtain the metal, the oxide of which the earth or the alkali was supposed to be. One chemist thought he had obtained a metal by heating the earth baryta with charcoal, but from the properties of his metal we know that he had not worked with a pure specimen of baryta, and that his supposed metallic base of baryta was simply a little iron or other metal, previously present in the baryta, or charcoal, or crucible which he employed. But if Lavoisier's view were correct--if all bases contained oxygen--it followed that all salts are oxygen compounds. Acids all contain oxygen, said Lavoisier; this was soon regarded as one of the fundamental facts of chemistry. Earths and alkalis are probably oxides of metals; this before long became an article of faith with all orthodox chemists. Salts are produced by the union of acids and bases, therefore all salts contain oxygen: the conclusion was readily adopted by almost every one. When the controversy between Lavoisier and the phlogistic chemists was at its height, the followers of Stahl had taunted Lavoisier with being unable to explain the production of hydrogen (or phlogiston as they thought) during the solution of metals in acids; but when Lavoisier learned the composition of water, he had an answer sufficient to quell these taunts. The metal, said Lavoisier, decomposes the water which is always present along with the acid, hydrogen is thus evolved, and the metallic calx or oxide so produced dissolves in the acid and forms a salt. If this explanation were correct--and there was an immense mass of evidence in its favour and apparently none against it--then all the salts produced by the action of acids on metals necessarily contained oxygen. The Lavoisierian view of a salt, as a compound of a metallic oxide--or base--with a non-metallic oxide--or acid--seemed the only explanation which could be accepted by any reasonable chemist: in the early years of this century it reigned supreme. But even during the lifetime of its founder this theory was opposed and opposed by the logic of facts. In 1787 Berthollet published an account of experiments on prussic acid,--the existence and preparation (from Prussian blue) of which acid had been demonstrated three or four years before by the Swedish chemist Scheele--which led him to conclude this compound to be a true acid, but free from oxygen. In 1796 the same chemist studied the composition and properties of sulphuretted hydrogen, and pronounced this body to be an acid containing no oxygen. But the experiments and reasoning of Berthollet were hidden by the masses of facts and the cogency of argument of the Lavoisierian chemists. The prevalent views regarding acids and bases were greatly strengthened by the earlier researches of Sir Humphry Davy, in which he employed the voltaic battery as an instrument in chemical investigation. Let us now consider some of the electro-chemical work of this brilliant chemist. In the spring of the year 1800 the electrical battery, which had recently been discovered by Volta, was applied by Nicholson and Carlisle to effect the decomposition of water. The experiments of these naturalists were repeated and confirmed by Davy, then resident at Bristol, who followed up this application of electricity to effect chemical changes by a series of experiments extending from 1800 to 1806, and culminating in the Bakerian Lecture delivered before the Royal Society in the latter year. The history of Davy's life during these years, years rich in results of the utmost importance to chemical science, will be traced in the sequel; meanwhile we are concerned only with the results of his chemical work. The first Bakerian Lecture of Humphry Davy, "On some Chemical Agencies of Electricity," deserves the careful study of all who are interested in the methods of natural science; it is a brilliant example of the disentanglement of a complex natural problem. Volta and others had subjected water to the action of a current of electricity, and had noticed the appearance of acid and alkali at the oppositely electrified metallic surfaces. According to some experimenters, the acid was nitrous, according to others, muriatic acid. One chemist asserted the production of a new and peculiar body which he called _the electric acid_. The alkali was generally said to be ammonia. When Davy passed an electric current through distilled water contained in glass vessels, connected by pieces of moist bladder, cotton fibre, or other vegetable matters, he found that nitric and hydrochloric acids were formed in the water surrounding the positively electrified plate or pole, and soda around the negatively electrified pole, of the battery. When the same piece of cotton fibre was repeatedly used for making connection between the glass vessels, and was washed each time in dilute nitric acid, Davy found that the production of muriatic acid gradually ceased; hence he traced the formation of this acid to the presence of the animal or vegetable substance used in the experiments. Finding that the glass vessels were somewhat corroded, and that the greater the amount of corrosion the greater was the amount of soda making its appearance around the negative pole, he concluded that the soda was probably a product of the decomposition of the glass by the electric current; he therefore modified the experiment. He passed an electric current through distilled water contained in small cups of agate, previously cleaned by boiling in distilled water for several hours, and connected by threads of the mineral asbestos, chosen as being quite free from vegetable matter; alkali and acid were still produced. The experiment was repeated several times with the same apparatus; acid and alkali were still produced, but the alkali decreased each time. The only conclusion to be drawn was that the alkali came from the water employed. Two small cups of gold were now used to contain the water; a very small amount of alkali appeared at the negative pole, and a little nitric acid at the positive pole. The quantity of acid slowly increased as the experiment continued, whereas the quantity of alkali remained the same as after a few minutes' action of the electric current. The production of alkali is probably due, said Davy, to the presence in the water of some substance which is not removed by distillation in a glass retort. By boiling down in a silver dish a quantity of the water he had used, a very small amount of solid matter was obtained, which after being heated was distinctly alkaline. Moreover when a little of this solid matter was added to the water contained in the two golden cups, there was a sudden and marked increase in the amount of alkali formed around the negative pole. Another quantity of the water which he had used was again distilled in a silver retort, and a little of the distillate was subjected to electrolysis as before. No alkali appeared. A little piece of glass was placed in the water; alkali quickly began to form. Davy thus conclusively proved that the alkali produced during the electrolysis (_i.e._ decomposition by the electric current) of water is not derived from the water itself, but from mineral impurities contained in the water, or in the vessel in which the water is placed during the experiment. But the production of nitric acid around the positive pole was yet to be accounted for. Before further experiments could be made it was necessary that Davy should form an hypothesis--that he should mentally connect the appearance of the nitric acid with some other phenomenon sufficient to produce this appearance; he could then devise experiments which would determine whether the connection supposed to exist between the two phenomena really did exist or not. Now, of the constituents of nitric acid--nitrogen, hydrogen and oxygen--all except the first named are present in pure water; nitrogen is present in large quantity in the ordinary atmosphere. It was only necessary to assume that some of the hydrogen and oxygen produced during the electrolysis of water seized on and combined with some of the nitrogen in the air which surrounded that water, and the continual production of nitric acid during the whole process of electrolysis was explained. But how was this assumption to be proved or disproved? Davy adopted a method frequently made use of in scientific investigations:--remove the assumed cause of a phenomenon; if the phenomenon ceases to be produced, the assumed cause is probably the real cause. Davy surrounded the little gold cups containing the water to be electrolysed with a glass jar which he connected with an air-pump; he exhausted most of the air from the jar and then passed the electric current through the water. Very little nitric acid appeared. He now again took out most of the air from the glass jar, admitted some hydrogen to supply its place, and again pumped this out. This process he repeated two or three times and then passed the electric current. _No_ acid appeared in the water. He admitted air into the glass vessel; nitric acid began to be produced. Thus he proved that whenever air was present in contact with the water being electrolysed, nitric acid made its appearance, and when the air was wholly removed the acid ceased to be produced. As he had previously shown that the production of this acid was not to be traced to impurities in the water, to the nature of the vessel used to contain the water, or to the nature of the material of which the poles of the battery were composed, the conclusion was forced upon him that the production of nitric acid in the water, and the presence of ordinary air around the water invariably existed together; that if one of these conditions was present, the other was also present--in other words, that one was the cause of the other. The result of this exhaustive and brilliant piece of work is summed up by Davy in these words: "It seems evident then that water, chemically pure, is decomposed by electricity into gaseous matter alone, into oxygen and hydrogen." From the effects of the electric current on glass, Davy argued that other earthy compounds would probably undergo change under similar conditions. He therefore had little cups of gypsum made, in which he placed pure water, and passed an electric current through the liquid. Lime was formed around the negative, and sulphuric acid around the positive pole. Using similar apparatus, he proved that the electric current decomposes very many minerals into an earthy or alkaline base and an acid. Picturing to himself the little particles of a salt as being split by the electric current each into two smaller particles, one possessed of acid and the other of alkaline properties, Davy thought it might be possible to intercept the progress of these smaller particles, which he saw ever travelling towards the positive and negative poles of the battery. He accordingly connected these small glass vessels by threads of washed asbestos; in one of the outer vessels he placed pure water, in the other an aqueous solution of sulphate of potash, and in the central vessel he placed ammonia. The negative pole of the battery being immersed in the sulphate of potash, and the positive pole in the water, it was necessary for the particles of sulphuric acid--produced by the decomposition of the sulphate of potash--to travel through the ammonia in the central vessel before they could find their way to the positive pole. Now, ammonia and sulphuric acid cannot exist in contact--they instantly combine to form sulphate of ammonia; the sulphuric acid particles ought therefore to be arrested by the ammonia. But the sulphuric acid made its appearance at the positive pole just as if the central vessel had contained water. It seemed that the mutual attraction ordinarily exerted between sulphuric acid and ammonia was overcome by the action of the electric current. Ammonia would generally present an insuperable barrier to the progress of sulphuric acid, but the electrical energy appeared to force the acid particles over this barrier; they passed towards their goal as if nothing stood in their way. Experiments are now multiplied by Davy, and the general conclusion drawn is that "Hydrogen, the alkaline substances, the metals and certain metallic oxides are attracted by negatively electrified metallic surfaces, and repelled by positively electrified metallic surfaces; and contrariwise, that oxygen and acid substances are attracted by positively electrified metallic surfaces, and repelled by negatively electrified metallic surfaces; and these attractive and repulsive forces are sufficiently energetic to destroy or suspend the usual operation of chemical affinity."[10] To account for this apparent suspension of the ordinary chemical laws, Davy supposes that chemical compounds are continually decomposed and re-formed throughout the liquid which is subjected to the electrical action. Thus, in the experiment with water, ammonia and sulphate of potash, he supposes that the sulphuric acid and ammonia do combine in the central vessel to form sulphate of ammonia, but that this compound is again decomposed, by the electrical energy, into sulphuric acid--which passes on towards the positive pole--and ammonia--which remains in the central vessel--ready to combine with more sulphuric acid as that comes travelling onwards from its source in the vessel containing sulphate of potash to its goal in the vessel containing water. The eye of the philosopher had pierced beneath the apparent stability of the chemical systems which he studied. To his vision there appeared in those few drops of water and ammonia and sulphate of potash a never-ceasing conflict of contending forces; there appeared a continual shattering and rebuilding of the particles of which the masses were composed. The whole was at rest, the parts were in motion; the whole was constant in chemical composition, the composition of each particle was changed a thousand times in the minutest portion of every second. To the mind of Davy, the electrolysis of every chemical compound was a new application of the great law established by Newton--"To every action there is an equal and opposite reaction." Each step made in chemical science since Davy's time has but served to emphasize the universality of this principle of action and reaction, a principle which has been too much overlooked in the chemical text-books, but the importance of which recent researches are beginning to impress on the minds of chemists. It is the privilege of the philosophic student of Nature to penetrate the veil with which she conceals her secrets from the vulgar gaze. To him are shown sights which "eye hath not seen," and by him are perceived sounds which "ear hath not heard." Each drop of water is seen by him not only to be built up of myriads of small parts, but each particle is seen to be in motion; many particles are being decomposed into still smaller particles of matter, different in properties from the original particles, but as the original particles are at the same time being reproduced, the continued existence of the drop of water with the properties of water is to him the result of the mutual action and reaction of contending forces. He knows that rest and permanence are gained, not by the cessation of action, but by the continuance of conflict; he knows that in the realm of natural phenomena, stable equilibrium is the resultant of the action of opposite forces, and that complete decomposition occurs only when one force becomes too powerful or another becomes too weak. Pursuing the train of thought initiated by the experiments which I have described, Davy entered upon a series of researches which led him to consider every chemical substance as possessing definite electrical relations towards every other substance. "As chemical attraction between two bodies seems to be destroyed by giving one of them an electrical state different from that which it naturally possessed--that is, by bringing it into a state similar to the other--so it may be increased by exalting its natural energy." Thus zinc, a metal easily oxidized, does not combine with oxygen when negatively electrified, whereas silver, a metal oxidized with difficulty, readily combines with oxygen when positively electrified. Substances in opposite electrical states appear to combine chemically, and the greater the electrical difference the greater the readiness with which chemical combination is effected. Electrical energy and chemical attraction or _affinity_ are evidently closely connected; perhaps, said Davy, they are both results of the same cause. Thus Davy arrived at the conception of a system of bodies as maintained in equilibrium by the mutual actions and reactions of both chemical and electrical forces; by increasing either of these a change is necessarily produced in the other. Under certain electrical conditions the bodies will exert no chemical action on one another, but such action may be started by changing these electrical conditions, or, on the other hand, by changes in the chemical relations of the bodies a change in the electrical relations may be induced. Thus Davy found that if plates of copper and sulphur are heated, the copper exhibits a positive and the sulphur a negative electrical condition; that these electrical states become more marked as temperature rises, until the melting point of sulphur is reached, when the copper and sulphur combine together chemically and produce sulphide of copper. When water is electrolysed, Davy looked on the oppositely electrified metallic plates in the battery as striving to attain a state of equilibrium; the negatively electrified zinc strives to gain positive electricity from the copper, which strives to gain negative electricity from the zinc. The water he regarded as the carrier of these electricities, the one in this direction, the other in that. In thus acting as a carrier, the water is itself chemically decomposed, with production of hydrogen and oxygen; but this chemical rearrangement of some of the substances which composed the original system (of battery and water) involves a fresh disturbance of electrical energy, and so the process proceeds until the whole of the water is decomposed or the whole of the copper or zinc plate is dissolved in the battery. If the water were not chemically decomposed, Davy thought that the zinc and copper in the battery would quickly attain the state of electrical equilibrium towards which they continually strive, and that the current would therefore quickly cease. Davy thought that "however strong the natural electrical energies of the elements of bodies may be, yet there is every probability of a limit to their strength; whereas the powers of our artificial instruments seem capable of indefinite increase." By making use of a very powerful battery, he hoped to be able to decompose substances generally regarded as simple bodies. Taking a wide survey of natural phenomena, he sees these two forces, which we call chemical and electrical, everywhere at work, and by their mutual actions upholding the material universe in equilibrium. In the outbreaks of volcanoes he sees the disturbance of this equilibrium by the undue preponderance of electrical force; and in the formation of complex minerals beneath the surface of the earth, he traces the action of those chemical attractions which are ever ready to bring about the combination of elements, if they are not held in check by the opposing influence of electrical energy. We shall see how the great and philosophical conception of Davy was used by Berzelius, and how, while undoubtedly gaining in precision, it lost much in breadth in being made the basis of a rigid system of chemical classification. Davy's hope that the new instrument of research placed in the hands of chemists by Volta would be used in the decomposition of supposed simple substances was soon to be realized. A year after the lecture "On some Chemical Agencies of Electricity," Davy was again the reader of the Bakerian Lecture; this year (1807) it was entitled, "On some New Phenomena of Chemical Change produced by Electricity, particularly the Decomposition of the Fixed Alkalis; and the Exhibition of the New Substances which constitute their Bases; and on the General Nature of Alkaline Bodies." In his first experiments on the effect of the electrical current on potash and soda, Davy used strong aqueous solutions of these alkalis, with the result that hydrogen and oxygen only were evolved. He then passed the current through melted potash kept liquid during the operation by the use of a spirit-lamp, the flame of which was fed with oxygen. Much light was evolved, and a great flame appeared at the negative pole; on changing the direction of the current, "aeriform globules, which inflamed in the air, rose through the potash." On the 6th of October 1807, a piece of potash was placed on a disc of platinum, which was made the negative pole of a very powerful battery; a platinum wire brought into contact with the upper surface of the potash served as the positive pole. When the current was passed, the potash became hot and soon melted; gas was evolved at the upper surface, and at the lower (negative) side "there was no liberation of elastic fluid, but small globules, having a high metallic lustre, and being precisely similar in visible characters to quicksilver appeared, some of which burst with explosion and bright flame as soon as they were formed, and others remained, and were merely tarnished, and finally covered by a white film which formed on their surfaces." When Davy saw these metallic globules burst through the crust of fusing potash, we are told by one of his biographers, "he could not contain his joy, he actually bounded about the room in ecstatic delight; and some little time was required for him to compose himself sufficiently to continue the experiment." This was the culminating point of the researches in which he had been continuously engaged for about six years. His interest and excitement were intense; the Bakerian Lecture was written "on the spur of the occasion, before the excitement of the mind had subsided," yet, says his biographer--and we may well agree with him--"yet it bears proof only of the maturest judgment; the greater part of it is as remarkable for experimental accuracy as for logical precision." But "to every action there is an equal and opposite reaction:" immediately after the delivery of the lecture, Davy was prostrated by a severe attack of illness, which confined him to bed for nine weeks, and was very nearly proving fatal. That the phenomenon just described was really the decomposition of potash, and the production of the metal of which this substance is an oxygenized compound, was proved by obtaining similar results whether plates of silver, copper, or gold, or vessels of plumbago, or even charcoal, were used to contain the potash, or whether the experiment was conducted in the air, or in a glass vessel from which air had been exhausted, or in glass tubes wherein the potash was confined by mercury. The decomposition of potash was followed within a few days by that of soda, from which substance metallic globules were obtained which took fire when exposed to the air. But the analysis of potash and soda was not sufficient for Davy; he determined to accomplish the synthesis of these substances. For this purpose he collected small quantities of the newly discovered metals, by conducting the electrolysis of potash and soda under experimental conditions such that the metals, as soon as produced, were plunged under the surface of naphtha, a liquid which does not contain oxygen, and which protected them from the action of the surrounding air. A weighed quantity of each metal was then heated in a stream of pure dry oxygen, the products were collected and weighed, and it was found that solutions of these products in water possessed all the properties of aqueous solutions of potash and soda. The new metals were now obtained in larger quantity by Davy, and their properties carefully determined by him; they were named _potassium_ and _sodium_ respectively. They were shown to possess all those properties which were generally accepted as characteristic of metal, except that of being heavy. The new metals were extremely light, lighter than water. For some time it was difficult to convince all chemists that a metal could be a very light substance. We are assured that a friend of Davy, who was shown potassium for the first time, and was asked what kind of substance he supposed it to be, replied, "It is metallic, to be sure;" "and then, balancing it on his finger, he added in a tone of confidence, 'Bless me, how heavy it is!'" Davy argued that since the alkalis, potash and soda, were found to be oxygen compounds of metals, the earths would probably also be found to be metallic oxides. In the year 1808 he succeeded in decomposing the three earths, lime, baryta and strontia, and in obtaining the metals _calcium_, _barium_ and _strontium_, but not in a perfectly pure condition, or in any quantity. He also got evidence of the decomposition of the earths silica, alumina, zirconia and beryllia, by the action of powerful electric currents, but he did not succeed in obtaining the supposed metallic bases of these substances. So far Davy's discoveries had all tended to confirm the generally accepted view which regarded alkalis and earths as metallic oxides. But we found that the outcome of these views was to regard all salts--and among these, of course, common salt--as oxygen compounds.[11] Acids were oxygen compounds, bases were oxygen compounds, and as salts were produced by the union of acids with bases, they, too, must necessarily be oxygen compounds. Berthollet had thrown doubt on the universality of Lavoisier's name "oxygen," _the_ acidifier, but he had not conclusively proved the existence of any acid which did not contain oxygen. The researches of Davy naturally led him to consider the prevalent views regarding acids, bases and salts. Muriatic (or as we now call it hydrochloric) acid had long been a stumbling-block to the thorough-going Lavoisierian chemists. Oxygen could not be detected in it, yet it ought to contain oxygen, because oxygen is the acidifier. Of course, if muriatic acid contains oxygen, the salts--muriates--produced by the action of this acid on alkalis and earths must also contain oxygen. Many years before this time the action of muriatic acid on manganese ore had been studied by the Swedish chemist Scheele, who had thus obtained a yellow-coloured gas with a very strong smell. Berthollet had shown that when a solution of this gas in water is exposed to sunlight, oxygen is evolved and muriatic acid is produced. The yellow gas was therefore supposed to be, and was called, "oxidized muriatic acid," and muriatic acid was itself regarded as composed of oxygen and an unknown substance or _radicle_. In 1809 Gay-Lussac and Thenard found that one volume of hydrogen united with one volume of the so-called oxidized muriatic acid to form muriatic acid; the presence of hydrogen in this acid was therefore proved. When Davy began (1810-11) to turn his attention specially to the study of salts, he adopted the generally accepted view that muriatic acid is a compound of oxygen and an unknown radicle, and that by the addition of oxygen to this compound oxidized muriatic acid is produced. But unless Davy could prove the presence of oxygen in muriatic acid he could not long hold the opinion that oxygen was really a constituent of this substance. He tried to obtain direct evidence of the presence of oxygen, but failed. He then set about comparing the action of muriatic acid on metals and metallic oxides with the action of the so-called oxidized muriatic acid on the same substances. He showed that salt-like compounds were produced by the action of oxidized muriatic acid either on metals or on the oxides of these metals, oxygen being evolved in the latter cases; and that the same compounds and water were produced by the action of muriatic acid on the same metallic oxides. These results were most easily and readily explained by assuming the so-called oxidized muriatic acid to be an elementary substance, and muriatic acid to be a compound of this element with hydrogen. To the new element thus discovered--for he who establishes the elementary nature of a substance may almost be regarded as its discoverer--Davy gave the name of _chlorine_, suggested by the yellow colour of the gas (from Greek, = _yellow_). He at once began to study the analogies of chlorine, to find by experiment which elements it resembled, and so to classify it. Many metals, he found, combined readily with chlorine, with evolution of heat and light. It acted, like oxygen, as a supporter of combustion; it was, like oxygen, attracted towards the negative pole of the voltaic battery; its compound with hydrogen was an acid; hence said Davy chlorine, like oxygen, is a supporter of combustion and also an acidifier. But it was very hard to get chemists to adopt these views. As Bacon says, "If false facts in Nature be once on foot, what through neglect of examination, the countenance of antiquity, and the use made of them in discourse, they are scarce ever retracted." Chemists had long been accustomed to systems which pretended to explain all chemical facts. The phlogistic theory, which had tyrannized over chemistry, had been succeeded by the Lavoisierian chemistry, which recognized one acidifier, and this also the one supporter of combustion. To ascribe these properties to any element other than oxygen appeared almost profane. But when Davy spoke of chlorine as an acidifier, he did not use this word in the same sense as that in which it was employed by the upholders of the oxygen theory of acids; he simply meant to express the fact that a compound containing chlorine as one of its constituents, but not containing oxygen, was a true acid. When Gay-Lussac attempted to prove that hydrogen is an _alkalizing principle_, Davy said, "This is an attempt to introduce into chemistry a doctrine of occult qualities, and to refer to some mysterious and inexplicable energy what must depend upon a peculiar corpuscular arrangement." And with regard to Gay-Lussac's strained use of analogies between hydrogen compounds and alkalis, he says, "The substitution of analogy for fact is the bane of chemical philosophy; the legitimate use of analogy is to connect facts together, and to guide to new experiments." But Davy's facts were so well established, and his experiments so convincing, that before two or three years had passed, most chemists were persuaded that chlorine was an element--_i.e._ a substance which had never been decomposed--and that muriatic acid was a compound of this element with hydrogen. Berzelius was among the last to adopt the new view. Wöhler tells us that in the winter of 1823, when he was working in the laboratory of Berzelius, Anna, while washing some basins, remarked that they smelt strongly of oxidized muriatic acid: "Now," said Berzelius, "listen to me, Anna. Thou must no longer say 'oxidized muriatic acid,' but 'chlorine;' that is better." This work on chlorine was followed up, in 1813, by the proof that the class of acidifiers and supporters of combustion contains a third elementary substance, viz. iodine. As Davy's views regarding acids and salts became developed, he seems to have more and more opposed the assumption that any one element is especially to be regarded as the acidifying element; but at the same time he seems to admit that most, if not all, acids contain hydrogen. Such oxides as sulphur trioxide, nitrogen pentoxide, etc., do not possess acid properties except in combination with water. But he of course did not say that all hydrogen compounds are acids; he rather regarded the possession by a substance of acid properties as dependent, to a great extent, on the nature of the elements other than hydrogen which it contained, or perhaps on the arrangement of all the elements in the particles of the acid. He regarded the hydrogen in an acid as capable of replacement by a metal, and to the metallic derivative--as it might be called--of the acid, thus produced, he gave the name of "salt." An acid might therefore be a compound of hydrogen with one other element--such were hydrochloric, hydriodic, hydrofluoric acids--or it might be a compound of hydrogen with two or more elements, of which one might or might not be oxygen--such were hydrocyanic acid and chloric or nitric acid. If the hydrogen in any of these acids were replaced by a metal a salt would be produced. A salt might therefore contain no oxygen, _e.g._ chloride or iodide of potassium; but in most cases salts did contain oxygen, _e.g._ chlorate or nitrate of potassium. Acids were thus divided into oxyacids (or acids which contain oxygen) and acids containing no oxygen; the former class including most of the known acids. The old view of salts as being compounds of acids (_i.e._ oxides of the non-metallic elements) and bases (_i.e._ oxides of metals) was overthrown, and salts came to be regarded as metallic derivatives of acids. From this time, these terms--acids, salts, bases--become of less importance than they formerly were in the history of chemical advance. In trying to explain Davy's electro-chemical theory I have applied the word _affinity_ to the mutual action and reaction between two substances which combine together to form a chemical compound. It is now necessary that we should look a little more closely into the history of this word _affinity_. Oil and water do not mix together, but oil and potash solution do; the former may be said not to have, and the latter to have, an affinity one for the other. When sulphur is heated, the yellow odourless solid, seizing upon oxygen in the air, combines with it to produce a colourless strongly smelling gas. Sulphur and oxygen are said to have strong affinity for each other. If equal weights of lime and magnesia be thrown into diluted nitric acid, after a time it is found that some of the lime, but very little of the magnesia, is dissolved. If an aqueous solution of lime be added to a solution of magnesia in nitric acid, the magnesia is precipitated in the form of an insoluble powder, while the lime remains dissolved in the acid. It is said that lime has a stronger affinity for nitric acid than magnesia has. Such reactions as these used to be cited as examples of _single elective affinity_--single, because one substance combined with one other, and elective, because a substance seemed to choose between two others presented to it, and to combine with one to the exclusion of the other. But if a neutral solution of magnesia in sulphuric acid is added to a neutral solution of lime in nitric acid, sulphate of lime and nitrate of magnesia are produced. The lime, it was said, leaves the nitric and goes to the sulphuric acid, which, having been deserted by the magnesia, is ready to receive it; at the same time the nitric acid from which the lime has departed combines with the magnesia formerly held by the sulphuric acid. Such a reaction was said to be an instance of _double affinities_. The chemical changes were caused, it was said, by the simultaneous affinity of lime for sulphuric acid, which was greater than its affinity for nitric acid, and the affinity of magnesia for nitric acid, which was greater than its affinity for sulphuric acid. If a number of salts were mixed, each base--supposing the foregoing statements to be correct--would form a compound with that acid for which it had the greatest affinity. It should then be possible to draw up tables of affinity. Such tables were indeed prepared. Here is an example:-- _Sulphuric Acid._ Baryta. Lime. Strontia. Ammonia. Potash. Magnesia. Soda. This table tells us that the affinity of baryta for sulphuric acid is greater than that of strontia for the same acid, that of strontia greater than that of potash, and so on. It also tells that potash will decompose a compound of sulphuric acid and soda, just as soda will decompose a compound of the same acid with lime, or strontia will decompose a compound with potash, etc. But Berthollet showed in the early years of this century that a large quantity of a body having a weak affinity for another will suffice to decompose a small quantity of a compound of this other with a third body for which it has a strong affinity. He showed, that is, that the formation or non-formation of a compound is dependent not only on the so-called affinities between the constituents, but also on the relative quantities of these constituents. Berthollet and other chemists also showed that affinity is much conditioned by temperature; that is, that two substances which show no tendency towards chemical union at a low temperature may combine when the temperature is raised. He, and they, also proved that the formation or non-formation of a compound is much influenced by its physical properties. Thus, if two substances are mixed in solution, and if by their mutual action a substance can be produced which is insoluble in the liquids present, that substance is generally produced whether the affinity between the original pair of substances be strong or weak. The outcome of Berthollet's work was that tables of affinity became almost valueless. To say that the affinity of this body for that was greater than its affinity for a third body was going beyond the facts, because the formation of this or that compound depended on many conditions much more complex than those connoted by the term "affinity." Yet the conception of affinity remained, although it could not be applied in so rigorous a way as had been done by the earlier chemists. If an element, A, readily combines with another element, B, under certain physical conditions, but does not, under the same conditions, combine with a third element, C, it may still be said that A and B have, and A and C have not, an affinity for each other. This general conception of affinity was applied by Berzelius to the atoms of elements. Affinity, said Berzelius, acts between unlike atoms, and causes them to unite to form a compound atom, unlike either of the original atoms; cohesion, on the other hand, acts between like atoms, causing them to hold together without producing any change in their properties. Affinity varies in different elements. Thus the affinity of gold for oxygen is very small; hence it is that gold is found in the earth in the metallic state, while iron, having a great affinity for oxygen, soon rusts when exposed to air, or when buried in the earth. Potassium and sodium have great affinities for oxygen, chlorine, etc.; yet the atoms of potassium and sodium do not themselves combine. The more any elements are alike chemically the smaller is their affinity for each other; the more any elements are chemically unlike the greater is their mutual affinity; but this affinity is modified by circumstances. Thus, said Berzelius, if equal numbers of atoms of A and B, having equal or nearly equal affinity for C, mutually react, compound atoms, AC and BC, will be produced, but atoms of A and B will remain. The amounts of AC and BC produced will be influenced by the greater or less affinity of A and B for C; but if there be a greater number of A than of B atoms, a greater amount of AC than of BC will be produced. In these cases all the reacting substances and the products of the actions are supposed to be liquids; but BC, if a solid substance, will be produced even if the affinity of A for C is greater than that of B for C. In some elements, Berzelius taught, affinity slumbers, and can be awakened only by raising the temperature. Thus carbon in the form of coal has no affinity for oxygen at ordinary temperatures; it has remained for ages in the earth without undergoing oxidation; but when coal is heated the affinities of carbon are awakened, combination with oxygen occurs, and heat is produced. But why is it that certain elementary atoms exhibit affinity for certain others? It depends, said Berzelius, on the electrical states of these atoms. According to the Berzelian theory, every elementary atom has attached to it a certain quantity of electricity, part of which is positive and part negative. This electricity is accumulated at two points on each atom, called respectively the positive pole and the negative pole; but in each atom one of these electricities so much preponderates over the other as to give the whole atom the character of either a positively or a negatively electrified body. When two atoms combine chemically the positive electricity in one neutralizes the negative electricity in the other. As we know that similar electricities repel, and opposite electricities attract each other, it follows that a markedly positive atom will exhibit strong affinity for a markedly negative atom, less strong affinity for a feebly negative, and little or no affinity for a positively electrified atom; but two similarly electrified atoms may exhibit affinity, because in every positive atom there is some negative electricity, as in every negative atom there is some positive electricity. Thus, in the atoms of copper and zinc positive electricity predominates, said Berzelius, but the zinc atoms are more positive than those of copper; hence, when the metals are brought into contact the negative electricity of the copper atoms is attracted and neutralized by the positive electricity of the zinc atoms, combination takes place, and the compound atom is still characterized by a predominance of positive electricity. Hence Berzelius identified "electrical polarity" with chemical affinity. Every atom was regarded by him as _both_ positively _and_ negatively electrified; but as one of these electricities was always much stronger than the other, every atom regarded as a whole appeared to be _either_ positively _or_ negatively electrified. Positive atoms showed affinity for negative atoms, and _vice versâ_. As a positive atom might become more positive by increasing the temperature of the atom, so might the affinity of this atom for that be more marked at high than at low temperatures. Now, if two elementary atoms unite, the compound atom must--according to the Berzelian views--be characterized either by positive or negative electricity. This compound atom, if positive, will exhibit affinity for other compound atoms in which negative electricity predominates; if negative, it will exhibit affinity for other positively electrified compound atoms. If two compound atoms unite chemically, the complex atom so produced will, again, be characterized by one or other of the two electricities, and as it is positive or negative, so will it exhibit affinity for positively or negatively electrified complex atoms. Thus Berzelius and his followers regarded every compound atom, however complex, as essentially built up of two parts, one of which was positively and the other negatively electrified, and which were held together chemically by virtue of the mutual attractions of these electricities; they regarded every compound atom as a _dual_ structure. The classification adopted by Berzelius was essentially a dualistic classification. His system has always been known in chemistry as _dualism_. Berzelius divided compound atoms (we should now say molecules) into three groups or orders-- _Compound atoms of the first order_, formed by the immediate combination of atoms of two, or in organic compounds of three, elementary substances. _Compound atoms of the second order_, formed by the combination of atoms of an element with atoms of the first order, or by the combination of two or more atoms of the first order. _Compound atoms of the third order_, formed by combination of two or more atoms of the second order. When an atom of the third order was decomposed by an electric current, it split up, according to the Berzelian teaching, into atoms of the second order--some positively, others negatively electrified. When an atom of the second order was submitted to electrolysis, it decomposed into atoms of the first order--some positively, others negatively electrified. Berzelius said that a base is an electro-positive oxide, and an acid is an electro-negative oxide. The more markedly positive an oxide is, the more basic it is; the more negative it is, the more is it characterized by acid properties. One outcome of this teaching regarding acids and bases was to overthrow the Lavoisierian conception of oxygen as the acidifying element. Some oxides are positive, others negative, said Berzelius; but acids are characterized by negative electricity, therefore the presence of oxygen in a compound does not always confer on that compound acid properties. We have already seen that silica was regarded by most chemists as a typical earth; but Berzelius found that in the electrolysis of compounds of silica, this substance appeared at the positive pole of the battery--that is, the atom of silica belonged to the negatively electrified order of atoms. Silica was almost certainly an oxide; but electro-negative oxides are, as a class, acids; therefore silica was probably an acid. The supposition of the acid character of silica was amply confirmed by the mineralogical analyses and experiments of Berzelius. He showed that most of the earthy minerals are compounds of silica with electro-positive metallic oxides, and that silica plays the part of an acid in these minerals; and in 1823 he obtained the element silicon, the oxide of which is silica. On this basis Berzelius reared a system of classification in mineralogy which much aided the advance of that branch of natural science. By the work of Berzelius and Davy the Lavoisierian conception of acid has now been much modified and extended; it has been rendered less rigid, and is therefore more likely than before to be a guide to fresh discoveries. The older view of acid and alkali was based, for the most part, on a qualitative study of the reactions of chemical substances: bodies were placed in the same class because they were all sour, or all turned vegetable blues to red, etc. This was followed by a closer study of the composition of substances, and by attempts to connect the properties of these substances with their composition; but when this attempt resulted in the promulgation of the dictum that "oxygen is the acidifying principle," it began to be perceived that a larger basis of fact must be laid before just conclusions could be drawn as to the connections between properties and composition of substances. This larger basis was laid by the two chemists whose work we have now reviewed. Of the life of one of these men I have already given such a sketch as I can from the materials available to me; of the life of the other we happily possess ample knowledge. Let us now consider the main features of this life. * * * * * HUMPHRY DAVY, the eldest son of Robert and Grace Davy, was born at Penzance, in Cornwall, on December 17, 1778, eight months that is before the birth of Berzelius. His parents resided on a small property which had belonged to their ancestors for several generations. Surrounded by many kind friends by whom he was much thought of, the boy appears to have passed a very happy childhood. Even at the age of five his quickness and penetration were marked by those around him, and at school these continued to be his predominant characteristics. Nurtured from his infancy in the midst of beautiful and romantic scenery, and endowed with great observing power and a lively imagination, young Davy seemed destined to be one of those from whose lips is "poured the deathless singing;" all through life he was characterized by a strongly marked poetic temperament. Humphry Davy was held in much esteem by his school friends as a composer of valentines and love letters, as a daring and entertaining teller of stories, and as a successful fireworks manufacturer. Such a combination of qualities would much endear him to his boy-companions. We are told that at the age of eight he used to mount on an empty cart, around which a circle of boys would collect to be entertained by the wonderful tales of the youthful narrator. Finishing his school education at the age of fifteen, he now began his own education of himself. In 1795 he was apprenticed to a surgeon and apothecary (afterwards a physician), in Penzance, with whom he learned the elements of medical science; but his time during the years which he spent under Mr. Borlase was much occupied in shooting, fishing, searching for minerals and geological specimens, composing poetry, and pursuing metaphysical speculations. He was now, as through life, an enthusiastic lover of Nature; his mind was extremely active, ranging over the most diverse subjects; he was full of imagination, and seemed certain to distinguish himself in any pursuit to which he should turn his attention. During the next three or four years Davy indulged freely in speculations in all manner of subjects; he started, as people generally do when young, from general principles and followed these out to many conclusions. Even in his study of physiology and other branches of science, he appears at this time to have adopted the speculative rather than the experimental method; but unlike most youthful metaphysicians he was ready to give up an opinion whenever it appeared to him incorrect. By the time he reached the age of twenty he had discarded this method of seeking for truth, and was ever afterwards distinguished by his careful working out of facts as the foundation for all his brilliant theories. Davy appears to have begun the study of chemistry about 1798 by reading Lavoisier's "Elements of Chemistry," the teachings of which he freely criticized. About this time Mr. Gregory Watt came to live at Penzance as a lodger with Davy's mother, and with him the young philosopher had much talk on chemical and other scientific subjects. He also became acquainted with Mr. Davies Gilbert--who was destined to succeed Davy as President of the Royal Society--and from him he borrowed books and received assistance of various kinds in his studies. It was during these years that Davy made experiments on heat, which were published some years later, and which are now regarded as laying the foundations of the modern theory according to which heat is due to the motions of the small parts of bodies. He arranged two brass plates so that one should carry a block of ice which might be caused to revolve in contact with the other plate; the plates were covered by a glass jar, from which he exhausted the air by means of a simple syringe of his own contrivance; the machine being placed on blocks of ice the plates were caused to revolve. The ice inside the jar soon melted; Davy concluded that the heat required to melt this ice could only be produced by the friction of the ice and brass, and that therefore heat could not be any form of ponderable matter. In the year 1798 Davy was asked to go to Bristol as superintendent of the laboratory of a new Pneumatic Institution started by Dr. Beddoes for the application of gases to the treatment of diseases. Davy had corresponded with Beddoes before this time regarding his experiments on heat, and the latter seems to have been struck with his great abilities and to have been anxious to secure him as experimenter for his institution. Davy was released from his engagements with Mr. Borlase, and, now about twenty years of age, set out for his new home, having made as he says all the experiments he could at Penzance, and eagerly looking forward to the better appliances and incitements to research which he hoped to find at Bristol. The Pneumatic Institution was supported by subscriptions, for the most part from scientific men. It was started on a scientific basis. Researches were to be made on gases of various kinds with the view of applying these as remedies in the alleviation of disease. An hospital for patients, a laboratory for experimental research, and a lecture theatre were provided. At this time many men of literary and intellectual eminence resided in Bristol; among these were Coleridge and Southey. Most of these men were visitors at the house of Dr. Beddoes, and many distinguished men came from various parts of the county to visit the institution. Davy thus entered on a sphere of labour eminently suited for the development of his genius. With ample mechanical appliances for research, with plenty of time at his disposal, surrounded by an atmosphere of inquiry and by men who would welcome any additions he could make to the knowledge of Nature, and being at the same time not without poetic and imaginative surroundings, by which he was ever spurred onwards in the pursuit of truth--placed in these circumstances, such an enthusiastic and diligent student of science as Davy could not but obtain results of value to his fellows. The state of chemical science at this time was evidently such as to incite the youthful worker. The chains with which Stahl and his successors had so long bound the limbs of the young science had been broken by Lavoisier; and although the French school of chemistry was at this time dominant, and not disinclined to treat as ignorant any persons who might differ from its teaching, yet there was plenty of life in the cultivators of chemistry. The controversy between Berthollet and Proust was about to begin; the Lavoisierian views regarding acids and salts were not altogether accepted by Gay-Lussac, Thenard and others; and from the laboratory of Berzelius there was soon to issue the first of those numerous researches which drew the attention of every chemist to the capital of Sweden. The voltaic battery had been discovered, and had opened up a region of possibilities in chemistry. Davy began his researches at the institution by experiments with nitrous oxide, a gas supposed by some people at that time to be capable of producing most harmful effects on the animal system. He had to make many experiments before he found a method for preparing the pure gas, and in the course of these experiments he added much to the stock of chemical knowledge regarding the compounds of nitrogen and oxygen. Having obtained fairly pure nitrous oxide, he breathed it from a silk bag; he experienced a "sensation analogous to gentle pressure on all the muscles;... the objects around me became dazzling and my hearing more acute;... at last an irresistible propensity to action was indulged in.... I recollect but indistinctly what followed; I know that my motions were various and violent." Southey and Coleridge breathed the gas; the poets only laughed a little. Encouraged by the results of these experiments, Davy proceeded to prepare and breathe nitric oxide--whereby he was rendered very ill--and then carburetted hydrogen--which nearly killed him. In his chemical note-book about this time, Davy says, "The perfection of chemical philosophy, or the laws of corpuscular motion, must depend on the knowledge of all the simple substances, their mutual attractions, and the ratio in which the attractions increase or diminish with increase or diminution of temperature.... The first step towards these laws will be the decomposition of those bodies which are at present undecompounded." And in the same note-book he suggests methods which he thinks might effect the decomposition of muriatic and boric acids, the alkalis and earths. Here are the germs of his future work. After about eight months' work at Bristol he published a volume of "Researches," which contained a great many new facts, and was characterized by vigour and novelty of conception. These researches had been carried out with intense application; each was struck off at a red heat. His mind during this time was filled with vast scientific conceptions, and he began also to think of fame. "An active mind, a deep ideal feeling of good, and a look towards future greatness," he tells us, sustained him. Count Rumford, the founder of the Royal Institution in London, was anxious to obtain a lecturer on chemistry for the Institution. Davy was strongly recommended, and after a little arrangement--concerning which Davy says in a letter, "I will accept of no appointment except on the sacred terms of independence"--he was appointed Assistant Lecturer on Chemistry and Director of the Laboratory. About a year later his official designation was changed to Professor of Chemistry. This appointment opened up a great sphere of research; "the sole and uncontrolled use of the apparatus of the institution for private experiments" was to be granted him, and he was promised "any apparatus he might need for new experiments." He had now the command of a good laboratory; he had not to undergo the drudgery of systematic teaching, but was only required to give lectures to a general audience. Before leaving Bristol he had commenced experiments on the chemical applications of the voltaic battery; these he at once followed up with the better apparatus now at his command. The results of this research, and his subsequent work on the alkalis and on muriatic acid and chlorine, have been already described. The circumstances of Davy's life had hitherto been most favourable; how nobly he had availed himself of these circumstances was testified by the work done by him. His first lecture was delivered in the spring of 1801, and at once he became famous. A friend of Davy says, "The sensation created by his first course of lectures at the Institution, and the enthusiastic admiration which they obtained, is scarcely to be imagined. Men of the first rank and talent, the literary and the scientific, the practical and the theoretical, blue-stockings and women of fashion, the old and the young--all crowded, eagerly crowded the lecture-room. His youth, his simplicity, his natural eloquence, his chemical knowledge, his happy illustrations and well-conducted experiments, excited universal attention and unbounded applause. Compliments, invitations and presents were showered upon him in abundance from all quarters; his society was courted by all, and all appeared proud of his acquaintance." One of his biographers says of these lectures, "He was always in earnest, and when he amused most, amusement appeared most foreign to his object. His great and first object was to instruct, and in conjunction with this, maintain the importance and dignity of science; indeed, the latter, and the kindling a taste for scientific pursuits, might rather be considered his main object, and the conveying instruction a secondary one." The greatest pains were taken by Davy in the composition and rehearsal of his lectures, and in the arrangement of experiments, that everything should tend towards the enlightenment of his audience. Surrounded by a brilliant society, invited to every fashionable entertainment, flattered by admirers, tempted by hopes of making money, Davy remained a faithful and enthusiastic student of Nature. "I am a lover of Nature," he writes at this time to a friend, "with an ungratified imagination. I shall continue to search for untasted charms, for hidden beauties. My _real_, my _waking_ existence, is amongst the objects of scientific research. Common amusements and enjoyments are necessary to me only as dreams to interrupt the flow of thoughts too nearly analogous to enlighten and vivify." During these years (_i.e._ from 1802 to 1812) he worked for the greater part of each day in the laboratory. Every week, almost every day, saw some fresh discovery of importance. He advanced from discovery to discovery. His work was characterized by that vast industry and extreme rapidity which belong only to the efforts of genius. Never, before or since, has chemical science made such strides in this country. In 1803 Davy was elected a Fellow, and in 1807 one of the secretaries of the Royal Society. In 1812 he retired from the professorship of chemistry at the Royal Institution; in the same year he was made a knight. The next two or three years were mostly spent in travelling abroad with his wife--he had married a widow lady, Mrs. Apreece, in 1812. During his visit to Paris he made several experiments on the then recently discovered iodine, and proved this substance to be an element. The work which Davy had accomplished in the seventeen years that had now elapsed since he began the study of chemistry, whether we consider it simply as a contribution to chemical science, or in the light of the influence it exerted on the researches of others, was of first-rate importance; but a fresh field now began to open before him, from which he was destined to reap the richest fruits. In the autumn of 1815 his attention was drawn to the subject of fire-damp in coal-mines. As he passed through Newcastle, on his return from a holiday spent in the Scottish Highlands, he examined various coal-mines and collected samples of fire-damp; in December of the same year his _safety-lamp_ was perfected, and soon after this it was in the hands of the miner. The steps in the discovery of this valuable instrument were briefly these. Davy established the fact that fire-damp is a compound of carbon and hydrogen; he found that this gas must be mixed with a large quantity of ordinary air before the mixture becomes explosive, that the temperature at which this explosion occurs is a high one, and that but little heat is produced during the explosion; he found that the explosive mixture could not be fired in narrow metallic tubes, and also that it was rendered non-explosive by addition of carbonic acid or nitrogen. He reasoned on these facts thus: "It occurred to me, as a _considerable_ heat was required for the inflammation of the fire-damp, and as it produced in burning a comparatively _small degree_ of heat, that the effect of carbonic acid and azote, and of the surfaces of small tubes, in preventing its explosion, depended on their cooling powers--upon their lowering the temperature of the exploding mixture so much that it was no longer sufficient for its continuous inflammation." He at once set about constructing a lamp in which it should be impossible for the temperature of ignition of a mixture of fire-damp and air to be attained, and which therefore, while burning, might be filled with this mixture without any danger of an explosion. He surrounded the flame of an oil-lamp with a cylinder of fine wire-gauze; this lamp when brought into an atmosphere containing fire-damp and air could not cause an explosion, because although small explosions might occur in the interior of the wire cylinder, so much heat was conducted away by the large metallic surface that the temperature of the explosive atmosphere outside the lamp could not attain that point at which explosion would occur. In 1818 Sir Humphry Davy was made a baronet, in recognition of his great services as the inventor of the safety-lamp; and in 1820 he was elected to the most honourable position which can be held by a man of science in this country, he became the President of the Royal Society. For seven years he was annually re-elected president, and during that time he was the central figure in the scientific society of England. During these years he continued his investigations chiefly on electro-chemical subjects and on various branches of applied science. In 1826 his health began to fail. An attack of paralysis in that year obliged him to relinquish most of his work. He went abroad and travelled in Italy and the Tyrol, sometimes strong enough to shoot or fish a little, or even to carry on electrical experiments; sometimes confined to his room, or to gentle exercise only. He resigned the presidentship of the Royal Society in 1827. In 1828 he visited Rome, where he was again attacked by paralysis, and thought himself dying, but he recovered sufficiently to attempt the journey homeward. At Geneva he became very ill, and expired in that city on the 29th of May 1829. During these later years of illness and suffering, his intense love of and delight in Nature were very apparent; he returned again to the simple tastes and pleasures of his early days. His intimate knowledge of natural appearances and of the sights and sounds of country life is conspicuous in the "Salmonia, or Days of Fly-fishing," written during his later years. Sir Humphry Davy was emphatically a genius. He was full of eager desire to know the secrets of the world in which he lived; he looked around him with wonder and delight, ever conscious of the vastness of the appearances which met his gaze; an exuberance of life and energy marked his actions; difficulties were encountered by him only to be overcome; he was depressed by no misfortunes, deterred by no obstacles, led aside from his object by no temptations, and held in bondage by no false analogies. His work must ever remain as a model to the student of science. A thorough and careful foundation of fact is laid; on this, hypotheses are raised, to be tested first by reasoning and argument, then by the tests of the laboratory, which alone are final. Analogies are seized; hints are eagerly taken up, examined, and acted on or dismissed. As he works in the laboratory, we see his mind ranging over the whole field of chemical knowledge, finding a solution of a difficulty here, or guessing at a solution there; combining apparently most diverse facts; examining phenomena which appear to have no connection; never dwelling too long on an hypothesis which cannot yield some clue to the object of research, but quickly discovering the road which will lead to the wished-for solution. Like so many great experimenters Davy accomplished wonders with little apparatus. When he went abroad for the first time he took with him two small boxes, one twenty, and the other twelve inches long, by about seven inches wide and four deep. With the apparatus contained in these boxes he established the elementary nature of iodine, and made a rough estimation of its atomic weight; he determined many of its analogies with chlorine, proving that, like chlorine, it is markedly electro-negative, and that its compounds are decomposed by chlorine; he accomplished the synthesis of hydriodic acid, and approximately determined the composition of iodide of nitrogen. But when it was necessary to employ delicate or powerful apparatus, he was able by the use of that also to obtain results of primary importance. The decomposition of potash, soda, baryta, lime and strontia could not have been effected had he not had at his command the resources of a well-furnished laboratory. Davy has had no successor in England. Much useful and some brilliant work has been done by English chemists since his day, but we still look back to the first quarter of the century as the golden age of chemistry in this country. On the roll wherein are written the names of England's greatest sons, there is inscribed but a single chemist--Humphry Davy. * * * * * I carried on the account of the work of Davy's great contemporary, Berzelius, to the time when he had fairly established dualistic views of the structure of chemical compounds, and when, by the application of a few simple rules regarding the combinations of elementary atoms, he had largely extended the bounds of the atomic theory of Dalton. Berzelius also did important work in the domain of organic chemistry. By numerous analyses of compounds of animal and vegetable origin, he clearly established the fact that the same laws of combination, the same fixity of composition, and the same general features of atomic structure prevail among the so-called organic as among the inorganic compounds. In doing this he broke down the artificial barrier which had been raised between the two branches of the science, and so prepared the way for modern chemistry, which has won its chief triumphs in the examination of organic compounds. By the many and great improvements which he introduced into analytical chemistry, and by the publication of his "Textbook of Chemistry," which went through several editions in French and German, and also of his yearly report on the advance of chemistry, Berzelius exerted a great influence on the progress of his favourite science. Wöhler tells us that when the spring of the year came, at which time his annual report had to be prepared, Berzelius shut himself up in his study, surrounded himself with books, and did not stir from the writing-table until the work was done. In his later days Berzelius was much engaged in controversy with the leaders of the new school, the rise and progress of which will be traced in the next chapter, but throughout this controversy he found time to add many fresh facts to those already known. He continued his researches until his death in 1848. The work of the great Swedish chemist is characterized by thoroughness in all its parts: to him every fact appeared to be of importance; although now perhaps only an isolated fact, he saw that some day it would find a place in a general scheme of classification. He worked in great measure on the lines laid down by Dalton and Davy; the enormous number and accuracy of his analyses established the law of multiple proportions on a sure basis, and his attempts to determine the constitution of compound atoms, while advancing the atomic theory of Dalton, drew attention to the all-important distinction between atom and molecule, and so prepared chemists for the acceptance of the generalization of Avogadro. The electro-chemical conceptions of Davy were modified by Berzelius; they were shorn of something of their elasticity, but were rendered more suited to be the basis of a rigid theory. * * * * * At the close of this transition period from the Lavoisierian to the modern chemistry, we find analytical chemistry established as an art; we find the atomic theory generally accepted, but we notice the existence of much confusion which has arisen from the non-acceptance of the distinction made by Avogadro between atom and molecule; we find the analogies between chemical affinity and electrical energy made the basis of a system of classification which regards every compound atom (or molecule) as built up of two parts, in one of which positive, and in the other negative electricity predominates; and accompanying this system of classification we find that an acid is no longer regarded as necessarily an oxygen compound, but rather as a compound possessed of certain properties which are probably due to the arrangement of the elementary atoms, among which hydrogen appears generally to find a place; we find that salts are for the most part regarded as metallic derivatives of acids; and we find that by the decomposition of the supposed elementary substances, potash, soda, lime, etc., the number of the elements has been extended, the application of a new instrument of research has been brilliantly rewarded, and the Lavoisierian description of "element" as the "attained, not the attainable, limit of research" has been emphasized. FOOTNOTES: [9] The history and meaning of these terms is considered on p. 171, _et seq._ [10] For an explanation of this expression, "chemical affinity," see p. 206, _et seq._ [11] These views have been already explained on pp. 182, 183. CHAPTER V. THE WORK OF GRAHAM. _Thomas Graham_, 1805-1869. The work of Graham, concerned as it mostly was with the development of the conception of atoms, connects the time of Dalton with that in which we are now living. I have therefore judged it advisable to devote a short chapter to a consideration of the life-work of this chemist, before proceeding to the third period of chemical advance, that, namely, which witnessed the development of organic chemistry through the labours of men who were Graham's contemporaries. The printed materials which exist for framing the story of Graham's life are very meagre, but as he appears, from the accounts of his friends, to have devoted himself entirely to scientific researches, we cannot go far wrong in regarding the history of his various discoveries as also the history of his life. * * * * * THOMAS GRAHAM was born in Glasgow, on December 21, 1805. His father, James Graham, a successful manufacturer, was in a position to give his son a good education. After some years spent in the ordinary school training, Graham entered Glasgow University at the early age of fourteen, and graduated as M. A. five years later. It was the intention of Graham's father that his son should enter the Scottish Church; but under the teaching of Dr. Thomas Thomson and others the lad imbibed so strong a love of natural science, that rather than relinquish the pursuit of his favourite study, he determined to be independent of his father and make a living for himself. His father was much annoyed at the determination of his son to pursue science, and vainly attempted to force him into the clerical profession. The quarrel between father and son increased in bitterness, and notwithstanding the intervention of friends the father refused to make his son any allowance for his maintenance; and although many years after a reconcilement was effected, yet at the time when Graham most needed his father's help he was left to struggle alone. Graham went to Edinburgh, where he pursued his studies under Hope and Leslie, professors of chemistry and physics respectively--men whose names were famous wherever natural science was studied. Graham's mother, for whom he had always the greatest respect and warmest love, and his sister Margaret helped him as best they could during this trying time. The young student found some literary occupation and a little teaching in Edinburgh, and sometimes he was asked to make investigations in subjects connected with applied chemistry. Thus he struggled on for four or five years, during which time he began to publish papers on chemico-physical subjects. In the year 1829 he was appointed Lecturer on Chemistry at the Mechanics' Institution in Glasgow, and next year he was removed to the more important position of lecturer on the same science at the Andersonian Institution in that city. This position he occupied for seven years, when he was elected Professor of Chemistry in the University of London (now University College): he had been elected to the Fellowship of the Royal Society in the preceding year. During his stay at the Andersonian Institution Graham had established his fame as a physical chemist; he had begun his work on acids and salts, and had established the fundamental facts concerning gaseous diffusion. These researches he continued in London, and from 1837 to 1854 he enriched chemical science with a series of papers concerned for the most part with attempts to trace the movements of the atoms of matter. In 1854 Graham succeeded Sir John Herschel in the important and honourable position of Master of the Mint. For some years after his appointment he was much engaged with the duties of his office, but about 1860 he again returned to his atomic studies, and in his papers on "Transpiration of Liquids" and on "Dialysis" he did much in the application of physical methods to solve chemical problems, and opened up new paths, by travelling on which his successors greatly advanced the limits of the science of chemistry. Graham was almost always at work; his holidays were "few and far between." By the year 1868 or so his general health began to grow feeble; in the autumn of 1869, during a visit to Malvern where he sought repose and invigorating air, he caught cold, which developed into inflammation of the lungs. On his return to London the disease was overcome by medical remedies, but he continued very weak, and gradually sank, till the end came on the 16th of September 1869. I have said that the seven years during which Graham held the lectureship on chemistry in the Andersonian Institution, Glasgow, witnessed the beginning alike of his work on salts and of that on gaseous diffusion. He showed that there exists a series of compounds of various salts, _e.g._ chloride of calcium, chloride of zinc, etc., with alcohol. He compared the alcohol in these salts, which he called _alcoates_, to the water in ordinary crystallized salts, and thus drew the attention of chemists to the important part played by water in determining the properties of many substances. Three years later (1833) appeared one of his most important papers, bearing on the general conception of acids: "Researches on the Arseniates, Phosphates, and Modifications of Phosphoric Acid." Chemists at this time knew that phosphoric acid--that is, the substance obtained by adding water to pentoxide of phosphorus--exhibited many peculiarities, but they were for the most part content to leave these unexplained. Graham, following up the analogy which he had already established between water and bases, prepared and carefully determined the composition of a series of phosphates, and concluded that pentoxide of phosphorus is able to combine with a base--say soda--in three different proportions, and thus to produce three different phosphates of soda. But as Graham accepted that view which regards a salt as a metallic derivative of an acid, he supposed that three different phosphoric acids ought to exist; these acids he found in the substances produced by the action of water on the oxide of phosphorus. He showed that just as the oxide combines with a base in three proportions, so does it combine with water in three proportions. This water he regarded as chemically analogous to the base in the three salts, one atom (we should now rather say molecule) of base could be replaced by one atom of water, two atoms of base by two atoms of water, or three atoms of base by three atoms of water. Phosphoric acid was therefore regarded by Graham as a compound of pentoxide of phosphorus and water, the latter being as essentially a part of the acid as the former. He distinguished between _monobasic_, _dibasic_, and _tribasic_ phosphoric acids: by the action of a base on the _monobasic acid_, one, and only one salt was produced; the _dibasic acid_ could furnish two salts, containing different proportions (or a different number of atoms) of the same base: and from the _tribasic acid_ three salts, containing the same base but in different proportions, could be obtained. Davy's view of an acid as a compound of water with a negative oxide was thus confirmed, and there was added to chemical science the conception of _acids of different basicity_. In 1836 Graham's paper on "Water as a Constituent of Salts" was published in the "Transactions of the Royal Society of Edinburgh." In this paper he inquires whether the water in crystalline salts can or cannot be removed without destroying the chemical individuality of the salts. He finds that in some crystalline salts part of the water can be easily removed by the application of heat, but the remainder only at very high temperatures. He distinguishes between those atoms of water which essentially belong to the compound atom of the salt, and those atoms which can be readily removed therefrom, which are as it were added on to, or built up around the exterior of the atom of salt. In this paper Graham began to distinguish what is now called _water of crystallization_ from _water of constitution_, a distinction pointed to by some of Davy's researches, but a distinction which has remained too much a mere matter of nomenclature since the days of Graham. In these researches Graham emphasized the necessity of the presence of hydrogen in all true acids; as he had drawn an analogy between water and bases, so now he saw in the hydrogen of acids the analogue of the metal of salts. He regarded the structure of the compound atom of an acid as similar to that of the compound atom of a salt; the hydrogen atom, or atoms, in the acid was replaced by a metallic atom, or atoms, and so a compound atom of the salt was produced. Davy and Berzelius had proved that hydrogen is markedly electro-positive; hydrogen appeared to Graham to belong to the class of metals. In making this bold hypothesis Graham necessarily paid little heed to those properties of metals which appeal to the senses of the observer. Metals, as a class, are lustrous, heavy, malleable substances; hydrogen is a colourless, inodourless, invisible, very light gas: how then can hydrogen be said to be metallic? I have again and again insisted on the need of imagination for the successful study of natural science. Although in science we deal with phenomena which we wish to measure and weigh and record in definite and precise language, yet he only is the successful student of science who can penetrate beneath the surface of things, who can form mental pictures different from those which appear before his bodily eye, and so can discern the intricate and apparently irregular analogies which explain the phenomena he is set to study. Graham was not as far as we can learn endowed, like Davy, with the sensitive nature of a poet, yet his work on hydrogen proves him to have possessed a large share of the gift of imagination. Picturing to himself the hydrogen atom as essentially similar in its chemical functions to the atom of a metal, he tracked this light invisible gas through many tortuous courses: he showed how it is absorbed and retained (_occluded_ as he said) by many metals; he found it in meteors which had come from far-away regions of space; and at last, the year before he died he prepared an alloy of palladium and the metal hydrogen, from which a few medals were struck, bearing the legend "Palladium-Hydrogenium 1869." Within the last few years hydrogen has been liquified and, it is said, solidified. Solid hydrogen is described as a steel-grey substance which fell upon the table with a sound like the ring of a metal. But Graham's most important work was concerned with the motion of the ultimate particles of bodies. He uses the word "atom" pretty much as Dalton did. He does not make a distinction between the atom of an element and the atom of a compound, but apparently uses the term as a convenient one to express the smallest undivided particle of any chemical substance which exhibits the properties of that substance. As Graham was chiefly concerned with the physical properties of chemical substances, or with those properties which are studied alike by chemistry and physics, the distinction between atom and molecule, so all-important in pure chemistry, might be, and to a great extent was, overlooked by him. In considering his work we shall however do well to use the terms "atom" and "molecule" in the sense in which they are now always used in chemistry, a sense which has been already discussed (see pp. 139-143). Many years before Graham began his work a curious fact had been recorded but not explained. In 1823 Döbereiner filled a glass jar with hydrogen and allowed the jar to stand over water: on returning after twelve hours he found that the water had risen about an inch and a half into the jar. Close examination of the jar showed the presence of a small crack in the glass. Many jars, tubes and flasks, all with small cracks in the glass, were filled with hydrogen and allowed to stand over water; in every case the water rose in the vessel. No rise of the water was however noticeable if the vessels were filled with ordinary air, nitrogen or oxygen. In 1831 Graham began the investigation of the peculiar phenomenon observed by Döbereiner. Repeating Döbereiner's experiments, Graham found that a portion of the hydrogen in the cracked vessels passed outwards through the small fissures, and a little air passed inwards: the water therefore rose in the jar, tube or flask, because there was a greater pressure on the surface of the water outside than upon that inside the vessel. Any gas lighter than air behaved like hydrogen; when gases heavier than air were employed the level of the water inside the vessel was slightly lowered after some hours. Graham found that the passage of gases through minute openings could be much more accurately studied by placing the gas to be examined in a glass tube one end of which was closed by a plug of dry plaster of Paris, than by using vessels with small fissures in the glass. The _diffusion-tube_ used by Graham generally consisted of a piece of glass tubing, graduated in fractions of a cubic inch and having a bulb blown near one end; the short end was closed by a thin plug of dry plaster of Paris (gypsum), the tube was filled with the gas to be examined, and the open end was immediately immersed in water. The water was allowed to rise until it had attained a constant level, when it was found that the whole of the gas originally in the tube had passed outwards through the porous plug, and air had passed inwards. The volume of gas originally in the tube being known, and the volume of air in the tube at the close of the experiment being measured, it was only necessary to divide the former by the latter number in order to obtain the number of volumes of gas which had passed outwards for each one volume of air which had passed inwards; in other words to obtain the _rate of diffusion_ compared with air of the gas under examination. Graham's results were gathered together in the statement, "The diffusion-rates of any two gases are inversely as the square roots of their densities." Thus, take oxygen and hydrogen: oxygen is sixteen times heavier than hydrogen, therefore hydrogen diffuses four times more rapidly than oxygen. Take hydrogen and air: the specific gravity of hydrogen is 0·0694, air being 1; the square root of 0·0694 is 0·2635, therefore hydrogen will diffuse more rapidly than air in the ratio of 0·2635:1. In the years 1846-1849 Graham resumed this inquiry; he now distinguished between _diffusion_, or the passage of gases through porous plates, and _transpiration_, or the passage of gases through capillary tubes. He showed that if a sufficiently large capillary tube be employed the rate of transpiration of a gas becomes constant, but that it is altogether different from the rate of diffusion of the same gas. He established the fact that there is a connection of some kind between the transpiration-rates and the chemical composition of gases, and in doing this he opened up a field of inquiry by cultivating which many important results have been gained within the last few years, and which is surely destined to yield more valuable fruit in the future. Returning to the diffusion of gases, Graham, after nearly thirty years' more or less constant labour, begins to speculate a little on the causes of the phenomena he had so studiously and perseveringly been examining. In his paper on "The Molecular Mobility of Gases," read to the Royal Society in 1863, after describing a new diffusion-tube wherein thin plates of artificial graphite were used in place of plaster of Paris, Graham says, "The pores of artificial graphite appear to be really so minute that a gas _in mass_ cannot penetrate the plate at all. It seems that molecules only can pass; and they may be supposed to pass wholly unimpeded by friction, for the smallest pores that can be imagined to exist in the graphite must be tunnels in magnitude to the ultimate atom of a gaseous body." He then shortly describes the molecular theory of matter, and shows how this theory--a sketch of which so far as it concerns us in this book has been given on pp. 123-125--explains the results which he has obtained. When a gas passed through a porous plate into a vacuum, or when one gas passed in one direction and another in the opposite direction through the same plate, Graham saw the molecules of each gas rushing through the "tunnels" of graphite or stucco. The average rate at which the molecules of a gas rushed along was the diffusion-rate of that gas. The lighter the gas the more rapid was the motion of its molecules. If a mixture of two gases, one much lighter than the other, were allowed to flow through a porous plate, the lighter gas would pass so much more quickly than the heavier gas that a partial separation of the two might probably be effected. Graham accomplished such a separation of oxygen and hydrogen, and of oxygen and nitrogen; and he described a simple instrument whereby this process of _atmolysis_, as he called it, might be effected. Graham's _tube atmolyser_ consisted of a long tobacco-pipe stem placed inside a rather shorter and considerably wider tube of glass; the pipe stem was fixed by passing through two corks, one at each end of the glass tube; through one of these corks there also passed a short piece of glass tubing. When the instrument was employed, the piece of short glass tubing was connected with an air-pump, and one end of the pipe stem with the gaseous mixture--say ordinary air. The air-pump being set in motion, the gaseous mixture was allowed to flow slowly through the pipe stem; the lighter ingredient of the mixture passed outwards through the pipe stem into the wide glass tube more rapidly than the heavier ingredient, and was swept away to the air-pump; the heavier ingredient could be collected, mixed with only a small quantity of the lighter, at the other end of the pipe stem. As Graham most graphically expressed it, "The stream of gas diminishes as it proceeds, like a river flowing over a pervious bed." Graham then contrived a very simple experiment whereby he was able to measure the rate of motion of the molecules of carbonic acid. He introduced a little carbonic acid into the lower part of a tall cylindrical jar, and at the close of certain fixed periods of time he determined the amount of carbonic acid which had diffused upwards through the air into the uppermost layer of the jar. Knowing the height of the jar, he now knew the distance through which a small portion of carbonic acid passed in a stated time, and regarding this small portion as consisting of a great many molecules, all moving at about equal rates, he had determined the average velocity of the molecules of carbonic acid. A similar experiment was performed with hydrogen. The general results were that the molecules of carbonic acid move about in still air with a velocity equal to seventy-three millimetres per minute, and that under the same conditions the molecules of hydrogen move with a velocity equal to about one-third of a metre per minute.[12] The Bakerian Lecture for 1849, read by Graham before the Royal Society, was entitled "On the Diffusion of Liquids." In this paper he describes a very large number of experiments made with a view to determine the rate at which a salt in aqueous solution diffuses, or passes upwards into a layer of pure water above it, the salt solution and the water not being separated by any intervening medium. Graham's method of procedure consisted in completely filling a small bottle with a salt solution of known strength, placing this bottle in a larger graduated vessel, and carefully filling the latter with water. Measured portions of the water in the larger vessel were withdrawn at stated intervals, and the quantity of salt in each portion was determined. Graham found that under these conditions salts diffused with very varying velocities. Groups of salts showed equal rates of diffusion. There appeared to be no definite connection between the molecular weights of the salts and their diffusion-rates; but as Graham constantly regarded diffusion, whether of gases or liquids, as essentially due to the movements of minute particles, he thought that the particles which moved about as wholes during diffusion probably consisted of groups of what might be called chemical molecules--in other words, Graham recognized various orders of small particles. As the atom was supposed to have a simpler structure than the molecule (if indeed it had a structure at all), so there probably existed groups of molecules which, under certain conditions, behaved as individual particles with definite properties. As Graham applied the diffusion of gases to the separation of two gases of unequal densities, so he applied the diffusion of liquids to the separation of various salts in solution. He showed also that some complex salts, such as the alums, were partially separated into their constituents during the process of diffusion. The prosecution of these researches led to most important results, which were gathered together in a paper on "Liquid Diffusion applied to Analysis," read to the Royal Society in 1861. Graham divided substances into those which diffused easily and quickly into water, and those which diffused very slowly; he showed that the former were all crystallizable substances, while the latter were non-crystallizable jelly-like bodies. Graham called these jelly-like substances _colloids;_ the easily diffusible substances he called _crystalloids_. He proved that a colloidal substance acts towards a crystalloid much as water does; that the crystalloid rapidly diffuses through the colloid, but that colloids are not themselves capable of diffusing through other colloids. On this fact was founded Graham's process of _dialysis_. As colloid he employed a sheet of parchment paper, which he stretched on a ring of wood or caoutchouc, and floated the apparatus so constructed--_the dialyser_--on the surface of pure water in a glass dish; he then poured into the dialyser the mixture of substances which it was desired to separate. Let us suppose that this mixture contained sugar and gum; the crystalloidal sugar soon passed through the parchment paper, and was found in the water outside, but the colloidal gum remained in the dialyser. If the mixture in the dialyser contained two crystalloids, the greater part of the more diffusible of these passed through the parchment in a short time along with only a little of the less diffusible; a partial separation was thus effected. This method of dialysis was applied by Graham to separate and obtain in the pure state many colloidal modifications of chemical compounds, such as aluminium and tin hydrates, etc. By his study of these peculiar substances Graham introduced into chemistry a new class of bodies, and opened up great fields of research. Matter in the colloidal state appears to be endowed with properties which are quite absent, or are hidden, when it is in the ordinary crystalloidal condition. Colloids are readily affected by the smallest changes in external conditions; they are eminently unstable bodies; they are, Graham said, always on the verge of an impending change, and minute disturbances in the surrounding conditions may precipitate this change at any moment. Crystalloids, on the other hand, are stable; they have definite properties, which are not changed without simultaneous large changes in surrounding conditions. But although, to use Graham's words, these classes of bodies "appear like different worlds of matter," there is yet no marked separating line between them. Ice is a substance which under ordinary conditions exhibits all the properties of crystalloids, but ice formed in contact with water just at the freezing point is not unlike a mass of partly dried gum; it shows no crystalline structure, but it may be rent and split like a lump of glue, and, like glue, the broken pieces may be pressed together again and caused to adhere into one mass. "Can any facts," asks Graham, "more strikingly illustrate the maxim that in Nature there are no abrupt transitions, and that distinctions of class are never absolute?" In the properties of colloids and crystalloids Graham saw an index of diversity of molecular structure. The smallest individual particle of a colloid appeared to him to be a much more complex structure than the smallest particle of a crystalloid. The colloidal molecule appeared to be formed by the gathering together of several crystalloidal molecules; such a complex structure might be expected readily to undergo change, whereas the simpler molecule of a crystalloid would probably present more definite and less readily altered properties. In this research Graham had again, as so often before, arrived at the conception of various orders of small particles. In the early days of the Daltonian theory it seemed that the recognition of atoms as ultimate particles, by the placing together of which masses of this or that kind of matter are produced, would suffice to explain all the facts of chemical combinations; but Dalton's application of the term "atom" to elements and compounds alike implied that an atom might itself have parts, and that one atom might be more complex than another. The way was thus already prepared for the recognition of more than one order of atoms, a recognition which was formulated three years after the appearance of Dalton's "New System" in the statement of Avogadro, "Equal volumes of gases contain equal numbers of molecules;" for we have seen that the application of this statement to actually occurring reactions between gases obliges us to admit that the molecules of hydrogen, oxygen and many other elementary gases are composed of two distinct parts or atoms. Berzelius it is true did not formally accept the generalization of Avogadro; but we have seen how the conception of atom which runs through his work is not that of an indivisible particle, but rather that of a little individual part of matter with definite properties, from which the mass of matter recognizable by our senses is constructed, just as the wall is built up of individual bricks. And as the bricks are themselves constructed of clay, which in turn is composed of silica and alumina, so may each of these little parts of matter be constructed of smaller parts; only as clay is not brick, and neither silica nor alumina is clay, so the properties of the parts of the atom--if it has parts--are not the properties of the atom, and a mass of matter constructed of these parts would not have the same properties as a mass of matter constructed of the atoms themselves. Another feature of Graham's work is found in the prominence which he gives to that view of a chemical compound which regards it as the resultant of the action and reaction of the parts of the compound. As the apparent stability of chemical compounds was seen by Davy to be the result of an equilibrium of contending forces, so did the seemingly changeless character of any chemical substance appear to Graham as due to the orderly changes which are continually proceeding among the molecules of which the substance is constructed. A piece of lime, or a drop of water, was to the mind of Graham the scene of a continual strife, for that minute portion of matter appeared to him to be constructed of almost innumerable myriads of little parts, each in more or less rapid motion, one now striking against another and now moving free for a little space. Interfere with those movements, alter the mutual action of those minute particles, and the whole building would fall to pieces. For more than thirty years Graham was content to trace the movements of molecules. During that time he devoted himself, with an intense and single-minded devotion, to the study of molecular science. Undaunted in early youth by the withdrawal of his father's support; unseduced in his middle age by the temptations of technical chemistry, by yielding to which he would soon have secured a fortune; undazzled in his later days by the honours of the position to which he had attained; Graham dedicated his life to the nobler object of advancing the bounds of natural knowledge, and so adding to those truths which must ever remain for the good and furtherance of humanity. FOOTNOTES: [12] A metre is equal to about thirty-nine inches; a millimetre is the one-thousandth part of a metre. CHAPTER VI. RISE AND PROGRESS OF ORGANIC CHEMISTRY--PERIOD OF LIEBIG AND DUMAS. _Justus Liebig, 1803-1873. Jean Baptiste André Dumas, born in 1800._ I have as yet said almost nothing with regard to the progress of organic chemistry, considered as a special branch of the science. It is however in this department that the greatest triumphs which mark the third period of chemical advance have been won. We must therefore now turn our attention to the work which has been done here. The ancients drew no such distinction between portions of their chemical knowledge, limited as it was, as is implied by the modern terms "organic" and "inorganic chemistry." An organic acid--acetic--was one of the earliest known substances belonging to the class of acids; many processes of chemical handicraft practised in the olden times dealt with the manufacture of substances, such as soap, leather or gum, which we should now call organic substances. Nor did the early alchemists, although working chiefly with mineral or inorganic substances, draw any strict division between the two branches of chemistry. The medical chemists of the sixteenth century dealt much with substances derived from plants and animals, such as benzoic and succinic acids, spirit of wine, oils, etc. But neither in their nomenclature nor in their practice did they sharply distinguish inorganic from organic compounds. They spoke of the _quintessence_ of arsenic and the _quintessence_ of alcohol; they applied the term "oil" alike to the products of the action of acids on metallic salts and to substances obtained from vegetables. But towards the end of the seventeenth century, at the time that is when the phlogistic theory began to gain pre-eminence, we find gradually springing up a division of chemical substances into mineral, animal and vegetable substances--a division which was based rather on a consideration of the sources whence the substances were derived than on the properties of the substances themselves, and therefore a division which was essentially a non-chemical one. About a century after this, systematic attempts began to be made to trace some peculiarity of composition as belonging to all compounds of organic, that is, of animal or vegetable, origin. As very many of the substances then known belonging to this class were more or less oil-like in their properties--oils, fats, balsams, gums, sugar, etc.--organic substances generally were said to be characterized by the presence in them of the _principle of oil_. Such a statement as this, although suited to the conceptions of that time, could not be received when Lavoisier had shown chemists how Nature ought be examined. With the definite conception of element introduced by the new chemistry, came an attempt to prove that organic compounds were built up of elements which were rarely found together in any one compound of inorganic origin. Substances of vegetable origin were said by Lavoisier to be composed of carbon, hydrogen and oxygen, while phosphorus and nitrogen, in addition to those three elements, entered into the composition of substances derived from animals. But neither could this definition of organic compounds be upheld in the face of facts. Wax and many oils contained only carbon and hydrogen, yet they were undoubtedly substances of vegetable or animal origin. If the presence of any two of the three elements, carbon, hydrogen and oxygen, were to be regarded as a sufficient criterion for the classification of a compound, then it was necessary that carbonic acid--obtained by the action of a mineral acid on chalk--should be called an organic compound. To Berzelius belongs the honour of being the chemist who first applied the general laws of chemical combination to all compounds alike, whether derived from minerals, animals, or vegetables. The ultimate particles, or molecules, of every compound were regarded by Berzelius as built up of two parts, each of which might itself be an elementary atom, or a group of elementary atoms. One of these parts, he said, was characterized by positive, the other by negative electricity. Every compound molecule, whatever was the nature or number of the elementary atoms composing it, was a dual structure (see p. 164). Organic chemistry came again to be a term somewhat loosely applied to the compounds derived from animals or vegetables, or in the formation of which the agency of living things was necessary. Most, if not all of these compounds contained carbon and some other element or elements, especially hydrogen, oxygen and nitrogen. But the progress of this branch of chemistry was impeded by the want of any trustworthy methods for analysing compounds containing carbon, oxygen and hydrogen. This want was to be supplied, and the science of organic chemistry, and so of chemistry in general, was to be immensely advanced by the labours of a new school of chemists, chief among whom were Liebig and Dumas. Let us shortly trace the work of these two renowned naturalists. The life-work of the first is finished; I write this story of the progress of his favourite science on the eighty-second birthday of the second of these great men, who is still with us a veteran crowned with glory, a true soldier in the battle against ignorance and so against want and crime. * * * * * JUSTUS LIEBIG was born at Darmstadt, on the 12th of May 1803. The main facts which mark his life regarded apart from his work as a chemist are soon told. Showing a taste for making experiments he was apprenticed by his father to an apothecary. Fortunately for science he did not long remain as a concoctor of drugs, but was allowed to enter the University of Bonn as a student of medicine. From Bonn he went to Erlangen, at which university he graduated in 1821. A year or two before this time Liebig had begun his career as an investigator of Nature, and he had already made such progress that the Grand Duke of Hesse-Darmstadt was prevailed on to grant him a small pension and allow him to prosecute his researches at Paris, which was then almost the only place where he could hope to find the conditions of success for the study of scientific chemistry. To Paris accordingly he went in 1823. He was so fortunate--thanks to the good graces of the renowned naturalist Alexander von Humboldt--as to be allowed to enter the laboratory of Gay-Lussac, where he continued the research on a class of explosive compounds, called _fulminates_, which he had begun before leaving Darmstadt. A year later Liebig was invited to return to his native country as Professor of Chemistry in the small University of Giessen--a name soon to be known wherever chemistry was studied, and now held dear by many eminent chemists who there learned what is meant by the scientific study of Nature. The year before Liebig entered the laboratory of Gay-Lussac there came to Paris a young and enthusiastic student who had already made himself known in the scientific world by his physiological researches, and who was now about to begin his career as a chemist. In that southern part of France which is rich in memories of the Roman occupation, not far from the remains of the great aqueduct which spans the valley of the Gardon, at no great distance from the famous cities of Arles and Nîmes, was born, in the town of Alais, on the 14th of July 1800, JEAN BAPTISTE ANDRÉ DUMAS. The father of Dumas was a man of considerable culture; he gave his son as good an education as could be obtained in the little town of his birth. At the age of fourteen young Dumas was a good classical scholar, and had acquired a fair knowledge of natural science. But for his deficiency in mathematics he would probably have entered for the examination which admitted those who passed it to join the French navy. But before he had made good his mathematical deficiencies the troublous nature of the times (1814-15) obliged his parents to think of some other profession for their son which would entail less sacrifice on their part. Like his great fellow-worker in after life he was apprenticed to an apothecary, and like him also, he soon forsook this sphere of usefulness. Desirous of better opportunities for the study of science, and overpowered by the miseries which war had brought upon the district of his birth, Dumas persuaded his father to allow him to go to Geneva. At Geneva Dumas found an atmosphere more suited to his scientific progress; chemistry, physics, botany, and other branches of natural science were taught by men whose names were everywhere known. He began experiments in chemistry with the crudest and most limited apparatus, but even with these he made discoveries which afterwards led to important work on the volumes occupied by the atoms of elementary substances. About the year 1818 Dumas became acquainted with Dr. J. L. Prévost, who had returned from studying in many of the most famous medical schools of Europe. Invited by Prévost to join in an investigation requiring medical, botanical and chemical knowledge, Dumas now began a series of researches which soon passed into the domain of animal physiology, and by the prosecution of which under many difficulties he laid the foundations of his future fame. But along with his physiological work Dumas carried on a research into the expansion of various ethers. This necessitated the preparation of a series of ethers in a state of purity; but so difficult did Dumas find this to be, so much time did he consume in this preliminary work, and so interested did he become in the chemical part of the investigation, that he abandoned the experiments on expansion, and set himself to solve some of the problems presented by the composition and chemical properties of the ethers. Dumas would probably have remained in Geneva had he not had a morning visit paid him in the year 1822. When at work in his laboratory one day, some one knocked and was bidden come in. "I was surprised to find myself face to face with a gentleman in a light-blue coat with metal buttons, a white waistcoat, nankeen breeches, and top-boots.... The wearer of this costume, his head somewhat bent, his eyes deep-set but keen, advanced with a pleasant smile, saying, 'Monsieur Dumas.' 'The same, sir; but excuse me.' 'I am M. de Humboldt, and did not wish to pass through Geneva without having had the pleasure of seeing you.'... I had only one chair. My visitor was pleased to accept it, whilst I resumed my elevated perch on the drawing stool.... 'I intend,' said M. de Humboldt, 'to spend some days in Geneva, to see old friends and to make new ones, and more especially to become acquainted with young people who are beginning their career. Will you act as my cicerone? I warn you however that my rambles begin early and end late. Now, could you be at my disposal, say from six in the morning till midnight?'" After some days spent as Humboldt had indicated the great naturalist left Geneva. Dumas tells us that the town seemed empty to him. "I felt as if spell-bound. The memorable hours I had spent with that irresistible enchanter had opened a new world to my mind." Dumas felt that he must go to Paris--that there he would have more scope and more opportunities for prosecuting science. A few kind words, a little genuine sympathy, and a little help from Humboldt were thus the means of fairly launching in their career of scientific inquiry these two young men, Liebig and Dumas. In Paris, whither he went in 1823, Dumas found a welcome. He soon made the acquaintance and gained the friendship of the great men who then made natural science so much esteemed in the French capital. When the year 1826 came, it saw him Professor of Chemistry at the Athenæum, and married to the lady whom he loved, and who has ever since fought the battle of life by his side. Liebig left Paris in 1824. By the year 1830 he had perfected and applied that method for the analysis of organic compounds which is now in constant use wherever organic chemistry is studied; by the same year Dumas had given the first warning of the attack which he was about to make on the great structure of dualism raised by Berzelius. In a paper, "On Some Points of the Atomic Theory," published in 1826, Dumas adopted the distinction made by Avogadro between molecules and atoms, or between the small particles of substances which remain undivided during physical actions, and the particles, smaller than these, which are undivided during chemical actions. But, unfortunately, Dumas did not mark these two conceptions by names sufficiently definite to enable the readers of his memoir to bear the distinction clearly in mind. The terms "atom" and "molecule" were not introduced into chemistry with the precise meanings now attached to them until some time after 1826. Although the idea of two orders of small particles underlies all the experimental work described by Dumas in this paper, yet the numbers which he obtained as representing the actual atomic weights of several elements--_e.g._ phosphorus, arsenic, tin, silicon--show that he had not himself carried out Avogadro's hypothesis to its legitimate conclusions. Two years after this Dumas employed the reaction wherein two volumes of gaseous hydrochloric acid are produced by the union of one volume of hydrogen with one volume of chlorine, as an argument which obliged him to conclude that, if Avogadro's physical hypothesis be accepted, the molecules of hydrogen and chlorine split, each into two parts, when these gases combine chemically. But Dumas did not at this time conclude that the molecular weight of hydrogen must be taken as twice its atomic weight, and that--hydrogen being the standard substance--the molecular weights of all gases must be represented by the specific gravities of these gases, referred to hydrogen as 2. I have already shortly discussed the method for finding the relative weights of elementary atoms which is founded on Avogadro's hypothesis, and, I think, have shown that this hypothesis leads to the definition of "atom" as the smallest amount of an element in one molecule of any compound of that element (see p. 142). This deduction from Avogadro's law is now a part and parcel of our general chemical knowledge. We wonder why it was not made by Dumas; but we must remember that a great mass of facts has been accumulated since 1826, and that this definition of "atom" has been gradually forced on chemists by the cumulative evidence of those facts. One thing Dumas did do, for which the thanks of every chemist ought to be given him; he saw the need of a convenient method for determining the densities of compounds in the gaseous state, and he supplied this need by that simple, elegant and trustworthy method, still in constant use, known as _Dumas's vapour density process_. While Dumas was working out the details of this analytical method, which was destined to be so powerful an instrument of research, Liebig was engaged in similar work; he was perfecting that process for the analysis of organic compounds which has since played so important a part in the advancement of this branch of chemical science. The processes in use during the first quarter of this century for determining the amounts of carbon, hydrogen, and oxygen in compounds of those elements, were difficult to conduct and gave untrustworthy results. Liebig adopted the principle of the method used by Lavoisier, viz. that the carbon in a compound can be oxidized, or burnt, to carbonic acid, and the hydrogen to water. He contrived a very simple apparatus wherein this burning might be effected and the products of the burning--carbonic acid and water--might be arrested and weighed. Liebig's apparatus remains now essentially as it was presented to the chemical world in 1830. Various improvements in details have been made; the introduction of gas in place of charcoal as a laboratory fuel has given the chemist a great command over the process of combustion, but in every part of the apparatus to-day made use of in the laboratory is to be traced the impress of the master's hand. A weighed quantity of the substance to be analyzed is heated with oxide of copper in a tube of hard glass; the carbon is burnt to carbonic acid and the hydrogen to water at the expense of the oxygen of the copper oxide. Attached to the combustion tube is a weighed tube containing chloride of calcium, a substance which greedily combines with water, and this tube is succeeded by a set of three or more small bulbs, blown in one piece of glass, and containing an aqueous solution of caustic potash, a substance with which carbonic acid readily enters into combination. The chloride of calcium tube and the potash bulbs are weighed before and after the experiment; the increase in weight of the former represents the amount of water, and the increase in weight of the latter the amount of carbonic acid obtained by burning a given weight of the compound under examination. As the composition of carbonic acid and of water is known, the amounts of carbon and of hydrogen in one hundred parts of the compound are easily found; the difference between the sum of these and one hundred represents the amount of oxygen in one hundred parts of the compound. If the compound should contain elements other than these three, those other elements are determined by special processes, the oxygen being always found by difference. Soon after his settlement at Giessen Liebig turned his attention to a class of organic compounds known as the _cyanates_; but Wöhler--who, while Liebig was in Paris in the laboratory of Gay-Lussac, was engaged in studying the intricacies of mineral chemistry under the guidance of Berzelius--had already entered on this field of research. The two young chemists compared notes, recognized each other's powers, and became friends; this friendship strengthened as life advanced, and some of the most important papers which enriched chemical science during the next thirty years bore the joint signatures of Liebig and Wöhler. I have already mentioned that when it was found necessary to abandon the Lavoisierian definition of organic chemistry as the chemistry of compounds containing carbon, hydrogen and oxygen, and sometimes also phosphorus or nitrogen, a definition was attempted to be based on the supposed fact that the formation of the compounds obtained from animals and plants could be accomplished only by the agency of a living organism. But the discovery made in 1828 by Wöhler, that _urea_--a substance specially characterized by its production in the animal economy, and in that economy only--could be built up from mineral materials, rendered this definition of organic chemistry impossible, and broke down the artificial barrier whereby naturalists attempted to separate two fields of study between which Nature made no division. We have here another illustration of the truth of the conception which underlies so many of the recent advances of science, which is the central thought of the noble structure reared by the greatest naturalist of our time, and which is expressed by one of the profoundest students of Nature that this age has seen in the words I have already quoted from the preface to the "Lyrical Ballads," "In Nature everything is distinct, but nothing defined into absolute independent singleness." From this time the progress of organic chemistry became rapid. Dumas continued the researches upon ethers which he had commenced at Geneva, and by the year 1829 or so he had established the relations which exist between ethers and alcohols on the one hand, and ethers and acids on the other. This research, a description of the details of which I cannot introduce here as it would involve the use of many technical terms and assume the possession by the reader of much technical knowledge, was followed by others, whereby Dumas established the existence of a series of compounds all possessed of the chemical properties of alcohol, all containing carbon, hydrogen and oxygen, but differing from one another by a constant amount of carbon and hydrogen. This discovery of a series of alcohols, distinguished by the possession of certain definite properties whereby they were marked off from all other so-called organic compounds, was as the appearance of a landmark to the traveller in a country where he is without a guide. The introduction of the comparative method of study into organic chemistry--the method, that is, which bases classification on a comparison of large groups of compounds, and which seeks to gather together those substances which are like and to separate those which are unlike--soon began to bear fruit. This method suggested to the experimenter new points of view from which to regard groups of bodies; analogies which were hidden when a few substances only were considered, became prominent as the range of view was widened. What the gentle Elia calls "fragments and scattered pieces of truth," "hints and glimpses, germs, and crude essays at a system," became important. There was work to be done, not only by the master spirits who, looking at things from a central position of vantage, saw the relative importance of the various detailed facts, but also by those who could only "beat up a little game peradventure, and leave it to knottier heads, more robust constitutions, to run it down." Twenty years before the time of which we are now speaking Davy had decomposed the alkalis potash and soda; as he found these substances to be metallic oxides, he thought it very probable that the other well-known alkali, ammonia, would also turn out to be the oxide of a metal. By the electrolysis of salts formed by the action of ammonia on acids, using mercury as one of the poles of the battery, Davy obtained a strange-looking spongy substance which he was inclined to regard as an alloy of the metallic base of ammonia with mercury. From the results of experiments by himself and others, Davy adopted a view of this alloy which regarded it as containing a _compound radicle_, or group of elementary atoms which in certain definite chemical changes behaved like a single elementary atom. To this compound radicle he gave the name of _ammonium_. As an aqueous solution of potash or soda was regarded as a compound of water and oxide of potassium or sodium, so an aqueous solution of ammonia was regarded as a compound of water and oxide of ammonium. When the composition of this substance, ammonium, came to be more accurately determined, it was found that it might be best represented as a compound atom built up of one atom of nitrogen and four atoms of hydrogen. The observed properties of many compounds obtained from ammonia, and the analogies observed between these and similar compounds obtained from potash and soda, could be explained by assuming in the compound atom (or better, in the molecule) of the ammonia salt, the existence of this group of atoms, acting as one atom, called ammonium. The reader will not fail to observe how essentially atomic is this conception of compound radicle. The ultimate particle, the molecule, of a compound has now come to be regarded as a structure built up of parts called atoms, just as a house is a structure built up of parts called stones and bricks, mortar and wood, etc. But there may be a closer relationship between some of the atoms in this molecule than between the other atoms. It may be possible to remove a group of atoms, and put another group--or perhaps another single atom--in the place of the group removed, without causing the whole atomic structure to fall to pieces; just as it may be possible to remove some of the bricks from the wall of a house, or a large wooden beam from beneath the lintels, and replace these by other bricks or by a single stone, or replace the large wooden beam by a smaller iron one, without involving the downfall of the entire house. The group of atoms thus removable--the compound radicle--may exist in a series of compounds. As we have an oxide, a sulphide, a chloride, a nitrate, etc., of sodium, so we may have an oxide, a sulphide, a chloride, a nitrate, etc., of ammonium. The compounds of sodium are possessed of many properties in common; this is partly explained by saying that they all contain one or more atoms of the element sodium. The compounds of ammonium possess many properties in common, and this is partly explained if we assume that they all contain one or more atoms of the compound radicle ammonium. The conception of compound radicle was carried by Berzelius to its utmost limits. We have learned that the Swedish chemist regarded every molecule as composed of two parts; in very many cases each of these parts was itself made up of more than one kind of atom--it was a compound radicle. But the Berzelian system tended to become too artificial: it drifted further and further away from facts. Of the two parts composing the dual molecular structure, one was of necessity positively, and the other negatively electrified. The greater number of the so-called organic compounds contained oxygen; oxygen was the most electro-negative element known; hence most organic compounds were regarded as formed by the coming together of one, two, or more atoms of oxygen, forming the negative part of the molecule, with one, two, or more atoms of a compound radicle, which formed the positive part of the molecule. From this dualistic view of the molecule there naturally arose a disposition to regard the compound radicles of organic chemistry as the non-oxygenated parts of the molecules of organic compounds. An organic compound came gradually to be regarded as a compound of oxygen with some other elements, which were all lumped together under the name of a compound radicle, and organic chemistry was for a time defined as the chemistry of compound radicles. From what has been said on p. 268, I think it will be evident that the idea of _substitution_ is a necessary part of the original conception of compound radicle; a group of atoms in a molecule may, it is said, be removed, and another group, or another atom, _substituted_ for that which is removed. Berzelius adopted this idea, but he made it too rigid; he taught that an electro-negative atom, or compound radicle, could be replaced or substituted only by another electro-negative atom or group of atoms, and a positively electrified atom or group of atoms, only by another electro-positive atom or compound radicle. Thus oxygen could perhaps be replaced by chlorine, but certainly not by hydrogen; while hydrogen might be replaced by a positively electrified atom, but certainly not by chlorine. The conceptions of compound radicles and of substitution held some such position in organic chemistry as that which I have now attempted to indicate when Dumas and Liebig began their work in this field. The visitors at one of the royal _soirées_ at the Tuileries were much annoyed by the irritating vapours which came from the wax candles used to illuminate the apartments; Dumas was asked to examine the candles and find the reason of their peculiar behaviour. He found that the manufacturer had used chlorine to bleach the wax, that some of this chlorine remained in the candles, and that the irritating vapours which had annoyed the guests of Charles X. contained hydrochloric acid, produced by the union of chlorine with part of the hydrogen of the wax. Candles bleached by some other means than chlorine were in future used in the royal palaces; and the unitary theory, which was to overthrow the dualism of Berzelius, began to arise in the mind of Dumas. The retention of a large quantity of chlorine by wax could scarcely be explained by assuming that the chlorine was present only as a mechanically held impurity. Dumas thoroughly investigated the action of chlorine on wax and other organic compounds; and in 1834 he announced that hydrogen in organic compounds can be exchanged for chlorine, every volume of hydrogen given up by the original compound being replaced by an equal volume of chlorine. Liebig and Wöhler made use of a similar conception to explain the results which they had obtained about this time in their study of the oil of bitter almonds, a study which will be referred to immediately. The progress of this bold innovation made by Dumas was much advanced by the experiments and reasonings of two French chemists, whose names ought always to be reverenced by students of chemistry as the names of a pair of brilliant naturalists to whom modern chemistry owes much. _Gerhardt_ was distinguished by clearness of vision and expression; _Laurent_ by originality, breadth of mind and power of speculation. Laurent appears to have been the first who made a clear statement of the fundamental conception of the unitary theory: "Many organic compounds, when treated with chlorine lose a certain number of equivalents of hydrogen, which passes off as hydrochloric acid. An equal number of equivalents of chlorine takes the place of the hydrogen so eliminated; thus the physical and chemical properties of the original substance are not profoundly changed. The chlorine occupies the place left vacant by the hydrogen; the chlorine plays in the new compound the same part as was played by the hydrogen in the original compound." The replacement of electro-positive hydrogen by electro-negative chlorine was against every canon of the dualistic chemistry; and to say that the physical and chemical properties of the original compound were not profoundly modified by this replacement, seemed to be to call in question the validity of the whole structure raised by the labours during a quarter of a century of one universally admitted to be among the foremost chemists of his age. But facts accumulated. By the action of chlorine on alcohol Liebig obtained _chloroform_ and _chloral_, substances which have since been so largely applied to the alleviation of human suffering; but it was Dumas who correctly determined the composition of these two compounds, and showed how they are related to alcohol and to one another. Liebig's reception of the corrections made by Dumas in his work furnishes a striking example of the true scientific spirit. "As an excellent illustration," said Liebig, "of the mode in which errors should be corrected, the investigation of chloral by Dumas may fitly be introduced. It carried conviction to myself, as I think to everybody else, not by the copious number of analytical data opposed to the not less numerous results which I had published, but because these data gave a simpler explanation both of the formation and of the changes of the substances in question." One of the most important contributions to the new views was made by Dumas in his paper on the action of chlorine on acetic acid (1833), wherein he proved that the product of this action, viz. _trichloracetic acid_, is related to the parent substance by containing three atoms of chlorine in place of three atoms of hydrogen in the molecule; that the new substance is, like the parent substance, a monobasic acid; that its salts are very analogous in properties to the salts of acetic acid; that the action of the same reagents on the two substances is similar; and finally, that the existence of many derivatives of these compounds could be foretold by the help of the new hypothesis, which derivatives ought not to exist according to the dualistic theory, but which, unfortunately for that theory, were prepared and analyzed by Dumas. I have alluded to a research by Liebig and Wöhler on oil of bitter almonds as marking an important stage in the advance of the anti-dualistic views. The paper alluded to was published in 1832. At that time it was known that _benzoic acid_ is formed by exposure of bitter-almond oil to the air. Liebig and Wöhler made many analyses of these two substances, and many experiments on the mutual relations of their properties, whereby they were led to regard the molecules of the oil as built up each of an atom of hydrogen and an atom of a compound radicle--itself a compound of carbon, hydrogen and oxygen--to which they gave the name of _benzoyl_.[13] Benzoic acid they regarded as a compound of the same radicle with another radicle, consisting of equal numbers of oxygen and hydrogen atoms. By the action of chlorine and other reagents on bitter-almond oil these chemists obtained substances which were carefully analyzed and studied, and the properties of which they showed could be simply explained by regarding them all as compounds of the radicle _benzoyl_ with chlorine and other atoms or groups of atoms. But this view, if adopted, necessitated the belief that chlorine atoms could replace oxygen atoms; and, generally, that the substitution of an electro-positive by a negative atom or group of atoms did not necessarily cause any great alteration in the properties of the molecule. Thus it was that the rigid conceptions of dualism were shown to be too rigid; that the possibility of an electro-positive radicle, or atom, replacing another of opposite electricity was recognized; and thus the view which regarded a compound molecule as one structure--atoms in which might be replaced by other atoms irrespective of the mutual electrical relations of these atoms--began to gain ground. From this time the molecule of a compound has been generally regarded as a unitary structure, as one whole, and the properties of the molecule as determined by the nature, number, and arrangement of all the atoms which together compose it. The unitary conception of a compound molecule appeared at first to be altogether opposed to the system of Berzelius; but as time went on, and as fresh facts came to be known, it was seen that the new view conserved at least one, and that perhaps the most important, of the thoughts which formed the basis of the Berzelian classification. Underlying the dualism of Berzelius was the conception of the molecule as an atomic structure; this was retained in the unitary system of Dumas, Gerhardt and Laurent. Berzelius had insisted that every molecule is a dual structure. This is taking too narrow a view of the possibilities of Nature, said the upholders of the new school. _This_ molecule may have a dual structure; _that_ may be built up of three parts. The structure of this molecule or of that can be determined only by a careful study of its relations with other molecules. For a time it seemed also as if the new chemistry could do without the compound radicle which had been so much used by Berzelius; but the pressure of facts soon drove the unitary chemists to recognize the value of that hypothesis which looked on parts of the molecule as sometimes more closely associated than other parts--which recognized the existence of atomic structures within the larger molecular structures. As a house is not simply a putting together of so many bricks, so much mortar, so many doors and windows, so many leaden pipes, etc., but rather a definite structure composed of parts, many of which are themselves also definite structures, such as the window and its accessory parts, the door with its lintel and handle, etc., so to the unitary chemists did the molecule appear to be built up of parts, some of which, themselves composed of yet smaller parts, discharged a particular function in the molecular economy. A general division of a plant might describe it as a structure consisting of a stem, a root, and leaves. Each of the parts, directly by its individual action and indirectly by the mutual action between it and all the other parts, contributes to the growth of the whole plant; but if the stem, or root, or leaves be further analyzed, each is found to consist of many parts, of fibres and cells and tissue, etc. We may liken the plant to the molecule of an organic compound; the root, the stem and the leaves to the compound radicles of which this molecule is built up, and the tissue, fibres, etc., to the elementary atoms which compose these compound radicles. The molecule is one whole, possessed of definite structure and performing a definite function by virtue of the nature and the arrangement of its parts. Many years elapsed after the publication of the researches of Dumas, and of Liebig and Wöhler, before such a conception of the molecule as this was widely accepted by chemists. The opposition of the older school, headed by their doughty champion Berzelius, had to be overcome; the infallibility of some of the younger members of the new school had to be checked; facts had to be accumulated, difficulties explained, weak analogies abandoned and strong ones rendered stronger by research; special views of the structure of this or that molecule, deduced from a single investigation, had to be supplemented and modified by wider views gained by the researches of many workers. It was not till 1867 that Liebig, when asked by Dumas at a dinner given during the French Exhibition to the foreign chemists, why he had abandoned organic chemistry, replied that "now, with the theory of substitution as a foundation, the edifice may be built up by workmen: masters are no longer needed." Laurent and Gerhardt did noble work in advancing the unitary theory; to them is largely due the fruitful conception of types, an outcome of Dumas's work, which owed its origin to the flickering of the wax candles in the Tuileries during the royal _soirée_. Chlorine can be substituted for hydrogen in acetic acid, and the product is closely related in its properties to the parent substance; various atoms or groups of atoms can be substituted by other groups in the derivatives of oil of bitter almonds, but a close analogy in properties runs through all these compounds: these facts might be more shortly expressed by saying that acetic and trichloracetic acids belong to the same _type_, and that the derivatives of bitter-almond oil likewise belong to one _type_. Laurent carried this conception into inorganic chemistry. Water and potash did not seem to have much in common, but Laurent said potash is not a compound of oxide of potassium and water, it is rather a derivative of water. The molecule of potash is derived from that of water by replacing one atom of hydrogen in the latter by one atom of potassium; water and potash belong to the same type. Thus there was constituted _the water type_. Light was at once thrown on many facts in organic chemistry. The analogies between alcohol and water, some of which were first pointed out by Graham (see p. 235), seemed to follow as a necessary consequence when the molecule of alcohol was regarded as built on the water type. In place of two atoms of hydrogen combined with one of oxygen, there was in the alcohol molecule one atom of the compound radicle _ethyl_ (itself composed of carbon and hydrogen), one atom of oxygen and one of hydrogen. Alcohol was water with one hydrogen atom substituted by one ethyl atom; the hydrogen atom was the atom of what we call an element, the ethyl was the atom of what we call a compound radicle. Gerhardt sought to refer all organic compounds to one or other of three types--the water type, the hydrochloric acid type, and the ammonia type. As new compounds were prepared and examined, other types had to be introduced. To follow the history of this conception would lead us into too many details; suffice it to say that the theory of types was gradually merged in the wider theory of equivalency, about which I shall have a little to say in the next chapter. One result of the introduction of types into chemical science, associated as it was with the unitary view of compound radicles, was to overthrow that definition of organic chemistry which had for some time prevailed, and which stated that organic chemistry is "the chemistry of compound radicles." Compound radicles, it is true, were more used in explaining the composition and properties of substances obtained from animals and vegetables than of mineral substances, but a definition of one branch of a science which practically included the other branch, from which the first was to be defined, could not be retained. Chemists became gradually convinced that a definition of organic chemistry was not required; that there was no distinction between so-called organic and inorganic compounds; and they have consented, but I scarcely think will much longer consent, to retain the terms "organic" and "inorganic," only because these terms have been so long in use. The known compounds of the element carbon are so numerous, and they have been so much studied and so well classified, that it has become more convenient for the student of chemistry to consider them as a group, to a great extent apart from the compounds of the other elements; to this group he still often gives the name of "organic compounds." * * * * * Liebig continued to hold the chair of Chemistry in the University of Giessen until the year 1852, when he was induced by the King of Bavaria to accept the professorship of the same science in the University of Munich. During the second quarter of this century Giessen was much resorted to by students of chemistry from all parts of the world, more especially from England. Many men who afterwards made their mark in chemical discovery worked under the guidance of the professor of Stockholm, but Giessen has the honour of being the place where a well-appointed chemical laboratory for scientific research was first started as a distinctly educational institution. The fame of Liebig as a discoverer and as a teacher soon filled the new institution with students, who were stirred to enthusiasm as they listened to his lectures, or saw him at work in his laboratory. "Liebig was not exactly what is called a fluent speaker," says Professor Hofmann, of Berlin, "but there was an earnestness, an enthusiasm in all he said, which irresistibly carried away the hearer. Nor was it so much the actual knowledge he imparted which produced this effect, as the wonderful manner in which he called forth the reflective powers of even the least gifted of his pupils. And what a boon was it, after having been stifled by an oppressive load of facts, to drink the pure breath of science such as it flowed from Liebig's lips! what a delight, after having perhaps received from others a sack full of dry leaves, suddenly in Liebig's lectures to see the living, growing tree!... We felt then, we feel still, and never while we live shall we forget, Liebig's marvellous influence over us; and if anything could be more astonishing than the amount of work he did with his own hands, it was probably the mountain of chemical toil which he got us to go through. Each word of his carried instruction, every intonation of his voice bespoke regard; his approval was a mark of honour, and of whatever else we might be proud, our greatest pride of all was having him for our master.... Of our young winnings in the noble playground of philosophical honour, more than half were free gifts to us from Liebig, and to his generous nature no triumphs of his own brought more sincere delight than that which he took in seeing his pupils' success, and in assisting, while he watched, their upward struggle." Liebig had many friends in England. He frequently visited this country, and was present at several meetings of the British Association. At the meeting of 1837 he was asked to draw up a report on the progress of organic chemistry; he complied, and in 1840 presented the world with a book which marks a distinct epoch in the applications of science to industrial pursuits--"Chemistry in its Applications to Agriculture and Physiology." In this book, and in his subsequent researches and works,[14] Liebig established and enforced the necessity which exists for returning to the soil the nourishing materials which are taken from it by the growth of crops; he suggested that manure rich in the salts which are needed by plants might be artificially manufactured, and by doing this he laid the foundation of a vast industry which has arisen during the last two decades. He strongly and successfully attacked the conception which prevailed among most students of physiology at that time, that chemical and physical generalizations could not be applied to explain the phenomena presented by the growth of living organisms. He was among the first to establish, as an induction from the results of many and varied experiments, the canon which has since guided all teachers of the science of life, that a true knowledge of biology must be based on a knowledge of chemistry and physics. But Liebig was not content to establish broad generalizations and to leave the working out of them to others; he descended from the heights of philosophical inquiry, and taught the housewife to make soup wherein the greatest amount of nourishment was conveyed to the invalid in the most easily digestible form; and has he not, by bringing within the reach of every one a portion of the animal nourishment which else had run to waste in the pampas of South America or the sheep-runs of Australia, made his name, in every English home, familiar as a household word? On the death of Berzelius in 1848, it was to Liebig that every chemist looked for a continuation of the annual Report on the progress of chemistry, which had now become the central magazine of facts, whither each worker in the science could resort to make himself acquainted with what had been done by others on any subject which he proposed to investigate. From that time to the present day Liebig's _Annalen_ has been the leading chemical journal of the world. Of the other literary work of Liebig--of his essays, his celebrated "Chemical Letters," his many reports, his severe and sometimes harsh criticisms of the work of others--of the details of the three hundred original papers wherein he embodied the results of his researches, I have not time, nor would this be the place, to speak. Honoured by every scientific society of any note in the world, crowned with the highest reward which England and France can offer to the man of science who is not an Englishman or a Frenchman--the Copley Medal and the associateship of the Institute--honoured and respected by every student of science, loved by each of the band of ardent natures whom he had trained and sent forth to battle for the good of their race, and, best of all, working himself to the last in explaining the wonders of Nature, he "passed into the silent land" on the 18th of April 1873, leaving the memory of a life nobly devoted to the service of humanity, and the imperishable record of many truths added to the common stock of the race. * * * * * The life-work of Dumas, other than that which I have already sketched, is so manifold and so varied, that to do more than refer to one or two leading points would carry us far beyond the limits within which I have tried to keep throughout this book. In one of his earliest papers Dumas adopted the atomic theory as the corner-stone of his chemical system; he was thus led to an experimental revision of the values generally accepted for the atomic weights of some of the elements. Among these revisions, that of the atomic weight of carbon holds a most important place, partly because of the excellency of the work, but more because of the other inquiries to which this work gave rise. Dumas's experiments were summed up in the statement that the atom of carbon is twelve times heavier than the atom of hydrogen. The experimental methods and the calculations used in this determination involved a knowledge of the atomic weight of oxygen; in order accurately to determine the value to be assigned to this constant, Dumas, in conjunction with Boussingault, undertook a series of experiments on the synthesis of water, which forms one of the classical researches of chemistry, and wherein the number 16 was established as representing the atomic weight of oxygen. Stas, from experiments conducted at a later time with the utmost care and under conditions eminently fitted to gain accurate results, obtained the number 15·96, in place of 16, for the atomic weight of oxygen; but in a paper recently published by the veteran Dumas, a source of error is pointed out which Stas had overlooked in his experiments, and it is shown that this error would tend slightly to increase the number obtained by Stas. As the values assigned to the atomic weights of the elements are the very fundamental data of chemistry, and as we are every day more clearly perceiving that the mutual relations between the properties of elements and compounds are closely connected with the relative weights of the elementary atoms, we can scarcely lay too much stress on such work as this done by Dumas and Stas. Not many years after the publication of Dalton's "New System," the hypothesis was suggested by Prout that the atomic weights of all the elements are represented by whole numbers--that of hydrogen being taken as unity--that the atom of each element is probably formed by the putting together of two, three, four, or more atoms of hydrogen, and that consequently there exists but a single elementary form of matter. Among the upholders of this hypothesis Dumas has held an important place. He modified the original statement of Prout, and suggested that all atomic weights are whole multiples of half of that of hydrogen (that is, are whole multiples of 1/2). The experiments of Stas seemed to negative this view, but later work--more especially the important critical revision of the results obtained by all the most trustworthy workers, conducted by Professor Clarke of Cincinnati, and published by the Smithsonian Institution as part of their series of "Constants of Nature"--has shown that we are in no wise warranted by facts in rejecting Prout's hypothesis as modified by Dumas, but that the balance of evidence is at present rather in its favour. It would be altogether out of place to discuss here an hypothesis which leads to some of the most abstruse speculations as to the nature of matter in which chemists have as yet ventured to indulge. I mention it only because it illustrates the far-reaching nature of the researches of the chemist whose work we are now considering, and also because it shows the shallowness of the scoffs in which some partly educated people indulge when they see scientific men occupying themselves for years with attempts to solve such a minute and, as they say, trivial question as whether the number 15·96 or the number 16 is to be preferred as representing the atomic weight of oxygen; "for in every speck of dust that falls lie hid the laws of the universe, and there is not an hour that passes in which you do not hold the infinite in your hand." Another and very different subject, which has been placed on a firm basis by the researches of Dumas, is the chemistry of fermentation. By his work on the action of beer-yeast on saccharine liquids, Dumas proved Liebig's view to be untenable--according to which the conversion of sugar into alcohol is brought about by the influence of chemical changes proceeding in the ferment; also that the view of Berzelius, who regarded alcoholic fermentation as due simply to the contact of the ferment with the sugar, was opposed to many facts; and lastly, Dumas showed that the facts were best explained by the view which regarded the change of sugar into alcohol as in no way different from other purely chemical changes, but as a change brought about, so far as our present knowledge goes, only by the agency of a growing organism of low form, such as yeast. In 1832 Dumas established at his own expense a laboratory for chemical research. When the Revolution of 1848 broke out Dumas's means were much diminished, and he could no longer afford to maintain his laboratory. The closing of this place, where so much sound work had been done, was generally regarded as a calamity to science. About this time Dumas received a visit from a person of unprepossessing appearance, who accosted him thus: "They assert that you have shut up your laboratory, but you have no right to do so. If you are in need of money, there," throwing a roll of bank-notes on the table, "take what you want. Do not stint yourself; I am rich, a bachelor, and have but a short time to live." Dumas's visitor turned out to be Dr. Jecker. He assured Dumas that he was now only paying a debt, since he had made a fortune by what he had learnt in the medical schools of Paris. Dumas could not however in those troublous times turn his mind continuously to experimental research, and therefore declined Dr. Jecker's offer with many protestations of good will and esteem. New work now began to press upon Dumas; his energy and his administrative powers were demanded by the State. Elected a member of the National Assembly in 1848, he was soon called by the President of the Republic to office as Minister of Agriculture and Commerce. He was made a senator under the second empire. He entered the municipal council of Paris about 1854, and was soon elected to the presidency. Under his presidency the great scheme for providing Paris with spring-water carried by aqueducts and tunnels was successfully accomplished; many improvements were made in the drainage of the city; the cost of gas was decreased, while the quality was improved, the constancy of the supply insured, and the appliances for burning the gas in the streets were altered and rendered more effective. Nominated to succeed Pelouze as Master of the Mint in 1868, Dumas held this honourable and important position only until the Franco-German war of 1870. Since that date he has relinquished political life; but as Permanent Secretary of the Academy Dumas now fills the foremost place in all affairs connected with science, whether pure or applied, in the French capital. In the work of these two chemists, Liebig and Dumas, we find admirable illustrations of the scientific method of examining natural appearances. In the broad general views which they both take of the phenomena to be studied, and the patient and persevering working out of details, we have shown us the combination of powers which are generally found in separate individuals. Dumas has always insisted on the need of comparing properties and reactions of groups of bodies, before any just knowledge can be gained as to the position of a single substance in the series studied by the chemist. It has been his aim as a teacher, we are assured by his friend, Professor Hofmann, never to present to his students "an isolated phenomenon, or a notion not logically linked with others." To him each chemical compound is one in a series which connects it directly with many other similar compounds, and indirectly with other more or less dissimilar compounds. Amid the overwhelming mass of facts which threaten nowadays to bury the science of chemistry, and crush the life out of it by their weight, Dumas tracks his way by the aid of general principles; but these principles are themselves generalized from the facts, and are not the offspring of his own fancy. We have, I think, found that throughout the progress of chemical science two dangers have beset the student. He has been often tempted to accumulate facts, to amass analytical details, to forget that he is a chemist in his desire to perfect the instrument of analysis by the use of which he raises the scaffolding of his science; on the other hand, he has been sometimes allured from the path of experiment by his own day-dreams. The discoveries of science have been so wonderful, and the conceptions of some of those who have successfully prosecuted science have been so grand, that the student has not unfrequently been tempted to rest in the prevailing theories of the day, and, forgetting that these ought only "to afford peaceful lodgings to the intellect for the time," he has rather allowed them to circumscribe it, until at last the mind "finds difficulty in breaking down the walls of what has become its prison, instead of its home." We may think that Dumas fell perhaps slightly into the former of these errors, when he did not allow his imagination a little more scope in dealing with the conception of "atom" and "molecule," the difference between which he had apprehended but not sufficiently marked by the year 1826 (see p. 261). We know, from his own testimony, that Liebig once fell into the latter error and that the consequences were disastrous. "I know a chemist"--meaning himself--"who ... undertook an investigation of the liquor from the salt-works. He found iodine in it, and observed, moreover, that the iodide of starch turned a fiery yellow by standing over-night. The phenomenon struck him; he saturated a large quantity of the liquor with chlorine, and obtained from this, by distillation, a considerable quantity of a liquid which coloured starch yellow, and externally resembled chloride of iodine, but differed from this compound in many properties. He explained, however, every discrepancy with satisfaction to himself; he contrived for himself a theory. Several months later, he received a paper of M. Balard's," announcing the discovery of bromine, "and on that same day he was able to publish the results of experiments on the behaviour of bromine with iron, platinum, and carbon; for Balard's bromine stood in his laboratory, labelled _liquid chloride of iodine_. Since that time he makes no more theories unless they are supported and confirmed by trustworthy experiments; and I can positively assert that he has not fared badly by so doing." Another point which we notice in the life-work of these two chemists is their untiring labour. They were always at work; wherever they might be, they were ready to notice passing events or natural phenomena, and to draw suggestions from these. As Davy proved the elementary character of iodine and established many of the properties of this substance during a visit to Paris, so we find Dumas making many discoveries during brief visits paid to his friends' laboratories when on excursions away from Paris. During a visit to Aix-les-Bains, he noticed that the walls of the bath-room were covered with small crystals of sulphate of lime. The waters of the bath, he knew, were charged with sulphuretted hydrogen, but they contained no sulphuric acid, nor could that acid be detected in the air of the bath-rooms. This observation was followed up by experiments which proved that a porous material, such as a curtain or an ordinary plastered wall, is able to bring about the union of oxygen with sulphuretted hydrogen, provided moisture be present and a somewhat high temperature be maintained. Again, we find Liebig and Dumas characterized by great mental honesty. "There is no harm in a man committing mistakes," said Liebig, "but great harm indeed in his committing none, for he is sure not to have worked.... An error you have become cognizant of, do not keep in your house from night till morning." Students of science, more than any other men, ought to be ready to acknowledge and correct the errors into which they fall. It is not difficult for them to do this: they have only to be continually going to Nature; for there they have a court of appeal always ready to hear their case, and to give an absolutely unbiased judgment: they have but to bring their theories and guesses to this judge to have them appraised at their true value. FOOTNOTES: [13] "In reviewing once more the facts elicited by our inquiry, we find them arranged around a common centre, a group of atoms preserving intact its nature, amid the most varied associations with other elements. This stability, this analogy, pervading all the phenomena, has induced us to consider this group as a sort of compound element, and to designate it by the special name of _benzoyl_."--Liebig and Wöhler, 1832. [14] "Animal Chemistry, or Chemistry in its Applications to Physiology and Pathology," 1842. "Researches on the Chemistry of Food," 1847. "The Natural Laws of Husbandry," 1862. CHAPTER VII. MODERN CHEMISTRY. On p. 162 I referred to the work of the German chemist Richter, by which the _equivalents_ of certain acids and bases were established. Those quantities of various acids which severally neutralized one and the same quantity of a given base, or those quantities of various bases which severally neutralized one and the same quantity of a given acid, were said to be equivalent. These were the quantities capable of performing a certain definite action. In considering the development of Dumas's substitution theory, we found that Laurent retained this conception of equivalency when he spoke of an equivalent of hydrogen being replaced by an equivalent of chlorine (see p. 272). A certain weight of chlorine was able to take the place and play the part of a certain weight of hydrogen in a compound; these weights, of hydrogen and chlorine, were therefore equivalent. This conception has been much used since Laurent's time, but it has for the most part been applied to the atoms of the elements. Hydrogen being taken as the standard substance, the elements have been divided into groups, in accordance with the number of hydrogen atoms with which one atom of each element is found to combine. Thus certain elements combine with hydrogen only in the proportion of one atom with one atom; others combine in the proportion of one atom with two atoms of hydrogen; others in the proportion of one atom with three atoms of hydrogen, and so on. The adjective _monovalent_, _divalent_, _trivalent_, etc., is prefixed to an element to denote that the atom of this element combines with one, or two, or three, etc., atoms of hydrogen to form a compound molecule. Let us consider what is implied in this statement--"The nitrogen atom is trivalent." This statement, if amplified, would run thus: "One atom of nitrogen combines with three atoms of hydrogen to form a compound molecule." Now, this implies (1) that the atomic weight of nitrogen is known, and (2) that the molecular weight, and the number of nitrogen and hydrogen atoms in the molecule, of a compound of nitrogen and hydrogen are also known. But before the atomic weight of an element can be determined, it is necessary (as we found on p. 146) to obtain, analyze, and take the specific gravities of a series of gaseous compounds of that element. The smallest amount of the element (referred to hydrogen as unity) in the molecule of any one of these gases will then be the atomic weight of the element. When it is said that "the molecular weight, and the number of nitrogen and hydrogen atoms in the molecule, of a compound of nitrogen and hydrogen are known," the statement implies that the compound in question has been obtained in a pure state, has been analyzed carefully, has been gasefied, and that a known volume of the gas has been weighed. When therefore we say that "the nitrogen atom is trivalent," we sum up a large amount of knowledge which has been gained by laborious experiment. This classification of the elements into groups of equivalent atoms--which we owe to Frankland, Williamson, Odling, and especially to Kekulé--has been of much service especially in advancing the systematic study of the compounds of carbon. It helps to render more precise the conception which has so long been gaining ground of the molecule as a definite structure. A monovalent element is regarded as one the atom of which acts on and is acted on by only one atom of hydrogen in a molecule; a divalent as one, the atom of which acts on and is acted on by two atoms of hydrogen--or other monovalent element--in a molecule; a trivalent element as one, the atom of which acts on and is acted on by three atoms of hydrogen--or other monovalent element--in a molecule; and so on. The fact that there often exist several compounds of carbon, the molecules of which are composed of the same numbers of the same atoms, finds a partial explanation by the aid of this conception of the elementary atom as a little particle of matter capable of binding to itself a certain limited number of other atoms to form a compound molecule. For if the observed properties of a compound are associated with a certain definite arrangement of the elementary atoms within the molecules of that compound, it would seem that any alteration in this arrangement ought to be accompanied by an alteration in the properties of the compound; in other words, the existence of more than one compound of the same elements united in the same proportions becomes possible and probable. I have said that such compounds exist: let me give a few examples. The alchemists poured a stream of mercury on to molten sulphur, and obtained a black substance, which was changed by heat into a brilliantly red-coloured body. We now know that the black and the red compounds alike contain only mercury and sulphur, and contain these elements united in the same proportions. Hydrogen, carbon, nitrogen and oxygen unite in certain proportions to produce a mobile, colourless, strongly acid liquid, which acts violently on the skin, causing blisters and producing great pain: if this liquid is allowed to stand for a little time in the air it becomes turbid, begins to boil, gets thicker, and at last explodes, throwing a white pasty substance about in all directions. This white solid is inodorous, is scarcely acid to the taste, and does not affect the skin; yet it contains the same elements, united in the same proportions, as were present in the strongly acid, limpid liquid from which it was produced. Two substances are known each containing carbon and hydrogen united in the same proportions: one is a gas with strong and irritating odour, and exerting a most disagreeable action on the eyes; the other is a clear, limpid, pleasant-smelling liquid. Phosphorus is a very poisonous substance: it readily takes fire in the air at ordinary temperatures, so that it must be kept under water; but a modification of phosphorus is known, containing no form of matter other than phosphorus, which is non-poisonous, does not take fire easily, and may be handled with safety. Once more, there is a compound of nitrogen and oxygen which presents the appearance of a deep-red, almost black gas; there is also a compound of nitrogen and oxygen which is a clear, colourless gas; yet both contain the same elements united in the same proportions. But a detailed consideration of _isomerism_, _i.e._ the existence of more than one compound built up of the same amounts of the same elements yet possessing different properties, would lead us too far from the main path of chemical advance which we wish to trace. The chemist is to-day continually seeking to connect the properties of the bodies he studies with the molecular structures of these bodies; the former he can observe, a knowledge of the latter he must gain by reasoning on the results of operations and experiments. His guide--the guide of Lavoisier and his successors--is this: "Similarity of properties is associated with similarity of composition"--by "composition" he generally means molecular composition. Many facts have been amassed of late years which illustrate the general statement that the properties of bodies are connected with the composition of those bodies. Thus a distinct connection has been traced between the tinctorial power and the molecular composition of certain dye-stuffs; in some cases it has even become possible to predict how a good dye-stuff may be made--to say that, inasmuch as this or that chemical reaction will probably give rise to the production of this or that compound, the atoms in the molecule of which we believe to have a certain arrangement relatively to one another, so this reaction or that will probably produce a dye possessed of strong tinctorial powers. The compound to the presence of which madder chiefly owes its dyeing powers is called _alizarine_; to determine the nature of the molecular structure of this compound was, for many years, the object of the researches of chemists; at last, thanks especially to the painstaking zeal of two German chemists, it became fairly clear that alizarine and a compound of carbon and hydrogen, called _anthracene_, were closely related in structure. Anthracene was obtained from alizarine, and, after much labour, alizarine was prepared from anthracene. Anthracene is contained in large quantities in the thick pitch which remains when coal-tar is distilled; this pitch was formerly of little or no value, but as soon as the chemical manufacturer found that in this black objectionable mass there lay hidden enormous stores of alizarine, he no longer threw away his coal-tar pitch, but sold it to the alizarine manufacturer for a large sum. Thus it has come to pass that little or no madder is now cultivated; madder-dyeing is now done by means of alizarine made from coal-tar: large tracts of ground, formerly used for growing the madder plant, are thus set free for the growth of wheat and other cereals. This discovery of a method for preparing alizarine artificially stimulated chemists to make researches into the chemical composition, and if possible to get to know something about the molecular structure of indigo. Those researches have very recently resulted in the knowledge of a series of reactions whereby this highly valuable and costly dye-stuff may be prepared from certain carbon compounds which, like anthracene, are found in coal-tar. These examples, while illustrating the connection that exists between the composition and the properties of bodies, also illustrate the need there is for giving a scientific chemical training to the man who is to devote his life to chemical manufactures. Pure and applied science are closely connected; he who would succeed well in the latter must have a competent and a practical knowledge of the former. That composition--molecular composition--and properties are closely related is generally assumed, almost as an axiom, in chemical researches nowadays. Lavoisier defined acids as substances containing oxygen; Davy regarded an acid as a compound the properties of which were conditioned by the nature and by the arrangement of all the elements which it contained; Liebig spoke of acids as substances containing "replaceable" hydrogen; the student of the chemistry of the carbon compounds now recognizes in an organic acid a compound containing hydrogen, but also carbon and oxygen, and he thinks that the atoms of hydrogen (or some of these atoms) in the molecule of such a compound are, in some way, closely related to atoms of oxygen and less closely to atoms of carbon, within that molecule,--in other words, the chemist now recognizes that, for carbon compounds at any rate, acids are acid not only because they contain hydrogen, but also because that hydrogen is related in a definite manner within the molecule to other elementary atoms; he recognizes that the acid or non-acid properties of a compound are conditioned, not only by the nature of the elements which together form that compound, but also by the arrangement of these elements. Davy's view of the nature of acids is thus confirmed and at the same time rendered more definite by the results of recent researches. The physical student is content to go no further than the molecule; the properties of bodies which he studies are regarded, for the most part, as depending on the size, the nature, and perhaps the grouping together of molecules. But the chemist seeks to go deeper than this. The molecule is too large a piece of matter for him; the properties which he studies are conceived by him to be principally conditioned by the nature, the number, and the arrangement of the parts of the molecule--of the atoms which together build up the molecule. In these elementary atoms he has, for the present, found the materials of which the heavens and the earth are made; but facts are being slowly gained which render it probable that these atoms are themselves structures--that they are built up of yet smaller parts, of yet simpler kinds of matter. To gather evidence for or against this supposition, the chemist has been obliged to go from the earth to the heavens, he has been obliged to form a new science, the science of spectroscopic analysis. This subject has been considered in "The Astronomers," belonging to this series of books; but the point of view from which the matter is there regarded is astronomical rather than chemical. I should like briefly to recall to the reader the fundamental facts of this branch of science. [Illustration: Fig. 4.] When a ray of light is allowed to pass through a glass prism and then fall on to a white surface, the image produced on this surface consists of a many-coloured band of light. The blue or violet part of this band is more bent away from the plane of the entering ray than the orange part, and the latter more than the red part of the band. This is roughly represented in Fig. 4, where _r_ is the ray of light passing through the prism P, and emerging as a sevenfold band of coloured lights, of which the violet, V, is most, and the red band, R, is least bent away from the plane of the ray _r_. If the surface--say a white screen--on which the many-coloured band of light, or _spectrum_, falls, is punctured by a small hole, so as to admit the passage of the violet, or blue, or orange, or red light only, and if this violet, etc., light is then passed through a second prism, no further breaking up of that light takes place. This state of matters is represented in the part of the figure towards the right hand, where the red ray, R, is shown as passing through the screen, and falling on to a second prism, P': the red ray is slightly bent out of its direct course, but is not subdivided; it falls on the second screen as a ray of red light, R'. But if a quantity of the metal sodium is vaporized in a hot non-luminous flame, and if the yellow light thus produced is passed through a prism, a spectrum is obtained consisting of a single yellow line (on a dark background), situated on that part of the screen where the orange-yellow band occurred when the ray of sunlight was split up by the action of the prism. In Fig. 5 the yellow light from a flame containing sodium is represented by the line Y. The light emitted by the glowing sodium vapour is said to be _monochromatic_. [Illustration: Fig. 5] Lastly, if the experiment is arranged so that a ray of sunlight or of light from an electric lamp passes through a layer of comparatively cool sodium vapour before reaching the prism, a spectrum is produced corresponding to the solar spectrum except that a black line appears in the position where the yellow line, characteristic of sodium, was noticed in the second experiment. [Illustration: Fig. 6.] Fig. 6 represents the result of this experiment: the ray of sunlight or electric light, _r_, passes through a quantity of sodium vapour, and is then decomposed by the prism; the spectrum produced is marked by the absence of light (or by a dark line) where the yellow line, Y, was before noticed. These are the fundamental facts of spectroscopic analysis: sunlight is decomposable into a band of many colours, that is, into a spectrum; light emitted by a glowing vapour is characterized by the presence of coloured lines, each of which occupies a definite position with reference to the various parts of the solar spectrum; sunlight--or the electric light--when allowed to pass through a mass of vapour, furnishes a spectrum characterized by the absence of those bright lines, the presence of which marked the spectrum of the light obtained by strongly heating the vapour through which the sunlight has passed. The spectrum obtained by decomposing the light emitted by glowing vapour of potassium is characterized by the presence of certain lines--call them A and B lines. We are asked what element (or elements) is present in a certain gas presented to us: we pass a beam of white light through this gas and then through a prism, and we obtain a continuous spectrum (_i.e._ a spectrum of many colours like the solar spectrum) with two dark lines in the same positions as those occupied by the lines A and B. We therefore conclude that the gas in question contains vapour of potassium. The solar spectrum, when carefully examined, is found to be crossed by a very large number of fine black lines; the exact positions of many hundreds of these lines have been carefully determined, and, in most cases, they are found to correspond to the positions of various bright lines noticed in the spectra of the lights emitted by hot vapours of various elementary bodies. Assume that the sun consists, broadly speaking, of an intensely hot and luminous central mass, formed to a large extent of the elementary substances which build up this earth, and that this central mass is surrounded by a cooler (but yet very hot) gaseous envelope of the same elements,--and we have a tolerably satisfactory explanation of the principal phenomena revealed by the spectroscopic study of the sun's light. On this assumption the central mass of glowing iron, chromium, magnesium, nickel, cobalt, hydrogen, etc., is sending out light; a portion of the light emitted by the glowing iron is quenched as it passes through a cloud of cooler iron vapour outside the central mass, a portion of the light emitted by the glowing chromium is quenched as it passes through a cloud of cooler chromium vapour, and so on; the black lines in the spectrum are the records of these various quenchings of this and that light. So far then the study of the solar spectrum appears to be tolerably simple, and this study generally confirms the proposition that the material of which the sun is composed is, broadly, identical with those forms of matter which we, on this earth, call the chemical elements. But whatever be the composition of the sun, it is, I think, evident that in dealing with a ray of light coming therefrom, we are dealing with a very complex phenomenon. According to the hypothesis which is now guiding us, the solar light which passes into our spectroscope has probably had its beginning in some central part of the sun, and has passed through very thick layers of hot metallic clouds, agitated perhaps by solar cyclones. Could we examine the light coming from some defined part of the sun, we should probably obtain valuable information. During a solar eclipse red prominences are seen projecting beyond the dark shadow of the moon, which covers the sun's disc. Analysis of the light emitted by these prominences has shown that they are phenomena essentially belonging to the sun itself, and that they consist of vast masses of intensely hot, glowing gaseous substances, among which hydrogen is present in large quantities. That these prominences are very hot, hotter than the average temperature of the ordinary solar atmosphere, is proved by the fact that the spectrum of the light coming from them is characterized by bright lines. By special arrangements which need not be discussed here, but which have been partly explained in "The Astronomers" (see pp. 334, 335 of that book), it has been shown that these prominences are in rapid motion: at one moment they shoot up to heights of many thousand miles, at another they recede towards the centre of the sun. We thus arrive at a picture of the solar atmosphere as consisting of layers of very hot gases, which are continually changing their relative positions and forms; sometimes ejections of intensely hot, glowing gases occur,--we call these prominences; sometimes down-rushes of gaseous matter occur,--we call these spots. Among the substances which compose the gaseous layers we recognize hydrogen, iron, magnesium, sodium, nickel, chromium, etc., but we also find substances which can at present be distinguished only by means of the wave-lengths of the light which they emit; thus we have 1474 stuff, 5017 stuff, 5369 stuff, etc. Let us now turn to another part of this subject. By a special arrangement of apparatus it is possible to observe the spectrum of the light emitted by a glowing vapour, parts of which are hotter than other parts, and to compare the lines in the spectrum of the light coming from the hottest parts with the lines in the spectrum of the light coming from the cooler parts of the vapour. If this is done for sodium vapour, certain lines are apparent in all the spectra, others only in the spectrum of the light coming from the hottest parts of the sodium vapour: the former lines are called "long lines," the latter "short lines." A rough representation of the long and short lines of sodium is given in Fig. 7. [Illustration: Fig. 7.--Long and short lines of sodium.] Now, suppose that the lines in the spectrum of the light emitted by glowing manganese vapour have been carefully mapped, and classed as long and short lines: suppose that the same thing has been done for the iron lines: now let a little manganese be mixed with much iron, let the mixture be vaporized, and let the light which is emitted be decomposed by the prism of a spectroscope, it will be found that the long lines of manganese alone make their appearance; let a little more manganese be added to the mixture, and now some of the shorter lines due to manganese begin to appear in the spectrum. Hence it has been concluded by Lockyer that if the spectrum of the light emitted by the glowing vapour of any element--call it A--is free from the long lines of any other element--say element B--this second element is not present as an impurity in the specimen of element A which is being examined. Lockyer has applied this conclusion to "purify" various elementary spectra. The spectrum of element A is carefully mapped, and the lines are divided into long and short lines, according as they are noticed in the spectrum of the light coming from all parts of the glowing vapour of A, or only in the spectrum of the light which comes from the hotter parts of that vapour. The spectra of elements B and C are similarly mapped and classified: then the three spectra are compared; the longest line in the spectrum of B is noted, if this line is found in the spectrum of A, it is marked with a negative sign--this means that so far as the evidence of this line goes B is present as an impurity in A; the next longest B line is searched for in the spectrum of A--if present it also is marked with a negative sign; a similar process of comparison and elimination is conducted with the spectra of A and C. In this way a "purified" spectrum of the light from A is obtained--a spectrum, that is, from which, according to Lockyer, all lines due to the presence of small quantities of B and C as impurities in A have been eliminated. [Illustration: Fig. 8.] Fig. 8 is given in order to make this "purifying" process more clearly understood. But when this process has been completed there remain, in many cases, a few short lines common to two or more elementary spectra: such lines are called by Lockyer _basic lines_. He supposes that these lines are due to light emitted by forms of matter simpler than our elements; he thinks that at very high temperatures some of the elements are decomposed, and that the _bases_ of these elements are produced and give out light, which light is analyzed by the spectroscope. Such short basic lines are marked in the spectra represented in Fig. 8 with a positive sign. Now, if the assumption made by Lockyer be admitted, viz. that the short lines, or some of the short lines, which are coincident in the "purified" spectra of various elements, are really due to light emitted by forms of matter into which our so-called elements are decomposed at very high temperatures, it follows that such lines should become more prominent in the spectra of the light emitted by elements the higher the temperature to which these elements are raised. But we know (see p. 308) that the prominences around the sun's disc are hotter than the average temperature of the solar atmosphere; hence the spectrum of the light coming from these prominences ought to be specially rich in "basic" lines: this supposition is confirmed by experiment. Lockyer has also shown that it is the "basic," and not the long lines, which are especially affected in the spectra of light coming from those parts of the solar atmosphere which are subjected to the action of cyclones, _i.e._ which are at abnormally high temperatures. And finally, a very marked analogy has been established between the changes in the spectrum of the light emitted by a compound substance as the temperature is raised, and the substance is gradually decomposed into its elements, and the spectrum of the light emitted by a so-called elementary substance as the temperature of that substance is increased. But it may be urged that Lockyer's method of "purifying" a spectrum is not satisfactory; that, although all the longer lines common to two spectra are eliminated, the coincident short lines which remain are due simply to very minute quantities of one element present as an impurity in the larger quantity of the other. Further, it has been shown that several of the so-called "basic" lines are resolved, by spectroscopes of great dispersive power, into groups of two or more lines, which lines are not coincident in different spectra. And moreover it is possible to give a fairly satisfactory explanation of the phenomena of solar chemistry without the aid of the hypothesis that our elements are decomposed in the sun into simpler forms of matter. Nevertheless this hypothesis has a certain amount of experimental evidence in its favour; it may be a true hypothesis. I do not think we are justified at present either in accepting it as the best guide to further research, or in wholly rejecting it. The researches to which this hypothesis has given rise have certainly thrown much light on the constitution of the sun and stars, and they have also been instrumental in forcing new views regarding the nature of the elements on the attention of chemists, and so of awakening them out of the slumber into which every class of men is so ready to fall. The tale told by the rays of light which travel to this earth from the sun and stars has not yet been fully read, but the parts which the chemist has spelt out seem to say that, although the forms of matter of which the earth is made are also those which compose the sun and stars, yet in the sun and stars some of the earthly elements are decomposed, and some of the earthly atoms are split into simpler forms. The tale, I say, told by the rays of light seems to bear this interpretation, but it is written in a language strange to the children of this earth, who can read it as yet but slowly; for the name given to the new science was "_Ge-Urania_, because its production was of earth and heaven. And it could not taste of death, by reason of its adoption into immortal palaces; but it was to know weakness, and reliance, and the shadow of human imbecility; and it went with a lame gait; but in its going it exceeded all mortal children in grace and swiftness." There are certain little particles so minute that at least sixty millions of them are required to compose the smallest portion of matter which can be seen by the help of a good microscope. Some of these particles are vibrating around the edge of an orb a million times larger than the earth, but at a distance of about ninety millions of miles away. The student of science is told to search around the edge of the orb till he finds these particles, and having found them, to measure the rates of their vibrations; and as an instrument with which to do this he is given--a glass prism! But he has accomplished the task; he has found the minute particles, and he has measured their vibration-periods. Chemistry is no longer confined to this earth: the chemist claims the visible universe as his laboratory, and the sunbeams as his servants. Davy decomposed soda and potash by using the powerful instrument given him by Volta; but the chemist to-day has thrown the element he is seeking to decompose into a crucible, which is a sun or a star, and awaits the result. The alchemists were right. There is a philosopher's stone; but that stone is itself a compound of labour, perseverance, and genius, and the gold which it produces is the gold of true knowledge, which shall never grow dim or fade away. CHAPTER VIII. SUMMARY AND CONCLUSION. We have thus traced some of the main paths along which Chemistry has advanced since the day when, ceasing to be guided by the dreams of men who toiled with but a single idea in the midst of a world of strange and complex phenomena, she began to recognize that Nature is complex but orderly, and so began to be a branch of true knowledge. In this review we have, I think, found that the remark made at the beginning of the introductory chapter is, on the whole, a just one. That the views of the alchemists, although sometimes very noble, were "vague and fanciful" is surely borne out by the quotations from their writings given in the first chapter. This period was followed by that wherein the accurate, but necessarily somewhat narrow conception of the Lavoisierian chemistry prevailed. Founded for the most part on the careful, painstaking, and quantitative study of one phenomenon--a very wide and far-reaching phenomenon, it is true--it was impossible that the classification introduced by the father of chemical science should be broad enough to include all the discoveries of those who came after him. But although this classification had of necessity to be revised and recast, the genius of Lavoisier enunciated certain truths which have remained the common possession of every chemical system. By proving that however the forms of matter may be changed the mass remains unaltered, he for the first time made a science of chemistry possible. He defined "element" once for all, and thus swept away the fabric of dreams raised by the alchemists on the visionary foundation of _earth_, _air_, _fire_ and _water_, or of _mercury_, _sulphur_ and _salt_. By his example, he taught that weighings and measurements must be made before accurate knowledge of chemical reactions can be hoped for; and by his teaching about oxygen being _the acidifier_--although we know that this teaching was erroneous in many details--he showed the possibility of a system of classification of chemical substances being founded on the actually observed properties and composition of those substances. Lavoisier gained these most important results by concentrating his attention on a few subjects of inquiry. That chemistry might become broad it was necessary that it should first of all become narrower. The period when the objects of the science were defined and some of its fundamental facts and conceptions were established, was succeeded, as we saw in our sketch, by that in which Dalton departed somewhat from the method of investigation adopted by most masters in science, and by concentrating his great mental powers on facts belonging to one branch of natural knowledge, elaborated a simple but very comprehensive theory, which he applied to explain the facts belonging to another branch of science. Chemistry was thus endowed with a grand and far-reaching conception, which has been developed and applied by successive generations of investigators: but we must not forget that it was the thorough, detailed work of Black and Lavoisier which made possible the great theory of Dalton. At the time when Dalton was thinking out his theory of atoms, Davy was advancing as a conqueror through the rich domain which the discovery of Volta had opened to chemistry. Dalton, trained to rely on himself, surrounded from his youth by an atmosphere in which "sweetness and light" did not predominate, thrown on the world at an early age, and obliged to support himself by the drudgery of teaching when he would fain have been engaged in research, and at the same time--if we may judge from his life as recorded by his biographers--without the sustaining presence of such an ideal as could support the emotional part of his nature during this time of struggle,--Dalton, we found, withdrew in great part from contact with other scientific workers, and communing only with himself, developed a theory which, while it showed him to be one in the chain of thinkers that begins in Democritus and Leucippus, was nevertheless stamped with the undeniable marks of his own individuality and genius, and at the same time was untouched by any of the hopes or fears, and unaffected by any of the passions, of our common humanity. Davy, on the other hand, was surrounded from childhood by scenes of great natural beauty and variety, by contact with which he was incited to eager desire for knowledge, while at the same time his emotions remained fresh and sensitive to outward impressions. Entering on the study of natural science when there was a pause in the march of discovery, but a pause presageful of fresh advances, he found outward circumstances singularly favourable to his success; seizing these favourable circumstances he made rapid advances. Like Lavoisier, he began his work by proving that there is no such thing in Nature as transmutation, in the alchemical meaning of the term; as Lavoisier had proved that water is not changed into earth, so did Davy prove that acid and alkali are not produced by the action of the electric current on pure water. We have shortly traced the development of the electro-chemical theory which Davy raised on the basis of experiment; we have seen how facts obliged him to doubt the accepted view of the composition of hydrochloric acid and chlorine, and how by the work he did on these subjects chemists have been finally convinced that an element is not a substance which _cannot be_, but a substance which _has not been_ decomposed, and how from this work has also arisen the modern theory of acids, bases and salts. We found that, by the labours of the great Swede J. J. Berzelius, the Daltonian theory was confirmed by a vast series of accurate analyses, and, in conjunction with a modification of the electro-chemical theory of Davy, was made the basis of a system of classification which endeavoured to include all chemical substances within its scope. The atom was the starting-point of the Berzelian system, but that chemist viewed the atom as a dual structure the parts of which held together by reason of their opposite electrical polarities. Berzelius, we saw, greatly improved the methods whereby atomic weights could be determined, and he recognized the importance of physical generalizations as aids in finding the atomic weights of chemical substances. But Berzelius came to believe too implicitly in his own view of Nature's working; his theory became too imperious. Chemists found it easier to accept than to doubt an interpretation of facts which was in great part undeniably true, and which formed a central luminous conception, shedding light on the whole mass of details which, without it, seemed confused and without meaning. If the dualistic stronghold was to be carried, the attack should be impetuous, and should be led by men, not only of valour, but also of discretion. We found that two champions appeared, and that, aided by others who were scarcely inferior soldiers to themselves, they made the attack, and made it with success. But when the heat of the battle was over and the bitterness of the strife forgotten, it was found that, although many pinnacles of the dualistic castle had been shattered, the foundation and great part of the walls remained; and, strange to say, the men who led the attack were content that these should remain. The atom could no longer be regarded as always composed of two parts, but must be looked on rather as one whole, the properties of which are defined by the properties and arrangements of all its parts; but the conception of the atom as a structure, and the assurance that something could be inferred regarding that structure from a knowledge of the reactions and general properties of the whole, remained when Dumas and Liebig had replaced the dualism of Berzelius by the unitary theory of modern chemistry; and these conceptions have remained to the present day, and are now ranked among the leading principles of chemical science; only we now speak of the "molecule" where Berzelius spoke of the "atom." Along with these advances made by Dumas, Liebig and others in rendering more accurate the general conception of atomic structure, we found that the recognition of the existence of more than one order of small particles was daily gaining ground in the minds of chemists. The distinction between what we now call atoms and molecules had been clearly stated by Avogadro in 1811; but the times were not ripe. The mental surroundings of the chemists of that age did not allow them fully to appreciate the work of Avogadro. The seed however was sown, and the harvest, although late, was plentiful. We saw that Dumas accepted, with some hesitation, the distinction drawn by Avogadro, but that failing to carry it to its legitimate conclusion, he did not reap the full benefit of his acceptance of the principle that the smallest particle of a substance which takes part in a physical change divides into smaller particles in those changes which we call chemical. To Gerhardt and Laurent we owe the full recognition, and acceptance as the foundation of chemical classification, of the atom as a particle of matter distinct from the molecule; they first distinctly placed the law of Avogadro--"Equal volumes of gases contain equal numbers of molecules"--in its true position as a law, which, resting on physical evidence and dynamical reasoning, is to be accepted by the chemist as the basis of his atomic theory. To the same chemists we are indebted for the formal introduction into chemical science of the conception of types, which, as we found, was developed by Frankland, Kekulé, and others, into the modern doctrine of equivalency of groups of elementary atoms. We saw that, in the use which he made of the laws of Mitscherlich, and of Dulong and Petit, Berzelius recognized the importance of the aid given by physical methods towards solving the atomic problems of chemistry; but among those who have most thoroughly availed themselves of such aids Graham must always hold a foremost place. Graham devoted the energies of his life to tracking the movements of atoms and molecules. He proved that gases pass through walls of solid materials, as they pass through spaces already occupied by other gases; and by measuring the rapidities of these movements he showed how it was possible to determine the rate of motion of a particle of gas so minute that a group of a hundred millions of them would be invisible to the unassisted vision. Graham followed the molecules as in their journeyings they came into contact with animal and vegetable membranes; he found that these membranes presented an insuperable barrier to the passage of some molecules, while others passed easily through. He thus arrived at a division of matter into colloidal and crystalloidal. He showed what important applications of this division might be made in practical chemistry, he discussed some of the bearings of this division on the general theory of the molecular constitution of matter, and thus he opened the way which leads into a new territory rich in promise to him who is able to follow the footsteps of its discoverer. Other investigators have followed on the general lines laid down by Graham; connections, more or less precise, have been established between chemical and physical properties of various groups of compounds. It has been shown that the boiling points, melting points, expansibilities by heat, amounts of heat evolved during combustion, in some cases tinctorial powers of dye-stuffs, and other physical constants of groups of compounds, vary with variations in the nature, number and arrangements of the atoms in the molecules of these compounds. But although much good work has been done in this direction, our ignorance far exceeds our knowledge regarding the phenomena which lie on the borderlands between chemistry and physics. It is probably here that chemists look most for fresh discoveries of importance. As each branch of natural science becomes more subdivided, and as the quantity of facts to be stored in the mind becomes daily more crushing, the student finds an ever-increasing difficulty in passing beyond the range of his own subject, and in gaining a broad view of the relative importance of the facts and the theories which to him appear so essential. In the days when the foundation of chemistry was laid by Black, Priestley, Lavoisier and Dalton, and when the walls began to be raised by Berzelius and Davy, it was possible for one man to hold in his mental grasp the whole range of subjects which he studied. Even when Liebig and Dumas built the fabric of organic chemistry the mass of facts to be considered was not so overpowering as it is now. But we have in great measure ourselves to blame; we have of late years too much fulfilled Liebig's words, when he said, that for rearing the structure of organic chemistry masters were no longer required--workmen would suffice. And I think we have sometimes fallen into another error also. Most of the builders of our science--notably Lavoisier and Davy, Liebig and Dumas--were men of wide general culture. Chemistry was for them a branch of natural science; of late years it has too much tended to degenerate into a handicraft. These men had lofty aims; they recognized--Davy perhaps more than any--the nobility of their calling. The laboratory was to them not merely a place where curious mixtures were made and strange substances obtained, or where elegant apparatus was exhibited and carefully prepared specimens were treasured; it was rather the entrance into the temple of Nature, the place where day by day they sought for truth, where, amid much that was unpleasant and much that was necessary mechanical detail, glimpses were sometimes given them of the order, harmony and law which reign throughout the material universe. It was a place where, stopping in the work which to the outsider appeared so dull and even so trivial, they sometimes, listening with attentive ear, might catch the boom of the "mighty waters rolling evermore," and so might return refreshed to work again. Chemistry was more poetical, more imaginative then than now; but without imagination no great work has been accomplished in science. When a student of science forgets that the particular branch of natural knowledge which he cultivates is part of a living and growing organism, and attempts to study it merely as a collection of facts, he has already Esau-like sold his birthright for a mess of pottage; for is it not the privilege of the scientific student of Nature always to work in the presence of "something which he can never know to the full, but which he is always going on to know"--to be ever encompassed about by the greatness of the subject which he seeks to know? Does he not recognize that, although some of the greatest minds have made this study the object of their lives, the sum of what is known is yet but as a drop in the ocean? and has he not also been taught that every honest effort made to extend the boundaries of natural knowledge must advance that knowledge a little way? It is not easy to remember the greatness of the issues which depend on scientific work, when that work is carried on, as it too often is, solely with the desire to gain a formal and definite answer to some question of petty detail. "That low man seeks a little thing to do, Sees it and does it: This high man, with a great thing to pursue, Dies ere he knows it. "That low man goes on adding one to one, His hundred's soon hit: This high man, aiming at a million, Misses a unit." INDEX. A Acids, connected by Lavoisier with oxygen, 91; Boyle's and other early definitions, 171; opposed in early medicine to alkalis, 172; grouped, 173; salts, 173; "the primordial acid," 174; oxygen not a necessary constituent, 184; new division of acids by Davy, 205; acids of different basicity, 237; modern conception of acids, 301. Affinity, chemical, apparently suspended by electricity, 191; history of term "affinity," 206; tables of, 207; dependent on electric states, 210. Air, composition of, determined by Cavendish, 79; Dalton's investigations, 116. Alchemy, 5; alchemical symbols of metals, 11; quotations from alchemists, 15, 17; alchemical poetry, 18. Alcoates, 235. Alkalis, 171; fixed and volatile, 173; mild and caustic, examined by Black, 176; connection with earths, 178; name of "base" given by Rouelle, 179; Gay-Lussac's alkalizing principle, 203. Ammonia, discovered by Priestley, 66. Atmolysis, 243. Atomic theory, dawn of, 117; early views of Greek philosophers, 123; of Epicurus and Lucretius, 124; of Newton and Bernoulli, 125; Dalton's new views--combination in simple multiples, 127, _et seq._; the theory made known by Dr. Thomson, 129; it is opposed at first by Davy, 130; Dalton's rules for arriving at atomic weights, 132; more accurately applied by Berzelius, 133, 162; diagrams of atoms, 118, 136; the theory as carried out by Gay-Lussac and Avogadro, 138, _et seq._; conception of the molecule, 140; molecular and atomic weight, 145; Graham's work on molecular reactions, 249; Berzelius's dualistic views, 212; they are attacked by Dumas, 260; conception of the compound radicle, 267; Laurent's unitary theory, 272; modern conception of molecule, 275; revision of atomic weights, 285; equivalency of atoms, 295. Avogadro, his elucidation of the atomic theory, 138, _et seq._; introduces the idea of molecules, 140; law known as Avogadro's law, 143. B Base (of salts), 179; basic lines in spectrum, 311. Becher, John J., born at Speyer, 26; his three principles of metals, 26; his principle of inflammability, 48; his views on acids, 174. Berthollet, analyzes ammonia, 66; adheres to the Lavoisierian theory of combustion, 95; questions doctrine of fixity of composition, 126; and necessary presence of oxygen in acids, 184; shows variable nature of affinities, 208. Berzelius, Johann J., 106; determines weights of elementary atoms, 133; his birth and education, 157; works at Stockholm, 159; his slight appliances and large discoveries, 161; he reviews Dalton's atomic theory, 162; his views superseded by Avogadro's generalization, 165; he accepts law of isomorphism, 166; and Davy's discovery of chlorine, 204; his views on affinity of atoms, 209; his dual classification, 212; works at organic chemistry, 220; his dualism attacked by Dumas, 260. Black, Joseph, born at Bordeaux, 30; his education, 31; his thesis on magnesia and discovery of "fixed air," 33, _et seq._; inquiries into latent heat, 39; professor at Edinburgh, 41; his death and character, 41, _et seq._; _resumé_ of his work, 102; his examination of alkalis, 176. Boyle, Hon. Robert, 25; his "Sceptical Chymist," 76; law known as "Boyle's law," 77; opposes doctrine of elementary principles, 93; his definition of an acid, 171; extends the knowledge of salts, 177. Bromine, discovered by Balard, 291. C Carbonic acid gas, or "fixed air," studied by Black, 35; by Priestley, 57, 69. Cavendish, Hon. Henry, rediscovers hydrogen, 63, 78; and composition of water and air, 78. Chloral, } produced by Liebig, composition determined by Dumas, 273. Chloroform,} Chlorine, discovered by Davy, 202; replaces hydrogen in organic compounds, 271. Colloids, 247. Combination in multiple proportions, 127. Combustion, studied by early chemists, 24 (_vide_ "Phlogistic theory"); studied by Black, 47; his views of Lavoisier's theory, 51; Priestley's views of combustion, 62; Lavoisier's experiments, 83, _et seq._; Liebig's combustion-tube, 263. Compound radicle, 267; the idea of substitution, 270, 276. Conservation of mass, doctrine of, 82. Crystallization, water of, 237. Crystalloids, 247. D Dalton, John, his birth and education, 107; "answers to correspondents," 109; his meteorological observations, 110; teaches at Manchester, 110; colour-blind, 111; pressures of gaseous mixtures, 113; strives after general laws, 115; first view of atomic theory, 117; visits Paris, 120; honours conferred on him, 121, 122; dies, 123; consideration of atomic theory (which see), 123, _et seq._; his "New System of Chemical Philosophy," 129; fixes atomic weight of hydrogen, 130; small use he makes of books, 148; inaccurate as an experimenter, 149; his method compared with Priestley's, 151. Davy, Sir Humphry, 106; opposes the atomic theory, 129; accepts same, 130; studies the chemical aspects of electricity, 185; experiments on the acid and alkali said to be produced by electrolyzing water, 186; apparent suspension of chemical affinities by action of electricity, 191; discovers potassium, 197; and sodium, 198; the metallic bases of earths, 200; proves the elementary nature of chlorine, 202; Davy's birth and youth, 215; experiments on heat, 217; his work at Bristol, 218; inhales gases, 220; lectures at the Royal Institution, 222; discovers iodine and invents safety-lamp, 224; dies, 226. Dialysis, 247. Diffusion-rates of gases, 241; distinguished from transpiration-rates, 242; diffusion-rates of liquids, 245. Dulong, his law of atomic heat, 168. Dumas, Jean B. A., birth and education, 257; physiological studies, 258; meets Von Humboldt, 259; attacks the dualism of Berzelius, 260; Dumas's vapour density process, 262; ethers and alcohols, 265; chlorine in connection with organic compounds, 271; determines composition of chloral and chloroform, 273; studies fermentation, 287; member of the National Assembly, 288; takes office, 289. E Earths, 177; Stahl's views, 178; the connection between earths and alkalis, 178; their metallic bases, 182, 200. Economy of waste materials, 300. Electric affinity, 191, 210. Electricity, Volta's battery, 185; used to decompose water, 185; new metals discovered by its help, 197. Elements: old doctrine of elementary principles opposed by Boyle, 93; modern definition of element, 95 (_vide_ "Spectroscopic analysis"--basic lines, 311). Equivalency, conception of, 294. F Fermentation, studied by Dumas, 287. Fourcroy, calls Lavoisier's views "La chimie Française,", 95 G Gay-Lussac, 138, 143, 201, 203, 257. Gerhardt, 272, 279. Graham, Thomas, early life, 233; made Master of the Mint, 234; his death, 235; studies alcoates, 235; formulates conception of acids of different basicity, 237; considers hydrogen a metal, 238; investigates phenomena observed by Döbereiner, 240; diffusion-rates of gases, 241; of liquids, 245; his atmolyzer, 243; his dialyzer, 247; studies movements and reactions of molecules, 249. H Hales's experiments on gases, 34. Heat, Black's study of latent heat, 39; specific heat, 98; Dalton lectures on, 117; law of capacity for heat, 168; heat as produced by friction, 217. Helmholtz, 143; vortex atoms, 125. Hooke, Robert, his "Micographia," 24; studies combustion, 34. Humboldt, Alexander von, assists Liebig, 256; and Dumas, 259. Hydrochloric acid discovered by Priestley, 66; a stumbling-block to Lavoisierian chemists, 200; studied by Davy, 201. Hydrogen, rediscovered by Cavendish, 63; experimented on by Priestley, 66; its atomic weight decided by Dalton, 130; Graham considers it a metal, 238. I Iodine, discovered by Davy, 224. Isomerism, 297. Isomorphism, law of, 167. L Laplace, assists Lavoisier, 90. Latent heat, Black's theory of, 39. Laurent, his unitary theory, 272, 278. Lavoisier, Antoine L., born at Paris, 79; confutes idea of transmutation, 81; paper on calcination of tin, 84; meets Priestley, 61, 85; his theory of combustion, 51, 86; his chemical nomenclature, 96; he is guillotined, 99; _resumé_ of his work, 103; his views on salts, 183, 184. Liebig, Justus, birth, 256; Humboldt and Gay-Lussac, 257; his improved combustion-tube, 263; studies the cyanates, 264; distinction between organic and inorganic chemistry effaced, 265; produces chloroform and chloral, 273; benzoyl, 274; he leaves Giessen for Munich, 280; his practical and economic discoveries, 283; death, 284; his failure to discover bromine, 291. Lockyer, his work with spectroscope, 310 (and _vide_ "Spectroscopic analysis"). M Mayow, John, studies combustion, 24. Metals, new, discovered by Berzelius, 101; by Davy, 197; hydrogen a metal, 238. Meyer, his views on acids, 174. Mitscherlich's law of isomorphism, 167. Molecule, conception of, 140; molecular weight, 145; molecular mobility of gases, 242; movements and reactions of molecules, 249; modern conception of, 275. Morveau, De, embraces Lavoisier's views, 96. Muriatic acid (_vide_ "Hydrochloric acid,") 119. N Nitric acid, discovered by Priestley, 65; produced by electrolysis, 188. Nomenclature, Lavoisier's system of, 96. O Oil, principle of, 254. Organic chemistry, worked at by Berzelius, 229; attempts to define it, 253; loose application of the term, 255; Wöhler's manufacture of urea abolishes distinction of organic and inorganic chemistry, 265. Oxygen discovered by Priestley, 59; Lavoisier's experiments, 87; it is viewed by him as an acidifier, 91, 175; Berthollet shows it not a necessary constituent of acids, 184 (_vide_ "Acids"). P Paracelsus, 13; his pamphlet, "Tripus Aureus," etc., 19. Petit, 168. Phlogistic theory, 26; enunciated by Stahl, 27; abandoned by Black, 46; phlogiston described as a kind of motion, 49; discovery of dephlogisticated air, 59; the theory overthrown by Lavoisier, 92. Phosphoric acid, 86. Pneumatic trough, invented by Priestley, 57. Potassium, discovered by Davy, 197. Prussic acid, discovered by Berthollet, 184. Priestley, Joseph, born, 52; bred for the ministry, 53; writes on electricity, 55; his pneumatic trough, 57; discovers oxygen, 59; meets Lavoisier, 61, 85; goes to Birmingham, 65; his experiments on hydrogen, 66; his house burnt by rioters, 71; emigrates to America, 72; dies there, 73; _resumé_ of his work, 102; his method compared with that of Dalton, 151. Q Quantitative analysis neglected by early chemists, 29; first accurately employed by Black, 33; used by Lavoisier, 87. R Respiration explained by Lavoisier, 91. Revolution, French, its effect on Priestley, 70; Lavoisier guillotined, 99. Richter's equivalents of acids and bases, 162. Ripley, Canon, an alchemist, his poems, 18. Rouelle, invents term "base," 179; his studies on salts, 181. S Salts, 173; "principle of salt" opposed by Boyle, 177; earth or alkali the _base_ of salts, 179; Rouelle's inquiries, 181; Lavoisier's definition, 184; considered as metallic derivatives of acids, 205; alcoholic salts, 235. "Sceptical Chymist, The," by Hon. Robert Boyle, 76-93. Shelburne, Earl of, patron of Priestley, 58; to whom he grants an annuity, 65. Spectroscopic analysis, 302; lines in solar spectrum, 306; the solar atmosphere, 308; Lockyer's mapping of the lines, 310; basic lines, 311; objections to his hypothesis, 313. Stahl, George Ernest, born at Anspach, 27; enunciates the phlogistic theory, 27, 48; his "primordial acid," 174; his essential property of earths, 178. Sulphur dioxide, discovered by Priestley, 66. Sulphur salts, discovered by Berzelius, 161. T Transmutation, confuted by Lavoisier, 81. Transpiration of gases, 242. Types, 279. V Valentine, Basil, an alchemist, 15; his views on alkalis, 174. Van Helmont, 24. Vitriols, 180. Volta's electric pile, 184. W Water, its composition discovered by Cavendish, 68-78; nearly discovered by Priestley, 68; confirmed by Lavoisier, 90; decomposed by electricity, 185. Weight of ultimate particles, 117, 132; molecular and atomic, 145; revision of atomic weights, 285. Wöhler, his account of visit to Berzelius, 160, 204, 229; studies cyanates with Liebig, 264; results of his discovery as to urea, 265. Wollaston, supports atomic theory, 130. PRINTED BY WILLIAM CLOWES AND SONS, LIMITED, LONDON AND BECCLES. 
22914	----	Color title-page images were generously provided by the University of Pennsylvania Schoenberg Center for Electronic Text & Image (http://dewey.library.upenn.edu/sceti). Transcriber's Notes: This e-book was prepared from a facsimile of the 1661 first edition and contains spelling, capitalization, and punctuation inconsistencies typical of the era. These have been preserved as they appear in the original. Printer errors have also been preserved. Those mentioned in the Errata at the end of the book are noted with [Errata: corrected text]. Other obvious printer errors are noted with [Transcriber's Note: corrected text] where the meaning might be unclear without the correction. See also the printer's note preceding the Errata, which contains material omitted from the text (the place where it should be inserted is marked in the text with a Transcriber's Note). There are a number of sidenotes in this book, most of which function as footnotes (e.g., citations to other works) and some of which function as true sidenotes. For the sake of clarity, sidenotes functioning as footnotes have been converted to numbered footnotes, with number markers at appropriate places in the text. A character with a macron is represented by an equal sign. E.g., [=a] indicates "a" with macron. A table of contents has been provided for the reader's convenience. THE SCEPTICAL CHYMIST: OR CHYMICO-PHYSICAL Doubts & Paradoxes, Touching the SPAGYRIST'S PRINCIPLES Commonly call'd HYPOSTATICAL, As they are wont to be Propos'd and Defended by the Generality of ALCHYMISTS. Whereunto is præmis'd Part of another Discourse relating to the same Subject. BY The Honourable _ROBERT BOYLE_, Esq; _LONDON,_ Printed by _J. Cadwell_ for _J. Crooke_, and are to be Sold at the _Ship_ in St. _Paul's_ Church-Yard. _MDCLXI._ CONTENTS A Præface Introductory Physiological Considerations The First Part The Second Part The Third Part The Fourth Part The Fifth Part The Sixth Part The Conclusion Printer's Note Errata A PRÆFACE INTRODUCTORY _To the following Treatise._ _To give the Reader an account, Why the following Treatise is suffer'd to pass abroad so maim'd and imperfect, I must inform him that 'tis now long since, that to gratify an ingenious Gentleman, I set down some of the Reasons that kept me from fully acquiescing either in the Peripatetical, or in the Chymical Doctrine, of the Material Principles of mixt Bodies. This Discourse some years after falling into the hands of some Learned men, had the good luck to be so favourably receiv'd, and advantageously spoken of by them, that having had more then ordinary Invitations given me to make it publick, I thought fit to review it, that I might retrench some things that seem'd not so fit to be shewn to every Reader, And substitute some of those other things that occurr'd to me of the trials and observations I had since made. What became of my papers, I elsewhere mention in a Preface where I complain of it: But since I writ That, I found many sheets that belong'd to the subjects I am now about to discourse of. Wherefore seeing that I had then in my hands as much of the first Dialogue as was requisite to state the Case, and serve for an Introduction as well to the conference betwixt_ Carneades _and_ Eleutherius, _as to some other Dialogues, which for certain reasons are not now herewith publish'd, I resolv'd to supply, as well as I could, the Contents of a Paper belonging to the second of the following Discourses, which I could not possibly retrive, though it were the chief of them all. And having once more try'd the Opinion of Friends, but not of the same, about this imperfect work, I found it such, that I was content in complyance with their Desires; that not only it should be publish'd, but that it should be publish'd as soon as conveniently might be. I had indeed all along the Dialogues spoken of my self, as of a third Person; For, they containing Discourses which were among the first Treatises that I ventur'd long ago to write of matters Philosophical, I had reason to desire, with the Painter, to_ latere pone tabulam, _and hear what men would say of them, before I own'd my self to be their Author. But besides that now I find, 'tis not unknown to many who it is that writ them, I am made to believe that 'tis not inexpedient, they should be known to come from a Person not altogether a stranger to Chymical Affairs. And I made the lesse scruple to let them come abroad uncompleated, partly, because my affairs and Præ-ingagements to publish divers other Treatises allow'd me small hopes of being able in a great while to compleat these Dialogues. And partly, because I am not unapt to think, that they may come abroad seasonably enough, though not for the Authors reputation, yet for other purposes. For I observe, that of late Chymistry begins, as indeed it deserves, to be cultivated by Learned Men who before despis'd it; and to be pretended to by many who never cultivated it, that they may be thought not to ignore it: Whence it is come to passe, that divers Chymical Notions about Matters Philosophical are taken for granted and employ'd, and so adopted by very eminent Writers both Naturalists and Physitians. Now this I fear may prove somewhat prejudicial to the Advancement of solid Philosophy: For though I am a great Lover of Chymical Experiments, and though I have no mean esteem of divers Chymical Remedies, yet I distinguish these from their Notions about the causes of things, and their manner of Generation. And for ought I can hitherto discern, there are a thousand_ Phænomena _in Nature, besides a Multitude of Accidents relating to the humane Body, which will scarcely be clearly & satisfactorily made out by them that confine themselves to deduce things from Salt, Sulphur and Mercury, and the other Notions peculiar to the Chymists, without taking much more Notice than they are wont to do, of the Motions and Figures, of the small Parts of Matter, and the other more Catholick and Fruitful affections of Bodies. Wherefore it will not perhaps be now unseasonable to let our_ Carneades _warne Men, not to subscribe to the grand Doctrine of the Chymists touching their three Hypostatical Principles, till they have a little examin'd it, and consider'd, how they can clear it from his Objections, divers of which 'tis like they may never have thought on; since a Chymist scarce would, and none but a Chymist could propose them. I hope also it will not be unacceptable to several Ingenious Persons, who are unwilling to determine of any important Controversie, without a previous consideration of what may be said on both sides, and yet have greater desires to understand Chymical Matters, than Opportunities of learning them, to find here together, besides several Experiments of my own purposely made to Illustrate the Doctrine of the Elements, divers others scarce to be met with, otherwise then Scatter'd among many Chymical Books. And to Find these Associated Experiments so Deliver'd as that an Ordinary Reader, if he be but Acquainted with the usuall Chymical Termes, may easily enough Understand Them; and even a wary One may safely rely on Them. These Things I add, because a Person any Thing vers'd in the Writings of Chymists cannot but Discern by their obscure, Ambiguous, and almost Ænigmatical Way of expressing what they pretend to Teach, that they have no Mind, to be understood at all, but by_ the Sons of Art _(as they call them) nor to be Understood even by these without Difficulty And Hazardous Tryalls. Insomuch that some of Them Scarce ever speak so candidly, as when they make use of that known Chymical Sentence;_ Ubi palam locuti fumus, ibi nihil diximus. _And as the obscurity of what some Writers deliver makes it very difficult to be understood; so the Unfaithfulness of too many others makes it unfit to be reli'd on. For though unwillingly, Yet I must for the truths sake, and the Readers, warne him not to be forward to believe Chymical Experiments when they are set down only by way of Prescriptions, and not of Relations; that is, unless he that delivers them mentions his doing it upon his own particular knowledge, or upon the Relation of some credible person, avowing it upon his own experience. For I am troubled, I must complain, that even Eminent Writers, both Physitians and Philosophers, whom I can easily name, if it be requir'd, have of late suffer'd themselves to be so far impos'd upon, as to Publish and Build upon Chymical Experiments, which questionless they never try'd; for if they had, they would, as well as I, have found them not to be true. And indeed it were to be wish'd, that now that those begin to quote Chymical Experiments that are not themselves Acquainted with Chymical Operations, men would Leave off that Indefinite Way of Vouching the Chymists say this, or the Chymists affirme that, and would rather for each Experiment they alledge name the Author or Authors, upon whose credit they relate it; For, by this means they would secure themselves from the suspition of falshood (to which the other Practice Exposes them) and they would Leave the Reader to Judge of what is fit for him to Believe of what is Deliver'd, whilst they employ not their own great names to Countenance doubtfull Relations; and they will also do Justice to the Inventors or Publishers of true Experiments, as well as upon the Obtruders of false ones. Whereas by that general Way of quoting the Chymists, the candid Writer is Defrauded of the particular Praise, and the Impostor escapes the Personal Disgrace that is due to him._ _The remaining Part of this Præface must be imploy'd in saying something for_ Carneades, _and something for my Self._ _And first_, Carneades _hopes that he will be thought to have disputed civilly and Modestly enough for one that was to play the Antagonist and the Sceptick. And if he any where seem to sleight his Adversaries Tenents and Arguments, he is willing to have it look'd upon as what he was induc'd to, not so much by his Opinion of them, as the Examples of_ Themistius _and_ Philoponus, _and the custom of such kind of Disputes._ _Next, In case that some of his Arguments shall not be thought of the most Cogent sort that may be, he hopes it will be consider'd that it ought not to be Expected, that they should be So. For, his Part being chiefly but to propose Doubts and Scruples, he does enough, if he shews that his Adversaries Arguments are not strongly Concluding, though his own be not so neither. And if there should appear any disagreement betwixt the things he delivers in divers passages, he hopes it will be consider'd, that it is not necessary that all the things a Sceptick Proposes, should be consonant; since it being his work to Suggest doubts against the Opinion he questions, it is allowable for him to propose two or more severall_ Hypotheses _about the same thing: And to say that it may be accounted for this way, or that way, or the other Way, though these wayes be perhaps inconsistent among Themselves. Because it is enough for him, if either of the proposed_ Hypotheses _be but as probable as that he calls a question. And if he proposes many that are Each of them probable, he does the more satisfie his doubts, by making it appear the more difficult to be sure, that that which they alwayes differ from is the true. And our_ Carneades _by holding the Negative, he has this Advantage, that if among all the Instances he brings to invalidate all the Vulgar Doctrine of those he Disputes with, any one be Irrefragable, that alone is sufficient to overthrow a Doctrine which Universally asserts what he opposes. For, it cannot be true, that all Bodies whatsoever that are reckon'd among the Perfectly mixt Ones, are Compounded of such a Determinate Number of such or such Ingredients, in case any one such Body can be produc'd, that is not so compounded; and he hopes too, that Accurateness will be the less expected from him, because his undertaking obliges him to maintain such Opinions in Chymistry, and that chiefly by Chymical Arguments, as are Contrary to the very Principles of the Chymists; From whose writings it is not Therefore like he should receive any intentionall Assistance, except from some Passages of the Bold and Ingenious_ Helmont, _with whom he yet disagrees in many things (which reduce him to explicate Divers Chymical_ Phænomena, _according to other Notions;) And of whose Ratiocinations, not only some seem very Extravagant, but even the Rest are not wont to be as considerable as his Experiments. And though it be True indeed, that some_ Aristotelians _have occasionally written against the Chymical Doctrine he Oppugnes, yet since they have done it according to their Principles, And since our_ Carneades _must as well oppose their_ Hypothesis _as that of the Spagyrist, he was fain to fight his Adversaries with their own Weapons, Those of the Peripatetick being Improper, if not hurtfull for a Person of his Tenents; besides that those_ Aristotelians, _(at Least, those he met with,) that have written against the Chymists, seem to have had so little Experimental Knowledge in Chymical Matters, that by their frequent Mistakes and unskilfull Way of Oppugning, they have too often expos'd Themselves to the Derision of their Adversaries, for writing so Confidently against what they appear so little to understand._ _And Lastly_, Carneades _hopes, he shall doe the Ingenious this Piece of service, that by having Thus drawn the Chymists Doctrine out of their Dark and Smoakie Laboratories, and both brought it into the open light, and shewn the weakness of their Proofs, that have hitherto been wont to be brought for it, either Judicious Men shall henceforth be allowed calmly and after due information to disbelieve it, or those abler Chymists, that are zealous for the reputation of it, will be oblig'd to speak plainer then hitherto has been done, and maintain it by better Experiments and Arguments then Those_ Carneades _hath examin'd: so That he hopes, the Curious will one Way or other Derive either satisfaction or instruction from his endeavours. And as he is ready to make good the profession he makes in the close of his Discourse, he being ready to be better inform'd, so he expects either to be indeed inform'd, or to be let alone. For Though if any Truly knowing Chymists shall Think fit in a civil and rational way to shew him any truth touching the matter in Dispute That he yet discernes not,_ Carneades _will not refuse either to admit, or to own a Conviction: yet if any impertinent Person shall, either to get Himself a Name, or for what other end soever, wilfully or carelesly mistake the State of the Controversie, or the sence of his Arguments, or shall rail instead of arguing, as hath been done of Late in Print by divers Chymists;_[1] _or lastly, shall write against them in a canting way; I mean, shall express himself in ambiguous or obscure termes, or argue from experiments not intelligibly enough Deliver'd_, Carneades _professes, That he values his time so much, as not to think the answering such Trifles worth the loss of it._ [Footnote 1: G. and F. and H. and others, in their books against one another.] _And now having said thus much for_ Carneades, _I hope the Reader will give me leave to say something too for my self._ _And first, if some morose Readers shall find fault with my having made the Interlocutors upon occasion complement with one another, and that I have almost all along written these Dialogues in a stile more Fashionable then That of meer scholars is wont to be, I hope I shall be excus'd by them that shall consider, that to keep a due_ decorum _in the Discourses, it was fit that in a book written by a Gentleman, and wherein only Gentlemen are introduc'd as speakers, the Language should be more smooth, and the Expressions more civil than is usual in the more Scholastick way of writing. And indeed, I am not sorry to have this Opportunity of giving an example how to manage even Disputes with Civility; whence perhaps some Readers will be assisted to discern a Difference betwixt Bluntness of speech and Strength of reason, and find that a man may be a Champion for Truth, without being an Enemy to Civility; and may confute an Opinion without railing at Them that hold it; To whom he that desires to convince and not to provoke them, must make some amends by his Civility to their Persons, for his severity to their mistakes; and must say as little else as he can, to displease them, when he says that they are in an error._ _But perhaps other Readers will be less apt to find fault with the Civility of my Disputants, than the Chymists will be, upon the reading of some Passages of the following Dialogue, to accuse_ Carneades _of Asperity. But if I have made my Sceptick sometimes speak sleightingly of the Opinions he opposes, I hope it will not be found that I have done any more, than became the Part he was to act of an Opponent: Especially, if what I have made him say be compar'd with what the Prince of the Romane Orators himself makes both great Persons and Friends say of one anothers Opinions, in his excellent Dialogues,_ De Natura Deorum: _And I shall scarce be suspected of Partiality, in the case, by them that take Notice that there is full as much (if not far more) liberty of sleighting their Adversaries Tenents to be met with in the Discourses of those with whom_ Carneades _disputes. Nor needed I make the Interlocutors speak otherwise then freely in a Dialogue, wherein it was sufficiently intimated, that I meant not to declare my own Opinion of the Arguments propos'd, much lesse of the whole Controversy it self otherwise than as it may by an attentive Reader be guess'd at by some Passages of_ Carneades: _(I say, some Passages, because I make not all that he says, especially in the heat of Disputation, mine,) partly in this Discourse, and partly in some other Dialogues betwixt the same speakers (though they treat not immediately of the Elements) which have long layn by me, and expect the Entertainment that these present Discourses will meet with. And indeed they will much mistake me, that shall conclude from what I now publish, that I am at Defyance with Chymistry, or would make my Readers so. I hope the_ Specimina _I have lately publish'd of an attempt to shew the usefulness of Chymical Experiments to Contemplative Philosophers, will give those that shall read them other thoughts of me: & I had a design (but wanted opportunity) to publish with these Papers an Essay I have lying by me, the greater part of which is Apologetical for one sort of Chymists. And at least, as for those that know me, I hope the pain I have taken in the fire will both convince them, that I am far from being an Enemy to the Chymists Art, (though I am no friend to many that disgrace it by professing it,) and perswade them to believe me when I declare that I distinguish betwixt those Chymists that are either Cheats, or but Laborants, and the true_ Adepti; _By whom, could I enjoy their Conversation, I would both willingly and thankfully be instructed; especially concerning the Nature and Generation of Metals: And possibly, those that know how little I have remitted of my former addictedness to make Chymical Experiments, will easily believe, that one of the chief Designes of this Sceptical Discourse was, not so much to discredit Chymistry, as to give an occasion and a kind of necessity to the more knowing Artists to lay aside a little of their over-great Reservedness, & either explicate or prove the Chymical Theory better than ordinary Chymists have done, or by enriching us with some of their nobler secrets to evince that Their art is able to make amends even for the deficiencies of their Theory: And thus much I shall here make bold to add, that we shall much undervalue Chymistry, if we imagine, that it cannot teach us things farr more useful, not only to Physick but to Philosophy, than those that are hitherto known to vulgar Chymists. And yet as for inferiour Spagyrists themselves, they have by their labours deserv'd so well of the Common-wealth of Learning, that methinks 'tis Pity they should ever misse the Truth which they have so industriously sought. And though I be no Admirer of the Theorical Part of their Art, yet my conjectures will much deceive me, if the Practical Part be not much more cultivated than hitherto it has been, and do not both employ Philosophy and Philosophers, and help to make men such. Nor would I that have been diverted by other Studies as well as affairs, be thought to pretend being a profound Spagyrist, by finding so many faults in the Doctrine wherein the Generality of Chymists scruples not to Acquiesce: For besides that 'tis most commonly far easier to frame Objections against any propos'd_ Hypothesis, _than to propose an_ Hypothesis _not lyable to Objections (besides this I say) 'tis no such great matter, if whereas Beginners in Chymistry are commonly at once imbu'd with the Theory and Operations of their profession, I who had the good Fortune to Learn the Operations from illiterate Persons, upon whose credit I was not Tempted to take up any opinion about them, should consider things with lesse prejudice, and consequently with other Eyes than the Generality of Learners; And should be more dispos'd to accommodate the_ Phænomena _that occur'd to me to other Notions than to those of the Spagyrists. And having at first entertain'd a suspition That the Vulgar Principles were lesse General and comprehensive, or lesse considerately Deduc'd from Chymical Operations, than was believ'd; it was not uneasie for me both to Take notice of divers_ Phænomena, _overlook'd by prepossest Persons, that seem'd not to suite so well with the_ Hermetical _Doctrine; and, to devise some Experiments likely to furnish me with Objections against it, not known to many, that having practis'd Chymistry longer perchance then I have yet liv'd, may have far more Experience, Than I, of particular processes._ _To conclude, whether the Notions I have propos'd, and the Experiments I have communicated, be considerable, or not, I willingly leave others to Judge; and This only I shall say for my Self, That I have endeavour'd to deliver matters of Fact, so faithfully, that I may as well assist the lesse skilful Readers to examine the Chymical_ Hypothesis, _as provoke the Spagyrical Philosophers to illustrate it: which if they do, and that either the Chymical opinion, or the Peripatetick, or any other Theory of the Elements differing from that I am most inclin'd to, shall be intelligibly explicated, and duly prov'd to me; what I have hitherto discours'd will not hinder it from making a Proselyte of a Person that Loves Fluctuation of Judgment little enough to be willing to be eas'd of it by any thing but Error._ PHYSIOLOGICAL CONSIDERATIONS Touching _The experiments wont to be employed to evince either the IV Peripatetick Elements, or the III Chymical Principles of Mixt Bodies._ Part of the First Dialogue. I Perceive that divers of my Friends have thought it very strange to hear me speak so irresolvedly, as I have been wont to do, concerning those things which some take to be the Elements, and others to be the Principles of all mixt Bodies. But I blush not to acknowledge that I much lesse scruple to confess that I Doubt, when I do so, then to profess that I Know what I do not: And I should have much stronger Expectations then I dare yet entertain, to see Philosophy solidly establish't, if men would more carefully distinguish those things that they know, from those that they ignore or do but think, and then explicate clearly the things they conceive they understand, acknowledge ingenuously what it is they ignore, and profess so candidly their Doubts, that the industry of intelligent persons might be set on work to make further enquiries, and the easiness of less discerning Men might not be impos'd on. But because a more particular accompt will probably be expected of my unsatisfyedness not only with the Peripatetick, but with the Chymical Doctrine of the Primitive Ingredients of Bodies: It may possibly serve to satisfy others of the excusableness of my disatisfaction to peruse the ensuing Relation of what passed a while since at a meeting of persons of several opinions, in a place that need not here be named; where the subject whereof we have been speaking, was amply and variously discours'd of. It was on one of the fairest dayes of this Summer that the inquisitive _Eleutherius_ came to invite me to make a visit with him to his friend _Carneades_. I readily consented to this motion, telling him that if he would but permit me to go first and make an excuse at a place not far off, where I had at that hour appointed to meet, but not about a business either of moment, or that could not well admit of a delay, I would presently wait on him, because of my knowing _Carneades_ to be so conversant with nature and with Furnaces, and so unconfin'd to vulgar Opinions, that he would probably by some ingenious Paradox or other, give our mindes at least a pleasing Exercise, and perhaps enrich them with some solid instruction. _Eleutherius_ then first going with me to the place where my Apology was to be made, I accompanied him to the lodging of _Carneades_, where when we were come, we were told by the Servants, that he was retired with a couple of Friends (whose names they also told us) to one of the Arbours in his Garden, to enjoy under its coole shades a delightful protection from the yet troublesome heat of the Sun. _Eleutherius_ being perfectly acquainted with that Garden immediately led me to the Arbour, and relying on the intimate familiarity that had been long cherish'd betwixt him and _Carneades_; in spight of my Reluctancy to what might look like an intrusion upon his privacy, drawing me by the hand, he abruptly entered the Arbour, where we found _Carneades_, _Philoponus_, and _Themistius_, sitting close about a little round Table, on which besides paper, pen, and inke, there lay two or three open Books; _Carneades_ appeared not at all troubled at this surprise, but rising from the Table, received his Friend with open looks and armes, and welcoming me also with his wonted freedom and civility, invited us to rest our selves by him, which, as soon as we had exchanged with his two Friends (who were ours also) the civilities accustomed on such occasions, we did. And he presently after we had seated our selves, shutting the Books that lay open, and turning to us with a smiling countenance seemed ready to begin some such unconcerning discourse as is wont to pass or rather waste the time in promiscuous companies. But _Eleutherius_ guessing at what he meant to do, prevented him by telling him, I perceive _Carneades_ by the books that you have been now shutting, and much more by the posture wherein I found Persons qualifi'd [Errata: so qualify'd] to discourse of serious matters; and so accustom'd to do it, that you three were before our coming, engag'd in some Philosophical conference, which I hope you will either prosecute, and allow us to be partakers of, in recompence of the freedome we have us'd in presuming to surprise you, or else give us leave to repair the injury we should otherwise do you, by leaving you to the freedom we have interrupted, and punishing our selves for our boldness by depriving our selves of the happiness of your company. With these last words he and I rose up, as if we meant to be gone, But _Carneades_ suddenly laying hold on his arme, and stopping him by it, smileingly told him, We are not so forward to lose good company as you seem to imagine; especially since you are pleas'd to desire to be present at what we shall say, about such a Subject as that You found us considering. For that, being the number of the Elements, Principles, or Materiall Ingredients of Bodies, is an enquiry whose truth is of that Importance, and of that Difficulty, that it may as well deserve as require to be searched into by such skilfull Indagators of Nature as your selves. And therefore we sent to invite the bold and acute _Leucippus_ to lend us some light by his Atomical Paradox, upon which we expected such pregnant hints, that 'twas not without a great deal of trouble that we had lately word brought us that he was not to be found; and we had likewise begg'd the Assistance of your presence and thoughts, had not the messenger we employ'd to _Leucippus_ inform'd us, that as he was going, he saw you both pass by towards another part of the Town; And this frustrated expectation of _Leucippus_ his company, who told me but last night that he would be ready to give me a meeting where I pleas'd to day, having very long suspended our conference about the freshly mention'd Subject, it was so newly begun when you came in, that we shall scarce need to repeat any thing to acquaint you with what has pass'd betwixt us before your arrival, so that I cannot but look upon it as a fortunate Accident that you should come so seasonably, to be not hearers alone, but we hope Interlocutors at our conference. For we shall not only allow of your presence at it, but desire your Assistance in it; which I adde both for other reasons, and because though these learned Gentlemen (sayes he, turning to his two friends) need not fear to discourse before any Auditory, provided it be intelligent enough to understand them, yet for my part (continues he with a new smile,) I shall not dare to vent my unpremeditated thoughts before two such Criticks, unless by promising to take your turnes of speaking, You will allow me mine of quarrelling, with what has been said. He and his friends added divers things to convince us that they were both desirous that we should hear them, and resolved against our doing so, unless we allowed them sometimes to hear us. _Elutherius_ [Transcriber's Note: Eleutherius] after having a while fruitlesly endeavoured to obtain leave to be silent promis'd he would not be so alwayes, provided that he were permitted according to the freedom of his Genious and Principles to side with one of them in the managing of one Argument, and, if he saw cause, with his Antagonist, in the Prosecution of another, without being confin'd to stick to any one party or Opinion, which was after some debate accorded him. But I conscious to my own Disability's told them resolutely that _I_ was as much more willing as more fit to be a hearer then a speaker, among such knowing Persons, and on so abstruse a Subject. And that therefore I beseeched them without necessitating me to proclaim my weaknesses, to allow me to lessen them by being a silent Auditor of their Discourses: to suffer me to be at which I could present them no motive, save that their instructions would make them in me a more intelligent Admirer. I added, that I desir'd not to be idle whilst they were imploy'd, but would if they pleas'd, by writing down in short hand what should be delivered, preserve Discourses that I knew would merit to be lasting. At first _Carneades_ and his two friends utterly rejected this motion; and all that my Resoluteness to make use of my ears, not tongue, at their debates, could do, was to make them acquiesce in the Proposition of _Eleutherius_, who thinking himself concern'd, because he brought me thither, to afford me some faint assistance, was content that I should register their Arguments, that I might be the better able after the conclusion of their conference to give them my sence upon the Subject of it, (The number of Elements or Principles:) which he promis'd I should do at the end of the present Debates, if time would permit, or else at our next meeting. And this being by him undertaken in my name, though without my consent, the company would by no means receive my Protestation against it, but casting, all at once, their eyes on _Carneades_, they did by that and their unanimous silence, invite him to begin; which (after a short pause, during which he turn'd himself to _Eleutherius_ and me) he did in this manner. Notwithstanding the subtile reasonings I have met with in the books of the Peripateticks, and the pretty experiments that have been shew'd me in the Laboratories of Chymists, I am of so diffident, or dull a Nature, as to think that if neither of them can bring more cogent arguments to evince the truth of their assertion then are wont to be brought; a Man may rationally enough retain some doubts concerning the very number of those materiall Ingredients of mixt bodies, which some would have us call Elements, and others principles. Indeed when I considered that the Tenents concerning the Elements are as considerable amongst the Doctrines of natural Philosophy as the Elements themselves are among the bodies of the Universe, I expected to find those Opinions solidly establish'd, upon which so many others are superstructed. But when I took the pains impartially to examine the bodies themselves that are said to result from the blended Elements, and to torture them into a confession of their constituent Principles, I was quickly induc'd to think that the number of the Elements has been contended about by Philosophers with more earnestness then success. This unsatisfiedness of mine has been much wonder'd at, by these two Gentlemen (at which words he pointed at _Themistius_ and _Philoponus_) who though they differ almost as much betwixt themselves about the question we are to consider, as I do from either of them, yet they both agree very well in this, that there is a determinate number of such ingredients as I was just now speaking of, and that what that number is, I say not, may be, (for what may not such as they perswade?) but is wont to be clearly enough demonstrated both by Reason and Experience. This has occasion'd our present Conference. For our Discourse this afternoon, having fallen from one subject to another, and at length setl'd on this, they proffer'd to demonstrate to me, each of them the truth of his opinion, out of both the Topicks that I have freshly nam'd. But on the former (that of Reason strictly so taken) we declin'd insisting at the present, lest we should not have time enough before supper to go thorough the Reasons and Experiments too. The latter of which we unanimously thought the most requisite to be seriously examin'd. I must desire you then to take notice Gentlemen (continued _Carneades_) that my present business doth not oblige me so to declare my own opinion on the Subject in question, as to assert or deny the truth either of the Peripatetick, or the Chymical Doctrine concerning the number of the Elements, but only to shew you that neither of these Doctrines hath been satisfactorily proved by the arguments commonly alledged on its behalfe. So that if I really discern (as perhaps I think I do) that there may be a more rational account then ordinary, given of one of these opinions, I am left free to declare my self of it, notwithstanding my present engagement, it being obvious to all your observation, that a solid truth may be generally maintained by no other, then incompetent Arguments. And to this Declaration I hope it will be needless to add, that my task obliges me not to answer the Arguments that may be drawn either for _Themistius_ or _Philoponus's_ Opinion from the Topick of reason, as opposed to experiments; since 'tis these only that I am to examine and not all these neither, but such of them alone as either of them shall think fit to insist on, and as have hitherto been wont to be brought either to prove that 'tis the four Peripatetick Elements, or that 'tis the three Chymical Principles that all compounded bodies consist of. These things (adds _Carneades_) I thought my self obliged to premise, partly lest you should do these Gentlemen (pointing at _Themistius_ and _Philoponus_, and smiling on them) the injury of measuring their parts by the arguments they are ready to propose, the lawes of our Conference confining them to make use of those that the vulgar of Philosophers (for even of them there is a vulgar) has drawn up to their hands; and partly, that you should not condemn me of presumption for disputing against persons over whom I can hope for no advantage, that _I_ must not derive from the nature, or rules of our controversy, wherein I have but a negative to defend, and wherein too I am like on several occasions to have the Assistance of one of my disagreeing adversaries against the other. _Philoponus_ and _Themistius_ soon returned this complement with civilities of the like nature, in which _Eleutherius_ perceiving them engaged, to prevent the further loss of that time of which they were not like to have very much to spare, he minded them that their present businesse was not to exchange complements, but Arguments: and then addressing his speech to _Carneades_, I esteem it no small happinesse (saies he) that I am come here so luckily this Evening. For I have been long disquieted with Doubts concerning this very subject which you are now ready to debate. And since a Question of this importance is to be now discussed by persons that maintain such variety of opinions concerning it, and are both so able to enquire after truth, and so ready to embrace it by whomsoever and on what occasion soever it is presented them; I cannot but promise my self that I shall before we part either lose my Doubts or the hopes of ever finding them resolved; _Eleutherius_ paused not here; but to prevent their answer, added almost in the same breath; and I am not a little pleased to find that you are resolved on this occasion to insist rather on Experiments then Syllogismes. For I, and no doubt You, have long observed, that those Dialectical subtleties, that the Schoolmen too often employ about Physiological Mysteries, are wont much more to declare the wit of him that uses them, then increase the knowledge or remove the doubts of sober lovers of truth. And such captious subtleties do indeed often puzzle and sometimes silence men, but rarely satisfy them. Being like the tricks of Jugglers, whereby men doubt not but they are cheated, though oftentimes they cannot declare by what slights they are imposed on. And therefore I think you have done very wisely to make it your businesse to consider the _Phænomena_ relating to the present Question, which have been afforded by experiments, especially since it might seem injurious to our senses, by whose mediation we acquire so much of the knowledge we have of things corporal, to have recourse to far-fetched and abstracted Ratiocination [Errata: Ratiocinations], to know what are the sensible ingredients of those sensible things that we daily see and handle, and are supposed to have the liberty to untwist (if I may so speak) into the primitive bodies they consist of. He annexed that he wished therefore they would no longer delay his expected satisfaction, if they had not, as he feared they had, forgotten something preparatory to their debate; and that was to lay down what should be all along understood by the word Principle or Element. _Carneades_ thank'd him for his admonition, but told him that they had not been unmindful of so requisite a thing. But that being Gentlemen and very far from the litigious humour of loving to wrangle about words or terms or notions as empty; they had before his coming in, readily agreed promiscuously to use when they pleased, Elements and Principles as terms equivalent: and to understand both by the one and the other, those primitive and simple Bodies of which the mixt ones are said to be composed, and into which they are ultimately resolved. And upon the same account (he added) we agreed to discourse of the opinions to be debated, as we have found them maintained by the Generality of the assertors of the four Elements of the one party, and of those that receive the three Principles on the other, without tying our selves to enquire scrupulously what notion either _Aristotle_ or _Paracelsus_, or this or that Interpreter, or follower of either of those great persons, framed of Elements or Principles; our design being to examine, not what these or those writers thought or taught, but what we find to be the obvious and most general opinion of those, who are willing to be accounted Favourers of the Peripatetick or Chymical Doctrine, concerning this subject. I see not (saies _Eleutherius_) why you might not immediately begin to argue, if you were but agreed which of your two friendly Adversaries shall be first heard. And it being quickly resolv'd on that _Themistius_ should first propose the Proofs for his Opinion, because it was the antienter, and the more general, he made not the company expect long before he thus addressed himself to _Eleutherius_, as to the Person least interessed in the dispute. If you have taken sufficient notice of the late Confession which was made by _Carneades_, and which (though his Civility dressed it up in complementall Expressions) was exacted of him by his Justice, I suppose You will be easily made sensible, that I engage in this Controversie with great and peculiar Disadvantages, besides those which his Parts and my Personal Disabilities would bring to any other cause to be maintained by me against him. For he justly apprehending the force of truth, though speaking by no better a tongue then mine, has made it the chief condition of our Duell, that I should lay aside the best Weapons I have, and those I can best handle; Whereas if I were allowed the freedom, in pleading for the four Elements, to employ the Arguments suggested to me by Reason to demonstrate them, I should almost as little doubt of making You a Proselyte to those unsever'd Teachers, Truth and _Aristotle_, as I do of your Candour and your Judgment. And I hope you will however consider, that that great Favorite and Interpreter of Nature, _Aristotle_, who was (as his _Organum_ witnesses) the greatest Master of Logick that ever liv'd, disclaim'd the course taken by other petty Philosophers (Antient and Modern) who not attending the Coherence and Consequences of their Opinions, are more sollicitous to make each particular Opinion plausible independently upon the the [Transcriber's Note: extra "the" in original] rest, then to frame them all so, as not only to be consistent together, but to support each other. For that great Man in his vast and comprehensive Intellect, so fram'd each of his Notions, that being curiously adapted into one Systeme, they need not each of them any other defence then that which their mutuall Coherence gives them: As 'tis in an Arch, where each single stone, which if sever'd from the rest would be perhaps defenceless, is sufficiently secur'd by the solidity and entireness of the whole Fabrick of which it is a part. How justly this may be apply'd to the present case, I could easily shew You, if I were permitted to declare to You, how harmonious _Aristotles_ Doctrine of the Elements is with his other Principles of Philosophy; and how rationally he has deduc'd their number from that of the combinations of the four first Qualities from the kinds of simple Motion belonging to simple bodies, and from I know not how many other Principles and _Phænomena_ of Nature, which so conspire with his Doctrine of the Elements, that they mutually strengthen and support each other. But since 'tis forbidden me to insist on Reflections of this kind, I must proceed to tell You, that though the Assertors of the four Elements value Reason so highly, and are furnish'd with Arguments enough drawn from thence, to be satisfi'd that there must be four Elements, though no Man had ever yet made any sensible tryal to discover their Number, yet they are not destitute of Experience to satisfie others that are wont to be more sway'd by their senses then their Reason. And I shall proceed to consider the testimony of Experience, when I shall have first advertis'd You, that if Men were as perfectly rational as 'tis to be wish'd they were, this sensible way of Probation would be as needless as 'tis wont to be imperfect. For it is much more high and Philosophical to discover things _a priore_, then _a posteriore_. And therefore the Peripateticks have not been very sollicitous to gather Experiments to prove their Doctrines, contenting themselves with a few only, to satisfie those that are not capable of a Nobler Conviction. And indeed they employ Experiments rather to illustrate then to demonstrate their Doctrines, as Astronomers use Sphæres of pastboard, to descend to the capacities of such as must be taught by their senses, for want of being arriv'd to a clear apprehension of purely Mathematical Notions and Truths. I speak thus _Eleutherius_ (adds _Themistius_) only to do right to Reason, and not out of Diffidence of the Experimental proof I am to alledge. For though I shall name but one, yet it is such a one as will make all other appear as needless as it self will be found Satisfactory. For if You but consider a piece of green-Wood burning in a Chimney, You will readily discern in the disbanded parts of it the four Elements, of which we teach It and other mixt bodies to be compos'd. The fire discovers it self in the flame by its own light; the smoke by ascending to the top of the chimney, and there readily vanishing into air, like a River losing it self in the Sea, sufficiently manifests to what Element it belongs and gladly returnes. The water in its own form boyling and hissing at the ends of the burning Wood betrayes it self to more then one of our senses; and the ashes by their weight, their firiness, and their dryness, put it past doubt that they belong to the Element of Earth. If I spoke (continues _Themistius_) to less knowing Persons, I would perhaps make some Excuse for building upon such an obvious and easie _Analysis_, but 'twould be, I fear, injurious, not to think such an Apology needless to You, who are too judicious either to think it necessary that Experiments to prove obvious truths should be farr fetch'd, or to wonder that among so many mixt Bodies that are compounded of the four Elements, some of them should upon a slight _Analysis_ manifestly exhibite the Ingredients they consist of. Especially since it is very agreeable to the Goodness of Nature, to disclose, even in some of the most obvious Experiments that Men make, a Truth so important, and so requisite to be taken notice of by them. Besides that our _Analysis_ by how much the more obvious we make it, by so much the more suittable it will be to the Nature of that Doctrine which 'tis alledged to prove, which being as clear and intelligible to the Understanding as obvious to the sense, tis no marvail the learned part of Mankind should so long and so generally imbrace it. For this Doctrine is very different from the whimseys of _Chymists_ and other Modern Innovators, of whose _Hypotheses_ we may observe, as Naturalists do of less perfect Animals, that as they are hastily form'd, so they are commonly short liv'd. For so these, as they are often fram'd in one week, are perhaps thought fit to be laughed at the next; and being built perchance but upon two or three Experiments are destroyed by a third or fourth, whereas the doctrine of the four Elements was fram'd by _Aristotle_ after he had leasurely considered those Theories of former Philosophers, which are now with great applause revived, as discovered by these latter ages; And had so judiciously detected and supplyed the Errors and defects of former _Hypotheses_ concerning the Elements, that his Doctrine of them has been ever since deservedly embraced by the letter'd part of Mankind: All the Philosophers that preceded him having in their several ages contributed to the compleatness of this Doctrine, as those of succeeding times have acquiesc'd in it. Nor has an _Hypothesis_ so deliberately and maturely established been called in Question till in the last Century _Paracelsus_ and some few other sooty Empiricks, rather then (as they are fain to call themselves) Philosophers, having their eyes darken'd, and their Brains troubl'd with the smoke of their own Furnaces, began to rail at the Peripatetick Doctrine, which they were too illiterate to understand, and to tell the credulous World, that they could see but three Ingredients in mixt Bodies; which to gain themselves the repute of Inventors, they endeavoured to disguise by calling them, instead of Earth, and Fire, and Vapour, Salt, Sulphur, and Mercury; to which they gave the canting title of Hypostatical Principles: but when they came to describe them, they shewed how little they understood what they meant by them, by disagreeing as much from one another, as from the truth they agreed in opposing: For they deliver their _Hypotheses_ as darkly as their Processes; and 'tis almost as impossible for any sober Man to find their meaning, as 'tis for them to find their Elixir. And indeed nothing has spread their Philosophy, but their great Brags and undertakings; notwithstanding all which, (sayes _Themistius_ smiling) I scarce know any thing they have performed worth wondering at, save that they have been able to draw _Philoponus_ to their Party, and to engage him to the Defence of an unintelligible _Hypothesis_, who knowes so well as he does, that Principles ought to be like Diamonds, as well very clear, as perfectly solid. _Themistius_ having after these last words declared by his silence, that he had finished his Discourse, _Carneades_ addressing himself, as his Adversary had done, to _Eleutherius_, returned this Answer to it, I hop'd for [Errata: for a] Demonstration, but I perceive _Themistius_ hopes to put me off with a Harangue, wherein he cannot have given me a greater Opinion of his Parts, then he has given me Distrust for his _Hypothesis_, since for it even a Man of such Learning can bring no better Arguments. The Rhetorical part of his Discourse, though it make not the least part of it, I shall say nothing to, designing to examine only the Argumentative part, and leaving it to _Philoponus_ to answer those passages wherein either _Paracelsus_ or _Chymists_ are concern'd: I shall observe to You, that in what he has said besides, he makes it his Business to do these two things. The one to propose and make out an Experiment to demonstrate the common Opinion about the four Elements; And the other, to insinuate divers things which he thinks may repair the weakness of his Argument, from Experience, and upon other Accounts bring some credit to the otherwise defenceless Doctrine he maintains. To begin then with his Experiment of the burning Wood, it seems to me to be obnoxious to not a few considerable Exceptions. And first, if I would now deal rigidly with my Adversary, I might here make a great Question of the very way of Probation which he and others employ, without the least scruple, to evince, that the Bodies commonly call'd mixt, are made up of Earth, Air, Water, and Fire, which they are pleas'd also to call Elements; namely that upon the suppos'd _Analysis_ made by the fire, of the former sort of _Concretes_, there are wont to emerge Bodies resembling those which they take for the Elements. For not to Anticipate here what I foresee I shall have occasion to insist on, when I come to discourse with _Philoponus_ concerning the right that fire has to pass for the proper and Universal Instrument of Analysing mixt Bodies, not to Anticipate that, I say, if I were dispos'd to wrangle, I might alledge, that by _Themistius_ his Experiment it would appear rather that those he calls Elements, are made of those he calls mixt Bodies, then mix'd Bodies of the Elements. For in _Themistius's_ Analyz'd Wood, and in other Bodies dissipated and alter'd by the fire, it appears, and he confesses, that which he takes for Elementary Fire and Water, are made out of the Concrete; but it appears not that the Concrete was made up of Fire and Water. Nor has either He, or any Man, for ought I know, of his perswasion, yet prov'd that nothing can be obtained from a Body by the fire that was not _Pre-existent_ in it. At this unexpected objection, not only _Themistius_, but the rest of the company appear'd not a little surpriz'd; but after a while _Philoponus_ conceiving his opinion, as well as that of _Aristotle_, concern'd in that Objection, You cannot sure (sayes he to _Carneades_) propose this Difficulty; not to call it Cavill, otherwise then as an Exercise of wit, and not as laying any weight upon it. For how can that be separated from a thing that was not existent in it. When, for instance, a Refiner mingles Gold and Lead, and exposing this Mixture upon a Cuppell to the violence of the fire, thereby separates it into pure and refulgent Gold and Lead (which driven off together with the Dross of the Gold is thence call'd _Lithargyrium Auri_) can any man doubt that sees these two so differing substances separated from the Mass, that they were existent in it before it was committed to the fire. I should (replies _Carneades_) allow your Argument to prove something, if, as Men see the Refiners commonly take before hand both Lead and Gold to make the Mass you speak of, so we did see Nature pull down a parcell of the Element of Fire, that is fancy'd to be plac'd I know not how many thousand Leagues off, contiguous to the Orb of the Moon, and to blend it with a quantity of each of the three other Elements, to compose every mixt Body, upon whose Resolution the Fire presents us with Fire, and Earth, and the rest. And let me add, _Philoponus_, that to make your Reasoning cogent, it must be first prov'd, that the fire do's only take the Elementary Ingredients asunder, without otherwise altering them. For else 'tis obvious, that Bodies may afford substances which were not pre-existent in them; as Flesh too long kept produces Magots, and old Cheese Mites, which I suppose you will not affirm to be Ingredients of those Bodies. Now that fire do's not alwayes barely separate the Elementary parts, but sometimes at least alter also the Ingredients of Bodies, if I did not expect ere long a better occasion to prove it, I might make probable out of your very Instance, wherein there is nothing Elementary separated by the great violence of the Refiners fire: the Gold and Lead which are the two Ingredients separated upon the _Analysis_ being confessedly yet perfectly mixt Bodies, and the Litharge being Lead indeed; but such Lead as is differing in consistence and other Qualities from what it was before. To which I must add that I have sometimes seen, and so questionlesse have you much oftener, some parcells of Glasse adhering to the Test or Cuppel, and this Glass though Emergent as well as the Gold or Litharge upon your Analysis, you will not I hope allow to have been a third Ingredient of the Mass out of which the fire produc'd it. Both _Philoponus_ and _Themistius_ were about to reply, when _Eleutherius_ apprehending that the Prosecution of this Dispute would take up time, which might be better employ'd, thought fit to prevent them by saying to _Carneades_: You made at least half a Promise, when you first propos'd this Objection, that you would not (now at least) insist on it, nor indeed does it seem to be of absolute necessity to your cause, that you should. For though you should grant that there are Elements, it would not follow that there must be precisely four. And therefore I hope you will proceed to acquaint us with your other and more considerable Objections against _Themistius's_ Opinion, especially since there is so great a Disproportion in Bulke betwixt the Earth, Water and Air, on the one part, and those little parcells of resembling substances, that the fire separates from _Concretes_ on the other part, that I can scarce think that you are serious, when to lose no advantage against your Adversary, you seem to deny it to be rational, to conclude these great simple Bodies to be the Elements, and not the Products of compounded ones. What you alledge (replies _Carneades_) of the Vastness of the Earth and Water, has long since made me willing to allow them to be the greatest and chief Masses of Matter to be met with here below: But I think I could shew You, if You would give me leave, that this will prove only that the Elements, as You call them, are the chief Bodies that make up the neighbouring part of the World, but not that they are such Ingredients as every mixt Body must consist of. But since You challenge me of something of a Promise, though it be not an entire one, Yet I shall willingly perform it. And indeed I intended not when I first mention'd this Objection, to insist on it at present against _Themistius_, (as I plainly intimated in my way of proposing it:) being only desirous to let you see, that though I discern'd my Advantages, yet I was willing to forego some of them, rather then appear a rigid Adversary of a Cause so weak, that it may with safety be favourably dealt with. But I must here profess, and desire You to take Notice of it, that though I pass on to another Argument, it is not because I think this first invalid. For You will find in the Progress of our Dispute, that I had some reason to question the very way of Probation imploy'd both by Peripateticks and Chymists, to evince the being and number of the Elements. For that there are such, and that they are wont to be separated by the Analysis made by Fire, is indeed taken for granted by both Parties, but has not (for ought I know) been so much as plausibly attempted to be proved by either. Hoping then that when we come to that part of our Debate, wherein Considerations relating to this Matter are to be treated of, you will remember what I have now said, and that I do rather for a while suppose, then absolutely grant the truth of what I have question'd, I will proceed to another Objection. And hereupon _Eleutherius_ having promis'd him not to be unmindfull, when time should serve, of what he had declar'd. I consider then (sayes _Carneades_) in the next place, that there are divers Bodies out of which _Themistius_ will not prove in haste, that there can be so many Elements as four extracted by the Fire. And I should perchance trouble him if I should ask him what Peripatetick can shew us, (I say not, all the four Elements, for that would be too rigid a Question, but) any one of them extracted out of Gold by any degree of Fire whatsoever. Nor is Gold the only Bodie in Nature that would puzzle an _Aristotelian_, that is no more [Errata: (that is no more)] to analyze by the Fire into Elementary Bodies, since, for ought I have yet observ'd, both Silver and calcin'd _Venetian_ Talck, and some other Concretes, not necessary here to be nam'd, are so fixt, that to reduce any of them into four Heterogeneous Substances has hitherto prov'd a Task much too hard, not only for the Disciples of _Aristotle_, but those of _Vulcan_, at least, whilst the latter have employ'd only Fire to make the _Analysis_. The next Argument (continues _Carneades_) that I shall urge against _Themistius's_ Opinion shall be this, That as there are divers Bodies whose _Analysis_ by Fire cannot reduce them into so many Heterogeneous Substances or Ingregredients [Transcriber's Note: Ingredients] as four, so there are others which may be reduc'd into more, as the Blood (and divers other parts) of Men and other Animals, which yield when analyz'd five distinct Substances, Phlegme, Spirit, Oyle, Salt and Earth, as Experience has shewn us in distilling Mans Blood, Harts-Horns, and divers other Bodies that belonging to the Animal-Kingdom abound with not uneasily sequestrable Salt. THE SCEPTICAL CHYMIST: OR CHYMICO-PHYSICAL Doubts & Paradoxes, Touching the EXPERIMENTS WHEREBY VULGAR SPAGYRISTS Are wont to Endeavour to Evince their SALT, SULPHUR AND MERCURY, TO BE The True Principles of Things. _Utinam jam tenerentur omnia, & inoperta ac confessa Veritas esset! Nihil ex Decretis mutaremus. Nunc Veritatem cum eis qui docent, quærimus._ Sen. _LONDON,_ Printed for _J. Crooke_, and are to be sold at the Ship in St. _Pauls_ Church-Yard. 1661. THE SCEPTICAL CHYMIST. _The First Part._ I am (sayes _Carneades_) so unwilling to deny _Eleutherius_ any thing, that though, before the rest of the Company I am resolv'd to make good the part I have undertaken of a Sceptick; yet I shall readily, since you will have it so, lay aside for a while the Person of an Adversary to the Peripateticks and Chymists; and before I acquaint you with my Objections against their Opinions, acknowledge to you what may be (whether truly or not) tollerably enough added, in favour of a certain number of Principles of mixt Bodies, to that grand and known Argument from the _Analysis_ of compound Bodies, which I may possibly hereafter be able to confute. And that you may the more easily Examine, and the better Judge of what I have to say, I shall cast it into a pretty number of distinct Propositions, to which I shall not premise any thing; because I take it for granted, that you need not be advertis'd, that much of what I am to deliver, whether for or against a determinate number of Ingredients of mix'd Bodies, may be indifferently apply'd to the four Peripatetick Elements, and the three Chymical Principles, though divers of my Objections will more peculiarly belong to these last nam'd, because the Chymical _Hypothesis_ seeming to be much more countenanc'd by Experience then the other, it will be expedient to insist chiefly upon the disproving of that; especially since most of the Arguments that are imploy'd against it, may, by a little variation, be made to conclude, at least as strongly against the less plausible, _Aristotelian_ Doctrine. To proceed then to my Propositions, I shall begin with this. That [Sidenote: Propos. I.] _It seems not absurd to conceive that at the first Production of mixt Bodies, the Universal Matter whereof they among other Parts of the Universe consisted, was actually divided into little Particles of several sizes and shapes variously mov'd._ This (sayes _Carneades_) I suppose you will easily enough allow. For besides that which happens in the Generation, Corruption, Nutrition, and wasting of Bodies, that which we discover partly by our _Microscopes_ of the extream littlenesse of even the scarce sensible parts of Concretes; and partly by the Chymical Resolutions of mixt Bodies, and by divers other Operations of Spagyrical Fires upon them, seems sufficiently to manifest their consisting of parts very minute and of differing Figures. And that there does also intervene a various local Motion of such small Bodies, will scarce be denied; whether we chuse to grant the Origine of Concretions assign'd by _Epicurus_, or that related by _Moses_. For the first, as you well know, supposes not only all mixt Bodies, but all others to be produc'd by the various and casual occursions of Atomes, moving themselves to and fro by an internal Principle in the Immense or rather Infinite _Vacuum_. And as for the inspir'd Historian, He, informing us that the great and Wise Author of Things did not immediately create Plants, Beasts, Birds, &c. but produc'd them out of those portions of the pre-existent, though created, Matter, that he calls Water and Earth, allows us to conceive, that the constituent Particles whereof these new Concretes were to consist, were variously moved in order to their being connected into the Bodies they were, by their various Coalitions and Textures, to compose. But (continues _Carneades_) presuming that the first Proposition needs not be longer insisted on, I will pass on to the second, and tell you that [Sidenote: Propos. II.] _Neither is it impossible that of these minute Particles divers of the smallest and neighbouring ones were here and there associated into minute Masses or Clusters, and did by their Coalitions constitute great store of such little primary Concretions or Masses as were not easily dissipable into such Particles as compos'd them._ To what may be deduc'd, in favour of this Assertion, from the Nature of the Thing it self, I will add something out of Experience, which though I have not known it used to such a purpose, seems to me more fairly to make out that there May be Elementary Bodies, then the more questionable Experiments of Peripateticks and Chymists prove that there Are such. I consider then that Gold will mix and be colliquated not only with Silver, Copper, Tin and Lead, but with Antimony, _Regulus Martis_ and many other Minerals, with which it will compose Bodies very differing both from Gold, and the other Ingredients of the resulting Concretes. And the same Gold will also by common _Aqua Regis_, and (I speak it knowingly) by divers other _Menstruums_ be reduc'd into a seeming Liquor, in so much that the Corpuscles of Gold will, with those of the _Menstruum_, pass through Cap-Paper, and with them also coagulate into a Crystalline Salt. And I have further try'd, that with a small quantity of a certain Saline Substance I prepar'd, I can easily enough sublime Gold into the form of red Crystalls of a considerable length; and many other wayes may Gold be disguis'd, and help to constitute Bodies of very differing Natures both from It and from one another, and neverthelesse be afterward reduc'd to the self-same Numerical, Yellow, Fixt, Ponderous and Malleable Gold it was before its commixture. Nor is it only the fixedst of Metals, but the most fugitive, that I may employ in favour of our Proposition: for Quicksilver will with divers Metals compose an _Amalgam_, with divers _Menstruums_ it seems to be turn'd into a Liquor, with _Aqua fortis_ will be brought into either a red or white Powder or precipitate, with Oyl of Vitriol into a pale Yellow one, with Sulphur it will compose a blood-red and volatile Cinaber, with some Saline Bodies it will ascend in form of a Salt which will be dissoluble in water; with _Regulus_ of Antimony and Silver I have seen it sublim'd into a kinde of Crystals, with another Mixture I reduc'd it into a malleable Body, into a hard and brittle Substance by another: And some there are who affirm, that by proper Additaments they can reduce Quicksilver into Oyl, nay into Glass, to mention no more. And yet out of all these exotick Compounds, we may recover the very same running Mercury that was the main Ingredient of them, and was so disguis'd in them. Now the Reason (proceeds _Carneades_) that I have represented these things concerning Gold and Quicksilver, is, That it may not appear absurd to conceive, that such little primary Masses or Clusters, as our Proposition mentions, may remain undissipated, notwithstanding their entring into the composition of various Concretions, since the Corpuscle of Gold and Mercury, though they be not primary Concretions of the most minute Particles or matter, but confessedly mixt Bodies, are able to concurre plentifully to the composition of several very differing Bodies, without losing their own Nature or Texture, or having their cohæsion violated by the divorce of their associated parts or Ingredients. Give me leave to add (sayes _Eleutherius_) on this occasion, to what you now observ'd, that as confidently as some Chymists, and other modern Innovators in Philosophy are wont to object against the Peripateticks, That from the mixture of their four Elements there could arise but an inconsiderable variety of compound Bodies; yet if the _Aristotelians_ were but half as well vers'd in the works of Nature as they are in the Writings of their Master, the propos'd Objection would not so calmly triumph, as for want of Experiments they are fain to suffer it to do. For if we assigne to the Corpuscles, whereof each Element consists, a peculiar size and shape, it may easily enough be manifested, That such differingly figur'd Corpuscles may be mingled in such various Proportions, and may be connected so many several wayes, that an almost incredible number of variously qualified Concretes may be compos'd of them. Especially since the Corpuscles of one Element may barely, by being associated among themselves, make up little Masses of differing size and figure from their constituent parts: and since also to the strict union of such minute Bodies there seems oftentimes nothing requisite, besides the bare Contact of a great part of their Surfaces. And how great a variety of _Phænomena_ the same matter, without the addition of any other, and only several ways dispos'd or contexed, is able to exhibit, may partly appear by the multitude of differing Engins which by the contrivances of skilful Mechanitians, and the dexterity of expert Workmen, may be made of Iron alone. But in our present case being allow'd to deduce compound Bodies from four very differently qualified sorts of matter, he who shall but consider what you freshly took notice of concerning the new Concretes resulting from the mixture of incorporated Minerals, will scarce doubt but that the four Elements mannag'd by Natures Skill may afford a multitude of differing Compounds. I am thus far of your minde (sayes _Carneades_) that the _Aristotelians_ might with probability deduce a much greater number of compound Bodies from the mixture of their four Elements, than according to their present _Hypothesis_ they can, if instead of vainly attempting to deduce the variety and properties of all mixt Bodies from the Combinations and Temperaments of the four Elements, as they are (among them) endowd with the four first Qualities, they had endeavoured to do it by the Bulk and Figure of the smallest parts of those supposed Elements. For from these more Catholick and Fruitfull Accidents of the Elementary matter may spring a great variety of Textures, upon whose Account a multitude of compound Bodies may very much differ from one another. And what I now observe touching the four Peripatetick Elements, may be also applyed, _mutatis mutandis_, (as they speak) to the Chymical Principles. But (to take notice of that by the by) both the one and the other, must, I fear, call in to their assistance something that is not Elementary, to excite or regulate the motion of the parts of the matter, and dispose them after the manner requisite to the Constitution of particular Concretes. For that otherwise they are like to give us but a very imperfect account of the Origine of very many mixt Bodies, It would, I think, be no hard matter to perswade you, if it would not spend time, and were no Digression, to examine, what they are wont to alledge of the Origine of the Textures and Qualities of mixt Bodies, from a certain substantial Form, whose Origination they leave more obscure than what it is assum'd to explicate. But to proceed to a new Proposition. [Sidenote: Propos. III.] _I shall not peremptorily deny, that from most of such mixt Bodies as partake either of Animal or Vegetable Nature, there may by the Help of the Fire, be actually obtain'd a determinate number (whether Three, Four or Five, or fewer or more) of Substances, worthy of differing Denominations._ Of the Experiments that induce me to make this Concession, I am like to have occasion enough to mention several in the prosecution of my Discourse. And therefore, that I may not hereafter be oblig'd to trouble You and my self with needless Repetitions, I shall now only desire you to take notice of such Experiments, when they shall be mention'd, and in your thoughts referre them hither. To these three Concessions I have but this Fourth to add, That [Sidenote: Propos. IV.] _It may likewise be granted, that those distinct Substances, which Concretes generally either afford or are made up of, may without very much Inconvenience be call'd the Elements or Principles of them._ When I said, _without very much Inconvenience_, I had in my Thoughts that sober Admonition of _Galen_, _Cum de re constat, de verbis non est Litigandum_. And therefore also I scruple not to say _Elements_ or _Principles_, partly because the Chymists are wont to call the Ingredients of mixt Bodies, _Principles_, as the _Aristotelians_ name them _Elements_; I would here exclude neither. And, partly, because it seems doubtfull whether the same Ingredients may not be call'd _Principles_? as not being compounded of any more primary Bodies: and _Elements_, in regard that all mix'd Bodies are compounded of them. But I thought it requisite to limit my Concession by premising the words, _very much_, to the word _Inconvenience_, because that though the Inconvenience of calling the distinct Substances, mention'd in the Proposition _Elements_ or _Principles_, be not very great, yet that it is an Impropriety of Speech, and consequently in a matter of this moment not to be altogether overlook'd, You will perhaps think, as well as I, by that time you shall have heard the following part of my Discourse, by which you will best discern what Construction to put upon the former Propositions, and how far they may be look'd upon, as things that I concede as true, and how far as things I only represent as specious enough to be fit to be consider'd. And now _Eleutherius_ (continues _Carneades_) I must resume the person of a Sceptick, and as such, propose some part of what may be either dislik't, or at least doubted of in the common _Hypothesis_ of the Chymists: which if I examine with a little the more freedom, I hope I need not desire you (a Person to whom I have the Happinesse of being so well known) to look upon it as something more suitable to the Employment whereto the Company has, for this Meeting, doom'd me; then either to my Humour or my Custom. Now though I might present you many things against the Vulgar Chymical Opinion of the three Principles, and the Experiments wont to be alledg'd as Demonstrations of it, yet those I shall at present offer you may be conveniently enough comprehended in four Capital Considerations; touching all which I shall only premise this in general, That since it is not my present Task so much to assert an _Hypothesis_ of my own, as to give an Account wherefore I suspect the Truth of that of the Chymists, it ought not to be expected that all my Objections should be of the most cogent sort, since it is reason enough to Doubt of a propos'd Opinion, that there appears no cogent Reason for it. To come then to the Objections themselves; I consider in the first place, That notwithstanding what common Chymists have prov'd or taught, it may reasonably enough be Doubted, how far, and in what sence, Fire ought to be esteem'd the genuine and universal Instrument of analyzing mixt Bodies. This Doubt, you may remember, was formerly mention'd, but so transiently discours'd of, that it will now be fit to insist upon it; And manifest that it was not so inconsiderately propos'd as our Adversaries then imagin'd. But, before I enter any farther into this Disquisition, I cannot but here take notice, that it were to be wish'd, our Chymists had clearly inform'd us what kinde of Division of Bodies by Fire must determine the number of the Elements: For it is nothing near so easy as many seem to think, to determine distinctly the Effects of Heat, as I could easily manifest, if I had leasure to shew you how much the Operations of Fire may be diversify'd by Circumstances. But not wholly to pass by a matter of this Importance, I will first take notice to you, that _Guajacum_ (for Instance) burnt with an open Fire in a Chimney, is sequestred into Ashes and Soot, whereas the same Wood distill'd in a Retort does yield far other Heterogeneities, (to use the _Helmontian_ expression) and is resolv'd into Oyl, Spirit, Vinager, Water and Charcoal; the last of which to be reduc'd into Ashes, requires the being farther calcin'd then it can be in a close Vessel: Besides having kindled Amber, and held a clean Silver Spoon, or some other Concave and smooth Vessel over the Smoak of its Flame, I observ'd the Soot into which that Fume condens'd, to be very differing from any thing that I had observ'd to proceed from the steam of Amber purposely (for that is not usual) distilled _per se_ in close Vessels. Thus having, for Tryals sake, kindled Camphire, and catcht the Smoak that copiously ascended out of the Flame, it condens'd into a Black and unctuous Soot, which would not have been guess'd by the Smell or other Properties to have proceeded from Camphire: whereas having (as I shall otherwhere more fully declare) expos'd a quantity of that Fugitive Concrete to a gentle heat in a close Glass-Vessel, it sublim'd up without seeming to have lost any thing of its whiteness, or its Nature, both which it retain'd, though afterwards I so encreased the Fire as to bring it to Fusion. And, besides Camphire, there are divers other Bodies (that I elsewhere name) in which the heat in close Vessels is not wont to make any separation of Heterogeneities, but only a comminution of Parts, those that rise first being Homogeneal with the others, though subdivided into smaller Particles: whence Sublimations have been stiled, _The Pestles of the Chymists_. But not here to mention what I elsewhere take notice of, concerning common Brimstone once or twice sublim'd, that expos'd to a moderate Fire in Subliming-Pots, it rises all into dry, and almost tastless, Flowers; Whereas being expos'd to a naked Fire it affords store of a Saline and Fretting Liquor: Not to mention this, I say, I will further observe to you, that as it is considerable in the _Analysis_ of mixt Bodies, whether the Fire act on them when they are expos'd to the open Air, or shut up in close Vessels, so is the degree of Fire by which the _Analysis_ is attempted of no small moment. For a milde _Balneum_ will sever unfermented Blood (for Instance) but into Phlegme and _Caput mortuum_, the later whereof (which I have sometimes had) hard, brittle, and of divers Colours, (transparent almost like Tortoise-shell) press'd by a good Fire in a Retort yields a Spirit, an Oyl or two, and a volatile Salt, besides a [Errata: another] _Caput mortuum_. It may be also pertinent to our present Designe, to take notice of what happens in the making and distilling of Sope; for by one degree of Fire the Salt, the Water and the Oyl or Grease, whereof that factitious Concrete is made up, being boyl'd up together are easily brought to mingle and incorporate into one Mass; but by another and further degree of Heat the same Mass may be again divided into an oleagenous, an aqueous, a Saline, and an Earthy part. And so we may observe that impure Silver and Lead being expos'd together to a moderate Fire, will thereby be colliquated into one Mass, and mingle _per minima_, as they speak, whereas a much vehementer Fire will drive or carry off the baser Metals (I mean the Lead, and the Copper or other Alloy) from the Silver, though not, for ought appears, separate them from one another. Besides, when a Vegetable abounding in fixt Salt is analyz'd by a naked Fire, as one degree of Heat will reduce it into Ashes, (as the Chymists themselves teach us) so, by only a further degree of Fire, those Ashes may be vitrified and turn'd into Glass. I will not stay to examine how far a meere Chymist might on this occasion demand, If it be lawful for an _Aristotelian_ to make Ashes, (which he mistakes for meere Earth) pass for an Element, because by one degree of Fire it may be produc'd, why a Chymist may not upon the like Principle argue, that Glass is one of the Elements of many Bodies, because that also may be obtain'd from them, barely by the Fire? I will not, I say, lose time to examine this, but observe, that by a Method of applying the Fire, such similar Bodies may be obtain'd from a Concrete, as Chymists have not been able to separate; either by barely burning it in an open Fire, or by barely distilling it in close Vessels. For to me it seems very considerable, and I wonder that men have taken so little notice of it, that I have not by any of the common wayes of Distillation in close Vessels, seen any separation made of such a volatile Salt as is afforded us by Wood, when that is first by an open Fire divided into Ashes and Soot, and that Soot is afterwards plac'd in a strong Retort, and compell'd by an urgent Fire to part with its Spirit, Oyl and Salt; for though I dare not peremptorily deny, that in the Liquors of _Guajacum_ and other Woods distill'd in Retorts after the common manner, there may be Saline parts, which by reason of the Analogy may pretend to the name of some kinde of volatile Salts; yet questionless there is a great disparity betwixt such Salts and that which we have sometimes obtain'd upon the first Distillation of Soot (though for the most part it has not been separated from the first or second Rectification, and sometimes not till the third) For we could never yet see separated from Woods analyz'd only the vulgar way in close vessels any volatile Salt in a dry and Saline form, as that of Soot, which we have often had very Crystalline and Geometrically figur'd. And then, whereas the Saline parts of the Spirits of _Guajacum_, &c. appear upon distillation sluggish enough, the Salt of Soot seems to be one of the most volatile Bodies in all Nature; and if it be well made will readily ascend with the milde heat of a Furnace, warm'd only by the single Wieck of a Lamp, to the top of the highest Glass Vessels that are commonly made use of for Distillation: and besides all this, the taste and smell of the Salt of Soot are exceeding differing from those of the Spirits of _Guajacum_, &c. and the former not only smells and tastes much less like a vegetable Salt, than like that of Harts-horn, and other Animal Concretes; but in divers other Properties seems more of Kinne to the Family of Animals, than to that of vegetable Salts, as I may elsewhere (God permitting) have an occasion more particularly to declare. I might likewise by some other Examples manifest, That the Chymists, to have dealt clearly, ought to have more explicitly and particularly declar'd by what Degree of Fire, and in what manner of Application of it, they would have us Judge a Division made by the Fire to be a true _Analysis_ into their Principles, and the Productions of it to deserve the name of Elementary Bodies. But it is time that I proceed to mention the particular Reasons that incline me to Doubt, whether the Fire be the true and universal Analyzer of mixt Bodies; of which Reasons what has been already objected may pass for one. In the next place I observe, That there are some mixt Bodies from which it has not been yet made appear, that any degree of Fire can separate either Salt or Sulphur or Mercury, much less all the Three. The most obvious Instance of this Truth is Gold, which is a Body so fix'd, and wherein the Elementary Ingredients (if it have any) are so firmly united to each other, that we finde not in the operations wherein Gold is expos'd to the Fire, how violent soever, that it does discernably so much as lose of its fixednesse or weight, so far is it from being dissipated into those Principles, whereof one at least is acknowledged to be Fugitive enough; and so justly did the Spagyricall Poet somewhere exclaim, _Cuncta adeo miris illic compagibus harent._ And I must not omit on this occasion to mention to you, _Eleutherius_, the memorable Experiment that I remember I met with in _Gasto Claveus_,[2] who, though a Lawyer by Profession, seems to have had no small Curiosity and Experience in Chymical affairs: He relates then, that having put into one small Earthen Vessel an Ounce of the most pure Gold, and into another the like weight of pure Silver, he plac'd them both in that part of a Glass-house Furnace wherein the Workmen keep their Metal, (as our English Artificers call their Liquid Glass) continually melted, and that having there kept both the Gold and the Silver in constant Fusion for two Moneths together, he afterwards took them out of the Furnace and the Vessels, and weighing both of them again, found that the Silver had not lost above a 12th part of its weight, but the Gold had not of his lost any thing at all. And though our Author endeavours to give us of this a Scholastick Reason, which I suppose you would be as little satisfied with, as I was when I read it; yet for the matter of Fact, which will serve our present turne, he assures us, that though it be strange, yet Experience it self taught it him to be most true. [Footnote 2: _Gasto Claveus_ Apolog. Argur. & Chrysopera.] And though there be not perhaps any other Body to be found so perfectly fix'd as Gold, yet there are divers others so fix'd or compos'd, at least of so strictly united parts, that I have not yet observ'd the Fire to separate from them any one of the Chymists Principles. I need not tell you what Complaints the more Candid and Judicious of the Chymists themselves are wont to make of those Boasters that confidently pretend, that they have extracted the Salt or Sulphur of Quicksilver, when they have disguis'd it by Additaments, wherewith it resembles the Concretes whose Names are given it; whereas by a skilful and rigid _Examen_, it may be easily enough stript of its Disguises, and made to appear again in the pristine form of running Mercury. The pretended Salts and Sulphurs being so far from being Elementary parts extracted out of the Bodie of Mercurie, that they are rather (to borrow a terme of the Grammarians) De-compound Bodies, made up of the whole Metal and the _Menstruum_ or other Additaments imploy'd to disguise it. And as for Silver, I never could see any degree of Fire make it part with any of its three Principles. And though the Experiment lately mentioned from _Claveus_ may beget a Suspition that Silver may be dissipated by Fire, provided it be extreamly violent and very lasting: yet it will not necessarily follow, that because the Fire was able at length to make the Silver lose a little of its weight, it was therefore able to dissipate it into its Principles. For first I might alledge that I have observ'd little Grains of Silver to lie hid in the small Cavities (perhaps glas'd over by a vitrifying heat) in Crucibles, wherein Silver has been long kept in Fusion, whence some Goldsmiths of my Acquaintance make a Benefit by grinding such Crucibles to powder, to recover out of them the latent particles of Silver. And hence I might argue, that perhaps _Claveus_ was mistaken, and imagin'd that Silver to have been driven away by the Fire, that indeed lay in minute parts hid in his Crucible, in whose pores so small a quantity as he mist of so ponderous a Bodie might very well lie conceal'd. But Secondly, admitting that some parts of the Silver were driven away by the violence of the Fire, what proof is there that it was either the Salt, the Sulphur, or the Mercury of the Metal, and not rather a part of it homogeneous to what remain'd? For besides, that the Silver that was left seem'd not sensibly alter'd, which probably would have appear'd, had so much of any one of its Principles been separated from it: We finde in other Mineral Bodies of a less permanent nature than Silver, that the Fire may divide them into such minute parts, as to be able to carry them away with its self, without at all destroying their Nature. Thus we see that in the refining of Silver, the Lead that is mix'd with it (to carry away the Copper or other ignoble Mineral that embases the Silver) will, if it be let alone, in time evaporate away upon the Test; but if (as is most usual amongst those that refine great quantities of Metals together) the Lead be blown off from the Silver by Bellowes, that which would else have gone away in the Form of unheeded steams, will in great part be collected not far from the Silver, in the Form of a darkish Powder or Calx, which, because it is blown off from Silver, they call Litharge of Silver. And thus _Agricola_[3] in divers places informs us, when Copper, or the Oare of it is colliquated by the violence of the Fire with _Cadmia_, the Sparks that in great multitudes do fly upwards do, some of them, stick to the vaulted Roofs of the Furnaces, in the form of little and (for the most part) White Bubbles, which therefore the Greeks, and, in Imitation of them, our Drugsters call _Pompholix_: and others more heavy partly adhere to the sides of the Furnace, and partly (especially if the Covers be not kept upon the Pots) fall to the Ground, and by reason of their Ashy Colour as well as Weight were called by the same Greeks [Greek: spodos], which, I need not tell you, in their Language signifies Ashes. I might add, that I have not found that from Venetian Talck (I say Venetian, because I have found other kinds of that Mineral more open) from the _Lapis Ossifragus_, (which the Shops call _Ostiocolla_) from _Muscovia_ Glass, from pure and Fusible Sand, to mention now no other Concretes; those of my Acquaintance that have try'd have been able by the Fire to separate any one of the Hypostatical Principles, which you will the less scruple to believe, if you consider that Glass may be made by the bare Colliquation of the Salt and Earth remaining in the Ashes of a burnt Plant, and that yet common Glass, once made, does so far resist the violence of the Fire, that most Chymists think it a Body more undestroyable then Gold it self. For if the Artificer can so firmly unite such comparative gross Particles as those of Earth and Salt that make up common Ashes, into a Body indissoluble by Fire; why may not Nature associate in divers Bodies the more minute Elementary Corpuscles she has at hand too firmly to let them be separable by the Fire? And on this Occasion, _Eleutherius_, give me leave to mention to you two or three sleight Experiments, which will, I hope, be found more pertinent to our present Discourse, than at first perhaps they will appear. The first is, that, having (for Tryals sake) put a quantity of that Fugitive Concrete, Camphire, into a Glass Vessel, and plac'd it in a gentle Heat, I found it (not leaving behinde, according to my Estimate, not so much as one Grain) to sublime to the Top of the Vessel into Flowers: which in Whiteness, Smell, &c. seem'd not to differ from the Camphire it self. Another Experiment is that of _Helmont_, who in several places affirms, That a Coal kept in a Glass exactly clos'd will never be calcin'd to Ashes, though kept never so long in a strong Fire. To countenance which I shall tell you this Tryal of my own, That having sometimes distilled some Woods, as particularly Box, whilst our _Caput mortuum_ remain'd in the Retort, it continued black like Charcoal, though the Retort were Earthen, and kept red-hot in a vehement Fire; but as soon as ever it was brought out of the candent Vessel into the open Air, the burning Coals did hastily degenerate or fall asunder, without the Assistance of any new Calcination, into pure white Ashes. And to these two I shall add but this obvious and known Observation, that common Sulphur (if it be pure and freed from its Vinager) being leasurely sublim'd in close Vessels, rises into dry Flowers, which may be presently melted into a Bodie of the same Nature with that which afforded them. Though if Brimstone be burnt in the open Air it gives, you know, a penetrating Fume, which being caught in a Glass-Bell condenses into that acid Liquor called Oyl of Sulphur _per Campanam_. The use I would make of these Experiments collated with what I lately told you out of _Agricola_ is this, That even among the Bodies that are not fixt, there are divers of such a Texture, that it will be hard to make it appear, how the Fire, as Chymists are wont to imploy it, can resolve them into Elementary Substances. For some Bodies being of such a Texture that the Fire can drive them into the cooler and less hot part of the Vessels wherein they are included, and if need be, remove them from place to place to fly the greatest heat, more easily than it can divorce their Elements (especially without the Assistance of the Air) we see that our Chymists cannot Analyze them in close Vessels, and of other compound Bodies the open Fire can as little separate the Elements. For what can a naked Fire do to Analyze a mixt Bodie, if its component Principles be so minute, and so strictly united, that the Corpuscles of it need less heat to carry them up, than is requisite to divide them into their Principles. So that of some Bodies the Fire cannot in close Vessels make any _Analysis_ at all, and others will in the open Air fly away in the Forms of Flowers or Liquors, before the Heat can prove able to divide them into their Principles. And this may hold, whether the various similar parts of a Concrete be combin'd by Nature or by Art; For in factitious _Sal Armoniack_ we finde the common and the Urinous Salts so well mingled, that both in the open Fire, and in subliming Vessels they rise together as one Salt, which seems in such Vessels irresoluble by Fire alone. For I can shew you _Sal Armoniack_ which after the ninth Sublimation does still retain its compounded Nature. And indeed I scarce know any one Mineral, from which by Fire alone Chymists are wont to sever any Substance simple enough to deserve the name of an Element or Principle. For though out of native Cinnaber they distill Quicksilver, and though from many of those Stones that the Ancients called _Pyrites_ they sublime Brimstone, yet both that Quicksilver and this Sulphur being very often the same with the common Minerals that are sold in the Shops under those names, are themselves too much compounded Bodies to pass for the Elements of such. And thus much, _Eleutherius_, for the Second Argument that belongs to my First Consideration; the others I shall the lesse insist on, because I have dwelt so long upon this. [Footnote 3: _Agricola_ de Natura Fossil. Lib. 9. Cap. 11. & 12.] Proceed we then in the next place to consider, That there are divers Separations to be made by other means, which either cannot at all, or else cannot so well be made by the Fire alone. When Gold and Silver are melted into one Mass, it would lay a great Obligation upon Refiners and Goldsmiths to teach them the Art of separating them by the Fire, without the trouble and charge they are fain to be at to sever them. Whereas they may be very easily parted by the Affusion of Spirit of Nitre or _Aqua fortis_ (which the French therefore call _Eau de Depart_:) so likewise the Metalline part of Vitriol will not be so easily and conveniently separated from the Saline part even by a violent Fire, as by the Affusion of certain Alkalizate Salts in a liquid Form upon the Solution of Vitriol made in common water. For thereby the acid Salt of the Vitriol, leaving the Copper it had corroded to joyn with the added Salts, the Metalline part will be precipitated to the bottom almost like Mud. And that I may not give Instances only in De-compound Bodies, I will add a not useless one of another kinde. Not only Chymists have not been able (for ought is vulgarly known) by Fire alone to separate true Sulphur from Antimony; but though you may finde in their Books many plausible Processes of Extracting it, yet he that shall make as many fruitlesse Tryals as I have done to obtain it by, most of them will, I suppose, be easily perswaded, that the Productions of such Processes are Antimonial Sulphurs rather in Name than Nature. But though Antimony sublim'd by its self is reduc'd but to a volatile Powder, or Antimonial Flowers, of a compounded Nature like the Mineral that affords them: yet I remember that some years ago I sublim'd out of Antimony a Sulphur, and that in greater plenty then ever I saw obtain'd from that Mineral, by a Method which I shall therefore acquaint you with, because Chymists seem not to have taken notice of what Importance such Experiments may be in the Indagation of the Nature, and especially of the Number of the Elements. Having then purposely for Tryals sake digested eight Ounces of good and well powder'd Antimony with twelve Ounces of Oyl of Vitriol in a well stopt Glas-Vessel for about six or seven Weeks; and having caus'd the Mass (grown hard and brittle) to be distill'd in a Retort plac'd in Sand, with a strong Fire; we found the Antimony to be so opened, or alter'd by the _Menstruum_ wherewith it had been digested, That whereas crude Antimony, forc'd up by the Fire, arises only in Flowers, our Antimony thus handled afforded us partly in the Receiver, and partly in the Neck and at the Top of the Retort, about an Ounce of Sulphur, yellow and brittle like common Brimstone, and of so Sulphureous a smell, that upon the unluting the Vessels it infected the Room with a scarce supportable stink. And this Sulphur, besides the Colour and Smell, had the perfect Inflamability of common Brimstone, and would immediately kindle (at the Flame of a Candle) and burn blew like it. And though it seem'd that the long digestion wherein our Antimony and _Menstruum_ were detain'd, did conduce to the better unlocking of the Mineral, yet if you have not the leasure to make so long a Digestion, you may by incorporating with powder'd Antimony a convenient Quantity of Oyl of Vitriol, and committing them immediately to Distillation, obtain a little Sulphur like unto the common one, and more combustible than perhaps you will at first take notice of. For I have observ'd, that though (after its being first kindled) the Flame would sometimes go out too soon of its self, if the same Lump of Sulphur were held again to the Flame of a Candle, it would be rekindled and burn a pretty while, not only after the second, but after the third or fourth accension. You, to whom I think I shewed my way of discovering something of Sulphureous in Oyl of Vitriol, may perchance suspect, _Eleutherius_, either that this Substance was some Venereal Sulphur that lay hid in that Liquor, and was by this operation only reduc'd into a manifest Body; or else that it was a compound of the unctuous parts of the Antimony, and the Saline ones of the Vitriol, in regard that (as _Gunther_[4] informs us) divers learned men would have Sulphur to be nothing but a mixture made in the Bowels of the Earth of Vitriolate Spirits and a certain combustible Substance. But the Quantity of Sulphur we obtain'd by Digestion was much too great to have been latent in the Oyl of Vitriol. And that Vitriolate Spirits are not necessary to the Constitution of such a Sulphur as ours, I could easily manifest, if I would acquaint you with the several wayes by which I have obtain'd, though not in such plenty, a Sulphur of Antimony, colour'd and combustible like common Brimstone. And though I am not now minded to discover them, yet I shall tell you, that to satisfie some Ingenious Men, that distill'd Vitriolate Spirits are not necessary to the obtaining of such a Sulphur as we have been considering, I did by the bare distillation of only Spirit of Nitre, from its weight of crude Antimony separate, in a short time, a yellow and very inflamable Sulphur, which, for ought I know, deserves as much the name of an Element, as any thing that Chymists are wont to separate from any Mineral by the Fire. I could perhaps tell you of other Operations upon Antimony, whereby That may be extracted from it, which cannot be forc'd out of it by the Fire; but I shall reserve them for a fitter Opportunity, and only annex at present this sleight, but not impertinent Experiment. That whereas I lately observed to you, that the Urinous and common Salts whereof _Sal Armoniack_ consists, remain'd unsever'd by the Fire in many successive Sublimations, they may be easily separated, and partly without any Fire at all, by pouring upon the Concrete finely powder'd, a Solution of Salt of Tartar, or of the Salt of Wood-Ashes; for upon your diligently mixing of these you will finde your Nose invaded with a very strong smell of Urine, and perhaps too your Eyes forc'd to water by the same subtle and piercing Body that produces the stink; both these effects proceeding from hence, that by the Alcalizate Salt, the Sea Salt that enter'd the composition of the _Sal Armoniack_ is mortify'd and made more fixt, and thereby a divorce is made between it and the volatile Urinous Salt, which being at once set at liberty, and put into motion, begins presently to fly away, and to offend the Nostrils and Eyes it meets with by the way. And if the operation of these Salts be in convenient Glasses promoted by warmth, though but by that of a Bath, the ascending Steams may easily be caught and reduc'd into a penetrant Spirit, abounding with a Salt, which I have sometimes found to be separable in a Crystalline Form. I might add to these Instances, that whereas Sublimate, consisting, as you know, of Salts & Quicksilver combin'd and carried up together by Heat, may be Sublim'd, I know not how often, by a like degree of Fire, without suffering any divorce of the component Bodies, the Mercury may be easily sever'd from the adhering Salts, if the Sublimate be distill'd from Salt of Tartar, Quick Lime, or such Alcalizate Bodies. But I will rather observe to you, _Eleutherius_, what divers ingenious men have thought somewhat strange; that by such an Additament that seems but only to promote the Separation, there may be easily obtain'd from a Concrete that by the Fire alone is easily divisible into all the Elements that Vegetables are suppos'd to consist of, such a similar Substance as differs in many respects from them all, and consequently has by many of the most Intelligent Chymists been denied to be contain'd in the mixt Body. For I know a way, and have practis'd it, whereby common Tartar, without the addition of any thing that is not perfectly a Mineral except Salt-petre, may by one Distillation in an Earthen Retort be made to afford good store of real Salt, readily dissoluble in water, which I found to be neither acid, nor of the smell of Tartar, and to be almost as volatile as Spirit of Wine it self, and to be indeed of so differing a Nature from all that is wont to be separated by Fire from Tartar, that divers Learned Men, with whom I discours'd of it, could hardly be brought to beleeve, that so fugitive a Salt could be afforded by Tartar, till I assur'd it them upon my own Knowledge. And if I did not think you apt to suspect me to be rather too backward than too forward to credit or affirm unlikely things, I could convince you by what I have yet lying by me of that anomalous Salt. [Footnote 4: Lib. 1. Observat. Cap. 6.] The Fourth thing that I shall alledge to countenance my first Consideration is, That the Fire even when it divides a Body into Substances of divers Consistences, does not most commonly analyze it into Hypostatical Principles, but only disposes its parts into new Textures, and thereby produces Concretes of a new indeed, but yet of a compound Nature. This Argument it will be requisite for me to prosecute so fully hereafter, that I hope you will then confess that 'tis not for want of good Proofs that I desire leave to suspend my Proofs till the _Series_ of my Discourse shall make it more proper and seasonable to propose them. It may be further alledg'd on the behalf of my First Consideration, That some such distinct Substances may be obtain'd from some Concretes without Fire, as deserve no less the name of Elementary, than many that Chymists extort by the Violence of the Fire. We see that the Inflamable Spirit, or as the Chymists esteem it, the Sulphur of Wine, may not only be separated from it by the gentle heat of a Bath, but may be distill'd either by the help of the Sun-Beams, or even of a Dunghill, being indeed of so Fugitive a Nature, that it is not easy to keep it from flying away, even without the Application of external heat. I have likewise observ'd that a Vessel full of Urine being plac'd in a Dunghill, the Putrefaction is wont after some weeks so to open the Body, that the parts disbanding the Saline Spirit, will within no very long time, if the Vessel be not stopt, fly away of it self; Insomuch that from such Urine I have been able to distill little or nothing else than a nauseous Phlegme, instead of the active and piercing Salt and Spirit that it would have afforded, when first expos'd to the Fire, if the Vessel had been carefully stopt. And this leads me to consider in the Fifth place, That it will be very hard to prove, that there can no other Body or way be given which will as well as the Fire divide Concretes into several homogeneous Substances, which may consequently be call'd their Elements or Principles, as well as those separated or produc'd by the Fire. For since we have lately seen, that Nature can successefully employ other Instruments than the Fire to separate distinct Substances from mixt Bodies, how know we, but that Nature has made, or Art may make, some such Substance as may be a fit Instrument to Analyze mixt Bodies, or that some such Method may be found by Humane Industry or Luck, by whose means compound Bodies may be resolv'd into other Substances, than such as they are wont to be divided into by the Fire. And why the Products of such an _Analysis_ may not as justly be call'd the component Principles of the Bodies that afford them, it will not be easy to shew, especially since I shall hereafter make it evident, that the Substances which Chymists are wont to call the Salts, and Sulphurs, and Mercuries of Bodies, are not so pure and Elementary as they presume, and as their _Hypothesis_ requires. And this may therefore be the more freely press'd upon the Chymists, because neither the _Paracelsians_, nor the _Helmontians_ can reject it without apparent Injury to their respective Masters. For _Helmont_ do's more than once Inform his Readers, that both _Paracelsus_ and Himself were Possessors of the famous Liquor, _Alkahest_, which for its great power in resolving Bodies irresoluble by Vulgar Fires, he somewhere seems to call _Ignis Gehennæ_. To this Liquor he ascribes, (and that in great part upon his own Experience) such wonders, that if we suppose them all true, I am so much the more a Friend to Knowledge than to Wealth, that I should think the _Alkahest_ a nobler and more desireable Secret than the Philosophers Stone it self. Of this Universal Dissolvent he relates, That having digested with it for a competent time a piece of Oaken Charcoal, it was thereby reduc'd into a couple of new and distinct Liquors, discriminated from each other by their Colour and Situation, and that the whole body of the Coal was reduc'd into those Liquors, both of them separable from his Immortal _Menstruum_, which remain'd as fit for such Operations as before. And he moreover tells us in divers places of his Writings, that by this powerful, and unwearied Agent, he could dissolve Metals, Marchasites, Stones, Vegetable and Animal Bodies of what kinde soever, and even Glass it self (first reduc'd to powder,) and in a word, all kinds of mixt Bodies in the World into their several similar Substances, without any Residence or _Caput mortuum_. And lastly, we may gather this further from his Informations, That the homogeneous Substances obtainable from compound Bodies by his piercing Liquor, were oftentimes different enough both as to Number and as to Nature, from those into which the same Bodies are wont to be divided by common Fire. Of which I shall need in this place to mention no other proof, then that whereas we know that in our common _Analysis_ of a mixt Body, there remains a terrestrial and very fixt Substance, oftentimes associated with a Salt as fixt; Our Author tells us, that by his way he could Distill over all Concretes without any _Caput mortuum_, and consequently could make those parts of the Concrete volatile, which in the Vulgar _Analysis_ would have been fixt. So that if our Chymists will not reject the solemn and repeated Testimony of a Person, who cannot but be acknowledg'd for one of the greatest Spagyrists that they can boast of, they must not deny that there is to be found in Nature another Agent able to Analyze compound Bodies less violently, and both more genuinely and more universally than the Fire. And for my own part, though I cannot but say on this Occasion what (you know) our Friend Mr. _Boyle_ is wont to say, when he is askt his Opinion of any strange Experiment; _That He that hath seen it hath more Reason to beleeve it, than He that hath not_; yet I have found _Helmont_ so faithful a Writer, even in divers of his improbable Experiments (I alwayes except that Extravagant Treatise _De Magnetica Vulnerum Curatione_, which some of his Friends affirm to have been first publish'd by his Enemies) that I think it somewhat harsh to give him the Lye, especially to what he delivers upon his own proper Tryal. And I have heard from very credible Eye-witnesses some things, and seen some others my self, which argue so strongly, that a circulated Salt, or a _Menstruum_ (such as it may be) may by being abstracted from compound Bodies, whether Mineral, Animal, or Vegetable, leave them more unlockt than a wary Naturalist would easily beleeve, that I dare not confidently measure the Power of Nature and Art by that of the _Menstruums_, and other Instruments that eminent Chymists themselves are as yet wont to Empoly [Errata: employ] about the Analyzing of Bodies; nor Deny that a _Menstruum_ may at least from this or that particular Concrete obtain some apparently similar Substance, differing from any obtainable from the same Body by any degree or manner of Application of the Fire. And I am the more backward to deny peremptorily, that there may be such Openers of compound Bodies, because among the Experiments that make me speak thus warily, there wanted not some in which it appear'd not, that one of the Substances not separable by common Fires and _Menstruums_ could retain any thing of the Salt by which the separation was made. And here, _Eleutherius_, (sayes _Carneades_) I should conclude as much of my Discourse as belongs to the first Consideration I propos'd, but that I foresee, that what I have delivered will appear liable to two such specious Objections, that I cannot safely proceed any further till I have examin'd them. And first, one sort of Opposers will be forward to tell me, That they do not pretend by Fire alone to separate out of all compound Bodies their _Hypostatical_ Principles; it being sufficient that the Fire divides them into such, though afterwards they employ other Bodies to collect the similar parts of the Compound; as 'tis known, that though they make use of water to collect the Saline parts of Ashes from the Terrestrial wherewith they are blended, yet it is the Fire only that Incinerates Bodies, and reduces the fix'd part of them into the Salt and Earth, whereof Ashes are made up. This Objection is not, I confess, inconsiderable, and I might in great part allow of it, without granting it to make against me, if I would content my self to answer, that it is not against those that make it that I have been disputing, but against those Vulgar Chymists, who themselves believe, and would fain make others do so, That the Fire is not only an universal, but an adæquate [Transcriber's Note: adequate] and sufficient Instrument to analyze mixt Bodies with. For as to their Practice of Extracting the fix'd Salt out of Ashes by the Affusion of Water, 'tis obvious to alleadge, that the Water does only assemble together the Salt the Fire had before divided from the Earth: as a Sieve does not further break the Corn, but only bring together into two distinct heaps the Flour and the Bran, whose Corpuscles before lay promiscuously blended together in the Meal. This I say I might alleadge, and thereby exempt my self from the need of taking any farther notice of the propos'd Objection. But not to lose the Rise it may afford me of Illustrating the matter under Consideration, I am content briefly to consider it, as far forth as my present Disquisition may be concern'd in it. Not to repeat then what has been already answer'd, I say farther, that though I am so civil an Adversary, that I will allow the Chymists, after the Fire has done all its work, the use of fair Water to make their Extractions with, in such cases wherein the Water does not cooperate with the Fire to make the _Analysis_; yet since I Grant this but upon Supposition that the Water does only wash off the Saline Particles, which the Fire Alone has Before Extricated in the Analyz'd Body, it will not be Reasonable, that this Concession should Extend to other Liquors that may Add to what they Dissolve, nor so much as to other Cases than those Newly Mentioned: Which Limitation I Desire You would be Pleas'd to Bear in Mind till I shall Anon have Occasion to make Use of it. And This being thus Premis'd, I shall Proceed to Observe, First, That Many of the Instances I Propos'd in the Preceding Discourse are Such, that the Objection we are Considering will not at all Reach Them. For Fire can no more with the Assistance of Water than without it Separate any of the Three Principles, either from Gold, Silver, Mercury, or some Others of the Concretes named Above. Hence We may Inferre, That Fire is not an Universal Analyzer of all Mixt Bodies, since of Metals and Minerals, wherein Chymists have most Exercis'd Themselves, there Appear scarce Any which they are able to Analyze by Fire, Nay, from which they can Unquestionably Separate so much as any One of their Hypostatical Principles; Which may well Appear no small Disparagement as well to their _Hypothesis_ as to their Pretensions. It will also remain True, notwithstanding the Objection, That there may be Other Wayes than the wonted _Analysis_ by Fire, to Separate from a Compound Body Substances as Homogeneneous [Transcriber's Note: Homogeneous] as those that Chymists Scruple not to Reckon among their _Tria Prima_ (as some of them, for Brevity Sake, call their Three Principles.) And it Appears, That by Convenient Additaments such Substances may be Separated by the Help of the Fire, as could not be so by the Fire alone: Witness the Sulphur of Antimony. And Lastly, I must Represent, That since it appears too that the Fire is but One of the Instruments that must be Employ'd in the Resolution of Bodies, We may Reasonably Challenge the Liberty of doing Two Things. For when ever any _Menstruum_ or other Additament is Employ'd, together with the Fire to Obtain a Sulphur or a Salt from a Body, We may well take the Freedom to Examine, whether or no That _Menstruum_ do barely Help to Separate the Principle Obtain'd by It, or whether there Intervene not a Coalition of the Parts of the Body Wrought upon with Those of the _Menstruum_, whereby the Produc'd Concrete may be Judg'd to Result from the Union of Both. And it will be farther Allowable for Us to Consider, how far any Substance, Separated by the Help of such Additaments, Ought to pass for one of the _Tria Prima_; since by One Way of Handling the same Mixt Body it may according to the Nature of the Additaments, and the Method of Working upon it, be made to Afford differing Substances from those Obtainable from it by other Additaments, and another Method, nay and (as may appear by what I Formerly told You about Tartar) Differing from any of the Substances into which a Concrete is Divisible by the Fire without Additaments, though perhaps those Additaments do not, as Ingredients, enter the Composition of the Obtained Body, but only Diversify the Operation of the Fire upon the Concrete; and though that Concrete by the Fire alone may be Divided into a Number of Differing Substances, as Great as any of the Chymists that I have met with teach us that of the Elements to be. And having said thus much (sayes _Carneades_) to the Objection likely to be Propos'd by some Chymists, I am now to Examine that which I Foresee will be Confidently press'd by Divers Peripateticks, who, to Prove Fire to be the true Analyzer of Bodies, will Plead, That it is the very Definition of Heat given by _Aristotle_, and Generally Received, _Congregare Homogenea, & Heterogenea Segregare_, to Assemble Things of a Resembling, and Disjoyn those of a Differing Nature. To this I answer, That this Effect is far from being so Essential to Heat, as 'tis Generally Imagin'd; for it rather Seems, that the True and Genuine Property of Heat is, to set a Moving, and thereby to Dissociate the parts of Bodies, and Subdivide them into Minute Particles, without regard to their being Homogeneous or Heterogeneous, as is apparent in the Boyling of Water, the Distillation of Quicksilver, or the Exposing of Bodies to the action of the Fire, whose Parts either Are not (at least in that Degree of Heat Appear not) Dissimilar, where all that the Fire can do, is to Divide the Body into very Minute Parts which are of the same Nature with one another, and with their _Totum_, as their Reduction by Condensation Evinces. And even when the Fire seems most so _Congregare Homogenea, & Segregare Heterogenea_, it Produces that Effect but by Accident; For the Fire does but Dissolve the Cement, or rather Shatter the Frame, or [tructure [Errata: structure] that kept the Heterogeneous Parts of Bodies together, under one Common Form; upon which Dissolution the Component Particles of the Mixt, being Freed and set at Liberty, do Naturally, and oftentimes without any Operation of the Fire, Associate themselves each with its Like, or rather do take those places which their Several Degrees of Gravity and Levity, Fixedness or Volatility (either Natural, or Adventitious from the Impression of the Fire) Assigne them. Thus in the Distillation (for Instance) of Man's Blood, the Fire do's First begin to Dissolve the _Nexus_ or Cement of the Body; and then the Water, being the most Volatile, and Easy to be Extracted, is either by the Igneous Atomes, or the Agitation they are put into by the Fire, first carried up, till Forsaken by what carried it up, its Weight sinks it down into the Receiver: but all this while the other Principles of the Concrete Remain Unsever'd, and Require a stronger Degree of Heat to make a Separation of its more Fixt Elements; and therefore the Fire must be Increas'd which Carries over the Volatile Salt and the Spirit, they being, though Beleev'd to be Differing Principles, and though Really of Different Consistency, yet of an almost Equal Volatility. After them, as less Fugitive, comes over the Oyl, and leaves behinde the Earth and the _Alcali_, which being of an Equal Fixednesse, the Fire Severs them not, for all the Definition of the Schools. And if into a Red-hot Earthen or Iron Retort you cast the Matter to be Distill'd, You may Observe, as I have often done, that the Predominant Fire will Carry up all the Volatile Elements Confusedly in one Fume, which will afterwards take their Places in the Receiver, either according to the Degree of their Gravity, or according to the Exigency of their respective Textures; the Salt Adhering, for the most part, to the Sides and Top, and the Phlegme Fastening it self there too in great Drops, the Oyle and Spirit placing themselves Under, or Above one another, according as their Ponderousness makes them Swim or Sink. For 'tis Observable, that though Oyl or Liquid Sulphur be one of the Elements Separated by this Fiery _Analysis_, yet the Heat which Accidentally Unites the Particles of the other Volatile Principles, has not alwayes the same Operation on this, there being divers Bodies which Yield Two Oyls, whereof the One sinks to the Bottom of that Spirit on which the other Swims; as I can shew You in some Oyls of the same Deers Blood, which are yet by Me: Nay I can shew you Two Oyls carefully made of the same Parcel of Humane Blood, which not only Differ extreamly in Colour, but Swim upon one another without Mixture, and if by Agitation Confounded will of themselves Divorce again. And that the Fire doth oftentimes divide Bodies, upon the account that some of their Parts are more Fixt, and some more Volatile, how far soever either of these Two may be from a pure Elementary Nature is Obvious enough, if Men would but heed it in the Burning of Wood, which the Fire Dissipates into Smoake and Ashes: For not only the latter of these is Confessedly made up of two such Differing Bodies as Earth and Salt; but the Former being condens'd into that Soot which adheres to our Chimneys, Discovers it self to Contain both Salt and Oyl, and Spirit and Earth, (and some Portion of Phlegme too) which being, all almost, Equally Volatile to that Degree of Fire which Forces them up, (the more Volatile Parts Helping perhaps, as well as the Urgency of the Fire, to carry up the more Fixt ones, as I have often Try'd in Dulcify'd _Colcothar_, Sublim'd by _Sal Armoniack_ Blended with it) are carried Up together, but may afterwards be Separated by other Degrees of Fire, whose orderly Gradation allowes the Disparity of their Volatileness to Discover it self. Besides, if Differing Bodies United into one Mass be both sufficiently Fixt, the Fire finding no Parts Volatile enough to be Expell'd or carried up, makes no Separation at all; as may appear by a Mixture of Colliquated Silver and Gold, whose Component Metals may be easily Sever'd by _Aqua Fortis_, or _Aqua Regis_ (according to the Predominancy of the Silver or the Gold) but in the Fire alone, though vehement, the Metals remain unsever'd, the Fire only dividing the Body into smaller Particles (whose Littlenesse may be argu'd from their Fluidity) in which either the little nimble Atoms of Fire, or its brisk and numberless strokes upon the Vessels, hinder Rest and Continuity, without any Sequestration of Elementary Principles. Moreover, the Fire sometimes does not Separate, so much as Unite, Bodies of a differing Nature; provided they be of an almost resembling Fixedness, and have in the Figure of their Parts an Aptness to Coalition, as we see in the making of many Plaisters, Oyntments, &c. And in such Metalline Mixtures as that made by Melting together two parts of clean Brass with one of pure Copper, of which some Ingenious Trades-men cast such curious Patterns (for Gold and Silver Works) as I have sometimes taken great Pleasure to Look upon. Sometimes the Bodies mingled by the Fire are Differing enough as to Fixidity and Volatility, and yet are so combin'd by the first Operation of the Fire, that it self does scarce afterwards Separate them, but only Pulverize them; whereof an Instance is afforded us by the Common Preparation of _Mercurius Dulcis_, where the Saline Particles of the Vitriol, Sea Salt, and sometimes Nitre, Employ'd to make the Sublimate, do so unite themselves with the Mercurial Particles made use of, first to Make Sublimate, and then to Dulcifie it, that the Saline and Metalline Parts arise together in many successive Sublimations, as if they all made but one Body. And sometimes too the Fire does not only not Sever the Differing Elements of a Body, but Combine them so firmly, that Nature her self does very seldom, if ever, make Unions less Dissoluble. For the Fire meeting with some Bodies exceedingly and almost equally Fixt, instead of making a Separation, makes an Union so strict, that it self, alone, is unable to Dissolve it; As we see, when an Alcalizate Salt and the Terrestrial Residue of the Ashes are Incorporated with pure Sand, and by Vitrification made one permanent Body, (I mean the course or greenish sort of Glass) that mocks the greatest Violence of the Fire, which though able to Marry the Ingredients of it, yet is not able to Divorce them. I can shew you some pieces of Glass which I saw flow down from an Earthen Crucible purposely Expos'd for a good while, with Silver in it, to a very vehement Fire. And some that deal much in the Fusion of Metals Informe me, that the melting of a great part of a Crucible into Glass is no great Wonder in their Furnaces. I remember, I have Observ'd too in the Melting of great Quantities of Iron out of the Oar, by the Help of store of Charcoal (for they Affirm that Sea-Coal will not yield a Flame strong enough) that by the prodigious Vehemence of the Fire, Excited by vast Bellows (made to play by great Wheels turn'd about by Water) part of the Materials Expos'd to it was, instead of being Analyz'd, Colliquated, and turn'd into a Dark, Solid and very Ponderous Glass, and that in such Quantity, that in some places I have seen the very High-wayes, neer such Iron-works, mended with Heaps of such Lumps of Glasse, instead of Stones and Gravel. And I have also Observ'd, that some kind of Fire-stone it Self, having been employ'd in Furnaces wherein it was expos'd to very strong and lasting Fires, has had all its Fixt Parts so Wrought on by the Fire, as to be Perfectly Vitrifi'd, which I have try'd by Forcing from it Pretty large Pieces of Perfect and Transparent Glass. And lest You might think, _Eleutherius_, that the Question'd Definition of Heat may be Demonstrated, by the Definition which is wont to be given and Acquiesc'd in, of its contrary Quality, Cold, whose property is taught to be _tam Homogenea, quam Heterogenea congregare_; Give me leave to represent to You, that neither is this Definition unquestionable; for not to Mention the Exceptions, which a _Logician_, as such, may Take at it, I Consider that the Union of Heterogeneous Bodies which is Suppos'd to be the Genuine Production of Cold, is not Perform'd by every Degree of Cold. For we see for Instance that in the Urine of Healthy Men, when the Liquor has been Suffer'd a while to stand, the Cold makes a Separation of the Thinner Part from the Grosser, which Subsides to the Bottom, and Growes Opacous there; whereas if the Urinal be Warme, these Parts readily Mingle again, and the whole Liquor becomes Transparent as before. And when, by Glaciation, Wood, Straw, Dust, Water, &c. are Suppos'd to be United into one Lump of Ice, the Cold does not Cause any Real Union or Adunation, (if I may so Speak) of these Bodies, but only Hardening the Aqueous Parts of the Liquor into Ice, the other Bodies being Accidentally Present in that Liquor are frozen up in it, but not Really United. And accordingly if we Expose a Heap of Mony Consisting of Gold, Silver and Copper Coynes, or any other Bodies of Differing Natures, which are Destitute of Aqueous Moisture, Capable of Congelation, to never so intense a Cold, we find not that these Differing Bodies are at all thereby so much as Compacted, much less United together; and even in Liquors Themselves we find _Phænomena_ which Induce us to Question the Definition which we are examining. If _Paracelsus_ his Authority were to be look't upon as a Sufficient Proof in matters of this Nature, I might here insist on that Process of his, whereby he Teaches that the Essence of Wine may be Sever'd from the Phlegme and Ignoble Part by the Assistance of Congelation: and because much Weight has been laid upon this Process, not only by _Paracelsians_, but other Writers, some of whom seem not to have perus'd it themselves, I shall give You the entire Passage in the Authors own Words, as I lately found them in the sixth Book of his _Archidoxis_, an Extract whereof I have yet about me; and it sounds thus. _De Vino sciendum est, fæcem phlegmaque ejus esse Mineram, & Vini substantiam esse corpus in quo conservatur Essentia, prout auri in auro latet Essentia. Juxta quod Practicam nobis ad Memoriam ponimus, ut non obliviscamur, ad hunc modum: Recipe Vinum vetustissimum & optimum quod habere poteris, calore saporeque ad placitum, hoc in vas vitreum infundas ut tertiam ejus partem impleat, & sigillo Hermetis occlusum in equino ventre mensibus quatuor, & in continuato calore teneatur qui non deficiat. Quo peracto, Hyeme cum frigus & gelu maxime sæviunt, his per mensem exponatur ut congeletur. Ad hunc modum frigus vini spiritum una cum ejus substantia protrudit in vini centrum, ac separat a phlegmate: Congelatum abjice, quod vero congelatum non est, id Spiritum cum substantia esse judicato. Hunc in Pelicanum positum in arenæ digestione non adeo calida per aliquod tempus manere finito; Postmodum eximito vini Magisterium, de quo locuti sumus._ But I dare not _Eleu._ lay much Weight upon this Process, because I have found that if it were True, it would be but seldom Practicable in this Country upon the best Wine: for Though this present Winter hath been Extraordinary Cold, yet in very Keen Frosts accompanied with lasting Snowes, I have not been able in any Measure to Freeze a thin Vial full of Sack; and even with Snow and Salt I could Freeze little more then the Surface of it; and I suppose _Eleu._ that tis not every Degree of Cold that is Capable of Congealing Liquors, which is able to make such an _Analysis_ (if I may so call it) of them by Separating their Aqueous and Spirituous Parts; for I have sometimes, though not often, frozen severally, Red-wine, Urine and Milk, but could not Observe the expected Separation. And the Dutch-Men that were forc'd to Winter in that Icie Region neer the Artick Circle, call'd _Nova Zembla_, although they relate, as we shall see below, that there was a Separation of Parts made in their frozen Beer about the middle of _November_, yet of the Freezing of their Back [Errata: Sack] in _December_ following they give but this Account: _Yea and our Sack, which is so hot, was Frozen very hard, so that when we were every Man to have his part, we were forc'd to melt it in the Fire; which we shar'd every second Day, about half a Pinte for a Man, wherewith we were forc'd to sustain our selves._ In which words they imply not, that their Back [Errata: Sack] was divided by the Frost into differing Substances, after such manner as their Beer had been. All which notwithstanding, _Eleu._ suppose that it may be made to appear, that even Cold sometimes may _Congregare Homogenea, & Heterogenea Segregare_: and to Manifest this I may tell you, that I did once, purposely cause to be Decocted in fair Water a Plant abounding with Sulphureous and Spirituous Parts, and having expos'd the Decoction to a keen North-Wind in a very Frosty Night, I observ'd, that the more Aqueous Parts of it were turn'd by the next Morning into Ice, towards the innermost part of which, the more Agile and Spirituous parts, as I then conjectur'd, having Retreated, to shun as much as might be their Environing Enemy, they had there preserv'd themselves unfrozen in the Form of a high colour'd Liquor, the Aqueous and Spirituous parts having been so sleightly (Blended rather than) United in the Decoction, that they were easily Separable by such a Degree of Cold as would not have been able to have Divorc'd the Parts of Urine or Wine, which by Fermentation or Digestion are wont, as Tryal has inform'd me, to be more intimately associated each with other. But I have already intimated, _Eleutherius_, that I shall not Insist on this Experiment, not only because, having made it but once I may possibly have been mistaken in it; but also (and that principally) because of that much more full and eminent Experiment of the Separative Virtue of extream Cold, that was made, against their Wills, by the foremention'd Dutch men that Winter'd in _Nova Zembla_; the Relation of whose Voyage being a very scarce Book, it will not be amiss to give you that Memorable part of it which concerns our present Theme, as I caus'd the Passage to be extracted out of the Englished Voyage it self. "_Gerard de Veer_, _John Cornelyson_ and Others, sent out of _Amsterdam_, _Anno Dom._ 1596. being forc'd by unseasonable Weather to Winter in _Nova Zembla_, neer Ice-Haven; on the thirteenth of _October_, Three of us (sayes the Relation) went aboard the Ship, and laded a Sled with Beer; but when we had laden it, thinking to go to our House with it, suddenly there arose such a Winde, and so great a Storm and Cold, that we were forc'd to go into the Ship again, because we were not able to stay without; and we could not get the Beer into the Ship again, but were forc'd to let it stand without upon the Sled: the Fourteenth, as we came out of the Ship, we found the Barrel of Beer standing upon the Sled, but it was fast frozen at the Heads; yet by reason of the great Cold, the Beer that purg'd out froze as hard upon the Side of the Barrel, as if it had been glu'd thereon: and in that sort we drew it to our House, and set the Barrel an end, and drank it up; but first we were forc'd to melt the Beer, for there was scarce any unfrozen Beer in the barrel; but in that thick Yiest that was unfrozen lay the Strength of the Beer, so that it was too strong to drink alone, and that which was frozen tasted like Water; and being melted we Mix'd one with the other, and so drank it; but it had neither Strength nor Taste." And on this Occasion I remember, that having the last very Sharp Winter purposely try'd to Freeze, among other Liquors, some Beer moderately strong, in Glass Vessels, with Snow and Salt, I observ'd, that there came out of the Neck a certain thick Substance, which, it seems, was much better able then the rest of the Liquor (that I found turn'd into Ice) to resist a Frost, and which, by its Colour and consistence seem'd mafestly [Transcriber's Note: manifestly] enough to be Yiest, whereat, I confess, I somewhat marvail'd, because I did not either discerne by the Taste, or find by Enquiry, that the Beer was at all too New to be very fit to be Drank. I might confirm the Dutchmens Relation, by what happen'd a while since to a neere Friend of mine, who complained to me, that having Brew'd some Beer or Ale for his own drinking in _Holland_ (where he then dwelt) the Keenness of the late bitter Winter froze the Drink so as to reduce it into Ice, and a small Proportion of a very Strong and Spirituous Liquor. But I must not entertain you any longer concerning Cold, not onely because you may think I have but lost my way into a Theme which does not directly belong to my present Undertaking; but because I have already enlarg'd my self too much upon the first Consideration I propos'd, though it appears so much a Paradox, that it seem'd to Require that I should say much to keep it from being thought a meere Extravagance; yet since I Undertook but to make the common Assumption of our Chymists and _Aristotelians_ appear Questionable, I hope I have so Perform'd that Task, that I may now Proceed to my Following Considerations, and Insist lesse on them than I have done on the First. THE SCEPTICAL CHYMIST. _The Second Part._ The Second Consideration I Desire to have Notice Taken of, is This, That it is not so Sure, as Both Chymists and _Aristotelians_ are wont to Think it, that every Seemingly Similar or Distinct Substance that is Separated from a Body by the Help of the Fire, was Pre existent in it as a Principle or Element of it. That I may not make this Paradox a Greater then I needs must, I will First Briefly Explain what the Proposition means, before I proceed to Argue for it. And I suppose You will easily Believe That I do not mean that any thing is separable from a Body by Fire, that was not Materially pre-existent in it; for it Far Exceeds the power of Meerly Naturall Agents, and Consequently of the Fire, to produce anew, so Much as one Atome of Matter, which they can but Modifie and Alter, not Create; which is so Obvious a Truth, that almost all Sects of Philosophers have Deny'd the Power of producing Matter to Second Causes; and the _Epicureans_ and some Others have Done the Like, in Reference to their Gods themselves. Nor does the Proposition peremptorily Deny but that some Things Obtain'd by the Fire from a Mixt Body, may have been more then barely Materially pre-existent in it, since there are Concretes, which before they be Expos'd to the Fire afford us several Documents of their abounding, some with Salt, and Others with Sulphur. For it will serve the present Turn, if it appear that diverse things Obtain'd from a Mixt Body expos'd to the Fire, were not its Ingredients Before: for if this be made to appear it, will [Errata: appear, it will] be Rationall enough to suspect that Chymists may Decieve themselves, and Others, in concluding Resolutely and Universally, those Substances to be the Elementary Ingredients of Bodies barely separated by the Fire, of which it yet may be Doubted Whether there be such or No; at least till some other Argument then that drawn from the _Analysis_ be Brought to resolve the Doubt. That then which I Mean by the Proposition I am Explaining, is, That it may without Absurdity be Doubted whether or no the Differing Substances Obtainable from a Concrete Dissipated by the Fire were so Exsistent in it in that Forme (at least as to their minute Parts) wherein we find them when the _Analysis_ is over, that the Fire did only Dis-joyne and Extricate the Corpuscles of one Principle from those of the other wherewith before they were Blended. Having thus Explain'd my Proposition, I shall endeavour to do two things, to prove it; The first of which is to shew that such Substances as Chymists call Principles May be produc'd _De novo_ (as they speak.) And the other is to make it probable that by the Fire we may Actually obtain from some Mixt Bodies such Substances as were not in the Newly Expounded sence, pre-existent in them. To begin then with the First of these, I Consider that if it be as true as 'tis probable, that Compounded Bodies Differ from One Another but in the Various Textures Resulting from the Bigness, Shape, Motion, and contrivance of their smal parts, It will not be Irrationall to conceive that one and the same parcel of the Universal Matter may by Various Alterations and Contextures be brought to Deserve the Name, somtimes of a Sulphureous, and sometimes of a Terrene, or Aqueous Body. And this I could more largely Explicate, but that our Friend Mr. _Boyle_ has promis'd us something about Qualities, wherein the Theme I now willingly Resign him, Will I Question not be Studiously Enquired into. Wherefore what I shall now advance in favour of what I have lately Deliver'd shall be Deduc'd from Experiments made Divers Years since. The first of which would have been much more considerable, but that by some intervening Accidents I was Necessitated to lose the best time of the year, for a trial of the Nature of that I design'd; it being about he [Transcriber's Note: the] middle of _May_ before I was able to begin an Experiment which should have then been two moneths old; but such as it was, it will not perhaps be impertinent to Give You this Narrative of it. At the time newly Mention'd, I caus'd My Gardiner (being by Urgent Occasions Hinder'd from being present myself) to dig out a convenient quantity of good Earth, and dry it well in an Oven, to weigh it, to put it in an Earthen pot almost level with the Surface of the ground, and to set in it a selected seed he had before received from me, for that purpose, of Squash, which is an Indian kind of Pompion, that Growes apace; this seed I Ordered Him to Water only with Rain or Spring Water. I did not (when my Occasions permitted me to visit it) without delight behold how fast it Grew, though unseasonably sown; but the Hastning Winter Hinder'd it from attaining any thing neer its due and Wonted magnitude; (for I found the same Autumn, in my Garden, some of those plants, by Measure, as big about as my Middle) and made me order the having it taken Up; Which about the Middle of _October_ was carefully Done by the same Gardiner, who a while after sent me this account of it; _I have Weighed the Pompion with the Stalk and Leaves, all which Weighed three pound wanting a quarter; Then I took the Earth, baked it as formerly, and found it just as much as I did at First, which made me think I had not dry'd it Sufficiently: then I put it into the Oven twice More, after the Bread was Drawn, and Weighed it the Second time, but found it Shrink little or nothing._ But to deal Candidly with You, _Eleutherius_, I must not conceal from You the Event of another Experiment of this Kind made this present Summer, wherein the Earth seems to have been much more Wasted; as may appear by the following account, Lately sent me by the same Gardiner, in these Words. _To give You an Account of your Cucumbers, I have Gain'd two Indifferent Fair Ones, the Weight of them is ten Pound and a Halfe, the Branches with the Roots Weighed four Pounds wanting two Ounces; and when I had weighed them I took the Earth, and bak'd it in several small Earthen Dishes in an Oven; and when I had so done, I found the Earth wanted a Pound and a halfe of what it was formerly; yet I was not satisfi'd, doubting the Earth was not dry: I put it into an Oven the Second Time, (after the Bread was drawn) and after I had taken it out and weighed it, I found it to be the Same Weight: So I Suppose there was no Moisture left in the Earth. Neither do I think that the Pound and Halfe that was wanting was Drawn away by the Cucumber but a great Part of it in the Ordering was in Dust (and the like) wasted: (the Cucumbers are kept by themselves, lest You should send for them.)_ But yet in this Tryal, _Eleutherius_, it appears that though some of the Earth, or rather the dissoluble Salt harbour'd in it, were wasted, the main Body of the Plant consisted of Transmuted Water. And I might add, that a year after I caus'd the formerly mentioned Experiment, touching large Pompions, to be reiterated, with so good success, that if my memory does not much mis-inform me, it did not only much surpass any that I made before, but seem'd strangely to conclude what I am pleading for; though (by reason I have unhappily lost the particular Account my Gardiner writ me up of the Circumstances) I dare not insist upon them. The like Experiment may be as conveniently try'd with the seeds of any Plant, whose growth is hasty, and its size Bulky. If Tobacco will in These Cold Climates Grow well in Earth undung'd, it would not be amiss to make a Tryal with it; for 'tis an annual Plant, that arises where it prospers, sometimes as high as a Tall Man; and I have had leaves of it in my Garden neer a Foot and a Halfe broad. But the next time I Try this Experiment, it shall be with several seeds of the same sort, in the same pot of Earth, that so the event may be the more Conspicuous. But because every Body has not Conveniency of time and place for this Experiment neither, I made in my Chamber, some shorter and more Expeditions [Transcriber's Note: Expeditious] Tryals. I took a Top of Spearmint, about an Inch Long, and put it into a good Vial full of Spring water, so as the upper part of the Mint was above the neck of the Glass, and the lower part Immers'd in the Water; within a few Dayes this Mint began to shoot forth Roots into the Water, and to display its Leaves, and aspire upwards; and in a short time it had numerous Roots and Leaves, and these very strong and fragrant of the Odour of the Mint: but the Heat of my Chamber, as I suppose, kill'd the Plant when it was grown to have a pretty thick Stalk, which with the various and ramified Roots, which it shot into the Water as if it had been Earth, presented in its Transparent Flower-pot a Spectacle not unpleasant to behold. The like I try'd with sweet Marjoram, and I found the Experiment succeed also, though somewhat more slowly, with Balme and Peniroyal, to name now no other Plants. And one of these Vegetables, cherish'd only by Water, having obtain'd a competent Growth, I did, for Tryals sake, cause to be Distill'd in a small Retort, and thereby obtain'd some Phlegme, a little Empyreumaticall Spirit, a small Quantity of adust Oyl, and a _Caput mortuum_; which appearing to be a Coal concluded it to consist of Salt and Earth: but the Quantity of it was so small that I forbore to Calcine it. The Water I us'd to nourish this Plant was not shifted nor renewed; and I chose Spring-water rather than Rain-water, because the latter is more discernably a kinde of [Greek: panspermia], which, though it be granted to be freed from grosser Mixtures, seems yet to Contain in it, besides the Steams of several Bodies wandering in the Air, which may be suppos'd to impregnate it, a certain Spirituous Substance, which may be Extracted out of it, and is by some mistaken for the Spirit of the World Corporify'd, upon what Grounds, and with what Probability, I may elsewhere perchance, but must not now, Discourse to you. But perhaps I might have sav'd a great part of my Labour. For I finde that _Helmont_ (an Author more considerable for his Experiments than many Learned men are pleas'd to think him) having had an Opportunity to prosecute an Experiment much of the same nature with those I have been now speaking of, for five Years together, obtain'd at the end of that time so notable a Quantity of Transmuted Water, that I should scarce Think it fit to have his Experiment, and Mine Mention'd together, were it not that the Length of Time Requisite to this may deterr the Curiosity of some, and exceed the leasure of Others; and partly, that so Paradoxical a Truth as that which these Experiments seem to hold forth, needs to be Confirm'd by more Witnesses then one, especially since the Extravagancies and Untruths to be met with in _Helmonts_ Treatise of the Magnetick Cure of Wounds, have made his Testimonies suspected in his other Writings, though as to some of the Unlikely matters of Fact he delivers in them, I might safely undertake to be his Compurgator. But that Experiment of his which I was mentioning to You, he sayes, was this. He took 200 pound of Earth dry'd in an Oven, and having put it into an Earthen Vessel and moisten'd it with Raine water he planted in it the Trunk of a Willow tree of five pound Weight; this he Water'd, as need required, with Rain or with Distill'd Water; and to keep the Neighbouring Earth from getting into the Vessell, he employ'd a plate of Iron tinn'd over and perforated with many holes. Five years being efflux'd, he took out the Tree and weighed it, and (with computing the leaves that fell during four Autumnes) he found it to weigh 169 pound, and about three Ounces. And Having again Dry'd the Earth it grew in, he found it want of its Former Weight of 200 Pound, about a couple only of Ounces; so that 164 pound of the Roots, Wood, and Bark, which Constituted the Tree, seem to have Sprung from the Water. And though it appears not that _Helmont_ had the Curiosity to make any _Analysis_ of this Plant, yet what I lately told You I did to One of the Vegetables I nourish'd with Water only, will I suppose keep You from Doubting that if he had Distill'd this Tree, it would have afforded him the like Distinct Substances as another Vegetable of the same kind. I need not Subjoyne that I had it also in my thoughts to try how Experiments to the same purpose with those I related to You would succeed in other Bodies then Vegetables, because importunate Avocations having hitherto hinder'd me from putting my Design in Practise, I can yet speak but Confecturally [Transcriber's Note: Conjecturally] of the Success: but the best is, that the Experiments already made and mention'd to you need not the Assistance of new Ones, to Verifie as much as my present task makes it concern me to prove by Experiments of this Nature. One would suspect (sayes _Eleutherius_ after his long silence) by what You have been discoursing, that You are not far from _Helmonts_ Opinion about the Origination of Compound Bodies, and perhaps too dislike not the Arguments which he imployes to prove it. What _Helmontian_ Opinion, and what Arguments do you mean (askes _Carneades_.) What You have been Newly Discoursing (replies _Eleutherius_) tells us, that You cannot but know that this bold and Acute Spagyrist scruples not to Assert that all mixt Bodies spring from one Element; and that Vegetables, Animals, Marchasites, Stones, Metalls, &c. are Materially but simple Water disguis'd into these Various Formes, by the plastick or Formative Virtue of their seeds. And as for his Reasons you may find divers of them scatter'd up and down his writings; the considerabl'st of which seem to be these three; The Ultimate Reduction of mixt Bodies into Insipid Water, the Vicissitude of the supposed Elements, and the production of perfectly mixt Bodies out of simple Water. And first he affirmes that the _Sal circulatus Paracelsi_, or his Liquor _Alkahest_, does adequately resolve Plants, Animals, and Mineralls into one Liquor or more, according to their several internall Disparities of Parts (without _Caput Mortuum_, or the Destruction of their seminal Virtues;) and that the _Alkahest_ being abstracted from these Liquors in the same weight and Virtue wherewith it Dissolv'd them, the Liquors may by frequent Cohobations from chalke or some other idoneous matter, be Totally depriv'd of their seminal Endowments, and return at last to their first matter, Insipid Water; some other wayes he proposes here and there, to divest some particular Bodies of their borrow'd shapes, and make them remigrate to their first Simplicity. The second Topick whence _Helmont_ drawes his Arguments, to prove Water to be the Material cause of Mixt Bodies, I told You was this, that the other suppos'd Elements may be transmuted into one another. But the Experiments by him here and there produc'd on this Occasion, are so uneasie to be made and to be judg'd of, that I shall not insist on them; not to mention, that if they were granted to be true, his Inference from them is somewhat disputable; and therefore I shall pass on to tell You, That as, in his First Argument, our Paradoxical Author endeavours to prove Water the Sole Element of Mixt Bodies, by their Ultimate Resolution, when by his _Alkahest_, or some other conquering Agent, the Seeds have been Destroy'd, which Disguis'd them, or when by time those seeds are Weari'd or Exantlated or unable to Act their Parts upon the Stage of the Universe any Longer: So in His Third Argument he Endeavours to evince the same Conclusion, by the constitution of Bodies which he asserts to be nothing but Water Subdu'd by Seminal Virtues. Of this he gives here and there in his Writings several Instances, as to Plants and Animals; but divers of them being Difficult either to be try'd or to be Understood, and others of them being not altogether Unobnoxious to Exceptions, I think you have singl'd out the Principal and less Questionable Experiment when you lately mention'd that of the Willow Tree. And having thus, Continues _Eleutherius_, to Answer your Question, given you a Summary Account of what I am Confident You know better then I do, I shall be very glad to receive Your Sence of it, if the giving it me will not too much Divert You from the Prosecution of your Discourse. That _If_ (replies _Carneades_) was not needlessly annex'd: for thorowly to examine such an Hypothesis and such Arguments would require so many Considerations, and Consequently so much time, that I should not now have the Liesure [Errata: leasure] to perfect such a Digression, and much less to finish my Principle [Errata: principal] Discourse. Yet thus much I shall tell You at present, that you need not fear my rejecting this Opinion for its Novelty; since, however the _Helmontians_ may in complement to their Master pretend it to be a new Discovery, Yet though the Arguments be for the most part his, the Opinion it self is very Antient: For _Diogenes Laertius_ and divers other Authors speak of _Thales_, as the first among the _Græcians_ that made disquisitions upon nature. And of this _Thales_, I Remember, _Tully_[5] informes us, that he taught all things were at first made of Water. And it seems by _Plutarch_ and _Justin Martyr_, that the Opinion was Ancienter then he: For they tell us that he us'd to defend his Tenet by the Testimony of _Homer_. And a Greek Author, (the _Scholiast_ of _Apollonius_) upon these Words [Greek: Ex iliou [Transcriber's Note: iluos] eblastêse chthôn autê],[6] _The Earth of Slime was made,_ Affirms (out of _Zeno_) that the _Chaos_, whereof all things were made, was, according to _Hesiod_, Water; which, settling first, became Slime, and then condens'd into solid Earth. And the same Opinion about the Generation of Slime seems to have been entertain'd by _Orpheus_, out of whom one of the Antients[7] cites this Testimony, [Greek: Ek tou hydatos ilui katistê.] _Of Water Slime was made._ [Footnote 5: De Natura Deorum.] [Footnote 6: Argonaut. 4.] [Footnote 7: Athenagoras.] It seems also by what is delivered in _Strabo_[8] out of another Author, concerning the _Indians_, That they likewise held that all things had differing Beginnings, but that of which the World was made, was Water. And the like Opinion has been by some of the Antients ascrib'd to the _Phoenicians_, from whom _Thales_ himself is conceiv'd to have borrow'd it; as probably the Greeks did much of their Theologie, and, as I am apt to think, of their Philosophy too; since the Devising of the Atomical _Hypothesis_ commonly ascrib'd to _Lucippus_ and his Disciple _Democritus_, is by Learned Men attributed to one _Moschus_ a _Phoenician_. And possibly the Opinion is yet antienter than so; For 'tis known that the _Phoenicians_ borrow'd most of their Learning from the _Hebrews_. And among those that acknowledge the Books of _Moses_, many have been inclin'd to think Water to have been the Primitive and Universal Matter, by perusing the Beginning of _Genesis_, where the Waters seem to be mention'd as the Material Cause, not only of Sublunary Compounded Bodies, but of all those that make up the Universe; whose Component Parts did orderly, as it were, emerge out of that vast Abysse, by the Operation of the Spirit of God, who is said to have been moving Himself as hatching Females do (as the Original [Hebrew: merachephet], _Meracephet_[9] is said to Import, and as it seems to signifie in one of the two other places, wherein alone I have met with it in the Hebrew Bible)[10] upon the Face of the Waters; which being, as may be suppos'd, Divinely Impregnated with the seeds of all things, were by that productive Incubation qualify'd to produce them. But you, I presume, Expect that I should Discourse of this Matter like a Naturalist, not a Philologer. Wherefore I shall add, to Countenance _Helmont's_ Opinion, That whereas he gives not, that I remember, any Instance of any Mineral Body, nor scarce of any Animal, generated of Water, a French Chymist, _Monsieur de Rochas_, has presented his Readers an Experiment, which if it were punctually such as he has deliver'd it, is very Notable. He then, Discoursing of the Generation of things according to certain Chymical and Metaphorical Notions (which I confess are not to me Intelligible) sets down, among divers Speculations not pertinent to our Subject, the following Narrative, which I shall repeat to you the sence of in English, with as little variation from the Literal sence of the French words, as my memory will enable me. _Having_ (sayes he) _discern'd such great Wonders by the Natural Operation of Water, I would know what may be done with it by Art Imitating Nature. Wherefore I took Water which I well knew not to be compounded, nor to be mix'd with any other thing than that Spirit of Life_ (whereof he had spoken before;) _and with a Heat Artificial, Continual and Proportionate, I prepar'd and dispos'd it by the above mention'd Graduations of Coagulation, Congelation, and Fixation, untill it was turn'd into Earth, which Earth produc'd Animals, Vegetables and Minerals. I tell not what Animals, Vegetables and Minerals, for that is reserv'd for another Occasion: but the Animals did Move of themselves, Eat, &c.--and by the true Anatomie I made of them, I found that they were compos'd of much Sulphur, little Mercury, and less Salt.--The Minerals began to grow and encrease by converting into their own Nature one part of the Earth thereunto dispos'd; they were solid and heavy. And by this truly Demonstrative Science, namely Chymistry, I found that they were compos'd of much Salt, little Sulphur, and less Mercury._ [Footnote 8: Universarum rerum primordia diverta esse, faciendi autem mundi initium aquam. Strabo. Geograp. lib. 15. circa medium.] [Footnote 9: Deuter. 32. 11.] [Footnote 10: Jerem. 23. 9.] But (sayes _Carneades_) I have some Suspitions concerning this strange Relation, which make me unwilling to Declare an Opinion of it, unless I were satisfied concerning divers Material Circumstances that our Author has left unmentioned; though as for the Generation of Living Creatures, both Vegetable and Sensitive, it needs not seem Incredible, since we finde that our common water (which indeed is often Impregnated with Variety of Seminal Principles and Rudiments) being long kept in a quiet place will putrifie and stink, and then perhaps too produce Moss and little Worms, or other Insects, according to the nature of the Seeds that were lurking in it. I must likewise desire you to take Notice, that as _Helmont_ gives us no Instance of the Production of Minerals out of Water, so the main Argument that he employ's to prove that they and other Bodies may be resolv'd into water, is drawn from the Operations of his _Alkahest_, and consequently cannot be satisfactorily Examin'd by You and Me. Yet certainly (sayes _Eleutherius_) You cannot but have somewhat wonder'd as well as I, to observe how great a share of Water goes to the making up of Divers Bodies, whose Disguises promise nothing neere so much. The Distillation of Eeles, though it yielded me some Oyle, and Spirit, and Volatile Salt, besides the _Caput mortuum_, yet were all these so disproportionate to the Phlegm that came from them (and in which at first they boyl'd as in a Pot of Water) that they seem'd to have bin nothing but coagulated Phlegm, which does likewise strangely abound in Vipers, though they are esteem'd very hot in Operation, and will in a Convenient Aire survive some dayes the loss of their Heads and Hearts, so vigorous is their Vivacity. Mans Bloud it self as Spirituous, and as Elaborate a Liquor as 'tis reputed, does so abound in Phlegm, that, the other Day, Distilling some of it on purpose to try the Experiment (as I had formerly done in Deers Bloud) out of about seven Ounces and a half of pure Bloud we drew neere six Ounces of Phlegm, before any of the more operative Principles began to arise, and Invite us to change the Receiver. And to satisfie my self that some of these Animall Phlegms were void enough of Spirit to deserve that Name, I would not content my self to taste them only, but fruitlesly pour'd on them acid Liquors, to try if they contain'd any Volatile Salt or Spirit, which (had there been any there) would probably have discover'd it self by making an Ebullition with the affused Liquor. And now I mention Corrosive Spirits, I am minded to Informe you, That though they seem to be nothing else but Fluid Salts, yet they abound in Water, as you may Observe, if either you Entangle, and so Fix their Saline Part, by making them Corrode some idoneous Body, or else if you mortifie it with a contrary Salt; as I have very manifestly Observ'd in the making a Medecine somewhat like _Helmont's Balsamus Samech_, with Distill'd Vinager instead of Spirit of Wine, wherewith he prepares it: For you would scarce Beleeve (what I have lately Observ'd) that of that acid Spirit, the Salt of Tartar, from which it is Distill'd, will by mortifying and retaining the acid Salt turn into worthless Phlegm neere twenty times its weight, before it be so fully Impregnated as to rob no more Distill'd Vinager of its Salt. And though Spirit of Wine Exquisitely rectify'd seem of all Liquors to be the most free from Water, it being so Igneous that it will Flame all away without leaving the least Drop behinde it, yet even this Fiery Liquor is by _Helmont_ not improbably affirm'd, in case what he relates be True, to be Materially Water, under a Sulphureous Disguise: For, according to him, in the making that excellent Medecine, _Paracelsus_ his _Balsamus Samech_, (which is nothing but _Sal Tartari_ dulcify'd by Distilling from it Spirit of Wine till the Salt be sufficiently glutted with its Sulphur, and suffer [Errata: and till it suffer] the Liquor to be drawn off, as strong as it was pour'd on) when the Salt of Tartar from which it is Distill'd hath retain'd, or depriv'd it of the Sulphureous parts of the Spirit of Wine, the rest, which is incomparably the greater part of the Liquor, will remigrate into Phlegm. I added that Clause [_In case what he Relates be True_] because I have not as yet sufficiently try'd it my self. But not only something of Experiment keeps me from thinking it, as many Chymists do, absurd, (though I have, as well as they, in vain try'd it with ordinary Salt of Tartar;) but besides that _Helmont_ often Relates it, and draws Consequences from it; A Person noted for his Sobernesse and Skill in Spagyrical Preparations, having been askt by me, Whether the Experiment might not be made to succeed, if the Salt and Spirit were prepar'd according to a way suitable to my Principles, he affirm'd to me, that he had that way I propos'd made _Helmont's_ Experiment succeed very well, without adding any thing to the Salt and Spirit. But our way is neither short nor Easie. I have indeed (sayes _Carneades_) sometimes wonder'd to see how much Phlegme may be obtain'd from Bodies by the Fire. But concerning that Phlegme I may anon have Occasion to note something, which I therefore shall not now anticipate. But to return to the Opinion of _Thales_, and of _Helmont_, I consider, that supposing the _Alkahest_ could reduce all Bodies into water, yet whether that water, because insipid, must be Elementary, may not groundlesly be doubted; For I remember the Candid and Eloquent _Petrus Laurembergius_ in his Notes upon _Sala's_ Aphorismes affirmes, that he saw an insipid _Menstruum_ that was a powerfull Dissolvent, and (if my Memory do not much mis-informe me) could dissolve Gold. And the water which may be Drawn from Quicksilver without Addition, though it be almost Tastless, You will I believe think of a differing Nature from simple Water, especially if you Digest in it Appropriated Mineralls. To which I shall add but this, that this Consideration may be further extended. For I see no Necessity to conceive that the Water mention'd in the Beginning of _Genesis_, as the Universal Matter, was simple and Elementary Water; since though we should Suppose it to have been an Agitated Congeries or Heap consisting of a great Variety of Seminal Principles and Rudiments, and of other Corpuscles fit to be subdu'd and Fashion'd by them, it might yet be a Body Fluid like Water, in case the Corpuscles it was made up of, were by their Creator made small enough, and put into such an actuall Motion as might make them Glide along one another. And as we now say, the Sea consists of Water, notwithstanding [Errata: (notwithstanding] the Saline, Terrestrial, and other Bodies mingl'd with it,) such a Liquor may well enough be called Water, because that was the greatest of the known Bodies whereunto it was like; Though, that a Body may be Fluid enough to appear a Liquor, and yet contain Corpuscles of a very differing Nature, You will easily believe, if You but expose a good Quantity of Vitriol in a strong Vessel to a Competent Fire. For although it contains both Aqueous, Earthy, Saline, Sulphureous, and Metalline Corpuscles, yet the whole Mass will at first be Fluid like water, and boyle like a seething pot. I might easily (Continues _Carneades_) enlarge my self on such Considerations, if I were Now Oblig'd to give You my Judgment of the _Thalesian_, and _Helmontian_, _Hypothesis_. But Whether or no we conclude that all things were at first Generated of Water, I may Deduce from what I have try'd Concerning the Growth of Vegetables, nourish'd with water, all that I now propos'd to my Self or need at present to prove, namely that Salt, Spirit, Earth, and ev'n Oyl (though that be thought of all Bodies the most opposite to Water) may be produc'd out of Water; and consequently that a Chymical Principle as well as a Peripatetick Element, may (in some cases) be Generated anew, or obtain'd from such a parcel of Matter as was not endow'd with the form of such a principle or Element before. And having thus, _Eleutherius_, Evinc'd that 'tis possible that such Substances as those that Chymists are wont to call their _Tria Prima_, may be Generated, anew: I must next Endeavour to make it Probable, that the Operation of the Fire does Actually (sometimes) not only divide Compounded Bodies into smal Parts, but Compound those Parts after a new Manner; whence Consequently, for ought we Know, there may Emerge as well Saline and Sulphureous Substances, as Bodies of other Textures. And perhaps it will assist us in our Enquiry after the Effects of the Operations of the Fire upon other Bodies, to Consider a little, what it does to those Mixtures which being Productions of the Art of Man, We best know the Composition of. You may then be pleas'd to take Notice that though Sope is made up by the Sope-Boylers of Oyle or Grease, and Salt, and Water Diligently Incorporated together, yet if You expose the Mass they Constitute to a Graduall Fire in a Retort, You shall then indeed make a Separation, but not of the same Substances that were United into Sope, but of others of a Distant and yet not an Elementary Nature, and especially of an Oyle very sharp and Fætid, and of a very Differing Quality from that which was Employ'd to make the Sope: fo [Errata: so] if you Mingle in a due Proportion, _Sal Armoniack_ with Quick-Lime, and Distill them by Degrees of Fire, You shall not Divide the _Sal Armoniack_ from the Quick-Lime, though the one be a Volatile, and the other a Fix'd Substance, but that which will ascend will be a Spirit much more Fugitive, Penetrant, and stinking, then _Sal Armoniack_; and there will remain with the Quick-Lime all or very near all the Sea Salt that concurr'd to make up the _Sal Armoniack_; concerning which Sea Salt I shall, to satisfie You how well it was United to the Lime, informe You, that I have by making the Fire at length very Vehement, caus'd both the Ingredients to melt in the Retort it self into one Mass and such Masses are apt to Relent in the Moist Air. If it be here Objected, that these Instances are taken from factitious Concretes which are more Compounded then those which Nature produces; I shall reply, that besides that I have Mention'd them as much to Illustrate what I propos'd, as to prove it, it will be Difficult to Evince that Nature her self does not make Decompound Bodies, I mean mingle together such mixt Bodies as are already Compounded of Elementary, or rather of more simple ones. For Vitriol (for Instance) though I have sometimes taken it out of Minerall Earths, where Nature had without any assistance of Art prepar'd it to my Hand, is really, though Chymists are pleas'd to reckon it among Salts, a De-compounded Body Consisting (as I shall have occasion to declare anon) of a Terrestriall Substance, of a Metal, and also of at least one Saline Body, of a peculiar and not Elementary Nature. And we see also in Animals, that their blood may be compos'd of Divers very Differing Mixt Bodies, since we find it observ'd that divers Sea-Fowle tast rank of the Fish on which they ordinarily feed; and _Hipocrates_ himself Observes, that a Child may be purg'd by the Milke of the Nurse, if she have taken _Elaterium_; which argues that the purging Corpuscles of the Medicament Concurr to make up the Milke of the Nurse; and that white Liquor is generally by Physitians suppos'd to be but blanch'd and alter'd Blood. And I remember I have observ'd, not farr from the _Alps_, that at a certain time of the Year the Butter of that Country was very Offensive to strangers, by reason of the rank tast of a certain Herb, whereon the Cows were then wont plentifully to feed. But (proceeds _Carneades_) to give you Instances of another kind, to shew that things may be obtain'd by the Fire from a Mixt Body that were not Pre-existent in it, let Me Remind You, that from many Vegetables there may without any Addition be Obtain'd Glass, a Body, which I presume You will not say was Pre-existent in it, but produc'd by the Fire. To which I shall add but this one Example more, namely that by a certain Artificial way of handling Quicksilver, You may without Addition separate from it at least a 5th. or 4th. part of a clear Liquor, which with an Ordinary Peripatetick would pass for Water, and which a Vulgar Chymist would not scruple to call Phlegme, and which, for ought I have yet seen or heard, is not reducible into Mercury again, and Consequently is more then a Disguise of it. Now besides that divers Chymists will not allow Mercury to have any or at least any Considerable Quantity of either of the Ignoble Ingredients, Earth and Water; Besides this, I say, the great Ponderousness of Quicksilver makes it very unlikely that it can have so much Water in it as may be thus obtain'd from it, since Mercury weighs 12 or 14 times as much as water of the same Bulk. Nay for a further Confirmation of this Argument, I will add this Strange Relation, that two Friends of mine, the one a Physitian, and the other a Mathematician, and both of them Persons of unsuspected Credit, have Solemnly assured me, that after many Tryals they made, to reduce Mercury into Water, in Order to a Philosophicall Work, upon Gold (which yet, by the way, I know prov'd Unsuccesfull) they did once by divers Cohobations reduce a pound of Quicksilver into almost a pound of Water, and this without the Addition of any other Substance, but only by pressing the Mercury by a Skillfully Manag'd Fire in purposely contriv'd Vessels. But of these Experiments our Friend (sayes _Carneades_, pointing at the Register of this Dialogue) will perhaps give You a more Particular Account then it is necessary for me to do: Since what I have now said may sufficiently evince, that the Fire may sometimes as well alter Bodies as divide them, and by it we may obtain from a Mixt Body what was not Pre-existent in it. And how are we sure that in no other Body what we call Phlegme is barely separated, not Produc'd by the Action of the Fire: Since so many other Mixt Bodies are of a much less Constant, and more alterable Nature, then Mercury, by many Tricks it is wont to put upon Chymists, and by the Experiments I told You of, about an hour since, Appears to be. But because I shall ere long have Occasion to resume into Consideration the Power of the Fire to produce new Concretes, I shall no longer insist on this Argument at present; only I must mind You, that if You will not dis-believe _Helmonts_ Relations, You must confess that the _Tria Prima_ are neither ingenerable nor incorruptible Substances; since by his _Alkahest_ some of them may be produc'd of Bodies that were before of another Denomination; and by the same powerfull _Menstruum_ all of them may be reduc'd into insipid Water. Here _Carneades_ was about to pass on to his Third Consideration, when _Eleutherius_ being desirous to hear what he could say to clear his second General Consideration from being repugnant to what he seem'd to think the true Theory of Mistion, prevented him by telling him, I somewhat wonder, _Carneades_, that You, who are in so many Points unsatisfied with the Peripatetick Opinion touching the Elements and Mixt Bodies, should also seem averse to that Notion touching the manner of Mistion, wherein the Chymists (though perhaps without knowing that they do so) agree with most of the Antient Philosophers that preceded _Aristotle_, and that for Reasons so considerable, that divers Modern Naturalists and Physitians, in other things unfavourable enough to the Spagyrists, do in this case side with them against the common Opinion of the Schools. If you should ask me (continues _Eleutherius_) what Reasons I mean? I should partly by the Writings of _Sennertus_ and other learned Men, and partly by my own Thoughts, be supply'd with more, then 'twere at present proper for me to Insist largely on. And therefore I shall mention only, and that briefly, three or four. Of these, I shall take the First from the state of the Controversie itself, and the genuine Notion of Mistion, which though much intricated by the Schoolmen, I take in short to be this, _Aristotle_, at least as many of his Interpreters expound him, and as indeed he Teaches in some places, where he professedly Dissents from the Antients, declares Mistion to be such a mutual Penetration, and perfect Union of the mingl'd Elements, that there is no Portion of the mixt Body, how Minute soever, which does not contain All, and Every of the Four Elements, or in which, if you please, all the Elements are not. And I remember, that he reprehends the Mistion taught by the Ancients, as too sleight or gross, for this Reason, that Bodies mixt according to their _Hypothesis_, though they appear so to humane Eyes, would not appear such to the acute Eyes of a _Lynx_, whose perfecter Sight would discerne the Elements, if they were no otherwise mingled, than as his Predecessors would have it, to be but Blended, not United; whereas the Antients, though they did not all Agree about what kind of Bodies were Mixt, yet they did almost unanimously hold, that in a compounded Bodie, though the _Miscibilia_, whether Elements, Principles, or whatever they pleas'd to call them, were associated in such small Parts, and with so much Exactness, that there was no sensible Part of the Mass but seem'd to be of the same Nature with the rest, and with the whole; Yet as to the Atomes, or other Insensible Parcels of Matter, whereof each of the _Miscibilia_ consisted, they retain'd each of them its own Nature, being but by Apposition or _Juxta_-Position united with the rest into one Bodie. So that although by virtue of this composition the mixt Body did perhaps obtain Divers new Qualities, yet still the Ingredients that Compounded it, retaining their own Nature, were by the Destruction of the _Compositum_ separable from each other, the minute Parts disingag'd from those of a differing Nature, and associated with those of their own sort returning to be again, Fire, Earth, or Water, as they were before they chanc'd to be Ingredients of that _Compositum_. This may be explain'd (Continues _Eleutherius_,) by a piece of Cloath made of white and black threds interwoven, wherein though the whole piece appear neither white nor black, but of a resulting Colour, that is gray, yet each of the white and black threds that compose it, remains what it was before, as would appear if the threds were pull'd asunder, and sorted each Colour by it self. This (pursues _Eleutherius_) being, as I understand it, the State of the Controversie, and the _Aristotelians_ after their Master Commonly Defining, that Mistion is _Miscibilium alteratorum Unio_, that seems to comport much better with the Opinion of the Chymists, then with that of their Adversaries, since according to that as the newly mention'd Example declares, there is but a _Juxta_-position of separable Corpuscles, retaining each its own Nature, whereas according to the _Aristotelians_, when what they are pleas'd to call a mixt Body results from the Concourse of the Elements, the _Miscibilia_ cannot so properly be said to be Alter'd, as Destroy'd, since there is no Part in the mixt Body, how small soever, that can be call'd either Fir [Transcriber's Note: Fire], or Air, or Water, or Earth. Nor indeed can I well understand, how Bodies can be mingl'd other wayes then as I have declar'd, or at least how they can be mingl'd, as our Peripateticks would have it. For whereas _Aristotle_ tells us, that if a Drop of Wine be put into ten thousand Measures of Water, the Wine being Overpower'd by so Vast a Quantity of Water will be turn'd into it, he speaks to my Apprehension, very improbably; For though One should add to that Quantity of Water as many Drops of Wine as would a Thousand times exceed it all, yet by his Rule the whole Liquor should not be a _Crama_, a Mixture of Wine and Water, wherein the Wine would be Predominant, but Water only; Since the Wine being added but by a Drop at a time would still Fall into nothing but Water, and Consequently would be turn'd into it. And if this would hold in Metals too, 'twere a rare secret for Goldsmiths, and Refiners; For by melting a Mass of Gold, or Silver, and by but casting into it Lead or Antimony, Grain after Grain, they might at pleasure, within a reasonable Compass of time, turn what Quantity they desire, of the Ignoble into the Noble Metalls. And indeed since a Pint of wine, and a pint of water, amount to about a Quart of Liquor, it seems manifest to sense, that these Bodies doe not Totally Penetrate one another, as one would have it; but that each retains its own Dimensions; and Consequently, that they are by being Mingl'd only divided into minute Bodies, that do but touch one another with their Surfaces, as do the Grains, of Wheat, Rye, Barley, &c. in a heap of severall sorts of Corn: And unless we say, that as when one measure of wheat, for Instance, is Blended with a hundred measures of Barley, there happens only a _Juxta_-position and Superficial Contact betwixt the Grains of wheat, and as many or thereabouts of the Grains of Barley. So when a Drop of wine is mingl'd with a great deal of water, there is but an Apposition of so many Vinous Corpuscles to a Correspondent Number of Aqueous ones; Unless I say this be said, I see not how that Absurdity will be avoyded, whereunto the Stoical Notion of mistion (namely by [Greek: synchysis] [Errata: [Greek: Synchysis]], or Confusion) was Liable, according to which the least Body may be co-extended with the greatest: Since in a mixt Body wherein before the Elements were Mingl'd there was, for Instance, but one pound of water to ten thousand of Earth, yet according to them there must not be the least part of that Compound, that Consisted not as well of Earth, as water. But I insist, Perhaps, too long (sayes _Eleutherius_) upon the proofs afforded me by the Nature of Mistion: Wherefore I will but name Two or Three other Arguments; whereof the first shall be, that according to _Aristotle_ himself, the motion of a mixt Body followes the Nature of the Predominant Element, as those wherein the Earth prevails, tend towards the Centre of heavy Bodies. And since many things make it Evident, that in divers Mixt Bodies the Elementary Qualities are as well Active, though not altogether so much so as in the Elements themselves, it seems not reasonable to deny the actual Existence of the Elements in those Bodies wherein they Operate. To which I shall add this Convincing Argument, that Experience manifests, and _Aristotle_ Confesses it, that the _Miscibilia_ may be again separated from a mixt Body, as is Obvious in the Chymical Resolutions of Plants and Animalls, which could not be unless they did actually retain their formes in it: For since, according to _Aristotle_, and I think according to truth, there is but one common Mass of all things, which he has been pleas'd to call _Materia Prima_; And since tis not therefore the Matter but the Forme that Constitutes and Discriminates Things, to say that the Elements remain not in a Mixt Body, according to their Formes, but according to their Matter, is not to say that they remain there at all; Since although those Portions of Matter were Earth and water, &c. before they concurr'd, yet the resulting Body being once Constituted, may as well be said to be simple as any of the Elements, the Matter being confessedly of the same Nature in all Bodies, and the Elementary Formes being according to this _Hypothesis_ perish'd and abolish'd. And lastly, and if we will Consult Chymical Experiments, we shall find the Advantages of the Chymical Doctrine above the Peripatetick Title little less then Palpable. For in that Operation that Refiners call Quartation, which they employ to purifie Gold, although three parts of Silver be so exquisitely mingl'd by Fusion with a fourth Part of Gold (whence the Operation is Denominated) that the resulting Mass acquires severall new Qualities, by virtue of the Composition, and that there is scarce any sensible part of it that is not Compos'd of both the metalls; Yet if You cast this mixture into _Aqua Fortis_, the Silver will be dissolv'd in the _Menstruum_, and the Gold like a dark or black Powder will fall to the Bottom of it, and either Body may be again reduc'd into such a Metal as it was before, which shews: that it retain'd its Nature, notwithstanding its being mixt _per Minima_ with the other: We likewise see, that though one part of pure Silver be mingled with eight or ten Parts, or more, of Lead, yet the Fire will upon the Cuppel easily and perfectly separate them again. And that which I would have you peculiarly Consider on this Occasion is, that not only in Chymicall Anatomies there is a Separation made of the Elementary Ingredients, but that some Mixt Bodies afford a very much greater Quantity of this or that Element or Principle than of another; as we see, that Turpentine and Amber yield much more Oyl and Sulphur than they do Water, whereas Wine, which is confess'd to be a perfectly mixt Bodie, yields but a little Inflamable Spirit, or Sulphur, and not much more Earth; but affords a vast proportion of Phlegm or water: which could not be, if as the Peripateticks suppose, every, even of the minutest Particles, were of the same nature with the whole, and consequently did contain both Earth and Water, and Aire, and Fire; Wherefore as to what _Aristotle_ principally, and almost only Objects, that unless his Opinion be admitted, there would be no true and perfect Mistion, but onely Aggregates or Heaps of contiguous Corpuscles, which, though the Eye of Man cannot discerne, yet the Eye of a _Lynx_ might perceive not to be of the same Nature with one another and with their _Totum_, as the Nature of Mistion requires, if he do not beg the Question, and make Mistion to consist in what other Naturalists deny to be requisite to it, yet He at least objects That as a great Inconvenience which I cannot take for such, till he have brought as Considerable Arguments as I have propos'd to prove the contrary, to evince that Nature makes other Mistions than such as I have allowed, wherein the _Miscibilia_ are reduc'd into minute Parts, and United as farr as sense can discerne: which if You will not grant to be sufficient for a true Mistion, he must have the same Quarrel with Nature her self, as with his Adversaries. Wherefore (Continues _Eleutherius_) I cannot but somewhat marvail that _Carneades_ should oppose the Doctrine of the Chymist in a Particular, wherein they do as well agree with his old Mistress, Nature, as dissent from his old Adversary, _Aristotle_. I must not (replies _Carneades_) engage my self at present to examine thorowly the Controversies concerning Mistion: And if there were no third thing, but that I were reduc'd to embrace absolutely and unreservedly either the Opinion of _Aristotle_, or that of the Philosophers that went before him, I should look upon the latter, which the Chymists have adopted, as the more defensible Opinion: But because differing in the Opinions about the Elements from both Parties, I think I can take a middle Course, and Discourse to you of Mistion after a way that does neither perfectly agree, nor perfectly disagree with either, as I will not peremptorily define, whether there be not Cases wherein some _Phænomena_ of Mistion seem to favour the Opinion that the Chymists Patrons borrow'd of the Antients, I shall only endeavour to shew You that there are some cases which may keep the Doubt, which makes up my second General Consideration from being unreasonable. I shall then freely acknowledge to You (sayes _Carneades_) that I am not over well satisfi'd with the Doctrine that is ascribed to _Aristotle_, concerning Mistion, especially since it teaches that the four Elements may again be separated from the mixt Body; whereas if they continu'd not in it, it would not be so much a Separation as a Production. And I think the Ancient Philosophers that Preceded _Aristotle_, and Chymists who have since receiv'd the same Opinion, do speak of this matter more intelligibly, if not more probably, then the Peripateticks: but though they speak Congruously enough, to their believing, that there are a certain Number of Primogeneal Bodies, by whose Concourse all those we call Mixts are Generated, and which in the Destruction of mixt Bodies do barely part company, and recede from one another, just such as they were when they came together; yet I, who meet with very few Opinions that I can entirely Acquiesce in, must confess to You that I am inclin'd to differ not only from the _Aristotelians_, but from the old Philosophers and the Chymists, about the Nature of Mistion: And if You will give me leave, I shall Briefly propose to you my present Notion of it, provided you will look upon it, not so much as an Assertion as an _Hypothesis_; in talking of which I do not now pretend to propose and debate the whole Doctrine of Mistion, but to shew that 'tis not Improbable, that sometimes mingl'd substances may be so strictly united, that it doth not by the usuall Operations of the Fire, by which Chymists are wont to suppose themselves to have made the _Analyses_ of mixt Bodies, sufficiently appear, that in such Bodies the _Miscibilia_ that concurr'd to make them up do each of them retain its own peculiar Nature: and by the _Spagyrists_ Fires may be more easily extricated and Recover'd, than Alter'd, either by a Change of Texture in the Parts of the same Ingredient, or by an Association with some parts of another Ingredient more strict than was that of the parts of this or that _Miscibile_ among themselves. At these words _Eleu._ having press'd him to do what he propos'd, and promis'd to do what he desir'd; I consider then (resumes _Carneades_) that, not to mention those improper Kinds of mistion, wherein _Homogeneous_ Bodies are Joyn'd, as when Water is mingl'd with water, or two Vessels full of the same kind of Wine with one another, the mistion I am now to Discourse of seems, Generally speaking, to be but an Union _per Minima_ of any two or more Bodies of differing Denominations; as when Ashes and Sand are Colliquated into Glass or Antimony, and Iron into _Regulus Martis_, or Wine and Water are mingl'd, and Sugar is dissolv'd in the Mixture. Now in this general notion of Mistion it does not appear clearly comprehended, that the _Miscibilia_ or Ingredients do in their small Parts so retain their Nature and remain distinct in the Compound, that they may thence by the Fire be again taken asunder: For though I deny not that in some Mistions of certain permanent Bodies this Recovery of the same Ingredients may be made, yet I am not convinc'd that it will hold in all or even in most, or that it is necessarily deducible from Chymicall Experiments, and the true Notion of Mistion. To explain this a little, I assume, that Bodies may be mingl'd, and that very durably, that are not Elementary or resolv'd [Errata: nor have been resolved] into Elements or Principles that they may be mingl'd; as is evident in the _Regulus_ of Colliquated Antimony, and Iron newly mention'd; and in Gold Coyne, which lasts so many ages; wherein generally the Gold is alloy'd by the mixture of a quantity, greater or lesser, (in our Mints they use about a 12th. part) of either silver, or Copper, or both. Next, I consider, that there being but one Universal matter of things, as 'tis known that the _Aristotelians_ themselves acknowledge, who call it _Materia Prima_ (about which nevertheless I like not all their Opinions,) the Portions of this matter seem to differ from One Another, but in certain Qualities or Accidents, fewer or more; upon whose Account the Corporeal Substance they belong to receives its Denomination, and is referr'd to this or that particular sort of Bodies; so that if it come to lose, or be depriv'd of those Qualities, though it ceases not to be a body, yet it ceases from being that kind of Body as a Plant, or Animal; or Red, Green, Sweet, Sowre, or the like. I consider that it very often happens that the small parts of Bodies cohere together but by immediate Contact and Rest; and that however, there are few Bodies whose minute Parts stick so close together, to what cause soever their Combination be ascrib'd, but that it is possible to meet with some other Body, whose small Parts may get between them, and so dis-joyn them; or may be fitted to cohere more strongly with some of them, then those some do with the rest; or at least may be combin'd so closely with them, as that neither the Fire, nor the other usual Instruments of Chymical Anatomies will separate them. These things being promis'd, I will not peremptorily deny, but that there may be some Clusters of Particles, wherein the Particles are so minute, and the Coherence so strict, or both, that when Bodies of Differing Denominations, and consisting of such durable Clusters, happen to be mingl'd, though the Compound Body made up of them may be very Differing from either of the Ingredients, yet each of the little Masses or Clusters may so retain its own Nature, as to be again separable, such as it was before. As when Gold and Silver being melted together in a Due Proportion (for in every Proportion, the Refiners will tell You that the Experiment will not succeed) _Aqua Fortis_ will dissolve the Silver, and leave the Gold untoucht; by which means, as you lately noted, both the Metalls may be recover'd from the mixed Mass. But (Continues _Carneades_) there are other Clusters wherein the Particles stick not so close together, but that they may meet with Corpuscles of another Denomination, which are dispos'd to be more closely United with some of them, then they were among themselves. And in such case, two thus combining Corpuscles losing that Shape, or Size, or Motion, or other Accident, upon whose Account they were endow'd with such a Determinate Quality or Nature, each of them really ceases to be a Corpuscle of the same Denomination it was before; and from the Coalition of these there may emerge a new Body, as really one, as either of the Corpuscles was before they were mingl'd, or, if you please, Confounded: Since this Concretion is really endow'd with its own Distinct qualities, and can no more by the Fire, or any other known way of _Analysis_, be divided again into the Corpuscles that at first concurr'd to make it, than either of them could by the same means be subdivided into other Particles. But (sayes _Eleutherius_) to make this more intelligible by particular examples; If you dissolve Copper in _Aqua Fortis_, or Spirit of Nitre, (for I remember not which I us'd, nor do I think it much Material) You may by Crystalizing the Solution Obtain a goodly Vitriol; which though by Virtue of the Composition it have manifestly diverse Qualities, not to be met with in either of the Ingredients, yet it seems that the Nitrous Spirits, or at least many of them, may in this Compounded Mass retain their former Nature; for having for tryal sake Distill'd this Vitrioll Spirit, there came over store of Red Fumes, which by that Colour, by their peculiar stinke, and by their Sourness, manifested themselves to be, Nitrous Spirits; and that the remaining Calx continu'd Copper, I suppose you'l easily beleeve. But if you dissolve _Minium_, which is but Lead Powder'd by the Fire, in good Spirit of Vinager, and Crystalize the Solution, you shall not only have a Saccharine Salt exceedingly differing from both its Ingredients; but the Union of some Parts of the _Menstruum_ with some of those of the Metal is so strict, that the Spirit of Vinager seems to be, as such, destroy'd, since the Saline Corpuscles have quite lost that acidity, upon whose Account the Liquor was call'd Spirit of Vinager; nor can any such Acid Parts as were put to the _Minium_ be Separated by any known way from the _Saccharum Saturni_ resulting from them both; for not only there is no Sowrness at all, but an admirable Sweetness to be tasted in the Concretion; and not only I found not that Spirit of Wine, which otherwise will immediately hiss when mingl'd with strong Spirit of Vinager, would hiss being pour'd upon _Saccharum Saturni_, wherein yet the Acid Salt of Vinager, did it Survive, may seem to be concentrated; but upon the Distillation of _Saccharum Saturni_ by its Self I found indeed a Liquor very Penetrant, but not at all Acid, and differing as well in smell and other Qualities, as in tast, from the Spirit of Vinager; which likewise seem'd to have left some of its Parts very firmly united to the _Caput Mortuum_, which though of a Leaden Nature was in smell, Colour, &c. differing from _Minium_; which brings into my mind, that though two Powders, the one Blew, and the other Yellow, may appear a Green mixture, without either of them losing its own Colour, as a good Microscope has sometimes inform'd me; yet having mingl'd _Minium_ and _Sal Armoniack_ in a requisite Proportion, and expos'd them in a Glass Vessel to the Fire, the whole Mass became White, and the Red Corpuscles were destroy'd; for though the Calcin'd Lead was separable from the Salt, yet you'l easily beleeve it did not part from it in the Forme of a Red Powder, such as was the _Minium_, when it was put to the _Sal Armoniack_. I leave it also to be consider'd, whether in Blood, and divers other Bodies, it be probable, that each of the Corpuscles that concurr to make a Compound Body doth, though some of them in some Cases may, retain its own Nature in it, so that Chymsts [Transcriber's Note: Chymists] may Extricate each sort of them from all the others, wherewith it concurr'd to make a Body of one Denomination. I know there may be a Distinction betwixt Matter _Immanent_, when the material Parts remain and retain their own Nature in the things materiated, as some of the Schoolmen speak, (in which sence Wood, Stones and Lime are the matter of a House,) and _Transient_, which in the materiated thing is so alter'd, as to receive a new Forme, without being capable of re-admitting again the Old. In which sence the Friends of this Distinction say, that _Chyle_ is the matter of Blood, and Blood that of a Humane Body, of all whose Parts 'tis presum'd to be the Aliment. I know also that it may be said, that of material Principles, some are _common_ to all mixt Bodies, as _Aristotles_ four Elements, or the Chymists _Tria Prima_; others _Peculiar_, which belong to this or that sort of Bodies; as Butter and a kind of whey may be said to be the Proper Principles of Cream: and I deny not, but that these Distinctions may in some Cases be of Use; but partly by what I have said already, and partly by what I am to say, You may easily enough guess in what sence I admit them, and discerne that in such a sence they will either illustrate some of my Opinions, or at least will not overthrow any of them. To prosecute then what I was saying before, I will add to this purpose, That since the Major part of Chymists Credit, what those they call Philosophers affirme of their Stone, I may represent to them, that though when Common Gold and Lead are mingled Together, the Lead may be sever'd almost un-alter'd from the Gold; yet if instead of Gold a _Tantillum_ of the Red _Elixir_ be mingled with the Saturn, their Union will be so indissoluble in the perfect Gold that will be produc'd by it, that there is no known, nor perhaps no possible way of separating the diffus'd _Elixir_ from the fixed Lead, but they both Constitute a most permanent Body, wherein the Saturne seems to have quite lost its Properties that made it be call'd Lead, and to have been rather transmuted by the _Elixir_, then barely associated to it. So that it seems not alwayes necessary, that the Bodies that are put together _per minima_, should each retain its own Nature; So as when the Mass it Self is dissipated by the Fire, to be more dispos'd to re-appear in its Pristine Forme, then in any new one, which by a stricter association of its Parts with those of some of the other Ingredients of the _Compositum_, then with one another, it may have acquired. And if it be objected, that unless the _Hypothesis_ I oppose be admitted, in such Cases as I have proposed there would not be an Union but a Destruction of mingled Bodies, which seems all one as to say, that of such Bodies there is no mistion at all; I answer, that _though_ the Substances that are mingl'd remain, only their Accidents are Destroy'd, and _though_ we may with tollerable Congruity call them _Miscibilia_, because they are Distinct Bodies before they are put together, however afterwards they are so Confounded that I should rather call them Concretions, or Resulting Bodies, than mixt ones; and _though_, perhaps, some other and better Account may be propos'd, upon which the name of mistion may remain; yet if what I have said be thought Reason, I shall not wrangle about Words, though I think it fitter to alter a Terme of Art, then reject a new Truth, because it suits not with it. If it be also Objected that this Notion of mine, concerning mixtion, though it may be allow'd, when Bodies already Compounded are put to be mingl'd, yet it is not applicable to those mixtions that are immediately made of the Elements, or Principles themselves; I Answer in the first place, that I here Consider the Nature of mixtion somewhat more Generally, then the Chymists, who yet cannot deny that there are oftentimes Mixtures, and those very durable ones, made of Bodies that are not Elementary. And in the next place, that though it may be probably pretended that in those Mixtures that are made immediately of the Bodies that are call'd Principles or Elements, the mingl'd Ingredients may better retain their own Nature in the Compounded Mass, and be more easily separated from thence; yet, besides that it may be doubted, whether there be any such Primary Bodies, I see not why the reason I alleadg'd, of the destructibility of the Ingredients of Bodies in General, may not sometimes be Applicable to Salt Sulphur or Mercury; 'till it be shewn upon what account we are to believe them Priviledged. And however, (if you please but to recall to mind, to what purpose I told you at First, I meant to speak of Mistion at this Time) you will perhaps allow that what I have hitherto Discoursed about it may not only give some Light to the Nature of it in general (especially when I shall have an Opportunity to Declare to you my thoughts on that subject more fully) but may on some Occasions also be Serviceable to me in the Insuing Part of this Discourse. But, to look back Now to that part of our Discourse, whence this Excursion concerning Mistion has so long diverted us, though we there Deduc'd, from the differing Substances obtained from a Plant nourished only with Water, and from some other things, that it was not necessary that nature should alwaies compound a Body at first of all such differing bodies as the fire could afterwards make it afford; yet this is not all that may be collected from those Experiments. For from them there seems also Deducible something that Subverts an other Foundation of the Chymical Doctrine. For since that (as we have seen) out of fair Water alone, not only Spirit, but Oyle, and Salt, and Earth may be Produced; It will follow that Salt and Sulphur are not Primogeneal Bodies, and principles, since they are every Day made out of plain Water by the Texture which the Seed or Seminal principle of plants puts it into. And this would not perhaps seem so strange, if through pride, or negligence, We were not Wont to Overlook the Obvious and Familiar Workings of Nature; For if We consider what slight Qualities they are that serve to denominate one of the _Tria Prima_, We shall find that Nature do's frequently enough work as great Alterations in divers parcells of matter: For to be readily dissoluble in water, is enough to make the body that is so, passe for a Salt. And yet I see not why from a new shufling and Disposition of the Component Particles of a body, it should be much harder for Nature to compose a body dissoluble in Water, of a portion of Water that was not so before, then of the Liquid substance of an Egg, which will easily mix with Water, to produce by the bare warmth of a hatching Hen, Membrans, Feathers, Tendons, and other parts, that are not dissoluble in Water as that Liquid Substance was: Nor is the Hardness and Brittleness of Salt more difficult for Nature to introduce into such a yielding body as Water, then it is for her to make the Bones of a Chick out of the tender Substance of the Liquors of an Egg. But instead of prosecuting this consideration, as I easily might, I will proceed, as soon as I have taken notice of an objection that lies in my Way. For I easily foresee it will be alledged, that the above mentioned Examples are all taken from Plants, and Animals, in whom the Matter is Fashioned by the Plastick power of the seed, or something analogous thereunto. Whereas the Fire do's not act like any of the Seminal Principles, but destroyes them all, when they come within its Reach. But to this I shall need at present to make but this easy Answer, That whether it be a Seminal Principle, or any other which fashions that Matter after those various manners I have mentioned to You, yet 'tis Evident, that either by the Plastick principle Alone, or that and Heat Together, or by some Other cause capable to contex the matter, it is yet possible that the matter may be Anew contriv'd into such Bodies. And 'tis only for the Possibility of this that I am now contending. THE SCEPTICAL CHYMIST. _The Third Part._ What I have hitherto Discours'd, _Eleutherius_, (sayes his Friend to Him) has, I presume, shew'n You, that a Considering Man may very well question the Truth of those very Suppositions which Chymists as well as Peripateticks, without proving, take for granted; and upon which Depends the Validity of the Inferences they draw from their Experiments. Wherefore having dispach't that, which though a Chymist Perhaps will not, yet I do, look upon as the most Important, as well as Difficult, part of my Task, it will now be Seasonable for me to proceed to the Consideration of the Experiments themselves, wherein they are wont so much to Triumph and Glory. And these will the rather deserve a serious Examination, because those that Alledge them are wont to do it with so much Confidence and Ostentation, that they have hitherto impos'd upon almost all Persons, without excepting Philosophers and Physitians themselves, who have read their Books, or heard them talk. For some learned Men have been content rather to beleeve what they so boldly Affirm, then be at the trouble and charge, to try whether or no it be True. Others again, who have Curiosity enough to Examine the Truth of what is Averr'd, want Skill and Opportunity to do what they Desire. And the Generality even of Learned Men, seeing the Chymists (not contenting themselves with the Schools to amuse the World with empty words) Actually Perform'd divers strange things, and, among those Resolve Compound Bodies into several Substances not known by former Philosophers to be contain'd in them: Men I say, seeing these Things, and Hearing with what Confidence Chymists Averr the Substances Obtain'd from Compound Bodies by the Fire to be the True Elements, or, (as they speak) Hypostaticall Principles of them, are forward to think it but Just as well as Modest, that according to the _Logicians_ Rule, the Skilfull _Artists_ should be Credited in their own Art; Especially when those things whose Nature they so Confidently take upon them to teach others are not only Productions of their own Skill, but such as others Know not else what to make of. But though (Continues _Carneades_) the Chymists have been able upon some or other of the mention'd Acounts, not only to Delight but Amaze, and almost to bewitch even Learned Men; yet such as You and I, who are not unpractis'd in the Trade, must not suffer our Selves to be impos'd upon by hard Names, or bold Assertions; nor to be dazl'd by that Light which should but assist us to discern things the more clearly. It is one thing to be able to help Nature to produce things, and another thing to Understand well the Nature of the things produc'd. As we see, that many Persons that can beget Children, are for all that as Ignorant of the Number and Nature of the parts, especially the internal ones, that Constitute a Childs Body, as they that never were Parents. Nor do I Doubt, but you'l excuse me, if as I thank the Chymists for the things their _Analysis_ shews me, so I take the Liberty to consider how many, and what they are, without being astonish'd at them; as if, whosoever hath Skill enough to shew men some new thing of his own making, had the Right to make them believe whatsoever he pleases to tell them concerning it. Wherefore I will now proceed to my Third General Consideration, which is, That it does not appear, that _Three_ is precisely and Universally the Number of the Distinct Substances or Elements, whereinto mixt Bodies are resoluble by the Fire; I mean that 'tis not prov'd by Chymists, that all the Compound Bodies, which are granted to be perfectly mixt, are upon their Chymical _Analysis_ divisible each of them into just Three Distinct Substances, neither more nor less, which are wont to be lookt upon as Elementary, or may as well be reputed so as those that are so reputed. Which last Clause I subjoyne, to prevent your Objecting, that some of the Substances I may have occasion to mention by and by, are not perfectly Homogeneous, nor Consequently worthy of the name of Principles. For that which I am now to consider, is, into how many Differing Substances, that may plausibly pass for the Elementary Ingredients of a mix'd Body, it may be Analyz'd by the Fire; but whether each of these be un-compounded, I reserve to examine, when I shall come to the next General Consideration; where I hope to evince, that the Substances which the Chymists not only allow, but assert to be the Component Principles of the Body resolv'd into them, are not wont to be uncompounded. Now there are two Kind of Arguments (pursues _Carneades_) which may be brought to make my Third Proposition seem probable; one sort of them being of a more Speculative Nature, and the other drawn from Experience. To begin then with the first of these. But as _Carneades_ was going to do as he had said, _Eleutherius_ interrupted him, by saying with a somewhat smiling countenance; If you have no mind I should think, that the Proverb, _That Good Wits have bad Memories_, is Rational and Applicable to You, You must not Forget now you are upon the Speculative Considerations, that may relate to the Number of the Elements; that your Self did not long since Deliver and Concede some Propositions in Favour of the Chymical Doctrine, which I may without disparagement to you think it uneasie, even for _Carneades_ to answer. I have not, replies he, Forgot the Concessions you mean; but I hope too, that you have not forgot neither with what Cautions they were made, when I had not yet assumed the Person I am now sustaining. But however, I shall to content You, so discourse of my Third general consideration, as to let You see, That I am not Unmindful of the things you would have me remember. To talk then again according to such principles as I then made use of, I shall represent, that if it be granted rational to suppose, as I then did, that the Elements consisted at first of certain small and primary Coalitions of the minute Particles of matter into Corpuscles very numerous, and very like each other, It will not be absurd to conceive, that such primary Clusters may be of far more sorts then three or five; and consequently, that we need not suppose, that in each of the compound Bodies we are treating of there should be found just three sorts of such primitive Coalitions, as we are speaking of. And if according to this Notion we allow a considerable number of differing Elements, I may add, that it seems very possible, that to the constitution of one sort of mixt Bodies two kinds of Elementary ones may suffice (as I lately Exemplify'd to you, in that most durable Concrete, Glass,) another sort of Mixts may be compos'd of three Elements, another of four, another of five, and another perhaps of many more. So that according to this Notion, there can be no determinate number assign'd, as that of the Elements; of all sorts of compound Bodies whatsoever, it being very probable that some Concretes consist of fewer, some of more Elements. Nay, it does not seem Impossible, according to these Principles, but that there may be two sorts of Mixts, whereof the one may not have any of all the same Elements as the other consists of; as we oftentimes see two words, whereof the one has not any one of the Letters to be met with in the other; or as we often meet with diverse Electuaries, in which no Ingredient (except Sugar) is common to any two of them. I will not here debate whether there may not be a multitude of these Corpuscles, which by reason of their being primary and simple, might be called Elementary, if several sorts of them should convene to compose any Body, which are as yet free, and neither as yet contex'd and entangl'd with primary Corpuscles of other kinds, but remains liable to be subdu'd and fashion'd by Seminal Principles, or the like powerful and Transmuting Agent, by whom they may be so connected among themselves, or with the parts of one of the bodies, as to make the compound Bodies, whose Ingredients they are, resoluble into more, or other Elements then those that Chymists have hitherto taken notice of. To all which I may add, that since it appears, by what I observ'd to you of the permanency of Gold and Silver, that even Corpuscles that are not of an Elementary but compounded Nature, may be of so durable a Texture, as to remain indissoluble in the ordinary _Analysis_ that Chymists make of Bodies by the Fire; 'Tis not impossible but that, though there were but three Elements, yet there may be a greater number of Bodies, which the wonted wayes of Anatomy will not discover to be no Elementary Bodies. But, sayes _Carneades_, having thus far, in compliance to you, talk't conjecturally of the number of the Elements, 'tis now time to consider, not of how many Elements it is possible that Nature may compound mix'd Bodies, but (at least as farr as the ordinary Experiments of Chymists will informe us) of how many she doth make them up. I say then, that it does not by these sufficiently appear to me, that there is any one determinate number of Elements to be uniformly met with in all the several sorts of Bodies allow'd to be perfectly mixt. And for the more distinct proof of this Proposition, I shall in the first place Represent, That there are divers Bodies, which I could never see by fire divided into so many as three Elementary substances. I would fain (as I said lately to _Philoponus_) see that fixt and noble Metal we call Gold separated into Salt, Sulphur and Mercury: and if any man will submit to a competent forfeiture in case of failing, I shall willingly in case of prosperous successe pay both for the Materials and the charges of such an Experiment. 'Tis not, that after what I have try'd my self I dare peremptorily deny, that there may out of Gold be extracted a certain substance, which I cannot hinder Chymists from calling its Tincture or Sulphur; and which leaves the remaining Body depriv'd of its wonted colour. Nor am I sure, that there cannot be drawn out of the same Metal a real quick and running Mercury. But for the Salt of Gold, I never could either see it, or be satisfied that there was ever such a thing separated, _in rerum natura_, by the relation of any credible eye witnesse. And for the several Processes that Promise that effect, the materials that must be wrought upon are somewhat too pretious and costly to be wasted upon so groundlesse adventures, of which not only the successe is doubtful, but the very possibility is not yet demonstrated. Yet that which most deterres me from such tryalls, is not their chargeablenesse, but their unsatisfactorinesse, though they should succeed. For the Extraction of this golden Salt being in Chymists Processes prescribed to be effected by corrosive _Menstruums_, or the Intervention of other Saline Bodies, it will remain doubtful to a wary person, whether the Emergent Salt be that of the Gold it self; or of the Saline Bodies or Spirits employ'd to prepare it; For that such disguises of Metals do often impose upon Artists, I am sure _Eleutherius_ is not so much a stranger to Chymistry as to ignore. I would likewise willingly see the three principles separated from the pure sort of Virgin-Sand, from _Osteocolla_, from refined Silver, from Quicksilver, freed from its adventitious Sulphur, from _Venetian_ Talk [Transcriber's Note: Talck], which by long detention in an extreme _Reverberium_, I could but divide into smaller Particles, (not the constituent principles,) Nay, which, when I caused it to be kept, I know not how long, in a Glasse-house fire, came out in the Figure it's Lumps had when put in, though alter'd to an almost _Amethystine_ colour; and from divers other Bodies, which it were now unnecessary to enumerate. For though I dare not absolutely affirme it to be impossible to Analyze these Bodies into their _Tria Prima_; yet because, neither my own Experiments, nor any competent Testimony hath hitherto either taught me how such an _Analysis_ may be made, or satisfy'd me, that it hath been so, I must take the Liberty to refrain from believing it, till the Chymists prove it, or give us intelligible and practicable Processes to performe what they pretend. For whilst they affect that _Ænigmatical_ obscurity with which they are wont to puzzle the Readers of their divulg'd Processes concerning the Analyticall Preparation of Gold or Mercury, they leave wary persons much unsatisfyed whether or no the differing Substances, they promise to produce, be truly the Hypostatical Principles, or only some intermixtures of the divided Bodies with those employ'd to work upon them, as is Evident in the seeming Crystalls of Silver, and those of Mercury; which though by some inconsiderately supposed to be the Salts of those Metalls, are plainly but mixtures of the Metalline Bodies, with the Saline parts of _Aqua fortis_ or other corrosive Liquors; as is evident by their being reducible into Silver or Quicksilver, as they were before. I cannot but Confesse (saith _Eleutherius_) that though Chymists may upon probable grounds affirm themselves Able to obtain their _Tria Prima_, from Animals and Vegetables, yet I have often wondred that they should so confidently pretend also to resolve all Metalline and other Mineral bodies into Salt, Sulphur, and Mercury. For 'tis a saying almost Proverbial, among those Chymists themselves that are accounted Philosophers; and our famous Countryman _Roger Bacon_ has particularly adopted it; that _Facilius est aurum facere quam destruere_. And I fear, with You, that Gold is not the only Mineral from which Chymists are wont fruitlessly to attempt the separating of their three Principles. I know indeed (continues _Eleutherius_) that the Learned _Sennertus_, even in that book where he takes not upon him to play the Advocate for the Chymists, but the Umpier betwixt them and the Peripateticks, expresses himself roundly, thus;[11] _Salem omnibus inesse (mixtis scilicet) & ex iis fieri posse omnibus in resolutionibus Chymicis versatis notissimum est._ And in the next Page, _Quod de sale dixi_, saies he, _Idem de Sulphure dici potest_: but by his favour I must see very good proofs, before I believe such general Assertions, how boldly soever made; and he that would convince me of their truth, must first teach me some true and practicable way of separating Salt and Sulphur from Gold, Silver, and those many different sort of Stones, that a violent Fire does not bring to Lime, but to Fusion; and not only I, for my own part, never saw any of those newly nam'd Bodies so resolved; but _Helmont_, who was much better vers'd in the Chymical Anatomizing of Bodies then either _Sennertus_ or _I_, has somewhere this resolute passage;[12] _Scio_ (saies he) _ex arena, silicibus & saxis, non Calcariis, nunquam Sulphur aut Mercurium trahi posse_; Nay _Quercetanus_ himself, though the grand stickler for the _Tria Prima_, has this Confession of the Irresolubleness of Diamonds;[13] _Adamas_ (saith he) _omnium factus Lapidum solidissimus ac durissimus ex arctissima videlicet trium principiorum unione ac Cohærentia, quæ nulla arte separationis in solutionem principiorum suorum spiritualium disjungi potest._ And indeed, pursues _Eleutherius_, I was not only glad, but somewhat surprized to find you inclined to Admit that there may be a Sulphur and a running Mercury drawn from Gold; for unlesse you do (as your expression seem'd to intimate) take the word Sulphur in a very loose sence, I must doubt whether our Chymists can separate a Sulphur from Gold: For when I saw you make the experiment that I suppose invited you to speak as you did, I did not judge the golden Tincture to be the true principle of Sulphur extracted from the body, but an aggregate of some such highly colour'd parts of the Gold, as a Chymist would have called a _Sulphur incombustible_, which in plain English seems to be little better than to call it a Sulphur and no Sulphur. And as for Metalline Mercuries, I had not _wondred_ at it, though you had expressed much more severity in speaking of them: For I remember that having once met an old and famous Artist, who had long been (and still is) Chymist to a great Monarch, the repute he had of a very honest man invited me to desire him to tell me ingenuously whether or no, among his many labours, he had ever really extracted a true and running Mercury out of Metalls; to which question he freely replyed, that he had never separated a true Mercury from any Metal; nor had ever seen it really done by any man else. And though Gold is, of all Metalls, That, whose Mercury Chymists have most endeavoured to extract, and which they do the most brag they have extracted; yet the Experienced _Angelus Sala_, in his _Spagyrical_ account of the seven _Terrestrial_ Planets (that is the seven metalls) affords us this memorable Testimony, to, our present purpose; _Quanquam_ (saies he) _&c. experientia tamen (quam stultorum Magistrum [Errata: Magistram] vocamus) certe Comprobavit, Mercurium auri adeo fixum, maturum, & arcte cum reliquis ejusdem corporis substantiis conjungi, ut nullo modo retrogredi possit._ To which he sub-joynes, that he himself had seen much Labour spent upon that Design, but could never see any such Mercury produc'd thereby. And I easily beleeve what he annexes; _that he had often seen Detected many tricks and Impostures of Cheating_ Alchymists. For, the most part of those that are fond of such _Charlatans_, being unskilfull or Credulous, or both, 'tis very easie for such as have some Skill, much craft, more boldness, and no Conscience, to impose upon them; and therefore, though many profess'd _Alchymists_, and divers Persons of Quality have told me that they have made or seen the Mercury of Gold, or of this or that other Metal; yet I have been still apt to fear that either these persons have had a Design to deceive others; or have not had Skill and circumspection enough to keep themselves from being deceived. [Footnote 11: Sennert. lib. de cons. & dissens. pag. 147.] [Footnote 12: Helmon. pag. 409.] [Footnote 13: Quercet. apud Billich. in Thessalo redivivo. pag. 99.] You recall to my mind (sayes _Carneades_) a certain Experiment I once devis'd, innocently to deceive some persons, and let them and others see how little is to be built upon the affirmation of those that are either unskillfull or unwary, when they tell us they have seen _Alchymists_ make the Mercury of this or that Metal; and to make this the more evident, I made my Experiment much more Slight, Short and Simple, than the Chymists usuall processes to Extract Metalline Mercuries; which Operations being commonly more Elaborate and Intricate, and requiring a much more longer time, give the _Alchymists_ a greater opportunity to Cozen, and Consequently are more Obnoxious to the Spectators suspicion. And that wherein I endeavour'd to make my Experiment look the more like a True _Analysis_, was, that I not only pretended as well as others to extract a Mercury from the Metal I wrought upon, but likewise to separate a large proportion of manifest and inflamable Sulphur. I take then, of the filings of Copper, about a Drachme or two, of common sublimate, powder'd, the like Weight, and _Sal Armoniack_ near about as much as of Sublimate; these three being well mingl'd together I put into a small Vial with a long neck, or, which I find better, into a Glass Urinall, which (having first stopped it with Cotton) to avoid the Noxious Fumes, I approach by degrees to a competent Fire of well kindled coals, or (which looks better, but more endangers the Glass) to the Flame of a candle; and after a while the bottom of the Glass being held Just upon the Kindled Coals, or in the flame, You may in about a quarter of an Hour, or perchance in halfe that time, perceive in the Bottom of the Glass some running Mercury; and if then You take away the Glass and break it, You shall find a Parcel of Quicksilver, Perhaps altogether, and perhaps part of it in the pores of the Solid Mass; You shall find too, that the remaining Lump being held to the Flame of the Candle will readily burn with a greenish Flame, and after a little while (perchance presently) will in the Air Acquire a Greenish Blew, which being the Colour that is ascrib'd to Copper, when its Body is unlocked, 'Tis easie to perswade Men that this is the True Sulphur of _Venus_, especially since not only the Salts may be Suppos'd partly to be Flown away, and partly to be Sublim'd to the upper part of the Glass, whose inside (will Commonly appear Whitened by them) but the Metal seems to be quite Destroy'd, the Copper no longer appearing in a Metalline Forme, but almost in that of a Resinous Lump; whereas indeed the Case is only this, That the Saline parts of the Sublimate, together with the _Sal Armoniack_, being excited and actuated by the Vehement heat, fall upon the Copper, (which is a Metal they can more easily corrode, than silver) whereby the small parts of the Mercury being freed from the Salts that kept them asunder, and being by the heat tumbled up and down after many Occursions, they Convene into a Conspicuous Mass of Liquor; and as for the Salts, some of the more Volatile of them Subliming to the upper part of the Glass, the others Corrode the Copper, and uniting themselves with it do strangely alter and Disguise its Metallick Form, and compose with it a new kind of Concrete inflamable like Sulphur; concerning which I shall not now say any thing, since I can Referr You to the Diligent Observations which I remember Mr. _Boyle_ has made concerning this Odde kind of Verdigrease. But Continues _Carneades_ smiling, you know I was not cut out for a Mountebank, and therefore I will hasten to resume the person of a Sceptick, and take up my discourse where You diverted me from prosecuting it. In the next place, then, I consider, that, as there are some Bodies which yield not so many as the three Principles; so there are many others, that in their Resolution Exhibite more principles than three; and that therefore the Ternary Number is not that of the Universal and Adequate Principles of Bodies. If you allow of the Discourse I ately [Errata: lately] made You, touching the primary Associations of the small Particles of matter, You will scarce think it improbable, that of such Elementary Corpuscles there may be more sorts then either three, or four, or five. And if you will grant, what will scarce be deny'd, that Corpuscles of a compounded Nature may in all the wonted Examples of Chymists pass for Elementary, I see not, why you should think it impossible, that as _Aqua Fortis_, or _Aqua Regis_ will make a Separation of colliquated Silver and Gold, though the Fire cannot; so there may be some Agent found out so subtile and so powerfull, at least in respect of those particular compounded Corpuscles, as to be able to resolve them into those more simple ones, whereof they consist, and consequently encrease the number of the Distinct Substances, whereinto the mixt Body has been hitherto thought resoluble. And if that be true, which I recited to you a while ago out of _Helmont_ concerning the Operations of the _Alkahest_, which divides Bodies into other Distinct Substances, both as to number and Nature, then the Fire does; it will not a little countenance my Conjecture. But confining our selves to such wayes of Analyzing mix'd Bodies, as are already not unknown to Chymists, it may without Absurdity be Question'd, whether besides those grosser Elements of Bodies, which they call Salt Sulphur and Mercury, there may not be Ingredients of a more Subtile Nature, which being extreamly little, and not being in themselves Visible, may escape unheeded at the Junctures of the Destillatory Vessels, though never so carefully Luted. For let me observe to you one thing, which though not taken notice of by Chymists, may be a notion of good Use in divers Cases to a Naturalist, that we may well suspect, that there may be severall Sorts of Bodies, which are not Immediate Objects of any one of our senses; since we See, that not only those little Corpuscles that issue out of the Loadstone, and perform the Wonders for which it is justly admired; But the _Effluviums_ of Amber, Jet, and other Electricall Concretes, though by their effects upon the particular Bodies dispos'd to receive their Action, they seem to fall under the Cognizance of our Sight, yet do they not as Electrical immediately Affect any of our senses, as do the bodies, whether minute or greater, that we See, Feel, Taste, &c. But, continues _Carneades_, because you may expect I should, as the Chymists do, consider only the sensible Ingredients of Mixt Bodies, let us now see, what Experience will, even as to these, suggest to us. It seems then questionable enough, whether from Grapes variously order'd there may not be drawn more distinct Substances by the help of the Fire, then from most other mixt Bodies. For the Grapes themselves being dryed into Raysins and distill'd, will (besides _Alcali_, Phlegm, and Earth) yield a considerable quantity of an Empyreumatical Oyle, and a Spirit of a very different nature from that of Wine. Also the unfermented Juice of Grapes affords other distil'd Liquors then Wine doth. The Juice of Grapes after fermentation will yield a _Spiritus Ardens_; which if competently rectifyed will all burn away without leaving any thing remaining. The same fermented Juice degenerating into Vinager, yields an acid and corroding Spirit. The same Juice turn'd [Errata: tunned] up, armes it self with Tartar; out of which may be separated, as out of other Bodies, Phlegme, Spirit, Oyle, Salt and Earth: not to mention what Substances may be drawn from the Vine it self, probably differing from those which are separated from Tartar, which is a body by it self, that has few resemblers in the World. And I will further consider that what force soever you will allow this instance, to evince that there are some Bodies that yield more Elements then others, it can scarce be deny'd but that the Major part of bodies that are divisible into Elements, yield more then three. For, besides those which the Chymists are pleased to name Hypostatical, most bodies contain two others, Phlegme and Earth, which concurring as well as the rest to the constitution of Mixts, and being as generally, if not more, found in their _Analysis_, I see no sufficient cause why they should be excluded from the number of Elements. Nor will it suffice to object, as the _Paracelsians_ are wont to do, that the _Tria prima_ are the most useful Elements, and the Earth and Water but worthlesse and unactive; for Elements being call'd so in relation to the constituting of mixt Bodies, it should be upon the account of its Ingrediency, not of its use, that any thing should be affirmed or denyed to be an Element: and as for the pretended uselessness of Earth and Water, it would be consider'd that usefulnesse, or the want of it, denotes only a Respect or Relation to us; and therefore the presence, or absence of it, alters not the Intrinsick nature of the thing. The hurtful Teeth of Vipers are for ought I know useless to us, and yet are not to be deny'd to be parts of their Bodies; and it were hard to shew of what greater Use to Us, then Phlegme and Earth, are those Undiscern'd Stars, which our New _Telescopes_ discover to Us, in many Blanched places of the Sky; and yet we cannot but acknowledge them Constituent and Considerably great parts of the Universe. Besides that whether or no the Phlegme and Earth be immediately Useful, but necessary to constitute the Body whence they are separated; and consequently, if the mixt Body be not Useless to us, those constituent parts, without which it could not have been That mixt Body, may be said not to be Unuseful to Us: and though the Earth and Water be not so conspicuously Operative (after separation) as the other three more active Principles, yet in this case it will not be amiss to remember the lucky Fable of _Menemius Aggrippa_, of the dangerous Sedition of the Hands and Legs, and other more busie parts of the Body, against the seemingly unactive Stomack. And to this case also we may not unfitly apply that Reasoning of an Apostle, to another purpose; _If the Ear shall say, because I Am not the Eye, I am not of the Body; Is it therefore not of the Body? If the whole Body were Eye, where were the Hearing? If the whole were for hearing, where the smelling?_ In a word, since Earth and water appear, as clearly and as generally as the other Principles upon the resolution of Bodies, to be the Ingredients whereof they are made up; and since they are useful, if not immediately to us, or rather to Physitians, to the Bodies they constitute, and so though in somewhat a remoter way, are serviceable to us; to exclude them out of the number of Elements, is not to imitate Nature. [Transcriber's Note: See the printer's note (beginning "The Authors constant Absence") at the end of the book for material that the printer inadvertently omitted from this page.] But, pursues _Carneades_, though I think it Evident, that Earth and Phlegme are to be reckon'd among the Elements of most Animal and Vegetable Bodies, yet 'tis not upon that Account alone, that I think divers Bodies resoluble into more Substances then three. For there are two Experiments, that I have sometimes made to shew, that at least some Mixts are divisible into more Distinct Substances then five. The one of these Experiments, though 'twill be more seasonable for me to mention it fully anon, yet in the mean time, I shall tell you thus much of it, That out of two Distill'd Liquors, which pass for Elements of the Bodies whence they are drawn, I can without Addition make a true Yellow and Inflamable Sulphur, notwithstanding that the two Liquors remain afterwards Distinct. Of the other Experiment, which perhaps will not be altogether unworthy your Notice, I must now give you this particular Account. I had long observ'd, that by the Destillation of divers Woods, both in Ordinary, and some unusuall sorts of Vessels, the Copious Spirit that came over, had besides a strong tast, to be met with in the Empyreumaticall Spirits of many other Bodies, an Acidity almost like that of Vinager: Wherefore I suspected, that though the sowrish Liquor Distill'd, for Instance, from Box-Wood, be lookt upon by Chymists as barely the Spirit of it, and therefore as one single Element or Principle; yet it does really consist of two Differing Substances, and may be divisible into them; and consequently, that such Woods and other Mixts as abound with such a Vinager, may be said to consist of one Element or Principle, more then the Chymists as yet are Aware of; Wherefore bethinking my self, how the separation of these two Spirits might be made, I Quickly found, that there were several wayes of Compassing it. But that of them which I shall at present mention, was this, Having Destill'd a Quantity of Box-Wood _per se_, and slowly rectify'd the sowrish Spirit, the better to free it both from Oyle and Phlegme, I cast into this Rectify'd Liquor a convenient Quantity of Powder'd Coral, expecting that the Acid part of the Liquor would Corrode the Coral, and being associated with it would be so retain'd by it, that the other part of the Liquor, which was not of an acid Nature, nor fit to fasten upon the Corals, would be permitted to ascend alone. Nor was I deceiv'd in my Expectation; For having gently abstracted the Liquor from the Coralls, there came over a Spirit of a Strong smell, and of a tast very piercing, but without any sourness; and which was in diverse qualities manifestly different, not only from a Spirit of Vinager, but from some Spirit of the same Wood, that I purposely kept by me without depriving it of its acid Ingredient. And to satisfy you, that these two Substances were of a very differing Nature, I might informe you of several Tryals that I made, but must not name some of them, because I cannot do so without making some unseasonable discoveries. Yet this I shall tell you at present, that the sowre Spirit of _Box_, not only would, as I just now related, dissolve Corals, which the other would not fasten on, but being pour'd upon Salt of Tartar would immediately boile and hiss, whereas the other would lye quietly upon it. The acid Spirit pour'd upon _Minium_ made a Sugar of Lead, which I did not find the other to do; some drops of this penetrant spirit being mingl'd with some drops of the blew Syrup of Violets seem'd rather to dilute then otherwise alter the colour; whereas the Acid Spirit turn'd the syrup of a reddish colour, and would probably have made it of as pure a red as Acid Salts are wont to do, had not its operation been hindered by the mixture of the other Spirit. A few drops of the compound Spirit being Shaken into a pretty quantity of the infusion of _Lignum Nephriticum_, presently destroyed all the blewish colour, whereas the other Spirit would not take it away. To all which it might be added, that having for tryals sake pour'd fair water upon the Corals that remained in the bottom of the glass wherein I had rectifyed the double spirit (if I may so call it) that was first drawn from the Box, I found according to my expectation that the Acid Spirit had really dissolved the Corals, and had coagulated with them. For by the affusion of fair Water, I Obtain'd a Solution, which (to note that singularity upon the bye) was red, whence the Water being evaporated, there remained a soluble Substance much like the Ordinary Salt of Coral, as Chymists are pleas'd to call that Magistery of Corals, which they make by dissolving them in common spirit of Vinager, and abstracting the _Menstruum ad Siccitatem_. I know not whether I should subjoine, on this occasion, that the simple spirit of Box, if Chymists will have it therefore Saline because it has a strong tast, will furnish us with a new kind of Saline Bodies, differing from those hitherto taken notice of. For whereas of the three chief sorts of Salts, the Acid, the Alcalizate, and the Sulphureous, there is none that seems to be friends with both the other two, as I may, e're it be long, have occasion to shew; I did not find but that the simple spirit of Box did agree very well (at least as farr as I had occasion to try it) both with the Acid and the other Salts. For though it would lye very quiet with salt of Tartar, Spirit of Urine, or other bodies, whose Salts were either of an Alcalizate or fugitive Nature; yet did not the mingling of Oyle of Vitriol it self produce any hissing or Effervescence, which you know is wont to ensue upon the Affusion of that highly Acid Liquor upon either of the Bodies newly mentioned. I think my self, sayes _Eleutherius_, beholden to you, for this Experiment; not only because I forsee you will make it helpful to you in the Enquiry you are now upon, but because it teaches us a Method, whereby we may prepare a numerous sort of new spirits, which though more simple then any that are thought Elementary, are manifestly endow'd with peculiar and powerfull qualities, some of which may probably be of considerable use in Physick, as well alone, as associated with other things; as one may hopefully guess by the redness of that Solution your sour Spirit made of Corals, and by some other circumstances of your Narrative. And suppose (pursues _Eleutherius_) that you are not so confin'd, for the separation of the Acid parts of these compound Spirits from the other, to employ Corals; but that you may as well make use of any Alcalizate Salt, or of Pearls, or Crabs eyes, or any other Body, upon which common Spirit of Vinager will easily work, and, to speak in an _Helmontian_ Phrase, Exantlate it self. I have not yet tryed, sayes _Carneades_, of what use the mention'd liquors may be in Physick, either as Medicines or as _Menstruums_: But I could mention now (and may another time) divers of the tryals that I made to satisfy my self of the difference of these two Liquors. But that, as I allow your thinking what you newly told me about Corals, I presume you will allow me, from what I have said already, to deduce this Corollary; That there are divers compound bodies, which may be resolv'd into four such differing Substances, as may as well merit the name of Principles, as those to which the Chymists freely give it. For since they scruple not to reckon that which I call the compound Spirit of Box, for the spirit, or as others would have it, the Mercury of that Wood, I see not, why the Acid liquor, and the other, should not each of them, especially that last named, be lookt upon as more worthy to be called an Elementary Principle; since it must needs be of a more simple nature then the Liquor, which was found to be divisible into that, and the Acid Spirit. And this further use (continues _Carneades_) may be made of our experiment to my present purpose, that it may give us a rise to suspect, that since a Liquor reputed by the Chymists to be, without dispute, Homogeneous, is by so slight a way divisible into two distinct and more simple Ingredients, some more skilful or happier Experimenter then I may find a way either further to divide one of these Spirits, or to resolve some or other, if not all, of those other Ingredients of mixt Bodies, that have hitherto pass'd among Chymists for their Elements or Principles. THE SCEPTICAL CHYMIST. _The Fourth Part._ And thus much (sayes _Carneades_) may suffice to be said of the _Number_ of the Distinct substances separable from mixt Bodies by the Fire: Wherefore I now proceed to consider the _nature_ of them, and shew you, That though they seem _Homogeneous_ Bodies, yet have they not the purity and simplicity that is requisite to Elements. And I should immediately proceed to the proof of my Assertion, but that the Confidence wherewith Chymists are wont to call each of the Substances we speak of by the name of Sulphur or Mercury, or the other of the Hypostaticall Principles, and the intollerabln [Errata: intolerable] Ambiguity they allow themselves ie [Errata: in] their Writings and Expressions, makes it necessary for me in Order to the Keeping you either from mistaking me, or thinking I mistake the Controversie, to take Notice to you and complain of the unreasonable Liberty they give themselves of playing with Names at pleasure. And indeed if I were oblig'd in this Dispute, to have such regard to the Phraseology of each particular Chymist, as not to Write any thing which this or that Author may not pretend, not to contradict this or that sence, which he may give as Occasion serves to his Ambiguous Expressions, I should scarce know how to dispute, nor which way to turn myself. For I find that even Eminent Writers, (such as _Raymund Lully_, _Paracelsus_ and others) do so abuse the termes they employ, that as they will now and then give divers things, one name; so they will oftentimes give one thing, many Names; and some of them (perhaps) such, as do much more properly signifie some Distinct Body of another kind; nay even in Technical Words or Termes of Art, they refrain not from this Confounding Liberty; but will, as I have Observ'd, call the same Substance, sometimes the Sulphur, and Sometimes the Mercury of a Body. And now I speak of Mercury, I cannot but take Notice, that the Descriptions they give us of that Principle or Ingredient of mixt Bodies, are so intricate, that even those that have Endeavour'd to Pollish and Illustrate the Notions of the Chymists, are fain to confess that they know not what to make of it, either by Ingenuous Acknowledgments, or Descriptions that are not Intelligible. I must confess (sayes _Eleutherius_) I have, in the reading of _Paracelsus_ and other Chymical Authors, been troubled to find, that such hard Words and Equivocal Expressions, as You justly complain of, do even when they treat of Principles, seem to be studiously affected by those Writers; whether to make themselves to be admir'd by their Readers, and their Art appear more Venerable and Mysterious, or, (as they would have us think) to conceal from them a Knowledge themselves judge inestimable. But whatever (sayes _Carneades_) these Men may promise themselves from a Canting way of delivering the Principles of Nature, they will find the Major part of Knowing Men so vain, as when they understand not what they read, to conclude, that it is rather the Writers fault then their own. And those that are so ambitious to be admir'd by the Vulgar, that rather then go without the Admiration of the Ignorant they will expose themselves to the contempt of the Learned, those shall, by my consent, freely enjoy their Option. As for the Mystical Writers scrupling to Communicate their Knowledge, they might less to their own Disparagement, and to the trouble of their Readers, have conceal'd it by writing no Books, then by Writing bad ones. If _Themistius_ were here, he would not stick to say, that Chymists write thus darkly, not because they think their Notions too precious to be explain'd, but because they fear that if they were explain'd, men would discern, that they are farr from being precious. And indeed, I fear that the chief Reason why Chymists have written so obscurely of their three Principles, may be, That not having Clear and Distinct Notions of them themselves, they cannot write otherwise then Confusedly of what they but Confusedly Apprehend: Not to say that divers of them, being Conscious to the Invalidity of their Doctrine, might well enough discerne that they could scarce keep themselves from being confuted, but by keeping themselves from being clearly understood. But though much may be said to Excuse the Chymists when they write Darkly, and Ænigmatically, about the Preparation of their _Elixir_, and Some few other grand _Arcana_, the divulging of which they may upon Grounds Plausible enough esteem unfit; yet when they pretend to teach the General Principles of Natural Philosophers, this Equivocall Way of Writing is not to be endur'd. For in such Speculative Enquiries, where the naked Knowledge of the Truth is the thing Principally aim'd at, what does he teach me worth thanks that does not, if he can, make his Notion intelligible to me, but by Mystical Termes, and Ambiguous Phrases darkens what he should clear up; and makes me add the Trouble of guessing at the sence of what he Equivocally expresses, to that of examining the Truth of what he seems to deliver. And if the matter of the Philosophers Stone, and the manner of preparing it, be such Mysteries as they would have the World believe them, they may Write Intelligibly and Clearly of the Principles of mixt Bodies in General, without Discovering what they call the Great Work. But for my part (Continues _Carneades_) what my Indignation at this Un-philosophical way of teaching Principles has now extorted from me, is meant chiefly to excuse my self, if I shall hereafter oppose any Particular Opinion or assertion, that some Follower of _Paracelsus_ or any Eminent Artist may pretend not to be his Masters. For, as I told you long since, I am not Oblig'd to examine private mens writings, (which were a Labour as endless as unprofitable) being only engag'd to examine those Opinions about the _Tria Prima_, which I find those Chymists I have met with to agree in most: And I Doubt not but my Arguments against their Doctrine will be in great part easily enough applicable ev'n to those private Opinions, which they do not so directly and expresly oppose. And indeed, that which I am now entering upon being the Consideration of the things themselves whereinto _Spagyrists_ resolve mixt Bodies by the Fire, If I can shew that these are not of an Elementary Nature, it will be no great matter what names these or those Chymists have been pleased to give them. And I question not that to a Wise man, and consequently to _Eleutherius_, it will be lesse considerable to know, what Men Have thought of Things, then what they Should have thought. In the fourth and last place, then, I consider, that as generally as Chymists are wont to appeal to Experience, and as confidently as they use to instance the several substances separated by the Fire from a Mixt Body, as a sufficient proof of their being its component Elements: Yet those differing Substances are many of them farr enough from Elementary simplicity, and may be yet look'd upon as mixt Bodies, most of them also retaining, somewhat at least, if not very much, of the Nature of those Concretes whence they were forc'd. I am glad (sayes _Eleutherius_) to see the Vanity or Envy of the canting Chymists thus discover'd and chastis'd; and I could wish, that Learned Men would conspire together to make these deluding Writers sensible, that they must no longe [Transcriber's Note: longer] hope with Impunity to abuse the World. For whilst such Men are quietly permitted to publish Books with promising Titles, and therein to Assert what they please, and contradict others, and ev'n themselves as they please, with as little danger of being confuted as of being understood, they are encourag'd to get themselves a name, at the cost of the Readers, by finding that intelligent Men are wont for the reason newly mention'd, to let their Books and Them alone: And the ignorant and credulous (of which the number is still much greater then that of the other) are forward to admire most what they least understand. But if Judicious men skill'd in Chymical affaires shall once agree to write clearly and plainly of them, and thereby keep men from being stunn'd, as it were, or imposd upon by dark or empty Words; 'tis to be hop'd that these men finding that they can no longer write impertinently and absurdly, without being laugh'd at for doing so, will be reduc'd either to write nothing, or Books that may teach us something, and not rob men, as formerly, of invaluable Time; and so ceasing to trouble the World with Riddles or Impertinencies, we shall either by their Books receive an Advantage, or by their silence escape an Inconvenience. But after all this is said (continues _Eleutherius_) it may be represented in favour of the Chymists, that, in one regard the Liberty they take in using names, if it be excusable at any time, may be more so when they speak of the substances whereinto their _Analysis_ resolves mixt Bodies: Since as Parents have the Right to name their own Children, it has ever been allow'd to the Authors of new Inventions, to Impose Names upon them. And therefore the subjects we speak of being so the Productions of the Chymist's Art, as not to be otherwise, but by it, obtainable; it seems but equitable to give the Artists leave to name them as they please: considering also that none are so fit and likely to teach us what those Bodies are, as they to whom we ow'd them. I told You already (sayes _Carneades_) that there is great Difference betwixt the being able to make Experiments, and the being able to give a Philosophical Account of them. And I will not now add, that many a Mine-digger may meet, whilst he follows his work, with a Gemm or a Mineral which he knowes not what to make of, till he shews it a Jeweller or a Mineralist to be inform'd what it is. But that which I would rather have here observ'd, is, That the Chymists I am now in debate with have given up the Liberty You challeng'd for them, of using Names at Pleasure, and confin'd Themselves by their Descriptions, though but such as they are, of their Principles; so that although they might freely have call'd any thing their _Analysis_ presents them with, either Sulphur, or Mercury, or Gas, or Blas, or what they pleas'd; yet when they have told me that Sulphur (for instance) is a Primogeneal and simple Body, Inflamable, Odorous, &c. they must give me leave to dis-believe them, if they tell me that a Body that is either compounded or uninflamable is such a Sulphur; and to think they play with words, when they teach that Gold and some other Minerals abound with an Incombustible Sulphur, which is as proper an Expression, as a Sun-shine Night, or Fluid Ice. But before I descend to the Mention of Particulars belonging to my Fourth Consideration, I think it convenient to premise a few Generals; some of which I shall the less need to insist on at present, because I have Touched on them already. And first I must invite you to take notice of a certain passage in _Helmont_;[14] which though I have not Found much heeded by his Readers, He Himself _mentions_ as a notable thing, and I take to be a very considerable one; for whereas the Distill'd oyle of _oyle-olive_, though drawn _per se_ is (as I have try'd) of a very sharp and fretting Quality, and of an odious tast, He tells us that Simple oyle being only digested with _Paracelsus's sal circulatum_, is reduc'd into dissimilar parts, and yields a sweet Oyle, very differing from the oyle distill'd, from [Errata: distill'd from] sallet oyle; as also that by the same way there may be separated from Wine a very sweet and gentle Spirit, partaking of a far other and nobler quality then that which is immediately drawn by distillation and call'd _Dephlegm'd Aqua vitæ_, from whose Acrimony this other spirit is exceedingly remote, although the _sal circulatum_ that makes these _Anatomies_ be separated from the Analyz'd Bodies, in the same weight and with the same qualities it had before; which Affirmation of _Helmont_ if we admit to be true, we must acknowledge that there may be a very great disparity betwixt bodies of the same denomination (as several oyles, or several spirits) separable from compound Bodies: For, besides the differences I shall anon take notice of, betwixt those distill'd Oyles that are commonly known to Chymists, it appears by this, that by means of the _Sal Circulatum_, There may be quite another sort of Oyles obtain'd from the same Body; and who knowes but that there may be yet other Agents found in Nature, by whose help there may, whether by Transmutation or otherwise, be obtain'd from the Bodies Vulgarly call'd Mixt, Oyles or other substances, Differing from those of the same Denomination, known either to Vulgar Chymists, or even to _Helmont_ Himself: but for fear You should tell me, that this is but a conjecture grounded upon another Man's Relation, whose Truth we have not the means to Experiment, I will not Insist upon it; but leaving You to Consider of it at leasure, I shall proceed to what is next. [Footnote 14: _Illud notabile, in vino esse Spiritum quendam mitiorem ulterioris & nobilioris qualitatis participem qu[=a] qui immediatè per distillationem elicitur diciturque aqua vitæ dephlegmata, quod facilius in simplici Olivarum oleo ad oculum spectatur. Quippe distillatum oleum absque laterum aut tigularum [Errata: tegularum] additamento, quodque oleum Philosophorum dicitur, multum dissert ab ejus oleitate; quæ elicitur prius reducto oleo simplici in partes dissimilares sola digestione & Salis circulati Paracelsici appositione; siquidem sal circulatum idem in pondere & quantitatibus pristinis ab oleo segregatur postquam oleum olivarum in sui heterogeneitates est dispositum. Dulce enim tunc Oleum Olivarum ex oleo, prout & suavissimus vini spiritus a vino hoc pacto separantur, longéque ab aquæ vitæ acrimoniâ distinctus._--Helmont. Aura vitalis, pag. 725.] Secondly, Then if that be True which was the Opinion of _Lucippus_, _Democritus_, and other prime _Anatomists_ of old, and is in our dayes reviv'd by no mean Philosophers; namely, That our Culinary Fire, such as Chymists use, consists of swarmes of little Bodies swiftly moving, which by their smallness and motion are able to permeate the sollidest and Compactest Bodies, and even Glass it Self; If this (I say) be True, since we see that In flints and other Concretes, the Fiery part is Incorporated with the Grosser, it will not be Irrationall to conjecture, that multitudes of these Fiery Corpuscles, getting in at the Pores of the Glass, may associate themselves with the parts of the mixt Body whereon they work, and with them Constitute new Kinds of Compound Bodies, according as the Shape, Size, and other Affections of the Parts of the Dissipated Body happen to dispose them, in Reference to such Combinations; of which also there may be the greater Number; if it be likewise granted that the Corpuscles of the Fire, though all exceeding minute, and very swiftly moved, are not all of the same bigness, nor Figure. And if I had not Weightier Considerations to Discourse to you of, I could name to you, to Countenance what I have newly said, some particular Experiments by which I have been Deduc'd to think, that the Particles of an open Fire working upon some Bodies may really Associate themselves therewith, and add to the Quantity. But because I am not so sure, that when the Fire works upon Bodies included in Glasses, it does it by a reall Trajection of the Fiery Corpuscles themselves, through the Substance of the Glass, I will proceed to what is next to be mention'd. I could (sayes _Eleutherius_) help you to some Proofes, whereby I think it may be made very probable, that when the Fire acts immediately upon a Body, some of its Corpuscles may stick to those of the burnt Body, as they seem to do in Quicklime, but in greater numbers, and more permanently. But for fear of retarding Your Progress, I shall desire you to deferr this Enquiry till another time, and proceed as you intended. You may then in the next place (sayes _Carneades_) observe with me, that not only there are some Bodies, as Gold, and Silver, which do not by the usual Examens, made by Fire, Discover themselves to be mixt; but if (as You may Remember I formerly told You) it be a De-compound Body that is Dissipable into several Substances, by being expos'd to the Fire it may be resolv'd into such as are neither Elementary, nor such as it was upon its last mixture Compounded of; but into new Kinds of mixts. Of this I have already given You some Examples in Sope, Sugar of Lead, and Vitrioll. Now if we shall Consider that there are some Bodies, as well Natural, (as that I last nam'd) as Factitious, manifestly De-compounded; That in the Bowells of the Earth Nature may, as we see she sometimes does, make strange Mixtures; That Animals are nourish'd with other Animals and Plants; And, that these themselves have almost all of them their Nutriment and Growth, _either_ from a certain Nitrous Juice Harbour'd in the Pores of the Earth, _or_ from the Excrements of Animalls, _or_ from the putrify'd Bodies, either of living Creatures or Vegetables, _or_ from other Substances of a Compounded Nature; If, I say, we consider this, it may seem probable, that there may be among the Works of Nature (not to mention those of Art) a greater Number of De-compound Bodies, then men take Notice of; And indeed, as I have formerly also observ'd, it does not at all appear, that all Mixtures must be of Elementary Bodies; but it seems farr more probable, that there are divers sorts of compound Bodies, even in regard of all or some of their Ingredients, consider'd Antecedently to their Mixture. For though some seem to be made up by the immediate Coalitions of the Elements, or Principles themselves, and therefore may be call'd _Prima Mista_, or _Mista Primaria_; yet it seems that many other Bodies are mingl'd (if I may so speak) at the second hand, their immediate Ingredients being not Elementary, but these primary Mixts newly spoken of; And from divers of these Secondary sort of Mixts may result, by a further Composition, a Third sort, and so onwards. Nor is it improbable, that some Bodies are made up of Mixt Bodies, not all of the same Order, but of several; as (for Instance) a Concrete may consist of Ingredients, whereof the one may have been a primary, the other a Secondary Mixt Body; (as I have in Native Cinnaber, by my way of Resolving it, found both that Courser the [Errata: delete "the"] part that seems more properly to be Oar, and a Combustible Sulphur, and a Running Mercury:) or perhaps without any Ingredient of this latter sort, it may be compos'd of Mixt Bodies, some of them of the first, and some of the third Kind; And this may perhaps be somewhat Illustrated by reflecting upon what happens in some Chymical Preparations of those Medicines which they call their _Bezoardicum's_. For first, they take Antimony and Iron, which may be look'd upon as _Prima Mista_; of these they compound a Starry _Regulus_, and to this they add according to their Intention, either Gold, or Silver, which makes with it a new and further Composition. To this they add Sublimate, which is it self a De-compound body, (consisting of common Quicksilver, and divers Salts United by Sublimation into a Crystalline Substance) and from this Sublimate, and the other Metalline Mixtures, they draw a Liquor, which may be allow'd to be of a yet more Compounded Nature. If it be true, as Chymists affirm it, that by this Art some of the Gold or Silver mingl'd with the _Regulus_ may be carry'd over the Helme with it by the Sublimate; as indeed a Skilfull and Candid person complain'd to me a while since, That an experienc'd Friend of His and mine, having by such a way brought over a great Deal of Gold, in hope to do something further with it, which might be gainfull to him, has not only miss'd of his Aim, but is unable to recover his Volatiliz'd Gold out of the Antimonial butter, wherewith it is strictly united. Now (Continues _Carneades_) if a Compound body consist of Ingredients that are not meerly Elementary; it is not hard to conceive, that the Substances into which the Fire Dissolves it, though seemingly Homogeneous enough, may be of a Compounded Nature, those parts of each body that are most of Kin associating themselves into a Compound of a new Kind. As when (for example sake) I have caus'd Vitrioll and _Sal Armoniack_, and Salt Petre to be mingl'd and Destill'd together, the Liquor that came over manifested it self not to be either Spirit of Nitre, or of _Sal Armoniack_, or of Vitrioll. For none of these would dissolve crude gold, which yet my Liquor was able readily to do; and thereby manifested it self to be a new Compound, consisting at least of Spirit of Nitre, and _Sal Armoniack_, (for the latter dissolv'd in the former, will Work on Gold) which nevertheless are not by any known way separable, and consequently would not pass for a Mixt Body, if we our selves did not, to obtain it, put and Distill together divers Concretes, whose Distinct Operations were known before hand. And, to add on this Occasion the Experiment I lately promis'd You, because it is Applicable to our present purpose, I shall Acquaint You, that suspecting the Common Oyle of Vitrioll not to be altogether such a simple Liquor as Chymists presume it, I mingl'd it with an equal or a Double Quantity (for I try'd the Experiment more then once) of common Oyle of Turpentine, such as together with the other Liquor I bought at the Drugsters. And having carefully (for the Experiment is Nice, and somewhat dangerous) Distill'd the Mixture in a small Glass Retort, I obtain'd according to my Desire, (besides the two Liquors I had put in) a pretty Quantity of a certain substance, which sticking all about the Neck of the Retort Discover'd it self to be Sulphur, not only by a very strong Sulphureous smell, and by the colour of Brimstone; but also by this, That being put upon a coal, it was immediately kindl'd, and burn'd like common Sulphur. And of this Substance I have yet by me some little Parcells, which You may command and examine when you please. So that from this Experiment I may deduce either one, or both of these Propositions, That a real Sulphur may be made by the Conjunction of two such Substances as Chymists take for Elementary, And which did not either of them apart appear to have any such body in it; or that Oyle of Vitrioll though a Distill'd Liquor, and taken for part of the Saline Principle of the Concrete that yields it, may yet be so Compounded a body as to contain, besides its Saline part, a Sulphur like common brimstone, which would hardly be it self a simple or un-compounded body. I might (pursues _Carneades_) remind You, that I formerly represented it, as possible, That as there may be more Elements then five, or six; so the Elements of one body may be Different from those of another; whence it would follow, that from the Resolution of De-compound body [Errata: bodies], there may result Mixts of an altogether new kind, by the Coalition of Elements that never perhaps conven'd before. I might, I say, mind You of this, and add divers things to this second Consideration; but for fear of wanting time I willingly pretermit them, to pass on to the third, which is this, That the Fire does not alwayes barely resolve or take asunder, but may also after a new manner mingle and compound together the parts (whether Elementary or not) of the Body Dissipated by it. This is so evident, sayes _Carneades_, in some obvious Examples, that I cannot but wonder at their Supiness that have not taken notice of it. For when Wood being burnt in a Chimney is dissipated by the Fire into Smoke and Ashes, that smoke composes soot, which is so far from being any one of the principles of the Wood, that (as I noted above) you may by a further _Analysis_ separate five or six distinct substances from it. And as for the remaining Ashes, the Chymists themselves teach us, that by a further degree of fire they may be indissolubly united into glass. 'Tis true, that the _Analysis_ which the Chymists principally build upon is made, not in the open air, but in close Vessels; but however, the Examples lately produc'd may invite you shrewdly to suspect, That heat may as well compound as dissipate the Parts of mixt Bodies: and not to tell you, that I have known a Vitrification made even in close vessels, I must remind you that the Flowers of Antimony, and those of Sulphur, are very mix'd Bodies, though they ascend in close vessells: And that 'twas in stopt glasses that I brought up the whole Body of Camphire. And whereas it may be objected, that all these Examples are of Bodies forc'd up in a dry, not a Fluid forme, as are the Liquors wont to be obtain'd by distillation; I answer, That besides that 'tis possible, that a Body may be chang'd from Consistent to Fluid, or from Fluid to Consistent, without being otherwise much altered, as may appear by the Easiness wherewith in Winter, without any Addition or Separation of Visible Ingredients, the same substance may be quickly harden'd into brittle Ice, and thaw'd again into Fluid Water; Besides this, I say it would be consider'd, that common Quick-silver it self, which the Eminentest Chymists confess to be a mixt Body, may be Driven over the Helme in its Pristine forme of Quicksilver, and consequently, in that of a Liquor. And certainly 'tis possible that very compounded Bodies may concur to Constitute Liquors; Since, not to mention that I have found it possible, by the help of a certain _Menstruum_, to distill Gold it self through a Retort, even with a Moderate Fire: Let us but consider what happens in Butter of Antimony. For if that be carefully rectify'd, it may be reduc'd into a very clear Liquor; and yet if You cast a quantity of fair water upon it, there will quickly precipitate a Ponderous and Vomitive Calx, which made before a considerable part of the Liquor, and yet is indeed (though some eminent Chymists would have it Mercurial) an Antimonial Body carryed over and kept dissolv'd by the Salts of the Sublimate, and consequently a compounded one; as You may find if You will have the Curiosity to Examine this White powder by a skilful Reduction. And that You may not think that Bodies as compounded as flowers of Brimstone cannot be brought to Concurr to Constitute Distill'd Liquors; And also That You may not imagine with Divers Learned Men that pretend no small skill in Chymistry, that at least no mixt Body can be brought over the Helme, but by corrosive Salts, I am ready to shew You, when You please, among other wayes of bringing over Flowers of Brimstone (perhaps I might add even Mineral Sulphurs) some, wherein I employ none but Oleaginous bodies to make Volatile Liquors, in which not only the colour, but (which is a much surer mark) the smell and some Operations manifest that there is brought over a Sulphur that makes part of the Liquor. One thing more there is, _Eleutherius_, sayes _Carneades_, which is so pertinent to my present purpose, that though I have touch'd upon it before, I cannot but on this occasion take notice of it. And it is this, That the Qualities or Accidents, upon whose account Chymists are wont to call a portion of Matter by the name of Mercury or some other of their Principles, are not such but that 'tis possible as Great (and therefore why not the like?) may be produc'd by such changes of Texture, and other Alterations, as the Fire may make in the small Parts of a Body. I have already prov'd, when I discours'd of the second General Consideration, by what happens to plants nourish'd only with fair water, and Eggs hatch'd into Chickens, that by changing the disposition of the component parts of a Body, Nature is able to effect as great Changes in a parcell of Matter reputed similar, as those requisite to Denominate one of the _Tria Prima_. And though _Helmont_ do somewhere wittily call the Fire the Destructor and the Artificial Death of Things; And although another Eminent Chymist and Physitian be pleas'd to build upon this, That Fire can never generate any thing but Fire; Yet You will, I doubt not, be of another mind, If You consider how many new sorts of mixt Bodies Chymists themselves have produc'd by means of the Fire: And particularly, if You consider how that Noble and Permanent Body, Glass, is not only manifestly produc'd by the violent action of the Fire, but has never, for ought we know, been produc'd any other way. And indeed it seems but an inconsiderate Assertion of some _Helmontians_, that every sort of Body of a Peculiar Denomination must be produc'd by some Seminal power; as I think I could evince, if I thought it so necessary, as it is for me to hasten to what I have further to discourse. Nor need it much move us, that there are some who look upon whatsoever the Fire is employ'd to produce, not as upon Natural but Artificial Bodies. For there is not alwaies such a difference as many imagine betwixt the one and the other: Nor is it so easy as they think, clearly to assigne that which Properly, Constantly, and Sufficiently, Discriminates them. But not to engage my self in so nice a Disquisition, it may now suffice to observe, that a thing is commonly termed Artificial, when a parcel of matter is by the Artificers hand, or Tools, or both, brought to such a shape or Form, as he Design'd before-hand in his Mind: Whereas in many of the Chymical Productions the effect would be produc'd whether the Artificer intended it or no; and is oftentimes very much other then he Intended or Look't for; and the Instruments employ'd, are not Tools Artificially fashion'd and shaped, like those of Tradesmen, for this or that particular Work; but, for the most part, Agents of Nature's own providing, and whose chief Powers of Operation they receive from their own Nature or Texture, not the Artificer. And indeed, the Fire is as well a Natural Agent as Seed: And the Chymist that imployes it, does but apply Natural Agents and Patients, who being thus brought together, and acting according to their respective Natures, performe the worke themselves; as Apples, Plums, or other fruit, are natural Productions, though the Gardiner bring and fasten together the Sciens of the Stock, and both Water, and do perhaps divers other wayes Contribute to its bearing fruit. But, to proceed to what I was going to say, You may observe with me, _Eleutherius_, that, as I told You once before, Qualities sleight enough may serve to Denominate a Chymical Principle. For, when they anatomize a compound Body by the Fire, if they get a Substance inflamable, and that will not mingle with Water, that they presently call Sulphur; what is sapid and Dissoluble in Water, that must pass for Salt; Whatsoever is fix'd and indissoluble in Water, that they name Earth. And I was going to add, that, whatsoever Volatile substance they know not what to make of, not to say, whatsoever they please, that they call Mercury. But that these Qualities may either be produc'd, otherwise then by such as they call Seminal Agents, or may belong to bodies of a compounded Nature, may be shewn, among other Instances, in Glass made of ashes, where the exceeding strongly-tasted _Alcalizate_ Salt joyning with the Earth becomes insipid, and with it constitutes a Body, which though also dry, fixt, and indissoluble in Water, is yet manifestly a mixt Body; and made so by the Fire itself. And I remmember to our present purpose, that _Helmont_,[15] amongst other Medicines that he commends, has a short processe, wherein, though the Directions for Practice are but obscurely intimated; yet I have some reason not to Dis-believe the Process, without affirming or denying any thing about the vertues of the remedy to be made by it. _Quando_ (sayes he) _oleum cinnamomi &c. suo sali alkali miscetur absque omni aqua, trium mensium artificiosa occultaque circulatione, totum in salem volatilem commutatum est, vere essentiam sui simplicis in nobis exprimit, & usque in prima nostri constitutivasese ingerit._ A not unlike Processe he delivers in another place; from whence, if we suppose him to say true, I may argue, that since by the Fire there may be produc'd a substance that is as well Saline and volatile as the Salt of Harts-horn, blood, &c. which pass for Elementary; and since that this Volatile Salt is really compounded of a Chymical Oyle and a fixt Salt, the one made Volatile by the other, and both associated by the fire, it may well be suspected that other Substances, emerging upon the Dissipation of Bodies by the Fire, may be new sorts of Mixts, and consist of Substances of differing natures; and particularly, I have sometimes suspected, that since the Volatile Salts of Blood, Harts-horn, &c. are figitive [Errata: fugitive] and endow'd with an exceeding strong smell, either that Chymists do Erroneously ascribe all odours to sulphurs, or that such Salts consist of some oyly parts well incorporated with the Saline ones. And the like conjecture I have also made concerning Spirit of Vinager, which, though the Chymists think one of the Principles of that Body, and though being an Acid Spirit it seems to be much less of kin then Volatile Salts to sulphurs; yet, not to mention its piercing smell; which I know not with what congruity the Chymist will deduce from Salt, I wonder they have not taken notice of what their own _Tyrocinium Chymicum_ teach us concerning the Destillation of _Saccharum Saturni_; out of which _Beguinus_[16] assures Us, that he distill'd, besides a very fine spirit, no lesse then two Oyles, the one blood-red and ponderous, but the other swimming upon the top of the Spirit, and of a yellow colour; of which he sayes that he kept then some by him, to verify what he delivers. And though I remember not that I have had two distinct Oyles from Sugar of Lead, yet that it will though distill'd without addition yield some Oyle, disagrees not with my Experience. I know the Chymists will be apt to pretend, that these Oyls are but the volatiliz'd sulphur of the lead; and will perhaps argue it from what _Beguinus_ relates, that when the Distillation is ended, you'l find a _Caput Mortuum_ extreamly black, and (as he speaks) _nullius momenti_, as if the Body, or at least the chief part of the Metal it self were by the distillation carried over the Helme. But since you know as well as I that _Saccharum Saturni_ is a kind of Magistery, made only by calcining of Lead _per se_, dissolving it in distill'd Vinager, and crystalizing the solution; if I had leasure to tell You how Differing a thing I did upon examination find the _Caput Mortuum_, so sleighted by _Beguinus_, to be from what he represents it, I believe you would think the conjecture propos'd less probable then one or other of these three; either that this Oyle did formerly concur to constitute the Spirit of Vinager, and so that what passes for a Chymical Principle may yet be further resoluble into distinct substances; or that some parts of the Spirit together with some parts of the Lead may constitute a Chymical Oyle, which therefore though it pass for Homogeneous, may be a very compounded Body: or at least that by the action of the Distill'd Vinager and the Saturnine Calx one upon another, part of the Liquor may be so alter'd as to be transmuted from an Acid Spirit into an Oyle. And though the truth of either of the two former conjectures would make the example I have reflected on more pertinent to my present argument; yet you'l easily discern, the Third and last Conjecture cannot be unserviceable to confirm some other passages of my discourse. [Footnote 15: Helmont pag. 412.] [Footnote 16: Tyroc. Chym. L. 1. C. 4.] To return then to what I was saying just before I mention'd _Helmont's_ Experiment, I shall subjoyne, That Chymists must confess also that in the perfectly Dephlegm'd spirit of Wine, or other Fermented Liquors, that which they call the Sulphur of the Concrete loses, by the Fermentation, the Property of Oyle, (which the Chymists likewise take to be the true Sulphur of the Mixt) of being unminglable with the Water. And if You will credit _Helmont_,[17] all [Errata: a pound] of the purest Spirit of Wine may barely by the help of pure Salt of Tartar (which is but the fixed Salt of Wine) be resolv'd or Transmuted into scarce half an ounce of Salt, and as much Elementary Water as amounts to the remaining part of the mention'd weight. And it may (as I think I formerly also noted) be doubted, whether that Fixt and Alcalizate Salt, which is so unanimously agreed on to be the Saline Principle of incinerated Bodies, be not, as 'tis Alcalizate, a Production of the Fire? For though the tast of Tartar, for Example, seem to argue that it contains a Salt before it be burn'd, yet that Salt being very Acid is of a quite Differing Tast from the Lixiviate Salt of Calcin'd Tartar. And though it be not truly Objected against the Chymists, that they obtain all Salts they make, by reducing the Body they work on into Ashes with Violent Fires, (since Hartshorn, Amber, Blood, and divers other Mixts yield a copious Salt before they be burn'd to Ashes) yet this Volatile Salt Differs much, as we shall see anon, from the Fixt Alcalizate Salt I speak of; which for ought I remember is not producible by any known Way, without Incineration. 'Tis not unknown to Chymists, that Quicksilver may be Precipitated, without Addition, into a dry Powder, that remains so in Water. And some eminent _Spagyrists_, and even _Raimund Lully_ himself, teach, that meerly by the Fire Quicksilver may in convenient Vessels be reduc'd (at least in great part) into a thin Liquor like Water, and minglable with it. So that by the bare Action of the Fire, 'tis possible, that the parts of a mixt Body should be so dispos'd after new and differing manners, that it may be sometimes of one consistence, sometimes of another; And may in one State be dispos'd to be mingl'd with Water, and in another not. I could also shew you, that Bodies from which apart Chymists cannot obtain any thing that is Combustible, may by being associated together, and by the help of the Fire, afford an inflamable Substance. And that on the other side, 'tis possible for a Body to be inflamable, from which it would very much puzzle any ordinary Chymist; and perhaps any other, to separate an inflamable Principle or Ingredient. Wherefore, since the Principles of Chymists may receive their Denominations from Qualities, which it often exceeds not the power of Art, nor alwayes that of the Fire to produce; And since such Qualities may be found in Bodies that differ so much in other Qualities from one another, that they need not be allow'd to agree in that pure and simple Nature, which Principles, to be so indeed, must have; it may justly be suspected, that many Productions of the Fire that are shew'd us by Chymists, as the Principles of the Concrete that afforded them, may be but a new kind of Mixts. And to annex, on this Occasion, to these arguments taken from the Nature of the thing, one of those which _Logicians_ call _ad Hominem_, I shall desire You to take Notice, that though _Paracelsus_ Himself, and some that are so mistaken as to think he could not be so, have ventur'd to teach, that not only the bodies here below, but the Elements themselves, and all the other Parts of the Universe, are compos'd of Salt, Sulphur and Mercury; yet the learned _Sennertus_, and all the more wary Chymists, have rejected that conceit, and do many of them confess, that the _Tria Prima_ are each of them made up of the four Elements; and others of them make Earth and Water concur with Salt, Sulphur and Mercury, to the Constitution of Mixt bodies. So that one sort of these _Spagyrists_, notwithstanding the specious Titles they give to the productions of the Fire, do in effect grant what I contend for. And, of the other sort I may well demand, to what Kind of Bodies the Phlegme and dead Earth, to be met with in Chymical Resolutions, are to be referr'd? For either they must say, with _Paracelsus_, but against their own Concessions as well as against Experience, that these are also compos'd of the _Tria Prima_, whereof they cannot separate any one from either of them; or else they must confess that two of the vastest Bodies here below, Earth, and Water, are neither of them compos'd of the _Tria Prima_; and that consequently those three are not the Universal, and Adequate Ingredients, neither of all Sublunary Bodies, nor even of all mixt Bodies. [Footnote 17: _Ostendi alias, quomodo lib. una aquæ vitæ combibita in sale Tartari siccato, vix fiat semuncia salis, cæterum totum corpus fiat aqua Elementalis. Helmont. in Aura vitali._] I know that the chief of these Chymists represent, that though the Distinct Substances into which they divide mixt bodies by the Fire, are not pure and Homogeneous; yet since the four Elements into which the _Aristotelians_ pretend to resolve the like bodies by the same Agent, are not simple neither, as themselves acknowledge, 'tis as allowable for the Chymists to call the one Principles, as for the Peripateticks to call the other Elements; since in both cases the Imposition of the name is grounded only upon the Predominancy of that Element whose name is ascrib'd to it. Nor shall I deny, that this Argument of the Chymists is no ill one against the _Aristotelians_. But what Answer can it prove to me, who you know am disputing against the _Aristotelian_ Elements, as the Chymicall Principles, and must not look upon any body as a true Principle or Element, but as yet compounded, which is not perfectly Homogeneous, but is further Resoluble into any number of Distinct Substances how small soever. And as for the Chymists calling a body Salt, or Sulphur, or Mercury, upon pretence that the Principle of the same name is predominant in it, That it self is an Acknowledgment of what I contend for; namely that these productions of the Fire, are yet compounded bodies. And yet whilst this is granted, it is affirm'd, but not prov'd, that the reputed Salt, or Sulphur, or Mercury, consists mainly of one body that deserves the name of a principle of the same Denomination. For how do Chymists make it appear that there are any such primitive and simple bodies in those we are speaking of; since 'tis upon the matter confess'd by the answer lately made, that these are not such? And if they pretend by Reason to evince what they affirm, what becomes of their confident boasts, that the Chymists [Errata: Chymist] (whom they therefore, after _Beguinus_, call a _Philosophus_ or _Opifex Sensatus_) can convince our Eyes, by manifestly shewing in any mixt body those simple substances he teaches them to be compos'd of? And indeed, for the Chymists to have recourse in this case to other proofs then Experiments, as it is to wave the grand Argument that has all this while been given out for a Demonstrative One; so it releases me from the obligation to prosecute a Dispute wherein I am not engag'd to Examine any but Experimentall proofs. I know it may plausibly Enough be Represented, in favour of the Chymists, that it being evident that much the greater part of any thing they call Salt, or Sulphur, or Mercury, is really such; it would be very rigid to deny those Substances the names ascribed them, only because of some sleight mixture of another Body; since not only the Peripateticks call particular parcels of matter Elementary, though they acknowledge that Elements are not to be anywhere found pure, at least here below; And since especially there is a manifest Analogie and Resemblance betwixt the bodies obtainable by Chymical Anatomies and the principles whose names are given them; I have, I say, consider'd that these things may be represented: But as for what is drawn from the Custome of the Peripateticks, I have already told You, that though it may be employ'd against Them, Yet it is not available against me who allow nothing to be an Element that is not perfectly Homogeneous. And whereas it is alledg'd, that the Predominant Principle ought to give a name to the substance wherein it abounds; I answer, that that might much more reasonably be said, if either we or the Chymists had seen Nature take pure Salt, pure Sulphur, and pure Mercury, and compound of them every sort of Mixt Bodies. But, since 'tis to experience that they appeal, we must not take it for granted, that the Distill'd Oyle (for instance) of a plant is mainly compos'd of the pure principle call'd Sulphur, till they have given us an ocular proof, that there is in that sort of Plants such an Homogeneous Sulphur. For as for the specious argument, which is drawn from the Resemblance betwixt the Productions of the Fire, and the Respective, either _Aristotelian_ Elements, or _Chymical_ Principles, by whose names they are call'd; it will appear more plausible then cogent, if You will but recall to mind the state of the controversie; which is not, whether or no there be obtain'd from mixt Bodies certain substances that agree in outward appearance, or in some Qualities with Quicksilver or Brimstone, or some such obvious or copious Body; But whether or no all Bodies confess'd to be perfectly mixt were compos'd of, and are resoluble into a determinate number of primary unmixt Bodies. For, if you keep the state of the question in your Eye, you'l easily discerne that there is much of what should be Demonstrated, left unprov'd by those Chymical Experiments we are Examining. But (not to repeat what I have already discover'd more at large) I shall now take notice, that it will not presently follow, that because a Production of the Fire has some affinity with some of the greater Masses of matter here below, that therefore they are both of the same Nature, and deserve the same Name; for the Chymists are not content, that flame should be look't upon as a parcel of the Element of Fire, though it be hot, dry, and active, because it wants some other Qualities belonging to the nature of Elementary fire. Nor will they let the Peripateticks call Ashes, or Quicklime, Earth, notwithstanding the many likenesses between them; because they are not tastlesse, as Elementary Earth ought to be: But if you should ask me, what then it is, that all the Chymical Anatomies of Bodies do prove, if they prove not that they consist of the three Principles into which the fire resolves them? I answer, that their Dissections may be granted to prove, that some mixt bodies (for in many it will not hold) are by the fire, when they are included in close Vessels, (for that Condition also is often requisite) dissolube [Transcriber's Note: dissoluble] into several Substances differing in some Qualities, but principally in Consistence. So that out of most of them may be obtain'd a fixt substance partly saline, and partly insipid, an unctuous Liquor, and another Liquor or more that without being unctuous have a manifest taste. Now if Chymists will agree to call the dry and sapid substance salt, the Unctous liquor Sulphur, and the other Mercury, I shall not much quarrel with them for so doing: But if they will tell me that Salt, Sulphur, and Mercury, are simple and primary bodies whereof each mixt body was actually compounded, and which was really in it antecedently to the operation of the fire, they must give me leave to doubt whether (whatever their other arguments may do) their Experiments prove all this. And if they will also tell me that the Substances their Anatomies are wont to afford them, are pure and similar, as Principles ought to be, they must give me leave to believe my own senses; and their own confessions, before their bare Assertions. And that you may not (_Eleutherius_) think I deal so rigidly with them, because I scruple to Take these Productions of the Fire for such as the Chymists would have them pass for, upon the account of their having some affinity with them; consider a little with me, that in regard an Element or Principle ought to be perfectly Similar and Homogeneous, there is no just cause why I should rather give the body propos'd the Name of this or that Element or Principle, because it has a resemblance to it in some obvious Quality, rather then deny it that name upon the account of divers other Qualities, wherein the propos'd Bodies are unlike; and if you do but consider what sleight and easily producible qualities they are that suffice, as I have already more then once observ'd, to Denominate a Chymical Principle or an Element, you'l not, I hope, think my wariness to be destitute either of Example, or else of Reason. For we see that the Chymists will not allow the _Aristotelians_ that the Salt in Ashes ought to be called Earth, though the Saline and Terrestrial part symbolize in weight, in dryness, in fixness and fusibility, only because the one is sapid and dissoluble in Water, and the other not: Besides, we see that sapidness and volatility are wont to denominate the Chymists Mercury or Spirit; and yet how many Bodies, think you, may agree in those Qualities which may yet be of very differing natures, and disagree in qualities either more numerous, or more considerable, or both. For not only Spirit of Nitre, Aqua Fortis, Spirit of Salt, Spirit of Oyle of Vitriol, Spirit of Allome, Spirit of Vinager, and all Saline Liquors Distill'd from Animal Bodies, but all the Acetous Spirits of Woods freed from their Vinager; All these, I say, and many others must belong to the Chymists Mercury, though it appear not why some of them should more be comprehended under one denomination then the Chymists Sulphur, or Oyle should likewise be; for their Distill'd Oyles are also Fluid, Volatile, and Tastable, as well as their Mercury; Nor is it Necessary, that their Sulphur should be Unctuous or Dissoluble in Water, since they generally referr Spirit of Wine to Sulphurs, although that Spirit be not Unctuous, and will freely mingle with Water. So that bare Inflamability must constitute the Essence of the Chymists Sulphur; as uninflamablenesse joyned with any taste is enough to intitle a Distill'd Liquor to be their Mercury. Now since I can further observe to You, that Spirit of Nitre and Spirit of Harts-horne being pour'd together will boile and hisse and tosse up one another into the air, which the Chymists make signes of great Antipathy in the Natures of Bodies (as indeed these Spirits differ much both in Taste, Smell, and Operations;) Since I elsewhere tell you of my having made two sorts of Oyle out of the same mans blood, that would not mingle with one another; And since I might tell You Divers Examples I have met with, of the Contrariety of Bodies which according to the Chymists must be huddl'd up together under one Denomination; I leave you to Judge whether such a multitude of Substances as may agree in these sleight Qualities, and yet Disagree in Others more Considerable, are more worthy to be call'd by the Name of a Principle (which ought to be pure and homogeneous,) than to have appellations given them that may make them differ, in name too, from the bodies from which they so wildly differ in Nature. And hence also, by the bye, you may perceive that 'tis not unreasonable to distrust the Chymists way of Argumentation, when being unable to shew us that such a Liquor is (for Example) purely saline, they prove, that at least salt is much the predominant principle, because that the propos'd substance is strongly tasted, and all Tast proceeds from salt; whereas those Spirits, such as spirit of Tartar, spirit of Harts-horn, and the like, which are reckoned to be the Mercuries of the Bodies that afford them, have manifestly a strong and piercing tast, and so has (according to what I formerly noted) the spirit of Box &c. even after the acid Liquor that concurr'd to compose it has been separated from it. And indeed, if sapidness belong not to the spirit or Mercurial Principle of Vegitables and Animals: I scarce know how it will be discriminated from their phlegm, since by the absence of Inflamability it must be distinguish'd from their sulphur, which affords me another Example, to prove how unacurate the Chymical Doctrine is in our present Case; since not only the spirits of Vegitables and Animals, but their Oyles are very strongly tasted, as he that shall but wet his tongue with Chymical Oyle of Cinnamon, or of Cloves, or even of Turpentine, may quickly find, to his smart. And not only I never try'd any Chymical Oyles whose tast was not very manifest and strong; but a skilful and inquisitive person who made it his business by elaborate operations to depurate Chymical Oyles, and reduce them to an Elementary simplicity, Informes us, that he never was able to make them at all Tastless; whence I might inferr, that the proof Chymists confidently give us of a bodies being saline, is so far from demonstrating the Predominancy, that it does not clearly Evince so much as the presence of the saline Principle in it. But I will not (pursues _Carneades_) remind you, that the Volatile salt of Harts-horn, Amber, Blood, &c. are exceeding strongly scented, notwithstanding that most Chymists deduce Odours from Sulphur, and from them argue the Predominancy of that Principle in the Odorous body, because I must not so much as add any new Examples of the incompetency of this sort of Chymical arguments; since having already detain'd You but too long in those generals that appertain to my fourth consideration, 'tis time that I proceed to the particulars themselves, to which I thought fit they should be previous: These Generals (continues _Carneades_) being thus premis'd, we might the better survey the Unlikeness that an attentive and unprepossess'd observer may take notice of in each sort of Bodies which the Chymists are wont to call the salts or sulphurs or Mercuries of the Concretes that yield Them, as if they had all a simplicity, and Identity of Nature: whereas salts if they were all Elementary would as little differ as do the Drops of pure and simple Water. 'Tis known that both Chymists and Physitians ascribe to the fixt salts of calcin'd Bodies the vertues of their concretes; and consequently very differing Operations. So we find the _Alkali_ of Wormwood much commended in distempers of the stomach; that of Eyebright for those that have a weak sight; and that of _Guaiacum_ (of which a great Quantity yields but a very little salt) is not only much commended in Venereal Diseases, but is believed to have a peculiar purgative vertue, which yet I have not had occasion to try. And though, I confess, I have long thought, that these _Alkalizate_ salts are, for the most part, very neer of kin, and retain very little of the properties of the Concretes whence they were separated; Yet being minded to Observe watchfully whether I could meet with any Exceptions to this General Observation, I observ'd at the Glasse-house, that sometimes the Metal (as the Workmen call it) or Masse of colliquated Ingredients, which by Blowing they fashion into Vessels of divers shapes, did sometimes prove of a very differing colour, and a somewhat differing Texture, from what was usuall. And having enquired whether the cause of such Accidents might not be derived from the peculiar Nature of the fixt salt employ'd to bring the sand to fusion, I found that the knowingst Workmen imputed these Mis-adventures to the Ashes, of [Errata: Ashes off] some certain kind of Wood, as having observ'd the ignobler kind of Glass I lately mention'd to be frequently produc'd when they had employ'd such sorts of Ashes which therefore they scruple to make use of, if they took notice of them beforehand. I remember also, that an Industrious Man of my acquaintance having bought a vast quantity of Tobacco stalks to make a fixt Salt with, I had the Curiosity to go see whether that Exotick Plant, which so much abounds in volatile salt, would afford a peculiar kind of _Alcali_; and I was pleas'd to find that in the _Lixivium_ of it, it was not necessary, as is usual, to evaporate all the Liquor, that there might be obtain'd a Saline Calx, consisting like lime quench'd in the Air of a heap of little Corpuscles of unregarded shapes; but the fixt salt shot into figur'd Crystal, almost as Nitre or _Sal-armoniack_ and other uncalcin'd salts are wont to do; And I further remember that I have observ'd in the fixt Salt of Urine, brought by depuration to be very white, a tast not so unlike to that of common salt, and very differing from the wonted caustick Lixiviate tast of other salts made by Incineration. But because the Instances I have alledg'd of the Difference of _Alcalizate_ salt are but few, and therefore I am still inclin'd to think, that most Chymists and many Physitians do, inconsideratly enough and without Warrant from Experience, ascribe the Vertues of the Concretes expos'd to Calcination, to the salts obtain'd by it; I shall rather, to shew the Disparity of salts, mention in the first Place the apparent Difference betwixt the Vegetable fixt salts and the Animal Volatile ones: As (for Example) betwixt salt of Tartar, and salt of Harts-horn; whereof the former is so fixt that 'twill indure the brunt of a violent Fire, and stand in fusion like a Metal; whereas the other (besides that it has a differing tast and a very differing smell) is so far from being fixt, that it will fly away in a gentle heat as easily as Spirit of Wine it self. And to this I shall add, in the next place, That even among the Volatile salts themselves, there is a considerable Difference, as appears by the distinct Properties of (for Instance) salt of Amber, salt of Urine, salt of Mans Skull, (so much extoll'd against the falling Sicknesse) and divers others which cannot escape an ordinary Observer. And this Diversity of Volatile salts I have observ'd to be somtimes Discernable even to the Eye, in their Figures. For the salt of Harts-horn I have observ'd to adhere to the Receiver in the forme almost of a _Parallelipipedon_; and of the Volatile salt of humane blood (long digested before distillation, with spirit of Wine) I can shew you store of graines of that Figure which _Geometricians_ call a _Rhombus_; though I dare not undertake that the Figures of these or other Saline Crystals (if I may so call Them) will be alwaies the same, whatever degree of Fire have been employ'd to force them up, or how hastily soever they have been made to convene in the spirits or liquors, in the lower part of which I have usually observ'd them after a while to shoot. And although, as I lately told You, I seldom found any Difference, as to Medical Vertues, in the fixt Salts of Divers Vegetables; and accordingly I have suspected that most of these volatile Salts, having so great a Resemblance in smell, in tast, and fugitiveness, differ but little, if at all, in their Medicinal properties: As indeed I have found them generally to agree in divers of them (as in their being somewhat Diaphoretick and very Deopilative; [Errata: Deopilative)] Yet I remember _Helmont_[18] somewhere informes us, that there is this Difference betwixt the saline spirit of Urine and that of Mans blood, that the former will not cure the Epilepsy, but the Latter will. Of the Efficacy also of the Salt of Common Amber against the same Disease in Children, (for in Grown Persons it is not a specifick) I may elsewhere have an Occasion to Entertain You. And when I consider that to the obtaining of these Volatile Salts (especially that of Urine) there is not requisite such a Destructive Violence of the Fire, as there is to get those Salts that must be made by Incineration, I am the more invited to conclude, that they may differ from one another, and consequently recede from an Elementary Simplicity. And, if I could here shew You what Mr. _Boyle_ has Observ'd, touching the Various Chymicall Distinctions of Salts; You would quickly discern, not only that Chymists do give themselves a strange Liberty to call Concretes Salts, that are according to their own Rules to be look'd upon as very Compounded Bodies; but that among those very Salts that seem Elementary, because produc'd upon the Anatomy of the Bodies that yield them, there is not only a visible Disparity, but, to speak in the common Language, a manifest Antipathy or Contrariety: As is evident in the Ebullition and hissing that is wont to ensue, when the Acid Spirit of Vitrioll, for Instance, is pour'd upon pot ashes, or Salt of Tartar. And I shall beg leave of this Gentleman, sayes _Carneades_, casting his Eyes on me, to let me observe to You out of some of his papers, particularly those wherein he treats of some Preparations of Urine, that not only one and the same body may have two Salts of a contrary Nature, as he exemplifies in the Spirit and _Alkali_ of Nitre; but that from the same body there may without addition be obtain'd three differing and Visible Salts. For He Relates, that he observ'd in Urine, not only a Volatile and Crystalline Salt, and a fixt Salt, but likewise a kind of _Sal Armoniack_, or such a Salt as would sublime in the form of a salt, and therefore was not fixt, and yet was far from being so fugitive as the Volatile salt; from which it seem'd also otherwise to differ. I have indeed suspected that this may be a _Sal Armoniack_ properly enough so call'd, as Compounded of the Volatile salt of Urine, and the fixt of the same Liquor, which, as I noted, is not unlike sea-salt; but that it self argues a manifest Difference betwixt the salts, since such a Volatile salt is not wont to Unite thus with an ordinary _Alcali_, but to fly away from it in the Heat. And on this occasion I remember that, to give some of my Friends an Ocular proof of the difference betwixt the fixt and Volatile salt (of the same Concrete) Wood, I devis'd the following Experiment. I took common Venetian sublimate, and dissolv'd as much of it as I well could in fair Water: then I took Wood Ashes, and pouring on them Warme Water, Dissolv'd their salt; and filtrating the Water, as soon as I found the _Lixivium_ sufficiently sharp upon the tongue, I reserv'd it for use: Then on part of the former solution of sublimate dropping a little of this Dissolv'd Fixt salt of Wood, the Liquors presently turn'd of an Orange Colour; but upon the other part of the clear solution of sublimate putting some of the Volatile salt of Wood (which abounds in the spirit of soot) the Liquor immediately turn'd white, almost like Milke, and after a while let fall a white sediment, as the other Liquor did a Yellow one. To all this that I have said concerning the Difference of salts, I might add what I Formerly told you, concerning the simple spirit of Box, and such like Woods, which differ much from the other salts hitherto mention'd, and yet would belong to the saline Principle, if Chymists did truly teach that all Tasts proceed from it. And I might also annex, what I noted to you out of _Helmont_[19] concerning Bodies, which, though they consist in great part of Chymical Oyles, do yet appear but Volatile salts; But to insist on these things, were to repeat; and therefore I shall proceed. [Footnote 18: _Error vero per distillationem nobis monstrat etiam Spiritum salinum plane volatilem odore nequicquam ut nec gustu distinguibilem a spiritu Urinæ; In eo tamen essentialiter diversum, quod spiritus talis cruoris curat Epilepsiam, non autem Spiritus salis lotii._ Helmont. Aura Vitalis.] [Footnote 19: _Aliquando oleum Cinnamomi, &c. suo sali Alcali miscetur absque omni aqua, trium mensium Artificiosa occultaque circulatione, totum in salem volatilem commutatum est. Helmont. Tria Prima Chymicorum, &c. pag. 412._] This Disparity is also highly eminent in the separated sulphurs or Chymical Oyles of things. For they contain so much of the scent, and tast, and vertues, of the Bodies whence they were drawn, that they seem to be but the Material _Crasis_ (if I may so speak) of their Concretes. Thus the Oyles of Cinnamon, Cloves, Nutmegs and other spices, seem to be but the United Aromatick parts that did ennoble those Bodies. And 'tis a known thing, that Oyl of Cinnamon, and oyle of Cloves, (which I have likewise observ'd in the Oyles of several Woods) will sink to the Bottom of Water: whereas those of Nutmegs and divers other Vegetables will swim upon it. The Oyle (abusively call'd spirit) of Roses swims at the Top of the Water in the forme of a white butter, which I remember not to have observ'd in any other Oyle drawn in any Limbeck; yet there is a way (not here to be declar'd) by which I have seen it come over in the forme of other Aromatick Oyles, to the Delight and Wonder of those that beheld it. In Oyle of Anniseeds, which I drew both with, and without Fermentation, I observ'd the whole Body of the Oyle in a coole place to thicken into the Consistence and Appearance of white Butter, which with the least heat resum'd its Former Liquidness. In the Oyl of Olive drawn over in a Retort, I have likewise more then once seen a spontaneous Coagulation in the Receiver: And I have of it by me thus Congeal'd; which is of such a strangely Penetrating scent, as if 'twould Perforate the Noses that approach it. The like pungent Odour I also observ'd in the Distill'd Liquor of common sope, which forc'd over from _Minium_, lately afforded an oyle of a most admirable Penetrancy; And he must be a great stranger, both to the Writings and preparations of Chymists, that sees not in the Oyles they distill from Vegetables and Animals, a considerable and obvious Difference. Nay I shall venture to add, _Eleutherius_, (what perhaps you will think of kin to a Paradox) that divers times out of the same Animal or Vegetable, there may be extracted Oyles of Natures obviously differing. To which purpose I shall not insist on the swimming and sinking Oyles, which I have sometimes observ'd to float on, and subside under the spirit of _Guajacum_, and that of divers other Vegetables Distill'd with a strong and lasting Fire; Nor shall I insist on the observation elsewhere mention'd, of the divers and unminglable oyles afforded us by Humane Blood long fermented and Digested with spirit of Wine, because these kind of oyles may seem chiefly to differ in Consistence and Weight, being all of them high colour'd and adust. But the Experiment which I devis'd to make out this Difference of the oyles of the same Vegetable, _ad Oculum_, (as they speak) was this that followes. I took a pound of Annisseeds, and having grosly beaten them, caused them to be put into a very large glass Retort almost filled with fair Water; and placing this Retort in a sand Furnace, I caus'd a very Gentle heat to be administer'd during the first day, and a great part of the second, till the Water was for the most part drawn off, and had brought over with it at least most of the Volatile and Aromatick Oyle of the seeds. And then encreasing the Fire, and changing the Receiver, I obtain'd besides an Empyreumatical Spirit, a quantity of adust oyle; whereof a little floated upon the Spirit, and the rest was more heavy, and not easily separable from it. And whereas these oyles were very dark, and smell'd (as Chymists speak) so strongly of the Fire, that their Odour did not betray from what Vegetables they had been forc'd; the other _Aromatick_ Oyle was enrich'd with the genuine smell and tast of the Concrete; and spontaneously coagulating it self into white butter did manifest self [Errata: it self] to be the true Oyle of Annisseeds; which Concrete I therefore chose to employ about this Experiment, that the Difference of these Oyles might be more conspicuous then it would have been, had I instead of it destill'd another Vegetable. I had almost forgot to take notice, that there is another sort of Bodies, which though not obtain'd from Concretes by Distillation, many Chymists are wont to call their Sulphur; not only because such substances are, for the most part, high colour'd (whence they are also, and that more properly, called Tinctures) as dissolv'd Sulphurs are wont to be; but especially because they are, for the most part, abstracted and separated from the rest of the Masse by Spirit of Wine: which Liquor those men supposing to be Sulphureous, they conclude, that what it works upon, and abstracts, must be a Sulphur also. And upon this account they presume, that they can sequester the sulphur even of Minerals and Metalls; from which 'tis known that they cannot by Fire alone separate it. To all This I shall answer; That if these sequestred substances where indeed the sulphurs of the Bodies whence they are drawn, there would as well be a great Disparity betwixt Chymical Sulphurs obtain'd by Spirit of Wine, as I have already shewn there is betwixt those obtain'd by Distillation in the forme of Oyles: which will be evident from hence, that not to urge that themselves ascribe distinct vertues to Mineral Tinctures, extolling the Tincture of Gold against such and such Diseases; the Tincture of Antimony, or of its Glass, against others; and the Tincture of Emerauld against others; 'tis plain, that in Tinctures drawn from Vegetables, if the superfluous spirit of Wine be distill'd off, it leaves at the bottom that thicker substance which Chymists use to call the Extract of the Vegetable. And that these Extracts are endow'd with very differing Qualities according to the Nature of the Particular Bodies that afforded them (though I fear seldom with so much of the specifick vertues as is wont to be imagin'd) is freely confess'd both by Physitians and Chymists. But, _Eleutherius_, (sayes _Carneades_) we may here take Notice that the Chymists do as well in this case, as in many others, allow themselves a License to abuse Words: For not again to argue from the differing properties of Tinctures, that they are not exactly pure and Elementary Sulphurs; they would easily appear not to be so much as Sulphur's, although we should allow Chymical Oyles to deserve that Name. For however in some Mineral Tinctures the Natural fixtness of the extracted Body does not alwayes suffer it to be easily further resoluble into differing substances; Yet in very many extracts drawn from Vegetables, it may very easily be manifested that the spirit of Wine has not sequestred the sulphureous Ingredient from the saline and Mercurial ones; but has dissolv'd (for I take it to be a Solution) the finer Parts of the Concrete (without making any nice distinction of their being perfectly Sulphureous or not) and united it self with them into a kind of Magistery; which consequently must contain Ingredients or Parts of several sorts. For we see that the stones that are rich in vitriol, being often drench'd with rain-Water, the Liquor will then extract a fine and transparent substance coagulable into Vitriol; and yet though this Vitriol be readily dissoluble in Water, it is not a true Elementary Salt, but, as You know, a body resoluble into very differing Parts, whereof one (as I shall have occasion to tell You anon) is yet of a Metalline, and consequently not of an Elementary Nature. You may consider also, that common Sulphur is readily dissoluble in Oyle of Turpentine, though notwithstanding its Name it abounds as well, if not as much, in Salt as in true Sulphur; witness the great quantity of saline Liquor it affords being set to flame away under a glasse Bell. Nay I have, which perhaps You will think strange, with the same Oyle of Turpentine alone easily enough dissolv'd crude Antimony finely powder'd into a Blood-red Balsam, wherewith perhaps considerable things may be perform'd in Surgery. And if it were now Requisite, I could tell You of some other Bodies (such as Perhaps You would not suspect) that I have been able to work upon with certain Chymical Oyles. But instead of digressing further I shall make this use of the Example I have nam'd. That 'tis not unlikely, but that Spirit of Wine which by its pungent tast, and by some other Qualities that argue it better (especially its Reduciblenesse, according to _Helmont_, into _Alcali_, and Water,) seems to be as well of a Saline as of a Sulphureous Nature, may well be suppos'd Capable of Dissolving Substances That are not meerly Elementary sulphurs, though perhaps they may abound with Parts that are of kin thereunto. For I find that Spirit of Wine will dissolve _Gumm Lacca_, _Benzoine_, and the _Resinous_ Parts of _Jallap_, and even of _Guaiacum_; whence we may well suspect that it may from Spices, Herbs, and other lesse compacted Vegetables, extract substances that are not perfect Sulphurs but mixt Bodies. And to put it past Dispute, there is many a Vulgar Extract drawn with Spirit of Wine, which committed to Distillation will afford such differing substances as will Loudly proclaim it to have been a very compounded Body. So that we may justly suspect, that even in Mineral Tinctures it will not alwaies follow, that because a red substance is drawn from the Concrete by spirit of Wine, that Substance is its true and Elementary Sulphur. And though some of these Extracts may perhaps be inflamable; Yet besides that others are not, and besides that their being reduc'd to such Minuteness of Parts may much facilitate their taking Fire; besides this, I say, We see that common Sulphur, common Oyle, Gumm Lac, and many Unctuous and Resinous Bodies, will flame well enough, though they be of very compounded natures: Nay Travellers of Unsuspected Credit assure Us, as a known thing, that in some Northern Countries where Firr trees and Pines abound, the poorer sort of Inhabitants use Long splinters of those Resinous Woods to burne instead of Candles. And as for the rednesse wont to be met with in such solutions, I could easily shew, that 'tis not necessary it should proceed from the Sulphur of the Concrete, Dissolv'd by the Spirit of Wine; if I had leasure to manifest how much Chymists are wont to delude themselves and others by the Ignorance of those other causes upon whose account spirit of Wine and other _Menstruums_ may acquire a red or some other high colour. But to returne to our Chymical Oyles, supposing that they were exactly pure; Yet I hope they would be, as the best spirit of Wine is, but the more inflamable and deflagrable. And therefore since an Oyle can be by the Fire alone immediately turn'd into flame, which is something of a very differing Nature from it: I shall Demand how this Oyle can be a Primogeneal and Incorruptible Body, as most Chymists would have their Principles; Since it is further resoluble into flame, which whether or no it be a portion of the Element of Fire, as an _Aristotelian_ would conclude, is certainly something of a very differing Nature from a Chymical Oyle, since it burnes, and shines, and mounts swiftly upwards; none of which a Chymical Oyle does, whilst it continues such. And if it should be Objected, that the Dissipated Parts of this flaming Oyle may be caught and collected again into Oyl or Sulphur; I shall demand, what Chymist appears to have ever done it; and without Examining whether it may not hence be as well said that sulphur is but compacted Fire, as that Fire is but diffus'd Sulphur, I shall leave you to consider whether it may not hence be argu'd, that neither Fire nor Sulphur are primitive and indestructible Bodies; and I shall further observe that, at least it will hence appear that a portion of matter may without being Compounded with new Ingredients, by having the Texture and Motion of its small parts chang'd, be easily, by the means of the Fire, endow'd with new Qualities, more differing from them it had before, then are those which suffice to discriminate the Chymists Principles from one another. We are next to Consider, whether in the Anatomy of mixt Bodies, that which Chymists call the Mercurial part of them be un-compounded, or no. But to tell You True, though Chymists do Unanimously affirm that their Resolutions discover a Principle, which they call Mercury, yet I find them to give of it Descriptions so Differing, and so Ænigmaticall, that I, who am not asham'd to confess that I cannot understand what is not sence, must acknowledge to you that I know not what to make of them. _Paracelsus_ himself, and therefore, as you will easily believe, many of his Followers, does somewhere call that Mercury which ascends upon the burning of Wood, as the Peripateticks are wont to take the same smoke for Air; and so seems to define Mercury by Volatility, or (if I may coyne such a Word) Effumability. But since, in this Example, both Volatile Salt and Sulphur make part of the smoke, which does indeed consist also both of Phlegmatick and Terrene Corpuscles, this Notion is not to be admitted; And I find that the more sober Chymists themselves disavow it. Yet to shew you how little of clearness we are to expect in the accounts even of latter _Spagyrists_, be pleas'd to take notice, that _Beguinus_, even in his _Tyrocinium Chymicum_,[20] written for the Instruction of Novices, when he comes to tell us what are meant by the _Tria Prima_, which for their being Principles ought to be defin'd the more accurately and plainly, gives us this Description of Mercury; _Mercurius_ (sayes he) _est liquor ille acidus, permeabilis, penetrabilis, æthereus, ac purissimus, a quo omnis Nutricatio, Sensus, Motus, Vires, Colores, Senectutisque Præproperæ retardatio._ Which words are not so much a Definition of it, as an _Encomium_: and yet _Quercetanus_ in his Description of the same Principle adds to these, divers other _Epithets_. But both of them, to skip very many other faults that may be found with their Metaphoricall Descriptions, speak incongruously to the Chymists own Principles. For if Mercury be an Acid Liquor, either Hermetical Philosophy must err in ascribing all Tasts to Salt, or else Mercury must not be a Principle, but Compounded of a Saline Ingredient and somewhat else. _Libavius_, though he find great fault with the obscurity of what the Chymists write concerning their Mercurial Principle, does yet but give us such a Negative Description of it, as _Sennertus_, how favourable soever to the _Tria Prima_, is not satisfi'd with. And this _Sennertus_ Himself, though the Learnedst Champion for the Hypostatical Principles, does almost as frequently as justly complain of the unsatisfactoriness of what the Chymists teach concerning their Mercury; and yet he himself (but with his wonted modesty) Substitutes instead of the Description of _Libavius_, another, which many Readers, especially if they be not Peripateticks, will not know what to make of. For scarce telling us any more, then that in all bodies that which is found besides Salt and Sulphur, and the Elements, or, as they call them, Phlegm and Dead Earth, is that Spirit which in _Aristotles_ Language may be call'd [Greek: ousian analogon [Errata: ousia analogos] tô tôn astrôn stoichaiô [Errata: astrôn stoicheiô]]. He sayes that which I confess is not at all satisfactory to me, who do not love to seem to acquiesce in any mans Mystical Doctrines, that I may be thought to understand them. [Footnote 20: _Chm. Tyrocin. lib. 1. Cap. 2._] If (sayes _Eleutherius_) I durst presume that the same thing would be thought clear by me, and those that are fond of such cloudy Expressions as You justly Tax the Chymists for, I should venture to offer to Consideration, whether or no, since the Mercurial Principle that arises from Distillation is unanimously asserted to be distinct from the salt and Sulphur of the same Concrete, that may not be call'd the Mercury of a Body, which though it ascend in Distillation, as do the Phlegme and Sulphur, is neither insipid like the former, nor inflamable like the latter. And therefore I would substitute to the too much abused Name of Mercury, the more clear and Familiar Appellation of Spirit, which is also now very much made use of even by the Chymists themselves, of our times, though they have not given us so Distinct an Explication, as were fit, of what may be call'd the Spirit of a mixt Body. I should not perhaps (sayes _Carneades_) much quarrel with your Notion of Mercury. But as for the Chymists, what they can mean, with congruity to their own Principles, by the Mercury of Animals and Vegetables, 'twill not be so easie to find out; for they ascribe Tasts only to the Saline Principle, and consequently would be much put to it to shew what Liquor it is, in the Resolution of Bodies, that not being insipid, for that they call Phlegme, neither is inflamable as Oyle or Sulphur, nor has any Tast; which according to them must proceed from a Mixture, at least, of Salt. And if we should take Spirit in the sence of the Word receiv'd among Modern Chymists and Physitians, for any Distill'd Liquor that is neither Phlegme nor oyle, the Appellation would yet appear Ambiguous enough. For, plainly, that which first ascends in the Distillation of Wine and Fermented Liquors, is generally as well by Chymists as others reputed a Spirit. And yet pure Spirit of Wine being wholly inflamable ought according to them to be reckon'd to the Sulphureous, not the Mercurial Principle. And among the other Liquors that go under the name of Spirits, there are divers which seem to belong to the family of Salts, such as are the Spirits of Nitre, Vitriol, Sea-Salt and others, and even the Spirit of Harts-horn, being, as I have try'd, in great part, if not totally reducible into Salt and Phlegme, may be suspected to be but a Volatile Salt disguis'd by the Phlegme mingl'd with it into the forme of a Liquor. However if this be a Spirit, it manifestly differs very much from that of Vinager, the Tast of the one being Acid, and the other Salt, and their Mixture in case they be very pure, sometimes occasioning an Effervescence like that of those Liquors the Chymists count most contrary to one another. And even among those Liquors that seem to have a better title then those hitherto mention'd, to the name of Spirits, there appears a sensible Diversity; For spirit of Oak, for instance, differs from that of Tartar, and this from that of Box, or of _Guaiacum_. And in short, even these spirits as well as other Distill'd Liquors manifest a great Disparity betwixt themselves, either in their Actions on our senses, or in their other operations. And (continues _Carneades_) besides this Disparity that is to be met with among those Liquors that the Modernes call spirits, & take for similar bodies, what I have formerly told you concerning the Spirit of Box-wood may let you see that some of those Liquors not only have qualities very differing from others, but may be further resolved into substances differing from one another. And since many moderne Chymists and other Naturalists are pleased to take the Mercurial spirit of Bodies for the same Principle, under differing names, I must invite you to observe, with me, the great difference that is conspicuous betwixt all the Vegetable and Animal spirits I have mention'd and running Mercury. I speak not of that which is commonly sold in shops that many of themselves will confesse to be a mixt Body; but of that which is separated from Metals, which by some Chymists that seem more Philosophers then the rest, and especially by the above mentioned _Claveus_, is (for distinction sake) called _Mercurius Corporum_. Now this Metalline Liquor being one of those three Principles of which Mineral Bodies are by _Spagyrists_ affirmed to be compos'd and to be resoluble into them, the many notorious Differences betwixt them and the Mercuries, as They call Them, of Vegetables and Animals will allow me to inferr, either that Minerals and the other two sorts of Mixt Bodies consist not of the same Elements, or that those Principles whereinto Minerals are immediately resolved, which Chymists with great ostentation shew us as the true principles, of them, are but Secundary Principles, or Mixts of a peculiar sort, which must be themselves reduc'd to a very differing forme, to be of the same kind with Vegetable and Animal Liquors. But this is not all; for although I formerly told You how Little Credit there is to be given to the Chymical Processes commonly to be met with, of Extracting the Mercuries of Metals, Yet I will now add, that supposing that the more Judicious of Them do not untruly affirme that they have really drawn true and running Mercury from several Metals (which I wish they had cleerly taught Us how to do also,) yet it may be still doubted whether such extracted Mercuries do not as well differ from common Quicksilver, and from one another, as from the Mercuries of Vegetables and Animalls. _Claveus_,[21] in his Apology, speaking of some _experiments_ whereby Metalline Mercuries may be fixt into the nobler metals, adds, that he spake of the Mercuries drawn from metals; because common Quicksilver by reason of its excessive coldnesse and moisture is unfit for that particular kind of operation; for which though a few lines before he prescribes in general the Mercuries of Metalline Bodies, yet he chiefly commends that drawn by art from silver. And elsewhere, in the same Book, he tells us, that he himself tryed, that by bare coction the quicksilver of Tin or Pewter (_argentum vivum ex stanno prolicitum_) may by an efficient cause, as he speaks, be turn'd into pure Gold. And the Experienc'd _Alexander van Suchten_, somewhere tells us, that by a way he intimates may be made a Mercury of Copper, not of the Silver colour of other Mercuries, but green; to which I shall add, that an eminent person, whose name his travells and learned writings have made famous, lately assur'd me that he had more then once seen the Mercury of Lead (which whatever Authors promise, you will find it very difficult to make, at least in any considerable quantity) fixt into perfect Gold. And being by me demanded whether or no any other Mercury would not as well have been changed by the same Operations, he assured me of the Negative. [Footnote 21: _Dixi autem de argento vivo a metallis prolicito, quod vulgare ob nimiam frigiditatem & humiditatem nimium concoctioni est contumax, nec ab auro solum alterato coerceri potest._ Gast. Clave. in Apoll.] And since I am fallen upon the mention of the Mercuries of metals, you will perhaps expect (_Eleutherius_!) that I should say something of their two other principles; but must freely confess to you, that what Disparity there may be between the salts and sulphurs of Metals and other Menerals [Transcriber's Note: Minerals], I am not my self experienced enough in the separations and examens of them, to venture to determine: (for as for the salts of Metals, I formerly represented it as a thing much to be question'd, whether they have any at all:) And for the processes of separation I find in Authors, if they were (what many of them are not) successfully practicable, as I noted above, yet they are to be performed by the assistance of other bodies, so hardly, if upon any termes at all, separable from them, that it is very difficult to give the separated principles all their due, and no more. But the Sulphur of Antimony which is vehemently vomitive, and the strongly scented Anodyne Sulphur of Vitriol inclines me to think that not only Mineral Sulphurs differ from Vegetable ones, but also from one another, retaining much of the nature of their Concretes. The salts of metals, and of some sort of minerals, You will easily guesse by [Errata: (by] the Doubts I formerly express'd, whether metals have any salt at all [Errata: all)], that I have not been so happy as yet to see, perhaps not for want of curiosity. But if _Paracelsus_ did alwaies write so consentaneously to himself that his opinion were _confidently_ to be collected from every place of his writings where he seems to expresse it, I might safely take upon me to tell you, that he both countenances in general what I have delivered in my Fourth main consideration, and in particular warrants me to suspect that there may be a difference in metalline and mineral Salts, as well as we find it in those of other bodies. For, _Sulphur_ (sayes he)[22] _aliud in auro, aliud in argento, aliud in ferro, aliud in plumbo, stanno, &c. sic aliud in Saphiro, aliud in Smaragdo, aliud in rubino, chrysolito, amethisto, magnete, &c. Item aliud in lapidibus, silice, salibus, fontibus, &c. nec vero tot sulphura tantum, sed & totidem salia; sal aliud in metallis, aliud in gemmis, aliud in lapidibus, aliud in salibus, aliud in vitriolo, aliud in alumine: similis etiam Mercurii est ratio. Alius in Metallis, alius in Gemmis, &c. Ita ut unicuique speciei suus peculiaris Mercurius sit. Et tamen res saltem tres sunt; una essentia est sulphur; una est sal; una est Mercurius. Addo quod & specialius adhuc singula dividantur; aurum enim non unum, sed multiplex, ut et non unum pyrum, pomum, sed idem multiplex; totidem etiam sulphura auri, salia auri, mercurii auri; idem competit etiam metallis & gemmis; ut quot saphyri præstantiores, lævioris, &c. tot etiam saphyrica sulphura, saphyrica salia, saphyrici Mercurii, &c. Idem verum etiam est de turconibus & gemmis aliis universis._ From which passage (_Eleutherius_) I suppose you will think I might without rashness conclude, either that my opinion is favoured by that of _Paracelsus_, or that _Paracelsus_ his opinion was not alwaies the same. But because in divers other places of his writings he seems to talk at a differing rate of the three Principles and the four Elements, I shall content my self to inferr from the alledg'd passage, that if his doctrine be not consistent with that Part of mine which it is brought to countenance, it is very difficult to know what his opinion concerning salt, sulphur and mercury, was; and that consequently we had reason about the beginning of our conferences, to decline taking upon us, either to examine or oppose it. [Footnote 22: Paracel. de Mineral. Tract. 1. pag. 141.] I know not whether I should on this occasion add, that those very bodies the Chymists call Phlegme and Earth do yet recede from an Elementary simplicity. That common Earth and Water frequently do so, notwithstanding the received contrary opinion, is not deny'd by the more wary of the moderne Peripateticks themselves: and certainly, most Earths are much lesse simple bodies then is commonly imagined even by Chymists, who do not so consideratly to prescribe and employ Earths Promiscuously in those distillations that require the mixture of some _caput mortuum_, to hinder the flowing together of the matter, and to retain its grosser parts. For I have found some Earths to yield by distillation a Liquor very far from being inodorous or insipid; and 'tis a known observation, that most kinds of fat Earth kept cover'd from the rain, and hindred from spending themselves in the production of vegetables, will in time become impregnated with Salt-Petre. But I must remember that the Water and Earths I ought here to speak of, are such as are separated from mixt Bodies by the fire; and therefore to restrain my Discourse to such, I shall tell you, That we see the Phlegme of Vitriol (for instance) is a very effectual remedie against burnes; and I know a very Famous and experienc'd _Physitian_, whose unsuspected secret (himself confess'd to me) it is, for the discussing of hard and Obstinate Tumours. The Phlegme of Vinager, though drawn exceeding leasurly in a digesting Furnace, I have purposely made tryall of; and sometimes found it able to draw, though slowly, a saccharine sweetness out of Lead; and as I remember by long Digestion, I dissolv'd Corpals [Errata: Corals] in it. The Phlegme of the sugar of Saturne is said to have very peculiar properties. Divers Eminent Chymists teach, that it will dissolve Pearls, which being precipitated by the spirit of the same concrete are thereby (as they say) rendred volatile; which has been confirmed to me, upon his own observation, by a person of great veracity. The Phlegme of Wine, and indeed divers other Liquors that are indiscriminately condemnd to be cast away as phlegm, are endow'd with qualities that make them differ both from meer water, and from each other; and whereas the Chymists are pleas'd to call the _caput mortuum_ of what they have distill'd (after they have by affusion of water drawn away its salt) _terra damnata_, or Earth, it may be doubted whether or no those earths are all of them perfectly alike: and it is scarce to be doubted, but that there are some of them which remain yet unreduc'd to an Elementary nature. The ashes of wood depriv'd of all the salt, and bone-Ashes, or calcin'd Harts-horn, which Refiners choose to make Tests of, as freest from Salt, seem unlike: and he that shall compare either of these insipid ashes to Lime, and much more to the _calx_ of Talk [Transcriber's Note: Talck] (though by the affusion of water they be exquisitely dulcify'd) will perhaps see cause to think them things of a somewhat differing nature. And it is evident in Colcothar that the exactest calcination, follow'd by an exquisite dulcification, does not alwaies reduce the remaining body into elementary earth; for after the salt or Vitriol (if the Calcination have been too faint) is drawn out of the Colcothar, the residue is not earth, but a mixt body, rich in Medical vertues (as experience has inform'd me) and which _Angelus Sala_ affirmes to be partly reducible into malleable Copper; which I judge very probable: for though when I was making Experiments upon Colcothar, I was destitute of a Furnace capable of giving a heat intense Enough to bring such a Calx to Fusion; yet having conjectur'd that if Colcothar abounded with that Metal, Aqua Fortis would find it out there, I put some dulcifi'd Colcothar into that _Menstruum_, and found the Liquor, according to my Expectation, presently Colour'd as Highly as if it had been an Ordinary Solution of Copper. THE SCEPTICAL CHYMIST. _The Fifth Part._ Here _Carneades_ making a pause, I must not deny (sayes his Friend to him) that I think You have sufficiently prov'd that these distinct Substances which Chymists are wont to obtain from Mixt Bodies, by their Vulgar Destillation, are not pure and simple enough to deserve, in Rigour of speaking, the Name of Elements, or Principles. But I suppose You have heard, that there are some Modern _Spagyrists_, who give out that they can by further and more Skilfull Purifications, so reduce the separated Ingredients of Mixt Bodies to an Elementary simplicity, That the Oyles (for Instance) extracted from all Mixts shall as perfectly resemble one another, as the Drops of Water do. If you remember (replies _Carneades_) that at the Beginning of our Conference with _Philoponus_, I declar'd to him before the rest of the Company, that I would not _engage_ my self at present to do any more then examine the usual proofs alledg'd by Chymists, for the Vulgar doctrine of their three Hypostatical Principles; You will easily perceive that I am not oblig'd to make answer to what you newly propos'd; and that it rather grants, then disproves what I have been contending for: Since by pretending to make so great a change in the reputed Principles that Destillation affords the common _Spagyrists_, 'tis plainly enough presuppos'd, that before such Artificial Depurations be made, the Substances to be made more simple were not yet simple enough to be look'd upon as Elementary; Wherefore in case the _Artists_ you speak of could perform what they give out they can, yet I should not need to be asham'd of having question'd the Vulgar Opinion touching the _tria Prima_. And as to the thing it self, I shall freely acknowledge to you, that I love not to be forward in determining things to be impossible, till I know and have consider'd the means by which they are propos'd to be effected. And therefore I shall not peremptorily deny either the possibility of what these _Artists_ promise, or my Assent to any just Inference; however destructive to my Conjectures, that may be drawn from their performances. But give me leave to tell you withall, that because such promises are wont (as Experience has more then once inform'd me) to be much more easily made, then made good by Chymists, I must withhold my Beliefe from their assertions, till their Experiments exact it; and must not be so easie as to expect before hand, an unlikely thing upon no stronger Inducements then are yet given me: Besides that I have not yet found by what I have heard of these Artists, that though they pretend to bring the several Substances into which the Fire has divided the Concrete, to an exquisite simplicity, They pretend also to be able by the Fire to divide all Concretes, Minerals, and others, into the same number of Distinct Substances. And in the mean time I must think it improbable, that they can either truly separate as many differing Bodies from Gold (for Instance) or _Osteocolla_, as we can do from Wine, or Vitriol; or that the Mercury (for Example) of Gold or Saturn would be perfectly of the same Nature with that of Harts-horn; and that the sulphur of Antimony would be but Numerically different from the Distill'd butter or oyle of Roses. But suppose (sayes _Eleutherius_) that you should meet with Chymists, who would allow you to take in Earth and Water into the number of the principles of Mixt Bodies; and being also content to change the Ambiguous Name of Mercury for that more intelligible one of spirit, should consequently make the principles of Compound Bodies to be Five; would you not think it something hard to reject so plausible an Opinion, only because the Five substances into which the Fire divides mixt Bodies are not exactly pure, and Homogeneous? For my part (Continues _Carneades_) I cannot but think it somewhat strange, in case this Opinion be not true, that it should fall out so luckily, that so great a Variety of Bodies should be Analyz'd by the Fire into just five Distinct substances; which so little differing from the Bodies that bear those names, may so Plausibly be call'd Oyle, Spirit, Salt, Water, and Earth. The Opinion You now propose (answers _Carneades_) being another then that I was engag'd to examine, it is not requisite for me to Debate it at present; nor should I have leisure to do it thorowly. Wherefore I shall only tell you in General, that though I think this Opinion in some respects more defensible then that of the Vulgar Chymists; yet you may easily enough learn from the past Discourse what may be thought of it: Since many of the Objections made against the Vulgar Doctrine of the Chymists seem, without much alteration, employable against this _Hypothesis_ also. For, besides that this Doctrine does as well as the other take it for granted, (what is not easie to be prov'd) that the Fire is the true and Adequate Analyzer of Bodies, and that all the Distinct substances obtainable from a mixt Body by the Fire, were so pre-existent in it, that they were but extricated from each other by the _Analysis_; Besides that this Opinion, too, ascribe [Errata: ascribes] to the Productions of the Fire an Elementary simplicity, which I have shewn not to belong to them; and besides that this Doctrine is lyable to some of the other Difficulties, wherewith That of the _Tria Prima_ is incumber'd; Besides all this, I say, this quinary number of Elements, (if you pardon the Expression) ought at least to have been restrain'd to the Generality of Animal and Vegetable Bodies, since not only among these there are some Bodies (as I formerly argu'd) which, for ought has yet been made to appear, do consist, either of fewer or more similar substances then precisely Five. But in the Mineral Kingdom, there is scarce one Concrete that has been evinc'd to be adequatly divisible into such five Principles or Elements, and neither more nor less, as this Opinion would have every mixt Body to consist of. And this very thing (continues _Carneades_) may serve to take away or lessen your Wonder, that just so many Bodies as five should be found upon the Resolution of Concretes. For since we find not that the fire can make any such _Analysis_ (into five Elements) of Metals and other Mineral Bodies, whose Texture is more strong and permanent, it remains that the Five Substances under consideration be Obtain'd from Vegetable and Animal Bodies, which (probably by reason of their looser Contexture) are capable of being Distill'd. And as to such Bodies, 'tis natural enough, that, whether we suppose that there are, or are not, precisely five Elements, there should ordinarily occurr in the Dissipated parts a five Fold Diversity of Scheme (if I may so speak.) For if the Parts do not remain all fix'd, as in Gold, Calcin'd Talck, &c. nor all ascend, as in the Sublimation of Brimstone, Camphire, &c. but after their Dissipation do associate themselves into new Schemes of Matter; it is very likely, that they will by the Fire be divided into fix'd and Volatile (I mean, in Reference to that degree of heat by which they are destill'd) and those Volatile parts will, for the most part, ascend either in a dry forme, which Chymists are pleas'd to call, if they be Tastless, Flowers; if Sapid, Volatile Salt; or in a Liquid Forme. And this Liquor must be either inflamable, and so pass for oyl, or not inflamable, and yet subtile and pungent, which may be call'd Spirit; or else strengthless or insipid, which may be nam'd Phlegme, or Water. And as for the fixt part, or _Caput Mortuum_, it will most commonly consist of Corpuscles, partly Soluble in Water, or Sapid, (especially if the Saline parts were not so Volatile, as to fly away before) which make up its fixt salt; and partly insoluble and insipid, which therefore seems to challenge the name of Earth. But although upon this ground one might easily enough have foretold, that the differing substances obtain'd from a perfectly mixt Body by the Fire would for the most part be reducible to the five newly mentioned States of Matter; yet it will not presently follow, that these five Distinct substances were simple and primogeneal bodies, so pre-existent in the Concrete that the fire does but take them asunder. Besides that it does not appear, that all Mixt Bodies, (witness, Gold, Silver, Mercury, &c.) Nay nor perhaps all Vegetables, which may appear by what we said above of _Camphire_, _Benzoin_, &c. are resoluble by Fire into just such differing Schemes of Matter. Nor will the Experiments formerly alledg'd permit us to look upon these separated Substances as Elementary, or uncompounded. Neither will it be a sufficient Argument of their being Bodies that deserve the Names which Chymists are pleas'd to give them, that they have an Analogy in point of Consistence, or either Volatility or Fixtness, or else some other obvious Quality, with the suppos'd Principles, whose names are ascrib'd to them. For, as I told you above, notwithstanding this Resemblance in some one Quality, there may be such a Disparity in others, as may be more fit to give them Differing Appellations, then the Resemblance is to give them one and the same. And indeed it seems but somewhat a gross Way of judging of the Nature of Bodies, to conclude without Scruple, that those must be of the same Nature that agree in some such General Quality, as Fluidity, Dryness, Volatility, and the like: since each of those Qualities, or States of Matter, may Comprehend a great Variety of Bodies, otherwise of a very differing Nature; as we may see in the Calxes of Gold, of Vitriol, and of Venetian Talck, compar'd with common Ashes, which yet are very dry, and fix'd by the vehemence of the Fire, as well as they. And as we may likewise gather from what I have formerly Observ'd, touching the Spirit of Box-Wood, which though a Volatile, Sapid, and not inflamable Liquor, as well as the Spirits of Harts-horn, of Blood and others, (and therefore has been hitherto call'd, the Spirit, and esteem'd for one of the Principles of the Wood that affords it;) may yet, as I told You, be subdivided into two Liquors, differing from one another, and one of them at least, from the Generality of other Chymical Spirits. But you may your self, if you please, (pursues _Carneades_) accommodate to the _Hypothesis_ you propos'd what other particulars you shall think applicable to it, in the foregoing Discourse. For I think it unseasonable for me to meddle now any further with a Controversie, which since it does not now belong to me, Leaves me at Liberty to Take my Own time to Declare my Self about it. _Eleutherius_ perceiving that _Carneades_ was somewhat unwilling to spend any more time upon the debate of this Opinion, and having perhaps some thoughts of taking hence a Rise to make him Discourse it more fully another time, thought not fit as then to make any further mention to him of the propos'd opinion, but told him; I presume I need not mind you, _Carneades_, That both the Patrons of the ternary number of Principles, and those that would have five Elements, endeavour to back their experiments with a specious Reason or two; and especially some of those Embracers of the Opinion last nam'd (whom I have convers'd with, and found them Learned men) assigne this Reason of the necessity of five distinct Elements; that otherwise mixt Bodies could not be so compounded and temper'd as to obtain a due consistence and competent Duration. For Salt (say they) is the _Basis_ of Solidity; and Permanency in Compound Bodies, without which the other four Elements might indeed be variously and loosly blended together, but would remain incompacted; but that Salt might be dissolv'd into minute Parts, and convey'd to the other Substances to be compacted by it, and with it, there is a Necessity of Water. And that the mixture may not be too hard and brittle, a Sulphureous or Oyly Principle must intervene to make the mass more tenacious; to this a Mercurial spirit must be superadded; which by its activity may for a while premeate [Transcriber's Note: permeate], and as it were leaven the whole Mass, and thereby promote the more exquisite mixture and incorporation of the Ingredients. To all which (lastly) a portion of Earth must be added, which by its drinesse and poracity [Errata: porosity] may soak up part of that water wherein the Salt was dissolv'd, and eminently concurr with the other ingredients to give the whole body the requisite consistence. I perceive (sayes _Carneades_ smiling) that if it be true, as 'twas lately rooted [Errata: noted] from the Proverb, _That good Wits have bad Memories_, You have that Title, as well as a better, to a place among the good Wits. For you have already more then once forgot, that I declar'd to you that I would at this Conference Examine only the Experiments of my Adversaries, not their Speculative Reasons. Yet 'tis not (Subjoynes _Carneades_) for fear of medling with the Argument you have propos'd, that I decline the examining it at present. For if when we are more at leasure, you shall have a mind that we may Solemnly consider of it together; I am confident we shall scarce find it insoluble. And in the mean time we may observe, that such a way of Arguing may, it seems, be speciously accommodated to differing _Hypotheses_. For I find that _Beguinus_, and other Assertors of the _Tria Prima_, pretend to make out by such a way, the requisiteness of their Salt, Sulphur and Mercury, to constitute mixt Bodies, without taking notice of any necessity of an Addition of Water and Earth. And indeed neither sort of Chymists seem to have duly consider'd how great Variety there is in the Textures and Consistences of Compound Bodie; sand [Errata: Bodies; and] how little the consistence and Duration of many of them seem to accommodate and be explicable by the propos'd Notion. And not to mention those almost incorruptible Substances obtainable by the Fire, which I have prov'd to be somewhat compounded, and which the Chymists will readily grant not to be perfectly mixt Bodies: (Not to mention these, I say) If you will but recall to mind some of those Experiments, whereby I shew'd You that out of common Water only mixt Bodies (and even living ones) of very differing consistences, and resoluble by Fire into as many Principles as other bodies acknowledg'd to be perfectly mixt; if you do this, I say, you will not, I suppose, be averse from beleeving, that Nature by a convenient disposition of the minute parts of a portion of matter may contrive bodies durable enough, and of this, or that, or the other Consistence, without being oblig'd to make use of all, much less of any Determinate quantity of each of the five Elements, or of the three Principles to compound such bodies of. And I have (pursues _Carneades_) something wonder'd, Chymists should not consider, that there is scarce any body in Nature so permanent and indissoluble as Glass; which yet themselves teach us may be made of bare Ashes, brought to fusion by the meer Violence of the Fire; so that, since Ashes are granted to consist but of pure Salt and simple Earth, sequestred from all the other Principles or Elements, they must acknowledge, That even Art it self can of two Elements only, or, if you please, one Principle and one Element, compound a Body more durable then almost any in the World. Which being undeniable, how will they prove that Nature cannot compound Mixt Bodies, and even durable Ones, under all the five Elements or material Principles. But to insist any longer on this Occasional Disquisition, Touching their Opinion that would Establish five Elements, were to remember as little as You did before, that the Debate of this matter is no part of my first undertaking; and consequently, that I have already spent time enough in what I look back upon but as a digression, or at best an Excursion. And thus, _Eleutherius_, (sayes _Carneades_) having at length gone through the four Considerations I propos'd to Discourse unto you, I hold it not unfit, for fear my having insisted so long on each of them may have made you forget their _Series_, briefly to repeat them by telling you, that Since, in the first place, it may justly be doubted whether or no the Fire be, as Chymists suppose it, the genuine and Universal Resolver of mixt Bodies; Since we may doubt, in the next place, whether or no all the Distinct Substances that may be obtain'd from a mixt body by the Fire were pre-existent there in the formes in which they were separated from it; Since also, though we should grant the Substances separable from mixt Bodies by the fire to have been their component Ingredients, yet the Number of such substances does not appear the same in all mixt Bodies; some of them being Resoluble into more differing substances than three, and Others not being Resoluble into so many as three. And Since, Lastly, those very substances that are thus separated are not for the most part pure and Elementary bodies, but new kinds of mixts; Since, I say, these things are so, I hope you will allow me to inferr, that the Vulgar Experiments (I might perchance have Added, the Arguments too) wont to be Alledg'd by Chymists to prove, that their three Hypostatical Principles do adequately compose all mixt Bodies, are not so demonstrative as to reduce a wary Person to acquiesce in their Doctrine, which, till they Explain and prove it better, will by its perplexing darkness be more apt to puzzle then satisfy considering men, and will to them appear incumbred with no small Difficulties. And from what has been hitherto deduc'd (continues _Carneades_) we may Learn, what to Judge of the common Practice of those Chymists, who because they have found that Diverse compound Bodies (for it will not hold in All) can be resolv'd into, or rather can be brought to afford two or three differing Substances more then the Soot and Ashes, whereinto the naked fire commonly divides them in our Chymnies, cry up their own Sect for the Invention of a New Philosophy, some of them, as _Helmont, &c._ styling themselves Philosophers by the Fire; and the most part not only ascribing, but as far as in them lies, engrossing to those of their Sect the Title of PHILOSOPHERS. But alas, how narrow is this Philosophy, that reaches but to some of those compound Bodies, which we find but upon, or in the crust or outside of our terrestrial Globe, which is it self but a point in comparison of the vast extended Universe, of whose other and greater parts the Doctrine of the _Tria Prima_ does not give us an Account! For what does it teach us, either of the Nature of the Sun, which Astronomers affirme to be eight-score and odd times bigger then the whole Earth? or of that of those numerous fixt Starrs, which, for ought we know, would very few, if any of them, appear inferiour in bulke and brightness to the Sun, if they were as neer us as He? What does the knowing that Salt, sulphur and Mercury, are the Principles of Mixt Bodies, informe us of the Nature of that vast, fluid, and Ætherial Substance, that seemes to make up the interstellar, and consequently much the greatest part of the World? for as for the opinion commonly ascrib'd to _Paracelsus_, as if he would have not only the four Peripatetick Elements, but even the Celestial parts of the Universe to consist of his three Principles, since the modern Chymists themselves have not thought so groundless a conceit worth their owning, I shall not think it Worth my confuting. But I should perchance forgive the Hypothesis I have been all this while examining, if, though it reaches but to a very little part of the World, it did at least give us a satisfactory account of those things to which 'tis said to reach. But I find not, that it gives us any other then a very imperfect information even about mixt Bodies themselves: For how will the knowledge of the _Tria Prima_ discover to us the Reason, why the Loadstone drawes a Needle and disposes it to respect the Poles, and yet seldom precisely points at them? how will this Hypothesis teach Us how a Chick is formed in the Egge, or how the Seminal Principles of Mint, Pompions, and other Vegitables, that I mention'd to You above, can fashion Water into Various Plants, each of them endow'd with its peculiar and determinate shape, and with divers specifick and discriminating Qualities? How does this Hypothesis shew us, how much Salt, how much Sulphur, and how much Mercury must be taken to make a Chick or a Pompion? and if We know that, what Principle is it, that manages these Ingredients, and contrives (for instance) such Liquors as the White and Yelk of an Egge into such a variety of Textures as is requisite to fashion the Bones, Veines, Arteries, Nerves, Tendons, Feathers, Blood, and other parts of a Chick; and not only to fashion each Limbe, but to connect them altogether, after that manner that is most congruous to the perfection of the Animal which is to Consist of Them? For to say, that some more fine and subtile part of either or all the Hypostatical Principles is the Director in all this business, and the Architect of all this Elaborate structure, is to give one occasion to demand again, what proportion and way of mixture of the _Tria Prima_ afforded this _Architectonick_ Spirit, and what Agent made so skilful and happy a mixture? And the Answer to this Question, if the Chymists will keep themselves within their three Principles, will be lyable to the same Inconvenience, that the Answer to the former was. And if it were not to intrench upon the Theame of a Friend of ours here present, I could easily prosecute the Imperfections of the Vulgar Chymists Philosophy, and shew you, that by going about to explicate by their three Principles, I say not, all the abstruse Properties of mixt Bodies, but even such Obvious and more familiar _Phænomena_ as _Fluidity_ and _Firmness_, The Colours and Figures of Stones, Minerals, and other compound Bodies, The Nutrition of either Plants or Animals, the Gravity of Gold or Quicksilver compar'd with Wine or Spirit of Wine; By attempting, I say, to render a reason of these (to omit a thousand others as difficult to account for) from any proportion of the three simple Ingredients, Chymists will be much more likely to discredit themselves and their _Hypothesis_, then satisfy an intelligent Inquirer after Truth. But (interposes _Eleutherus_) [Transcriber's Note: Eleutherius] This Objection seems no more then may be made against the four Peripatetick Elements. And indeed almost against any other _Hypothesis_, that pretends by any Determinate Number of Material Ingredients to render a reason of the _Phænomena_ of Nature. And as for the use of the Chymical Doctrine of the three Principles, I suppose you need not be told by me, that The great Champion of it, The Learned _Sennertus_,[23] assignes this noble use of the _Tria Prima_, That from Them, as the neerest and most Proper Principles, may be Deduc'd and Demonstrated the Properties which are in Mixt Bodies, and which cannot be Proximately (as They speak) deduc'd from the Elements. And This, sayes he, is chiefly Apparent, when we Inquire into the Properties and Faculties of Medecines. And I know (continues _Eleutherius_) That the Person You have assum'd, of an Opponent of the _Hermetick Doctrine_, will not so far prevaile against your Native and wonted Equity, as To keep You from acknowledging that Philosophy is much beholden to the Notions and Discoveries of Chymists. [Footnote 23: _Senn. de Cons. & Dissen. p. 165._] If the Chymists You speak of (Replyes _Carneades_) had been so modest, or so Discreet, as to propose their Opinion of the _Tria Prima_, but as a Notion useful among Others, to increase Humane knowledge, they had deserv'd more of our thanks; and less of our Opposition; but since the Thing that they pretend is not so much to contribute a Notion toward the Improvement of Philosophy, as to make this Notion attended [Errata: (attended] by a few lesse considerable ones) pass for a New Philosophy itself. Nay, since they boast so much of this phancie of theirs, that the famous _Quercetanus_ scruples not to write, that if his most certain Doctrine of the three Principles were sufficiently Learned, Examin'd, and Cultivated, it would easily Dispel all the Darkness that benights our minds, and bring in a Clear Light, that would remove all Difficulties. This School affording Theorems and Axiomes irrefragable, and to be admitted without Dispute by impartial Judges; and so useful withal, as to exempt us from the necessity of having recourse, for want of the knowledg of causes, to that Sanctuary of the igorant [Transcriber's Note: ignorant], Occult Qualities; since, I say, this Domestick Notion of the Chymists is so much overvalued by them, I cannot think it unfit, they should be made sensible of their mistake; and be admonish'd to take in more fruitful and comprehensive Principles, if they mean to give us an account of the _Phænomena_ of Nature; and not confine themselves and (as far as they can) others to such narrow Principles, as I fear will scarce inable them to give an account (I mean an intelligible one) of the tenth part (I say not) of all the _Phænomena_ of Nature; but even of all such as by the _Leucippian_ or some of the other sorts of Principles may be plausibly enough explicated. And though I be not unwilling to grant, that the incompetency I impute to the Chymical _Hypothesis_ is but the same which may be Objected against that of the four Elements, and divers other Doctrines that have been maintain'd by Learned men; yet since 'tis the Chymical _Hypothesis_ only which I am now examining, I see not why, if what I impute to it be a real inconvenience, either it should cease to be so, or I should scruple to object it, because either Theories are lyable thereunto, as well as the Hermetical. For I know not why a Truth should be thought lesse a Truth for the being fit to overthrow variety of Errors. I am oblig'd to You (continues _Carneades_, a little smiling) for the favourable Opinion You are pleas'd to express of my Equity, if there be no design in it. But I need not be tempted by an Artifice, or invited by a Complement, to acknowledge the great service that the Labours of Chymists have done the Lovers of useful Learning; nor even on this occasion shall their Arrogance hinder my Gratitude. But since we are as well examining to [Errata: delete "to"] the truth of their Doctrine as the merit of their industry, I must in order to the investigation of the first, continue a reply, to talk at the rate of the part I have assum'd; And tell you, that when I acknowledg the usefulness of the Labours of _Spagyrists_ to Natural Philosophy, I do it upon the score of their experiments, not upon that of Their Speculations; for it seems to me, that their Writings, as their Furnaces, afford as well smoke as light; and do little lesse obscure some subjects, then they illustrate others. And though I am unwilling to deny, that 'tis difficult for a man to be an Accomplisht Naturalist, that is a stranger to Chymistry, yet I look upon the common Operations and practices of Chymists, almost as I do on the Letters of the Alphabet, without whose knowledge 'tis very hard for a man to become a Philosopher; and yet that knowledge is very far from being sufficient to make him One. But (sayes _Carneades_, resuming a more serious Look) to consider a little more particularly what you alledg in favour of the Chymical Doctrine of the _Tria Prima_, though I shall readily acknowledge it not to be unuseful, and that the Divisers [Errata: devisers] and Embracers of it have done the Common-Wealth of Learning some service, by helping to destroy that excessive esteem, or rather veneration, wherewith the Doctrine of the four Elements was almost as generally as undeservedly entertain'd; yet what has been alledg'd concerning the usefulness of the _Tria Prima_, seems to me liable to no contemptible Difficulties. And first, as for the very way of Probation, which the more Learned and more Sober Champions of the Chymical cause employ to evince the Chymical Principles in Mixt Bodies, it seems to me to be farr enough from being convincing. This grand and leading Argument, your _Sennertus_ Himself, who layes Great weight upon it, and tells us, that the most Learned Philosophers employ this way of Reasoning to prove the most important things, proposes thus: _Ubicunque_ (sayes he) _pluribus eædem affectiones & qualitates insunt, per commune quoddam Principium insint necesse est, sicut omnia sunt Gravia propter terram, calida propter Ignem. At Colores, Odores, Sapores, esse_ [Greek: phlogiston] _& similia alia, mineralibus, Metallis, Gemmis, Lapidibus, Plantis, Animalibus insunt. Ergo per commune aliquod principium, & subiectum, insunt. At tale principium non sunt Elementa. Nullam enim habent ad tales qualitates producendas potentiam. Ergo alia principia, unde fluant, inquirenda sunt._ In the Recital of this Argument, (sayes _Carneades_) I therefore thought fit to retain the Language wherein the Author proposes it, that I might also retain the propriety of some Latine Termes, to which I do not readily remember any that fully answer in English. But as for the Argumentation it self, 'tis built upon a precarious supposition, that seems to me neither Demonstrable nor true; for, how does it appear, that where the same Quality is to be met with in many Bodies, it must belong to them upon the Account of some one Body whereof they all partake? (For that the Major of our Authors Argument is to be Understood of the Material Ingredients of bodies, appears by the Instances of Earth and Fire he annexes to explain it.) For to begin with that very Example which he is pleas'd to alledge for himself; how can he prove, that the Gravity of all Bodies proceeds from what they participate of the Element of Earth? Since we see, that not only common Water, but the more pure Distill'd Rain Water is heavy; and Quicksilver is much heavier than Earth it self; though none of my Adversaries has yet prov'd, that it contains any of that Element. And I the Rather make use of this Example of Quicksilver, because I see not how the Assertors of the Elements will give any better Account of it then the Chymists. For if it be demanded how it comes to be Fluid, they will answer, that it participates much of the Nature of Water. And indeed, according to them, Water may be the Predominant Element in it, since we see, that several Bodies which by Distillation afford Liquors that weigh more then their _Caput Mortuum_ do not yet consist of Liquor enough to be Fluid. Yet if it be demanded how Quicksilver comes to be so heavy, then 'tis reply'd, that 'tis by reason of the Earth that abounds in it; but since, according to them, it must consist also of air, and partly of Fire, which they affirm to be light Elements, how comes it that it should be so much heavier then Earth of the same bulk, though to fill up the porosities and other Cavities it be made up into a mass or paste with Water, which it self they allow to be a heavy Element. But to returne to our _Spagyrists_, we see that Chymical Oyles and fixt Salts, though never so exquisitely purify'd and freed from terrestrial parts, do yet remain ponderous enough. And Experience has inform'd me, that a pound, for instance, of some of the heaviest Woods, as _Guajacum_ that will sink in Water, being burnt to Ashes will yield a much less weight of them (whereof I found but a small part to be Alcalyzate) then much lighter Vegetables: As also that the black Charcoal of it will not sink as did the wood, but swim; which argues that the Differing Gravity of Bodies proceeds chiefly from their particular Texture, as is manifest in Gold, the closest and Compactest of Bodies, which is many times heavier then we can possibly make any parcell of Earth of the same Bulk. I will not examine, what may be argu'd touching the Gravity or Quality Analagous thereunto, of even Celestial bodies, from the motion of the spots about the Sun, d [Errata: and] from the appearing equality of the suppos'd Seas in the Moon; nor consider how little those _Phæmonea_ [Transcriber's Note: Phænomena] would agree with what _Sennertus_ presumes concerning Gravity. But further to invalidate his supposition, I shall demand, upon what Chymical Principle Fluidity depends? And yet Fluidity is, two or three perhaps excepted, the most diffused quality of the universe, and far more General then almost any other of those that are to be met with in any of the Chymicall Principles, or _Aristotelian_ Elements; since not only the Air, but that vast expansion we call Heaven, in comparison of which our Terrestrial Globe (supposing it were all Solid) is but a point; and perhaps to [Errata: too] the Sun and the fixt Stars are fluid bodies. I demand also, from which of the Chymical Principles Motion flowes; which yet is an affection of matter much more General then any that can be deduc'd from any of the three Chymical Principles. I might ask the like Question concerning Light, which is not only to be found in the Kindl'd Sulphur of mixt Bodis [Transcriber's Note: Bodies], but (not to mention those sorts of rotten Woods, and rotten Fish that shine in the Dark) in the tails of living Glow-wormes, and in the Vast bodies of the Sun and Stars. I would gladly also know, in which of the three Principles the Quality, we call Sound, resides as in its proper Subject; since either Oyl falling upon Oyle, or Spirit upon Spirit, or Salt upon Salt, in a great quantity, and from a considerable height, will make a noise, or if you please, create a sound, and (that the objection may reach the _Aristotelians_) so will also water upon water, and Earth upon Earth. And I could name other qualities to be met within divers bodies, of which I suppose my Adversaries will not in haste assign any Subject, upon whose Account it must needs be, that the quality belongs to all the other several bodies. And, before I proceed any further, I must here invite you to compare the supposition we are examining, with some other of the Chymical Tenents. For, first they do in effect teach that more then one quality may belong to, and be deduc'd from, one Principle. For, they ascribe to Salt Tasts, and the power of Coagulation; to sulphur, as well Odours as inflamableness; And some of them ascribe to Mercury, Colours; as all of them do effumability, as they speak. And on the other side, it is evident that Volatility belongs in common to all the three Principles, and to Water too. For 'tis manifest, that Chymical Oyles are Volatile; That also divers Salts Emerging, upon the Analysis of many Concretes, are very Volatile, is plain from the figitiveness [Errata: fugitivenesse] of Salt, of Harts-horne, flesh, &c. ascending in the Distillation of those bodies. How easily water may be made to ascend in Vapours, there is scarce any body that has not observ'd. And as for what they call the Mercuriall Principle of bodies, that is so apt to be rais'd in the form of Steam, that _Paracelsus_ and others define it by that aptness to fly up; so that (to draw that inference by the way) it seems not that Chymists have been accurate in their Doctrine of qualities, and their respective Principles, since they both derive several qualities from the same Principle, and must ascribe the same quality to almost all their Principles and other bodies besides. And thus much for the first thing taken for granted, without sufficient proof, by your _Sennertus_: And to add that upon the Bye (continues _Carneades_) we may hence learn what to judge of the way of Argumentation, which that fierce Champion of the _Aristotelians_ against the Chymists, _Anthonius Guntherus Billichius_[24] employes, where he pretends to prove against _Beguinus_, that not only the four Elements do immediately concur to Constitute every mixt body, and are both present in it, and obtainable from it upon its Dissolution; but that in the _Tria Prima_ themselves, whereinto Chymists are wont to resolve mixt Bodies, each of them clearly discovers it self to consist of four Elements. The Ratiocination it self (pursues _Carneades_) being somewhat unusual, I did the other Day Transcribe it, and (sayes He, pulling a Paper out of his Pocket) it is this. _Ordiamur, cum Beguino, a ligno viridi, quod si concremetur, videbis in sudore Aquam, in fumo Aerem, in flamma & Prunis Ignem, Terram in cineribus: Quod si Beguino placuerit ex eo colligere humidum aquosum, cohibere humidum oleaginosum, extrahere ex cineribus salem; Ego ipsi in unoquoque horum seorsim quatuor Elementa ad oculum demonstrabo, eodem artificio quo in ligno viridi ea demonstravi. Humorem aquosum admovebo Igni. Ipse Aquam Ebullire videbit, in Vapore Aerem conspiciet, Ignem sentiet in æstu, plus minus Terræ in sedimento apparebit. Humor porro Oleaginosus aquam humiditate & fluiditate per se, accensus vero Ignem flamma prodit, fumo Aerem, fuligine, nidore & amurca terram. Salem denique ipse Beguinus siccum vocat & Terrestrem, qui tamen nec fusus Aquam, nec caustica vi ignem celare potest; ignis vero Violentia in halitus versus nec ab Aere se alienum esse demonstrat; Idem de Lacte, de Ovis, de semine Lini, de Garyophyllis, de Nitro, de sale Marino, denique de Antimonio, quod fuit de Ligno viridi Judicium; eadem de illorum partibus, quas_ Beguinus _adducit, sententia, quæ de viridis ligni humore aquoso, quæ de liquore ejusdem oleoso, quæ de sale fuit._ [Footnote 24: _In Thessalo redivivo. Cap. 10. pag. 73. & 74._] This bold Discourse (resumes _Carneades_, putting up again his Paper,) I think it were not very difficult to confute, if his Arguments were as considerable as our time will probably prove short for the remaining and more necessary Part of my Discourse; wherefore referring You for an Answer to what was said concerning the Dissipated Parts of a burnt piece of green Wood, to what I told _Themistius_ on the like occasion, I might easily shew You, how sleightly and superficially our _Guntherus_ talks of the dividing the flame of Green Wood into his four Elements; _When_ he makes that vapour to be air, which being caught in Glasses and condens'd, presently discovers it self to have been but an Aggregate of innumerable very minute drops of Liquor; and _When_ he would prove the Phlegmes being compos'd of Fire by that Heat which is adventitious to the Liquor, and ceases upon the absence of what produc'd it (whether that be an Agitation proceeding from the motion of the External Fire, or the presence of a Multitude of igneous Atomes pervading the pores of the Vessel, and nimbly permeating the whole Body of the Water) I might, I say, urge these and divers other Weaknesses of His Discourse. But I will rather take Notice of what is more pertinent to the Occasion of this Digression, namely, that Taking it for Granted, that Fluidity (with which he unwarily seems to confound Humidity) must proceed from the Element of Water, he makes a Chymical Oyle to Consist of that Elementary Liquor; and yet in the very next Words proves, that it consists also of Fire, by its Inflamability; not remembring that exquisitely pure Spirit of Wine is both more Fluid then Water it self, and yet will Flame all away without leaving the Least Aqueous Moisture behind it; and without such an _Amurca_ and Soot as he would Deduce the presence of Earth from. So that the same Liquor may according to his Doctrine be concluded by its great Fluidity to be almost all Water; and by its burning all away to be all disguised Fire. And by the like way of Probation our Author would shew that the fixt salt of Wood is compounded of the four Elements. For (sayes he) being turn'd by the violence of the Fire into steames, it shews it self to be of kin to Air; whereas I doubt whether he ever saw a true fixt Salt (which to become so, must have already endur'd the violence of an Incinerating Fire) brought by the Fire alone to ascend in the Forme of Exhalations; but I do not doubt that if he did, and had caught those Exhalations in convenient Vessels, he would have found them as well as the Steames of common Salt, &c. of a Saline and not an Aereal Nature. And whereas our Authour takes it also for Granted, that the Fusibility of Salt must be Deduc'd from Water, it is indeed so much the Effect of heat variously agitating the Minute Parts of a Body, without regard to Water, that Gold (which by its being the heavyest and fixtest of Bodies, should be the most Earthy) will be brought to Fusion by a strong Fire; which sure is more likely to drive away then increase its Aqueous Ingredient, if it have any; and on the other side, for want of a sufficient agitation of its minute parts, Ice is not Fluid, but Solid; though he presumes also that the Mordicant Quality of Bodies must proceed from a fiery ingredient; whereas, not to urge that the Light and inflamable parts, which are the most likely to belong to the Element of Fire, must probably be driven away by that time the violence of the Fire has reduc'd the Body to ashes; Not to urge this, I I [Transcriber's Note: extra "I" in original] say, nor that Oyle of Vitriol which quenches Fire, burnes the Tongue and flesh of those that Unwarily tast or apply it, as a caustick doth, it is precarious to prove the Presence of Fire in fixt salts from their Caustick power, unlesse it were first shewn, that all the Qualities ascribed to salts must be deduc'd from those of the Elements; which, had I Time, I could easily manifest to be no easy talk. And not to mention that our Authour makes a Body as Homogeneous as any he can produce for Elementary, belong both to Water and Fire, Though it be neither Fluid nor Insipid, like Water; nor light and Volatile, like Fire; he seems to omit in this Anatomy the Element of Earth, save That he intimates, That the salt may pass for that; But since a few lines before, he takes Ashes for Earth, I see not how he will avoid an Inconsistency either betwixt the Parts of his Discourse or betwixt some of them and his Doctrine. For since There is a manifest Difference betwixt the Saline and the insipid Parts of Ashes, I see not how substances That Disagree in such Notable Qualities can be both said to be Portions of an Element, whose Nature requires that it be Homogeneous, especially in this case where an _Analysis_ by the Fire is suppos'd to have separated it from the admixture of other Elements, which are confess'd by most _Aristotelians_ to be Generally found in common Earth, and to render it impure. And sure if when we have consider'd for how little a Disparities sake the Peripateticks make these Symbolizing Bodies Aire and Fire to be two Distinct Elements, we shall also consider that the Saline part of Ashes is very strongly Tasted, and easily soluble in Water; whereas the other part of the same Ashes is insipid and indissoluble in the same Liquor: Not to add, that the one substance is Opacous, and the other somewhat Diaphanous, nor that they differ in Divers other Particulars; If we consider those things, I say, we shall hardly think that both these Substances are Elementary Earth; And as to what is sometimes objected, that their Saline Tast is only an Effect of Incineration and Adustion, it has been elsewhere fully reply'd to, when propos'd by _Themistius_, and where it has been prov'd against him, that however insipid Earth may perhaps by Additaments be turn'd into Salt, yet 'tis not like it should be so by the Fire alone: For we see that when we refine Gold and Silver, the violentest Fires We can Employ on them give them not the least Rellish of Saltness. And I think _Philoponus_ has rightly observ'd, that the Ashes of some Concretes contain very little salt if any at all; For Refiners suppose that bone-ashes are free from it, and therefore make use of them for Tests and Cuppels, which ought to be Destitute of Salt, lest the Violence of the Fire should bring them to Vitrification; And having purposely and heedfully tasted a Cuppel made of only bone-ashes and fair water, which I had caus'd to be expos'd to a Very Violent Fire, acuated by the Blast of a large pair of Double Bellows, I could not perceive that the force of the Fire had imparted to it the least Saltness, or so much as made it less Insipid. But (sayes _Carneades_) since neither You nor I love Repetitions, I shall not now make any of what else was urg'd against _Themistius_ but rather invite You to take notice with me that when our Authour, though a Learned Man, and one that pretends skill enough in Chymistry to reforme the whole Art, comes to make good his confident Undertaking, to give us an occular Demonstration of the immediate Presence of the four Elements in the resolution of Green Wood, He is fain to say things that agree very little with one another. For about the beginning of that passage of His lately recited to you, he makes the sweat as he calls it of the green Wood to be Water, the smoke Aire, the shining Matter Fire, and the Ashes Earth; whereas a few lines after, he will in each of these, nay (as I just now noted) in one Distinct Part of the Ashes, shew the four Elements. So that either the former _Analysis_ must be incompetent to prove that Number of Elements, since by it the burnt Concrete is not reduc'd into Elementary Bodies, but into such as are yet each of them compounded of the four Elements; or else these Qualities from which he endeavours to deduce the presence of all the Elements, in the fixt salt, and each of the other separated substances, will be but a precarious way of probation: especially if you consider, that the extracted _Alcali_ of Wood, being for ought appears at least as similar a Body as any that the Peripateticks can shew us, if its differing Qualities must argue the presence of Distinct Elements, it will scarce be possible for them by any way they know of employing the fire upon a Body, to shew that any Body is a Portion of a true Element: And this recals to my mind, that I am now but in an occasional excussion, which aiming only to shew that the Peripateticks as well as the Chymists take in our present Controversie something for granted which they ought to prove, I shall returne to my exceptions, where I ended the first of them, and further tell you, that neither is that the only precarious thing that I take notice of in _Sennertus_ his Argumentation; for when he inferrs, that because the Qualities he Mentions as Colours, Smels, and the like, belong not to the Elements; they therefore must to the Chymical Principles, he takes that for granted, which will not in haste be prov'd; as I might here manifest, but that I may by and by have a fitter opportunity to take notice of it. And thus much at present may suffice to have Discours'd against the Supposition, that almost every Quality must have some [Greek: dektikon prôton], as they speak, some Native receptacle, wherein as in its proper Subject of inhesion it peculiarly resides, and on whose account that quality belongs to the other Bodies, Wherein it is to be met with. Now this Fundamental supposition being once Destroy'd, whatsoever is built upon it, must fall to ruine of it self. But I consider further, that Chymists are (for ought I have found) far from being able to explicate by any of the _Tria Prima_, those qualities which they pretend to belong primarily unto it, and in mixt Bodies to Deduce from it. Tis true indeed, that such qualities are not explicable by the four Elements; but it will not therefore follow, that they are so by the three hermetical Principles; and this is it that seems to have deceiv'd the Chymists, and is indeed a very common mistake amongst most Disputants, who argue as if there could be but two Opinions concerning the Difficulty about which they contend; and consequently they inferr, that if their Adversaries Opinion be Erroneous, Their's must needs be the Truth; whereas many questions, and especially in matters Physiological, may admit of so many Differing _Hypotheses_, that 'twill be very inconsiderate and fallacious to conclude (except where the Opinions are precisely Contradictory) the Truth of one from the falsity of another. And in our particular case 'tis no way necessary, that the Properties of mixt Bodies must be explicable either by the Hermetical, or the _Aristotelian Hypothesis_, there being divers other and more plausible wayes of explaining them, and especially that, which deduces qualities from the motion, figure, and contrivance of the small parts of Bodies; as I think might be shewn, if the attempt were as seasonable, as I fear it would be Tedious. I will allow then, that the Chymists do not causelessly accuse the Doctrine of the four elements of incompetency to explain the Properties of Compound bodies. And for this Rejection of a Vulgar Error, they ought not to be deny'd what praise men may deserve for exploding a Doctrine whose Imperfections are so conspicuous, that men needed but not to shut their Eyes, to discover them. But I am mistaken, if our Hermetical Philosophers Themselves need not, as well as the Peripateticks, have Recourse to more Fruitfull and Comprehensive Principles then the _tria Prima_, to make out the Properties of the Bodies they converse with. Not to accumulate Examples to this purpose, (because I hope for a fitter opportunity to prosecute this Subject) let us at present only point at Colour, that you may guess by what they say of so obvious and familiar a Quality, how little Instruction we are to expect from the _Tria Prima_ in those more abstruse ones, which they with the _Aristotelians_ stile Occult. For about Colours, neither do they at all agree among themselves, nor have I met with any one, of which of the three Perswasions soever, that does intelligibly explicate Them. The Vulgar Chymists are wont to ascribe Colours to Mercury; _Paracelsus_ in divers places attributes them to Salt; and _Sennertus_,[25] having recited their differing Opinions, Dissents from both, and referrs Colours rather unto Sulphur. But how Colours do, nay, how they may, arise from either of these Principles, I think you will scarce say that any has yet intelligibly explicated. And if Mr. _Boyle_ will allow me to shew you the Experiments which he has collected about Colours, you will, I doubt not, confess that bodies exhibite colours, not upon the Account of the Predominancy of this or that Principle in them, but upon that of their Texture, and especially the Disposition of their superficial parts, whereby the Light rebounding thence to the Eye is so modifi'd, as by differing Impressions variously to affect the Organs of Sight. I might here take notice of the pleasing variety of Colours exhibited by the Triangular glass, (as 'tis wont to be call'd) and demand, what addition or decrement of either Salt, Sulphur, or Mercury, befalls the Body of the Glass by being Prismatically figur'd; and yet 'tis known, that without that shape it would not affor'd those colours as it does. But because it may be objected, that these are not real, but apparent Colours; that I may not lose time in examing the Distinction, I will alledge against the Chymists, a couple of examples of Real and Permanent Colours Drawn from Metalline Bodies, and represent, that without the addition of any extraneous body, Quicksilver may by the Fire alone, and that in glass Vessels, be depriv'd of its silver-like Colour, and be turn'd into a Red Body; and from this Red Body without Addition likewise may be obtain'd a Mercury Bright and Specular as it was before; So that I have here a lasting Colour Generated and Destroy'd (as I have seen) at pleasure, without adding or taking away either Mercury, Salt, or Sulphur; and if you take a clean and slender piece of harden'd steel, and apply to it the flame of a candle at some little distance short of the point, You shall not have held the Steel long in the flame, but You shall perceive divers Colours, as Yellow, Red and Blew, to appear upon the Surface of the metal, and as it were run along in chase of one another towards the point; So that the same body, and that in one and the same part, may not only have a new colour produc'd in it, but exhibite successively divers Colours within a minute of an hour, or thereabouts, and any of these Colours may by Removing the Steel from the Fire, become Permanent, and last many years. And this Production and Variety of Colours cannot reasonably be suppos'd to proceed from the Accession of any of the three Principles, to which of them soever Chymists will be pleas'd to ascribe Colours; especially considering, that if you but suddenly Refrigerate that Iron, First made Red hot, it will be harden'd and Colourless again; and not only by the Flame of a Candle, but by any other equivalent heat Conveniently appli'd, the like Colours will again be made to appear and succeed one another, as at the First. But I must not any further prosecute an Occasional Discourse, though that were not so Difficult for me to do, as I fear it would be for the Chymists to give a better Account of the other Qualities, by their Principles, then they have done of Colours. And your _Sennertus_ Himself (though an Author I much value) would I fear have been exceedingly puzl'd to resolve, by the _Tria Prima_, halfe that Catalogue of Problems, which he challenges the Vulgar Peripateticks to explicate by their four Elements.[26] And supposing it were true, that Salt or Sulphur were the Principle to which this or that Quality may be peculiarly referr'd, yet though he that teaches us this teaches us something concerning That quality, yet he Teaches us but something. For indeed he does not Teach us That which can in any Tollerable measure satisfie an inquisitive Searcher after Truth. For what is it to me to know, that such a quality resides in such a Principle or Element, whilst I remain altogether ignorant of the Cause of that quality, and the manner of its production and Operation? How little do I know more then any Ordinary Man of Gravity, if I know but that the Heaviness of mixt bodies proceeds from that of the Earth they are compos'd of, if I know not the reason why the Earth is Heavy? And how little does the Chymist teach the Philosopher of the Nature of Purgatition, if he only tells him that the Purgative Vertue of Medicines resides in their Salt? For, besides that this must not be conceded without Limitation, since the purging parts of many Vegetables Extracted by the Water wherein they are infus'd, are at most but such compounded Salts, (I mean mingl'd with Oyle, and Spirit, and Earth, as Tartar and divers other Subjects of the Vegetable Kingdom afford;) And since too that Quicksilver precipitated either with Gold, or without Addition, into a powder, is wont to be strongly enough Cathartical, though the Chymists have not yet prov'd, that either Gold or Mercury have any Salt at all, much less any that is Purgative; Besides this, I say, how little is it to me, to know That 'tis the Salt of the Rhubarb (for Instance) that purges, if I find That it does not purge as Salt; since scarce any Elementary Salt is in small quantity cathartical. And if I know not how Purgation in general is effected in a Humane Body? In a word, as 'tis one thing to know a mans Lodging, and another, to be acquainted with him; so it may be one thing to know the subject wherein a Quality principally resides, and another thing to have a right notion and knowledg of the quality its self. Now that which I take to be the reason of this Chymical Deficiency, is the same upon whose account I think the _Aristotelian_ and divers other Theories incompetent to explicate the Origen [Errata: origine] of Qualities. For I am apt to think, that men will never be able to explain the _Phænomena_ of Nature, while they endeavour to deduce them only from the Presence and Proportion of such or such material Ingredients, and consider such ingredients or Elements as Bodies in a state of rest; whereas indeed the greatest part of the affections of matter, and consequently of the _Phænomena_ of nature, seems to depend upon the motion and the continuance [Errata: contrivance] of the small parts of Bodies. For 'tis by motion that one part of matter acts upon another; and 'tis, for the most part, the texture of the Body upon which the moving parts strike, that modifies to motion or Impression, and concurrs with it to the production of those Effects which make up the chief part of the Naturalists Theme. [Footnote 25: _De Cons. & dissen. cap. 11. pag. 186._] [Footnote 26: _Sennert. de Con. seus. [Transcriber's Note: Consens.] & Dissens. pag. 165. 166._] But (sayes _Eleutherius_) me thinks for all this, you have left some part of what I alledg'd in behalf of the three principles, unanswer'd. For all that you have said will not keep this from being a useful Discovery, that since in the Salt of one Concrete, in the Sulphur of another and the Mercury of a third, the Medicinal vertue of it resides, that Principle ought to be separated from the rest, and there the desired faculty must be sought for. I never denyed (Replyes _Carneades_) that the Notion of the _Tria Prima_ may be of some use, but (continues he laughing) by what you now alledg for it, it will but appear That it is useful to Apothecaries, rather than to Philosophers, The being able to make things Operative being sufficient to those, whereas the Knowledge of Causes is the Thing looked after by These. And let me Tell You, _Eleutherius_, even this it self will need to be entertained with some caution. For first, it will not presently follow, That if the Purgative or other vertue of a simple may be easily extracted by Water or Spirit of Wine, it Resides in the Salt or Sulphur of the Concrete; Since unlesse the Body have before been resolved by the Fire, or some Other Powerful Agent, it will, for the most part, afford in the Liquors I have named, rather the finer compounded parts of it self, Than the Elementary ones. As I noted before, That Water will dissolve not only pure Salts, but Crystals of Tartar, Gumme Arabick, Myrr'h, and Other Compound Bodies. As also Spirit of Wine will Dissolve not only the pure Sulphur of Concretes, but likewise the whole Substance of divers Resinous Bodies, as Benzoin, the Gummous parts of Jallap, Gumme Lacca, and Other bodies that are counted perfectly Mixt. And we see that the Extracts made either with Water or Spirit of Wine are not of a simple and Elementary Nature, but Masses consisting of the looser Corpuscles, and finer parts of the Concretes whence they are Drawn; since by Distillation they may be Divided into more Elementary substances. Next, we may consider That even when there intervenes a Chymical resolution by he [Transcriber's Note: the] Fire, 'tis seldom in the Saline or Sulphureous principle, as such, that the desir'd Faculty of the Concrete Resides; But, as that Titular Salt or Sulphur is yet a mixt body, though the Saline or Sulphureous Nature be predominant in it. For, if in Chymical Resolutions the separated Substances were pure and simple Bodies, and of a perfect Elementary Nature; no one would be indued with more Specifick Vertues, than another; and their qualities would Differ as Little as do those of Water. And let me add this upon the bye, That even Eminent Chymists have suffer'd themselves to be reprehended by me for their over great Diligence in purifying some of the things they obtain by Fire from mixt Bodies. For though such compleatly purifyed Ingredients of Bodies might perhaps be more satisfactory to our Understanding; yet others are often more useful to our Lives, the efficacy of such Chymical Productions depending most upon what they retain of the Bodies whence they are separated, or gain by the new associations of the Dissipated among themselves; whereas if they were meerly Elementary, their uses would be comparatively very small; and the vertues of Sulphurs, Salts, or Other such Substances of one denomination, would be the very same. And by the Way (_Eleutherius_) I am inclin'd upon this ground to Think, That the artificial resolution of compound bodies by Fire does not so much enrich mankind, as it divides them into their supposed Principles; as upon the score of its making new compounds by now [Transcriber's Note: new] combinations of the dissipated parts of the resolv'd Body. For by this means the Number of mixt Bodies is considerably increased. And many of those new productions are indow'd with useful qualities, divers of which they owe not to the body from which they were obtein'd, but to Their newly Acquired Texture. But thirdly, that which is principally to be Noted is this, that as there are divers Concretes whose Faculties reside in some one or other of those differing Substances that Chymists call their Sulphurs, Salts, and Mercuries, and consequently may be best obtain'd, by analyzing the Concrete whereby the desired Principles may be had sever'd or freed from the rest; So there are other wherein the noblest properties lodge not in the Salt, or Sulphur, or Mercury, but depend immediately upon the form (or if you will) result from the determinate structure of the Whole Concrete; and consequently they that go about to extract the Vertues of such bodies, by exposing them to the Violence of the Fire, do exceedingly mistake, and take the way to Destroy what they would obtain. I remmember that _Helmont_ himself somewhere confesses, That as the Fire betters some things and improves their Vertues, so it spoyles others and makes them degenerate. And elsewhere he judiciously affirmes, that there may be sometimes greater vertue in a simple, such as Nature has made it, than in any thing that can by the fire be separated from it. And lest you should doubt whether he means by the vertues of things those that are Medical; he has in one place[27] this ingenuous confession; _Credo_ (sayes he) _simplicia in sua simplicitate esse sufficientia pro sanatione omnium morborum._ Nag. [Errata: Nay,] Barthias, even in a Comment upon _Beguinus_,[28] scruples not to make this acknowledgment; _Valde absurdum est_ (sayes he) _ex omnibus rebus extracta facere, salia, quintas essentias; præsertim ex substantiis per se plane vel subtilibus vel homogeneis, quales sunt uniones, Corallia, Moscus, Ambra, &c._ Consonantly whereunto he also tells Us (and Vouches the famous _Platerus_, for having candidly given the same Advertisement to his Auditors,) that some things have greater vertues, and better suited to our humane nature, when unprepar'd, than when they have past the Chymists Fire; as we see, sayes my Author, in Pepper; of which some grains swallowed perform more towards the relief of a Distempered stomack, than a great quantity of the Oyle of the same spice. [Footnote 27: Helmont Pharm. & Dispens. Nov. p. 458.] [Footnote 28: Vide Jer. ad Begu. Lib. 1. Cap. 17.] It has been (pursues _Carneades_) by our Friend here present observ'd concerning Salt-petre, that none of the substances into which the Fire is wont to divide it, retaines either the Tast, the cooling vertue, or some other of the properties of the Concrete; and that each of those Substances acquires new qualities, not to be found in the Salt-Petre it self. The shining property of the tayls of gloworms does survive but so short a time the little animal made conspicuous by it, that inquisitive men have not scrupled publickly to deride _Baptista Porta_ and others; who deluded perhaps with some Chymical surmises have ventur'd to prescribe the distillation of a Water from the tayles of Glowormes, as a sure way to obtain a liquor shining in the Dark. To which I shall now add no other example than that afforded us by Amber; which, whilst it remains an intire body, is endow'd with an Electrical faculty of drawing to it self fethers, strawes, and such like Bodies; which I never could observe either in its Salt, its Spirit, its Oyle, or in the Body I remember I once made by the reunion of its divided Elements; none of these having such a Texture as the intire Concrete. And however Chymists boldly deduce such and such properties from this or that proportion of their component Principles; yet in Concretes that abound with this or that Ingredient, 'tis not alwayes so much by vertue of its presence, nor its plenty, that the Concrete is qualify'd to perform such and such Effects; as upon the account of the particular texture of that and the other Ingredients, associated after a determinate Manner into one Concrete (though possibly such a proportion of that ingredient may be more convenient than an other for the constituting of such a body.) Thus in a clock the hand is mov'd upon the dyal, the bell is struck, and the other actions belonging to the engine are perform'd, not because the Wheeles are of brass or iron, or part of one metal and part of another, or because the weights are of Lead, but by Vertue of the size, shape, bigness, and co-aptation of the several parts; which would performe the same things though the wheels were of Silver, or Lead, or Wood, and the Weights of Stone or Clay; provided the Fabrick or Contrivance of the engine were the same: though it be not to be deny'd, that Brasse and Steel are more convenient materials to make clock-wheels of than Lead, or Wood. And to let you see, _Eleutherius_, that 'tis sometimes at least, upon the Texture of the small parts of a body, and not alwaies upon the presence, or recesse, or increase, or Decrement of any one of its Principle, that it may lose some such Qualities, and acquire some such others as are thought very strongly inherent to the bodies they Reside in. [Errata: in;] I will add to what may from my past discourse be refer'd to this purpose, this Notable Example, from my Own experience; That Lead may without any additament, and only by various applications of the Fire, lose its colour, and acquire sometimes a gray, sometimes a yellowish, sometimes a red, sometimes an _amethihstine_ [Transcriber's Note: amethistine] colour; and after having past through these, and perhaps divers others, again recover its leaden colour, and be made a bright body. That also this Lead, which is so flexible a metal, may be made as brittle as Glasse, and presently be brought to be again flexible and Malleable as before. And besides, that the same lead, which I find by _Microscopes_ to be one of the most opacous bodies in the World, may be reduced to a fine transparent glasse; whence yet it may returne to an opacous Nature again; and all this, as I said, without the addition of any extraneous body, and meerly by the manner and Method of exposing it to the Fire. But (sayes _Carneades_) after having already put you to so prolix a trouble, it is time for me to relieve you with a promise of putting speedily a period to it; And to make good that promise, I shall from all that I have hitherto discoursed with you, deduce but this one proposition by way of Corollary. [_That it may as yet be doubted, whether or no there be any determinate Number of Elements; Or, if you please, whether or no all compound bodies, do consist of the same number of Elementary ingredients or material Principles._] This being but an inference from the foregoing Discourse, it will not be requisite to insist at large on the proofs of it; But only to point at the chief of Them, and Referr You for Particulars to what has been already Delivered. In the First place then, from what has been so largely discours'd, it may appear, that the Experiments wont to be brought, whether by the common Peripateticks, or by the vulgar Chymists, to demonstrate that all mixt bodies are made up precisely either of the four Elements, or the three Hypostatical Principles, do not evince what they are alledg'd to prove. And as for the other common arguments, pretended to be drawn from Reason in favour of _Aristotelian Hypothesis_ (for the Chymists are wont to rely almost altogether upon Experiments) they are Commonly grounded upon such unreasonable or precarious Suppositions, that 'tis altogether as easie and as just for any man to reject them, as for those that take them for granted to assert them, being indeed all of them as indemonstrable as the conclusion to be inferr'd from them; and some of them so manifestly weak and prooflesse; that he must be a very courteous adversary, that can be willing to grant them; and as unskilful a one, that can be compelled to do so. In the next place, it may be considered, if what those Patriarchs of the _Spagyrists_, _Paracelsus_ and _Helmont_, do on divers occasions positively deliver, be true; namely that the _Alkahest_ does Resolve all mixt Bodies into other Principles than the fire, it must be decided which of the two resolutions (that made by the _Alkahest_, or that made by the fire) shall determine the number of the Elements, before we can be certain how many there are. And in the mean time, we may take notice in the last place, that as the distinct substances whereinto the _Alkahest_ divides bodies, are affirm'd to be differing in nature from those whereunto they are wont to be reduc'd by fire, and to be obtain'd from some bodies more in Number than from some others; since he tells us, he could totally reduce all sorts of Stones into Salt only, whereas of a coal he had two distinct Liquors.[29] So, although we should acquiesce in that resolution which is made by fire, we find not that all mixt bodies are thereby divided into the same number of Elements and Principles; some Concretes affordding more of them than others do; Nay and sometimes this or that Body affording a greater number of Differing substances by one way of management, than the same yields by another. And they that out of Gold, or Mercury, or Muscovy-glasse, will draw me as many distinct substances as I can separate from Vitriol, or from the juice of Grapes variously orderd, may teach me that which I shall very Thankfully learn. Nor does it appear more congruous to that variety that so much conduceth to the perfection of the Universe, that all elemented bodies be compounded of the same number of Elements, then it would be for a language, that all its words should consist of the same number of Letters. [Footnote 29: _Novi saxum & lapides omnes in merum salem suo saxo aut lapidi & æquiponderantem reducere absque omni prorsus sulphure aut Mercurio._ Helmont. pag. 409.] THE SCEPTICAL CHYMIST OR, _A Paradoxical Appendix to the Foregoing Treatise._ _The Sixth Part._ Here _Carneades_ Having Dispach't what he Thought Requisite to oppose against what the Chymists are wont to alledge for Proof of their three Principles, Paus'd awhile, and look'd about him, to discover whether it were Time for him and his Friend to Rejoyne the Rest of the Company. But _Eleutherius_ perceiving nothing yet to forbid Them to Prosecute their Discourse a little further, said to his Friend, (who had likewise taken Notice of the same thing) I halfe expected, _Carneades_, that after you had so freely declar'd Your doubting, whether there be any Determinate Number of Elements, You would have proceeded to question whether there be any Elements at all. And I confess it will be a Trouble to me if You defeat me of my Expectation; especially since you see the leasure we have allow'd us may probably suffice to examine that Paradox; because you have so largly Deduc'd already many Things pertinent to it, that you need but intimate how you would have them Apply'd, and what you would inferr from them. _Carneades_ having in Vain represented that their leasure could be but very short, that he had already prated very long, that he was unprepared to maintain so great and so invidious a Paradox, was at length prevail'd with to tell his Friend; Since, _Eleutherius_, you will have me Discourse _Ex Tempore_ of the Paradox you mention, I am content, (though more perhaps to express my Obedience, then my Opinion) to tell you that (supposing the Truth of _Helmonts_ and _Paracelsus's_ Alkahestical Experiments, if I may so call them) though it may seem extravagant, yet it is not absurd to doubt, whether, for ought has been prov'd, there be a necessity to admit any Elements, or Hypostatical Principles, at all. And, as formerly, so now, to avoid the needless trouble of Disputing severally with the _Aristotelians_ and the Chymists, I will address my self to oppose them I have last nam'd, Because their Doctrine about the Elements is more applauded by the Moderns, as pretending highly to be grounded upon Experience. And, to deal not only fairly but favourably with them, I will allow them to take in Earth and Water to their other Principles. Which I consent to, the rather that my Discourse may the better reach the Tenents of the Peripateticks; who cannot plead for any so probably as for those two Elements; that of fire above the Air being Generally by Judicious Men exploded as an Imaginary thing; And the Air not concurring to compose Mixt Bodies as one of their Elements, but only lodging in their pores, or Rather replenishing, by reason of its Weight and Fluidity, all those Cavities of bodies here below, whether compounded or not, that are big enough to admit it, and are not fill'd up with any grosser substance. And, to prevent mistakes, I must advertize You, that I now mean by Elements, as those Chymists that speak plainest do by their Principles, certain Primitive and Simple, or perfectly unmingled bodies; which not being made of any other bodies, or of one another, are the Ingredients of which all those call'd perfectly mixt Bodies are immediately compounded, and into which they are ultimately resolved: now whether there be any one such body to be constantly met with in all, and each, of those that are said to be Elemented bodies, is the thing I now question. By this State of the controversie you will, I suppose, Guess, that I need not be so absur'd [Errata: absurd] as to deny that there are such bodies as Earth, and Water, and Quicksilver, and Sulphur: But I look upon Earth and Water, as component parts of the Universe, or rather of the Terrestrial Globe, not of all mixt bodies. And though I will not peremptorily deny that there may sometimes either a running Mercury, or a Combustible Substance be obtain'd from a Mineral, or even a Metal; yet I need not Concede either of them to be an Element in the sence above declar'd; as I shall have occasion to shew you by and by. To give you then a brief account of the grounds I intend to proceed upon, I must tell you, that in matters of Philosophy, this seems to me a sufficient reason to doubt of a known and important proposition, that the Truth of it is not yet by any competent proof made to appear. And congruously herunto, if I shew that the grounds upon which men are perswaded that there are Elements are unable to satisfie a considering man, I suppose my doubts will appear rational. Now the Considerations that induce men to think that there are Elements, may be conveniently enough referr'd to two heads. Namely, the one, that it is necessary that Nature make use of Elements to constitute the bodies that are reputed Mixt. And the other, That the Resolution of such bodies manifests that nature had compounded them of Elementary ones. In reference to the former of these Considerations, there are two or three things that I have to Represent. And I will begin with reminding you of the Experiments I not long since related to you concerning the growth of pompions, mint, and other vegetables, out of fair water. For by those experiments its seems evident, that Water may be Transmuted into all the other Elements; from whence it may be inferr'd, both, That 'tis not every Thing Chymists will call Salt, Sulphur, or Spirit, that needs alwayes be a Primordiate and Ingenerable body. And that Nature may contex a Plant (though that be a perfectly mixt Concrete) without having all the Elements previously presented to her to compound it of. And, if you will allow the relation I mention'd out of _Mounsieur De Rochas_ to be True; then may not only plants, but Animals and Minerals too, be produced out of Water, And however there is little doubt to be made, but that the plants my tryals afforded me as they were like in so many other respects to the rest of the plants of the same Denomination; so they would, in case I had reduc'd them to putrefaction, have likewise produc'd Wormes or other insects, as well as the resembling Vegetables are wont to do; so that Water may, by Various Seminal Principles, be successively Transmuted into both plants and Animals. And if we consider that not only Men, but even sucking Children are, but too often, Tormented with Solid Stones, but that divers sorts of Beasts themselves, (whatever _Helmont_ against Experience think to the contrary) may be Troubled with great and Heavy stones in their Kidneys and Bladders, though they Feed but upon Grass and other Vegetables, that are perhaps but Disguised Water, it will not seem improbable that even some Concretes of a mineral Nature, may Likewise be form'd of Water. We may further Take notice, that as a Plant may be nourisht, and consequently may Consist of Common water; so may both plants and Animals, (perhaps even from their Seminal Rudiments) consist of compound Bodies, without having any thing meerly Elementary brought them by nature to be compounded by them: This is evident in divers men, who whilst they were Infants were fed only with Milk, afterwards Live altogether upon Flesh, Fish, wine, and other perfectly mixt Bodies. It may be seen also in sheep, who on some of our English Downs or Plains, grow very fat by feeding upon the grasse, without scarce drinking at all. And yet more manifestly in the magots that breed and grow up to their full bignesse within the pulps of Apples, Pears, or the like Fruit. We see also, that Dungs that abound with a mixt Salt give a much more speedy increment to corn and other Vegetables than Water alone would do: And it hath been assur'd me, by a man experienc'd in such matters, that sometimes when to bring up roots very early, the Mould they were planted in was made over-rich, the very substance of the Plant has tasted of the Dung. And let us also consider a Graft of one kind of Fruit upon the upper bough of a Tree of another kind. As for instance, the Ciens of a Pear upon a White-thorne; for there the ascending Liquor is already alter'd, either by the root, or in its ascent by the bark, or both wayes, and becomes a new mixt body: as may appear by the differing qualities to be met with in the saps of several trees; as particularly, the medicinal vertue of the Birch-Water (which I have sometimes drunk upon _Helmonts_ great and not undeserved commendation) Now the graft, being fasten'd to the stock must necessarily nourish its self, and produce its Fruit, only out of this compound Juice prepared for it by the Stock, being unable to come at any other aliment. And if we consider, how much of the Vegetable he feeds upon may (as we noted above) remain in an Animal; we may easily suppose, That the blood of that Animal who Feeds upon this, though it be a Well constituted Liquor, and have all the differing Corpuscles that make it up kept in order by one præsiding form, may be a strangely Decompounded Body, many of its parts being themselves decompounded. So little is it Necessary that even in the mixtures which nature her self makes in Animal and Vegetable Bodies, she should have pure Elements at hand to make her compositions of. Having said thus much touching the constitution of Plants and Animals, I might perhaps be able to say as much touching that of Minerals, and even Metalls, if it were as easy for us to make experiment in Order to the production of these, as of those. But the growth or increment of Minerals being usually a work of excessively long time, and for the most part perform'd in the bowels of the Earth, where we cannot see it, I must instead of Experiments make use, on this occasion, of Observations. That stones were not all made at once, but that are some of them now adayes generated, may (though it be deny'd by some) be fully prov'd by several examples, of which I shall now scarce alledg any other, then that famous place in _France_ known by the name of _Les Caves Gentieres_ [Errata: Goutieres], where the Water falling from the upper Parts of the cave to the ground does presently there condense into little stones, of such figures as the drops, falling either severally or upon one another, and coagulating presently into stone, chance to exhibit. Of these stones some Ingenuous Friends of ours, that went a while since to visit that place, did me the favour to present me with some that they brought thence. And I remember that both that sober Relator of his Voyages, _Van Linschoten_, and another good Author, inform us that in the Diamond Mines (as they call them) in the _East-Indies_, when having dig'd the Earth, though to no great depth, they find Diamonds and take them quite away; Yet in a very few years they find in the same place new Diamonds produc'd there since. From both which Relations, especially the first, it seems probable that Nature does not alwayes stay for divers Elementary Bodies, when she is to produce stones. And as for Metals themselves, Authors of good note assure us, that even they were not in the beginning produc'd at once altogether, but have been observ'd to grow; so that what was not a Mineral or Metal before became one afterwards. Of this it were easie to alledg many testimonies of professed Chymists. But that they may have the greater authority, I shall rather present you with a few borrowed from more unsuspected writers. _Sulphuris Mineram_ (as the inquisitive _P. Fallopius_ notes) _quæ nutrix est caloris subterranei fabri seu Archæi fontium & mineralium, Infra terram citissime renasci testantur Historiæ Metallicæ. Sunt enim loca e quibus si hoc anno sulphur effossum fuerit; intermissa fossione per quadriennium redeunt fossores & omnia sulphure, ut autea [Errata: antea], rursus inveniunt plena._ _Pliny_ Relates, _In Italiæ Insula Ilva, gigni ferri metallum._ Strabo _multo expressius; effossum ibi metallum semper regenerari. Nam si effossio spatio centum annorum intermittebatur, & iterum illuc revertebantur, fossores reperisse maximam copiam ferri regeneratam._ Which history not only is countenanced by _Fallopius_, from the Incom which the Iron of that Island yielded the Duke of _Florence_ in his time; but is mention'd more expressely to our purpose, by the Learned _Cesalpinus_. _Vena_ (sayes he) _ferri copiosissima est in Italia; ob eam nobilitata Ilva Tirrheni maris Insula incredibili copia, etiam nostris temporibus eam gignens: Nam terra quæ eruitur dum vena effoditur tota, procedente tempore in venam convertitur._ Which last clause is therefore very notable, because from thence we may deduce, that earth, by a Metalline plastick principle latent in it, may be in processe of time chang'd into a metal. And even _Agricola_ himself, though the Chymists complain of him as their adversary, acknowledges thus much and more; by telling us that at a Town called _Saga_ in _Germany_,[30] they dig up Iron in the Fields, by sinking ditches two foot deep; And adding, that within the space of ten years the Ditches are digged again for Iron since produced, As the same Metal is wont to be obtain'd in _Elva_. Also concerning Lead, not to mention what even _Galen_ notes, that it will increase both in bulk and Weight if it be long kept in Vaults or Sellars, where the Air is gross and thick, as he collects from the smelling of those pieces of Lead that were imploy'd to fasten together the parts of old Statues. Not to mention this, I say, _Boccacius Certaldus_, as I find him Quoted by a Diligent Writer, has this Passage touching the Growth of Lead. _Fessularum mons_ (sayes he) _in Hetruria, Florentiæ civitati imminens, lapides plumbarios habet; qui si excidantur, brevi temporis spatio, novis incrementis instaurantur; ut_ (annexes my Author) _tradit Boccacius Certaldus, qui id compotissimum [Errata: compertissimum] esse scribit. Nihil hoc novi est; sed de eadem Plinius, lib. 34. Hist. Natur. cap. 17. dudum prodidit, Inquiens, mirum in his solis plumbi metallis, quod derelicta fertilius reviviscunt. In plumbariis secundo Lapide ab Amberga dictis ad Asylum recrementa congesta in cumulos, exposita solibus pluviisque paucis annis, redunt suum metallum cum fenore._ I might Add to these, continues _Carneades_, many things that I have met with concerning the Generation of Gold and Silver. But, for fear of wanting time, I shall mention but two or three Narratives. The First you may find Recorded by _Gerhardus_ the Physick Professor, in these Words. _In valle_ (sayes he) _Joachimaca [Errata: Joachimica] argentum gramini [Errata: graminis] modo & more e Lapidibus mineræ velut e radice excrevisse digiti Longitudine, testis est Dr. Schreterus, qui ejusmodi venas aspectu jucundas & admirabiles Domi sua aliis sæpe monstravit & Donavit. Item Aqua cærulea Inventa est Annebergæ, ubi argentum erat adhuc in primo ente, quæ coagulata redacta est in calcem fixi & boni argenti._ [Footnote 30: _In Lygiis, ad Sagam opidum; in pratis eruitur ferrum, fossis ad altitudinem bipedaneam actis. Id decennio renatum denuo foditur non aliter ac Ilvæ ferrum._] The other two Relations I have not met with in Latine Authours, and yet they are both very memorable in themselves, and as pertinent to our present purpose. The first I meet with in the Commentary of _Johannes Valehius_ upon the _Kleine Baur_, In which that Industrious Chymist Relates, with many circumstances, that at a Mine-Town (If I may so English the German _Bergstat_) eight miles or Leagues distant from _Strasburg_ call'd _Mariakirch_, a Workman came to the Overseer, and desired employment; but he telling him that there was not any of the best sort at present for him, added that till he could be preferr'd to some such, he might in the mean time, to avoid idleness, work in a Grove or Mine-pit thereabouts, which at that time was little esteem'd. This Workman after some weeks Labour, had by a Crack appearing in the Stone upon a Stroak given near the wall, an Invitation Given him to Work his Way through, which as soon as he had done, his Eyes were saluted by a mighty stone or Lump which stood in the middle of the Cleft (that had a hollow place behind it) upright, and in shew like an armed-man; but consisted of pure fine Silver having no Vein or Ore by it, or any other Additament, but stood there free, having only underfoot something like a burnt matter; and yet this one Lump held in Weight above a 1000 marks, which, according to the Dutch, Account [Errata: Dutch account] makes 500 pound weight of fine silver. From which and other Circumstances my Author gathers; That by the warmth of the place, the Noble Metalline Spirits, (Sulphureous and Mercurial) were carri'd from the neighbouring Galleries or Vaults, through other smaller Cracks and Clefts, into that Cavity, and there collected as in a close Chamber or Cellar; whereinto when they were gotten, they did in process of time settle into the forementioned precious mass of Metal. The other Germane Relation is of That great Traveller and Laborious Chymist _Johannes_ (not _Georgus_) _Agricola_; who in his notes upon what _Poppius_ has written of Antimony, Relates, that when he was among the _Hungarian_ Mines in the deep Groves, he observ'd that there would often arise in them a warm Steam (not of that malignant sort which the Germains call _Shwadt_, which (sayes he) is a meer poyson, and often suffocates the Diggers [Errata: diggers)], which fasten'd it self to the Walls; and that coming again to review it after a couple of dayes, he discern'd that it was all very fast, and glistering; whereupon having collected it and Distill'd it _per Retortam_, he obtain'd from it a fine Spirit, adding, that the Mine-Men inform'd him, that this Steam or Damp of the English Mine [Errata: damp as the Englishmen also call it] (retaining the dutch Term) would at last have become a Metal, as Gold or Silver. I referr (sayes _Carneades_) to another Occasion, the Use that may be made of these Narratives towards the explicating the Nature of Metalls; and that of Fixtness, Malleableness, and some other Qualities conspicuous in them. And in the mean time, this I may at present deduce from these Observations, That 'tis not very probable, that, whensoever a Mineral, or even a Metall, is to be Generated in the Bowels of the Earth, Nature needs to have at hand both Salt, and Sulphur, and Mercury to Compound it of; for, not to urge that the two last Relations seem less to favour the Chymists than _Aristotle_, who would have Metals Generated of certain _Halitus_ or steams, the foremention'd Observations together, make it seem more Likely that the mineral Earths or those Metalline steams (wherewith probably such Earths are plentifully imbu'd) do contain in them some seminal Rudiment, or some thing Equivalent thereunto; by whose plastick power the rest of the matter, though perhaps Terrestrial and heavy, is in Tract of time fashion'd into this or That metalline Ore; almost as I formerly noted, that fair water was by the seminal Principle of Mint, Pompions, and other Vegetables, contriv'd into Bodies answerable to such Seeds. And that such Alterations of Terrestrial matter are not impossible, seems evident from that notable Practice of the Boylers of Salt-Petre, who unanimously observe, as well here in _England_ as in other Countries; That if an Earth pregnant with Nitre be depriv'd, by the affusion of water, of all its true and dissoluble Salt, yet the Earth will after some years yield them Salt-Petre again; For which reason some of the eminent and skillfullest of them keep it in heaps as a perpetual Mine of Salt Petre; whence it may appear, that the Seminal Principle of Nitre latent in the Earth does by degrees Transforme the neighbouring matter into a Nitrous Body; for though I deny that some Volatile Nitre may by such Earths be attracted (as they speak) out of the Air, yet that the innermost parts of such great heaps that lye so remote from the Air should borrow from it all the Nitre they abound with, is not probable, for other reasons besides the remoteness of the Air, though I have not the Leasure to mention them. And I remember, that a person of Great Credit, and well acquainted with the wayes of making Vitriol, affirm'd to me, that he had observ'd, that a kind of mineral which abounds in that Salt, being kept within Doors and not expos'd (as is usual) to the free Air and Rains, did of it self in no very long time turn into Vitriol, not only in the outward or superficial, but even in the internal and most Central parts. And I also remember, that I met with a certain kind of Merkasite that lay together in great Quantities under ground, which did, even in my chamber, in so few hours begin of it self to turne into Vitriol, that we need not distrust the newly recited narrative. But to return to what I was saying of Nitre; as Nature made this Salt-Petre out of the once almost and inodorous Earth it was bred in, and did not find a very stinking and corrosive Acid Liquor, and a sharp Alcalyzate Salt to compound it of, though these be the Bodies into which the Fire dissolves it; so it were not necessary that Nature should make up all Metals and other Minerals of Pre-existent Salt, and Sulphur, and Mercury, though such Bodies might by Fire be obtained from it. Which one consideration duly weigh'd is very considerable in the present controversy: And to this agree well the Relations of our two German Chymists; for besides that it cannot be convincingly prov'd, it is not so much as likely that so languid and moderate a heat as that within the Mines, should carry up to so great a heat [Errata: height], though in the forme of fumes, Salt, Sulphur and Mercury; since we find in our Distillations, that it requires a considerable Degree of Fire to raise so much as to the height of one foot not only Salt, but even Mercury it self, in close Vessels. And if it be objected, that it seems by the stink that is sometimes observ'd when Lightening falls down here below, that sulphureous steams may ascend very high without any extraordinary Degree of heat; It may be answer'd, among other things, that the Sulphur of Silver is by Chymists said to be a fixt Sulphur, though not altogether so well Digested as that of Gold. But, proceeds _Carneades_, If it had not been to afford You some hints concerning the Origine of Metals, I need not have deduc'd any thing from these Observations; It not being necessary to the Validity of my Argument that my Deductions from them should be irrefragable, because my Adversaries the _Aristotelians_ and Vulgar Chymists do not, I presume, know any better then I, _a priori_, of what ingredients Nature compounds Metals and Minerals. For their Argument to prove that those Bodies are made up of such Principles, is drawn _a posteriori_; I mean from this, that upon the _Analysis_ of Mineral bodies they are resolv'd into those differing substances. That we may therefore examine this Argument, Let us proceed to consider what can be alledg'd in behalf of the Elements from the Resolutions of Bodies by the fire; which you remember was the second Tophick [Transcriber's Note: Topick] whence I told you the Arguments of my Adversaries were desum'd. And that I may first dispatch what I have to say concerning Minerals, I will begin the remaining part of my discourse with considering how the fire divides them. And first, I have partly noted above, that though Chymists pretend from some to draw salt, from others running Mercury, and from others a Sulphur; Yet they have not hitherto taught us by any way in us [Errata: use] among them to separate any one principle, whether Salt, Sulphur, or Mercury, from all sorts of Minerals without exception. And thence I may be allow'd to conclude that there is not any of the Elements that is an Ingredient of all Bodies, since there are some of which it is not so. In the next place, supposing that either Sulphur or Mercury were obtainable from all sorts of Minerals. Yet still this Sulphur or Mercury would be but a compounded, not an Elementary body, as I told you already on another occasion. And certainly he that takes notice of the wonderful Operations of Quicksilver, whether it be common, or drawn from Mineral Bodies, can scarce be so inconsiderate as to think it of the very same nature with that immature and fugitive substance which in Vegetables and Animals Chymists have been pleas'd to call their Mercury. So that when Mercury is got by the help of the fire out of a metal or other Mineral Body, if we will not suppose that it was not pre-existent in it, but produc'd by the action of the fire upon the Concrete, we may at least suppose this Quicksilver to have been a perfect Body of its own kind (though perhaps lesse heterogeneous then more secundary mixts) which happen'd to be mingl'd _per minima_, and coagulated with the other substances, whereof the Metal or Mineral consisted. As may be exemplyfied partly by Native Vermillion wherein the Quicksilver and Sulphur being exquisitely blended both with one another, and that other course Mineral stuff (what ever it be) that harbours them, make up a red body differing enough from both; and yet from which part of the Quicksilver, and of the Sulphur, may be easily enough obtain'd; Partly by those Mines wherein nature has so curiously incorporated Silver with Lead, that 'tis extreamly difficult, and yet possible, to separate the former out of the Latter. [Errata: latter;] And partly too by native Vitriol, wherein the Metalline Corpuscles are by skill and industry separable from the saline ones, though they be so con-coagulated with them, that the whole Concrete is reckon'd among Salts. And here I further observe, that I never could see any Earth or Water, properly so call'd, separated from either Gold or Silver (to name now no other Metalline Bodies) and therefore to retort the argument upon my Adversaries, I may conclude, that since there are some bodies in which, for ought appears, there is neither Earth nor Water. [Errata: Water;] I may be allow'd to conclude that neither of those two is an Universal Ingredient of all those Bodies that are counted perfectly mixt, which I desire you would remember against Anon. It may indeed be objected, that the reason why from Gold or Silver we cannot separate any moisture, is, because that when it is melted out of the Oare, the vehement Fire requisite to its Fusion forc'd away all the aqueous and fugitive moisture; and the like fire may do from the materials of Glass. To which I shall Answer, that I Remember I read not long since in the Learned _Josephus Acosta_,[31] who relates it upon his own observation; that in _America_, (where he long lived) there is a kind of Silver which the _Indians_ call _Papas_, and sometimes (sayes he) they find pieces very fine and pure like to small round roots, the which is rare in that metal, but usuall in Gold; Concerning which metal he tells us, that besides this they find some which they call Gold in grains, which he tells us are small morsels of Gold that they find whole without mixture of any other metal, which hath no need of melting or Refining in the fire. [Footnote 31: _Acosta_ Natural and Moral history of the Indies, L. 3. c. 5, p. 212.] I remember that a very skilful and credible person affirmed to me, that being in the _Hungarian_ mines he had the good fortune to see a mineral that was there digg'd up, wherein pieces of Gold of the length, and also almost of the bigness of a humane Finger, grew in the Oar, as if they had been parts and Branches of Trees. And I have my self seen a Lump of whitish Mineral, that was brought as a Rarity to a Great and knowing Prince, wherein there grew here and there in the Stone, which looked like a kind of sparr, divers little Lumps of fine Gold, (for such I was assured that Tryal had manifested it to be) some of them Seeming to be about the Bigness of pease. But that is nothing to what our _Acosta_ subjoynes, which is indeed very memorable, namely, that of the morsels of Native and pure Gold, which we lately heard him mentioning he had now and then seen some that weighed many pounds;[32] to which I shall add, that I my self have seen a Lump of Oar not long since digged up, in whose stony part there grew, almost like Trees, divers parcels though not of Gold, yet of (what perhaps Mineralists will more wonder at) another Metal which seemed to be very pure or unmixt with any Heterogeneous Substances, and were some of them as big as my Finger, if not bigger. But upon Observations of this kind, though perhaps I could, yet I must not at present dwell any longer. [Footnote 32: See _Acosta_ in the fore-cited Place, and the passage of _Pliny_ quoted by him.] To proceed Therefore now (sayes _Carneades_) to the Consideration of the _Analysis_ of Vegetables, although my Tryals give me no cause to doubt but that out of most of them five differing Substances may be obtain'd by the fire, yet I think it will not be so easily Demonstrated that these deserve to be call'd Elements in the Notion above explain'd. And before I descend to particulars, I shall repeat and premise this General Consideration, that these differing substances that are call'd Elements or Principles, differ not from each other as Metals, Plants and Animals, or as such Creatures as are immediately produc'd each by its peculiar Seed, and Constitutes a distinct propagable sort of Creatures in the Universe; but these are only Various Schemes of matter or Substances that differ from each other, but in consistence (as Running Mercury and the same Metal congeal'd by the Vapor of Lead) and some very few other accidents, as Tast, or Smel, or Inflamability, or the want of them. So that by a change of Texture not impossible to be wrought by the Fire and other Agents that have the Faculty not only to dissociate the smal parts of Bodies, but afterwards to connect them after a new manner, the same parcell of matter may acquire or lose such accidents as may suffice to Denominate it Salt, or Sulphur, or Earth. If I were fully to clear to you my apprehensions concerning this matter, I should perhaps be obliged to acquaint you with divers of the Conjectures (for I must yet call them no more) I have had Concerning the Principles of things purely Corporeal: For though because I seem not satisfi'd with the Vulgar Doctrines, either of the Peripatetick or Paracelsian Schools, many of those that know me, (and perhaps, among Them, _Eleutherius_ himself) have thought me wedded to the Epicurean _Hypotheses_, (as others have mistaken me for an _Helmontian_;) yet if you knew how little Conversant I have been with _Epicurean_ Authors, and how great a part of _Lucretius_ himself I never yet had the Curiosity to read, you would perchance be of another mind; especially if I were to entertain you at large, I say not, of my present Notions; but of my former thoughts concerning the Principles of things. But, as I said above, fully to clear my Apprehensions would require a Longer Discourse than we can now have. For, I should tell you that I have sometimes thought it not unfit, that to the Principles which may be assign'd to things, as the World is now Constituted, we should, if we consider the Great Mass of matter as it was whilst the Universe was in making, add another, which may Conveniently enough be call'd an Architectonick Principle or power; by which I mean those Various Determinations, and that Skilfull Guidance of the motions of the small parts of the Universal matter by the most wise Author of things, which were necessary at the beginning to turn that confus'd _Chaos_ into this Orderly and beautifull World; and Especially, to contrive the Bodies of Animals and Plants, and the Seeds of those things whose kinds were to be propagated. For I confess I cannot well Conceive, how from matter, Barely put into Motion, and then left to it self, there could Emerge such Curious Fabricks as the Bodies of men and perfect Animals, and such yet more admirably Contriv'd parcels of matter, as the seeds of living Creatures. I should likewise tell you upon what grounds, and in what sence, I suspected the Principles of the World, as it now is, to be Three, _Matter_, _Motion_ and _Rest_. I say, _as the World now is_, because the present Fabrick of the Universe, and especially the seeds of things, together with the establisht Course of Nature, is a Requisite or Condition, upon whose account divers things may be made out by our three Principles, which otherwise would be very hard, if possible, to explicate. I should moreover declare in general (for I pretend not to be able to do it otherwise) not only why I Conceive that Colours, Odors, Tasts, Fluidness and Solidity, and those other qualities that Diversifie and Denominate Bodies may Intelligibly be Deduced from these three; _but how two of the Three_ Epicurean Principles (which, I need not tell, you [Transcriber's Note: tell you,] are Magnitude, Figure and Weight) are Themselves Deducible from Matter and Motion; since the Latter of these Variously Agitating, and, as it were, Distracting the Former, must needs disjoyne its parts; which being Actually separated must Each of them necessarily both be of some Size, and obtain some shape or other. Nor did I add to our Principles the _Aristotelean Privation_, partly for other Reasons, which I must not now stay to insist on; and partly because it seems to be rather an Antecedent, or a _Terminus a quo_, then a True Principle, as the starting-Post is none of the Horses Legs or Limbs. I should also explain why and how I made rest [Errata: Rest] to be, though not so considerable a Principle of things, as Motion, yet a Principle of them; partly because it is (for ought we know [Errata: know)] as Ancient at least as it, and depends not upon Motion, nor any other quality of matter; and partly, because it may enable the Body in which it happens to be, both to continue in a State of Rest till some external force put it out of that state, and to concur to the production of divers Changes in the bodies that hit against it, by either quite stopping or lessning their Motion (whilst the body formerly at Rest Receives all or part of it into it self) or else by giving a new Byass, or some other Modification, to Motion, that is, To the Grand and Primary instrument whereby Nature produces all the Changes and other Qualities that are to be met with in the World. I should likewise, after all this, explain to you how, although Matter, Motion and Rest, seem'd to me to be the Catholick Principles of the Universe, I thought the Principles of Particular bodies might be Commodiously enough reduc'd to two, namely _Matter_, and (what Comprehends the two other, and their effects) the result or Aggregate [Errata: Aggregate or complex] of those Accidents, which are the Motion or Rest, (for in some Bodies both are not to be found) the Bigness, Figure, Texture) [Errata: delete )] and the thence resulting Qualities of the small parts) [Errata: delete )] which are necessary to intitle the Body whereto they belong to this or that Peculiar Denomination; and discriminating it from others to appropriate it to a Determinate Kind of Things, as [Errata: (as] Yellowness, Fixtness, such a Degree of Weight, and of Ductility, do make the Portion of matter wherein they Concur, to be reckon'd among perfect metals, and obtain the name of Gold.) Which [Errata: This] Aggregate or result of Accidents you may, if You please, call either _Structure_ or Texture. [Errata: no paragraph break] Though [Errata: (Though] indeed, that do not so properly Comprehend the motion of the constituent parts especially in case some of them be Fluid [Errata: Fluid)], or what other appellation shall appear most Expressive. Or if, retaining the Vulgar Terme, You will call it the _Forme_ of the thing it denominates, I shall not much oppose it; Provided the word be interpreted to mean but what I have express'd, and not a Scholastick _Substantial Forme_, which so many intelligent men profess to be to them altogether Un-intelligible. But, sayes _Carneades_, if you remember that 'tis a Sceptick speaks to you, and that 'tis not so much my present Talk to make assertions as to suggest doubts, I hope you will look upon what I have propos'd, rather as a Narrative of my former conjectures touching the principles of things, then as a Resolute Declaration of my present opinions of them; especially since although they cannot but appear Very much to their Disadvantage, If you Consider Them as they are propos'd without those Reasons and Explanations by which I could perhaps make them appear much lesse extravagant; yet I want time to offer you what may be alledg'd to clear and countenance these notions; my design in mentioning them unto you at present being, _partly_, to bring some Light and Confirmation to divers passages of my discourse to you; _partly_ to shew you, that I do not (as you seem to have suspected) embrace all _Epicurus_ his principles; but Dissent from him in some main things, as well as from _Aristotle_ and the Chymists, in others; & _partly_ also, or rather chiefly, to intimate to you the grounds upon which I likewise differ from _Helmont_ in this, that whereas he ascribes almost all things, and even diseases themselves, to their determinate Seeds; I am of opinion, that besides the peculiar Fabricks of the Bodies of Plants and Animals (and perhaps also of some Metals and Minerals) which I take to be the Effects of seminal principles, there are many other bodies in nature which have and deserve distinct and Proper names, but yet do but result from such contextures of the matter they are made of, as may without determinate seeds be effected by heat, cold, artificial mixtures and compositions, and divers other causes which sometimes nature imployes of her own accord; and oftentimes man by his power and skill makes use of to fashion the matter according to his Intentions. This may be exemplified both in the productions of Nature, and in those of Art; of the first sort I might name multitudes; but to shew how sleight a variation of Textures without addition of new ingredients may procure a parcel of matter divers names, and make it be Lookt upon as Different Things; I shall invite you to observe with me, That Clouds, Rain, Hail, Snow, Froth, and Ice, may be but water, having its parts varyed as to their size and distance in respect of each other, and as to motion and rest. And among Artificial Productions we may take notice (to skip the Crystals of Tartar) of Glass, Regulus, Martis-Stellatus [Errata: Regulus Martis Stellatus], and particularly of the Sugar of Lead, which though made of that insipid Metal and sour salt of Vinager, has in it a sweetnesse surpassing that of common Sugar, and divers other qualities, which being not to be found in either of its two ingredients, must be confess'd to belong to the Concrete it self, upon the account of its Texture. This Consideration premis'd, it will be, I hope, the more easie to perswade you that the Fire may as well produce some new textures in a parcel of matter, as destroy the old. Wherefore hoping that you have not forgot the Arguments formerly imploy'd against the Doctrine of the _Tria prima_; namely that the Salt, Sulphur and Mercury, into which the Fire seems to resolve Vegetable and Animal Bodies, are yet compounded, not simple and Elementary Substances; And that (as appeared by the Experiment of Pompions) the _Tria prima_ may be made out of Water; hoping I say, that you remember These and the other Things that I formerly represented to the same purpose, I shall now add only, that if we doubt not the Truth of some of _Helmonts_ Relation [Errata: Relations], We may well doubt whether any of these Heterogeneities be (I say not pre-existent, so as to convene together, when a plant or Animal is to be constituted but) so much as in-existent in the Concrete whence they are obtain'd, when the Chymists [Errata: Chymist] first goes about to resolve it; For not to insist upon the un-inflamable Spirit of such Concretes, because that may be pretended to be but a mixture of Phlegme and Salt; the Oyle or Sulphur of Vegetables or Animals is, according to him, reducible by the help of Lixiviate Salts into Sope; as that Sope is by the help of repeated Distillations from a _Caput Mortuum_ of Chalk into insipid Water. And as for the saline substance that seems separable from mixt bodies; the same _Helmonts_ tryals[33] give us cause to think, That it may be a production of the Fire, which by transporting and otherwise altering the particles of the matter, does bring it to a Saline nature. [Footnote 33: _Omne autem Alcali addita pinguedine in aqueum liquorem, qui tandem mera & simplex aqua fit, reducitur, (ut videre est in Sapone, Lazurio lapide, &c.) quoties per adjuncta fixa semen Pinguedinis deponit._ Helmont.] For I know (sayes he, in the place formerly alledg'd to another purpose) a way to reduce all stones into a meer Salt of equal weight with the stone whence it was produc'd, and that without any of the least either Sulphur or Mercury; which asseveration of my Author would perhaps seem less incredible to You, if I durst acquaint You with all I could say upon that subject. And hence by the way you may also conclude that the Sulphur and Mercury, as they call them, that Chymists are wont to obtain from compound Bodies by the Fire, may possibly in many Cases be the productions of it; since if the same bodies had been wrought upon by the Agents employ'd by _Helmont_, they would have yielded neither Sulphur nor Mercury; and those portions of them which the Fire would have presented Us in the forme of Sulphureous and Mercurial Bodies would have, by _Helmonts_ method, been exhibited to us in the form of Salt. But though (sayes _Eleutherius_) You have alledg'd very plausible Arguments against the _tria Prima_, yet I see not how it will be possible for you to avoid acknowledging that Earth and Water are Elementary Ingredients, though not of Mineral Concretes, yet of all Animal and Vegetable Bodies; Since if any of these of what sort soever be committed to Distillation, there is regularly and constantly separated from it a phlegme or aqueous part and a _Caput Mortuum_ or Earth. I readily acknowledged (answers _Carneades_) it is not so easy to reject Water and Earth (and especially the former) as 'tis to reject the _Tria Prima_, from being the Elements of mixt Bodies; but 'tis not every difficult thing that is impossible. I consider then, as to Water, that the chief Qualities which make men give that name to any visible Substance, are, that it is Fluid or Liquid, and that it is insipid and inodorous. Now as for the tast of these qualities, I think you have never seen any of those separated substances that the Chymists call Phlegme which was perfectly devoyd both of Tast and Smell: and if you object, that yet it may be reasonably suppos'd, that since the whole Body is Liquid, the mass is nothing but Elementary Water faintly imbu'd with some of the Saline or Sulphureous parts of the same Concrete, which it retain'd with it upon its Separation from the Other Ingredients. To this I answer, That this Objection would not appear so stong [Transcriber's Note: strong] as it is plausible, if Chymists understood the Nature of Fluidity and Compactnesse; and that, as I formerly observ'd, to a Bodies being Fluid there is nothing necessary, but that it be divided into parts small enough; and that these parts be put into such a motion among themselves as to glide some this way and some that way, along each others Surfaces. So that, although a Concrete were never so dry, and had not any Water or other Liquor in-existent in it, yet such a Comminution of its parts may be made, by the fire or other Agents, as to turn a great portion of them into Liquor. Of this Truth I will give an instance, employ'd by our friend here present as one of the most conducive of his experiments to Illustrate the nature of Salts. If you Take, then, sea salt and melt it in the Fire to free it from the aqueous parts, and afterward distill it with a vehement Fire from burnt Clay, or any other, as dry a _Caput mortuum_ as you please, you will, as Chymists confess, [Errata: confesse (delete comma)] by teaching it drive over a good part of the Salt in the form of a Liquor. And to satisfy some ingenious men, That a great part of this Liquor was still true sea salt brought by the Operation of the Fire into Corpuscles so small, and perhaps so advantageously shap'd, as to be capable of the forme of a Fluid Body, He did in my presence poure to such spiritual salts a due proportion of the spirit (or salt and Phlegme) of Urine, whereby having evaporated the superfluous moisture, he soon obtain'd such another Concrete, both as to tast and smell, and easie sublimableness as common Salt _Armoniack_, which you know is made up of grosse and undistill'd sea salt united with the salts of Urine and of Soot, which two are very neer of kin to each other. And further, to manifest that the Corpuscles of sea salt and the Saline ones of Urine retain their several Natures in this Concrete, He mixt it with a convenient quantity of Salt of Tartar, and committing it to Distillation soon regain'd his spirit of Urine in a liquid form by its self, the Sea salt staying behind with the Salt of Tartar. Wherefore it is very possible that dry Bodies may by the Fire be reduc'd to Liquors without any separation of Elements, but barely by a certain kind of Dissipation and Comminution of the matter, whereby its parts are brought into a new state. And if it be still objected, that the Phlegme of mixt Bodies must be reputed water, because so weak a tast needs but a very small proportion of Salt to impart it; It may be reply'd, that for ought appears, common Salt and divers other bodies, though they be distill'd never so dry, and in never so close Vessels, will yield each of them pretty store of a Liquor, wherein though (as I lately noted) Saline Corpuscles abound, Yet there is besides a large proportion of Phlegme, as may easily be discovered by coagulating the Saline Corpuscles with any convenient Body; as I lately told you, our Friend coagulated part of the Spirit of Salt with Spirit of Urine: and as I have divers times separated a salt from Oyle of Vitriol it self (though a very ponderous Liquor and drawn from a saline body) by boyling it with a just quantity of Mercury, and then washing the newly coagulated salt from the Precipitate with fair Water. Now to what can we more probably ascribe this plenty of aqueous Substance afforded us by the Distillation of such bodies, than unto this, That among the various operations of the Fire upon the matter of a Concrete, divers particles of that matter are reduc'd to such a shape and bignesse as is requisite to compose such a Liquor as Chymists are wont to call Phlegme or Water. How I conjecture this change may be effected, 'tis neither necessary for me to tell you, nor possible to do so without a much longer discourse then were now seasonable. But I desire you would with me reflect upon what I formerly told you concerning the change of Quicksilver into Water; For that Water having but a very faint tast, if any whit more than divers of those liquors that Chymists referr to Phlegme; By that experiment it seems evident, that even a metalline body, and therefore much more such as are but Vegetable or Animal, may by a simple operation of the Fire be turn'd in great part into Water. And since those I dispute with are not yet able out of Gold, or Silver, or divers other Concretes to separate any thing like Water; I hope I may be allow'd to conclude against Them, that water it self is not an Universal and pre-existent Ingredient of Mixt Bodies. But as for those Chymists that, Supposing with me the Truth of what _Helmont_ relates of the _Alkahest's_ wonderful Effects, have a right to press me with his Authority concerning them, and to alledge that he could Transmute all reputedly mixt Bodies into insipid and meer Water; To those I shall represent, That though his Affirmations conclude strongly against the Vulgar Chymists (against whom I have not therefore scrupl'd to Employ Them) since they Evince that the Commonly reputed Principles or Ingredients of Things are not Permanent and indestructible, since they may be further reduc'd into Insipid Phlegme differing from them all; Yet till we can be allow'd to examine this Liquor, I think it not unreasonable to doubt whether it be not something else then meer Water. For I find not any other reason given by _Helmont_ of his Pronouncing it so, then that it is insipid. Now Sapour being an Accident or an Affection of matter that relates to our Tongue, Palate, and other Organs of Tast, it may very possibly be, that the small Parts of a Body may be of such a Size and Shape, as either by their extream Littleness, or by their slenderness, or by their Figure, to be unable to pierce into and make a perceptible Impression upon the Nerves or Membranous parts of the Organs of Tast, and what [Errata: yet] may be fit to work otherwise upon divers other Bodies than meer Water can, and consequently to Disclose it self to be of a Nature farr enough from Elementary. In Silke dyed Red or of any other Colour, whilst many Contiguous Threads makes up a skein, the Colour of the Silke is conspicuous; but if only a very few of them be lookt upon, the Colour will appear much fainter then before. But if You take out one simple Thread, you shall not easily be able to discern any Colour at all; So subtile an Object having not the Force to make upon the Optick Nerve an Impression great enough to be taken Notice of. It is also observ'd, that the best sort of Oyl-Olive is almost tastless, and yet I need not tell you how exceedingly distant in Nature Oyle is from Water. The Liquor into which I told you, upon the Relation of _Lully_, and [Errata: an] Eye-witness that Mercury might be Transmuted, has sometimes but a very Languid, if any Tast, and yet its Operations even upon some Mineral Bodies are very peculiar. Quicksilver it self also, though the Corpuscles it consists of be so very small as to get into the Pores of that Closest and compactest of Bodies, Gold, is yet (you know) altogether Tastless. And our _Helmont_ several times tells us, that fair Water wherein a little Quantity f [Errata: of] Quicksilver has lain for some time, though it acquire no certain Tast or other sensible Quality from the Quicksilver; Yet it has a power to destroy wormes in humane Bodies; which he does much, but not causelessly extoll. And I remember, a great Lady, that had been Eminent for her Beauty in Divers Courts, confess'd to me, that this insipid Liquor was of all innocent washes for the Face the best that she ever met with. And here let me conclude my Discourse, concerning such waters or Liquors as I have hitherto been examining, with these two Considerations. Whereof the first is, That by reason of our being wont to drink nothing but Wine, Bear, Cyder, or other strongly tasted Liquors, there may be in several of these Liquors, that are wont to pass for insipid Phlegme, very peculiar and Distinct, Tasts [Errata: distinct Tasts] though unheeded (and perhaps not to be perceiv'd) by Us. For to omit what Naturalists affirm of Apes, (and which probably may be true of divers other Animals) that they have a more exquisite palate than Men: among Men themselves, those that are wont to drink nothing but water may (as I have try'd in my self) Discern very sensibly a great Difference of Tasts in several waters, which one un-accustomed to drink water would take to be all alike insipid. And this is the _first_ of my two Considerations; the _Other_ is, That it is not impossible that the Corpuscles into which a body is dissipated by the Fire may by the Operation of the same fire have their figures so altered, or may be by associations with one another brought into little Masses of such a Size and Shape, as not to be fit to make sensible Impressions on the Tongue. And that you may not think such alterations impossible, be pleased to consider with me, that not only the sharpest Spirit of Vinager having dissolved as much Corall as it can, will Coagulate with it into a Substance, which though soluble in water, like salt, is incomparably less strongly Tasted then the Vinager was before; but (what is more considerable) though the Acid salts that are carried up with Quicksilver in the preparation of common sublimate are so sharp, that being moistened with water it will Corrode some of the Metals themselves; yet this Corrosive Sublimate being twice or thrice re-sublim'd with a full proportion of insipid Quicksilver, Constitutes (as you know) that Factitious Concrete, which the Chymists call _Mercurius dulcis_; not because it is sweet, but because the sharpness of the Corrosive Salts is so taken away by their Combination with the Mercurial Corpuscles, that the whole mixture when it is prepar'd is judg'd to be insipid. And thus (continues _Carneades_) having given you some Reasons why I refuse to admit Elementary water for a constant Ingredient of Mixt Bodies, It will be easie for me to give you an Account why I also reject Earth. For first, it may well be suspected that many Substances pass among Chymists under the name of Earth, because, like it, they are Dry, and Heavy, and Fixt, which yet are very farr from an Elementary Nature. This you will not think improbable, If you recall to mind what I formerly told you concerning what Chymists call the Dead Earth of things, and especially touching the copper to be drawn from the _Caput Mortuum_ of Vitriol; And if also you allow me to subjoyn a casual but memorable Experiment made by _Johannes Agricola_ upon the _Terra Damnata_ of Brimstone. Our Author then tells us (in his notes upon _Popius_ [Transcriber's Note: Poppius],) that in the year 1621 he made an Oyle of Sulphur; the remaining _Fæces_ he reverberated in a moderate Fire fourteen dayes; afterwards he put them well luted up in a Wind Oven, and gave them a strong Fire for six hours, purposing to calcine the _Fæces_ to a perfect Whiteness, that he might make someting [Transcriber's Note: something] else out of them. But coming to break the pot, he found above but very little _Fæces_, and those Grey and not White; but beneath there lay a fine Red _Regulus_ which he first marvell'd at and knew not what to make of, being well assured that not the least thing, besides the _Fæces_ of the Sulphur, came into the pot; and that the Sulphur it self had only been dissolv'd in Linseed Oyle; this _Regulus_ he found heavy and malleable almost as Lead; having caus'd a Goldsmith to draw him a Wire of it, he found it to be of the Fairest copper, and so rightly colour'd, that a Jew of _Prague_ offer'd him a great price for it. And of this Metal he sayes he had 12 _loth_ (or six ounces) out of one pound of Ashes or _Fæces_. And this Story may well incline us to suspect that since the _Caput Mortuum_ of the Sulphur was kept so long in the fire before it was found to be any thing else then a _Terra damnata_, there may be divers other Residences of Bodies which are wont to pass only for the Terrestrial _Fæces_ of things, and therefore to be thrown away as soon as the Distillation or Calcination of the Body that yielded them is ended; which yet if they were long and Skilfully examin'd by the fire would appear to be differing from Elementary Earth. And I have taken notice of the unwarrantable forwardness of common Chymists to pronounce things useless _Fæces_, by observing how often they reject the _Caput Mortuum_ of Verdegrease; which is yet so farr from deserving that Name, that not only by strong fires and convenient Additaments it may in some hours be reduc'd into copper, but with a certain Flux Powder I sometimes make for Recreation, I have in two or three minutes obtain'd that Metal from it. To which I may add, that having for tryall sake kept Venetian Taclk [Errata: Talck] in no less a heat than that of a glass Furnace, I found after all the Brunt of the fire it had indur'd, the remaining Body though brittle and discolour'd, had not lost very much of its former Bulke, and seem'd still to be nearer of kin to Talck than to meer Earth. And I remember too, that a candid Mineralist, famous for his Skill in trying of Oars, requesting me one day to procure him a certain _American_ Mineral Earth of a _Virtuoso_, who he thought would not refuse me; I enquir'd of him why he seem'd so greedy of it: he confess'd to me that this Gentleman having brought that Earth to the publick Say-Masters; and they upon their being unable by any means to bring it to fusion or make it fly away, he (the Relator) had procur'd a little of it; and having try'd it with a peculiar Flux separated from it neer a third part of pure Gold; so great mistakes may be committed in hastily concluding things to be Uselesse Earth. Next, it may be suppos'd, That as in the Resolution of Bodies by the Fire some of the dissipated Parts may, by their various occursion occasion'd by the heat, be brought to stick together so closely as to constitute Corpuscles too heavy for the Fire to carry away; the aggregate of which Corpuscles is wont to be call'd Ashes or Earrh [Errata: Earth]; So other Agents may resolve the Concrete into Minute Parts, after so differing a manner as not to produce any _Caput mortuum_, or dry and heavy Body. As you may remember _Helmont_ above inform'd us, that with his great Dissolvent he divided a Coal into two liquid and volatile Bodies, æquiponderant to the Coal, without any dry or fixt Residence at all. And indeed, I see not why it should be necessary that all Agents that resolve Bodies into portions of differingly qualifi'd matter must work on them the same way, and divide them into just such parts, both for nature and Number, as the Fire dissipates them into. For since, as I noted before, the Bulk and shape of the small Parts of bodies, together with their Fitness and Unfitness to be easily put into Motion, may make the liquors or other substances such Corpuscles compose, as much to differ from each other as do some of the Chymical principles: Why may not something happen in this case, not unlike what is usuall in the grosser divisions of bodies by Mechanical Instruments? Where we see that some Tools reduce Wood, for Instance, into darts [Errata: parts] of several shapes, bignesse, and other qualities, as Hatchets and Wedges divide it into grosser parts; some more long and slender, as splinters; and some more thick and irregular, as chips; but all of considerable bulk; but Files and Saws makes a Comminution of it into Dust; which, as all the others, is of the more solid sort of parts; whereas others divide it into long and broad, but thin and flexible parts, as do _Planes_: And of this kind of parts it self there is also a variety according to the Difference of the Tools employ'd to work on the Wood; the shavings made by the _plane_ being in some things differing from those shives or thin and flexible pieces of wood that are obtain'd by _Borers_, and these from some others obtainable by other Tools. Some Chymical Examples applicable to this purpose I have elsewhere given you. To which I may add, that whereas in a mixture of Sulphur and Salt of Tartar well melted and incorporated together, the action of pure spirit of wine digested on it is to separate the sulphureous from the Alcalizate Parts, by dissolving the former and leaving the latter, the action of Wine (probably upon the score of its copious Phlegme) upon the same mixture is to divide it into Corpuscles consisting of both Alcalizate and Sulphureous Parts united. And if it be objected, that this is but a Factitious Concrete; I answer, that however the instance may serve to illustrate what I propos'd, if not to prove it; and that Nature her self doth in the bowels of the Earth make Decompounded Bodies, as we see in Vitriol, Cinnaber, and even in Sulphur it self; I will not urge that the Fire divides new Milk into five differing Substances; but Runnet and Acid Liquors divide it into a Coagulated matter and a thin Whey: And on the other side churning divides it into Butter and Butter-milk, which may either of them be yet reduc'd to other substances differing from the former. I will not presse this, I say, nor other instances of this Nature, because I cannot in few words answer what may be objected, that these Concretes sequestred without the help of the Fire may by it be further divided into Hypostatical Principles. But I will rather represent, That whereas the same spirit of Wine will dissociare [Transcriber's Note: dissociate] the Parts of Camphire, and make them one Liquor with it self; _Aqua Fortis_ will also disjoyn them, and put them into motion; but so as to keep them together, and yet alter their Texture into the form of an Oyle. I know also an uncompounded Liquor, that an extraordinary Chymist would not allow to be so much as Saline, which doth (as I have try'd) from Coral it self (as fixt as divers judicious writers assert that Concrete to be) not only obtain a noble Tincture, Without the Intervention of Nitre or other Salts; but will carry over the Tincture in Distillation. And if some reasons did not forbid me, I could now tell you of a _Menstruum_ I make my self, that doth more odly dissociate the parts of Minerals very fixt in the fire. So that it seems not incredible, that there may be some Agent or way of Operation found, whereby this or that Concrete, if not all Firme Bodies, may be resolv'd into parts so very minute and so unapt to stick close to one another, that none of them may be fixt enough to stay behind in a strong Fire, and to be incapable of Distillation; nor consequently to be look'd upon as Earth. But to return to _Helmont_, the same Authour somewhere supply's me with another Argument against the Earth's being such an Element as my Adversaries would have it. For he somewhere affirms, that he can reduce all the Terrestrial parts of mixt bodies into insipid water; whence we may argue against the Earths being one of their Elements, even from that Notion of Elements which you may remember _Philoponus_ recited out of _Aristotle_ himself, when he lately disputed for his Chymists against _Themistius_. And here we may on this occasion consider, that since a Body from which the Fire hath driven away its looser parts is wont to be look'd upon as Earth, upon the Account of its being endow'd with both these qualities, Tastlessenesse and Fixtnesse, (for Salt of Tartar though Fixt passes not among the Chymists for Earth, because 'tis strongly Tasted) if it be in the power of Natural Agents to deprive the _Caput Mortuum_ of a body of either of those two Qualities, or to give them both to a portion of matter that had them not both before, the Chymists will not easily define what part of a resolv'd Concrete is earth, and make out, that that Earth is a primary, simple, and indestructible Body. Now there are some cases wherein the more skilful of the Vulgar Chymists themselves pretend to be able, by repeated Cohobations and other fit Operations, to make the Distilled parts of a Concrete bring its own _Caput Mortuum_ over the Helme, in the forme of a Liquor; in which state being both Fluid and Volatile, you will easily believe it would not be taken for Earth. And indeed by a skilful, but not Vulgar, way of managing some Concretes, there may be more effected in this kind, then you perhaps would easily think. And on the other side, that either Earth may be Generated, or at least Bodies that did not before appear to be neer Totally Earth, may be so alter'd as to pass for it, seems very possible, if _Helmont_[34] have done that by Art which he mentions in several places; especially where He sayes that he knowes wayes whereby Sulphur once dissolv'd is all of it fix'd into a Terrestrial Powder; and the whole Bodie of Salt-Petre may be turn'd into Earth: Which last he elsewhere sayes is Done by the Odour only of a certain Sulphureous Fire. And in another place He mentions one way of doing this, which I cannot give you an Account of; because the Materialls I had prepar'd for Trying it, were by a Servants mistake unhappily thrown away. [Footnote 34: _Novi item modos quibus totum Salpetiæ [Errata: sal-petræ] in terram convertitur, totumque Sulphur semel dissolutum fixetur in Pulvearem terreum. Helmont in Compl. atque Mist. Elementor. Sect. 24._] And these Last Arguments may be confirm'd by the Experiment I have often had occasion to mention concerning the Mint I produc'd out of Water. And partly by an Observation of _Rondeletius_ concerning the Growth of Animals also, Nourish'd but by Water, which I remember'd not to mention, when I discours'd to you about the Production of things out of Water. This Diligent Writer then in his instructive book of fishes,[35] affirmes That his Wife kept a fish in a Glass of water without any other Food for three years; in which space it was constantly augmented, till at last it could not come out of the Place at which it was put in, and at length was too big for the glass it self though that were of a large capacity. And because there is no just reason to doubt, that this Fish, if Distill'd, would have yielded the like differing substances with other Animals: And However, because the Mint which I had out of water afforded me upon Distillation a good quantity of Charcoal, I think I may from thence inferr, that Earth it self may be produc'd out of Water; or if you please, that water may be transmuted into Earth; and consequently, that though it could be prov'd that Earth is an Ingredient actually in-existent in the Vegetable and Animal Bodies whence it may be obtain'd by Fire: yet it would not necessarily follow, that Earth as a pre-existent Element Does with other Principles convene to make up those Bodies whence it seems to have been separated. [Footnote 35: _Lib. 1. cap. 2._] After all is said (sayes _Eleutherius_) I have yet something to Object, that I cannot but think considerable, since _Carneades_ Himself alledg'd it as such; for, (continues _Eleutherius_ smiling) I must make bold to try whether you can as luckily answer your own Arguments, as those of your Antagonists, I mean (pursues he) that part of your Concessions, wherein you cannot but remember that you supply'd your Adversaries with an Example to prove that there may be Elementary Bodies, by taking Notice that Gold may be an Ingredient in a multitude of differing Mixtures, and yet retain its Nature, notwithstanding all that the Chymists by their Fires and Corrosive Waters are able to do to Destroy it. I sufficiently intimated to you at that time (replies _Carneades_) that I propos'd this Example, chiefly to shew you how Nature may be Conceived to have made Elements, not to prove that she actually has made any; And you know, that _a posse ad esse_ the Inference will not hold. But (continues _Carneades_) to answer more directly to the Objection drawn from Gold, I must tell You, that though I know very well that divers of the more sober Chymists have complain'd of the Vulgar Chymists, as of Mountebanks or Cheats, for pretending so vainly, as hitherto they have done, to Destroy Gold; Yet I know a certain _Menstruum_ (which our Friend has made, and intends shortly to communicate to the Ingenious) of so piercing and powerfull a Quality, That if notwithstanding much care, and some skill, I did not much deceive myself, I have with it really destroy'd even refin'd Gold, and brought it into a Metalline Body of another colour and Nature, as I found by Tryals purposely made. And if some just Considerations did not for the present Forbid it, I could Perchance here shew you by another Experiment or Two of my own Trying, that such _Menstruums_ may be made as to entice away and retain divers parts, from Bodies, which even the more Judicious and Experienc'd _Spagyrists_ have pronounc'd irresoluble by the Fire. Though (which I Desire you would mark) in neither of these Instances, the Gold or Precious Stones be Analys'd into any of the _Tria Prima_, but only Reduc'd to new Concretes. And indeed there is a great Disparity betwixt the Operations of the several Agents whereby the Parts of a Body come to be Dissipated. As if (for Instance) you dissolve the purer sort of Vitriol in common Water, the Liquor will swallow up the Mineral, and so Dissociate its Corpuscles, that they will seem to make up but one Liquor with those of the water; and yet each of these Corpuscles retains its Nature and Texture, and remains a Vitriolate and Compounded Body. But if the same Vitriol be exposed to a strong Fire, it will then be divided not only, as before, into smaller parts, but into Heterogeneous Substances, each of the Vitriolate Corpuscles that remain'd entire in the water, being it self upon the Destruction of its former Texture dissipated or divided into new Particles of differing Qualities. But Instances more fitly applicable to this purpose, I have already given you. Wherefore to return to what I told you about the Destruction of Gold, that Experiment Invites me to Represent to you, that Though there were either Saline, or Sulphureous, or Terrestrial Portions of Matter, whose parts were so small, so firmly united together, or of a figure so fit to make them cohere to one another, (as we see that in quicksilver broken into little Globes, the Parts brought to touch one another do immediately re-imbody) that neither the Fire, nor the usual Agents employ'd by Chymists, are pierceing enough to divide their Parts, so as to destroy the Texture of the single Corpuscles; yet it would not necessarily follow, That such Permanent Bodies were Elementary, since tis possible there may be Agents found in Nature, some of whose parts may be of such a Size and Figure as to take better Hold of some parts of these seemingly Elementary Corpuscles than these parts do of the rest, and Consequently may carry away such parts with them, and so dissolve the Texture of the Corpuscle by pulling its parts asunder. And if it be said, that at least we may this way discover the Elementary Ingredients of Things, by observing into what Substances these Corpuscles that were reputed pure are divided; I answer, that it is not necessary that such a Discovery should be practicable. For if the Particles of the Dissolvent do take such firme hold of those of the Dissolved Body, they must constitute together new Bodies, as well as Destroy the Old; and the strickt Union, which according to this _Hypothesis_ may well be suppos'd betwixt the Parts of the Emergent Body, will make it as Little to be Expected that they should be pull'd asunder, but by little Parts of matter, that to Divide them Associate Themselves and stick extreamly close to those of them which they sever from their Former Adherents. Besides that it is not impossible, that a Corpuscle suppos'd to be Elementary may have its Nature changed, without suffering a Divorce of its parts, barely by a new Texture Effected by some powerfull Agent; as I formerly told you, the same portion of matter may easily by the Operation of the Fire be turn'd at pleasure into the form of a Brittle and Transparent, or an Opacous and Malleable Body. And indeed, if you consider how farr the bare Change of Texture, whether made by Art or Nature (or rather by Nature with or without the assistance of man) can go in producing such New Qualities in the same parcel of matter, and how many inanimate Bodies (such as are all the Chymical productions of the Fire) we know are Denominated and Distinguish'd not so much by any Imaginary Substantial Form, as by the aggregate of these Qualities. If you consider these Things, I say, and that the varying of either the figure, or the Size, or the Motion, or the Situation, or Connexion of the Corpuscles whereof any of these Bodies is compos'd, may alter the Fabrick of it, you will possibly be invited to suspect, with me, that there is no great need that Nature should alwayes have Elements before hand, whereof to make such Bodies as we call mixts. And that it is not so easie as Chymists and others have hitherto Imagin'd, to discern, among the many differing Substances that may without any extraordinary skill be obtain'd from the same portion of matter, Which ought to be esteemed exclusively to all the rest, its in-existent Elementary Ingredients; much lesse to determine what Primogeneal and Simple Bodies convened together to compose it. To exemplify this, I shall add to what I have already on several occasions Represented, but this single instance. You may remember (_Eleutherius_) that I formerly intimated to you, that besides Mint and Pompions, I produced divers other Vegetables of very differing Natures out of Water. Wherefore you will not, I presume, think it incongruous to suppose, that when a slender Vine-slip is set into the ground, and takes root, there it may likewise receive its Nutriment from the water attracted out of the earth by his roots, or impell'd by the warm'th of the sun, or pressure of the ambient air into the pores of them. And this you will the more easily believe, if you ever observ'd what a strange quantity of Water will Drop out of a wound given to the Vine, in a convenient place, at a seasonable time in the Spring; and how little of Tast or Smell this _Aqua Vitis_, as Physitians call it, is endow'd with, notwithstanding what concoction or alteration it may receive in its passage through the Vine, to discriminate it from common Water. Supposing then this Liquor, at its first entrance into the roots of the Vine, to be common Water; Let Us a little consider how many various Substances may be obtain'd from it; though to do so, I must repeat somewhat that I had a former occasion to touch upon. And first, this Liquor being Digested in the plant, and assimilated by the several parts of it, is turn'd into the Wood, Bark, Pith, Leaves, &c. of the Vine; The same Liquor may be further dry'd, and fashon'd into Vine-buds, and these a while after are advanced unto sour Grapes, which express'd yield Verjuice, a Liquor very differing in several qualities both from Wine and other Liquors obtainable from the Vine: These soure Grapes being by the heat of the Sun concocted and ripened, turne to well tasted Grapes; These if dry'd in the Sun and Distill'd, afford a fætid Oyle and a piercing _Empyreumatical_ Spirit, but not a Vinous Spirit; These dry'd Grapes or Raisins boyl'd in a convenient proportion of Water make a sweet Liquor, which being betimes distill'd afford an Oyle and Spirit much like those of the Raisins themselves; If the juice of the Grapes be squeez'd out and put to Ferment, it first becomes a sweet and turbid Liquor, then grows lesse sweet and more clear, and then affords in common Distillations not an Oyle but a Spirit, which, though inflamable like Oyle, differs much from it, in that it is not fat, and that it will readily mingle with Water. I have likewise without Addition obtain'd in processe of time (and by an easie way which I am ready to teach you) from one of the noblest sorts of Wine, pretty store of pure and curiously figured Crystals of Salt, together with a great proportion of a Liquor as sweet almost as Hony; and these I obtained not from Must, but True and sprightly Wine; besides the Vinous Liquor, the fermented Juice of Grapes is partly turned into liquid Dregs or Leeze, and partly into that crust or dry feculancy that is commonly called Tartar; and this Tartar may by the Fire be easily divided into five differing substances; four of which are not Acid, and the other not so manifestly Acid as the Tartar it self; The same Vinous Juice after some time, especially if it be not carefully kept, Degenerates into that very sour Liquor called Vinegar; from which you may obtain by the Fire a Spirit and a Crystalline Salt differing enough from the Spirit and Lixiviate Salt of Tartar. And if you pour the Dephlegm'd Spirit of the Vinegar upon the Salt of Tartar, there will be produc'd such a Conflict or Ebullition as if there were scarce two more contrary Bodies in Nature; and oftentimes in this Vinager you may observe part of the matter to be turned into an innumerable company of swimming Animals, which our Friend having divers years ago observed, hath in one of his Papers taught us how to discover clearly without the help of a _Microscope_. Into all these various Schemes of matter, or differingly Qualifyed Bodies, besides divers others that I purposely forbear to mention, may the Water that is imbib'd by the roots of the Vine be brought, partly by the formative power of the plant, and partly by supervenient Agents or Causes, without the visible concurrence of any extraneous Ingredient; but if we be allowed to add to the Productions of this transmuted Water a few other substances, we may much encrease the Variety of such Bodies; although in this second sort of Productions, the Vinous parts seem scarce to retain any thing of the much more fix'd Bodies wherewith they were mingl'd; but only to have by their Mixture with them acquir'd such a Disposition, that in their recess occasion'd by the Fire they came to be alter'd as to shape, or Bigness, or both, and associated after a New manner. Thus, as I formerly told you, I did by the Addition of a _Caput Mortuum_ of Antimony, and some other Bodies unfit for Distillation, obtain from crude Tartar, store of a very Volatile and Crystalline Salt, differing very much in smell and other Qualities from the usuall salts of Tartar. But (sayes _Eleutherius_, interrupting him at these Words) if you have no restraint upon you, I would very gladly before you go any further, be more particularly inform'd, how you make this Volatile Salt, because (you know) that such Multitudes of Chymists have by a scarce imaginable Variety of wayes, attempted in Vain the Volatilization of the Salt of Tartar, that divers learned _Spagyrists_ speak as if it were impossible, to make any thing out of Tartar, that shall be Volatile in a Saline Forme, or as some of them express it, _in forma sicca_. I am very farr from thinking (answers _Carneades_) that the Salt I have mention'd is that which _Paracelsus_ and _Helmont_ mean when they speak of _Sal Tartari Volatile_, and ascribe such great things to it. For the Salt I speak of falls extreamly short of those Virtues, not seeming in its Tast, Smel, and other Obvious Qualities, to differ very much (though something it do differ) from Salt of Harts-horn, and other Volatile Salts drawn from the Distill'd Parts of Animals. Nor have I yet made Tryals enough to be sure, that it is a pure Salt of Tartar without participating any thing at all of the Nitre, or Antimony. But because it seems more likely to proceed from the Tartar, than from any of the other Ingredients, and because the Experiment is in it self not Ignoble, and Luciferous enough (as shewing a new way to produce a Volatile Salt contrary to Acid Salts from Bodies that otherwise are Observ'd to yield no such Liquor, but either only, or chiefly, Acid ones,) I shall, to satisfie you, acquaint you before any of my other Friends with the way I now use (for I have formerly us'd some others) to make it. Take then of good Antimony, Salt-Petre and Tartar, of each an equal weight, and of Quicklime Halfe the Weight of any one of them; let these be powder'd and well mingl'd; this done, you must have in readiness a long neck or Retort of Earth, which must be plac'd in a Furnace for a naked Fire, and have at the top of it a hole of a convenient Bigness, at which you may cast in the Mixture, and presently stop it up again; this Vessel being fitted with a large Receiver must have Fire made under it, till the bottom of the sides be red hot, and then you must cast in the above prepar'd Mixture, by about halfe a spoonfull (more or less) at a time, at the hole made for that purpose; which being nimbly stopt, the Fumes will pass into the Receiver and condense there into a Liquor, that being rectifi'd will be of a pure golden Colour, and carry up that colour to a great height; this Spirit abounds in the Salt I told you of, part of which may easily enough be separated by the way I use in such cases, which is, to put the Liquor into a glass Egg, or bolthead with a long and narrow Neck. For if this be plac'd a little inclining in hot sand, there will sublime up a fine Salt, which, as I told you, I find to be much of kin to the Volatile Salts of Animals: For like them it has a Saltish, not an Acid Salt; it hisses upon the Affusion of Spirit of Nitre, or Oyle of Vitriol; it precipitates Corals Dissolv'd in Spirit of Vinager; it turnes the blew Syrup of Violets immediately green; it presently turnes the Solution of Sublimate into a Milkie whiteness; and in summ, has divers Operations like those that I have observ'd in that sort of Salts to which I have resembled it: and is so Volatile, that for Distinction sake, I call it _Tartari Fugitivus_ [Errata: Sal Tartari Fugitivus]. What virtues it may have in Physick I have not yet had the opportunity to Try; but I am apt to think they will not be despicable. And besides that a very Ingenious Friend of mine tells me he hath done great matters against the stone, with a Preparation not very much Differing from ours, a very Experienc'd Germane Chymist finding that I was unacquainted with the wayes of making this salt, told me that in a great City in his Country, a noted Chymist prizes it so highly, that he had a while since procur'd a Priviledge from the Magistrates, that none but He, or by his Licence, should vent a Spirit made almost after the same Way with mine, save that he leaves out one of the Ingredients, namely the Quick-lime. But, continues _Carneades_, to resume my Former Discourse where your Curiosity interrupted it; Tis also a common practice in _France_ to bury thin Plates of Copper in the Marc (as the French call it) or Husks of Grapes, whence the Juice has been squeez'd out in the Wine-press, and by this means the more saline parts of those Husks working by little and little upon the Copper, Coagulate Themselves with it into that Blewish Green Substance we in English call Verdigrease. Of which I therefore take Notice, because having Distill'd it in a Naked Fire, I found as I expected, that by the Association of the Saline with the Metalline parts, the former were so alter'd, that the Distill'd Liquor, even without Rectification, seem'd by smell and Tast, strong almost like _Aqua Fortis_, and very much surpassed the purest and most Rectifi'd Spirit of Vinager that ever I made. And this Spirit I therefore ascribe to the salt of the Husks alter'd by their Co-Mixture with the copper (though the Fire afterwards Divorce and Transmute them) because I found this later in the bottom of the Retort in the Forme of a _Crocus_ or redish powder: And because Copper is of too sluggish a Nature to be forc'd over in close Vessels by no stronger a heat. And that which is also somewhat Remarkable in the Destillation of good Verdigrease, (or at least of that sort that I us'd) is this, that I Never could observe that it yielded me any oyl, (unless a little black slime which was separated in Rectification may pass for Oyle) though both Tartar and Vinager, (especially the former) will by Destillation yield a Moderate proportion of it. If likewise you pour Spirit of Vinager upon Calcin'd Lead, the Acid Salt of the Liquor will by its Commixture with the Metalline parts, though Insipid, acquire in a few hours a more than Saccharine sweetness; and these Saline parts being by a strong Fire Destill'd from the Lead wherewith they were imbody'd, will, as I formerly also noted to a Different purpose, leave the Metal behind them alter'd in some qualities from what it was, and will themselves ascend, partly in the Forme of an unctuous Body or Oyle, partly in that of Phlegme; but for the greatest part in the Forme of a subtile Spirit, indow'd, besides divers new Qualities which I am not now willing to take notice of, with a strong smell very much other than that of Vinager, and a piercing tast quite differing both from the Sowerness of the Spirit of Vinager, and the Sweetness of the Sugar of Lead. To be short, As the difference of Bodies may depend meerly upon that of the schemes whereinto their Common matter is put; So the seeds of Things, the Fire and the other Agents are able to alter the minute parts of a Body (either by breaking them into smaller ones of differing shapes, or by Uniting together these Fragments with the unbroken Corpuscles, or such Corpuscles among Themselves) and the same Agents partly by Altering the shape or bigness of the Constituent Corpuscles of a Body, partly by driving away some of them, partly by blending others with them, and partly by some new manner of connecting them, may give the whole portion of matter a new Texture of its minute parts; and thereby make it deserve a new and Distinct name. So that according as the small parts of matter recede from each other, or work upon each other, or are connected together after this or that determinate manner, a Body of this or that denomination is produced, as some other Body happens thereby to be alter'd or destroy'd. Since then those things which Chymists produce by the help of the Fire are but inanimate Bodies; since such fruits of the Chymists skill differ from one another but in so few qualities that we see plainly that by fire and other Agents we can employ, we can easily enough work as great alterations upon matter, as those that are requisite to change one of these Chymical Productions into another; Since the same portion of matter may without being Compounded with any extraneous Body, or at least Element, be made to put on such a variety of formes, and consequently to be (successively) turn'd into so many differing Bodies. And since the matter cloath'd with so many differing formes was originally but water, and that in its passage thorow so many transformations, it was never reduc'd into any of those substances which are reputed to be the Principles or Elements of mixt Bodies, except by the violence of the fire, which it self divides not Bodies into perfectly simple or Elementary substances, but into new Compounds; Since, I say, these things are so, I see not why we must needs believe that there are any Primogeneal and simple Bodies, of which as of Pre-exsistent Elements Nature is obliged to compound all others. Nor do I see why we may not conceive that she may produce the Bodies accounted mixt out of one another by Variously altering and contriving their minute parts, without resolving the matter into any such simple or Homogeneous substances as are pretended. Neither, to dispatch, do I see why it should be counted absur'd [Transcriber's Note: absurd] to think, that when a Body is resolv'd by the Fire into its suppos'd simple Ingredients, those substances are not true and proper Elements, but rather were, as it were, Accidentally produc'd by the fire, which by Dissipating a Body into minute Parts does, if those parts be shut up in Close Vessels, for the most part necessarily bring them to Associate Themselves after another manner than before, and so bring Them into Bodies of such Different Consistences as the Former Texture of the Body, and Concurrent Circumstances make such disbanded particles apt to Constitute; as experience shews us (and I have both noted it, and prov'd it already) that as there are some Concretes whose parts when dissipated by fire are fitted to be put into such Schemes of matter as we call Oyle, and Salt, and Spirit; So there are others, such as are especially the greatest part of Minerals, whose Corpuscles being of another Size or figure, or perhaps contriv'd another Way, will not in the Fire yield Bodies of the like Consistences, but rather others of differing Textures; Not to mention, that from Gold and some other Bodies, we see not that the Fire separates any Distinct Substances at all; nor That even those Similar Parts of Bodies which the Chymists Obtain by the Fire, are the Elements whose names they bear, but Compound Bodies, upon which, for their resemblance to them in consistence, or some other obvious Quality, Chymists have been pleas'd to bestow such Appellations. THE CONCLUSION. These last Words of _Carneades_ being soon after follow'd by a noise which seem'd to come from the place where the rest of the Company was, he took it for a warning, that it was time for him to conclude or break off his Discourse; and told his Friend; By this time I hope you see, _Eleutherius_, that if _Helmonts_ Experiments be true, it is no absurdity to question whether that Doctrine be one, that doth not assert Any Elements in the sence before explain'd. But because that, as divers of my Arguments suppose the marvellous power of the _Alkahest_ in the Analyzing of Bodies, so the Effects ascrib'd to that power are so unparallell'd and stupendious, that though I am not sure but that there _may be_ such an Agent, yet little less than [Greek: autopsia] seems requisite to make a man sure there _is_. And consequently I leave it to you to judge, how farre those of my Arguments that are built upon _Alkahestical_ Operations are weakned by that Liquors being Matchless; and shall therefore desire you not to think that I propose this Paradox that rejects all Elements, as an Opinion equally probable with the former part of my discourse. For by that, I hope, you are satisfied, that the Arguments wont to be brought by Chymists, to prove That all Bodies consist of either Three Principles, or Five, are far from being so strong as those that I have employ'd to prove, that there is not any certain and Determinate number of such Principles or Elements to be met with Universally in all mixt Bodies. And I suppose I need not tell you, that these _Anti-Chymical_ Paradoxes might have been manag'd more to their Advantage; but that having not confin'd my Curiosity to Chymical Experiments, I who am but a young Man, and younger Chymist, can yet be but slenderly furnished with them, in reference to so great and difficult a Task as you impos'd upon me; Besides that, to tell you the Truth, I durst not employ some even of the best Experiments I am acquainted with, because I must not yet disclose them; but however, I think I may presume that what I have hitherto Discoursed will induce you to think, that Chymists have been much more happy in finding Experiments than the Causes of them; or in assigning the Principles by which they may best be explain'd. And indeed, when in the writings of _Paracelsus_ I meet with such Phantastick and Un-intelligible Discourses as that Writer often puzzels and tyres his Reader with, father'd upon such excellent Experiments, as though he seldom clearly teaches, I often find he knew; me thinks the Chymists, in their searches after truth, are not unlike the Navigators of _Solomons Tarshish_ Fleet, who brought home from their long and tedious Voyages, not only Gold, and Silver, and Ivory, but Apes and Peacocks too; For so the Writings of several (for I say not, all) of your Hermetick Philosophers present us, together with divers Substantial and noble Experiments, Theories, which either like Peacocks feathers make a great shew, but are neither solid nor useful; or else like Apes, if they have some appearance of being rational, are blemish'd with some absurdity or other, that when they are _Attentively_ consider'd, makes them appear Ridiculous. _Carneades_ having thus finish'd his Discourse against the received Doctrines of the _Elements_; _Eleutherius_ judging he should not have time to say much to him before their separation, made some haste to tell him; I confess, _Carneades_, that you have said more in favour of your Paradoxes then I expected. For though divers of the Experiments you have mention'd are no secrets, and were not unknown to me, yet besides that you have added many of your own unto them, you have laid them together in such a way, and apply'd them to such purposes, and made such Deductions From them, as I have not Hitherto met with. But though I be therefore inclin'd to think, that _Philoponus_, had he heard you, would scarce have been able in all points to defend the Chymical _Hypothesis_ against the arguments wherewith you have oppos'd it; yet me thinks that however your Objections seem to evince a great part of what they pretend to, yet they evince it not all; and the numerous tryals of those you call the vulgar Chymists, may be allow'd to prove something too. Wherefore, if it be granted you that you have made it probable, First, that the differing substances into which mixt Bodies are wont to be resolved by the Fire are not of a pure and an Elementary nature, especially for this Reason, that they yet retain so much of the nature of the Concrete that afforded them, as to appear to be yet somewhat compounded, and oftentimes to differ in one Concrete from Principles of the same denomination in another: Next, that as to the number of these differing substances, neither is it precisely three, because in most Vegetable and Animal bodies Earth and Phlegme are also to be found among their Ingredients; nor is there any one determinate number into which the Fire (as it is wont to be employ'd) does precisely and universally resolve all compound Bodies whatsoever, as well Minerals as others that are reputed perfectly mixt. Lastly, that there are divers Qualities which cannot well be refer'd to any of these Substances, as if they primarily resided in it and belong'd to it; and some other qualities, which though they seem to have their chief and most ordinary residence in some one of these Principles or Elements of mixt Bodies, are not yet so deducible from it, but that also some more general Principles must be taken in to explicate them. If, I say, the Chymists (continues _Eleutherius_) be so Liberall as to make you these three Concessions, I hope you will, on your part, be so civil and Equitable as to grant them these three other propositions, namely; First, that divers Mineral Bodies, and therefore probably all the rest, may be resolv'd into a Saline, a Sulphureous, and a Mercurial part; And that almost all Vegetable and Animal Concretes may, if not by the Fire alone, yet, by a skilfull Artist Employing the Fire as his chief Instrument, be divided into five differing Substances, Salt, Spirit, Oyle, Phlegme and Earth; of which the three former by reason of their being so much more Operative than the Two Later, deserve to be Lookt upon as the Three active Principles, and by way of Eminence to be call'd the three principles of mixt bodies. Next, that these Principles, Though they be not perfectly Devoid of all Mixture, yet may without inconvenience be stil'd the Elements of Compounded bodies, and bear the Names of those Substances which they most Resemble, and which are manifestly predominant in them; and that especially for this reason, that none of these Elements is Divisible by the Fire into Four or Five differing substances, like the Concrete whence it was separated. Lastly, That Divers of the Qualities of a mixt Body, and especially the Medical Virtues, do for the most part lodge in some One or Other of its principles, and may Therefore usefully be sought for in That Principle sever'd from the others. And in this also (pursues _Eleutherius_) methinks both you and the Chymists may easily agree, that the surest way is to Learn by particular Experiments, what differing parts particular Bodies do consist of, and by what wayes (either Actual or potential fire) they may best and most Conveniently be Separated, as without relying too much upon the Fire alone, for the resolving of Bodies, so without fruitlessly contending to force them into more Elements than Nature made Them up of, or strip the sever'd Principles so naked, as by making Them Exquisitely Elementary to make them almost useless, These things (subjoynes _Eleu._) I propose, without despairing to see them granted by you; not only because I know that you so much preferr the Reputation of _Candor_ before that of subtility, that your having once suppos'd a truth would not hinder you from imbracing it when clearly made out to you; but because, upon the present occasion, it will be no disparagement to you to recede from some of your Paradoxes, since the nature and occasion of your past Discourse did not oblige you to declare your own opinions, but only to personate an Antagonist of the Chymists. So that (concludes he, with a smile) you may now by granting what I propose, add the Reputation of Loving the truth sincerely to that of having been able to oppose it subtilly. _Carneades's_ haste forbidding him to answer this crafty piece of flattery; Till I shal (sayes he) have an opportunity to acquaint you with my own Opinions about the controversies I have been discoursing of, you will not, I hope, expect I should declare my own sence of the Arguments I have employ'd. Wherefore I shall only tell you thus much at present; that though not only an acute Naturalist, but even I my self could take plausible Exceptions at some of them; yet divers of them too are such as will not perhaps be readily answer'd, and will Reduce my Adversaries, at least, to alter and Reform their _Hypothesis_. I perceive I need not minde you that the Objections I made against the Quaternary of Elements and Ternary of Principles needed not to be oppos'd so much against the Doctrines Themselves (either of which, especially the latter, may be much more probably maintain'd than hitherto it seems to have been, by those Writers for it I have met with) as against the unaccurateness and the unconcludingness of the _Analytical_ Experiments vulgarly Relyed On to Demonstrate them. And therefore, if either of the two examin'd Opinions, or any other Theory of Elements, shall upon rational and Experimental grounds be clearly made out to me; 'Tis Obliging, but not irrational, in you to Expect, that I shall not be so farr in Love with my Disquieting Doubts, as not to be content to change them for undoubted truths. And (concludes _Carneades_ smiling) it were no great disparagement for a Sceptick to confesse to you, that as unsatisfy'd as the past discourse may have made you think me with the Doctrines of the Peripateticks, and the Chymists, about the Elements and Principles, I can yet so little discover what to acquiesce in, that perchance the Enquiries of others have scarce been more unsatisfactory to me, than my own have been to my self. _FINIS._ * * * * * The Authors constant Absence from the Presse, whilst the former Treatise was Printing, and the Nature of the Subject it self, wherewith ordinary Composers are not wont to be at all acquainted, will, 'tis hop'd, procure the Readers Excuse, till the next Edition, if the _Errata_ be somewhat numerous, and if among them there want not some grosser mistakes, which yet are not the only Blemishes these lines must take notice of and acknowledg; For the Author now perceives that through the fault of those to whom he had committed the former Treatise in loose Sheets, some Papers that belonged to it, have altogether miscarryed. And though it have luckily enough happen'd, for the most part, that the Omission of them does not marr the Cohærence of the rest; yet till the next design'd Edition afford an _opportunity_ of inserting them, it is thought fit that the Printer give notice of one Omission at the End of the first Dialogue; and that to these _Errata_ there be annex'd the ensuing sheet of Paper, that was casually lost, or forgotten by him that should have put it into the Presse; where it ought to have been inserted, in the 187. printed Page, at the break, betwixt the words, [_Nature_] in the 13th. line, and [_But_] in the next line after. Though it is to be noted here, that by the mistake of the Printer, in some Books, the number of 187 is placed at the top of two somewhat distant pages; and in such copies the following addition ought to be inserted in the latter of the two, as followeth. And on this occasion I cannot but take notice, that whereas the great Argument which the Chymists are wont to employ to vilify Earth and Water, and make them be look'd upon as useless and unworthy to be reckon'd among the Principles of Mixt Bodies, is, that they are not endow'd with Specifick Properties, but only with Elementary qualities; of which they use to speak very sleightingly, as of qualities contemptible and unactive: I see no sufficient Reason for this Practice of the Chymists: For 'tis confess'd that Heat is an Elementary Quality, and yet that an almost innumerable company of considerable Things are perform'd by Heat, is manifest to them that duly consider the various _Phænomena_ wherein it intervenes as a principall Actor; and none ought less to ignore or distrust this Truth then a Chymist. Since almost all the operations and Productions of his Art are performed chiefly by the means of Heat. And as for Cold it self, upon whose account they so despise the Earth and Water, if they please to read in the Voyages of our English and Dutch Navigators in _Nova Zembla_ and other Northern Regions what stupendious Things may be effected by Cold, they would not perhaps think it so despicable. And not to repeat what I lately recited to You out of _Paracelsus_ himself, who by the help of an intense Cold teaches to separate the Quintessence of Wine; I will only now observe to You, that the Conservation of the Texture of many Bodies both animate and inanimate do's so much depend upon the convenient motion both of their own Fluid and Looser Parts, and of the ambient Bodies, whether Air, Water, &c. that not only in humane Bodies we see that the immoderate or unseasonable coldness of the Air (especially when it finds such Bodies overheated) do's very frequently discompose the _Oeconomie_ of them, and occasion variety of Diseases; but in the solid and durable Body of Iron it self, in which one would not expect that suddain Cold should produce any notable change, it may have so great an operation, that if you take a Wire, or other slender piece of steel, and having brought it in the fire to a white heat, You suffer it afterwards to cool leasurely in the Air, it will when it is cold be much of the same hardnesse it was of before: Whereas if as soon as You remove it from the fire, you plunge it into cold water, it will upon the sudden Refrigeration acquire a very much greater hardness then it had before; Nay, and will become manifestly brittle. And that you may not impute this to any peculiar Quality in the Water, or other Liquor, or Unctuous matter, wherein such heated steel is wont to be quenched that it may be temper'd; I know a very skillful Tradesman, that divers times hardens steel by suddenly cooling it in a Body that is neither a liquor, nor so much as moist. A tryal of that Nature I remember I have seen made. And however by the operation that Water has upon steel quenched in it, whether upon the Account of its coldness and moisture, or upon that of any other of its qualities, it appears, that water is not alwaies so inefficacious and contemptible a Body, as our Chymists would have it passe for. And what I have said of the Efficacy of Cold and Heat, might perhaps be easily enough carried further by other considerations and experiments; were it not that having been mention'd only upon the Bye, I must not insist on it, but proceed to another Subject. _ERRATA._ Pag. 5. line. 6. read _so qualify'd_, 15. 19. _Ratiocinations_, 25. 15. _for a_, 33. 17. in a parenth. (_that is no more_), 51. 24. _besides another Caput_, 79. 10. _employ_, 86. 13. _structure_, 97. 13. _Sack_, ibid. 22. _Sack_, 104. 29. instead of _appear it, will_, leg. _appear, it will_, 118. 20. _leasure_, ibid. _principal_, 126. 20. _and till it suffer_, 129. 3. leg. in parenth. (_notwithstanding, &c._ 131. 15. _so_, 144. 15. [Greek: Synchysis], 151. 5. _nor have been resolved_, 180. 25. _Magistram_, 185. 15. _lately_, 188. 15. _tunned_, 200. 1. _intolerable_, ibid. 2. _in_, 209. 21. _tegularum_, 210. 7. _distill'd from_, 215. 25. dele _the_, 220. 1. _bodies_, 228. 11. [Transcriber's Note: 21.] _fugitive_, 231. 17. instead of _all_ lege _a pound_, 237. 6. _Chymist_, 248. 18. _Ashes off_, 251. 23. _Deopilative)_, 259. 6. _it self_, 269. 10. [Greek: ousia analogos], _ibid._ [Greek: astrôn stoicheiô], 276. 25. make a parenth. at the words, _by the_, and shut it after the words in the 27. line _at all_, 280. 11. _Corals_, 288. 6. _ascribes_, 294. 22. _porosity_, ibid. 28. _noted_, 296. 1. _Bodies_, 305. 8. _(attended_, 307. 12. dele _to_, 308. 12. _devisers_, 312. 14. _and_, 313. 3. _too_, 314. 24. _fugitivenesse_, 333. 13. _origine_, ibid. 24. _contrivance of_, 339. 1. _Nay, Barthias_, 142. [Transcriber's Note: 342.] 3. _in; I will_, 350. 26. _absurd_, 356. 11. [Transcriber's Note: 21.] _Goutieres_, 358. 6. _antea_, 360. 1. _compertissimum_, ibid. 18. _Joachimica_, ibid. 19 _graminis_, ibid. 23. _sua_ [Transcriber's Note: this appears to be correct on the original page 360], 362. 6. _Dutch account_, 363. 2. _diggers)_, ibid. 11. and 12. lin. read _damp as the Englishmen also call it_, 366. 25. _a height_, 368. 19. _in use_, 370. 9. _latter; And_, ibid. 24. _Water; I_, 377. 22. _Rest_, ibid. 25. _know)_, 378. 23. after _Aggregate_ insert _or complex_, ibid. 27. dele ), ibid. 28. dele ), 379. 4. before _as_ begin a parenth. which ends lin. 9. at _Gold_, ibid. instead of _Which_, put _This_, ibid. 12. with the word _Texture_ should be connected the next line, _Though_, and this word _Though_ is to have put before it a parenthesis, which is to end at the word _Fluid_ in the 16th. line, 383. 3. _Regulus Martis Stellatus_, 382. 3. _Relations_, ibid. 9. _Chymist_, 386. 29. _confesse by teaching it_, 391. 8. _and yet may_, 392. 1. _an_, ibid. 12. _of_, 393. [Transcriber's Note: line 5] _distinct Tasts_, 397. 13. _Talck_, 398. 18. _Earth_, 399. 18. _parts_, 404. 8. _sal-petræ_, 419. 20. after _it_ put in _Sal_. * * * * * _The Publisher doth advertise the Redaer [Transcriber's Note: Reader], that seeing there are divers Experiments related in this Treatise, which the Author is not unwilling to submit to the consideration also of Forraign Philosophers, he believes this piece will be very soon translated into Latin._ END. 
4524	----	FAMILIAR LETTERS ON CHEMISTRY, AND ITS RELATION TO COMMERCE, PHYSIOLOGY, AND AGRICULTURE, BY JUSTUS LIEBIG, M.D., PH. D., F.R.S., PROFESSOR OF CHEMISTRY IN THE UNIVERSITY OF GIESSEN. EDITED BY JOHN GARDNER, M.D., MEMBER OF THE CHEMICAL SOCIETY. Second Edition, Corrected. LONDON: MDCCCXLIV. PREFACE The Letters contained in this little Volume embrace some of the most important points of the science of Chemistry, in their application to Natural Philosophy, Physiology, Agriculture, and Commerce. Some of them treat of subjects which have already been, or will hereafter be, more fully discussed in my larger works. They were intended to be mere sketches, and were written for the especial purpose of exciting the attention of governments, and an enlightened public, to the necessity of establishing Schools of Chemistry, and of promoting, by every means, the study of a science so intimately connected with the arts, pursuits, and social well-being of modern civilised nations. For my own part I do not scruple to avow the conviction, that ere long, a knowledge of the principal truths of Chemistry will be expected in every educated man, and that it will be as necessary to the Statesman, the Political Economist, and the Practical Agriculturist, as it is already indispensable to the Physician, and the Manufacturer. In Germany, such of these Letters as have been already published, have not failed to produce some of the results anticipated. New professorships have been established in the Universities of Goettingen and Wuertzburg, for the express purpose of facilitating the application of chemical truths to the practical arts of life, and of following up the new line of investigation and research--the bearing of Chemistry upon Physiology, Medicine, and Agriculture,--which may be said to be only just begun. My friend, Dr. Ernest Dieffenbach, one of my first pupils, who is well acquainted with all the branches of Chemistry, Physics, Natural History, and Medicine, suggested to me that a collection of these Letters would be acceptable to the English public, which has so favourably received my former works. I readily acquiesced in the publication of an English edition, and undertook to write a few additional Letters, which should embrace some conclusions I have arrived at, in my recent investigations, in connection with the application of chemical science to the physiology of plants and agriculture. My esteemed friend, Dr. Gardner, has had the kindness to revise the manuscript and the proof sheets for publication, for which I cannot refrain expressing my best thanks. It only remains for me to add a hope, that this little offering may serve to make new friends to our beautiful and useful science, and be a remembrancer to those old friends who have, for many years past, taken a lively interest in all my labours. JUSTUS LIEBIG Giessen, Aug. 1843. CONTENTS LETTER I The Subject proposed. Materials employed for Chemical Apparatus:-- GLASS--CAOUTCHOUC--CORK--PLATINUM. THE BALANCE. The "Elements" of the Ancients, represent the forms of matter. Lavoisier and his successors. Study of the materials composing the Earth. Synthetic production of Minerals--LAPIS LAZULI. Organic Chemistry. LETTER II Changes of Form which every kind of Matter undergoes. Conversion of Gases into Liquids and Solids. Carbonic Acid--its curious properties in a solid state. Condensation of Gases by porous bodies. By Spongy Platinum. Importance of this property in Nature. LETTER III The Manufacture of Soda from Culinary Salt; its importance in the Arts and in Commerce. Glass--Soap--Sulphuric Acid. Silver Refining. Bleaching. TRADE IN SULPHUR. LETTER IV Connection of Theory with Practice. Employment of MAGNETISM as a moving power--its impracticability. Relation of Coals and Zinc as economic sources of Force. Manufacture of Beet-root Sugar--its impolicy. Gas for illumination. LETTER V ISOMERISM, or identity of composition in bodies with different chemical and physical properties. CRYSTALLISATION. AMORPHISM. ISOMORPHISM, or similarity of properties in bodies totally different in composition. LETTER VI ALLIANCE OF CHEMISTRY WITH PHYSIOLOGY. Division of Food into nourishment, and materials for combustion. Effects of Atmospheric Oxygen. Balance of CARBON and OXYGEN. LETTER VII ANIMAL HEAT, its laws and influence on the Animal Functions. Loss and SUPPLY. Influence of Climate. Fuel of Animal Heat. Agency of Oxygen in Disease. Respiration. LETTER VIII ALIMENTS. Constituents of the Blood. Fibrine, Albumen. Inorganic Substances. Isomerism of Fibrine, Albumen, and elements of nutrition. Relation of animal and vegetable organisms. LETTER IX Growth of Animals. Uses of Butter and Milk. Metamorphoses of Tissues. Food of Carnivora, and of the Horse. LETTER X Application of the preceding facts to Man. Division of human Food. Uses of Gelatine. LETTER XI CIRCULATION OF MATTER IN THE ANIMAL AND VEGETABLE KINGDOMS. The Ocean. AGRICULTURE. RESTITUTION OF AN EQUILIBRIUM IN THE SOIL. Causes of the exhaustion of Land. Virginia. England. Relief gained by importation of bones. Empirical farming unsatisfactory. Necessity for scientific principles. Influence of the atmosphere. Of Saline and Earthy matters of the soil. LETTER XII SCIENCE AND ART OF AGRICULTURE. NECESSITY OF CHEMISTRY. Rationale of agricultural processes. Washing for gold. LETTER XIII ILLUSTRATION OF THE NECESSITY OF CHEMISTRY TO ADVANCE AND PERFECT AGRICULTURE. Manner in which FALLOW ameliorates the soil. Uses of Lime. Effects of Burning. Of Marl. LETTER XIV NATURE AND EFFECTS OF MANURES. Animal bodies subject to constant waste. Parts separating--exuviae--waste vegetable matters--together contain all the elements of the soil and of food. Various value of excrements of different animals as manure. LETTER XV SOURCE OF THE CARBON AND NITROGEN OF PLANTS. Produce of Carbon in Forests and Meadows supplied only with mineral aliments prove it to be from the atmosphere. Relations between Mineral constituents, and Carbon and Nitrogen. Effects of the Carbonic Acid and Ammonia of Manures. Necessity of inorganic constituents to the formation of aliments, of blood, and therefore of nutrition. NECESSITY OF INQUIRIES by ANALYSIS to advance AGRICULTURE. LETTER XVI RESULTS OF THE AUTHOR'S LATEST INQUIRIES. Superlative importance of the PHOSPHATES OF LIME and ALKALIES to the cultivation of the CEREALIA. Sources of a SUPPLY of these MATERIALS. LETTERS ON CHEMISTRY LETTER I My dear Sir, The influence which the science of chemistry exercises upon human industry, agriculture, and commerce; upon physiology, medicine, and other sciences, is now so interesting a topic of conversation everywhere, that it may be no unacceptable present to you if I trace in a few familiar letters some of the relations it bears to these various sciences, and exhibit for you its actual effect upon the present social condition of mankind. In speaking of the present state of chemistry, its rise and progress, I shall need no apology if, as a preliminary step, I call your attention to the implements which the chemist employs--the means which are indispensable to his labours and to his success. These consist, generally, of materials furnished to us by nature, endowed with many most remarkable properties fitting them for our purposes; if one of them is a production of art, yet its adaptation to the use of mankind,--the qualities which render it available to us,--must be referred to the same source as those derived immediately from nature. Cork, Platinum, Glass, and Caoutchouc, are the substances to which I allude, and which minister so essentially to modern chemical investigations. Without them, indeed, we might have made some progress, but it would have been slow; we might have accomplished much, but it would have been far less than has been done with their aid. Some persons, by the employment of expensive substances, might have successfully pursued the science; but incalculably fewer minds would have been engaged in its advancement. These materials have only been duly appreciated and fully adopted within a very recent period. In the time of Lavoisier, the rich alone could make chemical researches; the necessary apparatus could only be procured at a very great expense. And first, of Glass: every one is familiar with most of the properties of this curious substance; its transparency, hardness, destitution of colour, and stability under ordinary circumstances: to these obvious qualities we may add those which especially adapt it to the use of the chemist, namely, that it is unaffected by most acids or other fluids contained within it. At certain temperatures it becomes more ductile and plastic than wax, and may be made to assume in our hands, before the flame of a common lamp, the form of every vessel we need to contain our materials, and of every apparatus required to pursue our experiments. Then, how admirable and valuable are the properties of Cork! How little do men reflect upon the inestimable worth of so common a substance! How few rightly esteem the importance of it to the progress of science, and the moral advancement of mankind!--There is no production of nature or art equally adapted to the purposes to which the chemist applies it. Cork consists of a soft, highly elastic substance, as a basis, having diffused throughout a matter with properties resembling wax, tallow, and resin, yet dissimilar to all of these, and termed suberin. This renders it perfectly impermeable to fluids, and, in a great measure, even to gases. It is thus the fittest material we possess for closing our bottles, and retaining their contents. By its means, and with the aid of Caoutchouc, we connect our vessels and tubes of glass, and construct the most complicated apparatus. We form joints and links of connexion, adapt large apertures to small, and thus dispense altogether with the aid of the brassfounder and the mechanist. Thus the implements of the chemist are cheaply and easily procured, immediately adapted to any purpose, and readily repaired or altered. Again, in investigating the composition of solid bodies,--of minerals,--we are under the necessity of bringing them into a liquid state, either by solution or fusion. Now vessels of glass, of porcelain, and of all non-metallic substances, are destroyed by the means we employ for that purpose,--are acted upon by many acids, by alkalies and the alkaline carbonates. Crucibles of gold and silver would melt at high temperatures. But we have a combination of all the qualities we can desire in Platinum. This metal was only first adapted to these uses about fifty years since. It is cheaper than gold, harder and more durable than silver, infusible at all temperatures of our furnaces, and is left intact by acids and alkaline carbonates. Platinum unites all the valuable properties of gold and of porcelain, resisting the action of heat, and of almost all chemical agents. As no mineral analysis could be made perfectly without platinum vessels, had we not possessed this metal, the composition of minerals would have yet remained unknown; without cork and caoutchouc we should have required the costly aid of the mechanician at every step. Even without the latter of these adjuncts our instruments would have been far more costly and fragile. Possessing all these gifts of nature, we economise incalculably our time--to us more precious than money! Such are our instruments. An equal improvement has been accomplished in our laboratory. This is no longer the damp, cold, fireproof vault of the metallurgist, nor the manufactory of the druggist, fitted up with stills and retorts. On the contrary, a light, warm, comfortable room, where beautifully constructed lamps supply the place of furnaces, and the pure and odourless flame of gas, or of spirits of wine, supersedes coal and other fuel, and gives us all the fire we need; where health is not invaded, nor the free exercise of thought impeded: there we pursue our inquiries, and interrogate Nature to reveal her secrets. To these simple means must be added "The Balance," and then we possess everything which is required for the most extensive researches. The great distinction between the manner of proceeding in chemistry and natural philosophy is, that one weighs, the other measures. The natural philosopher has applied his measures to nature for many centuries, but only for fifty years have we attempted to advance our philosophy by weighing. For all great discoveries chemists are indebted to the "balance"--that incomparable instrument which gives permanence to every observation, dispels all ambiguity, establishes truth, detects error, and guides us in the true path of inductive science. The balance, once adopted as a means of investigating nature, put an end to the school of Aristotle in physics. The explanation of natural phenomena by mere fanciful speculations, gave place to a true natural philosophy. Fire, air, earth, and water, could no longer be regarded as elements. Three of them could henceforth be considered only as significative of the forms in which all matter exists. Everything with which we are conversant upon the surface of the earth is solid, liquid, or aeriform; but the notion of the elementary nature of air, earth, and water, so universally held, was now discovered to belong to the errors of the past. Fire was found to be but the visible and otherwise perceptible indication of changes proceeding within the, so called, elements. Lavoisier investigated the composition of the atmosphere and of water, and studied the many wonderful offices performed by an element common to both in the scheme of nature, namely, oxygen: and he discovered many of the properties of this elementary gas. After his time, the principal problem of chemical philosophers was to determine the composition of the solid matters composing the earth. To the eighteen metals previously known were soon added twenty-four discovered to be constituents of minerals. The great mass of the earth was shown to be composed of metals in combination with oxygen, to which they are united in one, two, or more definite and unalterable proportions, forming compounds which are termed metallic oxides, and these, again, combined with oxides of other bodies, essentially different to metals, namely, carbon and silicium. If to these we add certain compounds of sulphur with metals, in which the sulphur takes the place of oxygen, and forms sulphurets, and one other body,--common salt,--(which is a compound of sodium and chlorine), we have every substance which exists in a solid form upon our globe in any very considerable mass. Other compounds, innumerably various, are found only in small scattered quantities. The chemist, however, did not remain satisfied with the separation of minerals into their component elements, i.e. their analysis; but he sought by synthesis, i.e. by combining the separate elements and forming substances similar to those constructed by nature, to prove the accuracy of his processes and the correctness of his conclusions. Thus he formed, for instance, pumice-stone, feldspar, mica, iron pyrites, &c. artificially. But of all the achievements of inorganic chemistry, the artificial formation of lapis lazuli was the most brilliant and the most conclusive. This mineral, as presented to us by nature, is calculated powerfully to arrest our attention by its beautiful azure-blue colour, its remaining unchanged by exposure to air or to fire, and furnishing us with a most valuable pigment, Ultramarine, more precious than gold! The analysis of lapis lazuli represented it to be composed of silica, alumina, and soda, three colourless bodies, with sulphur and a trace of iron. Nothing could be discovered in it of the nature of a pigment, nothing to which its blue colour could be referred, the cause of which was searched for in vain. It might therefore have been supposed that the analyst was here altogether at fault, and that at any rate its artificial production must be impossible. Nevertheless, this has been accomplished, and simply by combining in the proper proportions, as determined by analysis, silica, alumina, soda, iron, and sulphur. Thousands of pounds weight are now manufactured from these ingredients, and this artificial ultramarine is as beautiful as the natural, while for the price of a single ounce of the latter we may obtain many pounds of the former. With the production of artificial lapis lazuli, the formation of mineral bodies by synthesis ceased to be a scientific problem to the chemist; he has no longer sufficient interest in it to pursue the subject. He may now be satisfied that analysis will reveal to him the true constitution of minerals. But to the mineralogist and geologist it is still in a great measure an unexplored field, offering inquiries of the highest interest and importance to their pursuits. After becoming acquainted with the constituent elements of all the substances within our reach and the mutual relations of these elements, the remarkable transmutations to which the bodies are subject under the influence of the vital powers of plants and animals, became the principal object of chemical investigations, and the highest point of interest. A new science, inexhaustible as life itself, is here presented us, standing upon the sound and solid foundation of a well established inorganic chemistry. Thus the progress of science is, like the development of nature's works, gradual and expansive. After the buds and branches spring forth the leaves and blossoms, after the blossoms the fruit. Chemistry, in its application to animals and vegetables, endeavours jointly with physiology to enlighten us respecting the mysterious processes and sources of organic life. LETTER II My dear Sir, In my former letter I reminded you that three of the supposed elements of the ancients represent the forms or state in which all the ponderable matter of our globe exists; I would now observe, that no substance possesses absolutely any one of those conditions; that modern chemistry recognises nothing unchangeably solid, liquid, or aeriform: means have been devised for effecting a change of state in almost every known substance. Platinum, alumina, and rock crystal, it is true, cannot be liquified by the most intense heat of our furnaces, but they melt like wax before the flame of the oxy-hydrogen blowpipe. On the other hand, of the twenty-eight gaseous bodies with which we are acquainted, twenty-five may be reduced to a liquid state, and one into a solid. Probably, ere long, similar changes of condition will be extended to every form of matter. There are many things relating to this condensation of the gases worthy of your attention. Most aeriform bodies, when subjected to compression, are made to occupy a space which diminishes in the exact ratio of the increase of the compressing force. Very generally, under a force double or triple of the ordinary atmospheric pressure, they become one half or one third their former volume. This was a long time considered to be a law, and known as the law of Marriotte; but a more accurate study of the subject has demonstrated that this law is by no means of general application. The volume of certain gases does not decrease in the ratio of the increase of the force used to compress them, but in some, a diminution of their bulk takes place in a far greater degree as the pressure increases. Again, if ammoniacal gas is reduced by a compressing force to one-sixth of its volume, or carbonic acid is reduced to one thirty-sixth, a portion of them loses entirely the form of a gas, and becomes a liquid, which, when the pressure is withdrawn, assumes again in an instant its gaseous state--another deviation from the law of Marriotte. Our process for reducing gases into fluids is of admirable simplicity. A simple bent tube, or a reduction of temperature by artificial means, have superseded the powerful compressing machines of the early experimenters. The cyanuret of mercury, when heated in an open glass tube, is resolved into cyanogen gas and metallic mercury; if this substance is heated in a tube hermetically sealed, the decomposition occurs as before, but the gas, unable to escape, and shut up in a space several hundred times smaller than it would occupy as gas under the ordinary atmospheric pressure, becomes a fluid in that part of the tube which is kept cool. When sulphuric acid is poured upon limestone in an open vessel, carbonic acid escapes with effervescence as a gas, but if the decomposition is effected in a strong, close, and suitable vessel of iron, we obtain the carbonic acid in the state of liquid. In this manner it may be obtained in considerable quantities, even many pounds weight. Carbonic acid is separated from other bodies with which it is combined as a fluid under a pressure of thirty-six atmospheres. The curious properties of fluid carbonic acid are now generally known. When a small quantity is permitted to escape into the atmosphere, it assumes its gaseous state with extraordinary rapidity, and deprives the remaining fluid of caloric so rapidly that it congeals into a white crystalline mass like snow: at first, indeed, it was thought to be really snow, but upon examination it proved to be pure frozen carbonic acid. This solid, contrary to expectation, exercises only a feeble pressure upon the surrounding medium. The fluid acid inclosed in a glass tube rushes at once, when opened, into a gaseous state, with an explosion which shatters the tube into fragments; but solid carbonic acid can be handled without producing any other effect than a feeling of intense cold. The particles of the carbonic acid being so closely approximated in the solid, the whole force of cohesive attraction (which in the fluid is weak) becomes exerted, and opposes its tendency to assume its gaseous state; but as it receives heat from surrounding bodies, it passes into gas gradually and without violence. The transition of solid carbonic acid into gas deprives all around it of caloric so rapidly and to so great an extent, that a degree of cold is produced immeasurably great, the greatest indeed known. Ten, twenty, or more pounds weight of mercury, brought into contact with a mixture of ether and solid carbonic acid, becomes in a few moments firm and malleable. This, however, cannot be accomplished without considerable danger. A melancholy accident occurred at Paris, which will probably prevent for the future the formation of solid carbonic acid in these large quantities, and deprive the next generation of the gratification of witnessing these curious experiments. Just before the commencement of the lecture in the Laboratory of the Polytechnic School, an iron cylinder, two feet and a half long and one foot in diameter, in which carbonic acid had been developed for experiment before the class, burst, and its fragments were scattered about with the most tremendous force; it cut off both the legs of the assistant and killed him on the spot. This vessel, formed of the strongest cast-iron, and shaped like a cannon, had often been employed to exhibit experiments in the presence of the students. We can scarcely think, without shuddering, of the dreadful calamity such an explosion would have occasioned in a hall filled with spectators. When we had ascertained the fact of gases becoming fluid under the influence of cold or pressure, a curious property possessed by charcoal, that of absorbing gas to the extent of many times its volume,--ten, twenty, or even as in the case of ammoniacal gas or muriatic acid gas, eighty or ninety fold,--which had been long known, no longer remained a mystery. Some gases are absorbed and condensed within the pores of the charcoal, into a space several hundred times smaller than they before occupied; and there is now no doubt they there become fluid, or assume a solid state. As in a thousand other instances, chemical action here supplants mechanical forces. Adhesion or heterogeneous attraction, as it is termed, acquired by this discovery a more extended meaning; it had never before been thought of as a cause of change of state in matter; but it is now evident that a gas adheres to the surface of a solid body by the same force which condenses it into a liquid. The smallest amount of a gas,--atmospheric air for instance,--can be compressed into a space a thousand times smaller by mere mechanical pressure, and then its bulk must be to the least measurable surface of a solid body, as a grain of sand to a mountain. By the mere effect of mass,--the force of gravity,--gaseous molecules are attracted by solids and adhere to their surfaces; and when to this physical force is added the feeblest chemical affinity, the liquifiable gases cannot retain their gaseous state. The amount of air condensed by these forces upon a square inch of surface is certainly not measurable; but when a solid body, presenting several hundred square feet of surface within the space of a cubic inch, is brought into a limited volume of gas, we may understand why that volume is diminished, why all gases without exception are absorbed. A cubic inch of charcoal must have, at the lowest computation, a surface of one hundred square feet. This property of absorbing gases varies with different kinds of charcoal: it is possessed in a higher degree by those containing the most pores, i.e. where the pores are finer; and in a lower degree in the more spongy kinds, i.e. where the pores are larger. In this manner every porous body--rocks, stones, the clods of the fields, &c.,--imbibe air, and therefore oxygen; the smallest solid molecule is thus surrounded by its own atmosphere of condensed oxygen; and if in their vicinity other bodies exist which have an affinity for oxygen, a combination is effected. When, for instance, carbon and hydrogen are thus present, they are converted into nourishment for vegetables,--into carbonic acid and water. The development of heat when air is imbibed, and the production of steam when the earth is moistened by rain, are acknowledged to be consequences of this condensation by the action of surfaces. But the most remarkable and interesting case of this kind of action is the imbibition of oxygen by metallic platinum. This metal, when massive, is of a lustrous white colour, but it may be brought, by separating it from its solutions, into so finely divided a state, that its particles no longer reflect light, and it forms a powder as black as soot. In this condition it absorbs eight hundred times its volume of oxygen gas, and this oxygen must be contained within it in a state of condensation very like that of fluid water. When gases are thus condensed, i.e. their particles made to approximate in this extraordinary manner, their properties can be palpably shown. Their chemical actions become apparent as their physical characteristic disappears. The latter consists in the continual tendency of their particles to separate from each other; and it is easy to imagine that this elasticity of gaseous bodies is the principal impediment to the operation of their chemical force; for this becomes more energetic as their particles approximate. In that state in which they exist within the pores or upon the surface of solid bodies, their repulsion ceases, and their whole chemical action is exerted. Thus combinations which oxygen cannot enter into, decompositions which it cannot effect while in the state of gas, take place with the greatest facility in the pores of platinum containing condensed oxygen. When a jet of hydrogen gas, for instance, is thrown upon spongy platinum, it combines with the oxygen condensed in the interior of the mass; at their point of contact water is formed, and as the immediate consequence heat is evolved; the platinum becomes red hot and the gas is inflamed. If we interrupt the current of the gas, the pores of the platinum become instantaneously filled again with oxygen; and the same phenomenon can be repeated a second time, and so on interminably. In finely pulverised platinum, and even in spongy platinum, we therefore possess a perpetuum mobile--a mechanism like a watch which runs out and winds itself up--a force which is never exhausted--competent to produce effects of the most powerful kind, and self-renewed ad infinitum. Many phenomena, formerly inexplicable, are satisfactorily explained by these recently discovered properties of porous bodies. The metamorphosis of alcohol into acetic acid, by the process known as the quick vinegar manufacture, depends upon principles, at a knowledge of which we have arrived by a careful study of these properties. LETTER III My dear Sir, The manufacture of soda from common culinary salt, may be regarded as the foundation of all our modern improvements in the domestic arts; and we may take it as affording an excellent illustration of the dependence of the various branches of human industry and commerce upon each other, and their relation to chemistry. Soda has been used from time immemorial in the manufacture of soap and glass, two chemical productions which employ and keep in circulation an immense amount of capital. The quantity of soap consumed by a nation would be no inaccurate measure whereby to estimate its wealth and civilisation. Of two countries, with an equal amount of population, the wealthiest and most highly civilised will consume the greatest weight of soap. This consumption does not subserve sensual gratification, nor depend upon fashion, but upon the feeling of the beauty, comfort, and welfare, attendant upon cleanliness; and a regard to this feeling is coincident with wealth and civilisation. The rich in the middle ages concealed a want of cleanliness in their clothes and persons under a profusion of costly scents and essences, whilst they were more luxurious in eating and drinking, in apparel and horses. With us a want of cleanliness is equivalent to insupportable misery and misfortune. Soap belongs to those manufactured products, the money value of which continually disappears from circulation, and requires to be continually renewed. It is one of the few substances which are entirely consumed by use, leaving no product of any worth. Broken glass and bottles are by no means absolutely worthless; for rags we may purchase new cloth, but soap-water has no value whatever. It would be interesting to know accurately the amount of capital involved in the manufacture of soap; it is certainly as large as that employed in the coffee trade, with this important difference as respects Germany, that it is entirely derived from our own soil. France formerly imported soda from Spain,--Spanish sodas being of the best quality--at an annual expenditure of twenty to thirty millions of francs. During the war with England the price of soda, and consequently of soap and glass, rose continually; and all manufactures suffered in consequence. The present method of making soda from common salt was discovered by Le Blanc at the end of the last century. It was a rich boon for France, and became of the highest importance during the wars of Napoleon. In a very short time it was manufactured to an extraordinary extent, especially at the seat of the soap manufactories. Marseilles possessed for a time a monopoly of soda and soap. The policy of Napoleon deprived that city of the advantages derived from this great source of commerce, and thus excited the hostility of the population to his dynasty, which became favourable to the restoration of the Bourbons. A curious result of an improvement in a chemical manufacture! It was not long, however, in reaching England. In order to prepare the soda of commerce (which is the carbonate) from common salt, it is first converted into Glauber's salt (sulphate of soda). For this purpose 80 pounds weight of concentrated sulphuric acid (oil of vitriol) are required to 100 pounds of common salt. The duty upon salt checked, for a short time, the full advantage of this discovery; but when the Government repealed the duty, and its price was reduced to its minimum, the cost of soda depended upon that of sulphuric acid. The demand for sulphuric acid now increased to an immense extent; and, to supply it, capital was embarked abundantly, as it afforded an excellent remuneration. The origin and formation of sulphuric acid was studied most carefully; and from year to year, better, simpler, and cheaper methods of making it were discovered. With every improvement in the mode of manufacture, its price fell; and its sale increased in an equal ratio. Sulphuric acid is now manufactured in leaden chambers, of such magnitude that they would contain the whole of an ordinary-sized house. As regards the process and the apparatus, this manufacture has reached its acme--scarcely is either susceptible of improvement. The leaden plates of which the chambers are constructed, requiring to be joined together with lead (since tin or solder would be acted on by the acid), this process was, until lately, as expensive as the plates themselves; but now, by means of the oxy-hydrogen blowpipe, the plates are cemented together at their edges by mere fusion, without the intervention of any kind of solder. And then, as to the process: according to theory, 100 pounds weight of sulphur ought to produce 306 pounds of sulphuric acid; in practice 300 pounds are actually obtained; the amount of loss is therefore too insignificant for consideration. Again; saltpetre being indispensable in making sulphuric acid, the commercial value of that salt had formerly an important influence upon its price. It is true that 100 pounds of saltpetre only are required to 1000 pounds of sulphur; but its cost was four times greater than an equal weight of the latter. Travellers had observed near the small seaport of Yquiqui, in the district of Atacama, in Peru, an efflorescence covering the ground over extensive districts. This was found to consist principally of nitrate of soda. Advantage was quickly taken of this discovery. The quantity of this valuable salt proved to be inexhaustible, as it exists in beds extending over more than 200 square miles. It was brought to England at less than half the freight of the East India saltpetre (nitrate of potassa); and as, in the chemical manufacture neither the potash nor the soda were required, but only the nitric acid, in combination with the alkali, the soda-saltpetre of South America soon supplanted the potash-nitre of the East. The manufacture of sulphuric acid received a new impulse; its price was much diminished without injury to the manufacturer; and, with the exception of fluctuations caused by the impediments thrown in the way of the export of sulphur from Sicily, it soon became reduced to a minimum, and remained stationary. Potash-saltpetre is now only employed in the manufacture of gunpowder; it is no longer in demand for other purposes; and thus, if Government effect a saving of many hundred thousand pounds annually in gunpowder, this economy must be attributed to the increased manufacture of sulphuric acid. We may form an idea of the amount of sulphuric acid consumed, when we find that 50,000 pounds weight are made by a small manufactory, and from 200,000 to 600,000 pounds by a large one annually. This manufacture causes immense sums to flow annually into Sicily. It has introduced industry and wealth into the arid and desolate districts of Atacama. It has enabled us to obtain platina from its ores at a moderate and yet remunerating price; since the vats employed for concentrating this acid are constructed of this metal, and cost from 1000l. to 2000l. sterling. It leads to frequent improvements in the manufacture of glass, which continually becomes cheaper and more beautiful. It enables us to return to our fields all their potash--a most valuable and important manure--in the form of ashes, by substituting soda in the manufacture of glass and soap. It is impossible to trace, within the compass of a letter, all the ramifications of this tissue of changes and improvements resulting from one chemical manufacture; but I must still claim your attention to a few more of its most important and immediate results. I have already told you, that in the manufacture of soda from culinary salt, it is first converted into sulphate of soda. In this first part of the process, the action of sulphuric acid produces muriatic acid to the extent of one-and-a-half the amount of the sulphuric acid employed. At first, the profit upon the soda was so great, that no one took the trouble to collect the muriatic acid: indeed it had no commercial value. A profitable application of it was, however, soon discovered: it is a compound of chlorine, and this substance may be obtained from it purer than from any other source. The bleaching power of chlorine has long been known; but it was only employed upon a large scale after it was obtained from this residuary muriatic acid, and it was found that in combination with lime it could be transported to distances without inconvenience. Thenceforth it was used for bleaching cotton; and, but for this new bleaching process, it would scarcely have been possible for the cotton manufacture of Great Britain to have attained its present enormous extent,--it could not have competed in price with France and Germany. In the old process of bleaching, every piece must be exposed to the air and light during several weeks in the summer, and kept continually moist by manual labour. For this purpose, meadow land, eligibly situated, was essential. Now a single establishment near Glasgow bleaches 1400 pieces of cotton daily, throughout the year. What an enormous capital would be required to purchase land for this purpose! How greatly would it increase the cost of bleaching to pay interest upon this capital, or to hire so much land in England! This expense would scarcely have been felt in Germany. Besides the diminished expense, the cotton stuffs bleached with chlorine suffer less in the hands of skilful workmen than those bleached in the sun; and already the peasantry in some parts of Germany have adopted it, and find it advantageous. Another use to which cheap muriatic acid is applied, is the manufacture of glue from bones. Bone contains from 30 to 36 per cent. of earthy matter--chiefly phosphate of lime, and the remainder is gelatine. When bones are digested in muriatic acid they become transparent and flexible like leather, the earthy matter is dissolved, and after the acid is all carefully washed away, pieces of glue of the same shape as the bones remain, which are soluble in hot water and adapted to all the purposes of ordinary glue, without further preparation. Another important application of sulphuric acid may be adduced; namely, to the refining of silver and the separation of gold, which is always present in some proportion in native silver. Silver, as it is usually obtained from mines in Europe, contains in 16 ounces, 6 to 8 ounces of copper. When used by the silversmith, or in coining, 16 ounces must contain in Germany 13 ounces of silver, in England about 14 1/2. But this alloy is always made artificially by mixing pure silver with the due proportion of the copper; and for this purpose the silver must be obtained pure by the refiner. This he formerly effected by amalgamation, or by roasting it with lead; and the cost of this process was about 2l. for every hundred-weight of silver. In the silver so prepared, about 1/1200 to 1/2000th part of gold remained; to effect the separation of this by nitrio-hydrochloric acid was more expensive than the value of the gold; it was therefore left in utensils, or circulated in coin, valueless. The copper, too, of the native silver was no use whatever. But the 1/1000th part of gold, being about one and a half per cent. of the value of the silver, now covers the cost of refining, and affords an adequate profit to the refiner; so that he effects the separation of the copper, and returns to his employer the whole amount of the pure silver, as well as the copper, without demanding any payment: he is amply remunerated by that minute portion of gold. The new process of refining is a most beautiful chemical operation: the granulated metal is boiled in concentrated sulphuric acid, which dissolves both the silver and the copper, leaving the gold nearly pure, in the form of a black powder. The solution is then placed in a leaden vessel containing metallic copper; this is gradually dissolved, and the silver precipitated in a pure metallic state. The sulphate of copper thus formed is also a valuable product, being employed in the manufacture of green and blue pigments. Other immediate results of the economical production of sulphuric acid, are the general employment of phosphorus matches, and of stearine candles, that beautiful substitute for tallow and wax. Twenty-five years ago, the present prices and extensive applications of sulphuric and muriatic acids, of soda, phosphorus, &c., would have been considered utterly impossible. Who is able to foresee what new and unthought-of chemical productions, ministering to the service and comforts of mankind, the next twenty-five years may produce? After these remarks you will perceive that it is no exaggeration to say, we may fairly judge of the commercial prosperity of a country from the amount of sulphuric acid it consumes. Reflecting upon the important influence which the price of sulphur exercises upon the cost of production of bleached and printed cotton stuffs, soap, glass, &c., and remembering that Great Britain supplies America, Spain, Portugal, and the East, with these, exchanging them for raw cotton, silk, wine, raisins, indigo, &c., &c., we can understand why the English Government should have resolved to resort to war with Naples, in order to abolish the sulphur monopoly, which the latter power attempted recently to establish. Nothing could be more opposed to the true interests of Sicily than such a monopoly; indeed, had it been maintained a few years, it is highly probable that sulphur, the source of her wealth, would have been rendered perfectly valueless to her. Science and industry form a power to which it is dangerous to present impediments. It was not difficult to perceive that the issue would be the entire cessation of the exportation of sulphur from Sicily. In the short period the sulphur monopoly lasted, fifteen patents were taken out for methods to obtain back the sulphuric acid used in making soda. Admitting that these fifteen experiments were not perfectly successful, there can be no doubt it would ere long have been accomplished. But then, in gypsum, (sulphate of lime), and in heavy-spar, (sulphate of barytes), we possess mountains of sulphuric acid; in galena, (sulphate of lead), and in iron pyrites, we have no less abundance of sulphur. The problem is, how to separate the sulphuric acid, or the sulphur, from these native stores. Hundreds of thousands of pounds weight of sulphuric acid were prepared from iron pyrites, while the high price of sulphur consequent upon the monopoly lasted. We should probably ere long have triumphed over all difficulties, and have separated it from gypsum. The impulse has been given, the possibility of the process proved, and it may happen in a few years that the inconsiderate financial speculation of Naples may deprive her of that lucrative commerce. In like manner Russia, by her prohibitory system, has lost much of her trade in tallow and potash. One country purchases only from absolute necessity from another, which excludes her own productions from her markets. Instead of the tallow and linseed oil of Russia, Great Britain now uses palm oil and cocoa-nut oil of other countries. Precisely analogous is the combination of workmen against their employers, which has led to the construction of many admirable machines for superseding manual labour. In commerce and industry every imprudence carries with it its own punishment; every oppression immediately and sensibly recoils upon the head of those from whom it emanates. LETTER IV My dear Sir, One of the most influential causes of improvement in the social condition of mankind is that spirit of enterprise which induces men of capital to adopt and carry out suggestions for the improvement of machinery, the creation of new articles of commerce, or the cheaper production of those already in demand; and we cannot but admire the energy with which such men devote their talents, their time, and their wealth, to realise the benefits of the discoveries and inventions of science. For even when these are expended upon objects wholly incapable of realisation,--nay, even when the idea which first gave the impulse proves in the end to be altogether impracticable or absurd, immediate good to the community generally ensues; some useful and perhaps unlooked-for result flows directly, or springs ultimately, from exertions frustrated in their main design. Thus it is also in the pursuit of science. Theories lead to experiments and investigations; and he who investigates will scarcely ever fail of being rewarded by discoveries. It may be, indeed, the theory sought to be established is entirely unfounded in nature; but while searching in a right spirit for one thing, the inquirer may be rewarded by finding others far more valuable than those which he sought. At the present moment, electro-magnetism, as a moving power, is engaging great attention and study; wonders are expected from its application to this purpose. According to the sanguine expectations of many persons, it will shortly be employed to put into motion every kind of machinery, and amongst other things it will be applied to impel the carriages of railroads, and this at so small a cost, that expense will no longer be matter of consideration. England is to lose her superiority as a manufacturing country, inasmuch as her vast store of coals will no longer avail her as an economical source of motive power. "We," say the German cultivators of this science, "have cheap zinc, and, how small a quantity of this metal is required to turn a lathe, and consequently to give motion to any kind of machinery!" Such expectations may be very attractive, and yet they are altogether illusory! they will not bear the test of a few simple calculations; and these our friends have not troubled themselves to institute. With a simple flame of spirits of wine, under a proper vessel containing boiling water, a small carriage of 200 to 300 pounds weight can be put into motion, or a weight of 80 to 100 pounds may be raised to a height of 20 feet. The same effects may be produced by dissolving zinc in dilute sulphuric acid in a certain apparatus. This is certainly an astonishing and highly interesting discovery; but the question to be determined is, which of the two processes is the least expensive? In order to answer this question, and to judge correctly of the hopes entertained from this discovery, let me remind you of what chemists denominate "equivalents." These are certain unalterable ratios of effects which are proportionate to each other, and may therefore be expressed in numbers. Thus, if we require 8 pounds of oxygen to produce a certain effect, and we wish to employ chlorine for the same effect, we must employ neither more nor less than 35 1/2 pounds weight. In the same manner, 6 pounds weight of coal are equivalent to 32 pounds weight of zinc. The numbers representing chemical equivalents express very general ratios of effects, comprehending for all bodies all the actions they are capable of producing. If zinc be combined in a certain manner with another metal, and submitted to the action of dilute sulphuric acid, it is dissolved in the form of an oxide; it is in fact burned at the expense of the oxygen contained in the fluid. A consequence of this action is the production of an electric current, which, if conducted through a wire, renders it magnetic. In thus effecting the solution of a pound weight, for example, of zinc, we obtain a definite amount of force adequate to raise a given weight one inch, and to keep it suspended; and the amount of weight it will be capable of suspending will be the greater the more rapidly the zinc is dissolved. By alternately interrupting and renewing the contact of the zinc with the acid, and by very simple mechanical arrangements, we can give to the iron an upward and downward or a horizontal motion, thus producing the conditions essential to the motion of any machinery. This moving force is produced by the oxidation of the zinc; and, setting aside the name given to the force in this case, we know that it can be produced in another manner. If we burn the zinc under the boiler of a steam-engine, consequently in the oxygen of the air instead of the galvanic pile, we should produce steam, and by it a certain amount of force. If we should assume, (which, however, is not proved,) that the quantity of force is unequal in these cases,--that, for instance, we had obtained double or triple the amount in the galvanic pile, or that in this mode of generating force less loss is sustained,--we must still recollect the equivalents of zinc and coal, and make these elements of our calculation. According to the experiments of Despretz, 6 pounds weight of zinc, in combining with oxygen, develops no more heat than 1 pound of coal; consequently, under equal conditions, we can produce six times the amount of force with a pound of coal as with a pound of zinc. It is therefore obvious that it would be more advantageous to employ coal instead of zinc, even if the latter produced four times as much force in a galvanic pile, as an equal weight of coal by its combustion under a boiler. Indeed it is highly probable, that if we burn under the boiler of a steam-engine the quantity of coal required for smelting the zinc from its ores, we shall produce far more force than the whole of the zinc so obtained could originate in any form of apparatus whatever. Heat, electricity, and magnetism, have a similar relation to each other as the chemical equivalents of coal, zinc, and oxygen. By a certain measure of electricity we produce a corresponding proportion of heat or of magnetic power; we obtain that electricity by chemical affinity, which in one shape produces heat, in another electricity or magnetism. A certain amount of affinity produces an equivalent of electricity in the same manner as, on the other hand, we decompose equivalents of chemical compounds by a definite measure of electricity. The magnetic force of the pile is therefore limited to the extent of the chemical affinity, and in the case before us is obtained by the combination of the zinc and sulphuric acid. In the combustion of coal, the heat results from, and is measured by, the affinity of the oxygen of the atmosphere for that substance. It is true that with a very small expense of zinc, we can make an iron wire a magnet capable of sustaining a thousand pounds weight of iron; let us not allow ourselves to be misled by this. Such a magnet could not raise a single pound weight of iron two inches, and therefore could not impart motion. The magnet acts like a rock, which while at rest presses with a weight of a thousand pounds upon a basis; it is like an inclosed lake, without an outlet and without a fall. But it may be said, we have, by mechanical arrangements, given it an outlet and a fall. True; and this must be regarded as a great triumph of mechanics; and I believe it is susceptible of further improvements, by which greater force may be obtained. But with every conceivable advantage of mechanism, no one will dispute that one pound of coal, under the boiler of a steam-engine, will give motion to a mass several hundred times greater than a pound of zinc in the galvanic pile. Our experience of the employment of electro-magnetism as a motory power is, however, too recent to enable us to foresee the ultimate results of contrivances to apply it; and, therefore, those who have devoted themselves to solve the problem of its application should not be discouraged, inasmuch as it would undoubtedly be a most important achievement to supersede the steam-engine, and thus escape the danger of railroads, even at double their expense. Professor Weber of Gottingen has thrown out a suggestion, that if a contrivance could be devised to enable us to convert at will the wheels of the steam-carriage into magnets, we should be enabled to ascend and descend acclivities with great facility. This notion may ultimately be, to a certain extent, realised. The employment of the galvanic pile as a motory power, however, must, like every other contrivance, depend upon the question of its relative economy: probably some time hence it may so far succeed as to be adopted in certain favourable localities; it may stand in the same relation to steam power as the manufacture of beet sugar bears to that of cane, or as the production of gas from oils and resins to that from mineral coal. The history of beet-root sugar affords us an excellent illustration of the effect of prices upon commercial productions. This branch of industry seems at length, as to its processes, to be perfected. The most beautiful white sugar is now manufactured from the beet-root, in the place of the treacle-like sugar, having the taste of the root, which was first obtained; and instead of 3 or 4 per cent., the proportion obtained by Achard, double or even treble that amount is now produced. And notwithstanding the perfection of the manufacture, it is probable it will ere long be in most places entirely discontinued. In the years 1824 to 1827, the prices of agricultural produce were much lower than at present, while the price of sugar was the same. At that time one malter [1] of wheat was 10s., and one klafter [2] of wood 18s., and land was falling in price. Thus, food and fuel were cheap, and the demand for sugar unlimited; it was, therefore, advantageous to grow beet-root, and to dispose of the produce of land as sugar. All these circumstances are now different. A malter of wheat costs 18s.; a klafter of wood, 30s. to 36s. Wages have risen, but not in proportion, whilst the price of colonial sugar has fallen. Within the limits of the German commercial league, as, for instance, at Frankfort-on-the-Maine, a pound of the whitest and best loaf sugar is 7d.; the import duty is 31/d., or 30s. per cwt., leaving 31/d. as the price of the sugar. In the year 1827, then, one malter of wheat was equal to 40 lbs. weight of sugar, whilst at present that quantity of wheat is worth 70 lbs. of sugar. If indeed fuel were the same in price as formerly, and 70 lbs. of sugar could be obtained from the same quantity of the root as then yielded 40 lbs., it might still be advantageously produced; but the amount, if now obtained by the most approved methods of extraction, falls far short of this; and as fuel is double the price, and labour dearer, it follows that, at present, it is far more advantageous to cultivate wheat and to purchase sugar. There are, however, other elements which must enter into our calculations; but these serve to confirm our conclusion that the manufacture of beet-root sugar as a commercial speculation must cease. The leaves and residue of the root, after the juice was expressed, were used as food for cattle, and their value naturally increased with the price of grain. By the process formerly pursued, 75 lbs. weight of juice were obtained from 100 lbs. of beet-root, and gave 5 lbs. of sugar. The method of Schutzenbach, which was eagerly adopted by the manufacturers, produced from the same quantity of root 8 lbs. of sugar; but it was attended with more expense to produce, and the loss of the residue as food for cattle. The increased expense in this process arises from the larger quantity of fuel required to evaporate the water; for instead of merely evaporating the juice, the dry residue is treated with water, and we require fuel sufficient to evaporate 106 lbs. of fluid instead of 75 lbs., and the residue is only fit for manure. The additional 3 lbs. of sugar are purchased at the expense of much fuel, and the loss of the residue as an article of food. If the valley of the Rhine possessed mines of diamonds as rich as those of Golconda, Visiapoor, or the Brazils, they would probably not be worth the working: at those places the cost of extraction is 28s. to 30s. the carat. With us it amounts to three or four times as much--to more, in fact, than diamonds are worth in the market. The sand of the Rhine contains gold; and in the Grand Duchy of Baden many persons are occupied in gold-washing when wages are low; but as soon as they rise, this employment ceases. The manufacture of sugar from beet-root, in the like manner, twelve to fourteen years ago offered advantages which are now lost: instead, therefore, of maintaining it at a great sacrifice, it would be more reasonable, more in accordance with true natural economy, to cultivate other and more valuable productions, and with them purchase sugar. Not only would the state be the gainer, but every member of the community. This argument does not apply, perhaps, to France and Bohemia, where the prices of fuel and of colonial sugar are very different to those in Germany. The manufacture of gas for lighting, from coal, resin, and oils, stands with us on the same barren ground. The price of the materials from which gas is manufactured in England bears a direct proportion to the price of corn: there the cost of tallow and oil is twice as great as in Germany, but iron and coal are two-thirds cheaper; and even in England the manufacture of gas is only advantageous when the other products of the distillation of coal, the coke, &c., can be sold. It would certainly be esteemed one of the greatest discoveries of the age if any one could succeed in condensing coal gas into a white, dry, solid, odourless substance, portable, and capable of being placed upon a candlestick, or burned in a lamp. Wax, tallow, and oil, are combustible gases in a solid or fluid form, which offer many advantages for lighting, not possessed by gas: they furnish, in well-constructed lamps, as much light, without requiring the expensive apparatus necessary for the combustion of gas, and they are generally more economical. In large towns, or such establishments as hotels, where coke is in demand, and where losses in stolen tallow or oil must be considered, together with the labour of snuffing candles and cleaning lamps, the higher price of gas is compensated. In places where gas can be manufactured from resin, oil of turpentine, and other cheap oils, as at Frankfort, this is advantageous so long as it is pursued on small scale only. If large towns were lighted in the same manner, the materials would rise in price: the whole amount at present produced would scarcely suffice for two such towns as Berlin and Munich. But no just calculation can be made from the present prices of turpentine, resin, &c., which are not produced upon any large scale. [Footnote 1: Malter--a measure containing several bushels, but varying in different countries.] [Footnote 2: Klafter--a cord, a stack, measuring six feet every way.] LETTER V My dear Sir, Until very recently it was supposed that the physical qualities of bodies, i.e. hardness, colour, density, transparency, &c., and still more their chemical properties, must depend upon the nature of their elements, or upon their composition. It was tacitly received as a principle, that two bodies containing the same elements in the same proportion, must of necessity possess the same properties. We could not imagine an exact identity of composition giving rise to two bodies entirely different in their sensible appearance and chemical relations. The most ingenious philosophers entertained the opinion that chemical combination is an inter-penetration of the particles of different kinds of matter, and that all matter is susceptible of infinite division. This has proved to be altogether a mistake. If matter were infinitely divisible in this sense, its particles must be imponderable, and a million of such molecules could not weigh more than an infinitely small one. But the particles of that imponderable matter, which, striking upon the retina, give us the sensation of light, are not in a mathematical sense infinitely small. Inter-penetration of elements in the production of a chemical compound, supposes two distinct bodies, A and B, to occupy one and the same space at the same time. If this were so, different properties could not consist with an equal and identical composition. That hypothesis, however, has shared the fate of innumerable imaginative explanations of natural phenomena, in which our predecessors indulged. They have now no advocate. The force of truth, dependent upon observation, is irresistible. A great many substances have been discovered amongst organic bodies, composed of the same elements in the same relative proportions, and yet exhibiting physical and chemical properties perfectly distinct one from another. To such substances the term Isomeric (from 1/ao1/ equal and aei1/o1/ part) is applied. A great class of bodies, known as the volatile oils, oil of turpentine, essence of lemons, oil of balsam of copaiba, oil of rosemary, oil of juniper, and many others, differing widely from each other in their odour, in their medicinal effects, in their boiling point, in their specific gravity, &c., are exactly identical in composition,--they contain the same elements, carbon and hydrogen, in the same proportions. How admirably simple does the chemistry of organic nature present itself to us from this point of view! An extraordinary variety of compound bodies produced with equal weights of two elements! and how wide their dissimilarity! The crystallised part of the oil of roses, the delicious fragrance of which is so well known, a solid at ordinary temperatures, although readily volatile, is a compound body containing exactly the same elements, and in the same proportions, as the gas we employ for lighting our streets; and, in short, the same elements, in the same relative quantities, are found in a dozen other compounds, all differing essentially in their physical and chemical properties. These remarkable truths, so highly important in their applications, were not received and admitted as sufficiently established, without abundant proofs. Many examples have long been known where the analysis of two different bodies gave the same composition; but such cases were regarded as doubtful: at any rate, they were isolated observations, homeless in the realms of science: until, at length, examples were discovered of two or more bodies whose absolute identity of composition, with totally distinct properties, could be demonstrated in a more obvious and conclusive manner than by mere analysis; that is, they can be converted and reconverted into each other without addition and without subtraction. In cyanuric acid, hydrated cyanic acid, and cyamelide, we have three such isomeric compounds. Cyanuric acid is crystalline, soluble in water, and capable of forming salts with metallic oxides. Hydrated cyanic acid is a volatile and highly blistering fluid, which cannot be brought into contact with water without being instantaneously decomposed. Cyamelide is a white substance very like porcelain, absolutely insoluble in water. Now if we place the first,--cyanuric acid,--in a vessel hermetically sealed, and apply a high degree of heat, it is converted by its influence into hydrated cyanic acid; and, then, if this is kept for some time at the common temperature, it passes into cyamelide, no other element being present. And, again inversely, cyamelide can be converted into cyanuric acid and hydrated cyanic acid. We have three other bodies which pass through similar changes, in aldehyde, metaldehyde, and etaldehyde; and, again two, in urea and cyanuret of ammonia. Further, 100 parts of aldehyde hydrated butyric acid and acetic ether contain the same elements in the same proportion. Thus one substance may be converted into another without addition or subtraction, and without the participation of any foreign bodies in the change. The doctrine that matter is not infinitely divisible, but on the contrary, consists of atoms incapable of further division, alone furnishes us with a satisfactory explanation of these phenomena. In chemical combinations, the ultimate atoms of bodies do not penetrate each other, they are only arranged side by side in a certain order, and the properties of the compound depend entirely upon this order. If they are made to change their place--their mode of arrangement--by an impulse from without, they combine again in a different manner, and another compound is formed with totally different properties. We may suppose that one atom combines with one atom of another element to form a compound atom, while in other bodies two and two, four and four, eight and eight, are united; so that in all such compounds the amount per cent. of the elements is absolutely equal; and yet their physical and chemical properties must be totally different, the constitution of each atom being peculiar, in one body consisting of two, in another of four, in a third of eight, and in a fourth of sixteen simple atoms. The discovery of these facts immediately led to many most beautiful and interesting results; they furnished us with a satisfactory explanation of observations which were before veiled in mystery,--a key to many of Nature's most curious recesses. Again; solid bodies, whether simple or compound, are capable of existing in two states, which are known by the terms amorphous and crystalline. When matter is passing from a gaseous or liquid state slowly into a solid, an incessant motion is observed, as if the molecules were minute magnets; they are seen to repel each other in one direction, and to attract and cohere together in another, and in the end become arranged into a regular form, which under equal circumstances is always the same for any given kind of matter; that is, crystals are formed. Time and freedom of motion for the particles of bodies are necessary to the formation of crystals. If we force a fluid or a gas to become suddenly solid, leaving no time for its particles to arrange themselves, and cohere in that direction in which the cohesive attraction is strongest, no crystals will be formed, but the resulting solid will have a different colour, a different degree of hardness and cohesion, and will refract light differently; in one word, will be amorphous. Thus we have cinnabar as a red and a jet-black substance; sulphur a fixed and brittle body, and soft, semitransparent, and ductile; glass as a milk-white opaque substance, so hard that it strikes fire with steel, and in its ordinary and well-known state. These dissimilar states and properties of the same body are occasioned in one case by a regular, in the other by an irregular, arrangement of its atoms; one is crystalline, the other amorphous. Applying these facts to natural productions, we have reason to believe that clay-slate, and many kinds of greywacke, are amorphous feldspar, as transition limestone is amorphous marble, basalt and lava mixtures of amorphous zeolite and augite. Anything that influences the cohesion, must also in a certain degree alter the properties of bodies. Carbonate of lime, if crystallised at ordinary temperatures, possesses the crystalline form, hardness, and refracting power of common spar; if crystallised at a higher temperature, it has the form and properties of arragonite. Finally, Isomorphism, or the equality of form of many chemical compounds having a different composition, tends to prove that matter consists of atoms the mere arrangement of which produces all the properties of bodies. But when we find that a different arrangement of the same elements gives rise to various physical and chemical properties, and a similar arrangement of different elements produces properties very much the same, may we not inquire whether some of those bodies which we regard as elements may not be merely modifications of the same substance?--whether they are not the same matter in a different state of arrangement? We know in fact the existence of iron in two states, so dissimilar, that in the one, it is to the electric chain like platinum, and in the other it is like zinc; so that powerful galvanic machines have been constructed of this one metal. Among the elements are several instances of remarkable similarity of properties. Thus there is a strong resemblance between platinum and iridium; bromine and iodine; iron, manganese, and magnesium; cobalt and nickel; phosphorus and arsenic; but this resemblance consists mainly in their forming isomorphous compounds in which these elements exist in the same relative proportion. These compounds are similar, because the atoms of which they are composed are arranged in the same manner. The converse of this is also true: nitrate of strontia becomes quite dissimilar to its common state if a certain proportion of water is taken into its composition. If we suppose selenium to be merely modified sulphur, and phosphorus modified arsenic, how does it happen, we must inquire, that sulphuric acid and selenic acid, phosphoric and arsenic acid, respectively form compounds which it is impossible to distinguish by their form and solubility? Were these merely isomeric, they ought to exhibit properties quite dissimilar! We have not, I believe, at present the remotest ground to suppose that any one of those substances which chemists regard as elements can be converted into another. Such a conversion, indeed, would presuppose that the element was composed of two or more ingredients, and was in fact not an element; and until the decomposition of these bodies is accomplished, and their constituents discovered, all pretensions to such conversions deserve no notice. Dr. Brown of Edinburgh thought he had converted iron into rhodium, and carbon or paracyanogen into silicon. His paper upon this subject was published in the Transactions of the Royal Society of Edinburgh, and contained internal evidence, without a repetition of his experiments, that he was totally unacquainted with the principles of chemical analysis. But his experiments have been carefully repeated by qualified persons, and they have completely proved his ignorance: his rhodium is iron, and his silicon an impure incombustible coal. LETTER VI My dear Sir, One of the most remarkable effects of the recent progress of science is the alliance of chemistry with physiology, by which a new and unexpected light has been thrown upon the vital processes of plants and animals. We have now no longer any difficulty in understanding the different actions of aliments, poisons, and remedial agents--we have a clear conception of the causes of hunger, of the exact nature of death; and we are not, as formerly, obliged to content ourselves with a mere description of their symptoms. It is now ascertained with positive certainty, that all the substances which constitute the food of man must be divided into two great classes, one of which serves for the nutrition and reproduction of the animal body, whilst the other ministers to quite different purposes. Thus starch, gum, sugar, beer, wine, spirits, &c., furnish no element capable of entering into the composition of blood, muscular fibre, or any part which is the seat of the vital principle. It must surely be universally interesting to trace the great change our views have undergone upon these subjects, as well as to become acquainted with the researches from which our present knowledge is derived. The primary conditions of the maintenance of animal life, are a constant supply of certain matters, animal food, and of oxygen, in the shape of atmospheric air. During every moment of life, oxygen is absorbed from the atmosphere in the organs of respiration, and the act of breathing cannot cease while life continues. The observations of physiologists have demonstrated that the body of an adult man supplied abundantly with food, neither increases nor diminishes in weight during twenty-four hours, and yet the quantity of oxygen absorbed into his system, in that period, is very considerable. According to the experiments of Lavoisier, an adult man takes into his system from the atmosphere, in one year, no less than 746 pounds weight of oxygen; the calculations of Menzies make the quantity amount even to 837 pounds; but we find his weight at the end of the year either exactly the same or different one way or the other by at most a few pounds. What, it may be asked, has become of the enormous amount of oxygen thus introduced into the human system in the course of one year? We can answer this question satisfactorily. No part of the oxygen remains in the body, but is given out again, combined with carbon and hydrogen. The carbon and hydrogen of certain parts of the animal body combine with the oxygen introduced through the lungs and skin, and pass off in the forms of carbonic acid and vapour of water. At every expiration and every moment of life, a certain amount of its elements are separated from the animal organism, having entered into combination with the oxygen of the atmosphere. In order to obtain a basis for the approximate calculation, we may assume, with Lavoisier and Seguin, that an adult man absorbs into his system 32 1/2 ounces of oxygen daily,--that is, 46,037 cubic inches = 15,661 grains, French weight; and further, that the weight of the whole mass of his blood is 24 pounds, of which 80 per cent. is water. Now, from the known composition of the blood, we know that in order to convert its whole amount of carbon and hydrogen into carbonic acid and water, 64.102 grains of oxygen are required. This quantity will be taken into the system in four days and five hours. Whether the oxygen enters into combination directly with the elements of the blood, or with the carbon and hydrogen of other parts of the body, it follows inevitably--the weight of the body remaining unchanged and in a normal condition--that as much of these elements as will suffice to supply 24 pounds of blood, must be taken into the system in four days and five hours; and this necessary amount is furnished by the food. We have not, however, remained satisfied with mere approximation: we have determined accurately, in certain cases, the quantity of carbon taken daily in the food, and of that which passes out of the body in the faeces and urine combined--that is, uncombined with oxygen; and from these investigations it appears that an adult man taking moderate exercise consumes 13.9 ounces of carbon, which pass off through the skin and lungs as carbonic acid gas. [1] It requires 37 ounces of oxygen to convert 13 9/10 of carbon into carbonic acid. Again; according to the analysis of Boussingault, (Annales de Chim. et de Phys., lxx. i. p.136), a horse consumes 79 1/10 ounces of carbon in twenty-four hours, a milch cow 70 3/4 ounces; so that the horse requires 13 pounds 3 1/2 ounces, and the cow 11 pounds 10 3/4 ounces of oxygen. [2] As no part of the oxygen taken into the system of an animal is given off in any other form than combined with carbon or hydrogen, and as in a normal condition, or state of health, the carbon and hydrogen so given off are replaced by those elements in the food, it is evident that the amount of nourishment required by an animal for its support must be in a direct ratio with the quantity of oxygen taken in to its system. Two animals which in equal times take up by means of the lungs and skin unequal quantities of oxygen, consume an amount of food unequal in the same ratio. The consumption of oxygen in a given time may be expressed by the number of respirations; it is, therefore, obvious that in the same animal the quantity of nourishment required must vary with the force and number of respirations. A child breathes quicker than an adult, and, consequently, requires food more frequently and proportionably in larger quantity, and bears hunger less easily. A bird deprived of food dies on the third day, while a serpent, confined under a bell, respires so slowly that the quantity of carbonic acid generated in an hour can scarcely be observed, and it will live three months, or longer, without food. The number of respirations is fewer in a state of rest than during labour or exercise: the quantity of food necessary in both cases must be in the same ratio. An excess of food, a want of a due amount of respired oxygen, or of exercise, as also great exercise (which obliges us to take an increased supply of food), together with weak organs of digestion, are incompatible with health. But the quantity of oxygen received by an animal through the lungs not only depends upon the number of respirations, but also upon the temperature of the respired air. The size of the thorax of an animal is unchangeable; we may therefore regard the volume of air which enters at every inspiration as uniform. But its weight, and consequently the amount of oxygen it contains, is not constant. Air is expanded by heat, and contracted by cold--an equal volume of hot and cold air contains, therefore, an unequal amount of oxygen. In summer atmospheric air contains water in the form of vapour, it is nearly deprived of it in winter; the volume of oxygen in the same volume of air is smaller in summer than in winter. In summer and winter, at the pole and at the equator, we inspire an equal volume of air; the cold air is warmed during respiration and acquires the temperature of the body. In order, therefore, to introduce into the lungs a given amount of oxygen, less expenditure of force is necessary in winter than in summer, and for the same expenditure of force more oxygen is inspired in winter. It is also obvious that in an equal number of respirations we consume more oxygen at the level of the sea than on a mountain. The oxygen taken into the system is given out again in the same form, both in summer and winter: we expire more carbon at a low than at a high temperature, and require more or less carbon in our food in the same proportion; and, consequently, more is respired in Sweden than in Sicily, and in our own country and eighth more in winter than in summer. Even if an equal weight of food is consumed in hot and cold climates, Infinite Wisdom has ordained that very unequal proportions of carbon shall be taken in it. The food prepared for the inhabitants of southern climes does not contain in a fresh state more than 12 per cent. of carbon, while the blubber and train oil which feed the inhabitants of Polar regions contain 66 to 80 per cent. of that element. From the same cause it is comparatively easy to be temperate in warm climates, or to bear hunger for a long time under the equator; but cold and hunger united very soon produce exhaustion. The oxygen of the atmosphere received into the blood in the lungs, and circulated throughout every part of the animal body, acting upon the elements of the food, is the source of animal heat. [Footnote 1: This account is deduced from observations made upon the average daily consumption of about 30 soldiers in barracks. The food of these men, consisting of meat, bread, potatoes, lentils, peas, beans, butter, salt, pepper, &c., was accurately weighed during a month, and each article subjected to ultimate analysis. Of the quantity of food, beer, and spirits, taken by the men when out of barracks, we have a close approximation from the report of the sergeant; and from the weight and analysis of the faeces and urine, it appears that the carbon which passes off through these channels may be considered equivalent to the amount taken in that portion of the food, and of sour-crout, which was not included in the estimate.] [Footnote 2: 17.5 ounces = 0.5 kilogramme.] LETTER VII My dear Sir, The source of animal heat, its laws, and the influence it exerts upon the functions of the animal body, constitute a curious and highly interesting subject, to which I would now direct your attention. All living creatures, whose existence depends upon the absorption of oxygen, possess within themselves a source of heat, independent of surrounding objects. This general truth applies to all animals, and extends to the seed of plants in the act of germination, to flower-buds when developing, and fruits during their maturation. In the animal body, heat is produced only in those parts to which arterial blood, and with it the oxygen absorbed in respiration, is conveyed. Hair, wool, and feathers, receive no arterial blood, and, therefore, in them no heat is developed. The combination of a combustible substance with oxygen is, under all circumstances, the only source of animal heat. In whatever way carbon may combine with oxygen, the act of combination is accompanied by the disengagement of heat. It is indifferent whether this combination takes place rapidly or slowly, at a high or at a low temperature: the amount of heat liberated is a constant quantity. The carbon of the food, being converted into carbonic acid within the body, must give out exactly as much heat as if it had been directly burnt in oxygen gas or in common air; the only difference is, the production of the heat is diffused over unequal times. In oxygen gas the combustion of carbon is rapid and the heat intense; in atmospheric air it burns slower and for a longer time, the temperature being lower; in the animal body the combination is still more gradual, and the heat is lower in proportion. It is obvious that the amount of heat liberated must increase or diminish with the quantity of oxygen introduced in equal times by respiration. Those animals, therefore, which respire frequently, and consequently consume much oxygen, possess a higher temperature than others, which, with a body of equal size to be heated, take into the system less oxygen. The temperature of a child (102 deg) is higher than that of an adult (99 1/2 deg). That of birds (104 deg to 105.4 deg) is higher than that of quadrupeds (98 1/2 deg to 100.4 deg) or than that of fishes or amphibia, whose proper temperature is from 2.7 to 3.6 deg higher than that of the medium in which they live. All animals, strictly speaking, are warm-blooded; but in those only which possess lungs is the temperature of the body quite independent of the surrounding medium. The most trustworthy observations prove that in all climates, in the temperate zones as well as at the equator or the poles, the temperature of the body in man, and in what are commonly called warm-blooded animals, is invariably the same; yet how different are the circumstances under which they live! The animal body is a heated mass, which bears the same relation to surrounding objects as any other heated mass. It receives heat when the surrounding objects are hotter, it loses heat when they are colder, than itself. We know that the rapidity of cooling increases with the difference between the temperature of the heated body and that of the surrounding medium; that is, the colder the surrounding medium the shorter the time required for the cooling of the heated body. How unequal, then, must be the loss of heat in a man at Palermo, where the external temperature is nearly equal to that of the body, and in the polar regions, where the external temperature is from 70 deg to 90 deg lower! Yet, notwithstanding this extremely unequal loss of heat, experience has shown that the blood of the inhabitant of the arctic circle has a temperature as high as that of the native of the south, who lives in so different a medium. This fact, when its true significance is perceived, proves that the heat given off to the surrounding medium is restored within the body with great rapidity. This compensation must consequently take place more rapidly in winter than in summer, at the pole than at the equator. Now, in different climates the quantity of oxygen introduced into the system by respiration, as has been already shown, varies according to the temperature of the external air; the quantity of inspired oxygen increases with the loss of heat by external cooling, and the quantity of carbon or hydrogen necessary to combine with this oxygen must be increased in the same ratio. It is evident that the supply of the heat lost by cooling is effected by the mutual action of the elements of the food and the inspired oxygen, which combine together. To make use of a familiar, but not on that account a less just illustration, the animal body acts, in this respect, as a furnace, which we supply with fuel. It signifies nothing what intermediate forms food may assume, what changes it may undergo in the body; the last change is uniformly the conversion of its carbon into carbonic acid, and of its hydrogen into water. The unassimilated nitrogen of the food, along with the unburned or unoxidised carbon, is expelled in the urine or in the solid excrements. In order to keep up in the furnace a constant temperature, we must vary the supply of fuel according to the external temperature, that is, according to the supply of oxygen. In the animal body the food is the fuel; with a proper supply of oxygen we obtain the heat given out during its oxidation or combustion. In winter, when we take exercise in a cold atmosphere, and when consequently the amount of inspired oxygen increases, the necessity for food containing carbon and hydrogen increases in the same ratio; and by gratifying the appetite thus excited, we obtain the most efficient protection against the most piercing cold. A starving man is soon frozen to death. The animals of prey in the arctic regions, as every one knows, far exceed in voracity those of the torrid zone. In cold and temperate climates, the air, which incessantly strives to consume the body, urges man to laborious efforts in order to furnish the means of resistance to its action, while, in hot climates, the necessity of labour to provide food is far less urgent. Our clothing is merely an equivalent for a certain amount of food. The more warmly we are clothed the less urgent becomes the appetite for food, because the loss of heat by cooling, and consequently the amount of heat to be supplied by the food, is diminished. If we were to go naked, like certain savage tribes, or if in hunting or fishing we were exposed to the same degree of cold as the Samoyedes, we should be able with ease to consume 10 lbs. of flesh, and perhaps a dozen of tallow candles into the bargain, daily, as warmly clad travellers have related with astonishment of these people. We should then also be able to take the same quantity of brandy or train oil without bad effects, because the carbon and hydrogen of these substances would only suffice to keep up the equilibrium between the external temperature and that of our bodies. According to the preceding expositions, the quantity of food is regulated by the number of respirations, by the temperature of the air, and by the amount of heat given off to the surrounding medium. No isolated fact, apparently opposed to this statement, can affect the truth of this natural law. Without temporary or permanent injury to health, the Neapolitan cannot take more carbon and hydrogen in the shape of food than he expires as carbonic acid and water; and the Esquimaux cannot expire more carbon and hydrogen than he takes in the system as food, unless in a state of disease or of starvation. Let us examine these states a little more closely. The Englishman in Jamaica perceives with regret the disappearance of his appetite, previously a source of frequently recurring enjoyment; and he succeeds, by the use of cayenne pepper, and the most powerful stimulants, in enabling himself to take as much food as he was accustomed to eat at home. But the whole of the carbon thus introduced into the system is not consumed; the temperature of the air is too high, and the oppressive heat does not allow him to increase the number of respirations by active exercise, and thus to proportion the waste to the amount of food taken; disease of some kind, therefore, ensues. On the other hand, England sends her sick to southern regions, where the amount of the oxygen inspired is diminished in a very large proportion. Those whose diseased digestive organs have in a greater or less degree lost the power of bringing the food into the state best adapted for oxidation, and therefore are less able to resist the oxidising influence of the atmosphere of their native climate, obtain a great improvement in health. The diseased organs of digestion have power to place the diminished amount of food in equilibrium with the inspired oxygen, in the mild climate; whilst in a colder region the organs of respiration themselves would have been consumed in furnishing the necessary resistance to the action of the atmospheric oxygen. In our climate, hepatic diseases, or those arising from excess of carbon, prevail in summer; in winter, pulmonary diseases, or those arising from excess of oxygen, are more frequent. The cooling of the body, by whatever cause it may be produced, increases the amount of food necessary. The mere exposure to the open air, in a carriage or on the deck of a ship, by increasing radiation and vaporisation, increases the loss of heat, and compels us to eat more than usual. The same is true of those who are accustomed to drink large quantities of cold water, which is given off at the temperature of the body, 98 1/2 deg. It increases the appetite, and persons of weak constitution find it necessary, by continued exercise, to supply to the system the oxygen required to restore the heat abstracted by the cold water. Loud and long continued speaking, the crying of infants, moist air, all exert a decided and appreciable influence on the amount of food which is taken. We have assumed that carbon and hydrogen especially, by combining with oxygen, serve to produce animal heat. In fact, observation proves that the hydrogen of the food plays a no less important part than the carbon. The whole process of respiration appears most clearly developed, when we consider the state of a man, or other animal, totally deprived of food. The first effect of starvation is the disappearance of fat, and this fat cannot be traced either in the urine or in the scanty faeces. Its carbon and hydrogen have been given off through the skin and lungs in the form of oxidised products; it is obvious that they have served to support respiration. In the case of a starving man, 32 1/2 oz. of oxygen enter the system daily, and are given out again in combination with a part of his body. Currie mentions the case of an individual who was unable to swallow, and whose body lost 100 lbs. in weight during a month; and, according to Martell (Trans. Linn. Soc., vol. xi. p.411), a fat pig, overwhelmed in a slip of earth, lived 160 days without food, and was found to have diminished in weight, in that time, more than 120 lbs. The whole history of hybernating animals, and the well-established facts of the periodical accumulation, in various animals, of fat, which, at other periods, entirely disappears, prove that the oxygen, in the respiratory process, consumes, without exception, all such substances as are capable of entering into combination with it. It combines with whatever is presented to it; and the deficiency of hydrogen is the only reason why carbonic acid is the chief product; for, at the temperature of the body, the affinity of hydrogen for oxygen far surpasses that of carbon for the same element. We know, in fact, that the graminivora expire a volume of carbonic acid equal to that of the oxygen inspired, while the carnivora, the only class of animals whose food contains fat, inspire more oxygen than is equal in volume to the carbonic acid expired. Exact experiments have shown, that in many cases only half the volume of oxygen is expired in the form of carbonic acid. These observations cannot be gainsaid, and are far more convincing than those arbitrary and artificially produced phenomena, sometimes called experiments; experiments which, made as too often they are, without regard to the necessary and natural conditions, possess no value, and may be entirely dispensed with; especially when, as in the present case, Nature affords the opportunity for observation, and when we make a rational use of that opportunity. In the progress of starvation, however, it is not only the fat which disappears, but also, by degrees all such of the solids as are capable of being dissolved. In the wasted bodies of those who have suffered starvation, the muscles are shrunk and unnaturally soft, and have lost their contractibility; all those parts of the body which were capable of entering into the state of motion have served to protect the remainder of the frame from the destructive influence of the atmosphere. Towards the end, the particles of the brain begin to undergo the process of oxidation, and delirium, mania, and death close the scene; that is to say, all resistance to the oxidising power of the atmospheric oxygen ceases, and the chemical process of eremacausis, or decay, commences, in which every part of the body, the bones excepted, enters into combination with oxygen. The time which is required to cause death by starvation depends on the amount of fat in the body, on the degree of exercise, as in labour or exertion of any kind, on the temperature of the air, and finally, on the presence or absence of water. Through the skin and lungs there escapes a certain quantity of water, and as the presence of water is essential to the continuance of the vital motions, its dissipation hastens death. Cases have occurred, in which a full supply of water being accessible to the sufferer, death has not occurred till after the lapse of twenty days. In one case, life was sustained in this way for the period of sixty days. In all chronic diseases death is produced by the same cause, namely, the chemical action of the atmosphere. When those substances are wanting, whose function in the organism is to support the process of respiration, when the diseased organs are incapable of performing their proper function of producing these substances, when they have lost the power of transforming the food into that shape in which it may, by entering into combination with the oxygen of the air, protect the system from its influence, then, the substance of the organs themselves, the fat of the body, the substance of the muscles, the nerves, and the brain, are unavoidably consumed. The true cause of death in these cases is the respiratory process, that is, the action of the atmosphere. A deficiency of food, and a want of power to convert the food into a part of the organism, are both, equally, a want of resistance; and this is the negative cause of the cessation of the vital process. The flame is extinguished, because the oil is consumed; and it is the oxygen of the air which has consumed it. In many diseases substances are produced which are incapable of assimilation. By the mere deprivation of food, these substances are removed from the body without leaving a trace behind; their elements have entered into combination with the oxygen of the air. From the first moment that the function of the lungs or of the skin is interrupted or disturbed, compounds, rich in carbon, appear in the urine, which acquires a brown colour. Over the whole surface of the body oxygen is absorbed, and combines with all the substances which offer no resistance to it. In those parts of the body where the access of oxygen is impeded; for example, in the arm-pits, or in the soles of the feet, peculiar compounds are given out, recognisable by their appearance, or by their odour. These compounds contain much carbon. Respiration is the falling weight--the bent spring, which keeps the clock in motion; the inspirations and expirations are the strokes of the pendulum which regulate it. In our ordinary time-pieces, we know with mathematical accuracy the effect produced on their rate of going, by changes in the length of the pendulum, or in the external temperature. Few, however, have a clear conception of the influence of air and temperature on the health of the human body; and yet the research into the conditions necessary to keep it in the normal state is not more difficult than in the case of a clock. LETTER VIII My dear Sir, Having attempted in my last letter to explain to you the simple and admirable office subserved by the oxygen of the atmosphere in its combination with carbon in the animal body, I will now proceed to present you with some remarks upon those materials which sustain its mechanisms in motion, and keep up their various functions,--namely, the Aliments. If the increase in mass in an animal body, the development and reproduction of its organs depend upon the blood, then those substances only which are capable of being converted into blood can be properly regarded as nourishment. In order then to ascertain what parts of our food are nutritious, we must compare the composition of the blood with the composition of the various articles taken as food. Two substances require especial consideration as the chief ingredients of the blood; one of these separates immediately from the blood when it is withdrawn from the circulation. It is well known that in this case blood coagulates, and separates into a yellowish liquid, the serum of the blood, and a gelatinous mass, which adheres to a rod or stick in soft, elastic fibres, when coagulating blood is briskly stirred. This is the fibrine of the blood, which is identical in all its properties with muscular fibre, when the latter is purified from all foreign matters. The second principal ingredient of the blood is contained in the serum, and gives to this liquid all the properties of the white of eggs, with which it is indeed identical. When heated, it coagulates into a white elastic mass, and the coagulating substance is called albumen. Fibrine and albumen, the chief ingredients of blood, contain, in all, seven chemical elements, among which nitrogen, phosphorus, and sulphur are found. They contain also the earth of bones. The serum retains in solution sea salt and other salts of potash and soda, in which the acids are carbonic, phosphoric, and sulphuric acids. The globules of the blood contain fibrine and albumen, along with a red colouring matter, in which iron is a constant element. Besides these, the blood contains certain fatty bodies in small quantity, which differ from ordinary fats in several of their properties. Chemical analysis has led to the remarkable result, that fibrine and albumen contain the same organic elements united in the same proportion,--i.e., that they are isomeric, their chemical composition--the proportion of their ultimate elements--being identical. But the difference of their external properties shows that the particles of which they are composed are arranged in a different order. (See Letter V). This conclusion has lately been beautifully confirmed by a distinguished physiologist (Denis), who has succeeded in converting fibrine into albumen, that is, in giving it the solubility, and coagulability by heat, which characterise the white of egg. Fibrine and albumen, besides having the same composition, agree also in this, that both dissolve in concentrated muriatic acid, yielding a solution of an intense purple colour. This solution, whether made with fibrine or albumen, has the very same re-actions with all substances yet tried. Both albumen and fibrine, in the process of nutrition, are capable of being converted into muscular fibre, and muscular fibre is capable of being reconverted into blood. These facts have long been established by physiologists, and chemistry has merely proved that these metamorphoses can be accomplished under the influence of a certain force, without the aid of a third substance, or of its elements, and without the addition of any foreign element, or the separation of any element previously present in these substances. If we now compare the composition of all organised parts with that of fibrine and albumen, the following relations present themselves:-- All parts of the animal body which have a decided shape, which form parts of organs, contain nitrogen. No part of an organ which possesses motion and life is destitute of nitrogen; all of them contain likewise carbon and the elements of water; the latter, however, in no case in the proportion to form water. The chief ingredients of the blood contain nearly 17 per cent. of nitrogen, and from numerous analyses it appears that no part of an organ contains less than 17 per cent. of nitrogen. The most convincing experiments and observations have proved that the animal body is absolutely incapable of producing an elementary body, such as carbon or nitrogen, out of substances which do not contain it; and it obviously follows, that all kinds of food fit for the production either of blood, or of cellular tissue, membranes, skin, hair, muscular fibre, &c., must contain a certain amount of nitrogen, because that element is essential to the composition of the above-named organs; because the organs cannot create it from the other elements presented to them; and, finally, because no nitrogen is absorbed from the atmosphere in the vital process. The substance of the brain and nerves contains a large quantity of albumen, and, in addition to this, two peculiar fatty acids, distinguished from other fats by containing phosphorus (phosphoric acid?). One of these contains nitrogen (Fremy). Finally, water and common fat are those ingredients of the body which are destitute of nitrogen. Both are amorphous or unorganised, and only so far take part in the vital process as that their presence is required for the due performance of the vital functions. The inorganic constituents of the body are, iron, lime, magnesia, common salt, and the alkalies. The nutritive process is seen in its simplest form in carnivorous animals. This class of animals lives on the blood and flesh of the graminivora; but this blood and flesh are, in all their properties, identical with their own. Neither chemical nor physiological differences can be discovered. The nutriment of carnivorous animals is derived originally from blood; in their stomach it becomes dissolved, and capable of reaching all other parts of the body; in its passage it is again converted into blood, and from this blood are reproduced all those parts of their organisation which have undergone change or metamorphosis. With the exception of hoofs, hair, feathers, and the earth of bones, every part of the food of carnivorous animals is capable of assimilation. In a chemical sense, therefore, it may be said that a carnivorous animal, in supporting the vital process, consumes itself. That which serves for its nutrition is identical with those parts of its organisation which are to be renewed. The process of nutrition in graminivorous animals appears at first sight altogether different. Their digestive organs are less simple, and their food consists of vegetables, the great mass of which contains but little nitrogen. From what substances, it may be asked, is the blood formed, by means of which of their organs are developed? This question may be answered with certainty. Chemical researches have shown, that all such parts of vegetables as can afford nutriment to animals contain certain constituents which are rich in nitrogen; and the most ordinary experience proves that animals require for their support and nutrition less of these parts of plants in proportion as they abound in the nitrogenised constituents. Animals cannot be fed on matters destitute of these nitrogenised constituents. These important products of vegetation are especially abundant in the seeds of the different kinds of grain, and of peas, beans, and lentils; in the roots and the juices of what are commonly called vegetables. They exist, however, in all plants, without exception, and in every part of plants in larger or smaller quantity. These nitrogenised forms of nutriment in the vegetable kingdom may be reduced to three substances, which are easily distinguished by their external characters. Two of them are soluble in water, the third is insoluble. When the newly-expressed juices of vegetables are allowed to stand, a separation takes place in a few minutes. A gelatinous precipitate, commonly of a green tinge, is deposited, and this, when acted on by liquids which remove the colouring matter, leaves a grayish white substance, well known to druggists as the deposite from vegetable juices. This is one of the nitrogenised compounds which serves for the nutrition of animals, and has been named vegetable fibrine. The juice of grapes is especially rich in this constituent, but it is most abundant in the seeds of wheat, and of the cerealia generally. It may be obtained from wheat flour by a mechanical operation, and in a state of tolerable purity; it is then called gluten, but the glutinous property belongs, not to vegetable fibrine, but to a foreign substance, present in small quantity, which is not found in the other cerealia. The method by which it is obtained sufficiently proves that it is insoluble in water; although we cannot doubt that it was originally dissolved in the vegetable juice, from which it afterwards separated, exactly as fibrine does from blood. The second nitrogenised compound remains dissolved in the juice after the separation of the fibrine. It does not separate from the juice at the ordinary temperature, but is instantly coagulated when the liquid containing it is heated to the boiling point. When the clarified juice of nutritious vegetables, such as cauliflower, asparagus, mangelwurzel, or turnips, is made to boil, a coagulum is formed, which it is absolutely impossible to distinguish from the substance which separates as a coagulum, when the serum of blood, or the white of an egg, diluted with water, are heated to the boiling point. This is vegetable albumen. It is found in the greatest abundance in certain seeds, in nuts, almonds, and others, in which the starch of the gramineae is replaced by oil. The third nitrogenised constituent of the vegetable food of animals is vegetable caseine. It is chiefly found in the seeds of peas, beans, lentils, and similar leguminous seeds. Like vegetable albumen, it is soluble in water, but differs from it in this, that its solution is not coagulated by heat. When the solution is heated or evaporated, a skin forms on its surface, and the addition of an acid causes a coagulum, just as in animal milk. These three nitrogenised compounds, vegetable fibrine, albumen, and caseine, are the true nitrogenised constituents of the food of graminivorous animals; all other nitrogenised compounds occurring in plants, are either rejected by animals, as in the case of the characteristic principles of poisonous and medicinal plants, or else they occur in the food in such very small proportion, that they cannot possibly contribute to the increase of mass in the animal body. The chemical analysis of these three substances has led to the very interesting result that they contain the same organic elements, united in the same proportion by weight; and, what is still more remarkable, that they are identical in composition with the chief constituents of blood, animal fibrine, and albumen. They all three dissolve in concentrated muriatic acid with the same deep purple colour, and even in their physical characters, animal fibrine and albumen are in no respect different from vegetable fibrine and albumen. It is especially to be noticed, that by the phrase, identity of composition, we do not here intend mere similarity, but that even in regard to the presence and relative amount of sulphur, phosphorus, and phosphate of lime, no difference can be observed. How beautifully and admirably simple, with the aid of these discoveries, appears the process of nutrition in animals, the formation of their organs, in which vitality chiefly resides! Those vegetable principles, which in animals are used to form blood, contain the chief constituents of blood, fibrine and albumen, ready formed, as far as regards their composition. All plants, besides, contain a certain quantity of iron, which reappears in the colouring matter of the blood. Vegetable fibrine and animal fibrine, vegetable albumen and animal albumen, hardly differ, even in form; if these principles be wanting in the food, the nutrition of the animal is arrested; and when they are present, the graminivorous animal obtains in its food the very same principles on the presence of which the nutrition of the carnivora entirely depends. Vegetables produce in their organism the blood of all animals, for the carnivora, in consuming the blood and flesh of the graminivora, consume, strictly speaking, only the vegetable principles which have served for the nutrition of the latter. Vegetable fibrine and albumen take the form in the stomach of the graminivorous animal as animal fibrine and albumen do in that of the carnivorous animal. From what has been said, it follows that the development of the animal organism and its growth are dependent on the reception of certain principles identical with the chief constituents of blood. In this sense we may say that the animal organism gives to the blood only its form; that it is incapable of creating blood out of other substances which do not already contain the chief constituents of that fluid. We cannot, indeed, maintain that the animal organism has no power to form other compounds, for we know that it is capable of producing an extensive series of compounds, differing in composition from the chief constituents of blood; but these last, which form the starting-point of the series, it cannot produce. The animal organism is a higher kind of vegetable, the development of which begins with those substances with the production of which the life of an ordinary vegetable ends. As soon as the latter has borne seed, it dies, or a period of its life comes to a termination. In that endless series of compounds, which begins with carbonic acid, ammonia, and water, the sources of the nutrition of vegetables, and includes the most complex constituents of the animal brain, there is no blank, no interruption. The first substance capable of affording nutriment to animals is the last product of the creative energy of vegetables. The substance of cellular tissue and of membranes, of the brain and nerves, these the vegetable cannot produce. The seemingly miraculous in the productive agency of vegetables disappears in a great degree, when we reflect that the production of the constituents of blood cannot appear more surprising than the occurrence of the fat of beef and mutton in cocoa beans, of human fat in olive-oil, of the principal ingredient of butter in palm-oil, and of horse fat and train-oil in certain oily seeds. LETTER IX My dear Sir, The facts detailed in my last letter will satisfy you as to the manner in which the increase of mass in an animal, that is, its growth, is accomplished; we have still to consider a most important question, namely, the function performed in the animal system by substances destitute of nitrogen; such as sugar, starch, gum, pectine, &c. The most extensive class of animals, the graminivora, cannot live without these substances; their food must contain a certain amount of one or more of them, and if these compounds are not supplied, death quickly ensues. This important inquiry extends also to the constituents of the food of carnivorous animals in the earliest periods of life; for this food also contains substances, which are not necessary for their support in the adult state. The nutrition of the young of carnivora is obviously accomplished by means similar to those by which the graminivora are nourished; their development is dependent on the supply of a fluid, which the body of the mother secretes in the shape of milk. Milk contains only one nitrogenised constituent, known under the name of caseine; besides this, its chief ingredients are butter (fat), and sugar of milk. The blood of the young animal, its muscular fibre, cellular tissue, nervous matter, and bones, must have derived their origin from the nitrogenised constituent of milk--the caseine; for butter and sugar of milk contain no nitrogen. Now, the analysis of caseine has led to the result, which, after the details I have given, can hardly excite your surprise, that this substance also is identical in composition with the chief constituents of blood, fibrine and albumen. Nay more--a comparison of its properties with those of vegetable caseine has shown--that these two substances are identical in all their properties; insomuch, that certain plants, such as peas, beans, and lentils, are capable of producing the same substance which is formed from the blood of the mother, and employed in yielding the blood of the young animal. The young animal, therefore, receives in the form of caseine,--which is distinguished from fibrine and albumen by its great solubility, and by not coagulating when heated,--the chief constituent of the mother's blood. To convert caseine into blood no foreign substance is required, and in the conversion of the mother's blood into caseine, no elements of the constituents of the blood have been separated. When chemically examined, caseine is found to contain a much larger proportion of the earth of bones than blood does, and that in a very soluble form, capable of reaching every part of the body. Thus, even in the earliest period of its life, the development of the organs, in which vitality resides, is, in the carnivorous animal, dependent on the supply of a substance, identical in organic composition with the chief constituents of its blood. What, then, is the use of the butter and the sugar of milk? How does it happen that these substances are indispensable to life? Butter and sugar of milk contain no fixed bases, no soda nor potash. Sugar of milk has a composition closely allied to that of the other kinds of sugar, of starch, and of gum; all of them contain carbon and the elements of water, the latter precisely in the proportion to form water. There is added, therefore, by means of these compounds, to the nitrogenised constituents of food, a certain amount of carbon; or, as in the case of butter, of carbon and hydrogen; that is, an excess of elements, which cannot possibly be employed in the production of blood, because the nitrogenised substances contained in the food already contain exactly the amount of carbon which is required for the production of fibrine and albumen. In an adult carnivorous animal, which neither gains nor loses weight, perceptibly, from day to day, its nourishment, the waste of organised tissue, and its consumption of oxygen, stand to each other in a well-defined and fixed relation. The carbon of the carbonic acid given off, with that of the urine; the nitrogen of the urine, and the hydrogen given off as ammonia and water; these elements, taken together, must be exactly equal in weight to the carbon, nitrogen, and hydrogen of the metamorphosed tissues, and since these last are exactly replaced by the food, to the carbon, nitrogen, and hydrogen of the food. Were this not the case, the weight of the animal could not possibly remain unchanged. But, in the young of the carnivora, the weight does not remain unchanged; on the contrary, it increases from day to day by an appreciable quantity. This fact presupposes, that the assimilative process in the young animal is more energetic, more intense, than the process of transformation in the existing tissues. If both processes were equally active, the weight of the body could not increase; and were the waste by transformation greater, the weight of the body would decrease. Now, the circulation in the young animal is not weaker, but, on the contrary, more rapid; the respirations are more frequent; and, for equal bulks, the consumption of oxygen must be greater rather than smaller in the young than in the adult animal. But, since the metamorphosis of organised parts goes on more slowly, there would ensue a deficiency of those substances, the carbon and hydrogen of which are adapted for combination with oxygen; because, in the carnivora, nature has destined the new compounds, produced by the metamorphosis of organised parts, to furnish the necessary resistance to the action of the oxygen, and to produce animal heat. What is wanting for these purposes an Infinite Wisdom has supplied to the young in its natural food. The carbon and hydrogen of butter, and the carbon of the sugar of milk, no part of either of which can yield blood, fibrine, or albumen, are destined for the support of the respiratory process, at an age when a greater resistance is opposed to the metamorphosis of existing organisms; or, in other words, to the production of compounds, which, in the adult state, are produced in quantity amply sufficient for the purpose of respiration. The young animal receives the constituents of its blood in the caseine of the milk. A metamorphosis of existing organs goes on, for bile and urine are secreted; the materials of the metamorphosed parts are given off in the form of urine, of carbonic acid, and of water; but the butter and sugar of milk also disappear; they cannot be detected in the faeces. The butter and sugar of milk are given out in the form of carbonic acid and water, and their conversion into oxidised products furnishes the clearest proof that far more oxygen is absorbed than is required to convert the carbon and hydrogen of the metamorphosed tissues into carbonic acid and water. The change and metamorphosis of organised tissues going on in the vital process in the young animal, consequently yield, in a given time, much less carbon and hydrogen in the form adapted for the respiratory process than correspond to the oxygen taken up in the lungs. The substance of its organised parts would undergo a more rapid consumption, and would necessarily yield to the action of the oxygen, were not the deficiency of carbon and hydrogen supplied from another source. The continued increase of mass, or growth, and the free and unimpeded development of the organs in the young animal, are dependent on the presence of foreign substances, which, in the nutritive process, have no other function than to protect the newly-formed organs from the action of the oxygen. The elements of these substances unite with the oxygen; the organs themselves could not do so without being consumed; that is, growth, or increase of mass in the body,--the consumption of oxygen remaining the same,--would be utterly impossible. The preceding considerations leave no doubt as to the purpose for which Nature has added to the food of the young of carnivorous mammalia substances devoid of nitrogen, which their organism cannot employ for nutrition, strictly so called, that is, for the production of blood; substances which may be entirely dispensed with in their nourishment in the adult state. In the young of carnivorous birds, the want of all motion is an obvious cause of diminished waste in the organised parts; hence, milk is not provided for them. The nutritive process in the carnivora thus presents itself under two distinct forms; one of which we again meet with in the graminivora. In graminivorous animals, we observe, that during their whole life, their existence depends on a supply of substances having a composition identical with that of sugar of milk, or closely resembling it. Everything that they consume as food contains a certain quantity of starch, gum, or sugar, mixed with other matters. The function performed in the vital process of the graminivora by these substances is indicated in a very clear and convincing manner, when we take into consideration the very small relative amount of the carbon which these animals consume in the nitrogenised constituents of their food, which bears no proportion whatever to the oxygen absorbed through the skin and lungs. A horse, for example, can be kept in perfectly good condition, if he obtain as food 15 lbs. of hay and 4 1/2 lbs. of oats daily. If we now calculate the whole amount of nitrogen in these matters, as ascertained by analysis (1 1/2 per cent. in the hay, 2.2 per cent. in the oats), in the form of blood, that is, as fibrine and albumen, with the due proportion of water in blood (80 per cent.), the horse receives daily no more than 4 1/2 oz. of nitrogen, corresponding to about 8 lbs. of blood. But along with this nitrogen, that is, combined with it in the form of fibrine or albumen, the animal receives only about 14 1/2 oz. of carbon. Without going further into the calculation, it will readily be admitted, that the volume of air inspired and expired by a horse, the quantity of oxygen consumed, and, as a necessary consequence, the amount of carbonic acid given out by the animal, are much greater than in the respiratory process in man. But an adult man consumes daily abut 14 oz. of carbon, and the determination of Boussingault, according to which a horse expires 79 oz. daily, cannot be very far from the truth. In the nitrogenised constituents of his food, therefore, the horse receives rather less than the fifth part of the carbon which his organism requires for the support of the respiratory process; and we see that the wisdom of the Creator has added to his food the four-fifths which are wanting, in various forms, as starch, sugar, &c. with which the animal must be supplied, or his organism will be destroyed by the action of the oxygen. It is obvious, that in the system of the graminivora, whose food contains so small a portion, relatively, of the constituents of the blood, the process of metamorphosis in existing tissues, and consequently their restoration or reproduction, must go on far less rapidly than in the carnivora. Were this not the case, a vegetation a thousand times more luxuriant than the actual one would not suffice for their nourishment. Sugar, gum, and starch, would no longer be necessary to support life in these animals, because, in that case, the products of the waste, or metamorphosis of the organised tissues, would contain enough carbon to support the respiratory process. LETTER X My dear Sir, Let me now apply the principles announced in the preceding letters to the circumstances of our own species. Man, when confined to animal food, requires for his support and nourishment extensive sources of food, even more widely extended than the lion and tiger, because, when he has the opportunity, he kills without eating. A nation of hunters, on a limited space, is utterly incapable of increasing its numbers beyond a certain point, which is soon attained. The carbon necessary for respiration must be obtained from the animals, of which only a limited number can live on the space supposed. These animals collect from plants the constituents of their organs and of their blood, and yield them, in turn, to the savages who live by the chase alone. They, again, receive this food unaccompanied by those compounds, destitute of nitrogen, which, during the life of the animals, served to support the respiratory process. In such men, confined to an animal diet, it is the carbon of the flesh and of the blood which must take the place of starch and sugar. But 15 lbs. of flesh contain no more carbon than 4 lbs. of starch, and while the savage with one animal and an equal weight of starch should maintain life and health for a certain number of days, he would be compelled, if confined to flesh alone, in order to procure the carbon necessary for respiration, during the same time, to consume five such animals. It is easy to see, from these considerations, how close the connection is between agriculture and the multiplication of the human species. The cultivation of our crops has ultimately no other object than the production of a maximum of those substances which are adapted for assimilation and respiration, in the smallest possible space. Grain and other nutritious vegetables yield us, not only in starch, sugar, and gum, the carbon which protects our organs from the action of oxygen, and produces in the organism the heat which is essential to life, but also in the form of vegetable fibrine, albumen, and caseine, our blood, from which the other parts of our body are developed. Man, when confined to animal food, respires, like the carnivora, at the expense of the matters produced by the metamorphosis of organised tissues; and, just as the lion, tiger, hyaena, in the cages of a menagerie, are compelled to accelerate the waste of the organised tissues by incessant motion, in order to furnish the matter necessary for respiration, so, the savage, for the very same object, is forced to make the most laborious exertions, and go through a vast amount of muscular exercise. He is compelled to consume force merely in order to supply matter for respiration. Cultivation is the economy of force. Science teaches us the simplest means of obtaining the greatest effect with the smallest expenditure of power, and with given means to produce a maximum of force. The unprofitable exertion of power, the waste of force in agriculture, in other branches of industry, in science, or in social economy, is characteristic of the savage state, or of the want of knowledge. In accordance with what I have already stated, you will perceive that the substances of which the food of man is composed may be divided into two classes; into nitrogenised and non-nitrogenised. The former are capable of conversion into blood; the latter are incapable of this transformation. Out of those substances which are adapted to the formation of blood, are formed all the organised tissues. The other class of substances, in the normal state of health, serve to support the process of respiration. The former may be called the plastic elements of nutrition; the latter, elements of respiration. Among the former we reckon-- Vegetable fibrine. Vegetable albumen. Vegetable caseine. Animal flesh. Animal blood. Among the elements of respiration in our food, are-- Fat. Pectine. Starch. Bassorine. Gum. Wine. Cane sugar. Beer. Grape sugar. Spirits. Sugar of milk. The most recent and exact researches have established as a universal fact, to which nothing yet known is opposed, that the nitrogenised constituents of vegetable food have a composition identical with that of the constituents of the blood. No nitrogenised compound, the composition of which differs from that of fibrine, albumen, and caseine, is capable of supporting the vital process in animals. The animal organism unquestionably possesses the power of forming, from the constituents of its blood, the substance of its membranes and cellular tissue, of the nerves and brain, and of the organic part of cartilages and bones. But the blood must be supplied to it perfect in everything but its form--that is, in its chemical composition. If this be not done, a period is rapidly put to the formation of blood, and consequently to life. This consideration enables us easily to explain how it happens that the tissues yielding gelatine or chondrine, as, for example, the gelatine of skin or of bones, are not adapted for the support of the vital process; for their composition is different from that of fibrine or albumen. It is obvious that this means nothing more than that those parts of the animal organism which form the blood do not possess the power of effecting a transformation in the arrangement of the elements of gelatine, or of those tissues which contain it. The gelatinous tissues, the gelatine of the bones, the membranes, the cells and the skin suffer, in the animal body, under the influence of oxygen and moisture, a progressive alteration; a part of these tissues is separated, and must be restored from the blood; but this alteration and restoration are obviously confined within very narrow limits. While, in the body of a starving or sick individual, the fat disappears and the muscular tissue takes once more the form of blood, we find that the tendons and membranes retain their natural condition, and the limbs of the dead body their connections, which depend on the gelatinous tissues. On the other hand, we see that the gelatine of bones devoured by a dog entirely disappears, while only the bone earth is found in his excrements. The same is true of man, when fed on food rich in gelatine, as, for example, strong soup. The gelatine is not to be found either in the urine or in the faeces, and consequently must have undergone a change, and must have served some purpose in the animal economy. It is clear that the gelatine must be expelled from the body in a form different from that in which it was introduced as food. When we consider the transformation of the albumen of the blood into a part of an organ composed of fibrine, the identity in composition of the two substances renders the change easily conceivable. Indeed we find the change of a dissolved substance into an insoluble organ of vitality, chemically speaking, natural and easily explained, on account of this very identity of composition. Hence the opinion is not unworthy of a closer investigation, that gelatine, when taken in the dissolved state, is again converted, in the body, into cellular tissue, membrane and cartilage; that it may serve for the reproduction of such parts of these tissues as have been wasted, and for their growth. And when the powers of nutrition in the whole body are affected by a change of the health, then, even should the power of forming blood remain the same, the organic force by which the constituents of the blood are transformed into cellular tissue and membranes must necessarily be enfeebled by sickness. In the sick man, the intensity of the vital force, its power to produce metamorphoses, must be diminished as well in the stomach as in all other parts of the body. In this condition, the uniform experience of practical physicians shows that gelatinous matters in a dissolved state exercise a most decided influence on the state of the health. Given in a form adapted for assimilation, they serve to husband the vital force, just as may be done, in the case of the stomach, by due preparation of the food in general. Brittleness in the bones of graminivorous animals is clearly owing to a weakness in those parts of the organism whose function it is to convert the constituents of the blood into cellular tissue and membrane; and if we can trust to the reports of physicians who have resided in the East, the Turkish women, in their diet of rice, and in the frequent use of enemata of strong soup, have united the conditions necessary for the formation both of cellular tissue and of fat. LETTER XI My dear Sir, In the immense, yet limited expanse of the ocean, the animal and vegetable kingdoms are mutually dependent upon, and successive to each other. The animals obtain their constituent elements from the plants, and restore them to the water in their original form, when they again serve as nourishment to a new generation of plants. The oxygen which marine animals withdraw in their respiration from the air, dissolved in sea water, is returned to the water by the vital processes of sea plants; that air is richer in oxygen than atmospheric air, containing 32 to 33 per cent. Oxygen, also, combines with the products of the putrefaction of dead animal bodies, changes their carbon into carbonic acid, their hydrogen into water, and their nitrogen assumes again the form of ammonia. Thus we observe in the ocean a circulation takes place without the addition or subtraction of any element, unlimited in duration, although limited in extent, inasmuch as in a confined space the nourishment of plants exists in a limited quantity. We well know that marine plants cannot derive a supply of humus for their nourishment through their roots. Look at the great sea-tang, the Fucus giganteus: this plant, according to Cook, reaches a height of 360 feet, and a single specimen, with its immense ramifications, nourishes thousands of marine animals, yet its root is a small body, no larger than the fist. What nourishment can this draw from a naked rock, upon the surface of which there is no perceptible change? It is quite obvious that these plants require only a hold,--a fastening to prevent a change of place,--as a counterpoise to their specific gravity, which is less than that of the medium in which they float. That medium provides the necessary nourishment, and presents it to the surface of every part of the plant. Sea-water contains not only carbonic acid and ammonia, but the alkaline and earthy phosphates and carbonates required by these plants for their growth, and which we always find as constant constituents of their ashes. All experience demonstrates that the conditions of the existence of marine plants are the same which are essential to terrestrial plants. But the latter do not live like sea-plants, in a medium which contains all their elements and surrounds with appropriate nourishment every part of their organs; on the contrary, they require two media, of which one, namely the soil, contains those essential elements which are absent from the medium surrounding them, i.e. the atmosphere. Is it possible that we could ever be in doubt respecting the office which the soil and its component parts subserve in the existence and growth of vegetables?--that there should have been a time when the mineral elements of plants were not regarded as absolutely essential to their vitality? Has not the same circulation been observed on the surface of the earth which we have just contemplated in the ocean,--the same incessant change, disturbance and restitution of equilibrium? Experience in agriculture shows that the production of vegetables on a given surface increases with the supply of certain matters, originally parts of the soil which had been taken up from it by plants--the excrements of man and animals. These are nothing more than matters derived from vegetable food, which in the vital processes of animals, or after their death, assume again the form under which they originally existed, as parts of the soil. Now, we know that the atmosphere contains none of these substances, and therefore can replace none; and we know that their removal from a soil destroys its fertility, which may be restored and increased by a new supply. Is it possible, after so many decisive investigations into the origin of the elements of animals and vegetables, the use of the alkalies, of lime and the phosphates, any doubt can exist as to the principles upon which a rational agriculture depends? Can the art of agriculture be based upon anything but the restitution of a disturbed equilibrium? Can it be imagined that any country, however rich and fertile, with a flourishing commerce, which for centuries exports its produce in the shape of grain and cattle, will maintain its fertility, if the same commerce does not restore, in some form of manure, those elements which have been removed from the soil, and which cannot be replaced by the atmosphere? Must not the same fate await every such country which has actually befallen the once prolific soil of Virginia, now in many parts no longer able to grow its former staple productions--wheat and tobacco? In the large towns of England the produce both of English and foreign agriculture is largely consumed; elements of the soil indispensable to plants do not return to the fields,--contrivances resulting from the manners and customs of English people, and peculiar to them, render it difficult, perhaps impossible, to collect the enormous quantity of the phosphates which are daily, as solid and liquid excrements, carried into the rivers. These phosphates, although present in the soil in the smallest quantity, are its most important mineral constituents. It was observed that many English fields exhausted in that manner immediately doubled their produce, as if by a miracle, when dressed with bone earth imported from the Continent. But if the export of bones from Germany is continued to the extent it has hitherto reached, our soil must be gradually exhausted, and the extent of our loss may be estimated, by considering that one pound of bones contains as much phosphoric acid as a hundred-weight of grain. The imperfect knowledge of Nature and the properties and relations of matter possessed by the alchemists gave rise, in their time, to an opinion that metals as well as plants could be produced from a seed. The regular forms and ramifications seen in crystals, they imagined to be the leaves and branches of metal plants; and as they saw the seed of plants grow, producing root, stem and leaves, and again blossoms, fruit and seeds, apparently without receiving any supply of appropriate material, they deemed it worthy of zealous inquiry to discover the seed of gold, and the earth necessary for its development. If the metal seeds were once obtained, might they not entertain hopes of their growth? Such ideas could only be entertained when nothing was known of the atmosphere, and its participation with the earth, in administering to the vital processes of plants and animals. Modern chemistry indeed produces the elements of water, and, combining them, forms water anew; but it does not create those elements--it derives them from water; the new-formed artificial water has been water before. Many of our farmers are like the alchemists of old,--they are searching for the miraculous seed,--the means, which, without any further supply of nourishment to a soil scarcely rich enough to be sprinkled with indigenous plants, shall produce crops of grain a hundred-fold. The experience of centuries, nay, of thousands of years, is insufficient to guard men against these fallacies; our only security from these and similar absurdities must be derived from a correct knowledge of scientific principles. In the first period of natural philosophy, organic life was supposed to be derived from water only; afterwards, it was admitted that certain elements derived from the air must be superadded to the water; but we now know that other elements must be supplied by the earth, if plants are to thrive and multiply. The amount of materials contained in the atmosphere, suited to the nourishment of plants, is limited; but it must be abundantly sufficient to cover the whole surface of the earth with a rich vegetation. Under the tropics, and in those parts of our globe where the most genial conditions of fertility exist,--a suitable soil, a moist atmosphere, and a high temperature,--vegetation is scarcely limited by space; and, where the soil is wanting, it is gradually supplied by the decaying leaves, bark and branches of plants. It is obvious there is no deficiency of atmospheric nourishment for plants in those regions, nor are these wanting in our own cultivated fields: all that plants require for their development is conveyed to them by the incessant motions of the atmosphere. The air between the tropics contains no more than that of the arctic zones; and yet how different is the amount of produce of an equal surface of land in the two situations! This is easily explicable. All the plants of tropical climates, the oil and wax palms, the sugar cane, &c., contain only a small quantity of the elements of the blood necessary to the nutrition of animals, as compared with our cultivated plants. The tubers of the potato in Chili, its native country, where the plant resembles a shrub, if collected from an acre of land, would scarcely suffice to maintain an Irish family for a single day (Darwin). The result of cultivation in those plants which serve as food, is to produce in them those constituents of the blood. In the absence of the elements essential to these in the soil, starch, sugar and woody fibre, are perhaps formed; but no vegetable fibrine, albumen, or caseine. If we intend to produce on a given surface of soil more of these latter matters than the plants can obtain from the atmosphere or receive from the soil of the same surface in its uncultivated and normal state, we must create an artificial atmosphere, and add the needed elements to the soil. The nourishment which must be supplied in a given time to different plants, in order to admit a free and unimpeded growth, is very unequal. On pure sand, on calcareous soil, on naked rocks, only a few genera of plants prosper, and these are, for the most part, perennial plants. They require, for their slow growth, only such minute quantities of mineral substances as the soil can furnish, which may be totally barren for other species. Annual, and especially summer plants, grow and attain their perfection in a comparatively short time; they therefore do not prosper on a soil which is poor in those mineral substances necessary to their development. To attain a maximum in height in the short period of their existence, the nourishment contained in the atmosphere is not sufficient. If the end of cultivation is to be obtained, we must create in the soil an artificial atmosphere of carbonic acid and ammonia; and this surplus of nourishment, which the leaves cannot appropriate from the air, must be taken up by the corresponding organs, i.e. the roots, from the soil. But the ammonia, together with the carbonic acid, are alone insufficient to become part of a plant destined to the nourishment of animals. In the absence of the alkalies, the phosphates and other earthy salts, no vegetable fibrine, no vegetable caseine, can be formed. The phosphoric acid of the phosphate of lime, indispensable to the cerealia and other vegetables in the formation of their seeds, is separated as an excrement, in great quantities, by the rind and barks of ligneous plants. How different are the evergreen plants, the cacti, the mosses, the ferns, and the pines, from our annual grasses, the cerealia and leguminous vegetables! The former, at every time of the day during winter and summer, obtain carbon through their leaves by absorbing carbonic acid which is not furnished by the barren soil on which they grow; water is also absorbed and retained by their coriaceous or fleshy leaves with great force. They lose very little by evaporation, compared with other plants. On the other hand, how very small is the quantity of mineral substances which they withdraw from the soil during their almost constant growth in one year, in comparison with the quantity which one crop of wheat of an equal weight receives in three months! It is by means of moisture that plants receive the necessary alkalies and salts from the soil. In dry summers a phenomenon is observed, which, when the importance of mineral elements to the life of a plant was unknown, could not be explained. The leaves of plants first developed and perfected, and therefore nearer the surface of the soil, shrivel up and become yellow, lose their vitality, and fall off while the plant is in an active state of growth, without any visible cause. This phenomenon is not seen in moist years, nor in evergreen plants, and but rarely in plants which have long and deep roots, nor is it seen in perennials in autumn and winter. The cause of this premature decay is now obvious. The perfectly-developed leaves absorb continually carbonic acid and ammonia from the atmosphere, which are converted into elements of new leaves, buds, and shoots; but this metamorphosis cannot be effected without the aid of the alkalies, and other mineral substances. If the soil is moist, the latter are continually supplied to an adequate amount, and the plant retains its lively green colour; but if this supply ceases from a want of moisture to dissolve the mineral elements, a separation takes place in the plant itself. The mineral constituents of the juice are withdrawn from the leaves already formed, and are used for the formation of the young shoots; and as soon as the seeds are developed, the vitality of the leaves completely ceases. These withered leaves contain only minute traces of soluble salts, while the buds and shoots are very rich in them. On the other hand, it has been observed, that where a soil is too highly impregnated with soluble saline materials, these are separated upon the surface of the leaves. This happens to culinary vegetables especially, whose leaves become covered with a white crust. In consequence of these exudations the plant sickens, its organic activity decreases, its growth is disturbed; and if this state continues long, the plant dies. This is most frequently seen in foliaceous plants, the large surfaces of which evaporate considerable quantities of water. Carrots, pumpkins, peas, &c., are frequently thus diseased, when, after dry weather, the plant being near its full growth, the soil is moistened by short showers, followed again by dry weather. The rapid evaporation carries off the water absorbed by the root, and this leaves the salts in the plant in a far greater quantity than it can assimilate. These salts effloresce upon the surface of the leaves, and if they are herbaceous and juicy, produce an effect upon them as if they had been watered with a solution containing a greater quantity of salts than their organism can bear. Of two plants of the same species, this disease befalls that which is nearest its perfection; if one should have been planted later, or be more backward in its development, the same external cause which destroys the one will contribute to the growth of the other. LETTER XII My dear Sir, Having now occupied several letters with the attempt to unravel, by means of chemistry, some of the most curious functions of the animal body, and, as I hope, made clear to you the distinctions between the two kinds of constituent elements in food, and the purposes they severally subserve in sustaining life, let me now direct your attention to a scarcely less interesting and equally important subject--the means of obtaining from a given surface of the earth the largest amount of produce adapted to the food of man and animals. Agriculture is both a science and an art. The knowledge of all the conditions of the life of vegetables, the origin of their elements, and the sources of their nourishment, forms its scientific basis. From this knowledge we derive certain rules for the exercise of the ART, the principles upon which the mechanical operations of farming depend, the usefulness or necessity of these for preparing the soil to support the growth of plants, and for removing every obnoxious influence. No experience, drawn from the exercise of the art, can be opposed to true scientific principles, because the latter should include all the results of practical operations, and are in some instances solely derived therefrom. Theory must correspond with experience, because it is nothing more than the reduction of a series of phenomena to their last causes. A field in which we cultivate the same plant for several successive years becomes barren for that plant in a period varying with the nature of the soil: in one field it will be in three, in another in seven, in a third in twenty, in a fourth in a hundred years. One field bears wheat, and no peas; another beans or turnips, but no tobacco; a third gives a plentiful crop of turnips, but will not bear clover. What is the reason that a field loses its fertility for one plant, the same which at first flourished there? What is the reason one kind of plant succeeds in a field where another fails? These questions belong to Science. What means are necessary to preserve to a field its fertility for one and the same plant?--what to render one field fertile for two, for three, for all plants? These last questions are put by Art, but they cannot be answered by Art. If a farmer, without the guidance of just scientific principles, is trying experiments to render a field fertile for a plant which it otherwise will not bear, his prospect of success is very small. Thousands of farmers try such experiments in various directions, the result of which is a mass of practical experience forming a method of cultivation which accomplishes the desired end for certain places; but the same method frequently does not succeed, it indeed ceases to be applicable to a second or third place in the immediate neighbourhood. How large a capital, and how much power, are wasted in these experiments! Very different, and far more secure, is the path indicated by SCIENCE; it exposes us to no danger of failing, but, on the contrary, it furnishes us with every guarantee of success. If the cause of failure--of barrenness in the soil for one or two plants--has been discovered, means to remedy it may readily be found. The most exact observations prove that the method of cultivation must vary with the geognostical condition of the subsoil. In basalt, graywacke, porphyry, sandstone, limestone, &c., are certain elements indispensable to the growth of plants, and the presence of which renders them fertile. This fully explains the difference in the necessary methods of culture for different places; since it is obvious that the essential elements of the soil must vary with the varieties of composition of the rocks, from the disintegration of which they originated. Wheat, clover, turnips, for example, each require certain elements from the soil; they will not flourish where the appropriate elements are absent. Science teaches us what elements are essential to every species of plants by an analysis of their ashes. If therefore a soil is found wanting in any of those elements, we discover at once the cause of its barrenness, and its removal may now be readily accomplished. The empiric attributes all his success to the mechanical operations of agriculture; he experiences and recognises their value, without inquiring what are the causes of their utility, their mode of action: and yet this scientific knowledge is of the highest importance for regulating the application of power and the expenditure of capital,--for insuring its economical expenditure and the prevention of waste. Can it be imagined that the mere passing of the ploughshare or the harrow through the soil--the mere contact of the iron--can impart fertility miraculously? Nobody, perhaps, seriously entertains such an opinion. Nevertheless, the modus operandi of these mechanical operations is by no means generally understood. The fact is quite certain, that careful ploughing exerts the most favourable influence: the surface is thus mechanically divided, changed, increased, and renovated; but the ploughing is only auxiliary to the end sought. In the effects of time, in what in Agriculture are technically called fallows--the repose of the fields--we recognise by science certain chemical actions, which are continually exercised by the elements of the atmosphere upon the whole surface of our globe. By the action of its oxygen and its carbonic acid, aided by water, rain, changes of temperature, &c., certain elementary constituents of rocks, or of their ruins, which form the soil capable of cultivation, are rendered soluble in water, and consequently become separable from all their insoluble parts. These chemical actions, poetically denominates the "tooth of time," destroy all the works of man, and gradually reduce the hardest rocks to the condition of dust. By their influence the necessary elements of the soil become fitted for assimilation by plants; and it is precisely the end which is obtained by the mechanical operations of farming. They accelerate the decomposition of the soil, in order to provide a new generation of plants with the necessary elements in a condition favourable to their assimilation. It is obvious that the rapidity of the decomposition of a solid body must increase with the extension of its surface; the more points of contact we offer in a given time to the external chemical agent, the more rapid will be its action. The chemist, in order to prepare a mineral for analysis, to decompose it, or to increase the solubility of its elements, proceeds in the same way as the farmer deals with his fields--he spares no labour in order to reduce it to the finest powder; he separates the impalpable from the coarser parts by washing, and repeats his mechanical bruising and trituration, being assured his whole process will fail if he is inattentive to this essential and preliminary part of it. The influence which the increase of surface exercises upon the disintegration of rocks, and upon the chemical action of air and moisture, is strikingly illustrated upon a large scale in the operations pursued in the gold-mines of Yaquil, in Chili. These are described in a very interesting manner by Darwin. The rock containing the gold ore is pounded by mills into the finest powder; this is subjected to washing, which separates the lighter particles from the metallic; the gold sinks to the bottom, while a stream of water carries away the lighter earthy parts into ponds, where it subsides to the bottom as mud. When this deposit has gradually filled up the pond, this mud is taken out and piled in heaps, and left exposed to the action of the atmosphere and moisture. The washing completely removes all the soluble part of the disintegrated rock; the insoluble part, moreover, cannot undergo any further change while it is covered with water, and so excluded from the influence of the atmosphere at the bottom of the pond. But being exposed at once to the air and moisture, a powerful chemical action takes place in the whole mass, which becomes indicated by an efflorescence of salts covering the whole surface of the heaps in considerable quantity. After being exposed for two or three years, the mud is again subjected to the same process of washing, and a considerable quantity of gold is obtained, this having been separated by the chemical process of decomposition in the mass. The exposure and washing of the same mud is repeated six or seven times, and at every washing it furnishes a new quantity of gold, although its amount diminishes every time. Precisely similar is the chemical action which takes place in the soil of our fields; and we accelerate and increase it by the mechanical operations of our agriculture. By these we sever and extend the surface, and endeavour to make every atom of the soil accessible to the action of the carbonic acid and oxygen of the atmosphere. We thus produce a stock of soluble mineral substances, which serves as nourishment to a new generation of plants, materials which are indispensable to their growth and prosperity. LETTER XIII My dear Sir, Having in my last letter spoken of the general principles upon which the science and art of agriculture must be based, let me now direct your attention to some of those particulars between chemistry and agriculture, and demonstrate the impossibility of perfecting the important art of rearing food for man and animals, without a profound knowledge of our science. All plants cultivated as food require for their healthy sustenance the alkalies and alkaline earths, each in a certain proportion; and in addition to these, the cerealia do not succeed in a soil destitute of silica in a soluble condition. The combinations of this substance found as natural productions, namely, the silicates, differ greatly in the degree of facility with which they undergo decomposition, in consequence of the unequal resistance opposed by their integral parts to the dissolving power of the atmospheric agencies. Thus the granite of Corsica degenerates into a powder in a time which scarcely suffices to deprive the polished granite of Heidelberg of its lustre. Some soils abound in silicates so readily decomposable, that in every one or two years, as much silicate of potash becomes soluble and fitted for assimilation as is required by the leaves and straw of a crop of wheat. In Hungary, extensive districts are not uncommon where wheat and tobacco have been grown alternately upon the same soil for centuries, the land never receiving back any of those mineral elements which were withdrawn in the grain and straw. On the other hand, there are fields in which the necessary amount of soluble silicate of potash for a single crop of wheat is not separated from the insoluble masses in the soil in less than two, three, or even more years. The term fallow, in Agriculture, designates that period in which the soil, left to the influence of the atmosphere, becomes enriched with those soluble mineral constituents. Fallow, however, does not generally imply an entire cessation of cultivation, but only an interval in the growth of the cerealia. That store of silicates and alkalies which is the principal condition of their success is obtained, if potatoes or turnips are grown upon the same fields in the intermediate periods, since these crops do not abstract a particle of silica, and therefore leave the field equally fertile for the following crop of wheat. The preceding remarks will render it obvious to you, that the mechanical working of the soil is the simplest and cheapest method of rendering the elements of nutrition contained in it accessible to plants. But it may be asked, Are there not other means of decomposing the soil besides its mechanical subdivision?--are there not substances, which by their chemical operation will equally well or better render its constituents suitable for entering into vegetable organisms? Yes: we certainly possess such substances, and one of them, namely, quick-lime, has been employed for the last century past in England for this purpose; and it would be difficult to find a substance better adapted to this service, as it is simple, and in almost all localities cheap and easily accessible. In order to obtain correct views respecting the effect of quick-lime upon the soil, let me remind you of the first process employed by the chemist when he is desirous of analysing a mineral, and for this purpose wishes to bring its elements into a soluble state. Let the mineral to be examined be, for instance, feldspar; this substance, taken alone, even when reduced to the finest powder, requires for its solution to be treated with an acid for weeks or months; but if we first mix it with quick-lime, and expose the mixture to a moderately strong heat, the lime enters into chemical combination with certain elements of the feldspar, and its alkali (potass) is set free. And now the acid, even without heat, dissolves not only the lime, but also so much of the silica of the feldspar as to form a transparent jelly. The same effect which the lime in this process, with the aid of heat, exerts upon the feldspar, it produces when it is mixed with the alkaline argillaceous silicates, and they are for a long time kept together in a moist state. Common potters' clay, or pipe-clay, diffused through water, and added to milk of lime, thickens immediately upon mixing; and if the mixture is kept for some months, and then treated with acid, the clay becomes gelatinous, which would not occur without the admixture with the lime. The lime, in combining with the elements of the clay, liquifies it; and, what is more remarkable, liberates the greater part of its alkalies. These interesting facts were first observed by Fuchs, at Munich: they have not only led to a more intimate knowledge of the nature and properties of the hydraulic cements, but, what is far more important, they explain the effects of caustic lime upon the soil, and guide the agriculturist in the application of an invaluable means of opening it, and setting free its alkalies--substances so important, nay, so indispensable to his crops. In the month of October the fields of Yorkshire and Oxfordshire look as it they were covered with snow. Whole square miles are seen whitened over with quicklime, which during the moist winter months, exercises its beneficial influence upon the stiff, clayey soil, of those counties. According to the humus theory, quick-lime ought to exert the most noxious influence upon the soil, because all organic matters contained in it are destroyed by it, and rendered incapable of yielding their humus to a new vegetation. The facts are indeed directly contrary to this now abandoned theory: the fertility of the soil is increased by the lime. The cerealia require the alkalies and alkaline silicates, which the action of the lime renders fit for assimilation by the plants. If, in addition to these, there is any decaying organic matter present in the soil supplying carbonic acid, it may facilitate their development; but it is not essential to their growth. If we furnish the soil with ammonia, and the phosphates, which are indispensable to the cerealia, with the alkaline silicates, we have all the conditions necessary to ensure an abundant harvest. The atmosphere is an inexhaustible store of carbonic acid. A no less favourable influence than that of lime is exercised upon the soil of peaty land by the mere act of burning it: this greatly enhances its fertility. We have not long been acquainted with the remarkable change which the properties of clay undergo by burning. The observation was first made in the process of analysing the clay silicates. Many of these, in their natural state, are not acted on by acids, but they become perfectly soluble if heated to redness before the application of the acid. This property belongs to potters' clay, pipe-clay, loam, and many different modifications of clay in soils. In their natural state they may be boiled in concentrated sulphuric acid, without sensible change; but if feebly burned, as is done with the pipe-clay in many alum manufactories, they dissolve in the acid with the greatest facility, the contained silica being separated like jelly in a soluble state. Potters' clay belongs to the most sterile kinds of soil, and yet it contains within itself all the constituent elements essential to a most luxurious growth of plants; but their mere presence is insufficient to secure this end. The soil must be accessible to the atmosphere, to its oxygen, to its carbonic acid; these must penetrate it, in order to secure the conditions necessary to a happy and vigorous development of the roots. The elements present must be brought into that peculiar state of combination which will enable them to enter into plants. Plastic clay is wanting in these properties; but they are imparted to it by a feeble calcination. At Hardwicke Court, near Gloucester, I have seen a garden (Mr. Baker's) consisting of a stiff clay, which was perfectly sterile, become by mere burning extremely fertile. The operation was extended to a depth of three feet. This was an expensive process, certainly; but it was effectual. The great difference in the properties of burnt and unburnt clay is illustrated by what is seen in brick houses, built in moist situations. In the town of Flanders, for instance, where most buildings are of brick, effloresences of salts cover the surfaces of the walls, like a white nap, within a few days after they are erected. If this saline incrustation is washed away by the rain, it soon re-appears; and this is even observed on walls which, like the gateway of Lisle, have been erected for centuries. These saline incrustations consist of carbonates and sulphates, with alkaline bases; and it is well known these act an important part in vegetation. The influence of lime in their production is manifested by their appearing first at the place where the mortar and brick come into contact. It will now be obvious to you, that in a mixture of clay with lime, all the conditions exist for the solution of the silicated clay, and the solubility of the alkaline silicates. The lime gradually dissolving in water charged with carbonic acid, acts like milk of lime upon the clay. This explains also the favourable influence which marl (by which term all those varieties of clay rich in chalk are designated) exerts upon most kinds of soil. There are marly soils which surpass all others in fertility for all kinds of plants; but I believe marl in a burnt state must be far more effective, as well as other materials possessing a similar composition; as, for instance, those species of limestone which are adapted to the preparation of hydraulic cements,--for these carry to the soil not only the alkaline bases useful to plants, but also silica in a state capable of assimilation. The ashes of coals and lignite are also excellent means of ameliorating the soil, and they are used in many places for this purpose. The most suitable may be readily known by their property of forming a gelatinous mass when treated with acids, or by becoming, when mixed with cream of lime, like hydraulic cement,--solid and hard as stone. I have now, I trust, explained to your satisfaction, that the mechanical operations of agriculture--the application of lime and chalk to lands, and the burning of clay--depend upon one and the same scientific principle: they are means of accelerating the decomposition of the alkaline clay silicates, in order to provide plants, at the beginning of a new vegetation, with certain inorganic matters indispensable for their nutrition. LETTER XIV My dear Sir, I treated, in my last letter, of the means of improving the condition of the soil for agricultural purposes by mechanical operations and mineral agents. I have now to speak of the uses and effects of animal exuviae, and vegetable matters or manures--properly so called. In order to understand the nature of these, and the peculiarity of their influence upon our fields, it is highly important to keep in mind the source whence they are derived. It is generally known, that if we deprive an animal of food, the weight of its body diminishes during every moment of its existence. If this abstinence is continued for some time, the diminution becomes apparent to the eye; all the fat of the body disappears, the muscles decrease in firmness and bulk, and, if the animal is allowed to die starved, scarcely anything but skin, tendon, and bones, remain. This emaciation which occurs in a body otherwise healthy, demonstrates to us, that during the life of an animal every part of its living substance is undergoing a perpetual change; all its component parts, assuming the form of lifeless compounds, are thrown off by the skin, lungs, and urinary system, altered more or less by the secretory organs. This change in the living body is intimately connected with the process of respiration; it is, in truth, occasioned by the oxygen of the atmosphere in breathing, which combines with all the various matters within the body. At every inspiration a quantity of oxygen passes into the blood in the lungs, and unites with its elements; but although the weight of the oxygen thus daily entering into the body amounts to 32 or more ounces, yet the weight of the body is not thereby increased. Exactly as much oxygen as is imbibed in inspiration passes off in expiration, in the form of carbonic acid and water; so that with every breath the amount of carbon and hydrogen in the body is diminished. But the emaciation--the loss of weight by starvation--does not simply depend upon the separation of the carbon and hydrogen; but all the other substances which are in combination with these elements in the living tissues pass off in the secretions. The nitrogen undergoes a change, and is thrown out of the system by the kidneys. Their secretion, the urine, contains not only a compound rich in nitrogen, namely urea, but the sulphur of the tissues in the form of a sulphate, all the soluble salts of the blood and animal fluids, common salt, the phosphates, soda and potash. The carbon and hydrogen of the blood, of the muscular fibre, and of all the animal tissues which can undergo change, return into the atmosphere. The nitrogen, and all the soluble inorganic elements are carried to the earth in the urine. These changes take place in the healthy animal body during every moment of life; a waste and loss of substance proceeds continually; and if this loss is to be restored, and the original weight and substance repaired, an adequate supply of materials must be furnished, from whence the blood and wasted tissues may be regenerated. This supply is obtained from the food. In an adult person in a normal or healthy condition, no sensible increase or decrease of weight occurs from day to day. In youth the weight of the body increases, whilst in old age it decreases. There can be no doubt that in the adult, the food has exactly replaced the loss of substance: it has supplied just so much carbon, hydrogen, nitrogen, and other elements, as have passed through the skin, lungs, and urinary organs. In youth the supply is greater than the waste. Part of the elements of the food remain to augment the bulk of the body. In old age the waste is greater than the supply, and the body diminishes. It is unquestionable, that, with the exception of a certain quantity of carbon and hydrogen, which are secreted through the skin and lungs, we obtain, in the solid and fluid excrements of man and animals, all the elements of their food. We obtain daily, in the form of urea, all the nitrogen taken in the food both of the young and the adult; and further, in the urine, the whole amount of the alkalies, soluble phosphates and sulphates, contained in all the various aliments. In the solid excrements are found all those substances taken in the food which have undergone no alteration in the digestive organs, all indigestible matters, such as woody fibre, the green colouring matter of leaves ( chlorophyle), wax, &c. Physiology teaches us, that the process of nutrition in animals, that is, their increase of bulk, or the restoration of wasted parts, proceeds from the blood. The purpose of digestion and assimilation is to convert the food into blood. In the stomach and intestines, therefore, all those substances in the food capable of conversion into blood are separated from its other constituents; in other words, during the passage of the food through the intestinal canal there is a constant absorption of its nitrogen, since only azotised substances are capable of conversion into blood; and therefore the solid excrements are destitute of that element, except only a small portion, in the constitution of that secretion which is formed to facilitate their passage. With the solid excrements, the phosphates of lime and magnesia, which were contained in the food and not assimilated, are carried off, these salts being insoluble in water, and therefore not entering the urine. We may obtain a clear insight into the chemical constitution of the solid excrements without further investigation, by comparing the faeces of a dog with his food. We give that animal flesh and bones--substances rich in azotised matter--and we obtain, as the last product of its digestion, a perfectly white excrement, solid while moist, but becoming in dry air a powder. This is the phosphate of lime of the bones, with scarcely one per cent. of foreign organic matter. Thus we see that in the solid and fluid excrements of man and animals, all the nitrogen--in short, all the constituent ingredients of the consumed food, soluble and insoluble, are returned; and as food is primarily derived from the fields, we possess in those excrements all the ingredients which we have taken from it in the form of seeds, roots, or herbs. One part of the crops employed for fattening sheep and cattle is consumed by man as animal food; another part is taken directly--as flour, potatoes, green vegetables, &c.; a third portion consists of vegetable refuse, and straw employed as litter. None of the materials of the soil need be lost. We can, it is obvious, get back all its constituent parts which have been withdrawn therefrom, as fruits, grain and animals, in the fluid and solid excrements of man, and the bones, blood and skins of the slaughtered animals. It depends upon ourselves to collect carefully all these scattered elements, and to restore the disturbed equilibrium of composition in the soil. We can calculate exactly how much and which of the component parts of the soil we export in a sheep or an ox, in a quarter of barley, wheat or potatoes, and we can discover, from the known composition of the excrements of man and animals, how much we have to supply to restore what is lost to our fields. If, however, we could procure from other sources the substances which give to the exuviae of man and animals their value in agriculture, we should not need the latter. It is quite indifferent for our purpose whether we supply the ammonia (the source of nitrogen) in the form of urine, or in that of a salt derived from coal-tar; whether we derive the phosphate of lime from bones, apatite, or fossil excrements (the coprolithes). The principal problem for agriculture is, how to replace those substances which have been taken from the soil, and which cannot be furnished by the atmosphere. If the manure supplies an imperfect compensation for this loss, the fertility of a field or of a country decreases; if, on the contrary, more are given to the fields, their fertility increases. An importation of urine, or of solid excrements, from a foreign country, is equivalent to an importation of grain and cattle. In a certain time, the elements of those substances assume the form of grain, or of fodder, then become flesh and bones, enter into the human body, and return again day by day to the form they originally possessed. The only real loss of elements we are unable to prevent is of the phosphates, and these, in accordance with the customs of all modern nations, are deposited in the grave. For the rest, every part of that enormous quantity of food which a man consumes during his lifetime ( say in sixty or seventy years), which was derived from the fields, can be obtained and returned to them. We know with absolute certainty, that in the blood of a young or growing animal there remains a certain quantity of phosphate of lime and of the alkaline phosphates, to be stored up and to minister to the growth of the bones and general bulk of the body, and that, with the exception of this very small quantity, we receive back, in the solid and fluid excrements, all the salts and alkaline bases, all the phosphate of lime and magnesia, and consequently all the inorganic elements which the animal consumes in its food. We can thus ascertain precisely the quantity, quality, and composition of animal excrements, without the trouble of analysing them. If we give a horse daily 4 1/2 pounds' weight of oats, and 15 pounds of hay, and knowing that oats give 4 per cent. and hay 9 per cent. of ashes, we can calculate that the daily excrements of the horse will contain 21 ounces of inorganic matter which was drawn from the fields. By analysis we can determine the exact relative amount of silica, of phosphates, and of alkalies, contained in the ashes of the oats and of the hay. You will now understand that the constituents of the solid parts of animal excrements, and therefore their qualities as manure, must vary with the nature of the creature's food. If we feed a cow upon beetroot, or potatoes, without hay, straw or grain, there will be no silica in her solid excrements, but there will be phosphate of lime and magnesia. Her fluid excrements will contain carbonate of potash and soda, together with compounds of the same bases with inorganic acids. In one word, we have, in the fluid excrements, all the soluble parts of the ashes of the consumed food; and in the solid excrements, all those parts of the ashes which are insoluble in water. If the food, after burning, leaves behind ashes containing soluble alkaline phosphates, as is the case with bread, seeds of all kinds, and flesh, we obtain from the animal by which they are consumed a urine holding in solution these phosphates. If, however, the ashes of food contain no alkaline phosphates, but abound in insoluble earthy phosphates, as hay, carrots, and potatoes, the urine will be free from alkaline phosphates, but the earthy phosphates will be found in the faeces. The urine of man, of carnivorous and graminivorous animals, contains alkaline phosphates; that of herbivorous animals is free from these salts. The analysis of the excrements of man, of the piscivorous birds (as the guano), of the horse, and of cattle, furnishes us with the precise knowledge of the salts they contain, and demonstrates, that in those excrements, we return to the fields the ashes of the plants which have served as food,--the soluble and insoluble salts and earths indispensable to the development of cultivated plants, and which must be furnished to them by a fertile soil. There can be no doubt that, in supplying these excrements to the soil, we return to it those constituents which the crops have removed from it, and we renew its capability of nourishing new crops: in one word, we restore the disturbed equilibrium; and consequently, knowing that the elements of the food derived from the soil enter into the urine and solid excrements of the animals it nourishes, we can with the greatest facility determine the exact value of the different kinds of manure. Thus the excrements of pigs which we have fed with peas and potatoes are principally suited for manuring crops of potatoes and peas. In feeding a cow upon hay and turnips, we obtain a manure containing the inorganic elements of grasses and turnips, and which is therefore preferable for manuring turnips. The excrement of pigeons contains the mineral elements of grain; that of rabbits, the elements of herbs and kitchen vegetables. The fluid and solid excrements of man, however, contain the mineral elements of grain and seeds in the greatest quantity. LETTER XV My dear Sir, You are now acquainted with my opinions respecting the effects of the application of mineral agents to our cultivated fields, and also the rationale of the influence of the various kinds of manures; you will, therefore, now readily understand what I have to say of the sources whence the carbon and nitrogen, indispensable to the growth of plants, are derived. The growth of forests, and the produce of meadows, demonstrate that an inexhaustible quantity of carbon is furnished for vegetation by the carbonic acid of the atmosphere. We obtain from an equal surface of forest, or meadow-land, where the necessary mineral elements of the soil are present in a suitable state, and to which no carbonaceous matter whatever is furnished in manures, an amount of carbon, in the shape of wood and hay, quite equal, and oftimes more than is produced by our fields, in grain, roots, and straw, upon which abundance of manure has been heaped. It is perfectly obvious that the atmosphere must furnish to our cultivated fields as much carbonic acid, as it does to an equal surface of forest or meadow, and that the carbon of this carbonic acid is assimilated, or may be assimilated by the plants growing there, provided the conditions essential to its assimilation, and becoming a constituent element of vegetables, exist in the soil of these fields. In many tropical countries the produce of the land in grain or roots, during the whole year, depends upon one rain in the spring. If this rain is deficient in quantity, or altogether wanting, the expectation of an abundant harvest is diminished or destroyed. Now it cannot be the water merely which produces this enlivening and fertilising effect observed, and which lasts for weeks and months. The plant receives, by means of this water, at the time of its first development, the alkalies, alkaline earths, and phosphates, necessary to its organization. If these elements, which are necessary previous to its assimilation of atmospheric nourishment, be absent, its growth is retarded. In fact, the development of a plant is in a direct ratio to the amount of the matters it takes up from the soil. If, therefore, a soil is deficient in these mineral constituents required by plants, they will not flourish even with an abundant supply of water. The produce of carbon on a meadow, or an equal surface of forest land, is independent of a supply of carbonaceous manure, but it depends upon the presence of certain elements of the soil which in themselves contain no carbon, together with the existence of conditions under which their assimilation by plants can be effected. We increase the produce of our cultivated fields, in carbon, by a supply of lime, ashes, and marl, substances which cannot furnish carbon to the plants, and yet it is indisputable,--being founded upon abundant experience,--that in these substances we furnish to the fields elements which greatly increase the bulk of their produce, and consequently the amount of carbon. If we admit these facts to be established, we can no longer doubt that a deficient produce of carbon, or in other words, the barrenness of a field does not depend upon carbonic acid, because we are able to increase the produce, to a certain degree, by a supply of substances which do not contain any carbon. The same source whence the meadow and the forest are furnished with carbon, is also open to our cultivated plants. The great object of agriculture, therefore, is to discover the means best adapted to enable these plants to assimilate the carbon of the atmosphere which exists in it as carbonic acid. In furnishing plants, therefore, with mineral elements, we give them the power to appropriate carbon from a source which is inexhaustible; whilst in the absence of these elements the most abundant supply of carbonic acid, or of decaying vegetable matter, would not increase the produce of a field. With an adequate and equal supply of these essential mineral constituents in the soil, the amount of carbonic acid absorbed by a plant from the atmosphere in a given time is limited by the quantity which is brought into contact with its organs of absorption. The withdrawal of carbonic acid from the atmosphere by the vegetable organism takes place chiefly through its leaves; this absorption requires the contact of the carbonic acid with their surface, or with the part of the plant by which it is absorbed. The quantity of carbonic acid absorbed in a given time is in direct proportion to the surface of the leaves and the amount of carbonic acid contained in the air; that is, two plants of the same kind and the same extent of surface of absorption, in equal times and under equal conditions, absorb one and the same amount of carbon. In an atmosphere containing a double proportion of carbonic acid, a plant absorbs, under the same condition, twice the quantity of carbon. Boussingault observed, that the leaves of the vine, inclosed in a vessel, withdrew all the carbonic acid from a current of air which was passed through it, however great its velocity. (Dumas Lecon, p.23.) If, therefore, we supply double the quantity of carbonic acid to one plant, the extent of the surface of which is only half that of another living in ordinary atmospheric air, the former will obtain and appropriate as much carbon as the latter. Hence results the effects of humus, and all decaying organic substances, upon vegetation. If we suppose all the conditions for the absorption of carbonic acid present, a young plant will increase in mass, in a limited time, only in proportion to its absorbing surface; but if we create in the soil a new source of carbonic acid, by decaying vegetable substances, and the roots absorb in the same time three times as much carbonic acid from the soil as the leaves derive from the atmosphere, the plant will increase in weight fourfold. This fourfold increase extends to the leaves, buds, stalks, &c., and in the increased extent of the surface, the plant acquires an increased power of absorbing nourishment from the air, which continues in action far beyond the time when its derivation of carbonic acid through the roots ceases. Humus, as a source of carbonic acid in cultivated lands, is not only useful as a means of increasing the quantity of carbon--an effect which in most cases may be very indifferent for agricultural purposes--but the mass of the plant having increased rapidly in a short time, space is obtained for the assimilation of the elements of the soil necessary for the formation of new leaves and branches. Water evaporates incessantly from the surface of the young plant; its quantity is in direct proportion to the temperature and the extent of the surface. The numerous radical fibrillae replace, like so many pumps, the evaporated water; and so long as the soil is moist, or penetrated with water, the indispensable elements of the soil, dissolved in the water, are supplied to the plant. The water absorbed by the plant evaporating in an aeriform state leaves the saline and other mineral constituents within it. The relative proportion of these elements taken up by a plant, is greater, the more extensive the surface and more abundant the supply of water; where these are limited, the plant soon reaches its full growth, while if their supply is continued, a greater amount of elements necessary to enable it to appropriate atmospheric nourishment being obtained, its development proceeds much further. The quantity, or mass of seed produced, will correspond to the quantity of mineral constituents present in the plant. That plant, therefore, containing the most alkaline phosphates and earthy salts will produce more or a greater weight of seeds than another which, in an equal time has absorbed less of them. We consequently observe, in a hot summer, when a further supply of mineral ingredients from the soil ceases through want of water, that the height and strength of plants, as well as the development of their seeds, are in direct proportion to its absorption of the elementary parts of the soil in the preceding epochs of its growth. The fertility of the year depends in general upon the temperature, and the moisture or dryness of the spring, if all the conditions necessary to the assimilation of the atmospheric nourishment be secured to our cultivated plants. The action of humus, then, as we have explained it above, is chiefly of value in gaining time. In agriculture, this must ever be taken into account and in this respect humus is of importance in favouring the growth of vegetables, cabbages, &c. But the cerealia, and plants grown for their roots, meet on our fields, in the remains of the preceding crop, with a quantity of decaying vegetable substances corresponding to their contents of mineral nutriment from the soil, and consequently with a quantity of carbonic acid adequate to their accelerated development in the spring. A further supply of carbonic acid, therefore, would be quite useless, without a corresponding increase of mineral ingredients. From a morgen of good meadow land, 2,500 pounds weight of hay, according to the best agriculturists, are obtained on an average. This amount is furnished without any supply of organic substances, without manure containing carbon or nitrogen. By irrigation, and the application of ashes or gypsum, double that amount may be grown. But assuming 2,500 pounds weight of hay to be the maximum, we may calculate the amount of carbon and nitrogen derived from the atmosphere by the plants of meadows. According to elementary analysis, hay, dried at a temperature of 100 deg Reaumur, contains 45.8 per cent. of carbon, and 1 1/2 per cent. of nitrogen. 14 per cent. of water retained by the hay, dried at common temperatures, is driven off at 100 deg. 2,500 pounds weight of hay, therefore, corresponds to 2,150 pounds, dried at 100 deg. This shows us, that 984 pounds of carbon, and 32.2 pounds weight of nitrogen, have been obtained in the produce of one morgen of meadow land. Supposing that this nitrogen has been absorbed by the plants in the form of ammonia, the atmosphere contains 39.1 pounds weight of ammonia to every 3640 pounds weight of carbonic acid (=984 carbon, or 27 per cent.), or in other words, to every 1,000 pounds weight of carbonic acid, 10.7 pounds of ammonia, that is to about 1/100,000, the weight of the air, or 1/60,000 of its volume. For every 100 parts of carbonic acid absorbed by the surface of the leaves, the plant receives from the atmosphere somewhat more than one part of ammonia. With every 1,000 pounds of carbon, we obtain-- From a meadow . 32 7/10 pounds of nitrogen. From cultivated fields, In Wheat . 21 1/2 " " Oats . 22.3 " " Rye . 15.2 " " Potatoes . 34.1 " " Beetroot . 39.1 " " Clover . 44 " " Peas . 62 " " Boussingault obtained from his farm at Bechelbronn, in Alsace, in five years, in the shape of potatoes, wheat, clover, turnips, and oats, 8,383 of carbon, and 250.7 nitrogen. In the following five years, as beetroot, wheat, clover, turnips, oats, and rye, 8,192 of carbon, and 284.2 of nitrogen. In a further course of six years, potatoes, wheat, clover, turnips, peas, and rye, 10,949 of carbon, 356.6 of nitrogen. In 16 years, 27,424 carbon, 858 1/2 nitrogen, which gives for every 1,000 carbon, 31.3 nitrogen. From these interesting and unquestionable facts, we may deduce some conclusions of the highest importance in their application to agriculture. 1. We observe that the relative proportions of carbon and nitrogen, stand in a fixed relation to the surface of the leaves. Those plants, in which all the nitrogen may be said to be concentrated in the seeds, as the cerealia, contain on the whole less nitrogen than the leguminous plants, peas, and clover. 2. The produce of nitrogen on a meadow which receives no nitrogenised manure, is greater than that of a field of wheat which has been manured. 3. The produce of nitrogen in clover and peas, which agriculturists will acknowledge require no nitrogenised manure, is far greater than that of a potato or turnip field, which is abundantly supplied with such manures. Lastly. And this is the most curious deduction to be derived from the above facts,--if we plant potatoes, wheat, turnips, peas, and clover, (plants containing potash, lime, and silex,) upon the same land, three times manured, we gain in 16 years, for a given quantity of carbon, the same proportion of nitrogen which we receive from a meadow which has received no nitrogenised manure. On a morgen of meadow-land, we obtain in plants, containing silex, lime, and potash, 984 carbon, 32.2 nitrogen. On a morgen of cultivated land, in an average of 16 years, in plants containing the same mineral elements, silex, lime, and potash, 857 carbon, 26.8 nitrogen. If we add the carbon and nitrogen of the leaves of the beetroot, and the stalk and leaves of the potatoes, which have not been taken into account, it still remains evident that the cultivated fields, notwithstanding the supply of carbonaceous and nitrogenised manures, produced no more carbon and nitrogen than an equal surface of meadow-land supplied only with mineral elements. What then is the rationale of the effect of manure,--of the solid and fluid excrements of animals? This question can now be satisfactorily answered: that effect is the restoration of the elementary constituents of the soil which have been gradually drawn from it in the shape of grain and cattle. If the land I am speaking of had not been manured during those 16 years, not more than one-half, or perhaps than one-third part of the carbon and nitrogen would have been produced. We owe it to the animal excrements, that it equalled in production the meadow-land, and this, because they restored the mineral ingredients of the soil removed by the crops. All that the supply of manure accomplished, was to prevent the land from becoming poorer in these, than the meadow which produces 2,500 pounds of hay. We withdraw from the meadow in this hay as large an amount of mineral substances as we do in one harvest of grain, and we know that the fertility of the meadow is just as dependent upon the restoration of these ingredients to its soil, as the cultivated land is upon manures. Two meadows of equal surface, containing unequal quantities of inorganic elements of nourishment,--other conditions being equal,--are very unequally fertile; that which possesses most, furnishes most hay. If we do not restore to a meadow the withdrawn elements, its fertility decreases. But its fertility remains unimpaired, with a due supply of animal excrements, fluid and solid, and it not only remains the same, but may be increased by a supply of mineral substances alone, such as remain after the combustion of ligneous plants and other vegetables; namely, ashes. Ashes represent the whole nourishment which vegetables receive from the soil. By furnishing them in sufficient quantities to our meadows, we give to the plants growing on them the power of condensing and absorbing carbon and nitrogen by their surface. May not the effect of the solid and fluid excrements, which are the ashes of plants and grains, which have undergone combustion in the bodies of animals and of man, be dependent upon the same cause? Should not the fertility, resulting from their application, be altogether independent of the ammonia they contain? Would not their effect be precisely the same in promoting the fertility of cultivated plants, if we had evaporated the urine, and dried and burned the solid excrements? Surely the cerealia and leguminous plants which we cultivate must derive their carbon and nitrogen from the same source whence the graminea and leguminous plants of the meadows obtain them! No doubt can be entertained of their capability to do so. In Virginia, upon the lowest calculation, 22 pounds weight of nitrogen were taken on the average, yearly, from every morgen of the wheat-fields. This would amount, in 100 years, to 2,200 pounds weight. If this were derived from the soil, every morgen of it must have contained the equivalent of 110,000 pounds weight of animal excrements (assuming the latter, when dried, at the temperature of boiling water, to contain 2 per cent.). In Hungary, as I remarked in a former Letter, tobacco and wheat have been grown upon the same field for centuries, without any supply of nitrogenised manure. Is it possible that the nitrogen essential to, and entering into, the composition of these crops, could have been drawn from the soil? Every year renews the foliage and fruits of our forests of beech, oak, and chesnuts; the leaves, the acorns, the chesnuts, are rich in nitrogen; so are cocoa-nuts, bread-fruit, and other tropical productions. This nitrogen is not supplied by man, can it indeed be derived from any other source than the atmosphere? In whatever form the nitrogen supplied to plants may be contained in the atmosphere, in whatever state it may be when absorbed, from the atmosphere it must have been derived. Did not the fields of Virginia receive their nitrogen from the same source as wild plants? Is the supply of nitrogen in the excrements of animals quite a matter of indifference, or do we receive back from our fields a quantity of the elements of blood corresponding to this supply? The researches of Boussingault have solved this problem in the most satisfactory manner. If, in his grand experiments, the manure which he gave to his fields was in the same state, i.e. dried at 110 deg in a vacuum, as it was when analysed, these fields received, in 16 years, 1,300 pounds of nitrogen. But we know that by drying all the nitrogen escapes which is contained in solid animal excrements, as volatile carbonate of ammonia. In this calculation the nitrogen of the urine, which by decomposition is converted into carbonate of ammonia, has not been included. If we suppose it amounted to half as much as that in the dried excrements, this would make the quantity of nitrogen supplied to the fields 1,950 pounds. In 16 years, however, as we have seen, only 1,517 pounds of nitrogen, was contained in their produce of grain, straw, roots, et cetera--that is, far less than was supplied in the manure; and in the same period the same extent of surface of good meadow-land (one hectare = a Hessian morgen), which received no nitrogen in manure, 2,062 pounds of nitrogen. It is well known that in Egypt, from the deficiency of wood, the excrement of animals is dried, and forms the principal fuel, and that the nitrogen from the soot of this excrement was, for many centuries, imported into Europe in the form of sal ammoniac, until a method of manufacturing this substance was discovered at the end of the last century by Gravenhorst of Brunswick. The fields in the delta of the Nile are supplied with no other animal manures than the ashes of the burnt excrements, and yet they have been proverbially fertile from a period earlier than the first dawn of history, and that fertility continues to the present day as admirable as it was in the earliest times. These fields receive, every year, from the inundation of the Nile, a new soil, in its mud deposited over their surface, rich in those mineral elements which have been withdrawn by the crops of the previous harvest. The mud of the Nile contains as little nitrogen as the mud derived from the Alps of Switzerland, which fertilises our fields after the inundations of the Rhine. If this fertilising mud owed this property to nitrogenised matters; what enormous beds of animal and vegetable exuviae and remains ought to exist in the mountains of Africa, in heights extending beyond the limits of perpetual snow, where no bird, no animal finds food, from the absence of all vegetation! Abundant evidence in support of the important truth we are discussing, may be derived from other well known facts. Thus, the trade of Holland in cheese may be adduced in proof and illustration thereof. We know that cheese is derived from the plants which serve as food for cows. The meadow-lands of Holland derive the nitrogen of cheese from the same source as with us; i.e. the atmosphere. The milch cows of Holland remain day and night on the grazing-grounds, and therefore, in their fluid and solid excrements return directly to the soil all the salts and earthy elements of their food: a very insignificant quantity only is exported in the cheese. The fertility of these meadows can, therefore, be as little impaired as our own fields, to which we restore all the elements of the soil, as manure, which have been withdrawn in the crops. The only difference is, in Holland they remain on the field, whilst we collect them at home and carry them, from time to time, to the fields. The nitrogen of the fluid and solid excrements of cows, is derived from the meadow-plants, which receive it from the atmosphere; the nitrogen of the cheese also must be drawn from the same source. The meadows of Holland have, in the lapse of centuries, produced millions of hundredweights of cheese. Thousands of hundredweights are annually exported, and yet the productiveness of the meadows is in no way diminished, although they never receive more nitrogen than they originally contained. Nothing then can be more certain than the fact, that an exportation of nitrogenised products does not exhaust the fertility of a country; inasmuch as it is not the soil, but the atmosphere, which furnishes its vegetation with nitrogen. It follows, consequently, that we cannot increase the fertility of our fields by a supply of nitrogenised manure, or by salts of ammonia, but rather that their produce increases or diminishes, in a direct ratio, with the supply of mineral elements capable of assimilation. The formation of the constituent elements of blood, that is, of the nitrogenised principles in our cultivated plants, depends upon the presence of inorganic matters in the soil, without which no nitrogen can be assimilated even when there is a most abundant supply. The ammonia contained in animal excrements exercises a favourable effect, inasmuch as it is accompanied by the other substances necessary to accomplish its transition into the elements of the blood. If we supply ammonia associated with all the conditions necessary to its assimilation, it ministers to the nourishment of the plants; but if this artificial supply is not given they can derive all the needed nitrogen from the atmosphere--a source, every loss from which is restored by the decomposition of the bodies of dead animals and the decay of plants. Ammonia certainly favours, and accelerates, the growth of plants in all soils, wherein all the conditions of its assimilation are united; but it is altogether without effect, as respects the production of the elements of blood where any of these conditions are wanting. We can suppose that asparagin, the active constituent of asparagus, the mucilaginous root of the marsh-mallow, the nitrogenised and sulphurous ingredients of mustard-seed, and of all cruciferous plants, may originate without the aid of the mineral elements of the soil. But if the principles of those vegetables, which serve as food, could be generated without the co-operation of the mineral elements of blood, without potash, soda, phosphate of soda, phosphate of lime, they would be useless to us and to herbivorous animals as food; they would not fulfil the purpose for which the wisdom of the Creator has destined them. In the absence of alkalies and the phosphates, no blood, no milk, no muscular fibre can be formed. Without phosphate of lime our horses, sheep and cattle, would be without bones. In the urine and in the solid excrements of animals we carry ammonia, and, consequently, nitrogen, to our cultivated plants, and this nitrogen is accompanied by all the mineral elements of food exactly in the same proportions, in which both are contained in the plants which served as food to the animals, or what is the same, in those proportions in which both can serve as nourishment to a new generation of plants, to which both are essential. The effect of an artificial supply of ammonia, as a source of nitrogen, is, therefore, precisely analogous to that of humus as a source of carbonic acid--it is limited to a gain of time; that is, it accelerates the development of plants. This is of great importance, and should always be taken into account in gardening, especially in the treatment of the kitchen-garden; and as much as possible, in agriculture on a large scale, where the time occupied in the growth of the plants cultivated is of importance. When we have exactly ascertained the quantity of ashes left after the combustion of cultivated plants which have grown upon all varieties of soil, and have obtained correct analyses of these ashes, we shall learn with certainty which of the constituent elements of the plants are constant and which are changeable, and we shall arrive at an exact knowledge of the sum of all the ingredients we withdraw from the soil in the different crops. With this knowledge the farmer will be able to keep an exact record, of the produce of his fields in harvest, like the account-book of a well regulated manufactory; and then by a simple calculation he can determine precisely the substances he must supply to each field, and the quantity of these, in order to restore their fertility. He will be able to express, in pounds weight, how much of this or that element he must give in order to augment its fertility for any given kind of plants. These researches and experiments are the great desideratum of the present time. TO THE UNITED EFFORTS OF THE CHEMISTS OF ALL COUNTRIES WE MAY CONFIDENTLY LOOK FOR A SOLUTION OF THESE GREAT QUESTIONS, and by the aid of ENLIGHTENED AGRICULTURISTS we shall arrive at a RATIONAL system of GARDENING, HORTICULTURE, and AGRICULTURE, applicable to every country and all kinds of soil, and which will be based upon the immutable foundation of OBSERVED FACTS and PHILOSOPHICAL INDUCTION. LETTER XVI My dear Sir, My recent researches into the constituent ingredients of our cultivated fields have led me to the conclusion that, of all the elements furnished to plants by the soil and ministering to their nourishment, the phosphate of lime--or, rather, the phosphates generally--must be regarded as the most important. In order to furnish you with a clear idea of the importance of the phosphates, it may be sufficient to remind you of the fact, that the blood of man and animals, besides common salt, always contains alkaline and earthy phosphates. If we burn blood and examine the ashes which remain, we find certain parts of them soluble in water, and others insoluble. The soluble parts are, common salt and alkaline phosphates; the insoluble consist of phosphate of lime, phosphate of magnesia, and oxide of iron. These mineral ingredients of the blood--without the presence of which in the food the formation of blood is impossible--both man and animals derive either immediately, or mediately through other animals, from vegetable substances used as food; they had been constituents of vegetables, they had been parts of the soil upon which the vegetable substances were developed. If we compare the amount of the phosphates in different vegetable substances with each other, we discover a great variety, whilst there is scarcely any ashes of plants altogether devoid of them, and those parts of plants which experience has taught us are the most nutritious, contain the largest proportion. To these belong all seeds and grain, especially the varieties of bread-corn, peas, beans, and lentils. It is a most curious fact that if we incinerate grain or its flour, peas, beans, and lentils, we obtain ashes, which are distinguished from the ashes of all other parts of vegetables by the absence of alkaline carbonates. The ashes of these seeds when recently prepared, do not effervesce with acids; their soluble ingredients consist solely of alkaline phosphates, the insoluble parts of phosphate of lime, phosphate of magnesia, and oxide of iron: consequently, of the very same salts which are contained in blood, and which are absolutely indispensable to its formation. We are thus brought to the further indisputable conclusion that no seed suitable to become food for man and animals can be formed in any plant without the presence and co-operation of the phosphates. A field in which phosphate of lime, or the alkaline phosphates, form no part of the soil, is totally incapable of producing grain, peas, or beans. An enormous quantity of these substances indispensable to the nourishment of plants, is annually withdrawn from the soil and carried into great towns, in the shape of flour, cattle, et cetera. It is certain that this incessant removal of the phosphates must tend to exhaust the land and diminish its capability of producing grain. The fields of Great Britain are in a state of progressive exhaustion from this cause, as is proved by the rapid extension of the cultivation of turnips and mangel wurzel--plants which contain the least amount of the phosphates, and therefore require the smallest quantity for their development. These roots contain 80 to 92 per cent. of water. Their great bulk makes the amount of produce fallacious, as respects their adaptation to the food of animals, inasmuch as their contents of the ingredients of the blood, i.e. of substances which can be transformed into flesh, stands in a direct ratio to their amount of phosphates, without which neither blood nor flesh can be formed. Our fields will become more and more deficient in these essential ingredients of food, in all localities where custom and habits do not admit the collection of the fluid and solid excrements of man, and their application to the purposes of agriculture. In a former letter I showed you how great a waste of phosphates is unavoidable in England, and referred to the well-known fact that the importation of bones restored in a most admirable manner the fertility of the fields exhausted from this cause. In the year 1827 the importation of bones for manure amounted to 40,000 tons, and Huskisson estimated their value to be from L 100,000 to L 200,000 sterling. The importation is still greater at present, but it is far from being sufficient to supply the waste. Another proof of the efficacy of the phosphates in restoring fertility to exhausted land is afforded by the use of the guano--a manure which, although of recent introduction into England, has found such general and extensive application. We believe that the importation of one hundred-weight of guano is equivalent to the importation of eight hundred-weight of wheat--the hundred-weight of guano assumes in a time which can be accurately estimated the form of a quantity of food corresponding to eight hundred-weight of wheat. The same estimate is applicable in the valuation of bones. If it were possible to restore to the soil of England and Scotland the phosphates which during the last fifty years have been carried to the sea by the Thames and the Clyde, it would be equivalent to manuring with millions of hundred-weights of bones, and the produce of the land would increase one-third, or perhaps double itself, in five to ten years. We cannot doubt that the same result would follow if the price of the guano admitted the application of a quantity to the surface of the fields, containing as much of the phosphates as have been withdrawn from them in the same period. If a rich and cheap source of phosphate of lime and the alkaline phosphates were open to England, there can be no question that the importation of foreign corn might be altogether dispensed with after a short time. For these materials England is at present dependent upon foreign countries, and the high price of guano and of bones prevents their general application, and in sufficient quantity. Every year the trade in these substances must decrease, or their price will rise as the demand for them increases. According to these premises, it cannot be disputed, that the annual expense of Great Britain for the importation of bones and guano is equivalent to a duty on corn: with this difference only, that the amount is paid to foreigners in money. To restore the disturbed equilibrium of constitution of the soil,--to fertilise her fields,--England requires an enormous supply of animal excrements, and it must, therefore, excite considerable interest to learn, that she possesses beneath her soil beds of fossil guano, strata of animal excrements, in a state which will probably allow of their being employed as a manure at a very small expense. The coprolithes discovered by Dr. Buckland, (a discovery of the highest interest to Geology,) are these excrements; and it seems extremely probable that in these strata England possesses the means of supplying the place of recent bones, and therefore the principal conditions of improving agriculture--of restoring and exalting the fertility of her fields. In the autumn of 1842, Dr. Buckland pointed out to me a bed of coprolithes in the neighbourhood of Clifton, from half to one foot thick, inclosed in a limestone formation, extending as a brown stripe in the rocks, for miles along the banks of the Severn. The limestone marl of Lyme Regis consists, for the most part, of one-fourth part of fossil excrements and bones. The same are abundant in the lias of Bath, Eastern and Broadway Hill, near Evesham. Dr. Buckland mentions beds, several miles in extent, the substance of which consists, in many places, of a fourth part of coprolithes. Pieces of the limestone rock in Clifton, near Bristol, which is rich in coprolithes and organic remains, fragments of bones, teeth, &c., were subjected to analysis, and were found to contain above 18 per cent. of phosphate of lime. If this limestone is burned and brought in that state to the fields, it must be a perfect substitute for bones, the efficacy of which as a manure does not depend, as has been generally, but erroneously supposed, upon the nitrogenised matter which they contain, but on their phosphate of lime. The osseous breccia found in many parts of England deserves especial attention, as it is highly probable that in a short time it will become an important article of commerce. What a curious and interesting subject for contemplation! In the remains of an extinct animal world, England is to find the means of increasing her wealth in agricultural produce, as she has already found the great support of her manufacturing industry in fossil fuel,--the preserved matter of primeval forests,--the remains of a vegetable world. May this expectation be realised! and may her excellent population be thus redeemed from poverty and misery! 
44048	----	LEGAL CHEMISTRY. A GUIDE TO THE DETECTION OF POISONS, EXAMINATION OF TEA, STAINS, ETC., AS APPLIED TO CHEMICAL JURISPRUDENCE. TRANSLATED WITH ADDITIONS FROM THE FRENCH OF A. NAQUET, _Professor to the Faculty of Medicine of Paris_. BY J. P. BATTERSHALL, Nat. Sc. D., F.C.S. _SECOND EDITION, REVISED, WITH ADDITIONS._ NEW YORK: D. VAN NOSTRAND, PUBLISHER, 23 MURRAY STREET AND 27 WARREN STREET. 1884. COPYRIGHT. D. VAN NOSTRAND. 1876. Transcriber's Note: Text originally marked up as bold is surrounded by *, text in italics by _. Obvious printer errors have been corrected. A list of all other changes can be found at the end of the document. In the Appendix of the book, only the most obvious errors of punctuation were remedied. PREFACE. The importance of exact chemical analysis in a great variety of cases which come before the courts is now fully recognized, and the translation of this excellent little book on Legal Chemistry, by one of the most distinguished French Chemists, will be appreciated by a large class of American readers who are not able to consult the original. While it is to be regretted that the author has not presented a much more complete work, there is an advantage in the compact form of this treatise which compensates, in some degree, for its brevity. The translator has greatly increased the value of the book by a few additions and his copious index, and especially by the lists of works and memoirs which he has appended; and while he could have further increased its value by additions from other authors, we recognize the weight of the considerations which induced him to present it in the form given to it by the author. Some chapters will have very little value in this country at this day, but the translator could not, with propriety, omit anything contained in the original. C. F. CHANDLER. PREFACE TO THE SECOND EDITION. The principal change to note in this edition of the LEGAL CHEMISTRY is the addition of a chapter on Tea and its Adulteration. The general interest at present evinced concerning this species of sophistication appeared to call for a simple and concise method of examination which would include the requisite tests without entering upon an exhaustive treatment of the subject. The translator's practical experience in the testing of tea at the United States Laboratory of this city has enabled him to make a few suggestions in this regard which, he trusts, may be of use to those interested in food-analysis. Numerous additions have also been made to the bibliographical appendix. J. P. B. CONTENTS. PAGE INTRODUCTION 5 METHODS OF DESTRUCTION OF THE ORGANIC SUBSTANCES By means of Nitric Acid 8 " " Sulphuric Acid 9 " " Nitrate of Potassa 10 " " Potassa and Nitrate of Lime 12 " " Potassa and Nitric Acid 12 " " Chlorate of Potassa 13 " " Chlorine 13 " " _Aqua Regia_ 14 Dialysis 15 DETECTION OF POISONS, THE PRESENCE OF WHICH IS SUSPECTED. Detection of Arsenic 17 _Method used prior to Marsh's test_ 17 _Marsh's test_ 21 _Raspail's test_ 29 _Reinsch's test_ 30 Detection of Antimony 30 _Flandin and Danger's apparatus_ 32 _Naquet's apparatus_ 34 Detection of Mercury 36 _Smithson's pile_ 36 _Flandin and Danger's apparatus_ 37 Detection of Phosphorus 39 _Orfila's method_ 39 _Mistcherlich's method_ 40 _Dusart's method, as modified by Blondlot_ 40 _Fresenius and Neubauer's method_ 42 _Detection of Phosphorus by means of bisulphide of carbon_ 43 _Detection of Phosphorous Acid_ 45 _Estimation of Phosphorus_ 45 Detection of Acids 46 _Hydrochloric Acid_ 46 _Nitric_ " 47 _Sulphuric Acid_ 47 _Phosphoric_ " 48 _Oxalic_ " 49 _Acetic_ " 49 _Hydrocyanic_ " 50 Detection of alkalies and alkaline earths 52 Detection of chlorine, bromine and iodine 54 _Chlorine and Bleaching Chlorides_ 54 _Bromine_ 55 _Iodine_ 56 Detection of Metals 56 Detection of alkaloids and some ill-defined organic substances 65 _Stas's method_ 65 " " _as modified by Otto_ 69 " " " " _Uslar and Erdman_ 70 _Rodgers and Girdwood's method_ 71 _Prollius's method_ 72 _Graham and Hofman's method_ 73 _Application of Dialysis in the detection of Alkaloids_ 74 _Identification of the Alkaloid_ 74 _Identification of Digitaline, Picrotoxine and Colchicine_ 80 METHOD TO BE EMPLOYED WHEN NO CLEW TO THE NATURE OF THE POISON PRESENT CAN BE OBTAINED 85 Indicative tests 86 Determinative tests 94 MISCELLANEOUS EXAMINATIONS 96 Determination of the nature and color of the hair and beard 96 _Determination of the color of the hair and beard_ 96 _Determination of the nature of the hair_ 99 Examination of Fire-arms 100 _The gun is provided with a flint-lock and was charged with ordinary powder_ 100 _The gun is not provided with a flint-lock_ 103 Detection of human remains in the ashes of a fire-place 104 Examination of writings 105 Examination of writings, in cases where a sympathetic ink has been used 110 Falsification of coins and alloys 112 Examination of alimentary and pharmaceutical substances 114 _Flour and Bread_ 114 _Fixed Oils_ 128 _a Olive Oil intended for table use_ 128 _b Olive Oil intended for manufacturing purposes_ 130 _c Hempseed Oil_ 130 _Tea_ 130 _Milk_ 137 _Wine_ 142 _Vinegar_ 147 _Sulphate of Quinine_ 148 Examination of blood stains 150 Examination of spermatic stains 158 APPENDIX 163 Books of Toxicology, etc. 163 Memoirs on Toxicology, etc. 168 INDEX 187 LEGAL CHEMISTRY. The term Legal Chemistry is applied to that branch of the science which has for its office the solution of problems proposed in the interest of Justice. These most frequently relate to cases of poisoning. When the subject of the symptoms or anatomical lesions produced by the reception of a poison is under consideration, the services of a medical expert are resorted to; but when the presence or absence of a poison in the organs of a body, in the _egesta_ of an invalid or elsewhere is to be demonstrated, recourse is had to the legal chemist. Investigations of this character require great practice in manipulation, and, however well the methods of analysis may be described in the works on the subject, there would be great danger of committing errors were the examination executed by an inexperienced person. The detection of poisons, although perhaps the most important, is not the only subject that may come within the province of the legal chemist; indeed, it would be somewhat difficult to define, _a priori_, the multitude of questions that might arise. In addition to cases of supposed poisoning, the following researches are most often required: 1. The examination of fire-arms. 2. The analysis of ashes, in cases where the destruction of a human body is suspected. 3. The detection of alteration of writings, and of falsification of coins and precious alloys. 4. The analysis of alimentary substances. 5. The examination of stains produced by blood and by the spermatic fluid. Each of these researches justly demands a more extended consideration than the limits of this work would permit. The several subjects will be treated as briefly as possible, and at the same time, so as to convey an exact idea of the methods employed, leaving to the expert the selection of the particular one adapted to the case under investigation. We will first mention the methods used in the search for toxical substances. The poisons employed for criminal purposes are sometimes met with in a free state, either in the stomach or intestines of the deceased person, or in the bottles discovered in the room of the criminal or the victim. Under these circumstances, it is only necessary to establish their identity by means of their chemical properties, as directed in the general treatises on chemistry, or by their botanical, or zoological character, in case a vegetable or animal poison, such as cantharides, has been administered. Examinations of this class are extremely simple, the analysis of the substances found, confined to a few characteristic reactions, being a matter of no great difficulty. We will not here dwell longer upon this subject, inasmuch as the analytical methods used are identical with those employed in more complicated cases, with the sole difference that, instead of performing minute and laborious operations in order to extract the poisons from the organs in which they are contained, with a view of their subsequent identification, we proceed at once to establish their identity. The directions given in regard to complicated investigations apply, therefore, equally well to cases of a more simple nature. The detection of a poison mixed with the organic substances encountered in the stomach, or absorbed by, and intimately united with the tissues of the various organs is more difficult. If, however, other information than chemical can be obtained, indicating the poison supposed to be present, and the presence or absence of this one poison is the only thing to be determined, positive methods exist which admit of a speedy solution of the question. When, on the other hand, the chemical expert has not the advantage of extraneous information, but is simply asked,--whether the case be one of poisoning?--nothing being specified as to the nature of the poison used, the difficulty of his task is greatly increased. Up to the present time, the works on Toxicology have, it is true, given excellent special tests for the detection of particular poisons; but none have contained a reliable general method, which the chemical expert could use with the certainty of omitting nothing. Impressed with this need, we proposed, in 1859, in an inaugural dissertation then presented to the Faculty of Medicine, a general method, which, after some slight modifications, is now reproduced. The special methods which allow of the detection of various individual poisons will, however, first be indicated. In cases where the poison is mixed with organic matter, the latter must be removed as the first step in the investigation, as otherwise the reactions characteristic of the poison searched for would be obscured. When the poison itself is an organic substance, this separation is effected by processes modified according to the circumstances. If the detection or isolation of a metallic poison is to be accomplished, the most simple method consists in the destruction of the organic substances. The various methods for effecting this decomposition will now be described. I. METHODS OF DESTRUCTION OF THE ORGANIC SUBSTANCES. BY MEANS OF NITRIC ACID. In order to destroy the organic matters by this process, a quantity of nitric acid equal to one and a half times the weight of the substances taken is heated in a porcelain evaporating dish, the amount of acid being increased to four or six times that of the organic substances if these comprise the brains or liver. As soon as the acid becomes warm, the suspected organs, which have previously been cut into pieces, are added in successive portions: the organs become rapidly disintegrated, brownish-red vapors being evolved. When all is brought into solution, the evaporation is completed and the carbonaceous residue obtained separated from the dish and treated either with water, or with water acidulated with nitric acid, according to the nature of the poison supposed to be present. Several objections to this method exist, the most serious of which is based upon the fact that the carbonaceous residue, containing, as it may, nitric acid, readily takes fire and may therefore be consumed, or projected from the vessel. This objection is a grave one, and is not always entirely removed by the continual stirring of the materials. According to _M. Filhol_, the addition of 10 to 15 drops of sulphuric acid to the nitric acid taken obviates the difficulty; not having personally tested the question we cannot pronounce upon it. If it be the case, this process is an advantageous one, as it is not limited in its application, but can be used in the separation of all mineral poisons. BY MEANS OF SULPHURIC ACID. The organic matter to be decomposed is heated with about one-fifth of its weight of concentrated sulphuric acid, the complete solution of the materials being thus accomplished. The excess of acid is next removed by heating until a spongy carbonaceous mass remains. The further treatment of this residue depends upon the nature of the poison supposed to be present. If the sulphate of the suspected poison is a soluble and stable compound, the residue is directly treated with water; if, on the contrary, there is reason to think that the sulphate has suffered decomposition, the mass is taken up with dilute nitric acid; if, finally, the presence of arsenic is suspected, the residue is moistened with nitric acid, in order to convert this body into arsenic acid. The acid is afterwards removed by evaporation, the well pulverized residue boiled with distilled water, and the solution then filtered. This method, when applied in the detection of arsenic, is objectionable in that the carbonaceous residue, in contact with sulphuric acid, almost invariably contains sulphurous acid, detected by means of permanganate of potassa. This acid, being reduced in the presence of hydrogen, would cause the formation of insoluble sulphide of arsenic, and in this way prevent the detection of small amounts of arsenic by the use of Marsh's apparatus. _M. Gaultier de Claubry_, indeed, states that he has not been able to detect the presence of sulphurous acid in the carbonaceous residue; but one affirmative result would, in this case, outweigh twenty negative experiments. A further objection to this process consists in the fact that the materials to be destroyed almost always contain chlorides, which, in presence of sulphuric acid and an arsenical compound, might determine the formation of chloride of arsenic, a volatile body, and therefore one easily lost. This difficulty is doubtless of a less serious nature than the preceding, as the operation can be performed in a closed vessel provided with a receiver which admits of the condensation of the evolved vapors; but even then the process would be prolonged. The above method is still again objectionable on account of its too limited application, it being serviceable almost exclusively in cases where the poisoning has been caused by arsenic, for, if applied in other instances, a subsequent treatment would be necessary in order to redissolve the metal separated from its decomposed sulphate. BY MEANS OF NITRATE OF POTASSA. This method was formerly executed as follows: Nitrate of potassa was fused in a crucible, and the substances to be destroyed added in small portions to the fused mass. The organic matter soon acquired a pure white color; owing, however, to the imperfect admixture of the organic matter with the salt used for its decomposition, it was necessary to take a large excess of the latter. The following process, suggested by _M. Orfila_, remedies this inconvenience: The organs are placed in an evaporating dish, together with one tenth of their weight of caustic potassa, and a quantity of water varying with the weight of the substances taken. An amount of nitrate of potassa equal to twice the weight of the organic matter is next added, and the mixture evaporated to dryness. The residue is then thrown by fragments into a Hessian crucible heated to redness, the portions first taken being allowed to become perfectly white before more is added. Whichever process has been employed, the fused mass is decanted into a porcelain crucible, which has previously been heated in order to avoid danger of breakage. The portion remaining in the vessel is taken up by boiling with a small quantity of distilled water, and the solution so obtained likewise added to the crucible. The mass is then heated with sulphuric acid until all nitrous fumes are expelled, as these could give rise to an explosion, when, in the search for arsenic, the substance is introduced into Marsh's apparatus. As soon as the nitric acid is completely expelled, the liquid is allowed to cool; the greater portion of the sulphate of potassa formed now separating out in crystals. The fluid is next filtered and the crystalline salt remaining on the filter, washed, at first with a little distilled water, then with absolute alcohol, which is subsequently removed from the filtrate by boiling. This method is scarcely applicable otherwise than in the detection of arsenic, as in other instances the presence of a large amount of sulphate of potassa would be liable to affect the nicety of the reactions afterwards used. Its application, even in the search for arsenic, is not to be strongly recommended; on the contrary, the separation of the potassa salt by filtration is indispensable, as otherwise a double salt of zinc and potassium, which might be formed, being deposited upon the zinc used in Marsh's apparatus, would prevent the disengagement of hydrogen, and every chemist is too well aware of the difficulty of thoroughly washing a precipitate, not to fear the possible loss of arsenic by this operation. BY MEANS OF POTASSA AND NITRATE OF LIME. In this method the organic materials are heated with water and 10 to 15 per cent. of caustic potassa. As soon as disintegration is completed, nitrate of lime is added, and the mixture evaporated to dryness. A glowing coal is then placed upon the carbonaceous residue obtained: the mass, undergoing combustion, leaves a perfectly white residue. This residue dissolves in hydrochloric acid to a clear fluid which is then examined for poisons. The above process possesses the undeniable advantage of completely destroying the organic substances, at the same time avoiding the introduction of sulphate of potassa, the presence of which impairs the usefulness of the preceding method; but it necessitates the presence of numerous foreign bodies in the substance to be analysed, and this should be avoided. The _absolute purity_ of reagents is not always to be attained, and the results of an analysis are the more certain, in proportion as they are less numerous and more easily purified. BY MEANS OF POTASSA AND NITRIC ACID. It has been proposed, instead of using nitrate of lime, to dissolve the organic matter in potassa and then saturate the fluid with nitric acid. This method is evidently more complicated than the simple treatment with nitrate of potassa, and possesses, moreover, no advantages over the latter process. BY MEANS OF CHLORATE OF POTASSA. The organic materials are treated with an equal weight of pure hydrochloric acid, and water added, so as to form a clear pulp. This being accomplished, two grammes of chlorate of potassa are added to the mixture at intervals of about five minutes. The fluid is next filtered, and the insoluble residue remaining on the filter washed until the wash-water ceases to exhibit an acid reaction. The filtrate is then evaporated, an aqueous solution of sulphurous acid added, until the odor of this reagent remains distinctly perceptible, and the excess of the acid removed by boiling the solution for about an hour. The fluid is now adapted to further examination for arsenic, or other metallic poisons. This method is one of the best in use, both chlorate of potassa and hydrochloric acid being reagents easily procured in a state of great purity; their use, however, is liable to the objection that they convert silver and lead into insoluble chlorides. BY MEANS OF CHLORINE. _M. Jacquelain_ suggests, in the search for arsenic, the decomposition of the organic matters by means of a current of chlorine, and recommends the following process: The organic substances are bruised in a mortar and then macerated with water. The fluid so obtained, in which the organic matter is held suspended, is next placed in a flask into which a current of chlorine is passed until all the organic matter is deposited in colorless flakes on the bottom of the vessel. The flask is then well closed and allowed to stand for 24 hours, when the odor of the gas should still be perceptible. The fluid is now filtered, the filtrate concentrated by heating in a vessel which permits of the preservation of the volatile chloride of arsenic possibly present, and then examined for poisons. This process fails to possess the degree of generality desirable, and presents the disadvantage of requiring considerable time for its execution. BY MEANS OF AQUA REGIA. This method is exceedingly simple: _Aqua regia_ (a mixture of two parts of hydrochloric and one part of nitric acids) is placed in a tubular retort provided with a receiver, and the organic materials, which have previously been cut into small pieces, added; the reaction commences immediately; if it is not sufficiently active, it is accelerated by a gentle heat: lively effervescence now occurs, and the destruction of all non-oleaginous substances is soon accomplished. The latter substances alone are not immediately decomposed by _aqua regia_, which attacks them only after prolonged action. As soon as the operation is concluded, the apparatus is removed from the fire and taken apart. The fluid condensed in the receiver is added to that remaining in the retort, and the whole thoroughly cooled in an open dish. The fatty matters now form a solid crust upon the surface of the fluid, which is removed and washed with distilled water, and, the washings being added to the rest of the solution, the latter is directly examined for metallic poisons. It is recommended by _Gaultier de Claubry_, in cases where the detection of arsenic is desired, to saturate and afterwards boil the suspected fluid with sulphuric acid, in order to remove the nitric and hydrochloric acids present. DIALYSIS. The application of the dialytic method was first proposed by _Graham_. By its use we are enabled to distinguish between two large classes of bodies, viz., _colloids_ and _crystalloids_. Albumen, gelatine, and analogous substances are typical of colloid bodies; crystalloid substances, on the other hand, are those that are capable of crystallization, either directly or in their compounds, or, in case they are fluids, would possess this property when brought to the solid state. Graham discovered that when an aqueous solution containing a mixture of colloid and crystalloid substances is placed in a vessel having for its bottom a piece of parchment or animal membrane, and this is immersed in a larger vessel filled with water, all of the crystalloids contained in the first vessel transverse the porous membrane and are to be found in the larger vessel, the colloid bodies being retained above the membrane. The organic matter to be eliminated in toxicological researches being colloids, and the poisons usually employed being crystalloids, the value of dialysis as a method of separation is evident. The process is executed as follows: [Illustration: Fig. 1.] A wooden,--or better, a gutta-percha--cylinder (Fig. 1), 5 cubic centimetres in height and from 20 to 25 c. c. in diameter, is employed. A piece of moistened parchment is securely attached to one of the openings of the cylinder, which, upon drying, shrinks and completely closes the aperture. If its continuity becomes impaired, the pores of the membrane should be covered with the white of an egg which is subsequently coagulated by the application of heat. The organs previously cut into small pieces, or the materials found in the alimentary canal, etc., after having been allowed to digest for 24 hours in water at 32°[A]--or, in dilute acids, if the presence of an alkaloid is suspected,--are then placed in the upper vessel, which is termed the dialyser. The whole should form a layer not over 2 cubic centimetres in height. The dialyser is next placed in the larger vessel filled with distilled water. In about 24 hours three-quarters of the crystalloid substances present will have passed into the lower vessel. The solution is then evaporated over a water-bath, and submitted to analysis. The portion remaining in the dialyser is decomposed by one of the methods previously described, in order to effect the detection of any poisonous substances possibly present. Instead of the above apparatus, the one represented in Fig. 2 can be employed. The fluid under examination is placed in a bell-shaped jar, open at the top and closed below with a piece of parchment, which is then suspended in the centre of a larger vessel containing water. In other respects the operation is performed in the same manner as with the apparatus represented in Fig. 1. [Illustration: Fig. 2.] [A] The degrees of temperature given in the text refer to the centigrade Thermometer; their equivalents on the Fahrenheit scale can be obtained by means of the formula: 9/5 C° + 32 = F°. --_Trans._ II. DETECTION OF POISONS, THE PRESENCE OF WHICH IS SUSPECTED. DETECTION OF ARSENIC. It is frequently required, in chemical jurisprudence, to institute a search for arsenic in the remains of a deceased person, whose death is supposed to have been caused by the reception of a poison. Under these circumstances the poison is mixed with a mass of substances which would obscure its characteristic properties, and it becomes necessary, in order to accomplish its identification, to isolate it, and then, by decisive reactions, determine its character. Three methods exist which permit of this result; they are: 1st. The method used prior to Marsh's test. 2nd. Marsh's test. 3rd. A method more recent than Marsh's, proposed by _M. Raspail_. METHOD USED PRIOR TO MARSH'S TEST. The materials supposed to contain arsenic are boiled in water which has been rendered strongly alkaline by the addition of pure potassa. The fluid is then filtered, an excess of hydrochloric acid added, and a current of sulphuretted hydrogen conducted through it. If arsenic be present in the suspected fluid, it is soon precipitated as a yellow sulphide. In dilute solutions the formation of the precipitate fails to take place immediately, and only a yellow coloration of the fluid is perceptible; upon slightly boiling the solution, however, the precipitation of the sulphide is soon induced. The precipitate is collected on a filter, well washed with boiling water, and then removed, if present in a quantity sufficient to admit of this operation. It is next dissolved in ammonia,[B] and the solution so obtained subsequently evaporated to dryness on a watch-glass. The residue of sulphide of arsenic is placed in a tube closed at one end containing nitrate of potassa in a state of fusion: it is decomposed by this treatment into a mixture of sulphate and arsenate of potassa, the reaction being completed in about fifteen minutes. The mixture is now dissolved in water, and lime water added to the solution: a precipitate of arsenate of lime is formed, which is separated from the fluid by filtration, dried, mixed with charcoal, and introduced into a second tube. A few pieces of charcoal are then placed in the tube adjoining the mixture and exposed to a red heat, the part of the tube containing the arsenical compound being also heated. By this operation the arsenic acid is reduced to arsenic, which is deposited upon the cold portion of the tube in the form of a metallic mirror. This mirror is then identified by subsequent reactions. The method just described is no longer in use, although the precipitation of the arsenic by sulphuretted hydrogen is still often resorted to in its separation from the other metals with which it may be mixed. The destruction of the organic substances is, however, accomplished by means of chlorate of potassa and hydrochloric acid. To insure the complete precipitation of the arsenic, it is advisable to conduct sulphuretted hydrogen through the solution, at a temperature of 70° for twelve hours, and then allow the fluid to remain in a moderately warm place, until the odor of the gas is no longer perceptible, the vessel being simply covered with a piece of paper. The precipitate is next freed from the other metals possibly present, as directed in the general method of analysis, collected on a filter, and dissolved in ammonia. The ammoniacal solution is evaporated on a watch crystal, as previously described, and the residuary sulphide reduced to metallic arsenic. This reduction is effected by a process somewhat different from the one previously mentioned: the residue is fused, in a current of carbonic acid gas, with a mixture of carbonate of soda and cyanide of potassium. The apparatus employed is represented in Fig. 3: _a_, is an apparatus producing a constant supply of carbonic acid. Upon opening Mohr's clamp, _g_, the gas passes into the flask _h_, which contains sulphuric acid; it is then conducted, by means of the tube _i_, into the reduction tube _k_, which has an interior diameter of 8 mm. This tube is represented, in half size, in Fig 4. [B] The sulphur, usually accompanying the precipitate of sulphide of arsenic, is insoluble in ammonia.--_Trans._ [Illustration: Fig. 3.] [Illustration: Fig. 4.] The reduction is performed as follows: The sulphide of arsenic is ground in a small mortar, previously warmed, together with 12 parts of a mixture consisting of 3 parts of carbonate of soda and 1 part of cyanide of potassium, both salts being perfectly dry. The powder thus obtained is placed upon a piece of paper rolled in the form of a gutter, and introduced into the reduction tube. The latter is then turned half round its axis, so as to cause the mixture to fall in _de_ without soiling the other parts of the tube. The paper is now withdrawn and the apparatus mounted. Upon opening the clamp _g_, and strongly heating the mixture by either the flame of a gas or an alcohol lamp, a mirror-like ring of metallic arsenic is deposited at _h_, if this poison be present in the substances under examination. When the coating is too minute to permit of perfect identification, it should be driven by heat to a thinner part of the tube; in this way it is rendered easily visible, being condensed upon a smaller space. The above process possesses the advantage of not allowing arsenic to be confounded with any other body; it also permits of a quantitative estimation of the poison present. For this purpose, it is only necessary to previously weigh the watch-crystal, upon which the ammoniacal solution of sulphide of arsenic was evaporated, and to determine its increased weight after the evaporation; the difference of the two weighings multiplied by 0.8049, gives the corresponding weight of arsenious acid, and by 0.6098, the weight of the corresponding amount of metallic arsenic. MARSH'S TEST. Marsh's test is based upon the reduction of arsenious and arsenic acids by nascent hydrogen, and the subsequent transformation of these bodies into water and arsenetted hydrogen, a compound from which the arsenic can be readily isolated. When pure hydrogen is generated in a flask having two openings, one of which is provided with a perforated cork through which a safety-tube passes, the other with a tube bent at a right angle and drawn out to a small point at the free extremity, the evolved gas, if ignited, burns with a pale non-luminous flame. The air should be completely expelled from the apparatus before igniting the gas. Upon bringing a cold porcelain saucer in contact with the point of the flame, only water is formed. If, however, a small quantity of a solution containing arsenious or arsenic acids is introduced into the apparatus by means of the safety-tube, arsenetted hydrogen is produced. This gas burns with a bright flame, yielding fumes of arsenious acid. In case a large amount of the poison is present, it can be recognized by the appearance of the flame, and by inclining a glass tube towards it upon which a portion of the arsenious acid becomes deposited. These indications are, however, not distinguishable in presence of only a small amount of arsenic, and the following distinctive properties of the gas should be verified: 1st. At an elevated temperature it is decomposed into its two constituent elements. [Illustration: Fig. 5.] [Illustration: Fig. 6.] 2nd. The combustibility of the constituents differs: the arsenic being less combustible than the hydrogen, begins to burn only after the complete consumption of the latter body has taken place. For this reason the flame (Fig. 5) is composed of a dark portion _O_ and a luminous portion _I_, which surrounds the first. The maximum temperature exists in _O_ at the point of union of the two parts of the flame. Owing to an insufficient supply of oxygen, the complete combustion of the arsenic in this part of the flame is impossible, and if it be intersected by the cold surface _A B_, that body is deposited as a brown spot, possessing a metallic lustre. The metallic deposit originates, therefore, from the decomposition of the arsenetted hydrogen by heat and from its incomplete combustion. If the spot is not large, it fails to exhibit a metallic lustre; an experienced chemist, however, will be able to identify it by the aid of proper tests. Spots are sometimes obtained when the substance under examination does not contain the least trace of arsenic. These may be caused by antimony or by a portion of the zinc salt in the generating flask being carried over by the gaseous current. This difficulty is remedied by giving the apparatus the form represented in Fig. 6. _A_ is the flask in which the gas is generated. The delivery-tube _I_ connects with a second tube _H_, filled with asbestus or cotton; this is united by means of a cork with a third tube _C_, made of Bohemian glass. The latter tube is quite long, and terminates in a jet at its free end, enclosed in tin-foil;[C] it passes through the sheet-iron furnace _R_, supported upon _G_. The screen _D_ protects the portion _D E_ of the tube _C_ from the heat. The gas disengaged is ignited at _E_ and the porcelain dish _P_ is held by the hand in contact with the flame. The apparatus being mounted, zinc, water and some sulphuric acid are placed in the generating flask,[D] and the solution containing arsenious acid added: the evolution of gas commences immediately. The tube _H_ serves to retain any liquids that may be held suspended. The gas then passes through the part _C D_ of the tube _C_, which is heated by placing a few live coals upon the furnace _R_. The greater portion of the arsenetted hydrogen is decomposed here, and is deposited on the cold part of the tube, in a mirror-like ring. The small quantity of gas that escapes decomposition, if ignited at _E_, produces a metallic spot on the dish _P_. In order to determine that the spots are due to the presence of arsenic, and not produced by antimony, the following tests should be applied: [C] The fusing of the point of the tube is also prevented by platinizing it. The tube is drawn out, its end roughened by filing, and then immersed in solution of bichloride of platinum, so that a drop or two of the fluid adheres. The point, upon heating, now acquires a fine metallic lustre, and by repeating the operation a few times a good coating of platinum is produced both on the exterior and interior of the tube.--_Trans._ [D] The addition of a few drops of solution of bichloride of platinum to the mixture of zinc, water and sulphuric acid is advisable.--_Trans._ 1. The color of the spots is distinctive: arsenical spots are brown and exhibit a metallic lustre, whereas those originating from antimony possess a black color, especially near their border. This difference is, however, not perceptible when the deposits have a large surface. 2. If the mirror be arsenical, it is readily volatilized from one part of the tube to another, when the latter is heated, and a current of hydrogen, or carbonic acid gas made to pass through it. Spots that are due to the presence of antimony are much less volatile. 3. If the tube is held in an inclined position so that a current of air traverses it, and the part containing the arsenical mirror heated, the arsenic oxidizes and arsenious acid is sublimed and deposited higher up in the tube in the form of a ring, which exhibits octahedral crystals when examined with a magnifying glass. This ring should be further tested as follows: _a._ If it is dissolved in a drop of hydrochloric acid and a solution of sulphuretted hydrogen added, a yellow precipitate of sulphide of arsenic is formed. This compound is soluble in ammonia and in alkaline sulphides, but insoluble in hydrochloric acid. _b._ If the ring is dissolved in pure water and an ammoniacal solution of sulphate of copper added, a beautiful green precipitate ("_Scheele's green_"), consisting of arsenite of copper, is produced. 4. When produced by arsenic the spots are soluble in nitric acid, and upon evaporating the solution so obtained to dryness, a residue of arsenic acid, which is easily soluble in water, remains. If an ammoniacal solution of nitrate of silver is added to the aqueous solution of the residue, a brick-red precipitate is produced. Spots consisting of antimony give, when treated with nitric acid, a residue of an intermediate oxide, insoluble in water. 5. Upon treating the spots with a drop of solution of sulphide of ammonium, the sulphide of the metal present is formed: if sulphide of arsenic is produced its properties, as enumerated above, can be recognized. It may be added that the sulphide of antimony formed is soluble in hydrochloric acid, and possesses an orange red color, whereas sulphide of arsenic is yellow. 6. When spots originating from arsenic are treated with a solution of hypochlorite of soda (prepared by passing chlorine into solution of carbonate of soda), they are immediately dissolved; if, on the other hand, they are produced by antimony, they remain unaltered by this treatment. Such are the properties exhibited by soluble compounds of arsenic when treated by Marsh's process; the following precautions are, however, necessary when this test is made use of in medico-legal examinations. 1. If small white gritty particles, resembling arsenious acid, are discovered in the stomach or intestines, they are directly introduced into Marsh's apparatus. When this is not the case, the destruction of the organic matter is indispensable even though, instead of the organs themselves, the contents of the alimentary canal are taken. In the latter instance, the solids are separated from the fluids present by filtration, the solution evaporated to dryness and the residue united with the solid portion; the organic matter is then destroyed by one of the methods previously described. In the special case of arsenic, the separation of the poison from the accompanying organic materials can be accomplished by a process not yet mentioned which may prove to be of service. The suspected substances are distilled with common salt and concentrated sulphuric acid. By this operation the arsenic is converted into a volatile chloride which distils over. The poison is isolated by treating this compound with water, by which it is decomposed into hydrochloric and arsenious acids. We must give preference, however, to the method by means of chlorate of potassa and hydrochloric acid. 2. The solution having been obtained in a condition suitable for examination, the air is completely expelled from the apparatus by allowing the gas to evolve for some time, and the suspected fluid then introduced into the generating flask. Danger of explosion would be incurred were the gas ignited when mixed with air.[E] [E] The effervescence of the mixture is prevented by _slowly_ adding the arsenical solution to the generating flask. In order to avoid loss of arsenetted hydrogen, the cold dish should be directly applied to the flame even before the introduction of the suspected solution, and its position changed at short intervals, so as to allow the deposit to be formed on different parts.-_Trans._ 3. It is indispensable, in applying this test, to have a second apparatus in which only the reagents necessary to generate hydrogen are placed: in this way, if no spots are now produced by the use of the second apparatus, it is certain that those obtained when the first apparatus is employed do not originate from impurities present in the reagents used. It has come under the author's observation, however, that a sheet of zinc sometimes contains arsenic in one part and not in another; in fact, the shavings of this metal, as purchased for laboratory use, are often taken from lots previously collected, and may therefore have been prepared from several different sheets. If this be the case, it is supposable that the zinc used in the second apparatus may be free from arsenic, whereas the metal with which the suspected solution is brought in contact may contain this poison; serious danger would then exist of finding indications of the presence of arsenic in materials that did not originally contain a trace of the metal. In order to obviate this important objection, which might possibly place a human life in jeopardy, we propose the following modifications: Pure mercury is distilled and its absolute purity established. As the metal is a fluid and is therefore homogeneous, it is evident if one portion be found pure, the entire mass is so. Sodium is then fused under oil of naphtha, in order to cause the complete admixture of its particles, and the purity of the fused metal in regard to arsenic tested. An amalgam is next prepared by uniting the mercury and sodium. This is eminently adapted to toxicological investigations: in order to generate a supply of very pure hydrogen, it is only necessary to place the amalgam in water kept slightly acid by the addition of a few drops of sulphuric acid, by means of which the disengagement of gas is rendered more energetic.[F] [F] Owing to the impurities often occurring in zinc, the use of distilled magnesium in Marsh's apparatus has also been suggested. This metal is now to be obtained in a state of great purity; it is, however, sometimes contaminated with silicium, which body likewise gives rise to a metallic deposit, but one that is readily distinguished from arsenical spots by its insolubility in nitric acid, _aqua regia_, and in hypochlorite of soda. The presence of magnesium causes the precipitation of the non-volatile metals possibly contained in the fluid tested for arsenic.--_Trans._ It should be borne in mind that the solution introduced into Marsh's apparatus must not contain organic substances, and that, in case their destruction has been accomplished by means of nitric acid all traces of this compound are to be removed. The sulphuric acid used should also be completely freed from nitrous vapors. According to _M. Blondeau_, nascent hydrogen in the presence of nitrous compounds converts the acids of arsenic not into arsenetted hydrogen (As H{3}), but into the _solid_ arsenide of hydrogen (As{4} H{2}). This latter compound, upon which pure nascent hydrogen has no effect, is transformed into gaseous arsenetted hydrogen by the simultaneous action of nascent hydrogen and organic substances. These facts are of the greatest importance, for they might possibly cause a loss of arsenic when it is present, as well as determine its discovery when it is absent. The first case is supposable: should traces of nitric acid remain in the solution, the arsenic would be transformed into solid arsenide of hydrogen and its detection rendered impossible. The second case may also occur: if the zinc placed in the apparatus contains arsenic, and the sulphuric acid used contains nitrous compounds, the evolved gas will fail to exhibit any evidence of the presence of arsenic, owing to the formation of the solid arsenide of hydrogen. Upon adding the suspected solution, which, perchance, may still contain organic substances, this arsenide is converted into arsenetted hydrogen, and the presence of arsenic will be detected, although the solution under examination was originally free from this metal. RASPAIL'S METHOD. M. Raspail suggests the following method for detecting arsenic: The surface of a brass plate is rasped by filing. In this condition the plate may be regarded as an innumerable quantity of voltaic elements, formed by the juxtaposition of the molecules of zinc and copper. The suspected materials are boiled with caustic potassa, the solution filtered, a drop of the filtrate placed upon the brass plate, and a drop of chlorine water added. If the plate is then allowed to stand for a moment and the substance under examination contains arsenic, a mirror-like spot is soon deposited upon its surface. In order to avoid confounding this deposit with those produced by other metals, the substitution of granulated brass for the plate is in some cases advisable. The granulated metal is dipped successively in the suspected solution and in chlorine water. The granules retain a small quantity of the solutions and, owing to the action of the chlorine water, become covered with metallic spots, if arsenic be present. They are then dried, placed in a tube closed at one end, and exposed to the heat of an alcohol lamp. In case the spots are arsenical, the metal volatilizes and condenses in a ring upon the cold part of the tube, which is submitted to the tests previously described. This method can hardly be of great service, inasmuch as it extracts the poison from but a very small portion of the solution containing it: we have not, however, personally tested its merits.[G] [G] The omission in the text of Reinsch's test should be supplied. This test is based upon the fact that when solutions of arsenious acid or an arsenide are acidulated with hydrochloric acid and boiled with metallic copper, the latter becomes covered with a film consisting largely of metallic arsenic: it is extensively employed in chemico-legal examinations. The materials to be examined are completely disintegrated by boiling with hydrochloric acid, and the fluid filtered. Some pure copper gauze or foil, having a polished surface, is then immersed in the boiling solution, and notice taken of the formation of a grey deposit. If a coating be formed, fresh pieces of the metal are added, so long as they become affected. The copper is then withdrawn from the solution, thoroughly washed with water, and dried, either by means of the water-bath or by pressing between bibulous paper. It is next introduced into a dry tube, and heated over a spirit lamp. The arsenic present volatilizes and is oxidized to arsenious acid which forms a deposit, consisting of octahedral crystals, on the cold part of the tubes. These are subsequently tested by means of the reactions distinctive of arsenious acid. It need hardly be added that the absolute purity of both the hydrochloric acid and of the copper is to be carefully established. The deposit obtained in the above operation was formerly regarded as pure arsenic, but it has been proved to be an alloy consisting of 32 per cent. arsenic, and 68 per cent. copper. Reinsch's test possesses the advantage of requiring but little time for its execution, of being applicable to complex organic mixtures, and of effecting the detection of a very minute trace of the poison.--_Trans._ DETECTION OF ANTIMONY. Strictly speaking the salts of antimony are more therapeutic than poisonous in their action. In fact they usually act as emetics and, under certain circumstances, may be taken in large doses without incurring serious results. There are instances, however, in which their action is truly toxical, and it becomes necessary to effect their detection in the organs of a body. It should be remarked that these salts, if absorbed, remain by a kind of predilection in the liver and spleen. A special examination of these organs should therefore be instituted, particularly if the fluids of the alimentary canal are not at hand, which is frequently the case when some time has elapsed before the investigation is undertaken. The remarks made in the preceding article concerning the distinctive properties of arsenic and antimony need not be repeated here. The search for antimony is likewise executed by aid of Marsh's apparatus. We will confine ourselves to a description of a modification to this apparatus proposed by _MM. Flandin_ and _Danger_, and employed in the separation of antimony and arsenic, when a mixture of these metals is under examination. Another process, by means of which we arrive at the same result with greater certainty and by the use of a less expensive apparatus, will then be mentioned. We will, however, first indicate the preferable method of destruction of the organic substances. Were the decomposition performed by means of sulphuric acid, sulphate of antimony, a slightly soluble salt and one not well adapted to the subsequent treatment with nascent hydrogen, would be formed. In order to obtain the metal in a soluble state, the formation of a double tartrate of antimony and soda is desirable. This may be accomplished in the following manner: 1. A cold mixture of nitrate of soda, sulphuric acid, and the suspected materials is prepared in the proportion of 25 grammes of the nitrate to 39 grammes of the acid, and 100 grammes of the substance under examination. This mixture is heated and evaporated to dryness, and the decomposition of the organic matter completed in the usual manner. The carbonaceous residue obtained is pulverized, and then boiled with a solution of tartaric acid. By this treatment the antimonate of soda present is converted into a double tartrate of antimony and soda, which is easily soluble in water. The solution is filtered and then introduced into Marsh's apparatus. 2. Another method consists in heating the substances under examination with one half of their weight of hydrochloric acid for six hours on a sand-bath, avoiding boiling. The temperature is then increased until the liquid is in a state of ebullition, and 15 to 20 grammes of chlorate of potassa, for every 100 grammes of the suspected matter taken, added in successive portions, so that a quarter of an hour is required for the operation. The liquid is next filtered, and the resinous matter remaining on the filter well washed with distilled water; the washings being added to the principal solution. A strip of polished tin is then immersed in the liquid: in presence of a large amount of antimony the tin becomes covered with a black incrustation: if but a minute quantity of the metal is contained, only a few blackish spots are perceptible. After the tin has remained immersed for 24 hours, it is withdrawn and placed in a flask together with an amount of hydrochloric acid sufficient for its solution in the cold. If, after several hours, blackish particles are still observed floating in the liquid, they can be dissolved in a few drops of _aqua regia_. The solution may then be directly introduced into Marsh's apparatus. APPARATUS PROPOSED BY FLANDIN AND DANGER. [Illustration: Fig. 7.] This apparatus consists of a wide necked jar _A_ (Fig. 7) for the generation of the gas, the mouth of which is closed with a cork having two openings. The safety tube _S_, which is funnel-shaped at its upper extremity and has its lower end drawn out to a point, passes through one of these apertures; the other opening contains the small delivery tube _B_, open at both ends, and terminating in a point at its upper extremity: it is also provided with lateral openings, in order to prevent the solution being carried up to the flame. The second part of the apparatus is the condenser _C_, 0.03 metre in diameter, and 0.25 metre in length. This terminates at its lower extremity with a cone, and connects at the side with the tube _T_, slanting slightly downwards. In the interior of the condenser, the cooler _E_ is contained, the lower end of which is nearly in contact with the sides of the opening _O_. The combustion tube _D_, 0.01 metre in diameter, is connected by means of a cork with the tube _T_; it is bent at right angles, and encloses the tube _B_, in such a manner as to allow the evolved gas to burn in its interior. The dish _F_ is placed beneath the opening _O_. If the gas which burns in the combustion tube contains arsenetted hydrogen, water and arsenious acid are produced. A portion of this acid is retained in the tube _D_, the remainder is carried over, with the aqueous vapor, into _C_, where it condenses, and finally falls into the dish _F_. Both portions are subsequently examined by means of reactions necessary to establish the presence of the acid. If the ignited gas contains antimonetted hydrogen, water and an intermediate oxide of antimony are formed. The latter compound is entirely retained in the tube _D_ separated from the greater part of the arsenious acid, if this body be present, and can be brought into solution by means of a mixture of hydrochloric and tartaric acids. A fluid is then obtained which can be introduced into Marsh's apparatus, or otherwise examined for antimony. NAQUET'S APPARATUS. [Illustration: Fig. 8.] Although the separation of arsenic from antimony is the chief object in making use of the apparatus proposed by Flandin and Danger, it is evident that this result is not fully accomplished, since a small portion of arsenious acid remains in the tube _D_ (Fig. 7), together with the intermediate oxide of antimony. The following method secures the complete separation of these metals: An amalgam of sodium and mercury is introduced into the flask _A_, (Fig. 8), which is provided with two openings. The tube _B_, terminating in a funnel at its upper extremity, passes through one of these orifices. The other aperture contains a cork enclosing the small tube _C_, which is bent at a right angle and communicates, by means of a cork, with the larger tube _D_ filled with cotton or asbestus. A set of Liebig's bulbs, _E_, containing a solution of nitrate of silver, is attached to the other extremity of this tube. The apparatus being mounted, the solution under examination is slightly acidulated and introduced by means of the tube _B_ into the flask _A_: the disengagement of gas begins immediately. If arsenic and antimony are contained in the solution, arsenetted hydrogen and antimonetted hydrogen are evolved. Both gases are decomposed in passing through the solution of nitrate of silver contained in the Liebig bulbs: the arsenetted hydrogen causes a precipitation of metallic silver, all the arsenic remaining in solution as arsenious acid; the antimonetted hydrogen is decomposed into insoluble antimonate of silver. After the operation has continued for several hours, the apparatus is taken apart, the nitrate of silver solution thrown on a filter, and the precipitate thoroughly washed. An excess of hydrochloric acid is then added to the filtrate, and the precipitate formed separated from the solution by filtration, and well washed. The wash-water is added to the solution, and the whole then examined for arsenic by means of Marsh's test. The precipitate formed in the nitrate of silver solution, which contains antimonate of silver, is well dried, mixed with a mixture of carbonate and nitrate of soda, and calcined in a porcelain crucible for about three-quarters of an hour. The crucible is then removed from the fire, and the cooled mass treated with hydrochloric acid until a drop of the filtered fluid ceases to give a residue when evaporated upon a watch-glass to dryness. A current of sulphurous acid is now conducted through the filtered solution until the odor of this gas remains persistent. The excess of acid is then removed by boiling, and the solution placed in Marsh's apparatus and tested for antimony. DETECTION OF MERCURY. If a mercurial salt exists in a considerable quantity in the substances extracted from the alimentary canal, or ejected either by stools or vomiting, it can be isolated by treating these materials with water, filtering the liquid, and evaporating the filtrate to dryness. The residual mass is taken up with alcohol, and the solution again filtered and evaporated. Upon dissolving the residue obtained by this operation in ether and filtering and evaporating the solution, a residue is obtained which when dissolved in water forms a fluid wherein the presence of mercury can be detected by means of the ordinary tests. When, however, only a minute quantity of mercury is present, and this has been absorbed, its detection is more difficult. It will be necessary under these circumstances to make use of either Smithson's pile or Flandin and Danger's apparatus. SMITHSON'S PILE. Smithson's pile consists of a small plate of copper around which a piece of thin gold foil is wrapped. This is immersed in the solution to be tested for mercury, which has previously been slightly acidulated: if mercury be present, the plate acquires a white color which disappears upon exposure to the flame of a spirit-lamp. A similar reaction occurs in presence of tin, as this metal would likewise be deposited upon the plate, and, upon heating, would penetrate the metal and restore to it its natural color. The danger of mistake arising from this fact is obviated by introducing the copper plate into a tube closed at one end and bent at a right angle. The open extremity of the tube is drawn out to a fine point and immersed in water contained in a second tube also closed at one end. Upon heating the plate in the flame of an alcohol lamp, the white color disappears if produced by mercury, and at the same time this metal condenses in the narrow extremity of the tube. The metallic globules formed can be recognized either by the naked eye or with the aid of a lens, or by rubbing them with a piece of gold foil when the latter will acquire a white coating. When Smithson's pile is employed, the organic substances are most advantageously decomposed by means of chlorine. It is advisable to operate with as small a quantity of fluid as possible, for, owing to the volatility of bichloride of mercury, a portion of this salt may be lost by the evaporation of aqueous, alcoholic, and even etherial solutions, and the detection of minute quantities rendered impossible. APPARATUS PROPOSED BY FLANDIN AND DANGER. [Illustration: Fig. 9.] This apparatus consists of a stand _S_, (Fig. 9) supporting a balloon _A_, which serves as the reservoir of the suspected solution, and a funnel _B_, into which the neck of the balloon is dipped. The funnel _B_ is bent at a right angle and is drawn out at its lower end under which the dish _C_ is placed for the reception of the escaping fluids. A fine wire of pure gold, forming the negative electrode of a Bunsen's battery, passes through the lower extremity of the funnel. The end of this wire nearly comes in contact with a second wire, inserted in the upper part of the funnel, and connected with the positive pole of the battery. If the balloon filled with the solution is inverted and immersed in the funnel _B_, its neck will be submerged at first; soon, however, it becomes uncovered, owing to the depression of the level of the fluid caused by the escape of the latter through the tapering extremity of the funnel: a bubble of air then passes in the balloon and expels a drop of the solution. This process is repeated at short intervals, causing a continuous flow of the fluid, the rapidity of which is easily regulated by elevating or lowering the balloon, thus raising or depressing the level of the liquid. The apparatus having been mounted in this manner and the battery set in action, the disengagement of gas commences. Should mercury be contained in the solution under examination, this metal will be deposited upon the negative wire. When the operation is completed this wire is detached from the apparatus, washed with ether, and dried. It is then introduced into a small tube provided with a bulb, and the mercury volatilized by means of the blow pipe flame: the metal condenses in the bulb of the tube in globules which are readily recognized. They can also be dissolved in nitric acid, and the presence of a mercurial salt in the solution confirmed by further tests. The solution to be examined in the preceding apparatus, is prepared as follows: The suspected organic matter is treated with cold sulphuric acid of 66° _B._ until liquefied, and hypochlorite of lime, and distilled water then added: if necessary, the evolution of chlorine can be accelerated by a further addition of sulphuric acid. As soon as the liquid becomes clear, it is filtered, concentrated and examined as described above. The solution contains the mercury in the state of bichloride, a salt soluble in water and well adapted to the above test. The substitution of a large balloon, having a capacity of about 2 litres, in place of the small vessel of Flandin and Danger's apparatus, is to be recommended as doing away with the necessity of evaporation; an operation which invariably causes a loss of substance. The apparatus, modified in this manner, is the most delicate in use for the detection of mercury. DETECTION OF PHOSPHORUS. ORFILA'S METHOD. The solid substances found in the alimentary canal are mechanically separated from the fluids present by means of a linen cloth. They are then examined by aid of a magnifying glass, and any fragments of phosphorus found separated and preserved under water. If none are discovered, the presence of phosphorescent vapors may possibly be detected by examining the materials in the dark. In any case, a portion of the suspected materials should be treated with nitrate of silver: in presence of phosphorus the materials acquire, first, a reddish-brown, then, a black color. The remaining portion is spread upon a shovel and heated: a white flame, burning at various points of the mass, and originating from the combustion of phosphorus, is observed, if this body be contained in the substances under examination. This method is evidently far from perfect. MITSCHERLICH'S METHOD. Mistcherlich's method is based upon the luminosity of the vapors of phosphorus. The suspected materials are moistened with dilute sulphuric acid, and heated, in a flask communicating with a glass worm which passes through a glass cooler into a receiver. If the apparatus is placed in the dark, and the materials contain phosphorus, luminous vapors will be observed in the flask and receiver. When the quantity of the poison present is considerable, the phosphorous acid formed can be collected and its properties tested. DUSART'S METHOD, AS MODIFIED BY BLONDLOT. [Illustration: Fig. 10.] Dusart's process takes advantage of the facility with which hydrogen combines with phosphorus. The substances under examination are placed between two asbestus stoppers in a tube, one end of which tapers to a point, and a current of pure hydrogen conducted over them. In presence of phosphorus the evolved gas will burn with a green flame, and, upon bringing this in contact with a porcelain plate, red spots will be deposited upon the latter. _Blondlot_ prefers to introduce the suspected materials into the flask in which the hydrogen is generated. He employs the apparatus represented in Fig. 10: _a_ is a flask for evolving hydrogen; _b_ is a U tube, filled with fragments of pumice stone which are saturated with a concentrated solution of potassa; _c_ is a Mohr clamp; _d_ a screw-clamp; _e_ a platinum jet. This jet is necessary in order to avoid a yellow coloration of the flame by the soda contained in the glass. Pure hydrogen is at first evolved, in order to ascertain that the flame is colorless and red spots are not produced when it is intersected by a cold plate. The purity of the reagents used having thus been confirmed, the clamp _d_ is closed until the acid is forced back into _f_; and the materials to be examined are then added to the fluid. Upon opening the clamp the liquid passes from _f_ into _a_, and the evolution of gas recommences. The gas is then ignited: the flame possesses the characteristic properties mentioned above, if the suspected substances contain phosphorus. METHOD PROPOSED BY FRESENIUS AND NEUBAUER. According to this method, the materials are brought into a flask provided with a doubly-perforated stopper, and water, acidulated with sulphuric acid, added. The flask is then heated over a water-bath, and a current of carbonic acid conducted through the mixture for at least two hours. The gas, on leaving the flask, passes into a solution of nitrate of silver. Should no precipitate form in this solution, the absence of free phosphorus is established, for, were this body present, a portion would be volatilized, and a black precipitate, consisting of phosphide of silver, together with phosphoric acid, produced. The formation of a black precipitate is, however, not necessarily a proof of the presence of phosphorus. In order to conclusively determine the character of the precipitate, it is collected on a filter and examined by the method of Dusart and Blondlot. This process has given result in cases where none were obtained by Mistcherlich's method. It possesses, moreover, an advantage over the latter process, in not being influenced by the presence of foreign bodies; whereas, in Mistcherlich's method, some time must elapse before the luminosity of the vapors becomes apparent if ether or alcohol is contained in the solutions, and this phenomenon totally fails to appear in presence of oil of turpentine. DETECTION OF PHOSPHORUS BY THE USE OF BISULPHIDE OF CARBON. In a report read before the Academy of Sciences in 1856, presented by an examining commission, of which MM. _Dumas_, _Pelouze_ and _Claude Bernard_ were the reporters, the following results were contained: Phosphorus may remain, in the _free state_, in the organs fifteen days after death, and even then its isolation can easily be accomplished. For this purpose the stomach or intestines, and the articles of food contained therein, are cut into pieces and treated with bisulphide of carbon. Upon filtering the liquid, a solution is obtained containing all the phosphorus present, which exhibits the following properties: 1st, When ignited, it burns with a very luminous flame; 2nd, if allowed to spontaneously evaporate (the combustion of the phosphorus being prevented by the organic matter present [_Naquet_]) an inflammable residue is obtained, which, if dissolved in boiling monohydrated nitric acid, gives a solution that, after saturation with ammonia, produces a precipitate soluble in acids in solutions of barium salts. If the solution is mixed with perchloride of iron, and the sesquioxide of this metal subsequently eliminated by the addition of ammonia, it no longer causes a precipitation in barium solutions. The fluid acquires a yellow coloration when boiled with a solution of molybdate of ammonia. According to our personal experience, the apparatus employed by Flandin and Danger for the detection of arsenic, can also be made use of in the examination of the bisulphide of carbon solution. To this end, the fluid supposed to contain phosphorus is mixed with perfectly pure alcohol, and the mixture placed in a small spirit-lamp provided with a very loose asbestus wick. The lamp is then ignited and the flame introduced in the combustion tube _D_ (Fig. 11). [Illustration: Fig. 11.] By the combustion of the mixture, sulphurous, carbonic, phosphorous acids and water are formed. The water condenses in _c_, and, falling into the dish _F_, carries with it the sulphurous and phosphorous acids. The acid liquid collected in this way is evaporated to dryness, some nitric acid added, and the solution again evaporated. The remaining mass is then dissolved in water to which some ammonia is added, and the solution tested for phosphoric acid. This method is an advantageous one as the phosphoric acid formed must originate from phosphorus in the _free state_, and not from any phosphates which, owing to the presence of organic matter, might be contained in the bisulphide of carbon solution. It would, however, lead the analyst into error if the person, supposed to have been poisoned had eaten cerebral substances or eggs previous to death, as these contain glycero-phosphoric acid; it is therefore advisable to compare the results given by this process with those obtained by the use of other methods. DETECTION OF PHOSPHOROUS ACID. Provided free phosphorus has not been detected, it is necessary to search for phosphorous acid. To this end, the residue remaining in the flask, in either Mistcherlich's or Fresenius and Neubauer's method, is introduced into the apparatus of Dusard and Blondlot. If the phosphorus reaction appears, it is sufficient; otherwise, its production may have been hindered by the presence of organic matter. In case, therefore, the flame is colorless, the evolved gas is conducted into a neutral solution of nitrate of silver. If the materials contain phosphorous acid, a precipitate of phosphide of silver is formed which should be collected and washed. The precipitate, which is now free from organic matter, is then examined for phosphorous acid by means of the apparatus of Dusard and Blondlot. ESTIMATION OF PHOSPHORUS. The best process for determining quantitatively the amount of phosphorus present is the one recommended by Fresenius and Neubauer. The gaseous current is continued until a fresh nitrate of silver solution is no longer precipitated. The solution is filtered, the precipitate washed and then dissolved in nitric acid. The silver is next precipitated by addition of hydrochloric acid, the fluid again filtered, and the precipitate well washed. The washings are added to the filtrate, and the liquid concentrated in a porcelain capsule. A solution of sulphate of magnesia, containing ammonia, is next added to the fluid, and the phosphoric acid determined as pyrophosphate of magnesia: the precipitate formed, is washed, heated to redness, in order to convert it into the pyrophosphate, and then weighed. DETECTION OF ACIDS. The search for acids is to be instituted exclusively in the alimentary canal and its contents. Were acids contained in the other organs, their presence would be due to the blood in which they had previously been absorbed, and, as in this case they would be partially neutralized by the bases contained in the blood, a conclusive decision in regard to their original existence in the suspected materials would be impossible, the salts of the acids usually searched for being normal constituents of the blood. In order to detect the presence of acids, the alimentary canal and contents are first boiled with water which is renewed until the solution ceases to exhibit an acid reaction when tested with litmus paper. The fluid is then filtered, alcohol added to the filtrate, in order to precipitate organic substances, the liquid again filtered, and the solution tested separately for the various acids as directed below. HYDROCHLORIC ACID. The solution is placed in a retort provided with a receiver and distilled until the residual fluid assumes a pasty consistence: the operation is then discontinued. If hydrochloric acid be present in the materials under examination, the distillate will have an acid reaction, and, upon addition of solution of nitrate of silver, a white precipitate, which is easily soluble in ammonia but insoluble in nitric acid and in short possesses all the properties of chloride of silver, will be formed. NITRIC ACID. The distillate, obtained as in the preceding process, is neutralized by the addition of potassa or soda, and evaporated to dryness. The residue is mixed with copper filings, and introduced into a glass tube closed at one end and provided at the other with a cork through which a delivery-tube passes. Sulphuric acid is then added to the mixture, the cork inserted, the tube heated, and the evolved vapors conducted into a solution of protosulphate of iron. The latter solution acquires a brown coloration which, upon addition of sulphuric acid, changes to a violet, if nitric acid be present. Upon conducting the disengaged gas into a solution of narcotine, the latter acquires a beautiful red color. Another portion of the residue should deflagrate when saturated with an alkali and projected upon live coals. SULPHURIC ACID. In order to detect this acid, the solution obtained by treating the organs with water is not distilled but is concentrated to one-sixth of its original volume, and then agitated with ether for about ten minutes. By this treatment the ether takes up the free sulphuric acid, but not the acid sulphates present. After ten minutes contact, the ether is decanted and allowed to spontaneously evaporate. Upon treating the residue, which contains the free sulphuric acid and fatty substances, with water, a solution containing only the sulphuric acid is obtained. Nitrate of baryta is then added to a portion of the fluid: in presence of sulphuric acid, a white precipitate, insoluble in acids, is produced. If this is heated on charcoal before the blow-pipe, a mass is formed, which, when moistened with hydrochloric acid and placed upon a clean silver coin, produces a black spot on the metal. Another portion of the solution is mixed with copper and the mixture evaporated in a tube closed at one end: sulphurous acid is evolved towards the end of the operation. This gas is detected by allowing it to pass over paper saturated with a mixture of iodic acid and starch; a blue coloration is produced which, owing to the transformation of the iodine set free into hydriodic acid, subsequently disappears. (We have never been able to effect the disengagement of sulphurous acid spoken of above when an exceedingly dilute sulphuric acid was used, even upon evaporating the mixture to dryness, notwithstanding Orfila's statement that the reaction occurs very readily.) PHOSPHORIC ACID. The aqueous solution is evaporated to dryness, the residue taken up with alcohol of 44° B., the fluid again evaporated, and the second residue dissolved in water. Upon adding acetate of lead to the solution, a white precipitate is produced if phosphoric acid be present. The precipitate is washed, suspended in water and a current of sulphuretted hydrogen passed through the mixture. If the fluid is then filtered, and the excess of sulphuretted hydrogen expelled from the filtrate by boiling, a liquid possessing the distinctive properties of a solution of phosphoric acid will be obtained. This should then be submitted to the following tests: Some pulverized charcoal is added to a portion of the solution, the mixture evaporated to dryness, and the residue obtained introduced into a Hessian crucible heated to redness: in presence of a considerable amount of the acid, free phosphorous is liberated and burns with a bright flame in the upper part of the crucible. In case this reaction fails to occur, other portions of the fluid are treated with a solution of a baryta salt, which causes a white precipitate, soluble in nitric acid; with an ammoniated solution of sulphate of magnesia, which throws down a crystalline white precipitate; and by boiling with molybdate of ammonia, acidulated with nitric acid, which produces a yellow precipitation, or at least a yellow coloration of the solution. OXALIC ACID. The solution is subjected to the same treatment as in the search for phosphoric acid, with the exception that, instead of adding acetate of lead to the fluid obtained by taking up the residue left from the alcohol with water, it is divided into two portions which are examined separately. A solution of a lime salt is added to one portion: if oxalic acid be present, a precipitate, which is insoluble in acetic acid or in chloride of ammonium, and effervesces when slightly calcined and treated with hydrochloric acid, is formed. Nitrate of silver is added to the remaining portion of the solution: the formation of a precipitate, which detonates when dried and heated in a glass tube closed at one end, is further evidence of the presence of the acid. ACETIC ACID. The solution obtained by treating the alimentary canal with water is distilled, as in testing for nitric and hydrochloric acids, and the following properties verified in the distillate: 1st. It has an acid reaction, and possesses the odor of vinegar; 2nd, unless previously neutralized with a base, it fails to redden the per-salts of iron; 3rd, if the distillate is added to a solution of the per-salts mentioned and sulphuretted hydrogen conducted through the fluid, a black precipitate is formed; 4th, upon boiling the still acid fluid with a small quantity of starch, the property of the latter to become colored in presence of free iodine is not changed; 5th, if heated with an excess of litharge, a basic salt which restores the blue color to reddened litmus paper is produced. HYDROCYANIC ACID. The detection of hydrocyanic acid requires special precautions. The substances to be examined are mixed with water, if solids are present, and introduced into a retort provided with a delivery-tube which dips in a solution of nitrate of silver. The retort is then heated over a water-bath. If the evolved vapors produce a precipitate in the silver solution, the heating is continued until a fresh portion of the latter is no longer affected. The operation is now interrupted, hydrochloric acid added to the retort, and heat again applied. Should a second precipitation of cyanide of silver occur, the presence of a _cyanide_ in the suspected materials is indicated; whereas the formation of a precipitate by the simple action of heat would point to the presence of free hydrocyanic acid or cyanide of ammonium.[H] In case the latter compound is present, ammonia will be contained in the distillate. [H] Ferrocyanides and ferricyanides--non-poisonous compounds--likewise, evolve hydrocyanic acid when distilled with a strong acid. Their presence is indicated by stirring a small portion of the materials with water, filtering the fluid, acidulating the filtrate with hydrochloric acid, and testing two portions: one with sesquichloride of iron, the other with protosulphate of iron. If either of the above salts be present, a blue precipitate is produced.--_Trans._ In order to identify the cyanogen, a portion of the precipitate is collected upon a small filter, washed, dried, and then allowed to fall into a rather long tube, closed at one end, in the bottom of which some iodine has previously been placed. A column of carbonate of soda is then introduced above the precipitate for the purpose of retaining the excess of iodine probably taken. Upon heating the lower end of the tube, white fumes of iodide of cyanogen, which condense in needles upon the cold portion of the tube, are produced. These are easily recognized by aid of a magnifying glass. They are colorless and are readily volatilized by heat. Some ammonia is next added to a solution of protosulphate of iron, the precipitate formed thoroughly washed, and exposed to the air until it acquires a greenish hue. The iodide of cyanogen is then withdrawn from the tube and mixed with potassa-lye and the precipitate mentioned above. The mixture is evaporated to dryness, the residue obtained treated with water and the filtered solution then acidulated with hydrochloric acid. If a solution of a persalt of iron is now added to the fluid, a blue precipitate is formed. The addition of salts of copper produces a reddish precipitation. The remainder of the precipitate formed in the nitrate of silver solution is heated with sulphur and then boiled with an aqueous solution of chloride of sodium: if cyanogen is contained in the precipitate, a solution of sulphocyanate of soda will be formed, and upon adding sesquichloride of iron an intense red coloration produced. It is evident that the presence of another acid in the solution examined for hydrocyanic acid would render the detection of _cyanides_ impossible, but in all cases hydrocyanic acid can be separated without arriving at a decision in regard to its original state of combination. Nitric, hydrochloric, and several other acids would not be distilled at the temperature of the water-bath; an examination for these by the methods already described can therefore be instituted simultaneously with the search for hydrocyanic acid. DETECTION OF ALKALIES AND ALKALINE EARTHS. The separation of these bodies in the caustic state is a matter of difficulty owing to the great tendency they possess to become converted into carbonates; the carbonates of lime, baryta and strontia, moreover, being non-poisonous in their effects, will not be employed with criminal intent, and the carbonates of soda and potassa are extensively used as pharmaceutical preparations. Notwithstanding the small chances of success, the isolation of the compounds under consideration in the caustic state is to be attempted. To this intent, the organs to be analysed, together with their contents, are placed in a glass retort provided with a receiver, water added, and the mixture boiled. The distillate will contain the ammonia present. When, however, putrefaction has begun, the detection of this compound does not necessarily indicate its original presence in the suspected materials. If, after an hour's boiling, the fluid in the retort possess an alkaline reaction, it is to be examined for soda, potassa, strontia, baryta and lime. The undistilled solution is filtered, the filtrate evaporated to dryness, and the residual mass treated with alcohol. By this treatment, potassa and soda go in solution, lime, baryta and strontia[I]--as well as the alkaline carbonates--remaining undissolved. The potassa and soda are separated from the other salts present by filtering and evaporating the alcoholic solution to dryness and then calcining the residue in a silver crucible. The mass, which should still be alkaline, is then dissolved in dilute sulphuric acid. If the solution is turbid, traces of baryta or strontia may still be present and should be removed by filtration. Some hydrochloric acid and solution of bichloride of platinum are then added to a portion of the filtered liquid: in presence of _potassa_ a yellow precipitate is formed. [I] Baryta and strontia dissolve in alcohol, but only when they are anhydrous and the alcohol is absolute, which is not the case here. Another portion is treated with tartaric acid: a white granular precipitate is produced. Hydrofluosilicic acid is added to a third portion of the solution: the formation of a gelatinous precipitate is a further indication of the presence of potassa. If the preceding tests have given negative results, and a white precipitate is formed by the addition of antimonate of potassa to another portion of the solution, _soda_ is present. In both cases, it is necessary to confirm the results by means of the spectroscope. The above reactions are distinctive only in the absence of metals precipitated by sulphuretted hydrogen, sulphide of ammonium or carbonate of soda, and small portions of the solution should be tested with these reagents. In order to detect baryta, strontia and lime, the residue, insoluble in alcohol is dissolved in dilute nitric acid, and an excess of carbonate of ammonia added to the solution: the three bases, if present, are precipitated as carbonates. The precipitate formed is separated from the solution by filtration, dissolved on the filter in dilute hydrochloric acid, and the solution then filtered and divided into two parts: sulphuric acid is added to one, the fluid filtered from the precipitate of sulphate of baryta formed, and the filtrate treated with ammonia and oxalate of ammonia. If _lime_ be present,--although its sulphate is not easily soluble--sufficient will be contained in the filtrate to give a white precipitate of oxalate of lime. The remaining portion of the solution is evaporated to dryness, and the residue treated with absolute alcohol. Chloride of strontium goes into solution, chloride of barium remaining undissolved. If upon evaporating the alcoholic solution a residue is obtained which, when dissolved in water, produces turbidity in a solution of sulphate of lime, _strontia_ is present. The residue, insoluble in alcohol, is dissolved in water. If a precipitate is produced by the addition of sulphuric acid or hydrofluosilicic acid to the solution, _baryta_ is present. The latter reaction distinguishes baryta from strontia, which is not precipitated by hydrofluosilicic acid. Should the tests mentioned above fail to give affirmative results, and poisoning by means of baryta and strontia be nevertheless suspected, these compounds may possibly have remained in the materials contained in the alimentary canal, in the state of insoluble sulphates. To effect their detection under these circumstances the organic substances must be decomposed by means of sulphuric acid. The carbonaceous residue is calcined in a crucible at an elevated temperature, and the remaining mass treated with water. In this way, a solution of sulphides of barium and strontium is obtained, which is then tested as directed above. DETECTION OF CHLORINE, BROMINE, AND IODINE. CHLORINE AND BLEACHING CHLORIDES. The detection of chlorine is very difficult owing to the great tendency it possesses to become converted into chlorides or hydrochloric acid, and it is only when found in a free state that its discovery is of importance. In case the gas exists uncombined in the alimentary canal, its odor will be perceptible, and, upon boiling the suspected materials with water, vapors will be evolved which impart a blue color to paper saturated with a mixture of iodide of potassium and starch paste. If the addition of sulphuric acid is necessary in order to produce the above reactions, there is reason to suspect the presence of "chloride of lime" or "_Eau de Javelle_."[J] [J] The so-called "chloride of lime" is probably either a mixture of chloride and hypochlorite of calcium or an oxydichloride of the metal; "_Eau de Javelle_" is the corresponding potassium compound.--_Trans._ BROMINE. In case bromine exists in a free state at the time the autopsy is made, its presence will be detected by the reddish color and unpleasant odor it possesses. Its isolation is accomplished by treating the materials with bisulphide of carbon which, upon dissolving the bromine, acquires a red color. If potassa is then added to the solution, it combines with the bromine and, upon evaporating the decanted fluid, calcining the residue, and treating it with water, a solution of bromide of potassium is obtained. Upon adding chlorine-water and ether to a portion of the fluid, and shaking the mixture, the bromine is liberated and is dissolved by the ether. The etherial solution of bromine, which possesses a reddish-yellow color, does not mingle with, but floats upon the surface of the colorless aqueous solution. If nitrate of silver is added to another portion of the aqueous solution of bromide of potassium, a precipitate of bromide of silver, soluble in ammonia, is formed. In case the bromine has been converted into a bromide, it is necessary to boil the alimentary canal and the articles of food contained therein with water. The fluid is next filtered and agitated with chlorine-water and ether. The liberated bromine is dissolved by the ether, which acquires a reddish-yellow color. Upon decanting the solution, and treating it with potassa, bromide of potassium is formed, and can be detected as directed above. IODINE. The detection of iodine is accomplished by a process almost identical with the above. The isolation of the iodine having been effected, it remains to be ascertained that it imparts a blue color to starch paste, and a violet color to bisulphide of carbon. DETECTION OF METALS. Under this head we will indicate the systematic course of analysis to be pursued, supposing a mixture of several metals including arsenic and antimony, to be under examination. The organic substances are first destroyed by means of chlorate of potassa and hydrochloric acid. When this is accomplished, the excess of chlorine is removed by boiling and the liquid filtered. The portion remaining on the filter is preserved: it contains all the silver and a large portion of the lead, if these metals are present. We will designate the residue as A, the filtrate as B. TREATMENT OF RESIDUE A. The residue is calcined with a little carbonate of soda and cuttings of pure Swedish filtering paper, the chlorides present being reduced to the metallic state by this treatment. The residue is next taken up with water acidulated with nitric acid, and the solution filtered. An insoluble residue, that may remain, is washed with hot water until the wash-water ceases to precipitate solution of nitrate of silver, and dried. It is then dissolved in boiling nitric acid, the solution diluted with water, and filtered.[K] [K] If an insoluble residue remains by the treatment with nitric acid, it may consist of _tin_. In this case, it is dissolved in _aqua regia_, the metal precipitated by immersing a plate of zinc in the solution and then re-dissolved in boiling hydrochloric acid. Upon adding chloride of gold to the solution so obtained, a purple precipitate is formed. Sulphuretted hydrogen produces a brown precipitate, soluble in sulphide of ammonium, in presence of tin. Sulphuric acid is added to the filtrate: if no precipitate forms, the absence of _lead_, in the residue A, is indicated. If, on the contrary, a precipitate is produced, it is collected upon a filter and washed. In order to make sure that the precipitate consists of sulphate of lead, it is treated with a solution of tartrate of ammonia: it should dissolve, forming a solution in which sulphuretted hydrogen produces a black precipitate. The fluid which has failed to be precipitated by the addition of sulphuric acid, or the filtrate separated from the precipitate formed, can contain only silver. Upon adding hydrochloric acid, this metal is thrown down as a caseous white precipitate, which is soluble in ammonia, but insoluble in boiling nitric acid, and blackens upon protracted exposure to light. The formation of a precipitate possessing these properties, leaves no doubt as to the presence of _silver_. _Remark._--In the operations described above, as well as in those following, the difficulty in separating minute precipitates from the filter is often experienced. When the precipitate is to be dissolved in reagents that do not affect the paper, such as ammonia, tartrate of ammonia, and dilute acids, it can be brought in solution directly on the filter. In cases, however, where reagents which attack the paper are employed, the precipitate should be separated. This is accomplished by mixing a small quantity of pure silica, obtained by the decomposition of fluoride of silicium by water, with the solution, before filtering. The precipitate becomes intimately mixed with the silica, and can then be readily removed from the paper. The presence of silica does not interfere, it being insoluble in the reagents commonly made use of. TREATMENT OF FILTRATE B. A current of sulphuretted hydrogen is conducted for twelve hours through the solution, which is kept at a temperature of 70°. by means of a water-bath. The flask containing the liquid is then closed with a piece of paper, and allowed to remain in a moderately warm place until the odor of the gas is no longer perceptible. The solution is next filtered with the precaution mentioned in the preceding remark, and the precipitate (_a_) thoroughly washed. The water used in this operation is united to the filtrate, and the fluid (_b_) examined as directed further on. TREATMENT OF PRECIPITATE _a_. In order to free the precipitate from the organic substances possibly present, at the same time avoiding a loss of any metal, it is dried, moistened with nitric acid, and the mass heated on a water-bath. Some Swedish filtering paper is next added, the mixture well impregnated with sulphuric acid, and then maintained for several hours at a temperature of about 170°. until a small portion (afterwards returned) gives a colorless solution when treated with water. The residue is now heated with a mixture of one part of hydrochloric acid and eight parts of water, the liquid filtered, the matter remaining undissolved washed with dilute hydrochloric acid, and the washings united with the filtrate. The residue I. and the solution II. are separately examined as directed below. RESIDUE I. This may contain lead, mercury, tin, bismuth and antimony. It is heated for a considerable time with _aqua regia_, the solution filtered, and the second residue, should one remain, washed with dilute hydrochloric acid. If the second residue is fused with cyanide of potassium, the compounds present are reduced to the metallic state. The liberated metals are treated with nitric acid, which dissolves _lead_, but leaves _tin_ as insoluble metastannic acid. The nitrate of lead is then filtered from the metastannic acid, and both metals are identified as described in the treatment of residue A. The solution, obtained by the action of _aqua regia_ on residue I, is treated with sulphuretted hydrogen. The tin and antimony are separated from the lead, mercury and bismuth by treating the precipitate produced with sulphide of ammonium, which dissolves only the sulphides of the first two metals. The solution in sulphide of ammonium is afterwards examined for these metals, as directed under the head of solution IV., the search for arsenic, however, being here omitted. Upon treating the residue insoluble in sulphide of ammonium with nitric acid, lead, copper and bismuth go into solution, mercury remaining undissolved. The liquid is filtered, and the undissolved mercury submitted to the special examination previously described. Sulphuric acid is added to the solution and the precipitate of sulphate of lead formed, separated, washed, and examined as directed while treating of residue A. Finally, the solution separated from the lead is tested for _bismuth_ and _copper_, as in examination of precipitate III. SOLUTION II. The solution is concentrated by heating on a water-bath, a small quantity of carbonate of soda cautiously added to a portion, and notice taken if a precipitate forms. The part taken is then acidulated with a little hydrochloric acid, returned to the principal solution, and sulphuretted hydrogen conducted through the fluid, as in the examination of solution B. In case a precipitate fails to form, all metals are absent; if, on the contrary, a precipitate (_c_) is produced, it is examined as directed below. EXAMINATION OF PRECIPITATE _c_. If the solution merely became turbid, or the precipitate formed was of a pure white color, it consists probably of sulphur. It is, however, indispensable, even in this case, to collect the precipitate and examine it for _arsenic_. Provided it is of a pure yellow color, it is treated with ammonia. In case it is entirely dissolved by this treatment, and the addition of carbonate of ammonia failed to produce a precipitate in solution II., it is certain that arsenic, and no other metal, is present. Under these circumstances, the ammoniacal solution is examined as directed in the article on the detection of arsenic. If, on the other hand, the precipitate is not yellow, or being yellow, is but imperfectly soluble in ammonia, and a precipitate was formed by the addition of carbonate of ammonia to solution II., it is necessary to likewise search for tin, antimony, mercury, copper, bismuth and cadmium. In this case, the precipitate is placed in a small flask, allowed to digest for several hours with ammonia and sulphide of ammonium in a moderately warm place, and the solution filtered. The remaining residue (III.) is washed, labelled, and preserved for subsequent examination; the _filtrate_ (IV.) is treated as directed below. TREATMENT OF SOLUTION IV. The solution, to which the water used in washing the residue has been added, is evaporated to dryness, the residue obtained taken up with pure fuming nitric acid, and the liquid again evaporated. The second residue is next saturated with a solution of carbonate of soda. A mixture of 1 part of carbonate and 2 of nitrate of soda is then added, the mixture evaporated to dryness, and the residual mass heated to fusion. The fused mass, when cold, is treated with cold water, and any remaining residue washed with a mixture of equal parts of alcohol and water. The filtered fluids are now evaporated in order to remove the alcohol, sulphuric acid is then added, and the mixture heated until white fumes of the acid begin to evolve. In this way the complete expulsion of the nitric acid present is rendered certain. When cold, the residue is treated with water and the _solution_ introduced into Marsh's apparatus, or, in case a quantitative estimation of the arsenic is desired, it is treated with sulphuretted hydrogen and the weight of the precipitate formed determined, as directed under the detection of arsenic. Should a residue insoluble in water remain, it may contain tin, antimony and traces of copper. Upon dissolving it in _aqua regia_ and placing a sheet of pure zinc in the solution, these metals are thrown down in the metallic state. The precipitate is collected, the zinc present completely removed by treatment with _dilute_ hydrochloric acid, and the residue boiled with concentrated hydrochloric acid which dissolves the _tin_ present. The fluid is filtered and the _filtrate_ tested for this metal by adding solution of chloride of gold, which, in its presence, produces a purple precipitate, and, by treating it with sulphurated hydrogen, which forms a brown precipitate, soluble in sulphide of ammonium. If the _residue_, insoluble in concentrated hydrochloric acid, is thoroughly washed and then treated with nitric acid, the copper present goes in solution. The fluid is filtered, and ammonia added to the filtrate: in presence of _copper_, the solution acquires a blue color, and gives a reddish precipitate upon addition of ferrocyanide of potassium. _Antimony_, if present, remains by the treatment with nitric acid as an insoluble intermediate oxide. This is dissolved in hydrochloric acid, in which it is now soluble, and the solution introduced into Marsh's apparatus. TREATMENT OF PRECIPITATE III. This precipitate may contain the sulphides of mercury, copper, cadmium and bismuth. Upon treating it with nitric acid, all but the sulphide of mercury are dissolved. In case no residue remains, the absence of _mercury_ is indicated; if, on the other hand, a residue is left, it is well washed, dissolved in _aqua regia_, and the solution examined, either by means of Smithson's pile, or in the apparatus of Flandin and Danger. (_Vide Detection of Mercury._) Whether a residue remains or not, an excess of ammonia is next added to the filtered solution in nitric acid: the formation of a permanent precipitate denotes the presence of _bismuth_. In this case, the fluid is filtered, and the alkaline filtrate further tested for copper and cadmium. For this purpose, cyanide of potassium is added, and sulphuretted hydrogen conducted through the filtrate: if _cadmium_ be present, a yellow precipitate is produced, copper not being thrown down in presence of an alkaline cyanide. The precipitate of sulphide of cadmium is separated from the solution by filtration, and the filtrate saturated with hydrochloric acid. _Copper_, if present, is now precipitated as sulphide: its separation is completed by conducting sulphuretted hydrogen through the fluid. The precipitate is collected, washed, dissolved in nitric acid, and its identity established as previously directed. If the metal be present in sufficient quantity, it should be obtained in a metallic state upon a plate of iron; it is then coherent, possesses its natural color, and can conveniently be exhibited to the Jury. TREATMENT OF SOLUTION _b_. This solution may contain: cobalt, nickel, iron, manganese, chromium, zinc and aluminium. Of these, only zinc and chromium are poisonous; the search for these two metals is therefore all that is necessary in criminal cases. The solution is treated with a slight excess of ammonia, sulphide of ammonium added, and the fluid, after being allowed to stand for several hours, filtered. The precipitate may consist of sulphide of zinc and hydrated oxide of chromium, as well as of traces of sulphide of iron and phosphate of lime. If the suspected materials contained a _chromate_, this salt, in presence of hydrochloric acid and sulphuretted hydrogen, would be converted into sesquichloride of chromium a compound which is precipitated by sulphide of ammonium as a hydrated oxide. The precipitate is washed with water, to which a little sulphide of ammonium is added, then dried, and fused with four times its weight of a mixture of equal parts of carbonate and nitrate of potassa. After the mass has remained in a state of fusion for a quarter of an hour, it is treated with boiling water, mixed with a little alcohol, in order to decompose the manganate that would be present were manganese contained in the materials under examination. The alcohol is then expelled by boiling the fluid, and the solution filtered. The _filtrate_ may contain phosphate of potassa, originating from the phosphate of lime present, and _chromate of potassa_, resulting from the oxidation of the sesquioxide of chromium. In presence of the latter compound, the following reactions will occur in the solution: 1st., Upon acidulation with acetic acid and addition of solution of acetate of lead, a yellow precipitate, soluble in potassa, is formed; 2nd., if hydrochloric acid is added and sulphuretted hydrogen conducted into the solution, the latter acquires a green color, and, upon adding ammonia, a bluish-grey precipitate of chromic hydrate is produced; 3rd., if nitrate of silver is added to the solution, a brick-red precipitate is formed. The _precipitate_ remaining on the filter, may consist of zinc, mixed with the oxides of iron, nickel, cobalt, aluminium and manganese. It is dissolved in boiling hydrochloric acid, acetate of soda added, and the fluid boiled until no further precipitation occurs. The iron is now completely separated. The solution is then filtered, the precipitate washed, and an excess of potassa added to the _filtrate_; if the solution contains cobalt, nickel or manganese--which is improbable--a permanent precipitate is formed. This is separated from the fluid by filtration: its further examination is, however, unnecessary, as the metals of which it consists are not poisonous. The _filtrate_ may contain aluminium and _zinc_. The latter metal is detected by acidulating the filtrate with acetic acid, and adding a solution of sulphuretted hydrogen: in presence of zinc a white precipitate of its sulphide is formed. In case organic substances are present, the precipitation of chromium by sulphide of ammonium may possibly have been hindered, and the metal have passed into the filtrate. When, therefore, chromium is not detected in the precipitate, the filtrate should also be examined. For this purpose, the fluid is evaporated to dryness, and the residue obtained fused with a mixture of nitrate and carbonate of soda. The fused mass is then taken up with water, the solution acidulated with acetic acid, and a solution of acetate of lead added: if chromium be present, a yellow precipitate, soluble in potassa, is produced. DETECTION OF ALKALOIDS AND SOME ILL-DEFINED ORGANIC SUBSTANCES.[L] A general method for effecting the detection of alkaloids was first proposed by _Stas_. Since the publication of this method, modifications to it have been recommended by _Otto_, and by _L. Uslar_ and _J. Erdman_. Other processes have been suggested by _Rodgers_ and _Girwood_, by _E. Prollius_, and by _Graham_ and _Hofman_. The latter will doubtless become general in their application; but up to the present time they have been employed exclusively in the detection of strychnine. Dialysis has also been recently applied in the separation of alkaloids. [L] Colchicine, picrotoxine and digitaline. STAS'S METHOD. This method is based upon the facts: (_a_), that the acid salts of the alkaloids, especially those containing an excess of tartaric or oxalic acids, are decomposed by caustic alkalies and by the bicarbonates of soda and potassa; (_b_), that the alkaloids, when liberated in this manner, are combined with a certain amount of water which determines their solution in ether, although, in a desiccated state they may be insoluble in this menstruum; (_c_), that they may be extracted from their aqueous solutions by agitation with ether. Stas's original method is as follows: The suspected substances, if organs are contained, are cut into fine shreds, then mixed with absolute alcohol, 0.5 to 2. grammes of tartaric or oxalic acid added and the whole introduced into a flask and heated at a temperature of 60° to 75°. When quite cold, the mixture is filtered, and the undissolved portion remaining on the filter washed with absolute alcohol, the washings being added to the filtrate. The alcoholic solution is evaporated, either by placing it under a bell-jar connected with an air-pump, or by passing a current of air, having a temperature not exceeding 35° over it, until reduced to a quarter of its original volume: the complete expulsion of the alcohol being then rendered certain. If insoluble matter separates during this operation, the concentrated fluid is passed through a moistened filter, the water used in washing the residue being united to the filtrate which is then evaporated to dryness by aid of the air-pump or by placing the fluid in a bell-jar over concentrated sulphuric acid. When the evaporation is completed, the residue is treated with absolute alcohol, the alcohol allowed to evaporate at the ordinary temperature of the air, and the second residue dissolved in the smallest possible amount of water. The fluid thus obtained is placed in a test-tube, and a concentrated solution of bicarbonate of soda added so long as effervescence takes place. Ether is then added, the mixture thoroughly shaken, and after it has remained at rest for some time, a small portion of the supernatant ether removed and evaporated on a watch-glass: the residue obtained will consist of the alkaloid present. Two cases are now possible: the alkaloid is a solid, or it is a liquid and is volatile. The further treatment of the solution is modified according to these circumstances. _a._ THE ALKALOID IS LIQUID AND VOLATILE. If, upon the evaporation of the ether, oily streaks were left on the watch-glass, a volatile alkaloid is probably present. In this case, a solution of caustic potassa is added to the test-tube, the mixture shaken, the supernatant ether decanted[M] into a flask and the remaining solution again washed with ether until the last portion fails to leave a residue upon evaporation. The etherial fluids are then united, and two cubic centimetres of water, acidulated with one-fifth of its weight of sulphuric acid, added. This acid retains the alkaloid, which is now in the state of a pure acid-sulphate soluble in water, the animal matters present remaining dissolved in the ether. The ether, in which some sulphate of conia may be contained--although the greater portion of this compound would remain in the aqueous solution--is then decanted. The remaining aqueous solution of the pure sulphate of the alkaloid is placed in a test-tube, a solution of caustic potassa and some ether added, and the mixture well shaken. The ether is next decanted and allowed to spontaneously evaporate in a dry place at a very low temperature, and the ammonia possibly present is then removed by placing the vessel containing the residue over sulphuric acid. The residue now obtained consists of the alkaloid present in a state of purity, and can be directly identified by means of the reactions described further on. [M] The necessity of decanting etherial and other solutions is advantageously obviated by the use of a pipette.--_Trans._ _b._ THE ALKALOID IS SOLID. It sometimes occurs that ether fails to take up all of the alkaloid present in the fluid treated with bicarbonate of soda. Under these circumstances the fluid should be mixed with caustic potassa, the mixture shaken, and the ether decanted; this operation being repeated several times, until the entire amount of the alkaloid is removed; the ethereal fluids are then united in a capsule, and allowed to spontaneously evaporate. The result of the evaporation may be solid; more frequently, however, a milky liquid remains which restores the blue color to reddened litmus paper; if so, the presence of a vegetable alkaloid is certain. In order to purify the residue, a few drops of water, slightly acidulated with sulphuric acid, are added to the capsule, and the latter turned, so as to bring the fluid in contact with the substance at all points; in this manner a colorless and limpid fluid is obtained, the fatty substances adhering to the dish. The liquid is decanted into a second capsule, the remaining residue washed with a little acidulated water, and the washings likewise added to the principal solution. The fluid is now evaporated either _in vacuo_, or over sulphuric acid, to about three-fourths of its original volume a concentrated solution of neutral carbonate of potassa added, and the mixture treated with absolute alcohol, which dissolves the liberated alkaloid, and separates it from the sulphate of potassa formed and the excess of carbonate of potassa. The alcoholic solution is decanted and allowed to evaporate _in vacuo_ or in the air: the alkaloid now crystallizes out in a state suitable for further examination. MODIFICATIONS TO STAS'S METHOD, PROPOSED BY OTTO. In Stas's method, the loss of morphine is possible, for, if ether is not added immediately after the addition of carbonate of soda, this alkaloid crystallizes and is then no longer soluble in that menstruum; and, if the ethereal solution is not quickly decanted, the portion dissolved will likewise separate out in small crystals. In both cases, morphine will remain in the aqueous solution from which the other alkaloids have been extracted by the ether. _M. Otto_ recommends the addition of chloride of ammonium and a little soda-lye, in order to dissolve the alkaloid. Upon allowing the solution so obtained to stand for some time exposed to the air, crystals of morphine are deposited. According to the same authority, it is advisable to omit the distinction drawn by Stas between volatile and fixed alkaloids, and submit both to the treatment recommended for those that are volatile. Otto also recommends the agitation of the fluid containing the oxalates or tartrates of the alkaloids with ether, previously to their separation by means of bicarbonate of soda. By this treatment the elimination of the coloring matter present--as well as of _colchicine_, _digitaline_, _picrotoxine_, traces of _atropine_, and various impurities--is accomplished. As soon as the ether ceases to become colored and to leave a residue upon evaporation, alkali is added, and the operation concluded as usual. In this way the alkaloid is obtained, almost directly, in a pure condition. This last modification appears to us to be a very happy one, inasmuch as it greatly facilitates the purification of the alkaloid present. MODIFICATIONS TO STAS'S METHOD, PROPOSED BY USLAR AND ERDMAN. 1st. The materials to be examined are brought to the consistence of a thin paste, and digested for about two hours with water, to which some hydrochloric acid has been added, at a temperature of 60° to 80°. The mixture is then filtered through a moistened linen cloth, and the residue washed with warm acidulated water; the washings being added to the solution. 2nd. Some pure quartz sand--or, preferably, silica prepared by the decomposition of fluoride of silicium--is added to the filtrate, the fluid supersaturated with ammonia, and evaporated to dryness over a water-bath: the addition of silica renders the residue friable. 3rd. The residue is boiled repeatedly with amylic alcohol, which extracts all the alkaloid present as well as the fatty and coloring matters, and the extracts filtered through filter paper that has been moistened with amylic alcohol. 4th. The filtered fluid is thoroughly agitated with ten or twelve times its volume of almost boiling water acidulated with hydrochloric acid: the hydrochlorate of the alkaloid present goes into the aqueous solution, the fatty and coloring substances remaining dissolved in the oily supernatant layer. The latter is separated by means of a pipette, and the acid aqueous solution shaken with fresh quantities of amylic alcohol until completely decolorized. 5th. The aqueous solution is then concentrated, ammonia added, and the mixture well shaken with warm amylic alcohol, in which the alkaloid dissolves. As soon as the solution forms a supernatant layer upon the surface of the fluid, it is drawn off with a pipette and evaporated on a water-bath. In this manner, the alkaloid is usually obtained in a sufficient state of purity to admit of its immediate identification; if, however, a small portion turns brown when treated with concentrated sulphuric acid, the process of purification must be repeated. Under these circumstances it is re-dissolved in dilute hydrochloric acid, the solution repeatedly shaken with amylic alcohol, in order to extract the impurities present, and the alkaloid then extracted with ammonia and amylic alcohol, as previously directed. The method of _von Uslar_ and _Erdman_ differs from that of Stas merely in the substitution of amylic alcohol for ether, and of hydrochloric acid for oxalic or tartaric acid. It offers no advantages over Stas's method if the alkaloids present are soluble in ether but is even less advantageous in this case, inasmuch as its execution requires a longer time. In cases where the detection of morphine, or an unknown alkaloid, is desired, the use of amylic alcohol instead of ether is, it is true, preferable; still, with the exercise of care, ether can also be employed, and, as this process greatly facilitates examinations when no clew to the poison present exists and all alkaloids may possibly be absent, we prefer it to the one just described. RODGERS AND GIRDWOOD'S METHOD. This method--which as yet has only been employed in the detection of strychnine--is based upon the solubility of this alkaloid in chloroform. The substances under examination are digested with dilute hydrochloric acid, and the mixture filtered. The filtrate is then evaporated to dryness on the water-bath, the residue taken up with pure alcohol, the alcoholic solution evaporated, the second residue treated with water, and the solution so obtained filtered. The filtrate is next supersaturated with ammonia, and well shaken with chloroform, which, upon being separated by means of a pipette and evaporated, leaves the alkaloid in an impure state. Concentrated sulphuric acid is then poured upon the alkaloid: the latter is not affected by this treatment, whereas the foreign organic substances present are carbonized. After the lapse of several hours, the mixture is treated with water, the fluid filtered, and the strychnine extracted from the filtrate by means of ammonia and chloroform, as already described. The operation is repeated until the residue obtained by evaporating the chloroform is no longer affected by the treatment with sulphuric acid. PROLLIUS'S METHOD. The suspected substances are boiled with aqueous alcohol, mixed with tartaric acid, and evaporated at a gentle heat. The remaining aqueous solution is then passed through a moistened filter, ammonia added to the filtrate, and the mixture shaken with chloroform. The chloroform is separated, the last trace of the original solution removed by washing with water, three parts of alcohol added, and the fluid evaporated. If strychnine be present, it will now separate out in crystals. This method is applicable only in presence of a considerable quantity of strychnine, and is less serviceable than the one preceding. GRAHAM AND HOFMAN'S METHOD. This method, which is applied to the detection of strychnine in beer, is founded upon the fact that an aqueous solution of a strychnine salt yields the alkaloid to animal charcoal, from which it can be subsequently extracted by boiling with alcohol. The beer to be examined is shaken with 30 grammes of animal charcoal, and the mixture then allowed to stand twenty-four hours, with occasional shaking. The solution is next filtered, the animal charcoal washed with water, and boiled for half-an-hour with four times its weight of 90 per cent. alcohol. The apparatus represented in Fig. 12 is employed, in order to avoid a loss of substance in this operation. [Illustration: Fig. 12.] The alcohol is filtered hot, evaporated, and the residue obtained treated with a small quantity of solution of potassa, and then agitated with ether. Upon spontaneous evaporation, the ethereal solution leaves the strychnine present in a comparatively pure state. _Macadam_ proposes to use this process for the detection of strychnine in animal bodies. For this purpose, the suspected materials are heated with a solution of oxalic acid, as in Stas's method, and the strychnine detected in the filtered solution in the manner just described. This method is scarcely to be recommended: the use of animal charcoal is doubtless serviceable in the examination of beer, as it effects the separation of a small amount of strychnine from a large quantity of fluid, but its application to other researches is much less to be advised. APPLICATION OF DIALYSIS IN THE DETECTION OF ALKALOIDS. In order to apply the dialytic method to the separation of alkaloids, the suspected substances are heated with hydrochloric acid, and the solution introduced into the dialyzer. The hydrochlorates of the alkaloids, being crystalline bodies, transverse the membrane, and are contained, for the greater part, after twenty-four hours, in the outer solution. The fluid is then concentrated, and the alkaloids either directly precipitated, or purified by one of the preceding methods. IDENTIFICATION OF THE ALKALOID. The alkaloid having been isolated by one of the preceding methods, it remains to establish its identity. Owing to the small number of reactions characteristic of organic compounds, this is a matter of considerable difficulty. There are two cases possible: the alkaloid may either be volatile or fixed. THE ALKALOID IS VOLATILE. In this case it may consist of nicotine, conine or aniline: less known alkaloids (piccoline, etc.) may also be present. We will confine ourselves to the consideration of the three first mentioned. The alkaloid is divided into several portions which are placed on watch-glasses and submitted to the following tests: _a._ A drop is treated with nitric acid: this may, or may not, impart a red tint to the alkaloid; if it does, another drop is treated with dry hydrochloric acid gas: if it assumes a deep violet color, it probably consists of _conine_. _b._ In case a red color was not produced by the addition of nitric acid, another drop is treated with chloride of lime. If it acquires a violet tint, and two other drops, when heated, one with arsenic acid, the other with nitrate of mercury, become red, the body present consists of _aniline_. or an homologous base. _c._ Should the above tests fail to give positive results, and the substance, when treated with chlorine, assumes a blood-red color, and with hydrochloric acid does not change in the cold but turns to a deep violet color upon boiling, it probably consists of _nicotine_. THE ALKALOID IS FIXED. A very minute quantity is dissolved in the smallest possible amount of hydrochloric acid, and an excess of ammonia added. Three cases are now possible: (_a_) A precipitate, insoluble in an excess of the precipitant, is immediately formed; (_b_) a precipitate is formed, which, at first dissolves, but is subsequently deposited from the fluid; (_c_) no precipitate is produced, or, in case one forms, it dissolves in an excess of the precipitant and fails to separate out upon allowing the fluid to stand. _a. Ammonia produces a permanent precipitate._ A small quantity of an aqueous solution of carbonic acid is poured over the alkaloid in the water-glass, and notice taken whether it dissolves or not: in either case the mixture is evaporated on a water-bath to dryness, in order to avoid a loss of substance. CARBONIC ACID FAILS TO DISSOLVE THE ALKALOID. After the evaporation is completed, ether is added to the watch-glass: the alkaloid may, or may not, be dissolved. The ether is then evaporated at the ordinary temperature of the air. _Ether fails to dissolve the alkaloid._ It probably consists of _berberine_. In this case, it will possess a yellow color, and its hydrochlorate will give a reddish-brown precipitate upon addition of sulphide of ammonia. _Ether dissolves the alkaloid._--A small portion is treated with nitric acid. If an intense green coloration is produced, the remaining portion is dissolved in ether, and an ethereal solution of oxalic acid added. If the precipitate now formed does not dissolve upon the addition of a little water, there is reason to suppose the presence of _aricine_. Provided the addition of nitric acid did not produce a coloration, the mixture of the alkaloid and this acid is treated with a small quantity of sulphuric acid: if the fluid now acquires a red color, the substance probably consists of _narcotine_. Should both nitric and sulphuric acids fail to cause a reaction, the alkaloid is dissolved in ether, precipitated by an ethereal solution of oxalic acid, and the precipitate treated with a little water. If it dissolves, it probably consists of _papaverine_. CARBONIC ACID DISSOLVES THE ALKALOID. The substance is treated with ether, notice being taken if it dissolves, which is evaporated at the ordinary temperature of the air so as to prevent a loss of minute portions of the alkaloid. _Ether dissolves the alkaloid._--If nitric acid gives first a scarlet, then a yellow color, sulphuric acid a yellow, changing to red and violet, and hydrochloric acid a violet color, the alkaloid present is probably _veratrine_. If the above colorations are not produced, chlorine water is added to another portion of the substance, then ammonia; the formation of a green color, changing to violet and turning red upon a renewed addition of chlorine water, denotes the presence of _quinine_. In case all of these tests give but negative results, and the alkaloid is soluble in concentrated sulphuric acid, a solution being formed which assumes a reddish-violet tint when stirred with a glass rod previously dipped in bromine water, the presence of _delphine_. is indicated. _Ether fails to dissolve the alkaloid._--If the substance is capable of being sublimed,[N] it consists of _cinchonine_. [N] Cinchonine, when sublimed, condenses in minute brilliant needles.--_Trans._ _b. Ammonia produces a precipitate, which redissolves in an excess of the precipitant, but separates out after the lapse of an hour._ The substance is treated with cold absolute alcohol and its solubility in this menstruum noted. If it readily dissolves, it probably consists of _brucine_. The presence of this alkaloid is confirmed by applying the following tests: (1) Nitric acid imparts a blood-red color to the substance; (2) if treated with sulphuric acid, it acquires a reddish tint which subsequently changes to yellow and green; (3) chlorine at first fails to cause a coloration, but after some time a yellow color which afterwards changes to a red is produced; (4) upon treating the substance with bromine, it immediately assumes a violet tinge. In case the alkaloid is only slightly soluble in alcohol, there is reason to infer the presence of _strychnine_. The following confirmatory tests should be applied: (1) If the substance is treated with a mixture of sulphuric acid and an oxidizing body, such as bichromate of potassa, binoxide of manganese, or peroxide of lead it acquires a violet color, which changes into red and finally passes into a clear yellow; (2) the addition of bichloride of platinum produces a precipitation of the hydrochlorate. Should, however, the substance be only slightly soluble in alcohol, and the above reactions fail to take place, the presence of _solanine_. is indicated. In presence of this alkaloid the following reactions will occur: (1) Upon treating the substance with concentrated sulphuric acid, it assumes a rose tint, which changes after some time has elapsed first to a deep violet, then to a brown color; (2) a solution of a salt of the alkaloid reduces gold and silver salts; (3) the addition of oxalic acid produces a precipitate in the aqueous and even acid solution of its salts. _c. Ammonia fails to produce a precipitate, or redissolves permanently the one formed._ The solubility of the alkaloid in ether is ascertained. If it be soluble, it may consist of aconitine, atropine or codeine; if insoluble, of emetine or morphine. _The alkaloid is soluble in ether._--If bichloride of platinum fails to precipitate the hydrochlorate from a neutral solution of the alkaloid, and sulphuric acid causes it to assume a yellow color which subsequently changes to a reddish-violet, it probably consists of _aconitine_. In case bichloride of platinum causes a precipitate and sulphuric acid fails to produce the yellow coloration referred to above, the presence of either atropine or codeine is indicated. In order to decide which of these bases is present, the substance is dissolved in pure chloric acid and the solution allowed to spontaneously evaporate. If the alkaloid is deposited during this operation, it probably consists of _atropine_. If this is not the case, there is reason to infer the presence of _codeine_. _The alkaloid is insoluble in ether._--If it dissolves in acetone it probably consists of _emetine_. If acetone fails to dissolve it, the presence of _morphine_. is indicated. The following confirmatory tests should be applied: (1) Upon treating the substance with nitric acid, it acquires a blood-red color; (2) the addition of a solution of a persalt of iron produces an evanescent blue coloration; (3) chloride of gold is colored blue, when treated with the alkaloid; (4) the substance reduces iodic acid: this reduction is detected by adding to the acid a little starch-paste, which turns blue upon the liberation of the iodine; (5) permanganate of potassa, if heated with the substance, is reduced and acquires a green color. IDENTIFICATION OF DIGITALINE, PICROTOXINE AND COLCHICINE. It has already been remarked that in exhausting the first acid solution with ether--previous to the neutralization, according to Otto's method--colchicine, a weak alkaloid, digitaline, an indefinite mixture, picrotoxine (which appears to possess the properties of an acid), and traces of atropine, pass into solution. The ether is evaporated on a water-bath to dryness, the residuary mass treated with slightly warmed water and the solution filtered from the undissolved resinous matter. The aqueous solution is next rendered feebly alkaline by addition of soda lye, and then well agitated with ether, until this fluid ceases to leave a residue upon evaporation. The ethereal solution is now decanted, and the water present removed by means of chloride of calcium. If it is evaporated, a residue containing the _colchicine_, _digitaline_ and traces of atropine (mixed possibly with a minute quantity of picrotoxine, which is here left out of consideration) is obtained. _a._ The _alkaline solution_, from which the ether has been removed, is acidulated with hydrochloric acid and again shaken with ether. The _picrotoxine_ present is now dissolved, and upon dehydrating (by means of fused chloride of sodium) and evaporating the ethereal solution can be obtained in crystals. The crystals of picrotoxine are easily recognized by their forming in feathery tufts as well as by their length and silky brilliancy. Should crystals fail to form in a short time, it is advisable to take up the residue, left by the evaporations of the ether, with slightly warmed alcohol, and to allow the latter to spontaneously evaporate on a watch-glass, or, if the quantity of substance is exceedingly minute, on the slide of a microscope. After determining the form of the crystals, it should be ascertained that they possess an intense bitter taste and exhibit the other characteristic properties of picrotoxine. The following reaction is distinctive: If the crystals are dissolved in an aqueous solution of soda and a few drops of "Fehling's solution"[O] added, a reddish precipitate of cuprous oxide is formed. [O] An alkaline solution of tartrate of copper, employed in the examination of sugar, urine, and wine.--_Trans._ _b._ Provided picrotoxine has not been found, the _ethereal solution_ obtained by agitating the alkaline fluid with ether is to be examined for colchicine and digitaline. To this end, the residue obtained upon evaporating the solution to dryness is taken up with water, and the filtered fluid tested as follows: 1. It is ascertained if a drop of the solution possesses the bitter taste of digitaline. 2. Another drop is treated with solution of tannin; if either alkaloid be present, a precipitate is formed. 3. Two drops of the solution are next tested: one with tincture of iodine, the other with chloride of gold. These reagents precipitate colchicine, but do not affect solutions of digitaline or picrotoxine. Unfortunately traces of atropine, possibly present, would cause the same reaction; the test therefore fails to be conclusive. 4. Several portions of the solution are evaporated on watch crystals. Concentrated nitric acid is added to one portion: if colchicine be present, an evanescent violet coloration is produced, which changes to a light yellow upon addition of water, and to a pure yellow or reddish-orange color, if the mixture is saturated with a slight excess of caustic alkali. 5. Another portion of the residue is dissolved in a few drops of concentrated sulphuric acid, and the solution stirred with a glass rod moistened with bromine water: in presence of digitaline a violet-red color is produced. This coloration is more distinct when a small quantity of the alkaloid and an excess of sulphuric acid are present. 6. If a large amount of substance is at hand, the residue can be boiled with hydrochloric acid, and the green or brownish color and characteristic odor of digitaline produced, in case this body be present: this, however, is not a very delicate test. 7. Finally; it is advisable when the presence of digitaline is suspected to ascertain its physiological action. For this purpose, a minute quantity of the substance is placed upon the heart of a frog: in presence of the alkaloid, the pulsations are immediately retarded, or even arrested. * * * * * Although by means of the tests given above the existence of a special alkaloid, or of one of the ill-defined substances just mentioned, may be justly regarded as probable, its presence has not yet with certainty been demonstrated. This is especially true in cases where the compound possesses but few characteristic properties. When possible, the suspected substance should be obtained in a crystaline form, and then compared by aid of the microscope--if the small quantity present permits of no other examination--with crystals of the pure alkaloid, prepared under the same conditions. In case 20 or even 10 centigrammes of substance are at hand, it is best to convert the alkaloid into its hydrochlorate, and evaporate the solution of this salt to dryness. The residue, after being weighed, is dissolved in water, and a solution of sulphate of silver added. The precipitate of chloride of silver formed is collected and carefully weighed, in order to calculate the weight of the chlorine contained in the hydrochlorate and consequently the molecular weight of the alkaloid. The filtrate from the chloride of silver, which contains the alkaloid in the state of sulphate, is treated with hydrochloric acid, to remove the excess of silver present and the fluid then filtered. The filtrate is next shaken with potassa and ether. Upon decanting and evaporating the ethereal solution, a residue consisting of the alkaloid present is obtained, which is then purified by crystallization from alcohol. An elementary analysis of the alkaloid is now executed. _Certainty_ as to the presence of an individual alkaloid is attainable only when the execution of this confirmatory test is possible. The reactions previously described can be performed with fifteen centigrammes of substance, and this amount is sometimes contained in a cadaver. If but one or two centigrammes are at hand, it is still possible to detect the presence of an alkaloid; a conclusion, however, as to _which_ cannot be arrived at, especially if the substance found is a liquid or an amorphous body, and one that presents few distinctive properties. III. METHODS TO BE EMPLOYED, WHEN NO CLEW TO THE NATURE OF THE POISON PRESENT CAN BE OBTAINED. If poisoning has been caused by the administration of a mixture of numerous substances and these greatly differ in their properties, it is impossible to demonstrate in an incontestible manner the presence of each individual poison. This contingency fortunately but seldom arises; the criminal usually has recourse to one or two poisons, the detection of which is possible. It must not be imagined, however, that the presence of a poison in an organ can at once be detected with certainty by the mere application of a few tests; because, in searching for a substance which is absent, we may unwittingly destroy the one present, or, at least, transform it into combinations which would not allow of a definite conclusion as to its original condition. In order to follow a systematic method in researches of this nature, it is advisable to divide the materials under examination into three parts: one portion is preserved, in order to ascertain its physiological effects on animals, the chemical analysis having failed to give positive results. The other portions are submitted to analysis, but with slightly different objects in view; one is subjected to a series of tests which are adapted, under all circumstances, to place the chemist on the track of the poison present, and which, in some cases, may even give conclusive and definite results. Should these tests furnish only _indications_ of the nature of the poison, the remaining portion serves, with the assistance of this information, to establish beyond doubt the identity of the substance. INDICATIVE TESTS. Two cases may present themselves: the materials to be examined possess either an alkaline (or neutral) or an acid reaction. As the methods to be pursued in either of these cases differ somewhat, they will be treated separately. THE SUBSTANCE POSSESSES AN ACID REACTION. The materials are mixed with water, placed in a retort provided with a delivery-tube which dips in a solution of nitrate of silver, and heated over a water-bath: if a _cyanide_ be present, hydrocyanic acid will be disengaged, and a white precipitate of cyanide of silver formed: this is examined as previously directed (_vide_ p. 50). In case a precipitate is not produced by the above treatment, more water is added to the retort, and the mixture boiled for about an hour, care being taken to collect the evolved vapors in a well-cooled receiver. The portion remaining in the retort is thrown on a filter and the filtrate obtained united with the distillate. The residue remaining on the filter is next washed with boiling absolute alcohol, the washings being added to the aqueous solution. In this way, the suspected substances are divided into soluble and insoluble portions, which are examined separately, as directed below. _a._ LIQUID PORTION. If the addition of alcohol caused a precipitation of animal matters, these are separated by filtering the solution. The filtrate is then placed under a bell-jar over concentrated sulphuric acid until its volume is considerably reduced. The solution may contain organic and inorganic bases and acids. In order to detect all bodies that are present, the following course is pursued: (1). A current of sulphuretted hydrogen is conducted through the solution: the precipitation of some metals, usually thrown down by this gas, may fail to take place in this instance, owing to the presence of organic substances; however, some metals are precipitated, even in presence of organic compounds, and organic acids are but seldom present. In case a precipitate is formed, it is mixed with pure silica, collected on a filter, and treated with nitric acid. If the precipitate fails to dissolve, it is treated with _aqua regia_. In either case, the solution obtained is examined for metals by the ordinary methods. (2). The solution in which sulphuretted hydrogen failed to produce a precipitate, or the filtrate separated from the precipitate formed, is divided into two parts: one portion is treated with ether and a solution of potassa; the other with ether and a solution of soda. Both mixtures are then well agitated, and notice taken if the ether dissolves any thing: if so, the operation is repeated several times until all soluble substances are removed. The ethereal solutions are next decanted and united, and then submitted to the examination for alkaloids as directed pp. 65-84. (3). If--the above treatment giving either positive or negative results--a precipitate insoluble in ether is formed by the addition of potassa or soda, it is collected on a filter, washed, and dissolved in an acid. The solution is then tested for mineral bases. (4). In case no definite result has been obtained by the preceding operations, one of the portions (for instance, the one to which potassa was added) is tested for the acids possibly present in the state of salts. The solution is divided into two parts (A and B) which are examined separately: PORTION A.--This is evaporated to dryness and the residue divided into four parts which are then tested for hydrofluoric, nitric, oxalic, and acetic and formic acids. _a._ HYDROFLUORIC ACID.--A portion of the residue is heated in a platinum crucible with sulphuric acid, and the crucible covered with the convex face of a watch-crystal coated with wax in which lines have been traced with a pointed piece of wood. If, after gently heating the crucible for some time and removing the watch-crystal, the lines traced in the wax are found to be etched in the glass, the substance under examination contains a _fluoride_. _b._ NITRIC ACID.--If this acid be present, and a second portion of the residue is heated with sulphuric acid and copper, reddish-fumes are evolved. Upon conducting the vapors into a solution of sulphate of iron or narcotine, the reactions already mentioned in treating of nitric acid take place. _c._ OXALIC ACID.--The third portion of the residue is heated with sulphuric acid, and the evolved gas carefully collected. It should then be confirmed by an elementary analysis that the gas consists of equal volumes of carbonic oxide and carbonic acid. This test is not conclusive; it is also necessary to ascertain if the precipitate produced by the addition of a baryta solution (_vide_: under portion _B._) produces the same reaction, inasmuch as other organic bodies could give rise to carbonic oxide and carbonic acid, and the danger of both admitting the presence of oxalic acid, when it is absent, and omitting its detection, in case it is present, would be incurred. _d._ ACETIC AND FORMIC ACIDS.--The fourth portion of the residue is distilled with dilute sulphuric acid. After determining that a small portion, previously neutralized with a base, acquires a red color, upon addition of a solution of a persalt of iron, the distillate is divided into two parts. One portion is treated with bichloride of mercury: if _formic acid_ be present, metallic mercury is formed, with evolution of carbonic acid which produces turbidity in lime-water. The remaining portion of the fluid is digested, in the cold, with an excess of litharge: in presence of _acetic acid_, a soluble basic salt of lead, possessing an alkaline reaction, is produced. PORTION B.--The second portion of the solution is supersaturated with nitric acid, and this neutralized by addition of a slight excess of ammonia. The ammonia is then expelled by boiling the fluid, and a solution of nitrate of baryta added. If a _precipitate_ forms, it is collected and subsequently examined for sulphuric, phosphoric, oxalic and boric acids as directed below. The _filtrate_ is preserved and tested for hydrochloric, hydrobromic and hydriodic acids. _a._ OXALIC ACID.--A portion of the precipitate produced by the addition of nitrate of baryta is submitted to the test mentioned under the treatment of portion _A_. _b._ SULPHURIC ACID.--If an insoluble residue remains upon treating the remainder of the precipitate with dilute hydrochloric acid, it consists of sulphate of baryta and indicates the presence of _sulphuric acid_. _c._ PHOSPHORIC ACID.--An excess of solution of alum and ammonia is added to the portion of the precipitate dissolved in hydrochloric acid. If phosphoric acid be present, insoluble phosphate of alumina is precipitated. This is brought upon a filter: the _filtrate_ being preserved and subsequently examined for boric acid. Upon boiling the precipitate with solution of silicate of potassa, silicate of alumina is thrown down, and phosphate of potassa remains in solution. Chloride of ammonia is now added to the liquid--in order to eliminate the excess of silica from the silicate--and the solution filtered. The _filtrate_ is then tested for phosphates, by means of molybdate of ammonia (_vide_: _detection of phosphoric acid_, p. 48). _d._ BORIC ACID.--The filtrate from the precipitate of phosphate of alumina is evaporated to dryness, the residue mixed with sulphuric acid and alcohol, and the latter ignited. If the substance contains _boric acid_, the alcohol will burn with a _green_ flame. The _filtrate_, separated from the precipitate produced by the addition of nitrate of baryta, may contain hydrochloric, hydrobromic and hydriodic acids. In order to detect these compounds, some nitrate of silver is added to the solution, and the precipitate that may form carefully washed and decomposed by fusion with potassa. The mass is then dissolved in water, and the solution submitted to the following tests: _e._ HYDRIODIC ACID.--Some starch paste and nitric acid--containing nitrous acid in solution--are added to a portion of the solution: in presence of an _iodide_, the fluid immediately acquires a blue color. _f._ HYDROBROMIC ACID.--In case iodine has not been detected, chlorine water and ether are added to a second portion of the fluid, and the mixture well agitated. If _bromine_ be present, the ether will assume a _brown_ color. In case iodine is also contained in the fluid, and the detection of bromine is desired, it is necessary to acidulate the solution with hydrochloric acid, and then shake it with chloride of lime and bisulphide of carbon. The bisulphide of carbon dissolves the iodine, acquiring a _violet_ color, which disappears upon a renewed addition of chloride of lime; whereas, in presence of bromine an _orange_ coloration remains, even after the disappearance of the iodine reaction. _g._ HYDROCHLORIC ACID.--Since the substance under examination will already contain hydrochloric acid, it is unnecessary, in most cases, to institute a search for this compound. Nevertheless, it may be well to take a quantity of the solution, corresponding to a known weight of the original substance, and precipitate the acid by adding nitrate of silver. The precipitate formed is dried and weighed. It is then heated in a current of chlorine, in order to completely convert it into chloride of silver, and its weight again determined. Only in case the amount of chloride found is very large, is it to be inferred that the poisoning has been caused by hydrochloric acid. _h._ HYDROSULPHURIC ACID.--(_Sulphuretted hydrogen_). If the precipitate produced by nitrate of silver possesses a black color, it may consist of a _sulphide_. Upon treating a portion with solution of hyposulphite of soda, all but the sulphide of silver is dissolved. In case a residue remains, it is calcined with nitrate of soda, and the sulphate formed detected by adding a soluble barium salt to its solution. Sulphates, chlorides, carbonates and phosphates are most frequently met with in the preceding examination, and it should be carefully noticed which of these salts exist in the greatest abundance. If acids of comparatively rare occurrence (such as the oxalic and tartaric) are found, their approximate amount is also to be noted. These facts, together with the original acidity of the materials and the absence of other toxical bodies, would lead to the conclusion that the poisoning was caused by the reception of an acid, as well as to the identification of the special acid used. In subsequently effecting the detection of the poison by the determinative tests, the danger of destroying other poisons possibly contained in the substance will be obviated, as the question of the absence or presence of these latter will have been previously decided. (5). The examination for acids concluded, the various fluids which have accumulated, and from which the acids present have been separated, are united and the whole evaporated to dryness. The organic substances, present in the residue obtained, are destroyed by means of nitric acid, and the residual mass examined for _soda_. If this substance has not been introduced into the portion of fluid examined, and is discovered in a quantity largely in excess of the amount normally contained in the organism, it is probable that poisoning has been caused by its administration, and that an acid has also been given, either in order to mask the poison, or to act as an antidote. In this case, it is necessary to carefully search for acetic acid, as this is the substance usually employed as an antidote for alkalies. (6.) Whatever results have been obtained by the preceding examinations, the portion of the fluid which has been treated with soda (_vide_ p. 87) is evaporated to dryness. The organic matters possibly present are destroyed by means of nitric acid, or _aqua regia_, and the residue taken up with water. The solution so obtained is then examined for metals (including potassa, which salt has not been introduced into this portion of the fluid in any of the preceding operations) by the usual methods. (7). The soluble portion of the suspected materials having been thoroughly tested, the undissolved substances remaining on the filter are next examined. _b._ SOLID PORTION. (1). The organic matter present is first destroyed by treatment with _aqua regia_. The fluid is then evaporated to dryness, and the residue heated until the nitric acid is entirely expelled; the escaping vapors being collected in a cold receiver. The residue is next taken up with water, the solution filtered, and sulphuric acid added. Should a precipitate of sulphate of lime, sulphate of baryta or sulphate of strontia form, it is separated from the fluid and further examined. The filtered solution is then introduced into Marsh's apparatus, sodium amalgam being employed for generating the hydrogen, and tested for _arsenic_ and _antimony_ by means of the reactions previously given. (2). Whether one of the above poisons be discovered or not, the still acid fluid is removed from the flask, a current of chlorine conducted through it for several hours and the solution then examined for _mercury_ by Flandin and Danger's method. In case mercury is found it could scarcely have originated from the metal in Marsh's apparatus, as this would not be attacked by cold dilute sulphuric acid: however, to remove all doubts, the test should be repeated with a portion of the substances reserved for the examination by the determinative tests. (3). Whatever have been the results of the above examinations, it is still to be ascertained if the fluid, which has been successively treated by Marsh's and Flandin and Danger's methods, does not contain other metals. This is accomplished by means of the ordinary reactions. THE SUBSTANCE POSSESSES A NEUTRAL OR AN ALKALINE REACTION. The examination is conducted in precisely the same manner as in the preceding case, excepting that the materials are first acidulated with oxalic or tartaric acids. Particular attention should be given to the search for soda, potassa, lime, baryta and strontia, and the determinative tests subsequently applied according to the indications obtained. DETERMINATIVE TESTS. In many instances the tests we have termed indicative become determinative in their character. This is the case when the isolation of an alkaloid or a metal (unless mercury be found under the circumstances already mentioned) is accomplished; the results obtained are then _conclusive_. If, on the other hand,--not being able to separate either an alkaloid or a metal--upon saturating the originally acid fluid with potassa, or soda, the salts of these bases have been found in abundance, there is reason to _infer_ that the poisoning has been caused by an acid; or, if, after the neutralization of the originally alkaline solution with an acid, potassa or soda are discovered in a large quantity, poisoning by an alkali is _indicated_. In case the fluid is neutral, but more or less colored and odoriferous, and iodides or bromides are detected, we may justly _suspect_ that the poisoning has been caused by the reception of iodine or bromine. According to the indications furnished, iodine, bromine, one, or all of the acids, the caustic alkalies, etc., are then detected by means of the methods to be employed in cases where the expert has a clew to the poison present. In this manner, the presence of potassa and soda, and of bromine and iodine, even in mixtures, is easily ascertained. It only remains to mention the course to be pursued when suspicion exists that poisoning has been caused by the administration of a mixture of several acids. The suspected materials are boiled with water, and alcohol added to the solution in order to coagulate the animal matters. The solution is next filtered, the filtrate placed in a retort provided with a receiver and distilled until the residual portion acquires a pasty consistency. In this way, the acids present are separated into two classes: (_a_) those that are sufficiently volatile to have passed into the receiver, such as, acetic, nitric, hydrochloric and sulphuric acids (the latter acid will only be partially volatilized); and (_b_) those that remain in the retort. The former are detected by examining the distillate as previously directed. The residue remaining in the retort is treated with absolute alcohol, the fluid filtered, and a solution of acetate of lead added to the filtrate: sulphuric, phosphoric and oxalic acids, if present, are precipitated. The precipitate is suspended in water and decomposed by means of sulphuretted hydrogen. The acids contained are now set free, and are detected by applying the tests already mentioned. If there be reason to suspect the presence of both sulphuric and oxalic acids, the distillation is discontinued after a short time. The two acids are dissolved by shaking the moderately concentrated fluid remaining in the retort with ether, and, upon evaporating the solution, will be obtained in a state suitable for examination. Oxalic acid is then detected by means of sulphate of lime; sulphuric by means of oxalate of baryta. The above examinations would fail to effect the detection of _phosphorus_, and it is necessary to examine a separate portion of the original substance for this body. IV. MISCELLANEOUS EXAMINATIONS. DETERMINATION OF THE NATURE AND COLOR OF THE HAIR AND BEARD. A criminal, in order to conceal his identity, may change the color of the hair and beard by artificial means; either to a darker shade, in case they were naturally of a light color, or, to a lighter hue, if they were originally dark, and the chemical expert may be called upon to detect this artificial coloration, and restore the original color of the hair. It may also happen, that portions of hair still adhere to the clots of blood sometimes found on an instrument which has been employed in the commission of a crime, and consequently the question may arise as to the nature of the hair, whether it be human or animal. DETERMINATION OF THE COLOR OF THE HAIR AND BEARD. The mode of examination necessary when the hair has been blackened is different from that used when it has been decolorized. _The hair has been blackened._ As various methods of dyeing hair black are in use, the means of restoring the original color differ. The following are the methods most usually employed in dyeing: 1º. The hair is well rubbed with a pomade, in which finely pulverized charcoal is incorporated. This preparation, which is sold under the name of "_mélaïnocome_," possesses the disadvantage of soiling the fingers and clothing, even for several days after its application. 2º. The hair is moistened with a dilute solution of ammonia, and a perfectly neutral solution of a bismuth salt (chloride or nitrate) is then applied. It is subsequently washed, and allowed to remain in contact with a solution of sulphuretted hydrogen. 3º. The same operation is performed, a lead compound being substituted for the bismuth salt. 4º. A mixture of litharge, chalk, and slacked lime is applied, and the head covered with a warm cloth. The hair is afterwards washed, first with dilute vinegar, then with the yolk of an egg. 5º. The hair is first cleansed with the yolk of an egg, and then moistened with a solution of plumbate of lime; or, 6º. It is moistened with a solution of nitrate of silver, to which a quantity of ammonia sufficient to dissolve the precipitate first formed has been added. The first method merely causes a mechanical admixture of a coloring matter with the hair. In the four succeeding processes, a black metallic sulphide is produced; either by the subsequent application of a solution of sulphuretted hydrogen, or by the action of the sulphur normally present in the hair. In the last method, the formation of sulphide of silver doubtless occurs; but the principal change that takes place is probably due to the action of light, which, as is well known, decomposes the salts of silver. In order to restore the original color to hair which has been treated with "_mélaïnocome_," it is only necessary to dissolve in ether the fatty matters present, and then remove the charcoal by washing with water. In case the hair has been dyed by means of a bismuth or lead salt (as in methods 2, 3, 4 and 5), it is immersed for several hours in dilute hydrochloric acid: the metal present dissolves, as chloride, and the original color of the hair is rendered apparent. It then remains to detect the metal dissolved in the acid solution, in order to establish, beyond doubt, the fact that a dye has been employed. This is accomplished by means of the methods used for the detection of metals in cases of supposed poisoning. If, finally, an ammoniacal solution of nitrate of silver has been employed to cause the coloration, the hair is immersed, for some time, in a dilute solution of cyanide of potassium, and the fluid subsequently examined for silver. In case a portion of the salt has been converted into the sulphide, it will be difficult to restore the original color, as the removal of this compound is not easily effected. _The hair has been decolorized._ Black hair can be bleached by means of chlorine-water, the various shades of the blonde being produced by the more or less prolonged action of the reagent. In this case, the odor of chlorine is completely removed only with great difficulty, and the hair is rarely uniformly decolorized. The expert may therefore be able to observe indication that will greatly assist him in arriving at a definite conclusion. The hair should be carefully examined up to the roots: if several days have elapsed since the decolorization has been performed, the lower portion of the hair will have grown and will exhibit its natural color. No method has yet been proposed that restores the original color to bleached hair. It is very possible, however, that this end would be attained by allowing nascent hydrogen to act upon the decolorized hair. For this purpose, it would be necessary to immerse it in water containing some sodium amalgam, and slightly acidulated with acetic acid. DETERMINATION OF THE NATURE OF THE HAIR. In examinations of this character use is made of the microscope. The hair to be examined is suspended in syrup, oil, or glycerine and placed between two thin glass plates. Human hair is sometimes cylindrical; sometimes flattened. It consists either of a central canal, or of a longitudinal series of oblong cavities which contain oily coloring matter, and possesses the same diameter throughout its entire length. The brown hair of the beard and whiskers, medium-sized chestnut hair, the hair of a young blonde girl, and the downy hair of a young man possess respectively a diameter of 0.03 to 0.15; 0.08 to 0.09; 0.06; and 0.015 to 0.022 millimetres. These exhibit on the surface slightly projecting scales, which are irregularly sinuous at the border, separated from each other by a space of about 0.01 m.m., and are transparent, whatever may be their color. The hair of ruminants is short and stiff, and is characterized by containing cavities filled with air. Wool, however, forms an exception, as it consists of entire hairs, homogeneous in appearance and possessing imbricated scales, which bestow upon it the property of being felted. The hair of the horse, ox and cow never exceeds 12 m.m. in length, and is tapering, its diameter gradually diminishing from the base. It is perfectly opaque, and does not appear to possess a central canal; has a reddish color, and frequently exhibits lateral swellings, from which small filaments occasionally become detached, in the same manner as a twig separates itself from the parent branch. EXAMINATION OF FIRE-ARMS. (_Proposed by M. Boutigny._) The examination of fire-arms is sometimes useful in determining the date at which a weapon has been discharged or reloaded. The methods used in examinations of this nature vary, as the weapon under inspection is one provided with a flint or an ordinary percussion lock. The value of the tests employed is also affected by the kind of powder used; _i. e._, whether common gunpowder, gun-cotton or white gunpowder (prepared by mixing yellow prussiate of potassa, chlorate of potassa and sugar) has been taken. THE GUN IS PROVIDED WITH A FLINT-LOCK, AND WAS CHARGED WITH ORDINARY POWDER. In case the weapon has been wiped or exposed to moisture subsequent to its seizure, it is impossible to form any conclusion as to the date of its discharge, etc. It is therefore advisable, upon receiving the weapon, to carefully wrap the lock in a woollen cloth, and to close the barrel. The exterior of the gun is at first submitted to a careful examination, and notice taken of the approximate thickness of any existing rust spots. The fire-pan and adjacent portion of the barrel are also examined by aid of a magnifying glass, especial attention being given to the detection of traces of a moist and pulverulent incrustation of a greyish or blackish color, formed by the combustion of the gunpowder, and of crystals of sulphate of iron. If the weapon is loaded, the wad is withdrawn and the color of its cylindrical portion and of the powder, as well as the size of the ball or shot, noted. This preliminary examination ended, the barrel and fire-pan are separately washed with distilled water, and the washings passed through filter paper which has previously been well washed, first with pure hydrochloric acid, then with distilled water. The filtrate is next divided into three portions, and these separately examined for: (1) sulphuric acid, by addition of chloride of barium; (2) for iron, by oxidizing the salts contained in the fluid with a few drops of nitric acid and adding a solution of ferrocyanide of potassium, the presence of iron being indicated by the formation of a blue coloration, or a blue precipitate; and (3) for sulphides, by means of a solution of subacetate of lead. If a bluish-black incrustation is discovered on the fire-pan or on the neighboring portions of the barrel, and both rust and crystals of sulphate of iron are absent, and the washings, which were originally of a light-yellow color, assume a chocolate-brown coloration upon the addition of solution of subacetate of lead, _the gun has been discharged within two hours at the longest_. If the incrustation possesses a lighter color and traces of iron have been detected in the washings, but neither rust nor crystals have been discovered on the barrel or fire-pan, _the weapon has been discharged more than two, but less than twenty-four hours_. In case minute crystals of sulphate of iron and spots of rust are found, and the washings contain iron in a considerable quantity, _the weapon has been discharged at least twenty-four hours, at the longest ten days_. If the quantity of rust found is considerable, but iron is no longer to be detected, _the discharge of the gun occurred ten days, at the longest fifty days, previously_. _If the weapon has been reloaded immediately after its discharge without having been previously washed_, the portions of the wadding which have come in contact with the barrel will possess a greyish-black color during the first four days, the color gradually becoming lighter, until, at the fifteenth day, it turns grey and remains so permanently. In this case, the washings will contain sulphuric acid. The objection has been advanced to the last test that sulphuric acid might be discovered, even if the gun had not been discharged, if the paper of which the wadding was made contained plaster. M. Boutigny states, however, that this objection is untenable, if the wadding has not been moistened by the water introduced into the barrel. _In case the gun has been washed and dried before being reloaded_, the cylindrical portion of the wadding possesses an ochre-yellow color up to the first or second day, assumes a decided red hue on the days following, and acquires a clear rusty color on the sixth day. During the fifth day the powder also possesses a reddish appearance, owing to an admixture of rust. Sulphuric acid is not present in the washings. _If the weapon has been reloaded immediately after being washed_, the wadding possesses a greenish-yellow appearance for the first few hours, and subsequently acquires a reddish color, as in the preceding case. _If, finally, the barrel has been washed with turbid lime-water_, rust is still to be found and the wadding possesses the color mentioned above. The following colorations are also to be observed in case the gun has not been washed, or has been dried near a fire: BARREL DRIED NEAR A FIRE. UNWASHED BARREL. After 1 day slight reddish yellow color greenish yellow color. 2 or 3 days a little darker " reddish-brown " 4 days a redder " reddish-brown " 5 or more days a rusty-red " rusty-red. " THE GUN IS NOT PROVIDED WITH A FLINT LOCK. At present weapons having flint-locks have almost entirely gone out of use and have been superseded by the ordinary percussion gun; these latter, in turn, are being gradually replaced by breech-loaders, charged with or without a metallic cartridge. The indications obtained in the preceding examinations by means of the fire-pan, will therefore disappear; the results given by the inspection of the barrel may possibly hold good. In regard to breech-loaders, all the useful indications furnished by the coloration of the wadding and powder fail to occur; the latter being enclosed either in a paper cylinder or in a copper socket. The fact that gun cotton and white gunpowder are occasionally made use of, adds to the difficulty of obtaining reliable results by the mere inspection of a weapon. White gunpowder does not oxidize the gun, fails to give rise to any salt of iron, and possesses a white color; gun-cotton produces distinctive indications varying with its purity. Owing to these facts, it is evident that the method proposed by M. Boutigny is of no real value, save in the rare instances where a gun provided with a fire-pan, and charged with ordinary powder, is under examination, and the question of the lapse of time since the discharge of a weapon must remain undetermined so far as scientific tests are concerned. DETECTION OF HUMAN REMAINS IN THE ASHES OF A FIRE-PLACE. This class of examinations is particularly necessary when the crime of infanticide is suspected. As the complete incineration of a cadaver is a long and difficult operation, it frequently occurs that bones--partially or completely carbonized, but retaining their original form--are discovered by the careful examination of the ashes of the fire-place in which the combustion was accomplished. When this is not the case and complete incineration and disaggregation have occurred, recourse must be had to the indications furnished by a chemical analysis. These indications are reliable, however, only when the certainty exists that bones of animals have not been consumed in the same fire-place; otherwise, the results obtained are entirely worthless, the reactions given by ashes of animal bones being identical with those produced by the ashes of a human body. Two tests are employed to detect the presence of bones in the residue left by the combustion of animal matter. 1. A portion of the ashes is placed in a silver crucible, heated with potassa, and the mass afterwards treated with cold water. If animal matter is contained in the consumed materials, cyanide of potassium will be present in the aqueous solution. In order to detect this salt, the fluid is acidulated with hydrochloric acid, and a solution of persulphate of iron added: the formation of a blue precipitate indicates the presence of the cyanide. 2. The ashes are next examined for phosphate of lime. As wood, coal, and the other substances usually employed for heating purposes contain none or little of this salt, its detection in a notable quantity would lead to the inference that bones have been consumed. The ashes are allowed to digest for twenty-four hours with one-quarter of their weight of sulphuric acid. Water is next added to the pasty mixture, and the fluid filtered. If phosphate of lime be present, it is converted by this treatment into a soluble acid phosphate, which passes into the filtrate. Upon adding ammonia to the filtrate, a precipitate of neutral phosphate of lime is formed, neutral phosphate of ammonia remaining in solution. The fluid is again filtered, the filtrate acidulated with nitric acid, and then boiled with a solution of molybdate of ammonia likewise acidulated with nitric acid: in presence of a phosphate, a yellow precipitate, or at least a yellow coloration of the fluid, will be produced. It has been stated that the disengagement of sulphuretted hydrogen, upon treating the ashes with sulphuric acid, is an indication that the combustion of a human body has occurred; this reaction is, however, valueless, inasmuch as coal and certain vegetable ashes likewise evolve the gas when subjected to the same treatment. EXAMINATION OF WRITINGS. Contracts, checks, etc., are frequently altered with criminal intent, either by erasing the portion of the writing over the signature and substituting other matter, or by changing certain words, in order to modify the signification of a sentence. Writings are altered either by erasure or by washing. Erasure, although more easily executed, is seldom employed, as it renders the paper thin in places, and in this way leaves effects apparent even to the naked eye, and, although the original thickness can be restored by application of sandarac or alum, these substances possess properties differing from those exhibited by paper, and may, moreover, be completely removed, thus exposing the thinning of the paper. In case washing by means of chlorine has been resorted to, the sizing--which renders the paper non-bibulous, and which is only with difficulty replaced--may have been removed. Formerly paper was sized by immersion in a solution of gelatine; at present, however, a soap of resin, or wax, and alumina (a little starch being added) is more commonly used. In the latter case, the sizing is less easily removed by the action of water than when the gelatine preparation is employed; the detection of its attempted restoration is also a matter of less difficulty, as gelatine would be employed for this purpose, and this body possesses properties different from those exhibited by the substances normally contained in paper: iodine, for instance, which imparts a yellow color to gelatine, turns starch violet-blue. In order to detect the alteration of a writing, the following examinations are made: 1º. The paper is carefully examined in all of its parts, and in various positions, by aid of a lens. In this way, either thinned points, caused by erasure, or remaining traces of words, may possibly be discovered. 2º. The paper is next placed upon a perfectly clean piece of glass, and completely and uniformly moistened with water. The glass is then removed, and the transparency of the paper examined by aid of a lens. When uniform transparency is exhibited, and certain portions are neither more transparent nor more opaque than the rest of the paper, it is probable that erasure has not been attempted. If, on the other hand, opaque points are observed, it is almost certain that letters have been erased, and sandarac, which is not affected by water, subsequently applied. In case transparent points are detected, there is reason to suspect that words have been removed, and the spots either left intact or afterwards coated with a substance soluble in water, such as alum. 3º. The paper is dried and the above operation repeated with alcohol of 87 per cent. Indications may now be observed which failed to occur in the treatment with water; as well as these latter confirmed. As alcohol dissolves sandarac, the points that formerly appeared opaque may now become transparent. 4º. The paper is again dried, then placed under a sheet of very thin silk-paper, and a warm iron passed over it. This operation frequently causes the reappearance of words that have been partially obliterated. It is also advisable--as suggested by _M. Lassaigne_--to expose the paper to the action of iodine vapors. If alteration has not been attempted, the paper will acquire an uniform color; yellow, if sized with gelatine; violet blue, if sized with the mixture of soap, resin and starch. When, on the contrary, a subsequent sizing of gelatine has been applied in order to mask the alteration--the paper having been originally sized with the above mixture--it will assume in some portions a yellow, in others a violet-blue color. 5º. It is ascertained whether the paper possesses an acid reaction. If so, its acidity may result from the presence of hydrochloric acid, in case the paper was washed with chlorine, or of other acids. Alum, used to disguise erasure, would also cause an acid reaction. The mere detection of acidity is, in itself, of little importance, as, in the manufacture of paper, the pulp is bleached by means of chlorine, and this reagent may not have been entirely removed by washing. If, however, the paper is acid only in certain spots, and these points produce a red coloration upon blue litmus paper, having the form of letters, the indication is of value. In order to ascertain if this be the case, it is advisable, before wetting the paper, to slightly press it upon a sheet of moist litmus paper: the acid spots will then leave a reddish trace upon the latter. 6º. The manuscript under examination is again spread upon a glass-plate, and a solution of tannin (or preferably, a solution of ferrocyanide of potassium containing one per cent. of the salt, and acidulated with acetic acid) applied by means of a brush. If the original writing was executed with ordinary ink (which has as its base tannate of iron), and the washing has been but imperfectly performed, it is quite possible that a blue coloration will be produced by the action of the ferrocyanide. It is, however, often necessary to apply the above reagents several times before the original writing becomes apparent; indeed, in some cases months have elapsed before the reaction has occurred. In case the alteration or destruction of the document is feared in the above test, it is well to previously provide the court with a certified copy, and then proceed with the examination. 7º. If the paper possesses a friable appearance, it has possibly been washed with sulphuric acid. This property may however originate from other causes, and the presence of the acid should be confirmed by washing the document with distilled water, and adding a solution of chloride of barium to the washings. The precipitate should form in a considerable quantity, as a slight cloudiness could be due to sulphates contained in the water used in the preparation of the pulp. If much sulphuric acid be present, it may be so concentrated by heating as to cause the carbonization of the paper. 8º. It is also well, should washing with sulphuric acid be suspected, to ascertain, by aid of a lens, if the filaments on the surface of the manuscript possess an inflated appearance. This would be caused by the escape of carbonic acid, originating from the action of sulphuric acid upon the carbonates contained in the water used in the manufacture of the paper. 9º. Old ink is more difficult to remove than new, and it is therefore sometimes possible to cause the reappearance of old writings, over which words have been subsequently written. For this purpose, a solution containing 50 per cent. of oxalic acid is applied with a fine brush over the suspected points. As soon as the ink disappears, the acid is immediately removed by washing with water, and the paper dried. Upon now repeating the operation, the presence of a former writing may be detected after the complete disappearance of the words last written. 10º. According to _M. Lassaigne_, when the same ink has not been used throughout a document, washing with dilute hydrochloric acid will demonstrate the fact. This acid, while causing the gradual obliteration of characters written with ordinary ink--the shade of the paper not being altered--produces a red color, if ink containing log-wood has been employed, and a green coloration, in case the ink used contained Prussian blue. The expert may possibly be called upon to give evidence as to the existence of a "_trompe-l'oeil_;" as was the case in the trial of _M. de Preigne_, which took place at Montpelier in 1852. A "_trompe-l'oeil_" consists of two sheets of paper, glued together at the edges, but having the upper sheet shorter than the other which therefore extends below it. This species of fraud is executed by writing unimportant matter on the uppermost sheet, and then obtaining the desired signature, care being taken that it is written on the portion of the paper projecting below. The signature having been procured, it is only necessary to detach the two sheets in order to obtain a blank paper containing the signature, over which whatever is desired can be inserted. The trial referred to above, was in reference to a receipt for 3,000 francs. The expert, upon placing pieces of moistened paper upon the suspected document, noticed that they adhered to certain points, and that these formed a border around the paper but passing _above_ the signature. The fraudulency of the act was thus established, and so recognized by the court, although the accused was acquitted by the jury. Numerous means have been proposed, in order to render the falsification of documents a matter of difficulty. The most reliable of these is the use of "Grimpe's safety-paper," containing microscopic figures, the reproduction of which is impossible. Unfortunately, up to the present, the government has adopted methods less sure. EXAMINATION OF WRITINGS IN CASES WHERE A SYMPATHETIC INK HAS BEEN USED. Sympathetic inks are those which, although invisible at the time of writing, become apparent by the application of certain agents. They are of two classes: those which are rendered visible by the mere application of heat, such as chloride of cobalt, or the juice of onions; and those which are brought out only by the action of a reagent. The inks of the second class most frequently used are solutions of acetates of lead, and other metals which give a colored sulphide when treated with sulphuretted hydrogen. Characters written with a solution of ferrocyanide of potassium acquire a blue color, if washed with a solution of perchloride of iron. It is scarcely necessary to add that the latter solution can be used as the ink, and the ferrocyanide as the developer. When the presence of characters written with a sympathetic ink is suspected, the document is examined as follows: 1. The paper is at first warmed: if the ink used is of the first class, the characters will now become legible; otherwise the examination is continued as below. 2. The paper is exposed to the action of steam, in order to moisten the ink present (care being taken to avoid dissolving the characters), and a current of sulphuretted hydrogen allowed to act upon it. If the ink used consists of a lead, bismuth, or gold salt, a black coloration will ensue; if salts of cadmium or arsenic were employed, the characters will acquire a yellow color; if, finally, a salt of antimony was used, a red coloration will be produced. 3. If no coloration was caused by the action of sulphuretted hydrogen, it is probably that either a solution of ferrocyanide of potassium or a persalt of iron has been resorted to. Each of these solutions is separately applied on a small portion of paper by means of a brush, and notice taken if the characters become visible. The solution that produced the change is then applied over the entire sheet. 4. In case only negative results were obtained in the preceding operations, it must not yet be concluded that a sympathetic ink has not been used, although we are left without further recourse to chemical tests. Numerous organic compounds may have been resorted to, the detection of which is almost impossible; moreover, if a mistake was made in regard to the preparation supposed to have been used, the reagents employed for its detection may render the discovery of another ink absolutely impossible. It is therefore often necessary to apply mechanical tests. For this purpose, the paper is spread upon a glass plate, uniformly moistened with water, and a second plate placed over it: if the characters were written with a pulverulent substance suspended in water or mucilage, they may often be observed upon examining the transparency of the paper. In case the substance used is both colorless and soluble, the detection of the written characters will be more difficult; still, indelible traces may possibly have been left by the pen. If, however, the ink employed is a colorless and transparent organic compound of rare occurrence, and was applied with a fine pencil-brush which failed to affect the paper, it must be acknowledged that little or nothing can be definitely determined as to its presence or absence. FALSIFICATION OF COINS AND ALLOYS. In all civilized countries a fixed standard for coins and precious alloys is established by law, in order to prevent the perpetration of frauds which would be of serious injury to the public welfare. The substitution of coins consisting of an alloy inferior in value to the standard fixed by law, is too advantageous a fraud not to be often attempted. Coins are most frequently altered by _clipping_; by _stuffing_, that is, by boring the coin and inserting an alloy of small value; by _doubling_, which operation consists in covering its face with two thin laminæ taken from a genuine coin; and by applying a coating of gold or silver by means of electro-plating. In order to ascertain if a coin has been counterfeited, its weight should at first be determined. If it has been clipped, or consists of an alloy possessing a density less than that of silver or gold, the fact is immediately demonstrated by its decreased gravity. The coin is further tested by throwing it down upon a hard substance: gold and silver give a ringing sound, whereas the majority of other metals produce a dull sound. The result obtained by this latter test often fails to be reliable. A skilful counterfeiter may prepare an alloy equally sonorous and heavy as silver or gold; in fact, _M. Duloz_ exhibited to the author an alloy, prepared by him, possessing the density, sonorousness and lustre of silver; the composition of which, for obvious reasons, has not been published. In instances of this nature the fusibility of the coin should be determined, and the result obtained compared with the melting point of the legal alloy, or, this failing, a chemical analysis executed. In order to perform the latter test, the coin under examination is boiled with nitric acid: all metals are dissolved, with exception of gold and platinum, which remain unaltered, and tin and antimony, which are converted respectively into metastannic and antimonic acids. The fluid is filtered, the insoluble residue well washed, and then boiled with hydrochloric acid, which dissolves the metastannic and antimonic acids. The solution is again filtered, and the second residue dissolved in _aqua regia_. The metals dissolved in the several filtrates are then detected, either by the processes previously given for the detection of metallic poisons, or by the more complete methods contained in works on chemical analysis. This qualitative test is, however, insufficient, in case the falsification consisted in merely diminishing the proportions of the valuable metals contained in the alloy, without changing its qualitative composition: it is then necessary to execute a quantitative estimation of the metals present. As this operation requires considerable practice and the methods employed are to be found in all treatises on quantitative analysis, we will not reproduce them here. EXAMINATION OF ALIMENTARY AND PHARMACEUTICAL SUBSTANCES. We will next enumerate the methods employed in the detection of the principal adulterations to which flour, bread, oils of seeds, milk, wines, vinegar and the sulphate of quinine are subjected. These researches, united with those preceding, fail to embrace all the diverse examinations which the chemical expert may be expected to execute; but we do not claim to foresee all the contingencies that may arise, and will describe the steps to be pursued in instances which are anticipated, at the same time indicating general methods applicable to cases not here included. FLOUR AND BREAD. The adulterations to which flour and bread are exposed usually consist in adding damaged or an inferior grade of flour to wheaten flour, or in disguising the presence of a poor quality of flour by the addition of mineral substances, such as: plaster, chalk, lime, alum, and sulphate of copper. Good flour has a white color, possessing a slightly yellow tinge, but is entirely free from red, grey or black specks. It is soft to the touch and adheres to the fingers, acquiring, when compressed in the hand, a soft cushion-like form. If mixed with water, it forms an elastic, homogeneous, but slightly coherent dough, which can be extended out in thin layers. Flour of an inferior quality possess a dull white color, and does not assume the cushion-like condition mentioned above, when pressed in the hand, but escapes between the fingers: the dough formed is of a poorer quality. Flour which has been damaged by moisture has a dull or reddish-white hue, and possesses a mouldy, or even a noxious, odor, as well as a bitter and nauseous taste which produces a marked acid sensation in the throat. Occasionally the presence of moisture causes the growth of _fungi_, the introduction of which in the digestive organs would cause serious results. The constituents of pure flour are: _Gluten._ _Starch_, in the proportion of 50 to 75 per cent. _Dextrine_, in the proportion of several per cent. _Glucose_, in the proportion of several per cent. _Salts_, remaining in the ash obtained by the calcination of the flour, in a proportion not exceeding 2 per cent. _Water_, of which it loses 12 to 15 per cent., at the heat of a water-bath, and 15 to 20 per cent., at a temperature of 160°. _Bran_, (ligneous and fatty matter,) in a very small proportion, when the flour has been properly bolted. In the process of bread-making, the gluten undergoes fermentation by the action of the leaven and liberates carbonic acid, which causes the dough to become porous and swell up, or, as it is termed, to _rise_. Bread contains the same substances as flour, but gluten and starch are present in a state that does not admit of their separation by mechanical means, and glucose, if present at all, exists in a smaller quantity: the proportion of dextrine and water is, on the other hand, considerably increased. The bread of the Paris city bakeries contains 40 per cent. of water--the crumb, which forms 5/6 of the weight of the bread, containing 45 per cent.; the crust, which constitutes the remaining 1/6, containing 15 per cent. In army bread 43 per cent. of water are contained--the crumb, which constitutes 4/5 of the weight of the bread, holding 50 per cent.; the crust which forms the remaining 1/5, containing 15 per cent. The addition of common salt naturally increases the proportion of ash left upon calcining bread. Water is contained in stale bread in the same quantity as in fresh bread; but exists in a modified molecular condition: upon heating stale bread, it acquires the properties of fresh bread. The following substances are used in the adulteration of wheaten flour:[P] Potato-starch. Meals of various grains (rice, barley, corn, oats and rye). Vegetable meals, (beans, horse-beans, kidney-beans, peas, vetch, lentils, etc.). Darnel meal. Buckwheat flour. Linseed-meal. Mineral substances (plaster, chalk, lime, alum, and sulphate of copper). [P] Most of the substances here enumerated are rarely, if ever, used for the adulteration of flour in this country. The analyst should, however, give attention to the examination for such salts as alum, sulphate of copper, plaster, kaolin, etc.--_Trans._ In order to detect these substances, the gluten, the starch, and the ash are separately examined. _a._ EXAMINATION OF THE GLUTEN. In order to separate the gluten, two parts of the flour to be examined and one part of water are mixed into a paste, and this is placed in a fine linen sack, in which it is kneaded under a stream of water so long as the washings have a turbid appearance: these are preserved. The gluten obtained from good wheaten flour possesses a light-yellow color; emits a stale odor; and spreads out, when placed in a saucer. In case the flour has been too strongly heated in the grinding, or otherwise badly prepared, the gluten is granulous, difficult to collect in the hand, and somewhat resembles flint-stone in appearance. Gluten prepared from a mixture of equal parts of wheat and _rye_ is adhesive, blackish, without homogeneousness, spreads out more readily than pure wheaten gluten, separates easily and adheres somewhat to the fingers. Gluten obtained from a mixture of wheat and _barley_ is non-adhesive, of a dirty reddish-brown color, and appears to be formed of intertwined vermicular filaments. Gluten formed from a mixture of equal parts of wheat and _oats_ has a blackish-yellow color and exhibits, at the surface, numerous small white specks. The gluten from a mixture of wheat and _corn_ has a yellowish color, is non-adhesive, but firm, and does not readily spread. Gluten prepared from a mixture of wheat and _leguminous flour_ is neither cohesive nor elastic, and, if the proportion of the latter present be considerable, can be separated and passed through a sieve, like starch. The gluten obtained from a mixture of equal parts of wheat and _buckwheat_ flour is very homogeneous, and is as easily prepared as the gluten from pure wheaten flour. It possesses when moist a dark-grey color; which changes to a deep black upon drying. The proportion of gluten in flour is exceedingly variable: good flour contains from 10 to 11 per cent. of dry gluten; poor flour from 8 to 9 per cent. of moist gluten, equal to about one-third of its weight of the dry compound. _b._ EXAMINATION OF THE STARCH. The washings of the flour are allowed to stand for some time in a conical-shaped vessel. As soon as the amylaceous matter has entirely settled to the bottom of the vessel, the greater portion of the water is decanted, and the residual mass brought upon a small filter and allowed to dry. The residue is then examined for potato and rice starch. _Potato starch._ The grains of potato starch are much larger than those of wheaten starch. If a portion of the residue mentioned above is crushed in an agate mortar, the granules of potato starch present are ruptured, and their contents liberated; the wheaten starch remaining unaltered. The mass is then taken up with water, and the fluid filtered. If potato starch be present, the filtrate will acquire a blue color upon addition of an aqueous solution of iodine; otherwise, a yellow or violet-rose coloration is produced. It is necessary to avoid crushing the residue for too long a time, as the granules of wheaten starch would also become ruptured by prolonged comminution. Besides the difference presented by potato starch in the size of the granules in comparison to those of wheaten starch, the former swell to ten or fifteen times the volume of the latter, when treated with a solution of potassa: wheaten starch granules are not affected by the treatment, if the solution used does not contain more than 2 per cent. of the salt. The results obtained by the above operation should be confirmed by a microscopic examination. A portion of the residue is moistened with solution of iodine, then carefully dried, and placed on the slide of a microscope. The mass is next moistened with a solution containing 2 per cent. of potassa, and examined. The addition of iodine causes the potato starch granules to acquire a blue color, and renders their shape and volume more easily perceptible; thus allowing the two varieties of starch to be readily distinguished. Fig. 13 represents the relative size of the granules as observed under the microscope.[Q] [Q] It may be added, as a distinguishing property, that granules of potato starch, when viewed in polarized light by aid of a Nicol's prism, present a well-defined black cross, corresponding to the hilum; wheaten-starch fails to exhibit this phenomenon.--_Trans._ [Illustration: Fig. 13.] The presence of potato starch in bread is also detected by crushing a small portion of the sample under examination on the glass, and then adding a few drops of the alkaline solution. _Rice and Corn._--If rice or corn meal have been mixed with the flour, angular and translucent fragments (Fig. 14) are observed in the microscopic examination. Corn meal acquires a yellow color, if treated with dilute potassa solution. [Illustration: Fig. 14.] MISCELLANEOUS TESTS. _Linseed and rye meals._--If linseed meal is moistened with an aqueous solution containing 14 per cent. of potassa and examined under the microscope, numerous minute characteristic granules, smaller than the grains of potato-starch, are observed. These possess a vitreous appearance, sometimes a reddish color, and usually form in squares or very regular rectangles. The test is equally applicable to bread. The detection of linseed and rye meals is simultaneously effected by exhausting the suspected flour with ether, then filtering the solution and allowing it to evaporate. If the flour contains rye, the oil left by the evaporation, when heated with a solution of mercury in concentrated nitric acid, is converted into a solid substance having a fine red color; but it remains unaltered, if entirely due to linseed. In case the oil becomes solidified, the mercury salt present should be removed by washing with water, the residue taken up with boiling alcohol of 36° B. and the solution filtered: upon evaporating the alcoholic filtrate, a residue is obtained consisting of the linseed oil present. _Buckwheat._--Flour adulterated with buckwheat is less soft to the touch, does not pack as easily, and passes more readily through a sieve than pure wheaten flour. It presents, here and there, blackish particles, due to the perisperm of the grain, and has a dirty-white color. As previously remarked, the gluten obtained from a mixture of buckwheat and wheaten flour possesses a grey or even a black color. The starch furnished by buckwheat flour exhibits polyhedral agglomerations, analogous to those presented by corn. _Darnel._--The use of darnel in the adulteration of wheaten flour may give rise to serious sanitary results. To effect its detection, the flour to be examined is digested with alcohol of 35° B.: if the flour be pure, the alcohol remains limpid: it acquires a straw-yellow tint, due to traces of bran present, but--although a peculiar resin may be dissolved--the solution does not possess a disagreeable taste. When, on the contrary, darnel is present, the alcohol assumes a green tint, which gradually deepens, and possesses a bitter and nauseous taste; the residue, left by the evaporation of the tincture to dryness, has a greenish-yellow color, and a still more disagreeable flavor than the alcoholic solution. _Legumens._--Leguminous meals cannot be added otherwise than in small proportions to wheaten flour, owing to the rapidity with which they change the properties of the latter, and communicate to it their characteristic odor--noticeable upon treating the flour with a little boiling water. Their presence is also easily detected by the distinctive properties of the vegetable itself, and by the appearance of the amylaceous residue in the microscopic examination. In order to decide as to the presence of legumens, the washings containing the starchy matter of the flour, after the particles of gluten present have been separated by passing the fluid through a silk sieve, are divided into two portions. One portion is allowed to undergo fermentation, at a temperature of 18° to 20°: in case leguminous substances are not present, lactic fermentation occurs and the odor of sour milk is alone perceptible; if, on the other hand, legumens are contained in the fluid, rancid fermentation takes place, and an odor is emitted resembling that of decayed cheese. The remaining portion of the washings, after being decanted from the residue of amylaceous matter, is filtered and evaporated until a yellowish translucent pellicle appears upon its surface. The fluid is then again filtered from the coagulated albumen common to all flours, and the leguminous substances present coagulated by the addition, drop by drop, of acetic acid. The leguminous deposit produced appears white and flaky; when examined under the microscope, it presents lamilla emarginated at the border; it is odorless and tasteless; when dried, it assumes a horny appearance; it is insoluble, both in water and alcohol, and does not become gelatinous when treated with boiling water; it is readily soluble in potassa and other alkaline solutions, from which it is precipitated upon addition of nitric, hydrochloric, acetic, oxalic, and citric acids; upon protracted boiling in water, it loses its property of being soluble in ammonia. The above tests having been applied, the residue containing the starch is next examined. For this purpose, a small portion is moistened with a little water, a few drops of iodine solution added, and the mixture placed on the side of the microscope: the bluish grains contained in the polyhedral and cellular envelope (Fig. 15) are easily recognized. The mixture on the glass may also be treated with an aqueous solution of potassa (containing 10 per cent. of the salt), or with dilute hydrochloric acid: these reagents dissolve the starch present, leaving the reticulated tissue intact. Should this examination fail to give a definite result, the remaining portion of the amylaceous residue is subjected to a sort of levigation, and the part most slowly deposited separated. In this portion the reticulated tissues of the leguminous substances present are contained, and, as they are comparatively free from foreign matters, their identification is a matter of comparative ease. In case the presence of reticulated tissue is indicated, it is still necessary to apply confirmatory chemical tests. [Illustration: Fig. 15.] Meals prepared from beans, horse-beans, and lentils, contain a tannin which imparts a green or black color to salts of iron. The coloration is rendered very sensitive if a rather considerable quantity of the flour to be examined is passed through a silk sieve, and the remaining bran treated with a solution of sulphate of iron (_ferrico-ferrous_ sulphate): the reaction immediately occurs, even if the sample contains but 10 per cent. of bean meal. The meals of horse-beans and of vetches acquire a red color, when exposed to the successive action of nitric acid and of ammonia vapors. In order to apply this test, the suspected flour is placed upon the edge of a capsule containing nitric acid, the latter heated, and, as a yellow coloration appears, the acid removed and replaced by ammonia. The capsule is then set aside: if the flour is adulterated with either of the above vegetables, reddish spots, which are easily perceptible by aid of a magnifying glass, are soon produced. In case bread is to be examined, it is exhausted with water, the fluid passed through a sieve, the upper layer decanted, then evaporated, and the residue taken up with alcohol. The tincture so obtained is evaporated, and the second residuum treated with nitric acid and ammonia, as directed above. When meals prepared from beans, vetches, or lentils are heated on a water-bath with hydrochloric acid, diluted with three to four times its volume of water, a cellular tissue, possessing the color of wine-dregs, remains behind; flours of wheat, peas, and kidney-beans leave a colorless residue, when subjected to the same treatment. Finally; the grains of the starch (_fecula_) of legumens possess a volume about equal to that of potato granules, and exhibit either a longitudinal furrow in the direction of their longer axis, or a double furrow arranged in a star-like form. _c._ EXAMINATION OF THE ASH. Leguminous substances, and more particularly mineral salts, are detected by the examination of the ash left upon the incineration of the flour. _Detection of Legumens._--Pure wheaten flour furnishes an ash consisting of about 2 per cent. of its weight; whereas meals of legumens leave from 3 to 4 per cent. of their weight in ash. This difference is, however, too slight to furnish conclusive results; the analysis of the ash is also necessary. The ash of wheaten flour is non-deliquescent, dry, semi-fused, and chiefly consists of phosphates of potassa, soda, magnesia and lime, of sulphates, and of silica. The solution obtained by treating the ash with water has an alkaline reaction. The phosphates of the alkalies, present in the ash of wheat, exist in the state of pyrophosphates, and, as chlorides are absent, the addition of nitrate of silver to the aqueous solution of the ash produces a white precipitate, consisting entirely of pyrophosphate of silver, which is not affected by exposure to the light. The ash of leguminous meals is deliquescent and soluble in water, forming a _strongly_ alkaline solution, which contains both chlorides and _neutral_ phosphates. The latter give a clear yellow precipitate with nitrate of silver. Upon adding a solution of this salt to the aqueous solution of the ash, a _pale_ yellow precipitate, which turns violet if exposed to the light, is therefore produced. _Detection of mineral substances._--The principal mineral substances, that are fraudulently added to flour, are ground calcined bones, sand, lime, plaster, alum, and sulphate of copper. The two last named salts are almost invariably added in small quantities; alum renders the flour white, even when used in the proportion of one per cent.; sulphate of copper is added to impart a good appearance to bread made from a damaged flour. _a. Ground bones_ (carbonate and phosphate of lime).--The washings of the gluten are placed in a conical vessel, and, after some time has elapsed, the clear supernatant fluid is removed by means of a syphon, a conical shaped deposit remaining on the bottom of the vessel: two hours later, the fresh layer of fluid that has formed is removed with a pipette. As soon as the residue becomes nearly solid, it is detached from the vessel, placed upon a fragment of plaster, and allowed to dry. The bones, being heavier than the amylaceous substances, are to be found in the apex of the cone formed by the residue. This is detached, and incinerated: in case the ash obtained contains phosphate and carbonate of lime, the addition of hydrochloric acid will cause effervescence, and, upon adding ammonia to the acid solution, a white precipitate will be formed. If the solution is then filtered and oxalate of ammonia added to the filtrate, a precipitate will be produced which, when heated to redness, leaves a residue of caustic lime possessing an alkaline reaction. _b. Sand._--As this substance possesses a much greater specific gravity than the usual constituents of flour, it is only necessary, in order to accomplish its separation, to repeatedly stir the flour with water, and remove the deposit at first formed, which, if consisting of sand, will be insoluble in acids, and will grate, when placed between the teeth. _c. Carbonates of lime and magnesia; vegetable ashes._--Carbonic acid is always evolved, upon treating flour with hydrochloric acid. If the base present be calcium, upon adding oxalate of ammonia to the filtered solution--which has previously been neutralized with ammonia--a white precipitate, possessing the properties mentioned above, will be formed; in case the base is magnesia, the addition of oxalate of ammonia will fail to cause a precipitate, but upon adding solution of phosphate of ammonia to the fluid a granular precipitate of phosphate of ammonia and magnesia is produced; if, finally, the flour contains vegetable ashes--_i. e._ carbonates of the alkalies--bichloride of platinum will produce in the acid solution a yellow precipitate: the addition of vegetable ashes, moreover, would render the ash of the flour deliquescent and very strongly alkaline. _d. Lime._--In presence of lime, carbonic acid produces a white precipitate, when conducted into the filtered aqueous extract of the flour. _e. Plaster._--The flour is boiled with water acidulated with hydrochloric acid, the fluid filtered, and lime detected in the filtrate by means of ammonia and oxalate of ammonia. The presence of sulphuric acid is indicated by the formation of a precipitate insoluble in acids, upon addition of solution of chloride of barium. Upon calcining the flour without access of air, sulphate of lime is converted into the corresponding sulphide: the residue of the calcination, when treated with hydrochloric acid, evolves sulphuretted hydrogen, and the lime present in the filtered acid solution is likewise precipitated by the addition of ammonia and oxalate of ammonia. _f. Alum._--A portion of the flour to be examined is treated with water, the fluid filtered, and the filtrate divided in two portions: in one, sulphuric acid is detected by means of chloride of barium; in the other, alumina by adding a solution of potassa, which gives with its salts a white gelatinous precipitate, soluble in an excess of the reagent.[R] [R] If the detection of alum in bread is desired, a portion of the crumb is incinerated in a platinum dish, the ash is treated with concentrated hydrochloric acid, the filtered solution evaporated to dryness, and the residue treated with hydrochloric acid, which now leaves the silica present undissolved. The acid solution is then filtered, nearly neutralized with carbonate of soda, and an alcoholic solution of potassa added in excess. The earthy phosphates present are now precipitated, alumina remaining in solution. The use of aqueous potassa in this case--as well as in the case mentioned in the text--is not advisable, as it is seldom entirely free from alumina. Upon slightly acidulating the alkaline filtrate with hydrochloric acid, and adding carbonate of ammonia, the alumina present is precipitated, and may be dried and tested by means of the reaction with nitrate of cobalt before the blow-pipe. In the quantitative estimation of alumina, the phosphoric acid usually present in the precipitate should be removed. This is done by dissolving the precipitate in nitric acid and immersing a piece of metallic tin in the boiling solution: phosphoric acid is thrown down as a mixture of stannic oxide and phosphate, and the alumina is then precipitated as usual by carbonate of ammonia.--_Trans._ _g. Sulphate of copper._--About 200 grammes of the bread under examination are incinerated; the ash treated with nitric acid; the mixture evaporated until it acquires a sticky consistence, and the mass then taken up with water. The aqueous solution is next filtered; an excess of ammonia and several drops of solution of carbonate of ammonia added; the fluid again filtered, the filtrate slightly acidulated with nitric acid, and divided into two parts. It is then ascertained if sulphuretted hydrogen produces in one portion of the solution a brown precipitate of sulphide of copper, and if solution of ferrocyanide of potassium produces in the other a reddish-brown precipitate of ferrocyanide of copper.[S] [S] According to Wagner, if the ash, obtained by incinerating the adulterated bread, is washed with water, shining spangles of metallic copper are separated.--_Trans._ FIXED OILS. Olive oil designed for table use is frequently adulterated with the oils of poppy, sesamé, cotton-seed, pea-nuts, and other nuts; olive oil, intended for manufacturing purposes, is often mixed with colza and nut oils. The tests used are of a rather unsatisfactory character. In all instances, when the chemist is called upon to pronounce as to the adulteration of an oil, it is necessary to execute comparative experiments with the pure oil, and with admixtures arbitrarily prepared: it is only when this is done that the indications obtained are of value. EXAMINATION OF OLIVE OIL INTENDED FOR TABLE USE. _a._ The density of the oil is determined by means of a hydrometer (_oleometer_) provided with a scale giving the densities from 0.8 to 0.94, for the temperature of 15.° Pure olive oil possesses a specific gravity of 0.917; poppy oil one of 0.925; a mixture of the two, an intermediate density. Since the fixed oils are not definite chemical compounds, this test is seldom conclusive. _b._ Two or three cubic centimetres of concentrated nitric acid, containing nitric peroxide in solution (or a solution of mercury in strong nitric acid), are added to the oil to be examined, as well as to a sample of pure olive oil. The two samples are then allowed to stand in a room where the temperature does not exceed 10.° The _oleine_ of the olive oil is converted into solid _elaidine_, and the mixture after some time becomes sufficiently thick to remain in the vessel upon inversion. If the sample under examination is free from adulteration, it will solidify at the same time as the pure oil; whereas, the presence of one per cent. of poppy oil, or of other drying oils, suffices to retard the solidification for forty minutes. _c._ Fifteen grammes of the oil are mixed in a glass vessel with the same amount of strong sulphuric acid, the temperature of the two liquids being previously observed. The mixture is stirred with a thermometer, and the maximum temperature noted: pure olive oil produces an elevation of temperature of 37.°7; pure poppy oil, an elevation of 70.°5; and a mixture of the two an elevation of temperature intermediate between 37.°7 and 70.°5. _d._ One volume of nitric acid of sp. gr. 1.33 is agitated with 5 grammes of the oil, and notice taken of the coloration produced after the lapse of five minutes. If the olive oil is pure, it acquires a pale green color; in case it is mixed with sesamé or nut oil, a deep-red color appears: poppy oil also communicates a reddish coloration, but one less deep than the preceding. If an acid of sp. gr. 1.22 is taken, it is still less difficult to distinguish between sesamé, nut and poppy oils; the latter assumes, in this case, a pale yellowish-red color. Pea-nut oil fails to exhibit a coloration; but can be recognized by its conversion into a white solid, when mixed with 1/5 of its volume of a solution of caustic soda of sp. gr. 1.34. EXAMINATION OF OLIVE OIL INTENDED FOR MANUFACTURING PURPOSES. The chief adulterations are colza and nut oils. The latter is detected by means of the reaction with nitric acid, as described above. Colza oil is recognized by mixing 5 volumes of the sample to be examined, with 1 volume of sulphuric acid of sp. gr. 1.655: if colza or nut oils are present, a brown coloration ensues; under the same circumstances, pure olive oil assumes a pale greenish hue. In case the sample acquires a brown color when treated with sulphuric acid, and a red coloration is produced by the addition of nitric acid, it contains nut oil; if sulphuric acid produces a brown coloration, and nitric acid fails to change it, the presence of oil of colza is indicated. EXAMINATION OF HEMPSEED OIL. This oil is frequently adulterated with linseed oil. The reactions exhibited by these oils are nearly identical, and the detection of the admixture is extremely difficult. It is advisable to mix the suspected oil with sulphuric acid, notice being taken of the elevation of temperature produced, and to treat it with nitric acid and with dilute potassa solution, subjecting, at the same time, an artificial mixture of the two pure oils to the same treatment, and comparing the results obtained. TEA AND ITS ADULTERATION. Among alimentary substances probably no article is subjected to more adulteration than tea. The sophistications practised may be conveniently divided into three classes: 1. Additions made for the purpose of giving increased bulk and weight, which include foreign leaves and exhausted tea-leaves, and also certain mineral substances, such as metallic iron, sand, brick-dust, etc. 2. Substances added in order to produce an artificial appearance of strength in the tea decoction, catechu, or other bodies rich in tannin, and iron salts being chiefly resorted to for this purpose. 3. The imparting of a bright and shining appearance to the tea by means of various coloring mixtures or "facings," which adulteration, while sometimes practised upon black tea, is much more common with the green variety. This sophistication involves the use of steatite (soap-stone), sulphate of lime, China clay, Prussian blue, indigo, turmeric, and graphite; chromate of lead and copper salts being but very rarely employed. The compound most frequently used consists of a mixture of soap-stone (or gypsum) with Prussian blue, to which a little turmeric is sometimes added. Genuine tea is the prepared leaf of _Thea sinensis_. It contains: moisture, 6% to 10%; theine, 0.4% to 4.0%; tannin, (green) 20%, (black) 10%; ash, 5% to 6%; soluble extractive matters, 32% to 50%; and insoluble leaf, 47% to 54%. [Illustration: Fig. 16.] [Illustration: Fig. 17.] [Illustration: Fig. 18.] [Illustration: Fig. 19.] The presence of foreign leaves, and, in some instances, of mineral adulterants, in tea is best detected by means of a microscopic examination of the suspected sample. The genuine tea-leaf is characterized by its peculiar serrations and venations. Its border exhibits serrations which stop a little short of the stalk, while the venations extend from the central rib, nearly parallel to one another, but turn just before reaching the border of the leaf (see Fig. 16). The Chinese are said to employ ash, plum, camellia, velonia, and dog-rose leaves for admixture with tea, and the product is stated to be often subjected in England to the addition of the leaves of willow, sloe, beech, hawthorn, elm, box-poplar, horse-chestnut, and fancy oak (see Figs. 17, 18, and 19). For scenting purposes chulan flowers, rose, jasmine, and orange leaves are frequently employed. In the microscopic examination the sample should be moistened with hot water, spread out upon a glass plate, and then submitted to a careful inspection, especial attention being given to the general outline of the leaf and its serrations and venations. Most foreign leaves will, in this way, be identified by their botanical character. The presence of exhausted tea-leaves may also often be detected by their soft and disintegrated appearance. If a considerable quantity of the tea be placed in a long glass cylinder and agitated with water, the coloring and other abnormal bodies present frequently become detached, and either rise to the surface of the liquid as a sort of scum or fall to the bottom as a deposit. In this way Prussian blue, indigo, soap-stone, gypsum, sand, and turmeric can sometimes be separated and subsequently recognized by their characteristic microscopic appearance. The separated substances should also be chemically tested. Prussian blue is detected by heating with a solution of caustic soda, filtering, and acidulating the filtrate with acid, and then adding chloride of iron, when, in its presence, a blue color will be produced. Indigo is best discovered by its appearance under the microscope; it is not decolorized by caustic alkali, but it dissolves in sulphuric acid to a blue liquid. Soap-stone, gypsum, sand, metallic iron, etc., are identified by means of the usual chemical tests. A compound, very aptly termed "Lie-tea," is often met with. It forms little pellets consisting of tea-dust mixed with foreign leaves, sand, etc., and held together by means of gum or starch. This, when treated with boiling water, falls to powder. In the presence of catechu the tea infusion usually becomes muddy upon cooling; in case iron salts have been employed to deepen the color of the liquor, they can be detected by treating the ground tea-leaves with acetic acid and testing the solution with ferrocyanide of potassium. Tea should not turn black upon immersion in hydrosulphuric acid water, nor should it impart a blue color to ammonia solution. The infusion should be amber-colored, and not become reddened by the addition of an acid. TEA ASSAY. In the following tea assay proper the estimation of theine is not included. The processes suggested for this determination are rather unsatisfactory; and there appears, moreover, to exist no direct relation between the quality of tea and the proportion of theine contained. The tests here mentioned, in connection with those already given, will, it is believed, usually suffice to indicate to the analyst the presence of spent leaves, inorganic coloring matters, and other mineral adulterations. TANNIN.--A good process for the estimation of tannin in tea has been published by Allen (_Chem. News_, vol. xxix. p. 169 et seq.) A standard solution of lead acetate is prepared by dissolving 5 grammes of the salt in distilled water and diluting the liquid to 1,000 c.c. As an indicator, 5 milligrammes of potassic ferricyanide are dissolved in 5 c.c. of water, and an equal volume of strong ammonia-water added. The exact strength of the lead solution is to be determined by means of a solution of pure tannin of known strength. Two grammes of the tea to be tested are powdered, boiled with water, and, after filtering and thorough washing, the decoction is made up to a volume of 250 c.c.; 10 c.c. of the lead solution are now diluted with 90 c.c. of boiling water, and the tea infusion is gradually added from a burette until a few drops of the liquid, when filtered and added to a little of the indicator placed upon a porcelain slab, causes a pink coloration to appear; 125, divided by the number of c.c. of tea infusion found to be necessary to produce the pink color, will give directly the percentage of tannin in the sample examined. As previously stated, green tea contains 20% of tannin, and black tea 10%. In spent tea, however, only about 2% of tannin is present; and, although any tea deficient in this constituent could be fortified by the addition of catechu, its determination often affords indications of value. THE ASH--_a. Total Ash._--5 grammes of the sample are placed in a platinum vessel and heated over a Bunsen burner until complete incineration has been accomplished. The vessel is allowed to cool in a desiccator, and is then weighed as quickly as possible. In genuine tea the total ash should not be much below 5% or much above 6%, and it should not be magnetic; in "faced" teas the proportion of total ash is often 10% or 15%; in "lie-tea" it may reach 30%, and in spent leaves it may fall as low as 3%, the ash in this case being abnormally rich in lime salts and poor in potash salts. Tea-dust sometimes contains 10% of total ash without necessarily being considered bad in quality. In the proposed United States tea-adulteration law (1884) a maximum of 8% of total ash is allowed for tea-leaf. _b. Ash insoluble in water._--The total ash obtained in _a_ is washed into a beaker and boiled with water for a considerable time. It is then brought upon a filter and the insoluble residue washed, dried, ignited, and weighed. In unadulterated tea it will not exceed 3% of the sample taken. _c. Ash soluble in water._--This proportion is obtained by deducting ash insoluble in water from the total ash. Genuine tea contains from 3% to 3.5% of soluble ash, or at least 50% of the total ash, whereas in spent or exhausted tea the amount is often but 0.5%. _d. Ash insoluble in acid._--The ash insoluble in water is boiled with dilute hydrochloric acid and the residue separated by filtration, washed, ignited, and weighed. In pure tea the remaining ash ranges between 0.3% and 0.8%; in "faced" teas, or in teas adulterated by the addition of sand, etc., it may reach the proportion of 2% to 5%. Fragments of silica and brick-dust are occasionally to be found in the ash insoluble in acid. THE EXTRACT.--Two grammes of the carefully-sampled tea are boiled with water until all soluble matter is dissolved, water being added from time to time to prevent the solution becoming too concentrated. The solution is poured upon a tared filter, and the remaining insoluble leaf repeatedly washed with hot water until the filtered liquid becomes colorless. The filtrate is now diluted to a volume of 200 c.c., and of this 50 c.c. are taken and evaporated in a weighed dish over the steam-bath until the weight of the extract remains constant; its weight is then determined. Genuine tea affords from 32% to 50% of extract, according to its age and quality; in spent tea the proportion of extract will be greatly reduced. INSOLUBLE LEAF.--The insoluble leaf obtained in the preceding operation, together with the weighed filter, is placed in an air-bath and dried for at least eight hours at a temperature of 110° C.; its weight is then determined. In unadulterated tea the amount of insoluble leaf ranges between 47% and 54%; in exhausted tea it may reach a proportion of 75%. It should be noted that in the foregoing estimations the tea is taken in its ordinary air-dried condition. If it be desired to reduce the results obtained to a dry basis, an allowance for the moisture present in the sample (an average of 8%), or a direct determination of the same, must be made. The following tabulation gives the constituents of genuine tea so far as the ash, extract, and insoluble leaf are involved: _Total ash_--ranges between 4.7% and 6.2%. _Ash soluble in water_--ranges between 3% and 3.5%; should equal 50% of total ash. _Ash insoluble in water_--not over 2.75%. _Ash insoluble in acid_--ranges between 0.3% and 0.8%. _Extract_--ranges between 32% and 48%. _Insoluble leaf_--ranges between 43% and 58%. The table below may prove useful as indicating the requirements to be exacted when the chemist is asked to give an opinion concerning the presence of facing admixtures or of exhausted or foreign leaves in a sample of tea: _Total ash_--should not be under 4.5% or over 7%. _Ash soluble in water_--should not be under 40% of total ash. _Ash insoluble in water_--should not be over 3%. _Ash insoluble in acid_--should not be over 1%. _Extract_--should not be under 30%. _Insoluble leaf_--should not be over 60%. NOTE.--The British Society of Public Analysts adopt: _Total Ash_ (dry basis)--not over 8% (at least 3% should be soluble in water). _Extract_ (tea as sold)--not under 30%. MILK. The chief constituents of milk are water, butter, caseine, lactose (milk-sugar), traces of albumen and mineral salts. Butter is present in the form of minute globules, held in suspension; the caseine, for the greater part, is in solution, only a small portion being present in an insoluble suspended condition. In milk only a few days old, the _colostrum_ (the milk secreted during the first few days after parturition) consists largely of rather voluminous cellular conglomerations, containing a sufficient quantity of albumen to coagulate upon heating. The normal density of milk is 1.030, water being 1.000; the density rising to 1.036, if the fluid has been skimmed. Good milk contains, on an average, 3.7 per cent. of butter; 5.7 per cent. of lactose, and leaves upon evaporation 12 to 14 per cent. of solid matters.[T] The most common adulteration of milk consists in the addition of water. This fraud is detected by means of an areometer (_lactodensimeter_) which gives directly the specific gravity of the fluid under examination. Should the density be much below 1.030, it is certain that water has been added. It does not, however, necessarily follow if it is about 1.030 that the milk is pure, since the gravity of the fluid, which would be increased upon skimming, could be subsequently reduced to 1.030 by the addition of water. The lactodensimeter, therefore, although useful in the detection of a simple admixture, fails to give reliable results if the fraud perpetrated is a double one; and a determination of the proportion of butter present is also usually necessary. Numerous methods have been proposed to accomplish this estimation. The most preferable of these, owing to the rapidity with which the operation is executed, is the use of the lactoscope (_galactoscope_). This instrument consists of a tube provided with a glass plate fitted at one end, and with a movable glass plate at the other extremity. A few drops of the milk to be tested are placed between the two plates, and the tube lengthened, by screwing out the movable plate, until the fluid no longer transmits the light of a candle placed at a distance of one metre. As the opacity of milk is due to the butter present, it is evident that the proportion of this substance contained in the sample can be estimated by the relative distance which the plates have been separated. [T] The British Society of Public Analysts regard the following as the _minimum_ proportions of constituents in unadulterated milk: Fat 2.5 per cent. Solids, not fat 9. " " ---- Total 11.5 " " Water 88.5 " " --_Trans._ The lactoscope possesses, however, but a limited degree of precision. _M. Marchand_ substitutes to its use the following tests: A test-tube is graduated in three equal divisions, the upper one being subdivided into hundredths extending above, in order to determine accurately the correct volume of the fluid, expanded, as it is, by the temperature of 40°, at which the examination is executed. The first division of the tube is filled with milk, a drop, or two of strong potassa lye added, and the mixture well shaken: the second portion is then filled with ether, and the third with alcohol. The mixture is next again thoroughly agitated, and then exposed to a temperature of 40° in a water-bath. After standing for several hours, a layer of fatty matter becomes sufficiently separated to allow of measurement: but, as it contains some ether and as a small amount of butter may still be retained in the lower aqueous fluid, a correction of the results obtained is necessary. M. Marchand has compiled a table, which facilitates this correction (_vide_: _Journ. de Pharm., Novembre 1854_, and _Bulletin de l'Académie de Médecine, Paris, 1854_, xix., p. 1101). Previously to the introduction of Marchand's apparatus, use was made of the _lactometer_, which consists simply of a graduated glass tube, in which the suspected milk is allowed to remain for 24 hours, at a temperature of 15°. After the lapse of this time, the cream present completely separates as a supernatant layer, the thickness of which indicates the quality of the sample taken. _M. Lacomte_ recommends the addition of glacial acetic acid, in order to cause the more rapid separation of the cream. The estimation of the butter being accomplished, it is frequently needful to determine the amount of lactose present. For this purpose, recourse is had to Barreswil's method, based upon the reduction of cupro-potassic tartrate by milk-sugar in the presence of alkalies. A solution is prepared containing 40 grammes of pure crystallized sulphate of copper, 600 or 700 grammes of caustic soda lye of sp. gr. 1.12, and 160 grammes of neutral tartrate of potassa. The sulphate of copper and tartrate of potassa are previously dissolved separately in a little water, the three solutions united, and water added until the fluid acquires a volume of 1154.4 cubic centimetres. In order to standardize this test solution, a known weight of pure lactose is dissolved in water and the fluid added, drop by drop, from a graduated burette, to a small flask containing 10 cubic centimetres of the copper solution, diluted with 40 cubic centimetres of distilled water, and heated to boiling. At first a yellow precipitate forms, which gradually turns red, and is deposited on the bottom of the flask, leaving the solution colorless. As soon as the test solution is completely decolorized, the addition of the lactose solution is discontinued, and the weight of lactose corresponding to 10 cubic centimetres of the test fluid calculated from the quantity used. The standard of the test solution having been determined, the above operation is repeated, the milk under examination being substituted for the solution of pure lactose. The quantity of milk necessary to decolorize 10 cubic centimetres of the copper solution will evidently contain the same amount of lactose as the quantity of solution used in the preliminary test, and the actual amount of lactose present is very easily calculated. When an estimation of the solid matter contained in the milk is required, a known weight is evaporated to dryness over a water-bath, and the residue weighed. In performing this evaporation, the addition of a known amount of sand, or ground glass, is advisable. The amount of ash present is determined by incinerating the residue left by the evaporation. Foreign substances are sometimes added to milk, for the purpose of disguising the presence of an abnormal quantity of water, the principal of which are: chalk, bicarbonate of soda, emulsion of almonds, gum tragacanth, gum arabic, starch, flour, decoction of barley or rice, sugar, and cerebral substances. These bodies are detected as follows: _Chalk._--If chalk is contained in the milk, it readily subsides upon allowing the sample to remain at rest for some time in a flask, forming a deposit which effervesces when heated with hydrochloric acid, and dissolves to a solution, in which the characteristic properties of a lime salt can be recognized. _Bicarbonate of soda._--In presence of this compound the milk possesses a strongly alkaline reaction, furnishes a serum having a sharp and bitter taste, and leaves a residue of the salt upon evaporation. _Emulsion of almonds._--The milk has a specific gravity of at least, 1.033. If it is passed through a gauze, small opaque lumps are separated. When examined under the microscope, numerous minute globules, having a diameter of 1/400 of a millimetre, are observed, and, upon adding a few centigrammes of amygdaline to one or two grammes of the milk, the characteristic odor of bitter almonds is produced. _Gum tragacanth._--When shaken in a glass flask and allowed to rest, the milk deposits on the sides small transparent lumps, which usually present a slightly elongated or angular form. _Gum arabic._--The addition of alcohol produces an abundant white opaque precipitate. _Starch, flour, decoction of barley, rice, etc._--Upon boiling the suspected milk, and adding tincture of iodine, the amylaceous substances present produce a blue coloration in the fluid. _Sugar._--If yeast is added, and the mixture allowed to stand for some time at a temperature of 30°, alcoholic fermentation ensues; under these circumstances, lactose does not undergo fermentation. _Cerebral substances._--Adulteration by these substances is probably of much less frequent occurrence than was formerly supposed. The admixture is detected by evaporating the milk to dryness, dissolving the residue in ether, evaporating the etherial solution, and fusing the second residue, which consists of fatty matters, with nitrate of potassa in a platinum crucible. The mass is then taken up with water, and chloride of barium added to the solution. If cerebral substances were contained in the milk, ether will dissolve the fatty matters present, the phosphorus of which is converted into a soluble phosphate by the calcination with nitrate of potassa and is thrown down as a white precipitate, upon the addition of a solution of chloride of barium. This test may be confirmed by a microscopic examination of the milk, when the peculiar appearance of cerebral matter will be detected.[U] [U] Fragments of nerves, and other organic structures, are frequently observed in this examination.--_Trans._ WINE. The most common adulteration to which wines are subjected is the addition of water: wines having a rich color are frequently mixed by the dealer with lighter wines, and the fraud consummated by adding water. The detection of this adulteration is somewhat difficult, as water is a normal constituent of wine. In Paris the following method is usually employed: As soon as the wine is confiscated, it is ascertained what kinds of wine are manufactured by the inculpated dealer, and a statement obtained from him, giving the proportions of alcohol, etc., contained in the various brands. A wine is then prepared, according to the information received, an estimation of the alcohol contained in the prepared sample made, and the results compared with those furnished by a similar examination of the suspected wine. In case the proportion of alcohol is less in the suspected wine than in the prepared sample, it is evident that a fraudulent adulteration has been committed. If, however, the quantity of alcohol is the same in both wines, it does not necessarily follow that the wine has escaped admixture, since this body may have been added after the adulteration with water. In addition to the estimation of alcohol, it is also necessary to determine the amount of cream of tartar (bitartrate of potassa) present, as the proportion of this salt would be sensibly decreased by the addition of alcohol and water to the wine. This fraud could, however, be disguised by subsequently adding the proper amount of cream of tartar. It is also well to ascertain if two equal quantities of the prepared sample and the wine under examination require the same amount of solution of hypochlorite of lime for decolorization. In case the suspected wine has been adulterated, the quantity of hypochlorite solution used will be less than the amount necessary to decolorize the prepared wine. Foreign coloring matter may be added by the adulterator, but this fraud is easily detected by adding potassa to the sample: if its coloration is natural, a green tint is produced; whereas, if foreign matter has been introduced, the wine assumes various other colors upon the addition of the alkali.[V] [V] _Cotlini_ (_Ann. du genie civil_, No. 3, 1873) states that the following reactions occur when artificially colored wines are heated with potassa: Pure wine no precipitate greenish hue Elderberry violet " Beet-sugar red " Logwood red violet-red " Privet violet-blue " Turmeric light-blue " According to _M. de Cherville_ (_Quar. Jour. Sc._), a bright violet coloration is produced in the above test, if litmus be present. Fuchsin is separated by treatment with subacetate of lead and addition of amylic alcohol (_Jour. de Ph. et de Ch. Mar. 1873_).--_Trans._ The indications furnished by the above test are rendered valueless, if the wine has been artificially colored by the addition of the coloring matter of grape-skins; but the execution of this fraud would require some knowledge of chemistry, and fortunately adulterators, as a class, are deficient in this branch of science. Another method for detecting the addition of water is based upon the fact that fermented liquors do not contain air in solution, but only carbonic acid; whereas, water dissolves oxygen and nitrogen. It is executed as follows: The wine to be tested is placed in a flask, the delivery-tube of which is also filled, and heated; the evolved gas being collected in a tube filled with mercury. In case the wine is pure, the disengaged gas will be completely absorbed by potassa; if, on the other hand, water has been added, an unabsorbed residue, consisting of oxygen and nitrogen, will remain. This test is useless in case water, through which a current of carbonic acid gas has been passed for a considerable time, has been employed. Under these circumstances, however, the presence of the gas would probably be detected by the taste of the wine, as well as by the estimation just mentioned, since the sample would invariably contain a larger proportion of the gas than the standard with which it is compared; indeed, it would be almost impossible to prepare a solution which contained exactly the proportion of carbonic acid ordinarily present in wine. It remains to mention the methods employed in determining the amount of alcohol and cream of tartar contained in wine. The alcometrical method usually employed is based upon the difference in density possessed by pure alcohol and by mixtures of alcohol and water. _Gay-Lussac_ has proposed an areometer (_alcoholmeter_), provided with a scale which directly indicates the proportion of alcohol contained in a mixture. As the indications furnished by this instrument vary with the temperature, and the scale is constructed on the basis of a temperature of 15°, a correction of the results obtained is necessary if the determination is made at other temperatures. Gay-Lussac has compiled a table which indicates at once the required correction; the following formula can also be used: _x = c ± 0.4 t_, where _x_ is the quantity of alcohol present in the sample; _c_ the degree indicated by the alcoholmeter, and _t_ the number of degrees differing from the temperature of 15°: the second member of the formula is subtracted from, or added to the first, as the temperature at which the estimation is made is greater or less than 15°.[W] [W] Tralles alcoholmeter is almost exclusively employed in this country.--_Trans._ In case the wine to be examined contains substances other than water and alcohol, which would affect its density, it is necessary, before making use of the alcoholmeter, to distil the sample and subsequently examine the distillate, which will consist of a simple mixture of water and alcohol. Usually the distillation is discontinued as soon as one-third of the sample has passed over, and a quantity of distilled water, sufficient to render the volume of the mixture equal to the original volume of the wine, added to the distillate: the fluid remaining in the flask will be entirely free from alcohol. The addition of water to the distillate is not indispensable, but otherwise it is necessary to divide the degrees indicated by the alcoholmeter by 3, in order to reduce the result to the original volume of the wine taken. _M. Salleron_ offers for sale a small apparatus (Fig. 20) used in examinations of this character, consisting of a flask, closed with a gutta-percha cork, containing a tube which connects with a worm passing through a cooler. The flask is supported by an iron stand, and heated with a gas or spirit lamp. [Illustration: Fig. 20.] In order to estimate the cream of tartar, the wine is evaporated to the consistency of an extract, alcohol of 82° B. added, and the residue obtained calcined in a crucible. The amount of salt present in the fused mass is then determined by the alkalimetric method, as directed in all works on quantitative analysis. The carbonate obtained from 1 gr. of cream of tartar exactly saturates 9.75 cubic centimetres of a solution containing 100 grammes of sulphuric acid of 66° B., and 1800 grammes of distilled water. The detection of toxical substances, often contained in wine, is accomplished by the methods described under the head of detection of poisons. VINEGAR. Vinegar is frequently adulterated with water, and occasionally sulphuric acid is added to artificially increase its acidity. The ordinary reagents--such as chloride of barium, or nitrate of silver--are not adapted to the direct detection of sulphuric acid, or of other mineral acids, as sulphates and chlorides, which are as readily precipitated as the free acids, may also be present. The following method, proposed by _M. Payen_, is usually employed: Five centigrammes of starch (fecula) are added to a decilitre of table vinegar, the mixture boiled for 12 or 15 minutes, and, after the fluid has become _completely cooled_, a few drops of iodine solution added: dilute acetic acid does not affect starch, and, in case the vinegar is pure, a blue coloration is produced; if, on the other hand, even a minute quantity of a mineral acid be present, the starch is converted into dextrine, and the addition of iodine fails to cause a blue coloration. The water present is indirectly estimated by determining the amount of acetic acid contained in the vinegar. This can be accomplished in different ways: either the quantity of a standard solution of an alkali, necessary to exactly neutralize a measured quantity of the vinegar, is ascertained, or the vinegar is supersaturated with solution of baryta, the excess of the salt eliminated by conducting carbonic acid through the fluid, the precipitate removed by filtration, and the baryta salt in the filtrate precipitated by the addition of sulphuric acid. The second precipitate is then collected on a filter, washed, weighed, and the amount of acetic acid present calculated: this is done by multiplying its weight by 0.515. SULPHATE OF QUININE. Owing to the high price of this salt, it is frequently adulterated. The substances used for this purpose are: crystalline sulphate of lime, boric acid, mannite, sugar, starch, salicine, stearic acid, and the sulphates of cinchonine and quinidine. These bodies are detected as follows: _a._ Upon slightly warming 2 grammes of sulphate of quinine with 120 grammes of alcohol of 21° B., the pure salt completely dissolves; if, however, starch, magnesia, mineral salts, or various other foreign substances are present, they are left as insoluble residues. _b._ Those mineral substances that are soluble in alcohol are detected by calcining the suspected sample: pure sulphate of quinine is completely consumed; whereas, the mineral substances present remain behind as a residue. _c._ In presence of salicine, the salt acquires a deep red color, when treated with concentrated sulphuric acid. _d._ Stearic acid remains undissolved upon treating sulphate of quinine with acidulated water. _e._ To detect sugar and mannite, the sample is dissolved in acidulated water, and an excess of hydrate of baryta added: a precipitate, consisting of quinine and sulphate of baryta, is produced. Carbonic acid is then passed through the fluid, in order to precipitate the excess of baryta as insoluble carbonate, the fluid saturated with ammonia, to throw down the quinine which may have been re-dissolved by the carbonic acid, and the mixture filtered. If the salt be pure, no residue will be obtained upon evaporating the filtrate; a residue of sugar or mannite is formed, if these substances are present. _f._ Sulphate of quinine invariably contains 2 or 3 per cent. of cinchonine, originating, not from a fraudulent admixture, but from an incomplete purification of the salt. One of the best methods for detecting the respective quantities of quinine and cinchonine, present in a sample of the sulphate, is the following: Several grammes of ammonia and ether (which has previously been washed with water) are added to one or two grammes of the salt under examination, the mixture thoroughly agitated, and then allowed to remain at rest. The supernatant etherial solution contains all of the quinine; the cinchonine, which is almost completely insoluble, both in water and ether, remaining suspended between the layers of the two fluids. The ether is next removed by means of a stop-cock funnel, evaporated to dryness, and the weight of the residue obtained determined. The operation is then repeated, the ether being replaced by chloroform in which both quinine and cinchonine are soluble. The residue, formed by the evaporation of the second solution, will be heavier than the first residue: the difference between the two weighings gives the weight of the cinchonine present. _g._ The detection of the presence of sulphate of quinidine is based upon the difference in the solubilities of the oxalates of quinine and quinidine. Oxalate of quinidine is sufficiently soluble in cold water not to be precipitated by double decomposition when solutions of oxalate of ammonia and sulphate of quinidine are mixed. Under the same circumstances, quinine is almost completely thrown down. The test is applied as follows: The suspected salt is dissolved in water, a slight excess of oxalate of ammonia added, and the precipitate formed separated by filtration. If the salt be pure, the filtrate is scarcely rendered turbid by the addition of ammonia; when, however, sulphate of quinidine is present, it will be entirely contained in the filtrate, in which ammonia will produce an abundant precipitate. EXAMINATION OF BLOOD STAINS. This branch of legal chemistry formerly gave but very unreliable results. It is scarcely ten years since the reactions that are now regarded as only secondary and confirmative in their character, and far from conclusive, were the only ones in use: these are the tests based upon the presence of iron and albumen in the blood. Since then, great progress has been made in the methods employed. It must not be understood, however, that the question under consideration always admits of an easy and decisive solution: the stains are sometimes too greatly altered to be identified; but in cases where the distinctive reactions of blood can be produced, the real nature of the stains under examination can, at present, be determined with certainty. The tests more recently introduced consist in the production of small characteristic crystals, termed _haemin_ crystals, and in the use of the spectroscope. Crystals of haemin (first discovered by _Teichman_) are formed when dry blood is dissolved in concentrated acetic acid, and the solution evaporated to dryness: they are of a brownish-red color. _Brücke_ first suggested an analytical method, based upon this property of blood, which is equally characteristic and sensitive: It is only necessary to dissolve a minute portion of the matter to be examined (dried blood, or the residue left by the evaporation of the fluid obtained by treating the stain, or the dried blood, with cold water) in glacial acetic acid and evaporate the solution to dryness in order to obtain crystals of haemin, which can be readily recognized by means of a microscope having a magnifying power of 300 diameters. If the crystals originate from fresh blood, they appear as represented in Fig. 21; crystals from old blood are represented in Fig. 22. [Illustration: Fig. 21.] [Illustration: Fig. 22.] The former possess a reddish-brown, the latter a lighter color. The various methods now employed to produce haemin crystals were proposed by _Hoppe-Seyler_, by _Brücke_ and by _Erdman_. Whichever process is used, the suspected stains are at first carefully separated from the material upon which they are deposited. If they are present on linen, or other fabrics, the stained portions, which always remain somewhat stiff, are cut off: they will present a reddish-brown color, in case the cloth is not dyed: if the stains are on wood, they are removed by means of a sharp knife; if on stone or iron, they are detached by scraping. In case Hoppe-Seyler's method is used, the stains, separated as directed above, are macerated with a little _cold_ water (warm water would coagulate the albumen present, and consequently prevent solution taking place): the stains become soft, striae and brown or reddish clouds are observed, especially when the dried blood is fresh, and, at the same time, the objects upon which the stains were deposited are decolorized. Upon allowing the fluid obtained in this way to spontaneously evaporate on a watch-glass, a reddish brown or brownish residue is left, from which the crystals of haemin are prepared in the following manner: An almost imperceptible amount of common salt is added to the residue, then, six to eight drops of concentrated acetic acid, and the mass thoroughly mixed by stirring with a small glass rod. The mixture is at first heated over a small gas flame, then evaporated to dryness by the heat of a water-bath. If the stains were produced by blood, a microscopic examination of the residue will reveal the presence of haemin crystals. This method presents an objection: if the stained objects have been washed with warm water previously to the examination, the albumen will be coagulated, and the blood rendered insoluble; in this case, cold water will fail to dissolve anything, and the residue will not produce crystals when treated with acetic acid. In order to remedy this difficulty Brücke operates directly upon the stained woven or ligneous fibre, or the matter removed from the stone or iron: The materials are boiled in a test-tube with glacial acetic acid, the fluid decanted or filtered, a trace of common salt added, and the liquid then evaporated on a watch-glass at a temperature between 40 and 80°. If the stains really originated from blood, haemin crystals will now be easily perceptible upon examining the residue obtained under the microscope. The stained fabric, the matter removed from the stone or iron, or the residue left by the solution with which the stains have been treated, is placed on the glass, a trace of chloride of sodium added, and the whole covered with a thin glass plate. A drop of acetic acid is then placed at the edge of the plates--between which it is soon introduced by capillary attraction--and the mixture allowed to rest in the cold for a few moments. The mass is next brought into solution by slightly heating, and is then evaporated by holding the plate at a considerable distance above a gas burner. The fluid is examined from time to time under the microscope: when it is sufficiently concentrated, crystals, presenting the appearance represented in Figs. 21 or 22, will be observed. These are especially well-defined, if an insoluble substance is also present between the plates--which prevents their adhering. The fluid collects by capillary attraction at the points of contact of the plates as a more or less colored layer, in which the crystals are deposited. Should the above test fail to present distinctive indications at first, one or two fresh drops of acetic acid are introduced between the plates, and the examination is repeated. The result is not to be regarded as negative, until several trials have proved fruitless, as the stained portions are but slowly soluble, and crystallization may have been prevented by the too rapid evaporation of the acetic solution. Haemin crystals, once seen, can hardly be confounded with other substances; still, it is well to identify them by confirming their insolubility in water, alcohol, and cold acetic acid, as well as their instantaneous solubility in soda lye. The addition of common salt is ordinarily superfluous, as it is normally contained in the blood; but it is possible, if the stains were washed with warm water, that, in addition to the coagulation of the albumen, the solution of the salt may have taken place, in which case crystals will fail to form. The addition of salt is to remedy this possible contingency; albeit, the delicacy of the test is not affected, even if crystals of chloride of sodium are produced, as these are easily soluble in water, and are readily distinguished from those of haemin by aid of the microscope. The indications furnished by means of the spectroscope are less reliable than those given by the production of haemin crystals; moreover, the spectroscopic examination requires favorable weather for its execution. Still, the test should be employed in all possible instances. The course pursued is the following: The aqueous fluid, with which the stains have been treated, is placed in a watch glass, and evaporated _in vacuo_ over sulphuric acid; the last remaining portion of the fluid being united in the bottom of the glass by causing it to collect in a single drop. When the evaporation of fluid is completed, the watch-glass is placed before the narrowed slit of a spectroscope, and a ray of diffused light (or better, light reflected from a heliostat) made to pass through the part of the glass containing the residue. If the stains originate from blood, the absorption lines of _haemoglobin_, consisting of two large dark bands, to the right of the sodium line (_Frauenhofer's_ line D), will be observed in the spectrum. In case both of the above tests fail to give positive results, it is almost certain that the stains examined were not caused by blood. If, on the contrary, the reactions were produced, scarcely any doubt exists as to the presence of blood. Under these circumstances it is advisable to confirm the results by means of the tests that have been previously spoken of as being formerly exclusively employed; these are the following: _a._ 1/2 to 1 c. c. of ozonized oil of turpentine, _i. e._ turpentine which has been exposed to the air sufficiently long to acquire the property of decolorizing water that is slightly tinted with indigo--is introduced in a test-tube, and an equal volume of tincture of guaiacum added (the latter tincture is prepared by treating an inner portion of the resin with alcohol, until its brownish color is changed to a brownish-yellow). If upon adding some of the substance under examination to the above mixture a clear blue coloration ensues, and the insoluble matter thrown down possesses a deep blue color, the presence of coloring matter of the blood is indicated. The mixture also imparts a blue color to moistened spots from which the blood stains have been as completely extracted as possible. Unfortunately sulphate of iron gives the same reaction.[X] [X] Fresh gluten, gum arabic, and caseine also cause the blue coloration.--_Trans._ _b._ Upon heating the fluid obtained by treating the stains with cold water in a test-tube, its brown or reddish color disappears, and greyish-white flakes of coagulated albumen are thrown down. The precipitate acquires a brick-red color, when treated with an acid solution of nitrate of mercury containing nitrous acid. The albumen is also coagulated by the addition of nitric acid: it assumes a more or less yellow color, if heated with a slight excess of the acid. Chlorine-water, especially upon heating, likewise precipitates albumen in the form of white flakes. _c._ If the fluid is acidulated with a few drops of acetic acid, and a drop of ferrocyanide of potassium added, a white precipitate, or, at least, turbidity is produced. _d._ The flakes of albumen, separated by heating, dissolve in caustic alkalies to a solution, from which they are re-precipitated by nitric acid, or chlorine water. _e._ Upon treating blood stains with chlorine-water, a solution which contains chloride of iron, and acquires a red coloration by the addition of sulphocyanide of potassium, is formed. _f._ Should the stains have failed to be affected by cold water (which, as has already been remarked, is the case when they have been previously washed with hot water), they are treated with weak soda lye. Nitric acid, hydrochloric acid, and chlorine water will produce in the solution so obtained a white precipitate, which exhibits the general properties of albumen previously described. In case the stains are deposited upon linen, it is necessary to replace the soda by ammonia, in order to avoid dissolving the fabric. _g._ Solutions of the alkalies, which dissolve the albumen, leave the coloring matters intact, and consequently do not decolorize the fabric. If the latter is afterwards subjected to the action of hydrochloric acid, the coloring matter is dissolved, forming a solution that leaves upon evaporation to dryness a residue containing iron, which gives a blue coloration with ferrocyanide of potassium, and a red coloration with sulphocyanide of potassium. _h._ The coloring matter of blood dissolves in boiling alcohol, to which sulphuric acid has been added, to a brown dichroic fluid (appearing green by transmitted light, and red by reflected light). A mixture of rust and blood exhibits the same phenomenon. _i._ If substances containing blood are heated in a dry tube, an odor resembling that of burnt horn is emitted. In case the stained fabric is a substance that would produce this odor, (such as wool, silk, or hair), the test naturally loses all value. _j._ If the fluid obtained by treating the stains either with water or alkali is evaporated with a little carbonate of potassa, and the residue heated, at first at 100°, then to redness, in a glass tube to which a fresh quantity of carbonate of potassa has been added, cyanide of potassium is formed. When cold, the tube is cut above the part containing the fused mixture, the mass heated with iron-filings and water, the fluid filtered, and the filtrate then acidulated with hydrochloric acid: ferrocyanide of potassium will be present in the fluid, and upon adding a drop of solution of perchloride of iron a green, or blue, color will be produced, and a precipitate of Prussian blue gradually thrown down. If the stained cloth is non-nitrogenous (_per ex._: hemp, linen, or cotton), instead of treating it with water, it may be heated until pulverulent, mixed with carbonate of potassa, the mixture calcined, and the operation then completed as just described. This test having given affirmative results, the operations should be repeated with an unstained portion of the cloth, to remove all doubt that the indications obtained do not really originate from the fabric. In the present state of science, it is impossible to discriminate chemically between human and animal blood. _M. Barruel_, it is true, is able, not only to accomplish this, but also to distinguish the blood of the various species of animals by its odor! But this test has a somewhat hypothetical value for scientific purposes. In regard to the crystals of haemin, they do not present sufficient difference to allow the blood of different animals to be distinguished. We have not yet treated of the globules. It often occurs that these minute organs are so altered as to be no longer recognized in the microscopic examination; when, however, the stains are tolerably recent, they may be detected by examining the moistened stained cloth, directly under the microscope: a discrimination between animal and human blood is then possible: corpuscules of human blood possess the greater size: those of the sheep, for instance, have only one-half the diameter of the former. It is, however, but seldom that this distinction can be made use of.[Y] [Y] _Menstrual blood_ is recognized by the presence of epithelial cells.--_Trans._ EXAMINATION OF SPERMATIC STAINS. In cases where attempt at violence, rape or pederasty is suspected, the expert may be required to determine the nature of stains found on clothing, sheets, etc. The fact that the stains were produced by semen, may often be regarded, _per se_, as criminating evidence. This class of investigation possesses, therefore, considerable importance. _External appearance of the stains._--Dry spermatic stains are thin, and exhibit a greyish or, occasionally, a citron-yellow color, if present on white cloth. In case the fabric is colored, they appear whitish and, if on linen, present a glossy aspect. They are translucid, when observed by transmitted light. If the fabric, upon which the stains are deposited, is of a heavy texture, they are visible only on one side: under all circumstances, their circumference is irregular and undulated. These indications, however, are not conclusive, but vary according to whether the stains were produced by the thick semen of a vigorous man, or the aqueous seminal fluid of an aged and diseased person, or by semen more or less mixed with the prostatic fluid. Upon moistening spermatic stains, the distinctive stale odor of fresh semen is sometimes emitted, but this characteristic is usually obscured by the presence of foreign substances. Semen stains are soluble in water, forming a gummy fluid, in which chlorine, alcohol, bichloride of mercury, acetate and subacetate of lead produce a white precipitate, but which fails to be coagulated by heating. Plumbate of potassa does not impart a fawn-color to these stains, at a temperature above 20°, as is the case with those produced by albuminous substances. Persulphate of iron imparts to spermatic stains a pale yellow color, Sulphate of copper, a bluish grey color, Cupro-potassic tartrate, a bluish grey color, Nitrate of silver, a pale grey color, Nitric acid, a pale yellow color. The above reactions, separate or united, are insufficient; they are not very delicate, and are likewise produced by stains originating from the other varieties of mucus: the indications furnished by a microscopic examination of the stains are alone conclusive. _Microscopic examination._--Semen contains as its principal and fecundating constituent, peculiar vibratory filaments, (_spermatozoa_), held suspended in a viscous fluid. These filaments, when preserved in a warm and moist place, retain their activity for a considerable time: it is even possible that they may exhibit vitality in the organs, into which they have been voluntarily or forcibly ejaculated, for ten, or even twenty-four hours. When exposed to cold air, the spermatozoa quickly expire; still, they preserve their form for some time, and, as this is very characteristic, it is then easy to identify them; moreover, since they originate exclusively in the testicles, their detection may be considered as certain evidence of the presence of semen. In stains produced by aged persons, and by persons enfeebled by excesses, the spermatozoa fail to be presented; in case they are discovered, this fact evidently does not affect the certainty of the spermatic origin of the stains. The contrary conclusion is never absolutely certain: still, if the use of the microscope fails to establish the presence of spermatozoa, it is almost certain that the stains were not produced by semen. Of the various methods for obtaining from the stains a preparation adapted to the microscopic examination, the one proposed by M. Charles Robin is the most simple and reliable. A strip, 1 c. c. in size (comprising the entire stain, if this be small, containing its inner portion, if it be large), is cut from the fabric under examination, care being taken that the two extremities of the sample extend beyond the stained portion. One end of the cloth is then immersed in a capsule, or watch-glass, containing pure water: the stains become moistened by capillary attraction, and, in a space of time varying from twenty minutes to two hours, acquire the appearance of fresh semen. As soon as the stained portion becomes swollen and softened, the surface of the cloth is gently scraped with a spatula, and the substance removed placed on the slide of the microscope. The particles are next slightly detached, a drop of water added, if necessary, and the whole covered with a small plate of very thin glass. The preparation is then examined by a microscope, having a magnifying power of from 500 to 600 diameters. In this way, the presence of either entire or broken spermatozoa is readily detected. Their existence is rendered still more apparent, if the mucus present is dissolved by adding a drop of acetic acid to the preparation. Entire spermatozoa consist of long slender filaments, having a length of 0.04041 to 0.04512 millimetre; the anterior extremity presents an oval enlargement, either round or pyriform, exhibiting a double outline, when magnified to 500 diameters. This enlarged end is termed the "head;" the entire remaining portion being regarded as the "tail." In case the spermatozoa are broken, they are severed either near the head or in the middle of the tail, and a mass of detached fragments will be observed in the microscopic examination. The spermatozoa are not the only corpuscules revealed by the microscope; other substances, entirely different in character, are often observed. Although the detection of these bodies is, in itself, of no value, it will be well to enumerate and characterize them; they are: _a._ Oily globules. _b._ Leucocytes, or spherical and finely granulous globules of mucus. _c._ Corpuscules, originating from the seminal vesicles, termed sympexions. These are rounded or ovoid, possess an irregular outline, and are usually mixed with the spermatozoa and globules of mucus. _d._ Crystals of phosphate of magnesia, varying greatly in size; the largest are from 0.mm. 001 to 0.mm. 002 in length. The crystals formed upon cooling the semen, present the form of an oblique prism, with a rhomboidal base. Occasionally they are elongated and flattened; they then assume the form of a rhomboid. _e._ Epithelial cells; originating from the mucous follicles of the urethra. _f._ Irregular grains of dust; soluble in acetic and hydrochloric acids, with gaseous evolution. _g._ Brownish-red grains of rust; only slightly soluble in acetic acid, but easily soluble in hydrochloric acid. _h._ Filaments of the strained fabric; detected by their texture, and general appearance. _i._ Grains of starch, in case the cloth has been stiffened. These are almost invariably swollen, and are frequently broken and deformed. If the examination is to be secretly executed, and the cloth cannot well be cut, it is rolled in a cone, in such a way that the external side contains the stained portion. The lower extremity of the cone (which should be free from stains) is dipped in a watch-glass containing water, so as to avoid directly wetting the stains. The cone soon becomes moistened by absorption, and the operation is then completed in the same manner as when the fabric has been cut; which is always preferable, when possible. The examination of spermatic stains consists, then, in moistening the stains with water, separating them as completely as possible from the stained cloth, and determining the presence of the spermatozoa by means of the microscope. All other tests are valueless; even their execution for confirmatory purposes is not advisable; inasmuch as they fail to possess a distinctive character, and the reagents employed in their production may destroy the fabric, and thus prevent the formation of the only conclusive reaction--the detection of the spermatozoa. In case the stains are deposited upon a woman's chemise, they are usually present on both the front and back portions, and are sometimes to be found on the sleeves. When a man's shirt is under examination, especial attention should be given to the anterior portions. The pantaloons are also often stained; usually in the interior, but sometimes also on the exterior, just above the thighs. In reporting the decision to the court, as to the nature of the stains, their precise position should invariably be stated, as, by this means, the circumstances attending the commission of the crime may be, at least partially, elucidated. THE END. APPENDIX. The following list of the literature of toxicology, and its allied branches, will, it is hoped, be of service to those readers who are desirous of obtaining further information on the subjects treated in this work.--_Trans._ BOOKS. *Accum*; A treatise on adulteration of food, and culinary poisons. London, 1822. *Adrien*; Recherches sur le lait au point de vue de sa composition, de son analyse, de ses falsifications et surtout de l'approvisionnement de Paris. Paris, 1859. *Angell and Hehner*; Butter; its analysis and adulterations. London, 1874. *Anglada*; Traité de toxicologie. Paris, 1835. *Atcherly*; Adulteration of food. London, 1874. *Bandein*; Die Gifte und ihre Gegengifte. Basel, 1869. *Beck*; Elements of medical jurisprudence. Albany, 1851. *Bellini*; Lezionis perementali di Tossicologia. Firenze, 1865. *Bergman*; Zur Kentniss der putriden Gifte. Dorpat, 1868. *Bernard*; Leçons sur les substances toxiques. Paris, 1857. *Billard*; Considerations medico-légale sur les empoisonnements par les irritants. Paris, 1821. *Blondlot*; Sur la recherche de l'arsenic par la methode de Marsh. Nancy, 1857. _Ibid_; Sur la recherche toxicologique du phosphore par la coloration de la flamme. Nancy, 1861. _Ibid_; Sur le dosage de l'antimoine dans les recherches toxicologiques. Nancy, 1865. *Boettcher*; Ueber Blutkrystalle. Dorpat, 1862. *Bonsels*; Ein Beitrag zur Analyse des Arsens, vorzugsweise in gerichtlichen Fällen. Kiel, 1874. *Borie*; Catechisme toxicologique. Tuelle, 1841. *Bouchardt et Quevenne*; Du lait. Paris, 1857. *Bowman and Bloxam*; Medical chemistry. London, 1874. *Briand et Chaudé*; Manuel complet de médicine légale; contenant un manuel de chimie légale. Paris, 1873. *Buchner*; Toxikologie. Nüremburg, 1859. *Bureaux*; Histoire des falsifications des substances alimentaires. Paris, 1855. *Chapman*; Manual of Toxicology. London, 1853. *Chatin*; Recherches experimentals et considerations sur quelques princips de la toxicologie. Paris, 1844. *Chiaje*; Tossicologia. Napoli, 1835. *Chaussier*; Médicine légale. Paris, 1858. *Chevalier*; Dictionaire des alterations et falsifications des substances alimentaires, médicamenteuses et commerciales, avec l'indication des moyens de les reconnaitre. Paris, 1856. _Ibid_; Essais practiques sur l'examen chimique des vins, considéré sous la rapport judiciaire. Paris, 1857. *Christison*; A treatise on poisons. Edinburg, 1836. *Collier*; Paradoxology of poisoning. London, 1856. *Cooper*; Tracts on medical jurisprudence. Phila., 1819. *Cormenin*; Memoire sur l'empoisonnement par l'arsenic. Paris, 1842. *Cotter*; Adulteration of liquors. N. Y., 1874. *Cottereau*; Des alterations et des falsifications du vin, et des moyens physiques et chimiques employés pour les reconnaitre. Paris, 1851. *Cox*; Poisons; their effects, tests and antidotes. London, 1852. *Culbrush*; Lectures on the adulteration of food, and culinary poisons. Newburg, 1823. *Dalton*; Adulteration of food. London, 1857. *Divergie*; Médicine légale. Paris, 1852. *Dragendorff*; Beiträge zur gerichtlichen Chemie einzelner organischen Gifte. St. Petersburg, 1872. _Ibid_; Untersuchungen aus dem pharmaceutischen Institut in Dorpat. St. Petersburg, 1872. _Ibid_; Manuel de toxicologie; traduit par E. Ritter. Paris, 1873. *Druitt*; On wines. London, 1866. *Duflos*; Die wichtigsten Lebenbedürfnisse, ihre Aechtheit und Güte; Verunreinigungen, Verfälschungen, etc. Breslau, 1846. _Ibid_; Die Prüfung chemischer Gifte. Breslau, 1871. _Ibid_; Handbuch der angewandten gerichtlich-chemischen Analyse der chemischen Gifte; ihre Erkennung in reinem Zustand und in Gemischen betreffend. Leipzig, 1873. *Duflos u. Hirsch*; Das Arsen; seine Erscheinung, u. s. w. Breslau, 1842. *Dupasquier*; Consultation medico-légale relative à une accusation d'empoisonnement par le plomb. Lyon, 1843. *Erhard*; Die giftigen pflanzenalkaloiden und deren Ausmittelung auf mikroskopischem Wege. Passau, 1867. *Eulenberg*; Die Lehre von den schädlichen und giftigen Gasen. Braunschweig, 1849. *Flandin*; Traité des poisons. Paris, 1852. *Flandin et Danger*; De l'arsenic. Paris, 1853. *Fop*; Adulteration of food. London, 1855. *Fraise*; Alimentation publique; le lait, ses falsifications, etc. Nancy, 1864. *Frank*; Manuel de toxicologie; traduit de l'allemand par Vrankan. Anvers, 1803. *Fresenius*; Auffindung unorganischen Gifte in Speisen, u. s. w. Braunschweig, 1856. *Friedrich*; Die Verfälschung der Speisen und Getränke. Münster, 1859. *Galtier*; Traité de toxicologie. Paris, 1855. *Galtier de Claubry*; De la recherche des alcalis organiques dans les cas d'empoisonnement. Paris, 1862. *Ganeau*; Alterations et falsifications des farines. Lille, 1856. *Garnier*; Des falsification des substances alimentaires et des moyens de les reconnaitre. Paris, 1844. *Gerhardt*; Précis d'analyse pour la recherche des alterations et falsifications des produits chimiques et pharmaceutiques. Paris, 1860. *Garland*; Précis d'analyse chemique qualitative. Paris, 1855. *Gmelin*; Allgemeine Geschichte der thierischen und mineralischen Gifte. Erfurt, 1806. *Gorup-Besanez*; Anleitung zur qualitativen und quantitativen zoochemischen Analyse. Braunschweig, 1871. *Gosse*; Des taches, au point de vue medico-légale. Paris, 1862. *Griffin*; The chemical testing of wines and spirits. London, 1872. *Griffith and Taylor*; A practical manual of the general, chemical, and microscopical character of the blood, etc. London, 1843. *Guerin*; Nouvelle toxicologie. Paris, 1826. *Guy*; Principles of forensic medicine. London, 1843. *Gwosden*; Ueber die Darstellung des Hämin aus dem Blut und den qualitativen Nachweis minimaler Blutmengen. Wien, 1866. *Hager*; Untersuchungen. Leipzig, 1873. *Hartung-Schwarzkoff*; Chemie der organischen Alkalien. München, 1855. *Hassall*; Adulteration of food. London, 1855. *Van Hassett*; Handbuch der Giftlehre. Braunschweig, 1862. *Helwig*; Das mikroskop in der Toxikologie. Mainz, 1864. *Herman*; Lehrbuch der experimentellen Toxikologie. Berlin, 1875. *Hitzig*; Studien über Bleivergiftung. Berlin, 1870. *Hoffman*; Manual of chemical analysis. N. Y., 1873. *Hoppe-Seyler*; Handbuch der physiologisch und pathologisch chemischen Analyse. Berlin, 1870. _Ibid_; Medicinisch-chemische Untersuchungen. Berlin, 1871. *Horsley*; The toxicologist's Guide. London, 1866. *How*; Adulteration of food and drink. London, 1855. *Huseman*; Handbuch der Toxikologie. Berlin, 1870. *Jaillard*; De la toxicologie du bichromate de potasse. Strasbourg, 1861. *Jones (H. Bence)*; Chemistry of wines. London, 1874. *Klincke*; Die Verfälschung der Nahrungsmittel, Getränke, etc. Leipzig, 1858. *v. Kupffer*; Handbuch der Alkoholometrie. Wien, 1866. *de Lapparent*; Les moyens de constater la pureté des principales huiles fixes. Cherbourg, 1855. *Lefort*; Etudes chimiques et toxicologiques sur la morphine. Paris, 1861. *Legrand*; Traité de médicine légale et de jurisprudence médical. Paris, 1873. *Letheby*; On food. N. Y., 1872. *Lerwin*; Toxikologischen Tabellen. Berlin, 1856. *Liebreich*; Outlines of Toxicology. London, 1875. *Lindes*; Beiträge zur gerichtlichen Chemie. Berlin, 1852. *Lunel*; Guide pratique pour reconnaïtre les falsifications et alterations des substances alimentaires. Paris, 1874. *Malle*; Essai d'analyse toxique génerale. Strasbourg, 1838. *Marset*; Composition, adulteration, and analysis of food. London, 1856. *Marshall*; Remarks on arsenic. London, 1817. *Marx*; Geschichtlich Darstellung der Giftlehre. Göttingen, 1829. *Mata*; Tratado de medicina y cirugia legal. Paris, 1874. *Mayercon and Bergeret*; Recherches sur la passage de l'arsenic et de l'antimoine dans les tissus et les humeurs. Paris, 1874. *Meissner*; Aräometrie in ihrer Anwendung auf Chemie und Technik. Wien, 1816. *Mitchell*; Falsification of food. London, 1848. *Mohr*; Chemische Toxikologie. Braunschweig, 1874. *Monier*; Memoires sur l'analyse de la lait et des farines. Paris, 1858. *Montgarney*; Essai de toxicologie. Paris, 1818. *Muller*; Anleitung zur Prüfung der Kuhmilch. Bern, 1858. *Münk und Leyden*; Phosphorvergiftung. Berlin, 1865. *Neubauer*; Chemie des Weines. Wiesbaden, 1874. *Neuman*; Die Erkennung des Bluts bei gerichtlichen Untersuchungen. Leipzig, 1869. *Normandy*; The commercial hand-book of chemical analysis. London, 1875. *Odling*; A course of practical chemistry. London, 1872. *Oesterlen*; Das menschliche Haar und seine gerichtärtliche Bedeutung. Tübingen, 1875. *Orfila*; Rapport sur les moyens de constater la presence de l'arsenic dans les empoisonnements par ce toxique. Paris, 1841. _Ibid_; Traité de médicine légale. Paris, 1848. _Ibid_; Elements de chimie médicale. Paris, 1851. _Ibid_; Traité de toxicologie. Paris, 1852. *Otto*; Anleitung zur Ausmittelung der Gifte, und zur Erkennung der Blutflecken bei gerichtlich-chemischen Untersuchungen. Braunschweig, 1870. *Payen*; Substances alimentaires. Paris, 1856. *Pelliken*; Beiträge zur gerichtlichen Medizin, Toxikologie und Pharmakodynamik. Würztburg, 1858. *Petit Lafitte*; Instruction simplifiée pour la constatation des propriétées des altérations et des falsifications des principales, denrées alimentaires. Bordeaux, 1858. *Plaff*; Anleitung zur vornahme gericthlicher Blutuntersuchungen. Plauen, 1860. *Pierce*; Examination of drugs, chemicals, etc. Cambridge, 1852. *Planta*; Verhaltung der wichtigsten Alkaloiden gegen Reagenten. Heidelberg, 1846. *Pleck*; Toxicologia. Viennae, 1801. *Prescott*; Chemical examination of alcoholic liquors. N. Y., 1875. *Preyer*; Die Blutkrystalle. Jena, 1871. *Reese*; A manuel of Toxicology. Phila., 1874. *Reveil*; Introduction à un cours de toxicologie. Paris, 1859. *Reyer*; Die Blausäure physiologisch untersucht. Bonn., 1868. *Rich*; The analyst's annual note-book for 1874. London, 1875. *Ritter*; Ueber die Ermittelung von Blut, Samen und Excrementenflecken in Kriminalfällen. Würztburg, 1854. _Ibid_; Beiträge zur gerichtlichen Chemie. St. Petersburg, 1872. _Ibid_; Manuel de chimie practique, analytique, toxicologique et zoochimique. Paris, 1874. *Robinet (fils)*; Manuel practique d'analyse chimique des vins. Paris, 1872. *Rebuteau*; Elements de Toxicologie et de médecine légale appliquée à l'empoisonnements. Paris. 1873. *Roucher*; Recherches toxicologiques. Paris, 1852. *Roussin*; Falsification des vins par l'alun. Paris, 1861. *Ryan*; Medical Jurisprudence. London, 1836. *Schmidt*; Ein Beitrag zur Kentniss der milch. Dorpat 1874. *Schmidt*; Diagnostik verdächtlicher Flecken. Leipzig, 1848. *Schneider*; Die gerichtliche Chemie. Wien, 1852. *Schroff*; Toxikologische Versuche über Arsen. Wien, 1858. _Ibid_; Beiträge zur Kentniss des Aconite. *Simon*; Die Frauenmilch. Berlin, 1838. *Sonnenkalb*; L'Aniline et ses couleurs, au point de vue toxicologique. Leipzig, 1864. *Sonnenschein*; Ueber ein neues Reagent auf Alkaloiden. Berlin, 1857. _Ibid_; Handbuch der gerichtliche Chemie. Berlin, 1869. *Soubeiran*; Nouveau Dictionnaire des falsifications et des alterations des aliments, etc. Paris, 1874. *Speyer*; Recherche de la colchicine. Dorpat, 1870. *Spratt*; Toxicology. London, 1843. *Stowe*; A toxicological chart. London, 1872. *Tanner*; Memoranda on Poisons. London, 1872. *Tardieu*; Etude medico-légale sur l'empoisonnement. Paris, 1866. *Tardieu, Lorain et Roussin*; Empoisonnement par la strychnine, l'arsenic, et les sels de cuivre. Paris, 1865. *Tatra*; Traité d'empoisonnement par l'acide nitrique. Paris, 1802. *Taylor*; Poisoning by strychnine. London, 1856. _Ibid_; On poisons, in relation to medical jurisprudence and medicine. London, 1859. _Ibid_; A manual of medical jurisprudence. Phila., 1873. _Ibid_; The principles and practice of medical jurisprudence. Phila., 1873. *Thompson*; Medical jurisprudence. London, 1831. *Traill*; Medical jurisprudence. Phila., 1841. *Trommer*; Die Kuhmilch in Berzug auf ihre Verdünnung und Verfälschung. Berlin, 1859. *Valser*; Etude sur la recherche, les caractères distinctifs, et la dosage des alcaloïdes organiques naturels. Paris, 1862. *Vernois*; Du lait chez la femme dans l'etât de santé et dans l'etât de maladie. Paris, 1858. *Vogel*; Eine neue Milchprobe. Stuttgart, 1860. *Walchner*; Die Nahrungsmittel des menchens, ihre Verfälschungen und Verunreinigungen. Berlin, 1875. *Walther*; Ueber Erkennung des Arsens bei Arsenvergiftung. Bayreuth, 1854. *Wanklyn*; Milk Analysis. London, 1874. *Wenke*; Das Bier und seine Verfälschung. Weimar, 1861. *Werber*; Lehrbuch der praktischen Toxikologie. Erlangen, 1870. *Wharton and Stille*; Medical Jurisprudence. Phila., 1855. *Wickler*; Toxikologische Briefe. Weimar, 1852. *Wirthgen*; Die verschiedenen Methoden zur ermittelung von Blutflecken in forensischen Fallen. Erlangen, 1861. *Witting*; Uebersicht der wichtigsten Erfahrungen in der Toxikologie. Hannover, 1827. *Wöhler und Liebold*; Das forensisch-gerichtlichen Verfahren bei einer Arsenvergiftung. Berlin, 1847. *Wood*; Therapeutics, materia medica and Toxicology. Phila., 1874. *Wormely*; The micro-chemistry of Poisons. N. Y., 1867. *Wurtz*; Chimie médicale. Paris, 1868. *Zalewsky*; Untersuchung über das Conin. Dorpat, 1869. MEMOIRS. On poisons generally and those not elsewhere classified. *Accum*; Ed. month. Rev. iii, 276; Quar. Rev. xxiv, 341; Ed. Rev. xviii, 370. *Andrews*; Sill Am. Jour. [2] xlvii, 25. *Bouis*; Compt. rend. lxxiii. *Bunsen*; Ann. Ch. Pharm. cvi, 1. *Brunner*; Archiv. der Pharm. ccii, 4. *Cossa*; Gaz. Med. di Lomb., 1863. *Diakanow*; Med. Chem. Unters. ii, 144. *Duflos u. Millon*; Ann. Chem. Pharm. xlix, 308. *Elliot and Storer*; Am. Jour. Pharm., Sept., 1860 *Joubert*; Compt. Rend., No. 26. *Moitessier*; Annal d'Hygiene, 1868. *Orfila*; Mem. de l'acad. roy. de méd. viii. 493. *Otto*; Ann. chem. Pharm. c., 39. *Pellissie*; Jour. de Pharm. et de chim., Jan., 1874. *Reveil*; Compt. Rend. lx, 433. *Reynolds*; The Irish Hosp. Gaz. Feb. 15, 1873. *Selmi*; Gaz. Chim. Ital. 1874. fasc. I, ii. *Stein*; Polyt. Centralb., 1866, p. 1023 and 1870, pp. 1035, 1209. *Vierchow*; Arch. f. path. anat. xxi, 444. On the destruction of organic matter. *Brande*; Arch. f. Pharm. xlviii, 206. *Buchner*; N. rept. f. Pharm. xvii, 21. *Fresenius*; Zeitsch. f. anal. Chem. 1 Jahrg, 447. *Fype*; Jour. f. prakt. Chem. lv, 103. *Graham*; Phil. Mag. [4] xxiii. *Liebig*; Chem. Centbl., 1857, v. 357. *Ludwig*; Arch. f. Pharm. xcvii, p. 23. *Schacht*; Arch. f. Pharm. lxxvi, 139. *Schneider*; Jahrb. der Chem. 1851, 630. *Sonnenschein*; Deutsche Klinik, 1867, No. 3. *Wurtz*; Am. Jour. Sci. [2] xi, 405. On the detection of Arsenic. *Avery*; Sill Am. J. [2] xlvii, 25. *Barker*; Am. Chem. June, 1872. *Becker*; Arch. f. Pharm. xlvi, 287. *Bettendorff*; Zeitsch. f. Chem. v. 492, 592. *Blondlot*; Jahresb. 1863, 681; Compt. Rend. July 7, 1845. *Bloxam*; Jahresb. f. Chem. 1860. 645; Chem. Soc. Q. Jour. xiii, 14, 138. *Brescius*; Ding. poly. Jour., clxxxvi, 226. *Buchner*; Rept. f. Pharm. xii. *Christison*; Lond. and Edinb., Jour. Med. Sc., Sept., 1843; Med. Recorder, Apr., 1827. *Davy*; Jahresb., 1858, 609. *Draper*; Dingl. poly. Jour. cciv. 385. *Elliot and Storer*; Sill. Jour. 32, p. 380. *Erlenmeyer*; Zeitsch. f. Ch. u. Pharm. 1862, 38. *Feuchtwanger*; Sill. Jour. xix, 339. *Franck*; Zeit. f. anal. Chem. iv. 201. *Fresenius*; Arch. f. Pharm. lxii, 57; Ann. der Chem. u. Pharm. xliii. 361; ibid, xlix, 275; Zeits. f. anal. Chem. vi, 196; ibid ii, 19; ibid i. 483; Qual. Chem. Anal. p. 346. *Fresenius u. v. Baho*; Pogg, Anal. vol. xc, 565; Ann. Chem. Pharm. xlix, 287. *Fype*; Phil. mag. ii 487; Jour. f. prakt. Chem. lx. 103. *Gatehouse*; Chem. News. No. 699, 1873. *Gaultier de Claubry*; J. Pharm. [3] xxii, 125. *Graham*; Ann. Chem. Pharm. cxxi, 63: Elements of Chem. 2nd. edit. vol. ii, 215. *Gray*; Chem. News, v. 23 p. 73. *Hager*; Pharm. Zeitsch. 1870, No. 27: Ding. poly. Jour. vol. 207, No. 6; Centralhalle xiii, 195. *Hasson*; Compt. Rend, lxvii, 56. *Houzeau*; Ding. poly. Jour. Bd. 207, Heft. 2, 3. *Hume*; Phil. Mag. Sept. 1812, 109. *Keber*; Viertlj. f. gerichtl. Med. ix. 96. *Kirschgassner*; J. f. prakt. Chem. lxviii. 168; Jahresb., 1860, 170. *Lippirt*; J. f. prakt. Chem. lxviii, 168; Jahresb., 1860, 170. *Lois*; Oest. Zeitsch. f. prakt. Heilkunde, xlix, 1859. *Mayer*; Pharm. Zeitsch. Russ. 2 Jahrgang. *Meyer*; Ann. Chem. u. Pharm., lxvi. *Montmeja*; La France Méd., Jan. 8, 1873. *Odling*; Guys. Hosp. Rep. [3] v. 367; Zeitsch. f. anal. Chem. ii. 388. *Pearson*; Sill, Am. J. [2] xlviii, 190. *Puller*; Zeitsch. f. anal. Chem. x, 52. *Rose*; Pogg. Annal., vol. xc; Zeitsch. f. anal. Chem. i, 418; Chimie Anal. Paris, 1859, p. 405. *Roussin*; Jahresb. 1866, 801. *Saikowski*; Arch. f. path. Anat. xxxi, 400. *Selmi*; Dent. Chem. Gess. Ber. 1872, 477. *Schafer*; Jour. f. prakt. Chem. lxxxii, 286. *Schneider*; Wien. Akad. Ber. 1851, vi, 409 *Sklarek*; Arch. f. Anat. u. Phys. 1866, 481. *Slater*; Chem. Gaz. 1851, 57. *Sonnenschein*; Arch. f. Pharm, cxciii, 245: ibid. [2] cxliii, 250. *Taylor*; Guys. Hosp. Rep. ii, 83; ibid. vi; Pharm. Zeitsch. f. Russl. 10, Jahrg. 129. *Ugers*; Ann. Chem. Pharm. clix, 127. *Ures*; Dict. Arts, etc., new edit, i, 189. *Vitry*; Annal d'hygiène publ. xxxvi, 14. *Wackenroder*; Arch. f. Pharm. lxx, 14. *Watt's* Chem. Dict. i, 365; Supp. 215. *Werther*; J. pr. Chem. lxxxii, 235; Jahresb. 1861, 851. *Wiggers*; Canstatt's Jahresb. der Pharm. 1864. *Wittstein*; Zeitsch. f. anal. Chem. ii, 19. *Wohler*; Ann. der Chem. u. Pharm. lxix, 364; Mineral Analyse, Göttingen, 1861, 213. *Wood and Doremus*; N. Y. Med. Press, 1859, 543. *Zenger*; Zeitsch. f. Ch. Pharm. 1862, 38; Jahresb. 1862, 595. On the detection of Antimony. *Bellini*; Jhb. f. Pharm. 1868, p. 453. *Bottger*; Chem. Centralbl., 3 Jahrgang. *Bunsen*; Ann. Chem. Pharm. cvi, p. 3. *Hofman*; Ann. Chem. Pharm. p, 155; Chem. Soc. Quar. J. xiii, 79. *Millon and Levaran*; Compt. Rend. 21. *Odling*; Guys Hosp. Rep. [3] ii, 249. *Pfaff*; Pogg. Ann. f. Phys xl, 339. *Thompson*; Jour. f. prakt. Chem. ii, 369. *Vogel*; ibid, xiii, 57. On the detection of Mercury. *Buchner*; N. rept. f. Pharm. xvii, 272. *Erdman and Marchand*; Jour. f. prakt. Chem. xxxi. *Hittdorf*; Pogg. Annal. cvi. *Konig*; Jour. f. prakt. Chem. lxx. *Mayencon and Bergeret*; Jour. de l'Anat. et de la Physiol. 1873, No. 1; Jour. de Pharm. et de Chim., Aug., 1873. *Schneider*; Ber. d. Wien, Akad. d. Wiss. xl. *Wormley*; Chem. News, ii, No. 43. On the detection of Phosphorus. *Barrett*; Phil. Mag. [4] xxx, 321. *Blondlot*; Jour. de. Phy. et de Chim. 3 é serie xl, p. 25. *Bostelaer*; Jour. de Pharm. et de Chim., May, 1873. *Christoffle and Beilstein*; Ann. de Chim. v, iii, p. 80. *Dalmon*; Zeitsch. f. anal. Chem. 1871, 132. *Dusard*; Zeitsch. f. anal. Chem. i, 129; Compt. rend. xliii, 1126. *Ferrand*; La France med., Jan. 18, 1873. *Fresenius and Neubauer*; Zeitsch. f. Anal. Chem. i, 366. *Hager*; Zeitsch f. anal. Chem. 1870, 465. *Hoffman*; Jahresb. 1859, 663. *Klewer*; Pharm. Zeitsch. f. Russl., 386. *Kohler*; Poly. centralh., 1871, 263. *Lapeyrere*; La France méd., Jan. 4, 1873. *Lefort*; Jour. de Pharm. et de Chim., Aug., 1874. *Lispowitz*; Ann. f. Phys. u. Pharm. cviii, 625. *Mistcherlich*; Jour. f. prakt. Chem. lxvi, 238. *Mulder*; Arch. f. d. holl. Zeit. ii, 4; Zeitsch. f. Anal. Chem. ii, 3. *Otto*; Zeitsch. f. Chem. [2] ii, 733. *Pribram*; Zeitsch. f. anal. Chem. 1871, 109. *Ritter*; Thése de doctorat es sciences, Paris, 1872. *Scherer*; Ann. Ch. Pharm. cxii, 214. *Schieffendecker*; Zeitsch. f. anal. Chem. 1872, iii. *Schom*; Zeitsch. f. anal. Chem. [2] v, 664. *Wiggers*; Canstatt's Jahresb. f. Pharm. 1854. On the detection of Prussic Acid. *Almen*; Chem. Centralb., 1871, 797. *Bonjean*; Compt. rend. lxx, 532. *Braun*; Zeitsch. f. anal. Chem. iii, 464. *Duvignan and Parent*; Am. Med. Rec. 1819, 534. *Hagenbach*; Arch. f. path. Anat. xl, 125. *Hoppe-Seyler*; Vierschow's Arch. f. path. Anat 38. *Jacquemin*; Compt. rend. lxxxix, 1499, 1502. *Letheby*; Lond. Lanc. 1844, 244; ibid, vol. 2, p. 139. *Ralph*; N. Jahresb. f. Pharm. xxx, 179. *Rennard*; Pharm. Zeitsch. f. Russl. xii, No. 8. *Schonbein*; Zeitsch. f. anal. Chem. 1868, 503. *Siegel*; Arch. f. Heilkunde, 1858. *Struve*; Zeitsch. f. anal. Chem. 1873, i; Mon. Scien. Ques. Juin, 1874, 538. *Taylor*; Ann. Ch. Pharm. lxv, 263. On the detection of Alkaloids in general. *Anderson*; Pharm. Centralbl., 1848, 591. *Armstrong*; J. Chem. Soc., v. 8, p. 56. *Back*; Jour. f. prakt. Chem. Nos. 5-6, 1873. *Beas*; Jour. de Phys. et de Chim., Sept. 1872. *Bolton*; (trans. of the Stas-Otto method) Am. Chem., Nov., 1873. *Bonnemains*; Compt. Rend. xxxvi, 150. *Bouchardt*; Ann. de Phys. et de Chim., 3e série. t. ix. *Brunner*; Archiv der Pharm., April, 1873. *Buignet*; Jour. de Pharm. et de Chim. t. xx, 252. *Deane and Brady*; Chem. Soc. J. [2] iii, 34. *Deefs*; N. Jahresb. f. Pharm. ii, 31; Wittstein's Viertelj. vi. *Dragendorff*; Pharm. Zeitsch. f. Russl. ii, 459; Archiv der Pharm. May, 1874. *Erhard*; N. Jahresb. f. Pharm. xxv, 129, 193, 283; ibid, xxvi, 9, 129. *Ewers*; Pharm. Zeitsch. f. Russl. xii, No. 23. *Graham and Hofman*; Chem. Soc. Qu. J. v, 173; Pharm. J. Trans. xi, 504; Ann. Ch. Pharm. lxxxiii, 39. *Grandean*; Bull. Soc. Chim. [2] ii, 74. *Guy*; Pharm. Jour. ii, pp. 553, 602; ibid, iii, pp. 11, 112. *Hagers*; Chem. Ctbl., 1869, 131. *Horsley*; Chem. News, v, 355 *Huseman*; Ann. Chem. Pharm. cxxviii, 305. *Kletzinsky*; Mitthel. v. d. Geb. d. rein. u. angew. Chem. 1865. *Kohler*; Archiv der Pharm. Mar. 1873. *Kuhne*; Ann. Chem. Pharm. vol. civ. *Lefort*; Zeitsch. f. anal. Chem. i, 134. *Lehrman*; Archiv der Pharm. 2 Bd. lxxvi, 144. *Liebig*, Poggendorff u. Wohler; Handwörterb. d. Chem. 2 Aus. i, 464. *Macadams*; Pharm. Jour. Trans. xvi, 120, 160. *Marchattie*; Chem. News. x, 183. *Marme*; Bull. Soc. Chim [2] ix, 203; Zeitsch. f. rat. Med. 1867. *Mayer*; Jour. de Pharm. et de Chim., Oct. 1873; Oest Zeitsch. f. Pharm. ii, 232. *Nowak*; Dingls. poly. Jour., vol. 206, p. 422; Sitzber. d. Wiener Akad. d. Wissensch., 1872. *Otto*; Ann. Ch. Pharm. c, 39. *Orfila*; Jour. de. Chim. et Méd. [4] t. vii, 397. *Palm*; Pharm. Zeitsch. f. Russl. i, Jahxgang. *Pierce*; J. Chem. Soc., Nov. 1874. *Prollius*; Chem. Centralbl., 1857, 231. *Ritter*; Pharm. Zeitsch. f. Russl. 5-6 Jahrg. *Rodgers and Girdwood*; Jahresb. v. Liebig u. Kopp, 1857, 603; Pharm. Jour. Trans. xvi, 497. *Rorsch and Fasbender*; Deut. Chem. Gess. Ber. xii, 1064. *Scheibler*; Jahresb. 1863, 702; Arch. f. Pharm. lix; Jour. f. prakt. Chem. lxxx, 211. *Schneider*; Ann. Chem. Pharm., von Poggendorff, No. 9. *Schrage*; Archiv der Pharm., Dec., 1874. *Schroof*; Apothet. Jahrg., ix, 148. *Schulze*; Ann. Ch. Pharm. cxix, 177. *Schwanert*; Deut. Chem. Gess. Ber., No. 14, 1874. *Sonnenschein*; ibid, civ, 45. *Stas*; Bull. de l'Acad. Roy. de Méd. de Belgique, xi, 304 (1851); Ann. Ch. Pharm., lxxxiv, 379, J. Pharm. Chim., xxii, 281; Jahresb., 1851, 640; Jour. f. prakt. Chem., lix, 232. *Struve*; Zeitsch. f. anal. Chem., No. 2, 1873. *Thomas*; ibid, vol. i, 317. *v. Uslar and Erdman*; Ann. der Chem. u. Pharm., 120, p. 121; 122, p. 360. *de Vrij and van der Burg*; Jahresb. v. Liebig u. Kopp, 1857, 602. *Watts*; Chem. Dict., vol. i, p. 125. *Wagner*; Fresen. Zeitsch. f. anal. Chem., iv. On Atropine. *Brunner*; Archiv der Pharm., April, 1873. *Calmberg*; ibid. Nov., 1874. *Gulielmo*; Zeitsch. f. anal. Chem., ii, 404. *Helwig*; Wiener Akad. Ber. vii, 433. *Koppe*; Pharm. Zeitsch. f. Russl., 5 Jahrgang. *Pelikan*; ibid, 1 Jahrgang. *Wormley*; Chem. News, vol. ii, June, 1860. On Brucine. *Cotton*; Zeitsch. f. Chem. [2] v. 728. *Helwig*; Zeitsch. f. anal. Chem., iii, 43. *Luck*; Zeitsch. f. Chem. [2] vi, 275. *Mayer*; Rep. Chim. app., v, 102. *Strecker*; Ann. Ch. Pharem., xci, 76. *Trapp*; Jahresb. 1863, 702. *Wormley*; Chem. News, vol. ii, July, 1860. On Morphine. *Anderson*; Ann. Ch. Pharm., lxxv, 80. *Dupre*; Chem. News, viii, 267; Jahresb., 1863, 704. *Erdman*; Ann. Ch. Pharm. cxx, 88; ibid, cxxii, 360. *Flandin*; Compt. rend., xxxvi, 517. *Frohde*; Zeitsch. f. anal. Chem. v, 214; Arch. f. Pharm., clxxvi. *Huseman*; Ann. Ch. Pharm., cxxviii, 305. *Kalkbrunner*; Zeitsch. d. all. Oest. Apot. Ver., No. 27. *Lassaigne*; Ann. Ch. Pharm. [2] xxv, 102. *Lefert*; J. Pharm. [3] xl, 97. *Mermer*; J. Chim., xxiii, 12. *Wormley*; Chem. News, vol. ii, Sept., 1860. On Strychnine. *Bingley*; Chem. Gaz., 1856, 229. *Brieger*; Jahresb. pr. Pharm. xx, 87. *Cloetta*; Zeirsch. f. anal. Chem., v, 265. *Davy*; J. Pharm. [3] xxiv., 204. *Djurberg*; Chem Centralb., 1872, 153; Zeitsch. f. anal. Chem., 1872, 440. *Eboli*; Archiv der Pharm., cxxxv, 186. *Erdman and Marchand*; Jour. f. prakt. Chem., xxxi, 374. *Gorup-Besenez*; Handwörterb. [2] i, 468. *Graham and Hofman*; Pharm. Trans., xi, 504; Chem. Gaz., 1852, 197; Ann. Ch. Pharm., lxxxiii, 39. *Hagen*; Ann. Ch. Pharm. ciii, 159. *Hunefeld*; Schw., lx. 454. *Janssen*; Zeitsch. f. anal. Chem., 4 Jahrgang. *Jordan*; N. Repert., x, 156. *Letheby*; Pharm. J. Trans. xvi, 10. *Mack*; N. Br. Arch., xlvi, 314. *Marchand*; Chem. Gaz., June 15, 1844. *Mayer*; J. Pharm. [3] xlvi. *Reese*; Chem. News. 1862, 316. *Rousseau*; J. Chim. Méd. xx, 415. *Sonnenschein*; Jahresb. 1870, 1032; Ber. d. Deutsch. Chem. Gess. iii, 653. *Schroder*; N. Br. Arch., xciii, 190. *Thomas*; Amer. Jour. Pharm. 1862, 227. *Thompson*; Pharm. J. Trans., ix., 24. *Vogel*; N. Repert. Pharm., ii, 560. *de Vrij and van der Burg*; Pharm. J. Trans. xvi, 448. *Wagner*; Kopp's Jahresb., 1861, 857; Zeitsch. f. anal. Chem., vi, 387. *Wittstein*; Pharm. Viertelj., vi, 273. *Wormley*; Am. Jour. Sc. and Arts., xxviii, Sept., 1859. On the detection of Falsifications of Writings. *Lucas*; Chem. Centralb., 1868, 1517. *Knecht-Senefelder*; Technol., xxvi, 143. *Moride*; Compt. rend., lviii, 367; Ding. poly. Jour. clxxii, 390. *Vorwerk*; Ding. poly. Jour., clxxii, 158. *----*; Berl. ind. Z., 1864, 41. On the detection of adulterations in Flour and Bread. *Barral*; Compt. rend., lvi, 834. *Bastelaer*; Chem. Centralb., 1868, 1342. *Cailletet*; ibid, 1858, 1392. *Corput*; ibid, 1860, 207. *Crooks*; Chem. News., vol. xxxiii, 73. *Danckwort*; Archiv der Pharm. [2] xx, 47. *Davis*; Chem. News, xxv., 207. *Eulenberg and Vohl*; Poly. Centralb., cxcvii, 530. *Gobley*; Jour. de Pharm., April, 1844. *Hadon*; Chem. News, 1862. *Hager*; Ding. Poly. Jour., clxxiii, 159. *Harsley*; Archiv der Pharm., July and Dec., 1873; Chem. News, xxv, 230. *Moitessier*; Annal. d'Hygiene, 1868. *Odling*; J. Soc. Arts, April 9, 1858. *Oser*; Ding. poly. Jour., clxxxiii, 256. *Rivot*; Ann. de Phys. et de Chim., 3e série t, xlvii. *Rummel*; Ding. poly. Jour., cxxxix, 49. *Tasbender*; Ding. poly. Jour., No. 6, ccvi. *Wanklyn*; Archiv der Pharm., Dec., 1873; Chem. News, xxxiii, No. 736; Ber. Med. Jour., March 29, 1873. On the examination of Fatty Oils. *Behrens*; Ding. poly. Jour., cxxxi, 50. *Calvert*; Pharm. J. Trans., xiii, 356. *Clarke*; Chem. News, xxiii, 145. *Dingl*; Poly. Jour., clxxiv. *Donny*; Bull. Soc. d'Erc, 1864, 372; Jahresb., 1864, 734. *Dragendorff*; Pharm. Zeitsch. f. Russl., ii, 434. *Fluckiger*; Chem. Centralb., 1871, 55. *Glassner*; (trans.) Am. Chem., Dec., 1873. *Gobley*; J. Pharm. [3], iv, 285; ibid. v. 67. *Jacobson*; Bull. Soc. Chim., [2] vii, 96. *Langlies*; Zeitsch. f. anal. Chem., 1870, 534. *Ludwig*; Archiv der Pharm., [3] i, 1. *MacNaught*; Chem. Centralb., 1862, 742. *Massie*; Zeitsch. f. anal. Chem., 1871, 495. *Maumene*; Compt. rend., xxxv, 572. *Nickles*; Bull. Soc. Chim., [2] vi, 89 *Penot*; Bull. de Mullh., xxvi, 7; Jahresb., 1866, 827. *Roth*; Bull. de Mullh., 1864, 104. *Ure's* Dict. of Arts, etc., iii, 300. *Vogel*; Chem. Centralbl., 1863, 945. *Watt's* Dict. of Chem., iv., 182. On the examination of Milk. *Boussingault*; Ann. Chem. Phys. [4] xxv, 382. *Baumhauer*; J. pr. Chem., lxxxiv, 145. *Casselman*; Chem. Centralb., 1863, 689. *Dancer*; Chem. News, v, 21, p. 51. *Daubrawa*; Jour. f. prakt. Chem., lxxviii, 426. *Donne*; Compt. rend., xvii, pp. 585, 591. *Filhol and Joly*; Wurtz's Dict. de Chim., t. ii, p. 195. *Gmelin*; Handb. der Chem., viii, [2] 246-273. *Heeren*; Chem. Centralb., 1870, 304. *Hermstaedt*; Pharm. Centralb., 1833, 401. *Kletzinsky*; Chem. Centralb., 1861, 244. *Lade*; Chem. Centralb., 1858, 144. *Leconte*; ibid, 1854, 1465. *Lehman*; Lehrb. der Phys. Chem., 1863, ii, pp. 287, 301; (trans. by Day) ii, pp. 449, 475. *Macadams*; Am. Chem., May, 1875, 419. *Marchand*; Jour. de Pharm., Nov., 1854. *Michaelson*; Ding. poly. Jour., cxlix, 59. *Millon*; Compt. rend., lix, 396. *Muller*; Zeitsch. f. anal. Chem., No. 3, 1872. *Otto*; Ann. Chem. Pharm., cii, 47. *Pelouze and Fremy*; Traité de Chim. gen., [2 edit.] Paris, 1857, p. 195. *Pribram*; Dings. poly. Jour., cxcvii, 448 *Reichelt*; Bayr. K. u. Gwbl., 1859, 602. *Reineck*; Ding. poly. Jour., cci, 433. *Rosenthal*; Chem. Centralb., 1854, 1392. *Seely*; Sill. Am. J., vii, 293. *Vernois and Becqueret*; Ann. d'Hygiéne, April, 1853. *Voelcker*; Am. Chem., May, 1875, p. 412. *Vogel*; Poly. Notizbl., No. 10, 1874. *Wanklyn*; Pharm. Viertelj., xx, 201: Milk Jour., 1, 109, 160; Chem. News, xxviii, No. 623; ibid, No. 736; Pharm. Journ. Trans., [3] i, 605. On the detection of adulteration in Wine and Beer. WINE. *Beck*; Edinb. Phil. Jour., 1835. *Berthelot and Fleurien*; Compt. rend., lvii, 394. *Blume*; Dings. poly. Jour., clxx, 240. *Bolly and Paul*; Manual of Tech. Anal., p. 331. *Boyer and Coulet*; Compt. rend., lxxvi, 585. *Brande*; Phil. Trans., 1811. *Cotlini*; Ann. du Genie Civil, No. 3, 1873. *Cotlini and Fantazini*; Ann. di Chim. Appl. alla Medi., Juli, 1870. *Christison*; Edinb. Phil. Jour., 1838. *Diez*; Ann. Ch. Pharm., xcvi, 304. *Duclaux*; Ann. de Chim. et de Phys., July and Sept., 1874; Compt. rend. lxxviii, 1159. *Duffield*; Am. Jour. Pharm., Mar. 1862. *Dupre*; Chem. Soc. Jour. xx, 493. *Fantenelle*; J. Chim. Méd., iii, 332. *Faure*; J. Pharm., vii, 200. *Fischern*; Ann. Chem. Pharm., lviii, 705. *Fresenius*; ibid, lxiii, 384. *Geiger*; Mag. f. Pharm., xix, 266. *Geromont*; Ann. Ch. Pharm., xvii, 158. *Hager*; Zeitsch. f. anal. Chem., 1872, 337. *Hitchcock*; Edinb. Phil. Jour., xxxvii, 176. *Jacquemin*; Ann. de Chim. et de Phys. v, série, Nov., 1874; Compt. rend., lxxix, 523. *Kersting*; Ann. Ch. Pharm., lxx, 50. *Khol*; J. Chim. Méd., [4] ii, 251. *Liebig, Poggendorff and Wohler*; Handwörterb. ix, 676. *Ludersdorf*; J. f. prak. Chem., xxiv, 102. *Maisch*; Proc. Am. Pharm. Assn., 1863, 296; 1864, 291; 1866, 267. *Mallard*; J. Chim. Méd., iii, 326. *Maumene*; Bull. Soc. Chim., xxii, No. 1. *Miller*; Jour. de Pharm. et de Chim., Mar., 1873. *Mitis*; Baierisch. K. u. Gewerbeblatt, 1838. *Phipson*; Zeitsch. f. anal. Chem., ix, 121. *Reiman's* Farb. Zeit., Nos. 14-15, 1874. *Romei*; Mon. Scien., iii, t. iii, No. 382. *Salleron*; Compt. rend., lxxviii, No. 16. *Scheitz*; Arch. Pharm., [3] v, 331. *Schubert*; Pogg. Annal., lxx, 397. *Sestini*; Landwirthsch. Ver. Stat., xv, 9. *Tuchschmeidt*; Jahresb., 1871, 967. *Zierl*; Baierisch. Kunst. Gewerbebl, 1838. BEER. *Blas*; Viertelj. f. prakt. Pharm., xxi, 584. *Brunner*; Archiv der Pharm., April, 1873; Dings. poly. Jour., ccix, No. 6; Jour. de Pharm. et de Chim., Sept., 1873; Poly. Nolizblatt, No. 17, 1873. *Dietz*; Neues Jahresb. f. Pharm., xxxix, No. 1. *Dragendorff*; Archiv. der Pharm., April and May, 1874; Dings. poly. Jour., ccxiv, pp. 33, 389. *Dullo*; Wieck's Gaz., 1865, 64. *Gunckel*; Arch. f. Pharm., clxiv. *Kubinki*; Le Technol, No. 397; (trans.) Amer. Chem., Nov., 1874; Dings. poly. Jour. ccxi, 360. *Langley*; Chem. Centralb., 1865, 184. *Meme*; Compt. rend., 2me sem., No. 123. *Michælis*; Ill. Gewerbz., 1871, 8. *Muspratt's* Chem. i, 281. *Pohl*; Wiener Akad. Ber., xii, 88. *Ritter*; Pharm. Zeitsch. f. Russl., i, pp. 304, 414. *Shafhauel*; Ding. poly. Jour., cxxxii, 299. *Schmidt*; Jour. f. prakt. Chem., lxxxvii, 344. *Stolber*; ibid, xciv, iii. *Ure's* Dict. Chem., 4th edit., 1831, p. 203. *Vogel and Hammon's* Mitth., 1860, 184. *Wittstein*; Archiv der Pharm., Jan. 1875. On the testing of Vinegar. *Bussy and Buignet*; Jahresb., 1865, 69. *Greville*; Ding. poly. Jour., cxxxi, 139. *Liebig, Poggendorff and Wohler*; Handwörterb, ii, 867. *Mohr*; Ann. Ch. Pharm., xxxi, 277. *Mollerat*; Ann. Chim., lxviii, 88. *Nicholson*; Ding. pol. Jour., cxxxix, 441. *Otto*; Ann. Chem. Pharm., cii, 69. *Roscoe*; Chem. Soc. Jour., xv, 270. *Runge*; Gewz. Bayer. 1871, 4. *Strohl*; Jour. de Pharm. et de Chim., Sept., 1874. *Toorn*; Jour. f. Chem., vi, 171. *Wagner*; Chem. Tech., (English trans.) p. 467. *Williams*; Pharm. J. Trans., xiii, 594. On the detection of adulterations in Sulphate of Quinine. *Delondre and Henry*; J. Pharm., [3] xxi, 281. *Gmelin's* Handbuch, xvii, 280. *Guibourt*; J. Pharm., [3] xxi, 47. *Henry*; ibid, xiii, 107. *Hesse*; Ann. Ch. Pharm., cxxxv, 325; Jahresb., 1865, 441. *Korner*; Zeitsch. f. Chem., J. i, 150; Jahresb. 1862, 619. *Phillips*; Lond. Lanc., i, 820. *Riegel*; Jahresb. f. Pharm., xxv, 340. On the detection of Blood Stains. *Barruel*; Ann. d'Hygiéne pub., i. 267; ibid, No. 6, 1829. *Bertolet*; Am. Jour. Med., Sc., Jan., 1874. *Brucke*; Jahresb., 1857, 609. *Van Deen*; Zeitsch. f. anal. Chem., ii, 459. *Erdman*; Jour. pr. Chem., lxxxv, 1; Jahresb., 1862, 634. *Falck*; Ber. Klinisch. Wochb., 1872. *van Geuns and Gunning*; Zeitsch. f. anal. Chem., 1871, 508. *Gwosden*; Wiener Akad. Ber., liii, [2] 683; Jahresb., 1866, 746. *Helwig*; Zeitsch. f. anal. Chem., 1872, 244. *Hirsch*; N. J. Pharm., xxxii, 140. *Hoppe-Seyler*; Med. Chem. Unters., i, 298; Jahresb., 1867, 805. *Krauss*; Jahresb., 1861, 792. *Liebig, Poggendorff and Wohler*; Handwörterb., iv, 177. *Liman*; Jahresb., 1863, 715. *Lowe*; Pharm. Centralb., 1854, 137. *Mandl*; Lond. Lanc., Dec. 17, 1842, 176. *Muller*; Zeitsch. f. anal. Chem., 1872, iii. *Orfila*; Jour. des Progés des Sc., iv, 1827; Archiv. gen. de Méd., Fev., 1828. *Papillon*; Mon. Scien. Ques., Jan., 1874, 59. *Reynolds*; Br. Med. Jour., Jan. 4, 1873. *Rose*; Jahresb. der Pharm., ii, 365; Jahresb., 1854, 754. *Roussin*; Ann. d'Hyg. et de Méd. lég., 1865. *Scriba, Simon and Buchner*; Jahresb., 1859, 706. *Sonnenschein*; Jour. de Pharm. et de Chim., July, 1874; Mon. Scien., ii, 370. *Sorby*; Chem. News, 1865, xi, pp. 186, 194, 232, 256. *Struve*; Zeitsch. f. anal. Chem., 1872, 29. *Taylor*; Guy's Hosp. Rep., 1868. *Wicke*; Pharm. Centralb., 1854, 431. *Wittstein*; Arch. der Pharm., ii, 128. *Zollikopfer*; Ann. d. Chem. u. Pharm., xciii, 237; Pharm. Centralb., 1855, 217. On the detection of Spermatic Stains. *Bayard*; Ann. d'Hygiéne. pub., 1849, No. 43. *Renak*; Diagnostisch. u. Pathologisch. Unters. Berlin, 1845, pp. 148, 171. *Schmidt*; Diagnostik Verdäch. Flecken, Leipzig, 1848, pp. 42-48. * * * * * The following are the most important works relating to poisons and food-adulteration that have been issued since the publication of the first edition of this book: *Adam*; �tude sur les principales methodes d'essai et d'analyse du lait. Paris, 1879. *Averbeck*; Die Verfälschung der Nahrungsmittel. Bremen, 1878. *Bastide*; Vins sophistiqués. Beriès, 1876. *Bauer*; Die Verfälschung der Nahrungsmittel. Berlin, 1877. *Bell*; Analysis and adulteration of food. 1881. *Binz*; Intoxicationen. Tübingen, 1878. *Birnbaum*; Einfache Methoden zur Prüfung Lebensmittel. 1877. *Blane*; De la contrefaçon. *Blas*; De la présence de l'acide salicylique dans les bierres. Paris, 1879. *Blochman*; Ueber Verfälschung der Nahrungsmittel. Königsberg, 1881. *Blyth*; Dictionary of Hygiene. London, 1877. _Ibid_; Manual of chemistry. London, 1879. _Ibid_; Foods, composition and analysis. London, 1882. _Ibid_; Poisons, effects and detection of. London, 1882. *Boehn*; Herzgifte. *Bolley*; Manuel pratique d'essai et de recherches chimiques. Paris, 1877. *Bronner*; Chemistry of food and drink. London. *Caldwell*; Agricultural chemical analysis. N. Y., 1879. *Casper*; Handbuch der gerichtlichen Medizin. Berlin, 1881. *Church*; Food. N. Y., 1877. *Cooley's* Practical receipts. *Dannehl*; Die Verfälschung des Bieres. Berlin, 1877. *Dietzsch*; Die wichtigsten Nahrungsmittel, etc. Zurich, 1878. *Dragendorff*; Recherches des substances amères dans la bière. Paris, 1876. _Ibid_; Gerichtlich chemische Ermittellung von Giften. St. Petersburg, 1876. *Elsner*; Die Praxis Nahrungsmittel Chemikers. Leipzig, 1880. *Eulenberg*; Handbuch der Gewerbe-Hygiene. Berlin, 1876. *Falk*; Lehrbuch der praktischen Toxicologie. Stuttgart, 1880. *Flick*; Die Chemie im Dienst der öffentlichen Gesundheitspflege. Dresden, 1882. *Fluegge*; Lehrbuch der hygienischen Untersuchungsmethoden. Leipzig, 1881. *Focke*; Massregeln gegen Verfälschung der Nahrungsmittel. Chemnitz, 1877. *Fox*; Sanitary examination of water, air, and food. 1878. *Franchini*; Palmelle prodigieuse. Bologne, 1880. *Gamgee*; Text-book of physiological chemistry. London, 1880. *Gaultier*; La sophistication des vins. Paris, 1877. *Gimlini*; Experimentelle Untersuchung über die Wirkung des Aconitins. Erlangen, 1876. *Goppelsroeder*; Sur l'analyse des vins. Mulhouse, 1877. *Grandeau*; Handbuch für agricultur-chemische Analysen. Berlin, 1880. *Griessmayer*; Die Verfälschung der wichtigsten Nahrungs-und Genussmittel. 1880. *Hahn*; Die wichtigsten d. his jetzt bekannten Geheimmittel u. Specialitäten. 1876. *Hausner*; Fabrikation der Conserven und Conditen. Leipzig, 1877. *Hemming*; Aids to forensic medicine and toxicology. London, 1877. *Hilger*; Die wichtigsten Nahrungsmittel. Erlangen, 1879. *Hoffman*; Lehrbuch der gerichtlichen Medizin. Wien, 1880. *Hoppe-Seyler*; Physiologische Chemie. Berlin, 1878. *Husson*; Du vin. Paris, 1877. _Ibid_; Le lait, la créme, et le beurre. 1878. *Johnson's* Encyclopædia, vol. iv. p. 752. *Johnson*; Chemistry of common life. N. Y., 1880. *Judell*; Die Vergiftung mit Blausäure. Erlangen, 1876. *Kensington*; Analysis of foods. London, 1879. *Klencke*; Illustrirtes Lexicon der Verfälschung der Nahrungsmittel und Getränke. Leipzig, 1878. *Koenig*; Chemische Zusammensetzung der menschlichen Nahrungsmittel. *Lang*; Die Fabrikation der Kunstbutter, Sparbutter, und Butterin. 1878. *Lessner*; Atlas der gerichtlichen Medizin. Berlin, 1883. *Lieberman*; Anleitung zur chemischen Untersuchung auf der Gebiete der Medicinal-polizei. Stuttgart, 1877. *Lintner*; Lehrbuch der Bierbrauerei. 1877. *Loebner*; Massregeln gegen Verfälschung der Nahrungsmittel. Chemnitz, 1877. *Luerssen*; Medicinisch Botanik. Leipzig, 1883. *Maschka*; Handbuch der gerichtlichen Medizin. Tübingen, 1882. *Medicus*; Gerichtlich-chemische Prüfung von Nahrungs-und Genussmitteln. 1881. *Montgomery*; Essai de Toxicologie. Paris, 1878. *Muter*; A key to organic materia medica. 1879. *Ogston*; Lectures on medical jurisprudence. London, 1878. *Palm*; Die wichtigsten und gebrauchlichsten Nahrungsmittel. St. Petersburg, 1882. *Parkes*; Hygiene. Phila., 1878. *Pasteur*; �tudes sur la bière. Paris, 1876. *Pavy*; A treatise on food and dietetics. London, 1875. *Pennetier*; Leçons sur les matières premières organiques. Paris, 1881. *Praag*; Leerbock voor practische Giftleer. Utrecht. *Pratt*; Food adulteration. Chicago, 1880. *Prescott*; Proximate organic analysis. N. Y., 1882. *Ritter*; Des vins colorés par la fuchsine. Paris, 1876. *Reitleitner*; Die Analyse des Weines. Wien, 1877. *Schnacke*; Wörterbuch der Verfälschung. Jena, 1877. *Schmidt*; Anleitung sanitarisch-und polizeilich-chemischen Untersuchungen. Zurich, 1878. *Schroff*; Beitrag zur Kenntniss des Aconits. Wien, 1876. *Selmi*; Chimica applicata all' igiene alla economia domestica. Milan. *Sharples*; Food and its adulteration. Preston, 1879. *Smith*; On foods. N. Y., 1873. *Smith, Ed.*; Manual for medical officers of health. London, 1874. _Ibid_; Handbook for inspectors of nuisances. London. *Spon's* Encyclopædia. London, 1882. *Squibb*; Proper legislation on adulteration of food. N. Y., 1879. *Steirlin*; Ueber Weinverfälschung und Weinfarbung. Bern, 1877. _Ibid_; Das Bier und seine Verfälschung. Bern, 1878. *Thudicum and Dupre*; Wine. *Vogel*; Praktische Spectral-analyse. Nordlingen, 1877. *Wanklyn*; Tea, coffee, and cocoa. London, 1874. *Wanklyn and Cooper*; Bread analysis. London, 1881. *Wenyl*; Analytisches Hülfsbuch. Berlin, 1882. *Wittstein*; Taschenbuch des Nahrungs-und Genussmittel Lehre. Nordlingen, 1877. *Woodman*; Handbook of forensic medicine. London, 1877. *Wurtz*; Traité élémentaire de chimie médicale. Paris. MEMOIRS. Alkaloids. Journal Chem. Soc. i, 1877, p. 143; ibid, i, 1878, p. 151; ibid, May, 1882; ibid, ccxliv, 1883, p. 358. Trans. Internat'l Med. Cong., 1881, vol. i, p. 472. Virch., Arch. bd. 79, 1880, s. 292; ibid, bd. 87, 1882, s. 410. Archiv. d. Pharm., Jan. 7, 1882; ibid, [3] vii, pp. 23-26; ibid, [3] vi, p. 402. Liebig, Anal. bd. 708, 1881. Berl. Klin. Wochenschr. 1876, 27. Pflüger's, 23, 433. Lancet, Sept. 30, 1880; ibid, Nov. 28, 1882; ibid, Nov. 13, 1882. Bull. Farm. Milano, 1881, p. 197. Zeitsch. f. Anal. Chem. i, 517. Gazett. Chim. Ital. vi, 153-166. Pharm. Zeitschr. f. Russland, i, p. 277. Vierteljahrsschr. f. gericht. Med. xxiii, p. 78. Arsenic and Antimony. Archiv, f. exper. Path. u. Pharm., Leipzig, 1882. Pharm. Journ. Trans. [3] pp. 81-83. Med. Jahrbuch, 1880. Journ. d'Hygiène, Juil., 1878. Medical Times and Gaz. 1876, p. 367. Chem. News, Jan., 1881, p. 21; ibid, xxxiii., pp. 58 and 74. Am. Chem. Journ. ii, No. 4. Bull. Soc. Chim. [2] xxvi, p. 541; ibid, Jan. 7, 1877. Zeitsch. f. Anal. Chem. xiv, pp. 250, 281, 356; ibid, i, p. 445. Liebig, Anal. ccvii, p. 182. Lancet, 1879, p. 699; ibid, May 19, 1883. Journ. Chem. Soc. No. 1, 1876. Mercury, Copper and Lead. Zeit. f. Phys. Chem. 1882, i, p. 495. Analyst, 1878, p. 241. Chem. News, xxxi, p. 77; ibid, xxxi, p. 801; ibid, xxxiv, pp. 176, 200, and 313. Analyst, 1877, pp. 13 and 216. Journ. Chem. Soc. 1876, ii, p. 4. Dingl. Pol. Journ. ccxx, 446. Med. Gazette, xlviii, 1047. Prussic Acid. Analyst, Apr., 1877, p. 5. Bull. Gen. de Thér. No. 30. Am. Journ. Phys. Sci., Arnold, 1869. Virch., Arch. f. Path. Anat. bd. 38, p. 435. News Repert. f. Pharm., 18, 356. Journ. Chem. Soc. 1876, i, p. 112. Bericht. d. Deutsch. Chem. Gess. ix, p. 1023. Viertelj. f. Ger. Med. 1881, p. 193. Zeit. f. Anal. Chem. von Fresenius, xii, p. 4. Flour and Bread. Analyst, June, 1878; ibid, Jan., 1882; ibid, 1878, No. 28; ibid, vi, 1879, p. 126; ibid, iii, pp. 274, 355. Chem. News, 1873, 1879, xxxix, p. 80. Dingl. Pol. Journ. bd. 209. Journ. Pharm. [4] iv, 108. Chem. Centr'b't, 1877, 585. Pharm. Journ. xiii, 857. Journ. Chem. Med. 1878, p. 240. An. d. Chem. u. Pharm, bd. 10, 45 u. 101. Journ. f. Pract. Chem. xcix, 296; ciii, 65, 193, 233, 273. Zeit. Anal. Chem. 1878, p. 440; ibid, 1879, vol. xviii, p. 120. Chem. Soc. Jour. xxxv, p. 610. Jour. d'Hygiène, May, 1878. Pharm. Jour. Trans. 1876, cccxii, 1001. Pharmacographia, 1879, p. 62. Sanitary Engineer, vol. v, p. 66. Tea. Pharm. Journ. 1873; 3d series, 1874. Chem. News, xxx, 1874 (Allen); xxx, 125; xxviii, 186. Journ. Pharm. [2] xxvi, 63; xii, 234, 229. Analyst, June, 1877; 1876 (Wigner). Journ. Chem. Soc. 1875, 385, 1217; ix, 321, 33; 1858. Journ. f. Pract. Chem. x, 273; xciv, 65; li, 401. Bull. Soc. Chim. [2] xxvii, 199. Journ. de Pharm. d'Anvers, 1876, 121. Journ. Pharm. et Chim. 3 série, 1856, xxiv, 228. Repert. de Pharm. 1856, vii, p. 117. Journ. Chim. Méd. 2 série, 1844, x, 459; 1844, 24. Ann. Chem. Pharm. xxvi, 244; xxix, 271; xxxvi, 93. Ann. Chem. Pharm. lxxxii, 197; cxii, 96; i, 19; 1, 231; lxiii, 201; lxix, 120; lxxi; cxviii, 151. Ann. Chem. xxv, 63. Med. Press and Circular, 1871, p. 415. Kastu. Arch. vii, 266. Deut. Chem. Ges. Ber. ix, 1312. Parliamentary papers, 1871. Mag. Pharm. xix, 45. Ann. Chim. Phys. [3] xi, 138. Schweigg, Journ. Chem. Phys. lxi, 487; lxiv, 372. Phil. Mag. J. xxiii, 426; xiii, 21. Milk. Analyst, 1876, Jan. and May; 1877, p. 82; No. 21; Sept., Dec.; 1878, Jan.; p. 249; 1880, Mar. Chem. News, 1879. Journ. Chem. Soc. clxxxix, Sept., 1878. Comptes Rendus, t. 82, 1876. Ann. Chem. Pharm. lxi, 221. Milch Zeit. 1870, 1884. Wine and Beer. Analyst, 1877, pp. 26, 99, 146, 148. Ann. Chim. Phys. [5] ii, pp. 233-289. Bull. Soc. Chim. [2] xxv. Deut. Chem. Ges. Ber. ix, 1900. Comptes Rendus, lxxxiv, 348. Journ. Chim. Méd. t. ix, p. 495. Arch. Pharm. [3] v. 25, 23, bd. 185, p. 225. Chem. Soc. Journ. ii, 1877, p. 372. Ann. d'Hyg. et Méd. Lég. 1861, xvii, pp. 33, 430. Vinegar. Analyst, iii, 1878, p. 268; i, 1877, p. 105. Ann. d'Hyg. et Méd. Lég. 2 sér. t. xii. Pharm. Journ., Jul. 3, 1875. * * * * * Within the last few years the subject of food-adulteration has been so prominently brought before the public that, in many instances, the various State Boards of Health have commissioned their chemists to furnish reports on this subject. These may be found in the annual publications of the same, notably in the volumes issued by the Massachusetts, Michigan, New Jersey, and New York State Boards of Health. It may also be mentioned in this connection that the _Sanitary Engineer_ of New York, the _Analyst_ of London, the _Zeitschrift für Untersuchung von Lebensmitteln_, Eichstatt, and the _Zeitschrift gegen Verfälschung der Lebensmittel_, Leipzig, are journals devoted to the consideration of adulterations and the more recent methods employed for their detection. J. P. B. INDEX. A. Acetic Acid, 49, 89 Acids, 46, 95 Acetic, 49, 89 Boric, 90 Formic, 89 Hydriodic, 90 Hydrobromic, 90 Hydrochloric, 46 Hydrocyanic, 50 Hydrofluoric, 88 Hydrosulphuric, 91 Nitric, 47, 88 Oxalic, 49, 88, 89, 95 Phosphoric, 48, 90, 95 Phosphorous, 45 Sulphuric, 47, 89, 95 Aconitine, 79 Alcoholmeter (Gay-Lussac's), 145 Alkalies, 32, 93 Ammonia, 50 Baryta, 54 Lime, 53 Potassa, 53 Soda, 53 Strontia, 54 Alkaloids, 65 Aconitine, 79 Aniline, 75 Aricine, 77 Atropine, 80 Beberine, 76 Brucine, 78 Cinchonine, 78 Codeine, 80 Colchicine, 80 Conine, 75 Delphine, 78 Digitaline, 80 Emetine, 80 Morphine, 80 Narcotine, 77 Nicotine, 75 Papaverine, 77 Picrotoxine, 80 Quinine, 77 Solanine, 79 Strychnine, 78 Veratrine, 77 Alkaloids, separation of, by Stas's method, 65 Separation of, by Otto's method, 69 Separation of, by v. Uslar and Erdman's method, 70 Separation of, by Rodgers & Girdwood's method, 71 Separation of, by Prollius's method, 72 Separation of, by Graham & Hofman's method, 73 Separation of, by Dialysis, 74 Alkaloids, identification of, 74 Alloys, examination of, 112 Alum in flour and bread, 126 Aniline, 75 Antimony, 30, 62, 93 Detection of, by Flandin and Danger's method, 32 Detection of, by Naquet's method, 34 Aricine, 77 Arsenic, 17, 60, 93 Detection of, by the method used prior to Marsh's test, 17 Detection of, by Marsh's test, 21 Detection of, by Raspail's test, 29 Detection of, by Reinsch's test, 30 Arsenic, estimation of, 21 Ashes, examination of, 104 Atropine, 80 B. Barley meal in flour, 117 Baryta, 54 Barreswil's test for milk, 140 Berberine, 76 Bicarbonate of soda in milk, 141 Bismuth, 62 Blood stains, detection of, 150 Bleaching of hair, 98 Boric acid, 90 Boutigny's examination of fire-arms, 100 Bromine, 55, 90, 93, 94 Brücke's test for blood stains, 152 Brucine, 78 Buckwheat in flour, 117, 120 C. Cadmium, 63 Carbonate of lime and magnesia in flour, 125 Cerebral substances in milk, 142 Chalk in milk, 141 Chlorine, 54 Chromium, 64 Cinchonine in sulphate of quinine, 149 Codeine, 80 Conine, 75 Coins, examination of, 112 Colchicine, 80 Copper, 62, 63 Corn meal in flour, 117, 120 D. Darnel in flour, 121 Delphine, 78 Determinative tests for poisons, 94 Digitaline, 80 Dusart's test for phosphorus, 40 Dialysis, 15, 74 Dyeing of hair, 97 E. Emetine, 80 Emulsion of almonds in milk, 141 F. Fire-arms, examination of, 100 Weapons provided with a flint, 100 Weapons not provided with a flint, 103 Fixed Oils, examination of, 128 Hempseed, 130 Olive, 128 Flandin and Danger's test for antimony, 32 Flandin and Danger's test for mercury, 37 Food (flour and bread), 114 Examination of the gluten, 116 Examination of the starch, 118 Examination of the ash, 124 Formic acid, 89 Fresenius & Neubauer's test for phosphorus, 42 G. Galactoscope, 138 Graham and Hofman's method for alkaloids, 73 Ground bones in bread and flour, 125 Gum arabic in milk, 141 Gum tragacanth in milk, 141 H. Hæmin crystals, 150 Hair, examination of, 96 Hempseed oil, 130 Hoppe-Seyler's test for blood, 151 Hydriodic acid, 90 Hydrobromic acid, 90 Hydrochloric acid, 46, 91 Hydrocyanic acid, 50 Hydrofluoric acid, 88 Hydrosulphuric acid, 91 I. Iodides, 90, 94 Iodine, 56, 94 Indicative tests for poisons, 36 L. Lactodensimeter, 138 Lactometer, 139 Lactoscope, 138 Lassaigne's test for writings, 107 Lead, 57 Legumens in flour, 117, 121, 124 Lentils in flour, 123 Lime, 53 Lime in flour, 126 Linseed meal in flour, 120 M. Macadam's method for alkaloids, 73 Magnesia in sulphate of quinine, 148 Mannite in sulphate of quinine, 148 Marchand's test for milk, 139 Marsh's test for arsenic, 21 Mercury, 36, 62, 93 Detection of, by Smithson's pile, 36 Detection of, by Flandin and Danger's method, 37 Metals, 56 Antimony, 30, 62, 93 Arsenic, 17, 60, 93 Bismuth, 62 Cadmium, 63 Chromium, 64 Copper, 62, 63 Lead, 57 Mercury, 36, 62, 93 Silver, 57 Tin, 56, 61 Zinc, 64 Milk, examination of, 137 Mineral substances, in flour and bread, 124 In milk, 141 In sulphate of quinine, 148 Mistcherlich's test for phosphorus, 40 Morphine, 80 N. Naquet's test for antimony, 34 Narcotine, 77 Nicotine, 75 Nitric acid, 47, 88 O. Oatmeal in flour, 117 Oleometer, 128 Olive oil, 128 Orfila's test for phosphorus, 39 Organic matter Destruction of, by _aqua regia_, 14 Destruction of, by chlorate of potassa, 13 Destruction of, by chlorine, 13 Destruction of, by nitrate of potassa, 10 Destruction of, by nitric acid, 8 Destruction of, by potassa and nitrate of lime, 12 Destruction of, by potassa and nitric acid, 12 Destruction of, by sulphuric acid, 9 Otto's method for alkaloids, 69 Oxalic acid, 49, 88, 89, 95 P. Papaverine, 77 Payen's test for vinegar, 147 Phosphoric acid, 48, 90, 95 Phosphorous acid, 45 Phosphorus, 39, 95 Detection of, by Orfila's method, 39 Detection of, by Mistcherlich's method, 40 Detection of, by Dusart's method, 40 Detection of, by Fresenius and Neubauer's method, 42 Estimation of, 45 Picrotoxine, 80 Plaster in flour, 126 Poisons, detection of In cases where no clew exists, 85 In cases where a clew exists, 17 Destruction of the organic matter, 8 Indicative tests, 86 Determinative tests, 94 Potato meal in flour, 118 Potassa, 53, 93 Prollius' method for alkaloids, 72 Prussic acid, 50 Q. Quinine, 77 R. Raspail's test for arsenic, 29 Reinsch's test for arsenic, 30 Reveil's test for vinegar, 148 Rice meal in flour, 120 Robin's method for spermatic stains, 160 Rodgers and Girdwood's method for alkaloids, 71 Rye meal in flour, 117, 120 S. Salicine in sulphate of quinine, 148 Sand in flour, 125 Silver, 57 Smithson's pile, 36 Soda, 53, 92, 93 Solanine, 79 Spermatic stains, detection of, 158 Spermatozoa, 159 Starch in sulphate of quinine, 148 Stearic acid in sulphate of quinine, 148 Stas's method for alkaloids, 65 Strychnine, 78 Sugar in milk, 142 Sugar in sulphate of quinine, 148 Sulphate of copper in bread, 127 Sulphate of quinidine in sulphate of quinine, 149 Sulphate of quinine, examination of, 148 Sulphuretted hydrogen, 91 Sulphuric acid, 47, 89, 95 Sympathetic inks, tests for, 110 T. Tea, 130 Tin, 56, 61 U. v. Uslar and Erdman's method for alkaloids, 70 V. Veratrine, 77 Vinegar, examination of, 147 W. Wines, examination of, 142 Writings, examination of, 105 Z. Zinc, 64 BECKER & SONS, MANUFACTURERS OF Balances and Weights of Precision, FOR [Illustration] Chemists, Assayers, Jewelers, Druggists, _And in general for every use where accuracy is required_, No. 6 Murray St., New York. 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H.--Field Tactics for Infantry.* Illustrated. 18mo, cloth 75 ---- *Infantry Tactics.* 2 vols. 24mo. 2 00 2 vols. in one, cloth 1 50 Transcriber's Notes: The following corrections which did not concern obvious printer's errors have been made to the text. -In the Table of Content, the formatting of the entry for "Dialysis" was changed in order to indicate that this part is a section of the chapter "Methods of Destruction of the Organic Substances" -"treated with "_mélaïnocome_"" was: "treated with "melaniocome"" -The sentence "M. Salleron offers for sale a small apparatus (Fig. 20)" wrongly referred to Fig. 16. -"If the crystals originate from fresh blood, they appear as represented in Fig. 21; crystals from old blood are represented in Fig. 22." wrongly referred to Fig. 17 and 18; the same was the case in "The fluid is examined from time to time under the microscope: when it is sufficiently concentrated, crystals, presenting the appearance represented in Figs. 21 or 22, will be observed." -"an oxidizing body" was: "an oxydizing body" -"condenser" was: "condensor" -"areometer (alcoholmeter)" was: "areometer (alcoolmeter)" 
5073	----	THE CRAIG KENNEDY SERIES THE WAR TERROR BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER CONTENTS CHAPTER INTRODUCTION I. THE WAR TERROR II. THE ELECTRO-MAGNETIC GUN III. THE MURDER SYNDICATE IV. THE AIR PIRATE V. THE ULTRA-VIOLET RAY VI. THE TRIPLE MIRROR VII. THE WIRELESS WIRETAPPERS VIII. THE HOUSEBOAT MYSTERY IX. THE RADIO DETECTIVE X. THE CURIO SHOP XI. THE "PILLAR OF DEATH" XII. THE ARROW POISON XIII. THE RADIUM ROBBER XIV. THE SPINTHARISCOPE XV. THE ASPHYXIATING SAFE XVI. THE DEAD LINE XVII. THE PASTE REPLICA XVIII. THE BURGLAR'S MICROPHONE XIX. THE GERM LETTER XX. THE ARTIFICIAL KIDNEY XXI. THE POISON BRACELET XXII. THE DEVIL WORSHIPERS XXIII. THE PSYCHIC CURSE XXIV. THE SERPENT'S TOOTH XXV. THE "HAPPY DUST" XXVI. THE BINET TEST XXVII. THE LIE DETECTOR XXVIII. THE FAMILY SKELETON XXIX. THE LEAD POISONER XXX. THE ELECTROLYTIC MURDER XXXI. THE EUGENIC BRIDE XXXII. THE GERM PLASM XXXIII. THE SEX CONTROL XXXIV. THE BILLIONAIRE BABY XXXV. THE PSYCHANALYSIS XXXVI. THE ENDS OF JUSTICE INTRODUCTION As I look back now on the sensational events of the past months since the great European War began, it seems to me as if there had never been a period in Craig Kennedy's life more replete with thrilling adventures than this. In fact, scarcely had one mysterious event been straightened out from the tangled skein, when another, even more baffling, crowded on its very heels. As was to have been expected with us in America, not all of these remarkable experiences grew either directly or indirectly out of the war, but there were several that did, and they proved to be only the beginning of a succession of events which kept me busy chronicling for the Star the exploits of my capable and versatile friend. Altogether, this period of the war was, I am sure, quite the most exciting of the many series of episodes through which Craig has been called upon to go. Yet he seemed to meet each situation as it arose with a fresh mind, which was amazing even to me who have known him so long and so intimately. As was naturally to be supposed, also, at such a time, it was not long before Craig found himself entangled in the marvelous spy system of the warring European nations. These systems revealed their devious and dark ways, ramifying as they did tentacle-like even across the ocean in their efforts to gain their ends in neutral America. Not only so, but, as I shall some day endeavor to show later, when the ban of silence imposed by neutrality is raised after the war, many of the horrors of the war were brought home intimately to us. I have, after mature consideration, decided that even at present nothing but good can come from the publication at least of some part of the strange series of adventures through which Kennedy and I have just gone, especially those which might, if we had not succeeded, have caused most important changes in current history. As for the other adventures, no question can be raised about the propriety of their publication. At any rate, it came about that early in August, when the war cloud was just beginning to loom blackest, Kennedy was unexpectedly called into one of the strangest, most dangerous situations in which his peculiar and perilous profession had ever involved him. CHAPTER I THE WAR TERROR "I must see Professor Kennedy--where is he?--I must see him, for God's sake!" I was almost carried off my feet by the inrush of a wild-eyed girl, seemingly half crazed with excitement, as she cried out Craig's name. Startled by my own involuntary exclamation of surprise which followed the vision that shot past me as I opened our door in response to a sudden, sharp series of pushes at the buzzer, Kennedy bounded swiftly toward me, and the girl almost flung herself upon him. "Why, Miss--er--Miss--my dear young lady--what's the matter?" he stammered, catching her by the arm gently. As Kennedy forced our strange visitor into a chair, I observed that she was all a-tremble. Her teeth fairly chattered. Alternately her nervous, peaceless hands clutched at an imaginary something in the air, as if for support, then, finding none, she would let her wrists fall supine, while she gazed about with quivering lips and wild, restless eyes. Plainly, there was something she feared. She was almost over the verge of hysteria. She was a striking girl, of medium height and slender form, but it was her face that fascinated me, with its delicately molded features, intense unfathomable eyes of dark brown, and lips that showed her idealistic, high-strung temperament. "Please," he soothed, "get yourself together, please--try! What is the matter?" She looked about, as if she feared that the very walls had eyes and ears. Yet there seemed to be something bursting from her lips that she could not restrain. "My life," she cried wildly, "my life is at stake. Oh--help me, help me! Unless I commit a murder to-night, I shall be killed myself!" The words sounded so doubly strange from a girl of her evident refinement that I watched her narrowly, not sure yet but that we had a plain case of insanity to deal with. "A murder?" repeated Kennedy incredulously. "YOU commit a murder?" Her eyes rested on him, as if fascinated, but she did not flinch as she replied desperately, "Yes--Baron Kreiger--you know, the German diplomat and financier, who is in America raising money and arousing sympathy with his country." "Baron Kreiger!" exclaimed Kennedy in surprise, looking at her more keenly. We had not met the Baron, but we had heard much about him, young, handsome, of an old family, trusted already in spite of his youth by many of the more advanced of old world financial and political leaders, one who had made a most favorable impression on democratic America at a time when such impressions were valuable. Glancing from one of us to the other, she seemed suddenly, with a great effort, to recollect herself, for she reached into her chatelaine and pulled out a card from a case. It read simply, "Miss Paula Lowe." "Yes," she replied, more calmly now to Kennedy's repetition of the Baron's name, "you see, I belong to a secret group." She appeared to hesitate, then suddenly added, "I am an anarchist." She watched the effect of her confession and, finding the look on Kennedy's face encouraging rather than shocked, went on breathlessly: "We are fighting war with war--this iron-bound organization of men and women. We have pledged ourselves to exterminate all kings, emperors and rulers, ministers of war, generals--but first of all the financiers who lend money that makes war possible." She paused, her eyes gleaming momentarily with something like the militant enthusiasm that must have enlisted her in the paradoxical war against war. "We are at least going to make another war impossible!" she exclaimed, for the moment evidently forgetting herself. "And your plan?" prompted Kennedy, in the most matter-of-fact manner, as though he were discussing an ordinary campaign for social betterment. "How were you to--reach the Baron?" "We had a drawing," she answered with amazing calmness, as if the mere telling relieved her pent-up feelings. "Another woman and I were chosen. We knew the Baron's weakness for a pretty face. We planned to become acquainted with him--lure him on." Her voice trailed off, as if, the first burst of confidence over, she felt something that would lock her secret tighter in her breast. A moment later she resumed, now talking rapidly, disconnectedly, giving Kennedy no chance to interrupt or guide the conversation. "You don't know, Professor Kennedy," she began again, "but there are similar groups to ours in European countries and the plan is to strike terror and consternation everywhere in the world at once. Why, at our headquarters there have been drawn up plans and agreements with other groups and there are set down the time, place, and manner of all the--the removals." Momentarily she seemed to be carried away by something like the fanaticism of the fervor which had at first captured her, even still held her as she recited her incredible story. "Oh, can't you understand?" she went on, as if to justify herself. "The increase in armies, the frightful implements of slaughter, the total failure of the peace propaganda--they have all defied civilization! "And then, too, the old, red-blooded emotions of battle have all been eliminated by the mechanical conditions of modern warfare in which men and women are just so many units, automata. Don't you see? To fight war with its own weapons--that has become the only last resort." Her eager, flushed face betrayed the enthusiasm which had once carried her into the "Group," as she called it. I wondered what had brought her now to us. "We are no longer making war against man," she cried. "We are making war against picric acid and electric wires!" I confess that I could not help thinking that there was no doubt that to a certain type of mind the reasoning might appeal most strongly. "And you would do it in war time, too?" asked Kennedy quickly. She was ready with an answer. "King George of Greece was killed at the head of his troops. Remember Nazim Pasha, too. Such people are easily reached in time of peace and in time of war, also, by sympathizers on their own side. That's it, you see--we have followers of all nationalities." She stopped, her burst of enthusiasm spent. A moment later she leaned forward, her clean-cut profile showing her more earnest than before. "But, oh, Professor Kennedy," she added, "it is working itself out to be more terrible than war itself!" "Have any of the plans been carried out yet?" asked Craig, I thought a little superciliously, for there had certainly been no such wholesale assassination yet as she had hinted at. She seemed to catch her breath. "Yes," she murmured, then checked herself as if in fear of saying too much. "That is, I--I think so." I wondered if she were concealing something, perhaps had already had a hand in some such enterprise and it had frightened her. Kennedy leaned forward, observing the girl's discomfiture. "Miss Lowe," he said, catching her eye and holding it almost hypnotically, "why have you come to see me?" The question, pointblank, seemed to startle her. Evidently she had thought to tell only as little as necessary, and in her own way. She gave a little nervous laugh, as if to pass it off. But Kennedy's eyes conquered. "Oh, can't you understand yet?" she exclaimed, rising passionately and throwing out her arms in appeal. "I was carried away with my hatred of war. I hate it yet. But now--the sudden realization of what this compact all means has--well, caused something in me to--to snap. I don't care what oath I have taken. Oh, Professor Kennedy, you--you must save him!" I looked up at her quickly. What did she mean? At first she had come to be saved herself. "You must save him!" she implored. Our door buzzer sounded. She gazed about with a hunted look, as if she felt that some one had even now pursued her and found out. "What shall I do?" she whispered. "Where shall I go?" "Quick--in here. No one will know," urged Kennedy, opening the door to his room. He paused for an instant, hurriedly. "Tell me--have you and this other woman met the Baron yet? How far has it gone?" The look she gave him was peculiar. I could not fathom what was going on in her mind. But there was no hesitation about her answer. "Yes," she replied, "I--we have met him. He is to come back to New York from Washington to-day--this afternoon--to arrange a private loan of five million dollars with some bankers secretly. We were to see him to-night--a quiet dinner, after an automobile ride up the Hudson--" "Both of you?" interrupted Craig. "Yes--that--that other woman and myself," she repeated, with a peculiar catch in her voice. "To-night was the time fixed in the drawing for the--" The word stuck in her throat. Kennedy understood. "Yes, yes," he encouraged, "but who is the other woman?" Before she could reply, the buzzer had sounded again and she had retreated from the door. Quickly Kennedy closed it and opened the outside door. It was our old friend Burke of the Secret Service. Without a word of greeting, a hasty glance seemed to assure him that Kennedy and I were alone. He closed the door himself, and, instead of sitting down, came close to Craig. "Kennedy," he blurted out in a tone of suppressed excitement, "can I trust you to keep a big secret?" Craig looked at him reproachfully, but said nothing. "I beg your pardon--a thousand times," hastened Burke. "I was so excited, I wasn't thinking--" "Once is enough, Burke," laughed Kennedy, his good nature restored at Burke's crestfallen appearance. "Well, you see," went on the Secret Service man, "this thing is so very important that--well, I forgot." He sat down and hitched his chair close to us, as he went on in a lowered, almost awestruck tone. "Kennedy," he whispered, "I'm on the trail, I think, of something growing out of these terrible conditions in Europe that will tax the best in the Secret Service. Think of it, man. There's an organization, right here in this city, a sort of assassin's club, as it were, aimed at all the powerful men the world over. Why, the most refined and intellectual reformers have joined with the most red-handed anarchists and--" "Sh! not so loud," cautioned Craig. "I think I have one of them in the next room. Have they done anything yet to the Baron?" It was Burke's turn now to look from one to the other of us in unfeigned surprise that we should already know something of his secret. "The Baron?" he repeated, lowering his voice. "What Baron?" It was evident that Burke knew nothing, at least of this new plot which Miss Lowe had indicated. Kennedy beckoned him over to the window furthest from the door to his own room. "What have you discovered?" he asked, forestalling Burke in the questioning. "What has happened?" "You haven't heard, then?" replied Burke. Kennedy nodded negatively. "Fortescue, the American inventor of fortescite, the new explosive, died very strangely this morning." "Yes," encouraged Kennedy, as Burke came to a full stop to observe the effect of the information. "Most incomprehensible, too," he pursued. "No cause, apparently. But it might have been overlooked, perhaps, except for one thing. It wasn't known generally, but Fortescue had just perfected a successful electro-magnetic gun--powderless, smokeless, flashless, noiseless and of tremendous power. To-morrow he was to have signed the contract to sell it to England. This morning he is found dead and the final plans of the gun are gone!" Kennedy and Burke were standing mutely looking at each other. "Who is in the next room?" whispered Burke hoarsely, recollecting Kennedy's caution of silence. Kennedy did not reply immediately. He was evidently much excited by Burke's news of the wonderful electro-magnetic gun. "Burke," he exclaimed suddenly, "let's join forces. I think we are both on the trail of a world-wide conspiracy--a sort of murder syndicate to wipe out war!" Burke's only reply was a low whistle that involuntarily escaped him as he reached over and grasped Craig's hand, which to him represented the sealing of the compact. As for me, I could not restrain a mental shudder at the power that their first murder had evidently placed in the hands of the anarchists, if they indeed had the electro-magnetic gun which inventors had been seeking for generations. What might they not do with it--perhaps even use it themselves and turn the latest invention against society itself! Hastily Craig gave a whispered account of our strange visit from Miss Lowe, while Burke listened, open-mouthed. He had scarcely finished when he reached for the telephone and asked for long distance. "Is this the German embassy in Washington?" asked Craig a few moments later when he got his number. "This is Craig Kennedy, in New York. The United States Secret Service will vouch for me--mention to them Mr. Burke of their New York office who is here with me now. I understand that Baron Kreiger is leaving for New York to meet some bankers this afternoon. He must not do so. He is in the gravest danger if he--What? He left last night at midnight and is already here?" Kennedy turned to us blankly. The door to his room opened suddenly. There stood Miss Lowe, gazing wild-eyed at us. Evidently her supernervous condition had heightened the keenness of her senses. She had heard what we were saying. I tried to read her face. It was not fear that I saw there. It was rage; it was jealousy. "The traitress--it is Marie!" she shrieked. For a moment, obtusely, I did not understand. "She has made a secret appointment with him," she cried. At last I saw the truth. Paula Lowe had fallen in love with the man she had sworn to kill! CHAPTER II THE ELECTRO-MAGNETIC GUN "What shall we do?" demanded Burke, instantly taking in the dangerous situation that the Baron's sudden change of plans had opened up. "Call O'Connor," I suggested, thinking of the police bureau of missing persons, and reaching for the telephone. "No, no!" almost shouted Craig, seizing my arm. "The police will inevitably spoil it all. No, we must play a lone hand in this if we are to work it out. How was Fortescue discovered, Burke?" "Sitting in a chair in his laboratory. He must have been there all night. There wasn't a mark on him, not a sign of violence, yet his face was terribly drawn as though he were gasping for breath or his heart had suddenly failed him. So far, I believe, the coroner has no clue and isn't advertising the case." "Take me there, then," decided Craig quickly. "Walter, I must trust Miss Lowe to you on the journey. We must all go. That must be our starting point, if we are to run this thing down." I caught his significant look to me and interpreted it to mean that he wanted me to watch Miss Lowe especially. I gathered that taking her was in the nature of a third degree and as a result he expected to derive some information from her. Her face was pale and drawn as we four piled into a taxicab for a quick run downtown to the laboratory of Fortescue from which Burke had come directly to us with his story. "What do you know of these anarchists?" asked Kennedy of Burke as we sped along. "Why do you suspect them?" It was evident that he was discussing the case so that Paula could overhear, for a purpose. "Why, we received a tip from abroad--I won't say where," replied Burke guardedly, taking his cue. "They call themselves the 'Group,' I believe, which is a common enough term among anarchists. It seems they are composed of terrorists of all nations." "The leader?" inquired Kennedy, leading him on. "There is one, I believe, a little florid, stout German. I think he is a paranoiac who believes there has fallen on himself a divine mission to end all warfare. Quite likely he is one of those who have fled to America to avoid military service. Perhaps, why certainly, you must know him--Annenberg, an instructor in economics now at the University?" Craig nodded and raised his eyebrows in mild surprise. We had indeed heard of Annenberg and some of his radical theories which had sometimes quite alarmed the conservative faculty. I felt that this was getting pretty close home to us now. "How about Mrs. Annenberg?" Craig asked, recalling the clever young wife of the middle-aged professor. At the mere mention of the name, I felt a sort of start in Miss Lowe, who was seated next to me in the taxicab. She had quickly recovered herself, but not before I saw that Kennedy's plan of breaking down the last barrier of her reserve was working. "She is one of them, too," Burke nodded. "I have had my men out shadowing them and their friends. They tell me that the Annenbergs hold salons--I suppose you would call them that--attended by numbers of men and women of high social and intellectual position who dabble in radicalism and all sorts of things." "Who are the other leaders?" asked Craig. "Have you any idea?" "Some idea," returned Burke. "There seems to be a Frenchman, a tall, wiry man of forty-five or fifty with a black mustache which once had a military twist. There are a couple of Englishmen. Then there are five or six Americans who seem to be active. One, I believe, is a young woman." Kennedy checked him with a covert glance, but did not betray by a movement of a muscle to Miss Lowe that either Burke or himself suspected her of being the young woman in question. "There are three Russians," continued Burke, "all of whom have escaped from Siberia. Then there is at least one Austrian, a Spaniard from the Ferrer school, and Tomasso and Enrico, two Italians, rather heavily built, swarthy, bearded. They look the part. Of course there are others. But these in the main, I think, compose what might be called 'the inner circle' of the 'Group.'" It was indeed an alarming, terrifying revelation, as we began to realize that Miss Lowe had undoubtedly been telling the truth. Not alone was there this American group, evidently, but all over Europe the lines of the conspiracy had apparently spread. It was not a casual gathering of ordinary malcontents. It went deeper than that. It included many who in their disgust at war secretly were not unwilling to wink at violence to end the curse. I could not but reflect on the dangerous ground on which most of them were treading, shaking the basis of all civilization in order to cut out one modern excrescence. The big fact to us, just at present, was that this group had made America its headquarters, that plans had been studiously matured and even reduced to writing, if Paula were to be believed. Everything had been carefully staged for a great simultaneous blow or series of blows that would rouse the whole world. As I watched I could not escape observing that Miss Lowe followed Burke furtively now, as though he had some uncanny power. Fortescue's laboratory was in an old building on a side street several blocks from the main thoroughfares of Manhattan. He had evidently chosen it, partly because of its very inaccessibility in order to secure the quiet necessary for his work. "If he had any visitors last night," commented Kennedy when our cab at last pulled up before the place, "they might have come and gone unnoticed." We entered. Nothing had been disturbed in the laboratory by the coroner and Kennedy was able to gain a complete idea of the case rapidly, almost as well as if we had been called in immediately. Fortescue's body, it seemed, had been discovered sprawled out in a big armchair, as Burke had said, by one of his assistants only a few hours before when he had come to the laboratory in the morning to open it. Evidently he had been there undisturbed all night, keeping a gruesome vigil over his looted treasure house. As we gleaned the meager facts, it became more evident that whoever had perpetrated the crime must have had the diabolical cunning to do it in some ordinary way that aroused no suspicion on the part of the victim, for there was no sign of any violence anywhere. As we entered the laboratory, I noted an involuntary shudder on the part of Paula Lowe, but, as far as I knew, it was no more than might have been felt by anyone under the circumstances. Fortescue's body had been removed from the chair in which it had been found and lay on a couch at the other end of the room, covered merely by a sheet. Otherwise, everything, even the armchair, was undisturbed. Kennedy pulled back a corner of the sheet, disclosing the face, contorted and of a peculiar, purplish hue from the congested blood vessels. He bent over and I did so, too. There was an unmistakable odor of tobacco on him. A moment Kennedy studied the face before us, then slowly replaced the sheet. Miss Lowe had paused just inside the door and seemed resolutely bound not to look at anything. Kennedy meanwhile had begun a most minute search of the table and floor of the laboratory near the spot where the armchair had been sitting. In my effort to glean what I could from her actions and expressions I did not notice that Craig had dropped to his knees and was peering into the shadow under the laboratory table. When at last he rose and straightened himself up, however, I saw that he was holding in the palm of his hand a half-smoked, gold-tipped cigarette, which had evidently fallen on the floor beneath the table where it had burned itself out, leaving a blackened mark on the wood. An instant afterward he picked out from the pile of articles found in Fortescue's pockets and lying on another table a silver cigarette case. He snapped it open. Fortescue's cigarettes, of which there were perhaps a half dozen in the case, were cork-tipped. Some one had evidently visited the inventor the night before, had apparently offered him a cigarette, for there were any number of the cork-tipped stubs lying about. Who was it? I caught Paula looking with fascinated gaze at the gold-tipped stub, as Kennedy carefully folded it up in a piece of paper and deposited it in his pocket. Did she know something about the case, I wondered? Without a word, Kennedy seemed to take in the scant furniture of the laboratory at a glance and a quick step or two brought him before a steel filing cabinet. One drawer, which had not been closed as tightly as the rest, projected a bit. On its face was a little typewritten card bearing the inscription: "E-M GUN." He pulled the drawer open and glanced over the data in it. "Just what is an electro-magnetic gun?" I asked, interpreting the initials on the drawer. "Well," he explained as he turned over the notes and sketches, "the primary principle involved in the construction of such a gun consists in impelling the projectile by the magnetic action of a solenoid, the sectional coils or helices of which are supplied with current through devices actuated by the projectile itself. In other words, the sections of helices of the solenoid produce an accelerated motion of the projectile by acting successively on it, after a principle involved in the construction of electro-magnetic rock drills and dispatch tubes. "All projectiles used in this gun of Fortescue's evidently must have magnetic properties and projectiles of iron or containing large portions of iron are necessary. You see, many coils are wound around the barrel of the gun. As the projectile starts it does so under the attraction of those coils ahead which the current makes temporary magnets. It automatically cuts off the current from those coils that it passes, allowing those further on only to attract it, and preventing those behind from pulling it back." He paused to study the scraps of plans. "Fortescue had evidently also worked out a way of changing the poles of the coils as the projectile passed, causing them then to repel the projectile, which must have added to its velocity. He seems to have overcome the practical difficulty that in order to obtain service velocities with service projectiles an enormous number of windings and a tremendously long barrel are necessary as well as an abnormally heavy current beyond the safe carrying capacity of the solenoid which would raise the temperature to a point that would destroy the coils." He continued turning over the prints and notes in the drawer. When he finished, he looked up at us with an expression that indicated that he had merely satisfied himself of something he had already suspected. "You were right, Burke," he said. "The final plans are gone." Burke, who, in the meantime, had been telephoning about the city in a vain effort to locate Baron Kreiger, both at such banking offices in Wall Street as he might be likely to visit and at some of the hotels most frequented by foreigners, merely nodded. He was evidently at a loss completely how to proceed. In fact, there seemed to be innumerable problems--to warn Baron Kreiger, to get the list of the assassinations, to guard Miss Lowe against falling into the hands of her anarchist friends again, to find the murderer of Fortescue, to prevent the use of the electro-magnetic gun, and, if possible, to seize the anarchists before they had a chance to carry further their plans. "There is nothing more that we can do here," remarked Craig briskly, betraying no sign of hesitation. "I think the best thing we can do is to go to my own laboratory. There at least there is something I must investigate sooner or later." No one offering either a suggestion or an objection, we four again entered our cab. It was quite noticeable now that the visit had shaken Paula Lowe, but Kennedy still studiously refrained from questioning her, trusting that what she had seen and heard, especially Burke's report as to Baron Kreiger, would have its effect. Like everyone visiting Craig's laboratory for the first time, Miss Lowe seemed to feel the spell of the innumerable strange and uncanny instruments which he had gathered about him in his scientific warfare against crime. I could see that she was becoming more and more nervous, perhaps fearing even that in some incomprehensible way he might read her own thoughts. Yet one thing I did not detect. She showed no disposition to turn back on the course on which she had entered by coming to us in the first place. Kennedy was quickly and deftly testing the stub of the little thin, gold-tipped cigarette. "Excessive smoking," he remarked casually, "causes neuroses of the heart and tobacco has a specific affinity for the coronary arteries as well as a tremendous effect on the vagus nerve. But I don't think this was any ordinary smoke." He had finished his tests and a quiet smile of satisfaction flitted momentarily over his face. We had been watching him anxiously, wondering what he had found. As he looked up he remarked to us, with his eyes fixed on Miss Lowe, "That was a ladies' cigarette. Did you notice the size? There has been a woman in this case--presumably." The girl, suddenly transformed by the rapid-fire succession of discoveries, stood before us like a specter. "The 'Group,' as anarchists call it," pursued Craig, "is the loosest sort of organization conceivable, I believe, with no set membership, no officers, no laws--just a place of meeting with no fixity, where the comrades get together. Could you get us into the inner circle, Miss Lowe?" Her only answer was a little suppressed scream. Kennedy had asked the question merely for its effect, for it was only too evident that there was no time, even if she could have managed it, for us to play the "stool pigeon." Kennedy, who had been clearing up the materials he had used in the analysis of the cigarette, wheeled about suddenly. "Where is the headquarters of the inner circle?" he shot out. Miss Lowe hesitated. That had evidently been one of the things she had determined not to divulge. "Tell me," insisted Kennedy. "You must!" If it had been Burke's bulldozing she would never have yielded. But as she looked into Kennedy's eyes she read there that he had long since fathomed the secret of her wildly beating heart, that if she would accomplish the purpose of saving the Baron she must stop at nothing. "At--Maplehurst," she answered in a low tone, dropping her eyes from his penetrating gaze, "Professor Annenberg's home--out on Long Island." "We must act swiftly if we are to succeed," considered Kennedy, his tone betraying rather sympathy with than triumph over the wretched girl who had at last cast everything in the balance to outweigh the terrible situation into which she had been drawn. "To send Miss Lowe for that fatal list of assassinations is to send her either back into the power of this murderous group and let them know that she has told us, or perhaps to involve her again in the completion of their plans." She sank back into a chair in complete nervous and physical collapse, covering her face with her hands at the realization that in her new-found passion to save the Baron she had bared her sensitive soul for the dissection of three men whom she had never seen before. "We must have that list," pursued Kennedy decisively. "We must visit Annenberg's headquarters." "And I?" she asked, trembling now with genuine fear at the thought that he might ask her to accompany us as he had on our visit to Fortescue's laboratory that morning. "Miss Lowe," said Kennedy, bending over her, "you have gone too far now ever to turn back. You are not equal to the trip. Would you like to remain here? No one will suspect. Here at least you will be safe until we return." Her answer was a mute expression of thanks and confidence. CHAPTER III THE MURDER SYNDICATE Quickly now Craig completed his arrangements for the visit to the headquarters of the real anarchist leader. Burke telephoned for a high-powered car, while Miss Lowe told frankly of the habits of Annenberg and the chances of finding his place unguarded, which were good in the daytime. Kennedy's only equipment for the excursion consisted in a small package which he took from a cabinet at the end of the room, and, with a parting reassurance to Paula Lowe, we were soon speeding over the bridge to the borough across the river. We realized that it might prove a desperate undertaking, but the crisis was such that it called for any risk. Our quest took us to a rather dilapidated old house on the outskirts of the little Long Island town. The house stood alone, not far from the tracks of a trolley that ran at infrequent intervals. Even a hasty reconnoitering showed that to stop our motor at even a reasonable distance from it was in itself to arouse suspicion. Although the house seemed deserted, Craig took no chances, but directed the car to turn at the next crossroad and then run back along a road back of and parallel to that on which Annenberg's was situated. It was perhaps a quarter of a mile away, across an open field, that we stopped and ran the car up along the side of the road in some bushes. Annenberg's was plainly visible and it was not at all likely that anyone there would suspect trouble from that quarter. A hasty conference with Burke followed, in which Kennedy unwrapped his small package, leaving part of its contents with him, and adding careful instructions. Then Kennedy and I retraced our steps down the road, across by the crossroad, and at last back to the mysterious house. To all appearance there had been no need of such excessive caution. Not a sound or motion greeted us as we entered the gate and made our way around to the rear of the house. The very isolation of the house was now our protection, for we had no inquisitive neighbors to watch us for the instant when Kennedy, with the dexterity of a yeggman, inserted his knife between the sashes of the kitchen window and turned the catch which admitted us. We made our way on cautious tiptoe through a dining room to a living room, and, finding nothing, proceeded upstairs. There was not a soul, apparently, in the house, nor in fact anything to indicate that it was different from most small suburban homes, until at last we mounted to the attic. It was finished off in one large room across the back of the house and two in front. As we opened the door to the larger room, we could only gaze about in surprise. This was the rendezvous, the arsenal, literary, explosive and toxicological of the "Group." Ranged on a table were all the materials for bomb-making, while in a cabinet I fancied there were poisons enough to decimate a city. On the walls were pictures, mostly newspaper prints, of the assassins of McKinley, of King Humbert, of the King of Greece, of King Carlos and others, interspersed with portraits of anarchist and anti-militarist leaders of all lands. Kennedy sniffed. Over all I, too, could catch the faint odor of stale tobacco. No time was to be lost, however, and while Craig set to work rapidly going through the contents of a desk in the corner, I glanced over the contents of a drawer of a heavy mission table. "Here's some of Annenberg's literature," I remarked, coming across a small pile of manuscript, entitled "The Human Slaughter House." "Read it," panted Kennedy, seeing that I had about completed my part of the job. "It may give a clue." Hastily I scanned the mad, frantic indictment of war, while Craig continued in his search: "I see wild beasts all around me, distorted unnaturally, in a life and death struggle, with bloodshot eyes, with foaming, gnashing mouths. They attack and kill one another and try to mangle each other. I leap to my feet. I race out into the night and tread on quaking flesh, step on hard heads, and stumble over weapons and helmets. Something is clutching at my feet like hands, so that I race away like a hunted deer with the hounds at his heels--and ever over more bodies--breathless... out of one field into another. Horror is crooning over my head. Horror is crooning beneath my feet. And nothing but dying, mangled flesh! "Of a sudden I see nothing but blood before me. The heavens have opened and the red blood pours in through the windows. Blood wells up on an altar. The walls run blood from the ceiling to the floor and... a giant of blood stands before me. His beard and his hair drip blood. He seats himself on the altar and laughs from thick lips. The black executioner raises his sword and whirls it above my head. Another moment and my head will roll down on the floor. Another moment and the red jet will spurt from my neck. "Murderers! Murderers! None other than murderers!" I paused in the reading. "There's nothing here," I remarked, glancing over the curious document for a clue, but finding none. "Well," remarked Craig contemplatively, "one can at least easily understand how sensitive and imaginative people who have fallen under the influence of one who writes in that way can feel justified in killing those responsible for bringing such horrors on the human race. Hello--what's this?" He had discovered a false back of one of the drawers in the desk and had jimmied it open. On the top of innumerable papers lay a large linen envelope. On its face it bore in typewriting, just like the card on the drawer at Fortescue's, "E-M GUN." "It is the original envelope that contained the final plans of the electro-magnetic gun," he explained, opening it. The envelope was empty. We looked at each other a moment in silence. What had been done with the plans? Suddenly a bell rang, startling me beyond measure. It was, however, only the telephone, of which an extension reached up into the attic-arsenal. Some one, who did not know that we were there, was evidently calling up. Kennedy quickly unhooked the receiver with a hasty motion to me to be silent. "Hello," I heard him answer. "Yes, this is it." He had disguised his voice. I waited anxiously and watched his face to gather what response he received. "The deuce!" he exclaimed, with his hand over the transmitter so that his voice would not be heard at the other end of the line. "What's the matter?" I asked eagerly. "It was Mrs. Annenberg--I am sure. But she was too keen for me. She caught on. There must be some password or form of expression that they use, which we don't know, for she hung up the receiver almost as soon as she heard me." Kennedy waited a minute or so. Then he whistled into the transmitter. It was done apparently to see whether there was anyone listening. But there was no answer. "Operator, operator!" he called insistently, moving the hook up and down. "Yes, operator. Can you tell me what number that was which just called?" He waited impatiently. "Bleecker--7l80," he repeated after the girl. "Thank you. Information, please." Again we waited, as Craig tried to trace the call up. "What is the street address of Bleecker, 7180?" he asked. "Five hundred and one East Fifth--a tenement. Thank you." "A tenement?" I repeated blankly. "Yes," he cried, now for the first time excited. "Don't you begin to see the scheme? I'll wager that Baron Kreiger has been lured to New York to purchase the electro-magnetic gun which they have stolen from Fortescue and the British. That is the bait that is held out to him by the woman. Call up Miss Lowe at the laboratory and see if she knows the place." I gave central the number, while he fell to at the little secret drawer of the desk again. The grinding of the wheels of a passing trolley interfered somewhat with giving the number and I had to wait a moment. "Ah--Walter--here's the list!" almost shouted Kennedy, as he broke open a black-japanned dispatch box in the desk. I bent over it, as far as the slack of the telephone wire of the receiver at my ear would permit. Annenberg had worked with amazing care and neatness on the list, even going so far as to draw at the top, in black, a death's head. The rest of it was elaborately prepared in flaming red ink. Craig gasped to observe the list of world-famous men marked for destruction in London, Paris, Berlin, Rome, Vienna, St. Petersburg, and even in New York and Washington. "What is the date set?" I asked, still with my ear glued to the receiver. "To-night and to-morrow," he replied, stuffing the fateful sheet into his pocket. Rummaging about in the drawer of the table, I had come to a package of gold-tipped cigarettes which had interested me and I had left them out. Kennedy was now looking at them curiously. "What is to be the method, do you suppose?" I asked. "By a poison that is among the most powerful, approaching even cyanogen," he replied confidently, tapping the cigarettes. "Do you smell the odor in this room? What is it like?" "Stale tobacco," I replied. "Exactly--nicotine. Two or three drops on the mouth-end of a cigar or cigarette. The intended victim thinks it is only natural. But it is the purest form of the deadly alkaloid--fatal in a few minutes, too." He examined the thin little cigarettes more carefully. "Nicotine," he went on, "was about the first alkaloid that was recovered from the body by chemical analysis in a homicide case. That is the penetrating, persistent odor you smelled at Fortescue's and also here. It's a very good poison--if you are not particular about being discovered. A pound of ordinary smoking tobacco contains from a half to an ounce of it. It is almost entirely consumed by combustion; otherwise a pipeful would be fatal. Of course they may have thought that investigators would believe that their victims were inveterate smokers. But even the worst tobacco fiend wouldn't show traces of the weed to such an extent." Miss Lowe answered at last and Kennedy took the telephone. "What is at five hundred and one East Fifth?" he asked. "A headquarters of the Group in the city," she answered. "Why?" "Well, I believe that the plans of that gun are there and that the Baron--" "You damned spies!" came a voice from behind us. Kennedy dropped the receiver, turning quickly, his automatic gleaming in his hand. There was just a glimpse of a man with glittering bright blue eyes that had an almost fiendish, baleful glare. An instant later the door which had so unexpectedly opened banged shut, we heard a key turn in the lock--and the man dropped to the floor before even Kennedy's automatic could test its ability to penetrate wood on a chance at hitting something the other side of it. We were prisoners! My mind worked automatically. At this very moment, perhaps, Baron Kreiger might be negotiating for the electro-magnetic gun. We had found out where he was, in all probability, but we were powerless to help him. I thought of Miss Lowe, and picked up the receiver which Kennedy had dropped. She did not answer. The wire had been cut. We were isolated! Kennedy had jumped to the window. I followed to restrain him, fearing that he had some mad scheme for climbing out. Instead, quickly he placed a peculiar arrangement, from the little package he had brought, holding it to his eye as if sighting it, his right hand grasping a handle as one holds a stereoscope. A moment later, as I examined it more closely, I saw that instead of looking at anything he had before him a small parabolic mirror turned away from him. His finger pressed alternately on a button on the handle and I could see that there flashed in the little mirror a minute incandescent lamp which seemed to have a special filament arrangement. The glaring sun was streaming in at the window and I wondered what could possibly be accomplished by the little light in competition with the sun itself. "Signaling by electric light in the daytime may sound to you ridiculous," explained Craig, still industriously flashing the light, "but this arrangement with Professor Donath's signal mirror makes it possible, all right. "I hadn't expected this, but I thought I might want to communicate with Burke quickly. You see, I sight the lamp and then press the button which causes the light in the mirror to flash. It seems a paradox that a light like this can be seen from a distance of even five miles and yet be invisible to one for whom it was not intended, but it is so. I use the ordinary Morse code--two seconds for a dot, six for a dash with a four-second interval." "What message did you send?" I asked. "I told him that Baron Kreiger was at five hundred and one East Fifth, probably; to get the secret service office in New York by wire and have them raid the place, then to come and rescue us. That was Annenberg. He must have come up by that trolley we heard passing just before." The minutes seemed ages as we waited for Burke to start the machinery of the raid and then come for us. "No--you can't have a cigarette--and if I had a pair of bracelets with me, I'd search you myself," we heard a welcome voice growl outside the door a few minutes later. "Look in that other pocket, Tom." The lock grated back and there stood Burke holding in a grip of steel the undersized Annenberg, while the chauffeur who had driven our car swung open the door. "I'd have been up sooner," apologized Burke, giving the anarchist an extra twist just to let him know that he was at last in the hands of the law, "only I figured that this fellow couldn't have got far away in this God-forsaken Ducktown and I might as well pick him up while I had a chance. That's a great little instrument of yours, Kennedy. I got you, fine." Annenberg, seeing we were now four to one, concluded that discretion was the better part of valor and ceased to struggle, though now and then I could see he glanced at Kennedy out of the corner of his eye. To every question he maintained a stolid silence. A few minutes later, with the arch anarchist safely pinioned between us, we were speeding back toward New York, laying plans for Burke to dispatch warnings abroad to those whose names appeared on the fatal list, and at the same time to round up as many of the conspirators as possible in America. As for Kennedy, his main interest now lay in Baron Kreiger and Paula. While she had been driven frantic by the outcome of the terrible pact into which she had been drawn, some one, undoubtedly, had been trying to sell Baron Kreiger the gun that had been stolen from the American inventor. Once they had his money and he had received the plans of the gun, a fatal cigarette would be smoked. Could we prevent it? On we tore back to the city, across the bridge and down through the canyons of East Side streets. At last we pulled up before the tenement at five hundred and one. As we did so, one of Burke's men jumped out of the doorway. "Are we in time?" shouted Burke. "It's an awful mix-up," returned the man. "I can't make anything out of it, so I ordered 'em all held here till you came." We pushed past without a word of criticism of his wonderful acumen. On the top floor we came upon a young man, bending over the form of a girl who had fainted. On the floor of the middle of the room was a mass of charred papers which had evidently burned a hole in the carpet before they had been stamped out. Near by was an unlighted cigarette, crushed flat on the floor. "How is she?" asked Kennedy anxiously of the young man, as he dropped down on the other side of the girl. It was Paula. She had fainted, but was just now coming out of the borderland of unconsciousness. "Was I in time? Had he smoked it?" she moaned weakly, as there swam before her eyes, evidently, a hazy vision of our faces. Kennedy turned to the young man. "Baron Kreiger, I presume?" he inquired. The young man nodded. "Burke of the Secret Service," introduced Craig, indicating our friend. "My name is Kennedy. Tell what happened." "I had just concluded a transaction," returned Kreiger in good but carefully guarded English. "Suddenly the door burst open. She seized these papers and dashed a cigarette out of my hands. The next instant she had touched a match to them and had fallen in a faint almost in the blaze. Strangest experience I ever had in my life. Then all these other fellows came bursting in--said they were Secret Service men, too." Kennedy had no time to reply, for a cry from Annenberg directed our attention to the next room where on a couch lay a figure all huddled up. As we looked we saw it was a woman, her head sweating profusely, and her hands cold and clammy. There was a strange twitching of the muscles of the face, the pupils of her eyes were widely dilated, her pulse weak and irregular. Evidently her circulation had failed so that it responded only feebly to stimulants, for her respiration was slow and labored, with loud inspiratory gasps. Annenberg had burst with superhuman strength from Burke's grasp and was kneeling by the side of his wife's deathbed. "It--was all Paula's fault--" gasped the woman. "I--knew I had better--carry it through--like the Fortescue visit--alone." I felt a sense of reassurance at the words. At least my suspicions had been unfounded. Paula was innocent of the murder of Fortescue. "Severe, acute nicotine poisoning," remarked Kennedy, as he rejoined us a moment later. "There is nothing we can do--now." Paula moved at the words, as though they had awakened a new energy in her. With a supreme effort she raised herself. "Then I--I failed?" she cried, catching sight of Kennedy. "No, Miss Lowe," he answered gently. "You won. The plans of the terrible gun are destroyed. The Baron is safe. Mrs. Annenberg has herself smoked one of the fatal cigarettes intended for him." Kreiger looked at us, uncomprehending. Kennedy picked up the crushed, unlighted cigarette and laid it in the palm of his hand beside another, half smoked, which he had found beside Mrs. Annenberg. "They are deadly," he said simply to Kreiger. "A few drops of pure nicotine hidden by that pretty gilt tip would have accomplished all that the bitterest anarchist could desire." All at once Kreiger seemed to realize what he had escaped so narrowly. He turned toward Paula. The revulsion of her feelings at seeing him safe was too much for her shattered nerves. With a faint little cry, she tottered. Before any of us could reach her, he had caught her in his arms and imprinted a warm kiss on the insensible lips. "Some water--quick!" he cried, still holding her close. CHAPTER IV THE AIR PIRATE Rounding up the "Group" took several days, and it proved to be a great story for the Star. I was pretty fagged when it was all over, but there was a great deal of satisfaction in knowing that we had frustrated one of the most daring anarchist plots of recent years. "Can you arrange to spend the week-end with me at Stuyvesant Verplanck's at Bluffwood?" asked Kennedy over the telephone, the afternoon that I had completed my work on the newspaper of undoing what Annenberg and the rest had attempted. "How long since society took you up?" I asked airily, adding, "Is it a large house party you are getting up?" "You have heard of the so-called 'phantom bandit' of Bluffwood, haven't you?" he returned rather brusquely, as though there was no time now for bantering. I confess that in the excitement of the anarchists I had forgotten it, but now I recalled that for several days I had been reading little paragraphs about robberies on the big estates on the Long Island shore of the Sound. One of the local correspondents had called the robber a "phantom bandit," but I had thought it nothing more than an attempt to make good copy out of a rather ordinary occurrence. "Well," he hurried on, "that's the reason why I have been 'taken up by society,' as you so elegantly phrase it. From the secret hiding-places of the boudoirs and safes of fashionable women at Bluffwood, thousands of dollars' worth of jewels and other trinkets have mysteriously vanished. Of course you'll come along. Why, it will be just the story to tone up that alleged page of society news you hand out in the Sunday Star. There--we're quits now. Seriously, though, Walter, it really seems to be a very baffling case, or rather series of cases. The whole colony out there is terrorized. They don't know who the robber is, or how he operates, or who will be the next victim, but his skill and success seem almost uncanny. Mr. Verplanck has put one of his cars at my disposal and I'm up here at the laboratory gathering some apparatus that may be useful. I'll pick you up anywhere between this and the Bridge--how about Columbus Circle in half an hour?" "Good," I agreed, deciding quickly from his tone and manner of assurance that it would be a case I could not afford to miss. The Stuyvesant Verplancks, I knew, were among the leaders of the rather recherche society at Bluffwood, and the pace at which Bluffwood moved and had its being was such as to guarantee a good story in one way or another. "Why," remarked Kennedy, as we sped out over the picturesque roads of the north shore of Long Island, "this fellow, or fellows, seems to have taken the measure of all the wealthy members of the exclusive organizations out there--the Westport Yacht Club, the Bluffwood Country Club, the North Shore Hunt, and all of them. It's a positive scandal, the ease with which he seems to come and go without detection, striking now here, now there, often at places that it seems physically impossible to get at, and yet always with the same diabolical skill and success. One night he will take some baubles worth thousands, the next pass them by for something apparently of no value at all, a piece of bric-a-brac, a bundle of letters, anything." "Seems purposeless, insane, doesn't it?" I put in. "Not when he always takes something--often more valuable than money," returned Craig. He leaned back in the car and surveyed the glimpses of bay and countryside as we were whisked by the breaks in the trees. "Walter," he remarked meditatively, "have you ever considered the possibilities of blackmail if the right sort of evidence were obtained under this new 'white-slavery act'? Scandals that some of the fast set may be inclined to wink at, that at worst used to end in Reno, become felonies with federal prison sentences looming up in the background. Think it over." Stuyvesant Verplanck had telephoned rather hurriedly to Craig earlier in the day, retaining his services, but telling only in the briefest way of the extent of the depredations, and hinting that more than jewelry might be at stake. It was a pleasant ride, but we finished it in silence. Verplanck was, as I recalled, a large masterful man, one of those who demanded and liked large things--such as the estate of several hundred acres which we at last entered. It was on a neck of land with the restless waters of the Sound on one side and the calmer waters of the bay on the other. Westport Bay lay in a beautifully wooded, hilly country, and the house itself was on an elevation, with a huge sweep of terraced lawn before it down to the water's edge. All around, for miles, were other large estates, a veritable colony of wealth. As we pulled up under the broad stone porte-cochere, Verplanck, who had been expecting us, led the way into his library, a great room, literally crowded with curios and objects of art which he had collected on his travels. It was a superb mental workshop, overlooking the bay, with a stretch of several miles of sheltered water. "You will recall," began Verplanck, wasting no time over preliminaries, but plunging directly into the subject, "that the prominent robberies of late have been at seacoast resorts, especially on the shores of Long Island Sound, within, say, a hundred miles of New York. There has been a great deal of talk about dark and muffled automobiles that have conveyed mysterious parties swiftly and silently across country. "My theory," he went on self-assertively, "is that the attack has been made always along water routes. Under shadow of darkness, it is easy to slip into one of the sheltered coves or miniature fiords with which the north coast of the Island abounds, land a cut-throat crew primed with exact information of the treasure on some of these estates. Once the booty is secured, the criminal could put out again into the Sound without leaving a clue." He seemed to be considering his theory. "Perhaps the robberies last summer at Narragansett, Newport, and a dozen other New England places were perpetrated by the same cracksman. I believe," he concluded, lowering his voice, "that there plies to-day on the wide waters of the Sound a slim, swift motor boat which wears the air of a pleasure craft, yet is as black a pirate as ever flew the Jolly Roger. She may at this moment be anchored off some exclusive yacht club, flying the respectable burgee of the club--who knows?" He paused as if his deductions settled the case so far. He would have resumed in the same vein, if the door had not opened. A lady in a cobwebby gown entered the room. She was of middle age, but had retained her youth with a skill that her sisters of less leisure always envy. Evidently she had not expected to find anyone, yet nothing seemed to disconcert her. "Mrs. Verplanck," her husband introduced, "Professor Kennedy and his associate, Mr. Jameson--those detectives we have heard about. We were discussing the robberies." "Oh, yes," she said, smiling, "my husband has been thinking of forming himself into a vigilance committee. The local authorities are all at sea." I thought there was a trace of something veiled in the remark and fancied, not only then but later, that there was an air of constraint between the couple. "You have not been robbed yourself?" queried Craig tentatively. "Indeed we have," exclaimed Verplanck quickly. "The other night I was awakened by the noise of some one down here in this very library. I fired a shot, wild, and shouted, but before I could get down here the intruder had fled through a window, and half rolling down the terraces. Mrs. Verplanck was awakened by the rumpus and both of us heard a peculiar whirring noise." "Like an automobile muffled down," she put in. "No," he asserted vigorously, "more like a powerful motor boat, one with the exhaust under water." "Well," she shrugged, "at any rate, we saw no one." "Did the intruder get anything?" "That's the lucky part. He had just opened this safe apparently and begun to ransack it. This is my private safe. Mrs. Verplanck has another built into her own room upstairs where she keeps her jewels." "It is not a very modern safe, is it?" ventured Kennedy. "The fellow ripped off the outer casing with what they call a 'can-opener.'" "No. I keep it against fire rather than burglars. But he overlooked a box of valuable heirlooms, some silver with the Verplanck arms. I think I must have scared him off just in time. He seized a package in the safe, but it was only some business correspondence. I don't relish having lost it, particularly. It related to a gentlemen's agreement a number of us had in the recent cotton corner. I suppose the Government would like to have it. But--here's the point. If it is so easy to get in and get away, no one in Bluffwood is safe." "Why, he robbed the Montgomery Carter place the other night," remarked Mrs. Verplanck, "and almost got a lot of old Mrs. Carter's jewels as well as stuff belonging to her son, Montgomery, Junior. That was the first robbery. Mr. Carter, that is Junior--Monty, everyone calls him--and his chauffeur almost captured the fellow, but he managed to escape in the woods." "In the woods?" repeated Craig. Mrs. Verplanck nodded. "But they saved the loot he was about to take." "Oh, no one is safe any more," reiterated Verplanck. "Carter seems to be the only one who has had a real chance at him, and he was able to get away neatly." "But he's not the only one who got off without a loss," she put in significantly. "The last visit--" Then she paused. "Where was the last attempt?" asked Kennedy. "At the house of Mrs. Hollingsworth--around the point on this side of the bay. You can't see it from here." "I'd like to go there," remarked Kennedy. "Very well. Car or boat?" "Boat, I think." "Suppose we go in my little runabout, the Streamline II? She's as fast as any ordinary automobile." "Very good. Then we can get an idea of the harbor." "I'll telephone first that we are coming," said Verplanck. "I think I'll go, too," considered Mrs. Verplanck, ringing for a heavy wrap. "Just as you please," said Verplanck. The Streamline was a three-stepped boat which. Verplanck had built for racing, a beautiful craft, managed much like a racing automobile. As she started from the dock, the purring drone of her eight cylinders sent her feathering over the waves like a skipping stone. She sank back into the water, her bow leaping upward, a cloud of spray in her wake, like a waterspout. Mrs. Hollingsworth was a wealthy divorcee, living rather quietly with her two children, of whom the courts had awarded her the care. She was a striking woman, one of those for whom the new styles of dress seem especially to have been designed. I gathered, however, that she was not on very good terms with the little Westport clique in which the Verplancks moved, or at least not with Mrs. Verplanck. The two women seemed to regard each other rather coldly, I thought, although Mr. Verplanck, man-like, seemed to scorn any distinctions and was more than cordial. I wondered why Mrs. Verplanck had come. The Hollingsworth house was a beautiful little place down the bay from the Yacht Club, but not as far as Verplanck's, or the Carter estate, which was opposite. "Yes," replied Mrs. Hollingsworth when the reason for our visit had been explained, "the attempt was a failure. I happened to be awake, rather late, or perhaps you would call it early. I thought I heard a noise as if some one was trying to break into the drawing-room through the window. I switched on all the lights. I have them arranged so for just that purpose of scaring off intruders. Then, as I looked out of my window on the second floor, I fancied I could see a dark figure slink into the shadow of the shrubbery at the side of the house. Then there was a whirr. It might have been an automobile, although it sounded differently from that--more like a motor boat. At any rate, there was no trace of a car that we could discover in the morning. The road had been oiled, too, and a car would have left marks. And yet some one was here. There were marks on the drawing-room window just where I heard the sounds." Who could it be? I asked myself as we left. I knew that the great army of chauffeurs was infested with thieves, thugs and gunmen. Then, too, there were maids, always useful as scouts for these corsairs who prey on the rich. Yet so adroitly had everything been done in these cases that not a clue seemed to have been left behind by which to trace the thief. We returned to Verplanck's in the Streamline in record time, dined, and then found McNeill, a local detective, waiting to add his quota of information. McNeill was of the square-toed, double-chinned, bull-necked variety, just the man to take along if there was any fighting. He had, however, very little to add to the solution of the mystery, apparently believing in the chauffeur-and-maid theory. It was too late to do anything more that night, and we sat on the Verplanck porch, overlooking the beautiful harbor. It was a black, inky night, with no moon, one of those nights when the myriad lights on the boats were mere points in the darkness. As we looked out over the water, considering the case which as yet we had hardly started on, Kennedy seemed engrossed in the study in black. "I thought I saw a moving light for an instant across the bay, above the boats, and as though it were in the darkness of the hills on the other side. Is there a road over there, above the Carter house?" he asked suddenly. "There is a road part of the way on the crest of the hill," replied Mrs. Verplanck. "You can see a car on it, now and then, through the trees, like a moving light." "Over there, I mean," reiterated Kennedy, indicating the light as it flashed now faintly, then disappeared, to reappear further along, like a gigantic firefly in the night. "N-no," said Verplanck. "I don't think the road runs down as far as that. It is further up the bay." "What is it then?" asked Kennedy, half to himself. "It seems to be traveling rapidly. Now it must be about opposite the Carter house. There--it has gone." We continued to watch for several minutes, but it did not reappear. Could it have been a light on the mast of a boat moving rapidly up the bay and perhaps nearer to us than we suspected? Nothing further happened, however, and we retired early, expecting to start with fresh minds on the case in the morning. Several watchmen whom Verplanck employed both on the shore and along the driveways were left guarding every possible entrance to the estate. Yet the next morning as we met in the cheery east breakfast room, Verplanck's gardener came in, hat in hand, with much suppressed excitement. In his hand he held an orange which he had found in the shrubbery underneath the windows of the house. In it was stuck a long nail and to the nail was fastened a tag. Kennedy read it quickly. "If this had been a bomb, you and your detectives would never have known what struck you. "AQUAERO." CHAPTER V THE ULTRA-VIOLET RAY "Good Gad, man!" exclaimed Verplanck, who had read it over Craig's shoulder. "What do you make of THAT?" Kennedy merely shook his head. Mrs. Verplanck was the calmest of all. "The light," I cried. "You remember the light? Could it have been a signal to some one on this side of the bay, a signal light in the woods?" "Possibly," commented Kennedy absently, adding, "Robbery with this fellow seems to be an art as carefully strategized as a promoter's plan or a merchant's trade campaign. I think I'll run over this morning and see if there is any trace of anything on the Carter estate." Just then the telephone rang insistently. It was McNeill, much excited, though he had not heard of the orange incident. Verplanck answered the call. "Have you heard the news?" asked McNeill. "They report this morning that that fellow must have turned up last night at Belle Aire." "Belle Aire? Why, man, that's fifty miles away and on the other side of the island. He was here last night," and Verplanck related briefly the find of the morning. "No boat could get around the island in that time and as for a car--those roads are almost impossible at night." "Can't help it," returned McNeill doggedly. "The Halstead estate out at Belle Aire was robbed last night. It's spooky all right." "Tell McNeill I want to see him--will meet him in the village directly," cut in Craig before Verplanck had finished. We bolted a hasty breakfast and in one of Verplanck's cars hurried to meet McNeill. "What do you intend doing?" he asked helplessly, as Kennedy finished his recital of the queer doings of the night before. "I'm going out now to look around the Carter place. Can you come along?" "Surely," agreed McNeill, climbing into the car. "You know him?" "No." "Then I'll introduce you. Queer chap, Carter. He's a lawyer, although I don't think he has much practice, except managing his mother's estate." McNeill settled back in the luxurious car with an exclamation of satisfaction. "What do you think of Verplanck?" he asked. "He seems to me to be a very public-spirited man," answered Kennedy discreetly. That, however, was not what McNeill meant and he ignored it. And so for the next ten minutes we were entertained with a little retail scandal of Westport and Bluffwood, including a tale that seemed to have gained currency that Verplanck and Mrs. Hollingsworth were too friendly to please Mrs. Verplanck. I set the whole thing down to the hostility and jealousy of the towns people who misinterpret everything possible in the smart set, although I could not help recalling how quickly she had spoken when we had visited the Hollingsworth house in the Streamline the day before. Montgomery Carter happened to be at home and, at least openly, interposed no objection to our going about the grounds. "You see," explained Kennedy, watching the effect of his words as if to note whether Carter himself had noticed anything unusual the night before, "we saw a light moving over here last night. To tell the truth, I half expected you would have a story to add to ours, of a second visit." Carter smiled. "No objection at all. I'm simply nonplussed at the nerve of this fellow, coming back again. I guess you've heard what a narrow squeak he had with me. You're welcome to go anywhere, just so long as you don't disturb my study down there in the boathouse. I use that because it overlooks the bay--just the place to study over knotty legal problems." Back of, or in front of the Carter house, according as you fancied it faced the bay or not, was the boathouse, built by Carter's father, who had been a great yachtsman in his day and commodore of the club. His son had not gone in much for water sports and had converted the corner underneath a sort of observation tower into a sort of country law office. "There has always seemed to me to be something strange about that boathouse since the old man died," remarked McNeill in a half whisper as we left Carter. "He always keeps it locked and never lets anyone go in there, although they say he has it fitted beautifully with hundreds of volumes of law books, too." Kennedy had been climbing the hill back of the house and now paused to look about. Below was the Carter garage. "By the way," exclaimed McNeill, as if he had at last hit on a great discovery, "Carter has a new chauffeur, a fellow named Wickham. I just saw him driving down to the village. He's a chap that it might pay us to watch--a newcomer, smart as a steel trap, they say, but not much of a talker." "Suppose you take that job--watch him," encouraged Kennedy. "We can't know too much about strangers here, McNeill." "That's right," agreed the detective. "I'll follow him back to the village and get a line on him." "Don't be easily discouraged," added Kennedy, as McNeill started down the hill to the garage. "If he is a fox he'll try to throw you off the trail. Hang on." "What was that for?" I asked as the detective disappeared. "Did you want to get rid of him?" "Partly," replied Craig, descending slowly, after a long survey of the surrounding country. We had reached the garage, deserted now except for our own car. "I'd like to investigate that tower," remarked Kennedy with a keen look at me, "if it could be done without seeming to violate Mr. Carter's hospitality." "Well," I observed, my eye catching a ladder beside the garage, "there's a ladder. We can do no more than try." He walked over to the automobile, took a little package out, slipped it into his pocket, and a few minutes later we had set the ladder up against the side of the boathouse farthest away from the house. It was the work of only a moment for Kennedy to scale it and prowl across the roof to the tower, while I stood guard at the foot. "No one has been up there recently," he panted breathlessly as he rejoined me. "There isn't a sign." We took the ladder quietly back to the garage, then Kennedy led the way down the shore to a sort of little summerhouse cut off from the boathouse and garage by the trees, though over the top of a hedge one could still see the boathouse tower. We sat down, and Craig filled his lungs with the good salt air, sweeping his eye about the blue and green panorama as though this were a holiday and not a mystery case. "Walter," he said at length, "I wish you'd take the car and go around to Verplanck's. I don't think you can see the tower through the trees, but I should like to be sure." I found that it could not be seen, though I tried all over the place and got myself disliked by the gardener and suspected by a watchman with a dog. It could not have been from the tower of the boathouse that we had seen the light, and I hurried back to Craig to tell him so. But when I returned, I found that he was impatiently pacing the little rustic summerhouse, no longer interested in what he had sent me to find out. "What has happened?" I asked eagerly. "Just come out here and I'll show you something," he replied, leaving the summerhouse and approaching the boathouse from the other side of the hedge, on the beach, so that the house itself cut us off from observation from Carter's. "I fixed a lens on the top of that tower when I was up there," he explained, pointing up at it. "It must be about fifty feet high. From there, you see, it throws a reflection down to this mirror. I did it because through a skylight in the tower I could read whatever was written by anyone sitting at Carter's desk in the corner under it." "Read?" I repeated, mystified. "Yes, by invisible light," he continued. "This invisible light business, you know, is pretty well understood by this time. I was only repeating what was suggested once by Professor Wood of Johns Hopkins. Practically all sources of light, you understand, give out more or less ultraviolet light, which plays no part in vision whatever. The human eye is sensitive to but few of the light rays that reach it, and if our eyes were constituted just the least bit differently we should have an entirely different set of images. "But by the use of various devices we can, as it were, translate these ultraviolet rays into terms of what the human eye can see. In order to do it, all the visible light rays which show us the thing as we see it--the tree green, the sky blue--must be cut off. So in taking an ultraviolet photograph a screen must be used which will be opaque to these visible rays and yet will let the ultraviolet rays through to form the image. That gave Professor Wood a lot of trouble. Glass won't do, for glass cuts off the ultraviolet rays entirely. Quartz is a very good medium, but it does not cut off all the visible light. In fact there is only one thing that will do the work, and that is metallic silver." I could not fathom what he was driving at, but the fascination of Kennedy himself was quite sufficient. "Silver," he went on, "is all right if the objects can be illuminated by an electric spark or some other source rich in the rays. But it isn't entirely satisfactory when sunlight is concerned, for various reasons that I need not bore you with. Professor Wood has worked out a process of depositing nickel on glass. That's it up there," he concluded, wheeling a lower reflector about until it caught the image of the afternoon sun thrown from the lens on the top of the tower. "You see," he resumed, "that upper lens is concave so that it enlarges tremendously. I can do some wonderful tricks with that." I had been lighting a cigarette and held a box of safety wind matches in my hand. "Give me that matchbox," he asked. He placed it at the foot of the tower. Then he went off, I should say, without exaggeration, a hundred feet. The lettering on the matchbox could be seen in the silvered mirror, enlarged to such a point that the letters were plainly visible! "Think of the possibilities in that," he added excitedly. "I saw them at once. You can read what some one is writing at a desk a hundred, perhaps two hundred feet away." "Yes," I cried, more interested in the practical aspects of it than in the mechanics and optics. "What have you found?" "Some one came into the boathouse while you were away," he said. "He had a note. It read, 'Those new detectives are watching everything. We must have the evidence. You must get those letters to-night, without fail.'" "Letters--evidence," I repeated. "Who wrote it? Who received it?" "I couldn't see over the hedge who had entered the boathouse, and by the time I got around here he was gone." "Was it Wickham--or intended for Wickham?" I asked. Kennedy shrugged his shoulders. "We'll gain nothing by staying here," he said. "There is just one possibility in the case, and I can guard against that only by returning to Verplanck's and getting some of that stuff I brought up here with me. Let us go." Late in the afternoon though it was, after our return, Kennedy insisted on hurrying from Verplanck's to the Yacht Club up the bay. It was a large building, extending out into the water on made land, from which ran a long, substantial dock. He had stopped long enough only to ask Verplanck to lend him the services of his best mechanician, a Frenchman named Armand. On the end of the yacht club dock Kennedy and Armand set up a large affair which looked like a mortar. I watched curiously, dividing my attention between them and the splendid view of the harbor which the end of the dock commanded on all sides. "What is this?" I asked finally. "Fireworks?" "A rocket mortar of light weight," explained Kennedy, then dropped into French as he explained to Armand the manipulation of the thing. There was a searchlight near by on the dock. "You can use that?" queried Kennedy. "Oh, yes. Mr. Verplanck, he is vice-commodore of the club. Oh, yes, I can use that. Why, Monsieur?" Kennedy had uncovered a round brass case. It did not seem to amount to much, as compared to some of the complicated apparatus he had used. In it was a four-sided prism of glass--I should have said, cut off the corner of a huge glass cube. He handed it to us. "Look in it," he said. It certainly was about the most curious piece of crystal gazing I had ever done. Turn the thing any way I pleased and I could see my face in it, just as in an ordinary mirror. "What do you call it?" Armand asked, much interested. "A triple mirror," replied Kennedy, and again, half in English and half in French, neither of which I could follow, he explained the use of the mirror to the mechanician. We were returning up the dock, leaving Armand with instructions to be at the club at dusk, when we met McNeill, tired and disgusted. "What luck?" asked Kennedy. "Nothing," he returned. "I had a 'short' shadow and a 'long' shadow at Wickham's heels all day. You know what I mean. Instead of one man, two--the second sleuthing in the other's tracks. If he escaped Number One, Number Two would take it up, and I was ready to move up into Number Two's place. They kept him in sight about all the time. Not a fact. But then, of course, we don't know what he was doing before we took up tailing him. Say," he added, "I have just got word from an agency with which I correspond in New York that it is reported that a yeggman named 'Australia Mac,' a very daring and clever chap, has been attempting to dispose of some of the goods which we know have been stolen through one of the worst 'fences' in New York." "Is that all?" asked Craig, with the mention of Australia Mac showing the first real interest yet in anything that McNeill had done since we met him the night before. "All so far. I wired for more details immediately." "Do you know anything about this Australia Mac?" "Not much. No one does. He's a new man, it seems, to the police here." "Be here at eight o'clock, McNeill," said Craig, as we left the club for Verplanck's. "If you can find out more about this yeggman, so much the better." "Have you made any progress?" asked Verplanck as we entered the estate a few minutes later. "Yes," returned Craig, telling only enough to whet his interest. "There's a clue, as I half expected, from New York, too. But we are so far away that we'll have to stick to my original plan. You can trust Armand?" "Absolutely." "Then we shall transfer our activity to the Yacht Club to-night," was all that Kennedy vouchsafed. CHAPTER VI THE TRIPLE MIRROR It was the regular Saturday night dance at the club, a brilliant spectacle, faces that radiated pleasure, gowns that for startling combinations of color would have shamed a Futurist, music that set the feet tapping irresistibly--a scene which I shall pass over because it really has no part in the story. The fascination of the ballroom was utterly lost on Craig. "Think of all the houses only half guarded about here to-night," he mused, as we joined Armand and McNeill on the end of the dock. I could not help noting that that was the only idea which the gay, variegated, sparkling tango throng conveyed to him. In front of the club was strung out a long line of cars, and at the dock several speed boats of national and international reputation, among them the famous Streamline II, at our instant beck and call. In it Craig had already placed some rather bulky pieces of apparatus, as well as a brass case containing a second triple mirror like that which he had left with Armand. With McNeill, I walked back along the pier, leaving Kennedy with Armand, until we came to the wide porch, where we joined the wallflowers and the rocking-chair fleet. Mrs. Verplanck, I observed, was a beautiful dancer. I picked her out in the throng immediately, dancing with Carter. McNeill tugged at my sleeve. Without a word I saw what he meant me to see. Verplanck and Mrs. Hollingsworth were dancing together. Just then, across the porch I caught sight of Kennedy at one of the wide windows. He was trying to attract Verplanck's attention, and as he did so I worked my way through the throng of chatting couples leaving the floor until I reached him. Verplanck, oblivious, finished the dance; then, seeming to recollect that he had something to attend to, caught sight of us, and ran off during the intermission from the gay crowd to which he resigned Mrs. Hollingsworth. "What is it?" he asked. "There's that light down the bay," whispered Kennedy. Instantly Verplanck forgot about the dance. "Where?" he asked. "In the same place." I had not noticed, but Mrs. Verplanck, woman-like, had been able to watch several things at once. She had seen us and had joined us. "Would you like to run down there in the Streamline?" he asked. "It will only take a few minutes." "Very much." "What is it--that light again?" she asked, as she joined us in walking down the dock. "Yes," answered her husband, pausing to look for a moment at the stuff Kennedy had left with Armand. Mrs. Verplanck leaned over the Streamline, turned as she saw me, and said: "I wish I could go with you. But evening dress is not the thing for a shivery night in a speed boat. I think I know as much about it as Mr. Verplanck. Are you going to leave Armand?" "Yes," replied Kennedy, taking his place beside Verplanck, who was seated at the steering wheel. "Walter and McNeill, if you two will sit back there, we're ready. All right." Armand had cast us off and Mrs. Verplanck waved from the end of the float as the Streamline quickly shot out into the night, a buzzing, throbbing shape of mahogany and brass, with her exhausts sticking out like funnels and booming like a pipe organ. It took her only seconds to eat into the miles. "A little more to port," said Kennedy, as Verplanck swung her around. Just then the steady droning of the engine seemed a bit less rhythmical. Verplanck throttled her down, but it had no effect. He shut her off. Something was wrong. As he crawled out into the space forward of us where the engine was, it seemed as if the Streamline had broken down suddenly and completely. Here we were floundering around in the middle of the bay. "Chuck-chuck-chuck," came in quick staccato out of the night. It was Montgomery Carter, alone, on his way across the bay from the club, in his own boat. "Hello--Carter," called Verplanck. "Hello, Verplanck. What's the matter?" "Don't know. Engine trouble of some kind. Can you give us a line?" "I've got to go down to the house," he said, ranging up near us. "Then I can take you back. Perhaps I'd better get you out of the way of any other boats first. You don't mind going over and then back?" Verplanck looked at Craig. "On the contrary," muttered Craig, as he made fast the welcome line. The Carter dock was some three miles from the club on the other side of the bay. As we came up to it, Carter shut off his engine, bent over it a moment, made fast, and left us with a hurried, "Wait here." Suddenly, overhead, we heard a peculiar whirring noise that seemed to vibrate through the air. Something huge, black, monster-like, slid down a board runway into the water, traveled a few feet, in white suds and spray, rose in the darkness--and was gone! As the thing disappeared, I thought I could hear a mocking laugh flung back at us. "What is it?" I asked, straining my eyes at what had seemed for an instant like a great flying fish with finny tail and huge fins at the sides and above. "'Aquaero,'" quoted Kennedy quickly. "Don't you understand--a hydroaeroplane--a flying boat. There are hundreds of privately owned flying boats now wherever there is navigable water. That was the secret of Carter's boathouse, of the light we saw in the air." "But this Aquaero--who is he?" persisted McNeill. "Carter--Wickham--Australia Mac?" We looked at each other blankly. No one said a word. We were captured, just as effectively as if we were ironed in a dungeon. There were the black water, the distant lights, which at any other time I should have said would have been beautiful. Kennedy had sprung into Carter's boat. "The deuce," he exclaimed. "He's put her out of business." Verplanck, chagrined, had been going over his own engine feverishly. "Do you see that?" he asked suddenly, holding up in the light of a lantern a little nut which he had picked out of the complicated machinery. "It never belonged to this engine. Some one placed it there, knowing it would work its way into a vital part with the vibration." Who was the person, the only one who could have done it? The answer was on my lips, but I repressed it. Mrs. Verplanck herself had been bending over the engine when last I saw her. All at once it flashed over me that she knew more about the phantom bandit than she had admitted. Yet what possible object could she have had in putting the Streamline out of commission? My mind was working rapidly, piecing together the fragmentary facts. The remark of Kennedy, long before, instantly assumed new significance. What were the possibilities of blackmail in the right sort of evidence? The yeggman had been after what was more valuable than jewels--letters! Whose? Suddenly I saw the situation. Carter had not been robbed at all. He was in league with the robber. That much was a blind to divert suspicion. He was a lawyer--some one's lawyer. I recalled the message about letters and evidence, and as I did so there came to mind a picture of Carter and the woman he had been dancing with. In return for his inside information about the jewels of the wealthy homes of Bluffwood, the yeggman was to get something of interest and importance to his client. The situation called for instant action. Yet what could we do, marooned on the other side of the bay? From the Club dock a long finger of light swept out into the night, plainly enough near the dock, but diffused and disclosing nothing in the distance. Armand had trained it down the bay in the direction we had taken, but by the time the beam reached us it was so weak that it was lost. Craig had leaped up on the Carter dock and was capping and uncapping with the brass cover the package which contained the triple mirror. Still in the distance I could see the wide path of light, aimed toward us, but of no avail. "What are you doing?" I asked. "Using the triple mirror to signal to Armand. It is something better than wireless. Wireless requires heavy and complicated apparatus. This is portable, heatless, almost weightless, a source of light depending for its power on another source of light at a great distance." I wondered how Armand could ever detect its feeble ray. "Even in the case of a rolling ship," Kennedy continued, alternately covering and uncovering the mirror, "the beam of light which this mirror reflects always goes back, unerring, to its source. It would do so from an aeroplane, so high in the air that it could not be located. The returning beam is invisible to anyone not immediately in the path of the ray, and the ray always goes to the observer. It is simply a matter of pure mathematics practically applied. The angle of incidence equals the angle of reflection. There is not a variation of a foot in two miles." "What message are you sending him?" asked Verplanck. "To tell Mrs. Hollingsworth to hurry home immediately," Kennedy replied, still flashing the letters according to his code. "Mrs. Hollingsworth?" repeated Verplanck, looking up. "Yes. This hydroaeroplane yeggman is after something besides jewels to-night. Were those letters that were stolen from you the only ones you had in the safe?" Verplanck looked up quickly. "Yes, yes. Of course." "You had none from a woman--" "No," he almost shouted. Of a sudden it seemed to dawn on him what Kennedy was driving at--the robbery of his own house with no loss except of a packet of letters on business, followed by the attempt on Mrs. Hollingsworth. "Do you think I'd keep dynamite, even in the safe?" To hide his confusion he had turned and was bending again over the engine. "How is it?" asked Kennedy, his signaling over. "Able to run on four cylinders and one propeller," replied Verplanck. "Then let's try her. Watch the engine. I'll take the wheel." Limping along, the engine skipping and missing, the once peerless Streamline started back across the bay. Instead of heading toward the club, Kennedy pointed her bow somewhere between that and Verplanck's. "I wish Armand would get busy," he remarked, after glancing now and then in the direction of the club. "What can be the matter?" "What do you mean?" I asked. There came the boom as if of a gun far away in the direction in which he was looking, then another. "Oh, there it is. Good fellow. I suppose he had to deliver my message to Mrs. Hollingsworth himself first." From every quarter showed huge balls of fire, rising from the sea, as it were, with a brilliantly luminous flame. "What is it?" I asked, somewhat startled. "A German invention for use at night against torpedo and aeroplane attacks. From that mortar Armand has shot half a dozen bombs of phosphide of calcium which are hurled far into the darkness. They are so constructed that they float after a short plunge and are ignited on contact by the action of the salt water itself." It was a beautiful pyrotechnic display, lighting up the shore and hills of the bay as if by an unearthly flare. "There's that thing now!" exclaimed Kennedy. In the glow we could see a peculiar, birdlike figure flying through the air over toward the Hollingsworth house. It was the hydroaeroplane. Out from the little stretch of lawn under the accentuated shadow of the trees, she streaked into the air, swaying from side to side as the pilot operated the stabilizers on the ends of the planes to counteract the puffs of wind off the land. How could she ever be stopped? The Streamline, halting and limping, though she was, had almost crossed the bay before the light bombs had been fired by Armand. Every moment brought the flying boat nearer. She swerved. Evidently the pilot had seen us at last and realized who we were. I was so engrossed watching the thing that I had not noticed that Kennedy had given the wheel to Verplanck and was standing in the bow, endeavoring to sight what looked like a huge gun. In rapid succession half a dozen shots rang out. I fancied I could almost hear the ripping and tearing of the tough rubber-coated silken wings of the hydroaeroplane as the wind widened the perforation the gun had made. She had not been flying high, but now she swooped down almost like a gull, seeking to rest on the water. We were headed toward her now, and as the flying boat sank I saw one of the passengers rise in his seat, swing his arm, and far out something splashed in the bay. On the water, with wings helpless, the flying boat was no match for the Streamline now. She struck at an acute angle, rebounded in the air for a moment, and with a hiss skittered along over the waves, planing with the help of her exhaust under the step of the boat. There she was, a hull, narrow, scow-bowed, like a hydroplane, with a long pointed stern and a cockpit for two men, near the bow. There were two wide, winglike planes, on a light latticework of wood covered with silk, trussed and wired like a kite frame, the upper plane about five feet above the lower, which was level with the boat deck. We could see the eight-cylindered engine which drove a two-bladed wooden propeller, and over the stern were the air rudder and the horizontal planes. There she was, the hobbled steed now of the phantom bandit who had accomplished the seemingly impossible. In spite of everything, however, the flying boat reached the shore a trifle ahead of us. As she did so both figures in her jumped, and one disappeared quickly up the bank, leaving the other alone. "Verplanck, McNeill--get him," cried Kennedy, as our own boat grated on the beach. "Come, Walter, we'll take the other one." The man had seen that there was no safety in flight. Down the shore he stood, without a hat, his hair blown pompadour by the wind. As we approached Carter turned superciliously, unbuttoning his bulky khaki life preserver jacket. "Well?" he asked coolly. Not for a moment did Kennedy allow the assumed coolness to take him back, knowing that Carter's delay did not cover the retreat of the other man. "So," Craig exclaimed, "you are the--the air pirate?" Carter disdained to reply. "It was you who suggested the millionaire households, full of jewels, silver and gold, only half guarded; you, who knew the habits of the people; you, who traded that information in return for another piece of thievery by your partner, Australia Mac--Wickham he called himself here in Bluffwood. It was you---" A car drove up hastily, and I noted that we were still on the Hollingsworth estate. Mrs. Hollingsworth had seen us and had driven over toward us. "Montgomery!" she cried, startled. "Yes," said Kennedy quickly, "air pirate and lawyer for Mrs. Verplanck in the suit which she contemplated bringing--" Mrs. Hollingsworth grew pale under the ghastly, flickering light from the bay. "Oh!" she cried, realizing at what Kennedy hinted, "the letters!" "At the bottom of the harbor, now," said Kennedy. "Mr. Verplanck tells me he has destroyed his. The past is blotted out as far as that is concerned. The future is--for you three to determine. For the present I've caught a yeggman and a blackmailer." CHAPTER VII THE WIRELESS WIRETAPPERS Kennedy did not wait at Bluffwood longer than was necessary. It was easy enough now to silence Montgomery Carter, and the reconciliation of the Verplancks was assured. In the Star I made the case appear at the time to involve merely the capture of Australia Mac. When I dropped into the office the next day as usual, I found that I had another assignment that would take me out on Long Island. The story looked promising and I was rather pleased to get it. "Bound for Seaville, I'll wager," sounded a familiar voice in my ear, as I hurried up to the train entrance at the Long Island corner of the Pennsylvania Station. I turned quickly, to find Kennedy just behind me, breathless and perspiring. "Er--yes," I stammered in surprise at seeing him so unexpectedly, "but where did you come from? How did you know?" "Let me introduce Mr. Jack Waldon," he went on, as we edged our way toward the gate, "the brother of Mrs. Tracy Edwards, who disappeared so strangely from the houseboat Lucie last night at Seaville. That is the case you're going to write up, isn't it?" It was then for the first time that I noticed the excited young man beside Kennedy was really his companion. I shook hands with Waldon, who gave me a grip that was both a greeting and an added impulse in our general direction through the wicket. "Might have known the Star would assign you to this Edwards case," panted Kennedy, mopping his forehead, for the heat in the terminal was oppressive and the crowd, though not large, was closely packed. "Mr. Jameson is my right-hand man," he explained to Waldon, taking us each by the arm and urging us forward. "Waldon was afraid we might miss the train or I should have tried to get you, Walter, at the office." It was all done so suddenly that they quite took away what remaining breath I had, as we settled ourselves to swelter in the smoker instead of in the concourse. I did not even protest at the matter-of-fact assurance with which Craig assumed that his deduction as to my destination was correct. Waldon, a handsome young fellow in a flannel suit and yachting cap somewhat the worse for his evidently perturbed state of mind, seemed to eye me for the moment doubtfully, in spite of Kennedy's cordial greeting. "I've had all the first editions of the evening papers," I hinted as we sped through the tunnel, "but the stories seemed to be quite the same--pretty meager in details." "Yes," returned Waldon with a glance at Kennedy, "I tried to keep as much out of the papers as I could just now for Lucie's sake." "You needn't fear Jameson," remarked Kennedy. He fumbled in his pocket, then paused a moment and shot a glance of inquiry at Waldon, who nodded a mute acquiescence to him. "There seem to have been a number of very peculiar disappearances lately," resumed Kennedy, "but this case of Mrs. Edwards is by far the most extraordinary. Of course the Star hasn't had that--yet," he concluded, handing me a sheet of notepaper. "Mr. Waldon didn't give it out, hoping to avoid scandal." I took the paper and read eagerly, in a woman's hand: "MY DEAR MISS FOX: I have been down here at Seaville on our houseboat, the Lucie, for several days for a purpose which now is accomplished. "Already I had my suspicions of you, from a source which I need not name. Therefore, when the Kronprinz got into wireless communication with the station at Seaville I determined through our own wireless on the Lucie to overhear whether there would be any exchange of messages between my husband and yourself. "I was able to overhear the whole thing and I want you to know that your secret is no longer a secret from me, and that I have already told Mr. Edwards that I know it. You ruin his life by your intimacy which you seem to want to keep up, although you know you have no right to do it, but you shall not ruin mine. "I am thoroughly disillusioned now. I have not decided on what steps to take, but--" Only a casual glance was necessary to show me that the writing seemed to grow more and more weak as it progressed, and the note stopped abruptly, as if the writer had been suddenly interrupted or some new idea had occurred to her. Hastily I tried to figure it out. Lucie Waldon, as everybody knew, was a famous beauty, a marvel of charm and daintiness, slender, with big, soulful, wistful eyes. Her marriage to Tracy Edwards, the wealthy plunger and stockbroker, had been a great social event the year before, and it was reputed at the time that Edwards had showered her with jewels and dresses to the wonder and talk even of society. As for Valerie Fox, I knew she had won quick recognition and even fame as a dancer in New York during the previous winter, and I recalled reading three or four days before that she had just returned on the Kronprinz from a trip abroad. "I don't suppose you have had time to see Miss Fox," I remarked. "Where is she?" "At Beach Park now, I think," replied Waldon, "a resort a few miles nearer the city on the south shore, where there is a large colony of actors." I handed back the letter to Kennedy. "What do you make of it?" he asked, as he folded it up and put it back into his pocket. "I hardly know what to say," I replied. "Of course there have been rumors, I believe, that all was not exactly like a honeymoon still with the Tracy Edwardses." "Yes," returned Waldon slowly, "I know myself that there has been some trouble, but nothing definite until I found this letter last night in my sister's room. She never said anything about it either to mother or myself. They haven't been much together during the summer, and last night when she disappeared Tracy was in the city. But I hadn't thought much about it before, for, of course, you know he has large financial interests that make him keep in pretty close touch with New York and this summer hasn't been a particularly good one on the stock exchange." "And," I put in, "a plunger doesn't always make the best of husbands. Perhaps there is temperament to be reckoned with here." "There seem to be a good many things to be reckoned with," Craig considered. "For example, here's a houseboat, the Lucie, a palatial affair, cruising about aimlessly, with a beautiful woman on it. She gives a little party, in the absence of her husband, to her brother, his fiancee and her mother, who visit her from his yacht, the Nautilus. They break up, those living on the Lucie going to their rooms and the rest back to the yacht, which is anchored out further in the deeper water of the bay. "Some time in the middle of the night her maid, Juanita, finds that she is not in her room. Her brother is summoned back from his yacht and finds that she has left this pathetic, unfinished letter. But otherwise there is no trace of her. Her husband is notified and hurries out there, but he can find no clue. Meanwhile, Mr. Waldon, in despair, hurries down to the city to engage me quietly." "You remember I told you," suggested Waldon, "that my sister hadn't been feeling well for several days. In fact it seemed that the sea air wasn't doing her much good, and some one last night suggested that she try the mountains." "Had there been anything that would foreshadow the--er--disappearance?" asked Kennedy. "Only as I say, that for two or three days she seemed to be listless, to be sinking by slow and easy stages into a sort of vacant, moody state of ill health." "She had a doctor, I suppose?" I asked. "Yes, Dr. Jermyn, Tracy's own personal physician came down from the city several days ago." "What did he say?" "He simply said that it was congestion of the lungs. As far as he could see there was no apparent cause for it. I don't think he was very enthusiastic about the mountain air idea. The fact is he was like a good many doctors under the circumstances, noncommittal--wanted her under observation, and all that sort of thing." "What's your opinion?" I pressed Craig. "Do you think she has run away?" "Naturally, I'd rather not attempt to say yet," Craig replied cautiously. "But there are several possibilities. Yes, she might have left the houseboat in some other boat, of course. Then there is the possibility of accident. It was a hot night. She might have been leaning from the window and have lost her balance. I have even thought of drugs, that she might have taken something in her despondency and have fallen overboard while under the influence of it. Then, of course, there are the two deductions that everyone has made already--either suicide or murder." Waldon had evidently been turning something over in his mind. "There was a wireless outfit aboard the houseboat," he ventured at length. "What of that?" I asked, wondering why he was changing the subject so abruptly. "Why, only this," he replied. "I have been reading about wireless a good deal lately, and if the theories of some scientists are correct, the wireless age is not without its dangers as well as its wonders. I recall reading not long ago of a German professor who says there is no essential difference between wireless waves and the X-rays, and we know the terrible physical effects of X-rays. I believe he estimated that only one three hundred millionth part of the electrical energy generated by sending a message from one station to another near by is actually used up in transmitting the message. The rest is dispersed in the atmosphere. There must be a good deal of such stray electrical energy about Seaville. Isn't it possible that it might hit some one somewhere who was susceptible?" Kennedy said nothing. Waldon's was at least a novel idea, whether it was plausible or not. The only way to test it out, as far as I could determine, was to see whether it fitted with the facts after a careful investigation of the case itself. It was still early in the day and the trains were not as crowded as they would be later. Consequently our journey was comfortable enough and we found ourselves at last at the little vine-covered station at Seaville. One could almost feel that the gay summer colony was in a state of subdued excitement. As we left the quaint station and walked down the main street to the town wharf where we expected some one would be waiting for us, it seemed as if the mysterious disappearance of the beautiful Mrs. Edwards had put a damper on the life of the place. In the hotels there were knots of people evidently discussing the affair, for as we passed we could tell by their faces that they recognized us. One or two bowed and would have joined us, if Waldon had given any encouragement. But he did not stop, and we kept on down the street quickly. I myself began to feel the spell of mystery about the case as I had not felt it among the distractions of the city. Perhaps I imagined it, but there even seemed to be something strange about the houseboat which we could descry at anchor far down the bay as we approached the wharf. We were met, as Waldon had arranged, by a high-powered runabout, the tender to his own yacht, a slim little craft of mahogany and brass, driven like an automobile, and capable of perhaps twenty-five or thirty miles an hour. We jumped in and were soon skimming over the waters of the bay like a skipping stone. It was evident that Waldon was much relieved at having been able to bring assistance, in which he had as much confidence as he reposed in Kennedy. At any rate it was something to be nearing the scene of action again. The Lucie was perhaps seventy feet long and a most attractive craft, with a hull yachty in appearance and of a type which could safely make long runs along the coast, a stanch, seaworthy boat, of course without the speed of the regularly designed yacht, but more than making up in comfort for those on board what was lost in that way. Waldon pointed out with obvious pride his own trim yacht swinging gracefully at anchor a half mile or so away. As we approached the houseboat I looked her over carefully. One of the first things I noticed was that there rose from the roof the primitive inverted V aerial of a wireless telegraph. I thought immediately of the unfinished letter and its contents, and shaded my eyes as I took a good look at the powerful transatlantic station on the spit of sand perhaps three or four miles distant, with its tall steel masts of the latest inverted L type and the cluster of little houses below, in which the operators and the plant were. Waldon noticed what I was looking at, and remarked, "It's a wonderful station--and well worth a visit, if you have the time--one of the most powerful on the coast, I understand." "How did the Lucie come to be equipped with wireless?" asked Craig quickly. "It's a little unusual for a private boat." "Mr. Edwards had it done when she was built," explained Waldon. "His idea was to use it to keep in touch with the stock market on trips." "And it has proved effective?" asked Craig. "Oh, yes--that is, it was all right last winter when he went on a short cruise down in Florida. This summer he hasn't been on the boat long enough to use it much." "Who operates it?" "He used to hire a licensed operator, although I believe the engineer, Pedersen, understands the thing pretty well and could use it if necessary." "Do you think it was Pedersen who used it for Mrs. Edwards?" asked Kennedy. "I really don't know," confessed Waldon. "Pedersen denies absolutely that he has touched the thing for weeks. I want you to quiz him. I wasn't able to get him to admit a thing." CHAPTER VIII THE HOUSEBOAT MYSTERY We had by this time swung around to the side of the houseboat. I realized as we mounted the ladder that the marine gasoline engine had materially changed the old-time houseboat from a mere scow or barge with a low flat house on it, moored in a bay or river, and only with difficulty and expense towed from one place to another. Now the houseboat was really a fair-sized yacht. The Lucie was built high in order to give plenty of accommodation for the living quarters. The staterooms, dining rooms and saloon were really rooms, with seven or eight feet of head room, and furnished just as one would find in a tasteful and expensive house. Down in the hull, of course, was the gasoline motor which drove the propeller, so that when the owner wanted a change of scene all that was necessary was to get up anchor, start the motor and navigate the yacht-houseboat to some other harbor. Edwards himself met us on the deck. He was a tall man, with a red face, a man of action, of outdoor life, apparently a hard worker and a hard player. It was quite evident that he had been waiting for the return of Waldon anxiously. "You find us considerably upset, Professor Kennedy," he greeted Craig, as his brother-in-law introduced us. Edwards turned and led the way toward the saloon. As he entered and bade us be seated in the costly cushioned wicker chairs I noticed how sumptuously it was furnished, and particularly its mechanical piano, its phonograph and the splendid hardwood floor which seemed to invite one to dance in the cool breeze that floated across from one set of open windows to the other. And yet in spite of everything, there was that indefinable air of something lacking, as in a house from which the woman is gone. "You were not here last night, I understand," remarked Kennedy, taking in the room at a glance. "Unfortunately, no," replied Edwards, "Business has kept me with my nose pretty close to the grindstone this summer. Waldon called me up in the middle of the night, however, and I started down in my car, which enabled me to get here before the first train. I haven't been able to do a thing since I got here except just wait--wait--wait. I confess that I don't know what else to do. Waldon seemed to think we ought to have some one down here--and I guess he was right. Anyhow, I'm glad to see you." I watched Edwards keenly. For the first time I realized that I had neglected to ask Waldon whether he had seen the unfinished letter. The question was unnecessary. It was evident that he had not. "Let me see, Waldon, if I've got this thing straight," Edwards went on, pacing restlessly up and down the saloon. "Correct me if I haven't. Last night, as I understand it, there was a sort of little family party here, you and Miss Verrall and your mother from the Nautilus, and Mrs. Edwards and Dr. Jermyn." "Yes," replied Waldon with, I thought, a touch of defiance at the words "family party." He paused as if he would have added that the Nautilus would have been more congenial, anyhow, then added, "We danced a little bit, all except Lucie. She said she wasn't feeling any too well." Edwards had paused by the door. "If you'll excuse me a minute," he said, "I'll call Jermyn and Mrs. Edwards' maid, Juanita. You ought to go over the whole thing immediately, Professor Kennedy." "Why didn't you say anything about the letter to him?" asked Kennedy under his breath. "What was the use?" returned Waldon. "I didn't know how he'd take it. Besides, I wanted your advice on the whole thing. Do you want to show it to him?" "Perhaps it's just as well," ruminated Kennedy. "It may be possible to clear the thing up without involving anybody's name. At any rate, some one is coming down the passage this way." Edwards entered with Dr. Jermyn, a clean-shaven man, youthful in appearance, yet approaching middle age. I had heard of him before. He had studied several years abroad and had gained considerable reputation since his return to America. Dr. Jermyn shook hands with us cordially enough, made some passing comment on the tragedy, and stood evidently waiting for us to disclose our hands. "You have been Mrs. Edwards' physician for some time, I believe?" queried Kennedy, fencing for an opening. "Only since her marriage," replied the doctor briefly. "She hadn't been feeling well for several days, had she?" ventured Kennedy again. "No," replied Dr. Jermyn quickly. "I doubt whether I can add much to what you already know. I suppose Mr. Waldon has told you about her illness. The fact is, I suppose her maid Juanita will be able to tell you really more than I can." I could not help feeling that Dr. Jermyn showed a great deal of reluctance in talking. "You have been with her several days, though, haven't you?" "Four days, I think. She was complaining of feeling nervous and telegraphed me to come down here. I came prepared to stay over night, but Mr. Edwards happened to run down that day, too, and he asked me if I wouldn't remain longer. My practice in the summer is such that I can easily leave it with my assistant in the city, so I agreed. Really, that is about all I can say. I don't know yet what was the matter with Mrs. Edwards, aside from the nervousness which seemed to be of some time standing." He stood facing us, thoughtfully stroking his chin, as a very pretty and petite maid nervously entered and stood facing us in the doorway. "Come in, Juanita," encouraged Edwards. "I want you to tell these gentlemen just what you told me about discovering that Madame had gone--and anything else that you may recall now." "It was Juanita who discovered that Madame was gone, you know," put in Waldon. "How did you discover it?" prompted Craig. "It was very hot," replied the maid, "and often on hot nights I would come in and fan Madame since she was so wakeful. Last night I went to the door and knocked. There was no reply. I called to her, 'Madame, madame.' Still there was no answer. The worst I supposed was that she had fainted. I continued to call." "The door was locked?" inquired Kennedy. "Yes, sir. My call aroused the others on the boat. Dr. Jermyn came and he broke open the door with his shoulder. But the room was empty. Madame was gone." "How about the windows?" asked Kennedy. "Open. They were always open these nights. Sometimes Madame would sit by the window when there was not much breeze." "I should like to see the room," remarked Craig, with an inquiring glance at Edwards. "Certainly," he answered, leading the way down a corridor. Mrs. Edwards' room was on the starboard side, with wide windows instead of portholes. It was furnished magnificently and there was little about it that suggested the nautical, except the view from the window. "The bed had not been slept in," Edwards remarked as we looked about curiously. Kennedy walked over quickly to the wide series of windows before which was a leather-cushioned window seat almost level with the window, several feet above the level of the water. It was by this window, evidently, that Juanita meant that Mrs. Edwards often sat. It was a delightful position, but I could readily see that it would be comparatively easy for anyone accidentally or purposely to fall. "I think myself," Waldon remarked to Kennedy, "that it must have been from the open window that she made her way to the outside. It seems that all agree that the door was locked, while the window was wide open." "There had been no sound--no cry to alarm you?" shot out Kennedy suddenly to Juanita. "No, sir, nothing. I could not sleep myself, and I thought of Madame." "You heard nothing?" he asked of Dr. Jermyn. "Nothing until I heard the maid call," he replied briefly. Mentally I ran over again Kennedy's first list of possibilities--taken off by another boat, accident, drugs, suicide, murder. Was there, I asked myself, sufficient reason for suicide? The letter seemed to me to show too proud a spirit for that. In fact the last sentence seemed to show that she was contemplating the surest method of revenge, rather than surrender. As for accident, why should a person fall overboard from a large houseboat into a perfectly calm harbor? Then, too, there had been no outcry. Somehow, I could not seem to fit any of the theories in with the facts. Evidently it was like many another case, one in which we, as yet, had insufficient data for a conclusion. Suddenly I recalled the theory that Waldon himself had advanced regarding the wireless, either from the boat itself or from the wireless station. For the moment, at least, it seemed plausible that she might have been seated at the window, that she might have been affected by escaped wireless, or by electrolysis. I knew that some physicians had described a disease which they attributed to wireless, a sort of anemia with a marked diminution in the number of red corpuscles in the blood, due partly to the over etherization of the air by reason of the alternating currents used to generate the waves. "I should like now to inspect the little wireless plant you have here on the Lucie," remarked Kennedy. "I noticed the mast as we were approaching a few minutes ago." I had turned at the sound of his voice in time to catch Edwards and Dr. Jermyn eyeing each other furtively. Did they know about the letter, after all, I wondered? Was each in doubt about just how much the other knew? There was no time to pursue these speculations. "Certainly," agreed Mr. Edwards promptly, leading the way. Kennedy seemed keenly interested in inspecting the little wireless plant, which was of a curious type and not exactly like any that I had seen before. "Wireless apparatus," he remarked, as he looked it over, "is divided into three parts, the source of power whether battery or dynamo, the making and sending of wireless waves, including the key, spark, condenser and tuning coil, and the receiving apparatus, head telephones, antennae, ground and detector." Pedersen, the engineer, came in while we were looking the plant over, but seemed uncommunicative to all Kennedy's efforts to engage him in conversation. "I see," remarked Kennedy, "that it is a very compact system with facilities for a quick change from one wave length to another." "Yes," grunted Pedersen, as averse to talking, evidently, as others on the Lucie. "Spark gap, quenched type," I heard Kennedy mutter almost to himself, with a view to showing Pedersen that he knew something about it. "Break system relay--operator can overhear any interference while transmitting--transformation by a single throw of a six-point switch which tunes the oscillating and open circuits to resonance. Very clever--very efficient. By the way, Pedersen, are you the only person aboard who can operate this?" "How should I know?" he answered almost surlily. "You ought to know, if anybody," answered Kennedy unruffled. "I know that it has been operated within the past few days." Pedersen shrugged his shoulders. "You might ask the others aboard," was all he said. "Mr. Edwards pays me to operate it only for himself, when he has no other operator." Kennedy did not pursue the subject, evidently from fear of saying too much just at present. "I wonder if there is anyone else who could have operated it," said Waldon, as we mounted again to the deck. "I don't know," replied Kennedy, pausing on the way up. "You haven't a wireless on the Nautilus, have you?" Waldon shook his head. "Never had any particular use for it myself," he answered. "You say that Miss Verrall and her mother have gone back to the city?" pursued Kennedy, taking care that as before the others were out of earshot. "Yes." "I'd like to stay with you tonight, then," decided Kennedy. "Might we go over with you now? There doesn't seem to be anything more I can do here, unless we get some news about Mrs. Edwards." Waldon seemed only too glad to agree, and no one on the Lucie insisted on our staying. We arrived at the Nautilus a few minutes later, and while we were lunching Kennedy dispatched the tender to the Marconi station with a note. It was early in the afternoon when the tender returned with several packages and coils of wire. Kennedy immediately set to work on the Nautilus stretching out some of the wire. "What is it you are planning?" asked Waldon, to whom every action of Kennedy seemed to be a mystery of the highest interest. "Improvising my own wireless," he replied, not averse to talking to the young man to whom he seemed to have taken a fancy. "For short distances, you know, it isn't necessary to construct an aerial pole or even to use outside wires to receive messages. All that is needed is to use just a few wires stretched inside a room. The rest is just the apparatus." I was quite as much interested as Waldon. "In wireless," he went on, "the signals are not sent in one direction, but in all, so that a person within range of the ethereal disturbance can get them if only he has the necessary receiving apparatus. This apparatus need not be so elaborate and expensive as used to be thought needful if a sensitive detector is employed, and I have sent over to the station for a new piece of apparatus which I knew they had in almost any Marconi station. Why, I've got wireless signals using only twelve feet of number eighteen copper wire stretched across a room and grounded with a water pipe. You might even use a wire mattress on an iron bedstead." "Can't they find out by--er, interference?" I asked, repeating the term I had so often heard. Kennedy laughed. "No, not for radio apparatus which merely receives radiograms and is not equipped for sending. I am setting up only one side of a wireless outfit here. All I want to do is to hear what is being said. I don't care about saying anything." He unwrapped another package which had been loaned to him by the radio station and we watched him curiously as he tested it and set it up. Some parts of it I recognized such as the very sensitive microphone, and another part I could have sworn was a phonograph cylinder, though Craig was so busy testing his apparatus that now we could not ask questions. It was late in the afternoon when he finished, and we had just time to run up to the dock at Seaville and stop off at the Lucie to see if anything had happened in the intervening hours before dinner. There was nothing, except that I found time to file a message to the Star and meet several fellow newspaper men who had been sent down by other papers on the chance of picking up a good story. We had the Nautilus to ourselves, and as she was a very comfortable little craft, we really had a very congenial time, a plunge over her side, a good dinner, and then a long talk out on deck under the stars, in which we went over every phase of the case. As we discussed it, Waldon followed keenly, and it was quite evident from his remarks that he had come to the conclusion that Dr. Jermyn at least knew more than he had told about the case. Still, the day wore away with no solution yet of the mystery. CHAPTER IX THE RADIO DETECTIVE It was early the following morning when a launch drew up beside the Nautilus. In it were Edwards and Dr. Jermyn, wildly excited. "What's the matter?" called out Waldon. "They--they have found the body," Edwards blurted out. Waldon paled and clutched the rail. He had thought the world of his sister, and not until the last moment had he given up hope that perhaps she might be found to have disappeared in some other way than had become increasingly evident. "Where?" cried Kennedy. "Who?" "Over on Ten Mile Beach," answered Edwards. "Some fishermen who had been out on a cruise and hadn't heard the story. They took the body to town, and there it was recognized. They sent word out to us immediately." Waldon had already spun the engine of his tender, which was about the fastest thing afloat about Seaville, had taken Edwards over, and we were off in a cloud of spray, the nose of the boat many inches above the surface of the water. In the little undertaking establishment at Seaville lay the body of the beautiful young matron about whom so much anxiety had been felt. I could not help thinking what an end was this for the incomparable beauty. At the very height of her brief career the poor little woman's life had been suddenly snuffed out. But by what? The body had been found, but the mystery had been far from solved. As Kennedy bent over the body, I heard him murmur to himself, "She had everything--everything except happiness." "Was it drowning that caused her death?" asked Kennedy of the local doctor, who also happened to be coroner and had already arrived on the scene. The doctor shook his head. "I don't know," he said doubtfully. "There was congestion of the lungs--but I--I can't say but what she might have been dead before she fell or was thrown into the water." Dr. Jermyn stood on one side, now and then putting in a word, but for the most part silent unless spoken to. Kennedy, however, was making a most minute examination. As he turned the beautiful head, almost reverently, he saw something that evidently attracted his attention. I was standing next to him and, between us, I think we cut off the view of the others. There on the back of the neck, carefully, had been smeared something transparent, almost skin-like, which had easily escaped the attention of the rest. Kennedy tried to pick it off, but only succeeded in pulling off a very minute piece to which the flesh seemed to adhere. "That's queer," he whispered to me. "Water, naturally, has no effect on it, else it would have been washed off long before. Walter," he added, "just slip across the street quietly to the drug store and get me a piece of gauze soaked with acetone." As quickly and unostentatiously as I could I did so and handed him the wet cloth, contriving at the same time to add Waldon to our barrier, for I could see that Kennedy was anxious to be observed as little as possible. "What is it?" I whispered, as he rubbed the transparent skin-like stuff off, and dropped the gauze into his pocket. "A sort of skin varnish," he remarked under his breath, "waterproof and so adhesive that it resists pulling off even with a knife without taking the cuticle with it." Beneath, as the skin varnish slowly dissolved under his gentle rubbing, he had disclosed several very small reddish spots, like little cuts that had been made by means of a very sharp instrument. As he did so, he gave them a hasty glance, turned the now stony beautiful head straight again, stood up, and resumed his talk with the coroner, who was evidently getting more and more bewildered by the case. Edwards, who had completed the arrangements with the undertaker for the care of the body as soon as the coroner released it, seemed completely unnerved. "Jermyn," he said to the doctor, as he turned away and hid his eyes, "I can't stand this. The undertaker wants some stuff from the--er--boat," his voice broke over the name which had been hers. "Will you get it for me? I'm going up to a hotel here, and I'll wait for you there. But I can't go out to the boat--yet." "I think Mr. Waldon will be glad to take you out in his tender," suggested Kennedy. "Besides, I feel that I'd like a little fresh air as a bracer, too, after such a shock." "What were those little cuts?" I asked as Waldon and Dr. Jermyn preceded us through the crowd outside to the pier. "Some one," he answered in a low tone, "has severed the pneumogastric nerves." "The pneumogastric nerves?" I repeated. "Yes, the vagus or wandering nerve, the so-called tenth cranial nerve. Unlike the other cranial nerves, which are concerned with the special senses or distributed to the skin and muscles of the head and neck, the vagus, as its name implies, strays downward into the chest and abdomen supplying branches to the throat, lungs, heart and stomach and forms an important connecting link between the brain and the sympathetic nervous system." We had reached the pier, and a nod from Kennedy discouraged further conversation on the subject. A few minutes later we had reached the Lucie and gone up over her side. Kennedy waited until Jermyn had disappeared into the room of Mrs. Edwards to get what the undertaker had desired. A moment and he had passed quietly into Dr. Jermyn's own room, followed by me. Several quick glances about told him what not to waste time over, and at last his eye fell on a little portable case of medicines and surgical instruments. He opened it quickly and took out a bottle of golden yellow liquid. Kennedy smelled it, then quickly painted some on the back of his hand. It dried quickly, like an artificial skin. He had found a bottle of skin varnish in Dr. Jermyn's own medicine chest! We hurried back to the deck, and a few minutes later the doctor appeared with a large package. "Did you ever hear of coating the skin by a substance which is impervious to water, smooth and elastic?" asked Kennedy quietly as Waldon's tender sped along back to Seaville. "Why--er, yes," he said frankly, raising his eyes and looking at Craig in surprise. "There have been a dozen or more such substances. The best is one which I use, made of pyroxylin, the soluble cotton of commerce, dissolved in amyl acetate and acetone with some other substances that make it perfectly sterile. Why do you ask?" "Because some one has used a little bit of it to cover a few slight cuts on the back of the neck of Mrs. Edwards." "Indeed?" he said simply, in a tone of mild surprise. "Yes," pursued Kennedy. "They seem to me to be subcutaneous incisions of the neck with a very fine scalpel dividing the two great pneumogastric nerves. Of course you know what that would mean--the victim would pass away naturally by slow and easy stages in three or four days, and all that would appear might be congestion of the lungs. They are delicate little punctures and elusive nerves to locate, but after all it might be done as painlessly, as simply and as safely as a barber might remove some dead hairs. A country coroner might easily pass over such evidence at an autopsy--especially if it was concealed by skin varnish." I was surprised at the frankness with which Kennedy spoke, but absolutely amazed at the coolness of Jermyn. At first he said absolutely nothing. He seemed to be as set in his reticence as he had been when we first met. I watched him narrowly. Waldon, who was driving the boat, had not heard what was said, but I had, and I could not conceive how anyone could take it so calmly. Finally Jermyn turned to Kennedy and looked him squarely in the eye. "Kennedy," he said slowly, "this is extraordinary--most extraordinary," then, pausing, added, "if true." "There can be no doubt of the truth," replied Kennedy, eyeing Dr. Jermyn just as squarely. "What do you propose to do about it?" asked the doctor. "Investigate," replied Kennedy simply. "While Waldon takes these things up to the undertaker's, we may as well wait here in the boat. I want him to stop on the way back for Mr. Edwards. Then we shall go out to the Lucie. He must go, whether he likes it or not." It was indeed a most peculiar situation as Kennedy and I sat in the tender with Dr. Jermyn waiting for Waldon to return with Edwards. Not a word was spoken. The tenseness of the situation was not relieved by the return of Waldon with Edwards. Waldon seemed to realize without knowing just what it was, that something was about to happen. He drove his boat back to the Lucie again in record time. This was Kennedy's turn to be reticent. Whatever it was he was revolving in his mind, he answered in scarcely more than monosyllables whatever questions were put to him. "You are not coming aboard?" inquired Edwards in surprise as he and Jermyn mounted the steps of the houseboat ladder, and Kennedy remained seated in the tender. "Not yet," replied Craig coolly. "But I thought you had something to show me. Waldon told me you had." "I think I shall have in a short time," returned Kennedy. "We shall be back immediately. I'm just going to ask Waldon to run over to the Nautilus for a few minutes. We'll tow back your launch, too, in case you need it." Waldon had cast off obediently. "There's one thing sure," I remarked. "Jermyn can't get away from the Lucie until we return--unless he swims." Kennedy did not seem to pay much attention to the remark, for his only reply was: "I'm taking a chance by this maneuvering, but I think it will work out that I am correct. By the way, Waldon, you needn't put on so much speed. I'm in no great hurry to get back. Half an hour will be time enough." "Jermyn? What did you mean by Jermyn?" asked Waldon, as we climbed to the deck of the Nautilus. He had evidently learned, as I had, that it was little use to try to quiz Kennedy until he was ready to be questioned and had decided to try it on me. I had nothing to conceal and I told him quite fully all that I knew. Actually, I believe if Jermyn had been there, it would have taken both Kennedy and myself to prevent violence. As it was I had a veritable madman to deal with while Kennedy gathered up leisurely the wireless outfit he had installed on the deck of Waldon's yacht. It was only by telling him that I would certainly demand that Kennedy leave him behind if he did not control his feelings that I could calm him before Craig had finished his work on the yacht. Waldon relieved himself by driving the tender back at top speed to the Lucie, and now it seemed that Kennedy had no objection to traveling as fast as the many-cylindered engine was capable of going. As we entered the saloon of the houseboat, I kept close watch over Waldon. Kennedy began by slipping a record on the phonograph in the corner of the saloon, then facing us and addressing Edwards particularly. "You may be interested to know, Mr. Edwards," he said, "that your wireless outfit here has been put to a use for which you never intended it." No one said anything, but I am sure that some one in the room then for the first time began to suspect what was coming. "As you know, by the use of an aerial pole, messages may be easily received from any number of stations," continued Craig. "Laws, rules and regulations may be adopted to shut out interlopers and plug busybody ears, but the greater part of whatever is transmitted by the Hertzian waves can be snatched down by other wireless apparatus. "Down below, in that little room of yours," went on Craig, "might sit an operator with his ear-phone clamped to his head, drinking in the news conveyed surely and swiftly to him through the wireless signals--plucking from the sky secrets of finance and," he added, leaning forward, "love." In his usual dramatic manner Kennedy had swung his little audience completely with him. "In other words," he resumed, "it might be used for eavesdropping by a wireless wiretapper. Now," he concluded, "I thought that if there was any radio detective work being done, I might as well do some, too." He toyed for a moment with the phonograph record. "I have used," he explained, "Marconi's radiotelephone, because in connection with his receivers Marconi uses phonographic recorders and on them has captured wireless telegraph signals over hundreds of miles. "He has found that it is possible to receive wireless signals, although ordinary records are not loud enough, by using a small microphone on the repeating diaphragm and connected with a loud-speaking telephone. The chief difficulty was to get a microphone that would carry a sufficient current without burning up. There were other difficulties, but they have been surmounted and now wireless telegraph messages may be automatically recorded and made audible." Kennedy started the phonograph, running it along, stopping it, taking up the record at a new point. "Listen," he exclaimed at length, "there's something interesting, the WXY call--Seaville station--from some one on the Lucie only a few minutes ago, sending a message to be relayed by Seaville to the station at Beach Park. It seems impossible, but buzzing and ticking forth is this message from some one off this very houseboat. It reads: "Miss Valerie Fox, Beach Park. I am suspected of the murder of Mrs. Edwards. I appeal to you to help me. You must allow me to tell the truth about the messages I intercepted for Mrs. Edwards which passed between yourself on the ocean and Mr. Edwards in New York via Seaville. You rejected me and would not let me save you. Now you must save me." Kennedy paused, then added, "The message is signed by Dr. Jermyn!" At once I saw it all. Jermyn had been the unsuccessful suitor for Miss Fox's affections. But before I could piece out the rest of the tragic story, Kennedy had started the phonograph record at an earlier point which he had skipped for the present. "Here's another record--a brief one--also to Valerie Fox from the houseboat: 'Refuse all interviews. Deny everything. Will see you as soon as present excitement dies down.'" Before Kennedy could finish, Waldon had leaped forward, unable longer to control his feelings. If Kennedy had not seized his arm, I verily believe he would have cast Dr. Jermyn into the bay into which his sister had fallen two nights before in her terribly weakened condition. "Waldon," cried Kennedy, "for God's sake, man--wait! Don't you understand? The second message is signed Tracy Edwards." It came as quite as much a shock of surprise to me as to Waldon. "Don't you understand?" he repeated. "Your sister first learned from Dr. Jermyn what was going on. She moved the Lucie down here near Seaville in order to be near the wireless station when the ship bearing her rival, Valerie Fox, got in touch with land. With the help of Dr. Jermyn she intercepted the wireless messages from the Kronprinz to the shore--between her husband and Valerie Fox." Kennedy was hurrying on now to his irresistible conclusion. "She found that he was infatuated with the famous stage beauty, that he was planning to marry another, her rival. She accused him of it, threatened to defeat his plans. He knew she knew his unfaithfulness. Instead of being your sister's murderer, Dr. Jermyn was helping her get the evidence that would save both her and perhaps win Miss Fox back to himself." Kennedy had turned sharply on Edwards. "But," he added, with a glance that crushed any lingering hope that the truth had been concealed, "the same night that Dr. Jermyn arrived here, you visited your wife. As she slept you severed the nerves that meant life or death to her. Then you covered the cuts with the preparation which you knew Dr. Jermyn used. You asked him to stay, while you went away, thinking that when death came you would have a perfect alibi--perhaps a scapegoat. Edwards, the radio detective convicts you!" CHAPTER X THE CURIO SHOP Edwards crumpled up as Kennedy and I faced him. There was no escape. In fact our greatest difficulty was to protect him from Waldon. Kennedy's work in the case was over when we had got Edwards ashore and in the hands of the authorities. But mine had just begun and it was late when I got my story on the wire for the Star. I felt pretty tired and determined to make up for it by sleeping the next day. It was no use, however. "Why, what's the matter, Mrs. Northrop?" I heard Kennedy ask as he opened our door the next morning, just as I had finished dressing. He had admitted a young woman, who greeted us with nervous, wide-staring eyes. "It's--it's about Archer," she cried, sinking into the nearest chair and staring from one to the other of us. She was the wife of Professor Archer Northrop, director of the archeological department at the university. Both Craig and I had known her ever since her marriage to Northrop, for she was one of the most attractive ladies in the younger set of the faculty, to which Craig naturally belonged. Archer had been of the class below us in the university. We had hazed him, and out of the mild hazing there had, strangely enough, grown a strong friendship. I recollected quickly that Northrop, according to last reports, had been down in the south of Mexico on an archeological expedition. But before I could frame, even in my mind, the natural question in a form that would not alarm his wife further, Kennedy had it on his lips. "No bad news from Mitla, I hope?" he asked gently, recalling one of the main working stations chosen by the expedition and the reported unsettled condition of the country about it. She looked up quickly. "Didn't you know--he--came back from Vera Cruz yesterday?" she asked slowly, then added, speaking in a broken tone, "and--he seems--suddenly--to have disappeared. Oh, such a terrible night of worry! No word--and I called up the museum, but Doctor Bernardo, the curator, had gone, and no one answered. And this morning--I couldn't stand it any longer--so I came to you." "You have no idea, I suppose, of anything that was weighing on his mind?" suggested Kennedy. "No," she answered promptly. In default of any further information, Kennedy did not pursue this line of questioning. I could not determine from his face or manner whether he thought the matter might involve another than Mrs. Northrop, or, perhaps, something connected with the unsettled condition of the country from which her husband had just arrived. "Have you any of the letters that Archer wrote home?" asked Craig, at length. "Yes," she replied eagerly, taking a little packet from her handbag. "I thought you might ask that. I brought them." "You are an ideal client," commented Craig encouragingly, taking the letters. "Now, Mrs. Northrop, be brave. Trust me to run this thing down, and if you hear anything let me know immediately." She left us a moment later, visibly relieved. Scarcely had she gone when Craig, stuffing the letters into his pocket unread, seized his hat, and a moment later was striding along toward the museum with his habitual rapid, abstracted step which told me that he sensed a mystery. In the museum we met Doctor Bernardo, a man slightly older than Northrop, with whom he had been very intimate. He had just arrived and was already deeply immersed in the study of some new and beautiful colored plates from the National Museum of Mexico City. "Do you remember seeing Northrop here yesterday afternoon?" greeted Craig, without explaining what had happened. "Yes," he answered promptly. "I was here with him until very late. At least, he was in his own room, working hard, when I left." "Did you see him go?" "Why--er--no," replied Bernardo, as if that were a new idea. "I left him here--at least, I didn't see him go out." Kennedy tried the door of Northrop's room, which was at the far end, in a corner, and communicated with the hall only through the main floor of the museum. It was locked. A pass-key from the janitor quickly opened it. Such a sight as greeted us, I shall never forget. There, in his big desk-chair, sat Northrop, absolutely rigid, the most horribly contorted look on his features that I have ever seen--half of pain, half of fear, as if of something nameless. Kennedy bent over. His hands were cold. Northrop had been dead at least twelve hours, perhaps longer. All night the deserted museum had guarded its terrible secret. As Craig peered into his face, he saw, in the fleshy part of the neck, just below the left ear, a round red mark, with just a drop or two of now black coagulated blood in the center. All around we could see a vast amount of miscellaneous stuff, partly unpacked, partly just opened, and waiting to be taken out of the wrappings by the now motionless hands. "I suppose you are more or less familiar with what Northrop brought back?" asked Kennedy of Bernardo, running his eye over the material in the room. "Yes, reasonably," answered Bernardo. "Before the cases arrived from the wharf, he told me in detail what he had managed to bring up with him." "I wish, then, that you would look it over and see if there is anything missing," requested Craig, already himself busy in going over the room for other evidence. Doctor Bernardo hastily began taking a mental inventory of the stuff. While they worked, I tried vainly to frame some theory which would explain the startling facts we had so suddenly discovered. Mitla, I knew, was south of the city of Oaxaca, and there, in its ruined palaces, was the crowning achievement of the old Zapotec kings. No ruins in America were more elaborately ornamented or richer in lore for the archeologist. Northrop had brought up porphyry blocks with quaint grecques and much hieroglyphic painting. Already unpacked were half a dozen copper axes, some of the first of that particular style that had ever been brought to the United States. Besides the sculptured stones and the mosaics were jugs, cups, vases, little gods, sacrificial stones--enough, almost, to equip a new alcove in the museum. Before Northrop was an idol, a hideous thing on which frogs and snakes squatted and coiled. It was a fitting piece to accompany the gruesome occupant of the little room in his long, last vigil. In fact, it almost sent a shudder over me, and if I had been inclined to the superstitious, I should certainly have concluded that this was retribution for having disturbed the lares and penates of a dead race. Doctor Bernardo was going over the material a second time. By the look on his face, even I could guess that something was missing. "What is it?" asked Craig, following the curator closely. "Why," he answered slowly, "there was an inscription--we were looking at it earlier in the day--on a small block of porphyry. I don't see it." He paused and went back to his search before we could ask him further what he thought the inscription was about. I thought nothing myself at the time of his reticence, for Kennedy had gone over to a window back of Northrop and to the left. It was fully twenty feet from the downward slope of the campus there, and, as he craned his neck out, he noted that the copper leader of the rain pipe ran past it a few feet away. I, too, looked out. A thick group of trees hid the window from the avenue beyond the campus wall, and below us, at a corner of the building, was a clump of rhododendrons. As Craig bent over the sill, he whipped out a pocket lens. A moment later he silently handed the glass to me. As nearly as I could make out, there were five marks on the dust of the sill. "Finger-prints!" I exclaimed. "Some one has been clinging to the edge of the ledge." "In that case," Craig observed quietly, "there would have been only four prints." I looked again, puzzled. The prints were flat and well separated. "No," he added, "not finger-prints--toe-prints." "Toe-prints?" I echoed. Before he could reply, Craig had dashed out of the room, around, and under the window. There, he was carefully going over the soft earth around the bushes below. "What are you looking for?" I asked, joining him. "Some one--perhaps two--has been here," he remarked, almost under his breath. "One, at least, has removed his shoes. See those shoe-prints up to this point? The print of a boot-heel in soft earth shows the position and contour of every nail head. Bertillon has made a collection of such nails, certain types, sizes, and shapes used in certain boots, showing often what country the shoes came from. Even the number and pattern are significant. Some factories use a fixed number of nails and arrange them in a particular manner. I have made my own collection of such prints in this country. These were American shoes. Perhaps the clue will not lead us anywhere, though, for I doubt whether it was an American foot." Kennedy continued to study the marks. "He removed his shoes--either to help in climbing or to prevent noise--ah--here's the foot! Strange--see how small it is--and broad, how prehensile the toes--almost like fingers. Surely that foot could never have been encased in American shoes all its life. I shall make plaster casts of these, to preserve later." He was still scouting about on hands and knees in the dampness of the rhododendrons. Suddenly he reached his long arm in among the shrubs and picked up a little reed stick. On the end of it was a small cylinder of buff brown. He looked at it curiously, dug his nail into the soft mass, then rubbed his nail over the tip of his tongue gingerly. With a wry face, as if the taste were extremely acrid, he moistened his handkerchief and wiped off his tongue vigorously. "Even that minute particle that was on my nail makes my tongue tingle and feel numb," he remarked, still rubbing. "Let us go back again. I want to see Bernardo." "Had he any visitors during the day?" queried Kennedy, as he reentered the ghastly little room, while the curator stood outside, completely unnerved by the tragedy which had been so close to him without his apparently knowing it. Kennedy was squeezing out from the little wound on Northrop's neck a few drops of liquid on a sterilized piece of glass. "No; no one," Bernardo answered, after a moment. "Did you see anyone in the museum who looked suspicious?" asked Kennedy, watching Bernardo's face keenly. "No," he hesitated. "There were several people wandering about among the exhibits, of course. One, I recall, late in the afternoon, was a little dark-skinned woman, rather good-looking." "A Mexican?" "Yes, I should say so. Not of Spanish descent, though. She was rather of the Indian type. She seemed to be much interested in the various exhibits, asked me several questions, very intelligently, too. Really, I thought she was trying to--er--flirt with me." He shot a glance at Craig, half of confession, half of embarrassment. "And--oh, yes--there was another--a man, a little man, as I recall, with shaggy hair. He looked like a Russian to me. I remember, because he came to the door, peered around hastily, and went away. I thought he might have got into the wrong part of the building and went to direct him right--but before I could get out into the hall, he was gone. I remember, too, that, as I turned, the woman had followed me and soon was asking other questions--which, I will admit--I was glad to answer." "Was Northrop in his room while these people were here?" "Yes; he had locked the door so that none of the students or visitors could disturb him." "Evidently the woman was diverting your attention while the man entered Northrop's room by the window," ruminated Craig, as we stood for a moment in the outside doorway. He had already telephoned to our old friend Doctor Leslie, the coroner, to take charge of the case, and now was ready to leave. The news had spread, and the janitor of the building was waiting to lock the campus door to keep back the crowd of students and others. Our next duty was the painful one of breaking the news to Mrs. Northrop. I shall pass it over. Perhaps no one could have done it more gently than Kennedy. She did not cry. She was simply dazed. Fortunately her mother was with her, had been, in fact, ever since Northrop had gone on the expedition. "Why should anyone want to steal tablets of old Mixtec inscriptions?" I asked thoughtfully, as we walked sadly over the campus in the direction of the chemistry building. "Have they a sufficient value, even on appreciative Fifth Avenue, to warrant murder?" "Well," he remarked, "it does seem incomprehensible. Yet people do just such things. The psychologists tell us that there is a veritable mania for possessing such curios. However, it is possible that there may be some deeper significance in this case," he added, his face puckered in thought. Who was the mysterious Mexican woman, who the shaggy Russian? I asked myself. Clearly, at least, if she existed at all, she was one of the millions not of Spanish but of Indian descent in the country south of us. As I reasoned it out, it seemed to me as if she must have been an accomplice. She could not have got into Northrop's room either before or after Doctor Bernardo left. Then, too, the toe-and shoe-prints were not hers. But, I figured, she certainly had a part in the plot. While I was engaged in the vain effort to unravel the tragic affair by pure reason, Kennedy was at work with practical science. He began by examining the little dark cylinder on the end of the reed. On a piece of the stuff, broken off, he poured a dark liquid from a brown-glass bottle. Then he placed it under a microscope. "Microscopically," he said slowly, "it consists almost wholly of minute, clear granules which give a blue reaction with iodine. They are starch. Mixed with them are some larger starch granules, a few plant cells, fibrous matter, and other foreign particles. And then, there is the substance that gives that acrid, numbing taste." He appeared to be vacantly studying the floor. "What do you think it is?" I asked, unable to restrain myself. "Aconite," he answered slowly, "of which the active principle is the deadly poisonous alkaloid, aconitin." He walked over and pulled down a well-thumbed standard work on toxicology, turned the pages, then began to read aloud: Pure aconitin is probably the most actively poisonous substance with which we are acquainted and, if administered hypodermically, the alkaloid is even more powerfully poisonous than when taken by the mouth. As in the case of most of the poisonous alkaloids, aconitin does not produce any decidedly characteristic post-mortem appearances. There is no way to distinguish it from other alkaloids, in fact, no reliable chemical test. The physiological effects before death are all that can be relied on. Owing to its exceeding toxic nature, the smallness of the dose required to produce death, and the lack of tests for recognition, aconitin possesses rather more interest in legal medicine than most other poisons. It is one of the few substances which, in the present state of toxicology, might be criminally administered and leave no positive evidence of the crime. If a small but fatal dose of the poison were to be given, especially if it were administered hypodermically, the chances of its detection in the body after death would be practically none. CHAPTER XI THE "PILLAR OF DEATH" I was looking at him fixedly as the diabolical nature of what must have happened sank into my mind. Here was a poison that defied detection. I could see by the look on Craig's face that that problem, alone, was enough to absorb his attention. He seemed fully to realize that we had to deal with a criminal so clever that he might never be brought to justice. An idea flashed over me. "How about the letters?" I suggested. "Good, Walter!" he exclaimed. He untied the package which Mrs. Northrop had given him and glanced quickly over one after another of the letters. "Ah!" he exclaimed, fairly devouring one dated at Mitla. "Listen--it tells about Northrop's work and goes on: "'I have been much interested in a cavern, or subterraneo, here, in the shape of a cross, each arm of which extends for some twelve feet underground. In the center it is guarded by a block of stone popularly called "the Pillar of Death." There is a superstition that whoever embraces it will die before the sun goes down. "'From the subterraneo is said to lead a long, underground passage across the court to another subterranean chamber which is full of Mixtec treasure. Treasure hunters have dug all around it, and it is said that two old Indians, only, know of the immense amount of buried gold and silver, but that they will not reveal it.'" I started up. Here was the missing link which I had been waiting for. "There, at least, is the motive," I blurted out. "That is why Bernardo was so reticent. Northrop, in his innocence of heart, had showed him that inscription." Kennedy said nothing as he finally tied up the little packet of letters and locked it in his safe. He was not given to hasty generalizations; neither was he one who clung doggedly to a preconceived theory. It was still early in the afternoon. Craig and I decided to drop into the museum again in order to see Doctor Bernardo. He was not there and we sat down to wait. Just then the letter box in the door clicked. It was the postman on his rounds. Kennedy walked over and picked up the letter. The postmark bore the words, "Mexico City," and a date somewhat later than that on which Northrop had left Vera Cruz. In the lower corner, underscored, were the words, "Personal--Urgent." "I'd like to know what is in that," remarked Craig, turning it over and over. He appeared to be considering something, for he rose suddenly and shoved the letter into his pocket. I followed, and a few moments later, across the campus in his laboratory, he was working quickly over an X-ray apparatus. He had placed the letter in it. "These are what are known as 'low' tubes," he explained. "They give out 'soft rays.'" He continued to work for a few moments, then handed me the letter. "Now, Walter," he said, "if you will just hurry back to the museum and replace that letter, I think I will have something that will astonish you--though whether it will have any bearing on the case, remains to be seen." "What is it?" I asked, a few minutes later, when I had rejoined him, after returning the letter. He was poring intently over what looked like a negative. "The possibility of reading the contents of documents inclosed in a sealed envelope," he replied, still studying the shadowgraph closely, "has already been established by the well-known English scientist, Doctor Hall Edwards. He has been experimenting with the method of using X-rays recently discovered by a German scientist, by which radiographs of very thin substances, such as a sheet of paper, a leaf, an insect's body, may be obtained. These thin substances through which the rays used formerly to pass without leaving an impression, can now be radiographed." I looked carefully as he traced out something on the negative. On it was easily possible, following his guidance, to read the words inscribed on the sheet of paper inside. So admirably defined were all the details that even the gum on the envelope and the edges of the sheet of paper inside the envelope could be distinguished. "Any letter written with ink having a mineral basis can be radiographed," added Craig. "Even when the sheet is folded in the usual way, it is possible by taking a radiograph stereoscopically, to distinguish the writing, every detail standing out in relief. Besides, it can be greatly magnified, which aids in deciphering it if it is indistinct or jumbled up. Some of it looks like mirror writing. Ah," he added, "here's something interesting!" Together we managed to trace out the contents of several paragraphs, of which the significant parts were as follows: I am expecting that my friend Senora Herreria will be in New York by the time you receive this, and should she call on you, I know you will accord her every courtesy. She has been in Mexico City for a few days, having just returned from Mitla, where she met Professor Northrop. It is rumored that Professor Northrop has succeeded in smuggling out of the country a very important stone bearing an inscription which, I understand, is of more than ordinary interest. I do not know anything definite about it, as Senora Herreria is very reticent on the matter, but depend on you to find out if possible and let me know of it. According to the rumors and the statements of the senora, it seems that Northrop has taken an unfair advantage of the situation down in Oaxaca, and I suppose she and others who know about the inscription feel that it is really the possession of the government. You will find that the senora is an accomplished antiquarian and scholar. Like many others down here just now, she has a high regard for the Japanese. As you know, there exists a natural sympathy between some Mexicans and Japanese, owing to what is believed to be a common origin of the two races. In spite of the assertions of many to the contrary, there is little doubt left in the minds of students that the Indian races which have peopled Mexico were of Mongolian stock. Many words in some dialects are easily understood by Chinese immigrants. A secretary of the Japanese legation here was able recently to decipher old Mixtec inscriptions found in the ruins of Mitla. Senora Herreria has been much interested in establishing the relationship and, I understand, is acquainted with a Japanese curio dealer in New York who recently visited Mexico for the same purpose. I believe that she wishes to collaborate with him on a monograph on the subject, which is expected to have a powerful effect on the public opinion both here and at Tokyo. In regard to the inscription which Northrop has taken with him, I rely on you to keep me informed. There seems to be a great deal of mystery connected with it, and I am simply hazarding a guess as to its nature. If it should prove to be something which might interest either the Japanese or ourselves, you can see how important it may be, especially in view of the forthcoming mission of General Francisco to Tokyo. Very sincerely yours, DR. EMILIO SANCHEZ, Director. "Bernardo is a Mexican," I exclaimed, as Kennedy finished reading, "and there can be no doubt that the woman he mentioned was this Senora Herreria." Kennedy said nothing, but seemed to be weighing the various paragraphs in the letter. "Still," I observed, "so far, the only one against whom we have any direct suspicion in the case is the shaggy Russian, whoever he is." "A man whom Bernardo says looked like a Russian," corrected Craig. He was pacing the laboratory restlessly. "This is becoming quite an international affair," he remarked finally, pausing before me, his hat on. "Would you like to relax your mind by a little excursion among the curio shops of the city? I know something about Japanese curios--more, perhaps, than I do of Mexican. It may amuse us, even if it doesn't help in solving the mystery. Meanwhile, I shall make arrangements for shadowing Bernardo. I want to know just how he acts after he reads that letter." He paused long enough to telephone his instructions to an uptown detective agency which could be depended on for such mere routine work, then joined me with the significant remark: "Blood is thicker than water, anyhow, Walter. Still, even if the Mexicans are influenced by sentiment, I hardly think that would account for the interest of our friends from across the water in the matter." I do not know how many of the large and small curio shops of the city we visited that afternoon. At another time, I should have enjoyed the visits immensely, for anyone seeking articles of beauty will find the antique shops of Fifth and Fourth Avenues and the side streets well worth visiting. We came, at length, to one, a small, quaint, dusty rookery, down in a basement, entered almost directly from the street. It bore over the door a little gilt sign which read simply, "Sato's." As we entered, I could not help being impressed by the wealth of articles in beautiful cloisonne enamel, in mother-of-pearl, lacquer, and champleve. There were beautiful little koros, or incense burners, vases, and teapots. There were enamels incrusted, translucent, and painted, works of the famous Namikawa, of Kyoto, and Namikawa, of Tokyo. Satsuma vases, splendid and rare examples of the potter's art, crowded gorgeously embroidered screens depicting all sorts of brilliant scenes, among others the sacred Fujiyama rising in the stately distance. Sato himself greeted us with a ready smile and bow. "I am just looking for a few things to add to my den," explained Kennedy, adding, "nothing in particular, but merely whatever happens to strike my fancy." "Surely, then, you have come to the right shop," greeted Sato. "If there is anything that interests you, I shall be glad to show it." "Thank you," replied Craig. "Don't let me trouble you with your other customers. I will call on you if I see anything." For several minutes, Craig and I busied ourselves looking about, and we did not have to feign interest, either. "Often things are not as represented," he whispered to me, after a while, "but a connoiseur can tell spurious goods. These are the real thing, mostly." "Not one in fifty can tell the difference," put in the voice of Sato, at his elbow. "Well, you see I happen to know," Craig replied, not the least disconcerted. "You can't always be too sure." A laugh and a shrug was Sato's answer. "It's well all are not so keen," he said, with a frank acknowledgment that he was not above sharp practices. I glanced now and then at the expressionless face of the curio dealer. Was it merely the natural blankness of his countenance that impressed me, or was there, in fact, something deep and dark hidden in it, something of "East is East and West is West" which I did not and could not understand? Craig was admiring the bronzes. He had paused before one, a square metal fire-screen of odd design, with the title on a card, "Japan Gazing at the World." It represented Japan as an eagle, with beak and talons of burnished gold, resting on a rocky island about which great waves dashed. The bird had an air of dignity and conscious pride in its strength, as it looked out at the world, a globe revolving in space. "Do you suppose there is anything significant in that?" I asked, pointing to the continent of North America, also in gold and prominently in view. "Ah, honorable sir," answered Sato, before Kennedy could reply, "the artist intended by that to indicate Japan's friendliness for America and America's greatness." He was inscrutable. It seemed as if he were watching our every move, and yet it was done with a polite cordiality that could not give offense. Behind some bronzes of the Japanese Hercules destroying the demons and other mythical heroes was a large alcove, or tokonoma, decorated with peacock, stork, and crane panels. Carvings and lacquer added to the beauty of it. A miniature chrysanthemum garden heightened the illusion. Carved hinoki wood framed the panels, and the roof was supported by columns in the old Japanese style, the whole being a compromise between the very simple and quiet and the polychromatic. The dark woods, the lanterns, the floor tiles of dark red, and the cushions of rich gold and yellow were most alluring. It had the genuine fascination of the Orient. "Will the gentlemen drink a little sake?" Sato asked politely. Craig thanked him and said that we would. "Otaka!" Sato called. A peculiar, almost white-skinned attendant answered, and a moment later produced four cups and poured out the rice brandy, taking his own quietly, apart from us. I watched him drink, curiously. He took the cup; then, with a long piece of carved wood, he dipped into the sake, shaking a few drops on the floor to the four quarters. Finally, with a deft sweep, he lifted his heavy mustache with the piece of wood and drank off the draft almost without taking breath. He was a peculiar man of middle height, with a shock of dark, tough, woolly hair, well formed and not bad-looking, with a robust general physique, as if his ancestors had been meat eaters. His forehead was narrow and sloped backward; the cheekbones were prominent; nose hooked, broad and wide, with strong nostrils; mouth large, with thick lips, and not very prominent chin. His eyes were perhaps the most noticeable feature. They were dark gray, almost like those of a European. As Otaka withdrew with the empty cups, we rose to continue our inspection of the wonders of the shop. There were ivories of all descriptions. Here was a two-handled sword, with a very large ivory handle, a weirdly carved scabbard, and wonderful steel blade. By the expression of Craig's face, Sato knew that he had made a sale. Craig had been rummaging among some warlike instruments which Sato, with the instincts of a true salesman, was now displaying, and had picked up a bow. It was short, very strong, and made of pine wood. He held it horizontally and twanged the string. I looked up in time to catch a pleased expression on the face of Otaka. "Most people would have held it the other way," commented Sato. Craig said nothing, but was examining an arrow, almost twenty inches long and thick, made of cane, with a point of metal very sharp but badly fastened. He fingered the deep blood groove in the scooplike head of the arrow and looked at it carefully. "I'll take that," he said, "only I wish it were one with the regular reddish-brown lump in it." "Oh, but, honorable sir," apologized Sato, "the Japanese law prohibits that, now. There are few of those, and they are very valuable." "I suppose so," agreed Craig. "This will do, though. You have a wonderful shop here, Sato. Some time, when I feel richer, I mean to come in again. No, thank you, you need not send them; I'll carry them." We bowed ourselves out, promising to come again when Sato received a new consignment from the Orient which he was expecting. "That other Jap is a peculiar fellow," I observed, as we walked along uptown again. "He isn't a Jap," remarked Craig. "He is an Ainu, one of the aborigines who have been driven northward into the island of Yezo." "An Ainu?" I repeated. "Yes. Generally thought, now, to be a white race and nearer of kin to Europeans than Asiatics. The Japanese have pushed them northward and are now trying to civilize them. They are a dirty, hairy race, but when they are brought under civilizing influences they adapt themselves to their environment and make very good servants. Still, they are on about the lowest scale of humanity." "I thought Otaka was very mild," I commented. "They are a most inoffensive and peaceable people usually," he answered, "good-natured and amenable to authority. But they become dangerous when driven to despair by cruel treatment. The Japanese government is very considerate of them--but not all Japanese are." CHAPTER XII THE ARROW POISON Far into the night Craig was engaged in some very delicate and minute microscopic work in the laboratory. We were about to leave when there was a gentle tap on the door. Kennedy opened it and admitted a young man, the operative of the detective agency who had been shadowing Bernardo. His report was very brief, but, to me at least, significant. Bernardo, on his return to the museum, had evidently read the letter, which had agitated him very much, for a few moments later he hurriedly left and went downtown to the Prince Henry Hotel. The operative had casually edged up to the desk and overheard whom he asked for. It was Senora Herreria. Once again, later in the evening, he had asked for her, but she was still out. It was quite early the next morning, when Kennedy had resumed his careful microscopic work, that the telephone bell rang, and he answered it mechanically. But a moment later a look of intense surprise crossed his face. "It was from Doctor Leslie," he announced, hanging up the receiver quickly. "He has a most peculiar case which he wants me to see--a woman." Kennedy called a cab, and, at a furious pace, we dashed across the city and down to the Metropolitan Hospital, where Doctor Leslie was waiting. He met us eagerly and conducted us to a little room where, lying motionless on a bed, was a woman. She was a striking-looking woman, dark of hair and skin, and in life she must have been sensuously attractive. But now her face was drawn and contorted--with the same ghastly look that had been on the face of Northrop. "She died in a cab," explained Doctor Leslie, "before they could get her to the hospital. At first they suspected the cab driver. But he seems to have proved his innocence. He picked her up last night on Fifth Avenue, reeling--thought she was intoxicated. And, in fact, he seems to have been right. Our tests have shown a great deal of alcohol present, but nothing like enough to have had such a serious effect." "She told nothing of herself?" asked Kennedy. "No; she was pretty far gone when the cabby answered her signal. All he could get out of her was a word that sounded like 'Curio-curio.' He says she seemed to complain of something about her mouth and head. Her face was drawn and shrunken; her hands were cold and clammy, and then convulsions came on. He called an ambulance, but she was past saving when it arrived. The numbness seemed to have extended over all her body; swallowing was impossible; there was entire loss of her voice as well as sight, and death took place by syncope." "Have you any clue to the cause of her death?" asked Craig. "Well, it might have been some trouble with her heart, I suppose," remarked Doctor Leslie tentatively. "Oh, she looks strong that way. No, hardly anything organic." "Well, then I thought she looked like a Mexican," went on Doctor Leslie. "It might be some new tropical disease. I confess I don't know. The fact is," he added, lowering his voice, "I had my own theory about it until a few moments ago. That was why I called you." "What do you mean?" asked Craig, evidently bent on testing his own theory by the other's ignorance. Doctor Leslie made no answer immediately, but raised the sheet which covered her body and disclosed, in the fleshy part of the upper arm, a curious little red swollen mark with a couple of drops of darkened blood. "I thought at first," he added, "that we had at last a genuine 'poisoned needle' case. You see, that looked like it. But I have made all the tests for curare and strychnin without results." At the mere suggestion, a procession of hypodermic-needle and white-slavery stories flashed before me. "But," objected Kennedy, "clearly this was not a case of kidnaping. It is a case of murder. Have you tested for the ordinary poisons?" Doctor Leslie shook his head. "There was no poison," he said, "absolutely none that any of our tests could discover." Kennedy bent over and squeezed out a few drops of liquid from the wound on a microscope slide, and covered them. "You have not identified her yet," he added, looking up. "I think you will find, Leslie, that there is a Senora Herreria registered at the Prince Henry who is missing, and that this woman will agree with the description of her. Anyhow, I wish you would look it up and let me know." Half an hour later, Kennedy was preparing to continue his studies with the microscope when Doctor Bernardo entered. He seemed most solicitous to know what progress was being made on the case, and, although Kennedy did not tell much, still he did not discourage conversation on the subject. When we came in the night before, Craig had unwrapped and tossed down the Japanese sword and the Ainu bow and arrow on a table, and it was not long before they attracted Bernardo's attention. "I see you are a collector yourself," he ventured, picking them up. "Yes," answered Craig, offhand; "I picked them up yesterday at Sato's. You know the place?" "Oh, yes, I know Sato," answered the curator, seemingly without the slightest hesitation. "He has been in Mexico--is quite a student." "And the other man, Otaka?" "Other man--Otaka? You mean his wife?" I saw Kennedy check a motion of surprise and came to the rescue with the natural question: "His wife--with a beard and mustache?" It was Bernardo's turn to be surprised. He looked at me a moment, then saw that I meant it, and suddenly his face lighted up. "Oh," he exclaimed, "that must have been on account of the immigration laws or something of the sort. Otaka is his wife. The Ainus are much sought after by the Japanese as wives. The women, you know, have a custom of tattooing mustaches on themselves. It is hideous, but they think it is beautiful." "I know," I pursued, watching Kennedy's interest in our conversation, "but this was not tattooed." "Well, then, it must have been false," insisted Bernardo. The curator chatted a few moments, during which I expected Kennedy to lead the conversation around to Senora Herreria. But he did not, evidently fearing to show his hand. "What did you make of it?" I asked, when he had gone. "Is he trying to hide something?" "I think he has simplified the case," remarked Craig, leaning back, his hands behind his head, gazing up at the ceiling. "Hello, here's Leslie! What did you find, Doctor?" The coroner had entered with a look of awe on his face, as if Kennedy had directed him by some sort of necromancy. "It was Senora Herreria!" he exclaimed. "She has been missing from the hotel ever since late yesterday afternoon. What do you think of it?" "I think," replied Kennedy, speaking slowly and deliberately, "that it is very much like the Northrop case. You haven't taken that up yet?" "Only superficially. What do you make of it?" asked the coroner. "I had an idea that it might be aconitin poisoning," he said. Leslie glanced at him keenly for a moment. "Then you'll never prove anything in the laboratory," he said. "There are more ways of catching a criminal, Leslie," put in Craig, "than are set down in the medico-legal text-books. I shall depend on you and Jameson to gather together a rather cosmopolitan crowd here to-night." He said it with a quiet confidence which I could not gainsay, although I did not understand. However, mostly with the official aid of Doctor Leslie, I followed out his instructions, and it was indeed a strange party that assembled that night. There were Doctor Bernardo; Sato, the curio dealer; Otaka, the Ainu, and ourselves. Mrs. Northrop, of course, could not come. "Mexico," began Craig, after he had said a few words explaining why he had brought us together, "is full of historical treasure. To all intents and purposes, the government says, 'Come and dig.' But when there are finds, then the government swoops down on them for its own national museum. The finder scarcely gets a chance to export them. However, now seemed to be the time to Professor Northrop to smuggle his finds out of the country. "But evidently it could not be done without exciting all kinds of rumors and suspicions. Stories seem to have spread far and fast about what he had discovered. He realized the unsettled condition of the country--perhaps wanted to confirm his reading of a certain inscription by consultation with one scholar whom he thought he could trust. At any rate, he came home." Kennedy paused, making use of the silence for emphasis. "You have all read of the wealth that Cortez found in Mexico. Where are the gold and silver of the conquistadores? Gone to the melting pot, centuries ago. But is there none left? The Indians believe so. There are persons who would stop at nothing--even at murder of American professors, murder of their own comrades, to get at the secret." He laid his hand almost lovingly on his powerful little microscope as he resumed on another line of evidence. "And while we are on the subject of murders, two very similar deaths have occurred," he went on. "It is of no use to try to gloss them over. Frankly, I suspected that they might have been caused by aconite poisoning. But, in the case of such poisoning, not only is the lethal dose very small but our chemical methods of detection are nil. The dose of the active principle, aconitin nitrate, is about one six-hundredth of a grain. There are no color tests, no reactions, as in the case of the other organic poisons." I wondered what he was driving at. Was there, indeed, no test? Had the murderer used the safest of poisons--one that left no clue? I looked covertly at Sato's face. It was impassive. Doctor Bernardo was visibly uneasy as Kennedy proceeded. Cool enough up to the time of the mention of the treasure, I fancied, now, that he was growing more and more nervous. Craig laid down on the table the reed stick with the little darkened cylinder on the end. "That," he said, "is a little article which I picked up beneath Northrop's window yesterday. It is a piece of anno-noki, or bushi." I fancied I saw just a glint of satisfaction in Otaka's eyes. "Like many barbarians," continued Craig, "the Ainus from time immemorial have prepared virulent poisons with which they charged their weapons of the chase and warfare. The formulas for the preparations, as in the case of other arrow poisons of other tribes, are known only to certain members, and the secret is passed down from generation to generation as an heirloom, as it were. But in this case it is no longer a secret. It has now been proved that the active principle of this poison is aconite." "If that is the case," broke in Doctor Leslie, "it is hopeless to connect anyone directly in that way with these murders. There is no test for aconitin." I thought Sato's face was more composed and impassive than ever. Doctor Bernardo, however, was plainly excited. "What--no test--NONE?" asked Kennedy, leaning forward eagerly. Then, as if he could restrain the answer to his own question no longer, he shot out: "How about the new starch test just discovered by Professor Reichert, of the University of Pennsylvania? Doubtless you never dreamed that starch may be a means of detecting the nature of a poison in obscure cases in criminology, especially in cases where the quantity of poison necessary to cause death is so minute that no trace of it can be found in the blood. "The starch method is a new and extremely inviting subject to me. The peculiarities of the starch of any plant are quite as distinctive of the plant as are those of the hemoglobin crystals in the blood of an animal. I have analyzed the evidence of my microscope in this case thoroughly. When the arrow poison is introduced subcutaneously--say, by a person shooting a poisoned dart, which he afterward removes in order to destroy the evidence--the lethal constituents are rapidly absorbed. "But the starch remains in the wound. It can be recovered and studied microscopically and can be definitely recognized. Doctor Reichert has published a study of twelve hundred such starches from all sorts of plants. In this case, it not only proves to be aconitin but the starch granules themselves can be recognized. They came from this piece of arrow poison." Every eye was fixed on him now. "Besides," he rapped out, "in the soft soil beneath the window of Professor Northrop's room, I found footprints. I have only to compare the impressions I took there and those of the people in this room, to prove that, while the real murderer stood guard below the window, he sent some one more nimble up the rain pipe to shoot the poisoned dart at Professor Northrop, and, later, to let down a rope by which he, the instigator, could gain the room, remove the dart, and obtain the key to the treasure he sought." Kennedy was looking straight at Professor Bernardo. "A friend of mine in Mexico has written me about an inscription," he burst out. "I received the letter only to-day. As nearly as I can gather, there was an impression that some of Northrop's stuff would be valuable in proving the alleged kinship between Mexico and Japan, perhaps to arouse hatred of the United States." "Yes--that is all very well," insisted Kennedy. "But how about the treasure?" "Treasure?" repeated Bernardo, looking from one of us to another. "Yes," pursued Craig relentlessly, "the treasure. You are an expert in reading the hieroglyphics. By your own statement, you and Northrop had been going over the stuff he had sent up. You know it." Bernardo gave a quick glance from Kennedy to me. Evidently he saw that the secret was out. "Yes," he said huskily, in a low tone, "Northrop and I were to follow the directions after we had plotted them out and were to share it together on the next expedition, which I could direct as a Mexican without so much suspicion. I should still have shared it with his widow if this unfortunate affair had not exposed the secret." Bernardo had risen earnestly. "Kennedy," he cried, "before God, if you will get back that stone and keep the secret from going further than this room, I will prove what I have said by dividing the Mixtec treasure with Mrs. Northrop and making her one of the richest widows in the country!" "That is what I wanted to be sure of," nodded Craig. "Bernardo, Senora Herreria, of whom your friend wrote to you from Mexico, has been murdered in the same way that Professor Northrop was. Otaka was sent by her husband to murder Northrop, in order that they might obtain the so-called 'Pillar of Death' and the key to the treasure. Then, when the senora was no doubt under the influence of sake in the pretty little Oriental bower at the curio shop, a quick jab, and Otaka had removed one who shared the secret with them." He had turned and faced the pair. "Sato," he added, "you played on the patriotism of the senora until you wormed from her the treasure secret. Evidently rumors of it had spread from Mexican Indians to Japanese visitors. And then, Otaka, all jealousy over one whom she, no doubt, justly considered a rival, completed your work by sending her forth to die, unknown, on the street. Walter, ring up First Deputy O'Connor. The stone is hidden somewhere in the curio shop. We can find it without Sato's help. The quicker such a criminal is lodged safely in jail, the better for humanity." Sato was on his feet, advancing cautiously toward Craig. I knew the dangers, now, of anno-noki, as well as the wonders of jujutsu, and, with a leap, I bounded past Bernardo and between Sato and Kennedy. How it happened, I don't know, but, an instant later, I was sprawling. Before I could recover myself, before even Craig had a chance to pull the hair-trigger of his automatic, Sato had seized the Ainu arrow poison from the table, had bitten the little cylinder in half, and had crammed the other half into the mouth of Otaka. CHAPTER XIII THE RADIUM ROBBER Kennedy simply reached for the telephone and called an ambulance. But it was purely perfunctory. Dr. Leslie himself was the only official who could handle Sato's case now. We had planned a little vacation for ourselves, but the planning came to naught. The next night we spent on a sleeper. That in itself is work to me. It all came about through a hurried message from Murray Denison, president of the Federal Radium Corporation. Nothing would do but that he should take both Kennedy and myself with him post-haste to Pittsburgh at the first news of what had immediately been called "the great radium robbery." Of course the newspapers were full of it. The very novelty of an ultra-modern cracksman going off with something worth upward of a couple of hundred thousand dollars--and all contained in a few platinum tubes which could be tucked away in a vest pocket--had something about it powerfully appealing to the imagination. "Most ingenious, but, you see, the trouble with that safe is that it was built to keep radium IN--not cracksmen OUT," remarked Kennedy, when Denison had rushed us from the train to take a look at the little safe in the works of the Corporation. "Breaking into such a safe as this," added Kennedy, after a cursory examination, "is simple enough, after all." It was, however, a remarkably ingenious contrivance, about three feet in height and of a weight of perhaps a ton and a half, and all to house something weighing only a few grains. "But," Denison hastened to explain, "we had to protect the radium not only against burglars, but, so to speak, against itself. Radium emanations pass through steel and experiments have shown that the best metal to contain them is lead. So, the difficulty was solved by making a steel outer case enclosing an inside leaden shell three inches thick." Kennedy had been toying thoughtfully with the door. "Then the door, too, had to be contrived so as to prevent any escape of the emanations through joints. It is lathe turned and circular, a 'dead fit.' By means of a special contrivance any slight looseness caused by wear and tear of closing can be adjusted. And another feature. That is the appliance for preventing the loss of emanation when the door is opened. Two valves have been inserted into the door and before it is opened tubes with mercury are passed through which collect and store the emanation." "All very nice for the radium," remarked Craig cheerfully. "But the fellow had only to use an electric drill and the gram or more of radium was his." "I know that--now," ruefully persisted Denison. "But the safe was designed for us specially. The fellow got into it and got away, as far as I can see, without leaving a clue." "Except one, of course," interrupted Kennedy quickly. Denison looked at him a moment keenly, then nodded and said, "Yes--you are right. You mean one which he must bear on himself?" "Exactly. You can't carry a gram or more of radium bromide long with impunity. The man to look for is one who in a few days will have somewhere on his body a radium burn which will take months to heal. The very thing he stole is a veritable Frankenstein's monster bent on the destruction of the thief himself!" Kennedy had meanwhile picked up one of the Corporation's circulars lying on a desk. He ran his eye down the list of names. "So, Hartley Haughton, the broker, is one of your stockholders," mused Kennedy. "Not only one but THE one," replied Denison with obvious pride. Haughton was a young man who had come recently into his fortune, and, while no one believed it to be large, he had cut quite a figure in Wall Street. "You know, I suppose," added Denison, "that he is engaged to Felicie Woods, the daughter of Mrs. Courtney Woods?" Kennedy did not, but said nothing. "A most delightful little girl," continued Denison thoughtfully. "I have known Mrs. Woods for some time. She wanted to invest, but I told her frankly that this is, after all, a speculation. We may not be able to swing so big a proposition, but, if not, no one can say we have taken a dollar of money from widows and orphans." "I should like to see the works," nodded Kennedy approvingly. "By all means." The plant was a row of long low buildings of brick on the outskirts of the city, once devoted to the making of vanadium steel. The ore, as Denison explained, was brought to Pittsburgh because he had found here already a factory which could readily be turned into a plant for the extraction of radium. Huge baths and vats and crucibles for the various acids and alkalis and other processes used in treating the ore stood at various points. "This must be like extracting gold from sea water," remarked Kennedy jocosely, impressed by the size of the plant as compared to the product. "Except that after we get through we have something infinitely more precious than gold," replied Denison, "something which warrants the trouble and outlay. Yes, the fact is that the percentage of radium in all such ores is even less than of gold in sea water." "Everything seems to be most carefully guarded," remarked Kennedy as we concluded our tour of the well-appointed works. He had gone over everything in silence, and now at last we had returned to the safe. "Yes," he repeated slowly, as if confirming his original impression, "such an amount of radium as was stolen wouldn't occasion immediate discomfort to the thief, I suppose, but later no infernal machine could be more dangerous to him." I pictured to myself the series of fearful works of mischief and terror that might follow, a curse on the thief worse than that of the weirdest curses of the Orient, the danger to the innocent, and the fact that in the hands of a criminal it was an instrument for committing crimes that might defy detection. "There is nothing more to do here now," he concluded. "I can see nothing for the present except to go back to New York. The telltale burn may not be the only clue, but if the thief is going to profit by his spoils we shall hear about it best in New York or by cable from London, Paris, or some other European city." Our hurried departure from New York had not given us a chance to visit the offices of the Radium Corporation for the distribution of the salts themselves. They were in a little old office building on William Street, near the drug district and yet scarcely a moment's walk from the financial district. "Our head bookkeeper, Miss Wallace, is ill," remarked Denison when we arrived at the office, "but if there is anything I can do to help you, I shall be glad to do it. We depend on Miss Wallace a great deal. Haughton says she is the brains of the office." Kennedy looked about the well-appointed suite curiously. "Is this another of those radium safes?" he asked, approaching one similar in appearance to that which had been broken open already. "Yes, only a little larger." "How much is in it?" "Most of our supply. I should say about two and a half grams. Miss Wallace has the record." "It is of the same construction, I presume," pursued Kennedy. "I wonder whether the lead lining fits closely to the steel?" "I think not," considered Denison. "As I remember there was a sort of insulating air cushion or something of the sort." Denison was quite eager to show us about. In fact ever since he had hustled us out to view the scene of the robbery, his high nervous tension had given us scarcely a moment's rest. For hours he had talked radium, until I felt that he, like his metal, must have an inexhaustible emanation of words. He was one of those nervous, active little men, a born salesman, whether of ribbons or radium. "We have just gone into furnishing radium water," he went on, bustling about and patting a little glass tank. I looked closely and could see that the water glowed in the dark with a peculiar phosphorescence. "The apparatus for the treatment," he continued, "consists of two glass and porcelain receptacles. Inside the larger receptacle is placed the smaller, which contains a tiny quantity of radium. Into the larger receptacle is poured about a gallon of filtered water. The emanation from that little speck of radium is powerful enough to penetrate its porcelain holder and charge the water with its curative properties. From a tap at the bottom of the tank the patient draws the number of glasses of water a day prescribed. For such purposes the emanation within a day or two of being collected is as good as radium itself. Why, this water is five thousand times as radioactive as the most radioactive natural spring water." "You must have control of a comparatively large amount of the metal," suggested Kennedy. "We are, I believe, the largest holders of radium in the world," he answered. "I have estimated that all told there are not much more than ten grams, of which Madame Curie has perhaps three, while Sir Ernest Cassel of London is the holder of perhaps as much. We have nearly four grams, leaving about six or seven for the rest of the world." Kennedy nodded and continued to look about. "The Radium Corporation," went on Denison, "has several large deposits of radioactive ore in Utah in what is known as the Poor Little Rich Valley, a valley so named because from being about the barrenest and most unproductive mineral or agricultural hole in the hills, the sudden discovery of the radioactive deposits has made it almost priceless." He had entered a private office and was looking over some mail that had been left on his desk during his absence. "Look at this," he called, picking up a clipping from a newspaper which had been laid there for his attention. "You see, we have them aroused." We read the clipping together hastily: PLAN TO CORNER WORLD'S RADIUM LONDON.--Plans are being matured to form a large corporation for the monopoly of the existing and future supply of radium throughout the world. The company is to be called Universal Radium, Limited, and the capital of ten million dollars will be offered for public subscription at par simultaneously in London, Paris and New York. The company's business will be to acquire mines and deposits of radioactive substances as well as the control of patents and processes connected with the production of radium. The outspoken purpose of the new company is to obtain a world-wide monopoly and maintain the price. "Ah--a competitor," commented Kennedy, handing back the clipping. "Yes. You know radium salts used always to come from Europe. Now we are getting ready to do some exporting ourselves. Say," he added excitedly, "there's an idea, possibly, in that." "How?" queried Craig. "Why, since we should be the principal competitors to the foreign mines, couldn't this robbery have been due to the machinations of these schemers? To my mind, the United States, because of its supply of radium-bearing ores, will have to be reckoned with first in cornering the market. This is the point, Kennedy. Would those people who seem to be trying to extend their new company all over the world stop at anything in order to cripple us at the start?" How much longer Denison would have rattled on in his effort to explain the robbery, I do not know. The telephone rang and a reporter from the Record, who had just read my own story in the Star, asked for an interview. I knew that it would be only a question of minutes now before the other men were wearing a path out on the stairs, and we managed to get away before the onrush began. "Walter," said Kennedy, as soon as we had reached the street. "I want to get in touch with Halsey Haughton. How can it be done?" I could think of nothing better at that moment than to inquire at the Star's Wall Street office, which happened to be around the corner. I knew the men down there intimately, and a few minutes later we were whisked up in the elevator to the office. They were as glad to see me as I was to see them, for the story of the robbery had interested the financial district perhaps more than any other. "Where can I find Halsey Haughton at this hour?" I asked. "Say," exclaimed one of the men, "what's the matter? There have been all kinds of rumors in the Street about him to-day. Did you know he was ill?" "No," I answered. "Where is he?" "Out at the home of his fiancee, who is the daughter of Mrs. Courtney Woods, at Glenclair." "What's the matter?" I persisted. "That's just it. No one seems to know. They say--well--they say he has a cancer." Halsey Haughton suffering from cancer? It was such an uncommon thing to hear of a young man that I looked up quickly in surprise. Then all at once it flashed over me that Denison and Kennedy had discussed the matter of burns from the stolen radium. Might not this be, instead of cancer, a radium burn? Kennedy, who had been standing a little apart from me while I was talking with the boys, signaled to me with a quick glance not to say too much, and a few minutes later we were on the street again. I knew without being told that he was bound by the next train to the pretty little New Jersey suburb of Glenclair. It was late when we arrived, yet Kennedy had no hesitation in calling at the quaint home of Mrs. Courtney Woods on Woodridge Avenue. Mrs. Woods, a well-set-up woman of middle age, who had retained her youth and good looks in a remarkable manner, met us in the foyer. Briefly, Kennedy explained that we had just come in from Pittsburgh with Mr. Denison and that it was very important that we should see Haughton at once. We had hardly told her the object of our visit when a young woman of perhaps twenty-two or three, a very pretty girl, with all the good looks of her mother and a freshness which only youth can possess, tiptoed quietly downstairs. Her face told plainly that she was deeply worried over the illness of her fiance. "Who is it, mother?" she whispered from the turn in the stairs. "Some gentlemen from the company? Hartley's door was open when the bell rang, and he thought he heard something said about the Pittsburgh affair." Though she had whispered, it had not been for the purpose of concealing anything from us, but rather that the keen ears of her patient might not catch the words. She cast an inquiring glance at us. "Yes," responded Kennedy in answer to her look, modulating his tone. "We have just left Mr. Denison at the office. Might we see Mr. Haughton for a moment? I am sure that nothing we can say or do will be as bad for him as our going away, now that he knows that we are here." The two women appeared to consult for a moment. "Felicie," called a rather nervous voice from the second floor, "is it some one from the company?" "Just a moment, Hartley," she answered, then, lower to her mother, added, "I don't think it can do any harm, do you, mother?" "You remember the doctor's orders, my dear." Again the voice called her. "Hang the doctor's orders," the girl exclaimed, with an air of almost masculinity. "It can't be half so bad as to have him worry. Will you promise not to stay long? We expect Dr. Bryant in a few moments, anyway." CHAPTER XIV THE SPINTHARISCOPE We followed her upstairs and into Haughton's room, where he was lying in bed, propped up by pillows. Haughton certainly was ill. There was no mistake about that. He was a tall, gaunt man with an air about him that showed that he found illness very irksome. Around his neck was a bandage, and some adhesive tape at the back showed that a plaster of some sort had been placed there. As we entered his eyes traveled restlessly from the face of the girl to our own in an inquiring manner. He stretched out a nervous hand to us, while Kennedy in a few short sentences explained how we had become associated with the case and what we had seen already. "And there is not a clue?" he repeated as Craig finished. "Nothing tangible yet," reiterated Kennedy. "I suppose you have heard of this rumor from London of a trust that is going into the radium field internationally?" "Yes," he answered, "that is the thing you read to me in the morning papers, you remember, Felicie. Denison and I have heard such rumors before. If it is a fight, then we shall give them a fight. They can't hold us up, if Denison is right in thinking that they are at the bottom of this--this robbery." "Then you think he may be right?" shot out Kennedy quickly. Haughton glanced nervously from Kennedy to me. "Really," he answered, "you see how impossible it is for me to have an opinion? You and Denison have been over the ground. You know much more about it than I do. I am afraid I shall have to defer to you." Again we heard the bell downstairs, and a moment later a cheery voice, as Mrs. Woods met some one down in the foyer, asked, "How is the patient to-night?" We could not catch the reply. "Dr. Bryant, my physician," put in Haughton. "Don't go. I will assume the responsibility for your being here. Hello, Doctor. Why, I'm much the same to-night, thank you. At least no worse since I took your advice and went to bed." Dr. Bryant was a bluff, hearty man, with the personal magnetism which goes with the making of a successful physician. He had mounted the stairs quietly but rapidly, evidently prepared to see us. "Would you mind waiting in this little dressing room?" asked the doctor, motioning to another, smaller room adjoining. He had taken from his pocket a little instrument with a dial face like a watch, which he attached to Haughton's wrist. "A pocket instrument to measure blood pressure," whispered Craig, as we entered the little room. While the others were gathered about Haughton, we stood in the next room, out of earshot. Kennedy had leaned his elbow on a chiffonier. As he looked about the little room, more from force of habit than because he thought he might discover anything, Kennedy's eye rested on a glass tray on the top in which lay some pins, a collar button or two, which Haughton had apparently just taken off, and several other little unimportant articles. Kennedy bent over to look at the glass tray more closely, a puzzled look crossed his face, and with a glance at the other room he gathered up the tray and its contents. "Keep up a good courage," said Dr. Bryant. "You'll come out all right, Haughton." Then as he left the bedroom he added to us, "Gentlemen, I hope you will pardon me, but if you could postpone the remainder of your visit until a later day, I am sure you will find it more satisfactory." There was an air of finality about the doctor, though nothing unpleasant in it. We followed him down the stairs, and as we did so, Felicie, who had been waiting in a reception room, appeared before the portieres, her earnest eyes fixed on his kindly face. "Dr. Bryant," she appealed, "is he--is he, really--so badly?" The Doctor, who had apparently known her all her life, reached down and took one of her hands, patting it with his own in a fatherly way. "Don't worry, little girl," he encouraged. "We are going to come out all right--all right." She turned from him to us and, with a bright forced smile which showed the stuff she was made of, bade us good night. Outside, the Doctor, apparently regretting that he had virtually forced us out, paused before his car. "Are you going down toward the station? Yes? I am going that far. I should be glad to drive you there." Kennedy climbed into the front seat, leaving me in the rear where the wind wafted me their brief conversation as we sped down Woodbridge Avenue. "What seems to be the trouble?" asked Craig. "Very high blood pressure, for one thing," replied the Doctor frankly. "For which the latest thing is the radium water cure, I suppose?" ventured Kennedy. "Well, radioactive water is one cure for hardening of the arteries. But I didn't say he had hardening of the arteries. Still, he is taking the water, with good results. You are from the company?" Kennedy nodded. "It was the radium water that first interested him in it. Why, we found a pressure of 230 pounds, which is frightful, and we have brought it down to 150, not far from normal." "Still that could have nothing to do with the sore on his neck," hazarded Kennedy. The Doctor looked at him quickly, then ahead at the path of light which his motor shed on the road. He said nothing, but I fancied that even he felt there was something strange in his silence over the new complication. He did not give Kennedy a chance to ask whether there were any other such sores. "At any rate," he said, as he throttled down his engine with a flourish before the pretty little Glenclair station, "that girl needn't worry." There was evidently no use in trying to extract anything further from him. He had said all that medical ethics or detective skill could get from him. We thanked him and turned to the ticket window to see how long we should have to wait. "Either that doctor doesn't know what he is talking about or he is concealing something," remarked Craig, as we paced up and down the platform. "I am inclined to read the enigma in the latter way." Nothing more passed between us during the journey back, and we hurried directly to the laboratory, late as it was. Kennedy had evidently been revolving something over and over in his mind, for the moment he had switched on the light, he unlocked one of his air-and dust-proof cabinets and took from it an instrument which he placed on a table before him. It was a peculiar-looking instrument, like a round glass electric battery with a cylinder atop, smaller and sticking up like a safety valve. On that were an arm, a dial, and a lens fixed in such a way as to read the dial. I could not see what else the rather complicated little apparatus consisted of, but inside, when Kennedy brought near it the pole of a static electric machine two delicate thin leaves of gold seemed to fly wide apart when it was charged. Kennedy had brought the glass tray near the thing. Instantly the leaves collapsed and he made a reading through the lens. "What is it?" I asked. "A radioscope," he replied, still observing the scale. "Really a very sensitive gold leaf electroscope, devised by one of the students of Madame Curie. This method of detection is far more sensitive even than the spectroscope." "What does it mean when the leaves collapse?" I asked. "Radium has been near that tray," he answered. "It is radioactive. I suspected it first when I saw that violet color. That is what radium does to that kind of glass. You see, if radium exists in a gram of inactive matter only to the extent of one in ten-thousand million parts its presence can be readily detected by this radioscope, and everything that has been rendered radioactive is the same. Ordinarily the air between the gold leaves is insulating. Bringing something radioactive near them renders the air a good conductor and the leaves fall under the radiation." "Wonderful!" I exclaimed, marveling at the delicacy of it. "Take radium water," he went on, "sufficiently impregnated with radium emanations to be luminous in the dark, like that water of Denison's. It would do the same. In fact all mineral waters and the so-called curarive muds like fango are slightly radioactive. There seems to be a little radium everywhere on earth that experiments have been made, even in the interiors of buildings. It is ubiquitous. We are surrounded and permeated by radiations--that soil out there on the campus, the air of this room, all. But," he added contemplatively, "there is something different about that tray. A lot of radium has been near that, and recently." "How about that bandage about Haughton's neck?" I asked suddenly. "Do you think radium could have had anything to do with that?" "Well, as to burns, there is no particular immediate effect usually, and sometimes even up to two weeks or more, unless the exposure has been long and to a considerable quantity. Of course radium keeps itself three or four degrees warmer than other things about it constantly. But that isn't what does the harm. It is continually emitting little corpuscles, which I'll explain some other time, traveling all the way from twenty to one hundred and thirty thousand miles a second, and these corpuscles blister and corrode the flesh like quick-moving missiles bombarding it. The gravity of such lesions increases with the purity of the radium. For instance I have known an exposure of half an hour to a comparatively small quantity through a tube, a box and the clothes to produce a blister fifteen days later. Curie said he wouldn't trust himself in a room with a kilogram of it. It would destroy his eyesight, burn off his skin and kill him eventually. Why, even after a slight exposure your clothes are radioactive--the electroscope will show that." He was still fumbling with the glass plate and the various articles on it. "There's something very peculiar about all this," he muttered, almost to himself. Tired by the quick succession of events of the past two days, I left Kennedy still experimenting in his laboratory and retired, still wondering when the real clue was to develop. Who could it have been who bore the tell-tale burn? Was the mark hidden by the bandage about Haughton's neck the brand of the stolen tubes? Or were there other marks on his body which we could not see? No answer came to me, and I fell asleep and woke up without a radiation of light on the subject. Kennedy spent the greater part of the day still at work at his laboratory, performing some very delicate experiments. Finding nothing to do there, I went down to the Star office and spent my time reading the reports that came in from the small army of reporters who had been assigned to run down clues in the case which was the sensation of the moment. I have always felt my own lips sealed in such cases, until the time came that the story was complete and Kennedy released me from any further need of silence. The weird and impossible stories which came in not only to the Star but to the other papers surely did make passable copy in this instance, but with my knowledge of the case I could see that not one of them brought us a step nearer the truth. One thing which uniformly puzzled the newspapers was the illness of Haughton and his enforced idleness at a time which was of so much importance to the company which he had promoted and indeed very largely financed. Then, of course, there was the romantic side of his engagement to Felicie Woods. Just what connection Felicie Woods had with the radium robbery if any, I was myself unable quite to fathom. Still, that made no difference to the papers. She was pretty and therefore they published her picture, three columns deep, with Haughton and Denison, who were intimately concerned with the real loss in little ovals perhaps an inch across and two inches in the opposite dimension. The late afternoon news editions had gone to press, and I had given up in despair, determined to go up to the laboratory and sit around idly watching Kennedy with his mystifying experiments, in preference to waiting for him to summon me. I had scarcely arrived and settled myself to an impatient watch, when an automobile drove up furiously, and Denison himself, very excited, jumped out and dashed into the laboratory. "What's the matter?" asked Kennedy, looking up from a test tube which he had been examining, with an air for all the world expressive of "Why so hot, little man?" "I've had a threat," ejaculated Denison. He laid on one of the laboratory tables a letter, without heading and without signature, written in a disguised hand, with an evident attempt to simulate the cramped script of a foreign penmanship. "I know who did the Pittsburgh job. The same party is out to ruin Federal Radium. Remember Pittsburgh and be prepared! "A STOCKHOLDER." "Well?" demanded Kennedy, looking up. "That can have only one meaning," asserted Denison. "What is that?" inquired Kennedy coolly, as if to confirm his own interpretation. "Why, another robbery--here in New York, of course." "But who would do it?" I asked. "Who?" repeated Denison. "Some one representing that European combine, of course. That is only part of the Trust method--ruin of competitors whom they cannot absorb." "Then you have refused to go into the combine? You know who is backing it?" "No--no," admitted Denison reluctantly. "We have only signified our intent to go it alone, as often as anyone either with or without authority has offered to buy us out. No, I do not even know who the people are. They never act in the open. The only hints I have ever received were through perfectly reputable brokers acting for others." "Does Haughton know of this note?" asked Kennedy. "Yes. As soon as I received it, I called him up." "What did he say?" "He said to disregard it. But--you know what condition he is in. I don't know what to do, whether to surround the office by a squad of detectives or remove the radium to a regular safety deposit vault, even at the loss of the emanation. Haughton has left it to me." Suddenly the thought flashed across my mind that perhaps Haughton could act in this uninterested fashion because he had no fear of ruin either way. Might he not be playing a game with the combination in which he had protected himself so that he would win, no matter what happened? "What shall I do?" asked Denison. "It is getting late." "Neither," decided Kennedy. Denison shook his head. "No," he said, "I shall have some one watch there, anyhow." CHAPTER XV THE ASPHYXIATING SAFE Denison had scarcely gone to arrange for some one to watch the office that night, when Kennedy, having gathered up his radioscope and packed into a parcel a few other things from various cabinets, announced: "Walter, I must see that Miss Wallace, right away. Denison has already given me her address. Call a cab while I finish clearing up here. I don't like the looks of this thing, even if Haughton does neglect it." We found Miss Wallace at a modest boarding-house in an old but still respectable part of the city. She was a very pretty girl, of the slender type, rather a business woman than one given much to amusement. She had been ill and was still ill. That was evident from the solicitous way in which the motherly landlady scrutinized two strange callers. Kennedy presented a card from Denison, and she came down to the parlor to see us. "Miss Wallace," began Kennedy, "I know it is almost cruel to trouble you when you are not feeling like office work, but since the robbery of the safe at Pittsburgh, there have been threats of a robbery of the New York office." She started involuntarily, and it was evident, I thought, that she was in a very high-strung state. "Oh," she cried, "why, the loss means ruin to Mr. Denison!" There were genuine tears in her eyes as she said it. "I thought you would be willing to aid us," pursued Kennedy sympathetically. "Now, for one thing, I want to be perfectly sure just how much radium the Corporation owns, or rather owned before the first robbery." "The books will show it," she said simply. "They will?" commented Kennedy. "Then if you will explain to me briefly just the system you used in keeping account of it, perhaps I need not trouble you any more." "I'll go down there with you," she answered bravely. "I'm better to-day, anyhow, I think." She had risen, but it was evident that she was not as strong as she wanted us to think. "The least I can do is to make it as easy as possible by going in a car," remarked Kennedy, following her into the hall where there was a telephone. The hallway was perfectly dark, yet as she preceded us I could see that the diamond pin which held her collar in the back sparkled as if a lighted candle had been brought near it. I had noticed in the parlor that she wore a handsome tortoiseshell comb set with what I thought were other brilliants, but when I looked I saw now that there was not the same sparkle to the comb which held her dark hair in a soft mass. I noticed these little things at the time, not because I thought they had any importance, but merely by chance, wondering at the sparkle of the one diamond which had caught my eye. "What do you make of her?" I asked as Kennedy finished telephoning. "A very charming and capable girl," he answered noncommittally. "Did you notice how that diamond in her neck sparkled?" I asked quickly. He nodded. Evidently it had attracted his attention, too. "What makes it?" I pursued. "Well, you know radium rays will make a diamond fluoresce in the dark." "Yes," I objected, "but how about those in the comb?" "Paste, probably," he answered tersely, as we heard her foot on the landing. "The rays won't affect paste." It was indeed a shame to take advantage of Miss Wallace's loyalty to Denison, but she was so game about it that I knew only the utmost necessity on Kennedy's part would have prompted him to do it. She had a key to the office so that it was not necessary to wait for Denison, if indeed we could have found him. Together she and Kennedy went over the records. It seemed that there were in the safe twenty-five platinum tubes of one hundred milligrams each, and that there had been twelve of the same amount at Pittsburgh. Little as it seemed in weight it represented a fabulous fortune. "You have not the combination?" inquired Kennedy. "No. Only Mr. Denison has that. What are you going to do to protect the safe to-night?" she asked. "Nothing especially," evaded Kennedy. "Nothing?" she repeated in amazement. "I have another plan," he said, watching her intently. "Miss Wallace, it was too much to ask you to come down here. You are ill." She was indeed quite pale, as if the excitement had been an overexertion. "No, indeed," she persisted. Then, feeling her own weakness, she moved toward the door of Denison's office where there was a leather couch. "Let me rest here a moment. I do feel queer. I--" She would have fallen if he had not sprung forward and caught her as she sank to the floor, overcome by the exertion. Together we carried her in to the couch, and as we did so the comb from her hair clattered to the floor. Craig threw open the window, and bathed her face with water until there was a faint flutter of the eyelids. "Walter," he said, as she began to revive, "I leave her to you. Keep her quiet for a few moments. She has unintentionally given me just the opportunity I want." While she was yet hovering between consciousness and unconsciousness on the couch, he had unwrapped the package which he had brought with him. For a moment he held the comb which she had dropped near the radioscope. With a low exclamation of surprise he shoved it into his pocket. Then from the package he drew a heavy piece of apparatus which looked as if it might be the motor part of an electric fan, only in place of the fan he fitted a long, slim, vicious-looking steel bit. A flexible wire attached the thing to the electric light circuit and I knew that it was an electric drill. With his coat off he tugged at the little radium safe until he had moved it out, then dropped on his knees behind it and switched the current on in the electric drill. It was a tedious process to drill through the steel of the outer casing of the safe and it was getting late. I shut the door to the office so that Miss Wallace could not see. At last by the cessation of the low hum of the boring, I knew that he had struck the inner lead lining. Quietly I opened the door and stepped out. He was injecting something from an hermetically sealed lead tube into the opening he had made and allowing it to run between the two linings of lead and steel. Then using the tube itself he sealed the opening he had made and dabbed a little black over it. Quickly he shoved the safe back, then around it concealed several small coils with wires also concealed and leading out through a window to a court. "We'll catch the fellow this time," he remarked as he worked. "If you ever have any idea, Walter, of going into the burglary business, it would be well to ascertain if the safes have any of these little selenium cells as suggested by my friend, Mr. Hammer, the inventor. For by them an alarm can be given miles away the moment an intruder's bull's-eye falls on a hidden cell sensitive to light." While I was delegated to take Miss Wallace home, Kennedy made arrangements with a small shopkeeper on the ground floor of a building that backed up on the court for the use of his back room that night, and had already set up a bell actuated by a system of relays which the weak current from the selenium cells could operate. It was not until nearly midnight that he was ready to leave the laboratory again, where he had been busily engaged in studying the tortoiseshell comb which Miss Wallace in her weakness had forgotten. The little shopkeeper let us in sleepily and Kennedy deposited a large round package on a chair in the back of the shop, as well as a long piece of rubber tubing. Nothing had happened so far. As we waited the shopkeeper, now wide awake and not at all unconvinced that we were bent on some criminal operation, hung around. Kennedy did not seem to care. He drew from his pocket a little shiny brass instrument in a lead case, which looked like an abbreviated microscope. "Look through it," he said, handing it to me. I looked and could see thousands of minute sparks. "What is it?" I asked. "A spinthariscope. In that it is possible to watch the bombardment of the countless little corpuscles thrown off by radium, as they strike on the zinc blende crystal which forms the base. When radium was originally discovered, the interest was merely in its curious properties, its power to emit invisible rays which penetrated solid substances and rendered things fluorescent, of expending energy without apparent loss. "Then came the discovery," he went on, "of its curative powers. But the first results were not convincing. Still, now that we know the reasons why radium may be dangerous and how to protect ourselves against them we know we possess one of the most wonderful of curative agencies." I was thinking rather of the dangers than of the beneficence of radium just now, but Kennedy continued. "It has cured many malignant growths that seemed hopeless, brought back destroyed cells, exercised good effects in diseases of the liver and intestines and even the baffling diseases of the arteries. The reason why harm, at first, as well as good came, is now understood. Radium emits, as I told you before, three kinds of rays, the alpha, beta, and gamma rays, each with different properties. The emanation is another matter. It does not concern us in this case, as you will see." Fascinated as I was by the mystery of the case, I began to see that he was gradually arriving at an explanation which had baffled everyone else. "Now, the alpha rays are the shortest," he launched forth, "in length let us say one inch. They exert a very destructive effect on healthy tissue. That is the cause of injury. They are stopped by glass, aluminum and other metals, and are really particles charged with positive electricity. The beta rays come next, say, about an inch and a half. They stimulate cell growth. Therefore they are dangerous in cancer, though good in other ways. They can be stopped by lead, and are really particles charged with negative electricity. The gamma rays are the longest, perhaps three inches long, and it is these rays which effect cures, for they check the abnormal and stimulate the normal cells. They penetrate lead. Lead seems to filter them out from the other rays. And at three inches the other rays don't reach, anyhow. The gamma rays are not charged with electricity at all, apparently." He had brought a little magnet near the spinthariscope. I looked into it. "A magnet," he explained, "shows the difference between the alpha, beta, and gamma rays. You see those weak and wobbly rays that seem to fall to one side? Those are the alpha rays. They have a strong action, though, on tissues and cells. Those falling in the other direction are the beta rays. The gamma rays seem to flow straight." "Then it is the alpha rays with which we are concerned mostly now?" I queried, looking up. "Exactly. That is why, when radium is unprotected or insufficiently protected and comes too near, it is destructive of healthy cells, produces burns, sores, which are most difficult to heal. It is with the explanation of such sores that we must deal." It was growing late. We had waited patiently now for some time. Kennedy had evidently reserved this explanation, knowing we should have to wait. Still nothing happened. Added to the mystery of the violet-colored glass plate was now that of the luminescent diamond. I was about to ask Kennedy point-blank what he thought of them, when suddenly the little bell before us began to buzz feebly under the influence of a current. I gave a start. The faithful little selenium cell burglar alarm had done the trick. I knew that selenium was a good conductor of electricity in the light, poor in the dark. Some one had, therefore, flashed a light on one of the cells in the Corporation office. It was the moment for which Kennedy had prepared. Seizing the round package and the tubing, he dashed out on the street and around the corner. He tried the door opening into the Radium Corporation hallway. It was closed, but unlocked. As it yielded and we stumbled in, up the old worn wooden stairs of the building, I knew that there must be some one there. A terrific, penetrating, almost stunning odor seemed to permeate the air even in the hall. Kennedy paused at the door of the office, tried it, found it unlocked, but did not open it. "That smell is ethyldichloracetate," he explained. "That was what I injected into the air cushion of that safe between the two linings. I suppose my man here used an electric drill. He might have used thermit or an oxyacetylene blowpipe for all I would care. These fumes would discourage a cracksman from 'soup' to nuts," he laughed, thoroughly pleased at the protection modern science had enabled him to devise. As we stood an instant by the door, I realized what had happened. We had captured our man. He was asphyxiated! Yet how were we to get to him? Would Craig leave him in there, perhaps to die? To go in ourselves meant to share his fate, whatever might be the effect of the drug. Kennedy had torn the wrapping off the package. From it he drew a huge globe with bulging windows of glass in the front and several curious arrangements on it at other points. To it he fitted the rubber tubing and a little pump. Then he placed the globe over his head, like a diver's helmet, and fastened some air-tight rubber arrangement about his neck and shoulders. "Pump, Walter!" he shouted. "This is an oxygen helmet such as is used in entering mines filled with deadly gases." Without another word he was gone into the blackness of the noxious stifle which filled the Radium Corporation office since the cracksman had struck the unexpected pocket of rapidly evaporating stuff. I pumped furiously. Inside I could hear him blundering around. What was he doing? He was coming back slowly. Was he, too, overcome? As he emerged into the darkness of the hallway where I myself was almost sickened, I saw that he was dragging with him a limp form. A rush of outside air from the street door seemed to clear things a little. Kennedy tore off the oxygen helmet and dropped down on his knees beside the figure, working its arms in the most approved manner of resuscitation. "I think we can do it without calling on the pulmotor," he panted. "Walter, the fumes have cleared away enough now in the outside office. Open a window--and keep that street door open, too." I did so, found the switch and turned on the lights. It was Denison himself! For many minutes Kennedy worked over him. I bent down, loosened his collar and shirt, and looked eagerly at his chest for the tell-tale marks of the radium which I felt sure must be there. There was not even a discoloration. Not a word was said, as Kennedy brought the stupefied little man around. Denison, pale, shaken, was leaning back now in a big office chair, gasping and holding his head. Kennedy, before him, reached down into his pocket and handed him the spinthariscope. "You see that?" he demanded. Denison looked through the eyepiece. "Wh--where did you get so much of it?" he asked, a queer look on his face. "I got that bit of radium from the base of the collar button of Hartley Haughton," replied Kennedy quietly, "a collar button which some one intimate with him had substituted for his own, bringing that deadly radium with only the minutest protection of a thin strip of metal close to the back of his neck, near the spinal cord and the medulla oblongata which controls blood pressure. That collar button was worse than the poisoned rings of the Borgias. And there is more radium in the pretty gift of a tortoiseshell comb with its paste diamonds which Miss Wallace wore in her hair. Only a fraction of an inch, not enough to cut off the deadly alpha rays, protected the wearers of those articles." He paused a moment, while surging through my mind came one after another the explanations of the hitherto inexplicable. Denison seemed almost to cringe in the chair, weak already from the fumes. "Besides," went on Kennedy remorselessly, "when I went in there to drag you out, I saw the safe open. I looked. There was nothing in those pretty platinum tubes, as I suspected. European trust--bah! All the cheap devices of a faker with a confederate in London to send a cablegram--and another in New York to send a threatening letter." Kennedy extended an accusing forefinger at the man cowering before him. "This is nothing but a get-rich-quick scheme, Denison. There never was a milligram of radium in the Poor Little Rich Valley, not a milligram here in all the carefully kept reports of Miss Wallace--except what was bought outside by the Corporation with the money it collected from its dupes. Haughton has been fleeced. Miss Wallace, blinded by her loyalty to you--you will always find such a faithful girl in such schemes as yours--has been fooled. "And how did you repay it? What was cleverer, you said to yourself, than to seem to be robbed of what you never had, to blame it on a bitter rival who never existed? Then to make assurance doubly sure, you planned to disable, perhaps get rid of the come-on whom you had trimmed, and the faithful girl whose eyes you had blinded to your gigantic swindle. "Denison," concluded Kennedy, as the man drew back, his very face convicting him, "Denison, you are the radium robber--robber in another sense!" CHAPTER XVI THE DEAD LINE Maiden Lane, no less than Wall Street, was deeply interested in the radium case. In fact, it seemed that one case in this section of the city led to another. Naturally, the Star and the other papers made much of the capture of Denison. Still, I was not prepared for the host of Maiden Lane cases that followed. Many of them were essentially trivial. But one proved to be of extreme importance. "Professor Kennedy, I have just heard of your radium case, and I--I feel that I can--trust you." There was a note of appeal in the hesitating voice of the tall, heavily veiled woman whose card had been sent up to us with a nervous "Urgent" written across its face. It was very early in the morning, but our visitor was evidently completely unnerved by some news which she had just received and which had sent her posting to see Craig. Kennedy met her gaze directly with a look that arrested her involuntary effort to avoid it again. She must have read in his eyes more than in his words that she might trust him. "I--I have a confession to make," she faltered. "Please sit down, Mrs. Moulton," he said simply. "It is my business to receive confidences--and to keep them." She sank into, rather than sat down in, the deep leather rocker beside his desk, and now for the first time raised her veil. Antoinette Moulton was indeed stunning, an exquisite creature with a wonderful charm of slender youth, brightness of eye and brunette radiance. I knew that she had been on the musical comedy stage and had had a rapid rise to a star part before her marriage to Lynn Moulton, the wealthy lawyer, almost twice her age. I knew also that she had given up the stage, apparently without a regret. Yet there was something strange about the air of secrecy of her visit. Was there a hint in it of a disagreement between the Moultons, I wondered, as I waited while Kennedy reassured her. Her distress was so unconcealed that Craig, for the moment, laid aside his ordinary inquisitorial manner. "Tell me just as much or just as little as you choose, Mrs. Moulton," he added tactfully. "I will do my best." A look almost of gratitude crossed her face. "When we were married," she began again, "my husband gave me a beautiful diamond necklace. Oh, it must have been worth a hundred thousand dollars easily. It was splendid. Everyone has heard of it. You know, Lynn--er--Mr. Moulton, has always been an enthusiastic collector of jewels." She paused again and Kennedy nodded reassuringly. I knew the thought in his mind. Moulton had collected one gem that was incomparable with all the hundred thousand dollar necklaces in existence. "Several months ago." she went on rapidly, still avoiding his eyes and forcing the words from her reluctant lips, "I--oh, I needed money--terribly." She had risen and faced him, pressing her daintily gloved hands together in a little tremble of emotion which was none the less genuine because she had studied the art of emotion. "I took the necklace to a jeweler, Herman Schloss, of Maiden Lane, a man with whom my husband had often had dealings and whom I thought I could trust. Under a promise of secrecy he loaned me fifty thousand dollars on it and had an exact replica in paste made by one of his best workmen. This morning, just now, Mr. Schloss telephoned me that his safe had been robbed last night. My necklace is gone!" She threw out her hands in a wildly appealing gesture. "And if Lynn finds that the necklace in our wall safe is of paste--as he will find, for he is an expert in diamonds--oh--what shall I do? Can't you--can't you find my necklace?" Kennedy was following her now eagerly. "You were blackmailed out of the money?" he queried casually, masking his question. There was a sudden, impulsive drooping of her mouth, an evasion and keen wariness in her eyes. "I can't see that that has anything to do with the robbery," she answered in a low voice. "I beg your pardon," corrected Kennedy quickly. "Perhaps not. I'm sorry. Force of habit, I suppose. You don't know anything more about the robbery?" "N--no, only that it seems impossible that it could have happened in a place that has the wonderful burglar alarm protection that Mr. Schloss described to me." "You know him pretty well?" "Only through this transaction," she replied hastily. "I wish to heaven I had never heard of him." The telephone rang insistently. "Mrs. Moulton," said Kennedy, as he returned the receiver to the hook, "it may interest you to know that the burglar alarm company has just called me up about the same case. If I had need of an added incentive, which I hope you will believe I have not, that might furnish it. I will do my best," he repeated. "Thank you--a thousand times," she cried fervently, and, had I been Craig, I think I should have needed no more thanks than the look she gave him as he accompanied her to the door of our apartment. It was still early and the eager crowds were pushing their way to business through the narrow network of downtown streets as Kennedy and I entered a large office on lower Broadway in the heart of the jewelry trade and financial district. "One of the most amazing robberies that has ever been attempted has been reported to us this morning," announced James McLear, manager of the Hale Electric Protection, adding with a look half of anxiety, half of skepticism, "that is, if it is true." McLear was a stocky man, of powerful build and voice and a general appearance of having been once well connected with the city detective force before an attractive offer had taken him into this position of great responsibility. "Herman Schloss, one of the best known of Maiden Lane jewelers," he continued, "has been robbed of goods worth two or three hundred thousand dollars--and in spite of every modern protection. So that you will get it clearly, let me show you what we do here." He ushered us into a large room, on the walls of which were hundreds of little indicators. From the front they looked like rows of little square compartments, tier on tier, about the size of ordinary post office boxes. Closer examination showed that each was equipped with a delicate needle arranged to oscillate backward and forward upon the very minutest interference with the electric current. Under the boxes, each of which bore a number, was a series of drops and buzzers numbered to correspond with the boxes. "In nearly every office in Maiden Lane where gems and valuable jewelry are stored," explained McLear, "this electrical system of ours is installed. When the safes are closed at night and the doors swung together, a current of electricity is constantly shooting around the safes, conducted by cleverly concealed wires. These wires are picked up by a cable system which finds its way to this central office. Once here, the wires are safeguarded in such manner that foreign currents from other wires or from lightning cannot disturb the system." We looked with intense interest at this huge electrical pulse that felt every change over so vast and rich an area. "Passing a big dividing board," he went on, "they are distributed and connected each in its place to the delicate tangent galvanometers and sensitive indicators you see in this room. These instantly announce the most minute change in the working of the current, and each office has a distinct separate metallic circuit. Why, even a hole as small as a lead pencil in anything protected would sound the alarm here." Kennedy nodded appreciatively. "You see," continued McLear, glad to be able to talk to one who followed him so closely, "it is another evidence of science finding for us greater security in the use of a tiny electric wire than in massive walls of steel and intricate lock devices. But here is a case in which, it seems, every known protection has failed. We can't afford to pass that by. If we have fallen down we want to know how, as well as to catch the burglar." "How are the signals given?" I asked. "Well, when the day's business is over, for instance, Schloss would swing the heavy safe doors together and over them place the doors of a wooden cabinet. That signals an alarm to us here. We answer it and if the proper signal is returned, all right. After that no one can tamper with the safe later in the night without sounding an alarm that would bring a quick investigation." "But suppose that it became necessary to open the safe before the next morning. Might not some trusted employee return to the office, open it, give the proper signals and loot the safe?" "No indeed," he answered confidently. "The very moment anyone touches the cabinet, the alarm is sounded. Even if the proper code signal is returned, it is not sufficient. A couple of our trusted men from the central office hustle around there anyhow and they don't leave until they are satisfied that everything is right. We have the authorized signatures on hand of those who are supposed to open the safe and a duplicate of one of them must be given or there is an arrest." McLear considered for a moment. "For instance, Schloss, like all the rest, was assigned a box in which was deposited a sealed envelope containing a key to the office and his own signature, in this case, since he alone knew the combination. Now, when an alarm is sounded, as it was last night, and the key removed to gain entrance to the office, a record is made and the key has to be sealed up again by Schloss. A report is also submitted showing when the signals are received and anything else that is worth recording. Last night our men found nothing wrong, apparently. But this morning we learn of the robbery." "The point is, then," ruminated Kennedy, "what happened in the interval between the ringing of the alarm and the arrival of the special officers? I think I'll drop around and look Schloss' place over," he added quietly, evidently eager to begin at the actual scene of the crime. On the door of the office to which McLear took us was one of those small blue plates which chance visitors to Maiden Lane must have seen often. To the initiated--be he crook or jeweler--this simple sign means that the merchant is a member of the Jewelers' Security Alliance, enough in itself, it would seem, to make the boldest burglar hesitate. For it is the motto of this organization to "get" the thief at any cost and at any time. Still, it had not deterred the burglar in this instance. "I know people are going to think it is a fake burglary," exclaimed Schloss, a stout, prosperous-looking gem broker, as we introduced ourselves. "But over two hundred thousands dollars' worth of stones are gone," he half groaned. "Think of it, man," he added, "one of the greatest robberies since the Dead Line was established. And if they can get away with it, why, no one down here is protected any more. Half a billion dollars in jewels in Maiden Lane and John Street are easy prey for the cracksmen!" Staggering though the loss must have been to him, he had apparently recovered from the first shock of the discovery and had begun the fight to get back what had been lost. It was, as McLear had intimated, a most amazing burglary, too. The door of Schloss' safe was open when Kennedy and I arrived and found the excited jeweler nervously pacing the office. Surrounding the safe, I noticed a wooden framework constructed in such a way as to be a part of the decorative scheme of the office. Schloss banged the heavy doors shut. "There, that's just how it was--shut as tight as a drum. There was absolutely no mark of anyone tampering with the combination lock. And yet the safe was looted!" "How did you discover it?" asked Craig. "I presume you carry burglary insurance?" Schloss looked up quickly. "That's what I expected as a first question. No, I carried very little insurance. You see, I thought the safe, one of those new chrome steel affairs, was about impregnable. I never lost a moment's sleep over it; didn't think it possible for anyone to get into it. For, as you see, it is completely wired by the Hale Electric Protection--that wooden framework about it. No one could touch that when it was set without jangling a bell at the central office which would send men scurrying here to protect the place." "But they must have got past it," suggested Kennedy. "Yes--they must have. At least this morning I received the regular Hale report. It said that their wires registered last night as though some one was tampering with the safe. But by the time they got around, in less than five minutes, there was no one here, nothing seemed to be disturbed. So they set it down to induction or electrolysis, or something the matter with the wires. I got the report the first thing when I arrived here with my assistant, Muller." Kennedy was on his knees, going over the safe with a fine brush and some powder, looking now and then through a small magnifying glass. "Not a finger print," he muttered. "The cracksman must have worn gloves. But how did he get in? There isn't a mark of 'soup' having been used to blow it up, nor of a 'can-opener' to rip it open, if that were possible, nor of an electric or any other kind of drill." "I've read of those fellows who burn their way in," said Schloss. "But there is no hole," objected Kennedy, "not a trace of the use of thermit to burn the way in or of the oxyacetylene blowpipe to cut a piece out. Most extraordinary," he murmured. "You see," shrugged Schloss, "everyone will say it must have been opened by one who knew the combination. But I am the only one. I have never written it down or told anyone, not even Muller. You understand what I am up against?" "There's the touch system," I suggested. "You remember, Craig, the old fellow who used to file his finger tips to the quick until they were so sensitive that he could actually feel when he had turned the combination to the right plunger? Might not that explain the lack of finger prints also?" I added eagerly. "Nothing like that in this case, Walter," objected Craig positively. "This fellow wore gloves, all right. No, this safe has been opened and looted by no ordinarily known method. It's the most amazing case I ever saw in that respect--almost as if we had a cracksman in the fourth dimension to whom the inside of a closed cube is as accessible as is the inside of a plane square to us three dimensional creatures. It is almost incomprehensible." I fancied I saw Schloss' face brighten as Kennedy took this view. So far, evidently, he had run across only skepticism. "The stones were unset?" resumed Craig. "Mostly. Not all." "You would recognize some of them if you saw them?" "Yes indeed. Some could be changed only by re-cutting. Even some of those that were set were of odd cut and size--some from a diamond necklace which belonged to a--" There was something peculiar in both his tone and manner as he cut short the words. "To whom?" asked Kennedy casually. "Oh, once to a well-known woman in society," he said carefully. "It is mine, though, now--at least it was mine. I should prefer to mention no names. I will give a description of the stones." "Mrs. Lynn Moulton, for instance?" suggested Craig quietly. Schloss jumped almost as if a burglar alarm had sounded under his very ears. "How did you know? Yes--but it was a secret. I made a large loan on it, and the time has expired." "Why did she need money so badly?" asked Kennedy. "How should I know?" demanded Schloss. Here was a deepening mystery, not to be elucidated by continuing this line of inquiry with Schloss, it seemed. CHAPTER XVII THE PASTE REPLICA Carefully Craig was going over the office. Outside of the safe, there had apparently been nothing of value. The rest of the office was not even wired, and it seemed to have been Schloss' idea that the few thousands of burglary insurance amply protected him against such loss. As for the safe, its own strength and the careful wiring might well have been considered quite sufficient under any hitherto to-be-foreseen circumstances. A glass door, around the bend of a partition, opened from the hallway into the office and had apparently been designed with the object of making visible the safe so that anyone passing might see whether an intruder was tampering with it. Kennedy had examined the door, perhaps in the expectation of finding finger prints there, and was passing on to other things, when a change in his position caused his eye to catch a large oval smudge on the glass, which was visible when the light struck it at the right angle. Quickly he dusted it over with the powder, and brought out the detail more clearly. As I examined it, while Craig made preparations to cut out the glass to preserve it, it seemed to contain a number of minute points and several more or less broken parallel lines. The edges gradually trailed off into an indistinct faintness. Business, naturally, was at a standstill, and as we were working near the door, we could see that the news of Schloss' strange robbery had leaked out and was spreading rapidly. Scores of acquaintances in the trade stopped at the door to inquire about the rumor. To each, it seemed that Morris Muller, the working jeweler employed by Schloss, repeated the same story. "Oh," he said, "it is a big loss--yes--but big as it is, it will not break Mr. Schloss. And," he would add with the tradesman's idea of humor, "I guess he has enough to play a game of poker--eh?" "Poker?" asked Kennedy smiling. "Is he much of a player?" "Yes. Nearly every night with his friends he plays." Kennedy made a mental note of it. Evidently Schloss trusted Muller implicitly. He seemed like a partner, rather than an employee, even though he had not been entrusted with the secret combination. Outside, we ran into city detective Lieutenant Winters, the officer who was stationed at the Maiden Lane post, guarding that famous section of the Dead Line established by the immortal Byrnes at Fulton Street, below which no crook was supposed to dare even to be seen. Winters had been detailed on the case. "You have seen the safe in there?" asked Kennedy, as he was leaving to carry on his investigation elsewhere. Winters seemed to be quite as skeptical as Schloss had intimated the public would be. "Yes," he replied, "there's been an epidemic of robbery with the dull times--people who want to collect their burglary insurance, I guess." "But," objected Kennedy, "Schloss carried so little." "Well, there was the Hale Protection. How about that?" Craig looked up quickly, unruffled by the patronizing air of the professional toward the amateur detective. "What is your theory?" he asked. "Do you think he robbed himself?" Winters shrugged his shoulders. "I've been interested in Schloss for some time," he said enigmatically. "He has had some pretty swell customers. I'll keep you wised up, if anything happens," he added in a burst of graciousness, walking off. On the way to the subway, we paused again to see McLear. "Well," he asked, "what do you think of it, now?" "All most extraordinary," ruminated Craig. "And the queerest feature of all is that the chief loss consists of a diamond necklace that belonged once to Mrs. Antoinette Moulton." "Mrs. Lynn Moulton?" repeated McLear. "The same," assured Kennedy. McLear appeared somewhat puzzled. "Her husband is one of our old subscribers," he pursued. "He is a lawyer on Wall Street and quite a gem collector. Last night his safe was tampered with, but this morning he reports no loss. Not half an hour ago he had us on the wire congratulating us on scaring off the burglars, if there had been any." "What is your opinion," I asked. "Is there a gang operating?" "My belief is," he answered, reminiscently of his days on the detective force, "that none of the loot will be recovered until they start to 'fence' it. That would be my lay--to look for the fence. Why, think of all the big robberies that have been pulled off lately. Remember," he went on, "the spoils of a burglary consist generally of precious stones. They are not currency. They must be turned into currency--or what's the use of robbery? "But merely to offer them for sale at an ordinary jeweler's would be suspicious. Even pawnbrokers are on the watch. You see what I am driving at? I think there is a man or a group of men whose business it is to pay cash for stolen property and who have ways of returning gems into the regular trade channels. In all these robberies we get a glimpse of as dark and mysterious a criminal as has ever been recorded. He may be--anybody. About his legitimacy, I believe, no question has ever been raised. And, I tell you, his arrest is going to create a greater sensation than even the remarkable series of robberies that he has planned or made possible. The question is, to my mind, who is this fence?" McLear's telephone rang and he handed the instrument to Craig. "Yes, this is Professor Kennedy," answered Craig. "Oh, too bad you've had to try all over to get me. I've been going from one place to another gathering clues and have made good progress, considering I've hardly started. Why--what's the matter? Really?" An interval followed, during which McLear left to answer a personal call on another wire. As Kennedy hung up the receiver, his face wore a peculiar look. "It was Mrs. Moulton," he blurted out. "She thinks that her husband has found out that the necklace is paste." "How?" I asked. "The paste replica is gone from her wall safe in the Deluxe." I turned, startled at the information. Even Kennedy himself was perplexed at the sudden succession of events. I had nothing to say. Evidently, however, his rule was when in doubt play a trump, for, twenty minutes later found us in the office of Lynn Moulton, the famous corporation lawyer, in Wall Street. Moulton was a handsome man of past fifty with a youthful face against his iron gray hair and mustache, well dressed, genial, a man who seemed keenly in love with the good things of life. "It is rumored," began Kennedy, "that an attempt was made on your safe here at the office last night." "Yes," he admitted, taking off his glasses and polishing them carefully. "I suppose there is no need of concealment, especially as I hear that a somewhat similar attempt was made on the safe of my friend Herman Schloss in Maiden Lane." "You lost nothing?" Moulton put his glasses on and looked Kennedy in the face frankly. "Nothing, fortunately," he said, then went on slowly. "You see, in my later years, I have been something of a collector of precious stones myself. I don't wear them, but I have always taken the keenest pleasure in owning them and when I was married it gave me a great deal more pleasure to have them set in rings, pendants, tiaras, necklaces, and other forms for my wife." He had risen, with the air of a busy man who had given the subject all the consideration he could afford and whose work proceeded almost by schedule. "This morning I found my safe tampered with, but, as I said, fortunately something must have scared off the burglars." He bowed us out politely. What was the explanation, I wondered. It seemed, on the face of things, that Antoinette Moulton feared her husband. Did he know something else already, and did she know he knew? To all appearances he took it very calmly, if he did know. Perhaps that was what she feared, his very calmness. "I must see Mrs. Moulton again," remarked Kennedy, as we left. The Moultons lived, we found, in one of the largest suites of a new apartment hotel, the Deluxe, and in spite of the fact that our arrival had been announced some minutes before we saw Mrs. Moulton, it was evident that she had been crying hysterically over the loss of the paste jewels and what it implied. "I missed it this morning, after my return from seeing you," she replied in answer to Craig's inquiry, then added, wide-eyed with alarm, "What shall I do? He must have opened the wall safe and found the replica. I don't dare ask him point-blank." "Are you sure he did it?" asked Kennedy, more, I felt, for its moral effect on her than through any doubt in his own mind. "Not sure. But then the wall safe shows no marks, and the replica is gone." "Might I see your jewel case?" he asked. "Surely. I'll get it. The wall safe is in Lynn's room. I shall probably have to fuss a long time with the combination." In fact she could not have been very familiar with it for it took several minutes before she returned. Meanwhile, Kennedy, who had been drumming absently on the arms of his chair, suddenly rose and walked quietly over to a scrap basket that stood beside an escritoire. It had evidently just been emptied, for the rooms must have been cleaned several hours before. He bent down over it and picked up two scraps of paper adhering to the wicker work. The rest had evidently been thrown away. I bent over to read them. One was: --rest Nettie-- --dying to see-- The other read: --cherche to-d --love and ma --rman. What did it mean? Hastily, I could fill in "Dearest Nettie," and "I am dying to see you." Kennedy added, "The Recherche to-day," that being the name of a new apartment uptown, as well as "love and many kisses." But "--rman"--what did that mean? Could it be Herman--Herman Schloss? She was returning and we resumed our seats quickly. Kennedy took the jewel case from her and examined it carefully. There was not a mark on it. "Mrs. Moulton," he said slowly, rising and handing it back to her, "have you told me all?" "Why--yes," she answered. Kennedy shook his head gravely. "I'm afraid not. You must tell me everything." "No--no," she cried vehemently, "there is nothing more." We left and outside the Deluxe he paused, looked about, caught sight of a taxicab and hailed it. "Where?" asked the driver. "Across the street," he said, "and wait. Put the window in back of you down so I can talk. I'll tell you where to go presently. Now, Walter, sit back as far as you can. This may seem like an underhand thing to do, but we've got to get what that woman won't tell us or give up the case." Perhaps half an hour we waited, still puzzling over the scraps of paper. Suddenly I felt a nudge from Kennedy. Antoinette Moulton was standing in the doorway across the street. Evidently she preferred not to ride in her own car, for a moment later she entered a taxicab. "Follow that black cab," said Kennedy to our driver. Sure enough, it stopped in front of the Recherche Apartments and Mrs. Moulton stepped out and almost ran in. We waited a moment, then Kennedy followed. The elevator that had taken her up had just returned to the ground floor. "The same floor again," remarked Kennedy, jauntily stepping in and nodding familiarly to the elevator boy. Then he paused suddenly, looked at his watch, fixed his gaze thoughtfully on me an instant, and exclaimed. "By George--no. I can't go up yet. I clean forgot that engagement at the hotel. One moment, son. Let us out. We'll be back again." Considerably mystified, I followed him to the sidewalk. "You're entitled to an explanation," he laughed catching my bewildered look as he opened the cab door. "I didn't want to go up now while she is there, but I wanted to get on good terms with that boy. We'll wait until she comes down, then go up." "Where?" I asked. "That's what I am going through all this elaborate preparation to find out. I have no more idea than you have." It could not have been more than twenty minutes later when Mrs. Moulton emerged rather hurriedly, and drove away. While we had been waiting I had observed a man on the other side of the street who seemed unduly interested in the Recherche, too, for he had walked up and down the block no less than six times. Kennedy saw him, and as he made no effort to follow Mrs. Moulton, Kennedy did not do so either. In fact a little quick glance which she had given at our cab had raised a fear that she might have discovered that she was being followed. Kennedy and I paid off our cabman and sauntered into the Recherche in the most debonair manner we could assume. "Now, son, we'll go up," he said to the boy who, remembering us, and now not at all clear in his mind that he might not have seen us before that, whisked us to the tenth floor. "Let me see," said Kennedy, "it's number one hundred and--er---" "Three," prompted the boy. He pressed the buzzer and a neatly dressed colored maid responded. "I had an appointment here with Mrs. Moulton this morning," remarked Kennedy. "She has just gone," replied the maid, off her guard. "And was to meet Mr. Schloss here in half an hour," he added quickly. It was the maid's turn to look surprised. "I didn't think he was to be here," she said. "He's had some--" "Trouble at the office," supplied Kennedy. "That's what it was about. Perhaps he hasn't been able to get away yet. But I had the appointment. Ah, I see a telephone in the hall. May I?" He had stepped politely in, and by dint of cleverly keeping his finger on the hook in the half light, he carried on a one-sided conversation with himself long enough to get a good chance to look about. There was an air of quiet and refinement about the apartment in the Recherche. It was darkened to give the little glowing electric bulbs in their silken shades a full chance to simulate right. The deep velvety carpets were noiseless to the foot, and the draperies, the pictures, the bronzes, all bespoke taste. But the chief objects of interest to Craig were the little square green baize-covered tables on one of which lay neatly stacked a pile of gilt-edged cards and a mahogany box full of ivory chips of red, white and blue. It was none of the old-time gambling places, like Danfield's, with its steel door which Craig had once cut through with an oxyacetylene blowpipe in order to rescue a young spendthrift from himself. Kennedy seemed perfectly well satisfied merely with a cursory view of the place, as he hung up the receiver and thanked the maid politely for allowing him to use it. "This is up-to-date gambling in cleaned-up New York," he remarked as we waited for the elevator to return for us. "And the worst of it all is that it gets the women as well as the men. Once they are caught in the net, they are the most powerful lure to men that the gamblers have yet devised." We rode down in silence, and as we went down the steps to the street, I noticed the man whom we had seen watching the place, lurking down at the lower corner. Kennedy quickened his pace and came up behind him. "Why, Winters!" exclaimed Craig. "You here?" "I might say the same to you," grinned the detective not displeased evidently that our trail had crossed his. "I suppose you are looking for Schloss, too. He's up in the Recherche a great deal, playing poker. I understand he owns an interest in the game up there." Kennedy nodded, but said nothing. "I just saw one of the cappers for the place go out before you went in." "Capper?" repeated Kennedy surprised. "Antoinette Moulton a steerer for a gambling joint? What can a rich society woman have to do with a place like that or a man like Schloss?" Winters smiled sardonically. "Society ladies to-day often get into scrapes of which their husbands know nothing," he remarked. "You didn't know before that Antoinette Moulton, like many of her friends in the smart set, was a gambler--and loser--did you?" Craig shook his head. He had more of human than scientific interest in a case of a woman of her caliber gone wrong. "But you must have read of the famous Moulton diamonds?" "Yes," said Craig, blankly, as if it were all news to him. "Schloss has them--or at least had them. The jewels she wore at the opera this winter were paste, I understand." "Does Moulton play?" he asked. "I think so--but not here, naturally. In a way, I suppose, it is his fault. They all do it. The example of one drives on another." Instantly there flashed over my mind a host of possibilities. Perhaps, after all, Winters had been right. Schloss had taken this way to make sure of the jewels so that she could not redeem them. Suddenly another explanation crowded that out. Had Mrs. Moulton robbed the safe herself, or hired some one else to do it for her, and had that person gone back on her? Then a horrid possibility occurred to me. Whatever Antoinette Moulton may have been and done, some one must have her in his power. What a situation for the woman! My sympathy went out to her in her supreme struggle. Even if it had been a real robbery, Schloss might easily recover from it. But for her every event spelled ruin and seemed only to be bringing that ruin closer. We left Winters, still watching on the trail of Schloss, and went on uptown to the laboratory. CHAPTER XVIII THE BURGLAR'S MICROPHONE That night I was sitting, brooding over the case, while Craig was studying a photograph which he made of the smudge on the glass door down at Schloss'. He paused in his scrutiny of the print to answer the telephone. "Something has happened to Schloss," he exclaimed seizing his hat and coat. "Winters has been watching him. He didn't go to the Recherche. Winters wants me to meet him at a place several blocks below it Come on. He wouldn't say over the wire what it was. Hurry." We met Winters in less than ten minutes at the address he had given, a bachelor apartment in the neighborhood of the Recherche. "Schloss kept rooms here," explained Winters, hurrying us quickly upstairs. "I wanted you to see before anyone else." As we entered the large and luxuriously furnished living room of the jeweler's suite, a gruesome sight greeted us. There lay Schloss on the floor, face down, in a horribly contorted position. In one hand, clenched under him partly, the torn sleeve of a woman's dress was grasped convulsively. The room bore unmistakable traces of a violent struggle, but except for the hideous object on the floor was vacant. Kennedy bent down over him. Schloss was dead. In a corner, by the door, stood a pile of grips, stacked up, packed, and undisturbed. Winters who had been studying the room while we got our bearings picked up a queer-looking revolver from the floor. As he held it up I could see that along the top of the barrel was a long cylinder with a ratchet or catch at the butt end. He turned it over and over carefully. "By George," he muttered, "it has been fired off." Kennedy glanced more minutely at the body. There was not a mark on it. I stared about vacantly at the place where Winters had picked the thing up. "Look," I cried, my eye catching a little hole in the baseboard of the woodwork near it. "It must have fallen and exploded on the floor," remarked Kennedy. "Let me see it, Winters." Craig held it at arm's length and pulled the catch. Instead of an explosion, there came a cone of light from the top of the gun. As Kennedy moved it over the wall, I saw in the center of the circle of light a dark spot. "A new invention," Craig explained. "All you need to do is to move it so that little dark spot falls directly on an object. Pull the trigger--the bullet strikes the dark spot. Even a nervous and unskilled marksman becomes a good shot in the dark. He can even shoot from behind the protection of something--and hit accurately." It was too much for me. I could only stand and watch Kennedy as he deftly bent over Schloss again and placed a piece of chemically prepared paper flat on the forehead of the dead man. When he withdrew it, I could see that it bore marks of the lines on his head. Without a word, Kennedy drew from his pocket a print of the photograph of the smudge on Schloss' door. "It is possible," he said, half to himself, "to identify a person by means of the arrangement of the sweat glands or pores. Poroscopy, Dr. Edmond Locard, director of the Police Laboratory at Lyons, calls it. The shape, arrangement, number per square centimeter, all vary in different individuals. Besides, here we have added the lines of the forehead." He was studying the two impressions intensely. When he looked up from his examination, his face wore a peculiar expression. "This is not the head which was placed so close to the glass of the door of Schloss' office, peering through, on the night of the robbery, in order to see before picking the lock whether the office was empty and everything ready for the hasty attack on the safe." "That disposes of my theory that Schloss robbed himself," remarked Winters reluctantly. "But the struggle here, the sleeve of the dress, the pistol--could he have been shot?" "No, I think not," considered Kennedy. "It looks to me more like a case of apoplexy." "What shall we do?" asked Winters. "Far from clearing anything up, this complicates it." "Where's Muller?" asked Kennedy. "Does he know? Perhaps he can shed some light on it." The clang of an ambulance bell outside told that the aid summoned by Winters had arrived. We left the body in charge of the surgeon and of a policeman who arrived about the same time, and followed Winters. Muller lived in a cheap boarding house in a shabbily respectable street downtown, and without announcing ourselves we climbed the stairs to his room. He looked up surprised but not disconcerted as we entered. "What's the matter?" he asked. "Muller," shot out Winters, "we have just found Mr. Schloss dead!" "D-dead!" he stammered. The man seemed speechless with horror. "Yes, and with his grips packed as if to run away." Muller looked dazedly from one of us to the other, but shut up like a clam. "I think you had better come along with us as a material witness," burst out Winters roughly. Kennedy said nothing, leaving that sort of third degree work to the detective. But he was not idle, as Winters tried to extract more than the monosyllables, "I don't know," in answer to every inquiry of Muller about his employer's life and business. A low exclamation from Craig attracted my attention from Winters. In a corner he had discovered a small box and had opened it. Inside was a dry battery and a most peculiar instrument, something like a little flat telephone transmitter yet attached by wires to earpieces that fitted over the head after the manner of those of a wireless detector. "What's this?" asked Kennedy, dangling it before Muller. He looked at it phlegmatically. "A deaf instrument I have been working on," replied the jeweler. "My hearing is getting poor." Kennedy looked hastily from the instrument to the man. "I think I'll take it along with us," he said quietly. Winters, true to his instincts, had been searching Muller in the meantime. Besides the various assortment that a man carries in his pockets usually, including pens, pencils, notebooks, a watch, a handkerchief, a bunch of keys, one of which was large enough to open a castle, there was a bunch of blank and unissued pawn-tickets bearing the name, "Stein's One Per Cent. a Month Loans," and an address on the Bowery. Was Muller the "fence" we were seeking, or only a tool for the "fence" higher up? Who was this Stein? What it all meant I could only guess. It was a far cry from the wealth of Diamond Lane to a dingy Bowery pawnshop, even though pawnbroking at one per cent. a month--and more, on the side--pays. I knew, too, that diamonds are hoarded on the East Side as nowhere else in the world, outside of India. It was no uncommon thing, I had heard, for a pawnbroker whose shop seemed dirty and greasy to the casual visitor to have stored away in his vault gems running into the hundreds of thousands of dollars. "Mrs. Moulton must know of this," remarked Kennedy. "Winters, you and Jameson bring Muller along. I am going up to the Deluxe." I must say that I was surprised at finding Mrs. Moulton there. Outside the suite Winters and I waited with the unresisting Muller, while Kennedy entered. But through the door which he left ajar I could hear what passed. "Mrs. Moulton," he began, "something terrible has happened--" He broke off, and I gathered that her pale face and agitated manner told him that she knew already. "Where is Mr. Moulton?" he went on, changing his question. "Mr. Moulton is at his office," she answered tremulously. "He telephoned while I was out that he had to work to-night. Oh, Mr. Kennedy--he knows--he knows. I know it. He has avoided me ever since I missed the replica from-" "Sh!" cautioned Craig. He had risen and gone to the door. "Winters," he whispered, "I want you to go down to Lynn Moulton's office. Meanwhile Jameson can take care of Muller. I am going over to that place of Stein's presently. Bring Moulton up there. You will wait here, Walter, for the present," he nodded. He returned to the room where I could hear her crying softly. "Now, Mrs. Moulton," he said gently, "I'm afraid I must trouble you to go with me. I am going over to a pawnbroker's on the Bowery." "The Bowery?" she repeated, with a genuinely surprised shudder. "Oh, no, Mr. Kennedy. Don't ask me to go anywhere to-night. I am--I am in no condition to go anywhere--to do anything--I--" "But you must," said Kennedy in a low voice. "I can't. Oh--have mercy on me. I am terribly upset. You--" "It is your duty to go, Mrs. Moulton," he repeated. "I don't understand." she murmured. "A pawnbroker's?" "Come," urged Kennedy, not harshly but firmly, then, as she held back, added, playing a trump card, "We must work quickly. In his hands we found the fragments of a torn dress. When the police--" She uttered a shriek. A glance had told her, if she had deceived herself before, that Kennedy knew her secret. Antoinette Moulton was standing before him, talking rapidly. "Some one has told Lynn. I know it. There is nothing now that I can conceal. If you had come half an hour later you would not have found me. He had written to Mr. Schloss, threatening him that if he did not leave the country he would shoot him at sight. Mr. Schloss showed me the letter. "It had come to this. I must either elope with Schloss, or lose his aid. The thought of either was unendurable. I hated him--yet was dependent on him. "To-night I met him, in his empty apartment, alone. I knew that he had what was left of his money with him, that everything was packed up. I went prepared. I would not elope. My plan was no less than to make him pay the balance on the necklace that he had lost--or to murder him. "I carried a new pistol in my muff, one which Lynn had just bought. I don't know how I did it. I was desperate. "He told me he loved me, that Lynn did not, never had--that Lynn had married me only to show off his wealth and diamonds, to give him a social! position--that I was merely a--a piece of property--a dummy. "He tried to kiss me. It was revolting. I struggled away from him. "And in the struggle, the revolver fell from my muff and exploded on the floor. "At once he was aflame with suspicion. "'So--it's murder you want!' he shouted. 'Well, murder it shall be!' "I saw death in his eye as he seized my arm. I was defenseless now. The old passion came over him. Before he killed--he--would have his way with me. "I screamed. With a wild effort I twisted away from him. "He raised his hand to strike me, I saw his eyes, glassy. Then he sank back--fell to the floor--dead of apoplexy--dead of his furious emotions. "I fled. "And now you have found me." She had turned, hastily, to leave the room. Kennedy blocked the door. "Mrs. Moulton," he said firmly, "listen to me. What was the first question you asked me? 'Can I trust you?' And I told you you could. This is no time for--for suicide." He shot the word out bluntly. "All may not be lost. I have sent for your husband. Muller is outside." "Muller?" she cried. "He made the replica." "Very well. I am going to clear this thing up. Come. You MUST." It was all confused to me, the dash in a car to the little pawnbroker's on the first floor of a five-story tenement, the quick entry into the place by one of Muller's keys. Over the safe in back was a framework like that which had covered Schloss' safe. Kennedy tore it away, regardless of the alarm which it must have sounded. In a moment he was down before it on his knees. "This is how Schloss' safe was opened so quickly," he muttered, working feverishly. "Here is some of their own medicine." He had placed the peculiar telephone-like transmitter close to the combination lock and was turning the combination rapidly. Suddenly he rose, gave the bolts a twist, and the ponderous doors swung open. "What is it?" I asked eagerly. "A burglar's microphone," he answered, hastily looking over the contents of the safe. "The microphone is now used by burglars for picking combination locks. When you turn the lock, a slight sound is made when the proper number comes opposite the working point. It can be heard sometimes by a sensitive ear, although it is imperceptible to most persons. But by using a microphone it is an easy matter to hear the sounds which allow of opening the lock." He had taken a yellow chamois bag out of the safe and opened it. Inside sparkled the famous Moulton diamonds. He held them up--in all their wicked brilliancy. No one spoke. Then he took another yellow bag, more dirty and worn than the first. As he opened it, Mrs. Moulton could restrain herself no longer. "The replica!" she cried. "The replica!" Without a word, Craig handed the real necklace to her. Then he slipped the paste jewels into the newer of the bags and restored both it and the empty one to their places, banged shut the door of the safe, and replaced the wooden screen. "Quick!" he said to her, "you have still a minute to get away. Hurry--anywhere--away--only away!" The look of gratitude that came over her face, as she understood the full meaning of it was such as I had never seen before. "Quick!" he repeated. It was too late. "For God's sake, Kennedy," shouted a voice at the street door, "what are you doing here?" It was McLear himself. He had come with the Hale patrol, on his mettle now to take care of the epidemic of robberies. Before Craig could reply a cab drew up with a rush at the curb and two men, half fighting, half cursing, catapulted themselves into the shop. They were Winters and Moulton. Without a word, taking advantage of the first shock of surprise, Kennedy had clapped a piece of chemical paper on the foreheads of Mrs. Moulton, then of Moulton, and on Muller's. Oblivious to the rest of us, he studied the impressions in the full light of the counter. Moulton was facing his wife with a scornful curl of the lip. "I've been told of the paste replica--and I wrote Schloss that I'd shoot him down like the dog he is, you--you traitress," he hissed. She drew herself up scornfully. "And I have been told why you married me--to show off your wicked jewels and help you in your--" "You lie!" he cried fiercely. "Muller--some one--open this safe--whosever it is. If what I have been told is true, there is in it one new bag containing the necklace. It was stolen from Schloss to whom you sold my jewels. The other old bag, stolen from me, contains the paste replica you had made to deceive me." It was all so confused that I do not know how it happened. I think it was Muller who opened the safe. "There is the new yellow bag," cried Moulton, "from Schloss' own safe. Open it." McLear had taken it. He did so. There sparkled not the real gems, but the replica. "The devil!" Moulton exclaimed, breaking from Winters and seizing the old bag. He tore it open and--it was empty. "One moment," interrupted Kennedy, looking up quietly from the counter. "Seal that safe again, McLear. In it are the Schloss jewels and the products of half a dozen other robberies which the dupe Muller--or Stein, as you please--pulled off, some as a blind to conceal the real criminal. You may have shown him how to leave no finger prints, but you yourself have left what is just as good--your own forehead print. McLear--you were right. There's your criminal--Lynn Moulton, professional fence, the brains of the thing." CHAPTER XIX THE GERM LETTER Lynn Moulton made no fight and Kennedy did not pursue the case, for, with the rescue of Antoinette Moulton, his interest ceased. Blackmail takes various forms, and the Moulton affair was only one phase of it. It was not long before we had to meet a much stranger attempt. "Read the letter, Professor Kennedy. Then I will tell you the sequel." Mrs. Hunter Blake lay back in the cushions of her invalid chair in the sun parlor of the great Blake mansion on Riverside Drive, facing the Hudson with its continuous reel of maritime life framed against the green-hilled background of the Jersey shore. Her nurse, Miss Dora Sears, gently smoothed out the pillows and adjusted them so that the invalid could more easily watch us. Mrs. Blake, wealthy, known as a philanthropist, was not an old woman, but had been for years a great sufferer from rheumatism. I watched Miss Sears eagerly. Full-bosomed, fine of face and figure, she was something more than a nurse; she was a companion. She had bright, sparkling black eyes and an expression about her well-cut mouth which made one want to laugh with her. It seemed to say that the world was a huge joke and she invited you to enjoy the joke with her. Kennedy took the letter which Miss Sears proffered him, and as he did so I could not help noticing her full, plump forearm on which gleamed a handsome plain gold bracelet. He spread the letter out on a dainty wicker table in such a way that we both could see it. We had been summoned over the telephone to the Blake mansion by Reginald Blake, Mrs. Blake's eldest son. Reginald had been very reticent over the reason, but had seemed very anxious and insistent that Kennedy should come immediately. Craig read quickly and I followed him, fascinated by the letter from its very opening paragraph. "Dear Madam," it began. "Having received my diploma as doctor of medicine and bacteriology at Heidelberg in 1909, I came to the United States to study a most serious disease which is prevalent in several of the western mountain states." So far, I reflected, it looked like an ordinary appeal for aid. The next words, however, were queer: "I have four hundred persons of wealth on my list. Your name was--" Kennedy turned the page. On the next leaf of the letter sheet was pasted a strip of gelatine. The first page had adhered slightly to the gelatine. "Chosen by fate," went on the sentence ominously. "By opening this letter," I read, "you have liberated millions of the virulent bacteria of this disease. Without a doubt you are infected by this time, for no human body is impervious to them, and up to the present only one in one hundred has fully recovered after going through all its stages." I gasped. The gelatine had evidently been arranged so that when the two sheets were pulled apart, the germs would be thrown into the air about the person opening the letter. It was a very ingenious device. The letter continued, "I am happy to say, however, that I have a prophylactic which will destroy any number of these germs if used up to the ninth day. It is necessary only that you should place five thousand dollars in an envelope and leave it for me to be called for at the desk of the Prince Henry Hotel. When the messenger delivers the money to me, the prophylactic will be sent immediately. "First of all, take a match and burn this letter to avoid spreading the disease. Then change your clothes and burn the old ones. Enclosed you will find in a germ-proof envelope an exact copy of this letter. The room should then be thoroughly fumigated. Do not come into close contact with anyone near and dear to you until you have used the prophylactic. Tell no one. In case you do, the prophylactic will not be sent under any circumstances. Very truly yours, DR. HANS HOPF." "Blackmail!" exclaimed Kennedy, looking intently again at the gelatine on the second page, as I involuntarily backed away and held my breath. "Yes, I know," responded Mrs. Blake anxiously, "but is it true?" There could be no doubt from the tone of her voice that she more than half believed that it was true. "I cannot say--yet," replied Craig, still cautiously scanning the apparently innocent piece of gelatine on the original letter which Mrs. Blake had not destroyed. "I shall have to keep it and examine it." On the gelatine I could see a dark mass which evidently was supposed to contain the germs. "I opened the letter here in this room," she went on. "At first I thought nothing of it. But this morning, when Buster, my prize Pekinese, who had been with me, sitting on my lap at the time, and closer to the letter even than I was, when Buster was taken suddenly ill, I--well, I began to worry." She finished with a little nervous laugh, as people will to hide their real feelings. "I should like to see the dog," remarked Kennedy simply. "Miss Sears," asked her mistress, "will you get Buster, please?" The nurse left the room. No longer was there the laughing look on her face. This was serious business. A few minutes later she reappeared, carrying gingerly a small dog basket. Mrs. Blake lifted the lid. Inside was a beautiful little "Peke," and it was easy to see that Buster was indeed ill. "Who is your doctor?" asked Craig, considering. "Dr. Rae Wilson, a very well-known woman physician." Kennedy nodded recognition of the name. "What does she say?" he asked, observing the dog narrowly. "We haven't told anyone, outside, of it yet," replied Mrs. Blake. "In fact until Buster fell sick, I thought it was a hoax." "You haven't told anyone?" "Only Reginald and my daughter Betty. Betty is frantic--not with fear for herself, but with fear for me. No one can reassure her. In fact it was as much for her sake as anyone's that I sent for you. Reginald has tried to trace the thing down himself, but has not succeeded." She paused. The door opened and Reginald Blake entered. He was a young fellow, self confident and no doubt very efficient at the new dances, though scarcely fitted to rub elbows with a cold world which, outside of his own immediate circle, knew not the name of Blake. He stood for a moment regarding us through the smoke of his cigarette. "Tell me just what you have done," asked Kennedy of him as his mother introduced him, although he had done the talking for her over the telephone. "Done?" he drawled. "Why, as soon as mother told me of the letter, I left an envelope up at the Prince Henry, as it directed." "With the money?" put in Craig quickly. "Oh, no--just as a decoy." "Yes. What happened?" "Well, I waited around a long time. It was far along in the day when a woman appeared at the desk. I had instructed the clerk to be on the watch for anyone who asked for mail addressed to a Dr. Hopf. The clerk slammed the register. That was the signal. I moved up closer." "What did she look like?" asked Kennedy keenly. "I couldn't see her face. But she was beautifully dressed, with a long light flowing linen duster, a veil that hid her features and on her hands and arms a long pair of motoring doeskin gloves. By George, she was a winner--in general looks, though. Well, something about the clerk, I suppose, must have aroused her suspicions. For, a moment later, she was gone in the crowd. Evidently she had thought of the danger and had picked out a time when the lobby would be full and everybody busy. But she did not leave by the front entrance through which she entered. I concluded that she must have left by one of the side street carriage doors." "And she got away?" "Yes. I found that she asked one of the boys at the door to crank up a car standing at the curb. She slid into the seat, and was off in a minute." Kennedy said nothing. But I knew that he was making a mighty effort to restrain comment on the bungling amateur detective work of the son of our client. Reginald saw the look on his face. "Still," he hastened, "I got the number of the car. It was 200859 New York." "You have looked it up?" queried Kennedy quickly. "I didn't need to do it. A few minutes later Dr. Rae Wilson herself came out--storming like mad. Her car had been stolen at the very door of the hotel by this woman with the innocent aid of the hotel employees." Kennedy was evidently keenly interested. The mention of the stolen car had apparently at once suggested an idea to him. "Mrs. Blake," he said, as he rose to go, "I shall take this letter with me. Will you see that Buster is sent up to my laboratory immediately?" She nodded. It was evident that Buster was a great pet with her and that it was with difficulty she kept from smoothing his silky coat. "You--you won't hurt Buster?" she pleaded. "No. Trust me. More than that, if there is any possible way of untangling this mystery, I shall do it." Mrs. Blake looked rather than spoke her thanks. As we went downstairs, accompanied by Miss Sears, we could see in the music room a very interesting couple, chatting earnestly over the piano. Betty Blake, a slip of a girl in her first season, was dividing her attention between her visitor and the door by which we were passing. She rose as she heard us, leaving the young man standing alone at the piano. He was of an age perhaps a year or two older than Reginald Blake. It was evident that, whatever Miss Betty might think, he had eyes for no one else but the pretty debutante. He even seemed to be regarding Kennedy sullenly, as if he were a possible rival. "You--you don't think it is serious?" whispered Betty in an undertone, scarcely waiting to be introduced. She had evidently known of our visit, but had been unable to get away to be present upstairs. "Really, Miss Blake," reassured Kennedy, "I can't say. All I can do is to repeat what I have already said to your mother. Keep up a good heart and trust me to work it out." "Thank you," she murmured, and then, impulsively extending her small hand to Craig, she added, "Mr. Kennedy, if there is anything I can do to help you, I beg that you will call on me." "I shall not forget," he answered, relinquishing the hand reluctantly. Then, as she thanked him, and turned again to her guest, he added in a low tone to me, "A remarkable girl, Walter, a girl that can be depended on." We followed Miss Sears down the hall. "Who was that young man in the music room?" asked Kennedy, when we were out of earshot. "Duncan Baldwin," she answered. "A friend and bosom companion of Reginald." "He seems to think more of Betty than of her brother," Craig remarked dryly. Miss Sears smiled. "Sometimes, we think they are secretly engaged," she returned. We had almost reached the door. "By the way," she asked anxiously, "do you think there are any precautions that I should take for Mrs. Blake--and the rest?" "Hardly," answered Kennedy, after a moment's consideration, "as long as you have taken none in particular already. Still, I suppose it will do no harm to be as antiseptic as possible." "I shall try," she promised, her face showing that she considered the affair now in a much more serious light than she had before our visit. "And keep me informed of anything that turns up," added Kennedy handing her a card with the telephone number of the laboratory. As we left the Blake mansion, Kennedy remarked, "We must trace that car somehow--at least we must get someone working on that." Half an hour later we were in a towering office building on Liberty Street, the home of various kinds of insurance. Kennedy stopped before a door which bore the name, "Douglas Garwood: Insurance Adjuster." Briefly, Craig told the story of the stolen car, omitting the account of the dastardly method taken to blackmail Mrs. Blake. As he proceeded a light seemed to break on the face of Garwood, a heavyset man, whose very gaze was inquisitorial. "Yes, the theft has been reported to us already by Dr. Wilson herself," he interrupted. "The car was insured in a company I represent." "I had hoped so," remarked Kennedy, "Do you know the woman?" he added, watching the insurance adjuster who had been listening intently as he told about the fair motor car thief. "Know her?" repeated Garwood emphatically. "Why, man, we have been so close to that woman that I feel almost intimate with her. The descriptions are those of a lady, well-dressed, and with a voice and manner that would carry her through any of the fashionable hotels, perhaps into society itself." "One of a gang of blackmailers, then," I hazarded. Garwood shrugged his shoulders. "Perhaps," he acquiesced. "It is automobile thieving that interests me, though. Why," he went on, rising excitedly, "the gangs of these thieves are getting away with half a million dollars' worth of high-priced cars every year. The police seem to be powerless to stop it. We appeal to them, but with no result. So, now we have taken things into our own hands." "What are you doing in this case?" asked Kennedy. "What the insurance companies have to do to recover stolen automobiles," Garwood replied. "For, with all deference to your friend, Deputy O'Connor, it is the insurance companies rather than the police who get stolen cars back." He had pulled out a postal card from a pigeon hole in his desk, selecting it from several apparently similar. We read: $250.00 REWARD We will pay $100.00 for car, $150.00 additional for information which will convict the thief. When last seen, driven by a woman, name not known, who is described as dark-haired, well-dressed, slight, apparently thirty years old. The car is a Dixon, 1912, seven-passenger, touring, No. 193,222, license No. 200,859, New York; dark red body, mohair top, brass lamps, has no wind shield; rear axle brake band device has extra nut on turnbuckle not painted. Car last seen near Prince Henry Hotel, New York City, Friday, the 10th. Communicate by telegraph or telephone, after notifying nearest police department, with Douglas Garwood, New York City. "The secret of it is," explained Garwood, as we finished reading, "that there are innumerable people who keep their eyes open and like to earn money easily. Thus we have several hundreds of amateur and enthusiastic detectives watching all over the city and country for any car that looks suspicious." Kennedy thanked him for his courtesy, and we rose to go. "I shall be glad to keep you informed of anything that turns up," he promised. CHAPTER XX THE ARTIFICIAL KIDNEY In the laboratory, Kennedy quietly set to work. He began by tearing from the germ letter the piece of gelatine and first examining it with a pocket lens. Then, with a sterile platinum wire, he picked out several minute sections of the black spot on the gelatine and placed them in agar, blood serum, and other media on which they would be likely to grow. "I shall have to wait until to-morrow to examine them properly," he remarked. "There are colonies of something there, all right, but I must have them more fully developed." A hurried telephone call late in the day from Miss Sears told us that Mrs. Blake herself had begun to complain, and that Dr. Wilson had been summoned but had been unable to give an opinion on the nature of the malady. Kennedy quickly decided on making a visit to the doctor, who lived not far downtown from the laboratory. Dr. Rae Wilson proved to be a nervous little woman, inclined, I felt, to be dictatorial. I thought that secretly she felt a little piqued at our having been taken into the Blakes' confidence before herself, and Kennedy made every effort to smooth that aspect over tactfully. "Have you any idea what it can be?" he asked finally. She shook her head noncommittally. "I have taken blood smears," she answered, "but so far haven't been able to discover anything. I shall have to have her under observation for a day or two before I can answer that. Still, as Mrs. Blake is so ill, I have ordered another trained nurse to relieve Miss Sears of the added work, a very efficient nurse, a Miss Rogers." Kennedy had risen to go. "You have had no word about your car?" he asked casually. "None yet. I'm not worrying. It was insured." "Who is this arch criminal, Dr. Hopf?" I mused as we retraced our steps to the laboratory. "Is Mrs. Blake stricken now by the same trouble that seems to have affected Buster?" "Only my examination will show," he said. "I shall let nothing interfere with that now. It must be the starting point for any work that I may do in the case." We arrived at Kennedy's workshop of scientific crime and he immediately plunged into work. Looking up he caught sight of me standing helplessly idle. "Walter," he remarked thoughtfully adjusting a microscope, "suppose you run down and see Garwood. Perhaps he has something to report. And by the way, while you are out, make inquiries about the Blakes, young Baldwin, Miss Sears and this Dr. Wilson. I have heard of her before, at least by name. Perhaps you may find something interesting." Glad to have a chance to seem to be doing something whether it amounted to anything or not, I dropped in to see Garwood. So far he had nothing to report except the usual number of false alarms. From his office I went up to the Star where fortunately I found one of the reporters who wrote society notes. The Blakes, I found, as we already knew, to be well known and moving in the highest social circles. As far as known they had no particular enemies, other than those common to all people of great wealth. Dr. Wilson had a large practice, built up in recent years, and was one of the best known society physicians for women. Miss Sears was unknown, as far as I could determine. As for Duncan Baldwin, I found that he had become acquainted with Reginald Blake in college, that he came of no particular family and seemed to have no great means, although he was very popular in the best circles. In fact he had had, thanks to his friend, a rather meteoric rise in society, though it was reported that he was somewhat involved in debt as a result. I returned to the laboratory to find that Craig had taken out of a cabinet a peculiar looking arrangement. It consisted of thirty-two tubes, each about sixteen inches long, with S-turns, like a minute radiator. It was altogether not over a cubic foot in size, and enclosed in a glass cylinder. There were in it, perhaps, fifty feet of tubes, a perfectly-closed tubular system which I noticed Kennedy was keeping absolutely sterile in a germicidal solution of some kind. Inside the tubes and surrounding them was a saline solution which was kept at a uniform temperature by a special heating apparatus. Kennedy had placed the apparatus on the laboratory table and then gently took the little dog from his basket and laid him beside it. A few minutes later the poor little suffering Buster was mercifully under the influence of an anesthetic. Quickly Craig worked. First he attached the end of one of the tubes by means of a little cannula to the carotid artery of the dog. Then the other was attached to the jugular vein. As he released the clamp which held the artery, the little dog's feverishly beating heart spurted the arterial blood from the carotid into the tubes holding the normal salt solution and that pressure, in turn, pumped the salt solution which filled the tubes into the jugular vein, thus replacing the arterial blood that had poured into the tubes from the other end and maintaining the normal hydrostatic conditions in the body circulation. The dog was being kept alive, although perhaps a third of his blood was out of his body. "You see," he said at length, after we had watched the process a few minutes, "what I have here is in reality an artificial kidney. It is a system that has been devised by several doctors at Johns Hopkins. "If there is any toxin in the blood of this dog, the kidneys are naturally endeavoring to eliminate it. Perhaps it is being eliminated too slowly. In that case this arrangement which I have here will aid them. We call it vividiffusion and it depends for its action on the physical principle of osmosis, the passage of substances of a certain kind through a porous membrane, such as these tubes of celloidin. "Thus any substance, any poison that is dialyzable is diffused into the surrounding salt solution and the blood is passed back into the body, with no air in it, no infection, and without alteration. Clotting is prevented by the injection of a harmless substance derived from leeches, known as hirudin. I prevent the loss of anything in the blood which I want retained by placing in the salt solution around the tubes an amount of that substance equal to that held in solution by the blood. Of course that does not apply to the colloidal substances in the blood which would not pass by osmosis under any circumstances. But by such adjustments I can remove and study any desired substance in the blood, provided it is capable of diffusion. In fact this little apparatus has been found in practice to compare favorably with the kidneys themselves in removing even a lethal dose of poison." I watched in amazement. He was actually cleaning the blood of the dog and putting it back again, purified, into the little body. Far from being cruel, as perhaps it might seem, it was in reality probably the only method by which the animal could be saved, and at the same time it was giving us a clue as to some elusive, subtle substance used in the case. "Indeed," Kennedy went on reflectively, "this process can be kept up for several hours without injury to the dog, though I do not think that will be necessary to relieve the unwonted strain that has been put upon his natural organs. Finally, at the close of the operation, serious loss of blood is overcome by driving back the greater part of it into his body, closing up the artery and vein, and taking good care of the animal so that he will make a quick recovery." For a long time I watched the fascinating process of seeing the life blood coursing through the porous tubes in the salt solution, while Kennedy gave his undivided attention to the success of the delicate experiment. It was late when I left him, still at work over Buster, and went up to our apartment to turn in, convinced that nothing more would happen that night. The next morning, with characteristic energy, Craig was at work early, examining the cultures he had made from the black spots on the gelatine. By the look of perplexity on his face, I knew that he had discovered something that instead of clearing the mystery up, further deepened it. "What do you find?" I asked anxiously. "Walter," he exclaimed, laying aside the last of the slides which he had been staining and looking at intently through the microscope, "that stuff on the gelatine is entirely harmless. There was nothing in it except common mold." For the moment I did not comprehend. "Mold?" I repeated. "Yes," he replied, "just common, ordinary mold such as grows on the top of a jar of fruit or preserves when it is exposed to the air." I stifled an exclamation of incredulity. It seemed impossible that the deadly germ note should be harmless, in view of the events that had followed its receipt. Just then the laboratory door was flung open and Reginald Blake, pale and excited, entered. He had every mark of having been up all night. "What's the matter?" asked Craig. "It's about my mother," he blurted out. "She seems to be getting worse all the time. Miss Sears is alarmed, and Betty is almost ill herself with worry. Dr. Wilson doesn't seem to know what it is that affects her, and neither does the new nurse. Can you DO something?" There was a tone of appeal in his voice that was not like the self-sufficient Reginald of the day before. "Does there seem to be any immediate danger?" asked Kennedy. "Perhaps not--I can't say," he urged. "But she is gradually getting worse instead of better." Kennedy thought a moment. "Has anything else happened?" he asked slowly. "N-no. That's enough, isn't it?" "Indeed it is," replied Craig, trying to be reassuring. Then, recollecting Betty, he added, "Reginald, go back and tell your sister for me that she must positively make the greatest effort of her life to control herself. Tell her that her mother needs her--needs her well and brave. I shall be up at the house immediately. Do the best you can. I depend on you." Kennedy's words seemed to have a bracing effect on Reginald and a few moments later he left, much calmer. "I hope I have given him something to do which will keep him from mussing things up again," remarked Kennedy, mindful of Reginald's former excursion into detective work. Meanwhile Craig plunged furiously into his study of the substances he had isolated from the saline solution in which he had "washed" the blood of the little Pekinese. "There's no use doing anything in the dark," he explained. "Until we know what it is we are fighting we can't very well fight." For the moment I was overwhelmed by the impending tragedy that seemed to be hanging over Mrs. Blake. The more I thought of it, the more inexplicable became the discovery of the mold. "That is all very well about the mold on the gelatine strip in the letter," I insisted at length. "But, Craig, there must be something wrong somewhere. Mere molds could not have made Buster so ill, and now the infection, or whatever it is, has spread to Mrs. Blake herself. What have you found out by studying Buster?" He looked up from his close scrutiny of the material in one of the test tubes which contained something he had recovered from the saline solution of the diffusion apparatus. I could read on his face that whatever it was, it was serious. "What is it?" I repeated almost breathlessly. "I suppose I might coin a word to describe it," he answered slowly, measuring his phrases. "Perhaps it might be called hyper-amino-acidemia." I puckered my eyes at the mouth-filling term Kennedy smiled. "It would mean," he explained, "a great quantity of the amino-acids, non-coagulable, nitrogenous compounds in the blood. You know the indols, the phenols, and the amins are produced both by putrefactive bacteria and by the process of metabolism, the burning up of the tissues in the process of utilizing the energy that means life. But under normal circumstances, the amins are not present in the blood in any such quantities as I have discovered by this new method of diffusion." He paused a moment, as if in deference to my inability to follow him on such an abstruse topic, then resumed, "As far as I am able to determine, this poison or toxin is an amin similar to that secreted by certain cephalopods found in the neighborhood of Naples. It is an aromatic amin. Smell it." I bent over and inhaled the peculiar odor. "Those creatures," he continued, "catch their prey by this highly active poison secreted by the so-called salivary glands. Even a little bit will kill a crab easily." I was following him now with intense interest, thinking of the astuteness of a mind capable of thinking of such a poison. "Indeed, it is surprising," he resumed thoughtfully, "how many an innocent substance can be changed by bacteria into a virulent poison. In fact our poisons and our drugs are in many instances the close relations of harmless compounds that represent the intermediate steps in the daily process of metabolism." "Then," I put in, "the toxin was produced by germs, after all?" "I did not say that," he corrected. "It might have been. But I find no germs in the blood of Buster. Nor did Dr. Wilson find any in the blood smears which she took from Mrs. Blake." He seemed to have thrown the whole thing back again into the limbo of the unexplainable, and I felt nonplussed. "The writer of that letter," he went on, waving the piece of sterile platinum wire with which he had been transferring drops of liquid in his search for germs, "was a much more skillful bacteriologist than I thought, evidently. No, the trouble does not seem to be from germs breathed in, or from germs at all--it is from some kind of germ-free toxin that has been injected or otherwise introduced." Vaguely now I began to appreciate the terrible significance of what he had discovered. "But the letter?" I persisted mechanically. "The writer of that was quite as shrewd a psychologist as bacteriologist," pursued Craig impressively. "He calculated the moral effect of the letter, then of Buster's illness, and finally of reaching Mrs. Blake herself." "You think Dr. Rae Wilson knows nothing of it yet?" I queried. Kennedy appeared to consider his answer carefully. Then he said slowly: "Almost any doctor with a microscope and the faintest trace of a scientific education could recognize disease germs either naturally or feloniously implanted. But when it comes to the detection of concentrated, filtered, germ-free toxins, almost any scientist might be baffled. Walter," he concluded, "this is not mere blackmail, although perhaps the visit of that woman to the Prince Henry--a desperate thing in itself, although she did get away by her quick thinking--perhaps that shows that these people are ready to stop at nothing. No, it goes deeper than blackmail." I stood aghast at the discovery of this new method of scientific murder. The astute criminal, whoever he might be, had planned to leave not even the slender clue that might be afforded by disease germs. He was operating, not with disease itself, but with something showing the ultimate effects, perhaps, of disease with none of the preliminary symptoms, baffling even to the best of physicians. I scarcely knew what to say. Before I realized it, however, Craig was at last ready for the promised visit to Mrs. Blake. We went together, carrying Buster, in his basket, not recovered, to be sure, but a very different little animal from the dying creature that had been sent to us at the laboratory. CHAPTER XXI THE POISON BRACELET We reached the Blake mansion and were promptly admitted. Miss Betty, bearing up bravely under Reginald's reassurances, greeted us before we were fairly inside the door, though she and her brother were not able to conceal the fact that their mother was no better. Miss Sears was out, for an airing, and the new nurse, Miss Rogers, was in charge of the patient. "How do you feel, this morning?" inquired Kennedy as we entered the sun-parlor, where Mrs. Blake had first received us. A single glance was enough to satisfy me of the seriousness of her condition. She seemed to be in almost a stupor from which she roused herself only with difficulty. It was as if some overpowering toxin were gradually undermining her already weakened constitution. She nodded recognition, but nothing further. Kennedy had set the dog basket down near her wheel-chair and she caught sight of it. "Buster?" she murmured, raising her eyes. "Is--he--all right?" For answer, Craig simply raised the lid of the basket. Buster already seemed to have recognized the voice of his mistress, and, with an almost human instinct, to realize that though he himself was still weak and ill, she needed encouragement. As Mrs. Blake stretched out her slender hand, drawn with pain, to his silky head, he gave a little yelp of delight and his little red tongue eagerly caressed her hand. It was as though the two understood each other. Although Mrs. Blake, as yet, had no more idea what had happened to her pet, she seemed to feel by some subtle means of thought transference that the intelligent little animal was conveying to her a message of hope. The caress, the sharp, joyous yelp, and the happy wagging of the bushy tail seemed to brighten her up, at least for the moment, almost as if she had received a new impetus. "Buster!" she exclaimed, overjoyed to get her pet back again in so much improved condition. "I wouldn't exert myself too much, Mrs. Blake," cautioned Kennedy. "Were--were there any germs in the letter?" she asked, as Reginald and Betty stood on the other side of the chair, much encouraged, apparently, at this show of throwing off the lethargy that had seized her. "Yes, but about as harmless as those would be on a piece of cheese," Kennedy hastened. "But I--I feel so weak, so played out--and my head--" Her voice trailed off, a too evident reminder that her improvement had been only momentary and prompted by the excitement of our arrival. Betty bent down solicitously and made her more comfortable as only one woman can make another. Kennedy, meanwhile, had been talking to Miss Rogers, and I could see that he was secretly taking her measure. "Has Dr. Wilson been here this morning?" I heard him ask. "Not yet," she replied. "But we expect her soon." "Professor Kennedy?" announced a servant. "Yes?" answered Craig. "There is someone on the telephone who wants to speak to you. He said he had called the laboratory first and that they told him to call you here." Kennedy hurried after the servant, while Betty and Reginald joined me, waiting, for we seemed to feel that something was about to happen. "One of the unofficial detectives has unearthed a clue," he whispered to me a few moments later when he returned. "It was Garwood." Then to the others he added, "A car, repainted, and with the number changed, but otherwise answering the description of Dr. Wilson's has been traced to the West Side. It is somewhere in the neighborhood of a saloon and garage where drivers of taxicabs hang out. Reginald, I wish you would come along with us." To Betty's unspoken question Craig hastened to add, "I don't think there is any immediate danger. If there is any change--let me know. I shall call up soon. And meanwhile," he lowered his voice to impress the instruction on her, "don't leave your mother for a moment--not for a moment," he emphasized. Reginald was ready and together we three set off to meet Garwood at a subway station near the point where the car had been reported. We had scarcely closed the front door, when we ran into Duncan Baldwin, coming down the street, evidently bent on inquiring how Mrs. Blake and Betty were. "Much better," reassured Kennedy. "Come on, Baldwin. We can't have too many on whom we can rely on an expedition like this." "Like what?" he asked, evidently not comprehending. "There's a clue, they think, to that car of Dr. Wilson's," hastily explained Reginald, linking his arm into that of his friend and falling in behind us, as Craig hurried ahead. It did not take long to reach the subway, and as we waited for the train, Craig remarked: "This is a pretty good example of how the automobile is becoming one of the most dangerous of criminal weapons. All one has to do nowadays, apparently, after committing a crime, is to jump into a waiting car and breeze away, safe." We met Garwood and under his guidance picked our way westward from the better known streets in the heart of the city, to a section that was anything but prepossessing. The place which Garwood sought was a typical Raines Law hotel on a corner, with a saloon on the first floor, and apparently the requisite number of rooms above to give it a legal license. We had separated a little so that we would not attract undue attention. Kennedy and I entered the swinging doors boldly, while the others continued across to the other corner to wait with Garwood and take in the situation. It was a strange expedition and Reginald was fidgeting while Duncan seemed nervous. Among the group of chauffeurs lounging at the bar and in the back room anyone who had ever had any dealings with the gangs of New York might have recognized the faces of men whose pictures were in the rogues' gallery and who were members of those various aristocratic organizations of the underworld. Kennedy glanced about at the motley crowd. "This is a place where you need only to be introduced properly," he whispered to me, "to have any kind of crime committed for you." As we stood there, observing, without appearing to do so, through an open window on the side street I could tell from the sounds that there was a garage in the rear of the hotel. We were startled to hear a sudden uproar from the street. Garwood, impatient at our delay, had walked down past the garage to reconnoiter. A car was being backed out hurriedly, and as it turned and swung around the corner, his trained eye had recognized it. Instantly he had reasoned that it was an attempt to make a getaway, and had raised an alarm. Those nearest the door piled out, keen for any excitement. We, too, dashed out on the street. There we saw passing an automobile, swaying and lurching at the terrific speed with which its driver, urged it up the avenue. As he flashed by he looked like an Italian to me, perhaps a gunman. Garwood had impressed a passing trolley car into service and was pursuing the automobile in it, as it swayed on its tracks as crazily as the motor did on the roadway, running with all the power the motorman could apply. A mounted policeman galloped past us, blazing away at the tires. The avenue was stirred, as seldom even in its strenuous life, with reports of shots, honking of horns, the clang of trolley bells and the shouts of men. The pursuers were losing when there came a rattle and roar from the rear wheels which told that the tires were punctured and the heavy car was riding on its rims. A huge brewery wagon crossing a side street paused to see the fun, effectually blocking the road. The car jolted to a stop. The chauffeur leaped out and a moment later dived down into a cellar. In that congested district, pursuit was useless. "Only an accomplice," commented Kennedy. "Perhaps we can get him some other way if we can catch the man--or woman--higher up." Down the street now we could see Garwood surrounded by a curious crowd but in possession of the car. I looked about for Duncan and Reginald. They had apparently been swallowed up in the crowds of idlers which seemed to be pouring out of nowhere, collecting to gape at the excitement, after the manner of a New York crowd. As I ran my eye over them, I caught sight of Reginald near the corner where we had left him in an incipient fight with someone who had a fancied grievance. A moment later we had rescued him. "Where's Duncan?" he panted. "Did anything happen to him? Garwood told us to stay here--but we got separated." Policemen had appeared on the heels of the crowd and now, except for a knot following Garwood, things seemed to be calming down. The excitement over, and the people thinning out, Kennedy still could not find any trace of Duncan. Finally he glanced in again through the swinging doors. There was Duncan, evidently quite upset by what had occurred, fortifying himself at the bar. Suddenly from above came a heavy thud, as if someone had fallen on the floor above us, followed by a suppressed shuffling of feet and a cry of help. Kennedy sprang toward a side door which led out into the hall to the hotel room above. It was locked. Before any of the others he ran out on the street and into the hall that way, taking the stairs two at a time, past a little cubby-hole of an "office" and down the upper hall to a door from which came the cry. It was a peculiar room into which we burst, half bedroom, half workshop, or rather laboratory, for on a deal table by a window stood a rack of test-tubes, several beakers, and other paraphernalia. A chambermaid was shrieking over a woman who was lying lethargic on the floor. I looked more closely. It was Dora Sears. For the moment I could not imagine what had happened. Had the events of the past few days worked on her mind and driven her into temporary insanity? Or had the blackmailing gang of automobile thieves, failing in extorting money by their original plan, seized her? Kennedy bent over and tried to lift her up. As he did so, the gold bracelet, unclasped, clattered to the floor. He picked it up and for a moment looked at it. It was hollow, but in that part of it where it unclasped could be seen a minute hypodermic needle and traces of a liquid. "A poison bracelet," he muttered to himself, "one in which enough of a virulent poison could be hidden so that in an emergency death could cheat the law." "But this Dr. Hopf," exclaimed Reginald, who stood behind us looking from the insensible girl to the bracelet and slowly comprehending what it all meant, "she alone knows where and who he is!" We looked at Kennedy. What was to be done? Was the criminal higher up to escape because one of his tools had been cornered and had taken the easiest way to get out? Kennedy had taken down the receiver of the wall telephone in the room. A moment later he was calling insistently for his laboratory. One of the students in another part of the building answered. Quickly he described the apparatus for vividiffusion and how to handle it without rupturing any of the delicate tubes. "The large one," he ordered, "with one hundred and ninety-two tubes. And hurry." Before the student appeared, came an ambulance which some one in the excitement had summoned. Kennedy quickly commandeered both the young doctor and what surgical material he had with him. Briefly he explained what he proposed to do and before the student arrived with the apparatus, they had placed the nurse in such a position that they were ready for the operation. The next room which was unoccupied had been thrown open to us and there I waited with Reginald and Duncan, endeavoring to explain to them the mysteries of the new process of washing the blood. The minutes lengthened into hours, as the blood of the poisoned girl coursed through its artificial channel, literally being washed of the toxin from the poisoned bracelet. Would it succeed? It had saved the life of Buster. But would it bring back the unfortunate before us, long enough even for her to yield her secret and enable us to catch the real criminal. What if she died? As Kennedy worked, the young men with me became more and more fascinated, watching him. The vividiffusion apparatus was now in full operation. In the intervals when he left the apparatus in charge of the young ambulance surgeon Kennedy was looking over the room. In a trunk which was open he found several bundles of papers. As he ran his eye over them quickly, he selected some and stuffed them into his pocket, then went back to watch the working of the apparatus. Reginald, who had been growing more and more nervous, at last asked if he might call up Betty to find out how his mother was. He came back from the telephone, his face wrinkled. "Poor mother," he remarked anxiously, "do you think she will pull through, Professor? Betty says that Dr. Wilson has given her no idea yet about the nature of the trouble." Kennedy thought a moment. "Of course," he said, "your mother has had no such relative amount of the poison as Buster has had. I think that undoubtedly she will recover by purely natural means. I hope so. But if not, here is the apparatus," and he patted the vividiffusion tubes in their glass case, "that will save her, too." As well as I could I explained to Reginald the nature of the toxin that Kennedy had discovered. Duncan listened, putting in a question now and then. But it was evident that his thoughts were on something else, and now and then Reginald, breaking into his old humor, rallied him about thinking of Betty. A low exclamation from both Kennedy and the surgeon attracted us. Dora Sears had moved. The operation of the apparatus was stopped, the artery and vein had been joined up, and she was slowly coming out from under the effects of the anesthetic. As we gathered about her, at a little distance, we heard her cry in her delirium, "I--I would have--done--anything--for him." We strained our ears. Was she talking of the blackmailer, Dr. Hopf? "Who?" asked Craig, bending over close to her ear. "I--I would--have done anything," she repeated as if someone had contradicted her. She went on, dreamily, ramblingly, "He--is--is--my brother. I--" She stopped through weakness. "Where is Dr. Hopf?" asked Kennedy, trying to recall her fleeting attention. "Dr. Hopf? Dr. Hopf?" she repeated, then smiling to herself as people will when they are leaving the borderline of anesthesia, she repeated the name, "Hopf?" "Yes," persisted Kennedy. "There is no Dr. Hopf," she added. "Tell me--did--did they--" "No Dr. Hopf?" Kennedy insisted. She had lapsed again into half insensibility. He rose and faced us, speaking rapidly. "New York seems to have a mysterious and uncanny attraction for odds and ends of humanity, among them the great army of adventuresses. In fact there often seems to be something decidedly adventurous about the nursing profession. This is a girl of unusual education in medicine. Evidently she has traveled--her letters show it. Many of them show that she has been in Italy. Perhaps it was there that she heard of the drug that has been used in this case. It was she who injected the germ-free toxin, first into the dog, then into Mrs. Blake, she who wrote the blackmail letter which was to have explained the death." He paused. Evidently she had heard dimly, was straining every effort to hear. In her effort she caught sight of our faces. Suddenly, as if she had seen an apparition, she raised herself with almost superhuman strength. "Duncan!" she cried. "Duncan! Why--didn't you--get away--while there was time--after you warned me?" Kennedy had wheeled about and was facing us. He was holding in his hand some of the letters he had taken from the trunk. Among others was a folded piece of parchment that looked like a diploma. He unfolded it and we bent over to read. It was a diploma from the Central Western College of Nursing. As I read the name written in, it was with a shock. It was not Dora Sears, but Dora Baldwin. "A very clever plot," he ground out, taking a step nearer us. "With the aid of your sister and a disreputable gang of chauffeurs you planned to hasten the death of Mrs. Blake, to hasten the inheritance of the Blake fortune by your future wife. I think your creditors will have less chance of collecting now than ever, Duncan Baldwin." CHAPTER XXII THE DEVIL WORSHIPERS Tragic though the end of the young nurse, Dora Baldwin, had been, the scheme of her brother, in which she had become fatally involved, was by no means as diabolical as that in the case that confronted us a short time after that. I recall this case particularly not only because it was so weird but also because of the unique manner in which it began. "I am damned--Professor Kennedy--damned!" The words rang out as the cry of a lost soul. A terrible look of inexpressible anguish and fear was written on the face of Craig's visitor, as she uttered them and sank back, trembling, in the easy chair, mentally and physically convulsed. As nearly as I had been able to follow, Mrs. Veda Blair's story had dealt mostly with a Professor and Madame Rapport and something she called the "Red Lodge" of the "Temple of the Occult." She was not exactly a young woman, although she was a very attractive one. She was of an age that is, perhaps, even more interesting than youth. Veda Blair, I knew, had been, before her recent marriage to Seward Blair, a Treacy, of an old, though somewhat unfortunate, family. Both the Blairs and the Treacys had been intimate and old Seward Blair, when he died about a year before, had left his fortune to his son on the condition that he marry Veda Treacy. "Sometimes," faltered Mrs. Blair, "it is as though I had two souls. One of them is dispossessed of its body and the use of its organs and is frantic at the sight of the other that has crept in." She ended her rambling story, sobbing the terrible words, "Oh--I have committed the unpardonable sin--I am anathema--I am damned--damned!" She said nothing of what terrible thing she had done and Kennedy, for the present, did not try to lead the conversation. But of all the stories that I have heard poured forth in the confessional of the detective's office, hers, I think, was the wildest. Was she insane? At least I felt that she was sincere. Still, I wondered what sort of hallucination Craig had to deal with, as Veda Blair repeated the incoherent tale of her spiritual vagaries. Almost, I had begun to fancy that this was a case for a doctor, not for a detective, when suddenly she asked a most peculiar question. "Can people affect you for good or evil, merely by thinking about you?" she queried. Then a shudder passed over her. "They may be thinking about me now!" she murmured in terror. Her fear was so real and her physical distress so evident that Kennedy, who had been listening silently for the most part, rose and hastened to reassure her. "Not unless you make your own fears affect yourself and so play into their hands," he said earnestly. Veda looked at him a moment, then shook her head mournfully. "I have seen Dr. Vaughn," she said slowly. Dr. Gilbert Vaughn, I recollected, was a well-known alienist in the city. "He tried to tell me the same thing," she resumed doubtfully. "But--oh--I know what I know! I have felt the death thought--and he knows it!" "What do you mean?" inquired Kennedy, leaning forward keenly. "The death thought," she repeated, "a malicious psychic attack. Some one is driving me to death by it. I thought I could fight it off. I went away to escape it. Now I have come back--and I have not escaped. There is always that disturbing influence--always--directed against me. I know it will--kill me!" I listened, startled. The death thought! What did it mean? What terrible power was it? Was it hypnotism? What was this fearsome, cruel belief, this modern witchcraft that could unnerve a rich and educated woman? Surely, after all, I felt that this was not a case for a doctor alone; it called for a detective. "You see," she went on, heroically trying to control herself, "I have always been interested in the mysterious, the strange, the occult. In fact my father and my husband's father met through their common interest. So, you see, I come naturally by it. "Not long ago I heard of Professor and Madame Rapport and their new Temple of the Occult. I went to it, and later Seward became interested, too. We have been taken into a sort of inner circle," she continued fearfully, as though there were some evil power in the very words themselves, "the Red Lodge." "You have told Dr. Vaughn?" shot out Kennedy suddenly, his eyes fixed on her face to see what it would betray. Veda leaned forward, as if to tell a secret, then whispered in a low voice, "He knows. Like us--he--he is a--Devil Worshiper!" "What?" exclaimed Kennedy in wide-eyed astonishment. "A Devil Worshiper," she repeated. "You haven't heard of the Red Lodge?" Kennedy nodded negatively. "Could you get us--initiated?" he hazarded. "P--perhaps," she hesitated, in a half-frightened tone. "I--I'll try to get you in to-night." She had risen, half dazed, as if her own temerity overwhelmed her. "You--poor girl," blurted out Kennedy, his sympathies getting the upper hand for the moment as he took the hand she extended mutely. "Trust me. I will do all in my power, all in the power of modern science to help you fight off this--influence." There must have been something magnetic, hypnotic in his eye. "I will stop here for you," she murmured, as she almost fled from the room. Personally, I cannot say that I liked the idea of spying. It is not usually clean and wholesome. But I realized that occasionally it was necessary. "We are in for it now," remarked Kennedy half humorously, half seriously, "to see the Devil in the twentieth century." "And I," I added, "I am, I suppose, to be the reporter to Satan." We said nothing more about it, but I thought much about it, and the more I thought, the more incomprehensible the thing seemed. I had heard of Devil Worship, but had always associated it with far-off Indian and other heathen lands--in fact never among Caucasians in modern times, except possibly in Paris. Was there such a cult here in my own city? I felt skeptical. That night, however, promptly at the appointed time, a cab called for us, and in it was Veda Blair, nervous but determined. "Seward has gone ahead," she explained. "I told him that a friend had introduced you, that you had studied the occult abroad. I trust you to carry it out." Kennedy reassured her. The curtains were drawn and we could see nothing outside, though we must have been driven several miles, far out into the suburbs. At last the cab stopped. As we left it we could see nothing of the building, for the cab had entered a closed courtyard. "Who enters the Red Lodge?" challenged a sepulchral voice at the porte-cochere. "Give the password!" "The Serpent's Tooth," Veda answered. "Who are these?" asked the voice. "Neophytes," she replied, and a whispered parley followed. "Then enter!" announced the voice at length. It was a large room into which we were first ushered, to be inducted into the rites of Satan. There seemed to be both men and women, perhaps half a dozen votaries. Seward Blair was already present. As I met him, I did not like the look in his eye; it was too stary. Dr. Vaughn was there, too, talking in a low tone to Madame Rapport. He shot a quick look at us. His were not eyes but gimlets that tried to bore into your very soul. Chatting with Seward Blair was a Mrs. Langhorne, a very beautiful woman. To-night she seemed to be unnaturally excited. All seemed to be on most intimate terms, and, as we waited a few minutes, I could not help recalling a sentence from Huysmans: "The worship of the Devil is no more insane than the worship of God. The worshipers of Satan are mystics--mystics of an unclean sort, it is true, but mystics none the less." I did not agree with it, and did not repeat it, of course, but a moment later I overheard Dr. Vaughn saying to Kennedy: "Hoffman brought the Devil into modern life. Poe forgoes the aid of demons and works patiently and precisely by the scientific method. But the result is the same." "Yes," agreed Kennedy for the sake of appearances, "in a sense, I suppose, we are all devil worshipers in modern society--always have been. It is fear that rules and we fear the bad--not the good." As we waited, I felt, more and more, the sense of the mysterious, the secret, the unknown which have always exercised a powerful attraction on the human mind. Even the aeroplane and the submarine, the X-ray and wireless have not banished the occult. In it, I felt, there was fascination for the frivolous and deep appeal to the intellectual and spiritual. The Temple of the Occult had evidently been designed to appeal to both types. I wondered how, like Lucifer, it had fallen. The prime requisite, I could guess already, however, was--money. Was it in its worship of the root of all evil that it had fallen? We passed soon into another room, hung entirely in red, with weird, cabalistic signs all about, on the walls. It was uncanny, creepy. A huge reproduction in plaster of one of the most sardonic of Notre Dame's gargoyles seemed to preside over everything--a terrible figure in such an atmosphere. As we entered, we were struck by the blinding glare of the light, in contrast with the darkened room in which we had passed our brief novitiate, if it might be called such. Suddenly the lights were extinguished. The great gargoyle shone with an infernal light of its own! "Phosphorescent paint," whispered Kennedy to me. Still, it did not detract from the weird effect to know what caused it. There was a startling noise in the general hush. "Sata!" cried one of the devotees. A door opened and there appeared the veritable priest of the Devil--pale of face, nose sharp, mouth bitter, eyes glassy. "That is Rapport," Vaughn whispered to me. The worshipers crowded forward. Without a word, he raised his long, lean forefinger and began to single them out impressively. As he did so, each spoke, as if imploring aid. He came to Mrs. Langhorne. "I have tried the charm," she cried earnestly, "and the one whom I love still hates me, while the one I hate loves me!" "Concentrate!" replied the priest, "concentrate! Think always 'I love him. He must love me. I want him to love me. I love him. He must love me.' Over and over again you must think it. Then the other side, 'I hate him. He must leave me. I want him to leave me. I hate him--hate him.'" Around the circle he went. At last his lean finger was outstretched at Veda. It seemed as if some imp of the perverse were compelling her unwilling tongue to unlock its secrets. "Sometimes," she cried in a low, tremulous voice, "something seems to seize me, as if by the hand and urge me onward. I cannot flee from it." "Defend yourself!" answered the priest subtly. "When you know that some one is trying to kill you mentally, defend yourself! Work against it by every means in your power. Discourage! Intimidate! Destroy!" I marveled at these cryptic utterances. They shadowed a modern Black Art, of which I had had no conception--a recrudescence in other language of the age-old dualism of good and evil. It was a sort of mental malpractice. "Over and over again," he went on speaking to her, "the same thought is to be repeated against an enemy. 'You know you are going to die! You know you are going to die!' Do it an hour, two hours, at a time. Others can help you, all thinking in unison the same thought." What was this, I asked myself breathlessly--a new transcendental toxicology? Slowly, a strange mephitic vapor seemed to exhale into the room--or was it my heightened imagination? CHAPTER XXIII THE PSYCHIC CURSE There came a sudden noise--nameless--striking terror, low, rattling. I stood rooted to the spot. What was it that held me? Was it an atavistic joy in the horrible or was it merely a blasphemous curiosity? I scarcely dared to look. At last I raised my eyes. There was a live snake, upraised, his fangs striking out viciously--a rattler! I would have drawn back and fled, but Craig caught my arm. "Caged," he whispered monosyllabically. I shuddered. This, at least, was no drawing-room diablerie. "It is Ophis," intoned Rapport, "the Serpent--the one active form in Nature that cannot be ungraceful!" The appearance of the basilisk seemed to heighten the tension. At last it broke loose and then followed the most terrible blasphemies. The disciples, now all frenzied, surrounded closer the priest, the gargoyle and the serpent. They worshiped with howls and obscenities. Mad laughter mingled with pale fear and wild scorn in turns were written on the hectic faces about me. They had risen--it became a dance, a reel. The votaries seemed to spin about on their axes, as it were, uttering a low, moaning chant as they whirled. It was a mania, the spirit of demonism. Something unseen seemed to urge them on. Disgusted and stifled at the surcharged atmosphere, I would have tried to leave, but I seemed frozen to the spot. I could think of nothing except Poe's Masque of the Red Death. Above all the rest whirled Seward Blair himself. The laugh of the fiend, for the moment, was in his mouth. An instant he stood--the oracle of the Demon--devil-possessed. Around whirled the frantic devotees, howling. Shrilly he cried, "The Devil is in me!" Forward staggered the devil dancer--tall, haggard, with deep sunken eyes and matted hair, face now smeared with dirt and blood-red with the reflection of the strange, unearthly phosphorescence. He reeled slowly through the crowd, crooning a quatrain, in a low, monotonous voice, his eyelids drooping and his head forward on his breast: If the Red Slayer think he slays, Or the slain think he is slain, They know not well the subtle ways I keep and pass and turn again! Entranced the whirling crowd paused and watched. One of their number had received the "power." He was swaying slowly to and fro. "Look!" whispered Kennedy. His fingers twitched, his head wagged uncannily. Perspiration seemed to ooze from every pore. His breast heaved. He gave a sudden yell--ear-piercing. Then followed a screech of hellish laughter. The dance had ended, the dancers spellbound at the sight. He was whirling slowly, eyes protruding now, mouth foaming, chest rising and falling like a bellows, muscles quivering. Cries, vows, imprecations, prayers, all blended in an infernal hubbub. With a burst of ghastly, guttural laughter, he shrieked, "I AM the Devil!" His arms waved--cutting, sawing, hacking the air. The votaries, trembling, scarcely moved, breathed, as he danced. Suddenly he gave a great leap into the air--then fell, motionless. They crowded around him. The fiendish look was gone--the demoniac laughter stilled. It was over. The tension of the orgy had been too much for us. We parted, with scarcely a word, and yet I could feel that among the rest there was a sort of unholy companionship. Silently, Kennedy and I drove away in the darkened cab, this time with Seward and Veda Blair and Mrs. Langhorne. For several minutes not a word was said. I was, however, much occupied in watching the two women. It was not because of anything they said or did. That was not necessary. But I felt that there was a feud, something that set them against each other. "How would Rapport use the death thought, I wonder?" asked Craig speculatively, breaking the silence. Blair answered quickly. "Suppose some one tried to break away, to renounce the Lodge, expose its secrets. They would treat him so as to make him harmless--perhaps insane, confused, afraid to talk, paralyzed, or even to commit suicide or be killed in an accident. They would put the death thought on him!" Even in the prosaic jolting of the cab, away from the terrible mysteries of the Red Lodge, one could feel the spell. The cab stopped. Seward was on his feet in a moment and handing Mrs. Langhorne out at her home. For a moment they paused on the steps for an exchange of words. In that moment I caught flitting over the face of Veda a look of hatred, more intense, more real, more awful than any that had been induced under the mysteries of the rites at the Lodge. It was gone in an instant, and as Seward rejoined us I felt that, with Mrs. Langhorne gone, there was less restraint. I wondered whether it was she who had inspired the fear in Veda. Although it was more comfortable, the rest of our journey was made in silence and the Blairs dropped us at our apartment with many expressions of cordiality as we left them to proceed to their own. "Of one thing I'm sure," I remarked, entering the room where only a few short hours before Mrs. Blair had related her strange tale. "Whatever the cause of it, the devil dancers don't sham." Kennedy did not reply. He was apparently wrapped up in the consideration of the remarkable events of the evening. As for myself, it was a state of affairs which, the day before, I should have pronounced utterly beyond the wildest bounds of the imagination of the most colorful writer. Yet here it was; I had seen it. I glanced up to find Kennedy standing by the light examining something he had apparently picked up at the Red Lodge. I bent over to look at it, too. It was a little glass tube. "An ampoule, I believe the technical name of such a container is," he remarked, holding it closer to the light. In it were the remains of a dried yellow substance, broken up minutely, resembling crystals. "Who dropped it?" I asked. "Vaughn, I think," he replied. "At least, I saw him near Blair, stooping over him, at the end, and I imagine this is what I saw gleaming for an instant in the light." Kennedy said nothing more, and for my part I was thoroughly at sea and could make nothing out of it all. "What object can such a man as Dr. Vaughn possibly have in frequenting such a place?" I asked at length, adding, "And there's that Mrs. Langhorne--she was interesting, too." Kennedy made no direct reply. "I shall have them shadowed to-morrow," he said briefly, "while I am at work in the laboratory over this ampoule." As usual, also, Craig had begun on his scientific studies long before I was able to shake myself loose from the nightmares that haunted me after our weird experience of the evening. He had already given the order to an agency for the shadowing, and his next move was to start me out, also, looking into the history of those concerned in the case. As far as I was able to determine, Dr. Vaughn had an excellent reputation, and I could find no reason whatever for his connection with anything of the nature of the Red Lodge. The Rapports seemed to be nearly unknown in New York, although it was reported that they had come from Paris lately. Mrs. Langhorne was a divorcee from one of the western states, but little was known about her, except that she always seemed to be well supplied with money. It seemed to be well known in the circle in which Seward Blair moved that he was friendly with her, and I had about reached the conclusion that she was unscrupulously making use of his friendship, perhaps was not above such a thing as blackmail. Thus the day passed, and we heard no word from Veda Blair, although that was explained by the shadows, whose trails crossed in a most unexpected manner. Their reports showed that there was a meeting at the Red Lodge during the late afternoon, at which all had been present except Dr. Vaughn. We learned also from them the exact location of the Lodge, in an old house just across the line in Westchester. It was evidently a long and troublesome analysis that Craig was engaged in at the laboratory, for it was some hours after dinner that night when he came into the apartment, and even then he said nothing, but buried himself in some of the technical works with which his library was stocked. He said little, but I gathered that he was in great doubt about something, perhaps, as much as anything, about how to proceed with so peculiar a case. It was growing late, and Kennedy was still steeped in his books, when the door of the apartment, which we happened to have left unlocked, was suddenly thrown open and Seward Blair burst in on us, wildly excited. "Veda is gone!" he cried, before either of us could ask him what was the matter. "Gone?" repeated Kennedy. "How--where?" "I don't know," Blair blurted out breathlessly. "We had been out together this afternoon, and I returned with her. Then I went out to the club after dinner for a while, and when I got back I missed her--not quarter of an hour ago. I burst into her room--and there I found this note. Read it. I don't know what to do. No one seems to know what has become of her. I've called up all over and then thought perhaps you might help me, might know some friend of hers that I don't know, with whom she might have gone out." Blair was plainly eager for us to help him. Kennedy took the paper from him. On it, in a trembling hand, were scrawled some words, evidently addressed to Blair himself: "You would forgive me and pity me if you knew what I have been through. "When I refused to yield my will to the will of the Lodge I suppose I aroused the enmity of the Lodge. "To-night as I lay in bed, alone, I felt that my hour had come, that mental forces that were almost irresistible were being directed against me. "I realized that I must fight not only for my sanity but for my life. "For hours I have fought that fight. "But during those hours, some one, I won't say who, seemed to have developed such psychic faculties of penetration that they were able to make their bodies pass through the walls of my room. "At last I am conquered. I pray that you--" The writing broke off abruptly, as if she had left it in wild flight. "What does that mean?" asked Kennedy, "the 'will of the Lodge'?" Blair looked at us keenly. I fancied that there was even something accusatory in the look. "Perhaps it was some mental reservation on her part," he suggested. "You do not know yourself of any reason why she should fear anything, do you?" he asked pointedly. Kennedy did not betray even by the motion of an eyelash that we knew more than we should ostensibly. There was a tap at the door. I sprang to open it, thinking perhaps, after all, it was Veda herself. Instead, a man, a stranger, stood there. "Is this Professor Kennedy?" he asked, touching his hat. Craig nodded. "I am from the psychopathic ward of the City Hospital--an orderly, sir," the man introduced. "Yes," encouraged Craig, "what can I do for you?" "A Mrs. Blair has just been brought in, sir, and we can't find her husband. She's calling for you now." Kennedy stared from the orderly to Seward Blair, startled, speechless. "What has happened?" asked Blair anxiously. "I am Mr. Blair." The orderly shook his head. He had delivered his message. That was all he knew. "What do you suppose it is?" I asked, as we sped across town in a taxicab. "Is it the curse that she dreaded?" Kennedy said nothing and Blair appeared to hear nothing. His face was drawn in tense lines. The psychopathic ward is at once one of the most interesting and one of the most depressing departments of a large city hospital, harboring, as it does, all from the more or less harmless insane to violent alcoholics and wrecked drug fiends. Mrs. Blair, we learned, had been found hatless, without money, dazed, having fallen, after an apparently aimless wandering in the streets. For the moment she lay exhausted on the white bed of the ward, eyes glazed, pupils contracted, pulse now quick, now almost evanescent, face drawn, breathing difficult, moaning now and then in physical and mental agony. Until she spoke it was impossible to tell what had happened, but the ambulance surgeon had found a little red mark on her white forearm and had pointed it out, evidently with the idea that she was suffering from a drug. At the mere sight of the mark, Blair stared as though hypnotized. Leaning over to Kennedy, so that the others could not hear, he whispered, "It is the mark of the serpent!" Our arrival had been announced to the hospital physician, who entered and stood for a moment looking at the patient. "I think it is a drug--a poison," he said meditatively. "You haven't found out yet what it is, then?" asked Craig. The physician shook his head doubtfully. "Whatever it is," he said slowly, "it is closely allied to the cyanide groups in its rapacious activity. I haven't the slightest idea of its true nature, but it seems to have a powerful affinity for important nerve centers of respiration and muscular coordination, as well as for disorganizing the blood. I should say that it produces death by respiratory paralysis and convulsions. To my mind it is an exact, though perhaps less active, counterpart of hydrocyanic acid." Kennedy had been listening intently at the start, but before the physician had finished he had bent over and made a ligature quickly with his handkerchief. Then he dispatched a messenger with a note. Next he cut about the minute wound on her arm until the blood flowed, cupping it to increase the flow. Now and then he had them administer a little stimulant. He had worked rapidly, while Blair watched him with a sort of fascination. "Get Dr. Vaughn," ordered Craig, as soon as he had a breathing spell after his quick work, adding, "and Professor and Madame Rapport. Walter, attend to that, will you? I think you will find an officer outside. You'll have to compel them to come, if they won't come otherwise," he added, giving the address of the Lodge, as we had found it. Blair shot a quick look at him, as though Craig in his knowledge were uncanny. Apparently, the address had been a secret which he thought we did not know. I managed to find an officer and dispatch him for the Rapports. A hospital orderly, I thought, would serve to get Dr. Vaughn. CHAPTER XXIV THE SERPENT'S TOOTH I had scarcely returned to the ward when, suddenly, an unnatural strength seemed to be infused into Veda. She had risen in bed. "It shall not catch me!" she cried in a new paroxysm of nameless terror. "No--no--it is pursuing me. I am never out of its grasp. I have been thought six feet underground--I know it. There it is again--still driving me--still driving me! "Will it never stop? Will no one stop it? Save me! It--is the death thought!" She had risen convulsively and had drawn back in abject, cowering terror. What was it she saw? Evidently it was very real and very awful. It pursued her relentlessly. As she lay there, rolling her eyes about, she caught sight of us and recognized us for the first time, although she had been calling for us. "They had the thought on you, too, Professor Kennedy," she almost screamed. "Hour after hour, Rapport and the rest repeated over and over again, 'Why does not some one kill him? Why does he not die?' They knew you--even when I brought you to the Red Lodge. They thought you were a spy." I turned to Kennedy. He had advanced and was leaning over to catch every word. Blair was standing behind me and she had not seen her husband yet. A quick glance showed me that he was trembling from head to foot like a leaf, as though he, too, were pursued by the nameless terror. "What did they do?" Kennedy asked in a low tone. Fearfully, gripping the bars of the iron bed, as though they were some tangible support for her mind, she answered: "They would get together. 'Now, all of you,' they said, 'unite yourselves in thought against our enemy, against Kennedy, that he must leave off persecuting us. He is ripe for destruction!'" Kennedy glanced sidewise at me, with a significant look. "God grant," she implored, "that none haunt me for what I have done in my ignorance!" Just then the door opened and my messenger entered, accompanied by Dr. Vaughn. I had turned to catch the expression on Blair's face just in time. It was a look of abject appeal. Before Dr. Vaughn could ask a question, or fairly take in the situation, Kennedy had faced him. "What was the purpose of all that elaborate mummery out at the Red Lodge?" asked Kennedy pointblank. I think I looked at Craig in no less amazement than Vaughn. In spite of the dramatic scenes through which we had passed, the spell of the occult had not fallen on him for an instant. "Mummery?" repeated Dr. Vaughn, bending his penetrating eyes on Kennedy, as if he would force him to betray himself first. "Yes," reiterated Craig. "You know as well as I do that it has been said that it is a well-established fact that the world wants to be deceived and is willing to pay for the privilege." Dr. Vaughn still gazed from one to the other of us defiantly. "You know what I mean," persisted Kennedy, "the mumbo-jumbo--just as the Haitian obi man sticks pins in a doll or melts a wax figure of his enemy. That is supposed to be an outward sign. But back of this terrible power that people believe moves in darkness and mystery is something tangible--something real." Dr. Vaughn looked up sharply at him, I think mistaking Kennedy's meaning. If he did, all doubt that Kennedy attributed anything to the supernatural was removed as he went on: "At first I had no explanation of the curious events I have just witnessed, and the more I thought about them, the more obscure did they seem. "I have tried to reason the thing out," he continued thoughtfully. "Did auto-suggestion, self-hypnotism explain what I have seen? Has Veda Blair been driven almost to death by her own fears only?" No one interrupted and he answered his own question. "Somehow the idea that it was purely fear that had driven her on did not satisfy me. As I said, I wanted something more tangible. I could not help thinking that it was not merely subjective. There was something objective, some force at work, something more than psychic in the result achieved by this criminal mental marauder, whoever it is." I was following Kennedy's reasoning now closely. As he proceeded, the point that he was making seemed more clear to me. Persons of a certain type of mind could be really mentally unbalanced by such methods which we had heard outlined, where the mere fact of another trying to exert power over them became known to them. They would, as a matter of fact, unbalance themselves, thinking about and fighting off imaginary terrors. Such people, I could readily see, might be quickly controlled, and in the wake of such control would follow stifled love, wrecked homes, ruined fortunes, suicide and even death. Dr. Vaughn leaned forward critically. "What did you conclude, then, was the explanation of what you saw last night?" he asked sharply. Kennedy met his question squarely, without flinching. "It looks to me," he replied quietly, "like a sort of hystero-epilepsy. It is well known, I believe, to demonologists--those who have studied this sort of thing. They have recognized the contortions, the screams, the wild, blasphemous talk, the cataleptic rigidity. They are epileptiform." Vaughn said nothing, but continued to weigh Kennedy as if in a balance. I, who knew him, knew that it would take a greater than Vaughn to find him wanting, once Kennedy chose to speak. As for Vaughn, was he trying to hide behind some technicality in medical ethics? "Dr. Vaughn," continued Craig, as if goading him to the point of breaking down his calm silence, "you are specialist enough to know these things as well, better than I do. You must know that epilepsy is one of the most peculiar diseases. "The victim may be in good physical condition, apparently. In fact, some hardly know that they have it. But it is something more than merely the fits. Always there is something wrong mentally. It is not the motor disturbance so much as the disturbance of consciousness." Kennedy was talking slowly, deliberately, so that none could drop a link in the reasoning. "Perhaps one in ten epileptics has insane periods, more or less," he went on, "and there is no more dangerous form of insanity. Self-consciousness is lost, and in this state of automatism the worst of crimes have been committed without the subsequent knowledge of the patient. In that state they are no more responsible than are the actors in one's dreams." The hospital physician entered, accompanied by Craig's messenger, breathless. Craig almost seized the package from his hands and broke the seal. "Ah--this is what I wanted," he exclaimed, with an air of relief, forgetting for the time the exposition of the case that he was engaged in. "Here I have some anti-crotalus venine, of Drs. Flexner and Noguchi. Fortunately, in the city it is within easy reach." Quickly, with the aid of the physician he injected it into Veda's arm. "Of all substances in nature," he remarked, still at work over the unfortunate woman, "none is so little known as the venom of serpents." It was a startling idea which the sentence had raised in my mind. All at once I recalled the first remark of Seward Blair, in which he had repeated the password that had admitted us into the Red Lodge--"the Serpent's Tooth." Could it have been that she had really been bitten at some of the orgies by the serpent which they worshiped hideously hissing in its cage? I was sure that, at least until they were compelled, none would say anything about it. Was that the interpretation of the almost hypnotized look on Blair's face? "We know next to nothing of the composition of the protein bodies in the venoms which have such terrific, quick physiological effects," Kennedy was saying. "They have been studied, it is true, but we cannot really say that they are understood--or even that there are any adequate tests by which they can be recognized. The fact is, that snake venoms are about the safest of poisons for the criminal." Kennedy had scarcely propounded this startling idea when a car was heard outside. The Rapports had arrived, with the officer I had sent after them, protesting and threatening. They quieted down a bit as they entered, and after a quick glance around saw who was present. Professor Rapport gave one glance at the victim lying exhausted on the bed, then drew back, melodramatically, and cried, "The Serpent--the mark of the serpent!" For a moment Kennedy gazed full in the eyes of them all. "WAS it a snake bite?" he asked slowly, then, turning to Mrs. Blair, after a quick glance, he went on rapidly, "The first thing to ascertain is whether the mark consists of two isolated punctures, from the poison-conducting teeth or fangs of the snake, which are constructed like a hypodermic needle." The hospital physician had bent over her at the words, and before Kennedy could go on interrupted: "This was not a snake bite; it was more likely from an all-glass hypodermic syringe with a platinum-iridium needle." Professor Rapport, priest of the Devil, advanced a step menacingly toward Kennedy. "Remember," he said in a low, angry tone, "remember--you are pledged to keep the secrets of the Red Lodge!" Craig brushed aside the sophistry with a sentence. "I do not recognize any secrets that I have to keep about the meeting this afternoon to which you summoned the Blairs and Mrs. Langhorne, according to reports from the shadows I had placed on Mrs. Langhorne and Dr. Vaughn." If there is such a thing as the evil eye, Rapport's must have been a pair of them, as he realized that Kennedy had resorted to the simple devices of shadowing the devotees. A cry, almost a shriek, startled us. Kennedy's encounter with Rapport had had an effect which none of us had considered. The step or two in advance which the prophet had taken had brought him into the line of vision of the still half-stupefied Veda lying back of Kennedy on the hospital cot. The mere sight of him, the sound of his voice and the mention of the Red Lodge had been sufficient to penetrate that stupor. She was sitting bolt upright, a ghastly, trembling specter. Slowly a smile seemed to creep over the cruel face of the mystic. Was it not a recognition of his hypnotic power? Kennedy turned and laid a gentle hand on the quaking convulsed figure of the woman. One could feel the electric tension in the air, the battle of two powers for good or evil. Which would win--the old fascination of the occult or the new power of science? It was a dramatic moment. Yet not so dramatic as the outcome. To my surprise, neither won. Suddenly she caught sight of her husband. Her face changed. All the prehistoric jealousy of which woman is capable seemed to blaze forth. "I will defend myself!" she cried. "I will fight back! She shall not win--she shall not have you--no--she shall not--never!" I recalled the strained feeling between the two women that I had noticed in the cab. Was it Mrs. Langhorne who had been the disturbing influence, whose power she feared, over herself and over her husband? Rapport had fallen back a step, but not from the mind of Kennedy. "Here," challenged Craig, facing the group and drawing from his pocket the glass ampoule, "I picked this up at the Red Lodge last night." He held it out in his hand before the Rapports so that they could not help but see it. Were they merely good actors? They betrayed nothing, at least by face or action. "It is crotalin," he announced, "the venom of the rattlesnake--crotalus horridus. It has been noticed that persons suffering from certain diseases of which epilepsy is one, after having been bitten by a rattlesnake, if they recover from the snake bite, are cured of the disease." Kennedy was forging straight ahead now in his exposure. "Crotalin," he continued, "is one of the new drugs used in the treatment of epilepsy. But it is a powerful two-edged instrument. Some one who knew the drug, who perhaps had used it, has tried an artificial bite of a rattler on Veda Blair, not for epilepsy, but for another, diabolical purpose, thinking to cover up the crime, either as the result of the so-called death thought of the Lodge or as the bite of the real rattler at the Lodge." Kennedy had at last got under Dr. Vaughn's guard. All his reticence was gone. "I joined the cult," he confessed. "I did it in order to observe and treat one of my patients for epilepsy. I justified myself. I said, 'I will be the exposer, not the accomplice, of this modern Satanism.' I joined it and--" "There is no use trying to shield anyone, Vaughn," rapped out Kennedy, scarcely taking time to listen. "An epileptic of the most dangerous criminal type has arranged this whole elaborate setting as a plot to get rid of the wife who brought him his fortune and now stands in the way of his unholy love of Mrs. Langhorne. He used you to get the poison with which you treated him. He used the Rapports with money to play on her mysticism by their so-called death thought, while he watched his opportunity to inject the fatal crotalin." Craig faced the criminal, whose eyes now showed more plainly than words his deranged mental condition, and in a low tone added, "The Devil is in you, Seward Blair!" CHAPTER XXV THE "HAPPY DUST" Veda Blair's rescue from the strange use that was made of the venom came at a time when the city was aroused as it never had been before over the nation-wide agitation against drugs. Already, it will be recalled, Kennedy and I had had some recent experience with dope fiends of various kinds, but this case I set down because it drew us more intimately into the crusade. "I've called on you, Professor Kennedy, to see if I can't interest you in the campaign I am planning against drugs." Mrs. Claydon Sutphen, social leader and suffragist, had scarcely more than introduced herself when she launched earnestly into the reason for her visit to us. "You don't realize it, perhaps," she continued rapidly, "but very often a little silver bottle of tablets is as much a necessary to some women of the smart set as cosmetics." "I've heard of such cases," nodded Craig encouragingly. "Well, you see I became interested in the subject," she added, "when I saw some of my own friends going down. That's how I came to plan the campaign in the first place." She paused, evidently nervous. "I've been threatened, too," she went on, "but I'm not going to give up the fight. People think that drugs are a curse only to the underworld, but they have no idea what inroads the habit has made in the upper world, too. Oh, it is awful!" she exclaimed. Suddenly, she leaned over and whispered, "Why, there's my own sister, Mrs. Garrett. She began taking drugs after an operation, and now they have a terrible hold on her. I needn't try to conceal anything. It's all been published in the papers--everybody knows it. Think of it--divorced, disgraced, all through these cursed drugs! Dr. Coleman, our family physician, has done everything known to break up the habit, but he hasn't succeeded." Dr. Coleman, I knew, was a famous society physician. If he had failed, I wondered why she thought a detective might succeed. But it was evidently another purpose she had in mind in introducing the subject. "So you can understand what it all means to me, personally," she resumed, with a sigh. "I've studied the thing--I've been forced to study it. Why, now the exploiters are even making drug fiends of mere--children!" Mrs. Sutphen spread out a crumpled sheet of note paper before us on which was written something in a trembling scrawl. "For instance, here's a letter I received only yesterday." Kennedy glanced over it carefully. It was signed "A Friend," and read: "I have heard of your drug war in the newspapers and wish to help you, only I don't dare to do so openly. But I can assure you that if you will investigate what I am about to tell you, you will soon be on the trail of those higher up in this terrible drug business. There is a little center of the traffic on West 66th Street, just off Broadway. I cannot tell you more, but if you can investigate it, you will be doing more good than you can possibly realize now. There is one girl there, whom they call 'Snowbird.' If you could only get hold of her quietly and place her in a sanitarium you might save her yet." Craig was more than ordinarily interested. "And the children--what did you mean by that?" "Why, it's literally true," asserted Mrs. Sutphen in a horrified tone. "Some of the victims are actually school children. Up there in 66th Street we have found a man named Armstrong, who seems to be very friendly with this young girl whom they call 'Snowbird.' Her real name, by the way, is Sawtelle, I believe. She can't be over eighteen, a mere child, yet she's a slave to the stuff." "Oh, then you have actually already acted on the hint in the letter?" asked Craig. "Yes," she replied, "I've had one of the agents of our Anti-Drug Society, a social worker, investigating the neighborhood." Kennedy nodded for her to go on. "I've even investigated myself a little, and now I want to employ some one to break the thing up. My husband had heard of you and so here I am. Can you help me?" There was a note of appeal in her voice that was irresistible to a man who had the heart of Kennedy. "Tell me just what you have discovered so far," he asked simply. "Well," she replied slowly, "after my agent verified the contents of the letter, I watched until I saw this girl--she's a mere child, as I said--going to a cabaret in the neighborhood. What struck me was that I saw her go in looking like a wreck and come out a beautiful creature, with bright eyes, flushed cheeks, almost youthful again. A most remarkable girl she is, too," mused Mrs. Sutphen, "who always wears a white gown, white hat, white shoes and white stockings. It must be a mania with her." Mrs. Sutphen seemed to have exhausted her small store of information, and as she rose to go Kennedy rose also. "I shall be glad to look into the case, Mrs. Sutphen," he promised. "I'm sure there is something that can be done--there must be." "Thank you, ever so much," she murmured, as she paused at the door, something still on her mind. "And perhaps, too," she added, "you may run across my sister, Mrs. Garrett." "Indeed," he assured her, "if there is anything I can possibly do that will assist you personally, I shall be only too happy to do it." "Thank you again, ever so much," she repeated with just a little choke in her voice. For several moments Kennedy sat contemplating the anonymous letter which she had left with him, studying both its contents and the handwriting. "We must go over the ground up there again," he remarked finally. "Perhaps we can do better than Mrs. Sutphen and her drug investigator have done." Half an hour later we had arrived and were sauntering along the street in question, walking slowly up and down in the now fast-gathering dusk. It was a typical cheap apartment block of variegated character, with people sitting idly on the narrow front steps and children spilling out into the roadway in imminent danger of their young lives from every passing automobile. On the crowded sidewalk a creation in white hurtled past us. One glance at the tense face in the flickering arc light was enough for Kennedy. He pulled my arm and we turned and followed at a safe distance. She looked like a girl who could not have been more than eighteen, if she was as old as that. She was pretty, too, but already her face was beginning to look old and worn from the use of drugs. It was unmistakable. In spite of the fact that she was hurrying, it was not difficult to follow her in the crowd, as she picked her way in and out, and finally turned into Broadway where the white lights were welcoming the night. Under the glare of a huge electric sign she stopped a moment, then entered one of the most notorious of the cabarets. We entered also at a discreet distance and sat down at a table. "Don't look around, Walter," whispered Craig, as the waiter took our order, "but to your right is Mrs. Sutphen." If he had mentioned any other name in the world, I could not have been more surprised. I waited impatiently until I could pick her out from the corner of my eye. Sure enough, it was Mrs. Sutphen and another woman. What they were doing there I could not imagine, for neither had the look of habitues of such a place. I followed Kennedy's eye and found that he was gazing furtively at a flashily dressed young man who was sitting alone at the far end in a sort of booth upholstered in leather. The girl in white, whom I was now sure was Miss Sawtelle, went over and greeted him. It was too far to see just what happened, but the young woman after sitting down rose and left almost immediately. As nearly as I could make out, she had got something from him which she had dropped into her handbag and was now hugging the handbag close to herself almost as if it were gold. We sat for a few minutes debating just what to do, when Mrs. Sutphen and her friend rose. As she passed out, a quick, covert glance told us to follow. We did so and the two turned into Broadway. "Let me present you to Miss McCann," introduced Mrs. Sutphen as we caught up with them. "Miss McCann is a social worker and trained investigator whom I'm employing." We bowed, but before we could ask a question, Mrs. Sutphen cried excitedly: "I think I have a clue, anyway. We've traced the source of the drugs at least as far as that young fellow, 'Whitecap,' whom you saw in there." I had not recognized his face, although I had undoubtedly seen pictures of him before. But no sooner had I heard the name than I recognized it as that of one of the most notorious gang leaders on the West Side. Not only that, but Whitecap's gang played an important part in local politics. There was scarcely a form of crime or vice to which Whitecap and his followers could not turn a skilled hand, whether it was swinging an election, running a gambling club, or dispensing "dope." "You see," she explained, "even before I saw you, my suspicions were aroused and I determined to obtain some of the stuff they are using up here, if possible. I realized it would be useless for me to try to get it myself, so I got Miss McCann from the Neighborhood House to try it. She got it and has turned the bottle over to me." "May I see it?" asked Craig eagerly. Mrs. Sutphen reached hastily into her handbag, drew forth a small brown glass bottle and handed it to him. Craig retreated into one of the less dark side streets. There he pulled out the paraffinned cork from the bottle, picked out a piece of cotton stuffed in the neck of the bottle and poured out some flat tablets that showed a glistening white in the palm of his hand. For an instant he regarded them. "I may keep these?" he asked. "Certainly," replied Mrs. Sutphen. "That's what I had Miss McCann get them for." Kennedy dropped the bottle into his pocket. "So that was the gang leader, 'Whitecap,'" he remarked as we turned again to Broadway. "Yes," replied Mrs. Sutphen. "At certain hours, I believe he can be found at that cabaret selling this stuff, whatever it is, to anyone who comes properly introduced. The thing seems to be so open and notorious that it amounts to a scandal." We parted a moment later, Mrs. Sutphen and Miss McCann to go to the settlement house, Craig and I to continue our investigations. "First of all, Walter," he said as we swung aboard an uptown car, "I want to stop at the laboratory." In his den, which had been the scene of so many triumphs, Kennedy began a hasty examination of the tablets, powdering one and testing it with one chemical after another. "What are they?" I asked at length when he seemed to have found the right reaction which gave him the clue. "Happy dust," he answered briefly. "Happy dust?" I repeated, looking at him a moment in doubt as to whether he was joking or serious. "What is that?" "The Tenderloin name for heroin--a comparatively new derivative of morphine. It is really morphine treated with acetic acid which renders it more powerful than morphine alone." "How do they take them? What's the effect?" I asked. "The person who uses heroin usually powders the tablets and snuffs the powder up the nose," he answered. "In a short time, perhaps only two or three weeks, one can become a confirmed victim of 'happy dust.' And while one is under its influence he is morally, physically and mentally irresponsible." Kennedy was putting away the paraphernalia he had used, meanwhile talking about the drug. "One of the worst aspects of it, too," he continued, "is the desire of the user to share his experience with some one else. This passing on of the habit, which seems to be one of the strongest desires of the drug fiend, makes him even more dangerous to society than he would otherwise be. It makes it harder for anyone once addicted to a drug to shake it off, for his friends will give him no chance. The only thing to do is to get the victim out of his environment and into an entirely new scene." The laboratory table cleared again, Kennedy had dropped into a deep study. "Now, why was Mrs. Sutphen there?" he asked aloud. "I can't think it was solely through her interest for that girl they call Snowbird. She was interested in her, but she made no attempt to interfere or to follow her. No, there must have been another reason." "You don't think she's a dope fiend herself, do you?" I asked hurriedly. Kennedy smiled. "Hardly, Walter. If she has any obsession on the subject, it is more likely to lead her to actual fanaticism against all stimulants and narcotics and everything connected with them. No, you might possibly persuade me that two and two equal five--but not seventeen. It's not very late. I think we might make another visit to that cabaret and see whether the same thing is going on yet." CHAPTER XXVI THE BINET TEST We rode downtown again and again sauntered in, this time with the theater crowd. Our first visit had been so quiet and unostentatious that the second attracted no attention or comment from the waiters, or anyone else. As we sat down we glanced over, and there in his corner still was Whitecap. Apparently his supply of the dope was inexhaustible, for he was still dispensing it. As we watched the tenderloin habitues come and go, I came soon to recognize the signs by the mere look on the face--the pasty skin, the vacant eye, the nervous quiver of the muscles as though every organ and every nerve were crying out for more of the favorite nepenthe. Time and again I noticed the victims as they sat at the tables, growing more and more haggard and worn, until they could stand it no longer. Then they would retire, sometimes after a visit across the floor to Whitecap, more often directly, for they had stocked themselves up with the drug evidently after the first visit to him. But always they would come back, changed in appearance, with what seemed to be a new lease of life, but nevertheless still as recognizable as drug victims. It was not long, as we waited, before another woman, older than Miss Sawtelle, but dressed in an extreme fashion, hurried into the cabaret and with scarcely a look to right or left went directly to Whitecap's corner. I noticed that she, too, had the look. There was a surreptitious passing of a bottle in exchange for a treasury note, and she dropped into the seat beside him. Before he could interfere, she had opened the bottle, crushed a tablet or two in a napkin, and was holding it to her face as though breathing the most exquisite perfume. With one quick inspiration of her breath after another, she was snuffing the powder up her nose. Whitecap with an angry gesture pulled the napkin from her face, and one could fancy his snarl under his breath, "Say--do you want to get me in wrong here?" But it was too late. Some at least of the happy dust had taken effect, at least enough to relieve the terrible pangs she must have been suffering. As she rose and retired, with a hasty apology to Whitecap for her indiscretion, Kennedy turned to me and exclaimed, "Think of it. The deadliest of all habits is the simplest. No hypodermic; no pipe; no paraphernalia of any kind. It's terrible." She returned to sit down and enjoy herself, careful not to obtrude herself on Whitecap lest he might become angry at the mere sight of her and treasure his anger up against the next time when she would need the drug. Already there was the most marvelous change in her. She seemed captivated by the music, the dancing, the life which a few moments before she had totally disregarded. She was seated alone, not far from us, and as she glanced about Kennedy caught her eye. She allowed her gaze to rest on us for a moment, the signal for a mild flirtation which ended in our exchange of tables and we found ourselves opposite the drug fiend, who was following up the taking of the dope by a thin-stemmed glass of a liqueur. I do not recall the conversation, but it was one of those inconsequential talks that Bohemians consider so brilliant and everybody else so vapid. As we skimmed from one subject to another, treating the big facts of life as if they were mere incidents and the little as if they overshadowed all else, I could see that Craig, who had a faculty of probing into the very soul of anyone, when he chose, was gradually leading around to a subject which I knew he wanted, above all others, to discuss. It was not long before, as the most natural remark in the world following something he had made her say, just as a clever prestidigitator forces a card, he asked, "What was it I saw you snuffing over in the booth--happy dust?" She did not even take the trouble to deny it, but nodded a brazen "Yes." "How did you come to use it first?" he asked, careful not to give offense in either tone or manner. "The usual way, I suppose," she replied with a laugh that sounded harsh and grating. "I was ill and I found out what it was the doctor was giving me." "And then?" "Oh, I thought I would use it only as long as it served my purpose and, when that was over, give it up." "But--?" prompted Craig hypnotically. "Instead, I was soon using six, eight, ten tablets of heroin a day. I found that I needed that amount in order to live. Then it went up by leaps to twenty, thirty, forty." "Suppose you couldn't get it, what then?" "Couldn't get it?" she repeated with an unspeakable horror. "Once I thought I'd try to stop. But my heart skipped beats; then it seemed to pound away, as if trying to break through my ribs. I don't think heroin is like other drugs. When one has her 'coke'--that's cocaine--taken away, she feels like a rag. Fill her up and she can do anything again. But, heroin--I think one might murder to get it!" The expression on the woman's face was almost tragic. I verily believe that she meant it. "Why," she cried, "if anyone had told me a year ago that the time would ever come when I would value some tiny white tablets above anything else in the world, yes, and even above my immortal soul, I would have thought him a lunatic." It was getting late, and as the woman showed no disposition to leave, Kennedy and I excused ourselves. Outside Craig looked at me keenly. "Can you guess who that was?" "Although she didn't tell us her name," I replied, "I am morally certain that it was Mrs. Garrett." "Precisely," he answered, "and what a shame, too, for she must evidently once have been a woman of great education and refinement." He shook his head sadly. "Walter, there isn't likely to be anything that we can do for some hours now. I have a little experiment I'd like to make. Suppose you publish for me a story in the Star about the campaign against drugs. Tell about what we have seen to-night, mention the cabaret by indirection and Whitecap directly. Then we can sit back and see what happens. We've got to throw a scare into them somehow, if we are going to smoke out anyone higher up than Whitecap. But you'll have to be careful, for if they suspect us our usefulness in the case will be over." Together, Kennedy and I worked over our story far into the night down at the Star office, and the following day waited to see whether anything came of it. It was with a great deal of interest tempered by fear that we dropped into the cabaret the following evening. Fortunately no one suspected us. In fact, having been there the night before, we had established ourselves, as it were, and were welcomed as old patrons and good spenders. I noticed, however, that Whitecap was not there. The story had been read by such of the dope fiends as had not fallen too far to keep abreast of the times and these and the waiters were busy quietly warning off a line of haggard-eyed, disappointed patrons who came around, as usual. Some of them were so obviously dependent on Whitecap that I almost regretted having written the story, for they must have been suffering the tortures of the damned. It was in the midst of a reverie of this sort that a low exclamation from Kennedy recalled my attention. There was Snowbird with a man considerably older than herself. They had just come in and were looking about frantically for Whitecap. But Whitecap had been too frightened by the story in the Star to sell any more of the magic happy dust openly in the cabaret, at least. The pair, nerve-racked and exhausted, sat down mournfully in a seat near us, and as they talked earnestly in low tones we had an excellent opportunity for studying Armstrong for the first time. He was not a bad-looking man, or even a weak one. In back of the dissipation of the drugs one fancied he could read the story of a brilliant life wrecked. But there was little left to admire or respect. As the couple talked earnestly, the one so old, the other so young in vice, I had to keep a tight rein on myself to prevent my sympathy for the wretched girl getting the better of common sense and kicking the older man out of doors. Finally Armstrong rose to go, with a final imploring glance from the girl. Obviously she had persuaded him to forage about to secure the heroin, by hook or crook, now that the accustomed source of supply was cut off so suddenly. It was also really our first chance to study the girl carefully under the light, for her entrance and exit the night before had been so hurried that we had seen comparatively little of her. Craig was watching her narrowly. Not only were the effects of the drug plainly evident on her face, but it was apparent that the snuffing the powdered tablets was destroying the bones in her nose, through shrinkage of the blood vessels, as well as undermining the nervous system and causing the brain to totter. I was wondering whether Armstrong knew of any depot for the secret distribution of the drug. I could not believe that Whitecap was either the chief distributer or the financial head of the illegal traffic. I wondered who indeed was the man higher up. Was he an importer of the drug, or was he the representative of some chemical company not averse to making an illegal dollar now and then by dragging down his fellow man? Kennedy and I were trying to act as if we were enjoying the cabaret show and not too much interested in the little drama that was being acted before us. I think little Miss Sawtelle noticed, however, that we were looking often her way. I was amazed, too, on studying her more closely to find that there was something indefinably queer about her, aside from the marked effect of the drugs she had been taking. What it was I was at a loss to determine, but I felt sure from the expression on Kennedy's face that he had noticed it also. I was on the point of asking him if he, too, observed anything queer in the girl, when Armstrong hurried in and handed her a small package, then almost without a word stalked out again, evidently as much to Snowbird's surprise as to our own. She had literally seized the package, as though she were drowning and grasping at a life buoy. Even the surprise at his hasty departure could not prevent her, however, from literally tearing the wrapper off, and in the sheltering shadow of the table cloth pouring forth the little white pellets in her lap, counting them as a miser counts his gold, "The old thief!" she exclaimed aloud. "He's held out twenty-five!" I don't know which it was that amazed me most, the almost childish petulance and ungovernable temper of the girl which made her cry out in spite of her surroundings and the circumstances, or the petty rapacity of the man who could stoop to such a low level as to rob her in this seeming underhand manner. There was no time for useless repining now. The call of outraged nature for its daily and hourly quota of poison was too imperative. She dumped the pellets back into the bottle hastily, and disappeared. When she came back, it was with that expression I had come to know so well. At least for a few hours there was a respite for her from the terrific pangs she had been suffering. She was almost happy, smiling. Even that false happiness, I felt, was superior to Armstrong's moral sense blunted by drugs. I had begun to realize how lying, stealing, crimes of all sorts might be laid at the door of this great evil. In her haste to get where she could snuff the heroin she had forgotten a light wrap lying on her chair. As she returned for it, it fell to the floor. Instantly Kennedy was on his feet, bending over to pick it up. She thanked him, and the smile lingered a moment on her face. It was enough. It gave Kennedy the chance to pursue a conversation, and in the free and easy atmosphere of the cabaret to invite her to sit over at our table. At least all her nervousness was gone and she chatted vivaciously. Kennedy said little. He was too busy watching her. It was quite the opposite of the case of Mrs. Garrett. Yet I was at a loss to define what it was that I sensed. Still the minutes sped past and we seemed to be getting on famously. Unlike his action in the case of the older woman where he had been sounding the depths of her heart and mind, in this case his idea seemed to be to allow the childish prattle to come out and perhaps explain itself. However, at the end of half an hour when we seemed to be getting no further along, Kennedy did not protest at her desire to leave us, "to keep a date," as she expressed it. "Waiter, the check, please," ordered Kennedy leisurely. When he received it, he seemed to be in no great hurry to pay it, but went over one item after another, then added up the footing again. "Strange how some of these waiters grow rich?" Craig remarked finally with a gay smile. The idea of waiters and money quickly brought some petty reminiscences to her mind. While she was still talking, Craig casually pulled a pencil out of his pocket and scribbled some figures on the back of the waiter's check. From where I was sitting beside him, I could see that he had written some figures similar to the following: 5183 47395 654726 2964375 47293815 924738651 2146073859 "Here's a stunt," he remarked, breaking into the conversation at a convenient point. "Can you repeat these numbers after me?" Without waiting for her to make excuse, he said quickly "5183." "5183," she repeated mechanically. "47395," came in rapid succession, to which she replied, perhaps a little slower than before, "47395." "Now, 654726," he said. "654726," she repeated, I thought with some hesitation. "Again, 2964375," he shot out. "269," she hesitated, "73--" she stopped. It was evident that she had reached the limit. Kennedy smiled, paid the check and we parted at the door. "What was all that rigmarole?" I inquired as the white figure disappeared down the street. "Part of the Binet test, seeing how many digits one can remember. An adult ought to remember from eight to ten, in any order. But she has the mentality of a child. That is the queer thing about her. Chronologically she may be eighteen years or so old. Mentally she is scarcely more than eight. Mrs. Sutphen was right. They have made a fiend out of a mere child--a defective who never had a chance against them." CHAPTER XXVII THE LIE DETECTOR As the horror of it all dawned on me, I hated Armstrong worse than ever, hated Whitecap, hated the man higher up, whoever he might be, who was enriching himself out of the defective, as well as the weakling, and the vicious--all three typified by Snowbird, Armstrong and Whitecap. Having no other place to go, pending further developments of the publicity we had given the drug war in the Star, Kennedy and I decided on a walk home in the bracing night air. We had scarcely entered the apartment when the hall boy called to us frantically: "Some one's been trying to get you all over town, Professor Kennedy. Here's the message. I wrote it down. An attempt has been made to poison Mrs. Sutphen. They said at the other end of the line that you'd know." We faced each other aghast. "My God!" exclaimed Kennedy. "Has that been the effect of our story, Walter? Instead of smoking out anyone--we've almost killed some one." As fast as a cab could whisk us around to Mrs. Sutphen's we hurried. "I warned her that if she mixed up in any such fight as this she might expect almost anything," remarked Mr. Sutphen nervously, as he met us in the reception room. "She's all right, now, I guess, but if it hadn't been for the prompt work of the ambulance surgeon I sent for, Dr. Coleman says she would have died in fifteen minutes." "How did it happen?" asked Craig. "Why, she usually drinks a glass of vichy and milk before retiring," replied Mr. Sutphen. "We don't know yet whether it was the vichy or the milk that was poisoned, but Dr. Coleman thinks it was chloral in one or the other, and so did the ambulance surgeon. I tell you I was scared. I tried to get Coleman, but he was out on a case, and I happened to think of the hospitals as probably the quickest. Dr. Coleman came in just as the young surgeon was bringing her around. He--oh, here he is now." The famous doctor was just coming downstairs. He saw us, but, I suppose, inasmuch as we did not belong to the Sutphen and Coleman set, ignored us. "Mrs. Sutphen will be all right now," he said reassuringly as he drew on his gloves. "The nurse has arrived, and I have given her instructions what to do. And, by the way, my dear Sutphen, I should advise you to deal firmly with her in that matter about which her name is appearing in the papers. Women nowadays don't seem to realize the dangers they run in mixing in in all these reforms. I have ordered an analysis of both the milk and vichy, but that will do little good unless we can find out who poisoned it. And there are so many chances for things like that, life is so complex nowadays--" He passed out with scarcely a nod at us. Kennedy did not attempt to question him. He was thinking rapidly. "Walter, we have no time to lose," he exclaimed, seizing a telephone that stood on a stand near by. "This is the time for action. Hello--Police Headquarters, First Deputy O'Connor, please." As Kennedy waited I tried to figure out how it could have happened. I wondered whether it might not have been Mrs. Garrett. Would she stop at anything if she feared the loss of her favorite drug? But then there were so many others and so many ways of "getting" anybody who interfered with the drug traffic that it seemed impossible to figure it out by pure deduction. "Hello, O'Connor," I heard Kennedy say; "you read that story in the Star this morning about the drug fiends at that Broadway cabaret? Yes? Well, Jameson and I wrote it. It's part of the drug war that Mrs. Sutphen has been waging. O'Connor, she's been poisoned--oh, no--she's all right now. But I want you to send out and arrest Whitecap and that fellow Armstrong immediately. I'm going to put them through a scientific third degree up in the laboratory to-night. Thank you. No--no matter how late it is, bring them up." Dr. Coleman had gone long since, Mr. Sutphen had absolutely no interest further than the recovery of Mrs. Sutphen just now, and Mrs. Sutphen was resting quietly and could not be seen. Accordingly Kennedy and I hastened up to the laboratory to wait until O'Connor could "deliver the goods." It was not long before one of O'Connor's men came in with Whitecap. "While we're waiting," said Craig, "I wish you would just try this little cut-out puzzle." I don't know what Whitecap thought, but I know I looked at Craig's invitation to "play blocks" as a joke scarcely higher in order than the number repetition of Snowbird. Whitecap did it, however, sullenly, and under compulsion, in, I should say about two minutes. "I have Armstrong here myself," called out the voice of our old friend O'Connor, as he burst into the room. "Good!" exclaimed Kennedy. "I shall be ready for him in just a second. Have Whitecap held here in the anteroom while you bring Armstrong into the laboratory. By the way, Walter, that was another of the Binet tests, putting a man at solving puzzles. It involves reflective judgment, one of the factors in executive ability. If Whitecap had been defective, it would have taken him five minutes to do that puzzle, if at all. So you see he is not in the class with Miss Sawtelle. The test shows him to be shrewd. He doesn't even touch his own dope. Now for Armstrong." I knew enough of the underworld to set Whitecap down, however, as a "lobbygow"--an agent for some one higher up, recruiting both the gangs and the ranks of street women. Before us, as O'Connor led in Armstrong, was a little machine with a big black cylinder. By means of wires and electrodes Kennedy attached it to Armstrong's chest. "Now, Armstrong," he began in an even tone, "I want you to tell the truth--the whole truth. You have been getting heroin tablets from Whitecap." "Yes, sir," replied the dope fiend defiantly. "To-day you had to get them elsewhere." No answer. "Never mind," persisted Kennedy, still calm, "I know. Why, Armstrong, you even robbed that girl of twenty-five tablets." "I did not," shot out the answer. "There were twenty-five short," accused Kennedy. The two faced each other. Craig repeated his remark. "Yes," replied Armstrong, "I held out the tablets, but it was not for myself, I can get all I want. I did it because I didn't want her to get above seventy-five a day. I have tried every way to break her of the habit that has got me--and failed. But seventy-five--is the limit!" "A pretty story!" exclaimed O'Connor. Craig laid his hand on his arm to check him, as he examined a record registered on the cylinder of the machine. "By the way, Armstrong, I want you to write me out a note that I can use to get a hundred heroin tablets. You can write it all but the name of the place where I can get them." Armstrong was on the point of demurring, but the last sentence reassured him. He would reveal nothing by it--yet. Still the man was trembling like a leaf. He wrote: "Give Whitecap one hundred shocks--A Victim." For a moment Kennedy studied the note carefully. "Oh--er--I forgot, Armstrong, but a few days ago an anonymous letter was sent to Mrs. Sutphen, signed 'A Friend.' Do you know anything about it?" "A note?" the man repeated. "Mrs. Sutphen? I don't know anything about any note, or Mrs. Sutphen either." Kennedy was still studying his record. "This," he remarked slowly, "is what I call my psychophysical test for falsehood. Lying, when it is practiced by an expert, is not easily detected by the most careful scrutiny of the liar's appearance and manner. "However, successful means have been developed for the detection of falsehood by the study of experimental psychology. Walter, I think you will recall the test I used once, the psychophysical factor of the character and rapidity of the mental process known as the association of ideas?" I nodded acquiescence. "Well," he resumed, "in criminal jurisprudence, I find an even more simple and more subjective test which has been recently devised. Professor Stoerring of Bonn has found out that feelings of pleasure and pain produce well-defined changes in respiration. Similar effects are produced by lying, according to the famous Professor Benussi of Graz. "These effects are unerring, unequivocal. The utterance of a false statement increases respiration; of a true statement decreases. The importance and scope of these discoveries are obvious." Craig was figuring rapidly on a piece of paper. "This is a certain and objective criterion," he continued as he figured, "between truth and falsehood. Even when a clever liar endeavors to escape detection by breathing irregularly, it is likely to fail, for Benussi has investigated and found that voluntary changes in respiration don't alter the result. You see, the quotient obtained by dividing the time of inspiration by the time of expiration gives me the result." He looked up suddenly. "Armstrong, you are telling the truth about some things--downright lies about others. You are a drug fiend--but I will be lenient with you, for one reason. Contrary to everything that I would have expected, you are really trying to save that poor half-witted girl whom you love from the terrible habit that has gripped you. That is why you held out the quarter of the one hundred tablets. That is why you wrote the note to Mrs. Sutphen, hoping that she might be treated in some institution." Kennedy paused as a look of incredulity passed over Armstrong's face. "Another thing you said was true," added Kennedy. "You can get all the heroin you want. Armstrong, you will put the address of that place on the outside of the note, or both you and Whitecap go to jail. Snowbird will be left to her own devices--she can get all the 'snow,' as some of you fiends call it, that she wants from those who might exploit her." "Please, Mr. Kennedy," pleaded Armstrong. "No," interrupted Craig, before the drug fiend could finish. "That is final. I must have the name of that place." In a shaky hand Armstrong wrote again. Hastily Craig stuffed the note into his pocket, and ten minutes later we were mounting the steps of a big brownstone house on a fashionable side street just around the corner from Fifth Avenue. As the door was opened by an obsequious colored servant, Craig handed him the scrap of paper signed by the password, "A Victim." Imitating the cough of a confirmed dope user, Craig was led into a large waiting room. "You're in pretty bad shape, sah," commented the servant. Kennedy nudged me and, taking the cue, I coughed myself red in the face. "Yes," he said. "Hurry--please." The servant knocked at a door, and as it was opened we caught a glimpse of Mrs. Garrett in negligee. "What is it, Sam?" she asked. "Two gentlemen for some heroin tablets, ma'am." "Tell them to go to the chemical works--not to my office, Sam," growled a man's voice inside. With a quick motion, Kennedy had Mrs. Garrett by the wrist. "I knew it," he ground out. "It was all a fake about how you got the habit. You wanted to get it, so you could get and hold him. And neither one of you would stop at anything, not even the murder of your sister, to prevent the ruin of the devilish business you have built up in manufacturing and marketing the stuff." He pulled the note from the hand of the surprised negro. "I had the right address, the place where you sell hundreds of ounces of the stuff a week--but I preferred to come to the doctor's office where I could find you both." Kennedy had firmly twisted her wrist until, with a little scream of pain, she let go the door handle. Then he gently pushed her aside, and the next instant Craig had his hand inside the collar of Dr. Coleman, society physician, proprietor of the Coleman Chemical Works downtown, the real leader of the drug gang that was debauching whole sections of the metropolis. CHAPTER XXVIII THE FAMILY SKELETON Surprised though we were at the unmasking of Dr. Coleman, there was nothing to do but to follow the thing out. In such cases we usually ran into the greatest difficulty--organized vice. This was no exception. Even when cases involved only a clever individual or a prominent family, it was the same. I recall, for example, the case of a well-known family in a New York suburb, which was particularly difficult. It began in a rather unusual manner, too. "Mr. Kennedy--I am ruined--ruined." It was early one morning that the telephone rang and I answered it. A very excited German, breathless and incoherent, was evidently at the other end of the wire. I handed the receiver to Craig and picked up the morning paper lying on the table. "Minturn--dead?" I heard Craig exclaim. "In the paper this morning? I'll be down to see you directly." Kennedy almost tore the paper from me. In the next to the end column where late news usually is dropped was a brief account of the sudden death of Owen Minturn, one of the foremost criminal lawyers of the city, in Josephson's Baths downtown. It ended: "It is believed by the coroner that Mr. Minturn was shocked to death and evidence is being sought to show that two hundred and forty volts of electricity had been thrown into the attorney's body while he was in the electric bath. Joseph Josephson, the proprietor of the bath, who operated the switchboard, is being held, pending the completion of the inquiry." As Kennedy hastily ran his eye over the paragraphs, he became more and more excited himself. "Walter," he cried, as he finished, "I don't believe that that was an accident at all." "Why?" I asked. He already had his hat on, and I knew he was going to Josephson's breakfastless. I followed reluctantly. "Because," he answered, as we hustled along in the early morning crowd, "it was only yesterday afternoon that I saw Minturn at his office and he made an appointment with me for this very morning. He was a very secretive man, but he did tell me this much, that he feared his life was in danger and that it was in some way connected with that Pearcy case up in Stratfield, Connecticut, where he has an estate. You have read of the case?" Indeed I had. It had seemed to me to be a particularly inexplicable affair. Apparently a whole family had been poisoned and a few days before old Mr. Randall Pearcy, a retired manufacturer, had died after a brief but mysterious illness. Pearcy had been married a year or so ago to Annette Oakleigh, a Broadway comic opera singer, who was his second wife. By his first marriage he had had two children, a son, Warner, and a daughter, Isabel. Warner Pearcy, I had heard, had blazed a vermilion trail along the Great White Way, but his sister was of the opposite temperament, interested in social work, and had attracted much attention by organizing a settlement in the slums of Stratfield for the uplift of the workers in the Pearcy and other mills. Broadway, as well as Stratfield, had already woven a fantastic background, for the mystery and hints had been broadly made that Annette Oakleigh had been indiscreetly intimate with a young physician in the town, a Dr. Gunther, a friend, by the way, of Minturn. "There has been no trial yet," went on Kennedy, "but Minturn seems to have appeared before the coroner's jury at Stratfield and to have asserted the innocence of Mrs. Pearcy and that of Dr. Gunther so well that, although the jury brought in a verdict of murder by poison by some one unknown, there has been no mention of the name of anyone else. The coroner simply adjourned the inquest so that a more careful analysis might be made of the vital organs. And now comes this second tragedy in New York." "What was the poison?" I asked. "Have they found out yet?" "They are pretty sure, so Minturn told me, that it was lead poisoning. The fact not generally known is," he added in a lower tone, "that the cases were not confined to the Pearcy house. They had even extended to Minturn's too, although about that he said little yesterday. The estates up there adjoin, you know." Owen Minturn, I recalled, had gained a formidable reputation by his successful handling of cases from the lowest strata of society to the highest. Indeed it was a byword that his appearance in court indicated two things--the guilt of the accused and a verdict of acquittal. "Of course," Craig pursued as we were jolted from station to station downtown, "you know they say that Minturn never kept a record of a case. But written records were as nothing compared to what that man must have carried only in his head." It was a common saying that, if Minturn should tell all he knew, he might hang half a dozen prominent men in society. That was not strictly true, perhaps, but it was certain that a revelation of the things confided to him by clients which were never put down on paper would have caused a series of explosions that would have wrecked at least some portions of the social and financial world. He had heard much and told little, for he had been a sort of "father confessor." Had Minturn, I wondered, known the name of the real criminal? Josephson's was a popular bath on Forty-second Street, where many of the "sun-dodgers" were accustomed to recuperate during the day from their arduous pursuit of pleasure at night and prepare for the resumption of their toil during the coming night. It was more than that, however, for it had a reputation for being conducted really on a high plane. We met Josephson downstairs. He had been released under bail, though the place was temporarily closed and watched over by the agents of the coroner and the police. Josephson appeared to be a man of some education and quite different from what I had imagined from hearing him over the telephone. "Oh, Mr. Kennedy," he exclaimed, "who now will come to my baths? Last night they were crowded, but to-day--" He ended with an expressive gesture of his hands. "One customer I have surely lost, young Mr. Pearcy," he went on. "Warner Pearcy?" asked Craig. "Was he here last night?" "Nearly every night," replied Josephson, now glib enough as his first excitement subsided and his command of English returned. "He was a neighbor of Mr. Minturn's, I hear. Oh, what luck!" growled Josephson as the name recalled him to his present troubles. "Well," remarked Kennedy with an attempt at reassurance as if to gain the masseur's confidence, "I know as well as you that it is often amazing what a tremendous shock a man may receive and yet not be killed, and no less amazing how small a shock may kill. It all depends on circumstances." Josephson shot a covert look at Kennedy. "Yes," he reiterated, "but I cannot see how it COULD be. If the lights had become short-circuited with the bath, that might have thrown a current into the bath. But they were not. I know it." "Still," pursued Kennedy, watching him keenly, "it is not all a question of current. To kill, the shock must pass through a vital organ--the brain, the heart, the upper spinal cord. So, a small shock may kill and a large one may not. If it passes in one foot and out by the other, the current isn't likely to be as dangerous as if it passes in by a hand or foot and then out by a foot or hand. In one case it passes through no vital organ; in the other it is very likely to do so. You see, the current can flow through the body only when it has a place of entrance and a place of exit. In all cases of accident from electric light wires, the victim is touching some conductor--damp earth, salty earth, water, something that gives the current an outlet and--" "But even if the lights had been short-circuited," interrupted Josephson, "Mr. Minturn would have escaped injury unless he had touched the taps of the bath. Oh, no, sir, accidents in the medical use of electricity are rare. They don't happen here in my establishment," he maintained stoutly. "The trouble was that the coroner, without any knowledge of the physiological effects of electricity on the body, simply jumped at once to the conclusion that it was the electric bath that did it." "Then it was for medical treatment that Mr. Minturn was taking the bath?" asked Kennedy, quickly taking up the point. "Yes, of course," answered the masseur, eager to explain. "You are acquainted with the latest treatment for lead poisoning by means of the electric bath?" Kennedy nodded. "I know that Sir Thomas Oliver, the English authority who has written much on dangerous trades, has tried it with marked success." "Well, sir, that was why Mr. Minturn was here. He came here introduced by a Dr. Gunther of Stratfield." "Indeed?" remarked Kennedy colorlessly, though I could see that it interested him, for evidently Minturn had said nothing of being himself a sufferer from the poison. "May I see the bath?" "Surely," said Josephson, leading the way upstairs. It was an oaken tub with metal rods on the two long sides, from which depended prismatic carbon rods. Kennedy examined it closely. "This is what we call a hydro-electric bath," Josephson explained. "Those rods on the sides are the electrodes. You see there are no metal parts in the tub itself. The rods are attached by wiring to a wall switch out here." He pointed to the next room. Kennedy examined the switch with care. "From it," went on Josephson, "wires lead to an accumulator battery of perhaps thirty volts. It uses very little current. Dr. Gunther tested it and found it all right." Craig leaned over the bath, and from the carbon electrodes scraped off a white powder in minute crystals. "Ordinarily," Josephson pursued, "lead is eliminated by the skin and kidneys. But now, as you know, it is being helped along by electrolysis. I talked to Dr. Gunther about it. It is his opinion that it is probably eliminated as a chloride from the tissues of the body to the electrodes in the bath in which the patient is wholly or partly immersed. On the positive electrodes we get the peroxide. On the negative there is a spongy metallic form of lead. But it is only a small amount." "The body has been removed?" asked Craig. "Not yet," the masseur replied. "The coroner has ordered it kept here under guard until he makes up his mind what disposition to have made of it." We were next ushered into a little room on the same floor, at the door of which was posted an official from the coroner. "First of all," remarked Craig, as he drew back the sheet and began, a minute examination of the earthly remains of the great lawyer, "there are to be considered the safeguards of the human body against the passage through it of a fatal electric current--the high electric resistance of the body itself. It is particularly high when the current must pass through joints such as wrists, knees, elbows, and quite high when the bones of the head are concerned. Still, there might have been an incautious application of the current to the head, especially when the subject is a person of advanced age or latent cerebral disease, though I don't know that that fits Mr. Minturn. That's strange," he muttered, looking up, puzzled. "I can find no mark of a burn on the body--absolutely no mark of anything." "That's what I say," put in Josephson, much pleased by what Kennedy said, for he had been waiting anxiously to see what Craig discovered on his own examination. "It's impossible." "It's all the more remarkable," went on Craig, half to himself and ignoring Josephson, "because burns due to electric currents are totally unlike those produced in other ways. They occur at the point of contact, usually about the arms and hands, or the head. Electricity is much to be feared when it involves the cranial cavity." He completed his examination of the head which once had carried secrets which themselves must have been incandescent. "Then, too, such burns are most often something more than superficial, for considerable heat is developed which leads to massive destruction and carbonization of the tissues to a considerable depth. I have seen actual losses of substance--a lump of killed flesh surrounded by healthy tissues. Besides, such burns show an unexpected indolence when compared to the violent pains of ordinary burns. Perhaps that is due to the destruction of the nerve endings. How did Minturn die? Was he alone? Was he dead when he was discovered?" "He was alone," replied Josephson, slowly endeavoring to tell it exactly as he had seen it, "but that's the strange part of it. He seemed to be suffering from a convulsion. I think he complained at first of a feeling of tightness of his throat and a twitching of the muscles of his hands and feet. Anyhow, he called for help. I was up here and we rushed in. Dr. Gunther had just brought him and then had gone away, after introducing him, and showing him the bath." Josephson proceeded slowly, evidently having been warned that anything he said might be used against him. "We carried him, when he was this way, into this very room. But it was only for a short time. Then came a violent convulsion. It seemed to extend rapidly all over his body. His legs were rigid, his feet bent, his head back. Why, he was resting only on his heels and the back of his head. You see, Mr. Kennedy, that simply could not be the electric shock." "Hardly," commented Kennedy, looking again at the body. "It looks more like a tetanus convulsion. Yet there does not seem to be any trace of a recent wound that might have caused lockjaw. How did he look?" "Oh, his face finally became livid," replied Josephson. "He had a ghastly, grinning expression, his eyes were wide, there was foam on his mouth, and his breathing was difficult." "Not like tetanus, either," revised Craig. "There the convulsion usually begins with the face and progresses to the other muscles. Here it seems to have gone the other way." "That lasted a minute or so," resumed the masseur. "Then he sank back--perfectly limp. I thought he was dead. But he was not. A cold sweat broke out all over him and he was as if in a deep sleep." "What did you do?" prompted Kennedy. "I didn't know what to do. I called an ambulance. But the moment the door opened, his body seemed to stiffen again. He had one other convulsion--and when he grew limp he was dead." CHAPTER XXIX THE LEAD POISONER It was a gruesome recital and I was glad to leave the baths finally with Kennedy. Josephson was quite evidently relieved at the attitude Craig had taken toward the coroner's conclusion that Minturn had been shocked to death. As far as I could see, however, it added to rather than cleared up the mystery. Craig went directly uptown to his laboratory, in contrast with our journey down, in abstracted silence, which was his manner when he was trying to reason out some particularly knotty problem. As Kennedy placed the white crystals which he had scraped off the electrodes of the tub on a piece of dark paper in the laboratory, he wet the tip of his finger and touched just the minutest grain to his tongue. The look on his face told me that something unexpected had happened. He held a similar minute speck of the powder out to me. It was an intensely bitter taste and very persistent, for even after we had rinsed out our mouths it seemed to remain, clinging persistently to the tongue. He placed some of the grains in some pure water. They dissolved only slightly, if at all. But in a tube in which he mixed a little ether and chloroform they dissolved fairly readily. Next, without a word, he poured just a drop of strong sulphuric acid on the crystals. There was not a change in them. Quickly he reached up into the rack and took down a bottle labeled "Potassium Bichromate." "Let us see what an oxidizing agent will do," he remarked. As he gently added the bichromate, there came a most marvelous, kaleidoscopic change. From being almost colorless, the crystals turned instantly to a deep blue, then rapidly to purple, lilac, red, and then the red slowly faded away and they became colorless again. "What is it?" I asked, fascinated. "Lead?" "N-no," he replied, the lines of his forehead deepening. "No. This is sulphate of strychnine." "Sulphate of strychnine?" I repeated in astonishment. "Yes," he reiterated slowly. "I might have suspected that from the convulsions, particularly when Josephson said that the noise and excitement of the arrival of the ambulance brought on the fatal paroxysm. That is symptomatic. But I didn't fully realize it until I got up here and tasted the stuff. Then I suspected, for that taste is characteristic. Even one part diluted seventy thousand times gives that decided bitter taste." "That's all very well," I remarked, recalling the intense bitterness yet on my tongue. "But how do you suppose it was possible for anyone to administer it? It seems to me that he would have said something, if he had swallowed even the minutest part of it. He must have known it. Yet apparently he didn't. At least he said nothing about it--or else Josephson is concealing something." "Did he swallow it--necessarily?" queried Kennedy, in a tone calculated to show me that the chemical world, at least, was full of a number of things, and there was much to learn. "Well, I suppose if it had been given hypodermically, it would have a more violent effect," I persisted, trying to figure out a way that the poison might have been given. "Even more unlikely," objected Craig, with a delight at discovering a new mystery that to me seemed almost fiendish. "No, he would certainly have felt a needle, have cried out and said something about it, if anyone had tried that. This poisoned needle business isn't as easy as some people seem to think nowadays." "Then he might have absorbed it from the water," I insisted, recalling a recent case of Kennedy's and adding, "by osmosis." "You saw how difficult it was to dissolve in water," Craig rejected quietly. "Well, then," I concluded in desperation. "How could it have been introduced?" "I have a theory," was all he would say, reaching for the railway guide, "but it will take me up to Stratfield to prove it." His plan gave us a little respite and we paused long enough to lunch, for which breathing space I was duly thankful. The forenoon saw us on the train, Kennedy carrying a large and cumbersome package which he brought down with him from the laboratory and which we took turns in carrying, though he gave no hint of its contents. We arrived in Stratfield, a very pretty little mill town, in the middle of the afternoon, and with very little trouble were directed to the Pearcy house, after Kennedy had checked the parcel with the station agent. Mrs. Pearcy, to whom we introduced ourselves as reporters of the Star, was a tall blonde. I could not help thinking that she made a particularly dashing widow. With her at the time was Isabel Pearcy, a slender girl whose sensitive lips and large, earnest eyes indicated a fine, high-strung nature. Even before we had introduced ourselves, I could not help thinking that there was a sort of hostility between the women. Certainly it was evident that there was as much difference in temperament as between the butterfly and the bee. "No," replied the elder woman quickly to a request from Kennedy for an interview, "there is nothing that I care to say to the newspapers. They have said too much already about this--unfortunate affair." Whether it was imagination or not, I fancied that there was an air of reserve about both women. It struck me as a most peculiar household. What was it? Was each suspicious of the other? Was each concealing something? I managed to steal a glance at Kennedy's face to see whether there was anything to confirm my own impression. He was watching Mrs. Pearcy closely as she spoke. In fact his next few questions, inconsequential as they were, seemed addressed to her solely for the purpose of getting her to speak. I followed his eyes and found that he was watching her mouth, in reality. As she answered I noted her beautiful white teeth. Kennedy himself had trained me to notice small things, and at the time, though I thought it was trivial, I recall noticing on her gums, where they joined the teeth, a peculiar bluish-black line. Kennedy had been careful to address only Mrs. Pearcy at first, and as he continued questioning her, she seemed to realize that he was trying to lead her along. "I must positively refuse to talk any more," she repeated finally, rising. "I am not to be tricked into saying anything." She had left the room, evidently expecting that Isabel would follow. She did not. In fact I felt that Miss Pearcy was visibly relieved by the departure of her stepmother. She seemed anxious to ask us something and now took the first opportunity. "Tell me," she said eagerly, "how did Mr. Minturn die? What do they really think of it in New York?" "They think it is poisoning," replied Craig, noting the look on her face. She betrayed nothing, as far as I could see, except a natural neighborly interest. "Poisoning?" she repeated. "By what?" "Lead poisoning," he replied evasively. She said nothing. It was evident that, slip of a girl though she was, she was quite the match of anyone who attempted leading questions. Kennedy changed his method. "You will pardon me," he said apologetically, "for recalling what must be distressing. But we newspapermen often have to do things and ask questions that are distasteful. I believe it is rumored that your father suffered from lead poisoning?" "Oh, I don't know what it was--none of us do," she cried, almost pathetically. "I had been living at the settlement until lately. When father grew worse, I came home. He had such strange visions--hallucinations, I suppose you would call them. In the daytime he would be so very morose and melancholy. Then, too, there were terrible pains in his stomach, and his eyesight began to fail. Yes, I believe that Dr. Gunther did say it was lead poisoning. But--they have said so many things--so many things," she repeated, plainly distressed at the subject of her recent bereavement. "Your brother is not at home?" asked Kennedy, quickly changing the subject. "No," she answered, then with a flash as though lifting the veil of a confidence, added: "You know, neither Warner nor I have lived here much this year. He has been in New York most of the time and I have been at the settlement, as I already told you." She hesitated, as if wondering whether she should say more, then added quickly: "It has been repeated often enough; there is no reason why I shouldn't say it to you. Neither of us exactly approved of father's marriage." She checked herself and glanced about, somewhat with the air of one who has suddenly considered the possibility of being overheard. "May I have a glass of water?" asked Kennedy suddenly. "Why, certainly," she answered, going to the door, apparently eager for an excuse to find out whether there was some one on the other side of it. There was not, nor any indication that there had been. "Evidently she does not have any suspicions of THAT," remarked Kennedy in an undertone, half to himself. I had no chance to question him, for she returned almost immediately. Instead of drinking the water, however, he held it carefully up to the light. It was slightly turbid. "You drink the water from the tap?" he asked, as he poured some of it into a sterilized vial which he drew quickly from his vest pocket. "Certainly," she replied, for the moment nonplussed at his strange actions. "Everybody drinks the town water in Stratfield." A few more questions, none of which were of importance, and Kennedy and I excused ourselves. At the gate, instead of turning toward the town, however, Kennedy went on and entered the grounds of the Minturn house next door. The lawyer, I had understood, was a widower and, though he lived in Stratfield only part of the time, still maintained his house there. We rang the bell and a middle-aged housekeeper answered. "I am from the water company," he began politely. "We are testing the water, perhaps will supply consumers with filters. Can you let me have a sample?" She did not demur, but invited us in. As she drew the water, Craig watched her hands closely. She seemed to have difficulty in holding the glass, and as she handed it to him, I noticed a peculiar hanging down of the wrist. Kennedy poured the sample into a second vial, and I noticed that it was turbid, too. With no mention of the tragedy to her employer, he excused himself, and we walked slowly back to the road. Between the two houses Kennedy paused, and for several moments appeared to be studying them. We walked slowly back along the road to the town. As we passed the local drug store, Kennedy turned and sauntered in. He found it easy enough to get into conversation with the druggist, after making a small purchase, and in the course of a few minutes we found ourselves gossiping behind the partition that shut off the arcana of the prescription counter from the rest of the store. Gradually Kennedy led the conversation around to the point which he wanted, and asked, "I wish you'd let me fix up a little sulphureted hydrogen." "Go ahead," granted the druggist good-naturedly. "I guess you can do it. You know as much about drugs as I do. I can stand the smell, if you can." Kennedy smiled and set to work. Slowly he passed the gas through the samples of water he had taken from the two houses. As he did so the gas, bubbling through, made a blackish precipitate. "What is it?" asked the druggist curiously. "Lead sulphide," replied Kennedy, stroking his chin. "This is an extremely delicate test. Why, one can get a distinct brownish tinge if lead is present in even incredibly minute quantities." He continued to work over the vials ranged on the table before him. "The water contains, I should say, from ten to fifteen hundredths of a grain of lead to the gallon," he remarked finally. "Where did it come from?" asked the druggist, unable longer to restrain his curiosity. "I got it up at Pearcy's," Kennedy replied frankly, turning to observe whether the druggist might betray any knowledge of it. "That's strange," he replied in genuine surprise. "Our water in Stratfield is supplied by a company to a large area, and it has always seemed to me to be of great organic purity." "But the pipes are of lead, are they not?" asked Kennedy. "Y-yes," answered the druggist, "I think in most places the service pipes are of lead. But," he added earnestly as he saw the implication of his admission, "water has never to my knowledge been found to attack the pipes so as to affect its quality injuriously." He turned his own faucet and drew a glassful. "It is normally quite clear," he added, holding the glass up. It was in fact perfectly clear, and when he passed some of the gas through it nothing happened at all. Just then a man lounged into the store. "Hello, Doctor," greeted the druggist. "Here are a couple of fellows that have been investigating the water up at Pearcy's. They've found lead in it. That ought to interest you. This is Dr. Gunther," he introduced, turning to us. It was an unexpected encounter, one I imagine that Kennedy might have preferred to take place under other circumstances. But he was equal to the occasion. "We've been sent up here to look into the case for the New York Star," Kennedy said quickly. "I intended to come around to see you, but you have saved me the trouble." Dr. Gunther looked from one of us to the other. "Seems to me the New York papers ought to have enough to do without sending men all over the country making news," he grunted. "Well," drawled Kennedy quietly, "there seems to be a most remarkable situation up there at Pearcy's and Minturn's, too. As nearly as I can make out several people there are suffering from unmistakable signs of lead poisoning. There are the pains in the stomach, the colic, and then on the gums is that characteristic line of plumbic sulphide, the distinctive mark produced by lead. There is the wrist-drop, the eyesight affected, the partial paralysis, the hallucinations and a condition in old Pearcy's case almost bordering on insanity--to enumerate the symptoms that seem to be present in varying degrees in various persons in the two houses." Gunther looked at Kennedy, as if in doubt just how to take him. "That's what the coroner says, too--lead poisoning," put in the druggist, himself as keen as anyone else for a piece of local news, and evidently not averse to stimulating talk from Dr. Gunther, who had been Pearcy's physician. "That all seems to be true enough," replied Gunther at length guardedly. "I recognized that some time ago." "Why do you think it affects each so differently?" asked the druggist. Dr. Gunther settled himself easily back in a chair to speak as one having authority. "Well," he began slowly, "Miss Pearcy, of course, hasn't been living there much until lately. As for the others, perhaps this gentleman here from the Star knows that lead, once absorbed, may remain latent in the system and then make itself felt. It is like arsenic, an accumulative poison, slowly collecting in the body until the limit is reached, or until the body, becoming weakened from some other cause, gives way to it." He shifted his position slowly, and went on, as if defending the course of action he had taken in the case. "Then, too, you know, there is an individual as well as family and sex susceptibility to lead. Women are especially liable to lead poisoning, but then perhaps in this case Mrs. Pearcy comes of a family that is very resistant. There are many factors. Personally, I don't think Pearcy himself was resistant. Perhaps Minturn was not, either. At any rate, after Pearcy's death, it was I who advised Minturn to take the electrolysis cure in New York. I took him down there," added Gunther. "Confound it, I wish I had stayed with him. But I always found Josephson perfectly reliable in hydrotherapy with other patients I sent to him, and I understood that he had been very successful with cases sent to him by many physicians in the city." He paused and I waited anxiously to see whether Kennedy would make some reference to the discovery of the strychnine salts. "Have you any idea how the lead poisoning could have been caused?" asked Kennedy instead. Dr. Gunther shook his head. "It is a puzzle to me," he answered. "I am sure of only one thing. It could not be from working in lead, for it is needless to say that none of them worked." "Food?" Craig suggested. The doctor considered. "I had thought of that. I know that many cases of lead poisoning have been traced to the presence of the stuff in ordinary foods, drugs and drinks. I have examined the foods, especially the bread. They don't use canned goods. I even went so far as to examine the kitchen ware to see if there could be anything wrong with the glazing. They don't drink wines and beers, into which now and then the stuff seems to get." "You seem to have a good grasp of the subject," flattered Kennedy, as we rose to go. "I can hardly blame you for neglecting the water, since everyone here seems to be so sure of the purity of the supply." Gunther said nothing. I was not surprised, for, at the very least, no one likes to have an outsider come in and put his finger directly on the raw spot. What more there might be to it, I could only conjecture. We left the druggist's and Kennedy, glancing at his watch, remarked: "If you will go down to the station, Walter, and get that package we left there, I shall be much obliged to you. I want to make just one more stop, at the office of the water company, and I think I shall just about have time for it. There's a pretty good restaurant across the street. Meet me there, and by that time I shall know whether to carry out a little plan I have outlined or not." CHAPTER XXX THE ELECTROLYTIC MURDER We dined leisurely, which seemed strange to me, for it was not Kennedy's custom to let moments fly uselessly when he was on a case. However, I soon found out why it was. He was waiting for darkness. As soon as the lights began to glow in the little stores on the main street, we sallied forth, taking the direction of the Pearcy and Minturn houses. On the way he dropped into the hardware store and purchased a light spade and one of the small pocket electric flashlights, about which he wrapped a piece of cardboard in such a way as to make a most effective dark lantern. We trudged along in silence, occasionally changing from carrying the heavy package to the light spade. Both the Pearcy and Minturn houses were in nearly total darkness when we arrived. They set well back from the road and were plentifully shielded by shrubbery. Then, too, at night it was not a much frequented neighborhood. We could easily hear the footsteps of anyone approaching on the walk, and an occasional automobile gliding past did not worry us in the least. "I have calculated carefully from an examination of the water company's map," said Craig, "just where the water pipe of the two houses branches off from the main in the road." After a measurement or two from some landmark, we set to work a few feet inside, under cover of the bushes and the shadows, like two grave diggers. Kennedy had been wielding the spade vigorously for a few minutes when it touched something metallic. There, just beneath the frost line, we came upon the service pipe. He widened the hole, and carefully scraped off the damp earth that adhered to the pipe. Next he found a valve where he shut off the water and cut out a small piece of the pipe. "I hope they don't suspect anything like this in the houses with their water cut off," he remarked as he carefully split the piece open lengthwise and examined it under the light. On the interior of the pipe could be seen patchy lumps of white which projected about an eighth of an inch above the internal surface. As the pipe dried in the warm night air, they could easily be brushed off as a white powder. "What is it--strychnine?" I asked. "No," he replied, regarding it thoughtfully with some satisfaction. "That is lead carbonate. There can be no doubt that the turbidity of the water was due to this powder in suspension. A little dissolves in the water, while the scales and incrustations in fine particles are carried along in the current. As a matter of fact the amount necessary to make the water poisonous need not be large." He applied a little instrument to the cut ends of the pipe. As I bent over, I could see the needle on its dial deflected just a bit. "My voltmeter," he said, reading it, "shows that there is a current of about 1.8 volts passing through this pipe all the time." "Electrolysis of water pipes!" I exclaimed, thinking of statements I had heard by engineers. "That's what they mean by stray or vagabond currents, isn't it?" He had seized the lantern and was eagerly following up and down the line of the water pipe. At last he stopped, with a low exclamation, at a point where an electric light wire supplying the Minturn cottage crossed overhead. Fastened inconspicuously to the trunk of a tree which served as a support for the wire was another wire which led down from it and was buried in the ground. Craig turned up the soft earth as fast as he could, until he reached the pipe at this point. There was the buried wire wound several times around it. As quickly and as neatly as he could he inserted a connection between the severed ends of the pipe to restore the flow of water to the houses, turned on the water and covered up the holes he had dug. Then he unwrapped the package which we had tugged about all day, and in a narrow path between the bushes which led to the point where the wire had tapped the electric light feed he placed in a shallow hole in the ground a peculiar apparatus. As nearly as I could make it out, it consisted of two flat platforms between which, covered over and projected, was a slip of paper which moved forward, actuated by clockwork, and pressed on by a sort of stylus. Then he covered it over lightly with dirt so that, unless anyone had been looking for it, it would never be noticed. It was late when we reached the city again, but Kennedy had one more piece of work and that devolved on me. All the way down on the train he had been writing and rewriting something. "Walter," he said, as the train pulled into the station, "I want that published in to-morrow's papers." I looked over what he had written. It was one of the most sensational stories I have ever fathered, beginning, "Latest of the victims of the unknown poisoner of whole families in Stratfield, Connecticut, is Miss Isabel Pearcy, whose father, Randall Pearcy, died last week." I knew that it was a "plant" of some kind, for so far he had discovered no evidence that Miss Pearcy had been affected. What his purpose was, I could not guess, but I got the story printed. The next morning early Kennedy was quietly at work in the laboratory. "What is this treatment of lead poisoning by electrolysis?" I asked, now that there had come a lull when I might get an intelligible answer. "How does it work?" "Brand new, Walter," replied Kennedy. "It has been discovered that ions will flow directly through the membranes." "Ions?" I repeated. "What are ions?" "Travelers," he answered, smiling, "so named by Faraday from the Greek verb, io, to go. They are little positive and negative charges of electricity of which molecules are composed. You know some believe now that matter is really composed of electrical energy. I think I can explain it best by a simile I use with my classes. It is as though you had a ballroom in which the dancers in couples represent the neutral molecules. There are a certain number of isolated ladies and gentlemen--dissociated ions--" "Who don't know these new dances?" I interrupted. "They all know this dance," he laughed. "But, to be serious in the simile, suppose at one end of the room there is a large mirror and at the other a buffet with cigars and champagne. What happens to the dissociated ions?" "Well, I suppose you want me to say that the ladies gather about the mirror and the men about the buffet." "Exactly. And some of the dancing partners separate and follow the crowd. Well, that room presents a picture of what happens in an electrolytic solution at the moment when the electric current is passing through it." "Thanks," I laughed. "That was quite adequate to my immature understanding." Kennedy continued at work, checking up and arranging his data until the middle of the afternoon, when he went up to Stratfield. Having nothing better to do, I wandered out about town in the hope of running across some one with whom to while away the hours until Kennedy returned. I found out that, since yesterday, Broadway had woven an entirely new background for the mystery. Now it was rumored that the lawyer Minturn himself had been on very intimate terms with Mrs. Pearcy. I did not pay much attention to the rumor, for I knew that Broadway is constitutionally unable to believe that anybody is straight. Kennedy had commissioned me to keep in touch with Josephson and I finally managed to get around to the Baths, to find them still closed. As I was talking with him, a very muddy and dusty car pulled up at the door and a young man whose face was marred by the red congested blood vessels that are in some a mark of dissipation burst in on us. "What--closed up yet--Joe?" he asked. "Haven't they taken Minturn's body away?" "Yes, it was sent up to Stratfield to-day," replied the masseur, "but the coroner seems to want to worry me all he can." "Too bad. I was up almost all last night, and to-day I have been out in my car--tired to death. Thought I might get some rest here. Where are you sending the boys--to the Longacre?" "Yes. They'll take good care of you till I open up again. Hope to see you back again, then, Mr. Pearcy," he added, as the young man turned and hurried out to his car again. "That was that young Pearcy, you know. Nice boy--but living the life too fast. What's Kennedy doing--anything?" I did not like the jaunty bravado of the masseur which now seemed to be returning, since nothing definite had taken shape. I determined that he should not pump me, as he evidently was trying to do. I had at least fulfilled Kennedy's commission and felt that the sooner I left Josephson the better for both of us. I was surprised at dinner to receive a wire from Craig saying that he was bringing down Dr. Gunther, Mrs. Pearcy and Isabel to New York and asking me to have Warner Pearcy and Josephson at the laboratory at nine o'clock. By strategy I managed to persuade Pearcy to come, and as for Josephson, he could not very well escape, though I saw that as long as nothing more had happened, he was more interested in "fixing" the police so that he could resume business than anything else. As we entered the laboratory that night, Kennedy, who had left his party at a downtown hotel to freshen up, met us each at the door. Instead of conducting us in front of his laboratory table, which was the natural way, he led us singly around through the narrow space back of it. I recall that as I followed him, I half imagined that the floor gave way just a bit, and there flashed over me, by a queer association of ideas, the recollection of having visited an amusement park not long before where merely stepping on an innocent-looking section of the flooring had resulted in a tremendous knocking and banging beneath, much to the delight of the lovers of slap-stick humor. This was serious business, however, and I quickly banished the frivolous thought from my mind. "The discovery of poison, and its identification," began Craig at last when we had all arrived and were seated about him, "often involves not only the use of chemistry but also a knowledge of the chemical effect of the poison on the body, and the gross as well as microscopic changes which it produces in various tissues and organs--changes, some due to mere contact, others to the actual chemicophysiological reaction between the poison and the body." His hand was resting on the poles of a large battery, as he proceeded: "Every day the medical detective plays a more and more important part in the detection of crime, and I might say that, except in the case of crime complicated by a lunacy plea, his work has earned the respect of the courts and of detectives, while in the case of insanity the discredit is the fault rather of the law itself. The ways in which the doctor can be of use in untangling the facts in many forms of crime have become so numerous that the profession of medical detective may almost be called a specialty." Kennedy repeated what he had already told me about electrolysis, then placed between the poles of the battery a large piece of raw beef. He covered the negative electrode with blotting paper and soaked it in a beaker near at hand. "This solution," he explained, "is composed of potassium iodide. In this other beaker I have a mixture of ordinary starch." He soaked the positive electrode in the starch and then jammed the two against the soft red meat. Then he applied the current. A few moments later he withdrew the positive electrode. Both it and the meat under it were blue! "What has happened?" he asked. "The iodine ions have actually passed through the beef to the positive pole and the paper on the electrode. Here we have starch iodide." It was a startling idea, this of the introduction of a substance by electrolysis. "I may say," he resumed, "that the medical view of electricity is changing, due in large measure to the genius of the Frenchman, Dr. Leduc. The body, we know, is composed largely of water, with salts of soda and potash. It is an excellent electrolyte. Yet most doctors regard the introduction of substances by the electric current as insignificant or nonexistent. But on the contrary the introduction of drugs by electrolysis is regular and far from being insignificant may very easily bring about death. "That action," he went on, looking from one of us to another, "may be therapeutic, as in the cure for lead poisoning by removing the lead, or it may be toxic--as in the case of actually introducing such a poison as strychnine into the body by the same forces that will remove the lead." He paused a moment, to enforce the point which had already been suggested. I glanced about hastily. If anyone in his little audience was guilty, no one betrayed it, for all were following him, fascinated. Yet in the wildly throbbing brain of some one of them the guilty knowledge must be seared indelibly. Would the mere accusation be enough to dissociate the truth from, that brain or would Kennedy have to resort to other means? "Some one," he went on, in a low, tense voice, leaning forward, "some one who knew this effect placed strychnine salts on one of the electrodes of the bath which Owen Minturn was to use." He did not pause. Evidently he was planning to let the force of his exposure be cumulative, until from its sheer momentum it carried everything before it. "Walter," he ordered quickly. "Lend me a hand." Together we moved the laboratory table as he directed. There, in the floor, concealed by the shadow, he had placed the same apparatus which I had seen him bury in the path between the Pearcy and Minturn estates at Stratfield. We scarcely breathed. "This," he explained rapidly, "is what is known as a kinograph--the invention of Professor HeleShaw of London. It enables me to identify a person by his or her walk. Each of you as you entered this room has passed over this apparatus and has left a different mark on the paper which registers." For a moment he stopped, as if gathering strength for the final assault. "Until late this afternoon I had this kinograph secreted at a certain place in Stratfield. Some one had tampered with the leaden water pipes and the electric light cable. Fearful that the lead poisoning brought on by electrolysis might not produce its result in the intended victim, that person took advantage of the new discoveries in electrolysis to complete that work by introducing the deadly strychnine during the very process of cure of the lead poisoning." He slapped down a copy of a newspaper. "In the news this morning I told just enough of what I had discovered and colored it in such a way that I was sure I would arouse apprehension. I did it because I wanted to make the criminal revisit the real scene of the crime. There was a double motive now--to remove the evidence and to check the spread of the poisoning." He reached over, tore off the paper with a quick, decisive motion, and laid it beside another strip, a little discolored by moisture, as though the damp earth had touched it. "That person, alarmed lest something in the cleverly laid plot, might be discovered, went to a certain spot to remove the traces of the diabolical work which were hidden there. My kinograph shows the footsteps, shows as plainly as if I had been present, the exact person who tried to obliterate the evidence." An ashen pallor seemed to spread over the face of Miss Pearcy, as Kennedy shot out the words. "That person," he emphasized, "had planned to put out of the way one who had brought disgrace on the Pearcy family. It was an act of private justice." Mrs. Pearcy could stand the strain no longer. She had broken down and was weeping incoherently. I strained my ears to catch what she was murmuring. It was Minturn's name, not Gunther's, that was on her lips. "But," cried Kennedy, raising an accusatory finger from the kinograph tracing and pointing it like the finger of Fate itself, "but the self-appointed avenger forgot that the leaden water pipe was common to the two houses. Old Mr. Pearcy, the wronged, died first. Isabel has guessed the family skeleton--has tried hard to shield you, but, Warner Pearcy, you are the murderer!" CHAPTER XXXI THE EUGENIC BRIDE Scandal, such as that which Kennedy unearthed in this Pearcy case, was never much to his liking, yet he seemed destined, about this period of his career, to have a good deal of it. We had scarcely finished with the indictment that followed the arrest of young Pearcy, when we were confronted by a situation which was as unique as it was intensely modern. "There's absolutely no insanity in Eugenia's family," I heard a young man remark to Kennedy, as my key turned in the lock of the laboratory door. For a moment I hesitated about breaking in on a confidential conference, then reflected that, as they had probably already heard me at the lock, I had better go in and excuse myself. As I swung the door open, I saw a young man pacing up and down the laboratory nervously, too preoccupied even to notice the slight noise I had made. He paused in his nervous walk and faced Kennedy, his back to me. "Kennedy," he said huskily, "I wouldn't care if there was insanity in her family--for, my God!--the tragedy of it all now--I love her!" He turned, following Kennedy's eyes in my direction, and I saw on his face the most haggard, haunting look of anxiety that I had ever seen on a young person. Instantly I recognized from the pictures I had seen in the newspapers young Quincy Atherton, the last of this famous line of the family, who had attracted a great deal of attention several months previously by what the newspapers had called his search through society for a "eugenics bride," to infuse new blood into the Atherton stock. "You need have no fear that Mr. Jameson will be like the other newspaper men," reassured Craig, as he introduced us, mindful of the prejudice which the unpleasant notoriety of Atherton's marriage had already engendered in his mind. I recalled that when I had first heard of Atherton's "eugenic marriage," I had instinctively felt a prejudice against the very idea of such cold, calculating, materialistic, scientific mating, as if one of the last fixed points were disappearing in the chaos of the social and sex upheaval. Now, I saw that one great fact of life must always remain. We might ride in hydroaeroplanes, delve into the very soul by psychanalysis, perhaps even run our machines by the internal forces of radium--even marry according to Galton or Mendel. But there would always be love, deep passionate love of the man for the woman, love which all the discoveries of science might perhaps direct a little less blindly, but the consuming flame of which not all the coldness of science could ever quench. No tampering with the roots of human nature could ever change the roots. I must say that I rather liked young Atherton. He had a frank, open face, the most prominent feature of which was his somewhat aristocratic nose. Otherwise he impressed one as being the victim of heredity in faults, if at all serious, against which he was struggling heroically. It was a most pathetic story which he told, a story of how his family had degenerated from the strong stock of his ancestors until he was the last of the line. He told of his education, how he had fallen, a rather wild youth bent in the footsteps of his father who had been a notoriously good clubfellow, under the influence of a college professor, Dr. Crafts, a classmate of his father's, of how the professor had carefully and persistently fostered in him an idea that had completely changed him. "Crafts always said it was a case of eugenics against euthenics," remarked Atherton, "of birth against environment. He would tell me over and over that birth gave me the clay, and it wasn't such bad clay after all, but that environment would shape the vessel." Then Atherton launched into a description of how he had striven to find a girl who had the strong qualities his family germ plasm seemed to have lost, mainly, I gathered, resistance to a taint much like manic depressive insanity. And as he talked, it was borne in on me that, after all, contrary to my first prejudice, there was nothing very romantic indeed about disregarding the plain teachings of science on the subject of marriage and one's children. In his search for a bride, Dr. Crafts, who had founded a sort of Eugenics Bureau, had come to advise him. Others may have looked up their brides in Bradstreet's, or at least the Social Register. Atherton had gone higher, had been overjoyed to find that a girl he had met in the West, Eugenia Gilman, measured up to what his friend told him were the latest teachings of science. He had been overjoyed because, long before Crafts had told him, he had found out that he loved her deeply. "And now," he went on, half choking with emotion, "she is apparently suffering from just the same sort of depression as I myself might suffer from if the recessive trait became active." "What do you mean, for instance?" asked Craig. "Well, for one thing, she has the delusion that my relatives are persecuting her." "Persecuting her?" repeated Craig, stifling the remark that that was not in itself a new thing in this or any other family. "How?" "Oh, making her feel that, after all, it is Atherton family rather than Gilman health that counts--little remarks that when our baby is born, they hope it will resemble Quincy rather than Eugenia, and all that sort of thing, only worse and more cutting, until the thing has begun to prey on her mind." "I see," remarked Kennedy thoughtfully. "But don't you think this is a case for a--a doctor, rather than a detective?" Atherton glanced up quickly. "Kennedy," he answered slowly, "where millions of dollars are involved, no one can guess to what lengths the human mind will go--no one, except you." "Then you have suspicions of something worse?" "Y-yes--but nothing definite. Now, take this case. If I should die childless, after my wife, the Atherton estate would descend to my nearest relative, Burroughs Atherton, a cousin." "Unless you willed it to--" "I have already drawn a will," he interrupted, "and in case I survive Eugenia and die childless, the money goes to the founding of a larger Eugenics Bureau, to prevent in the future, as much as possible, tragedies such as this of which I find myself a part. If the case is reversed, Eugenia will get her third and the remainder will go to the Bureau or the Foundation, as I call the new venture. But," and here young Atherton leaned forward and fixed his large eyes keenly on us, "Burroughs might break the will. He might show that I was of unsound mind, or that Eugenia was, too." "Are there no other relatives?" "Burroughs is the nearest," he replied, then added frankly, "I have a second cousin, a young lady named Edith Atherton, with whom both Burroughs and I used to be very friendly." It was evident from the way he spoke that he had thought a great deal about Edith Atherton, and still thought well of her. "Your wife thinks it is Burroughs who is persecuting her?" asked Kennedy. Atherton shrugged his shoulders. "Does she get along badly with Edith? She knows her I presume?" "Of course. The fact is that since the death of her mother, Edith has been living with us. She is a splendid girl, and all alone in the world now, and I had hopes that in New York she might meet some one and marry well." Kennedy was looking squarely at Atherton, wondering whether he might ask a question without seeming impertinent. Atherton caught the look, read it, and answered quite frankly, "To tell the truth, I suppose I might have married Edith, before I met Eugenia, if Professor Crafts had not dissuaded me. But it wouldn't have been real love--nor wise. You know," he went on more frankly, now that the first hesitation was over and he realized that if he were to gain anything at all by Kennedy's services, there must be the utmost candor between them, "you know cousins may marry if the stocks are known to be strong. But if there is a defect, it is almost sure to be intensified. And so I--I gave up the idea--never had it, in fact, so strongly as to propose to her. And when I met Eugenia all the Athertons on the family tree couldn't have bucked up against the combination." He was deadly in earnest as he arose from the chair into which he had dropped after I came in. "Oh, it's terrible--this haunting fear, this obsession that I have had, that, in spite of all I have tried to do, some one, somehow, will defeat me. Then comes the situation, just at a time when Eugenia and I feel that we have won against Fate, and she in particular needs all the consideration and care in the world--and--and I am defeated." Atherton was again pacing the laboratory. "I have my car waiting outside," he pleaded. "I wish you would go with me to see Eugenia--now." It was impossible to resist him. Kennedy rose and I followed, not without a trace of misgiving. The Atherton mansion was one of the old houses of the city, a somber stone dwelling with a garden about it on a downtown square, on which business was already encroaching. We were admitted by a servant who seemed to walk over the polished floors with stealthy step as if there was something sacred about even the Atherton silence. As we waited in a high-ceilinged drawing-room with exquisite old tapestries on the walls, I could not help feeling myself the influence of wealth and birth that seemed to cry out from every object of art in the house. On the longer wall of the room, I saw a group of paintings. One, I noted especially, must have been Atherton's ancestor, the founder of the line. There was the same nose in Atherton, for instance, a striking instance of heredity. I studied the face carefully. There was every element of strength in it, and I thought instinctively that, whatever might have been the effects of in-breeding and bad alliances, there must still be some of that strength left in the present descendant of the house of Atherton. The more I thought about the house, the portrait, the whole case, the more unable was I to get out of my head a feeling that though I had not been in such a position before, I had at least read or heard something of which it vaguely reminded me. Eugenia Atherton was reclining listlessly in her room in a deep leather easy chair, when Atherton took us up at last. She did not rise to greet us, but I noted that she was attired in what Kennedy once called, as we strolled up the Avenue, "the expensive sloppiness of the present styles." In her case the looseness with which her clothes hung was exaggerated by the lack of energy with which she wore them. She had been a beautiful girl, I knew. In fact, one could see that she must have been. Now, however, she showed marks of change. Her eyes were large, and protruding, not with the fire of passion which is often associated with large eyes, but dully, set in a puffy face, a trifle florid. Her hands seemed, when she moved them, to shake with an involuntary tremor, and in spite of the fact that one almost could feel that her heart and lungs were speeding with energy, she had lost weight and no longer had the full, rounded figure of health. Her manner showed severe mental disturbance, indifference, depression, a distressing deterioration. All her attractive Western breeziness was gone. One felt the tragedy of it only too keenly. "I have asked Professor Kennedy, a specialist, to call, my dear," said Atherton gently, without mentioning what the specialty was. "Another one?" she queried languorously. There was a colorless indifference in the tone which was almost tragic. She said the words slowly and deliberately, as though even her mind worked that way. From the first, I saw that Kennedy had been observing Eugenia Atherton keenly. And in the role of specialist in nervous diseases he was enabled to do what otherwise would have been difficult to accomplish. Gradually, from observing her mental condition of indifference which made conversation extremely difficult as well as profitless, he began to consider her physical condition. I knew him well enough to gather from his manner alone as he went on that what had seemed at the start to be merely a curious case, because it concerned the Athertons, was looming up in his mind as unusual in itself, and was interesting him because it baffled him. Craig had just discovered that her pulse was abnormally high, and that consequently she had a high temperature, and was sweating profusely. "Would you mind turning your head, Mrs. Atherton?" he asked. She turned slowly, half way, her eyes fixed vacantly on the floor until we could see the once striking profile. "No, all the way around, if you please," added Kennedy. She offered no objection, not the slightest resistance. As she turned her head as far as she could, Kennedy quickly placed his forefinger and thumb gently on her throat, the once beautiful throat, now with skin harsh and rough. Softly he moved his fingers just a fraction of an inch over the so-called "Adam's apple" and around it for a little distance. "Thank you," he said. "Now around to the other side." He made no other remark as he repeated the process, but I fancied I could tell that he had had an instant suspicion of something the moment he touched her throat. He rose abstractedly, bowed, and we started to leave the room, uncertain whether she knew or cared. Quincy had fixed his eyes silently on Craig, as if imploring him to speak, but I knew how unlikely that was until he had confirmed his suspicion to the last slightest detail. We were passing through a dressing room in the suite when we met a tall young woman, whose face I instantly recognized, not because I had ever seen it before, but because she had the Atherton nose so prominently developed. "My cousin, Edith," introduced Quincy. We bowed and stood for a moment chatting. There seemed to be no reason why we should leave the suite, since Mrs. Atherton paid so little attention to us even when we had been in the same room. Yet a slight movement in her room told me that in spite of her lethargy she seemed to know that we were there and to recognize who had joined us. Edith Atherton was a noticeable woman, a woman of temperament, not beautiful exactly, but with a stateliness about her, an aloofness. The more I studied her face, with its thin sensitive lips and commanding, almost imperious eyes, the more there seemed to be something peculiar about her. She was dressed very simply in black, but it was the simplicity that costs. One thing was quite evident--her pride in the family of Atherton. And as we talked, it seemed to be that she, much more than Eugenia in her former blooming health, was a part of the somber house. There came over me again the impression I had received before that I had read or heard something like this case before. She did not linger long, but continued her stately way into the room where Eugenia sat. And at once it flashed over me what my impression, indefinable, half formed, was. I could not help thinking, as I saw her pass, of the lady Madeline in "The Fall of the House of Usher." CHAPTER XXXII THE GERM PLASM I regarded her with utter astonishment and yet found it impossible to account for such a feeling. I looked at Atherton, but on his face I could see nothing but a sort of questioning fear that only increased my illusion, as if he, too, had only a vague, haunting premonition of something terrible impending. Almost I began to wonder whether the Atherton house might not crumble under the fierceness of a sudden whirlwind, while the two women in this case, one representing the wasted past, the other the blasted future, dragged Atherton down, as the whole scene dissolved into some ghostly tarn. It was only for a moment, and then I saw that the more practical Kennedy had been examining some bottles on the lady's dresser before which we had paused. One was a plain bottle of pellets which might have been some homeopathic remedy. "Whatever it is that is the matter with Eugenia," remarked Atherton, "it seems to have baffled the doctors so far." Kennedy said nothing, but I saw that he had clumsily overturned the bottle and absently set it up again, as though his thoughts were far away. Yet with a cleverness that would have done credit to a professor of legerdemain he had managed to extract two or three of the pellets. "Yes," he said, as he moved slowly toward the staircase in the wide hall, "most baffling." Atherton was plainly disappointed. Evidently he had expected Kennedy to arrive at the truth and set matters right by some sudden piece of wizardry, and it was with difficulty that he refrained from saying so. "I should like to meet Burroughs Atherton," he remarked as we stood in the wide hall on the first floor of the big house. "Is he a frequent visitor?" "Not frequent," hastened Quincy Atherton, in a tone that showed some satisfaction in saying it. "However, by a lucky chance he has promised to call to-night--a mere courtesy, I believe, to Edith, since she has come to town on a visit." "Good!" exclaimed Kennedy. "Now, I leave it to you, Atherton, to make some plausible excuse for our meeting Burroughs here." "I can do that easily." "I shall be here early," pursued Kennedy as we left. Back again in the laboratory to which Atherton insisted on accompanying us in his car, Kennedy busied himself for a few minutes, crushing up one of the tablets and trying one or two reactions with some of the powder dissolved, while I looked on curiously. "Craig," I remarked contemplatively, after a while, "how about Atherton himself? Is he really free from the--er--stigmata, I suppose you call them, of insanity?" "You mean, may the whole trouble lie with him?" he asked, not looking up from his work. "Yes--and the effect on her be a sort of reflex, say, perhaps the effect of having sold herself for money and position. In other words, does she, did she, ever love him? We don't know that. Might it not prey on her mind, until with the kind help of his precious relatives even Nature herself could not stand the strain--especially in the delicate condition in which she now finds herself?" I must admit that I felt the utmost sympathy for the poor girl whom we had just seen such a pitiable wreck. Kennedy closed his eyes tightly until they wrinkled at the corners. "I think I have found out the immediate cause of her trouble," he said simply, ignoring my suggestion. "What is it?" I asked eagerly. "I can't imagine how they could have failed to guess it, except that they never would have suspected to look for anything resembling exophthalmic goiter in a person of her stamina," he answered, pronouncing the word slowly. "You have heard of the thyroid gland in the neck?" "Yes?" I queried, for it was a mere name to me. "It is a vascular organ lying under the chin with a sort of little isthmus joining the two parts on either side of the windpipe," he explained. "Well, when there is any deterioration of those glands through any cause, all sorts of complications may arise. The thyroid is one of the so-called ductless glands, like the adrenals above the kidneys, the pineal gland and the pituitary body. In normal activity they discharge into the blood substances which are carried to other organs and are now known to be absolutely essential. "The substances which they secrete are called 'hormones'--those chemical messengers, as it were, by which many of the processes of the body are regulated. In fact, no field of experimental physiology is richer in interest than this. It seems that few ordinary drugs approach in their effects on metabolism the hormones of the thyroid. In excess they produce such diseases as exophthalmic goiter, and goiter is concerned with the enlargement of the glands and surrounding tissues beyond anything like natural size. Then, too, a defect in the glands causes the disease known as myxedema in adults and cretinism in children. Most of all, the gland seems to tell on the germ plasm of the body, especially in women." I listened in amazement, hardly knowing what to think. Did his discovery portend something diabolical, or was it purely a defect in nature which Dr. Crafts of the Eugenics Bureau had overlooked? "One thing at a time, Walter," cautioned Kennedy, when I put the question to him, scarcely expecting an answer yet. That night in the old Atherton mansion, while we waited for Borroughs to arrive, Kennedy, whose fertile mind had contrived to kill at least two birds with one stone, busied himself by cutting in on the regular telephone line and placing an extension of his own in a closet in the library. To it he attached an ordinary telephone receiver fastened to an arrangement which was strange to me. As nearly as I can describe it, between the diaphragm of the regular receiver and a brownish cylinder, like that of a phonograph, and with a needle attached, was fitted an air chamber of small size, open to the outer air by a small hole to prevent compression. The work was completed expeditiously, but we had plenty of time to wait, for Borroughs Atherton evidently did not consider that an evening had fairly begun until nine o'clock. He arrived at last, however, rather tall, slight of figure, narrow-shouldered, designed for the latest models of imported fabrics. It was evident merely by shaking hands with Burroughs that he thought both the Athertons and the Burroughses just the right combination. He was one of those few men against whom I conceive an instinctive prejudice, and in this case I felt positive that, whatever faults the Atherton germ plasm might contain, he had combined others from the determiners of that of the other ancestors he boasted. I could not help feeling that Eugenia Atherton was in about as unpleasant an atmosphere of social miasma as could be imagined. Burroughs asked politely after Eugenia, but it was evident that the real deference was paid to Edith Atherton and that they got along very well together. Burroughs excused himself early, and we followed soon after. "I think I shall go around to this Eugenics Bureau of Dr. Crafts," remarked Kennedy the next day, after a night's consideration of the case. The Bureau occupied a floor in a dwelling house uptown which had been remodeled into an office building. Huge cabinets were stacked up against the walls, and in them several women were engaged in filing blanks and card records. Another part of the office consisted of an extensive library on eugenic subjects. Dr. Crafts, in charge of the work, whom we found in a little office in front partitioned off by ground glass, was an old man with an alert, vigorous mind on whom the effects of plain living and high thinking showed plainly. He was looking over some new blanks with a young woman who seemed to be working with him, directing the force of clerks as well as the "field workers," who were gathering the vast mass of information which was being studied. As we introduced ourselves, he introduced Dr. Maude Schofield. "I have heard of your eugenic marriage contests," began Kennedy, "more especially of what you have done for Mr. Quincy Atherton." "Well--not exactly a contest in that case, at least," corrected Dr. Crafts with an indulgent smile for a layman. "No," put in Dr. Schofield, "the Eugenics Bureau isn't a human stock farm." "I see," commented Kennedy, who had no such idea, anyhow. He was always lenient with anyone who had what he often referred to as the "illusion of grandeur." "We advise people sometimes regarding the desirability or the undesirability of marriage," mollified Dr. Crafts. "This is a sort of clearing house for scientific race investigation and improvement." "At any rate," persisted Kennedy, "after investigation, I understand, you advised in favor of his marriage with Miss Gilman." "Yes, Eugenia Gilman seemed to measure well up to the requirements in such a match. Her branch of the Gilmans has always been of the vigorous, pioneering type, as well as intellectual. Her father was one of the foremost thinkers in the West; in fact had long held ideas on the betterment of the race. You see that in the choice of a name for his daughter--Eugenia." "Then there were no recessive traits in her family," asked Kennedy quickly, "of the same sort that you find in the Athertons?" "None that we could discover," answered Dr. Crafts positively. "No epilepsy, no insanity of any form?" "No. Of course, you understand that almost no one is what might be called eugenically perfect. Strictly speaking, perhaps not over two or three per cent. of the population even approximates that standard. But it seemed to me that in everything essential in this case, weakness latent in Atherton was mating strength in Eugenia and the same way on her part for an entirely different set of traits." "Still," considered Kennedy, "there might have been something latent in her family germ plasm back of the time through which you could trace it?" Dr. Crafts shrugged his shoulders. "There often is, I must admit, something we can't discover because it lies too far back in the past." "And likely to crop out after skipping generations," put in Maude Schofield. She evidently did not take the same liberal view in the practical application of the matter expressed by her chief. I set it down to the ardor of youth in a new cause, which often becomes the saner conservatism of maturity. "Of course, you found it much easier than usual to get at the true family history of the Athertons," pursued Kennedy. "It is an old family and has been prominent for generations." "Naturally," assented Dr. Crafts. "You know Burroughs Atherton on both lines of descent?" asked Kennedy, changing the subject abruptly. "Yes, fairly well," answered Crafts. "Now, for example," went on Craig, "how would you advise him to marry?" I saw at once that he was taking this subterfuge as a way of securing information which might otherwise have been withheld if asked for directly. Maude Schofield also saw it, I fancied, but this time said nothing. "They had a grandfather who was a manic depressive on the Atherton side," said Crafts slowly. "Now, no attempt has ever been made to breed that defect out of the family. In the case of Burroughs, it is perhaps a little worse, for the other side of his ancestry is not free from the taint of alcoholism." "And Edith Atherton?" "The same way. They both carry it. I won't go into the Mendelian law on the subject. We are clearing up much that is obscure. But as to Burroughs, he should marry, if at all, some one without that particular taint. I believe that in a few generations by proper mating most taints might be bred out of families." Maude Schofield evidently did not agree with Dr. Crafts on some point, and, noticing it, he seemed to be in the position both of explaining his contention to us and of defending it before his fair assistant. "It is my opinion, as far as I have gone with the data," he added, "that there is hope for many of those whose family history shows certain nervous taints. A sweeping prohibition of such marriages would be futile, perhaps injurious. It is necessary that the mating be carefully made, however, to prevent intensifying the taint. You see, though I am a eugenist I am not an extremist." He paused, then resumed argumentatively: "Then there are other questions, too, like that of genius with its close relation to manic depressive insanity. Also, there is decrease enough in the birth rate, without adding an excuse for it. No, that a young man like Atherton should take the subject seriously, instead of spending his time in wild dissipation, like his father, is certainly creditable, argues in itself that there still must exist some strength in his stock. "And, of course," he continued warmly, "when I say that weakness in a trait--not in all traits, by any means--should marry strength and that strength may marry weakness, I don't mean that all matches should be like that. If we are too strict we may prohibit practically all marriages. In Atherton's case, as in many another, I felt that I should interpret the rule as sanely as possible." "Strength should marry strength, and weakness should never marry," persisted Maude Schofield. "Nothing short of that will satisfy the true eugenist." "Theoretically," objected Crafts. "But Atherton was going to marry, anyhow. The only thing for me to do was to lay down a rule which he might follow safely. Besides, any other rule meant sure disaster." "It was the only rule with half a chance of being followed and at any rate," drawled Kennedy, as the eugenists wrangled, "what difference does it make in this case? As nearly as I can make out it is Mrs. Atherton herself, not Atherton, who is ill." Maude Schofield had risen to return to supervising a clerk who needed help. She left us, still unconvinced. "That is a very clever girl," remarked Kennedy as she shut the door and he scanned Dr. Crafts' face dosely. "Very," assented the Doctor. "The Schofields come of good stock?" hazarded Kennedy. "Very," assented Dr. Crafts again. Evidently he did not care to talk about individual cases, and I felt that the rule was a safe one, to prevent Eugenics from becoming Gossip. Kennedy thanked him for his courtesy, and we left apparently on the best of terms both with Crafts and his assistant. CHAPTER XXXIII THE SEX CONTROL I did not see Kennedy again that day until late in the afternoon, when he came into the laboratory carrying a small package. "Theory is one thing, practice is another," he remarked, as he threw his hat and coat into a chair. "Which means--in this case?" I prompted. "Why, I have just seen Atherton. Of course I didn't repeat our conversation of this morning, and I'm glad I didn't. He almost makes me think you are right, Walter. He's obsessed by the fear of Burroughs. Why, he even told me that Burroughs had gone so far as to take a leaf out of his book, so to speak, get in touch with the Eugenics Bureau as if to follow his footsteps, but really to pump them about Atherton himself. Atherton says it's all Burroughs' plan to break his will and that the fellow has even gone so far as to cultivate the acquaintance of Maude Schofield, knowing that he will get no sympathy from Crafts." "First it was Edith Atherton, now it is Maude Schofield that he hitches up with Burroughs," I commented. "Seems to me that I have heard that one of the first signs of insanity is belief that everyone about the victim is conspiring against him. I haven't any love for any of them--but I must be fair." "Well," said Kennedy, unwrapping the package, "there IS this much to it. Atherton says Burroughs and Maude Schofield have been seen together more than once--and not at intellectual gatherings either. Burroughs is a fascinating fellow to a woman, if he wants to be, and the Schofields are at least the social equals of the Burroughs. Besides," he added, "in spite of eugenics, feminism, and all the rest--sex, like murder, will out. There's no use having any false ideas about THAT. Atherton may see red--but, then, he was quite excited." "Over what?" I asked, perplexed more than ever at the turn of events. "He called me up in the first place. 'Can't you do something?' he implored. 'Eugenia is getting worse all the time.' She is, too. I saw her for a moment, and she was even more vacant than yesterday." The thought of the poor girl in the big house somehow brought over me again my first impression of Poe's story. Kennedy had unwrapped the package which proved to be the instrument he had left in the closet at Atherton's. It was, as I had observed, like an ordinary wax cylinder phonograph record. "You see," explained Kennedy, "it is nothing more than a successful application at last of, say, one of those phonographs you have seen in offices for taking dictation, placed so that the feebler vibrations of the telephone affect it. Let us see what we have here." He had attached the cylinder to an ordinary phonograph, and after a number of routine calls had been run off, he came to this, in voices which we could only guess at but not recognize, for no names were used. "How is she to-day?" "Not much changed--perhaps not so well." "It's all right, though. That is natural. It is working well. I think you might increase the dose, one tablet." "You're sure it is all right?" (with anxiety). "Oh, positively--it has been done in Europe." "I hope so. It must be a boy--and an ATHERTON?" "Never fear." That was all. Who was it? The voices were unfamiliar to me, especially when repeated mechanically. Besides they may have been disguised. At any rate we had learned something. Some one was trying to control the sex of the expected Atherton heir. But that was about all. Who it was, we knew no better, apparently, than before. Kennedy did not seem to care much, however. Quickly he got Quincy Atherton on the wire and arranged for Atherton to have Dr. Crafts meet us at the house at eight o'clock that night, with Maude Schofield. Then he asked that Burroughs Atherton be there, and of course, Edith and Eugenia. We arrived almost as the clock was striking, Kennedy carrying the phonograph record and another blank record, and a boy tugging along the machine itself. Dr. Crafts was the next to appear, expressing surprise at meeting us, and I thought a bit annoyed, for he mentioned that it had been with reluctance that he had had to give up some work he had planned for the evening. Maude Schofield, who came with him, looked bored. Knowing that she disapproved of the match with Eugenia, I was not surprised. Burroughs arrived, not as late as I had expected, but almost insultingly supercilious at finding so many strangers at what Atherton had told him was to be a family conference, in order to get him to come. Last of all Edith Atherton descended the staircase, the personification of dignity, bowing to each with a studied graciousness, as if distributing largess, but greeting Burroughs with an air that plainly showed how much thicker was blood than water. Eugenia remained upstairs, lethargic, almost cataleptic, as Atherton told us when we arrived. "I trust you are not going to keep us long, Quincy," yawned Burroughs, looking ostentatiously at his watch. "Only long enough for Professor Kennedy to say a few words about Eugenia," replied Atherton nervously, bowing to Kennedy. Kennedy cleared his throat slowly. "I don't know that I have much to say," began Kennedy, still seated. "I suppose Mr. Atherton has told you I have been much interested in the peculiar state of health of Mrs. Atherton?" No one spoke, and he went on easily: "There is something I might say, however, about the--er--what I call the chemistry of insanity. Among the present wonders of science, as you doubtless know, none stirs the imagination so powerfully as the doctrine that at least some forms of insanity are the result of chemical changes in the blood. For instance, ill temper, intoxication, many things are due to chemical changes in the blood acting on the brain. "Go further back. Take typhoid fever with its delirium, influenza with its suicide mania. All due to toxins--poisons. Chemistry--chemistry--all of them chemistry." Craig had begun carefully so as to win their attention. He had it as he went on: "Do we not brew within ourselves poisons which enter the circulation and pervade the system? A sudden emotion upsets the chemistry of the body. Or poisonous food. Or a drug. It affects many things. But we could never have had this chemical theory unless we had had physiological chemistry--and some carry it so far as to say that the brain secretes thought, just as the liver secretes bile, that thoughts are the results of molecular changes." "You are, then, a materialist of the most pronounced type," asserted Dr. Crafts. Kennedy had been reaching over to a table, toying with the phonograph. As Crafts spoke he moved a key, and I suspected that it was in order to catch the words. "Not entirely," he said. "No more than some eugenists." "In our field," put in Maude Schofield, "I might express the thought this way--the sociologist has had his day; now it is the biologist, the eugenist." "That expresses it," commented Kennedy, still tinkering with the record. "Yet it does not mean that because we have new ideas, they abolish the old. Often they only explain, amplify, supplement. For instance," he said, looking up at Edith Atherton, "take heredity. Our knowledge seems new, but is it? Marriages have always been dictated by a sort of eugenics. Society is founded on that." "Precisely," she answered. "The best families have always married into the best families. These modern notions simply recognize what the best people have always thought--except that it seems to me," she added with a sarcastic flourish, "people of no ancestry are trying to force themselves in among their betters." "Very true, Edith," drawled Burroughs, "but we did not have to be brought here by Quincy to learn that." Quincy Atherton had risen during the discussion and had approached Kennedy. Craig continued to finger the phonograph abstractedly, as he looked up. "About this--this insanity theory," he whispered eagerly. "You think that the suspicions I had have been justified?" I had been watching Kennedy's hand. As soon as Atherton had started to speak, I saw that Craig, as before, had moved the key, evidently registering what he said, as he had in the case of the others during the discussion. "One moment, Atherton," he whispered in reply, "I'm coming to that. Now," he resumed aloud, "there is a disease, or a number of diseases, to which my remarks about insanity a while ago might apply very well. They have been known for some time to arise from various affections of the thyroid glands in the neck. These glands, strange to say, if acted on in certain ways can cause degenerations of mind and body, which are well known, but in spite of much study are still very little understood. For example, there is a definite interrelation between them and sex--especially in woman." Rapidly he sketched what he had already told me of the thyroid and the hormones. "These hormones," added Kennedy, "are closely related to many reactions in the body, such as even the mother's secretion of milk at the proper time and then only. That and many other functions are due to the presence and character of these chemical secretions from the thyroid and other ductless glands. It is a fascinating study. For we know that anything that will upset--reduce or increase--the hormones is a matter intimately concerned with health. Such changes," he said earnestly, leaning forward, "might be aimed directly at the very heart of what otherwise would be a true eugenic marriage. It is even possible that loss of sex itself might be made to follow deep changes of the thyroid." He stopped a moment. Even if he had accomplished nothing else he had struck a note which had caused the Athertons to forget their former superciliousness. "If there is an oversupply of thyroid hormones," continued Craig, "that excess will produce many changes, for instance a condition very much like exophthalmic goiter. And," he said, straightening up, "I find that Eugenia Atherton has within her blood an undue proportion of these thyroid hormones. Now, is it overfunction of the glands, hyper-secretion--or is it something else?" No one moved as Kennedy skillfully led his disclosure along step by step. "That question," he began again slowly, shifting his position in the chair, "raises in my mind, at least, a question which has often occurred to me before. Is it possible for a person, taking advantage of the scientific knowledge we have gained, to devise and successfully execute a murder without fear of discovery? In other words, can a person be removed with that technical nicety of detail which will leave no clue and will be set down as something entirely natural, though unfortunate?" It was a terrible idea he was framing, and he dwelt on it so that we might accept it at its full value. "As one doctor has said," he added, "although toxicologists and chemists have not always possessed infallible tests for practical use, it is at present a pretty certain observation that every poison leaves its mark. But then on the other hand, students of criminology have said that a skilled physician or surgeon is about the only person now capable of carrying out a really scientific murder. "Which is true? It seems to me, at least in the latter case, that the very nicety of the handiwork must often serve as a clue in itself. The trained hand leaves the peculiar mark characteristic of its training. No matter how shrewdly the deed is planned, the execution of it is daily becoming a more and more difficult feat, thanks to our increasing knowledge of microbiology and pathology." He had risen, as he finished the sentence, every eye fixed on him, as if he had been a master hypnotist. "Perhaps," he said, taking off the cylinder from the phonograph and placing on one which I knew was that which had lain in the library closet over night, "perhaps some of the things I have said will explain or be explained by the record on this cylinder." He had started the machine. So magical was the effect on the little audience that I am tempted to repeat what I had already heard, but had not myself yet been able to explain: "How is she to-day?" "Not much changed--perhaps not so well." "It's all right, though. That is natural. It is working well. I think you might increase the dose one tablet." "You're sure it is all right?" "Oh, positively--it has been done in Europe." "I hope so. It must be a boy--and an ATHERTON." "Never fear." No one moved a muscle. If there was anyone in the room guilty of playing on the feelings and the health of an unfortunate woman, that person must have had superb control of his own feelings. "As you know," resumed Kennedy thoughtfully, "there are and have been many theories of sex control. One of the latest, but by no means the only one, is that it can be done by use of the extracts of various glands administered to the mother. I do not know with what scientific authority it was stated, but I do know that some one has recently said that adrenalin, derived from the suprarenal glands, induces boys to develop--cholin, from the bile of the liver, girls. It makes no difference--in this case. There may have been a show of science. But it was to cover up a crime. Some one has been administering to Eugenia Atherton tablets of thyroid extract--ostensibly to aid her in fulfilling the dearest ambition of her soul--to become the mother of a new line of Athertons which might bear the same relation to the future of the country as the great family of the Edwards mothered by Elizabeth Tuttle." He was bending over the two phonograph cylinders now, rapidly comparing the new one which he had made and that which he had just allowed to reel off its astounding revelation. "When a voice speaks into a phonograph," he said, half to himself, "its modulations received on the diaphragm are written by a needle point upon the surface of a cylinder or disk in a series of fine waving or zigzag lines of infinitely varying depth or breadth. Dr. Marage and others have been able to distinguish vocal sounds by the naked eye on phonograph records. Mr. Edison has studied them with the microscope in his world-wide search for the perfect voice. "In fact, now it is possible to identify voices by the records they make, to get at the precise meaning of each slightest variation of the lines with mathematical accuracy. They can no more be falsified than handwriting can be forged so that modern science cannot detect it or than typewriting can be concealed and attributed to another machine. The voice is like a finger print, a portrait parle--unescapable." He glanced up, then back again. "This microscope shows me," he said, "that the voices on that cylinder you heard are identical with two on this record which I have just made in this room." "Walter," he said, motioning to me, "look." I glanced into the eyepiece and saw a series of lines and curves, peculiar waves lapping together and making an appearance in some spots almost like tooth marks. Although I did not understand the details of the thing, I could readily see that by study one might learn as much about it as about loops, whorls, and arches on finger tips. "The upper and lower lines," he explained, "with long regular waves, on that highly magnified section of the record, are formed by the voice with no overtones. The three lines in the middle, with rhythmic ripples, show the overtones." He paused a moment and faced us. "Many a person," he resumed, "is a biotype in whom a full complement of what are called inhibitions never develops. That is part of your eugenics. Throughout life, and in spite of the best of training, that person reacts now and then to a certain stimulus directly. A man stands high; once a year he falls with a lethal quantity of alcohol. A woman, brilliant, accomplished, slips away and spends a day with a lover as unlike herself as can be imagined. "The voice that interests me most on these records," he went on, emphasizing the words with one of the cylinders which he still held, "is that of a person who has been working on the family pride of another. That person has persuaded the other to administer to Eugenia an extract because 'it must be a boy and an Atherton.' That person is a high-class defective, born with a criminal instinct, reacting to it in an artful way. Thank God, the love of a man whom theoretical eugenics condemned, roused us in--" A cry at the door brought us all to our feet, with hearts thumping as if they were bursting. It was Eugenia Atherton, wild-eyed, erect, staring. I stood aghast at the vision. Was she really to be the Lady Madeline in this fall of the House of Atherton? "Edith--I--I missed you. I heard voices. Is--is it true--what this man--says? Is my--my baby--" Quincy Atherton leaped forward and caught her as she reeled. Quickly Craig threw open a window for air, and as he did so leaned far out and blew shrilly on a police whistle. The young man looked up from Eugenia, over whom he was bending, scarcely heeding what else went on about him. Still, there was no trace of anger on his face, in spite of the great wrong that had been done him. There was room for only one great emotion--only anxiety for the poor girl who had suffered so cruelly merely for taking his name. Kennedy saw the unspoken question in his eyes. "Eugenia is a pure normal, as Dr. Crafts told you," he said gently. "A few weeks, perhaps only days, of treatment--the thyroid will revert to its normal state--and Eugenia Gilman will be the mother of a new house of Atherton which may eclipse even the proud record of the founder of the old." "Who blew the whistle?" demanded a gruff voice at the door, as a tall bluecoat puffed past the scandalized butler. "Arrest that woman," pointed Kennedy. "She is the poisoner. Either as wife of Burroughs, whom she fascinates and controls as she does Edith, she planned to break the will of Quincy or, in the other event, to administer the fortune as head of the Eugenics Foundation after the death of Dr. Crafts, who would have followed Eugenia and Quincy Atherton." I followed the direction of Kennedy's accusing finger. Maude Schofield's face betrayed more than even her tongue could have confessed. CHAPTER XXXIV THE BILLIONAIRE BABY Coming to us directly as a result of the talk that the Atherton case provoked was another that involved the happiness of a wealthy family to a no less degree. "I suppose you have heard of the 'billionaire baby,' Morton Hazleton III?" asked Kennedy of me one afternoon shortly afterward. The mere mention of the name conjured up in my mind a picture of the lusty two-year-old heir of two fortunes, as the feature articles in the Star had described that little scion of wealth--his luxurious nursery, his magnificent toys, his own motor car, a trained nurse and a detective on guard every hour of the day and night, every possible precaution for his health and safety. "Gad, what a lucky kid!" I exclaimed involuntarily. "Oh, I don't know about that," put in Kennedy. "The fortune may be exaggerated. His happiness is, I'm sure." He had pulled from his pocketbook a card and handed it to me. It read: "Gilbert Butler, American representative, Lloyd's." "Lloyd's?" I queried. "What has Lloyd's to do with the billion-dollar baby?" "Very much. The child has been insured with them for some fabulous sum against accident, including kidnaping." "Yes?" I prompted, "sensing" a story. "Well, there seem to have been threats of some kind, I understand. Mr. Butler has called on me once already to-day to retain my services and is going to--ah--there he is again now." Kennedy had answered the door buzzer himself, and Mr. Butler, a tall, sloping-shouldered Englishman, entered. "Has anything new developed?" asked Kennedy, introducing me. "I can't say," replied Butler dubiously. "I rather think we have found something that may have a bearing on the case. You know Miss Haversham, Veronica Haversham?" "The actress and professional beauty? Yes--at least I have seen her. Why?" "We hear that Morton Hazleton knows her, anyhow," remarked Butler dryly. "Well?" "Then you don't know the gossip?" he cut in. "She is said to be in a sanitarium near the city. I'll have to find that out for you. It's a fast set she has been traveling with lately, including not only Hazleton, but Dr. Maudsley, the Hazleton physician, and one or two others, who if they were poorer might be called desperate characters." "Does Mrs. Hazleton know of--of his reputed intimacy?" "I can't say that, either. I presume that she is no fool." Morton Hazleton, Jr., I knew, belonged to a rather smart group of young men. He had been mentioned in several near-scandals, but as far as I knew there had been nothing quite as public and definite as this one. "Wouldn't that account for her fears?" I asked. "Hardly," replied Butler, shaking his head. "You see, Mrs. Hazleton is a nervous wreck, but it's about the baby, and caused, she says, by her fears for its safety. It came to us only in a roundabout way, through a servant in the house who keeps us in touch. The curious feature is that we can seem to get nothing definite from her about her fears. They may be groundless." Butler shrugged his shoulders and proceeded, "And they may be well-founded. But we prefer to run no chances in a case of this kind. The child, you know, is guarded in the house. In his perambulator he is doubly guarded, and when he goes out for his airing in the automobile, two men, the chauffeur and a detective, are always there, besides his nurse, and often his mother or grandmother. Even in the nursery suite they have iron shutters which can be pulled down and padlocked at night and are constructed so as to give plenty of fresh air even to a scientific baby. Master Hazleton was the best sort of risk, we thought. But now--we don't know." "You can protect yourselves, though," suggested Kennedy. "Yes, we have, under the policy, the right to take certain measures to protect ourselves in addition to the precautions taken by the Hazletons. We have added our own detective to those already on duty. But we--we don't know what to guard against," he concluded, perplexed. "We'd like to know--that's all. It's too big a risk." "I may see Mrs. Hazleton?" mused Kennedy. "Yes. Under the circumstances she can scarcely refuse to see anyone we send. I've arranged already for you to meet her within an hour. Is that all right?" "Certainly." The Hazleton home in winter in the city was uptown, facing the river. The large grounds adjoining made the Hazletons quite independent of the daily infant parade which one sees along Riverside Drive. As we entered the grounds we could almost feel the very atmosphere on guard. We did not see the little subject of so much concern, but I remembered his much heralded advent, when his grandparents had settled a cold million on him, just as a reward for coming into the world. Evidently, Morton, Sr., had hoped that Morton, Jr., would calm down, now that there was a third generation to consider. It seemed that he had not. I wondered if that had really been the occasion of the threats or whatever it was that had caused Mrs. Hazleton's fears, and whether Veronica Haversham or any of the fast set around her had had anything to do with it. Millicent Hazleton was a very pretty little woman, in whom one saw instinctively the artistic temperament. She had been an actress, too, when young Morton Hazleton married her, and at first, at least, they had seemed very devoted to each other. We were admitted to see her in her own library, a tastefully furnished room on the second floor of the house, facing a garden at the side. "Mrs. Hazleton," began Butler, smoothing the way for us, "of course you realize that we are working in your interests. Professor Kennedy, therefore, in a sense, represents both of us." "I am quite sure I shall be delighted to help you," she said with an absent expression, though not ungraciously. Butler, having introduced us, courteously withdrew. "I leave this entirely in your hands," he said, as he excused himself. "If you want me to do anything more, call on me." I must say that I was much surprised at the way she had received us. Was there in it, I wondered, an element of fear lest if she refused to talk suspicion might grow even greater? One could see anxiety plainly enough on her face, as she waited for Kennedy to begin. A few moments of general conversation then followed. "Just what is it you fear?" he asked, after having gradually led around to the subject. "Have there been any threatening letters?" "N-no," she hesitated, "at least nothing--definite." "Gossip?" he hinted. "No." She said it so positively that I fancied it might be taken for a plain "Yes." "Then what is it?" he asked, very deferentially, but firmly. She had been looking out at the garden. "You couldn't understand," she remarked. "No detective--" she stopped. "You may be sure, Mrs. Hazleton, that I have not come here unnecessarily to intrude," he reassured her. "It is exactly as Mr. Butler put it. We--want to help you." I fancied there seemed to be something compelling about his manner. It was at once sympathetic and persuasive. Quite evidently he was taking pains to break down the prejudice in her mind which she had already shown toward the ordinary detective. "You would think me crazy," she remarked slowly. "But it is just a--a dream--just dreams." I don't think she had intended to say anything, for she stopped short and looked at him quickly as if to make sure whether he could understand. As for myself, I must say I felt a little skeptical. To my surprise, Kennedy seemed to take the statement at its face value. "Ah," he remarked, "an anxiety dream? You will pardon me, Mrs. Hazleton, but before we go further let me tell you frankly that I am much more than an ordinary detective. If you will permit me, I should rather have you think of me as a psychologist, a specialist, one who has come to set your mind at rest rather than to worm things from you by devious methods against which you have to be on guard. It is just for such an unusual case as yours that Mr. Butler has called me in. By the way, as our interview may last a few minutes, would you mind sitting down? I think you'll find it easier to talk if you can get your mind perfectly at rest, and for the moment trust to the nurse and the detectives who are guarding the garden, I am sure, perfectly." She had been standing by the window during the interview and was quite evidently growing more and more nervous. With a bow Kennedy placed her at her ease on a chaise lounge. "Now," he continued, standing near her, but out of sight, "you must try to remain free from all external influences and impressions. Don't move. Avoid every use of a muscle. Don't let anything distract you. Just concentrate your attention on your psychic activities. Don't suppress one idea as unimportant, irrelevant, or nonsensical. Simply tell me what occurs to you in connection with the dreams--everything," emphasized Craig. I could not help feeling surprised to find that she accepted Kennedy's deferential commands, for after all that was what they amounted to. Almost I felt that she was turning to him for help, that he had broken down some barrier to her confidence. He seemed to exert a sort of hypnotic influence over her. "I have had cases before which involved dreams," he was saying quietly and reassuringly. "Believe me, I do not share the world's opinion that dreams are nothing. Nor yet do I believe in them superstitiously. I can readily understand how a dream can play a mighty part in shaping the feelings of a high-tensioned woman. Might I ask exactly what it is you fear in your dreams?" She sank her head back in the cushions, and for a moment closed her eyes, half in weariness, half in tacit obedience to him. "Oh, I have such horrible dreams," she said at length, "full of anxiety and fear for Morton and little Morton. I can't explain it. But they are so horrible." Kennedy said nothing. She was talking freely at last. "Only last night," she went on, "I dreamt that Morton was dead. I could see the funeral, all the preparations, and the procession. It seemed that in the crowd there was a woman. I could not see her face, but she had fallen down and the crowd was around her. Then Dr. Maudsley appeared. Then all of a sudden the dream changed. I thought I was on the sand, at the seashore, or perhaps a lake. I was with Junior and it seemed as if he were wading in the water, his head bobbing up and down in the waves. It was like a desert, too--the sand. I turned, and there was a lion behind me. I did not seem to be afraid of him, although I was so close that I could almost feel his shaggy mane. Yet I feared that he might bite Junior. The next I knew I was running with the child in my arms. I escaped--and--oh, the relief!" She sank back, half exhausted, half terrified still by the recollection. "In your dream when Dr. Maudsley appeared," asked Kennedy, evidently interested in filling in the gap, "what did he do?" "Do?" she repeated. "In the dream? Nothing." "Are you sure?" he asked, shooting a quick glance at her. "Yes. That part of the dream became indistinct. I'm sure he did nothing, except shoulder through the crowd. I think he had just entered. Then that part of the dream seemed to end and the second part began." Piece by piece Kennedy went over it, putting it together as if it were a mosaic. "Now, the woman. You say her face was hidden?" She hesitated. "N--no. I saw it. But it was no one I knew." Kennedy did not dwell on the contradiction, but added, "And the crowd?" "Strangers, too." "Dr. Maudsley is your family physician?" he questioned. "Yes." "Did he call--er--yesterday?" "He calls every day to supervise the nurse who has Junior in charge." "Could one always be true to oneself in the face of any temptation?" he asked suddenly. It was a bold question. Yet such had been the gradual manner of his leading up to it that, before she knew it, she had answered quite frankly, "Yes--if one always thought of home and her child, I cannot see how one could help controlling herself." She seemed to catch her breath, almost as though the words had escaped her before she knew it. "Is there anything besides your dream that alarms you," he asked, changing the subject quickly, "any suspicion of--say the servants?" "No," she said, watching him now. "But some time ago we caught a burglar upstairs here. He managed to escape. That has made me nervous. I didn't think it was possible." "Anything else?" "No," she said positively, this time on her guard. Kennedy saw that she had made up her mind to say no more. "Mrs. Hazleton," he said, rising. "I can hardly thank you too much for the manner in which you have met my questions. It will make it much easier for me to quiet your fears. And if anything else occurs to you, you may rest assured I shall violate no confidences in your telling me." I could not help the feeling, however, that there was just a little air of relief on her face as we left. CHAPTER XXXV THE PSYCHANALYSIS "H--M," mused Kennedy as we walked along after leaving the house. "There were several 'complexes,' as they are called, there--the most interesting and important being the erotic, as usual. Now, take the lion in the dream, with his mane. That, I suspect, was Dr. Maudsley. If you are acquainted with him, you will recall his heavy, almost tawny beard." Kennedy seemed to be revolving something in his mind and I did not interrupt. I had known him too long to feel that even a dream might not have its value with him. Indeed, several times before he had given me glimpses into the fascinating possibilities of the new psychology. "In spite of the work of thousands of years, little progress has been made in the scientific understanding of dreams," he remarked a few moments later. "Freud, of Vienna--you recall the name?--has done most, I think in that direction." I recalled something of the theories of the Freudists, but said nothing. "It is an unpleasant feature of his philosophy," he went on, "but Freud finds the conclusion irresistible that all humanity underneath the shell is sensuous and sensual in nature. Practically all dreams betray some delight of the senses and sexual dreams are a large proportion. There is, according to the theory, always a wish hidden or expressed in a dream. The dream is one of three things, the open, the disguised or the distorted fulfillment of a wish, sometimes recognized, sometimes repressed. "Anxiety dreams are among the most interesting and important Anxiety may originate in psycho-sexual excitement, the repressed libido, as the Freudists call it. Neurotic fear has its origin in sexual life and corresponds to a libido which has been turned away from its object and has not succeeded in being applied. All so-called day dreams of women are erotic; of men they are either ambition or love. "Often dreams, apparently harmless, turn out to be sinister if we take pains to interpret them. All have the mark of the beast. For example, there was that unknown woman who had fallen down and was surrounded by a crowd. If a woman dreams that, it is sexual. It can mean only a fallen woman. That is the symbolism. The crowd always denotes a secret. "Take also the dream of death. If there is no sorrow felt, then there is another cause for it. But if there is sorrow, then the dreamer really desires death or absence. I expect to have you quarrel with that. But read Freud, and remember that in childhood death is synonymous with being away. Thus for example, if a girl dreams that her mother is dead, perhaps it means only that she wishes her away so that she can enjoy some pleasure that her strict parent, by her presence, denies. "Then there was that dream about the baby in the water. That, I think, was a dream of birth. You see, I asked her practically to repeat the dreams because there were several gaps. At such points one usually finds first hesitation, then something that shows one of the main complexes. Perhaps the subject grows angry at the discovery. "Now, from the tangle of the dream thought, I find that she fears that her husband is too intimate with another woman, and that perhaps unconsciously she has turned to Dr. Maudsley for sympathy. Dr. Maudsley, as I said, is not only bearded, but somewhat of a social lion. He had called on her the day before. Of such stuff are all dream lions when there is no fear. But she shows that she has been guilty of no wrongdoing--she escaped, and felt relieved." "I'm glad of that," I put in. "I don't like these scandals. On the Star when I have to report them, I do it always under protest. I don't know what your psychanalysis is going to show in the end, but I for one have the greatest sympathy for that poor little woman in the big house alone, surrounded by and dependent on servants, while her husband is out collecting scandals." "Which suggests our next step," he said, turning the subject. "I hope that Butler has found out the retreat of Veronica Haversham." We discovered Miss Haversham at last at Dr. Klemm's sanitarium, up in the hills of Westchester County, a delightful place with a reputation for its rest cures. Dr. Klemm was an old friend of Kennedy's, having had some connection with the medical school at the University. She had gone up there rather suddenly, it seemed, to recuperate. At least that was what was given out, though there seemed to be much mystery about her, and she was taking no treatment as far as was known. "Who is her physician?" asked Kennedy of Dr. Klemm as we sat in his luxurious office. "A Dr. Maudsley of the city." Kennedy glanced quickly at me in time to check an exclamation. "I wonder if I could see her?" "Why, of course--if she is willing," replied Dr. Klemm. "I will have to have some excuse," ruminated Kennedy. "Tell her I am a specialist in nervous troubles from the city, have been visiting one of the other patients, anything." Dr. Klemm pulled down a switch on a large oblong oak box on his desk, asked for Miss Haversham, and waited a moment. "What is that?" I asked. "A vocaphone," replied Kennedy. "This sanitarium is quite up to date, Klemm." The doctor nodded and smiled. "Yes, Kennedy," he replied. "Communicating with every suite of rooms we have the vocaphone. I find it very convenient to have these microphones, as I suppose you would call them, catching your words without talking into them directly as you have to do in the telephone and then at the other end emitting the words without the use of an earpiece, from the box itself, as if from a megaphone horn. Miss Haversham, this is Dr. Klemm. There is a Dr. Kennedy here visiting another patient, a specialist from New York. He'd like very much to see you if you can spare a few minutes." "Tell him to come up." The voice seemed to come from the vocaphone as though she were in the room with us. Veronica Haversham was indeed wonderful, one of the leading figures in the night life of New York, a statuesque brunette of striking beauty, though I had heard of often ungovernable temper. Yet there was something strange about her face here. It seemed perhaps a little yellow, and I am sure that her nose had a peculiar look as if she were suffering from an incipient rhinitis. The pupils of her eyes were as fine as pin heads, her eyebrows were slightly elevated. Indeed, I felt that she had made no mistake in taking a rest if she would preserve the beauty which had made her popularity so meteoric. "Miss Haversham," began Kennedy, "they tell me that you are suffering from nervousness. Perhaps I can help you. At any rate it will do no harm to try. I know Dr. Maudsley well, and if he doesn't approve--well, you may throw the treatment into the waste basket." "I'm sure I have no reason to refuse," she said. "What would you suggest?" "Well, first of all, there is a very simple test I'd like to try. You won't find that it bothers you in the least--and if I can't help you, then no harm is done." Again I watched Kennedy as he tactfully went through the preparations for another kind of psychanalysis, placing Miss Haversham at her ease on a davenport in such a way that nothing would distract her attention. As she reclined against the leather pillows in the shadow it was not difficult to understand the lure by which she held together the little coterie of her intimates. One beautiful white arm, bare to the elbow, hung carelessly over the edge of the davenport, displaying a plain gold bracelet. "Now," began Kennedy, on whom I knew the charms of Miss Haversham produced a negative effect, although one would never have guessed it from his manner, "as I read off from this list of words, I wish that you would repeat the first thing, anything," he emphasized, "that comes into your head, no matter how trivial it may seem. Don't force yourself to think. Let your ideas flow naturally. It depends altogether on your paying attention to the words and answering as quickly as you can--remember, the first word that comes into your mind. It is easy to do. We'll call it a game," he reassured. Kennedy handed a copy of the list to me to record the answers. There must have been some fifty words, apparently senseless, chosen at random, it seemed. They were: head to dance salt white lie green sick new child to fear water pride to pray sad stork to sing ink money to marry false death angry foolish dear anxiety long needle despise to quarrel to kiss ship voyage finger old bride to pay to sin expensive family pure window bread to fall friend ridicule cold rich unjust luck to sleep "The Jung association word test is part of the Freud psychanalysis, also," he whispered to me, "You remember we tried something based on the same idea once before?" I nodded. I had heard of the thing in connection with blood-pressure tests, but not this way. Kennedy called out the first word, "Head," while in his hand he held a stop watch which registered to one-fifth of a second. Quickly she replied, "Ache," with an involuntary movement of her hand toward her beautiful forehead. "Good," exclaimed Kennedy. "You seem to grasp the idea better than most of my patients." I had recorded the answer, he the time, and we found out, I recall afterward, that the time averaged something like two and two-fifths seconds. I thought her reply to the second word, "green," was curious. It came quickly, "Envy." However, I shall not attempt to give all the replies, but merely some of the most significant. There did not seem to be any hesitation about most of the words, but whenever Kennedy tried to question her about a word that seemed to him interesting she made either evasive or hesitating answers, until it became evident that in the back of her head was some idea which she was repressing and concealing from us, something that she set off with a mental "No Thoroughfare." He had finished going through the list, and Kennedy was now studying over the answers and comparing the time records. "Now," he said at length, running his eye over the words again, "I want to repeat the performance. Try to remember and duplicate your first replies," he said. Again we went through what at first had seemed to me to be a solemn farce, but which I began to see was quite important. Sometimes she would repeat the answer exactly as before. At other times a new word would occur to her. Kennedy was keen to note all the differences in the two lists. One which I recall because the incident made an impression on me had to do with the trio, "Death--life--inevitable." "Why that?" he asked casually. "Haven't you ever heard the saying, 'One should let nothing which one can have escape, even if a little wrong is done; no opportunity should be missed; life is so short, death inevitable'?" There were several others which to Kennedy seemed more important, but long after we had finished I pondered this answer. Was that her philosophy of life? Undoubtedly she would never have remembered the phrase if it had not been so, at least in a measure. She had begun to show signs of weariness, and Kennedy quickly brought the conversation around to subjects of apparently a general nature, but skillfully contrived so as to lead the way along lines her answers had indicated. Kennedy had risen to go, still chatting. Almost unintentionally he picked up from a dressing table a bottle of white tablets, without a label, shaking it to emphasize an entirely, and I believe purposely, irrelevant remark. "By the way," he said, breaking off naturally, "what is that?" "Only something Dr. Maudsley had prescribed for me," she answered quickly. As he replaced the bottle and went on with the thread of the conversation, I saw that in shaking the bottle he had abstracted a couple of the tablets before she realized it. "I can't tell you just what to do without thinking the case over," he concluded, rising to go. "Yours is a peculiar case, Miss Haversham, baffling. I'll have to study it over, perhaps ask Dr. Maudsley If I may see you again. Meanwhile, I am sure what he is doing is the correct thing." Inasmuch as she had said nothing about what Dr. Maudsley was doing, I wondered whether there was not just a trace of suspicion in her glance at him from under her long dark lashes. "I can't see that you have done anything," she remarked pointedly. "But then doctors are queer--queer." That parting shot also had in it, for me, something to ponder over. In fact I began to wonder if she might not be a great deal more clever than even Kennedy gave her credit for being, whether she might not have submitted to his tests for pure love of pulling the wool over his eyes. Downstairs again, Kennedy paused only long enough to speak a few words with his friend Dr. Klemm. "I suppose you have no idea what Dr. Maudsley has prescribed for her?" he asked carelessly. "Nothing, as far as I know, except rest and simple food." He seemed to hesitate, then he said under his voice, "I suppose you know that she is a regular dope fiend, seasons her cigarettes with opium, and all that." "I guessed as much," remarked Kennedy, "but how does she get it here?" "She doesn't." "I see," remarked Craig, apparently weighing now the man before him. At length he seemed to decide to risk something. "Klemm," he said, "I wish you would do something for me. I see you have the vocaphone here. Now if--say Hazleton--should call--will you listen in on that vocaphone for me?" Dr. Klemm looked squarely at him. "Kennedy," he said, "it's unprofessional, but---" "So it is to let her be doped up under guise of a cure." "What?" he asked, startled. "She's getting the stuff now?" "No, I didn't say she was getting opium, or from anyone here. All the same, if you would just keep an ear open---" "It's unprofessional, but--you'd not ask it without a good reason. I'll try." It was very late when we got back to the city and we dined at an uptown restaurant which we had almost to ourselves. Kennedy had placed the little whitish tablets in a small paper packet for safe keeping. As we waited for our order he drew one from his pocket, and after looking at it a moment crushed it to a powder in the paper. "What is it?" I asked curiously. "Cocaine?" "No," he said, shaking his head doubtfully. He had tried to dissolve a little of the powder in some water from the glass before him, but it would not dissolve. As he continued to look at it his eye fell on the cut-glass vinegar cruet before us. It was full of the white vinegar. "Really acetic acid," he remarked, pouring out a little. The white powder dissolved. For several minutes he continued looking at the stuff. "That, I think," he remarked finally, "is heroin." "More 'happy dust'?" I replied with added interest now, thinking of our previous case. "Is the habit so extensive?" "Yes," he replied, "the habit is comparatively new, although in Paris, I believe, they call the drug fiends, 'heroinomaniacs.' It is, as I told you before, a derivative of morphine. Its scientific name is diacetyl-morphin. It is New York's newest peril, one of the most dangerous drugs yet. Thousands are slaves to it, although its sale is supposedly restricted. It is rotting the heart out of the Tenderloin. Did you notice Veronica Haversham's yellowish whiteness, her down-drawn mouth, elevated eyebrows, and contracted eyes? She may have taken it up to escape other drugs. Some people have--and have just got a new habit. It can be taken hypodermically, or in a tablet, or by powdering the tablet to a white crystalline powder and snuffing up the nose. That's the way she takes it. It produces rhinitis of the nasal passages, which I see you observed, but did not understand. It has a more profound effect than morphine, and is ten times as powerful as codeine. And one of the worst features is that so many people start with it, thinking it is as harmless as it has been advertised. I wouldn't be surprised if she used from seventy-five to a hundred one-twelfth grain tablets a day. Some of them do, you know." "And Dr. Maudsley," I asked quickly, "do you think it is through him or in spite of him?" "That's what I'd like to know. About those words," he continued, "what did you make of the list and the answers?" I had made nothing and said so, rather quickly. "Those," he explained, "were words selected and arranged to strike almost all the common complexes in analyzing and diagnosing. You'd think any intelligent person could give a fluent answer to them, perhaps a misleading answer. But try it yourself, Walter. You'll find you can't. You may start all right, but not all the words will be reacted to in the same time or with the same smoothness and ease. Yet, like the expressions of a dream, they often seem senseless. But they have a meaning as soon as they are 'psychanalyzed.' All the mistakes in answering the second time, for example, have a reason, if we can only get at it. They are not arbitrary answers, but betray the inmost subconscious thoughts, those things marked, split off from consciousness and repressed into the unconscious. Associations, like dreams, never lie. You may try to conceal the emotions and unconscious actions, but you can't." I listened, fascinated by Kennedy's explanation. "Anyone can see that that woman has something on her mind besides the heroin habit. It may be that she is trying to shake the habit off in order to do it; it may be that she seeks relief from her thoughts by refuge in the habit; and it may be that some one has purposely caused her to contract this new habit in the guise of throwing off an old. The only way by which to find out is to study the case." He paused. He had me keenly on edge, but I knew that he was not yet in a position to answer his queries positively. "Now I found," he went on, "that the religious complexes were extremely few; as I expected the erotic were many. If you will look over the three lists you will find something queer about every such word as, 'child, 'to marry,' 'bride,' 'to lie,' 'stork,' and so on. We're on the right track. That woman does know something about that child." "My eye catches the words 'to sin,' 'to fall,' 'pure,' and others," I remarked, glancing over the list. "Yes, there's something there, too. I got the hint for the drug from her hesitation over 'needle' and 'white.' But the main complex has to do with words relating to that child and to love. In short, I think we are going to find it to be the reverse of the rule of the French, that it will be a case of 'cherchez l'homme.'" Early the next day Kennedy, after a night of studying over the case, journeyed up to the sanitarium again. We found Dr. Klemm eager to meet us. "What is it?" asked Kennedy, equally eager. "I overheard some surprising things over the vocaphone," he hastened. "Hazleton called. Why, there must have been some wild orgies in that precious set of theirs, and, would you believe it, many of them seem to have been at what Dr. Maudsley calls his 'stable studio,' a den he has fixed up artistically over his garage on a side street." "Indeed?" "I couldn't get it all, but I did hear her repeating over and over to Hazleton, 'Aren't you all mine? Aren't you all mine?' There must be some vague jealousy lurking in the heart of that ardent woman. I can't figure it out." "I'd like to see her again," remarked Kennedy. "Will you ask her if I may?" CHAPTER XXXVI THE ENDS OF JUSTICE A few minutes later we were in the sitting room of her suite. She received us rather ungraciously, I thought. "Do you feel any better?" asked Kennedy. "No," she replied curtly. "Excuse me for a moment. I wish to see that maid of mine. Clarisse!" She had hardly left the room when Kennedy was on his feet. The bottle of white tablets, nearly empty, was still on the table. I saw him take some very fine white powder and dust it quickly over the bottle. It seemed to adhere, and from his pocket he quickly drew a piece of what seemed to be specially prepared paper, laid it over the bottle where the powder adhered, fitting it over the curves. He withdrew it quickly, for outside we heard her light step, returning. I am sure she either saw or suspected that Kennedy had been touching the bottle of tablets, for there was a look of startled fear on her face. "Then you do not feel like continuing the tests we abandoned last night?" asked Kennedy, apparently not noticing her look. "No, I do not," she almost snapped. "You--you are detectives. Mrs. Hazleton has sent you." "Indeed, Mrs. Hazleton has not sent us," insisted Kennedy, never for an instant showing his surprise at her mention of the name. "You are. You can tell her, you can tell everybody. I'll tell--I'll tell myself. I won't wait. That child is mine--mine--not hers. Now--go!" Veronica Haversham on the stage never towered in a fit of passion as she did now in real life, as her ungovernable feelings broke forth tempestuously on us. I was astounded, bewildered at the revelation, the possibilities in those simple words, "The child is mine." For a moment I was stunned. Then as the full meaning dawned on me I wondered in a flood of consciousness whether it was true. Was it the product of her drug-disordered brain? Had her desperate love for Hazleton produced a hallucination? Kennedy, silent, saw that the case demanded quick action. I shall never forget the breathless ride down from the sanitarium to the Hazleton house on Riverside Drive. "Mrs. Hazleton," he cried, as we hurried in, "you will pardon me for this unceremonious intrusion, but it is most important. May I trouble you to place your fingers on this paper--so?" He held out to her a piece of the prepared paper. She looked at him once, then saw from his face that he was not to be questioned. Almost tremulously she did as he said, saying not a word. I wondered whether she knew the story of Veronica, or whether so far only hints of it had been brought to her. "Thank you," he said quickly. "Now, if I may see Morton?" It was the first time we had seen the baby about whom the rapidly thickening events were crowding. He was a perfect specimen of well-cared-for, scientific infant. Kennedy took the little chubby fingers playfully in his own. He seemed at once to win the child's confidence, though he may have violated scientific rules. One by one he pressed the little fingers on the paper, until little Morton crowed with delight as one little piggy after another "went to market." He had deserted thousands of dollars' worth of toys just to play with the simple piece of paper Kennedy had brought with him. As I looked at him, I thought of what Kennedy had said at the start. Perhaps this innocent child was not to be envied after all. I could hardly restrain my excitement over the astounding situation which had suddenly developed. "That will do," announced Kennedy finally, carelessly folding up the paper and slipping it into his pocket. "You must excuse me now." "You see," he explained on the way to the laboratory, "that powder adheres to fresh finger prints, taking all the gradations. Then the paper with its paraffine and glycerine coating takes off the powder." In the laboratory he buried himself in work, with microscope compasses, calipers, while I fumed impotently at the window. "Walter," he called suddenly, "get Dr. Maudsley on the telephone. Tell him to come immediately to the laboratory." Meanwhile Kennedy was busy arranging what he had discovered in logical order and putting on it the finishing touches. As Dr. Maudsley entered Kennedy greeted him and began by plunging directly into the case in answer to his rather discourteous inquiry as to why he had been so hastily summoned. "Dr. Maudsley," said Craig, "I have asked you to call alone because, while I am on the verge of discovering the truth in an important case affecting Morton Hazleton and his wife, I am frankly perplexed as to how to go ahead." The doctor seemed to shake with excitement as Kennedy proceeded. "Dr. Maudsley," Craig added, dropping his voice, "is Morton III the son of Millicent Hazleton or not? You were the physician in attendance on her at the birth. Is he?" Maudsley had been watching Kennedy furtively at first, but as he rapped out the words I thought the doctor's eyes would pop out of his head. Perspiration in great beads collected on his face. "P--professor K--Kennedy," he muttered, frantically rubbing his face and lower jaw as if to compose the agitation he could so ill conceal, "let me explain." "Yes, yes--go on," urged Kennedy. "Mrs. Hazleton's baby was born--dead. I knew how much she and the rest of the family had longed for an heir, how much it meant. And I--substituted for the dead child a newborn baby from the maternity hospital. It--it belonged to Veronica Haversham--then a poor chorus girl. I did not intend that she should ever know it. I intended that she should think her baby was dead. But in some way she found out. Since then she has become a famous beauty, has numbered among her friends even Hazleton himself. For nearly two years I have tried to keep her from divulging the secret. From time to time hints of it have leaked out. I knew that if Hazleton with his infatuation of her were to learn---" "And Mrs. Hazleton, has she been told?" interrupted Kennedy. "I have been trying to keep it from her as long as I can, but it has been difficult to keep Veronica from telling it. Hazleton himself was so wild over her. And she wanted her son as she---" "Maudsley," snapped out Kennedy, slapping down on the table the mass of prints and charts which he had hurriedly collected and was studying, "you lie! Morton is Millicent Hazleton's son. The whole story is blackmail. I knew it when she told me of her dreams and I suspected first some such devilish scheme as yours. Now I know it scientifically." He turned over the prints. "I suppose that study of these prints, Maudsley, will convey nothing to you. I know that it is usually stated that there are no two sets of finger prints in the world that are identical or that can be confused. Still, there are certain similarities of finger prints and other characteristics, and these similarities have recently been exhaustively studied by Bertilion, who has found that there are clear relationships sometimes between mother and child in these respects. If Solomon were alive, doctor, he would not now have to resort to the expedient to which he did when the two women disputed over the right to the living child. Modern science is now deciding by exact laboratory methods the same problem as he solved by his unique knowledge of feminine psychology. "I saw how this case was tending. Not a moment too soon, I said to myself, 'The hand of the child will tell.' By the very variations in unlike things, such as finger and palm prints, as tabulated and arranged by Bertillon after study in thousands of cases, by the very loops, whorls, arches and composites, I have proved my case. "The dominancy, not the identity, of heredity through the infinite varieties of finger markings is sometimes very striking. Unique patterns in a parent have been repeated with marvelous accuracy in the child. I knew that negative results might prove nothing in regard to parentage, a caution which it is important to observe. But I was prepared to meet even that. "I would have gone on into other studies, such as Tammasia's, of heredity in the veining of the back of the hands; I would have measured the hands, compared the relative proportion of the parts; I would have studied them under the X-ray as they are being studied to-day; I would have tried the Reichert blood crystal test which is being perfected now so that it will tell heredity itself. There is no scientific stone I would have left unturned until I had delved at the truth of this riddle. Fortunately it was not necessary. Simple finger prints have told me enough. And best of all, it has been in time to frustrate that devilish scheme you and Veronica Haversham have been slowly unfolding." Maudsley crumpled up, as it were, at Kennedy's denunciation. He seemed to shrink toward the door. "Yes," cried Kennedy, with extended forefinger, "you may go--for the present. Don't try to run away. You're watched from this moment on." Maudsley had retreated precipitately. I looked at Kennedy inquiringly. What to do? It was indeed a delicate situation, requiring the utmost care to handle. If the story had been told to Hazleton, what might he not have already done? He must be found first of all if we were to meet the conspiracy of these two. Kennedy reached quickly for the telephone. "There is one stream of scandal that can be dammed at its source," he remarked, calling a number. "Hello. Klemm's Sanitarium? I'd like to speak with Miss Haversham. What--gone? Disappeared? Escaped?" He hung up the receiver and looked at me blankly. I was speechless. A thousand ideas flew through our minds at once. Had she perceived the import of our last visit and was she now on her way to complete her plotted slander of Millicent Hazleton, though it pulled down on herself in the end the whole structure? Hastily Kennedy called Hazleton's home, Butler, and one after another of Hazleton's favorite clubs. It was not until noon that Butler himself found him and came with him, under protest, to the laboratory. "What is it--what have you found?" cried Butler, his lean form a-quiver with suppressed excitement. Briefly, one fact after another, sparing Hazleton nothing, Kennedy poured forth the story, how by hint and innuendo Maudsley had been working on Millicent, undermining her, little knowing that he had attacked in her a very tower of strength, how Veronica, infatuated by him, had infatuated him, had led him on step by step. Pale and agitated, with nerves unstrung by the life he had been leading, Hazleton listened. And as Kennedy hammered one fact after another home, he clenched his fists until the nails dug into his very palms. "The scoundrels," he ground out, as Kennedy finished by painting the picture of the brave little broken-hearted woman fighting off she knew not what, and the golden-haired, innocent baby stretching out his arms in glee at the very chance to prove that he was what he was. "The scoundrels--take me to Maudsley now. I must see Maudsley. Quick!" As we pulled up before the door of the reconstructed stable-studio, Kennedy jumped out. The door was unlocked. Up the broad flight of stairs, Hazleton went two at a time. We followed him closely. Lying on the divan in the room that had been the scene of so many orgies, locked in each other's arms, were two figures--Veronica Haversham and Dr. Maudsley. She must have gone there directly after our visit to Dr. Klemm's, must have been waiting for him when he returned with his story of the exposure to answer her fears of us as Mrs. Hazleton's detectives. In a frenzy of intoxication she must have flung her arms blindly about him in a last wild embrace. Hazleton looked, aghast. He leaned over and took her arm. Before he could frame the name, "Veronica!" he had recoiled. The two were cold and rigid. "An overdose of heroin this time," muttered Kennedy. My head was in a whirl. Hazleton stared blankly at the two figures abjectly lying before him, as the truth burned itself indelibly into his soul. He covered his face with his hands. And still he saw it all. Craig said nothing. He was content to let what he had shown work in the man's mind. "For the sake of--that baby--would she--would she forgive?" asked Hazleton, turning desperately toward Kennedy. Deliberately Kennedy faced him, not as scientist and millionaire, but as man and man. "From my psychanalysis," he said slowly, "I should say that it IS within your power, in time, to change those dreams." Hazleton grasped Kennedy's hand before he knew it. "Kennedy--home--quick. This is the first manful impulse I have had for two years. And, Jameson--you'll tone down that part of it in the newspapers that Junior--might read--when he grows up?" THE END 
5094	----	THE CRAIG KENNEDY SERIES THE ROMANCE OF ELAINE A DETECTIVE NOVEL Sequel to the "Exploits" BY ARTHUR B. REEVE CONTENTS CHAPTER I THE SERPENT SIGN II THE CRYPTIC RING III THE WATCHING EYE IV THE VENGEANCE OF WU FANG V THE SHADOWS OF WAR VI THE LOST TORPEDO VII THE GRAY FRIAR VIII THE VANISHING MAN IX THE SUBMARINE HARBOR X THE CONSPIRATORS XI THE WIRELESS DETECTIVE XII THE DEATH CLOUD XIII THE SEARCHLIGHT GUN XIV THE LIFE CHAIN XV THE FLASH XVI THE DISAPPEARING HELMETS XVII THE TRIUMPH OF ELAINE THE ROMANCE OF ELAINE CHAPTER I THE SERPENT SIGN Rescued by Kennedy at last from the terrible incubus of Bennett's persecution in his double life of lawyer and master criminal, Elaine had, for the first time in many weeks, a feeling of security. Now that the strain was off, however, she felt that she needed rest and a chance to recover herself and it occurred to her that a few quiet days with "Aunt" Tabitha, who had been her nurse when she was a little girl, would do her a world of good. She sent for Aunt Tabby, yet the fascination of the experiences through which she had just gone still hung over her. She could not resist thinking and reading about them, as she sat, one morning, with the faithful Rusty in the conservatory of the Dodge house. I had told the story at length in the Star, and the heading over it caught her eye. It read: THE CLUTCHING HAND DEAD ------ Double Life Exposed by Craig Kennedy Perry Bennett, the Famous Young Lawyer, Takes Poison--Kennedy Now on Trail of Master Criminal's Hidden Millions. ---- As Elaine glanced down the column, Jennings announced that Aunt Tabby, as she loved to call her old friend, had arrived, and was now in the library with Aunt Josephine. With an exclamation of delight, Elaine dropped the paper and, followed by Rusty, almost ran into the library. Aunt Tabby was a stout, elderly, jolly-faced woman, precisely the sort whom Elaine needed to watch over her just now. "Oh, I'm so glad to see you," half laughed Elaine as she literally flung herself into her nurse's arms. "I feel so unstrung--and I thought that if I could just run off for a few days with you and Joshua in the country where no one would know, it might make me feel better. You have always been so good to me. Marie! Are my things packed? Very well. Then, get my wraps." Her maid left the room. "Bless your soul," mothered Aunt Tabby stroking her soft golden hair, "I'm always glad to have you in that fine house you bought me. And, faith, Miss Elaine, the house is a splendid place to rest in but I don't know what's the matter with it lately. Joshua says its haunts--" "Haunts?" repeated Elaine in amused surprise. "Why, what do you mean?" Marie entered with the wraps before Aunt Tabby could reply and Jennings followed with the baggage. "Nonsense," continued Elaine gaily, as she put on her coat, and turned to bid Aunt Josephine good-bye. "Good-bye, Tabitha," said her real aunt. "Keep good care of my little girl." "That I will," returned the nurse. "We don't have all these troubles out in the country that you city folks have." Elaine went out, followed by Rusty and Jennings with the luggage. "Now for a long ride in the good fresh air," sighed Elaine as she leaned back on the cushions of the Dodge limousine and patted Rusty, while the butler stowed away the bags. The air certainly did, if anything, heighten the beauty of Elaine and at last they arrived at Aunt Tabby's, tired and hungry. The car stopped and Elaine, Aunt Tabby and the dog got out. There, waiting for them, was "Uncle" Joshua, as Elaine playfully called him, a former gardener of the Dodges, now a plain, honest countryman on whom the city was fast encroaching, a jolly old fellow, unharmed by the world. Aunt Tabby's was an attractive small house, not many miles from New York, yet not in the general line of suburban travel. . . . . . . . Kennedy and I had decided to bring Bennett's papers and documents over to the laboratory to examine them. We were now engaged in going over the great mass of material which he had collected, in the hope of finding some clue to the stolen millions which he must have amassed as a result of his villainy. The table was stacked high. A knock at the door told us that the expressman had arrived and a moment later he entered, delivering a heavy box. Kennedy signed for it and started to unpack it. I was hard at work, when I came across a large manila envelope carefully sealed, on which were written the figures "$7,000,000." Too excited even to exclaim, I tore the envelope open and examined the contents. Inside was another envelope. I opened that. It contained merely a blank piece of paper! With characteristic skill at covering his tracks, Bennett had also covered his money. Puzzled, I turned the paper over and over, looking at it carefully. It was a large sheet of paper, but it showed nothing. "Huh!" I snorted to myself, "confound him." Yet I could not help smiling at my own folly, a minute later, in thinking that the Clutching Hand would leave any information in such an obvious place as an envelope. I threw the paper into a wire basket on the desk and went on sorting the other stuff. Kennedy had by this time finished unpacking the box, and was examining a bottle which he had taken from it. "Come here, Walter," he called at length. "Ever see anything like that?" "I can't say," I confessed, getting up to go to him. "What is it?" "Bring a piece of paper." he added. I went back to the desk where I had been working and looked about hastily. My eye fell on the blank sheet of paper which I had taken from Bennett's envelope, and I picked it up from the basket. "Here's one," I said, handing it to him. "What are you doing?" Kennedy did not answer directly, but began to treat the paper with the liquid from the bottle. Then he lighted a Bunsen burner and thrust the paper into the flame. The paper did not burn! "A new system of fire-proofing," laughed Craig, enjoying my astonishment. He continued to hold the paper in the flame. Still it did not burn. "See?" he went on, withdrawing it, and starting to explain the properties of the new fire-proofer. He had scarcely begun, when he stopped in surprise. He had happened to glance at the paper again, bent over to examine it more intently, and was now looking at it in surprise. I looked also. There, clearly discernible on the paper, was a small part of what looked like an architect's drawing of a fireplace. Craig looked up at me, nonplussed. "Where did you say you got that?" he asked. "It was a blank piece of paper among Bennett's effects," I returned, as mystified as he, pointing at the littered desk at which I had been working. Kennedy said nothing, but thrust the paper back again into the flame. Slowly, the heat of the burner seemed to bring out the complete drawing of the fireplace. We looked at it, even more mystified. "What is it, do you suppose?" I queried. "I think," he replied slowly, "that it was drawn with sympathetic ink. The heat of the burner brought it out into sight." What was it about? . . . . . . . Elaine had gone to bed that night at Aunt Tabby's in the room which her old nurse had fixed up especially for her. It was a very attractive little room with dainty chintz curtains and covers and for the first time in many weeks Elaine slept soundly and fearlessly. Down-stairs, in the living-room, Rusty also was asleep, his nose between his paws. The living-room was in keeping with everything at Aunt Tabby's, plain, neat, homelike. On one side was a large fireplace that gave to it an air of quaint hospitality. Suddenly Rusty woke up, his ears pointed at this fireplace. He stood a moment, listening, then, with a bark of alarm he sped swiftly from the living-room, up the stairs at a bound, until he came to Elaine's room. Elaine felt his cold nose at her hand and stirred, then awoke. "What is it, Rusty?" she asked, mindful of the former days when Rusty gave warning of the Clutching Hand and his emissaries. Rusty wagged his tail. Something was wrong. Elaine followed him down to the living-room. She went over and lighted the electric lamp on the table, then turned to Rusty. "Well, Rusty?" she asked, almost as if he were human. She had no need to repeat the question. Rusty was looking straight at the fireplace. Elaine listened. Sure enough, she heard strange noises. Was that Aunt Tabby's "haunt"? Whatever it was, it sounded as if it came up from the very depths of the earth. She could not make out just what it sounded like. It might have been some one striking a piece of iron, a bolt, with a sledge. What was it? She continued to listen in wonder, then ran to Aunt Tabby's bedroom door, on the first floor, and knocked. Aunt Tabby woke up and shook Joshua. "Aunt Tabby! Aunt Tabby!" called Elaine. "Yes, my dear," answered the old nurse, now fully awake and straightening her nightcap. "Joshua!" Together the old couple came out into the living-room, still in their nightclothes, Joshua yawning sleepily still. "Listen!" whispered Elaine. There was the noise again. This time it was more as though some one were beating a rat-tat-tat with something on a rock. It was weird, uncanny, as all stood there, none knowing where the strange noises came from. "It's the haunts!" cried Aunt Tabby, trembling a bit. "For three nights now we've been hearing these noises." Around and around the room they walked, still trying to locate the strange sounds. Were they under the floor? It was impossible to say. They gave it up and stood there, looking blankly at each other. Was it the work of human or superhuman hands? Finally Joshua went to a table drawer and opened it. He took out a huge, murderous-looking revolver. "Here, Miss Elaine," he urged, pressing it on her, "take this--keep it near you!" The noises ceased at length, as strangely as they had begun. Half an hour later, they had all gone back to bed and were asleep. But Elaine's sleep now was fitful, a constant procession of faces flitted before her closed eyes. Suddenly, she woke with a start and stared into the semi-darkness. Was that face real, or a dream face? Was it the hideous helmeted face that had dragged her down into the sewer once? That man was dead. Who was this? She gazed at the bedroom window, holding the huge revolver tightly. There, vague in the night light, appeared a figure. Surely that was no dream face of the oxygen helmet. Besides, it was not the same helmet. She sat bolt upright and fired, pointblank, at the window, shivering the glass. A second later she had leaped from the bed, switched on the lights and was running to the sill. Down-stairs, Aunt Tabby and Uncle Joshua had heard the shot. Joshua was now wide awake. He seized his old shotgun and ran out into the livingroom. Followed by Aunt Tabby, he hurried to Elaine. "Wh-what was it?" he asked, puffing at the exertion of running up-stairs. "I saw--a face--at the window--with some kind of thing over it!" gasped Elaine. "It was like one I saw once before." Uncle Joshua did not wait to hear any more. With the gun pointed ahead of him, ready for instant action, he ran out of the room and into the garden, beneath Elaine's window. He looked about for signs of an intruder. There was not a sound. No one was about, here. "I don't see any one," he called up to Elaine and Aunt Tabby in the window. He happened to look down at the ground. Before him was a small box. He picked it up. "Here's something, though," he said. Joshua went back into the house. "What is it?" asked Elaine as he rejoined the women. She took the curious little box and unfastened the cover. As she opened it, she drew back. There in the box was a little ivory figure of a man, all hunched up and shrunken, a hideous figure. She recoiled from it--it reminded her too much of the Chinese devil-god she had seen,--and she dropped the box. For a moment all stood looking at it in horrified amazement. . . . . . . . It was the afternoon following the day of our strange discovery of the fireplace done in sympathetic ink on the apparently blank sheet of paper in Bennett's effects, when the speaking-tube sounded and I answered it. "Why--it's Elaine," I exclaimed. Kennedy's face showed the keenest pleasure at the unexpected visit. "Tell her to come right up," he said quickly. I opened the door for her. "Why--Elaine--I'm awfully glad to see you," he greeted, "but I thought you were rusticating." "I was, but, Craig, it seems to me that wherever I go, something happens," she returned. "You know, Aunt Tabby said there were haunts. I thought it was an old woman's fear--but last night I heard the strangest noises out there, and I thought I saw a face at the window--a face in a helmet. And when Joshua went out, this is what he found on the ground under my window." She handed Kennedy a box, a peculiar affair which she touched gingerly and only with signs of the greatest aversion. Kennedy opened it. There, in the bottom of the box, was a little ivory devil-god. He looked at it curiously a moment. "Let me see," he ruminated, still regarding the sign. "The house you bought for Aunt Tabby, once belonged to Bennett, didn't it?" Elaine nodded her head. "Yes, but I don't see what that can have to do with it," she agreed, adding with a shudder, "Bennett is dead." Kennedy had taken a piece of paper from the desk where he had put it away carefully. "Have you ever seen anything that looks like this?" he asked, handing her the paper. Elaine looked at the plan carefully, as Kennedy and I scanned her face. She glanced up, her expression showing plainly the wonder she felt. "Why, yes," she answered. "That looks like Aunt Tabby's fireplace in the living-room." Kennedy said nothing for a moment. Then he seized his hat and coat. "If you don't mind," he said, "we'll go back there with you." "Mind?" she repeated. "Just what I had hoped you would do." . . . . . . . Wu Fang, the Chinese master mind, had arrived in New York. Beside Wu, the inscrutable, Long Sin, astute though he was, was a mere pigmy--his slave, his advance agent, as it were, a tentacle sent out to discover the most promising outlet for the nefarious talents of his master. New York did not know of the arrival of Wu Fang, the mysterious--yet. But down in the secret recesses of Chinatown, in the ways that are devious and dark, the oriental crooks knew--and trembled. Thus it happened that Long Sin was not permitted to enjoy even the foretaste of Bennett's spoils which he had forced from him after his weird transformation into his real self, the Clutching Hand, when the Chinaman had given him the poisoned draught that had put him into his long sleep. He had obtained the paper showing where the treasure amassed by the Clutching Hand was hidden, but Wu Fang, his master, had come. Wu had immediately established himself in the most sumptuous of apartments, hidden behind the squalid exterior of the ordinary tenement building in Chinatown. The night following his arrival, Wu Fang was reclining on a divan, when his servant announced that Long Sin was at the door. As Long Sin entered, it was evident that, cunning and shrewd though he was himself, Wu was indeed his master. He approached in fear and awe, cringing low. "Have you brought the map with you?" asked Wu. Long Sin bowed low again, and drew from under his coat the paper which he had obtained from Bennett. For a moment the two, master and slave in guile, bent over, closely studying it. At one point in the map Long Sin's bony finger paused over a note which Bennett had made: BEWARE POISONED GAS UPON OPENING COMPARTMENT. "And you think you can trace it out?" asked Wu. "Without a doubt," bowed Long Sin. He went over to a bag near-by, which he had already sent up by another servant, and opened it. Inside was an oxygen helmet. He replaced it, after showing it to Wu. "With the aid of the science of the white devil, we shall overcome the science of the white devil," purred Long Sin subtly. Outside, Wu had already ordered a car to wait, and together the two drove off rapidly. Into the country, they sped, until at last they came to a lonely turn in a lonely road, somewhat removed from the section that was rapidly being built up as population reached out from the city, but on a single-tracked trolley line. Long Sin alighted and disappeared with a parting word of instruction from Wu who remained in the car. The Chinaman carried with him the heavy bag with the oxygen helmet. Along this interurban trolley the cars made only half-hourly trips at this time of night. Long Sin hurried down the road until he came to a trolley pole, then looked hastily at his watch. It was twenty minutes at least before the next car would pass. Quickly, almost monkey-like, he climbed up the pole, carrying with him the end of a wire which he had taken from the bag. Having thrown this over the feed wire, he slid quickly to the ground again. Then, carrying the other end of the wire in his rubber-gloved hands, he made his way through the underbrush, in and out, almost like the serpent he was, until he came to a passageway in the rough and uncleared hillside--a small opening formed by the rocks. It was dark inside, but he did not hesitate to enter, carrying the wire and the bag with him. . . . . . . . It was nightfall before we arrived with Elaine at Aunt Tabby's. We entered the living-room and Elaine introduced us both to Aunt Tabby and her husband. It was difficult to tell whether Elaine's old nurse was more glad to see her than the faithful Rusty who almost overwhelmed her even after so short an absence. In the midst of the greetings, I took occasion to look over the living-room. It was a very cozy room, simply and tastefully furnished, and I fancied that I could see in the neatness of Aunt Tabby a touch of Elaine's hand, for she had furnished it for her faithful old friend. I followed Kennedy's eyes, and saw that he was looking at the fireplace. Sure enough, it was the same in design as the fireplace which the heat had so unexpectedly brought out in sympathetic ink on the blank sheet of paper. Kennedy lost no time in examining it, and we crowded around him as he went over it inch by inch, following the directions on the drawing. At one point in the drawing a peculiar protuberance was marked. Kennedy was evidently hunting for that. He found it at last and pressed the sort of lever in several ways. Nothing seemed to happen. But finally, almost by chance, he seemed to discover the secret. A small section at the side of the fireplace opened up, disclosing an iron ladder, leading down into one of those characteristic hiding-places in which the Clutching Hand used to delight. Kennedy looked at the mysterious opening some time, as if trying to fathom the mystery. "Let's go down and explore it," I suggested, taking a step toward the ladder. Kennedy reached out and pulled me back. Then without a word he pressed the little lever and the door closed. "I think we'd better wait a while, Walter," he decided. "I would rather hear Aunt Tabby's haunts myself." He carefully went over not only the rest of the house but the grounds about it, without discovering anything. Aunt Tabby, with true country hospitality, seemed unable to receive guests without feeding them, and, although we had had a big dinner at a famous road-house on the way out, still none of us could find it in our hearts to refuse her hospitality. Even that diversion, however, did not prevent us from talking of nothing else but the strange noises, and I think, as we waited, we all got into the frame of mind which would have manufactured them even if there had been none. We were sitting about the room when suddenly the most weird and uncanny rappings began. Rusty was on his feet in a moment, barking like mad. We looked from one to another. It was impossible to tell where the noises came from, or even to describe them. They were certainly not ghostly rappings. In fact, they sounded more like some twentieth century piece of machinery. We listened a moment, then Kennedy walked over to the fireplace. "You can explore it with me now, Walter," he said quietly, touching the lever and opening the panel which disclosed the ladder. He started down the ladder and I followed closely. Elaine was about to join us, when Kennedy paused on the topmost round and looked up at her. "No, no, young lady," he said with mock severity, "you have been through enough already--you stay where you are." Elaine argued and begged but Kennedy was obdurate. It was only when Aunt Tabby and Joshua added their entreaties that she consented reluctantly to remain. Together, Craig and I descended into the darkness about eight or ten feet. There we found a passageway, excavated through the earth and rock, along which we crept. It was crooked and uneven, and we stumbled, but kept going slowly ahead. Kennedy, who was a few feet in front of me, stopped suddenly and I almost fell over him. "What is it?" I whispered. . . . . . . . Long Sin had made his way from the opening of the cave to the point on the plan which was marked by a cross, and there he had set up his electric drill which was connected to the trolley wire. He was working furiously to take advantage of the fifteen minutes or so before the next car would pass. The tunnel had been widened out at this point into a small subterranean chamber. It was dug out of the earth and the roof was roughly propped up, most of the weight being borne by one main wooden prop which, in the dampness, had now become old and rotten. On one side it was evident that Long Sin had already been at work, digging and drilling through the earth and rock. He had gone so far now that he had disclosed what looked like the face of a small safe set directly into the rock. As he worked he would stop from time to time and consult the map. Then he would take up drilling again. He had now come to the point on which Bennett had written his warning. Quickly he opened the bag and took out the oxygen helmet, which he adjusted carefully over his head. Then he set to work with redoubled energy. It was that drill as well as his pounding on the rock which had so alarmed Elaine and Aunt Tabby the night before and which now had been the signal for Kennedy's excursion of discovery. . . . . . . . Our man, whoever he was, must have heard us approaching down the tunnel, for he paused in his work and the noise of the drill ceased. He looked about a moment, then went over to the prop and examined it, looking up at the roof of the chamber above him. Evidently he feared that it was not particularly strong. From our vantage point around the bend in the passageway we could see this strange and uncouth figure. "Who is it, do you think?" I whispered, crouching back against the wall for fear that he might look even around a corner or through the earth and discover us. As I spoke, my hand loosened a piece of rock that jutted out and before I knew it there was a crash. "Confound it, Walter," exclaimed Kennedy. Down the passageway the figure was now thoroughly on the alert, staring with his goggle-like eyes into the blackness in our direction. It was not the roof above him that was unsafe. He was watched, and he did not hesitate a minute to act. He seized the bag and picked his way quickly through the passage as if thoroughly familiar with every turn of the walls and roughness of the floor. We were discovered and if we were to accomplish anything, it was now or never. Kennedy dashed forward and I followed close after him. We were making much better time than our strange visitor and were gaining on him rapidly. Nearer and nearer we came to him, for, in spite of his familiarity with the cavern he was hampered by the outlandish head-gear that he wore. It was only another instant, when Kennedy would have laid his hands on him. Suddenly he half turned, raised his arm and dashed something to the earth much as a child explodes a toy torpedo. I fully expected that it was a bomb; but, as a moment later, I found that Kennedy and I were still unharmed, I knew that it must be some other product of this devilish genius. The thickest and most impenetrable smoke seemed to pervade the narrow cavern! "A Chinese smoke bomb!" sputtered and coughed Kennedy, as he retreated a minute, then with renewed vigor endeavored to penetrate the dense and opaque fumes. We managed to go ahead still, but the intruder had exploded one after another of his peculiar bombs, always keeping ahead of the smoke which he created, and we found that under its cover he had made good his escape, probably reaching the entrance of the cave in the underbrush. At the other end of the passageway, up in the living-room of the cottage, the draught had carried large quantities of the smoke. Elaine, Aunt Tabby and Joshua coughing and choking, saw it, and opened a window, which seemed to cause a current of air to sweep through the whole length of the passageway and helped to clear away the fumes rapidly. Long Sin, meanwhile, had started to work his way through the bushes to reach the waiting car, with Wu, then paused and listened. Hearing no sound, he replaced the helmet which he had taken off. Pursuit was now useless for us. With revolvers drawn, we crept back along the passageway until we came again to the chamber itself. There, on the floor, lay a bag of tools, opened, as though somebody had been working with them. "Caught red-handed!" exclaimed Kennedy with great satisfaction. He looked at the tools a minute and then at the electric drill, and finally an idea seemed to strike him. He took up the drill and advanced toward the safe. Then he turned on the current and applied the drill. The drill was of the very latest design and it went quickly through the steel. But beyond that there was another thin steel partition. This Kennedy tackled next. The drill went through and he withdrew it. Instantly the most penetrating and nauseous odor seemed to pervade everything. Kennedy cried out. But his warning was too late. We staggered back, overcome by the escaping gas and fell to the ground. . . . . . . . Long Sin, with his oxygen helmet on again, had returned to the passageway and was now stealthily creeping back. He came to the chamber and there discovered us lying on the ground, overcome. He bent down and, to his great satisfaction, saw that we were really unconscious. Quickly he moved over to the safe and pried open the last thin steel plate. Inside was a small box. He picked it up and tried to open it, but it was locked. There was no time to work over it here, and he took it under his arm and started to leave. He paused a moment to look at us, then took out a piece of paper and a pencil and on the paper wrote, "Thanks for your trouble." Beneath, it was signed by his special stamp--the serpent's head, mouth open and fangs showing. Long Sin looked at us a moment, then a subtle smile seemed to spread over his face. At last he had us in his power. He drew out a long, wicked-looking Chinese knife and stuck it through the note. Then he felt the edge of the knife. It was keen. . . . . . . . In the sitting-room, Elaine, Aunt Tabby and Joshua had been listening intently at the fireplace but heard nothing. They were now getting decidedly worried. Finally, the fumes which we had released made their way to the room. They were considerably diluted by fresh air by that time, but, although they were nauseous, were not sufficient to overcome any one. Still, the smell was terrible. "I can't stand it any longer," cried Elaine. "I'm going down there to see what has become of them." Aunt Tabby and Joshua tried to stop her, but she broke away from them and went down the ladder. Rusty leaped down after her. Joshua tried to follow, but Aunt Tabby held him back. He would have gone, too, if she had not managed to strike the spring and shut the door, closing up the passageway. Joshua got angry then. "You are making a coward of me," he cried, beating on the panel with the butt of his gun and struggling to open it. He seemed unable to fathom the secret. Elaine was now making her way as rapidly as she could through the tunnel, with Rusty beside her. . . . . . . . It was just as Long Sin had raised his knife that the sound of her footsteps alarmed him. He paused and leaped to his feet. There was no time for either to retreat. He started toward Elaine, and seized her roughly. Back and forth over the rocky floor they struggled. As they fought,--she with frantic strength, he craftily,--he backed her slowly up against the prop that upheld the roof. He raised his keen knife. She recoiled. The prop, none too strong, suddenly gave way under her weight. The whole roof of the chamber fell with a crash, earth and stone overwhelming Elaine and her assailant. . . . . . . . By this time Joshua had left the house and had gone out into the garden to get something to pry open the fireplace door. Of a sudden, to his utter amazement, a few feet from him, it seemed as if the very earth sank in his garden, leaving a yawning chasm. He looked, unable to make it out. Before his very eyes a strange figure, the figure of Long Sin in his oxygen helmet, appeared, struggling up, as if by magic from the very earth, shaking the debris off himself, as a dog would shake off the water after a plunge in a pond. Long Sin was gone in a moment. Then again the earth began to move. A paw appeared, then a sharp black nose, and a moment later, Rusty, too, dug himself out. Joshua had run into the house to get a spade when Rusty, like a shot, bolted for the house, took the window at a leap and all covered with earth landed before Joshua and Aunt Tabby. "See!--he went down there--now he's here!" cried Aunt Tabby, pointing at the fireplace, then looking at the window. Rusty was running back and forth from Joshua to the window. "Follow him!" cried Aunt Tabby. Rusty led the way back again to the garden, to the cave-in. "Elaine!" gasped Aunt Tabby. By this time Joshua was digging furiously. Rusty, too, seemed to understand. He threw back the earth with his paws, helping with every ounce of strength in his little body. At last the spade turned up a bit of cloth. "Elaine!" Aunt Tabby cried out again. She was in a sort of little pocket, protected by the fortunate formation of the earth as it fell, yet almost suffocated, weak but conscious. Aunt Tabby rushed up as Joshua laid down the spade and lifted out Elaine. They were about to carry her into the house, when she cried weakly, but with all her remaining strength. "No--no--Dig! Craig--Walter!" she managed to gasp. Rusty, too, was still at it. Joshua fell to again. Man and dog worked with a will. "There they are!" cried Elaine, as all three pulled us out, unconscious but still alive. Though we did not know it, they carried us into the house, while Elaine and Aunt Tabby bustled about to get something to revive us. At last I opened my eyes and saw the motherly Aunt Tabby bending over me. Craig was already revived, weak but ready now to do anything Elaine ordered, as she held his hand and stroked his forehead softly. . . . . . . . Meanwhile Long Sin had made his way to the automobile where his master, Wu, waited impatiently. "Did you get it?" asked Wu eagerly. Long Sin showed him the box. "Hurry, master!" he cried breathlessly, leaping into the car and struggling to take off the helmet as they drove away. "They may be here--at any moment." The machine was off like a shot and even if we had been able to follow, we could not now have caught it. Back in Wu's sumptuous apartment, later, Wu and his slave, Long Sin, after their hurried ride, dismissed all the servants and placed the little box on the table. Wu rose and locked the door. Then, together, they took a sharp instrument and tried to pry off the lid of the box. The lid flew off. They gazed in eagerly. Inside was a smaller box, which Wu seized eagerly and opened. There, on the plush cushion lay merely a round knobbed ring! Was this the end of their great expectations? Were Bennett's millions merely mythical? The two stared at each other in chagrin. Wu was the first to speak. "Where there should have been seven million dollars," he muttered to himself, "why is there only a mystic ring?" CHAPTER II THE CRYPTIC RING Kennedy had been engaged for some time in the only work outside of the Dodge case which he had consented to take for weeks. Our old friend, Dr. Leslie, the Coroner, had appealed to him to solve a very ticklish point in a Tong murder case which had set all Chinatown agog. It was, indeed, a very bewildering case. A Chinaman named Li Chang, leader of the Chang Wah Tong, had been poisoned, but so far no one had been able to determine what poison it was or even to prove that there had been a poison, except for the fact that the man was dead, and Kennedy had taken the thing up in a great measure because of the sudden turn in the Dodge case which had brought us into such close contact with the Chinese. I had been watching Kennedy with interest, for the Tong wars always make picturesque newspaper stories, when a knock at the door announced the arrival of Dr. Leslie, anxious for some result. "Have you been able to find out anything yet?" he greeted Kennedy eagerly as Craig looked up from his microscope. Kennedy turned and nodded. "Your dead man was murdered by means of aconite, of which, you know, the active principle is the deadly alkaloid aconitine." Craig pulled down from the shelf above him one of his well-thumbed standard works on toxicology. He turned the pages and read: "Pure aconite is probably the most actively poisonous substance with which we are acquainted. It does not produce any decidedly characteristic post-mortem appearances, and, in fact, there is no reliable chemical test to prove its presence. The chances of its detection in the body after death are very slight." Dr. Leslie looked up. "Then there is no test, none?" he asked. "There is one that is brand new," replied Kennedy slowly. "It is the new starch-grain test just discovered by Professor Reichert, of the University of Pennsylvania. The peculiarities of the starch grains of various plants are quite as great as those of the blood crystals, which, you will recall, Walter, we used once. "The starch grains of the poison have remained in the wound. I have recovered them from the dead man's blood and have studied them microscopically. They can be definitely recognized. This is plainly a case of aconite poisoning--probably suggested to the Oriental mind by the poison arrows of the Ainus of Northern Japan." Dr. Leslie and I both looked through the microscope, comparing the starch grains which Kennedy had discovered with those of scores of micro-photographs which lay scattered over the table. "There are several treatments for aconite poisoning," ruminated Kennedy. "I would say that one of the latest and best is digitalin given hypodermically." He took down a bottle of digitalin from a cabinet, adding, "only it was too late in this case." . . . . . . . Just what the relations were between Long Sin and the Chong Wah Tong I have never been able to determine exactly. But one thing was certain: Long Sin on his arrival in New York had offended the Tong and now that his master, Wu Fang, was here the offence was even greater, for the criminal society brooked no rival. In the dark recesses of a poorly furnished cellar, serving as the Tong headquarters, the new leader and several of his most trusted followers were now plotting revenge. Long Sin, they believed, was responsible for the murder, and, with truly Oriental guile, they had obtained a hold over Wu Fang's secretary. Their plan decided on, the Chinamen left the headquarters and made their way separately up-town. They rejoined one another in the shelter of a rather poor house, before which was a board fence, in the vicinity of a fashionable apartment house. A moment's conference followed, and then the secretary glided away. . . . . . . . Wu had taken another apartment up-town in one of the large apartment houses near a parkway; for he was far too subtle to operate from his real headquarters back of the squalid exterior of Chinatown. There Long Sin was now engaged in making all possible provisions for the safety of his master. Any one who had been walking along the boulevard and had happened to glance up at the roof of the tall apartment building might have seen Long Sin's figure silhouetted against the sky on the top of the mansard roof near a flagpole. He had just finished fastening to the flagpole a stout rope which stretched taut across an areaway some twenty or thirty feet wide to the next building, where it was fastened to a chimney. Again and again he tested it, and finally with a nod of satisfaction descended from the roof and went to the apartment of Wu. There, alone, he paused for a few minutes to gaze in wonder at the cryptic ring which had been the net result so far of his efforts to find the millions which Bennett, as the Clutching Hand, had hidden. He wore it, strangely enough, over his index finger, and as he examined it he shook his head in doubt. Neither he nor his master had yet been able to fathom the significance of the ring. Long Sin thought that he was unobserved. But outside, looking through the keyhole, was Wu's secretary, who had stolen in on the mission which had been set for him at the Tong headquarters. Long Sin went over to a desk and opened a secret box in which Wu had placed several packages of money with which to bribe those whom he wished to get into his power. It was Long Sin's mission to carry out this scheme, so he packed the money into a bag, drew his coat more closely about him and left the room. No sooner had he gone than the secretary hurried into the room, paused a moment to make sure that Long Sin was not coming back, then hurried over to a closet near-by. From a secret hiding-place he drew out a small bow and arrow. He sat down at a table and hastily wrote a few Chinese characters on a piece of paper, rolling up the note into a thin quill which he inserted into a prepared place in the arrow. Then he raised the window and deftly shot the arrow out. Down the street, back of the board fence, where the final conference has taken place, was a rather sleepy-looking Chinaman, taking an occasional puff at a cigarette doped with opium. He jumped to his feet suddenly. With a thud an arrow had buried itself quivering in the fence. Quickly he seized it, drew out the note and read it. In the Canton vernacular it read briefly: "He goes with much money." It was enough. Instantly the startling news overcame the effect of the dope, and the Chinaman shuffled off quickly to the Tong headquarters. They were waiting for him there, and he had scarcely delivered the message before their plans were made. One by one they left the headquarters, hiding in doorways, basements and areaways along the narrow street. . . . . . . . Long Sin was making his rounds, visiting all those whom the glitter of Wu's money could corrupt. Suddenly from the shadows of a narrow street, lined with the stores of petty Chinese merchants, half a dozen lithe and murderous figures leaped out behind Long Sin and seized him. He struggled, but they easily threw him down. Any one who has visited Chinatown knows that at every corner and bend of the crooked streets stands a policeman. It was scarcely a second before the noise of the scuffle was heard, but it was too late. The half dozen Tong men had seized the money which Long Sin carried and had deftly stripped him of everything else of value. The sound of the approaching policeman now alarmed them. Just as the new Tong leader had raised an axe to bring it down with crushing force on Long Sin's skull a shot rang out and the axe fell from the broken wrist of the Chinaman. In another moment the policeman had seized him. Then followed a sharp fight in which the Tong men's knowledge of jiu-jitsu stood them in good stead. The policeman was hurled aside, the Tong leader broke away, and one by one his followers disappeared through dark hallways and alleyways, leaving the policeman with only two prisoners and Long Sin lying on the sidewalk. But the ring and the money were gone. "Are you hurt much?" demanded the burly Irish officer, assisting Long Sin to his feet, none too gently. Long Sin was furious over the loss of the precious ring, yet he knew to involve himself in the white man's law would end only in disaster both for him and his master. He forced a painful smile, shook his head and managed to get away down the street muttering. He made his way up-town and back to the apartment of Wu, and there, pacing up and down in a fury, attended to his wounds. His forefinger, from which the ring had been so ruthlessly snatched, was a constant reminder to him of the loss. Any one who could have studied the vengefulness of his face would have seen that it boded ill for some one. . . . . . . . It was the day after her return from Aunt Tabby's that Kennedy called again upon Elaine to find that she and Aunt Josephine were engaged in the pleasant pastime of arranging an entertainment. Jennings announced Craig and held back the portieres as he entered. "Oh, good!" cried Elaine as she saw him. "You are just in time. I was going to send you this, but I should much rather give it to you." She handed him a tastefully engraved sheet of paper which he read with interest: Miss Elaine Dodge requests the honor of your presence at an Oriental Reception on April 6th, at 8 o'clock. "Very interesting," exclaimed Craig enthusiastically. "I shall be delighted to come." He looked about a moment at the library which Elaine was already rearranging for the entertainment. "Then you must work," she cried gaily. "You are just in time to help me buy the decorations. No objections--come along." She took Kennedy's arm playfully. "But I have a very important investigation for the Coroner that I am--" "No excuses," she cried, laughingly, dragging him out. Among the many places which Elaine had down on her shopping list was a small Chinese curio shop on lower Fifth avenue. They entered and were greeted with a profound bow by the proprietor. He was the new Tong leader, and this up-town shop was his cover. In actual fact, he was what might have been called a Chinese fence for stolen goods. In their interest in the wealth of strange and curious ornaments displayed in the shop they did not notice that the Chinaman's wrist was bound tightly under his flowing sleeve. Elaine explained what it was she wanted, and with Kennedy's aid selected a number of Chinese hangings and decorations. They were about to leave the shop when Elaine's eye was attracted by a little show case in which were many quaint and valuable Chinese ornaments in gold and silver and covered ivory. "What an odd looking thing," she said, pointing out a knobbed ring which reposed on the black velvet of the case. "Quite odd," agreed Kennedy. The subtle Chinaman stood by the pile of hangings on the counter which Elaine had bought, overjoyed at such a large sale. Praising the ring to Elaine, he turned insinuatingly to Kennedy. There was nothing else for Craig to do--he bought the ring, and the Chinaman proved again his ability as a merchant. From the curio shop where Elaine had completed her purchases they drove to Kennedy's laboratory. I had been at work on a story for the Star when they entered. "You will be there, too, Mr. Jameson?" coaxed Elaine, as she told of their morning's work. I needed no urging. We were in the midst of planning the entertainment when a slight cough behind me made me start and turn quickly. There stood Long Sin, the astute Chinaman who had delivered the bomb to Kennedy and had betrayed Bennett. We had seen very little of him since then. Long Sin bowed low and shuffled over closer to Kennedy. I noticed that Elaine eyed Long Sin sharply. But as yet we had seen no reason to suspect him, so cleverly had he covered his tracks. Kennedy, having used him once to capture Bennett, was still not unwilling to use him in attempting to discover where Bennett's hidden millions lay. "I am in great trouble, Professor Kennedy," began Long Sin in a low tone. "You don't know the Chinese of the city, but if you did you would know what blackmailers there are among them. I have refused to pay blackmail to the Chong Wah Tong, and since then it has been trouble, trouble, trouble." Kennedy looked up quickly at the name Chong Wah Tong, thinking of the investigation which the Coroner had asked him to make into the murder. He and Long Sin moved a few steps away, discussing the affair. Elaine and I were still talking over the entertainment. She happened to place her hand on the desk near Long Sin. My back was toward him and I did not see him start suddenly and look at her hand. On it was the ring--the ring which, unknown to us, Long Sin had found in the passageway under Aunt Tabby's garden, of which he had been robbed, and which now, by a strange chance, had come into Elaine's possession. It was a peculiar situation for Long Sin, although as yet we did not know it. He could not lay claim to the mystic ring, for then Kennedy would make him prove his ownership, and the whole affair of which we still knew nothing would be exposed. He acted quickly. Long Sin decided to recover the ring by stealth. Elaine was still talking enthusiastically about her party, when Long Sin turned from Kennedy and moved toward us with a bow. "The lady speaks of an Oriental reception," he remarked. "Would she care to engage a magician?" Elaine turned to him surprised. "Do you mean that you are a magician?" she asked, puzzled. Long Sin smiled quietly. He reached over and took a small bottle from Kennedy's laboratory table. Holding it in his hand almost directly before us, he made a few sleight-of-hand passes, and, presto! the bottle had disappeared. A few more passes, and a test tube appeared in its place. Before we knew it he had caused the test tube to disappear and the bottle to reappear. We all applauded enthusiastically. "I don't think that is such a bad idea after all," nodded Kennedy to Elaine. "Perhaps not," she agreed, a little doubtfully. "I hadn't intended to have such a thing, but--why, of course, that would interest everybody." . . . . . . . It was the night of the reception. The Dodge library was transformed. The Oriental hangings which Elaine and Kennedy had purchased seemed to breathe mysticism. At the far end of the room a platform had been arranged to form a stage on which Long Sin was to perform his sleight-of-hand. The drawing-room also was decorated like the library. At the other end of the room Elaine and Aunt Josephine, in picturesque Oriental costume, were greeting the guests. Every one seemed to be delighted with the novelty of the affair. We came in just a bit ahead of Long Sin, and Elaine greeted us. Almost everybody had arrived when Elaine turned to the guests and introduced Long Sin with a little speech. Long Sin bowed and every one applauded. He made his way to the platform in the library and mounted it. I shall not attempt to describe the amazing series of tricks which he performed. His hands and fingers seemed to move like lightning. Among other things, I remember he took up a cover from a table near-by. He held it up before us. Instantly it seemed that a flock of pigeons flew out of it around the room. How he did it I don't know. They were real pigeons, however, and the trick brought down the house. Long Sin bowed. Another of his feats which I recall was nothing less than kindling a fire on a small bit of tin and, as the flames mounted, he deliberately stepped into them, apparently as unharmed as a salamander. So it went from one thing to another. The entertainment was brilliant in itself, but Long Sin seemed to put the finishing touch to it. In fact, I suppose that it was a couple of hours that he continued to amuse us. He had finished and every one crowded about him to congratulate him on his skill. His only answer, however, was his inscrutable smile. "This is wonderful, wonderful," I repeated as I happened to meet Elaine alone. We walked into the conservatory while the guests were crowding around Long Sin. She seated herself for the first time during the evening. "May I get you an ice?" I suggested. She thanked me, and I hurried off. As I passed through the drawing-room I did not notice that Long Sin had managed to escape further congratulations of the guests. Just then a waiter passed through with ices on a tray. I called to him and he stopped. A moment later Long Sin himself took an ice from the tray and retreated back of the portieres. No one was about, and he hastily drew a bottle from his pocket. On the bottle was a Chinese label. He palmed the bottle, and any one who had chanced to see him would have noticed that he passed it two or three times over the ice, then, lifting the portieres, entered the drawing-room again. He had made the circuit of the rooms in such a way as to bring himself out directly in my path. With a smile he stopped before me, rubbing both hands together. "It is for Miss Elaine?" he asked. I nodded. By this time several of the guests who were fascinated with Long Sin gathered about us. Long Sin fluttered open a Chinese fan which he had used in his tricks, passed it over my hand, and in some incomprehensible way I felt the plate with the ice literally disappear from my grasp. My face must have shown my surprise. A burst of laughter from the other guests greeted me. I looked at Long Sin, half angry, yet unable to say anything, for the joke was plainly on me. He smiled, made another pass with the fan, and instantly the plate with the ice was back in my hand. There was nothing for me but to take the joke in the spirit in which the other guests had taken it. I laughed with them and managed to get away. Meanwhile Kennedy had been moving from one to another of the guests seeking Elaine. He had already taken an ice from the waiter and was going in the direction of the conservatory. There he found her. "Won't you take this ice?" he asked, handing it to her. "It is very kind of you," she said, "but I have already sent Walter for one." Kennedy insisted and she took it. She had already started to eat it when I appeared in the doorway. I was rather vexed at Long Sin for having delayed me, and I mumbled something about it. Kennedy laughed, rather pleased at having beaten me. "Never mind, Walter," he said with a smile, "I'll take it. And er--I don't think that Elaine will object if you play the host for a little while with Aunt Josephine," he hinted. I saw that three was a crowd and I turned to retrace my steps to the drawing-room. Kennedy, however, was not alone. Back of the palms in the conservatory two beady black eyes were eagerly watching. Long Sin had noted every movement as his cleverly laid plan miscarried. Chatting with animation, Kennedy tasted the ice. He had taken only a couple of spoonfuls when a look of wonder and horror seemed to spread over his face. He rose quickly. A cold sweat seemed to break out all over him. His nerves almost refused to respond. His tongue seemed to be paralyzed and the muscles of his throat seemed to be like steel bands. He took only a few steps, began to stagger, and finally sank down on the floor. Elaine screamed. We rushed in from the library and drawing-room. There lay Kennedy on the floor, his face most terribly contorted. We gathered around him and he tried to raise himself and speak, but seemed unable to utter a sound. He had fallen near the fountain and one hand drooped over into the water. As he fell back he seemed to have only just enough strength to withdraw his hand from the fountain. On the stone coping, slowly and laboriously, he moved his finger. "What's the matter, old man?" I asked, bending over him. There was no answer, but he managed to turn his head, and I followed the direction of his eyes. With trembling finger he was tracing out, one by one, some letters. I looked and it flashed over me what he meant. He had written with the water: "Digitalin--lab--" I jumped up and almost without a word dashed out of the conservatory, down the hall and into the first car waiting outside. "To the laboratory," I directed, giving the driver the directions, "and drive like the deuce!" Fortunately there was no one to stop us, and I know we broke all the speed laws of New York. I dashed into the laboratory, almost broke open the cabinet, and seized the bottle of digitalin and a hypodermic syringe, then rushed madly out again and into the car. Meanwhile some of the guests had lifted up Kennedy, too excited to notice Long Sin in his hiding-place. They had laid Craig down on a couch and were endeavoring to revive him. Some one had already sent for a doctor, but the aconite was working quickly on its victim, and he was slowly stiffening out. Elaine was frantic. I scarcely waited for the car to stop in front of the house. I opened the door and rushed in. Without a word I thrust the antidote and the syringe into the hands of the doctor and he went to work immediately. We watched with anxiety. Finally Kennedy's eyes opened and gradually his breathing seemed to become more normal. The antidote had been given in time. . . . . . . . Kennedy was considerably broken up by the narrow escape which he had had, and, naturally, even the next morning, did not feel like himself. In the excitement of leaving Elaine's we had forgotten the bottle of digitalin. As for myself, I had been so overjoyed at seeing my old friend restored that I would have forgotten anything. Kennedy looked rather wan and peaked, but insisted on going to the laboratory as usual. "Do you remember what became of the bottle of digitalin?" he asked, fumbling in the closet. Mechanically I felt in my own pockets; it was not there. I shook my head. "I don't seem to remember what became of it--perhaps we left it there. In fact, we must have left it there." "I don't like to have such things lying around loose," remarked Kennedy, taking up his hat and coat with forced energy. "I think we had better get it." Elaine had spent rather a sleepless night after the attempt to poison her which had miscarried and resulted in poisoning Kennedy. To keep her mind off the thing, she had already started to take down the decorations. Jennings and Marie, as well as a couple of workmen, were restoring the library to its normal condition under the direction of Aunt Josephine. The telephone rang and Elaine answered it. Her face showed that something startling had happened. "It was Jameson," she cried, almost dropping the receiver, overcome. They all hurried to her. "He says that Mr. Kennedy and he were visiting that Chinaman this morning and Mr. Kennedy suffered a relapse--is dying there, in the Chinaman's apartment. He wants us to come quickly and bring that medicine that they used last night. He says it is on the tabaret in the library. Marie, will you look for it? And, Jennings, get the car right away." Jennings hurried from the room, and a moment later Marie had found the bottle behind some ornaments on the tabaret and came back with it. Scarcely knowing what to do, Elaine, followed by Aunt Josephine, had rushed from the house, hatless and coatless, just as the car swung around from the garage in the rear. Jennings went out with the wraps. They seized them and leaped into the car, which started off swiftly. It was only a matter of minutes when they pulled up before the apartment house where Wu had taken the suite from which Long Sin had telephoned the message in my name. Together Elaine and Aunt Josephine hurried in. . . . . . . . Kennedy went directly from the laboratory to the Dodge house. I don't think I ever saw such an expression of surprise on anybody's face as that on Jennings's when he opened the door and saw us. He was aghast. Back of him we could see Marie. She looked as if she had seen a ghost. "Is Miss Elaine in?" asked Kennedy. Jennings was even too dumfounded to speak. "Why, what's the matter?" demanded Kennedy. "Then--er--you are not ill again?" he managed to blurt out. "Ill again?" repeated Kennedy. "Why," explained Jennings, "didn't Mr. Jameson just now telephone that you had had a relapse in the apartment of that Chinaman, and for Miss Elaine to hurry over there right away with that bottle of medicine?" Kennedy waited to hear no more. Seizing me by the arm, he turned and dashed down the steps and back again into the taxicab in which we had come. . . . . . . . In Wu's apartment Long Sin was giving his secretary and another Chinaman the most explicit instructions. As he finished each nodded and showed him a Chinese dirk concealed under his blouse. Just then a knock sounded at the door. The secretary opened it, and Aunt Josephine and Elaine almost ran in. Before they knew it, the secretary had locked the door. Long Sin rose and bowed with a smile. "Where is Mr. Kennedy?" demanded Elaine. Long Sin bowed again, spreading out his hands, palm outward. "Mr. Kennedy? He is not here." Then, straightening up, he faced the two women squarely. "You have a ring that means much to me," he said quickly. "The only way to get it from you was to bring you here." He was pointing now at the ring on Elaine's finger. She looked at it a moment in surprise, then at the menacing Chinaman, and turned quickly. She ran to the door. It was locked. Long Sin, motionless, smiled. "There is no way to get out," he murmured. Aunt Josephine was standing now with her back to the door leading into another room. She happened to look up and saw the secretary, who was near her and half turned away. From where she was standing she could see the murderous dirk up his sleeve. She acted instantly. Without a word she summoned all her strength and struck him. The secretary stumbled. "Elaine," she cried, "look out! they have knives." Before Elaine knew it Aunt Josephine had taken her by the arm, had pulled her into the back room, and, although Long Sin and the others had rushed forward, managed to slam the door and lock it. The Chinamen set to work immediately to pry it open. While they were at work on the doer, which was already swaying, Aunt Josephine and Elaine were running about, trying to find an outlet from the room. There seemed to be no way out. Even the windows were locked. "I don't know why they want the ring," whispered Aunt Josephine, "but they won't get it. Give it to me, Elaine." She almost seized the ring, hiding it in her waist. As she did so the door burst open and Wu, Long Sin and the other Chinamen rushed in. A second later they seized Elaine and Aunt Josephine. . . . . . . . Kennedy and I dashed up before the apartment house in which we knew that Long Sin lived, leaped out of the car and hurried in. It was on the second floor, and we did not wait for the elevator but took the steps two at a time. Kennedy found the door locked. Instantly he whipped out his revolver and shot the lock in pieces. We threw ourselves against the door, the broken lock gave way and we rushed in through the front room. No one was there, but in a back room we could hear sounds. It was Elaine and Aunt Josephine struggling with the Chinamen. Long Sin and the others had seized Elaine and Aunt Josephine was trying to help her just as we rushed in. With a blow Kennedy knocked out the secretary, while I struggled with the other Chinamen who blocked the way. Then Kennedy went directly at Long Sin. They struggled furiously. Long Sin, with his wonderful knowledge of jiu-jitsu, might not have been a match for six other Chinamen, but he was for one white man. With a mighty effort he threw Kennedy, rushed for the door and, as he passed through the outside room, seized a Tong axe from the wall. Afraid of the wonderful jiu-jitsu, I had picked up the first thing handy, which was a tabaret. I literally broke it over the head of my Chinaman, then turned and dashed out after Long Sin just as Kennedy picked himself up and followed. I caught up with the Chinaman and we had a little struggle, but he managed to break away and raised his axe threateningly. A shout from Kennedy caused him to turn and run down the flight of stairs, Kennedy closely behind him. In the main hall of the apartment house were two elevator shafts facing the street entrance, some twenty-five or thirty feet away. Through the street door the janitor and two or three other men were running in. They had heard the noise of the fighting above. Escape to the street was cut off. We were behind him on the flight of stairs. Long Sin did not hesitate a moment. He ran to the elevator, the door of which was open, seized the elevator boy and sent him sprawling on the marble floor. Then he slammed the door and the elevator shot up. Kennedy was only a few feet behind, and he took in the situation at a glance. He leaped into the other elevator, and before the surprised boy could interfere shot it up only a few feet behind Long Sin. Up the two elevators rose, Kennedy firing as best he could at Long Sin, while the shots reverberated through the elevator shaft like cannon. It was a wild race to the roof. Long Sin had the start, and as the elevator reached the top floor he flung it open, dashed out and through a door up to the roof itself. A second later Kennedy's elevator stopped. Craig leaped out and fired his last shot at the legs of Long Sin as he disappeared at the top of the flight of stairs to the roof. He flung the revolver from him and followed. Without a moment's hesitation Kennedy threw himself at Long Sin. They struggled with each other. Finally Long Sin managed to wrench one arm lose and raise the Tong axe over Kennedy's head. Kennedy dodged back. As he did so he tripped on the very edge of the roof and went sliding down the slates of the mansard. Fortunately he was able to catch himself in the gutter. It was the opportunity that Long Sin wanted. He started across the rope, which he had stretched from this apartment house to the building across the court, with all the deftness of the most expert Chinese acrobat. By this time I had reached the roof, followed by the janitor and the elevator boys. Kennedy was now crawling up the mansard, helping himself as best he could by some of the ornamental ironwork. I hurried over with the janitor, and together we pulled him out of danger. Long Sin had reached the roof on the opposite side as we ran across in the direction of the taut rope. A moment later he returned and bowed at us mockingly, then disappeared behind a skylight. Kennedy did not stop an instant. "You fellows go down to the street and see if you can head him off that way," he cried. "Stay here, Walter." Before I knew it he had seized the rope and was going across to the other building, hand over hand. It was a perilous undertaking, but his blood was up. Kennedy had almost reached the other roof when suddenly from behind the skylight stepped Long Sin. With a wicked leer, he advanced to the edge of the roof, his axe upraised. I looked across the yawning chasm, horrified. Slowly Long Sin raised the axe above his head, gathering all the strength which he had, waiting for Kennedy to approach closer. Kennedy stopped. Swiftly the axe descended, slashing the rope at one blow. Like the weight of a pendulum Kennedy swung back against our own building, managing to keep his hold on the rope with superhuman strength. I bent far over the edge of the roof, fully expecting to see him dashed to pieces at the bottom of the court. There was a tremendous shattering of glass. The rope had been just long enough to make him strike a window and he had gone crashing through the glass three floors below. I dashed down the stairs and into the apartment. Kennedy was lying on the floor badly cut. I raised him up. He was dazed and considerably overcome; but as he staggered to his feet with my help I saw that no bones were broken. "Help me, quick, Walter," he urged, moving toward the elevators. Meanwhile Long Sin had quickly dived down into the next building. A few moments later he had come out on the ground floor at the rear. Gazing about to see whether he was followed, he disappeared. . . . . . . . Back in the apartment, Elaine and Aunt Josephine were just about to run out when the two Chinamen who had been knocked out recovered. One of them threw himself on Elaine. Aunt Josephine tried to ward him off, but the other one struck her and threw her down. Before she could recover they had seized Elaine. With a hasty guttural exclamation they picked her up and ran out. Instead of going down-stairs they crossed the hallway, slamming the door behind them. As Kennedy and I reached the ground floor we saw the janitor and one of the elevator boys on either side of Aunt Josephine. "Elaine! Elaine!" she cried. "What's the matter?" demanded Kennedy, leaning heavily on me. "They have kidnapped her," cried Aunt Josephine. Kennedy pulled himself together. "Tell me, quick--how did it happen?" he demanded of Aunt Josephine. "It was the ring," she cried, handing it to him. Kennedy took the ring and looked at it for a moment. Then he turned to us blankly. All the rooms were empty. Elaine had been spirited away. CHAPTER III THE WATCHING EYE Not a clue was left by the kidnappers when they so mysteriously spirited Elaine away from the apartment of Wu Fang. She had disappeared as completely as if she had vanished into the thin air. Kennedy was frantic. Wu and Long Sin themselves seemed to have vanished, too. Where they held her, what had happened to her was a sealed book. And yet, no move of ours was made, no matter how secret, that it did not seem to be known to them. It was as though a weird, uncanny eye glared at us, watching everything. Craig neglected no possibility in his eager search. He even visited the little house in the country which Elaine had given to Aunt Tabby, and spent several hours examining the collapsed subterranean chamber in the vain hope that it might yield a clue. But it had not. It was half filled with debris from above, where the pillar had given way that night when we had all so nearly lost our lives. Still, there was enough room in what remained of the cavern so that we could move about. Kennedy had even dug away some of the earth and rock, in the hope of discovering some trace of the strange visitor whom we had surprised at work. But here, also, he had found nothing. It was maddening. What might at any moment be happening to Elaine--and he powerless to help her? Unescapably, he was forced to the conclusion that not only Elaine's amazing disappearance, but the tragic succession of events which had preceded it, had been caused, in some way, by the curiously engraved ring which Aunt Josephine had taken from Elaine. Craig had taken possession of the mystic ring himself, and now, forced back on this sole clue, it had occurred to him that if the ring were so valuable, other attempts would, without doubt, be made to get possession of it. I came into the laboratory, one afternoon, to find Kennedy surrounded by jeweler's tools, hard at work making an exact copy of the ring. "What do you think of it, Walter?" he asked, holding up the replica. "Perfect," I replied, admiringly. "What are you going to do with it?" "I can't say--yet," answered Kennedy, forlornly, "but if I understand these Chinese criminals at all, I know that the only way we can ever track them is through some trick. Perhaps the replica will suggest something to us later." He placed the copy in a velvet-lined box closely resembling that in which the real ring lay, and dropped both into his pocket. "Let's see if Aunt Josephine has received any word," he remarked abruptly, putting on his hat and coat, and nodding to me to follow. Kennedy and I were not the only visitors to the subterranean chamber where it had seemed that the clue to the Clutching Hand's millions might be found. It was as though that hidden, watching eye followed us. The night after our own unsuccessful search, Wu Fang, accompanied by Long Sin, made his way into the cavern. As they flashed their electric bull's-eyes about the place, they could see readily that we had already been digging there. Wu examined the safe which had been broken into, while Long Sin repeated his experiences there. "And you say there was nothing else in it?" demanded Wu. "Nothing but the ring which they got from me," replied Long Sin, ruefully. "Strange--very strange," ruminated Wu, still regarding the empty strong box. Long Sin was now going over the walls of the cavern minutely, his close-set, beady black eyes examining every square inch of it. A sudden low guttural exclamation caused Wu to turn to him quickly. Long Sin had discovered, back of the debris, a small oblong slot, cut into the rock. Above it were some peculiar marks. Wu hurried over to his henchman, and together they tried to decipher what had been scratched on the rock. As Long Sin's slender and sinister forefinger traced over the inscription, Wu suddenly caught him by the elbow. "The ring!" he cried, as at last he interpreted the meaning of the cryptic characters. But what about the ring? For a moment Wu looked at the slot in deep thought. Then he reached down and withdrew a ring from his own finger and dropped it through the slot. They listened a moment. They could hear the ring tinkle as though it were running down some sort of track-like declivity inside the rock. Then, faintly, they could hear it drop. It had fallen into a little cup of a compartment below at their feet. Nothing happened. Wu recovered his ring. But he had hit at last upon the Clutching Hand's secret! Bennett had devised a ring-lock which would open, the treasure vault. No other ring except the one which he had so carefully hidden was of the size or weight that would move the lever which would set the machinery working to open the treasure house. Again Wu tried another of his own rings, and a third time Long Sin dropped in a ring from his finger. Still there was no result. "The ring which we lost is the key to the puzzle--the only key," exclaimed Wu Fang finally. "We must recover it at all hazard." To his subtle mind a plan of action seemed to unfold almost instantly. "There is no good remaining here," he added. "And we have gained nothing by the capture of the girl, unless we can use her to recover the ring." Long Sin followed his master with a sort of intuition. "If we have to steal it," he suggested deferentially, "it can be accomplished best by making use of Chong Wah Tong." The Tong was the criminal band which they had offended, which had in fact stolen the ring from Long Sin and sold it to Elaine. Yet in a game such as this enmity could not last when it was mutually disadvantageous. Wu took the suggestion. He decided instantly to make peace with his enemies--and use them. Later that night, in his car, Wu stopped near the little curio shop kept by the new Tong leader. Long Sin alighted and entered the shop, while the Tong man eyed him suspiciously. "My master has come to make peace," he began, saluting the Tong leader behind the counter. Nothing, in reality, could have pleased the Tong men more, for in their hearts they feared the master-like subtlety of Wu Fang. The conference was short and Long Sin with a bow left quickly to rejoin Wu, while the Tong leader disappeared into a back room of the shop where several of the inner circle sat. "All is well, master," reported Long Sin when he had made his way back to the car around the corner in which Wu was waiting. Wu smiled and a moment later followed by his slave in crime entered the curio shop and passed through with great dignity into the room in the rear. As the two entered, the Tong men bowed with great respect. "Let us be enemies no more," began Wu briefly. "Let us rather help each other as brothers." He extended his right hand, palm down, as he spoke. For a moment the Tong leader parleyed with the others, then stepped forward and laid his own hand, palm down, over that of Wu. One by one the others did the same, including Long Sin, the aggrieved. Peace was restored. Wu had risen to go, and the Tong men were bowing a respectful farewell. He turned and saw a large vase. For a moment he paused before it. It was an enormous affair and was apparently composed of a mosaic of rare Chinese enamels, cunningly put together by the deft and patient fingers of the oriental craftsmen. Extending from the widely curving bowl below was an extremely long, narrow, tapering neck. Wu looked at it intently; then an idea seemed to strike him. He called the Tong leader and the others about him. Quickly he outlined the details of a plan. . . . . . . . "Have you received any word yet?" asked Aunt Josephine anxiously, when Jennings had ushered us into the Dodge library. Kennedy shook his head sadly. There was no need to repeat the question to Aunt Josephine. The tears in her eyes told only too plainly that she herself had heard nothing, either. Craig bent over and placed his hand on her shoulder. For the moment, none of us could control our emotions. A few minutes later, Jennings entered the room softly again. "The expressmen are outside, ma'am, with a large package," he said. "A package?" inquired Aunt Josephine, looking up, surprised. "For me--are you sure?" Jennings bowed and repeated his remark. Aunt Josephine followed him out into the hall. There, already, the delivery men had set down a huge oriental vase with a remarkably long and narrow neck. It was, as befitted such a really beautiful object of art, most carefully crated. But to Aunt Josephine it came as a complete surprise. "I can't imagine who could have sent it," she temporized. "Are you quite sure it is for me?" The expressman, with a book, looked up from the list of names down which he was running his finger. "This is Mrs. Dodge, isn't it?" he asked, pointing with his pencil to the entry with the address following it. There seemed to be no name of a shipper. "Yes," she replied dubiously, "but I don't understand it. Wait just a moment." She went to the library door. "Mr. Kennedy," she said, "may I trouble you and Mr. Jameson a moment?" We followed her into the hall and there stood gazing at the mysterious gift while she related its recent history. "Why not set it up in the library?" I suggested, seeing that the expressmen were getting restive at the delay. "If there is any mistake, they will send for it soon. No one ever gets anything for nothing." Aunt Josephine turned to the expressmen and nodded. With the aid of Jennings they carried the vase into the library and there it was uncrated, while Kennedy continued to question the man with the book, without eliciting any further information than that he thought it had been reconsigned from another express company. He knew nothing more than that it had been placed on his wagon, properly marked and prepaid. When Kennedy rejoined us, the vase had been completely uncrated, Aunt Josephine signed for it, and, grumbling a bit, the expressmen left. There we stood, nonplussed by the curious gift. Craig walked around the vase, looking at it critically. I had a feeling of being watched, one of those sensations which psychologists tell us are utterly baseless and unfounded. I was glad I had not said anything about it when he tapped the vase with his cane, then stuck it down the long narrow neck, working it around as well as he could. The neck was so long and narrow, however, that his stick could not fully explore the inside of the vase, but it seemed to me to be quite empty. "Well, there's nothing in it, anyhow," I ventured. I had spoken too soon. Kennedy withdrew his cane and on the ferrule, adhering as though by some sticky substance, was a note. Kennedy pulled it off and unfolded it, while we gathered about him. "Maybe it's from Elaine," cried Aunt Josephine, grasping at a straw. We read: DEAR AUNT JOSEPHINE, This is a token that I am unharmed. Have Mr. Kennedy give the ring to the man at the corner of Williams and Brownlee Avenues at midnight to-night, and they will surrender me to him.--ELAINE. P. S. Have him come alone or my life will be in danger. We looked at each other in amazement. "I thought something like this would happen," remarked Craig at length. "Oh," cried Aunt Josephine, "it's too good to be true." "We'll do it," exclaimed Kennedy quickly, "only this is the ring that we'll give them." He drew from his pocket the replica of the ring which he had made and showed it to Aunt Josephine. Then he drew from another pocket the real ring, replacing the replica. "Here's the real one," he said in a low tone. "Guard it as you would guard your life." She took the ring, almost fearfully. It seemed as if nothing but misfortune had followed it. Still, she realized that it was necessary that she should take care of it, if the plan was to work. "And, oh, Mr. Kennedy," she implored, as we rose to go, "please get back my little girl for me." Craig clasped her hand. "I'll try my best," he replied fervently, patting her shoulder to cheer her up, as she sank into a chair. Aunt Josephine was worn out with the sleepless nights of worry since Elaine's disappearance. After we had gone, she tried to eat dinner, but found that she had no appetite. All the evening she sat in the library, with a book at which she stared, though she scarcely read a page. However, as the hours lengthened, she found herself nodding through sheer exhaustion. It was getting late and her thoughts were still on Elaine, At the desk in the library, she was examining the curious ring, which she had taken from her jewel case, thinking of the terrible train of events that had followed it. Although she had intended to sit up until she received some word from Kennedy that night, the long strain had told on her and in spite of her worry about Elaine, she decided, at length, to retire. She replaced the ring in the case, locked the case, and turned out the lights. "Good night, Jennings," she said, as she passed the faithful old butler in the hall. "Good night, ma'am," he replied, pausing on his rounds to see that the doors and windows were locked. Aunt Josephine, clasping the jewel case tightly, mounted the stairs and entered her room. She locked the door carefully and put the jewelry case under her pillow. Then she switched off the light. The moment Jennings's footsteps ceased down-stairs in the library, a small piece of the vase seemed to break away from the rest of the mosaic, as though it were knocked out from the inside. Then a large piece fell out, and another. At last from the strange hiding-place a lithe figure, as shiny as though bathed in oil, naked except for a loin-cloth, seemed to squirm forth like a serpent. It was Wu Fang--the watchful eye which, literally as well as figuratively, had been leveled at us in one form or another ever since the kidnapping of Elaine. Silently he tiptoed to the doorway and listened. There was not a sound. Just as noiselessly then he went back to the library table and muffling the telephone bell, took down the receiver. He whispered a number, waited, then whispered some directions. A moment later he wormed his way out of the library and into the drawing-room. On he went cautiously, snake-like, up the stairs until he came to the door of Aunt Josephine's room. He bent down and listened. There was no sound except Aunt Josephine's breathing. Silently he drew from a fold in the loin-cloth a screwdriver and removed the screws from the hinges of the door. Quietly he pushed the bedroom door open, pivoting it on the lock, just far enough open so that he could slip through. Creeping along the floor, like a reptile whose sign he had assumed, he came nearer and nearer Aunt Josephine's bed. As he paused for a moment his quick eye seemed to catch sight of the bulging lump under her pillow. His long thin hand reached out for it. Aunt Josephine moved restlessly in her sleep. Instantly he seized a murderous-looking Chinese dirk fastened to his side and raised it above her head ready to strike on the slightest outcry. She moved slightly, and relapsed into sound sleep again. Holding the knife above her, Wu slowly and quietly removed the jewel-case from under her pillow. . . . . . . . In a country road-house Long Sin was waiting patiently. The telephone rang and the proprietor answered. Long Sin was at his side almost before he could hand over the receiver. It was Long Sin's master, Wu. "Beware," came the whispered message over the wire. "Kennedy has made a false ring. I'll get the real one. By the great Devil of Gobi, you must cut him off." "It is done," returned Long Sin, hanging up the receiver in great excitement. He hurried out of the room and left the road-house. Down the road in an automobile, bound between two Chinamen, one at her head and the other at her feet, was Elaine, wrapped around in blankets, not even her face visible. The guards looked up startled as Long Sin streaked out of the shadow to the car. "Quick!" he ordered. "The master will get the ring himself. I will take care of Kennedy." An instant and they were gone, while Long Sin slunk back into the shadows from which he had come. Through the underbrush the wily Chinaman made his way to an old barn, which stood back some distance from the road, and entered the front door. There was another door in the rear, and one quite large window. In the dim light of a lantern hanging from a rafter could be seen several large barrels in a corner. Without a moment's hesitation, Long Sin seized a bucket and placed it under the spiggot of one of the barrels. The liquid poured forth into the bucket and he emptied the contents on the floor, filling the bucket again and again and swinging it right and left in every direction until the barrel had finally run dry. Then he moved over to the window, which he examined carefully. Satisfied with what he had done, he drew a slip of paper from his pocket and hastily wrote a note, resting the paper on an old box. When he had finished writing, he folded up the note and thrust it into a little hollow carved Chinese figure which he took also from his pocket. These were, apparently, his emergency preparations which he was ready to execute in case he received such a message from his master as he had actually received. With a final hasty glance about he extinguished the lantern, letting the moonlight stream fitfully through the single window. Then he left the barn, with both front and rear doors open. Taking advantage of every bit of shelter, he made his way across the field in the direction of the crossroads, finally dropping down behind a huge rock some yards from the finger post that pointed each way to Williams and Brownlee Avenues. . . . . . . . Late that night, Kennedy left his apartment prepared to follow the instructions in the note which had been so strangely delivered in the vase. As he climbed into a roadster, he tucked the robe most carefully into a corner under the leather seat. "For heaven's sake, Craig," I gasped from under the robe, "let me have a little air." I had taken my place under the robe before the car was driven up before the apartment, lest some emissary of Wu Fang might be watching to see that there was no such trick. "You'll get air enough when we get started, Walter," he laughed back under his breath, apparently addressing the engine. Kennedy was a hard driver when he wanted to be and enough was at stake to-night to make him drive hard. He whizzed along in the roadster, and I was indeed glad enough to huddle up under the robe. We had reached a point in the suburbs which was deserted and I did not recognize a thing when he pulled up by the side of the road with a jerk. I peered through a crease in the corner of the robe, and saw him slide out from under the wheel and stand by the side of the car, looking up and down. Ahead of us the road curved sharply and I had no idea what was there, though Kennedy seemed to know the place. A moment later he pulled the robe partly off me, and bent down as though examining the batteries on the side of the car. "Get out on the other side in the shadow of the car, Walter," he whispered hoarsely. "Go down the road a bit--only cut in and keep under cover. This is Williams Avenue. You'll see a big rock. Hide behind it. Ahead you'll see Brownlee Avenue. Be prepared for anything. I shall have to trust the rest to you. I don't know myself what's going to happen." I slid out and went along the edge of the road, as Craig had directed, and finally crouched behind a huge rock, feeling on as much tension as if I had been a boy playing at Wild West. Only this might at any moment develop into the reality of a Wild Far East. After a moment to give me a chance, Craig himself left the car pulled up close by the side of the road and went ahead on foot. At last he came to the cross-roads just around the bend, where in the moonlight he could read the sign: "Williams Avenue" and "Brownlee Avenue." He stood there a moment, then glanced at his watch which registered both hands approaching the hour of twelve. He gazed about at the deserted country. Had the appointment been a hoax, after all, a scheme to get him away from the city for some purpose? Suddenly, at his feet in the dust of the road something heavy seemed to drop. He looked about quickly. No one was in sight. He reached down and picked up a little Chinese figure. Tapping it with his knuckle, he examined it curiously. It was hollow. From the inside he drew out a piece of paper. He strained his eyes in the moonlight and managed to make out: The Serpent is all-wise, and his fang is fatal. You have signed the white girl's death warrant. Beneath this sinister warning was stamped the serpent sign of Wu Fang. It was not a hoax, and Kennedy stood there a moment gazing about in tense anxiety. Had that uncanny watching eye observed his every action? Was it staring at him now in the blackness? . . . . . . . Meanwhile, I had made my way stealthily, peering into the bushes and careful not even to step on anything that would make a noise and was now, as I have said, crouched behind the big rock to which Craig had directed me. I heard him go along the road and looked about cautiously, but could hear and see nothing else. I had begun to wonder whether Kennedy might not have made a mistake when, suddenly, from behind the shadow of another rock, ahead of me, but toward Brownlee Avenue, I saw a tall, gaunt figure of a man rise in the moonlight, almost as if it had sprung from the very earth. My heart gave a leap, as he quickly raised his right arm and hurled something as far as he could in the direction that Kennedy had taken. If it had been a bomb, followed by an explosion, I would not have been surprised. But no sound followed as the figure dropped back as if it had been a wraith. I stole out from my own hiding-place in the shadow of my rock and darted quickly to the shelter of a bush, nearer the figure. The figure was no wraith. It turned to steal away. I remembered Kennedy's parting words. If the man ever gained the darkness of a clump of woods, just beyond us, he was as good as safe. This was the time to act. I leaped at him and we went down, rolling over and over in the underbrush and stubble. We fought fiercely, but I could not seem to get a glimpse of his face which was muffled. He was powerful and stronger than I and after a tough tussle he broke loose. But I had succeeded, nevertheless. I had delayed him just long enough. Kennedy heard the sound of the struggle and was now crashing through the hedge at the cross-roads in our direction. I managed to pick myself up, just as Kennedy reached my side and, together, we followed the retreating figure, as it made its way among the shadows. Across the open space before us we followed him and at last saw him dive into an old barn. A moment later we followed hot-foot into the barn. As we entered, we could hear a peculiar grating noise, as though a door was swung on its rusty hinges. The front door was open. Evidently the man had gone through and closed the back door. We threw ourselves against the back door. But it did not yield. There was no time to waste and we turned to rush out again by the way we had come, just as the front door was slammed shut. The man had trapped us. He had left both doors open, had run through, braced the back door, then had rushed around outside just in time to brace the front door also. We could hear his feet crunching the dry leaves and twigs as he went around the side of the barn again. Together we threw ourselves against the front door, but, although it yielded a little he had barred it so that it would resist our united strength for some time. Again and again we threw ourselves against it. It was horribly dark in there, except for an oblong spot where the moonlight streamed in through a window. Suddenly the pale silver of the moonlight on the floor reddened. The man had struck a match and thrown it into a mass of oil-soaked straw and gunpowder which protruded through one of the weather-beaten boards, near the floor. It was only a matter of a second or so now when the fire swept into the barn itself. There was no beating it out. Some one had literally soaked the straw and the floor with oil. It seemed as though the whole place burst into a sudden blaze of tinder. Outside, we could hear footsteps rapidly retreating toward the shelter of the clump of woods. For a second I looked dismayed at the rapidly-mounting flames. "A very pretty situation," I forced with a laugh. "But I hope he doesn't think we'll stay here and burn, with a perfectly good window in full view." I took a step toward the window, but before I could take another, Kennedy yanked me back. "Don't think for a moment that he overlooked that," he shouted. Craig looked around hastily. In a corner, just back of us was a long pole. He snatched it up and moved cautiously toward the window, keeping the pole as level as possible as he endeavored to get a leverage on the sash. The flames were mounting faster and higher, licking up everything. "Keep back, Walter," he muttered, "just as far as you can." He had scarcely raised the window a fraction of an inch when an old rusty, heavy anvil and a bent worn plowshare crashed down to the floor directly over the spot where I should have been if he had not dragged me away. I started back, aghast. Nothing had been overlooked to finish us off. "I think you may try it safely now, all right," smiled Kennedy coolly. We climbed out of the window, not an instant too soon from the raging inferno about us. Having gained the clump of woods, the gaunt figure had paused long enough to gloat over his clever scheme. Instead, he saw us making good our escape. With a gesture of intense fury he turned. There was nothing more for him to do but to zigzag his way to safety across country. The barn was now burning fiercely and it was almost as light as day about us. Kennedy paused only long enough to look down at the ground where the fire had been started. "See, Walter," he exclaimed pointing to a square indention in the soft soil. "No white man ever made a footprint like that." I bent over. The prints had the squareness of those paper-layered soles of a Chinaman. "Long Sin," came the name involuntarily to my lips, for I knew that Wu would delegate just such a job to his faithful slave. Kennedy did not pause an instant longer, but in the light of the burning barn, as best he could, started to follow the trail in a desperate endeavor either to overtake Long Sin, or at least to find the final direction in which he would go. . . . . . . . At the entrance of the passageway which led to the little underground chamber in which we had sought the treasure hidden by the Clutching Hand, Wu Fang was seated on a rock waiting impatiently, though now and then indulging in a sinister smile at the subtle trick by which he had recovered the ring. The sound of approaching footsteps disturbed him. He was far too clever to leave anything to chance and, like a serpent, he wriggled behind another rock and waited. It was only a glance, however, that he needed to allay his suspicions. It was Long Sin, breathless. Wu stepped out beside him so quietly that even the acute Long Sin did not hear. "Well?" he said in a guttural tone. Long Sin drew back in fear. "I have failed, oh master," he replied in an imploring tone. "Even now they follow my tracks." It was bad enough to confess defeat without the fear of capture. Wu frowned. "We must work quickly, then," he muttered. He picked up a dark lantern near-by, indicating another to Long Sin. They entered the cave, flashing the lights ahead of them. "Be careful," ordered Wu, proceeding gingerly from one stepping-stone to another. "We shall be followed no further than this." He paused a moment and pointed his finger at the earth. Everywhere, except here and there where a stone projected, was a sticky, slimy substance. It was an old trick of primitive races. "Bird lime," hissed Wu, pointing at the viscid substance made of the juice of the holly bark, extracted by boiling, and mixed with a third part of nut oil and grease. They passed on from stone to stone until they came to the subterranean chamber itself. Without a moment's hesitation, Wu made his way toward the rock in which they had found the slot with its cryptic inscription. Long Sin watched his master in silent admiration as, at last, he drew forth the mystic ring for which they had dared all. Without a word, Wu dropped it in the slot. It tinkled down the runway, a protuberance hit a trigger and pushed it a hair's breadth. A noise behind them caused the two to turn startled. Even Wu had not expected it. On the other side of the chamber, a great rock in the ground slowly turned, as though on a pivot. They watched, fascinated. Even then Wu did not forget the precious ring, but as the rock turned, reached down quickly and recovered it from the cup at the floor. Inch by inch the pivoted rock moved on its axis. They flashed their lanterns full on it and, as it moved, they could see disclosed huge piles of gold and silver in coins and bars and ornaments, a chest literally filled with brilliants, set and unset, rubies, emeralds, precious stones of every conceivable variety, a cave that would have staggered even Aladdin--the rich reward of the countless marauding operations of Bennett's other personality. For a moment they could merely stand in avaricious exultation. . . . . . . . Painfully and slowly, we managed to trail Long Sin's footprints, until we came to a road where they were lost in the hard macadam. There was no time to stop. We must follow the road on the chance that he had taken it. But which way? Kennedy chose the most likely direction, for the trail had been at an angle to the road and Long Sin was not likely to double back. We had not gone many rods before Kennedy paused a minute and looked about in the moonlight. "It's right, Walter," he cried. "Do you recognize it?" I looked about. Then it flashed over me. This was the back road that led past the entrance to the treasure vault at Aunt Tabby's. We went on now more quickly, listening carefully to catch any sounds, but heard nothing. At last Kennedy stopped, then plunged among the rocks and bushes beside the road. We were at the cave. "You go in this way, Walter," he directed. "I'll go around and down where it caved in." I groped my way along through the darkness. I had gone only a yard or two, when it seemed as though something had grasped my foot. With a great wrench I managed to pull it loose. But the weight on my other foot had imbedded it deeper. I struggled to free this foot and got the other caught. My revolver, which I had drawn, was jarred from my hand and in the effort to recover it, I lost my balance. Unable to move a foot in time to catch myself, I fell forward. My hands were now covered by the slimy, sticky stuff, and the more I struggled, the worse I seemed to get entangled. . . . . . . . Wu and Long Sin paused only a minute in astonishment. Then they literally fell upon the wealth that lay before them, gloating over the gold, stuffing their hands into the jewels, lifting them up and letting the priceless gems run through their fingers. Suddenly they paused. There was the slight tinkle of a Chinese bell. Kennedy had reached Aunt Tabby's garden, outside the roof of the subterranean chamber where it had given way, had gone down carefully over the earth and rock, and in doing so had broken a string stretched across the passageway. The tinkle of a bell attached to it aroused his attention and he stopped short, a second, to look about. Wu Fang had arranged a primitive alarm. Quickly, Wu and Long Sin blew out their lanterns while Wu gave the rock a push. Slowly, as it had opened, it now closed and they stood there listening. I was still struggling in the bird lime, getting myself more and more covered with it, when the reverberation of revolver shots reached me. Wu and Long Sin had opened fire on Kennedy, and Kennedy was replying in kind. In the cavern it sounded like a veritable bombardment. As they retreated, they came nearer and nearer to me and I could see the revolvers spitting fire in the darkness. So intent were they on Kennedy that they forgot me. I watched them fearfully as they hopped deftly from one stone to another to avoid the lime--and were gone. "Craig! Craig!" I managed to cry feebly. "Be careful. Keep to the stones." He strained his eyes toward the ground in the darkness, at the sound of my voice. Then he struck a match and instantly took in the situation which, to me, under any other circumstances, would have been ludicrous. Stepping from stone to stone, he followed the retreating Chinamen. But they had already reached the mouth of the cave and were making their way rapidly down the road to a bend, in the opposite direction from which we had come. There, Wu's automobile was waiting. They leaped into it and the driver, without a word, shot the car off into the darkness of early dawn. A moment later, Kennedy appeared, but they had made their getaway. Baffled, he turned and retraced his steps to the cave. I don't think that I ever welcomed him more sincerely than I did as, finally, I crawled slowly out from the bird lime, exhausted by the effort that I had made to free myself from the sticky mess. "They got away, Walter," he said, lighting a lantern they had dropped. "By George," he added, I think a little vexed that I had not been able to stop them, "you are a sight!" He was about to laugh, when I fainted. I can remember nothing until I woke up over by the wall of the chamber where he dragged me. Kennedy had been working hard to revive me, and, as I opened my eyes, he straightened up. His eye suddenly caught something on the rock beside him. There was a little slot carved in it, and above the slot was a peculiar inscription. For several minutes, Kennedy puzzled over it, as Wu had done. Then he discovered the little cup near the ground. "The ring!" he suddenly cried out. I was too muddled to appreciate at once what he meant, but I saw him reach into his fob pocket and draw forth the replica of the trinket which had caused so much disaster, as if it had been cursed by the Clutching Hand himself. He dropped it into the slot. Struggling to my feet, I saw across from me the very rock itself moving. Was it an hallucination, born of my nervous condition? "Look, Craig!" I cried involuntarily, pointing. He turned. No, it was not a vision. It actually moved. Together we watched. Slowly the rock turned on a pivot. There were disclosed to our astonished eyes the hidden millions of the Clutching Hand. I looked from the gold and jewels to Kennedy, in speechless amazement. "We have beaten them, anyhow," I cried. Slowly Craig shook his head sadly. "Yes," he murmured, "we have found the Clutching Hand's millions, but we have lost Elaine." CHAPTER IV THE VENGEANCE OF WU FANG Elaine was still in the power of Wu Fang. Kennedy had thwarted the Chinese master criminal in his search for the millions amassed by the Clutching Hand. But any joy that we might have derived from this success was completely obscured by the fear that Wu might wreak some diabolical vengeance on Elaine. It was a ticklish situation. In fact, I doubt whether Craig would have discovered the treasure at all, if our pursuit of Wu and Long Sin the night before had not literally forced us into doing so. Nor were Kennedy's fears unfounded. Wu and Long Sin had scarcely reached the secret apartment back of the deceptive exterior of the Chinatown tenement, when the subtle Chinaman began to contemplate his revenge. Long Sin was smoking a Chinese pipe, resting after their hurried flight, while Wu, the tireless, was seated at a table at the other end of the room. At last Wu Fang took up a long Chinese dirk from the table before him, looked at it, turned it over, felt its edge. It was keen and the point was sharp. He rose and deliberately walked across to a door leading into a back room. On a couch lay Elaine and with her, as a guardian, was Weepy Mary whom the Clutching Hand had used to lure her to the church where the faked record of her father's marriage was supposed to be. Indeed, though Wu had lost the Clutching Hand's millions, he had seen his chance and had fallen heir to what was left of Bennett's criminal organization. As Wu, the Serpent, entered and advanced slowly towards Elaine, she crouched back from him in deadly fear. He stopped before her without a word and his menacing eye seemed to read her very thoughts. Slowly he drew from under his robe the Chinese dirk. He felt the edge of it again and gazed significantly at Elaine. She shrank back even further, as far as the divan would permit. It was a critical moment. Just then Long Sin entered. "One of the five millions waits outside," he reported simply, with a bow. Wu understood. It had been a pleasant fiction of his that although he did not, of course, absolutely control such a stupendous organization he could, by his subtle power, force almost unlimited allegiance from the simple coolies in that district of China from which he came. Out in the front room, just a moment before, a knock at the door had disturbed Long Sin, and a Chinese servant had announced a visitor. Long Sin had waved to the servant to usher him in and a poorly clad coolie had entered. He bowed as Long Sin faced him. "Where is the master?" he had asked. Long Sin had not deigned to speak. With a mere wave of his hand, he indicated that he would be the bearer of the message, and had followed Wu through the door of the back room. So, almost by chance, Wu was interrupted in the brutal vengeance which had first come to his mind. He sheathed the knife and, still without a word, went back into the main room, giving a nod to Weepy Mary to guard Elaine closely. Wu eyed the coolie until the newcomer could almost feel the master's penetrating gaze, although his head was bowed in awe. Quickly the coolie thrust his hand under his blouse and drew forth a package. With another bow, he advanced. "For your enemies, oh master," he said, handing the package over to Wu. For the first time since the loss of the treasure, Wu Fang seemed to take an interest in something besides revenge. The coolie started to open the package, removed the paper wrapper, and then a silk wrapping inside. Finally he came to a box, from which he drew a leather pouch, each operation conducted with greater care as it became evident that the contents were especially precious in some way. Then he took from the pouch a small vial. "What is it?" demanded Wu Fang, as the coolie displayed it. The coolie drew forth now a magnifying glass and a glass slide. Opening the vial with great care he shook something out on the slide, then placed it under the lens. "Look!" he said simply. Wu bent over and looked. Under the lens what had formerly seemed to be merely a black speck of dirt became now one of the most weird and uncanny little creatures to be found in all the realm of nature. It seemed to be all legs and feelers moving at once. A normal person would have looked at the creature only with the greatest repugnance. Wu regarded it with a sort of unholy fascination. "And it is?" he queried. "What the white man calls the African tick which carries the recurrent fever," answered the coolie deferentially. A flash of intense exultation seemed to darken Wu Fang's sinister face. Several times he paced up and down the room, as he contemplated the sight which he had just seen. Then he came to a sudden determination. "Wait," he said to the coolie, as he moved slowly again into the back room. Long Sin had remained there. With Weepy Mary he was guarding Elaine when Wu Fang reentered. Elaine was thoroughly aroused by this time. Even the fact that Wu no longer held the murderous dirk did not serve to reassure her, for the look on his face was even more terrible than before. He smiled cunningly to himself. "Suffering is a state of mind," he said in a low tone, "and I have decided that it would be poor revenge for me to harm you. You are free." Nothing could have come as a greater surprise to Elaine. Even Long Sin had not expected any such speech as this. Elaine, however, was wonder-stricken. "Do you--do you really mean it?" she asked, scarcely able to believe what her ears heard. Wu merely nodded, and with a wave of his hand to Long Sin indicated that Elaine was to be released. Long Sin, the slave, did not stop to question his master, but merely moved over to a closet and took out the hat and wraps which Elaine had worn when she had been kidnapped in the up-town apartment. He handed them over to her and she put them on with trembling hands. No one stopped her and she nerved herself to take several steps toward the door. She had scarcely crossed half the room. "Wait!" ordered Wu sharply. Was he merely torturing her, as a cat might torture a mouse? She stopped obediently, afraid to look at him. "This will be the vengeance of Wu Fang," he went on impressively. "Slowly, one by one, your friends will weaken and die, then your family, until finally only you are left. Then will come your turn." He stopped again and raised his long lean forefinger. "Go," he hissed. "I wish you much joy." He turned to Long Sin and whispered a word to him. A moment later, Long Sin drew forth a large silken handkerchief and tied it tightly over Elaine's eyes. Then he took her hand and led her out. There was to be no chance by which she could lead a raiding party back to the den in which she had been held. I don't think that in all our friendship I have ever seen Kennedy so utterly depressed as he was when we returned after the discovery of the vast fortune which Bennett had cleverly secreted. I came upon him in the laboratory the next morning while he was trying to read. He had laid aside his scientific work, and now he had even laid aside his book. There seemed to be absolutely nothing to do until some new clue turned up. I placed my hand on his shoulder, but the words that would encourage him died on my lips. Several times I started to speak, but each time I checked myself. There did not seem to be anything that would be appropriate for such an occasion. A sharp ring at the telephone made both of us fairly jump, so nervous had we become. Kennedy reached over instantly for the instrument in the vague hope that at last there was some news. As I watched his face, it changed first from despair to wonder, and finally it seemed to light up with the most remarkable look of relief and happiness that one could imagine. "I shall be right over," he cried, jamming the receiver down on the hook, and in the same motion reaching for his hat and coat. "Walter," he cried, "it is Elaine! They have let her go!" I seized my own hat and coat in time to follow him and we dashed out of the laboratory. The suspense under which Aunt Josephine had been living had told on her. Her niece, Elaine's cousin, Mary Brown, who lived at Rockledge, had come into the city to comfort Aunt Josephine and they had been sitting, that morning, in the library. Marie, the maid was busy about the room, while Aunt Josephine talked sadly over Elaine's strange disappearance. She was on the verge of tears. Suddenly a startled cry from Jennings out in the hall caused both ladies to jump to their feet. They could scarcely believe what they heard as the faithful old butler cried out the name. "Why--Miss Elaine!" he gasped. An instant later Elaine herself burst into the room and flung herself into Aunt Josephine's arms. All talking and half crying from joy at once, they crowded about her. Breathlessly she answered the questions that flew thick and fast. In the excitement Aunt Josephine had seized the telephone and called our number. She did not even wait to break the good news, but handed the telephone to Elaine herself. We left the laboratory on the run, too fast to notice that just around the building line at the corner stood a limousine with shades drawn. Even if we had paused to glance back, we could not have seen Wu Fang and Long Sin inside, gazing out through the corner of the curtains. They were in European dress now and had evidently come prepared for just what they knew was likely to happen. In all the strange series of events, I doubt whether we had ever made better time from the laboratory over to the Dodge house than we did now. We were admitted by the faithful Jennings and almost ran into the library. "Oh, Craig!" cried Elaine, as Kennedy, almost speechless, seized her by both hands. For a few seconds none of us could speak. Then followed a veritable flood of eager conversation. I watched Elaine carefully, in fact we all did, for she seemed, in spite of the excitement of her return, to be almost a complete nervous wreck from the terrible experiences she had undergone. "Won't you come and stay with me a few days up in the country, dear?" urged Mary at last. Elaine thought a moment, then turned to Aunt Josephine. "Yes," considered her aunt, "I think it would do you good." Still she hesitated; then shyly looked at Kennedy and laughed. "You, too, Craig, must be fagged out," she said frankly. "Come up there with us and take a rest." Kennedy smiled. "I shall be delighted," he accepted promptly. "You, too, Mr. Jameson," she added, turning to me. I hesitated a moment and Kennedy tried to catch my eye. I was just about to speak when he brought his heel down sharply on my toe. I looked at him again and caught just the trace of a nod of his head. I saw that I was de trop. "No, thank you," I replied. "I'm afraid I'd better not go. Really, I have too much work staring at me. I can't get away--but it's very kind of you to think of asking me." We chatted, then left a few moments later so that Kennedy could pack. Around the corner from the laboratory, as we dashed out, had been, as I have said, Wu Fang and Long Sin looking out from the limousine. No sooner had we disappeared across the campus than their driver started up the car and they sped around to our apartment. Cautiously they alighted and walked down the street. Then making sure they were not observed, they entered and mounted the stairs to our doorway. Long Sin was stationed down the hall on guard while Wu Fang drew from his pocket a blank key, a file and a candle. He lighted the candle and held the key in its flame until it was covered with soot. Then he inserted the key in the keyhole, turned it and took the key out. Working quickly now, he examined the key sharply. In the soot were slight scratches indicating where it struck and prevented the turning of the lock. He filed the key, trying it again and again. Finally he finished, and opened the door. Beckoning Long Sin, he entered our rooms. As they stood there, Wu Fang gazed about our living-room, keenly. He was evidently considering where to place something, for, one after another, he picked up several articles on the desk and examined them. Each time that he laid one down he shook his head. Finally his eye rested on the telephone. It seemed to suggest an idea to him and he crossed over to it. Carefully holding down the receiver on the hook, he unscrewed the case which holds the diaphragm, while with his clever fingers he held the rest of the instrument intact. Then he removed from his pocket the vial which the coolie had given him and placed its contents on the diaphragm itself. Quickly now he replaced the receiver, and, having finished their work, Long Sin and Wu Fang stealthily crept out. A second time, as we approached our apartment after the visit to Elaine, we were too excited to notice the limousine in which were Wu and Long Sin. But no sooner had we entered than Long Sin left the car with a final word of instruction from his master. Up-stairs, in the apartment, Kennedy began hurriedly to pack, and I helped him as well as I could. We were in the midst of it when the telephone rang and I answered it. "Hello!" I called. There was no response. "Hello, Hello!" I repeated, raising my voice. Still there was no answer. I worked the hook up and down but could get no reply. Finally, disgusted, I hung up. A moment later, I recall now, it seemed to me as though some one had stuck a pin into the lobe of my ear. Still, I thought nothing of it in the excitement of Kennedy's departure, and went to work again to help him pack. We had scarcely got back to work, when the telephone bell jangled again, and a second time I answered it. "Is Mr. Kennedy there?" came back a strange voice. I handed the instrument to Craig. "Hello," he called. "Who is this?" No response. "Hello, hello," he shouted, working the hook as I had done and, as in my case, there was still no answer. "Some crank," he exclaimed, jamming down the receiver in disgust and returning to his packing. Neither of us thought anything of it at the time, but now I recall that I did see Kennedy once or twice press the lobe of his ear as though something had hurt it. We did not know until later that in a pay station down the street our arch enemy, Long Sin, had been calling us up and then, with a wicked smile, refusing to speak to us. . . . . . . . It was about a week later that I came home late one night from the Star, feeling pretty done up. Whatever it was, a violent fever seemed to have come on me suddenly. I thought nothing of it, at first, because I soon grew better. But while it lasted, I had the most intense shivering, excruciating pains in my limbs, and delirious headache. I recall, too, that I felt a peculiar soreness on the ear. It was all like nothing I had ever had before. Indeed the next morning when I woke up, I felt a lassitude that made it quite hard enough even to lounge about in my bath-robe. Finally, feeling no better, I decided to see a doctor. I put on my clothes with a decided effort and went out. The nearest doctor was about half a block away and we scarcely knew him, for neither Kennedy nor I were exactly sickly. "Well," asked the doctor, as he closed the door of his office and turned to me. "What seems to be the matter?" I tried to smile. "I feel as though I had been celebrating not wisely but too well," I replied, trying to cheer up, "but as a matter of fact I have been leading the simple life." He sounded me and pounded me, looked at my tongue and my eyes, listened to my heart and lungs, though I don't think he treated my symptoms very seriously. In fact, I might have known what he would do. He talked a little while on generalities, diet and exercise then walked over to a cabinet, and emptied out a few pills into a little paper box. "Take one every hour," he said, handing them to me, and carefully returning the bottle to the cabinet so that I could not see what was on the label. "Cut your cigarettes to three a day, and don't drink coffee. Four dollars, please." I suppose I ought to have been cured, and in fact I was cured--of going to that doctor. I paid him and went back to the apartment, my head soon in a whirl from a new onset of the fever. I managed to get back into my bath-robe, and threw myself down on the divan, propped up with pillows. I had taken the pills but they had no more effect than sugar of milk. By this time, I was much more delirious and was crying out. I saw faces about me, but I did not see the faces which were actually out by our hall door. Wu Fang and Long Sin had waited patiently for their revenge. Now that they thought sufficient time had elapsed, they had stolen stealthily to the apartment door. While Long Sin watched, Wu listened. "The white devil has it," whispered Wu Fang, as he rejoined his fellow conspirator. How long I should have remained in this state, and in fact how long I did remain, I don't know. Vaguely, I recall that our acquaintance, Johnson, who had the apartment across the hall, at last heard my cries and came out to his own door. He needed only a moment to listen at ours to know that something was wrong. "Why, what's the matter, Jameson?" he asked, poking his head in and looking anxiously at me. I could only rave some reply, and he tried his best to quiet me. "What's the matter, old man?" he repeated. "Tell me. Shall I send for a doctor?" Somehow or other I knew the state I was in. I knew it was Johnson, yet it all seemed unreal to me. With a great effort I gathered all my scattered wits and managed to shout out, "Telegraph Kennedy--Rockledge." By this time Johnson himself was thoroughly alarmed. He did not lose a second in dictating a telegram over the telephone. . . . . . . . At about the same time, up at Rockledge, Kennedy and Elaine, with her cousin Mary Brown, were starting out for a horseback ride through the hills. They were chatting gaily, but Kennedy was forcing himself to do so. In fact, they had scarcely gone half a mile when Kennedy, who was riding between the two and fighting off by sheer nerve the illness he felt, suddenly fell over in half a faint on the horse's neck. Elaine and Mary reined up their horses. "Why, Craig," cried Elaine, startled, "what's the matter?" The sound of her voice seemed to arouse him. He braced up. "Oh, nothing, I guess," he said with a forced smile. "I'm all right." It was no use, however. They had to cut short the ride, and Kennedy returned to the house, glad to drop down in an easy chair on the porch, while Elaine hovered about him solicitously. His head buzzed, his skin was hot and dry, his eyes had an unnatural look. Every now and then he would place his hand to his ear as though he felt some pain. They had already summoned the country doctor, but it took him some time to get out to the house. Suddenly a messenger boy rode up on his bicycle and mounted the porch steps. "Telegram for Mr. Kennedy," he announced, looking about and picking out Craig naturally as the person he wanted. Kennedy nodded and took the yellow envelope while Elaine signed for it. Listlessly he tore it open. It read: CRAIG KENNEDY, c/o Wellington Brown, Rockledge, N. J. Jameson very ill. Wants you. Better come. JOHNSON. The message seemed to rouse Kennedy in spite of his fever. His face showed keen alarm, which he endeavored to conceal from Elaine. But her quick eye had caught the look. "I must see Walter," he exclaimed, rising rather weakly and going into the house. How he ever did it is still, I think, a mystery to him, but he managed to pack up and, in spite of the alternating fever and chills, made the journey back to the city. When at last Craig arrived at our apartment, it must have seemed to him that he found me almost at death's door. I was terribly ill and weak by that time, but had refused to see the doctor again and Johnson had managed to get me into bed. Ill himself, Kennedy threw himself down for a moment exhausted. "When did this thing come on Walter?" he asked of Johnson. "Yesterday, I think, at least as nearly as I can find out," replied our friend. Craig was decidedly worried. "There's only one person in New York to call on," he murmured, pulling himself out of bed and getting into the living-room as best he could. "Is that you, Godowski?" he asked over the telephone. "Well, doctor, this is Kennedy. Come over to my apartment, quick. I've a case--two cases for you." Godowski was a world-famous scientist in his line and had specialized in bacteriology, mainly in tropical diseases. As Kennedy hung up the receiver, he made his way back again to the bedroom, scratching his ear. He noticed that I was doing the same in my delirium. "Has Walter been scratching his ear?" he asked of Johnson. Johnson nodded. "That's strange," considered Craig thoughtfully. "I've been doing the same." He turned back into the living-room and for a moment looked about. Finally his eye happened to fall on the telephone and an idea seemed to occur to him. He went over to the instrument and unscrewed the receiver. Carefully he looked inside. Then he looked closer. There was something peculiar about it and he picked up a blank sheet of white paper, dusting off the diaphragm on it. There, on the paper, were innumerable little black specks. Just then, outside, Dr. Godowski's car drew up and he jumped out, swinging his black bag. Not being acquainted with what we were going through, Godowski did not notice the almond-eyed Chinaman who was watching down the street. "How do you do, doctor," greeted Craig faintly, at the door. "What seems to be the difficulty?" inquired the doctor eagerly. "I don't know," returned Craig, "but I have my suspicions. I'm too ill to verify them myself. So I've called on you. Look at Jameson first," he added. While Godowski was examining me, Craig managed to get out his microscope and was looking through it at the strange black specks on the paper. There, under the lens, he could see the most remarkable, almost microscopic creature, all legs and feelers, a most vicious object. Weak though he was, he could not help an exclamation of exultation at his discovery, just as Godowski had finished with me. "Look!" he cried, calling the doctor. "I know what the trouble is, Godowski." He had started to tell, but the excitement of the journey and the exertion were so great that he could hardly mumble. "Here--look--on this paper," he cried. "From the telephone--" He had risen and was handing the paper to the scientist when his weakness overcame him. He fell flat on his face on the floor and dropped the paper, spilling the contents. Godowski, now thoroughly alarmed, bent over Craig. But the delirium had overcome Kennedy, too. Unable to make any sense out of Craig's broken wanderings, Godowski lost no time in taking samples of our blood. Then he hurried away to his laboratory in his car. As he did so, however, Long Sin leaped into a taxicab which was waiting and followed. . . . . . . . In Godowski's laboratory, where he was studying tropical diseases, the bacteriologist set to work at once to confirm his own growing suspicions. From a monkey which he had there for experimental purposes, he drew off some blood samples. Then, with the aid of his assistant, he took the blood samples he had obtained from us. The monkey's blood, under the microscope, seemed full of rather elongated wriggling germs of a peculiar species. In and out they made their way among the blood corpuscles each like a dart aimed at life itself. Then he took the samples of our blood. In them were the same germs--carried by that gruesome tick! "The spirillum!" he muttered. "They are infected with African recurrent fever. The only remedy is atoxyl, administered intravenously, after the manner of Professor Ehrlich's famous '606'." Godowski had rung the call box hastily for a messenger, when Long Sin, who had managed stealthily to creep up to the doctor's laboratory window, scowled, through at the action--then moved away. While his assistant gathered the apparatus, the doctor wrote: MISS ANNE SEPTIX, 301 W. --th St. Please go at once to the apartment of Craig Kennedy,--Claremont Ave. Surgical case. GODOWSKI, M. D. The boy arrived finally and the doctor gave him a generous tip to hurry with the note. He had not turned the corner, however, when Long Sin appeared. Subtly he played on the boy's cupidity to get him to deliver a note of his own, even offered to deliver the boy's note for him. The flash of a five dollar bill made the rest easy. As the boy disappeared on a fake errand, Long Sin, with the real note hurried down-town, smiling wickedly. "They have discovered the fever, Master," he reported in the den. Wu was beside himself with rage. Before he could speak, however, Long Sin spread out Godowski's message. "But I have this," he added. It took merely a glance to suggest to Wu a new plan of action. He rose and moved quickly into the back room. "Come," he ordered Weepy Mary. "You must dress up as a nurse--immediately." Quickly she donned one of the numerous disguises while Wu planned his campaign. "Here," he directed when she was ready, handing her a little vial. "You must infect every instrument the doctor uses on Kennedy and Jameson,--see?" She nodded and a moment later was on her way uptown. . . . . . . . Meanwhile Godowski himself had arrived at our apartment, much to the relief of our friend Johnson, and was unpacking his instruments. Quickly he improvised two operating tables, and placed one of us on each. Then, with his assistant, he put on his white robes, mask, gloves and other precautions for asepsis, setting out the apparatus for the intravenous administration of the drug that would kill the spirillum. Godowski was busy with the atoxyl, mixing it in a normal salt solution. He would drop in a few drops of an acid, then a few drops of an alkaline solution, so as to keep the mixture neutral. Finally, he poured the solution into a container, to the bottom of which was attached a long tube. This container he raised high over our heads, clamping the tube. Then he fastened a tiny needle to the end of the tube, so that it could be inserted in our arms, catching skillfully a vein--a very difficult piece of work in which he excelled. The liquid would then flow by the force of gravity from the container down through the tube, through the hollow needle and into the vein where it would act on the germs of the fever. They had finished their preparations and were waiting for Miss Septix. "She ought to be here, now," muttered Godowski impatiently, looking at his watch. Just then a cab drove up outside. "Perhaps that is she," he exclaimed. "It must be." A few moments later the door of the apartment opened. His face showed his disappointment. It was a stranger. "Miss Septix is ill," she introduced, "and sent me to take her place." The doctor looked about. "Very well, then," he said briskly, seeing his preparations. "Are you ready to go ahead?" She nodded and threw off her coat that covered her immaculate white uniform. The specialist plunged whole-heartedly into his work of saving us now. "Hand me that needle, please," he directed the false nurse. She moved over to the table near-by and took it up, pausing only long enough to dip it secretly into a vial she carried with her. "Please hurry," repeated the doctor. She turned from the table and handed it to him. He adjusted it and already held it poised for the thrust which was not to cure but to poison us further. "Weepy Mary!" cried a frightened voice at our door. Elaine had been deeply alarmed by the sudden illness of Kennedy and the message from Jameson. No sooner had Kennedy gone, than it flashed over her that Wu Fang had predicted something like this. "The threat!" she exclaimed, seeking her cousin. "Mary, I must go to the city--right away." On the next train, then, she had been speeding back to New York, and, arriving at the station, she realized that there was not a moment to lose. She called a cab, drove directly to our apartment, and hurried in, without even ringing the bell. One glance at the improvised hospital was enough to alarm her. But the sight that had transfixed her was of a woman whose face she remembered only too well, though Kennedy and I had never seen her. "Please, Miss," began Godowski's assistant, trying to quiet Elaine, while Godowski turned in vexation to his work. "No, no!" repeated Elaine. "This woman is no nurse. She is a criminal!" Godowski paused. It was true he did not know the woman. He gazed from Elaine to Weepy Mary in doubt. The game was up. Weepy Mary dropped a piece of gauze which she had soaked in the solution from the vial which Wu had given her and bolted for the door. So sudden was her flight that no one was quick enough to stop her. She managed to reach the hall and slam the door. Down she rushed to the street, Godowski's assistant after her. There, awaiting, was Long Sin's car. She leaped in and was off in a moment. The assistant had just time to dive at the running-board. But his grip was poor and Long Sin easily threw him off. "You--you fool!" he hissed at Mary, as soon as the danger of pursuit was over and the assistant had gone back into the apartment. "Oh, sir," she begged, "it was not my fault. Miss Dodge came in--unexpectedly--she recognized me. If I had not fled, they would have caught me--perhaps you, too." Long Sin was furious. He threatened her and she cowered back. However, there was nothing to be gained by that and he subsided and drove quickly down-town. The excitement more than ever alarmed Elaine now. "Tell me," she appealed to Dr. Godowski, "what is the matter?" "In some way," he replied quickly, "they have become infected by the bite of an African tick which carries spirillum fever." "She got away, in a cab," panted the assistant, returning. Godowski raised his hands in despair. "I was just about to start," he cried. "Everything is ready. I can't send for another nurse. Every minute counts." Elaine had thrown off her coat and hat. Her sleeves were up in a moment and before the doctor knew what she was about she was scrubbing her hands in the antiseptic wash. "Only--show me--what to do," she cried. "I will be the nurse!" . . . . . . . Several days later, when we had recovered sufficiently from the diabolical attack that had been made upon us, Kennedy was again at work in the laboratory, while I was writing. We still felt rather weak, but Godowski's skill had pulled us out all right. Our speaking-tube sounded and I knew that it was Elaine and Aunt Josephine. "How do you feel?" inquired Elaine anxiously, as she almost ran across the laboratory to Craig. "Fine!" he exaggerated, brightly. "Really?" she repeated anxiously. "Look!" he said, turning to his microscope. He took some blood from a test tube in our electric incubator and placed a drop on a slide. It was some of the blood infected by the germs carried by the tick. "That is how our blood looked--before the new nurse arrived," he smiled, while Elaine looked at it in horror. Then he pricked his arm and let a drop smear on another slide. "Now look at that--perfectly normal," he added. "Oh--I'm so glad," she exclaimed radiantly. "Normal--thanks to you. You saved us. You were just in time," cried Craig taking both her hands in his. He was about to kiss her, when she broke away. "Craig," she whispered, blushing and looking hastily at us. Aunt Josephine and I could only smile at the disgusted glance Craig gave us, as he thrust his hands in his pockets and wished us a thousand miles away at that moment. CHAPTER V SHADOWS OF WAR For a long time Kennedy had, I knew, been at work at odd moments in the laboratory secretly. What it was that he was working on, even I was unable to guess, so closely had he guarded his secret. But that it was something momentous, I was assured. Long Sin had already been arrested and it was a day or two after the escape of Wu himself who had come just in time to prevent the confession by one of his emissaries of the whereabouts of his secret den. Kennedy had Chase and another detective whom he frequently employed on routine matters at work over the clues developed by his use of the sphygmograph. Elaine, anxious for news, had dropped in on us at the laboratory just as Kennedy was hastily opening his mail. Craig came to a large letter with an official look, slit open the envelope, and unfolded the letter. "Hurrah!" he cried, jumping up and thrusting the letter before us. "Read that." Across the top of the paper were embossed in blue the formidable words: United States Navy Department, Washington, D. C. The letter was most interesting: PROFESSOR CRAIG KENNEDY, The University, New York City. DEAR SIR, Your telautomatic torpedo model was tested yesterday and I take great pleasure in stating that it was entirely successful. There is no doubt that the United States is safe from attack as long as we retain its secret. Very sincerely yours, DANIEL WATERS, Ass't Sec'y. "Oh, Craig," congratulated Elaine, as she handed back the note. "I'm so glad for your sake. How famous you will be!" "When are we going to see the wonderful invention, Craig?" I added as I grasped his hand and, in return, he almost broke the bones in mine wringing it. "As soon as you wish," he replied, moving over to the safe near-by and opening it. "Here's the only other model in existence besides the model I sent to Washington." He held up before us a cigar-shaped affair of steel, about eight inches long, with a tiny propeller and rudder of a size to correspond. Above was a series of wires, four or five inches in length, which, he explained, were the aerials by which the torpedo was controlled. "The principle of the thing," he went on proudly, "is that I use wireless waves to actuate relays on the torpedo. The power is in the torpedo; the relay releases it. That is, I send a child with a message; the grown man, through the relay, does the work. So, you see, I can sit miles away in safety and send my little David out anywhere to strike down a huge Goliath." It was not difficult to catch his enthusiasm over the marvellous invention, though we could not follow him through the mazes of explanation about radio-combinators, telecommutators and the rest of the technicalities. I may say, however, that on his radio-combinator he had a series of keys marked "Forward," "Back," "Start," "Stop," "Rudder Right," "Rudder Left," and so on. He had scarcely finished his brief description when there came a knock at the door. I answered it. It was Chase and his assistant, whom Kennedy had employed in the affair. "We've found the place on Pell Street that we think is Wu Fang's," they reported excitedly. "It's in number fourteen, as you thought. We've left an operative disguised as a blind beggar to watch the place." "Oh, good!" exclaimed Elaine, as Craig and I hurried out after Chase and his man with her. "May I go with you?" "Really, Elaine," objected Craig, "I don't think it's safe. There's no telling what may happen. In fact, I think Walter and I had better not be seen there even with Chase." She pouted and pleaded, but Craig was obdurate. Finally she consented to wait for us at home provided we brought her the news at the earliest moment and demonstrated the wonderful torpedo as well. Craig was only too glad to promise and we waved good-bye as her car whisked her off. Half an hour later we turned into Chinatown from the shadow of the elevated railroad on Chatham Square, doing our best to affect a Bowery slouch. We had not gone far before we came to the blind beggar. He was sitting by number fourteen with a sign on his breast, grinding industriously at a small barrel organ before him on which rested a tin cup. We passed him and Kennedy took out a coin from his pocket and dropped it into the cup. As he did so, he thrust his hand into the cup and quickly took out a piece of paper which he palmed. The blind beggar thanked and blessed us, and we dodged into a doorway where Kennedy opened the paper: "Wu Fang gone out." "What shall we do?" I asked. "Go in anyhow," decided Kennedy quickly. We left the shelter of the doorway and walked boldly up to the door. Deftly Kennedy forced it and we entered. We had scarcely mounted the stairs to the den of the Serpent, when a servant in a back room, hearing a noise, stuck his head in the door. Kennedy and I made a dash at him and quickly overpowered him, snapping the bracelets on his wrists. "Watch him, Walter," directed Craig as he made his way into the back room. . . . . . . . In the devious plots and schemes of Wu Fang, his nefarious work had brought him into contact not only with criminals of the lowest order but with those high up in financial and diplomatic circles. Thus it happened that at such a crisis as Kennedy had brought about for him Wu had suddenly been called out of the city and had received an order from a group of powerful foreign agents known secretly as the Intelligence Office to meet an emissary at a certain rocky promontory on the Connecticut shore of Long Island Sound the very day after Kennedy's little affair with him in the laboratory and the day before the letter from Washington arrived. Though he was mortally afraid of Kennedy's pursuit, there was nothing to do but obey this imperative summons. Quietly he slipped out of town, the more readily when he realized that the summons would take him not far from the millionaire cottage colony where Elaine had her summer home, which, however, she had not yet opened. There, on the rocky shore, he sat gazing out at the waves, waiting, when suddenly, from around the promontory, came a boat rowed by two stalwart sailors. It carried as passengers two dark-complexioned, dark-haired men, foreigners evidently, though carefully dressed so as to conceal both their identity and nationality. As the boat came up to a strip of sandy beach among the rocks, the sailors held it while their two passengers jumped out. Then they rowed away as quickly as they had come. The two mysterious strangers saluted Wu. "We are under orders from the Intelligence Office," introduced one who seemed to be the leader, "to get this American, Kennedy." A subtle smile overspread Wu's face. He said nothing but this adventure promised to serve more than one end. "Information has just come to us," the stranger went on, "that Kennedy has invented a new wireless automatic torpedo. Already a letter is on its way informing him that it has been accepted by the Navy." The other man who had been drawing a cigar-shaped outline on the wet sand looked up. "We must get those models," he put in, adding, "both of them--the one he has and that the government has. Can it be done?" "I can get them," answered Wu sinisterly. And so, while Kennedy was drawing together the net about Wu, that wily criminal had already planned an attack on him in an unexpected quarter. Down in Washington the very morning that our pursuit of Wu came to a head, the officials of the navy department, both naval and civil, were having the final conference at which they were to accept officially Kennedy's marvellous invention which, it was confidently believed, would ultimately make war impossible. Seated about a long table in one of the board rooms were not only the officers but the officials of the department whose sanction was necessary for the final step. By a window sat a stenographer who was transcribing, as they were taken, the notes of the momentous meeting. They had just completed the examination of the torpedo and laid it on the end of the table scarcely an arm's length from the stenographer. As he finished a page of notes he glanced quickly at his watch. It was exactly three o'clock. Hastily he reached over for the torpedo and with one swift, silent movement tossed it out of the window. Down below, in a clump of rhododendrons, for several moments had been crouching one of the men who had borne the orders to Wu Fang at the strange meeting on the promontory. His eyes seemed riveted at the window above him. Suddenly the supreme moment for which this dastardly plot had been timed came. As the torpedo model dropped from the window, he darted forward, caught it, turned, and in an instant he was gone. . . . . . . . Wu Fang himself had returned after setting in motion the forces which he found necessary to call to aid the foreign agents in their plots against Kennedy's torpedo. As Wu approached the door of his den and was about to enter, his eye fell on our outpost, the blind beggar. Instantly his suspicions were aroused. He looked the beggar over with a frown, thought a moment, then turned and instead of entering went up the street. He made the circuit of the block and now came to an alley on the next street that led back of the building in which he had his den. Still frowning, he gazed about, saw that he was not followed, and entered a doorway. Up the stairs he made his way until he came to an empty loft. Quickly he went over to the blank wall and began feeling cautiously about as if for a secret spring hidden in the plaster. "No one in the back room," said Kennedy rejoining me in the den itself with the prisoner. "He's out, all right." Before Craig was a mirror. As he looked into it, at an angle, he could see a part of the decorations of the wall behind him actually open out. For an instant the evil face of Wu Fang appeared. Without a word, Craig walked into the back room. As he did so, Wu Fang, knife in hand, stealthily opened the sliding panel its full length and noiselessly entered the room behind me. With knife upraised for instant action he moved closer and closer to me. He had almost reached me and paused to gloat as he poised the knife ready to strike, when I heard a shout from Kennedy, and a scuffle. Craig had leaped out from behind a screen near the doorway to the back room where he had hidden to lure Wu on. With a powerful grasp, he twisted the knife from Wu's hand and it fell with a clatter on the floor. I was at Wu myself an instant later. He was a powerful fighter, but we managed to snap the handcuffs on him finally, also. "Walter," panted Kennedy straightening himself out after the fracas, "I'll stay here with the prisoners. Go get the police." I hurried out and rushed down the street seeking an officer. Up in the den, Wu Fang, silent, stood with his back to the wall, scowling sullenly. Close beside him hung a sort of bell-cord, just out of reach. Kennedy, revolver in hand, was examining the writing-table to discover whatever evidence he could. Slowly, imperceptibly, inch by inch, Wu moved toward the bell-cord. He was reaching out with his manacled hands to seize it when Kennedy, alert, turned, saw him, and instantly shot. Wu literally crumpled up and dropped to the floor as Craig bounded over to him. By this time I had found a policeman and he had summoned the wagon from the Elizabeth Street station, a few blocks away. As we drove up before the den, I leaped out and the police followed. Imagine my surprise at seeing Wu stretched on the floor. Kennedy had tried to staunch the flow of blood from a wound on Wu's shoulder with a handkerchief and now was making a temporary bandage which he bound on him. "How are you, sergeant?" nodded Kennedy. "Well, I guess you'll admit I made good this time." The sergeant smiled, recalling a previous occasion when the slippery Wu had squirmed through our fingers. Kennedy's restless eye fell on the bell-rope which had caused the trouble. Somehow, he seemed to have an irresistible desire to pull that rope. He gazed about the room. "Walter, you and the sergeant take the prisoners into the next room," he said. "I want to see what this thing really is." We moved Wu and his servant and stood in the doorway. Craig gave the rope a yank. Instantly there was an explosion. A concealed shotgun in the wall fired, scattering shot all over the front of Wu's table, just where we had been standing, knocking over and breaking vases, scattering papers and in general wrecking everything before it. "So, that's it," whistled Craig. "You fellows can come back now. Two of you men I'm going to leave here to watch the place and make other arrests if you can. Come on." With Kennedy I left the tenement while the sergeant marched the prisoners out, and we drove off with them. Quite a crowd had collected outside by the time we came out. Among them, naturally, were many Chinamen, and we could not see two of them hiding behind the rest on the outskirts, jabbering in low tones together and making hasty plans. As we clanged away down the street they followed more slowly on foot. Common humanity dictated that we take Wu first of all to a hospital and get him fixed up and to a hospital we went. Kennedy and I entered with our prisoners, closely guarded by the police. Craig handed Wu over to two young doctors and a nurse. By this time Wu was very weak from loss of blood. Still he had his iron nerve and that was carrying him through. The two young doctors and the nurse had scarcely begun to take off Craig's rude bandage to replace it properly, when a noise outside told us that a weeping and gesticulating delegation of Chinese had arrived. "Keep 'em back," called one of the doctors to an attendant. The attendant tried to drive them away, but nothing could force them back more than an inch or two as, in broken English, they sought to find out how Wu was. Their importunity proved too much for only one attendant. Still gibbering and gesticulating, the crowd brushed past him as if he had been a mere reed. The attendant raged about until he lost his head. But it was no use. There was nothing for him to do but to follow them in. Kennedy by this time had finished talking to the doctors and handing Wu over to them. They had taken him into a room in the dispensary. Just then the chattering crowd pushed in, some asking questions, others bewailing the fate of the great Wu Fang. They were so insistent that at last one of the doctors was forced to demand that the police drive them out. They started to push them back. In the melee, one of their number managed to get away from the rest and reach the doorway to the emergency room. He was, as we found out later, dressed almost precisely like Wu, although he had on a somewhat different cap. In build and size as well as features he was a veritable Dromio. The other Chinaman drew back behind the screen which hid the doorway to the emergency room and concealed himself. Meanwhile, Kennedy and I were laughing at the truly ludicrous antics of the astounded Celestials, thunderstruck at the capture of the peerless leader, while the police forced them back. "Well, good-bye," nodded Craig to the first doctor and nurse who had attended Wu Fang outside. "Good-bye. We'll fix him up and take good care that he doesn't cheat the law," they said, with a nod to the sergeant. . . . . . . . In the emergency room, Wu was placed on an operating table and there was bound up properly, though he was terribly weak now. Back of the screen, however, the other Chinaman was hiding, able to get an occasional glance at what was going on. There happened to be a table near him on which were gauze, cotton and other things. He reached over and took the gauze and quickly made it into a bandage, keeping one eye on the bandaging of Wu. Then he placed the bandage over his own shoulder and arm in the same way that he saw the doctors doing with Wu. They had finished with Wu and one of the doctors moved over to the doorway to call the sergeant. For the moment the rest had left Wu alone, his eyes apparently half closed through weakness. Each was busy about his own especial task. From behind the screen which was only a few feet from the operating table, the secreted Chinaman stepped out. Quickly he placed his own hat on Wu and took Wu's, then took Wu's place on the table while Wu slipped behind the screen. The doctor turned to the supposed Wu. "Come now," he ordered, handing him over to the police. "Here he is at last." The sergeant started to lead the prisoner out. As he did so, he looked sharply at him. He could scarcely believe his eyes. There was something wrong. All Chinaman might look alike to some people but not to him. "That's not Wu Fang!" he exclaimed. Instantly there was the greatest excitement. The doctors were astounded as all rushed into the emergency room again. One of them looked behind the screen. There was an open window. "That's how he got away," he cried. Meanwhile, several blocks from the hospital, Wu, still weak but more than ever nerved up, came out of his place of concealment, gazed up and down the street, and, seeing no one following, hurried away from the hospital as fast as his shaky legs would bear him. . . . . . . . Confident that at last our arch enemy was safely landed in the hands of the police, Kennedy and I had left the hospital and were hastening to Elaine with the news. We stopped at the laboratory only long enough to get the torpedo from the safe and at a toy store where Craig bought a fine little clockwork battleship. We found Elaine and Aunt Josephine in the conservatory and quickly Kennedy related how we had captured Wu. But, like all inventors, his pet was the torpedo and soon we were absorbed in his description of it. As he unwrapped it, Elaine drew back, timidly, from the fearful engine of destruction. Kennedy smiled. "No, it isn't dangerous," he said reassuringly. "I've removed its charge and put in a percussion cap. Let me show you, on a small scale, how it works," he added, winding up the battleship and placing it in the fountain. Next he placed the torpedo in the water at the other end of the tank. "Come over here," he said, indicating to us to follow him into the palms. There he had placed the strange wireless apparatus which controlled the torpedo. He pressed a lever. We peered out through the fronds of the palms. That uncanny little cigar-shaped thing actually started to move over the surface of the water. "Of course I could make it dive," explained Craig, "but I want you to see it work." Around the tank it went, turned, cut a figure eight, as Kennedy manipulated the levers. Then it headed straight toward the battleship. It struck. There was a loud report, a spurt of water. One of the skeleton masts fell over. The battleship heeled over, and slowly sank, bow first. "Wonderful!" exclaimed Elaine. "That was very realistic." We brushed our way out through the thick palms, congratulating Kennedy on the perfect success of his demonstration. So astonished were we that we did not hear the doorbell ring. Jennings answered it and admitted two men. "Is Professor Kennedy here?" asked one. "We have been to his apartment and to the laboratory." "I'll see," said Jennings discretely, taking the card of one of them and leaving them in the drawing-room. "Two gentlemen to see you, Mr. Kennedy," Jennings interrupted our congratulations, handing Craig a card. "Shall I tell them you are here, sir?" Craig glanced at the card. "I wonder what that can be?" he said, turning the card toward us. It was engraved: W. R. Barnes U. S. Secret Service. "Yes, I'll see them," he said, then to us, "Please excuse me?" Elaine, Aunt Josephine and I strolled off in the palms toward the Fifth Avenue side, while Jennings went out toward the back of the house. "Well, gentlemen," greeted Kennedy as he met the two detectives, "what can I do for you?" The leader looked about, then leaned over and whispered, "We've just had word, Professor, that your model of the torpedo has been stolen from the Navy Department in Washington." "Stolen?" repeated Kennedy, staring aghast. "Yes. We fear that an agent of a foreign government has found a traitor in the department." Rapidly Kennedy's mind pictured what might be done with the deadly weapon in the hands of an enemy. "And," added the Secret Service man, "we have reason to believe that this foreign agent is using a Chinaman, Wu Fang." "But Wu has been arrested," replied Craig. "I arrested him myself. The police have him now." "Then you don't know of his escape?" Kennedy could only stare as they told the story. Suddenly, down the hall, came cries of, "Help! Help!" . . . . . . . While Craig was showing us the torpedo, the criminal machinery which Wu had set in motion at orders from the foreign agents was working rapidly. Outside the Dodge house, a man had shadowed us. He waited until we went in, then slunk in himself by the back way and climbed through an open window into the cellar. Quietly he made his way up through the cellar until finally he reached the library. Listening carefully he could hear us talking in the conservatory. Stealthily he moved out of the library. We had left the conservatory when he entered, peering through the palms. On he stole till he came to the fountain. He looked about. There, bobbing up and down, was the model of the torpedo for which he had dared so much. He picked it up and looked at it, gloating. The crook was about to move back toward the library, hugging the precious model close to himself when he heard Jennings coming. He started back to the conservatory. Jennings entered just in time to catch a fleeting glimpse of some one. His suspicions were roused and he followed. The crook reached the conservatory and opened a glass window leading out into the little garden beside the house. He was about to step out when the sound of voices in the garden arrested him. Elaine, Aunt Josephine and I had gone out and Elaine was showing me a new rose which had just been sent her. The crook fell back and dropped down behind the palms. Jennings looked about, but saw no one and stood there puzzled. Then the crook, fearing that he might be captured at any moment, looked about to see where he might hide the torpedo. There did not seem to be any place. Quickly he began to dig out the earth in one of the palm pots. He dropped the torpedo, wrapped still in the handkerchief, into the hole and covered it up. Jennings was clearly puzzled. He had seen some one rush in, but the conservatory was apparently empty. He had just turned to go out when he saw a palm move. There was a face! He made a dive for it and in a moment both he and the crook were rolling over and over. . . . . . . . Kennedy and the Secret Service men were talking earnestly when they heard the cry for help and the scuffle. They rushed out and into the conservatory in time to see the crook, who had broken away, knock out Jennings. He sprang to his feet and darted away. Kennedy's mind was working rapidly. Had the man been after the other model? The detectives went after him. But Craig went for the torpedo. As he looked in the tank, it was gone! He turned and followed the crook. I was still in the garden with Elaine and Aunt Josephine when I heard sounds of a struggle and a moment later a man emerged through the window of the conservatory followed by two other men. I went for him, but he managed to elude me and dashed for the wall in the back of the garden. The Secret Service men fired at him but he kept on. A moment later Craig came through the window. "Did any of you take the torpedo?" he asked. "No," replied Elaine, "we left it just as you had it." Kennedy seemed wild with anxiety. "Then both models have been stolen!" he cried, dashing after the Secret Service men with me close behind. The crook by this time had reached the top of the wall. Just as he was about to let himself down safely on the other side, a shot struck him. He pitched over and we ran forward. But he had just enough of a start. In spite of the shock and the wound he managed to pick himself up and with the help of a confederate hobbled into a waiting car, which sped away just as we came over the wall. We dropped to the ground just as another car approached. Craig commandeered it from its astonished driver, the Secret Service men and I piled in and we were off in a few seconds in hot pursuit. . . . . . . . Down at the terminal where trains came in from Washington, Wu, much better now, was waiting. He had pulled a long coat over his Chinese clothes and wore a slouch hat. As he looked at the incoming passengers he spied the man he was waiting for, the young crook who had been waiting in the shrubbery outside the Navy Building when the torpedo model was thrown out. The man had the model carefully wrapped up, under his arm. As his eye travelled over the crowd he recognized Wu but did not betray it. He walked by and, as he passed, hastily handed Wu the package containing the model. Wu slipped it under his coat. Then each went his way, in opposite directions. . . . . . . . It was a close race between the car bearing the two crooks and that which Kennedy had impressed into service, but we kept on up through the city and out across the country, into Connecticut. Time and again they almost got away until it became a question of following tire tracks. Once we came to a cross-road and Kennedy stopped and leaped out. Deeply planted in the mud, he could see the tracks of the car ahead leading out by the left road. Close beside the tire tracks were the footprints of two men going up the right hand road toward the Sound. "You follow the car and the driver," decided Craig, hastily indicating the road by which it had gone. "I'll follow the footprints." The Secret Service men jumped back into the car and Kennedy and I went along the shore road following the two crooks. Already the wounded crook, supported by his pal, had made his way down to the water and had come to a long wharf. There, near the land-end, they had a secret hiding-place into which they went. The other crook drew forth a smoke signal and began to prepare it. Kennedy and I were able, now, to move faster than they. As we came in sight of the wharf, Kennedy paused. "There they are, two of them," he indicated. I could just make them out in their hiding-place. The fellow who had stolen the torpedo was by this time so weak from loss of blood that he could hardly hold his head up, while the other hurried to fix-the smoke signal. He happened to glance up, and saw us. "Come, Red, brace up," he muttered. "They're on our trail." The wounded man was almost too weak to answer. "I--I can't," he gasped weakly, "You--go." Then, with a great effort, remembering the mission on which he had been sent, he whispered hoarsely, "I hid the second torpedo model in the Dodge house in the bottom of--" He tried hard to finish, but he was too weak. He fell back, dead. His pal had waited as long as he dared to learn the secret. He jumped up and ran out just as we burst into the hiding-place. Kennedy dropped down by the dead man and searched him, while I dashed after the other fellow. But I was not so well acquainted with the lay of the land as he and, before I knew it, he had darted into another of his numerous hiding-places. I hunted about, but I had lost the track. When I returned, I found Kennedy writing a hasty note. "I couldn't follow him, Craig," I confessed. "Too bad," frowned Craig evidently greatly worried by what had happened, as he folded the note. "Walter," he added seriously, "I want you to go find the fellow." He handed me the note. "And if anything separates us to-day--give this note to Elaine." I did not pay much attention to the tone he assumed, but often afterward I pondered over it and the serious and troubled look on his face. I was too chagrined at losing my man to think much of it then. I took the note and hurried out again after him. Meanwhile, as nearly as I can now make out, Kennedy searched the dead man again. There was certainly no clue to his identity on him, nor had he the torpedo model. Craig looked about. Suddenly, he fell flat on his stomach. There was Wu Fang himself, coming to the wharf, carrying the model of the torpedo which had been stolen in Washington and brought up to him by his emissary. Kennedy, crouching down and taking advantage of every object that sheltered him, crawled cautiously into an angle. Unsuspecting, Wu came to the land-end of the wharf. There he saw his lieutenant, dead--and the smoke signal still beside him, unlighted. He bent over in amazement and examined the man. From his hiding-place Kennedy crept stealthily. He had scarcely got within reach of Wu when the alert Chinaman seemed to sense his presence. He rose quickly and swung around. The two arch enemies gazed at each other a moment silently. Each knew it was the final, fatal encounter. Slowly Wu drew a long knife and leaped at Kennedy who grappled with him. They struggled mercilessly. In the struggle, Craig managed to tear the torpedo out of Wu's hands, just as they rolled over. It fell on a rock. Instantly an explosion tore a hole in the sand, scattering the gravel all about. Relentlessly the combat raged. Out on the wharf itself they went, right up to the edge. Then both went over into the water, locked in each other's vice-like grip. Even in the water, they struggled, frantically. . . . . . . . My search for the escaped crook was unsuccessful. Somehow, however, it led me across country to a road. As I approached, I heard a car and looked up. There were the Secret Service men. I called them and stepped out of the bushes. They stopped and jumped out of the car and I ran to them. "Come back with me," I urged. "We found two of them. One is dead. Craig sent me to trace the other. I've lost the trail. Perhaps you can find it for me." We crashed through the brush quickly. Suddenly I heard something that caused me to start. It sounded like an explosion. "There's the place--over there," I pointed, pausing and indicating the direction of the wharf whence had come the explosion. What was it? We did not stop a moment, but hurried in that direction. We reached the shore where we saw marks of the explosion and of a fight. Out on the pier I ran breathlessly. I rushed to the very edge and gazed over, then climbed down the slippery piling and peered into the black water beneath. A few bubbles seemed to ooze up from below. Was that all? No, as I gazed down I saw that some dark object was there. Slowly Wu Fang's body floated to the surface and lay there, rocked by the waves. Deep in his breast stuck his own knife with its handle of the Sign of the Serpent! I reached down and seized him, as I peered about for Kennedy. There was nothing more there. "Craig!" I called desperately, "Craig!" There was no answer. The silence, the echo of the lapping water under the wharf was appalling, mocking. I managed to call the Secret Service men and they got Wu Fang's body up on the wharf. But I could not leave the spot. Where was Craig? There was not a sign of him. I could not realize it, even when the men brought grappling irons and began to search the black water. It was all a hideous dream. I saw and heard, in a daze. . . . . . . . It was not until late that night that I returned to the Dodge house. I had delayed my return as long as I could, but I knew that I must see Elaine some time. As I entered even Jennings must have seen that something was wrong. Elaine, who was sitting in the library with Aunt Josephine, rose as she saw me. "Did you get them?" she asked eagerly. I could not speak. She seemed to read the tragic look on my haggard face and stopped. "Why," she gasped, clutching at the desk, "what is the matter?" As gently as I could, I told her of the chase, of leaving Craig, of the explosion, of the marks of the struggle and of the finding of Wu Fang. As I finished, I thought she would faint. "And you--you went over everything about the wharf?" "Everything. The men even dragged for the--" I checked myself over the fateful word. Elaine looked at me wildly. I thought that she would lose her reason. She did not cry. The shock was too great for that. Suddenly I remembered the note. "Before I left him--the last time," I blurted out, "he wrote a note--to you." I pulled the crumpled paper from my pocket and Elaine almost tore it from me--the last word from him--and read: DEAREST: I may not return until the case is settled and I have found the stolen torpedo. Matters involving millions of lives and billions of dollars hang on the plot back of it. No matter what happens, have no fear. Trust me. Lovingly, CRAIG. She finished reading the note and slowly laid it down. Then she picked it up and read it again. Slowly she turned to me. I think I have never seen so sublime a look of faith on any one's face before. If I had not seen and heard what I had, it might have shaken my own convictions. "He told me to trust him and to have no fear," she said simply, gripping herself mentally and physically by main force, then with an air of defiance she looked at me. "I do not believe that he is dead!" I tried to comfort her. I wanted to do so. But I could do nothing but shake my head sadly. My own heart was full to overflowing. An intimacy such as had been ours could not be broken except with a shock that tore my soul. I knew that the poor girl had not seen what I had seen. Yet I could not find it in my heart to contradict her. She saw my look, read my mind. "No," she cried, still defiant, "no--a thousand times, no! I tell you--he is not dead!" CHAPTER VI THE LOST TORPEDO From the rocks of a promontory that jutted out not far from the wharf where Wu Fang's body was found and Kennedy had disappeared, opened up a beautiful panorama of a bay on one side and the Sound on the other. It was a deserted bit of coast. But any one who had been standing near the promontory the next day might have seen a thin line as if the water, sparkling in the sunlight, had been cut by a huge knife. Gradually a thin steel rod seemed to rise from the water itself, still moving ahead, though slowly now as it pushed its way above the surface. After it came a round cylinder of steel, studded with bolts. It was the hatch of a submarine and the rod was the periscope. As the submarine lay there at rest, the waves almost breaking over it, the hatch slowly opened and a hand appeared groping for a hold. Then appeared a face with a tangle of curly black hair and keen forceful eyes. After it the body of a man rose out of the hatch, a tall, slender, striking person. He reached down into the hold of the boat and drew forth a life preserver. "All right," he called down in an accent slightly foreign, as he buckled on the belt. "I shall communicate with you as soon as I have something to report." Then he deliberately plunged overboard and struck out for the shore. Hand over hand, he churned his way through the water toward the beach until at last his feet touched bottom and he waded out, shaking the water from himself like a huge animal. The coming of the stranger had not been entirely unheralded. Along the shore road by which Kennedy and I had followed the crooks whom we thought had the torpedo, on that last chase, was waiting now a powerful limousine with its motor purring. A chauffeur was sitting at the wheel and inside, at the door, sat a man peering out along the road to the beach. Suddenly the man in the machine signalled to the driver. "He comes," he cried eagerly. "Drive down the road, closer, and meet him." The chauffeur shot his car ahead. As the swimmer strode shivering up the roadway, the car approached him. The assistant swung open the door and ran forward with a thick, warm coat and hat. Neither the master nor the servant spoke as they met, but the man wrapped the coat about him, hurried into the car, the driver turned and quickly they sped toward the city. Secret though the entrance of the stranger had been planned, however, it was not unobserved. Along the beach, on a boulder, gazing thoughtfully out to sea and smoking an old briar pipe sat a bent fisherman clad in an oilskin coat and hat and heavy, ungainly boots. About his neck was a long woolen muffler which concealed the lower part of his face quite as effectually as his scraggly, grizzled whiskers. Suddenly, he seemed to discover something that interested him, slowly rose, then turned and almost ran up the shore. Quickly he dropped behind a large rock and waited, peering out. As the limousine bearing the stranger, on whom the fisherman had kept his eyes riveted, turned and drove away, the old salt rose from behind his rock, gazed after the car as if to fix every line of it in his memory and then he, too, quickly disappeared up the road. The stranger's car had scarcely disappeared when the fisherman turned from the shore road into a clump of stunted trees and made his way to a hut. Not far away stood a small, unpretentious closed car, also with a driver. "I shall be ready in a minute," the fisherman nodded almost running into the hut, as the driver moved his car up closer to the door. The larger motor had disappeared far down the bend of the road when the fisherman reappeared. In an almost incredible time he had changed his oilskins and muffler for a dark coat and silk hat. He was no longer a fisherman, but a rather fussy-looking old gentleman, bewhiskered still, with eyes looking out keenly from a pair of gold-rimmed glasses. "Follow that car--at any cost," he ordered simply as he let himself into the little motor, and the driver shot ahead down a bit of side road and out into the main shore road again, urging the car forward to overtake the one ahead. Such was the entrance of the stranger--Marcius Del Mar--into America. . . . . . . . How I managed to pass the time during the first days after the strange disappearance of Kennedy, I don't know. It was all like a dream--the apartment empty, the laboratory empty, my own work on the Star uninteresting, Elaine broken-hearted, life itself a burden. Hoping against hope the next day I decided to drop around at the Dodge house. As I entered the library unannounced, I saw that Elaine, with a faith for which I envied her, was sitting at a table, her back toward the door. She was gazing sadly at a photograph. Though I could not see it, I needed not to be told whose it was. She did not hear me come in, so engrossed was she in her thoughts. Nor did she notice me at first as I stood just behind her. Finally I put my hand on her shoulder as if I had been an elder brother. She looked up into my face. "Have you heard from him yet?" she asked anxiously. I could only shake my head sadly. She sighed. Involuntarily she rose and together we moved toward the garden, the last place we had seen him about the house. We had been pacing up and down the garden talking earnestly only a short time when a man made his way in from the Fifth Avenue gate. "Is this Miss Dodge?" he asked. "Yes," she replied eagerly. Neither Elaine nor I knew him at the time, though I think she thought he might be the bearer of some message from Craig. As a matter of fact he was the emissary to whom the stenographer had thrown the torpedo model from the Navy Building in Washington. His visit was only a part of a deep-laid scheme. Only a few minutes before, three crooks--among them our visitor--had stopped just below the house on a side street. To him the others had given final instructions and a note, and he had gone on, leaving the two standing there. "I have a note for you," he said, bowing and handing an envelope to Elaine, which she tore open and read. WASHINGTON, D. C. MISS ELAINE DODGE, Fifth Avenue, New York. MY DEAR MISS DODGE, The bearer, Mr. Bailey, of the Secret Service, would like to question you regarding the disappearance of Mr. Kennedy and the model of his torpedo. MORGAN BERTRAND, U. S. Secret Service. Even as we were talking the other two crooks had already moved up and had made their way around back of the stone wall that cut off the Dodge garden back of the house. There they stood, whispering eagerly and gazing furtively over the wall as their man talked to Elaine. After a moment I stepped aside, while Elaine read the note, and as he asked her a few questions, I could not help feeling that the affair had a very suspicious look. The more I thought of it, the less I liked it. Finally I could stand it no longer. "I beg your pardon," I excused myself to the alleged Mr. Bailey, "but may I speak to Miss Dodge alone just a minute?" He bowed, rather ungraciously I thought, and Elaine followed me aside while I told her my fears. "I don't like the looks of it myself," she agreed. "Yes, I'll be very careful what I say." While we were talking I could see out of the corner of my eye that the fellow was looking at us askance and frowning. But if I had had an X-ray eye, I might have seen his two companions on the other side of the wall, peering over as they had been before and showing every evidence of annoyance at my interference. The man resumed his questioning of Elaine regarding the torpedo and she replied guardedly, as in fact she could not do otherwise. Suddenly we heard shouts on the other side of the wall, as though some one were attacking some one else. There seemed to be several of them, for a man quickly flung himself over the wall and ran to us. "They're after us," he shouted to Bailey. Instantly our visitor drew a gun and followed the newcomer as he ran to get out of the garden in the opposite direction. Just then a tall, well-dressed, striking man came over the wall, accompanied by another dressed as a policeman, and rushed toward us. . . . . . . . The car bearing the mysterious stranger, Del Mar, kept on until it reached New York, then made its way through the city until it came to the Hotel La Coste. Del Mar jumped out of the car, his wet clothes covered completely by the long coat. He registered and rode up in the elevator to rooms which had already been engaged for him. In his suite a valet was already unpacking some trunks and laying out clothes when Del Mar and his assistant entered. With an exclamation of satisfaction at his unostentatious entry into the city, Del Mar threw off his heavy coat. The valet hastened to assist him in removing the clothes still wet and wrinkled from his plunge into the sea. Scarcely had Del Mar changed his clothes than he received two visitors. Strangely enough they were men dressed in the uniform of policemen. "First of all we must convince them of our honesty," he said looking fixedly at the two men. "Orders have been given to the men employed by Wu Fang to be about in half an hour. We must pretend to arrest them on sight. You understand?" "Yes, sir," they nodded. "Very well, come on," Del Mar ordered taking up his hat and preceding them from the room. Outside the La Coste, Del Mar and his two policemen entered the car which had driven Del Mar from the sea coast and were quickly whisked away, up-town, until they came near the Dodge house. Del Mar leaped from the car followed by his two policemen. "There they are, already," he whispered, pointing up the avenue. All three hastened up the avenue now where, beside a wall, they could see two men looking through intently as though very angry at something going on inside. "Arrest them!" shouted Del Mar as his own men ran forward. The fight was short and sharp, with every evidence of being genuine. One of the men managed to break away and jump the garden wall, with Del Mar and one of the policemen after him, while the other only reached the wall to be dragged down by the other policeman. Elaine and I had been, as I have said, talking with the man named Bailey who posed as a Secret Service man, when the rumpus began. As the man came over the fence, warning Bailey, it was evident that neither of them had time to escape. With his club the policeman struck the newcomer of the two flat while the tall, athletic gentleman leaped upon Bailey and before we knew it had him disarmed. In a most clean-cut and professional way he snapped the bracelets on the man. Elaine was astounded at the kaleidoscopic turn of affairs, too astounded even to make an outcry. As for me, it was all so sudden that I had no chance to take part in it. Besides I should not have known quite on which side to fight. So I did nothing. But as it was over so quickly, I took a step forward to our latest arrival. "Beg pardon, old man," I began, "but don't you think this is just a little raw? What's it all about?" The newest comer eyed me for a moment, then with quiet dignity drew from his pocket and handed me his card which read simply: M. Del Mar, Private Investigator. As I looked up, I saw Del Mar's other policeman bringing in another manacled man. "These are crooks--foreign agents," replied Del Mar pointing to the prisoners. "The government has employed me to run them down." "What of this?" asked Elaine holding up the note from Bertrand. "A fake, a forgery," reiterated Del Mar, looking at it a moment critically. Then to the men uniformed as police he ordered, "You can take them to jail. They're the fellows, all right." As the prisoners were led off, Del Mar turned to Elaine. "Would you mind answering a few questions about these men?" "Why--no," she hesitated. "But I think we'd better go into the house, after such a thing as this. It makes me feel nervous." With Del Mar I followed Elaine in through the conservatory. . . . . . . . Del Mar had scarcely registered at the La Coste when the smaller car which had been waiting at the fisherman's hut drew up before the hotel entrance. From it alighted the fussy old gentleman who bore such a remarkable resemblance to the fisherman, hastily paid his driver and entered the hotel. He went directly to the desk and with well-manicured finger, scarcely reminiscent of a fisherman, began tracing the names down the list until he stopped before one which read: Marcius Del Mar and valet. Washington, D. C. Room 520. With a quick glance about, he made a note of it, and turned away, leaving the La Coste to take up quarters of his own in the Prince Henry down the street. Not until Del Mar had left with his two policemen did the fussy old gentleman reappear in the La Coste. Then he rode up to Del Mar's room and rapped at the door. "Is Mr. Del Mar in?" he inquired of the valet. "No, sir," replied that functionary. The little old man appeared to consider, standing a moment dandling his silk hat. Absent-mindedly he dropped it. As the valet stooped to pick it up, the old gentleman exhibited an agility and strength scarcely to be expected of his years. He seized the valet, while with one foot he kicked the door shut. Before the surprised servant knew what was going on, his assailant had whipped from his pocket a handkerchief in which was concealed a thin tube of anesthetic. Then leaving the valet prone in a corner with the handkerchief over his face, he proceeded to make a systematic search of the rooms, opening all drawers, trunks and bags. He turned pretty nearly everything upside down, then started on the desk. Suddenly he paused. There was a paper. He read it, then with an air of extreme elation shoved it into his pocket. As he was going out he stopped beside the valet, removed the handkerchief from his face and bound him with a cord from the portieres. Then, still immaculate in spite of his encounter, he descended in the elevator, reentered a waiting car and drove off. Quite evidently, however, he wanted to cover his tracks for he had not gone a half dozen blocks before he stopped, paid and tipped the driver generously, and disappeared into the theatre crowd. Back again in the Prince Henry, whither the fussy little old man made his way as quickly as he could through a side street, he went quietly up to his room. His door was now locked. He did not have to deny himself to visitors, for he had none. Still, his room was cluttered by a vast amount of paraphernalia and he was seated before a table deep in work. First of all he tied a handkerchief over his nose and mouth. Then he took up a cartridge from the table and carefully extracted the bullet. Into the space occupied by the bullet he poured a white powder and added a wad of paper, like a blank cartridge, placing the cartridge in the chamber of a revolver and repeating the operation until he had it fully loaded. It was his own invention of an asphyxiating bullet. Perhaps half an hour later, the old gentleman, his room cleaned up and his immaculate appearance restored, sauntered forth from the hotel down the street like a veritable Turveydrop, to show himself. . . . . . . . Elaine seemed quite impressed with our new friend, Del Mar, as we made our way to the library, though I am not sure but that it was a pose on her part. At any rate he seemed quite eager to help us. "What do you suppose has become of Mr. Kennedy?" asked Elaine. Del Mar looked at her earnestly. "I should be glad to search for him," he returned quickly. "He was the greatest man in our profession. But first I must execute the commission of the Secret Service. We must find his torpedo model before it falls into foreign hands." We talked for a few moments, then Del Mar with a glance at his watch excused himself. We accompanied him to the door, for he was indeed a charming man. I felt that, if in fact he were assigned to the case, I ought to know him better. "If you're going down-town," I ventured, "I might accompany you part of the way." "Delighted," agreed Del Mar. Elaine gave him her hand and he took it in such a deferential way that one could not help liking him. Elaine was much impressed. As Del Mar and I walked down the avenue, he kept up a running fire of conversation until at last we came near the La Coste. "Charmed to have met you, Mr. Jameson," he said, pausing. "We shall see a great deal of each other I hope." I had not yet had time to say good-bye myself when a slight exclamation at my side startled me. Turning suddenly, I saw a very brisk, fussy old gentleman who had evidently been hurrying through the crowd. He had slipped on something on the sidewalk and lost his balance, falling near us. We bent over and assisted him to his feet. As I took hold of his hand, I felt a peculiar pressure from him. He had placed something in my hand. My mind worked quickly. I checked my first impulse to speak and, more from curiosity than anything else, kept the thing he had passed to me surreptitiously. "Thank you, gentlemen," he puffed, straightening himself out. "One of the infirmities of age. Thank you, thank you." In a moment he had bustled off quite comically. Again Del Mar said good-bye and I did not urge him to stay. He had scarcely gone when I looked at the thing the old man had placed in my hand. It was a little folded piece of paper. I opened it slowly. Inside was printed in pencil, disguised: "BE CAREFUL. WATCH HIM." I read it in amazement. What did it mean? . . . . . . . At the La Coste, Del Mar was met by two of his men in the lobby and they rode up to his room. Imagine their surprise when they opened the door and found the valet lying bound on the floor. "Who the deuce did this?" demanded Del Mar as they loosened him. The valet rose weakly to his feet. "A little old man with gray whiskers," he managed to gasp. Del Mar looked at him in surprise. Instantly his active mind recalled the little old man who had fallen before us on the street. Who--what was he? "Come," he said quickly, beckoning his two companions who had come in with him. Some time later, Del Mar's car stopped just below the Dodge house. "You men go around back of the house and watch," ordered Del Mar. As they disappeared he turned and went up the Dodge steps. . . . . . . . I walked back after my strange experience with the fussy little old gentleman, feeling more than ever, now that Craig was gone, that both Elaine and Aunt Josephine needed me. As we sat talking in the library, Rusty, released from the chain on which Jennings kept him, bounded with a rush into the library. "Good old fellow," encouraged Elaine, patting him. Just then Jennings entered and a moment later was followed by Del Mar, who bowed as we welcomed him. "Do you know," he began, "I believe that the lost torpedo model is somewhere in this house and I have reason to anticipate another attempt of foreign agents to find it. If you'll pardon me, I've taken the liberty of surrounding the place with some men we can trust." While Del Mar was speaking, Elaine picked up a ribbon from the table and started to tie it about Rusty's neck. As Del Mar proceeded she paused, still holding the ribbon. Rusty, who hated ribbons, saw his chance and quietly sidled out, seeking refuge in the conservatory. Alone in the conservatory, Rusty quickly forgot about the ribbon and began nosing about the palms. At last he came to the pot in which the torpedo model had been buried in the soft earth by the thief the night it had been stolen from the fountain. Quickly Elaine recalled herself and, seeing the ribbon in her hand and Rusty gone, called him. There was no answer, and she excused herself, for it was against the rules for Rusty to wander about. In his haste the thief had left just a corner of the handkerchief sticking out of the dirt. What none of us had noticed, Rusty's keen eyes and nose discovered and his instinct told him to dig for it. In a moment he uncovered the torpedo and handkerchief and sniffed. Just then he heard his mistress calling him. Rusty had been whipped for digging in the conservatory and now, with his tail between his legs, he seized the torpedo in his mouth and bolted for the door of the drawing-room, for he had heard voices in the library. As he did so he dropped the handkerchief and the little propeller, loosened by his teeth, fell off. Elaine entered the conservatory, still calling. Rusty was not there. He had reached the stairs, scurrying up to the attic, still holding the torpedo model in his mouth. He pushed open the attic door and ran in. Rusty's last refuge in time of trouble was back of a number of trunks, among which were two of almost the same size and appearance. Behind one of them, he had hidden a miscellaneous collection of bones, pieces of biscuit and things dear to his heart. He dropped the torpedo among these treasures. Del Mar, meanwhile, had followed Elaine through the hall and into the conservatory. As he entered he could see her stooping down to look through the palms for Rusty. She straightened up and went on out. Del Mar followed. Beside the palm pot where Rusty had found the torpedo, he happened to see the old handkerchief soiled with dirt. Near-by lay the little propeller. He picked them up. "She has found it!" he exclaimed in wonder, following Elaine. By this time Rusty had responded to Elaine's calls and came tearing down-stairs again. "Naughty Rusty," chided Elaine, tying the ribbon on him. "So--you have found him at last?" remarked Del Mar looking quickly at Elaine to see if she would get a double meaning. "Yes. He's had a fine time running away," she replied. Del Mar was scarcely able to conceal his suspicion of her. Was she a clever actress, hiding her discovery, he wondered? . . . . . . . Outside, on the lawn, Del Mar's men had been looking about, but had discovered nothing. They paused a moment to speak. "Look out!" whispered one of them. "There's some one coming." They dropped down in the shadow. There in the light of the street lamps was the fussy old gentleman coming across the lawn. He stole up to the door of the conservatory and looked through. Del Mar's men crawled a few feet closer. The little old man entered the conservatory and looked about again stealthily. The two men followed him in noiselessly and watched as he bent over the palm pot from which the dog had dug up the torpedo. He looked at the hole curiously. Just then he heard sounds behind him and sprang to his feet. "Hands up!" ordered one of the men covering him with a gun. The little old man threw up his hands, raising his cane still in his right hand. The man with the gun took a step closer. As he did so, the little old man brought down his cane with a quick blow and knocked the gun out of his hand. The second man seized the cane. The old man jerked the cane back and was standing there with a thin tough steel rapier. It was a sword-cane. Del Mar's man held the sheath. As the man attacked with the sheath, the little old man parried, sent it flying from his grasp, and wounded him. The wounded man sank down, while the little old man ran off through the palms, followed by the other of Del Mar's men. Around the hall, he ran, and back into the conservatory where he picked up a heavy chair and threw it through the glass, dropping himself behind a convenient hiding-place near-by. Del Mar's man, close after him, mistaking the crash of glass for the escape of the man he was pursuing, went on through the broken exit. Then the little old man doubled on his tracks and made for the front of the house. . . . . . . . With Aunt Josephine I had remained in the library. "What's that?" I exclaimed at the first sounds. "A fight?" Together we rushed for the conservatory. The fight followed so quickly by the crash of glass also alarmed Elaine and Del Mar in the hallway and they hurried toward the library, which we had just left, by another door. As they entered, they saw a little old gentleman rushing in from the conservatory and locking the door behind him. He whirled about, and he and Del Mar recognized each other at once. They drew guns together, but the little old man fired first. His bullet struck the wall back of Del Mar and a cloud of vapor was instantly formed, enveloping Del Mar and even Elaine. Del Mar fell, overcome, while Elaine sank more slowly. The little old man ran forward. In the conservatory, Aunt Josephine and I heard the shooting, just as one of Del Mar's men ran in again. With him we ran back toward the library. By this time the whole house was aroused. Jennings and Marie were hurrying down-stairs, crying for help and making their way to the library also. In the library, the little old man bent over Del Mar and Elaine. But it was only a moment later that he heard the whole house aroused. Quickly he shut and locked the folding-doors to the drawing-room, as, with Del Mar's man, I was beating at the rear library door. "I'll go around," I suggested, hurrying off, while Del Mar's man tried to beat in the door. Inside the little old man who had been listening saw that there was no means of escape. He pulled off his coat and vest and turned them inside out. On the inside he had prepared an exact copy of Jennings' livery. It was only a matter of seconds before he had completed his change. For a moment he paused and looked at the two prostrate figures before him. Then he took a rose from a vase on the table and placed it in Elaine's hand. Finally, with his whiskers and wig off he moved to the rear door where Del Mar's man was beating and opened it. "Look," he cried pointing in an agitated way at Del Mar and Elaine. "What shall we do?" Del Mar's man, who had never seen Jennings, ran to his master and the little old man, in his new disguise, slipped quietly into the hall and out the front door, where he had a taxicab waiting for him, down the street. A moment later I burst open the other library door and Aunt Josephine followed me in, just as Jennings himself and Marie entered from the drawing-room. It was only a moment before we had Del Mar, who was most in need of care, on the sofa and Elaine, already regaining consciousness, lay back in a deep easy chair. As Del Mar moved, I turned again to Elaine who was now nearly recovered. "How do you feel?" I asked anxiously. Her throat was parched by the asphyxiating fumes, but she smiled brightly, though weakly. "Wh-where did I get that?" she managed to gasp finally, catching sight of the rose in her hand. "Did you put it there?" I shook my head and she gazed at the rose, wondering. Whoever the little man was, he was gone. I longed for Craig. CHAPTER VII THE GRAY FRIAR So confident was Elaine that Kennedy was still alive that she would not admit to herself what to the rest of us seemed obvious. She even refused to accept Aunt Josephine's hints and decided to give a masquerade ball which she had planned as the last event of the season before she closed the Dodge town house and opened her country house on the shore of Connecticut. It was shortly after the strange appearance of the fussy old gentleman that I dropped in one afternoon to find Elaine addressing invitations, while Aunt Josephine helped her. As we chatted, I picked up one from the pile and mechanically contemplated the address: "M. Del Mar, Hotel La Coste, New York City." "I don't like that fellow," I remarked, shaking my head dubiously. "Oh, you're--jealous, Walter," laughed Elaine, taking the envelope away from me and piling it again with the others. Thus it was that in the morning's mail, Del Mar, along with the rest of us, received a neatly engraved little invitation: Miss Elaine Dodge requests the pleasure of your presence at the masquerade ball to be given at her residence on Friday evening June 1st. "Good!" he exclaimed, reaching for the telephone, "I'll go." In a restaurant in the white light district two of those who had been engaged in the preliminary plot to steal Kennedy's wireless torpedo model, the young woman stenographer who had betrayed her trust and the man to whom she had passed the model out of the window in Washington, were seated at a table. So secret had been the relations of all those in the plot that one group did not know the other and the strangest methods of communication had been adopted. The man removed a cover from a dish. Underneath, perhaps without even the waiter's knowledge, was a note. "Here are the orders at last," he whispered to the girl, unfolding and reading the note. "Look. The model of the torpedo is somewhere in her house. Go to-night to the ball as a masquerader and search for it." "Oh, splendid!" exclaimed the girl. "I'm crazy for a little society after this grind. Pay the check and let's get out and choose our costumes." The man paid the check and they left hurriedly. Half an hour later they were at a costumer's shop choosing their disguises, both careful to get the fullest masks that would not excite suspicion. It was the night of the masquerade. During the afternoon Elaine had been thinking more than ever of Kennedy. It all seemed unreal to her. More than once she stopped to look at his photograph. Several times she checked herself on the point of tears. "No," she said to herself with a sort of grim determination. "No--he IS alive. He will come back to me--he WILL." And yet she had a feeling of terrific loneliness which even her most powerful efforts could not throw off. She was determined to go through with the ball, now that she had started it, but she was really glad when it came time to dress, for even that took her mind from her brooding. As Marie finished helping her put on a very effective and conspicuous costume, Aunt Josephine entered her dressing-room. "Are you ready, my dear?" she asked, adjusting the mask which she carried so that no one would recognize her as Martha Washington. "In just a minute, Auntie," answered Elaine, trying hard to put out of her mind how Craig would have liked her dress. Somewhat earlier, in my own apartment, I had been arraying myself as Boum-Boum and modestly admiring the imitation I made of a circus clown as I did a couple of comedy steps before the mirror. But I was not really so light-hearted. I could not help thinking of what this night might have been if Kennedy had been alive. Indeed, I was glad to take up my white mask, throw a long coat over my outlandish costume and hurry off in my waiting car in order to forget everything that reminded me of him in the apartment. Already a continuous stream of guests was trickling in through the canopy from the curb to the Dodge door, carriages and automobiles arriving and leaving amid great gaping from the crowd on the sidewalk. As I entered the ballroom it was really a brilliant and picturesque assemblage. Of course I recognized Elaine in spite of her mask, almost immediately. Characteristically, she was talking to the one most striking figure on the floor, a tall man in red--a veritable Mephistopheles. As the music started, Elaine and his Satanic Majesty laughingly fox-trotted off but were not lost to me in the throng. I soon found myself talking to a young lady in a spotted domino. She seemed to have a peculiar fascination for me, yet she did not monopolize all my attention. As we trotted past the door, I could see down the hall. Jennings was still admitting late arrivals, and I caught a glimpse of one costumed as a gray friar, his cowl over his head and his eyes masked. Chatting, we had circled about to the conservatory. A number of couples were there and, through the palms, I saw Elaine and Mephisto laughingly make their way. As my spotted domino partner and I swung around again, I happened to catch another glimpse of the gray friar. He was not dancing, but walking, or rather stalking, about the edge of the room, gazing about as if searching for some one. In the conservatory, Elaine and Mephisto had seated themselves in the breeze of an open window, somewhat in the shadow. "You are Miss Dodge," he said earnestly. "You knew me?" she laughed. "And you?" He raised his mask, disclosing the handsome face and fascinating eyes of Del Mar. "I hope you don't think I'm here in character," he laughed easily, as she started a bit. "I--I--well, I didn't think it was you," she blurted out. "Ah--then there is some one else you care more to dance with?" "No--no one--no." "I may hope, then?" He had moved closer and almost touched her hand. The pointed hood of the gray friar in the palms showed that at last he saw what he sought. "No--no. Please--excuse me," she murmured rising and hurrying back to the ballroom. A subtle smile spread over the gray friar's masked face. Of course I had known Elaine. Whether she knew me at once I don't know or whether it was an accident, but she approached me as I paused in the dance a moment with my domino girl. "From the--sublime--to the ridiculous," she cried excitedly. My partner gave her a sharp glance. "You will excuse me?" she said, and, as I bowed, almost ran off to the conservatory, leaving Elaine to dance off with me. . . . . . . . Del Mar, quite surprised at the sudden flight of Elaine from his side, followed more slowly through the palms. As he did so he passed a Mexican attired in brilliant native costume. At a sign from Del Mar he paused and received a small package which Del Mar slipped to him, then passed on as though nothing had happened. The keen eyes of the gray friar, however, had caught the little action and he quietly slipped out after the Mexican bolero. Just then the domino girl hurried into the conservatory. "What's doing?" she asked eagerly. "Keep close to me," whispered Del Mar, as she nodded and they left the conservatory, not apparently together. Up-stairs, away from the gayety of the ballroom, the bolero made his way until he came to Elaine's room, dimly lighted. With a quick glance about, he entered cautiously, closed the door, and approached a closet which he opened. There was a safe built into the wall. As he stooped over, the man unwrapped the package Del Mar had handed him and took out a curious little instrument. Inside was a dry battery and a most peculiar instrument, something like a little flat telephone transmitter, yet attached by wires to ear-pieces that fitted over the head after the manner of those of a wireless detector. He adjusted the head-piece and held the flat instrument against the safe, close to the combination which he began to turn slowly. It was a burglar's microphone, used for picking combination locks. As the combination turned, a slight sound was made when the proper number came opposite the working point. Imperceptible ordinarily to even the most sensitive ear, to an ear trained it was comparatively easy to recognize the fall of the tumblers over this microphone. As he worked, the door behind him opened softly and the gray friar entered, closing it and moving noiselessly over back of the shelter of a big mahogany high-boy, around which he could watch. At last the safe was opened. Rapidly the man went through its contents. "Confound it!" he muttered. "She didn't put it here--anyhow." The bolero started to close the safe when he heard a noise in the room and looked cautiously back of him. Del Mar himself, followed by the domino girl, entered. "I've opened it," whispered the emissary stepping out of the closet and meeting them, "but I can't find the--" "Hands up--all of you!" They turned in time to see the gray friar's gun yawning at them. Most politely he lined them up. Still holding his gun ready, he lifted up the mask of the domino girl. "So--it's you," he grunted. He was about to lift the mask of the Mexican, when the bolero leaped at him. Del Mar piled in. But sounds down-stairs alarmed them and the emissary, released, fled quickly with the girl. The gray friar, however, kept his hold on Mephistopheles, as if he had been wrestling with a veritable devil. . . . . . . . Down in the hall, I had again met my domino girl, a few minutes after I had resigned Elaine to another of her numerous admirers. "I thought you deserted me," I said, somewhat piqued. "You deserted me," she parried, nervously. "However, I'll forgive you if you'll get me an ice." I hastened to do so. But no sooner had I gone than Del Mar stalked through the hall and went up-stairs. My domino girl was watching for him, and followed. When I returned with the ice, I looked about, but she was gone. It was scarcely a moment later, however, that I saw her hurry down-stairs, accompanied by the Mexican bolero. I stepped forward to speak to her, but she almost ran past me without a word. "A nut," I remarked under my breath, pushing back my mask. I started to eat the ice myself, when, a moment later, Elaine passed through the hall with a Spanish cavalier. "Oh, Walter, here you are," she laughed. "I've been looking all over for you. Thank you very much, sire," she bowed with mock civility to the cavalier. "It was only one dance, you know. Please let me talk to Boum-Boum." The cavalier bowed reluctantly and left us. "What are you doing here alone?" she asked, taking off her own mask. "How warm it is." Before I could reply, I heard some one coming down-stairs back of me, but not in time to turn. "Elaine's dressing-table," a voice whispered in my ear. I turned suddenly. It was the gray friar. Before I could even reach out to grasp his robe, he was gone. "Another nut!" I exclaimed involuntarily. "Why, what did he say?" asked Elaine. "Something about your dressing-table." "My dressing-table?" she repeated. We ran quickly up the steps. Elaine's room showed every evidence of having been the scene of a struggle, as she went over to the table. There she picked up a rose and under it a piece of paper on which were some words printed with pencil roughly. "Look," she cried, as I read with her: Do honest assistants search safes? Let no one see this but Jameson. "What does it mean?" I asked. "My safe!" she cried moving to a closet. As she opened the door, imagine our surprise at seeing Del Mar lying on the floor, bound and gagged before the open safe. "Get my scissors on the dresser," cried Elaine. I did so, hastily cutting the cords that bound Del Mar. "What does it all mean?" asked Elaine as he rose and stretched himself. Still clutching his throat, as if it hurt, Del Mar choked, "I found a man, a foreign agent, searching the safe. But he overcame me and escaped." "Oh--then that is what the--" Elaine checked herself. She had been about to hand the note to Del Mar when an idea seemed to come to her. Instead, she crumpled it up and thrust it into her bosom. On the street the bolero and the domino girl were hurrying away as fast as they could. Meanwhile, the gray friar had overcome Del Mar, had bound and gagged him, and trust him into the closet. Then he wrote the note and laid it, with a rose from a vase, on Elaine's dressing-table before he, too, followed. More than ever I was at a loss to make it out. . . . . . . . It was the day after the masquerade ball that a taxicab drove up to the Dodge house and a very trim but not over-dressed young lady was announced as "Miss Bertholdi." "Miss Dodge?" she inquired as Jennings held open the portieres and she entered the library where Elaine and Aunt Josephine were. If Elaine had only known, it was the domino girl of the night before who handed her a note and sat down, looking about so demurely, while Elaine read: MY DEAR MISS DODGE, The bearer, Miss Bertholdi, is an operative of mine. I would appreciate it if you would employ her in some capacity in your house, as I have reason to believe that certain foreign agents will soon make another attempt to find Kennedy's lost torpedo model. Sincerely, M. DEL MAR. Elaine looked up from reading the note. Miss Bertholdi was good to look at, and Elaine liked pretty girls about her. "Jennings," she ordered, "call Marie." To the butler and her maid, Elaine gave the most careful instructions regarding Miss Bertholdi. "She can help you finish the packing, first," she concluded. The girl thanked her and went out with Jennings and Marie, asking Jennings to pay her taxicab driver with money she gave him, which he did, bringing her grip into the house. Later in the day, Elaine had both Marie and Bertholdi carrying armsful of her dresses from the closets in her room up to the attic where the last of her trunks were being packed. On one of the many trips, Bertholdi came alone into the attic, her arms full as usual. Before her were two trunks, very much alike, open and nearly packed. She laid her armful of clothes on a chair near-by and pulled one of the trunks forward. On the floor lay the trays of both trunks already packed. Bertholdi began packing her burden in one trunk which was marked in big white letters, "E. Dodge." Down in Elaine's room at the time Jennings entered. "The expressman for the trunks is here, Miss Elaine," he announced. "Is he? I wonder whether they are all ready," Elaine replied hurrying out of the room. "Tell him to wait." In the attic, Bertholdi was still at work, keeping her eyes open to execute the mission on which Del Mar had sent her. Rusty, forgotten in the excitement by Jennings, had roamed at will through the house and seemed quite interested. For this was the trunk behind which he had his cache of treasures. As Bertholdi started to move behind the trunk, Rusty could stand it no longer. He darted ahead of her into his hiding-place. Among the dog biscuit and bones was the torpedo model which he had dug up from the palm pot in the conservatory. He seized it in his mouth and turned to carry it off. There, in his path, was his enemy, the new girl. Quick as a flash, she saw what it was Rusty had, and grabbed at it. "Get out!" she ordered, looking at her prize in triumph and turning it over and over in her hands. At that moment she heard Elaine on the stairs. What should she do? She must hide it. She looked about. There was the tray, packed and lying on the floor near the trunk marked, "E. Dodge." She thrust it hastily into the tray pulling a garment over it. "Nearly through?" panted Elaine. "Yes, Miss Dodge." "Then please tell the expressman to come up." Bertholdi hesitated, chagrined. Yet there was nothing to do but obey. She looked at the trunk by the tray to fix it in her mind, then went down-stairs. As she left the room, Elaine lifted the tray into the trunk and tried to close the lid. But the tray was too high. She looked puzzled. On the floor was another tray almost identical. "The wrong trunk," she smiled to herself, lifting the tray out and putting the other one in, while she placed the first tray with the torpedo concealed in the other, unmarked, trunk where it belonged. Then she closed the first trunk. A moment later the expressman entered, with Bertholdi. "You may take that one," indicated Elaine. "Miss Dodge, here's something else to go in," said Bertholdi in desperation, picking up a dress. "Never mind. Put it in the other trunk." Bertholdi was baffled, but she managed to control herself. She must get word to Del Mar about that trunk marked "E. Dodge." . . . . . . . Late that afternoon, before a cheap restaurant might have been seen our old friend who had posed as Bailey and as the Mexican. He entered the restaurant and made his way to the first of a row of booths on one side. "Hello," he nodded to a girl in the booth. Bertholdi nodded back and he took his seat. She had begged an hour or two off on some pretext. Outside the restaurant, a heavily-bearded man had been standing looking intently at nothing in particular when Bertholdi entered. As Bailey came along, he followed and took the next booth, his hat pulled over his eyes. In a moment he was listening, his ear close up to the partition. "Well, what luck?" asked Bailey. "Did you get a clue?" "I had the torpedo model in my hands," she replied, excitedly telling the story. "It is in a trunk marked 'E. Dodge.'" All this and more the bearded stranger drank in eagerly. A moment later Bailey and Bertholdi left the booth and went out of the restaurant followed cautiously by the stranger. On the street the two emissaries of Del Mar stopped a moment to talk. "All right, I'll telephone him," she said as they parted in opposite directions. The stranger took an instant to make up his mind, then followed the girl. She continued down the street until she came to a store with telephone booths. The bearded stranger followed still, into the next booth but did not call a number. He had his ear to the wall. He could hear her call Del Mar, and although he could not hear Del Mar's answers, she repeated enough for him to catch the drift. Finally, she came out, and the stranger, instead of following her further, took the other direction hurriedly. . . . . . . . Del Mar himself received the news with keen excitement. Quickly he gave instructions and prepared to leave his rooms. A short time later his car pulled up before the La Coste and, in a long duster and cap, Del Mar jumped in, and was off. Scarcely had his car swung up the avenue when, from an alleyway down the street from the hotel, the chug-chug of a motor-cycle sounded. A bearded man, his face further hidden by a pair of goggles, ran out with his machine, climbed on and followed. On out into the country Del Mar's car sped. At every turn the motor-cycle dropped back a bit, observed the turn, then crept up and took it, too. So they went for some time. . . . . . . . On the level of the Grand Central where the trains left for the Connecticut shore where Elaine's summer home was located, Bailey was now edging his way through the late crowd down the platform. He paused before the baggage-car just as one of the baggage motor trucks rolled up loaded high with trunks and bags. He stepped back as the men loaded the luggage on the car, watching carefully. As they tossed on one trunk marked "E. Dodge," he turned with a subtle look and walked away. Finally he squirmed around to the other platform. No one was looking and he mounted the rear of the baggage-car and opened the door. There was the baggageman sitting by the side door, his back to Bailey. Bailey closed the door softly and squeezed behind a pile of trunks and bags. . . . . . . . Finally Del Mar reached a spot on the railroad where there were both a curve and a grade ahead. He stopped his car and got out. Down the road the bearded and goggled motorcyclist stopped just in time to avoid observation. To make sure, he drew a pocket field-glass and leveled it ahead. "Wait here," ordered Del Mar. "I'll call when I want you." Back on the road the bearded cyclist could see Del Mar move down the track though he could not hear the directions. It was not necessary, however. He dragged his machine into the bushes, hid it, and hurried down the road on foot. Del Mar's chauffeur was waiting idly at the wheel when suddenly the cold nose of a revolver was stuck under his chin. "Not a word--and hands up--or I'll let the moonlight through you," growled out a harsh voice. Nevertheless, the chauffeur managed to lurch out of the car and the bearded stranger, whose revolver it was, found that he would have to shoot. Del Mar was not far enough away to risk it. The chauffeur flung himself on him and they struggled fiercely, rolling over and over in the dust of the road. But the bearded stranger had a grip of steel and managed to get his fingers about the chauffeur's throat as an added insurance against a cry for help. He choked him literally into insensibility. Then, with a strength that he did not seem to possess, he picked up the limp, blue-faced body and carried it off the road and around the car. . . . . . . . In the baggage-car, the baggageman was smoking a surreptitious pipe of powerful tobacco between stations and contemplating the scenery thoughtfully through the open door. As the engine slowed up to take a curve and a grade, Bailey who had now and then taken a peep out of a little grated window above him, crept out from his hiding-place. Already he had slipped a dark silk mask over his face. As he made his way among the trunks and boxes, the train lurched and the baggageman who had his back to Bailey heard him catch himself. He turned and leaped to his feet. Bailey closed with him instantly. Over and over they rolled. Bailey had already drawn his revolver before he left his hiding-place. A shot, however, would have been fatal to his part in the plans and was only a last resort for it would have brought the trainmen. Finally Bailey rolled his man over and getting his right arm free, dealt the baggageman a fierce blow with the butt of the gun. The train was now pulling slowly up the grade. More time had been spent in overcoming the baggageman than he expected and Bailey had to work quickly. He dragged the trunk marked "E. Dodge" from the pile to the door and glanced out. . . . . . . . Just around the curve in the railroad, Del Mar was waiting, straining his eyes down the track. There was the train, puffing up the grade. As it approached he rose and waved his arms. It was the signal and he waited anxiously. Had his plans been carried out? The train passed. From the baggage-car came a trunk catapulted out by a strong arm. It hurtled through the air and landed with its own and the train's momentum. Over it rolled in the bushes, then stopped--unbroken, for Elaine had had it designed to resist even the most violent baggage-smasher. Del Mar ran to it. As the tail light of the train disappeared he turned around in the direction from which he had come, placed his two hands to his mouth and shouted. . . . . . . . From the side of the road by Del Mar's car the bearded motor-cyclist had just emerged, buttoning the chauffeur's clothes and adjusting his goggles to his own face. As he approached the car, he heard a shout. Quickly he tore off the black beard which had been his disguise and tossed it into the grass. Then he drew the coat high up about his neck. "All right!" he shouted back, starting along the road. Together he and Del Mar managed to scramble up the embankment to the road and, one at each handle of the trunk, they carried it back to the car, piling it in the back. The improvised chauffeur started to take his place at the wheel and Del Mar had his foot on the running-board to get beside him, when the now unbearded stranger suddenly swung about and struck Del Mar full in the face. It sent him reeling back into the dust. The engine of the car had been running and before Del Mar could recover consciousness, the stranger had shot the car ahead, leaving Del Mar prone in the roadway. . . . . . . . The train, with Bailey on it, had not gained much speed, yet it was a perilous undertaking to leap. Still, it was more so now to remain. The baggageman stirred. It was now a case of murder or a getaway. Bailey jumped. Scratched and bruised and shaken, he scrambled to his feet in the briars along the track. He staggered up to the road, pulled himself together, then hurried back as fast as his barked shins would let him. He came to the spot which he recognized as that where he had thrown off the trunk. He saw the trampled and broken bushes and made for the road. He had not gone far when he saw, far down, Del Mar suddenly attacked and thrown down, apparently by his own chauffeur. Bailey ran forward, but it was too late. The car was gone. As he came up to Del Mar lying outstretched in the road, Del Mar was just recovering consciousness. "What was the matter?" he asked. "Was he a traitor?" He caught sight of the real chauffeur on the ground, stripped. Del Mar was furious. "No," he swore, "it was that confounded gray friar again, I think. And he has the trunk, too!" . . . . . . . Speeding up the road the former masquerader and motor-cyclist stopped at last. Eagerly he leaped out of Del Mar's car and dragged the trunk over the side regardless of the enamel. It was the work of only a moment for him to break the lock with a pocket jimmy. One after another he pulled out and shook the clothes until frocks and gowns and lingerie lay strewn all about. But there was not a thing in the trunk that even remotely resembled the torpedo model. The stranger scowled. Where was it? CHAPTER VIII THE VANISHING MAN Del Mar had evidently, by this time, come to the conclusion that Elaine was the storm centre of the peculiar train of events that followed the disappearance of Kennedy and his wireless torpedo. At any rate, as soon as he learned that Elaine was going to her country home for the summer, he took a bungalow some distance from Dodge Hall. In fact, it was more than a bungalow, for it was a pretentious place surrounded by a wide lawn and beautiful shade trees. There, on the day that Elaine decided to motor in from the city, Del Mar arrived with his valet. Evidently he lost no time in getting to work on his own affairs, whatever they might be. Inside his study, which was the largest room in the house, a combination of both library and laboratory, he gave an order or two to his valet, then immediately sat down to his new desk. He opened a drawer and took out a long hollow cylinder, closed at each end by air-tight caps, on one of which was a hook. Quickly he wrote a note and read it over: "Install submarine bell in place of these clumsy tubes. Am having harbor and bridges mined as per instructions from Government. D." He unscrewed the cap at one end of the tube, inserted the note and closed it. Then he pushed a button on his desk. A panel in the wall opened and one of the men who had played policeman once for him stepped out and saluted. "Here's a message to send below," said Del Mar briefly. The man bowed and went back through the panel, closing it. Del Mar cleaned up his desk and then went out to look his new quarters over, to see whether everything had been prepared according to his instructions. From the concealed entrance to a cave on a hillside, Del Mar's man who had gone through the panel in the bungalow appeared a few minutes later and hurried down to the shore. It was a rocky coast with stretches of cliffs and now and then a ravine and bit of sandy beach. Gingerly he climbed down the rocks to the water. He took from his pocket the metal tube which Del Mar had given him and to the hook on one end attached a weight of lead. A moment he looked about cautiously. Then he threw the tube into the water and it sank quickly. He did not wait, but hurried back into the cave entrance. . . . . . . . Elaine, Aunt Josephine and I motored down to Dodge Hall from the city. Elaine's country house was on a fine estate near the Long Island Sound and after the long run we were glad to pull up before the big house and get out of the car. As we approached the door, I happened to look down the road. "Well, that's the country, all right," I exclaimed, pointing down the road. "Look." Lumbering along was a huge heavy hay rack on top of which perched a farmer chewing a straw. Following along after him was a dog of a peculiar shepherd breed which I did not recognize. Atop of the hay the old fellow had piled a trunk and a basket. To our surprise the hay rack stopped before the house. "Miss Dodge?" drawled the farmer nasally. "Why, what do you suppose he can want?" asked Elaine moving out toward the wagon while we followed. "Yes?" "Here's a trunk, Miss Dodge, with your name on it," he went on dragging it down. "I found it down by the railroad track." It was the trunk marked "E. Dodge" which had been thrown off the train, taken by Del Mar and rifled by the motor-cyclist. "How do you suppose it ever got here?" cried Elaine in wonder. "Must have fallen off the train," I suggested. "You might have collected the insurance under this new baggage law!" "Jennings," called Elaine. "Get Patrick and carry the trunk in." Together the butler and the gardener dragged it off. "Thank you," said Elaine, endeavoring to pay the farmer. "No, no, Miss," he demurred as he clucked to his horses. We waved to the old fellow. As he started to drive away, he reached down into the basket and drew out some yellow harvest apples. One at a time he tossed them to us as he lumbered off. "Truly rural," remarked a voice behind us. It was Del Mar, all togged up and carrying a magazine in his hand. We chatted a moment, then Elaine started to go into the house with Aunt Josephine. With Del Mar I followed. As she went Elaine took a bite of the apple. To her surprise it separated neatly into two hollow halves. She looked inside. There was a note. Carefully she unfolded it and read. Like the others, it was not written but printed in pencil: Be careful to unpack all your trunks yourself. Destroy this note.--A FRIEND. What did these mysterious warnings mean, she asked herself in amazement. Somehow so far they had worked out all right. She tore up the note and threw the pieces away. Del Mar and I stopped for a moment to talk. I did not notice that he was not listening to me, but was surreptitiously watching Elaine. Elaine went into the house and we followed. Del Mar, however, dropped just a bit behind and, as he came to the place where Elaine had thrown the pieces of paper, dropped his magazine. He stooped to pick it up and gathered the pieces, then rejoined us. "I hope you'll excuse me," said Elaine brightly. "We've just arrived and I haven't a thing unpacked." Del Mar bowed and Elaine left us. Aunt Josephine followed shortly. Del Mar and I sat down at a table. As he talked he placed the magazine in his lap beneath the table, on his knees. I could not see, but he was in reality secretly putting together the torn note which the farmer had thrown to Elaine. Finally he managed to fit all the pieces. A glance down was enough. But his face betrayed nothing. Still under the table, he swept the pieces into his pocket and rose. "I'll drop in when you are more settled," he excused himself, strolling leisurely out again. . . . . . . . Up in the bedroom Elaine's maid, Marie, had been unpacking. "Well, what do you know about that?" she exclaimed as Jennings and Patrick came dragging in the banged-up trunk. "Very queer," remarked Jennings, detailing the little he had seen, while Patrick left. The entrance of Elaine put an end to the interesting gossip and Marie started to open the trunk. "No, Marie," said Elaine. "I'll unpack them my self. You can put the things away later. You and Jennings may go." Quickly she took the things out of the battered trunk. Then she started on the other trunk which was like it but not marked. She threw out a couple of garments, then paused, startled. There was the lost torpedo--where Bertholdi had stuck it in her haste! Elaine picked it up and looked at it in wonder as it recalled all those last days before Kennedy was lost. For the moment she did not know quite what to make of it. What should she do? Finally she decided to lock it up in the bureau drawer and tell me. Not only did she lock the drawer but, as she left her room, she took the key of the door from the lock inside and locked it outside. . . . . . . . Del Mar did not go far from the house, however. He scarcely reached the edge of the grounds where he was sure he was not observed when he placed his fingers to his lips and whistled. An instant later two of his men appeared from behind a hedge. "You must get into her room," he ordered. "That torpedo is in her luggage somewhere, after all." They bowed and disappeared again into the shrubbery while Del Mar turned and retraced his steps to the house. In the rear of the house the two emissaries of Del Mar stole out of the shelter of some bushes and stood for a moment looking. Elaine's windows were high above them, too high to reach. There seemed to be no way to get to them and there was no ladder in sight. "We'll have to use the Dutch house-man's method," decided one. Together they went around the house toward the laundry. It was only a few minutes later that they returned. No one was about. Quickly one of them took off his coat. Around his waist he had wound a coil of rope. Deftly he began to climb a tree whose upper branches fell over the roof. Cat-like he made his way out along a branch and managed to reach the roof. He made his way along the ridge pole to a chimney which was directly back of and in line with Elaine's windows. Then he uncoiled the rope and made one end fast to the chimney. Letting the other end fall free down the roof, he carefully lowered himself over the edge. Thus it was not difficult to get into Elaine's room by stepping on the window-sill and going through the open window. The man began a rapid search of the room, turning up and pawing everything that Elaine had unpacked. Then he began on the little writing-desk, the dresser and the bureau drawers. A subtle smile flashed over his face as he came to one drawer that was locked. He pulled a sectional jimmy from his coat and forced it open. There lay the precious torpedo. The man clutched at it with a look of exultation. Without another glance at the room he rushed to the window, seized the rope and pulled himself to the roof, going as he had come. . . . . . . . It did not take me long to unpack the few things I had brought and I was soon back again in the living-room, where Aunt Josephine joined me in a few minutes. Just as Elaine came hurriedly down the stairway and started toward me, Del Mar entered from the porch. She stopped. Del Mar watched her closely. Had she found anything? He was sure of it. Her hesitation was only for a moment, however. "Walter," she said, "may I speak to you a moment? Excuse us, please?" Aunt Josephine went out toward the back of the house to see how the servants were getting on, while I followed Elaine up-stairs. Del Mar with a bow seated himself and opened his magazine. No sooner had we gone, however, than he laid it down and cautiously followed us. Elaine was evidently very much excited as she entered her dainty little room and closed the door. "Walter," she cried, "I've found the torpedo!" We looked about at the general disorder. "Why," she exclaimed nervously, "some one has been here--and I locked the door, too." She almost ran over to her bureau drawer. It had been jimmied open in the few minutes while she was down-stairs. The torpedo was gone. We looked at each other, aghast. Behind us, however, we did not see the keen and watchful eyes of Del Mar, opening the door and peering in. As he saw us, he closed the door softly, went down-stairs and out of the house. . . . . . . . Perhaps half a mile down the road, the farmer abandoned his hay rack and now, followed by his peculiar dog, walked back. He stopped at a point in the road where he could see the Dodge house in the distance, sat on the rail fence and lighted a blackened corn-cob pipe. There he sat for some time apparently engrossed in his own thoughts about the weather, the dog lying at his feet. Now and then he looked fixedly toward Dodge Hall. Suddenly his vagrant attention seemed to be riveted on the house. He drew a field-glass from his pocket and levelled it. Sure enough, there was a man coming out of a window, pulling himself up to the roof by a rope and going across the roof tree. He lowered the glasses quickly and climbed off the fence with a hitherto unwonted energy. "Come, Searchlight," he called to the dog, as together they moved off quickly in the direction he had been looking. Del Mar's men were coming through the hedge that surrounded the Dodge estate just as the farmer and his dog stepped out in front of them from behind a thicket. "Just a minute," he called. "I want to speak to you." He enforced his words with a vicious looking gun. It was two to one and they closed with him. Before he could shoot, they had knocked the gun out of his hand. Then they tried to break away and run. But the farmer seized one of them and held him. Meanwhile the dog developed traits all his own. He ran in and out between the legs of the other man until he threw him. There he stood, over him. The man attempted to rise. Again the dog threw him and kept him down. He was a trained Belgian sheep hound, a splendid police dog. "Confound the brute," growled the man, reaching for his gun. As he drew it, the dog seized his wrist and with a cry the man dropped the gun. That, too, was part of the dog's training. While the farmer and the other man struggled on the ground, the torpedo worked its way half from the man's pocket. The farmer seized it. The man fell back, limp, and the farmer, with the torpedo in one hand, grasped at the gun on the ground and straightened up. He had no sooner risen than the man was at him again. His unconsciousness had been merely feigned. The struggle was renewed. At that point, the hedge down the road parted and Del Mar stepped out. A glance was enough to tell him what was going on. He drew his gun and ran swiftly toward the combatants. As Del Mar approached, his man succeeded in knocking the torpedo from the farmer's hand. There it lay, several feet away. There seemed to be no chance for either man to get it. Quickly the farmer bent his wrist, aiming the gun deliberately at the precious torpedo. As fast as he could he pulled the trigger. Five of the six shots penetrated the little model. So surprised was his antagonist that the farmer was able to knock him out with the butt of his gun. He broke away and fled, whistling on a police whistle for the dog just as Del Mar ran up. A couple of shots from Del Mar flew wild as the farmer and his dog disappeared. Del Mar stopped and picked up the model. It had been shot into an unrecognizable mass of scrap. In a fury, Del Mar dashed it on the ground, cursing his men as he did so. The strange disappearance of the torpedo model from Elaine's room worried both of us. Doubtless if Kennedy had been there he would have known just what to do. But we could not decide. "Really," considered Elaine, "I think we had better take Mr. Del Mar into our confidence." "Still, we've had a great many warnings," I objected. "I know that," she persisted, "but they have all come from very unreliable sources." "Very well," I agreed finally, "then let's drive over to his bungalow." Elaine ordered her little runabout and a few moments later we climbed into it and Elaine shot the car away. As we rode along, the country seemed so quiet that no one would ever have suspected that foreign agents lurked all about. But it was just under such a cover that the nefarious bridge and harbor-mining work ordered by Del Mar's superiors was going ahead quietly. As our car climbed a hill on the other side of which, in the valley, was a bridge, we could not see one of Del Mar's men in hiding at the top. He saw us, however, and immediately wigwagged with his handkerchief to several others down at the bridge where they were attaching a pair of wires to the planking. "Some one coming," muttered one who was evidently a lookout. The men stopped work immediately and hid in the brush. Our car passed over the bridge and we saw nothing wrong. But no sooner had we gone than the men crept out and resumed work which had progressed to the point where they were ready to carry the wires of an electric connection through the grass, concealing them as they went. In the study of his bungalow, all this time, Del Mar was striding angrily up and down, while his men waited in silence. Finally he paused and turned to one of them. "See that the coast is clear and kept clear," he ordered. "I want to go down." The man saluted and went out through the panel. A moment later Del Mar gave some orders to the other man who also saluted and left the house by the front door, just as our car pulled up. Del Mar, the moment the man was gone, put on his hat and moved toward the panel in the wall. He was about to enter when he heard some one coming down the hall to the study and stepped back, closing the panel. It was the butler announcing us. We had entered Del Mar's bungalow and now were conducted to his library. There Elaine told him the whole story, much to his apparent surprise, for Del Mar was a wonderful actor. "You see," he said as she finished telling of the finding and the losing of the torpedo, "just what I had feared would happen has happened. Doubtless the foreign agents have the deadly weapon, now. However, I'll not quit. Perhaps we may run them down yet." He reassured us and we thanked him as we said good-bye. Outside, Elaine and I got into the car again and a moment later spun off, making a little detour first through the country before hitting the shore road back again to Dodge Hall. On the rocky shore of the promontory, several men were engaged in sinking a peculiar heavy disk which they submerged about ten or twelve feet. It seemed to be held by a cable and to it wires were attached, apparently so that when a key was pressed a circuit was closed. It was an "oscillator", a new system for the employment of sound for submarine signalling, using water instead of air as a medium to transmit sound waves. It was composed of a ring magnet, a copper tube lying in an air-gap in a magnetic field and a stationary central armature. The tube was attached to a steel diaphragm. Really it was a submarine bell which could be used for telegraphing or telephoning both ways through water. The men finished executing the directions of Del Mar and left, carefully concealing the land connections and key of the bell, while we were still at Del Mar's. We had no sooner left, however, than one of the men who had been engaged in installing the submarine bell entered the library. "Well?" demanded Del Mar. "The bell is installed, sir," he said. "It will be working soon." "Good," nodded Del Mar. He went to a drawer and from it took a peculiar looking helmet to which was attached a sort of harness fitting over the shoulders and carrying a tank of oxygen. The head-piece was a most weird contrivance, with what looked like a huge glass eye in front. It was in reality a submarine life-saving apparatus. Del Mar put it on, all except the helmet which he carried with him, and then, with his assistant, went out through the panel in the wall. Through the underground passage the two groped their way, lighted by an electric torch, until at last they came to the entrance hidden in the underbrush, near the shore. Del Mar went over to the concealed station from which the submarine bell was sounded and pressed the key as a signal. Then he adjusted the submarine helmet to his head and deliberately waded out into the water, further and further, up to his head, then deeper still. As he disappeared into the water, his emissary turned and went back toward the shore road. . . . . . . . The ride around through the country and back to the shore, road from Del Mar's was pleasant. In fact it was always pleasant to be with Elaine, especially in a car. We were spinning along at a fast clip when we came to a rocky part of the coast. As we made a turn a sharp breeze took off my hat and whirled it far off the road and among the rocks of the shore. Elaine shut down the engine, with a laugh at me, and we left the car by the road while we climbed down the rocks after the hat. It had been carried into the water, close to shore and, still laughing, we clambered over the rocks. Elaine insisted on getting it herself and in fact did get it. She was just about to hand it to me, when something bobbed up in the water just in front of us. She reached for it and fished it out. It was a cylinder with air-tight caps on both ends, in one of which was a hook. "What do you suppose it is?" she asked, looking it over as we made our way up the rocks again to the car. "Where did it come from?" We did not see a man standing by our car, but he saw us. It was Del Mar's man who had paused on his way to watch us. As we approached he hid on the other side of the road. By this time we had reached the car and opened the cylinder. Inside was a note which read: "Chief arrived safely. Keep watch." "What does it mean?" repeated Elaine, mystified. Neither of us could guess and I doubt whether we would have understood any better if we had seen a sinister face peering at us from behind a rock near-by, although doubtless the man knew what was in the tube and what it meant. We climbed into the car and started again. As we disappeared, the man came from behind the rocks and ran quickly up to the top of the hill. There, from the bushes, he pulled out a peculiar instrument composed of a strange series of lenses and mirrors set up on a tripod. Eagerly he placed the tripod, adjusting the lenses and mirrors in the sunlight. Then he began working them, and it was apparent that he was flashing light beams, using a Morse code. It was a heliograph. Down the shore on the top of the next hill sat the man who had already given the signal with the handkerchief to those in the valley who were working on the mining of the bridge. As he sat there, his eye caught the flash of the heliograph signal. He sprang up and watched intently. Rapidly he jotted down the message that was being flashed in the sunlight: Dodge girl has message from below. Coming in car. Blow first bridge she crosses. Down the valley the lookout made his way as fast as he could. As he approached the two men who had been mining the bridge, he whistled sharply. They answered and hurried to meet him. "Just got a heliograph," he panted. "The Dodge girl must have picked up one of the messages that came from below. She's coming over the hill now in a car. We've got to blow up the bridge as she crosses." The men were hurrying now toward the bridge which they had mined. Not a moment was to be lost, for already they could see us coming over the crest of the hill. In a few seconds they reached the hidden plunger firing-box which had been arranged to explode the charge under the bridge. There they crouched in the brush ready to press the plunger the moment our car touched the planking. One of the men crept out a little nearer the road. "They're coming!" he called back, dropping down again. "Get ready!" . . . . . . . Del Mar's emissaries had not reckoned, however, that any one else might be about to whom the heliograph was an open book. But, further over on the hill, hiding among the trees, the old farmer and his dog were sitting quietly. The old man was sweeping the Sound with his glasses, as if he expected to see something any moment. To his surprise, however, he caught a flash of the heliograph from the land. Quickly he turned and jotted down the signals. As he did so, he seemed greatly excited, for the message read: Dodge girl has message from below. Coming in car. Blow first bridge she crosses. Quickly he turned his glasses down the road. There he could see our car rapidly approaching. He put up his glasses and hurried down the hill toward the bridge. Then he broke into a run, the dog scouting ahead. We were going along the road nicely now, coasting down the hill. As we approached the bridge, Elaine slowed up a bit, to cross, for the planking was loose. Just then the farmer who had been running down the hill saw us. "Stop!" he shouted. But we did not hear. He ran after us, but such a chase was hopeless. He stopped, in despair. With a gesture of vexation he took a step or two mechanically off the road. Elaine and I were coming fast to the bridge now. In their hiding-place, Del Mar's men were watching breathlessly. The leader was just about to press the plunger when all of a sudden a branch in the thicket beside him crackled. There stood the farmer and his dog! Instantly the farmer seemed to take in the situation. With a cry he threw himself at the man who had the plunger. Another man leaped at the farmer. The dog settled him. The others piled in and a terrific struggle followed. It was all so rapid that, to all, seconds seemed like hours. We were just starting to cross the bridge. One of the men broke away and crawled toward the plunger box. Our car was now in the middle of the bridge. Over and over rolled the men, the dog doing his best to help his master. The man who had broken away reached toward the plunger. With a shout he pushed it down. . . . . . . . Our car had just cleared the bridge when we were startled by a terrific roar behind us. It was as though a thousand tires had blown out at once. Elaine shut off the engine automatically and we looked back. The whole bridge had been blown up. A second before we had been in the middle of it. As the explosion came, the men who had been struggling in the thicket, paused, startled, and stared out. At that instant the old farmer saw his chance. It was all over and he bolted, calling the dog. Along the road to the bridge he ran, two of the men after him. "Come back," growled the leader. "Let him go. Do you want us all to get caught?" As the farmer ran up to the bridge, he saw it in ruins. But down the road he could see Elaine and myself, sitting in the car, staring back at the peril which we had so narrowly escaped. His face lighted up in as great joy as a few moments before it had showed despair. "What can that have been?" asked Elaine, starting to get out of the car. "What caused it?" "I don't know," I returned, taking her arm firmly. "But enough has happened to-day. If it was intended for us, we'd better not stop. Some one might take a shot at us. Come. We have the car. We can get out before any one does anything more. Let's do it. Things are going on about us of which we know nothing. The safest thing is to get away." Elaine looked at the bridge in ruins and shuddered. It was the closest we could have been to death and have escaped. Then she turned to the wheel quickly and the little car fairly jumped ahead. "Oh, if Craig were only here," she murmured. "He would know what to do." As we disappeared over the crest of the next hill, safe, the old farmer and his dog looked hard at us. The silence after the explosion was ominous. He glanced about. No one was pursuing him. That seemed ominous, too. But if they did pursue he was prepared to elude them. They must never recognize the old farmer. As he turned, he deliberately pulled off his beard, then plunged again into the woods and was lost. CHAPTER IX THE SUBMARINE HARBOR It was not long after the almost miraculous escape of Elaine and myself from the blowing up of the bridge on the shore road that Del Mar returned from his mysterious mission which had, apparently, taken him actually down to the bottom of the sea. The panel in the wall of his library opened and in the still dripping submarine suit, holding under his arm the weird helmet, Del Mar entered. No sooner had he begun to remove his wet diving-suit than the man who had signalled with the heliograph that we had found Del Mar's message from "below," whatever that might mean, entered the house and was announced by the valet. "Let him come in immediately," ordered Del Mar, placing his suit in a closet. Then to the man, as he entered, he said, "Well, what's new?" "Quite a bit," returned the man, frowning still over Elaine's accidental discovery of the under-water communication. "The Dodge girl happened to pick up one of the tubes with a message just after you went down. I tried to get her by blowing up the bridge, but it didn't work, somehow." "We'll have to silence her," remarked Del Mar angrily with a sinister frown. "You stay here and wait for orders." A moment later he made his way down to a private dock on his grounds and jumped aboard a trim little speed boat moored there. He started the motor and off the boat feathered in a cloud of spray. It was only a moment by water before he reached the Dodge dock. There he tied his boat and hurried up the dock. . . . . . . . Elaine and I arrived home without any further experiences after our hairbreadth escape from the explosion at the bridge. We were in doubt at first, however, just what to do about the mysterious message which we had picked up in the harbor. "Really, Walter," remarked Elaine, after we had considered the matter for some time, "I think we ought to send that message to the government at Washington." Already she had seated herself at her desk and began to write, while I examined the metal tube and the note again. "There," she said at length, handing me the note she had written. "How does that sound?" I read it while she addressed the envelope. "Very good," I replied, handing it back. She folded it and shoved it into the envelope on which she had written: Chief, Secret Service, Washington, D. C. I was studying the address, wondering whether this was just the thing to do, when Elaine decided the matter by energetically ringing the bell for Jennings. "Post that, Jennings, please," she directed. The butler bowed just as the door-bell rang. He turned to go. "Just a minute," I interrupted. "I think perhaps I'd better mail it myself, after all." He handed me the letter and went out. "Yes, Walter," agreed Elaine, "that would be better. Register it, too." "How do you do?" greeted a suave voice. It was Del Mar. As he passed me to speak to Elaine, apparently by accident, he knocked the letter from my hand. "I beg your pardon," he apologized, quickly stooping and picking it up. Though he managed to read the address, he maintained his composure and handed the letter back to me. I started to go out, when Elaine called to me. "Excuse me just a moment, Mr. Del Mar?" she queried, accompanying me out on the porch. Already a saddle horse had been brought around for me. "Perhaps you'd better put a special delivery stamp on it, too, Walter," she added, walking along with me. "And be very careful." "I will," I promised, as I rode off. Del Mar, alone, seized the opportunity to go over quietly to the telephone. It was the work of only a moment to call up his bungalow where the emissary who had placed the submarine bell was waiting for orders. Quickly Del Mar whispered his instructions which the man took, and hung up the receiver. "I hope you'll pardon me," said Elaine, entering just as Del Mar left the telephone. "Mr. Jameson was going into town and I had a number of little things I wanted him to do. Won't you sit down?" They chatted for a few moments, but Del Mar did not stay very long. He excused himself shortly and Elaine bade him good-bye at the door as he walked off, apparently, down the road I had taken. . . . . . . . Del Mar's emissary hurried from the bungalow and almost ran down the road until he came to a spot where two men were hiding. "Jameson is coming with a letter which the Dodge girl has written to the Secret Service," he cried pointing excitedly up the road. "You've got to get it, see?" I was cantering along nicely down the road by the shore, when suddenly, from behind some rocks and bushes, three men leaped out at me. One of them seized the horse's bridle, while the other two quickly dragged me out of the saddle. It was very unexpected, but I had time enough to draw my gun and fire once. I hit one of the men, too, in the arm, and he staggered back, the blood spurting all over the road. But before I could fire at the others, they knocked the gun from my hand. Frightened, the horse turned and bolted, riderless. Together, they dragged me off the road and into the thicket where I was tied and gagged and laid on the ground while one of them bound up the wounded arm of the man I had hit. It was not long before one of them began searching me. "Aha!" he growled, pulling the letter from my pocket and looking at it with satisfaction. "Here it is." He tore the letter open, throwing the envelope on the ground, and read it. "There, confound you," he muttered. "The government 'll never get that. Come on, men. Bring him this way." He shoved the letter into his pocket and led the way through the underbrush, while the others half-dragged, half-pushed me along. We had not gone very far before one of the three men, who appeared to be the leader, paused. "Take him to the hang-out," he ordered gruffly. "I'll have to report to the Chief." He disappeared down toward the shore of the harbor while the others prodded me along. . . . . . . . Down near the Dodge dock, along the shore, walked a man wearing a broad-brimmed hat and a plain suit of duck. His prim collar and tie comported well with his smoked glasses. Instinctively one would have called him "Professor", though whether naturalist, geologist, or plain "bugologist", one would have had difficulty in determining. He seemed, as a matter-of-fact, to be a naturalist, for he was engrossed in picking up specimens. But he was not so much engrossed as to fail to hear the approach of footsteps down the gravel walk from Dodge Hall to the dock. He looked up in time to see Del Mar coming, and quietly slipped into the shrubbery up on the shore. On the dock, Del Mar stood for some minutes, waiting. Finally, along the shore came another figure. It was the emissary to whom Del Mar had telephoned and who had searched me. The naturalist drew back into his hiding-place, peering out keenly. "Well?" demanded Del Mar. "What luck?" "We've got him," returned the man with brief satisfaction. "Here's the letter she was sending to the Secret Service." Del Mar seized the note which the man handed to him and read it eagerly. "Good," he exclaimed. "That would have put an end to the whole operations about here. Come on. Get into the boat." For some reason best known to himself, the naturalist seemed to have lost all interest in his specimens and to have a sudden curiosity about Del Mar's affairs. As the motor-boat sped off, he came slowly and cautiously out of his hiding-place and gazed fixedly at Del Mar. No sooner had Del Mar's boat got a little distance out into the harbor than the naturalist hurried down the Dodge dock. There was tied Elaine's own fast little runabout. He jumped into it and started the engine, following quickly in Del Mar's wake. "Look," called the emissary to Del Mar, spying the Dodge boat with the naturalist in it, skimming rapidly after them. Del Mar strained his eyes back through his glass at the pursuing boat. But the naturalist, in spite of his smoked glasses, seemed not to have impaired his eyesight by his studies. He caught the glint of the sun on the lens at Del Mar's eye and dropped down into the bottom of his own boat where he was at least safe from scrutiny, if his boat were not. Del Mar lowered his glass. "That's the Dodge boat," he said thoughtfully. "I don't like the looks of that fellow. Give her more speed." . . . . . . . Del Mar had not been gone long before Elaine decided to take a ride herself. She ordered her horse around from the stables while she donned her neat little riding-habit. A few minutes later, as the groom held the horse, she mounted and rode away, choosing the road by which I had gone, expecting to meet me on the return from town. She was galloping along at a good clip when suddenly her horse shied at something. "Whoa, Buster," pacified Elaine. But it was of no use. Buster still reared up. "Why, what is the matter?" she asked. "What do you see?" She looked down at the ground. There was a spot of blood in the dust. Buster was one of those horses to whom the sight of blood is terrifying. Elaine pulled up beside the road. There was a revolver lying in the grass. She dismounted and picked it up. No sooner had she looked at it than she discovered the initials "W. J." carved on the butt. "Walter Jameson!" she exclaimed, realizing suddenly that it was mine. "It's been fired, too!" Her eye fell again on the blood spots. "Blood and--footprints--into the brush!" she gasped in horror, following the trail. "What could have happened to Walter?" With the revolver, Elaine followed where the bushes were trampled down until she came to the place where I had been bound. There she spied some pieces of paper lying on the ground and picked them up. She put them together. They were pieces of the envelope of the letter which we had decided to send to Washington. "Which way did they take him?" she asked, looking all about but discovering no trail. She was plainly at a loss what course to pursue. "What would Craig do?" she asked herself. Finding no answer, she stood thinking a moment, slowly tearing the envelope to pieces. If she were to do anything at all, it must be done quickly. Suddenly an idea seemed to occur to her. She threw the pieces of paper into the air and let them blow away. It was unscientific detection, perhaps, but the wind actually took them and carried them in the direction in which the men had forced me to walk. "That's it!" cried Elaine to herself. "I'll follow that direction." . . . . . . . Meanwhile, the men had hurried me off along a trail that led to the foot of a cliff. Then the trail wound up the cliff. We climbed it until we reached the top. There in the rock was a rude stairway. I drew back. But one man drew a gun and the other preceded me down. Along the steep stone steps cut out in the face of the rock, they forced me. Below, in a rift in the very wall of the cliff, was a cave in which already were two more of Del Mar's men, talking in low tones, in the dim light. As we made our way down the breakneck stairway, the foremost of my captors stepped on a large flat rock. As he did so, it gave way slightly under his foot. A light in the cave flashed up. Under the rock was a secret electric connection which operated a lamp. "Some one coming," muttered the two men, on guard instantly. It was a somewhat precarious footing as we descended and for the moment I was more concerned for my safety from a fall than anything else. Once my foot did slip and a shower of pebbles and small pieces of rock started down the face of the cliff. As we passed down, the man behind me, still keeping me covered, raised the flat stone on the top step. Carefully, he reset the connection of the alarm rock, a series of metal points that bent under the weight of a person and made a contact which signalled down in the cavern the approach of any one who did not know the secret. As he did so, the light in the cavern went out. "It's all right," said one of the men down there, with a look of relief. We now went down the perilous stairway until we came to the cave. "I've got a prisoner--orders of the Chief," growled one of my captors, thrusting me in roughly. They forced me into a corner where they tied me again, hand and foot. Then they began debating in low, sinister tones, what was to be done with me next. Once in a while I could catch a word. Fear made my senses hypersensitive. They were arguing whether they should make away with me now or later! Finally the leader rose. "It's three to one," I heard him mutter. "He dies now." He turned and took a menacing step toward me. "Hands up!" It was a shrill, firm voice that rang out at the mouth of the cave as a figure cut off what little light there was. . . . . . . . Elaine passed along, hunting for the trail. Suddenly a shower of pebbles came falling down from a cliff above her. Some of them hit her and she looked up quickly. There she could see me being led along by my captors. She hid in the brush and watched. During all the operations of the descent of the rock stairway and the resetting of the alarm, she continued to watch, straining her eyes to see what they were doing. As we entered the cave, she stepped out from her concealment and looked sharply up at us, as we disappeared. Then she climbed the path up the cliff until she came to the flight of stone steps leading downward again. Already she had seen the man behind me doing something with the stone that formed the top step. She stooped down and examined the stone. Carefully she raised it and looked underneath before stepping on it. There she could see the electric connection. She set the stone aside and looked again down the dangerous stairway. It made her shudder. "I must get him," she murmured to herself. "Yes, I must. Even now it may be too late." With a supreme effort of determination she got herself together, drew my gun which she had picked up, and started down the cliff, stepping noiselessly. At last Elaine came to the cave. She stood just aside from the door, gun in hand, and listened, aghast. Inside she could hear voices of four men, and they were arguing whether they should kill me or not. It was four against one woman, but she did not falter. They had just decided to make away with me immediately and the leader had turned toward me with the threat still on his lips. It was now or never. Resolutely she took a step forward and into the cave. "Hands up!" she demanded, firmly. The thing was so unexpected in the security of their secret hiding-place protected by the rock alarm that, before they knew it, Elaine had them all lined up against the wall. Keeping them carefully covered, she moved over toward me. She picked up a knife that lay near-by and started to cut the ropes which held me. As she did so, one of the men, with an oath, leaped forward to rush her. But Elaine was not to be caught off her guard. Instantly she fired. The man staggered back, and fell. That cooled the ardor of the other three considerably, especially now as I was free, too. While she held them up still, with their hands in the air, I went through their pockets, taking out their weapons. Then, still keeping them covered, we backed out of the cave. Backward we made our way up the dangerous flight of steps again with guns levelled at the cave entrance, Elaine going up first. Once a head stuck itself out of the cave entrance. I fired instantly and it jerked itself back in again just in time. That was the only trouble we had, apparently. Cautiously and slowly we made our way toward the top of the cliff. . . . . . . . One look backward from his motor-boat was enough for Del Mar. He must evade that inquisitive naturalist. He turned to his man. "Get out that apparatus," he ordered. The man opened a locker and brought out the curious submarine rescue helmet and suit. Del Mar took them up and began to put the suit on, stooping down in the shelter of the boat so that his actions could not be seen by the naturalist in the pursuing boat. The naturalist was all this time peering ahead keenly at Del Mar's boat, trying to make it out. He bent over and adjusted the engine to get up more speed and the boat shot ahead faster. By this time, Del Mar had put on the submarine apparatus, all except the helmet, and was crouching low in the boat. Hastily, he rolled a piece of canvas into the semblance of a body, put his coat and hat on it and set it on the seat which he had occupied before. Just then Del Mar's boat ran around the promontory where Wu Fang had met the submarine that had brought Del Mar into the country and landed him so strangely. The boat slowed down under shelter of the rocks and Del Mar added a pair of heavy lead-soled shoes to his outfit in order to weight himself down. Finally he put on the helmet, let himself over the side of the boat, and disappeared into the water. His aide started the motor and the boat shot ahead again, with the dummy still occupying Del Mar's seat. As the boat swung out and made a wide sweeping curve away from the point at which Del Mar had gone overboard, the naturalist in the Dodge boat came around the promontory and saw it, changing his course accordingly, and gaining somewhat. . . . . . . . Del Mar sank, upright and rapidly, down in the shallow water to the bottom. Once having his feet on something approaching firm ground, he gazed about through the window-like eye of the helmet until he got his bearings. Then he began to walk heavily along the bottom of the harbor, over sand and rocks. It was a strange walk that he took, half stumbling, slowly and cumbersomely groping his way like a queer under-water animal. If any one could have seen him, he would have noted that Del Mar was going toward the base of a huge rocky cliff that jutted far out into the harbor, where the water was deep, a dangerous point, avoided by craft of all kinds. Far over his head the waves beat on the rocks angrily. But down there, concealed beneath the surface of the harbor, was a sort of huge arch of stone, through which a comparatively rapid current ran as the tide ebbed and flowed. Del Mar let himself be carried along with the current which was now running in and thus with comparative ease made his way, still groping, through the arch. Once under it and a few feet beyond, he deliberately kicked off the leaden-soled shoes and, thus lightened, rose rapidly to the surface of the water. As he bobbed up, a strange sight met his eyes--not strange however, to Del Mar. Above, the rocks formed a huge dome over the water which the tides forced in and out through the secret entrance through which he came. No other entrance, apparently, except that from the waters of the harbor led to this peculiar den. Lying quietly moored to the rocky piers lay three submarine boats. Further back, on a ledge of rocks, blasted out, stood a little building, a sort of office or headquarters. Near-by was a shed where were kept gas and oil, supplies and ammunition, in fact everything that a submarine might need. This was the reason for Del Mar's presence in the neighborhood. It was the secret submarine harbor of the foreign agents who were operating in America! Already a sentry, pacing up and down, had seen the bubbles in the water that indicated that some one had come through the archway and was down "below," as Del Mar and his men called it. Gazing down the sentry saw the queer helmeted figure float up from the bottom of the pool. He reached out and helped the figure clamber up out of the water to the ledge on which he stood. Del Mar saluted, and the sentry returned the secret salute, helping him remove the dripping helmet and suit. A moment later, in the queer little submarine office, Del Mar had evidently planned to take up the nefarious secret work on which he was engaged. Several men of a naval and military bearing were seated about a table, already, studying maps and plans and documents of all descriptions. They did not seem to belong to any nation in particular. In fact their uniforms, if such they might be called, were of a character to disguise their nationality. But that they were hostile to the country under which they literally had their hidden retreat, of that there could be no doubt. How high Del Mar stood in their counsels could have been seen at a glance from the instant deference exhibited at the mere mention of his name by the sentry who entered with the submarine suit while Del Mar got himself together after his remarkable trip. The men at the council table rose and saluted as Del Mar himself entered. He returned the salute and quietly made his way to the head of the table where he took a seat, naturally. "This is the area in which we must work first of all," he began, drawing toward him a book and opening it. "And we must strike quickly, for if they heed the advice in this book, it may be too late for us to take advantage of their foolish unpreparedness." It was a book entitled "Defenseless America", written by a great American inventor, Hudson Maxim. Del Mar turned the pages until he came to and pointed out a map. The others gathered about him, leaning forward eagerly as he talked to them. There, on the map, with a radius of some one hundred and seventy miles, was drawn a big segment of a circle, with Peekskill, New York, as a centre. "That is the heart of America," said Del Mar, earnestly. "It embraces New York, Boston, Philadelphia. But that is not the point. Here are the great majority of the gun and armor factories, the powder and cartridge works, together with the principal coal fields of Pennsylvania." He brought his fist down decisively on the table. "If we hold this section," he declared, "we practically hold America!" Eagerly the other emissaries listened as Del Mar laid before them the detailed facts which he was collecting, the greater mission than the mere capture of Kennedy's wireless torpedo which had brought him into the country. Detail after detail of their plans they discussed as they worked out the gigantic scheme. It was a war council of a secret advance guard of the enemies of America! . . . . . . . Meanwhile, Del Mar's man in his boat, cutting a wide circle and avoiding the Dodge boat carrying the naturalist, made his way across the harbor until he came to the shore. There he landed and proceeded up the beach to the foot of a rocky cliff, where he turned and followed a trail up it to the top. It was the same path already travelled by my captors with me and later followed by Elaine. As he came stealthily out from under cover, Del Mar's man gazed down the stairway. He drew back at what he saw. Slowly he pulled a gun from his pocket, watching down the steps with tense interest. There he could see Elaine and myself wearily climbing toward the top, our backs toward him, as we covered the men in the cave. So surprised was he at what he saw that he forgot that his boat below had been followed by the mysterious naturalist, who, the moment Del Mar's man had landed, put on the last burst of speed and ran the Dodge boat close to the spot where the aide had left Del Mar's. A glance into the boat sufficed to tell the naturalist that the figure in it was only a dummy. He did not pause, but followed the trail up the hill, until he was close after the emissary ahead, going more slowly. Only a few feet further along the cliff, the naturalist paused, too, keeping well under cover, for the man was now just ahead of him. He looked fixedly at him and saw him gaze down the cliff. Then he saw him slowly draw a gun. Who could be below? Quickly the naturalist's mind seemed to work. He crouched down, as if ready to spring. The emissary slowly raised his revolver and took careful aim at the backs of Elaine and myself, as we came up the steps. But before he could pull the trigger, the naturalist, more like one of the wild animals which he studied than like a human being, sprang from his concealment in the bushes and pounced on the man from behind, seizing him firmly. Over and over they rolled, struggling almost to the brink of the precipice. Elaine and I had got almost to the top of the flight of steps, when suddenly we heard a shout above us and sounds of a terrific struggle. We turned, to see two men, neither of whom we knew, fighting. One seemed to be a professor of natural history from his dress and general appearance. The other had a sinister nondescript look. Nearer and nearer the edge of the cliff they rolled. We crouched closer to the rocky wall, gazing up at the death grapple of the two. Who they were we did not know but that one was fighting for and the other against us we could readily see. The more vicious of the two seemed to be forcing the naturalist slowly back, when, with a superhuman effort, the naturalist braced himself. His foot was actually on a small ledge of rock directly at the edge of the cliff. He swung around quickly and struck the other man. The vicious looking man pitched headlong over the cliff. We shrank back closer to the rock as the man hurtled through the air only a few feet from us. Down below, we could hear him land with a sickening thud. Far over the edge Elaine leaned in a sort of fascination at the awful sight. For a moment, I thought the very imp of the perverse had got possession of her and that she herself would fall over. She brushed her hand unsteadily over her eyes and staggered. I caught her just in time. It was only an instant before the brave girl recovered control of herself. Then, together, we started again to climb up. As we did so the naturalist looked down and caught sight of us approaching. Hastily he hid in the bushes. We reached the top of the stairway and gazed about for the victor in the contest. To our surprise he was gone. "Come," I urged. "We had better get away, quickly." As Elaine and I disappeared, the naturalist slowly emerged again from the bushes and looked after us. Then he gave a hasty glance over the edge of the cliff at the man, twisted and motionless, far below. If we had looked back we might have seen the naturalist shake his head in a manner strangely reminiscent as he turned and gazed again after us. CHAPTER X THE CONSPIRATORS "You remember Lieutenant Woodward, the inventor of trodite?" I asked Elaine one day after I had been out for a ride through the country. "Very well indeed," she nodded with a look of wistfulness as the mention of his name recalled Kennedy. "Why?" "He's stationed at Fort Dale, not very far from here, at the entrance of the Sound," I answered. "Then let's have him over at my garden party to-night," she exclaimed, sitting down and writing. DEAR LIEUTENANT, I have just learned that you are stationed at Fort Dale and would like to have you meet some of my friends at a little garden party I am holding to-night. Sincerely, ELAINE DODGE. Thus it was that a few hours afterward, in the officers' quarters at the Fort, an orderly entered with the mail and handed a letter to Lieutenant Woodward. He opened it and read the invitation with pleasure. He had scarcely finished reading and was hastening to write a reply when the orderly entered again and saluted. "A Professor Arnold to see you, Lieutenant," he announced. "Professor Arnold?" repeated Woodward. "I don't know any Professor Arnold. Well, show him in, anyhow." The orderly ushered in a well-dressed man with a dark, heavy beard and large horn spectacles. Woodward eyed him curiously and a bit suspiciously, as the stranger seated himself and made a few remarks. The moment the orderly left the room, however, the professor lowered his voice to a whisper. Woodward listened in amazement, looked at him more closely, then laughed and shook hands cordially. The professor leaned over again. Whatever it was that he said, it made a great impression on the Lieutenant. "You know this fellow Del Mar?" asked Professor Arnold finally. "No," replied Woodward. "Well, he's hanging around Miss Dodge all the time," went on Arnold. "There's something queer about his presence here at this time." "I've an invitation to a garden party at her house to-night," remarked Woodward. "Accept," urged the professor, "and tell her you are bringing a friend." Woodward resumed writing and when he had finished handed the note to the stranger, who read: DEAR MISS DODGE, I shall be charmed to be with you to-night and with your permission will bring my friend, Professor Arnold. Truly yours, EDWARD WOODWARD. "Good," nodded the professor, handing the note back. Woodward summoned an orderly. "See that that is delivered at Dodge Hall to Miss Dodge herself as soon as possible," he directed, as the orderly took the note and saluted. Elaine, Aunt Josephine and I were in the garden when Lieut. Woodward's orderly rode up and delivered the letter. Elaine opened it and read. "That's all right," she thanked the orderly. "Oh, Walter, he's coming to the garden party, and is going to bring a friend of his, a Professor Arnold." We chatted a few moments about the party. "Oh," exclaimed Elaine suddenly, "I have an idea." "What is it?" we asked, smiling at her enthusiasm. "We'll have a fortune teller," she cried. "Aunt Josephine, you shall play the part." "All right, if you really want me," consented Aunt Josephine smiling indulgently as we urged her. . . . . . . . Down in the submarine harbor that afternoon, Del Mar and his men were seated about the conference table. "I've traced out the course and the landing points of the great Atlantic cable," he said. "We must cut it." Del Mar turned to one of the men. "Take these plans to the captain of the steamer and tell him to get ready," he went on. "Find out and send me word when the cutting can be done best." The man saluted and went out. Leaving the submarine harbor in the usual manner, he made his way to a dock on the shore around the promontory and near the village. Tied to it was a small tramp steamer. The man walked down the dock and climbed aboard the boat. There several rough looking sailors were lolling and standing about. The emissary selected the captain, a more than ordinarily tough looking individual. "Mr. Del Mar sends you the location of the Atlantic cable and the place where he thinks it best to pick it up and cut it," he said. The captain nodded. "I understand," he replied. "I'll send him word later when it can be done best." A few minutes after dispatching his messenger, Del Mar left the submarine harbor himself and entered his bungalow by way of the secret entrance. There he went immediately to his desk and picked up the mail that had accumulated in his absence. One letter he read: DEAR MR. DEL MAR, We shall be pleased to see you at a little garden party we are holding to-night. Sincerely, ELAINE DODGE. As he finished reading, he pushed the letter carelessly aside as though he had no time for such frivolity. Then an idea seemed to occur to him. He picked it up again and read it over. "I'll go," he said to himself, simply. . . . . . . . That night Dodge Hall was a blaze of lights and life, overflowing to the wide verandas and the garden. Guests in evening clothes were arriving from all parts of the summer colony and were being received by Elaine. Already some of them were dancing on the veranda. Among the late arrivals were Woodward and his friend, Professor Arnold. "I'm so glad to know that you are stationed at Fort Dale," greeted Elaine. "I hope it will be for all summer." "I can't say how long it will be, but I shall make every effort to make it all summer," he replied gallantly. "Let me present my friend, Professor Arnold." The professor bowed low and unprofessionally over Elaine's hand and a moment later followed Woodward out into the next room as the other guests arrived to be greeted by Elaine. For a moment, however, she looked after him curiously. Once she started to follow as though to speak to him. Just then, however, Del Mar entered. "Good evening," he interrupted, suavely. He stood for a moment with Elaine and talked. One doorway in the house was draped and a tent had been erected in the room. Over the door was a sign which read: "The past and the future are an open book to Ancient Anna." There Aunt Josephine held forth in a most effective disguise as a fortune teller. Aunt Josephine had always had a curious desire to play the old hag in amateur dramatics and now she had gratified her desire to the utmost. Probably none of the guests knew that Ancient Anna was in reality Elaine's guardian. Elaine being otherwise occupied, I had selected one of the prettiest of the girls and we were strolling through the house, seeking a quiet spot for a chat. "Why don't you have your fortune told by Ancient Anna?" laughed my companion as we approached the tent. "Do you tell a good fortune reasonably?" I joked, entering. "Only the true fortunes, young man," returned Ancient Anna severely, starting in to read my palm. "You are very much in love," she went on, "but the lady is not in this tent." Very much embarrassed, I pulled my hand away. "How shocking!" mocked my companion, making believe to be very much annoyed. "I don't think I'll have my fortune told," she decided as we left the room. We sauntered along to the veranda where another friend claimed my companion for a dance which she had promised. As I strolled on alone, Del Mar and Elaine were already finishing a dance. He left her a moment later and I hurried over, glad of the opportunity to see her at last. Del Mar made his way alone among the guests and passed Aunt Josephine disguised as the old hag seated before her tent. Just then a waiter came through with a tray of ices. As he passed, Del Mar stopped him, reached out and took an ice. Under the ice, as he had known, was a note. He took the note surreptitiously, turned and presented the ice to Ancient Anna with a bow. "Thank you, kind sir," she curtsied, taking it. Del Mar stepped aside and glanced at the little slip of paper. Then he crumpled it up and threw it aside, walking away. No sooner had he gone than Aunt Josephine reached out and picked up the paper. She straightened it and looked at it. There was nothing on the paper but a crude drawing of a sunrise on the ocean. "What's that?" asked Aunt Josephine, in surprise. Just then Elaine and Lieutenant Woodward came in and stopped before the tent. Aunt Josephine motioned to Elaine to come in and Elaine followed. Lieutenant Woodward started after her. "No, no, young man," laughed Ancient Anna, shaking her forefinger at him, "I don't want you. It's the pretty young lady I want." Woodward stood outside, though he did not know quite what it was all about. While he was standing there, Professor Arnold came up. He had not exactly made a hit with the guests. At least, he seemed to make little effort to do so. He and Woodward walked away, talking earnestly. In the tent Aunt Josephine handed Elaine the piece of paper she had picked up. "What does it mean?" asked Elaine, studying the curious drawing in surprise. "I'm sure I don't know," confessed Aunt Josephine. "Nor I." Meanwhile Lieutenant Woodward and his friend had moved to a corner of the veranda and stood looking intently into the moonlight. There was Del Mar deep in conversation with a man who had slipped out, at a quiet signal, from his hiding-place in the shrubbery. "That fellow is up to something, mark my words," muttered Arnold under his breath. "I'd like to make an arrest, but I've got to have some proof." They continued watching Del Mar but, so far at least, he did nothing that would have furnished them any evidence of anything. So the party went on, most merrily until, long after the guests had left, Elaine sat in her dressing-gown up in her room, about to retire. Her maid had left her and she picked up the slip of paper from her dresser, looking at it thoughtfully. "What can a crude drawing of a sunrise on the sea mean?" she asked herself. For a long time she studied the paper, thinking it over. At last an idea came to her. "I'll bet I have it," she exclaimed to herself. "Something is going to happen on the water at sunrise." She took a pretty little alarm clock from the table, set it, and placed it near her bed. Returning from the party to his library, Del Mar entered. Except for the moonlight streaming in through the windows the room was dark. He turned on the lights and crossed to the panel in the wall. As he touched a button the panel opened. Del Mar switched off the lights and went through the panel, closing it. Outside, at the other end of the passageway, was one of his men, waiting in the shadows as Del Mar came up. For a moment they talked. "I'll be there, at sunrise," agreed Del Mar, as the man left and he reentered the secret passage. While he was conferring, at the library window appeared a face. It was Professor Arnold's. Cautiously he opened the window and listened. Then he entered. First he went over to the door and set a chair under the knob. Next he drew an electric pocket bull's-eye and flashed it about the room. He glanced about and finally went over to Del Mar's desk where he examined a batch of letters, his back to the secret panel. Arnold was running rapidly through the papers on the desk, as he flashed his electric bull's-eye on them, when the panel in the wall opened slowly and Del Mar stepped into the room noiselessly. To his surprise he saw a round spot of light from an electric flashlight focussed on his desk. Some one was there! He drew a gun. Arnold started suddenly. He heard the cocking of a revolver. But he did not look around. He merely thought an instant, quicker than lightning, then pulled out a spool of black thread with one hand, while with the other he switched off the light, and dived down on his stomach on the floor in the shadow. "Who's that?" demanded Del Mar. "Confound it! I should have fired at sight." The room was so dark now that it was impossible to see Arnold. Del Mar gazed intently. Suddenly Arnold's electric torch glowed forth in a spot across the room. Del Mar blazed at it, firing every chamber of his revolver, then switched on the lights. No one was in the room. But the door was open. Del Mar gazed about, vexed, then ran to the open door. For a second or two he peered out in rage, finally turning back into the empty room. On the mantlepiece lay the torch of the intruder. It was one in which the connection is made by a ring falling on a piece of metal. The ring had been left up by Arnold. Connection had been made as he was leaving the room by pulling the thread which he had fastened to the ring. Del Mar followed the thread as it led around the room to the doorway. "Curse him!" swore Del Mar, smashing down the innocent torch on the floor in fury, as he rushed to the desk and saw his papers all disturbed. Outside, Arnold had made good his escape. He paused in the moonlight and listened. No one was pursuing. He drew out two or three of the letters which he had taken from Del Mar's desk, and hastily ran through them. "Not a thing in them," he exclaimed, tearing them up in disgust and hurrying away. At the first break of dawn the little alarm dock awakened Elaine. She started up and rubbed her eyes at the suddenness of the awakening, then quickly reached out and stopped the bell so that it would not disturb others in the house. She jumped out of bed hurriedly and dressed. Armed with a spy glass, Elaine let herself out of the house quietly. Directly to the shore she went, walking along the beach. Suddenly she paused. There were three men. Before she could level her glass at them, however, they disappeared. "That's strange," she said to herself, looking through the glass. "There's a steamer at the dock that seems to be getting ready for something. I wonder what it can be doing so early." She moved along in the direction of the dock. At the dock the disreputable steamer to which Del Mar had dispatched his emissary was still tied, the sailors now working under the gruff orders of the rough captain. About a capstan were wound the turns of a long wire rope at the end of which was a three-pronged drag-hook. "You see," the captain was explaining, "we'll lower this hook and drag it along the bottom. When it catches anything we'll just pull it up. I have the location of the cable. It ought to be easy to grapple." Already, on the shore, at an old deserted shack of a fisherman, two of Del Mar's men had been waiting since before sun-up, having come in a dirty, dingy fishing smack anchored offshore. "Is everything ready?" asked Del Mar, coming up. "Everything, sir," returned the two, following him along the shore. "Who's that?" cautioned one of the men, looking ahead. They hid hastily, for there was Elaine. She had seen the three and was about to level her glass in their direction as they hid. Finally she turned and discovered the steamer. As she moved toward it, Del Mar and the others came out from behind a rock and stole after her. Elaine wandered on until she came to the dock. No one paid any attention to her, apparently, and she made her way along the dock and even aboard the boat without being observed. No sooner had she got on the boat, however, than Del Mar and his men appeared on the dock and also boarded the steamer. The captain was still explaining to the men just how the drag-hook worked when Elaine came up quietly on the deck. She stood spellbound as she heard him outline the details of the plot. Scarcely knowing what she did, she crouched back of a deckhouse and listened. Behind her, Del Mar and his men came along, cat-like. A glance was sufficient to tell them that she had overheard what the captain was saying. "Confound that girl!" ground out Del Mar. "Will she always cross my path? We'll get her this time!" The men scattered as he directed them. Sneaking up quietly, they made a sudden rush and seized her. As she struggled and screamed, they dragged her off, thrusting her into the captain's cabin and locking the door. "Cast off!" ordered Del Mar. A few moments later, out in the harbor, Del Mar was busy directing the dragging for the Atlantic cable at a spot where it was known to run. They let the drag-hook down over the side and pulled it along slowly on the bottom. In the cabin, Elaine beat on the door and shouted in vain for help. I had decided to do some early morning fishing the day after the party, and knowing that Elaine and the others were usually late risers, I said nothing about it, determined to try my luck alone. So it happened that only a few minutes after Elaine let herself out quietly, I did the same, carrying my fishing-tackle. I made my way toward the shore, undecided whether to fish from a dock or boat. Finally I determined to do some casting from the shore. I had cast once or twice before I was aware that I was not alone in the immediate neighborhood. Some distance away I saw a little steamer at a wharf. A couple of men ran along the deck, apparently cautioning the captain against something. Then I saw them run to one side and drag out a girl, screaming and struggling as they hurried her below. I could scarcely believe my eyes. It was Elaine! Only a second I looked. They were certainly too many for me. I dropped my rod and line and ran toward the dock, however. As I came down it, I saw that I was too late. The little steamer had cast off and was now some distance from the dock. I looked about for a motor-boat in desperation--anything to follow them in. But there was nothing, absolutely nothing, not even a rowboat. I ran back along the dock as I had come and struck out down the shore. . . . . . . . Out at the parade grounds at Fort Dale, in spite of the early hour, there was some activity, for the army is composed of early risers. Lieutenant Woodward and Professor Arnold left the house in which the Lieutenant was quartered, where he had invited Arnold to spend the night. Already an orderly had brought around two horses. They mounted for an early morning ride through the country. Off they clattered, naturally bending their course toward the shore. They came soon to a point in the road where it emerged from the hills and gave them a panoramic view of the harbor and sound. "Wait a minute," called the professor. Woodward reined up and they gazed off over the water. "What's that--an oyster boat?" asked Woodward, looking in the direction Arnold indicated. "I don't think so, so early," replied Arnold, pulling out his pocket glass and looking carefully. Through it he could see that something like a hook was being cast over the steamer's side and drawn back again. "They're dragging for something," he remarked as they brought up an object dark and covered with seagrowth, then threw it overboard as though it was not what they wanted. "By George--the Atlantic cable lands here--they're going to cut it!" Woodward took the glasses himself and looked in in surprise. "That's right," he cried, his surprise changed to alarm in an instant. "Here, take the glass again and watch. I must get back to the Fort." He swung his horse about and galloped off, leaving Arnold sitting in the saddle gazing at the strange boat through his glass. By the time Woodward reached the parade ground again, a field-gun and its company were at drill. He dashed furiously across the field. "What's the trouble?" demanded the officer in charge of the gun. Woodward blurted out what he had just seen. "We must stop it--at any cost," he added, breathlessly. The officer turned to the company. A moment later the order to follow Woodward rang out, the horses were wheeled about, and off the party galloped. On they went, along the road which Woodward and Arnold had already traversed. Arnold was still gazing, impatiently now, through the glass. He could see the fore-deck of the ship where Del Mar, muffled up, and his men had succeeded in dragging the cable to the proper position on the deck. They laid it down and Del Mar was directing the preparations for cutting it. Arnold lowered his glass and looked about helplessly. Just then Lieutenant Woodward dashed up with the officer and company and the field-gun. They wheeled it about and began pointing it and finding the range. Would they never get it? Arnold was almost beside himself. One of Del Mar's men seized an axe and was about to deliver the fatal blow. He swung it and for a moment held it poised over his head. Suddenly a low, deep rumble of a reverberation echoed and reechoed from the hills over the water. The field-gun had bellowed defiance. A solid shot crashed through the cabin, smashing the door. Astounded, the men jumped back. As they did so, in their fear, the cable, released, slipped back over the rail in a great splash of safety into the water and sank. "The deuce take you--you fools," swore Del Mar, springing forward in rage, and looking furiously toward the shore. Two of the men had been hit by splinters. It was impossible to drag again. Besides, again the gun crew loaded and fired. The first shot had dismantled the doorway of the cabin. Elaine crouched fearfully in the furthest corner, not knowing what to expect next. Suddenly another shot tore through just beside the door, smashing the woodwork terrifically. She shrank back further, in fright. Anything was better than this hidden terror. Nerved up, she ran through the broken door. Arnold was gazing through his glass at the effect of the shots. He could now see Del Mar and the others leaping into a swift little motor-boat alongside the steamer which they had been using to help them in dragging for the cable. Just then he saw Elaine run, screaming, out from the cabin and leap overboard. "Stop!" shouted Arnold in a fever of excitement, lowering his glass. "There's a girl--by Jove--it's Miss Dodge!" "Impossible!" exclaimed Woodward. "I tell you, it is," reiterated Arnold, thrusting the glass into the Lieutenant's hand. The motor-boat had started when Del Mar saw Elaine in the water. "Look," he growled, pointing, "There's the Dodge girl." Elaine was swimming frantically away from the boat. "Get her," he ordered, shielding his face so that she could not see it. They turned the boat and headed toward her. She struck out harder than ever for the shore. On came the motor-boat. Arnold and Woodward looked at each other in despair. What could they do? . . . . . . . Somehow, by a sort of instinct, I suppose, I made my way as quickly as I could along the shore toward Fort Dale, thinking perhaps of Lieutenant Woodward. As I came upon the part of the grounds of the Fort that sloped down to the beach, I saw a group of young officers standing about a peculiar affair on the shore in the shallow water--half bird, half boat. As I came closer, I recognized it as a Thomas hydroaeroplane. It suggested an idea and I hurried, shouting. One of the men, seated in it, was evidently explaining its working to the others. "Wait," he said, as he saw me running down the shore, waving and shouting at them. "Let's see what this fellow wants." It was, as I soon learned, the famous Captain Burnside, of the United States Aerial Corps. Breathless, I told him what I had seen and that we were all friends of Woodward's. Burnside thought a moment, and quickly made up his mind. "Come--quick--jump up here with me," he called. Then to the other men, "I'll be back soon. Wait here. Let her go!" I had jumped up and they spun the propeller. The hydroaeroplane feathered along the water, throwing a cloud of white spray, then slowly rose in the air. The sensation of flying was delightful, as the fresh morning wind cut our faces. We seemed to be hardly moving. It was the earth or rather the water that rushed past under us. But I forgot all about my sensations in my anxiety for Elaine. As we rose we could see over the curve in the shore. "Look!" I exclaimed, straining my eyes. "She's overboard. There's a motor-boat after her. Faster--over that way!" "Yes, yes," shouted Burnside above the roar of the engine which almost made conversation impossible. He shifted the planes a bit and crowded on more speed. The men in the boat saw us. One figure, tall, muffled, had a familiar look, but I could not place it and in the excitement of the chase had no chance to try. But I could see that he saw us and was angry. Apparently the man gave orders to turn, for the boat swung around just as we swooped down and ran along the water. Elaine was exhausted. Would we be in time? We planed along the water, while the motor-boat sped off with its baffled passengers. Finally we stopped, in a cloud of spray. Together, Burnside and I reached down and caught Elaine, not a moment too soon, dragging her into the boat of the hydroaeroplane. If we had not had all we could do, we might have heard a shout of encouragement and relief from the hill where Woodward and Arnold and the rest were watching anxiously. I threw my coat about her, as the brave girl heroically clung to us, half conscious. "Oh--Walter," she murmured, "you were just in time." "I wish I could have been sooner," I apologized. "They--they didn't cut the cable--did they?" she asked, as we rose from the water again, bearing her now to safety. "I did my best." CHAPTER XI THE WIRELESS DETECTIVE Del Mar made his way cautiously along the bank of a little river at the mouth of which he left the boat after escaping from the little steamer. Quite evidently he was worried by the failure to cut the great Atlantic cable and he was eager to see whether any leak had occurred in the organization which, as secret foreign agent, he had so carefully built up in America. As he skirted the shore of the river, he came to a falls. Here he moved even more cautiously than before, looking about to make certain that no one had followed him. It was a beautiful sheet of water that tumbled with a roar over the ledge of rock, then raced away swiftly to the sea in a cloud of spray. Assured that he was alone, he approached a crevice in the rocks, near the falls. With another hasty look about, he reached in and pulled a lever. Instantly a most marvellous change took place, incredible almost beyond belief. The volume of water that came over the falls actually and rapidly decreased until it almost stopped, dripping slowly in a thin veil. There was the entrance of a cave--literally hidden behind the falls! Del Mar walked in. Inside was the entrance to another, inner cave, higher up in the sheer stone of the wall that the waters had eroded. From the floor to this entrance led a ladder. Del Mar climbed it, then stopped just inside the entrance to the inner cave. For a moment he paused. Then he pressed another lever. Almost immediately the thin trickle of water grew until at last the roaring falls completely covered the cave entrance. It was a clever concealment, contrived by damming the river above and arranging a new outlet controlled by flood-gates. There Del Mar stood, in the inner cave. A man sat at a table, a curious gear fastened over his head and covering his ears. Before him was a huge apparatus from which flared a big bluish-green spark, snapping and crackling above the thunder of the waves. From the apparatus ran wires apparently up through cables that penetrated the rocky roof of the cavern and the river above. It was Del Mar's secret wireless station, close to the hidden submarine harbor which had been established beneath the innocent rocks of the promontory up the coast. Far overhead, on the cliff over the falls, were the antennae of the wireless. "How is she working?" asked Del Mar. "Pretty well," answered the man. "No interference?" queried Del Mar, adjusting the apparatus. The man shook his head in the negative. "We must get a quenched spark apparatus," went on Del Mar, pleased that nothing was wrong here. "This rotary gap affair is out of date. By the way, I want you to be ready to send a message, to be relayed across to our people. I've got to consult the board below in the harbor, first, however. I'll send a messenger to you." "Very well, sir," returned the man, saluting as Del Mar went out. Out at Fort Dale, Lieutenant Woodward was still entertaining his new friend, Professor Arnold, and had introduced him to Colonel Swift, the commanding officer at the Fort. They were discussing the strange events of the early morning, when an orderly entered, saluted Colonel Swift and handed him a telegram. The Colonel tore it open and read it, his face growing grave. Then he handed it to Woodward, who read: WASHINGTON, D. C. Radio station using illegal wave length in your vicinity. Investigate and report. BRANDON, Radio Bureau. Professor Arnold shook his head slowly, as he handed the telegram back. "There's a wireless apparatus of my own on my yacht," he remarked slowly. "I have an instrument there which I think can help you greatly. Let's see what we can do." "All right," nodded Colonel Swift to Woodward. "Try." The two went out and a few minutes later, on the shore, jumped into Arnold's fast little motor-boat and sped out across the water until they swung around alongside the trim yacht which Arnold was using. It was a compact and comfortable little craft with lines that indicated both gracefulness and speed. On one of the masts, as they approached, Woodward noticed the wireless aerial. They climbed up the ladder over the side and made their way directly to the wireless room, where Arnold sat down and at once began to adjust the apparatus. Woodward seemed keenly interested in inspecting the plant which was of a curious type and not exactly like any that he had seen before. "Wireless apparatus," explained Arnold, still at work, "as you know, is divided into three parts, the source of power, the making and sending of wireless waves, including the key, spark, condenser and tuning coil, and the receiving apparatus--head telephones, antennae, ground and detector. This is a very compact system with facilities for a quick change from one wave length to another. It has a spark gap, quenched type, break system relay--operator can hear any interference while transmitting--transformation by a single throw of a six-point switch which tunes the oscillating and open circuits to resonance." Woodward watched him keenly, following his explanation carefully, as Arnold concluded. "You might call it a radio detective," he added. Even the startling experience of the morning when she was carried off and finally jumped from the little tramp steamer that had attempted to cut the cable did not dampen Elaine's ardor. She missed the guiding hand of Kennedy, yet felt impelled to follow up and investigate the strange things that had been happening in the neighborhood of her summer home since his disappearance. I succeeded in getting her safely home after Burnside and I rescued her in the hydroaeroplane, but no sooner had she changed her clothes for dry ones than she disappeared herself. At least I could not find her, though, later, I found that she had stolen away to town and there had purchased a complete outfit of men's clothes from a second hand dealer. Cautiously, with the large bundle under her arm, she returned to Dodge Hall and almost sneaked into her own home and up-stairs to her room. She locked the door and hastily unwrapped the bundle taking out a tattered suit and the other things, holding them up and laughing gleefully as she took off her own pretty clothes and donned these hideous garments. Quickly she completed her change of costume and outward character. As she surveyed herself in the dainty mirror of her dressing-table she laughed again at the incongruity of her pretty boudoir and the rough men's clothes she was wearing. Deftly she arranged her hair so that her hat would cover it. She picked a black mustache from the table and stuck it on her soft upper lip. It tickled and she made a wry face over it. Then she hunted up a cigarette from the bundle which she had brought in, lighted it and stuck it in the corner of her mouth, letting it droop jauntily. It made her cough tremendously and she threw it away. Finally she went to the door and down-stairs. No one was about. She opened the door and gazed around. All was quiet. It was a new role for her, but, with a bold front, she went out and passed down to the gate of the grounds, pulling her hat down over her eyes and assuming a tough swagger. Only a few minutes before, down in the submarine harbor, the officers of the board of foreign agents had been grouped about Del Mar, who had entered and taken his place at their head, very angry over the failure to cut the cable. As they concluded their hasty conference, he wrote a message on a slip of paper. "Take this to our wireless station," he ordered, handing it to one of the men. The man took it, rose, and went to a wardrobe from which he extracted one of the submarine suits. With the message in his hand, he went out of the room, buckling on the suit. A few minutes later the messenger in the submarine suit bobbed up out of the water, near the promontory, and climbed slowly over the rocks toward a crevice, where he began to take off the diving outfit. Having finished, he hid the suit among the rocks and then went along to the little river, carefully skirting its banks into the ravine in which were the falls and the wireless cave. In her disguise, Elaine had made her way by a sort of instinct along the shore to the rocky promontory where we had discovered the message in the tin tube in the water. Something, she knew not what, was going on about there, and she reasoned that it was not all over yet. She was right. As she looked about keenly she did see something, and she hid among the rocks. It was a man, all dripping, in an outlandish helmet and suit. She saw him slink into a crevice and take off the suit, then, as he moved toward the river ravine, she stole up after him. Suddenly she stopped stark still, surprised, and stared. The man had actually gone up to the very waterfall. He had pressed what looked like a lever and the water over the falls seemed to stop. Then he walked directly through into a cave. In the greatest wonder, Elaine crept along toward the falls. Inside the cave Del Mar's emissary started to climb a ladder to an inner cave. As he reached the top, he glanced out and saw Elaine by the entrance. With an oath he jumped into the inner entrance. His hand reached eagerly for a lever in the rocks and as he found and held it, he peered out carefully. Elaine cautiously came from behind a rock where she had hidden herself and seeing no one apparently watching, now, advanced until she stood directly under the trickle of water which had once been the falls. She gazed into the cave, curiously uncertain whether she dared to go in alone or not. The emissary jerked fiercely at the lever as he saw Elaine. Above the falls a dam had been built and by a system of levers the gates could be operated so that the water could be thrown over the falls or diverted away, at will. As the man pressed the lever, the flood gates worked quickly. Elaine stood gazing eagerly into the blackness of the cave. Just then a great volume of water from above crashed down on her, with almost crushing weight. How she lived through it she never knew. But, fortunately, she had not gone quite far enough to get the full force of the water. Still, the terrific flood easily overcame her. She was swept, screaming, down the stream. . . . . . . . Rather alarmed at the strange disappearance of Elaine after I brought her home, I had started out along the road to the shore to look for her, thinking that she might perhaps have returned there. As I walked along a young tough--at least at the time I thought it was a young tough, so good was the disguise she had assumed and so well did she carry it off--slouched past me. What such a character could be doing in the neighborhood I could not see. But he was so noticeably tough that I turned and looked. He kept his eyes averted as if afraid of being recognized. "Great Caesar," I muttered to myself, "that's a roughneck. This place is sure getting to be a hang-out for gunmen." I shrugged my shoulders and continued my walk. It was no business of mine. Finding no trace of Elaine, I returned to the house. Aunt Josephine was in the library, alone. "Where's Elaine?" I asked anxiously. "I don't know," she replied. "I don't think she's at home." "Well, I can't find her anywhere," I frowned wandering out at a loss what to do, and thrusting my hands deep in my pockets as an aid to thought. Somehow, I felt, I didn't seem to get on well as a detective without Kennedy. Yet, so far, a kind providence seemed to have watched over us. Was it because we were children--or--I rejected that alternative. Walking along leisurely I made my way down to the shore. At a bridge that crossed a rather turbulent stream as it tumbled its way toward the sea, I paused and looked at the water reflectively. Suddenly my vagrant interest was aroused. Up the stream I saw some one struggling in the water and shouting for help as the current carried her along, screaming. It was Elaine. The hat and mustache of her disguise were gone and her beautiful Titian hair was spread out on the water as it carried her now this way, now that, while she struck out with all her strength to keep afloat. I did not stop to think how or why she was there. I swung over the bridge rail, stripping off my coat, ready to dive. On she came with the swift current to the bridge. As she approached I dived. It was not a minute too soon. In her struggles she had become thoroughly exhausted. She was a good swimmer but the fight with nature was unequal. I reached her in a second or so and took her hand. Half pulling, half shoving her, I struck out for the shore. We managed to make it together where the current was not quite so strong and climbed safely up a rock. Elaine sank down, choking and gasping, not unconscious but pretty much all in and exhausted. I looked at her in amazement. She was the tough character I had just seen. "Why, where in the world did you get those togs?" I queried. "Never mind my clothes, Walter," she gasped. "Take me home for some dry ones. I have a clue." She rose, determined to shake off the effects of her recent plunge and went toward the house. As I helped her she related breathlessly what she has just seen. Meanwhile, back of that wall of water, the wireless operator in the cave was sending the messages which Del Mar's emissary dictated to him, one after another. . . . . . . . With the high resistance receiving apparatus over his head, Arnold was listening to the wireless signals that came over his "radio detective" on the yacht, moving the slider back and forth on a sort of tuning coil, as he listened. Woodward stood close beside him. "As you know," Arnold remarked, "by the use of an aerial, messages may be easily received from any number of stations. Laws, rules, and regulations may be adopted by the government to shut out interlopers and to plug busybody ears, but the greater part of whatever is transmitted by the Hertzian waves can be snatched down by this wireless detective of mine. Here I can sit in my wireless room with this ear-phone clamped over my head drinking in news, plucking the secrets of others from the sky--in other words, this is eavesdropping by a wireless wire-tapper." "Are you getting anything now?" asked Woodward. Arnold nodded, as he seized a pencil and started to write. The lieutenant bent forward in tense interest. Finally Arnold read what he had written and with a peculiar, quiet smile handed it over. Woodward read. It was a senseless jumble of dots and dashes of the Morse code but, although he was familiar with the code, he could make nothing out of it. "It's the Morse code all right," he said, handing it back with a puzzled look, "but it doesn't make any sense." Arnold smiled again, took the paper, and without a word wrote on it some more. Then he handed it back to Woodward. "An old trick," he said. "Reverse the dots and dashes and see what you get." Woodward looked at it, as Arnold had reversed it and his face lighted up. "Harbor successfully mined," he quoted in surprise. "I'll show you another thing about this radio detective of mine," went on Arnold energetically. "It's not only a wave length measurer, but by a process of my own I can determine approximately the distance between the sending and the receiving points of a message." He attached another, smaller machine to the wireless detector. In the face was a moving finger which swung over a dial marked off in miles from one upward. As Arnold adjusted the new detector, the hand began to move slowly. Woodward looked eagerly. It did not move far, but came to rest above the figure "2." "Not so very far away, you see, Lieutenant," remarked Arnold, pointing at the dial face. He seized his glass and hurried to the deck, levelling it at the shore, leaning far over the rail in his eagerness. As he swept the shore, he stopped suddenly. There was a house-roof among the trees with a wireless aerial fastened to the chimney, but not quite concealed by the dense foliage. "Look," he cried to Woodward, with an exclamation of satisfaction, handing over the glass. Woodward looked. "A secret wireless station, all right," he agreed, lowering the glass after a long look. "We'd better get over there right away," planned Arnold, leading the way to the ladder over the side of the yacht and calling to the sailor who had managed the little motor-boat to follow him. Quickly they skimmed across to the shore. "I think we'd better send to the Fort for some men," considered Arnold as they landed. "We may need reinforcements before we get through." Woodward nodded and Arnold hastily wrote a note on a rather large scrap of paper which he happened to have in his pocket. "Take this to Colonel Swift at Fort Dale," he directed the sailor. "And hurry!" The sailor loped off, half on a run, as Arnold and Woodward left down the shore, proceeding carefully. At top speed, Arnold's sailor made his way to Fort Dale and was directed by the sentry to Colonel Swift who was standing before the headquarters with several officers. "A message from Lieutenant Woodward and Professor Arnold," he announced, approaching the commanding officer and handing him the note. Colonel Swift tore it open and read: Have located radio aerial in the woods along shore. Please send squad of men with bearer.--ARNOLD. "You just left them?" queried the Colonel. "Yes sir," replied the sailor. "We came ashore in his boat. I don't know exactly where they went but I know the direction and we can catch up with them easily if we hurry, sir." The colonel handed the note quickly to a cavalry officer beside him who read it, saluted at the orders that followed, turned and strode off, hastily stuffing the paper in his belt, as the sailor went, too. Meanwhile, Del Mar's valet was leaving the bungalow and walking down the road on an errand for his master. Up the road he heard the clatter of hoofs. He stepped back off the road and from his covert he could see a squad of cavalry headed by the captain and a sailor cantering past. The captain turned in the saddle to speak to the sailor, who rode like a horse marine, and as he did so, the turning of his body loosened a paper which he had stuffed quickly into his belt. It fell to the ground. In their hurry the troop, close behind, rode over it. But it did not escape the quick eye of Del Mar's valet. They had scarcely disappeared around a bend in the road when he stepped out and pounced on the paper, reading it eagerly. Every line of his face showed fear as he turned and ran back to the bungalow. "See what I found," he cried breathlessly bursting in on Del Mar who was seated at his desk, having returned from the harbor. Del Mar read it with a scowl of fury. Then he seized his hat, and a short hunter's axe, and disappeared through the panel into the subterranean passage which took him by the shortest cut through the very hill to the shore. Slowly Arnold and Woodward made their way along the shore, carefully searching for the spot where they had seen the house with the aerial. At last they came to a place where they could see the deserted house, far up on the side of a ravine above a river and a waterfalls. They dived into the thick underbrush for cover and went up the hill. Some distance off from the house, they parted the bushes and gazed off across an open space at the ramshackle building. As they looked they could see a man hurry across from the opposite direction and into the house. "As I live, I think that's Del Mar," muttered Arnold. Woodward nodded, doubtfully, though. In the house, Del Mar hurried to a wall where he found and pressed a concealed spring. A small cabinet in the plaster opened and he took out a little telephone which he rang and through which he spoke hastily. "Pull in the wires," he shouted. "We're discovered, I think." Down in the wireless station in the cave, the operator at his instrument heard the signal of the telephone and quickly answered it. "All right, sir," he returned with a look of great excitement and anxiety. "Cut the wires and I'll pull them in." Putting back the telephone, Del Mar ran to the window and looked out between the broken slats of the closed blinds. "Confound them!" he muttered angrily. He could see Arnold and Woodward cautiously approaching. A moment later he stepped back and pulled a silk mask over his upper face, leaving only his eyes visible. Then he seized his hunter's axe and dashed up the stairs. Through the scuttle of the roof he came, making his way over to the chimney to which the wireless antennae were fastened. Hastily he cut the wires which ran through the roof from the aerial. As he did so he saw them disappear through the roof. Below, in the cave, down in the ravine back of the falls, the operator was hastily hauling in the wire Del Mar had cut. Viciously next, Del Mar fell upon the wooden aerial itself, chopping it right and left with powerful blows. He broke it off and threw it over the roof. Below, Arnold and Woodward, taking advantage of every tree and shrub for concealment, had almost reached the house when the broken aerial fell with a bang almost on them. In surprise they dropped back of a tree and looked up. But from their position they could see nothing. Together they drew their guns and advanced more cautiously at the house. Del Mar made his way back quickly over the roof, back through the scuttle and down the stairs again. Should he go out? He looked out of the window. Then he went to the door. An instant he paused thinking and listening, his axe raised, ready for a blow. Arnold and Woodward, by this time, had reached the door which swung open on its rusty hinges. Woodward was about to go in when he felt a hand on his arm. "Wait," cautioned Arnold. He took off his hat and jammed it on the end of a stick. Slowly he shoved the door open, then thrust the hat and stick just a fraction of a foot forward. Del Mar, waiting, alert, saw the door open and a hat. He struck at it hard with the axe and merely the hat and stick fell to the floor. "Now, come on," shouted Arnold to Woodward. In the other hand, Del Mar held a chair. As Woodward dashed in with Arnold beside him, Del Mar shied the chair at their feet. Woodward fell over it in a heap and as he did so the delay was all that Del Mar had hoped to gain. Without a second's hesitation he dived through an open window, just as Arnold ran forward, avoiding Woodward and the chair. It was spectacular, but it worked. Arnold fired, but even that was not quick enough. He turned and with Woodward who had picked himself up in spite of his barked shins and they ran back through the door by which they had entered. Recovering himself, Del Mar dashed for the woods just as Arnold and Woodward ran around the side of the house, still blazing away after him, as they followed, rapidly gaining. Elaine changed her clothes quickly. Meanwhile she had ordered horses for both of us and a groom brought them around from the stables. It took me only a short time to jump into some dry things and I waited impatiently. She was ready very soon, however, and we mounted and cantered off, again in the direction of the shore where she had seen the remarkable waterfall, of which she had told me. We had not gone far when we heard sounds, as if an army were bearing down on us. "What's that?" I asked. Elaine turned and looked. It was a squad of cavalry. "Why, it's Lieutenant Woodward's friend, Captain Price," she exclaimed, waving to the captain at the head of the squad. A moment later Captain Price pulled up and bowed. Quickly we told him of what Elaine had just discovered. "That's strange," he said. "This man--" indicating the sailor--"has just told me that Lieutenant Woodward and Professor Arnold are investigating a wireless outfit over near there. Perhaps there's some connection." "May we join you?" she asked. "By all means," he returned. "I was about to suggest it myself." We fell in behind with the rest and were off again. Under the direction of the sailor we came at last to the ravine where we looked about searchingly for some trace of Arnold and Woodward. "What's that noise?" exclaimed one of the cavalrymen. We could hear shots, above us. "They may need us," cried Elaine, impatiently. It was impossible to ride up the sheer height above. "Dismount," ordered Captain Price. His men jumped down and we followed him. Elaine struggled up, now helped by me, now helping me. Further down the hill from the deserted house which we could see above us at the top was an underground passage which had been built to divert part of the water above the falls for power. Through it the water surged and over this boiling stream ran a board walk, the length of the tunnel. Into this tunnel we could see that a masked man had made his way. As he did so, he turned for just a moment and fired a volley of shots. Elaine screamed. There were Arnold and Woodward, his targets, coming on boldly, as yet unhit. They rushed in after him, in spite of his running fire, returning his shots and darting toward the tunnel entrance through which he still blazed back at them. From our end of the ravine, we could see precisely what was going on. "Come--the other end of the tunnel," shouted Price, who had evidently been over the ground and knew it. We made our way quickly to it and it seemed as if we had our man trapped, like a rat in a hole. In the tunnel the man was firing back at his pursuers as he ran along the board walk for our end. He looked up just in time as he approached us. There he could see Price and his cavalry waiting, cutting off retreat. We were too many for him. He turned and took a step back. There were Arnold and Woodward with levelled guns peering in as though they could not see very clearly. In a moment their eyes would become accustomed as his to the darkness. What should he do? There was not a second to waste. He looked down at the planks beneath him and the black water slipping past on its way to the power station. It was a desperate chance. But it was all that was left. He dropped down and let himself without even a splash into the water. Arnold and Woodward took a step into the darkness, scarcely knowing what to expect, their eyes a bit better accustomed to the dusk. But if they had been there an hour, in all probability they could not have seen what was at their very feet. Del Mar had sunk and was swimming under water in the swift black current sweeping under them. As they entered, he passed out, nerved up to desperation. Down the stream, just before it took its final plunge to the power wheel, Del Mar managed by a superhuman effort to reach out and grasp a wooden support of the flooring again and pull himself out of the stream. Smiling grimly to himself, he hurried up the bank. "Some one's coming," whispered Price. "Get ready." We levelled our guns. I was about to fire. "Look out! Don't shoot!" warned a voice sharply. It was Elaine. Her keen eyes and quick perception had recognized Arnold, leading Woodward. We lowered our guns. "Did you see a man, masked, come out here?" cried Woodward. "No--he must have gone your way," we called. "No, he couldn't." Arnold was eagerly questioning the captain as Elaine and I approached. "Dropped into the water--risked almost certain death," he muttered, half turning and seeing us. "I want to congratulate you on your nerve for going in there," began Elaine, advancing toward the professor. Apparently he neither heard nor saw us, for he turned as soon as he had finished with Price and went into the cave as though he were too busy to pay any attention to anything else. Elaine looked up at me, in blank astonishment. "What an impolite man," she murmured, gazing at the figure all stooped over as it disappeared in the darkness of the tunnel. CHAPTER XII THE DEATH CLOUD Off a lonely wharf in a deserted part of the coast some miles from the promontory which afforded Del Mar his secret submarine harbor, a ship was riding at anchor. On the wharf a group of men, husky lascars, were straining their eyes at the mysterious craft. "Here she comes," muttered one of the men, "at last." From the ship a large yawl had put out. As she approached the wharf it could be seen that she was loaded to the gunwales with cases and boxes. She drew up close to the wharf and the men fell to unloading her, lifting up the boxes as though they were weighted with feathers instead of metal and explosives. Down the shore, at the same time, behind a huge rock, crouched a rough looking tramp. His interest in the yawl and its cargo was even keener than that of the lascars. "Supplies," he muttered, moving back cautiously and up the bluff. "I wonder where they are taking them?" Marcus Del Mar had chosen an old and ruined hotel not far from the shore as his storehouse and arsenal. Already he was there, pacing up and down the rotted veranda which shook under his weight. "Come, hurry up," he called impatiently as the first of the men carrying a huge box on his back made his appearance up the hill. One after another they trooped in and Del Mar led them to the hotel, unlocking the door. Inside, the old hostelry was quite as ramshackle as outside. What had once been the dining-room now held nothing but a long, rickety table and several chairs. "Put them there," ordered Del Mar, directing the disposal of the cases. "Then you can begin work. I shall be back soon." He went out and as he did so, two men seized guns from a corner near-by and followed him. On the veranda he paused and turned to the men. "If any one approaches the house--any one, you understand--make him a prisoner and send for me," he ordered. "If he resists, shoot." "Yes, sir," they replied, moving over and stationing themselves one at each angle of the narrow paths that ran before the old house. Del Mar turned and plunged deliberately into the bushes, as if for a cross country walk, unobserved. Meanwhile, by another path up the bluff, the tramp had made his way parallel to the line taken by the men. He paused at the top of the bluff where some bushes overhung and parted them. "Their headquarters," he remarked to himself, under his breath. Elaine, Aunt Josephine and I were on the lawn that forenoon when a groom in resplendent livery came up to us. "Miss Elaine Dodge?" he bowed. Elaine took the note he offered and he departed with another bow. "Oh, isn't that delightful," she cried with pleasure, handing the note to me. I read it: "The Wilkeshire Country Club will be honored if Miss Dodge and her friends will join the paper chase this afternoon. L.H. Brown, Secretary." "I suppose a preparation for the fox or drag hunting season?" I queried. "Yes," she replied. "Will you go?" "I don't ride very well," I answered, "but I'll go." "Oh, and here's Mr. Del Mar," she added, turning. "You'll join us at the Wilkeshire hunt in a paper chase this afternoon, surely, Mr. Del Mar?" "Charmed, I'm sure," he agreed gracefully. For several minutes we chatted, planning, then he withdrew. "I shall meet you on the way to the Club," he promised. It was not long before Elaine was ready, and from the stable a groom led three of the best trained cross-country horses in the neighborhood, for old Taylor Dodge, Elaine's father, had been passionately fond of hunting, as had been both Elaine and Aunt Josephine. We met on the porch and a few minutes later mounted and cantered away. On the road Del Mar joined us and we galloped along to the Hunt Club, careful, however, to save the horses as much as possible for the dash over the fields. . . . . . . . For some time the uncouth tramp continued gazing fixedly out of the bushes at the deserted hotel. Suddenly, he heard a noise and dropped flat on the ground, looking keenly about. Through the trees he could see one of Del Mar's men stationed on sentry duty. He was leaning against a tree, on the alert. The tramp rose cautiously and moved off in another direction to that in which he had been making his way, endeavoring to flank the sentry. Further along, however, another of Del Mar's men was standing in the same attentive manner near a path that led from the woods. As the tramp approached, the sentry heard a crackle of the brush and stepped forward. Before the tramp knew it, he was covered by a rifle from the sentry in an unexpected quarter. Any one but the sentry, with half an eye, might have seen that the fear he showed was cleverly feigned. He threw his hands above his head even before he was ordered and in general was the most tractable captive imaginable. The sentry blew a whistle, whereat the other sentry ran in. "What shall we do with him," asked the captor. "Master's orders to take any one to the rendezvous," responded the other firmly, "and lock him up." Together they forced the tramp to march double quick toward the old hotel. One sentry dropped back at the door and the other drove the tramp before him into the hotel, avoiding the big room on the side where the men were at work and forcing him up-stairs to the attic which had once been the servant's quarters. There was no window in the room and it was empty. The only light came in through a skylight in the roof. The sentry thrust the tramp into this room and tried a door leading to the next room. It was locked. At the point of his gun the sentry frisked the tramp for weapons, but found none. As he did so the tramp trembled mightily. But no sooner had the sentry gone than the tramp smiled quietly to himself. He tried both doors. They were locked. Then he looked at the skylight and meditated. Down below, although he did not know it, in the bare dining-room which had been arranged into a sort of chemical laboratory, Del Mar's men were engaged in manufacturing gas bombs much like those used in the war in Europe. Before them was a formidable array of bottles and retorts. The containers for the bombs were large and very brittle globes of hard rubber. As the men made the gas and forced it under tremendous pressure into tubes, they protected themselves by wearing goggles for the eyes and large masks of cloth and saturated cotton over their mouths and noses. Satisfied with the safety of his captive, the sentry made his way down-stairs and out again to report to Del Mar. At the bungalow, Del Mar's valet was setting the library in order when he heard a signal in the secret passage. He pressed the button on the desk and opened the panel. From it the sentry entered. "Where is Mr. Del Mar?" he asked hurriedly, looking around. "We've been followed to the headquarters by a tramp whom I've captured, and I don't know what to do with him." "He is not here," answered the valet. "He has gone to the Country Club." "Confound it," returned the sentry, vexed at the enforced waste of time. "Do you think you can reach him?" "If I hurry, I may," nodded the valet. "Then do so," directed the sentry. He moved back into the panel and disappeared while the valet closed it. A moment later he, too, picked up his hat and hurried out. At the Wilkeshire Club a large number of hunters had arrived for the imitation meet. Elaine, Aunt Josephine, Del Mar and myself rode up and were greeted by them as the Master of Fox Hounds assembled us. Off a bit, a splendid pack of hounds was held by the huntsman while they debated whether to hold a paper chase or to try a drag hunt. "You start your cross-country riding early," commented Del Mar. "Yes," answered Elaine. "You see we can hardly wait until autumn and the weather is so fine and cool, we feel that we ought to get into trim during the summer. So we have paper chases and drag hunts as soon as we can, mainly to please the younger set." The chase was just about to start, when the valet came up. Del Mar caught his eye and excused himself to us. What he said, we could not hear, but Del Mar frowned, nodded and dismissed him. Just then the horn sounded and we went off, dashing across the road into a field in full chase after the hounds, taking the fences and settling down to a good half hour's run over the most beautiful country I have ever seen. The hounds had struck the trail, which of course, as was finally decided, was nothing but that laid by an anise-seed bag dragged over the ground. It was none the less, in fact perhaps more interesting for that. The huntsman winded his horn and mirthful shouts of "Gone away!" sounded in imitation of a real hunt. The blast of the horn once heard is never forgotten, thrilling the blood and urging one on. The M. F. H. seemed to be everywhere at once, restraining those who were too eager and saving the hounds often from being ridden down by those new to the hunt who pressed them. Elaine was one of the foremost. Her hunter was one carefully trained, and she knew all the tricks of the game. Somehow, I got separated, at first, from the rest and followed, until finally I caught up, and then kept behind one of the best riders. Del Mar also got separated, but, as I afterward learned, by intention, for he deliberately rode out of the course at the first opportunity he had and let Elaine and the rest of us pass without seeing him. Elaine's blood was up, but somehow, in spite of herself, she went astray, for the hounds had distanced the fleetest riders and she, in an attempt at a short cut over the country which she thought she knew so well, went a mile or so out of the way. She pulled up in a ravine and looked about. Intently she listened. There was no sign of the hunt. She was hot and tired and thirsty and, at a loss just to join the field again, she took this chance to dismount and drink from a clear stream fed by mountain springs. As she did so, floating over the peaceful woodland air came the faint strains of the huntsman's horn, far, far off. She looked about, straining her eyes and ears to catch the direction of sound. Just then her horse caught the winding of the horn. His ears went erect and without waiting he instantly galloped off, leaving her. Elaine called and ran after him, but it was too late. She stopped and looked dejectedly as he disappeared. Then she made her way up the side of the ravine, slowly. On she climbed until, to her surprise, she came to the ruins of an old hotel. She remembered, as a child, when it had been famous as a health resort, but it was all changed now--a wreck. She looked at it a moment, then, as she had nothing better to do, approached it. She advanced toward a window of the dining-room and looked in. . . . . . . . Del Mar waited only until the last straggler had passed. Then he dashed off as fast as his horse would carry him straight toward the deserted hotel which served him as headquarters for the supplies he was accumulating. As he rode up, one of his sentries appeared, as if from nowhere, and, seeing who it was, saluted. "Here, take care of this horse," ordered Del Mar, dismounting and turning the animal over to the man, who led him to the rear of the building as Del Mar entered the front door, after giving a secret signal. There were his men in goggles and masks at the work, which his knock had interrupted. "Give me a mask before I enter the room," he ordered of the man who had answered his signal. The man handed the mask and goggles to him, as well as a coat, which he put on quickly. Then he entered the room and looked at the rapid progress of the work. "Where's the prisoner?" asked Del Mar a moment later, satisfied at the progress of his men. "In the attic room," one of his lieutenants indicated. "I'd like to take a look at him," added Del Mar, just about to turn and leave the room. As he did so, he happened to glance at one of the windows. There, peering through the broken shutters, was a face--a girl's face--Elaine! "Just what I wanted guarded against," he cried angrily, pointing at the window. "Now--get her!" The men had sprung up at his alarm. They could all see her and with one accord dashed for the door. Elaine sprang back and they ran as they saw that she was warned. In genuine fear now she too ran from the window. But it was too late. For just then the sentry who had taken Del Mar's horse came from behind the building cutting off her retreat. He seized her just as the other men ran out. Elaine stared. She could make nothing of them. Even Del Mar, in his goggles and breathing mask was unrecognizable. "Take her inside," he ordered disguising his voice. Then to the sentry he added, "Get on guard again and don't let any one through." Elaine was hustled into the big deserted hallway of the hotel, just as the tramp had been. "You may go back to work," Del Mar signed to the other men, who went on, leaving one short but athletic looking fellow with Del Mar and Elaine. "Lock her up, Shorty," ordered Del Mar, "and bring the other prisoner to me down here." None too gently the man forced Elaine up-stairs ahead of him. . . . . . . . In the attic, the tramp, pacing up and down, heard footsteps approach on the stairs and enter the next room. Quickly he ran to the doorway and peered through the keyhole. There he could see Elaine and the small man enter. He locked the door to the hall, then quickly took a step toward the door into the tramp's room. There was just time enough for the tramp to see his approach. He ran swiftly and softly over to the further corner and dropped down as if sound asleep. The key turned in the lock and the small man entered, careful to lock the door to Elaine's room. He moved over to where the tramp was feigning sleep. "Get up," he growled, kicking him. The tramp sat up, yawning and rubbing his eyes. "Come now, be reasonable," demanded the man. "Follow me." He started toward the door into the hall. He never reached it. Scarcely was his hand on the knob when the tramp seized him and dragged him to the floor. One hand on the man's throat and his knees on his chest, the tramp tore off the breathing mask and goggles. Already he had the man trussed up and gagged. Quickly the tramp undressed the man and left him in his underclothes, still struggling to get loose, as he took Shorty's clothes, including the strange head-gear, and unlocked the door into the next room with the key he also took from him. Elaine was pacing anxiously up and down the little room into which she had been thrown, greatly frightened. Suddenly the door through which her captor had left opened hurriedly again. A most disreputable looking tramp entered and locked the door again. Elaine started back in fear. He motioned to her to be quiet. "You'll never get out alive," he whispered, speaking rapidly and thickly, as though to disguise his voice. "Here--take these clothes. Do just as I say. Put them on. Put on the mask and goggles. Cover up your hair. It is your only chance." He laid the clothes down and went out into the hallway. Outside he listened carefully at the head of the stairs and looked about expecting momentarily to be discovered. Elaine understood only that suddenly a friend in need had appeared. She changed her clothes quickly, finding fortunately that they fitted her pretty well. By pulling the hat over her hair and the goggles over her eyes and tying on the breathing mask, she made a very presentable man. Cautiously she pushed open the door into the hallway. There was the tramp. "What shall I do?" she asked. "Don't talk," he whispered close to her ear. "Go out--and if you meet any one, just salute and walk past." "Yes--yes, I understand," she nodded back, "and--thank you." He gave her no time to say more, even if it had been safe, but turned and locked the door of her room. Trying to keep the old stairway from creaking and betraying her, she went down. She managed to reach the lower hallway without seeing anybody or being discovered. Quietly she went to the door and out. She had not gone far when she met an armed man, the sentry, who had been concealed in the shrubbery. "Who goes there?" he challenged. Elaine did not betray herself by speaking, but merely saluted and passed on as fast as she could without exciting further suspicion. Nonplused, the man turned and watched her curiously as she moved away down the path. "Where's HE going?" the sentry muttered, still staring. Elaine in her eagerness was not looking as carefully where she was going as she was thinking about getting away in safety. Suddenly an overhanging branch of a tree caught her hat and before she knew it pulled it off her head. There was no concealing her golden hair now. "Stop!" shouted the sentry. Elaine did not pause, but dived into the bushes on the side of the path, just as the man fired and ran forward, still shouting for her to halt. She ran as fast as she could, pulling off the goggles and mask and looking back now and then in terror at her pursuer who was rapidly gaining on her. Before she could catch herself she missed her footing and slipped over the edge of a gorge. Down she went, with a rush. It was unfortunate, dangerous, but, after all, it was the only thing that saved her, at least for the time. Half falling, half sliding, scratching herself and tearing her clothes, she descended. The sentry checked himself just in time at the top of the gorge and leaned as far over the edge as he dared. He raised his gun again and fired. But Elaine's course was so hidden by the trees and so zigzag that he missed again. A moment he hesitated, then started and climbed down after her as fast as he could. At the bottom of the hill she picked herself up and dashed again into the woods, the sentry still after her and gaining again. At the same time, we who were still in the chase had circled about the country until we were very near where we started. Following the dogs over a rail fence, I drew up suddenly, hearing a scream. There was Elaine, on foot, running as if her life depended on it. I needed no second glance. Behind her was a man with a rifle, almost overtaking her. As luck would have it, the momentum of my horse carried me right at them. Careful to avoid Elaine, I rode square at the man, striking at him viciously with my riding crop before he knew what had struck him. The fellow dropped, stunned. I leaped from my horse and ran to her, just as the rest of the hunt came up. Eagerly questioning us, they gathered about. Having waited until he was sure that Elaine had got away safely, the old tramp slowly and carefully followed down the stairs of the ruined hotel. As he went down, he heard a shot from the woods. Could it be one of the sentries? He looked about keenly, hesitating just what to do. In an instant, down below, he heard the scurry of footsteps from the improvised laboratory and shouts. He turned and stealthily ran up-stairs, just as the door opened. The tramp had not been the only one who had been alarmed by the shot of the sentry. Del Mar was talking again to the men when it rang out. "What's that?" he exclaimed. "Another intruder?" The men stared at him blankly, while Del Mar dashed for the door, followed by them all. In the hall he issued his orders quickly. "Here, you fellows," he called dividing the men, "get outside and see what is doing. You other men follow me. I want you to see if everything's all right up above." Meanwhile the tramp had gained the upper hallway and dashed past the room which he occupied. Outside, in the hall, Del Mar and his men rushed up to the door of the room in which Elaine had been thrown. It was locked and they broke in. She was gone! On into the next room they dashed, bearing down this door also. There was Shorty, trussed up in his underclothes. They hastened to release him. "Where are they--where's the tramp?" demanded Del Mar angrily. "I think I heard some one on the roof," replied Shorty weakly. He was right. The tramp had managed to get through a scuttle on the roof. Then he climbed down to the edge and began to let himself hand over hand down the lightning rod. Reaching the ground safely, he scurried about to the back of the building. There, tied, was the horse which Del Mar had ridden to the hunt. He untied it, mounted and dashed off down the path through the woods, taking the shortest cut in the direction of Fort Dale. Dusty and flecked with foam, the tramp and his mount, a strange combination, were instantly challenged by the sentry at the Fort. "I must see Lieutenant Woodward immediately," urged the tramp. A heated argument followed until finally a corporal of the guards was called and led off the tramp toward the headquarters. It was only a few minutes before Woodward was convinced of the identity of the tramp with his friend, Professor Arnold. At the head of a squad of cavalry, Woodward and the tramp dashed off. Already on the qui vive, Elaine heard the sound of hoof-beats long before the rest of us crowded around her. For the moment we all stood ready to repel an attack from any quarter. But it was not meant for us. It was Woodward at the head of a score or so of cavalrymen. With him rode a tramp on a horse which was strangely familiar to me. "Oh," cried Elaine, "there's the man who saved me!" As they passed, the tramp paused a moment and looked at us sharply. Although he carefully avoided Elaine's eyes, I fancied that only when he saw that she was safe was he satisfied to gallop off and rejoin the cavalry. . . . . . . . Around the old hotel, in every direction, Del Mar's men were searching for the tramp and Elaine, while in the hotel another search was in progress. "Have you discovered anything?" asked Del Mar, entering. "No, sir," they reported. "Confound it!" swore Del Mar, going up-stairs again. Here also were men searching. "Find anything?" he asked briefly. "No luck," returned one. Del Mar went on up to the top floor and out through the open scuttle to the roof. "That's how he got away, all right," he muttered to himself, then looking up he exclaimed under his breath, as his eye caught something far off, "The deuce--what's that?" Leaning down to the scuttle, he called, "Jenkins--my field-glasses--quick!" One of his men handed them to him and he adjusted them, gazing off intently. There he could see what looked like a squad of cavalry galloping along headed by an officer and a rough looking individual. "Come--we must get ready for an attack!" he shouted diving down the scuttle again. In the laboratory dining-room, his men, recalled, hastily took his orders. Each of them seized one of the huge black rubber newly completed gas bombs and ran out, making for a grove near-by. Quickly as Del Mar had acted, it was not done so fast but that the troop of cavalry as they pulled up on the top of a hill and followed the directing finger of the tramp could see men running to the cover of the grove. "Forward!" shouted Woodward. As if all were one machine, the men and horses shot ahead, until they came to the grove about the old hotel. There they dismounted and spread out in a semi-circular order, advancing on the grove. As they did so, shots rang out from behind the trees. Del Mar's men, from the shelter were firing at them. But it seemed hopeless for the fugitives. "Ready!" ordered Del Mar as the cavalrymen advanced, relentless. Each of his men picked up one of the big black gas bombs and held it high up over his head. "Come on!" urged Woodward. His men broke into a charge on the grove. "Throw them!" ordered Del Mar. As far as he could hurl it, each of the men sent one of the black globes hurtling through the air. They fell almost simultaneously, a long line of them, each breaking into a thousand bits. Instantly dense, greenish-yellow fumes seemed to pour forth, enveloping everything. The wind which Del Mar had carefully noted when he chose the position in the grove, was blowing from his men toward the only position from which an attack could be made successfully. Against Woodward's men as they charged, it seemed as if a tremendous, slow-moving wall of vapor were advancing from the trees. It was only a moment before it completely wrapped them in its stifling, choking, suffocating embrace. Some fell, overcome. Others tried to run, clutching frantically at their throats and rubbing their eyes. "Get back--quick--till it rolls over," choked Woodward. Those who were able to do so, picked up their stupefied comrades and retreated, as best they could, stumbling blindly back from the fearful death cloud of chlorine. Meantime, under cover of this weird defence, Del Mar and his men, their own faces covered and unrecognizable in their breathing masks and goggles, dashed to one side, with a shout and disappeared walking and running behind and even through the safety of their impregnable gas barrier. More slowly we of the hunt had followed Woodward's cavalry until, some distance off, we stood, witnessing and wondering at the attack. To our utter amazement we saw them carrying off their wounded and stupefied men. We hurried forward and gathered about, offering whatever assistance we could to resuscitate them. As Elaine and I helped, we saw the unkempt figure of the tramp borne in and laid down. He was not completely overcome, having had presence of mind to tie a handkerchief over his nose and mouth. Elaine hurried toward him with an exclamation of sympathy. Just recovering full consciousness, he heard her. With the greatest difficulty, he seemed to summon some reserve force not yet used. He struggled to his feet and staggered off, as though he would escape us. "What a strange old codger," mused Elaine, looking from me at the retreating figure. "He saved my life--yet he won't even let me thank him--or help him!" CHAPTER XIII THE SEARCHLIGHT GUN "I don't understand it," remarked Elaine one day as, with Aunt Josephine and myself, she was discussing the strange events that had occurred since the disappearance of Kennedy, "but, somehow, it is as if a strange Providence seems to be watching over us." "Nor do I," I agreed. "It does seem that, although we do not see it, a mysterious power for good is about us. It's uncanny." "A package for you, Miss Dodge," announced Marie, coming in with a small parcel which had been delivered by a messenger who did not wait for an answer. Elaine took it, looked at it, turned it over, and then looked at the written address again. "It's not the handwriting of any one which I recognize," she mused. "Now, I suppose I ought to be suspicious of it Yet, I'm going to open it." She did so. Inside, the paper wrapping covered a pasteboard box. She opened that. There lay a revolver, which she picked up and turned over. It was a curious looking weapon. "I never knew so much about firearms as I have learned in the past few weeks," remarked Elaine. "But what do you suppose this is--and who sent it to me--and why?" She held the gun up. From the barrel stuck out a little rolled-up piece of paper. "See," she cried, reading and handing the paper to me, "there it is again--that mysterious power." Aunt Josephine and I read the note: DEAR MISS DODGE: This weapon shoots exactly into the center of the light disc. Keep it by you.--A FRIEND. "Let me see it," I asked, taking the gun. Sure enough, along the barrel was a peculiar tube. "A searchlight gun," I exclaimed, puzzled, though still my suspicions were not entirely at rest. "Suppose it's sighted wrong," I could not help considering. "It might be a plant to save some one from being shot." "That's easily settled," returned Elaine. "Let's try it." "Oh, mercy no,--not here," remonstrated Aunt Josephine. "Why not--down cellar?" persisted Elaine. "It can't hurt anything there." "I think it would be a good plan," I agreed, "just to make sure that it is all right." Accordingly we three went down cellar. There, Elaine found the light switch and turned it. Eagerly I hunted about for a mark. There, in some rubbish that had not yet been carted away, was a small china plate. I set it up on a small shelf across the room and took the gun. But Elaine playfully wrenched it from my hand. "No," she insisted, "it was sent to me. Let me try it first." Reluctantly I consented. "Switch off the light, Walter, please," she directed, standing a few paces from the plate. I did so. In the darkness Elaine pointed the gun and pulled a little ratchet. Instantly a spot of light showed on the wall. She moved the revolver and the spot of light moved with it. As it rested on a little decorative figure in the center of the plate, she pulled the trigger. The gun exploded with a report, deafening, in the confined cellar. I switched on the light and we ran forward. There was the plate--smashed into a hundred bits. The bullet had struck exactly in the centre of the little bull's-eye of light. "Splendid," cried Elaine enthusiastically, as we looked at each other in surprise. Though none of us guessed it, half an hour before, in the seclusion of his yacht, Woodward's friend, Professor Arnold, had been standing with the long barrelled gun in his hand, adjusting the tube which ran beneath the barrel. In one hand he held the gun; in the other was a piece of paper. As he brought the paper before the muzzle and pressed a ratchet by gripping the revolver handle, a distinct light appeared on the paper, thrown out from the tube under the barrel. Having adjusted the tube and sighted it, Arnold wrote a hasty note on another piece of paper and inserted it into the barrel of the gun, with the end sticking out just a bit. Then he wrapped the whole thing up in a box, rang a bell, and handed the package to a servant with explicit instructions as to its delivery to the right person and only to that person. Down in the submarine harbor, Del Mar was in conference with his board of strategy and advice, laying the plan for the attack on America. "Ever since we have been at work," he remarked, "Elaine Dodge has been busy hindering and frustrating us. That girl must go!" Before him, on the table, he placed a square package. "It must stop," he added ominously, tapping the package. "But how?" asked one of the men. "We've done our best." "This is a bomb," replied Del Mar, continuing to tap the package. "When our man--let me see, X had better do it,--arrives, have him look in the secret cavern by the landing-place. There I will leave it. I want him to put it in her house to-night." He handed the bomb to one of his men who took it gingerly. Then with a few more words of admonition, he took up his diving helmet and left the headquarters, followed by the man. Several minutes later, Del Mar, alone, emerged from the water just outside the submarine harbor and took off his helmet. He made his way over the rocks, carrying the bomb, until he came to a little fissure in the rocks, like a cavern. There he hid the bomb carefully. Still carrying the helmet, he hurried along until he came to the cave entrance that led to the secret passage to the panel in his bungalow library. Up through the secret passage he went, reaching the panel and opening it by a spring. In the library Del Mar changed his wet clothes and hid them, then set to work on an accumulation of papers on his desk. . . . . . . . That afternoon, Elaine decided to go for a little ride through the country in her runabout. As she started to leave her room, dressed for the trip, it was as though a premonition of danger came to her. She paused, then turned back and took from the drawer the searchlight gun which had been sent to her. She slipped it into the pocket of her skirt and went out. Off she drove at a fast clip, thoroughly enjoying the ride until, near a bend in the road, as it swept down toward the shore, she stopped and got out, attracted by some wild flowers. They grew in such profusion that it seemed no time before she had a bunch of them. On she wandered, down to the rocks, watching the restless waters of the Sound. Finally she found herself walking alone along the shore, one arm full of flowers, while with her free hand she amused herself by skimming flat stones over the water. As she turned to pick up one, her eye caught something in the rocks and she stared at it. There in a crevice, as though it had been hidden, was a strange square package. She reached down and picked it up. What could it be? While she was examining it, back of her, another of those strange be-helmeted figures came up out of the water. It watched her for an instant, then sank back into the water again. Elaine, holding the package in her hand, walked up the shore, oblivious to the strange eye that had been fixed on her. "I must show this to Lieutenant Woodward," she said to herself. In the car she placed the package, then jumped in herself carefully and started off. A moment after she had gone, the diver reappeared, looking about cautiously. This time the coast was clear and he came all the way out, taking off his helmet and placed it in the secret hiding-place which Del Mar and his men used. Then, with another glance, now of anger, in the direction of Elaine, he hurried up the shore. Meanwhile, as fast as her light runabout would carry her, Elaine whizzed over to Fort Dale. As she entered the grounds, the sentry saluted her, though that part of the formalities of admission was purely perfunctory, for every one at the Fort knew her now. "Is Lieutenant Woodward in?" she inquired. "Yes ma'am," returned the sentry. "I will send for him." A corporal appeared and took a message for her to Woodward. It was only a few minutes before Lieutenant Woodward himself appeared. "What is the trouble, Miss Dodge?" he asked solicitously, noting the look on her face. "I don't know what it is," she replied dubiously. "I've found something among the rocks. Perhaps it is a bomb." Woodward looked at the package, studying it. "Professor Arnold is investigating this affair for us," he remarked. "Perhaps you'd better take the package to him on his yacht. I'm sorry I can't go with you, but just now I'm on duty." "That's a good idea," she agreed. "Only I'm sorry you can't go along with me." She started up the car and drove off as Woodward turned back to the Fort with a lingering look. Del Mar was hard at work in the library when, suddenly, he heard a sound at the panel. He reached over and pressed a button on his desk, and the panel opened. Through it came the diver still wearing his dripping suit and carrying the weird helmet under his arm. "That Dodge girl has crossed us again!" he exclaimed excitedly. "How?" demanded Del Mar, with an oath. "I saw her on the rocks just now. She happened to stumble on the bomb which you left there to be placed." "And then?" demanded Del Mar. "She took it with her in her car." "The deuce!" ejaculated the foreign agent, furiously. "You must get the men out and hunt the country thoroughly. She must not escape now at any cost." The diving man dove back into the panel to escape Del Mar's wrath, while Del Mar hurried out, leaving his valet in the library. Quickly, Del Mar made his way to a secret hiding-place in the hills back of the bay. There he found his picked band of men armed with rifles. As briefly as he could he told them of what had happened. "We must get her this time--dead or alive," he ordered. "Now scatter about the country. Keep in touch with each other and when you find her, close in on her at any cost." The men saluted and left in various directions to scour the country. Del Mar himself picked up a rifle and followed shortly, passing down a secret trail to the road where he had a car with a chauffeur waiting. Still carrying the rifle, he climbed in and the man shot the car along down the road. . . . . . . . On the top of a hill one of the men was posted as a sort of lookout. Gazing over the country carefully, his eye was finally arrested by something at which he stared eagerly. Far away, on the road, he could see a car in which was a girl, alone. Waving in the breeze was a red feather in her hat. He looked more sharply. It was Elaine Dodge. The man turned and waved a signal with a handkerchief to another man far off. Down the valley another of Del Mar's men was waiting and watching. As soon as he saw the signal, he waved back and ran along the road. As Del Mar whizzed along, he could see one of his men approaching over the road, waving to him. "Stop!" he ordered his driver. The man hurried forward. "I've got the signal," he panted. "They have seen her car over the hill." "Good," exclaimed Del Mar, pulling a black silk mask over his eyes. "Now, get off quickly. We've got to catch her." They sped away again in a cloud of dust. But even while Del Mar was speeding toward her, another of his men had discovered her presence, so vigilant were they. He had been keeping a sharp watch on the road, when he was suddenly all attention. He saw a car, through the foliage. Quickly, his rifle went to his shoulder. Through the sight he could just cover Elaine's head, for her hat, with a bright red feather in it, showed plainly just over the bushes. He aimed carefully and fired. I had been out for a tramp over the hills with no destination in particular. As I swung along the road, I heard the throbbing of a car coming up the hill, the cut-out open. I turned, for cars make walking on country roads somewhat hazardous nowadays. As I did so, some one in the car waved to me. I looked again. It was Elaine. "Where are you going?" she called. "Where are YOU going?" I returned, laughing. "I've just had a very queer experience--found something down on the rocks," she replied seriously, pointing to the square package on the floor of the car. "I took it to Lieutenant Woodward and he advised me to take it to Professor Arnold on his yacht. I think it is a bomb. I wish you'd go with me." Before I could answer, up the hill a rifle shot cracked. There was a whirr in the air and a bullet sang past us, cutting the red feather off Elaine's hat. "Duck!" I cried, jumping into the car, "And drive like the dickens!" She turned and we fairly ricocheted down that road back again. Behind us, a man, a stranger whom we did not pause to observe, rushed from the bushes and fired after us again. Suddenly another rifle shot cracked. It was from another car that had stealthily sneaked up on us--coming fast, recklessly. "There's her car," pointed one of the occupants to a man who was masked in black. "Yes," he nodded. "Give her a little more gas!"' "Crouch down," I muttered, "as low as you can." We did so, racing for life, the more powerful motor behind us overhauling us every instant. We were coming to a very narrow part of the road where it turned, on one side a sheer hill, on the other a stream several feet down. If we had an accident, I thought, it might be ticklish for us, supposing the square package really to be a bomb. What if it should go off? The idea suggested another, instantly. The car behind was only a few feet off. As we reached the narrow road by the stream, I rose up. As far as I could, back of me, I hurled the infernal machine. It fell. We received a shower of dirt and small stones, but the cover of the car protected us. Where the bomb landed, however, it cut a deep hole in the roadway. On came Del Mar's car, the driver frantically tugging at the emergency brake. But it was of no use. There was not room to turn aside. The car crashed into the hole, like a gigantic plow. It took one header over the side of the road and down several feet into the stream, just as the masked man and the driver jumped far ahead into the water. Safe now in our car which was slackening its terrific speed, I looked back. "They've been thrown!" I cried. "We're all right." On the edge of the water, just covered by some wreckage, the chauffeur lay motionless. The masked man crawled from under the wreckage and looked at him a moment. "Dead!" he exclaimed, still mechanically gripping a rifle in his hand. Angrily he raised it at us and fired. A moment later, some other men gathered from all directions about him, each armed. "Don't mind the wreck," he cried, exasperated. "Fire!" A volley was delivered at us. But the distance was now apparently too great. We were just congratulating ourselves on our escape, when a stray shot whizzed past, striking a piece directly out of the head of the steering-post, almost under Elaine's hands. Naturally she lost control, though fortunately we were not going so fast now. Crazily, our car swerved from side to side of the road, as she vainly tried to control both its speed and direction. On the very edge of the ditch, however, it stopped. We looked back. There we could see a group of men who seemed to spring out of the woods, as if from nowhere, at the sound of the shots. A shout went up at the sight of the bullet taking effect, and they ran forward at us. One of their number, I could see, masked, who had been in the wrecked car, stumbled forward weakly, until finally he sank down. A couple of the others ran to him. "Go on," he must have urged vehemently. "One of you is enough to stay with me. I'm going back to the submarine harbor. The rest--go on--report to me there." As the rest ran toward us, there was nothing for us to do but to abandon the car ourselves and run for it. We left the road and struck into the trackless woods, followed closely now by two of the men who had outdistanced the rest. Through the woods we fled, taking advantage of such shelter as we could find. "Look, here's a cave," cried Elaine, as we plunged, exhausted and about ready to drop, down into a ravine. We hurried in and the bushes swung over the cave entrance. Inside we stopped short and gazed about. It was dark and gloomy. We looked back. There was no hope there. They had been overtaking us. On down a passageway, we went. The two men who were pursuing us plunged down the ravine also. As ill-luck would have it, they saw the cave entrance and dashed in, then halted. Crouching in the shadow we could see their figures silhouetted in the dim light of the entrance of the cavern. One stopped at the entrance while the other advanced. He was a big fellow and powerfully built and the other fellow was equally burly. I made up my mind to fight to the last though I knew it was hopeless. It was dark. I could not even see the man advancing now. Quickly Elaine reached into her pocket and drew out something. "Here, Walter, take this," she cried. I seized the object. It was the searchlight gun. Hastily I aimed it, the spot of light glowing brightly. Indeed, I doubt whether I could have shot very accurately otherwise. As the man approached cautiously down the passageway the bright disc of light danced about until finally it fell full on his breast. I fired. The man fell forward instantly. Again I fired, this time at the man in the cave entrance. He jumped back, dropping his gun which exploded harmlessly. His hand was wounded. Quickly he drew back and disappeared among the trees. We waited in tense silence, and then cautiously looked out of the mouth of the cave. No one seemed to be about. "Come--let's make a dash for it," urged Elaine. We ran out and hurried on down the ravine, apparently not followed. Back among the trees, however, the man had picked up a rifle which he had hidden. While he was binding up his hand with a handkerchief, he saw us. Painfully he tried to aim his gun. But it was too heavy for his weakened arm and the pain was too great. He had to lower it. With a muttered imprecation, he followed us at a distance. Evidently, to us, we had eluded the pursuers, for no one seemed now to be following, at least as far as we could determine. We kept on, however, until we came to the water's edge. There, down the bay, we could see Professor Arnold's yacht. "Let us see Professor Arnold, anyhow," said Elaine, leading the way along the shore. We came at last, without being molested, to a little dock. A sailor was standing beside it and moored to it was a swift motor-boat. Out at anchor was the yacht. "You are Professor Arnold's man?" asked Elaine. "Yes'm," he replied, remembering her. "Is the Professor out on his boat?" we asked. He nodded. "Did you want to see him?" "Very much," answered Elaine. "I'll take you out," he offered. We jumped into the motor-boat, he started the engine and we planed out over the water. Though we did not see him, the man whom I had wounded was still watching us from the shore, noting every move. He had followed us at a distance across the woods and fields and down along the shore to the dock, had seen us talking to Arnold's man, and get into the boat. From the shore he continued to watch us skim across the bay and pull up alongside the yacht. As we climbed the ladder, he turned and hurried back the way he had come. . . . . . . . Elaine and I climbed aboard the yacht where we could see the Professor sitting in a wicker deck chair. "Why, how do you do?" he welcomed us, adjusting his glasses so that his eyes seemed, if anything, more opaque than before. I could not help thinking that, although he was glad to see us, there was a certain air of restraint about him. Quickly Elaine related the story of finding the bomb in the rocks and the peculiar events and our escape which followed. Once, at the mention of the searchlight gun, Professor Arnold raised his hand and coughed back of it. I felt sure that it was to hide an involuntary expression of satisfaction and that it must be he who had sent the gun to Elaine. He was listening attentively to her, while I stood by the rail, now and then looking out over the water. Far away I noted something moving over the surface, like a rod, followed by a thin wake of foam. "Look!" I exclaimed, "What's that?" Elaine turned to me, as Arnold seized his glasses. "Why, it seems to be moving directly at us," exclaimed Elaine. "By George, it's the periscope of a submarine," cried Arnold a moment later, lowering his glasses. He did not hesitate an instant. "Get the yacht under way," he ordered the captain, who immediately shouted his orders to the rest. Quickly the engine started and we plowed ahead, that ominous looking periscope following. In the submarine harbor to which he had been taken, Del Mar found that he had been pretty badly shaken up by the accident to his car. His clothes were torn and his face and body scratched. No bones were broken, however, though the shock had been great. Several of his men were endeavoring to fix him up in the little submarine office, but he was angry, very angry. At such a juncture, a man in a dripping diving-suit entered and pulled off his helmet, after what had evidently been a hasty trip from the land through the entrance and up again into the harbor. As he approached, Del Mar saw that the man's hand was bound up. "What's the matter?" demanded Del Mar. "How did you get that?" "That fellow Jameson and the girl did it," he replied, telling what had happened in the cave. "Some one must have given them one of those new searchlight guns." Del Mar, already ugly, was beside himself with rage now. "Where are they?" he asked. "I saw them go out to the yacht of that Professor Arnold." "He's the fellow that gave her the gun," almost hissed Del Mar. "On the yacht, are they?" An evil smile seemed to spread over his face. "Then we'll get them all, this time. Man the submarine--the Z99." All left the office on the run, hurrying around the ledge and down into the open hatch of the submarine. Del Mar came along a moment later, giving orders sharply and quickly. The hatch was closed and the vessel sealed. On all sides were electrical devices and machines to operate the craft and the torpedoes--an intricate system of things which it seemed as if no human mind could possibly understand. Del Mar threw on a switch. The submarine hummed and trembled. Slowly she sank in the harbor until she was at the level of the underwater entrance through the rocks. Carefully she was guided out through this entrance into the waters of the larger, real harbor. Del Mar took his place at the periscope, the eye of the submarine. Anxiously he turned it about and bent over the image which it projected. "There it is," he muttered, picking out Arnold's yacht and changing the course of the submarine so that it was headed directly at it, the planes turned so that they kept the boat just under the surface with only the periscope showing above. Forward, about the torpedo discharge tubes men were busy, testing the doors, and getting ready the big automobile torpedoes. "They must have seen us," muttered Del Mar. "They've started the yacht. But we can beat them, easily. Are you ready?" "Yes," called back the men forward, pushing a torpedo into the lock-like compartment from which it was launched. "Let it go, then," bellowed Del Mar. The torpedo shot out into the water, travelling under her own power, straight at the yacht. . . . . . . . Elaine and I looked back. The periscope was much nearer than before. "Can we outdistance the submarine?" I asked of Arnold. Arnold shook his head, his face grave. On came the thin line of foam. "I'm afraid we'll have to leave the yacht," he said warningly. "My little motor-boat is much faster." Arnold shouted his orders as he led us down the ladder to the motor-boat into which we jumped, followed by as many of the crew as could get in, while the others leaped into the water from the rail of the yacht and struck out for the shore which was not very distant. "What's that?" cried Elaine, horrified, pointing back. The water seemed to be all churned up. A long cigar-shaped affair was slipping along near enough to the surface so that we could just make it out--murderous, deadly, aimed right at the heart of the yacht. "A torpedo!" exclaimed Arnold. "Cast off!" We moved off from the yacht as swiftly as the speedy little open motor-boat would carry us, not a minute too soon. The torpedo struck the yacht almost exactly amidships. A huge column of water spurted up into the air as though a gigantic whale were blowing off. The yacht itself seemed lifted from the water and literally broken in half like a brittle rod of glass and dropped back into the water. Below in the submarine, Del Mar was still at the periscope directing things. "A hit!" he cried exultingly. "We got the whole bunch this time!" He turned to the men to congratulate them, a smile on his evil face. But as he looked again, he caught sight of our little motor-boat skimming safely away on the other side of the wreck. "The deuce!" he muttered. "Try another. Here's the direction." Furiously he swore as the men guided the submarine and loaded another torpedo into a tube. As the tube came into position, they let the torpedo go. An instant later it was hissing its way at us. "See, there's another!" I cried, catching sight of it. All looked. Sure enough, through the water could be seen another of those murderous messengers dashing at us. Arnold ran forward and seized the wheel himself, swinging the boat around hard to starboard and the land. We turned just in time. The torpedo, brainless but deadly, dashed past us harmlessly. As fast as we could now we made for the shore. No one could catch us with such a start, not even the swiftest torpedo. We had been rescued by Arnold's quick wit from a most desperate situation. Somewhere below the water, I could imagine a man consumed with fury over our escape, as the periscope disappeared and the submarine made off. We were safe. But, looking out over the water, we could not help shuddering at the perils beneath its apparently peaceful surface. CHAPTER XIV THE LIFE CHAIN Early one morning, a very handsome woman of the adventuress type arrived with several trunks at the big summer hotel, just outside the town, the St. Germain. Among the many fashionable people at the watering-place, however, she attracted no great attention and in the forenoon she quietly went out in her motor for a ride. It was Madame Larenz, one of Del Mar's secret agents who, up to this time, had been engaged in spying on wealthy and impressionable American manufacturers. Her airing brought her, finally, to the bungalow of Del Mar and there she was admitted in a manner that showed that Del Mar trusted her highly. "Now," he instructed, after a few minutes chat, "I want you to get acquainted with Miss Dodge. You know how to interest her. She's quite human. Pretty gowns appeal to her. Get her to the St. Germain. Then I'll tell you what to do." A few minutes later the woman left in her car, so rapidly driven that no one would recognize her. It was early in the afternoon that Aunt Josephine was sitting on the veranda, when an automobile drove up and a very stylishly gowned and bonnetted woman stepped out. "Good afternoon," she greeted Aunt Josephine ingratiatingly as she approached the house. "I am Madame Larenz of New York and Paris. Perhaps you have heard of my shops on Fifth Avenue and the Rue de la Paix." Aunt Josephine had heard the name, though she did not know that this woman had assumed it without being in any way connected with the places she mentioned. "I'm establishing a new sort of summer service at the better resorts," the woman explained. "You see, my people find it annoying to go into the city for gowns. So I am bringing the latest Paris models out to them. Is Miss Dodge at home?" "I think she is playing tennis," returned Aunt Josephine. "Oh, yes, I see her, thank you," the woman murmured, moving toward the tennis court, back of the house. Elaine and I had agreed to play a couple of games and were tossing rackets for position. "Very well," laughed Elaine, as she won the toss, "take the other court." It was a cool day and I felt in good spirits. Just to see whether I could do it still, I jumped over the net. Our game had scarcely started when we were interrupted by the approach of a stunning looking woman. "Miss Dodge?" she greeted. "Will you excuse me a moment?" Elaine paused in serving the ball and the woman handed her a card from her delicate gold mesh bag. It read simply: Mme. Larenz Paris Gowns Elaine looked at the card a moment while the woman repeated what she had already told Aunt Josephine. "You have them here, then?" queried Elaine, interested. "Yes, I have some very exclusive models which I am showing at my suite in the St. Germain." "Oh, how lovely," exclaimed Elaine. "I must see them." They talked a few minutes, while I waited patiently for Elaine to start the game again. That game, however, was destined never to be finished. More weighty matters were under discussion. I wondered what they were talking about and, suppressing a yawn, I walked toward them. As I approached, I heard scattered remarks about styles and dress fabrics. Elaine had completely forgotten tennis and me. She took a couple of steps away from the court with the woman, as I came up. "Aren't you going to play?" I asked. "I know you'll excuse me, Walter," smiled Elaine. "My frocks are all so frightfully out of date. And here's a chance to get new ones, very reasonably, too." They walked off and I could not help scowling at the visitor. On toward the house Elaine and Madame Larenz proceeded and around it to the front porch where Aunt Josephine was standing. "Just think, Auntie," cried Elaine, "real Paris gowns down here without the trouble of going to the city--and cheaply, too." Aunt Josephine was only mildly interested, but that did not seem to worry Madame Larenz. "I shall be glad to see you at three, Miss Dodge," she said as she got into her car again and drove off. By that time, I had caught up with Elaine again. "Just one game," I urged. "Please excuse me,--this time, Walter," she pleaded, laughing. "You don't know how sadly I'm in need of new frocks." It was no use of further urging her. Tennis was out of her mind for good that day. Accordingly, I mounted to my room and there quickly donned my riding clothes. When I came down, I found Aunt Josephine still on the veranda. In addition to my horse which I had telephoned for, Elaine's little runabout had been driven to the door. While I was talking to Aunt Josephine, Elaine came down-stairs and walked over to the car. "May I go with you?" I pleaded. "No, Walter," she replied laughing merrily. "You can't go. I want to try them on." Properly squelched, I retreated. Elaine drove away and a moment later, I mounted and cantered off leisurely. Near Del Mar's bungalow might have been seen again the mysterious naturalist, walking along the road with a butterfly net in his hand and what appeared to be a leather specimen case, perhaps six inches long, under his other arm. As Madame Larenz whizzed past in her car, he looked up keenly in spite of his seeming near-sightedness and huge smoked glasses. He watched her closely, noting the number of the car, then turned and followed it. Madame Larenz drew up, a second time, before Del Mar's. As she got out and entered, the naturalist, having quickened his pace, came up and watched her go in. Then, after taking in the situation for a moment, he made his way around the side of the bungalow. "Is Mr. Del Mar at home?" inquired Madame Larenz, as the valet ushered her into the library. "No ma'am," he returned. "Mr. Del Mar is out. But he left word that if you came before he got back, you were to leave word." The woman sat down at the desk and wrote hastily. When she had finished the short note, she read it over and folded it up. "Tell Mr. Del Mar I've left a note here on his desk," she said to the valet. A moment later she left the library, followed by the valet, who accompanied her to her car and assisted her in. "The hotel," she directed to her driver, as he started off, while the valet returned to the bungalow. Outside, the naturalist had come through the shrubbery and had been looking in at the library window, watching every move of Madame Larenz as she wrote. As she went out, he paused just a second to look about. Then he drew a long knife from his pocket, forced the window catch, and quickly climbed into the room. Directly to the desk he went and hurriedly ran over the papers on it. There was the note. He picked it up and read it eagerly. "My apartment--St. Germain--3 P. M. "LARENZ." For a moment he seemed to consider what to do. Then he replaced the note. Suddenly he heard the sound of footsteps. It was the valet returning. Quickly the naturalist ran to the window and jumped out. A moment later, the valet entered the library again. "That's strange," he exclaimed under his breath, "I don't recall opening that window over there to-day." He looked puzzled. But as no one was about, he went over and shut it. Some distance down the road, the naturalist quietly emerged in safety from the bushes. With scarcely a moment's hesitation, his mind thoroughly made up to his course, he hurried along the road. Meanwhile, at the St. Germain, Madame Larenz entered and passed through the rotunda of the hotel, followed by many admiring glances of the men. Up in her room stood several large trunks, open. From them had been taken a number of gowns which were scattered about or hung up for exhibition. As she entered, quickly she selected one of the trunks whose contents were more smart than the rest and laid the gowns out most fetchingly about the room. In the office of the hotel a few moments later, the naturalist entered. He looked around curiously, then went to the desk and glanced over the register. At the name "Mme Larenz, Paris, Room 22," he paused. For some seconds he stood thinking. Then he deliberately walked over to a leather chair and took a prominent seat near-by in the lobby. He had discarded his net, but still had the case which now he had shoved into his pocket. From a table, he picked up a newspaper. It was not long before Del Mar pulled up before the hotel and entered in his usual swagger manner. He had returned to the bungalow, read the note and hurried over to the St. Germain. He crossed the lobby, back to the office. As he did so, the naturalist had his face hidden deeply in the open newspaper. But no sooner had Del Mar passed than the newspaper fell unappreciated and he gazed after him, as he left the lobby by the back way. It was only a few minutes after she had completed arranging her small stock so that it looked quite impressive, that Madame Larenz heard a knock at the door and recognized Del Mar's secret code. She opened the door and he strode in. "I got your note," he said briefly, coming directly to business and telling her just what he wanted done. "Let me see," he concluded, glancing at his watch. "It is after three now. She ought to be here any minute." Outside, Elaine drove up to the rather garish entrance of the St. Germain and one of the boys in uniform ran forward to open the door and take charge of the car. She, too, crossed the lobby without seeing the old naturalist, though nothing escaped him. As she passed, he started to rise and cross toward her, then appeared to change his mind. Elaine went on out through the back of the lobby, directed by a boy, and mounted a flight of stairs, in preference to taking the lift to the second, or sort of mezzanine floor. Down along the corridor she went, hunting for number twenty-two. At last she found it at the end, and knocked. Del Mar and Madame Larenz were still talking in low tones when they heard a light tap on the door. "There she is, now," whispered Larenz. "All right. Let her in," answered Del Mar, leaping quietly to a closet. "I'll hide here until I get the signal. Do just as I told you." Outside, at the same time, according to his carefully concocted plans, Del Mar's car had driven up and stopped close to the side of the hotel, which was on a slight hill that brought the street level here not so far below the second story windows. Three of his most trusted men were in the car. Madame Larenz opened the door. "Oh, I'm so glad you came," she rattled on to Elaine. "You see, I've got to get started. Not a customer yet. But if you'll only take a few gowns, other people will come to me. I'll let you have them cheaply, too. Just look at this one." She held up one filmy, creamy creation that looked like a delicate flower. "I'd like to try it on," cried Elaine, fingering it rapturously. "By all means," agreed Madame. "We are alone. Do so." With deft fingers, Larenz helped her take off her own very pretty dress. As Elaine slipped the soft gown over her head, with her head and arms engaged in its multitudinous folds, Madame Larenz, a powerful woman, seized her. Elaine was effectually gagged and bound in the gown itself. Instantly, Del Mar flung himself from the closet, disguising his voice. Together, they wrapped the dress about Elaine even more tightly to prevent her screaming. Madame 'Larenz seized a blanket and threw that over Elaine's head, also, while Del Mar ran to the window. There were his men in the car, waiting below. "Are you ready?" he called softly to them. They looked about carefully. There was no one on that side of the hotel just at the moment. "Ready," responded one. "Quick!" Together, Del Mar and Madame Larenz passed Elaine, ineffectually struggling, out of the window. The men seized her and placed her in the bottom of the car, which was covered. Then they shot away, taking a back road up the hill. Hurriedly the naturalist went through the lobby in the direction Elaine had gone, and a moment later reached the corridor above. Down it, he could hear some one coming out of room twenty-two. He slid into an angle and hid. It was Del Mar and the woman he had seen at the bungalow. They passed by without discovering him, nor could he make out anything that they said. What mischief was afoot? Where was Elaine? He ran to the door and tried it. It was locked. Quickly, he took from his pocket a skeleton key and unlocked it. There was Elaine's hat and dress lying in a heap on the bed. But she was not there. He was now thoroughly alarmed. She could not have passed him in the hall. Therefore she must have gone or been taken out through the window. That would never have been voluntary, especially leaving her things there. The window was still open. He ran to it. One glance out was enough. He leaped to the ground. Sure enough, there were automobile tracks in the dust. "Del Mar's car," he muttered to himself, studying them. He fairly ran around the side of the hotel. There he came suddenly upon Elaine's car standing alone, and recognized it. There was no time for delay. He jumped into it, and let the swift little racer out as he turned and gathered momentum to shoot up the hill on high speed. Meanwhile, I had been jogging along through the country, lonely and disconsolate. I don't know how it happened, but I suppose it was by some subconscious desire. At any rate I found myself at the road that came out across one leading to the St. Germain and it occurred to me that Elaine might by this time have purchased enough frocks to clothe her for a year. At any rate I quickened my pace in the hope of seeing her. Suddenly, my horse shied and a familiar little car flashed past me. But the driver was not familiar. It was Elaine's roadster. In it was a stranger--a man who looked like a "bugologist," as nearly as I can describe him. Was he running off with her car while she was waiting inside the hotel? I galloped after him. Del Mar's automobile, with Elaine bound and gagged in it, drove rapidly by back and unfrequented ways into the country until at last it pulled up before an empty two-story house in a sort of grove of trees. The men leaped out, lifted Elaine, and carried her bodily into the house, taking her up-stairs and into an upper room. She had fainted when they laid her down and loosened the dress from about her face so that she could breathe. There they left her, on the floor, her hands and feet bound, and went out. How long she lay there, she never knew, but at last the air revived her and she regained consciousness and sat up. Her muscles were sore and her head ached. But she set her teeth and began struggling with the cords that bound her, managing at last to pull the dress over herself at least. In Elaine's car, the naturalist drove slowly at times, following the tracks of the automobile ahead. At last, however, he came to a place where he saw that the tracks went up a lonely side road. To approach in a car was to warn whoever was there. He ran the cat up alongside the road in the bushes and jumped out leaving it and following the tracks up the side roadway. As he approached a single deserted house, he left even the narrow road altogether and plunged into the woods, careful to proceed noiselessly. Through the bushes, near the house, he peered. There he could see one of Del Mar's men in the doorway, apparently talking to others behind him. Stealthily the naturalist crept around, still hiding, until he was closer to the house on the other side. At last he worked his way around to the rear door. He tried it. It was bolted and even the skeleton key was unavailing to slide the bolt. Seconds were precious. Quickly, he went to the corner of the house. There was a water-leader. He began to climb it, risking its precarious support. On the roof at last, the naturalist crawled along, looking for some way of getting into the house. But he could not seem to find any. Carefully, he crawled to the edge of the roof and looked over. Below, he could hear sounds, but could make nothing of them. From his pocket, he took the leather case and opened it. There was a peculiar arrangement, like some of the collapsible arms on which telephone instruments are often fastened to a desk or wall, capable of being collapsed into small space or of being extended for some distance. On the thing was arranged a system of mirrors, which the naturalist adjusted. It was a pocket periscope. He thrust the thing over the edge of the roof and down, and looked through it. Below, he could see into the room from which came the peculiar sounds. He looked anxiously. There he could see Elaine endeavoring still to loosen the cords and unable to do so. Only for a moment he looked. Then he folded up the pocket periscope into the case and shoved it back into his pocket. Quickly he crossed the roof again, and slid back down the rain-pipe. At the door stood three of Del Mar's men waiting for Del Mar who had told them he would follow immediately. The naturalist had by this time reached the ground and was going along carefully back of the house. He drew his revolver and, pointing it down, fired. Then he dodged back of an extension and disappeared for the moment. Instantly, the three men sprang up and ran toward the spot where it seemed the shot had been fired. There was no one about the side of the house. But the wind had carried the smoke into some bushes beside the grove and they crashed into the bushes, beating about. At the same time, the naturalist, having first waited until he saw which way the men were going, dashed about the house in the opposite direction. Then he slipped, unopposed and unobserved, in through the open front door, up the stairs and along to the room into which he had just been looking. He unlocked the door, and entered. Elaine was still struggling with the cords when she caught sight of the stranger. "Not a word," he cautioned under his breath. She was indeed too frightened to cry out. Quickly, he loosened her, still holding his finger to his lips to enjoin silence. "Follow me," he whispered. She obeyed mechanically, and they went out into the hall. On down-stairs went the naturalist, Elaine still keeping close after him. He looked out through the front door, then drew back. Quickly he went through the lower hall until he came to the back door in the kitchen, Elaine following. He unbolted the door and opened it. "Run," he said, simply, pointing out of the door. "They're coming back the other way. I'll hold them." She needed no further urging, but darted from the house as he closed the door after her. . . . . . . . It was just at this point that Del Mar came riding along the main road on horseback. He pulled up suddenly as he saw a car run in alongside the road. "That's Elaine's runabout," he muttered, as he dismounted and tied his horse. "How came it here?" He approached the car, much worried by its unaccountable presence there instead of before the St. Germain. Then he drew his gun and hurried up the side road. He heard a shot and quickened his pace. In the woods unexpectedly he came upon his three men still beating about, searching with drawn revolvers for the person who had fired the shot. "Well?" he demanded sharply, "what's all this?" "Some one fired a shot," they explained, somewhat crestfallen. "It was a trick, you fools," he answered testily. "Get back to your prisoner." Without a word they turned and hurried toward the house, Del Mar following. "You two go in," he ordered the foremost. "I'll go around the house with Patrick." As Del Mar and the other man ran around the corner, they could just catch a fleeting glimpse on some one disappearing among the trees. It was Elaine. The man hurried forward, blazing away with his gun. Running, breathless, Elaine heard the shot behind her which Del Mar's man had fired in his eagerness. The bullet struck a tree near her with a "ping!" She glanced back and saw the man. But she did not stop. Instead, she redoubled her efforts, running zigzag in among the trees where they were thickest. Del Mar, a little bit behind his man where she could not recognize him, urged the man on, following carefully. On fled Elaine, her heart beating fast. Suddenly she stopped and almost cried out in vexation. A stream blocked her retreat, a stream, swift and deep. She looked back, terrified. Her pursuers were coming ahead fast now in her direction. Wildly she gazed around. There was a canoe on the bank. In an instant she jumped in, untied it, and seized the paddle. Off she went, striking for the opposite shore. But the current was racing swiftly, and she was already tired and exhausted. She could scarcely make any headway at all in the fierce eddies. But at least, she thought hurriedly, she was getting further and further away from them down-stream. Up above, Del Mar and his man came to the edge of the water. There they stood for a moment looking down. "There she is," pointed the man. Del Mar raised his revolver and fired. Suddenly a bullet struck Elaine's paddle and broke it. Clutching the useless splintered shaft, she was now at the mercy of the current, swept along like a piece of driftwood. She looked about frantically. What was that roaring noise? It was the waterfalls ahead! . . . . . . . In the meantime, Del Mar's other two men had entered the house and had run up-stairs, knowing well his wrath if anything had happened. As they did so, the naturalist poked his head cautiously out of the kitchen where he had been hiding, and saw them. Then he followed noiselessly, his revolver ready. Headlong they ran into the room where they had left Elaine. She was gone! Before they could turn, the naturalist locked the door, turned and took the steps down, two at a time. Then he ran out of the front door and into the woods at an angle to the direction taken by Elaine, turning and going down hill, where a rapid, swollen stream curved about through a gorge. As he reached the stream, he heard a shot above, and a scream. He looked up. There was Elaine, swept down toward him. Below he knew the stream tumbled over a tall cataract into the gorge below. What could he do? A sudden crackling of the twigs caused him to turn and catch sight of me, just coming up. For, as best I could on horseback, I had followed Elaine's car until at last I saw that it had been abandoned. Thoroughly alarmed, I rode on, past a deserted house until suddenly I heard a shot and a scream. It seemed to come from below me and I leaped off my horse, making for it as fast as I could, racing toward a stream whose roar I could hear. There on the bank I came upon a queer old codger, looking about wildly. Was he the automobile thief? I ran forward, ready to seize him. But as I did so, he whirled about and with a strength remarkable in one so old seized my own wrist before I could get his. "Look!" he cried simply, pointing up the stream. I did. A girl in a canoe was coming down toward the falls, screaming, her paddle broken and useless. My heart leaped into my mouth. It was Elaine! "Come," he panted eagerly to me. "I can save her. You must do just as I say." He pointed to an overhanging rock near-by and we ran to it. By this time Elaine was almost upon us, each second getting nearer the veritable maelstrom above the falls. From the rock overhung also a tree at the very edge of the water. There was nothing to do but obey him. Above, though we did not see them, Del Mar and his man were gloating over the result of their work. But they were gloating too soon. We came to the rock and the tree. "Here," cried the new-found friend, "I'll get hold of the tree and then hold you." Instantly he threw himself on his stomach, hooking his leg about the tree trunk. I crawled out over the ledge of slippery rock to the very edge and looked over. It was the only chance. The old naturalist seized my legs in his hands. I slid down the rock, letting myself go. Literally, his presence of mind had invented what was really a life chain, a human rope. On came the canoe, Elaine in it as white as death, crying out and trying to stop or guide it as, nearer and nearer through the smooth-worn walls of the chasm, it whirled to the falls. With a grip of steel, the naturalist held to the tree which swayed and bent, while also he held me, as if in a vise, head down. On came Elaine--directly at us. She stood up and balanced herself, a dangerous feat in a canoe at any time, but doubly so in those dark, swirling, treacherous waters. "Steady!" I encouraged. "Grab my arms!" As the canoe reached us, she gave a little jump and seized my forearms. Her hands slipped, but I grasped her own arms, and we held each other. The momentum of her body was great. For an instant I thought we were all going over. But the naturalist held his grip and slowly began to pull himself and us up the slippery rock. A second later the canoe crashed over the falls in a cloud of spray and pounding water. As we reached the bank above the rock, I almost lifted Elaine and set her down, trembling and gasping for breath. Before either of us knew it the queer old fellow had plunged into the bushes and was gone without another word. "Walter," she cried, "call him back, I must tell him how much I owe him--my life!" But he had disappeared, absolutely. We shouted after him. It was of no use. "Well, what do you think of that?" cried Elaine. "He saved my life--then didn't wait even to be thanked." Who was he? We looked at each other a moment. But neither of us spoke what was in our hearts. CHAPTER XV THE FLASH Alone in the doorway before his rude shack on the shore of the promontory sat an old fisherman, gazing out fixedly at the harbor as though deeply concerned over the weather, which, as usual, was unseasonable. Suddenly he started and would have disappeared into his hut but for the fact that, although he could not himself be seen, he had already seen the intruder. It was a trooper from Fort Dale. He galloped up and, as though obeying to the letter his instructions, deliberately dropped an envelope at the feet of the fisherman. Then, without a word, he galloped away again. The fisherman picked up the envelope and opened it quickly. Inside was a photograph and a note. He read: FORT DALE PROFESSOR ARNOLD, J. Smith, clerk in the War Department, has disappeared. We are not sure, but fear that he has a copy of the new Sandy Hook Defense Plans. It is believed he is headed your way. He walks with a slight limp. Look out for him. LIEUTENANT WOODWARD. For a long time the fisherman appeared to study the face on the photograph until he had it indelibly implanted in his memory, as if by some system such as that of the immortal Bertillon and his clever "portrait parle," or spoken picture, for scientific identification and apprehension. It was not a pleasant face and there were features that were not easily forgotten. Finally he turned and entered his hut. Hastily he took off his stained reefer. From a wooden chest he drew another outfit of clothes. The transformation was complete. When he issued forth from his hut again, it was no longer the aged disciple of Izaac Walton. He was now a trim chauffeur, bearded and goggled. . . . . . . . In the library of his bungalow, Del Mar was pacing up and down, now and then scowling to himself, as though there flashed over his mind stray recollections of how some of his most cherished plans were miscarrying. Still, on the whole, he had nothing to complain of. For, a moment later the valet entered with a telegram for which he had evidently been waiting. Del Mar seized it eagerly and tore open the yellow envelope. On the blank was printed in the usual way the following non-committal message: WASHINGTON, D. C., August 12, 1915. MR. DEL MAR, What you request is coming. Answer to sign of the ring.--SMITH. "Good," muttered Del Mar as he finished reading. "Strange, what a little gold will do--when you know how to dispose of it." He smiled cynically to himself at the sentiment. . . . . . . . At the little railroad station, they were quite proud of the fact that at least two of the four hacks had been replaced already by taxicabs. It was, then, with some surprise and not a little open jealousy that they saw a new taxicab drive up and take its stand by the platform. If the chauffeur, transformed from the lonely fisherman, had expected a cordial reception, he might better have stayed before his hut, for the glances the other drivers gave him were as black and lowering as the clouds he had been looking at. The new chauffeur got off his seat. Instead of trying to brazen it out, he walked over to the others who were standing in a group waiting for the approaching train whose whistle had already sounded. "I'm not going to locate here permanently," he said, pulling out a roll of bills as he spoke. "Leave any fare I claim to me," he added, passing a bill of a good denomination to each of the four jehus. They looked at him curiously. But what business of theirs was it? The money felt good. "All right, bo," they agreed. Thundering down the platform came the afternoon train, a great event in the town life. As the baggage was being tossed off, the passengers alighted and the five hackmen swarmed at them. "Keb, sir, kerridge. Taxi, lady!" From the Pullman alighted a widow, in deep mourning. As she got off and moved down the platform, it was apparent that she walked with a pronounced limp. At the end of the platform, the chauffeurs were still calling, while the newcomer looked over the crowd hastily. Suddenly he caught sight of the face of the widow. He stepped forward, as she approached. The others held back as they had agreed and paid no attention. It was like forcing a card. He held the door open and she entered the cab, unsuspecting. "Mr. Del Mar's," she directed, simply. As the new taxicab driver cranked his engine and climbed into the seat, he was careful to let no action of his, however small, betray the intense satisfaction he felt at the working of his scheme. He pulled away from the station. On through the pretty country roads the chauffeur drove the heavily veiled widow until at last they came to Del Mar's bungalow. At the gate he stopped and ran around to open the door to assist his fare to alight. "Wait for me," she said, without paying him yet. "I shall not be long and I want to be driven back to the station to catch the four twenty-nine to New York." As she limped up the gravel walk, he watched her closely. She went to the door and rang the bell, and the valet admitted her. Del Mar was still sitting, thinking, in the library. "Mr. Del Mar?" she inquired. The voice was not exactly soft, and Del Mar eyed her suspiciously. Was this the person he expected, or a "plant?" "Yes," he answered, guardedly, "I am Mr. Del Mar. And you?" The widow, too, evidently wished to make no mistake. As she spoke, she raised her hand. By that simple action she displayed a curious and conspicuous seal ring on her finger. It was the sign of the ring for which Del Mar had been waiting. He extended his own left hand. On the ring finger was another ring, but not similar. As he did so, the widow took the ring from her own finger and placed it on the little finger of Del Mar. "Good!" he exclaimed. Every action of the sign of the ring had been carried out. The woman raised her thick veil, disclosing the face of--a man! It was the same face, also, that had appeared in the photograph sent to the old fisherman by Woodward. Awkwardly, the man searched in the front of his shirtwaist and drew forth a paper which Del Mar almost seized in his eagerness. It was a pen and ink copy of a Government map, showing a huge spit of sand in the sea before a harbor, Sandy Hook and New York. On it were indicated all the defenses, the positions of guns, everything. Together, Del Mar and Smith bent over it, while the renegade clerk explained each mark on the traitorous map. They were too occupied to see a face flattened against the pane of a window near-by. The chauffeur had no intention of remaining inactive outside while he knew that something that interested him was transpiring inside. He had crept up by the side of the house to the window. But he could see little and hear nothing. A moment he strained every sense. It was no use. He must devise some other way. How could he get into that room? Slowly he returned to his car, thinking it over. There he stood for a moment revolving in his mind what to do. He looked up the road. An idea came to him. There he saw a little runabout approaching rapidly. Quickly he went around to the front of his car and lifted up the hood. Then he bent over and pretended to be tinkering with his engine. As the car was about to pass he deliberately stepped back, apparently not seeing the runabout, and was struck and knocked down. The runabout stopped, the emergency brakes biting hard. . . . . . . . Elaine had asked me to go shopping in the village with her that afternoon. While I waited for her in her little car, she came down at last, carrying a little handbag. We drove off a moment later. It was a delightful ride, not too warm, but sunny. Without realizing it, we found ourselves on the road that led past Del Mar's. As we approached, I saw that there was a taxicab standing in front of the gate. The hood was lifted and the driver was apparently tinkering with his engine. "Let's not stop," said Elaine, who had by this time a peculiar aversion to the man. As we passed the driver, apparently not seeing us, stepped out and, before we could turn out, we had knocked him down. We stopped and ran back. There he lay on the road, seemingly unconscious. We lifted him up and I looked toward Del Mar's house. "Help!" I shouted at the top of my voice. The valet came to the door. Hearing me, the valet ran out down the walk. "All right," he cried. "I'll be there in a minute." With his help I picked up the taxicab chauffeur and we carried him into the house. Del Mar was talking with a person who looked like a widow, when they heard our approach up the walk carrying the injured man. So engrossed had they been in discerning what the stolen document contained that, as we finally entered, the widow had only time to drop her veil and conceal her identity as the renegade Smith. Del Mar still held the plan in his hand. The valet and I entered with Elaine and we placed the chauffeur on a couch near Del Mar's desk. I remember that there was this strange woman all in black, heavily veiled, in the room at the time. "I think we ought to telephone for a doctor," said Elaine placing her hand-bag on the desk and excitedly telling Del Mar how we had accidentally knocked the man down. "Call up my doctor, Henry," said Del Mar, hastily thrusting the plan into a book lying on the desk. We gathered about the man, trying to revive him. "Have you a little stimulant?" I asked, turning from him. Del Mar moved toward a cellarette built into the wall. We were all watching him, our backs to the chauffeur, when suddenly he must have regained consciousness very much. Like a flash his hand shot out. He seized the plan from between the leaves of the book. He had not time to get away with it himself. Perhaps he might be searched. He opened Elaine's bag, and thrust it in. The valet by this time had finished telephoning and spoke to Del Mar. "The doctor will be here shortly, Miss Dodge," said Del Mar. "You need not wait, if you don't care to. I'll take care of him." "Oh, thank you--ever so much," she murmured. "Of course it wasn't our fault, but I feel sorry for the poor fellow. Tell the doctor to send me the bill." She and Del Mar shook hands. I thought he held her hand perhaps a little longer and a little tighter than usual. At any rate Elaine seemed to think so. "Why, what a curious ring, Mr. Del Mar," she said, finally releasing her own hand from his grasp. Then she looked quickly at the woman, half joking, as if the ring had something to do with the strange woman. She looked back at the ring. Del Mar smiled, shook his head and laughed easily. Then Elaine picked up her bag and we went out. A moment later we climbed back into the car and were off again. . . . . . . . Having left us at the door, Del Mar hurried back to the library. He went straight to the desk and picked up the book, eager now to make sure of the safety of the plan. It was gone! "Did you, Smith--" he began hastily, then checked himself, knowing that the clerk had not taken the plan. Del Mar walked over to the couch and stood a moment looking at the chauffeur. "I wonder who he is," he said to himself. "I don't recall ever seeing him at the station or in the village." He leaned over closer. "The deuce!" he exclaimed, "that's a fake beard the fellow has on." Del Mar made a lunge for it. As he did so, the chauffeur leaped to his feet and drew a gun. "Hands up!" he shouted. "And the first man that moves is a dead one!" Before the secret agent knew it, both he and Smith were covered. The chauffeur took a step toward Smith and unceremoniously jerked off the widow's weeds, as well as the wig. At that very moment one of Del Mar's men came up to the secret panel that opened from the underground passageway into his library. He was about to open it when he heard a sound on the other side that startled him. He listened a moment, then slid it just a short distance and looked in. There he saw a chauffeur holding up Del Mar and Smith. Having pulled the disguise from Smith, he went next around Del Mar and took his gun from his pocket, then passed his hands over the folds of Smith's dress, but found no weapon. He stepped back away from them. At that point the man quietly slid the panel all the way open and silently stepped into the room, behind the chauffeur. Cautiously he began sneaking up on him. As he did so, Del Mar and Smith watched, fascinated. Somehow their faces must have betrayed that something was wrong. For, as the newcomer leaped at him, the chauffeur turned suddenly and fired. The shot wounded the man. It was a signal for a free-for-all fight. Del Mar and Smith leaped at the intruder. Over and over they rolled, breaking furniture, overturning and smashing bric-a-brac. Del Mar's revolver was knocked out of the chauffeur's hand. With a blow of a chair, the chauffeur laid out Smith, entangled in his unfamiliar garments, shook himself loose from the two others, and made a rush at the door. Del Mar paused only long enough to pick up the revolver from the floor. Instantly he fired at the retreating form. But the chauffeur had passed out and banged shut the door. Down the walk he sped and out to the gate, into his car, the engine of which he had left running. Hard after him came Del Mar and the rest, joined now by Henry, the valet. One shot was left in the chauffeur's revolver and he blazed away as he leaped into the car. "He's got me," groaned Smith as he stumbled and fell forward. On kept Del Mar and the others. They caught up with the car just as it was starting. But the chauffeur knocked the gun from Del Mar's hand before he could get a good aim and fire, at the same time bowling over the man who had come through the panel. Off the car went, now rapidly gaining speed. Del Mar had just time to swing on the rear of it. Around the rapidly-driven car, he climbed, hanging on for dear life, over the mud-guard and toward the running-board. On sped the car, swaying crazily back and forth, Del Mar crouched on the running-board and working his way slowly and perilously to the front seat. The chauffeur felt the weight of some one on that side. Just as he turned to see what it was, Del Mar leaped at him. Still holding the wheel, the chauffeur fought him off with his free hand, Del Mar holding on to some spare tires with one hand, also. Handicapped by having the steering-wheel to manage, nevertheless the chauffeur seemed quite well able to give a good account of himself. . . . . . . . Somehow, Elaine and I must have been hoodooed that day. We had not been gone five minutes from Del Mar's after the accident to the chauffeur, when we heard a mysterious knock in the engine. "More engine trouble," I sighed. "Pull up along the road and I'll see if I can fix it." We stopped and both got out. There was no fake about this trouble or about the dirt and grease I acquired on my hands and face, tinkering with that motor. For, regardless of my immaculate flannels, I had to set to work. A huge spot of grease spattered on me. Elaine laughed outright. "Here, let me powder your nose, Walter," she cried undismayed at our trouble, gayly opening her bag. "Well--of all things--what's this, and where did it come from?" I turned from the engine and looked. She was holding some kind of plan or document in her hand. In blank surprise she examined it. It looked like a fort or a series of forts. But I was sure at a glance that it was not Fort Dale. "What do you think it is, Walter?" she asked, handing it to me. I took it and examined it carefully. Incredible as it seemed, I figured out quickly that it must be nothing short of a plan of the new defenses at Sandy Hook. "I don't know what it all means," I said. "But I do know that we won't get any dinner till I get this engine running again." I fell to work again, eager to get away with our dangerous prize, Elaine now and then advising me. Finally I turned the engine over. For a wonder it ran smoothly. "Well, that's all right, at last," I sighed, wiping the grease off my hands on a piece of waste. "What's the matter now?" exclaimed Elaine, turning quickly and looking up the road along which we had just come. There, lurching along at full speed was a car. Two men were actually fighting on the front of it regardless of speed and safety. As it neared us, I saw it was the taxicab that had been standing before Del Mar's. I looked closer at it. To my utter amazement, who should be driving it but the very chauffeur whom we had left at Del Mar's only a few minutes before, apparently unconscious. He could not have been hurt very badly, for he was not only able to drive but was fighting off a man clinging on the running-board. On rushed the car, directly at us. Just as it passed us, the chauffeur seemed to summon all his strength. He struck a powerful blow at the man, recoiled and straightened out his car just in time. The man fell, literally at our feet. It was Del Mar himself! On sped the taxicab. Bruised though he must have been by the fall, Del Mar nevertheless raised himself by the elbow and fired every chamber of his revolver as fast as he could pump the bullets. I must say that I admired the man's pluck. Elaine and I hurried over to him. I still had in my hand the queer paper which she had found so strangely in her hand-bag. "Why, what's all this about?" I asked eagerly. Before I could raise him up, Del Mar had regained his feet. "Just a plain crook, who attacked me," he muttered, brushing off his clothes to cover up the quick recognition of what it was that I was holding in my hand, for he had seen the plan immediately. "Can't we drive you back?" asked Elaine, quite forgetting our fears of Del Mar in the ugly predicament in which he just had been. "We've had trouble but I guess we can get you back." "Thank you," he said, forcing a smile. "I think anything would be an improvement on my ride here and I'm sure you can do more than you claim." He climbed up and sat on the floor of the roadster, his feet outside, and we drove off. At last we pulled up at Dodge Hall again. "Won't you come in?" asked Elaine as we got out. "Thank you, I believe I will for a few minutes," consented Del Mar, concealing his real eagerness to follow me. "I'm all shaken up." As we entered the living-room, I was thinking about the map. I opened a table drawer, hastily took the plan from my pocket and locked it in the drawer. Elaine, meanwhile, was standing with Del Mar who was talking, but in reality watching me closely. A smile of satisfaction seemed to flit over his face as he saw what I had done and now knew where the paper was. I turned to him. "How are you now?" I asked. "Oh, I'm much better--all right," he answered. Then he looked at his watch. "I've a very important appointment. If you'll excuse me, I'll walk over to my place. Thank you again, Miss Dodge, ever so kindly." He bowed low and was gone. . . . . . . . Down the road past where we had turned, before a pretty little shingle house, the taxicab chauffeur stopped. One of the bullets had taken effect on him and his shoulder was bleeding. But the worst, as he seemed to think it, was that another shot had given him a flat tire. He jumped out and looked up the road whence he had come. No one was following. Still, he was worried. He went around to look at the tire. But he was too weak now from loss of blood. It had been nerve and reserve force that had carried him through. Now that the strain was off, he felt the reaction to the full. Just then the doctor and his driver, whom the valet had already summoned to Del Mar's, came speeding down the road. The doctor saw the chauffeur fall in a half faint, stopped his car and ran to him. The chauffeur had kept up as long as he could. He had now sunk down beside his machine in the road. A moment later they picked him up and carried him into the house. There was no acting about his hurts now. In the house they laid the man down on a couch and the doctor made a hasty examination. "How is he?" asked one of the kind Samaritans. "The wound is not dangerous," replied the physician, "but he's lost a lot of blood. He cannot be moved for some time yet." . . . . . . . We talked about nothing else at Dodge Hall after dressing for dinner but the strange events over at Del Mar's and what had followed. The more I thought about it, the more it seemed to me that we would never be left over night in peaceful possession of the plan which both Elaine and I decided ought on the following day to be sent to Washington. Accordingly I cudgelled my brain for some method of protecting both ourselves and it. The only thing I could think of was a scheme once adopted by Kennedy in another case. How I longed for him. But I had to do my best alone. I had a small quick shutter camera that had belonged to Craig and just as we were about to retire, I brought it into the living-room with a package I had had sent up from the village. "What are you going to do?" asked Elaine curiously. I assumed an air of mystery but did not say, for I was not sure but that even now some one was eavesdropping. It was not late, but the country air made us all sleepy and Aunt Josephine, looking at the clock, soon announced that she was going to retire. She had no sooner said good-night than Elaine began again to question me. But I had determined not to tell her what I was doing, for if my imitation of Kennedy failed, I knew that she would laugh at me. "Oh, very well," she said finally in pique, "then, if you're going to be so secret about it, you can sit up alone--there!" She flounced off to bed. Sure as I could be at last that I was alone, I opened the package. There were the tools that I had ordered, a coil of wire and some dry cells. Then I went to the table, unlocked the drawer and put the plan in my pocket. I had determined that whether the idea worked or not, no one was to get the plan except by overcoming me. Although I was no expert at wiring, I started to make the connections under the table with the drawer, not a very difficult thing to do as long as it was to be only temporary and for the night. From the table I ran the wires along the edge of the carpet until I came to the book-case. There, masked by the books, I placed the little quick shutter camera, and at a distance also concealed the flash-light pan. Next I aimed the camera carefully and focussed it on a point above the drawer on the writing-table where any one would be likely to stand if he attempted to open it. Then I connected the shutter of the camera and a little spark coil in the flash-pan with the wires, using an apparatus to work the shutter such as I recalled having seen Craig use. Finally I covered the sparking device with the flash-light powder, gave a last look about and snapped off the light. Up in my bedroom, I must say I felt like "some" detective and I could not help slapping myself on the chest for the ingenuity with which I had duplicated Craig. Then I lay down on the bed with my clothes on and picked up a book, determined to keep awake to see if anything happened. It was a good book, but I was tired and in spite of myself I nodded over it, and then dropped it. . . . . . . . In his bungalow, now that Smith had gone back again to New York and Washington, Del Mar was preparing to keep the important engagement he had told us about, another of his nefarious nocturnal expeditions. He drew a cap on his head, well over his ears and forehead. His eyes and face he concealed as well as he could with a mask to be put on later. To his equipment he added a gun. Then with a hasty word or two to his valet, he went out. By back ways so that even in the glare of automobile headlights he would not be recognized, he made his way to Dodge Hall. As he saw the house looming up in the moonlight he put on his mask and approached cautiously. Gaining the house, he opened a window, noiselessly turning the catch as deftly as a house-breaker, and climbed into the living-room. A moment he looked around, then tiptoed over to the table. He looked at it to be sure that it was the right one and the right drawer. Then he bent down to force the drawer open. "Pouf!" a blinding flash came and a little metallic click of the shutter, followed by a cloud of smoke. As quick as it happened, there went through Del Mar's head, the explanation. It was a concealed camera. He sprang back, clapping his hands over his face. Out of range for a moment, he stood gazing about the room, trying to locate the thing. Suddenly he heard footsteps. He dived through the window that he had opened, just as some one ran in and switched on the lights. . . . . . . . Half asleep, I heard a muffled explosion, as if of a flash-light. I started up and listened. Surely some one was moving about down-stairs. I pulled my gun from my pocket and ran out of the room. Down the steps I flung myself, two at a time. In the living-room, I switched on the lights in time to see some one disappear through an open window. I ran to the window and looked out. There was a man, half doubled up, running around the side of the house and into a clump of bushes, then apparently lost. I shot out of the window and called. My only answer was an imprecation and return volley that shattered the glass above my head. I ducked hastily and fell flat on the floor, for in the light streaming out, I must have been a good mark. I was not the only one who heard the noise. The shots quickly awakened Elaine and she leaped out of bed and put on her kimono. Then she lighted the lights and ran down-stairs. The intruder had disappeared by this time and I had got up and was peering out of the window as she came breathlessly into the living-room. "What's the matter, Walter?" she asked. "Some one broke into the house after those plans," I replied. "He escaped, but I got his picture, I think, by this device of Kennedy's. Let's go into a dark room and develop it." There was no use trying to follow the man further. To Elaine's inquiry of what I meant, I replied by merely going over to the spot where I had hidden the camera and disconnecting it. We went up-stairs where I had rigged up an impromptu dark room for my amateur photographic work some days before. Elaine watched me closely. At last I found that I had developed something. As I drew the film through the hypo tray and picked it up, I held it to the red light. Elaine leaned over and looked at the film with me. There was a picture of a masked man, his cap down, in a startled attitude, his hands clapped to his face, completely hiding what the mask and cap did not hide. "Well, I'll be blowed!" I cried in chagrin at the outcome of what I thought had been my cleverest coup. A little exclamation of astonishment escaped Elaine. I turned to her. "What is it?" I asked. "The ring!" she cried. I looked again more closely. On the little finger of the left hand was a peculiar ring. Once seen, I think it was not readily forgotten. "The ring!" she repeated excitedly. "Don't you remember--that ring? I saw it on Mr. Del Mar's hand--at his house--this afternoon!" I could only stare. At last we had a real clue! In his bungalow, Del Mar at that moment threw down his hat and tore off his mask furiously. What had he done? For a long time he sat there, his chin on his hand, gazing fixedly before him, planning to protect himself and revenge. CHAPTER XVI THE DISAPPEARING HELMETS It was early the following morning that, very excited, Elaine and I showed Aunt Josephine the photograph which we had snapped and developed by using Kennedy's trick method. "But who is it?" asked Aunt Josephine examining the print carefully and seeing nothing but a face masked and with a pair of hands before it, a seal ring on the little finger of one hand. "Oh, I forgot that you hadn't seen the ring before," explained Elaine. "Why, we knew him at once, in spite of everything, by that seal ring--Mr. Del Mar!" "Mr. Del Mar?" repeated Aunt Josephine, looking from one to the other of us, incredulous. "I saw the ring at his own bungalow and on his own finger," reiterated Elaine positively. "But what are you going to do, now?" asked Aunt Josephine. "Have him arrested, of course," Elaine replied. Still talking over the strange experience of the night before, we went out on the veranda. "Well, of all the nerve!" exclaimed Elaine, catching sight of a man coming up the gravel walk. "If that isn't Henry, Mr. Del Mar's valet!" The valet advanced as though nothing had happened and, indeed, I suppose that as far as he knew nothing had happened or was known to us. He bowed and handed Elaine a note which she tore open quickly and read. "Would you go?" she asked, handing the note over to me. It read: DEAR MISS DODGE, If you and Mr. Jameson will call on me to-day, I will have something of interest to tell you concerning my investigations in the case of the disappearance of Craig Kennedy. Sincerely, M. DEL MAR. "Yes," I asserted, "I would go." "Tell Mr. Del Mar we shall see him as soon as possible," nodded Elaine to the valet who bowed and left quickly. "What is it?" inquired Aunt Josephine, rejoining us. "A note from Mr. Del Mar," replied Elaine showing it to her. "Well," queried Aunt Josephine, "what are you going to do?" "We're going, of course," cried Elaine. "You're not," blurted out Aunt Josephine. "Why, just think. He's sure to do something." But Elaine and I had made up our minds. "I know it," I interjected. "He's sure to try something that will show his hand--and then I've got him." Perhaps I threw out my chest a little more than was necessary, but then I figured that Elaine with her usual intuition had for once agreed with me and that it must be all right. I drew my gun and twirled the cylinder about as I spoke. Indeed I felt, since the success of the snapshot episode, that I was a match for several Del Mar's. "Yes, Walter is right," agreed Elaine. Aunt Josephine continued to shake her head sagely in protest. But Elaine waved all her protestations aside and ran into the house to get ready for the visit. Half an hour later, two saddle horses were brought around to the front of Dodge Hall and Elaine and I sallied forth. Aunt Josephine was still protesting against our going to Del Mar's, but we had made up our minds to carry the thing through. "You know," she insisted, "that Mr. Kennedy is not around to protect you two children. Something will surely happen to you if you don't keep out of this affair." "Oh, Auntie," laughed Elaine, a bit nervously, however, "don't be a kill-joy. Suppose Craig isn't about? Who's going to do this, if Walter and I don't?" In spite of all, we mounted and rode away. . . . . . . . Del Mar, still continuing his nefarious work of mining American harbors and bridges, had arrived at a scheme as soon as he returned from the attempt to get back from us the Sandy Hook plans. Smith, who had stolen the plans from the War Department, was still at the bungalow. Early in the morning, Del Mar had seated himself at his desk and wrote a letter. "Here, Henry," he directed his valet, "take this to Miss Dodge." As the valet went out, he wrote another note. "Read that," he said, handing it over to Smith. "It's a message I want you to take to headquarters right away." It was worded cryptically: A. A. L. N. Y. Closely watched. Must act soon or all will be discovered.--M. Smith read the note, nodded, and put it into his pocket, as he started to the door. "No, no," shouted Del Mar, calling him back. "This thing means that you'll have to be careful in your getaway. You'd better go out through my secret passage," he added, pointing to the panel in the library wall. He pressed the button on the desk and Smith left through the hidden passage. Down it he groped and at the other end emerged. Seeing no one around, he made his way to the road. There seemed to be no one who looked at all suspicious on the road, either, and Smith congratulated himself on his easy escape. On a bridge over a creek, however, as Smith approached, was one inoffensive-looking person who might have been a minister or a professor. He was leaning on the rail in deep thought, gazing at the creek that ran beneath him, and now and then flashing a sharp glance about. Suddenly he saw something approaching. Instantly he dodged to the farther end of the bridge and took refuge behind a tree. Smith walked on over the bridge, oblivious to the fact that he was watched. No sooner had he disappeared than the inquisitive stranger emerged again from behind the tree. It was the mysterious Professor Arnold who many times had shown a peculiar interest in the welfare of Elaine and myself. Evidently he had recognized Del Mar's messenger, for after watching him a moment he turned and followed. At the railroad station, just before the train for New York pulled in, the waiting crowd was increased by one stranger. Smith had come in and taken his place unostentatiously among them. But if he thought he was to be lost in the little crowd, he was much mistaken. Arnold had followed, but not so quickly that he had not had time to pick up the two policemen that the town boasted, both of whom were down at the station at the time. "There he is," indicated Arnold, "the fellow with the slight limp. Bring him to my room in the St. Germain Hotel." "All right, sir," replied the officers, edging their way to the platform as Arnold retreated back of the station and disappeared up the street. Just then the train pulled into the station and the passengers crowded forward to mount the steps. Smith was just about to push his way on with them, when the officers elbowed through the crowd. "You're wanted," hissed one of them, seizing his shoulder. But Smith, in spite of his deformity, was not one to submit to arrest without a struggle. He fought them off and broke away, running toward the baggage-room. As he rushed in, they followed. One of them was gaining on him and took a flying football tackle. The other almost fell over the twisted mass of arms and legs. The struggle now was short and sharp and ended in the officers slipping the bracelets over the wrists of Smith. While the passengers and bystanders crowded about to watch the excitement, they led him off quickly. . . . . . . . In his rooms at the St. Germain, cluttered with test tubes and other paraphernalia which indicated his scientific tendencies, Professor Arnold entered and threw off his hat, lighting a cigarette and waiting impatiently. He had not as long to wait as he had expected. A knock sounded at the door and he opened it. There was Smith handcuffed and forced in by the two policemen. "Good work," commended Arnold, at once setting to work to search the prisoner who fumed but could not resist. "What have we here?" drawled Arnold in mock courtesy and surprise as he found and drew forth from Smith's pocket a bundle of papers, which he hastily ran through. "Ah!" he muttered, coming to Del Mar's note, which he opened and read. "What's this? 'A. A. L. N. Y. Closely watched. Must act soon or all will be discovered. M.' Now, what's all that?" Arnold pondered the text deeply. "You may take him away, now," he concluded, glancing up from the note to the officers. "Thank you." "All right, sir," they returned, prodding Smith along out. Still studying the note, Arnold sat down at the desk. Thoughtfully he picked up a pencil. Under the letters A. A. L. he slowly wrote "Anti-American League" and under the initial M the name, "Martin." "Now is the time, if ever, to use that new telaphotograph instrument which I have installed for the War Department in Washington and carry around with me," he said to himself, rising and going to a closet. He took out a large instrument composed of innumerable coils and a queer battery of selenium cells. It was the receiver of the new instrument by which a photograph could be sent over a telegraph wire. Down-stairs, in the telegraph room of the hotel, Arnold secured the services of one of the operators. Evidently by the way they obeyed him they had received orders from the company regarding him, and knew him well there. "I wish you'd send this message right away to Washington," he said, handing in a blank he had already written. The clerk checked it over: U. S. WAR DEPARTMENT, Washington, D. C. Wire me immediately photograph and personal history of Martin arrested two years ago as head of Anti-American League.--ARNOLD. As the message was ticked off, Arnold attached his receiving telaphotograph instrument to another wire. It was a matter scarcely of seconds before a message was flashed back to Arnold from Washington: Martin escaped from Fort Leavenworth six months ago. Thought to be in Europe. Photograph follows. EDWARDS. "Very well," nodded Arnold with satisfaction. "I think I know what is going on here now. Let us wait for the photograph." He went over to the new selenium telaphotograph and began adjusting it. Far away, in Washington, in a room in the War Department where Arnold had already installed his system for the secret government service, a clerk was also working over the sending part of the apparatus. No sooner had the clerk finished his preparations and placed a photograph in the transmitter than the buzzing of the receiver which Arnold had installed announced to him that the marvellous transmission of a picture over a wire, one of the very newest triumphs of science, was in progress. In the little telegraph office of the St. Germain, the clerks and operators crowded about Arnold, watching breathlessly. "By Jove, it works!" cried one, no longer sceptical. Slowly a print was being evolved before their eyes as if by a spirit hand. Arnold watched the synchronizer apparatus carefully as, point after point, the picture developed. He bent over closely, his attention devoted to every part of the complicated apparatus. At last the transmission of the photograph was completed and the machine came to rest. Arnold almost tore the print from the receiver and held it up to examine it. A smile of intense satisfaction crossed his face. "At last!" he muttered. There was a photograph of the man who had been identified with the arch conspirators of two years before, Martin. Only, now he had changed his name and appeared in a new role. It was Marcus Del Mar! . . . . . . . Already, in the library of his bungalow, Del Mar had summoned one of his trusted men and was talking to him, when Henry, the valet, reentered after his trip to see us. "They're coming as soon as they can," he reported. Del Mar smiled a cynical smile. "Good," he exclaimed triumphantly, then, looking about at the electric fixtures, added to the man, "Let us see where to install the thing." He walked over to the door and put his hand on the knob, then pointed back at the fixtures. "That's the idea," he cried. "You can run the line from the brackets to this door-knob and the mat. How's that?" "Very clever," flattered the man, putting on a heavy pair of rubber gloves. Taking a pair of pliers and other tools from a closet in the library, he began removing the electric fixture from the wall. As Del Mar directed, the man ran a wire from the fixture along the moulding, and down the side of a door, where he made a connection. In the meantime Del Mar brought out a wire mat and laid it in front of the door where any one who entered or left would be sure to step on it. The various connections made, the man placed a switch in the concealment of a heavily-curtained window and replaced everything as he found it. Thus it was that Elaine and I came at last to Del Mar's bungalow, I must admit, with some misgivings. But I had gone too far to draw back now and Elaine was more eager even than I was. We dismounted, tethered our horses and went toward the house, where I rang the bell. Preparations for our reception had just been completed and Del Mar was issuing his final instructions to his man, when the valet, Henry, ran in hastily. "They're here, sir, now," he announced excitedly. "All right, I'm ready," nodded Del Mar, turning to his man again and indicating a place back of the folds of the heavy curtains by the window. "You get back there by that switch. Don't move--don't even breathe. Now, Henry, let them in." As his valet withdrew Del Mar gazed about his library to make sure that everything was all right. Just then the valet reappeared and ushered us in. "Good morning," greeted Del Mar pleasantly. "I see that you got my note and I'm glad you were so prompt. Won't you be seated?" Both Elaine and I were endeavoring to appear at ease. But there was a decided tension in the atmosphere. We sat down, however. Del Mar did not seem to notice anything wrong. "I've something at last to report to you about Kennedy," he said a moment later, clearing his throat. . . . . . . . Aunt Josephine turned from us as Elaine and I rode off on our horses from Dodge Hall considerably worried. Then an idea seemed to occur to her and she walked determinedly into the house. "Jennings," she called to the butler, "have the limousine brought around from the garage immediately." "Yes, ma'am," acquiesced the faithful Jennings, hurrying out. It was only a few minutes later that the car pulled around before the door. Aunt Josephine bustled out and entered. "Fort Dale," she directed the driver, greatly agitated. "Ask for Lieutenant Woodward." Out at Fort Dale, Woodward was much astonished when an orderly announced that Aunt Josephine was waiting in her car to see him on very urgent business. He ordered that she be admitted at once. "I hope there's nothing wrong?" he inquired anxiously, as he noted the excitement and the worried look on her face. "I--I'm afraid there may be," she replied, sitting down and explaining what Elaine and I had just done. The Lieutenant listened gravely. "And," she concluded, "they wouldn't listen to me, Lieutenant. Can't you follow them and keep them out of trouble?" Woodward who had been listening to her attentively jumped up as she concluded. "Yes," he cried sympathetically, "I can. I'll go myself with some of the men from the post. If they get into any scrape, I'll rescue them." Almost before she could thank him, Woodward had hurried from his office, followed by her. On the parade grounds were some men. Quickly he issued his orders and a number of them sprang up as he detailed them off for the duty. It was only a moment before they returned, armed. An instant later three large touring cars from the Fort swept up before the office of Woodward. Into them the armed men piled. "Hurry--to the Del Mar bungalow," ordered the Lieutenant, jumping up with the driver of the first car. "We must see that nothing happens to Miss Dodge and Mr. Jameson." They shot away in a cloud of dust, followed hard by the other two cars, dashing at a breakneck speed over the good roads. In the narrow, wooded roadway near Del Mar's, Woodward halted his car and the soldiers all jumped out and gathered about him as hastily he issued his directions. "Surround the house, first," he ordered. "Then arrest any one who goes in or out." They scattered, forming a wide circle. As soon as word was passed that the circle was completed, they advanced cautiously at a signal from Woodward, taking advantage of every concealment. . . . . . . . Around in the kitchen back of Del Mar's, Henry, the valet, had retired to visit one of the maids. He was about to leave when he happened to look out of the window. "What's that?" he muttered to himself. He stepped back and peered cautiously through the window again. There he could see a soldier, moving stealthily behind a bush. He drew back further and thought a minute. He must not alarm us. Then he wrote a few words on a piece of paper and tore it so that he could hold it in his palm. Next he hurried from the kitchen and entered the study. Del Mar had scarcely begun to outline to us a long and circumstantial pseudo-investigation into what he was pleased to hint had been the death of Kennedy, when we were interrupted again by the entrance of his valet. "Excuse me, sir," apologized Henry, as Del Mar frowned, then noted that something was wrong. As the valet said the words, he managed surreptitiously to hand to Del Mar the paper which he had written, now folded up into a very small space. I had turned from Del Mar when the valet entered, apparently to speak to Elaine, but in reality to throw them off their guard. Under that cover I was able to watch the precious pair from the tail of my eye, I saw Del Mar nod to the valet as though he understood that some warning was about to be conveyed. Although nothing was said, Del Mar was indicating by dumb show orders of some kind. I had no idea what it was all about but I stood ready to whip out my gun on the slightest suspicious move from either. "I hope you'll pardon me, Miss Dodge," Del Mar deprecated, as the valet retreated toward the door to the kitchen and pantry. "But, you see, I have to be housekeeper here, too, it seems." Actually, though he was talking to us, it was in a way that enabled him by palming something in his hand, I fancied, to look at it. It was, though I did not know it, the hastily scrawled warning of the valet. It must have been hard to read, for I managed by a quick shift at last to catch just a fleeting glimpse that it was a piece of paper he held in his hand. What was it, I asked myself, that he should be so secret about it? Clearly, I reasoned, it must be something that was of interest to Elaine and myself. If I must act ever, I concluded, now was the time to do so. Suddenly I reached out and snatched the note from his hand. But before I could read it Del Mar had sprung to his feet. At the same instant a man leaped out from behind the curtains. But I was on my guard. Already I had drawn my revolver and had them all covered before they could make another move. "Back into that corner--by the window--all of you," I ordered, thinking thus to get them together, more easily covered. Then, handing the note, with my other hand, to Elaine, I said to her, "See what it says--quick." Eagerly she took it and read aloud, "House surrounded by soldiers." "Woodward," I cried. Still keeping them covered, I smiled quietly to myself and took one step after another slowly to the door. Elaine followed. I reached the door and I remember that I had to step on a metal mat to do so. I put my hand behind me and grasped the knob about to open the door. As I did so, the man who had jumped from behind the curtain suddenly threw down his upraised hands. Before I could fire, instantaneously in fact, I felt a thrill as though a million needles had been thrust into all parts of my body at once paralyzing every muscle and nerve. The gun fell from my nerveless hand, clattering to the floor. The man had thrown an electric switch which had completed a circuit from the metal mat to the door-knob through my body and then to the light and power current of high power. There I was, held a prisoner, by the electric current! At the same instant, also, Del Mar with an oath leaped forward and seized Elaine by the arms. I struggled with the door-knob but I could no more let go than I could move my feet off that mat. It was torture. "Henry!" called Del Mar to the valet. "Yes, sir." "Open the cabinet. Give me the helmets and the suits." The valet did so, bringing out a number of queer looking head-pieces with a single weird eye of glass in the front, as well as rubber suits of an outlandish design. While he was doing so, Del Mar stuffed a handkerchief into Elaine's mouth to keep her quiet. By this time, Del Mar, as well as the man from behind the curtains and the valet were provided with suits, and one at a time holding Elaine, the others put them on. Del Mar moved toward Elaine, holding an extra helmet. He strapped it on her, then started to force her into a suit. I struggled still, but in vain, to free myself from the door-knob and mat. It was more than I could stand, and I sank down, half conscious. I revived only long enough to see that Del Mar had forced one of the suits on Elaine finally. Then he pressed a button hidden on the side of his desk and a secret panel in the wall opened. Picking up Elaine he and the others hurried through into what looked like a dark passage and the panel closed. They were gone. I put forth all my remaining strength in one last desperate struggle. Somehow, I managed to kick the wire mat from under my feet, breaking the contact. I staggered toward the panel, but fell to the floor, unconscious. . . . . . . . Outside, the iron ring, as Woodward had planned it, of soldiers were looking about, alert for any noise or movement. Suddenly, two of them who had been watching the grounds attentively signalled to each other that they saw something. From the shrubbery emerged a most curious and uncouth figure, all in rags, with long, unkempt hair and beard, sallow complexion, and carrying a long staff. It might have been a tramp or a hermit, perhaps, who was making his way toward the house. The two soldiers stole up noiselessly, close to him. Almost before he knew it, the hermit felt himself seized from behind by four powerful arms. Escape was impossible. "Let me go," he pleaded. "Can't you see I'm harming no one?" But the captors were obdurate. "Tell it to the Lieutenant," they rejoined grimly forcing him to go before them by twisting his arms, "Our orders were to seize any one entering or leaving." Protests were in vain. The hermit was forced to go before Lieutenant Woodward who was just in the rear directing the advance. "Well," demanded Woodward, "what's your business?" For an instant the hermit stood mute. What should he do? He has reason to know that the situation must be urgent. Slowly he raised his beard so that Woodward could see not only that it was false but what his features looked like. "Arnold!" gasped Woodward, startled. "What brings you here? Elaine and Jameson are in the house. We have it surrounded." Half an hour before, in the St. Germain, Arnold had no sooner received the telaphotograph than he hurried up to his room. From a closet he had produced another of his numerous disguises and quickly put it on. With scant white locks falling over his shoulders and long scraggly beard, he had made himself into a veritable wild man. Then he had put on the finishing touches and had made his way toward Del Mar's. A look of intense anxiety now flashed over Arnold's face as he heard Woodward's words. "But," he cried, "there is an underground passage from the house to the shore." "The deuce!" muttered Woodward, more alarmed now than ever. "Come, men,--to the house," he shouted out his orders as they passed them around the line. "Arnold, lead the way!" Together the soldier and the strange figure rushed to the front door of the bungalow. All was still inside. Heavy as it was, they broke it down and burst in. "Walter, there's Walter!" cried Woodward as he saw me lying on the floor of the study when they ran in. They hurried to me and as quickly as they could started to bring me around. "Where's Elaine?" asked the strange figure of the hermit. Weakly, I was able only to point to the panel. But it was enough. The soldiers understood. They dashed for it, looking for a button or an opening. Finding neither, they started to bang on it and batter it in with the butts of their guns. It was only seconds before it was splintered to kindling. There was the passage. Instantly, Woodward, the hermit, and the rest plunged into it utterly regardless of danger. On through the tunnel they went until at last they came, unmolested, to the end. There they paused to look about. The hermit pointed to the ground. Clearly there were footprints, leading to the shore. They followed them on down to the beach. "Look!" pointed the hermit. Off in the water they could now see the most curious sights. Four strangely helmeted creatures were wading out, each like a huge octopus-head, without tentacles. Only a few seconds before, Del Mar and his companions, carrying Elaine had emerged from the secret entrance of the tunnel and had dashed for the shore of the promontory. Stopping only an instant to consider what was to be done, Del Mar had seen some one else emerge from the tunnel. "Come--we must get down there quickly," he shouted, hurriedly issuing orders, as all three, carrying Elaine, waded out into the water. At sight of the strange figures the soldiers raised their guns and a volley of shot rang out. "Stop!" shouted the hermit, his hair streaming wildly as he ran before the guns and threw up as many as he could grasp with his outstretched arms. "Do you want to kill her?" "Her?" repeated Woodward. All stood there, wonderingly, gazing at the queer creatures. What did it mean? Slowly, they disappeared--literally under the water. They were gone--with Elaine! CHAPTER XVII THE TRIUMPH OF ELAINE Half carrying, half forcing Elaine down into the water, Del Mar and his two men, all four of the party clad in the outlandish submarine suits, bore the poor girl literally along the bottom of the bay until they reached a point which they knew to be directly under the entrance to the secret submarine harbor. Del Mar's mind was working feverishly. Though he now had in his power the girl he both loved and also feared as the stumbling-block in the execution of his nefarious plans against America, he realized that in getting her he had been forced to betray the precious secret of the harbor itself. At the point where he knew that the harbor was above him, hidden safely beneath the promontory, he took from under his arm a float which he released. Upward it shot through the water. Above, in the harbor, a number of his men were either on guard or lounging about. "A signal from the chief," cried a sentry, pointing to the float as it bobbed up. "Kick off the lead shoes," signalled Del Mar to the others, under the water. They did so and rose slowly to the surface, carrying Elaine up with them. The men at the surface were waiting for them and helped to pull Del Mar and his companions out of the water. "Come into the office, right away," beckoned Del Mar anxiously, removing his helmet and leading the way. In the office, the others removed their helmets, while Del Mar took the head-gear off Elaine. She stared about her bewildered. "Where am I?" she demanded. "A woman!" exclaimed the men in the harbor in surprise. "Never mind where you are," growled Del Mar, plainly worried. Then to the men, he added, "We can't stay any longer. The harbor is discovered. Get ready to leave immediately." Murmurs of anger and anxiety rose from the men as Del Mar related briefly between orders what had just happened. Immediately there was a general scramble to make ready for the escape. In the corner of the office, Elaine, again in her skirt and shirtwaist which the diving-suit had protected, sat open-eyed watching the preparations of the men for the hasty departure. Some had been detailed to get the rifles which they handed around to those as yet unarmed. Del Mar took one as well as a cartridge belt. "Guard her," he shouted to one man indicating Elaine, "and if she gets away this time, I'll shoot you." Then he led the others down the ledge until he came to a submarine boat. The rest followed, still making preparations for a hasty flight. . . . . . . . Woodward along with Professor Arnold, in his disguise as a hermit, stood for a moment surrounded by the soldiers, after the disappearance of Elaine and Del Mar in the water. "I see it all, now," cried the hermit, "the submarine, the strange disappearances, the messages in the water. They have a secret harbor under those cliffs, with an entrance beneath the water line." Hastily he wrote a note on a piece of paper. "Send one of your men to my headquarters with that," he said, handing it to Woodward to read: RODGERS,--Send new submarine telescope by bearer. You will find it in case No. 17, closet No. 3.--ARNOLD. "Right away," nodded Woodward, comprehending and calling a soldier whom he dispatched immediately with hurried instructions. The soldier saluted and left almost on a run. Then Woodward turned and with Arnold lead the men up the shore, still conferring on the best means of attacking the harbor. On a wharf along the shore Woodward, Arnold and the soldiers gathered, waiting for the telescope. Already Woodward had had a fast launch brought up, ready for use. . . . . . . . When Woodward, Arnold and the attacking party had discovered me unconscious in Del Mar's study, there had been no time to wait for me to regain full consciousness. They had placed me on a couch and run into the secret passageway after Elaine. Now, however, I slowly regained my senses and, looking about, vaguely began to realize what had happened. My first impulse was to search the study, looking in all the closets and table drawers. In a corner was a large chest, I opened it. Inside were several of the queer helmets and suits which I had seen Del Mar use and one of which he had placed on Elaine. For some moments I examined them curiously, wondering what their use could be. Somehow it seemed to me, if Del Mar had used them in the escape, we should need them in the pursuit. Then my eye fell on the broken panel. I entered it and groped cautiously down the passageway. At the end I gazed about, trying to discover which way they had all gone. At last, down on the shore, before a wharf I could see Woodward, the strange old hermit and the rest. I ran toward them, calling. . . . . . . . By this time the soldier who had been sent for the submarine telescope arrived at last, with the telescope in sections in several long cases. "Good!" exclaimed the old hermit, almost seizing the package which the soldier handed him. He unwrapped it and joined the various sections together. It was, as I have said, a submarine telescope, but after a design entirely new, differing from the ordinary submarine telescope. It had an arm bent at right angles, with prismatic mirrors so that it was not only possible to see the bottom of the sea but by an adjustment also to see at right angles, or, as it were, around a corner. It was while he was joining this contrivance together that I came up from the end of the secret passage down to the wharf. "Why, here's Jameson," greeted Woodward. "I'm glad you're so much better." "Where's Elaine?" I interrupted breathlessly. They began to tell me. "Aren't you going to follow?" I cried. "Follow? How can we follow?" Excitedly I told of my discovery of the helmets. "Just the thing!" exclaimed the hermit. "Send some one back to get them." Woodward quickly detached several soldiers to go with me and I hurried back to the bungalow, while others carried the submarine telescope to the boat. It was only a few minutes later that in Del Mar's own car, I drove up to the wharf again and we unloaded the curious submarine helmets and suits. Quickly Woodward posted several of his men to act as sentries on the beach, then with the rest we climbed into the launch and slipped off down the shore. The launch which Woodward had commandeered moved along in the general direction which they had seen Del Mar and his men take with Elaine. With the telescope over the side, we cruised about slowly in a circle, Arnold gazing through the eyepiece. All of us were by this time in the diving-suits which I had brought from Del Mar's, except that we had not yet strapped on the helmets. Suddenly Arnold raised his hand and signalled to stop the launch. "Look!" he cried, indicating the eyepiece of the submarine telescope which he had let down over the side. Woodward gazed into the eyepiece and then I did, also. There we could see the side of a submerged submarine a short distance away, through the cave-like entrance of what appeared to be a great under-water harbor. "What shall we do?" queried Woodward. "Attack it now before they are prepared," replied the hermit decisively. "Put on the helmets." All of us except those who were running the launch buckled on the head-pieces, wrapping our guns in waterproof covers which we had found with the suits. As soon as we had finished, one after another, we let ourselves over the side of the boat and sank to the bottom. On the bottom we gathered and slowly, in the heavy unaccustomed helmets and cumbersome suits, we made our way in a body through the entrance of the harbor. Upward through the archway we went, clinging to rocks, anything, but always upward. As we emerged a shot rang out. One of our men threw up his arms and fell back into the water. On we pressed. . . . . . . . Elaine sat in a corner of the office, mute, while the man who was guarding her, heavily armed, paced up and down. Suddenly an overwhelming desire came over her to attempt an escape. But no sooner had she made a motion as though to run through the door than the man seized her and drove her back to her corner. "Take your positions here," ordered Del Mar to several of the men. "If you see anybody come up through the water, these hand grenades ought to settle them." Along the ledge the men were stationed each with a pile of the grenades before him. "See!" cried one of them from the ledge as he caught sight of one of our helmets appearing. The others crouched and stared. Del Mar himself hurried forward and gazed in the direction the man indicated. There they could see Woodward, Arnold and the rest of us just beginning to climb up out of the water. Del Mar aimed and fired. One of the men had thrown up his arms with a cry and fallen back into the water. Invaders seemed to swarm up now in every direction from the water. On the semi-circular ledge about one side of the harbor, Del Mar's men were now ranged in close order near a submarine, whose hatch was open to receive them, ready to repel the attack and if necessary retreat into the under-sea boat. They fired sharply at the figures that rose from the water. Many of the men fell back, hit, but, in turn, a large number managed to gain a foothold on the ledge. Led by Woodward and Arnold, they formed quickly and stripped off the waterproof coverings of their weapons, returning the fire sharply. Things were more equal now. Several of Del Mar's men had fallen. The smoke of battle filled the narrow harbor. In the office Elaine listened keenly to the shots. What did it all mean? Clearly it could be nothing less than assistance coming. The man on guard heard also and his uncontrollable curiosity took him to the door. As he gazed out Elaine saw her chance. She made a rush at him and seized him, wresting the rifle from his hands before he knew it. She sprang back just as he drew his revolver and fired at her. The shot just narrowly missed her, but she did not lose her presence of mind. She fired the rifle in turn and the man fell. A little shudder ran over her. She had killed a man! But the firing outside grew fiercer. She had no time to think. She stepped over the body, her face averted, and ran out. There she could see Del Mar and his men. Many of them by this time had been killed or wounded. "We can't beat them; they are too many for us," muttered Del Mar. "We'll have to get away if we can. Into the submarine!" he ordered. Hastily they began to pile into the open hatch. Just as Del Mar started to follow them, he caught sight of Elaine running out of the office. Almost in one leap he was at her side. Before she could raise her rifle and fire he had seized it. She managed, however, to push him off and get away from him. She looked about for some weapon. There on the ledge lay one of the hand grenades. She picked it up and hurled it at him, but he dodged and it missed him. On it flew, landing close to the submarine. As it exploded, another of Del Mar's men toppled over into the water. Between volleys, Woodward, Arnold and the rest pulled off their helmets. "Elaine!" cried Arnold, catching sight of her in the hands of Del Mar. Quickly, at the head of such men as he could muster, the hermit led a charge. In the submarine the last man was waiting for Del Mar. As the hermit ran forward with several soldiers between Del Mar and the submarine, it was evident that Del Mar would be cut off. The man at the hatch climbed down into the boat. It was useless to wait. He banged shut and clamped the hatch. Slowly the submarine began to sink. Del Mar by this time had overcome Elaine and started to run toward the submarine with her. But then he stopped short. There was a queer figure of a hermit leading some soldiers. He was cut off. "Back into the office!" he growled, dragging Elaine. He banged shut the door just as the hermit and the soldiers made a rush at him. On the door they battered. But it was in vain. The door was locked. In the office Del Mar hastily went to a corner, after barring the door, and lifted a trap-door in the floor, known only to himself. Elaine did not move or make any attempt to escape, for Del Mar in addition to having a vicious looking automatic in his hand kept a watchful eye on her. Outside the office, the soldiers, led by the hermit and Woodward continued to batter at the door. "Now--go down that stairway--ahead of me," ordered Del Mar. Elaine obeyed tensely, and he followed into his emergency exit, closing the trap. "Beat harder, men," urged the hermit, as the soldiers battered at the door. They redoubled their efforts and the door bent and swayed. At last it fell in under the sheer weight of the blows. "By George--he's gone--with Elaine," cried the hermit, looking at the empty office. Feverishly they hunted about for a means of escape but could find none. "Pound the floor and walls with the butts of your guns," ordered Arnold. "There must be some place that is hollow." They did so, going over all inch by inch. Meanwhile, through the passage, along a rocky stairway, Del Mar continued to drive Elaine before him, up and ever up to the level of the land. At last Elaine, followed by Del Mar, emerged from the rocky passage in a cleft in the cliffs, far above the promontory. "Go on!" he ordered, forcing her to go ahead of him. They came finally to a small hut on a cliff overlooking the real harbor. "Enter!" demanded Del Mar. Still meekly, she obeyed. Del Mar seized her and before she knew it had her bound and gagged. Down in the little office our men continued to search for the secret exit. "Here's a place that gives an echo," shouted one of them. As he found the secret trap and threw it open, the hermit stripped off the cumbersome diving-suit and jumped in, followed by Woodward, myself and the soldiers. Upward we climbed until at last we came to the opening. There we paused and looked about. Where was Del Mar? Where was Elaine? We could see no trace of them. Finally, however, Arnold discovered the trail in the grass and we followed him, slowly picking up the tracks. . . . . . . . Knowing that the submarine would cruise about and wait for him, Del Mar decided to leave Elaine in the hut while he went out and searched for a boat in which to look for the submarine. Coming out of the hut, he gazed about and moved off cautiously. Stealthily he went down to the shore and there looked up and down intently. A short distance away from him was a pier in the process of construction. Men were unloading spiles from a cable car that ran out on the pier on a little construction railway, as well as other material with which to fill in the pier. At the end of the dock lay a power-boat, moored, evidently belonging to some one interested in the work on the pier. The workmen had just finished unloading a car full and were climbing back on the empty car, which looked as if it had once been a trolley. As Del Mar looked over the scene of activity, he caught sight of the powerboat. "Just what I want," he muttered to himself. "I must get Elaine. I can get away in that." The workmen signalled to the engineer above and the car ran up the wharf and up an incline at the shore-end. The moment the car disappeared, Del Mar hurried away in the direction he had come. At the top of the grade, he noticed, was a donkey engine which operated the cable that drew the car up from the dock, and at the top of the incline was a huge pile of material. The car had been drawn up to the top of the grade by this time. There the engineer who operated the engine stopped it. Just then the whistle blew for the noon hour. The men quit work and went to get their dinner pails, while the engineer started to draw the fire. Beside the engine, he began to chop some wood, while the car was held at the top of the grade by the cable. . . . . . . . In our pursuit we came at last in sight of a lonely hut. Evidently that must be a rendezvous of Del Mar. But was he there? Was Elaine there? We must see first. While we were looking about and debating what was the best thing to do, who should appear hurrying up the hill but Del Mar himself, going toward the hut. As we caught sight of him, Arnold sprang forward. Woodward and I, followed by the soldiers also jumped out. Del Mar turned and ran down the hill again with us after him, in full cry. While we had been waiting, some of the soldiers had deployed down the hill and now, hearing our shouts, turned, and came up again. Beside his engine, we could see an engineer chopping wood. He paused now in his chopping and was gazing out over the bay. Suddenly he had seen something out in the water that had attracted his attention and was staring at it. There it moved, nothing less than a half-submerged submarine. As the engineer gazed off at it, Del Mar came up, unseen, behind him and stood there, also watching the submarine, fascinated. Just then behind him Del Mar heard us pursuing. He looked about as we ran toward him and saw that we had formed a wide circle, with the men down the hill, that almost completely surrounded him. There was no chance for escape. It was hopeless. But it was not Del Mar's nature to give up. He gave one last glance about. There was the trolley car that had been converted into a cable way. It offered just one chance in a thousand. Suddenly his face assumed an air of desperate determination. He sprang toward the engineer and grappled with him, seeking to wrest the axe from his hand. Every second counted. Our circle was now narrowing down and closing in on him. Del Mar managed to knock out the engineer, taken by surprise, just as our men fired a volley. In the struggle, Del Mar was unharmed. Instead he just managed to get the axe. An instant later a leap landed him on the cable car. With a blow of the axe he cut the cable. The car began to move slowly down the hill on the grade. Some of the men were down below in its path. But the onrushing cable car was too much for them. They could only leap aside to save themselves. On down the incline, gathering momentum every second, the car dashed, Del Mar swaying crazily but keeping his footing. We followed as fast as we could, but it was useless. Out on the wharf it sped at a terrific pace. At the end it literally catapulted itself into the water, crashing from the end of the pier. As it did so, Del Mar gave a flying leap out into the harbor, struck the water with a clean dive and disappeared. On down the hill we hurried. There in the water was Del Mar swimming rapidly. Almost before we knew it, we saw him raise his hand and signal, shouting. There only a few yards away was the periscope of a submarine. As we watched, we could see that it had seen him, had turned in his direction. Would they get him? We watched, fascinated. Some of our men fired, as accurately as they could at a figure bobbing so uncertainly on the water. Meanwhile the submarine approached closer and rose a bit so that the hatchway cleared the waves. It opened. One of the foreign agents assisted Del Mar in. He had escaped at last! . . . . . . . It was most heart-breaking to have had Del Mar so nearly in our grasp and then to have lost him. We looked from one to another, in despair. Only Arnold, in his disguise as a hermit, seemed undiscouraged. Suddenly he turned to Woodward. "What time is it?" he asked eagerly. "A little past noon." "The Kennedy wireless torpedo!" he exclaimed. "It arrived to-day. Burnside is trying it out." Suddenly there flashed over me the recollection of the marvellous invention that Kennedy had made for the Government just before his disappearance, as well as the memory of the experience I had had once with the intrepid Burnside. Woodward's face showed a ray of interest and hope in the overwhelming gloom that had settled on us all. "You and Jameson go to Fort Dale, quick," directed Arnold eagerly. "I'm not fit. Get Burnside. Have him bring the torpedo in the air-boat." We needed no further urging. It was a slender chance. But I reflected that the submarine could not run through the bay totally submerged. It must have its periscope in view. We hurried away, leaving Arnold, who slowly mounted the hill again. How we did it, I don't know, but we managed to get to the Fort in record time. There near the aeroplane hangar, sure enough, was Burnside with some other men adjusting the first real wireless Kennedy torpedo, the last word in scientific warfare, making an aerial torpedo-boat. We ran up to the hangar calling to Burnside excitedly. It was only a moment later, that he began to issue orders in his sharp staccato. His men swarmed forward and took the torpedo from the spot where they had been examining it, adjusting it now beneath the hydroaeroplane. "Jameson, you come with me," he asked. "You went before." We rose quickly from the surface and planed along out over the harbor. Far off we could see the ripple from the periscope of the submarine that was bearing Del Mar away. Would Kennedy's invention for which Del Mar had dared so much in the first place prove his final undoing? We sped ahead. Down below in the submersible Del Mar was giving hasty orders to his men, to dip down as soon as all the shipping and the sand bars were cleared. I strained my eyes through the glasses reporting feverishly to Burnside what I saw so that he could steer his course. "There it is," I urged. "Keep on--just to the left." "I see it," returned Burnside a moment later catching with his naked eye the thin line of foam on the water left by the periscope. "Would you mind getting that torpedo ready?" he continued. "I'll tell you just what to do. They'll try to duck as soon as they see us, but it won't be any use. They can't get totally submerged fast enough." Following Burnside's directions I adjusted the firing apparatus of the torpedo. "Let it go!" shouted Burnside. I did so, as he volplaned down almost to the water. The torpedo fell, sank, bobbed up, then ran along just tinder the surface. Already I was somewhat familiar with the wireless device that controlled it, so that while Burnside steadied the aircraft I could direct it, as he coached me. The submarine saw it coming now. But it was too late. It could not turn; it could not submerge in time. A terrific explosion followed as the torpedo came in contact with the boat, throwing a column of water high in the air. A yawning hole was blown in the very side of the submarine. One could see the water rush in. Inside, Del Mar and his men were now panic-stricken. Some of them desperately tried to plug the hole. But it was hopeless. Others fell, fainting, from the poisonous gases that were developed. Of them all, Del Mar's was the only cool head. He realized that all was over. There was nothing left to do but what other submarine heroes had done in better causes. He seized a piece of paper and hastily wrote: Tell my emperor I failed only because Craig Kennedy was against me.--DEL MAR. He had barely time to place the message in a metal float near-by. Down the submarine, now full of water, sank. With his last strength he flung the message clear of the wreckage as it settled on the mud on the bottom of the bay. Burnside and I could but stare in grim satisfaction at the end of the enemy of ourselves and our country. . . . . . . . Up the hillside plodded Professor Arnold still in his wild disguise as the hermit. Now and then he turned and cast an anxious glance out over the bay at the fast disappearing periscope of the submarine. Once he paused. That was when he saw the hydroaeroplane with Burnside and myself carrying the wireless torpedo. Again he paused as he plodded up, this time with a gasp, of extreme satisfaction. He has seen the water-spout and heard the explosion that marked the debacle of Del Mar. The torpedo had worked. The most dangerous foreign agent of the coalition of America's enemies was dead, and his secrets had gone with him to the bottom of the sea. Perhaps no one would ever know what the nation had been spared. He did not pause long, now. More eagerly he plodded up the hill, until he came to the hut. He pushed open the door. There lay Elaine, still bound. Quickly he cut the cords and tore the gag from her mouth. As he did so, his own beard fell off. He was no longer the hermit. Nor was he what I myself had thought him, Arnold. "Craig!" cried Elaine in eager surprise. Kennedy said not a word as he grasped her two hands. "And you were always around us, protecting Walter and me," she half laughed, half cried hysterically. "I knew it--I knew it!" Kennedy said nothing. His heart was too happy. "Yes," he said simply, as he gazed deeply into her great eyes, "my work on the case is done." THE END 
5054	----	THE CRAIG KENNEDY SERIES THE DREAM DOCTOR BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER Contents CHAPTER I The Dream Doctor II The Soul Analysis III The Sybarite IV The Beauty Shop V The Phantom Circuit VI The Detectaphone VII The Green Curse VIII The Mummy Case IX The Elixir of Life X The Toxin of Death XI The Opium Joint XII The "Dope Trust" XIII The Kleptomaniac XIV The Crimeometer XV The Vampire XVI The Blood Test XVII The Bomb Maker XVIII The "Coke" Fiend XIX The Submarine Mystery XX The Wireless Detector XXI The Ghouls XXII The X-Ray "Movies" XXIII The Death House XXIV The Final Day THE DREAM DOCTOR I THE DREAM DOCTOR "Jameson, I want you to get the real story about that friend of yours, Professor Kennedy," announced the managing editor of the Star, early one afternoon when I had been summoned into the sanctum. From a batch of letters that had accumulated in the litter on the top of his desk, he selected one and glanced over it hurriedly. "For instance," he went on reflectively, "here's a letter from a Constant Reader who asks, 'Is this Professor Craig Kennedy really all that you say he is, and, if so, how can I find out about his new scientific detective method?'" He paused and tipped back his chair. "Now, I don't want to file these letters in the waste basket. When people write letters to a newspaper, it means something. I might reply, in this case, that he is as real as science, as real as the fight of society against the criminal. But I want to do more than that." The editor had risen, as if shaking himself momentarily loose from the ordinary routine of the office. "You get me?" he went on, enthusiastically, "In other words, your assignment, Jameson, for the next month is to do nothing except follow your friend Kennedy. Start in right now, on the first, and cross-section out of his life just one month, an average month. Take things just as they come, set them down just as they happen, and when you get through give me an intimate picture of the man and his work." He picked up the schedule for the day and I knew that the interview was at an end. I was to "get" Kennedy. Often I had written snatches of Craig's adventures, but never before anything as ambitious as this assignment, for a whole month. At first it staggered me. But the more I thought about it, the better I liked it. I hastened uptown to the apartment on the Heights which Kennedy and I had occupied for some time. I say we occupied it. We did so during those hours when he was not at his laboratory at the Chemistry Building on the University campus, or working on one of those cases which fascinated him. Fortunately, he happened to be there as I burst in upon him. "Well?" he queried absently, looking up from a book, one of the latest untranslated treatises on the new psychology from the pen of the eminent scientist, Dr. Freud of Vienna, "what brings you uptown so early?" Briefly as I could, I explained to him what it was that I proposed to do. He listened without comment and I rattled on, determined not to allow him to negative it. "And," I added, warming up to the subject, "I think I owe a debt of gratitude to the managing editor. He has crystallised in my mind an idea that has long been latent. Why, Craig," I went on, "that is exactly what you want--to show people how they can never hope to beat the modern scientific detective, to show that the crime-hunters have gone ahead faster even than--" The telephone tinkled insistently. Without a word, Kennedy motioned to me to "listen in" on the extension on my desk, which he had placed there as a precaution so that I could corroborate any conversation that took place over our wire. His action was quite enough to indicate to me that, at least, he had no objection to the plan. "This is Dr. Leslie--the coroner. Can you come to the Municipal Hospital--right away?" "Right away, Doctor," answered Craig, hanging up the receiver. "Walter, you'll come, too?" A quarter of an hour later we were in the courtyard of the city's largest hospital. In the balmy sunshine the convalescing patients were sitting on benches or slowly trying their strength, walking over the grass, clad in faded hospital bathrobes. We entered the office and quickly were conducted by an orderly to a little laboratory in a distant wing. "What's the matter?" asked Craig, as we hurried along. "I don't know exactly," replied the man, "except that it seems that Price Maitland, the broker, you know, was picked up on the street and brought here dying. He died before the doctors could relieve him." Dr. Leslie was waiting impatiently for us. "What do you make of that, Professor Kennedy?" The coroner spread out on the table before us a folded half-sheet of typewriting and searched Craig's face eagerly to see what impression it made on him. "We found it stuffed in Maitland's outside coat pocket," he explained. It was dateless and brief: Dearest Madeline: May God in his mercy forgive me for what I am about to do. I have just seen Dr. Ross. He has told me the nature of your illness. I cannot bear to think that I am the cause, so I am going simply to drop out of your life. I cannot live with you, and I cannot live without you. Do not blame me. Always think the best you can of me, even if you could not give me all. Good-bye. Your distracted husband, PRICE. At once the idea flashed over me that Maitland had found himself suffering from some incurable disease and had taken the quickest means of settling his dilemma. Kennedy looked up suddenly from the note. "Do you think it was a suicide?" asked the coroner. "Suicide?" Craig repeated. "Suicides don't usually write on typewriters. A hasty note scrawled on a sheet of paper in trembling pen or pencil, that is what they usually leave. No, some one tried to escape the handwriting experts this way." "Exactly my idea," agreed Dr. Leslie, with evident satisfaction. "Now listen. Maitland was conscious almost up to the last moment, and yet the hospital doctors tell me they could not get a syllable of an ante-mortem statement from him." "You mean he refused to talk?" I asked. "No," he replied; "it was more perplexing than that Even if the police had not made the usual blunder of arresting him for intoxication instead of sending him immediately to the hospital, it would have made no difference. The doctors simply could not have saved him, apparently. For the truth is, Professor Kennedy, we don't even know what was the matter with him." Dr. Leslie seemed much excited by the case, as well he might be. "Maitland was found reeling and staggering on Broadway this morning," continued the coroner. "Perhaps the policeman was not really at fault at first for arresting him, but before the wagon came Maitland was speechless and absolutely unable to move a muscle." Dr. Leslie paused as he recited the strange facts, then resumed: "His eyes reacted, all right. He seemed to want to speak, to write, but couldn't. A frothy saliva dribbled from his mouth, but he could not frame a word. He was paralysed, and his breathing was peculiar. They then hurried him to the hospital as soon as they could. But it was of no use." Kennedy was regarding the doctor keenly as he proceeded. Dr. Leslie paused again to emphasise what he was about to say. "Here is another strange thing. It may or may not be of importance, but it is strange, nevertheless. Before Maitland died they sent for his wife. He was still conscious when she reached the hospital, could recognise her, seemed to want to speak, but could neither talk nor move. It was pathetic. She was grief-stricken, of course. But she did not faint. She is not of the fainting kind. It was what she said that impressed everyone. 'I knew it--I knew it,' she cried. She had dropped on her knees by the side of the bed. 'I felt it. Only the other night I had the horrible dream. I saw him in a terrific struggle. I could not see what it was--it seemed to be an invisible thing. I ran to him--then the scene shifted. I saw a funeral procession, and in the casket I could see through the wood--his face--oh, it was a warning! It has come true. I feared it, even though I knew it was only a dream. Often I have had the dream of that funeral procession and always I saw the same face, his face. Oh, it is horrible--terrible!'" It was evident that Dr. Leslie at least was impressed by the dream. "What have you done since?" asked Craig. "I have turned loose everyone I could find available," replied Dr. Leslie, handing over a sheaf of reports. Kennedy glanced keenly over them as they lay spread out on the table. "I should like to see the body," he said, at length. It was lying in the next room, awaiting Dr. Leslie's permission to be removed. "At first," explained the doctor, leading the way, "we thought it might be a case of knock-out drops, chloral, you know--or perhaps chloral and whiskey, a combination which might unite to make chloroform in the blood. But no. We have tested for everything we can think of. In fact there seems to be no trace of a drug present. It is inexplicable. If Maitland really committed suicide, he must have taken SOMETHING--and as far as we can find out there is no trace of anything. As far as we have gone we have always been forced back to the original idea that it was a natural death--perhaps due to shock of some kind, or organic weakness." Kennedy had thoughtfully raised one of the lifeless hands and was examining it. "Not that," he corrected. "Even if the autopsy shows nothing, it doesn't prove that it was a natural death. Look!" On the back of the hand was a tiny, red, swollen mark. Dr. Leslie regarded it with pursed-up lips as though not knowing whether it was significant or not. "The tissues seemed to be thickly infiltrated with a reddish serum and the blood-vessels congested," he remarked slowly. "There was a frothy mucus in the bronchial tubes. The blood was liquid, dark, and didn't clot. The fact of the matter is that the autopsical research revealed absolutely nothing but a general disorganisation of the blood-corpuscles, a most peculiar thing, but one the significance of which none of us here can fathom. If it was poison that he took or that had been given to him, it was the most subtle, intangible, elusive, that ever came to my knowledge. Why, there is absolutely no trace or clue--" "Nor any use in looking for one in that way," broke in Kennedy decisively. "If we are to make any progress in this case, we must look elsewhere than to an autopsy. There is no clue beyond what you have found, if I am right. And I think I am right. It was the venom of the cobra." "Cobra venom?" repeated the coroner, glancing up at a row of technical works. "Yes. No, it's no use trying to look it up. There is no way of verifying a case of cobra poisoning except by the symptoms. It is not like any other poisoning in the world." Dr. Leslie and I looked at each other, aghast at the thought of a poison so subtle that it defied detection. "You think he was bitten by a snake?" I blurted out, half incredulous. "Oh, Walter, on Broadway? No, of course not. But cobra venom has a medicinal value. It is sent here in small quantities for various medicinal purposes. Then, too, it would be easy to use it. A scratch on the hand in the passing crowd, a quick shoving of the letter into the pocket of the victim--and the murderer would probably think to go undetected." We stood dismayed at the horror of such a scientific murder and the meagreness of the materials to work on in tracing it out. "That dream was indeed peculiar," ruminated Craig, before we had really grasped the import of his quick revelation. "You don't mean to say that you attach any importance to a dream?" I asked hurriedly, trying to follow him. Kennedy merely shrugged his shoulders, but I could see plainly enough that he did. "You haven't given this letter out to the press?" he asked. "Not yet," answered Dr. Leslie. "Then don't, until I say to do so. I shall need to keep it." The cab in which we had come to the hospital was still waiting. "We must see Mrs. Maitland first," said Kennedy, as we left the nonplused coroner and his assistants. The Maitlands lived, we soon found, in a large old-fashioned brownstone house just off Fifth Avenue. Kennedy's card with the message that it was very urgent brought us in as far as the library, where we sat for a moment looking around at the quiet refinement of a more than well-to-do home. On a desk at one end of the long room was a typewriter. Kennedy rose. There was not a sound of any one in either the hallway or the adjoining rooms. A moment later he was bending quietly over the typewriter in the corner, running off a series of characters on a sheet of paper. A sound of a closing door upstairs, and he quickly jammed the paper into his pocket, retraced his steps, and was sitting quietly opposite me again. Mrs. Maitland was a tall, perfectly formed woman of baffling age, but with the impression of both youth and maturity which was very fascinating. She was calmer now, and although she seemed to be of anything but a hysterical nature, it was quite evident that her nervousness was due to much more than the shock of the recent tragic event, great as that must have been. It may have been that I recalled the words of the note, "Dr. Ross has told me the nature of your illness," but I fancied that she had been suffering from some nervous trouble. "There is no use prolonging our introduction, Mrs. Maitland," began Kennedy. "We have called because the authorities are not yet fully convinced that Mr. Maitland committed suicide." It was evident that she had seen the note, at least. "Not a suicide?" she repeated, looking from one to the other of us. "Mr. Masterson on the wire, ma'am," whispered a maid. "Do you wish to speak to him? He begged to say that he did not wish to intrude, but he felt that if there--" "Yes, I will talk to him--in my room," she interrupted. I thought that there was just a trace of well-concealed confusion, as she excused herself. We rose. Kennedy did not resume his seat immediately. Without a word or look he completed his work at the typewriter by abstracting several blank sheets of paper from the desk. A few moments later Mrs. Maitland returned, calmer. "In his note," resumed Kennedy, "he spoke of Dr. Ross and--" "Oh," she cried, "can't you see Dr. Ross about it? Really I--I oughtn't to be--questioned in this way--not now, so soon after what I've had to go through." It seemed that her nerves were getting unstrung again. Kennedy rose to go. "Later, come to see me," she pleaded. "But now--you must realise--it is too much. I cannot talk--I cannot." "Mr. Maitland had no enemies that you know of?" asked Kennedy, determined to learn something now, at least. "No, no. None that would--do that." "You had had no quarrel?" he added. "No--we never quarrelled. Oh, Price--why did you? How could you?" Her feelings were apparently rapidly getting the better of her. Kennedy bowed, and we withdrew silently. He had learned one thing. She believed or wanted others to believe in the note. At a public telephone, a few minutes later, Kennedy was running over the names in the telephone book. "Let me see--here's an Arnold Masterson," he considered. Then turning the pages he went on, "Now we must find this Dr. Ross. There--Dr. Sheldon Ross--specialist in nerve diseases--that must be the one. He lives only a few blocks further uptown." Handsome, well built, tall, dignified, in fact distinguished, Dr. Ross proved to be a man whose very face and manner were magnetic, as should be those of one who had chosen his branch of the profession. "You have heard, I suppose, of the strange death of Price Maitland?" began Kennedy when we were seated in the doctor's office. "Yes, about an hour ago." It was evident that he was studying us. "Mrs. Maitland, I believe, is a patient of yours?" "Yes, Mrs. Maitland is one of my patients," he admitted interrogatively. Then, as if considering that Kennedy's manner was not to be mollified by anything short of a show of confidence, he added: "She came to me several months ago. I have had her under treatment for nervous trouble since then, without a marked improvement." "And Mr. Maitland," asked Kennedy, "was he a patient, too?" "Mr. Maitland," admitted the doctor with some reticence, "had called on me this morning, but no, he was not a patient." "Did you notice anything unusual?" "He seemed to be much worried," Dr. Ross replied guardedly. Kennedy took the suicide note from his pocket and handed it to him. "I suppose you have heard of this?" asked Craig. The doctor read it hastily, then looked up, as if measuring from Kennedy's manner just how much he knew. "As nearly as I could make out," he said slowly, his reticence to outward appearance gone, "Maitland seemed to have something on his mind. He came inquiring as to the real cause of his wife's nervousness. Before I had talked to him long I gathered that he had a haunting fear that she did not love him any more, if ever. I fancied that he even doubted her fidelity." I wondered why the doctor was talking so freely, now, in contrast with his former secretiveness. "Do you think he was right?" shot out Kennedy quickly, eying Dr. Ross keenly. "No, emphatically, no; he was not right," replied the doctor, meeting Craig's scrutiny without flinching. "Mrs. Maitland," he went on more slowly as if carefully weighing every word, "belongs to a large and growing class of women in whom, to speak frankly, sex seems to be suppressed. She is a very handsome and attractive woman--you have seen her? Yes? You must have noticed, though, that she is really frigid, cold, intellectual." The doctor was so sharp and positive about his first statement and so careful in phrasing the second that I, at least, jumped to the conclusion that Maitland might have been right, after all. I imagined that Kennedy, too, had his suspicions of the doctor. "Have you ever heard of or used cobra venom in any of your medical work?" he asked casually. Dr. Ross wheeled in his chair, surprised. "Why, yes," he replied quickly. "You know that it is a test for blood diseases, one of the most recently discovered and used parallel to the old tests. It is known as the Weil cobra-venom test." "Do you use it often?" "N--no," he replied. "My practice ordinarily does not lie in that direction. I used it not long ago, once, though. I have a patient under my care, a well-known club-man. He came to me originally--" "Arnold Masterson?" asked Craig. "Yes--how did you know his name?" "Guessed it," replied Craig laconically, as if he knew much more than he cared to tell. "He was a friend of Mrs. Maitland's, was he not?" "I should say not," replied Dr. Ross, without hesitation. He was quite ready to talk without being urged. "Ordinarily," he explained confidentially, "professional ethics seals my lips, but in this instance, since you seem to know so much, I may as well tell more." I hardly knew whether to take him at his face value or not. Still he went on: "Mrs. Maitland is, as I have hinted at, what we specialists would call a consciously frigid but unconsciously passionate woman. As an intellectual woman she suppresses nature. But nature does and will assert herself, we believe. Often you will find an intellectual woman attracted unreasonably to a purely physical man--I mean, speaking generally, not in particular cases. You have read Ellen Key, I presume? Well, she expresses it well in some of the things she has written about affinities. Now, don't misunderstand me," he cautioned. "I am speaking generally, not of this individual case." I was following Dr. Ross closely. When he talked so, he was a most fascinating man. "Mrs. Maitland," he resumed, "has been much troubled by her dreams, as you have heard, doubtless. The other day she told me of another dream. In it she seemed to be attacked by a bull, which suddenly changed into a serpent. I may say that I had asked her to make a record of her dreams, as well as other data, which I thought might be of use in the study and treatment of her nervous troubles. I readily surmised that not the dream, but something else, perhaps some recollection which it recalled, worried her. By careful questioning I discovered that it was--a broken engagement." "Yes," prompted Kennedy. "The bull-serpent, she admitted, had a half-human face--the face of Arnold Masterson!" Was Dr. Ross desperately shifting suspicion from himself? I asked. "Very strange--very," ruminated Kennedy. "That reminds me again. I wonder if you could let me have a sample of this cobra venom?" "Surely. Excuse me; I'll get you some." The doctor had scarcely shut the door when Kennedy began prowling around quietly. In the waiting-room, which was now deserted, stood a typewriter. Quickly Craig ran over the keys of the machine until he had a sample of every character. Then he reached into drawer of the desk and hastily stuffed several blank sheets of paper into his pocket. "Of course I need hardly caution you in handling this," remarked Dr. Ross, as he returned. "You are as well acquainted as I am with the danger attending its careless and unscientific uses." "I am, and I thank you very much," said Kennedy. We were standing in the waiting-room. "You will keep me advised of any progress you make in the case?" the doctor asked. "It complicates, as you can well imagine, my treatment of Mrs. Maitland." "I shall be glad to do so," replied Kennedy, as we departed. An hour later found us in a handsomely appointed bachelor apartment in a fashionable hotel overlooking the lower entrance to the Park. "Mr. Masterson, I believe?" inquired Kennedy, as a slim, debonair, youngish-old man entered the room in which we had been waiting. "I am that same," he smiled. "To what am I indebted for this pleasure?" We had been gazing at the various curios with which he had made the room a veritable den of the connoisseur. "You have evidently travelled considerably," remarked Kennedy, avoiding the question for the time. "Yes, I have been back in this country only a few weeks," Masterson replied, awaiting the answer to the first question. "I called," proceeded Kennedy, "in the hope that you, Mr. Masterson, might be able to shed some light on the rather peculiar case of Mr. Maitland, of whose death, I suppose, you have already heard." "I?" "You have known Mrs. Maitland a long time?" ignored Kennedy. "We went to school together." "And were engaged, were you not?" Masterson looked at Kennedy in ill-concealed surprise. "Yes. But how did you know that? It was a secret--only between us two--I thought. She broke it off--not I." "She broke off the engagement?" prompted Kennedy. "Yes--a story about an escapade of mine and all that sort of thing, you know--but, by Jove! I like your nerve, sir." Masterson frowned, then added: "I prefer not to talk of that. There are some incidents in a man's life, particularly where a woman is concerned, that are forbidden." "Oh, I beg pardon," hastened Kennedy, "but, by the way, you would have no objection to making a statement regarding your trip abroad and your recent return to this country--subsequent to--ah--the incident which we will not refer to?" "None whatever. I left New York in 1908, disgusted with everything in general, and life here in particular--" "Would you object to jotting it down so that I can get it straight?" asked Kennedy. "Just a brief resume, you know." "No. Have you a pen or a pencil?" "I think you might as well dictate it; it will take only a minute to run it off on the typewriter." Masterson rang the bell. A young man appeared noiselessly. "Wix," he said, "take this: 'I left New York in 1908, travelling on the Continent, mostly in Paris, Vienna, and Rome. Latterly I have lived in London, until six weeks ago, when I returned to New York.' Will that serve?" "Yes, perfectly," said Kennedy, as he folded up the sheet of paper which the young secretary handed to him. "Thank you. I trust you won't consider it an impertinence if I ask you whether you were aware that Dr. Ross was Mrs. Maitland's physician?" "Of course I knew it," Masterson replied frankly. "I have given him up for that reason, although he does not know it yet. I most strenuously object to being the subject of--what shall I call it?--his mental vivisection." "Do you think he oversteps his position in trying to learn of the mental life of his patients?" queried Craig. "I would rather say nothing further on that, either," replied Masterson. "I was talking over the wire to Mrs. Maitland a few moments ago, giving her my condolences and asking if there was anything I could do for her immediately, just as I would have done in the old days--only then, of course, I should have gone to her directly. The reason I did not go, but telephoned, was because this Ross seems to have put some ridiculous notions into her head about me. Now, look here; I don't want to discuss this. I've told you more than I intended, anyway." Masterson had risen. His suavity masked a final determination to say no more. II The Soul Analysis The day was far advanced after this series of very unsatisfactory interviews. I looked at Kennedy blankly. We seemed to have uncovered so little that was tangible that I was much surprised to find that apparently he was well contented with what had happened in the case so far. "I shall be busy for a few hours in the laboratory, Walter," he remarked, as we parted at the subway. "I think, if you have nothing better to do, that you might employ the time in looking up some of the gossip about Mrs. Maitland and Masterson, to say nothing of Dr. Ross," he emphasised. "Drop in after dinner." There was not much that I could find. Of Mrs. Maitland there was practically nothing that I already did not know from having seen her name in the papers. She was a leader in a certain set which was devoting its activities to various social and moral propaganda. Masterson's early escapades were notorious even in the younger smart set in which he had moved, but his years abroad had mellowed the recollection of them. He had not distinguished himself in any way since his return to set gossip afloat, nor had any tales of his doings abroad filtered through to New York clubland. Dr. Ross, I found to my surprise, was rather better known than I had supposed, both as a specialist and as a man about town. He seemed to have risen rapidly in his profession as physician to the ills of society's nerves. I was amazed after dinner to find Kennedy doing nothing at all. "What's the matter?" I asked. "Have you struck a snag?" "No," he replied slowly, "I was only waiting. I told them to be here between half-past eight and nine." "Who?" I queried. "Dr. Leslie," he answered. "He has the authority to compel the attendance of Mrs. Maitland, Dr. Ross, and Masterson." The quickness with which he had worked out a case which was, to me, one of the most inexplicable he had had for a long time, left me standing speechless. One by one they dropped in during the next half-hour, and, as usual, it fell to me to receive them and smooth over the rough edges which always obtruded at these little enforced parties in the laboratory. Dr. Leslie and Dr. Ross were the first to arrive. They had not come together, but had met at the door. I fancied I saw a touch of professional jealousy in their manner, at least on the part of Dr. Ross. Masterson came, as usual ignoring the seriousness of the matter and accusing us all of conspiring to keep him from the first night of a light opera which was opening. Mrs. Maitland followed, the unaccustomed pallor of her face heightened by the plain black dress. I felt most uncomfortable, as indeed I think the rest did. She merely inclined her head to Masterson, seemed almost to avoid the eye of Dr. Ross, glared at Dr. Leslie, and absolutely ignored me. Craig had been standing aloof at his laboratory table, beyond a nod of recognition paying little attention to anything. He seemed to be in no hurry to begin. "Great as science is," he commenced, at length, "it is yet far removed from perfection. There are, for instance, substances so mysterious, subtle, and dangerous as to set the most delicate tests and powerful lenses at naught, while they carry death most horrible in their train." He could scarcely have chosen his opening words with more effect. "Chief among them," he proceeded, "are those from nature's own laboratory. There are some sixty species of serpents, for example, with deadly venom. Among these, as you doubtless have all heard, none has brought greater terror to mankind than the cobra-di-capello, the Naja tripudians of India. It is unnecessary for me to describe the cobra or to say anything about the countless thousands who have yielded up their lives to it. I have here a small quantity of the venom"--he indicated it in a glass beaker. "It was obtained in New York, and I have tested it on guinea-pigs. It has lost none of its potency." I fancied that there was a feeling of relief when Kennedy by his actions indicated that he was not going to repeat the test. "This venom," he continued, "dries in the air into a substance like small scales, soluble in water but not in alcohol. It has only a slightly acrid taste and odour, and, strange to say, is inoffensive on the tongue or mucous surfaces, even in considerable quantities. All we know about it is that in an open wound it is deadly swift in action." It was difficult to sit unmoved at the thought that before us, in only a few grains of the stuff, was enough to kill us all if it were introduced into a scratch of our skin. "Until recently chemistry was powerless to solve the enigma, the microscope to detect its presence, or pathology to explain the reason for its deadly effect. And even now, about all we know is that autopsical research reveals absolutely nothing but the general disorganisation of the blood corpuscles. In fact, such poisoning is best known by the peculiar symptoms--the vertigo, weak legs, and falling jaw. The victim is unable to speak or swallow, but is fully sensible. He has nausea, paralysis, an accelerated pulse at first followed rapidly by a weakening, with breath slow and laboured. The pupils are contracted, but react to the last, and he dies in convulsions like asphyxia. It is both a blood and a nerve poison." As Kennedy proceeded, Mrs. Maitland never took her large eyes from his face. Kennedy now drew from a large envelope in which he protected it, the typewritten note which had been found on Maitland. He said nothing about the "suicide" as he quietly began a new line of accumulating evidence. "There is an increasing use of the typewriting machine for the production of spurious papers," he began, rattling the note significantly. "It is partly due to the great increase in the use of the typewriter generally, but more than all is it due to the erroneous idea that fraudulent typewriting cannot be detected. The fact is that the typewriter is perhaps a worse means of concealing identity than is disguised handwriting. It does not afford the effective protection to the criminal that is supposed. On the contrary, the typewriting of a fraudulent document may be the direct means by which it can be traced to its source. First we have to determine what kind of machine a certain piece of writing was done with, then what particular machine." He paused and indicated a number of little instruments on the table. "For example," he resumed, "the Lovibond tintometer tells me its story of the colour of the ink used in the ribbon of the machine that wrote this note as well as several standard specimens which I have been able to obtain from three machines on which it might have been written. "That leads me to speak of the quality of the paper in this half-sheet that was found on Mr. Maitland. Sometimes such a half-sheet may be mated with the other half from which it was torn as accurately as if the act were performed before your eyes. There was no such good fortune in this case, but by measurements made by the vernier micrometer caliper I have found the precise thickness of several samples of paper as compared to that of the suicide note. I need hardly add that in thickness and quality, as well as in the tint of the ribbon, the note points to person as the author." No one moved. "And there are other proofs--unescapable," Kennedy hurried on. "For instance, I have counted the number of threads to the inch in the ribbon, as shown by the letters of this note. That also corresponds to the number in one of the three ribbons." Kennedy laid down a glass plate peculiarly ruled in little squares. "This," he explained, "is an alignment test plate, through which can be studied accurately the spacing and alignment of typewritten characters. There are in this pica type ten to the inch horizontally and six to the inch vertically. That is usual. Perhaps you are not acquainted with the fact that typewritten characters are in line both ways, horizontally and vertically. There are nine possible positions for each character which may be assumed with reference to one of these little standard squares of the test plate. You cannot fail to appreciate what an immense impossibility there is that one machine should duplicate the variations out of the true which the microscope detects for several characters on another. "Not only that, but the faces of many letters inevitably become broken, worn, battered, as well as out of alignment, or slightly shifted in their position on the type bar. The type faces are not flat, but a little concave to conform to the roller. There are thousands of possible divergences, scars, and deformities in each machine. "Such being the case," he concluded, "typewriting has an individuality like that of the Bertillon system, finger-prints, or the portrait parle." He paused, then added quickly: "What machine was it in this case? I have samples here from that of Dr. Boss, from a machine used by Mr. Masterson's secretary, and from a machine which was accessible to both Mr. and Mrs. Maitland." Kennedy stopped, but he was not yet prepared to relieve the suspense of two of those whom his investigation would absolve. "Just one other point," he resumed mercilessly, "a point which a few years ago would have been inexplicable--if not positively misleading and productive of actual mistake. I refer to the dreams of Mrs. Maitland." I had been expecting it, yet the words startled me. What must they have done to her? But she kept admirable control of herself. "Dreams used to be treated very seriously by the ancients, but until recently modern scientists, rejecting the ideas of the dark ages, have scouted dreams. To-day, however, we study them scientifically, for we believe that whatever is, has a reason. Dr. Ross, I think, is acquainted with the new and remarkable theories of Dr. Sigmund Freud, of Vienna?" Dr. Ross nodded. "I dissent vigorously from some of Freud's conclusions," he hastened. "Let me state them first," resumed Craig. "Dreams, says Freud, are very important. They give us the most reliable information concerning the individual. But that is only possible"--Kennedy emphasised the point--"if the patient is in entire rapport with the doctor. "Now, the dream is not an absurd and senseless jumble, but a perfect mechanism and has a definite meaning in penetrating the mind. It is as though we had two streams of thought, one of which we allow to flow freely, the other of which we are constantly repressing, pushing back into the subconscious, or unconscious. This matter of the evolution of our individual mental life is too long a story to bore you with at such a critical moment. "But the resistances, the psychic censors of our ideas, are always active, except in sleep. Then the repressed material comes to the surface. But the resistances never entirely lose their power, and the dream shows the material distorted. Seldom does one recognise his own repressed thoughts or unattained wishes. The dream really is the guardian of sleep to satisfy the activity of the unconscious and repressed mental processes that would otherwise disturb sleep by keeping the censor busy. In the case of a nightmare the watchman or censor is aroused, finds himself overpowered, so to speak, and calls on consciousness for help. "There are three kinds of dreams--those which represent an unrepressed wish as fulfilled, those that represent the realisation of a repressed wish in an entirely concealed form, and those that represent the realisation of a repressed wish in a form insufficiently or only partially concealed. "Dreams are not of the future, but of the past, except as they show striving for unfulfilled wishes. Whatever may be denied in reality we nevertheless can realise in another way--in our dreams. And probably more of our daily life, conduct, moods, beliefs than we think, could be traced to preceding dreams." Dr. Ross was listening attentively, as Craig turned to him. "This is perhaps the part of Freud's theory from which you dissent most strongly. Freud says that as soon as you enter the intimate life of a patient you begin to find sex in some form. In fact, the best indication of abnormality would be its absence. Sex is one of the strongest of human impulses, yet the one subjected to the greatest repression. For that reason it is the weakest point in our cultural development. In a normal life, he says, there are no neuroses. Let me proceed now with what the Freudists call the psychanalysis, the soul analysis, of Mrs. Maitland." It was startling in the extreme to consider the possibilities to which this new science might lead, as he proceeded to illustrate it. "Mrs. Maitland," he continued, "your dream of fear was a dream of what we call the fulfilment of a suppressed wish. Moreover, fear always denotes a sexual idea underlying the dream. In fact, morbid anxiety means surely unsatisfied love. The old Greeks knew it. The gods of fear were born of the goddess of love. Consciously you feared the death of your husband because unconsciously you wished it." It was startling, dramatic, cruel, perhaps, merciless--this dissecting of the soul of the handsome woman before us; but it had come to a point where it was necessary to get at the truth. Mrs. Maitland, hitherto pale, was now flushed and indignant. Yet the very manner of her indignation showed the truth of the new psychology of dreams, for, as I learned afterward, people often become indignant when the Freudists strike what is called the "main complex." "There are other motives just as important," protested Dr. Boss. "Here in America the money motive, ambition--" "Let me finish," interposed Kennedy. "I want to consider the other dream also. Fear is equivalent to a wish in this sort of dream. It also, as I have said, denotes sex. In dreams animals are usually symbols. Now, in this second dream we find both the bull and the serpent, from time immemorial, symbols of the continuing of the life-force. Dreams are always based on experiences or thoughts of the day preceding the dreams. You, Mrs. Maitland, dreamed of a man's face on these beasts. There was every chance of having him suggested to you. You think you hate him. Consciously you reject him; unconsciously you accept him. Any of the new psychologists who knows the intimate connection between love and hate, would understand how that is possible. Love does not extinguish hate; or hate, love. They repress each other. The opposite sentiment may very easily grow." The situation was growing more tense as he proceeded. Was not Kennedy actually taxing her with loving another? "The dreamer," he proceeded remorselessly, "is always the principal actor in a dream, or the dream centres about the dreamer most intimately. Dreams are personal. We never dream about matters that really concern others, but ourselves. "Years ago," he continued, "you suffered what the new psychologists call a 'psychic trauma'--a soul-wound. You were engaged, but your censored consciousness rejected the manner of life of your fiance. In pique you married Price Maitland. But you never lost your real, subconscious love for another." He stopped, then added in a low tone that was almost inaudible, yet which did not call for an answer, "Could you--be honest with yourself, for you need say not a word aloud--could you always be sure of yourself in the face of any situation?" She looked startled. Her ordinarily inscrutable face betrayed everything, though it was averted from the rest of us and could be seen only by Kennedy. She knew the truth that she strove to repress; she was afraid of herself. "It is dangerous," she murmured, "to be with a person who pays attention to such little things. If every one were like you, I would no longer breathe a syllable of my dreams." She was sobbing now. What was back of it all? I had heard of the so-called resolution dreams. I had heard of dreams that kill, of unconscious murder, of the terrible acts of the subconscious somnambulist of which the actor has no recollection in the waking state until put under hypnotism. Was it that which Kennedy was driving at disclosing? Dr. Ross moved nearer to Mrs. Maitland as if to reassure her. Craig was studying attentively the effect of his revelation both on her and on the other faces before him. Mrs. Maitland, her shoulders bent with the outpouring of the long-suppressed emotion of the evening and of the tragic day, called for sympathy which, I could see, Craig would readily give when he had reached the climax he had planned. "Kennedy," exclaimed Masterson, pushing aside Dr. Ross, as he bounded to the side of Mrs. Maitland, unable to restrain himself longer, "Kennedy, you are a faker--nothing but a damned dream doctor--in scientific disguise." "Perhaps," replied Craig, with a quiet curl of the lip. "But the threads of the typewriter ribbon, the alignment of the letters, the paper, all the 'fingerprints' of that type-written note of suicide were those of the machine belonging to the man who caused the soul-wound, who knew Madeline Maitland's inmost heart better than herself--because he had heard of Freud undoubtedly, when he was in Vienna--who knew that he held her real love still, who posed as a patient of Dr. Ross to learn her secrets as well as to secure the subtle poison of the cobra. That man, perhaps, merely brushed against Price Maitland in the crowd, enough to scratch his hand with the needle, shove the false note into his pocket--anything to win the woman who he knew loved him, and whom he could win. Masterson, you are that man!" The next half hour was crowded kaleidoscopically with events--the call by Dr. Leslie for the police, the departure of the Coroner with Masterson in custody, and the efforts of Dr. Ross to calm his now almost hysterical patient, Mrs. Maitland. Then a calm seemed to settle down over the old laboratory which had so often been the scene of such events, tense with human interest. I could scarcely conceal my amazement, as I watched Kennedy quietly restoring to their places the pieces of apparatus he had used. "What's the matter?" he asked, catching my eye as he paused with the tintometer in his hand. "Why," I exclaimed, "that's a fine way to start a month! Here's just one day gone and you've caught your man. Are you going to keep that up? If you are--I'll quit and skip to February. I'll choose the shortest month, if that's the pace!" "Any month you please," he smiled grimly, as he reluctantly placed the tintometer in its cabinet. There was no use. I knew that any other month would have been just the same. "Well," I replied weakly, "all I can hope is that every day won't be as strenuous as this has been. I hope, at least, you will give me time to make some notes before you start off again." "Can't say," he answered, still busy returning paraphernalia to its accustomed place. "I have no control over the cases as they come to me--except that I fan turn down those that don't interest me." "Then," I sighed wearily, "turn down the next one. I must have rest. I'm going home to sleep." "Very well," he said, making no move to follow me. I shook my head doubtfully. It was impossible to force a card on Kennedy. Instead of showing any disposition to switch off the laboratory lights, he appeared to be regarding a row of half-filled test-tubes with the abstraction of a man who has been interrupted in the midst of an absorbing occupation. "Good night," I said at length. "Good night," he echoed mechanically. I know that he slept that night--at least his bed had been slept in when I awoke in the morning. But he was gone. But then, it was not unusual for him, when the fever for work was on him, to consider even five or fewer hours a night's rest. It made no difference when I argued with him. The fact that he thrived on it himself and could justify it by pointing to other scientists was refutation enough. Slowly I dressed, breakfasted, and began transcribing what I could from the hastily jotted down notes of the day before. I knew that the work, whatever it was, in which he was now engaged must be in the nature of research, dear to his heart. Otherwise, he would have left word for me. No word came from him, however, all day, and I had not only caught up in my notes, but, my appetite whetted by our first case, had become hungry for more. In fact I had begun to get a little worried at the continued silence. A hand on the knob of the door or a ring of the telephone would hare been a welcome relief. I was gradually becoming aware of the fact that I liked the excitement of the life as much as Kennedy did. I knew it when the sudden sharp tinkle of the telephone set my heart throbbing almost as quickly as the little bell hammer buzzed. "Jameson, for Heaven's sake find Kennedy immediately and bring him over here to the Novella Beauty Parlour. We've got the worst case I've been up against in a long time. Dr. Leslie, the coroner, is here, and says we must not make a move until Kennedy arrives." I doubt whether in all our long acquaintance I had ever heard First Deputy O'Connor more wildly excited and apparently more helpless than he seemed over the telephone that night. "What is it?" I asked. "Never mind, never mind. Find Kennedy," he called back almost brusquely. "It's Miss Blanche Blaisdell, the actress--she's been found dead here. The thing is an absolute mystery. Now get him, GET HIM." It was still early in the evening, and Kennedy had not come in, nor had he sent any word to our apartment. O'Connor had already tried the laboratory. As for myself, I had not the slightest idea where Craig was. I knew the case must be urgent if both the deputy and the coroner were waiting for him. Still, after half an hour's vigorous telephoning, I was unable to find a trace of Kennedy in any of his usual haunts. In desperation I left a message for him with the hall-boy in case he called up, jumped into a cab, and rode over to the laboratory, hoping that some of the care-takers might still be about and might know something of his whereabouts. The janitor was able to enlighten me to the extent of telling me that a big limousine had called for Kennedy an hour or so before, and that he had left in great haste. I had given it up as hopeless and had driven back to the apartment to wait for him, when the hall-boy made a rush at me just as I was paying my fare. "Mr. Kennedy on the wire, sir," he cried as he half dragged me into the hall. "Walter," almost shouted Kennedy, "I'm over at the Washington Heights Hospital with Dr. Barron--you remember Barron, in our class at college? He has a very peculiar case of a poor girl whom he found wandering on the street and brought here. Most unusual thing. He came over to the laboratory after me in his car. Yes, I have the message that you left with the hall-boy. Come up here and pick me up, and we'll ride right down to the Novella. Goodbye." I had not stopped to ask questions and prolong the conversation, knowing as I did the fuming impatience of O'Connor. It was relief enough to know that Kennedy was located at last. He was in the psychopathic ward with Barron, as I hurried in. The girl whom he had mentioned over the telephone was then quietly sleeping under the influence of an opiate, and they were discussing the case outside in the hall. "What do you think of it yourself?" Barron was asking, nodding to me to join them. Then he added for my enlightenment: "I found this girl wandering bareheaded in the street. To tell the truth, I thought at first that she was intoxicated, but a good look showed me better than that. So I hustled the poor thing into my car and brought her here. All the way she kept crying over and over: 'Look, don't you see it? She's afire! Her lips shine--they shine, they shine.' I think the girl is demented and has had some hallucination." "Too vivid for a hallucination," remarked Kennedy decisively. "It was too real to her. Even the opiate couldn't remove the picture, whatever it was, from her mind until you had given her almost enough to kill her, normally. No, that wasn't any hallucination. Now, Walter, I'm ready." III THE SYBARITE We found the Novella Beauty Parlour on the top floor of an office-building just off Fifth Avenue on a side street not far from Forty-second Street. A special elevator, elaborately fitted up, wafted us up with express speed. As the door opened we saw a vista of dull-green lattices, little gateways hung with roses, windows of diamond-paned glass get in white wood, rooms with little white enamelled manicure-tables and chairs, amber lights glowing with soft incandescence in deep bowers of fireproof tissue flowers. There was a delightful warmth about the place, and the seductive scents and delicate odours betokened the haunt of the twentieth-century Sybarite. Both O'Connor and Leslie, strangely out of place in the enervating luxury of the now deserted beauty-parlour, were still waiting for Kennedy with a grim determination. "A most peculiar thing," whispered O'Connor, dashing forward the moment the elevator door opened. "We can't seem to find a single cause for her death. The people up here say it was a suicide, but I never accept the theory of suicide unless there are undoubted proofs. So far there have been none in this case. There was no reason for it." Seated in one of the large easy-chairs of the reception-room, in a corner with two of O'Connor's men standing watchfully near, was a man who was the embodiment of all that was nervous. He was alternately wringing his hands and rumpling his hair. Beside him was a middle-sized, middle-aged lady in a most amazing state of preservation, who evidently presided over the cosmetic mysteries beyond the male ken. She was so perfectly groomed that she looked as though her clothes were a mould into which she had literally been poured. "Professor and Madame Millefleur--otherwise Miller,"--whispered O'Connor, noting Kennedy's questioning gaze and taking his arm to hurry him down a long, softly carpeted corridor, flanked on either side by little doors. "They run the shop. They say one of the girls just opened the door and found her dead." Near the end, one of the doors stood open, and before it Dr. Leslie, who had preceded us, paused. He motioned to us to look in. It was a little dressing-room, containing a single white-enamelled bed, a dresser, and a mirror. But it was not the scant though elegant furniture that caused us to start back. There under the dull half-light of the corridor lay a woman, most superbly formed. She was dark, and the thick masses of her hair, ready for the hairdresser, fell in a tangle over her beautifully chiselled features and full, rounded shoulders and neck. A scarlet bathrobe, loosened at the throat, actually accentuated rather than covered the voluptuous lines of her figure, down to the slender ankle which had been the beginning of her fortune as a danseuse. Except for the marble pallor of her face it was difficult to believe that she was not sleeping. And yet there she was, the famous Blanche Blaisdell, dead--dead in the little dressing-room of the Novella Beauty Parlour, surrounded as in life by mystery and luxury. We stood for several moments speechless, stupefied. At last O'Connor silently drew a letter from his pocket. It was written on the latest and most delicate of scented stationery. "It was lying sealed on the dresser when we arrived," explained O'Connor, holding it so that we could not see the address. "I thought at first she had really committed suicide and that this was a note of explanation. But it is not. Listen. It is just a line or two. It reads: 'Am feeling better now, though that was a great party last night. Thanks for the newspaper puff which I have just read. It was very kind of you to get them to print it. Meet me at the same place and same time to-night. Your Blanche.' The note was not stamped, and was never sent. Perhaps she rang for a messenger. At any rate, she must have been dead before she could send it. But it was addressed to--Burke Collins." "Burke Collins!" exclaimed Kennedy and I together in amazement. He was one of the leading corporation lawyers in the country, director in a score of the largest companies, officer in half a dozen charities and social organisations, patron of art and opera. It seemed impossible, and I at least did not hesitate to say so. For answer O'Connor simply laid the letter and envelope down on the dresser. It seemed to take some time to convince Kennedy. There it was in black and white, however, in Blanche Blaisdell's own vertical hand. Try to figure it out as I could, there seemed to be only one conclusion, and that was to accept it. What it was that interested him I did not know, but finally he bent down and sniffed, not at the scented letter, but at the covering on the dresser. When he raised his head I saw that he had not been looking at the letter at all, but at a spot on the cover near it. "Sn-ff, sn-ff," he sniffed, thoughtfully closing his eyes as if considering something. "Yes--oil of turpentine." Suddenly he opened his eyes, and the blank look of abstraction that had masked his face was broken through by a gleam of comprehension that I knew flashed the truth to him intuitively. "Turn out that light in the corridor," he ordered quickly. Dr. Leslie found and turned the switch. There we were alone, in the now weird little dressing-room, alone with that horribly lovely thing lying there cold and motionless on the little white bed. Kennedy moved forward in the darkness. Gently, almost as if she were still the living, pulsing, sentient Blanche Blaisdell who had entranced thousands, he opened her mouth. A cry from O'Connor, who was standing in front of me, followed. "What's that, those little spots on her tongue and throat? They glow. It is the corpse light!" Surely enough, there were little luminous spots in her mouth. I had heard somewhere that there is a phosphorescence appearing during decay of organic substances which once gave rise to the ancient superstition of "corpse lights" and the will-o'-the-wisp. It was really due, I knew, to living bacteria. But there surely had been no time for such micro-organisms to develop, even in the almost tropic heat of the Novella. Could she have been poisoned by these phosphorescent bacilli? What was it--a strange new mouth-malady that had attacked this notorious adventuress and woman of luxury? Leslie had flashed up the light again before Craig spoke. We were all watching him keenly. "Phosphorus, phosphoric acid, or phosphoric salve," Craig said slowly, looking eagerly about the room as if in search of something that would explain it. He caught sight of the envelope still lying on the dresser. He picked it up, toyed with it, looked at the top where O'Connor had slit it, then deliberately tore the flap off the back where it had been glued in sealing the letter. "Put the light out again," he asked. Where the thin line of gum was on the back of the flap, in the darkness there glowed the same sort of brightness that we had seen in a speck here and there on Blanche Blaisdell's lips and in her mouth. The truth flashed over me. Some one had placed the stuff, whatever it was, on the flap of the envelope, knowing that she must touch her lips to it to seal it She had done so, and the deadly poison had entered her mouth. As the light went up again Kennedy added: "Oil of turpentine removes traces of phosphorus, phosphoric acid, or phosphoric salve, which are insoluble in anything else except ether and absolute alcohol. Some one who knew that tried to eradicate them, but did not wholly succeed. O'Connor, see if you can find either phosphorus, the oil, or the salve anywhere in the shop." Then as O'Connor and Leslie hurriedly disappeared he added to me: "Another of those strange coincidences, Walter. You remember the girl at the hospital? 'Look, don't you see it? She's afire. Her lips shine--they shine, they shine!'" Kennedy was still looking carefully over the room. In a little wicker basket was a newspaper which was open at the page of theatrical news, and as I glanced quickly at it I saw a most laudatory paragraph about her. Beneath the paper were some torn scraps. Kennedy picked them up and pieced them together. "Dearest Blanche," they read. "I hope you're feeling better after that dinner last night. Can you meet me to-night? Write me immediately. Collie." He placed the scraps carefully in his wallet. There was nothing more to be done here apparently. As we passed down the corridor we could hear a man apparently raving in good English and bad French. It proved to be Millefleur--or Miller--and his raving was as overdone as that of a third-rate actor. Madame was trying to calm him. "Henri, Henri, don't go on so," she was saying. "A suicide--in the Novella. It will be in all the papers. We shall be ruined. Oh--oh!" "Here, can that sob stuff," broke in one of O'Connor's officers. "You can tell it all when the chief takes you to headquarters, see?" Certainly the man made no very favourable impression by his actions. There seemed to be much that was forced about them, that was more incriminating than a stolid silence would have been. Between them Monsieur and Madame made out, however, to repeat to Kennedy their version of what had happened. It seemed that a note addressed to Miss Blaisdell had been left by some one on the desk in the reception-room. No one knew who left it, but one of the girls had picked it up and delivered it to her in her dressing-room. A moment later she rang her bell and called for one of the girls named Agnes, who was to dress her hair. Agnes was busy, and the actress asked her to get paper, a pen, and ink. At least it seemed that way, for Agnes got them for her. A few minutes later her bell rang again, and Agnes went down, apparently to tell her that she was now ready to dress her hair. The next thing any one knew was a piercing shriek from the girl. She ran down the corridor, still shrieking, out into the reception-room and rushed into the elevator, which happened to be up at the time. That was the last they had seen of her. The other girls saw Miss Blaisdell lying dead, and a panic followed. The customers dressed quickly and fled, almost in panic. All was confusion. By that time a policeman had arrived, and soon after O'Connor and the coroner had come. There was little use in cross-questioning the couple. They had evidently had time to agree on the story; that is, supposing it were not true. Only a scientific third degree could have shaken them, and such a thing was impossible just at that time. From the line of Kennedy's questions I could see that he believed that there was a hiatus somewhere in their glib story, at least some point where some one had tried to eradicate the marks of the poison. "Here it is. We found it," interrupted O'Connor, holding up in his excitement a bottle covered with black cloth to protect it from the light. "It was in the back of a cabinet in the operating-room, and it is marked 'Ether phosphore".' Another of oil of turpentine was on a shelf in another cabinet. Both seem to have been used lately, judging by the wetness of the bottoms of the glass stoppers." "Ether phosphore, phosphorated ether," commented Kennedy, reading the label to himself. "A remedy from the French Codex, composed, if I remember rightly, of one part phosphorus and fifty parts sulphuric ether. Phosphorus is often given as a remedy for loss of nerve power, neuralgia, hysteria, and melancholia. In quantities from a fiftieth to a tenth or so of a grain free phosphorus is a renovator of nerve tissue and nerve force, a drug for intense and long-sustained anxiety of mind and protracted emotional excitement--in short, for fast living." He uncorked the bottle, and we tasted the stuff. It was unpleasant and nauseous. "I don't see why it wasn't used in the form of pills. The liquid form of a few drops on gum arabic is hopelessly antiquated." The elevator door opened with a clang, and a well-built, athletic looking man of middle age with an acquired youngish look about his clothes and clean-shaven face stepped out. His face was pale, and his hand shook with emotion that showed that something had unstrung his usually cast-iron nerves. I recognised Burke Collins at once. In spite of his nervousness he strode forward with the air of a man accustomed to being obeyed, to having everything done for him merely because he, Burke Collins, could afford to pay for it and it was his right. He seemed to know whom he was seeking, for he immediately singled out O'Connor. "This is terrible, terrible," he whispered hoarsely. "No, no, no, I don't want to see her. I can't, not yet. You know I thought the world of that poor little girl. Only," and here the innate selfishness of the man cropped out, "only I called to ask you that nothing of my connection with her be given out. You understand? Spare nothing to get at the truth. Employ the best men you have. Get outside help if necessary. I'll pay for anything, anything. Perhaps I can use some influence for you some day, too. But, you understand--the scandal, you know. Not a word to the newspapers." At another time I feel sure that O'Connor would have succumbed. Collins was not without a great deal of political influence, and even a first deputy may be "broke" by a man with influence. But now here was Kennedy, and he wished to appear in the best light. He looked at Craig. "Let me introduce Professor Kennedy," he said. "I've already called him in." "Very happy to have the pleasure of meeting you," said Collins, grasping Kennedy's hand warmly. "I hope you will take me as your client in this case. I'll pay handsomely. I've always had a great admiration for your work, and I've heard a great deal about it." Kennedy is, if anything, as impervious to blandishment as a stone, as the Blarney Stone is itself, for instance. "On one condition," he replied slowly, "and that is that I go ahead exactly as if I were employed by the city itself to get at the truth." Collins bit his lip. It was evident that he was not accustomed to being met in this independent spirit. "Very well," he answered at last. "O'Connor has called you in. Work for him and--well, you know, if you need anything just draw on me for it. Only if you can, keep me out of it. I'll tell everything I can to help you--but not to the newspapers." He beckoned us outside. "Those people in there," he nodded his head back in the direction of the Millefleurs, "do you suspect them? By George, it does look badly for them, doesn't it, when you come to think of it? Well, now, you see, I'm frank and confidential about my relations with Blan--er--Miss Blaisdell. I was at a big dinner with her last night with a party of friends. I suppose she came here to get straightened out. I hadn't been able to get her on the wire to-day, but at the theatre when I called up they told me what had happened, and I came right over here. Now please remember, do everything, anything but create a scandal. You realise what that would mean for me." Kennedy said nothing. He simply laid down on the desk, piece by piece, the torn letter which he had picked up from the basket, and beside it he spread out the reply which Blanche had written. "What?" gasped Collins as he read the torn letter. "I send that? Why, man alive, you're crazy. Didn't I just tell you I hadn't heard from her until I called up the theatre just now?" I could not make out whether he was lying or not when he said that he had not sent the note. Kennedy picked up a pen. "Please write the same thing as you read in the note on this sheet of the Novella paper. It will be all right. You have plenty of witnesses to that." It must have irked Collins even to have his word doubted, but Kennedy was no respecter of persons. He took the pen and wrote. "I'll keep your name out of it as much as possible," remarked Kennedy, glancing intently at the writing and blotting it. "Thank you," said Collins simply, for once in his life at a loss for words. Once more he whispered to O'Connor, then he excused himself. The man was so obviously sincere, I felt, as far as his selfish and sensual limitations would permit, that I would not have blamed Kennedy for giving him much more encouragement than he had given. Kennedy was not through yet, and now turned quickly again to the cosmetic arcadia which had been so rudely stirred by the tragedy. "Who is this girl Agnes who discovered Miss Blaisdell?" he shot out at the Millefleurs. The beauty-doctor was now really painful in his excitement. Like his establishment, even his feelings were artificial. "Agnes?" he repeated. "Why, she was one of Madame's best hair-dressers. See--my dear--show the gentlemen the book of engagements." It was a large book full of girls' names, each an expert in curls, puffs, "reinforcements," hygienic rolls, transformators, and the numberless other things that made the fearful and wonderful hair-dresses of the day. Agnes's dates were full, for a day ahead. Kennedy ran his eye over the list of patrons. "Mrs. Burke Collins, 3:30," he read. "Was she a patron, too?" "Oh, yes," answered Madame. "She used to come here three times a week. It was not vanity. We all knew her, and we all liked her." Instantly I could read between the lines, and I felt that I had been too charitable to Burke Collins. Here was the wife slaving to secure that beauty which would win back the man with whom she had worked and toiled in the years before they came to New York and success. The "other woman" came here, too, but for a very different reason. Nothing but business seemed to impress Millefleur, however. "Oh, yes," he volunteered, "we have a fine class. Among my own patients I have Hugh Dayton, the actor, you know, leading man in Blanche Blaisdell's company. He is having his hair restored. Why, I gave him a treatment this afternoon. If ever there is a crazy man, it is he. I believe he would kill Mr. Collins for the way Blanche Blaisdell treats him. They were engaged--but, oh, well," he gave a very good imitation of a French shrug, "it is all over now. Neither of them will get her, and I--I am ruined. Who will come to the Novella now?" Adjoining Millefleur's own room was the writing room from which the poisoned envelope had been taken to Miss Blaisdell. Over the little secretary was the sign, "No woman need be plain who will visit the Novella," evidently the motto of the place. The hair-dressing room was next to the little writing-room. There were manicure rooms, steam-rooms, massage-rooms, rooms of all descriptions, all bearing mute testimony to the fundamental instinct, the feminine longing for personal beauty. Though it was late when Kennedy had finished his investigation, he insisted on going directly to his laboratory. There he pulled out from a corner a sort of little square table on which was fixed a powerful light such as might be used for a stereopticon. "This is a simple little machine," he explained, as be pasted together the torn bits of the letter which he had fished out of the scrap-basket, "which detectives use in studying forgeries. I don't know that it has a name, although it might be called a 'rayograph.' You see, all you have to do is to lay the thing you wish to study flat here, and the system of mirrors and lenses reflects it and enlarges it on a sheet." He had lowered a rolled-up sheet of white at the opposite end of the room, and there, in huge characters, stood forth plainly the writing of the note. "This letter," he resumed, studying the enlargement carefully, "is likely to prove crucial. It's very queer. Collins says he didn't write it, and if he did he surely is a wonder at disguising his hand. I doubt if any one could disguise what the rayograph shows. Now, for instance, this is very important. Do you see how those strokes of the long letters are--well, wobbly? You'd never see that in the original, but when it is enlarged you see how plainly visible the tremors of the hand become? Try as you may, you can't conceal them. The fact is that the writer of this note suffered from a form of heart disease. Now let us look at the copy that Collins made at the Novella." He placed the copy on the table of the rayograph. It was quite evident that the two had been written by entirely different persons. "I thought he was telling the truth," commented Craig, "by the surprised look on his face the moment I mentioned the note to Miss Blaisdell. Now I know he was. There is no such evidence of heart trouble in his writing as in the other. Of course that's all aside from what a study of the handwriting itself might disclose. They are not similar at all. But there is an important clue there. Find the writer of that note who has heart trouble, and we either have the murderer or some one close to the murderer." I remembered the tremulousness of the little beauty-doctor, his third-rate artificial acting of fear for the reputation of the Novella, and I must confess I agreed with O'Connor and Collins that it looked black for him. At one time I had suspected Collins himself, but now I could see perfectly why he had not concealed his anxiety to hush up his connection with the case, while at the same time his instinct as a lawyer, and I had almost added, lover, told him that justice must be done. I saw at once how, accustomed as he was to weigh evidence, he had immediately seen the justification for O'Connor's arrest of the Millefleurs. "More than that," added Kennedy, after examining the fibres of the paper under a microscope, "all these notes are written on the same kind of paper. That first torn note to Miss Blaisdell was written right in the Novella and left so as to seem to have been sent in from outside." It was early the following morning when Kennedy roused me with the remark: "I think I'll go up to the hospital. Do you want to come along? We'll stop for Barron on the way. There is a little experiment I want to try on that girl up there." When we arrived, the nurse in charge of the ward told us that her patient had passed a fairly good night, but that now that the influence of the drug had worn off she was again restless and still repeating the words that she had said over and over before. Nor had she been able to give any clearer account of herself. Apparently she had been alone in the city, for although there was a news item about her in the morning papers, so far no relative or friend had called to identify her. Kennedy had placed himself directly before her, listening intently to her ravings. Suddenly he managed to fix her eye, as if by a sort of hypnotic influence. "Agnes!" he called in a sharp tone. The name seemed to arrest her fugitive attention. Before she could escape from his mental grasp again he added: "Your date-book is full. Aren't you going to the Novella this morning?" The change in her was something wonderful to see. It was as though she had come out of a trance. She sat up in bed and gazed about blankly. "Yes, yes, I must go," she cried as if it were the most natural thing in the world. Then she realised the strange surroundings and faces. "Where is my hat--wh-where am I? What has happened?" "You are all right," soothed Kennedy gently. "Now rest. Try to forget everything for a little while, and you will be all right. You are among friends." As Kennedy led us out she fell back, now physically exhausted, on the pillow. "I told you, Barron," he whispered, "that there was more to this case than you imagined. Unwittingly you brought me a very important contribution to a case of which the papers are full this morning, the case of the murdered actress, Blanche Blaisdell." IV THE BEAUTY SHOP It was only after a few hours that Kennedy thought it wise to try to question the poor girl at the hospital. Her story was simple enough in itself, but it certainly complicated matters considerably without throwing much light on the case. She had been busy because her day was full, and she had yet to dress the hair of Miss Blaisdell for her play that night. Several times she had been interrupted by impatient messages from the actress in her little dressing-booth, and one of the girls had already demolished the previous hair-dressing in order to save time. Once Agnes had run down for a few seconds to reassure her that she would be through in time. She had found the actress reading a newspaper, and when Kennedy questioned her she remembered seeing a note lying on the dresser. "Agnes," Miss Blaisdell had said, "will you go into the writing-room and bring me some paper, a pen, and ink? I don't want to go in there this way. There's a dear good girl." Agnes had gone, though it was decidedly no part of her duty as one of the highest paid employes of the Novella. But they all envied the popular actress, and were ready to do anything for her. The next thing she remembered was finishing the coiffure she was working on and going to Miss Blaisdell. There lay the beautiful actress. The light in the corridor had not been lighted yet, and it was dark. Her lips and mouth seemed literally to shine. Agnes called her, but she did not move; she touched her, but she was cold. Then she screamed and fled. That was the last she remembered. "The little writing-room," reasoned Kennedy as we left the poor little hair-dresser quite exhausted by her narrative, "was next to the sanctum of Millefleur, where they found that bottle of ether phosphore and the oil of turpentine. Some one who knew of that note or perhaps wrote it must have reasoned that an answer would be written immediately. That person figured that the note would be the next thing written and that the top envelope of the pile would be used. That person knew of the deadly qualities of too much phosphorised ether, and painted the gummed flap of the envelope with several grains of it. The reasoning held good, for Agnes took the top envelope with its poisoned flap to Miss Blaisdell. No, there was no chance about that. It was all clever, quick reasoning." "But," I objected, "how about the oil of turpentine?" "Simply to remove the traces of the poison. I think you will see why that was attempted before we get through." Kennedy would say no more, but I was content because I could see that he was now ready to put his theories, whatever they were, to the final test. He spent the rest of the day working at the hospital with Dr. Barron, adjusting a very delicate piece of apparatus down in a special room, in the basement. I saw it, but I had no idea what it was or what its use might be. Close to the wall was a stereopticon which shot a beam of light through a tube to which I heard them refer as a galvanometer, about three feet distant. In front of this beam whirled a five-spindled wheel, governed by a chronometer which erred only a second a day. Between the poles of the galvanometer was stretched a slender thread of fused quartz plated with silver, only one one-thousandth of a millimetre in diameter, so tenuous that it could not be seen except in a bright light. It was a thread so slender that it might have been spun by a microscopic spider. Three feet farther away was a camera with a moving film of sensitised material, the turning of which was regulated by a little flywheel. The beam of light focused on the thread in the galvanometer passed to the photographic film, intercepted only by the five spindles of the wheel, which turned once a second, thus marking the picture off into exact fifths of a second. The vibrations of the microscopic quartz thread were enormously magnified on the sensitive film by a lens and resulted in producing a long zig-zag, wavy line. The whole was shielded by a wooden hood which permitted no light, except the slender ray, to strike it. The film revolved slowly across the field, its speed regulated by the flywheel, and all moved by an electric motor. I was quite surprised, then, when Kennedy told me that the final tests which he was arranging were not to be held at the hospital at all, but in his laboratory, the scene of so many of his scientific triumphs over the cleverest of criminals. While he and Dr. Barren were still fussing with the machine he despatched me on the rather ticklish errand of gathering together all those who had been at the Novella at the time and might possibly prove important in the case. My first visit was to Hugh Dayton, whom I found in his bachelor apartment on Madison Avenue, apparently waiting for me. One of O'Connor's men had already warned him that any attempt to evade putting in an appearance when he was wanted would be of no avail. He had been shadowed from the moment that it was learned that he was a patient of Millefleur's and had been at the Novella that fatal afternoon. He seemed to realise that escape was impossible. Dayton was one of those typical young fellows, tall, with sloping shoulders and a carefully acquired English manner, whom one sees in scores on Fifth Avenue late in the afternoon. His face, which on the stage was forceful and attractive, was not prepossessing at close range. Indeed it showed too evident marks of excesses, both physical and moral, and his hand was none too steady. Still, he was an interesting personality, if not engaging. I was also charged with delivering a note to Burke Collins at his office. The purport of it was, I knew, a request couched in language that veiled a summons that Mrs. Collins was of great importance in getting at the truth, and that if he needed an excuse himself for being present it was suggested that he appear as protecting his wife's interests as a lawyer. Kennedy had added that I might tell him orally that he would pass over the scandal as lightly as possible and spare the feelings of both as much as he could. I was rather relieved when this mission was accomplished, for I had expected Collins to demur violently. Those who gathered that night, sitting expectantly in the little armchairs which Kennedy's students used during his lectures, included nearly every one who could cast any light on what had happened at the Novella. Professor and Madame Millefleur were brought up from the house of detention, to which both O'Connor and Dr. Leslie had insisted that they be sent. Millefleur was still bewailing the fate of the Novella, and Madame had begun to show evidences of lack of the constant beautification which she was always preaching as of the utmost importance to her patrons. Agnes was so far recovered as to be able to be present, though I noticed that she avoided the Millefleurs and sat as far from them as possible. Burke Collins and Mrs. Collins arrived together. I had expected that there would be an icy coolness if not positive enmity between them. They were not exactly cordial, though somehow I seemed to feel that now that the cause of estrangement was removed a tactful mutual friend might have brought about a reconciliation. Hugh Dayton swaggered in, his nervousness gone or at least controlled. I passed behind him once, and the odour that smote my olfactory sense told me too plainly that he had fortified himself with a stimulant on his way from the apartment to the laboratory. Of course O'Connor and Dr. Leslie were there, though in the background. It was a silent gathering, and Kennedy did not attempt to relieve the tension even by small talk as he wrapped the forearms of each of us with cloths steeped in a solution of salt. Upon these cloths he placed little plates of German silver to which were attached wires which led back of a screen. At last he was ready to begin. "The long history of science," he began as he emerged from behind the screen, "is filled with instances of phenomena, noted at first only for their beauty or mystery, which have been later proved to be of great practical value to mankind. A new example is the striking phenomenon of luminescence. Phosphorus, discovered centuries ago, was first merely a curiosity. Now it is used for many practical things, and one of the latest uses is as a medicine. It is a constituent of the body, and many doctors believe that the lack of it causes, and that its presence will cure, many ills. But it is a virulent and toxic drug, and no physician except one who knows his business thoroughly should presume to handle it. Whoever made a practice of using it at the Novella did not know his business, or he would have used it in pills instead of in the nauseous liquid. It is not with phosphorised ether as a medicine that we have to deal in this case. It is with the stuff as a poison, a poison administered by a demon." Craig shot the word out so that it had its full effect on his little audience. Then he paused, lowered his voice, and resumed on a new subject. "Up in the Washington Heights Hospital," he went on, "is an apparatus which records the secrets of the human heart. That is no figure of speech, but a cold scientific fact. This machine records every variation of the pulsations of the heart with such exquisite accuracy that it gives Dr. Barron, who is up there now, not merely a diagram of the throbbing organ of each of you seated here in my laboratory a mile away, but a sort of moving-picture of the emotions by which each heart here is swayed. Not only can Dr. Barron diagnose disease, but he can detect love, hate, fear, joy, anger, and remorse. This machine is known as the Einthoven 'string galvanometer,' invented by that famous Dutch physiologist of Leyden." There was a perceptible movement in our little audience at the thought that the little wires that ran back of the screen from the arms of each were connected with this uncanny instrument so far away. "It is all done by the electric current that the heart itself generates," pursued Kennedy, hammering home the new and startling idea. "That current is one of the feeblest known to science, for the dynamo that generates it is no ponderous thing of copper wire and steel castings. It is just the heart itself. The heart sends over the wire its own telltale record to the machine which registers it. The thing takes us all the way back to Galvani, who was the first to observe and study animal electricity. The heart makes only one three-thousandth of a volt of electricity at each beat. It would take over two hundred thousand men to light one of these incandescent lamps, two million or more to run a trolley-car. Yet just that slight little current is enough to sway the gossamer strand of quartz fibre up there at what we call the 'heart station.' So fine is this machine that the pulse-tracings produced by the sphygmograph, which I have used in other cases up to this time, are clumsy and inexact." Again he paused as if to let the fear of discovery sink deep into the minds of all of us. "This current, as I have said, passes from each one of you in turn over a wire and vibrates a fine quartz fibre up there in unison with each heart here. It is one of the most delicate bits of mechanism ever made, beside which the hairspring of a watch is coarse. Each of you in turn, is being subjected to this test. More than that, the record up there shows not only the beats of the heart but the successive waves of emotion that vary the form of those beats. Every normal individual gives what we call an 'electro-cardiogram,' which follows a certain type. The photographic film on which this is being recorded is ruled so that at the heart station Dr. Barron can read it. There are five waves to each heart-beat, which he letters P, Q, R, S, and T, two below and three above a base line on the film. They have all been found to represent a contraction of a certain portion of the heart. Any change of the height, width, or time of any one of those lines shows that there is some defect or change in the contraction of that part of the heart. Thus Dr. Barron, who has studied this thing carefully, can tell infallibly not only disease but emotion." It seemed as if no one dared look at his neighbour, as if all were trying vainly to control the beating of their own hearts. "Now," concluded Kennedy solemnly as if to force the last secret from the wildly beating heart of some one in the room, "it is my belief that the person who had access to the operating-room of the Novella was a person whose nerves were run down, and in addition to any other treatment that person was familiar with the ether phosphore. This person knew Miss Blaisdell well, saw her there, knew she was there for the purpose of frustrating that person's own dearest hopes. That person wrote her the note, and knowing that she would ask for paper and an envelope in order to answer it, poisoned the flap of the envelope. Phosphorus is a remedy for hysteria, vexatious emotions, want of sympathy, disappointed and concealed affections--but not in the quantities that this person lavished on that flap. Whoever it was, not life, but death, and a ghastly death, was uppermost in that person's thoughts." Agnes screamed. "I saw him take something and rub it on her lips, and the brightness went away. I--I didn't mean to tell, but, God help me, I must." "Saw whom?" demanded Kennedy, fixing her eye as he had when he had called her back from aphasia. "Him--Millefleur--Miller," she sobbed, shrinking back as if the very confession appalled her. "Yes," added Kennedy coolly, "Miller did try to remove the traces of the poison after he discovered it, in order to protect himself and the reputation of the Novella." The telephone bell tinkled. Craig seized the receiver. "Yes, Barron, this is Kennedy. You received the impulses all right? Good. And have you had time to study the records? Yes? What's that? Number seven? All right. I'll see you very soon and go over the records again with you. Good-bye." "One word more," he continued, now facing us. "The normal heart traces its throbs in regular rhythm. The diseased or overwrought heart throbs in degrees of irregularity that vary according to the trouble that affects it, both organic and emotional. The expert like Barron can tell what each wave means, just as he can tell what the lines in a spectrum mean. He can see the invisible, hear the inaudible, feel the intangible, with mathematical precision. Barron has now read the electro-cardiograms. Each is a picture of the beating of the heart that made it, and each smallest variation has a meaning to him. Every passion, every emotion, every disease, is recorded with inexorable truth. The person with murder in his heart cannot hide it from the string galvanometer, nor can that person who wrote the false note in which the very lines of the letters betray a diseased heart hide that disease. The doctor tells me that that person was number--" Mrs. Collins had risen wildly and was standing before us with blazing eyes. "Yes," she cried, pressing her hands on her breast as if it were about to burst and tell the secret before her lips could frame the words, "yes, I killed her, and I would follow her to the end of the earth if I had not succeeded. She was there, the woman who had stolen from me what was more than life itself. Yes, I wrote the note, I poisoned the envelope. I killed her." All the intense hatred that she had felt for that other woman in the days that she had vainly striven to equal her in beauty and win back her husband's love broke forth. She was wonderful, magnificent, in her fury. She was passion personified; she was fate, retribution. Collins looked at his wife, and even he felt the spell. It was not crime that she had done; it was elemental justice. For a moment she stood, silent, facing Kennedy. Then the colour slowly faded from her cheeks. She reeled. Collins caught her and imprinted a kiss, the kiss that for years she had longed and striven for again. She looked rather than spoke forgiveness as he held her and showered them on her. "Before Heaven," I heard him whisper into her ear, "with all my power as a lawyer I will free you from this." Gently Dr. Leslie pushed him aside and felt her pulse as she dropped limply into the only easy chair in the laboratory. "O'Connor," he said at length, "all the evidence that we really have hangs on an invisible thread of quartz a mile away. If Professor Kennedy agrees, let us forget what has happened here to-night. I will direct my jury to bring in a verdict of suicide. Collins, take good care of her." He leaned over and whispered so she could not hear. "I wouldn't promise her six weeks otherwise." I could not help feeling deeply moved as the newly reunited Collinses left the laboratory together. Even the bluff deputy, O'Connor, was touched by it and under the circumstances did what seemed to him his higher duty with a tact of which I had believed him scarcely capable. Whatever the ethics of the case, he left it entirely to Dr. Leslie's coroner's jury to determine. Burke Collins was already making hasty preparations for the care of his wife so that she might have the best medical attention to prolong her life for the few weeks or months before nature exacted the penalty which was denied the law. "That's a marvellous piece of apparatus," I remarked, standing over the connections with the string galvanometer, after all had gone. "Just suppose the case had fallen into the hands of some of these old-fashioned detectives--" "I hate post-mortems--on my own cases," interrupted Kennedy brusquely. "To-morrow will be time enough to clear up this mess. Meanwhile, let us get this thing out of our minds." He clapped his hat on his head decisively and deliberately walked out of the laboratory, starting off at a brisk pace in the moonlight across the campus to the avenue where now the only sound was the noisy rattle of an occasional trolley car. How long we walked I do not know. But I do know that for genuine relaxation after a long period of keen mental stress, there is nothing like physical exercise. We turned into our apartment, roused the sleepy hall-boy, and rode up. "I suppose people think I never rest," remarked Kennedy, carefully avoiding any reference to the exciting events of the past two days. "But I do. Like every one else, I have to. When I am working hard on a case--well, I have my own violent reaction against it--more work of a different kind. Others choose white lights, red wines and blue feelings afterwards. But I find, when I reach that state, that the best anti-toxin is something that will chase the last case from your brain by getting you in trim for the next unexpected event." He had sunk into an easy chair where he was running over in his mind his own plans for the morrow. "Just now I must recuperate by doing no work at all," he went on slowly undressing. "That walk was just what I needed. When the fever of dissipation comes on again, I'll call on you. You won't miss anything, Walter." Like the famous Finnegan, however, he was on again and gone again in the morning. This time I had no misgivings, although I should have liked to accompany him, for on the library table he had scrawled a little note, "Studying East Side to-day. Will keep in touch with you. Craig." My daily task of transcribing my notes was completed and I thought I would run down to the Star to let the editor know how I was getting along on my assignment. I had scarcely entered the door when the office boy thrust a message into my hand. It stopped me even before I had a chance to get as far as my own desk. It was from Kennedy at the laboratory and bore a time stamp that showed that it must have been received only a few minutes before I came in. "Meet me at the Grand Central," it read, "immediately." Without going further into the office, I turned and dropped down in the elevator to the subway. As quickly as an express could take me, I hurried up to the new station. "Where away?" I asked breathlessly, as Craig met me at the entrance through which he had reasoned I would come. "The coast or Down East?" "Woodrock," he replied quickly, taking my arm and dragging me down a ramp to the train that was just leaving for that fashionable suburb. "Well," I queried eagerly, as the train started. "Why all this secrecy?" "I had a caller this afternoon," he began, running his eye over the other passengers to see if we were observed. "She is going back on this train. I am not to recognise her at the station, but you and I are to walk to the end of the platform and enter a limousine bearing that number." He produced a card on the back of which was written a number in six figures. Mechanically I glanced at the name as he handed the card to me. Craig was watching intently the expression on my face as I read, "Miss Yvonne Brixton." "Since when were you admitted into society?" I gasped, still staring at the name of the daughter of the millionaire banker, John Brixton. "She came to tell me that her father is in a virtual state of siege, as it were, up there in his own house," explained Kennedy in an undertone, "so much so that, apparently, she is the only person he felt he dared trust with a message to summon me. Practically everything he says or does is spied on; he can't even telephone without what he says being known." "Siege?" I repeated incredulously. "Impossible. Why, only this morning I was reading about his negotiations with a foreign syndicate of bankers from southeastern Europe for a ten-million-dollar loan to relieve the money stringency there. Surely there must be some mistake in all this. In fact, as I recall it, one of the foreign bankers who is trying to interest him is that Count Wachtmann who, everybody says, is engaged to Miss Brixton, and is staying at the house at Woodrock. Craig, are you sure nobody is hoaxing you?" "Read that," he replied laconically, handing me a piece of thin letter-paper such as is often used for foreign correspondence. "Such letters have been coming to Mr. Brixton, I understand, every day." The letter was in a cramped foreign scrawl: JOHN BRIXTON, Woodrock, New York. American dollars must not endanger the peace of Europe. Be warned in time. In the name of liberty and progress we have raised the standard of conflict without truce or quarter against reaction. If you and the American bankers associated with you take up these bonds you will never live to receive the first payment of interest. THE RED BROTHERHOOD OF THE BALKANS. I looked up inquiringly. "What is the Red Brotherhood?" I asked. "As nearly as I can make out," replied Kennedy, "it seems to be a sort of international secret society. I believe it preaches the gospel of terror and violence in the cause of liberty and union of some of the peoples of southeastern Europe. Anyhow, it keeps its secrets well. The identity of the members is a mystery, as well as the source of its funds, which, it is said, are immense." "And they operate so secretly that Brixton can trust no one about him?" I asked. "I believe he is ill," explained Craig. "At any rate, he evidently suspects almost every one about him except his daughter. As nearly as I could gather, however, he does not suspect Wachtmann himself. Miss Brixton seemed to think that there were some enemies of the Count at work. Her father is a secretive man. Even to her, the only message he would entrust was that he wanted to see me immediately." At Woodrock we took our time in getting off the train. Miss Brixton, a tall, dark-haired, athletic girl just out of college, had preceded us, and as her own car shot out from the station platform we leisurely walked down and entered another bearing the number she had given Kennedy. We seemed to be expected at the house. Hardly had we been admitted through the door from the porte-cochere, than we were led through a hall to a library at the side of the house. From the library we entered another door, then down a flight of steps which must have brought us below an open courtyard on the outside, under a rim of the terrace in front of the house for a short distance to a point where we descended three more steps. At the head of these three steps was a great steel and iron door with heavy bolts and a combination lock of a character ordinarily found only on a safe in a banking institution. The door was opened, and we descended the steps, going a little farther in the same direction away from the side of the house. Then we turned at a right angle facing toward the back of the house but well to one side of it. It must have been, I figured out later, underneath the open courtyard. A few steps farther brought us to a fair-sized, vaulted room. V THE PHANTOM CIRCUIT Brixton had evidently been waiting impatiently for our arrival. "Mr. Kennedy?" he inquired, adding quickly without waiting for an answer: "I am glad to see you. I suppose you have noticed the precautions we are taking against intruders? Yet it seems to be all of no avail. I can not be alone even here. If a telephone message comes to me over my private wire, if I talk with my own office in the city, it seems that it is known. I don't know what to make of it. It is terrible. I don't know what to expect next." Brixton had been standing beside a huge mahogany desk as we entered. I had seen him before at a distance as a somewhat pompous speaker at banquets and the cynosure of the financial district. But there was something different about his looks now. He seemed to have aged, to have grown yellower. Even the whites of his eyes were yellow. I thought at first that perhaps it might be the effect of the light in the centre of the room, a huge affair set in the ceiling in a sort of inverted hemisphere of glass, concealing and softening the rays of a powerful incandescent bulb which it enclosed. It was not the light that gave him the altered appearance, as I concluded from catching a casual confirmatory glance of perplexity from Kennedy himself. "My personal physician says I am suffering from jaundice," explained Brixton. Rather than seeming to be offended at our notice of his condition he seemed to take it as a good evidence of Kennedy's keenness that he had at once hit on one of the things that were weighing on Brixton's own mind. "I feel pretty badly, too. Curse it," he added bitterly, "coming at a time when it is absolutely necessary that I should have all my strength to carry through a negotiation that is only a beginning, important not so much for myself as for the whole world. It is one of the first times New York bankers have had a chance to engage in big dealings in that part of the world. I suppose Yvonne has shown you one of the letters I am receiving?" He rustled a sheaf of them which he drew from a drawer of his desk, and continued, not waiting for Kennedy even to nod: "Here are a dozen or more of them. I get one or two every day, either here or at my town house or at the office." Kennedy had moved forward to see them. "One moment more," Brixton interrupted, still holding them. "I shall come back to the letters. That is not the worst. I've had threatening letters before. Have you noticed this room?" We had both seen and been impressed by it. "Let me tell you more about it," he went on. "It was designed especially to be, among other things, absolutely soundproof." We gazed curiously about the strong room. It was beautifully decorated and furnished. On the walls was a sort of heavy, velvety green wall-paper. Exquisite hangings were draped about, and on the floor were thick rugs. In all I noticed that the prevailing tint was green. "I had experiments carried out," he explained languidly, "with the object of discovering methods and means for rendering walls and ceilings capable of effective resistance to sound transmission. One of the methods devised involved the use under the ceiling or parallel to the wall, as the case might be, of a network of wire stretched tightly by means of pulleys in the adjacent walls and not touching at any point the surface to be protected against sound. Upon the wire network is plastered a composition formed of strong glue, plaster of Paris, and granulated cork, so as to make a flat slab, between which and the wall or ceiling is a cushion of confined air. The method is good in two respects: the absence of contact between the protective and protected surfaces and the colloid nature of the composition used. I have gone into the thing at length because it will make all the more remarkable what I am about to tell you." Kennedy had been listening attentively. As Brixton proceeded I had noticed Kennedy's nostrils dilating almost as if he were a hound and had scented his quarry. I sniffed, too. Yes, there was a faint odour, almost as if of garlic in the room. It was unmistakable. Craig was looking about curiously, as if to discover a window by which the odour might have entered. Brixton, with his eyes following keenly every move, noticed him. "More than that" he added quickly, "I have had the most perfect system of modern ventilation installed in this room, absolutely independent from that in the house." Kennedy said nothing. "A moment ago, Mr. Kennedy, I saw you and Mr. Jameson glancing up at the ceiling. Sound-proof as this room is, or as I believe it to be, I--I hear voices, voices from--not through, you understand, but from--that very ceiling. I do not hear them now. It is only at certain times when I am alone. They repeat the words in some of these letters--'You must not take up those bonds. You must not endanger the peace of the world. You will never live to get the interest.' Over and over I have heard such sentences spoken in this very room. I have rushed out and up the corridor. There has been no one there. I have locked the steel door. Still I have heard the voices. And it is absolutely impossible that a human being could get close enough to say them without my knowing and finding out where he is." Kennedy betrayed by not so much as the motion of a muscle even a shade of a doubt of Brixton's incredible story. Whether because he believed it or because he was diplomatic, Craig took the thing at its face value. He moved a blotter so that he could stand on the top of Brixton's desk in the centre of the room. Then he unfastened and took down the glass hemisphere over the light. "It is an Osram lamp of about a hundred candlepower, I should judge," he observed. Apparently he had satisfied himself that there was nothing concealed in the light itself. Laboriously, with such assistance as the memory of Mr. Brixton could give, he began tracing out the course of both the electric light and telephone wires that led down into the den. Next came a close examination of the ceiling and side walls, the floor, the hangings, the pictures, the rugs, everything. Kennedy was tapping here and there all over the wall, as if to discover whether there was any such hollow sound as a cavity might make. There was none. A low exclamation from him attracted my attention, though it escaped Brixton. His tapping had raised the dust from the velvety wall-paper wherever he had tried it. Hastily, from a corner where it would not be noticed, he pulled off a piece of the paper and stuffed it into his pocket. Then followed a hasty examination of the intake of the ventilating apparatus. Apparently satisfied with his examination of things in the den, Craig now prepared to trace out the course of the telephone and light wires in the house. Brixton excused himself, asking us to join him in the library up-stairs after Craig had completed his investigation. Nothing was discovered by tracing the lines back, as best we could, from the den. Kennedy therefore began at the other end, and having found the points in the huge cellar of the house where the main trunk and feed wires entered, he began a systematic search in that direction. A separate line led, apparently, to the den, and where this line feeding the Osram lamp passed near a dark storeroom in a corner Craig examined more closely than ever. Seemingly his search was rewarded, for he dived into the dark storeroom and commenced lighting matches furiously to discover what was there. "Look, Walter," he exclaimed, holding a match so that I could see what he had unearthed. There, in a corner concealed by an old chest of drawers, stood a battery of five storage-cells connected with an instrument that looked very much like a telephone transmitter, a rheostat, and a small transformer coil. "I suppose this is a direct-current lighting circuit," he remarked, thoughtfully regarding his find. "I think I know what this is, all right. Any amateur could do it, with a little knowledge of electricity and a source of direct current. The thing is easily constructed, the materials are common, and a wonderfully complicated result can be obtained. What's this?" He had continued to poke about in the darkness as he was speaking. In another corner he had discovered two ordinary telephone receivers. "Connected up with something, too, by George!" he ejaculated. Evidently some one had tapped the regular telephone wires running into the house, had run extensions into the little storeroom, and was prepared to overhear everything that was said either to or by those in the house. Further examination disclosed that there were two separate telephone systems running into Brixton's house. One, with its many extensions, was used by the household and by the housekeeper; the other was the private wire which led, ultimately, down into Brixton's den. No sooner had he discovered it than Kennedy became intensely interested. For the moment he seemed entirely to forget the electric-light wires and became absorbed in tracing out the course of the telephone trunk-line and its extensions. Continued search rewarded him with the discovery that both the household line and the private line were connected by hastily improvised extensions with the two receivers he had discovered in the out-of-the-way corner of a little dark storeroom. "Don't disturb a thing," remarked Kennedy, cautiously picking up even the burnt matches he had dropped in his hasty search. "We must devise some means of catching the eavesdropper red handed. It has all the marks of being an inside job." We had completed our investigation of the basement without attracting any attention, and Craig was careful to make it seem that in entering the library we came from the den, not from the cellar. As we waited in the big leather chairs Kennedy was sketching roughly on a sheet of paper the plan of the house, drawing in the location of the various wires. The door opened. We had expected John Brixton. Instead, a tall, spare foreigner with a close-cropped moustache entered. I knew at once that it must be Count Wachtmann, although I had never seen him. "Ah, I beg your pardon," he exclaimed in English which betrayed that he had been under good teachers in London. "I thought Miss Brixton was here." "Count Wachtmann?" interrogated Kennedy, rising. "The same," he replied easily, with a glance of inquiry at us. "My friend and I are from the Star" said Kennedy. "Ah! Gentlemen of the press?" He elevated his eyebrows the fraction of an inch. It was so politely contemptuous that I could almost have throttled him. "We are waiting to see Mr. Brixton," explained Kennedy. "What is the latest from the Near East?" Wachtmann asked, with the air of a man expecting to hear what he could have told you yesterday if he had chosen. There was a movement of the portieres, and a woman entered. She stopped a moment. I knew it was Miss Brixton. She had recognised Kennedy, but her part was evidently to treat him as a total stranger. "Who are these men, Conrad?" she asked, turning to Wachtmann. "Gentlemen of the press, I believe, to see your father, Yvonne," replied the count. It was evident that it had not been mere newspaper talk about this latest rumored international engagement. "How did you enjoy it?" he asked, noticing the title of a history which she had come to replace in the library. "Very well--all but the assassinations and the intrigues," she replied with a little shudder. He shot a quick, searching look at her face. "They are a violent people--some of them," he commented quickly. "You are going into town to-morrow?" I heard him ask Miss Brixton, as they walked slowly down the wide hall to the conservatory a few moments later. "What do you think of him?" I whispered to Kennedy. I suppose my native distrust of his kind showed through, for Craig merely shrugged his shoulders. Before he could reply Mr. Brixton joined us. "There's another one--just came," he ejaculated, throwing a letter down on the library table. It was only a few lines this time: "The bonds will not be subject to a tax by the government, they say. No--because if there is a war there won't be any government to tax them!" The note did not appear to interest Kennedy as much as what he had discovered. "One thing is self-evident, Mr. Brixton," he remarked. "Some one inside this house is spying, is in constant communication with a person or persons outside. All the watchmen and Great Danes on the estate are of no avail against the subtle, underground connection that I believe exists. It is still early in the afternoon. I shall make a hasty trip to New York and return after dinner. I should like to watch with you in the den this evening." "Very well," agreed Brixton. "I shall arrange to have you met at the station and brought here as secretly as I can." He sighed, as if admitting that he was no longer master of even his own house. Kennedy was silent during most of our return trip to New York. As for myself, I was deeply mired in an attempt to fathom Wachtmann. He baffled me. However, I felt that if there was indeed some subtle, underground connection between some one inside and someone outside Brixton's house, Craig would prepare an equally subtle method of meeting it on his own account. Very little was said by either of us on the journey up to the laboratory, or on the return to Woodrock. I realised that there was very little excuse for a commuter not to be well informed. I, at least, had plenty of time to exhaust the newspapers I had bought. Whether or not we returned without being observed, I did not know, but at least we did find that the basement and dark storeroom were deserted, as we cautiously made our way again it to the corner where Craig had made his enigmatical discoveries of the afternoon. While I held a pocket flashlight Craig was busy concealing another instrument of his own in the little storeroom. It seemed to be a little black disk about as big as a watch, with a number of perforated holes in one face. Carelessly he tossed it into the top drawer of the chest under some old rubbish, shut the drawer tight and ran a flexible wire out of the back of the chest. It was a simple matter to lay the wire through some bins next the storeroom and then around to the passageway down to the subterranean den of Brixton. There Craig deposited a little black box about the size of an ordinary kodak. For an hour or so we sat with Brixton. Neither of us said anything, and Brixton was uncommunicatively engaged in reading a railroad report. Suddenly a sort of muttering, singing noise seemed to fill the room. "There it is!" cried Brixton, clapping the book shut and looking eagerly at Kennedy. Gradually the sound increased in pitch. It seemed to come from the ceiling, not from any particular part of the room, but merely from somewhere overhead. There was no hallucination about it. We all heard. As the vibrations increased it was evident that they were shaping themselves into words. Kennedy had grasped the black box the moment the sound began and was holding two black rubber disks to his ears. At last the sound from overhead became articulate It was weird, uncanny. Suddenly a voice said distinctly: "Let American dollars beware. They will not protect American daughters." Craig had dropped the two ear-pieces and was gazing intently at the Osram lamp in the ceiling. Was he, too, crazy? "Here, Mr. Brixton, take these two receivers of the detectaphone," said Kennedy. "Tell me whether you can recognise the voice." "Why, it's familiar," he remarked slowly. "I can't place it, but I've heard it before. Where is it? What is this thing, anyhow?" "It is someone hidden in the storeroom in the basement," answered Craig. "He is talking into a very sensitive telephone transmitter and--" "But the voice--here?" interrupted Brixton impatiently. Kennedy pointed to the incandescent lamp in the ceiling. "The incandescent lamp," he said, "is not always the mute electrical apparatus it is supposed to be. Under the right conditions it can be made to speak exactly as the famous 'speaking-arc,' as it was called by Professor Duddell, who investigated it. Both the arc-light and the metal-filament lamp can be made to act as telephone receivers." It seemed unbelievable, but Kennedy was positive. "In the case of the speaking-arc or 'arcophone,' as it might be called," he continued, "the fact that the electric arc is sensitive to such small variations in the current over a wide range of frequency has suggested that a direct-current arc might be used as a telephone receiver. All that is necessary is to superimpose a microphone current on the main arc current, and the arc reproduces sounds and speech distinctly, loud enough to be heard several feet. Indeed, the arc could be used as a transmitter, too, if a sensitive receiver replaced the transmitter at the other end. The things needed are an arc-lamp, an impedance coil, or small transformer-coil, a rheostat, and a source of energy. The alternating current is not adapted to reproduce speech, but the ordinary direct current is. Of course, the theory isn't half as simple as the apparatus I have described." He had unscrewed the Osram lamp. The talking ceased immediately. "Two investigators named Ort and Ridger have used a lamp like this as a receiver," he continued. "They found that words spoken were reproduced in the lamp. The telephonic current variations superposed on the current passing through the lamp produce corresponding variations of heat in the filament, which are radiated to the glass of the bulb, causing it to expand and contract proportionately, and thus transmitting vibrations to the exterior air. Of course, in sixteen-and thirty-two-candle-power lamps the glass is too thick, and the heat variations are too feeble." Who was it whose voice Brixton had recognised as familiar over Kennedy's hastily installed detectaphone? Certainly he must have been a scientist of no mean attainment. That did not surprise me, for I realised that from that part of Europe where this mystical Red Brotherhood operated some of the most famous scientists of the world had sprung. A hasty excursion into the basement netted us nothing. The place was deserted. We could only wait. With parting instructions to Brixton in the use of the detectaphone we said good night, were met by a watchman and escorted as far as the lodge safely. Only one remark did Kennedy make as we settled ourselves for the long ride in the accommodation train to the city. "That warning means that we have two people to protect--both Brixton and his daughter." Speculate as I might, I could find no answer to the mystery, nor to the question, which was also unsolved, as to the queer malady of Brixton himself, which his physician diagnosed as jaundice. VI THE DETECTAPHONE Far after midnight though it had been when we had at last turned in at our apartment, Kennedy was up even earlier than usual in the morning. I found him engrossed in work at the laboratory. "Just in time to see whether I'm right in my guess about the illness of Brixton," he remarked, scarcely looking up at me. He had taken a flask with a rubber stopper. Through one hole in it was fitted a long funnel; through another ran a glass tube, connecting with a large U-shaped drying-tube filled with calcium chloride, which in turn connected with a long open tube with an up-turned end. Into the flask Craig dropped some pure granulated zinc coated with platinum. Then he covered it with dilute sulphuric acid through the funnel tube. "That forms hydrogen gas," he explained, "which passes through the drying-tube and the ignition-tube. Wait a moment until all the air is expelled from the tubes." He lighted a match and touched it to the open upturned end. The hydrogen, now escaping freely, was ignited with a pale-blue flame. Next, he took the little piece of wall-paper I had seen him tear off in the den, scraped off some powder from it, dissolved it, and poured it into the funnel-tube. Almost immediately the pale, bluish flame turned to bluish white, and white fumes were formed. In the ignition-tube a sort of metallic deposit appeared. Quickly he made one test after another. I sniffed. There was an unmistakable smell of garlic in the air. "Arseniureted hydrogen," commented Craig. "This is the Marsh test for arsenic. That wall-paper in Brixton's den has been loaded down with arsenic, probably Paris green or Schweinfurth green, which is aceto-arsenite of copper. Every minute he is there he is breathing arseniureted hydrogen. Some one has contrived to introduce free hydrogen into the intake of his ventilator. That acts on the arsenic compounds in the wall-paper and hangings and sets free the gas. I thought I knew the smell the moment I got a whiff of it. Besides, I could tell by the jaundiced look of his face that he was being poisoned. His liver was out of order, and arsenic seems to accumulate in the liver." "Slowly poisoned by minute quantities of gas," I repeated in amazement. "Some one in that Red Brotherhood is a diabolical genius. Think of it--poisoned wall-paper!" It was still early in the forenoon when Kennedy excused himself, and leaving me to my own devices disappeared on one of his excursions into the underworld of the foreign settlements on the East Side. About the middle of the afternoon he reappeared. As far as I could learn all that he had found out was that the famous, or rather infamous, Professor Michael Kumanova, one of the leaders of the Red Brotherhood, was known to be somewhere in this country. We lost no time in returning again to Woodrock late that afternoon. Craig hastened to warn Brixton of his peril from the contaminated atmosphere of the den, and at once a servant was set to work with a vacuum cleaner. Carefully Craig reconnoitred the basement where the eavesdropping storeroom was situated. Finding it deserted, he quickly set to work connecting the two wires of the general household telephone with what looked very much like a seamless iron tube, perhaps six inches long and three inches in diameter. Then he connected the tube also with the private wire of Brixton in a similar manner. "This is a special repeating-coil of high efficiency," he explained in answer to my inquiry. "It is absolutely balanced as to resistance, number of turns, and everything. I shall run this third line from the coil into Brixton's den, and then, if you like, you can accompany me on a little excursion down to the village where I am going to install another similar coil between the two lines at the local telephone central station opposite the railroad." Brixton met us about eight o'clock that night in his now renovated den. Apparently, even the little change from uncertainty to certainty so far had had a tonic effect on him. I had, however, almost given up the illusion that it was possible for us to be even in the den without being watched by an unseen eye. It seemed to me that to one who could conceive of talking through an incandescent lamp seeing, even through steel and masonry, was not impossible. Kennedy had brought with him a rectangular box of oak, in one of the large faces of which were two square boles. As he replaced the black camera-like box of the detectaphone with this oak box he remarked: "This is an intercommunicating telephone arrangement of the detectaphone. You see, it is more sensitive than anything of the sort ever made before. The arrangement of these little square holes is such as to make them act as horns or magnifiers of a double receiver. We can all hear at once what is going on by using this machine." We had not been waiting long before a peculiar noise seemed to issue from the detectaphone. It was as though a door had been opened and shut hastily. Some one had evidently entered the storeroom. A voice called up the railroad station and asked for Michael Kronski, Count Wachtmann's chauffeur. "It is the voice I heard last night," exclaimed Brixton. "By the Lord Harry, do you know, it is Janeff the engineer who has charge of the steam heating, the electric bells, and everything of the sort around the place. My own engineer--I'll land the fellow in jail before I'll--" Kennedy raised his hand. "Let us hear what he has to say," remonstrated Craig calmly. "I suppose you have wondered why I didn't just go down there last night and grab the fellow. Well, you see now. It is my invariable rule to get the man highest up. This fellow is only one tool. Arrest him, and as likely as not we should allow the big criminal to escape." "Hello, Kronski!" came over the detectaphone. "This is Janeff. How are things going?" Wachtmann's chauffeur must have answered that everything was all right. "You knew that they had discovered the poisoned wall-paper?" asked Janeff. A long parley followed. Finally, Janeff repeated what apparently had been his instructions. "Now, let me see," he said. "You want me to stay here until the last minute so that I can overhear whether any alarm is given for her? All right. You're sure it is the nine-o'clock train she is due on? Very well. I shall meet you at the ferry across the Hudson. I'll start from here as soon as I hear the train come in. We'll get the girl this time. That will bring Brixton to terms sure. You're right. Even if we fail this time, we'll succeed later. Don't fail me. I'll be at the ferry as soon as I can get past the guards and join you. There isn't a chance of an alarm from the house. I'll cut all the wires the last thing before I leave. Good-bye." All at once it dawned on me what they were planning--the kidnapping of Brixton's only daughter, to hold her, perhaps, as a hostage until he did the bidding of the gang. Wachtmann's chauffeur was doing it and using Wachtmann's car, too. Was Wachtmann a party to it? What was to be done? I looked at my watch. It was already only a couple of minutes of nine, when the train would be due. "If we could seize that fellow in the closet and start for the station immediately we might save Yvonne," cried Brixton, starting for the door. "And if they escape you make them more eager than ever to strike a blow at you and yours," put in Craig coolly. "No, let us get this thing straight. I didn't think it was as serious as this, but I'm prepared to meet any emergency." "But, man," shouted Brixton, "you don't suppose anything in the world counts beside her, do you?" "Exactly the point," urged Craig. "Save her and capture them--both at once." "How can you?" fumed Brixton. "If you attempt to telephone from here, that fellow Janeff will overhear and give a warning." Regardless of whether Janeff was listening or not, Kennedy was eagerly telephoning to the Woodrock central down in the village. He was using the transmitter and receiver that were connected with the iron tube which he had connected to the two regular house lines. "Have the ferry held at any cost," he was ordering. "Don't let the next boat go out until Mr. Brixton gets there, under any circumstances. Now put that to them straight, central. You know Mr. Brixton has just a little bit of influence around here, and somebody's head will drop if they let that boat go out before he gets there." "Humph!" ejaculated Brixton. "Much good that will do. Why, I suppose our friend Janeff down in the storeroom knows it all now. Come on, let's grab him." Nevertheless there was no sound from the detectaphone which would indicate that he had overheard and was spreading the alarm. He was there yet, for we could hear him clear his throat once or twice. "No," replied Kennedy calmly, "he knows nothing about it. I didn't use any ordinary means to prepare against the experts who have brought this situation about. That message you heard me send went out over what we call the 'phantom circuit.'" "The phantom circuit?" repeated Brixton, chafing at the delay. "Yes, it seems fantastic at first, I suppose," pursued Kennedy calmly; "but, after all, it is in accordance with the laws of electricity. It's no use fretting and fuming, Mr. Brixton. If Janeff can wait, we'll have to do so, too. Suppose we should start and this Kronski should change his plans at the last minute? How would we find it out? By telepathy? Believe me, sir, it is better to wait here a minute and trust to the phantom circuit than to mere chance." "But suppose he should cut the line," I put in. Kennedy smiled. "I have provided for that, Walter, in the way I installed the thing. I took good care that we could not be cut off that way. We can hear everything ourselves, but we cannot be overheard. He knows nothing. You see, I took advantage of the fact that additional telephones or so-called phantom lines can be superposed on existing physical lines. It is possible to obtain a third circuit from two similar metallic circuits by using for each side of this third circuit the two wires of each of the other circuits in multiple. All three circuits are independent, too. "The third telephone current enters the wires of the first circuit, as it were, and returns along the wires of the second circuit. There are several ways of doing it. One is to use retardation or choke-coils bridged across the two metallic circuits at both ends, with taps taken from the middle points of each. But the more desirable method is the one you saw me install this afternoon. I introduced repeating-coils into the circuits at both ends. Technically, the third circuit is then taken off from the mid-points of the secondaries or line windings of these repeating coils. "The current on a long-distance line is alternating in character, and it passes readily through a repeating-coil. The only effect it has on the transmission is slightly reducing the volume. The current passes into the repeating-coil, then divides and passes through the two line wires. At the other end the halves balance, so to speak. Thus, currents passing over a phantom circuit don't set up currents in the terminal apparatus of the side circuits. Consequently, a conversation carried on over the phantom circuit will not be heard in either side circuit, nor does a conversation on one side circuit affect the phantom. We could all talk at once without interfering with each other." "At any other time I should be more than interested," remarked Brixton grimly, curbing his impatience to be doing something. "I appreciate that, sir," rejoined Kennedy. "Ah, here it is. I have the central down in the village. Yes? They will hold the boat for us? Good. Thank you. The nine-o'clock train is five minutes late? Yes--what? Count Wachtmann's car is there? Oh, yes, the train is just pulling in. I see. Miss Brixton has entered his car alone. What's that? His chauffeur has started the car without waiting for the Count, who is coming down the platform?" Instantly Kennedy was on his feet. He was dashing up the corridor and the stairs from the den and down into the basement to the little storeroom. We burst into the place. It was empty. Janeff had cut the wires and fled. There was not a moment to lose. Craig hastily made sure that he had not discovered or injured the phantom circuit. "Call the fastest car you have in your garage, Mr. Brixton," ordered Kennedy. "Hello, hello, central! Get the lodge at the Brixton estate. Tell them if they see the engineer Janeff going out to stop him. Alarm the watchman and have the dogs ready. Catch him at any cost, dead, or alive." A moment later Brixton's car raced around, and we piled in and were off like a whirlwind. Already we could see lights moving about and hear the baying of dogs. Personally, I wouldn't have given much for Janeff's chances of escape. As we turned the bend in the road just before we reached the ferry, we almost ran into two cars standing before the ferry house. It looked as though one had run squarely in front of the other and blocked it off. In the slip the ferry boat was still steaming and waiting. Beside the wrecked car a man was lying on the ground groaning, while another man was quieting a girl whom he was leading to the waiting-room of the ferry. Brixton, weak though he was from his illness, leaped out of our car almost before we stopped and caught the girl in his arms. "Father!" she exclaimed, clinging to him. "What's this?" he demanded sternly, eying the man. It was Wachtmann himself. "Conrad saved me from that chauffeur of his," explained Miss Brixton. "I met him on the train, and we were going to ride up to the house together. But before Conrad could get into the car this fellow, who had the engine running, started it. Conrad jumped into another car that was waiting at the station. He overlook us and dodged in front so as to cut the chauffeur off from the ferry." "Curse that villain of a chauffeur," muttered Wachtmann, looking down at the wounded man. "Do you know who he is?" asked Craig with a searching glance at Wachtmann's face. "I ought to. His name is Kronski, and a blacker devil an employment bureau never furnished." "Kronski? No," corrected Kennedy. "It is Professor Kumanova, whom you perhaps have heard of as a leader of the Red Brotherhood, one of the cleverest scientific criminals who ever lived. I think you'll have no more trouble negotiating your loan or your love affair, Count," added Craig, turning on his heel. He was in no mood to receive the congratulations of the supercilious Wachtmann. As far as Craig was concerned, the case was finished, although I fancied from a flicker of his eye as he made some passing reference to the outcome that when he came to send in a bill to Brixton for his services he would not forget the high eyebrowed Count. I followed in silence as Craig climbed into the Brixton car and explained to the banker that it was imperative that he should get back to the city immediately. Nothing would do but that the car must take us all the way back, while Brixton summoned another from the house for himself. The ride was accomplished swiftly in record time. Kennedy said little. Apparently the exhilaration of the on-rush of cool air was quite in keeping with his mood, though for my part, I should have preferred something a little more relaxing of the nervous tension. "We've been at it five days, now," I remarked wearily as I dropped into an easy chair in our own quarters. "Are you going to keep up this debauch?" Kennedy laughed. "No," he said with a twinkle of scientific mischief, "no, I'm going to sleep it off." "Thank heaven!" I muttered. "Because," he went on seriously, "that case interrupted a long series of tests I am making on the sensitiveness of selenium to light, and I want to finish them up soon. There's no telling when I shall be called on to use the information." I swallowed hard. He really meant it. He was laying out more work for himself. Next morning I fully expected to find that he had gone. Instead he was preparing for what he called a quiet day in the laboratory. "Now for some REAL work," he smiled. "Sometimes, Walter, I feel that I ought to give up this outside activity and devote myself entirely to research. It is so much more important." I could only stare at him and reflect on how often men wanted to do something other than the very thing that nature had evidently intended them to do, and on how fortunate it was that we were not always free agents. He set out for the laboratory and I determined that as long as he would not stop working, neither would I. I tried to write. Somehow I was not in the mood. I wrote AT my story, but succeeded only in making it more unintelligible. I was in no fit condition for it. It was late in the afternoon. I had made up my mind to use force, if necessary, to separate Kennedy from his study of selenium. My idea was that anything from the Metropolitan to the "movies" would do him good, and I had almost carried my point when a big, severely plain black foreign limousine pulled up with a rush at the laboratory door. A large man in a huge fur coat jumped out and the next moment strode into the room. He needed no introduction, for we recognised at once J. Perry Spencer, one of the foremost of American financiers and a trustee of the university. With that characteristic directness which I have always thought accounted in large measure for his success, he wasted scarcely a word in coming straight to the object of his visit. "Professor Kennedy," he began, chewing his cigar and gazing about with evident interest at the apparatus Craig had collected in his warfare of science with crime, "I have dropped in here as a matter of patriotism. I want you to preserve to America those masterpieces of art and literature which I have collected all over the world during many years. They are the objects of one of the most curious pieces of vandalism of which I have ever heard. Professor Kennedy," he concluded earnestly, "could I ask you to call on Dr. Hugo Lith, the curator of my private museum, as soon as you can possibly find it convenient?" "Most assuredly, Mr. Spencer," replied Craig, with a whimsical side glance at me that told without words that this was better relaxation to him than either the Metropolitan or the "movies." "I shall be glad to see Dr. Lith at any time--right now, if it is convenient to him." The millionaire connoisseur consulted his watch. "Lith will be at the museum until six, at least. Yes, we can catch him there. I have a dinner engagement at seven myself. I can give you half an hour of the time before then. If you're ready, just jump into the car, both of you." The museum to which he referred was a handsome white marble building, in Renaissance, fronting on a side street just off Fifth Avenue and in the rear of the famous Spencer house, itself one of the show places of that wonderful thoroughfare. Spencer had built the museum at great cost simply to house those treasures which were too dear to him to entrust to a public institution. It was in the shape of a rectangle and planned with special care as to the lighting. Dr. Lith, a rather stout, mild-eyed German savant, plunged directly into the middle of things as soon as we had been introduced. "It is a most remarkable affair, gentlemen," he began, placing for us chairs that must have been hundreds of years old. "At first it was only those objects in the museum, that were green that were touched, like the collection of famous and historic French emeralds. But soon we found it was other things, too, that were missing--old Roman coins of gold, a collection of watches, and I know not what else until we have gone over the--" "Where is Miss White?" interrupted Spencer, who had been listening somewhat impatiently. "In the library, sir. Shall I call her?" "No, I will go myself. I want her to tell her experience to Professor Kennedy exactly as she told it to me. Explain while I am gone how impossible it would be for a visitor to do one, to say nothing of all, of the acts of vandalism we have discovered." VII THE GREEN CURSE The American Medici disappeared into his main library, where Miss White was making a minute examination to determine what damage had been done in the realm over which she presided. "Apparently every book with a green binding has been mutilated in some way," resumed Dr. Lith, "but that was only the beginning. Others have suffered, too, and some are even gone. It is impossible that any visitor could have done it. Only a few personal friends of Mr. Spencer are ever admitted here, and they are never alone. No, it is weird, mysterious." Just then Spencer returned with Miss White. She was an extremely attractive girl, slight of figure, but with an air about her that all the imported gowns in New York could not have conferred. They were engaged in animated conversation, so much in contrast with the bored air with which Spencer had listened to Dr. Lith that even I noticed that the connoisseur was completely obliterated in the man, whose love of beauty was by no means confined to the inanimate. I wondered if it was merely his interest in her story that impelled Spencer. The more I watched the girl the more I was convinced that she knew that she was interesting to the millionaire. "For example," Dr. Lith was saying, "the famous collection of emeralds which has disappeared has always been what you Americans call 'hoodooed.' They hare always brought ill luck, and, like many things of the sort to which superstition attaches, they have been 'banked,' so to speak, by their successive owners in museums." "Are they salable; that is, could any one dispose of the emeralds or the other curios with reasonable safety and at a good price?" "Oh, yes, yes," hastened Dr. Lith, "not as collections, but separately. The emeralds alone cost fifty thousand dollars. I believe Mr. Spencer bought them for Mrs. Spencer some years before she died. She did not care to wear them, however, and had them placed here." I thought I noticed a shade of annoyance cross the face of the magnate. "Never mind that," he interrupted. "Let me introduce Miss White. I think you will find her story one of the most uncanny you have ever heard." He had placed a chair for her and, still addressing us but looking at her, went on: "It seems that the morning the vandalism was first discovered she and Dr. Lith at once began a thorough search of the building to ascertain the extent of the depredations. The search lasted all day, and well into the night. I believe it was midnight before you finished?" "It was almost twelve," began the girl, in a musical voice that was too Parisian to harmonize with her plain Anglo-Saxon name, "when Dr. Lith was down here in his office checking off the objects in the catalogue which were either injured or missing. I had been working in the library. The noise of something like a shade flapping in the wind attracted my attention. I listened. It seemed to come from the art-gallery, a large room up-stairs where some of the greatest masterpieces in this country are hung. I hurried up there. "Just as I reached the door a strange feeling seemed to come over me that I was not alone in that room. I fumbled for the electric light switch, but in my nervousness could not find it. There was just enough light in the room to make out objects indistinctly. I thought I heard a low, moaning sound from an old Flemish copper ewer near me. I had heard that it was supposed to groan at night." She paused and shuddered at her recollection, and looked about as if grateful for the flood of electric light that now illuminated everything. Spencer reached over and touched her arm to encourage her to go on. She did not seem to resent the touch. "Opposite me, in the middle of the open floor," she resumed, her eyes dilated and her breath coming and going rapidly, "stood the mummy-case of Ka, an Egyptian priestess of Thebes, I think. The case was empty, but on the lid was painted a picture of the priestess! Such wonderful eyes! They seem to pierce right through your very soul. Often in the daytime I have stolen off to look at them. But at night--remember the hour of night, too--oh, it was awful, terrible. The lid of the mummy-case moved, yes, really moved, and seemed to float to one side. I could see it. And back of that carved and painted face with the piercing eyes was another face, a real face, real eyes, and they looked out at me with such hatred from the place that I knew was empty--" She had risen and was facing us with wild terror written on her face as if in appeal for protection against something she was powerless to name. Spencer, who had not taken his hand off her arm, gently pressed her back into the easy chair and finished the story. "She screamed and fainted. Dr. Lith heard it and rushed up-stairs. There she lay on the floor. The lid of the sarcophagus had really been moved. He saw it. Not a thing else had been disturbed. He carried her down here and revived her, told her to rest for a day or two, but--" "I cannot, I cannot," she cried. "It is the fascination of the thing. It brings me back here. I dream of it. I thought I saw those eyes the other night. They haunt me. I fear them, and yet I would not avoid them, if it killed me to look. I must meet and defy the power. What is it? Is it a curse four thousand years old that has fallen on me?" I had heard stories of mummies that rose from their sleep of centuries to tell the fate of some one when it was hanging in the balance, of mummies that groaned and gurgled and fought for breath, frantically beating with their swathed hands in the witching hours of the night. And I knew that the lure of these mummies was so strong for some people that they were drawn irresistibly to look upon and confer with them. Was this a case for the oculists, the spiritualists, the Egyptologists, or for a detective? "I should like to examine the art gallery, in fact, go over the whole museum," put in Kennedy in his most matter-of-fact tone. Spencer, with a glance at his watch, excused himself, nodding to Dr. Lith to show us about, and with a good night to Miss White which was noticeable for its sympathy with her fears, said, "I shall be at the house for another half-hour at least, in case anything really important develops." A few minutes later Miss White left for the night, with apparent reluctance, and yet, I thought, with just a little shudder as she looked back up the staircase that led to the art-gallery. Dr. Lith led us into a large vaulted marble hall and up a broad flight of steps, past beautiful carvings and frescoes that I should have liked to stop and admire. The art-gallery was a long room in the interior and at the top of the building, windowless but lighted by a huge double skylight each half of which must have been some eight or ten feet across. The light falling through this skylight passed through plate glass of marvellous transparency. One looked up at the sky as if through the air itself. Kennedy ignored the gallery's profusion of priceless art for the time and went directly to the mummy-case of the priestess Ka. "It has a weird history," remarked Dr. Lith. "No less than seven deaths, as well as many accidents, have been attributed to the malign influence of that greenish yellow coffin. You know the ancient Egyptians used to chant as they buried their sacred dead: 'Woe to him who injures the tomb. The dead shall point out the evildoer to the Devourer of the Underworld. Soul and body shall be destroyed.'" It was indeed an awesome thing. It represented a woman in the robes of an Egyptian priestess, a woman of medium height, with an inscrutable face. The slanting Egyptian eyes did, as Miss White had said, almost literally stare through you. I am sure that any one possessing a nature at all affected by such things might after a few minutes gazing at them in self-hypnotism really convince himself that the eyes moved and were real. Even as I turned and looked the other way I felt that those penetrating eyes were still looking at me, never asleep, always keen and searching. There was no awe about Kennedy. He carefully pushed aside the lid and peered inside. I almost expected to see some one in there. A moment later he pulled out his magnifying-glass and carefully examined the interior. At last he was apparently satisfied with his search. He had narrowed his attention down to a few marks on the stone, partly in the thin layer of dust that had collected on the bottom. "This was a very modern and material reincarnation," he remarked, as he rose. "If I am not mistaken, the apparition wore shoes, shoes with nails in the heels, and nails that are not like those in American shoes. I shall have to compare the marks I have found with marks I have copied from shoe-nails in the wonderful collection of M. Bertillon. Offhand, I should say that the shoes were of French make." The library having been gone over next without anything attracting Kennedy's attention particularly, he asked about the basement or cellar. Dr. Lith lighted the way, and we descended. Down there were innumerable huge packing-cases which had just arrived from abroad, full of the latest consignment of art treasures which Spencer had purchased. Apparently Dr. Lith and Miss White had been so engrossed in discovering what damage had been done to the art treasures above that they had not had time to examine the new ones in the basement. Kennedy's first move was to make a thorough search of all the little grated windows and a door which led out into a sort of little areaway for the removal of ashes and refuse. The door showed no evidence of having been tampered with, nor did any of the windows at first sight. A low exclamation from Kennedy brought us to his side. He had opened one of the windows and thrust his hand out against the grating, which had fallen on the outside pavement with a clang. The bars had been completely and laboriously sawed through, and the whole thing had been wedged back into place so that nothing would be detected at a cursory glance. He was regarding the lock on the window. Apparently it was all right; actually it had been sprung so that it was useless. "Most persons," he remarked, "don't know enough about jimmies. Against them an ordinary door-lock or window-catch is no protection. With a jimmy eighteen inches long even an anaemic burglar can exert a pressure sufficient to lift two tons. Not one window in a thousand can stand that strain. The only use of locks is to keep out sneak-thieves and compel the modern scientific educated burglar to make a noise. But making a noise isn't enough here, at night. This place with all its fabulous treasures must be guarded constantly, now, every hour, as if the front door were wide open." The bars replaced and the window apparently locked as before, Craig devoted his efforts to examining the packing cases in the basement. As yet apparently nothing down there had been disturbed. But while rummaging about, from an angle formed behind one of the cases he drew forth a cane, to all appearances an ordinary Malacca walking-stick. He balanced it in his hand a moment, then shook his head. "Too heavy for a Malacca," he ruminated. Then an idea seemed to occur to him. He gave the handle a twist. Sure enough, it came off, and as it did so a bright little light flashed up. "Well, what do you think of that?" he exclaimed. "For a scientific dark-lantern that is the neatest thing I have ever seen. An electric light cane, with a little incandescent lamp and a battery hidden in it. This grows interesting. We must at last have found the cache of a real gentleman burglar such as Bertillon says exists only in books. I wonder if he has anything else hidden back here." He reached down and pulled out a peculiar little instrument--a single blue steel cylinder. He fitted a hard rubber cap snugly into the palm of his hand, and with the first and middle fingers encircled the cylinder over a steel ring near the other end. A loud report followed, and a vase, just unpacked, at the opposite end of the basement was shattered as if by an explosion. "Phew!" exclaimed Kennedy. "I didn't mean to do that. I knew the thing was loaded, but I had no idea the hair-spring ring at the end was so delicate as to shoot it off at a touch. It's one of those aristocratic little Apache pistols that one can carry in his vest pocket and hide in his hand. Say, but that stung! And back here is a little box of cartridges, too." We looked at each other in amazement at the chance find. Apparently the vandal had planned a series of visits. "Now, let me see," resumed Kennedy. "I suppose our very human but none the less mysterious intruder expected to use these again. Well, let him try. I'll put them back here for the present. I want to watch in the art-gallery to-night." I could not help wondering whether, after all, it might not be an inside job and the fixing of the window merely a blind. Or was the vandal fascinated by the subtle influence of mysticism that so often seems to emanate from objects that have come down from the remote ages of the world? I could not help asking myself whether the story that Miss White had told was absolutely true. Had there been anything more than superstition in the girl's evident fright? She had seen something, I felt sure, for it was certain she was very much disturbed. But what was it she had really seen? So far all that Kennedy had found had proved that the reincarnation of the priestess Ka had been very material. Perhaps the "reincarnation" had got in in the daytime and had spent the hours until night in the mummy-case. It might well have been chosen as the safest and least suspicious hiding-place. Kennedy evidently had some ideas and plans, for no sooner had he completed arrangements with Dr. Lith so that we could get into the museum that night to watch, than he excused himself. Scarcely around the corner on the next business street he hurried into a telephone booth. "I called up First Deputy O'Connor," he explained as he left the booth a quarter of an hour later. "You know it is the duty of two of O'Connor's men to visit all the pawn-shops of the city at least once a week, looking over recent pledges and comparing them with descriptions of stolen articles. I gave him a list from that catalogue of Dr. Lith's and I think that if any of the emeralds, for instance, have been pawned his men will be on the alert and will find it out." We had a leisurely dinner at a near-by hotel, during most of which time Kennedy gazed vacantly at his food. Only once did he mention the case, and that was almost as if he were thinking aloud. "Nowadays," he remarked, "criminals are exceptionally well informed. They used to steal only money and jewels; to-day it is famous pictures and antiques also. They know something about the value of antique bronze and marble. In fact, the spread of a taste for art has taught the enterprising burglar that such things are worth money, and he, in turn, has educated up the receivers of stolen goods to pay a reasonable percentage of the value of his artistic plunder. The success of the European art thief is enlightening the American thief. That's why I think we'll find some of this stuff in the hands of the professional fences." It was still early in the evening when we returned to the museum and let ourselves in with the key that Dr. Lith had loaned Kennedy. He had been anxious to join us in the watch, but Craig had diplomatically declined, a circumstance that puzzled me and set me thinking that perhaps he suspected the curator himself. We posted ourselves in an angle where we could not possibly be seen even if the full force of the electrolier were switched on. Hour after hour we waited. But nothing happened. There were strange and weird noises in plenty, not calculated to reassure one, but Craig was always ready with an explanation. It was in the forenoon of the day after our long and unfruitful vigil in the art-gallery that Dr. Lith himself appeared at our apartment in a great state of perturbation. "Miss White has disappeared," he gasped, in answer to Craig's hurried question. "When I opened the museum, she was not there as she is usually. Instead, I found this note." He laid the following hastily written message on the table: Do not try to follow me. It is the green curse that has pursued me from Paris. I cannot escape it, but I may prevent it from affecting others. LUCILLE WHITE. That was all. We looked at each other at a loss to understand the enigmatic wording--"the green curse." "I rather expected something of the sort," observed Kennedy. "By the way, the shoenails were French, as I surmised. They show the marks of French heels. It was Miss White herself who hid in the mummy-case." "Impossible," exclaimed Dr. Lith incredulously. As for myself, I had learned that it was of no use being incredulous with Kennedy. A moment later the door opened, and one of O'Connor's men came in bursting with news. Some of the emeralds had been discovered in a Third Avenue pawn-shop. O'Connor, mindful of the historic fate of the Mexican Madonna and the stolen statue of the Egyptian goddess Neith, had instituted a thorough search with the result that at least part of the pilfered jewels had been located. There was only one clue to the thief, but it looked promising. The pawnbroker described him as "a crazy Frenchman of an artist," tall, with a pointed black beard. In pawning the jewels he had given the name of Edouard Delaverde, and the city detectives were making a canvass of the better known studios in hope of tracing him. Kennedy, Dr. Lith and myself walked around to the boarding-house where Miss White lived. There was nothing about it, from the landlady to the gossip, to distinguish it from scores of other places of the better sort. We had no trouble in finding out that Miss White had not returned home at all the night before. The landlady seemed to look on her as a woman of mystery, and confided to us that it was an open secret that she was not an American at all, but a French girl whose name, she believed, was really Lucille Leblanc--which, after all, was White. Kennedy made no comment, but I wavered between the conclusions that she had been the victim of foul play and that she might be the criminal herself, or at least a member of a band of criminals. No trace of her could be found through the usual agencies for locating missing persons. It was the middle of the afternoon, however, when word came to us that one of the city detectives had apparently located the studio of Delaverde. It was coupled with the interesting information that the day before a woman roughly answering the description of Miss White had been seen there. Delaverde himself was gone. The building to which the detective took us was down-town in a residence section which had remained as a sort of little eddy to one side of the current of business that had swept everything before it up-town. It was an old building and large, and was entirely given over to studios of artists. Into one of the cheapest of the suites we were directed. It was almost bare of furniture and in a peculiarly shiftless state of disorder. A half-finished picture stood in the centre of the room, and several completed ones were leaning against the wall. They were of the wildest character imaginable. Even the conceptions of the futurists looked tame in comparison. Kennedy at once began rummaging and exploring. In a corner of a cupboard near the door he disclosed a row of dark-colored bottles. One was filled halfway with an emerald-green liquid. He held it up to the light and read the label, "Absinthe." "Ah," he exclaimed with evident interest, looking first at the bottle and then at the wild, formless pictures. "Our crazy Frenchman was an absintheur. I thought the pictures were rather the product of a disordered mind than of genius." He replaced the bottle, adding: "It is only recently that our own government placed a ban on the importation of that stuff as a result of the decision of the Department of Agriculture that it was dangerous to health and conflicted with the pure food law. In France they call it the 'scourge,' the 'plague,' the 'enemy,' the 'queen of poisons.' Compared with other alcoholic beverages it has the greatest toxicity of all. There are laws against the stuff in France, Switzerland, and Belgium. It isn't the alcohol alone, although there is from fifty to eighty per cent. in it, that makes it so deadly. It is the absinthe, the oil of wormwood, whose bitterness has passed into a proverb. The active principle absinthin is a narcotic poison. The stuff creates a habit most insidious and difficult to break, a longing more exacting than hunger. It is almost as fatal as cocaine in its blasting effects on mind and body. "Wormwood," he pursued, still rummaging about, "has a special affinity for the brain-cells and the nervous system in general. It produces a special affliction of the mind, which might be called absinthism. Loss of will follows its use, brutishness, softening of the brain. It gives rise to the wildest hallucinations. Perhaps that was why our absintheur chose first to destroy or steal all things green, as if there were some merit in the colour, when he might have made away with so many more valuable things. Absintheurs have been known to perform some of the most intricate manoeuvres, requiring great skill and the use of delicate tools. They are given to disappearing, and have no memory of their actions afterward." On an ink-spattered desk lay some books, including Lombroso's "Degenerate Man" and "Criminal Woman." Kennedy glanced at them, then at a crumpled manuscript that was stuck into a pigeonhole. It was written in a trembling, cramped, foreign hand, evidently part of a book, or an article. "Oh, the wickedness of wealth!" it began. "While millions of the poor toilers slave and starve and shiver, the slave-drivers of to-day, like the slave-drivers of ancient Egypt, spend the money wrung from the blood of the people in useless and worthless toys of art while the people have no bread, in old books while the people have no homes, in jewels while the people have no clothes. Thousands are spent on dead artists, but a dollar is grudged to a living genius. Down with such art! I dedicate my life to righting the wrongs of the proletariat. Vive l'anarchism!" The thing was becoming more serious. But by far the most serious discovery in the now deserted studio was a number of large glass tubes in a corner, some broken, others not yet used and standing in rows as if waiting to be filled. A bottle labelled "Sulphuric Acid" stood at one end of a shelf, while at the other was a huge jar full of black grains, next a bottle of chlorate of potash. Kennedy took a few of the black grains and placed them on a metal ash-tray. He lighted a match. There was a puff and a little cloud of smoke. "Ah," he exclaimed, "black gunpowder. Our absintheur was a bomb-maker, an expert perhaps. Let me see. I imagine he was making an explosive bomb, ingeniously contrived of five glass tubes. The centre one, I venture, contained sulphuric acid and chlorate of potash separated by a close-packed wad of cotton wool. Then the two tubes on each side probably contained the powder, and perhaps the outside tubes were filled with spirits of turpentine. When it is placed in position, it is so arranged that the acid in the center tube is uppermost and will thus gradually soak through the cotton wool and cause great heat and an explosion by contact with the potash. That would ignite the powder in the next tubes, and that would scatter the blazing turpentine, causing a terrific explosion and a widespread fire. With an imperative idea of vengeance, such as that manuscript discloses, either for his own wrongs as an artist or for the fancied wrongs of the people, what may this absintheur not be planning now? He has disappeared, but perhaps he may be more dangerous if found than if lost." VIII THE MUMMY CASE The horrible thought occurred to me that perhaps he was not alone. I had seen Spencer's infatuation with his attractive librarian. The janitor of the studio-building was positive that a woman answering her description had been a visitor at the studio. Would she be used to get at the millionaire and his treasures? Was she herself part of the plot to victimise, perhaps kill, him? The woman had been much of an enigma to me at first. She was more so now. It was barely possible that she, too, was an absintheur, who had shaken off the curse for a time only to relapse into it again. If there were any thoughts like these passing through Kennedy's mind he did not show it, at least not in the shape of hesitating in the course he had evidently mapped out to follow. He said little, but hurried off from the studio in a cab up-town again to the laboratory. A few minutes later we were speeding down to the museum. There was not much time for Craig to work if he hoped to be ready for anything that might happen that night. He began by winding coil after coil of copper wire about the storeroom in the basement of the museum. It was not a very difficult matter to conceal it, so crowded was the room, or to lead the ends out through a window at the opposite side from that where the window had been broken open. Up-stairs in the art-gallery he next installed several boxes such as those which I had seen him experimenting with during his tests of selenium on the afternoon when Mr. Spencer had first called on us. They were camera-like boxes, about ten inches long, three inches or so wide, and four inches deep. One end was open, or at least looked as though the end had been shoved several inches into the interior of the box. I looked into one of the boxes and saw a slit in the wall that had been shoved in. Kennedy was busy adjusting the apparatus, and paused only to remark that the boxes contained two sensitive selenium surfaces balanced against two carbon resistances. There was also in the box a clockwork mechanism which Craig wound up and set ticking ever so softly. Then he moved a rod that seemed to cover the slit, until the apparatus was adjusted to his satisfaction, a delicate operation, judging by the care he took. Several of these boxes were installed, and by that time it was quite late. Wires from the apparatus in the art-gallery also led outside, and these as well as the wires from the coils down in the basement he led across the bit of garden back of the Spencer house and up to a room on the top floor. In the upper room he attached the wires from the storeroom to what looked like a piece of crystal and a telephone receiver. Those from the art-gallery terminated in something very much like the apparatus which a wireless operator wears over his head. Among other things which Craig had brought down from the laboratory was a package which he had not yet unwrapped. He placed it near the window, still wrapped. It was quite large, and must have weighed fifteen or twenty pounds. That done, he produced a tape-measure and began, as if he were a surveyor, to measure various distances and apparently to calculate the angles and distances from the window-sill of the Spencer house to the skylight, which was the exact centre of the museum. The straight distance, if I recall correctly, was in the neighborhood of four hundred feet. These preparations completed, there was nothing left to do but to wait for something to happen. Spencer had declined to get alarmed about our fears for his own safety, and only with difficulty had we been able to dissuade him from moving heaven and earth to find Miss White, a proceeding which must certainly have disarranged Kennedy's carefully laid plans. So interested was he that he postponed one of the most important business conferences of the year, growing out of the anti-trust suits, in order to be present with Dr. Lith and ourselves in the little upper back room. It was quite late when Kennedy completed his hasty arrangements, yet as the night advanced we grew more and more impatient for something to happen. Craig was apparently even more anxious than he had been the night before, when we watched in the art-gallery itself. Spencer was nervously smoking, lighting one cigar furiously from another until the air was almost blue. Scarcely a word was spoken as hour after hour Craig sat with the receiver to his ear, connected with the coils down in the storeroom. "You might call this an electric detective," he had explained to Spencer. "For example, if you suspected that anything out of the way was going on in a room anywhere this would report much to you even if you were miles away. It is the discovery of a student of Thorne Baker, the English electrical expert. He was experimenting with high-frequency electric currents, investigating the nature of the discharges used for electrifying certain things. Quite by accident he found that when the room on which he was experimenting was occupied by some person his measuring-instruments indicated that fact. He tested the degree of variation by passing the current first through the room and then through a sensitive crystal to a delicate telephone receiver. There was a distinct change in the buzzing sound heard through the telephone when the room was occupied or unoccupied. What I have done is to wind single loops of plain wire on each side of that room down there, as well as to wind around the room a few turns of concealed copper wire. These collectors are fitted to a crystal of carborundum and a telephone receiver." We had each tried the thing and could hear a distinct buzzing in the receiver. "The presence of a man or woman in that room would be evident to a person listening miles away," he went on. "A high-frequency current is constantly passing through that storeroom. That is what causes that normal buzzing." It was verging on midnight when Kennedy suddenly cried: "Here, Walter, take this receiver. You remember how the buzzing sounded. Listen. Tell me if you, too, can detect the change." I clapped the receiver quickly to my ear. Indeed I could tell the difference. In place of the load buzzing there was only a mild sound. It was slower and lower. "That means," he said excitedly, "that some one has entered that pitch-dark storeroom by the broken window. Let me take the receiver back again. Ah, the buzzing is coming back. He is leaving the room. I suppose he has found the electric light cane and the pistol where he left them. Now, Walter, since you have become accustomed to this thing take it and tell me what you hear." Craig had already seized the other apparatus connected with the art-gallery and had the wireless receiver over his head. He was listening with rapt attention, talking while he waited. "This is an apparatus," he was saying, "that was devised by Dr. Fournier d'Albe, lecturer on physics at Birmingham University, to aid the blind. It is known as the optophone. What I am literally doing now is to HEAR light. The optophone translates light into sound by means of that wonderful little element, selenium, which in darkness is a poor conductor of electricity, but in light is a good conductor. This property is used in the optophone in transmitting an electric current which is interrupted by a special clockwork interrupter. It makes light and darkness audible in the telephone. This thing over my head is like a wireless telephone receiver, capable of detecting a current of even a quarter of a microampere." We were all waiting expectantly for Craig to speak. Evidently the intruder was now mounting the stairs to the art-gallery. "Actually I can hear the light of the stars shining in through that wonderful plate glass skylight of yours, Mr. Spencer," he went on. "A few moments ago when the moon shone through I could hear it, like the rumble of a passing cart. I knew it was the moon both because I could see that it must be shining in and because I recognised the sound. The sun would thunder like a passing express-train if it were daytime now. I can distinguish a shadow passing between the optophone and the light. A hand moved across in front of it would give a purring sound, and a glimpse out of a window in daylight would sound like a cinematograph reeling off a film. "Ah, there he is." Craig was listening with intense excitement now. "Our intruder has entered the art-gallery. He is flashing his electric light cane about at various objects, reconnoitring. No doubt if I were expert enough and had had time to study it, I could tell you by the sound just what he is looking at." "Craig," I interrupted, this time very excited myself, "the buzzing from the high-frequency current is getting lower and lower." "By George, then, there is another of them," he replied. "I'm not surprised. Keep a sharp watch. Tell me the moment the buzzing increases again." Spencer could scarcely control his impatience. It had been a long time since he had been a mere spectator, and he did not seem to relish being held in check by anybody. "Now that you are sure the vandal is there," he cut in, his cigar out in his excitement, "can't we make a dash over there and get him before he has a chance to do any more damage? He might be destroying thousands of dollars' worth of stuff while we are waiting here." "And he could destroy the whole collection, building and all, including ourselves into the bargain, if he heard so much as a whisper from us," added Kennedy firmly. "That second person has left the storeroom, Craig," I put in. "The buzzing has returned again full force." Kennedy tore the wireless receiver from his ear. "Here, Walter, never mind about that electric detective any more, then. Take the optophone. Describe minutely to me just exactly what you hear." He had taken from his pocket a small metal ball. I seized the receiver from him and fitted it to my ear. It took me several instants to accustom my ears to the new sounds, but they were plain enough, and I shouted my impressions of their variations. Kennedy was busy at the window over the heavy package, from which he had torn the wrapping. His back was toward us, and we could not see what he was doing. A terrific din sounded in my ears, almost splitting my ear-drums. It was as though I had been suddenly hurled into a magnified cave of the winds and a cataract mightier than Niagara was thundering at me. It was so painful that I cried out in surprise and involuntarily dropped the receiver to the floor. "It was the switching on of the full glare of the electric lights in the art-gallery," Craig shouted. "The other person must have got up to the room quicker than I expected. Here goes." A loud explosion took place, apparently on the very window-sill of our room. Almost at the same instant there was a crash of glass from the museum. We sprang to the window, I expecting to see Kennedy injured, Spencer expecting to see his costly museum a mass of smoking ruins. Instead we saw nothing of the sort. On the window-ledge was a peculiar little instrument that looked like a miniature field-gun with an elaborate system of springs and levers to break the recoil. Craig had turned from it so suddenly that he actually ran full tilt into us. "Come on," he cried breathlessly, bolting from the room, and seizing Dr. Lith by the arm as he did so. "Dr. Lith, the keys to the museum, quick! We must get there before the fumes clear away." He was taking the stairs two at a time, dragging the dignified curator with him. In fewer seconds than I can tell it we were in the museum and mounting the broad staircase to the art-gallery. An overpowering gas seemed to permeate everything. "Stand back a moment," cautioned Kennedy as we neared the door. "I have just shot in here one of those asphyxiating bombs which the Paris police invented to war against the Apaches and the motor-car bandits. Open all the windows back here and let the air clear. Walter, breathe as little of it as you can--but--come here--do you see?--over there, near the other door--a figure lying on the floor? Make a dash in after me and carry it out. There is just one thing more. If I am not back in a minute come in and try to get me." He had already preceded me into the stifling fumes. With a last long breath of fresh air I plunged in after him, scarcely knowing what would happen to me. I saw the figure on the floor, seized it, and backed out of the room as fast as I could. Dizzy and giddy from the fumes I had been forced to inhale, I managed to drag the form to the nearest window. It was Lucille White. An instant later I felt myself unceremoniously pushed aside. Spencer had forgotten all about the millions of dollars' worth of curios, all about the suspicions that had been entertained against her, and had taken the half-conscious burden from me. "This is the second time I have found you here, Edouard," she was muttering in her half-delirium, still struggling. "The first time--that night I hid in the mummy-case, you fled when I called for help. I have followed you every moment since last night to prevent this. Edouard, don't, DON'T! Remember I was--I am your wife. Listen to me. Oh, it is the absinthe that has spoiled your art and made it worthless, not the critics. It is not Mr. Spencer who has enticed me away, but you who drove me away, first from Paris, and now from New York. He has been only--No! No!--" she was shrieking now, her eyes wide open as she realised it was Spencer himself she saw leaning over her. With a great effort she seemed to rouse herself. "Don't stay. Run--run. Leave me. He has a bomb that may go off at any moment. Oh--oh--it is the curse of absinthe that pursues me. Will you not go? Vite! Vite!" She had almost fainted and was lapsing into French, laughing and crying alternately, telling him to go, yet clinging to him. Spencer paid no attention to what she had said of the bomb. But I did. The minute was up, and Kennedy was in there yet. I turned to rush in again to warn him at any peril. Just then a half-conscious form staggered against me. It was Craig himself. He was holding the infernal machine of the five glass tubes that might at any instant blow us into eternity. Overcome himself, he stumbled. The sinking sensation in my heart I can never describe. It was just a second that I waited for the terrific explosion that was to end it all for us, one long interminable second. But it did not come. Limp as I was with the shock, I dropped down beside him and bent over. "A glass of water, Walter," he murmured, "and fan me a bit. I didn't dare trust myself to carry the thing complete, so I emptied the acid into the sarcophagus. I guess I must have stayed in there too long. But we are safe. See if you can drag out Delaverde. He is in there by the mummy-case." Spencer was still holding Lucille, although she was much better in the fresh air of the hall. "I understand," he was muttering. "You have been following this fiend of a husband of yours to protect the museum and myself from him. Lucille, Lucille--look at me. You are mine, not his, whether he is dead or alive. I will free you from him, from the curse of the absinthe that has pursued you." The fumes had cleared a great deal by this time. In the centre of the art-gallery we found a man, a tall, black-bearded Frenchman, crazy indeed from the curse of the green absinthe that had ruined him. He was scarcely breathing from a deadly wound in his chest. The hair-spring ring of the Apache pistol had exploded the cartridge as he fell. Spencer did not even look at him, as he carried his own burden down to the little office of Dr. Lith. "When a rich man marries a girl who has been earning her own living, the newspapers always distort it," he whispered aside to me a few minutes later. "Jameson, you're a newspaperman--I depend on you to get the facts straight this time." Outside, Kennedy grasped my arm. "You'll do that, Walter?" he asked persuasively. "Spencer is a client that one doesn't get every day. Just drop into the Star office and give them the straight story, I'll promise you I'll not take another case until you are free again to go on with me in it." There was no denying him. As briefly as I could I rehearsed the main facts to the managing editor late that night. I was too tired to write it at length, yet I could not help a feeling of satisfaction as he exclaimed, "Great stuff, Jameson,--great." "I know," I replied, "but this six-cylindered existence for a week wears you out." "My dear boy," he persisted, "if I had turned some one else loose on that story, he'd have been dead. Go to it--it's fine." It was a bit of blarney, I knew. But somehow or other I liked it. It was just what I needed to encourage me, and I hurried uptown promising myself a sound sleep at any rate. "Very good," remarked Kennedy the next morning, poking his head in at my door and holding up a copy of the Star into which a very accurate brief account of the affair had been dropped at the last moment. "I'm going over to the laboratory. See you there as soon as you can get over." "Craig," I remarked an hour or so later as I sauntered in on him, hard at work, "I don't see how you stand this feverish activity." "Stand it?" he repeated, holding up a beaker to the light to watch a reaction. "It's my very life. Stand it? Why, man, if you want me to pass away--stop it. As long as it lasts, I shall be all right. Let it quit and I'll--I'll go back to research work," he laughed. Evidently he had been waiting for me, for as he talked, he laid aside the materials with which he had been working and was preparing to go out. "Then, too," he went on, "I like to be with people like Spencer and Brixton. For example, while I was waiting here for you, there came a call from Emery Pitts." "Emery Pitts?" I echoed. "What does he want?" "The best way to find out is--to find out," he answered simply. "It's getting late and I promised to be there directly. I think we'd better take a taxi." A few minutes later we were ushered into a large Fifth Avenue mansion and were listening to a story which interested even Kennedy. "Not even a blood spot has been disturbed in the kitchen. Nothing has been altered since the discovery of the murdered chef, except that his body has been moved into the next room." Emery Pitts, one of the "thousand millionaires of steel," overwrought as he was by a murder in his own household, sank back in his easy-chair, exhausted. Pitts was not an old man; indeed, in years he was in the prime of life. Yet by his looks he might almost have been double his age, the more so in contrast with Minna Pitts, his young and very pretty wife, who stood near him in the quaint breakfast-room and solicitously moved a pillow back of his head. Kennedy and I looked on in amazement. We knew that he had recently retired from active business, giving as a reason his failing health. But neither of us had thought, when the hasty summons came early that morning to visit him immediately at his house, that his condition was as serious as it now appeared. "In the kitchen?" repeated Kennedy, evidently not prepared for any trouble in that part of the house. Pitts, who had closed his eyes, now reopened them slowly and I noticed how contracted were the pupils. "Yes," he answered somewhat wearily, "my private kitchen which I have had fitted up. You know, I am on a diet, have been ever since I offered the one hundred thousand dollars for the sure restoration of youth. I shall have you taken out there presently." He lapsed again into a half dreamy state, his head bowed on one hand resting on the arm of his chair. The morning's mail still lay on the table, some letters open, as they had been when the discovery had been announced. Mrs. Pitts was apparently much excited and unnerved by the gruesome discovery in the house. "You have no idea who the murderer might be?" asked Kennedy, addressing Pitts, but glancing keenly at his wife. "No," replied Pitts, "if I had I should have called the regular police. I wanted you to take it up before they spoiled any of the clues. In the first place we do not think it could have been done by any of the other servants. At least, Minna says that there was no quarrel." "How could any one have got in from the outside?" asked Craig. "There is a back way, a servants' entrance, but it is usually locked. Of course some one might have obtained a key to it." Mrs. Pitts had remained silent throughout the dialogue. I could not help thinking that she suspected something, perhaps was concealing something. Yet each of them seemed equally anxious to have the marauder apprehended, whoever he might be. "My dear," he said to her at length, "will you call some one and have them taken to the kitchen?" IX THE ELIXIR OF LIFE As Minna Pitts led us through the large mansion preparatory to turning us over to a servant she explained hastily that Mr. Pitts had long been ill and was now taking a new treatment under Dr. Thompson Lord. No one having answered her bell in the present state of excitement of the house, she stopped short at the pivoted door of the kitchen, with a little shudder at the tragedy, and stood only long enough to relate to us the story as she had heard it from the valet, Edward. Mr. Pitts, it seemed, had wanted an early breakfast and had sent Edward to order it. The valet had found the kitchen a veritable slaughter-house, with, the negro chef, Sam, lying dead on the floor. Sam had been dead, apparently, since the night before. As she hurried away, Kennedy pushed open the door. It was a marvellous place, that antiseptic or rather aseptic kitchen, with its white tiling and enamel, its huge ice-box, and cooking-utensils for every purpose, all of the most expensive and modern make. There were marks everywhere of a struggle, and by the side of the chef, whose body now lay in the next room awaiting the coroner, lay a long carving-knife with which he had evidently defended himself. On its blade and haft were huge coagulated spots of blood. The body of Sam bore marks of his having been clutched violently by the throat, and in his head was a single, deep wound that penetrated the skull in a most peculiar manner. It did not seem possible that a blow from a knife could have done it. It was a most unusual wound and not at all the sort that could have been made by a bullet. As Kennedy examined it, he remarked, shaking his head in confirmation of his own opinion, "That must have been done by a Behr bulletless gun." "A bulletless gun?" I repeated. "Yes, a sort of pistol with a spring-operated device that projects a sharp blade with great force. No bullet and no powder are used in it. But when it is placed directly over a vital point of the skull so that the aim is unerring, a trigger lets a long knife shoot out with tremendous force, and death is instantaneous." Near the door, leading to the courtyard that opened on the side street, were some spots of blood. They were so far from the place where the valet had discovered the body of the chef that there could be no doubt that they were blood from the murderer himself. Kennedy's reasoning in the matter seemed irresistible. He looked under the table near the door, covered with a large light cloth. Beneath the table and behind the cloth he found another blood spot. "How did that land there?" he mused aloud. "The table-cloth is bloodless." Craig appeared to think a moment. Then he unlocked and opened the door. A current of air was created and blew the cloth aside. "Clearly," he exclaimed, "that drop of blood was wafted under the table as the door was opened. The chances are all that it came from a cut on perhaps the hand or face of the murderer himself." It seemed to be entirely reasonable, for the bloodstains about the room were such as to indicate that he had been badly cut by the carving-knife. "Whoever attacked the chef must have been deeply wounded," I remarked, picking up the bloody knife and looking about at the stains, comparatively few of which could have come from the one deep fatal wound in the head of the victim. Kennedy was still engrossed in a study of the stains, evidently considering that their size, shape, and location might throw some light on what had occurred. "Walter," he said finally, "while I'm busy here, I wish you would find that valet, Edward. I want to talk to him." I found him at last, a clean-cut young fellow of much above average intelligence. "There are some things I have not yet got clearly, Edward," began Kennedy. "Now where was the body, exactly, when you opened the door?" Edward pointed out the exact spot, near the side of the kitchen toward the door leading out to the breakfast room and opposite the ice-box. "And the door to the side street?" asked Kennedy, to all appearances very favorably impressed by the young man. "It was locked, sir," he answered positively. Kennedy was quite apparently considering the honesty and faithfulness of the servant. At last he leaned over and asked quickly, "Can I trust you?" The frank, "Yes," of the young fellow was convincing enough. "What I want," pursued Kennedy, "is to have some one inside this house who can tell me as much as he can see of the visitors, the messengers that come here this morning. It will be an act of loyalty to your employer, so that you need have no fear about that." Edward bowed, and left us. While I had been seeking him, Kennedy had telephoned hastily to his laboratory and had found one of his students there. He had ordered him to bring down an apparatus which he described, and some other material. While we waited Kennedy sent word to Pitts that he wanted to see him alone for a few minutes. The instrument appeared to be a rubber bulb and cuff with a rubber bag attached to the inside. From it ran a tube which ended in another graduated glass tube with a thin line of mercury in it like a thermometer. Craig adjusted the thing over the brachial artery of Pitts, just above the elbow. "It may be a little uncomfortable, Mr. Pitts," he apologised, "but it will be for only a few minutes." Pressure through the rubber bulb shut off the artery so that Kennedy could no longer feel the pulse at the wrist. As he worked, I began to see what he was after. The reading on the graded scale of the height of the column of mercury indicated, I knew, blood pressure. This time, as he worked, I noted also the flabby skin of Pitts as well as the small and sluggish pupils of his eyes. He completed his test in silence and excused himself, although as we went back to the kitchen I was burning with curiosity. "What was it?" I asked. "What did you discover?" "That," he replied, "was a sphygmomanometer, something like the sphygmograph which we used once in another case. Normal blood pressure is 125 millimetres. Mr. Pitts shows a high pressure, very high. The large life insurance companies are now using this instrument. They would tell you that a high pressure like that indicates apoplexy. Mr. Pitts, young as he really is, is actually old. For, you know, the saying is that a man is as old as his arteries. Pitts has hardening of the arteries, arteriosclerosis--perhaps other heart and kidney troubles, in short pre-senility." Craig paused: then added sententiously as if to himself: "You have heard the latest theories about old age, that it is due to microbic poisons secreted in the intestines and penetrating the intestinal walls? Well, in premature senility the symptoms are the same as in senility, only mental acuteness is not so impaired." We had now reached the kitchen again. The student had also brought down to Kennedy a number of sterilised microscope slides and test-tubes, and from here and there in the masses of blood spots Kennedy was taking and preserving samples. He also took samples of the various foods, which he preserved in the sterilised tubes. While he was at work Edward joined us cautiously. "Has anything happened?" asked Craig. "A message came by a boy for Mrs. Pitts," whispered the valet. "What did she do with it?" "Tore it up." "And the pieces?" "She must have hidden them somewhere." "See if you can get them." Edward nodded and left us. "Yes," I remarked after he had gone, "it does seem as if the thing to do was to get on the trail of a person bearing wounds of some kind. I notice, for one thing, Craig, that Edward shows no such marks, nor does any one else in the house as far as I can see. If it were an 'inside job' I fancy Edward at least could clear himself. The point is to find the person with a bandaged hand or plastered face." Kennedy assented, but his mind was on another subject. "Before we go we must see Mrs. Pitts alone, if we can," he said simply. In answer to his inquiry through one of the servants she sent down word that she would see us immediately in her sitting-room. The events of the morning had quite naturally upset her, and she was, if anything, even paler than when we saw her before. "Mrs. Pitts," began Kennedy, "I suppose you are aware of the physical condition of your husband?" It seemed a little abrupt to me at first, but he intended it to be. "Why," she asked with real alarm, "is he so very badly?" "Pretty badly," remarked Kennedy mercilessly, observing the effect of his words. "So badly, I fear, that it would not require much more excitement like to-day's to bring on an attack of apoplexy. I should advise you to take especial care of him, Mrs. Pitts." Following his eyes, I tried to determine whether the agitation of the woman before us was genuine or not. It certainly looked so. But then, I knew that she had been an actress before her marriage. Was she acting a part now? "What do you mean?" she asked tremulously. "Mrs. Pitts," replied Kennedy quickly, observing still the play of emotion on her delicate features, "some one, I believe, either regularly in or employed in this house or who had a ready means of access to it must have entered that kitchen last night. For what purpose, I can leave you to judge. But Sam surprised the intruder there and was killed for his faithfulness." Her startled look told plainly that though she might have suspected something of the sort she did not think that any one else suspected, much less actually perhaps knew it. "I can't imagine who it could be, unless it might be one of the servants," she murmured hastily; adding, "and there is none of them that I have any right to suspect." She had in a measure regained her composure, and Kennedy felt that it was no use to pursue the conversation further, perhaps expose his hand before he was ready to play it. "That woman is concealing something," remarked Kennedy to me as we left the house a few minutes later. "She at least bears no marks of violence herself of any kind," I commented. "No," agreed Craig, "no, you are right so far." He added: "I shall be very busy in the laboratory this afternoon, and probably longer. However, drop in at dinner time, and in the meantime, don't say a word to any one, but just use your position on the Star to keep in touch with anything the police authorities may be doing." It was not a difficult commission, since they did nothing but issue a statement, the net import of which was to let the public know that they were very active, although they had nothing to report. Kennedy was still busy when I rejoined him, a little late purposely, since I knew that he would be over his head in work. "What's this--a zoo?" I asked, looking about me as I entered the sanctum that evening. There were dogs and guinea pigs, rats and mice, a menagerie that would have delighted a small boy. It did not look like the same old laboratory for the investigation of criminal science, though I saw on a second glance that it was the same, that there was the usual hurly-burly of microscopes, test-tubes, and all the paraphernalia that were so mystifying at first but in the end under his skilful hand made the most complicated cases seem stupidly simple. Craig smiled at my surprise. "I'm making a little study of intestinal poisons," he commented, "poisons produced by microbes which we keep under more or less control in healthy life. In death they are the little fellows that extend all over the body and putrefy it. We nourish within ourselves microbes which secrete very virulent poisons, and when those poisons are too much for us--well, we grow old. At least that is the theory of Metchnikoff, who says that old age is an infectious chronic, disease. Somehow," he added thoughtfully, "that beautiful white kitchen in the Pitts home had really become a factory for intestinal poisons." There was an air of suppressed excitement in his manner which told me that Kennedy was on the trail of something unusual. "Mouth murder," he cried at length, "that was what was being done in that wonderful kitchen. Do you know, the scientific slaying of human beings has far exceeded organised efforts at detection? Of course you expect me to say that; you think I look at such things through coloured glasses. But it is a fact, nevertheless. "It is a very simple matter for the police to apprehend the common murderer whose weapon is a knife or a gun, but it is a different thing when they investigate the death of a person who has been the victim of the modern murderer who slays, let us say, with some kind of deadly bacilli. Authorities say, and I agree with them, that hundreds of murders are committed in this country every year and are not detected because the detectives are not scientists, while the slayers have used the knowledge of the scientists both to commit and to cover up the crimes. I tell you, Walter, a murder science bureau not only would clear up nearly every poison mystery, but also it would inspire such a wholesome fear among would-be murderers that they would abandon many attempts to take life." He was as excited over the case as I had ever seen him. Indeed it was one that evidently taxed his utmost powers. "What have you found?" I asked, startled. "You remember my use of the sphygmomanometer?" he asked. "In the first place that put me on what seems to be a clear trail. The most dreaded of all the ills of the cardiac and vascular systems nowadays seems to be arterio-sclerosis, or hardening of the arteries. It is possible for a man of forty-odd, like Mr. Pitts, to have arteries in a condition which would not be encountered normally in persons under seventy years of age. "The hard or hardening artery means increased blood pressure, with a consequent increased strain on the heart. This may lead, has led in this case, to a long train of distressing symptoms, and, of course, to ultimate death. Heart disease, according to statistics, is carrying off a greater percentage of persons than formerly. This fact cannot be denied, and it is attributed largely to worry, the abnormal rush of the life of to-day, and sometimes to faulty methods of eating and bad nutrition. On the surface, these natural causes might seem to be at work with Mr. Pitts. But, Walter, I do not believe it, I do not believe it. There is more than that, here. Come, I can do nothing more to-night, until I learn more from these animals and the cultures which I have in these tubes. Let us take a turn or two, then dine, and perhaps we may get some word at our apartment from Edward." It was late that night when a gentle tap at the door proved that Kennedy's hope had not been unfounded. I opened it and let in Edward, the valet, who produced the fragments of a note, torn and crumpled. "There is nothing new, sir," he explained, "except that Mrs. Pitts seems more nervous than ever, and Mr. Pitts, I think, is feeling a little brighter." Kennedy said nothing, but was hard at work with puckered brows at piecing together the note which Edward had obtained after hunting through the house. It had been thrown into a fireplace in Mrs. Pitts's own room, and only by chance had part of it been unconsumed. The body of the note was gone altogether, but the first part and the last part remained. Apparently it had been written the very morning on which the murder was discovered. It read simply, "I have succeeded in having Thornton declared ..." Then there was a break. The last words were legible, and were,"... confined in a suitable institution where he can cause no future harm." There was no signature, as if the sender had perfectly understood that the receiver would understand. "Not difficult to supply some of the context, at any rate," mused Kennedy. "Whoever Thornton may be, some one has succeeded in having him declared 'insane,' I should supply. If he is in an institution near New York, we must be able to locate him. Edward, this is a very important clue. There is nothing else." Kennedy employed the remainder of the night in obtaining a list of all the institutions, both public and private, within a considerable radius of the city where the insane might be detained. The next morning, after an hour or so spent in the laboratory apparently in confirming some control tests which Kennedy had laid out to make sure that he was not going wrong in the line of inquiry he was pursuing, we started off in a series of flying visits to the various sanitaria about the city in search of an inmate named Thornton. I will not attempt to describe the many curious sights and experiences we saw and had. I could readily believe that any one who spent even as little time as we did might almost think that the very world was going rapidly insane. There were literally thousands of names in the lists which we examined patiently, going through them all, since Kennedy was not at all sure that Thornton might not be a first name, and we had no time to waste on taking any chances. It was not until long after dusk that, weary with the search and dust-covered from our hasty scouring of the country in an automobile which Kennedy had hired after exhausting the city institutions, we came to a small private asylum up in Westchester. I had almost been willing to give it up for the day, to start afresh on the morrow, but Kennedy seemed to feel that the case was too urgent to lose even twelve hours over. It was a peculiar place, isolated, out-of-the-way, and guarded by a high brick wall that enclosed a pretty good sized garden. A ring at the bell brought a sharp-eyed maid to the door. "Have you--er--any one here named Thornton--er--?" Kennedy paused in such a way that if it were the last name he might come to a full stop, and if it were a first name he could go on. "There is a Mr. Thornton who came yesterday," she snapped ungraciously, "but you can not see him, It's against the rules." "Yes--yesterday," repeated Kennedy eagerly, ignoring her tartness. "Could I--" he slipped a crumpled treasury note into her hand--"could I speak to Mr. Thornton's nurse?" The note seemed to render the acidity of the girl slightly alkaline. She opened the door a little further, and we found ourselves in a plainly furnished reception room, alone. We might have been in the reception-room of a prosperous country gentleman, so quiet was it. There was none of the raving, as far as I could make out, that I should have expected even in a twentieth century Bedlam, no material for a Poe story of Dr. Tarr and Professor Feather. At length the hall door opened, and a man entered, not a prepossessing man, it is true, with his large and powerful hands and arms and slightly bowed, almost bulldog legs. Yet he was not of that aggressive kind which would make a show of physical strength without good and sufficient cause. "You have charge of Mr. Thornton?" inquired Kennedy. "Yes," was the curt response. "I trust he is all right here?" "He wouldn't be here if he was all right," was the quick reply. "And who might you be?" "I knew him in the old days," replied Craig evasively. "My friend here does not know him, but I was in this part of Westchester visiting and having heard he was here thought I would drop in, just for old time's sake. That is all." "How did you know he was here?" asked the man suspiciously. "I heard indirectly from a friend of mine, Mrs. Pitts." "Oh." The man seemed to accept the explanation at its face value. "Is he very--very badly?" asked Craig with well-feigned interest. "Well," replied the man, a little mollified by a good cigar which I produced, "don't you go a-telling her, but if he says the name Minna once a day it is a thousand times. Them drug-dopes has some strange delusions." "Strange delusions?" queried Craig. "Why, what do you mean?" "Say," ejaculated the man. "I don't know you, You come here saying you're friends of Mr. Thornton's. How do I know what you are?" "Well," ventured Kennedy, "suppose I should also tell you I am a friend of the man who committed him." "Of Dr. Thompson Lord?" "Exactly. My friend here knows Dr. Lord very well, don't you, Walter?" Thus appealed to I hastened to add, "Indeed I do." Then, improving the opening, I hastened: "Is this Mr. Thornton violent? I think this is one of the most quiet institutions I ever saw for so small a place." The man shook his head. "Because," I added, "I thought some drug fiends were violent and had to be restrained by force, often." "You won't find a mark or a scratch on him, sir," replied the man. "That ain't our system." "Not a mark or scratch on him," repeated Kennedy thoughtfully. "I wonder if he'd recognise me?" "Can't say," concluded the man. "What's more, can't try. It's against the rules. Only your knowing so many he knows has got you this far. You'll have to call on a regular day or by appointment to see him, gentlemen." There was an air of finality about the last statement that made Kennedy rise and move toward the door with a hearty "Thank you, for your kindness," and a wish to be remembered to "poor old Thornton." As we climbed into the car he poked me in the ribs. "Just as good for the present as if we had seen him," he exclaimed. "Drug-fiend, friend of Mrs. Pitts, committed by Dr. Lord, no wounds." Then he lapsed into silence as we sped back to the city. "The Pitts house," ordered Kennedy as we bowled along, after noting by his watch that it was after nine. Then to me he added, "We must see Mrs. Pitts once more, and alone." We waited some time after Kennedy sent up word that he would like to see Mrs. Pitts. At last she appeared. I thought she avoided Kennedy's eye, and I am sure that her intuition told her that he had some revelation to make, against which she was steeling herself. Craig greeted her as reassuringly as he could, but as she sat nervously before us, I could see that she was in reality pale, worn, and anxious. "We have had a rather hard day," began Kennedy after the usual polite inquiries about her own and her husband's health had been, I thought, a little prolonged by him. "Indeed?" she asked. "Have you come any closer to the truth?" Kennedy met her eyes, and she turned away. "Yes, Mr. Jameson and I have put in the better part of the day in going from one institution for the insane to another." He paused. The startled look on her face told as plainly as words that his remark had struck home. Without giving her a chance to reply, or to think of a verbal means of escape, Craig hurried on with an account of what we had done, saying nothing about the original letter which had started us on the search for Thornton, but leaving it to be inferred by her that he knew much more than he cared to tell. "In short, Mrs. Pitts," he concluded firmly, "I do not need to tell you that I already know much about the matter which you are concealing." The piling up of fact on fact, mystifying as it was to me who had as yet no inkling of what it was tending toward, proved too much for the woman who knew the truth, yet did not know how much Kennedy knew of it. Minna Pitts was pacing the floor wildly, all the assumed manner of the actress gone from her, yet with the native grace and feeling of the born actress playing unrestrained in her actions. "You know only part of my story," she cried, fixing him with her now tearless eyes. "It is only a question of time when you will worm it all out by your uncanny, occult methods. Mr. Kennedy, I cast myself on you." X THE TOXIN OF DEATH The note of appeal in her tone was powerful, but I could not so readily shake off my first suspicions of the woman. Whether or not she convinced Kennedy, he did not show. "I was only a young girl when I met Mr. Thornton," she raced on. "I was not yet eighteen when we were married. Too late, I found out the curse of his life--and of mine. He was a drug fiend. From the very first life with him was insupportable. I stood it as long as I could, but when he beat me because he had no money to buy drugs, I left him. I gave myself up to my career on the stage. Later I heard that he was dead--a suicide. I worked, day and night, slaved, and rose in the profession--until, at last, I met Mr. Pitts." She paused, and it was evident that it was with a struggle that she could talk so. "Three months after I was married to him, Thornton suddenly reappeared, from the dead it seemed to me. He did not want me back. No, indeed. All he wanted was money. I gave him money, my own money, for I made a great deal in my stage days. But his demands increased. To silence him I have paid him thousands. He squandered them faster than ever. And finally, when it became unbearable, I appealed to a friend. That friend has now succeeded in placing this man quietly in a sanitarium for the insane." "And the murder of the chef?" shot out Kennedy. She looked from one to the other of us in alarm. "Before God, I know no more of that than does Mr. Pitts." Was she telling the truth? Would she stop at anything to avoid the scandal and disgrace of the charge of bigamy? Was there not something still that she was concealing? She took refuge in the last resort--tears. Encouraging as it was to have made such progress, it did not seem to me that we were much nearer, after all, to the solution of the mystery. Kennedy, as usual, had nothing to say until he was absolutely sure of his ground. He spent the greater part of the next day hard at work over the minute investigations of his laboratory, leaving me to arrange the details of a meeting he planned for that night. There were present Mr. and Mrs. Pitts, the former in charge of Dr. Lord. The valet, Edward, was also there, and in a neighbouring room was Thornton in charge of two nurses from the sanitarium. Thornton was a sad wreck of a man now, whatever he might have been when his blackmail furnished him with an unlimited supply of his favourite drugs. "Let us go back to the very start of the case," began Kennedy when we had all assembled, "the murder of the chef, Sam." It seemed that the mere sound of his voice electrified his little audience. I fancied a shudder passed over the slight form of Mrs. Pitts, as she must have realised that this was the point where Kennedy had left off, in his questioning her the night before. "There is," he went on slowly, "a blood test so delicate that one might almost say that he could identify a criminal by his very blood-crystals--the fingerprints, so to speak, of his blood. It was by means of these 'hemoglobin clues,' if I may call them so, that I was able to get on the right trail. For the fact is that a man's blood is not like that of any other living creature. Blood of different men, of men and women differ. I believe that in time we shall be able to refine this test to tell the exact individual, too. "What is this principle? It is that the hemoglobin or red colouring-matter of the blood forms crystals. That has long been known, but working on this fact Dr. Reichert and Professor Brown of the University of Pennsylvania have made some wonderful discoveries. "We could distinguish human from animal blood before, it is true. But the discovery of these two scientists takes us much further. By means of blood-crystals we can distinguish the blood of man from that of the animals and in addition that of white men from that of negroes and other races. It is often the only way of differentiating between various kinds of blood. "The variations in crystals in the blood are in part of form and in part of molecular structure, the latter being discovered only by means of the polarising microscope. A blood-crystal is only one two-thousand-two-hundred-and-fiftieth of an inch in length and one nine-thousandth of an inch in breadth. And yet minute as these crystals are, this discovery is of immense medico-legal importance. Crime may now be traced by blood-crystals." He displayed on his table a number of enlarged micro-photographs. Some were labelled, "Characteristic crystals of white man's blood"; others "Crystallisation of negro blood"; still others, "Blood-crystals of the cat." "I have here," he resumed, after we had all examined the photographs and had seen that there was indeed a vast amount of difference, "three characteristic kinds of crystals, all of which I found in the various spots in the kitchen of Mr. Pitts. There were three kinds of blood, by the infallible Reichert test." I had been prepared for his discovery of two kinds, but three heightened the mystery still more. "There was only a very little of the blood which was that of the poor, faithful, unfortunate Sam, the negro chef," Kennedy went on. "A little more, found far from his body, is that of a white person. But most of it is not human blood at all. It was the blood of a cat." The revelation was startling. Before any of us could ask, he hastened to explain. "It was placed there by some one who wished to exaggerate the struggle in order to divert suspicion. That person had indeed been wounded slightly, but wished it to appear that the wounds were very serious. The fact of the matter is that the carving-knife is spotted deeply with blood, but it is not human blood. It is the blood of a cat. A few years ago even a scientific detective would have concluded that a fierce hand-to-hand struggle had been waged and that the murderer was, perhaps, fatally wounded. Now, another conclusion stands, proved infallibly by this Reichert test. The murderer was wounded, but not badly. That person even went out of the room and returned later, probably with a can of animal blood, sprinkled it about to give the appearance of a struggle, perhaps thought of preparing in this way a plea of self-defence. If that latter was the case, this Reichert test completely destroys it, clever though it was." No one spoke, but the same thought was openly in all our minds. Who was this wounded criminal? I asked myself the usual query of the lawyers and the detectives--Who would benefit most by the death of Pitts? There was but one answer, apparently, to that. It was Minna Pitts. Yet it was difficult for me to believe that a woman of her ordinary gentleness could be here to-night, faced even by so great exposure, yet be so solicitous for him as she had been and then at the same time be plotting against him. I gave it up, determining to let Kennedy unravel it in his own way. Craig evidently had the same thought in his mind, however, for he continued: "Was it a woman who killed the chef? No, for the third specimen of blood, that of the white person, was the blood of a man; not of a woman." Pitts had been following closely, his unnatural eyes now gleaming. "You said he was wounded, you remember," he interrupted, as if casting about in his mind to recall some one who bore a recent wound. "Perhaps it was not a bad wound, but it was a wound nevertheless, and some one must have seen it, must know about it. It is not three days." Kennedy shook his head. It was a point that had bothered him a great deal. "As to the wounds," he added in a measured tone "although this occurred scarcely three days ago, there is no person even remotely suspected of the crime who can be said to bear on his hands or face others than old scars of wounds." He paused. Then he shot out in quick staccato, "Did you ever hear of Dr. Carrel's most recent discovery of accelerating the healing of wounds so that those which under ordinary circumstances might take ten days to heal might be healed in twenty-four hours?" Rapidly, now, he sketched the theory. "If the factors that bring about the multiplication of cells and the growth of tissues were discovered, Dr. Carrel said to himself, it would perhaps become possible to hasten artificially the process of repair of the body. Aseptic wounds could probably be made to cicatrise more rapidly. If the rate of reparation of tissue were hastened only ten times, a skin wound would heal in less than twenty-four hours and a fracture of the leg in four or five days. "For five years Dr. Carrel has been studying the subject, applying various extracts to wounded tissues. All of them increased the growth of connective tissue, but the degree of acceleration varied greatly. In some cases it was as high, as forty times the normal. Dr. Carrel's dream of ten times the normal was exceeded by himself." Astounded as we were by this revelation, Kennedy did not seem to consider it as important as one that he was now hastening to show us. He took a few cubic centimetres of some culture which he had been preparing, placed it in a tube, and poured in eight or ten drops of sulphuric acid. He shook it. "I have here a culture from some of the food that I found was being or had been prepared for Mr. Pitts. It was in the icebox." Then he took another tube. "This," he remarked, "is a one-to-one-thousand solution of sodium nitrite." He held it up carefully and poured three or four cubic centimetres of it into the first tube so that it ran carefully down the side in a manner such as to form a sharp line of contact between the heavier culture with the acid and the lighter nitrite solution. "You see," he said, "the reaction is very clear cut if you do it this way. The ordinary method in the laboratory and the text-books is crude and uncertain." "What is it?" asked Pitts eagerly, leaning forward with unwonted strength and noting the pink colour that appeared at the junction of the two liquids, contrasting sharply with the portions above and below. "The ring or contact test for indol," Kennedy replied, with evident satisfaction. "When the acid and the nitrites are mixed the colour reaction is unsatisfactory. The natural yellow tint masks that pink tint, or sometimes causes it to disappear, if the tube is shaken. But this is simple, clear, delicate--unescapable. There was indol in that food of yours, Mr. Pitts." "Indol?" repeated Pitts. "Is," explained Kennedy, "a chemical compound--one of the toxins secreted by intestinal bacteria and responsible for many of the symptoms of senility. It used to be thought that large doses of indol might be consumed with little or no effect on normal man, but now we know that headache, insomnia, confusion, irritability, decreased activity of the cells, and intoxication are possible from it. Comparatively small doses over a long time produce changes in organs that lead to serious results. "It is," went on Kennedy, as the full horror of the thing sank into our minds, "the indol-and phenol-producing bacteria which are the undesirable citizens of the body, while the lactic-acid producing germs check the production of indol and phenol. In my tests here to-day, I injected four one-hundredths of a grain of indol into a guinea-pig. The animal had sclerosis or hardening of the aorta. The liver, kidneys, and supra-renals were affected, and there was a hardening of the brain. In short, there were all the symptoms of old age." We sat aghast. Indol! What black magic was this? Who put it in the food? "It is present," continued Craig, "in much larger quantities than all the Metchnikoff germs could neutralise. What the chef was ordered to put into the food to benefit you, Mr. Pitts, was rendered valueless, and a deadly poison was added by what another--" Minna Pitts had been clutching for support at the arms of her chair as Kennedy proceeded. She now threw herself at the feet of Emery Pitts. "Forgive me," she sobbed. "I can stand it no longer. I had tried to keep this thing about Thornton from you. I have tried to make you happy and well--oh--tried so hard, so faithfully. Yet that old skeleton of my past which I thought was buried would not stay buried. I have bought Thornton off again and again, with money--my money--only to find him threatening again. But about this other thing, this poison, I am as innocent, and I believe Thornton is as--" Craig laid a gentle hand on her lips. She rose wildly and faced him in passionate appeal. "Who--who is this Thornton?" demanded Emery Pitts. Quickly, delicately, sparing her as much as he could, Craig hurried over our experiences. "He is in the next room," Craig went on, then facing Pitts added: "With you alive, Emery Pitts, this blackmail of your wife might have gone on, although there was always the danger that you might hear of it--and do as I see you have already done--forgive, and plan to right the unfortunate mistake. But with you dead, this Thornton, or rather some one using him, might take away from Minna Pitts her whole interest in your estate, at a word. The law, or your heirs at law, would never forgive as you would." Pitts, long poisoned by the subtle microbic poison, stared at Kennedy as if dazed. "Who was caught in your kitchen, Mr. Pitts, and, to escape detection, killed your faithful chef and covered his own traces so cleverly?" rapped out Kennedy. "Who would have known the new process of healing wounds? Who knew about the fatal properties of indol? Who was willing to forego a one-hundred-thousand-dollar prize in order to gain a fortune of many hundreds of thousands?" Kennedy paused, then finished with irresistibly dramatic logic; "Who else but the man who held the secret of Minna Pitts's past and power over her future so long as he could keep alive the unfortunate Thornton--the up-to-date doctor who substituted an elixir of death at night for the elixir of life prescribed for you by him in the daytime--Dr. Lord." Kennedy had moved quietly toward the door. It was unnecessary. Dr. Lord was cornered and knew it. He made no fight. In fact, instantly his keen mind was busy outlining his battle in court, relying on the conflicting testimony of hired experts. "Minna," murmured Pitts, falling back, exhausted by the excitement, on his pillows, "Minna--forgive? What is there to forgive? The only thing to do is to correct. I shall be well--soon now--my dear. Then all will be straightened out." "Walter," whispered Kennedy to me, "while we are waiting, you can arrange to have Thornton cared for at Dr. Hodge's Sanitarium." He handed me a card with the directions where to take the unfortunate man. When at last I had Thornton placed where no one else could do any harm through him, I hastened back to the laboratory. Craig was still there, waiting alone. "That Dr. Lord will be a tough customer," he remarked. "Of course you're not interested in what happens in a case after we have caught the criminal. But that often is really only the beginning of the fight. We've got him safely lodged in the Tombs now, however." "I wish there was some elixir for fatigue," I remarked, as we closed the laboratory that night. "There is," he replied. "A homeopathic remedy--more fatigue." We started on our usual brisk roundabout walk to the apartment. But instead of going to bed, Kennedy drew a book from the bookcase. "I shall read myself to sleep to-night," he explained, settling deeply in his chair. As for me, I went directly to my room, planning that to-morrow I would take several hours off and catch up in my notes. That morning Kennedy was summoned downtown and had to interrupt more important duties in order to appear before Dr. Leslie in the coroner's inquest over the death of the chef. Dr. Lord was held for the Grand Jury, but it was not until nearly noon that Craig returned. We were just about to go out to luncheon, when the door buzzer sounded. "A note for Mr. Kennedy," announced a man in a police uniform, with a blue anchor edged with white on his coat sleeve. Craig tore open the envelope quickly with his forefinger. Headed "Harbour Police, Station No. 3, Staten Island," was an urgent message from our old friend Deputy Commissioner O'Connor. "I have taken personal charge of a case here that is sufficiently out of the ordinary to interest you," I read when Kennedy tossed the note over to me and nodded to the man from the harbour squad to wait for us. "The Curtis family wish to retain a private detective to work in conjunction with the police in investigating the death of Bertha Curtis, whose body was found this morning in the waters of Kill van Kull." Kennedy and I lost no time in starting downtown with the policeman who had brought the note. The Curtises, as we knew, were among the prominent families of Manhattan and I recalled having heard that at one time Bertha Curtis had been an actress, in spite of the means and social position of her family, from whom she had become estranged as a result. At the station of the harbour police, O'Connor and another man, who was in a state of extreme excitement, greeted us almost before we had landed. "There have been some queer doings about here," exclaimed the deputy as he grasped Kennedy's hand, "but first of all let me introduce Mr. Walker Curtis." In a lower tone as we walked up the dock O'Connor continued, "He is the brother of the girl whose body the men in the launch at the station found in the Kill this morning. They thought at first that the girl had committed suicide, making it doubly sure by jumping into the water, but he will not believe it and,--well, if you'll just come over with us to the local undertaking establishment, I'd like to have you take a look at the body and see if your opinion coincides with mine. "Ordinarily," pursued O'Connor, "there isn't much romance in harbour police work nowadays, but in this case some other elements seem to be present which are not usually associated with violent deaths in the waters of the bay, and I have, as you will see, thought it necessary to take personal charge of the investigation. "Now, to shorten the story as much as possible, Kennedy, you know of course that the legislature at the last session enacted laws prohibiting the sale of such drugs as opium, morphine, cocaine, chloral and others, under much heavier penalties than before. The Health authorities not long ago reported to us that dope was being sold almost openly, without orders from physicians, at several scores of places and we have begun a crusade for the enforcement of the law. Of course you know how prohibition works in many places and how the law is beaten. The dope fiends seem to be doing the same thing with this law. "Of course nowadays everybody talks about a 'system' controlling everything, so I suppose people would say that there is a 'dope trust.' At any rate we have run up against at least a number of places that seem to be banded together in some way, from the lowest down in Chinatown to one very swell joint uptown around what the newspapers are calling 'Crime Square.' It is not that this place is pandering to criminals or the women of the Tenderloin that interests us so much as that its patrons are men and women of fashionable society whose jangled nerves seem to demand a strong narcotic. "This particular place seems to be a headquarters for obtaining them, especially opium and its derivatives. "One of the frequenters of the place was this unfortunate girl, Bertha Curtis. I have watched her go in and out myself, wild-eyed, nervous, mentally and physically wrecked for life. Perhaps twenty-five or thirty persons visit the place each day. It is run by a man known as 'Big Jack' Clendenin who was once an actor and, I believe, met and fascinated Miss Curtis during her brief career on the stage. He has an attendant there, a Jap, named Nichi Moto, who is a perfect enigma. I can't understand him on any reasonable theory. A long time ago we raided the place and packed up a lot of opium, pipes, material and other stuff. We found Clendenin there, this girl, several others, and the Jap. I never understood just how it was but somehow Clendenin got off with a nominal fine and a few days later opened up again. We were watching the place, getting ready to raid it again and present such evidence that Clendenin couldn't possibly beat it, when all of a sudden along came this--this tragedy." We had at last arrived at the private establishment which was doing duty as a morgue. The bedraggled form that had been bandied about by the tides all night lay covered up in the cold damp basement. Bertha Curtis had been a girl of striking beauty once. For a long time I gazed at the swollen features before I realised what it was that fascinated and puzzled me about her. Kennedy, however, after a casual glance had arrived at at least a part of her story. "That girl," he whispered to me so that her brother could not hear, "has led a pretty fast life. Look at those nails, yellow and dark. It isn't a weak face, either. I wouldn't be surprised if the whole thing, the Oriental glamour and all that, fascinated her as much as the drug." So far the case with its heartrending tragedy had all the earmarks of suicide. XI THE OPIUM JOINT O'Connor drew back the sheet which covered her and in the calf of the leg disclosed an ugly bullet hole. Ugly as it was, however, it was anything but dangerous and seemed to indicate nothing as to the real cause of her death. He drew from his pocket a slightly misshapen bullet which had been probed from the wound and handed it to Kennedy, who examined both the wound and the bullet carefully. It seemed to be an ordinary bullet except that in the pointed end were three or four little round, very shallow wells or depressions only the minutest fraction of an inch deep. "Very extraordinary," he remarked slowly. "No, I don't think this was a case of suicide. Nor was it a murder for money, else the jewels would have been taken." O'Connor looked approvingly at me. "Exactly what I said," he exclaimed. "She was dead before her body was thrown into the water." "No, I don't agree with you there," corrected Craig, continuing his examination of the body. "And yet it is not a case of drowning exactly, either." "Strangled?" suggested O'Connor. "By some jiu jitsu trick?" I put in, mindful of the queer-acting Jap at Clendenin's. Kennedy shook his head. "Perhaps the shock of the bullet wound rendered her unconscious and in that state she was thrown in," ventured Walker Curtis, apparently much relieved that Kennedy coincided with O'Connor in disagreeing with the harbour police as to the suicide theory. Kennedy shrugged his shoulders and looked at the bullet again. "It is very extraordinary," was all he replied. "I think you said a few moments ago, O'Connor, that there had been some queer doings about here. What did you mean?" "Well, as I said, the work of the harbour squad isn't ordinarily very remarkable. Harbour pirates aren't murderous as a rule any more. For the most part they are plain sneak thieves or bogus junk dealers who work with dishonest pier watchmen and crooked canal boat captains and lighter hands. "But in this instance," continued the deputy, his face knitting at the thought that he had to confess another mystery to which he had no solution, "it is something quite different. You know that all along the shore on this side of the island are old, dilapidated and, some of them, deserted houses. For several days the residents of the neighbourhood have been complaining of strange occurrences about one place in particular which was the home of a wealthy family in a past generation. It is about a mile from here, facing the road along the shore, and has in front of it and across the road the remains of an old dock sticking out a few feet into the water at high tide. "Now, as nearly as any one can get the story, there seems to have been a mysterious, phantom boat, very swift, without lights, and with an engine carefully muffled down which has been coming up to the old dock for the past few nights when the tide was high enough. A light has been seen moving on the dock, then suddenly extinguished, only to reappear again. Who carried it and why, no one knows. Any one who has tried to approach the place has had a scare thrown into him which he will not easily forget. For instance, one man crept up and though he did not think he was seen he was suddenly shot at from behind a tree. He felt the bullet pierce his arm, started to run, stumbled, and next morning woke up in the exact spot on which he had fallen, none the worse for his experience except that he had a slight wound that will prevent his using his right arm for some time for heavy work. "After each visit of the phantom boat there is heard, according to the story of the few neighbours who have observed it, the tramp of feet up the overgrown stone walk from the dock and some have said that they heard an automobile as silent and ghostly as the boat. We have been all through the weird old house, but have found nothing there, except enough loose boards and shutters to account for almost any noise or combination of noises. However, no one has said there was anything there except the tramp of feet going back and forth on the old pavements outside. Two or three times shots have been heard, and on the dock where most of the alleged mysterious doings have taken place we have found one very new exploded shell of a cartridge." Craig took the shell which O'Connor drew from another pocket and trying to fit the bullet and the cartridge together remarked "both from a .44, probably one of those old-fashioned, long-barrelled makes." "There," concluded O'Connor ruefully, "you know all we know of the thing so far." "I may keep these for the present?" inquired Kennedy, preparing to pocket the shell and the bullet, and from his very manner I could see that as a matter of fact he already knew a great deal more about the case than the police. "Take us down to this old house and dock, if you please." Over and over, Craig paced up and down the dilapidated dock, his keen eyes fastened to the ground, seeking some clue, anything that would point to the marauders. Real persons they certainly were, and not any ghostly crew of the bygone days of harbour pirates, for there was every evidence of some one who had gone up and down the walk recently, not once but many times. Suddenly Kennedy stumbled over what looked like a sardine tin can, except that it had no label or trace of one. It was lying in the thick long matted grass by the side of the walk as if it had tumbled there and had been left unnoticed. Yet there was nothing so very remarkable about it in itself. Tin cans were lying all about, those marks of decadent civilisation. But to Craig it had instantly presented an idea. It was a new can. The others were rusted. He had pried off the lid and inside was a blackish, viscous mass. "Smoking opium," Craig said at last. We retraced our steps pondering on the significance of the discovery. O'Connor had had men out endeavouring all day to get a clue to the motor car that had been mentioned in some of the accounts given by the natives. So far the best he had been able to find was a report of a large red touring car which crossed from New York on a late ferry. In it were a man and a girl as well as a chauffeur who wore goggles and a cap pulled down over his head so that he was practically unrecognisable. The girl might have been Miss Curtis and, as for the man, it might have been Clendenin. No one had bothered much with them; no one had taken their number; no one had paid any attention where they went after the ferry landed. In fact, there would have been no significance to the report if it had not been learned that early in the morning on the first ferry from the lower end of the island to New Jersey a large red touring car answering about the same description had crossed, with a single man and driver but no woman. "I should like to watch here with you to-night, O'Connor," said Craig as we parted. "Meet us here. In the meantime I shall call on Jameson with his well-known newspaper connections in the white light district," here he gave me a half facetious wink, "to see what he can do toward getting me admitted to this gilded palace of dope up there on Forty-fourth Street." After no little trouble Kennedy and I discovered our "hop joint" and were admitted by Nichi Moto, of whom we had heard. Kennedy gave me a final injunction to watch, but to be very careful not to seem to watch. Nichi Moto with an eye to business and not to our absorbing more than enough to whet our descriptive powers quickly conducted us into a large room where, on single bamboo couches or bunks, rather tastefully made, perhaps half a dozen habitues lay stretched at full length smoking their pipes in peace, or preparing them in great expectation from the implements on the trays before them. Kennedy relieved me of the responsibility of cooking the opium by doing it for both of us and, incidentally, dropping a hint not to inhale it and to breathe as little of it as possible. Even then it made me feel badly, though he must have contrived in some way to get even less of the stuff than I. A couple of pipes, and Kennedy beckoned to Nichi. "Where is Mr. Clendenin?" he asked familiarly. "I haven't seen him yet." The Japanese smiled his engaging smile. "Not know," was all he said, and yet I knew the fellow at least knew better English, if not more facts. Kennedy had about started on our faking a third "pipe" when a new, unexpected arrival beckoned excitedly to Nichi. I could not catch all that was said but two words that I did catch were "the boss" and "hop toy," the latter the word for opium. No sooner had the man disappeared without joining the smokers than Nichi seemed to grow very restless and anxious. Evidently he had received orders to do something. He seemed anxious to close the place and get away. I thought that some one might have given a tip that the place was to be raided, but Kennedy, who had been closer, had overheard more than I had and among other things he had caught the word, "meet him at the same place." It was not long before we were all politely hustled out. "At least we know this," commented Kennedy, as I congratulated myself on our fortunate escape, "Clendenin was not there, and there is something doing to-night, for he has sent for Nichi." We dropped into our apartment to freshen up a bit against the long vigil that we knew was coming that night. To our surprise Walker Curtis had left a message that he wished to see Kennedy immediately and alone, and although I was not present I give the substance of what he said. It seemed that he had not wished to tell O'Connor for fear that it would get into the papers and cause an even greater scandal, but it had come to his knowledge a few days before the tragedy that his sister was determined to marry a very wealthy Chinese merchant, an importer of tea, named Chin Jung. Whether or not this had any bearing on the case he did not know. He thought it had, because for a long time, both when she was on the stage and later, Clendenin had had a great influence over her and had watched with a jealous eye the advances of every one else. Curtis was especially bitter against Clendenin. As Kennedy related the conversation to me on our way over to Staten Island I tried to piece the thing together, but like one of the famous Chinese puzzles, it would not come out. I had to admit the possibility that it was Clendenin who might have quarrelled over her attachment to Chin Jung, even though I have never yet been able to understand what the fascination is that some Orientals have over certain American girls. All that night we watched patiently from a vantage point of an old shed near both the house and the decayed pier. It was weird in the extreme, especially as we had no idea what might happen if we had success and saw something. But there was no reward for our patience. Absolutely nothing happened. It was as though they knew, whoever they were, that we were there. During the hours that passed O'Connor whiled away the time in a subdued whisper now and then in telling us of his experiences in Chinatown which he was now engaged in trying to clean up. From Chinatown, its dens, its gamblers and its tongs we drifted to the legitimate business interests there, and I, at least, was surprised to find that there were some of the merchants for whom even O'Connor had a great deal of respect. Kennedy evidently did not wish to violate in any way the confidence of Walker Curtis, and mention of the name of Chin Jung, but by a judicious question as to who the best men were in the Celestial settlement he did get a list of half a dozen or so from O'Connor. Chin Jung was well up in the list. However, the night wore away and still nothing happened. It was in the middle of the morning when we were taking a snatch of sleep in our own rooms uptown that the telephone began to ring insistently. Kennedy, who was resting, I verily believe, merely out of consideration for my own human frailties, was at the receiver in an instant. It proved to be O'Connor. He had just gone back to his office at headquarters and there he had found a report of another murder. "Who is it?" asked Kennedy, "and why do you connect it with this case?" O'Connor's answer must have been a poser, judging from the look of surprise on Craig's face. "The Jap--Nichi Moto?" he repeated. "And it is the same sort of non-fatal wound, the same evidence of asphyxia, the same circumstances, even down to the red car reported by residents in the neighbourhood." Nothing further happened that day except this thickening of the plot by the murder of the peculiar-acting Nichi. We saw his body and it was as O'Connor said. "That fellow wasn't on the level toward Clendenin," Craig mused after we had viewed the second murder in the case. "The question is, who and what was he working for?" There was as yet no hint of answer, and our only plan was to watch again that night. This time O'Connor, not knowing where the lightning would strike next, took Craig's suggestion and we determined to spend the time cruising about in the fastest of the police motor boats, while the force of watchers along the entire shore front of the city was quietly augmented and ordered to be extra vigilant. O'Connor at the last moment had to withdraw and let us go alone, for the worst, and not the unexpected, happened in his effort to clean up Chinatown. The war between the old rivals, the Hep Sing Tong and the On Leong Tong, those ancient societies of troublemakers in the little district, had broken out afresh during the day and three Orientals had been killed already. It is not a particularly pleasant occupation cruising aimlessly up and down the harbour in a fifty-foot police boat, staunch and fast as she may be. Every hour we called at a police post to report and to keep in touch with anything that might interest us. It came at about two o'clock in the morning and of all places, near the Battery itself. From the front of a ferry boat that ran far down on the Brooklyn side, what looked like two flashlights gleamed out over the water once, then twice. "Headlights of an automobile," remarked Craig, scarcely taking more notice of it, for they might have simply been turned up and down twice by a late returning traveller to test them. We were ourselves near the Brooklyn shore. Imagine our surprise to see an answering light from a small boat in the river which was otherwise lightless. We promptly put out our own lights and with every cylinder working made for the spot where the light had flashed up on the river. There was something there all right and we went for it. On we raced after the strange craft, the phantom that had scared Staten Island. For a mile or so we seemed to be gaining, but one of our cylinders began to miss--the boat turned sharply around a bend in the shore. We had to give it up as well as trying to overtake the ferry boat going in the opposite direction. Kennedy's equanimity in our apparent defeat surprised me. "Oh, it's nothing, Walter," he said. "They slipped away to-night, but I have found the clue. To-morrow as soon as the Customs House is open you will understand. It all centres about opium." At least a large part of the secret was cleared, too, as a result of Kennedy's visit to the Customs House. After years of fighting with the opium ring on the Pacific coast, the ring had tried to "put one over" on the revenue officers and smuggle the drug in through New York. It did not take long to find the right man among the revenue officers to talk with. Nor was Kennedy surprised to learn that Nichi Moto had been in fact a Japanese detective, a sort of stool pigeon in Clendenin's establishment working to keep the government in touch with the latest scheme. The finding of the can of opium on the scene of the murder of Bertha Curtis, and the chase after the lightless motor boat had at last placed Kennedy on the right track. With one of the revenue officers we made a quick trip to Brooklyn and spent the morning inspecting the ships from South American ports docked in the neighbourhood where the phantom boat had disappeared. From ship to ship we journeyed until at last we came to one on which, down in the chain locker, we found a false floor with a locker under that. There was a compartment six feet square and in it lay, neatly packed, fourteen large hermetically sealed cylinders, each full of the little oblong tins such as Kennedy had picked up the other day--forty thousand dollars' worth of the stuff at one haul, to say nothing of the thousands that had already been landed at one place or another. It had been a good day's work, but as yet it had not caught the slayer or cleared up the mystery of Bertha Curtis. Some one or something had had a power over the girl to lure her on. Was it Clendenin? The place in Forty-fourth Street, on inquiry, proved to be really closed as tight as a drum. Where was he? All the deaths had been mysterious, were still mysterious. Bertha Curtis had carried her secret with her to the grave to which she had been borne, willingly it seemed, in the red car with the unknown companion and the goggled chauffeur. I found myself still asking what possible connection she could have with smuggling opium. Kennedy, however, was indulging in no such speculations. It was enough for him that the scene had suddenly shifted and in a most unexpected manner. I found him voraciously reading practically everything that was being printed in the papers about the revival of the tong war. "They say much about the war, but little about the cause," was his dry comment. "I wish I could make up my mind whether it is due to the closing of the joints by O'Connor, or the belief that one tong is informing on the other about opium smuggling." Kennedy passed over all the picturesque features in the newspapers, and from it all picked out the one point that was most important for the case which he was working to clear up. One tong used revolvers of a certain make; the other of a different make. The bullet which had killed Bertha Curtis and later Nichi Moto was from a pistol like that of the Hep Sings. The difference in the makes of guns seemed at once to suggest something to Kennedy and instead of mixing actively in the war of the highbinders he retired to his unfailing laboratory, leaving me to pass the time gathering such information as I could. Once I dropped in on him but found him unsociably surrounded by microscopes and a very sensitive arrangement for taking microphotographs. Some of his negatives were nearly a foot in diameter, and might have been, for all I knew, pictures of the surface of the moon. While I was there O'Connor came in. Craig questioned him about the war of the tongs. "Why," O'Connor cried, almost bubbling over with satisfaction, "this afternoon I was waited on by Chin Jung, you remember?--one of the leading merchants down there. Of course you know that Chinatown doesn't believe in hurting business and it seems that he and some of the others like him are afraid that if the tong war is not hushed up pretty soon it will cost a lot--in money. They are going to have an anniversary of the founding of the Chinese republic soon and of the Chinese New Year and they are afraid that if the war doesn't stop they'll be ruined." "Which tong does he belong to?" asked Kennedy, still scrutinising a photograph through his lens. "Neither," replied O'Connor. "With his aid and that of a Judge of one of our courts who knows the Chinaman like a book we have had a conference this afternoon between the two tongs and the truce is restored again for two weeks." "Very good," answered Kennedy, "but it doesn't catch the murderer of Bertha Curtis and the Jap. Where is Clendenin, do you suppose?" "I don't know, but it at least leaves me free to carry on that case. What are all these pictures?" "Well," began Kennedy, taking his glass from his eye and wiping it carefully, "a Paris crime specialist has formulated a system for identifying revolver bullets which is very like that of Dr. Bertillon for identifying human beings." He picked up a handful of the greatly enlarged photographs. "These are photographs of bullets which he has sent me. The barrel of every gun leaves marks on the bullet that are always the same for the same barrel but never identical for two different barrels. In these big negatives every detail appears very distinctly and it can be decided with absolute certainty whether a given bullet was fired from a given revolver. Now, using this same method, I have made similar greatly enlarged photographs of the two bullets that have figured so far in this case. The bullet that killed Miss Curtis shows the same marks as that which killed Nichi." He picked up another bunch of prints. "Now," he continued, "taking up the firing pin of a rifle or the hammer of a revolver, you may not know it but they are different in every case. Even among the same makes they are different, and can be detected. "The cartridge in either a gun or revolver is struck at a point which is never in the exact centre or edge, as the case may be, but is always the same for the same weapon. Now the end of the hammer when examined with the microscope bears certain irregularities of marking different from those of every other gun and the shell fired in it is impressed with the particular markings of that hammer, just as paper is by type. On making microphotographs of firing pins or hammers, with special reference to the rounded ends and also photographs of the corresponding rounded depressions in the primers fired by them it is forced on any one that cartridges fired by each individual rifle or pistol can positively be identified. "You will see on the edge of the photographs I have made a rough sketch calling attention to the 'L'-shaped mark which is the chief characteristic of this hammer, although there are other detailed markings which show well under the microscope but not well in a photograph. You will notice that the characters on the firing hammer are reversed on the cartridge in the same way that a metal type and the character printed by it are reversed as regards one another. Again, depressions on the end of the hammer become raised characters on the cartridge, and raised characters on the hammer become depressions on the cartridge. "Look at some of these old photographs and you will see that they differ from this. They lack the 'L' mark. Some have circles, others a very different series of pits and elevations, a set of characters when examined and measured under the microscope utterly different from those in every other case. Each is unique, in its pits, lines, circles and irregularities. The laws of chance are as much against two of them having the same markings as they are against the thumb prints of two human subjects being identical. The firing-pin theory, which was used in a famous case in Maine, is just as infallible as the finger-print theory. In this case when we find the owner of the gun making an 'L' mark we shall have the murderer." Something, I could see, was working on O'Connor's mind. "That's all right," he interjected, "but you know in neither case was the victim shot to death. They were asphyxiated." "I was coming to that," rejoined Craig. "You recall the peculiar marking on the nose of those bullets? They were what is known as narcotic bullets, an invention of a Pittsburg scientist. They have the property of lulling their victims to almost instant slumber. A slight scratch from these sleep-producing bullets is all that is necessary, as it was in the case of the man who spied on the queer doings on Staten Island. The drug, usually morphia, is carried in tiny wells on the cap of the bullet, is absorbed by the system and acts almost instantly." The door burst open and Walker Curtis strode in excitedly. He seemed surprised to see us all there, hesitated, then motioned to Kennedy that he wished to see him. For a few moments they talked and finally I caught the remark from Kennedy, "But, Mr. Curtis, I must do it. It is the only way." Curtis gave a resigned nod and Kennedy turned to us. "Gentlemen," he said, "Mr. Curtis in going over the effects of his sister has found a note from Clendenin which mentions another opium joint down in Chinatown. He wished me to investigate privately, but I have told him it would be impossible." At the mention of a den in the district he was cleaning up O'Connor had pricked up his ears. "Where is it?" he demanded. Curtis mentioned a number on Dover Street. "The Amoy restaurant," ejaculated O'Connor, seizing the telephone. A moment later he was arranging with the captain at the Elizabeth Street station for the warrants for an instant raid. XII THE "DOPE TRUST" As we hurried into Chinatown from Chatham Square we could see that the district was celebrating its holidays with long ropes of firecrackers, and was feasting to reed discords from the pipes of its most famous musicians, and was gay with the hanging out of many sunflags, red with an eighteen-rayed white sun in the blue union. Both the new tong truce and the anniversary were more than cause for rejoicing. Hurried though it was, the raid on the Hep Sing joint had been carefully prepared by O'Connor. The house we were after was one of the oldest of the rookeries, with a gaudy restaurant on the second floor, a curio shop on the street level, while in the basement all that was visible was a view of a huge and orderly pile of tea chests. A moment before the windows of the dwellings above the restaurant had been full of people. All had faded away even before the axes began to swing on the basement door which had the appearance of a storeroom for the shop above. The flimsy outside door went down quickly. But it was only a blind. Another door greeted the raiders. The axes swung noisily and the crowbars tore at the fortified, iron-clad, "ice box" door inside. After breaking it down they had to claw their way through another just like it. The thick doors and tea chests piled up showed why no sounds of gambling and other practices ever were heard outside. Pushing aside a curtain we were in the main room. The scene was one of confusion showing the hasty departure of the occupants. Kennedy did not stop here. Within was still another room, for smokers, anything but like the fashionable place we had seen uptown. It was low, common, disgusting. The odour everywhere was offensive; everywhere was filth that should naturally breed disease. It was an inferno reeking with unwholesome sweat and still obscured with dense fumes of smoke. Three tiers of bunks of hardwood were built along the walls. There was no glamour here; all was sordid. Several Chinamen in various stages of dazed indolence were jabbering in incoherent oblivion, a state I suppose of "Oriental calm." There, in a bunk, lay Clendenin. His slow and uncertain breathing told of his being under the influence of the drug, and he lay on his back beside a "layout" with a half-cooked pill still in the bowl of his pipe. The question was to wake him up. Craig began slapping him with a wet towel, directing us how to keep him roused. We walked him about, up and down, dazed, less than half sensible, dreaming, muttering, raving. A hasty exclamation from O'Connor followed as he drew from the scant cushions of the bunk a long-barreled pistol, a .44 such as the tong leaders used, the same make as had shot Bertha Curtis and Nichi. Craig seized it and stuck it into his pocket. All the gamblers had fled, all except those too drugged to escape. Where they had gone was indicated by a door leading up to the kitchen of the restaurant. Craig did not stop but leaped upstairs and then down again into a little back court by means of a fire-escape. Through a sort of short alley we groped our way, or rather through an intricate maze of alleys and a labyrinth of blind recesses. We were apparently back of a store on Pell Street. It was the work of only a moment to go through another door and into another room, filled with smoky, dirty, unpleasant, fetid air. This room, too, seemed to be piled with tea chests. Craig opened one. There lay piles and piles of opium tins, a veritable fortune in the drug. Mysterious pots and pans, strainers, wooden vessels, and testing instruments were about. The odour of opium in the manufacture was unmistakable, for smoking opium is different from the medicinal drug. There it appeared the supplies of thousands of smokers all over the country were stored and prepared. In a corner a mass of the finished product lay weltering in a basin like treacle. In another corner was the apparatus for remaking yen-shee or once-smoked opium. This I felt was at last the home of the "dope trust," as O'Connor had once called it, the secret realm of a real opium king, the American end of the rich Shanghai syndicate. A door opened and there stood a Chinaman, stoical, secretive, indifferent, with all the Oriental cunning and cruelty hall-marked on his face. Yet there was a fascination and air of Eastern culture about him in spite of that strange and typical Oriental depth of intrigue and cunning that shone through, great characteristics of the East. No one said a word as Kennedy continued to ransack the place. At last under a rubbish heap he found a revolver wrapped up loosely in an old sweater. Quickly, under the bright light, Craig drew Clendenin's pistol, fitted a cartridge into it and fired at the wall. Again into the second gun he fitted another and a second shot rang out. Out of his pocket came next the small magnifying glass and two unmounted microphotographs. He bent down over the exploded shells. "There it is," cried Craig scarcely able to restrain himself with the keenness of his chase, "there it is--the mark like an 'L.' This cartridge bears the one mark, distinct, not possible to have been made by any other pistol in the world. None of the Hep Sings, all with the same make of weapons, none of the gunmen in their employ, could duplicate that mark." "Some bullets," reported a policeman who had been rummaging further in the rubbish. "Be careful, man," cautioned Craig. "They are doped. Lay them down. Yes, this is the same gun that fired the shot at Bertha Curtis and Nichi Moto--fired narcotic bullets in order to stop any one who interfered with the opium smuggling, without killing the victim." "What's the matter?" asked O'Connor, arriving breathless from the gambling room after hearing the shots. The Chinaman stood, still silent, impassive. At sight of him O'Connor gasped out, "Chin Jung!" "Real tong leader," added Craig, "and the murderer of the white girl to whom he was engaged. This is the goggled chauffeur of the red car that met the smuggling boat, and in which Bertha Curtis rode, unsuspecting, to her death." "And Clendenin?" asked Walker Curtis, not comprehending. "A tool--poor wretch. So keen had the hunt for him become that he had to hide in the only safe place, with the coolies of his employer. He must have been in such abject terror that he has almost smoked himself to death." "But why should the Chinaman shoot my sister?" asked Walker Curtis amazed at the turn of events. "Your sister," replied Craig, almost reverently, "wrecked though she was by the drug, was at last conscience stricken when she saw the vast plot to debauch thousands of others. It was from her that the Japanese detective in the revenue service got his information--and both of them have paid the price. But they have smashed the new opium ring--we have captured the ring-leaders of the gang." Out of the maze of streets, on Chatham Square again, we lost no time in mounting to the safety of the elevated station before some murderous tong member might seek revenge on us. The celebration in Chinatown was stilled. It was as though the nerves of the place had been paralysed by our sudden, sharp blow. A downtown train took me to the office to write a "beat," for the Star always made a special feature of the picturesque in Chinatown news. Kennedy went uptown. Except for a few moments in the morning, I did not see Kennedy again until the following afternoon, for the tong war proved to be such an interesting feature that I had to help lay out and direct the assignments covering its various details. I managed to get away again as soon as possible, however, for I knew that it would not be long before some one else in trouble would commandeer Kennedy to untangle a mystery, and I wanted to be on the spot when it started. Sure enough, it turned out that I was right. Seated with him in our living room, when I came in from my hasty journey uptown in the subway, was a man, tall, thick-set, with a crop of closely curling dark hair, a sharp, pointed nose, ferret eyes, and a reddish moustache, curled at the ends. I had no difficulty in deciding what he was, if not who he was. He was the typical detective who, for the very reason that he looked the part, destroyed much of his own usefulness. "We have lost so much lately at Trimble's," he was saying, "that it is long past the stage of being merely interesting. It is downright serious--for me, at least. I've got to make good or lose my job. And I'm up against one of the cleverest shoplifters that ever entered a department-store, apparently. Only Heaven knows how much she has got away with in various departments so far, but when it comes to lifting valuable things like pieces of jewelry which run into the thousands, that is too much." At the mention of the name of the big Trimble store I had recognised at once what the man was, and it did not need Kennedy's rapid-fire introduction of Michael Donnelly to tell me that he was a department store detective. "Have you no clue, no suspicions?" inquired Kennedy. "Well, yes, suspicions," measured Donnelly slowly. "For instance, one day not long ago a beautifully dressed and refined-looking woman called at the jewellery department and asked to see a diamond necklace which we had just imported from Paris. She seemed to admire it very much, studied it, tried it on, but finally went away without making up her mind. A couple of days later she returned and asked to see it again. This time there happened to be another woman beside her who was looking at some pendants. The two fell to talking about the necklace, according to the best recollection of the clerk, and the second woman began to examine it critically. Again the prospective buyer went away. But this time after she had gone, and when he was putting the things back into the safe, the clerk examined the necklace, thinking that perhaps a flaw had been discovered in it which had decided the woman against it. It was a replica in paste; probably substituted by one of these clever and smartly dressed women for the real necklace." Before Craig had a chance to put another question, the buzzer on our door sounded, and I admitted a dapper, soft-spoken man of middle size, who might have been a travelling salesman or a bookkeeper. He pulled a card from his case and stood facing us, evidently in doubt how to proceed. "Professor Kennedy?" he asked at length, balancing the pasteboard between his fingers. "Yes," answered Craig. "What can I do for you?" "I am from Shorham, the Fifth Avenue jeweller, you know," he began brusquely, as he handed the card to Kennedy. "I thought I'd drop in to consult you about a peculiar thing that happened at the store recently, but if you are engaged, I can wait. You see, we had on exhibition a very handsome pearl dogcollar, and a few days ago two women came to--" "Say," interrupted Kennedy, glancing from the card to the face of Joseph Bentley, and then at Donnelly. "What is this--a gathering of the clans? There seems to be an epidemic of shoplifting. How much were you stung for?" "About twenty thousand altogether," replied Bentley with rueful frankness. "Why? Has some one else been victimised, too?" XIII THE KLEPTOMANIAC Quickly Kennedy outlined, with Donnelly's permission, the story we had just heard. The two store detectives saw the humour of the situation, as well as the seriousness of it, and fell to comparing notes. "The professional as well as the amateur shop-lifter has always presented to me an interesting phase of criminality," remarked Kennedy tentatively, during a lull in their mutual commiseration. "With thousands of dollars' worth of goods lying unprotected on the counters, it is really no wonder that some are tempted to reach out and take what they want." "Yes," explained Donnelly, "the shop-lifter is the department-store's greatest unsolved problem. Why, sir, she gets more plunder in a year than the burglar. She's costing the stores over two million dollars. And she is at her busiest just now with the season's shopping in full swing. It's the price the stores have to pay for displaying their goods, but we have to do it, and we are at the mercy of the thieves. I don't mean by that the occasional shoplifter who, when she gets caught, confesses, cries, pleads, and begs to return the stolen article. They often get off. It is the regulars who get the two million, those known to the police, whose pictures are, many of them, in the Rogues' Gallery, whose careers and haunts are known to every probation officer. They are getting away with loot that means for them a sumptuous living." "Of course we are not up against the same sort of swindlers that you are," put in Bentley, "but let me tell you that when the big jewelers do get up against anything of the sort they are up against it hard." "Have you any idea who it could be?" asked Kennedy, who had been following the discussion keenly. "Well, some idea," spoke up Donnelly. "From what Bentley says I wouldn't be surprised to find that it was the same person in both cases. Of course you know how rushed all the stores are just now. It is much easier for these light-fingered individuals to operate during the rush than at any other time. In the summer, for instance, there is almost no shop-lifting at all. I thought that perhaps we could discover this particular shoplifter by ordinary means, that perhaps some of the clerks in the jewellery department might be able to identify her. We found one who said that he thought he might recognise one of the women if he saw her again. Perhaps you did not know that we have our own little rogues' gallery in most of the big department-stores. But there didn't happen to be anything there that he recognised. So I took him down to Police Headquarters. Through plate after plate of pictures among the shoplifters in the regular Rogues' Gallery the clerk went. At last he came to one picture that caused him to stop. 'That is one of the women I saw in the store that day,' he said. 'I'm sure of it.'" Donnelly produced a copy of the Bertillon picture. "What?" exclaimed Bentley, as he glanced at it and then at the name and history on the back. "Annie Grayson? Why, she is known as the queen of shoplifters. She has operated from Christie's in London to the little curio-shops of San Francisco. She has worked under a dozen aliases and has the art of alibi down to perfection. Oh, I've heard of her many times before. I wonder if she really is the person we're looking for. They say that Annie Grayson has forgotten more about shoplifting than the others will ever know." "Yes," continued Donnelly, "and here's the queer part of it. The clerk was ready to swear that he had seen the woman in the store at some time or other, but whether she had been near the counter where the necklace was displayed was another matter. He wasn't so sure about that." "Then how did she get it?" I asked, much interested. "I don't say that she did get it," cautioned Donnelly. "I don't know anything about it. That is why I am here consulting Professor Kennedy." "Then who did get it, do you think?" I demanded. "We have a great deal of very conflicting testimony from the various clerks," Donnelly continued. "Among those who are known to have visited the department and to have seen the necklace is another woman, of an entirely different character, well known in the city." He glanced sharply at us, as if to impress us with what he was about to say, then he leaned over and almost whispered the name. "As nearly as I can gather out of the mass of evidence, Mrs. William Willoughby, the wife of the broker down in Wall Street, was the last person who was seen looking at the diamonds." The mere breath of such a suspicion would have been enough, without his stage-whisper method of imparting the information. I felt that it was no wonder that, having even a suspicion of this sort, he should be in doubt how to go ahead and should wish Kennedy's advice. Ella Willoughby, besides being the wife of one of the best known operators in high-class stocks and bonds, was well known in the society columns of the newspapers. She lived in Glenclair, where she was a leader of the smarter set at both the church and the country club. The group who preserved this neat balance between higher things and the world, the flesh and the devil, I knew to be a very exclusive group, which, under the calm suburban surface, led a sufficiently rapid life. Mrs. Willoughby, in addition to being a leader, was a very striking woman and a beautiful dresser, who set a fast pace for the semi-millionaires who composed the group. Here indeed was a puzzle at the very start of the case. It was in all probability Mrs. Willoughby who had looked at the jewels in both cases. On the other hand, it was Annie Grayson who had been seen on at least one occasion, yet apparently had had nothing whatever to do with the missing jewels, at least not so far as any tangible evidence yet showed. More than that, Donnelly vouchsafed the information that he had gone further and that some of the men work-ing under him had endeavoured to follow the movements of the two women and had found what looked to be a curious crossing of trails. Both of them, he had found, had been in the habit of visiting, while shopping, the same little tea-room on Thirty-third Street, though no one had ever seen them together there, and the coincidence might be accounted for by the fact that many Glenclair ladies on shopping expeditions made this tea-room a sort of rendezvous. By inquiring about among his own fraternity Donnelly had found that other stores also had reported losses recently, mostly of diamonds and pearls, both black and white. Kennedy had been pondering the situation for some time, scarcely uttering a word. Both detectives were now growing restless, waiting for him to say something. As for me, I knew that if anything were said or done it would be in Kennedy's own good time. I had learned to have implicit faith and confidence in him, for I doubt if Craig could have been placed in a situation where he would not know just what to do after he had looked over the ground. At length he leisurely reached across the table for the suburban telephone book, turned the pages quickly, snapped it shut, and observed wearily and, as it seemed, irrelevantly: "The same old trouble again about accurate testimony. I doubt whether if I should suddenly pull a revolver and shoot Jameson, either of you two men could give a strictly accurate account of just what happened." No one said anything, as he raised his hands from his habitual thinking posture with finger-tips together, placed both hands back of his head, and leaned back facing us squarely. "The first step," he said slowly, "must be to arrange a 'plant.' As nearly as I can make out the shoplifters or shoplifter, whichever it may prove to be, have no hint that any one is watching them yet. Now, Donnelly, it is still very early. I want you to telephone around to the newspapers, and either in the Trimble advertisements or in the news columns have it announced that your jewellery department has on exhibition a new and special importation of South African stones among which is one--let me see, let's call it the 'Kimberley Queen.' That will sound attractive. In the meantime find the largest and most perfect paste jewel in town and have it fixed up for exhibition and labelled the Kimberley Queen. Give it a history if you can; anything to attract attention. I'll see you in the morning. Good-night, and thank you for coming to me with this case." It was quite late, but Kennedy, now thoroughly interested in following the chase, had no intention of waiting until the morrow before taking action on his own account. In fact he was just beginning the evening's work by sending Donnelly off to arrange the "plant." No less interested in the case than himself, I needed no second invitation, and in a few minutes we were headed from our rooms toward the laboratory, where Kennedy had apparatus to meet almost any conceivable emergency. From a shelf in the corner he took down an oblong oak box, perhaps eighteen inches in length, in the front of which was set a circular metal disk with a sort of pointer and dial. He lifted the lid of the box, and inside I could see two shiny caps which in turn he lifted, disclosing what looked like two good-sized spools of wire. Apparently satisfied with his scrutiny, he snapped the lid shut and wrapped up the box carefully, consigning it to my care, while he hunted some copper wire. From long experience with Kennedy I knew better than to ask what he had in mind to do. It was enough to know that he had already, in those few minutes of apparent dreaming while Donnelly and Bentley were fidgeting for words, mapped out a complete course of action. We bent our steps toward the under-river tube, which carried a few late travellers to the railroad terminal where Kennedy purchased tickets for Glenclair. I noticed that the conductor on the suburban train eyed us rather suspiciously as though the mere fact that we were not travelling with commutation tickets at such an hour constituted an offence. Although I did not yet know the precise nature of our adventure, I remembered with some misgiving that I had read of police dogs in Glenclair which were uncomfortably familiar with strangers carrying bundles. However, we got along all right, perhaps because the dogs knew that in a town of commuters every one was privileged to carry a bundle. "If the Willoughbys had been on a party line," remarked Craig as we strode up Woodridge Avenue trying to look as if it was familiar to us, "we might have arranged this thing by stratagem. As it is, we shall have to resort to another method, and perhaps better, since we shall have to take no one into our confidence." The avenue was indeed a fine thoroughfare, lined on both sides with large and often imposing mansions, surrounded with trees and shrubbery, which served somewhat to screen them. We came at last to the Willoughby house, a sizable colonial residence set up on a hill. It was dark, except for one dim light in an upper story. In the shadow of the hedge, Craig silently vaulted the low fence and slipped up the terraces, as noiselessly as an Indian, scarcely crackling a twig or rustling a dead leaf on the ground. He paused as he came to a wing on the right of the house. I had followed more laboriously, carrying the box and noting that he was not looking so much at the house as at the sky, apparently. It did not take long to fathom what he was after. It was not a star-gazing expedition; he was following the telephone wire that ran in from the street to the corner of the house near which we were now standing. A moment's inspection showed him where the wire was led down, on the outside and entered through the top of a window. Quickly he worked, though in a rather awkward position, attaching two wires carefully to the telephone wires. Next he relieved me of the oak box with its strange contents, and placed it under the porch where it was completely hidden by some lattice-work which extended down to the ground on this side. Then he attached the new wires from the telephone to it and hid the connecting wires as best he could behind the swaying runners of a vine. At last, when he had finished to his satisfaction, we retraced our steps, to find that our only chance of getting out of town that night was by trolley that landed us, after many changes, in our apartment in New York, thoroughly convinced of the disadvantages of suburban detective work. Nevertheless the next day found us out sleuthing about Glenclair, this time in a more pleasant role. We had a newspaper friend or two out there who was willing to introduce us about without asking too many questions. Kennedy, of course, insisted on beginning at the very headquarters of gossip, the country club. We spent several enjoyable hours about the town, picking up a good deal of miscellaneous and useless information. It was, however, as Kennedy had suspected. Annie Grayson had taken up her residence in an artistic little house on one of the best side streets of the town. But her name was no longer Annie Grayson. She was Mrs. Maud Emery, a dashing young widow of some means, living in a very quiet but altogether comfortable style, cutting quite a figure in the exclusive suburban community, a leading member of the church circle, an officer of the Civic League, prominent in the women's club, and popular with those to whom the established order of things was so perfect that the only new bulwark of their rights was an anti-suffrage society. In fact, every one was talking of the valuable social acquisition in the person of this attractive young woman who entertained lavishly and was bracing up an otherwise drooping season. No one knew much about her, but then, that was not necessary. It was enough to accept one whose opinions and actions were not subversive of the social order in any way. The Willoughbys, of course, were among the most prominent people in the town. William Willoughby was head of the firm of Willoughby & Walton, and it was the general opinion that Mrs. Willoughby was the head of the firm of Ella & William Willoughby. The Willoughbys were good mixers, and were spoken well of even by the set who occupied the social stratum just one degree below that in which they themselves moved. In fact, when Mrs. Willoughby had been severely injured in an automobile accident during the previous summer Glenclair had shown real solicitude for her and had forgotten a good deal of its artificiality in genuine human interest. Kennedy was impatiently waiting for an opportunity to recover the box which he had left under the Willoughby porch. Several times we walked past the house, but it was not until nightfall that he considered it wise to make the recovery. Again we slipped silently up the terraces. It was the work of only a moment to cut the wires, and in triumph Craig bore off the precious oak box and its batteries. He said little on our journey back to the city, but the moment we had reached the laboratory he set the box on a table with an attachment which seemed to be controlled by pedals operated by the feet. "Walter," he explained, holding what looked like an earpiece in his hand, "this is another of those new little instruments that scientific detectives to-day are using. A poet might write a clever little verse en-titled, 'The telegraphone'll get you, if you don't watch out.' This is the latest improved telegraphone, a little electromagnetic wizard in a box, which we detectives are now using to take down and 'can' telephone conversations and other records. It is based on an entirely new principle in every way different from the phonograph. It was discovered by an inventor several years ago, while experimenting in telephony. "There are no disks or cylinders of wax, as in the phonograph, but two large spools of extremely fine steel wire. The record is not made mechanically on a cylinder, but electromagnetically on this wire. Small portions of magnetism are imparted to fractions of the steel wire as it passes between two carbon electric magnets. Each impression represents a sound wave. There is no apparent difference in the wire, no surface abrasion or other change, yet each particle of steel undergoes an electromagnetic transformation by which the sound is indelibly imprinted on it until it is wiped out by the erasing magnet. There are no cylinders to be shaved; all that is needed to use the wire again is to pass a magnet over it, automatically erasing any previous record that you do not wish to preserve. You can dictate into it, or, with this plug in, you can record a telephone conversation on it. Even rust or other deterioration of the steel wire by time will not affect this electromagnetic registry of sound. It can be read as long as steel will last. It is as effective for long distances as for short, and there is wire enough on one of these spools for thirty minutes of uninterrupted record." Craig continued to tinker tantalisingly with the machine. "The principle on which it is based," he added, "is that a mass of tempered steel may be impressed with and will retain magnetic fluxes varying in density and in sign in adjacent portions of its mass. There are no indentations on the wire or the steel disk. Instead there is a deposit of magnetic impulse on the wire, which is made by connecting up an ordinary telephone transmitter with the electromagnets and talking through the coil. The disturbance set up in the coils by the vibration of the diaphragm of the transmitter causes a deposit of magnetic impulse on the wire, the coils being connected with dry batteries. When the wire is again run past these coils, with a receiver such as I have here in circuit with the coils, a light vibration is set up in the receiver diaphragm which reproduces the sound of speech." He turned a switch and placed an ear-piece over his head, giving me another connected with it. We listened eagerly. There were no foreign noises in the machine, no grating or thumping sounds, as he controlled the running off of the steel wire by means of a foot-pedal. We were listening to everything that had been said over the Willoughby telephone during the day. Several local calls to tradesmen came first, and these we passed over quickly. Finally we heard the following conversation: "Hello. Is that you, Ella? Yes, this is Maud. Good-morning. How do you feel to-day?" "Good-morning, Maud. I don't feel very well. I have a splitting headache." "Oh, that's too bad, dear. What are you doing for it?" "Nothing--yet. If it doesn't get better I shall have Mr. Willoughby call up Dr. Guthrie." "Oh, I hope it gets better soon. You poor creature, don't you think a little trip into town might make you feel better? Had you thought of going to-day?" "Why, no. I hadn't thought of going in. Are you going?" "Did you see the Trimble ad. in the morning paper?" "No, I didn't see the papers this morning. My head felt too bad." "Well, just glance at it. It will interest you. They have the Kimberley Queen, the great new South African diamond on exhibition there." "They have? I never heard of it before, but isn't that interesting. I certainly would like to see it. Have you ever seen it?" "No, but I have made up my mind not to miss a sight of it. They say it is wonderful. You'd better come along. I may have something interesting to tell you, too." "Well, I believe I will go. Thank you, Maud, for suggesting it. Perhaps the little change will make me feel better. What train are you going to take? The ten-two? All right, I'll try to meet you at the station. Good-bye, Maud." "Good-bye, Ella." Craig stopped the machine, ran it back again and repeated the record. "So," he commented at the conclusion of the repetition, "the 'plant' has taken root. Annie Grayson has bitten at the bait." A few other local calls and a long-distance call from Mr. Willoughby cut short by his not finding his wife at home followed. Then there seemed to have been nothing more until after dinner. It was a call by Mr. Willoughby himself that now interested us. "Hello! hello! Is that you, Dr. Guthrie? Well, Doctor, this is Mr. Willoughby talking. I'd like to make an appointment for my wife to-morrow." "Why, what's the trouble, Mr. Willoughby? Nothing serious, I hope." "Oh, no, I guess not. But then I want to be sure, and I guess you can fix her up all right. She complains of not being able to sleep and has been having pretty bad headaches now and then." "Is that so? Well, that's too bad. These women and their headaches--even as a doctor they puzzle me. They often go away as suddenly as they come. However, it will do no harm to see me." "And then she complains of noises in her ears, seems to hear things, though as far as I can make out, there is nothing--at least nothing that I hear." "Um-m, hallucinations in hearing, I suppose. Any dizziness?" "Why, yes, a little once in a while." "How is she now?" "Well, she's been into town this afternoon and is pretty tired, but she says she feels a little better for the excitement of the trip." "Well, let me see. I've got to come down Woodridge Avenue to see a patient in a few minutes anyhow. Suppose I just drop off at your place?" "That will be fine. You don't think it is anything serious, do you, Doctor?" "Oh, no. Probably it's her nerves. Perhaps a little rest would do her good. We'll see." The telegraphone stopped, and that seemed to be the last conversation recorded. So far we had learned nothing very startling, I thought, and was just a little disappointed. Kennedy seemed well satisfied, however. Our own telephone rang, and it proved to be Donnelly on the wire. He had been trying to get Kennedy all day, in order to report that at various times his men at Trimble's had observed Mrs. Willoughby and later Annie Grayson looking with much interest at the Kimberley Queen, and other jewels in the exhibit. There was nothing more to report. "Keep it on view another day or two," ordered Kennedy. "Advertise it, but in a quiet way. We don't want too many people interested. I'll see you in the morning at the store--early." "I think I'll just run back to Glenclair again to-night," remarked Kennedy as he hung up the receiver. "You needn't bother about coming, Walter. I want to see Dr. Guthrie a moment. You remember him? We met him to-day at the country club, a kindly looking, middle-aged fellow?" I would willingly have gone back with him, but I felt that I could be of no particular use. While he was gone I pondered a good deal over the situation. Twice, at least, previously some one had pilfered jewellery from stores, leaving in its place worthless imitations. Twice the evidence had been so conflicting that no one could judge of its value. What reason, I asked myself, was there to suppose that it would be different now? No shoplifter in her senses was likely to lift the great Kimberley Queen gem with the eagle eyes of clerks and detectives on her, even if she did not discover that it was only a paste jewel. And if Craig gave the woman, whoever she was, a good opportunity to get away with it, it would be a case of the same conflicting evidence; or worse, no evidence. Yet the more I thought of it, the more apparent to me was it that Kennedy must have thought the whole thing out before. So far all that had been evident was that he was merely preparing a "plant." Still, I meant to caution him when he returned that one could not believe his eyes, certainly not his ears, as to what might happen, unless he was unusually skilful or lucky. It would not do to rely on anything so fallible as the human eye or ear, and I meant to impress it on him. What, after all, had been the net result of our activities so far? We had found next to nothing. Indeed, it was all a greater mystery than ever. It was very late when Craig returned, but I gathered from the still fresh look on his face that he had been successful in whatever it was he had had in mind when he made the trip. "I saw Dr. Guthrie," he reported laconically, as we prepared to turn in. "He says that he isn't quite sure but that Mrs. Willoughby may have a touch of vertigo. At any rate, he has consented to let me come out to-morrow with him and visit her as a specialist in nervous diseases from New York. I had to tell him just enough about the case to get him interested, but that will do no harm. I think I'll set this alarm an hour ahead. I want to get up early to-morrow, and if I shouldn't be here when you wake, you'll find me at Trimble's." XIV THE CRIMEOMETER The alarm wakened me all right, but to my surprise Kennedy had already gone, ahead of it. I dressed hurriedly, bolted an early breakfast, and made my way to Trimble's. He was not there, and I had about concluded to try the laboratory, when I saw him pulling up in a cab from which he took several packages. Donnelly had joined us by this time, and together we rode up in the elevator to the jewelry department. I had never seen a department-store when it was empty, but I think I should like to shop in one under those conditions. It seemed incredible to get into the elevator and go directly to the floor you wanted. The jewelry department was in the front of the building on one of the upper floors, with wide windows through which the bright morning light streamed attractively on the glittering wares that the clerks were taking out of the safes and disposing to their best advantage. The store had not opened yet, and we could work unhampered. From his packages, Kennedy took three black boxes. They seemed to have an opening in front, while at one side was a little crank, which, as nearly as I could make out, was operated by clockwork released by an electric contact. His first problem seemed to be to dispose the boxes to the best advantage at various angles about the counter where the Kimberley Queen was on exhibition. With so much bric-a-brac and other large articles about, it did not appear to be very difficult to conceal the boxes, which were perhaps four inches square on the ends and eight inches deep. From the boxes with the clockwork attachment at the side he led wires, centring at a point at the interior end of the aisle where we could see but would hardly be observed by any one standing at the jewelry counter. Customers had now begun to arrive, and we took a position in the background, prepared for a long wait. Now and then Donnelly casually sauntered past us. He and Craig had disposed the store detectives in a certain way so as to make their presence less obvious, while the clerks had received instructions how to act under the circumstance that a suspicious person was observed. Once when Donnelly came up he was quite excited. He had just received a message from Bentley that some of the stolen property, the pearls, probably, from the dog collar that had been taken from Shorham's, had been offered for sale by a "fence" known to the police as a former confederate of Annie Grayson. "You see, that is one great trouble with them all," he remarked, with his eye roving about the store in search of anything irregular. "A shoplifter rarely becomes a habitual criminal until after she passes the age of twenty-five. If they pass that age without quitting, there is little hope of their getting right again, as you see. For by that time they have long since begun to consort with thieves of the other sex." The hours dragged heavily, though it was a splendid chance to observe at leisure the psychology of the shopper who looked at much and bought little, the uncomfortableness of the men who had been dragged to the department store slaughter to say "Yes" and foot the bills, a kaleidoscopic throng which might have been interesting if we had not been so intent on only one matter. Kennedy grasped my elbow in vise-like fingers. Involuntarily I looked down at the counter where the Kimberley Queen reposed in all the trappings of genuineness. Mrs. Willoughby had arrived again. We were too far off to observe distinctly just what was taking place, but evidently Mrs. Willoughby was looking at the gem. A moment later another woman sauntered casually up to the counter. Even at a distance I recognised Annie Grayson. As nearly as I could make out they seemed to exchange remarks. The clerk answered a question or two, then began to search for something apparently to show them. Every one about them was busy, and, obedient to instructions from Donnelly, the store detectives were in the background. Kennedy was leaning forward watching as intently as the distance would permit. He reached over and pressed the button near him. After a minute or two the second woman left, followed shortly by Mrs. Willoughby herself. We hurried over to the counter, and Kennedy seized the box containing the Kimberley Queen. He examined it carefully. A flaw in the paste jewel caught his eye. "There has been a substitution here," he cried. "See! The paste jewel which we used was flawless; this has a little carbon spot here on the side." "One of my men has been detailed to follow each of them," whispered Donnelly. "Shall I order them to bring Mrs. Willoughby and Annie Grayson to the superintendent's office and have them searched?" "No," Craig almost shouted. "That would spoil everything. Don't make a move until I get at the real truth of this affair." The case was becoming more than ever a puzzle to me, but there was nothing left for me to do but to wait until Kennedy was ready to accompany Dr. Guthrie to the Willoughby house. Several times he tried to reach the doctor by telephone, but it was not until the middle of the afternoon that he succeeded. "I shall be quite busy the rest of the afternoon, Walter," remarked Craig, after he had made his appointment with Dr. Guthrie. "If you will meet me out at the Willoughbys' at about eight o'clock, I shall be much obliged to you." I promised, and tried to devote myself to catching up with my notes, which were always sadly behind when Kennedy had an important case. I did not succeed in accomplishing much, however. Dr. Guthrie himself met me at the door of the beautiful house on Woodridge Avenue and with a hearty handshake ushered me into the large room in the right wing outside of which we had placed the telegraphone two nights before. It was the library. We found Kennedy arranging an instrument in the music-room which adjoined the library. From what little knowledge I have of electricity I should have said it was, in part at least, a galvanometer, one of those instruments which register the intensity of minute electric currents. As nearly as I could make out, in this case the galvanometer was so arranged that its action swung to one side or the other a little concave mirror hung from a framework which rested on the table. Directly in front of it was an electric light, and the reflection of the light was caught in the mirror and focused by its concavity upon a point to one side of the light. Back of it was a long strip of ground glass and an arrow point, attached to which was a pen which touched a roll of paper. On the large table in the library itself Kennedy had placed in the centre a transverse board partition, high enough so that two people seated could see each other's faces and converse over it, but could not see each other's hands. On one side of the partition were two metal domes which were fixed to a board set on the table. On the other side, in addition to space on which he could write, Kennedy had arranged what looked like one of these new miniature moving-picture apparatuses operated by electricity. Indeed, I felt that it must be that, for directly in front of it, hanging on the wall, in plain view of any one seated on the side of the table containing the metal domes, was a large white sheet. The time for the experiment, whatever its nature might be, had at last arrived, and Dr. Guthrie introduced Mr. and Mrs. Willoughby to us as specialists whom he had persuaded with great difficulty to come down from New York. Mr. Willoughby he requested to remain outside until after the tests. She seemed perfectly calm as she greeted us, and looked with curiosity at the paraphernalia which Kennedy had installed in her library. Kennedy, who was putting some finishing touches on it, was talking in a low voice to reassure her. "If you will sit here, please, Mrs. Willoughby, and place your hands on these two brass domes--there, that's it. This is just a little arrangement to test your nervous condition. Dr. Guthrie, who understands it, will take his position outside in the music-room at that other table. Walter, just switch off that light, please. "Mrs. Willoughby, I may say that in testing, say, the memory, we psychologists have recently developed two tests, the event test, where something is made to happen before a person's eyes and later he is asked to describe it, and the picture test, where a picture is shown for a certain length of time, after which the patient is also asked to describe what was in the picture. I have endeavoured to combine these two ideas by using the moving-picture machine which you see here. I am going to show three reels of films." As nearly as I could make out Kennedy had turned on the light in the lantern on his side of the table. As he worked over the machine, which for the present served to distract Mrs. Willoughby's attention from herself, he was asking her a series of questions. From my position I could see that by the light of the machine he was recording both the questions and the answers, as well as the time registered to the fifth of a second by a stop-watch. Mrs. Willoughby could not see what he was doing under the pretence of working over his little moving-picture machine. He had at last finished the questioning. Suddenly, without any warning, a picture began to play on the sheet. I must say that I was startled myself. It represented the jewelry counter at Trimble's, and in it I could see Mrs. Willoughby herself in animated conversation with one of the clerks. I looked intently, dividing my attention between the picture and the woman. But so far as I could see there was nothing in this first film that incriminated either of them. Kennedy started on the second without stopping. It was practically the same as the first, only taken from a different angle. He had scarcely run it half through when Dr. Guthrie opened the door. "I think Mrs. Willoughby must have taken her hands off the metal domes," he remarked; "I can get no record out here." I had turned when he opened the door, and now I caught a glimpse of Mrs. Willoughby standing, her hands pressed tightly to her head as if it were bursting, and swaying as if she would faint. I do not know what the film was showing at this point, for Kennedy with a quick movement shut it off and sprang to her side. "There, that will do, Mrs. Willoughby. I see that you are not well," he soothed. "Doctor, a little something to quiet her nerves. I think we can complete our work merely by comparing notes. Call Mr. Willoughby, Walter. There, sir, if you will take charge of your wife and perhaps take her for a turn or two in the fresh air, I think we can tell you in a few moments whether her condition is in any way serious or not." Mrs. Willoughby was on the verge of hysterics as her husband supported her out of the room. The door had scarcely shut before Kennedy threw open a window and seemed to beckon into the darkness. As if from nowhere, Donnelly and Bentley sprang no and were admitted. Dr. Guthrie had now returned from the music-room, bearing a sheet of paper on which was traced a long irregular curve at various points on which marginal notes had been written hastily. Kennedy leaped directly into the middle of things with his characteristic ardour. "You recall," he began, "that no one seemed to know just who took the jewels in both the cases you first reported? 'Seeing is believing,' is an old saying, but in the face of such reports as you detectives gathered it is in a fair way to lose its force. And you were not at fault, either, for modern psychology is proving by experiments that people do not see even a fraction of the things they confidently believe they see. "For example, a friend of mine, a professor in a Western university, has carried on experiments with scores of people and has not found one who could give a completely accurate description of what he had seen, even in the direct testimony; while under the influence of questions, particularly if they were at all leading, witnesses all showed extensive inaccuracies in one or more particulars, and that even though they are in a more advantageous position for giving reports than were your clerks who were not prepared. Indeed, it is often a wonder to me that witnesses of ordinary events who are called upon in court to relate what they saw after a considerable lapse of time are as accurate as they are, considering the questioning they often go through from interested parties, neighbours and friends, and the constant and often biased rehearsing of the event. The court asks the witness to tell the truth, the whole truth, and nothing but the truth. How can he? In fact, I am often surprised that there is such a resemblance between the testimony and the actual facts of the case! "But I have here a little witness that never lies, and, mindful of the fallibility of ordinary witnesses, I called it in. It is a new, compact, little motion camera which has just been perfected to do automatically what the big moving-picture making cameras do." He touched one of the little black boxes such as we had seen him install in the jewelry department at Trimble's. "Each of these holds one hundred and sixty feet of film," he resumed, "enough to last three minutes, taking, say, sixteen pictures to the foot and running about one foot a second. You know that less than ten or eleven pictures a second affect the retina as separate, broken pictures. The use of this compact little motion camera was suggested to me by an ingenious but cumbersome invention recently offered to the police in Paris--the installation on the clock-towers in various streets of cinematograph apparatus directed by wireless. The motion camera as a detective has now proved its value. I have here three films taken at Trimble's, from different angles, and they clearly show exactly what actually occurred while Mrs. Willoughby and Annie Grayson were looking at the Kimberley Queen." He paused as if analysing the steps in his own mind. "The telegraphone gave me the first hint of the truth," he said. "The motion camera brought me a step nearer, but without this third instrument, while I should have been successful, I would not have got at the whole truth." He was fingering the apparatus on the library table connected with that in the music-room. "This is the psychometer for testing mental aberrations," he explained. "The scientists who are using it to-day are working, not with a view to aiding criminal jurisprudence, but with the hope of making such discoveries that the mental health of the race may be bettered. Still, I believe that in the study of mental diseases these men are furnishing the knowledge upon which future criminologists will build to make the detection of crime an absolute certainty. Some day there will be no jury, no detectives, no witnesses, no attorneys. The state will merely submit all suspects to tests of scientific instruments like these, and as these instruments can not make mistakes or tell lies their evidence will be conclusive of guilt or innocence. "Already the psychometer is an actual working fact. No living man can conceal his emotions from the uncanny instrument. He may bring the most gigantic of will-powers into play to conceal his inner feelings and the psychometer will record the very work which he makes this will-power do. "The machine is based upon the fact that experiments have proved that the human body's resistance to an electrical current is increased with the increase of the emotions. Dr. Jung, of Zurich, thought that it would be a very simple matter to record these varying emotions, and the psychometer is the result--simple and crude to-day compared with what we have a right to expect in the future. "A galvanometer is so arranged that its action swings a mirror from side to side, reflecting a light. This light falls on a ground-glass scale marked off into centimetres, and the arrow is made to follow the beam of light. A pen pressing down on a metal drum carrying a long roll of paper revolved by machinery records the variations. Dr. Guthrie, who had charge of the recording, simply sat in front of the ground glass and with the arrow point followed the reflection of the light as it moved along the scale, in this way making a record on the paper on the drum, which I see he is now holding in his hand. "Mrs. Willoughby, the subject, and myself, the examiner, sat here, facing each other over this table. Through those metal domes on which she was to keep her hands she received an electric current so weak that it could not be felt even by the most sensitive nerves. Now with every increase in her emotion, either while I was putting questions to her or showing her the pictures, whether she showed it outwardly or not, she increased her body's resistance to the current that was being passed in through her hands. The increase was felt by the galvanometer connected by wires in the music-room, the mirror swung, the light travelled on the scale, the arrow was moved by Dr. Guthrie, and her varying emotions were recorded indelibly upon the revolving sheet of paper, recorded in such a way as to show their intensity and reveal to the trained scientist much of the mental condition of the subject." Kennedy and Dr. Guthrie now conversed in low tones. Once in a while I could catch a scrap of the conversation--"not an epileptic," "no abnormal conformation of the head," "certain mental defects," "often the result of sickness or accident." "Every time that woman appeared there was a most peculiar disturbance," remarked Dr. Guthrie as Kennedy took the roll of paper from him and studied it carefully. At length the light seemed to break through his face. "Among the various kinds of insanity," he said, slowly measuring his words, "there is one that manifests itself as an irresistible impulse to steal. Such terms as neuropath and kleptomaniac are often regarded as rather elegant names for contemptible excuses invented by medical men to cover up stealing. People are prone to say cynically, 'Poor man's sins; rich man's diseases.' Yet kleptomania does exist, and it is easy to make it seem like crime when it is really persistent, incorrigible, and irrational stealing. Often it is so great as to be incurable. Cases have been recorded of clergymen who were kleptomaniacs and in one instance a dying victim stole the snuffbox of his confessor. "It is the pleasure and excitement of stealing, not the desire for the object stolen, which distinguishes the kleptomaniac from the ordinary thief. Usually the kleptomaniac is a woman, with an insane desire to steal for the mere sake of stealing. The morbid craving for excitement which is at the bottom of so many motiveless and useless crimes, again and again has driven apparently sensible men and women to ruin and even to suicide. It is a form of emotional insanity, not loss of control of the will, but perversion of the will. Some are models in their lucid intervals, but when the mania is on them they cannot resist. The very act of taking constitutes the pleasure, not possession. One must take into consideration many things, for such diseases as kleptomania belong exclusively to civilisation; they are the product of an age of sensationalism. Naturally enough, woman, with her delicately balanced nervous organisation, is the first and chief offender." Kennedy had seated himself at the table and was writing hastily. When he had finished, he held the papers in his hand to dry. He handed one sheet each to Bentley and Donnelly. We crowded about. Kennedy had simply written out two bills for the necklace and the collar of pearls. "Send them in to Mr. Willoughby," he added. "I think he will be glad to pay them to hush up the scandal." We looked at each other in amazement at the revelation. "But what about Annie Grayson?" persisted Donnelly. "I have taken care of her," responded Kennedy laconically. "She is already under arrest. Would you like to see why?" A moment later we had all piled into Dr. Guthrie's car, standing at the door. At the cosy little Grayson villa we found two large eyed detectives and a very angry woman waiting impatiently. Heaped up on a table in the living room was a store of loot that readily accounted for the ocular peculiarity of the detectives. The jumble on the table contained a most magnificent collection of diamonds, sapphires, ropes of pearls, emeralds, statuettes, and bronze and ivory antiques, books in rare bindings, and other baubles which wealth alone can command. It dazzled our eyes as we made a mental inventory of the heap. Yet it was a most miscellaneous collection. Beside a pearl collar with a diamond clasp were a pair of plain leather slippers and a pair of silk stockings. Things of value and things of no value were mixed as if by a lunatic. A beautiful neck ornament of carved coral lay near a half-dozen common linen handkerchiefs. A strip of silk hid a valuable collection of antique jewellery. Besides diamonds and precious stones by the score were gold and silver ornaments, silks, satins, laces, draperies, articles of virtu, plumes, even cutlery and bric-a-brac. All this must have been the result of countless excursions to the stores of New York and innumerable clever thefts. We could only look at each other in amazement and wonder at the defiance written on the face of Annie Grayson. "In all this strange tangle of events," remarked Kennedy, surveying the pile with obvious satisfaction, "I find that the precise instruments of science have told me one more thing. Some one else discovered Mrs. Willoughby's weakness, led her on, suggested opportunities to her, used her again and again, profited by her malady, probably to the extent of thousands of dollars. My telegraphone record hinted at that. In some way Annie Grayson secured the confidence of Mrs. Willoughby. The one took for the sake of taking; the other received for the sake of money. Mrs. Willoughby was easily persuaded by her new friend to leave here what she had stolen. Besides, having taken it, she had no further interest in it. "The rule of law is that every one is responsible who knows the nature and consequences of his act. We have absolute proof that you, Annie Grayson, although you did not actually commit any of the thefts yourself, led Mrs. Willoughby on and profited by her. Dr. Guthrie will take care of the case of Mrs. Willoughby. But the law must deal with you for playing on the insanity of a kleptomaniac--the cleverest scheme yet of the queen of shoplifters." As Kennedy turned nonchalantly from the detectives who had seized Annie Grayson, he drew a little red folder from his pocket. "You see, Walter," he smiled, "how soon one gets into a habit? I'm almost a regular commuter, now. You know, they are always bringing out these little red folders just when things grow interesting." I glanced over his shoulder. He was studying the local timetable. "We can get the last train from Glenclair if we hurry," he announced, stuffing the folder back into his pocket. "They will take her to Newark by trolley, I suppose. Come on." We made our hasty adieux and escaped as best we could the shower of congratulations. "Now for a rest," he said, settling back into the plush covered seat for the long ride into town, his hat down over his eyes and his legs hunched up against the back of the next seat. Across in the tube and uptown in a nighthawk cab we went and at last we were home for a good sleep. "This promises to be an off-day," Craig remarked, the next morning over the breakfast table. "Meet me in the forenoon and we'll take a long, swinging walk. I feel the need of physical exercise." "A mark of returning sanity!" I exclaimed. I had become so used to being called out on the unexpected, now, that I almost felt that some one might stop us on our tramp. Nothing of the sort happened, however, until our return. Then a middle-aged man and a young girl, heavily veiled, were waiting for Kennedy, as we turned in from the brisk finish in the cutting river wind along the Drive. "Winslow is my name, sir," the man began, rising nervously as we entered the room, "and this is my only daughter, Ruth." Kennedy bowed and we waited for the man to proceed. He drew his hand over his forehead which was moist with perspiration in spite of the season. Ruth Winslow was an attractive young woman, I could see at a glance, although her face was almost completely hidden by the thick veil. "Perhaps, Ruth, I had better--ah--see these gentlemen alone?" suggested her father gently. "No, father," she answered in a tone of forced bravery, "I think not. I can stand it. I must stand it. Perhaps I can help you in telling about the--the case." Mr. Winslow cleared his throat. "We are from Goodyear, a little mill-town," he proceeded slowly, "and as you doubtless can see we have just arrived after travelling all day." "Goodyear," repeated Kennedy slowly as the man paused. "The chief industry, of course, is rubber, I suppose." "Yes," assented Mr. Winslow, "the town centres about rubber. Our factories are not the largest but are very large, nevertheless, and are all that keep the town going. It is on rubber, also, I fear, that the tragedy which I am about to relate hangs. I suppose the New York papers have had nothing to say of the strange death of Bradley Cushing, a young chemist in Goodyear who was formerly employed by the mills but had lately set up a little laboratory of his own?" Kennedy turned to me. "Nothing unless the late editions of the evening papers have it," I replied. "Perhaps it is just as well," continued Mr. Winslow. "They wouldn't have it straight. In fact, no one has it straight yet. That is why we have come to you. You see, to my way of thinking Bradley Cushing was on the road to changing the name of the town from Goodyear to Cushing. He was not the inventor of synthetic rubber about which you hear nowadays, but he had improved the process so much that there is no doubt that synthetic rubber would soon have been on the market cheaper and better than the best natural rubber from Para. "Goodyear is not a large place, but it is famous for its rubber and uses a great deal of raw material. We have sent out some of the best men in the business, seeking new sources in South America, in Mexico, in Ceylon, Malaysia and the Congo. What our people do not know about rubber is hardly worth knowing, from the crude gum to the thousands of forms of finished products. Goodyear is a wealthy little town, too, for its size. Naturally all its investments are in rubber, not only in our own mills but in companies all over the world. Last year several of our leading citizens became interested in a new concession in the Congo granted to a group of American capitalists, among whom was Lewis Borland, who is easily the local magnate of our town. When this group organised an expedition to explore the region preparatory to taking up the concession, several of the best known people in Goodyear accompanied the party and later subscribed for large blocks of stock. "I say all this so that you will understand at the start just what part rubber plays in the life of our little community. You can readily see that such being the case, whatever advantage the world at large might gain from cheap synthetic rubber would scarcely benefit those whose money and labour had been expended on the assumption that rubber would be scarce and dear. Naturally, then, Bradley Cushing was not precisely popular with a certain set in Goodyear. As for myself, I am frank to admit that I might have shared the opinion of many others regarding him, for I have a small investment in this Congo enterprise myself. But the fact is that Cushing, when he came to our town fresh from his college fellowship in industrial chemistry, met my daughter." Without taking his eyes off Kennedy, he reached over and patted the gloved hand that clutched the arm of the chair alongside his own. "They were engaged and often they used to talk over what they would do when Bradley's invention of a new way to polymerise isoprene, as the process is called, had solved the rubber question and had made him rich. I firmly believe that their dreams were not day dreams, either. The thing was done. I have seen his products and I know something about rubber. There were no impurities in his rubber." Mr. Winslow paused. Ruth was sobbing quietly. "This morning," he resumed hastily, "Bradley Cushing was found dead in his laboratory under the most peculiar circumstances. I do not know whether his secret died with him or whether some one has stolen it. From the indications I concluded that he had been murdered." Such was the case as Kennedy and I heard it then. Ruth looked up at him with tearful eyes wistful with pain, "Would Mr. Kennedy work on it?" There was only one answer. XV THE VAMPIRE As we sped out to the little mill-town on the last train, after Kennedy had insisted on taking us all to a quiet little restaurant, he placed us so that Miss Winslow was furthest from him and her father nearest. I could hear now and then scraps of their conversation as he resumed his questioning, and knew that Mr. Winslow was proving to be a good observer. "Cushing used to hire a young fellow of some scientific experience, named Strong," said Mr. Winslow as he endeavoured to piece the facts together as logically as it was possible to do. "Strong used to open his laboratory for him in the morning, clean up the dirty apparatus, and often assist him in some of his experiments. This morning when Strong approached the laboratory at the usual time he was surprised to see that though it was broad daylight there was a light burning. He was alarmed and before going in looked through the window. The sight that he saw froze him. There lay Cushing on a workbench and beside him and around him pools of coagulating blood. The door was not locked, as we found afterward, but the young man did not stop to enter. He ran to me and, fortunately, I met him at our door. I went back. "We opened the unlocked door. The first thing, as I recall it, that greeted me was an unmistakable odour of oranges. It was a very penetrating and very peculiar odour. I didn't understand it, for there seemed to be something else in it besides the orange smell. However, I soon found out what it was, or at least Strong did. I don't know whether you know anything about it, but it seems that when you melt real rubber in the effort to reduce it to carbon and hydrogen, you get a liquid substance which is known as isoprene. Well, isoprene, according to Strong, gives out an odour something like ether. Cushing, or some one else, had apparently been heating isoprene. As soon as Strong mentioned the smell of ether I recognised that that was what made the smell of oranges so peculiar. "However, that's not the point. There lay Cushing on his back on the workbench, just as Strong had said. I bent over him, and in his arm, which was bare, I saw a little gash made by some sharp instrument and laying bare an artery, I think, which was cut. Long spurts of blood covered the floor for some distance around and from the veins in his arm, which had also been severed, a long stream of blood led to a hollow in the cement floor where it had collected. I believe that he bled to death." "And the motive for such a terrible crime?" queried Craig. Mr. Winslow shook his head helplessly. "I suppose there are plenty of motives," he answered slowly, "as many motives as there are big investments in rubber-producing ventures in Goodyear." "But have you any idea who would go so far to protect his investments as to kill?" persisted Kennedy. Mr. Winslow made no reply. "Who," asked Kennedy, "was chiefly interested in the rubber works where Cushing was formerly employed?" "The president of the company is the Mr. Borland whom I mentioned," replied Mr. Winslow. "He is a man of about forty, I should say, and is reputed to own a majority of the--" "Oh, father," interrupted Miss Winslow, who had caught the drift of the conversation in spite of the pains that had been taken to keep it away from her, "Mr. Borland would never dream of such a thing. It is wrong even to think of it." "I didn't say that he would, my dear," corrected Mr. Winslow gently. "Professor Kennedy asked me who was chiefly interested in the rubber works and Mr. Borland owns a majority of the stock." He leaned over and whispered to Kennedy, "Borland is a visitor at our home, and between you and me, he thinks a great deal of Ruth." I looked quickly at Kennedy, but he was absorbed in looking out of the car window at the landscape which he did not and could not see. "You said there were others who had an interest in outside companies," cross-questioned Kennedy. "I take it that you mean companies dealing in crude rubber, the raw material, people with investments in plantations and concessions, perhaps. Who are they? Who were the men who went on that expedition to the Congo with Borland which you mentioned?" "Of course, there was Borland himself," answered Winslow. "Then there was a young chemist named Lathrop, a very clever and ambitious fellow who succeeded Cushing when he resigned from the works, and Dr. Harris, who was persuaded to go because of his friendship for Borland. After they took up the concession I believe all of them put money into it, though how much I can't say." I was curious to ask whether there were any other visitors at the Winslow house who might be rivals for Ruth's affections, but there was no opportunity. Nothing more was said until we arrived at Goodyear. We found the body of Cushing lying in a modest little mortuary chapel of an undertaking establishment on the main street. Kennedy at once began his investigation by discovering what seemed to have escaped others. About the throat were light discolourations that showed that the young inventor had been choked by a man with a powerful grasp, although the fact that the marks had escaped observation led quite obviously to the conclusion that he had not met his death in that way, and that the marks probably played only a minor part in the tragedy. Kennedy passed over the doubtful evidence of strangulation for the more profitable examination of the little gash in the wrist. "The radial artery has been cut," he mused. A low exclamation from him brought us all bending over him as he stooped and examined the cold form. He was holding in the palm of his hand a little piece of something that shone like silver. It was in the form of a minute hollow cylinder with two grooves on it, a cylinder so tiny that it would scarcely have slipped over the point of a pencil. "Where did you find it?" I asked eagerly. He pointed to the wound. "Sticking in the severed end of a piece of vein," he replied, half to himself, "cuffed over the end of the radial artery which had been severed, and done so neatly as to be practically hidden. It was done so cleverly that the inner linings of the vein and artery, the endothelium as it is called, were in complete contact with each other." As I looked at the little silver thing and at Kennedy's face, which betrayed nothing, I felt that here indeed was a mystery. What new scientific engine of death was that little hollow cylinder? "Next I should like to visit the laboratory," he remarked simply. Fortunately, the laboratory had been shut and nothing had been disturbed except by the undertaker and his men who had carried the body away. Strong had left word that he had gone to Boston, where, in a safe deposit box, was a sealed envelope in which Cushing kept a copy of the combination of his safe, which had died with him. There was, therefore, no hope of seeing the assistant until the morning. Kennedy found plenty to occupy his time in his minute investigation of the laboratory. There, for instance, was the pool of blood leading back by a thin dark stream to the workbench and its terrible figure, which I could almost picture to myself lying there through the silent hours of the night before, with its life blood slowly oozing away, unconscious, powerless to save itself. There were spurts of arterial blood on the floor and on the nearby laboratory furniture, and beside the workbench another smaller and isolated pool of blood. On a table in a corner by the window stood a microscope which Cushing evidently used, and near it a box of fresh sterilised slides. Kennedy, who had been casting his eye carefully about taking in the whole laboratory, seemed delighted to find the slides. He opened the box and gingerly took out some of the little oblong pieces of glass, on each of which he dropped a couple of minute drops of blood from the arterial spurts and the venous pools on the floor. Near the workbench were circular marks, much as if some jars had been set down there. We were watching him, almost in awe at the matter of fact manner in which, he was proceeding in what to us was nothing but a hopeless enigma, when I saw him stoop and pick up a few little broken pieces of glass. There seemed to be blood spots on the glass, as on other things, but particularly interesting to him. A moment later I saw that he was holding in his hand what were apparently the remains of a little broken vial which he had fitted together from the pieces. Evidently it had been used and dropped in haste. "A vial for a local anesthetic," he remarked. "This is the sort of thing that might be injected into an arm or leg and deaden the pain of a cut, but that is all. It wouldn't affect the consciousness or prevent any one from resisting a murderer to the last. I doubt if that had anything directly to do with his death, or perhaps even that this is Cushing's blood on it." Unlike Winslow I had seen Kennedy in action so many times that I knew it was useless to speculate. But I was fascinated, for the deeper we got into the case, the more unusual and inexplicable it seemed. I gave that end of it up, but the fact that Strong had gone to secure the combination of the safe suggested to me to examine that article. There was certainly no evidence of robbery or even of an attempt at robbery there. "Was any doctor called?" asked Kennedy. "Yes," he replied. "Though I knew it was of no use I called in Dr. Howe, who lives up the street from the laboratory. I should have called Dr. Harris, who used to be my own physician, but since his return from Africa with the Borland expedition, he has not been in very good health and has practically given up his practice. Dr. Howe is the best practising physician in town, I think." "We shall call on him to-morrow," said Craig, snapping his watch, which already marked far after midnight. Dr. Howe proved, the next day, to be an athletic-looking man, and I could not help noticing and admiring his powerful frame and his hearty handshake, as he greeted us when we dropped into his office with a card from Winslow. The doctor's theory was that Cushing had committed suicide. "But why should a young man who had invented a new method of polymerising isoprene, who was going to become wealthy, and was engaged to a beautiful young girl, commit suicide?" The doctor shrugged his shoulders. It was evident that he, too, belonged to the "natural rubber set" which dominated Goodyear. "I haven't looked into the case very deeply, but I'm not so sure that he had the secret, are you?" Kennedy smiled. "That is what I'd like to know. I suppose that an expert like Mr. Borland could tell me, perhaps?" "I should think so." "Where is his office?" asked Craig. "Could you point it out to me from the window?" Kennedy was standing by one of the windows of the doctor's office, and as he spoke he turned and drew a little field glass from his pocket. "Which end of the rubber works is it?" Dr. Howe tried to direct him but Kennedy appeared unwarrantably obtuse, requiring the doctor to raise the window, and it was some moments before he got his glasses on the right spot. Kennedy and I thanked the doctor for his courtesy and left the office. We went at once to the office of Dr. Harris, to whom Winslow had also given us cards. We found him an anaemic man, half asleep. Kennedy tentatively suggested the murder of Cushing. "Well, if you ask me my opinion," snapped out the doctor, "although I wasn't called into the case, from what I hear, I'd say that he was murdered." "Some seem to think it was suicide," prompted Kennedy. "People who have brilliant prospects and are engaged to pretty girls don't usually die of their own accord," rasped Harris. "So you think he really did have the secret of artificial rubber?" asked Craig. "Not artificial rubber. Synthetic rubber. It was the real thing, I believe." "Did Mr. Borland and his new chemist Lathrop believe it, too?" "I can't say. But I should surely advise you to see them." The doctor's face was twitching nervously. "Where is Borland's office?" repeated Kennedy, again taking from his pocket the field glass and adjusting it carefully by the window. "Over there," directed Harris, indicating the corner of the works to which we had already been directed. Kennedy had stepped closer to the window before him and I stood beside him looking out also. "The cut was a very peculiar one," remarked Kennedy, still adjusting the glasses. "An artery and a vein had been placed together so that the endothelium, or inner lining of each, was in contact with the other, giving a continuous serous surface. Which window did you say was Borland's? I wish you'd step to the other window and raise it, so that I can be sure. I don't want to go wandering all over the works looking for him." "Yes," the doctor said as he went, leaving him standing beside the window from which he had been directing us, "yes, you surely should see Mr. Borland. And don't forget that young chemist of his, Lathrop, either, If I can be of any more help to you, come back again." It was a long walk through the village and factory yards to the office of Lewis Borland, but we were amply repaid by finding him in and ready to see us. Borland was a typical Yankee, tall, thin, evidently predisposed to indigestion, a man of tremendous mental and nervous energy and with a hidden wiry strength. "Mr. Borland," introduced Kennedy, changing his tactics and adopting a new role, "I've come down to you as an authority on rubber to ask you what your opinion is regarding the invention of a townsman of yours named Cushing." "Cushing?" repeated Borland in some surprise. "Why--" "Yes," interrupted Kennedy, "I understand all about it. I had heard of his invention in New York and would have put some money into it if I could have been convinced. I was to see him to-day, but of course, as you were going to say, his death prevents it. Still, I should like to know what you think about it." "Well," Borland added, jerking out his words nervously, as seemed to be his habit, "Cushing was a bright young fellow. He used to work for me until he began to know too much about the rubber business." "Do you know anything about his scheme?" insinuated Kennedy. "Very little, except that it was not patented yet, I believe, though he told every one that the patent was applied for and he expected to get a basic patent in some way without any interference." "Well," drawled Kennedy, affecting as nearly as possible the air of a promoter, "if I could get his assistant, or some one who had authority to be present, would you, as a practical rubber man, go over to his laboratory with me? I'd join you in making an offer to his estate for the rights to the process, if it seemed any good." "You're a cool one," ejaculated Borland, with a peculiar avaricious twinkle in the corners of his eyes. "His body is scarcely cold and yet you come around proposing to buy out his invention and--and, of all persons, you come to me." "To you?" inquired Kennedy blandly. "Yes, to me. Don't you know that synthetic rubber would ruin the business system that I have built up here?" Still Craig persisted and argued. "Young man," said Borland rising at length as if an idea had struck him, "I like your nerve. Yes, I will go. I'll show you that I don't fear any competition from rubber made out of fusel oil or any other old kind of oil." He rang a bell and a boy answered. "Call Lathrop," he ordered. The young chemist, Lathrop, proved to be a bright and active man of the new school, though a good deal of a rubber stamp. Whenever it was compatible with science and art, he readily assented to every proposition that his employer laid down. Kennedy had already telephoned to the Winslows and Miss Winslow had answered that Strong had returned from Boston. After a little parleying, the second visit to the laboratory was arranged and Miss Winslow was allowed to be present with her father, after Kennedy had been assured by Strong that the gruesome relics of the tragedy would be cleared away. It was in the forenoon that we arrived with Borland and Lathrop. I could not help noticing the cordial manner with which Borland greeted Miss Winslow. There was something obtrusive even in his sympathy. Strong, whom we met now for the first time, seemed rather suspicious of the presence of Borland and his chemist, but made an effort to talk freely without telling too much. "Of course you know," commenced Strong after proper urging, "that it has long been the desire of chemists to synthesise rubber by a method that will make possible its cheap production on a large scale. In a general way I know what Mr. Cushing had done, but there are parts of the process which are covered in the patents applied for, of which I am not at liberty to speak yet." "Where are the papers in the case, the documents showing the application for the patent, for instance?" asked Kennedy. "In the safe, sir," replied Strong. Strong set to work on the combination which he had obtained from the safe deposit vault. I could see that Borland and Miss Winslow were talking in a low tone. "Are you sure that it is a fact?" I overheard him ask, though I had no idea what they were talking about. "As sure as I am that the Borland Rubber Works are a fact," she replied. Craig also seemed to have overheard, for he turned quickly. Borland had taken out his penknife and was moistening the blade carefully preparing to cut into a piece Of the synthetic rubber. In spite of his expressed scepticism, I could see that he was eager to learn what the product was really like. Strong, meanwhile, had opened the safe and was going over the papers. A low exclamation from him brought us around the little pile of documents. He was holding a will in which nearly everything belonging to Cushing was left to Miss Winslow. Not a word was said, although I noticed that Kennedy moved quickly to her side, fearing that the shock of the discovery might have a bad effect on her, but she took it with remarkable calmness. It was apparent that Cushing had taken the step of his own accord and had said nothing to her about it. "What does anything amount to?" she said tremulously at last. "The dream is dead without him in it." "Come," urged Kennedy gently. "This is enough for to-day." An hour later we were speeding back to New York. Kennedy had no apparatus to work with out at Goodyear and could not improvise it. Winslow agreed to keep us in touch with any new developments during the few hours that Craig felt it was necessary to leave the scene of action. Back again in New York, Craig took a cab directly for his laboratory, leaving me marooned with instructions not to bother him for several hours. I employed the time in a little sleuthing on my own account, endeavouring to look up the records of those involved in the case. I did not discover much, except an interview that had been given at the time of the return of his expedition by Borland to the Star, in which he gave a graphic description of the dangers from disease that they had encountered. I mention it because, though it did not impress me much when I read it, it at once leaped into my mind when the interminable hours were over and I rejoined Kennedy. He was bending over a new microscope. "This is a rubber age, Walter," he began, "and the stories of men who have been interested in rubber often sound like fiction." He slipped a slide under the microscope, looked at it and then motioned to me to do the same. "Here is a very peculiar culture which I have found in some of that blood," he commented. "The germs are much larger than bacteria and they can be seen with a comparatively low power microscope swiftly darting between the blood cells, brushing them aside, but not penetrating them as some parasites, like that of malaria, do. Besides, spectroscope tests show the presence of a rather well-known chemical in that blood." "A poisoning, then?" I ventured. "Perhaps he suffered from the disease that many rubber workers get from the bisulphide of carbon. He must have done a good deal of vulcanising of his own rubber, you know." "No," smiled Craig enigmatically, "it wasn't that. It was an arsenic derivative. Here's another thing. You remember the field glass I used?" He had picked it up from the table and was pointing at a little hole in the side, that had escaped my notice before. "This is what you might call a right-angled camera. I point the glass out of the window and while you think I am looking through it I am really focusing it on you and taking your picture standing there beside me and out of my apparent line of vision. It would deceive the most wary." Just then a long-distance call from Winslow told us that Borland had been to call on Miss Ruth and, in as kindly a way as could be, had offered her half a million dollars for her rights in the new patent. At once it flashed over me that he was trying to get control of and suppress the invention in the interests of his own company, a thing that has been done hundreds of times. Or could it all have been part of a conspiracy? And if it was his conspiracy, would he succeed in tempting his friend, Miss Winslow, to fall in with this glittering offer? Kennedy evidently thought, also, that the time for action had come, for without a word he set to work packing his apparatus and we were again headed for Goodyear. XVI THE BLOOD TEST We arrived late at night, or rather in the morning, but in spite of the late hour Kennedy was up early urging me to help him carry the stuff over to Cushing's laboratory. By the middle of the morning he was ready and had me scouring about town collecting his audience, which consisted of the Winslows, Borland and Lathrop, Dr. Howe, Dr. Harris, Strong and myself. The laboratory was darkened and Kennedy took his place beside an electric moving picture apparatus. The first picture was different from anything any of us had ever seen on a screen before. It seemed to be a mass of little dancing globules. "This," explained Kennedy, "is what you would call an educational moving picture, I suppose. It shows normal blood corpuscles as they are in motion in the blood of a healthy man. Those little round cells are the red corpuscles and the larger irregular cells are the white corpuscles." He stopped the film. The next picture was a sort of enlarged and elongated house fly, apparently, of sombre grey color, with a narrow body, thick proboscis and wings that overlapped like the blades of a pair of shears. "This," he went on, "is a picture of the now well known tse-tse fly found over a large area of Africa. It has a bite something like a horse-fly and is a perfect blood-sucker. Vast territories of thickly populated, fertile country near the shores of lakes and rivers are now depopulated as a result of the death-dealing bite of these flies, more deadly than the blood-sucking, vampirish ghosts with which, in the middle ages, people supposed night air to be inhabited. For this fly carries with it germs which it leaves in the blood of its victims, which I shall show next." A new film started. "Here is a picture of some blood so infected. Notice that worm-like sheath of undulating membrane terminating in a slender whip-like process by which it moves about. That thing wriggling about like a minute electric eel, always in motion, is known as the trypanosome. "Isn't this a marvellous picture? To see the micro-organism move, evolve and revolve in the midst of normal cells, uncoil and undulate in the fluids which they inhabit, to see them play hide and seek with the blood corpuscles and clumps of fibrin, turn, twist, and rotate as if in a cage, to see these deadly little trypanosomes moving back and forth in every direction displaying their delicate undulating membranes and shoving aside the blood cells that are in their way while by their side the leucocytes, or white corpuscles, lazily extend or retract their pseudopods of protoplasm. To see all this as it is shown before us here is to realise that we are in the presence of an unknown world, a world infinitesimally small, but as real and as complex as that about us. With the cinematograph and the ultra-microscope we can see what no other forms of photography can reproduce. "I have secured these pictures so that I can better mass up the evidence against a certain person in this room. For in the blood of one of you is now going on the fight which you have here seen portrayed by the picture machine. Notice how the blood corpuscles in this infected blood have lost their smooth, glossy appearance, become granular and incapable of nourishing the tissues. The trypanosomes are fighting with the normal blood cells. Here we have the lowest group of animal life, the protozoa, at work killing the highest, man." Kennedy needed nothing more than the breathless stillness to convince him of the effectiveness of his method of presenting his case. "Now," he resumed, "let us leave this blood-sucking, vampirish tse-tse fly for the moment. I have another revelation to make." He laid down on the table under the lights, which now flashed up again, the little hollow silver cylinder. "This little instrument," Kennedy explained, "which I have here is known as a canula, a little canal, for leading off blood from the veins of one person to another--in other words, blood transfusion. Modern doctors are proving themselves quite successful in its use. "Of course, like everything, it has its own peculiar dangers. But the one point I wish to make is this: In the selection of a donor for transfusion, people fall into definite groups. Tests of blood must be made first to see whether it 'agglutinates,' and in this respect there are four classes of persons. In our case this matter had to be neglected. For, gentlemen, there were two kinds of blood on that laboratory floor, and they do not agglutinate. This, in short, was what actually happened. An attempt was made to transfuse Cushing's blood as donor to another person as recipient. A man suffering from the disease caught from the bite of the tse-tse fly--the deadly sleeping sickness so well known in Africa--has deliberately tried a form of robbery which I believe to be without parallel. He has stolen the blood of another! "He stole it in a desperate attempt to stay an incurable disease. This man had used an arsenic compound called atoxyl, till his blood was filled with it and its effects on the trypanosomes nil. There was but one wild experiment more to try--the stolen blood of another." Craig paused to let the horror of the crime sink into our minds. "Some one in the party which went to look over the concession in the Congo contracted the sleeping sickness from the bites of those blood-sucking flies. That person has now reached the stage of insanity, and his blood is full of the germs and overloaded with atoxyl. "Everything had been tried and had failed. He was doomed. He saw his fortune menaced by the discovery of the way to make synthetic rubber. Life and money were at stake. One night, nerved up by a fit of insane fury, with a power far beyond what one would expect in his ordinary weakened condition, he saw a light in Cushing's laboratory. He stole in stealthily. He seized the inventor with his momentarily superhuman strength and choked him. As they struggled he must have shoved a sponge soaked with ether and orange essence under his nose. Cushing went under. "Resistance overcome by the anesthetic, he dragged the now insensible form to the work bench. Frantically he must have worked. He made an incision and exposed the radial artery, the pulse. Then he must have administered a local anesthetic to himself in his arm or leg. He secured a vein and pushed the cut end over this little canula. Then he fitted the artery of Cushing over that and the blood that was, perhaps, to save his life began flowing into his depleted veins. "Who was this madman? I have watched the actions of those whom I suspected when they did not know they were being watched. I did it by using this neat little device which looks like a field glass, but is really a camera that takes pictures of things at right angles to the direction in which the glass seems to be pointed. One person, I found, had a wound on his leg, the wrapping of which he adjusted nervously when he thought no one was looking. He had difficulty in limping even a short distance to open a window." Kennedy uncorked a bottle and the subtle odor of oranges mingled with ether stole through the room. "Some one here will recognize that odour immediately. It is the new orange-essence vapour anesthetic, a mixture of essence of orange with ether and chloroform. The odour hidden by the orange which lingered in the laboratory, Mr. Winslow and Mr. Strong, was not isoprene, but really ether. "I am letting some of the odour escape here because in this very laboratory it was that the thing took place, and it is one of the well-known principles of psychology that odours are powerfully suggestive. In this case the odour now must suggest the terrible scene of the other night to some one before me. More than that, I have to tell that person that the blood transfusion did not and could not save him. His illness is due to a condition that is incurable and cannot be altered by transfusion of new blood. That person is just as doomed to-day as he was before he committed--" A figure was groping blindly about. The arsenic compounds with which his blood was surcharged had brought on one of the attacks of blindness to which users of the drug are subject. In his insane frenzy he was evidently reaching desperately for Kennedy himself. As he groped he limped painfully from the soreness of his wound. "Dr. Harris," accused Kennedy, avoiding the mad rush at himself, and speaking in a tone that thrilled us, "you are the man who sucked the blood of Cushing into your own veins and left him to die. But the state will never be able to exact from you the penalty of your crime. Nature will do that too soon for justice. Gentlemen, this is the murderer of Bradley Cushing, a maniac, a modern scientific vampire." I regarded the broken, doomed man with mingled pity and loathing, rather than with the usual feelings one has toward a criminal. "Come," said Craig. "The local authorities can take care of this case now." He paused just long enough for a word of comfort to the poor, broken-hearted girl. Both Winslow answered with a mute look of gratitude and despair. In fact, in the confusion we were only too glad to escape any more such mournful congratulations. "Well," Craig remarked, as we walked quickly down the street, "if we have to wait here for a train, I prefer to wait in the railroad station. I have done my part. Now my only interest is to get away before they either offer me a banquet or lynch me." Actually, I think he would have preferred the novelty of dealing with a lynching party, if he had had to choose between the two. We caught a train soon, however, and fortunately it had a diner attached. Kennedy whiled away the time between courses by reading the graft exposures in the city. As we rolled into the station late in the afternoon, he tossed aside the paper with an air of relief. "Now for a quiet evening in the laboratory," he exclaimed, almost gleefully. By what stretch of imagination he could call that recreation, I could not see. But as for quietness, I needed it, too. I had fallen wofully behind in my record of the startling events through which he was conducting me. Consequently, until late that night I pecked away at my typewriter trying to get order out of the chaos of my hastily scribbled notes. Under ordinary circumstances, I remembered, the morrow would have been my day of rest on the Star. I had gone far enough with Kennedy to realise that on this assignment there was no such thing as rest. "District Attorney Carton wants to see me immediately at the Criminal Courts Building, Walter," announced Kennedy, early the following morning. Clothed, and as much in my right mind as possible after the arduous literary labours of the night before, I needed no urging, for Carton was an old friend of all the newspaper men. I joined Craig quickly in a hasty ride down-town in the rush hour. On the table before the square-jawed, close-cropped, fighting prosecutor, whom I knew already after many a long and hard-fought campaign both before and after election, lay a little package which had evidently come to him in the morning's mail by parcel-post. "What do you suppose is in that, Kennedy?" he asked, tapping it gingerly. "I haven't opened it yet, but I think it's a bomb. Wait--I'll have a pail of water sent in here so that you can open it, if you will. You understand such things." "No--no," hastened Kennedy, "that's exactly the wrong thing to do. Some of these modern chemical bombs are set off in precisely that way. No. Let me dissect the thing carefully. I think you may be right. It does look as if it might be an infernal machine. You see the evident disguise of the roughly written address?" Carton nodded, for it was that that had excited his suspicion in the first place. Meanwhile, Kennedy, without further ceremony, began carefully to remove the wrapper of brown Manila paper, preserving everything as he did so. Carton and I instinctively backed away. Inside, Craig had disclosed an oblong wooden box. "I realise that opening a bomb is dangerous business," he pursued slowly, engrossed in his work and almost oblivious to us, "but I think I can take a chance safely with this fellow. The dangerous part is what might be called drawing the fangs. No bombs are exactly safe toys to have around until they are wholly destroyed, and before you can say you have destroyed one, it is rather a ticklish business to take out the dangerous element." He had removed the cover in the deftest manner without friction, and seemingly without disturbing the contents in the least. I do not pretend to know how he did it; but the proof was that we could see him still working from our end of the room. On the inside of the cover was roughly drawn a skull and cross-bones, showing that the miscreant who sent the thing had at least a sort of grim humour. For, where the teeth should have been in the skull were innumerable match-heads. Kennedy picked them out with as much sang-froid as if he were not playing jackstraws with life and death. Then he removed the explosive itself and the various murderous slugs and bits of metal embedded in it, carefully separating each as if to be labelled "Exhibit A," "B," and so on for a class in bomb dissection. Finally, he studied the sides and bottom of the box. "Evidence of chlorate-of-potash mixture," Kennedy muttered to himself, still examining the bomb. "The inside was a veritable arsenal--a very unusual and clever construction." "My heavens!" breathed Carton. "I would rather go through a campaign again." XVII THE BOMB MAKER We stared at each other in blank awe, at the various parts, so innocent looking in the heaps on the table, now safely separated, but together a combination ticket to perdition. "Who do you suppose could have sent it?" I blurted out when I found my voice, then, suddenly recollecting the political and legal fight that Carton was engaged in at the time, I added, "The white slavers?" "Not a doubt," he returned laconically. "And," he exclaimed, bringing down both hands vigorously in characteristic emphasis on the arms of his office chair, "I've got to win this fight against the vice trust, as I call it, or the whole work of the district attorney's office in clearing up the city will be discredited--to say nothing of the risk the present incumbent runs at having such grateful friends about the city send marks of their affection and esteem like this." I knew something already of the situation, and Carton continued thoughtfully: "All the powers of vice are fighting a last-ditch battle against me now. I think I am on the trail of the man or men higher up in this commercialised-vice business--and it is a business, big business, too. You know, I suppose, that they seem to have a string of hotels in the city, of the worst character. There is nothing that they will stop at to protect themselves. Why, they are using gangs of thugs to terrorise any one who informs on them. The gunmen, of course, hate a snitch worse than poison. There have been bomb outrages, too--nearly a bomb a day lately--against some of those who look shaky and seem to be likely to do business with my office. But I'm getting closer all the time." "How do you mean?" asked Kennedy. "Well, one of the best witnesses, if I can break him down by pressure and promises, ought to be a man named Haddon, who is running a place in the Fifties, known as the Mayfair. Haddon knows all these people. I can get him in half an hour if you think it worth while--not here, but somewhere uptown, say at the Prince Henry." Kennedy nodded. We had heard of Haddon before, a notorious character in the white-light district. A moment later Carton had telephoned to the Mayfair and had found Haddon. "How did you get him so that he is even considering turning state's evidence?" asked Craig. "Well," answered Carton slowly, "I suppose it was partly through a cabaret singer and dancer, Loraine Keith, at the Mayfair. You know you never get the truth about things in the underworld except in pieces. As much as any one, I think we have been able to use her to weave a web about him. Besides, she seems to think that Haddon has treated her shamefully. According to her story, he seems to have been lavishing everything on her, but lately, for some reason, has deserted her. Still, even in her jealousy she does not accuse any other woman of winning him away." "Perhaps it is the opposite--another man winning her," suggested Craig dryly. "It's a peculiar situation," shrugged Carton. "There is another man. As nearly as I can make out there is a fellow named Brodie who does a dance with her. But he seems to annoy her, yet at the same time exercises a sort of fascination over her." "Then she is dancing at the Mayfair yet?" hastily asked Craig. "Yes. I told her to stay, not to excite suspicion." "And Haddon knows?" "Oh, no. But she has told us enough about him already so that we can worry him, apparently, just as what he can tell us would worry the others interested in the hotels. To tell the truth, I think she is a drug fiend. Why, my men tell me that they have seen her take just a sniff of something and change instantly--become a willing tool." "That's the way it happens," commented Kennedy. "Now, I'll go up there and meet Haddon," resumed Carton. "After I have been with him long enough to get into his confidence, suppose you two just happen along." Half an hour later Kennedy and I sauntered into the Prince Henry, where Carton had made the appointment in order to avoid suspicion that might arise if he were seen with Haddon at the Mayfair. The two men were waiting for us--Haddon, by contrast with Carton, a weak-faced, nervous man, with bulgy eyes. "Mr. Haddon," introduced Carton, "let me present a couple of reporters from the Star--off duty, so that we can talk freely before them, I can assure you. Good fellows, too, Haddon." The hotel and cabaret keeper smiled a sickly smile and greeted us with a covert, questioning glance. "This attack on Mr. Carton has unnerved me," he shivered. "If any one dares to do that to him, what will they do to me?" "Don't get cold feet, Haddon," urged Carton. "You'll be all right. I'll swing it for you." Haddon made no reply. At length he remarked: "You'll excuse me for a moment. I must telephone to my hotel." He entered a booth in the shadow of the back of the cafe, where there was a slot-machine pay-station. "I think Haddon has his suspicions," remarked Carton, "although he is too prudent to say anything yet." A moment later he returned. Something seemed to have happened. He looked less nervous. His face was brighter and his eyes clearer. What was it, I wondered? Could it be that he was playing a game with Carton and had given him a double cross? I was quite surprised at his next remark. "Carton," he said confidently, "I'll stick." "Good," exclaimed the district attorney, as they fell into a conversation in low tones. "By the way," drawled Kennedy, "I must telephone to the office in case they need me." He had risen and entered the same booth. Haddon and Carton were still talking earnestly. It was evident that, for some reason, Haddon had lost his former halting manner. Perhaps, I reasoned, the bomb episode had, after all, thrown a scare into him, and he felt that he needed protection against his own associates, who were quick to discover such dealings as Carton had forced him into. I rose and lounged back to the booth and Kennedy. "Whom did he call?" I whispered, when Craig emerged perspiring from the booth, for I knew that that was his purpose. Craig glanced at Haddon, who now seemed absorbed in talking to Carton. "No one," he answered quickly. "Central told me there had not been a call from this pay-station for half an hour." "No one?" I echoed almost incredulously. "Then what did he do? Something happened, all right." Kennedy was evidently engrossed in his own thoughts, for he said nothing. "Haddon says he wants to do some scouting about," announced Carton, when we rejoined them. "There are several people whom he says he might suspect. I've arranged to meet him this afternoon to get the first part of this story about the inside working of the vice trust, and he will let me know if anything develops then. You will be at your office?" "Yes, one or the other of us," returned Craig, in a tone which Haddon could not hear. In the meantime we took occasion to make some inquiries of our own about Haddon and Loraine Keith. They were evidently well known in the select circle in which they travelled. Haddon had many curious characteristics, chief of which to interest Kennedy was his speed mania. Time and again he had been arrested for exceeding the speed limit in taxicabs and in a car of his own, often in the past with Loraine Keith, but lately alone. It was toward the close of the afternoon that Carton called up hurriedly. As Kennedy hung up the receiver, I read on his face that something had gone wrong. "Haddon has disappeared," he announced, "mysteriously and suddenly, without leaving so much as a clue. It seems that he found in his office a package exactly like that which was sent to Carton earlier in the day. He didn't wait to say anything about it, but left. Carton is bringing it over here." Perhaps a quarter of an hour later, Carton himself deposited the package on the laboratory table with an air of relief. We looked eagerly. It was addressed to Haddon at the Mayfair in the same disguised handwriting and was done up in precisely the same fashion. "Lots of bombs are just scare bombs," observed Craig. "But you never can tell." Again Kennedy had started to dissect. "Ah," he went on, "this is the real thing, though, only a little different from the other. A dry battery gives a spark when the lid is slipped back. See, the explosive is in a steel pipe. Sliding the lid off is supposed to explode it. Why, there is enough explosive in this to have silenced a dozen Haddons." "Do you think he could have been kidnapped or murdered?" I asked. "What is this, anyhow--gang-war?" "Or perhaps bribed?" suggested Carton. "I can't say," ruminated Kennedy. "But I can say this: that there is at large in this city a man of great mechanical skill and practical knowledge of electricity and explosives. He is trying to make sure of hiding something from exposure. We must find him." "And especially Haddon," Carton added quickly. "He is the missing link. His testimony is absolutely essential to the case I am building up." "I think I shall want to observe Loraine Keith without being observed," planned Kennedy, with a hasty glance at his watch. "I think I'll drop around at this Mayfair I have heard so much about. Will you come?" "I'd better not," refused Carton. "You know they all know me, and everything quits wherever I go. I'll see you soon." As we drove in a cab over to the Mayfair, Kennedy said nothing. I wondered how and where Haddon had disappeared. Had the powers of evil in the city learned that he was weakening and hurried him out of the way at the last moment? Just what had Loraine Keith to do with it? Was she in any way responsible? I felt that there were, indeed, no bounds to what a jealous woman might dare. Beside the ornate grilled doorway of the carriage entrance of the Mayfair stood a gilt-and-black easel with the words, "Tango Tea at Four." Although it was considerably after that time, there was a line of taxi-cabs before the place and, inside, a brave array of late-afternoon and early-evening revellers. The public dancing had ceased, and a cabaret had taken its place. We entered and sat down at one of the more inconspicuous of the little round tables. On a stage, at one side, a girl was singing one of the latest syncopated airs. "We'll just stick around a while, Walter," whispered Craig. "Perhaps this Loraine Keith will come in." Behind us, protected both by the music and the rustle of people coming and going, a couple talked in low tones. Now and then a word floated over to me in a language which was English, sure enough, but not of a kind that I could understand. "Dropped by a flatty," I caught once, then something about a "mouthpiece," and the "bulls," and "making a plant." "A dip--pickpocket--and his girl, or gun-moll, as they call them," translated Kennedy. "One of their number has evidently been picked up by a detective and he looks to them for a good lawyer, or mouth-piece." Besides these two there were innumerable other interesting glimpses into the life of this meeting-place for the half-and underworlds. A motion in the audience attracted me, as if some favourite performer were about to appear, and I heard the "gun-moll" whisper, "Loraine Keith." There she was, a petite, dark-haired, snappy-eyed girl, chic, well groomed, and gowned so daringly that every woman in the audience envied and every man craned his neck to see her better. Loraine wore a tight-fitting black dress, slashed to the knee. In fact, everything was calculated to set her off at best advantage, and on the stage, at least, there was something recherche about her. Yet, there was also something gross about her, too. Accompanying her was a nervous-looking fellow whose washed-out face was particularly unattractive. It seemed as if the bone in his nose was going, due to the shrinkage of the blood-vessels. Once, just before the dance began, I saw him rub something on the back of his hand, raise it to his nose, and sniff. Then he took a sip of a liqueur. The dance began, wild from the first step, and as it developed, Kennedy leaned over and whispered, "The danse des Apaches." It was acrobatic. The man expressed brutish passion and jealousy; the woman, affection and fear. It seemed to tell a story--the struggle of love, the love of the woman against the brutal instincts of the thug, her lover. She was terrified as well as fascinated by him in his mad temper and tremendous superhuman strength. I wondered if the dance portrayed the fact. The music was a popular air with many rapid changes, but through all there was a constant rhythm which accorded well with the abandon of the swaying dance. Indeed, I could think of nothing so much as of Bill Sykes and Nancy as I watched these two. It was the fight of two frenzied young animals. He would approach stealthily, seize her, and whirl her about, lifting her to his shoulder. She was agile, docile, and fearful. He untied a scarf and passed it about her; she leaned against it, and they whirled giddily about. Suddenly, it seemed that he became jealous. She would run; he follow and catch her. She would try to pacify him; he would become more enraged. The dance became faster and more furious. His violent efforts seemed to be to throw her to the floor, and her streaming hair now made it seem more like a fight than a dance. The audience hung breathless. It ended with her dropping exhausted, a proper finale to this lowest and most brutal dance. Panting, flushed, with an unnatural light in their eyes, they descended to the audience and, scorning the roar of applause to repeat the performance, sat at a little table. I saw a couple of girls come over toward the man. "Give us a deck, Coke," said one, in a harsh voice. He nodded. A silver quarter gleamed momentarily from hand to hand, and he passed to one girl stealthily a small white-paper packet. Others came to him, both men and women. It seemed to be an established thing. "Who is that?" asked Kennedy, in a low tone, of the pickpocket back of us. "Coke Brodie," was the laconic reply. "A cocaine fiend?" "Yes, and a lobbygow for the grapevine system of selling the dope under this new law." "Where does he get the supply to sell?" asked Kennedy, casually. The pickpocket shrugged his shoulders. "No one knows, I suppose," Kennedy commented to me. "But he gets it in spite of the added restrictions and peddles it in little packets, adulterated, and at a fabulous price for such cheap stuff. The habit is spreading like wildfire. It is a fertile means of recruiting the inmates in the vice-trust hotels. A veritable epidemic it is, too. Cocaine is one of the most harmful of all habit-forming drugs. It used to be a habit of the underworld, but now it is creeping up, and gradually and surely reaching the higher strata of society. One thing that causes its spread is the ease with which it can be taken. It requires no smoking-dens, no syringe, no paraphernalia--only the drug itself." Another singer had taken the place of the dancers. Kennedy leaned over and whispered to the dip. "Say, do you and your gun-moll want to pick up a piece of change to get that mouthpiece I heard you talking about?" The pickpocket looked at Craig suspiciously. "Oh, don't worry; I'm all right," laughed Craig. "You see that fellow, Coke Brodie? I want to get something on him. If you will frame that sucker to get away with a whole front, there's a fifty in it." The dip looked, rather than spoke, his amazement. Apparently Kennedy satisfied his suspicions. "I'm on," he said quickly. "When he goes, I'll follow him. You keep behind us, and we'll deliver the goods." "What's it all about?" I whispered. "Why," he answered, "I want to get Brodie, only I don't want to figure in the thing so that he will know me or suspect anything but a plain hold-up. They will get him; take everything he has. There must be something on that man that will help us." Several performers had done their turns, and the supply of the drug seemed to have been exhausted. Brodie rose and, with a nod to Loraine, went out, unsteadily, now that the effect of the cocaine had worn off. One wondered how this shuffling person could ever have carried through the wild dance. It was not Brodie who danced. It was the drug. The dip slipped out after him, followed by the woman. We rose and followed also. Across the city Brodie slouched his way, with an evident purpose, it seemed, of replenishing his supply and continuing his round of peddling the stuff. He stopped under the brow of a thickly populated tenement row on the upper East Side, as though this was his destination. There he stood at the gate that led down to a cellar, looking up and down as if wondering whether he was observed. We had slunk into a doorway. A woman coming down the street, swinging a chatelaine, walked close to him, spoke, and for a moment they talked. "It's the gun-moll," remarked Kennedy. "She's getting Brodie off his guard. This must be the root of that grapevine system, as they call it." Suddenly from the shadow of the next house a stealthy figure sprang out on Brodie. It was our dip, a dip no longer but a regular stick-up man, with a gun jammed into the face of his victim and a broad hand over his mouth. Skilfully the woman went through Brodie's pockets, her nimble fingers missing not a thing. "Now--beat it," we heard the dip whisper hoarsely, "and if you raise a holler, we'll get you right, next time." Brodie fled as fast as his weakened nerves would permit his shaky limbs to move. As he disappeared, the dip sent something dark hurtling over the roof of the house across the street and hurried toward us. "What was that?" I asked. "I think it was the pistol on the end of a stout cord. That is a favourite trick of the gunmen after a job. It destroys at least a part of the evidence. You can't throw a gun very far alone, you know. But with it at the end of a string you can lift it up over the roof of a tenement. If Brodie squeals to a copper and these people are caught, they can't hold them under the pistol law, anyhow." The dip had caught sight of us, with his ferret eyes in the doorway. Quickly Kennedy passed over the money in return for the motley array of objects taken from Brodie. The dip and his gun-moll disappeared into the darkness as quickly as they had emerged. There was a curious assortment--the paraphernalia of a drug fiend, old letters, a key, and several other useless articles. The pickpocket had retained the money from the sale of the dope as his own particular honorarium. "Brodie has led us up to the source of his supply," remarked Kennedy, thoughtfully regarding the stuff. "And the dip has given us the key to it. Are you game to go in?" A glance up and down the street showed it still deserted. We wormed our way in the shadow to the cellar before which Brodie had stood. The outside door was open. We entered, and Craig stealthily struck a match, shading it in his hands. At one end we were confronted by a little door of mystery, barred with iron and held by an innocent enough looking padlock. It was this lock, evidently, to which the key fitted, opening the way into the subterranean vault of brick and stone. Kennedy opened it and pushed back the door. There was a little square compartment, dark as pitch and delightfully cool and damp. He lighted a match, then hastily blew it out and switched on an electric bulb which it disclosed. "Can't afford risks like that here," he exclaimed, carefully disposing of the match, as our eyes became accustomed to the light. On every side were pieces of gas-pipe, boxes, and paper, and on shelves were jars of various materials. There was a work-table littered with tools, pieces of wire, boxes, and scraps of metal. "My word!" exclaimed Kennedy, as he surveyed the curious scene before us, "this is a regular bomb factory--one of the most amazing exhibits that the history of crime has ever produced." XVIII THE "COKE" FIEND I followed him in awe as he made a hasty inventory of what we had discovered. There were as many as a dozen finished and partly finished infernal machines of various sizes and kinds, some of tremendous destructive capacity. Kennedy did not even attempt to study them. All about were high explosives, chemicals, dynamite. There was gunpowder of all varieties, antimony, blasting-powder, mercury cyanide, chloral hydrate, chlorate of potash, samples of various kinds of shot, some of the outlawed soft-nosed dumdum bullets, cartridges, shells, pieces of metal purposely left with jagged edges, platinum, aluminum, iron, steel--a conglomerate mass of stuff that would have gladdened an anarchist. Kennedy was examining a little quartz-lined electric furnace, which was evidently used for heating soldering irons and other tools. Everything had been done, it seemed, to prevent explosions. There were no open lights and practically no chance for heat to be communicated far among the explosives. Indeed, everything had been arranged to protect the operator himself in his diabolical work. Kennedy had switched on the electric furnace, and from the various pieces of metal on the table selected several. These he was placing together in a peculiar manner, and to them he attached some copper wire which lay in a corner in a roll. Under the work-table, beneath the furnace, one could feel the warmth of the thing slightly. Quickly he took the curious affair, which he had hastily shaped, and fastened it under the table at that point, then led the wires out through a little barred window to an air-shaft, the only means of ventilation of the place except the door. While he was working I had been gingerly inspecting the rest of the den. In a corner, just beside the door, I had found a set of shelves and a cabinet. On both were innumerable packets done up in white paper. I opened one and found it contained several pinches of a white, crystalline substance. "Little portions of cocaine," commented Kennedy, when I showed him what I had found. "In the slang of the fiends, 'decks.'" On the top of the cabinet he discovered a little enamelled box, much like a snuff-box, in which were also some of the white flakes. Quickly he emptied them out and replaced them with others from jars which had not been made up into packets. "Why, there must be hundreds of ounces of the stuff here, to say nothing of the various things they adulterate it with," remarked Kennedy. "No wonder they are so careful when it is a felony even to have it in your possession in such quantities. See how careful they are about the adulteration, too. You could never tell except from the effect whether it was the pure or only a few-per-cent.-pure article." Kennedy took a last look at the den, to make sure that nothing had been disturbed that would arouse suspicion. "We may as well go," he remarked. "To-morrow, I want to be free to make the connection outside with that wire in the shaft." Imagine our surprise, the next morning, when a tap at our door revealed Loraine Keith herself. "Is this Professor Kennedy?" she asked, gazing at us with a half-wild expression which she was making a tremendous effort to control. "Because if it is, I have something to tell him that may interest Mr. Carton." We looked at her curiously. Without her make-up she was pallid and yellow in spots, her hands trembling, cold, and sweaty, her eyes sunken and glistening, with pupils dilated, her breathing short and hurried, restless, irresolute, and careless of her personal appearance. "Perhaps you wonder how I heard of you and why I have come to you," she went on. "It is because I have a confession to make. I saw Mr. Haddon just before he was--kidnapped." She seemed to hesitate over the word. "How did you know I was interested?" asked Kennedy keenly. "I heard him mention your name with Mr. Carton's." "Then he knew that I was more than a reporter for the Star," remarked Kennedy. "Kidnapped, you say? How?" She shot a glance half of suspicion, half of frankness, at us. "That's what I must confess. Whoever did it must have used me as a tool. Mr. Haddon and I used to be good friends--I would be yet." There was evident feeling in her tone which she did not have to assume. "All I remember yesterday was that, after lunch, I was in the office of the Mayfair when he came in. On his desk was a package. I don't know what has become of it. But he gave one look at it, seemed to turn pale, then caught sight of me. 'Loraine,' he whispered, 'we used to be good friends. Forgive me for turning you down. But you don't understand. Get me away from here--come with me--call a cab.' "Well, I got into the cab with him. We had a chauffeur whom we used to have in the old days. We drove furiously, avoiding the traffic men. He told the driver to take us to my apartment--and--and that is the last I remember, except a scuffle in which I was dragged from the cab on one side and he on the other." She had opened her handbag and taken from it a little snuff-box, like that which we had seen in the den. "I--I can't go on," she apologised, "without this stuff." "So you are a cocaine fiend, also?" remarked Kennedy. "Yes, I can't help it. There is an indescribable excitement to do something great, to make a mark, that goes with it. It's soon gone, but while it lasts I can sing and dance, do anything until every part of my body begins crying for it again. I was full of the stuff when this happened yesterday; had taken too much, I guess." The change in her after she had snuffed some of the crystals was magical. From a quivering wretch she had become now a self-confident neurasthenic. "You know where that stuff will land you, I presume?" questioned Kennedy. "I don't care," she laughed hollowly. "Yes, I know what you are going to tell me. Soon I'll be hunting for the cocaine bug, as they call it, imagining that in my skin, under the flesh, are worms crawling, perhaps see them, see the little animals running around and biting me. Oh, you don't know. There are two souls to the cocainist. One is tortured by the suffering which the stuff brings; the other laughs at the fears and pains. But it brings such thoughts! It stimulates my mind, makes it work without, against my will, gives me such visions--oh, I can not go on. They would kill me if they knew I had come to you. Why have I? Has not Haddon cast me off? What is he to me, now?" It was evident that she was growing hysterical. I wondered whether, after all, the story of the kidnapping of Haddon might not be a figment of her brain, simply an hallucination due to the drug. "They?" inquired Kennedy, observing her narrowly. "Who?" "I can't tell. I don't know. Why did I come? Why did I come?" She was reaching again for the snuff-box, but Kennedy restrained her. "Miss Keith," he remarked, "you are concealing something from me. There is some one," he paused a moment, "whom you are shielding." "No, no," she cried. "He was taken. Brodie had nothing to do with it, nothing. That is what you mean. I know. This stuff increases my sensitiveness. Yet I hate Coke Brodie--oh--let me go. I am all unstrung. Let me see a doctor. To-night, when I am better, I will tell all." Loraine Keith had torn herself from him, had instantly taken a pinch of the fatal crystals, with that same ominous change from fear to self-confidence. What had been her purpose in coming at all? It had seemed at first to implicate Brodie, but she had been quick to shield him when she saw that danger. I wondered what the fascination might be which the wretch exercised over her. "To-night--I will see you to-night," she cried, and a moment later she was gone, as unexpectedly as she had come. I looked at Kennedy blankly. "What was the purpose of that outburst?" I asked. "I can't say," he replied. "It was all so incoherent that, from what I know of drug fiends, I am sure she had a deep-laid purpose in it all. It does not change my plans." Two hours later we had paid a deposit on an empty flat in the tenement-house in which the bomb-maker had his headquarters, and had received a key to the apartment from the janitor. After considerable difficulty, owing to the narrowness of the air-shaft, Kennedy managed to pick up the loose ends of the wire which had been led out of the little window at the base of the shaft, and had attached it to a couple of curious arrangements which he had brought with him. One looked like a large taximeter from a motor cab; the other was a diminutive gas-metre, in looks at least. Attached to them were several bells and lights. He had scarcely completed installing the thing, whatever it was, when a gentle tap at the door startled me. Kennedy nodded, and I opened it. It was Carton. "I have had my men watching the Mayfair," he announced. "There seems to be a general feeling of alarm there, now. They can't even find Loraine Keith. Brodie, apparently, has not shown up in his usual haunts since the episode of last night." "I wonder if the long arm of this vice trust could have reached out and gathered them in, too?" I asked. "Quite likely," replied Carton, absorbed in watching Kennedy. "What's this?" A little bell had tinkled sharply, and a light had flashed up on the attachments to the apparatus. "Nothing. I was just testing it to see if it works. It does, although the end which I installed down below was necessarily only a makeshift. It is not this red light with the shrill bell that we are interested in. It is the green light and the low-toned bell. This is a thermopile." "And what is a thermopile?"' queried Carton. "For the sake of one who has forgotten his physics," smiled Kennedy, "I may say this is only another illustration of how all science ultimately finds practical application. You probably have forgotten that when two half-rings of dissimilar metals are joined together and one is suddenly heated or chilled, there is produced at the opposite connecting point a feeble current which will flow until the junctures are both at the same temperature. You might call this a thermo-electric thermometer, or a telethermometer, or a microthermometer, or any of a dozen names." "Yes," I agreed mechanically, only vaguely guessing at what he had in mind. "The accurate measurement of temperature is still a problem of considerable difficulty," he resumed, adjusting the thermometer. "A heated mass can impart vibratory motion to the ether which fills space, and the wave-motions of ether are able to reproduce in other bodies motions similar to those by which they are caused. At this end of the line I merely measure the electromotive force developed by the difference in temperature of two similar thermo-electric junctions, opposed. We call those junctions in a thermopile 'couples,' and by getting the recording instruments sensitive enough, we can measure one one-thousandth of a degree. "Becquerel was the first, I believe, to use this property. But the machine which you see here was one recently invented for registering the temperature of sea water so as to detect the approach of an iceberg. I saw no reason why it should not be used to measure heat as well as cold. "You see, down there I placed the couples of the thermopile beneath the electric furnace on the table. Here I have the mechanism, operated by the feeble current from the thermopile, opening and closing switches, and actuating bells and lights. Then, too, I have the recording instrument. The thing is fundamentally very simple and is based on well-known phenomena. It is not uncertain and can be tested at any time, just as I did then, when I showed a slight fall in temperature. Of course it is not the slight changes I am after, not the gradual but the sudden changes in temperature." "I see," said Carton. "If there is a drop, the current goes one way and we see the red light; a rise and it goes the other, and we see a green light." "Exactly," agreed Kennedy. "No one is going to approach that chamber down-stairs as long as he thinks any one is watching, and we do not know where they are watching. But the moment any sudden great change is registered, such as turning on that electric furnace, we shall know it here." It must have been an hour that we sat there discussing the merits of the case and speculating on the strange actions of Loraine Keith. Suddenly the red light flashed out brilliantly. "What's that?" asked Carton quickly. "I can't tell, yet," remarked Kennedy. "Perhaps it is nothing at all. Perhaps it is a draught of cold air from opening the door. We shall have to wait and see." We bent over the little machine, straining our eyes and ears to catch the visual and audible signals which it gave. Gradually the light faded, as the thermopile adjusted itself to the change in temperature. Suddenly, without warning, a low-toned bell rang before us and a bright-green light flashed up. "That can have only one meaning," cried Craig excitedly. "Some one is down there in that inferno--perhaps the bomb-maker himself." The bell continued to ring and the light to glow, showing that whoever was there had actually started the electric furnace. What was he preparing to do? I felt that, even though we knew there was some one there, it did us little good. I, for one, had no relish for the job of bearding such a lion in his den. We looked at Kennedy, wondering what he would do next. From the package in which he had brought the two registering machines he quietly took another package, wrapped up, about eighteen inches long and apparently very heavy. As he did so he kept his attention fixed on the telethermometer. Was he going to wait until the bomb-maker had finished what he had come to accomplish? It was perhaps fifteen minutes after our first alarm that the signals began to weaken. "Does that mean that he has gone--escaped?" inquired Carton anxiously. "No. It means that his furnace is going at full power and that he has forgotten it. It is what I am waiting for. Come on." Seizing the package as he hurried from the room, Kennedy dashed out on the street and down the outside cellar stairs, followed by us. He paused at the thick door and listened. Apparently there was not a sound from the other side, except a whir of a motor and a roar which might have been from the furnace. Softly he tried the door. It was locked on the inside. Was the bomb-maker there still? He must be. Suppose he heard us. Would he hesitate a moment to send us all to perdition along with himself? How were we to get past that door? Really, the deathlike stillness on the other side was more mysterious than would have been the detonation of some of the criminal's explosive. Kennedy had evidently satisfied himself on one point. If we were to get into that chamber we must do it ourselves, and we must do it quickly. From the package which he carried he pulled out a stubby little cylinder, perhaps eighteen inches long, very heavy, with a short stump of a lever projecting from one side. Between the stonework of a chimney and the barred door he laid it horizontally, jamming in some pieces of wood to wedge it tighter. Then he began to pump on the handle vigorously. The almost impregnable door seemed slowly to bulge. Still there was no sign of life from within. Had the bomb-maker left before we arrived? "This is my scientific sledge-hammer," panted Kennedy, as he worked the little lever backward and forward more quickly--"a hydraulic ram. There is no swinging of axes or wielding of crowbars necessary in breaking down an obstruction like this, nowadays. Such things are obsolete. This little jimmy, if you want to call it that, has a power of ten tons. That ought to be enough." It seemed as if the door were slowly being crushed in before the irresistible ten-ton punch of the hydraulic ram. Kennedy stopped. Evidently he did not dare to crush the door in altogether. Quickly he released the ram and placed it vertically. Under the now-yawning door jamb he inserted a powerful claw of the ram and again he began to work the handle. A moment later the powerful door buckled, and Kennedy deftly swung it outward so that it fell with a crash on the cellar floor. As the noise reverberated, there came a sound of a muttered curse from the cavern. Some one was there. We pressed forward. On the floor, in the weird glare of the little furnace, lay a man and a woman, the light playing over their ghastly, set features. Kennedy knelt over the man, who was nearest the door. "Call a doctor, quick," he ordered, reaching over and feeling the pulse of the woman, who had half fallen out of her chair. "They will, be all right soon. They took what they thought was their usual adulterated cocaine--see, here is the box in which it was. Instead, I filled the box with the pure drug. They'll come around. Besides, Carton needs both of them in his fight." "Don't take any more," muttered the woman, half conscious. "There's something wrong with it, Haddon." I looked more closely at the face in the half-darkness. It was Haddon himself. "I knew he'd come back when the craving for the drug became intense enough," remarked Kennedy. Carton looked at Kennedy in amazement. Haddon was the last person in the world whom he had evidently expected to discover here. "How--what do you mean?" "The episode of the telephone booth gave me the first hint. That is the favourite stunt of the drug fiend--a few minutes alone, and he thinks no one is the wiser about his habit. Then, too, there was the story about his speed mania. That is a frequent failing of the cocainist. The drug, too, was killing his interest in Loraine Keith--that is the last stage. "Yet under its influence, just as with his lobbygow and lieutenant, Brodie, he found power and inspiration. With him it took the form of bombs to protect himself in his graft." "He can't--escape this time--Loraine. We'll leave it--at his house--you know--Carton--" We looked quickly at the work-table. On it was a gigantic bomb of clockwork over which Haddon had been working. The cocaine which was to have given him inspiration had, thanks to Kennedy, overcome him. Beside Loraine Keith were a suit-case and a Gladstone. She had evidently been stuffing the corners full of their favourite nepenthe, for, as Kennedy reached down and turned over the closely packed woman's finery and the few articles belonging to Haddon, innumerable packets from the cabinet dropped out. "Hulloa--what's this?" he exclaimed, as he came to a huge roll of bills and a mass of silver and gold coin. "Trying to double-cross us all the time. That was her clever game--to give him the hours he needed to gather what money he could save and make a clean getaway. Even cocaine doesn't destroy the interest of men and women in that," he concluded, turning over to Carton the wealth which Haddon had amassed as one of the meanest grafters of the city of graft. Here was a case which I could not help letting the Star have immediately. Notes or no notes, it was local news of the first order. Besides, anything that concerned Carton was of the highest political significance. It kept me late at the office and I overslept. Consequently I did not see much of Craig the next morning, especially as he told me he had nothing special, having turned down a case of a robbery of a safe, on the ground that the police were much better fitted to catch ordinary yeggmen than he was. During the day, therefore, I helped in directing the following up of the Haddon case for the Star. Then, suddenly, a new front page story crowded this one of the main headlines. With a sigh of relief, I glanced at the new thriller, found it had something to do with the Navy Department, and that it came from as far away as Washington. There was no reason now why others could not carry on the graft story, and I left, not unwillingly. My special work just now was keeping on the trail of Kennedy, and I was glad to go back to the apartment and wait for him. "I suppose you saw that despatch from Washington in this afternoon's papers?" he queried, as he came in, tossing a late edition of the Record down on my desk. Across the front page extended a huge black scare-head: "NAVY'S MOST VITAL SECRET STOLEN." "Yes," I shrugged, "but you can't get me much excited by what the rewrite men on the Record say." "Why?" he asked, going directly into his own room. "Well," I replied, glancing through the text of the story, "the actual facts are practically the same as in the other papers. Take this, for instance, 'On the night of the celebration of the anniversary of the battle of Manila there were stolen from the Navy Department plans which the Record learns exclusively represent the greatest naval secret in the world.' So much for that paragraph--written in the office. Then it goes on: "The whole secret-service machinery of the Government has been put in operation. No one has been able to extract from the authorities the exact secret which was stolen, but it is believed to be an invention which will revolutionise the structure and construction of the most modern monster battleships. Such knowledge, it is said, in the hands of experts might prove fatal in almost any fight in which our newer ships met others of about equal fighting power, as with it marksmen might direct a shot that would disable our ships. "It is the opinion of the experts that the theft was executed by a skilled draughtsman or other civilian employe. At any rate, the thief knew what to take and its value. There is, at least, one nation, it is asserted, which faces the problem of bringing its ships up to the standard of our own to which the plans would be very valuable. "The building had been thrown open to the public for the display of fireworks on the Monument grounds before it. The plans are said to have been on one of the draughting-tables, drawn upon linen to be made into blue-prints. They are known to have been on the tables when the draughting-room was locked for the night. "The room is on the third floor of the Department and has a balcony looking out on the Monument. Many officers and officials had their families and friends on the balcony to witness the celebration, though it is not known that any one was in the draughting-room itself. All were admitted to the building on passes. The plans were tacked to a draughting-board in the room, but when it was opened in the morning the linen sheet was gone, and so were the thumb-tacks. The plans could readily have been rolled into a small bundle and carried under a coat or wrap. "While the authorities are trying to minimise the actual loss, it is believed that this position is only an attempt to allay the great public concern." I paused. "Now then," I added, picking up one of the other papers I had brought up-town myself, "take the Express. It says that the plans were important, but would have been made public in a few months, anyhow. Here: "The theft--or mislaying, as the Department hopes it will prove to be--took place several days ago. Official confirmation of the report is lacking, but from trustworthy unofficial sources it is learned that only unimportant parts of plans are missing, presumably minor structural details of battle-ship construction, and other things of a really trivial character, such as copies of naval regulations, etc. "The attempt to make a sensational connection between the loss and a controversy which is now going on with a foreign government is greatly to be deplored and is emphatically asserted to be utterly baseless. It bears traces of the jingoism of those 'interests' which are urging naval increases. "There is usually very little about a battle-ship that is not known before her keel is laid, or even before the signing of the contracts. At any rate, when it is asserted that the plans represent the dernier cri in some form of war preparation, it is well to remember that a 'last cry' is last only until there is a later. Naval secrets are few, anyway, and as it takes some years to apply them, this loss cannot be of superlative value to any one. Still, there is, of course, a market for such information in spite of the progress toward disarmament, but the rule in this case will be the rule as in a horse trade, 'Caveat emptor.'" "So there you are," I concluded. "You pay your penny for a paper, and you take your choice." "And the Star," inquired Kennedy, coming to the door and adding with an aggravating grin, "the infallible?" "The Star," I replied, unruffled, "hits the point squarely when it says that whether the plans were of immediate importance or not, the real point is that if they could be stolen, really important things could be taken also. For instance, 'The thought of what the thief might have stolen has caused much more alarm than the knowledge of what he has succeeded in taking.' I think it is about time those people in Washington stopped the leak if--" The telephone rang insistently. "I think that's for me," exclaimed Craig, bounding out of his room and forgetting his quiz of me. "Hello--yes--is that you, Burke? At the Grand Central--half an hour--all right. I'm bringing Jameson. Good-bye." Kennedy jammed down the receiver on the hook. XIX THE SUBMARINE MYSTERY "The Star was not far from right, Walter," he added, seriously. "If the battleship plans could be stolen, other things could be--other things were. You remember Burke of the secret service? I'm going up to Lookout Hill on the Connecticut shore of the Sound with him to-night. The rewrite men on the Record didn't have the facts, but they had accurate imaginations. The most vital secret that any navy ever had, that would have enabled us in a couple of years to whip the navies of the world combined against us, has been stolen." "And that is?" I asked. "The practical working-out of the newest of sciences, the science of telautomatics." "Telautomatics?" I repeated. "Yes. There is something weird, fascinating about the very idea. I sit up here safely in this room, turning switches, pressing buttons, depressing levers. Ten miles away a vehicle, a ship, an aeroplane, a submarine obeys me. It may carry enough of the latest and most powerful explosive that modern science can invent, enough, if exploded, to rival the worst of earthquakes. Yet it obeys my will. It goes where I direct it. It explodes where I want it. And it wipes off the face of the earth anything which I want annihilated. "That's telautomatics, and that is what has been stolen from our navy and dimly sensed by you clever newspaper men, from whom even the secret service can't quite hide everything. The publication of the rumour alone that the government knows it has lost something has put the secret service in a hole. What might have been done quietly and in a few days has got to be done in the glare of the limelight and with the blare of a brass band--and it has got to be done right away, too. Come on, Walter. I've thrown together all we shall need for one night--and it doesn't include any pajamas, either." A few minutes later we met our friend Burke of the secret service at the new terminal. He had wired Kennedy earlier in the day saying that he would be in New York and would call him up. "The plans, as I told you in my message," began Burke, when we had seated ourselves in a compartment of the Pullman, "were those of Captain Shirley, covering the wireless-controlled submarine. The old captain is a thoroughbred, too. I've known him in Washington. Comes of an old New England, family with plenty of money but more brains. For years he has been working on this science of radio-telautomatics, has all kinds of patents, which he has dedicated to the United States, too. Of course the basic, pioneer patents are not his. His work has been in the practical application of them. And, Kennedy, there are some secrets about his latest work that he has not patented; he has given them outright to the Navy Department, because they are too valuable even to patent." Burke, who liked a good detective tale himself, seemed pleased at holding Kennedy spellbound. "For instance," he went on, "he has on the bay up here a submarine which can be made into a crewless dirigible. He calls it the Turtle, I believe, because that was the name of the first American submarine built by Dr. Bushnell during the Revolution, even before Fulton." "You have theories of your own on the case?" asked Craig. "Well, there are several possibilities. You know there are submarine companies in this country, bitter rivals. They might like to have those plans. Then, too, there are foreign governments." He paused. Though he said nothing, I felt that there was no doubt what he hinted at. At least one government occurred to me which would like the plans above all others. "Once some plans of a submarine were stolen, I recall," ruminated Kennedy. "But that theft, I am satisfied, was committed in behalf of a rival company." "But, Kennedy," exclaimed Burke, "it was bad enough when the plans were stolen. Now Captain Shirley wires me that some one must have tampered with his model. It doesn't work right. He even believes that his own life may be threatened. And there is scarcely a real clue," he added dejectedly. "Of course we are watching all the employes who had access to the draughting-room and tracing everybody who was in the building that night. I have a complete list of them. There are three or four who will bear watching. For instance, there is a young attache of one of the embassies, named Nordheim." "Nordheim!" I echoed, involuntarily. I had expected an Oriental name. "Yes, a German. I have been looking up his record, and I find that once he was connected in some way with the famous Titan Iron Works, at Kiel, Germany. We began watching him day before yesterday, but suddenly he disappeared. Then, there is a society woman in Washington, a Mrs. Bayard Brainard, who was at the Department that night. We have been trying to find her. To-day I got word that she was summering in the cottage colony across the bay from Lookout Hill. At any rate, I had to go up there to see the captain, and I thought I'd kill a whole flock of birds with one stone. The chief thought, too, that if you'd take the case with us you had best start on it up there. Next, you will no doubt want to go back to Washington with me." Lookout Hill was the name of the famous old estate of the Shirleys, on a point of land jutting out into Long Island Sound and with a neighbouring point enclosing a large, deep, safe harbour. On the highest ground of the estate, with a perfect view of both harbour and sound, stood a large stone house, the home of Captain Shirley, of the United States navy, retired. Captain Shirley, a man of sixty-two or three, bronzed and wiry, met us eagerly. "So this is Professor Kennedy; I'm glad to meet you, sir," he welcomed, clasping Craig's hand in both of his--a fine figure as he stood erect in the light of the portecochere. "What's the news from Washington, Burke? Any clues?" "I can hardly tell," replied the secret service man, with assumed cheerfulness. "By the way, you'll have to excuse me for a few minutes while I run back into town on a little errand. Meanwhile, Captain, will you explain to Professor Kennedy just how things are? Perhaps he'd better begin by seeing the Turtle herself." Burke had not waited longer than to take leave. "The Turtle," repeated the captain, leading the way into the house. "Well, I did call it that at first. But I prefer to call it the Z99. You know the first submarines, abroad at least, were sometimes called Al, A2, A3, and so on. They were of the diving, plunging type, that is, they submerged on an inclined keel, nose down, like the Hollands. Then came the B type, in which the hydroplane appeared; the C type, in which it was more prominent, and a D type, where submergence is on a perfectly even keel, somewhat like our Lakes. Well, this boat of mine is a last word--the Z99. Call it the Turtle, if you like." We were standing for a moment in a wide Colonial hall in which a fire was crackling in a huge brick fireplace, taking the chill off the night air. "Let me give you a demonstration, first," added the captain. "Perhaps Z99 will work--perhaps not." There was an air of disappointment about the old veteran as he spoke, uncertainly now, of what a short time ago he had known to be a certainty and one of the greatest it had ever been given the inventive mind of man to know. A slip of a girl entered from the library, saw us, paused, and was about to turn back. Silhouetted against the curtained door, there was health, animation, gracefulness, in every line of her wavy chestnut hair, her soft, sparkling brown eyes, her white dress and hat to match, which contrasted with the healthy glow of tan on her full neck and arms, and her dainty little white shoes, ready for anything from tennis to tango. "My daughter Gladys, Professor Kennedy and Mr. Jameson," introduced the captain. "We are going to try the Z99 again, Gladys." A moment later we four were walking to the edge of the cliff where Captain Shirley had a sort of workshop and signal-station. He lighted the gas, for Lookout Hill was only on the edge of the town and boasted gas, electricity, and all modern improvements, as well as the atmosphere of old New England. "The Z99 is moored just below us at my private dock," began the captain. "I have a shed down there where we usually keep her, but I expected you, and she is waiting, thoroughly overhauled. I have signalled to my men--fellows I can trust, too, who used to be with me in the navy--to cast her off. There--now we are ready." The captain turned a switch. Instantly a couple of hundred feet below us, on the dark and rippling water, a light broke forth. Another signal, and the light changed. It was moving. "The principle of the thing," said Captain Shirley, talking to us but watching the moving light intently, "briefly, is that I use the Hertzian waves to actuate relays on the Z99. That is, I send a child with a message, the grown man, through the relay, so to speak, does the work. So, you see, I can sit up here and send my little David out anywhere to strike down a huge Goliath. "I won't bore you, yet, with explanations of my radio-combinator, the telecommutator, the aerial coherer relay, and the rest of the technicalities of wireless control of dirigible, self-propelled vessels. They are well known, beginning with pioneers like Wilson and Gardner in England, Roberts in Australia, Wirth and Lirpa in Germany, Gabet in France, and Tesla, Edison, Sims, and the younger Hammond in our own country. "The one thing, you may not know, that has kept us back while wireless telegraphy has gone ahead so fast is that in wireless we have been able to discard coherers and relays and use detectors and microphones in their places. But in telautomatics we have to keep the coherer. That has been the barrier. The coherer until recently has been spasmodic, until we had Hammond's mercury steel-disc coherer and now my own. Why," he cried, "we are just on the threshold, now, of this great science which Tesla has named telautomatics--the electric arm that we can stretch out through space to do our work and fight our battles." It was not difficult to feel the enthusiasm of the captain over an invention of such momentous possibilities, especially as the Z99 was well out in the harbour now and we could see her flashing her red and green signal-lights back to us. "You see," the captain resumed, "I have twelve numbers here on the keys of this radio-combinator--forward, back, stop propeller motor, rudder right, rudder left, stop steering motor, light signals front, light signals rear, launch torpedoes, and so on. The idea is that of a delayed contact. The machinery is always ready, but it delays a few seconds until the right impulse is given, a purely mechanical problem. I take advantage of the delay to have the message repeated by a signal back to me. I can even change it, then. You can see for yourself that it really takes no experience to run the thing when all is going right. Gladys has done it frequently herself. All you have to do is to pay attention, and press the right key for the necessary change. It is when things go wrong that even an expert like myself--confound it--there's something wrong!" The Z99 had suddenly swerved. Captain Shirley's brow knitted. We gathered around closer, Gladys next to her father and leaning anxiously over the transmitting apparatus. "I wanted to turn her to port yet she goes to starboard, and signals starboard, too. There--now--she has stopped altogether. What do you think of that?" Gladys stroked the old seafarer's hand gently, as he sat silently at the table, peering with contracted brows out into the now brilliantly moonlit night. Shirley looked up at his daughter, and the lines on his face relaxed as though he would hide his disappointment from her eager eyes. "Confound that light! What's the matter with it?" he exclaimed, changing the subject, and glancing up at the gas-fixture. Kennedy had already been intently looking at the Welsbach burner overhead, which had been flickering incessantly. "That gas company!" added the Captain, shaking his head in disgust, and showing annoyance over a trivial thing to hide deep concern over a greater, as some men do. "I shall use the electricity altogether after this contract with the company expires. I suppose you literary men, Mr. Jameson, would call that the light that failed." There was a forced air about his attempt to be facetious that did not conceal, but rather accentuated, the undercurrent of feelings in him. "On the contrary," broke in Kennedy, "I shouldn't be surprised to find that it is the light that succeeded." "How do you mean?" "I wouldn't have said anything about it if you hadn't noticed it yourself. In fact, I may be wrong. It suggests something to me, but it will need a good deal of work to verify it, and then it may not be of any significance. Is that the way the Z99 has behaved always lately?" "Yes, but I know that she hasn't broken down of herself," Captain Shirley asserted. "It never did before, not since I perfected that new coherer. And now it always does, perhaps fifteen or twenty minutes after I start her out." Shirley was watching the lights as they serpentined their way to us across the nearly calm water of the bay, idly toying with the now useless combinator. "Wait here," he said, rising hurriedly. "I must send my motor-boat out there to pick her up and tow her in." He was gone down the flight of rustic steps on the face of the cliff before we could reply. "I wish father wouldn't take it to heart so," murmured Gladys. "Sometimes I fear that success or failure of this boat means life or death to him." "That is exactly why we are here," reassured Kennedy, turning earnestly to her, "to help him to settle this thing at once. This is a beautiful spot," he added, as we stood on the edge of the cliff and looked far out over the tossing waves of the sound. "What is on that other point?" asked Kennedy, turning again toward the harbour itself. "There is a large cottage colony there," she replied. "Of course many of the houses are still closed so early in the season, but it is a beautiful place in the summer. The hotel over there is open now, though." "You must have a lively time when the season is at its height," ventured Kennedy. "Do you know a cottager there, a Mrs. Brainard?" "Oh, yes, indeed. I have known her in Washington for some time." "No doubt the cottagers envy you your isolation here," remarked Kennedy, turning and surveying the beautifully kept grounds. "I should think it would be pleasant, too, to have an old Washington friend here." "It is. We often invite our friends over for lawn-parties and other little entertainments. Mrs. Brainard has just arrived and has only had time to return my first visit to her, but I expect we shall have some good times this summer." It was evident, at least, that Gladys was not concealing anything about her friend, whether there was any suspicion or not of her. We had gone into the house to await the return of Captain Shirley. Burke had just returned, his face betraying that he was bursting with news. "She's here, all right," he remarked in an undertone to Kennedy, "in the Stamford cottage--quite an outfit. French chauffeur, two Japanese servants, maids, and all." "The Stamford cottage?" repeated Gladys. "Why, that is where Mrs. Brainard lives." She gave a startled glance at Kennedy, as she suddenly seemed to realise that both he and the secret-service man had spoken about her friend. "Yes," said Burke, noting on the instant the perfect innocence of her concern. "What do you know about Mrs. Brainard? Who, where is, Mr. Brainard?" "Dead, I believe," Gladys hesitated. "Mrs. Brainard has been well known in Washington circles for years. Indeed, I invited her with us the night of the Manila display." "And Mr. Nordheim?" broke in Burke. "N-no," she hesitated. "He was there, but I don't know as whose guest." "Did he seem very friendly with. Mrs. Brainard?" pursued the detective. I thought I saw a shade of relief pass over her face as she answered, "Yes." I could only interpret it that perhaps Nordheim had been attentive to Gladys herself and that she had not welcomed his attentions. "I may as well tell you," she said, at length. "It is no secret in our set, and I suppose you would find it out soon, anyhow. It is said that he is engaged to Mrs. Brainard--that is all." "Engaged?" repeated Burke. "Then that would account for his being at the hotel here. At least, it would offer an excuse." Gladys was not slow to note the stress that Burke laid on the last word. "Oh, impossible," she began hurriedly, "impossible that he could have known anything about this other matter. Why, she told me he was to sail suddenly for Germany and came up here for a last visit before he went, and to arrange to come back on his return. Oh, he could know nothing--impossible." "Why impossible?" persisted Burke. "They have submarines in Germany, don't they? And rival companies, too." "Who have rival companies?" inquired a familiar voice. It was Captain Shirley, who had returned out of breath from his long climb up the steps from the shore. "The Germans. I was speaking of an attache named Nordheim." "Who is Nordheim?" inquired the captain. "You met him at the Naval building, that night, don't you remember?" replied Gladys. "Oh, yes, I believe I do--dimly. He was the man who seemed so devoted to Mrs. Brainard." "I think he is, too, father," she replied hastily. "He has been suddenly called to Berlin and planned to spend the last few days here, at the hotel, so as to be near her. She told me that he had been ordered back to Washington again before he sailed and had had to cut his visit short." "When did you first notice the interference with the Turtle?" asked Burke. "I received your message this morning." "Yesterday morning was the first," replied the captain. "He arrived the night before and did not leave until yesterday afternoon," remarked Burke. "And we arrived to-night," put in Craig quietly. "The interference is going on yet." "Then the Japs," I cut in, at last giving voice to the suspicion I had of the clever little Orientals. "They could not have stolen the plans," asserted Burke, shaking his head. "No, Nordheim and Mrs. Brainard were the only ones who could have got into the draughting room the night of the Manila celebration." "Burke," said Kennedy, rising, "I wish you would take me into town. There are a few messages I would like to send. You will excuse us, Captain, for a few hours? Good evening, Miss Shirley." As he bowed I heard Kennedy add to her: "Don't worry about your father. Everything will come out all right soon." Outside, in the car which Burke had hired, Craig added: "Not to town. That was an excuse not to alarm Miss Shirley too much over her friend. Take us over past the Stamford cottage, first." The Stamford cottage was on the beach, between the shore front and the road. It was not a new place but was built in the hideous style of some thirty years ago with all sorts of little turned and knobby ornaments. We paused down the road a bit, though not long enough to attract attention. There were lights on every floor of the cottage, although most of the neighbouring cottages were dark. "Well protected by lightning-rods," remarked Kennedy, as he looked the Stamford cottage over narrowly. "We might as well drive on. Keep an eye on the hotel, Burke. It may be that Nordheim intends to return, after all." "Assuming that he has left," returned the secret-service man. "But you said he had left," said Kennedy. "What do you mean?" "I hardly know myself," wearily remarked Burke, on whom the strain of the case, to which we were still fresh, had begun to tell. "I only know that I called up Washington after I heard he had been at the hotel, and no one at our headquarters knew that he had returned. They may have fallen down, but they were to watch both his rooms and the embassy." "H-m," mused Kennedy. "Why didn't you say that before?" "Why, I assumed that he had gone back, until you told me there was interference to-night, too. Now, until I can locate him definitely I'm all at sea--that's all." It was now getting late in the evening, but Kennedy had evidently no intention of returning yet to Lookout Hill. We paused at the hotel, which was in the centre of the cottage colony, and flanked by a hill that ran back of the colony diagonally and from which a view of both the hotel and the cottages could be obtained. Burke's inquiries developed the fact that Nordheim had left very hurriedly and in some agitation. "To tell you the truth," confided the clerk, with whom Burke had ingratiated himself, "I thought he acted like a man who was watched." Late as it was, Kennedy insisted on motoring to the railroad station and catching the last train to New York. As there seemed to be nothing that I could do at Lookout Hill, I accompanied him on the long and tedious ride, which brought us back to the city in the early hours of the morning. We stopped just long enough to run up to the laboratory and to secure a couple of little instruments which looked very much like small incandescent lamps in a box. Then, by the earliest train from New York, we returned to Lookout Hill, with only such sleep as Kennedy had predicted, snatched in the day coaches of the trains and during a brief wait in the station. A half-hour's freshening up with a dip in the biting cold water of the bay, breakfast with Captain Shirley and Miss Gladys, and a return to the excitement of the case, had to serve in place of rest. Burke disappeared, after a hasty conference with Kennedy, presumably to watch Mrs. Brainard, the hotel, and the Stamford cottage to see who went in and out. "I've had the Z99 brought out of its shed," remarked the captain, as we rose from the breakfast-table. "There was nothing wrong as far as I could discover last night or by a more careful inspection this morning. I'd like to have you take a look at her now, in the daylight." "I was about to suggest," remarked Kennedy, as we descended the steps to the shore, "that perhaps, first, it might be well to take a short run in her with the crew, just to make sure that there is nothing wrong with the machinery." "A good idea," agreed the captain. We came to the submarine, lying alongside the dock and looking like a huge cigar. The captain preceded us down the narrow hatchway, and I followed Craig. The deck was cleared, the hatch closed, and the vessel sealed. XX THE WIRELESS DETECTOR Remembering Jules Verne's enticing picture of life on the palatial Nautilus, I may as well admit that I was not prepared for a real submarine. My first impression, as I entered the hold, was that of discomfort and suffocation. I felt, too, that I was too close to too much whirring machinery. I gazed about curiously. On all sides were electrical devices and machines to operate the craft and the torpedoes. I thought, also, that the water outside was uncomfortably close; one could almost feel it. The Z99 was low roofed, damp, with an intricate system of rods, controls, engines, tanks, stop-cocks, compasses, gauges--more things than it seemed the human mind, to say nothing of wireless, could possibly attend to at once. "The policy of secrecy which governments keep in regard to submarines," remarked the captain, running his eye over everything at once, it seemed, "has led them to be looked upon as something mysterious. But whatever you may think of telautomatics, there is really no mystery about an ordinary submarine." I did not agree with our "Captain Nemo," as, the examination completed, he threw in a switch. The motor started. The Z99 hummed and trembled. The fumes of gasoline were almost suffocating at first, in spite of the prompt ventilation to clear them off. There was no escape from the smell. I had heard of "gasoline heart," but the odour only made me sick and dizzy. Like most novices, I suppose, I was suffering excruciating torture. Not so, Kennedy. He got used to it in no time; indeed, seemed to enjoy the very discomfort. I felt that there was only one thing necessary to add to it, and that was the odour of cooking. Cooking, by the way, on a submarine is uncertain and disagreeable. There was a little electric heater, I found, which might possibly have heated enough water for one cup of coffee at a time. In fact, space was economised to the utmost. Only the necessaries of life were there. Every inch that could be spared was given over to machinery. It was everywhere, compact, efficient--everything for running the boat under water, guiding it above and below, controlling its submersion, compressing air, firing torpedoes, and a thousand other things. It was wonderful as it was. But when one reflected that all could be done automatically, or rather telautomatically, it was simply astounding. "You see," observed Captain Shirley, "when she is working automatically neither the periscope nor the wireless-mast shows. The wireless impulses are carried down to her from an inconspicuous float which trails along the surface and carries a short aerial with a wire running down, like a mast, forming practically invisible antennae." As he was talking the boat was being "trimmed" by admitting water as ballast into the proper tanks. "The Z99," he went on, "is a submersible, not a diving, submarine. That is to say, the rudder guides it and changes the angle of the boat. But the hydroplanes pull it up and down, two pairs of them set fore and aft of the centre of gravity. They lift or lower the boat bodily on an even keel, not by plunging and diving. I will now set the hydroplanes at ten degrees down and the horizontal rudder two degrees up, and the boat will submerge to a depth of thirty feet and run constant at that depth." He had shut off the gasoline motor and started the storage-battery electric motor, which was used when running submerged. The great motors gave out a strange, humming sound. The crew conversed in low, constrained tones. There was a slightly perceptible jar, and the boat seemed to quiver just a bit from stem to stern. In front of Shirley was a gauge which showed the depth of submergence and a spirit-level which showed any inclination. "Submerged," he remarked, "is like running on the surface under dense-fog conditions." I did not agree with those who have said there is no difference running submerged or on the surface. Under way on the surface was one thing. But when we dived it was most unpleasant. I had been reassured at the start when I heard that there were ten compressed-air tanks under a pressure of two thousand pounds to the square inch. But only once before had I breathed compressed air and that was when one of our cases once took us down into the tunnels below the rivers of New York. It was not a new sensation, but at fifty feet depth I felt a little tingling all over my body, a pounding of the ear-drums, and just a trace of nausea. Kennedy smiled as I moved about. "Never mind, Walter," he said. "I know how you feel on a first trip. One minute you are choking from lack of oxygen, then in another part of the boat you are exhilarated by too much of it. Still," he winked, "don't forget that it is regulated." "Well," I returned, "all I can say is that if war is hell, a submarine is war." I had, however, been much interested in the things about me. Forward, the torpedo-discharge tubes and other apparatus about the little doors in the vessel's nose made it look somewhat like the shield used in boring a tunnel under compressed air. "Ordinary torpedo-boats use the regular automobile torpedo," remarked Captain Shirley, coming ubiquitously up behind me. "I improve on that. I can discharge the telautomobile torpedo, and guide it either from the boat, as we are now, or from the land station where we were last night, at will." There was something more than pride in his manner. He was deadly in earnest about his invention. We had come over to the periscope, the "eye" of the submarine when she is running just under the surface, but of no use that we were below. "Yes," he remarked, in answer to my half-spoken question, "that is the periscope. Usually there is one fixed to look ahead and another that is movable, in order to take in what is on the sides and in the rear. I have both of those. But, in addition, I have the universal periscope, the eye that sees all around, three hundred and sixty degrees--a very clever application of an annular prism with objectives, condenser, and two eyepieces of low and high power." A call from one of the crew took him into the stern to watch the operation of something, leaving me to myself, for Kennedy was roaming about on a still hunt for anything that might suggest itself. The safety devices, probably more than any other single thing, interested me, for I had read with peculiar fascination of the great disasters to the Lutin, the Pluviose, the Farfardet, the A8, the Foca, the Kambala, the Japanese No 6, the German U3, and others. Below us I knew there was a keel that could be dropped, lightening the boat considerably. Also, there was the submarine bell, immersed in a tank of water, with telephone receivers attached by which one could "listen in," for example, before rising, say, from sixty feet to twenty feet, and thus "hear" the hulls of other ships. The bell was struck by means of air pressure, and was the same as that used for submarine signalling on ships. Water, being dense, is an excellent conductor of sound. Even in the submarine itself, I could hear the muffled clang of the gong. Then there were buoys which could be released and would fly to the surface, carrying within them a telephone, a light, and a whistle. I knew also something of the explosion dangers on a submarine, both from the fuel oil used when running on the surface, and from the storage batteries used when running submerged. Once in a while a sailor would take from a jar a piece of litmus paper and expose it, showing only a slight discolouration due to carbon dioxide. That was the least of my troubles. For a few moments, also, the white mice in a cage interested me. White mice were carried because they dislike the odour of gasoline and give warning of any leakage by loud squeals. The fact was that there was so much of interest that, the first discomfort over, I was, like Kennedy, beginning really to enjoy the trip. I was startled suddenly to hear the motors stop. There was no more of that interminable buzzing. The Z99 responded promptly to the air pressure that was forcing the water out of the tanks. The gauge showed that we were gradually rising on an even keel. A man sprang up the narrow hatchway and opened the cover through which we could see a little patch of blue sky again. The gasoline motor was started, and we ran leisurely back to the dock. The trip was over--safely. As we landed I felt a sense of gladness to get away from that feeling of being cut off from the world. It was not fear of death or of the water, as nearly as I could analyse it, but merely that terrible sense of isolation from man and nature as we know it. A message from Burke was waiting for Kennedy at the wharf. He read it quickly, then handed it to Captain Shirley and myself. Have just received a telegram from Washington. Great excitement at the embassy. Cipher telegram has been despatched to the Titan Iron Works. One of my men in Washington reports a queer experience. He had been following one of the members of the embassy staff, who saw he was being shadowed, turned suddenly on the man, and exclaimed, "Why are you hounding us still?" What do you make of it? No trace yet of Nordheim BURKE. The lines in Craig's face deepened in thought as he folded the message and remarked abstractedly, "She works all right when you are aboard." Then he recalled himself. "Let us try her again without a crew." Five minutes later we had ascended to the aerial conning-tower, and all was in readiness to repeat the trial of the night before. Vicious and sly the Z99 looked in the daytime as she slipped off, under the unseen guidance of the wireless, with death hidden under her nose. Just as during the first trial we had witnessed, she began by fulfilling the highest expectations. Straight as an arrow she shot out of the harbour's mouth, half submerged, with her periscope sticking up and bearing the flag proudly flapping, leaving behind a wake of white foam. She turned and re-entered the harbour, obeying Captain Shirley's every whim, twisting in and out of the shipping much to the amazement of the old salts, who had never become used to the weird sight. She cut a figure eight, stopped, started again. Suddenly I could see by the look on Captain Shirley's face that something was wrong. Before either of us could speak, there was a spurt of water out in the harbour, a cloud of spray, and the Z99 sank in a mass of bubbles. She had heeled over and was resting on the mud and ooze of the harbour bottom. The water had closed over her, and she was gone. Instantly all the terrible details of the sinking of the Lutin and other submarines flashed over me. I fancied I could see on the Z99 the overturned accumulators. I imagined the stifling fumes, the struggle for breath in the suddenly darkened hull. Almost as if it had happened half an hour ago, I saw it. "Thank God for telautomatics," I murmured, as the thought swept over me of what we had escaped. "No one was aboard her, at least." Chlorine was escaping rapidly from the overturned storage batteries, for a grave danger lurks in the presence of sea water, in a submarine, in combination with any of the sulphuric acid. Salt water and sulphuric acid produce chlorine gas, and a pint of it inside a good-sized submarine would be sufficient to render unconscious the crew of a boat. I began to realise the risks we had run, which my confidence in Captain Shirley had minimised. I wondered whether hydrogen in dangerous quantities might not be given off, and with the short-circuiting of the batteries perhaps explode. Nothing more happened, however. All kinds of theories suggested themselves. Perhaps in some way the gasoline motor had been started while the boat was depressed, the "gas" had escaped, combined with air, and a spark had caused an explosion. There were so many possibilities that it staggered me. Captain Shirley sat stunned. Yet here was the one great question, Whence had come the impulse that had sent the famous Z99 to her fate? "Could it have been through something internal?" I asked. "Could a current from one of the batteries have influenced the receiving apparatus?" "No," replied the captain mechanically. "I have a secret method of protecting my receiving instruments from such impulses within the hull." Kennedy was sitting silently in the corner, oblivious to us up to this point. "But not to impulses from outside the hull," he broke in. Unobserved, he had been bending over one of the little instruments which had kept us up all night and bad cost a tedious trip to New York and back. "What's that?" I asked. "This? This is a little instrument known as the audion, a wireless electric-wave detector." "Outside the hull?" repeated Shirley, still dazed. "Yes," cried Kennedy excitedly. "I got my first clue from that flickering Welsbach mantle last night. Of course it flickered from the wireless we were using, but it kept on. You know in the gas-mantle there is matter in a most mobile and tenuous state, very sensitive to heat and sound vibrations. "Now, the audion, as you see, consists of two platinum wings, parallel to the plane of a bowed filament of an incandescent light in a vacuum. It was invented by Dr. Lee DeForest to detect wireless. When the light is turned on and the little tantalum filament glows, it is ready for business. "It can be used for all systems of wireless--singing spark, quenched spark, arc sets, telephone sets; in fact, it will detect a wireless wave from whatever source it is sent. It is so susceptible that a man with one attached to an ordinary steel-rod umbrella on a rainy night can pick up wireless messages that are being transmitted within some hundreds of miles radius." The audion buzzed. "There--see? Our wireless is not working. But with the audion you can see that some wireless is, and a fairly near and powerful source it is, too." Kennedy was absorbed in watching the audion. Suddenly he turned and faced us. He had evidently reached a conclusion. "Captain," he cried, "can you send a wireless message? Yes? Well, this is to Burke. He is over there back of the hotel on the hill with some of his men. He has one there who understands wireless, and to whom I have given another audion. Quick, before this other wireless cuts in on us again. I want others to get the message as well as Burke. Send this: 'Have your men watch the railroad station and every road to it. Surround the Stamford cottage. There is some wireless interference from that direction.'" As Shirley, with a half-insane light in his eyes, flashed the message mechanically through space, Craig rose and signalled to the house. Under the portecochere I saw a waiting automobile, which an instant later tore up the broken-stone path and whirled around almost on two wheels near the edge of the cliff. Glowing with health and excitement, Gladys Shirley was at the wheel herself. In spite of the tenseness of the situation, I could not help stopping to admire the change in the graceful, girlish figure of the night before, which was now all lithe energy and alertness in her eager devotion to carrying out the minutest detail of Kennedy's plan to aid her father. "Excellent, Miss Shirley," exclaimed Kennedy, "but when I asked Burke to have you keep a car in readiness, I had no idea you would drive it yourself." "I like it," she remonstrated, as he offered to take the wheel. "Please--please--let me drive. I shall go crazy if I'm not doing something. I saw the Z99 go down. What was it? Who--" "Captain," called Craig. "Quick--into the car. We must hurry. To the Stamford house, Miss Shirley. No one can get away from it before we arrive. It is surrounded." Everything was quiet, apparently, about the house as our wild ride around the edge of the harbour ended under the deft guidance of Gladys Shirley. Here and there, behind a hedge or tree, I could see a lurking secret-service man. Burke joined us from behind a barn next door. "Not a soul has gone in or out," he whispered. "There does not seem to be a sign of life there." Craig and Burke had by this time reached the broad veranda. They did not wait to ring the bell, but carried the door down literally off its hinges. We followed closely. A scream from the drawing-room brought us to a halt. It was Mrs. Brainard, tall, almost imperial in her loose morning gown, her dark eyes snapping fire at the sudden intrusion. I could not tell whether she had really noticed that the house was watched or was acting a part. "What does this mean?" she demanded. "What--Gladys--you--" "Florence--tell them--it isn't so--is it? You don't know a thing about those plans of father's that were--stolen--that night." "Where is Nordheim?" interjected Burke quickly, a little of his "third degree" training getting the upper hand. "Nordheim?" "Yes--you know. Tell me. Is he here?" "Here? Isn't it bad enough to hound him, without hounding me, too? Will you merciless detectives drive us all from, place to place with your brutal suspicions?" "Merciless?" inquired Burke, smiling with sarcasm. "Who has been hounding him?" "You know very well what I mean," she repeated, drawing herself up to her full height and patting Gladys's hand to reassure her. "Read that message on the table." Burke picked up a yellow telegram dated New York, two days before. It was as I feared when I left you. The secret service must have rummaged my baggage both here and at the hotel. They have taken some very valuable papers of mine. "Secret service--rummage baggage?" repeated Burke, himself now in perplexity. "That is news to me. We have rummaged no trunks or bags, least of all Nordheim's. In fact, we have never been able to find them at all." "Upstairs, Burke--the servants' quarters," interrupted Craig impatiently. "We are wasting time here." Mrs. Brainard offered no protest. I began to think that the whole thing was indeed a surprise to her, and that she had, in fact, been reading, instead of making a studied effort to appear surprised at our intrusion. Room after room was flung open without finding any one, until we reached the attic, which had been finished off into several rooms. One door was closed. Craig opened it cautiously. It was pitch dark in spite of the broad daylight outside. We entered gingerly. On the floor lay two dark piles of something. My foot touched one of them. I drew back in horror at the feeling. It was the body of a man. Kennedy struck a light, and as he bent over in its little circle of radiance, he disclosed a ghastly scene. "Hari-kiri!" he ejaculated. "They must have got my message to Burke and have seen that the house was surrounded." The two Japanese servants had committed suicide. "Wh-what does it all mean?" gasped Mrs. Brainard, who had followed us upstairs with Gladys. Burke's lip curled slightly and he was about to speak. "It means," hastened Kennedy, "that you have been double crossed, Mrs. Brainard. Nordheim stole those plans of Captain Shirley's submarine for his Titan Iron Works. Then the Japs stole them from his baggage at the hotel. He thought the secret service had them. The Japs waited here just long enough to try the plans against the Z99 herself--to destroy Captain Shirley's work by his own method of destruction. It was clever, clever. It would make his labours seem like a failure and would discourage others from keeping up the experiments. They had planned to steal a march on the world. Every time the Z99 was out they worked up here with their improvised wireless until they found the wave-length Shirley was using. It took fifteen or twenty minutes, but they managed, finally, to interfere so that they sent the submarine to the bottom of the harbour. Instead of being the criminal, Burke, Mrs. Brainard is the victim, the victim both of Nordheim and of her servants." Craig had thrown open a window and had dropped down on his knees before a little stove by which the room was heated. He was poking eagerly in a pile of charred paper and linen. "Shirley," he cried, "your secret is safe, even though the duplicate plans were stolen. There will be no more interference." The Captain seized Craig by both hands and wrung them like the handle of a pump. "Oh, thank you--thank you--thank you," cried Gladys, running up and almost dancing with joy at the change in her father. "I--I could almost--kiss you!" "I could let you," twinkled Craig, promptly, as she blushed deeply. "Thank you, too, Mrs. Brainard," he added, turning to acknowledge her congratulations also. "I am glad I have been able to be of service to you." "Won't you come back to the house for dinner?" urged the Captain. Kennedy looked at me and smiled. "Walter," he said, "this is no place for two old bachelors like us." Then turning, he added, "Many thanks, sir,--but, seriously, last night we slept principally in day coaches. Really I must turn the case over to Burke now and get back to the city to-night early." They insisted on accompanying us to the station, and there the congratulations were done all over again. "Why," exclaimed Kennedy, as we settled ourselves in the Pullman after waving a final good-bye, "I shall be afraid to go back to that town again. I--I almost did kiss her!" Then his face settled into its usual stern lines, although softened, I thought. I am sure that it was not the New England landscape, with its quaint stone fences, that he looked at out of the window, but the recollection of the bright dashing figure of Gladys Shirley. It was seldom that a girl made so forcible an impression on Kennedy, I know, for on our return he fairly dived into work, like the Z99 herself, and I did not see him all the next day until just before dinner time. Then he came in and spent half an hour restoring his acid-stained fingers to something like human semblance. He said nothing about his research work of the day, and I was just about to remark that a day had passed without its usual fresh alarum and excursion, when a tap on the door buzzer was followed by the entrance of our old friend Andrews, head of the Great Eastern Life Insurance Company's own detective service. "Kennedy," he began, "I have a startling case for you. Can you help me out with it?" As he sat down heavily, he pulled from his immense black wallet some scraps of paper and newspaper cuttings. "You recall, I suppose," he went on, unfolding the papers without waiting for an answer, "the recent death of young Montague Phelps, at Woodbine, just outside the city?" Kennedy nodded. The death of Phelps, about ten days before, had attracted nation-wide attention because of the heroic fight for life he had made against what the doctors admitted had puzzled them--a new and baffling manifestation of coma. They had laboured hard to keep him awake, but had not succeeded, and after several days of lying in a comatose state he had finally succumbed. It was one of those strange but rather frequent cases of long sleeps reported in the newspapers, although it was by no means one which might be classed as record-breaking. The interest in Phelps lay, a great deal, in the fact that the young man had married the popular dancer, Anginette Petrovska, a few months previously. His honeymoon trip around the world had suddenly been interrupted, while the couple were crossing Siberia, by the news of the failure of the Phelps banking-house in Wall Street and the practical wiping-out of his fortune. He had returned, only to fall a victim to a greater misfortune. "A few days before his death," continued Andrews, measuring his words carefully, "I, or rather the Great Eastern, which had been secretly investigating the case, received this letter. What do you think of it?" He spread out on the table a crumpled note in a palpably disguised handwriting: TO WHOM IT MAY CONCERN: You would do well to look Into the death of Montague Phelps, Jr. I accuse no one, assert nothing. But when a young man apparently in the best of health, drops off so mysteriously and even the physician in the case can give no very convincing information, that case warrants attention. I know what I know. AN OUTSIDER. XXI THE GHOULS "H-M," mused Kennedy, weighing the contents of the note carefully, "one of the family, I'll be bound--unless the whole thing is a hoax. By the way, who else is there in the immediate family?" "Only a brother, Dana Phelps, younger and somewhat inclined to wildness, I believe. At least, his father did not trust him with a large inheritance, but left most of his money in trust. But before we go any further, read that." Andrews pulled from the papers a newspaper cutting on which he had drawn a circle about the following item. As we read, he eyed us sharply. PHELPS TOMB DESECRATED Last night, John Shaughnessy, a night watchman employed by the town of Woodbine, while on his rounds, was attracted by noises as of a violent struggle near the back road in the Woodbine Cemetery, on the outskirts of the town. He had varied his regular rounds because of the recent depredations of motor-car yeggmen who had timed him in pulling off several jobs lately. As he hurried toward the large mausoleum of the Phelps family, he saw two figures slink away in opposite directions in the darkness. One of them, he asserts positively, seemed to be a woman in black, the other a man whom he could not see clearly. They readily eluded pursuit in the shadows, and a moment later he heard the whir of a high-powered car, apparently bearing them away. At the tomb there was every evidence of a struggle. Things had been thrown about; the casket had been broken open, but the body of Montague Phelps, Jr., which had been interred there about ten days ago, was not touched or mutilated. It was a shocking and extraordinary violation. Shaughnessy believes that some personal jewels may have been buried with Phelps and that the thieves were after them, that they fought over the loot, and in the midst of the fight were scared away. The vault is of peculiar construction, a costly tomb in which repose the bodies of the late Montague Phelps, Sr., of his wife, and now of his eldest son. The raid had evidently been carefully planned to coincide with a time when Shaughnessy would ordinarily have been on the other side of the town. The entrance to the tomb had been barred, but during the commotion the ghouls were surprised and managed to escape without accomplishing their object and leaving no trace. Mrs. Phelps, when informed of the vandalism, was shocked, and has been in a very nervous state since the tomb was forced open. The local authorities seem extremely anxious that every precaution should be taken to prevent a repetition of the ghoulish visit to the tomb, but as yet the Phelps family has taken no steps. "Are you aware of any scandal, any skeleton in the closet in the family?" asked Craig, looking up. "No--not yet," considered Andrews. "As soon as I heard of the vandalism, I began to wonder what could have happened in the Phelps tomb, as far as our company's interests were concerned. You see, that was yesterday. To-day this letter came along," he added, laying down a second very dirty and wrinkled note beside the first. It was quite patently written by a different person from the first; its purport was different, indeed quite the opposite of the other. "It was sent to Mrs. Phelps," explained Andrews, "and she gave it out herself to the police." Do not show this to the police. Unless you leave $5000 in gold in the old stump in the swamp across from the cemetery, you will have reason to regret it. If you respect the memory of the dead, do this, and do it quietly. BLACK HAND. "Well," I ejaculated, "that's cool. What threat would be used to back this demand on the Phelpses?" "Here's the situation," resumed Andrews, puffing violently on his inevitable cigar and toying with the letters and clippings. "We have already held up payment of the half-million dollars of insurance to the widow as long as we can consistently do so. But we must pay soon, scandal or not, unless we can get something more than mere conjecture." "You are already holding it up?" queried Craig. "Yes. You see, we investigate thoroughly every suspicious death. In most cases, no body is found. This case is different in that respect. There is a body, and it is the body of the insured, apparently. But a death like this, involving the least mystery, receives careful examination, especially if, as in this case, it has recently been covered by heavy policies. My work has often served to reverse the decision of doctors and coroners' juries. "An insurance detective, as you can readily appreciate, Kennedy, soon comes to recognise the characteristics in the crimes with which he deals. For example, writing of the insurance plotted for rarely precedes the conspiracy to defraud. That is, I know of few cases in which a policy originally taken out in good faith has subsequently become the means of a swindle. "In outright-murder cases, the assassin induces the victim to take out insurance in his favour. In suicide cases, the insured does so himself. Just after his return home, young Phelps, who carried fifty thousand dollars already, applied for and was granted one of the largest policies we have ever written--half a million." "Was it incontestible without the suicide clause?" asked Kennedy. "Yes," replied Andrews, "and suicide is the first and easiest theory. Why, you have no idea how common the crime of suicide for the sake of the life insurance is becoming. Nowadays, we insurance men almost believe that every one who contemplates ending his existence takes out a policy so as to make his life, which is useless to him, a benefit, at least, to some one--and a nightmare to the insurance detective." "I know," I cut in, for I recalled having been rather interested in the Phelps case at the time, "but I thought the doctors said finally that death was due to heart failure." "Doctor Forden who signed the papers said so," corrected Andrews. "Heart failure--what does that mean? As well say breath failure, or nerve failure. I'll tell you what kind of failure I think it was. It was money failure. Hard times and poor investments struck Phelps before he really knew how to handle his small fortune. It called him home and--pouf!--he is off--to leave to his family a cool half-million by his death. But did he do it himself or did some one else do it? That's the question." "What is your theory," inquired Kennedy absently, "assuming there is no scandal hidden in the life of Phelps before or after he married the Russian dancer?" "I don't know, Kennedy," confessed Andrews. "I have had so many theories and have changed them so rapidly that all I lay claim to believing, outside of the bald facts that I have stated, is that there must have been some poison. I rather sense it, feel that there is no doubt of it, in fact. That is why I have come to you. I want you to clear it up, one way or another. The company has no interest except in getting at the truth." "The body is really there?" asked Kennedy. "You saw it?" "It was there no later than this afternoon, and in an almost perfect state of preservation, too." Kennedy seemed to be looking at and through Andrews as if he would hypnotise the truth out of him. "Let me see," he said quickly. "It is not very late now. Can we visit the mausoleum to-night?" "Easily. My car is down-stairs. Woodbine is not far, and you'll find it a very attractive suburb, aside from this mystery." Andrews lost no time in getting us out to Woodbine, and on the fringe of the little town, one of the wealthiest around the city, he deposited us at the least likely place of all, the cemetery. A visit to a cemetery is none too enjoyable even on a bright day. In the early night it is positively uncanny. What was gruesome in the daylight became doubly so under the shroud of darkness. We made our way into the grounds through a gate, and I, at least, even with all the enlightenment of modern science, could not restrain a weird and creepy sensation. "Here is the Phelps tomb," directed Andrews, pausing beside a marble structure of Grecian lines and pulling out a duplicate key of a new lock which had been placed on the heavy door of grated iron. As we entered, it was with a shudder at the damp odour of decay. Kennedy had brought his little electric bull's-eye, and, as he flashed it about, we could see at a glance that the reports had not been exaggerated. Everything showed marks of a struggle. Some of the ornaments had been broken, and the coffin itself had been forced open. "I have had things kept just as we found them," explained Andrews. Kennedy peered into the broken coffin long and attentively. With a little effort I, too, followed the course of the circle of light. The body was, as Andrews had said, in an excellent, indeed a perfect, state of preservation. There were, strange to say, no marks of decay. "Strange, very strange," muttered Kennedy to himself. "Could it have been some medical students, body-snatchers?" I asked musingly. "Or was it simply a piece of vandalism? I wonder if there could have been any jewels buried with him, as Shaughnessy said? That would make the motive plain robbery." "There were no jewels," said Andrews, his mind not on the first part of my question, but watching Kennedy intently. Craig had dropped on his knees on the damp, mildewed floor, and bringing his bull's-eye close to the stones, was examining some spots here and there. "There could not have been any substitution?" I whispered, with, my mind still on the broken coffin. "That would cover up the evidence of a poisoning, you know." "No," replied Andrews positively, "although bodies can be obtained cheaply enough from a morgue, ostensibly for medical purposes. No, that is Phelps, all right." "Well, then," I persisted, "body-snatchers, medical students?" "Not likely, for the same reason," he rejected. We bent over closer to watch Kennedy. Apparently he had found a number of round, flat spots with little spatters beside them. He was carefully trying to scrape them up with as little of the surrounding mould as possible. Suddenly, without warning, there was a noise outside, as if a person were moving through the underbrush. It was fearsome in its suddenness. Was it human or wraith? Kennedy darted to the door in time to see a shadow glide silently away, lost in the darkness of the fine old willows. Some one had approached the mausoleum for a second time, not knowing we were there, and had escaped. Down the road we could hear the purr of an almost silent motor. "Somebody is trying to get in to conceal something here," muttered Kennedy, stifling his disappointment at not getting a closer view of the intruder. "Then it was not a suicide," I exclaimed. "It was a murder!" Craig shook his head sententiously. Evidently he not prepared yet to talk. With another look at the body in the broken casket he remarked: "To-morrow I want to call on Mrs. Phelps and Doctor Forden, and, if it is possible to find him, Dana Phelps. Meanwhile, Andrews, if you and Walter will stand guard here, there is an apparatus which I should like to get from my laboratory and set up here before it is too late." It was far past the witching hour of midnight, when graveyards proverbially yawn, before Craig returned in the car. Nothing had happened in the meantime except those usual eery noises that one may hear in the country at night anywhere. Our visitor of the early evening seemed to have been scared away for good. Inside the mausoleum, Kennedy set up a peculiar machine which he attached to the electric-light circuit in the street by a long wire which he ran loosely over the ground. Part of the apparatus consisted of an elongated box lined with lead, to which were several other attachments, the nature of which I did not understand, and a crank-handle. "What's that?" asked Andrews curiously, as Craig set up a screen between the apparatus and the body. "This is a calcium-tungsten screen," remarked Kennedy, adjusting now what I know to be a Crookes' tube on the other side of the body itself, so that the order was: the tube, the body, the screen, and the oblong box. Without a further word we continued to watch him. At last, the apparatus adjusted apparently to his satisfaction, he brought out a jar of thick white liquid and a bottle of powder. "Buttermilk and a couple of ounces of bismuth sub-carbonate," he remarked, as he mixed some in a glass, and with a pump forced it down the throat of the body, now lying so that the abdomen was almost flat against the screen. He turned a switch and the peculiar bluish effulgence, which always appears when a Crookes' tube is being used, burst forth, accompanied by the droning of his induction-coil and the welcome smell of ozone produced by the electrical discharge in the almost fetid air of the tomb. Meanwhile, he was gradually turning the handle of the crank attached to the oblong box. He seemed so engrossed in the delicateness of the operation that we did not question him, in fact did not move. For Andrews, at least, it was enough to know that he had succeeded in enlisting Kennedy's services. Well along toward morning it was before Kennedy had concluded his tests, whatever they were, and had packed away his paraphernalia. "I'm afraid it will take me two or three days to get at this evidence, even now," he remarked, impatient at even the limitations science put on his activity. We had started back for a quick run to the city and rest. "But, anyhow, it will give us a chance to do some investigating along other lines." Early the next day, in spite of the late session of the night before, Kennedy started me with him on a second visit to Woodbine. This time he was armed with a letter of introduction from Andrews to Mrs. Phelps. She proved to be a young woman of most extraordinary grace and beauty, with a superb carriage such as only years of closest training under the best dancers of the world could give. There was a peculiar velvety softness about her flesh and skin, a witching stoop to her shoulders that was decidedly continental, and in her deep, soulful eyes a half-wistful look that was most alluring. In fact, she was as attractive a widow as the best Fifth Avenue dealers in mourning goods could have produced. I knew that 'Ginette Phelps had been, both as dancer and wife, always the centre of a group of actors, artists, and men of letters as well as of the world and affairs. The Phelpses had lived well, although they were not extremely wealthy, as fortunes go. When the blow fell, I could well fancy that the loss of his money had been most serious to young Montague, who had showered everything as lavishly as he was able upon his captivating bride. Mrs. Phelps did not seem to be overjoyed at receiving us, yet made no open effort to refuse. "How long ago did the coma first show itself?" asked Kennedy, after our introductions were completed. "Was your husband a man of neurotic tendency, as far as you could judge?" "Oh, I couldn't say when it began," she answered, in a voice that was soft and musical and under perfect control. "The doctor would know that better. No, he was not neurotic, I think." "Did you ever see Mr. Phelps take any drugs--not habitually, but just before this sleep came on?" Kennedy was seeking his information in a manner and tone that would cause as little offence as possible "Oh, no," she hastened. "No, never--absolutely." "You called in Dr. Forden the last night?" "Yes, he had been Montague's physician many years ago, you know." "I see," remarked Kennedy, who was thrusting about aimlessly to get her off her guard. "By the way, you know there is a great deal of gossip about the almost perfect state of preservation of the body, Mrs. Phelps. I see it was not embalmed." She bit her lip and looked at Kennedy sharply. "Why, why do you and Mr. Andrews worry me? Can't you see Doctor Forden?" In her annoyance I fancied that there was a surprising lack of sorrow. She seemed preoccupied. I could not escape the feeling that she was putting some obstacle in our way, or that from the day of the discovery of the vandalism, some one had been making an effort to keep the real facts concealed. Was she shielding some one? It flashed over me that perhaps, after all, she had submitted to the blackmail and had buried the money at the appointed place. There seemed to be little use in pursuing the inquiry, so we excused ourselves, much, I thought, to her relief. We found Doctor Forden, who lived on the same street as the Phelpses several squares away, most fortunately at home. Forden was an extremely interesting man, as is, indeed, the rule with physicians. I could not but fancy, however, that his hearty assurance that he would be glad to talk freely on the case was somewhat forced. "You were sent for by Mrs. Phelps, that last night, I believe, while Phelps was still alive?" asked Kennedy. "Yes. During the day it had been impossible to arouse him, and that night, when Mrs. Phelps and the nurse found him sinking even deeper into the comatose state, I was summoned again. He was beyond hope then. I did everything I could, but he died a few moments after I arrived." "Did you try artificial respiration?" asked Kennedy. "N-no," replied Forden. "I telephoned here for my respirator, but by the time it arrived at the house it was too late. Nothing had been omitted while he was still struggling with the spark of life. When that went out what was the use?" "You were his personal physician?" "Yes." "Had you ever noticed that he took any drug?" Doctor Forden shot a quick glance at Kennedy. "Of course not. He was not a drug fiend." "I didn't mean that he was addicted to any drug. But had he taken anything lately, either of his own volition or with the advice or knowledge of any one else?" "Of course not." "There's another strange thing I wish to ask your opinion about," pursued Kennedy, not to be rebuffed. "I have seen his body. It is in an excellent state of preservation, almost lifelike. And yet I understand, or at least it seems, that it was not embalmed." "You'll have to ask the undertaker about that," answered the doctor brusquely. It was evident that he was getting more and more constrained in his answers. Kennedy did not seem to mind it, but to me it seemed that he must be hiding something. Was there some secret which medical ethics kept locked in his breast? Kennedy had risen and excused himself. The interviews had not resulted in much, I felt, yet Kennedy did not seem to care. Back in the city again, he buried himself in his laboratory for the rest of the day, most of the time in his dark room, where he was developing photographic plates or films, I did not know which. During the afternoon Andrews dropped in for a few moments to report that he had nothing to add to what had already developed. He was not much impressed by the interviews. "There's just one thing I want to speak about, though," he said at length, unburdening his mind. "That tomb and the swamp, too, ought to be watched. Last night showed me that there seems to be a regular nocturnal visitor and that we cannot depend on that town night watchman to scare him off. Yet if we watch up there, he will be warned and will lie low. How can we watch both places at once and yet remain hidden?" Kennedy nodded approval of the suggestion. "I'll fix that," he replied, anxious to return to his photographic labours. "Meet me, both of you, on the road from the station at Woodbine, just as it is getting dusk." Without another word he disappeared into the dark room. We met him that night as he had requested. He had come up to Woodbine in the baggage-car of the train with a powerful dog, for all the world like a huge, grey wolf. "Down, Schaef," he ordered, as the dog began to show an uncanny interest in me. "Let me introduce my new dog-detective," he chuckled. "She has a wonderful record as a police-dog." We were making our way now through the thickening shadows of the town to the outskirts. "She's a German sheep-dog, a Schaferhund," he explained. "For my part, it is the English bloodhound in the open country and the sheep-dog in the city and the suburbs." Schaef seemed to have many of the characteristics of the wild, prehistoric animal, among them the full, upright ears of the wild dog which are such a great help to it. She was a fine, alert, upstanding dog, hardy, fierce, and literally untiring, of a tawny light brown like a lioness, about the same size and somewhat of the type of the smooth-coated collie, broad of chest and with a full brush of tail. Untamed though she seemed, she was perfectly under Kennedy's control, and rendered him absolute and unreasoning obedience. At the cemetery we established a strict watch about the Phelps mausoleum and the swamp which lay across the road, not a difficult thing to do as far as concealment went, owing to the foliage. Still, for the same reason, it was hard to cover the whole ground. In the shadow of a thicket we waited. Now and then we could hear Schaef scouting about in the underbrush, crouching and hiding, watching and guarding. As the hours of waiting in the heavily laden night air wore on, I wondered whether our vigil in this weird place would be rewarded. The soughing of the night wind in the evergreens, mournful at best, was doubly so now. Hour after hour we waited patiently. At last there was a slight noise from the direction opposite the mausoleum and toward the swamp next to the cemetery. Kennedy reached out and drew us back into the shadow deeper. "Some one is prowling about, approaching the mausoleum on that side, I think," he whispered. Instantly there recurred to me the thought I had had earlier in the day that perhaps, after all, the five thousand dollars of hush money, for whatever purpose it might be extorted, had been buried in the swamp by Mrs. Phelps in her anxiety. Had that been what she was concealing? Perhaps the blackmailer had come to reconnoitre, and, if the money was there, to take it away. Schaef, who had been near us, was sniffing eagerly. From our hiding-place we could just see her. She had heard the sounds, too, even before we had, and for an instant stood with every muscle tense. Then, like an arrow, she darted into the underbrush. An instant later, the sharp crack of a revolver rang out. Schaef kept right on, never stopping a second, except, perhaps, for surprise. "Crack!" almost in her face came a second spit of fire in the darkness, and a bullet crashed through the leaves and buried itself in a tree with a ping. The intruder's marksmanship was poor, but the dog paid no attention to it. "One of the few animals that show no fear of gunfire," muttered Kennedy, in undisguised admiration. "G-R-R-R," we heard from the police-dog. "She has made a leap at the hand that holds the gun," cried Kennedy, now rising and moving rapidly in the same direction. "She has been taught that a man once badly bitten in the hand is nearly out of the fight." We followed, too. As we approached we were just in time to see Schaef running in and out between the legs of a man who had heard us approach and was hastily making tracks for the road. As he tripped, she lunged for his back. Kennedy blew shrilly on a police whistle. Reluctantly, Schaef let go. One could see that with all her canine instinct she wanted to "get" that man. Her jaws were open, as, with longing eyes, she stood over the prostrate form in the grass. The whistle was a signal, and she had been taught to obey unquestioningly. "Don't move until we get to you, or you are a dead man," shouted Kennedy, pulling an automatic as he ran. "Are you hurt?" There was no answer, but as we approached, the man moved, ever so little, through curiosity to see his pursuers. Schaef shot forward. Again the whistle sounded and she dropped back. We bent over to seize him as Kennedy secured the dog. "She's a devil," ground out the prone figure on the grass. "Dana Phelps!" exclaimed Andrews, as the man turned his face toward us. "What are you doing, mixed up in this?" Suddenly there was a movement in the rear, toward the mausoleum itself. We turned, but it was too late. Two dark figures slunk through the gloom, bearing something between them. Kennedy slipped the leash off Schaef and she shot out like a unchained bolt of lightning. There was the whir of a high-powered machine which must have sneaked up with the muffler on during the excitement. They had taken a desperate chance and had succeeded. They were gone! XXII THE X-RAY "MOVIES" Still holding Dana Phelps between us, we hurried toward the tomb and entered. While our attention had been diverted in the direction of the swamp, the body of Montague Phelps had been stolen. Dana Phelps was still deliberately brushing off his clothes. Had he been in league with them, executing a flank movement to divert our attention? Or had it all been pure chance? "Well?" demanded Andrews. "Well?" replied Dana. Kennedy said nothing, and I felt that, with our capture, the mystery seemed to have deepened rather than cleared. As Andrews and Phelps faced each other, I noticed that the latter was now and then endeavouring to cover his wrist, where the dog had torn his coat sleeve. "Are you hurt badly?" inquired Kennedy. Dana said nothing, but backed away. Kennedy advanced, insisting on looking at the wounds. As he looked he disclosed a semicircle of marks. "Not a dog bite," he whispered, turning to me and fumbling in his pocket. "Besides, those marks are a couple of days old. They have scabs on them." He had pulled out a pencil and a piece of paper, and, unknown to Phelps, was writing in the darkness. I leaned over. Near the point, in the tube through which the point for writing was, protruded a small accumulator and tiny electric lamp which threw a little disc of light, so small that it could be hidden by the hand, yet quite sufficient to guide Craig in moving the point of his pencil for the proper formation of whatever he was recording on the surface of the paper. "An electric-light pencil," he remarked laconically, in an undertone. "Who were the others?" demanded Andrews of Dana. There was a pause as though he were debating whether or not to answer at all. "I don't know," he said at length. "I wish I did." "You don't know?" queried Andrews, with incredulity. "No, I say I wish I did know. You and your dog interrupted me just as I was about to find out, too." We looked at each other in amazement. Andrews was frankly skeptical of the coolness of the young man. Kennedy said nothing for some moments. "I see you don't want to talk," he put in shortly. "Nothing to talk about," grunted Dana, in disgust. "Then why are you here?" "Nothing but conjecture. No facts, only suspicions," said Dana, half to himself. "You expect us to believe that?" insinuated Andrews. "I can't help what you believe. That is the fact." "And you were not with them?" "No." "You'll be within call, if we let you go now, any time that we want you?" interrupted Kennedy, much to the surprise of Andrews. "I shall stay in Woodbine as long as there is any hope of clearing up this case. If you want me, I suppose I shall have to stay anyhow, even if there is a clue somewhere else." "I'll take your word for it," offered Kennedy. "I'll give it." I must say that I rather liked the young chap, although I could make nothing out of him. As Dana Phelps disappeared down the road, Andrews turned to Kennedy. "What did you do that for?" he asked, half critically. "Because we can watch him, anyway," answered Craig, with a significant glance at the now empty casket. "Have him shadowed, Andrews. It may lead to something and it may not. But in any case don't let him get out of reach." "Here we are in a worse mystery than ever," grumbled Andrews. "We have caught a prisoner, but the body is gone, and we can't even show that he was an accomplice." "What were you writing?" I asked Craig, endeavouring to change the subject to one more promising. "Just copying the peculiar shape of those marks on Phelps' arm. Perhaps we can improve on the finger-print method of identification. Those were the marks of human teeth." He was glancing casually at his sketch as he displayed it to us. I wondered whether he really expected to obtain proof of the identity of at least one of the ghouls by the tooth-marks. "It shows eight teeth, one of them decayed," he remarked. "By the way, there's no use watching here any longer. I have some more work to do in the laboratory which will keep me another day. To-morrow night I shall be ready. Andrews, in the mean time I leave the shadowing of Dana to you, and with the help of Jameson I want you to arrange to have all those connected with the case at my laboratory to-morrow night without fail." Andrews and I had to do some clever scheming to bring pressure to bear on the various persons interested to insure their attendance, now that Craig was ready to act. Of course there was no difficulty in getting Dana Phelps. Andrews's shadows reported nothing in his actions of the following day that indicated anything. Mrs. Phelps came down to town by train and Doctor Forden motored in. Andrews even took the precaution to secure Shaughnessy and the trained nurse, Miss Tracy, who had been with Montague Phelps during his illness but had not contributed anything toward untangling the case. Andrews and myself completed the little audience. We found Kennedy heating a large mass of some composition such as dentists use in taking impressions of the teeth. "I shall be ready in a moment," he excused himself, still bending over his Bunsen flame. "By the way, Mr. Phelps, if you will permit me." He had detached a wad of the softened material. Phelps, taken by surprise, allowed him to make an impression of his teeth, almost before he realised what Kennedy was doing. The precedent set, so to speak, Kennedy approached Doctor Forden. He demurred, but finally consented. Mrs. Phelps followed, then the nurse, and even Shaughnessy. With a quick glance at each impression, Kennedy laid them aside to harden. "I am ready to begin," he remarked at length, turning to a peculiar looking instrument, something like three telescopes pointing at a centre in which was a series of glass prisms. "These five senses of ours are pretty dull detectives sometimes," Kennedy began. "But I find that when we are able to call in outside aid we usually find that there are no more mysteries." He placed something in a test-tube in line before one of the barrels of the telescopes, near a brilliant electric light. "What do you see, Walter?" he asked, indicating an eyepiece. I looked. "A series of lines," I replied. "What is it?" "That," he explained, "is a spectroscope, and those are the lines of the absorption spectrum. Each of those lines, by its presence, denotes a different substance. Now, on the pavement of the Phelps mausoleum I found, you will recall, some roundish spots. I have made a very diluted solution of them which is placed in this tube. "The applicability of the spectroscope to the differentiation of various substances is too well known to need explanation. Its value lies in the exact nature of the evidence furnished. Even the very dilute solution which I have been able to make of the material scraped from these spots gives characteristic absorption bands between the D and E lines, as they are called. Their wave-lengths are between 5774 and 5390. It is such a distinct absorption spectrum that it is possible to determine with certainty that the fluid actually contains a certain substance, even though the microscope might fail to give sure proof. Blood--human blood--that was what those stains were." He paused. "The spectra of the blood pigments," he added, "of the extremely minute quantities of blood and the decomposition products of hemoglobin in the blood are here infallibly shown, varying very distinctly with the chemical changes which the pigments may undergo." Whose blood was it? I asked myself. Was it of some one who had visited the tomb, who was surprised there or surprised some one else there? I was hardly ready for Kennedy's quick remark. "There were two kinds of blood there. One was contained in the spots on the floor all about the mausoleum. There are marks on the arm of Dana Phelps which he probably might say were made by the teeth of my police-dog, Schaef. They are human tooth-marks, however. He was bitten by some one in a struggle. It was his blood on the floor of the mausoleum. Whose were the teeth?" Kennedy fingered the now set impressions, then resumed: "Before I answer that question, what else does the spectroscope show? I found some spots near the coffin, which has been broken open by a heavy object. It had slipped and had injured the body of Montague Phelps. From the injury some drops had oozed. My spectroscope tells me that that, too, is blood. The blood and other muscular and nervous fluids of the body had remained in an aqueous condition instead of becoming pectous. That is a remarkable circumstance." It flashed over me what Kennedy had been driving at in his inquiry regarding embalming. If the poisons of the embalming fluid had not been injected, he had now clear proof regarding anything his spectroscope discovered. "I had expected to find a poison, perhaps an alkaloid," he continued slowly, as he outlined his discoveries by the use of one of the most fascinating branches of modern science, spectroscopy. "In cases of poisoning by these substances, the spectroscope often has obvious advantages over chemical methods, for minute amounts will produce a well-defined spectrum. The spectroscope 'spots' the substance, to use a police idiom, the moment the case is turned over to it. There was no poison there." He had raised his voice to emphasise the startling revelation. "Instead, I found an extraordinary amount of the substance and products of glycogen. The liver, where this substance is stored, is literally surcharged in the body of Phelps." He had started his moving-picture machine. "Here I have one of the latest developments in the moving-picture art," he resumed, "an X-ray moving picture, a feat which was until recently visionary, a science now in its infancy, bearing the formidable names of biorontgenography, or kinematoradiography." Kennedy was holding his little audience breathless as he proceeded. I fancied I could see Anginette Phelps give a little shudder at the prospect of looking into the very interior of a human body. But she was pale with the fascination of it. Neither Forden nor the nurse looked to the right or to the left. Dana Phelps was open-eyed with wonder. "In one X-ray photograph, or even in several," continued Kennedy, "it is difficult to discover slight motions. Not so in a moving picture. For instance, here I have a picture which will show you a living body in all its moving details." On the screen before us was projected a huge shadowgraph of a chest and abdomen. We could see the vertebrae of the spinal column, the ribs, and the various organs. "It is difficult to get a series of photographs directly from a fluorescent screen," Kennedy went on. "I overcome the difficulty by having lenses of sufficient rapidity to photograph even faint images on that screen. It is better than the so-called serial method, by which a number of separate X-ray pictures are taken and then pieced together and rephotographed to make the film. I can focus the X-rays first on the screen by means of a special quartz objective which I have devised. Then I take the pictures. "Here, you see, are the lungs in slow or rapid respiration. There is the rhythmically beating heart, distinctly pulsating in perfect outline. There is the liver, moving up and down with the diaphragm, the intestines, and the stomach. You can see the bones moving with the limbs, as well as the inner visceral life. All that is hidden to the eye by the flesh is now made visible in striking manner." Never have I seen an audience at the "movies" so thrilled as we were now, as Kennedy swayed our interest at his will. I had been dividing my attention between Kennedy and the extraordinary beauty of the famous Russian dancer. I forgot Anginette Phelps entirely. Kennedy placed another film in the holder. "You are now looking into the body of Montague Phelps," he announced suddenly. We leaned forward eagerly. Mrs. Phelps gave a half-suppressed gasp. What was the secret hidden in it? There was the stomach, a curved sack something like a bagpipe or a badly made boot, with a tiny canal at the toe connecting it with the small intestine. There were the heart and lungs. "I have rendered the stomach visible," resumed Kennedy, "made it 'metallic,' so to speak, by injecting a solution of bismuth in buttermilk, the usual method, by which it becomes more impervious to the X-rays and hence darker in the skiagraph. I took these pictures not at the rate of fourteen or so a second, like the others, but at intervals of a few seconds. I did that so that, when I run them off, I get a sort of compressed moving picture. What you see in a short space of time actually took much longer to occur. I could have either kind of picture, but I prefer the latter. "For, you will take notice that there is movement here--of the heart, of the lungs, of the stomach--faint, imperceptible under ordinary circumstances, but nevertheless, movement." He was pointing at the lungs. "A single peristaltic contraction takes place normally in a very few seconds. Here it takes minutes. And the stomach. Notice what the bismuth mixture shows. There is a very slow series of regular wave-contractions from the fundus to the pylorus. Ordinarily one wave takes ten seconds to traverse it; here it is so slow as almost to be unnoticed." What was the implication of his startling, almost gruesome, discovery? I saw it clearly, yet hung on his words, afraid to admit even to myself the logical interpretation of what I saw. "Reconstruct the case," continued Craig excitedly. "Mr. Phelps, always a bon vivant and now so situated by marriage that he must be so, comes back to America to find his personal fortune--gone. "What was left? He did as many have done. He took out a new large policy on his life. How was he to profit by it? Others have committed suicide, have died to win. Cases are common now where men have ended their lives under such circumstances by swallowing bichloride-of-mercury tablets, a favourite method, it seems, lately. "But Phelps did not want to die to win. Life was too sweet to him. He had another scheme." Kennedy dropped his voice. "One of the most fascinating problems in speculation as to the future of the race under the influence of science is that of suspended animation. The usual attitude is one of reserve or scepticism. There is no necessity for it. Records exist of cases where vital functions have been practically suspended, with no food and little air. Every day science is getting closer to the control of metabolism. In the trance the body functions are so slowed as to simulate death. You have heard of the Indian fakirs who bury themselves alive and are dug up days later? You have doubted it. But there is nothing improbable in it. "Experiments have been made with toads which have been imprisoned in porous rock where they could get the necessary air. They have lived for months in a stupor. In impervious rock they have died. Frozen fish can revive; bears and other animals hibernate. There are all gradations from ordinary sleep to the torpor of death. Science can slow down almost to a standstill the vital processes so that excretions disappear and respiration and heart-beat are almost nil. "What the Indian fakir does in a cataleptic condition may be duplicated. It is not incredible that they may possess some vegetable extract by which they perform their as yet unexplained feats of prolonged living burial. For, if an animal free from disease is subjected to the action of some chemical and physical agencies which have the property of reducing to the extreme limit the motor forces and nervous stimulus, the body of even a warm-blooded animal may be brought down to a condition so closely resembling death that the most careful examination may fail to detect any signs of life. The heart will continue working regularly at low tension, supplying muscles and other parts with sufficient blood to sustain molecular life, and the stomach would naturally react to artificial stimulus. At any time before decomposition of tissue has set in, the heart might be made to resume its work and life come back. "Phelps had travelled extensively. In Siberia he must undoubtedly have heard of the Buriats, a tribe of natives who hibernate, almost like the animals, during the winters, succumbing to a long sleep known as the 'leshka.' He must have heard of the experiments of Professor Bakhmetieff, who studied the Buriats and found that they subsisted on foods rich in glycogen, a substance in the liver which science has discovered makes possible life during suspended animation. He must have heard of 'anabiose,' as the famous Russian calls it, by which consciousness can be totally removed and respiration and digestion cease almost completely." "But--the body--is gone!" some one interrupted. I turned. It was Dana Phelps, now leaning forward in wide-eyed excitement. "Yes," exclaimed Craig. "Time was passing rapidly. The insurance had not been paid. He had expected to be revived and to disappear with Anginette Phelps long before this. Should the confederates of Phelps wait? They did not dare. To wait longer might be to sacrifice him, if indeed they had not taken a long chance already. Besides, you yourself had your suspicions and had written the insurance company hinting at murder." Dana nodded, involuntarily confessing. "You were watching them, as well as the insurance investigator, Mr. Andrews. It was an awful dilemma. What was to be done? He must be resuscitated at any risk. "Ah--an idea! Rifle the grave--that was the way to solve it. That would still leave it possible to collect the insurance, too. The blackmail letter about the five thousand dollars was only a blind, to lay on the mythical Black Hand the blame for the desecration. Brought into light, humidity, and warmth, the body would recover consciousness and the life-functions resume their normal state after the anabiotic coma into which Phelps had drugged himself. "But the very first night the supposed ghouls were discovered. Dana Phelps, already suspicious regarding the death of his brother, wondering at the lack of sentiment which Mrs. Phelps showed, since she felt that her husband was not really dead--Dana was there. His suspicions were confirmed, he thought. Montague had been, in reality, murdered, and his murderers were now making away with the evidence. He fought with the ghouls, yet apparently, in the darkness, he did not discover their identity. The struggle was bitter, but they were two to one. Dana was bitten by one of them. Here are the marks of teeth--teeth--of a woman." Anginette Phelps was sobbing convulsively. She had risen and was facing Doctor Forden with outstretched hands. "Tell them!" she cried wildly. Forden seemed to have maintained his composure only by a superhuman effort. "The--body is--at my office," he said, as we faced him with deathlike stillness. "Phelps had told us to get him within ten days. We did get him, finally. Gentlemen, you, who were seeking murderers, are, in effect, murderers. You kept us away two days too long. It was too late. We could not revive him. Phelps is really dead!" "The deuce!" exclaimed Andrews, "the policy is incontestible!" As he turned to us in disgust, his eyes fell on Anginette Phelps, sobered down by the terrible tragedy and nearly a physical wreck from real grief. "Still," he added hastily, "we'll pay without a protest." She did not even hear him. It seemed that the butterfly in her was crushed, as Dr. Forden and Miss Tracy gently led her away. They had all left, and the laboratory was again in its normal state of silence, except for the occasional step of Kennedy as he stowed away the apparatus he had used. "I must say that I was one of the most surprised in the room at the outcome of that case," I confessed at length. "I fully expected an arrest." He said nothing, but went on methodically restoring his apparatus to its proper place. "What a peculiar life you lead, Craig," I pursued reflectively. "One day it is a case that ends with such a bright spot in our lives as the recollection of the Shirleys; the next goes to the other extreme of gruesomeness and one can hardly think about it without a shudder. And then, through it all, you go with the high speed power of a racing motor." "That last case appealed to me, like many others," he ruminated, "just because it was so unusual, so gruesome, as you call it." He reached into the pocket of his coat, hung over the back of a chair. "Now, here's another most unusual case, apparently. It begins, really, at the other end, so to speak, with the conviction, begins at the very place where we detectives send a man as the last act of our little dramas." "What?" I gasped, "another case before even this one is fairly cleaned up? Craig--you are impossible. You get worse instead of better." "Read it," he said, simply. Kennedy handed me a letter in the angular hand affected by many women. It was dated at Sing Sing, or rather Ossining. Craig seemed to appreciate the surprise which my face must have betrayed at the curious combination of circumstances. "Nearly always there is the wife or mother of a condemned man who lives in the shadow of the prison," he remarked quietly, adding, "where she can look down at the grim walls, hoping and fearing." I said nothing, for the letter spoke for itself. I have read of your success as a scientific detective and hope that you will pardon me for writing to you, but it is a matter of life or death for one who is dearer to me than all the world. Perhaps you recall reading of the trial and conviction of my husband, Sanford Godwin, at East Point. The case did not attract much attention in New York papers, although he was defended by an able lawyer from the city. Since the trial, I have taken up my residence here in Ossining in order to be near him. As I write I can see the cold, grey walls of the state prison that holds all that is dear to me. Day after day, I have watched and waited, hoped against hope. The courts are so slow, and lawyers are so technical. There have been executions since I came here, too--and I shudder at them. Will this appeal be denied, also? My husband was accused of murdering by poison--hemlock, they alleged--his adoptive parent, the retired merchant, Parker Godwin, whose family name he took when he was a boy. After the death of the old man, a later will was discovered in which my husband's inheritance was reduced to a small annuity. The other heirs, the Elmores, asserted, and the state made out its case on the assumption, that the new will furnished a motive for killing old Mr. Godwin, and that only by accident had it been discovered. Sanford is innocent. He could not have done it. It is not in him to do such a thing. I am only a woman, but about some things I know more than all the lawyers and scientists, and I KNOW that he is innocent. I cannot write all. My heart is too full. Cannot you come and advise me? Even if you cannot take up the case to which I have devoted my life, tell me what to do. I am enclosing a check for expenses, all I can spare at present. Sincerely yours, NELLA GODWIN. "Are you going?" I asked, watching Kennedy as he tapped the check thoughtfully on the desk. "I can hardly resist an appeal like that," he replied, absently replacing the check in the envelope with the letter. XXIII THE DEATH HOUSE In the early forenoon, we were on our way by train "up the river" to Sing Sing, where, at the station, a line of old-fashioned cabs and red-faced cabbies greeted us, for the town itself is hilly. The house to which we had been directed was on the hill, and from its windows one could look down on the barracks-like pile of stone with the evil little black-barred slits of windows, below and perhaps a quarter of a mile away. There was no need to be told what it was. Its very atmosphere breathed the word "prison." Even the ugly clutter of tall-chimneyed workshops did not destroy it. Every stone, every grill, every glint of a sentry's rifle spelt "prison." Mrs. Godwin was a pale, slight little woman, in whose face shone an indomitable spirit, unconquered even by the slow torture of her lonely vigil. Except for such few hours that she had to engage in her simple household duties, with now and then a short walk in the country, she was always watching that bleak stone house of atonement. Yet, though her spirit was unconquered, it needed no physician to tell one that the dimming of the lights at the prison on the morning set for the execution would fill two graves instead of one. For she had come to know that this sudden dimming of the corridor lights, and then their almost as sudden flaring-up, had a terrible meaning, well known to the men inside. Hers was no less an agony than that of the men in the curtained cells, since she had learned that when the lights grow dim at dawn at Sing Sing, it means that the electric power has been borrowed for just that little while to send a body straining against the straps of the electric chair, snuffing out the life of a man. To-day she had evidently been watching in both directions, watching eagerly the carriages as they climbed the hill, as well as in the direction of the prison. "How can I ever thank you, Professor Kennedy," she greeted us at the door, keeping back with difficulty the tears that showed how much it meant to have any one interest himself in her husband's case. There was that gentleness about Mrs. Godwin that comes only to those who have suffered much. "It has been a long fight," she began, as we talked in her modest little sitting-room, into which the sun streamed brightly with no thought of the cold shadows in the grim building below. "Oh, and such a hard, heartbreaking fight! Often it seems as if we had exhausted every means at our disposal, and yet we shall never give up. Why cannot we make the world see our case as we see it? Everything seems to have conspired against us--and yet I cannot, I will not believe that the law and the science that have condemned him are the last words in law and science." "You said in your letter that the courts were so slow and the lawyers so--" "Yes, so cold, so technical. They do not seem to realise that a human life is at stake. With them it is almost like a game in which we are the pawns. And sometimes I fear, in spite of what the lawyers say, that without some new evidence, it--it will go hard with him." "You have not given up hope in the appeal?" asked Kennedy gently. "It is merely on technicalities of the law," she replied with quiet fortitude, "that is, as nearly as I can make out from the language of the papers. Our lawyer is Salo Kahn, of the big firm of criminal lawyers, Smith, Kahn." "Conine," mused Kennedy, half to himself. I could not tell whether he was thinking of what he repeated or of the little woman. "Yes, the active principle of hemlock," she went on. "That was what the experts discovered, they swore. In the pure state, I believe, it is more poisonous than anything except the cyanides. And it was absolutely scientific evidence. They repeated the tests in court. There was no doubt of it. But, oh, he did not do it. Some one else did it. He did not--he could not." Kennedy said nothing for a few minutes, but from his tone when he did speak it was evident that he was deeply touched. "Since our marriage we lived with old Mr. Godwin in the historic Godwin House at East Point," she resumed, as he renewed his questioning. "Sanford--that was my husband's real last name until he came as a boy to work for Mr. Godwin in the office of the factory and was adopted by his employer--Sanford and I kept house for him. "About a year ago he began to grow feeble and seldom went to the factory, which Sanford managed for him. One night Mr. Godwin was taken suddenly ill. I don't know how long he had been ill before we heard him groaning, but he died almost before we could summon a doctor. There was really nothing suspicious about it, but there had always been a great deal of jealousy of my husband in the town and especially among the few distant relatives of Mr. Godwin. What must have started as an idle, gossipy rumour developed into a serious charge that my husband had hastened his old guardian's death. "The original will--THE will, I call it--had been placed in the safe of the factory several years ago. But when the gossip in the town grew bitter, one day when we were out, some private detectives entered the house with a warrant--and they did actually find a will, another will about which we knew nothing, dated later than the first and hidden with some papers in the back of a closet, or sort of fire proof box, built into the wall of the library. The second will was identical with the first in language except that its terms were reversed and instead of being the residuary legatee, Sanford was given a comparatively small annuity, and the Elmores were made residuary legatees instead of annuitants." "And who are these Elmores?" asked Kennedy curiously. "There are three, two grandnephews and a grandniece, Bradford, Lambert, and their sister Miriam." "And they live--" "In East Point, also. Old Mr. Godwin was not very friendly with his sister, whose grandchildren they were. They were the only other heirs living, and although Sanford never had anything to do with it, I think they always imagined that he tried to prejudice the old man against them." "I shall want to see the Elmores, or at least some one who represents them, as well as the district attorney up there who conducted the case. But now that I am here, I wonder if it is possible that I could bring any influence to bear to see your husband?" Mrs. Godwin sighed. "Once a month," she replied, "I leave this window, walk to the prison, where the warden is very kind to me, and then I can see Sanford. Of course there are bars between us besides the regular screen. But I can have an hour's talk, and in those talks he has described to me exactly every detail of his life in the--the prison. We have even agreed on certain hours when we think of each other. In those hours I know almost what he is thinking." She paused to collect herself. "Perhaps there may be some way if I plead with the warden. Perhaps--you may be considered his counsel now--you may see him." A half hour later we sat in the big registry room of the prison and talked with the big-hearted, big-handed warden. Every argument that Kennedy could summon was brought to bear. He even talked over long distance with the lawyers in New York. At last the rules were relaxed and Kennedy was admitted on some technicality as counsel. Counsel can see the condemned as often as necessary. We were conducted down a flight of steps and past huge steel-barred doors, along corridors and through the regular prison until at last we were in what the prison officials called the section for the condemned. Every one else calls this secret heart of the grim place, the death house. It is made up of two rows of cells, some eighteen or twenty in all, a little more modern in construction than the twelve hundred archaic caverns that pass for cells in the main prison. At each end of the corridor sat a guard, armed, with eyes never off the rows of cells day or night. In the wall, on one side, was a door--the little green door--the door from the death house to the death chamber. While Kennedy was talking to the prisoner, a guard volunteered to show me the death chamber and the "chair." No other furniture was there in the little brick house of one room except this awful chair, of yellow oak with broad, leather straps. There it stood, the sole article in the brightly varnished room of about twenty-five feet square with walls of clean blue, this grim acolyte of modern scientific death. There were the wet electrodes that are fastened to the legs through slits in the trousers at the calves; above was the pipe-like fixture, like a gruesome helmet of leather that fits over the head, carrying the other electrode. Back of the condemned was the switch which lets loose a lethal store of energy, and back of that the prison morgue where the bodies are taken. I looked about. In the wall to the left toward the death house was also a door, on this side yellow. Somehow I could not get from my mind the fascination of that door--the threshold of the grave. Meanwhile Kennedy sat in the little cage and talked with the convicted man across the three-foot distance between cell and screen. I did not see him at that time, but Kennedy repeated afterward what passed, and it so impressed me that I will set it down as if I had been present. Sanford Godwin was a tall, ashen-faced man, in the prison pallor of whose face was written the determination of despair, a man in whose blue eyes was a queer, half-insane light of hope. One knew that if it had not been for the little woman at the window at the top of the hill, the hope would probably long ago have faded. But this man knew she was always there, thinking, watching, eagerly planning in aid of any new scheme in the long fight for freedom. "The alkaloid was present, that is certain," he told Kennedy. "My wife has told you that. It was scientifically proved. There is no use in attacking that." Later on he remarked: "Perhaps you think it strange that one in the very shadow of the death chair"--the word stuck in his throat--"can talk so impersonally of his own case. Sometimes I think it is not my case, but some one else's. And then--that door." He shuddered and turned away from it. On one side was life, such as it was; on the other, instant death. No wonder he pleaded with Kennedy. "Why, Walter," exclaimed Craig, as we walked back to the warden's office to telephone to town for a car to take us up to East Point, "whenever he looks out of that cage he sees it. He may close his eyes--and still see it. When he exercises, he sees it. Thinking by day and dreaming by night, it is always there. Think of the terrible hours that man must pass, knowing of the little woman eating her heart out. Is he really guilty? I must find out. If he is not, I never saw a greater tragedy than this slow, remorseless approach of death, in that daily, hourly shadow of the little green door." East Point was a queer old town on the upper Hudson, with a varying assortment of industries. Just outside, the old house of the Godwins stood on a bluff overlooking the majestic river. Kennedy had wanted to see it before any one suspected his mission, and a note from Mrs. Godwin to a friend had been sufficient. Carefully he went over the deserted and now half-wrecked house, for the authorities had spared nothing in their search for poison, even going over the garden and the lawns in the hope of finding some of the poisonous shrub, hemlock, which it was contended had been used to put an end to Mr. Godwin. As yet nothing had been done to put the house in order again and, as we walked about, we noticed a pile of old tins in the yard which had not been removed. Kennedy turned them over with his stick. Then he picked one up and examined it attentively. "H-m--a blown can," he remarked. "Blown?" I repeated. "Yes. When the contents of a tin begin to deteriorate they sometimes give off gases which press out the ends of the tin. You can see how these ends bulge." Our next visit was to the district attorney, a young man, Gordon Kilgore, who seemed not unwilling to discuss the case frankly. "I want to make arrangements for disinterring the body," explained Kennedy. "Would you fight such a move?" "Not at all, not at all," he answered brusquely. "Simply make the arrangements through Kahn. I shall interpose no objection. It is the strongest, most impregnable part of the case, the discovery of the poison. If you can break that down you will do more than any one else has dared to hope. But it can't be done. The proof was too strong. Of course it is none of my business, but I'd advise some other point of attack." I must confess to a feeling of disappointment when Kennedy announced after leaving Kilgore that, for the present, there was nothing more to be done at East Point until Kahn had made the arrangements for reopening the grave. We motored back to Ossining, and Kennedy tried to be reassuring to Mrs. Godwin. "By the way," he remarked, just before we left, "you used a good deal of canned goods at the Godwin house, didn't you?" "Yes, but not more than other people, I think," she said. "Do you recall using any that were--well, perhaps not exactly spoiled, but that had anything peculiar about them?" "I remember once we thought we found some cans that seemed to have been attacked by mice--at least they smelt so, though how mice could get through a tin can we couldn't see." "Mice?" queried Kennedy. "Had a mousey smell? That's interesting. Well, Mrs. Godwin, keep up a good heart. Depend on me. What you have told me to-day has made me more than interested in your case. I shall waste no time in letting you know when anything encouraging develops." Craig had never had much patience with red tape that barred the way to the truth, yet there were times when law and legal procedure had to be respected, no matter how much they hampered, and this was one of them. The next day the order was obtained permitting the opening again of the grave of old Mr. Godwin. The body was exhumed, and Kennedy set about his examination of what secrets it might hide. Meanwhile, it seemed to me that the suspense was terrible. Kennedy was moving slowly, I thought. Not even the courts themselves could have been more deliberate. Also, he was keeping much to himself. Still, for another whole day, there was the slow, inevitable approach of the thing that now, I, too, had come to dread--the handing down of the final decision on the appeal. Yet what could Craig do otherwise, I asked myself. I had become deeply interested in the case by this time and spent the time reading all the evidence, hundreds of pages of it. It was cold, hard, brutal, scientific fact, and as I read I felt that hope faded for the ashen-faced man and the pallid little woman. It seemed the last word in science. Was there any way of escape? Impatient as I was, I often wondered what must have been the suspense of those to whom the case meant everything. "How are the tests coming along?" I ventured one night, after Kahn had arranged for the uncovering of the grave. It was now two days since Kennedy had gone up to East Point to superintend the exhumation and had returned to the city with the materials which had caused him to keep later hours in the laboratory than I had ever known even the indefatigable Craig to spend on a stretch before. He shook his head doubtfully. "Walter," he admitted, "I'm afraid I have reached the limit on the line of investigation I had planned at the start." I looked at him in dismay. "What then?" I managed to gasp. "I am going up to East Point again to-morrow to look over that house and start a new line. You can go." No urging was needed, and the following day saw us again on the ground. The house, as I have said, had been almost torn to pieces in the search for the will and the poison evidence. As before, we went to it unannounced, and this time we had no difficulty in getting in. Kennedy, who had brought with him a large package, made his way directly to a sort of drawing-room next to the large library, in the closet of which the will had been discovered. He unwrapped the package and took from it a huge brace and bit, the bit a long, thin, murderous looking affair such as might have come from a burglar's kit. I regarded it much in that light. "What's the lay?" I asked, as he tapped over the walls to ascertain of just what they were composed. Without a word he was now down on his knees, drilling a hole in the plaster and lath. When he struck an obstruction he stopped, removed the bit, inserted another, and began again. "Are you going to put in a detectaphone?" I asked again. He shook his head. "A detectaphone wouldn't be of any use here," he replied. "No one is going to do any talking in that room." Again the brace and bit were at work. At last the wall had been penetrated, and he quickly removed every trace from the other side that would have attracted attention to a little hole in an obscure corner of the flowered wall-paper. Next, he drew out what looked like a long putty-blower, perhaps a foot long and three-eighths of an inch in diameter. "What's that?" I asked, as he rose after carefully inserting it. "Look through it," he replied simply, still at work on some other apparatus he had brought. I looked. In spite of the smallness of the opening at the other end, I was amazed to find that I could see nearly the whole room on the other side of the wall. "It's a detectascope," he explained, "a tube with a fish-eye lens which I had an expert optician make for me." "A fish-eye lens?" I repeated. "Yes. The focus may be altered in range so that any one in the room may be seen and recognised and any action of his may be detected. The original of this was devised by Gaillard Smith, the adapter of the detectaphone. The instrument is something like the cytoscope, which the doctors use to look into the human interior. Now, look through it again. Do you see the closet?" Again I looked. "Yes," I said, "but will one of us have to watch here all the time?" He had been working on a black box in the meantime, and now he began to set it up, adjusting it to the hole in the wall which he enlarged on our side. "No, that is my own improvement on it. You remember once we used a quick-shutter camera with an electric attachment, which moved the shutter on the contact of a person with an object in the room? Well, this camera has that quick shutter. But, in addition, I have adapted to the detectascope an invention by Professor Robert Wood, of Johns Hopkins. He has devised a fish-eye camera that 'sees' over a radius of one hundred and eighty degrees--not only straight in front, but over half a circle, every point in that room. "You know the refracting power of a drop of water. Since it is a globe, it refracts the light which reaches it from all directions. If it is placed like the lens of a camera, as Dr. Wood tried it, so that one-half of it catches the light, all the light caught will be refracted through it. Fishes, too, have a wide range of vision. Some have eyes that see over half a circle. So the lens gets its name. Ordinary cameras, because of the flatness of their lenses, have a range of only a few degrees, the widest in use, I believe, taking in only ninety-six, or a little more than a quarter of a circle. So, you see, my detectascope has a range almost twice as wide as that of any other." Though I did not know what he expected to discover and knew that it was useless to ask, the thing seemed very interesting. Craig did not pause, however, to enlarge on the new machine, but gathered up his tools and announced that our next step would be a visit to a lawyer whom the Elmores had retained as their personal counsel to look after their interests, now that the district attorney seemed to hare cleared up the criminal end of the case. Hollins was one of the prominent attorneys of East Point, and before the election of Kilgore as prosecutor had been his partner. Unlike Kilgore, we found him especially uncommunicative and inclined to resent our presence in the case as intruders. The interview did not seem to me to be productive of anything. In fact, it seemed as if Craig were giving Hollins much more than he was getting. "I shall be in town over night," remarked Craig. "In fact, I am thinking of going over the library up at the Godwin house soon, very carefully." He spoke casually. "There may be, you know, some finger-prints on the walls around that closet which might prove interesting." A quick look from Hollins was the only answer. In fact, it was seldom that he uttered more than a monosyllable as we talked over the various aspects of the case. A half-hour later, when he had left and had gone to the hotel, I asked Kennedy suspiciously, "Why did you expose your hand to Hollins, Craig?" He laughed. "Oh, Walter," he remonstrated, "don't you know that it is nearly always useless to look for finger-prints, except under some circumstances, even a few days afterward? This is months, not days. Why on iron and steel they last with tolerable certainty only a short time, and not much longer on silver, glass, or wood. But they are seldom permanent unless they are made with ink or blood or something that leaves a more or less indelible mark. That was a 'plant.'" "But what do you expect to gain by it?" "Well," he replied enigmatically, "no one is necessarily honest." It was late in the afternoon when Kennedy again visited the Godwin house and examined the camera. Without a word he pulled the detectascope from the wall and carried the whole thing to the developing-room of the local photographer. There he set to work on the film and I watched him in silence. He seemed very much excited as he watched the film develop, until at last he held it up, dripping, to the red light. "Some one has entered that room this afternoon and attempted to wipe off the walls and woodwork of that closet, as I expected," he exclaimed. "Who was it?" I asked, leaning over. Kennedy said nothing, but pointed to a figure on the film. I bent closer. It was the figure of a woman. "Miriam!" I exclaimed in surprise. XXIV THE FINAL DAY I looked aghast at him. If it had been either Bradford or Lambert, both of whom we had come to know since Kennedy had interested himself in the case, or even Hollins or Kilgore, I should not have been surprised. But Miriam! "How could she have any connection with the case?" I asked incredulously. Kennedy did not attempt to explain. "It is a fatal mistake, Walter, for a detective to assume that he knows what anybody would do in any given circumstances. The only safe course for him is to find out what the persons in question did do. People are always doing the unexpected. This is a case of it, as you see. I am merely trying to get back at facts. Come; I think we might as well not stay over night, after all. I should like to drop off on the way back to the city to see Mrs. Godwin." As we rode up the hill I was surprised to see that there was no one at the window, nor did any one seem to pay attention to our knocking at the door. Kennedy turned the knob quickly and strode in. Seated in a chair, as white as a wraith from the grave, was Mrs. Godwin, staring straight ahead, seeing nothing, hearing nothing. "What's the matter?" demanded Kennedy, leaping to her side and grasping her icy hand. The stare on her face seemed to change slightly as she recognised him. "Walter--some water--and a little brandy--if there is any. Tell me--what has happened?" From her lap a yellow telegram had fluttered to the floor, but before he could pick it up, she gasped, "The appeal--it has been denied." Kennedy picked up the paper. It was a message, unsigned, but not from Kahn, as its wording and in fact the circumstances plainly showed. "The execution is set for the week beginning the fifth," she continued, in the same hollow, mechanical voice. "My God--that's next Monday!" She had risen now and was pacing the room. "No! I'm not going to faint. I wish I could. I wish I could cry. I wish I could do something. Oh, those Elmores--they must have sent it. No one would have been so cruel but they." She stopped and gazed wildly out of the window at the prison. Neither of us knew what to say for the moment. "Many times from this window," she cried, "I have seen a man walk out of that prison gate. I always watch to see what he does, though I know it is no use. If he stands in the free air, stops short, and looks up suddenly, taking a long look at every house--I hope. But he always turns for a quick, backward look at the prison and goes half running down the hill. They always stop in that fashion, when the steel door opens outward. Yet I have always looked and hoped. But I can hope no more--no more. The last chance is gone." "No--not the last chance," exclaimed Craig, springing to her side lest she should fall. Then he added gently, "You must come with me to East Point--immediately." "What--leave him here--alone--in the last days? No--no--no. Never. I must see him. I wonder if they have told him yet." It was evident that she had lost faith in Kennedy, in everybody, now. "Mrs. Godwin," he urged. "Come--you must. It is a last chance." Eagerly he was pouring out the story of the discovery of the afternoon by the little detectascope. "Miriam?" she repeated, dazed. "She--know anything--it can't be. No--don't raise a false hope now." "It is the last chance," he urged again. "Come. There is not an hour to waste now." There was no delay, no deliberation about Kennedy now. He had been forced out into the open by the course of events, and he meant to take advantage of every precious moment. Down the hill our car sped to the town, with Mrs. Godwin still protesting, but hardly realising what was going on. Regardless of tolls, Kennedy called up his laboratory in New York and had two of his most careful students pack up the stuff which he described minutely to be carried to East Point immediately by train. Kahn, too, was at last found and summoned to meet us there also. Miles never seemed longer than they did to us as we tore over the country from Ossining to East Point, a silent party, yet keyed up by an excitement that none of us had ever felt before. Impatiently we awaited the arrival of the men from Kennedy's laboratory, while we made Mrs. Godwin as comfortable as possible in a room at the hotel. In one of the parlours Kennedy was improvising a laboratory as best he could. Meanwhile, Kahn had arrived, and together we were seeking those whose connection with, or interest in, the case made necessary their presence. It was well along toward midnight before the hasty conference had been gathered; besides Mrs. Godwin, Salo Kahn, and ourselves, the three Elmores, Kilgore, and Hollins. Strange though it was, the room seemed to me almost to have assumed the familiar look of the laboratory in New York. There was the same clutter of tubes and jars on the tables, but above all that same feeling of suspense in the air which I had come to associate with the clearing up of a case. There was something else in the air, too. It was a peculiar mousey smell, disagreeable, and one which made it a relief to have Kennedy begin in a low voice to tell why he had called us together so hastily. "I shall start," announced Kennedy, "at the point where the state left off--with the proof that Mr. Godwin died of conine, or hemlock poisoning. Conine, as every chemist knows, has a long and well-known history. It was the first alkaloid to be synthesised. Here is a sample, this colourless, oily fluid. No doubt you have noticed the mousey odour in this room. As little as one part of conine to fifty thousand of water gives off that odour--it is characteristic. "I have proceeded with extraordinary caution in my investigation of this case," he went on. "In fact, there would have been no value in it, otherwise, for the experts for the people seem to have established the presence of conine in the body with absolute certainty." He paused and we waited expectantly. "I have had the body exhumed and have repeated the tests. The alkaloid which I discovered had given precisely the same results as in their tests." My heart sank. What was he doing--convicting the man over again? "There is one other test which I tried," he continued, "but which I can not take time to duplicate tonight. It was testified at the trial that conine, the active principle of hemlock, is intensely poisonous. No chemical antidote is known. A fifth of a grain has serious results; a drop is fatal. An injection of a most minute quantity of real conine will kill a mouse, for instance, almost instantly. But the conine which I have isolated in the body is inert!" It came like a bombshell to the prosecution, so bewildering was the discovery. "Inert?" cried Kilgore and Hollins almost together. "It can't be. You are making sport of the best chemical experts that money could obtain. Inert? Read the evidence--read the books." "On the contrary," resumed Craig, ignoring the interruption, "all the reactions obtained by the experts have been duplicated by me. But, in addition, I tried this one test which they did not try. I repeat: the conine isolated in the body is inert." We were too perplexed to question him. "Alkaloids," he continued quietly, "as you know, have names that end in 'in' or 'ine'--morphine, strychnine, and so on. Now there are two kinds of alkaloids which are sometimes called vegetable and animal. Moreover, there is a large class of which we are learning much which are called the ptomaines--from ptoma, a corpse. Ptomaine poisoning, as every one knows, results when we eat food that has begun to decay. "Ptomaines are chemical compounds of an alkaloidal nature formed in protein substances during putrefaction. They are purely chemical bodies and differ from the toxins. There are also what are called leucomaines, formed in living tissues, and when not given off by the body they produce auto-intoxication. "There are more than three score ptomaines, and half of them are poisonous. In fact, illness due to eating infected foods is much more common than is generally supposed. Often there is only one case in a number of those eating the food, due merely to that person's inability to throw off the poison. Such cases are difficult to distinguish. They are usually supposed to be gastro-enteritis. Ptomaines, as their name shows, are found in dead bodies. They are found in all dead matter after a time, whether it is decayed food or a decaying corpse. "No general reaction is known by which the ptomaines can be distinguished from the vegetable alkaloids. But we know that animal alkaloids always develop either as a result of decay of food or of the decay of the body itself." At one stroke Kennedy had reopened the closed case and had placed the experts at sea. "I find that there is an animal conine as well as the true conine," he hammered out. "The truth of this matter is that the experts have confounded vegetable conine with cadaveric conine. That raises an interesting question. Assuming the presence of conine, where did it come from?" He paused and began a new line of attack. "As the use of canned goods becomes more and more extensive, ptomaine poisoning is more frequent. In canning, the cans are heated. They are composed of thin sheets of iron coated with tin, the seams pressed and soldered with a thin line of solder. They are filled with cooked food, sterilised, and closed. The bacteria are usually all killed, but now and then, the apparatus does not work, and they develop in the can. That results in a 'blown can'--the ends bulge a little bit. On opening, a gas escapes, the food has a bad odour and a bad taste. Sometimes people say that the tin and lead poison them; in practically all cases the poisoning is of bacterial, not metallic, origin. Mr. Godwin may have died of poisoning, probably did. But it was ptomaine poisoning. The blown cans which I have discovered would indicate that." I was following him closely, yet though this seemed to explain a part of the case, it was far from explaining all. "Then followed," he hurried on, "the development of the usual ptomaines in the body itself. These, I may say, had no relation to the cause of death itself. The putrefactive germs began their attack. Whatever there may have been in the body before, certainly they produced a cadaveric ptomaine conine. For many animal tissues and fluids, especially if somewhat decomposed, yield not infrequently compounds of an oily nature with a mousey odour, fuming with hydrochloric acid and in short, acting just like conine. There is ample evidence, I have found, that conine or a substance possessing most, if not all, of its properties is at times actually produced in animal tissues by decomposition. And the fact is, I believe, that a number of cases have arisen, in which the poisonous alkaloid was at first supposed to have been discovered which were really mistakes." The idea was startling in the extreme. Here was Kennedy, as it were, overturning what had been considered the last word in science as it had been laid down by the experts for the prosecution, opinions so impregnable that courts and juries had not hesitated to condemn a man to death. "There have been cases," Craig went on solemnly, "and I believe this to be one, where death has been pronounced to have been caused by wilful administration of a vegetable alkaloid, which toxicologists would now put down as ptomaine-poisoning cases. Innocent people have possibly already suffered and may in the future. But medical experts--" he laid especial stress on the word--"are much more alive to the danger of mistake than formerly. This was a case where the danger was not considered, either through carelessness, ignorance, or prejudice. "Indeed, ptomaines are present probably to a greater or less extent in every organ which is submitted to the toxicologist for examination. If he is ignorant of the nature of these substances, he may easily mistake them for vegetable alkaloids. He may report a given poison present when it is not present. It is even yet a new line of inquiry which has only recently been followed, and the information is still comparatively small and inadequate. "It is very difficult, perhaps impossible, for the chemist to state absolutely that he has detected true conine. Before he can do it, the symptoms and the post-mortem appearance must agree; analysis must be made before, not after, decomposition sets in, and the amount of the poison found must be sufficient to experiment with, not merely to react to a few usual tests. "What the experts asserted so positively, I would not dare to assert. Was he killed by ordinary ptomaine poisoning, and had conine, or rather its double, developed first in his food along with other ptomaines that were not inert? Or did the cadaveric conine develop only in the body after death? Chemistry alone can not decide the question so glibly as the experts did. Further proof must be sought Other sciences must come to our aid." I was sitting next to Mrs. Godwin. As Kennedy's words rang out, her hand, trembling with emotion, pressed my arm. I turned quickly to see if she needed assistance. Her face was radiant. All the fees for big cases in the world could never have compensated Kennedy for the mute, unrestrained gratitude which the little woman shot at him. Kennedy saw it, and in the quick shifting of his eyes to my face, I read that he relied on me to take care of Mrs. Godwin while he plunged again into the clearing up of the mystery. "I have here the will--the second one," he snapped out, turning and facing the others in the room. Craig turned a switch in an apparatus which his students had brought from New York. From a tube on the table came a peculiar bluish light. "This," he explained, "is a source of ultraviolet rays. They are not the bluish light which you see, but rays contained in it which you can not see. "Ultraviolet rays have recently been found very valuable in the examination of questioned documents. By the use of a lens made of quartz covered with a thin film of metallic silver, there has been developed a practical means of making photographs by the invisible rays of light above the spectrum--these ultraviolet rays. The quartz lens is necessary, because these rays will not pass through ordinary glass, while the silver film acts as a screen to cut off the ordinary light rays and those below the spectrum. By this means, most white objects are photographed black and even transparent objects like glass are black. "I obtained the copy of this will, but under the condition from the surrogate that absolutely nothing must be done to it to change a fibre of the paper or a line of a letter. It was a difficult condition. While there are chemicals which are frequently resorted to for testing the authenticity of disputed documents such as wills and deeds, their use frequently injures or destroys the paper under test. So far as I could determine, the document also defied the microscope. "But ultraviolet photography does not affect the document tested in any way, and it has lately been used practically in detecting forgeries. I have photographed the last page of the will with its signatures, and here it is. What the eye itself can not see, the invisible light reveals." He was holding the document and the copy, just an instant, as if considering how to announce with best effect what he had discovered. "In order to unravel this mystery," he resumed, looking up and facing the Elmores, Kilgore, and Hollins squarely, "I decided to find out whether any one had had access to that closet where the will was hidden. It was long ago, and there seemed to be little that I could do. I knew it was useless to look for fingerprints. "So I used what we detectives now call the law of suggestion. I questioned closely one who was in touch with all those who might have had such access. I hinted broadly at seeking fingerprints which might lead to the identity of one who had entered the house unknown to the Godwins, and placed a document where private detectives would subsequently find it under suspicious circumstances. "Naturally, it would seem to one who was guilty of such an act, or knew of it, that there might, after all, be finger-prints. I tried it. I found out through this little tube, the detectascope, that one really entered the room after that, and tried to wipe off any supposed finger-prints that might still remain. That settled it. The second will was a forgery, and the person who entered that room so stealthily this afternoon knows that it is a forgery." As Kennedy slapped down on the table the film from his camera, which had been concealed, Mrs. Godwin turned her now large and unnaturally bright eyes and met those of the other woman in the room. "Oh--oh--heaven help us--me, I mean!" cried Miriam, unable to bear the strain of the turn of events longer. "I knew there would be retribution--I knew--I knew--" Mrs. Godwin was on her feet in a moment. "Once my intuition was not wrong though all science and law was against me," she pleaded with Kennedy. There was a gentleness in her tone that fell like a soft rain on the surging passions of those who had wronged her so shamefully. "Professor Kennedy, Miriam could not have forged--" Kennedy smiled. "Science was not against you, Mrs. Godwin. Ignorance was against you. And your intuition does not go contrary to science this time, either." It was a splendid exhibition of fine feeling which Kennedy waited to have impressed on the Elmores, as though burning it into their minds. "Miriam Elmore knew that her brothers had forged a will and hidden it. To expose them was to convict them of a crime. She kept their secret, which was the secret of all three. She even tried to hide the finger-prints which would have branded her brothers. "For ptomaine poisoning had unexpectedly hastened the end of old Mr. Godwin. Then gossip and the 'scientists' did the rest. It was accidental, but Bradford and Lambert Elmore were willing to let events take their course and declare genuine the forgery which they had made so skilfully, even though it convicted an innocent man of murder and killed his faithful wife. As soon as the courts can be set in motion to correct an error of science by the truth of later science, Sing Sing will lose one prisoner from the death house and gain two forgers in his place." Mrs. Godwin stood before us, radiant. But as Kennedy's last words sank into her mind, her face clouded. "Must--must it be an eye for an eye and a tooth for a tooth?" she pleaded eagerly. "Must that grim prison take in others, even if my husband goes free?" Kennedy looked at her long and earnestly, as if to let the beauty of her character, trained by its long suffering, impress itself on his mind indelibly. He shook his head slowly. "I'm afraid there is no other way, Mrs. Godwin," he said gently taking her arm and leaving the others to be dealt with by a constable whom he had dozing in the hotel lobby. "Kahn is going up to Albany to get the pardon--there can be no doubt about it now," he added. "Mrs. Godwin, if you care to do so, you may stay here at the hotel, or you may go down with us on the midnight train as far as Ossining. I will wire ahead for a conveyance to meet you at the station. Mr. Jameson and I must go on to New York." "The nearer I am to Sanford now, the happier I shall be," she answered, bravely keeping back the tears of happiness. The ride down to New York, after our train left Ossining, was accomplished in a day coach in which our fellow passengers slept in every conceivable attitude of discomfort. Yet late, or rather early, as it was, we found plenty of life still in the great city that never sleeps. Tired, exhausted, I was at least glad to feel that finally we were at home. "Craig," I yawned, as I began to throw off my clothes, "I'm ready to sleep a week." There was no answer. I looked up at him almost resentfully. He had picked up the mail that lay under our letter slot and was going through it as eagerly as if the clock registered P.M. instead of A.M. "Let me see," I mumbled sleepily, checking over my notes, "how many days have we been at it?" I turned the pages slowly, after the manner in which my mind was working. "It was the twenty-sixth when you got that letter from Ossining," I calculated, "and to-day makes the thirtieth. My heavens--is there still another day of it? Is there no rest for the wicked?" Kennedy looked up and laughed. He was pointing at the calendar on the desk before him. "There are only thirty days in the month," he remarked slowly. "Thank the Lord," I exclaimed. "I'm all in!" He tipped his desk-chair back and bit the amber of his meerchaum contemplatively. "But to-day is the first," he drawled, turning the leaf on the calendar with just a flicker of a smile. THE END 
5087	----	THE TREASURE-TRAIN BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER CONTENTS CHAPTER I. THE TREASURE-TRAIN II. THE TRUTH-DETECTOR III. THE SOUL-ANALYSIS IV. THE MYSTIC POISONER V. THE PHANTOM DESTROYER VI. THE BEAUTY MASK VII. THE LOVE METER VIII. THE VITAL PRINCIPLE IX. THE RUBBER DAGGER X. THE SUBMARINE MINE XI. THE GUN-RUNNER XII. THE SUNKEN TREASURE I THE TREASURE-TRAIN "I am not by nature a spy, Professor Kennedy, but--well, sometimes one is forced into something like that." Maude Euston, who had sought out Craig in his laboratory, was a striking girl, not merely because she was pretty or because her gown was modish. Perhaps it was her sincerity and artlessness that made her attractive. She was the daughter of Barry Euston, president of the Continental Express Company, and one could readily see why, aside from the position her father held, she should be among the most-sought-after young women in the city. Miss Euston looked straight into Kennedy's eyes as she added, without waiting for him to ask a question: "Yesterday I heard something that has made me think a great deal. You know, we live at the St. Germaine when we are in town. I've noticed for several months past that the lobbies are full of strange, foreign-looking people. "Well, yesterday afternoon I was sitting alone in the tea-room of the hotel, waiting for some friends. On the other side of a huge palm I heard a couple whispering. I have seen the woman about the hotel often, though I know that she doesn't live there. The man I don't remember ever having seen before. They mentioned the name of Granville Barnes, treasurer of father's company--" "Is that so?" cut in Kennedy, quickly. "I read the story about him in the papers this morning." As for myself, I was instantly alive with interest, too. Granville Barnes had been suddenly stricken while riding in his car in the country, and the report had it that he was hovering between life and death in the General Hospital. The chauffeur had been stricken, too, by the same incomprehensible malady, though apparently not so badly. How the chauffeur managed to save the car was a miracle, but he brought it to a stop beside the road, where the two were found gasping, a quarter of an hour later, by a passing motorist, who rushed them to a doctor, who had them transferred to the hospital in the city. Neither of them seemed able or willing to throw any light on what had happened. "Just what was it you overheard?" encouraged Kennedy. "I heard the man tell the woman," Miss Euston replied, slowly, "that now was the chance--when any of the great warring powers would welcome and wink at any blow that might cripple the other to the slightest degree. I heard him say something about the Continental Express Company, and that was enough to make me listen, for, you know, father's company is handling the big shipments of gold and securities that are coming here from abroad by way of Halifax. Then I heard her mention the names of Mr. Barnes and of Mr. Lane, too, the general manager." She paused, as though not relishing the idea of having the names bandied about. "Last night the--the attack on him--for that is all that I can think it was--occurred." As she stopped again, I could not help thinking what a tale of strange plotting the casual conversation suggested. New York, I knew, was full of high-class international crooks and flimflammers who had flocked there because the great field of their operations in Europe was closed. The war had literally dumped them on us. Was some one using a band of these crooks for ulterior purposes? The idea opened up wide possibilities. "Of course," Miss Euston continued, "that is all I know; but I think I am justified in thinking that the two things--the shipment of gold here and the attack--have some connection. Oh, can't you take up the case and look into it?" She made her appeal so winsomely that it would have been difficult to resist even if it had not promised to prove important. "I should be glad to take up the matter," replied Craig, quickly, adding, "if Mr. Barnes will let me." "Oh, he must!" she cried. "I haven't spoken to father, but I know that he would approve of it. I know he thinks I haven't any head for business, just because I wasn't born a boy. I want to prove to him that I can protect the companies interests. And Mr. Barnes--why, of course he will approve." She said it with an assurance that made me wonder. It was only then that I recollected that it had been one of the excuses for printing her picture in the society columns of the Star so often that the pretty daughter of the president of the Continental was being ardently wooed by two of the company's younger officials. Granville Barnes himself was one. The other was Rodman Lane, the young general manager. I wished now that I had paid more attention to the society news. Perhaps I should have been in a better position to judge which of them it was whom she really had chosen. As it was, two questions presented themselves to me. Was it Barnes? And had Barnes really been the victim of an attack--or of an accident? Kennedy may have been thinking the problems over, but he gave no evidence of it. He threw on his hat and coat, and was ready in a moment to be driven in Miss Euston's car to the hospital. There, after the usual cutting of red tape which only Miss Euston could have accomplished, we were led by a white-uniformed nurse through the silent halls to the private room occupied by Barnes. "It's a most peculiar case," whispered the young doctor in charge, as we paused at the door. "I want you to notice his face and his cough. His pulse seems very weak, almost imperceptible at times. The stethoscope reveals subcrepitant sounds all over his lungs. It's like bronchitis or pneumonia--but it isn't either." We entered. Barnes was lying there almost in a state of unconsciousness. As we stood watching him he opened his eyes. But he did not see us. His vision seemed to be riveted on Miss Euston. He murmured something that we could not catch, and, as his eyes closed again, his face seemed to relax into a peaceful expression, as though he were dreaming of something happy. Suddenly, however, the old tense lines reappeared. Another idea seemed to have been suggested. "Is--Lane--hiring the men--himself?" he murmured. The sight of Maude Euston had prompted the thought of his rival, now with a clear field. What did it mean? Was he jealous of Lane, or did his words have a deeper meaning? What difference could it have made if Lane had a free hand in managing the shipment of treasure for the company? Kennedy looked long and carefully at the face of the sick man. It was blue and cyanosed still, and his lips had a violet tinge. Barnes had been coughing a great deal. Now and then his mouth was flecked with foamy blood, which the nurse wiped gently away. Kennedy picked up a piece of the blood-soaked gauze. A moment later we withdrew from the room as quietly as we had entered and tiptoed down the hall, Miss Euston and the young doctor following us more slowly. As we reached the door, I turned to see where she was. A distinguished-looking elderly gentleman, sitting in the waiting-room, had happened to glance up as she passed and had moved quickly to the hall. "What--you here, Maude?" we heard him say. "Yes, father. I thought I might be able to do something for Granville." She accompanied the remark with a sidelong glance and nod at us, which Kennedy interpreted to mean that we might as well keep in the background. Euston himself, far from chiding her, seemed rather to be pleased than otherwise. We could not hear all they said, but one sentence was wafted over. "It's most unfortunate, Maude, at just this time. It leaves the whole matter in the hands of Lane." At the mention of Lane, which her father accompanied by a keen glance, she flushed a little and bit her lip. I wondered whether it meant more than that, of the two suitors, her father obviously preferred Barnes. Euston had called to see Barnes, and, as the doctor led him up the hall again, Miss Euston rejoined us. "You need not drive us back," thanked Kennedy. "Just drop us at the Subway. I'll let you know the moment I have arrived at any conclusion." On the train we happened to run across a former classmate, Morehead, who had gone into the brokerage business. "Queer about that Barnes case, isn't it?" suggested Kennedy, after the usual greetings were over. Then, without suggesting that we were more than casually interested, "What does the Street think of it?" "It is queer," rejoined Morehead. "All the boys down-town are talking about it--wondering how it will affect the transit of the gold shipments. I don't know what would happen if there should be a hitch. But they ought to be able to run the thing through all right." "It's a pretty ticklish piece of business, then?" I suggested. "Well, you know the state of the market just now--a little push one way or the other means a lot. And I suppose you know that the insiders on the Street have boosted Continental Express up until it is practically one of the 'war stocks,' too. Well, good-by--here's my station." We had scarcely returned to the laboratory, however, when a car drove up furiously and a young man bustled in to see us. "You do not know me," he introduced, "but I am Rodman Lane, general manager of the Continental Express. You know our company has had charge of the big shipments of gold and securities to New York. I suppose you've read about what happened to Barnes, our treasurer. I don't know anything about it--haven't even time to find out. All I know is that it puts more work on me, and I'm nearly crazy already." I watched him narrowly. "We've had little trouble of any kind so far," he hurried on, "until just now I learned that all the roads over which we are likely to send the shipments have been finding many more broken rails than usual." Kennedy had been following him keenly. "I should like to see some samples of them," he observed. "You would?" said Lane, eagerly. "I've a couple of sections sawed from rails down at my office, where I asked the officials to send them." We made a hurried trip down to the express company's office. Kennedy examined the sections of rails minutely with a strong pocket-lens. "No ordinary break," he commented. "You can see that it was an explosive that was used--an explosive well and properly tamped down with wet clay. Without tamping, the rails would have been bent, not broken." "Done by wreckers, then?" Lane asked. "Certainly not defective rails," replied Kennedy. "Still, I don't think you need worry so much about them for the next train. You know what to guard against. Having been discovered, whoever they are, they'll probably not try it again. It's some new wrinkle that must be guarded against." It was small comfort, but Craig was accustomed to being brutally frank. "Have you taken any other precautions now that you didn't take before?" "Yes," replied Lane, slowly; "the railroad has been experimenting with wireless on its trains. We have placed wireless on ours, too. They can't cut us off by cutting wires. Then, of course, as before, we shall use a pilot-train to run ahead and a strong guard on the train itself. But now I feel that there may be something else that we can do. So I have come to you." "When does the next shipment start?" asked Kennedy. "To-morrow, from Halifax." Kennedy appeared to be considering something. "The trouble," he said, at length, "is likely to be at this end. Perhaps before the train starts something may happen that will tell us just what additional measures to take as it approaches New York." While Kennedy was at work with the blood-soaked gauze that he had taken from Barnes, I could do nothing but try to place the relative positions of the various actors in the little drama that was unfolding. Lane himself puzzled me. Sometimes I felt almost sure that he knew that Miss Euston had come to Kennedy, and that he was trying, in this way, to keep in touch with what was being done for Barnes. Some things I knew already. Barnes was comparatively wealthy, and had evidently the stamp of approval of Maude Euston's father. As for Lane, he was far from wealthy, although ambitious. The company was in a delicate situation where an act of omission would count for as much as an act of commission. Whoever could foresee what was going to happen might capitalize that information for much money. If there was a plot and Barnes had been a victim, what was its nature? I recalled Miss Euston's overheard conversation in the tea-room. Both names had been mentioned. In short, I soon found myself wondering whether some one might not have tempted Lane either to do or not to do something. "I wish you'd go over to the St. Germaine, Walter," remarked Kennedy, at length, looking up from his work. "Don't tell Miss Euston of Lane's visit. But ask her if she will keep an eye out for that woman she heard talking--and the man, too. They may drop in again. And tell her that if she hears anything else, no matter how trivial, about Barnes, she must let me know." I was glad of the commission. Not only had I been unable to arrive anywhere in my conjectures, but it was something even to have a chance to talk with a girl like Maude Euston. Fortunately I found her at home and, though she was rather disappointed that I had nothing to report, she received me graciously, and we spent the rest of the evening watching the varied life of the fashionable hostelry in the hope of chancing on the holders of the strange conversation in the tea-room. Once in a while an idea would occur to her of some one who was in a position to keep her informed if anything further happened to Barnes, and she would despatch a messenger with a little note. Finally, as it grew late and the adventuress of the tea-room episode seemed unlikely to favor the St. Germaine with her presence again that night, I made my excuses, having had the satisfaction only of having delivered Kennedy's message, without accomplishing anything more. In fact, I was still unable to determine whether there was any sentiment stronger than sympathy that prompted her to come to Kennedy about Barnes. As for Lane, his name was scarcely mentioned except when it was necessary. It was early the next morning that I rejoined Craig at the laboratory. I found him studying the solution which he had extracted from the blood-soaked gauze after first removing the blood in a little distilled water. Before him was his new spectroscope, and I could see that now he was satisfied with what the uncannily delicate light-detective had told him. He pricked his finger and let a drop of blood fall into a little fresh distilled water, some of which he placed in the spectroscope. "Look through it," he said. "Blood diluted with water shows the well-known dark bands between D and E, known as the oxyhemoglobin absorption." I looked as he indicated and saw the dark bands. "Now," he went on, "I add some of this other liquid." He picked up a bottle of something with a faint greenish tinge. "See the bands gradually fade?" I watched, and indeed they did diminish in intensity and finally disappear, leaving an uninterrupted and brilliant spectrum. "My spectroscope," he said, simply, "shows that the blood-crystals of Barnes are colorless. Barnes was poisoned--by some gas, I think. I wish I had time to hunt along the road where the accident took place." As he said it, he walked over and drew from a cabinet several peculiar arrangements made of gauze. He was about to say something more when there came a knock at the door. Kennedy shoved the gauze arrangements into his pocket and opened it. It was Maude Euston, breathless and agitated. "Oh, Mr. Kennedy, have you heard?" she cried. "You asked me to keep a watch whether anything more happened to Mr. Barnes. So I asked some friends of his to let me know of anything. He has a yacht, the Sea Gull, which has been lying off City Island. Well, last night the captain received a message to go to the hospital, that Mr. Barnes wanted to see him. Of course it was a fake. Mr. Barnes was too sick to see anybody on business. But when the captain got back, he found that, on one pretext or another, the crew had been got ashore--and the Sea Gull is gone--stolen! Some men in a small boat must have overpowered the engineer. Anyhow, she has disappeared. I know that no one could expect to steal a yacht--at least for very long. She'd be recognized soon. But they must know that, too." Kennedy looked at his watch. "It is only a few hours since the train started from Halifax," he considered. "It will be due in New York early to-morrow morning--twenty million dollars in gold and thirty millions in securities--a seven-car steel train, with forty armed guards!" "I know it," she said, anxiously, "and I am so afraid something is going to happen--ever since I had to play the spy. But what could any one want with a yacht?" Kennedy shrugged his shoulders non-committally. "It is one of the things that Mr. Lane must guard against," he remarked, simply. She looked up quickly. "Mr. Lane?" she repeated. "Yes," replied Kennedy; "the protection of the train has fallen on him. I shall meet the train myself when it gets to Worcester and come in on it. I don't think there can be any danger before it reaches that point." "Will Mr. Lane go with you?" "He must," decided Kennedy. "That train must be delivered safely here in this city." Maude Euston gave Craig one of her penetrating, direct looks. "You think there is danger, then?" "I cannot say," he replied. "Then I am going with you!" she exclaimed. Kennedy paused and met her eyes. I do not know whether he read what was back of her sudden decision. At least I could not, unless there was something about Rodman Lane which she wished to have cleared up. Kennedy seemed to read her character and know that a girl like Maude Euston would be a help in any emergency. "Very well," he agreed; "meet us at Mr. Lane's office in half an hour. Walter, see whether you can find Whiting." Whiting was one of Kennedy's students with whom he had been lately conducting some experiments. I hurried out and managed to locate him. "What is it you suspect?" I asked, when we returned. "A wreck--some spectacular stroke at the nations that are shipping the gold?" "Perhaps," he replied, absently, as he and Whiting hurriedly assembled some parts of instruments that were on a table in an adjoining room. "Perhaps?" I repeated. "What else might there be?" "Robbery." "Robbery!" I exclaimed. "Of twenty million dollars? Why, man, just consider the mere weight of the metal!" "That's all very well," he replied, warming up a bit as he saw that Whiting was getting things together quickly. "But it needs only a bit of twenty millions to make a snug fortune--" He paused and straightened up as the gathering of the peculiar electrical apparatus, whatever it was, was completed. "And," he went on quickly, "consider the effect on the stock-market of the news. That's the big thing." I could only gasp. "A modern train-robbery, planned in the heart of dense traffic!" "Why not?" he queried. "Nothing is impossible if you can only take the other fellow unawares. Our job is not to be taken unawares. Are you ready, Whiting?" "Yes, sir," replied the student, shouldering the apparatus, for which I was very thankful, for my arms had frequently ached carrying about some of Kennedy's weird but often weighty apparatus. We piled into a taxicab and made a quick journey to the office of the Continental Express. Maude Euston had already preceded us, and we found her standing by Lane's desk as he paced the floor. "Please, Miss Euston, don't go," he was saying as we entered. "But I want to go," she persisted, more than ever determined, apparently. "I have engaged Professor Kennedy just for the purpose of foreseeing what new attack can be made on us," he said. "You have engaged Professor Kennedy?" she asked. "I think I have a prior claim there, haven't I?" she appealed. Kennedy stood for a moment looking from one to the other. What was there in the motives that actuated them? Was it fear, hate, love, jealousy? "I can serve my two clients only if they yield to me," Craig remarked, quietly. "Don't set that down, Whiting. Which is it--yes or no?" Neither Lane nor Miss Euston looked at each other for a moment. "Is it in my hands?" repeated Craig. "Yes," bit off Lane, sourly. "And you, Miss Euston?" "Of course," she answered. "Then we all go," decided Craig. "Lane, may I install this thing in your telegraph-room outside?" "Anything you say," Lane returned, unmollified. Whiting set to work immediately, while Kennedy gave him the final instructions. Neither Lane nor Miss Euston spoke a word, even when I left the room for a moment, fearing that three was a crowd. I could not help wondering whether she might not have heard something more from the woman in the tea-room conversation than she had told us. If she had, she had been more frank with Lane than with us. She must have told him. Certainly she had not told us. It was the only way I could account for the armed truce that seemed to exist as, hour after hour, our train carried us nearer the point where we were to meet the treasure-train. At Worcester we had still a long wait for the argosy that was causing so much anxiety and danger. It was long after the time scheduled that we left finally, on our return journey, late at night. Ahead of us went a dummy pilot-train to be sacrificed if any bridges or trestles were blown up or if any new attempts were made at producing artificially broken rails. We four established ourselves as best we could in a car in the center of the treasure-train, with one of the armed guards as company. Mile after mile we reeled off, ever southward and westward. We must have crossed the State of Connecticut and have been approaching Long Island Sound, when suddenly the train stopped with a jerk. Ordinarily there is nothing to grow alarmed about at the mere stopping of a train. But this was an unusual train under unusual circumstances. No one said a word as we peered out. Down the track the signals seemed to show a clear road. What was the matter? "Look!" exclaimed Kennedy, suddenly. Off a distance ahead I could see what looked like a long row of white fuses sticking up in the faint starlight. From them the fresh west wind seemed to blow a thick curtain of greenish-yellow smoke which swept across the track, enveloping the engine and the forward cars and now advancing toward us like the "yellow wind" of northern China. It seemed to spread thickly on the ground, rising scarcely more than sixteen or eighteen feet. A moment and the cloud began to fill the air about us. There was a paralyzing odor. I looked about at the others, gasping and coughing. As the cloud rolled on, inexorably increasing in density, it seemed literally to grip the lungs. It flashed over me that already the engineer and fireman had been overcome, though not before the engineer had been able to stop the train. As the cloud advanced, the armed guards ran from it, shouting, one now and then falling, overcome. For the moment none of us knew what to do. Should we run and desert the train for which we had dared so much? To stay was death. Quickly Kennedy pulled from his pocket the gauze arrangements he had had in his hand that morning just as Miss Euston's knock had interrupted his conversation with me. Hurriedly he shoved one into Miss Euston's hands, then to Lane, then to me, and to the guard who was with us. "Wet them!" he cried, as he fitted his own over his nose and staggered to a water-cooler. "What is it?" I gasped, hoarsely, as we all imitated his every action. "Chlorin gas," he rasped back, "the same gas that overcame Granville Barnes. These masks are impregnated with a glycerin solution of sodium phosphate. It was chlorin that destroyed the red coloring matter in Barnes's blood. No wonder, when this action of just a whiff of it on us is so rapid. Even a short time longer and death would follow. It destroys without the possibility of reconstitution, and it leaves a dangerous deposit of albumin. How do you feel?" "All right," I lied. We looked out again. The things that looked like fuses were not bombs, as I had expected, but big reinforced bottles of gas compressed at high pressure, with the taps open. The supply was not inexhaustible. In fact, it was decidedly limited. But it seemed to have been calculated to a nicety to do the work. Only the panting of the locomotive now broke the stillness as Kennedy and I moved forward along the track. Crack! rang out a shot. "Get on the other side of the train--quick!" ordered Craig. In the shadow, aside from the direction in which the wind was wafting the gas, we could now just barely discern a heavy but powerful motor-truck and figures moving about it. As I peered out from the shelter of the train, I realized what it all meant. The truck, which had probably conveyed the gas-tanks from the rendezvous where they had been collected, was there now to convey to some dark wharf what of the treasure could be seized. There the stolen yacht was waiting to carry it off. "Don't move--don't fire," cautioned Kennedy. "Perhaps they will think it was only a shadow they saw. Let them act first. They must. They haven't any too much time. Let them get impatient." For some minutes we waited. Sure enough, separated widely, but converging toward the treasure-train at last, we could see several dark figures making their way from the road across a strip of field and over the rails. I made a move with my gun. "Don't," whispered Kennedy. "Let them get together." His ruse was clever. Evidently they thought that it had been indeed a wraith at which they had fired. Swiftly now they hurried to the nearest of the gold-laden cars. We could hear them, breaking in where the guards had either been rendered unconscious or had fled. I looked around at Maude Euston. She was the calmest of us all as she whispered: "They are in the car. Can't we DO something?" "Lane," whispered Kennedy, "crawl through under the trucks with me. Walter, and you, Dugan," he added, to the guard, "go down the other side. We must rush them--in the car." As Kennedy crawled under the train again I saw Maude Euston follow Lane closely. How it happened I cannot describe, for the simple reason that I don't remember. I know that it was a short, sharp dash, that the fight was a fight of fists in which guns were discharged wildly in the air against the will of the gunner. But from the moment when Kennedy's voice rang out in the door, "Hands up!" to the time that I saw that we had the robbers lined up with their backs against the heavy cases of the precious metal for which they had planned and risked so much, it is a blank of grim death-struggle. I remember my surprise at seeing one of them a woman, and I thought I must be mistaken. I looked about. No; there was Maude Euston standing just beside Lane. I think it must have been that which recalled me and made me realize that it was a reality and not a dream. The two women stood glaring at each other. "The woman in the tea-room!" exclaimed Miss Euston. "It was about this--robbery--then, that I heard you talking the other afternoon." I looked at the face before me. It was, had been, a handsome face. But now it was cold and hard, with that heartless expression of the adventuress. The men seemed to take their plight hard. But, as she looked into the clear, gray eyes of the other woman, the adventuress seemed to gain rather than lose in defiance. "Robbery?" she repeated, bitterly. "This is only a beginning." "A beginning. What do you mean?" It was Lane who spoke. Slowly she turned toward him. "You know well enough what I mean." The implication that she intended was clear. She had addressed the remark to him, but it was a stab at Maude Euston. "I know only what you wanted me to do--and I refused. Is there more still?" I wondered whether Lane could really have been involved. "Quick--what DO you mean?" demanded Kennedy, authoritatively. The woman turned to him: "Suppose this news of the robbery is out? What will happen? Do you want me to tell you, young lady?" she added, turning again to Maude Euston. "I'll tell you. The stock of the Continental Express Company will fall like a house of cards. And then? Those who have sold it at the top price will buy it back again at the bottom. The company is sound. The depression will not last--perhaps will be over in a day, a week, a month. Then the operators can send it up again. Don't you see? It is the old method of manipulation in a new form. It is a war-stock gamble. Other stocks will be affected the same way. This is our reward--what we can get out of it by playing this game for which the materials are furnished free. We have played it--and lost. The manipulators will get their reward on the stock-market this morning. But they must still reckon with us--even if we have lost." She said it with a sort of grim humor. "And you have put Granville Barnes out of the way, first?" I asked, remembering the chlorin. She laughed shrilly. "That was an accident--his own carelessness. He was carrying a tank of it for us. Only his chauffeur's presence of mind in throwing it into the shrubbery by the road saved his life and reputation. No, young man; he was one of the manipulators, too. But the chief of them was--" She paused as if to enjoy one brief moment of triumph at least. "The president of the company," she added. "No, no, no!" cried Maude Euston. "Yes, yes, yes! He does not dare deny it. They were all in it." "Mrs. Labret--you lie!" towered Lane, in a surging passion, as he stepped forward and shook his finger at her. "You lie and you know it. There is an old saying about the fury of a woman scorned." She paid no attention to him whatever. "Maude Euston," she hissed, as though Lane had been as inarticulate as the boxes of gold about, "you have saved your lover's reputation--perhaps. At least the shipment is safe. But you have ruined your father. The deal will go through. Already that has been arranged. You may as well tell Kennedy to let us go and let the thing go through. It involves more than us." Kennedy had been standing back a bit, carefully keeping them all covered. He glanced a moment out of the corner of his eye at Maude Euston, but said nothing. It was a terrible situation. Had Lane really been in it? That question was overshadowed by the mention of her father. Impulsively she turned to Craig. "Oh, save him!" she cried. "Can't anything be done to save my father in spite of himself?" "It is too late," mocked Mrs. Labret. "People will read the account of the robbery in the papers, even if it didn't take place. They will see it before they see a denial. Orders will flood in to sell the stock. No; it can't be stopped." Kennedy glanced momentarily at me. "Is there still time to catch the last morning edition of the Star, Walter?" he asked, quietly. I glanced at my watch. "We may try. It's possible." "Write a despatch--an accident to the engine--train delayed--now proceeding--anything. Here, Dugan, you keep them covered. Shoot to kill if there's a move." Kennedy had begun feverishly setting up the part of the apparatus which he had brought after Whiting had set up his. "What can you do?" hissed Mrs. Labret. "You can't get word through. Orders have been issued that the telegraph operators are under no circumstances to give out news about this train. The wireless is out of commission, too--the operator overcome. The robbery story has been prepared and given out by this time. Already reporters are being assigned to follow it up." I looked over at Kennedy. If orders had been given for such secrecy by Barry Euston, how could my despatch do any good? It would be held back by the operators. Craig quickly slung a wire over those by the side of the track and seized what I had written, sending furiously. "What are you doing?" I asked. "You heard what she said." "One thing you can be certain of," he answered, "that despatch can never be stolen or tapped by spies." "Why--what is this?" I asked, pointing to the instrument. "The invention of Major Squier, of the army," he replied, "by which any number of messages may be sent at the same time over the same wire without the slightest conflict. Really it consists in making wireless electric waves travel along, instead of inside, the wire. In other words, he had discovered the means of concentrating the energy of a wireless wave on a given point instead of letting it riot all over the face of the earth. "It is the principle of wireless. But in ordinary wireless less than one-millionth part of the original sending force reaches the point for which it is intended. The rest is scattered through space in all directions. If the vibrations of a current are of a certain number per second, the current will follow a wire to which it is, as it were, attached, instead of passing off into space. "All the energy in wireless formerly wasted in radiation in every direction now devotes itself solely to driving the current through the ether about the wire. Thus it goes until it reaches the point where Whiting is--where the vibrations correspond to its own and are in tune. There it reproduces the sending impulse. It is wired wireless." Craig had long since finished sending his wired wireless message. We waited impatiently. The seconds seemed to drag like hours. Far off, now, we could hear a whistle as a train finally approached slowly into our block, creeping up to see what was wrong. But that made no difference now. It was not any help they could give us that we wanted. A greater problem, the saving of one man's name and the re-establishment of another, confronted us. Unexpectedly the little wired wireless instrument before us began to buzz. Quickly Kennedy seized a pencil and wrote as the message that no hand of man could interfere with was flashed back to us. "It is for you, Walter, from the Star," he said, simply handing me what he had written on the back of an old envelope. I read, almost afraid to read: Robbery story killed. Black type across page-head last edition, "Treasure-train safe!" McGRATH. "Show it to Miss Euston," Craig added, simply, gathering up his wired wireless set, just as the crew from the train behind us ran up. "She may like to know that she has saved her father from himself through misunderstanding her lover." I thought Maude Euston would faint as she clutched the message. Lane caught her as she reeled backward. "Rodman--can you--forgive me?" she murmured, simply, yielding to him and looking up into his face. II THE TRUTH DETECTOR "You haven't heard--no one outside has heard--of the strange illness and the robbery of my employer, Mr. Mansfield--'Diamond Jack' Mansfield, you know." Our visitor was a slight, very pretty, but extremely nervous girl, who had given us a card bearing the name Miss Helen Grey. "Illness--robbery?" repeated Kennedy, at once interested and turning a quick glance at me. I shrugged my shoulders in the negative. Neither the Star nor any of the other papers had had a word about it. "Why, what's the trouble?" he continued to Miss Grey. "You see," she explained, hurrying on, "I'm Mr. Mansfield's private secretary, and--oh, Professor Kennedy, I don't know, but I'm afraid it is a case for a detective rather than a doctor." She paused a moment and leaned forward nearer to us. "I think he has been poisoned!" The words themselves were startling enough without the evident perturbation of the girl. Whatever one might think, there was no doubt that she firmly believed what she professed to fear. More than that, I fancied I detected a deeper feeling in her tone than merely loyalty to her employer. "Diamond Jack" Mansfield was known in Wall Street as a successful promoter, on the White Way as an assiduous first-nighter, in the sporting fraternity as a keen plunger. But of all his hobbies, none had gained him more notoriety than his veritable passion for collecting diamonds. He came by his sobriquet honestly. I remembered once having seen him, and he was, in fact, a walking De Beers mine. For his personal adornment, more than a million dollars' worth of gems did relay duty. He had scores of sets, every one of them fit for a king of diamonds. It was a curious hobby for a great, strong man, yet he was not alone in his love of and sheer affection for things beautiful. Not love of display or desire to attract notice to himself had prompted him to collect diamonds, but the mere pleasure of owning them, of associating with them. It was a hobby. It was not strange, therefore, to suspect that Mansfield might, after all, have been the victim of some kind of attack. He went about with perfect freedom, in spite of the knowledge that crooks must have possessed about his hoard. "What makes you think he has been poisoned?" asked Kennedy, betraying no show of doubt that Miss Grey might be right. "Oh, it's so strange, so sudden!" she murmured. "But how do you think it could have happened?" he persisted. "It must have been at the little supper-party he gave at his apartment last night," she answered, thoughtfully, then added, more slowly, "and yet, it was not until this morning, eight or ten hours after the party, that he became ill." She shuddered. "Paroxysms of nausea, followed by stupor and such terrible prostration. His valet discovered him and sent for Doctor Murray--and then for me." "How about the robbery?" prompted Kennedy, as it became evident that it was Mansfield's physical condition more than anything else that was on Miss Grey's mind. "Oh yes"--she recalled herself--"I suppose you know something of his gems? Most people do." Kennedy nodded. "He usually keeps them in a safe-deposit vault downtown, from which he will get whatever set he feels like wearing. Last night it was the one he calls his sporting-set that he wore, by far the finest. It cost over a hundred thousand dollars, and is one of the most curious of all the studies in personal adornment that he owns. All the stones are of the purest blue-white and the set is entirely based on platinum. "But what makes it most remarkable is that it contains the famous M-1273, as he calls it. The M stands for Mansfield, and the figures represent the number of stones he had purchased up to the time that he acquired this huge one." "How could they have been taken, do you think?" ventured Kennedy. Miss Grey shook her head doubtfully. "I think the wall safe must have been opened somehow," she returned. Kennedy mechanically wrote the number, M-1273, on a piece of paper. "It has a weird history," she went on, observing what he had written, "and this mammoth blue-white diamond in the ring is as blue as the famous Hope diamond that has brought misfortune through half the world. This stone, they say, was pried from the mouth of a dying negro in South Africa. He had tried to smuggle it from the mine, and when he was caught cursed the gem and every one who ever should own it. One owner in Amsterdam failed; another in Antwerp committed suicide; a Russian nobleman was banished to Siberia, and another went bankrupt and lost his home and family. Now here it is in Mr. Mansfield's life. I--I hate it!" I could not tell whether it was the superstition or the recent events themselves which weighed most in her mind, but, at any rate, she resumed, somewhat bitterly, a moment later: "M-1273! M is the thirteenth letter of the alphabet, and 1, 2, 7, 3 add up to thirteen. The first and last numbers make thirteen, and John Mansfield has thirteen letters in his name. I wish he had never worn the thing--never bought it!" The more I listened to her the more impressed I was with the fact that there was something more here than the feeling of a private secretary. "Who were in the supper-party?" asked Kennedy. "He gave it for Madeline Hargrave--the pretty little actress, you know, who took New York by storm last season in 'The Sport' and is booked, next week, to appear in the new show, 'The Astor Cup.'" Miss Grey said it, I thought, with a sort of wistful envy. Mansfield's gay little bohemian gatherings were well known. Though he was not young, he was still somewhat of a Lothario. "Who else was there?" asked Kennedy. "Then there was Mina Leitch, a member of Miss Hargrave's new company," she went on. "Another was Fleming Lewis, the Wall Street broker. Doctor Murray and myself completed the party." "Doctor Murray is his personal physician?" ventured Craig. "Yes. You know when Mr. Mansfield's stomach went back on him last year it was Doctor Murray who really cured him." Kennedy nodded. "Might this present trouble be a recurrence of the old trouble?" She shook her head. "No; this is entirely different. Oh, I wish that you could go with me and see him!" she pleaded. "I will," agreed Kennedy. A moment later we were speeding in a taxicab over to the apartment. "Really," she remarked, nervously, "I feel lost with Mr. Mansfield so ill. He has so many interests downtown that require constant attention that just the loss of time means a great deal. Of course, I understand many of them--but, you know, a private secretary can't conduct a man's business. And just now, when I came up from the office, I couldn't believe that he was too ill to care about things until I actually saw him." We entered the apartment. A mere glance about showed that; even though Mansfield's hobby was diamonds, he was no mean collector of other articles of beauty. In the big living-room, which was almost like a studio, we met a tall, spare, polished-mannered man, whom I quickly recognized as Doctor Murray. "Is he any better?" blurted out Miss Grey, even before our introductions were over. Doctor Murray shook his head gravely. "About the same," he answered, though one could find little reassurance in his tone. "I should like to see him," hinted Kennedy, "unless there is some real reason why I should not." "No," replied the doctor, absently; "on the contrary, it might perhaps rouse him." He led the way down the hall, and Kennedy and I followed, while Miss Grey attempted to busy herself over some affairs at a huge mahogany table in the library just off the living-room. Mansfield had shown the same love of luxury and the bizarre even in the furnishing of his bedroom, which was a black-and-white room with furniture of Chinese lacquer and teakwood. Kennedy looked at the veteran plunger long and thoughtfully as he lay stretched out, listless, on the handsome bed. Mansfield seemed completely indifferent to our presence. There was something uncanny about him. Already his face was shrunken, his skin dark, and his eyes were hollow. "What do you suppose it is?" asked Kennedy, bending over him, and then rising and averting his head so that Mansfield could not hear, even if his vagrant faculties should be attracted. "His pulse is terribly weak and his heart scarcely makes a sound." Doctor Murray's face knit in deep lines. "I'm afraid," he said, in a low tone, "that I will have to admit not having been able to diagnose the trouble, I was just considering whom I might call in." "What have you done?" asked Kennedy, as the two moved a little farther out of ear-shot of the patient. "Well," replied the doctor, slowly, "when his valet called me in, I must admit that my first impression was that I had to deal with a case of diphtheria. I was so impressed that I even took a blood smear and examined it. It showed the presence of a tox albumin. But it isn't diphtheria. The antitoxin has had no effect. No; it isn't diphtheria. But the poison is there. I might have thought it was cholera, only that seems so impossible here in New York." Doctor Murray looked at Kennedy with no effort to conceal his perplexity. "Over and over I have asked myself what it could be," he went on. "It seems to me that I have thought over about everything that is possible. Always I get back to the fact that there is that tox albumin present. In some respects, it seems like the bite of a poisonous animal. There are no marks, of course, and it seems altogether impossible, yet it acts precisely as I have seen snake bites affect people. I am that desperate that I would try the Noguchi antivenene, but it would have no more effect than the antitoxin. No; I can only conclude that there is some narcotic irritant which especially affects the lungs and heart." "Will you let me have one of the blood smears?" asked Kennedy. "Certainly," replied the doctor, reaching over and taking a glass slide from several lying on a table. For some time after we left the sick-room Craig appeared to be considering what Doctor Murray had said. Seeking to find Miss Grey in the library, we found ourselves in the handsome, all-wood-paneled dining-room. It still showed evidences of the late banquet of the night before. Craig paused a moment in doubt which way to go, then picked up from the table a beautifully decorated menu-card. As he ran his eye down it mechanically, he paused. "Champignons," he remarked, thoughtfully. "H-m!--mushrooms." Instead of going on toward the library, he turned and passed through a swinging door into the kitchen. There was no one there, but it was in a much more upset condition than the dining-room. "Pardon, monsieur," sounded a voice behind us. It was the French chef who had entered from the direction of the servants' quarters, and was now all apologies for the untidy appearance of the realm over which he presided. The strain of the dinner had been too much for his assistants, he hastened to explain. "I see that you had mushrooms--creamed," remarked Kennedy. "Oui, monsieur," he replied; "some that Miss Hargrave herself sent in from her mushroom-cellar out in the country." As he said it his eye traveled involuntarily toward a pile of ramekins on a table. Kennedy noticed it and deliberately walked over to the table. Before I knew what he was about he had scooped from them each a bit of the contents and placed it in some waxed paper that was lying near by. The chef watched him curiously. "You would not find my kitchen like this ordinarily," he remarked. "I would not like to have Doctor Murray see it, for since last year, when monsieur had the bad stomach, I have been very careful." The chef seemed to be nervous. "You prepared the mushrooms yourself?" asked Kennedy, suddenly. "I directed my assistant," came back the wary reply. "But you know good mushrooms when you see them?" "Certainly," he replied, quickly. "There was no one else in the kitchen while you prepared them?" "Yes," he answered, hurriedly; "Mr. Mansfield came in, and Miss Hargrave. Oh, they are very particular! And Doctor Murray, he has given me special orders ever since last year, when monsieur had the bad stomach," he repeated. "Was any one else here?" "Yes--I think so. You see, I am so excited--a big dinner--such epicures--everything must be just so--I cannot say." There seemed to be little satisfaction in quizzing the chef, and Kennedy turned again into the dining-room, making his way back to the library, where Miss Grey was waiting anxiously for us. "What do you think?" she asked, eagerly. "I don't know what to think," replied Kennedy. "No one else has felt any ill effects from the supper, I suppose?" "No," she replied; "at least, I'm sure I would have heard by this time if they had." "Do you recall anything peculiar about the mushrooms?" shot out Kennedy. "We talked about them some time, I remember," she said, slowly. "Growing mushrooms is one of Miss Hargrave's hobbies out at her place on Long Island." "Yes," persisted Kennedy; "but I mean anything peculiar about the preparation of them." "Why, yes," she said, suddenly; "I believe that Miss Hargrave was to have superintended them herself. We all went out into the kitchen. But it was too late. They had been prepared already." "You were all in the kitchen?" "Yes; I remember. It was before the supper and just after we came in from the theater-party which Mr. Mansfield gave. You know Mr. Mansfield is always doing unconventional things like that. If he took a notion, he would go into the kitchen of the Ritz." "That is what I was trying to get out of the chef--Francois," remarked Kennedy. "He didn't seem to have a very clear idea of what happened. I think I'll see him again--right away." We found the chef busily at work, now, cleaning up. As Kennedy asked him a few inconsequential questions, his eye caught a row of books on a shelf. It was a most complete library of the culinary arts. Craig selected one and turned the pages over rapidly. Then he came back to the frontispiece, which showed a model dinner-table set for a number of guests. He placed the picture before Francois, then withdrew it in, I should say, about ten seconds. It was a strange and incomprehensible action, but I was more surprised when Kennedy added: "Now tell me what you saw." Francois was quite overwhelming in his desire to please. Just what was going on in his mind I could not guess, nor did he betray it, but quickly he enumerated the objects on the table, gradually slowing up as the number which he recollected became exhausted. "Were there candles?" prompted Craig, as the flow of Francois's description ceased. "Oh yes, candles," he agreed, eagerly. "Favors at each place?" "Yes, sir." I could see no sense in the proceeding, yet knew Kennedy too well to suppose, for an instant, that he had not some purpose. The questioning over, Kennedy withdrew, leaving poor Francois more mystified than ever. "Well," I exclaimed, as we passed through the dining-room, "what was all that?" "That," he explained, "is what is known to criminologists as the 'Aussage test.' Just try it some time when you get a chance. If there are, say, fifty objects in a picture, normally a person may recall perhaps twenty of them." "I see," I interrupted; "a test of memory." "More than that," he replied. "You remember that, at the end, I suggested several things likely to be on the table. They were not there, as you might have seen if you had had the picture before you. That was a test of the susceptibility to suggestion of the chef. Francois may not mean to lie, but I'm afraid we'll have to get along without him in getting to the bottom of the case. You see, before we go any further we know that he is unreliable--to say the least. It may be that nothing at all happened in the kitchen to the mushrooms. We'll never discover it from him. We must get it elsewhere." Miss Grey had been trying to straighten out some of the snarls which Mansfield's business affairs had got into as a result of his illness; but it was evident that she had difficulty in keeping her mind on her work. "The next thing I'd like to see," asked Kennedy, when we rejoined her, "is that wall safe." She led the way down the hall and into an ante-room to Mansfield's part of the suite. The safe itself was a comparatively simple affair inside a closet. Indeed, I doubt whether it had been seriously designed to be burglar-proof. Rather it was merely a protection against fire. "Have you any suspicion about when the robbery took place?" asked Kennedy, as we peered into the empty compartment. "I wish I had been called in the first thing when it was discovered. There might have been some chance to discover fingerprints. But now, I suppose, every clue of that sort has been obliterated." "No," she replied; "I don't know whether it happened before or after Mr. Mansfield was discovered so ill by his valet." "But at least you can give me some idea of when the jewels were placed in the safe." "It must have been before the supper, right after our return from the theater." "So?" considered Kennedy. "Then that would mean that they might have been taken by any one, don't you see? Why did he place them in the safe so soon, instead of wearing them the rest of the evening?" "I hadn't thought of that way of looking at it," she admitted. "Why, when we came home from the theater I remember it had been so warm that Mr. Mansfield's collar was wilted and his dress shirt rumpled. He excused himself, and when he returned he was not wearing the diamonds. We noticed it, and Miss Hargrave expressed a wish that she might wear the big diamond at the opening night of 'The Astor Cup.' Mr. Mansfield promised that she might and nothing more was said about it." "Did you notice anything else at the dinner--no matter how trivial?" asked Kennedy. Helen Grey seemed to hesitate, then said, in a low voice, as though the words were wrung from her: "Of course, the party and the supper were given ostensibly to Miss Hargrave. But--lately--I have thought he was paying quite as much attention to Mina Leitch." It was quite in keeping with what we knew of "Diamond Jack." Perhaps it was this seeming fickleness which had saved him from many entangling alliances. Miss Grey said it in such a way that it seemed like an apology for a fault in his character which she would rather have hidden. I could not but fancy that it mitigated somewhat the wistful envy I had noticed before when she spoke of Madeline Hargrave. While he had been questioning her Kennedy had been examining the wall safe, particularly with reference to its accessibility from the rest of the apartment. There appeared to be no reason why one could not have got at it from the hallway as well as from Mansfield's room. The safe itself seemed to yield no clue, and Kennedy was about to turn away when he happened to glance down at the dark interior of the closet floor. He stooped down. When he rose he had something in his hand. It was just a little thin piece of something that glittered iridescently. "A spangle from a sequin dress," he muttered to himself; then, turning to Miss Grey, "Did any one wear such a dress last night?" Helen Grey looked positively frightened. "Miss Hargrave!" she murmured, simply. "Oh, it cannot be--there must be some mistake!" Just then we heard voices in the hall. "But, Murray, I don't see why I can't see him," said one. "What good will it do, Lewis?" returned the other, which I recognized as that of Doctor Murray. "Fleming Lewis," whispered Miss Grey, taking a step out into the hallway. A moment later Doctor Murray and Lewis had joined us. I could see that there was some feeling between the two men, though what it was about I could not say. As Miss Grey introduced us, I glanced hastily out of the corner of my eye at Kennedy. Involuntarily his hand which held the telltale sequin had sought his waistcoat pocket, as though to hide it. Then I saw him check the action and deliberately examine the piece of tinsel between his thumb and forefinger. Doctor Murray saw it, too, and his eyes were riveted on it, as though instantly he saw its significance. "What do you think--Jack as sick as a dog, and robbed, too, and yet Murray says I oughtn't to see him!" complained Lewis, for the moment oblivious to the fact that all our eyes were riveted on the spangle between Kennedy's fingers. And then, slowly it seemed to dawn on him what it was. "Madeline's!" he exclaimed, quickly. "So Mina did tear it, after all, when she stepped on the train." Kennedy watched the faces before us keenly. No one said anything. It was evident that some such incident had happened. But had Lewis, with a quick flash of genius, sought to cover up something, protect somebody? Miss Grey was evidently anxious to transfer the scene at least to the living-room, away from the sick-room, and Kennedy, seeing it, fell in with the idea. "Looks to me as though this robbery was an inside affair," remarked Lewis, as we all stood for a moment in the living-room. "Do you suppose one of the servants could have been 'planted' for the purpose of pulling it off?" The idea was plausible enough. Yet, plausible as the suggestion might seem, it took no account of the other circumstances of the case. I could not believe that the illness of Mansfield was merely an unfortunate coincidence. Fleming Lewis's unguarded and blunt tendency to blurt out whatever seemed uppermost in his mind soon became a study to me as we talked together in the living-room. I could not quite make out whether it was studied and astute or whether it was merely the natural exuberance of youth. There was certainly some sort of enmity between him and the doctor, which the remark about the spangle seemed to fan into a flame. Miss Grey manoeuvered tactfully, however, to prevent a scene. And, after an interchange of remarks that threw more heat than light on the matter, Kennedy and I followed Lewis out to the elevator, with a parting promise to keep in touch with Miss Grey. "What do you think of the spangle?" I queried of Craig as Lewis bade us a hasty good-by and climbed into his car at the street-entrance. "Is it a clue or a stall?" "That remains to be seen," he replied, noncommittally. "Just now the thing that interests me most is what I can accomplish at the laboratory in the way of finding out what is the matter with Mansfield." While Kennedy was busy with the various solutions which he made of the contents of the ramekins that had held the mushrooms, I wandered over to the university library and waded through several volumes on fungi without learning anything of value. Finally, knowing that Kennedy would probably be busy for some time, and that all I should get for my pains by questioning him would be monosyllabic grunts until he was quite convinced that he was on the trail of something, I determined to run into the up-town office of the Star and talk over the affair as well as I could without violating what I felt had been given us in confidence. I could not, it turned out, have done anything better, for it seemed to be the gossip of the Broadway cafes and cabarets that Mansfield had been plunging rather deeply lately and had talked many of his acquaintances into joining him in a pool, either outright or on margins. It seemed to be a safe bet that not only Lewis and Doctor Murray had joined him, but that Madeline Hargrave and Mina Leitch, who had had a successful season and some spare thousands to invest, might have gone in, too. So far the fortunes of the stock-market had not smiled on Mansfield's schemes, and, I reflected, it was not impossible that what might be merely an incident to a man like Mansfield could be very serious to the rest of them. It was the middle of the afternoon when I returned to the laboratory with my slender budget of news. Craig was quite interested in what I had to say, even pausing for a few moments in his work to listen. In several cages I saw that he had a number of little guinea-pigs. One of them was plainly in distress, and Kennedy had been watching him intently. "It's strange," he remarked. "I had samples of material from six ramekins. Five of them seem to have had no effect whatever. But if the bit that I gave this fellow causes such distress, what would a larger quantity do?" "Then one of the ramekins was poisoned?" I questioned. "I have discovered in it, as well as in the blood smear, the tox albumin that Doctor Murray mentioned," he said, simply, pulling out his watch. "It isn't late. I think I shall have to take a trip out to Miss Hargrave's. We ought to do it in an hour and a half in a car." Kennedy said very little as we sped out over the Long Island roads that led to the little colony of actors and actresses at Cedar Grove. He seemed rather to be enjoying the chance to get away from the city and turn over in his mind the various problems which the case presented. As for myself, I had by this time convinced myself that, somehow, the mushrooms were involved. What Kennedy expected to find I could not guess. But from what I had read I surmised that it must be that one of the poisonous varieties had somehow got mixed with the others, one of the Amanitas, just as deadly as the venom of the rattler or the copperhead. I knew that, in some cases, Amanitas had been used to commit crimes. Was this such a case? We had no trouble in finding the estate of Miss Hargrave, and she was at home. Kennedy lost no time introducing himself and coming to the point of his visit. Madeline Hargrave was a slender, willowy type of girl, pronouncedly blond, striking, precisely the type I should have imagined that Mansfield would have been proud to be seen with. "I've just heard of Mr. Mansfield's illness," she said, anxiously. "Mr. Lewis called me up and told me. I don't see why Miss Grey or Doctor Murray didn't let me know sooner." She said it with an air of vexation, as though she felt slighted. In spite of her evident anxiety to know about the tragedy, however, I did not detect the depth of feeling that Helen Grey had shown. In fact, the thoughtfulness of Fleming Lewis almost led me to believe that it was he, rather than Mansfield, for whom she really cared. We chatted a few minutes, as Kennedy told what little we had discovered. He said nothing about the spangle. "By the way," remarked Craig, at length, "I would very much like to have a look at that famous mushroom-cellar of yours." For the first time she seemed momentarily to lose her poise. "I've always had a great interest in mushrooms," she explained, hastily. "You--you do not think it could be the mushrooms--that have caused Mr. Mansfield's illness, do you?" Kennedy passed off the remark as best he could under the circumstances. Though she was not satisfied with his answer, she could not very well refuse his request, and a few minutes later we were down in the dark dampness of the cellar back of the house, where Kennedy set to work on a most exhaustive search. I could see by the expression on his face, as his search progressed, that he was not finding what he had expected. Clearly, the fungi before us were the common edible mushrooms. The upper side of each, as he examined it, was white, with brownish fibrils, or scales. Underneath, some were a beautiful salmon-pink, changing gradually to almost black in the older specimens. The stem was colored like the top. But search as he might for what I knew he was after, in none did he find anything but a small or more often no swelling at the base, and no "cup," as it is called. As he rose after his thorough search, I saw that he was completely baffled. "I hardly thought you'd find anything," Miss Hargrave remarked, noticing the look on his face. "I've always been very careful of my mushrooms." "You have certainly succeeded admirably," he complimented. "I hope you will let me know how Mr. Mansfield is," she said, as we started back toward our car on the road. "I can't tell you how I feel. To think that, after a party which he gave for me, he should be taken ill, and not only that but be robbed at the same time! Really, you must let me know--or I shall have to come up to the city." It seemed gratuitous for Kennedy to promise, for I knew that he was by no means through with her yet; but she thanked him, and we turned back toward town. "Well," I remarked, as we reeled off the miles quickly, "I must say that that puts me all at sea again. I had convinced myself that it was a case of mushroom poisoning. What can you do now?" "Do?" he echoed. "Why, go on. This puts us a step nearer the truth, that's all." Far from being discouraged at what had seemed to me to be a fatal blow to the theory, he now seemed to be actually encouraged. Back in the city, he lost no time in getting to the laboratory again. A package from the botanical department of the university was waiting there for Kennedy, but before he could open it the telephone buzzed furiously. I could gather from Kennedy's words that it was Helen Grey. "I shall be over immediately," he promised, as he hung up the receiver and turned to me. "Mansfield is much worse. While I get together some material I must take over there, Walter, I want you to call up Miss Hargrave and tell her to start for the city right away--meet us at Mansfield's. Then get Mina Leitch and Lewis. You'll find their numbers in the book--or else you'll have to get them from Miss Grey." While I was delivering the messages as diplomatically as possible Kennedy had taken a vial from a medicine-chest, and then from a cabinet a machine which seemed to consist of a number of collars and belts fastened to black cylinders from which ran tubes. An upright roll of ruled paper supported by a clockwork arrangement for revolving it, and a standard bearing a recording pen, completed the outfit. "I should much have preferred not being hurried," he confessed, as we dashed over in the car to Mansfield's again, bearing the several packages. "I wanted to have a chance to interview Mina Leitch alone. However, it has now become a matter of life or death." Miss Grey was pale and worn as she met us in the living-room. "He's had a sinking-spell," she said, tremulously. "Doctor Murray managed to bring him around, but he seems so much weaker after it. Another might--" She broke off, unable to finish. A glance at Mansfield was enough to convince any one that unless something was done soon the end was not far. "Another convulsion and sinking-spell is about all he can stand," remarked Doctor Murray. "May I try something?" asked Kennedy, hardly waiting for the doctor to agree before he had pulled out the little vial which I had seen him place in his pocket. Deftly Kennedy injected some of the contents into Mansfield's side, then stood anxiously watching the effect. The minutes lengthened. At least he seemed to be growing no worse. In the next room, on a table, Kennedy was now busy setting out the scroll of ruled paper and its clockwork arrangement, and connecting the various tubes from the black cylinders in such a way that the recording pen just barely touched on the scroll. He had come back to note the still unchanged condition of the patient when the door opened and a handsome woman in the early thirties entered, followed by Helen Grey. It was Mina Leitch. "Oh, isn't it terrible! I can hardly believe it!" she cried, paying no attention to us as she moved over to Doctor Murray. I recalled what Miss Grey had said about Mansfield's attentions. It was evident that, as far as Mina was concerned, her own attentions were monopolized by the polished physician. His manner in greeting her told me that Doctor Murray appreciated it. Just then Fleming Lewis bustled in. "I thought Miss Hargrave was here," he said, abruptly, looking about. "They told me over the wire she would be." "She should be here any moment," returned Kennedy, looking at his watch and finding that considerably over an hour had elapsed since I had telephoned. What it was I could not say, but there was a coldness toward Lewis that amounted to more than latent hostility. He tried to appear at ease, but it was a decided effort. There was no mistaking his relief when the tension was broken by the arrival of Madeline Hargrave. The circumstances were so strange that none of them seemed to object while Kennedy began to explain, briefly, that, as nearly as he could determine, the illness of Mansfield might be due to something eaten at the supper. As he attached the bands about the necks and waists of one after another of the guests, bringing the little black cylinders thus close to the middle of their chests, he contrived to convey the impression that he would like to determine whether any one else had been affected in a lesser degree. I watched most intently the two women who had just come in. One would certainly not have detected from their greeting and outward manner anything more than that they were well acquainted. But they were an interesting study, two quite opposite types. Madeline, with her baby-blue eyes, was of the type that craved admiration. Mina's black eyes flashed now and then imperiously, as though she sought to compel what the other sought to win. As for Fleming Lewis, I could not fail to notice that he was most attentive to Madeline, though he watched, furtively, but none the less keenly, every movement and word of Mina. His preparations completed, Kennedy opened the package which had been left at the laboratory just before the hasty call from Miss Grey. As he did so he disclosed several specimens of a mushroom of pale-lemon color, with a center of deep orange, the top flecked with white bits. Underneath, the gills were white and the stem had a sort of veil about it. But what interested me most, and what I was looking for, was the remains of a sort of dirty, chocolate-colored cup at the base of the stem. "I suppose there is scarcely any need of saying," began Kennedy, "that the food which I suspect in this case is the mushrooms. Here I have some which I have fortunately been able to obtain merely to illustrate what I am going to say. This is the deadly Amanita muscaria, the fly-agaric." Madeline Hargrave seemed to be following him with a peculiar fascination. "This Amanita," resumed Kennedy, "has a long history, and I may say that few species are quite so interesting. Macerated in milk, it has been employed for centuries as a fly-poison, hence its name. Its deadly properties were known to the ancients, and it is justly celebrated because of its long and distinguished list of victims. Agrippina used it to poison the Emperor Claudius. Among others, the Czar Alexis of Russia died of eating it. "I have heard that some people find it only a narcotic, and it is said that in Siberia there are actually Amanita debauchees who go on prolonged tears by eating the thing. It may be that it does not affect some people as it does others, but in most cases that beautiful gossamer veil which you see about the stem is really a shroud. "The worst of it is," he continued, "that this Amanita somewhat resembles the royal agaric, the Amanita caesarea. It is, as you see, strikingly beautiful, and therefore all the more dangerous." He ceased a moment, while we looked in a sort of awe at the fatally beautiful thing. "It is not with the fungus that I am so much interested just now, however," Kennedy began again, "but with the poison. Many years ago scientists analyzed its poisonous alkaloids and found what they called bulbosine. Later it was named muscarin, and now is sometimes known as amanitin, since it is confined to the mushrooms of the Amanita genus. "Amanitin is a wonderful and dangerous alkaloid, which is absorbed in the intestinal canal. It is extremely violent. Three to five one-thousandths of a gram, or six one-hundredths of a grain, are very dangerous. More than that, the poisoning differs from most poisons in the long time that elapses between the taking of it and the first evidences of its effects. "Muscarin," Kennedy concluded, "has been chemically investigated more often than any other mushroom poison and a perfect antidote has been discovered. Atropin, or belladonna, is such a drug." For a moment I looked about at the others in the room. Had it been an accident, after all? Perhaps, if any of the others had been attacked, one might have suspected that it was. But they had not been affected at all, at least apparently. Yet there could be no doubt that it was the poisonous muscarin that had affected Mansfield. "Did you ever see anything like that?" asked Kennedy, suddenly, holding up the gilt spangle which he had found on the closet floor near the wall safe. Though no one said a word, it was evident that they all recognized it. Lewis was watching Madeline closely. But she betrayed nothing except mild surprise at seeing the spangle from her dress. Had it been deliberately placed there, it flashed over me, in order to compromise Madeline Hargrave and divert suspicion from some one else? I turned to Mina. Behind the defiance of her dark eyes I felt that there was something working. Kennedy must have sensed it even before I did, for he suddenly bent down over the recording needle and the ruled paper on the table. "This," he shot out, "is a pneumograph which shows the actual intensity of the emotions by recording their effects on the heart and lungs together. The truth can literally be tapped, even where no confession can be extracted. A moment's glance at this line, traced here by each of you, can tell the expert more than words." "Then it was a mushroom that poisoned Jack!" interrupted Lewis, suddenly. "Some poisonous Amanita got mixed with the edible mushrooms?" Kennedy answered, quickly, without taking his eyes off the line the needle was tracing: "No; this was a case of the deliberate use of the active principle itself, muscarin--with the expectation that the death, if the cause was ever discovered, could easily be blamed on such a mushroom. Somehow--there were many chances--the poison was slipped into the ramekin Francois was carefully preparing for Mansfield. The method does not interest me so much as the fact--" There was a slight noise from the other room where Mansfield lay. Instantly we were all on our feet. Before any of us could reach the door Helen Grey had slipped through it. "Just a second," commanded Kennedy, extending the sequin toward us to emphasize what he was about to say. "The poisoning and the robbery were the work of one hand. That sequin is the key that has unlocked the secret which my pneumograph has recorded. Some one saw that robbery committed--knew nothing of the contemplated poisoning to cover it. To save the reputation of the robber--at any cost--on the spur of the moment the ruse of placing the sequin in the closet occurred." Madeline Hargrave turned to Mina, while I recalled Lewis's remark about Mina's stepping on the train and tearing it. The defiance in her black eyes flashed from Madeline to Kennedy. "Yes," she cried; "I did it! I--" As quickly the defiance had faded. Mina Leitch had fainted. "Some water--quick!" cried Kennedy. I sprang through the door into Mansfield's room. As I passed I caught sight of Helen Grey supporting the head of Mansfield--both oblivious to actresses, diamonds, everything that had so nearly caused a tragedy. "No," I heard Kennedy say to Lewis as I returned; "it was not Mina. The person she shielded was wildly in love with her, insanely jealous of Mansfield for even looking at her, and in debt so hopelessly in Mansfield's ventures that only the big diamond could save him--Doctor Murray himself!" III THE SOUL-ANALYSIS "Here's the most remarkable appeal," observed Kennedy, one morning, as he tossed over to me a letter. "What do you make of that?" It read: MONTROSE, CONN. MY DEAR PROFESSOR KENNEDY: You do not know me, but I have heard a great deal about you. Please, I beg of you, do not disregard this letter. At least try to verify the appeal I am making. I am here at the Belleclaire Sanatorium, run by Dr. Bolton Burr, in Montrose. But it is not a real sanatorium. It is really a private asylum. Let me tell my story briefly. After my baby was born I devoted myself to it. But, in spite of everything, it died. Meanwhile my husband neglected me terribly. After the baby's death I was a nervous wreck, and I came up here to rest. Now I find I am being held here as an insane patient. I cannot get out. I do not even know whether this letter will reach you. But the chambermaid here has told me she will post it for me. I am ill and nervous--a wreck, but not insane, although they will tell you that the twilight-sleep treatment affected my mind. But what is happening here will eventually drive me insane if some one does not come to my rescue. Cannot you get in to see me as a doctor or friend? I will leave all to you after that. Yours anxiously, JANET (MRS. ROGER) CRANSTON. "What do you make of it yourself?" I returned, handing back the letter. "Are you going to take it up?" He slowly looked over the letter again. "Judging by the handwriting," he remarked, thoughtfully, "I should say that the writer is laboring under keen excitement--though there is no evidence of insanity on the face of it. Yes; I think I'll take up the case." "But how are you going to get in?" I asked. "They'll never admit you willingly." Kennedy pondered a minute. "I'll get in, all right," he said, at length; "come on--I'm going to call on Roger Cranston first." "Roger Cranston?" I repeated, dumfounded. "Why, he'll never help you! Ten to one he's in on it." "We'll have to take a chance," returned Kennedy, hurrying me out of the laboratory. Roger Cranston was a well-known lawyer and man about town. We found him in his office on lower Broadway. He was young and distinguished-looking, which probably accounted for the fact that his office had become a sort of fashionable court of domestic relations. "I'm a friend of Dr. Bolton Burr, of Montrose," introduced Kennedy. Cranston looked at him keenly, but Kennedy was a good actor. "I have been studying some of the patients at the sanatorium, and I have seen Mrs. Cranston there." "Indeed!" responded Cranston. "I'm all broken up by it myself." I could not resist thinking that he took it very calmly, however. "I should like very much to make what we call a psychanalysis of Mrs. Cranston's mental condition," Kennedy explained. "A psychanalysis?" repeated Cranston. "Yes; you know it is a new system. In the field of abnormal psychology, the soul-analysis is of first importance. To-day, this study is of the greatest help in neurology and psychiatry. Only, I can't make it without the consent of the natural guardian of the patient. Doctor Burr tells me that you will have no objection." Cranston thoughtfully studied the wall opposite. "Well," he returned, slowly, "they tell me that without treatment she will soon be hopelessly insane--perhaps dangerously so. That is all I know. I am not a specialist. If Doctor Burr--" He paused. "If you can give me just a card," urged Kennedy, "that is all Doctor Burr wishes." Cranston wrote hastily on the back of one of his cards what Kennedy dictated. Please allow Doctor Kennedy to make a psychanalysis of my wife's mental condition. "You will let me know--if there is--any hope?" he asked. "As soon as I can," replied Kennedy, "I'll let you have a copy of my report." Cranston thanked us and bowed us to the door suavely. "Well," I remarked, as we rode down in the elevator, "that was clever. He fell for it, too. You're an artist. Do you think he was posing?" Kennedy shrugged his shoulders. We lost no time in getting the first train for Montrose, before Cranston had time to reconsider and call up Doctor Burr. The Belleclaire Sanatorium was on the outskirts of the town. It was an old stone house, rather dingy, and surrounded by a high stone wall surmounted by sharp pickets. Dr. Bolton Burr, who was at the head of the institution, met us in the plainly furnished reception-room which also served as his office. Through a window we could see some of the patients walking or sitting about on a small stretch of scraggly grass between the house and the wall. Doctor Burr was a tall and commanding-looking man with a Vandyke beard, and one would instinctively have picked him out anywhere as a physician. "I believe you have a patient here--Mrs. Roger Cranston," began Kennedy, after the usual formalities. Doctor Burr eyed us askance. "I've been asked by Mr. Cranston to make an examination of his wife," pursued Craig, presenting the card which he had obtained from Roger Cranston. "H'm!" mused Doctor Burr, looking quickly from the card to Kennedy with a searching glance. "I wish you would tell me something of the case before I see her," went on Kennedy, with absolute assurance. "Well," temporized Doctor Burr, twirling the card, "Mrs. Cranston came to me after the death of her child. She was in a terrible state. But we are slowly building up her shattered nerves by plain, simple living and a tonic." "Was she committed by her husband?" queried Kennedy, unexpectedly. Whether or not Doctor Burr felt suspicious of us I could not tell. But he seemed eager to justify himself. "I have the papers committing her to my care," he said, rising and opening a safe in the corner. He laid before us a document in which appeared the names of Roger Cranston and Julia Giles. "Who is this Julia Giles?" asked Kennedy, after he had read the document. "One of our nurses," returned the doctor. "She has had Mrs. Cranston under observation ever since she arrived." "I should like to see both Miss Giles and Mrs. Cranston," insisted Kennedy. "It is not that Mr. Cranston is in any way dissatisfied with your treatment, but he thought that perhaps I might be of some assistance to you." Kennedy's manner was ingratiating but firm, and he hurried on, lest it should occur to Doctor Burr to call up Cranston. The doctor, still twirling the card, finally led us through the wide central hall and up an old-fashioned winding staircase to a large room on the second floor. He tapped at the door, which was opened, disclosing an interior tastefully furnished. Doctor Burr introduced us to Miss Giles, conveying the impression, which Kennedy had already given, that he was a specialist, and I his assistant. Janet Cranston was a young and also remarkably beautiful girl. One could see traces of sorrow in her face, which was exceedingly, though not unpleasingly, pale. The restless brilliancy of her eyes spoke of some physical, if not psychical, disorder. She was dressed in deep mourning, which heightened her pallor and excited a feeling of mingled respect and interest. Thick brown coils of chestnut hair were arranged in such a manner as to give an extremely youthful appearance to her delicate face. Her emotions were expressed by the constant motion of her slender fingers. Miss Giles was a striking woman of an entirely different type. She seemed to be exuberant with health, as though nursing had taught her not merely how to take care of others, but had given her the secret of caring, first of all, for herself. I could see, as Doctor Burr introduced us to his patient, that Mrs. Cranston instantly recognized Kennedy's interest in her case. She received us with a graceful courtesy, but she betrayed no undue interest that might excite suspicion, nor was there any hint given of the note of appeal. I wondered whether that might not be an instance of the cunning for which I had heard that the insane are noted. She showed no sign of insanity, however. I looked about curiously to see if there were evidences of the treatment which she was receiving. On a table stood a bottle and a glass, as well as a teaspoon, and I recalled the doctor's remark about the tonic. "You look tired, Mrs. Cranston," remarked Kennedy, thoughtfully. "Why not rest while we are here, and then I will be sure my visit has had no ill effects." "Thank you," she murmured, and I was much impressed by the sweetness of her voice. As he spoke, Kennedy arranged the pillows on a chaise lounge and placed her on it with her head slightly elevated. Having discussed the subject of psychanalysis with Kennedy before, I knew that this was so that nothing might distract her from the free association of ideas. He placed himself near her head, and motioned to us to stand farther back of him, where she could not see us. "Avoid all muscular exertion and distraction," he continued. "I want you to concentrate your attention thoroughly. Tell me anything that comes into your mind. Tell all you know of your symptoms. Concentrate, and repeat all you think of. Frankly express all the thoughts that you have, even though they may be painful and embarrassing." He said this soothingly, and she seemed to understand that much depended upon her answers and the fact of not forcing her ideas. "I am thinking of my husband," Mrs. Cranston began, finally, in a dreamy tone. "What of him?" suggested Kennedy. "Of how the baby--separated us--and--" She paused, almost in tears. From what I knew of the method of psychanalysis, I recalled it was the gaps and hesitations which were most important in arriving at the truth regarding the cause of her trouble. "Perhaps it was my fault; perhaps I was a better mother than wife. I thought I was doing what he would want me to do. Too late I see my mistake." It was easy to read into her story that there had been other women in his life. It had wounded her deeply. Yet it was equally plain that she still loved him. "Go on," urged Kennedy, gently. "Oh yes," she resumed, dreamily; "I am thinking about once, when I left him, I wandered through the country. I remember little except that it was the country through which we had passed on an automobile trip on our honeymoon. Once I thought I saw him, and I tried to get to him. I longed for him, but each time, when I almost reached him, he would disappear. I seemed to be so deserted and alone. I tried to call him, but my tongue refused to say his name. It must have been hours that I wandered about, for I recall nothing after that until I was found, disheveled and exhausted." She paused and closed her eyes, while I could see that Kennedy considered this gap very important. "Don't stop," persisted Kennedy. "Once we quarreled over one of his clients who was suing for a divorce. I thought he was devoting too much time and attention to her. While there might not have been anything wrong, still I was afraid. In my anger and anxiety I accused him. He retorted by slamming the door, and I did not see him for two or three days. I realized my nervous condition, and one day a mutual friend of ours introduced me to Doctor Burr and advised me to take a rest-cure at his sanatorium. By this time Roger and I were on speaking-terms again. But the death of the baby and the quarrel left me still as nervous as before. He seemed anxious to have me do something, and so I came here." "Do you remember anything that happened after that?" asked Craig, for the first time asking a mildly leading question. "Yes; I recall everything that happened when I came here," she went on. "Roger came up with me to complete the necessary arrangements. We were met at the station by Doctor Burr and this woman who has since been my nurse and companion. On the way up from the station to the sanatorium Doctor Burr was very considerate of me, and I noticed that my husband seemed interested in Miss Giles and the care she was to take of me." Kennedy flashed a glance at me from a note-book in which he was apparently busily engaged in jotting down her answers. I did not know just what interpretation to put on it, but surmised that it meant that he had struck what the new psychologists call a "complex," in the entrance of Miss Giles into the case. Before we realized it there came a sudden outburst of feeling. "And now--they are keeping me here by force!" she cried. Doctor Burr looked at us significantly, as much as to say, "Just what might be expected, you see." Kennedy nodded, but made no effort to stop Mrs. Cranston. "They have told Roger that I am insane, and I know he must believe it or he would not leave me here. But their real motive, I can guess, is mercenary. I can't complain about my treatment here--it costs enough." By this time she was sitting bolt upright, staring straight ahead as though amazed at her own boldness in speaking so frankly before them. "I feel all right at times--then--it is as though I had a paralysis of the body, but not of the mind--not of the mind," she repeated, tensely. There was a frightened look on her face, and her voice was now wildly appealing. What would have followed I cannot guess, for at that instant there came a noise outside from another of the rooms as though pandemonium had broken loose. By the shouting and confusion, one might easily have wondered whether keepers and lunatics might not have exchanged places. "It is just one of the patients who has escaped from his room," explained Doctor Burr; "nothing to be alarmed about. We'll soon have him quieted." Doctor Burr hurried out into the corridor while Miss Giles was looking out of the door. Quickly Kennedy reached over and abstracted several drops from a bottle of tonic on the table, pouring it into his handkerchief, which he rolled up tightly and stuffed into his pocket. Mrs. Cranston watched him pleadingly, and clasped her hands in mute appeal, with a hasty glance at Miss Giles. Kennedy said nothing, either, but rapidly folded up a page of the note-book on which he had been writing and shoved it into Mrs. Cranston's hand, together with something he had taken from his pocket. She understood, and quickly placed it in her corsage. "Read it--when you are absolutely alone," he whispered, just as Miss Giles shut the door and turned to us. The excitement subsided almost as quickly as it had arisen, but it had been sufficient to put a stop to any further study of the case along those lines. Miss Giles's keen eyes missed no action or movement of her patient. Doctor Burr returned shortly. It was evident from his manner that he wished to have the visit terminated, and Kennedy seemed quite willing to take the hint. He thanked Mrs. Cranston, and we withdrew quietly, after bidding her good-by in a manner as reassuring as we could make it under the circumstances. "You see," remarked Doctor Burr, as we walked down the hall, "she is quite unstrung still. Mr. Cranston comes up here once in a while, and we notice that after these visits she is, if anything, worse." Down the hall a door had been left open, and we could catch a glimpse of a patient rolled in a blanket, while two nurses forced something down his throat. Doctor Burr hastily closed the door as we passed. "That is the condition Mrs. Cranston might have got into if she had not come to us when she did," he said. "As it is, she is never violent and is one of the most tractable patients we have." We left shortly, without finding out whether Doctor Burr suspected us of anything or not. As we made our way back to the city, I could not help the feeling of depression such as Poe mentioned at seeing the private madhouse in France. "That glimpse we had into the other room almost makes one recall the soothing system of Doctor Maillard. Is Doctor Burr's system better?" I asked. "A good deal of what we used to think and practise is out of date now," returned Kennedy. "I think you are already familiar with the theory of dreams that has been developed by Dr. Sigmund Freud, of Vienna. But perhaps you are not aware of the fact that Freud's contribution to the study of insanity is of even greater scientific value than his dream theories taken by themselves. "Hers, I feel sure now, is what is known as one of the so-called 'border-line cases,'" he continued. "It is clearly a case of hysteria--not the hysteria one hears spoken of commonly, but the condition which scientists know as such. We trace the impulses from which hysterical conditions arise, penetrate the disguises which these repressed impulses or wishes must assume in order to appear in the consciousness. Such transformed impulses are found in normal people, too, sometimes. The hysteric suffers mostly from reminiscences which, paradoxically, may be completely forgotten. "Obsessions and phobias have their origin, according to Freud, in sexual life. The obsession represents a compensation or substitute for an unbearable sexual idea and takes its place in consciousness. In normal sexual life, no neurosis is possible, say the Freudists. Sex is the strongest impulse, yet subject to the greatest repression, and hence the weakest point of our cultural development. Hysteria arises through the conflict between libido and sex-repression. Often sex-wishes may be consciously rejected but unconsciously accepted. So when they are understood every insane utterance has a reason. There is really method in madness. "When hysteria in a wife gains her the attention of an otherwise inattentive husband it fills, from the standpoint of her deeper longing, an important place, and, in a sense, may be said to be desirable. The great point about the psychanalytic method, as discovered by Breuer and Freud, is that certain symptoms of hysteria disappear when the hidden causes are brought to light and the repressed desires are gratified." "How does that apply to Mrs. Cranston?" I queried. "Mrs. Cranston," he replied, "is suffering from what the psychanalysts call a psychic trauma--a soul-wound, as it were. It is the neglect, in this case, of her husband, whom she deeply loves. That, in itself, is sufficient to explain her experience wandering through the country. It was the region which she associated with her first love-affair, as she told us. The wave of recollection that swept over her engulfed her mind. In other words, reason could no longer dominate the cravings for a love so long suppressed. Then, when she saw, or imagined she saw, one who looked like her lover the strain was too great." It was the middle of the afternoon when we reached the laboratory. Kennedy at once set to work studying the drops of tonic which had been absorbed in the handkerchief. As Kennedy worked, I began thinking over again of what we had seen at the Belleclaire Sanatorium. Somehow or other, I could not get out of my mind the recollection of the man rolled in the blanket and trussed up as helpless as a mummy. I wondered whether that alone was sufficient to account for the quickness with which he had been pacified. Then I recalled Mrs. Cranston's remark about her mental alertness and physical weakness. Had it anything to do with the "tonic"? "Suppose, while I am waiting," I finally suggested to Craig, "I try to find out what Cranston does with his time since his wife has been shut off from the world." "That's a very good idea," acquiesced Kennedy. "Don't take too long, however, for I may strike something important here any minute." After several inquiries over the telephone, I found that since his wife had been in Montrose Cranston had closed his apartment and was living at one of his clubs. Having two or three friends who were members, I did not hesitate to drop around. Unfortunately, none of my friends happened to be there, and I was forced, finally, to ask for Cranston himself, although all that I really wanted to know was whether he was there or not. One of the clerks told me that he had been in, but had left in a taxicab only a short time before. As there was a cab-stand outside the club, I determined to make an inquiry and perhaps discover the driver who had had him. The starter knew him, and when I said that it was very important business on which I wanted to see him he motioned to a driver who had just pulled up. A chance for another fare and a generous tip were all that was necessary to induce him to drive me to the Trocadero, a fashionable restaurant and cabaret, where he had taken Cranston a short time before. It was crowded when I entered, and, avoiding the headwaiter, I stood by the door a few minutes and looked over the brilliant and gay throng. Finally, I managed to catch a glimpse of Cranston's head at a table in a far corner. As I made my way down the line of tables, I was genuinely amazed to see that he was with a woman. It was Julia Giles! She must have come down on the next train after we did, but, at any rate, it looked as though she had lost no time in seeking out Cranston after our visit. I took a seat at a table next them. They were talking about Kennedy, and, during a lull in the music, I overheard him asking her just what Craig had done. "It was certainly very clever in him to play both you and Doctor Burr the way he did. He told Doctor Burr that you had sent him, and told you that Doctor Burr had sent him. By whom do you suppose he really was sent?" "Could it have been my wife?" "It must have been, but how she did it is more than I can imagine." "How is she, anyway?" he asked. "Sometimes she seems to be getting along finely, and then, other days, I feel quite discouraged about her. Her case is very obstinate." "Perhaps I had better go out and see Burr," he considered. "It is early in the evening. I'll drive you out in my car. I'll stay at the sanatorium tonight, and then, perhaps, I'll know a little better what we can do." It was his tone rather than his words which gave me the impression that he was more interested in being with Miss Giles than with Mrs. Cranston. I wondered whether it was a plot of Cranston's and Miss Giles's. Had he been posing before Kennedy, and were they really trying to put Mrs. Cranston out of the way? As the music started up again, I heard her say, "Can't we have just one more dance?" A moment later they were lost in the gay whirl on the dancing-floor. They made a handsome couple, and it was evident that it was not the first time that they had dined and danced together. The music ceased, and they returned to their places reluctantly, while Cranston telephoned for his car to be brought around to the cabaret. I hastened back to the laboratory to inform Craig what I had seen. As I told my story he looked up at me with a sudden flash of comprehension. "I am glad to know where they will all be tonight," he said. "Some one has been giving her henbane--hyoscyamin. I have just discovered it in the tonic." "What's henbane?" I asked. "It is a drug derived from the hyoscyamus plant, much like belladonna, though more distinctly sedative. It is a hypnotic used often in mania and mental excitement. The feeling which Mrs. Cranston described is one of its effects. You recall the brightness of her eyes? That is one of the effects of the mydriatic alkaloids, of which this is one. The ancients were familiar with several of its peculiar properties, as they knew of the closely allied poison hemlock. "Many of the text-books at the present time fail to say anything about the remarkable effect produced by large doses of this terrible alkaloid. This effect can be described technically so as to be intelligible, but no description can convey, even approximately, the terrible sensation produced in many insane patients by large doses. In a general way, it is the condition of paralysis of the body without the corresponding paralysis of the mind." "And it's this stuff that somebody has been putting into her tonic?" I asked, startled. "Do you suppose that is part of Burr's system, or did Miss Giles lighten her work by putting it into the tonic?" Kennedy did not betray his suspicion, but went on describing the drug which was having such a serious effect on Mrs. Cranston. "The victim lies in an absolutely helpless condition sometimes with his muscles so completely paralyzed that he cannot so much as move a finger, cannot close his lips or move his tongue to moisten them. This feeling of helplessness is usually followed by unconsciousness and then by a period of depression. The combined feeling of helplessness and depression is absolutely unlike any other feeling imaginable, if I may judge from the accounts of those who have experienced it. Other sensations, such as pain, may be judged, in a measure, by comparison with other painful sensations, but the sensation produced by hyoscyamin in large doses seems to have no basis for comparison. There is no kindred feeling. Practically every institution for the insane used it a few years ago for controlling patients, but now better methods have been devised." "The more I think of what I saw at the Trocadero," I remarked, "the more I wonder if Miss Giles has been seeking to win Cranston herself." "In large-enough doses and repeated often enough," continued Kennedy, "I suppose the toxic effect of the drug might be to produce insanity. At any rate, if we are going to do anything, it might better be done at once. They are all out there now. If we act to-night, surely we shall have the best chance of making the guilty person betray himself." Kennedy telephoned for a fast touring-car, and in half an hour, while he gathered some apparatus together, the car was before the door. In it he placed a couple of light silk-rope ladders, some common wooden wedges, and an instrument which resembled a surveyor's transit with two conical horns sticking out at the ends. We made the trip out of New York and up the Boston post-road, following the route which Cranston and Miss Giles must have taken some hours before us. In the town of Montrose, Kennedy stopped only long enough to get a bite to eat and to study up in the roads in the vicinity. It was long after midnight when we struck up into the country. The night was very dark, thick, and foggy. With the engine running as muffled as possible and the lights dimmed, Kennedy quietly jammed on the brakes as we pulled up along the side of the road. A few rods farther ahead I could make out the Belleclaire Sanatorium surrounded by its picketed stone wall. Not a light was visible in any of the windows. "Now that we're here," I whispered, "what can we do?" "You remember the paper I gave Mrs. Cranston when the excitement in the hall broke loose?" "Yes," I nodded, as we moved over under the shadow of the wall. "I wrote on a sheet from my note-book," said Kennedy, "and told her to be ready when she heard a pebble strike the window; and I gave her a piece of string to let down to the ground." Kennedy threw the silk ladder up until it caught on one of the pickets; then, with the other ladder and the wedges, he reached the top of the wall, followed by me. We pulled the first ladder up as we clung to the pickets, and let it down again inside. Noiselessly we crossed the lawn. Above was Mrs. Cranston's window. Craig picked up some bits of broken stone from a walk about the house and threw them gently against the pane. Then we drew back into the shadow of the house, lest any prying eyes might discover us. In a few minutes the window on the second floor was stealthily opened. The muffled figure of Mrs. Cranston appeared in the dim light; then a piece of string was lowered. To it Kennedy attached a light silk ladder and motioned in pantomime for her to draw it up. It took her some time to fasten the ladder to one of the heavy pieces of furniture in the room. Swaying from side to side, but clinging with frantic desperation to the ladder while we did our best to steady it, she managed to reach the ground. She turned from the building with a shudder, and whispered: "This terrible place! How can I ever thank you for getting me out of it?" Kennedy did not pause long enough to say a word, but hurried her across to the final barrier, the wall. Suddenly there was a shout of alarm from the front of the house under the columns. It was the night watchman, who had discovered us. Instantly Kennedy seized a chair from a little summer-house. "Quick, Walter," he cried, "over the wall with Mrs. Cranston, while I hold him! Then throw the ladder back on this side. I'll join you in a moment, as soon as you get her safely over." A chair is only an indifferent club, if that is all one can think of using it for. Kennedy ran squarely at the watchman, holding it out straight before him. Only once did I cast a hasty glance back. There was the man pinned to the wall by the chair, with Kennedy at the other end of it and safely out of reach. Mrs. Cranston and I managed to scramble over the wall, although she tore her dress on the pickets before we reached the other side. I hustled her into the car and made everything ready to start. It was only a couple of minutes after I threw the ladder back before Craig rejoined us. "How did you get away from the watchman?" I demanded, breathlessly, as we shot away. "I forced him back with the chair into the hall and slammed the door. Then I jammed a wedge under it," he chuckled. "That will hold it better than any lock. Every push will jam it tighter." Above the hubbub, inside now, we could hear a loud gong sounding insistently. All about were lights flashing up at the windows and moving through the passageways. Shouts came from the back of the house as a door was finally opened there. But we were off now, with a good start. I could imagine the frantic telephoning that was going on in the sanatorium. And I knew that the local police of Montrose and every other town about us were being informed of the escape. They were required by the law to render all possible assistance, and, as the country boasted several institutions quite on a par with Belleclaire, an attempt at an escape was not an unusual occurrence. The post-road by which we had come was therefore impossible, and Kennedy swung up into the country, in the hope of throwing off pursuit long enough to give us a better chance. "Take the wheel, Walter," he muttered. "I'll tell you what turns to make. We must get to the State line of New York without being stopped. We can beat almost any car. But that is not enough. A telephone message ahead may stop us, unless we can keep from being seen." I took the wheel, and did not stop the car as Kennedy climbed over the seat. In the back of the car, where Mrs. Cranston was sitting, he hastily adjusted the peculiar apparatus. "Sounds at night are very hard to locate," he explained. "Up this side road, Walter; there is some one coming ahead of us." I turned and shot up the detour, stopping in the shadow of some trees, where we switched off every light and shut down the engine. Kennedy continued to watch the instrument before him. "What is it?" I whispered. "A phonometer," he replied. "It was invented to measure the intensity of sound. But it is much more valuable as an instrument that tells with precision from what direction a sound comes. It needs only a small dry battery and can be carried around easily. The sound enters the two horns of the phonometer, is focused at the neck, and strikes on a delicate diaphragm, behind which is a needle. The diaphragm vibrates and the needle moves. The louder the sound the greater the movement of this needle. "At this end, where it looks as though I were sighting like a surveyor, I am gazing into a lens, with a tiny electric bulb close to my eye. The light of this bulb is reflected in a mirror which is moved by the moving needle. When the sound is loudest the two horns are at right angles to the direction whence it comes. So it is only necessary to twist the phonometer about on its pivot until the sound is received most loudly in the horns and the band of light is greatest. I know then that the horns are at right angles to the direction from which the sound proceeds, and that, as I lift my head, I am looking straight toward the source of the sound. I can tell its direction to a few degrees." I looked through it myself to see how sound was visualized by light. "Hush!" cautioned Kennedy. Down on the main road we could see a car pass along slowly in the direction of Montrose, from which we had come. Without the phonometer to warn us, it must inevitably have met us and blocked our escape over the road ahead. That danger passed, on we sped. Five minutes, I calculated, and we should cross the State line to New York and safety. We had been going along nicely when, "Bang!" came a loud report back of us. "Confound it!" muttered Kennedy; "a blowout always when you least expect it." We climbed out of the car and had the shoe off in short order. "Look!" cried Janet Cranston, in a frightened voice, from the back of the car. The light of the phonometer had flashed up. A car was following us. "There's just one chance!" cried Kennedy, springing to the wheel. "We might make it on the rim." Banging and pounding, we forged ahead, straining our eyes to watch the road, the distance, the time, and the phonometer all at once. It was no use. A big gray roadster was overtaking us. The driver crowded us over to the very edge of the road, then shot ahead, and, where the road narrowed down, deliberately pulled up across the road in such a way that we had to run into him or stop. Quickly Craig's automatic gleamed in the dim beams from the side lights. "Just a minute," cautioned a voice. "It was a plot against me, quite as much as it was against her--the nurse to lead me on, while the doctor got a rich patient. I suspected all was not right. That's why I gave you the card. I knew you didn't come from Burr. Then, when I heard nothing from you, I let the Giles woman think I was coming to Montrose to be with her. But, really, I wanted to beat that fake asylum--" Two piercing headlights shone down the road back of us. We waited a moment until they, too, came to a stop. "Here they are!" shouted the voice of a man, as he jumped out, followed by a woman. Kennedy stepped forward, waving his automatic menacingly. "You are under arrest for conspiracy--both of you!" he cried, as we recognized Doctor Burr and Miss Giles. A little cry behind me startled me, and I turned. Janet Cranston had flung herself into the arms of the only person who could heal her wounded soul. IV THE MYSTIC POISONER "It's almost as though he had been struck down by a spirit hand, Kennedy." Grady, the house detective of the Prince Edward Charles Hotel, had routed us out of bed in the middle of the night with a hurried call for help, and now met us in the lobby of the fashionable hostelry. All that he had said over the wire was that there had been a murder--"an Englishman, a Captain Shirley." "Why," exclaimed Grady, lowering his voice as he led us through the lobby, "it's the most mysterious thing, I think, that I've ever seen!" "In what way?" prompted Kennedy. "Well," continued Grady, "it must have been just a bit after midnight that one of the elevator-boys heard what sounded like a muffled report in a room on the tenth floor. There were other employees and some guests about at the time, and it was only a matter of seconds before they were on the spot. Finally, the sound was located as having come probably from Captain Shirley's room. But the door was locked--on the inside. There was no response, although some one had seen him ride up in the elevator scarcely five minutes before. By that time they had sent for me. We broke in. There was Shirley, alone, fully dressed, lying on the floor before a writing-table. His face was horribly set, as though he had perhaps seen something that frightened and haunted him--though I suppose it might have been the pain that did it. I think he must have heard something, jumped from the chair, perhaps in fear, then have fallen down on the floor almost immediately. "We hurried over to him. He was still alive, but could not speak. I turned him over, tried to rouse him and make him comfortable. It was only then that I saw that he was really conscious. But it seemed as if his tongue and most of his muscles were paralyzed. Somehow he managed to convey to us the idea that it was his heart that troubled him most. "Really, at first I thought it was a case of suicide. But there was no sign of a weapon about and not a trace of poison--no glass, no packet. There was no wound on him, either--except a few slight cuts and scratches on his face and hands. But none of them looked to be serious. And yet, before we could get the house physician up to him he was dead." "And with not a word?" queried Kennedy. "That's the strangest part of it. No; not a word spoken. But as he lay there, even in spite of his paralyzed muscles, he was just able to motion with his hands. I thought he wanted to write, and gave him a pencil and a piece of paper. He clutched at them, but here is all he was able to do." Grady drew from his pocket a piece of paper and handed it to us. On it were printed in trembling, irregular characters, "G A D," the "D" scarcely finished and trailing off into nothing. What did it all mean? How had Shirley met his death, and why? "Tell me something about him," said Kennedy, studying the paper with a frown. Grady shrugged his shoulders. "An Englishman--that's about all I know. Looked like one of the younger sons who so frequently go out to seek their fortunes in the colonies. By his appearance, I should say he had been in the Far East--India, no doubt. And I imagine he had made good. He seemed to have plenty of money. That's all I know about him." "Is anything missing from his room?" I asked. "Could it have been a robbery?" "I searched the room hastily," replied Grady. "Apparently not a thing had been touched. I don't think it was robbery." By this time we had made our way through the lobby and were in the elevator. "I've kept the room just as it was," went on Grady to Kennedy, lowering his voice. "I've even delayed a bit in notifying the police, so that you could get here first." A moment later we entered the rooms, a fairly expensive suite, consisting of a sitting-room, bedroom, and bath. Everything was in a condition to indicate that Shirley had just come in when the shot, if shot it had been, was fired. There, on the floor, lay his body, still in the same attitude in which he had died and almost as Grady had found him gasping. Grady's description of the horrible look on his face was, if anything, an understatement. As I stood with my eyes riveted on the horror-stricken face on the floor, Kennedy had been quietly going over the furniture and carpet about the body. "Look!" he exclaimed at last, scarcely turning to us. On the chair, the writing-table, and even on the walls were little pitted marks and scratches. He bent down over the carpet. There, reflecting the electric light, scattered all about, were little fine pieces of something that glittered. "You have a vacuum cleaner, I suppose?" inquired Craig, rising quickly. "Certainly--a plant in the cellar." "No; I mean one that is portable." "Yes; we have that, too," answered Grady, hurrying to the room telephone to have the cleaner sent up. Kennedy now began to look through Shirley's baggage. There was, however, nothing to indicate that it had been rifled. I noted, among other things, a photograph of a woman in Oriental dress, dusky, languorous, of more than ordinary beauty and intelligence. On it something was written in native characters. Just then a boy wheeled the cleaner down the hall, and Kennedy quickly shoved the photograph into his pocket. First, Kennedy removed the dust that was already in the machine. Then he ran the cleaner carefully over the carpet, the upholstery, everything about that corner of the room where the body lay. When he had finished he emptied out the dust into a paper and placed it in his pocket. He was just finishing when there came a knock at the door, and it was opened. "Mr. Grady?" said a young man, entering hurriedly. "Oh, hello, Glenn! One of the night clerks in the office, Kennedy," introduced the house detective. "I've just heard of the--murder," Glenn began. "I was in the dining-room, being relieved for my little midnight luncheon as usual, when I heard of it, and I thought that perhaps you might want to know something that happened just before I went off duty." "Yes; anything," broke in Kennedy. "It was early in the evening," returned the clerk, slowly, "when a messenger left a little package for Captain Shirley--said that Captain Shirley had had it sent himself and asked that it be placed in his room. It was a little affair in a plain, paper-wrapped parcel. I sent one of the boys up with it and a key, and told him to put the package on the writing-desk tip here." Kennedy looked at me. That, then, was the way something, whatever it might be, was introduced into the room. "When the captain came in," resumed the night clerk, "I saw there was a letter for him in the mailbox and handed it to him. He stood before the office desk while he opened it. I thought he looked queer. The contents seemed to alarm him." "What was in it?" asked Kennedy. "Could you see?" "I got one glimpse. It seemed to be nothing but a little scarlet bead with a black spot on it. In his surprise, he dropped a piece of paper from the envelope in which the bead had been wrapped up. I thought it was strange, and, as he hurried over to the elevator, I picked it up. Here it is." The clerk handed over a crumpled piece of notepaper. On it was scrawled the word "Gadhr," and underneath, "Beware!" I spelled out the first strange word. It had an ominous sound--"Gadhr." Suddenly there flashed through my mind the letters Shirley had tried to print but had not finished, "G A D." Kennedy looked at the paper a moment. "Gadhr!" he exclaimed, in a low, tense tone. "Revolt--the native word for unrest in India, the revolution!" We stared at each other blankly. All of us had been reading lately in the despatches about the troubles there, hidden under the ban of the censorship. I knew that the Hindu propaganda in America was as yet in its infancy, although several plots and conspiracies had been hatched here. "Is there any one in the hotel whom you might suspect?" asked Kennedy. Grady cleared his throat and looked at the night clerk significantly. "Well," he answered, thoughtfully, "across the hall there is a new guest who came to-day--or, rather, yesterday--a Mrs. Anthony. We don't know anything about her, except that she looks like a foreigner. She did not come directly from abroad, but must have been living in New York for some time. They tell me she asked for a room on this floor, at this end of the hall." "H'm!" considered Kennedy. "I'd like to see her--without being seen." "I think I can arrange that," acquiesced Grady. "You and Jameson stay in the bedroom. I'll ask her to come over here, and then you can get a good look at her." The plan satisfied Kennedy, and together we entered the bedroom, putting out the light and leaving the door just a trifle ajar. A moment later Mrs. Anthony entered. I heard a suppressed gasp from Kennedy. "The woman in the photograph!" he whispered to me. I studied her face minutely from our coign of vantage. There was, indeed, a resemblance, too striking to be mere coincidence. In the presence of Grady, she seemed to be nervous and on guard, as though she knew, intuitively, that she was suspected. "Did you know Captain Shirley?" shot out Grady. Kennedy looked over at me and frowned. I knew that something more subtle than New York police methods would be necessary in order to get anything from a woman like this. "No," she replied, quietly. "You see, I just came here to-day." Her voice had an English accent. "Did you hear a shot?" "No," she replied. "The voices in the hall wakened me, though I did not know what was the matter until just now." "Then you made no effort to find out?" inquired Grady, suspiciously. "I am alone here in the city," she answered, simply. "I was afraid to intrude." Throughout she gave the impression that she was strangely reticent about herself. Evidently Kennedy had not much faith that Grady would elicit anything of importance. He tiptoed to the door that led from the bedroom to the hall and found that it could be opened from the inside. While Grady continued his questioning, Craig and I slipped out into the hall to the room which Mrs. Anthony occupied. It was a suite much plainer than that occupied by Shirley. Craig switched on the light and looked about hastily and keenly. For a moment he stood before a dressing-table on which were several toilet articles. A jewel-case seemed to attract his attention, and he opened it. Inside were some comparatively trifling trinkets. The thing that caused him to exclaim, however, was a necklace, broken and unstrung. I looked, too. It was composed of little crimson beads, each with a black spot on it! Quickly he drew from his pocket the photograph he had taken from Shirley's baggage. As I looked at it again there could be no doubt now in my mind of the identity of the original. It was the same face. And about the neck, in the picture, was a necklace, plainly the same as that before us. "What are the beads?" I asked, fingering them. "I've never seen anything like them." "Not beads at all," he replied. "They are Hindu prayer-beans, sometimes called ruttee, jequirity beans, seeds of the plant known to science as Abrus precatorius. They produce a deadly poison--abrin." He slipped four or five of them into his pocket. Then he resumed his cursory search of the room. There, on a writing-pad, was a note which Mrs. Anthony had evidently been engaged in writing. Craig pored over it for some time, while I fidgeted. It was nothing but a queer jumble of letters: SOWC FSSJWA EKNLFFBY WOVHLX IHWAJYKH 101MLEL EPJNVPSL WCLURL GHIHDA ELBA. "Come," I cautioned; "she may return any moment." Quickly he copied off the letters. "It's a cipher," he said, simply, "a new and rather difficult one, too, I imagine. But I may be able to decipher it." Kennedy withdrew from the room and, instead of going back to Shirley's, rode down in the elevator to find the night clerk. "Had Captain Shirley any friends in the city?" asked Craig. Glenn shrugged his shoulders. "He was out most of the time," he replied. "He seemed to be very occupied about something. No, I don't think I ever saw him speak to a soul here, except a word to the waiters and the boys. Once, though," he recollected, "he was called up by a Mrs. Beekman Rogers." "Mrs. Beekman Rogers," repeated Kennedy, jotting the name down and looking it up in the telephone-book. She lived on Riverside Drive, and, slender though the information was, Kennedy seemed glad to get it. Grady joined us a moment later, having been wondering where we had disappeared. "You saw her?" he asked. "What did you think of her?" "Worth watching," was all Kennedy would say. "Did you get anything out of her?" Grady shook his head. "But I am convinced she knows something," he insisted. Kennedy was about to reply when he was interrupted by the arrival of a couple of detectives from the city police, tardily summoned by Grady. "I shall let you know the moment I have discovered anything," he said, as he bade Grady good-by. "And thank you for letting me have a chance at the case before all the clues had been spoiled." Late though it was, in the laboratory Kennedy set to work examining the dust which he had swept up by the vacuum cleaner, as well as the jequirity beans he had taken from Mrs. Anthony's jewel-case. I do not know how much sleep he had, but I managed to snatch a few hours' rest, and early in the morning I found him at work again, examining the cipher message which he had copied. "By the way," he said, scarcely looking up as he saw me again, "there is something quite important which you can do for me." Rather pleased to be of some use, I waited eagerly. "I wish you'd go out and see what you can find out about that Mrs. Beekman Rogers," he continued. "I've some work here that will keep me for several hours; so come back to me here." It was such a commission as he had often given me before, and, through my connection with the Star, I found no difficulty in executing it. I found that Mrs. Rogers was well known in a certain circle of society in the city. She was wealthy and had the reputation of having given quite liberally to many causes that had interested her. Just now, her particular fad was Oriental religions, and some of her bizarre beliefs had attracted a great deal of attention. A couple of years before she had made a trip around the world, and had lived in India for several months, apparently fascinated by the life and attracted to the mysteries of Oriental faiths. With my budget of information I hastened back again to join Kennedy at the laboratory. I could see that the cipher was still unread. From that, I conjectured that it was, as he had guessed, constructed on some new and difficult plan. "What do you think of Mrs. Rogers?" I asked, as I finished reciting what I had learned. "Is it possible that she can be in this revolutionary propaganda?" He shook his head doubtfully. "Much of the disaffection that exists in India to-day," he replied, "is due to the encouragement and financial assistance which it has received from people here in this country, although only a fraction of the natives of India have ever heard of us. Much of the money devoted to the cause of revolution and anarchy in India is contributed by worthy people who innocently believe that their subscriptions are destined to promote the cause of native enlightenment. I prefer to believe that there is some such explanation in her case. At any rate, I think that we had better make a call on Mrs. Rogers." Early that afternoon, accordingly, we found ourselves at the door of the large stone house on Riverside Drive in which Mrs. Rogers lived. Kennedy inquired for her, and we were admitted to a large reception-room, the very decorations of which showed evidence of her leaning toward the Orient. Mrs. Rogers proved to be a widow of baffling age, good-looking, with a certain indefinable attractiveness. Kennedy's cue was obvious. It was to be an eager neophyte in the mysteries of the East, and he played the part perfectly without overdoing it. "Perhaps you would like to come to some of the meetings of our Cult of the Occult," she suggested. "Delighted, I am sure," returned Kennedy. She handed him a card. "We have a meeting this afternoon at four," she explained. "I should be glad to welcome you among us." Kennedy thanked her and rose to go, preferring to say nothing more just then about the problems which vexed us in the Shirley case, lest it should make further investigation more difficult. Nothing more had happened at the hotel, as we heard from Grady a few minutes later, and, as there was some time before the cult met, we returned to the laboratory. Things had evidently progressed well, even in the few hours that he had been studying his meager evidence. Not only was he making a series of delicate chemical tests, but, in cases, he had several guinea-pigs which he was using also. He now studied through a microscope some of the particles of dust from the vacuum cleaner. "Little bits of glass," he said, briefly, taking his eye from the eyepiece. "Captain Shirley was not shot." "Not shot?" I repeated. "Then how was he killed?" Kennedy eyed me gravely. "Shirley was murdered by a poisoned bomb!" I said nothing, for the revelation was even more startling than I had imagined. "In that package which was placed in his room," he went on, "must have been a little infernal machine of glass, constructed so as to explode the moment the wrapper was broken. The flying pieces of glass injected the poison as by a myriad of hypodermic needles--the highly poisonous toxin of abrin, product of the jequirity, which is ordinarily destroyed in the stomach but acts powerfully if injected into the blood. Shirley died of jequirity poisoning, or rather of the alkaloid in the bean. It has been used in India for criminal poisoning for ages. Only, there it is crushed, worked into a paste, and rolled into needle-pointed forms which prick the skin. Abrin is composed of two albuminous bodies, one of which resembles snake-venom in all its effects, attacking the heart, making the temperature fall rapidly, and leaving the blood fluid after death. It is a vegetable toxin, quite comparable with ricin from the castor-oil bean." In spite of my horror at the diabolical plot that had been aimed at Shirley, my mind ran along, keenly endeavoring to piece together the scattered fragments of the case. Some one, of course, had sent the package while he was out and had it placed in his room. Had it been the same person who had sent the single jequirity bean? My mind instantly reverted to the strange woman across the hall, the photograph in his luggage, and the broken necklace in the jewel-case. Kennedy continued looking at the remainder of the jequirity beans and a liquid he had developed from some of them. Finally, with a glance at his watch, he placed a tube of the liquid in a leather case in his pocket. "This may not be the only murder," he remarked, sententiously. "It is best to be prepared. Come; we must get up to that meeting." We journeyed up-town and arrived at the little private hall which the Cult of the Occult had hired somewhat ahead of the time set for the meeting, as Kennedy had aimed to do. Mrs. Rogers was already there and met us at the door. "So glad to see you," she welcomed, leading us in. As we entered we could breathe the characteristic pervading odor of sandalwood. Rich Oriental hangings were on the walls, interspersed with cabalistic signs, while at one end was a raised dais. Mrs. Rogers introduced us to a rather stout, middle-aged, sallow-faced individual in a turban and flowing robes of rustling purple silk. His eyes were piercing, small, and black. The plump, unhealthy, milk-white fingers of his hands were heavy with ornate rings. He looked like what I should have imagined a swami to be, and such, I found, was indeed his title. "The Swami Rajmanandra," introduced Mrs. Rogers. He extended his flabby hand in welcome, while Kennedy eyed him keenly. We were not permitted many words with the swami, however, for Mrs. Rogers next presented us to a younger but no less interesting-looking Oriental who was in Occidental dress. "This is Mr. Singh Bandematarain," said Mrs. Rogers. "You know, he has been sent here by the nizam of his province to be educated at the university." Mrs. Rogers then hastened to conduct us to seats as, one by one, the worshipers entered. They were mostly women of the aristocratic type who evidently found in this cult a new fad to occupy their jaded craving for the sensational. In the dim light, there was something almost sepulchral about the gathering, and their complexions seemed as white as wax. Again the door opened and another woman entered. I felt the pressure of Kennedy's hand on my arm and turned my eyes unobtrusively. It was Mrs. Anthony. Quietly she seemed to glide over the floor toward the swami and, for a moment, stood talking to him. I saw Singh eye her with a curious look. Was it fear or suspicion? I had come expecting to see something weird and wild, perhaps the exhibition of an Indian fakir--I know not what. In that, at least, I was disappointed. The Swami Rajmanandra, picturesque though he was, talked most fascinatingly about his religion, but either the theatricals were reserved for an inner circle or else we were subtly suspected, for I soon found myself longing for the meeting to close so that we could observe those whom we had come to watch. I had almost come to the conclusion that our mission had been a failure when the swami concluded and the visitors swarmed forward to talk with the holy man from the East. Kennedy managed to make his way about the circle to Mrs. Rogers and soon was in an animated conversation. "Were you acquainted with a Captain Shirley?" he asked, finally, as she opened the way for the question by a remark about her life in Calcutta. "Y-yes," she replied, hesitating; "I read in the papers this morning that he was found dead, most mysteriously. Terrible, wasn't it? Yes, I met him in Calcutta while I was there. Why, he was on his way to London, and came to New York and called on me." My eye followed the direction of Mrs. Rogers's. She was talking to us, but really her attention was centered on Mrs. Anthony and the swami together. As I glanced back at her I caught sight of Singh, evidently engaged in watching the same two that I was. Did he have some suspicion of Mrs. Anthony? Why was he watching Mrs. Rogers? I determined to study the two women more closely. I saw that Kennedy had already noticed what I had seen. "One very peculiar thing," he said, deliberately modulating his voice so that it could be heard by those about us, "was that, just before he was killed, some one sent a prayer-bean from a necklace to him." At the mention of the necklace I saw that Mrs. Rogers was all attention. Involuntarily she shot a glance at Mrs. Anthony, as if she noted that she was not wearing the necklace now. "Is that Englishwoman a member of the cult?" queried Kennedy, a moment later, as, quite naturally, he looked over at Mrs. Anthony. "Who is she?" "Oh," replied Mrs. Rogers, quickly, "she isn't an Englishwoman at all. She is a Hindu--I believe, a former nautch-girl, daughter of a nautch-girl. She passes by the name of Mrs. Anthony, but really her name is Kalia Dass. Every one in Calcutta knew her." Kennedy quietly drew his card-case from his pocket and handed a card to Mrs. Rogers. "I should like to talk to you about her some time," he said, in a careful whisper. "If anything happens--don't hesitate to call on me." Before Mrs. Rogers could recover from her surprise Kennedy had said good-by and we were on our way to the laboratory. "That's a curious situation," I observed. "Can you make it out? How does Shirley fit into this thing?" Craig hesitated a moment, as though debating whether to say anything, even to me, about his suspicions. "Suppose," he said, slowly, "that Shirley was a secret agent of the British government, charged with the mission of finding out whether Mrs. Rogers was contributing--unknowingly, perhaps--to hatching another Indian mutiny? Would that suggest anything to you?" "And the nautch-girl whom he had known in Calcutta followed him, hoping to worm from him the secrets which he--" "Not too fast," he cautioned. "Let us merely suppose that Shirley was a spy. If I am not mistaken, we shall see something happen soon, as a result of what I said to Mrs. Rogers." Excited now by the possibilities opened up by his conjecture regarding Shirley, which I knew must have amounted to a certainty in his mind, I watched him impatiently, as he calmly set to work cleaning up the remainder of the laboratory investigation in the affair. It was scarcely half an hour later that a car drove up furiously to our door and Mrs. Rogers burst in, terribly agitated. "You remember," she cried, breathlessly, "you said that a jequirity bean was sent to Captain Shirley?" "Yes," encouraged Kennedy. "Well, after you left, I was thinking about it. That Kalia Dass used to wear a necklace of them, but she didn't have it on to-day. I began thinking about it. While she was talking to the swami I went over. I've noticed how careful she always is of her hand-bag. So I managed to catch my hand in the loop about her wrist. It dropped on the floor. We both made a dive for it, but I got it. I managed, also, to open the catch and, when I picked it up to hand to her, with an apology, what should roll out but a score of prayer-beans! Some papers dropped out, too. She almost tore them from my hands; in fact, one of them did tear. After it was over I had this scrap, a corner torn off one of them." Kennedy took the scrap which she handed to him and studied it carefully, while we looked over his shoulder. On it was a queer alphabetical table. Across the first line were the letters singly, each followed by a dash. Then, in squares underneath, were pairs of letters--AA, BA, CA, DA, and so on, while, vertically, the column on the left read: AA, AB, AC, AD, and so on. "Thank you, Mrs. Rogers," Craig said, rising. "This is very important." She seemed reluctant to go, but, as there was no excuse for staying longer, she finally left. Kennedy immediately set to work studying the scrap of paper and the cipher message he had copied, while I stifled my impatience as best I could. I could do nothing but reflect on the possibility of what a jealous woman might do. Mrs. Rogers had given us one example. Did the same explanation shed any light on the mystery of the nautch-girl and the jequirity bean sent to Shirley? There was no doubt now that Shirley had known her in Calcutta--intimately, also. Perhaps the necklace had some significance. At least, he must have remembered it, as his agitation over the single bean and the word "Gadhr" seemed to indicate. If she had sent it to him, was it as a threat? To all appearance, he had not known that she was in New York, much less that she was at the same hotel and on the same floor. Why had she followed him? Had she misinterpreted his attentions to Mrs. Rogers? Longing to ask Kennedy the myriad questions that flashed through my mind, I turned to him as he scowled at the scrap of paper and the cipher before him. Presently he glanced up at me, still scowling. "It's no use, Walter," he said; "I can't make it out without the key--at least, it will take so long to discover the key that it may be useless." Just then the telephone-bell rang and he sprang to it eagerly. As I listened I gathered that it was another hurried call from Grady. "Something has happened to Mrs. Anthony!" cried Craig, as he hooked up the receiver and seized his hat. A second time we posted to the Prince Edward Charles, spurred by the mystery that surrounded the case. No one met us in the lobby this time, and we rode up directly in the elevator to Mrs. Anthony's room. As we came down the hall and Grady met us at the door, he did not need to tell us that something was wrong. One experience like that with Shirley had put the hotel people on guard, and the house physician was already there, administering stimulants to Mrs. Anthony, who was lying on the bed. "It's just like the other case," whispered Grady. "There are the same scratches on her face and hands." The doctor glanced about at us. By the look on his face, I read that it was a losing fight. Kennedy bent down. The floor about the door was covered with little glittering slivers of glass. On Mrs. Anthony's face was the same drawn look as on Shirley's. Was it a suicide? Had we been getting too close on her trail, or had Mrs. Anthony been attacked? Had some one been using her, and now was afraid of her and sought to get her out of the way for safety? What was the secret locked in her silent lips? The woman was plainly dying. Would she carry the secret with her, after all? Kennedy quickly drew from his pocket the vial which I had seen him place there in the laboratory early in the day. From the doctor's case he selected a hypodermic and coolly injected a generous dose of the stuff into her arm. "What is it?" asked the doctor, as we all watched her face anxiously. "The antitoxin to abrin," he replied. "I developed some of it at the same time that I was studying the poison. If an animal that is immune to a toxin is bled and the serum collected, the antitoxin in it may be injected into a healthy animal and render it immune. Ricin and abrin are vegetable protein toxins of enormous potency and exert a narcotic action. Guinea-pigs fed on them in proper doses attain such a degree of immunity that, in a short time, they can tolerate four hundred times the fatal dose. The serum also can be used to neutralize the toxin in another animal, to a certain extent." We crowded about Kennedy and the doctor, our eyes riveted on the drawn face before us. Would the antitoxin work? Meanwhile, Kennedy moved over to the writing-table which he had examined on our first visit to the room. Covered up in the writing-pad was still the paper which he had copied. Only, Mrs. Anthony had added much more to it. He looked at it desperately. What good would it do if, after hours, his cleverness might solve the cipher--too late? Mrs. Anthony seemed to be struggling bravely. Once I thought she was almost conscious. Glazed though her eyes looked, she saw Kennedy vaguely, with the paper in his hand. Her lips moved. Kennedy bent down, though whether he heard or read her lip movements I do not know. "Her pocket-book!" he exclaimed. We found it crushed under her coat which she had taken off when she entered. Craig opened it and drew forth a crumpled sheet of paper from which a corner had been torn. It exactly fitted the scrap that Mrs. Rogers had given us. There, contained within twenty-seven horizontal and twenty-seven vertical lines, making in all six hundred and seventy-six squares, was every possible combination of two letters of the alphabet. Kennedy looked up, still in desperation. It did him no good. He could have completed the table himself. "In--the--lining." Her lips managed to frame the words. Kennedy literally tore the bag apart. There was nothing but a plain white blank card. With a superhuman effort she moved her lips again. "Smelling-salts," she seemed to say. I looked about. On the dressing-table stood a little dark-green bottle. I pulled the ground-glass stopper from it and a most pungent odor of carbonate of ammonia filled the room. Quickly I held it under her nose, but she shook her head weakly. Kennedy seemed to understand. He snatched the bottle from me and held the card directly over its mouth. As the fumes of the ammonia poured out, I saw faintly on the card the letters HR. We turned to Mrs. Anthony. The effort had used up her strength. She had lapsed again into unconsciousness as Craig bent over her. "Will she live?" lasted. "I think so," he replied, adding a hasty word to the doctor. "What's that? Look!" I exclaimed, pointing to the card from which the letters HR had already faded as mysteriously as they had appeared, leaving the card blank again. "It is the key!" he cried, excitedly. "Written in sympathetic ink. At last we have it all." On the queer alphabetical table which the two pieces of paper made, he now wrote quickly the alphabet again, horizontally across the top, starting with H, and vertically down the side, starting with R, thus: H I J K L M N O P Q R S T U V W X Y Z A B C D E F G R a- b- c- d- e- f- g- h- i- j- k- l- m- n- o- p- q- r- s- t- u- v- w- x- y- z-S aa ba ca da ea fa ga ha ia ja ka la ma na oa pa qa ra sa ta ua va wa xa ya za T ab bb cb db eb fb gb hb ib jb kb lb mb nb ob pb qb rb sb tb ub vb wb xb yb zb U ac bc cc dc ec fc gc hc ic jc kc lc mc nc oc pc qc rc sc tc uc vc wc xc yc zc V ad bd cd dd ed fd gd hd id jd kd ld md nd od pd qd rd sd td ud vd wd xd yd zd W ae be ce de ee fe ge he ie je ke le me ne oe pe qe re se te ue ve we xe ye ze X af bf cf df ef ff gf hf if jf kf lf mf nf of pf qf rf sf tf uf vf wf xf yf zf Y ag bg cg dg eg fg gg hg ig jg kg lg mg ng og pg qg rg sg tg ug vg wg xg yg zg Z ah bh ch dh eh fh gh hh ih jh kh lh mh nh oh ph qh rh sh th uh vy wh xh yh zh & ai bi ci di ei fi gi hi ii ji ki li mi ni oi pi qi ri si ti ui vi wi xi yi zi A aj bj cj dj ej fj gj hj ij jj kj lj mj nj oj pj qj rj sj tj uj vj wj xj yj zj B ak bk ck dk ek fk gk hk ik jk kk lk mk nk ok pk qk rk sk tk uk vk wk xk yk zk C al bl cl dl el fl gl hl il jl kl ll ml nl ol pl ql rl sl tl ul vl wl xl yl zl D am bm cm dm em fm gm hm im jm km lm mm nm om pm qm rm sm tm um vm wm xm ym zm E an bn cn dn en fn gn hn in jn kn ln mn nn on pn qn rn sn tn un vn wn xn yn zn F ao bo co do eo fo go ho io jo ko lo mo no oo po qo ro so to uo vo wo xo yo zo G ap bp cp dp ep fp gp hp ip jp kp lp mp np op pp qp rp sp tp up vp wp xp yp zp H aq bq cq dq eq fq gq hq iq jq kq lq mq nq oq pq qq rq sq tq uq vq wq xq yq zq I ar br cr dr er fr gr hr ir jr kr lr mr nr or pr qr rr sr tr ur vr wr xr yr zr J as bs cs ds es fs gs hs is js ks ls ms ns os ps qs rs ss ts us vs ws xs ys zs K at bt ct dt et ft gt ht it jt kt lt mt nt ot pt qt rt st tt ut vt wt xt yt zt L au bu cu du eu fu gu hu iu ju ku lu mu nu ou pu qu ru su tu uu vu wu xu yu zu M av bv cv dv ev fv gv hv iv jv kv lv mv nv ov pv qv rv sv tv uv vv wv xv yv zv N aw bw cw dw ew fw gw hw iw jw kw lw mw nw ow pw qw rw sw tw uw vw ww xw yw zw O ax bx cx dx ex fx gx hx ix jx kx lx mx nx ox px qx rx sx tx ux vx wx xx yx zx P ay by cy dy ey fy gy hy iy jy ky ly my ny oy py qy ry sy ty uy vy wy xy yy zy Q az bz cz dz ez fz gz hz iz jz kz lz mz nz oz pz qz rz sz tz uz vz wz xz yz zz "See!" exclaimed Kennedy, triumphantly, working rapidly. "Take the word 'war' for instance. The square which contains WA is in line S, column D. So I put down SD. The odd letter R, with a dash, is in line R, column Y. So I put down RY. WAR thus becomes SDRY. Working it backward from SDRY, I take the two letters SD. In line S, column D, I find WA in the square, and in line R, column Y, I find just R--making the translation of the cipher read 'War.' Now," he went on, excitedly, "take the message we have: "SOWC FSSJWA EKNLFFBY WOVHLX IHWAJYKH 101MLEL EPJNVPSL WCLURL GHIHDA ELBA. "I translate each pair of letters as I come to them." He was writing rapidly. There was the message: Have located New York headquarters at 101 Eveningside Avenue, Apartment K. Kennedy did not pause, but dashed from the room, followed by Grady and myself. As our taxi pulled up on the avenue, we saw that the address was a new but small apartment-house. We entered and located Apartment K. Casting about for a way to get in, Craig discovered that the fire-escape could be reached from a balcony by the hall window. He swung himself over the gap, and we followed. It was the work of only a minute to force the window-latch. We entered. No one was there. As we pressed after him, he stopped short and flashed his electric bull's-eye about with an exclamation of startled surprise. There was a fully equipped chemical and electrical laboratory. There were explosives enough to have blown not only us but a whole block to kingdom come. More than that, it was a veritable den of poisons. On a table stood beakers and test-tubes in which was crushed a paste that still showed parts of the red ruttee beans. "Some one planned here to kill Shirley, get him out of the way," reconstructed Kennedy, gazing about; "some one working under the cloak of Oriental religion." "Mrs. Anthony?" queried Grady. Kennedy shook his head. "On the contrary, like Shirley, she was an agent of the Indian Secret Service. The rest of the cipher shows it. She was sent to watch some one else, as he was sent to watch Mrs. Rogers. Neither could have known that the other was on the case. She found out, first, that the package with the prayer-bean and the word 'Gadhr' was an attempt to warn and save Shirley, whom she had known in Calcutta and still loved, but feared to compromise. She must have tried to see him, but failed. She hesitated to write, but finally did. Then some one must have seen that she was dangerous. Another poisoned bomb was sent to her. No; the nautch-girl is innocent." "'Sh!" cautioned Grady. Outside we could hear the footsteps of some one coming along the hall. Kennedy snapped off his light. The door opened. "Stand still! One motion and I will throw it!" As Kennedy's voice rang out from the direction of the table on which stood the half-finished glass bombs, Grady and I flung ourselves forward at the intruder, not knowing what we would encounter. A moment later Kennedy had found the electric switch and flashed up the lights. It was Singh, who had used both Mrs. Rogers's money and Raimanandra's religion to cover his conspiracy of revolt. V THE PHANTOM DESTROYER "Guy Fawkes himself would shudder in that mill. Think of it--five explosions on five successive days, and not a clue!" Our visitor had presented a card bearing the name of Donald MacLeod, chief of the Nitropolis Powder Company's Secret Service. It was plain that he was greatly worried over the case about which he had at last been forced to consult Kennedy. As he spoke, I remembered having read in the despatches about the explosions, but the accounts had been so meager that I had not realized that there was anything especially unusual about them, for it was at the time when accidents in and attacks on the munitions-plants were of common occurrence. "Why," went on MacLeod, "the whole business is as mysterious as if there were some phantom destroyer at work! The men are so frightened that they threaten to quit. Several have been killed. There's something strange about that, too. There are ugly rumors of poisonous gases being responsible, quite as much as the explosions, though, so far, I've been able to find nothing in that notion." "What sort of place is it?" asked Kennedy, interested at once. "Well, you see," explained MacLeod, "since the company's business has increased so fast lately, it has been forced to erect a new plant. Perhaps you have heard of the Old Grove Amusement Park, which failed? It's not far from that." MacLeod looked at us inquiringly, and Kennedy nodded to go on, though I am sure neither of us was familiar with the place. "They've called the new plant Nitropolis--rather a neat name for a powder-works, don't you think?" resumed MacLeod. "Everything went along all right until a few days ago. Then one of the buildings, a storehouse, was blown up. We couldn't be sure that it was an accident, so we redoubled our precautions. It was of no use. That started it. The very next day another building was blown up, then another, until now there have been five of them. What may happen to-day Heaven only knows! I want to get back as soon as I can." "Rather too frequent, I must admit, to be coincidences," remarked Kennedy. "No; they can't all be accidents," asserted MacLeod, confidently. "There's too great regularity for that. I think I've considered almost everything. I don't see how they can be from bombs placed by workmen. At least, it's not a bit likely. Besides, the explosions all occur in broad daylight, not at night. We're very careful about the men we employ, and they're watched all the time. The company has a guard of its own, twenty-five picked men, under me--all honorably discharged United States army men." "You have formed no theory of your own?" queried Kennedy. MacLeod paused, then drew from his pocket the clipping of a despatch from the front in which one of the war correspondents reported the destruction of wire entanglements with heat supposed to have been applied by the use of reflecting mirrors. "I'm reduced to pure speculation," he remarked. "To-day they seem to be reviving all the ancient practices. Maybe some one is going at it like Archimedes." "Not impossible," returned Craig, handing back the clipping. "Buffon tested the probability of the achievement of Archimedes in setting fire to the ships of Marcellus with mirrors and the sun's rays. He constructed a composite mirror of a hundred and twenty-eight plane mirrors, and with it he was able to ignite wood at two hundred and ten feet. However, I shrewdly suspect that, even if this story is true, they are using hydrogen or acetylene flares over there. But none of these things would be feasible in your case. You'd know it." "Could it be some one who is projecting a deadly wireless force which causes the explosions?" I put in, mindful of a previous case of Kennedy's. "We all know that inventors have been working for years on the idea of making explosives obsolete and guns junk. If some one has hit on a way of guiding an electric wave through the air and concentrating power at a point, munitions-plants could be wiped out." MacLeod looked anxiously from me to Kennedy, but Craig betrayed nothing by his face except his interest. "Sometimes I have imagined I heard a peculiar, faint, whirring noise in the air," he remarked, thoughtfully. "I thought of having the men on the watch for air-ships, but they've never seen a trace of one. It might be some power either like this," he added, shaking the clipping, "or like that which Mr. Jameson suggests." "It's something like that you meant, I presume, when you called it a 'phantom destroyer' a moment ago?" asked Kennedy. MacLeod nodded. "If you're interested," he pursued, hastily, "and feel like going down there to look things over, I think the best place for you to go would be to the Sneddens'. They're some people who have seen a chance to make a little money out of the boom. Many visitors are now coming and going on business connected with the new works. They have started a boarding-house--or, rather, Mrs. Snedden has. There's a daughter, too, who seems to be very popular." Kennedy glanced whimsically at me. "Well, Walter," he remarked, tentatively, "entirely aside from the young lady, this ought to make a good story for the Star." "Indeed it ought!" I replied, enthusiastically. "Then you'll go down to Nitropolis?" queried MacLeod, eagerly. "You can catch a train that will get you there about noon. And the company will pay you well." "MacLeod, with the mystery, Miss Snedden, and the remuneration, you are irresistible," smiled Kennedy. "Thank you," returned the detective. "You won't regret it. I can't tell you how much relieved I feel to have some one else, and, above all, yourself, on the case. You can get a train in half an hour. I think it would be best for you to go as though you had no connection with me--at least for the present." Kennedy agreed, and MacLeod excused himself, promising to be on the train, although not to ride with us, in case we should be the target of too inquisitive eyes. For a few moments, while our taxicab was coming, Kennedy considered thoughtfully what the company detective had said. By the time the vehicle arrived he had hurriedly packed up some apparatus in two large grips, one of which it fell to my lot to carry. The trip down to Nitropolis was uninteresting, and we arrived at the little station shortly after noon. MacLeod was on the train, but did not speak to us, and it was perhaps just as well, for the cabmen and others hanging about the station were keenly watching new arrivals, and any one with MacLeod must have attracted attention. We selected or were, rather, selected by one of the cabmen and driven immediately to the Snedden house. Our cover was, as Craig and I had decided, to pose as two newspaper men from New York, that being the easiest way to account for any undue interest we might show in things. The powder-company's plant was situated on a large tract of land which was surrounded by a barbed-wire fence, six feet high and constructed in a manner very similar to the fences used in protecting prison-camps in war-times. At various places along the several miles of fence gates were placed, with armed guards. Many other features were suggestive of war-times. One that impressed us most was that each workman had to carry a pass similar, almost, to a passport. This entire fence, we learned, was patrolled day and night by armed guards. A mile or so from the plant, or just outside the main gate, quite a settlement had grown up, like a mushroom, almost overnight--the product of a flood of new money. Originally, there had been only one house for some distance about--that of the Sneddens. But now there were scores of houses, mostly those of officials and managers, some of them really pretentious affairs. MacLeod himself lived in one of them, and we could see him ahead of us, being driven home. The workmen lived farther along the line, in a sort of company town, which at present greatly resembled a Western mining-camp, though ultimately it was to be a bungalow town. Just at present, however, it was the Snedden house that interested us most, for we felt the need of getting ourselves established in this strange community. It was an old-fashioned farm-house and had been purchased very cheaply by Snedden several years before. He had altered it and brought it up to date, and the combination of old and new proved to be typical of the owner as well as of the house. Kennedy carried off well the critical situation of our introduction, and we found ourselves welcomed rather than scrutinized as intruders. Garfield Snedden was much older than his second wife, Ida. In fact, she did not seem to be much older than Snedden's daughter Gertrude, whom MacLeod had already mentioned--a dashing young lady, never intended by nature to vegetate in the rural seclusion that her father had sought before the advent of the powder-works. Mrs. Snedden was one of those capable women who can manage a man without his knowing it. Indeed, one felt that Snedden, who was somewhat of both student and dreamer, needed a manager. "I'm glad your train was on time," bustled Mrs. Snedden. "Luncheon will be ready in a few moments now." We had barely time to look about before Gertrude led us into the dining-room and introduced us to the other boarders. Knowing human nature, Kennedy was careful to be struck with admiration and amazement at everything we had seen in our brief whirl through Nitropolis. It was not a difficult or entirely assumed feeling, either, when one realized that, only a few short months before, the region had been nothing better than an almost hopeless wilderness of scrub-pines. We did not have to wait long before the subject uppermost in our minds was brought up--the explosions. Among the boarders there were at least two who, from the start, promised to be interesting as well as important. One was a tall, slender chap named Garretson, whose connection with the company, I gathered from the conversation, took him often on important matters to New York. The other was an older man, Jackson, who seemed to be connected with the management of the works, a reticent fellow, more given to listening to others than to talking himself. "Nothing has happened so far to-day, anyhow," remarked Garretson, tapping the back of his chair with his knuckle, as a token of respect for that evil spirit who seems to be exorcised by knocking wood. "Oh," exclaimed Gertrude, with a little half-suppressed shudder, "I do hope those terrible explosions are at last over!" "If I had my way," asserted Garretson, savagely, "I'd put this town under martial law until they WERE over." "It may come to that," put in Jackson, quietly. "Quite in keeping with the present tendency of the age," agreed Snedden, in a tone of philosophical disagreement. "I don't think it makes much difference how you accomplish the result, Garfield," chimed in his wife, "as long as you accomplish it, and it is one that should be accomplished." Snedden retreated into the refuge of silence. Though this was only a bit of the conversation, we soon found out that he was an avowed pacifist. Garretson, on the other hand, was an ardent militarist, a good deal of a fire-eater. I wondered whether there might not be a good deal of the poseur about him, too. It needed no second sight to discover that both he and Gertrude were deeply interested in each other. Garretson was what Broadway would call "a live one," and, though there is nothing essentially wrong in that, I fancied that I detected, now and then, an almost maternal solicitude on the part of her stepmother, who seemed to be watching both the young man and her husband alternately. Once Jackson and Mrs. Snedden exchanged glances. There seemed to be some understanding between them. The time to return to the works was approaching, and we all rose. Somehow, Gertrude and Garretson seemed naturally to gravitate toward the door together. Some distance from the house there was a large barn. Part of it had been turned into a garage, where Garretson kept a fast car. Jackson, also, had a roadster. In fact, in this new community, with its superabundant new wealth, everybody had a car. Kennedy and I sauntered out after the rest. As we turned an angle of the house we came suddenly upon Garretson in his racer, talking to Gertrude. The crunch of the gravel under our feet warned them before we saw them, but not before we could catch a glimpse of a warning finger on the rosy lips of Gertrude. As she saw us she blushed ever so slightly. "You'll be late!" she cried, hastily. "Mr. Jackson has been gone five minutes." "On foot," returned Garretson, nonchalantly. "I'll overtake him in thirty seconds." Nevertheless, he did not wait longer, but swung up the road at a pace which was the admiration of all speed-loving Nitropolitans. Craig had ordered our taxicab driver to stop for us after lunch, and, without exciting suspicion, managed to stow away the larger part of the contents of our grips in his car. Still without openly showing our connection with MacLeod, Kennedy sought out the manager of the works, and, though scores of correspondents and reporters from various newspapers had vainly applied for permission to inspect the plant, somehow we seemed to receive the freedom of the place and without exciting suspicion. Craig's first move was to look the plant over. As we approached it our attention was instantly attracted to the numerous one-story galvanized-iron buildings that appeared to stretch endlessly in every direction. They seemed to be of a temporary nature, though the power-plants, offices, and other necessary buildings were very substantially built. The framework of the factory-buildings was nothing but wood, covered by iron sheathing, and even the sides seemed to be removable. The floors, however, were of concrete. "They serve their purpose well," observed Kennedy, as we picked our way about. "Explosions at powder-mills are frequent, anyhow. After an explosion there is very little debris to clear away, as you may imagine. These buildings are easily repaired or replaced, and they keep a large force of men for these purposes, as well as materials for any emergency." One felt instinctively the hazard of the employment. Everywhere were signs telling what not and what to do. One that stuck in my mind was, "It is better to be careful than sorry." Throughout the plant at frequent intervals were first-aid stations with kits for all sorts of accidents, including respirators, for workmen were often overcome by ether or alcohol fumes. Everything was done to minimize the hazard, yet one could not escape the conviction that human life and limb were as much a cost of production in this industry as fuel and raw material. Once, in our wanderings about the plant, I recall we ran across both Garretson and Jackson in one of the offices. They did not see us, but seemed to be talking very earnestly about something. What it was we could not guess, but this time it seemed to be Jackson who was doing most of the talking. Kennedy watched them as they parted. "There's something peculiar under the surface with those people at the boarding-house," was all he observed. "Come; over there, about an eighth of a mile, I think I see evidences of the latest of the explosions. Let's look at it." MacLeod had evidently reasoned that, sooner of later, Kennedy would appear in this part of the grounds, and as we passed one of the shops he joined us. "You mentioned something about rumors of poisonous gases," hinted Craig, as we walked along. "Yes," assented MacLeod; "I don't know what there is in it. I suppose you know that there is a very poisonous gas, carbon monoxide, or carbonic oxide, formed in considerable quantity by the explosion of several of the powders commonly used in shells. The gas has the curious power of combining with the blood and refusing to let go, thus keeping out the oxygen necessary for life. It may be that that is what accounts for what we've seen--that it is actual poisoning to death of men not killed by the immediate explosion." We had reached the scene of the previous day's disaster. No effort had yet been made to clear it up. Kennedy went over it carefully. What it was he found I do not know, but he had not spent much time before he turned to me. "Walter," he directed, "I wish you would go back to the office near the gate, where I left that paraphernalia we brought down. Carry it over--let me see--there's an open space there on that knoll. I'll join you there." Whatever was in the packages was both bulky and heavy, and I was glad to reach the hillside he had indicated. Craig was waiting for me there with MacLeod, and at once opened the packages. From them he took a thin steel rod, which he set up in the center of the open space. To it he attached a frame and to the frame what looked like four reversed megaphones. Attached to the frame, which was tubular, was an oak box with a little arrangement of hard rubber and metal which fitted into the ears. For some time Kennedy's face wore a set, far-away expression, as if he were studying something. "The explosions seem always to occur in the middle of the afternoon," observed MacLeod, fidgeting apprehensively. Kennedy motioned petulantly for silence. Then suddenly he pulled the tubes out of his ears and gazed about sharply. "There's something in the air!" he cried. "I can hear it!" MacLeod and I strained our eyes. There was nothing visible. "This is an anti-aircraft listening-post, such as the French use," explained Craig, hurriedly. "Between the horns and the microphone in the box you can catch the hum of an engine, even when it is muffled. If there's an aeroplane or a Zeppelin about, this thing would locate it." Still, there was nothing that we could see, though now the sound was just perceptible to the ear if one strained his attention a bit. I listened. It was plain in the detector; yet nothing was visible. What strange power could it be that we could not see or feel in broad daylight? Just then came a low rumbling, and then a terrific roar from the direction of the plant. We swung about in time to see a huge cloud of debris lifted literally into the air above the tree-tops and dropped to earth again. The silence that succeeded the explosion was eloquent. The phantom destroyer had delivered his blow again. "The distillery--where we make the denatured alcohol!" cried MacLeod, gazing with tense face as from other buildings, we could see men pouring forth, panic-stricken, and the silence was punctured by shouts. Kennedy bent over his detector. "That same mysterious buzzing," he muttered, "only fainter." Together we hastened now toward the distillery, another of those corrugated-iron buildings. It had been completely demolished. Here and there lay a dark, still mass. I shuddered. They were men! As we ran toward the ruin we crossed a baseball-field which the company had given the men. I looked back for Kennedy. He had paused at the wire backstop behind the catcher. Something caught in the wires interested him. By the time I reached him he had secured it--a long, slender metal tube, cleverly weighted so as to fall straight. "Not a hundred per cent. of hits, evidently," he muttered. "Still, one was enough." "What is it?" asked MacLeod. "An incendiary pastille. On contact, the nose burns away anything it hits, goes right through corrugated iron. It carries a charge of thermit ignited by this piece of magnesium ribbon. You know what thermit will penetrate with its thousands of degrees of heat. Only the nose of this went through the netting and never touched a thing. This didn't explode anything, but another one did. Thousands of gallons of alcohol did the rest." Kennedy had picked up his other package as we ran, and was now busily unwrapping it. I looked about at the crowd that had collected, and saw that there was nothing we could do to help. Once I caught sight of Gertrude's face. She was pale, and seemed eagerly searching for some one. Then, in the crowd, I lost her. I turned to MacLeod. He was plainly overwhelmed. Kennedy was grimly silent and at work on something he had jammed into the ground. "Stand back!" he cautioned, as he touched a match to the thing. With a muffled explosion, something whizzed and shrieked up into the air like a sky-rocket. Far above, I could now see a thing open out like a parachute, while below it trailed something that might have been the stick of the rocket. Eagerly Kennedy followed the parachute as the wind wafted it along and it sank slowly to the earth. When, at last, he recovered it I saw that between the parachute and the stick was fastened a small, peculiar camera. "A Scheimpflug multiple camera," he explained as he seized it almost ravenously. "Is there a place in town where I can get the films in this developed quickly?" MacLeod, himself excited now, hurried us from the scene of the explosion to a local drug-store, which combined most of the functions of a general store, even being able to improvise a dark-room in which Kennedy could work. It was some time after the excitement over the explosion had quieted down that MacLeod and I, standing impatiently before the drug-store, saw Snedden wildly tearing down the street in his car. He saw us and pulled up at the curb with a jerk. "Where's Gertrude?" he shouted, wildly. "Has any one seen my daughter?" Breathlessly he explained that he had been out, had returned to find his house deserted, Gertrude gone, his wife gone, even Jackson's car gone from the barn. He had been to the works. Neither Garretson nor Jackson had been seen since the excitement of the explosion, they told him. Garretson's racer was gone, too. There seemed to have been a sort of family explosion, also. Kennedy had heard the loud talking and had left his work to the druggist to carry on and joined us. There was no concealment now of our connection with MacLeod, for it was to him that every one in town came when in trouble. In almost no time, so accurately did he keep his fingers on the fevered pulse of Nitropolis, MacLeod had found out that Gertrude had been seen driving away from the company's grounds with some one in Garretson's car, probably Garretson himself. Jackson had been seen hurrying down the street. Some one else had seen Ida Snedden in Jackson's car, alone. Meanwhile, over the wire, MacLeod had sent out descriptions of the four people and the two cars, in the hope of intercepting them before they could be plunged into the obscurity of any near-by city. Not content with that, MacLeod and Kennedy started out in the former's car, while I climbed in with Snedden, and we began a systematic search of the roads out of Nitropolis. As we sped along, I could not help feeling, though I said nothing, that, somehow, the strange disappearances must have something to do with the mysterious phantom destroyer. I did not tell even Snedden about the little that Kennedy had discovered, for I had learned that it was best to let Craig himself tell, at his own time and in his own way. But the man seemed frantic in his search, and I could not help the impression that there was something, perhaps only a suspicion, that he knew which might shed some light. We were coming down the river, or, rather, the bay, after a fruitless search of unfrequented roads and were approaching the deserted Old Grove Amusement Park, to which excursions used, years ago, to come in boats. No one could make it pay, and it was closed and going to ruin. There had been some hint that Garretson's racer might have disappeared down this unfrequented river road. As we came to a turn in the road, we could see Kennedy and MacLeod in their car, coming up. Instead of keeping on, however, they turned into the grove, Kennedy leaning far over the running-board as MacLeod drove slowly, following his directions, as though Craig were tracing something. With a hurried exclamation of surprise, Snedden gave our car the gas and shot ahead, swinging around after them. They were headed, following some kind of tire-tracks, toward an old merry-go-round that was dismantled and all boarded up. They heard us coming and stopped. "Has any one told you that Garretson's car went down the river road, too?" called Snedden, anxiously. "No; but some one thought he saw Jackson's car come down here," called back MacLeod. "Jackson's?" exclaimed Snedden. "Maybe both are right," I ventured, as we came closer. "What made you turn in here?'" "Kennedy thought he saw fresh tire-tracks running into the grove." We were all out of our cars by this time, and examining the soft roadway with Craig. It was evident to any one that a car had been run in, and not so very long ago, in the direction of the merry-go-round. We followed the tracks on foot, bending about the huge circle of a building until we came to the side away from the road. The tracks seemed to run right in under the boards. Kennedy approached and touched the boards. They were loose. Some one had evidently been there, had taken them down, and put them up. In fact, by the marks on them, it seemed as though he had made a practice of doing so. MacLeod and Kennedy unhooked the boarding, while Snedden looked on in a sort of daze. They had taken down only two or three sections, which indicated that that whole side might similarly be removed, when I heard a low, startled exclamation from Snedden. We peered in. There, in the half-light of the gloomy interior, we could see a car. Before we knew it Snedden had darted past us. An instant later I distinguished what his more sensitive eye had seen--a woman, all alone in the car, motionless. "Ida!" he cried. There was no answer. "She--she's dead!" he shouted. It was only too true. There was Ida Snedden, seated in Jackson's car in the old deserted building, all shut up--dead. Yet her face was as pink as if she were alive and the blood had been whipped into her cheeks by a walk in the cold wind. We looked at one another, at a loss. How did she get there--and why? She must have come there voluntarily. No one had seen any one else with her in the car. Snedden was now almost beside himself. "Misfortunes never come singly," he wailed. "My daughter Gertrude gone--now my wife dead. Confound that young fellow Garretson--and Jackson, too! Where are they? Why have they fled? The scoundrels--they have stolen my whole family. Oh, what shall I do? what shall I do?" Trying to quiet Snedden, at the same time we began to look about the building. On one side was a small stove, in which were still the dying coals of a fire. Near by were a work-bench, some tools, pieces of wire, and other material. Scattered about were pieces of material that looked like celluloid. Some one evidently used the place as a secret workshop. Kennedy picked up a piece of the celluloid-like stuff and carefully touched a match to it. It did not burn rapidly as celluloid does, and Craig seemed more than ever interested. MacLeod himself was no mean detective. Accustomed to action, he had an idea of what to do. "Wait here!" he called back, dashing out. "I'm going to the nearest house up the road for help. I'll be back in a moment." We heard him back and turn his car and shoot away. Meanwhile, Kennedy was looking over carefully Jackson's roadster. He tapped the gas-tank in the rear, then opened it. There was not a drop of gas in it. He lifted up the hood and looked inside at the motor. Whatever he saw there, he said nothing. Finally, by siphoning some gas from Snedden's tank and making some adjustments, he seemed to have the car in a condition again for it to run. He was just about to start it when MacLeod returned, carrying a canary-bird in a cage. "I've telephoned to town," he announced. "Some one will be here soon now. Meanwhile, an idea occurred to me, and I borrowed this bird. Let me see whether the idea is any good." Kennedy, by this time, had started the engine. MacLeod placed the bright little songster near the stove on the work-bench and began to watch it narrowly. More than ever up in the air over the mystery, I could only watch Kennedy and MacLeod, each following his own lines. It might, perhaps, have been ten minutes after MacLeod returned, and during that time he had never taken his eyes off the bird, when I began to feel a little drowsy. A word from MacLeod roused me. "There's carbon monoxide in the air, Kennedy!" he exclaimed. "You know how this gas affects birds." Kennedy looked over intently. The canary had begun to show evident signs of distress over something. "It must be that this stove is defective," pursued MacLeod, picking up the poor little bird and carrying it quickly into the fresh air, where it could regain its former liveliness. Then, when he returned, he added, "There must be some defect in the stove or the draught that makes it send out the poisonous gas." "There's some gas," agreed Kennedy. "It must have cleared away mostly, though, or we couldn't stand it ourselves." Craig continued to look about the car and the building, in the vain hope of discovering some other clue. Had Mrs. Snedden been killed by the carbonic oxide? Was it a case of gas poisoning? Then, too, why had she been here at all? Who had shut her up? Had she been overcome first and, in a stupor, been unable to move to save herself? Above all, what had this to do with the mysterious phantom slayer that had wrecked so much of the works in less than a week? It was quite late in the afternoon when, at last, people came from the town and took away both the body of Mrs. Snedden and Jackson's car. Snedden could only stare and work his fingers, and after we had seen him safely in the care of some one we could trust Kennedy, MacLeod, and I climbed into MacLeod's car silently. "It's too deep for me," acknowledged MacLeod. "What shall we do next?" "Surely that fellow must have my pictures developed by this time," considered Kennedy. "Shoot back there." "They came out beautifully--all except one," reported the druggist, who was somewhat of a camera fiend himself. "That's a wonderful system, sir." Kennedy thanked him for his trouble and took the prints. With care he pieced them together, until he had several successive panoramas of the country taken from various elevations of the parachute. Then, with a magnifying-glass, he went over each section minutely. "Look at that!" he pointed out at last with the sharp tip of a pencil on one picture. In what looked like an open space among some trees was a tiny figure of a man. It seemed as if he were hacking at something with an ax. What the something was did not appear in the picture. "I should say that it was half a mile, perhaps a mile, farther away than that grove," commented Kennedy, making a rough calculation. "On the old Davis farm," considered MacLeod. "Look and see if you can't make out the ruins of a house somewhere near-by. It was burned many years ago." "Yes, yes," returned Kennedy, excitedly; "there's the place! Do you think we can get there in a car before it's dark?" "Easily," replied MacLeod. It was only a matter of minutes before we three were poking about in a tangle of wood and field, seeking to locate the spot where Kennedy's apparatus had photographed the lone axman. At last, in a large, cleared field, we came upon a most peculiar heap of debris. As nearly as I could make out, it was a pile of junk, but most interesting junk. Practically all of it consisted in broken bits of the celluloid-like stuff we had seen in the abandoned building. Twisted inextricably about were steel wires and bits of all sorts of material. In the midst of the wreckage was something that looked for all the world like the remains of a gas-motor. It was not rusted, either, which indicated that it had been put there recently. As he looked at it, Craig's face displayed a smile of satisfaction. "Looks as though it might have been an aeroplane of the tractor type," he vouchsafed, finally. "Surely there couldn't have been an accident," objected MacLeod. "No aviator could have lived through it, and there's no body." "No; it was purposely destroyed," continued Craig. "It was landed here from somewhere else for that purpose. That was what the man in the picture was doing with the ax. After the last explosion something happened. He brought the machine here to destroy the evidence." "But," persisted MacLeod, "if there had been an aeroplane hovering about we should have seen it in the air, passing over the works at the time of the explosion." Kennedy picked the pieces, significantly. "Some one about here has kept abreast of the times, if not ahead. See; the planes were of this non-inflammable celluloid that made it virtually transparent and visible only at a few hundred feet in the air. The aviator could fly low and so drop those pastilles accurately--and unseen. The engine had one of those new muffler-boxes. He would have been unheard, too, except for that delicate air-ship detector." MacLeod and I could but stare at each other, aghast. Without a doubt it was in the old merry-go-round building that the phantom aviator had established his hangar. What the connection was between the tragedy in the Snedden family and the tragedy in the powder-works we did not know, but, at least, now we knew that there was some connection. It was growing dark rapidly, and, with some difficulty, we retraced our steps to the point where we had left the car. We whirled back to the town, and, of course, to the Snedden house. Snedden was sitting in the parlor when we arrived, by the body of his wife, staring, speechless, straight before him, while several neighbors were gathered about, trying to console him. We had scarcely entered when a messenger-boy came up the path from the gate. Both Kennedy and MacLeod turned toward him, expecting some reply to the numerous messages of alarm sent out earlier in the afternoon. "Telegram for Mrs. Snedden," announced the boy. "MRS. Snedden?" queried Kennedy, surprised, then quickly: "Oh yes, that's all right. I'll take care of it." He signed for the message, tore it open, and read it. For a moment his face, which had been clouded, smoothed out, and he took a couple of turns up and down the hall, as though undecided. Finally he crumpled the telegram abstractedly and shoved it into his pocket. We followed him as he went into the parlor and stood for several moments, looking fixedly on the strangely flushed face of Mrs. Snedden. "MacLeod," he said, finally, turning gravely toward us, and, for the present, seeming to ignore the presence of the others, "this amazing series of crimes has brought home to me forcibly the alarming possibilities of applying modern scientific devices to criminal uses. New modes and processes seem to bring new menaces." "Like carbon-monoxide poisoning?" suggested MacLeod. "Of course it has long been known as a harmful gas, but--" "Let us see," interrupted Kennedy. "Walter, you were there when I examined Jackson's car. There was not a drop of gasolene in the tank, you will recall. Even the water in the radiator was low. I lifted the hood. Some one must have tampered with the carburetor. It was adjusted so that the amount of air in the mixture was reduced. More than that, I don't know whether you noticed it or not, but the spark and gas were set so that, when I did put gasolene in the tank, I had but to turn the engine over and it went. In other words, that car had been standing there, the engine running, until it simply stopped for want of fuel." He paused while we listened intently, then resumed. "The gas-engine and gas-motor have brought with them another of those unanticipated menaces of which I spoke. Whenever the explosion of the combustible mixture is incomplete or of moderated intensity a gas of which little is known may be formed in considerable quantities. "In this case, as in several others that have come to my attention, vapors arising from the combustion must have emitted certain noxious products. The fumes that caused Ida Snedden's death were not of carbon monoxide from the stove, MacLeod. They were splitting-products of gasolene, which are so new to science that they have not yet been named. "Mrs. Snedden's death, I may say for the benefit of the coroner, was due to the absorption of some of these unidentified gaseous poisons. They are as deadly as a knife-thrust through the heart, under certain conditions. Due to the non-oxidation of some of the elements of gasolene, they escape from the exhaust of every running gas-engine. In the open air, where only a whiff or two would be inhale now and then, they are not dangerous. But in a closed room they may kill in an incredibly short time. In fact, the condition has given rise to an entirely new phenomenon which some one has named 'petromortis.'" "Petromortis?" repeated Snedden, who, for the first time, began to show interest in what was going on about him. "Then it was an accident?" "I did not say it was an accident," corrected Craig. "There is an old adage that murder will out. And this expression of human experience is only repeated in what we modern scientific detectives are doing. No man bent on the commission of a crime can so arrange the circumstances of that crime that it will afterward appear, point by point, as an accident." Kennedy had us all following him breathlessly now. "I do not consider it an accident," he went on, rapidly piecing together the facts as we had found them. "Ida Snedden was killed because she was getting too close to some one's secret. Even at luncheon, I could see that she had discovered Gertrude's attachment for Garretson. How she heard that, following the excitement of the explosion this afternoon, Gertrude and Garretson had disappeared, I do not pretend to know. But it is evident that she did hear, that she went out and took Jackson's car, probably to pursue them. If we have heard that they went by the river road, she might have heard it, too. "In all probability she came along just in time to surprise some one working on the other side of the old merry-go-round structure. There can be no reason to conceal the fact longer. From that deserted building some one was daily launching a newly designed invisible aeroplane. As Mrs. Snedden came along, she must have been just in time to see that person at his secret hangar. What happened I do not know, except that she must have run the car off the river road and into the building. The person whom she found must have suddenly conceived a method of getting her out of the way and making it look like an accident of some kind, perhaps persuaded her to stay in the car with the engine running, while he went off and destroyed the aeroplane which was damning evidence now." Startling as was the revelation of an actual phantom destroyer, our minds were more aroused as to who might be the criminal who had employed such an engine of death. Kennedy drew from his pocket the telegram which had just arrived, and spread it out flat before us on a table. It was dated Philadelphia, and read: MRS. IDA SNEDDEN, Nitropolis: Garretson and Gertrude were married to-day. Have traced them to the Wolcott. Try to reconcile Mr. Snedden. HUNTER JACKSON. I saw at once that part of the story. It was just a plain love-affair that had ended in an elopement at a convenient time. The fire-eating Garretson had been afraid of the Sneddens and Jackson, who was their friend. Before I could even think further, Kennedy had drawn out the films taken by the rocket-camera. "With the aid of a magnifying-glass," he was saying, "I can get just enough of the lone figure in this picture to identify it. These are the crimes of a crazed pacifist, one whose mind had so long dwelt on the horrors of--" "Look out!" shouted MacLeod, leaping in front of Kennedy. The strain of the revelation had been too much. Snedden--a raving maniac--had reeled forward, wildly and impotently, at the man who had exposed him. VI THE BEAUTY MASK "Oh, Mr. Jameson, if they could only wake her up--find out what is the matter--do something! This suspense is killing both mother and myself." Scenting a good feature story, my city editor had sent me out on an assignment, my sole equipment being a clipping of two paragraphs from the morning Star. GIRL IN COMA SIX DAYS--SHOWS NO SIGN OF REVIVAL Virginia Blakeley, the nineteen-year-old daughter of Mrs. Stuart Blakeley, of Riverside Drive, who has been in a state of coma for six days, still shows no sign of returning consciousness. Ever since Monday some member of her family has been constantly beside her. Her mother and sister have both vainly tried to coax her back to consciousness, but their efforts have not met with the slightest response. Dr. Calvert Haynes, the family physician, and several specialists who have been called in consultation, are completely baffled by the strange malady. Often I had read of cases of morbid sleep lasting for days and even for weeks. But this was the first case I had ever actually encountered and I was glad to take the assignment. The Blakeleys, as every one knew, had inherited from Stuart Blakeley a very considerable fortune in real estate in one of the most rapidly developing sections of upper New York, and on the death of their mother the two girls, Virginia and Cynthia, would be numbered among the wealthiest heiresses of the city. They lived in a big sandstone mansion fronting the Hudson and it was with some misgiving that I sent up my card. Both Mrs. Blakeley and her other daughter, however, met me in the reception-room, thinking, perhaps, from what I had written on the card, that I might have some assistance to offer. Mrs. Blakeley was a well-preserved lady, past middle-age, and very nervous. "Mercy, Cynthia!" she exclaimed, as I explained my mission, "it's another one of those reporters. No, I cannot say anything--not a word. I don't know anything. See Doctor Haynes. I--" "But, mother," interposed Cynthia, more calmly, "the thing is in the papers. It may be that some one who reads of it may know of something that can be done. Who can tell?" "Well, I won't say anything," persisted the elder woman. "I don't like all this publicity. Did the newspapers ever do anything but harm to your poor dear father? No, I won't talk. It won't do us a bit of good. And you, Cynthia, had better be careful." Mrs. Blakeley backed out of the door, but Cynthia, who was a few years older than her sister, had evidently acquired independence. At least she felt capable of coping with an ordinary reporter who looked no more formidable than myself. "It is quite possible that some one who knows about such cases may learn of this," I urged. She hesitated as her mother disappeared, and looked at me a moment, then, her feelings getting the better of her, burst forth with the strange appeal I have already quoted. It was as though I had come at just an opportune moment when she must talk to some outsider to relieve her pent-up feelings. By an adroit question here and there, as we stood in the reception-hall, I succeeded in getting the story, which seemed to be more of human interest than of news. I even managed to secure a photograph of Virginia as she was before the strange sleep fell on her. Briefly, as her sister told it, Virginia was engaged to Hampton Haynes, a young medical student at the college where his father was a professor of diseases of the heart. The Hayneses were of a fine Southern family which had never recovered from the war and had finally come to New York. The father, Dr. Calvert Haynes, in addition to being a well-known physician, was the family physician of the Blakeleys, as I already knew. "Twice the date of the marriage has been set, only to be postponed," added Cynthia Blakeley. "We don't know what to do. And Hampton is frantic." "Then this is really the second attack of the morbid sleep?" I queried. "Yes--in a few weeks. Only the other wasn't so long--not more than a day." She said it in a hesitating manner which I could not account for. Either she thought there might be something more back of it or she recalled her mother's aversion to reporters and did not know whether she was saying too much or not. "Do you really fear that there is something wrong?" I asked, significantly, hastily choosing the former explanation. Cynthia Blakeley looked quickly at the door through which her mother had retreated. "I--I don't know," she replied, tremulously. "I don't know why I am talking to you. I'm so afraid, too, that the newspapers may say something that isn't true." "You would like to get at the truth, if I promise to hold the story back?" I persisted, catching her eye. "Yes," she answered, in a low tone, "but--" then stopped. "I will ask my friend, Professor Kennedy, at the university, to come here," I urged. "You know him?" she asked, eagerly. "He will come?" "Without a doubt," I reassured, waiting for her to say no more, but picking up the telephone receiver on a stand in the hall. Fortunately I found Craig at his laboratory and a few hasty words were all that was necessary to catch his interest. "I must tell mother," Cynthia cried, excitedly, as I hung up the receiver. "Surely she cannot object to that. Will you wait here?" As I waited for Craig, I tried to puzzle the case out for myself. Though I knew nothing about it as yet, I felt sure that I had not made a mistake and that there was some mystery here. Suddenly I became aware that the two women were talking in the next room, though too low for me to catch what they were saying. It was evident, however, that Cynthia was having some difficulty in persuading her mother that everything was all right. "Well, Cynthia," I heard her mother say, finally, as she left the room for one farther back, "I hope it will be all right--that is all I can say." What was it that Mrs. Blakeley so feared? Was it merely the unpleasant notoriety? One could not help the feeling that there was something more that she suspected, perhaps knew, but would not tell. Yet, apparently, it was aside from her desire to have her daughter restored to normal. She was at sea, herself, I felt. "Poor dear mother!" murmured Cynthia, rejoining me in a few moments. "She hardly knows just what it is she does want-except that we want Virginia well again." We had not long to wait for Craig. What I had told him over the telephone had been quite enough to arouse his curiosity. Both Mrs. Blakeley and Cynthia met him, at first a little fearfully, but quickly reassured by his manner, as well as my promise to see that nothing appeared in the Star which would be distasteful. "Oh, if some one could only bring back our little girl!" cried Mrs. Blakeley, with suppressed emotion, leading the way with her daughter up-stairs. It was only for a moment that I could see Craig alone to explain the impressions I had received, but it was enough. "I'm glad you called me," he whispered. "There is something queer." We followed them up to the dainty bedroom in flowered enamel where Virginia Blakeley lay, and it was then for the first time that we saw her. Kennedy drew a chair up beside the little white bed and went to work almost as though he had been a physician himself. Partly from what I observed myself and partly from what he told me afterward, I shall try to describe the peculiar condition in which she was. She lay there lethargic, scarcely breathing. Once she had been a tall, slender, fair girl, with a sort of wild grace. Now she seemed to be completely altered. I could not help thinking of the contrast between her looks now and the photograph in my pocket. Not only was her respiration slow, but her pulse was almost imperceptible, less than forty a minute. Her temperature was far below normal, and her blood pressure low. Once she had seemed fully a woman, with all the strength and promise of precocious maturity. But now there was something strange about her looks. It is difficult to describe. It was not that she was no longer a young woman, but there seemed to be something almost sexless about her. It was as though her secondary sex characteristics were no longer feminine, but--for want of a better word--neuter. Yet, strange to say, in spite of the lethargy which necessitated at least some artificial feeding, she was not falling away. She seemed, if anything, plump. To all appearances there was really a retardation of metabolism connected with the trance-like sleep. She was actually gaining in weight! As he noted one of these things after another, Kennedy looked at her long and carefully. I followed the direction of his eyes. Over her nose, just a trifle above the line of her eyebrows, was a peculiar red mark, a sore, which was very disfiguring, as though it were hard to heal. "What is that?" he asked Mrs. Blakeley, finally. "I don't know," she replied, slowly. "We've all noticed it. It came just after the sleep began." "You have no idea what could have caused it?" "Both Virginia and Cynthia have been going to a face specialist," she admitted, "to have their skins treated for freckles. After the treatment they wore masks which were supposed to have some effect on the skin. I don't know. Could it be that?" Kennedy looked sharply at Cynthia's face. There was no red mark over her nose. But there were certainly no freckles on either of the girls' faces now, either. "Oh, mother," remonstrated Cynthia, "it couldn't be anything Doctor Chapelle did." "Doctor Chapelle?" repeated Kennedy. "Yes, Dr. Carl Chapelle," replied Mrs. Blakeley. "Perhaps you have heard of him. He is quite well known, has a beauty-parlor on Fifth Avenue. He--" "It's ridiculous," cut in Cynthia, sharply. "Why, my face was worse than Virgie's. Car--He said it would take longer." I had been watching Cynthia, but it needed only to have heard her to see that Doctor Chapelle was something more than a beauty specialist to her. Kennedy glanced thoughtfully from the clear skin of Cynthia to the red mark on Virginia. Though he said nothing, I could see that his mind was on it. I had heard of the beauty doctors who promise to give one a skin as soft and clear as a baby's--and often, by their inexpert use of lotions and chemicals, succeed in ruining the skin and disfiguring the patient for life. Could this be a case of that sort? Yet how explain the apparent success with Cynthia? The elder sister, however, was plainly vexed at the mention of the beauty doctor's name at all, and she showed it. Kennedy made a mental note of the matter, but refrained from saying any more about it. "I suppose there is no objection to my seeing Doctor Haynes?" asked Kennedy, rising and changing the subject. "None whatever," returned Mrs. Blakeley. "If there's anything you or he can do to bring Virginia out of this--anything safe--I want it done," she emphasized. Cynthia was silent as we left. Evidently she had not expected Doctor Chapelle's name to be brought into the case. We were lucky in finding Doctor Haynes at home, although it was not the regular time for his office hours. Kennedy introduced himself as a friend of the Blakeleys who had been asked to see that I made no blunders in writing the story for the Star. Doctor Haynes did not question the explanation. He was a man well on toward the sixties, with that magnetic quality that inspires the confidence so necessary for a doctor. Far from wealthy, he had attained a high place in the profession. As Kennedy finished his version of our mission, Doctor Haynes shook his head with a deep sigh. "You can understand how I feel toward the Blakeleys," he remarked, at length. "I should consider it unethical to give an interview under any circumstances--much more so under the present." "Still," I put in, taking Kennedy's cue, "just a word to set me straight can't do any harm. I won't quote you directly." He seemed to realize that it might be better to talk carefully than to leave all to my imagination. "Well," he began, slowly, "I have considered all the usual causes assigned for such morbid sleep. It is not auto-suggestion or trance, I am positive. Nor is there any trace of epilepsy. I cannot see how it could be due to poisoning, can you?" I admitted readily that I could not. "No," he resumed, "it is just a case of what we call narcolepsy--pathological somnolence--a sudden, uncontrollable inclination to sleep, occurring sometimes repeatedly or at varying intervals. I don't think it hysterical, epileptic, or toxemic. The plain fact of the matter, gentlemen, is that neither myself nor any of my colleagues whom I have consulted have the faintest idea what it is--yet." The door of the office opened, for it was not the hour for consulting patients, and a tall, athletic young fellow, with a keen and restless face, though very boyish, entered. "My son," the doctor introduced, "soon to be the sixth Doctor Haynes in direct line in the family." We shook hands. It was evident that Cynthia had not by any means exaggerated when she said that he was frantic over what had happened to his fiancee. Accordingly, there was no difficulty in reverting to the subject of our visit. Gradually I let Kennedy take the lead in the conversation so that our position might not seem to be false. It was not long before Craig managed to inject a remark about the red spot over Virginia's nose. It seemed to excite young Hampton. "Naturally I look on it more as a doctor than a lover," remarked his father, smiling indulgently at the young man, whom it was evident he regarded above everything else in the world. "I have not been able to account for it, either. Really the case is one of the most remarkable I have ever heard of." "You have heard of a Dr. Carl Chapelle?" inquired Craig, tentatively. "A beauty doctor," interrupted the young man, turning toward his father. "You've met him. He's the fellow I think is really engaged to Cynthia." Hampton seemed much excited. There was unconcealed animosity in the manner of his remark, and I wondered why it was. Could there be some latent jealousy? "I see," calmed Doctor Haynes. "You mean to infer that this--er--this Doctor Chapelle--" He paused, waiting for Kennedy to take the initiative. "I suppose you've noticed over Miss Blakeley's nose a red sore?" hazarded Kennedy. "Yes," replied Doctor Haynes, "rather refractory, too. I--" "Say," interrupted Hampton, who by this time had reached a high pitch of excitement, "say, do you think it could be any of his confounded nostrums back of this thing?" "Careful, Hampton," cautioned the elder man. "I'd like to see him," pursued Craig to the younger. "You know him?" "Know him? I should say I do. Good-looking, good practice, and all that, but--why, he must have hypnotized that girl! Cynthia thinks he's wonderful." "I'd like to see him," suggested Craig. "Very well," agreed Hampton, taking him at his word. "Much as I dislike the fellow, I have no objection to going down to his beauty-parlor with you." "Thank you," returned Craig, as we excused ourselves and left the elder Doctor Haynes. Several times on our journey down Hampton could not resist some reference to Chapelle for commercializing the profession, remarks which sounded strangely old on his lips. Chapelle's office, we found, was in a large building on Fifth Avenue in the new shopping district, where hundreds of thousands of women passed almost daily. He called the place a Dermatological Institute, but, as Hampton put it, he practised "decorative surgery." As we entered one door, we saw that patients left by another. Evidently, as Craig whispered, when sixty sought to look like sixteen the seekers did not like to come in contact with one another. We waited some time in a little private room. At last Doctor Chapelle himself appeared, a rather handsome man with the manner that one instinctively feels appeals to the ladies. He shook hands with young Haynes, and I could detect no hostility on Chapelle's part, but rather a friendly interest in a younger member of the medical profession. Again I was thrown forward as a buffer. I was their excuse for being there. However, a newspaper experience gives you one thing, if no other--assurance. "I believe you have a patient, a Miss Virginia Blakeley?" I ventured. "Miss Blakeley? Oh yes, and her sister, also." The mention of the names was enough. I was no longer needed as a buffer. "Chapelle," blurted out Hampton, "you must have done something to her when you treated her face. There's a little red spot over her nose that hasn't healed yet." Kennedy frowned at the impetuous interruption. Yet it was perhaps the best thing that could have happened. "So," returned Chapelle, drawing back and placing his head on one side as he nodded it with each word, "you think I've spoiled her looks? Aren't the freckles gone?" "Yes," retorted Hampton, bitterly, "but on her face is this new disfigurement." "That?" shrugged Chapelle. "I know nothing of that--nor of the trance. I have only my specialty." Calm though he appeared outwardly, one could see that Chapelle was plainly worried. Under the circumstances, might not his professional reputation be at stake? What if a hint like this got abroad among his rich clientele? I looked about his shop and wondered just how much of a faker he was. Once or twice I had heard of surgeons who had gone legitimately into this sort of thing. But the common story was that of the swindler--or worse. I had heard of scores of cases of good looks permanently ruined, seldom of any benefit. Had Chapelle ignorantly done something that would leave its scar forever? Or was he one of the few who were honest and careful? Whatever the case, Kennedy had accomplished his purpose. He had seen Chapelle. If he were really guilty of anything the chances were all in favor of his betraying it by trying to cover it up. Deftly suppressing Hampton, we managed to beat a retreat without showing our hands any further. "Humph!" snorted Hampton, as we rode down in the elevator and hopped on a 'bus to go up-town. "Gave up legitimate medicine and took up this beauty doctoring--it's unprofessional, I tell you. Why, he even advertises!" We left Hampton and returned to the laboratory, though Craig had no present intention of staying there. His visit was merely for the purpose of gathering some apparatus, which included a Crookes tube, carefully packed, a rheostat, and some other paraphernalia which we divided. A few moments later we were on our way again to the Blakeley mansion. No change had taken place in the condition of the patient, and Mrs. Blakeley met us anxiously. Nor was the anxiety wholly over her daughter's condition, for there seemed to be an air of relief when Kennedy told her that we had little to report. Up-stairs in the sick-room, Craig set silently to work, attaching his apparatus to an electric-light socket from which he had unscrewed the bulb. As he proceeded I saw that it was, as I had surmised, his new X-ray photographing machine which he had brought. Carefully, from several angles, he took photographs of Virginia's head, then, without saying a word, packed up his kit and started away. We were passing down the hall, after leaving Mrs. Blakeley, when a figure stepped out from behind a portiere. It was Cynthia, who had been waiting to see us alone. "You--don't think Doctor Chapelle had anything to do with it?" she asked, in a hoarse whisper. "Then Hampton Haynes has been here?" avoided Kennedy. "Yes," she admitted, as though the question had been quite logical. "He told me of your visit to Carl." There was no concealment, now, of her anxiety. Indeed, I saw no reason why there should be. It was quite natural that the girl should worry over her lover, if she thought there was even a haze of suspicion in Kennedy's mind. "Really I have found out nothing yet," was the only answer Craig gave, from which I readily deduced that he was well satisfied to play the game by pitting each against all, in the hope of gathering here and there a bit of the truth. "As soon as I find out anything I shall let you and your mother know. And you must tell me everything, too." He paused to emphasize the last words, then slowly turned again toward the door. From the corner of my eye I saw Cynthia take a step after him, pause, then take another. "Oh, Professor Kennedy," she called. Craig turned. "There's something I forgot," she continued. "There's something wrong with mother!" She paused, then resumed: "Even before Virginia was taken down with this--illness I saw a change. She is worried. Oh, Professor Kennedy, what is it? We have all been so happy. And now--Virgie, mother--all I have in the world. What shall I do?" "Just what do you mean?" asked Kennedy, gently. "I don't know. Mother has been so different lately. And now, every night, she goes out." "Where?" encouraged Kennedy, realizing that his plan was working. "I don't know. If she would only come back looking happier." She was sobbing, convulsively, over she knew not what. "Miss Blakeley," said Kennedy, taking her hand between both of his, "only trust me. If it is in my power I shall bring you all out of this uncertainty that haunts you." She could only murmur her thanks as we left. "It is strange," ruminated Kennedy, as we sped across the city again to the laboratory. "We must watch Mrs. Blakeley." That was all that was said. Although I had no inkling of what was back of it all, I felt quite satisfied at having recognized the mystery even on stumbling on it as I had. In the laboratory, as soon as he could develop the skiagraphs he had taken, Kennedy began a minute study of them. It was not long before he looked over at me with the expression I had come to recognize when he found something important. I went over and looked at the radiograph which he was studying. To me it was nothing but successive gradations of shadows. But to one who had studied roentgenography as Kennedy had each minute gradation of light and shade had its meaning. "You see," pointed out Kennedy, tracing along one of the shadows with a fine-pointed pencil, and then along a corresponding position on another standard skiagraph which he already had, "there is a marked diminution in size of the sella turcica, as it is called. Yet there is no evidence of a tumor." For several moments he pondered deeply over the photographs. "And it is impossible to conceive of any mechanical pressure sufficient to cause such a change," he added. Unable to help him on the problem, whatever it might be, I watched him pacing up and down the laboratory. "I shall have to take that picture over again--under different circumstances," he remarked, finally, pausing and looking at his watch. "To-night we must follow this clue which Cynthia has given us. Call a cab, Walter." We took a stand down the block from the Blakeley mansion, near a large apartment, where the presence of a cab would not attract attention. If there is any job I despise it is shadowing. One must keep his eyes riveted on a house, for, once let the attention relax and it is incredible how quickly any one may get out and disappear. Our vigil was finally rewarded when we saw Mrs. Blakeley emerge and hurry down the street. To follow her was easy, for she did not suspect that she was being watched, and went afoot. On she walked, turning off the Drive and proceeding rapidly toward the region of cheap tenements. She paused before one, and as our cab cruised leisurely past we saw her press a button, the last on the right-hand side, enter the door, and start up the stairs. Instantly Kennedy signaled our driver to stop and together we hopped out and walked back, cautiously entering the vestibule. The name in the letter-box was "Mrs. Reba Rinehart." What could it mean? Just then another cab stopped up the street, and as we turned to leave the vestibule Kennedy drew back. It was too late, however, not to be seen. A man had just alighted and, in turn, had started back, also realizing that it was too late. It was Chapelle! There was nothing to do but to make the best of it. "Shadowing the shadowers?" queried Kennedy, keenly watching the play of his features under the arc-light of the street. "Miss Cynthia asked me to follow her mother the other night," he answered, quite frankly. "And I have been doing so ever since." It was a glib answer, at any rate, I thought. "Then, perhaps you know something of Reba Rinehart, too," bluffed Kennedy. Chapelle eyed us a moment, in doubt how much we knew. Kennedy played a pair of deuces as if they had been four aces instead. "Not much," replied Chapelle, dubiously. "I know that Mrs. Blakeley has been paying money to the old woman, who seems to be ill. Once I managed to get in to see her. It's a bad case of pernicious anemia, I should say. A neighbor told me she had been to the college hospital, had been one of Doctor Haynes's cases, but that he had turned her over to his son. I've seen Hampton Haynes here, too." There was an air of sincerity about Chapelle's words. But, then, I reflected that there had also been a similar ring to what we had heard Hampton say. Were they playing a game against each other? Perhaps--but what was the game? What did it all mean and why should Mrs. Blakeley pay money to an old woman, a charity patient? There was no solution. Both Kennedy and Chapelle, by a sort of tacit consent, dismissed their cabs, and we strolled on over toward Broadway, watching one another, furtively. We parted finally, and Craig and I went up to our apartment, where he sat for hours in a brown study. There was plenty to think about even so far in the affair. He may have sat up all night. At any rate, he roused me early in the morning. "Come over to the laboratory," he said. "I want to take that X-ray machine up there again to Blakeley's. Confound it! I hope it's not too late." I lost no time in joining him and we were at the house long before any reasonable hour for visitors. Kennedy asked for Mrs. Blakeley and hurriedly set up the X-ray apparatus. "I wish you would place that face mask which she was wearing exactly as it was before she became ill," he asked. Her mother did as Kennedy directed, replacing the rubber mask as Virginia had worn it. "I want you to preserve that mask," directed Kennedy, as he finished taking his pictures. "Say nothing about it to any one. In fact, I should advise putting it in your family safe for the present." Hastily we drove back to the laboratory and Kennedy set to work again developing the second set of skiagraphs. I had not long to wait, this time, for him to study them. His first glance brought me over to him as he exclaimed loudly. At the point just opposite the sore which he had observed on Virginia's forehead, and overlying the sella turcica, there was a peculiar spot on the radiograph. "Something in that mask has affected the photographic plate," he explained, his face now animated. Before I could ask him what it was he had opened a cabinet where he kept many new things which he studied in his leisure moments. From it I saw him take several glass ampules which he glanced at hastily and shoved into his pocket as we heard a footstep out in the hall. It was Chapelle, very much worried. Could it be that he knew his society clientele was at stake, I wondered. Or was it more than that? "She's dead!" he cried. "The old lady died last night!" Without a word Kennedy hustled us out of the laboratory, stuffing the X-ray pictures into his pocket, also, as we went. As we hurried down-town Chapelle told us how he had tried to keep a watch by bribing one of the neighbors, who had just informed him of the tragedy. "It was her heart," said one of the neighbors, as we entered the poor apartment. "The doctor said so." "Anemia," insisted Chapelle, looking carefully at the body. Kennedy bent over, also, and examined the poor, worn frame. As he did so he caught sight of a heavy linen envelope tucked under her pillow. He pulled it out gently and opened it. Inside were several time-worn documents and letters. He glanced over them hastily, unfolding first a letter. "Walter," he whispered, furtively, looking at the neighbors in the room and making sure that none of them had seen the envelope already. "Read these. That's her story." One glance was sufficient. The first was a letter from old Stuart Blakeley. Reba Rinehart had been secretly married to him--and never divorced. One paper after another unfolded her story. I thought quickly. Then she had had a right in the Blakeley millions. More than that, the Blakeleys themselves had none, at least only what came to them by Blakeley's will. I read on, to see what, if any, contest she had intended to make. And as I read I could picture old Stuart Blakeley to myself--strong, direct, unscrupulous, a man who knew what he wanted and got it, dominant, close-mouthed, mysterious. He had understood and estimated the future of New York. On that he had founded his fortune. According to the old lady's story, the marriage was a complete secret. She had demanded marriage when he had demanded her. He had pointed out the difficulties. The original property had come to him and would remain in his hands only on condition that he married one of his own faith. She was not of the faith and declined to become so. There had been other family reasons, also. They had been married, with the idea of keeping it secret until he could arrange his affairs so that he could safely acknowledge her. It was, according to her story, a ruse. When she demanded recognition he replied that the marriage was invalid, that the minister had been unfrocked before the ceremony. She was not in law his wife and had no claim, he asserted. But he agreed to compromise, in spite of it all. If she would go West and not return or intrude, he would make a cash settlement. Disillusioned, she took the offer and went to California. Somehow, he understood that she was dead. Years later he married again. Meanwhile she had invested her settlement, had prospered, had even married herself, thinking the first marriage void. Then her second husband died and evil times came. Blakeley was dead, but she came East. Since then she had been fighting to establish the validity of the first marriage and hence her claim to dower rights. It was a moving story. As we finished reading, Kennedy gathered the papers together and took charge of them. Taking Chapelle, who by this time was in a high state of excitement over both the death and the discovery, Kennedy hurried to the Blakeley mansion, stopping only long enough to telephone to Doctor Haynes and his son. Evidently the news had spread. Cynthia Blakeley met us in the hall, half frightened, yet much relieved. "Oh, Professor Kennedy," she cried, "I don't know what it is, but mother seems so different. What is it all about?" As Kennedy said nothing, she turned to Chapelle, whom I was watching narrowly. "What is it, Carl?" she whispered. "I--I can't tell," he whispered back, guardedly. Then, with an anxious glance at the rest of us, "Is your sister any better?" Cynthia's face clouded. Relieved though she was about her mother, there was still that horror for Virginia. "Come," I interrupted, not wishing to let Chapelle get out of my sight, yet wishing to follow Kennedy, who had dashed up-stairs. I found Craig already at the bedside of Virginia. He had broken one of the ampules and was injecting some of the extract in it into the sleeping girl's arm. Mrs. Blakeley bent over eagerly as he did so. Even in her manner she was changed. There was anxiety for Virginia yet, but one could feel that a great weight seemed to be lifted from her. So engrossed was I in watching Kennedy that I did not hear Doctor Haynes and Hampton enter. Chapelle heard, however, and turned. For a moment he gazed at Hampton. Then with a slight curl of the lip he said, in a low tone, "Is it strictly ethical to treat a patient for disease of the heart when she is suffering from anemia--if you have an interest in the life and death of the patient?" I watched Hampton's face closely. There was indignation in every line of it. But before he could reply Doctor Haynes stepped forward. "My son was right in the diagnosis," he almost shouted, shaking a menacing finger at Chapelle. "To come to the point, sir, explain that mark on Miss Virginia's forehead!" "Yes," demanded Hampton, also taking a step toward the beauty doctor, "explain it--if you dare." Cynthia suppressed a little cry of fear. For a moment I thought that the two young men would forget everything in the heat of their feelings. "Just a second," interposed Kennedy, quickly stepping between them. "Let me do the talking." There was something commanding about his tone as he looked from one to the other of us. "The trouble with Miss Virginia," he added, deliberately, "seems to lie in one of what the scientists have lately designated the 'endocrine glands'--in this case the pituitary. My X-ray pictures show that conclusively. "Let me explain for the benefit of the rest. The pituitary is an oval glandular body composed of two lobes and a connecting area, which rest in the sella turcica, enveloped by a layer of tissue, about under this point." He indicated the red spot on her forehead as he spoke. "It is, as the early French surgeons called it, l'organe enigmatique. The ancients thought it discharged the pituita, or mucus, into the nose. Most scientists of the past century asserted that it was a vestigial relic of prehistoric usefulness. To-day we know better. "One by one the functions of the internal secretions are being discovered. Our variously acquired bits of information concerning the ductless glands lie before us like the fragments of a modern picture puzzle. And so, I may tell you, in connection with recent experimental studies of the role of the pituitary, Doctor Cushing and other collaborators at Johns Hopkins have noticed a marked tendency to pass into a profoundly lethargic state when the secretion of the pituitary is totally or nearly so removed." Kennedy now had every eye riveted on him as he deftly led the subject straight to the case of the poor girl before us. "This," he added, with a wave of his hand toward her, "is much like what is called the Frohlich syndrome--the lethargy, the subnormal temperature, slow pulse, and respiration, lowered blood pressure, and insensitivity, the growth of fat and the loss of sex characteristics. It has a name--dystrophia adiposogenitalis." He nodded to Doctor Haynes, but did not pause. "This case bears a striking resemblance to the pronounced natural somnolence of hibernation. And induced hypopituitarism--under activity of the gland--produces a result just like natural hibernation. Hibernation has nothing to do with winter, or with food, primarily; it is connected in some way with this little gland under the forehead. "As the pituitary secretion is lessened, the blocking action of the fatigue products in the body be-comes greater and morbid somnolence sets in. There is a high tolerance of carbohydrates which are promptly stored as fat. I am surprised, Doctor Haynes, that you did not recognize the symptoms." A murmur from Mrs. Blakeley cut short Doctor Haynes's reply. I thought I noticed a movement of the still face on the white bed. "Virgie! Virgie!" called Mrs. Blakeley, dropping on her knee beside her daughter. "I'm here--mother!" Virginia's eyes opened ever so slightly. Her face turned just an inch or two. She seemed to be making a great effort, but it lasted only a moment. Then she slipped back into the strange condition that had baffled skilled physicians and surgeons for nearly a week. "The sleep is being dispelled," said Kennedy, quietly placing his hand on Mrs. Blakeley's shoulder. "It is a sort of semi-consciousness now and the improvement should soon be great." "And that?" I asked, touching the empty ampule from which he had injected the contents into her. "Pituitrin--the extract of the anterior lobe of the pituitary body. Some one who had an object in removing her temporarily probably counted on restoring her to her former blooming womanhood by pituitrin--and by removing the cause of the trouble." Kennedy reached into his pocket and drew forth the second X-ray photograph he had taken. "Mrs. Blakeley, may I trouble you to get that beauty mask which your daughter wore?" Mechanically Mrs. Blakeley obeyed. I expected Chapelle to object, but not a word broke the death-like stillness. "The narcolepsy," continued Kennedy, taking the mask, "was due, I find, to something that affected the pituitary gland. I have here a photograph of her taken when she was wearing the mask." He ran his finger lightly over the part just above the eyes. "Feel that little lump, Walter," he directed. I did so. It was almost imperceptible, but there was something. "What is it?" I asked. "Located in one of the best protected and most inaccessible parts of the body," Kennedy considered, slowly, "how could the pituitary be reached? If you will study my skiagraph, you will see how I got my first clue. There was something over that spot which caused the refractory sore. What was it? Radium--carefully placed in the mask with guards of lead foil in such a way as to protect the eyes, but direct the emission full at the gland which was to be affected, and the secretions stopped." Chapelle gave a gasp. He was pale and agitated. "Some of you have already heard of Reba Rinehart," shot out Kennedy, suddenly changing the subject. Mrs. Blakeley could not have been more astounded if a bomb had dropped before her. Still kneeling before Virginia's bed, she turned her startled face at Kennedy, clasping her hands in appeal. "It was for my girls that I tried to buy her off--for their good name--their fortune--their future," she cried, imploringly. Kennedy bent down, "I know that is all," he reassured, then, facing us, went on: "Behind that old woman was a secret of romantic interest. She was contemplating filing suit in the courts to recover a widow's interest in the land on which now stand the homes of millionaires, hotel palaces, luxurious apartments, and popular theaters--millions of dollars' worth of property." Cynthia moved over and drew her arms about the convulsed figure of her mother. "Some one else knew of this old marriage of Stuart Blakeley," proceeded Kennedy, "knew of Reba Rinehart, knew that she might die at any moment. But until she died none of the Blakeleys could be entirely sure of their fortune." It flashed over me that Chapelle might have conceived the whole scheme, seeking to gain the entire fortune for Cynthia. "Who was interested enough to plot this postponement of the wedding until the danger to the fortune was finally removed?" I caught sight of Hampton Haynes, his eyes riveted on the face on the bed before us. Virginia stirred again. This time her eyes opened wider. As if in a dream she caught sight of the face of her lover and smiled wanly. Could it have been Hampton? It seemed incredible. "The old lady is dead," pursued Kennedy, tensely. "Her dower right died with her. Nothing can be gained by bringing her case back again--except to trouble the Blakeleys in what is rightfully theirs." Gathering up the beauty mask, the X-ray photographs, and the papers of Mrs. Rinehart, Kennedy emphasized with them the words as he whipped them out suddenly. "Postponing the marriage, at the possible expense of Chapelle, until Reba Rinehart was dead, and trusting to a wrong diagnosis and Hampton's inexperience as the surest way of bringing that result about quickly, it was your inordinate ambition for your son, Doctor Haynes, that led you on. I shall hold these proofs until Virginia Blakeley is restored completely to health and beauty." VII THE LOVE METER "Since we brought him home, my brother just tosses and gasps for air. Oh, I think Eulalie and I shall both go mad!" The soft, pleading voice of Anitra Barrios and her big, appealing brown eyes filled with tears were doubly affecting as, in spite of her own feelings, she placed her hand on that of a somewhat younger girl who had accompanied her to the laboratory. "We were to have been married next month," sobbed Eulalie Sandoval. "Can't you come and see Jose, Professor Kennedy? There must be something you can do. We fear he is dying--yes, dying." "Poor little girl!" murmured Anitra, still patting her hand affectionately, then to us, "You know, Eulalie is the sister of Manuel Sandoval, who manages the New York business of my brother." She paused. "Oh, I can't believe it, myself. It's all so strange, so sudden." For the moment her own grief overwhelmed Anitra, and both sister and sweetheart of Jose Barrios clung to each other. "What is the trouble?" soothed Craig. "What has happened? How can I help you?" "Everything was so happy with us," cried Anitra, "until Jose and I came to New York--and--now--" She broke down again. "Please be calm," encouraged Kennedy. "Tell me everything--anything." With an effort Anitra began again. "It was last night--quite late--at his office at the foot of Wall Street--he was there alone," she strove to connect her broken thoughts. "Some one--I think it must have been the janitor--called me up at home and said that my brother was very ill. Eulalie was there with me. We hurried down to him. When we got there Jose was on the floor by his desk, unconscious, struggling for breath, just as he is now." "Did you observe anything peculiar?" queried Kennedy. "Was there anything that might give you a hint of what had happened?" Anitra Barrios considered. "Nothing," she replied, slowly, "except that the windows were all closed. There was a peculiar odor in the room. I was so excited over Jose, though, that I couldn't tell you just what it was like." "What did you do?" inquired Craig. "What could we do, just two girls, all alone? It was late. The streets were deserted. You know how they are down-town at night. We took him home, to the hotel, in a cab, and called the hotel physician, Doctor Scott." Both girls were again weeping silently in each other's arms. If there was anything that moved Kennedy to action it was distress of this sort. Without a word he rose from his desk, and I followed him. Anitra and Eulalie seemed to understand. Though they said nothing, they looked their gratitude as we four left the laboratory. On the way down to the hotel Anitra continued to pour out her story in a fragmentary way. Her brother and she, it seemed, had inherited from their father a large sugar-plantation in Santa Clara, the middle province of Cuba. Jose had not been like many of the planters. He had actually taken hold of the plantation, after the revolution had wrecked it, and had re-established it on modern, scientific lines. Now it was one of the largest independent plantations on the island. To increase its efficiency, he had later established a New York office to look after the sale of the raw sugar and had placed it in charge of a friend, Manuel Sandoval. A month or so before he had come to New York with his sister to sell the plantation, to get the high price that the boom in sugar had made it worth. It was while he had been negotiating for the sale that he had fallen in love with Eulalie and they had become engaged. Doctor Scott met us in the sitting-room of the suite which Anitra and her brother occupied, and, as she introduced us, with an anxious glance in the direction of the door of the sick-room, he shook his head gravely, though he did his best to seem encouraging. "It's a case of poisoning of some kind, I fear," he whispered aside to us, at the first opportunity. "But I can't quite make out just what it is." We followed the doctor into the room. Eulalie had preceded us and had dropped down on her knees by the bed, passing her little white hand caressingly over the pale and distorted face of Jose. He was still unconscious, gasping and fighting for breath, his features pinched and skin cold and clammy. Kennedy examined the stricken man carefully, first feeling his pulse. It was barely perceptible, rapid, thready, and irregular. Now and then there were muscular tremblings and convulsive movements of the limbs. Craig moved over to the side of the room away from the two girls, where Doctor Scott was standing. "Sometimes," I heard the doctor venture, "I think it is aconite, but the symptoms are not quite the same. Besides, I don't see how it could have been administered. There's no mark on him that might have come from a hypodermic, no wound, not even a scratch. He couldn't have swallowed it. Suicide is out of the question. But his nose and throat are terribly swollen and inflamed. It's beyond me." I tried to recall other cases I had seen. There was one case of Kennedy's in which several deaths had occurred due to aconite. Was this another of that sort? I felt unqualified to judge, where Doctor Scott himself confessed his inability. Kennedy himself said nothing, and from his face I gathered that even he had no clue as yet. As we left the sick-room, we found that another visitor had arrived and was standing in the sitting-room. It was Manuel Sandoval. Sandoval was a handsome fellow, tall, straight as an arrow, with bushy dark hair and a mustache which gave him a distinguished appearance. Born in Cuba, he had been educated in the United States, had taken special work in the technology of sugar, knew the game from cane to centrifugal and the ship to the sugar trust. He was quite as much a scientist as a business man. He and Eulalie talked for a moment in low tones in Cuban Spanish, but it needed only to watch his eyes to guess where his heart was. He seemed to fairly devour every move that Anitra made about the apartment. A few minutes later the door opened again and a striking-looking man entered. He was a bit older than Sandoval, but still young. As he entered he bowed to Sandoval and Eulalie but greeted Anitra warmly. "Mr. Burton Page," introduced Anitra, turning to us quickly, with just the trace of a flush on her face. "Mr. Page has been putting my brother in touch with people in New York who are interested in Cuban sugar-plantations." A call from Doctor Scott for some help took both girls into the sick-room for a moment. "Is Barrios any better?" asked Page, turning to Sandoval. Sandoval shook his head in the negative, but said nothing. One could not help observing that there seemed to be a sort of antipathy between the two, and I saw that Craig was observing them both closely. Page was a typical, breezy Westerner, who had first drifted to New York as a mining promoter. Prom that he had gone into selling ranches, and, by natural stages, into the promotion of almost anything in the universe. Sugar being at the time uppermost in the mind of the "Street," Page was naturally to be found crammed with facts about that staple. One could not help being interested in studying a man of his type, as long as one kept his grip on his pocket-book. For he was a veritable pied piper when it came to enticing dollars to follow him, and in his promotions he had the reputation of having amassed an impressive pile of dollars himself. No important change in the condition of Barrios had taken place, except that he was a trifle more exhausted, and Doctor Scott administered a stimulant. Kennedy, who was eager to take up the investigation of the case on the outside in the hope of discovering something that might be dignified into being a clue, excused himself, with a nod to Anitra to follow into the hall. "I may look over the office?" Craig ventured when we were alone with her. "Surely," she replied, frankly, opening her handbag which was lying on a table near the door. "I have an equal right in the business with my brother. Here are the keys. The office has been closed to-day." Kennedy took the keys, promising to let her know the moment he discovered anything important, and we hurried directly down-town. The office of the Barrios Company was at the foot of Wall Street, where the business of importing touched on the financial district. From the window one could see freighters unloading their cargoes at the docks. In the other direction, capital to the billions was represented. But in all that interesting neighborhood nothing just at present could surpass the mystery of what had taken place in the lonely little office late the night before. Kennedy passed the rail that shut the outer office off from a sort of reception space. He glanced about at the safe, the books, papers, and letter-files. It would take an accountant and an investigator days, perhaps weeks, to trace out anything in them, if indeed it were worth while at all. Two glass doors opened at one end to two smaller private offices, one belonging evidently to Sandoval, the other to Barrios. What theory Craig formed I could not guess, but as he tiptoed from the hall door, past the rail, to the door of Jose's office, I could see that first of all he was trying to discover whether it was possible to enter the outer office and reach Jose's door unseen and unheard by any one sitting at the desk inside. Apparently it was easily possible, and he paused a moment to consider what good that knowledge might do. As he did so his eye rested on the floor. A few feet away stood one of the modern "sanitary" desks. In this case the legs of the desk raised the desk high enough from the floor so that one could at least see where the cleaning-woman had left a small pile of unsanitary dust near the wall. Suddenly Kennedy bent down and poked something out of the pile of dust. There on the floor was an empty shell of a cartridge. Kennedy picked it up and looked at it curiously. What did it mean? I recalled that Doctor Scott had particularly said that Barrios had not been wounded. Still regarding the cartridge shell, Kennedy sat down at the desk of Barrios. Looking for a piece of paper in which to wrap the shell, he pulled out the middle drawer of the desk. In a back corner was a package of letters, neatly tied. We glanced at them. The envelopes bore the name of Jose Barrios and were in the handwriting of a woman. Some were postmarked Cuba; others, later, New York. Kennedy opened one of them. I could not restrain an exclamation of astonishment. I had expected that they were from Eulalie Sandoval. But they were signed by a name that we had not heard--Teresa de Leon! Hastily Kennedy read through the open letter. Its tone seemed to be that of a threat. One sentence I recall was, "I would follow you anywhere--I'll make you want me." One after another Kennedy ran through them. All were vague and veiled, as though the writer wished by some circumlocution to convey an idea that would not be apparent to some third, inquisitive party. What was back of it all? Had Jose been making love to another woman at the same time that he was engaged to Eulalie Sandoval? As far as the contents of the letters went there was nothing to show that he had done anything wrong. The mystery of the "other woman" only served to deepen the mystery of what little we already knew. Craig dropped the letters into his pocket along with the shell, and walked around into the office of Sandoval. I followed him. Quickly he made a search, but it did not seem to net him anything. Meanwhile I had been regarding a queer-looking instrument that stood on a flat table against one wall. It seemed to consist of a standard on each end of which was fastened a disk, besides several other arrangements the purpose of which I had not the slightest idea. Between the two ends rested a glass tube of some liquid. At one end was a lamp; the other was fitted with an eyepiece like a telescope. Beside the instrument on the table lay some more glass-capped tubes and strewn about were samples of raw sugar. "It is a saccharimeter," explained Kennedy, also looking at it, "an instrument used to detect the amount of sugar held in solution, a form of the polariscope. We won't go into the science of it now. It's rather abstruse." He was about to turn back into the outer office when an idea seemed to occur to him. He took the cartridge from his pocket and carefully scraped off what he could of the powder that still adhered to the outer rim. It was just a bit, but he dissolved it in some liquid from a bottle on the table, filled one of the clean glass tubes, capped the open end, and placed this tube in the saccharimeter where the first one I noticed had been. Carefully he lighted the lamp, then squinted through the eyepiece at the tube of liquid containing what he had derived from the cartridge. He made some adjustments, and as he did so his face indicated that at last he began to see something dimly. The saccharimeter had opened the first rift in the haze that surrounded the case. "I think I know what we have here," he said, briefly, rising and placing the tube and its contents in his pocket with the other things he had discovered. "Of course it is only a hint. This instrument won't tell me finally. But it is worth following up." With a final glance about to make sure that we had overlooked nothing, Kennedy closed and locked the outside door. "I'm going directly up to the laboratory, Walter," decided Kennedy. "Meanwhile you can help me very much if you will look up this Teresa de Leon. I noticed that the New York letters were written on the stationery of the Pan-America Hotel. Get what you can. I leave it to you. And if you can find out anything about the others, so much the better. I'll see you as soon as you finish." It was rather a large contract. If the story had reached the newspaper stage, I should have known how to go about it. For there is no detective agency in the world like the Star, and even on the slender basis that we had, with a flock of reporters deployed at every point in the city, with telephones, wires, and cables busily engaged, I might have gathered priceless information in a few hours. But, as it was, whatever was to be got must be got by me alone. I found Teresa de Leon registered at the Pan-America, as Craig had surmised. Such inquiries as I was able to make about the hotel did not show a trace of reason for believing that Jose Barrios had been numbered among her visitors. While that proved nothing as to the relations of the two, it was at least reassuring as far as Anitra and Eulalie were concerned, and, after all, as in such cases, this was their story. Not having been able to learn much about the lady, I decided finally to send up my card, and to my satisfaction she sent back word that she would receive me in the parlor of the hotel. Teresa de Leon proved to be a really striking type of Latin-American beauty. She was no longer young, but there was an elusiveness about her personality that made a more fascinating study than youth. I felt that with such a woman directness might be more of a surprise than subtlety. "I suppose you know that Senor Barrios is very seriously ill?" I ventured, in answer to her inquiring gaze that played from my card to my face. For a fleeting instant she looked startled. Yet she betrayed nothing as to whether it was fear or surprise. "I have called his office several times," she replied, "but no one answered. Even Senor Sandoval was not there." I felt that she was countering as cleverly as I might lead. "Then you know Mr. Sandoval also?" I asked, adding, "and Mr. Page?" "I have known Senor Barrios a long time in Cuba," she answered, "and the others, too--here." There was something evasive about her answers. She was trying to say neither too much nor too little. She left one in doubt whether she was trying to shield herself or to involve another. Though we chatted several minutes, I could gain nothing that would lead me to judge how intimately she knew Barrios. Except that she knew Sandoval and Page, her conversation might have been a replica of the letters we had discovered. Even when she hinted politely, but finally, that the talk was over she left me in doubt even whether she was an adventuress. The woman was an enigma. Had revenge or jealousy brought her to New York, or was she merely a tool in the hands of another? I was not ready to return to Kennedy merely with another unanswered question, and I determined to stop again at the hotel where Barrios and his sister lived, in the hope of picking up something there. The clerk at the desk told me that no one had called since we had been there, adding: "Except the tall gentleman, who came back. I think Senorita Barrios came down and met him in the tea-room." Wondering whether it was Page or Sandoval the clerk meant, I sauntered down the corridor past the door of the tea-room. It was Page with whom Anitra was talking. There was no way in which I could hear what was said, although Page was very earnest and Anitra showed plainly that she was anxious to return to the sick-room up-stairs. As I watched, I took good care that I should not be seen. It was well that I did, for once when I looked about I saw that some one else in another doorway was watching them, too, so intently that he did not see me. It was Sandoval. Jealousy of Page was written in every line of his face. Studying the three, while I could not escape the rivalry of the two men, I was unable to see now or recollect anything that had happened which would convey even an inkling of her feelings toward them. Yet I was convinced that that way lay a problem quite as important as relations between the other triangle of Eulalie, Teresa, and Barrios. I was not psychologist enough to deal with either triangle. There was something that distinctly called for the higher mathematics of Kennedy. Determined not to return to him entirely empty-mouthed, I thought it would be a good opportunity to see Eulalie alone, and hurried to the elevator, which whisked me up to the Barrios apartment. Doctor Scott had not left his patient, though he seemed to realize that Eulalie was a most efficient nurse. "No change," whispered the doctor, "except that he is reaching a crisis." Interested as I was in the patient, it had been for the purpose of seeing Eulalie that I had come, and I was glad when Doctor Scott left us a moment. "Has Mr. Kennedy found out anything yet?" she asked, in a tremulous whisper. "I think he is on the right track now," I encouraged. "Has anything happened here? Remember--it is quite as important that you should tell him all as it is for him to tell you." She looked at me a moment, then drew from a fold of her waist a yellow paper. It was a telegram. I took it and read: Beware of Teresa de Leon, Hotel Pan-America. A FRIEND. "You know her?" I asked, folding the telegram, but not returning it. Eulalie looked at me frankly and shook her head. "I have no idea who she is." "Or of who sent the telegram?" "None at all." "When did you receive it?" "Only a few minutes ago." Here was another mystery. Who had sent the anonymous telegram to Eulalie so soon after it had been evident that Kennedy had entered the case? What was its purpose? "I may keep this?" I asked, indicating the telegram. "I was about to send it to Professor Kennedy," she replied. "Oh, I hope he will find something Won't you go to him and tell him to hurry?" I needed no urging, not only for her sake, but also because I did not wish to be seen or to have the receipt of the telegram by Kennedy known so soon. In the hotel I stopped only long enough to see that Anitra was now hurrying toward the elevator, eager to get back to her brother and oblivious to every one around. What had become of Page and the sinister watcher whom he had not seen I did not know, nor did I have time to find out. A few moments later I rejoined Kennedy at the laboratory. He was still immersed in work, and, scarcely stopping, nodded to me to tell what I had discovered. He listened with interest until I came to the receipt of the anonymous telegram. "Did you get it?" he asked, eagerly. He almost seized it from my hands as I pulled it out of my pocket and studied it intently. "Strange," he muttered. "Any of them might have sent it." "Have you discovered anything?" I asked, for I had been watching him, consumed by curiosity, as I told my story. "Do you know yet how the thing was done?" "I think I do," he replied, abstractedly. "How was it?" I prompted, for his mind was now on the telegram. "A poison-gas pistol," he resumed, coming back to the work he had just been doing. "Instead of bullets, this pistol used cartridges charged with some deadly powder. It might have been something like the anesthetic pistol devised by the police authorities in Paris some years ago when the motor bandits were operating." "But who could have used it?" I asked. Kennedy did not answer directly. Either he was not quite sure yet or did not feel that the time was ripe to hazard a theory. "In this case," he continued, after a moment's thought, "I shouldn't be surprised if even the wielder of the pistol probably wore a mask, doubly effective, for disguise and to protect the wielder from the fumes that were to overcome the victim." "You have no idea who it was?" I reiterated. Before Kennedy could answer there came a violent ring at the laboratory bell, and I hurried to the door. It was one of the bell-boys from the hotel where the Barrioses had their apartment, with a message for Kennedy. Craig tore it open and read it hurriedly. "From Doctor Scott," he said, briefly, in answer to my anxious query. "Barrios is dead." Even though I had been prepared for the news by my last visit, death came as a shock, as it always does. I had felt all along that Kennedy had been called in too late to do anything to save Barrios, but I had been hoping against hope. But I knew that it was not too late to catch the criminal who had done the dastardly, heartless deed. A few hours and perhaps all clues might have been covered up. But there is always something that goes wrong with crime, always some point where murder cannot be covered up. I think if people could only be got to realize it, as my experience both on the Star and with Kennedy have impressed it on me, murder would become a lost art. Without another word Kennedy seized his hat and together we hurried to the hotel. We found Anitra crying softly to herself, while near her sat Eulalie, tearless, stunned by the blow, broken-hearted. In the realization of the tragedy everything had been forgotten, even the mysterious anonymous telegram signed, Judas-like, "A Friend." Sandoval, we learned, had been there when the end came, and had now gone out to make what arrangements were necessary. I had nothing against the man, but I could not help feeling that, now that the business was all Anitra's, might he not be the one to profit most by the death? The fact was that Kennedy had expressed so little opinion on the case so far that I might be pardoned for suspecting any one--even Teresa de Leon, who must have seen Jose slipping away from her in spite of her pursuit, whatever actuated it. It was while I was in the midst of these fruitless speculations that Doctor Scott beckoned us outside, and we withdrew quietly. "I don't know that there is anything more that I can do," he remarked, "but I promised Senor Sandoval that I would stay here until he came back. He begged me to, seems scarcely to know how to do enough to comfort his sister and Senorita Barrios." I listened to the doctor keenly. Was it possible that Sandoval had one of those Jekyll-Hyde natures which seem to be so common in some of us? Had his better nature yielded to his worse? To my mind that has often been an explanation of crime, never an adequate defense. Kennedy was about to say something when the elevator door down the hall opened. I expected that it was Sandoval returning, but it was Burton Page. "They told me you were here," he said, greeting us. "I have been looking all over for you, down at your laboratory and at your apartment. Would you mind stepping down around the bend in the hall?" We excused ourselves from Doctor Scott, wondering what Page had to reveal. "I knew Sandoval had not returned," he began as soon as we were out of ear-shot of the doctor, "and I don't want to see him--again--not after what happened this afternoon. The man is crazy." We had reached an alcove and sank down into a soft settee. "Why, what was that?" I asked, recalling the look of hate on the man's face as he had watched Page talking to Anitra in the tea-room. "I'm giving you this for what it may be worth," began Page, turning from me to Kennedy. "Down in the lobby this afternoon, after you had been gone some time, I happened to run into Sandoval. He almost seized hold of me. 'You have been at the office,' he said. 'You've been rummaging around there.' Well, I denied it flatly. 'Who took those letters?' he shot back at me. All I could do was to look at him. 'I don't know about any letters. What letters?' I asked. Oh, he's a queer fellow all right. I thought he was going to kill me by the black look he gave me. He cooled down a bit, but I didn't wait for any apology. The best thing to do with these hot-headed people is to cut out and let them alone." "How do you account for his strange actions?" asked Kennedy. "Have you ever heard anything more that he did?" Page shrugged his shoulders as if in doubt whether to say anything, then decided quickly. "The other day I heard Barrios and Sandoval in the office. They were quite excited. Barrios was talking loudly. I didn't know at first what it was all about. But I soon found out. Sandoval had gone to him, as the head of the family, following their custom, I believe, to ask whether he might seek to win Anitra." "Have you ever heard of Teresa de Leon?" interrupted Kennedy suddenly. Page looked at him and hesitated. "There's some scandal, there, I'm afraid," he nodded, combining his answers. "I heard Sandoval say something about her to Barrios that day--warn him against something. That was when the argument was heated. It seemed to make Barrios angry. Sandoval said something about Barrios refusing to let him court Anitra while at the same time Barrios was engaged to Eulalie. Barrios retorted that the cases were different. He said he had decided that Anitra was going to marry an American millionaire." There could be no doubt about how Page himself interpreted the remark. It was evident that he took it to mean himself. "Sandoval had warned against this De Leon?" asked Kennedy, evidently having in mind the anonymous telegram. "Something--I don't know what it was all about," returned Page, then added, in a burst of confidence: "I never heard of the lady until she came to New York and introduced herself to me. For a time she was interesting. But I'm too old for that sort of thing. Besides, she always impressed me as though she had some ulterior motive, as though she was trying to get at something through me. I cut it all out." Kennedy nodded, but for a moment said nothing. "I think I'll be getting out," remarked Page, with a half smile. "I don't want a knife in the back. I thought you ought to know all this, though. And if I hear anything else I'll let you know." Kennedy thanked him and together we rode down in the next elevator, parting with Page at the hotel entrance. It was still early in the evening, and Kennedy had no intention now of wasting a moment. He beckoned for a cab and directed the man to drive immediately to the Pan-America. This time Teresa de Leon was plainly prepared for a visit, though I am not sure that she was prepared to receive two visitors. "I believe you were acquainted with Senior Barrios, who died to-night?" opened Kennedy, after I had introduced him. "He was acquainted with me," she corrected, with a purr in her voice that suggested claws. "You were not married to him," shot out Kennedy; then before she could reply, "nor even engaged." "He had known me a long time. We were intimate--" "Friends," interrupted Kennedy, leaving no doubt as to the meaning of his emphasis. She colored. It was evident that, at least to her, it was more than friendship. "Senor Sandoval says," romanced Kennedy, in true detective style, "that you wrote--" It was her turn to interrupt. "If Senor Sandoval says anything against me, he tells what is not--the truth." In spite of Kennedy's grilling she was still mistress of herself. "You introduced yourself to Burton Page, and--" "You had better remember your own proverb," she retorted. "Don't believe anything you hear and only half you see." Kennedy snapped down the yellow telegram before her. It was a dramatic moment. The woman did not flinch at the anonymous implication. Straight into Kennedy's eyes she shot a penetrating glance. "Watch both of THEM," she replied, shortly, then turned and deliberately swept out of the hotel parlor as though daring us to go as far as we cared. "I think we have started forces working for us," remarked Kennedy, coolly consulting his watch. "For the present at least let us retire to the laboratory. Some one will make a move. My game is to play one against the other--until the real one breaks." We had scarcely switched on the lights and Kennedy was checking over the results he had obtained during his afternoon's investigations, when the door was flung open and a man dashed in on us unexpectedly. It was Sandoval, and as he advanced furiously at Kennedy I more than feared that Page's idea was correct. "It was you, Kennedy," he hissed, "who took those letters from Jose's desk. It is you--or Page back of you--who are trying to connect me with that woman, De Leon. But let me tell you--" A sharp click back of Sandoval caused him to cut short the remark and look about apprehensively. Kennedy's finger, sliding along the edge of the laboratory table, had merely found an electric button by which he could snap the lock on the door. "We are two to one," returned Kennedy, nonchalantly. "That was nothing but the lock on the door closing. Mr. Jameson has a revolver in the top drawer of his desk over there. You will pardon me if I do a little telephoning--through the central office of the detective bureau? Some of our friends may not be overanxious to come here, and it may be necessary to compel their attendance." Sandoval subsided into a sullen silence as Kennedy made arrangements to have Burton Page, Anitra, Eulalie, and Teresa de Leon hurried to us at once. There was nothing for me to do but watch Sandoval as Kennedy prepared a little instrument with a scale and dial upon which rested an indicator resembling a watch hand, something like the new horizontal clocks which have only one hand to register seconds, minutes, and hours. In them, like a thermometer held sidewise, the hand moves along from zero to twenty-four. In this instrument a little needle did the same thing. Pairs of little wire-like strings ran to the instrument. Kennedy had finished adjusting another instrument which was much like the saccharimeter, only more complicated, when the racing of an engine outside announced the arrival of the party in one of the police department cars. Between us, Craig and I lost no time in disposing the visitors so that each was in possession of a pair of the wire-like strings, and then disdaining to explain why he had gathered them together so unceremoniously, Kennedy turned and finished adjusting the other apparatus. "Most people regard light, so abundant, so necessary, so free as a matter of course," he remarked, contemplatively. "Not one person in ten thousand ever thinks of its mysterious nature or ever attempts to investigate it. In fact, most of us are in utter darkness as to light." He paused, tapped the machine and went on, "This is a polarimeter--a simple polariscope--a step beyond the saccharimeter," he explained, with a nod at Sandoval. "It detects differences of structure in substances not visible in ordinary light. "Light is polarized in several ways--by reflection, by transmission, but most commonly through what I have here, a prism of calcite, or Iceland spar, commonly called a Nicol prism. Light fully polarized consists of vibrations transverse to the direction of the ray, all in one plane. Ordinary light has transverse vibrations in all planes. Certain substances, due to their molecular structure, are transparent to vibrations in one plane, but opaque to those at right angles. "Here we have," he explained, tapping the parts in order, "a source of light, passing in through this aperture, here a Nicol polarizer, next a liquid to be examined in a glass-capped tube; here on this other side an arrangement of quartz plates with rotary power which I will explain in a moment, next an analyzer, and finally the aperture for the eye of an observer." Kennedy adjusted the glass tube containing the liquid which bore the substance scraped from the cartridge--he had picked up in the office of Jose. "Look through the eyepiece, Walter," he directed. The field appeared halved. He made an adjustment and at once the field of vision appeared wholly the same tint. When he removed the tube it was dark. "If a liquid has not what we call rotary power both halves of the double disk appear of the same tint," he explained. "If it has rotary power, the halves appear of different tints and the degree of rotation is measured by the alteration of thickness of this double quartz plate necessary to counteract it. It is, as I told Mr. Jameson early to-day, a rather abstruse subject, this of polarized light. I shall not bore you with it, but I think you will see in a moment why it is necessary, perhaps why some one who knew thought it would never be used. "What I am getting at now is that some substances with the same chemical formula rotate polarized light to the right, are dextro-rotary, as, for instance, what is known as dextrose. Others rotate it to the left, are levo-rotary, as the substance called levose. Both of them are glucose. So there are substances which give the same chemical reactions which can only be distinguished by their being left or right rotary." Craig took a bit of crystalline powder and dissolved it in ether. Then he added some strong sulphuric acid. The liquid turned yellow, then slowly a bright scarlet. Beside the first he repeated the operation with another similar-looking powder, with the identical result. "Both of those," he remarked, holding up the vials, "were samples of pure veratrine, but obtained from different sources. You see the brilliant reaction--unmistakable. But it makes all the difference in the world in this case what was the source of the veratrine. It may mean the guilt or innocence of one of you." He paused, to let the significance of his remark sink in. "Veratrine," he resumed, "is a form of hellebore, known to gardeners for its fatal effect on insects. There are white and green hellebore, Veratrum alba and Veratrum viride. It is the pure alkaloid, or rather one of them, that we have to deal with here--veratrine. "There are various sources of veratrine. For instance, there is the veratrine that may be derived from the sabadilla seeds which grow in the West Indies and Mexico. It is used, I am informed, by the Germans in their lachrymatory and asphyxiating bombs." The mention of the West Indies brought, like a flash, to my mind Sandoval and Senorita de Leon. "Then, too," continued Kennedy, "there is a plant out in our own Western country, of which you may have heard, known as the death camas, very fatal to cattle when they eat it. The active principle in this is also veratrine." I began to see what Kennedy was driving at. If it were veratrine derived from death camas it would point toward Page. "Abderhalden, the great German physiological chemist, has discovered that substances that once get into the blood produce specific ferments. Not long ago, in a case, I showed it by the use of dialyzing membranes. But Abderhalden has found that the polariscope can show it also. And in this case only the polariscope can show what chemistry cannot show when we reach the point of testing Senor Barrios's blood--if that becomes necessary." It was plain that Kennedy was confident. "There are other sources of drugs of the nature used in this case to asphyxiate and kill, but the active principle of all is veratrine. The point is, veratrine from what source? The sabadilla is dextro-rotary; the death camas is levo-rotary. Which is it here?" As I tried to figure out the ramifications of the case, I could see that it was a cruel situation for one or the other of the girls. Was one of her lovers the murderer of Anitra's brother? Or was her own brother the murderer of Eulalie's lover? I looked at the faces before me, now tensely watching Kennedy, forgetful of the wire-like strings which they held in their hands. I studied Teresa de Leon intently for a while. She was still the enigma which she had been the first time I saw her. Kennedy paused long enough to look through the eyepiece again as if to reassure himself finally that he was right. There was a tantalizing suspense as we waited for the verdict of science on this intensely human tragedy. Then he turned to the queer instrument over which the needle-hand was moving. "Though some scientists would call this merely a sensitive form of galvanometer," he remarked, "it is, to me, more than that. It registers feelings, emotions. It has been registering your own every moment that I have been talking. "But most of all it registers the grand passion. I might even call it a love meter. Love might seem to be a subject which could not be investigated. But even love can be attributed to electrical forces, or, perhaps better, is expressed by the generation of an electric current, as though the attraction between men and women were the giving off of electrons or radiations of one to the other. I have seen this galvanometer stationary during the ordinary meeting of men and women, yet exhibit all sorts of strange vibrations when true lovers meet." Not used to Kennedy's peculiar methods, they were now on guard, ignorant of the fact that that alone was sufficient to corroborate unescapably any evidence they had already given of their feelings toward each other. Kennedy passed lightly over the torn and bleeding heart of Eulalie. But, much as he disliked to do so, he could not so quickly pass Anitra. In spite of her grief, I could see that she was striving to control herself. A quick blush suffused her face and her breath came and went faster. "This record," went on Kennedy, lowering his voice, "tells me that two men are in love with Anitra Barrios. I will not say which exhibits the deeper, truer passion. You shall see for yourself in a moment. But, more than that, it tells me which of the two she cares for most--a secret her heart would never permit her lips to disclose. Nor will I disclose it. "One of them, with supreme egotism, was so sure that he would win her heart that he plotted this murder of her brother so that she would have the whole estate to bring to him--a terrible price for a dowry. My love meter tells me, however, that Anitra has something to say about it yet. She does not love this man. "As for Teresa de Leon, it was jealousy that impelled her to follow Jose Barrios from Cuba to New York. The murderer, in his scheming, knew it, saw a chance to use her, to encourage her, perhaps throw suspicion on her, if necessary. When I came uncomfortably close to him he even sent an anonymous telegram that might point toward her. It was sent by the same person who stole in Barrios's office and shot him with an asphyxiating pistol which discharged a fatal quantity of pure veratrine full at him. "My love meter, in registering hidden emotions, supplements what the polarimeter tells me. It was the levo-rotary veratrine of the fatal death camas which you used, Page," concluded Craig, as again the electric attachment clicked shut the lock on the laboratory door. VIII THE VITAL PRINCIPLE "That's the handwriting of a woman--a jealous woman," remarked Kennedy, handing to me a dainty note on plain paper which had come in the morning mail. I did not stop to study the writing, for the contents of the letter were more fascinating than even Kennedy's new science of graphology. You don't know me [the note read], but I know of your work of scientific investigation. Let me inform you of something that ought to interest you. In the Forum Apartments you will find that there is some strange disease affecting the Wardlaw family. It is a queer disease of the nerves. One is dead. Others are dying. Look into it. A FRIEND. As I read it I asked myself vainly what it could mean. There was no direct accusation against any one, yet the implication was plain. A woman had been moved by one of the primal passions to betray--some one. I looked up from the note on the table at Craig. He was still studying the handwriting. "It's that peculiar vertical, angular hand affected by many women," he commented, half to himself. "Even at a glance you can see that it's written hastily, as if under the stress of excitement and sudden resolution. You'll notice how those capitals--" The laboratory door opened, interrupting him. "Hello, Kennedy," greeted Doctor Leslie, our friend, the coroner's physician, who had recently been appointed Health Commissioner of the city. It was the first time we had seen him since the appointment and we hastened to congratulate him. He thanked us absently, and it was evident that there was something on his mind, some problem which, in his new office, he felt that he must solve if for no other purpose than to justify his reputation. Craig said nothing, preferring to let the commissioner come to the point in his own way. "Do you know, Kennedy," he said, at length, turning in his chair and facing us, "I believe we have found one of the strangest cases in the history of the department." The commissioner paused, then went on, quickly, "It looks as if it were nothing less than an epidemic of beriberi--not on a ship coming into port as so often happens, but actually in the heart of the city." "Beriberi--in New York?" queried Craig, incredulously. "It looks like it," reiterated Leslie, "in the family of a Doctor Wardlaw, up-town here, in the Forum--" Kennedy had already shoved over the letter he had just received. Leslie did not finish the sentence, but read the note in amazement. "What are the symptoms?" inquired Craig. "What makes you think it is beriberi, of all things?" "Because they show the symptoms of beriberi," persisted Leslie, doggedly. "You know what they are like. If you care to go into the matter I think I can convince you." The commissioner was still holding the letter and gazing, puzzled, from it to us. It seemed as if he regarded it merely as confirming his own suspicions that something was wrong, even though it shed no real light on the matter. "How did you first hear of it?" prompted Kennedy. Leslie answered frankly. "It came to the attention of the department as the result of a reform I have inaugurated. When I went in office I found that many of the death certificates were faulty, and in the course of our investigations we ran across one that seemed to be most vaguely worded. I don't know yet whether it was ignorance--or something worse. But it started an inquiry. I can't say that I'm thoroughly satisfied with the amended certificate of the physician who attended Mrs. Marbury, the mother of Doctor Wardlaw's wife, who died about a week ago--Doctor Aitken." "Then Wardlaw didn't attend her himself?" asked Kennedy. "Oh no. He couldn't, under the circumstances, as I'll show you presently, aside from the medical ethics of the case. Aitken was the family physician of the Marburys." Kennedy glanced at the note. "One is dead. Others are dying," he read. "Who are the others? Who else is stricken?" "Why," continued Leslie, eager to unburden his story, "Wardlaw himself has the marks of a nervous affection as plainly as the eye can see it. You know what it is in this disease, as though the nerves were wasting away. But he doesn't seem half as badly affected as his wife. They tell me Maude Marbury was quite a beauty once, and photographs I have seen prove it. She's a wreck now. And, of course, the old lady must have been the most seriously affected of them all." "Who else is there in the household?" inquired Kennedy, growing more and more interested. "Well," answered Leslie, slowly, "they've had a nurse for some time, Natalie Langdale. Apparently she has escaped." "Any servants?" "Some by the day; only one regularly--a Japanese, Kato. He goes home at night, too. There's no evidence of the disease having affected him." I caught Leslie's eye as he gave the last information. Though I did not know much about beriberi, I had read of it, and knew that it was especially prevalent in the Orient. I did not know what importance to attach to Kato and his going home at night. "Have you done any investigating yourself?" asked Kennedy. Leslie hesitated a moment, as though deprecating his own efforts in that line, though when he spoke I could see no reason why he should, except that it had so often happened that Kennedy had seen the obvious which was hidden from most of those who consulted him. "Yes," he replied, "I thought perhaps there might be some motive back of it all which I might discover. Possibly it was old Mrs. Marbury's fortune--not a large one, but substantial. So it occurred to me that the will might show it. I have been to the surrogate." "And?" prompted Kennedy, approvingly. "Mrs. Marbury's will has already been offered for probate. It directs, among other things, that twenty-five thousand dollars be given by her daughter, to whom she leaves the bulk of her fortune, to Doctor Aitken, who had been Mr. Marbury's physician and her own." Leslie looked at us significantly, but Kennedy made no comment. "Would you like to go up there and see them?" urged the commissioner, anxious to get Craig's final word on whether he would co-operate in the affair. "I certainly should," returned Kennedy, heartily, folding up the letter which had first attracted his interest. "It looks as if there were more to this thing than a mere disease, however unusual." Doctor Leslie could not conceal his satisfaction, and without delaying a moment more than was necessary hurried us out into one of the department cars, which he had left waiting outside, and directed the driver to take us to the Forum Apartments, one of the newest and most fashionable on the Drive. Miss Langdale met us at the door and admitted us into the apartment. She was a striking type of trained nurse, one of those who seem bubbling over with health and vivacity. She seemed solicitous of her patients and reluctant to have them disturbed, yet apparently not daring to refuse to admit Doctor Leslie. There was nothing in her solicitude, however, that one could take exception to. Miss Langdale conducted us softly down a hallway through the middle of the apartment, and I noted quickly how it was laid out. On one side we passed a handsomely furnished parlor and dining-room, opposite which were the kitchen and butler's pantry, and, farther along, a bedroom and the bath. On down the hall, on the right, was Doctor Wardlaw's study, or rather den, for it was more of a library than an office. The nurse led the way, and we entered. Through the windows one caught a beautiful vista of the Drive, the river, and the Jersey shore. I gazed about curiously. Around the room there were bookcases and cabinets, a desk, some easy-chairs, and in the corner a table on which were some of Wardlaw's paraphernalia, for, although he was not a practising physician, he still specialized in his favorite branches of eye and ear surgery. Miss Langdale left us a moment, with a hasty excuse that she must prepare Mrs. Wardlaw for the unexpected visit. The preparation, however, did not take long, for a moment later Maude Wardlaw entered, supported by her nurse. Her lips moved mechanically as she saw us, but we could not hear what she said. As she walked, I could see that she had a peculiar gait, as though she were always lifting her feet over small obstacles. Her eyes, too, as she looked at us, had a strange squint, and now and then the muscles of her face twitched. She glanced from Leslie to Kennedy inquiringly, as Leslie introduced us, implying that we were from his office, then dropped into the easy-chair. Her breathing seemed to be labored and her heart action feeble, as the nurse propped her up comfortably. As Mrs. Wardlaw's hand rested on the arm of the chair I saw that there was a peculiar flexion of her wrist which reminded me of the so-called "wrist-drop" of which I had heard. It was almost as if the muscles of her hands and arms, feet and legs, were weak and wasting. Once she had been beautiful, and even now, although she seemed to be a wreck of her former self, she had a sort of ethereal beauty that was very touching. "Doctor is out--just now," she hesitated, in a tone that hinted at the loss of her voice. She turned appealingly to Miss Langdale. "Oh," she murmured, "I feel so badly this morning--as if pins and needles were sticking in me--vague pains in all my limbs--" Her voice sank to a whisper and only her lips moved feebly. One had only to see her to feel sympathy. It seemed almost cruel to intrude under the circumstances, yet it was absolutely necessary if Craig were to accomplish anything. Maude Wardlaw, however, did not seem to comprehend the significance of our presence, and I wondered how Kennedy would proceed. "I should like to see your Japanese servant, Kato," he began, directly, somewhat to my surprise, addressing himself rather to Miss Langdale than to Mrs. Wardlaw. The nurse nodded and left the room without a word, as though appreciating the anomalous position in which she was placed as temporary mistress of the household. A few moments later Kato entered. He was a typical specimen of the suave Oriental, and I eyed him keenly, for to me East was East and West was West, and I was frankly suspicious, especially as I saw no reason to be otherwise in Kennedy's manner. I waited eagerly to see what Craig would do. "Sit here," directed Kennedy, indicating a straight-backed chair, on which the Japanese obediently sat. "Now cross your knees." As Kato complied, Kennedy quickly brought his hand, held flat and palm upward, sharply against the Jap's knee just below the kneecap. There was a quick reflex jerk of the leg below the knee in response. "Quite natural," Kennedy whispered, turning to Leslie, who nodded. He dismissed Kato without further questioning, having had an opportunity to observe whether he showed any of the symptoms that had appeared in the rest of the family. Craig and the Health Commissioner exchanged a few words under their breath, then Craig crossed the room to Mrs. Wardlaw. The entrance of Kato had roused her momentarily and she had been watching what was going on. "It is a simple test," explained Kennedy, indicating to Miss Langdale that he wished to repeat it on her patient. Mrs. Wardlaw's knee showed no reflex! As he turned to us, we could see that Kennedy's face was lined deeply with thought, and he paced up and down the room once or twice, considering what he had observed. I could see that even this simple interview had greatly fatigued Mrs. Wardlaw. Miss Langdale said nothing, but it was plainly evident that she objected strongly to the strain on her patient's strength. "That will be sufficient," nodded Craig, noticing the nurse. "Thank you very much. I think you had better let Mrs. Wardlaw rest in her own room." On the nurse's arm Mrs. Wardlaw withdrew and I looked inquiringly from Kennedy to Doctor Leslie. What was it that had made this beautiful woman such a wreck? It seemed almost as though the hand of fate had stretched out against one who had all to make her happy--wealth, youth, a beautiful home--for the sullen purpose of taking away what had been bestowed so bounteously. "It is polyneuritis, all right, Leslie," Craig agreed, the moment we were alone. "I think so," coincided Leslie, with a nod. "It's the CAUSE I can't get at. Is it polyneuritis of beriberi--or something else?" Kennedy did not reply immediately. "Then there are other causes?" I inquired of Leslie. "Alcohol," he returned, briefly. "I don't think that figures in this instance. At least I've seen no evidence." "Perhaps some drug?" I hazarded at a venture. Leslie shrugged. "How about the food?" inquired Craig. "Have you made any attempt to examine it?" "I have," replied the commissioner. "When I came up here first I thought of that. I took samples of all the food that I could find in the ice-box, the kitchen, and the butler's pantry. I have the whole thing, labeled, and I have already started to test them out. I'll show you what I have done when we go down to the department laboratory." Kennedy had been examining the books in the bookcase and now pulled out a medical dictionary. It opened readily to the heading, "Polyneuritis--multiple neuritis." I bent over and read with him. In the disease, it seemed, the nerve fibers themselves in the small nerves broke down and the affection was motor, sensory, vasomotor, or endemic. All the symptoms described seemed to fit what I had observed in Mrs. Wardlaw. "Invariably," the article went on, "it is the result of some toxic substance circulating in the blood. There is a polyneuritis psychosis, known as Korsakoff's syndrome, characterized by disturbances of the memory of recent events and false reminiscences, the patient being restless and disorientated." I ran my finger down the page until I came to the causes. There were alcohol, lead, arsenic, bisulphide of carbon, diseases such as diabetes, diphtheria, typhoid, and finally, much to my excitement, was enumerated beriberi, with the added information, "or, as the Japanese call it, kakke." I placed my finger on the passage and was about to say something about my suspicions of Kato when we heard the sound of footsteps in the hall, and Craig snapped the book shut, returning it hastily to the bookcase. It was Miss Langdale who had made her patient comfortable in bed and now returned to us. "Who is this Kato?" inquired Craig, voicing what was in my own mind. "What do you know about him?" "Just a young Japanese from the Mission downtown," replied the nurse, directly. "I don't suppose you know, but Mrs. Wardlaw used to be greatly interested in religious and social work among the Japanese and Chinese; would be yet, but," she added, significantly, "she is not strong enough. They employed him before I came here, about a year ago, I think." Kennedy nodded, and was about to ask another question, when there was a slight noise out in the hall. Thinking it might be Kato himself, I sprang to the door. Instead, I encountered a middle-aged man, who drew back in surprise at seeing me, a stranger. "Oh, good morning, Doctor Aitken!" greeted Miss Langdale, in quite the casual manner of a nurse accustomed to the daily visit at about this hour. As for Doctor Aitken, he glanced from Leslie, whom he knew, to Kennedy, whom he did not know, with a very surprised look on his face. In fact, I got the impression that after he had been admitted he had paused a moment in the hall to listen to the strange voices in the Wardlaw study. Leslie nodded to him and introduced us, without quite knowing what to say or do, any more than Doctor Aitken. "A most incomprehensible case," ventured Aitken to us. "I can't, for the life of me, make it out." The doctor showed his perplexity plainly, whether it was feigned or not. "I'm afraid she's not quite so well as usual," put in Miss Langdale, speaking to him, but in a manner that indicated that first of all she wished any blame for her patient's condition to attach to us and not to herself. Doctor Aitken pursed up his lips, bowed excusingly to us, and turned down the hall, followed by the nurse. As they passed on to Mrs. Wardlaw's room, I am sure they whispered about us. I was puzzled by Doctor Aitken. He seemed to be sincere, yet, under the circumstances, I felt that I must be suspicious of everybody and everything. Alone again for a moment, Kennedy turned his attention to the furniture of the room, and finally paused before a writing-desk in the corner. He tried it. It was not locked and he opened it. Quickly he ran through a pile of papers carefully laid under a paper-weight at the back. A suppressed exclamation from him called my attention to something that he had discovered. There lay two documents, evidently recently drawn up. As we looked over the first, we saw that it was Doctor Wardlaw's will, in which he had left everything to his wife, although he was not an especially wealthy man. The other was the will of Mrs. Wardlaw. We devoured it hastily. In substance it was identical with the first, except that at the end she had added two clauses. In the first she had done just as her mother had directed. Twenty-five thousand dollars had been left to Doctor Aitken. I glanced at Kennedy, but he was reading on, taking the second clause. I read also. Fifty thousand dollars was given to endow the New York Japanese Mission. Immediately the thought of Kato and what Miss Langdale had just told us flashed through my mind. A second time we heard the nurse's footsteps on the hardwood floor of the hall. Craig closed the desk softly. "Doctor Aitken is ready to go," she announced. "Is there anything more you wish to ask?" Kennedy spoke a moment with the doctor as he passed out, but, aside from the information that Mrs. Wardlaw was, in his opinion, growing worse, the conversation added nothing to our meager store of information. "I suppose you attended Mrs. Marbury?" ventured Kennedy of Miss Langdale, after the doctor had gone. "Not all the time," she admitted. "Before I came there was another nurse, a Miss Hackstaff." "What was the matter? Wasn't she competent?" Miss Langdale avoided the question, as though it were a breach of professional etiquette to cast reflections on another nurse, although whether that was the real reason for her reticence did not appear. Craig seemed to make a mental note of the fact. "Have you seen anything--er--suspicious about this Kato?" put in Leslie, while Kennedy frowned at the interruption. Miss Langdale answered quickly, "Nothing." "Doctor Aitken has never expressed any suspicion?" pursued Leslie. "Oh no," she returned. "I think I would have known it if he had any. No, I've never heard him even hint at anything." It was evident that she wished us to know that she was in the confidence of the doctor. "I think we'd better be going," interrupted Kennedy, hastily, not apparently pleased to have Leslie break in in the investigation just at present. Miss Langdale accompanied us to the door, but before we reached it it was opened from the outside by a man who had once been and yet was handsome, although one could see that he had a certain appearance of having neglected himself. Leslie nodded and introduced us. It was Doctor Wardlaw. As I studied his face I could see that, as Leslie had already told us, it plainly bore the stigma of nervousness. "Has Doctor Aitken been here?" he inquired, quickly, of the nurse. Then, scarcely waiting for her even to nod, he added: "What did he say? Is Mrs. Wardlaw any better?" Miss Langdale seemed to be endeavoring to make as optimistic a report as the truth permitted, but I fancied Wardlaw read between the lines. As they talked it was evident that there was a sort of restraint between them. I wondered whether Wardlaw might not have some lurking suspicion against Aitken, or some one else. If he had, even in his nervousness he did not betray it. "I can't tell you how worried I am," he murmured, almost to himself. "What can this thing be?" He turned to us, and, although he had just been introduced, I am sure that our presence seemed to surprise him, for he went on talking to himself, "Oh yes--let me see--oh yes, friends of Doctor--er--Leslie." I had been studying him and trying to recall what I had just read of beriberi and polyneuritis. There flashed over my mind the recollection of what had been called Korsakoff's syndrome, in which one of the mental disturbances was the memory of recent events. Did not this, I asked myself, indicate plainly enough that Leslie might be right in his suspicions of beriberi? It was all the more apparent a moment later when, turning to Miss Langdale, Wardlaw seemed almost instantly to forget our presence again. At any rate, his anxiety was easy to see. After a few minutes' chat during which Craig observed Wardlaw's symptoms, too, we excused ourselves, and the Health Commissioner undertook to conduct us to his office to show us what he had done so far. As for me, I could not get Miss Langdale out of my mind, and especially the mysterious letter to Kennedy. What of it and what of its secret sender? None of us said much until, half an hour later, in the department laboratory, Leslie began to recapitulate what he had already done in the case. "You asked whether I had examined the food," he remarked, pausing in a corner before several cages in which were a number of pigeons, separated and carefully tagged. With a wave of his hand at one group of cages he continued: "These fellows I have been feeding exclusively on samples of the various foods which I took from the Wardlaw family when I first went up there. Here, too, are charts showing what I have observed up to date. Over there are the 'controls'--pigeons from the same group which have been fed regularly on the usual diet so that I can check my tests." Kennedy fell to examining the pigeons carefully as well as the charts and records of feeding and results. None of the birds fed on what had been taken from the apartment looked well, though some were worse than others. "I want you to observe this fellow," pointed out Leslie at last, singling out one cage. The pigeon in it was a pathetic figure. His eyes seemed dull and glazed. He paid little or no attention to us; even his food and water did not seem to interest him. Instead of strutting about, he seemed to be positively wabbly on his feet. Kennedy examined this one longer and more carefully than any of the rest. "There are certainly all the symptoms of beriberi, or rather, polyneuritis, in pigeons, with that bird," admitted Craig, finally, looking up at Leslie. The commissioner seemed to be gratified. "You know," he remarked, "beriberi itself is a common disease in the Orient. There has been a good deal of study of it and the cause is now known to be the lack of something in the food, which in the Orient is mostly rice. Polishing the rice, which removes part of the outer coat, also takes away something that is necessary for life, which scientists now call 'vitamines.'" "I may take some of these samples to study myself?" interrupted Kennedy, as though the story of vitamines was an old one to him. "By all means," agreed Leslie. Craig selected what he wanted, keeping each separate and marked, and excused himself, saying that he had some investigations of his own that he wished to make and would let Leslie know the result as soon as he discovered anything. Kennedy did not go back directly to the laboratory, however. Instead, he went up-town and, to my surprise, stopped at one of the large breweries. What it was that he was after I could not imagine, but, after a conference with the manager, he obtained several quarts of brewer's yeast, which he had sent directly down to the laboratory. Impatient though I was at this seeming neglect of the principal figures in the case, I knew, nevertheless, that Kennedy had already schemed out his campaign and that whatever it was he had in mind was of first importance. Back at last in his own laboratory, Craig set to work on the brewer's yeast, deriving something from it by the plentiful use of a liquid labeled "Lloyd's reagent," a solution of hydrous aluminum silicate. After working for some time, I saw that he had obtained a solid which he pressed into the form of little whitish tablets. He had by no means finished, but, noticing my impatience, he placed the three or four tablets in a little box and handed them to me. "You might take these over to Leslie in the department laboratory, Walter," he directed. "Tell him to feed them to that wabbly-looking pigeon over there--and let me know the moment he observes any effect." Glad of the chance to occupy myself, I hastened on the errand, and even presided over the first feeding of the bird. When I returned I found that Kennedy had finished his work with the brewer's yeast and was now devoting himself to the study of the various samples of food which he had obtained from Leslie. He was just finishing a test of the baking-powder when I entered, and his face showed plainly that he was puzzled by something that he had discovered. "What is it?" I asked. "Have you found out anything?" "This seems to be almost plain sodium carbonate," he replied, mechanically. "And that indicates?" I prompted. "Perhaps nothing, in itself," he went on, less abstractedly. "But the use of sodium carbonate and other things which I have discovered in other samples disengages carbon dioxide at the temperature of baking and cooking. If you'll look in that public-health report on my desk you'll see how the latest investigations have shown that bicarbonate of soda and a whole list of other things which liberate carbon dioxide destroy the vitamines Leslie was talking about. In other words, taken altogether I should almost say there was evidence that a concerted effort was being made to affect the food--a result analogous to that of using polished rice as a staple diet--and producing beriberi, or, perhaps more accurately, polyneuritis. I can be sure of nothing yet, but--it's worth following up." "Then you think Kato--" "Not too fast," cautioned Craig. "Remember, others had access to the kitchen, too." In spite of his hesitancy, I could think only of the two paragraphs we had read in Mrs. Wardlaw's will, and especially of the last. Might not Kato have been forced or enticed into a scheme that promised a safe return and practically no chance of discovery? What gruesome mystery had been unveiled by the anonymous letter which had first excited our curiosity? It was late in the afternoon that Commissioner Leslie called us up, much excited, to inform us that the drooping pigeon was already pecking at food and beginning to show some interest in life. Kennedy seemed greatly gratified as he hung up the receiver. "Almost dinner-time," he commented, with a glance at his watch. "I think we'll make another hurried visit to the Wardlaw apartment." We had no trouble getting in, although as outsiders we were more tolerated than welcome. Our excuse was that Kennedy had some more questions which we wished to ask Miss Langdale. While we waited for her we sat, not in the study, but in the parlor. The folding-doors into the dining-room were closed, but across the hall we could tell by the sound when Kato was in the kitchen and when he crossed the hall. Once I heard him in the dining-room. Before I knew it Kennedy had hastily tiptoed across the hall and into the kitchen. He was gone only a couple of minutes, but it was long enough to place in the food that was being prepared, and in some unprepared, either the tablets he had made or a powder he had derived from them crushed up. When he returned I saw from his manner that the real purpose of the visit had been accomplished, although when Miss Langdale appeared he went through the form of questioning her, mostly on Mrs. Marbury's sickness and death. He did not learn anything that appeared to be important, but at least he covered up the reason for his visit. Outside the apartment, Kennedy paused a moment. "There's nothing to do now but await developments," he meditated. "Meanwhile, there is no use for us to double up our time together. I have decided to watch Kato to-night. Suppose you shadow Doctor Aitken. Perhaps we may get a line on something that way." The plan seemed admirable to me. In fact, I had been longing for some action of the sort all the afternoon, while Kennedy had been engaged in the studies which he evidently deemed more important. Accordingly, after dinner, we separated, Kennedy going back to the Forum Apartments to wait until Kato left for the night, while I walked farther up the Drive to the address given in the directory as that of Doctor Aitken. It happened to be the time when the doctor had his office hours for patients, so that I was sure at least that he was at home when I took my station just down the street, carefully scrutinizing every one who entered and left his house. Nothing happened, however, until the end of the hour during which he received office calls. As I glanced down the street I was glad that I had taken an inconspicuous post, for I could see Miss Langdale approaching. She was not in her nurse's uniform, but seemed to be off duty for an hour or two, and I must confess she was a striking figure, even in that neighborhood which was noted for its pretty and daintily gowned girls. Almost before I knew it she had entered the English-basement entrance of Doctor Aitken's. I thought rapidly. What could be the purpose of her visit? Above all, how was I, on the outside, to find out? I walked down past the house. But that did no good. In a quandary, I stopped. Hesitation would get me nothing. Suddenly an idea flashed through my mind. I turned in and rang the bell. "It's past the doctor's office hours," informed a servant who opened the door. "He sees no one after hours." "But," I lied, "I have an appointment. Don't disturb him. I can wait." The waiting-room was empty, I had seen, and I was determined to get in at any cost. Reluctantly the servant admitted me. For several moments I sat quietly alone, fearful that the doctor might open the double doors of his office and discover me. But nothing happened and I grew bolder. Carefully I tiptoed to the door. It was of solid oak and practically impervious to sound. The doors fitted closely, too. Still, by applying my ear, I could make out the sound of voices on the other side. I strained my ears both to catch a word now and then and to be sure that I might hear the approach of anybody outside. Was Aitken suspiciously interested in the pretty nurse--or was she suspiciously interested in him? Suddenly their voices became a trifle more distinct. "Then you think Doctor Wardlaw has it, too?" I heard her ask. I did not catch the exact reply, but it was in the affirmative. They were approaching the door. In a moment it would be opened. I waited to hear no more, but seized my hat and dashed for the entrance from the street just in time to escape observation. Miss Langdale came out shortly, the doctor accompanying her to the door, and I followed her back to the Forum. What I had heard only added to the puzzle. Why her anxiety to know whether Wardlaw himself was affected? Why Aitken's solicitude in asserting that he was? Were they working together, or were they really opposed? Which might be using the other? My queries still unanswered, I returned to Aitken's and waited about some time, but nothing happened, and finally I went on to our own apartment. It was very late when Craig came in, but I was still awake and waiting for him. Before I could ask him a question he was drawing from me what I had observed, listening attentively. Evidently he considered it of great importance, though no remark of his betrayed what interpretation he put on the episode. "Have you found anything?" I managed to ask, finally. "Yes, indeed," he nodded, thoughtfully. "I shadowed Kato from the Forum. It must have been before Miss Langdale came out that he left. He lives down-town in a tenement-house. There's something queer about that Jap." "I think there is," I agreed. "I don't like his looks." "But it wasn't he who interested me so much to-night," Craig went on, ignoring my remark, "as a woman." "A woman?" I queried, in surprise. "A Jap, too?" "No, a white woman, rather good-looking, too, with dark hair and eyes. She seemed to be waiting for him. Afterward I made inquiries. She has been seen about there before." "Who was she?" I asked, fancying perhaps Miss Langdale had made another visit while she was out, although from the time it did not seem possible. "I followed her to her house. Her name is Hackstaff--" "The first trained nurse!" I exclaimed. "Miss Hackstaff is an enigma," confessed Kennedy. "At first I thought that perhaps she might be one of those women whom the Oriental type fascinated, that she and Kato might be plotting. Then I have considered that perhaps her visits to Kato may be merely to get information--that she may have an ax to grind. Both Kato and she will bear watching, and I have made arrangements to have it done. I've called on that young detective, Chase, whom I've often used for the routine work of shadowing. There's nothing more that we can do now until to-morrow, so we might as well turn in." Early the next day Kennedy was again at work, both in his own laboratory and in that of the Health Department, making further studies of the food and the effect it had on the pigeons, as well as observing what changes were produced by the white tablets he had extracted from the yeast. It was early in the forenoon when the buzzer on the laboratory door sounded and I opened the door to admit Chase in a high state of excitement. "What has happened?" asked Craig, eagerly. "Many things," reported the young detective, breathlessly. "To begin with, I followed Miss Hackstaff from her apartment this morning. She seemed to be worked up over something--perhaps had had a sleepless night. As nearly as I could make out she was going about aimlessly. Finally, however, I found that she was getting into the neighborhood of Doctor Aitken and of the Forum. Well, when we got to the Forum she stopped and waited in front of it--oh, I should say almost half an hour. I couldn't make out what it was she wanted, but at last I found out." He paused a moment, then raced on, without urging. "Miss Langdale came out--and you should have seen the Hackstaff woman go for her." He drew in his breath sharply at the reminiscence. "I thought there was going to be a murder done--on Riverside Drive. Miss Langdale screamed and ran back into the apartment. There was a good deal of confusion. The hall-boys came to the rescue. In the excitement, I managed to slip into the elevator with her. No one seemed to think it strange then that an outsider should be interested. I went up with her--saw Wardlaw, as she poured out the story. He's a queer one. Is he RIGHT?" "Why?" asked Craig, indulgently. "He seems so nervous; things upset him so easily. Yet, after we had taken care of Miss Langdale and matters had quieted down, I thought I might get some idea of the cause of the fracas and asked him if he knew of any reason. Why, he looked at me kind of blankly, and I swear he acted as though he had almost forgotten it already. I tell you, he's not RIGHT." Remembering our own experience, I glanced significantly at Craig. "Korsakoff's syndrome?" I queried, laconically. "Another example of a mind confused even on recent events?" Kennedy, however, was more interested in Chase. "What did Miss Hackstaff do?" he asked. "I don't know. I missed her. When I got out again she was gone." "Pick her up again," directed Craig. "Perhaps you'll get her at her place. And see, this time, if you can get what I asked you." "I'll try," returned Chase, much pleased at the words of commendation which Craig added as he left us again. On what errand Chase had gone I could not guess, except that it had something to do with this strange woman who had so unexpectedly entered the case. Nor was Craig any more communicative. There were evidently many problems which only events could clear up even in his mind. Though he did not say anything, I knew that he was as impatient as I was, and as Leslie, too, who called up once or twice to learn whether he had discovered anything. There was nothing to do but wait. It was early in the afternoon that the telephone rang and I answered it. It was Chase calling Kennedy. I heard only half the conversation and there was not much of that, but I knew that something was about to happen. Craig hastily summoned a cab, then in rapid succession called up Doctor Aitken and Leslie, for whom we stopped as our driver shot us over to the Forum Apartments. There was no ceremony or unnecessary explanation about our presence, as Kennedy entered and directed Miss Langdale to bring her patients into the little office-study of Doctor Wardlaw. Miss Langdale obeyed reluctantly. When she returned I felt that it was appreciable that a change had taken place. Mrs. Wardlaw, at least, was improved. She was still ill, but she seemed to take a more lively interest in what was going on about her. As for Doctor Wardlaw, however, I could not see that there had been any improvement in him. His nervousness had not abated. Kato, whom Kennedy summoned at the same time, preserved his usual imperturbable exterior. Miss Langdale, in spite of the incident of the morning, was quite as solicitous as ever of her charges. We had not long to wait for Doctor Aitken. He arrived, inquiring anxiously what had happened, although Kennedy gave none of us any satisfaction immediately as to the cause of his quick action. Aitken fidgeted uneasily, glancing from Kennedy to Leslie, then to Miss Langdale, and back to Kennedy, without reading any explanation in the faces. I knew that Craig was secretly taking his time both for its effect on those present and to give Chase a chance. "Our poisons and our drugs," he began, leisurely, at length, "are in many instances the close relatives of harmless compounds that represent the intermediate steps in the daily process of metabolism. There is much that I might say about protein poisons. However, that is not exactly what I want to talk about--at least first." He stopped to make sure that he had the attention of us all. As a matter of fact, his manner was such that he attracted even the vagrant interest of the Wardlaws. "I do not know how much of his suspicions Commissioner Leslie has communicated to you," he resumed, "but I believe that you have all heard of the disease beriberi so common in the Far East and known to the Japanese as kakke. It is a form of polyneuritis and, as you doubtless know, is now known to be caused, at least in the Orient, by the removal of the pericarp in the polishing of rice. Our milling of flour is, in a minor degree, analogous. To be brief, the disease arises from the lack in diet of certain substances or bodies which modern scientists call vitamines. Small quantities of these vital principles are absolutely essential to normal growth and health and even to life itself. They are nitrogenous compounds and their absence gives rise to a class of serious disorders in which the muscles surrender their store of nitrogen first. The nerves seems to be the preferred creditors, so to speak. They are affected only after the muscles begin to waste. It is an abstruse subject and it is not necessary for me to go deeper into it now." I controlled my own interest in order to watch those about me. Kato, for one, was listening attentively, I saw. "In my studies of the diet of this household," continued Kennedy, "I have found that substances have been used in preparing food which kill vitamines. In short, the food has been denatured. Valuable elements, necessary elements, have been taken away." "I, sir, not always in kitchen, sir," interrupted Kato, still deferential. "I not always know--" With a peremptory wave of his hand Kennedy silenced the Jap. "It has long been a question," he hurried on, "whether these vitamines are tangible bodies or just special arrangements of molecules. Recently government investigators have discovered that they are bodies that can be isolated by a special process from the filtrate of brewer's yeast by Lloyd's reagent. Five grams of this"--he held up some of the tablets he had made--"for a sixty-kilogram person each day are sufficient. Unknown to you, I have introduced some of this substance into the food already deficient in vitamines. I fancy that even now I can detect a change," he nodded toward Mrs. Wardlaw. There was a murmur of surprise in the room, but before Craig could continue further the door opened and Mrs. Wardlaw uttered a nervous exclamation. There stood Chase with a woman. I recognized her immediately from Kennedy's description as Miss Hackstaff. Chase walked deliberately over to Kennedy and handed him something, while the nurse glanced calmly, almost with pity, at Mrs. Wardlaw, ignoring Wardlaw, then fixing her gaze venomously on Miss Langdale. Recalling the incident of the morning, I was ready to prevent, if necessary, a repetition now. Neither moved. But it was a thrilling, if silent, drama as the two women glared at each other. Kennedy was hastily comparing the anonymous note he had received with something Chase had brought. "Some one," he shot out, suddenly, looking up and facing us, "has, as I have intimated, been removing or destroying the vital principle in the food--these vitamines. Clearly the purpose was to make this case look like an epidemic of beriberi, polyneuritis. That part has been clear to me for some time. It has been the source of this devilish plot which has been obscure. Just a moment, Kato, I will do the talking. My detective, Chase, has been doing some shadowing for me, as well as some turning over of past history. He has found a woman, a nurse, more than a nurse, a secret lover, cast off in favor of another. Miss Hackstaff--you wrote that letter--it is your hand--for revenge--on Miss Langdale and--" "You shan't have him!" almost hissed Helen Hackstaff. "If I cannot--no one shall!" Natalie Langdale faced her, defiant. "You are a jealous, suspicious person," she cried. "Doctor Aitken knows--" "One moment," interrupted Craig. "Mrs. Marbury is gone. Mrs. Wardlaw is weakened. Yet all who are affected with nerve troubles are not necessarily suffering from polyneuritis. Some one here has been dilettanting with death. It is of no use," he thundered, turning suddenly on a cowering figure. "You stood to win most, with the money and your unholy love. But Miss Hackstaff, cast off, has proved your Nemesis. Your nervousness is the nervousness not of polyneuritis, but of guilt, Doctor Wardlaw!" IX THE RUBBER DAGGER "Hypnotism can't begin to accomplish what Karatoff claims. He's a fake, Kennedy, a fake." Professor Leslie Gaines of the Department of Experimental Psychology at the university paced excitedly up and down Craig's laboratory. "There have been complaints to the County Medical Society," he went on, without stopping, "and they have taken the case up and arranged a demonstration for this afternoon. I've been delegated to attend it and report." I fancied from his tone and manner that there was just a bit more than professional excitement involved. We did not know Gaines intimately, though of course Kennedy knew of him and he of Kennedy. Some years before, I recollected, he had married Miss Edith Ashmore, whose family was quite prominent socially, and the marriage had attracted a great deal of attention at the time, for she had been a student in one of his courses when he was only an assistant professor. "Who is Karatoff, anyhow?" asked Kennedy. "What is known about him?" "Dr. Galen Karatoff--a Russian, I believe," returned Gaines. "He claims to be able to treat disease by hypnotism-suggestion, he calls it, though it is really something more than that. As nearly as I can make out it must almost amount to thought transference, telepathy, or some such thing. Oh, he has a large following; in fact, some very well-known people in the smart set are going to him. Why," he added, facing us, "Edith--my wife--has become interested in his hypnotic clinics, as he calls them. I tell her it is more than half sham, but she won't believe it." Gaines paused and it was evident that he hesitated over asking something. "When is the demonstration?" inquired Kennedy, with unconcealed interest. The professor looked at his watch. "I'm going over there now; in fact, I'm just a bit late--only, I happened to think of you and it occurred to me that perhaps if you could add something to my report it might carry weight. Would you like to come with me? Really, I should think that it might interest you." So far Kennedy had said little besides asking a question or two. I knew the symptoms. Gaines need not have hesitated or urged him. It was just the thing that appealed to him. "How did Mrs. Gaines become interested in the thing?" queried Craig, a moment later, outside, as we climbed into the car with the professor. "Through an acquaintance who introduced her to Karatoff and the rest. Carita Belleville, the dancer, you know?" Kennedy glanced at me and I nodded that I had heard of her. It was only a few nights before that I had seen Carita at one of the midnight revues, doing a dance which was described as the "hypnotic whirl," a wild abandon of grace and motion. Carita Belleville had burst like a meteor on the sky of the "Great White Way," blazing a gorgeous trail among the fixed stars of that gay firmament. She had even been "taken up" by society, or at least a certain coterie of it, had become much sought after to do exhibition dancing at social affairs, and now was well known in the amusement notes of the newspapers and at the fashionable restaurants. She had hosts of admirers and I had no doubt that Mrs. Gaines might well have fallen under the spell of her popularity. "What is Miss Belleville's interest in Karatoff?" pursued Craig, keenly. Gaines shrugged his shoulders. "Notoriety, perhaps," he replied. "It is a peculiar group that Karatoff has gathered about him, they tell me." There was something unsatisfactory about the answer and I imagined that Gaines meant purposely to leave it so as not to prejudice the case. Somehow, I felt that there must be something risque in the doings of Karatoff and his "patients." At any rate, it was only natural with anything that Carita Belleville was likely to be concerned with. There was little time for further questions, for our destination was not far down the Drive from the university, and the car pulled up before one of the new handsome and ornate "studio apartments" up-town. We followed Gaines into the building, and the hall-boy directed us to a suite on the first floor. A moment later we were admitted by Karatoff himself to what had become known as his "hypnotic clinic," really a most artistically furnished studio. Karatoff himself was a tall, dark-haired fellow, bearded, somewhat sallow. Every feature of his remarkable face, however, was subordinate to a pair of wonderful, deep-set, piercing eyes. Even as he spoke, greeting Gaines on the rather ticklish mission he had come, and accepting us with a quick glance and nod, we could see instantly that he was, indeed, a fascinating fellow, every inch a mystic. His clinic, or, as I have said, studio, carried out well the impression of mysticism that one derived from the strange personality who presided over it. There were only two or three rooms in the apartment, one being the large room down the end of a very short hall to which he conducted us. It was darkened, necessarily, since it was on the first floor of the tall building, and the air seemed to be heavy with odors that suggested the Orient. Altogether there was a cultivated dreaminess about it that was no less exotic because studied. Doctor Karatoff paused at the door to introduce us, and we could see that we were undergoing a close scrutiny from the party who were assembled there. On a quaint stand tea was brewing and the whole assemblage had an atmosphere of bohemian camaraderie which, with the professions of Karatoff, promised well that Kennedy was not wasting time. I watched particularly the exchange of greetings between Professor Gaines and Edith Gaines, who was already there. Neither of them seemed to be perfectly at ease, though they betrayed as little as they could. However, one could not help noticing that each was watching the other, naturally. Edith Gaines was a pretty little woman, petite, light of hair, dainty, the very type of woman who craved for and thrived on attention. Here at least there seemed to be no lack of it. There was only one other woman in the room who attracted the men equally, Carita Belleville herself. Carita was indeed a stunning woman, tall, slender, dark, with a wonderful pair of magnetic eyes. As I watched, I could see that both women were quite friendly with Doctor Karatoff--perhaps even rivals for his attentions. I saw Gaines watching Carita attentively, never in the mean time failing for long to lose sight of Mrs. Gaines. Was he trying to estimate the relative popularity of the two in this strange group? If so, I failed to see any approval of either. Introductions were now coming so fast that neither Kennedy nor I had much opportunity except for the most cursory observation of the people. Among the men, however, I noticed two especially who proved worth observation. One was Armand Marchant, well known as a broker, not so much for his professional doings as for his other activities. Though successful, he was better known as one of those who desert Wall Street promptly at the hour of closing, to be found late in the afternoon at the tea dances up-town. Another was Cyril Errol, a man of leisure, well known also in the club world. He had inherited an estate, small, perhaps, but ample to allow him to maintain appearances. Errol impressed you as being one to whom the good things of the world appealed mightily, a hedonist, and, withal, very much attracted to and by the ladies. It was fortunate that the serving of tea enabled us to look about and get our bearings. In spite of the suppressed excitement and obvious restraint of the occasion, we were able to learn much over the tea-cups. Errol seemed to vibrate between the group about Mrs. Gaines and that about Miss Belleville, welcome wherever he went, for he was what men commonly call a "good mixer." Marchant, on the other hand, was almost always to be found not far from Edith Gaines. Perhaps it was the more brilliant conversation that attracted him, for it ran on many subjects, but it was difficult to explain it so to my satisfaction. All of which I saw Gaines duly noting, not for the report he had to make to the Medical Society, but for his own information. In fact, it was difficult to tell the precise degree of disapproval with which he regarded Karatoff, Errol, and Marchant, in turn, as he noted the intimacy of Edith Gaines with them. I wished that we might observe them all when they did not know it, for I could not determine whether she was taking pleasure in piquing the professor or whether she was holding her admirers in leash in his presence. At any rate, I felt I need lay no claim to clairvoyance to predict the nature of the report that Gaines would prepare. The conversation was at its height when Karatoff detached himself from one of the groups and took a position in a corner of the room, alone. Not a word was said by him, yet as if by magic the buzz of conversation ceased. Karatoff looked about as though proud of the power of even his silence. Whatever might be said of the man, at least his very presence seemed to command respect from his followers. I had expected that he would make some reference to Gaines and ourselves and the purpose of the meeting, but he avoided the subject and, instead, chose to leap right into the middle of things. "So that there can be no question about what I am able to do," he began, "I wish each of you to write on a piece of paper what you would like to have me cause any one to do or say under hypnotism. You will please fold the paper tightly, covering the writing. I will read the paper to myself, still folded up, will hypnotize the subject, and will make the subject do whatever is desired. That will be preliminary to what I have to say later about my powers in hypnotic therapeutics." Pieces of paper and little lead-pencils were distributed by an attendant and in the rustling silence that followed each cudgeled his brain for something that would put to the test the powers of Karatoff. Thinking, I looked about the room. Near the speaker stood a table on which lay a curious collection of games and books, musical instruments, and other things that might suggest actions to be performed in the test. My eye wandered to a phonograph standing next the table. Somehow, I could not get Mrs. Gaines and Carita Belleville out of my head. Slowly I wrote, "Have Mrs. Gaines pick out a record, play it on the phonograph, then let her do as she pleases." Some moments elapsed while the others wrote. Apparently they were trying to devise methods of testing Doctor Karatoff's mettle. Then the papers were collected and deposited on the table beside him. Apparently at random Karatoff picked out one of the folded papers, then, seemingly without looking at it and certainly without unfolding it, as far as I could determine, he held it up to his forehead. It was an old trick, I knew. Perhaps he had palmed a sponge wet with alcohol or some other liquid, had brushed it over the paper, making the writing visible through it, and drying out rapidly so as to leave the paper opaque again long before any of us saw it a second time. Or was he really exercising some occult power? At any rate, he read it, or pretended to read it, at least. "I am asked to hypnotize Mrs. Gaines," he announced, dropping the paper unconcernedly on the table beside the other pile, as though this were mere child's play for his powers. It was something of a shock to realize that it was my paper he had chanced to pick up first, and I leaned forward eagerly, watching. Mrs. Gaines rose and every eye was riveted on her as Karatoff placed her in an easy-chair before him. There was an expectant silence, as Karatoff moved the chair so that she could concentrate her attention only on a bright silver globe suspended from the ceiling. The half-light, the heavy atmosphere, the quiet, assured manner of the chief actor in the scene, all combined to make hypnotization as nearly possible as circumstances could. Karatoff moved before her, passing his hands with a peculiar motion before her eyes. It seemed an incredibly short time in which Edith Gaines yielded to the strange force which fascinated the group. "Quite susceptible," murmured Kennedy, beside me, engrossed in the operation. "It is my test," I whispered back, and he nodded. Slowly Edith Gaines rose from the chair, faced us with unseeing eyes, except as Karatoff directed. Karatoff himself was a study. It seemed as if he had focused every ounce of his faculties on the accomplishment of the task in hand. Slowly still the woman moved, as if in a dream walk, over toward the phonograph, reached into the cabinet beneath it and drew forth a book of records. Karatoff faced us, as if to assure us that at that point he had resigned his control and was now letting her act for her subconscious self. Her fingers passed over page after page until finally she stopped, drew forth the record, placed it on the machine, wound it, then placed the record on the revolving disk. My first surprise was quickly changed to gratification. She had picked out the music to the "Hypnotic Whirl." I bent forward, more intent. What would she do next? As she turned I could see, even in the dim light, a heightened color in her cheeks, as though the excitement of the catchy music had infected her. A moment later she was executing, and very creditably, too, an imitation of Carita herself in the Revue. What did it mean? Was it that consciously or unconsciously she was taking the slender dancer as her model? The skill and knowledge that she put into the dance showed plainly. Next to Kennedy, I saw Gaines leaning far forward, looking now at his wife, now at the little group. I followed his eyes. To my surprise, I saw Marchant, his gaze riveted on Edith Gaines as if she had been the star performer in a play. Evidently my chance request to Karatoff had been builded better than I knew. I ran my gaze over the others. Errol was no less engrossed than Marchant. Quickly I glanced at Carita, wondering whether she might be gratified by the performance of a pupil. Whether it was natural grace or real hypnotism in the "Hypnotic Whirl," I was surprised to see on Carita's face something that looked strangely akin to jealousy. It was as though some other woman had usurped her prerogative. She leaned over to speak to Errol with the easy familiarity of an old admirer. I could not hear what was said and perhaps it was inconsequential. In fact, it must have been the very inconsequentiality of his reply that piqued her. He glanced at Marchant a moment, as if she had said something about him, then back at Edith Gaines. On his part, Professor Gaines was growing more and more furious. I had just about decided that the little drama in the audience was of far more importance and interest than even the dance, when the music ceased. Karatoff approached, took Mrs. Gaines by the hand, led her back to the chair, and, at a word, she regained her normal consciousness. As she rose, still in a daze it seemed, it was quite evident that she had no waking realization of what had happened, for she walked back and sat down beside her husband, quite as though nothing had happened. As for me, I could not help wondering what had actually happened. What did it all mean? Had Mrs. Gaines expressed her own self--or was it Karatoff--or Marchant--or Errol? What was the part played by Carita Belleville? Gaines did not betray anything to her, but their mutual attitude was eloquent. There was something of which he disapproved and she knew it, some lack of harmony. What was the cause? As for Karatoff's exhibition, it was all truly remarkable, whether in his therapeutics the man was a faker or not. Karatoff seemed to realize that he had made a hit. Without giving any one a chance to question him, he reached down quickly and picked up another of the papers, repeating the process through which he had gone before. "Mr. Errol," he summoned, placing the second folded paper on the table with the first. Errol rose and went forward and Karatoff placed him in the chair as he had Mrs. Gaines. There seemed to be no hesitation, at least on the part of Karatoff's followers, to being hypnotized. Whatever it was written on the paper, the writer had evidently not trusted to chance, as I had, but had told specifically what to do. At the mute bidding of Karatoff Errol rose. We watched breathlessly. Deliberately he walked across the room to the table, and, to the astonishment of all save one, picked up a rubber dagger, one of those with which children play, which was lying in the miscellaneous pile on the table. I had not noticed it, but some one's keen eye had, and evidently it had suggested a melodramatic request. Quickly Errol turned. If he had been a motion-picture actor, he could not have portrayed better the similitude of hate that was written on his face. A few strides and he had advanced toward our little audience, now keyed up to the highest pitch of excitement by the extraordinary exhibition. "Of course," remarked Karatoff, as at a word Errol paused, still poising the dagger, "you know that under hypnotism in the psychological laboratory a patient has often struck at his 'enemy' with a rubber dagger, going through all the motions of real passion. Now!" No word was said by Karatoff to indicate to Errol what it was that he was to do. But a gasp went up from some one as he took another step and it was evident that it was Marchant whom he had singled out. For just a moment Errol poised the rubber dagger over his "victim," as if gloating. It was dramatic, realistic. As Errol paused, Marchant smiled at the rest of us, a sickly smile, I thought, as though he would have said that the play was being carried too far. Never for a moment did Errol take from him the menacing look. It was only a moment in the play, yet it was so unexpected that it seemed ages. Then, swiftly, down came the dagger on Marchant's left side just over the breast, the rubber point bending pliantly as it descended. A sharp cry escaped Marchant. I looked quickly. He had fallen forward, face down, on the floor. Edith Gaines screamed as we rushed to Marchant and turned him over. For the moment, as Kennedy, Karatoff, and Gaines bent over him and endeavored to loosen his collar and apply a restorative, consternation reigned in the little circle. I bent over, too, and looked first at Marchant's flushed face, then at Kennedy. Marchant was dead! There was not a mark on him, apparently. Only a moment before he had been one of us. We could look at one another only in amazement, tinged with fear. Killed by a rubber dagger? Was it possible? "Call an ambulance--quick!" directed Kennedy to me, though I knew that he knew it was of no use except as a matter of form. We stood about the prostrate form, stunned. In a few moments the police would be there. Instinctively we looked at Karatoff. Plainly he was nervous and overwrought now. His voice shook as he brought Errol out of the trance, and Errol, dazed, uncomprehending, struggled to take in the horribly unreal tragedy which greeted his return to consciousness. "It--it was an accident," muttered Karatoff, eagerly trying to justify himself, though trembling for once in his life. "Arteriosclerosis, perhaps, hardening of the arteries, some weakness of the heart. I never--" He cut the words short as Edith Gaines reeled and fell into her husband's arms. She seemed completely prostrated by the shock. Or was it weakness following the high mental tension of her own hypnotization? Together we endeavored to revive her, waiting for the first flutter of her eyelids, which seemed an interminable time. Errol in the mean time was pacing the floor like one in a dream. Events had followed one another so fast in the confusion that I had only an unrelated series of impressions. It was not until a moment later that I realized the full import of the affair, when I saw Kennedy standing near the table in the position Karatoff had assumed, a strange look of perplexity on his face. Slowly I realized what was the cause. The papers on which were written the requests for the exhibitions of Karatoff's skill were gone! Whatever was done must be done quickly, and Kennedy looked about with a glance that missed nothing. Before I could say a word about the papers he had crossed the room to where Marchant had been standing in the little group about Edith Gaines as we entered. On a side-table stood the teacup from which he had been sipping. With his back to the rest, Kennedy drew from his breast pocket a little emergency case he carried containing a few thin miniature glass tubes. Quickly he poured the few drops of the dregs of the tea into one of the tubes, then into others tea from the other cups. Again he looked at the face of Marchant as though trying to read in the horrified smile that had petrified on it some mysterious secret hidden underneath. Slowly the question was shaping in my mind, was it, as Karatoff would have us believe, an accident? The clang of a bell outside threw us all into worse confusion, and a moment later, almost together, a white-coated surgeon and a blue-coated policeman burst into the room. It seemed almost no time, in the swirl of events, before the policeman was joined by a detective assigned by the Central Office to that district. "Well, doctor," demanded the detective as he entered, "what's the verdict?" "Arteriosclerosis, I think," replied the young surgeon. "They tell me there was some kind of hypnotic seance going on. One of them named Errol struck at him with a rubber dagger, and--" "Get out!" scoffed the Central Office man. "Killed by a rubber dagger! Say, what do you think we are? What did you find when you entered, sergeant?" The policeman handed the detective the rubber dagger which he had picked up, forgotten, on the floor where Errol had dropped it when he came out from the hypnotization. The detective took it gingerly and suspiciously, with a growl. "I'll have the point of this analyzed. It may be--well--we won't say what may be. But I can tell you what is. You, Doctor Karatoff, or whatever your name is, and you, Mr. Errol, are under arrest. It's a good deal easier to take you now than it will be later. Then if you can get a judge to release you, we'll at least know where you are." "This is outrageous, preposterous!" stormed Karatoff. "Can't help it," returned the officer, coolly. "Why," exclaimed Carita Belleville, excitedly projecting herself before the two prisoners, "it's ridiculous! Even the ambulance surgeon says it was arteriosclerosis, an accident. I--" "Very well, madam," calmed the sergeant. "So much the better. They'll get out of our hands that much quicker. Just at present it is my duty." Errol was standing silent, his eyes averted from the hideous form on the floor, not by word or action betraying a feeling. The police moved to the door. Weak and trembling still from the triple shock she had received, Edith Gaines leaned heavily on the arm of her husband, but it was, as nearly as I could make out, only for physical support. "I told you, Edith, it was a dangerous business," I heard him mutter. "Only I never contemplated that they'd carry it this far. Now you see what such foolishness can lead to." Weak though she was, she drew away and flashed a glance at him, resenting his man's "I-told-you-so" manner. The last I saw of them in the confusion was as they drove off in the car, still unreconciled. Kennedy seemed well contented, for the present at least, to allow the police a free hand with Errol and Karatoff. As for me, Mrs. Gaines and Carita Belleville presented a perplexing problem, but I said nothing, for he was hurrying back now to his laboratory. At once he drew forth the little tube containing the few drops of tea and emptied a drop or two into a beaker of freshly distilled water as carefully as if the tea had been some elixir of life. As he was examining the contents of the beaker his face clouded with thought. "Do you find anything?" I asked, eagerly. Kennedy shook his head. "There's something wrong," he hazarded. "Perhaps it's only fancy, but I am sure that there is something with a slight odor in the tea, something tea-like, but with a more bitter taste, something that would be nauseous if not concealed in the tea. There's more than tannin and sugar here." "Then you think that some one present placed something in the tea?" I inquired, shuddering at the thought that we had run some unknown danger. "I can't just say, without further investigation of this and the other samples I took." "Still, you have eliminated that ridiculous dagger theory," I ventured. "The police can never appreciate the part it played," Craig answered, non-committally, laying out various chemicals preparatory to his exhaustive analysis. "I began to suspect something the moment I noticed that those notes which we all wrote were gone. When we find out about this tea we may find who took them. Perhaps the mystery is not such a mystery after all, then." There seemed to be nothing that I could do, in the mean time, except to refrain from hindering Kennedy in his investigations, and I decided to leave him at the laboratory while I devoted my time to watching what the police might by chance turn up, even if they should prove to be working on the wrong angle of the case. I soon found that they were showing energy, if nothing else. Although it was so soon after the death of Marchant, they had determined that there could not have been anything but rubber on the end of the toy dagger which had excited the doubts of the detective. As for the autopsy that was performed on Marchant, it did, indeed, show that he was suffering from hardening of the arteries, due to his manner of living, as Karatoff had asserted. Indeed, the police succeeded in showing that it was just for that trouble that Marchant was going to Karatoff, which, to my mind, seemed quite sufficient to establish the therapeutic hypnotist as all that Gaines had accused him of being. Even to my lay mind the treatment of arteriosclerosis by mental healing seemed, to say the least, incongruous. Yet the evidence against Karatoff and Errol was so flimsy that they had little trouble in getting released on bail, though, of course, it was fixed very high. My own inquiries among the other reporters on the Star who might know something offered a more promising lead. I soon found that Errol had none too savory a reputation. His manner of life had added nothing to his slender means, and there was a general impression among his fellow club-members that unfortunate investments had made serious inroads into the principal of his fortune. Still, I hesitated to form even an opinion on gossip. Quite unsatisfied with the result of my investigation, I could not restrain my impatience to get back to the laboratory to find out whether Kennedy had made any progress in his tests of the tea. "If you had been five minutes earlier," he greeted me, "you would have been surprised to find a visitor." "A visitor?" I repeated. "Who?" "Carita Belleville," he replied, enjoying my incredulity. "What could she want?" I asked, at length. "That's what I've been wondering," he agreed "Her excuse was plausible. She said that she had just heard why I had come with Gaines. I suppose it was half an hour that she spent endeavoring to convince me that Karatoff and Errol could not possibly have had any other connection than accidental with the death of Marchant." "Could it have been a word for them and half an hour for herself?" I queried, mystified. Kennedy shrugged. "I can't say. At any rate, I must see both Karatoff and Errol, now that they are out. Perhaps they did send her, thinking I might fall for her. She hinted pretty broadly at using my influence with Gaines on his report. Then, again, she may simply have been wondering how she herself stood." "Have you found anything?" I asked, noticing that his laboratory table was piled high with its usual paraphernalia. "Yes," he replied, laconically, taking a bottle of concentrated sulphuric acid and pouring a few drops in a beaker of slightly tinged water. The water turned slowly to a beautiful green. No sooner was the reaction complete than he took some bromine and added it. Slowly again the water changed, this time from the green to a peculiar violet red. Adding more water restored the green color. "That's the Grandeau test," he nodded, with satisfaction. "I've tried the physiological test, too, with frogs from the biological department, and it shows the effect on the heart that I--" "What shows the effect?" I interrupted, somewhat impatiently. "Oh, to be sure," he smiled. "I forgot I hadn't told you what I suspected. Why, digitalis--foxglove, you know. I suppose it never occurred to the police that the rubber dagger might have covered up a peculiar poisoning? Well, if they'll take the contents of the stomach, in alcohol, with a little water acidulated, strain off the filtrate and try it on a dog, they will see that its effect is the effect of digitalis. Digitalis is an accumulative poison and a powerful stimulant of arterial walls, by experimental evidence an ideal drug for the purpose of increasing blood pressure. Don't you see it?" he added, excitedly. "The rubber dagger was only a means to an end. Some one who knew the weakness of Marchant first placed digitalis in his tea. That was possible because of the taste of the tea. Then, in the excitement of the act pantomimed by Errol, Marchant's disease carried him off, exactly as was to be expected under the circumstances. It was clever, diabolically clever. Whoever did it destroyed the note in which the act was suggested and counted that no one would ever stop to search for a poison in the tangle of events." Slowly but clearly I began to realize how certainly Kennedy was reconstructing the strange case. But who was it? What was the motive back of this sinister murder that had been so carefully planned that no one would ever suspect a crime? I had hardly framed the queries when our telephone rang. It was the Central Office man. The detective had anticipated my own line of inquiry, only had gone much further with it. He had found a clear record of the business relations existing between Errol and Marchant. One episode consisted of a stock deal between them in which Errol had invested in a stock which Marchant was promoting and was known to be what brokers call "cats and dogs." That, I reasoned, must have been the basis of the gossip that Errol had suffered financial losses that seriously impaired his little fortune. It was an important item and Kennedy accepted it gladly, but said nothing of his own discovery. The time had not arrived yet to come out into the open. For a few moments after the talk with the detective Kennedy seemed to be revolving the case, as though in doubt whether the new information cleared it up or added to the mystery. Then he rose suddenly. "We must find Karatoff," he announced. Whatever might have been the connection of the hypnotist with this strange case, he was far too clever to betray himself by any such misstep as seeming to avoid inquiry. We found him easily at his studio apartment, nor did we have any difficulty in gaining admittance. He knew that he was watched and that frankness was his best weapon of defense. "Of course," opened Kennedy, "you know that investigation has shown that you were right in your diagnosis of the trouble with Marchant. Was it arteriosclerosis for which you were treating him?" "It would be unprofessional to discuss it," hastily parried Karatoff, "but, since Mr. Marchant is now dead, I think I may say that it was. In fact, few persons, outside of those whom I have associated about me, realize to what a wonderful extent hypnotism may be carried in the treatment of disease. Why, I have even had wonderful success with such disorders as diabetes mellitus. We are only on the threshold of understanding what a wonderful thing is the human mind in its effect on the material body." "But another patient might have known what Marchant was being treated for?" interrupted Kennedy, ignoring the defense of Karatoff, which was proceeding along the stereotyped lines of such vagaries which seem never to be without followers. Karatoff looked at him a moment in surprise. Evidently he was doing some hasty mental calculation to determine what was Craig's ulterior motive. And, in spite of his almost uncanny claims and performances, I could see that he was able to read Kennedy's mind no whit better than myself. "I suppose so," he admitted. "No doctor was ever able to control his patients' tongues. Sometimes they boast of their diseases." "Especially if they are women?" hinted Kennedy, watching the effect of the remark keenly. "I have just had the pleasure of a visit from Carita Belleville in my laboratory." "Indeed?" returned Karatoff, with difficulty restraining his curiosity. "Miss Belleville has been very kind in introducing me to some of her friends and acquaintances, and I flatter myself that I have been able to do them much good." "Then she was not a patient?" pursued Kennedy, studiously avoiding enlightening Karatoff on the visit. "Rather a friend," he replied, quickly. "It was she who introduced Mr. Errol." "They are quite intimate, I believe," put in Kennedy at a chance. "Really, I knew very little about it," Karatoff avoided. "Did she introduce Mr. Marchant?" "She introduced Mrs. Gaines, who introduced Mr. Marchant," the hypnotist replied, with apparent frankness. "You were treating Mrs. Gaines?" asked Craig, again shifting the attack unexpectedly. "Yes," admitted Karatoff, stopping. "I imagine her trouble was more mental than physical," remarked Kennedy, in a casual tone, as though feeling his way. Karatoff looked up keenly, but was unable to read Kennedy's face. "I think," he said, slowly, "that one trouble was that Mrs. Gaines liked the social life better than the simple life." "Your clinic, Mr. Marchant, and the rest better than her husband and the social life at the university," amplified Kennedy. "I think you are right. She had drifted away from her husband, and when a woman does that she has hosts of admirers--of a certain sort. I should say that Mr. Errol was the kind who would care more for the social life than the simple life, as you put it, too." I did not gather in what direction Kennedy was tending, but it was evident that Karatoff felt more at ease. Was it because the quest seemed to be leading away from himself? "I had noticed something of the sort," he ventured. "I saw that they were alike in that respect, but, of course, Mr. Marchant was her friend." Suddenly the implication flashed over me, but before I could say anything Kennedy cut in, "Then Mr. Errol might have been enacting under hypnotism what were really his own feelings and desires?" "I cannot say that," replied Karatoff, seeking to dodge the issue. "But under the influence of suggestion I suppose it is true that an evil-minded person might suggest to another the commission of a crime, and the other, deprived of free will, might do it. The rubber dagger has often been used for sham murders. The possibility of actual murder cannot be denied. In this case, however, there can be no question that it was an unfortunate accident." "No question?" demanded Kennedy, directly. If Karatoff was concealing anything, he made good concealment. Either to protect himself or another he showed no evidence of weakening his first theory of the case. "No question as far as I know," he reiterated. I wondered whether Kennedy planned to enlighten him on the results of his laboratory tests, but was afraid to look at either for fear of betraying some hint. I was glad I did not. Kennedy's next question carried him far afield from the subject. "Did you know that the Medical Society were interested in you and your clinic before the demonstration before Professor Gaines was arranged?" "I suspected some one was interested," answered Karatoff, quickly, "But I had no idea who it might be. As I think it over now, perhaps it was Professor Gaines who instigated the whole inquiry. He would most likely be interested. My work is so far in advance of any that the conservative psychologists do that he would naturally feel hostile, would he not?" "Especially with the added personal motive of knowing that his wife was one of your patients, along with Carita Belleville, Marchant, Errol, and the rest," added Kennedy. Karatoff smiled. "I would not have said that myself. But since you have said it, I cannot help admitting its truth. Don't you suppose I could predict the nature of any report he would make?" Karatoff faced Kennedy squarely. There was an air almost of triumph in his eyes. "I think I had better say no more, except under the advice of my lawyer," he remarked, finally. "When the police want me, they can find me here." Quite evident to me now, as we went out of the studio, was the fact that Karatoff considered himself a martyr, that he was not only the victim of an accident, but of persecution as well. "The fishing was good," remarked Kennedy, tersely, as we reached the street. "Now before I see Errol I should like to see Gaines again." I tried to reason it out as we walked along in silence. Marchant had known Edith Gaines intimately. Carita Belleville had known Errol as well. I recalled Errol hovering about Mrs. Gaines at the tea and the incident during the seance when Carita Belleville had betrayed her annoyance over some remark by Errol. The dancing by Edith Gaines had given a flash of the jealous nature of the woman. Had it been interest in Errol that had led her to visit the laboratory? Kennedy was weaving a web about some one, I knew. But about whom? As we passed a corner, he paused, entered a drugstore and called up several numbers at a pay-station telephone booth. Then we turned into the campus and proceeded rapidly toward the laboratory of the psychological department. Gaines was there, sitting at his desk, writing, as we entered. "I'm glad to see you," he greeted, laying down his work. "I am just finishing the draft of my report on that Karatoff affair. I have been trying to reach you by telephone to know whether you would add anything to it. Is there anything new?" "Yes," returned Kennedy, "there is something new. I've just come from Karatoff's and on the way I decided suddenly that it was time we did something. So I have called up, and the police will bring Errol here, as well as Miss Belleville. Karatoff will come--he won't dare stay away; and I also took the liberty of calling Mrs. Gaines." "To come here?" repeated Gaines, in mild surprise. "All of them?" "Yes. I hope you will pardon me for intruding, but I want to borrow some of your psychological laboratory apparatus, and I thought the easiest way would be to use it here rather than take it all over to my place and set it up again." "I'm sure everything is at your service," offered Gaines. "It's a little unexpected, but if the others can stand the chaotic condition of the room, I guess we can." Kennedy had been running his eye over the various instruments which Gaines and his students used in their studies, and was now examining something in a corner on a little table. It was a peculiar affair, quite simple, but conveying to me no idea of its use. There seemed to be a cuff, a glass chamber full of water into which it fitted, tubes and wires that attached various dials and recording instruments to the chamber, and what looked like a chronograph. "That is my new plethysmograph," remarked Gaines, noting with some satisfaction how Kennedy had singled it out. "I've heard the students talk of it," returned Kennedy. "It's an improved apparatus, Walter, that records one's blood flow." I nodded politely and concealed my ignorance in a discreet silence, hoping that Gaines would voluntarily enlighten us. "One of my students is preparing an exhaustive table," went on Gaines, as I had hoped, "showing the effects on blood distribution of different stimuli--for instance, cold, heat, chloroform, arenalin, desire, disgust, fear; physical conditions, drugs, emotions--all sorts of things can be studied by this plethysmograph which can be set to record blood flow through the brain, the extremities, any part of the body. When the thing is charted I think we shall have opened up a new field." "Certainly a very promising one for me," put in Kennedy. "How has this machine been improved? I've seen the old ones, but this is the first time I've seen this. How does it work?" "Well," explained Gaines, with just a touch of pride, "you see, for studying blood flow in the extremities, I slip this cuff over my arm, we'll say. Suppose it is the effect of pain I want to study. Just jab that needle in my other arm. Don't mind. It's in the interest of science. See, when I winced then, the plethysmograph recorded it. It smarts a bit and I'm trying to imagine it smarts worse. You'll see how pain affects blood flow." As he watched the indicator, Kennedy asked one question after another about the working of the machine, and the manner in which the modern psychologist was studying every emotion. "By the way, Walter," he interrupted, glancing at his watch, "call up and see if they've started with Errol and the rest yet. Don't stop, Gaines. I must understand this thing before they get here. It's just the thing I want." "I should be glad to let you have it, then," replied Gaines. "I think I'll need something new with these people," went on Kennedy. "Why, do you know what I've discovered?" "No, but I hope it's something I can add to my report?" "Perhaps. We'll see. In the first place, I found that digitalis had been put in Marchant's tea." "They'll be here directly," I reported from the telephone, hanging it up and joining them again. "It couldn't have been an accident, as Karatoff said," went on Kennedy, rapidly. "The drug increased the blood pressure of Marchant, who was already suffering from hardening of the arteries. In short, it is my belief that the episode of the rubber dagger was deliberately planned, an elaborate scheme to get Marchant out of the way. No one else seems to have noticed it, but those slips of paper on which we all wrote have disappeared. At the worst, it would look like an accident, Karatoff would be blamed, and--" There was a noise outside as the car pulled up. "Here, let me take this off before any of them see it," whispered Gaines, removing the cuff, just as the door opened and Errol and Karatoff, Carita Belleville and Edith Gaines entered. Before even a word of greeting passed, Kennedy stepped forward. "It was NOT an accident," he repeated. "It was a deliberately planned, apparently safe means of revenge on Marchant, the lover of Mrs. Gaines. Without your new plethysmograph, Gaines, you might have thrown it on an innocent person!" X THE SUBMARINE MINE "Here's the bullet. What I want you to do, Professor Kennedy, is to catch the crank who fired it." Capt. Lansing Marlowe, head of the new American Shipbuilding Trust, had summoned us in haste to the Belleclaire and had met us in his suite with his daughter Marjorie. Only a glance was needed to see that it was she, far more than her father, who was worried. "You must catch him," she appealed. "Father's life is in danger. Oh, you simply MUST." I knew Captain Marlowe to be a proverbial fire-eater, but in this case, at least, he was no alarmist. For, on the table, as he spoke, he laid a real bullet. Marjorie Marlowe shuddered at the mere sight of it and glanced apprehensively at him as if to reassure herself. She was a tall, slender girl, scarcely out of her teens, whose face was one of those quite as striking for its character as its beauty. The death of her mother a few years before had placed on her much of the responsibility of the captain's household and with it a charm added to youth. More under the spell of her plea than even Marlowe's vigorous urging, Kennedy, without a word, picked up the bullet and examined it. It was one of the modern spitzer type, quite short, conical in shape, tapering gradually, with the center of gravity back near the base. "I suppose you know," went on the captain, eagerly, "that our company is getting ready to-morrow to launch the Usona, the largest liner that has ever been built on this side of the water--the name is made up of the initials of the United States of North America. "Just now," he added, enthusiastically, "is what I call the golden opportunity for American shipping. While England and Germany are crippled, it's our chance to put the American flag on the sea as it was in the old days, and we're going to do it. Why, the shipyards of my company are worked beyond their capacity now." Somehow the captain's enthusiasm was contagious. I could see that his daughter felt it, that she was full of fire over the idea. But at the same time something vastly more personal weighed on her mind. "But, father," she interrupted, anxiously, "tell them about the BULLET." The captain smiled indulgently as though he would say that he was a tough old bird to wing. It was only a mask to hide the fighting spirit underneath. "We've had nothing but trouble ever since we laid the keel of that ship," he continued, pugnaciously, "strikes, a fire in the yard, delays, about everything that could happen. Lately we've noticed a motor-boat hanging about the river-front of the yards. So I've had a boat of my own patrolling the river." "What sort of craft is this other?" inquired Kennedy, interested at once. "A very fast one--like those express cruisers that we hear so much about now." "Whose is it? Who was in it? Have you any idea?" Marlowe shook his head doubtfully. "No idea. I don't know who owns the boat or who runs it. My men tell me they think they've seen a woman in it sometimes, though. I've been trying to figure it out. Why should it be hanging about? It can't be spying. There isn't any secrecy about the Usona. Why is it? It's a mystery." "And the shot?" prompted Craig, tapping the bullet. "Oh yes, let me tell you. Last night, Marjorie and I arrived from Bar Harbor on my yacht, for the launching. It's anchored off the yard now. Well, early this morning, while it was still gray and misty, I was up. I'll confess I'm worried over to-morrow. I hadn't been able to forget that cruiser. I was out on the deck, peering into the mist, when I'm sure I saw her. I was just giving a signal to the boat we have patrolling, when a shot whistled past me and the bullet buried itself in the woodwork of the main saloon back of me. I dug it out of the wood with my knife--so you see I got it almost unflattened. That's all I have got, too. The cruiser made a getaway, clean." "I'm sure it was aimed at him," Marjorie exclaimed. "I don't think it was chance. Don't you see? They've tried everything else. Now if they could get my father, the head of the company, that would be a blow that would cripple the trust." Marlowe patted his daughter's hand reassuringly and smiled again, as though not to magnify the incident. "Marjorie was so alarmed," he confessed, "that nothing would satisfy her but that I should come ashore and stay here at the Belleclaire, where we always put up when we are in town." The telephone rang and Marjorie answered it. "I hope you'll pardon me," she excused, hanging up the receiver. "They want me very much down-stairs." Then appealing, she added: "I'll have to leave you with father. But, please, you must catch that crank who is threatening him." "I shall do my level best," promised Kennedy. "You may depend on that." "You see," explained the captain as she left us, "I've invited quite a large party to attend the launching, for one reason or another. Marjorie must play hostess. They're mostly here at the hotel. Perhaps you saw some of them as you came in." Craig was still scanning the bullet. "It looks almost as if some one had dum-dummed it," he remarked, finally. "It's curiously done, too. Just look at those grooves." Both the captain and I looked. It had a hard jacket of cupro-nickel, like the army bullet, covering a core of softer metal. Some one had notched or scored the jacket as if with a sharp knife, though not completely through it. Had it been done for the purpose of inflicting a more frightful wound if it struck the captain? "There've been other shots, too," went on Marlowe. "One of my watchmen was wounded the night before. It didn't took like a serious wound, in the leg. Yet the poor fellow seems to be in a bad way, they tell me." "How is that?" asked Craig, glancing up quickly from studying the bullet. "The wound seems to be all puffed up, and very painful. It won't heal, and he seems to be weak and feverish. Why, I'm afraid the man will die." "I'd like to see that case," remarked Kennedy, thoughtfully. "Very well. I'll have you driven to the hospital where we have had to take him." "I'd like to see the yards, too, and the Usona," he added. "All right. After you go to the hospital I'll meet you at the yards at noon. Now if you'll come down-stairs with me, I'll get my car and have you taken to the hospital first." We followed Marlowe into the elevator and rode down. In the large parlor we saw that Marjorie Marlowe had joined a group of the guests, and the captain turned aside to introduce us. Among them I noticed a striking-looking woman, somewhat older than Marjorie. She turned as we approached and greeted the captain cordially. "I'm so glad there was nothing serious this morning," she remarked, extending her hand to him. "Oh, nothing at all, nothing at all," he returned, holding the hand, I thought, just a bit longer than was necessary. Then he turned to us, "Miss Alma Hillman, let me present Professor Kennedy and Mr. Jameson." I was not so preoccupied in taking in the group that I did not notice that the captain was more than ordinarily attentive to her. Nor can I say that I blamed him, for, although he might almost have been her father in age, there was a fascination about her that youth does not often possess. Talking with her had been a young man, slender, good-looking, with almost a military bearing. "Mr. Ogilvie Fitzhugh," introduced Marjorie, seeing that her father was neglecting his duties. Fitzhugh bowed and shook hands, murmured something stereotyped, and turned again to speak to Marjorie. I watched the young people closely. If Captain Marlowe was interested in Alma, it was more than evident that Fitzhugh was absolutely captivated by Marjorie, and I fancied that Marjorie was not averse to him, for he had a personality and a manner which were very pleasing. As the conversation ran gaily on to the launching and the gathering party of notables who were expected that night and the next day, I noticed that a dark-eyed, dark-haired, olive-complexioned young man approached and joined us. "Doctor Gavira," said Marlowe, turning to us, his tone indicating that he was well acquainted about the hotel. "He is our house physician." Gavira also was welcomed in the party, chatting with animation. It was apparent that the physician also was very popular with the ladies, and it needed only half an eye to discern that Fitzhugh was jealous when he talked to Marjorie, while Marlowe but ill concealed his restlessness when Gavira spoke to Alma. As for Alma, she seemed to treat all men impartially, except that just now it pleased her to bestow the favor of her attention on the captain. Just then a young lady, all in white, passed. Plainly she did not belong to the group, though she was much interested in it. As his eye roved over the parlor, Gavira caught her glance and bowed. She returned it, but her look did not linger. For a moment she glanced sharply at Fitzhugh, still talking to Marjorie, then at Marlowe and Alma Hillman. She was a very pretty girl with eyes that it was impossible to control. Perhaps there was somewhat of the flirt in her. It was not that that interested me. For there was something almost akin to jealousy in the look she gave the other woman. Marlowe was too engrossed to see her and she passed on slowly. What did it mean, if anything? The conversation, as usual at such times, consisted mostly of witticisms, and just at present we had a rather serious bit of business in hand. Kennedy did not betray any of the impatience that I felt, yet I knew he was glad when Marlowe excused himself and we left the party and passed down the corridor while the captain called his car. "I don't know how you are going to get at this thing," he remarked, pausing after he had sent a boy for his driver. "But I'll have to rely on you. I've told you all I know. I'll see you at noon, at the yards. My man will take you there." As he turned and left us I saw that he was going in the direction of the barber-shop. Next to it and in connection with it, though in a separate room, was a manicure. As we passed we looked in. There, at the manicure's table, sat the girl who had gone by us in the parlor and had looked so sharply at Marlowe and Alma. The boy had told us that the car was waiting at a side entrance, but Kennedy seemed now in no haste to go, the more so when Marlowe, instead of going into the barber-shop, apparently changed his mind and entered the manicure's. Craig stopped and watched. Prom where we were we could see Marlowe, though his back was turned, and neither he nor the manicure could see us. For a moment the captain paused and spoke, then sat down. Quite evidently he had a keen eye for a pretty face and trim figure. Nor was there any mistaking the pains which the manicure took to please her rich and elderly customer. After watching them a moment Kennedy lounged over to the desk in the lobby. "Who is the little manicure girl?" he asked. The clerk smiled. "Seems as if she was a good drawing-card for the house, doesn't it?" he returned. "All the men notice her. Why, her name is Rae Melzer." He turned to speak to another guest before Kennedy could follow with another inquiry. As we stood before the desk, a postman, with the parcel post, arrived. "Here's a package addressed to Dr. Fernando Gavira," he said, brusquely. "It was broken in the mail. See?" Kennedy, waiting for the clerk to be free again, glanced casually at the package at first, then with a sudden, though concealed, interest. I followed his eye. In the crushed box could be seen some thin broken pieces of glass and a wadding of cotton-wool. As the clerk signed for another package Craig saw a chance, reached over and abstracted two or three of the broken pieces of glass, then turned with his back to the postman and clerk and examined them. One I saw at once had a rim around it. It was quite apparently the top of a test-tube. The other, to which some cotton-wool still adhered, was part of the rounded bowl. Quickly Craig dropped the pieces into one of the hotel envelopes that stood in a rack on the desk, then, changing his mind about asking more now about the little manicure, strode out of the side entrance where Marlowe's car was waiting for us. Hurriedly we drove across town to the City Hospital, where we had no difficulty in being admitted and finding, in a ward, on a white cot, the wounded guard. Though his wound was one that should not have bothered him much, it had, as Marlowe said, puffed up angrily and in a most peculiar manner. He was in great pain with it and was plainly in a bad way. Though he questioned the man, Craig did not get anything out of him except that the shot had come from a cruiser which had been hanging about and was much faster than the patrol boat. The nurse and a young intern seemed inclined to be reticent, as though we might imply that the mail's condition reflected on the care he had received, which they were at pains to convince us had been perfect. Puzzled himself, Craig did not say much, but as he pondered the case, shook his head gravely to himself and finally walked out of the hospital abstractedly. "We have almost an hour before we are to meet Marlowe at the yard," he considered, as we came to the car. "I think I'll go up to the laboratory first." In the quiet of his own workshop, Kennedy carefully examined again the peculiar grooves on the bullet. He was about to scrape it, but paused. Instead, he filled a tube with a soapy solution, placed the bullet in it, and let it stand. Next he did the same with the pieces of glass from the envelope. Then he opened a drawer and from a number of capillary pipettes selected a plain capillary tube of glass. He held it in the flame of a burner until it was red hot. Then carefully he drew out one end of the tube until it was hair fine. Again he heated the other end, but this time he let the end alone, except that he allowed it to bend by gravity, then cool. It now had a siphon curve. Another tube he treated in the same way. By this time he was ready to proceed with what he had in mind. He took a glass slide and on it placed a drop from each of the tubes containing the bullet and the glass. That done, he placed the bent, larger end of the capillary tubes in turn on each of the drops on the slide. The liquid ascended the tubes by capillary attraction and siphoned over the curve, running as he turned the tubes up to the finely pointed ends. Next in a watch glass he placed some caustic soda and in another some pyrogallic acid, from each of which he took just a drop, as he had done before, inclining the tubes to let the fluid gravitate to the throttle end. Finally in the flame he sealed both the tip and butt of the tubes. "There's a bubble of air in there," he remarked. "The acid and the soda will absorb the oxygen from it. Then I can tell whether I'm right. By the way, we'll have to hurry if we're to be on time to meet Marlowe in the yard," he announced, glancing at his watch as he placed the tubes in his little electric incubator. We were a little late as the chauffeur pulled in at the executive offices at the gate of the shipyard, and Marlowe was waiting impatiently for us. Evidently he wanted action, but Kennedy said nothing yet of what he suspected and appeared now to be interested only in the yard. It was indeed something to interest any one. Everywhere were tokens of feverish activity, in office, shop, and slip. As we picked our way across, little narrow and big wide gauge engines and trains whistled and steamed about. We passed rolling-mills, forging-machines, and giant shearing-machines, furnaces for heating the frames or ribs, stone floors on which they could be pegged out and bent to shape, places for rolling and trimming the plates, everything needed from the keel plates to the deck. In the towering superstructure of the building slip we at last came to the huge steel monster itself, the Usona. As we approached, above us rose her bow, higher than a house, with poppets both there and at the stern, as well as bracing to support her. All had been done up to the launching, the stem and stern posts set in place, her sides framed and plated up, decks laid, bulkheads and casings completed, even much of her internal fitting done. Overhead and all about the huge monster was a fairy network of steel, the vast permanent construction of columns and overhead girders. Suspended beneath was a series of tracks carrying traveling and revolving cranes capable of handling the heaviest pieces. We climbed to the top and looked down at the vast stretch of hundreds of feet of deck. It was so vast that it seemed rather the work of a superman than of the puny little humans working on her. As I looked down the slip where the Usona stood inclined about half an inch to the foot, I appreciated as never before what a task it was merely to get her into the water. Below again, Marlowe explained to us how the launching ways were composed of the ground ways, fastened to the ground as the name implied, and the sliding ways that were to move over them. The sliding ways, he said, were composed of a lower course and an upper course, on which rested the "cradle," fitting closely the side of the ship. To launch her, she must be lifted slightly by the sliding ways and cradle from the keel blocks and bilge blocks, and this was done by oak wedges, hundreds of which we could see jammed between the upper and lower courses of sliding ways. Next he pointed out the rib-bands which were to keep the sliding ways on the ground ways, and at the bow the points on either side where the sliding and ground ways were bolted together by two huge timbers known as sole pieces. "You see," he concluded, "it is a gigantic task to lift thousands of tons of steel and literally carry it a quarter of a mile to forty feet of water in less than a minute. Everything has to be calculated to a nicety. It's a matter of mathematics--the moment of weight, the moment of buoyancy, and all that. This launching apparatus is strong, but compared to the weight it has to carry it is really delicate. Why, even a stray bolt in the ways would be a serious matter. That's why we have to have this eternal vigilance." As he spoke with a significant look at Kennedy, I felt that it was no wonder that Marlowe was alarmed for the safety of the ship. Millions were at stake for just that minute of launching. It was all very interesting and we talked with men whom it was a pleasure to see handling great problems so capably. But none could shed any light on the problem which it was Kennedy's to solve. And yet I felt sure, as I watched Craig, that unsatisfactory as it appeared to Marlowe and to myself, he was slowly forming some kind of theory, or at least plan of action, in his head. "You'll find me either here or at the hotel--I imagine," returned Marlowe to Kennedy's inquiry as we parted from him. "I've instructed all the men to keep their eyes open. I hope some of us have something to report soon." Whether or not the remark was intended as a hint to Kennedy, it was unnecessary. He was working as fast and as surely as he could, going over in hours what others had failed to fathom in weeks. Late in the afternoon we got back to the laboratory and Craig began immediately by taking from the little electric incubator the two crooked tubes he had left there. Breaking off the ends with tweezers, he began examining on slides the two drops that exuded, using his most powerful microscope. I was forced to curb my impatience as he proceeded carefully, but I knew that Craig was making sure of his ground at each step. "I suppose you're bursting with curiosity," he remarked at last, looking up from his examination of one of the slides. "Well, here is a drop that shows what was in the grooves of that bullet. Just take a look." I applied my eye to the microscope. All I could see was some dots and rods, sometimes something that looked like chains of dots and rods, the rods straight with square ends, sometimes isolated, but more usually joined end to end in long strings. "What is it?" I asked, not much enlightened by what he had permitted me to see. "Anaerobic bacilli and spores," he replied, excitedly. "The things that produce the well-known 'gas gangrene' of the trenches, the gas phlegmon bacilli--all sorts, the bacillus aerogenes capsulatus, bacillus proteus, pyogenic cocci, and others, actively gas-forming microbes that can't live in air. The method I took to develop and discover them was that of Col. Sir Almroth Wright of the British army medical corps." "And that is what was on the bullet?" I queried. "The spores or seeds," he replied. "In the tubes, by excluding the air, I have developed the bacilli. Why, Walter," he went on, seriously, "those are among the microbes most dreaded in the infection of wounds. The spores live in the earth, it has been discovered, especially in cultivated soil, and they are extraordinarily long-lived, lying dormant for years, waiting for a chance to develop. These rods you saw are only from five to fifteen thousandths of a millimeter long and not more than one-thousandth of a millimeter broad. "You can't see them move here, because the air has paralyzed them. But these vibrios move among the corpuscles of the blood just as a snake moves through the grass, to quote Pasteur. If I colored them you would see that each is covered with fine vibrating hairs three or four times as long as itself. At certain times an oval mass forms in them. That is the spore which lives so long and is so hard to kill. It was the spores that were on the bullet. They resist any temperature except comparatively high and prolonged, and even resist antiseptics for a long time. On the surface of a wound they aren't so bad; but deep in they distil minute gas bubbles, puff up the surrounding tissues, and are almost impossible to combat." As he explained what he had found, I could only stare at him while the diabolical nature of the attack impressed itself on my mind. Some one had tried to murder Marlowe in this most hideous way. No need to be an accurate marksman when a mere scratch from such a bullet meant ultimate death anyhow. Why had it been done and where had the cultures come from? I asked myself. I realized fully the difficulty of trying to trace them. Any one could purchase germs, I knew. There was no law governing the sale. Craig was at work again over his microscope. Again he looked up at me. "Here on this other film I find the same sort of wisp-like anaerobes," he announced. "There was the same thing on those pieces of glass that I got." In my horror at the discovery, I had forgotten the broken package that had come to the hotel desk while we stood there. "Then it was Gavira who was receiving spores and cultures of the anaerobes!" I exclaimed, excitedly. "But that doesn't prove that it was he who used them," cautioned Craig, adding, "not yet, at least." Important as the discoveries were which he had made, I was not much farther along in fixing the guilt of anybody in particular in the case. Kennedy, however, did not seem to be perturbed, though I wondered what theory he could have worked out. "I think the best thing for us to do will be to run over to the Belleclaire," he decided as he doffed his laboratory coat and carefully cleansed his hands in an antiseptic almost boiling hot. "I should like to see Marlowe again, and, besides, there we can watch some of these people around him." Whom he meant other than Gavira I had no idea, but I felt sure that with the launching now only a matter of hours something was bound to happen soon. Marlowe was out when we arrived; in fact, had not yet returned from the yard. Nor had many of the guests remained at the hotel during the day. Most of them had been out sightseeing, though now they were returning, and as they began to gather in the hotel parlor Marjorie was again called on to put them at their ease. Fitzhugh had returned and had wasted no time dressing and getting down-stairs again to be near Marjorie. Gavira also appeared, having been out on a case. "I wish you would call up the shipyard, Walter," asked Kennedy, as we stood in the lobby, where we could see best what was going on. "Tell him I would like to see him very urgently." I found the number and entered a booth, but, as often happens, the telephone central was overwhelmed by the rush of early-evening calls, and after waiting some time the only satisfaction I got was that the line was busy. Meanwhile I decided to stick about the booth so that I could get the yard as soon as possible. From where I stood I could see that Kennedy was closely watching the little manicure, Rae Melzer. A moment later I saw Alma Hillman come out of the manicure shop, and before any one else could get in to monopolize the fascinating little manicure I saw Craig saunter over and enter. I was so interested in what he was doing that for the moment I forgot about my call and found myself unconsciously moving over in that direction, too. As I looked in I saw that he was seated at the little white table, in much the same position as Marlowe had been, deeply in conversation with the girl, though of course I could not make out what they were talking about. Once she turned to reach something on a shelf back of her. Quick as a flash Kennedy abstracted a couple of the nearest implements, one being a nail file and the other, I think, a brush. A moment later she resumed her work, Kennedy still talking and joking with her, though furtively observing. "Where is my nail file--and brush?" I could imagine her saying, as she hunted for them in pretty confusion, aided by Kennedy who, when he wanted to, could act the Fitzhugh and Gavira as well as they. The implements were not to be found and from a drawer she took another set. Just then Gavira passed on his way to his office in the front of the building, saw me, and smiled. "Kennedy's cut you out," he laughed, catching a glimpse through the door. "Never mind. I used to think I had some influence there myself--till the captain came along. I tell you these oldsters can give us points." I laughed, too, and joined him down the hall, not because I cared what he thought, but because his presence had reminded me of my original mission to call up Marlowe. However, I decided to postpone calling another moment and take advantage of the chance to talk to the house physician. "Yes," I agreed, as long as he had opened the subject. "I fancy the captain likes young people. He seems to enjoy being with them--Miss Hillman, for instance." Gavira shot a sidelong glance at me. "The Belleclaire's a dangerous place for a wealthy widower," he returned. "I had some hopes in that direction myself--in spite of Fitzhugh--but the captain seems to leave us all at the post. Still, I suppose I may still be a brother to her--and physician. So, I should worry." The impression I got of Gavira was that he enjoyed his freedom too much ever to fall in love, though an intimacy now and then with a clever girl like Alma Hillman was a welcome diversion. "I'm sorry I sha'n't be able to be with you until late to-night," he said, as he paused at his office door. "I'm in the medical corps of the Guard and I promised to lecture to-night on gunshot wounds. Some of my material got smashed up, but I have my lantern slides, anyhow. I'll try to see you all later, though." Was that a clever attempt at confession and avoidance on his part? I wondered. But, then, I reflected he could not possibly know that we knew he had anaerobic microbes and spores in his possession. I had cleared up nothing and I hastened to call up the shipyard, sure that the line could not be busy still. Whatever it was that was the matter, central seemed unable to get me my number. Instead, I found myself cut right into a conversation that did not concern me, evidently the fault of the hotel switchboard operator. I was about to protest when the words I heard stopped me in surprise. A man and a woman were talking, though I could not recognize the voices and no names were used. "I tell you I won't be a party to that launching scheme," I heard the man's voice. "I wash my hands of it. I told you that all along." "Then you're going to desert us?" came back the woman's voice, rather tartly. "It's for that girl. Well, you'll regret it. I'll turn the whole organization on you--I will--you--you--" The voices trailed off, and, try as I could to get the operator to find out who it was, I could not. Who was it? What did it mean? Kennedy had finished with the manicure some time before and was waiting for me impatiently. "I haven't been able to get Marlowe," I hastened, "but I've had an earful." He listened keenly as I told him what I had heard, adding also the account of my encounter with Gavira. "It's just as I thought--I'll wager," he muttered, excitedly, under his breath, taking a hurried turn down the corridor, his face deeply wrinkled. "Well! Anything new? I expected to hear from you, but haven't," boomed the deep voice of Marlowe, who had just come in from an entrance in another direction from that which we were pacing. "No clue yet to my crank?" Without a word, Kennedy drew Marlowe aside into a little deserted alcove. Marlowe followed, puzzled at the air of mystery. Alone, Craig leaned over toward him. "It's no crank," he whispered, in a low tone. "Marlowe, I am convinced that there is a concerted effort to destroy your plans for American commerce building. There isn't the slightest doubt in my mind that it is more serious than you think--perhaps a powerful group of European steamship men opposed to you. It is economic war! You know they have threatened it at meetings reported in the press all along. Well, it's here!" Half doubting, half convinced, Marlowe drew back. One after another he shot a rapid fire of questions. Who, then, was their agent who had fired the shot? Who was it who had deserted, as I had heard over the wire? Above all, what was it they had planned for the launching? The deeper he got the more the beads of perspiration came out on his sunburnt forehead. The launching was only eighteen hours off, too, and ten of them were darkness. What could be done? Kennedy's mind was working rapidly in the crisis as Marlowe appealed to him, almost helplessly. "May I have your car to-night?" asked Craig, pausing. "Have it? I'll give it to you if it'll do any good." "I'll need it only a few hours. I think I have a scheme that will work perfectly--if you are sure you can guard the inside of the yard to-morrow." "I'm sure of that. We spent hours to-day selecting picked men for the launching, going over everything." Late as it was to start out of town, Craig drove across the bridge and out on Long Island, never stopping until we came to a small lake, around the shores of which he skirted, at last pausing before a huge barn-like structure. As the door swung open to his honking the horn, the light which streamed forth shone on a sign above, "Sprague Aviation School." Inside I could make out enough to be sure that it was an aeroplane hangar. "Hello, Sprague!" called Kennedy, as a man appeared in the light. The man came closer. "Why, hello, Kennedy! What brings you out here at such an hour?" Craig had jumped from the car, and together the two went into the hangar, while I followed. They talked in low tones, but as nearly as I could make out Kennedy was hiring a hydro-aeroplane for to-morrow with as much nonchalance as if it had been a taxicab. As Kennedy and his acquaintance, Sprague, came to terms, my eye fell on a peculiar gun set up in a corner. It had a tremendous cylinder about the barrel, as though it contained some device to cool it. It was not a machine-gun of the type I had seen, however, yet cartridges seemed to be fed to it from a disk on which they were arranged radially rather than from a band. Kennedy had risen to go and looked about at me. "Oh, a Lewis gun!" he exclaimed, seeing what I was looking at. "That's an idea. Sprague, can you mount that on the plane?" Sprague nodded. "That's what I have it here for," he returned. "I've been testing it. Why, do you want it?" "Indeed I do! I'll be out here early in the morning, Sprague." "I'll be ready for you, sir," promised the aviator. Speeding back to the city, Kennedy laid out an extensive program for me to follow on the morrow. Together we arranged an elaborate series of signals, and that night, late as it was, Craig returned to the laboratory, where he continued his studies with the microscope, though what more he expected to discover I did not know. In spite of his late hours, it was Craig who wakened me in the morning, already prepared to motor out to the aviation school to meet Sprague. Hastily he rehearsed our signals, which consisted mostly of dots and dashes in the Morse code which Craig was to convey with a flag and I to receive with the aid of a powerful glass. I must admit that I felt somewhat lost when, later in the morning, I took my place alone on the platform that had been built for the favored few of the launching party at the bow of the huge Usona, without Craig. Already, however, he had communicated at least a part of his plan to Marlowe, and the captain and Marjorie were among the first to arrive. Marjorie never looked prettier in her life than she did now, on the day when she was to christen the great liner, nor, I imagine, had the captain ever been more proud of her. They had scarcely greeted me when we heard a shout from the men down at the end of the slip that commanded a freer view of the river. We craned our necks and in a moment saw what it was. They had sighted the air-boat coming down the river. I turned the glass on the mechanical bird as it soared closer. Already Kennedy had made us on the platform and had begun to signal as a test. At least a part of the suspense was over for me when I discovered that I could read what he sent. So fixed had my attention been that I had not noticed that slowly the members of the elect launching party had arrived, while other thousands of the less favored crowded into the spaces set apart for them. On the stand now with us were Fitzhugh and Miss Hillman, while, between glances at Kennedy, I noticed little Rae Melzer over at the right, and Doctor Gavira, quite in his element, circulating about from one group to another. Every one seemed to feel that thrill that comes with a launching, the appreciation that there is a maximum of risk in a minimum of time. Down the slip the men were driving home the last of the huge oak wedges which lifted the great Usona from the blocks and transferred her weight to the launching ways as a new support. All along the stationary, or ground, ways and those which were to glide into the water with the cradle and the ship, trusted men were making the final examination to be as sure as human care can be that all was well. As the clock neared noon, which was high water, approximately, all the preparatory work was done. Only the sole pieces before us held the ship in place. It was as though all bridges had been burned. High overhead now floated the hydro-aeroplane, on which I kept my eye fixed almost hypnotically. There was still no signal from Kennedy, however. What was it he was after? Did he expect to see the fast express cruiser, lurking like a corsair about the islands of the river? If so, he gave no sign. Men were quitting now the work of giving the last touches to the preparations. Some were placing immense jack-screws which were to give an initial impulse if it were needed to start the ship down the ways. Others were smearing the last heavy dabs of tallow, lard oil, and soft soap on the ways, and graphite where the ways stretched two hundred feet or so out into the water, for the ship was to travel some hundreds of feet on the land and in the water, and perhaps an equal distance out beyond the end of the ways. Late comers still crowded in. Men now reported that everything was ready. Steadily the time of high water approached. "Saw the sole pieces!" finally rang out the order. That was a thing that must be done by two gangs, one on each side, and evenly, too. If one gang got ahead of the other, they must stop and let the second catch up. "Zip--zip--zip," came the shrill singing tone of the saws. Was everything all right? Kennedy and Sprague were still circling overhead, at various altitudes. I redoubled my attention at the glass. Suddenly I saw Craig's flag waving frantically. A muffled exclamation came from my lips involuntarily. Marlowe, who had been watching me, leaned closer. "What is it--for God's sake?" he whispered, hoarsely. "Stop them!" I shouted as I caught Kennedy's signal. At a hurried order from Marlowe the gangs quit. A hush fell over the crowd. Kennedy was circling down now until at last the air-boat rested on the water and skimmed along toward the ways. Out on the ways, as far as they were not yet submerged, some men ran, as if to meet him, but Kennedy began signaling frantically again. Though I had not been expecting it, I made it out. "He wants them to keep back," I called, and the word was passed down the length of the ship. Instead of coming to rest before the slip, the plane turned and went away, making a complete circle, then coming to rest. To the surprise of every one, the rapid staccato bark of the Lewis gun broke the silence. Kennedy was evidently firing, but at what? There was nothing in sight. Suddenly there came a tremendous detonation, which made even the launching-slip tremble, and a huge column of water, like a geyser, rose in the air about eight hundred feet out in the river, directly in front of us. The truth flashed over us in an instant. There, ten feet or so in the dark water out in the river, Craig had seen a huge circular object, visible only against a sandy bottom from the hydro-aeroplane above, as the sun-rays were reflected through the water. It was a contact submarine mine. Marlowe looked at me, his face almost pale. The moment the great hulk of the Usona in its wild flight to the sea would have hit that mine, tilting it, she would have sunk in a blast of flame. The air-boat now headed for the shore, and a few moments later, as Craig climbed into our stand, Marlowe seized him in congratulation too deep for words. "Is it all right?" sang out one of the men in the gangs, less impressionable than the rest. "If there is still water enough," nodded Craig. Again the order to saw away the sole pieces was given, and the gangs resumed. "Zip--zip," again went the two saws. There were perhaps two inches more left, when the hull quivered. There was a crashing and rending as the timbers broke away. Marjorie Marlowe, alert, swung the bottle of champagne in its silken net on a silken cord and it crashed on the bow as she cried, gleefully, "I christen thee Usona!" Down the ship slid, with a slow, gliding motion at first, rapidly gathering headway. As her stern sank and finally the bow dipped into the water, cheers broke forth. Then a cloud of smoke hid her. There was an ominous silence. Was she wrecked, at last, after all? A puff of wind cleared the smoke. "Just the friction of the ways--set the grease on fire," shouted Marlowe. "It always does that." Wedges, sliding ways, and other parts of the cradle floated to the surface. The tide took her and tugs crept up and pulled her to the place selected for temporary mooring. A splash of a huge anchor, and there she rode--safe! In the revulsion of feeling, every eye on the platform turned involuntarily to Kennedy. Marlowe, still holding his hand, was speechless. Marjorie leaned forward, almost hysterical. "Just a moment," called Craig, as some turned to go down. "There is just one thing more." There was a hush as the crowd pressed close. "There's a conspiracy here," rang out Craig's voice, boldly, "a foreign trade war. From the start I suspected something and I tried to reason it out. Having failed to stop the work, failed to kill Marlowe--what was left? Why, the launching. How? I knew of that motor-boat. What else could they do with it? I thought of recent tests that have been made with express cruisers as mine-planters. Could that be the scheme? The air-boat scheme occurred to me late last night. It at least was worth trying. You see what has happened. Now for the reckoning. Who was their agent? I have something here that will interest you." Kennedy was speaking rapidly. It was one of those occasions in which Kennedy's soul delighted. Quickly he drew a deft contrast between the infinitely large hulk of the Usona as compared to the infinitely small bacteria which he had been studying the day before. Suddenly he drew forth from his pocket the bullet that had been fired at Marlowe, then, to the surprise of even myself, he quietly laid a delicate little nail file and brush in the palm of his hand beside the bullet. A suppressed cry from Rae Melzer caused me to recollect the file and brush she had missed. "Just a second," raced on Kennedy. "On this file and brush I found spores of those deadly anaerobes--dead, killed by heat and an antiseptic, perhaps a one-per-cent. solution of carbolic acid at blood heat, ninety-eight degrees--dead, but nevertheless there. I suppose the microscopic examination of finger-nail deposits is too minute a thing to appeal to most people. But it has been practically applied in a number of criminal cases in Europe. Ordinary washing and even cleaning doesn't alter microscope findings. In this case this trifling clue is all that leads to the real brain of this plot, literally to the hand that directed it." He paused a moment. "Yesterday I found that anaerobe cultures were being received by some one in the Belleclaire, and--" "They were stolen from me. Some one must have got into my office, where I was studying them." Doctor Gavira had pressed forward earnestly, but Craig did not pause again. "Who were these agents sent over to wage this secret war at any cost?" he repeated. "One of them, I know now, fell in love with the daughter of the man against whom he was to plot." Marjorie cast a furtive glance at Fitzhugh. "Love has saved him. But the other? To whom do these deadly germs point? Who dum-dummed and poisoned the bullet? Whose own fingers, in spite of antiseptics and manicures, point inexorably to a guilty self?" Rae Melzer could restrain herself no longer. She was looking at the file and brush, as if with a hideous fascination. "They are mine--you took them," she cried, impulsively. "It was she--always having her nails manicured--she who had been there just before--she--Alma Hillman!" XI THE GUN-RUNNER "With the treaty ratified, if the deal goes through we'll all be rich." Something about the remark which rose over the babel of voices arrested Kennedy's attention. For one thing, it was a woman's voice, and it was not the sort of remark to be expected from a woman, at least not in such a place. Craig had been working pretty hard and began to show the strain. We had taken an evening off and now had dropped in after the theater at the Burridge, one of the most frequented midnight resorts on Broadway. At the table next to us--and the tables at the Burridge were so close that one almost rubbed elbows with those at the next--sat a party of four, two ladies in evening gowns and two men in immaculate black and white. "I hope you are right, Leontine," returned one of the men, with an English accent. "The natural place for the islands is under the American flag, anyway." "Yes," put in the other; "the people have voted for it before. They want it." It was at the time that the American and Danish governments were negotiating about the transfer of the Danish West Indies, and quite evidently they were discussing the islands. The last speaker seemed to be a Dane, but the woman with him, evidently his wife, was not. It was a curious group, worth more than a passing glance. For a moment Craig watched them closely. "That woman in blue," he whispered, "is a typical promoter." I recognized the type which is becoming increasingly frequent in Wall Street as the competition in financial affairs grows keener and women enter business and professional life. There were plenty of other types in the brilliantly lighted dining-room, and we did not dwell long on the study of our neighbors. A few moments later Kennedy left me and was visiting another table. It was a habit of his, for he had hundreds of friends and acquaintances, and the Burridge was the place to which every one came. This time I saw that he had stopped before some one whom I recognized. It was Captain Marlowe of the American Shipping Trust, to whom Kennedy had been of great assistance at the time of the launching of his great ship, the Usona. Marlowe's daughter Marjorie was not with him, having not yet returned from her honeymoon trip, and he was accompanied by a man whose face was unfamiliar to me. As I recognized who it was to whom Kennedy was speaking, I also rose and made my way over to the table. As I approached, the captain turned from Kennedy and greeted me cordially. "Mr. Whitson," he introduced the man with him. "Mr. Whitson is sailing to-morrow for St. Thomas on the Arroyo. We're preparing to extend our steamship lines to the islands as soon as the formalities of the purchase are completed." Marlowe turned again to Kennedy and went on with the remark he had evidently been making. "Of course," I heard him say, "you know we have Mexico practically blockaded as far as arms and munitions go. Yet, Kennedy, through a secret channel I know that thousands of stands of arms and millions of rounds of ammunition are filtering in there. It's shameful. I can't imagine anything more traitorous. Whoever is at the bottom of it ought to swing. It isn't over the border that they are going. We know that. The troops are there. How is it, then?" Marlowe looked at us as if he expected Kennedy to catch some one by pure reason. Kennedy said nothing, but it was not because he was not interested. "Think it over," pursued Marlowe, who was a patriot above everything else. "Perhaps it will occur to you how you can be of the greatest service to the country. The thing is damnable--damnable." Neither Kennedy nor I having anything definite to contribute to the subject, the conversation drifted to the islands and Whitson's mission. Whitson proved to be very enthusiastic about it. He knew the islands well and had already made a trip there for Marlowe. A few moments later we shook hands and returned to our own table. It was getting late and the only type that was left to study was the common Broadway midnight-life genus. We paid our check and were about to leave. For an instant we stopped at the coat-room to watch the late arrivals and the departing throng. "Hello!" greeted a familiar voice beside us. "I've been looking all over town for you. They told me you had gone to the theater and I thought I might possibly find you here." We turned. It was our old friend Burke, of the Secret Service, accompanied by a stranger. "I'd like you to meet Mr. Sydney, the new special consular agent whom the government is sending to the Danish West Indies to investigate and report on trade conditions," he introduced. "We're off for St. Thomas on the Arroyo, which sails to-morrow noon." "Great Scott!" ejaculated Kennedy. "Is everybody daffy over those little islands? What takes you down there, Burke?" Burke looked about hastily, then drew us aside into a recess in the lobby. "I don't suppose you know," he explained, lowering his voice, "but since these negotiations began, the consular service has been keenly interested in the present state and the possibilities of the islands. The government sent one special agent there, named Dwight. Well, he died a few days ago. It was very suspicious, so much so that the authorities in the island investigated. Yet the doctors in the island have found no evidence of anything wrong, no poison. Still, it is very mysterious--and, you know," he hinted, "there are those who don't want us down there." The Secret Service man paused as though he had put the case as briefly and pointedly as he could, then went on: "I've been assigned to accompany the new consul down there and investigate. I've no particular orders and the chief will honor any reasonable expense account--but--" He hesitated and stopped, looking keenly at Kennedy's face. I saw what he was driving at. "Well--to come to the point--what I wanted to see you about, Kennedy, is to find out whether you would go with me. I think," he added, persuasively, "it would be quite worth your while. Besides, you look tired. You're working too hard. The change will do you good. And your conscience needn't trouble you. You'll be working, all right." Burke had been quick to note the haggard expression on Kennedy's face and turn it into an argument to carry his point. Kennedy smiled as he read the other's enthusiasm. I would have added my own urging, only I knew that nothing but a sense of duty would weigh with Craig. "I'd like to think the proposal over," he conceded, much to my surprise. "I'll let you know in the morning." "Mind," wheedled Burke, "I won't take no for an answer. We need you." The Secret Service man was evidently delighted by the reception Kennedy had given his scheme. Just then I caught sight of the party of four getting their hats and wraps preparatory to leaving, and Kennedy eyed them sharply. Marlowe and Whitson passed. As they did so I could not help seeing Whitson pause and shoot a quick glance at the four. It was a glance of suspicion and it was not lost on Craig. Did they know more of this Mexican gun-running business than Marlowe had hinted at? I watched Kennedy's face. Evidently his mind was at work on the same idea as mine. Burke accompanied us almost all the way home, with Sydney adding his urging. I could tell that the whole combination of circumstances at the Burridge had had an effect on Kennedy. I went to bed, tired, but through the night I knew Craig was engaged on some work about which he seemed to be somewhat secretive. When I saw him again in the laboratory, in the morning, he had before him a large packing-case of stout wood bound with steel bands. "What's that?" I asked, mystified. He opened the lid, a sort of door, on which was a strong lock, and I looked inside. "My traveling laboratory," he remarked, with pride. I peered in more closely. It was a well-stocked armamentarium, as the doctors would have called it. I shall not make any attempt to describe its contents. They were too varied and too numerous, a little bit of everything, it seemed. In fact, Craig seemed to have epitomized the sciences and arts. It was not that he had anything so wonderful, or even comparable to the collection of his laboratory. But as I ran my eye over the box I would have wagered that from the contents he might have made shift to duplicate in some makeshift form almost anything that he might need. It was truly amazing, representing in miniature his study of crime for years. "Then you are going with Burke to St. Thomas?" I queried, realizing the significance of it. Kennedy nodded. "I've been thinking of what I would do if an important case ever called me away. Burke's proposal hurried me, that's all. And you are going, also," he added. "You have until noon to break the news to the Star." I did not say anything more, fearful lest he might change his mind. I knew he needed the rest, and that no matter what the case was in the islands he could not work as hard as he was doing in New York. Accordingly my own arrangements with the Star were easily made. I had a sort of roving commission, anyhow, since my close association with Kennedy. Moreover, the possibility of turning up something good in the islands, which were much in the news at the time, rather appealed to the managing editor. If Kennedy could arrange his affairs, I felt that the least I could do was to arrange my own. Thus it came about that Craig and I found ourselves in the forenoon in a taxicab, on the front of which was loaded the precious box as well as our other hastily packed luggage, and we were on our way over to Brooklyn to the dock from which the Arroyo sailed. Already the clearance papers had been obtained, and there was the usual last-moment confusion among the passengers as the hour for sailing approached. It seemed as if we had scarcely boarded the ship when Kennedy was as gay as a school-boy on an unexpected holiday. I realized at once what was the cause. The change of scene, the mere fact of cutting loose, were having their effect. As we steamed slowly down the bay, I ran my eye over the other passengers at the rail, straining their eyes to catch the last glimpse of the towers of New York. There were Burke and Sydney, but they were not together, and, to all appearances, did not know each other. Sydney, of course, could not conceal his identity, nor did he wish to, no matter how beset with unseen perils might be his mission. But Burke was down on the passenger-list as, and had assumed the role of, a traveling salesman for a mythical novelty-house in Chicago. That evidently was part of the plan they had agreed on between themselves. Kennedy took the cue. As I studied the various groups, I paused suddenly, surprised. There was the party which had sat at the table next to us at the Burridge the night before. Kennedy had already seen them and had been watching them furtively. Just then Craig jogged my elbow. He had caught sight of Whitson edging his way in our direction. I saw what it was that Craig meant. He wanted purposely to avoid him. I wondered why, but soon I saw what he was up to. He wanted introductions to come about naturally, as they do on shipboard if one only waits. On deck and in the lounging and smoking rooms it did not take long for him to contrive ways of meeting and getting acquainted with those he wished to know, without exciting suspicion. Thus, by the time we sat down to dinner in the saloon we were all getting fairly chummy. We had met Burke quite as naturally as if we were total strangers. It was easy to make it appear that Whitson and Sydney were shipboard acquaintances. Nor was it difficult to secure an introduction to the other party of four. The girl whom we had heard addressed as Leontine seemed to be the leader of the group. Leontine Cowell was a striking personality. Her clear blue eyes directed a gaze at one which tested one's mettle to meet. I was never quite sure whether she remembered seeing us at the Burridge, whether she penetrated the parts we were playing. She was none the less feminine because she had aspirations in a commercial way. As Kennedy had first observed, she was well worth study. Her companion, Barrett Burleigh, was a polished, deferential Englishman, one of those who seem to be citizens of the world rather than subjects of any particular country. I wondered what were the real relations of the two. Jorgen Erickson was, as I had surmised, a Dane. He proved to be one of the largest planters in the island, already wealthy and destined to be wealthier if real estate advanced. The other woman, Nanette, was his wife. She was also a peculiarly interesting type, a Frenchwoman from Guadeloupe. Younger and more vivacious than her husband, her snappy black eyes betokened an attractive personality. Leontine Cowell, it seemed, had been in the islands not long before, had secured options on some score of plantations at a low figure, and made no secret of her business. When the American flag at last flew over the islands she stood to win out of the increase of land values a considerable fortune. Erickson also, in addition to his own holdings, had been an agent for some other planters and thus had met Leontine, who had been the means of interesting some American capital. As for Burleigh, it seemed that he had made the acquaintance of Leontine in Wall Street. He had been in the Caribbean and the impending changes in the Danish West Indies had attracted his notice. Whether he had some money to invest in the speculation or hoped to profit by commissions derived from sales did not appear. But at any rate some common bond had thrown the quartet together. I need not dwell on the little incidents of life on ship. It must have been the second day out that I observed Leontine and Sydney together on the promenade-deck. They seemed to be quite interested in each other, though I felt sure that Leontine was making a play for him. At any rate, Burleigh was jealous. Whatever might be the scheme, it was apparent that the young Englishman was head over heels in love with her. What did it mean? Was she playing with Sydney, seeking to secure his influence to further her schemes? Or did it mask some deeper, more sinister motive? From what I had seen of Sydney, I could not think that he was the man to take such an affair seriously. I felt that he must be merely amusing himself. Busy with my speculations, I was astonished soon after to realize that the triangle had become a hexagon, so to speak. Whitson and Nanette Erickson seemed to be much in each other's company. But, unlike Burleigh, Erickson seemed to be either oblivious or complacent. Whatever it might all portend, I found that it did not worry Kennedy, although he observed closely. Burke, however, was considerably excited and even went so far as to speak to Sydney, over whom he felt a sort of guardianship. Sydney turned the matter off lightly. As for me, I determined to watch both of these women closely. Kennedy spent much time not only in watching the passengers, but in going about the ship, talking to the captain and crew and every one who knew anything about the islands. In fact, he collected enough information in a few days to have satisfied any ordinary tourist for weeks. Even the cargo did not escape his attention, and I found that he was especially interested in the rather heavy shipments of agricultural implements that were consigned to various planters in the islands. So great was his interest that I began to suspect that it had some bearing on the gun-running plot that had been hinted at by Marlowe. It was the evening after one of Kennedy's busy days scouting about that he quietly summoned both Burke and Sydney to our cabin. "There's something queer going on," announced Craig, when he was sure that we were all together without having been observed. "Frankly, I must confess that I don't understand it--yet." "You needn't worry about me," interrupted Sydney, hastily. "I can take care of myself." Kennedy smiled quietly. We knew what Sydney meant. He seemed to resent Burke's solicitude over his acquaintance with Leontine and was evidently warning us off. Kennedy, however, avoided the subject. "I may as well tell you," he resumed, "that I was quite as much influenced by a rumor that arms were somehow getting into Mexican ports as I was by your appeal, Burke, in coming down here. So far I've found nothing that proves my case. But, as I said, there is something under the surface which I don't understand. We have all got to stick together, trust no one but ourselves, and, above all, keep our eyes open." It was all that was said, but I was relieved to note that Sydney seemed greatly impressed. Still, half an hour later, I saw him sitting in a steamer-chair beside Leontine again, watching the beautiful play of the moonlight on the now almost tropical ocean after we had emerged from the Gulf Stream. I felt that it was rather dangerous, but at least he had had his warning. Seeking Kennedy, I found him at last in the smoking-room, to my surprise talking with Erickson. I joined them, wondering how I was to convey to Craig what I had just seen without exciting suspicion. They were discussing the commercial and agricultural future of the islands under the American flag, especially the sugar industry, which had fallen into a low estate. "I suppose," remarked Kennedy, casually, "that you are already modernizing your plant and that others are doing the same, getting ready for a revival." Erickson received the remark stolidly. "No," he replied, slowly. "Some of us may be doing so, but as for me, I shall be quite content to sell if I can get my price." "The planters are not putting in modern machinery, then?" queried Kennedy, innocently, while there flashed over me what he had discovered about shipments of agricultural implements. Erickson shook his head. "Some of them may be. But for one that is, I know twenty whose only thought is to sell out and take a profit." The conversation trailed off on other subjects and I knew that Kennedy had acquired the information which he sought. As neatly as I could I drew him apart from Erickson. "Strange he should tell me that," ruminated Kennedy as we gained a quiet corner of the deck. "I know that there is a lot of stuff consigned to planters in the island, some even to himself." "He must be lying, then," I hastened. "Perhaps these promoters are really plotters. By the way, what I wanted to tell you was that I saw Sydney and Leontine together again." He was about to reply when the sound of some one approaching caused us to draw back farther into the shadow. It proved to be Whitson and Nanette. "Then you do not like St. Thomas?" we heard Whitson remark, as if he were repeating something she had just said. "There is nothing there," she replied. "Why, there aren't a hundred miles of good roads and not a dozen automobiles." Evidently the swiftness of life in New York of which she had tasted was having its effect. "St. Croix, where we have the plantation, is just as bad. Part of the time we live there, part of the time at Charlotte Amalie in St. Thomas. But there is little difference. I hope Jorgen is able to sell. At least I should like to live a part of the year in the States." "Would he like that, too?" "Many of us would," she replied, quickly. "For many years things have been getting worse with us. Just now it seems a bit better because of the high price of sugar. But who knows how long that will last? Oh, I wish something would happen soon so that we might make enough money to live as I want to live. Think; here the best years of life are slipping away. Unless we do something soon, it will be too late! We must make our money soon." There was an air of impatience in her tone, of restless dissatisfaction. I felt also that there was an element of danger, too, in a woman just passing from youth making a confidant of another man. It was a mixed situation with the quartet whom we were watching. One thing was sufficiently evident. They were all desperately engaged in the pursuit of wealth. That was a common bond. Nor had I seen anything to indicate that they were over-scrupulous in that pursuit. Within half an hour I had seen Leontine with Sydney and Nanette with Whitson. Both Sydney as consular agent and Whitson through his influence with the shipping trust possessed great influence. Had the party thought it out and were they now playing the game with the main chance in view? I looked inquiringly at Kennedy as the voices died away while the couple walked slowly down the deck. He said nothing, but he was evidently pondering deeply on some problem, perhaps that which the trend of affairs had raised in my own mind. Our delay had not been long, but it had been sufficient to cause us to miss finding Leontine and Sydney. We did, however, run across Burke, bent evidently on watching, also. "I don't like this business," he confessed, as we paused to compare experiences. "I've been thinking of that Mexican business you hinted at, Kennedy. You know the islands would be an ideal out-of-the-way spot from which to start gun-running expeditions to Mexico. I don't like this Leontine and Burleigh. They want to make money too bad." Kennedy smiled. "Burleigh doesn't seem to approve of everything, though," he remarked. "Perhaps not. That's one reason why I think it may be more dangerous for Sydney than he realizes. I know she's a fascinating girl. All the more reason to watch out for her. But I can't talk to Sydney," he sighed. It was an enigma and I had not solved it, though I felt much as Burke did. Kennedy seemed to have determined to allow events to take their course, perhaps in the hope that developments would be quicker that way than by interfering with something which we did not understand. In the smoking-room, after we left Burke, Kennedy and I came upon Erickson and Burleigh. They had just finished a game of poker with some of the other passengers, in which Burleigh's usual run of luck and skill had been with him. "Lucky at cards, unlucky in love," remarked Burleigh as we approached. He said it with an air of banter, yet I could not help feeling that there was a note of seriousness at the bottom of it. Had he known that Leontine had been with Sydney on the deck? His very success at poker had its effect on me. I found myself eying him as if he had been one of the transatlantic card sharps, perhaps an international crook. Yet when I considered I was forced to admit that I had nothing on which to base such a judgment. Erickson presented a different problem, to my mind, There was indeed something queer about him. Either he had not been perfectly frank with us in regard to the improvement of his properties or he was concealing something much more sinister. Again and again my mind reverted to the hints that had been dropped by Marlowe, and I recalled the close scrutiny Whitson had given the four that night. So far, I had felt that in any such attempt we might count on Whitson playing a lone hand and perhaps finding out something to our advantage. It was the morning of the last day of the voyage that most of the passengers gathered on the deck for the first glimpse of the land to which we had been journeying. Before us lay the beautiful and picturesque harbor and town of Charlotte Amalie, one of the finest harbors in the West Indies, deep enough to float the largest vessels, with shipyards, dry-docks, and repair shops. From the deck it was a strikingly beautiful picture, formed by three spurs of mountains covered with the greenest of tropical foliage. From the edge of the dancing blue waves the town itself rose on the hills, presenting an entrancing panorama. All was bustle and excitement as the anchor plunged into the water, for not only was this the end of our journey, but the arrival of the boat from New York was an event for the town. There was much to watch, but I let nothing interfere with my observation of how the affair between Sydney and Leontine was progressing. To my surprise, I saw that this morning she was bestowing the favor of her smile rather on Burleigh. It was Sydney's turn now to feel the pangs of jealousy, and I must admit that he bore them with better grace than Burleigh, whatever that might indicate. As I watched the two and recalled their intimacy at the Burridge the first night we had seen them, I almost began to wonder whether I might not have been wrong about Leontine. Had it been that I had distrusted the woman merely because I was suspicious of the type, both male and female? Had I been finding food for suspicion because I was myself suspicious? Erickson was standing beside Sydney, while we were not far away. Evidently he had been saving up a speech for the occasion and now was prepared to deliver it. "Mr. Sydney," he began, with a wave of his arm that seemed to include us all, "it is a pleasure to welcome you here to our island. Last night it occurred to me that we ought to do something to show that we appreciate it. You must come to dinner to-night at my villa here in the town. You are all invited, all of us who have become so enjoyably acquainted on this voyage which I shall never forget. Believe me when I say that it will be even more a tribute to you personally than because of the official position you are to hold among us." It was a graceful invitation, more so than I had believed Erickson capable of framing. Sydney could do nothing less than thank him cordially and accept, as we all did. Indeed, I could see that Kennedy was delighted at the suggestion. It would give him an opportunity to observe them all under circumstances different enough to show something. While we were thanking Erickson, I saw that Whitson had taken the occasion also to thank Mrs. Erickson, with whom he had been talking, just a bit apart from the group. He made no secret of his attentions, though I thought she was a bit embarrassed by them at such a time. Indeed, she started rather abruptly toward the group which was now intent on surveying the town, and as she did so, I noted that she had forgotten her hand-bag, which lay on a deck-chair near where they had been sitting. I picked it up to restore it. Some uncontrollable curiosity prompted me and I hesitated. All were still looking at the town. I opened the bag. Inside was a little bottle of grayish liquid. What should I do? Any moment she or Whitson might turn around. Hastily I pulled off the cap of my fountain-pen and poured into it some of the liquid, replacing the cork in the bottle and dropping it back into the bag, while I disposed of the cap as best I could without spilling its contents. Whether either she or any one else had observed me, I was not going to run any chances of being seen. I called a passing steward. "Mrs. Erickson forgot her bag," I said, pointing hastily to it. "You'll find her over there with Mr. Whitson." Then I mingled in the crowd to watch her. She did not seem to show any anxiety when she received it. I lost no time in getting back to Kennedy and telling him what I had found, and a few moments later he made an excuse to go to our state-room, as eager as I was to know what had been in the little bottle. First he poured out a drop of the liquid from the cap of my fountain-pen in some water. It did not dissolve. Successively he tried alcohol, ether, then pepsin. None of them had any effect on it. Finally, however, he managed to dissolve it in ammonia. "Relatively high amount of sulphur," he muttered, after a few moments more of study. "Keratin, I believe." "A poison?" I asked. Kennedy shook his head. "No; harmless." "Then what is it for?" He shrugged his shoulders. He may have had some half-formed idea, but if he did it was still indefinite and he refused to commit himself. Instead, he placed the sample in his traveling laboratory, closed and locked it, and, with our luggage, the box was ready to be taken ashore. Nearly every one had gone ashore by the time we returned to the deck. Whitson was there yet, talking to the captain, for the shipping at the port interested him. I wondered whether he, too, might be suspicious of those cases consigned to Erickson and others. If so, he said nothing of it. By this time several vessels that looked as if they might be lighters, though fairly large, had pulled up. It seemed that they had been engaged to carry shipments of goods to the other islands of St. John and St. Croix. Kennedy seemed eager now to get ashore, and we went, accompanied by Whitson, and after some difficulty established ourselves in a small hotel. Most of the tourists were sightseeing, and, while we had no time for that, still we could not help doing so, in going about the town. Charlotte Amalie, I may say, proved to be one of the most picturesque towns in the Windward Islands. The walls of the houses were mostly of a dazzling whiteness, though some were yellow, others gray, orange, blue. But the roofs were all of a generous bright red which showed up very effectively among the clumps of green trees. Indeed, the town seemed to be one of gaily tinted villas and palaces. There were no factories, no slums. Nature had provided against that and man had not violated the provision. The people whom we met on the streets were mostly negroes, though there was a fair sprinkling of whites. What pleased us most was that nearly everywhere we went English was spoken. I had half expected Danish. But there was even very little Spanish spoken. Burke was waiting for us, and in spite of his playing the role of traveling salesman managed to direct us about so that we might as quickly as possible pick up the thread of the mysterious death of Dwight. It did not take long to gather such meager information as there was about the autopsy that had followed the strange death of Sydney's predecessor. We were able to find out little from either the authorities or the doctor who had investigated the case. Under the stress of suspicion, both the stomach and the contents of the stomach of the unfortunate man had been examined. No trace of anything out of the way had been found, and there the matter had rested, except for suspicion. One of our first visits was to the American consulate. There Sydney, by virtue of his special commission, had, with characteristic energy, established himself with the consul. Naturally, he, too, had been making inquiries. But they had led nowhere. There seemed to be no clue to the mysterious death of Dwight, not even a hint as to the cause. All that we were able to discover, after some hours of patient inquiry, was that Dwight had suffered from great prostration, marked cyanosis, convulsions, and coma. Whether it was the result of some strange disease or of a poison no one, not even the doctor, was prepared to say. All that was known was that the blow, if blow it had been, was swift, sudden, sure. We ran across Whitson once or twice during the day, busily engaged renewing acquaintance with merchants and planters whom he had known before, but I do not recall having seen either Burleigh or Leontine, which, at the time, I thought rather strange, for the town was small and strangers were few. The more I thought of it the more firmly convinced I was that Dwight had discovered some secret which it was extremely inconvenient for somebody to have known. What was it? Was it connected with the rumors we had heard of gun-running to Mexico? Erickson had invited us to come late in the afternoon to the dinner and we did not delay in getting there. His house proved to be a veritable palace on the side of one of the hills rising abruptly back of the shore. Flights of massive stone steps, quaint walls covered with creepers, balustrades overlooking charming gardens, arcades from which one looked out on splendid vistas and shady terraces combined to make it a veritable paradise such as can be found only in tropical and subtropical lands. Most wonderful of all was the picture of the other hills unfolded, especially of the two ruined pirates' castles belonging to semi-mythical personages, Bluebeard and Blackbeard. The Ericksons were proud of their home, as well they might be, in spite of the complaints we had heard Nanette utter and the efforts of Erickson to sell his holdings. Mrs. Erickson proved to be a charming hostess and the host extended a hospitality such as one rarely meets. It quite made me uncomfortable to accept it at the same time that I knew we must view it all with suspicion. Nor did it make matters any better, but rather worse, to feel that there was some color of excuse for the suspicion. Burleigh arrived proudly with Leontine, followed closely by Sydney. At once the game was on again, Leontine pitting one against the other. Whitson came, his attentions to Mrs. Erickson a trifle restrained, but still obvious. Burke and ourselves completed the party. To the repeated urging of Erickson we made ourselves quite as much at home as we politely could. Kennedy and Burke, acting under his instructions, seemed to be ubiquitous. Yet, beyond a continuation of the drama that had been unfolded on the ship it did not seem to me at first that we were getting anywhere. Kennedy and I were passing alone along a colonnade that opened off from the large dining-hall, when Craig paused and looked in through an open door at the massive table set for the dinner. A servant had just completed setting out cocktails at the various places, pouring them from a huge tankard, for the purpose, which had been standing on a sideboard. Guests had been walking past through the colonnade ever since we arrived, but at the moment there was no one about, and even the servant had disappeared. Kennedy stepped lightly into the dining-hall and looked about sharply. Instinctively I stepped to a window where I could hear any one approaching. Out of the corner of my eye I saw him narrowly scrutinizing the table. Finally he pulled from his pocket a clean linen handkerchief. Into an empty glass he poured the contents of one of the cocktail-glasses, straining the liquid through the handkerchief. Then he poured the filtrate, if I may call it such, back into the original glass. A second he treated in the same way, and a third. He had nearly completed the round of the table when I heard a light step. My warning came only just in time. It was Burleigh. He saw us standing now in the colonnade, made some hasty remark, then walked on, as if in search for some one. Had it been interest in Leontine or in the dining-room that had drawn him thither? Kennedy was now looking closely at the handkerchief, and I looked also. In the glasses had been innumerable little seeds as if from the fruit juice used in concocting the appetizer. The fine meshes of the linen had extracted them. What were they? I took one in my fingers and crushed it between my nails. There was an unmistakable odor of bitter almonds. What did it mean? We had no time now for speculation. Our prolonged absence might be noticed and we hastened to join the other guests after finishing the round of glasses in which he had been interrupted. How, in my suppressed excitement, I managed to get through that dinner I do not know. It was a brilliant affair, yet I found that I had completely lost my appetite, as well one might after having observed Kennedy's sleuthing. However, the dinner progressed, though each course that brought it nearer a conclusion afforded me an air of relief. I was quite ready when, over the coffee, Kennedy contrived to make some excuse for us, promising to call again and perhaps to visit the Erickson plantation. In the secrecy of our room in the little hotel, Craig was soon deeply buried in making use of his traveling laboratory. As he worked I could no longer restrain my impatience. "What about that little bottle of keratin?" I asked, eagerly. "Oh yes," he replied, not looking up from the tests he was making. "Well, keratin, you know, is also called epidermose. It is a scleroprotein present largely in cuticular structures such as hair, nails, horn. I believe it is usually prepared from pieces of horn steeped in pepsin, hydrochloric acid, and water for a long time. Then the residue is dissolved in ammonia and acetic acid." "But what's its use?" I demanded. "You said it was harmless." "Why, the pepsin of the stomach won't digest it," he returned. "For that reason its chief use is for coating what are known as 'enteric capsules.' Anything coated with keratin is carried on through the stomach into the intestines. It is used much in hot countries in order to introduce drugs into the intestines in the treatment of the tropical diseases that affect the intestines." He paused and devoted his entire attention to his work, but he had told me enough to assure me that at least the bottle of keratin I had found had proved to be a clue. I waited as long as I could, then interrupted again. "What are the seeds?" I queried. "Have you found out yet?" He paused as though he had not quite finished his hasty investigation, yet had found out enough to convince him. "There seem to be two kinds. I wish I had had time to keep each lot separate. Some of them are certainly quite harmless. But there are others, I find, that have been soaked in nitro-benzol, artificial oil of bitter almonds. Even a few drops, such as might be soaked up in this way, might be fatal. The new and interesting phase, to me, is that they were all carefully coated with keratin. Really, they are keratin-coated enteric capsules of nitro-benzol, a deadly poison." I looked at him, aghast at what some of us had been rescued from by his prompt action. "You see," he went on, excitedly, "that is why the autopsies probably showed nothing. These doctors down here sought for a poison in the stomach. But if the poison had been in the stomach the odor alone would have betrayed it. You smelt it when you crushed a seed. But the poisoning had been devised to avoid just that chance of discovery. There was no poison in the stomach. Death was delayed long enough, also, to divert suspicion from the real poisoner. Some one has been diabolically clever in covering up the crimes." I could only gasp my amazement. "Then," I blurted out, "you think the Ericksons--" Our door burst open. It was Burke, in wild excitement. "Has anybody--died?" I managed to demand. He seemed not to hear, but dashed to the window and threw it open. "Look!" he exclaimed. We did. In the late twilight, through the open sash we could see the landlocked basin of the harbor. But it was not that at which Burke pointed. On the horizon an ugly dark cloud rose menacingly. In the strange, unearthly murkiness, I could see people of the town pouring out into the narrow streets, wildly, fearfully, with frantic cries and gesticulations. For a moment I gazed at the sight blankly. Then I realized that sweeping on us was one of those sudden, deadly West-Indian hurricanes. Our harbor was sheltered from the north and east winds. But this wind was southern born, rare, oncoming in a fury against which we had no protection. Hastily closing his armamentarium, Kennedy also hurried out on the street. The gale had become terrific already in the few minutes that had elapsed. From our terrace we could see the water, gray and olive, with huge white breakers, like gnashing teeth, coming on to rend and tear everything in their path. It was as though we stood in an amphitheater provided by nature for a great spectacle, the bold headlands standing out like the curves of a stadium. I looked about. The Ericksons had just driven up with Burleigh and Leontine, as well as Whitson, all of whom were stopping at our hotel, and were about to take Sydney on to the consulate when the approach of the storm warned them to stay. Leontine had hurried into the hotel, evidently fearful of the loss of something she treasured, and the rest were standing apart from the trees and buildings, where the formation of the land offered some protection. As we joined them I peered at the pale faces in the ghastly, unnatural light. Was it, in a sense, retribution? Suddenly, without further warning, the storm broke. Trees were turned up by roots, like weeds, the buildings rocked as if they had been houses of cards. It was a wild, catastrophic spectacle. "Leontine," I heard a voice mutter by my side, as a form catapulted itself past through the murkiness into the crazily swaying hotel. It was Burleigh. I turned to speak to Kennedy. He was gone. Where to find him I had no idea. The force of the wind was such that search was impossible. All we could do was to huddle back of such protection as the earth afforded against the million needles of rain that cut into our faces. The wind almost blew me flat to the earth as, no longer able to stand the suspense, I stumbled toward the hotel, thinking perhaps he had gone to save his armamentarium, although if I had stopped to think I should have realized that that strong box was about the safest piece of property on the island. I was literally picked up and hurled against an object in the darkness--a man. "In the room--more keratin--more seeds." It was Kennedy. He had taken advantage of the confusion to make a search which otherwise might have been more difficult. Together we struggled back to our shelter. Just then came a crash, as the hotel crumpled under the fierce stress of the storm. Out of the doorway struggled a figure just in time to clear the falling walls. It was Burleigh, a huge gash from a beam streaming blood down his forehead which the rain washed away almost as it oozed. In his arms, clinging about his neck, was Leontine, no longer the sophisticated, but in the face of this primeval danger just a woman. Burleigh staggered with his burden a little apart from us, and in spite of everything I could fancy him blessing the storm that had given him his opportunity. Far from abating, the storm seemed increasing in fury, as though all the devils of the underworld were vexed at anything remaining undestroyed. It seemed as if even the hills on which the old pirates had once had their castles must be rocking. "My God!" exclaimed a thick voice, as an arm shot out, pointing toward the harbor. There was the Arroyo tugging at every extra mooring that could be impressed into service. The lighters had broken or been cut away and were scudding, destruction-bent, squarely at the shore almost below us. A moment and they had crashed on the beach, a mass of timbers and spars, while the pounding waves tore open and flung about heavy cases as though they were mere toys. Then, almost as suddenly as it had come, the storm began to abate, the air cleared, and nothing remained but the fury of the waves. "Look!" exclaimed Kennedy, pointing down at the strange wreckage that strewed the beach. "Does that look like agricultural machinery?" We strained our eyes. Kennedy did not pause. "The moment I heard that arms were getting into Mexico I suspected that somewhere here in the Caribbean munitions were being transhipped. Perhaps they have been sent to Atlantic ports ostensibly for the Allies. They have got down here disguised. Even before the storm exposed them I had reasoned it out. From this port, the key to the vast sweep of mainland, I reasoned that they were being taken over to secret points on the coast where big ships could not safely go. It was here that blockade-runners were refitted in our Civil War. It is here that this new gun-running plot has been laid." He turned quickly to Sydney. "The only obstacle between the transfer of the arms and success was the activity of an American consulate. Those lighters were not to carry goods to other islands. They were really destined for Mexico. It was profitable. And the scheme for removing opposition was evidently safe." Kennedy was holding up another bottle of keratin and some fruit seeds. "I found these in a room in the hotel," he added. I did not comprehend. "But," I cut in, "the hand-bag--the dinner--what of them?" "A plant--a despicable trespass on hospitality--all part of a scheme to throw the guilt on some one else, worthy of a renegade and traitor." Craig wheeled suddenly, then added, with an incisive gesture, "I suppose you know that there is reputed to have been on one of these hills the headquarters of the old pirate, Teach--'the mildest manner'd man that ever scuttled ship or cut a throat!'" Kennedy paused, then added, quickly, "In respect to covering up your gun-running, Whitson, you are superior even to Teach!" XII THE SUNKEN TREASURE "Get story Everson and bride yacht Belle Aventure seeking treasure sunk Gulf liner Antilles." Kennedy and I had proceeded after a few leisurely days in St. Thomas to Porto Rico. We had no particular destination, and San Juan rather appealed to us as an objective point because it was American. It was there that I found waiting for me the above message by wireless from the Star in New York. San Juan was, as we had anticipated, a thoroughly Americanized town and I lost no time in getting around at once to the office of the leading newspaper, the Colonial News. The editor, Kenmore, proved to be a former New York reporter who had come out in answer to an advertisement by the proprietors of the paper. "What's the big story here now?" I asked by way of preface, expecting to find that colonial newspapermen were provincial. "What's the big story?" repeated Kenmore, impatiently pushing aside a long leader on native politics and regarding me thoughtfully. "Well, I'm not superstitious, but a honeymoon spent trying to break into Davy Jones's locker for sunken treasure--I guess that's a good story, isn't it?" I showed him my message and he smiled. "You see, I was right," he exclaimed. "They're searching now at the Cay d'Or, the Golden Key, one of the southernmost of the Bahamas, I suppose you would call it. I wish I was like you. I'd like to get away from this political stuff long enough to get the story." He puffed absently on a fragrant native cigar. "I met them all when they were here, before they started," he resumed, reminiscently. "It was certainly a picturesque outfit--three college chums--one of them on his honeymoon, and the couple chaperoning the bride's sister. There was one of the college boys--a fellow named Gage--who fairly made news." "How was that?" inquired Kennedy, who had accompanied me, full of zest at the prospect of mixing in a story so romantic. "Oh, I don't know that it was his fault--altogether," replied Kenmore. "There's a young lady here in the city, the daughter of a pilot, Dolores Guiteras. She had been a friend of some one in the expedition, I believe. I suppose that's how Gage met her. I don't think either of them really cared for each other. Perhaps she was a bit jealous of the ladies of the party. I don't know anything much about it, only I remember one night in the cafe of the Palace Hotel, I thought Gage and another fellow would fight a duel--almost--until Everson dropped in and patched the affair up and the next day his yacht left for Golden Key." "I wish I'd been here to go with them," I considered. "How do you suppose I'll be able to get out there, now?" "You might be able to hire a tug," shrugged Kenmore. "The only one I know is that of Captain Guiteras. He's the father of this Dolores I told you about." The suggestion seemed good, and after a few moments more of conversation, absorbing what little Kenmore knew, we threaded our way across the city to the home of the redoubtable Guiteras and his pretty daughter. Guiteras proved to be a man of about fifty, a sturdy, muscular fellow, his face bronzed by the tropical sun. I had scarcely broached the purpose of my visit when his restless brown eyes seemed literally to flash. "No, sir," he exclaimed, emphatically. "You cannot get me to go on any such expedition. Mr. Everson came here first and tried to hire my tug. I wouldn't do it. No, sir--he had to get one from Havana. Why, the whole thing is unlucky--hoodooed, you call it. I will not touch it." "But," I remonstrated, surprised at his unexpected vehemence, "I am not asking you to join the expedition. We are only going to--" "No, no," he interrupted. "I will not consider it. I--" He cut short his remarks as a young woman, radiant in her Latin-American beauty, opened the door, hesitated at sight of us, then entered at a nod from him. We did not need to be told that this was the Dolores whom Kenmore's rumor had credited with almost wrecking Everson's expedition at the start. She was a striking type, her face, full of animation and fire, betraying more of passion than of intellect. A keen glance of inquiry from her wonderful eyes at her father was followed by a momentary faraway look, and she remained silent, while Guiteras paused, as if considering something. "They say," he continued, slowly, his features drawn sharply, "that there was loot of Mexican churches on that ship--the jewels of Our Lady of the Rosary at Puebla.... That ship was cursed, I tell you!" he added, scowling darkly. "No one was lost on it, though," I ventured at random. "I suppose you never heard the story of the Antilles?" he inquired, turning swiftly toward me. Then, without stopping: "She had just sailed from San Juan before she was wrecked--on her way to New York from Vera Cruz with several hundred Mexican refugees. Treasure? Yes; perhaps millions, money that belonged to wealthy families in Mexico--and some that had the curse on it. "You asked a moment ago if everybody wasn't rescued. Well, everybody was rescued from the wreck except Captain Driggs. I don't know what happened. No one knows. The fire had got into the engine-room and the ship was sinking fast. Passengers saw him, pale, like a ghost, some said. Others say there was blood streaming from his head. When the last boat-load left they couldn't find him. They had to put off without him. It was a miracle that no one else was lost." "How did the fire start?" inquired Kennedy, much interested. "No one knows that, either," answered Guiteras, shaking his head slowly. "I think it must have been smoldering in the hold for hours before it was discovered. Then the pumps either didn't work properly or it had gained too great headway for them. I've heard many people talk of it and of the treasure. No, sir, you wouldn't get me to touch it. Maybe you'll call it superstition. But I won't have anything to do with it. I wouldn't go with Mr. Everson and I won't go with you. Perhaps you don't understand, but I can't help it." Dolores had stood beside her father while he was speaking, but had said nothing, though all the time she had been regarding us from beneath her long black eyelashes. Arguments with the old pilot had no effect, but I could not help feeling that somehow she was on our side, that whether she shared his fears and prejudices, her heart was really somewhere near the Key of Gold. There seemed to be nothing for us to do but wait until some other way turned up to get out to the expedition, or perhaps Dolores succeeded in changing the captain's mind. We bowed ourselves out, not a little puzzled by the enigma of the obdurate old man and his pretty daughter. Try as I might among the busy shipping of the port, I could find no one else willing at any reasonable price to change his plans to accommodate us. It was early the next morning that a young lady, very much perturbed, called on us at our hotel, scarcely waiting even the introduction of her plainly engraved card bearing the name, Miss Norma Sanford. "Perhaps you know of my sister, Asta Sanford, Mrs. Orrin Everson," she began, speaking very rapidly as if under stress. "We're down here on Asta's honeymoon in Orrin's yacht, the Belle Aventure." Craig and I exchanged glances, but she did not give us a chance to interrupt. "It all seems so sudden, so terrible," she cried, in a burst of wild, incoherent feeling. "Yesterday Bertram Traynor died, and we've put back to San Juan with his body. I'm so worried for Orrin and my sister. I heard you were here, Professor Kennedy, and I couldn't rest until I saw you." She was looking anxiously at Craig. I wondered whether she had heard of our visit to the Guiterases and what she knew about that other woman. "I don't quite understand," interposed Kennedy, with an effort to calm her. "Why do you fear for your sister and Mr. Everson? Was there something--suspicious--about the death of Mr. Traynor?" "Indeed I think there was," she replied, quickly. "None of us has any idea how it happened. Let me tell you about our party. You see, there are three college chums, Orrin and two friends, Bertram Traynor and Donald Gage. They were all on a cruise down here last winter, the year after they graduated. It was in San Juan that Orrin first met Mr. Dominick, who was the purser on the Antilles--you know, that big steamer of the Gulf Line that was burned last year and went down with seven million dollars aboard?" Kennedy nodded to the implied query, and she went on: "Mr. Dominick was among those saved, but Captain Driggs was lost with his ship. Mr. Dominick had been trying to interest some one here in seeking the treasure. They knew about where the Antilles went down, and the first thing he wanted to do was to locate the wreck exactly. After that was done of course Mr. Dominick knew about the location of the ship's strong room and all that." "That, of course, was common knowledge to any one interested enough to find out, though," suggested Kennedy. "Of course," she agreed. "Well, a few months later Orrin met Mr. Dominick again, in New York. In the mean time he had been talking the thing over with various people and had become acquainted with a man who had once been a diver for the Interocean Marine Insurance Company--Owen Kinsale. Anyhow, so the scheme grew. They incorporated a company, the Deep Sea Engineering Company, to search for the treasure. That is how Orrin started. They are using his yacht and Mr. Dominick is really in command, though Mr. Kinsale has the actual technical knowledge." She paused, but again her feelings seemed to get the better of her. "Oh," she cried, "I've been afraid all along, lately. It's dangerous work. And then, the stories that have been told of the ship and the treasure. It seems ill-fated. Professor Kennedy," she appealed, "I wish you would come and see us. We're not on the yacht just now. We came ashore as soon as we arrived back, and Asta and Orrin are at the Palace Hotel now. Perhaps Orrin can tell you more. If you can do nothing more than quiet my fears--" Her eyes finished the sentence. Norma Sanford was one of those girls who impress you as quite capable of taking care of themselves. But in the presence of the tragedy and a danger which she felt but could not seem to define, she felt the need of outside assistance and did not hesitate to ask it. Nor was Kennedy slow in responding. He seemed to welcome a chance to help some one in distress. We found Everson and his young wife at the hotel, quite different now from the care-free adventurers who had set out only a few days before to wrest a fortune from chance. I had often seen portraits of the two Sanford sisters in the society pages of the papers in the States and knew that the courtship of Orrin Everson and Asta Sanford had been a true bit of modern romance. Asta Everson was a unique type of girl. She had begun by running fast motor cars and boats. That had not satisfied her, and she had taken up aviation. Once, even, she had tried deep-sea diving herself. It seemed as if she had been born with the spirit of adventure. To win her, Everson had done about everything from Arctic exploration one summer when he was in college to big-game hunting in Africa, and mountain-climbing in the Andes. Odd though the romance might seem to be, one could not help feeling that the young couple were splendidly matched in their tastes. Each had that spirit of restlessness which, at least, sent them out playing at pioneering. Everson had organized the expedition quite as much in the spirit of revolt against a prosaic life of society at home as for gain. It had appealed strongly to Asta. She had insisted that nothing so much as a treasure hunt would be appropriate for their wedding-trip and they had agreed on the unconventional. Accordingly, she and her sister had joined Everson and his party, Norma, though a year younger, being quite like her sister in her taste for excitement. "Of course, you understand," explained Everson, as he hurriedly tried to give us some idea of what had happened, "we knew that the Antilles had sunk somewhere off the Cay d'Or. It was first a question of locating her. That was all that we had been doing when Bertram died. It is terrible, terrible. I can't believe it. I can't understand it." In spite of his iron nerve, the tragedy seemed to have shaken Everson profoundly. "You had done nothing that might have been dangerous?" asked Kennedy, pointedly. "Nothing," emphasized Everson. "You see, we located the wreck in a way somewhat similar to the manner in which they sweep the seas for mines and submarines. It was really very simple, though it took us some time. All we did was to drag a wire at a fixed depth between the yacht and the tug, or rather, I suppose you'd almost call it a trawler, which I chartered from Havana. What we were looking for was to have the wire catch on some obstruction. It did, too, not once, but many times, due to the unevenness of the ocean bed. Once we located a wreck, but it was in shallow water, a small boat, not the one we were looking for." "But you succeeded finally?" "Yes, only day before yesterday we located her. We marked the spot with a buoy and were getting ready for real work. It was just after that that Bertram was taken ill and died so suddenly. We've left Dominick, Kinsale, Gage, and the rest on the trawler there, while I came here with Traynor's body. God! but it was awful to have to send the news back to New York. I don't know what to think or what to do." "How did he die?" asked Kennedy, endeavoring to gain the confidence of young Everson. "Do you recall any of his symptoms?" "It came on him so suddenly," he replied, "that we hadn't much time to think. As nearly as we could make out, it began with a faintness and difficulty in breathing. We asked him how he felt--but it seemed as if he was deaf. I thought it might be the 'bends'--you know, caisson disease--and we started to put him in the medical lock which we had for the divers, but before we could get it ready he was unconscious. It was all so sudden that it stunned us. I can't make it out at all." Neither Asta nor Norma seemed able to tell anything. In fact, the blow had been so swift and unexpected, so incomprehensible, that it had left them thoroughly alarmed. The body of Traynor had already been brought ashore and placed in a local undertaking shop. With Everson, Kennedy and I hastened to visit it. Traynor had been an athlete and powerfully built, which made his sudden death seem all the more strange. Without a word, Craig set to work immediately examining his body, while we stood aside, watching him in anxious silence. Kennedy consumed the greater part of the morning in his careful investigation, and after some time Everson began to get restless, wondering how his wife and sister-in-law were getting on in his absence. To keep him company I returned to the hotel with him, leaving Kennedy to pursue his work alone. There was nothing much that either of us could say or do, but I thought I observed, on closer acquaintance with Norma, that she had something weighing on her mind. Was it a suspicion of which she had not told us? Evidently she was not prepared to say anything yet, but I determined, rather than try to quiz her, to tell Kennedy, in the hope that she might confide in him what she would not breathe to any one else. It was perhaps an hour or more later that we returned to Craig. He was still at work, though from his manner it was evident that his investigations had begun to show something, however slight. "Have you found anything?" asked Everson, eagerly. "I think I have," returned Craig, measuring his words carefully. "Of course you know the dangers of diving and the view now accepted regarding the rapid effervescence of the gases which are absorbed in the body fluids during exposure to pressure. I think you know that experiment has proved that when the pressure is suddenly relieved the gas is liberated in bubbles within the body. That is what seems to do the harm. His symptoms, as you described them, seemed to indicate that. It is like charged water in a bottle. Take out the cork and the gas inside which has been under pressure bubbles up. In the human body, air and particularly the nitrogen in the air, literally form death bubbles." Everson said nothing as he regarded Kennedy's face searchingly, and Craig went on: "Set free in the spinal cord, for instance, such bubbles may cause partial paralysis, or in the heart may lead to stoppage of the circulation. In this case I am quite sure that what I have found indicates air in the arteries, the heart, and the blood vessels of the brain. It must have been a case of air embolism, insufflation." Though Everson seemed all along to have suspected something of the sort, Kennedy's judgment left him quite as much at a loss for an explanation. Kennedy seemed to understand, as he went on: "I have tried to consider all the ways such a thing could have happened," he considered. "It is possible that air might have been introduced into the veins by a hypodermic needle or other instrument. But I find no puncture of the skin or other evidence that would support that theory. I have looked for a lesion of the lungs, but find none. Then how could it have occurred? Had he done any real deep diving?" Everson shook his head slowly. "No," he replied. "As I said, it wouldn't have been so incomprehensible if he had. Besides, if we had been diving, we should have been on the lookout. No, Bertram had only tested the apparatus once, after we located the wreck. He didn't much more than go under the surface--nothing like the practice dives we all made up in Long Island Sound before we came down here. He was only testing the pumps and other things to see whether they had stood the voyage. Why, it was nothing at all! I don't see how it could have given any one the 'bends'--much less a fellow like Traynor. Why, I think he could have stood more than Kinsale with a little practice. Kennedy, I can't get it out of my mind that there's something about this that isn't RIGHT." Craig regarded Everson gravely. "Frankly," he confessed, "I must say that I don't understand it myself--at this distance." "Would you come out to the Key with me?" hastened Everson, as though grasping at a possible solution. "I should be delighted to help you in any manner that I can," returned Craig, heartily. Everson could not find words to express his gratitude as we hurried back to the hotel. In the excitement, I had completely forgotten the despatch from the Star, but now I suddenly realized that here, ready to hand, was the only way of getting out to the Key of Gold and securing the story. Asta Everson and Norma, especially, were overjoyed at the news that Kennedy had consented to accompany them back to the wreck. Evidently they had great faith in him, from what they had heard at home. Accordingly, Everson lost no time in preparing to return to the yacht. Nothing more now could be done for poor Traynor, and delay might mean much in clearing up the mystery, if mystery it should prove. We were well on our way toward the landing place before I realized that we were going over much the same route that Kennedy and I had taken the day before to reach the home of Guiteras. I was just about to say something about it to Kennedy, and of the impression that Norma had made on me, when suddenly a figure darted from around a corner and confronted us. We stopped in surprise. It was no other than Dolores herself--not the quiet, subdued Dolores we had seen the day before, but an almost wild, passionate creature. What it was that had transformed her I could not imagine. It was not ourselves that she seemed to seek, nor yet the Eversons. She did not pause until she had come close to Norma herself. For a moment the two women, so different in type, faced each other, Dolores fiery with the ardent beauty of her race, Norma pulsating with life and vigor, yet always mistress of herself. "I warn you!" cried Dolores, unable to restrain herself. "You thought the other was yours--and he was not. Do not seek revenge. He is mine--MINE, I tell you. Win your own back again. I was only making sport of him. But mine--beware!" For a moment Norma gazed at her, then, without a word, turned aside and walked on. Another instant and Dolores was gone as suddenly as she had appeared. Asta looked inquiringly, but Norma made no attempt at explanation. What did it mean? Had it anything to do with the dispute in the hotel which Kenmore had witnessed? At the landing we parted for a time with Everson, to return to our hotel and get what little we needed, including Kennedy's traveling laboratory, while Everson prepared quarters for our reception on the yacht. "What do you make of that Dolores incident?" I hastened to ask the moment we were alone. "I don't know," he replied, "except that I feel it has an important bearing on the case. There is something that Norma hasn't told us, I fear." While we waited for a wagon to transfer our goods to the dock, Kennedy took a moment to call up Kenmore on the News. As he turned to me from the telephone, I saw that what he had learned had not helped him much in his idea of the case. "It was the Interocean Company which had insured the Antilles," was all he said. Instantly I thought of Kinsale and his former connection. Was he secretly working with them still? Was there a plot to frustrate Everson's plans? At least the best thing to do was to get out to the wreck and answer our many questions at first hand. The Belle Aventure was a trim yacht of perhaps seventy feet, low, slim, and graceful, driven by a powerful gas-engine and capable of going almost anywhere. An hour later we were aboard and settled in a handsomely appointed room, where Craig lost no time in establishing his temporary traveling crime clinic. It was quite late before we were able to start, for Everson had a number of commissions to attend to on this his first visit to port since he had set out so blithely. Finally, however, we had taken aboard all that he needed and we slipped out quietly past the castle on the point guarding the entrance to the harbor. All night we plowed ahead over the brilliant, starry, tropical sea, making splendid time, for the yacht was one of the fastest that had ever been turned out by the builders. Now and then I could see that Kennedy was furtively watching Norma, in the hope that she might betray whatever secret it was she was guarding so jealously. Though she betrayed nothing, I felt sure that it had to do with some member of the expedition and that it was a more than ordinarily complicated affair of the heart. The ladies had retired, leaving us with Everson in the easy wicker chairs on the after-deck. "I can't seem to get out of my mind, Everson, that meeting with the Spanish girl on the street," suddenly remarked Kennedy, in the hope of getting something by surprise. "You see, I had already heard of a little unpleasantness in a hotel cafe, before the expedition started. Somehow I feel that there must be some connection." For a moment Everson regarded Kennedy under the soft rays of the electric light under the awning as it swayed in the gentle air, then looked out over the easy swell of the summer sea. "I don't understand it myself," he remarked, at length, lowering his voice. "When we came down here Dominick knew that girl, Dolores, and of course Kinsale met her right away, too. I thought Gage was head over ears in love with Norma--and I guess he is. Only that night in the cafe I just didn't like the way he proposed a toast to Dolores. He must have met her that day. Maybe he was a bit excited. What she said to-day might mean that it was her fault. I don't know. But since we've been out to the Key I fancy Norma has been pretty interested in Dominick. And Kinsale doesn't hesitate to show that he likes her. It all sets Donald crazy. It's so mixed up. I can't make anything of it. And Norma--well, even Asta can't get anything out of her. I wish to Heaven you could straighten the thing out." We talked for some time, without getting much more light than Everson had been able at first to shed on the affair, and finally we retired, having concluded that only time and events would enable us to get at the truth. It was early in the morning that I was wakened by a change in the motion of the boat. There was very little vibration from the engine, but this motion was different. I looked out of the port-hole which had been very cleverly made to resemble a window and found that we had dropped anchor. The Key of Gold was a beautiful green island, set, like a sparkling gem, in a sea of deepest turquoise. Slender pines with a tuft of green at the top rose gracefully from the wealth of foliage below and contrasted with the immaculate white of the sandy beach that glistened in the morning sun. Romance seemed to breathe from the very atmosphere of the place. We found that the others on the yacht were astir, too, and, dressing hastily, we went out on deck. Across the dancing waves, which seemed to throw a mocking challenge to the treasure-seekers to find what they covered, we could see the trawler. Already a small power-boat had put out from her and was plowing along toward us. It was as the boat came alongside us that we met Gage for the first time. He was a tall, clean-cut fellow, but even at a glance I recognized that his was an unusual type. I fancied that both proctors and professors had worried over him when he was in college. Particularly I tried to discover how he acted when he met Norma. It was easy to see that he was very eager to greet her, but I fancied that there was some restraint on her part. Perhaps she felt that we were watching and was on her guard. Dominick greeted Everson warmly. He was a man of about thirty-five and impressed one as having seen a great deal of the world. His position as purser had brought him into intimate contact with many people, and he seemed to have absorbed much from them. I could imagine that, like many people who had knocked about a great deal, he might prove a very fascinating person to know. Kinsale, on the other hand, was a rather silent fellow and therefore baffling. In his own profession of deep-sea diving he was an expert, but beyond that I do not think he had much except an ambition to get ahead, which might be praiseworthy or not, according as he pursued it. I fancied that next to Everson himself, Norma placed more confidence in Dominick than in any of the others, which seemed to be quite natural, though it noticeably piqued Gage. On the part of all three, Gage, Dominick, and Kinsale, it was apparent that they were overjoyed at the return of Norma, which also was quite natural, for even a treasure-hunt has hours of tedium and there could be nothing tedious when she was about. Asta was undoubtedly the more fascinating, but she was wrapped up in Everson. It was not long before Kennedy and I also fell under the spell of Norma's presence and personality. We hurried through breakfast and lost no time in accepting Everson's invitation to join him, with the rest, in the little power-boat on a visit to the trawler. It was Dominick who took upon himself the task of explaining to us the mysteries of treasure-hunting as we saw them. "You see," he remarked, pointing out to us what looked almost like a strangely developed suit of armor, "we have the most recent deep-sea diving-outfit which will enable us to go from two hundred to three hundred feet down--farther, and establish a record if we had to do it. It won't be necessary, though. The Antilles lies in about two hundred and fifty feet of water, we have found. This armor has to be strong, for, with the air pressure inside, it must resist a pressure of nearly half a pound per square inch for each foot we go--to be exact, something like a hundred and five pounds per square inch at the depth of the wreck. Perhaps if Traynor had been diving we might have thought that that was the trouble." It was the first reference since we arrived to the tragedy. "He had only had the suit on once," went on Dominick, confirming Everson, "and that was merely to test the pumps and valves and joints. Even Kinsale, here, hasn't been down. Still, we haven't been idle. I have something to report. With our instruments we have discovered that the ship has heeled over and that it will be a bit harder job to get into my office and get out the safe than we hoped--but feasible." Kennedy showed more interest in the diving apparatus than he had shown in anything else so far. The trawler was outfitted most completely as a tender, having been anchored over the exact spot at which the descents were to be made, held by four strong cables, with everything in readiness for action. I saw him cast a quick glance at the others. For the moment Dominick, Gage, and Kinsale seemed to have forgotten us in their interest explaining to Norma what had been accomplished in her absence. He seized the occasion to make an even closer examination of the complicated apparatus. So carefully had accident been guarded against that even a device for the purification of the air had been installed in the machine which forced the fresh air down to the diver, compressed. It was this apparatus which I saw Kennedy studying most, especially one part where the air was passed through a small chamber containing a chemical for the removal of carbon dioxide. As he looked up, I saw a peculiar expression on his face. Quickly he removed the chemical, leaving the tube through which the air passed empty. "I think the air will be pure enough without any such treatment," he remarked, glancing about to be sure no one had observed. "How is that?" I inquired, eagerly. "Well, you know air is a mechanical mixture of gases, mainly oxygen and nitrogen. Here's something that gives it an excess of nitrogen and a smaller percentage of oxygen. Nitrogen is the more dangerous gas for one under compressed air. It is the more inert nitrogen that refuses to get out of the blood after one has been under pressure, that forms the bubbles of gas which cause all the trouble, the 'bends,' compressed-air sickness, you know." "Then that is how Traynor died?" I whispered, coming hastily to the conclusion. "Some one placed the wrong salt in there--took out oxygen, added nitrogen, instead of removing carbon dioxide?" Norma had turned toward us. It was too early for Kennedy to accuse anybody, whatever might be his suspicions. He could not yet come from under cover. "I think so," was all he replied. A moment later the group joined us. "No one has been down on the wreck yet?" inquired Craig, at which Everson turned quickly to the three companions he had left in charge, himself anxious to know. "No," replied Kinsale before any one else could answer. "Mr. Dominick thought we'd better wait until you came back." "Then I should like to be the first," cut in Craig, to my utter surprise. Remonstrance had no effect with him. Neither Norma nor Asta could dissuade him. As for the rest of us, our objections seemed rather to confirm him in his purpose. Accordingly, in spite of the danger, which now no one no more than he knew, all the preparations were made for the first dive. With the aid of Kinsale, whom I watched closely, though no more so than Craig, he donned the heavy suit of rubberized reinforced canvas, had the leads placed on his feet and finally was fitted with the metal head and the "bib"--the whole weighing hardly short of three hundred pounds. It was with serious misgiving that I saw him go over the side of the trawler and shoot down into the water with its dark mystery and tragedy. The moments that he was down seemed interminable. Suspiciously I watched every move that the men made, fearful that they might do something. I longed for the technical knowledge that would have enabled me to handle the apparatus. I tried to quiet my fears by reasoning that Craig must have had perfect confidence in the value of his discovery if he were willing to risk his life on it, yet I felt that at least a show of vigilance on my part might bluff any one off from an attempt to tamper again with the air-supply. I stuck about closely. Yet, when there came a hasty signal on the indicator from below, although I felt that he had been down for ages, I knew that it had been only a very short time. Could it be a signal of trouble? Had some one again tampered with the apparatus? Would they never bring him up? It seemed as if they were working fearfully slow. I remembered how quickly he had shot down. What had seemed then only a matter of seconds and minutes now seemed hours. It was only by sheer will power that I restrained myself as I realized that going under the air pressure might be done safely quite fast, that he must come out slowly, by stages, that over the telephone that connected with his helmet he was directing the decompression in accordance with the latest knowledge that medical science had derived of how to avoid the dread caisson disease. I don't know when I have felt more relief than I did at seeing his weird headgear appear at the surface. The danger from the "bends" might not be entirely over yet, but at least it was Craig himself, safe, at last. As he came over the side of the trawler I ran to him. It was like trying to greet a giant in that outlandish suit which was so clumsy out of the water. Craig's back was turned to the others, and when I realized the reason I stood aghast. He had brought up a skull and had handed the gruesome thing to me with a motion of secrecy. Meanwhile he hastened to get out of the cumbersome suit, and, to my delight, showed no evidence yet of any bad effects. That he should have made the descent and returned so successfully I felt must be a surprise to some one. Who was it? I could not help thinking of Kinsale again. Was he working for two masters? Was he still employed by the insurance company? Was this a scheme to capture all the rich salvage of the ship instead of that percentage to which Everson had secured an agreement with the underwriters? Kennedy lost no time in getting back to the Belle Aventure with the skull which I had concealed for him. It was a strange burden and I was not loath to resign it to him. None of the others, apparently, knew that he had brought up anything with him, and to all questions he replied as though he had merely been testing out the apparatus and, except in a most cursory way, had not made an examination of the ship, although what he had observed confirmed the investigations they had already made from the surface. In our cabin, Kennedy set to work immediately after opening his traveling laboratory and taking from it a small kit of tools and some materials that looked almost like those for an actor's make-up. I saw that he wished to be left alone and retired as gracefully as I could, determined to employ the time in watching the others. I found Norma seated in one of the wicker chairs on the after-deck, talking earnestly with Dominick, and, hesitating whether I should interrupt them, I paused between the library and the sumptuously fitted main saloon. I was glad that I did, for just that moment of hesitation was enough for me to surprise a man peering out at them through the curtains of a window, with every evidence of intense dislike of the situation. Looking closer, I saw that it was Gage. Had I expected anything of the sort I should have gone even more cautiously. As it was, though I surprised him, he heard me in time to conceal his real intentions by some trivial action. It seemed as if our arrival had been succeeded by a growth of suspicion among the members of the little party. Each, as far as I could make out, was now on guard, and, remembering that Kennedy had often said that that was a most fruitful time, since it was just under such circumstances that even the cleverest could not help incriminating himself, I hastened back to let Craig know how matters were. He was at work now on a most grotesque labor, and, as he placed on it the finishing touches, he talked abstractedly. "What I am using, Walter," he explained, "might be called a new art. Lately science has perfected the difficult process of reconstructing the faces of human beings of whom only the skull or a few bones, perhaps, are obtainable. "To the unskilled observer a fleshless skull presents little human likeness and certainly conveys no notion of the exact appearance in life of the person to whom it belonged. But by an ingenious system of building up muscles and skin upon the bones of the skull this appearance can be reproduced with scientific accuracy. "The method, I might say, has been worked out independently by Professor von Froriep, in Germany, and by Dr. Henri Martin, in France. Its essential principle consists in ascertaining from the examination of many corpses the normal thickness of flesh that overlies a certain bone in a certain type of face. From these calculations the scientists by elaborate processes build up a face on the skull." I watched him, with an uncontrollable fascination. "For instance," he went on, "a certain type of bone always has nearly the same thickness of muscle over it. A very fine needle with graduations of hundredths of an inch is used in these measurements. As I have done here, a great number of tiny plaster pyramids varying in height according to the measurements obtained by these researches are built up over the skull, representing the thickness of the muscles. The next step will be to connect them together by a layer of clay the surface of which is flush with the tips of the pyramids. Then wax and grease paint and a little hair will complete it. You see, it is really scientific restoration of the face. I must finish it. Meanwhile, I wish you would watch Norma. I'll join you in a short time." Norma was not on deck when I returned, nor did I see any one else for some time. I walked forward, and paused at the door to the little wireless-room on the yacht, intending to ask the operator if he had seen her. "Where's Mr. Kennedy?" he inquired, before I had a chance to put my own question. "Some one has been in this wireless-room this morning and must have been sending messages. Things aren't as I left them. I think he ought to know." Just then Everson himself came up from below, his face almost as white as the paint on the sides of his yacht. Without a word, he drew me aside, looking about fearfully as though he were afraid of being overheard. "I've just discovered half a dozen sticks of dynamite in the hold," he whispered, hoarsely, staring wide-eyed at me. "There was a timing device, set for to-night. I've severed it. Where's Kennedy?" "Your wireless has been tampered with, too," I blurted out, telling what I had just learned. We looked at each other blankly. Clearly some one had plotted to blow up the yacht and all of us on board. Without another word, I took his arm and we walked toward our state-room, where Kennedy was at work. As we entered the narrow passage to it I heard low voices. Some one was there before us. Kennedy had shut the door and was talking in the hall. As we turned the corner I saw that it was Norma, whom I had forgotten in the surprise of the two discoveries that had been so suddenly made. As we approached she glanced significantly at Kennedy as if appealing to him to tell something. Before he could speak, Everson himself interrupted, telling of his discovery of the dynamite and of what the wireless operator had found. There was a low exclamation from Norma. "It's a plot to kidnap me!" she cried, in a smothered voice. "Professor Kennedy--I told you I thought so!" Everson and I could only look our inquiries at the startling new turn of events. "Miss Sanford has just been to her state-room," hastily explained Craig. "There she found that some one had carefully packed up a number of her things and hidden them, as if waiting a chance to get them off safely. I think her intuition is correct. There would be no motive for robbery--here." Vainly I tried to reason it out. As I thought, I recalled that Gage had seemed insanely jealous of both Dominick and Kinsale, whenever he saw either with Norma. Did Gage know more about these mysterious happenings than appeared? Why had he so persistently sought her? Had Norma instinctively fled from his attentions? "Where are the others?" asked Craig, quickly. I turned to Everson. I had not yet had time to find out. "Gone back to the trawler," he replied. "Signal them to come aboard here directly," ordered Craig. It seemed an interminable time as the message was broken out in flags to the trawler, which was not equipped with the wireless. Even the hasty explanation which Kennedy had to give to Asta Everson, as she came out of her cabin, wondering where Orrin had gone, served only to increase the suspense. It was as though we were living over a powder-magazine that threatened to explode at any moment. What did the treachery of one member of the expedition mean? Above all, who was it? We had been so intent watching from the deck the all too slow approach of the little power-boat from the trawler that we had paid no attention to what was on our other quarter. "A tug approaching, sir," reported the man on watch to Everson. "Seems to be heading for us, sir." We turned to look. Who was she, friend or foe? We knew not what to expect. Everson, pale but with a firm grip on his nerves, did not move from the deck as the power-boat came alongside, and Dominick, Gage, and Kinsale swung themselves up the ladder to us. "It's the tug of that pilot, Guiteras, sir," interposed the man who had spoken before. Not a word was spoken, though I fancied that a quiet smile flitted over Kennedy's face as we waited. The tug ranged up alongside us. To my utter astonishment, I saw Dolores, her black eyes eagerly scanning our faces. Was she looking for Gage, I wondered? It was only a moment when the party that had put out from the tug also came tumbling aboard. "I got your message, Kennedy, and brought Guiteras. He wouldn't join the expedition, but he thought more of his daughter than of anything else." It was Kenmore, who had at last achieved his wish to get on the treasure-hunt story. Everson looked inquiringly at Craig. "Message?" repeated Kennedy. "I sent no message." It was Kenmore's turn to stare. Had some one hoaxed him into a wild-goose chase, after all? "Nothing? About Dolores being deserted, and--" "He shall marry my daughter!" boomed a gruff voice as Guiteras shouldered his way through the little group, his hand shooting back to a pocket where bulged a huge Colt. Like a flash Kennedy, who had been watching, caught his wrist. "Just a second, Captain," he shouted, then turned to us, speaking rapidly and excitedly. "This thing has all been carefully, diabolically laid out. All who stood in the way of the whole of the treasure were to be eliminated. One person has sought to get it all--at any cost." In Craig's own hand now gleamed a deadly automatic while with the other he held Guiteras's wrist. "But," he added, tensely, "an insane passion has wrecked the desperate scheme. A woman has been playing a part--leading the man on to his own destruction in order to save the man she really loves." I looked over at Norma. She was pale and agitated, then burning and nervous by turns. It was only by a most heroic effort that she seemed able to restrain herself, her eyes riveted on Kennedy's face, weighing every word to see whether it balanced with a feeling in her own heart. "The Antilles," shot out Kennedy, suddenly, "was burned and sunk, not by accident, but with a purpose. That purpose has run through all the events I have seen--the use of Mr. Everson, his yacht, his money, his influence. Come!" He strode down the passage to our state-room, and we followed in awed silence. "It is a vast, dastardly crime--to get the Mexican millions," he went on, pausing, his hand on the knob of the door while we crowded the narrow passage. "I have brought up from the wreck a skull which I found near a safe, unlocked so that entrance would be easy. The skull shows plainly that the man had been hit on the head by some blunt instrument, crushing him. Had he discovered something that it was inconvenient to know? You have heard the stories of the ill-fated ship--" Craig flung open the door suddenly. We saw a weird face--the head apparently streaming blood from a ghastly wound. There was a shrill cry beside me. "It's his ghost--Captain Driggs! God save me--it's his ghost come to haunt me and claim the treasure!" I turned quickly. Dominick had broken down. "You were--just leading him on--tell me--Norma." I turned again quickly. It was Gage, who had taken Norma's hand, quivering with excitement. "You never cared for her?" she asked, with the anxiety that showed how in her heart she loved him. "Never. It was part of the plot. I sent the message to get her here to show you. I didn't know you were playing a game--" Suddenly the sharp crack of a pistol almost deafened us in the close passageway. As the smoke cleared, I saw Dolores, her eyes blazing with hatred, jealousy, revenge. In her hand was the pistol she had wrenched from her father. On the floor across the door-sill sprawled a figure. Dominick had paid the price of his faithlessness to her also. THE END 
5151	----	THE CRAIG KENNEDY SERIES THE EXPLOITS OF ELAINE BY ARTHUR B. REEVE CONTENTS CHAPTER I THE CLUTCHING HAND II THE TWILIGHT SLEEP III THE VANISHING JEWELS IV "THE FROZEN SAFE" V THE POISONED ROOM VI THE VAMPIRE VII THE DOUBLE TRAP VIII THE HIDDEN VOICE IX THE DEATH RAY X THE LIFE CURRENT XI THE HOUR OF THREE XII THE BLOOD CRYSTALS XIII THE DEVIL WORSHIPPERS XIV THE RECKONING THE EXPLOITS OF ELAINE CHAPTER I THE CLUTCHING HAND "Jameson, here's a story I wish you'd follow up," remarked the managing editor of the Star to me one evening after I had turned in an assignment of the late afternoon. He handed me a clipping from the evening edition of the Star and I quickly ran my eye over the headline: "THE CLUTCHING HAND" WINS AGAIN NEW YORK'S MYSTERIOUS MASTER CRIMINAL PERFECTS ANOTHER COUP CITY POLICE COMPLETELY BAFFLED "Here's this murder of Fletcher, the retired banker and trustee of the University," he explained. "Not a clue--except a warning letter signed with this mysterious clutching fist. Last week it was the robbery of the Haxworth jewels and the killing of old Haxworth. Again that curious sign of the hand. Then there was the dastardly attempt on Sherburne, the steel magnate. Not a trace of the assailant except this same clutching fist. So it has gone, Jameson--the most alarming and most inexplicable series of murders that has ever happened in this country. And nothing but this uncanny hand to trace them by." The editor paused a moment, then exclaimed, "Why, this fellow seems to take a diabolical--I might almost say pathological--pleasure in crimes of violence, revenge, avarice and self-protection. Sometimes it seems as if he delights in the pure deviltry of the thing. It is weird." He leaned over and spoke in a low, tense tone. "Strangest of all, the tip has just come to us that Fletcher, Haxworth, Sherburne and all the rest of those wealthy men were insured in the Consolidated Mutual Life. Now, Jameson, I want you to find Taylor Dodge, the president, and interview him. Get what you can, at any cost." I had naturally thought first of Kennedy, but there was no time now to call him up and, besides, I must see Dodge immediately. Dodge, I discovered over the telephone, was not at home, nor at any of the clubs to which he belonged. Late though it was I concluded that he was at his office. No amount of persuasion could get me past the door, and, though I found out later and shall tell soon what was going on there, I determined, about nine o'clock, that the best way to get at Dodge was to go to his house on Fifth Avenue, if I had to camp on his front doorstep until morning. The harder I found the story to get, the more I wanted it. With some misgivings about being admitted, I rang the bell of the splendid, though not very modern, Dodge residence. An English butler, with a nose that must have been his fortune, opened the door and gravely informed me that Mr. Dodge was not at home, but was expected at any moment. Once in, I was not going lightly to give up that advantage. I bethought myself of his daughter, Elaine, one of the most popular debutantes of the season, and sent in my card to her, on a chance of interesting her and seeing her father, writing on the bottom of the card: "Would like to interview Mr. Dodge regarding Clutching Hand." Summoning up what assurance I had, which is sometimes considerable, I followed the butler down the hall as he bore my card. As he opened the door of the drawing room I caught a vision of a slip of a girl, in an evening gown. Elaine Dodge was both the ingenue and the athlete--the thoroughly modern type of girl--equally at home with tennis and tango, table talk and tea. Vivacious eyes that hinted at a stunning amber brown sparkled beneath masses of the most wonderful auburn hair. Her pearly teeth, when she smiled, were marvellous. And she smiled often, for life to her seemed a continuous film of enjoyment. Near her I recognized from his pictures, Perry Bennett, the rising young corporation lawyer, a mighty good looking fellow, with an affable, pleasing way about him, perhaps thirty-five years old or so, but already prominent and quite friendly with Dodge. On a table I saw a book, as though Elaine had cast it down when the lawyer arrived to call on the daughter under pretense of waiting for her father. Crumpled on the table was the Star. They had read the story. "Who is it, Jennings?" she asked. "A reporter, Miss Dodge," answered the butler glancing superciliously back at me, "and you know how your father dislikes to see anyone here at the house," he added deferentially to her. I took in the situation at a glance. Bennett was trying not to look discourteous, but this was a call on Elaine and it had been interrupted. I could expect no help from that quarter. Still, I fancied that Elaine was not averse to trying to pique her visitor and determined at least to try it. "Miss Dodge," I pleaded, bowing as if I had known them all my life, "I've been trying to find your father all the evening. It's very important." She looked up at me surprised and in doubt whether to laugh or stamp her pretty little foot in indignation at my stupendous nerve. She laughed. "You are a very brave young man," she replied with a roguish look at Bennett's discomfiture over the interruption of the tete-a-tete. There was a note of seriousness in it, too, that made me ask quickly, "Why?" The smile flitted from her face and in its place came a frank earnest expression which I later learned to like and respect very much. "My father has declared he will eat the very next reporter who tries to interview him here," she answered. I was about to prolong the waiting time by some jolly about such a stunning girl not having by any possibility such a cannibal of a parent, when the rattle of the changing gears of a car outside told of the approach of a limousine. The big front door opened and Elaine flung herself in the arms of an elderly, stern-faced, gray-haired man. "Why, Dad," she cried, "where have you been? I missed you so much at dinner. I'll be so glad when this terrible business gets cleared up. Tell--me. What is on your mind? What is it that worries you now?" I noticed then that Dodge seemed wrought-up and a bit unnerved, for he sank rather heavily into a chair, brushed his face with his handkerchief and breathed heavily. Elaine hovered over him solicitously, repeating her question. With a mighty effort he seemed to get himself together. He rose and turned to Bennett. "Perry," he exclaimed, "I've got the Clutching Hand!" The two men stared at each other. "Yes," continued Dodge, "I've just found out how to trace it, and tomorrow I am going to set the alarms of the city at rest by exposing--" Just then Dodge caught sight of me. For the moment I thought perhaps he was going to fulfill his threat. "Who the devil--why didn't you tell me a reporter was here, Jennings?" he sputtered indignantly, pointing toward the door. Argument, entreaty were of no avail. He stamped crustily into the library, taking Bennett with him and leaving me with Elaine. Inside I could hear them talking, and managed to catch enough to piece together the story. I wanted to stay, but Elaine, smiling at my enthusiasm, shook her head and held out her hand in one of her frank, straight-arm hand shakes. There was nothing to do but go. At least, I reflected, I had the greater part of the story--all except the one big thing, however,--the name of the criminal. But Dodge would know him tomorrow! I hurried back to the Star to write my story in time to catch the last morning edition. . . . . . . . . Meanwhile, if I may anticipate my story, I must tell of what we later learned had happened to Dodge so completely to upset him. Ever since the Consolidated Mutual had been hit by the murders, he had had many lines out in the hope of enmeshing the perpetrator. That night, as I found out the next day, he had at last heard of a clue. One of the company's detectives had brought in a red-headed, lame, partly paralyzed crook who enjoyed the expressive monniker of "Limpy Red." "Limpy Red" was a gunman of some renown, evil faced and having nothing much to lose, desperate. Whoever the master criminal of the Clutching Hand might have been he had seen fit to employ Limpy but had not taken the precaution of getting rid of him soon enough when he was through. Wherefore Limpy had a grievance and now descended under pressure to the low level of snitching to Dodge in his office. "No, Governor," the trembling wretch had said as he handed over a grimy envelope, "I ain't never seen his face--but here is directions how to find his hang-out." As Limpy ambled out, he turned to Dodge, quivering at the enormity of his unpardonable sin in gang-land, "For God's sake, Governor," he implored, "don't let on how you found out!" And yet Limpy Red had scarcely left with his promise not to tell, when Dodge, happening to turn over some papers came upon an envelope left on his own desk, bearing that mysterious Clutching Hand! He tore it open, and read in amazement: "Destroy Limpy Red's instructions within the next hour." Dodge gazed about in wonder. This thing was getting on his nerves. He determined to go home and rest. Outside the house, as he left his car, pasted over the monogram on the door, he had found another note, with the same weird mark and the single word: "Remember!" Much of this I had already gathered from what I overheard Dodge telling Bennett as they entered the library. Some, also, I have pieced together from the story of a servant who overheard. At any rate, in spite of the pleadings of young Bennett, Dodge refused to take warning. In the safe in his beautifully fitted library he deposited Limpy's document in an envelope containing all the correspondence that had lead up to the final step in the discovery. . . . . . . . . It was late in the evening when I returned to our apartment and, not finding Kennedy there, knew that I would discover him at the laboratory. "Craig," I cried as I burst in on him, "I've got a case for you--greater than any ever before!" Kennedy looked up calmly from the rack of scientific instruments that surrounded him, test tubes, beakers, carefully labelled bottles. He had been examining a piece of cloth and had laid it aside in disappointment near his magnifying glass. Just now he was watching a reaction in a series of test tubes standing on his table. He was looking dejectedly at the floor as I came in. "Indeed?" he remarked coolly going back to the reaction. "Yes," I cried. "It is a scientific criminal who seems to leave no clues." Kennedy looked up gravely. "Every criminal leaves a trace," he said quietly. "If it hasn't been found, then it must be because no one has ever looked for it in the right way." Still gazing at me keenly, he added, "Yes, I already knew there was such a man at large. I have been called in on that Fletcher case--he was a trustee of the University, you know." "All right," I exclaimed, a little nettled that he should have anticipated me even so much in the case. "But you haven't heard the latest." "What is it?" he asked with provoking calmness, "Taylor Dodge," I blurted out, "has the clue. To-morrow he will track down the man!" Kennedy fairly jumped as I repeated the news. "How long has he known?" he demanded eagerly. "Perhaps three or four hours," I hazarded. Kennedy gazed at me fixedly. "Then Taylor Dodge is dead!" he exclaimed, throwing off his acid-stained laboratory smock and hurrying into his street clothes. "Impossible!" I ejaculated. Kennedy paid no attention to the objection. "Come, Walter," he urged. "We must hurry, before the trail gets cold." There was something positively uncanny about Kennedy's assurance. I doubted--yet I feared. It was well past the middle of the night when we pulled up in a night-hawk taxicab before the Dodge house, mounted the steps and rang the bell. Jennings answered sleepily, but not so much so that he did not recognize me. He was about to bang the door shut when Kennedy interposed his foot. "Where is Mr. Dodge?" asked Kennedy. "Is he all right?" "Of course he is--in bed," replied the butler. Just then we heard a faint cry, like nothing exactly human. Or was it our heightened imaginations, under the spell of the darkness? "Listen!" cautioned Kennedy. We did, standing there now in the hall. Kennedy was the only one of us who was cool. Jennings' face blanched, then he turned tremblingly and went down to the library door whence the sounds had seemed to come. He called but there was no answer. He turned the knob and opened the door. The Dodge library was a large room. In the center stood a big flat-topped desk of heavy mahogany. It was brilliantly lighted. At one end of the desk was a telephone. Taylor Dodge was lying on the floor at that end of the desk--perfectly rigid--his face distorted--a ghastly figure. A pet dog ran over, sniffed frantically at his master's legs and suddenly began to howl dismally. Dodge was dead! "Help!" shouted Jennings. Others of the servants came rushing in. There was for the moment the greatest excitement and confusion. Suddenly a wild figure in flying garments flitted down the stairs and into the library, dropping beside the dead man, without seeming to notice us at all. "Father!" shrieked a woman's voice, heart broken. "Father! Oh--my God--he--he is dead!" It was Elaine Dodge. With a mighty effort, the heroic girl seemed to pull herself together. "Jennings," she cried, "Call Mr. Bennett--immediately!" From the one-sided, excited conversation of the butler over the telephone, I gathered that Bennett had been in the process of disrobing in his own apartment uptown and would be right down. Together, Kennedy, Elaine and myself lifted Dodge to a sofa and Elaine's aunt, Josephine, with whom she lived, appeared on the scene, trying to quiet the sobbing girl. Kennedy and I withdrew a little way and he looked about curiously. "What was it?" I whispered. "Was it natural, an accident, or--or murder?" The word seemed to stick in my throat. If it was a murder, what was the motive? Could it have been to get the evidence which Dodge had that would incriminate the master criminal? Kennedy moved over quietly and examined the body of Dodge. When he rose, his face had a peculiar look. "Terrible!" he whispered to me. "Apparently he had been working at his accustomed place at the desk when the telephone rang. He rose and crossed over to it. See! That brought his feet on this register let into the floor. As he took the telephone receiver down a flash of light must have shot from it to his ear. It shows the characteristic electric burn." "The motive?" I queried. "Evidently his pockets had been gone through, though none of the valuables were missing. Things on his desk show that a hasty search has been made." Just then the door opened and Bennett burst in. As he stood over the body, gazing down at it, repressing the emotions of a strong man, he turned to Elaine and in a low voice, exclaimed, "The Clutching Hand did this! I shall consecrate my life to bring this man to justice!" He spoke tensely and Elaine, looking up into his face, as if imploring his help in her hour of need, unable to speak, merely grasped his hand. Kennedy, who in the meantime had stood apart from the rest of us, was examining the telephone carefully. "A clever crook," I heard him mutter between his teeth. "He must have worn gloves. Not a finger print--at least here." . . . . . . . . Perhaps I can do no better than to reconstruct the crime as Kennedy later pieced these startling events together. Long after I had left and even after Bennett left, Dodge continued working in his library, for he was known as a prodigious worker. Had he taken the trouble, however, to pause and peer out into the moonlight that flooded the back of his house, he might have seen the figures of two stealthy crooks crouching in the half shadows of one of the cellar windows. One crook was masked by a handkerchief drawn tightly about his lower face, leaving only his eyes visible beneath the cap with visor pulled down over his forehead. He had a peculiar stoop of the shoulders and wore his coat collar turned up. One hand, the right, seemed almost deformed. It was that which gave him his name in the underworld--the Clutching Hand. The masked crook held carefully the ends of two wires attached to an electric feed, and sending his pal to keep watch outside, he entered the cellar of the Dodge house through a window whose pane they had carefully removed. As he came through the window he dragged the wires with him, and, alter a moment's reconnoitering attached them to the furnace pipe of the old-fashioned hot-air heater where the pipe ran up through the floor to the library above. The other wire was quickly attached to the telephone where its wires entered. Upstairs, Dodge, evidently uneasy in his mind about the precious "Limpy Red" letter, took it from the safe along with most of the other correspondence and, pressing a hidden spring in the wall, opened a secret panel, placed most of the important documents in this hiding place. Then he put some blank sheets of paper in an envelope and returned it to the safe. Downstairs the masked master criminal had already attached a voltmeter to the wires he had installed, waiting. Just then could be heard the tinkle of Dodge's telephone and the old man rose to answer it. As he did so he placed his foot on the iron register, his hand taking the telephone and the receiver. At that instant came a powerful electric flash. Dodge sank on the floor grasping the instrument, electrocuted. Below, the master criminal could scarcely refrain from exclaiming with satisfaction as his voltmeter registered the powerful current that was passing. A moment later the criminal slid silently into Dodge's room. Carefully putting on rubber gloves and avoiding touching the register, he wrenched the telephone from the grasp of the dead man, replacing it in its normal position. Only for a second did he pause to look at his victim as he destroyed the evidence of his work. Minutes were precious. First Dodge's pockets, then his desk engaged his attention. There was left the safe. As he approached the strong box, the master criminal took two vials from his pockets. Removing a bust of Shakespeare that stood on the safe, he poured the contents of the vials in two mixed masses of powder forming a heap on the safe, into which he inserted two magnesium wires. He lighted them, sprang back, hiding his eyes from the light, and a blinding gush of flame, lasting perhaps ten seconds, poured out from the top of the safe. It was not an explosion, but just a dazzling, intense flame that sizzled and crackled. It seemed impossible, but the glowing mass was literally sinking, sinking down into the cold steel. At last it burned through--as if the safe had been of tinder! Without waiting a moment longer than necessary, the masked criminal advanced again and actually put his hand down through the top of the safe, pulling out a bunch of papers. Quickly he thrust them all, with just a glance, into his pocket. Still working quickly, he took the bust of the great dramatist which he had removed and placed it under the light. Next from his pocket he drew two curious stencils, as it were, which he had apparently carefully prepared. With his hands, still carefully gloved, he rubbed the stencils on his hair, as if to cover them with a film of natural oils. Then he deliberately pressed them over the statue in several places. It was a peculiar action and he seemed to fairly gloat over it when it was done, and the bust returned to its place, covering the hole. As noiselessly as he had come, he made his exit after one last malignant look at Dodge. It was now but the work of a moment to remove the wires he had placed, and climb out of the window, taking them and destroying the evidence down in the cellar. A low whistle from the masked crook, now again in the shadow, brought his pal stealthily to his side. "It's all right," he whispered hoarsely to the man. "Now, you attend to Limpy Red." The villainous looking pal nodded and without another word the two made their getaway, safely, in opposite directions. . . . . . . . . When Limpy Red, still trembling, left the office of Dodge earlier in the evening, he had repaired as fast as his shambling feet would take him to his favorite dive upon Park Row. There he might have been seen drinking with any one who came along, for Limpy had money--blood money,--and the recollection of his treachery and revenge must both be forgotten and celebrated. Had the Bowery "sinkers" not got into his eyes, he might have noticed among the late revellers, a man who spoke to no one but took his place nearby at the bar. Limpy had long since reached the point of saturation and, lurching forth from his new found cronies, he sought other fields of excitement. Likewise did the newcomer, who bore a strange resemblance to the look-out who had been stationed outside at the Dodge house a scant half hour before. What happened later was only a matter of seconds. It came when the hated snitch--for gangdom hates the informer worse than anything else dead or alive--had turned a sufficiently dark and deserted corner. A muffled thud, a stifled groan followed as a heavy section of lead pipe wrapped in a newspaper descended on the crass skull of Limpy. The wielder of the improvised but fatal weapon permitted himself the luxury of an instant's cruel smile--then vanished into the darkness leaving another complete job for the coroner and the morgue. It was the vengeance of the Clutching Hand--swift, sure, remorseless. And yet it had not been a night of complete success for the master criminal, as anyone might have seen who could have followed his sinuous route to a place of greater safety. Unable to wait longer he pulled the papers he had taken from the safe from his pocket. His chagrin at finding them to be blank paper found only one expression of foiled fury--that menacing clutching hand! . . . . . . . . Kennedy had turned from his futile examination for marks on the telephone. There stood the safe, a moderate sized strong box but of a modern type. He tried the door. It was locked. There was not a mark on it. The combination had not been tampered with. Nor had there been any attempt to "soup" the safe. With a quick motion he felt in his pocket as if looking for gloves. Finding none, he glanced about, and seized a pair of tongs from beside the grate. With them, in order not to confuse any possible finger prints on the bust, he lifted it off. I gave a gasp of surprise. There, in the top of the safe, yawned a gaping hole through which one could have thrust his arm! "What is it?" we asked, crowding about him. "Thermit," he replied laconically. "Thermit?" I repeated. "Yes--a compound of iron oxide and powdered aluminum invented by a chemist at Essen, Germany. It gives a temperature of over five thousand degrees. It will eat its way through the strongest steel." Jennings, his mouth wide open with wonder, advanced to take the bust from Kennedy. "No--don't touch it," he waved him off, laying the bust on the desk. "I want no one to touch it--don't you see how careful I was to use the tongs that there might be no question about any clue this fellow may have left on the marble?" As he spoke, Craig was dusting over the surface of the bust with some black powder. "Look!" exclaimed Craig suddenly. We bent over. The black powder had in fact brought out strongly some peculiar, more or less regular, black smudges. "Finger prints!" I cried excitedly. "Yes," nodded Kennedy, studying them closely. "A clue--perhaps." "What--those little marks--a clue?" asked a voice behind us. I turned and saw Elaine, looking over our shoulders, fascinated. It was evidently the first time she had realized that Kennedy was in the room. "How can you tell anything by that?'" she asked. "Why, easily," he answered picking up a brass blotting-pad which lay on the desk. "You see, I place my finger on this weight--so. I dust the powder over the mark--so. You could see it even without the powder on this glass. Do you see those lines? There are various types of markings--four general types--and each person's markings are different, even if of the same general type--loop, whorl, arch, or composite." He continued working as he talked. "Your thumb marks, for example, Miss Dodge, are different from mine. Mr. Jameson's are different from both of us. And this fellow's finger prints are still different. It is mathematically impossible to find two alike in every respect." Kennedy was holding the brass blotter near the bust as he talked. I shall never forget the look of blank amazement on his face as he bent over closer. "My God!" he exclaimed excitedly, "this fellow is a master criminal! He has actually made stencils or something of the sort on which by some mechanical process he has actually forged the hitherto infallible finger prints!" I, too, bent over and studied the marks on the bust and those Kennedy had made on the blotter to show Elaine. THE FINGER PRINTS ON THE BUST WERE KENNEDY'S OWN. CHAPTER II THE TWILIGHT SLEEP Kennedy had thrown himself wholeheartedly into the solution of the mysterious Dodge case. Far into the night, after the challenge of the forged finger print, he continued at work, endeavoring to extract a clue from the meagre evidence--the bit of cloth and trace of poison already obtained from other cases, and now added the strange succession of events that surrounded the tragedy we had just witnessed. We dropped around at the Dodge house the next morning. Early though it was, we found Elaine, a trifle paler but more lovely than ever, and Perry Bennett themselves vainly endeavoring to solve the mystery of the Clutching Hand. They were at Dodge's desk, she in the big desk chair, he standing beside her, looking over some papers. "There's nothing there," Bennett was saying as we entered. I could not help feeling that he was gazing down at Elaine a bit more tenderly than mere business warranted. "Have you--found anything?" queried Elaine anxiously, turning eagerly to Kennedy. "Nothing--yet," he answered shaking his head, but conveying a quiet idea of confidence in his tone. Just then Jennings, the butler, entered, bringing the morning papers. Elaine seized the Star and hastily opened it. On the first page was the story I had telephone down very late in the hope of catching a last city edition. We all bent over and Craig read aloud: "CLUTCHING HAND" STILL AT LARGE NEW YORK'S MASTER CRIMINAL REMAINS UNDETECTED--PERPETRATES NEW DARING MURDER AND ROBBERY OF MILLIONAIRE DODGE He had scarcely finished reading the brief but alarming news story that followed and laid the paper on the desk, when a stone came smashing through the window from the street. Startled, we all jumped to our feet. Craig hurried to the window. Not a soul was in sight! He stooped and picked up the stone. To it was attached a piece of paper. Quickly he unfolded it and read: "Craig Kennedy will give up his search for the "Clutching Hand"--or die!" Later I recalled that there seemed to be a slight noise downstairs, as if at the cellar window through which the masked man had entered the night before. In point of fact, one who had been outside at the time might actually have seen a sinister face at that cellar window, but to us upstairs it was invisible. The face was that of the servant, Michael. Without another word Kennedy passed into the drawing room and took his hat and coat. Both Elaine and Bennett followed. "I'm afraid I must ask you to excuse me--for the present," Craig apologized. Elaine looked at him anxiously. "You--you will not let that letter intimidate you?" she pleaded, laying her soft white hand on his arm. "Oh, Mr. Kennedy," she added, bravely keeping back the tears, "avenge him! All the money in the world would be too little to pay--if only--" At the mere mention of money Kennedy's face seemed to cloud, but only for a moment. He must have felt the confiding pressure of her hand, for as she paused, appealingly, he took her hand in his, bowing slightly over it to look closer into her upturned face. "I'll try," he said simply. Elaine did not withdraw her hand as she continued to look up at him. Craig looked at her, as I had never seen him look at a woman before in all our long acquaintance. "Miss Dodge," he went on, his voice steady as though he were repressing something, "I will never take another case until the 'Clutching Hand' is captured." The look of gratitude she gave him would have been a princely reward in itself. I did not marvel that all the rest of that day and far into the night Kennedy was at work furiously in his laboratory, studying the notes, the texture of the paper, the character of the ink, everything that might perhaps suggest a new lead. It was all, apparently, however, without result. . . . . . . . . It was some time after these events that Kennedy, reconstructing what had happened, ran across, in a strange way which I need not tire the reader by telling, a Dr. Haynes, head of the Hillside Sanitarium for Women, whose story I shall relate substantially as we received it from his own lips: It must have been that same night that a distinguished visitor drove up in a cab to our Hillside Sanitarium, rang the bell and was admitted to my office. I might describe him as a moderately tall, well-built man with a pleasing way about him. Chiefly noticeable, it seems to me, were his mustache and bushy beard, quite medical and foreign. I am, by the way, the superintending physician, and that night I was sitting with Dr. Thompson, my assistant, in the office discussing a rather interesting case, when an attendant came in with a card and handed it to me. It read simply, "Dr. Ludwig Reinstrom, Coblenz." "Here's that Dr. Reinstrom, Thompson, about whom my friend in Germany wrote the other day," I remarked, nodding to the attendant to admit Dr. Reinstrom. I might explain that while I was abroad some time ago, I made a particular study of the "Daemmerschlaf"--otherwise, the "twilight sleep," at Freiburg where it was developed and at other places in Germany where the subject had attracted great attention. I was much impressed and had imported the treatment to Hillside. While we waited I reached into my desk and drew out the letter to which I referred, which ended, I recall: "As Dr. Reinstrom is in America, he will probably call on you. I am sure you will be glad to know him. "With kindest regards, I am, "Fraternally yours, "EMIL SCHWARZ, M. D., "Director, Leipsic Institute of Medicine." "Most happy to meet you, Dr. Reinstrom," I greeted the new arrival, as he entered our office. For several minutes we sat and chatted of things medical here and abroad. "What is it, Doctor," I asked finally, "that interests you most in America?" "Oh," he replied quickly with an expressive gesture, "it is the broadmindedness with which you adopt the best from all over the world, regardless of prejudice. For instance, I am very much interested in the new twilight sleep. Of course you have borrowed it largely from us, but it interests me to see whether you have modified it with practice. In fact I have come to the Hillside Sanitarium particularly to see it used. Perhaps we may learn something from you." It was most gracious and both Dr. Thompson and myself were charmed by our visitor. I reached over and touched a call-button and our head nurse entered from a rear room. "Are there any operations going on now?" I asked. She looked mechanically at her watch. "Yes, there are two cases, now, I think," she answered. "Would you like to follow our technique, Doctor?" I asked, turning to Dr. Reinstorm. "I should be delighted," he acquiesced. A moment later we passed down the corridor of the Sanitarium, still chatting. At the door of a ward I spoke to the attendant who indicated that a patient was about to be anesthetized, and Reinstrom and I entered the room. There, in perfect quiet, which is an essential part of the treatment, were several women patients lying in bed in the ward. Before us two nurses and a doctor were in attendance on one. I spoke to the Doctor, Dr. Holmes, by the way, who bowed politely to the distinguished Dr. Reinstrom, then turned quickly to his work. "Miss Sears," he asked of one of the nurses, "will you bring me that hypodermic needle? How are you getting on, Miss Stern?" to the other who was scrubbing the patient's arm with antiseptic soap and water, thoroughly sterilizing the skin. "You will see, Dr. Reinstrom." I interposed in a low tone, "that we follow in the main your Freiburg treatment. We use scopolamin and narkophin." I held up the bottle, as I said it, a rather peculiar shaped bottle, too. "And the pain?" he asked. "Practically the same as in your experience abroad. We do not render the patient unconscious, but prevent her from remembering anything that goes on." Dr. Holmes, the attending physician, was just starting the treatment. Filling his hypodermic, he selected a spot on the patient's arm, where it had been scrubbed and sterilized, and injected the narcotic. "How simply you do it all, here!" exclaimed Reinstrom in surprise and undisguised admiration. "You Americans are wonderful!" "Come--see a patient who is just recovering," I added, much flattered by the praise, which, from a German physician, meant much. Reinstrom followed me out of the door and we entered a private room of the hospital where another woman patient lay in bed carefully watched by a nurse. "How do you do?" I nodded to the nurse in a modulated tone. "Everything progressing favorably?" "Perfectly," she returned, as Reinstrom, Haynes and myself formed a little group about the bedside of the unconscious woman. "And you say they have no recollection of anything that happens?" asked Reinstrom. "Absolutely none--if the treatment is given properly," I replied confidently. I picked up a piece of bandage which was the handiest thing about me and tied it quite tightly about the patient's arm. As we waited, the patient, who was gradually coming from under the drug, roused herself. "What is that--it hurts!" she said putting her hand on the bandage I had tied tightly. "That is all right. Just a moment. I'll take it off. Don't you remember it?" I asked. She shook her head. I smiled at Reinstrom. "You see, she has no recollection of my tying the bandage on her arm," I pointed out. "Wonderful!" ejaculated Reinstrom as we left the room. All the way back to the office he was loud in his praises and thanked us most heartily, as he put on his hat and coat and shook hands a cordial good-bye. Now comes the strange part of my story. After Reinstrom had gone, Dr. Holmes, the attending physician of the woman whom we had seen anesthetized, missed his syringe and the bottle of scopolamine. "Miss Sears," he asked rather testily, "what have you done with the hypodermic and the scopolamine?" "Nothing," she protested. "You must have done something." She repeated that she had not. "Well, it is very strange then," he said, "I am positive I laid the syringe and the bottle right here on this tray on the table." Holmes, Miss Sears and Miss Stern all hunted, but it could not be found. Others had to be procured. I thought little of it at the time, but since then it has occurred to me that it might interest you, Professor Kennedy, and I give it to you for what it may be worth. It was early the next morning that I awoke to find Kennedy already up and gone from our apartment. I knew he must be at the laboratory, and, gathering the mail, which the postman had just slipped through the letter slot, I went over to the University to see him. As I looked over the letters to cull out my own, one in a woman's handwriting on attractive notepaper addressed to him caught my eye. As I came up the path to the Chemistry Building I saw through the window that, in spite of his getting there early, he was finding it difficult to keep his mind on his work. It was the first time I had ever known anything to interfere with science in his life. I thought of the letter again. Craig had lighted a Bunsen burner under a large glass retort. But he had no sooner done so than he sat down on a chair and, picking up a book which I surmised might be some work on toxicology, started to read. He seemed not to be able, for the moment, to concentrate his mind and after a little while closed the book and gazed straight ahead of him. Again I thought of the letter, and the vision that, no doubt, he saw of Elaine making her pathetic appeal for his help. As he heard my footstep in the hall, it must have recalled him for he snapped the book shut and moved over quickly to the retort. "Well," I exclaimed as I entered, "you are the early bird. Did you have any breakfast?" I tossed down the letters. He did not reply. So I became absorbed in the morning paper. Still, I did not neglect to watch him covertly out of the corner of my eye. Quickly he ran over the letters, instead of taking them, one by one, in his usual methodical way. I quite complimented my own superior acumen. He selected the dainty note. A moment Craig looked at it in anticipation, then tore it open eagerly. I was still watching his face over the top of the paper and was surprised to see that it showed, first, amazement, then pain, as though something had hurt him. He read it again--then looked straight ahead, as if in a daze. "Strange, how much crime there is now," I commented, looking up from the paper I had pretended reading. No answer. "One would think that one master criminal was enough," I went on. Still no answer. He continued to gaze straight ahead at blankness. "By George," I exclaimed finally, banging my fist on the table and raising my voice to catch his attention, "you would think we had nothing but criminals nowadays." My voice must have startled him. The usually imperturbable old fellow actually jumped. Then, as my question did not evidently accord with what was in his mind, he answered at random, "Perhaps--I wonder if--" and then he stopped, noncommittally. Suddenly he jumped up, bringing his tightly clenched fist down with a loud clap into the palm of his hand. "By heaven!" he exclaimed, "I--I will!" Startled at his incomprehensible and unusual conduct I did not attempt to pursue the conversation but let him alone as he strode hastily to the telephone. Almost angrily he seized the receiver and asked for a number. It was not like Craig and I could not conceal my concern. "Wh-what's the matter, Craig?" I blurted out eagerly. As he waited for the number, he threw the letter over to me. I took it and read: "Professor Craig Kennedy, "The University, The Heights, City. "Dear Sir,-- "I have come to the conclusion that your work is a hindrance rather than an assistance in clearing up my father's death and I hereby beg to state that your services are no longer required. This is a final decision and I beg that you will not try to see me again regarding the matter. "Very truly yours, ELAINE DODGE." If it had been a bomb I could not have been more surprised. A moment before I think I had just a sneaking suspicion of jealousy that a woman--even Elaine--should interest my old chums. But now all that was swept away. How could any woman scorn him? I could not make it out. Kennedy impatiently worked the receiver up and down, repeating the number. "Hello--hello," he repeated, "Yes--hello. Is Miss--oh--good morning, Miss Dodge." He was hurrying along as if to give her no chance to cut him off. "I have just received a letter, Miss Dodge, telling me that you don't want me to continue investigating your father's death, and not to try to see you again about--" He stopped. I could hear the reply, as sometimes one can when the telephone wire conditions are a certain way and the quality of the voice of the speaker a certain kind. "Why--no--Mr. Kennedy, I have written you no letter." The look of mingled relief and surprise that crossed Craig's face spoke volumes. "Miss Dodge," he almost shouted, "this is a new trick of the Clutching Hand. I--I'll be right over." Craig hung up the receiver and turned from the telephone. Evidently he was thinking deeply. Suddenly his face seemed to light up. He made up his mind to something and a moment later he opened the cabinet--that inexhaustible storehouse from which he seemed to draw weird and curious instruments that met the ever new problems which his strange profession brought to him. I watched curiously. He took out a bottle and what looked like a little hypodermic syringe, thrust them into his pocket and, for once, oblivious to my very existence, deliberately walked out of the laboratory. I did not propose to be thus cavalierly dismissed. I suppose it would have looked ridiculous to a third party but I followed him as hastily as if he had tried to shut the door on his own shadow. We arrived at the corner above the Dodge house just in time to see another visitor--Bennett--enter. Craig quickened his pace. Jennings had by this time become quite reconciled to our presence and a moment later we were entering the drawing room, too. Elaine was there, looking lovelier than ever in the plain black dress, which set off the rosy freshness of her face. "And, Perry," we heard her say, as we were ushered in, "someone has even forged my name--the handwriting and everything--telling Mr. Kennedy to drop the case--and I never knew." She stopped as we entered. We bowed and shook hands with Bennett. Elaine's Aunt Josephine was in the room, a perfect duenna. "That's the limit!" exclaimed Bennett. "Miss Dodge has just been telling me,--" "Yes," interrupted Craig. "Look, Miss Dodge, this is it." He handed her the letter. She almost seized it, examining it carefully, her large eyes opening wider in wonder. "This is certainly my writing and my notepaper," she murmured, "but I never wrote the letter!" Craig looked from the letter to her keenly. No one said a word. For a moment Kennedy hesitated, thinking. "Might I--er--see your room, Miss Dodge?" he asked at length. Aunt Josephine frowned. Bennett and I could not conceal our surprise. "Why, certainly," nodded Elaine, as she led the way upstairs. It was a dainty little room, breathing the spirit of its mistress. In fact it seemed a sort of profanation as we all followed in after her. For a moment Kennedy stood still, then he carefully looked about. At the side of the bed, near the head, he stooped and picked up something which he held in the palm of his hand. I bent over. Something gleamed in the morning sunshine--some little thin pieces of glass. As he tried deftly to fit the tiny little bits together, he seemed absorbed in thought. Quickly he raised it to his nose, as if to smell it. "Ethyl chloride!" he muttered, wrapping the pieces carefully in a paper and putting them into his pocket. An instant later he crossed the room to the window and examined it. "Look!" he exclaimed. There, plainly, were marks of a jimmy which had been inserted near the lock to pry it open. "Miss Dodge," he asked, "might I--might I trouble you to let me see your arm?" Wonderingly she did so and Kennedy bent almost reverently over her plump arm examining it. On it was a small dark discoloration, around which was a slight redness and tenderness. "That," he said slowly, "is the mark of a hypodermic needle." As he finished examining Elaine's arm he drew the letter from his pocket. Still facing her he said in a low tone, "Miss Dodge--you did write this letter--but under the influence of the new 'twilight sleep.'" We looked at one another amazed. Outside, if we had been at the door in the hallway, we might have seen the sinister-faced Michael listening. He turned and slipped quietly away. "Why, Craig," I exclaimed excitedly, "what do you mean?" "Exactly what I say. With Miss Dodge's permission I shall show you. By a small administration of the drug which will injure you in no way, Miss Dodge, I think I can bring back the memory of all that occurred to you last night. Will you allow me?" "Mercy, no!" protested Aunt Josephine. Craig and Elaine faced each other as they had the day before when she had asked him whether the sudden warning of the Clutching Hand would intimidate him. She advanced a step nearer. Elaine trusted him. "Elaine!" protested Aunt Josephine again. "I want the experiment to be tried," she said quietly. A moment later Kennedy had placed her in a wing chair in the corner of the room. "Now, Mrs. Dodge," he said, "please bring me a basin and a towel." Aunt Josephine, reconciled, brought them. Kennedy dropped an antiseptic tablet into the water and carefully sterilized Elaine's arm just above the spot where the red mark showed. Then he drew the hypodermic from his pocket--carefully sterilizing it, also, and filling it with scopolamine from the bottle. "Just a moment, Miss Dodge," he encouraged as he jabbed the needle into her arm. She did not wince. "Please lie back on the couch," he directed. Then turning to us he added, "It takes some time for this to work. Our criminal got over that fact and prevented an outcry by using ethyl chloride first. Let me reconstruct the scene." As we watched Elaine going under slowly, Craig talked. "That night," he said, "warily, the masked criminal of the Clutching Hand might have been seen down below us in the alley. Up here, Miss Dodge, worn out by the strain of her father's death, let us say, was nervously trying to read, to do anything that would take her mind off the tragedy. Perhaps she fell asleep. "Just then the Clutching Hand appeared. He came stealthily through that window which he had opened. A moment he hesitated, seeing Elaine asleep. Then he tiptoed over to the bed, let us say, and for a moment looked at her, sleeping. "A second later he had thrust his hand into his pocket and had taken out a small glass bulb with a long thin neck. That was ethyl chloride, a drug which produces a quick anesthesia. But it lasts only a minute or two. That was enough, As he broke the glass neck of the bulb--letting the pieces fall on the floor near the bed--he shoved the thing under Elaine's face, turning his own head away and holding a handkerchief over his own nose. The mere heat of his hand was enough to cause the ethyl chloride to spray out and overcome her instantly. He stepped away from her a moment and replaced the now empty vial in his pocket. "Then he took a box from his pocket, opened it. There must have been a syringe and a bottle of scopolamine. Where they came from I do not know, but perhaps from some hospital. I shall have to find that out later. He went to Elaine, quickly jabbing the needle, with no resistance from her now. Slowly he replaced the bottle and the needle in his pocket. He could not have been in any hurry now, for it takes time for the drug to work." Kennedy paused. Had we known at the time, Michael--he of the sinister face--must have been in the hallway, careful that no one saw him. A tap at the door and the Clutching Hand, that night, must have beckoned him. A moment's parley and they separated--Clutching Hand going back to Elaine, who was now under the influence of the second drug. "Our criminal," resumed Kennedy thoughtfully, "may have shaken Elaine. She did not answer. Then he may have partly revived her. She must have been startled. Clutching Hand, perhaps, was half crouching, with a big ugly blue steel revolver leveled full in her face. "'One word and I shoot!' he probably cried. 'Get up!' "Trembling, she must have done so. 'Your slippers and a kimono,' he would naturally have ordered. She put them on mechanically. Then he must have ordered her to go out of the door and down the stairs. Clutching Hand must have followed and as he did so he would have cautiously put out the lights." We were following, spell-bound, Kennedy's graphic reconstruction of what must have happened. Evidently he had struck close to the truth. Elaine's eyes were closed. Gently Kennedy led her along. "Now, Miss Dodge," he encouraged, "try--try hard to recollect just what it was that happened last night--everything." As Kennedy paused after his quick recital, she seemed to tremble all over. Slowly she began to speak. We stood awestruck. Kennedy had been right! The girl was now living over again those minutes that had been forgotten--blotted out by the drug. And it was all real to her, too,--terribly real. She was speaking, plainly in terror. "I see a man--oh, such a figure--with a mask. He holds a gun in my face--he threatens me. I put on my kimono and slippers, as he tells me. I am in a daze. I know what I am doing--and I don't know. I go out with him, downstairs, into the library." Elaine shuddered again at the recollection. "Ugh! The room is dark, the room where he killed my father. Moonlight outside streams in. This masked man and I come in. He switches on the lights. "'Go to the safe,' he says, and I do it, the new safe, you know. 'Do you know the combination?' he asks me. 'Yes,' I reply, too frightened to say no. "'Open it then,' he says, waving that awful revolver closer. I do so. Hastily he rummages through it, throwing papers here and there. But he seems not to find what he is after and turns away, swearing fearfully. "'Hang it!' he cries to me. 'Where else did your father keep papers?' I point in desperation at the desk. He takes one last look at the safe, shoves all the papers he has strewn on the floor back again and slams the safe shut. "'Now, come on!' he says, indicating with the gun that he wants me to follow him away from the safe. At the desk he repeats the search. But he finds nothing. Almost I think he is about to kill me. 'Where else did your father keep papers?' he hisses fiercely, still threatening me with the gun. "I am too frightened to speak. But at last I am able to say, 'I--I don't know!' Again he threatens me. 'As God is my judge,' I cry, 'I don't know.' It is fearful. Will he shoot me? "Thank heaven! At last he believes me. But such a look of foiled fury I have never seen on any human face before. "'Sit down!' he growls, adding, 'at the desk.' I do. "'Take some of your notepaper--the best.' I do that, too. "'And a pen,' he goes on. My fingers can hardly hold it. "'Now--write!' he says, and as he dictates, I write--" "This?" interjected Kennedy, eagerly holding up the letter that he had received from her. Elaine looked it over with her drug-laden eyes. "Yes," she nodded, then lapsed again to the scene itself. "He reads it over and as he does so says, 'Now, address an envelope.' Himself he folds the letter, seals the envelope, stamps it, and drops it into his pocket, hastily straightening the desk. "'Now, go ahead of me--again. Leave the room--no, by the hall door. We are going back upstairs.' I obey him, and at the door he switches off the lights. How I stand it, I don't know. I go upstairs, mechanically, into my own room--I and this masked man. "'Take off the kimono and slippers!' he orders. I do that. 'Get into bed!' he growls. I crawl in fearfully. For a moment he looks about,--then goes out--with a look back as he goes. Oh! Oh! That hand--which he raises at me--THAT HAND!" The poor girl was sitting bolt upright, staring straight at the hall door, as we watched and listened, fascinated. Kennedy was bending over, soothing her. She gave evidences of coming out from the effect of the drug. I noticed that Bennett had suddenly moved a step in the direction of the door at which she stared. "My God!" he muttered, staring, too. "Look!" We did look. A letter was slowly being inserted under the door. I took a quick step forward. That moment I felt a rough tug at my arm, and a voice whispered, "Wait--you chump!" It was Kennedy. He had whipped out his automatic and had carefully leveled it at the door. Before he could fire, however, Bennett had rushed ahead. I followed. We looked down the hall. Sure enough, the figure of a man could be seen disappearing around an angle. I followed Bennett out of the door and down the hall. Words cannot keep pace with what followed. Together we rushed to the backstairs. "Down there, while I go down the front!" cried Bennett. I went down and he turned and went down the other flight. As he did so, Craig followed him. Suddenly, in the drawing room, I bumped into a figure on the other side of the portieres. I seized him. We struggled. Rip! The portieres came down, covering me entirely. Over and over we went, smashing a lamp. It was vicious. Another man attacked me, too. "I--I've got him--Kennedy!" I heard a voice pant over me. A scream followed from Aunt Josephine. Suddenly the portieres were pulled off me. "The deuce!" puffed Kennedy. "It's Jameson!" Bennett had rushed plump into me, coming the other way, hidden by the portieres. If we had known at the time, our Michael of the sinister face had gained the library and was standing in the center of the room. He had heard me coming and had fled to the drawing room. As we finished our struggle in the library, he rose hastily from behind the divan in the other room where he had dropped and had quietly and hastily disappeared through another door. Laughing and breathing hard, they helped me to my feet. It was no joke to me. I was sore in every bone. "Well, where DID he go?" insisted Bennett. "I don't know--perhaps back there," I cried. Bennett and I argued a moment, then started and stopped short. Aunt Josephine had run downstairs and now was shoving the letter into Craig's hands. We gathered about him, curiously. He opened it. On it was that awesome Clutching Hand again. Kennedy read it. For a moment he stood and studied it, then slowly crushed it in his hand. Just then Elaine, pale and shaken from the ordeal she had voluntarily gone through, burst in upon us from upstairs. Without a word she advanced to Craig and took the letter from him. Inside, as on the envelope, was that same signature of the Clutching Hand. Elaine gazed at it wild-eyed, then at Craig. Craig smilingly reached for the note, took it, folded it and unconcernedly thrust it into his pocket. "My God!" she cried, clasping her hands convulsively and repeating the words of the letter. "YOUR LAST WARNING!" CHAPTER III THE VANISHING JEWELS Banging away at my typewriter, the next day, in Kennedy's laboratory, I was startled by the sudden, insistent ringing of the telephone near me. "Hello," I answered, for Craig was at work at his table, trying still to extract some clue from the slender evidence thus far elicited in the Dodge mystery. "Oh, Mr. Kennedy," I heard an excited voice over the wire reply, "my friend, Susie Martin is here. Her father has just received a message from that Clutching Hand and--" "Just a moment, Miss Dodge," I interrupted. "This is Mr. Jameson." "Oh!" came back the voice, breathless and disappointed. "Let me have Mr. Kennedy--quick." I had already passed the telephone to Craig and was watching him keenly as he listened over it. The anticipation of a message from Elaine did not fade, yet his face grew grave as he listened. He motioned to me for a pad and pencil that lay near me. "Please read the letter again, slower, Miss Dodge," he asked, adding, "There isn't time for me to see it--just yet. But I want it exactly. You say it is made up of separate words and type cut from newspapers and pasted on note paper?" I handed him paper and pencil. "All right now, Miss Dodge, go ahead." As he wrote, he indicated to me by his eyes that he wanted me to read. I did so: "Sturtevant Martin, Jeweler, "739 1/2 Fifth Ave., "New York City. "SIR: "As you have failed to deliver the $10,000, I shall rob your main diamond case at exactly noon today." "Thank you, Miss Dodge," continued Kennedy, laying down the pencil. "Yes, I understand perfectly--signed by that same Clutching Hand. Let me see," he pondered, looking at his watch. "It is now just about half past eleven. Very well. I shall meet you and Miss Martin at Mr. Martin's store directly." It lacked five minutes of noon when Kennedy and I dashed up before Martin's and dismissed our taxi-cab. A remarkable scene greeted us as we entered the famous jewelry shop. Involuntarily I drew back. Squarely in front of us a man had suddenly raised a revolver and leveled it at us. "Don't!" cried a familiar voice. "That is Mr. Kennedy!" Just then, from a little knot of people, Elaine Dodge sprang forward with a cry and seized the gun. Kennedy turned to her, apparently not half so much concerned about the automatic that yawned at him as about the anxiety of the pretty girl who had intervened. The too eager plainclothesman lowered the gun sheepishly. Sturtevant Martin was a typical society business man, quietly but richly dressed. He was inclined to be pompous and affected a pair of rather distinguished looking side whiskers. In the excitement I glanced about hurriedly. There were two or three policemen in the shop and several plainclothesmen, some armed with formidable looking sawed-off shot guns. Directly in front of me was a sign, tacked up on a pillar, which read, "This store will be closed at noon today. Martin & Co." All the customers were gone. In fact the clerks had had some trouble in clearing the shop, as many of them expressed not only surprise but exasperation at the proceeding. Nevertheless the clerks had politely but insistently ushered them out. Martin himself was evidently very nervous and very much alarmed. Indeed no one could blame him for that. Merely to have been singled out by this amazing master criminal was enough to cause panic. Already he had engaged detectives, prepared for whatever might happen, and they had advised him to leave the diamonds in the counter, clear the store, and let the crooks try anything, if they dared. I fancied that he was somewhat exasperated at his daughter's presence, too, but could see that her explanation of Elaine's and Perry Bennett's interest in the Clutching Hand had considerably mollified him. He had been talking with Bennett as we came in and evidently had a high respect for the young lawyer. Just back of us, and around the corner, as we came in, we had noticed a limousine which had driven up. Three faultlessly attired dandies had entered a doorway down the street, as we learned afterwards, apparently going to a fashionable tailor's which occupied the second floor of the old-fashioned building, the first floor having been renovated and made ready for renting. Had we been there a moment sooner we might have seen, I suppose, that one of them nodded to a taxicab driver who was standing at a public hack stand a few feet up the block. The driver nodded unostentatiously back to the men. In spite of the excitement, Kennedy quietly examined the show case, which was, indeed, a veritable treasure store of brilliants. Then with a keen scrutinizing glance he looked over the police and detectives gathered around. There was nothing to do now but wait, as the detectives had advised. I looked at a large antique grandfather's clock which was standing nearby. It now lacked scarcely a minute of twelve. Slowly the hands of the clock came nearer together at noon. We all gathered about the show case with its glittering hoard of wealth, forming a circle at a respectful distance. Martin pointed nervously at the clock. In deep-lunged tones the clock played the chords written, I believe, by Handel. Then it began striking. As it did so, Martin involuntarily counted off the strokes, while one of the plainclothesmen waved his shotgun in unison. Martin finished counting. Nothing had happened. We all breathed a sigh of relief. "Well, it is still there!" exclaimed Martin, pointing at the show-case, with a forced laugh. Suddenly came a rending and crashing sound. It seemed as if the very floor on which we stood was giving way. The show-case, with all its priceless contents, went smashing down into the cellar below. The flooring beneath the case had been cut through! All crowded forward, gazing at the black yawning cavern. A moment we hesitated, then gingerly craned our necks over the edge. Down below, three men, covered with linen dusters and their faces hidden by masks, had knocked the props away from the ceiling of the cellar, which they had sawed almost through at their leisure, and the show case had landed eight or ten feet below, shivered into a thousand bits. A volley of shots whizzed past us, and another. While one crook was hastily stuffing the untold wealth of jewels into a burlap bag, the others had drawn revolvers and were firing up through the hole in the floor, desperately. Martin, his detectives, and the rest of us fell back from the edge of the chasm hastily, to keep out of range of the hail of bullets. "Look out!" cried someone behind us, before we could recover from our first surprise and return the fire. One of the desperadoes had taken a bomb from under his duster, lighted it, and thrown it up through the hole in the floor. It sailed up over our heads and landed near our little group on the floor, the fuse sputtering ominously. Quickly we divided and backed away even further. I heard an exclamation of fear from Elaine. Kennedy had pushed his way past us and picked up the deadly infernal machine in his bare hands. I watched him, fascinated. As near as he dared, he approached the hole in the floor, still holding the thing off at arm's length. Would he never throw it? He was coolly holding it, allowing the fuse to burn down closer to the explosion point. It was now within less than an inch sure death. Suddenly he raised it and hurled the deadly thing down through the hole. We could hear the imprecations of the crooks as it struck the cellar floor, near them. They had evidently been still cramming jewelry into the capacious maw of the bag. One of them, discovering the bomb, must have advanced toward it, then retreated when he saw how imminent was the explosion. "Leave the store--quick!" rang out Kennedy's voice. We backed away as fast as those behind us would permit. Kennedy and Bennett were the last to leave, in fact paused at the door. Down below the crooks were beating a hasty retreat through a secret entrance which they had effected. "The bag! The bag!" we could hear one of them bellow. "The bomb--run!" cried another voice gruffly. A second later came an ominous silence. The last of the three must have fled. The explosion that followed lifted us fairly off our feet. A great puff of smoke came belching up through the hole, followed by the crashing of hundreds of dollars' worth of glass ware in the jewelry shop as fragments of stone, brick and mortar and huge splinters of wood were flung with tremendous force in every direction from the miniature volcano. As the smoke from the explosion cleared away, Kennedy could be seen, the first to run forward. Meanwhile Martin's detectives had rushed down a flight of back stairs that led into a coal cellar. With coal shovels and bars, anything they could lay hands on, they attacked the door that opened forward from the coal cellar into the front basement where the robbers had been. A moment Kennedy and Bennett paused on the brink of the abyss which the bomb had made, waiting for the smoke to decrease. Then they began to climb down cautiously over the piled up wreckage. The explosion had set the basement afire, but the fire had not gained much headway, by the time they reached the basement. Quickly Kennedy ran to the door into the coal cellar and opened it. From the other side, Martin, followed by the police and the detectives, burst in. "Fire!" cried one of the policemen, leaping back to turn in an alarm from the special apparatus upstairs. All except Martin began beating out the flames, using such weapons as they already held in their hands to batter down the door. To Martin there was one thing paramount--the jewels. In the midst of the confusion, Elaine, closely followed by her friend Susie, made her way fearlessly into the stifle of smoke down the stairs. "There are your jewels, Mr. Martin," cried Kennedy, kicking the precious burlap bag with his foot as if it had been so much ordinary merchandise, and turning toward what was in his mind the most important thing at stake--the direction taken by the agents of the Clutching Hand. "Thank heaven!" ejaculated Martin, fairly pouncing on the bag and tearing it open. "They didn't get away with them--after all!" he exclaimed, examining the contents with satisfaction. "See--you must have frightened them off at just the right moment when you sent the bomb back at them." Elaine and Susie pressed forward eagerly as he poured forth the sparkling stream of gems, intact. "Wasn't he just simply wonderful!" I heard Susie whisper to Elaine. Elaine did not answer. She had eyes or ears for nothing now in the melee but Kennedy. . . . . . . . . Events were moving rapidly. The limousine had been standing innocently enough at the curb near the corner, with the taxicab close behind it. Less than ten minutes after they had entered, three well-dressed men came out of the vacant shop, apparently from the tailor's above, and climbed leisurely into their car. As the last one entered, he half turned to the taxicab driver, hiding from passers-by the sign of the Clutching Hand which the taxicab driver returned, in the same manner. Then the big car whirled up the avenue. All this we learned later from a street sweeper who was at work nearby. Down below, while the police and detectives were putting out the fire, Kennedy was examining the wall of the cellar, looking for the spot where the crooks had escaped. "A secret door!" he exclaimed, as he paused after tapping along the wall to determine its character. "You can see how the force of the explosion has loosened it." Sure enough, when he pointed it out to us, it was plainly visible. One of the detectives picked up a crowbar and others, still with the hastily selected implements they had seized to fight the fire, started in to pry it open. As it yielded, Kennedy pushed his way through. Elaine, always utterly fearless, followed. Then the rest of us went through. There seemed to be nothing, however, that would help us in the cellar next door, and Kennedy mounted the steps of a stairway in the rear. The stairway led to a sort of storeroom, full of barrels and boxes, but otherwise characterless. When I arrived Kennedy was gingerly holding up the dusters which the crooks had worn. "We're on the right trail," commented Elaine as he showed them to her, "but where do you suppose the owners are?" Craig shrugged his shoulders and gave a quick look about. "Evidently they came in from and went away by the street," he observed, hurrying to the door, followed by Elaine. On the sidewalk, he gazed up the avenue, then catching sight of the street cleaner, called to him. "Yes, sir," replied the man, stolidly looking up from his work. "I see three gentlemen come out and get into an automobile." "Which way did they go?" asked Kennedy. For answer the man jerked his thumb over his shoulder in the general direction uptown. "Did you notice the number of the car?" asked Craig eagerly. The man shrugged his shoulders blankly. With keen glance, Kennedy strained his eyes. Far up the avenue, he could descry the car threading its way in and out among the others, just about disappearing. A moment later Craig caught sight of the vacant taxicab and crooked his finger at the driver, who answered promptly by cranking his engine. "You saw that limousine standing there?" asked Craig. "Yes," nodded the chauffeur with a show of alertness. "Well, follow it," ordered Kennedy, jumping into the cab. "Yes, sir." Craig was just about to close the door when a slight figure flashed past us and a dainty foot was placed on the step. "Please, Mr. Kennedy," pleaded Elaine, "let me go. They may lead to my father's slayer." She said it so earnestly that Craig could scarcely have resisted if he had wanted to do so. Just as Elaine and Kennedy were moving off, I came out of the vacant store, with Bennett and the detectives. "Craig!" I called. "Where are you going?" Kennedy stuck his head out of the window and I am quite sure that he was not altogether displeased that I was not with him. "Chasing that limousine," he shouted back. "Follow us in another car." A moment later he and Elaine were gone. Bennett and I looked about. "There are a couple of cabs--down there," I pointed out at the other end of the block. "I'll take one you take the other." Followed by a couple of the detectives, I jumped into the first one I came to, excitedly telling the driver to follow Kennedy's taxi, directing him with my head out of the window. "Mr. Jameson, please--can't I go with you?" I turned. It was Susie Martin. "One of you fellows, go in the other car," I asked the detectives. Before the man could move, Mr. Martin himself appeared. "No, Susan, I--I won't allow it," he ordered. "But Elaine went," she pouted. "Well, Elaine is--ah--I won't have it," stormed Martin. There was no time to waste. With a hasty apology, I drove off. Who, besides Bennett, went in the other car, I don't know, but it made no difference, for we soon lost them. Our driver, however, was a really clever fellow. Far ahead now we could see the limousine drive around a corner, making a dangerous swerve. Kennedy's cab followed, skidding dangerously near a pole. But the taxicab was no match for the powerful limousine. On uptown they went, the only thing preventing the limousine from escaping being the fear of pursuit by traffic police if the driver let out speed. They were content to manage to keep just far enough ahead to be out of danger of having Kennedy overhaul them. As for us, we followed as best we could, on uptown, past the city line, and out into the country. There Kennedy lost sight altogether of the car he was trailing. Worse than that, we lost sight of Kennedy. Still we kept on blindly, trusting to luck and common sense in picking the road. I was peering ahead over the driver's shoulder, the window down, trying to direct him, when we approached a fork in the road. Here was a dilemma which must be decided at once rightly or wrongly. As we neared the crossroad, I gave an involuntary exclamation. Beside the road, almost on it, lay the figure of a man. Our driver pulled up with a jerk and I was out of the car in an instant. There lay Kennedy! Someone had blackjacked him. He was groaning and just beginning to show signs of consciousness as I bent over. "What's the matter, old man?" I asked, helping him to his feet. He looked about dazed a moment, then seeing me and comprehending, he pointed excitedly, but vaguely. "Elaine!" he cried. "They've kidnapped Elaine!" What had really happened, as we learned later from Elaine and others, was that when the cross roads was reached, the three crooks in the limousine had stopped long enough to speak to an accomplice stationed there, according to their plan for a getaway. He was a tough looking individual who might have been hoboing it to the city. When, a few minutes later, Kennedy and Elaine had approached the fork, their driver had slowed up, as if in doubt which way to go. Craig had stuck his head out of the window, as I had done, and, seeing the crossroads, had told the chauffeur to stop. There stood the hobo. "Did a car pass here, just now--a big car?" called Craig. The man put his hand to his ear, as if only half comprehending. "Which way did the big car go?" repeated Kennedy. The hobo approached the taxicab sullenly, as if he had a grudge against cars in general. One question after another elicited little that could be construed as intelligence. If Craig had only been able to see, he would have found out that, with his back toward the taxicab driver, the hobo held one hand behind him and made the sign of the Clutching Hand, glancing surreptitiously at the driver to catch the answering sign, while Craig gazed earnestly up the two roads. At last Craig gave him up as hopeless. "Well--go ahead--that way," he indicated, picking the most likely road. As the chauffeur was about to start, he stalled his engine. "Hurry!" urged Craig, exasperated at the delays. The driver got out and tried to crank the engine. Again and again he turned it over, but, somehow, it refused to start. Then he lifted the hood and began to tinker. "What's the matter?" asked Craig, impatiently jumping out and bending over the engine, too. The driver shrugged his shoulders. "Must be something wrong with the ignition, I guess," he replied. Kennedy looked the car over hastily. "I can't see anything wrong," he frowned. "Well, there is," growled the driver. Precious minutes were speeding away, as they argued. Finally with his characteristic energy, Kennedy put the taxicab driver aside. "Let me try it," he said. "Miss Dodge, will you arrange that spark and throttle?" Elaine, equal to anything, did so, and Craig bent down and cranked the engine. It started on the first spin. "See!" he exclaimed. "There wasn't anything, after all." He took a step toward the taxicab. "Say," objected the driver, nastily, interposing himself between Craig and the wheel which he seemed disposed to take now, "who's running this boat, anyhow?" Surprised, Kennedy tried to shoulder the fellow out of the way. The driver resisted sullenly. "Mr. Kennedy--look out!" cried Elaine. Craig turned. But it was too late. The rough looking fellow had wakened to life. Suddenly he stepped up behind Kennedy with a blackjack. As the heavy weight descended, Craig crumpled up on the ground, unconscious. With a scream, Elaine turned and started to run. But the chauffeur seized her arm. "Say, bo," he asked of the rough fellow, "what does Clutching Hand want with her? Quick! There's another cab likely to be along in a moment with that fellow Jameson in it." The rough fellow, with an oath, seized her and dragged her into the taxicab. "Go ahead!" he growled, indicating the road. And away they sped, leaving Kennedy unconscious on the side of the road where we found him. . . . . . . . . "What are we to do?" I asked helplessly of Kennedy, when we had at last got him on his feet. His head still ringing from the force of the blow of the blackjack, Craig stooped down, then knelt in the dust of the road, then ran ahead a bit where it was somewhat muddy. "Which way--which way?" he muttered to himself. I thought perhaps the blow had affected him and leaned over to see what he was doing. Instead, he was studying the marks made by the tire of the Clutching Hand cab. Very decidedly, there in the road, the little anti-skid marks on the tread of the tire showed--some worn, some cut--but with each revolution the same marks reappearing unmistakably. More than that, it was an unusual make of tire. Craig was actually studying the finger prints, so to speak, of an automobile! More slowly now and carefully, we proceeded, for a mistake meant losing the trail of Elaine. Kennedy absolutely refused to get inside our cab, but clung tightly to a metal rod outside while he stood on the running board--now straining his eyes along the road to catch any faint glimpse of either taxi or limousine, or the dust from them, now gazing intently at the ground following the finger prints of the taxicab that was carrying off Elaine. All pain was forgotten by him now in the intensity of his anxiety for her. We came to another crossroads and the driver glanced at Craig. "Stop!" he ordered. In another instant he was down in the dirt, examining the road for marks. "That way!" he indicated, leaping back to the running board. We piled back into the car and proceeded under Kennedy's direction, as fast as he would permit. So it continued, perhaps for a couple of hours. At last Kennedy stopped the cab and slowly directed the driver to veer into an open space that looked peculiarly lonesome. Near it stood a one story brick factory building, closed, but not abandoned. As I looked about at the unattractive scene, Kennedy already was down on his knees in the dirt again, studying the tire tracks. They were all confused, showing that the taxicab we were following had evidently backed in and turned several times before going on. "Crossed by another set of tire tracks!" he exclaimed excitedly, studying closer. "That must have been the limousine, waiting." Laboriously he was following the course of the cars in the open space, when the one word escaped him, "Footprints!" He was up and off in a moment, before we could imagine what he was after. We had got out of the cab, and followed him as, down to the very shore of a sort of cove or bay, he went. There lay a rusty, discarded boiler on the beach, half submerged in the rising tide. At this tank the footprints seemed to go right down the sand and into the waves which were slowly obliterating them. Kennedy gazed out as if to make out a possible boat on the horizon, where the cove widened out. "Look!" he cried. Farther down the shore, a few feet, I had discovered the same prints, going in the opposite direction, back toward the place from which we had just come. I started to follow them, but soon found myself alone. Kennedy had paused beside the old boiler. "What is it?" I asked, retracing my steps. He did not answer, but seemed to be listening. We listened also. There certainly was a most peculiar noise inside that tank. Was it a muffled scream? Kennedy reached down and picked up a rock, hitting the tank a resounding blow. As the echo died down, he listened again. Yes, there was a sound--a scream perhaps--a woman's voice, faint, but unmistakable. I looked at his face inquiringly. Without a word I read in it the confirmation of the thought that had flashed into my mind. Elaine Dodge was inside! . . . . . . . . First had come the limousine, with its three bandits, to the spot fixed on as a rendezvous. Later had come the taxicab. As it hove into sight, the three well-dressed crooks had drawn revolvers, thinking perhaps the plan for getting rid of Kennedy might possibly have miscarried. But the taxicab driver and the rough-faced fellow had reassured them with the sign of the Clutching Hand, and the revolvers were lowered. As they parleyed hastily, the rough-neck and the fake chauffeur lifted Elaine out of the taxi. She was bound and gagged. "Well, now we've got her, what shall we do with her?" asked one. "It's got to be quick. There's another cab," put in the driver. "The deuce with that." "The deuce with nothing," he returned. "That fellow Kennedy's a clever one. He may come to. If he does, he won't miss us. Quick, now!" "I wish I'd broken his skull," muttered the roughneck. "We'd better leave her somewhere here," remarked one of the better-dressed three. "I don't think the chief wants us to kill her--yet," he added, with an ominous glance at Elaine, who in spite of threats was not cowed, but was vainly struggling at her bonds. "Well, where shall it be?" asked another. They looked about. "See," cried the third. "See that old boiler down there at the edge of the water? Why not put her in there? No one'll ever think to look in such a place." Down by the water's edge, where he pointed, lay a big boiler such as is used on stationary engines, with its end lapped by the waves. With a hasty expression of approval, the rough-neck picked Elaine up bodily, still struggling vainly, and together they carried her, bound and gagged, to the tank. The opening, which was toward the water, was small, but they managed, roughly, to thrust her in. A moment later and they had rolled up a huge boulder against the small entrance, bracing it so that it would be impossible for her to get out from the inside. Then they drove off hastily. Inside the old boiler lay Elaine, still bound and gagged. If she could only scream! Someone might hear. She must get help. There was water in the tank. She managed to lean up inside it, standing as high as the walls would allow her, trying to keep her head above the water. Frantically, she managed to loosen the gag. She screamed. Her voice seemed to be bound around by the iron walls as was she herself. She shuddered, The water was rising--had reached her chest, and was still rising, slowly, inexorably. What should she do? Would no one hear her? The water was up to her neck now. She held her head as high as she could and screamed again. What was that? Silence? Or was someone outside? . . . . . . . . Coolly, in spite of the emergency, Kennedy took in the perilous situation. The lower end of the boiler, which was on a slant on the rapidly shelving beach, was now completely under water and impossible to get at. Besides, the opening was small, too small. We pulled away the stone, but that did no good. No one could hope to get in and then out again that way alive--much less with a helpless girl. Yet something must be done. The tank was practically submerged inside, as I estimated quickly. Blows had no effect on the huge iron trap which had been built to resist many pounds of pressure. Kennedy gazed about frantically and his eye caught the sign on the factory: OXYACETYLENE WELDING CO. "Come, Walter," he cried, running up the shore. A moment later, breathless, we reached the doorway. It was, of course, locked. Kennedy whipped out his revolver and several well-directed shots through the keyhole smashed the lock. We put our shoulders to it and swung the door open, entering the factory. There was not a soul about, not even a watchman. Hastily we took in the place, a forge and a number of odds and ends of metal sheets, rods, pipes and angles. Beside a workbench stood two long cylinders, studded with bolts. "That's what I'm looking for," exclaimed Craig. "Here, Walter, take one. I'll take the other--and the tubes--and--" He did not pause to finish, but seized up a peculiar shaped instrument, like a huge hook, with a curved neck and sharp beak. Really it was composed of two metal tubes which ran into a cylinder or mixing chamber above the nozzle, while parallel to them ran another tube with a nozzle of its own. We ran, for there was no time to lose. As nearly as I could estimate it, the water must now be slowly closing over Elaine. "What is it?" I asked as he joined up the tubes from the tanks to the peculiar hook-like apparatus he carried. "An oxyacetylene blowpipe," he muttered back feverishly working. "Used for welding and cutting, too," he added. With a light he touched the nozzle. Instantly a hissing, blinding flame-needle made the steel under it incandescent. The terrific heat from one nozzle made the steel glow. The stream of oxygen from the second completely consumed the hot metal. And the force of the blast carried a fine spray of disintegrated metal before it. It was a brilliant sight. But it was more than that. Through the very steel itself, the flame, thousands of degrees hot, seemed to eat its way in a fine line, as if it were a sharp knife cutting through ordinary cardboard. With tense muscles Kennedy skillfully guided the terrible instrument that ate cold steel, wielding the torch as deftly as if it had been, as indeed it was, a magic wand of modern science. He was actually cutting out a huge hole in the still exposed surface of the tank--all around, except for a few inches, to prevent the heavy piece from falling inward. As Kennedy carefully bent outward the section of the tank which he had cut, he quickly reached down and lifted Elaine, unconscious, out of the water. Gently he laid her on the sand. It was the work of only a moment to cut the cords that bound her hands. There she lay, pale and still. Was she dead? Kennedy worked frantically to revive her. At last, slowly, the color seemed to return to her pale lips. Her eyelids fluttered. Then her great, deep eyes opened. As she looked up and caught sight of Craig bending anxiously over her, she seemed to comprehend. For a moment both were silent. Then Elaine reached up and took his hand. There was much in the look she gave him--admiration, confidence,--love itself. Heroics, however, were never part of Kennedy's frank make-up. The fact was that her admiration, even though not spoken, plainly embarrassed him. Yet he forgot that as he looked at her lying there, frail and helpless. He stroked her forehead gently, laying back the wet ringlets of her hair. "Craig," she murmured, "you--you've saved my life!" Her tone was eloquent. "Elaine," he whispered, still gazing into her wonderful eyes, "the Clutching Hand shall pay for this! It is a fight to the finish between us!" CHAPTER IV "THE FROZEN SAFE" Kennedy swung open the door of our taxicab as we pulled up, safe at last, before the Dodge mansion, after the rescue of Elaine from the brutal machinations of the Clutching Hand. Bennett was on the step of the cab in a moment and, together, one on each side of Elaine, they assisted her out of the car and up the steps to the house. As they mounted the steps, Kennedy called back to me, "Pay the driver, Walter, please." It was the first time I had thought of that. As it happened, I had quite a bankroll with me and, in my hurry, I peeled off a ten dollar bill and tossed it to the fellow, intending to be generous and tell him to keep the change. "Say," he exclaimed, pointing to the clock, "come across--twenty-three, sixty." Protesting, I peeled off some more bills. Having satisfied this veritable anaconda and gorged his dilating appetite for banknotes, I turned to follow the others. Jennings had opened the door immediately. Whether it was that he retained a grudge against me or whether he did not see me, he would have closed it before I could get up there. I called and took the steps two at a time. Elaine's Aunt Josephine was waiting for us in the drawing room, very much worried. The dear old lady was quite scandalized as Elaine excitedly told of the thrilling events that had just taken place. "And to think they--actually--carried you!" she exclaimed, horrified, adding, "And I not--" "But Mr. Kennedy came along and saved me just in time," interrupted Elaine with a smile. "I was well chaperoned!" Aunt Josephine turned to Craig gratefully. "How can I ever thank you enough, Mr. Kennedy," she said fervently. Kennedy was quite embarrassed. With a smile, Elaine perceived his discomfiture, not at all displeased by it. "Come into the library," she cried gaily, taking his arm. "I've something to show you." Where the old safe which had been burnt through had stood was now a brand new safe of the very latest construction and design--one of those that look and are so formidable. "Here is the new safe," she pointed out brightly. "It is not only proof against explosives, but between the plates is a lining that is proof against thermit and even that oxy-acetylene blowpipe by which you rescued me from the old boiler. It has a time lock, too, that will prevent its being opened at night, even if anyone should learn the combination." They stood before the safe a moment and Kennedy examined it closely with much interest. "Wonderful!" he admired. "I knew you'd approve of it," cried Elaine, much pleased. "Now I have something else to show you." She paused at the desk and from a drawer took out a portfolio of large photographs. They were very handsome photographs of herself. "Much more wonderful than the safe," remarked Craig earnestly. Then, hesitating and a trifle embarrassed, he added, "May I--may I have one?" "If you care for it," she said, dropping her eyes, then glancing up at him quickly. "Care for it?" he repeated. "It will be one of the greatest treasures." She slipped the picture quickly into an envelope. "Come," she interrupted. "Aunt Josephine will be wondering where we are. She--she's a demon chaperone." Bennett, Aunt Josephine and myself were talking earnestly as Elaine and Craig returned. "Well," said Bennett, glancing at his watch and rising as he turned to Elaine, "I'm afraid I must go, now." He crossed over to where she stood and shook hands. There was no doubt that Bennett was very much smitten by his fair client. "Good-bye, Mr. Bennett," she murmured, "and thank you so much for what you have done for me today." But there was something lifeless about the words. She turned quickly to Craig, who had remained standing. "Must you go, too, Mr. Kennedy?" she asked, noticing his position. "I'm afraid Mr. Jameson and I must be back on the job before this Clutching Hand gets busy again," he replied reluctantly. "Oh, I hope you--we get him soon!" she exclaimed, and there was nothing lifeless about the way she gave Craig her hand, as Bennett, he and I left a moment later. . . . . . . . . That morning I had noticed Kennedy fussing some time at the door of our apartment before we went over to the laboratory. As nearly as I could make out he had placed something under the rug at the door out into the hallway. When we approached our door, now, Craig paused. By pressing a little concealed button he caused a panel in the wall outside to loosen, disclosing a small, boxlike plate in the wall underneath. It was about a foot long and perhaps four inches wide. Through it ran a piece of paper which unrolled from one coil and wound up on another, actuated by clockwork. Across the blank white paper ran an ink line traced by a stylographic pen, such as I had seen in mechanical pencils used in offices, hotels, banks and such places. Kennedy examined the thing with interest. "What is it?" I asked. "A new seismograph," he replied, still gazing carefully at the rolled up part of the paper. "I have installed it because it registers every footstep on the floor of our apartment. We can't be too careful with this Clutching Hand. I want to know whether we have any visitors or not in our absence. This straight line indicates that we have not. Wait a moment." Craig hastily unlocked the door and entered. Inside, I could see him pacing up and down our modest quarters. "Do you see anything, Walter?" he called. I looked at the seismograph. The pen had started to trace its line, no longer even and straight, but zigzag, at different heights across the paper. He came to the door. "What do you think of it?" he inquired. "Splendid idea," I answered enthusiastically. Our apartment was, as I have said, modest, consisting of a large living room, two bedrooms, and bath--an attractive but not ornate place, which we found very cosy and comfortable. On one side of the room was a big fire place, before which stood a fire screen. We had collected easy chairs and capacious tables and desks. Books were scattered about, literally overflowing from the crowded shelves. On the walls were our favorite pictures, while for ornament, I suppose I might mention my typewriter and now and then some of Craig's wonderful scientific apparatus as satisfying our limited desire for the purely aesthetic. We entered and fell to work at the aforementioned typewriter, on a special Sunday story that I had been forced to neglect. I was not so busy, however, that I did not notice out of the corner of my eye that Kennedy had taken from its cover Elaine Dodge's picture and was gazing at it ravenously. I put my hand surreptitiously over my mouth and coughed. Kennedy wheeled on me and I hastily banged a sentence out on the machine, making at least half a dozen mistakes. I had finished as much of the article as I could do then and was smoking and reading it over. Kennedy was still gazing at the picture Miss Dodge had given him, then moving from place to place about the room, evidently wondering where it would look best. I doubt whether he had done another blessed thing since we returned. He tried it on the mantel. That wouldn't do. At last he held it up beside a picture of Galton, I think, of finger print and eugenics fame, who hung on the wall directly opposite the fireplace. Hastily he compared the two. Elaine's picture was of precisely the same size. Next he tore out the picture of the scientist and threw it carelessly into the fireplace. Then he placed Elaine's picture in its place and hung it up again, standing off to admire it. I watched him gleefully. Was this Craig? Purposely I moved my elbow suddenly and pushed a book with a bang on the floor. Kennedy actually jumped. I picked up the book with a muttered apology. No, this was not the same old Craig. Perhaps half an hour later, I was still reading. Kennedy was now pacing up and down the room, apparently unable to concentrate his mind on any but one subject. He stopped a moment before the photograph, looked at it fixedly. Then he started his methodical walk again, hesitated, and went over to the telephone, calling a number which I recognized. "She must have been pretty well done up by her experience," he said apologetically, catching my eye. "I was wondering if--Hello--oh, Miss Dodge--I--er--I--er--just called up to see if you were all right." Craig was very much embarrassed, but also very much in earnest. A musical laugh rippled over the telephone. "Yes, I'm all right, thank you, Mr. Kennedy--and I put the package you sent me into the safe, but--" "Package?" frowned Craig. "Why, I sent you no package, Miss Dodge. In the safe?" "Why, yes, and the safe is all covered with moisture--and so cold." "Moisture--cold?" he repeated quickly. "Yes, I have been wondering if it is all right. In fact, I was going to call you up, only I was afraid you'd think I was foolish." "I shall be right over," he answered hastily, clapping the receiver back on its hook. "Walter," he added, seizing his hat and coat, "come on--hurry!" A few minutes later we drove up in a taxi before the Dodge house and rang the bell. Jennings admitted us sleepily. . . . . . . . . It could not have been long after we left Miss Dodge late in the afternoon that Susie Martin, who had been quite worried over our long absence after the attempt to rob her father, dropped in on Elaine. Wide-eyed, she had listened to Elaine's story of what had happened. "And you think this Clutching Hand has never recovered the incriminating papers that caused him to murder your father?" asked Susie. Elaine shook her head. "No. Let me show you the new safe I've bought. Mr. Kennedy thinks it wonderful." "I should think you'd be proud of it," admired Susie. "I must tell father to get one, too." At that very moment, if they had known it, the Clutching Hand with his sinister, masked face, was peering at the two girls from the other side of the portieres. Susie rose to go and Elaine followed her to the door. No sooner had she gone than the Clutching Hand came out from behind the curtains. He gazed about a moment, then moving over to the safe about which the two girls had been talking, stealthily examined it. He must have heard someone coming, for, with a gesture of hate at the safe itself, as though he personified it, he slipped back of the curtains again. Elaine had returned and as she sat down at the desk to go over some papers which Bennett had left relative to settling up the estate, the masked intruder stealthily and silently withdrew. "A package for you, Miss Dodge," announced Michael later in the evening as Elaine, in her dainty evening gown, was still engaged in going over the papers. He carried it in his hands rather gingerly. "Mr. Kennedy sent it, ma'am. He says it contains clues and will you please put it in the new safe for him." Elaine took the package eagerly and examined it. Then she pulled open the heavy door of the safe. "It must be getting cold out, Michael," she remarked. "This package is as cold as ice." "It is, ma'am," answered Michael, deferentially with a sidelong glance that did not prevent his watching her intently. She closed the safe and, with a glance at her watch, set the time lock and went upstairs to her room. No sooner had Elaine disappeared than Michael appeared again, cat-like, through the curtains from the drawing room, and, after a glance about the dimly lighted library, discovering that the coast was clear, motioned to a figure hiding behind the portieres. A moment, and Clutching Hand himself came out. He moved over to the safe and looked it over. Then he put out his hand and touched it. "Good, Michael," he exclaimed with satisfaction. "Listen!" cautioned Michael. Someone was coming and they hastily slunk behind the protecting portieres. It was Marie, Elaine's maid. She turned up the lights and went over to the desk for a book for which Elaine had evidently sent her. She paused and appeared to be listening. Then she went to the door. "Jennings!" she beckoned. "What is it, Marie?" he replied. She said nothing, but as he came up the hall led him to the center of the room. "Listen! I heard sighs and groans!" Jennings looked at her a moment, puzzled, then laughed. "You girls!" he exclaimed. "I suppose you'll always think the library haunted, now." "But, Jennings, listen," she persisted. Jennings did listen. Sure enough, there were sounds, weird, uncanny. He gazed about the room. It was eerie. Then he took a few steps toward the safe. Marie put out her hand to it, and started back. "Why, that safe is all covered with cold sweat!" she cried with bated breath. Sure enough the face of the safe was beaded with dampness. Jennings put his hand on it and quickly drew it away, leaving a mark on the dampness. "Wh-what do you think of that?" he gasped. "I'm going to tell Miss Dodge," cried Marie, genuinely frightened. A moment later she burst into Elaine's room. "What is the matter, Marie?" asked Elaine, laying down her book. "You look as if you had seen a ghost." "Ah, but, mademoiselle--it ees just like that. The safe--if mademoiselle will come downstairs, I will show it you." Puzzled but interested, Elaine followed her. In the library Jennings pointed mutely at the new safe. Elaine approached it. As they stood about new beads of perspiration, as it were, formed on it. Elaine touched it, and also quickly withdrew her hand. "I can't imagine what's the matter," she said. "But--well--Jennings, you may go--and Marie, also." When the servants had gone she still regarded the safe with the same wondering look, then turning out the light, she followed. She had scarcely disappeared when, from the portiered doorway nearby, the Clutching Hand appeared, and, after gazing out at them, took a quick look at the safe. "Good!" he muttered. Noiselessly Michael of the sinister face moved in and took a position in the center of the room, as if on guard, while Clutching Hand sat before the safe watching it intently. "Someone at the door--Jennings is answering the bell," Michael whispered hoarsely. "Confound it!" muttered Clutching Hand, as both moved again behind the heavy velour curtains. . . . . . . . . "I'm so glad to see you, Mr. Kennedy," greeted Elaine unaffectedly as Jennings admitted us. She had heard the bell and was coming downstairs as we entered. We three moved toward the library and someone switched on the lights. Craig strode over to the safe. The cold sweat on it had now turned to icicles. Craig's face clouded with thought as he examined it more closely. There was actually a groaning sound from within. "It can't be opened," he said to himself. "The time lock is set for tomorrow morning." Outside, if we had not been so absorbed in the present mystery, we might have seen Michael and the Clutching Hand listening to us. Clutching Hand looked hastily at his watch. "The deuce!" he muttered under his breath, stifling his suppressed fury. We stood looking at the safe. Kennedy was deeply interested, Elaine standing close beside him. Suddenly he seemed to make up his mind. "Quick--Elaine!" he cried, taking her arm. "Stand back!" We all retreated. The safe door, powerful as it was, had actually begun to warp and bend. The plates were bulging. A moment later, with a loud report and concussion the door blew off. A blast of cold air and flakes like snow flew out. Papers were scattered on every side. We stood gazing, aghast, a second, then ran forward. Kennedy quickly examined the safe. He bent down and from the wreck took up a package, now covered with white. As quickly he dropped it. "That is the package that was sent," cried Elaine. Taking it in a table cover, he laid it on the table and opened it. Inside was a peculiar shaped flask, open at the top, but like a vacuum bottle. "A Dewar flask!" ejaculated Craig. "What is it?" asked Elaine, appealing to him. "Liquid air!" he answered. "As it evaporated, the terrific pressure of expanding air in the safe increased until it blew out the door. That is what caused the cold sweating and the groans." We watched him, startled. On the other side of the portieres Michael and Clutching Hand waited. Then, in the general confusion, Clutching Hand slowly disappeared, foiled. "Where did this package come from?" asked Kennedy of Jennings suspiciously. Jennings looked blank. "Why," put in Elaine, "Michael brought it to me." "Get Michael," ordered Kennedy. "Yes, sir," nodded Jennings. A moment later he returned. "I found him, going upstairs," reported Jennings, leading Michael in. "Where did you get this package?" shot out Kennedy. "It was left at the door, sir, by a boy, sir." Question after question could not shake that simple, stolid sentence. Kennedy frowned. "You may go," he said finally, as if reserving something for Michael later. A sudden exclamation followed from Elaine as Michael passed down the hall again. She had moved over to the desk, during the questioning, and was leaning against it. Inadvertently she had touched an envelope. It was addressed, "Craig Kennedy." Craig tore it open, Elaine bending anxiously over his shoulder, frightened. We read: "YOU HAVE INTERFERED FOR THE LAST TIME. IT IS THE END." Beneath it stood the fearsome sign of the Clutching Hand! . . . . . . . . The warning of the Clutching Hand had no other effect on Kennedy than the redoubling of his precautions for safety. Nothing further happened that night, however, and the next morning found us early at the laboratory. It was the late forenoon, when after a hurried trip down to the office, I rejoined Kennedy at his scientific workshop. We walked down the street when a big limousine shot past. Kennedy stopped in the middle of a remark. He had recognized the car, with a sort of instinct. At the same moment I saw a smiling face at the window of the car. It was Elaine Dodge. The car stopped in something less than twice its length and then backed toward us. Kennedy, hat off, was at the window in a moment. There were Aunt Josephine, and Susie Martin, also. "Where are you boys going?" asked Elaine, with interest, then added with a gaiety that ill concealed her real anxiety, "I'm so glad to see you--to see that--er--nothing has happened from that dreadful Clutching Hand." "Why, we were just going up to our rooms," replied Kennedy. "Can't we drive you around?" We climbed in and a moment later were off. The ride was only too short for Kennedy. We stepped out in front of our apartment and stood chatting for a moment. "Some day I want to show you the laboratory," Craig was saying. "It must be so--interesting!" exclaimed Elaine enthusiastically. "Think of all the bad men you must have caught!" "I have quite a collection of stuff here at our rooms," remarked Craig, "almost a museum. Still," he ventured, "I can't promise that the place is in order," he laughed. Elaine hesitated. "Would you like to see it?" she wheedled of Aunt Josephine. Aunt Josephine nodded acquiescence, and a moment later we all entered the building. "You--you are very careful since that last warning?" asked Elaine as we approached our door. "More than ever--now," replied Craig. "I have made up my mind to win." She seemed to catch at the words as though they had a hidden meaning, looking first at him and then away, not displeased. Kennedy had started to unlock the door, when he stopped short. "See," he said, "this is a precaution I have just installed. I almost forgot in the excitement." He pressed a panel and disclosed the box-like apparatus. "This is my seismograph which tells me whether I have had any visitors in my absence. If the pen traces a straight line, it is, all right; but if--hello--Walter, the line is wavy." We exchanged a significant glance. "Would you mind--er--standing down the hall just a bit while I enter?" asked Craig. "Be careful," cautioned Elaine. He unlocked the door, standing off to one side. Then he extended his hand across the doorway. Still nothing happened. There was not a sound. He looked cautiously into the room. Apparently there was nothing. . . . . . . . . It had been about the middle of the morning that an express wagon had pulled up sharply before our apartment. "Mr. Kennedy live here?" asked one of the expressmen, descending with his helper and approaching our janitor, Jens Jensen, a typical Swede, who was coming up out of the basement. Jens growled a surly, "Yes--but Mr. Kannady, he bane out." "Too bad--we've got this large cabinet he ordered from Grand Rapids. We can't cart it around all day. Can't you let us in so we can leave it?" Jensen muttered. "Wall--I guess it bane all right." They took the cabinet off the wagon and carried it upstairs. Jensen opened our door, still grumbling, and they placed the heavy cabinet in the living room. "Sign here." "You fallers bane a nuisance," protested Jens, signing nevertheless. Scarcely had the sound ox their footfalls died away in the outside hallway when the door of the cabinet slowly opened and a masked face protruded, gazing about the room. It was the Clutching Hand! From the cabinet he took a large package wrapped in newspapers. As he held it, looking keenly about, his eye rested on Elaine's picture. A moment he looked at it, then quickly at the fireplace opposite. An idea seemed to occur to him. He took the package to the fireplace, removed the screen, and laid the package over the andirons with one end pointing out into the room. Next he took from the cabinet a couple of storage batteries and a coil of wire. Deftly and quickly he fixed them on the package. Meanwhile, before an alleyway across the street and further down the long block the express wagon had stopped. The driver and his helper clambered out and for a moment stood talking in low tones, with covert glances at our apartment. They moved into the alley and the driver drew out a battered pair of opera glasses, levelling them at our windows. Having completed fixing the batteries and wires, Clutching Hand ran the wires along the moulding on the wall overhead, from the fireplace until he was directly over Elaine's picture. Skillfully, he managed to fix the wires, using them in place of the picture wires to support the framed photograph. Then he carefully moved the photograph until it hung very noticeably askew on the wall. The last wire joined, he looked about the room, then noiselessly moved to the window and raised the shade. Quickly he raised his hand and brought the fingers slowly together. It was the sign. Off in the alley, the express driver and his helper were still gazing up through the opera glass. "What d'ye see, Bill?" he asked, handing over the glass. The other took it and looked. "It's him--the Hand, Jack," whispered the helper, handing the glasses back. They jumped into the wagon and away it rattled. Jensen was smoking placidly as the wagon pulled up the second time. "Sorry," said the driver sheepishly, "but we delivered the cabinet to the wrong Mr. Kennedy." He pulled out the inevitable book to prove it. "Wall, you bane fine fallers," growled Jensen, puffing like a furnace, in his fury. "You cannot go up agane." "We'll get fired for the mistake," pleaded the helper. "Just this once," urged the driver, as he rattled some loose change in his pocket. "Here--there goes a whole day's tips." He handed Jens a dollar in small change. Still grumpy but mollified by the silver Jens let them go up and opened the door to our rooms again. There stood the cabinet, as outwardly innocent as when it came in. Lugging and tugging they managed to get the heavy piece of furniture out and downstairs again, loading it on the wagon. Then they drove off with it, accompanied by a parting volley from Jensen. In an unfrequented street, perhaps half a mile away, the wagon stopped. With a keen glance around, the driver and his helper made sure that no one was about. "Such a shaking up as you've given me!" growled a voice as the cabinet door opened. "But I've got him this time!" It was the Clutching Hand. "There, men, you can leave me here," he ordered. He motioned to them to drive off and, as they did so, pulled off his masking handkerchief and dived into a narrow street leading up to a thoroughfare. . . . . . . . . Craig gazed into our living room cautiously. "I can't see anything wrong," he said to me as I stood just beside him. "Miss Dodge," he added, "will you and the rest excuse me if I ask you to wait just a moment longer?" Elaine watched him, fascinated. He crossed the room, then went into each of our other rooms. Apparently nothing was wrong and a minute later he reappeared at the doorway. "I guess it's all right," he said. "Perhaps it was only Jensen, the janitor." Elaine, Aunt Josephine and Susie Martin entered. Craig placed chairs for them, but still I could see that he was uneasy. From time to time, while they were admiring one of our treasures after another, he glanced about suspiciously. Finally he moved over to a closet and flung the door open, ready for anything. No one was in the closet and he closed it hastily. "What is the trouble, do you think?" asked Elaine wonderingly, noticing his manner. "I--I can't just say," answered Craig, trying to appear easy. She had risen and with keen interest was looking at the books, the pictures, the queer collection of weapons and odds and ends from the underworld that Craig had amassed in his adventures. At last her eye wandered across the room. She caught sight of her own picture, occupying a place of honor--but hanging askew. "Isn't that just like a man!" she exclaimed laughingly. "Such housekeepers as you are--such carelessness!" She had taken a step or two across the room to straighten the picture. "Miss Dodge!" almost shouted Kennedy, his face fairly blanched, "Stop!" She turned, her stunning eyes filled with amazement at his suddenness. Nevertheless she moved quickly to one side, as he waved his arms, unable to speak quickly enough. Kennedy stood quite still, gazing at the picture, askew, with suspicion. "That wasn't that way when we left, was it, Walter?" he asked. "It certainly was not," I answered positively, "There was more time spent in getting that picture just right than I ever saw you spend on all the rest of the room." Craig frowned. As for myself, I did not know what to make of it. "I'm afraid I shall have to ask you to step into this back room," said Craig at length to the ladies. "I'm sorry--but we can't be too careful with this intruder, whoever he was." They rose, surprised, but, as he continued to urge them, they moved into my room. Elaine, however, stopped at the door. For a moment Kennedy appeared to be considering. Then his eye fell on a fishing rod that stood in a corner. He took it and moved toward the picture. On his hands and knees, to one side, down as close as he could get to the floor, with the rod extended at arm's length, he motioned to me to do the same, behind him. Elaine, unable to repress her interest took a half step forward, breathless, from the doorway, while Susie Martin and Aunt Josephine stood close behind her. Carefully Kennedy reached out with the pole and straightened the picture. As he did so there was a flash, a loud, deafening report, and a great puff of smoke from the fireplace. The fire screen was riddled and overturned. A charge of buckshot shattered the precious photograph of Elaine. We had dropped flat on the floor at the report. I looked about. Kennedy was unharmed, and so were the rest. With a bound he was at the fireplace, followed by Elaine and the rest of us. There, in what remained of a package done up roughly in newspaper, was a shot gun with its barrel sawed off about six inches from the lock, fastened to a block of wood, and connected to a series of springs on the trigger, released by a little electromagnetic arrangement actuated by two batteries and leading by wires up along the moulding to the picture where the slightest touch would complete the circuit. The newspapers which were wrapped about the deadly thing were burning, and Kennedy quickly tore them off, throwing them into the fireplace. A startled cry from Elaine caused us to turn. She was standing directly before her shattered picture where it hung awry on the wall. The heavy charges of buckshot had knocked away large pieces of paper and plaster under it. "Craig!" she gasped. He was at her side in a second. She laid one hand on his arm, as she faced him. With the other she traced an imaginary line in the air from the level of the buckshot to his head and then straight to the infernal thing that had lain in the fireplace. "And to think," she shuddered, "that it was through ME that he tried to kill you!" "Never mind," laughed Craig easily, as they gazed into each other's eyes, drawn together by their mutual peril, "Clutching Hand will have to be cleverer than this to get either of us--Elaine!" CHAPTER V THE POISONED ROOM Elaine and Craig were much together during the next few days. Somehow or other, it seemed that the chase of the Clutching Hand involved long conferences in the Dodge library and even, in fact, extended to excursions into that notoriously crime-infested neighborhood of Riverside Drive with its fashionable processions of automobiles and go-carts--as far north, indeed, as that desperate haunt known as Grant's Tomb. More than that, these delvings into the underworld involved Kennedy in the necessity of wearing a frock coat and silk hat in the afternoon, and I found that he was selecting his neckwear with a care that had been utterly foreign to him during all the years previous that I had known him. It all looked very suspicious to me. But, to return to the more serious side of the affair. Kennedy and Elaine had scarcely come out of the house and descended the steps, one afternoon, when a sinister face appeared in a basement areaway nearby. The figure was crouched over, with his back humped up almost as if deformed, and his left hand had an unmistakable twist. It was the Clutching Hand. He wore a telephone inspector's hat and coat and carried a bag slung by a strap over his shoulder. For once he had left off his mask, but, in place of it, his face was covered by a scraggly black beard. In fact, he seemed to avoid turning his face full, three-quarters or even profile to anyone, unless he had to do so. As much as possible he averted it, but he did so in a clever way that made it seem quite natural. The disguise was effective. He saw Kennedy and Miss Dodge and slunk unobtrusively against a railing, with his head turned away. Laughing and chatting, they passed. As they walked down the street, Clutching Hand turned and gazed after them. Involuntarily the menacing hand clutched in open hatred. Then he turned in the other direction and, going up the steps of the Dodge house, rang the bell. "Telephone inspector," he said in a loud tone as Michael, in Jennings' place for the afternoon, opened the door. He accompanied the words with the sign and Michael, taking care that the words be heard, in case anyone was listening, admitted him. As it happened, Aunt Josephine was upstairs in Elaine's room. She was fixing flowers in a vase on the dressing table of her idolized niece. Meanwhile, Rusty, the collie, lay, half blinking, on the floor. "Who is this?" she asked, as Michael led the bogus telephone inspector into the room. "A man from the telephone company," he answered deferentially. Aunt Josephine, unsophisticated, allowed them to enter without a further question. Quickly, like a good workman, Clutching Hand went to the telephone instrument and by dint of keeping his finger on the hook and his back to Aunt Josephine succeeded in conveying the illusion that he was examining it. Aunt Josephine moved to the door. Not so, Rusty. He did not like the looks of the stranger and he had no scruples against letting it be known. As she put her hand on the knob to go out into the hall, Rusty uttered a low growl which grew into a full-lunged snarl at the Clutching Hand. Clutching Hand kicked at him vigorously, if surreptitiously. Rusty barked. "Lady," he disguised his voice, "will yer please ter call off the dog? Me and him don't seem to cotton to each other." "Here, Rusty," she commanded, "down!" Together Aunt Josephine and Michael removed the still protesting Rusty. No sooner was the door shut than the Clutching Hand moved over swiftly to it. For a few seconds, he stood gazing at them as they disappeared down-stairs. Then he came back into the center of the room. Hastily he opened his bag and from it drew a small powder-spraying outfit such as I have seen used for spraying bug-powder. He then took out a sort of muzzle with an elastic band on it and slipped it over his head so that the muzzle protected his nose and mouth. He seemed to work a sort of pumping attachment and from the nozzle of the spraying instrument blew out a cloud of powder which he directed at the wall. The wall paper was one of those rich, fuzzy varieties and it seemed to catch the powder. Clutching Hand appeared to be more than satisfied with the effect. Meanwhile, Michael, in the hallway, on guard to see that no one bothered the Clutching Hand at his work, was overcome by curiosity to see what his master was doing. He opened the door a little bit and gazed stealthily through the crack into the room. Clutching Hand was now spraying the rug close to the dressing table of Elaine and was standing near the mirror. He stooped down to examine the rug. Then, as he raised his head, he happened to look into the mirror. In it he could see the full reflection of Michael behind him, gazing into the room. "The scoundrel!" muttered Clutching Hand, with repressed fury at the discovery. He rose quickly and shut off the spraying instrument, stuffing it into the bag. He took a step or two toward the door. Michael drew back, fearfully, pretending now to be on guard. Clutching Hand opened the door and, still wearing the muzzle, beckoned to Michael. Michael could scarcely control his fears. But he obeyed, entering Elaine's room after the Clutching Hand, who locked the door. "Were you watching me?" demanded the master criminal, with rage. Michael, trembling all over, shook his head. For a moment Clutching Hand looked him over disdainfully at the clumsy lie. Then he brutally struck Michael in the face, knocking him down. An ungovernable, almost insane fury seemed to possess the man as he stood over the prostrate footman, cursing. "Get up!" he ordered. Michael obeyed, thoroughly cowed. "Take me to the cellar, now," he demanded. Michael led the way from the room without a protest, the master criminal following him closely. Down into the cellar, by a back way, they went, Clutching Hand still wearing his muzzle and Michael saying not a word. Suddenly Clutching Hand turned on him and seized him by the collar. "Now, go upstairs, you," he muttered, shaking him until his teeth fairly chattered, "and if you watch me again--I'll kill you!" He thrust Michael away and the footman, overcome by fear, hurried upstairs. Still trembling and fearful, Michael paused In the hallway, looking back resentfully, for even one who is in the power of a super-criminal is still human and has feelings that may be injured. Michael put his hand on his face where the Clutching Hand had struck him. There he waited, muttering to himself. As he thought it over, anger took the place of fear. He slowly turned in the direction of the cellar. Closing both his fists, Michael made a threatening gesture at his master in crime. Meanwhile, Clutching Hand was standing by the electric meter. He examined it carefully, feeling where the wires entered and left it starting to trace them out. At last he came to a point where it seemed suitable to make a connection for some purpose he had in mind. Quickly he took some wire from his bag and connected it with the electric light wires. Next, he led these wires, concealed of course, along the cellar floor, in the direction of the furnace. The furnace was one of the old hot air heaters and he paused before it as though seeking something. Then he bent down beside it and uncovered a little tank. He took off the top on which were cast in the iron the words: "This tank must be kept full of water." He thrust his hand gingerly into it, bringing it out quickly. The tank was nearly full of water and he brought his hand out wet. It was also hot. But he did not seem to mind that, for he shook his head with a smile of satisfaction. Next, from his capacious bag he took two metal poles, or electrodes, and fastened them carefully to the ends of the wires, placing them at opposite ends of the tank in the water. For several moments he watched. The water inside the tank seemed the same as before, only on each electrode there appeared bubbles, on one bubbles of oxygen, on the other of hydrogen. The water was decomposing under the current by electrolysis. Another moment he surveyed his work to see that he had left no loose ends. Then he picked up his bag and moved toward the cellar steps. As he did so, he removed the muzzle from his nose and quietly let himself out of the house. . . . . . . . . The next morning, Rusty, who had been Elaine's constant companion since the trouble had begun, awakened his mistress by licking her hand as it hung limply over the side of her bed. She awakened with a start and put her hand to her head. She felt ill. "Poor old fellow," she murmured, half dazedly, for the moment endowing her pet with her own feelings, as she patted his faithful shaggy head. Rusty moved away again, wagging his tail listlessly. The collie, too, felt ill. Elaine watched him as he walked, dejected, across the room and then lay down. "Why, Miss Elaine--what ees ze mattair? You are so pale!" exclaimed the maid, Marie, as she entered the room a moment later with the morning's mail on a salver. "I don't feel well, Marie," she replied, trying with her slender white hand to brush the cobwebs from her brain. "I--I wish you'd tell Aunt Josephine to telephone Dr. Hayward." "Yes, mademoiselle," answered Marie, deftly and sympathetically straightening out the pillows. Languidly Elaine took the letters one by one off the salver. She looked at them, but seemed not to have energy enough to open them. Finally she selected one and slowly tore it open. It had no superscription, but it at once arrested her attention and transfixed her with terror. It read: "YOU ARE SICK THIS MORNING. TOMORROW YOU WILL BE WORSE. THE NEXT DAY YOU WILL DIE UNLESS YOU DISCHARGE CRAIG KENNEDY." It was signed by the mystic trademark of the fearsome Clutching Hand! Elaine drew back into the pillows, horror stricken. Quickly she called to Marie. "Go--get Aunt Josephine--right away!" As Marie almost flew down the hall, Elaine still holding the letter convulsively, pulled herself together and got up, trembling. She almost seized the telephone as she called Kennedy's number. . . . . . . . . Kennedy, in his stained laboratory apron, was at work before his table, while I was watching him with intense interest, when the telephone rang. Without a word he answered the call and I could see a look of perturbation cross his face. I knew it was from Elaine, but could tell nothing about the nature of the message. An instant later he almost tore off the apron and threw on his hat and coat. I followed him as he dashed out of the laboratory. "This is terrible--terrible," he muttered, as we hurried across the campus of the University to a taxi-cab stand. A few minutes later, when we arrived at the Dodge mansion, we found Aunt Josephine and Marie doing all they could under the circumstances. Aunt Josephine had just given her a glass of water which she drank eagerly. Rusty had, meanwhile, crawled under the bed, caring only to be alone and undisturbed. Dr. Hayward had arrived and had just finished taking her pulse and temperature as our cab pulled up. Jennings who had evidently been expecting us let us in without a word and conducted us up to Elaine's room. We knocked. "Mr. Kennedy and Mr. Jameson," we could hear Marie whisper in a subdued voice. "Tell them to come in," answered Elaine eagerly. We entered. There she lay, beautiful as ever, but with a whiteness of her fresh cheek that was too etherially unnatural. Elaine was quite ill indeed. "Oh--I'm so glad to see you," she breathed, with an air of relief as Kennedy advanced. "Why--what is the matter?" asked Craig, anxiously. Dr. Hayward shook his head dubiously, but Kennedy did not notice him, for, as he approached Elaine, she drew from the covers where she had concealed it a letter and handed it to him. Craig took it and read: "YOU ARE SICK THIS MORNING. TOMORROW YOU WILL BE WORSE. THE NEXT DAY YOU WILL DIE UNLESS YOU DISCHARGE CRAIG KENNEDY." At the signature of the Clutching Hand he frowned, then, noticing Dr. Hayward, turned to him and repeated his question, "What is the matter?" Dr. Hayward continued shaking his head. "I cannot diagnose her symptoms," he shrugged. As I watched Kennedy's face, I saw his nostrils dilating, almost as if he were a hound and had scented his quarry. I sniffed, too. There seemed to be a faint odor, almost as if of garlic, in the room. It was unmistakable and Craig looked about him curiously but said nothing. As he sniffed, he moved impatiently and his foot touched Rusty, under the bed. Rusty whined and moved back lazily. Craig bent over and looked at him. "What's the matter with Rusty?" he asked. "Is he sick, too?" "Why--yes," answered Elaine, following Craig with her deep eyes. "Poor Rusty. He woke me up this morning. He feels as badly as I do, poor old fellow." Craig reached down and gently pulled the collie out into the room. Rusty crouched down close to the floor. His nose was hot and dry and feverish. He was plainly ill. "How long has Rusty been in the room?" asked Craig. "All night," answered Elaine. "I wouldn't think of being without him now." Kennedy lifted the dog by his front paws. Rusty submitted patiently, but without any spirit. "May I take Rusty along with me?" he asked finally. Elaine hesitated. "Surely," she said at length, "only, be gentle with him." Craig looked at her as though it would be impossible to be otherwise with anything belonging to Elaine. "Of course," he said simply. "I thought that I might be able to discover the trouble from studying him." We stayed only a few minutes longer, for Kennedy seemed to realize the necessity of doing something immediately and even Dr. Hayward was fighting in the dark. As for me, I gave it up, too. I could find no answer to the mystery of what was the peculiar malady of Elaine. Back in the laboratory, Kennedy set to work immediately, brushing everything else aside. He began by drawing off a little of Rusty's blood in a tube, very carefully. "Here, Walter," he said pointing to the little incision he had made. "Will you take care of him?" I bound up the wounded leg and gave the poor beast a drink of water. Rusty looked at me gratefully from his big sad brown eyes. He seemed to appreciate our gentleness and to realize that we were trying to help him. In the meantime, Craig had taken a flask with a rubber stopper. Through one hole in it was fitted a long funnel; through another ran a glass tube. The tube connected with a large U-shaped drying tube filled with calcium chloride, which, in turn, connected with a long open tube with an upturned end. Into the flask, Craig dropped some pure granulated zinc. Then he covered it with dilute sulphuric acid, poured in through the funnel tube. "That forms hydrogen gas," he explained to me, "which passes through the drying tube and the ignition tube. Wait a moment until all the air is expelled from the tubes." He lighted a match and touched it to the open, upturned end. The hydrogen, now escaping freely, was ignited with a pale blue flame. A few moments later, having extracted something like a serum from the blood he had drawn off from Rusty. He added the extract to the mixture in the flask, pouring it in, also through the funnel tube. Almost immediately the pale, bluish flame turned to bluish white, and white fumes were formed. In the ignition tube a sort of metallic deposit appeared. Quickly Craig made one test after another. As he did so, I sniffed. There was an unmistakable odor of garlic in the air which made me think of what I had already noticed in Elaine's room. "What is it?" I asked, mystified. "Arseniuretted hydrogen," he answered, still engaged in verifying his tests. "This is the Marsh test for arsenic." I gazed from Kennedy to the apparatus, then to Rusty and a picture of Elaine, pale and listless, flashed before me. "Arsenic!" I repeated in horror. . . . . . . . . I had scarcely recovered from the surprise of Kennedy's startling revelation when the telephone rang again. Kennedy seized the receiver, thinking evidently that the message might be from or about Elaine. But from the look on his face and from his manner, I could gather that, although it was not from Elaine herself, it was about something that interested him greatly. As he talked, he took his little notebook and hastily jotted down something in it. Still, I could not make out what the conversation was about. "Good!" I heard him say finally. "I shall keep the appointment--absolutely." His face wore a peculiar puzzled look as he hung up the receiver. "What was it?" I asked eagerly. "It was Elaine's footman, Michael," he replied thoughtfully. "As I suspected, he says that he is a confederate of the Clutching Hand and if we will protect him he will tell us the trouble with Elaine." I considered a moment. "How's that?" I queried. "Well," added Craig, "you see, Michael has become infuriated by the treatment he received from the Clutching Hand. I believe he cuffed him in the face yesterday. Anyway, he says he has determined to get even and betray him. So, after hearing how Elaine was, he slipped out of the servant's door and looking about carefully to see that he wasn't followed, he went straight to a drug store and called me up. He seemed extremely nervous and fearful." I did not like the looks of the thing, and said so. "Craig," I objected vehemently, "don't go to meet him. It is a trap." Kennedy had evidently considered my objection already. "It may be a trap," he replied slowly, "but Elaine is dying and we've got to see this thing through." As he spoke, he took an automatic from a drawer of a cabinet and thrust it into his pocket. Then he went to another drawer and took out several sections of thin tubing which seemed to be made to fasten together as a fishing pole is fastened, but were now separate, as if ready for travelling. "Well--are you coming, Walter?" he asked finally--the only answer to my flood of caution. Then he went out. I followed, still arguing. "If YOU go, _I_ go," I capitulated. "That's all there is to it." Following the directions that Michael had given over the telephone Craig led me into one of the toughest parts of the lower West Side. "Here's the place," he announced, stopping across the street from a dingy Raines Law Hotel. "Pretty tough," I objected. "Are you sure?" "Quite," replied Kennedy, consulting his note book again. "Well, I'll be hanged if I'll go in that joint," I persisted. It had no effect on Kennedy. "Nonsense, Walter," he replied, crossing the street. Reluctantly I followed and we entered the place. "I want a room," asked Craig as we were accosted by the proprietor, comfortably clad in a loud checked suit and striped shirt sleeves. "I had one here once before--forty-nine, I think." "Fifty--" I began to correct. Kennedy trod hard on my toes. "Yes, forty-nine," he repeated. The proprietor called a stout negro porter, waiter, and bell-hop all combined in one, who led us upstairs. "Fohty-nine, sah," he pointed out, as Kennedy dropped a dime into his ready palm. The negro left us and as Craig started to enter, I objected, "But, Craig, it was fifty-nine, not forty-nine. This is the wrong room." "I know it," he replied. "I had it written in the book. But I want forty-nine--now. Just follow me, Walter." Nervously I followed him into the room. "Don't you understand?" he went on. "Room forty-nine is probably just the same as fifty-nine, except perhaps the pictures and furniture, only it is on the floor below." He gazed about keenly. Then he took a few steps to the window and threw it open. As he stood there he took the parts of the rods he had been carrying and fitted them together until he had a pole some eight or ten feet long. At one end was a curious arrangement that seemed to contain lenses and a mirror. At the other end was an eye-piece, as nearly as I could make out. "What is that?" I asked as he completed his work. "That? That is an instrument something on the order of a miniature submarine periscope," Craig replied, still at work. I watched him, fascinated at his resourcefulness. He stealthily thrust the mirror end of the periscope out of the window and up toward the corresponding window up stairs. Then he gazed eagerly through the eye-piece. "Walter--look!" he exclaimed to me. I did. There, sure enough, was Michael, pacing up and down the room. He had already preceded us. In his scared and stealthy manner, he had entered the Raines Law hotel which announced "Furnished Rooms for Gentlemen Only." There he had sought a room, fifty-nine, as he had said. As he came into the room, he had looked about, overcome by the enormity of what he was about to do. He locked the door. Still, he had not been able to avoid gazing about fearfully, as he was doing now that we saw him. Nothing had happened. Yet he brushed his hand over his forehead and breathed a sigh of relief. The air seemed to be stifling him and already he had gone to the window and thrown it open. Then he had gazed out as though there might be some unknown peril in the very air. He had now drawn back from the window and was considering. He was actually trembling. Should he flee? He whistled softly to himself to keep his shaking fears under control. Then he started to pace up and down the room in nervous impatience and irresolution. As I looked at him nervously walking to and fro, I could not help admitting that things looked safe enough and all right to me. Kennedy folded the periscope up and we left our room, mounting the remaining flight of stairs. In fifty-nine we could hear the measured step of the footman. Craig knocked. The footsteps ceased. Then the door opened slowly and I could see a cold blue automatic. "Look out!" I cried. Michael in his fear had drawn a gun. "It's all right, Michael," reassured Craig calmly. "All right, Walter," he added to me. The gun dropped back into the footman's pocket. We entered and Michael again locked the door. Not a word had been spoken by him so far. Next Michael moved to the center of the room and, as I realized later, brought himself in direct lines with the open window. He seemed to be overcome with fear at his betrayal and stood there breathing heavily. "Professor Kennedy," he began, "I have been so mistreated that I have made up my mind to tell you all I know about this Clutching--" Suddenly he drew a sharp breath and both his hands clutched at his own breast. He did not stagger and fall in the ordinary manner, but seemed to bend at the knees and waist and literally crumple down on his face. We ran to him. Craig turned him over gently on his back and examined him. He called. No answer. Michael was almost pulseless. Quickly Craig tore off his collar and bared his breast, for the man seemed to be struggling for breath. As he did so, he drew from Michael's chest a small, sharp-pointed dart. "What's that?" I ejaculated, horror stricken. "A poisoned blow gun dart such as is used by the South American Indians on the upper Orinoco," he said slowly. He examined it carefully. "What is the poison?" I asked. "Curari," he replied simply. "It acts on the respiratory muscles, paralyzing them, and causing asphyxiation." The dart seemed to have been made of a quill with a very sharp point, hollow, and containing the deadly poison in the sharpened end. "Look out!" I cautioned as he handled it. "Oh, that's all right," he answered casually. "If I don't scratch myself, I am safe enough. I could swallow the stuff and it wouldn't hurt me--unless I had an abrasion of the lips or some internal cut." Kennedy continued to examine the dart until suddenly I heard a low exclamation of surprise from him. Inside the hollow quill was a thin sheet of tissue paper, tightly rolled. He drew it out and read: "To know me is DEATH Kennedy--Take Warning!" Underneath was the inevitable Clutching Hand sign. We jumped to our feet. Kennedy rushed to the window and slammed it shut, while I seized the key from Michael's pocket, opened the door and called for help. A moment before, on the roof of a building across the street, one might have seen a bent, skulking figure. His face was copper colored and on his head was a thick thatch of matted hair. He looked like a South American Indian, in a very dilapidated suit of castoff American clothes. He had slipped out through a doorway leading to a flight of steps from the roof to the hallway of the tenement. His fatal dart sent on its unerring mission with a precision born of long years in the South American jungle, he concealed the deadly blow-gun in his breast pocket, with a cruel smile, and, like one of his native venomous serpents, wormed his way down the stairs again. . . . . . . . . My outcry brought a veritable battalion of aid. The hotel proprietor, the negro waiter, and several others dashed upstairs, followed shortly by a portly policeman, puffing at the exertion. "What's the matter, here?" he panted. "Ye're all under arrest!" Kennedy quietly pulled out his card case and taking the policeman aside showed it to him. "We had an appointment to meet this man--in that Clutching Hand case, you know. He is Miss Dodge's footman," Craig explained. Then he took the policeman into his confidence, showing him the dart and explaining about the poison. The officer stared blankly. "I must get away, too," hurried on Craig. "Officer, I will leave you to take charge here. You can depend on me for the inquest." The officer nodded. "Come on, Walter," whispered Craig, eager to get away, then adding the one word, "Elaine!" I followed hastily, not slow to understand his fear for her. Nor were Craig's fears groundless. In spite of all that could be done for her, Elaine was still in bed, much weaker now than before. While we had been gone, Dr. Hayward, Aunt Josephine and Marie were distracted. More than that, the Clutching Hand had not neglected the opportunity, either. Suddenly, just before our return, a stone had come hurtling through the window, without warning of any kind, and had landed on Elaine's bed. Below, as we learned some time afterwards, a car had drawn up hastily and the evil-faced crook whom the Clutching Hand had used to rid himself of the informer, "Limpy Red," had leaped out and hurled the stone through the window, as quickly leaping back into the car and whisking away. Elaine had screamed. All had reached for the stone. But she had been the first to seize it and discover that around it was wrapped a piece of paper on which was the ominous warning, signed as usual by the Hand: "Michael is dead. Tomorrow, you. Then Kennedy. Stop before it is too late." Elaine had sunk back into her pillows, paler than ever from this second shock, while the others, as they read the note, were overcome by alarm and despair, at the suddenness of the thing. It was just then that Kennedy and I arrived and were admitted. "Oh, Mr. Kennedy," cried Elaine, handing him the note. Craig took it and read. "Miss Dodge," he said, as he held the note out to me, "you are suffering from arsenic poisoning--but I don't know yet how it is being administered." He gazed about keenly. Meanwhile, I had taken the crumpled note from him and was reading it. Somehow, I had leaned against the wall. As I turned, Craig happened to glance at me. "For heaven's sake, Walter," I heard him exclaim. "What have you been up against?" He fairly leaped at me and I felt him examining my shoulder where I had been leaning on the wall. Something on the paper had come off and had left a white mark on my shoulder. Craig looked puzzled from me to the wall. "Arsenic!" he cried. He whipped out a pocket lens and looked at the paper. "This heavy fuzzy paper is fairly loaded with it, powdered," he reported. I looked, too. The powdered arsenic was plainly discernible. "Yes, here it is," he continued, standing absorbed in thought. "But why did it work so effectively?" He sniffed as he had before. So did I. There was still the faint smell of garlic. Kennedy paced the room. Suddenly, pausing by the register, an idea seemed to strike him. "Walter," he whispered, "come down cellar with me." "Oh--be careful," cried Elaine, anxious for him. "I will," he called back. As he flashed his pocket electric bull's-eye about, his gaze fell on the electric meter. He paused before it. In spite of the fact that it was broad daylight, it was running. His face puckered. "They are using no current at present in the house," he ruminated. "Yet the meter is running." He continued to examine the meter. Then he began to follow the electric wires along. At last he discovered a place where they had been tampered with and tapped by other wires. "The work of the Clutching Hand!" he muttered. Eagerly he followed the wires to the furnace and around to the back. There they led right into a little water tank. Kennedy yanked them out. As he did so he pulled something with them. "Two electrodes--the villain placed there," he exclaimed, holding them up triumphantly for me to see. "Y-yes," I replied dubiously, "but what does it all mean?" "Why, don't you see? Under the influence of the electric current the water was decomposed and gave off oxygen and hydrogen. The free hydrogen passed up the furnace pipe and combining with the arsenic in the wall paper formed the deadly arseniuretted hydrogen." He cast the whole improvised electrolysis apparatus on the floor and dashed up the cellar steps. "I've found it!" he cried, hurrying into Elaine's room. "It's in this room--a deadly gas--arseniuretted hydrogen." He tore open the windows and threw them all open. "Have her moved," he cried to Aunt Josephine. "Then have a vacuum cleaner go over every inch of wall, carpet and upholstery." Standing beside her, he breathlessly explained his discovery. "That wall paper has been loaded down with arsenic, probably Paris green or Schweinfurth green, which is aceto-arsenite of copper. Every minute you are here, you are breathing arseniuretted hydrogen. The Clutching Hand has cleverly contrived to introduce the nascent gas into the room. That acts on the arsenic compounds in the wall paper and hangings and sets free the gas. I thought I knew the smell the moment I got a whiff of it. You are slowly being poisoned by minute quantities of the deadly gas. This Clutching Hand is a diabolical genius. Think of it--poisoned wall paper!" No one said a word. Kennedy reached down and took the two Clutching Hand messages Elaine had received. "I shall want to study these notes, more, too," he said, holding them up to the wall at the head of the bed as he flashed his pocket lens at them. "You see, Elaine, I may be able to get something from studying the ink, the paper, the handwriting--" Suddenly both leaped back, with a cry. Their faces had been several inches apart. Something had whizzed between them and literally impaled the two notes on the wall. Down the street, on the roof of a carriage house, back of a neighbor's, might have been seen the uncouth figure of the dilapidated South American Indian crouching behind a chimney and gazing intently at the Dodge house. As Craig had thrown open Elaine's window and turned to Elaine, the figure had crouched closer to his chimney. Then with an uncanny determination he slowly raised the blow-gun to his lips. I jumped forward, followed by Dr. Hayward, Aunt Josephine, and Marie. Kennedy had a peculiar look as he pulled out from the wall a blow-gun dart similar in every way to that which had killed Michael. "Craig!" gasped Elaine, reaching up and laying her soft white hand on his arm in undisguised fear for him, "you--you must give up this chase for the Clutching Hand!" "Give up the chase for the Clutching Hand?" he repeated in surprise. "Never! Not until either he or I is dead!" There was both fear and admiration mingled in her look, as he reached down and patted her dainty shoulder encouragingly. CHAPTER VI THE VAMPIRE Kennedy went the next day to the Dodge house, and, as usual, Perry Bennett was there in the library with Elaine, still going over the Clutching Hand case, in their endeavor to track down the mysterious master criminal. Bennett seemed as deeply as ever in love with Elaine. Still, as Jennings admitted Craig, it was sufficiently evident by the manner in which Elaine left Bennett and ran to meet Craig that she had the highest regard for him. "I've brought you a little document that may interest you," remarked Kennedy, reaching into his pocket and pulling out an envelope. Elaine tore it open and looked at the paper within. "Oh, how thoughtful of you!" she exclaimed in surprise. It was a permit from the police made out in her name allowing her to carry a revolver. A moment later, Kennedy reached into his coat pocket and produced a little automatic which he handed to her. "Thank you," she cried eagerly. Elaine examined the gun with interest, then, raising it, pointed it playfully at Bennett. "Oh--no--no!" exclaimed Kennedy, taking her arm quickly, and gently deflecting the weapon away. "You mustn't think it is a toy. It explodes at a mere touch of the trigger--when that safety ratchet is turned." Bennett had realized the danger and had jumped back, almost mechanically. As he did so, he bumped into a suit of medieval armor standing by the wall, knocking it over with a resounding crash. "I beg pardon," he ejaculated, "I'm very sorry. That was very awkward of me." Jennings, who had been busy about the portieres at the doorway, started to pick up the fallen knight. Some of the pieces were broken, and the three gathered about as the butler tried to fit them together again as best he could. "Too bad, too bad," apologized Bennett profusely. "I really forgot how close I was to the thing." "Oh, never mind," returned Elaine, a little crestfallen, "It is smashed all right--but it was my fault. Jennings, send for someone to repair it." She turned to Kennedy. "But I do wish you would teach me how to use this thing," she added, touching the automatic gingerly. "Gladly," he returned. "Won't you join us, Mr. Bennett?" asked Elaine. "No," the young lawyer smiled, "I'm afraid I can't. You see, I had an engagement with another client and I'm already late." He took his hat and coat and, with a reluctant farewell, moved toward the hallway. A moment later Elaine and Craig followed, while Jennings finished restoring the armor as nearly as possible as it had been. . . . . . . . . It was late that night that a masked figure succeeded in raising itself to the narrow ornamental ledge under Elaine's bedroom window. Elaine was a light sleeper and, besides, Rusty, her faithful collie, now fully recovered from the poison, was in her room. Rusty growled and the sudden noise wakened her. Startled, Elaine instantly thought of the automatic. She reached under her pillow, keeping very quiet, and drew forth the gun that Craig had given her. Stealthily concealing her actions under the covers, she levelled the automatic at the figure silhouetted in her window and fired three times. The figure fell back. Down in the street, below, the assistant of the Clutching Hand who had waited while Taylor Dodge was electrocuted, was waiting now as his confederate, "Pitts Slim"--which indicated that he was both wiry in stature and libellous in delegating his nativity--made the attempt. As Slim came tumbling down, having fallen back from the window above, mortally wounded, the confederate lifted him up and carried him out of sight hurriedly. Elaine, by this time, had turned on the lights and had run to the window to look out. Rusty was barking loudly. In a side street, nearby, stood a waiting automobile, at the wheel of which sat another of the emissaries of the Clutching Hand. The driver looked up, startled, as he saw his fellow hurry around the corner carrying the wounded Pitts Slim. It was the work of just a moment to drop the wounded man, as comfortably as possible under the circumstances, in the rear seat, while his pals started the car off with a jerk in the hurry of escape. Jennings, having hastily slipped his trousers on over his pajamas came running down the hall, while Marie, frightened, came in the other direction. Aunt Josephine appeared a few seconds later, adding to the general excitement. "What's the matter?" she asked, anxiously. "A burglar, I think," exclaimed Elaine, still holding the gun in her hand. "Someone tried to get into my window." "My gracious," cried Aunt Josephine, in alarm, "where will this thing end?" Elaine was doing her best now to quiet the fears of her aunt and the rest of the household. "Well," she laughed, a little nervously, now that it was all over, "I want you all to go to bed and stop worrying about me. Don't you see, I'm perfectly able to take care of myself? Besides, there isn't a chance, now, of the burglar coming back. Why, I shot him." "Yes," put in Aunt Josephine, "but--" Elaine laughingly interrupted her and playfully made as though she were driving them out of her room, although they were all very much concerned over the affair. However, they went finally, and she locked the door. "Rusty!" she called, "Down there!" The intelligent collie seemed to understand. He lay down by the doorway, his nose close to the bottom of the door and his ears alert. Finally Elaine, too, retired again. . . . . . . . . Meanwhile the wounded man was being hurried to one of the hangouts of the mysterious Clutching Hand, an old-fashioned house in the Westchester suburbs. It was a carefully hidden place, back from the main road, surrounded by trees, with a driveway leading up to it. The car containing the wounded Pitts Slim drew up and the other two men leaped out of it. With a hurried glance about, they unlocked the front door with a pass-key and entered, carrying the man. Indoors was another emissary of the Clutching Hand, a rather studious looking chap. "Why, what's the matter?" he exclaimed, as the crooks entered his room, supporting their half-fainting, wounded pal. "Slim got a couple of pills," they panted, as they laid him on a couch. "How?" demanded the other. "Trying to get into the Dodge house. Elaine did it." Slim was, quite evidently, badly wounded and was bleeding profusely. A glance at him was enough for the studious-looking chap. He went to a secret panel and, pressing it down, took out what was apparently a house telephone. In another part of this mysterious house was the secret room of the Clutching Hand himself where he hid his identity from even his most trusted followers. It was a small room, lined with books on every conceivable branch of science that might aid him and containing innumerable little odds and ends of paraphernalia that might help in his nefarious criminal career. His telephone rang and he took down the receiver. "Pitts Slim's been wounded--badly--Chief," was all he waited to hear. With scarcely a word, he hung up the receiver, then opened a table drawer and took out his masking handkerchief. Next he went to a nearby bookcase, pressed another secret spring, and a panel opened. He passed through, the handkerchief adjusted. Across, in the larger, outside study, another panel opened and the Clutching Hand, all crouched up, transformed, appeared. Without a word he advanced to the couch on which the wounded crook lay and examined him. "How did it happen?" he asked at length. "Miss Dodge shot him," answered the others, "with an automatic." "That Craig Kennedy must have given it to her!" he exclaimed with suppressed fury. For a moment the Clutching Hand stopped to consider. Then he seized the regular telephone. "Dr. Morton?" he asked as he got the number he called. Late as it was the doctor, who was a well-known surgeon in that part of the country, answered, apparently from an extension of his telephone near his bed. The call was urgent and apparently from a family which he did not feel that he could neglect. "Yes, I'll be there--in a few moments," he yawned, hanging up the receiver and getting out of bed. Dr. Morton was a middle-aged man, one of those medical men in whose judgment one instinctively relies. From the brief description of the "hemorrhage" which the Clutching Hand had cleverly made over the wire, he knew that a life was at stake. Quickly he dressed and went out to his garage, back of the house to get his little runabout. It was only a matter of minutes before the doctor was speeding over the now deserted suburban roads, apparently on his errand of mercy. At the address that had been given him, he drew up to the side of the road, got out and ran up the steps to the door. A ring at the bell brought a sleepy man to the door, in his trousers and nightshirt. "How's the patient?" asked Dr. Morton, eagerly. "Patient?" repeated the man, rubbing his eyes. "There's no one sick here." "Then what did you telephone for?" asked the doctor peevishly, "Telephone? I didn't call up anyone, I was asleep." Slowly it dawned on the doctor that it was a false alarm and that he must be the victim of some practical joke. "Well, that's a great note," he growled, as the man shut the door. He descended the steps, muttering harsh language at some unknown trickster. As he climbed back into his machine and made ready to start, two men seemed to rise before him, as if from nowhere. As a matter of fact, they had been sent there by the Clutching Hand and were hiding in a nearby cellar way until their chance came. One man stood on the running board, on either side of him, and two guns yawned menacingly at him. "Drive ahead--that way!" muttered one man, seating himself in the runabout with his gun close to the doctor's ribs. The other kept his place on the running board, and on they drove in the direction of the mysterious, dark house. Half a mile, perhaps, down the road, they halted and left the car beside the walk. Dr. Morton was too surprised to marvel at anything now and he realized that he was in the power of two desperate men. Quickly, they blindfolded him. It seemed an interminable walk, as they led him about to confuse him, but at last he could feel that they had taken him into a house and along passageways, which they were making unnecessarily long in order to destroy all recollection that they could. Finally he knew that he was in a room in which others were present. He suppressed a shudder at the low, menacing voices. A moment later he felt them remove the bandage from his eyes, and, blinking at the light, he could see a hard-faced fellow, pale and weak, on a blood-stained couch. Over him bent a masked man and another man stood nearby, endeavoring by improvised bandages to stop the flow of blood. "What can you do for this fellow?" asked the masked man. Dr. Morton, seeing nothing else to do, for he was more than outnumbered now, bent down and examined him. As he rose, he said, "He will be dead from loss of blood by morning, no matter if he is properly bandaged." "Is there nothing that can save him?" whispered the Clutching Hand hoarsely. "Blood transfusion might save him," replied the Doctor. "But so much blood would be needed that whoever gives it would be liable to die himself." Clutching Hand stood silent a moment, thinking, as he gazed at the man who had been one of his chief reliances. Then, with a menacing gesture, he spoke in a low, bitter tone. "SHE WHO SHOT HIM SHALL SUPPLY THE BLOOD." . . . . . . . . A few quick directions followed to his subordinates, and as he made ready to go, he muttered, "Keep the doctor here. Don't let him stir from the room." Then, with the man who had aided him in the murder of Taylor Dodge, he sallied out into the blackness that precedes dawn. It was just before early daybreak when the Clutching Hand and his confederate reached the Dodge House in the city and came up to the back door, over the fences. As they stood there, the Clutching Hand produced a master key and started to open the door. But before he did so, he took out his watch. "Let me see," he ruminated. "Twenty minutes past four. At exactly half past, I want you to do as I told you--see?" The other crook nodded. "You may go," ordered the Clutching Hand. As the crook slunk away, Clutching Hand stealthily let himself into the house. Noiselessly he prowled through the halls until he came to Elaine's doorway. He gave a hasty look up and down the hall. There was no sound. Quickly he took a syringe from his pocket and bent down by the door. Inserting the end under it, he squirted some liquid through which vaporized rapidly in a wide, fine stream of spray. Before he could give an alarm, Rusty was overcome by the noxious fumes, rolled over on his back and lay still. Outside, the other crook was waiting, looking at his watch. As the hand slowly turned the half hour, he snapped the watch shut. With a quick glance up and down the deserted street, he deftly started up the rain pipe that passed near Elaine's window. This time there was no faithful Rusty to give warning and the second intruder, after a glance at Elaine, still sleeping, went quickly to the door, dragged the insensible dog out of the way, turned the key and admitted the Clutching Hand. As he did so he closed the door. Evidently the fumes had not reached Elaine, or if they had, the inrush of fresh air revived her, for she waked and quickly reached for the gun. In an instant the other crook had leaped at her. Holding his hand over her mouth to prevent her screaming he snatched the revolver away before she could fire it. In the meantime the Clutching Hand had taken out some chloroform and, rolling a towel in the form of a cone, placed it over her face. She struggled, gasping and gagging, but the struggles grew weaker and weaker and finally ceased altogether. When Elaine was completely under the influence of the drug, they lifted her out of bed, the chloroform cone still over her face, and quietly carried her to the door which they opened stealthily. Downstairs they carried her until they came to the library with its new safe and there they placed her on a couch. . . . . . . . . At an early hour an express wagon stopped before the Dodge house and Jennings, half dressed, answered the bell. "We've come for that broken suit of armor to be repaired," said a workman. Jennings let the men in. The armor was still on the stand and the repairers took armor, stand, and all, laying it on the couch where they wrapped it in the covers they had brought for the purpose. They lifted it up and started to carry it out. "Be careful," cautioned the thrifty Jennings. Rusty, now recovered, was barking and sniffing at the armor. "Kick the mutt off," growled one man. The other did so and Rusty snarled and snapped at him. Jennings took him by the collar and held him as the repairers went out, loaded the armor on the wagon, and drove off. Scarcely had they gone, while Jennings straightened out the disarranged library, when Rusty began jumping about, barking furiously. Jennings looked at him in amazement, as the dog ran to the window and leaped out. He had no time to look after the dog, though, for at that very instant he heard a voice calling, "Jennings! Jennings!" It was Marie, almost speechless. He followed her as she led the way to Miss Elaine's room. There Marie pointed mutely at the bed. Elaine was not there. There, too, were her clothes, neatly folded, as Marie had hung them for her. "Something must have happened to her!" wailed Marie. Jennings was now thoroughly alarmed. Meanwhile the express wagon outside was driving off, with Rusty tearing after it. "What's the matter?" cried Aunt Josephine coming in where the footman and the maid were arguing what was to be done. She gave one look at the bed, the clothes, and the servants. "Call Mr. Kennedy!" she cried in alarm. . . . . . . . . "Elaine is gone--no one knows how or where," announced Craig as he leaped out of bed that morning to answer the furious ringing of our telephone bell. It was very early, but Craig dressed hurriedly and I followed as best I could, for he had the start of me, tieless and collarless. When we arrived at the Dodge house, Aunt Josephine and Marie were fully dressed. Jennings let us in. "What has happened?" demanded Kennedy breathlessly. While Aunt Josephine tried to tell him, Craig was busy examining the room. "Let us see the library," he said at length. Accordingly down to the library we went. Kennedy looked about. He seemed to miss something. "Where is the armor?" he demanded. "Why, the men came for it and took it away to repair," answered Jennings. Kennedy's brow clouded in deep thought. Outside we had left our taxi, waiting. The door was open and a new footman, James, was sweeping the rug, when past him flashed a dishevelled hairy streak. We were all standing there still as Craig questioned Jennings about the armor. With a yelp Rusty tore frantically into the room. A moment he stopped and barked. We all looked at him in surprise. Then, as no one moved, he seemed to single out Kennedy. He seized Craig's coat in his teeth and tried to drag him out. "Here, Rusty--down, sir, down!" called Jennings. "No, Jennings, no," interposed Craig. "What's the matter, old fellow?" Craig patted Rusty whose big brown eyes seemed mutely appealing. Out of the doorway he went, barking still. Craig and I followed while the rest stood in the vestibule. Rusty was trying to lead Kennedy down the street! "Wait here," called Kennedy to Aunt Josephine, as he stepped with me on the running board of the cab. "Go on, Rusty, good dog!" Rusty needed no urging. With an eager yelp he started off, still barking, ahead of us, our car following. On we went, much to the astonishment of those who were on the street at such an early hour. It seemed miles that we went, but at last we came to a peculiarly deserted looking house. Here Rusty turned in and began scratching at the door. We jumped off the cab and followed. The door was locked when we tried and from inside we could get no answer. We put our shoulders to it and burst it in. Rusty gave a leap forward with a joyous bark. We followed, more cautiously. There were pieces of armor strewn all over the floor. Rusty sniffed at them and looked about, disappointed, then howled. I looked from the armor to Kennedy, in blank amazement. "Elaine was kidnapped--in the armor," he cried. . . . . . . . . He was right. Meanwhile, the armor repairers had stopped at last at this apparently deserted house, a strange sort of repair shop. Still keeping it wrapped in blankets, they had taken the armor out of the wagon and now laid it down on an old broken bed. Then they had unwrapped it and taken off the helmet. There was Elaine! She had been stupefied, bound and gagged. Piece after piece of the armor they removed, finding her still only half conscious. "Sh! What's that?" cautioned one of the men. They paused and listened. Sure enough, there was a sound outside. They opened the window cautiously. A dog was scratching on the door, endeavoring to get in. It was Rusty. "I think it's her dog," said the man, turning. "We'd better let him in. Someone might see him." The other nodded and a moment later the door opened and in ran Rusty. Straight to Elaine he went, starting to lick her hand. "Right--her dog," exclaimed the other man, drawing a gun and hastily levelling it at Rusty. "Don't!" cautioned the first. "It would make too much noise. You'd better choke him!" The fellow grabbed for Rusty. Rusty was too quick. He jumped. Around the room they ran. Rusty saw the wide open window--and his chance. Out he went and disappeared, leaving the man cussing at him. A moment's argument followed, then they wrapped Elaine in the blankets alone, still bound and gagged, and carried her out. . . . . . . . . In the secret den, the Clutching Hand was waiting, gazing now and then at his watch, and then at the wounded man before him. In a chair his first assistant sat, watching Dr. Morton. A knock at the door caused them to turn their heads. The crook opened it and in walked the other crooks who had carried off Elaine in the suit of armor. Elaine was now almost conscious, as they sat her down in a chair and partly loosed her bonds and the gag. She gazed about, frightened. "Oh--help! help!" she screamed as she caught sight of the now familiar mask of the Clutching Hand. "Call all you want--here, young lady," he laughed unnaturally. "No one can hear. These walls are soundproof!" Elaine shrank back. "Now, doc.," he added harshly to Dr. Morton. "It was she who shot him. Her blood must save him." Dr. Morton recoiled at the thought of torturing the beautiful young girl before him. "Are--you willing--to have your blood transfused?" he parleyed. "No--no--no!" she cried in horror, Dr. Morton turned to the desperate criminal. "I cannot do it." "The deuce you can't!" A cold steel revolver pressed down on Dr. Morton's stomach. In the other hand the master crook held his watch. "You have just one minute to make up your mind." Dr. Morton shrank back. The revolver followed. The pressure of a fly's foot meant eternity for him. "I--I'll try!" The other crooks next carried Elaine, struggling, and threw her down beside the wounded man. Together they arranged another couch beside him. Dr. Morton, still covered by the gun, bent over the two, the hardened criminal and the delicate, beautiful girl. Clutching Hand glared fiendishly, insanely. From his bag he took a little piece of something that shone like silver. It was in the form of a minute, hollow cylinder, with two grooves on it, a cylinder so tiny that it would scarcely have slipped over the point of a pencil. "A cannulla," he explained, as he prepared to make an incision in Elaine's arm and in the arm of the wounded rogue. He cuffed it over the severed end of the artery, so cleverly that the inner linings of the vein and artery, the endothelium as it is called, were in complete contact with each other. Clutching Hand watched eagerly, as though he had found some new, scientific engine of death in the little hollow cylinder. A moment and the blood that was, perhaps, to save the life of the wounded felon was coursing into his veins from Elaine. A moment later, Dr. Morton looked up at the Clutching Hand and nodded, "Well, it's working!" At Elaine's head, Clutching Hand himself was administering just enough ether to keep her under and prevent a struggle that would wreck all. The wounded man had not been anesthetized and seemed feebly conscious of what was being done to save him. All were now bending over the two. Dr. Morton bent closest over Elaine. He looked at her anxiously, felt her pulse, watched her breathing, then pursed up his lips. "This is--dangerous," he ventured, gazing askance at the grim Clutching Hand. "Can't help it," came back laconically and relentlessly. The doctor shuddered. The man was a veritable vampire! . . . . . . . . Outside the deserted house, Kennedy and I were looking helplessly about. Suddenly Kennedy dashed back and reappeared a minute later with a couple of pieces of armor. He held them down to Rusty and the dog sniffed at them. But Rusty stood still. Kennedy pointed to the ground. Nothing doing. In leading us where he had been before, Rusty had reached the end of his canine ability. Everything we could do to make Rusty understand that we wanted him to follow a trail was unavailing. He simply could not do it. Kennedy coaxed and scolded. Rusty merely sat up on his hind legs and begged with those irresistible brown eyes. "You can't make a bloodhound out of a collie," despaired Craig, looking about again helplessly. Then he reached into his pocket and pulled out a police whistle. He blew three sharp blasts. Would it bring help? . . . . . . . . While we were thus despairing, the continued absence of Dr. Morton from home had alarmed his family and had set in motion another train of events. When he did not return, and could not be located at the place to which he was supposed to have gone, several policemen had been summoned to his house, and they had come, finally, with real bloodhounds from a suburban station. There were the tracks of his car. That the police themselves could follow, while two men came along holding in leash the pack, leaders of which were "Searchlight" and "Bob." It had not been long before the party came across the deserted runabout beside the road. There they had stopped, for a moment. It was just then that they heard Kennedy's call, and one of them had been detailed to answer it. "Well, what do YOU want?" asked the officer, eyeing Kennedy suspiciously as he stood there with the armor. "What's them pieces of tin--hey?" Kennedy quickly flashed his own special badge. "I want to trail a girl," he exclaimed hurriedly. "Can I find a bloodhound about here?" "A hound? Why, we have a pack--over there." "Bring them--quick!" ordered Craig. The policeman, who was an intelligent fellow, saw at once that, as Kennedy said, the two trails probably crossed. He shouted and in a few seconds the others, with the pack, came. A brief parley resulted in our joining forces. Kennedy held the armor down to the dogs. "Searchlight" gave a low whine, then, followed by "Bob" and the others, was off, all with noses close to the ground. We followed. The armor was, after all, the missing link. Through woods and fields the dogs led us. Would we be in time to rescue Elaine? . . . . . . . . In the mysterious haunt of the Clutching Hand, all were still standing around Elaine and the wounded Pitts Slim. Just then a cry from one of the group startled the rest. One of them, less hardened than the Clutching Hand, had turned away from the sight, had gone to the window, and had been attracted by something outside. "Look!" he cried. From the absolute stillness of death, there was now wild excitement among the crooks. "Police! Police!" they shouted to each other as they fled by a doorway to a secret passage. Clutching Hand turned to his first assistant. "You--go--too," he ordered. . . . . . . . . The dogs had led us to a strange looking house, and were now baying and leaping up against the door. We did not stop to knock, but began to break through, for inside we could hear faintly sounds of excitement and cries of "Police--police!" The door yielded and we rushed into a long hallway. Up the passage we went until we came to another door. An instant and we were all against it. It was stout, but it shook before us. The panels began to yield. . . . . . . . . On the other side of that door from us, the master crook stood for a moment. Dr. Morton hesitated, not knowing quite what to do. Just then the wounded Pitts Slim lifted his hand feebly. He seemed vaguely to understand that the game was up. He touched the Clutching Hand. "You did your best, Chief," he murmured thickly. "Beat it, if you can. I'm a goner, anyway." Clutching Hand hesitated by the wounded crook. This was the loyalty of gangland, worthy a better cause. He could not bring himself to desert his pal. He was undecided, still. But there was the door, bulging, and a panel bursting. He moved over to a panel in the wall and pushed a spring. It slid open and he stepped through. Then it closed--not a second too soon. Back in his private room, he quickly stepped to a curtained iron door. Pushing back the curtains, he went through it and disappeared, the curtains falling back. At the end of the passageway, he stopped, in a sort of grotto or cave. As he came out, he looked back. All was still. No one was about. He was safe here, at least! Off came the mask and he turned down the road a few rods distant beyond some bushes, as little concerned about the wild happenings as any other passer-by might have been. . . . . . . . . At the very moment when we burst in, Dr. Morton, seeing his chance, stopped the blood transfusion, working frantically to stop the flow of blood. Kennedy sprang to Elaine's side, horrified by the blood that had spattered over everything. With a mighty effort he checked a blow that he had aimed at Dr. Morton, as it flashed over him that the surgeon, now free again, was doing his best to save the terribly imperilled life of Elaine. Just then the police burst through the secret panel and rushed on, leaving us alone, with the unconscious, scarcely breathing Elaine. From the sounds we could tell that they had come to the private room of the Clutching Hand. It was empty and they were non-plussed. "Not a window!" called one. "What are those curtains?" They pulled them back, disclosing an iron door. They tried it but it was bolted on the other side. Blows had no effect. They had to give it up for the instant. A policeman now stood beside Elaine and the wounded burglar who was muttering deliriously to himself. He was pretty far gone, as the policeman knelt down and tried to get a statement out of him. "Who was that man who left you--last--the Clutching Hand?" Not a word came from the crook. The policeman repeated his question. With his last strength, he looked disdainfully at the officer's pad and pencil. "The gangster never squeals," he snarled, as he fell back. Dr. Morton had paid no attention whatever to him, but was working desperately now over Elaine, trying to bring her back to life. "Is she--going to--die?" gasped Craig, frantically. Every eye was riveted on Dr. Morton. "She is all right," he muttered. "But the man is going to die." At the sound of Craig's voice Elaine had feebly opened her eyes. "Thank heaven," breathed Craig, with a sigh of relief, as his hand gently stroked Elaine's unnaturally cold forehead. CHAPTER VII THE DOUBLE TRAP Mindful of the sage advice that a time of peace is best employed in preparing for war, I was busily engaged in cleaning my automatic gun one morning as Kennedy and I were seated in our living room. Our door buzzer sounded and Kennedy, always alert, jumped up, pushing aside a great pile of papers which had accumulated in the Dodge case. Two steps took him to the wall where the day before he had installed a peculiar box about four by six inches long connected in some way with a lens-like box of similar size above our bell and speaking tube in the hallway below. He opened it, disclosing an oblong plate of ground glass. "I thought the seismograph arrangement was not quite enough after that spring-gun affair," he remarked, "so I have put in a sort of teleview of my own invention--so that I can see down into the vestibule downstairs. Well--just look who's here!" "Some new fandangled periscope arrangement, I suppose?" I queried moving slowly over toward it. However, one look was enough to interest me. I can express it only in slang. There, framed in the little thing, was a vision of as swell a "chicken" as I have ever seen. I whistled under my breath. "Um!" I exclaimed shamelessly, "A peach! Who's your friend?" I had never said a truer word than in my description of her, though I did not know it at the time. She was indeed known as "Gertie the Peach" in the select circle to which she belonged. Gertie was very attractive, though frightfully over-dressed. But, then, no one thinks anything of that now, in New York. Kennedy had opened the lower door and our fair visitor was coming upstairs. Meanwhile he was deeply in thought before the "teleview." He made up his mind quickly, however. "Go in there, Walter," he said, seizing me quickly and pushing me into my room. "I want you to wait there and watch her carefully." I slipped the gun into my pocket and went, just as a knock at the door told me she was outside. Kennedy opened the door, disclosing a very excited young woman. "Oh, Professor Kennedy," she cried, all in one breath, with much emotion, "I'm so glad I found you in. I can't tell you. Oh--my jewels! They have been stolen--and my husband must not know of it. Help me to recover them--please!" She had not paused, but had gone on in a wild, voluble explanation. "Just a moment, my dear young lady," interrupted Craig, finding at last a chance to get a word in edgewise. "Do you see that table--and all those papers? Really, I can't take your case. I am too busy as it is even to take the cases of many of my own clients." "But, please, Professor Kennedy--please!" she begged. "Help me. It means--oh, I can't tell you how much it means to me!" She had come close to him and had laid her warm, little soft hand on his, in ardent entreaty. From my hiding place in my room, I could not help seeing that she was using every charm of her sex and personality to lure him on, as she clung confidingly to him. Craig was very much embarrassed, and I could not help a smile at his discomfiture. Seriously, I should have hated to have been in his position. Gertie had thrown her arms about Kennedy, as if in wildest devotion. I wondered what Elaine would have thought, if she had a picture of that! "Oh," she begged him, "please--please, help me!" Still Kennedy seemed utterly unaffected by her passionate embrace. Carefully he loosened her fingers from about his neck and removed the plump, enticing arms. Gertie sank into a chair, weeping, while Kennedy stood before her a moment in deep abstraction. Finally he seemed to make up his mind to something. His manner toward her changed. He took a step to her side. "I WILL help you," he said, laying his hand on her shoulder. "If it is possible I will recover your jewels. Where do you live?" "At Hazlehurst," she replied, gratefully. "Oh, Mr. Kennedy, how can I ever thank you?" She seemed overcome with gratitude and took his hand, pressed it, even kissed it. "Just a minute," he added, carefully extricating his hand. "I'll be ready in just a minute." Kennedy entered the room where I was listening. "What's it all about, Craig?" I whispered, mystified. For a moment he stood thinking, apparently reconsidering what he had just done. Then his second thought seemed to approve it. "This is a trap of the Clutching Hand, Walter," he whispered, adding tensely, "and we're going to walk right into it." I looked at him in amazement. "But, Craig," I demurred, "that's foolhardy. Have her trailed--anything--but---" He shook his head and with a mere motion of his hand brushed aside my objections as he went to a cabinet across the room. From one shelf he took out a small metal box and from another a test tube, placing the test tube in his waistcoat pocket, and the small box in his coatpocket, with excessive care. Then he turned and motioned to me to follow him out into the other room. I did so, stuffing my "gatt" into my pocket. "Let me introduce my friend, Mr. Jameson," said Craig, presenting me to the pretty crook. The introduction quickly over, we three went out to get Craig's car which he kept at a nearby garage. . . . . . . . . That forenoon, Perry Bennett was reading up a case. In the outer office Milton Schofield, his office boy, was industriously chewing gum and admiring his feet cocked up on the desk before him. The door to the waiting room opened and an attractive woman of perhaps thirty, dressed in extreme mourning, entered with a boy. Milton cast a glance of scorn at the "little dude." He was in reality about fourteen years old but was dressed to look much younger. Milton took his feet down in deference to the lady, but snickered openly at the boy. A fight seemed imminent. "Did you wish to see Mr. Bennett?" asked the precocious Milton politely on one hand while on the other he made a wry grimace. "Yes--here is my card," replied the woman. It was deeply bordered in black. Even Milton was startled at reading it: "Mrs. Taylor Dodge." He looked at the woman in open-mouthed astonishment. Even he knew that Elaine's mother had been dead for years. The woman, however, true to her name in the artistic coterie in which she was leader, had sunk into a chair and was sobbing convulsively, as only "Weepy Mary" could. It was so effective that even Milton was visibly moved. He took the card in, excitedly, to Bennett. "There's a woman outside--says she is Mrs. Dodge!" he cried. If Milton had had an X-ray eye he could have seen her take a cigarette from her handbag and light it nonchalantly the moment he was gone. As for Bennett, Milton, who was watching him closely, thought he was about to discharge him on the spot for bothering him. He took the card, and his face expressed the most extreme surprise, then anger. He thought a moment. "Tell that woman to state her business in writing," he thundered curtly at Milton. As the boy turned to go back to the waiting room, Weepy Mary, hearing him coming, hastily shoved the cigarette into her "son's" hand. "Mr. Bennett says for you to write out what it is you want to see him about," reported Milton, indicating the table before which she was sitting. Mary had automatically taken up sobbing, with the release of the cigarette. She looked at the table on which were letter paper, pens and ink. "I may write here?" she asked. "Surely, ma'am," replied Milton, still very much overwhelmed by her sorrow. Weepy Mary sat there, writing and sobbing. In the midst of his sympathy, however, Milton sniffed. There was an unmistakable odor of tobacco smoke about the room. He looked sharply at the "son" and discovered the still smoking cigarette. It was too much for Milton's outraged dignity. Bennett did not allow him that coveted privilege. This upstart could not usurp it. He reached over and seized the boy by the arm and swung him around till he faced a sign in the corner on the wall. "See?" he demanded. The sign read courteously: "No Smoking in This Office--Please. "PERRY BENNETT." "Leggo my arm," snarled the "son," putting the offending cigarette defiantly into his mouth. Milton coolly and deliberately reached over and, with an exaggerated politeness swiftly and effectively removed it, dropping it on the floor and stamping defiantly on it. "Son" raised his fists pugnaciously, for he didn't care much for the role he was playing, anyhow. Milton did the same. There was every element of a gaudy mix-up, when the outer door of the office suddenly swung open and Elaine Dodge entered. Gallantry was Milton's middle name and he sprang forward to hold the door, and then opened Bennett's door, as he ushered in Elaine. As she passed "Weepy Mary," who was still writing at the table and crying bitterly, Elaine hesitated and looked at her curiously. Even after Milton had opened Bennett's door, she could not resist another glance. Instinctively Elaine seemed to scent trouble. Bennett was still studying the black-bordered card, when she greeted him. "Who is that woman?" she asked, still wondering about the identity of the Niobe outside. At first he said nothing. But finally, seeing that she had noticed it, he handed Elaine the card, reluctantly. Elaine read it with a gasp. The look of surprise that crossed her face was terrible. Before she could say anything, however, Milton had returned with the sheet of paper on which "Weepy Mary" had written and handed it to Bennett. Bennett read it with uncontrolled astonishment. "What is it?" demanded Elaine. He handed it to her and she read: "As the lawful wife and widow of Taylor Dodge, I demand my son's rights and my own. "MRS. TAYLOR DODGE." Elaine gasped at it. "She--my father's wife!" she exclaimed, "What effrontery! What does she mean?" Bennett hesitated. "Tell me," Elaine cried, "Is there--can there be anything in it? No--no--there isn't!" Bennett spoke in a low tone. "I have heard a whisper of some scandal or other connected with your father--but--" He paused. Elaine was first shocked, then indignant. "Why--such a thing is absurd. Show the woman in!" "No--please--Miss Dodge. Let me deal with her." By this time Elaine was furious. "Yes--I WILL see her." She pressed the button on Bennett's desk and Milton responded. "Milton, show the--the woman in," she ordered, "and that boy, too." As Milton turned to crook his finger at "Weepy Mary," she nodded surreptitiously and dug her fingers sharply into "son's" ribs. "Yell--you little fool,--yell," she whispered. Obedient to his "mother's" commands, and much to Milton's disgust, the boy started to cry in close imitation of his elder. Elaine was still holding the paper in her hands when they entered. "What does all this mean?" she demanded. "Weepy Mary," between sobs, managed to blurt out, "You are Miss Elaine Dodge, aren't you? Well, it means that your father married me when I was only seventeen and this boy is his son--your half brother." "No--never," cried Elaine vehemently, unable to restrain her disgust. "He never married again. He was too devoted to the memory of my mother." "Weepy Mary" smiled cynically. "Come with me and I will show you the church records and the minister who married us." "You will?" repeated Elaine defiantly. "Well, I'll just do as you ask. Mr. Bennett shall go with me." "No, no, Miss Dodge--don't go. Leave the matter to me," urged Bennett. "I will take care of HER. Besides, I must be in court in twenty minutes." Elaine paused, but she was thoroughly aroused. "Then I will go with her myself," she cried defiantly. In spite of every objection that Bennett made, "Weepy Mary," her son, and Elaine went out to call a taxicab to take them to the railroad station where they could catch a train to the little town where the woman asserted she had been married. . . . . . . . . Meanwhile, before a little country church in the town, a closed automobile had drawn up. As the door opened, a figure, humped up and masked, alighted. It was the Clutching Hand. The car had scarcely pulled away, when he gave a long rap, followed by two short taps, at the door of the vestry, a secret code, evidently. Inside the vestry room a well-dressed man but with a very sinister face heard the knock and a second later opened the door. "What--not ready yet?" growled the Clutching Hand. "Quick--now--get on those clothes. I heard the train whistle as I came in the car. In which closet does the minister keep them?" The crook, without a word, went to a closet and took out a suit of clothes of ministerial cut. Then he hastily put them on, adding some side-whiskers, which he had brought with him. At about the same time, Elaine, accompanied by "Weepy Mary" and her "son," had arrived at the little tumble-down station and had taken the only vehicle in sight, a very ancient carriage. It ambled along until, at last, it pulled up before the vestry room door of the church, just as the bogus minister was finishing his transformation from a frank crook. Clutching Hand was giving him final instructions. Elaine and the others alighted and approached the church, while the ancient vehicle rattled away. "They're coming," whispered the crook, peering cautiously out of the window. Clutching Hand moved silently and snake-like into the closet and shut the door. "How do you do, Dr. Carton?" greeted "Weepy Mary." "I guess you don't remember me." The clerical gentleman looked at her fixedly a moment. "Remember you?" he repeated. "Of course, my dear. I remember everyone I marry." "And you remember to whom you married me?" "Perfectly. To an older man--a Taylor Dodge." Elaine was overcome. "Won't you step in?" he asked suavely. "Your friend here doesn't seem well." They all entered. "And you--you say--you married this--this woman to Taylor Dodge?" queried Elaine, tensely. The bogus minister seemed to be very fatherly. "Yes," he assented, "I certainly did so." "Have you the record?" asked Elaine, fighting to the last. "Why, yes. I can show you the record." He moved over to the closet. "Come over here," he asked. He opened the door. Elaine screamed and drew back. There stood her arch enemy, the Clutching Hand himself. As he stepped forth, she turned, wildly, to run--anywhere. But strong arms seized her and forced her into a chair. She looked at the woman and the minister. It was a plot! A moment Clutching Hand looked Elaine over. "Put the others out," he ordered the other crook. Quickly the man obeyed, leading "Weepy Mary" and her "son" to the door, and waving them away as he locked it. They left, quite as much in the dark about the master criminal's identity as Elaine. "Now, my pretty dear," began the Clutching Hand as the lock turned in the vestry door, "we shall be joined shortly by your friend, Craig Kennedy, and," he added with a leer, "I think your rather insistent search for a certain person will cease." Elaine drew back in the chair, horrified, at the implied threat. Clutching Hand laughed, diabolically. . . . . . . . . While these astounding events were transpiring in the little church, Kennedy and I had been tearing across the country in his big car, following the directions of our fair friend. We stopped at last before a prosperous, attractive-looking house and entered a very prettily furnished but small parlor. Heavy portieres hung over the doorway into the hall, over another into a back room and over the bay windows. "Won't you sit down a moment?" coaxed Gertie. "I'm quite blown to pieces after that ride. My, how you drive!" As she pulled aside the hall portieres, three men with guns thrust their hands out. I turned. Two others had stepped from the back room and two more from the bay window. We were surrounded. Seven guns were aimed at us with deadly precision. "No--no--Walter--it's no use," shouted Kennedy calmly restraining my hand which I had clapped on my own gun. At the same time, with his other hand, he took from his pocket the small can which I had seen him place there, and held it aloft. "Gentlemen," he said quietly. "I suspected some such thing. I have here a small box of fulminate of mercury. If I drop it, this building and the entire vicinity will be blown to atoms. Go ahead--shoot!" he added, nonchalantly. The seven of them drew back, rather hurriedly. Kennedy was a dangerous prisoner. He calmly sat down in an arm chair, leaning back as he carefully balanced the deadly little box of fulminate of mercury on his knee. He placed his finger tips together and smiled at the seven crooks, who had gathered together, staring breathlessly at this man who toyed with death. Gertie ran from the room. For a moment they looked at each other, undecided, then one by one, they stepped away from Kennedy toward the door. The leader was the last to go. He had scarcely taken a step. "Stop!" ordered Kennedy. The crook did so. As Craig moved toward him, he waited, cold sweat breaking out on his face. "Say," he whined, "you let me be!" It was ineffectual. Kennedy, still smiling confidently, came closer, still holding the deadly little box, balanced between two fingers. He took the crook's gun and dropped it into his pocket. "Sit down!" ordered Craig. Outside, the other six parleyed in hoarse whispers. One raised a gun, but the woman and the others restrained him and fled. "Take me to your master!" demanded Kennedy. The crook remained silent. "Where is he?" repeated Craig. "Tell me!" Still the man remained silent. Craig looked the fellow over again. Then, still with that confident smile, he reached into his inside pocket and drew forth the tube I had seen him place there. "No matter how much YOU accuse me," added Craig casually, "no one will ever take the word of a crook that a reputable scientist like me would do what I am about to do." He had taken out his penknife and opened it. Then he beckoned to me. "Bare his arm and hold his wrist, Walter," he said. Craig bent down with the knife and the tube, then paused a moment and turned the tube so that we could see it. On the label were the ominous words: Germ culture 6248A Bacillus Leprae (Leprosy) Calmly he took the knife and proceeded to make an incision in the man's arm. The crook's feelings underwent a terrific struggle. "No--no--no--don't," he implored. "I will take you to the Clutching Hand--even if it kills me!" Kennedy stepped back, replacing the tube in his pocket. "Very well, go ahead!" he agreed. We followed the crook, Craig still holding the deadly box of fulminate of mercury carefully balanced so that if anyone shot him from a hiding place it would drop. . . . . . . . . No sooner had we gone than Gertie hurried to the nearest telephone to inform the Clutching Hand of our escape. Elaine had sunk back into the chair, as the telephone rang. Clutching Hand answered it. A moment later, in uncontrollable fury he hurled the instrument to the floor. "Here--we've got to act quickly--that devil has escaped again," he hissed. "We must get her away. You keep her here. I'll be back--right away--with a car." He dashed madly from the church, pulling off his mask as he gained the street. . . . . . . . . Kennedy had forced the crook ahead of us into the car which was waiting and I followed, taking the wheel this time. "Which way, now--quick!" demanded Craig, "And if you get me in wrong--I've got that tube yet--you remember." Our crook started off with a whole burst of directions that rivalled the motor guide--"through the town, following trolley tracks, jog right, jog left under the R. R. bridge, leaving trolley tracks; at cemetery turn left, stopping at the old stone church." "Is this it?" asked Craig incredulously. "Yes--as I live," swore the crook in a cowed voice. He had gone to pieces. Kennedy jumped from the machine. "Here, take this gun, Walter," he said to me. "Don't take your eyes off the fellow--keep him covered." Craig walked around the church, out of sight, until he came to a small vestry window and looked in. There was Elaine, sitting in a chair, and near her stood an elderly looking man in clerical garb, which to Craig's trained eye was quite evidently a disguise. Elaine happened just then to glance at the window and her eyes grew wide with astonishment at the sight of Craig. He made a hasty motion to her to make a dash for the door. She nodded quietly. With a glance at her guardian, she suddenly made a rush. He was at her in a moment, pouncing on her, cat-like. Kennedy had seized an iron bar that lay beside the window where some workmen had been repairing the stone pavement, and, with a blow shattered the glass and the sash. At the sound of the smashing glass the crook turned and with a mighty effort threw Elaine aside, drawing his revolver. As he raised it, Elaine sprang at him and frantically seized his wrist. Utterly merciless, the man brought the butt of the gun down with full force on Elaine's head. Only her hat and hair saved her, but she sank unconscious. Then he turned at Craig and fired twice. One shot grazed Craig's hat, but the other struck him in the shoulder and Kennedy reeled. With a desperate effort he pulled himself together and leaped forward again, closing with the fellow and wrenching the gun from him before he could fire again. It fell to the floor with a clang. Just then the man broke away and made a dash for the door leading back into the church itself, with Kennedy after him. At the foot of a flight of stairs, he turned long enough to pick up a chair. As Kennedy came on, he deliberately smashed it over Craig's head. Kennedy warded off the blow as best he could, then, still undaunted, started up the stairs after the fellow. Up they went, into the choir loft and then into the belfry itself. There they came to sheer hand to hand struggle. Kennedy tripped on a loose board and would have fallen backwards, if he had not been able to recover himself just in time. The crook, desperate, leaped for the ladder leading further up into the steeple. Kennedy followed. Elaine had recovered consciousness almost immediately and, hearing the commotion, stirred and started to rise and look about. From the church she could hear sounds of the struggle. She paused just long enough to seize the crook's revolver lying on the floor. She hurried into the church and up into the belfry, thence up the ladder, whence the sounds came. The crook by this time had gained the outside of the steeple through an opening. Kennedy was in close pursuit. On the top of the steeple was a great gilded cross, considerably larger than a man. As the crook clambered outside, he scaled the steeple, using a lightning rod and some projecting points to pull himself up, desperately. Kennedy followed unhesitatingly. There they were, struggling in deadly combat, clinging to the gilded cross. The first I knew of it was a horrified gasp from my own crook. I looked up carefully, fearing it was a stall to get me off my guard. There were Kennedy and the other crook, struggling, swaying back and forth, between life and death. I looked at my man. What should I do? Should I leave him and go to Craig? If I did, might he not pick us both off, from a safe vantage point, by some sharp-shooting skill? There was nothing I could do. Kennedy was clinging to a lightning rod on the cross. It broke. I gasped as Craig reeled back. But he managed to catch hold of the rod further down and cling to it. The crook seemed to exult diabolically. Holding with both hands to the cross, he let himself out to his full length and stamped on Kennedy's fingers, trying every way to dislodge him. It was all Kennedy could do to keep his hold. I cried out in agony at the sight, for he had dislodged one of Craig's hands. The other could not hold on much longer. He was about to fall. Just then I saw a face at the little window opening out from the ladder to the outside of the steeple--a woman's face, tense with horror. It was Elaine! Quickly a hand followed and in it was a revolver. Just as the crook was about to dislodge Kennedy's other hand, I saw a flash and a puff of smoke and a second later, heard a report--and another--and another. Horrors! The crook who had taken refuge seemed to stagger back, wildly, taking a couple of steps in the thin air. Kennedy regained his hold. With a sickening thud, the body of the crook landed on the ground around the corner of the church from me. "Come--you!" I ground out, covering my own crook with the pistol, "and if you attempt a getaway, I'll kill you, too!" He followed, trembling, unnerved. We bent over the man. It seemed that every bone in his body must be broken. He groaned, and before I could even attempt anything for him, he was dead. . . . . . . . . As Kennedy let himself slowly and painfully down the lightning rod, Elaine seized him and, with all her strength, pulled him in through the window. He was quite weak now from loss of blood. "Are you--all right?" she gasped, as they reached the foot of the ladder in the belfry. Craig looked down at his torn and soiled clothes. Then, in spite of the smarting pain of his wounds, he smiled, "Yes--all right!" "Thank heaven!" she murmured fervently, trying to staunch the flow of blood. Craig gazed at her eagerly. The great look of relief in her face seemed to take away all the pain from his own face. In its place came a look of wonder--and hope. He could not resist. "This time--it was you--saved me!" he cried, "Elaine!" Involuntarily his arms sought hers--and he held her a moment, looking deep into her wonderful eyes. Then their faces came slowly together in their first kiss. CHAPTER VIII THE HIDDEN VOICE "Jameson--wake up!" The strain of the Dodge case was beginning to tell on me, for it was keeping us at work at all kinds of hours to circumvent the Clutching Hand, by far the cleverest criminal with whom Kennedy had ever had anything to do. I had slept later than usual that morning and, in a half doze, I heard a voice calling me, strangely like Kennedy's and yet unlike it. I leaped out of bed, still in my pajamas, and stood for a moment staring about. Then I ran into the living room. I looked about, rubbing my eyes, startled. No one was there. "Hey--Jameson--wake up!" It was spooky. I ran back into Craig's room. He was gone. There was no one in any of our rooms. The surprise had now thoroughly awakened me. "Where--the deuce--are you?" I demanded. Suddenly I heard the voice again--no doubt about it, either. "Here I am--over on the couch!" I scratched my head, puzzled. There was certainly no one on that couch. A laugh greeted me. Plainly, though, it came from the couch. I went over to it and, ridiculous as it seemed, began to throw aside the pillows. There lay nothing but a little oblong oaken box, perhaps eight or ten inches long and three or four inches square at the ends. In the face were two peculiar square holes and from the top projected a black disc, about the size of a watch, fastened on a swinging metal arm. In the face of the disc were several perforated holes. I picked up the strange looking thing in wonder and from that magic oak box actually came a burst of laughter. "Come over to the laboratory, right away," pealed forth a merry voice. "I've something to show you." "Well," I gasped, "what do you know about that?" Very early that morning Craig had got up, leaving me snoring. Cases never wearied him. He thrived on excitement. He had gone over to the laboratory and set to work in a corner over another of those peculiar boxes, exactly like that which he had already left in our rooms. In the face of each of these boxes, as I have said, were two square holes. The sides of these holes converged inward into the box, in the manner of a four sided pyramid, ending at the apex in a little circle of black, perhaps half an inch across. Satisfied at last with his work, Craig had stood back from the weird apparatus and shouted my name. He had enjoyed my surprise to the fullest extent, then had asked me to join him. Half an hour afterward I walked into the laboratory, feeling a little sheepish over the practical joke, but none the less curious to find out all about it. "What is it?" I asked indicating the apparatus. "A vocaphone," he replied, still laughing, "the loud speaking telephone, the little box that hears and talks. It talks right out in meeting, too--no transmitter to hold to the mouth, no receiver to hold to the ear. You see, this transmitter is so sensitive that it picks up even a whisper, and the receiver is placed back of those two megaphone-like pyramids." He was standing at a table, carefully packing up one of the vocaphones and a lot of wire. "I believe the Clutching Hand has been shadowing the Dodge house," he continued thoughtfully. "As long as we watch the place, too, he will do nothing. But if we should seem, ostentatiously, not to be watching, perhaps he may try something, and we may be able to get a clue to his identity over this vocaphone. See?" I nodded. "We've got to run him down somehow," I agreed. "Yes," he said, taking his coat and hat. "I am going to connect up one of these things in Miss Dodge's library and arrange with the telephone company for a clear wire so that we can listen in here, where that fellow will never suspect." . . . . . . . . At about the same time that Craig and I sallied forth on this new mission, Elaine was arranging some flowers on a stand near the corner of the Dodge library where the secret panel was in which her father had hidden the papers for the possession of which the Clutching Hand had murdered him. They did not disclose his identity, we knew, but they did give directions to at least one of his hang-outs and were therefore very important. She had moved away from the table, but, as she did so, her dress caught in something in the woodwork. She tried to loosen it and in so doing touched the little metallic spring on which her dress had caught. Instantly, to her utter surprise, the panel moved. It slid open, disclosing a strong box. Elaine took it amazed, looked at it a moment, then carried it to a table and started to pry it open. It was one of those tin dispatch boxes which, as far as I have ever been able to determine, are chiefly valuable for allowing one to place a lot of stuff in a receptacle which is very convenient for a criminal. She had no trouble in opening it. Inside were some papers, sealed in an envelope and marked "Limpy Red Correspondence." "They must be the Clutching Hand papers!" she exclaimed to herself, hesitating a moment in doubt what to do. The fatal documents seemed almost uncanny. Their very presence frightened her. What should she do? She seized the telephone and eagerly called Kennedy's number. "Hello," answered a voice. "Is that you, Craig?" she asked excitedly. "No, this is Mr. Jameson." "Oh, Mr. Jameson, I've discovered the Clutching Hand papers," she began, more and more excited. "Have you read them?" came back the voice quickly. "No--shall I?" "Then don't unseal them," cautioned the voice. "Put them back exactly as you found them and I'll tell Mr. Kennedy the moment I can get hold of him." "All right," nodded Elaine. "I'll do that. And please get him--as soon as you possibly can." "I will." "I'm going out shopping now," she returned, suddenly. "But, tell him I'll be back--right away." "Very well." Hanging up the receiver, Elaine dutifully replaced the papers in the box and returned the box to its secret hiding place, pressing the spring and sliding the panel shut. A few minutes later she left the house in the Dodge car. . . . . . . . . Outside our laboratory, leaning up against a railing, Dan the Dude, an emissary of the Clutching Hand, whose dress now greatly belied his underworld "monniker," had been shadowing us, watching to see when we left. The moment we disappeared, he raised his hand carefully above his head and made the sign of the Clutching Hand. Far down the street, in a closed car, the Clutching Hand himself, his face masked, gave an answering sign. A moment later he left the car, gazing about stealthily. Not a soul was in sight and he managed to make his way to the door of our laboratory without being observed. Then he opened it with a pass key which he must have obtained in some way by working the janitor or the university officials. Probably he thought that the papers might be at the laboratory, for he had repeatedly failed to locate them at the Dodge house. At any rate he was busily engaged in ransacking drawers and cabinets in the laboratory, when the telephone suddenly rang. He did not want to answer it, but if it kept on ringing someone outside might come in. An instant he hesitated. Then, disguising his voice as much as he could to imitate mine, he took off the receiver. "Hello!" he answered. His face was a study in all that was dark as he realized that it was Elaine calling. He clenched his crooked hand even more viciously. "Have you read them?" he asked, curbing his impatience as she unsuspectingly poured forth her story, supposedly to me. "Then don't unseal them," he hastened to reply. "Put them back. Then there can be no question about them. You can open them before witnesses." For a moment he paused, then added, "Put them back and tell no one of their discovery. I will tell Mr. Kennedy the moment I can get him." A smile spread over his sinister face as Elaine confided in him her intention to go shopping. "A rather expensive expedition for you, young lady," he muttered to himself as he returned the receiver to the hook. Clutching Hand lost no further time at the laboratory. He had thus, luckily for him, found out what he wanted. The papers were not there after all, but at the Dodge house. Suppose she should really be gone on only a short shopping trip and should return to find that she had been fooled over the wire? Quickly, he went to the telephone again. "Hello, Dan," he called when he got his number. "Miss Dodge is going shopping. I want you and the other Falsers to follow her--delay her all you can. Use your own judgment." It was what had come to be known in his organization as the "Brotherhood of Falsers." There, in the back room of a low dive, were Dan the Dude, the emissary who had been loitering about the laboratory, a gunman, Dago Mike, a couple of women, slatterns, one known as Kitty the Hawk, and a boy of eight or ten, whom they called Billy. Before them stood large schooners of beer, while the precocious youngster grumbled over milk. "All right, Chief," shouted back Dan, their leader as he hung up the telephone after noting carefully the hasty instructions. "We'll do it--trust us." The others, knowing that a job was to lighten the monotony of existence, gathered about him. They listened intently as he detailed to them the orders of the Clutching Hand, hastily planning out the campaign like a division commander disposing his forces in battle and assigning each his part. With alacrity the Brotherhood went their separate ways. . . . . . . . . Elaine had not been gone long from the house when Craig and I arrived there. She had followed the telephone instructions of the Clutching Hand and had told no one. "Too bad," greeted Jennings, "but Miss Elaine has just gone shopping and I don't know when she'll be back." Shopping being an uncertain element as far as time was concerned, Kennedy asked if anyone else was at home. "Mrs. Dodge is in the library reading, sir," replied Jennings, taking it for granted that we would see her. Aunt Josephine greeted us cordially and Craig set down the vocaphone package he was carrying. She nodded to Jennings to leave us and he withdrew. "I'm not going to let anything happen here to Miss Elaine again if I can help it," remarked Craig in a low tone, a moment later, gazing about the library. "What are you thinking of doing?" asked Aunt Josephine keenly. "I'm going to put in a vocaphone," he returned unwrapping it. "What's that?" she asked. "A loud speaking telephone--connected with my laboratory," he explained, repeating what he had already told me, while she listened almost awe-struck at the latest scientific wonder. He was looking about, trying to figure out just where it could be placed to best advantage, when he approached the suit of armor. "I see you have brought it back and had it repaired," he remarked to Aunt Josephine. Suddenly his face lighted up. "Ah--an idea!" he exclaimed. "No one will ever think to look INSIDE that." It was indeed an inspiration. Kennedy worked quickly now, placing the little box inside the breast plate of the ancient armourer with the top of the instrument projecting right up into the helmet. It was a strange combination--the medieval and the ultra-modern. "Now, Mrs. Dodge," he said finally, as he had completed installing the thing and hiding the wire under carpets and rugs until it ran out to the connection which he made with the telephone, "don't breathe a word of it--to anyone. We don't know who to trust or suspect." "I shall not," she answered, by this time thoroughly educated in the value of silence. Kennedy looked at his watch. "I've got an engagement with the telephone company, now," he said rather briskly, although I knew that if Elaine had been there the company and everything could have gone hang for the present. "Sorry not to have seen Miss Elaine," he added as we bowed ourselves out, "but I think we've got her protected now." "I hope so," sighed her aunt. . . . . . . . . Elaine's car had stopped finally at a shop on Fifth Avenue. She stepped out and entered, leaving her chauffeur to wait. As she did so, Dan and Billy sidled along the crowded sidewalk. "There she is, Billy," pointed out Dan as Elaine disappeared through the swinging doors of the shop. "Now, you wait right here," he instructed stealthily, "and when she comes out--you know what to do. Only, be careful." Dan the Dude left Billy, and Billy surreptitiously drew from under his coat a dirty half loaf of bread. With a glance about, he dropped it into the gutter close to the entrance to Elaine's car. Then he withdrew a little distance. When Elaine came out and approached her car, Billy, looking as cold and forlorn as could be, shot forward. Pretending to spy the dirty piece of bread in the gutter, he made a dive for it, just as Elaine was about to step into the car. Elaine, surprised, drew back. Billy picked up the piece of bread and, with all the actions of having discovered a treasure, began to gnaw at it voraciously. Shocked at the disgusting sight, she tried to take the bread away from him. "I know it's dirty, Miss," whimpered Billy, "but it's the first food I've seen for four days." Instantly Elaine was full of sympathy. She had taken the food away. That would not suffice. "What's your name, little boy?" she asked. "Billy," he replied, blubbering. "Where do you live?" "With me mother and father--they're sick--nothing to eat--" He was whimpering an address far over on the East Side. "Get into the car," Elaine directed. "Gee--but this is swell," he cried, with no fake, this time. On they went, through the tenement canyons, dodging children and pushcarts, stopping first at a grocer's, then at a butcher's and a delicatessen. Finally the car stopped where Billy directed. Billy hobbled out, followed by Elaine and her chauffeur, his arms piled high with provisions. She was indeed a lovely Lady Bountiful as a crowd of kids quickly surrounded the car. In the meantime Dago Mike and Kitty the Hawk had gone to a wretched flat, before which Billy stopped. Kitty sat on the bed, putting dark circles under her eyes with a blackened cork. She was very thin and emaciated, but it was dissipation that had done it. Dago Mike was correspondingly poorly dressed. He had paused beside the window to look out. "She's coming," he announced finally. Kitty hastily jumped into the rickety bed, while Mike took up a crutch that was standing idly in a corner. She coughed resignedly and he limped about, forlorn. They had assumed their parts which were almost to the burlesque of poverty, when the door was pushed open and Billy burst in followed by Elaine and the chauffeur. "Oh, ma--oh, pa," he cried running forward and kissing his pseudo-parents, as Elaine, overcome with sympathy, directed the chauffeur to lay the things on a shaky table. "God bless you, lady, for a benevolent angel!" muttered the pair, to which Elaine responded by moving over to the wretched bed and bending down to stroke the forehead of the sick woman. Billy and Mike exchanged a sly wink. Just then the door opened again. All were genuinely surprised this time, for a prim, spick and span, middle-aged woman entered. "I am Miss Statistix, of the organized charities," she announced, looking around sharply. "I saw your car standing outside, Miss, and the children below told me you were up here. I came up to see whether you were aiding really DESERVING poor." She laid a marked emphasis on the word, pursing up her lips. There was no mistaking the apprehension that these fine birds of prey had of her, either. Miss Statistix took a step forward, looking in a very superior manner from Elaine to the packages of food and then at these prize members of the Brotherhood. She snorted contemptuously. "Why--wh-what's the matter?" asked Elaine, fidgeting uncomfortably, as if she were herself guilty, in the icy atmosphere that now seemed to envelope all things. "This man is a gunman, that woman is a bad woman, the boy is Billy the Bread-Snatcher," she answered precisely, drawing out a card on which to record something, "and you, Miss, are a fool!" "Ya!" snarled the two precious falsers, "get out o' here!" There was no combating Miss Statistix. She overwhelmed all arguments by the very exactness of her personality. "YOU get out!" she countered. Kitty and Mike, accompanied by Billy, sneaked out. Elaine, now very much embarrassed, looked about, wondering at the rapid-fire change. Miss Statistix smiled pityingly. "Such innocence!" she murmured sadly shaking her head as she lead Elaine to the door. "Don't you know better than to try to help anybody without INVESTIGATING?" Elaine departed, speechless, properly squelched, followed by her chauffeur. . . . . . . . . Meanwhile, a closed car, such as had stood across from the laboratory, had drawn up not far from the Dodge house. Near it was a man in rather shabby clothes and a visored cap on which were the words in dull gold lettering, "Metropolitan Window Cleaning Co." He carried a bucket and a small extension ladder. In the darkened recesses of the car was the Clutching Hand himself, masked as usual. He had his watch in his hand and was giving most minute instructions to the window cleaner about something. As the latter turned to go, a sharp observer would have noted that it was Dan the Dude, still further disguised. A few moments later, Dan appeared at the servants' entrance of the Dodge house and rang the bell. Jennings, who happened to be down there, came to the door. "Man to clean the windows," saluted the bogus cleaner, touching his hat in a way quietly to call attention to the words on it and drawing from his pocket a faked written order. "All right," nodded Jennings examining the order and finding it apparently all right. Dan followed him in, taking the ladder and bucket upstairs, where Aunt Josephine was still reading. "The man to clean the windows, ma'am," apologized Jennings. "Oh, very well," she nodded, taking up her book, to go. Then, recalling the frequent injunctions of Kennedy, she paused long enough to speak quietly to Jennings. "Stay here and watch him," she whispered as she went out. Jennings nodded, while Dan opened a window and set to work. . . . . . . . . Elaine had scarcely started again in her car down the crowded narrow street. From her position she could not possibly have seen Johnnie, another of the Brotherhood, watching her eagerly up the street. But as her car approached, Johnnie, with great determination, pulled himself together and ran forward across the street. She saw that. "Oh!" she screamed, her heart almost stopping. He had fallen directly in front of the wheels of the car, apparently, and although the chauffeur stopped with a jolt, it seemed that the boy had been run over. They jumped out. There he was, sure enough, under the very wheels. People came running now in all directions and lifted him up, groaning piteously. He seemed literally twisted into a knot which looked as if every bone in his body was broken or dislocated. Elaine was overcome. For, following their natural instincts the crowd began pushing in with cries of "Lynch the driver!" It would have gone hard with him, too, if she had not interfered. "Here!" cried Elaine, stepping in. "It wasn't his fault. The boy ran across the street right in front of the car. Now--we're just going to rush this boy to the hospital--right away!" She lifted Johnnie gently into the car herself and they drove off, to a very vigorous blowing of the horn. A few moments later they pulled up before the ambulance entrance to the hospital. "Quick!" beckoned Elaine to the attendants, who ran out and carried Johnnie, still a complicated knot of broken bones, inside. In the reception room were a couple of nurses and a young medical student, when Johnnie was carried in and laid on the bed. The student, more interested in Elaine than the boy, examined him. His face wore a puzzled look and there was every reason to believe that Johnnie was seriously injured. At that moment the door opened and an elderly, gray-bearded house physician entered. The others stepped back from the bed respectfully. He advanced and examined Johnnie. The doctor looked at the boy a moment, then at Elaine. "I will now effect a miraculous cure by the laying on of hands," he announced, adding quickly, "--and of feet!" To the utter surprise of all he seized the boy by the coat collar, lifting him up and actually bouncing him on the floor. Then he picked him up, shook him and ran him out of the room, delivering one last kick as he went through the door. By the way Johnnie went, it was quite evident that he was no more injured than the chauffeur. Elaine did not know whether to be angry or to laugh, but finally joined in the general laugh. "That was Double-Jointed Johnnie," puffed the doctor, as he returned to them, "one of the greatest accident fakers in the city." Elaine, having had two unfortunate experiences during the day, now decided to go home and the doctor politely escorted her to her car. . . . . . . . . From his closed car, the Clutching Hand gazed intently at the Dodge house. He could see Dan on the ladder, now washing the library window, his back toward him. Dan turned slowly and made the sign of the hand. Turning to his chauffeur, the master criminal spoke a few words in a low tone and the driver hurried off. A few minutes later the driver might have been seen entering a near-by drug store and going into the telephone booth. Without a moment's hesitation he called up the Dodge house and Marie, Elaine's maid, answered. "Is Jennings there?" he asked. "Tell him a friend wants to speak to him." "Wait a minute," she answered. "I'll get him." Marie went toward the library, leaving the telephone off the hook. Dan was washing the windows, half inside, half outside the house, while Jennings was trying to be very busy, although it was apparent that he was watching Dan closely. "A friend of yours wants to speak to you over the telephone, Jennings," said Marie, as she came into the library. The butler responded slowly, with a covert glance at Dan. No sooner had they gone, however, than Dan climbed all the way into the room, ran to the door and looked after them. Then he ran to the window. Across and down the street, the Clutching Hand was gazing at the house. He had seen Dan disappear and suspected that the time had come. Sure enough, there was the sign of the hand. He hastily got out of the car and hurried up the street. All this time the chauffeur was keeping Jennings busy over the telephone with some trumped-up story. As the master criminal came in by the ladder through the open window, Dan was on guard, listening down the hallway. A signal from Dan, and Clutching Hand slid back of the portieres. Jennings was returning. "I've finished these windows," announced Dan as the butler reappeared. "Now, I'll clean the hall windows." Jennings followed like a shadow, taking the bucket. No sooner had they gone than Clutching Hand stealthily came from behind the portieres. One of the maids was sweeping in the hall as Dan went toward the window, about to wash it. "I wonder whether I locked these windows?" muttered Jennings, pausing in the hallway. "I guess I'd better make sure." He had taken only a step toward the library again, when Dan watchfully caught sight of him. It would never do to have Jennings snooping around there now. Quick action was necessary. Dan knocked over a costly Sevres vase. "There--clumsy--see what you've done!" berated Jennings, starting to pick up the pieces. Dan had acted his part well and promptly. In the library, Clutching Hand was busily engaged at that moment beside the secret panel searching for the spring that released it. He ran his finger along the woodwork, pausing here and there without succeeding. "Confound it!" he muttered, searching feverishly. . . . . . . . . Kennedy, having made the arrangements with the telephone company by which he had a clear wire from the Dodge house to his laboratory, had rejoined me there and was putting on the finishing touches to his installation of the vocaphone. Every now and then he would switch it on, and we would listen in as he demonstrated the wonderful little instrument to me. He had heard the window cleaner and Jennings, but thought nothing of it at the time. Once, however, Craig paused and I saw him listening more intently than usual. "They've gone out," he muttered, "but surely there is someone in the Dodge library." I listened; too. The thing was so sensitive that even a whisper could be magnified and I certainly did hear something. Kennedy frowned. What was that scratching noise? Could it be Jennings? Perhaps it was Rusty. Just then we could distinguish a sound as though someone had moved about. "No--that's not Jennings," cried Craig. "He went out." He looked at me a moment. The same stealthy noise was repeated. "It's the Clutching Hand!" he exclaimed excitedly. . . . . . . . . A moment later, Dan hurried into the Dodge library. "For heaven's sake, Chief, hurry!" he whispered hoarsely. "The falsers must have fallen down. The girl herself is coming!" Dan himself had no time to waste. He retreated into the hallway just as Jennings was opening the door for Elaine. Marie took her wraps and left her, while Elaine handed her numerous packages to Jennings. Dan watched every motion. "Put them away, Jennings," she said softly. Jennings had obeyed and gone upstairs. Elaine moved toward the library. Dan took a quiet step or two behind her, in the same direction. In the library, Clutching Hand was now frantically searching for the spring. He heard Elaine coming and dodged behind the curtains again just as she entered. With a hasty look about, she saw no one. Then she went quickly to the panel, found the spring, and pressed it. So many queer things had happened to her since she went out that she had begun to worry over the safety of the papers. The panel opened. They were there, all right. She opened the box and took them out, hesitating to break the seal before Kennedy arrived. Stealthy and tiger-like the Clutching Hand crept up behind her. As he did so, Dan gazed in through the portieres from the hall. With a spring, Clutching Hand leaped at Elaine, snatching at the papers. Elaine clung to them tenaciously in spite of the surprise, and they struggled for them, Clutching Hand holding one hand over her mouth to prevent her screaming. Instantly Dan was there, aiding his chief. "Choke her! Strangle her! Don't let her scream!" he ground out. They fought viciously. Would they succeed? It was two desperate, unscrupulous men against one frail girl. Suddenly, from the man in armor in the corner, as if by a miracle came a deep, loud voice. "Help! Help! Murder! Police! They are strangling me!" The effect was terrific. Clutching Hand and Dan, hardened in crime as they were, fell back, dazed, overcome for the moment at the startling effect. They looked about. Not a soul. Then to their utter consternation, from the vizor of the helmet again came the deep, vibrating warning. "Help! Murder! Police!" . . . . . . . . Kennedy and I had been listening over the vocaphone, for the moment non-plussed at the fellow's daring. Then we heard from the uncanny instrument, "For Heaven's sake, Chief, hurry! The falsers have fallen down. The girl herself is coming!" What it meant we did not know. But Craig was almost beside himself, as he ordered me to try to get the police by telephone, if there was any way to block them. Only instant action would count, however. What to do? He could hear the master criminal plainly fumbling, now. "Yes, that's the Clutching Hand," he repeated. "Wait," I cautioned, "someone else is coming!" By a sort of instinct he seemed to recognize the sounds. "Elaine!" he exclaimed, paling. Instantly followed, in less time than I can tell it, the sounds of a suppressed scuffle. "He has seized her--gagged her," I cried in an agony of suspense. We could now hear everything that was going on in the library. Craig was wildly excited. As for me, I was speechless. Here was the vocaphone we had installed. It had warned us. But what could we do? I looked blankly at Kennedy. He was equal to the emergency. He calmly turned a switch. Then, at the top of his lungs, he shouted, "Help! Help! Police! They are strangling me!" I looked at him in amazement. What did he think he could do--blocks away? "It works both ways," he muttered. "Help! Murder! Police!" We could hear the astounded cursing of the two men. Also, down the hall, now, we could hear footsteps approaching in answer to his call for help--Aunt Josephine, Jennings, Marie, and others, all shouting out that there were cries in the library. "The deuce! What is it?" muttered a gruff voice. "The man in armor!" hissed Clutching Hand. "Here they come, too, Chief!" There was a parting scuffle. "There--take that!" A loud metallic ringing came from the vocaphone. Then, silence! What had happened . . . . . . . . In the library, recovered from their first shock of surprise, Dan cried out to the Clutching Hand, "The deuce. What is it?" Then, looking about, Clutching Hand quickly took in the situation. "The man in armor!" he pointed out. Dan was almost dead with fright at the weird thing. "Here they come, too, Chief," he gasped, as, down the hall he could hear the family shouting out that someone was in the library. With a parting thrust, Clutching Hand sent Elaine reeling. She held on to only a corner of the papers. He had the greater part of them. They were torn and destroyed, anyway. Finally, with all the venomousness of which he was capable, Clutching Hand rushed at the armor suit, drew back his gloved fist, and let it shoot out squarely in a vicious solar plexus blow. "There--take that!" he roared. The suit rattled, furiously. Out of it spilled the vocaphone with a bang on the floor. An instant later those in the hall rushed in. But the Clutching Hand and Dan were gone out of the window, the criminal carrying the greater part of the precious papers. Some ran to Elaine, others to the window. The ladder had been kicked away and the criminals were gone. Leaping into the waiting car, they had been whisked away. "Hello! Hello! Hello!" called a voice, apparently from nowhere. "What is that?" cried Elaine, still blankly wondering. She had risen by this time and was gazing about, wondering at the strange voice. Suddenly her eye fell on the armor scattered all over the floor. She spied the little oak box. "Elaine!" Apparently the voice came from that. Besides, it had a familiar ring to her ears. "Yes--Craig!" she cried. "This is my vocaphone--the little box that hears and talks," came back to her. "Are you all right?" "Yes--all right,--thanks to the vocaphone." She had understood in an instant. She seized the helmet and breastplate to which the vocaphone still was attached and was holding them close to herself. . . . . . . . . Kennedy had been calling and listening intently over the machine, wondering whether it had been put out of business in some way. "It works--yet!" he cried excitedly to me. "Elaine!" "Yes, Craig," came back over the faithful little instrument. "Are you all right?" "Yes--all right." "Thank heaven!" breathed Craig, pushing me aside. Literally he kissed that vocaphone as if it had been human! CHAPTER IX THE DEATH RAY Kennedy was reading a scientific treatise one morning, while I was banging on the typewriter, when a knock at the laboratory door disturbed us. By some intuition, Craig seemed to know who it was. He sprang to open the door, and there stood Elaine Dodge and her lawyer, Perry Bennett. Instantly, Craig read from the startled look on Elaine's face that something dreadful had happened. "Why--what's the matter?" he asked, solicitously. "A--another letter--from the Clutching Hand!" she exclaimed breathlessly. "Mr. Bennett was calling on me, when this note was brought in. We both thought we'd better see you at once about it and he was kind enough to drive me here right away in his car." Craig took the letter and we both read, with amazement: "Are you an enemy of society? If not, order Craig Kennedy to leave the country by nine o'clock to-morrow morning. Otherwise, a pedestrian will drop dead outside his laboratory every hour until he leaves." The note was signed by the now familiar sinister hand, and had, added, a postscript, which read: "As a token of his leaving, have him place a vase of flowers on his laboratory window to-day." "What shall we do?" queried Bennett, evidently very much alarmed at the threat. "Do?" replied Kennedy, laughing contemptuously at the apparently futile threat, "why, nothing. Just wait." . . . . . . . . The day proved uneventful and I paid no further attention to the warning letter. It seemed too preposterous to amount to anything. Kennedy, however, with his characteristic foresight, as I learned afterwards, had not been entirely unprepared, though he had affected to treat the thing with contempt. His laboratory, I may say, was at the very edge of the University buildings, with the campus back of it, but opening on the other side on a street that was ordinarily not overcrowded. We got up as usual the next day and, quite early, went over to the laboratory. Kennedy, as was his custom, plunged straightway into his work and appeared absorbed by it, while I wrote. "There IS something queer going on, Walter," he remarked. "This thing registers some kind of wireless rays--infra-red, I think,--something like those that they say that Italian scientist, Ulivi, claims he has discovered and called the 'F-rays.'" "How do you know?" I asked, looking up from my work. "What's that instrument you are using?" "A bolometer, invented by the late Professor Langley," he replied, his attention riveted on it. Some time previously, Kennedy had had installed on the window ledge one of those mirror-like arrangements, known as a "busybody," which show those in a room what is going on on the street. As I moved over to look at the bolometer, I happened to glance into the busybody and saw that a crowd was rapidly collecting on the sidewalk. "Look, Craig!" I called hastily. He hurried over to me and looked. We could both see in the busybody mirror a group of excited passersby bending over a man lying prostrate on the sidewalk. He had evidently been standing on the curbstone outside the laboratory and had suddenly put his hand to his forehead. Then he had literally crumpled up into a heap, as he sank to the ground. The excited crowd lifted him up and bore him away, and I turned in surprise to Craig. He was looking at his watch. It was now only a few moments past nine o'clock! Not quarter of an hour later, our door was excitedly flung open and Elaine and Perry Bennett arrived. "I've just heard of the accident," she cried, fearfully. "Isn't it terrible. What had we better do?" For a few moments no one said a word. Then Kennedy began carefully examining the bolometer and some other recording instruments he had, while the rest of us watched, fascinated. Somehow that "busybody" seemed to attract me. I could not resist looking into it from time to time as Kennedy worked. I was scarcely able to control my excitement when, again, I saw the same scene enacted on the sidewalk before the laboratory. Hurriedly I looked at my watch. It was ten o'clock! "Craig!" I cried. "Another!" Instantly he was at my side, gazing eagerly. There was a second innocent pedestrian lying on the sidewalk while a crowd, almost panic-stricken, gathered about him. We watched, almost stunned by the suddenness of the thing, until finally, without a word, Kennedy turned away, his face set in tense lines. "It's no use," he muttered, as we gathered about him. "We're beaten. I can't stand this sort of thing. I will leave to-morrow for South America." I thought Elaine Dodge would faint at the shock of his words coming so soon after the terrible occurrence outside. She looked at him, speechless. It happened that Kennedy had some artificial flowers on a stand, which he had been using long before in the study of synthetic coloring materials. Before Elaine could recover her tongue, he seized them and stuck them into a tall beaker, like a vase. Then he deliberately walked to the window and placed the beaker on the ledge in a most prominent position. Elaine and Bennett, to say nothing of myself, gazed at him, awe-struck. "Is--is there no other way but to surrender?" she asked. Kennedy mournfully shook his head. "I'm afraid not," he answered slowly. "There's no telling how far a fellow who has this marvellous power might go. I think I'd better leave to save you. He may not content himself with innocent outsiders always." Nothing that any of us could say, not even the pleadings of Elaine herself could move him. The thought that at eleven o'clock a third innocent passerby might lie stricken on the street seemed to move him powerfully. When, at eleven, nothing happened as it had at the other two hours, he was even more confirmed in his purpose. Entreaties had no effect, and late in the morning, he succeeded in convincing us all that his purpose was irrevocable. As we stood at the door, mournfully bidding our visitors farewell until the morrow, when he had decided to sail, I could see that he was eager to be alone. He had been looking now and then at the peculiar instrument which he had been studying earlier in the day and I could see on his face a sort of subtle intentness. "I'm so sorry--Craig," murmured Elaine, choking back her emotion, and finding it impossible to go on. "So am I, Elaine," he answered, tensely. "But--perhaps--when this trouble blows over--" He paused, unable to speak, turned, and shook his head. Then with a forced gaiety he bade Elaine and Perry Bennett adieu, saying that perhaps a trip might do him good. They had scarcely gone out and Kennedy closed the door carefully, when he turned and went directly to the instrument which I had seen him observing so interestedly. Plainly, I could see that it was registering something. "What's the matter?" I asked, non-plussed. "Just a moment, Walter," he replied evasively, as if not quite sure of himself. He walked fairly close to the window this time, keeping well out of the direct line of it, however, and there stood gazing out into the street. A glint, as if of the sun shining on a pair of opera glasses could be seen from a window across the way. "We are being watched," he said slowly, turning and looking at me fixedly, "but I don't dare investigate lest it cost the lives of more unfortunates." He stood for a moment in deep thought. Then he pulled out a suitcase and began silently to pack it. . . . . . . . . Although we had not dared to investigate, we knew that from a building, across the street, emissaries of the Clutching Hand were watching for our signal of surrender. The fact was, as we found out later, that in a poorly furnished room, much after the fashion of that which, with the help of the authorities, we had once raided in the suburbs, there were at that moment two crooks. One of them was the famous, or rather the infamous, Professor LeCroix, with whom in a disguise as a doctor we had already had some experience when he stole from the Hillside Sanitarium the twilight sleep drugs. The other was the young secretary of the Clutching Hand who had given the warning at the suburban headquarters at the time when they were endeavoring to transfuse Elaine Dodge's blood to save the life of the crook whom she had shot. This was the new headquarters of the master criminal, very carefully guarded. "Look!" cried LeCroix, very much elated at the effect that had been produced by his infra-red rays, "There is the sign--the vase of flowers. We have got him this time!" LeCroix gleefully patted a peculiar instrument beside him. Apparently it was a combination of powerful electric arcs, the rays of which were shot through a funnel-like arrangement into a converter or, rather, a sort of concentration apparatus from which the dread power could be released through a tube-like affair at one end. It was his infra-red heat wave, F-ray, engine. "I told you--it would work!" cried LeCroix. . . . . . . . . I did not argue any further with Craig about his sudden resolution to go away. But it is a very solemn proceeding to pack up and admit defeat after such a brilliant succession of cases as had been his until we met this master criminal. He was unshakeable, however, and the next morning we closed the laboratory and loaded our baggage, which was considerable, on a taxicab. Neither of us said much, but I saw a quick look of appreciation on Craig's face as we pulled up at the wharf and saw that the Dodge car was already there. He seemed deeply moved that Elaine should come at such an early hour to have a last word. Our cab stopped and Kennedy moved over toward her car, directing two porters, whom I noticed that he chose with care, to wait at one side. One of them was an old Irishman with a slight limp; the other a wiry Frenchman with a pointed beard. In spite of her pleadings, however, Kennedy held to his purpose and, as we shook hands for the last time, I thought that Elaine would almost break down. "Here, you fellows, now," directed Craig, turning brusquely to the porters, "hustle that baggage right aboard." "Can't we go on the ship, too?" asked Elaine, appealingly. "I'm sorry--I'm afraid there isn't time," apologized Craig. We finally tore ourselves away, followed by the porters carrying as much as they could. "Bon voyage!" cried Elaine, bravely keeping back a choke in her voice. Near the gangplank, in the crowd, I noticed a couple of sinister faces watching the ship's officers and the passengers going aboard. Kennedy's quick eye spotted them, too, but he did not show in any way that he noticed anything as, followed by our two porters, we quickly climbed the gangplank. A moment Craig paused by the rail and waved to Elaine and Bennett who returned the salute feelingly. I paused at the rail, too, speculating how we were to get the rest of our baggage aboard in time, for we had taken several minutes saying good-bye. "In there," pointed Kennedy quickly to the porters, indicating our stateroom which was an outside room. "Come, Walter." I followed him in with a heavy heart. . . . . . . . . Outside could be seen the two sinister faces in the crowd watching intently, with eyes fixed on the stateroom. Finally one of the crooks boarded the ship hastily, while the other watched the two porters come out of the stateroom and pause at the window, speaking back into the room as though answering commands. Then the porters quickly ran along the deck and down the plank, to get the rest of the luggage. As they approached the Dodge car, Elaine, Aunt Josephine and Perry Bennett were straining their eyes to catch a last glimpse of us. The porters took a small but very heavy box and, lugging and tugging, hastened toward the boat with it. But they were too late. The gang plank was being hauled in. They shouted, but the ship's officers waved them back. "Too late!" one of the deckhands shouted, a little pleased to see that someone would be inconvenienced for tardiness. The porters argued. But it was no use. All they could do was to carry the box back to the Dodge car. Miss Dodge was just getting in as they returned. "What shall we do with this and the other stuff?" asked the Irish porter. She looked at the rest of the tagged luggage and the box which was marked: Scientific Instruments Valuable Handle with care. "Here--pile them in here," she said indicating the taxicab. "I'll take charge of them." Meanwhile one of our sinister faced friends had just had time to regain the shore after following us aboard ship and strolling past the window of our stateroom. He paused long enough to observe one of the occupants studying a map, while the other was opening a bag. "They're gone!" he said to the other as he rejoined him on the dock, giving a nod of his head and a jerk of his thumb at the ship. "Yes," added the other crook, "and lost most of their baggage, too." . . . . . . . . Slowly the Dodge car proceeded through the streets up from the river front, followed by the taxicab, until at last the Dodge mansion, was reached. There Elaine and Aunt Josephine got out and Bennett stood talking with them a moment. Finally he excused himself reluctantly for it was now late, even for a lawyer, to get to his office. As he hurried over to the subway, Elaine nodded to the porters in the taxicab, "Take that stuff in the house. We'll have to send it by the next boat." Then she followed Aunt Josephine while the porters unloaded the boxes and bags. Elaine sighed moodily as she walked slowly in. "Here, Marie," she cried petulantly to her maid, "take these wraps of mine." Marie ventured no remark, but, like a good servant, took them. A moment later Aunt Josephine left her and Elaine went into the library and over to a table. She stood there an instant, then sank down into a chair, taking up Kennedy's picture and gazing at it with eyes filled by tears. Just then Jennings came into the room, ushering the two porters laden with the boxes and bags. "Where shall I have them put these things, Miss Elaine?" he inquired. "Oh--anywhere," she answered hurriedly, replacing the picture. Jennings paused. As he did so, one of the porters limped forward. "I've a message for you, Miss," he said in a rich Irish brogue, with a look at Jennings, "to be delivered in private." Elaine glanced at him surprised. Then she nodded to Jennings who disappeared. As he did so, the Irishman limped to the door and drew together the portieres. Then he came back closer to Elaine. A moment she looked at him, not quite knowing from his strange actions whether to call for help or not. . . . . . . . . At a motion from Kennedy, as he pulled off his wig, I pulled off the little false beard. Elaine looked at us, transformed, startled. "Wh--what--" she stammered. "Oh--I'm--so--glad. How--" Kennedy said nothing. He was thoroughly enjoying her face. "Don't you understand?" I explained, laughing merrily. "I admit that I didn't until that last minute in the stateroom on the boat when we didn't come back to wave a last good-bye. But all the care that Craig took in selecting the porters was the result of work he did yesterday, and the insistence with which he chose our travelling clothes had a deep-laid purpose." She said nothing, and I continued. "The change was made quickly in the stateroom. Kennedy's man threw on the coat and hat he wore, while Craig donned the rough clothes of the porter and added a limp and a wig. The same sort of exchange of clothes was made by me and Craig clapped a Van Dyck beard on my chin." "I--I'm so glad," she repeated. "I didn't think you'd--" She cut the sentence short, remembering her eyes and the photograph as we entered, and a deep blush crimsoned her face. "Mum's the word," cautioned Kennedy, "You must smuggle us out of the house, some way." . . . . . . . . Kennedy lost no time in confirming the suspicions of his bolometer as to the cause of the death of the two innocent victims of the machinations of the Clutching Hand. Both of them, he had learned, had been removed to a nearby undertaking shop, awaiting the verdict of the coroner. We sought out the shop and prevailed on the undertaker to let us see the bodies. As Kennedy pulled down the shroud from the face of the first victim, he disclosed on his forehead a round dark spot about the size of a small coin. Quickly, he moved to the next coffin and, uncovering the face, disclosed a similar mark. "What is it?" I asked, awestruck. "Why," he said, "I've heard of a certain Viennese, one LeCroix I believe, who has discovered or perfected an infra-red ray instrument which shoots its power a great distance with extreme accuracy and leaves a mark like these." "Is he in New York?" I inquired anxiously. "Yes, I believe he is." Kennedy seemed indisposed to answer more until he knew more, and I saw that he would prefer not being questioned for the present. We thanked the undertaker for his courtesy and went out. . . . . . . . . Meanwhile Elaine had called up Perry Bennett. "Mr. Bennett," she exclaimed over the wire, "just guess who called on me?" "Who?" he answered, "I give it up." "Mr. Kennedy and Mr. Jameson," she called back. "Is that so?" he returned. "Isn't that fine? I didn't think he was the kind to run away like that. How did it happen?" Elaine quickly told the story as I had told her. Had she known it, however, Bennett's valet, Thomas, was at that very moment listening at the door, intensely interested. As Bennett hung up the receiver, Thomas entered the room. "If anyone calls me," ordered Bennett, "take the message, particularly if it is from Miss Dodge. I must get downtown--and tell her after I finish my court work for the day I shall be right up." "Yes sir," nodded the valet with a covert glance at his master. Then, as Bennett left, he followed him to the door, paused, thought a moment, then, as though coming to a sudden decision, went out by an opposite door. It was not long afterward that a knock sounded at the door of the new headquarters of the Clutching Hand. LeCroix and the secretary were there, as well as a couple of others. "The Chief!" exclaimed one. The secretary opened the door, and, sure enough, the Clutching Hand entered. "Well, how did your infra-red rays work?" he asked LeCroix. "Fine." "And they're gone?" "Yes. The flowers were in the window yesterday. Two of our men saw them on the boat." There came another knock. This time, as the door opened, it was Thomas, Bennett's faithless valet, who entered. "Say," blurted out the informer, "do you know Kennedy and Jameson are back?" "Back?" cried the crooks. "Yes,--they didn't go. Changed clothes with the porters. I just heard Miss Dodge telling Mr. Bennett." Clutching Hand eyed him keenly, then seemed to burst into an ungovernable fury. Quickly he began volleying orders at the valet and the others. Then, with the secretary and two of the other crooks he left by another door from that by which he had sent the valet forth. . . . . . . . . Leaving the undertaker's, Kennedy and I made our way, keeping off thoroughfares, to police headquarters, where, after making ourselves known, Craig made arrangements for a raid on the house across the street from the laboratory where we had seen the opera glass reflection. Then, as secretly as we had come, we went out again, letting ourselves into the laboratory, stealthily looking up and down the street. We entered by a basement door, which Kennedy carefully locked again. No sooner had we disappeared than one of the Clutching Hand's spies who had been watching behind a barrel of rubbish gave the signal of the hand down the street to a confederate and, going to the door, entered by means of a skeleton key. We entered our laboratory which Kennedy had closed the day before. With shades drawn, it now looked deserted enough. I dropped into a chair and lighted a cigarette with a sigh of relief, for really I had thought, until the boat sailed, that Kennedy actually contemplated going away. Kennedy went over to a cabinet and, from it, took out a notebook and a small box. Opening the notebook on the laboratory table, he rapidly turned the pages. "Here, Walter," he remarked. "This will answer your questions about the mysterious deadly ray." I moved over to the table, eager to satisfy my curiosity and read the notes which he indicated with his finger. INFRA-RED RAY NOTES The infra-red ray which has been developed by LeCroix from the experiments of the Italian scientist Ulivi causes, when concentrated by an apparatus perfected by LeCroix, an instantaneous combustion of nonreflecting surfaces. It is particularly deadly in its effect on the brain centers. It can be diverted, it is said however, by a shield composed of platinum backed by asbestos. Next Kennedy opened the case which he had taken out of the cabinet and from it he took out the platinum-asbestos mirror, which was something of his own invention. He held it up and in pantomime showed me just how it would cut off the deadly rays. He had not finished even that, when a peculiar noise in the laboratory itself disturbed him and he hastily thrust the asbestos platinum shield into his pocket. Though we had not realized it, our return had been anticipated. Suddenly, from a closet projected a magazine gun and before we could move, the Clutching Hand himself slowly appeared, behind us. "Ah!" he exclaimed with mock politeness, "so, you thought you'd fool me, did you? Well!" Just then, two other crooks, who had let themselves in by the skeleton key through the basement jumped into the room through that door covering us. We started to our feet, but in an instant found ourselves both sprawling on the floor. In the cabinet, beneath the laboratory table, another crook had been hidden and he tackled us with all the skill of an old football player against whom we had no defence. Four of them were upon us instantly. . . . . . . . . At the same time, Thomas, the faithless valet of Bennett, had been dispatched by the Clutching Hand to commandeer his master's roadster in his absence, and, carrying out the instructions, he had driven up before Elaine's house at the very moment when she was going out for a walk. Thomas jumped out of the car and touched his hat deferentially. "A message from Mr. Bennett, ma'am," he explained. "Mr. Kennedy and Mr. Bennett have sent me to ask you to come over to the laboratory." Unsuspecting, Elaine stepped into the car and drove off. Instead, however, of turning and pulling up on the laboratory side of the street, Thomas stopped opposite it. He got out and Elaine, thinking that perhaps it was to save time that he had not turned the car around, followed. But when the valet, instead of crossing the street, went up to a door of a house and rang the bell, she began to suspect that all was not as it should be. "What are you going here for, Thomas?" she asked. "There's the laboratory--over there." "But, Miss Dodge," he apologized, "Mr. Kennedy and Mr. Bennett are here. They told me they'd be here." The door was opened quickly by a lookout of the Clutching Hand and the valet asked if Craig and Elaine's lawyer were in. Of course the lookout replied that they were and, before Elaine knew it, she was jostled into the dark hallway and the door was banged shut. Resistance was useless now and she was hurried along until another door was opened. There she saw LeCroix and the other crooks. And, as the door slammed, she caught sight of the fearsome Clutching Hand himself. She drew back, but was too frightened even to scream. With a harsh, cruel laugh, the super-criminal beckoned to her to follow him and look down through a small trap door. Unable now to resist, she looked. There she saw us. To that extent the valet had told the truth. Kennedy was standing in deep thought, while I sat on an old box, smoking a cigarette--very miserable. . . . . . . . . Was this to be the sole outcome of Kennedy's clever ruse, I was wondering. Were we only to be shipwrecked in sight of port? Watching his chance, when the street was deserted, the Clutching Hand and his followers had hustled us over to the new hangout across from the laboratory. There they had met more crooks and had thrust us into this vile hole. As the various ineffectual schemes for escape surged through my head, I happened to look up and caught a glance of horror on Craig's face. I followed his eyes. There, above us, was Elaine! I saw her look from us to the Clutching Hand in terror. But none of us uttered a word. "I will now show you, my dear young lady," almost hissed the Clutching Hand at length, "as pretty a game of hide and seek as you have ever seen." As he said it, another trap door near the infra-red ray machine was opened and a beam of light burst through. I knew it was not that which we had to fear, but the invisible rays that accompanied it, the rays that had affected the bolometer. Just then a spot of light showed near my foot, moving about the cement floor until it fell on my shoe. Instantly, the leather charred, even before I could move. Kennedy and I leaped to our feet and drew back. The beam followed us. We retreated further. Still it followed, inexorably. Clutching Hand was now holding Elaine near the door where she could not help seeing, laughing diabolically while he directed LeCroix and the rest to work the infra-red ray apparatus through the trap. As we dodged from corner to corner, endeavoring to keep the red ray from touching us, the crooks seemed in no hurry, but rather to enjoy prolonging the torture as does a cat with a mouse. "Please--oh, please--stop!" begged Elaine. Clutching Hand only laughed with fiendish delight and urged his men on. The thing was getting closer and closer. Suddenly we heard a strange voice ring out above us. "Police!" "Where?" growled the Clutching Hand in fury. "Outside--a raid! Run! He's told them!" Already we could hear the hammers and axes of the police whom Kennedy had called upon before, as they battered at the outside door. At that door a moment before, the lookout suddenly had given a startled stare and a suppressed cry. Glancing down the street he had seen a police patrol in which were a score or more of the strongarm squad. They had jumped out, some carrying sledgehammers, others axes. Almost before he could cry out and retreat to give a warning, they had reached the door and the first resounding blows had been struck. The lookout quickly had fled and drawn the bolts of a strong inner door, and the police began battering that impediment. Instantly, Clutching Hand turned to LeCroix at the F-ray machine. "Finish them!" he shouted. We were now backed up against a small ell in the wall of the cellar. It was barely large enough to hold us, but by crowding we were able to keep out of the reach of the ray. The ray shot past the ell and struck a wall a couple of inches from us. I looked. The cement began to crumble under the intense heat. Meanwhile, the police were having great difficulty with the steelbolt-studded door into the room. Still, it was yielding a bit. "Hurry!" shouted Clutching Hand to LeCroix. Kennedy had voluntarily placed himself in front of me in the ell. Carefully, to avoid the ray, he took the asbestos-platinum shield from his pocket and slid it forward as best he could over the wall to the spot where the ray struck. It deflected the ray. But so powerful was it that even that part of the ray which was deflected could be seen to strike the ceiling in the corner which was of wood. Instantly, before Kennedy could even move the shield, the wood burst into flames. Above us now smoke was pouring into the room where the deflected ray struck the floor and flames broke out. "Confound him!" ground out Clutching Hand, as they saw it. The other crooks backed away and stood, hesitating, not knowing quite what to do. The police had by this time finished battering in the door and had rushed into the outer passage. While the flames leaped up, the crooks closed the last door into the room. "Run!" shouted Clutching Hand, as they opened a secret gate disclosing a spiral flight of iron steps. A moment later all had disappeared except Clutching Hand himself. The last door would hold only a few seconds, but Clutching Hand was waiting to take advantage of even that. With a last frantic effort he sought to direct the terrific ray at us. Elaine acted instantly. With all her strength she rushed forward, overturning the machine. Clutching Hand uttered a growl and slowly raised his gun, taking aim with the butt for a well-directed blow at her head. Just then the door yielded and a policeman stuck his head and shoulders through. His revolver rang out and Clutching Hand's automatic flew out of his grasp, giving him just enough time to dodge through and slam the secret door in the faces of the squad as they rushed in. Back of the house, Clutching Hand and the other crooks were now passing through a bricked passage. The fire had got so far beyond control by this time that it drove the police back from their efforts to open the secret door. Thus the Clutching Hand had made good his escape through the passage which led out, as we later discovered, to the railroad tracks along the river. "Down there--Mr. Kennedy--and Mr. Jameson," cried Elaine, pointing at the trap which was hidden in the stifle. The fire had gained terrific headway, but the police seized a ladder and stuck it down into the basement. Choking and sputtering, half suffocated, we staggered up. "Are you hurt?" asked Elaine anxiously, taking Craig's arm. "Not a bit--thanks to you!" he replied, forgetting all in meeting the eager questioning of her wonderful eyes. CHAPTER X THE LIFE CURRENT Assignments were being given out on the Star one afternoon, and I was standing talking with several other reporter in the busy hum of typewriters and clicking telegraphs. "What do you think of that?" asked one of the fellows. "You're something of a scientific detective, aren't you?" Without laying claim to such a distinction, I took the paper and read: THE POISONED KISS AGAIN Three More New York Women Report Being Kissed by Mysterious Stranger--Later Fell into Deep Unconsciousness. What Is It? I had scarcely finished, when one of the copy boys, dashing past me, called, "You're wanted on the wire, Mr. Jameson." I hurried over to the telephone and answered. A musical voice responded to my hurried hello, and I hastened to adopt my most polite tone. "Is this Mr. Jameson?" asked the voice. "Yes," I replied, not recognizing it. "Well, Mr. Jameson, I've heard of you on the Star and I've just had a very strange experience. I've had the poisoned kiss." The woman did not pause to catch my exclamation of astonishment, but went on, "It was like this. A man ran up to me on the street and kissed me--and--I don't know how it was--but I became unconscious--and I didn't come to for an hour--in a hospital--fortunately. I don't know what would have happened if it hadn't been that someone came to my assistance and the man fled. I thought the Star would be interested." "We are," I hastened to reply. "Will you give me your name?" "Why, I am Mrs. Florence Leigh of number 20 Prospect Avenue," returned the voice. "Really, Mr. Jameson, something ought to be done about these cases." "It surely had," I assented, with much interest, writing her name eagerly down on a card. "I'll be out to interview you, directly." The woman thanked me and I hung up the receiver. "Say," I exclaimed, hurrying over to the editor's desk, "here's another woman on the wire who says she has received the poisoned kiss. "Suppose you take that assignment," the editor answered, sensing a possible story. I took it with alacrity, figuring out the quickest way by elevated and surface car to reach the address. The conductor of the trolley indicated Prospect Avenue and I hurried up the street until I came to the house, a neat, unpretentious place. Looking at the address on the card first to make sure, I rang the bell. I must say that I could scarcely criticize the poisoned kisser's taste, for the woman who had opened the door certainly was extraordinarily attractive. "And you really were--put out by a kiss?" I queried, as she led me into a neat sitting room. "Absolutely--as much as if it had been by one of these poisoned needles you read about," she replied confidently, hastening on to describe the affair volubly. It was beyond me. "May I use your telephone?" I asked. "Surely," she answered. I called the laboratory. "Is that you, Craig?" I inquired. "Yes, Walter," he answered, recognizing my voice. "Say, Craig," I asked breathlessly, "what sort of kiss would suffocate a person." My only answer was an uproarious laugh from him at the idea. "I know," I persisted, "but I've got the assignment from the Star--and I'm out here interviewing a woman about it. It's all right to laugh--but here I am. I've found a case--names, dates and places. I wish you'd explain the thing, then." "Oh, all right, Walter," he replied indulgently. "I'll meet you as soon as I can and help you out." I hung up the receiver with an air of satisfaction. At least now I would get an explanation of the woman's queer story. "I'll clear this thing up," I said confidently. "My friend, Craig Kennedy, the scientific detective is coming out here." "Good! That fellow who attacked me ought to be shown up. All women may not be as fortunate as I." We waited patiently. Her story certainly was remarkable. She remembered every detail up to a certain point--and then, as she said, all was blankness. The bell rang and the woman hastened to the door admitting Kennedy. "Hello, Walter," he greeted. "This is certainly a most remarkable case, Craig," I said, introducing him, and telling briefly what I had learned. "And you actually mean to say that a kiss had the effect--" Just then the telephone interrupted. "Yes," she reasserted quickly. "Excuse me a second." She answered the call. "Oh--why--yes, he's here. Do you want to speak to him? Mr. Jameson, it's the Star." "Confound it!" I exclaimed, "isn't that like the old man--dragging me off this story before it's half finished in order to get another. I'll have to go. I'll get this story from you, Craig." . . . . . . . . The day before, in the suburban house, the Clutching Hand had been talking to two of his emissaries, an attractive young woman and a man. They were Flirty Florrie and Dan the Dude. "Now, I want you to get Kennedy," he said. "The way to do it is to separate Kennedy and Elaine--see?" "All right, Chief, we'll do it," they replied. "I've rigged it so that you'll reach him through Jameson, understand?" They nodded eagerly as he told them the subtle plan. Clutching Hand had scarcely left when Flirty Florrie began by getting published in the papers the story which I had seen. The next day she called me up from the suburban house. Having got me to promise to see her, she had scarcely turned from the telephone when Dan the Dude walked in from the next room. "He's coming," she said. Dan was carrying a huge stag head with a beautifully branched pair of antlers. Under his arm was a coil of wire which he had connected to the inside of the head. "Fine!" he exclaimed. Then, pointing to the head, he added, "It's all ready. See how I fixed it? That ought to please the Chief." Dan moved quickly to the mantle and mounted a stepladder there by which he had taken down the head, and started to replace the head above the mantle. He hooked the head on a nail. "There," he said, unscrewing one of the beautiful brown glass eyes of the stag. Back of it could be seen a camera shutter. Dan worked the shutter several times to see whether it was all right. "One of those new quick shutter cameras," he explained. Then he ran a couple of wires along the moulding, around the room and into a closet, where he made the connection with a sort of switchboard on which a button was marked, "SHUTTER" and the switch, "WIND FILM." "Now, Flirty," he said, coming out of the closet and pulling up the shade which let a flood of sunlight into the room, "you see, I want you to stand here--then, do your little trick. Get me?" "I get you Steve," she laughed. Just then the bell rang. "That must be Jameson," she cried. "Now--get to your corner." With a last look Dan went into the closet and shut the door. Perhaps half an hour later, Clutching Hand himself called me up on the telephone. It was he--not the Star--as I learned only too late. . . . . . . . . I had scarcely got out of the house, as Craig told me afterwards, when Flirty Florrie told all over again the embroidered tale that had caught my ear. Kennedy said nothing, but listened intently, perhaps betraying in his face the scepticism he felt. "You see," she said, still voluble and eager to convince him, "I was only walking on the street. Here,--let me show you. It was just like this." She took his arm and before he knew it, led him to the spot on the floor near the window which Dan had indicated. Meanwhile Dan was listening attentively in his closet. "Now--stand there. You are just as I was--only I didn't expect anything." She was pantomiming someone approaching stealthily while Kennedy watched her with interest, tinged with doubt. Behind Craig, in his closet, Dan was reaching for the switchboard button. "You see," she said advancing quickly and acting her words, "he placed his hands on my shoulders--so--then threw his arms about my neck--so." She said no more, but imprinted a deep, passionate kiss on Kennedy's mouth, clinging closely to him. Before Kennedy could draw away, Dan, in the closet, had pressed the button and the switch several times in rapid succession. "Th-that's very realistic," gasped Craig, a good deal taken aback by the sudden osculatory assault. He frowned. "I--I'll look into the case," he said, backing away. "There may be some scientific explanation--but--er--" He was plainly embarrassed and hastened to make his adieux. Kennedy had no more than shut the door before Dan, with a gleeful laugh, burst out of the closet and flung his own arms about Florrie in an embrace that might have been poisoned, it is true, but was none the less real for that. . . . . . . . . How little impression the thing made on Kennedy can be easily seen from the fact that on the way downtown that afternoon he stopped at Martin's, on Fifth Avenue, and bought a ring--a very handsome solitaire, the finest Martin had in the shop. It must have been about the time that he decided to stop at Martin's that the Dodge butler, Jennings, admitted a young lady who presented a card on which was engraved the name Miss FLORENCE LEIGH 20 Prospect Avenue. As he handed Elaine the card, she looked up from the book she was reading and took it. "I don't know her," she said puckering her pretty brow. "Do you? What does she look like?" "I never saw her before, Miss Elaine," Jennings shrugged. "But she is very well dressed." "All right, show her in, Jennings. I'll see her." Elaine moved into the drawing room, Jennings springing forward to part the portieres for her and passing through the room quickly where Flirty Florrie sat waiting. Flirty Florrie rose and stood gazing at Elaine, apparently very much embarrassed, even after Jennings had gone. There was a short pause. The woman was the first to speak. "It IS embarrassing," she said finally, "but, Miss Dodge, I have come to you to beg for my love." Elaine looked at her non-plussed. "Yes," she continued, "you do not know it, but Craig Kennedy is infatuated with you." She paused again, then added, "But he is engaged to me." Elaine stared at the woman. She was dazed. She could not believe it. "There is the ring," Flirty Florrie added indicating a very impressive paste diamond. Elaine frowned but said nothing. Her head was in a whirl. She could not believe. Although Florrie was very much embarrassed, she was quite as evidently very much wrought up. Quickly she reached into her bag and drew out two photographs, without a word, handing them to Elaine. Elaine took them reluctantly. "There's the proof," Florrie said simply, choking a sob. Elaine looked with a start. Sure enough, there was the neat living room in the house on Prospect Avenue. In one picture Florrie had her arms over Kennedy's shoulders. In the other, apparently, they were passionately kissing. Elaine slowly laid the photographs on the table. "Please--please, Miss Dodge--give me back my lost love. You are rich and beautiful--I am poor. I have only my good looks. But--I--I love him--and he--loves me--and has promised to marry me." Filled with wonder, and misgivings now, and quite as much embarrassed at the woman's pleadings as the woman herself had acted a moment before, Elaine tried to wave her off. "Really--I--I don't know anything about all this. It--it doesn't concern me. Please--go." Florrie had broken down completely and was weeping softly into a lace handkerchief. She moved toward the door. Elaine followed her. "Jennings--please see the lady to the door." Back in the drawing room, Elaine almost seized the photographs and hurried into the library where she could be alone. There she stood gazing at them--doubt, wonder, and fear battling on her plastic features. Just then she heard the bell and Jennings in the hall. She shoved the photographs away from her on the table. It was Kennedy himself, close upon the announcement of the butler. He was in a particularly joyous and happy mood, for he had stopped at Martin's. "How are you this afternoon?" he greeted Elaine gaily. Elaine had been too overcome by what had just happened to throw it off so easily, and received him with a quickly studied coolness. Still, Craig, man-like, did not notice it at once. In fact he was too busy gazing about to see that neither Jennings, Marie, nor the duenna Aunt Josephine were visible. They were not and he quickly took the ring from his pocket. Without waiting, he showed it to Elaine. In fact, so sure had he been that everything was plain sailing, that he seemed to take it almost for granted. Under other circumstances, he would have been right. But not tonight. Elaine very coolly admired the ring, as Craig might have eyed a specimen on a microscope slide. Still, he did not notice. He took the ring, about to put it on her finger. Elaine drew away. Concealment was not in her frank nature. She picked up the two photographs. "What have you to say about those?" she asked cuttingly. Kennedy, quite surprised, took them and looked at them. Then he let them fall carelessly on the table and dropped into a chair, his head back in a burst of laughter. "Why--that was what they put over on Walter," he said. "He called me up early this afternoon--told me he had discovered one of these poisoned kiss cases you have read about in the papers. Think of it--all that to pull a concealed camera! Such an elaborate business--just to get me where they could fake this thing. I suppose they've put some one up to saying she's engaged?" Elaine was not so lightly affected. "But," she said severely, repressing her emotion, "I don't understand, MR. Kennedy, how scientific inquiry into 'the poisoned kiss' could necessitate this sort of thing." She pointed at the photographs accusingly. "But," he began, trying to explain. "No buts," she interrupted. "Then you believe that I--" "How can you, as a scientist, ask me to doubt the camera," she insinuated, very coldly turning away. Kennedy rapidly began to see that it was far more serious than he had at first thought. "Very well," he said with a touch of impatience, "if my word is not to be taken--I--I'll--" He had seized his hat and stick. Elaine did not deign to answer. Then, without a word he stalked out of the door. As he did so, Elaine hastily turned and took a few steps after him, as if to recall her words, then stopped, and her pride got the better of her. She walked slowly back to the chair by the table--the chair he had been sitting in--sank down into it and cried. . . . . . . . . Kennedy was moping in the laboratory the next day when I came in. Just what the trouble was, I did not know, but I had decided that it was up to me to try to cheer him up. "Say, Craig," I began, trying to overcome his fit of blues. Kennedy, filled with his own thoughts, paid no attention to me. Still, I kept on. Finally he got up and, before I knew it, he took me by the ear and marched me into the next room. I saw that what he needed chiefly was to be let alone, and he went back to his chair, dropping down into it and banging his fists on the table. Under his breath he loosed a small volley of bitter expletives. Then he jumped up. "By George--I WILL," he muttered. I poked my head out of the door in time to see him grab up his hat and coat and dash from the room, putting his coat on as he went. "He's a nut today," I exclaimed to myself. Though I did not know, yet, of the quarrel, Kennedy had really struggled with himself until he was willing to put his pride in his pocket and had made up his mind to call on Elaine again. As he entered, he saw that it was really of no use, for only Aunt Josephine was in the library. "Oh, Mr. Kennedy," she said innocently enough, "I'm so sorry she isn't here. There's been something troubling her and she won't tell me what it is. But she's gone to call on a young woman, a Florence Leigh, I think." "Florence Leigh!" exclaimed Craig with a start and a frown. "Let me use your telephone." I had turned my attention in the laboratory to a story I was writing, when I heard the telephone ring. It was Craig. Without a word of apology for his rudeness, which I knew had been purely absent-minded, I heard him saying, "Walter--meet me in half an hour outside that Florence Leigh's house." He was gone in a minute, giving me scarcely time to call back that I would. Then, with a hasty apology for his abruptness, he excused himself, leaving Aunt Josephine wondering at his strange actions. At about the same time that Craig had left the laboratory, at the Dodge house Elaine and Aunt Josephine had been in the hall near the library. Elaine was in her street dress. "I'm going out, Auntie," she said with an attempted gaiety. "And," she added, "if anyone should ask for me, I'll be there." She had showed her a card on which was engraved, the name and address of Florence Leigh. "All right, dear," answered Aunt Josephine, not quite clear in her mind what subtle change there was in Elaine. . . . . . . . . Half an hour later I was waiting near the house in the suburbs to which I had been directed by the strange telephone call the day before. I noticed that it was apparently deserted. The blinds were closed and a "To Let" sign was on the side of the house. "Hello, Walter," cried Craig at last, bustling along. He stopped a moment to look at the house. Then, together, we went up the steps and we rang the bell, gazing about. "Strange," muttered Craig. "The house looks deserted." He pointed out the sign and the generally unoccupied look of the place. Nor was there any answer to our ring. Kennedy paused only a second, in thought. "Come on, Walter," he said with a sudden decision. "We've got to get in here somehow." He led the way around the side of the house to a window, and with a powerful grasp, wrenched open the closed shutters. He had just smashed the window viciously with his foot when a policeman appeared. "Hey, you fellows--what are you doing there?" he shouted. Craig paused a second, then pulled his card from his pocket. "Just the man I want," he parried, much to the policeman's surprise, "There's something crooked going on here. Follow us in." We climbed into the window. There was the same living room we had seen the day before. But it was now bare and deserted. Everything was gone except an old broken chair. Craig and I were frankly amazed at the complete and sudden change and I think the policeman was a little surprised, for he had thought the place occupied. "Come on," cried Kennedy, beckoning us on. Quickly he rushed through the house. There was not a thing in it to change the deserted appearance of the first floor. At last it occurred to Craig to grope his way down cellar. There was nothing there, either, except a bin, as innocent of coal as Mother Hubbard's cupboard was of food. For several minutes we hunted about without discovering a thing. Kennedy had been carefully going over the place and was at the other side of the cellar from ourselves when I saw him stop and gaze at the floor. He was not looking, apparently, so much as listening. I strained my ears, but could make out nothing. Before I could say anything, he raised his hand for silence. Apparently he had heard something. "Hide," he whispered suddenly to us. Without another word, though for the life of me I could make nothing out of it, I pulled the policeman into a little angle of the wall nearby, while Craig slipped into a similar angle. We waited a moment. Nothing happened. Had he been seeing things or hearing things, I wondered? From our hidden vantage we could now see a square piece in the floor, perhaps five feet in diameter, slowly open up as though on a pivot. Beneath it we could make out a tube-like hole, perhaps three feet across, with a covered top. It slowly opened. A weird and sinister figure of a man appeared. Over his head he wore a peculiar helmet with hideous glass pieces over the eyes, and tubes that connected with a tank which he carried buckled to his back. As he slowly dragged himself out, I could wonder only at the outlandish headgear. Quickly he closed down the cover of the tube, but not before a vile effluvium seemed to escape, and penetrate even to us in our hiding places. As he moved forward, Kennedy gave a flying leap at him, and we followed with a regular football interference. It was the work of only a moment for us to subdue and hold him, while Craig ripped off the helmet. It was Dan the Dude. "What's that thing?" I puffed, as I helped Craig with the headgear. "An oxygen helmet," he replied. "There must be air down the tube that cannot be breathed." He went over to the tube. Carefully he opened the top and gazed down, starting back a second later, with his face puckered up at the noxious odor. "Sewer gas," he ejaculated, as he slammed the cover down. Then he added to the policeman, "Where do you suppose it comes from?" "Why," replied the officer, "the St. James Drain--an old sewer--is somewhere about these parts." Kennedy puckered his face as he gazed at our prisoner. He reached down quickly and lifted something off the man's coat. "Golden hair," he muttered. "Elaine's!" A moment later he seized the man and shook him roughly. "Where is she--tell me?" he demanded. The man snarled some kind of reply, refusing to say a word about her. "Tell me," repeated Kennedy. "Humph!" snorted the prisoner, more close-mouthed than ever. Kennedy was furious. As he sent the man reeling away from him, he seized the oxygen helmet and began putting it on. There was only one thing to do--to follow the clue of the golden strands of hair. Down into the pest hole he went, his head protected by the oxygen helmet. As he cautiously took one step after another down a series of iron rungs inside the hole, he found that the water was up to his chest. At the bottom of the perpendicular pit was a narrow low passage way, leading off. It was just about big enough to get through, but he managed to grope along it. He came at last to the main drain, an old stone-walled sewer, as murky a place as could well be imagined, filled with the foulest sewer gas. He was hardly able to keep his feet in the swirling, bubbling water that swept past, almost up to his neck. The minutes passed as the policeman and I watched our prisoner in the cellar, by the tube. I looked anxiously at my watch. "Craig!" I shouted at last, unable to control my fears for him. No answer. To go down after him seemed out of the question. By this time, Craig had come to a small open chamber into which the sewer widened. On the wall he found another series of iron rungs up which he climbed. The gas was terrible. As he neared the top of the ladder, he came to a shelf-like aperture in the sewer chamber, and gazed about. It was horribly dark. He reached out and felt a piece of cloth. Anxiously he pulled on it. Then he reached further into the darkness. There was Elaine, unconscious, apparently dead. He shook her, endeavoring to wake her up. But it was no use. In desperation Craig carried her down the ladder. With our prisoner, we could only look helplessly around. Again and again I looked at my watch as the minutes lengthened. Suppose the oxygen gave out? "By George, I'm going down after him," I cried in desperation. "Don't do it," advised the policeman. "You'll never get out." One whiff of the horrible gas told me that he was right. I should not have been able to go fifty feet in it. I looked at him in despair. It was impossible. "Listen," said the policeman, straining his ears. There was indeed a faint noise from the black depths below us. A rope alongside the rough ladder began to move, as though someone was pulling it taut. We gazed down. "Craig! Craig!" I called. "Is that you?" No answer. But the rope still moved. Perhaps the helmet made it impossible for him to hear. He had struggled back in the swirling current almost exhausted by his helpless burden. Holding Elaine's head above the surface of the water and pulling on the rope to attract my attention, for he could neither hear nor shout, he had taken a turn of the rope about Elaine. I tried pulling on it. There was something heavy on the other end and I kept on pulling. At last I could make out Kennedy dimly mounting the ladder. The weight was the unconscious body of Elaine which he steadied as he mounted. I tugged harder and he slowly came up. Together, at last, the policeman and I reached down and pulled them out. We placed Elaine on the cellar floor, as comfortably as was possible, and the policeman began his first-aid motions for resuscitation. "No--no," cried Kennedy, "Not here--take her up where the air is fresher." With his revolver still drawn to overawe the prisoner, the policeman forced him to aid us in carrying her up the rickety flight of cellar steps. Kennedy followed quickly, unscrewing the oxygen helmet as he went. In the deserted living room we deposited our senseless burden, while Kennedy, the helmet off now, bent over her. "Quick--quick!" he cried to the officer, "An ambulance!" "But the prisoner," the policeman indicated. "Hurry--hurry--I'll take care of him," urged Craig, seizing the policeman's pistol and thrusting it into his pocket. "Walter--help me." He was trying the ordinary methods of resuscitation. Meanwhile the officer had hurried out, seeking the nearest telephone, while we worked madly to bring Elaine back. Again and again Kennedy bent and outstretched her arms, trying to induce respiration. So busy was I that for the moment I forgot our prisoner. But Dan had seen his chance. Noiselessly he picked up the old chair in the room and with it raised was approaching Kennedy to knock him out. Before I knew it myself, Kennedy had heard him. With a half instinctive motion, he drew the revolver from his pocket and, almost before I could see it, had shot the man. Without a word he returned the gun to his pocket and again bent over Elaine, without so much as a look at the crook who sank to the floor, dropping the chair from his nerveless hands. Already the policeman had got an ambulance which was now tearing along to us. Frantically Kennedy was working. A moment he paused and looked at me--hopeless. Just then, outside, we could hear the ambulance, and a doctor and two attendants hurried up to the door. Without a word the doctor seemed to appreciate the gravity of the case. He finished his examination and shook his head. "There is no hope--no hope," he said slowly. Kennedy merely stared at him. But the rest of us instinctively removed our hats. Kennedy gazed at Elaine, overcome. Was this the end? It was not many minutes later that Kennedy had Elaine in the little sitting room off the laboratory, having taken her there in the ambulance, with the doctor and two attendants. Elaine's body had been placed on a couch, covered by a blanket, and the shades were drawn. The light fell on her pale face. There was something incongruous about death and the vast collection of scientific apparatus, a ghastly mocking of humanity. How futile was it all in the presence of the great destroyer? Aunt Josephine had arrived, stunned, and a moment later, Perry Bennett. As I looked at the sorrowful party, Aunt Josephine rose slowly from her position on her knees where she had been weeping silently beside Elaine, and pressed her hands over her eyes, with every indication of faintness. Before any of us could do anything, she had staggered into the laboratory itself, Bennett and I following quickly. There I was busy for some time getting restoratives. Meanwhile Kennedy, beside the couch, with an air of desperate determination, turned away and opened a cabinet. From it he took a large coil and attached it to a storage battery, dragging the peculiar apparatus near Elaine's couch. To an electric light socket, Craig attached wires. The doctor watched him in silent wonder. "Doctor," he asked slowly as he worked, "do you know of Professor Leduc of the Nantes Ecole de Medicin?" "Why--yes," answered the doctor, "but what of him?" "Then you know of his method of electrical resuscitation." "Yes--but--" He paused, looking apprehensively at Kennedy. Craig paid no attention to his fears, but approaching the couch on which Elaine lay, applied the electrodes. "You see," he explained, with forced calmness, "I apply the anode here--the cathode there." The ambulance surgeon looked on excitedly, as Craig turned on the current, applying it to the back of the neck and to the spine. For some minutes the machine worked. Then the young doctor's eyes began to bulge. "My heavens!" he cried under his breath. "Look!" Elaine's chest had slowly risen and fallen. Kennedy, his attention riveted on his work, applied himself with redoubled efforts. The young doctor looked on with increased wonder. "Look! The color in her face! See her lips!" he cried. At last her eyes slowly fluttered open--then closed. Would the machine succeed? Or was it just the galvanic effect of the current? The doctor noticed it and quickly placed his ear to her heart. His face was a study in astonishment. The minutes sped fast. To us outside, who had no idea what was transpiring in the other room, the minutes were leaden-feeted. Aunt Josephine, weak but now herself again, was sitting nervously. Just then the door opened. I shall never forget the look on the young ambulance surgeon's face, as he murmured under his breath, "Come here--the age of miracles is not passed--look!" Raising his finger to indicate that we were to make no noise, he led us into the other room. Kennedy was bending over the couch. Elaine, her eyes open, now, was gazing up at him, and a wan smile flitted over her beautiful face. Kennedy had taken her hand, and as he heard us enter, turned half way to us, while we stared in blank wonder from Elaine to the weird and complicated electrical apparatus. "It is the life-current," he said simply, patting the Leduc apparatus with his other hand. CHAPTER XI THE HOUR OF THREE With the ominous forefinger of his Clutching Hand extended, the master criminal emphasized his instructions to his minions. "Perry Bennett, her lawyer, is in favor again with Elaine Dodge," he was saying. "She and Kennedy are on the outs even yet. But they may become reconciled. Then she'll have that fellow on our trail again. Before that happens, we must 'get' her--see?" It was in the latest headquarters to which Craig had chased the criminal, in one of the toughest parts of the old Greenwich village, on the west side of New York, not far from the river front. They were all seated in a fairly large but dingy old room, in which were several chairs, a rickety table and, against the wall, a roll-top desk on the top of which was a telephone. Several crooks of the gang were sitting about, smoking. "Now," went on Clutching Hand, "I want you, Spike, to follow them. See what they do--where they go. It's her birthday. Something's bound to occur that will give you a lead. All you've got to do is to use your head. Get me?" Spike rose, nodded, picked up his hat and coat and squirmed out on his mission, like the snake that he was. . . . . . . . . It was, as Clutching Hand had said, Elaine's birthday. She had received many callers and congratulations, innumerable costly and beautiful tokens of remembrance from her countless friends and admirers. In the conservatory of the Dodge house Elaine, Aunt Josephine, and Susie Martin were sitting discussing not only the happy occasion, but, more, the many strange events of the past few weeks. "Well," cried a familiar voice behind them. "What would a certain blonde young lady accept as a birthday present from her family lawyer?" All three turned in surprise. "Oh, Mr. Bennett," cried Elaine. "How you startled us!" He laughed and repeated his question, adopting the tone that he had once used in the days when he had been more in favor with the pretty heiress, before the advent of Kennedy. Elaine hesitated. She was thinking not so much of his words as of Kennedy. To them all, however, it seemed that she was unable to make up her mind what, in the wealth of her luxury, she would like. Susie Martin had been wondering whether, now that Bennett was here, she were not de trop, and she looked at her wrist watch mechanically. As she did so, an idea occurred to her. "Why not one of these?" she cried impulsively, indicating the watch. "Father has some beauties at the shop." "Oh, good," exclaimed Elaine, "how sweet!" She welcomed the suggestion, for she had been thinking that perhaps Bennett might be hinting too seriously at a solitaire. "So that strikes your fancy?" he asked. "Then let's all go to the shop. Miss Martin will personally conduct the tour, and we shall have our pick of the finest stock." A moment later the three young people went out and were quickly whirled off down the Avenue in the Dodge town car. It was too gay a party to notice a sinister figure following them in a cab. But as they entered the fashionable jewelry shop, Spike, who had alighted, walked slowly down the street. Chatting with animation, the three moved over to the watch counter, while the crook, with a determination not to risk missing anything, entered the shop door, too. "Mr. Thomas," asked Susie as her father's clerk bowed to them, "please show Miss Dodge the wrist watches father was telling about." With another deferential bow, the clerk hastened to display a case of watches and they bent over them. As each new watch was pointed out, Elaine was delighted. Unobserved, the crook walked over near enough to hear what was going on. At last, with much banter and yet care, Elaine selected one that was indeed a beauty and was about to snap it on her dainty wrist, when the clerk interrupted. "I beg pardon," he suggested, "but I'd advise you to leave it to be regulated, if you please." "Yes, indeed," chimed in Susie. "Father always advises that." Reluctantly, Elaine handed it over to the clerk. "Oh, thank you, ever so much, Mr. Bennett," she said as he unobtrusively paid for the watch and gave the address to which it was to be sent when ready. A moment later they went out and entered the car again. As they did so, Spike, who had been looking various things in the next case over as if undecided, came up to the watch counter. "I'm making a present," he remarked confidentially to the clerk. "How about those bracelet watches?" The clerk pulled out some of the cheaper ones. "No," he said thoughtfully, pointing out a tray in the show case, "something like those." He ended by picking out one identically like that which Elaine had selected, and started to pay for it. "Better have it regulated," repeated the clerk. "No," he objected hastily, shaking his head and paying the money quickly. "It's a present--and I want it tonight." He took the watch and left the store hurriedly. . . . . . . . . In the laboratory, Kennedy was working over an oblong oak box, perhaps eighteen inches in length and half as high. In the box I could see, besides other apparatus, two good sized spools of fine wire. "What's all that?" I asked inquisitively. "Another of the new instruments that scientific detectives use," he responded, scarcely looking up, "a little magnetic wizard, the telegraphone." "Which is?" I prompted. "Something we detectives might use to take down and 'can' telephone and other conversations. When it is attached properly to a telephone, it records everything that is said over the wire." "How does it work?" I asked, much mystified. "Well, it is based on an entirely new principle, in every way different from the phonograph," he explained. "As you can see there are no discs or cylinders, but these spools of extremely fine steel wire. The record is not made mechanically on a cylinder, but electromagnetically on this wire." "How?" I asked, almost incredulously. "To put it briefly," he went on, "small portions of magnetism, as it were, are imparted to fractions of the steel wire as it passes between two carbon electric magnets. Each impression represents a sound wave. There is no apparent difference in the wire, yet each particle of steel undergoes an electromagnetic transformation by which the sound is indelibly imprinted on it." "Then you scrape the wire, just as you shave records to use it over again?" I suggested. "No," he replied. "You pass a magnet over it and the magnet automatically erases the record. Rust has no effect. The record lasts as long as steel lasts." Craig continued to tinker tantalizingly with the machine which had been invented by a Dane, Valdemar Poulsen. He had scarcely finished testing out the telegraphone, when the laboratory door opened and a clean-cut young man entered. Kennedy, I knew, had found that the routine work of the Clutching Hand case was beyond his limited time and had retained this young man, Raymond Chase, to attend to that. Chase was a young detective whom Craig had employed on shadowing jobs and as a stool pigeon on other cases, and we had all the confidence in the world in him. Just now what worried Craig was the situation with Elaine, and I fancied that he had given Chase some commission in connection with that. "I've got it, Mr. Kennedy," greeted Chase with quiet modesty. "Good," responded Craig heartily. "I knew you would." "Got what?" I asked a moment later. Kennedy nodded for Chase to answer. "I've located the new residence of Flirty Florrie," he replied. I saw what Kennedy was after at once. Flirty Florrie and Dan the Dude had caused the quarrel between himself and Elaine. Dan the Dude was dead. But Flirty Florrie might be forced to explain it. "That's fine," he added, exultingly. "Now, I'll clear that thing up." He took a hasty step to the telephone, put his hand on the receiver and was about to take it off the hook. Then he paused, and I saw his face working. The wound Elaine had given his feelings was deep. It had not yet quite healed. Finally, his pride, for Kennedy's was a highly sensitive nature, got the better of him. "No," he said, half to himself, "not--yet." Elaine had returned home. Alone, her thoughts naturally went back to what had happened recently to interrupt a friendship which had been the sweetest in her life. "There MUST be some mistake," she murmured pensively to herself, thinking of the photograph Flirty had given her. "Oh, why did I send him away? Why didn't I believe him?" Then she thought of what had happened, of how she had been seized by Dan the Dude in the deserted house, of how the noxious gas had overcome her. They had told her of how Craig had risked his life to save her, how she had been brought home, still only half alive, after his almost miraculous work with the new electric machine. There was his picture. She had not taken that away. As she looked at it, a wave of feeling came over her. Mechanically, she put out her hand to the telephone. She was about to take off the receiver, when something seemed to stay her hand. She wanted him to come to her. And, if either of them had called the other just then, they would have probably crossed wires. Of such stuff are the quarrels of lovers. Craig's eye fell on the telegraphone, and an idea seemed to occur to him. "Walter, you and Chase bring that thing along," he said a moment later. He paused long enough to take a badge from the drawer of a cabinet, and went out. We followed him, lugging the telegraphone. At last we came to the apartment house at which Chase had located the woman. "There it is," he pointed out, as I gave a groan of relief, for the telegraphone was getting like lead. Kennedy nodded and drew from his pocket the badge I had seen him take from the cabinet. "Now, Chase," he directed, "you needn't go in with us. Walter and I can manage this, now. But don't get out of touch with me. I shall need you any moment--certainly tomorrow." I saw that the badge read, Telephone Inspector. "Walter," he smiled, "you're elected my helper." We entered the apartment house hall and found a Negro boy in charge of the switchboard. It took Craig only a moment to convince the boy that he was from the company and that complaints had been made by some anonymous tenant. "You look over that switchboard, Kelly," he winked at me, "while I test out the connections back here. There must be something wrong with the wires or there wouldn't be so many complaints." He had gone back of the switchboard and the Negro, still unsuspicious, watched without understanding what it was all about. "I don't know," Craig muttered finally for the benefit of the boy, "but I think I'll have to leave that tester after all. Say, if I put it here, you'll have to be careful not to let anyone meddle with it. If you do, there'll be the deuce to pay. See?" Kennedy had already started to fasten the telegraphone to the wires he had selected from the tangle. At last he finished and stood up. "Don't disturb it and don't let anyone else touch it," he ordered. "Better not tell anyone--that's the best way. I'll be back for it tomorrow probably." "Yas sah," nodded the boy, with a bow, as we went out. We returned to the laboratory, where there seemed to be nothing we could do now except wait for something to happen. Kennedy, however, employed the time by plunging into work, most of the time experimenting with a peculiar little coil to which ran the wires of an ordinary electric bell. Back in the new hang-out, the Clutching Hand was laying down the law to his lieutenants and heelers, when Spike at last entered. "Huh!" growled the master criminal, covering the fact that he was considerably relieved to see him at last, "where have YOU been? I've been off on a little job myself and got back." Spike apologized profusely. He had succeeded so easily that he had thought to take a little time to meet up with an old pal whom he ran across, just out of prison. "Yes sir," he replied hastily, "well, I went over to the Dodge house, and I saw them finally. Followed them into a jewelry shop. That lawyer bought her a wrist watch. So I bought one just like it. I thought perhaps we could--" "Give it to me," growled Clutching Hand, seizing it the moment Slim displayed it. "And don't butt in--see?" From the capacious desk, the master criminal pulled a set of small drills, vices, and other jeweler's tools and placed them on the table. "All right," he relented. "Now, do you see what I have just thought of--no? This is just the chance. Look at me." The heelers gathered around him, peering curiously at their master as he worked at the bracelet watch. Carefully he plied his hands to the job, regardless of time. "There," he exclaimed at last, holding the watch up where they could all see it. "See!" He pulled out the stem to set the hands and slowly twisted it between his thumb and finger. He turned the hands until they were almost at the point of three o'clock. Then he held the watch out where all could see it. They bent closer and strained their eyes at the little second hand ticking away merrily. As the minute hand touched three, from the back of the case, as if from the casing itself, a little needle, perhaps a quarter of an inch, jumped out. It seemed to come from what looked like merely a small inset in the decorations. "You see what will happen at the hour of three?" he asked. No one said a word, as he held up a vial which he had drawn from his pocket. On it they could read the label, "Ricinus." "One of the most powerful poisons in the world!" he exclaimed. "Enough here to kill a regiment!" They fairly gasped and looked at it with horror, exchanging glances. Then they looked at him in awe. There was no wonder that Clutching Hand kept them in line, once he had a crook in his power. Opening the vial carefully, he dipped in a thin piece of glass and placed a tiny drop in a receptacle back of the needle and on the needle itself. Altogether it savored of the ancient days of the Borgias with their weird poisoned rings. Then he dropped the vial back into his pocket, pressed a spring, and the needle went back into its unsuspected hiding place. "I've set my invention to go off at three o'clock," he concluded. "Tomorrow forenoon, it will have to be delivered early--and I don't believe we shall be troubled any longer by Miss Elaine Dodge," he added venomously. Even the crooks, hardened as they were, could only gasp. Calmly he wrapped up the apparently innocent engine of destruction and handed it to Spike. "See that she gets it in time," he said merely. "I will, sir," answered Spike, taking it gingerly. Flirty Florrie had returned that afternoon, late, from some expedition on which she had been sent. Rankling in her heart yet was the death of her lover, Dan the Dude. For, although in her sphere of crookdom they are neither married nor given in marriage, still there is a brand of loyalty that higher circles might well copy. Sacred to the memory of the dead, however, she had one desire--revenge. Thus when she arrived home, she went to the telephone to report and called a number, 4494 Greenwich. "Hello, Chief," she repeated. "This is Flirty. Have you done anything yet in the little matter we talked about?" "Say--be careful of names--over the wire," came a growl. "You know--what I mean." "Yes. The trick will be pulled off at three o'clock." "Good!" she exclaimed. "Good-bye and thank you." With his well-known caution Clutching Hand did not even betray names over the telephone if he could help it. Flirty hung up the receiver with satisfaction. The manes of the departed Dan might soon rest in peace! The next day, early in the forenoon, a young man with a small package carefully done up came to the Dodge house. "From Martin's, the jeweler's, for Miss Dodge," he said to Jennings at the door. Elaine and Aunt Josephine were sitting in the library when Jennings announced him. "Oh, it's my watch," cried Elaine. "Show him in." Jennings bowed and did so. Spike entered, and handed the package to Elaine, who signed her name excitedly and opened it. "Just look, Auntie," she exclaimed. "Isn't it stunning?" "Very pretty," commented Aunt Josephine. Elaine put the watch on her wrist and admired it. "Is it all right?" asked Spike. "Yes, yes," answered Elaine. "You may go." He went out, while Elaine gazed rapturously at the new trinket while it ticked off the minutes--this devilish instrument. Early the same morning Kennedy went around again to the apartment house and, cautious not to be seen by Flirty, recovered the telegraphone. Together we carried it to the laboratory. There he set up a little instrument that looked like a wedge sitting up on end, in the face of which was a dial. Through it he began to run the wire from the spools, and, taking an earpiece, put another on my head over my ears. "You see," he explained, "the principle on which this is based is that a mass of tempered steel may be impressed with and will retain magnetic fluxes varying in density and in sign in adjacent portions of itself--little deposits of magnetic impulse. "When the telegraphone is attached to the telephone wire, the currents that affect the receiver also affect the coils of the telegraphone and the disturbance set up causes a deposit of magnetic impulse on the steel wire. "When the wire is again run past these coils with a receiver such as I have here in circuit with the coils, a light vibration is set up in the receiver diaphragm which reproduces the sound of speech." He turned a switch and we listened eagerly. There was no grating and thumping, as he controlled the running off of the wire. We were listening to everything that had been said over the telephone during the time since we left the machine. First came several calls from people with bills and she put them off most adroitly. Then we heard a call that caused Kennedy to look at me quickly, stop the machine and start at that point over again. "That's what I wanted," he said as we listened in: "Give me 4494 Greenwich." "Hello." "Hello, Chief. This is Flirty. Have you done anything yet in the little matter we talked about? "Say--be careful of names--over the wire." "You know--what I mean." "Yes, the trick will be pulled off at three o'clock. "Good! Good-bye and thank you!" "Good-bye." Kennedy stopped the machine and I looked at him blankly. "She called Greenwich 4494 and was told that the trick would be pulled off at three o'clock today," he ruminated. "What trick?" I asked. He shook his head. "I don't know. That is what we must find out. I hadn't expected a tip like that. What I wanted was to find out how to get at the Clutching Hand." He paused and considered a minute, then moved to the telephone. "There's only one thing to do and that's to follow out my original scheme," he said energetically. "Information, please." "Where is Greenwich 4494?" he asked a moment later. The minutes passed. "Thank you," he cried, writing down on a pad an address over on the west side near the river front. Then turning to me he explained, "Walter, we've got him at last!" Craig rose and put on his hat and coat, thrusting a pair of opera glasses into his pocket, in case we should want to observe the place at a distance. I followed him excitedly. The trail was hot. Kennedy and I came at last to the place on the West Side where the crooked streets curved off. Instead of keeping on until he came to the place we sought, he turned and quickly slipped behind the shelter of a fence. There was a broken board in the fence and he bent down, gazing through with the opera glasses. Across the lot was the new headquarters, a somewhat dilapidated old-fashioned brick house of several generations back. Through the glass we could see an evil-countenanced crook slinking along. He mounted the steps and rang the bell, turning as he waited. From a small aperture in the doorway looked out another face, equally evil. Under cover, the crook made the sign of the clutching hand twice and was admitted. "That's the place, all right," whispered Kennedy with satisfaction. He hurried to a telephone booth where he called several numbers. Then we returned to the laboratory, while Kennedy quickly figured out a plan of action. I knew Chase was expected there soon. From the table he picked up the small coil over which I had seen him working, and attached it to the bell and some batteries. He replaced it on the table, while I watched curiously. "A selenium cell," he explained. "Only when light falls on it does it become a good conductor of electricity. Then the bell will ring." Just before making the connection he placed his hat over the cell. Then he lifted the hat. The light fell on it and the bell rang. He replaced the hat and the bell stopped. It was evidently a very peculiar property of the substance, selenium. Just then there came a knock at the door. I opened it. "Hello, Chase," greeted Kennedy. "Well, I've found the new headquarters all right,--over on the west side." Kennedy picked up the selenium cell and a long coil of fine wire which he placed in a bag. Then he took another bag already packed and, shifting them between us, we hurried down town. Near the vacant lot, back of the new headquarters, was an old broken down house. Through the rear of it we entered. I started back in astonishment as we found eight or ten policemen already there. Kennedy had ordered them to be ready for a raid and they had dropped in one at a time without attracting attention. "Well, men," he greeted them, "I see you found the place all right. Now, in a little while Jameson will return with two wires. Attach them to the bell which I will leave here. When it rings, raid the house. Jameson will lead you to it. Come, Walter," he added, picking up the bags. Ten minutes later, outside the new headquarters, a crouched up figure, carrying a small package, his face hidden under his soft hat and up-turned collar, could have been seen slinking along until he came to the steps. He went up and peered through the aperture of the doorway. Then he rang the bell. Twice he raised his hand and clenched it in the now familiar clutch. A crook inside saw it through the aperture and opened the door. The figure entered and almost before the door was shut tied the masking handkerchief over his face, which hid his identity from even the most trusted lieutenants. The crook bowed to the chief, who, with a growl as though of recognition, moved down the hall. As he came to the room from which Spike had been sent on his mission, the same group was seated in the thick tobacco smoke. "You fellows clear out," he growled. "I want to be alone." "The old man is peeved," muttered one, outside, as they left. The weird figure gazed about the room to be sure that he was alone. When Craig and I left the police he had given me most minute instructions which I was now following out to the letter. "I want you to hide there," he said, indicating a barrel back of the house next to the hang-out. "When you see a wire come down from the headquarters, take it and carry it across the lot to the old house. Attach it to the bell; then wait. When it rings, raid the Clutching Hand joint." I waited what seemed to be an interminable time back of the barrel and it is no joke hiding back of a barrel. Finally, however, I saw a coil of fine wire drop rapidly to the ground from a window somewhere above. I made a dash for it, as though I were trying to rush the trenches, seized my prize and without looking back to see where it came from, beat a hasty retreat. Around the lot I skirted, until at last I reached the place where the police were waiting. Quickly we fastened the wire to the bell. We waited. Not a sound from the bell. Up in the room in the joint, the hunched up figure stood by the table. He had taken his hat off and placed it carefully on the table, and was now waiting. Suddenly a noise at the door startled him. He listened. Then he backed away from the door and drew a revolver. As the door slowly opened there entered another figure, hat over his eyes, collar up, a handkerchief over his face, the exact counterpart of the first! For a moment each glared at the other. "Hands up!" shouted the first figure, hoarsely, moving the gun and closing the door, with his foot. The newcomer slowly raised his crooked hand over his head, as the blue steel revolver gaped menacingly. With a quick movement of the other hand, the first sinister figure removed the handkerchief from his face and straightened up. It was Kennedy! "Come over to the center of the room," ordered Kennedy. Clutching Hand obeyed, eyeing his captor closely. "Now lay your weapons on the table." He tossed down a revolver. The two still faced each other. "Take off that handkerchief!" It was a tense moment. Slowly Clutching Hand started to obey. Then he stopped. Kennedy was just about to thunder, "Go on," when the criminal calmly remarked, "You've got ME all right, Kennedy, but in twenty minutes Elaine Dodge will be dead!" He said it with a nonchalance that might have deceived anyone less astute than Kennedy. Suddenly there flashed over Craig the words: "THE TRICK WILL BE PULLED OFF AT THREE O'CLOCK!" There was no fake about that. Kennedy frowned. If he killed Clutching Hand, Elaine would die. If he fought, he must either kill or be killed. If he handed Clutching Hand over, all he had to do was to keep quiet. He looked at his watch. It was twenty-five minutes of three. What a situation! He had caught a prisoner he dared not molest--yet. "What do you mean--tell me?" demanded Kennedy with forced calm. "Yesterday Mr. Bennett bought a wrist watch for Elaine," the Clutching Hand said quietly. "They left it to be regulated. One of my men bought one just like it. Mine was delivered to her today." "A likely story!" doubted Kennedy. For answer, the Clutching Hand pointed to the telephone. Kennedy reached for it. "One thing," interrupted the Clutching Hand. "You are a man of honor." "Yes--yes. Go on." "If I tell you what to do, you must promise to give me a fighting chance." "Yes, yes." "Call up Aunt Josephine, then. Do just as I say." Covering Clutching Hand, Kennedy called a number. "This is Mr. Kennedy, Mrs. Dodge. Did Elaine receive a present of a wrist watch from Mr. Bennett?" "Yes," she replied, "for her birthday. It came this forenoon." Kennedy hung up the receiver and faced Clutching Hand puzzled as the latter said, "Call up Martin, the jeweler." Again Kennedy obeyed. "Has the watch purchased for Miss Elaine Dodge been delivered?" he asked the clerk. "No," came back the reply, "the watch Mr. Bennett bought is still here being regulated." Kennedy hung up the receiver. He was stunned. "The watch will cause her death at three o'clock," said the Clutching Hand. "Swear to leave here without discovering my identity and I will tell you how. You can save her!" A moment Kennedy thought. Here was a quandary. "No," he shouted, seizing the telephone. Before Kennedy could move, Clutching Hand had pulled the telephone wires with almost superhuman strength from the junction box. "In that watch," he hissed, "I have set a poisoned needle in a spring that will be released and will plunge it into her arm at exactly three o'clock. On the needle is ricinus!" Craig advanced, furious. As he did so, Clutching Hand pointed calmly to the clock. It was twenty minutes of three! With a mental struggle, Kennedy controlled his loathing of the creature before him. "All right--but you'll hear from me--sooner than you suspect," he shouted, starting for the door. Then he came back and lifted his hat, hiding as much as possible the selenium cell, letting the light fall on it. "Only Elaine's life has saved you." With a last threat he dashed out. He hailed a cab, returning from some steamship wharves not far away. "Quick!" he ordered, giving the Dodge address on Fifth Avenue. Minute after minute the police and I waited. Was anything wrong? Where was Craig? Just then a tremor grew into a tinkle, then came the strong burr of the bell. Kennedy needed us. With a shout of encouragement to the men I dashed out and over to the old house. Meanwhile Clutching Hand himself had approached the table to recover his weapon and had noticed the queer little selenium cell. He picked it up and for the first time saw the wire leading out. "The deuce!" he cried. "He's planned to get me anyhow!" Clutching Hand rushed to the door--then stopped short. Outside he could hear the police and myself. We had shot the lock on the outside and were already inside. Clutching Hand slammed shut his door and pulled down over it a heavy wooden bar. A few steps took him to the window. There were police in the back yard, too. He was surrounded. But he did not hurry. He knew what to do with every second. At the desk he paused and took out a piece of cardboard. Then with a heavy black marking pencil, he calmly printed on it, while we battered at the barricaded door, a few short feet away. He laid the sign on the desk, then on another piece of cardboard, drew crudely a hand with the index finger, pointing. This he placed on a chair, indicating the desk. Just as the swaying and bulging door gave way, Clutching Hand gave the desk a pull. It opened up--his getaway. He closed it with a sardonic smile in our direction, just before the door crashed in. We looked about. There was not a soul in the room, nothing but the selenium cell, the chairs, the desk. "Look!" I cried catching sight of the index finger, and going over to the desk. We rolled back the top. There on the flat top was a sign: Dear Blockheads: Kennedy and I couldn't wait. Yours as ever, Then came that mysterious sign of the Clutching Hand. We hunted over the rooms, but could find nothing that showed a clue. Where was Clutching Hand? Where was Kennedy? In the next house Clutching Hand had literally come out of an upright piano into the room corresponding to that he had left. Hastily he threw off his handkerchief, slouch hat, old coat and trousers. A neat striped pair of trousers replaced the old, frayed and baggy pair. A new shirt, then a sporty vest and a frock coat followed. As he put the finishing touches on, he looked for all the world like a bewhiskered foreigner. With a silk hat and stick, he surveyed himself, straightening his tie. At the door of the new headquarters, a few seconds later, I stood with the police. "Not a sign of him anywhere," growled one of the officers. Nor was there. Down the street we could see only a straight well-dressed, distinguished looking man who had evidently walked down to the docks to see a friend off, perhaps. Elaine was sitting in the library reading when Aunt Josephine turned to her. "What time is it, dear?" she asked. Elaine glanced at her pretty new trinket. "Nearly three, Auntie--a couple of minutes," she said. Just then there came the sound of feet running madly down the hall way. They jumped up, startled. Kennedy, his coat flying, and hat jammed over his eyes, had almost bowled over poor Jennings in his mad race down the hall. "Well," demanded Elaine haughtily, "what's--" Before she knew what was going on, Craig hurried up to her and literally ripped the watch off her wrist, breaking the beautiful bracelet. He held it up, gingerly. Elaine was speechless. Was this Kennedy? Was he possessed by such an inordinate jealousy of Bennett? As he held the watch up, the second hand ticked around and the minute hand passed the meridian of the hour. A viciously sharp little needle gleamed out--then sprang back into the filigree work again. "Well," she gasped again, "what's the occasion of THIS?" Craig gazed at Elaine in silence. Should he defend his rudeness, if she did not understand? She stamped her foot, and repeated the question a third time. "What do you mean, sir, by such conduct?" Slowly he bowed. "I just don't like the kind of birthday presents you receive," he said, turning on his heel. "Good afternoon." CHAPTER XII THE BLOOD CRYSTALS "On your right is the residence of Miss Elaine Dodge, the heiress, who is pursuing the famous master criminal known as the Clutching Hand." The barker had been grandiloquently pointing out the residences of noted New Yorkers as the big sightseeing car lumbered along through the streets. The car was filled with people and he plied his megaphone as though he were on intimate terms with all the city's notables. No one paid any attention to the unobtrusive Chinaman who sat inconspicuously in the middle of the car. He was Mr. Long Sin, but no one saw anything particularly mysterious about an oriental visitor more or less viewing New York City. Long was of the mandarin type, with drooping mustache, well dressed in American clothes, and conforming to the new customs of an occidentalized China. Anyone, however, who had been watching Long Sin would have seen that he showed much interest whenever any of the wealthy residents of the city were mentioned. The name of Elaine Dodge seemed particularly to strike him. He listened with subtle interest to what the barker said and looked keenly at the Dodge house. The sight-seeing car had passed the house, when he rose slowly and motioned that he wanted to be let off. The car stopped, he alighted and slowly rambled away, evidently marvelling greatly at the strange customs of these uncouth westerners. Elaine was going out, when she met Perry Bennett almost on the steps of the house. "I've brought you the watch," remarked Bennett; "thought I'd like to give it to you myself." He displayed the watch which he himself had bought a couple of days before for her birthday. He had called for it himself at the jeweller's where it had now been regulated. "Oh, thank you," exclaimed Elaine. "Won't you come in?" They had scarcely greeted each other, when Long Sin strolled along. Neither of them, however, had time to notice the quiet Chinaman who passed the house, looking at Elaine sharply out of the corner of his eye. They entered and Long disappeared down the street. "Isn't it a beauty?" cried Elaine, holding it out from her, as they entered the library and examining it with great appreciation. "And, oh, do you know, the strangest thing happened yesterday? Sometimes Mr. Kennedy acts too queerly for anything." She related how Craig had burst in on her and Aunt Josephine and had almost torn the other watch off her wrist. "Another watch?" repeated Bennett, amazed. "It must have been a mistake. Kennedy is crazy." "I don't understand it, myself," murmured Elaine. Long Sin had continued his placid way, revolving some dark and devious plan beneath his impassive Oriental countenance. He was no ordinary personage. In fact he was astute enough to have no record. He left that to his tools. This remarkable criminal had established himself in a hired apartment downtown. It was furnished in rather elegant American style, but he had added to it some most valuable Oriental curios which gave it a fascinating appearance. Long Sin, now in rich Oriental costume, was reclining on a divan smoking a strange looking pipe and playing with two pet white rats. Each white rat had a gold band around his leg, to which was connected a gold chain about a foot in length, and the chains ended in rings which were slipped over Long's little fingers. Ordinarily, he carried the pets up the capacious sleeve of each arm. A servant, also in native costume, entered and bowed deferentially. "A Miss Mary Carson," she lisped in soft English. "Let the lady enter," waved Long Sin, with a smile of subtle satisfaction. The girl bowed again and silently left the room, returning with a handsome, very well dressed white woman. It would be difficult to analyze just what the fascination was that Long Sin exercised over Mary Carson. But as the servant left the room, Mary bowed almost as deferentially as the little Chinese girl. Long merely nodded in reply. After a moment, he slowly rose and took from a drawer a newspaper clipping. Without a word, he handed it to Mary. She looked at it with interest, as one woman always does at the picture of another pretty woman. It was a newspaper cut of Elaine, under which was: ELAINE DODGE, THE HEIRESS, WHOSE BATTLE WITH THE CLUTCHING HAND IS CREATING WORLD WIDE INTEREST. "Now," he began, at last, breaking the silence, "I'll show you just what I want you to do." He went over to the wall and took down a curious long Chinese knife from a scabbard which hung there conspicuously. "See that?" he added, holding it up. Before she could say a word, he had plunged the knife, apparently, into his own breast. "Oh!" cried Mary, startled. She expected to see him fall. But nothing happened. Long Sin laughed. It was an Oriental trick knife in which the blade telescoped into the handle. "Look at it," he added, handing it to her. Long Sin took a bladder of water from a table nearby and concealed it under his coat. "Now, you stab me," he directed. Mary hesitated. But he repeated the command and she plunged the knife gingerly at him. It telescoped. He made her try it over and she stabbed more resolutely. The water from the bladder poured out. "Good!" cried Long Sin, much pleased. "Now," he added, seating himself beside her, "I want you to lure Elaine here." Mary looked at him inquiringly as he returned the knife to its scabbard on the wall. "Remember where it is," he continued. "Now, if you will come into the other room I will show you how to get her." I had been amusing myself by rigging up a contrivance by which I could make it possible to see through or rather over, a door. The idea had been suggested to me by the cystoscope which physicians use in order to look down one's throat, and I had calculated that by using three mirrors placed at proper angles, I could easily reflect rays down to the level of my eye. Kennedy, who had been busy in the other end of the laboratory, happened to look over in my direction. "What's the big idea, Walter?" he asked. It was, I admit, a rather cumbersome and clumsy affair. "Well, you see, Craig," I explained, "you put the top mirror through the transom of a door and--" Kennedy interrupted with a hearty burst of laughter. "But suppose the door has no transom?" he asked, pointing to our own door. I scratched my head, thoughtfully. I had assumed that the door would have a transom. A moment later, Craig went to the cabinet and drew out a tube about as big around as a putty blower and as long. "Now, here's what I call my detectascope," he remarked. "None of your mirrors for me." "I know," I said somewhat nettled, "but what can you see through that putty blower? A key hole is just as good." "Do you realize how little you can really see through a key hole?" he replied confidently. "Try it over there." I did and to tell the truth I could see merely a little part of the hall. Then Kennedy inserted the detectascope. "Look through that," he directed. I put my eye to the eye-piece and gazed through the bulging lens of the other end. I could see almost the whole hall. "That," he explained, "is what is known as a fish-eye lens--a lens that looks through an angle of some 180 degrees, almost twice that of the widest angle lens I know of." I said nothing, but tossed my own crude invention into the corner, while Craig went back to work. Elaine was playing with "Rusty" when Jennings brought in a card on which was engraved the name, "Miss Mary Carson," and underneath, in pencil, was written "Belgian Relief Committee." "How interesting," commented Elaine, rising and accompanying Jennings back into the drawing room. "I wonder what she wants. Very pleased to meet you, Miss Carson," she greeted her visitor. "You see, Miss Dodge," began Mary, "we're getting up this movement to help the Belgians and we have splendid backing. Just let me show you some of the names on our committee." She handed Elaine a list which read: BELGIAN RELIEF COMMITTEE Mrs. Warburton Fish Mrs. Hamilton Beekman Mrs. C. August Iselm Mrs. Belmont Rivington Mrs. Rupert Solvay. "I've just been sent to see if I cannot persuade you to join the committee and attend a meeting at Mrs. Rivington's," she went on. "Why, er," considered Elaine thoughtfully, "er--yes. It must be all right with such people in it." "Can you go with me now?" "Just as well as later," agreed Elaine. They went out together, and, as they were leaving the house a man who had been loitering outside looked at Elaine, then fixedly at her companion. No sooner had they gone than he sped off to a car waiting around the corner. In the dark depths was a sinister figure, the master criminal himself. The watcher had been an emissary of the Clutching Hand. "Chief," he whispered eagerly, "You know Adventuress Mary? Well, she's got Elaine Dodge in tow!" "The deuce!" cried Clutching Hand. "Then we must teach Mary Carson, or whoever she is working for, a lesson. No one shall interfere with our affairs. Follow them!" Elaine and Mary had gone downtown, talking animatedly, and walked down the avenue toward Mrs. Rivington's apartment. Meanwhile, Long Sin, still in his Chinese costume, was explaining to the servant just what he wished done, pointing out the dagger on the wall and replacing the bladder under his jacket. A box of opium was on the table, and he was giving most explicit directions. It was into such a web that Elaine was being unwittingly led by Mary. Entering the hallway of the apartment, Mary rang the bell. Long heard it. "Answer it," he directed the servant who hastened to do so, while Long glided like a serpent into a back room. The servant opened the door and Elaine and Mary entered. He closed the door and almost before they knew locked it and was gone into the back room. Elaine gazed about in trepidation. But before she could say anything, Mary, with a great show of surprise, exclaimed, "Why, I must have made a mistake. This isn't Mrs. Rivington's apartment. How stupid of me." They looked at each other a moment. Then each laughed nervously, as together they started to go out of the door. It was locked! Quickly they ran to another door. It was locked, also. Then they went to the windows. Behind the curtains they were barred and looked out on a blank brick wall in a little court. "Oh," cried Mary wringing her hands, stricken in mock panic, "oh, I'm so frightened. This may be the den of Chinese white slavers!" She had picked up some Chinese articles on a table, including the box that Long had left there. It had a peculiar odor. "Opium!" she whispered, showing it to Elaine. The two looked at each other, Elaine genuinely worried now. Just then, the Chinaman entered and stood a moment gazing at them. They turned and Elaine recoiled from him. Long bowed. "Oh sir," cried Mary, "We've made a mistake. Can't you tell us how to get out?" Long's only answer was to spread out his hands in polite deprecation and shrug his suave shoulders. "No speke Englis," he said, gliding out again from the room and closing the door. Elaine and Mary looked about in despair. "What shall we do?" asked Elaine. Mary said nothing, but with a hasty glance discovered on the wall the knife which Long had already told her about. She took it from its scabbard. As she did so the Chinaman returned with a tray on which were queer drinks and glasses. At the sight of Mary with the knife he scowled blackly, laid the tray down, and took a few steps in her direction. She brandished the knife threateningly, then, as if her nerve failed her, fainted letting the knife fall carefully on the floor so that it struck on the handle and not on the blade. Long quickly caught her as she fainted and carried her out of the room, banging shut the door. Elaine followed in a moment, loyally, to protect her supposed friend, but found that the door had a snap lock on the other side. She looked about wildly and in a moment Long reappeared. As he advanced slowly and insinuatingly, she drew back, pleading. But her words fell on seemingly deaf ears. She had picked up the knife which Mary had dropped and when at last Long maneuvred to get her cornered and was about to seize her, she nerved herself up and stabbed him resolutely. Long staggered back--and fell. As he did so, he pressed the bladder which he had already placed under his coat. A dark red fluid, like blood, oozed out all over him and ran in a pool on the floor. Elaine, too horror-stricken at what had happened even to scream, dropped the knife and bent over him. He did not move. She staggered back and ran through the now open door. As she did so, Long seemed suddenly to come to life. He raised himself and looked after her, then with a subtle smile sank back into his former assumed posture on the floor. When Elaine reached the other room, she found Mary there with the Chinese servant who was giving her a glass of water. At the sight of her, the servant paused, then withdrew into another room further back. Mary, now apparently recovering from her faintness, smiled wanly at Elaine. "It's all right," she murmured. "He is a Chinese prince who thought we were callers." At the reassuring nod of Mary toward the front room, Elaine was overcome. "I--I killed him!" she managed to gasp. "What?" cried Mary, starting up and trembling violently. "You killed him?" "Yes," sobbed Elaine, "he came at me--I had the knife--I struck at him--" The two girls ran into the other room. There Mary looked at the motionless body on the floor and recoiled, horrified. Elaine noticing some spots on her hands and seeing that they were stained by the blood of Long Sin, wiped the spots off on her hankerchief, dropping it on the floor. "Ugh!" exclaimed a guttural voice behind them. It was the servant who had come in. Even his ordinarily impassive Oriental face could not conceal the horror and fear at the sight of his master lying on the floor in a pool of gore. Elaine was now more frightened than ever, if that were possible. "You--kill him--with knife?" insinuated the Chinese. Elaine was dumb. The servant did not wait for an answer, but hastily opened the hall door. To Elaine it seemed that something must be done quickly. A moment and all the house would be in uproar. Instead, he placed his finger on his lips. "Quick--no word," he said, leading the way to the hall door, "and--you must not leave that--it will be a clue," he added, picking up the bloody handkerchief and pressing it into Elaine's hand. They quickly ran out into the hall. "Go--quick!" he urged again, "and hide the handkerchief in the bag. Let no one see it!" He shut the door. As they hurried away, Elaine breathed a sigh of relief. "Why did he let us go, though?" she whispered, her head in a whirl. "I don't know," panted Mary, "but anyhow, thank heaven, we are out of it. Come," she added, taking Elaine's arm, "not a soul has seen us except the servant. Let us get away as quietly as we can." They had reached the street. Afraid to run, they hurried as fast as they could until they turned the first corner. Elaine looked back. No one was pursuing. "We must separate," added Mary. "Let us go different ways. I will see you later. Perhaps they will think some enemy has murdered him." They pressed each other's hands and parted. Meanwhile in the front room, Long Sin was on his feet again brushing himself off and mopping up the blood. "It worked very well, Sam," he said to the servant. They were conversing eagerly and laughing and did not hear a noise in the back room. A sinister figure had made its way by means of a fire-escape to a rear window that was not barred, and silently he had stolen in on them. Cat-like, he advanced, but instead of striking at them, he quietly took a seat in a chair close behind them, a magazine revolver in his hand. They turned at a slight noise and saw him. Genuine fright was now on their faces as they looked at him, open mouthed. "What's all this?" he growled. "I am known as the Clutching Hand. I allow no interferences with my affairs. Tell me what you are doing here with Elaine Dodge." Their beady almond eyes flashed fear. Clutching Hand moved menacingly. There was nothing for the astute Long Sin to do but to submit. Cowed by the well-known power of the master criminal, he took Clutching Hand into his confidence. With a low bow, Long Sin spread out his hands in surrender and submission. "I will tell you, honorable sir," he said at length. "Go on!" growled the criminal. Quickly Long rehearsed what had happened, from the moment the idea of blackmail had entered his head. "How about Mary Carson?" asked Clutching Hand. "I saw her here." Long gave a glance of almost superstitious dread at the man, as if he had an evil eye. "She will be back--is here now," he added, opening the door at a knock and admitting her. Adventuress Mary had hurried back to see that all was right. This time Mary was genuinely scared at the forbidding figure of which she had heard. "It is all right," pacified Long. "Henceforth we work with the honorable Clutching Hand." Clutching Hand continued to emphasize his demands on them, punctuating his sentences by flourishes of the gun as he gave them the signs and passwords which would enable them to work with his own emissaries. It was a strange initiation. At home at last, Elaine sank down into a deep library chair and stared straight ahead. She saw visions of arrest and trial, of the terrible electric chair with herself in it, bound, and of the giving of the fatal signal for turning on the current. Were such things as these going to happen to her, without Kennedy's help? Why had they quarreled? She buried her face in her hands and wept. Then she could stand it no longer. She had not taken off her street clothes. She rose and almost fled from the house. Kennedy and I were still in the laboratory when a knock sounded at the door. I went to the door and opened it. There stood Elaine Dodge. It was a complete surprise to Craig. There was silence between them for a moment and they merely looked at each other. Elaine was pale and woebegone. At last Kennedy took a quick step toward her and led her to a chair. Still he felt a sort of constraint. "What IS the matter?" he asked at length. She hesitated, then suddenly burst out, "Craig--I--I am--a murderess!" I have never seen such a look on Craig's face. I know he wanted to laugh and say, "YOU--a murderess?" yet he would not have offended even her self accusation for the world. He managed to do the right thing and say nothing. Then she poured forth the story substantially as I have set it down, but without the explanation which at that time was not known to any of us. "Oh," expostulated Craig, "there must be some mistake. It's impossible--impossible." "No," she asserted. "Look--here's my handkerchief all spotted with blood." She opened the bag and displayed the blood-spotted handkerchief. He took it and examined it carefully. "Elaine," he said earnestly, not at all displeased, I could see that something had come up that might blot out the past unfortunate misunderstanding, "there simply must be something wrong here. Leave this handkerchief with me. I'll do my best." There was still a little restraint between them. She was almost ready to beg his pardon, for all the coolness there had been between them, yet still hesitated. "Thank you," she said simply as she left the laboratory. Craig went to work abruptly without a word. On the laboratory table he placed his splendid microscope and several cases of slides as well as innumerable micro-photographs. He had been working for some time when he looked up. "Ever hear of Dr. Edward Reichert of the University of Pennsylvania and his wonderful discoveries of how blood crystals vary in different species?" he asked. I had not, but did not admit it. "Well," he went on, "there is a blood test so delicate that one might almost say that he could identify a criminal by the finger prints, so to speak, of his blood crystals. The hemoglobin or red coloring matter forms crystals and the variations of these crystals both in form and molecular construction are such that they set apart every species of animal from every other, and even the races of men--perhaps may even set apart individuals. Here, Walter, we have sample of human blood crystals." I looked through the microscope as he directed. There I could see the crystals sharply defined. "And here," he added, "are the crystals of the blood on Elaine's handkerchief." I looked again as he changed the slides. There was a marked difference and I looked up at him quickly. "It is dog's blood--not human blood," he said simply. I looked again at the two sets of slides. There could be no doubt that there was a plain difference. "Wonderful!" I exclaimed. "Yes--wonderful," he agreed, "but what's the game back of all this--that's the main question now." Long after Clutching Hand had left, Long Sin was giving instructions to his servant and Adventuress Mary just how he had had to change his plans as a result of the unexpected visit. "Very well," nodded Mary as she left him, "I will do as you say--trust me." It was not much later, then, that Elaine received a second visit from Mary. "Show her in, Jennings," she said to the butler nervously. Indeed, she felt that every eye must be upon her. Even Jennings would know of her guilt soon. Anxiously, therefore, Elaine looked at her visitor. "Do you know why the servant allowed us to leave the apartment?" whispered Mary with a glance about fearfully, as if the walls had ears. "No--why?" inquired Elaine anxiously. "He's a tong man who has been chosen to do away with the Prince. He followed me, and says you have done his work for him. If you will give him ten thousand dollars for expenses, he will attend to hiding the body." Here at least was a way out. "But do you think that is all right? Can he do it?" asked Elaine eagerly. "Do it? Why those tong men can do anything for money. Only one must be careful not to offend them." Mary was very convincing. "Yes, I suppose you are right," agreed Elaine, finally. "I had better do as you say. It is the safest way out of the trouble. Yes, I'll do it. I'll stop at the bank now and get the money." They rose and Mary preceded her, eager to get away from the house. At the door, however, Elaine asked her to wait while she ran back on some pretext. In the library she took off the receiver of the telephone and quickly called a number. Our telephone rang in the middle of our conversation on blood crystals and Kennedy himself answered it. It was Elaine asking Craig's advice. "They have offered to hush the thing up for ten thousand dollars," she said, in a muffled voice. She seemed bent on doing it and no amount of argument from him could stop her. She simply refused to accept the evidence of the blood crystals as better than what her own eyes told her she had seen and done. "Then wait for half an hour," he answered, without arguing further. "You can do that without exciting suspicion. Go with her to her hotel and hand her over the money." "All right--I'll do it," she agreed. "What is the hotel?" Craig wrote on a slip of paper what she told him--"Room 509, Hotel La Coste." "Good--I'm glad you called me. Count on me," he finished as he hung up the receiver. Hastily he threw on his street coat. "Go into the back room and get me that brace and bit, Walter," he asked. I did so. When I returned, I saw that he had placed the detectascope and some other stuff in a bag. He shoved in the brace and bit also. "Come on--hurry!" he urged. We must have made record time in getting to the Coste. It was an ornate place, where merely to breathe was expensive. We entered and by some excuse Kennedy contrived to get past the vigilant bellhops. We passed the telephone switchboard and entered the elevator, getting off at the fifth floor. With a hasty glance up and down the corridor, to make sure no one was about, Kennedy came to room 509, then passed to the next, 511, opening the door with a skeleton key. We entered and Craig locked the door behind us. It was an ordinary hotel room, but well-furnished. Fortunately it was unoccupied. Quietly Craig went to the door which led to the next room. It was, of course, locked also. He listened a moment carefully. Not a sound. Quickly, with an exclamation of satisfaction, he opened that door also and went into 509. This room was much like that in which we had already been. He opened the hall door. "Watch here, Walter," he directed, "Let me know at the slightest alarm." Craig had already taken the brace and bit from the bag and started to bore through the wall into room 511, selecting a spot behind a picture of a Spanish dancer--a spot directly back of her snapping black eyes. He finished quickly and inserted the detectascope so that the lens fitted as an eye in the picture. The eye piece was in Room 511. Then he started to brush up the pieces of plaster on the floor. "Craig," I whispered hastily as I heard an elevator door, "someone's coming!" He hurried to the door and looked. "There they are," he said, as we saw Elaine and Mary rounding the corner of the hall. Across the hall, although we did not know it at the time, in room 540, already, Long Sin had taken up his station, just to be handy. There he had been with his servant, playing with his two trained white rats. Long placed them up his capacious sleeves and carefully opened the door to look out. Unfortunately he, was just in time to see the door of 509 open and disclose us. His subtle glance detected our presence without our knowing it. Hastily picking up the brace and bit and the rest of the debris, and with a last look at the detectascope, which was hardly noticeable, even if one already knew it was there, we hurried into 511 and shut the door. Kennedy mounted a chair and applied his eye to the detectascope. Just then Mary and Elaine entered the next room, Mary opening the door with a regular key. "Won't you step in?" she asked. Elaine did so and Mary hesitated in the hall. Long Sin had slipped out on noiseless feet and taken refuge behind some curtains. As he saw her alone, he beckoned to Mary. "There's a stranger in the next room," he whispered. "I don't like him. Take the money and as quickly as possible get out and go to my apartment." At the news that there was a suspicious stranger about, Mary showed great alarm. Everything was so rapid, now, that the slightest hesitation meant disaster. Perhaps, by quickness, even a suspicious stranger could be fooled, she reasoned. At any rate, Long Sin was resourceful. She had better trust him. Mary followed Elaine into the room, where she had seated herself already, and locked the door. "Have you the money there?" she asked. "Yes," nodded Elaine, taking out the package of bills which she had got from the bank during the half hour delay. All this we could see by gazing alternately through the detectascope. Elaine handed Mary the money. Mary counted it slowly. At last she looked up. "It's all right," she said. "Now, I'll take this to that tong leader--he's in a room only just across the hall." She went out. Kennedy at the detectascope was very excited as this went on. He now jumped off the chair on which he had been standing and rushed to the door to head her off. To our surprise, in spite of the fact that we could turn the key in the lock, it was impossible to open it! It was only a moment that Craig paused at the door. The next moment he burst into 509, followed closely by me. With a scream, Elaine was on her feet in an instant. There was no time for explanations, however. He rushed to the door to go out, but it was locked--somehow, on the outside. The skeleton key would not work, at any rate. He shot the lock, and dashed out, calling back, "Walter, stay there--with Elaine." Mary had just succeeded in getting on the elevator as Kennedy hurried down the hall. The door was closed and the car descended. He rang the push bell furiously, but there was no answer. Had he got so far in the chase, only to be outwitted? He dashed back to the room, with us, and jerked down the telephone receiver. "Hello--hello--hello!" he called. No answer. There seemed to be no way to get a connection. What was the matter? He hurried down the hall again. No sooner had Elaine and Mary actually gone into the room, than Long and his servant stole out of 540, across the hall. Somewhere they had obtained a strong but thin rope. Quickly and silently Long tied the handle of the door 511 in which we were to the handle of 540 which he was vacating. As both doors opened inward and were opposite, they were virtually locked. Then Long and his servant hurried down the hallway to the elevator. Down in the hotel lobby, with his followers, the Chinaman paused before the telephone switchboard where two girls were at work. "You may go," ordered Long, and, as his man left, he moved over closer to the switchboard. He was listening eagerly and also watching an indicator that told the numbers of the rooms which called, as they flashed into view. Just as a call from "509" flashed up, Long slipped the rings off his little fingers and loosened the white rats on the telephone switchboard itself. With a shriek, the telephone system of the Coste went temporarily out of business. The operators fled to the nearest chairs, drawing their skirts about them. There was the greatest excitement among all the women in the corridor. Such a display of hosiery was never contemplated by even the most daring costumers. Shouts from the bellboys who sought to catch the rats who scampered hither and thither in frightened abandon mingled with the shrieks of the ladies. Kennedy had succeeded in finding the alcove of the floor clerk in charge of the fifth floor. There on his desk was an instrument having a stylus on the end of two arms, connected to a system of magnets. It was a telautograph. Unceremoniously, Craig pushed the clerk out of his seat and sat down himself. It was a last chance, now that the telephone was out of commission. Downstairs, in the hotel office, where the excitement had not spread to everyone, was the other end of the electric long distance writer. It started to write, as Kennedy wrote, upstairs: "HOUSE DETECTIVE--QUICK--HOLD WOMAN WITH BLUE CHATELAINE BAG, GETTING OUT OF ELEVATOR." The clerks downstairs saw it and shouted above the din of the rat-baiting. "McCann--McCann!" The clerk had torn off the message from the telautograph register, and handed it to the house man who pushed his way to the desk. Quickly the detective called to the bell-hops. Together they hurried after the well-dressed woman who had just swept out of the elevator. Mary had already passed through the excited lobby and out, and was about to cross the street--safe. McCann and the bell-hops were now in full cry after her. Flight was useless. She took refuge in indignation and threats. But McCann was obdurate. She passed quickly to tears and pleadings. It had no effect. They insisted on leading her back. The game was up. Even an offer of money failed to move their adamantine hearts. Nothing would do but that she must face her accusers. In the meantime Long Sin had recovered his precious and useful pets. Life in the Coste had assumed something of its normal aspect, and Craig had succeeded in getting an elevator. It was just as Mary was led in threatening and pleading by turns that he stepped off in the lobby. There was, however, still just enough excitement to cover a little pantomime. Long Sin had been about to slip out of a side door, thinking all was well, when he caught sight of Mary being led back. She had also seen him, and began to struggle again. Quickly he shook his head, indicating for her to stop. Then slowly he secretly made the sign of the Clutching Hand at her. It meant that she must not snitch. She obeyed instantly, and he quietly disappeared. "Here," cried Kennedy, "take her up in the elevator. I'll prove the case." With the house detective and Kennedy, Mary was hustled into the elevator and whisked back as she had escaped. In the meantime I had gathered up what stuff we had in the room we had entered and had returned with Kennedy's bag. "Wh--what's it all about?" inquired Elaine excitedly. I tried to explain. Just then, out in the hall we could hear loud voices, and that of Mary above the rest. Kennedy, a man who looked like a detective, and some bell-boys were leading her toward us. "Now--not a word of who she is in the papers, McCann," Kennedy was saying, evidently about Elaine. "You know it wouldn't sound well for La Coste. As for that woman--well, I've got the money back. You can take her off--make the charge." As the house man left with Mary, I handed Craig his bag. We moved toward the door, and as we stood there a moment with Elaine, he quietly handed over to her the big roll of bills. She took it, with surprise still written in her big blue eyes. "Oh--thank you--I might have known it was only a blackmail scheme," she cried eagerly. Craig held out his hand and she took it quickly, gazing into his eyes. Craig bowed politely, not quite knowing what to do under the circumstances. If he had been less of a scientist, he might have understood the look on her face, but, with a nod to me, he turned, and went. As she looked first at him, then at the paltry ten thousand in her hand, Elaine stamped her little foot in vexation. "I'm glad I DIDN'T say anything more," she cried. "No--no--he shall beg my pardon first--there!" CHAPTER XIII THE DEVIL WORSHIPPERS Elaine was seated in the drawing room with Aunt Josephine one afternoon, when her lawyer, Perry Bennett, dropped in unexpectedly. He had hardly greeted them when the butler, Jennings, in his usual impassive manner announced that Aunt Josephine was wanted on the telephone. No sooner were Elaine and Bennett alone, than Elaine, turning to him, exclaimed impulsively, "I'm so glad you have come. I have been longing to see you and to tell you about a strange dream I have had." "What was it?" he asked, with instant interest. Leaning back in her chair and gazing before her tremulously, Elaine continued, "Last night, I dreamed that father came to me and told me that if I would give up Kennedy and put my trust in you, I would find the Clutching Hand. I don't know what to think of it." Bennett, who had been listening intently, remained silent for a few moments. Then, putting down his tea cup, he moved over nearer to Elaine and bent over her. "Elaine," he said in a low tone, his remarkable eyes looking straight into her own, "you must know that I love you. Then give me the right to protect you. It was your father's dearest wish, I believe, that we should marry. Let me share your dangers and I swear that sooner or later there will be an end to the Clutching Hand. Give me your answer, Elaine," he urged, "and make me the happiest man in all the world." Elaine listened, and not unsympathetically, as Bennett continued to plead for her answer. "Wait a little while--until to-morrow," she replied finally, as if overcome by the recollections of her weird dream and the unexpected sequel of his proposal. "Let it be as you wish, then," agreed Bennett quietly. He took her hand and kissed it passionately. An instant later Aunt Josephine returned. Elaine, unstrung by what had happened, excused herself and went into the library. She sank into one of the capacious arm chairs, and passing her hand wearily over her throbbing forehead, closed her eyes in deep thought. Involuntarily, her mind travelled back over the rapid succession of events of the past few weeks and the part that she had thought, at least, Kennedy had come to play in her life. Then she thought of their recent misunderstanding. Might there not be some simple explanation of it, after all, which she had missed? What should she do? She solved the problem by taking up the telephone and asking for Kennedy's number. I was chatting with Craig in his laboratory, and, at the same time, was watching him in his experimental work. Just as a call came on the telephone, he was pouring some nitro-hydrochloric acid into a test tube to complete a reaction. The telephone tinkled and he laid down the bottle of acid on his desk, while he moved a few steps to answer the call. Whoever the speaker was, Craig seemed deeply interested, and, not knowing who was talking on the wire, I was eager to learn whether it was anyone connected with the case of the Clutching Hand. "Yes, this is Mr. Kennedy," I heard Craig say. I moved over toward him and whispered eagerly, "Is there anything new?" A little impatient at being interrupted, Kennedy waved me off. It occurred to me that he might need a pad and pencil to make a note of some information and I reached over the desk for them. As I did so my arm inadvertently struck the bottle of acid, knocking it over on the top of the desk. Its contents streamed out saturating the telephone wires before I could prevent it. In trying to right the bottle my hand came in contact with the acid which burned like liquid fire, and I cried out in pain. Craig hastily laid down the receiver, seized me and rushed me to the back of the laboratory where he drenched my hand with a neutralizing liquid. He bound up the wounds caused by the acid, which proved to be slight, after all, and then returned to the telephone. To his evident annoyance, he discovered that the acid had burned through the wires and cut off all connection. Though I did not know it, my hand was, in a sense at least, the hand of fate. At the other end of the line, Elaine was listening impatiently for a response to her first eager words of inquiry. She was astounded to find, at last, that Kennedy had apparently left the telephone without any explanation or apology. "Why--he rang off," she exclaimed angrily to herself, as she hung up the receiver and left the room. She rejoined her Aunt Josephine and Bennett who had been chatting together in the drawing room, still wondering at the queer rebuff she had, seemingly, experienced. Bennett rose to go, and, as he parted from Elaine, found an opportunity to whisper a few words reminding her of her promised reply on the morrow. Piqued, at Kennedy, she flashed Bennett a meaning glance which gave him to understand that his suit was not hopeless. In the center of a devious and winding way, quite unknown to all except those who knew the innermost secrets of the Chinese quarter and even unknown to the police, there was a dingy tenement house, apparently inhabited by hardworking Chinamen, but in reality the headquarters of the notorious devil worshippers, a sect of Satanists, banned even in the Celestial Empire. The followers of the cult comprised some of the most dangerous Chinese criminals, thugs, and assassins, besides a number of dangerous characters who belonged to various Chinese secret societies. At the head of this formidable organization was Long Sin, the high priest of the Devil God, and Long Sin had, as we knew, already joined forces with the notorious Clutching Hand. The room in which the uncanny rites of the devil worshippers were conducted was a large apartment decorated in Chinese style, with highly colored portraits of some of the devil deities and costly silken hangings. Beside a large dais depended a huge Chinese gong. On the dais itself stood, or rather sat, an ugly looking figure covered with some sort of metallic plating. It almost seemed to be the mummy of a Chinaman covered with gold leaf. It was thin and shrunken, entirely nude. Into this room came Long Sin attired in an elaborate silken robe. He advanced and kowtowed before the dais with its strange figure, and laid down an offering before it, consisting of punk sticks, little dishes of Chinese cakes, rice, a jar of oil, and some cooked chicken and pork. Then he bowed and kowtowed again. This performance was witnessed by twenty or thirty Chinamen who knelt in the rear of the room. As Long Sin finished his devotions they filed past the dais, bowing and scraping with every sign of abject reverence both for the devil deity and his high priest. At the same time an aged Chinaman carrying a prayer wheel entered the place and after prostrating himself devoutedly placed the machine on a sort of low stool or tabourette and began turning it slowly, muttering. Each revolution of this curious wheel was supposed to offer a prayer to the god of the netherworld. A few moments later, Long Sin, who had been bowing before the metallic figure in deepest reverence, suddenly sprang to his feet. His glazed eye and excited manner indicated that he had received a message from the lips of the strange idol. The worshippers who had prostrated themselves in awe at the sight of their high priest in the unholy frenzy, all rose to their feet and crowded forward. At the same time Long Sin advanced a step to meet them, holding his arms outstretched as if to compel silence while he delivered his message. Long Sin struck several blows on the resounding gong and then raised his voice in solemn tones. "Ksing Chau, the Terrible, demands a consort. She is to be foreign--fair of face and with golden hair." Amazed at this unexpected message, the Chinamen prostrated themselves again and their unhallowed devotions terminated a few moments later amid suppressed excitement as they filed out. At the same time, in a room of the adjoining house, the Clutching Hand himself was busily engaged making the most elaborate preparations for some nefarious scheme which his fertile mind had evolved. The room had been fitted up as a medium's seance parlor, with black hangings on the walls, while at one side there was a square cabinet of black cloth, with a guitar lying before it. Two of the Clutching Hand's most trusted confederates and a hard-faced woman of middle age, dressed in plain black, were putting the finishing touches to this apartment, when their Chief entered. Clutching Hand gazed about the room, now and then giving an order or two to make more effective the setting for the purpose which he had in mind. Finally he nodded in approval and stepped over to the fire place where logs were burning brightly in a grate. Pressing a spring in the mantelpiece, the master criminal effected an instant transformation. The logs in the fireplace, still burning, disappeared immediately through the side of the brick tiling and a metal sheet covered them. An aperture opened at the back, as if by magic. Through this opening Clutching Hand made his way quickly and disappeared. Emerging on the other side of the peculiar fireplace, Clutching Hand pushed aside a curtain which barred the way and looked into the Chinese temple, taking up a position behind the metallic figure on the dais. The Chinamen had by this time finished their devotions, if such they might be called, and the last one was leaving, while Long Sin stood alone on the dais. The noise of the departing Satanists had scarcely died away when Clutching Hand stepped out. "Follow me," he ordered hoarsely seizing Long Sin by the arm and leading him away. They passed through the passageway of the fireplace and, having entered the seance room, Clutching Hand began briefly explaining the purpose of the preparations that had been made. Long Sin wagged his head in voluble approval. As Clutching Hand finished, the Chinaman turned to the hard-faced woman who was to act the part of medium and added some directions to those Clutching Hand had already given. The medium nodded acquiescence, and a moment later, left the room to carry out some ingenious plot framed by the master mind of the criminal world. . . . . . . . . Elaine was standing in the library gazing sadly at Kennedy's portrait, thinking over recent events and above all the rebuff over the telephone which she supposed she had received. It all seemed so unreal to her. Surely, she felt in her heart, she could not have been so mistaken in the man. Yet the facts seemed to speak for themselves. In spite of it all, she was almost about to kiss the portrait when something seemed to stay her hands. Instead she laid the picture down, with a sigh. A moment later, Jennings entered with a card on a salver. Elaine took it and saw with surprise the name of her caller: MADAME SAVETSKY, MEDIUM Beneath the engraved name were the words written in ink, "I have a message from the spirit of your father." "Yes, I will see her," cried Elaine eagerly, in response to the butler's inquiry. She followed Jennings into the adjoining room and there found herself face to face with the hard-featured woman who had only a few moments before left the Clutching Hand. Elaine looked rather than spoke her inquiry. "Your father, my dear," purred the medium with a great pretence of suppressed excitement, "appeared to me, the other night, from the spirit world. I was in a trance and he asked me to deliver a message to you." "What was the message?" asked Elaine breathlessly, now aroused to intense interest. "I must go into a trance again to get it," replied the insinuating Savetsky, "and if you like I can try it at once, provided we can be left alone long enough." "Please--don't wait," urged Elaine, pulling the portieres of the doors closer, as if that might insure privacy. Seated in her chair, the medium muttered wildly for a few moments, rolled her eyes and with some convulsive movements pretended to go into a trance. Savetsky seemed about to speak and Elaine, in the highest state of nervous tension, listened, trying to make something of the gibberish mutterings. Suddenly the curtains were pushed aside and Aunt Josephine and Bennett, who had just come in, entered. "I can do nothing here," exclaimed Savetsky, starting up and looking about severely. "You must come to my seance chamber where we shall not be interrupted." "I will," cried Elaine, vexed at the intrusion at that moment. "I must have that message--I must." "What's all this, Elaine?" demanded Aunt Josephine. Hurriedly, Elaine poured forth to her aunt and Bennett the story of the medium's visit and the promised message from her father in the other world. Aunt Josephine, who was not one easily to be imposed on, strongly objected to Elaine's proposal to accompany Savetsky to the seance chamber, but Elaine would not be denied. She pleaded with her aunt, urging that she be allowed to go. "It might be safe for Elaine to go," Bennett finally suggested to Aunt Josephine, "if you and I accompanied her." All this time the medium was listening closely to the conversation. Elaine looked at her inquiringly. With a shrug, she indicated that she had no objection to having Elaine escorted to the parlor by her friends. At last Aunt Josephine, influenced by Elaine's pleadings and Bennett's suggestion, gave in and agreed to join in the visit. A few moments later, in the Dodge car, Elaine, the medium, and her two escorts started for the Chinese quarter. . . . . . . . . At the house, the medium opened the door with her key and ushered in her three visitors. Long Sin who had been watching for their arrival from the window now hastily withdrew from the seance room and disappeared behind the black curtains. Entering the room the medium at once prepared for the seance by pulling down the window shades. Then she seated herself in a chair beside the cabinet, and appeared to fall off slowly into a trance. Her strange proceedings were watched with the greatest curiosity by Elaine as well as Aunt Josephine and Bennett, who had taken seats placed at one side of the room. The room itself was dimly lighted, and the curtains of the cabinet seemed, in the obscurity, to sway back and forth as if stirred by some ghostly breeze. All of them were now quite on edge with excitement. Suddenly an indistinct face was seen to be peering through the black curtains, as it were. The guitar, as if lifted by an invisible hand, left the cabinet, floated about close to the ceiling, and returned again. It was eerie. At last a voice, deep, sepulchral, was heard in slow and solemn tones. "I am Eeko--the spirit of Taylor Dodge. I will give no message until one named Josephine leaves the room." No sooner had the words been uttered than the medium came writhing out of her trance. "What happened?" she asked, looking at Elaine. Elaine reported the spirit's words. "We can get nothing if your Aunt stays here," Savetsky added, insisting that Aunt Josephine must go. "Your father cannot speak while she is present." Aunt Josephine, annoyed by what she had heard, indignantly refused to go and was deaf to all Elaine's pleadings. "I think it will be all right," finally acquiesced Bennett, seeing how bent Elaine was on securing the message. "I'll stay and protect her." Aunt Josephine finally agreed. "Very well, then," she protested, marching out of the room in a high state of indignation. She had scarcely left the house, however, when she began to suspect that all was not as it ought to be. In fact, the idea had no sooner occurred to her than she decided to call on Kennedy and she ordered the chauffeur to take her as quickly as possible to the laboratory. . . . . . . . . Kennedy had not been in the laboratory all the day, after my experience with the acid and I was impatiently awaiting his arrival. At last there came a knock at the door and I opened it hurriedly. There was a messenger boy who handed me a note. I tore it open. It was from Kennedy and read, "I shall probably be away for two or three days. Call up Elaine and tell her to beware of a certain Madame Savetsky." I was still puzzling over the note and was just about to call up Elaine when the speaking tube was blown and to my surprise I found it was Aunt Josephine who had called. "Where is Mr. Kennedy?" she asked, greatly agitated. "He has gone away for a few days," I replied blankly. "Is there anything I can do?" She was very excited and hastily related what had happened at the parlor of the medium. "What was her name?" I asked anxiously. "Madame Savetsky," she replied, to my surprise. Astounded, I picked up Craig's note from the desk and handed it to her without a word. She read it with breathless eagerness. "Come back there with me, please," she begged, almost frantic with fear now. "Something terrible may have happened." . . . . . . . . Aunt Josephine had hardly left Savetsky when the trance was resumed and, in a few minutes, there came all sorts of supernatural manifestations. The table beside Elaine began to turn and articles on it dropped to the floor. Violent rappings followed in various parts of the room. Both Elaine and Bennett who sat together in silence were much impressed by the marvellous phenomena--not being able to see, in the darkness, the concealed wires that made them possible. Suddenly, from the mysterious shadows of the cabinet, there appeared the spirit of Long Sin, whose death Elaine still believed she had caused when Adventuress Mary had lured her to the apartment. Elaine was trembling with fear at the apparition. As before, a strange voice sounded in the depths of the cabinet and again a message was heard, in low, solemn tones. "I am Keka, and I have with me Long Sin. His blood cries for vengeance." Elaine was overcome with horror at the words. From the cabinet ran a thick stream of red, like blood, from which she recoiled, shuddering. Then a dim, ghostly figure, apparently that of Long Sin, appeared. The face was horribly distorted. It seemed to breathe the very odor of the grave. With arms outstretched, the figure glided from the cabinet and approached Elaine. She shrank back further in fright, too horrified even to scream. At the same moment, the medium drew a vapor pistol from her dress, and, as the ghost of Long Sin leaped at Elaine, Savetsky darted forward and shot a stream of vapor full in Bennett's face. Bennett dropped unconscious, the lights in the darkened room flashed up, and several of the men of the Clutching Hand rushed in. Quickly the fireplace was turned on its cleverly constructed hinges, revealing the hidden passage. Before any effective resistance could be made, Elaine and Bennett were hustled through the passage, securely bound, and placed on a divan in a curtained chamber back of the altar of the devil worshippers. There they lay when Long Sin, now in his priestly robes, entered. He looked at them a moment. Then he left the room with a sinister laugh. . . . . . . . . It was at that moment that I, little dreaming of what had been taking place, arrived with Aunt Josephine at the house of the medium. She answered my ring and admitted us. To our surprise, the seance room was empty. "Where is the young lady who was here?" I asked. "Miss Dodge and the gentleman just left a few minutes ago," the medium explained, as we looked about. She seemed eager to satisfy us that Elaine was not there. Apparently there was no excuse for disputing her word, but, as we turned to leave, I happened to notice a torn handkerchief lying on the floor near the fireplace. It flashed over me that perhaps it might afford a clue. As I passed it, I purposely dropped my soft hat over it and picked up the hat, securing the handkerchief without attracting Savetsky's attention. Aunt Josephine was keen now for returning home to find out whether Elaine was there or not. No sooner had she entered the car and driven off, than I examined the handkerchief. It was torn, as if it had been crushed in the hand during a struggle and wrenched away. I looked closer. In the corner was the initial, "E." That was enough. Without losing another precious moment I hurried around to the nearest police station, where I happened to be known, having had several assignments for the Star in that part of the city, and gave an alarm. The sergeant detailed several roundsmen, and a man in plainclothes, and together we returned to the house, laying a careful plan to surround it secretly, while the plainclothesman and I obtained admittance. . . . . . . . . Meanwhile, the Chinese devil worshippers had again gathered in their cursed temple and Long Sin, in his priestly robe, appeared on the dais. The worshippers kowtowed reverently to him, while at the back again stood the aged Chinaman patiently turning his prayer wheel. Two braziers, or smoke pots, had been placed on the dais, one of which Long Sin touched with a stick causing it to burst out into dense fumes. Standing before them, he chanted in nasal tones, "The white consort of the great Ksing Chau has been found. It is his will that she now be made his." As he finished intoning the message, Long Sin signaled to two young Chinamen to go into the anteroom. A moment later they returned with Elaine. Frightened though she was, Elaine made no attempt to struggle, even when they had cut her bonds. She was busily engaged in seeking some method of escape. Her eyes travelled ever the place quickly. Apparently, there was no means of exit that was not guarded. Long Sin saw her look, and smiled quietly. They had carried her up to the dais, and now Long Sin faced her and sternly ordered her to kowtow to the gruesome metallic figure. She refused, but instantly the Chinamen seized her arm and twisted it, until they had compelled her to fall to her knees. Having forced her to kowtow, Long Sin turned to the assembled devil dancers. "With magic and rare drugs," he chanted, "she shall be made to pass beyond and her body encased in precious gold shall be the consort of Ksing Chau--forever and ever." He made another sign and several pots and braziers were brought out and placed on the dais beside Elaine. She was, by this time, completely overcome by the horror of the situation. There was apparently no escape. With callous deviltry, the oriental satanists had made every arrangement for embalming and preserving the body of Elaine. Pots filled with sticky black material were slowly heated, amid weird incantations, while other Chinamen laid out innumerable sheets of gold leaf. At last all seemed to be in readiness to proceed. "Hold her," ordered Long Sin in guttural Chinese to the two attendants, as he approached her. Long Sin held in his hand a small, profusely decorated pot from which smoke was escaping. As he approached he passed this receptacle under her nose once, twice, three times. Gradually Elaine fell into unconsciousness. . . . . . . . . While Elaine was facing death in the power of the devil worshippers, I had reached the house of Savetsky next door with the police, and the place had been quietly surrounded. With the plainclothesman, a daring and intelligent fellow, I went to the door and rang the bell. "What can I do for you?" asked the medium, admitting us. "My friend, here," I parleyed, "is in great business trouble. Can your controlling spirit give him advice?" We had managed to gain the interior of the seance room, and I suppose there was nothing else for her to say, under the circumstances, but, "Why--yes,--if the conditions are good, the control can probably tell us just what he wants to know." Savetsky set to work preparing the room for a seance. As she moved over to the window to pull down the shades, she must have caught sight of one or two of the policemen who had incautiously exposed themselves from the hiding places in which I had disposed them before we entered. At any rate, Savetsky did not lose a jot of her remarkable composure. "I'm sorry," she remarked merely, "but I'm afraid my control is weak and cannot work today." She took a step toward the door, motioning us to leave. Neither of us paid any attention to that hint, but remained seated as we had been before. "Go!" she exclaimed at length, for the first time showing a trace of nervousness. Evidently her suspicions had been fully confirmed by our actions. We tried to argue with her to gain time. But it was of no use. Almost before I knew what she was doing, she made a dash for something in the corner of the room. It was time for open action, and I seized her quickly. My detective was on his feet in an instant. "I'll take care of her," he ground out, seizing her wrists in his vice-like grasp. "You give the signal." I rushed to the window, threw up the shade and opened the sash, waving our preconcerted sign, turning again toward the room. With a sudden accession of desperate strength, Savetsky broke away from the plainclothesman and again attempted to get at something concealed on the wall. I had turned just in time to fling myself between her and whatever object she had in mind. As the detective took her again and twisted her arm until she cried out in pain, I hastily investigated the wall. She had evidently been attempting to press a button that rang a concealed bell. What did it all mean? . . . . . . . . Elaine, now completely unconscious, was being held by the Chinamen, while her arm was smeared with sticky black material from the cauldron by Long Sin. As the high priest of Satan worked, the devil worshippers kowtowed obediently. Suddenly the aged Chinaman with the prayer wheel stopped his incessant, impious turning, and rising, held up his hand as if to command attention. Amid a general exclamation of wonder, he walked to the dais and mounted it, turning and facing the worshippers. "This is nonsense," he cried in a loud tone. "Why should our great Ksing Chau desire a white devil? I, a great grandfather, demand to know." The effect on the worshippers was electric. They paused in their obeisance and stared at the speaker, then at their high priest. Shaking with rage, Long Sin ordered the intruder off the dais. But the aged devotee refused to go. "Throw him out," he ordered his attendants. For answer, as the two young Chinamen approached, the old Chinaman threw them down to the floor with a quick jiu-jitsu movement. His strength seemed miraculous for so aged a man. Furious now beyond expression, Long Sin stepped forward himself. He seized the beard and queue of the intruder. To his utter amazement, they came off! It was Kennedy! With his automatic drawn, before the astounded devil dancers could recover themselves, Craig stood at bay. Long Sin leaped behind the big gong. As the Chinamen rushed forward to seize him, Kennedy shot the leader of Long Sin's attendants and struck down the other with a blow. The rush was checked for the moment. But the odds were fearful. Kennedy seized Elaine's yielding body and, pushing back the curtains to the anteroom, succeeded in gaining it, and locking the door into the main temple. Bennett was still lying on the floor tightly bound. With a few deft cuts by a Chinese knife which he had picked up, Kennedy released him. At the same time, Chinamen were trying to batter down the door, Kennedy's last bulwark. It was swaying under their repeated blows. Kennedy rushed to the door and fired through it at random to check the attack for a few moments. . . . . . . . . While Kennedy was thus besieged by the devil worshippers in the anteroom, several policemen and detectives gathered in the seance room with us, next door, where Savetsky was held a defiant and mute prisoner. I had discovered the bell, and, taking that as a guide, I started to trace the course of a wire which ran alongside the wall, feeling certain that it would give me a clue to some adjoining room to which Elaine might possibly have been taken. To the fireplace I traced the bell, and, in pulling on the wire, I luckily pressed a secret spring. To my amazement, the whole fireplace swung out of sight and disclosed a secret passageway. I looked through it. It was almost at that precise instant that the door of the anteroom burst open and the Chinamen swarmed in, urged on by the insane exhortations of Long Sin. To my utter amazement, I recognized Kennedy's voice. In the first onslaught, Craig shot one Chinaman dead, then closed with the others, slashing right and left with the Chinese knife he had picked up. Bennett came to his aid, but was immediately overcome by two Chinamen, who evidently had been detailed for that purpose. Meanwhile, Kennedy and the others were engaged in a terrible life and death struggle. They fought all over the room, dismantling it, and even tearing the hangings from the wall. It was just as the Chinese was about to overpower him that I led the police and detectives through the passageway of the fireplace. It was a glorious fight that followed. Long Sin and his Chinamen were no match for the police and were soon completely routed, the police striking furiously in all directions and clearing the room. Instantly, Kennedy thought of the fair object of all this melee. He rushed to the divan on which he had placed Elaine. She was slowly returning to consciousness. As she opened her eyes, for an instant, she gazed at Craig, then at Bennett. Still not comprehending just what had happened, she gave her hand to Bennett. Bennett lifted her to her feet and slowly assisted her as she tried to walk away. Kennedy watched them, more stupefied than if he had been struck over the head by Long Sin. . . . . . . . . Police and detectives were now taking the captured Chinamen away, as Bennett, his arm about Elaine, led her gently out. A young detective had slipped the bracelets over Long Sin's wrist, and I was standing beside him. Kennedy, in a daze at the sight of Elaine and Bennett, passed us, scarcely noticing who we were. As Craig collected his scattered forces, Long Sin motioned to him, as if he had a message to deliver. Kennedy frowned suspiciously. He was about to turn away, when the Chinaman began pleading earnestly for a chance to say a few words. "Step aside for a moment, you fellows, won't you please," Craig asked. "I will hear what you have to say, Long Sin." Long Sin looked about craftily. "What is it?" prompted Craig, seeing that at last they were all alone. Long Sin again looked around. "Swear that I will go free and not suffer," Long Sin whispered, "and I will betray the great Clutching Hand." Kennedy studied the Chinaman keenly for a moment. Then, seemingly satisfied with the scrutiny, he nodded slowly assent. As Craig did so, I saw Long Sin lean over and whisper into Kennedy's ear. Craig started back in horror and surprise. CHAPTER XIV THE RECKONING Pacing up and down his den in the heart of Chinatown, Long Sin was thinking over his bargain with Kennedy to betray the infamous Clutching Hand. It was a small room in a small and unpretentious house, but it adequately expressed the character of the subtle Oriental. The den was lavishly furnished, while the guileful Long Sin himself wore a richly figured lounging gown of the finest and costliest silk, chosen for the express purpose of harmonizing with the luxurious Far Eastern hangings and furniture so as to impress his followers and those whom he might choose as visitors. At length he seated himself at a teakwood table, still deliberating over the promise he had been forced to make to Kennedy. He sat for some moments, deeply absorbed in thought. Suddenly an idea seemed to strike him. Lifting a little hammer, he struck a Chinese gong on the table at his side. At the same time, he leaned over and turned a knob at the side of a large roll-top desk. A few seconds later a sort of hatchway, covered by a rug on the floor, in one corner of the room, was slowly lifted and Long Sin's secretary, a sallow, cadaverous Chinaman, appeared from below. He stepped noiselessly into the room and shuffled across to Long Sin. Long Sin scowled, as though something had interfered with his own plans, but tore open the envelope without a word, spreading out on his lap the sheet of paper it contained. The letter bore a typewritten message, all in capitals, which read: "BE AT HEADQUARTERS AT 12. DESTROY THIS IMMEDIATELY." At the bottom of the note appeared the sinister signature of the Clutching Hand. As soon as he had finished reading the note, the Chinaman turned to his obsequious secretary, who stood motionless, with folded arms and head meekly bent. "Very well," he said with an imperious wave of his hand. "You may go." Bowing low again, the secretary shuffled across and down again through the hatchway, closing the door as he descended. Long Sin read the note once more, while his inscrutable face assumed an expression of malicious cunning. Then he glanced at his heavy gold watch. With an air of deliberation, he reached for a match and struck it. He had just placed the paper in the flame when suddenly he seemed to change his mind. He hastily blew out the match which had destroyed only a corner of the paper, then folded the note carefully and placed it in his pocket. A few moments later, with a malignant chuckle, Long Sin rose slowly and left the room. . . . . . . . . Meanwhile, the master criminal was busily engaged in putting the finishing touches to a final scheme of fiendish ingenuity for the absolute destruction of Craig Kennedy. He had been at work in a small room, fitted up as a sort of laboratory, in the mysterious house which now served as his headquarters. On all sides were shelves filled with bottles of deadly liquids and scientific apparatus for crime. Jars of picric acid, nitric acid, carboys of other chemicals, packages labelled gunpowder, gun cotton and nitroglycerine, as well as carefully stoppered bottles of prussic acid, and the cyanides, arsenic and other poisons made the place bear the look of a veritable devil's workshop. Clutching Hand, at a bench in one corner, had just completed an infernal machine of diabolical cunning, and was wrapping it carefully in paper to make an innocent package. He was interrupted by a knock at the door. Laying down the bomb he went to answer the summons with a stealthy movement. There stood Long Sin, who had disguised himself as a Chinese laundryman. "On time--good!" growled Clutching Hand surlily as he closed the door with equal care. No time was wasted in useless formalities. "This is a bomb," he went on, pointing to the package. "Carry it carefully. On no account let it slip, or you are a dead man. It must be in Kennedy's laboratory before night. Understand? Can you arrange it?" Long Sin looked the dangerous package over, then with an impassive look, replied, "Have no fear. I can do it. It will be in the laboratory within an hour. Trust me." Long Sin nodded sagely, while Clutching Hand growled his approval as he opened the door and let out the Chinaman. Long Sin departed as stealthily as he had come, the frightful engine of destruction hugged up carefully under his wide-sleeved coolie shirt. For a moment Clutching Hand gave himself up to the exquisite contemplation of what he had just done, then turned to clean up his workshop. . . . . . . . . In Kennedy's laboratory I was watching Craig make some experiments with a new X-ray apparatus which had just arrived, occasionally looking through the fluoroscope when he was examining some unusually interesting object. We were oblivious to the passage of time, and only a call over our speaking tube diverted our attention. I opened the door and a few seconds later Long Sin himself entered. Kennedy looked up inquiringly as the Chinaman approached, holding out a package which he carried. "A bomb," he said, in the most matter of fact way. "I promised to have it placed in your laboratory before night." The placid air with which the grotesque looking Chinaman imparted this astounding information was in itself preposterous. His actions and words as he laid the package down gingerly on the laboratory table indicated that he was telling the truth. Kennedy and I stared at each other in blank amazement for a moment. Then the humor of the thing struck us both and we laughed outright. Clutching Hand had told him to deliver it--and he had done so! Hastily I filled a pail with water and brought it to Kennedy. "If it is really a bomb," I remarked, "why not put the thing out of commission?" "No, no, Walter," he cried quickly, shaking his head. "If it's a chemical bomb, the water might be just the thing to make the chemicals run together and set it off. No, let us see what the new X-ray machine can tell us, first." He took the bomb and carefully placed it under the wonderful rays, then with the fluoroscope over his eyes studied the shadow cast by the rays on its sensitive screen. For several minutes he continued safely studying it from every angle, until he thoroughly understood it. "It's a bomb, sure enough," Craig exclaimed, looking up from it at last to me. "It's timed by an ingenious and noiseless little piece of clockwork, in there, too. And it's powerful enough to blow us all, the laboratory included, to kingdom come." As he spoke, and before I could remonstrate with him, he took the infernal machine and placed it on a table where he set to work on the most delicate and dangerous piece of dissection of which I have ever heard. Carefully unwrapping the bomb and unscrewing one part while he held another firm, he finally took out of it a bottle of liquid and some powder. Then he placed a few grains of the powder on a dish and dropped on it a drop or two of the liquid. There was a bright flash, as the powder ignited instantly. "Just what I expected," commented Kennedy with a nod, as he examined the clever workmanship of the bomb. One thing that interested him was that part of the contents had been wrapped in paper to keep them in place. This paper he was now carefully examining with a hand lens. As nearly as I could make it out, the paper contained part of a typewritten chemical formula, which read: TINCTURE OF IODINE THREE PARTS OF--- He looked up from his study of the microscope to Long Sin. "Tell me just how it happened that you got this bomb," he asked. Without hesitation, the Chinaman recited the circumstances, beginning with the note by which he had been summoned. "A note?" repeated Kennedy, eagerly. "Was it typewritten?" Long Sin reached into his pocket and produced the note itself, which he had not burned. As Craig studied the typewritten message from the Clutching Hand I could see that he was growing more and more excited. "At last he has given us something typewritten," he exclaimed. "To most people, I suppose, it seems that typewriting is the best way to conceal identity. But there are a thousand and one ways of identifying typewriting. Clutching Hand knew that. That was why he was so careful to order this note destroyed. As for the bomb, he figured that it would destroy itself." He was placing one piece of typewriting after another under the lens, scrutinizing each letter closely. "Look, Walter," he remarked at length, taking a fine tipped pencil and pointing at the distinguishing marks as he talked, "You will notice that all the 'T's' in this note are battered and faint as well as just a trifle out of alignment. Now I will place the paper from the bomb under the lens and you will also see that the 'T's' in the scrap of formula have exactly the same appearance. That indicated, without the possibility of a doubt, taken in connection with a score of other peculiarities in the letters which I could pick out that both were written on the same typewriter. I have selected the 'T' because it is the most marked." I strained my eyes to look. Sure enough, Kennedy was right. There was that unmistakable identity between the T's in the formula and the note. Kennedy had been gazing at the floor, his face puckered in thought as I looked. Suddenly he slapped his hands together, as if he had made a great discovery. "I've struck it!" he exclaimed, jumping up. "I was wondering where I had seen typewriting that reminds me of this. Walter, get on your coat and hat. We are on the right trail at last." With Long Sin we hurried out of the laboratory, leaving him at the nearest taxicab stand, where we jumped into a waiting car. "It is the clue of the battered 'T's,'" Craig muttered. . . . . . . . . Aunt Josephine was in the library knitting when the butler, Jennings, announced us. We were admitted at once, for Aunt Josephine had never quite understood what was the trouble between Elaine and Craig, and had a high regard for him. "Where is--Miss Dodge?" inquired Kennedy, with suppressed excitement as we entered. "I think she's out shopping and I don't know just when she will be back," answered Aunt Josephine, with some surprise. "Why? Is it anything important--any news?" "Very important," returned Kennedy excitedly. "I think I have the best clue yet. Only--it will be necessary to look through some of the household correspondence immediately to see whether there are certain letters. I wouldn't be surprised if she had some--perhaps not very personal--but I MUST see them." Aunt Josephine seemed nonplussed at first. I thought she was going to refuse to allow Craig to proceed. But finally she assented. Kennedy lost no time. He went to a desk where Elaine generally sat, and quickly took out several typewritten letters. He examined them closely, rejecting one after another, until finally he came to one that seemed to interest him. He separated it from the rest and fell to studying it, comparing it with the paper from the bomb and the note which Long Sin had received from the Clutching Hand. Then he folded the letter so that both the signature and the address could not be read by us. A portion of the letter, I recall, read something like this: "This is his contention: whereas TRUTH is the only goal and MATTER is non-existent-- "Look at this, Walter," remarked Craig, with difficulty restraining himself, "What do you make of it?" A glance at the typewriting was sufficient to show me that Kennedy had indeed made an important discovery. The writing of the letter which he had just found in Elaine's desk corresponded in every respect with that in the Clutching Hand note and that on the bomb formula. In each instance there were the same faintness, the same crooked alignment, the same battered appearance of all the letter T's. We stared at each other almost too dazed to speak. . . . . . . . . At that moment we were startled by the sudden appearance of Elaine herself, who had come in unexpectedly from her shopping expedition. She entered the room carrying in her arms a huge bunch of roses which she had evidently just received. Her face was half buried in the fragrant blossoms, but was fairer than even they in their selected elegance. The moment she saw Craig, however, she stopped short with a look of great surprise. Kennedy, on his part, who was seated at the desk still tracing out the similarities of the letters, stood up, half hesitating what to say. He bowed and she returned his salutation with a very cool nod. Her keen eye had not missed the fact that several of her letters lay scattered over the top of the desk. "What are you doing with my letters, Mr. Kennedy?" she asked, in an astonished tone, evidently resenting the unceremoniousness with which he had apparently been overhauling her correspondence. As guardedly as possible, Kennedy met her inquiry, which I could not myself blame her for making. "I beg pardon, Miss Dodge," he said, "but a matter has just come up which necessitated merely a cursory examination of some purely formal letters which might have an important bearing on the discovery of the Clutching Hand. Your Aunt had no idea where you were, nor of when you might return, and the absolute necessity for haste in such an important matter is my only excuse for examining a few minor letters without first obtaining your permission." She said nothing. At another time, such an explanation would have been instantly accepted. Now, however, it was different. Kennedy read the look on her face, and an instant later turned to Aunt Josephine and myself. "I would very much appreciate a chance to say a few words to Miss Dodge alone," he intimated. "I have had no such opportunity for some time. If you would be so kind as to leave us in the library--for a few minutes--" He did not finish the sentence. Aunt Josephine had already begun to withdraw and I followed. . . . . . . . . For a moment or two, Craig and Elaine looked at each other, neither saying a word, each wondering just what was in the other's mind. Kennedy was wondering if there was any X-ray that might read a woman's heart, as he was accustomed to read others of nature's secrets. He cleared his throat, the obvious manner of covering up his emotion. "Elaine," he said at length, dropping the recent return to "Miss Dodge," for the moment, "Elaine, is there any truth in this morning's newspaper report of--of you?" She had dropped her eyes. But he persisted, taking a newspaper clipping from his pocket and handing it to her. Her hand trembled as she glanced over the item: SOCIETY NOTES Dame Rumor is connecting the name of Miss Elaine Dodge, the heiress, with that of Perry Bennett, the famous young lawyer. The announcement of an engagement between them at any time would not surprise-- Elaine read no further. She handed back the clipping to Kennedy. As her eyes met his, she noticed his expression of deep concern, and hesitated with the reply she had evidently been just about to make. Still, as she lowered her head, it seemed to give silent confirmation to the truth of the newspaper report. Kennedy said nothing. But his eyes continued to study her face, even when it was averted. He suppressed his feelings with a great effort, then, without a word, bowed and left the room. "Walter," he exclaimed as he rejoined us in the drawing room, where I was chatting with Aunt Josephine, "we must be off again. The trail follows still further." I rose and much to the increased mystification of Aunt Josephine, left the house. An hour or so later, Elaine, whose mind was now in a whirl from what had happened, decided to call on Perry Bennett. Two or three clerks were in the outer office when she arrived, but the office boy, laying down a dime novel, rose to meet her and informed her that Mr. Bennett was alone. As Elaine entered his private office, Bennett rose to greet her effusively and they exchanged a few words. "I mustn't forget to thank you for those lovely roses you sent me," she exclaimed at length. "They were beautiful and I appreciated them ever so much." Bennett acknowledged her thanks with a smile, she sat down familiarly on his desk, and they plunged into a vein of social gossip. A moment later, Bennett led the conversation around until he found an opportunity to make a tactful allusion to the report of their engagement in the morning papers. He had leaned over and now attempted to take her hand. She withdrew it, however. There was something about his touch which, try as she might, she could not like. Was it mere prejudice, or was it her keen woman's intuition? Bennett looked at her a moment, suppressing a momentary flash of anger that had reddened his face, and controlled himself as if by a superhuman effort. "I believe you really love that man Kennedy," he exclaimed, in a tone that was almost a hiss. "But I tell you, Elaine, he is all bluff. Why, he has been after that Clutching Hand now for three months--and what has he accomplished? Nothing!" He paused. Through Elaine's mind there flashed the contrast with Kennedy's even temper and deferential manner. In spite of their quarrel and the coolness, she found herself resenting the remark. Still she said nothing, though her expressive face showed much. Bennett, by another effort, seemed to grip his temper again. He paced up and down the room. Then he changed the subject abruptly, and the conversation was resumed with some constraint. . . . . . . . . While Elaine and Bennett were talking, Kennedy and I had entered the office. Craig stopped the boy who was about to announce us and asked for Bennett's secretary instead, much to my astonishment. The boy merely indicated the door of one of the other private offices, and we entered. We found the secretary, hard at work at the typewriter, copying a legal document. Without a word, Kennedy at once locked the door. The secretary rose in surprise, but Craig paid no attention to him. Instead he calmly walked over to the machine and began to examine it. "Might I ask--" began the secretary. "You keep quiet," ordered Kennedy, with a nod to me to watch the fellow. "You are under arrest--and the less you say, the better for you." I shall never forget the look that crossed the secretary's face. Was it the surprise of an innocent man? Taking the man's place at the machine, Kennedy removed the legal paper that was in it and put in a new sheet. Then he tapped out, as we watched: BE AT HEADQUARTERS AT 12. DESTROY THIS IMMEDIATELY TINCTURE OF IODINE THREE PARTS OF---- This is his contention:--whereas TRUTH is the only goal and MATTER is non-existent-- T T T T "Look, Walter," he exclaimed as he drew out the paper from the machine. I bent over and together we compared the T's with those in the Clutching Hand letter, the paper from the bomb and the letter which Craig had taken from Elaine's desk. As Craig pointed out the resemblances with a pencil, my amazement gradually changed into comprehension and comprehension into conviction. The meaning of it all began to dawn on me. The writing was identical. There were no differences! . . . . . . . . While we were locked in the secretary's office, Bennett and Elaine were continuing their chat on various social topics. Suddenly, however, with a glance at the clock, Bennett told Elaine that he had an important letter to dictate, and that it must go off at once. She said that she would excuse him a few minutes and he pressed a button to call his secretary. Of course the secretary did not appear. Bennett left his office, with some annoyance, and went into the adjoining room the door to which Kennedy had not locked. He hesitated a moment, then opened the door quietly. To his astonishment, he saw Kennedy, the secretary, and myself apparently making a close examination of the typewriter. Gliding rather than walking back into his own office, he closed the door and locked it. Almost instantly, fear and fury at the presence of his hated rival, Kennedy, turned Bennett, as it were, from the Jekyll of a polished lawyer and lover of Elaine into an insanely jealous and revengeful Mr. Hyde. The strain was more than his warped mind could bear. With a look of intense horror and loathing, Elaine watched him slowly change from the composed, calm, intellectual Bennett she knew and respected into a repulsive, mad figure of a man. His stature even seemed to be altered. He seemed to shrivel up and become deformed. His face was terribly distorted. And his long, sinewy hand slowly twisted and bent until he became the personal embodiment of the Clutching Hand. As Elaine, transfixed with terror, watched Bennett's astounding metamorphosis, he ran to the door leading to the outer office and hastily locked that, also. Then, with his eyes gleaming with rage and his hands working in murderous frenzy, he crouched, nearer and nearer, towards Elaine. She shrank back, screaming again and again in terror. He WAS the Clutching Hand! . . . . . . . . In spite of closed doors, we could now plainly hear Elaine's shrieks. Craig, the secretary and myself made a rush for the door to Bennett's private office. Finding it locked, we began to batter it. By this time, however, Bennett had hurled himself upon Elaine and was slowly choking her. Kennedy quickly found that it was impossible to batter down the door in time by any ordinary means. Quickly he seized the typewriter and hurled it through the panels. Then he thrust his hand through the opening and turned the catch. As we flung ourselves into the room, Bennett rushed into a closet in a corner, slamming the door behind him. It was composed of sheet iron and effectually prevented anyone from breaking through. Kennedy and I tried vainly, however, to pry it open. While we were thus endeavoring to force an entrance, Bennett, in a sort of closet, had put on the coat, hat and mask which he invariably wore in the character of the Clutching Hand. Then he cautiously opened a secret door in the back of the closet and slowly made an exit. . . . . . . . . Meanwhile, the secretary had been doing his best to revive Elaine, who was lying in a chair, hysterical and half unconscious from the terrible shock she had experienced. Intent on discovering Bennett's whereabouts, Kennedy and I examined the wall of the office, thinking there might possibly be some button or secret spring which would open the closet door. While we were doing so, the door of a large safe in the secretary's office gradually opened and the Clutching Hand emerged from it, stepping carefully towards the door leading to the outer office, intent on escaping in that direction. At that moment, I caught sight of him, and leaping into the secretary's office, I drew my revolver and ordered him to throw up his hands. He obeyed. Holding up both hands, he slowly drew near the door to his private office. Suddenly he dropped one hand and pressed a hidden spring in the wall. Instantly a heavy iron door shot out and closed over the wooden door. Entrance to the private office was absolutely cut off. With an angry snarl, the Clutching Hand leaped at me. As he did so, I fired twice. He staggered back. . . . . . . . . The shots were heard by Kennedy and Elaine, as well as the secretary, and at the same instant they discovered the iron door which barred the entrance to the secretary's office. Rushing into the outer office, they found the clerks excitedly attempting to open the door of the secretary's office which was locked. Kennedy drew a revolver and shot through the lock, bursting open the door. They rushed into the room. Clutching Hand was apparently seated in a chair at a desk, his face buried in his arms, while I was apparently disappearing through the door. Kennedy and the clerks pounced upon the figure in the chair and tore off his mask. To their astonishment, they discovered that it was myself! My shots had missed and Clutching Hand had leaped on me with maddened fury. Dressed in my coat and hat, which he had deftly removed after overpowering me and substituting his own clothes, Clutching Hand had by this time climbed through the window of the outer office and was making his way down the fire escape to the street. He reached the foot of the iron steps leaped off and ran quickly away. Shouting a few directions to the secretary, the clerks and Elaine, Kennedy climbed through the window and darted down the fire escape in swift pursuit. The Clutching Hand, however, managed to elude capture again. Turning the street corner he leaped into a taxi which happened to be standing there, and, hastily giving the driver directions, was driven rapidly away. By the time Kennedy reached the street Clutching Hand had disappeared. . . . . . . . . While these exciting events were occurring in Bennett's office some queer doings were in progress in the heart of Chinatown. Deep underground, in one of the catacombs known only to the innermost members of the Chinese secret societies, was Long Sin's servant, Tong Wah, popularly known as "the hider," engaged in some mysterious work. A sinister-looking Chinaman, dressed in coolie costume, he was standing at a table in a dim and musty, high-ceilinged chamber, faced with stone and brick. Before him were several odd shaped Chinese vials, and from these he was carefully measuring certain proportions, as if concocting some powerful potion. He stepped back and looked around suspiciously as he suddenly heard footsteps above. The next moment Long Sin, who had entered through a trap door, climbed down a long ladder and walked into the room. Approaching Tong Wah, he asked: "When will the death-drink be ready?" "It is now prepared," was the reply. Long Sin took the bowl in which the liquor had been mixed, and, having examined it, he gave a nod and a grunt of satisfaction. Then he mounted the ladder again and disappeared. As soon as he had gone Tong Wah, picking up several of the vials, went out through an iron door at the end of the room. A few minutes later the Clutching Hand drove up to Long Sin's house in the taxicab and, after paying the chauffeur, went to the door and knocked sharply. In response to his knocking Long Sin appeared on the threshold and motioned to Bennett to come in, evidently astonished to see him. As he entered, Bennett made a secret sign and said: "I am the Clutching Hand. Kennedy is close on my trail, and I have come to be hidden." In a tone which betrayed alarm and fear the Chinaman intimated that he had no place in which Bennett could be concealed with any degree of safety. For a moment Bennett glared savagely at Long Sin. "I possess hidden plunder worth seven million dollars," he pleaded quickly, "and if by your aid I can make a getaway, a seventh is yours." The Chinaman's cupidity was clearly excited by Bennett's offer, while the bare mention of the amount at stake was sufficient to overcome all his scruples. After exchanging a few words he finally agreed to all the Clutching Hand said. Opening a trap door in the floor of the room in which they were standing, he led Bennett down a step-ladder into the subterranean chamber in which Tong Wah had so recently been preparing his mysterious potion. As Bennett sank into a chair and passed his hands over his brow in utter weariness, Long Sin poured into a cup some of the liquor of death which Tong Wah had mixed. He handed it to Bennett, who drank it eagerly. "How do you propose to help me to escape?" asked Bennett huskily. Without a word Long Sin went to the wall, and, grasping one of the stones, pressed it back, opening a large receptacle, in which there were two glass coffins apparently containing two dead Chinamen. Pulling out the coffins, he pushed them before Bennett, who rose to his feet and gazed upon them with wonder. Long Sin broke the silence: "These men," he said, "are not dead; but they have been in this condition for many months. It is what is called in your language suspended animation." "Is that what you intend to do with me?" asked Bennett, shrinking back in terror. The Chinaman nodded in affirmation as he pushed back the coffins. Overcome by the horror of the idea Bennett, with a groan, sank back into the chair, shaking his head as if to indicate that the plan was far too terrible to carry out. With a sinister smile and a shrug of his shoulders Long Sin pointed to the cup from which Bennett had drunk. "But, dear master," he remarked suavely, "you have already drunk a full dose of the potion which causes insensibility, and it is overcoming you. Even now," he added, "you are too weak to rise." Bennett made frantic efforts to move from his seat, but the potion was already taking effect, and through sheer weakness he found he was unable to get on his feet in spite of all his struggles. With a malicious chuckle Long Sin moved closer to his victim and spoke again. "Divulge where your seven million dollars are hidden," he suggested craftily, "and I will give you an antidote." By this time Bennett, who was becoming more rigid each moment, was unable to speak, but by a movement of his head and an expression in his eyes he indicated that he was ready to agree to the Chinaman's proposal. "Where have you hidden the seven million dollars?" repeated Long Sin. Slowly, and after a desperate struggle, Bennett managed to raise one hand and pointed to his breast pocket. The Chinaman instantly thrust in his hand and drew out a map. For some moments Long Sin examined the map intently, and, with a grin of satisfaction, he placed it in his own pocket. Then he mixed what he declared was a sure antidote, and, pouring some of the liquor into a cup, he held it to Bennett's lips. As Bennett opened his mouth to drink it, Long Sin with a laugh slowly pulled the cup away and poured its contents on the floor. Bennett's body had now become still more rigid. Every sign of intelligence had left his face, and although his eyes did not close, a blank stare came over his countenance, indicating plainly that the drug had destroyed all consciousness. . . . . . . . . By this time, I was slowly recovering my senses in the secretary's office, where Bennett had left me in the disguise of the Clutching Hand. Elaine, the secretary, and the clerks were gathered round me, doing all they could to revive me. Meanwhile, Kennedy had enlisted the aid of two detectives and was scouring the city for a trace of Bennett or the taxicab in which he had fled. Somehow, Kennedy suspected, instinctively, that Long Sin might give a clue to Bennett's whereabouts, and a few moments later, we were all on our way in a car to Long Sin's house. Though we did not know it, Long Sin, at the moment when Kennedy knocked at his door, was feeling in his inside pocket to see that the map he had taken from Bennett was perfectly safe. Finding that he had it, he smiled with his peculiar oriental guile. Then he opened the door, and stood for a moment, silent. "Where is Bennett?" demanded Kennedy. Long Sin eyed us all, then with a placid smile, said, "Follow me. I will show you." He opened a trap door, and we climbed down after Craig, entering a subterranean chamber, led by Long Sin. There was Bennett seated rigidly in the chair beside the table from which the vials and cups, about which we then knew nothing, had been removed. "How did it happen?" asked Kennedy. "He came here," replied Long Sin, with a wave of his hand, "and before I could stop him he did away with himself." In dumb show, the Chinaman indicated that Bennett had taken poison. "Well, we've got him," mused Kennedy, shaking his head sadly, adding, after a pause, "but he is dead." Elaine, who had followed us down, covered her eyes with her hands, and was sobbing convulsively. I thought she would faint, but Kennedy led her gently away into an upper room. As he placed her in an easy chair, he bent over her, soothingly. "Did you--did you--really--love him?" he asked in a low tone, nodding in the direction from which he had led her. Still shuddering, and with an eager look at Kennedy, Elaine shook her beautiful head. Then, slowly rising to her feet, she looked at Craig appealingly. For a moment he looked down into her two great lakes of eyes. "Forgive me," murmured Elaine, holding out her hand. Then she added in a voice tense with emotion, "Thank you for saving me." Kennedy took her hand. For a moment he held it. Then he drew her towards him, unresisting. THE END 
5007	----	THE CRAIG KENNEDY SERIES THE POISONED PEN BY ARTHUR. B. REEVE FRONTISPIECE BY WILL FOSTER CONTENTS CHAPTER I THE POISONED PEN II THE YEGGMAN III THE GERM OF DEATH IV THE FIREBUG V THE CONFIDENCE KING VI THE SAND-HOG VII THE WHITE SLAVE VIII THE FORGER IX THE UNOFFICIAL SPY X THE SMUGGLER XI THE INVISIBLE RAY XII THE CAMPAIGN GRAFTER THE POISONED PEN I THE POISONED PEN Kennedy's suit-case was lying open on the bed, and he was literally throwing things into it from his chiffonier, as I entered after a hurried trip up-town from the Star office in response to an urgent message from him. "Come, Walter," he cried, hastily stuffing in a package of clean laundry without taking off the wrapping-paper, "I've got your suit-case out. Pack up whatever you can in five minutes. We must take the six o'clock train for Danbridge." I did not wait to hear any more. The mere mention of the name of the quaint and quiet little Connecticut town was sufficient. For Danbridge was on everybody's lips at that time. It was the scene of the now famous Danbridge poisoning case--a brutal case in which the pretty little actress, Vera Lytton, had been the victim. "I've been retained by Senator Adrian Willard," he called from his room, as I was busy packing in mine. "The Willard family believe that that young Dr. Dixon is the victim of a conspiracy--or at least Alma Willard does, which comes to the same thing, and--well, the senator called me up on long-distance and offered me anything I would name in reason to take the case. Are you ready? Come on, then. We've simply got to make that train." As we settled ourselves in the smoking-compartment of the Pullman, which for some reason or other we had to ourselves, Kennedy spoke again for the first time since our frantic dash across the city to catch the train. "Now let us see, Walter," he began. "We've both read a good deal about this case in the papers. Let's try to get our knowledge in an orderly shape before we tackle the actual case itself." "Ever been in Danbridge?" I asked. "Never," he replied. "What sort of place is it?" "Mighty interesting," I answered; "a combination of old New England and new, of ancestors and factories, of wealth and poverty, and above all it is interesting for its colony of New-Yorkers--what shall I call it?--a literary-artistic-musical combination, I guess." "Yes," he resumed, "I thought as much. Vera Lytton belonged to the colony. A very talented girl, too--you remember her in 'The Taming of the New Woman' last season? Well, to get back to the facts as we know them at present. "Here is a girl with a brilliant future on the stage discovered by her friend, Mrs. Boncour, in convulsions--practically insensible--with a bottle of headache-powder and a jar of ammonia on her dressing-table. Mrs. Boncour sends the maid for the nearest doctor, who happens to be a Dr. Waterworth. Meanwhile she tries to restore Miss Lytton, but with no result. She smells the ammonia and then just tastes the headache-powder, a very foolish thing to do, for by the time Dr. Waterworth arrives he has two patients." "No?" I corrected, "only one, for Miss Lytton was dead when he arrived, according to his latest statement." "Very well, then--one. He arrives, Mrs. Boncour is ill, the maid knows nothing at all about it, and Vera Lytton is dead. He, too, smells the ammonia, tastes the headache-powder--just the merest trace--and then he has two patients, one of them himself. We must see him, for his experience must have been appalling. How he ever did it I can't imagine, but he saved both himself and Mrs. Boncour from poisoning--cyanide, the papers say, but of course we can't accept that until we see. It seems to me, Walter, that lately the papers have made the rule in murder cases: When in doubt, call it cyanide." Not relishing Kennedy in the humour of expressing his real opinion of the newspapers, I hastily turned the conversation back again by asking, "How about the note from Dr. Dixon?" "Ah, there is the crux of the whole case--that note from Dixon. Let us see. Dr. Dixon is, if I am informed correctly, of a fine and aristocratic family, though not wealthy. I believe it has been established that while he was an interne in a city hospital he became acquainted with Vera Lytton, after her divorce from that artist Thurston. Then comes his removal to Danbridge and his meeting and later his engagement with Miss Willard. On the whole, Walter, judging from the newspaper pictures, Alma Willard is quite the equal of Vera Lytton for looks, only of a different style of beauty. Oh, well, we shall see. Vera decided to spend the spring and summer at Danbridge in the bungalow of her friend, Mrs. Boncour, the novelist. That's when things began to happen." "Yes," I put in, "when you come to know Danbridge as I did after that summer when you were abroad, you'll understand, too. Everybody knows everybody else's business. It is the main occupation of a certain set, and the per-capita output of gossip is a record that would stagger the census bureau. Still, you can't get away from the note, Craig. There it is, in Dixon's own handwriting, even if he does deny it: 'This will cure your headache. Dr. Dixon.' That's a damning piece of evidence." "Quite right," he agreed hastily; "the note was queer, though, wasn't it? They found it crumpled up in the jar of ammonia. Oh, there are lots of problems the newspapers have failed to see the significance of, let alone trying to follow up." Our first visit in Danbridge was to the prosecuting attorney, whose office was not far from the station on the main street. Craig had wired him, and he had kindly waited to see us, for it was evident that Danbridge respected Senator Willard and every one connected with him. "Would it be too much to ask just to see that note that was found in the Boncour bungalow?" asked Craig. The prosecutor, an energetic young man, pulled out of a document-case a crumpled note which had been pressed flat again. On it in clear, deep black letters were the words, just as reported: This will cure your headache. DR. DIXON. "How about the handwriting?" asked Kennedy. The lawyer pulled out a number of letters. "I'm afraid they will have to admit it," he said with reluctance, as if down in his heart he hated to prosecute Dixon. "We have lots of these, and no handwriting expert could successfully deny the identity of the writing." He stowed away the letters without letting Kennedy get a hint as to their contents. Kennedy was examining the note carefully. "May I count on having this note for further examination, of course always at such times and under such conditions as you agree to?" The attorney nodded. "I am perfectly willing to do anything not illegal to accommodate the senator," he said. "But, on the other hand, I am here to do my duty for the state, cost whom it may." The Willard house was in a virtual state of siege. Newspaper reporters from Boston and New York were actually encamped at every gate, terrible as an army, with cameras. It was with some difficulty that we got in, even though we were expected, for some of the more enterprising had already fooled the family by posing as officers of the law and messengers from Dr. Dixon. The house was a real, old colonial mansion with tall white pillars, a door with a glittering brass knocker, which gleamed out severely at you as you approached through a hedge of faultlessly trimmed boxwoods. Senator, or rather former Senator, Willard met us in the library, and a moment later his daughter Alma joined him. She was tall, like her father, a girl of poise and self-control. Yet even the schooling of twenty-two years in rigorous New England self-restraint could not hide the very human pallor of her face after the sleepless nights and nervous days since this trouble had broken on her placid existence. Yet there was a mark of strength and determination on her face that was fascinating. The man who would trifle with this girl, I felt, was playing fast and loose with her very life. I thought then, and I said to Kennedy afterward: "If this Dr. Dixon is guilty, you have no right to hide it from that girl. Anything less than the truth will only blacken the hideousness of the crime that has already been committed." The senator greeted us gravely, and I could not but take it as a good omen when, in his pride of wealth and family and tradition, he laid bare everything to us, for the sake of Alma Willard. It was clear that in this family there was one word that stood above all others, "Duty." As we were about to leave after an interview barren of new facts, a young man was announced, Mr. Halsey Post. He bowed politely to us, but it was evident why he had called, as his eye followed Alma about the room. "The son of the late Halsey Post, of Post & Vance, silversmiths, who have the large factory in town, which you perhaps noticed," explained the senator. "My daughter has known him all her life. A very fine young man." Later, we learned that the senator had bent every effort toward securing Halsey Post as a son-in-law, but his daughter had had views of her own on the subject. Post waited until Alma had withdrawn before he disclosed the real object of his visit. In almost a whisper, lest she should still be listening, he said, "There is a story about town that Vera Lytton's former husband--an artist named Thurston--was here just before her death." Senator Willard leaned forward as if expecting to hear Dixon immediately acquitted. None of us was prepared for the next remark. "And the story goes on to say that he threatened to make a scene over a wrong he says he has suffered from Dixon. I don't know anything more about it, and I tell you only because I think you ought to know what Danbridge is saying under its breath." We shook off the last of the reporters who affixed themselves to us, and for a moment Kennedy dropped in at the little bungalow to see Mrs. Boncour. She was much better, though she had suffered much. She had taken only a pinhead of the poison, but it had proved very nearly fatal. "Had Miss Lytton any enemies whom you think of, people who were jealous of her professionally or personally?" asked Craig. "I should not even have said Dr. Dixon was an enemy," she replied evasively. "But this Mr. Thurston," put in Kennedy quickly. "One is not usually visited in perfect friendship by a husband who has been divorced." She regarded him keenly for a moment. "Halsey Post told you that," she said. "No one else knew he was here. But Halsey Post was an old friend of both Vera and Mr. Thurston before they separated. By chance he happened to drop in the day Mr. Thurston was here, and later in the day I gave him a letter to forward to Mr. Thurston, which had come after the artist left. I'm sure no one else knew the artist. He was here the morning of the day she died, and--and--that's every bit I'm going to tell you about him, so there. I don't know why he came or where he went." "That's a thing we must follow up later," remarked Kennedy as we made our adieus. "Just now I want to get the facts in hand. The next thing on my programme is to see this Dr. Waterworth." We found the doctor still in bed; in fact, a wreck as the result of his adventure. He had little to correct in the facts of the story which had been published so far. But there were many other details of the poisoning he was quite willing to discuss frankly. "It was true about the jar of ammonia?" asked Kennedy. "Yes," he answered. "It was standing on her dressing-table with the note crumpled up in it, just as the papers said." "And you have no idea why it was there?" "I didn't say that. I can guess. Fumes of ammonia are one of the antidotes for poisoning of this kind." "But Vera Lytton could hardly have known that," objected Kennedy. "No, of course not. But she probably did know that ammonia is good for just that sort of faintness which she must have experienced after taking the powder. Perhaps she thought of sal volatile, I don't know. But most people know that ammonia in some form is good for faintness of this sort, even if they don't know anything about cyanides and---" "Then it was cyanide?" interrupted Craig. "Yes," he replied slowly. It was evident that he was suffering great physical and nervous anguish as the result of his too intimate acquaintance with the poisons in question. "I will tell you precisely how it was, Professor Kennedy. When I was called in to see Miss Lytton I found her on the bed. I pried open her jaws and smelled the sweetish odour of the cyanogen gas. I knew then what she had taken, and at the moment she was dead. In the next room I heard some one moaning. The maid said that it was Mrs. Boncour, and that she was deathly sick. I ran into her room, and though she was beside herself with pain I managed to control her, though she struggled desperately against me. I was rushing her to the bathroom, passing through Miss Lytton's room. 'What's wrong?' I asked as I carried her along. 'I took some of that,' she replied, pointing to the bottle on the dressing-table. "I put a small quantity of its crystal contents on my tongue. Then I realised the most tragic truth of my life. I had taken one of the deadliest poisons in the world. The odour of the released gas of cyanogen was strong. But more than that, the metallic taste and the horrible burning sensation told of the presence of some form of mercury, too. In that terrible moment my brain worked with the incredible swiftness of light. In a flash I knew that if I added malic acid to the mercury--perchloride of mercury or corrosive sublimate--I would have calomel or subchloride of mercury, the only thing that would switch the poison out of my system and Mrs. Boncour's. "Seizing her about the waist, I hurried into the dining-room. On a sideboard was a dish of fruit. I took two apples. I made her eat one, core and all. I ate the other. The fruit contained the malic acid I needed to manufacture the calomel, and I made it right there in nature's own laboratory. But there was no time to stop. I had to act just as quickly to neutralise that cyanide, too. Remembering the ammonia, I rushed back with Mrs. Boncour, and we inhaled the fumes. Then I found a bottle of peroxide of hydrogen. I washed out her stomach with it, and then my own. Then I injected some of the peroxide into various parts of her body. The peroxide of hydrogen and hydrocyanic acid, you know, make oxamide, which is a harmless compound. "The maid put Mrs. Boncour to bed, saved. I went to my house, a wreck. Since then I have not left this bed. With my legs paralysed I lie here, expecting each hour to be my last." "Would you taste an unknown drug again to discover the nature of a probable poison?" asked Craig. "I don't know," he answered slowly, "but I suppose I would. In such a case a conscientious doctor has no thought of self. He is there to do things, and he does them, according to the best that is in him. In spite of the fact that I haven't had one hour of unbroken sleep since that fatal day, I suppose I would do it again." When we were leaving, I remarked: "That is a martyr to science. Could anything be more dramatic than his willing penalty for his devotion to medicine?" We walked along in silence. "Walter, did you notice he said not a word of condemnation of Dixon, though the note was before his eyes? Surely Dixon has some strong supporters in Danbridge, as well as enemies." The next morning we continued our investigation. We found Dixon's lawyer, Leland, in consultation with his client in the bare cell of the county jail. Dixon proved to be a clear-eyed, clean-cut young man. The thing that impressed me most about him, aside from the prepossession in his favour due to the faith of Alma Willard, was the nerve he displayed, whether guilty or innocent. Even an innocent man might well have been staggered by the circumstantial evidence against him and the high tide of public feeling, in spite of the support that he was receiving. Leland, we learned, had been very active. By prompt work at the time of the young doctor's arrest he had managed to secure the greater part of Dr. Dixon's personal letters, though the prosecutor secured some, the contents of which had not been disclosed. Kennedy spent most of the day in tracing out the movements of Thurston. Nothing that proved important was turned up, and even visits to near-by towns failed to show any sales of cyanide or sublimate to any one not entitled to buy them. Meanwhile, in turning over the gossip of the town, one of the newspapermen ran across the fact that the Boncour bungalow was owned by the Posts, and that Halsey Post, as the executor of the estate, was a more frequent visitor than the mere collection of the rent would warrant. Mrs. Boncour maintained a stolid silence that covered a seething internal fury when the newspaperman in question hinted that the landlord and tenant were on exceptionally good terms. It was after a fruitless day of such search that we were sitting in the reading-room of the Fairfield Hotel. Leland entered. His face was positively white. Without a word he took us by the arm and led us across Main Street and up a flight of stairs to his office. Then he locked the door. "What's the matter?" asked Kennedy. "When I took this case," he said, "I believed down in my heart that Dixon was innocent. I still believe it, but my faith has been rudely shaken. I feel that you should know about what I have just found. As I told you, we secured nearly all of Dr. Dixon's letters. I had not read them all then. But I have been going through them to-night. Here is a letter from Vera Lytton herself. You will notice it is dated the day of her death." He laid the letter before us. It was written in a curious greyish-black ink in a woman's hand, and read: DEAR HARRIS: Since we agreed to disagree we have at least been good friends, if no longer lovers. I am not writing in anger to reproach you with your new love, so soon after the old. I suppose Alma Willard is far better suited to be your wife than is a poor little actress--rather looked down on in this Puritan society here. But there is something I wish to warn you about, for it concerns us all intimately. We are in danger of an awful mix-up if we don't look out. Mr. Thurston--I had almost said my husband, though I don't know whether that is the truth or not--who has just come over from New York, tells me that there is some doubt about the validity of our divorce. You recall he was in the South at the time I sued him, and the papers were served on him in Georgia, He now says the proof of service was fraudulent and that he can set aside the divorce. In that case you might figure in a suit for alienating my affections. I do not write this with ill will, but simply to let you know how things stand. If we had married, I suppose I would be guilty of bigamy. At any rate, if he were disposed he could make a terrible scandal. Oh, Harris, can't you settle with him if he asks anything? Don't forget so soon that we once thought we were going to be the happiest of mortals--at least I did. Don't desert me, or the very earth will cry out against you. I am frantic and hardly know what I am writing. My head aches, but it is my heart that is breaking. Harris, I am yours still, down in my heart, but not to be cast off like an old suit for a new one. You know the old saying about a woman scorned. I beg you not to go back on Your poor little deserted VERA. As we finished reading, Leland exclaimed, "That never must come before the jury." Kennedy was examining the letter carefully. "Strange," he muttered. "See how it was folded. It was written on the wrong side of the sheet, or rather folded up with the writing outside. Where have these letters been?" "Part of the time in my safe, part of the time this afternoon on my desk by the window." "The office was locked, I suppose?" asked Kennedy. "There was no way to slip this letter in among the others since you obtained them?" "None. The office has been locked, and there is no evidence of any one having entered or disturbed a thing." He was hastily running over the pile of letters as if looking to see whether they were all there. Suddenly he stopped. "Yes," he exclaimed excitedly, "one of them is gone." Nervously he fumbled through them again. "One is gone," he repeated, looking at us, startled. "What was it about?" asked Craig. "It was a note from an artist, Thurston, who gave the address of Mrs. Boncour's bungalow--ah, I see you have heard of him. He asked Dixon's recommendation of a certain patent headache medicine. I thought it possibly evidential, and I asked Dixon about it. He explained it by saying that he did not have a copy of his reply, but as near as he could recall, he wrote that the compound would not cure a headache except at the expense of reducing heart action dangerously. He says he sent no prescription. Indeed, he thought it a scheme to extract advice without incurring the charge for an office call and answered it only because he thought Vera had become reconciled to Thurston again. I can't find that letter of Thurston's. It is gone." We looked at each other in amazement. "Why, if Dixon contemplated anything against Miss Lytton, should he preserve this letter from her?" mused Kennedy. "Why didn't he destroy it?" "That's what puzzles me," remarked Leland. "Do you suppose some one has broken in and substituted this Lytton letter for the Thurston letter?" Kennedy was scrutinising the letter, saying nothing. "I may keep it?" he asked at length. Leland was quite willing and even undertook to obtain some specimens of the writing of Vera Lytton. With these and the letter Kennedy was working far into the night and long after I had passed into a land troubled with many wild dreams of deadly poisons and secret intrigues of artists. The next morning a message from our old friend First Deputy O'Connor in New York told briefly of locating the rooms of an artist named Thurston in one of the co-operative studio apartments. Thurston himself had not been there for several days and was reported to have gone to Maine to sketch. He had had a number of debts, but before he left they had all been paid--strange to say, by a notorious firm of shyster lawyers, Kerr & Kimmel. Kennedy wired back to find out the facts from Kerr & Kimmel and to locate Thurston at any cost. Even the discovery of the new letter did not shake the wonderful self-possession of Dr. Dixon. He denied ever having received it and repeated his story of a letter from Thurston to which he had replied by sending an answer, care of Mrs. Boncour, as requested. He insisted that the engagement between Miss Lytton and himself had been broken before the announcement of his engagement with Miss Willard. As for Thurston, he said the man was little more than a name to him. He had known perfectly all the circumstances of the divorce, but had had no dealings with Thurston and no fear of him. Again and again he denied ever receiving the letter from Vera Lytton. Kennedy did not tell the Willards of the new letter. The strain had begun to tell on Alma, and her father had had her quietly taken to a farm of his up in the country. To escape the curious eyes of reporters, Halsey Post had driven up one night in his closed car. She had entered it quickly with her father, and the journey had been made in the car, while Halsey Post had quietly dropped off on the outskirts of the town, where another car was waiting to take him back. It was evident that the Willard family relied implicitly on Halsey, and his assistance to them was most considerate. While he never forced himself forward, he kept in close touch with the progress of the case, and now that Alma was away his watchfulness increased proportionately, and twice a day he wrote a long report which was sent to her. Kennedy was now bending every effort to locate the missing artist. When he left Danbridge, he seemed to have dropped out of sight completely. However, with O'Connor's aid, the police of all New England were on the lookout. The Thurstons had been friends of Halsey's before Vera Lytton had ever met Dr. Dixon, we discovered from the Danbridge gossips, and I, at least, jumped to the conclusion that Halsey was shielding the artist, perhaps through a sense of friendship when he found that Kennedy was interested in Thurston's movement. I must say I rather liked Halsey, for he seemed very thoughtful of the Willards, and was never too busy to give an hour or so to any commission they wished carried out without publicity. Two days passed with not a word from Thurston. Kennedy was obviously getting impatient. One day a rumour was received that he was in Bar Harbour; the next it was a report from Nova Scotia. At last, however, came the welcome news that he had been located in New Hampshire, arrested, and might be expected the next day. At once Kennedy became all energy. He arranged for a secret conference in Senator Willard's house, the moment the artist was to arrive. The senator and his daughter made a flying trip back to town. Nothing was said to any one about Thurston, but Kennedy quietly arranged with the district attorney to be present with the note and the jar of ammonia properly safeguarded. Leland of course came, although his client could not. Halsey Post seemed only too glad to be with Miss Willard, though he seemed to have lost interest in the case as soon as the Willards returned to look after it themselves. Mrs. Boncour was well enough to attend, and even Dr. Waterworth insisted on coming in a private ambulance which drove over from a near-by city especially for him. The time was fixed just before the arrival of the train that was to bring Thurston. It was an anxious gathering of friends and foes of Dr. Dixon who sat impatiently waiting for Kennedy to begin this momentous exposition that was to establish the guilt or innocence of the calm young physician who sat impassively in the jail not half a mile from the room where his life and death were being debated. "In many respects this is the most remarkable case that it has ever been my lot to handle," began Kennedy. "Never before have I felt so keenly my sense of responsibility. Therefore, though this is a somewhat irregular proceeding, let me begin by setting forth the facts as I see them. "First, let us consider the dead woman. The question that arises here is, Was she murdered or did she commit suicide? I think you will discover the answer as I proceed. Miss Lytton, as you know, was, two years ago, Mrs. Burgess Thurston. The Thurstons had temperament, and temperament is quite often the highway to the divorce court. It was so in this case. Mrs. Thurston discovered that her husband was paying much attention to other women. She sued for divorce in New York, and he accepted service in the South, where he happened to be. At least it was so testified by Mrs. Thurston's lawyer. "Now here comes the remarkable feature of the case. The law firm of Kerr & Kimmel, I find, not long ago began to investigate the legality of this divorce. Before a notary Thurston made an affidavit that he had never been served by the lawyer for Miss Lytton, as she was now known. Her lawyer is dead, but his representative in the South who served the papers is alive. He was brought to New York and asserted squarely that he had served the papers properly. "Here is where the shrewdness of Mose Kimmel, the shyster lawyer, came in. He arranged to have the Southern attorney identify the man he had served the papers on. For this purpose he was engaged in conversation with one of his own clerks when the lawyer was due to appear. Kimmel appeared to act confused, as if he had been caught napping. The Southern lawyer, who had seen Thurston only once, fell squarely into the trap and identified the clerk as Thurston. There were plenty of witnesses to it, and it was point number two for the great Mose Kimmel. Papers were drawn up to set aside the divorce decree. "In the meantime, Miss Lytton, or Mrs. Thurston, had become acquainted with a young doctor in a New York hospital, and had become engaged to him. It matters not that the engagement was later broken. The fact remains that if the divorce were set aside an action would lie against Dr. Dixon for alienating Mrs. Thurston's affections, and a grave scandal would result. I need not add that in this quiet little town of Danbridge the most could be made of such a suit." Kennedy was unfolding a piece of paper. As he laid it down, Leland, who was sitting next to me, exclaimed under his breath: "My God, he's going to let the prosecutor know about that letter. Can't you stop him?" It was too late. Kennedy had already begun to read Vera's letter. It was damning to Dixon, added to the other note found in the ammonia-jar. When he had finished reading, you could almost hear the hearts throbbing in the room. A scowl overspread Senator Willard's features. Alma Willard was pale and staring wildly at Kennedy. Halsey Post, ever solicitous for her, handed her a glass of water from the table. Dr. Waterworth had forgotten his pain in his intense attention, and Mrs. Boncour seemed stunned with astonishment. The prosecuting attorney was eagerly taking notes. "In some way," pursued Kennedy in an even voice, "this letter was either overlooked in the original correspondence of Dr. Dixon or it was added to it later. I shall come back to that presently. My next point is that Dr. Dixon says he received a letter from Thurston on the day the artist visited the Boncour bungalow. It asked about a certain headache compound, and his reply was brief and, as nearly as I can find out, read, 'This compound will not cure your headache except at the expense of reducing heart action dangerously.' "Next comes the tragedy. On the evening of the day that Thurston left, after presumably telling Miss Lytton about what Kerr & Kimmel had discovered, Miss Lytton is found dying with a bottle containing cyanide and sublimate beside her. You are all familiar with the circumstances and with the note discovered in the jar of ammonia. Now, if the prosecutor will be so kind as to let me see that note--thank you, sir. This is the identical note. You have all heard the various theories of the jar and have read the note. Here it is in plain, cold black and white--in Dr. Dixon's own handwriting, as you know, and reads: 'This will cure your headache. Dr. Dixon.'" Alma Willard seemed as one paralysed. Was Kennedy, who had been engaged by her father to defend her fiance, about to convict him? "Before we draw the final conclusion," continued Kennedy gravely, "there are one or two points I wish to elaborate. Walter, will you open that door into the main hall?" I did so, and two policemen stepped in with a prisoner. It was Thurston, but changed almost beyond recognition. His clothes were worn, his beard shaved off, and he had a generally hunted appearance. Thurston was visibly nervous. Apparently he had heard all that Kennedy had said and intended he should hear, for as he entered he almost broke away from the police officers in his eagerness to speak. "Before God," he cried dramatically, "I am as innocent as you are of this crime, Professor Kennedy." "Are you prepared to swear before ME," almost shouted Kennedy, his eyes blazing, "that you were never served properly by your wife's lawyers in that suit?" The man cringed back as if a stinging blow had been delivered between his eyes. As he met Craig's fixed glare he knew there was no hope. Slowly, as if the words were being wrung from him syllable by syllable, he said in a muffled voice: "No, I perjured myself. I was served in that suit. But--" "And you swore falsely before Kimmel that you were not?" persisted Kennedy. "Yes," he murmured. "But--" "And you are prepared now to make another affidavit to that effect?" "Yes," he replied. "If--" "No buts or ifs, Thurston," cried Kennedy sarcastically. "What did you make that affidavit for? What is YOUR story?" "Kimmel sent for me. I did not go to him. He offered to pay my debts if I would swear to such a statement. I did not ask why or for whom. I swore to it and gave him a list of my creditors. I waited until they were paid. Then my conscience"--I could not help revolting at the thought of conscience in such a wretch, and the word itself seemed to stick in his throat as he went on and saw how feeble an impression he was making on us--"my conscience began to trouble me. I determined to see Vera, tell her all, and find out whether it was she who wanted this statement. I saw her. When at last I told her, she scorned me. I can confirm that, for as I left a man entered. I now knew how grossly I had sinned, in listening to Mose Kimmel. I fled. I disappeared in Maine. I travelled. Every day my money grew less. At last I was overtaken, captured, and brought back here." He stopped and sank wretchedly down in a chair and covered his face with his hands. "A likely story," muttered Leland in my ear. Kennedy was working quickly. Motioning the officers to be seated by Thurston, he uncovered a jar which he had placed on the table. The colour had now appeared in Alma's cheeks, as if hope had again sprung in her heart, and I fancied that Halsey Post saw his claim on her favour declining correspondingly. "I want you to examine the letters in this case with me," continued Kennedy. "Take the letter which I read from Miss Lytton, which was found following the strange disappearance of the note from Thurston." He dipped a pen into a little bottle, and wrote on a piece of paper: What is your opinion about Cross's Headache Cure? Would you recommend it for a nervous headache? BURGESS THURSTON, c/o MRS. S. BONCOUR. Craig held up the writing so that we could all see that he had written what Dixon declared Thurston wrote in the note that had disappeared. Then he dipped another pen into a second bottle, and for some time he scrawled on another sheet of paper. He held it up, but it was still perfectly blank. "Now," he added, "I am going to give a little demonstration which I expect to be successful only in a measure. Here in the open sunshine by this window I am going to place these two sheets of paper side by side. It will take longer than I care to wait to make my demonstration complete, but I can do enough to convince you." For a quarter of an hour we sat in silence, wondering what he would do next. At last he beckoned us over to the window. As we approached he said, "On sheet number one I have written with quinoline; on sheet number two I wrote with a solution of nitrate of silver." We bent over. The writing signed "Thurston" on sheet number one was faint, almost imperceptible, but on paper number two, in black letters, appeared what Kennedy had written: "Dear Harris: Since we agreed to disagree we have at least been good friends." "It is like the start of the substituted letter, and the other is like the missing note," gasped Leland in a daze. "Yes," said Kennedy quickly. "Leland, no one entered your office. No one stole the Thurston note. No one substituted the Lytton letter. According to your own story, you took them out of the safe and left them in the sunlight all day. The process that had been started earlier in ordinary light, slowly, was now quickly completed. In other words, there was writing which would soon fade away on one side of the paper and writing which was invisible but would soon appear on the other. "For instance, quinoline rapidly disappears in sunlight. Starch with a slight trace of iodine writes a light blue, which disappears in air. It was something like that used in the Thurston letter. Then, too, silver nitrate dissolved in ammonia gradually turns black as it is acted on by light and air. Or magenta treated with a bleaching-agent in just sufficient quantity to decolourise it is invisible when used for writing. But the original colour reappears as the oxygen of the air acts upon the pigment. I haven't a doubt but that my analyses of the inks are correct and on one side quinoline was used and on the other nitrate of silver. This explains the inexplicable disappearance of evidence incriminating one person, Thurston, and the sudden appearance of evidence incriminating another, Dr. Dixon. Sympathetic ink also accounts for the curious circumstance that the Lytton letter was folded up with the writing apparently outside. It was outside and unseen until the sunlight brought it out and destroyed the other, inside, writing--a change, I suspect, that was intended for the police to see after it was completed, not for the defence to witness as it was taking place." We looked at each other aghast. Thurston was nervously opening and shutting his lips and moistening them as if he wanted to say something but could not find the words. "Lastly," went on Craig, utterly regardless of Thurston's frantic efforts to speak, "we come to the note that was discovered so queerly crumpled up in the jar of ammonia on Vera Lytton's dressing-table. I have here a cylindrical glass jar in which I place some sal-ammoniac and quicklime. I will wet it and heat it a little. That produces the pungent gas of ammonia. "On one side of this third piece of paper I myself write with this mercurous nitrate solution. You see, I leave no mark on the paper as I write. I fold it up and drop it into the jar-and in a few seconds withdraw it. Here is a very quick way of producing something like the slow result of sunlight with silver nitrate. The fumes of ammonia have formed the precipitate of black mercurous nitrate, a very distinct black writing which is almost indelible. That is what is technically called invisible rather than sympathetic ink." We leaned over to read what he had written. It was the same as the note incriminating Dixon: This will cure your headache. DR. DIXON. A servant entered with a telegram from New York. Scarcely stopping in his exposure, Kennedy tore it open, read it hastily, stuffed it into his pocket, and went on. "Here in this fourth bottle I have an acid solution of iron chloride, diluted until the writing is invisible when dry," he hurried on. "I will just make a few scratches on this fourth sheet of paper--so. It leaves no mark. But it has the remarkable property of becoming red in vapour of sulpho-cyanide. Here is a long-necked flask of the gas, made by sulphuric acid acting on potassium sulpho-cyanide. Keep back, Dr. Waterworth, for it would be very dangerous for you to get even a whiff of this in your condition. Ah! See--the scratches I made on the paper are red." Then hardly giving us more than a moment to let the fact impress itself on our minds, he seized the piece of paper and dashed it into the jar of ammonia. When he withdrew it, it was just a plain sheet of white paper again. The red marks which the gas in the flask had brought out of nothingness had been effaced by the ammonia. They had gone and left no trace. "In this way I can alternately make the marks appear and disappear by using the sulpho-cyanide and the ammonia. Whoever wrote this note with Dr. Dixon's name on it must have had the doctor's reply to the Thurston letter containing the words, 'This will not cure your headache.' He carefully traced the words, holding the genuine note up to the light with a piece of paper over it, leaving out the word 'not' and using only such words as he needed. This note was then destroyed. "But he forgot that after he had brought out the red writing by the use of the sulpho-cyanide, and though he could count on Vera Lytton's placing the note in the jar of ammonia and hence obliterating the writing, while at the same time the invisible writing in the mercurous nitrate involving Dr. Dixon's name would be brought out by the ammonia indelibly on the other side of the note--he forgot"--Kennedy was now speaking eagerly and loudly--"that the sulpho-cyanide vapours could always be made to bring back to accuse him the words that the ammonia had blotted out." Before the prosecutor could interfere, Kennedy had picked up the note found in the ammonia-jar beside the dying girl and had jammed the state's evidence into the long-necked flask of sulpho-cyanide vapour. "Don't fear," he said, trying to pacify the now furious prosecutor, "it will do nothing to the Dixon writing. That is permanent now, even if it is only a tracing." When he withdrew the note, there was writing on both sides, the black of the original note and something in red on the other side. We crowded around, and Craig read it with as much interest as any of us: "Before taking the headache-powder, be sure to place the contents of this paper in a jar with a little warm water." "Hum," commented Craig, "this was apparently written on the outside wrapper of a paper folded about some sal-ammoniac and quicklime. It goes on: "'Just drop the whole thing in, PAPER AND ALL. Then if you feel a faintness from the medicine the ammonia will quickly restore you. One spoonful of the headache-powder swallowed quickly is enough.'" No name was signed to the directions, but they were plainly written, and "PAPER AND ALL" was underscored heavily. Craig pulled out some letters. "I have here specimens of writing of many persons connected with this case, but I can see at a glance which one corresponds to the writing on this red death-warrant by an almost inhuman fiend. I shall, however, leave that part of it to the handwriting experts to determine at the trial. Thurston, who was the man whom you saw enter the Boncour bungalow as you left--the constant visitor?" Thurston had not yet regained his self-control, but with trembling forefinger he turned and pointed to Halsey Post. "Yes, ladies and gentlemen," cried Kennedy as he slapped the telegram that had just come from New York down on the table decisively, "yes, the real client of Kerr & Kimmel, who bent Thurston to his purposes, was Halsey Post, once secret lover of Vera Lytton till threatened by scandal in Danbridge--Halsey Post, graduate in technology, student of sympathetic inks, forger of the Vera Lytton letter and the other notes, and dealer in cyanides in the silver-smithing business, fortune-hunter for the Willard millions with which to recoup the Post & Vance losses, and hence rival of Dr. Dixon for the love of Alma Willard. That is the man who wielded the poisoned pen. Dr. Dixon is innocent." II THE YEGGMAN "Hello! Yes, this is Professor Kennedy. I didn't catch the name--oh, yes--President Blake of the Standard Burglary Insurance Company. What--really? The Branford pearls--stolen? Maid chloroformed? Yes, I'll take the case. You'll be up in half an hour? All right, I'll be here. Goodbye." It was through this brief and businesslike conversation over the telephone that Kennedy became involved in what proved to be one of the most dangerous cases he had ever handled. At the mention of the Branford pearls I involuntarily stopped reading, and listened, not because I wanted to pry into Craig's affairs, but because I simply couldn't help it. This was news that had not yet been given out to the papers, and my instinct told me that there must be something more to it than the bare statement of the robbery. "Some one has made a rich haul," I commented. "It was reported, I remember, when the Branford pearls were bought in Paris last year that Mrs. Branford paid upward of a million francs for the collection." "Blake is bringing up his shrewdest detective to co-operate with me in the case," added Kennedy. "Blake, I understand, is the head of the Burglary Insurance Underwriters' Association, too. This will be a big thing, Walter, if we can carry it through." It was the longest half-hour that I ever put in, waiting for Blake to arrive. When he did come, it was quite evident that my surmise had been correct. Blake was one of those young old men who are increasingly common in business today. There was an air of dignity and keenness about his manner that showed clearly how important he regarded the case. So anxious was he to get down to business that he barely introduced himself and his companion, Special Officer Maloney, a typical private detective. "Of course you haven't heard anything except what I have told you over the wire," he began, going right to the point. "We were notified of it only this noon ourselves, and we haven't given it out to the papers yet, though the local police in Jersey are now on the scene. The New York police must be notified tonight, so that whatever we do must be done before they muss things up. We've got a clue that we want to follow up secretly. These are the facts." In the terse, straightforward language of the up-to-date man of efficiency, he sketched the situation for us. "The Branford estate, you know, consists of several acres on the mountain back of Montclair, overlooking the valley, and surrounded by even larger estates. Branford, I understand, is in the West with a party of capitalists, inspecting a reported find of potash salts. Mrs. Branford closed up the house a few days ago and left for a short stay at Palm Beach. Of course they ought to have put their valuables in a safe deposit vault. But they didn't. They relied on a safe that was really one of the best in the market--a splendid safe, I may say. Well, it seems that while the master and mistress were both away the servants decided on having a good time in New York. They locked up the house securely--there's no doubt of that--and just went. That is, they all went except Mrs. Branford's maid, who refused to go for some reason or other. We've got all the servants, but there's not a clue to be had from any of them. They just went off on a bust, that's clear. They admit it. "Now, when they got back early this morning they found the maid in bed--dead. There was still a strong odor of chloroform about the room. The bed was disarranged as if there had been a struggle. A towel had been wrapped up in a sort of cone, saturated with chloroform, and forcibly held over the girl's nose. The next thing they discovered was the safe--blown open in a most peculiar manner. I won't dwell on that. We're going to take you out there and show it to you after I've told you the whole story. "Here's the real point. It looks all right, so far. The local police say that the thief or thieves, whoever they were, apparently gained access by breaking a back window. That's mistake number one. Tell Mr. Kennedy about the window, Maloney." "It's just simply this," responded the detective. "When I came to look at the broken window I found that the glass had fallen outside in such a way as it could not have fallen if the window had been broken from the outside. The thing was a blind. Whoever did it got into the house in some other way and then broke the glass later to give a false clue." "And," concluded Blake, taking his cigar between his thumb and forefinger and shaking it to give all possible emphasis to his words, "we have had our agent at Palm Beach on long-distance 'phone twice this afternoon. Mrs. Branford did NOT go to Palm Beach. She did NOT engage rooms in any hotel there. And furthermore she never had any intention of going there. By a fortunate circumstance Maloney picked up a hint from one of the servants, and he has located her at the Grattan Inn in this city. In other words, Mrs. Branford has stolen her own jewels from herself in order to collect the burglary insurance--a common-enough thing in itself, but never to my knowledge done on such a large scale before." The insurance man sank back in his chair and surveyed us sharply. "But," interrupted Kennedy slowly, "how about--" "I know--the maid," continued Blake. "I do not mean that Mrs. Branford did the actual stealing. Oh, no. That was done by a yeggman of experience. He must have been above the average, but everything points to the work of a yeggman. She hired him. But he overstepped the mark when he chloroformed the maid." For a moment Kennedy said nothing. Then he remarked: "Let us go out and see the safe. There must be some clue. After that I want to have a talk with Mrs. Branford. By the way," he added, as we all rose to go down to Blake's car, "I once handled a life insurance case for the Great Eastern. I made the condition that I was to handle it in my own way, whether it went for or against the company. That's understood, is it, before I undertake the case?" "Yes, yes," agreed Blake. "Get at the truth. We're not seeking to squirm out of meeting an honest liability. Only we want to make a signal example if it is as we have every reason to believe. There has been altogether too much of this sort of fake burglary to collect insurance, and as president of the underwriters it is my duty and intention to put a stop to it. Come on." Maloney nodded his head vigorously in assent with his chief. "Never fear," he murmured. "The truth is what will benefit the company, all right. She did it." The Branford estate lay some distance back from the railroad station, so that, although it took longer to go by automobile than by train, the car made us independent of the rather fitful night train service and the local cabmen. We found the house not deserted by the servants, but subdued. The body of the maid had been removed to a local morgue, and a police officer was patrolling the grounds, though of what use that could be I was at a loss to understand. Kennedy was chiefly interested in the safe. It was of the so-called "burglar-proof" variety, spherical in shape, and looking for all the world like a miniature piece of electrical machinery. "I doubt if anything could have withstood such savage treatment as has been given to this safe," remarked Craig as he concluded a cursory examination of it. "It shows great resistance to high explosives, chiefly, I believe, as a result of its rounded shape. But nothing could stand up against such continued assaults." He continued to examine the safe while we stood idly by. "I like to reconstruct my cases in my own mind," explained Kennedy, as he took his time in the examination. "Now, this fellow must have stripped the safe of all the outer trimmings. His next move was to make a dent in the manganese surface across the joint where the door fits the body. That must have taken a good many minutes of husky work. In fact, I don't see how he could have done it without a sledge-hammer and a hot chisel. Still, he did it and then--" "But the maid," interposed Maloney. "She was in the house. She would have heard and given an alarm." For answer, Craig simply went to a bay-window and raised the curtain. Pointing to the lights of the next house, far down the road, he said, "I'll buy the best cigars in the state if you can make them hear you on a blustery night like last night. No, she probably did scream. Either at this point, or at the very start, the burglar must have chloroformed her. I don't see any other way to explain it. I doubt if he expected such a tough proposition as he found in this safe, but he was evidently prepared to carry it through, now that he was here and had such an unexpectedly clear field, except for the maid. He simply got her out of the way, or his confederates did--in the easiest possible way, poor girl." Returning to the safe, he continued: "Well, anyhow, he made a furrow perhaps an inch and a half long and a quarter of an inch wide and, I should say, not over an eighth of an inch deep. Then he commenced to burgle in earnest. Under the dent he made a sort of little cup of red clay and poured in the 'soup'--the nitroglycerin--so that it would run into the depression. Then he exploded it in the regular way with a battery and a fulminate cap. I doubt if it did much more than discolour the metal at first. Still, with the true persistency of his kind, he probably repeated the dose, using more and more of the 'soup' until the joint was stretched a little, and more of an opening made so that the 'soup' could run in. "Again and again he must have repeated and increased the charges. Perhaps he used two or three cups at a time. By this time the outer door must have been stretched so as to make it easy to introduce the explosive. No doubt he was able to use ten or twelve ounces of the stuff at a charge. It must have been more like target-practice than safe-blowing. But the chance doesn't often come--an empty house and plenty of time. Finally the door must have bulged a fraction of an inch or so, and then a good big charge and the outer portion was ripped off and the safe turned over. There was still two or three inches of manganese steel protecting the contents, wedged in so tight that it must have seemed that nothing could budge it. But he must have kept at it until we have the wreck that we see here," and Kennedy kicked the safe with his foot as he finished. Blake was all attention by this time, while Maloney gasped, "If I was in the safe-cracking business, I'd make you the head of the firm." "And now," said Craig, "let us go back to New York and see if we can find Mrs. Branford." "Of course you understand," explained Blake as we were speeding back, "that most of these cases of fake robberies are among small people, many of them on the East Side among little jewellers or other tradesmen. Still, they are not limited to any one class. Indeed, it is easier to foil the insurance companies when you sit in the midst of finery and wealth, protected by a self-assuring halo of moral rectitude, than under less fortunate circumstances. Too often, I'm afraid, we have good-naturedly admitted the unsolved burglary and paid the insurance claim. That has got to stop. Here's a case where we considered the moral hazard a safe one, and we are mistaken. It's the last straw." Our interview with Mrs. Branford was about as awkward an undertaking as I have ever been concerned with. Imagine yourself forced to question a perfectly stunning woman, who was suspected of plotting so daring a deed and knew that you suspected her. Resentment was no name for her feelings. She scorned us, loathed us. It was only by what must have been the utmost exercise of her remarkable will-power that she restrained herself from calling the hotel porters and having us thrown out bodily. That would have put a bad face on it, so she tolerated our presence. Then, of course, the insurance company had reserved the right to examine everybody in the household, under oath if necessary, before passing on the claim. "This is an outrage," she exclaimed, her eyes flashing and her breast rising and falling with suppressed emotion, "an outrage. When my husband returns I intend to have him place the whole matter in the hands of the best attorney in the city. Not only will I have the full amount of the insurance, but I will have damages and costs and everything the law allows. Spying on my every movement in this way--it is an outrage! One would think we were in St. Petersburg instead of New York." "One moment, Mrs. Branford," put in Kennedy, as politely as he could. "Suppose--" "Suppose nothing," she cried angrily. "I shall explain nothing, say nothing. What if I do choose to close up that lonely big house in the suburbs and come to the city to live for a few days--is it anybody's business except mine?" "And your husband's?" added Kennedy, nettled at her treatment of him. She shot him a scornful glance. "I suppose Mr. Branford went out to Arizona for the express purpose of collecting insurance on my jewels," she added sarcastically with eyes that snapped fire. "I was about to say," remarked Kennedy as imperturbably as if he were an automaton, "that supposing some one took advantage of your absence to rob your safe, don't you think the wisest course would be to be perfectly frank about it?" "And give just one plausible reason why you wished so much to have it known that you were going to Palm Beach when in reality you were in New York?" pursued Maloney, while Kennedy frowned at his tactless attempt at a third degree. If she had resented Kennedy, she positively flew up in the air and commenced to aviate at Maloney's questioning. Tossing her head, she said icily: "I do not know that you have been appointed my guardian, sir. Let us consider this interview at an end. Good-night," and with that she swept out of the room, ignoring Maloney and bestowing one biting glance on Blake, who actually winced, so little relish did he have for this ticklish part of the proceedings. I think we all felt like schoolboys who had been detected robbing a melon-patch or in some other heinous offence, as we slowly filed down the hall to the elevator. A woman of Mrs. Branford's stamp so readily and successfully puts one in the wrong that I could easily comprehend why Blake wanted to call on Kennedy for help in what otherwise seemed a plain case. Blake and Maloney were some distance ahead of us, as Craig leaned over to me and whispered. "That Maloney is impossible. I'll have to shake him loose in some way. Either we handle this case alone or we quit." "Right-o," I agreed emphatically. "He's put his foot in it badly at the very start. Only, be decent about it, Craig. The case is too big for you to let it slip by." "Trust me, Walter. I'll do it tactfully," he whispered, then to Blake he added as we overtook them: "Maloney is right. The case is simple enough, after all. But we must find out some way to fasten the thing more closely on Mrs. Branford. Let me think out a scheme to-night. I'll see you tomorrow." As Blake and Maloney disappeared down the street in the car, Kennedy wheeled about and walked deliberately back into the Grattan Inn again. It was quite late. People were coming in from the theatres, laughing and chatting gaily. Kennedy selected a table that commanded a view of the parlour as well as of the dining-room itself. "She was dressed to receive some one--did you notice?" he remarked as we sat down and cast our eyes over the dizzy array of inedibles on the card before us. "I think it is worth waiting a while to see who it is." Having ordered what I did not want, I glanced about until my eye rested on a large pier-glass at the other end of the dining-room. "Craig," I whispered excitedly, "Mrs. B. is in the writing-room--I can see her in that glass at the end of the room, behind you." "Get up and change places with me as quietly as you can, Walter," he said quickly. "I want to see her when she can't see me." Kennedy was staring in rapt attention at the mirror. "There's a man with her, Walter," he said under his breath. "He came in while we were changing places--a fine-looking chap. By Jove, I've seen him before somewhere. His face and his manner are familiar to me. But I simply can't place him. Did you see her wraps in the chair? No? Well, he's helping her on with them. They're going out. GARCON, L'ADDITION--VITE" We were too late, however, for just as we reached the door we caught a fleeting glimpse of a huge new limousine. "Who was that man who just went out with the lady?" asked Craig of the negro who turned the revolving-door at the carriage entrance. "Jack Delarue, sah--in 'The Grass Widower,' sah," replied the doorman. "Yes, sah, he stays here once in a while. Thank you, sah," as Kennedy dropped a quarter into the man's hand. "That complicates things considerably," he mused as we walked slowly down to the subway station. "Jack Delarue--I wonder if he is mixed up in this thing also." "I've heard that 'The Grass Widower' isn't such a howling success as a money-maker," I volunteered. "Delarue has a host of creditors, no doubt. By the way, Craig," I exclaimed, "don't you think it would be a good plan to drop down and see O'Connor? The police will have to be informed in a few hours now, anyhow. Maybe Delarue has a criminal record." "A good idea, Walter," agreed Craig, turning into a drug-store which had a telephone booth. "I'll just call O'Connor up, and we'll see if he does know anything about it." O'Connor was not at headquarters, but we finally found him at his home, and it was well into the small hours when we arrived there. Trusting to the first deputy's honour, which had stood many a test, Craig began to unfold the story. He had scarcely got as far as describing the work of the suspected hired yeggman, when O'Connor raised both hands and brought them down hard on the arms of his chair. "Say," he ejaculated, "that explains it!" "What?" we asked in chorus. "Why, one of my best stool-pigeons told me to-day that there was something doing at a house in the Chatham Square district that we have been watching for a long time. It's full of crooks, and to-day they've all been as drunk as lords, a sure sign some one has made a haul and been generous with the rest, And one or two of the professional 'fences' have been acting suspiciously, too. Oh, that explains it all right." I looked at Craig as much as to say, "I told you so," but he was engrossed in what O'Connor was saying. "You know," continued the police officer, "there is one particular 'fence' who runs his business under the guise of a loan-shark's office. He probably has a wider acquaintance among the big criminals than any other man in the city. From him crooks can obtain anything from a jimmy to a safe-cracking outfit. I know that this man has been trying to dispose of some unmounted pearls to-day among jewellers in Maiden Lane. I'll bet he has been disposing of some of the Branford pearls, one by one. I'll follow that up. I'll arrest this 'fence' and hold him till he tells me what yeggman came to him with the pearls." "And if you find out, will you go with me to that house near Chatham Square, providing it was some one in that gang?" asked Craig eagerly. O'Connor shook his head. "I'd better keep out of it. They know me too well. Go alone. I'll get that stool-pigeon--the Gay Cat is his name--to go with you. I'll help you in any way. I'll have any number of plain-clothes men you want ready to raid the place the moment you get the evidence. But you'll never get any evidence if they know I'm in the neighbourhood." The next morning Craig scarcely ate any breakfast himself and made me bolt my food most unceremoniously. We were out in Montclair again before the commuters had started to go to New York, and that in spite of the fact that we had stopped at his laboratory on the way and had got a package which he carried carefully. Kennedy instituted a most thorough search of the house from cellar to attic in daylight. What he expected to find, I did not know, but I am quite sure nothing escaped him. "Now, Walter," he said after he had ransacked the house, "there remains just one place. Here is this little wall safe in Mrs. Branford's room. We must open it." For an hour if not longer he worked over the combination, listening to the fall of the tumblers in the lock. It was a simple little thing and one of the old-timers in the industry would no doubt have opened it in short order. The perspiration stood out on his forehead, so intent was he in working the thing. At last it yielded. Except for some of the family silver, the safe was empty. Carefully noting how the light shone on the wall safe, Craig unwrapped the package he had brought and disclosed a camera. He placed it on a writing-desk opposite the safe, in such a way that it was not at all conspicuous, and focused it on the safe. "This is a camera with a newly-invented between-lens shutter of great illumination and efficiency," he explained. "It has always been practically impossible to get such pictures, but this new shutter has so much greater speed than anything ever invented before that it is possible to use it in detective work. I'll just run these fine wires like a burglar alarm, only instead of having an alarm I'll attach them to the camera so that we can get a picture. I've proved its speed up to one two-thousandth of a second. It may or it may not work. If it does we'll catch somebody, right in the act." About noon we went down to Liberty Street, home of burglary insurance. I don't think Blake liked it very much because Kennedy insisted on playing the lone hand, but he said nothing, for it was part of the agreement. Maloney seemed rather glad than otherwise. He had been combing out some tangled clues of his own about Mrs. Branford. Still, Kennedy smoothed things over by complimenting the detective on his activity, and indeed he had shown remarkable ability in the first place in locating Mrs. Branford. "I started out with the assumption that the Branfords must have needed money for some reason or other," said Maloney. "So I went to the commercial agencies to-day and looked up Branford. I can't say he has been prosperous; nobody has been in Wall Street these days, and that's just the thing that causes an increase in fake burglaries. Then there is another possibility," he continued triumphantly. "I had a man up at the Grattan Inn, and he reports to me that Mrs. Stanford was seen with the actor Jack Delarue last night, I imagine they quarrelled, for she returned alone, much agitated, in a taxi-cab. Any way you look at it, the clues are promising--whether she needed money for Branford's speculations or for the financing of that rake Delarue." Maloney regarded Craig with the air of an expert who could afford to patronise a good amateur--but after all an amateur. Kennedy said nothing, and of course I took the cue. "Yes," agreed Blake, "you see, our original hypothesis was a pretty good one. Meanwhile, of course, the police are floundering around in a bog of false scents." "It would make our case a good deal stronger," remarked Kennedy quietly, "if we could discover some of the stolen jewellery hidden somewhere by Mrs. Branford herself." He said nothing of his own unsuccessful search through the house, but continued: "What do you suppose she has done with the jewels? She must have put them somewhere before she got the yeggman to break the safe. She'd hardly trust them in his hands. But she might have been foolish enough for that. Of course it's another possibility that he really got away with them. I doubt if she has them at Grattan Inn, or even if she would personally put them in a safe deposit vault. Perhaps Delarue figures in that end of it. We must let no stone go unturned." "That's right," meditated Maloney, apparently turning something over in his mind as if it were a new idea. "If we only had some evidence, even part of the jewels that she had hidden, it would clinch the case. That's a good idea, Kennedy." Craig said nothing, but I could see, or fancied I saw, that he was gratified at the thought that he had started Maloney off on another trail, leaving us to follow ours unhampered. The interview with Blake was soon over, and as we left I looked inquiringly at Craig. "I want to see Mrs. Branford again," he said. "I think we can do better alone today than we did last night." I must say I half expected that she would refuse to see us and was quite surprised when the page returned with the request that we go up to her suite. It was evident that her attitude toward us was very different from that of the first interview. Whether she was ruffled by the official presence of Blake or the officious presence of Maloney, she was at least politely tolerant of us. Or was it that she at last began to realise that the toils were closing about her and that things began to look unmistakably black? Kennedy was quick to see his advantage. "Mrs. Branford," he began, "since last night I have come into the possession of some facts that are very important. I have heard that several loose pearls which may or may not be yours have been offered for sale by a man on the Bowery who is what the yeggmen call a 'fence.'" "Yeggmen--'fence'?" she repeated. "Mr. Kennedy, really I do not care to discuss the pearls any longer. It is immaterial to me what becomes of them. My first desire is to collect the insurance. If anything is recovered I am quite willing to deduct that amount from the total. But I must insist on the full insurance or the return of the pearls. As soon as Mr. Branford arrives I shall take other steps to secure redress." A boy rapped at the door and brought in a telegram which she tore open nervously. "He will be here in four days," she said, tearing the telegram petulantly, and not at all as if she were glad to receive it. "Is there anything else that you wish to say?" She was tapping her foot on the rug as if anxious to conclude the interview. Kennedy leaned forward earnestly and played his trump card boldly. "Do you remember that scene in 'The Grass Widower,'" he said slowly, "where Jack Delarue meets his runaway wife at the masquerade ball?" She coloured slightly, but instantly regained her composure. "Vaguely," she murmured, toying with the flowers in her dress. "In real life," said Kennedy, his voice purposely betraying that he meant it to have a personal application, "husbands do not forgive even rumours of--ah--shall we say affinities?--much less the fact." "In real life," she replied, "wives do not have affinities as often as some newspapers and plays would have us believe." "I saw Delarue after the performance last night," went on Kennedy inexorably. "I was not seen, but I saw, and he was with----" She was pacing the room now in unsuppressed excitement. "Will you never stop spying on me?" she cried. "Must my every act be watched and misrepresented? I suppose a distorted version of the facts will be given to my husband. Have you no chivalry, or justice, or--or mercy?" she pleaded, stopping in front of Kennedy. "Mrs. Branford," he replied coldly, "I cannot promise what I shall do. My duty is simply to get at the truth about the pearls. If it involves some other person, it is still my duty to get at the truth. Why not tell me all that you really know about the pearls and trust me to bring it out all right?" She faced him, pale and haggard. "I have told," she repeated steadily. "I cannot tell any more--I know nothing more." Was she lying? I was not expert enough in feminine psychology to judge, but down in my heart I knew that the woman was hiding something behind that forced steadiness. What was it she was battling for? We had reached an impasse. It was after dinner when I met Craig at the laboratory. He had made a trip to Montclair again, where his stay had been protracted because Maloney was there and he wished to avoid him. He had brought back the camera, and had had another talk with O'Connor, at which he had mapped out a plan of battle. "We are to meet the Gay Cat at the City Hall at nine o'clock," explained Craig laconically. "We are going to visit a haunt of yeggmen, Walter, that few outsiders have ever seen. Are you game? O'Connor and his men will be close by--hiding, of course." "I suppose so," I replied slowly. "But what excuse are you going to have for getting into this yegg-resort?" "Simply that we are two newspaper men looking for an article, without names, dates, or places--just a good story of yeggmen and tramps. I've got a little--well, we'll call it a little camera outfit that I'm going to sling over my shoulder. You are the reporter, remember, and I'm the newspaper photographer. They won't pose for us, of course, but that will be all right. Speaking about photographs, I got one out at Montclair that is interesting. I'll show it to you later in the evening--and in case anything should happen to me, Walter, you'll find the original plate locked here in the top drawer of my desk. I guess we'd better be getting downtown." The house to which we were guided by the Gay Cat was on a cross street within a block or two of Chatham Square. If we had passed it casually in the daytime there would have been nothing to distinguish it above the other ramshackle buildings on the street, except that the other houses were cluttered with children and baby-carriages, while this one was vacant, the front door closed, and the blinds tightly drawn. As we approached, a furtive figure shambled from the basement areaway and slunk off into the crowd for the night's business of pocket-picking or second-story work. I had had misgivings as to whether we would be admitted at all--I might almost say hopes--but the Gay Cat succeeded in getting a ready response at the basement door. The house itself was the dilapidated ruin of what had once been a fashionable residence in the days when society lived in the then suburban Bowery. The iron handrail on the steps was still graceful, though rusted and insecure. The stones of the steps were decayed and eaten away by time, and the front door was never opened. As we entered the low basement door, I felt that those who entered here did indeed abandon hope. Inside, the evidences of the past grandeur were still more striking. What had once been a drawing-room was now the general assembly room of the resort. Broken-down chairs lined the walls, and the floor was generously sprinkled with sawdust. A huge pot-bellied stove occupied the centre of the room, and by it stood a box of sawdust plentifully discoloured with tobacco-juice. Three or four of the "guests"--there was no "register" in this yeggman's hotel--were seated about the stove discussing something in a language that was English, to be sure, but of a variation that only a yegg could understand. I noted the once handsome white marble mantel, now stained by age, standing above the unused grate. Double folding-doors led to what, I imagine, was once a library. Dirt and grime indescribable were everywhere. There was the smell of old clothes and old cooking, the race odours of every nationality known to the metropolis. I recalled a night I once spent in a Bowery lodging-house for "local colour." Only this was infinitely worse. No law regulated this house. There was an atmosphere of cheerlessness that a half-blackened Welsbach mantle turned into positive ghastliness. Our guide introduced us. There was a dead silence as eight eyes were craftily fixed on us, sizing us up. What should I say? Craig came to the rescue. To him the adventure was a lark. It was novel, and that was merit enough. "Ask about the slang," he suggested. "That makes a picturesque story." It seemed to me innocuous enough, so I engaged in conversation with a man whom the Gay Cat had introduced as the proprietor. Much of the slang I already knew by hearsay, such as "bulls" for policemen, a "mouthpiece" for a lawyer to defend one when he is "ditched" or arrested; in fact, as I busily scribbled away I must have collected a lexicon of a hundred words or so for future reference. "And names?" I queried. "You have some queer nicknames." "Oh, yes," replied the man. "Now here's the Gay Cat--that's what we call a fellow who is the finder, who enters a town ahead of the gang. Then there's Chi Fat--that means he's from Chicago and fat. And Pitts Slim--he's from Pittsburgh and--" "Aw, cut it," broke in one of the others. "Pitts Slim'll be here to-night. He'll give you the devil if he hears you talking to reporters about him." The proprietor began to talk of less dangerous subjects. Craig succeeded in drawing out from him the yegg recipe for making "soup." "It's here in this cipher," said the man, drawing out a dirty piece of paper. "It's well known, and you can have this. Here's the key. It was written by 'Deafy' Smith, and the police pinched it." Craig busily translated the curious document: Take ten or a dozen sticks of dynamite, crumble it up fine, and put it in a pan or washbowl, then pour over it enough alcohol, wood or pure, to cover it well. Stir it up well with your hands, being careful to break all the lumps. Leave it set for a few minutes. Then get a few yards of cheesecloth and tear it up in pieces and strain the mixture through the cloth into another vessel. Wring the sawdust dry and throw it away. The remains will be the soup and alcohol mixed. Next take the same amount of water as you used of alcohol and pour it in. Leave the whole set for a few minutes. "Very interesting," commented Craig. "Safeblowing in one lesson by correspondence school. The rest of this tells how to attack various makes, doesn't it?" Just then a thin man in a huge, worn ulster came stamping upstairs from the basement, his collar up and his hat down over his eyes. There was something indefinably familiar about him, but as his face and figure were so well concealed, I could not tell just why I thought so. Catching a glimpse of us, he beat a retreat across the opposite end of the room, beckoning to the proprietor, who joined him outside the door. I thought I heard him ask: "Who are those men? Who let them in?" but I could not catch the reply. One by one the other occupants of the room rose and sidled out, leaving us alone with the Gay Cat. Kennedy reached over to get a cigarette from my case and light it from one that I was smoking. "That's our man, I think," he whispered--"Pitts Slim." I said nothing, but I would have been willing to part with a large section of my bank-account to be up on the Chatham Square station of the Elevated just then. There was a rush from the half-open door behind us. Suddenly everything turned black before me; my eyes swam; I felt a stinging sensation on my head and a weak feeling about the stomach; I sank half-conscious to the floor. All was blank, but, dimly, I seemed to be dragged and dropped down hard. How long I lay there I don't know. Kennedy says it was not over five minutes. It may have been so, but to me it seemed an age. When I opened my eyes I was lying on my back on a very dirty sofa in another room. Kennedy was bending over me with blood streaming from a long deep gash on his head. Another figure was groaning in the semi-darkness opposite; it was the Gay Cat. "They blackjacked us," whispered Kennedy to me as I staggered to my feet. "Then they dragged us through a secret passage into another house. How do you feel?" "All right," I answered, bracing myself against a chair, for I was weak from the loss of blood, and dizzy. I was sore in every joint and muscle. I looked about, only half comprehending. Then my recollection flooded back with a rush. We had been locked in another room after the attack, and left to be dealt with later. I felt in my pocket. I had left my watch at the laboratory, but even the dollar watch I had taken and the small sum of money in my pocketbook were gone. Kennedy still had his camera slung over his shoulder, where he had fastened it securely. Here we were, imprisoned, while Pitts Slim, the man we had come after, whoever he was, was making his escape. Somewhere across the street was O'Connor, waiting in a room as we had agreed. There was only one window in our room, and it opened on a miserable little dumbwaiter air-shaft. It would be hours yet before his suspicions would be aroused and he would discover which of the houses we were held in. Meanwhile what might not happen to us? Kennedy calmly set up his tripod. One leg had been broken in the rough-house, but he tied it together with his handkerchief, now wet with blood. I wondered how he could think of taking a picture. His very deliberation set me fretting and fuming, and I swore at him under my breath. Still, he worked calmly ahead. I saw him take the black box and set it on the tripod. It was indistinct in the darkness. It looked like a camera, and yet it had some attachment at the side that was queer, including a little lamp. Craig bent and attached some wires about the box. At last he seemed ready. "Walter," he whispered, "roll that sofa quietly over against the door. There, now the table and that bureau, and wedge the chairs in. Keep that door shut at any cost. It's now or never--here goes." He stopped a moment and tinkered with the box on the tripod. "Hello! Hello! Hello! Is that you, O'Connor?" he shouted. I watched him in amazement. Was the man crazy? Had the blow affected his brain? Here he was, trying to talk into a camera. A little signalling-bell in the box commenced to ring, as if by spirit hands. "Shut up in that room," growled a voice from outside the door. "By God, they've barricaded the door. Come on, pals, we'll kill the spies." A smile of triumph lighted up Kennedy's pale face. "It works, it works," he cried as the little bell continued to buzz. "This is a wireless telephone you perhaps have seen announced recently--good for several hundred feet--through walls and everything. The inventor placed it in a box easily carried by a man, including a battery, and mounted on an ordinary camera tripod so that the user might well be taken for a travelling photographer. It is good in one direction only, but I have a signalling-bell here that can be rung from the other end by Hertzian waves. Thank Heaven, it's compact and simple. "O'Connor," he went on, "it is as I told you. It was Pitts Slim. He left here ten or fifteen minutes ago--I don't know by what exit, but I heard them say they would meet at the Central freightyards at midnight. Start your plain-clothes men out and send some one here, quick, to release us. We are locked in a room in the fourth or fifth house from the corner. There's a secret passage to the yegg-house. The Gay Cat is still unconscious, Jameson is groggy, and I have a bad scalp wound. They are trying to beat in our barricade. Hurry." I think I shall never get straight in my mind the fearful five minutes that followed, the battering at the door, the oaths, the scuffle outside, the crash as the sofa, bureau, table, and chairs all yielded at once--and my relief when I saw the square-set, honest face of O'Connor and half a dozen plainclothes men holding the yeggs who would certainly have murdered us this time to protect their pal in his getaway. The fact is I didn't think straight until we were halfway uptown, speeding toward the railroad freight-yards in O'Connor's car. The fresh air at last revived me, and I began to forget my cute and bruises in the renewed excitement. We entered the yards carefully, accompanied by several of the railroad's detectives, who met us with a couple of police dogs. Skulking in the shadow under the high embankment that separated the yards with their interminable lines of full and empty cars on one side and the San Juan Hill district of New York up on the bluff on the other side, we came upon a party of three men who were waiting to catch the midnight "side-door Pullman"--the fast freight out of New York. The fight was brief, for we outnumbered them more than three to one. O'Connor himself snapped a pair of steel bracelets on the thin man, who seemed to be leader of the party. "It's all up, Pitts Slim," he ground out from his set teeth. One of our men flashed his bull's-eye on the three prisoners. I caught myself as in a dream. Pitts Slim was Maloney, the detective. An hour later, at headquarters, after the pedigrees had been taken, the "mugging" done, and the jewels found on the three yeggs checked off from the list of the Branford pearls, leaving a few thousand dollars' worth unaccounted for, O'Connor led the way into his private office. There were Mrs. Branford and Blake, waiting. Maloney sullenly refused to look at his former employer, as Blake rushed over and grasped Kennedy's hand, asking eagerly: "How did you do it, Kennedy? This is the last thing I expected." Craig said nothing, but slowly opened a now crumpled envelope, which contained an untoned print of a photograph. He laid it on the desk. "There is your yeggman--at work," he said. We bent over to look. It was a photograph of Maloney in the act of putting something in the little wall safe in Mrs. Branford's room. In a flash it dawned on me--the quick-shutter camera, the wire connected with the wall safe, Craig's hint to Maloney that if some of the jewels were found hidden in a likely place in the house, it would furnish the last link in the chain against her, Maloney's eager acceptance of the suggestion, and his visit to Montclair during which Craig had had hard work to avoid him. "Pitts Slim, alias Maloney," added Kennedy, turning to Blake, "your shrewdest private detective, was posing in two characters at once very successfully. He was your trusted agent in possession of the most valuable secrets of your clients, at the same time engineering all the robberies that you thought were fakes, and then working up the evidence incriminating the victims themselves. He got into the Branford house with a skeleton key, and killed the maid. The picture shows him putting this shield-shaped brooch in the safe this afternoon--here's the brooch. And all this time he was the leader of the most dangerous band of yeggmen in the country." "Mrs. Branford," exclaimed Blake, advancing and bowing most profoundly, "I trust that you understand my awkward position? My apologies cannot be too humble. It will give me great pleasure to hand you a certified check for the missing gems the first thing in the morning." Mrs. Branford bit her lip nervously. The return of the pearls did not seem to interest her in the least. "And I, too, must apologise for the false suspicion I had of you and--and--depend on me, it is already forgotten," said Kennedy, emphasising the "false" and looking her straight in the eyes. She read his meaning and a look of relief crossed her face. "Thank you," she murmured simply, then dropping her eyes she added in a lower tone which no one heard except Craig: "Mr. Kennedy, how can I ever thank you? Another night, and it would have been too late to save me from myself." III THE GERM OF DEATH By this time I was becoming used to Kennedy's strange visitors and, in fact, had begun to enjoy keenly the uncertainty of not knowing just what to expect from them next. Still, I was hardly prepared one evening to see a tall, nervous foreigner stalk noiselessly and unannounced into our apartment and hand his card to Kennedy without saying a word. "Dr. Nicholas Kharkoff--hum--er, Jameson, you must have forgotten to latch the door. Well, Dr. Kharkoff, what can I do for you? It is evident something has upset you." The tall Russian put his forefinger to his lips and, taking one of our good chairs, placed it by the door. Then he stood on it and peered cautiously through the transom into the hallway. "I think I eluded him this time," he exclaimed, as he nervously took a seat. "Professor Kennedy, I am being followed. Every step that I take somebody shadows me, from the moment I leave my office until I return. It is enough to drive me mad. But that is only one reason why I have come here to-night. I believe that I can trust you as a friend of justice--a friend of Russian freedom?" He had included me in his earnest but somewhat vague query, so that I did not withdraw. Somehow, apparently, he had heard of Kennedy's rather liberal political views. "It is about Vassili Saratovsky, the father of the Russian revolution, as we call him, that I have come to consult you," he continued quickly. "Just two weeks ago he was taken ill. It came on suddenly, a violent fever which continued for a week. Then he seemed to grow better, after the crisis had passed, and even attended a meeting of our central committee the other night. But in the meantime Olga Samarova, the little Russian dancer, whom yon have perhaps seen, fell ill in the same way. Samarova is an ardent revolutionist, you know. This morning the servant at my own home on East Broadway was also stricken, and--who knows?--perhaps it will be my turn next. For to-night Saratovsky had an even more violent return of the fever, with intense shivering, excruciating pains in the limbs, and delirious headache. It is not like anything I ever saw before. Can you look into the case before it grows any worse, Professor?" Again the Russian got on the chair and looked over the transom to be sure that he was not being overheard. "I shall be only too glad to help you in any way I can," returned Kennedy, his manner expressing the genuine interest that he never feigned over a particularly knotty problem in science and crime. "I had the pleasure of meeting Saratovsky once in London. I shall try to see him the first thing in the morning." Dr. Kharkov's face fell. "I had hoped you would see him to-night. If anything should happen----" "Is it as urgent as that?" "I believe it is," whispered Kharkoff, leaning forward earnestly. "We can call a taxicab--it will not take long, sir. Consider, there are many lives possibly at stake," he pleaded. "Very well, I will go," consented Kennedy. At the street door Kharkoff stopped short and drew Kennedy back. "Look--across the street in the shadow. There is the man. If I start toward him he will disappear; he is very clever. He followed me from Saratovsky's here, and has been waiting for me to come out." "There are two taxicabs waiting at the stand," suggested Kennedy. "Doctor, you jump in the first, and Jameson and I will take the second. Then he can't follow us." It was done in a moment, and we were whisked away, to the chagrin of the figure, which glided impotently out of the shadow in vain pursuit, too late even to catch the number of the cab. "A promising adventure," commented Kennedy, as we bumped along over New York's uneven asphalt. "Have you ever met Saratovsky?" "No," I replied dubiously. "Will you guarantee that he will not blow us up with a bomb?" "Grandmother!" replied Craig. "Why, Walter, he is the most gentle, engaging old philosopher----" "That ever cut a throat or scuttled a ship?" I interrupted. "On the contrary," insisted Kennedy, somewhat nettled, "he is a patriarch, respected by every faction of the revolutionists, from the fighting organisation to the believers in non-resistance and Tolstoy. I tell you, Walter, the nation that can produce a man such as Saratovsky deserves and some day will win political freedom. I have heard of this Dr. Kharkoff before, too. His life would be a short one if he were in Russia. A remarkable man, who fled after those unfortunate uprisings in 1905. Ah, we are on Fifth Avenue. I suspect that he is taking us to a club on the lower part of the avenue, where a number of the Russian reformers live, patiently waiting and planning for the great 'awakening' in their native land." Kharkoff's cab had stopped. Our quest had indeed brought us almost to Washington Square. Here we entered an old house of the past generation. As we passed through the wide hall, I noted the high ceilings, the old-fashioned marble mantels stained by time, the long, narrow rooms and dirty-white woodwork, and the threadbare furniture of black walnut and horsehair. Upstairs in a small back room we found the venerable Saratovsky, tossing, half-delirious with the fever, on a disordered bed. His was a striking figure in this sordid setting, with a high intellectual forehead and deep-set, glowing coals of eyes which gave a hint at the things which had made his life one of the strangest among all the revolutionists of Russia and the works he had done among the most daring. The brown dye was scarcely yet out of his flowing white beard--a relic of his last trip back to his fatherland, where he had eluded the secret police in the disguise of a German gymnasium professor. Saratovsky extended a thin, hot, emaciated hand to us, and we remained standing. Kennedy said nothing for the moment. The sick man motioned feebly to us to come closer. "Professor Kennedy," he whispered, "there is some deviltry afoot. The Russian autocracy would stop at nothing. Kharkoff has probably told you of it. I am so weak----" He groaned and sank back, overcome by a chill that seemed to rack his poor gaunt form. "Kazanovitch can tell Professor Kennedy something, Doctor. I am too weak to talk, even at this critical time. Take him to see Boris and Ekaterina." Almost reverently we withdrew, and Kharkoff led us down the hall to another room. The door was ajar, and a light disclosed a man in a Russian peasant's blouse, bending laboriously over a writing-desk. So absorbed was he that not until Kharkoff spoke did he look up. His figure was somewhat slight and his face pointed and of an ascetic mould. "Ah!" he exclaimed. "You have recalled me from a dream. I fancied I was on the old mir with Ivan, one of my characters. Welcome, comrades." It flashed over me at once that this was the famous Russian novelist, Boris Kazanovitch. I had not at first connected the name with that of the author of those gloomy tales of peasant life. Kazanovitch stood with his hands tucked under his blouse. "Night is my favourite time for writing," he explained. "It is then that the imagination works at its best." I gazed curiously about the room. There seemed to be a marked touch of a woman's hand here and there; it was unmistakable. At last my eye rested on a careless heap of dainty wearing apparel on a chair in the corner. "Where is Nevsky?" asked Dr. Kharkoff, apparently missing the person who owned the garments. "Ekaterina has gone to a rehearsal of the little play of Gershuni's escape from Siberia and betrayal by Rosenberg. She will stay with friends on East Broadway to-night. She has deserted me, and here I am all alone, finishing a story for one of the American magazines." "Ah, Professor Kennedy, that is unfortunate," commented Kharkoff. "A brilliant woman is Mademoiselle Nevsky--devoted to the cause. I know only one who equals her, and that is my patient downstairs, the little dancer, Samarova." "Samarova is faithful--Nevsky is a genius," put in Kazanovitch. Kharkoff said nothing for a time, though it was easy to see he regarded the actress highly. "Samarova," he said at length to us, "was arrested for her part in the assassination of Grand Duke Sergius and thrown into solitary confinement in the fortress of St. Peter and St. Paul. They tortured her, the beasts--burned her body with their cigarettes. It was unspeakable. But she would not confess, and finally they had to let her go. Nevsky, who was a student of biology at the University of St. Petersburg when Von Plehve was assassinated, was arrested, but her relatives had sufficient influence to secure her release. They met in Paris, and Nevsky persuaded Olga to go on the stage and come to New York." "Next to Ekaterina's devotion to the cause is her devotion to science," said Kazanovitch, opening a door to a little room. Then he added: "If she were not a woman, or if your universities were less prejudiced, she would be welcome anywhere as a professor. See, here is her laboratory. It is the best we--she can afford. Organic chemistry, as you call it in English, interests me too, but of course I am not a trained scientist--I am a novelist." The laboratory was simple, almost bare. Photographs of Koch, Ehrlich, Metchnikoff, and a number of other scientists adorned the walls. The deeply stained deal table was littered with beakers and test-tubes. "How is Saratovsky?" asked the writer of the doctor, aside, as we gazed curiously about. Kharkoff shook his head gravely. "We have just come from his room. He was too weak to talk, but he asked that you tell Mr. Kennedy anything that it is necessary he should know about our suspicions." "It is that we are living with the sword of Damocles constantly dangling over our heads, gentlemen," cried Kazanovitch passionately, turning toward us. "You will excuse me if I get some cigarettes downstairs? Over them I will tell you what we fear." A call from Saratovsky took the doctor away also at the same moment, and we were left alone. "A queer situation, Craig," I remarked, glancing involuntarily at the heap of feminine finery on the chair, as I sat down before Kazanovitch's desk. "Queer for New York; not for St. Petersburg," was his laconic reply, as he looked around for another chair. Everything was littered with books, and papers, and at last he leaned over and lifted the dress from the chair to place it on the bed, as the easiest way of securing a seat in the scantily furnished room. A pocketbook and a letter fell to the floor from the folds of the dress. He stooped to pick them up, and I saw a strange look of surprise on his face. Without a moment's hesitation he shoved the letter into his pocket and replaced the other things as he had found them. A moment later Kazanovitch returned with a large box of Russian cigarettes. "Be seated, sir," he said to Kennedy, sweeping a mass of books and papers off a large divan. "When Nevsky is not here the room gets sadly disarranged. I have no genius for order." Amid the clouds of fragrant light smoke we waited for Kazanovitch to break the silence. "Perhaps you think that the iron hand of the Russian prime minister has broken the backbone of revolution in Russia," he began at length. "But because the Duma is subservient, it does not mean that all is over. Not at all. We are not asleep. Revolution is smouldering, ready to break forth at any moment. The agents of the government know it. They are desperate. There is no means they would not use to crush us. Their long arm reaches even to New York, in this land of freedom." He rose and excitedly paced the room. Somehow or other, this man did not prepossess me. Was it that I was prejudiced by a puritanical disapproval of the things that pass current in Old World morality? Or was it merely that I found the great writer of fiction seeking the dramatic effect always at the cost of sincerity? "Just what is it that you suspect?" asked Craig, anxious to dispense with the rhetoric and to get down to facts. "Surely, when three persons are stricken, you must suspect something." "Poison," replied Kazanovitch quickly. "Poison, and of a kind that even the poison doctors of St. Petersburg have never employed. Dr. Kharkoff is completely baffled. Your American doctors--two were called in to see Saratovsky--say it is the typhus fever. But Kharkoff knows better. There is no typhus rash. Besides"--and he leaned forward to emphasise his words--"one does not get over typhus in a week and have it again as Saratovsky has." I could see that Kennedy was growing impatient. An idea had occurred to him, and only politeness kept him listening to Kazanovitch longer. "Doctor," he said, as Kharkoff entered the room again, "do you suppose you could get some perfectly clean test-tubes and sterile bouillon from Miss Nevsky's laboratory? I think I saw a rack of tubes on the table." "Surely," answered Kharkoff. "You will excuse us, Mr. Kazanovitch," apologised Kennedy briskly, "but I feel that I am going to have a hard day to-morrow and--by the way, would you be so kind as to come up to my laboratory some time during the day, and continue your story." On the way out Craig took the doctor aside for a moment, and they talked earnestly. At last Craig motioned to me. "Walter," he explained, "Dr. Kharkoff is going to prepare some cultures in the test-tubes to-night so that I can make a microscopic examination of the blood of Saratovsky, Samarova, and later of his servant. The tubes will be ready early in the morning, and I have arranged with the doctor for you to call and get them if you have no objection." I assented, and we started downstairs. As we passed a door on the second floor, a woman's voice called out, "Is that you, Boris?" "No, Olga, this is Nicholas," replied the doctor. "It is Samarova," he said to us as he entered. In a few moments he rejoined us. "She is no better," he continued, as we again started away. "I may as well tell you, Professor Kennedy, just how matters stand here. Samarova is head over heels in love with Kazanovitch--you heard her call for him just now? Before they left Paris, Kazanovitch showed some partiality for Olga, but now Nevsky has captured him. She is indeed a fascinating woman, but as for me, if Olga would consent to become Madame Kharkoff, it should be done tomorrow, and she need worry no longer over her broken contract with the American theatre managers. But women are not that way. She prefers the hopeless love. Ah, well, I shall let you know if anything new happens. Good-night, and a thou-sand thanks for your help, gentlemen." Nothing was said by either of us on our journey uptown, for it was late and I, at least, was tired. But Kennedy had no intention of going to bed, I found. Instead, he sat down in his easy chair and shaded his eyes, apparently in deep thought. As I stood by the table to fill my pipe for a last smoke, I saw that he was carefully regarding the letter he had picked up, turning it over and over, and apparently debating with himself what to do with it. "Some kinds of paper can be steamed open without leaving any trace," he remarked in answer to my unspoken question, laying the letter down before me. I read the address: "M. Alexander Alexandrovitch Orloff,--Rue de----, Paris, France." "Letter-opening has been raised to a fine art by the secret service agents of foreign countries," he continued. "Why not take a chance? The simple operation of steaming a letter open is followed by reburnishing the flap with a bone instrument, and no trace is left. I can't do that, for this letter is sealed with wax. One way would be to take a matrix of the seal before breaking the wax and then replace a duplicate of it. No, I won't risk it. I'll try a scientific way." Between two pieces of smooth wood, Craig laid the letter flat, so that the edges projected about a thirty-second of an inch. He flattened the projecting edge of the envelope, then roughened it, and finally slit it open. "You see, Walter, later I will place the letter back, apply a hair line of strong white gum, and unite the edges of the envelope under pressure. Let us see what we have here." He drew out what seemed to be a manuscript on very thin paper, and spread it out flat on the table before us. Apparently it was a scientific paper on a rather unusual subject, "Spontaneous Generation of Life." It was in longhand and read: Many thanks for the copy of the paper by Prof. Betaillon of Dijon on the artificial fertilization of the eggs of frogs. I consider it a most important advance in the artificial generation of life. I will not attempt to reproduce in facsimile the entire manuscript, for it is unnecessary, and, in fact, I merely set down part of its contents here because it seemed so utterly valueless to me at the time. It went on to say: While Betaillon punctured the eggs with a platinum needle and developed them by means of electric discharges, Loeb in America placed eggs of the sea-urchin in a strong solution of sea water, then in a bath where they were subjected to the action of butyric acid. Finally they were placed in ordinary sea water again, where they developed in the natural manner. Delage at Roscorf used a liquid containing salts of magnesia and tannate of ammonia to produce the same result. In his latest book on the Origin of Life Dr. Charlton Bastian tells of using two solutions. One consisted of two or three drops of dilute sodium silicate with eight drops of liquor ferri pernitratis to one ounce of distilled water. The other was composed of the same amount of the silicate with six drops of dilute phosphoric acid and six grains of ammonium phosphate. He filled sterilised tubes, sealed them hermetically, and heated them to 125 or 145 degrees, Centigrade, although 60 or 70 degrees would have killed any bacteria remaining in them. Next he exposed them to sunlight in a south window for from two to four months. When the tubes were opened Dr. Bastian found organisms in them which differed in no way from real bacteria. They grew and multiplied. He contends that he has proved the possibility of spontaneous generation of life. Then there were the experiments of John Butler Burke of Cambridge, who claimed that he had developed "radiobes" in tubes of sterilised bouillon by means of radium emanations. Daniel Berthelot in France last year announced that he had used the ultra-violet rays to duplicate nature's own process of chlorophyll assimilation. He has broken up carbon dioxide and water-vapour in the air in precisely the same way that the green cells of plants do it. Leduc at Nantes has made crystals grow from an artificial "egg" composed of certain chemicals. These crystals show all the apparent vital phenomena without being actually alive. His work is interesting, for it shows the physical forces that probably control minute life cells, once they are created. "What do you make of it?" asked Kennedy, noting the puzzled look on my face as I finished reading. "Well, recent research in the problem of the origin of life may be very interesting," I replied. "There are a good many chemicals mentioned here--I wonder if any of them is poisonous? But I am of the opinion that there is something more to this manuscript than a mere scientific paper." "Exactly, Walter," said Kennedy in half raillery. "What I wanted to know was how you would suggest getting at that something." Study as I might, I could make nothing out of it. Meanwhile Craig was busily figuring with a piece of paper and a pencil. "I give it up, Craig," I said at last. "It is late. Perhaps we had better both turn in, and we may have some ideas on it in the morning." For answer he merely shook his head and continued to scribble and figure on the paper. With a reluctant good-night I shut my door, determined to be up early in the morning and go for the tubes that Kharkoff was to prepare. But in the morning Kennedy was gone. I dressed hastily, and was just about to go out when he hurried in, showing plainly the effects of having spent a sleepless night. He flung an early edition of a newspaper on the table. "Too late," he exclaimed. "I tried to reach Kharkoff, but it was too late." "Another East Side Bomb Outrage," I read. "While returning at a late hour last night from a patient, Dr. Nicholas Kharkoff, of--East Broadway, was severely injured by a bomb which had been placed in his hallway earlier in the evening. Dr. Kharkoff, who is a well-known physician on the East Side, states that he has been constantly shadowed by some one unknown for the past week or two. He attributes his escape with his life to the fact that since he was shadowed he has observed extreme caution. Yesterday his cook was poisoned and is now dangerously ill. Dr. Kharkoff stands high in the Russian community, and it is thought by the police that the bomb was placed by a Russian political agent, as Kharkoff has been active in the ranks of the revolutionists." "But what made you anticipate it?" I asked of Kennedy, considerably mystified. "The manuscript," he replied. "The manuscript? How? Where is it?" "After I found that it was too late to save Kharkoff and that he was well cared for at the hospital, I hurried to Saratovsky's. Kharkoff had fortunately left the tubes there, and I got them. Here they are. As for the manuscript in the letter, I was going to ask you to slip upstairs by some strategy and return it where I found it, when you went for the tubes this morning. Kazanovitch was out, and I have returned it myself, so you need not go, now." "He's coming to see you today, isn't he?" "I hope so. I left a note asking him to bring Miss Nevsky, if possible, too. Come, let us breakfast and go over to the laboratory. They may arrive at any moment. Besides, I'm interested to see what the tubes disclose." Instead of Kazanovitch awaiting us at the laboratory, however, we found Miss Nevsky, haggard and worn. She was a tall, striking girl with more of the Gaul than the Slav in her appearance. There was a slightly sensuous curve to her mouth, but on the whole her face was striking and intellectual. I felt that if she chose she could fascinate a man so that he would dare anything. I never before understood why the Russian police feared the women revolutionists so much. It was because they were themselves, plus every man they could influence. Nevsky appeared very excited. She talked rapidly, and fire flashed from her grey eyes. "They tell me at the club," she began, "that you are investigating the terrible things that are happening to us. Oh, Professor Kennedy, it is awful! Last night I was staying with some friends on East Broadway. Suddenly we heard a terrific explosion up the street. It was in front of Dr. Kharkoff's house. Thank Heaven, he is still alive I But I was so unnerved I could not sleep. I fancied I might be the next to go. "Early this morning I hastened to return to Fifth Avenue. As I entered the door of my room I could not help thinking of the horrible fate of Dr. Kharkoff. For some unknown reason, just as I was about to push the door farther open, I hesitated and looked--I almost fainted. There stood another bomb just inside. If I had moved the door a fraction of an inch it would have exploded. I screamed, and Olga, sick as she was, ran to my assistance--or perhaps she thought something had happened to Boris. It is standing there yet. None of us dares touch it. Oh, Professor Kennedy, it is dreadful, dreadful. And I cannot find Boris--Mr. Kazanovitch, I mean. Saratovsky, who is like a father to us all, is scarcely able to speak. Dr. Kharkoff is helpless in the hospital. Oh, what are we to do, what are we to do?" She stood trembling before us, imploring. "Calm yourself, Miss Nevsky," said Kennedy in a reassuring tone. "Sit down and let us plan. I take it that it was a chemical bomb and not one with a fuse, or you would have a different story to tell. First of all, we must remove it. That is easily done." He called up a near-by garage and ordered an automobile. "I will drive it myself," he ordered, "only send a man around with it immediately." "No, no, no," she cried, running toward him, "you must not risk it. It is bad enough that we should risk our lives. But strangers must not. Think, Professor Kennedy. Suppose the bomb should explode at a touch! Had we not better call the police and let them take the risk, even if it does get into the papers?" "No," replied Kennedy firmly. "Miss Nevsky, I am quite willing to take the risk. Besides, here comes the automobile." "You are too kind," she exclaimed. "Kazanovitch himself could do no more. How am I ever to thank you?" On the back of the automobile Kennedy placed a peculiar oblong box, swung on two concentric rings balanced on pivots, like a most delicate compass. We rode quickly downtown, and Kennedy hurried into the house, bidding us stand back. With a long pair of tongs he seized the bomb firmly. It was a tense moment. Suppose his hand should unnecessarily tremble, or he should tip it just a bit--it might explode and blow him to atoms. Keeping it perfectly horizontal he carried it carefully out to the waiting automobile and placed it gingerly in the box. "Wouldn't it be a good thing to fill the box with water?" I suggested, having read somewhere that that was the usual way of opening a bomb, under water. "No," he replied, as he closed the lid, "that wouldn't do any good with a bomb of this sort. It would explode under water just as well as in air. This is a safety bomb-carrier. It is known as the Cardan suspension. It was invented by Professor Cardono, an Italian. You see, it is always held in a perfectly horizontal position, no matter how you jar it. I am now going to take the bomb to some safe and convenient place where I can examine it at my leisure. Meanwhile, Miss Nevsky, I will leave you in charge of Mr. Jameson." "Thank you so much," she said. "I feel better now. I didn't dare go into my own room with that bomb at the door. If Mr. Jameson can only find out what has become of Mr. Kazanovitch, that is all I want. What do you suppose has happened to him? Is he, too, hurt or ill?" "Very well, then," Craig replied. "I will commission you, Walter, to find Kazanovitch. I shall be back again shortly before noon to examine the wreck of Kharkoff's office. Meet me there. Goodbye, Miss Nevsky." It was not the first time that I had had a roving commission to find some one who had disappeared in New York. I started by inquiring for every possible place that he might be found. No one at the Fifth Avenue house could tell me anything definite, though they were able to give me a number of places where he was known. I consumed practically the whole morning going from one place to another on the East Side. Some of the picturesque haunts of the revolutionists would have furnished material for a story in themselves. But nowhere had they any word of Kazanovitch, until I visited a Polish artist who was illustrating his stories. He had been there, looking very worn and tired, and had talked vacantly about the sketches which the artist had showed him. After that I lost all trace of him again. It was nearly noon as I hurried to meet Craig at Kharkoff's. Imagine my surprise to see Kazanovitch already there, seated in the wrecked office, furiously smoking cigarettes and showing evident signs of having something very disturbing on his mind. The moment he caught sight of me, he hurried forward. "Is Professor Kennedy coming soon?" he inquired eagerly. "I was going up to his laboratory, but I called up Nevsky, and she said he would be here at noon." Then he put his hand up to my ear and whispered, "I have found out who it was who shadowed Kharkoff." "Who?" I asked, saying nothing of my long search of the morning. "His name is Revalenko--Feodor Revalenko. I saw him standing across the street in front of the house last night after you had gone. When Kharkoff left, he followed him. I hurried out quietly and followed both of them. Then the explosion came. This man slipped down a narrow street as soon as he saw Kharkoff fall. As people were running to Kharkoff's assistance, I did the same. He saw me following him and ran, and I ran, too, and overtook him. Mr. Jameson, when I looked into his face I could not believe it. Revalenko--he is one of the most ardent members of our organisation. He would not tell me why he had followed Kharkoff. I could make him confess nothing. But I am sure he is an agent provocateur of the Russian government, that he is secretly giving away the plans that we are making, everything. We have a plot on now--perhaps he has informed them of that. Of course he denied setting the bomb or trying to poison any of us, but he was very frightened. I shall denounce him at the first opportunity." I said nothing. Kazanovitch regarded me keenly to see what impression the story made on me, but I did not let my looks betray anything, except proper surprise, and he seemed satisfied. It might be true, after all, I reasoned, the more I thought of it. I had heard that the Russian consul-general had a very extensive spy system in the city. In fact, even that morning I had had pointed out to me some spies at work in the public libraries, watching what young Russians were reading. I did not doubt that there were spies in the very inner circle of the revolutionists themselves. At last Kennedy appeared. While Kazanovitch poured forth his story, with here and there, I fancied, an elaboration of a particularly dramatic point, Kennedy quickly examined the walls and floor of the wrecked office with his magnifying-glass. When he had concluded his search, he turned to Kazanovitch. "Would it be possible," he asked, "to let this Revalenko believe that he could trust you, that it would be safe for him to visit you to-night at Saratovsky's? Surely you can find some way of reassuring him." "Yes, I think that can be arranged," said Kazanovitch. "I will go to him, will make him think I have misunderstood him, that I have not lost faith in him, provided he can explain all. He will come. Trust me." "Very well, then. To-night at eight I shall be there," promised Kennedy, as the novelist and he shook hands. "What do you think of the Revalenko story?" I asked of Craig, as we started uptown again. "Anything is possible in this case," he answered sententiously. "Well," I exclaimed, "this all is truly Russian. For intrigue they are certainly the leaders of the world to-day. There is only one person that I have any real confidence in, and that is old Saratovsky himself. Somebody is playing traitor, Craig. Who is it?" "That is what science will tell us to-night," was his brief reply. There was no getting anything out of Craig until he was absolutely sure that his proofs had piled up irresistibly. Promptly at eight we met at the old house on Fifth Avenue. Kharkoff's wounds had proved less severe than had at first been suspected, and, having recovered from the shock, he insisted on being transferred from the hospital in a private ambulance so that he could be near his friends. Saratovsky, in spite of his high fever, ordered that the door to his room be left open and his bed moved so that he could hear and see what passed in the room down the hall. Nevsky was there and Kazanovitch, and even brave Olga Samarova, her pretty face burning with the fever, would not be content until she was carried upstairs, although Dr. Kharkoff protested vigorously that it might have fatal consequences. Revalenko, an enigma of a man, sat stolidly. The only thing I noticed about him was an occasional look of malignity at Nevsky and Kazanovitch when he thought he was unobserved. It was indeed a strange gathering, the like of which the old house had never before harboured in all its varied history. Every one was on the qui vive, as Kennedy placed on the table a small wire basket containing some test-tubes, each tube corked with a small wadding of cotton. There was also a receptacle holding a dozen glass-handled platinum wires, a microscope, and a number of slides. The bomb, now rendered innocuous by having been crushed in a huge hydraulic press, lay in fragments in the box. "First, I want you to consider the evidence of the bomb," began Kennedy. "No crime, I firmly believe, is ever perpetrated without leaving some clue. The slightest trace, even a drop of blood no larger than a pin-head, may suffice to convict a murderer. The impression made on a cartridge by the hammer of a pistol, or a single hair found on the clothing of a suspected person, may serve as valid proof of crime. "Until lately, however, science was powerless against the bomb-thrower. A bomb explodes into a thousand parts, and its contents suddenly become gaseous. You can't collect and investigate the gases. Still, the bomb-thrower is sadly deceived if he believes the bomb leaves no trace for the scientific detective. It is difficult for the chemist to find out the secrets of a shattered bomb. But it can be done. "I examined the walls of Dr. Kharkoff's house, and fortunately was able to pick out a few small fragments of the contents of the bomb which had been thrown out before the flame ignited them. I have analysed them, and find them to be a peculiar species of blasting-gelatine. It is made at only one factory in this country, and I have a list of purchasers for some time back. One name, or rather the description of an assumed name, in the list agrees with other evidence I have been able to collect. Moreover, the explosive was placed in a lead tube. Lead tubes are common enough. However, there is no need of further evidence." He paused, and the revolutionists stared fixedly at the fragments of the now harmless bomb before them. "The exploded bomb," concluded Craig, "was composed of the same materials as this, which I found unexploded at the door of Miss Nevsky's room--the same sort of lead tube, the same blasting-gelatine. The fuse, a long cord saturated in sulphur, was merely a blind. The real method of explosion was by means of a chemical contained in a glass tube which was inserted after the bomb was put in place. The least jar, such as opening a door, which would tip the bomb ever so little out of the horizontal, was all that was necessary to explode it. The exploded bomb and the unexploded were in all respects identical--the same hand set both." A gasp of astonishment ran through the circle. Could it be that one of their own number was playing false? In at least this instance in the warfare of the chemist and the dynamiter the chemist had come out ahead. "But," Kennedy hurried along, "the thing that interests me most about this case is not the evidence of the bombs. Bombs are common enough weapons, after all. It is the evidence of almost diabolical cunning that has been shown in the effort to get rid of the father of the revolution, as you like to call him." Craig cleared his throat and played with our feelings as a cat does with a mouse. "Strange to say, the most deadly, the most insidious, the most elusive agency for committing murder is one that can be obtained and distributed with practically no legal restrictions. Any doctor can purchase disease germs in quantities sufficient to cause thousands and thousands of deaths without giving any adequate explanation for what purpose he requires them. More than that, any person claiming to be a scientist or having some acquaintance with science and scientists can usually obtain germs without difficulty. Every pathological laboratory contains stores of disease germs, neatly sealed up in test-tubes, sufficient to depopulate whole cities and even nations. With almost no effort, I myself have actually cultivated enough germs to kill every person within a radius of a mile of the Washington Arch down the street. They are here in these test-tubes." We scarcely breathed. Suppose Kennedy should let loose this deadly foe, these germs of death, whatever they were? Yet that was precisely what some fiend incarnate had done, and that fiend was sitting in the room with us. "Here I have one of the most modern dark-field microscopes," he resumed. "On this slide I have placed a little pin-point of a culture made from the blood of Saratovsky. I will stain the culture. Now--er--Walter, look through the microscope under this powerful light and tell us what you see on the slide." I bent over. "In the darkened field I see a number of germs like dancing points of coloured light," I said. "They are wriggling about with a peculiar twisting motion." "Like a corkscrew," interrupted Kennedy, impatient to go on. "They are of the species known as Spirilla. Here is another slide, a culture from the blood of Samarova." "I see them there, too," I exclaimed. Every one was now crowding about for a glimpse, as I raised my head. "What is this germ?" asked a hollow voice from the doorway. We looked, startled. There stood Saratovsky, more like a ghost than a living being. Kennedy sprang forward and caught him as he swayed, and I moved up an armchair for him. "It is the spirillum Obermeieri," said Kennedy, "the germ of the relapsing fever, but of the most virulent Asiatic strain. Obermeyer, who discovered it, caught the disease and died of it, a martyr to science." A shriek of consternation rang forth from Samarova. The rest of us paled, but repressed our feelings. "One moment," added Kennedy hastily. "Don't be unnecessarily alarmed. I have something more to say. Be calm for a moment longer." He unrolled a blue-print and placed it on the table. "This," he continued, "is the photographic copy of a message which, I suppose, is now on its way to the Russian minister to France in Paris. Some one in this room besides Mr. Jameson and myself has seen this letter before. I will hold it up as I pass around and let each one see it." In intense silence Kennedy passed before each of us, holding up the blue-print and searchingly scanning the faces. No one betrayed by any sign that he recognised it. At last it came to Revalenko himself. "The checkerboard, the checkerboard!" he cried, his eyes half starting from their sockets as he gazed at it. "Yes," said Kennedy in a low tone, "the checkerboard. It took me some time to figure it out. It is a cipher that would have baffled Poe. In fact, there is no means of deciphering it unless you chance to know its secret. I happened to have heard of it a long time ago abroad, yet my recollection was vague, and I had to reconstruct it with much difficulty. It took me all night to do it. It is a cipher, however, that is well known among the official classes of Russia. "Fortunately I remember the crucial point, without which I should still be puzzling over it. It is that a perfectly innocent message, on its face, may be used to carry a secret, hidden message. The letters which compose the words, instead of being written continuously along, as we ordinarily write, have, as you will observe if you look twice, breaks, here and there. These breaks in the letters stand for numbers. "Thus the first words are 'Many thanks.' The first break is at the end of the letter 'n,' between it and the 'y.' There are three letters before this break. That stands for the number 3. "When you come to the end of a word, if the stroke is down at the end of the last letter, that means no break; if it is up, it means a break. The stroke at the end of the 'y' is plainly down. Therefore there is no break until after the 't.' That gives us the number 2. So we get 1 next, and again 1, and still again 1; then 5; then 5; then 1; and so on. "Now, take these numbers in pairs, thus 3-2; 1-1; 1-5; 5-1. By consulting this table you can arrive at the hidden message." He held up a cardboard bearing the following arrangement of the letters of the alphabet: 1 2 3 4 5 1 A B C D E 2 F G H IJ K 3 L M N O P 4 Q R S T U 5 V W X Y Z "Thus," he continued, "3-2 means the third column and second line. That is 'H.' Then 1-1 is 'A '; 1-5 is 'V '; 5-1 is 'E'--and we get the word 'Have.'" Not a soul stirred as Kennedy unfolded the cipher. What was the terrible secret in that scientific essay I had puzzled so unsuccessfully over, the night before? "Even this can be complicated by choosing a series of fixed numbers to be added to the real numbers over and over again. Or the order of the alphabet can be changed. However, we have the straight cipher only to deal with here." "And what for Heaven's sake does it reveal?" asked Saratovsky, leaning forward, forgetful of the fever that was consuming him. Kennedy pulled out a piece of paper on which he had written the hidden message and read: "Have successfully inoculated S. with fever. Public opinion America would condemn violence. Think best death should appear natural. Samarova infected also. Cook unfortunately took dose in food intended Kharkoff. Now have three cases. Shall stop there at present. Dangerous excite further suspicion health authorities." Rapidly I eliminated in my mind the persons mentioned, as Craig read. Saratovsky of course was not guilty, for the plot had centred about him. Nor was little Samarova, nor Dr. Kharkoff. I noted Revalenko and Kazanovitch glaring at each other and hastily tried to decide which I more strongly suspected. "Will get K.," continued Kennedy. "Think bomb perhaps all right. K. case different from S. No public sentiment." "So Kharkoff had been marked for slaughter," I thought. Or was "K." Kazanovitch? I regarded Revalenko more closely. He was suspiciously sullen. "Must have more money. Cable ten thousand rubles at once Russian consul-general. Will advise you plot against Czar as details perfected here. Expect break up New York band with death of S." If Kennedy himself had thrown a bomb or scattered broadcast the contents of the test-tubes, the effect could not have been more startling than his last quiet sentence--and sentence it was in two senses. "Signed," he said, folding the paper up deliberately, "Ekaterina Nevsky." It was as if a cable had snapped and a weight had fallen. Revalenko sprang up and grasped Kazanovitch by the hand. "Forgive me, comrade, for ever suspecting you," he cried. "And forgive me for suspecting you," replied Kazanovitch, "but how did you come to shadow Kharkoff?" "I ordered him to follow Kharkoff secretly and protect him," explained Saratovsky. Olga and Ekaterina faced each other fiercely. Olga was trembling with emotion. Nevsky stood coldly, defiantly. If ever there was a consummate actress it was she, who had put the bomb at her own door and had rushed off to start Kennedy on a blind trail. "You traitress," cried Olga passionately, forgetting all in her outraged love. "You won his affections from me by your false beauty--yet all the time you would have killed him like a dog for the Czar's gold. At last you are unmasked--you Azeff in skirts. False friend--you would have killed us all--Saratovsky, Kharkoff--" "Be still, little fool," exclaimed Nevsky contemptuously. "The spirilla fever has affected your brains. Bah! I will not stay with those who are so ready to suspect an old comrade on the mere word of a charlatan. Boris Kazanovitch, do you stand there SILENT and let this insult be heaped upon me?" For answer, Kazanovitch deliberately turned his back on his lover of a moment ago and crossed the room. "Olga," he pleaded, "I have been a fool. Some day I may be worthy of your love. Fever or not, I must beg your forgiveness." With a cry of delight the actress flung her arms about Boris, as he imprinted a penitent kiss on her warm lips. "Simpleton," hissed Nevsky with curling lips. "Now you, too, will die." "One moment, Ekaterina Nevsky," interposed Kennedy, as he picked up some vacuum tubes full of a golden-yellow powder, that lay on the table. "The spirilla, as scientists now know, belong to the same family as those which cause what we call, euphemistically, the 'black plague.' It is the same species as that of the African sleeping sickness and the Philippine yaws. Last year a famous doctor whose photograph I see in the next room, Dr. Ehrlich of Frankfort, discovered a cure for all these diseases. It will rid the blood of your victims of the Asiatic relapsing fever germs in forty-eight hours. In these tubes I have the now famous salvarsan." With a piercing shriek of rage at seeing her deadly work so quickly and completely undone, Nevsky flung herself into the little laboratory behind her and bolted the door. Her face still wore the same cold, contemptuous smile, as Kennedy gently withdrew a sharp scalpel from her breast. "Perhaps it is best this way, after all," he said simply. IV THE FIREBUG A big, powerful, red touring-car, with a shining brass bell on the front of it, was standing at the curb before our apartment late one afternoon as I entered. It was such a machine as one frequently sees threading its reckless course in and out among the trucks and street-cars, breaking all rules and regulations, stopping at nothing, the bell clanging with excitement, policemen holding back traffic instead of trying to arrest the driver--in other words, a Fire Department automobile. I regarded it curiously for a moment, for everything connected with modern fire-fighting is interesting. Then I forgot about it as I was whisked up in the elevator, only to have it recalled sharply by the sight of a strongly built, grizzled man in a blue uniform with red lining. He was leaning forward, earnestly pouring forth a story into Kennedy's ear. "And back of the whole thing, sir," I heard him say as he brought his large fist down on the table, "is a firebug--mark my words." Before I could close the door, Craig caught my eye, and I read in his look that he had a new case--one that interested him greatly. "Walter," he cried, "this is Fire Marshal McCormick. It's all right, McCormick. Mr. Jameson is an accessory both before and after the fact in my detective cases." A firebug!--one of the most dangerous of criminals. The word excited my imagination at once, for the newspapers had lately been making much of the strange and appalling succession of apparently incendiary fires that had terrorised the business section of the city. "Just what makes you think that there is a firebug--one firebug, I mean--back of this curious epidemic of fires?" asked Kennedy, leaning back in his morrischair with his finger-tips together and his eyes half closed as if expecting a revelation from some subconscious train of thought while the fire marshal presented his case. "Well, usually there is no rhyme or reason about the firebug," replied McCormick, measuring his words, "but this time I think there is some method in his madness. You know the Stacey department-stores and their allied dry-goods and garment-trade interests?" Craig nodded. Of course we knew of the gigantic dry-goods combination. It had been the talk of the press at the time of its formation, a few months ago, especially as it included among its organisers one very clever business woman, Miss Rebecca Wend. There had been considerable opposition to the combination in the trade, but Stacey had shattered it by the sheer force of his personality. McCormick leaned forward and, shaking his forefinger to emphasise his point, replied slowly, "Practically every one of these fires has been directed against a Stacey subsidiary or a corporation controlled by them." "But if it has gone as far as that," put in Kennedy, "surely the regular police ought to be of more assistance to you than I." "I have called in the police," answered McCormick wearily, "but they haven't even made up their minds whether it is a single firebug or a gang. And in the meantime, my God, Kennedy, the firebug may start a fire that will get beyond control!" "You say the police haven't a single clue to any one who might be responsible for the fires?" I asked, hoping that perhaps the marshal might talk more freely of his suspicions to us than he had already expressed himself in the newspaper interviews I had read. "Absolutely not a clue--except such as are ridiculous," replied McCormick, twisting his cap viciously. No one spoke. We were waiting for McCormick to go on. "The first fire," he began, repeating his story for my benefit, although Craig listened quite as attentively as if he had not heard it already, "was at the big store of Jones, Green leaders have been arrested, but I can't say we have anything against any of them. Still, Max Bloom, the manager of this company, insists that the fire was set for revenge, and indeed it looks as much like a fire for revenge as the Jones-Green fire does"--here he lowered his voice confidentially--"for the purpose of collecting insurance. "Then came the fire in the Slawson Building, a new loft-building that had been erected just off Fourth Avenue. Other than the fact that the Stacey interests put up the money for financing this building there seemed to be no reason for that fire at all. The building was reputed to be earning a good return on the investment, and I was at a loss to account for the fire. I have made no arrests for it--just set it down as the work of a pure pyromaniac, a man who burns buildings for fun, a man with an inordinate desire to hear the fire-engines screech through the streets and perhaps get a chance to show a little heroism in 'rescuing' tenants. However, the adjuster for the insurance company, Lazard, and the adjuster for the insured, Hartstein, have reached an agreement, and I believe the insurance is to be paid." "But," interposed Kennedy, "I see no evidence of organised arson so far." "Wait," replied the fire marshal. "That was only the beginning, you understand. A little later came a fire that looked quite like an attempt to mask a robbery by burning the building afterward. That was in a silk-house near Spring Street. But after a controversy the adjusters have reached an agreement on that case. I mention these fires because they show practically all the types of work of the various kinds of firebug--insurance, revenge, robbery, and plain insanity. But since the Spring Street fire, the character of the fires has been more uniform. They have all been in business places, or nearly all." Here the fire marshal launched forth into a catalogue of fires of suspected incendiary origin, at least eight in all. I took them down hastily, intending to use the list some time in a box head with an article in the Star. When he had finished his list I hastily counted up the number of killed. There were six, two of them firemen, and four employees. The money loss ranged into the millions. McCormick passed his hand over his forehead to brush off the perspiration. "I guess this thing has got on my nerves," he muttered hoarsely. "Everywhere I go they talk about nothing else. If I drop into the restaurant for lunch, my waiter talks of it. If I meet a newspaper man, he talks of it. My barber talks of it--everybody. Sometimes I dream of it; other times I lie awake thinking about it. I tell you, gentlemen, I've sweated blood over this problem." "But," insisted Kennedy, "I still can't see why you link all these fires as due to one firebug. I admit there is an epidemic of fires. But what makes you so positive that it is all the work of one man?" "I was coming to that. For one thing, he isn't like the usual firebug at all. Ordinarily they start their fires with excelsior and petroleum, or they smear the wood with paraffin or they use gasoline, benzine, or something of that sort. This fellow apparently scorns such crude methods. I can't say how he starts his fires, but in every case I have mentioned we have found the remains of a wire. It has something to do with electricity--but what, I don't know. That's one reason why I think these fires are all connected. Here's another." McCormick pulled a dirty note out of his pocket and laid it on the table. We read it eagerly: Hello, Chief! Haven't found the firebug yet, have you? You will know who he is only when I am dead and the fires stop. I don't suppose you even realise that the firebug talks with you almost every day about catching the firebug. That's me. I am the real firebug, that is writing this letter. I am going to tell you why I am starting these fires. There's money in it--an easy living. They never caught me in Chicago or anywhere, so you might as well quit looking for me and take your medicine. A. SPARK. "Humph!" ejaculated Kennedy, "he has a sense of humour, anyhow--A. Spark!" "Queer sense of humour," growled McCormick, gritting his teeth. "Here's another I got to-day: Say, Chief: We are going to get busy again and fire a big department-store next. How does that suit Your Majesty? Wait till the fun begins when the firebug gets to work again. A. SPARK. "Well, sir, when I got that letter," cried McCormick, "I was almost ready to ring in a double-nine alarm at once--they have me that bluffed out. But I said to myself, 'There's only one thing to do--see this man Kennedy.' So here I am. You see what I am driving at? I believe that firebug is an artist at the thing, does it for the mere fun of it and the ready money in it. But more than that, there must be some one back of him. Who is the man higher up--we must catch him. See?" "A big department-store," mused Kennedy. "That's definite--there are only a score or so of them, and the Stacey interests control several. Mac, I'll tell you what I'll do. Let me sit up with you to-night at headquarters until we get an alarm. By George, I'll see this case through to a finish!" The fire marshal leaped to his feet and bounded over to where Kennedy was seated. With one hand on Craig's shoulder and the other grasping Craig's hand, he started to speak, but his voice choked. "Thanks," he blurted out huskily at last. "My reputation in the department is at stake, my promotion, my position itself, my--my family--er--er--" "Not a word, sir," said Kennedy, his features working sympathetically. "To-night at eight I will go on watch with you. By the way, leave me those A. Spark notes." McCormick had so far regained his composure as to say a hearty farewell. He left the room as if ten years had been lifted off his shoulders. A moment later he stuck his head in the door again. "I'll have one of the Department machines call for you, gentlemen," he said. After the marshal had gone, we sat for several minutes in silence. Kennedy was reading and rereading the notes, scowling to himself as if they presented a particularly perplexing problem. I said nothing, though my mind was teeming with speculations. At length he placed the notes very decisively on the table and snapped out the remark, "Yes, it must be so." "What?" I queried, still drumming away at my typewriter, copying the list of incendiary fires against the moment when the case should be complete and the story "released for publication," as it were. "This note," he explained, picking up the first one and speaking slowly, "was written by a woman." I swung around in my chair quickly. "Get out!" I exclaimed sceptically. "No woman ever used such phrases." "I didn't say composed by a woman--I said written by a woman," he replied. "Oh," I said, rather chagrined. "It is possible to determine sex from handwriting in perhaps eighty cases out of a hundred," Kennedy went on, enjoying my discomfiture. "Once I examined several hundred specimens of writing to decide that point to my satisfaction. Just to test my conclusions I submitted the specimens to two professional graphologists. I found that our results were slightly different, but I averaged the thing up to four cases out of five correct. The so-called sex signs are found to be largely influenced by the amount of writing done, by age, and to a certain extent by practice and professional requirements, as in the conventional writing of teachers and the rapid hand of bookkeepers. Now in this case the person who wrote the first note was only an indifferent writer. Therefore the sex signs are pretty likely to be accurate. Yes, I'm ready to go on the stand and swear that this note was written by a woman and the second by a man." "Then there's a woman in the case, and she wrote the first note for the firebug--is that what you mean?" I asked. "Exactly. There nearly always is a woman in the case, somehow or other. This woman is closely connected with the firebug. As for the firebug, whoever it may be, he performs his crimes with cold premeditation and, as De Quincey said, in a spirit of pure artistry. The lust of fire propels him, and he uses his art to secure wealth. The man may be a tool in the hands of others, however. It's unsafe to generalise on the meagre facts we now have. Oh, well, there is nothing we can do just yet. Let's take a walk, get an early dinner, and be back here before the automobile arrives." Not a word more did Kennedy say about the case during our stroll or even on the way downtown to fire headquarters. We found McCormick anxiously waiting for us. High up in the sandstone tower at headquarters, we sat with him in the maze of delicate machinery with which the fire game is played in New York. In great glass cases were glistening brass and nickel machines with discs and levers and bells, tickers, sheets of paper, and annunciators without number. This was the fire-alarm telegraph, the "roulettewheel of the fire demon," as some one has aptly called it. "All the alarms for fire from all the boroughs, both from the regular alarm-boxes and the auxiliary systems, come here first over the network of three thousand miles or more of wire nerves that stretch out through the city," McCormick was explaining to us. A buzzer hissed. "Here's an alarm now," he exclaimed, all attention. "Three," "six," "seven," the numbers appeared on the annunciator. The clerks in the office moved as if they were part of the mechanism. Twice the alarm was repeated, being sent out all over the city. McCormick relapsed from his air of attention. "That alarm was not in the shopping district," he explained, much relieved. "Now the fire-houses in the particular district where that fire is have received the alarm instantly. Four engines, two hook-and-ladders, a water-tower, the battalion chief, and a deputy are hurrying to that fire. Hello, here comes another." Again the buzzer sounded. "One," "four," "five" showed in the annunciator. Even before the clerks could respond, McCormick had dragged us to the door. In another instant we were wildly speeding uptown, the bell on the front of the automobile clanging like a fire-engine, the siren horn going continuously, the engine of the machine throbbing with energy until the water boiled in the radiator. "Let her out, Frank," called McCormick to his chauffeur, as we rounded into a broad and now almost deserted thoroughfare. Like a red streak in the night we flew up that avenue, turned into Fourteenth Street on two wheels, and at last were on Sixth Avenue. With a jerk and a skid we stopped. There were the engines, the hose-carts, the hook-and-ladders, the salvage corps, the police establishing fire lines--everything. But where was the fire? The crowd indicated where it ought to be--it was Stacey's. Firemen and policemen were entering the huge building. McCormick shouldered in after them, and we followed. "Who turned in the alarm?" he asked as we mounted the stairs with the others. "I did," replied a night watchman on the third landing. "Saw a light in the office on the third floor back--something blazing. But it seems to be out now." We had at last come to the office. It was dark and deserted, yet with the lanterns we could see the floor of the largest room littered with torn books and ledgers. Kennedy caught his foot in something. It was a loose wire on the floor. He followed it. It led to an electric-light socket, where it was attached. "Can't you turn on the lights?" shouted McCormick to the watchman. "Not here. They're turned on from downstairs, and they're off for the night. I'll go down if you want me to and--" "No," roared Kennedy. "Stay where you are until I follow the wire to the other end." At last we came to a little office partitioned off from the main room. Kennedy carefully opened the door. One whiff of the air from it was sufficient. He banged the door shut again. "Stand back with those lanterns, boys," he ordered. I sniffed, expecting to smell illuminating-gas. Instead, a peculiar, sweetish odour pervaded the air. For a moment it made me think of a hospital operating-room. "Ether," exclaimed Kennedy. "Stand back farther with those lights and hold them up from the floor." For a moment he seemed to hesitate as if at loss what to do next. Should he open the door and let this highly inflammable gas out or should he wait patiently until the natural ventilation of the little office had dispelled it? While he was debating he happened to glance out of the window and catch sight of a drug-store across the street. "Walter," he said to me, "hurry across there and get all the saltpeter and sulphur the man has in the shop." I lost no time in doing so. Kennedy dumped the two chemicals into a pan in the middle of the main office, about three-fifths saltpeter and two-fifths sulphur, I should say. Then he lighted it. The mass burned with a bright flame but without explosion. We could smell the suffocating fumes from it, and we retreated. For a moment or two we watched it curiously at a distance. "That's very good extinguishing-powder," explained Craig as we sniffed at the odour. "It yields a large amount of carbon dioxide and sulphur dioxide. Now--before it gets any worse--I guess it's safe to open the door and let the ether out. You see this is as good a way as any to render safe a room full of inflammable vapour. Come, we'll wait outside the main office for a few minutes until the gases mix." It seemed hours before Kennedy deemed it safe to enter the office again with a light. When we did so, we made a rush for the little cubby-hole of an office at the other end. On the floor was a little can of ether, evaporated of course, and beside it a small apparatus apparently used for producing electric sparks. "So, that's how he does it," mused Kennedy, fingering the can contemplatively. "He lets the ether evaporate in a room for a while and then causes an explosion from a safe distance with this little electric spark. There's where your wire comes in, McCormick. Say, my man, you can switch on the lights from downstairs, now." As we waited for the watchman to turn on the lights I exclaimed, "He failed this time because the electricity was shut off." "Precisely, Walter," assented Kennedy. "But the flames which the night watchman saw, what of them?" put in McCormick, considerably mystified. "He must have seen something." Just then the lights winked up. "Oh, that was before the fellow tried to touch off the ether vapour," explained Kennedy. "He had to make sure of his work of destruction first--and, judging by the charred papers about, he did it well. See, he tore leaves from the ledgers and lighted them on the floor. There was an object in all that. What was it? Hello! Look at this mass of charred paper in the corner." He bent down and examined it carefully. "Memoranda of some kind, I guess. I'll save this burnt paper and look it over later. Don't disturb it. I'll take it away myself." Search as we might, we could find no other trace of the firebug, and at last we left. Kennedy carried the charred paper carefully in a large hat-box. "There'll be no more fires to-night, McCormick," he said. "But I'll watch with you every night until we get this incendiary. Meanwhile I'll see what I can decipher, if anything, in this burnt paper." Next day McCormick dropped in to see us again. This time he had another note, a disguised scrawl which read: Chief: I'm not through. Watch me get another store yet. I won't fall down this time. A. SPARK. Craig scowled as he read the note and handed it to me. "The man's writing this time--like the second note," was all he said. "McCormick, since we know where the lightning is going to strike, don't you think it would be wiser to make our headquarters in one of the engine-houses in that district?" The fire marshal agreed, and that night saw us watching at the fire-house nearest the department-store region. Kennedy and I were assigned to places on the hose-cart and engine, respectively, Kennedy being in the hose-cart so that he could be with McCormick. We were taught to descend one of the four brass poles hand under elbow, from the dormitory on the second floor. They showed us how to jump into the "turn-outs"--a pair of trousers opened out over the high top boots. We were given helmets which we placed in regulation fashion on our rubber coats, turned inside out with the right armhole up. Thus it came about that Craig and I joined the Fire Department temporarily. It was a novel experience for us both. "Now, Walter," said Kennedy, "as long as we have gone so far, we'll 'roll' to every fire, just like the regulars. We won't take any chances of missing the firebug at any time of night or day." It proved to be a remarkably quiet evening with only one little blaze in a candy-shop on Seventh Avenue. Most of the time we sat around trying to draw the men out about their thrilling experiences at fires. But if there is one thing the fireman doesn't know it is the English language when talking about himself. It was quite late when we turned into the neat white cots upstairs. We had scarcely fallen into a half doze in our strange surroundings when the gong downstairs sounded. It was our signal. We could hear the rapid clatter of the horses' hoofs as they were automatically released from their stalls and the collars and harness mechanically locked about them. All was stir, and motion, and shouts. Craig and I had bounded awkwardly into our paraphernalia at the first sound. We slid ungracefully down the pole and were pushed and shoved into our places, for scientific management in a New York fire-house has reached one hundred per cent. efficiency, and we were not to be allowed to delay the game. The oil-torch had been applied to the engine, and it rolled forth, belching flames. I was hanging on for dear life, now and then catching sight of the driver urging his plunging horses onward like a charioteer in a modern Ben Hur race. The tender with Craig and McCormick was lost in the clouds of smoke and sparks that trailed behind us. On we dashed until we turned into Sixth Avenue. The glare of the sky told us that this time the firebug had made good. "I'll be hanged if it isn't the Stacey store again," shouted the man next me on the engine as the horses lunged up the avenue and stopped at the allotted hydrant. It was like a war game. Every move had been planned out by the fire-strategists, even down to the hydrants that the engines should take at a given fire. Already several floors were aflame, the windows glowing like open-hearth furnaces, the glass bulging and cracking and the flames licking upward and shooting out in long streamers. The hose was coupled up in an instant, the water turned on, and the limp rubber and canvas became as rigid as a post with the high pressure of the water being forced through it. Company after company dashed into the blazing "fireproof" building, urged by the hoarse profanity of the chief. Twenty or thirty men must have disappeared into the stifle from which the police retreated. There was no haste, no hesitation. Everything moved as smoothly as if by clockwork. Yet we could not see one of the men who had disappeared into the burning building. They had been swallowed up, as it were. For that is the way with the New York firemen. They go straight to the heart of the fire. Now and then a stream of a hose spat out of a window, showing that the men were still alive and working. About the ground floors the red-helmeted salvage corps were busy covering up what they could of the goods with rubber sheets to protect them from water. Doctors with black bags and white trousers were working over the injured. Kennedy and I were busy about the engine, and there was plenty for us to do. Above the shrill whistle for more coal I heard a voice shout, "Began with an explosion--it's the firebug, all right." I looked up. It was McCormick, dripping and grimy, in a high state of excitement, talking to Kennedy. I had been so busy trying to make myself believe that I was really of some assistance about the engine that I had not taken time to watch the fire itself. It was now under control. The sharp and scientific attack had nipped what might have been one of New York's historic conflagrations. "Are you game to go inside?" I heard McCormick ask. For answer Kennedy simply nodded. As for me, where Craig went I went. The three of us drove through the scorching door, past twisted masses of iron still glowing dull red in the smoke and steam, while the water hissed and spattered and slopped. The smoke was still suffocating, and every once in a while we were forced to find air close to the floor and near the wall. My hands and arms and legs felt like lead, yet on we drove. Coughing and choking, we followed McCormick to what had been the heart of the fire, the office. Men with picks and axes and all manner of cunningly devised instruments were hacking and tearing at the walls and woodwork, putting out the last smouldering sparks while a thousand gallons of water were pouring in at various parts of the building where the fire still showed spirit. There on the floor of the office lay a charred, shapeless, unrecognisable mass. What was that gruesome odour in the room? Burned human flesh? I recoiled from what had once been the form of a woman. McCormick uttered a cry, and as I turned my eyes away, I saw him holding a wire with the insulation burned off. He had picked it up from the wreckage of the floor. It led to a bent and blackened can--that had once been a can of ether. My mind worked rapidly, but McCormick blurted out the words before I could form them, "Caught in her own trap at last!" Kennedy said nothing, but as one of the firemen roughly but reverently covered the remains with a rubber sheet, he stooped down and withdrew from the breast of the woman a long letter-file. "Come, let us go," he said. Back in our apartment again we bathed our racking heads, gargled our parched throats, and washed out our bloodshot eyes, in silence. The whole adventure, though still fresh and vivid in my mind, seemed unreal, like a dream. The choking air, the hissing steam, the ghastly object under the tarpaulin--what did it all mean? Who was she? I strove to reason it out, but could find no answer. It was nearly dawn when the door opened and McCormick came in and dropped wearily into a chair. "Do you know who that woman was?" he gasped. "It was Miss Wend herself." "Who identified her?" asked Kennedy calmly. "Oh, several people. Stacey recognised her at once. Then Hartstein, the adjuster for the insured, and Lazard, the adjuster for the company, both of whom had had more or less to do with her in connection with settling up for other fires, recognised her. She was a very clever woman, was Miss Wend, and a very important cog in the Stacey enterprises. And to think she was the firebug, after all. I can hardly believe it." "Why believe it?" asked Kennedy quietly. "Why believe it?" echoed McCormick. "Stacey has found shortages in his books due to the operation of her departments. The bookkeeper who had charge of the accounts in her department, a man named Douglas, is missing. She must have tried to cover up her operations by fires and juggling the accounts. Failing in that she tried to destroy Stacey's store itself, twice. She was one of the few that could get into the office unobserved. Oh, it's a clear case now. To my mind, the heavy vapours of ether--they are heavier than air, you know--must have escaped along the surface of the floor last night and become ignited at a considerable distance from where she expected. She was caught in a back-draught, or something of the sort. Well, thank God, we've seen the last of this firebug business. What's that?" Kennedy had laid the letter-file on the table. "Nothing. Only I found this embedded in Miss Wend's breast right over her heart." "Then she was murdered?" exclaimed McCormick. "We haven't come to the end of this case yet," replied Craig evasively. "On the contrary, we have just got our first good clue. No, McCormick, your theory will not hold water. The real point is to find this missing bookkeeper at any cost. You must persuade him to confess what he knows. Offer him immunity--he was only a pawn in the hands of those higher up." McCormick was not hard to convince. Tired as he was, he grabbed up his hat and started off to put the final machinery in motion to wind up the long chase for the firebug. "I must get a couple of hours' sleep," he yawned as he left us, "but first I want to start something toward finding Douglas. I shall try to see you about noon." I was too exhausted to go to the office. In fact, I doubt if I could have written a line. But I telephoned in a story of personal experiences at the Stacey fire and told them they could fix it up as they chose and even sign my name to it. About noon McCormick came in again, looking as fresh as if nothing had happened. He was used to it. "I know where Douglas is," he announced breathlessly. "Fine," said Kennedy, "and can you produce him at any time when it is necessary?" "Let me tell you what I have done. I went down to the district attorney from here--routed him out of bed. He has promised to turn loose his accountants to audit the reports of the adjusters, Hartstein and Lazard, as well as to make a cursory examination of what Stacey books there are left. He says he will have a preliminary report ready to-night, but the detailed report will take days, of course. "It's the Douglas problem that is difficult, though. I haven't seen him, but one of the central-office men, by shadowing his wife, has found that he is in hiding down on the East Side. He's safe there; he can't make a move to get away without being arrested. The trouble is that if I arrest him, the people higher up will know it and will escape before I can get his confession and the warrants. I'd much rather have the whole thing done at once. Isn't there some way we can get the whole Stacey crowd together, make the arrest of Douglas and nab the guilty ones in the case, all together without giving them a chance to escape or to shield the real firebug?" Kennedy thought a moment. "Yes," he answered slowly. "There is. If you can get them all together at my laboratory to-night at, say, eight o'clock, I'll give you two clear hours to make the arrest of Douglas, get the confession, and swear out the warrants. All that you'll need to do is to let me talk a few minutes this afternoon with the judge who will sit in the night court to-night. I shall install a little machine on his desk in the court, and we'll catch the real criminal--he'll never get a chance to cross the state line or disappear in any way. You see, my laboratory will be neutral ground. I think you can get them to come, inasmuch as they know the bookkeeper is safe and that dead women tell no tales." When next I saw Kennedy it was late in the afternoon, in the laboratory. He was arranging something in the top drawer of a flat-top desk. It seemed to be two instruments composed of many levers and discs and magnets, each instrument with a roll of paper about five inches wide. On one was a sort of stylus with two silk cords attached at right angles to each other near the point. On the other was a capillary glass tube at the junction of two aluminum arms, also at right angles to each other. It was quite like old times to see Kennedy at work in his laboratory preparing for a "seance." He said nothing as I watched him curiously, and I asked nothing. Two sets of wires were attached to each of the instruments, and these he carefully concealed and led out the window. Then he arranged the chairs on the opposite side of the desk from his own. "Walter," he said, "when our guests begin to arrive I want you to be master of ceremonies. Simply keep them on the opposite side of the desk from me. Don't let them move their chairs around to the right or left. And, above all, leave the doors open. I don't want any one to be suspicious or to feel that he is shut in in any way. Create the impression that they are free to go and come when they please." Stacey arrived first in a limousine which he left standing at the door of the Chemistry Building. Bloom and Warren came together in the latter's car. Lazard came in a taxicab which he dismissed, and Hartstein came up by the subway, being the last to arrive. Every one seemed to be in good humour. I seated them as Kennedy had directed. Kennedy pulled out the extension on the left of his desk and leaned his elbow on it as he began to apologise for taking up their time at such a critical moment. As near as I could make out, he had quietly pulled out the top drawer of his desk on the right, the drawer in which I had seen him place the complicated apparatus. But as nothing further happened I almost forgot about it in listening to him. He began by referring to the burned papers he had found in the office. "It is sometimes possible," he continued, "to decipher writing on burned papers if one is careful. The processes of colour photography have recently been applied to obtain a legible photograph of the writing on burned manuscripts which are unreadable by any other known means. As long as the sheet has not been entirely disintegrated positive results can be obtained every time. The charred manuscript is carefully arranged in as near its original shape as possible, on a sheet of glass and covered with a drying varnish, after which it is backed by another sheet of glass. "By using carefully selected colour screens and orthochromatic plates a perfectly legible photograph of the writing may be taken, although there may be no marks on the charred remains that are visible to the eye. This is the only known method in many cases. I have here some burned fragments of paper which I gathered up after the first attempt to fire your store, Mr. Stacey." Stacey coughed in acknowledgment. As for Craig, he did not mince matters in telling what he had found. "Some were notes given in favour of Rebecca Wend and signed by Joseph Stacey," he said quietly. "They represent a large sum of money in the aggregate. Others were memoranda of Miss Wend's, and still others were autograph letters to Miss Wend of a very incriminating nature in connection with the fires by another person." Here he laid the "A. Spark" letters on the desk before him. "Now," he added "some one, in a spirit of bravado, sent these notes to the fire marshal at various times. Curiously enough, I find that the handwriting of the first one bears a peculiar resemblance to that of Miss Wend, while the second and third, though disguised also, greatly suggest the handwriting of Miss Wend's correspondent." No one moved. But I sat aghast. She had been a part of the conspiracy, after all, not a pawn. Had they played fair? "Taking up next the remarkable succession of fires," resumed Kennedy, "this case presents some unique features. In short, it is a clear case of what is known as a 'firebug trust.' Now just what is a firebug trust? Well, it is, as near as I can make out, a combination of dishonest merchants and insurance adjusters engaged in the business of deliberately setting fires for profit. These arson trusts are not the ordinary kind of firebugs whom the firemen plentifully damn in the fixed belief that one-fourth of all fires are kindled by incendiaries. Such 'trusts' exist all over the country. They have operated in Chicago, where they are said to have made seven hundred and fifty thousand dollars in one year. Another group is said to have its headquarters in Kansas City. Others have worked in St. Louis, Pittsburgh, Cleveland, and Buffalo. The fire marshals of Illinois, Kentucky, Tennessee, and Ohio have investigated their work. But until recently New York has been singularly free from the organised work of this sort. Of course we have plenty of firebugs and pyromaniacs in a small way, but the big conspiracy has never come to my personal attention before. "Now, the Jones-Green fire, the Quadrangle fire, the Slawson Building fire, and the rest, have all been set for one purpose--to collect insurance. I may as well say right here that some people are in bad in this case, but that others are in worse. Miss Wend was originally a party to the scheme. Only the trouble with Miss Wend was that she was too shrewd to be fooled. She insisted that she have her full share of the pickings. In that case it seems to have been the whole field against Miss Wend, not a very gallant thing, nor yet according to the adage about honour among thieves. "A certain person whose name I am frank to say I do not know--yet--conceived the idea of destroying the obligations of the Stacey companies to Miss Wend as well as the incriminating evidence which she held of the 'firebug trust,' of which she was a member up to this time. The plan only partly succeeded. The chief coup, which was to destroy the Stacey store into the bargain, miscarried. "What was the result? Miss Wend, who had been hand in glove with the 'trust,' was now a bitter enemy, perhaps would turn state's evidence. What more natural than to complete the conspiracy by carrying out the coup and at the same time get rid of the dangerous enemy of the conspirators? I believe that Miss Wend was lured under some pretext or other to the Stacey store on the night of the big fire. The person who wrote the second and third 'A. Spark' letters did it. She was murdered with this deadly instrument"--Craig laid the letter-file on the table--"and it was planned to throw the entire burden of suspicion on her by asserting that there was a shortage in the books of her department." "Pooh!" exclaimed Stacey, smoking complacently at his cigar. "We have been victimised in those fires by people who have grudges against us, labour unions and others. This talk of an arson trust is bosh--yellow journalism. More than that, we have been systematically robbed by a trusted head of a department, and the fire at Stacey's was the way the thief took to cover--er--her stealings. At the proper time we shall produce the bookkeeper Douglas and prove it." Kennedy fumbled in the drawer of the desk, then drew forth a long strip of paper covered with figures. "All the Stacey companies," he said, "have been suffering from the depression that exists in the trade at present. They are insolvent. Glance over that, Stacey. It is a summary of the preliminary report of the accountants of the district attorney who have been going over your books to-day." Stacey gasped. "How did you get it? The report was not to be ready until nine o'clock, and it is scarcely a quarter past now." "Never mind how I got it. Go over it with the adjusters, anybody. I think you will find that there was no shortage in Miss Wend's department, that you were losing money, that you were in debt to Miss Wend, and that she would have received the lion's share of the proceeds of the insurance if the firebug scheme had turned out as planned." "We absolutely repudiate these figures as fiction," said Stacey, angrily turning toward Kennedy after a hurried consultation. "Perhaps, then, you'll appreciate this," replied Craig, pulling another piece of paper from the desk. "I'll read it. 'Henry Douglas, being duly sworn, deposes and says that one'--we'll call him 'Blank' for the present--'with force and arms did feloniously, wilfully, and intentionally kill Rebecca Wend whilst said Blank was wilfully burning and setting on fire--'" "One moment," interrupted Stacey. "Let me see that paper." Kennedy laid it down so that only the signature showed. The name was signed in a full round hand, "Henry Douglas." "It's a forgery," cried Stacey in rage. "Not an hour before I came into this place I saw Henry Douglas. He had signed no such paper then. He could not have signed it since, and you could not have received it. I brand that document as a forgery." Kennedy stood up and reached down into the open drawer on the right of his desk. From it he lifted the two machines I had seen him place there early in the evening. "Gentlemen," he said, "this is the last scene of the play you are enacting. You see here on the desk an instrument that was invented many years ago, but has only recently become really practical. It is the telautograph--the long-distance writer. In this new form it can be introduced into the drawer of a desk for the use of any one who may wish to make inquiries, say, of clerks without the knowledge of a caller. It makes it possible to write a message under these conditions and receive an answer concerning the personality or business of the individual seated at one's elbow without leaving the desk or seeming to make inquiries. "With an ordinary pencil I have written on the paper of the transmitter. The silk cord attached to the pencil regulates the current which controls a pencil at the other end of the line. The receiving pencil moves simultaneously with my pencil. It is the principle of the pantagraph cut in half, one half here, the other half at the end of the line, two telephone wires in this case connecting the halves. "While we have been sitting here I have had my right hand in the half-open drawer of my desk writing with this pencil notes of what has transpired in this room. These notes, with other evidence, have been simultaneously placed before Magistrate Brenner in the night court. At the same time, on this other, the receiving, instrument the figures of the accountants written in court have been reproduced here. You have seen them. Meanwhile, Douglas was arrested, taken before the magistrate, and the information for a charge of murder in the first degree perpetrated in committing arson has been obtained. You have seen it. It came in while you were reading the figures." The conspirators seemed dazed. "And now," continued Kennedy, "I see that the pencil of the receiving instrument is writing again. Let us see what it is." We bent over. The writing started: "County of New York. In the name of the People of the State of New York--" Kennedy did not wait for us to finish reading. He tore the writing from the telautograph and waved it over his head. "It is a warrant. You are all under arrest for arson. But you, Samuel Lazard, are also under arrest for the murder of Rebecca Wend and six other persons in fires which you have set. You are the real firebug, the tool of Joseph Stacey, perhaps, but that will all come out in the trial. McCormick, McCormick," called Craig, "it's all right. I have the warrant. Are the police there?" There was no answer. Lazard and Stacey made a sudden dash for the door, and in an instant they were in Stacey's waiting car. The chauffeur took off the brake and pulled the lever. Suddenly Craig's pistol flashed, and the chauffeur's arms hung limp and useless on the steering-wheel. As McCormick with the police loomed up, a moment late, out of the darkness and after a short struggle clapped the irons on Stacey and Lazard in Stacey's own magnificently upholstered car, I remarked reproachfully to Kennedy: "But, Craig, you have shot the innocent chauffeur. Aren't you going to attend to him?" "Oh," replied Kennedy nonchalantly, "don't worry about that. They were only rock-salt bullets. They didn't penetrate far. They'll sting for some time, but they're antiseptic, and they'll dissolve and absorb quickly." V THE CONFIDENCE KING "Shake hands with Mr. Burke of the secret service, Professor Kennedy." It was our old friend First Deputy O'Connor who thus in his bluff way introduced a well-groomed and prosperous-looking man whom he brought up to our apartment one evening. The formalities were quickly over. "Mr. Burke and I are old friends," explained O'Connor. "We try to work together when we can, and very often the city department can give the government service a lift, and then again it's the other way--as it was in the trunk-murder mystery. Show Professor Kennedy the 'queer,' Tom." Burke drew a wallet out of his pocket, and from it slowly and deliberately selected a crisp, yellow-backed hundred-dollar bill. He laid it flat on the table before us. Diagonally across its face from the upper left-to the lower right-hand corner extended two parallel scorings in indelible ink. Not being initiated into the secrets of the gentle art of "shoving the queer," otherwise known as passing counterfeit money, I suppose my questioning look betrayed me. "A counterfeit, Walter," explained Kennedy. "That's what they do with bills when they wish to preserve them as records in the secret service and yet render them valueless." Without a word Burke handed Kennedy a pocket magnifying-glass, and Kennedy carefully studied the bill. He was about to say something when Burke opened his capacious wallet again and laid down a Bank of England five-pound note which had been similarly treated. Again Kennedy looked through the glass with growing amazement written on his face, but before he could say anything, Burke laid down an express money-order on the International Express Company. "I say," exclaimed Kennedy, putting down the glass, "stop! How many more of these are there?" Burke smiled. "That's all," he replied, "but it's not the worst." "Not the worst? Good heavens, man, next you'll tell me that the government is counterfeiting its own notes! How much of this stuff do you suppose has been put into circulation?" Burke chewed a pencil thoughtfully, jotted down some figures on a piece of paper, and thought some more. "Of course I can't say exactly, but from hints I have received here and there I should think that a safe bet would be that some one has cashed in upward of half a million dollars already." "Whew," whistled Kennedy, "that's going some. And I suppose it is all salted away in some portable form. What an inventory it must be--good bills, gold, diamonds, and jewellery. This is a stake worth playing for." "Yes," broke in O'Connor, "but from my standpoint, professionally, I mean, the case is even worse than that. It's not the counterfeits that bother us. We understand that, all right. But," and he leaned forward earnestly and brought his fist down hard on the table with a resounding Irish oath, "the finger-print system, the infallible finger-print system, has gone to pieces. We've just imported this new 'portrait parle' fresh from Paris and London, invented by Bertillon and all that sort of thing--it has gone to pieces, too. It's a fine case, this is, with nothing left of either scientific or unscientific criminal-catching to rely on. There--what do you know about that?" "You'll have to tell me the facts first," said Kennedy. "I can't diagnose your disease until I know the symptoms." "It's like this," explained Burke, the detective in him showing now with no effort at concealment. "A man, an Englishman, apparently, went into a downtown banker's office about three months ago and asked to have some English bank-notes exchanged for American money. After he had gone away, the cashier began to get suspicious. He thought there was something phoney in the feel of the notes. Under the glass he noticed that the little curl on the 'e' of the 'Five' was missing. It's the protective mark. The water-mark was quite equal to that of the genuine--maybe better. Hold that note up to the light and see for yourself. "Well, the next day, down to the Custom House, where my office is, a man came who runs a swell gambling-house uptown. He laid ten brand-new bills on my desk. An Englishman had been betting on the wheel. He didn't seem to care about winning, and he cashed in each time with a new one-hundred-dollar bill. Of course he didn't care about winning. He cared about the change--that was his winning. The bill on the table is one of the original ten, though since then scores have been put into circulation. I made up my mind that it was the same Englishman in both cases. "Then within a week, in walked the manager of the Mozambique Hotel--he had been stung with the fake International Express money-order--same Englishman, too, I believe." "And you have no trace of him?" asked Kennedy eagerly. "We had him under arrest once--we thought. A general alarm was sent out, of course, to all the banks and banking-houses. But the man was too clever to turn up in that way again. In one gambling-joint which women frequent a good deal, a classy dame who might have been a duchess or a--well, she was a pretty good loser and always paid with hundred-dollar bills. Now, you know women are NOT good losers. Besides, the hundred-dollar-bill story had got around among the gambling-houses. This joint thought it worth taking a chance, so they called me up on the 'phone, extracted a promise that I'd play fair and keep O'Connor from raiding them, but wouldn't I please come up and look over the dame of the yellow bills? Of course I made a jump at it. Sure enough, they were the same counterfeits. I could tell because the silk threads were drawn in with coloured ink. But instead of making an arrest I decided to trail the lady. "Now, here comes the strange part of it. Let me see, this must have been over two months ago. I followed her out to a suburban town, Riverwood along the Hudson, and to a swell country house overlooking the river, private drive, stone gate, hedges, old trees, and all that sort of thing. A sporty-looking Englishman met her at the gate with one of those big imported touring-cars, and they took a spin. "I waited a day or so, but nothing more happened, and I began to get anxious. Perhaps I was a bit hasty. Anyhow I watched my chance and made an arrest of both of them when they came to New York on a shopping expedition. You should have heard that Englishman swear. I didn't know such language was possible. But in his pocket we found twenty more of those hundred-dollar bills--that was all. Do you think he owned up? Not a bit of it. He swore he had picked the notes up in a pocketbook on the pier as he left the steamer. I laughed. But when he was arraigned in court he told the magistrate the same story and that he had advertised his find at the time. Sure enough, in the files of the papers we discovered in the lost-and-found column the ad., just as he claimed. We couldn't even prove that he had passed the bills. So the magistrate refused to hold them, and they were both released. But we had had them in our power long enough to take their finger-prints and get descriptions and measurements of them, particularly by this new 'portrait parle' system. We felt we could send out a strange detective and have him pick them out of a crowd--you know the system, I presume?" Kennedy nodded, and I made a mental note of finding out more about the "portrait parle" later. Burke paused, and O'Connor prompted, "Tell them about Scotland Yard, Tom." "Oh, yes," resumed Burke. "Of course I sent copies of the finger-prints to Scotland Yard. Within two weeks they replied that one set belonged to William Forbes, a noted counterfeiter, who, they understood, had sailed for South Africa but had never arrived there. They were glad to learn that he was in America, and advised me to look after him sharply. The woman was also a noted character--Harriet Wollstone, an adventuress." "I suppose you have shadowed them ever since?" Kennedy asked. "Yes, a few days after they were arrested the man had an accident with his car. It was said he was cranking the engine and that it kicked back and splintered the bone in his forearm. Anyhow, he went about with his hand and arm in a sling." "And then?" "They gave my man the slip that night in their fast touring-car. You know automobiles have about made shadowing impossible in these days. The house was closed up, and it was said by the neighbours that Williams and Mrs. Williams--as they called themselves--had gone to visit a specialist in Philadelphia. Still, as they had a year's lease on the house, I detailed a man to watch it more or less all the time. They went to Philadelphia all right; some of the bills turned up there. But we saw nothing of them. "A short time ago, word came to me that the house was open again. It wasn't two hours later that the telephone rang like mad. A Fifth Avenue jeweller had just sold a rope of pearls to an Englishwoman who paid for it herself in crisp new one-hundred-dollar bills. The bank had returned them to him that very afternoon--counterfeits. I didn't lose any time making a second arrest up at the house of mystery at Riverwood. I had the county authorities hold them--and, now, O'Connor, tell the rest of it. You took the finger-prints up there." O'Connor cleared his throat as if something stuck in it, in the telling. "The Riverwood authorities refused to hold them," he said with evident chagrin. "As soon as I heard of the arrest I started up myself with the finger-print records to help Burke. It was the same man, all right--I'll swear to that on a stack of Bibles. So will Burke. I'll never forget that snub nose--the concave nose, the nose being the first point of identification in the 'portrait parle.' And the ears, too--oh, it was the same man, all right. But when we produced the London finger-prints which tallied with the New York fingerprints which we had made--believe it or not, but it is a fact, the Riverwood finger-prints did not tally at all." He laid the prints on the table. Kennedy examined them closely. His face clouded. It was quite evident that he was stumped, and he said so. "There are some points of agreement," he remarked, "but more points of difference. Any points of difference are usually considered fatal to the finger-print theory." "We had to let the man go," concluded Burke. "We could have held the woman, but we let her go, too, because she was not the principal in the case. My men are shadowing the house now and have been ever since then. But the next day after the last arrest, a man from New York, who looked like a doctor, made a visit. The secret-service man on the job didn't dare leave the house to follow him, but as he never came again perhaps it doesn't matter. Since then the house has been closed." The telephone rang. It was Burke's office calling him. As he talked we could gather that something tragic must have happened at Riverwood, and we could hardly wait until he had finished. "There has been an accident up there," he remarked as he hung up the receiver rather petulantly. "They returned in the car this afternoon with a large package in the back of the tonneau. But they didn't stay long. After dark they started out again in the car. The accident was at the bad railroad crossing just above Riverwood. It SEEMS Williams's car got stalled on the track just as the Buffalo express was due. No one saw it, but a man in a buggy around the bend in the road heard a woman scream. He hurried down. The train had smashed the car to bits. How the woman escaped was a miracle, but they found the man's body up the tracks, horribly mangled. It was Williams, they say. They identified him by the clothes and by letters in his pockets. But my man tells me he found a watch on him with 'W. F.' engraved on it. His hands and arms and head must have been right under the locomotive when it struck him, I judge." "I guess that winds the case up, eh?" exclaimed O'Connor with evident chagrin. "Where's the woman?" "They said she was in the little local hospital, but not much hurt. Just the shock and a few bruises." O'Connor's question seemed to suggest an idea to Burke, and he reached for the telephone again. "Riverwood 297," he ordered; then to us as he waited he said: "We must hold the woman. Hello, 297? The hospital? This is Burke of the secret service. Will you tell my man, who must be somewhere about, that I would like to have him hold that woman who was in the auto smash until I can--what? Gone? The deuce!" He hung up the receiver angrily. "She left with a man who called for her about half an hour ago," he said. "There must be a gang of them. Forbes is dead, but we must get the rest. Mr. Kennedy, I'm sorry to have bothered you, but I guess we can handle this alone, after all. It was the finger-prints that fooled us, but now that Forbes is out of the way it's just a straight case of detective work of the old style which won't interest you." "On the contrary," answered Kennedy, "I'm just beginning to be interested. Does it occur to you that, after all, Forbes may not be dead?" "Not dead?" echoed Burke and O'Connor together. "Exactly; that's just what I said--not dead. Now stop and think a moment. Would the great Forbes be so foolish as to go about with a watch marked 'W. F.' if he knew, as he must have known, that you would communicate with London and by means of the prints find out all about him?" "Yes," agreed Burke, "all we have to go by is his watch found on Williams. I suppose there is some possibility that Forbes may still be alive." "Who is this third man who comes in and with whom Harriet Wollstone goes away so willingly?" put in O'Connor. "You said the house had been closed--absolutely closed?" Burke nodded. "Been closed ever since the last arrest. There's a servant who goes in now and then, but the car hasn't been there before to-night, wherever it has been." "I should like to watch that house myself for a while," mused Kennedy. "I suppose you have no objections to my doing so?" "Of course not. Go ahead," said Burke. "I will go along with you if you wish, or my man can go with you." "No," said Kennedy, "too many of us might spoil the broth. I'll watch alone to-night and will see you in the morning. You needn't even say anything to your man there about us." "Walter, what's on for to-night?" he asked when they had gone. "How are you fixed for a little trip out to Riverwood?" "To tell the truth, I had an engagement at the College Club with some of the fellows." "Oh, cut it." "That's what I intend to do," I replied. It was a raw night, and we bundled ourselves up in old football sweaters under our overcoats. Half an hour later we were on our way up to Riverwood. "By the way, Craig," I asked, "I didn't like to say anything before those fellows. They'd think I was a dub. But I don't mind asking you. What is this 'portrait parle' they talk about, anyway?" "Why, it's a word-picture--a 'spoken picture,' to be literal. I took some lessons in it at Bertillon's school when I was in Paris. It's a method of scientific apprehension of criminals, a sort of necessary addition and completion to the methods of scientific identification of them after they are arrested. For instance, in trying to pick out a given criminal from his mere description you begin with the nose. Now, noses are all concave, straight, or convex. This Forbes had a nose that was concave, Burke says. Suppose you were sent out to find him. Of all the people you met, we'll say, roughly, two-thirds wouldn't interest you. You'd pass up all with straight or convex noses. Now the next point to observe is the ear. There are four general kinds of ears-triangular, square, oval, and round, besides a number of other differences which are clear enough after you study ears. This fellow is a pale man with square ears and a peculiar lobe to his ear. So you wouldn't give a second glance to, say, three-fourths of the square-eared people. So by a process of elimination of various features, the eyes, the mouth, the hair, wrinkles, and so forth, you would be able to pick your man out of a thousand--that is, if you were trained." "And it works?" I asked rather doubtfully. "Oh, yes. That's why I'm taking up this case. I believe science can really be used to detect crime, any crime, and in the present instance I've just pride enough to stick to this thing until--until they begin to cut ice on the Styx. Whew, but it will be cold out in the country to-night, Walter--speaking about ice." It was quite late when we reached Riverwood, and Kennedy hurried along the dimly lighted streets, avoiding the main street lest some one might be watching or following us. He pushed on, following the directions Burke had given him. The house in question was a large, newly built affair of concrete, surrounded by trees and a hedge, directly overlooking the river. A bitter wind swept in from the west, but in the shadow of an evergreen tree and of the hedge Kennedy established our watch. Of all fruitless errands this seemed to me to be the acme. The house was deserted; that was apparent, I thought, and I said so. Hardly had I said it when I heard the baying of a dog. It did not come from the house, however, and I concluded that it must have come from the next estate. "It's in the garage," whispered Kennedy. "I can hardly think they would go away and leave a dog locked up in it. They would at least turn him loose." Hour after hour we waited. Midnight passed, and still nothing happened. At last when the moon had disappeared under the clouds, Kennedy pulled me along. We had seen not a sign of life in the house, yet he observed all the caution he would have if it had been well guarded. Quickly we advanced over the open space to the house, approaching in the shadow as much as possible, on the side farthest from the river. Tiptoeing over the porch, Kennedy tried a window. It was fastened. Without hesitation he pulled out some instruments. One of them was a rubber suction-cup, which he fastened to the window-pane. Then with a very fine diamond-cutter he proceeded to cut out a large section. It soon fell and was prevented from smashing on the floor by the string and the suction-cup. Kennedy put his hand in and unlatched the window, and we stepped in. All was silent. Apparently the house was deserted. Cautiously Kennedy pressed the button of his pocket storage-battery lamp and flashed it slowly about the room. It was a sort of library, handsomely furnished. At last the beam of light rested on a huge desk at the opposite end. It seemed to interest Kennedy, and we tiptoed over to it. One after another he opened the drawers. One was locked, and he saved that until the last. Quietly as he could, he jimmied it open, muffling the jimmy in a felt cloth that was on a table. Most people do not realise the disruptive force that there is in a simple jimmy. I didn't until I saw the solid drawer with its heavy lock yield with just the trace of a noise. Kennedy waited an instant and listened. Nothing happened. Inside the drawer was a most nondescript collection of useless articles. There were a number of pieces of fine sponge, some of them very thin and cut in a flat oval shape, smelling of lysol strongly; several bottles, a set of sharp little knives, some paraffin, bandages, antiseptic gauze, cotton--in fact, it looked like a first-aid kit. As soon as he saw it Kennedy seemed astonished but not at a loss to account for it. "I thought he left that sort of thing to the doctors, but I guess he took a hand in it himself," he muttered, continuing to fumble with the knives in the drawer. It was no time to ask questions, and I did not. Kennedy rapidly stowed away the things in his pockets. One bottle he opened and held to his nose. I could distinguish immediately the volatile smell of ether. He closed it quickly, and it, too, went into his pocket with the remark, "Somebody must have known how to administer an anaesthetic--probably the Wollstone woman." A suppressed exclamation from Kennedy caused me to look. The drawer had a false back. Safely tucked away in it reposed a tin box, one of those so-called strong-boxes which are so handy in that they save a burglar much time and trouble in hunting all over for the valuables he has come after. Kennedy drew it forth and laid it on the desk. It was locked. Even that did not seem to satisfy Kennedy, who continued to scrutinise the walls and corners of the room as if looking for a safe or something of that sort. "Let's look in the room across the hall," he whispered. Suddenly a piercing scream of a woman rang out upstairs. "Help! Help! There's some one in the house! Billy, help!" I felt an arm grasp me tightly, and for a moment a chill ran over me at being caught in the nefarious work of breaking and entering a dwelling-house at night. But it was only Kennedy, who had already tucked the precious little tin box under his arm. With a leap he dragged me to the open window, cleared it, vaulted over the porch, and we were running for the clump of woods that adjoined the estate on one side. Lights flashed in all the windows of the house at once. There must have been some sort of electric-light system that could be lighted instantly as a "burglar-expeller." Anyhow, we had made good our escape. As we lost ourselves in the woods I gave a last glance back and saw a lantern carried from the house to the garage. As the door was unlocked I could see, in the moonlight, a huge dog leap out and lick the hands and face of a man. Quickly we now crashed through the frozen underbrush. Evidently Kennedy was making for the station by a direct route across country instead of the circuitous way by the road and town. Behind us we could hear a deep baying. "By the Lord, Walter," cried Kennedy, for once in his life thoroughly alarmed, "it's a bloodhound, and our trail is fresh." Closer it came. Press forward as we might, we could never expect to beat that dog. "Oh, for a stream," groaned Kennedy, "but they are all frozen--even the river." He stopped short, fumbled in his pocket, and drew out the bottle of ether. "Raise your foot, Walter," he ordered. I did so and he smeared first mine and then his with the ether. Then we doubled on our trail once or twice and ran again. "The dog will never be able to pick up the ether as our trail," panted Kennedy; "that is, if he is any good and trained not to go off on wild-goose chases." On we hurried from the woods to the now dark and silent town. It was indeed fortunate that the dog had been thrown off our scent, for the station was closed, and, indeed, if it had been open I am sure the station agent would have felt more like locking the door against two such tramps as we were, carrying a tin box and pursued by a dog, than opening it for us. The best we could do was to huddle into a corner until we succeeded in jumping a milk-train that luckily slowed down as it passed Riverwood station. Neither of us could wait to open the tin box in our apartment, and instead of going uptown Kennedy decided it would be best to go to a hotel near the station. Somehow we succeeded in getting a room without exciting suspicion. Hardly had the bellboy's footsteps ceased echoing in the corridor than Kennedy was at work wrenching off the lid of the box with such leverage as the scanty furnishings of the room afforded. At last it yielded, and we looked in curiously, expecting to find fabulous wealth in some form. A few hundred dollars and a rope of pearls lay in it. It was a good "haul," but where was the vast spoil the counterfeiters had accumulated? We had missed it. So far we were completely baffled. "Perhaps we had better snatch a couple of hours' sleep," was all that Craig said, stifling his chagrin. Over and over in my mind I was turning the problem of where they had hidden the spoil. I dozed off, still thinking about it and thinking that, even should they be captured, they might have stowed away perhaps a million dollars to which they could go back after their sentences were served. It was still early for New York when Kennedy roused me by talking over the telephone in the room. In fact, I doubt if he had slept at all. Burke was at the other end of the wire. His man had just reported that something had happened during the night at Riverwood, but he couldn't give a very clear account. Craig seemed to enjoy the joke immensely as he told his story to Burke. The last words I heard were: "All right. Send a man up here to the station--one who knows all the descriptions of these people. I'm sure they will have to come into town to-day, and they will have to come by train, for their car is wrecked. Better watch at the uptown stations, also." After a hasty breakfast we met Burke's man and took our places at the exit from the train platforms. Evidently Kennedy had figured out that the counterfeiters would have to come into town for some reason or other. The incoming passengers were passing us in a steady stream, for a new station was then being built, and there was only a temporary structure with one large exit. "Here is where the 'portrait parle' ought to come in, if ever," commented Kennedy as he watched eagerly. And yet neither man nor woman passed us who fitted the description. Train after train emptied its human freight, yet the pale man with the concave nose and the peculiar ear, accompanied perhaps by a lady, did not pass us. At last the incoming stream began to dwindle down. It was long past the time when the counterfeiters should have arrived if they had started on any reasonable train. "Perhaps they have gone up to Montreal, instead," I ventured. Kennedy shook his head. "No," he answered. "I have an idea that I was mistaken about the money being kept at Riverwood. It would have been too risky. I thought it out on the way back this morning. They probably kept it in a safe deposit vault here. I had figured that they would come down and get it and leave New York after last night's events. We have failed--they have got by us. Neither the 'portrait parle' nor the ordinary photography nor any other system will suffice alone against the arch-criminal back of this, I'm afraid. Walter, I am sore and disgusted. What I should have done was to accept Burke's offer--surround the house with a posse if necessary, last night, and catch the counterfeiters by sheer force. I was too confident. I thought I could do it with finesse, and I have failed. I'd give anything to know what safe deposit vault they kept the fake money in." I said nothing as we strolled away, leaving Burke's man still to watch, hoping against hope. Kennedy walked disconsolately through the station, and I followed. In a secluded part of the waiting-room he sat down, his face drawn up in a scowl such as I had never seen. Plainly he was disgusted with himself--with only himself. This was no bungling of Burke or any one else. Again the counterfeiters had escaped from the hand of the law. As he moved his fingers restlessly in the pockets of his coat, he absently pulled out the little pieces of sponge and the ether bottle. He regarded them without much interest. "I know what they were for," he said, diving back into his pocket for the other things and bringing out the sharp little knives in their case. I said nothing, for Kennedy was in a deep study. At last he put the things back into his pocket. As he did so his hand encountered something which he drew forth with a puzzled air. It was the piece of paraffin. "Now, what do you suppose that was for?" he asked, half to himself. "I had forgotten that. What was the use of a piece of paraffin? Phew, smell the antiseptic worked into it." "I don't know," I replied, rather testily. "If you would tell me what the other things were for I might enlighten you, but--" "By George, Walter, what a chump I am!" cried Kennedy, leaping to his feet, all energy again. "Why did I forget that lump of paraffin? Why, of course--I think I can guess what they have been doing--of course. Why, man alive, he walked right past us, and we never knew it. Boy, boy," he shouted to a newsboy who passed, "what's the latest sporting edition you have?" Eagerly he almost tore a paper open and scanned the sporting pages. "Racing at Lexington begins to-morrow," he read. "Yes, I'll bet that's it. We don't have to know the safe deposit vault, after all. It would be too late, anyhow. Quick, let us look up the train to Lexington." As we hurried over to the information booth, I gasped, in a whirl: "Now, look here, Kennedy, what's all this lightning calculation? What possible connection is there between a lump of paraffin and one of the few places in the country where they still race horses?" "None," he replied, not stopping an instant. "None. The paraffin suggested to me the possible way in which our man managed to elude us under our very eyes. That set my mind at work again. Like a flash it occurred to me: Where would they be most likely to go next to work off some of the bills? The banks are on, the jewellery-houses are on, the gambling-joints are on. Why, to the racetracks, of course. That's it. Counterfeiters all use the bookmakers, only since racing has been killed in New York they have had to resort to other means here. If New York has suddenly become too hot, what more natural than to leave it? Here, let me see--there's a train that gets there early to-morrow, the best train, too. Say, is No. 144 made up yet?" he inquired at the desk. "No. 144 will be ready in fifteen minutes. Track 8." Kennedy thanked the man, turned abruptly, and started for the still closed gate at Track 8. "Beg pardon--why, hulloa--it's Burke," he exclaimed as we ran plump into a man staring vacantly about. It was not the gentleman farmer of the night before, nor yet the supposed college graduate. This man was a Western rancher; his broad-brimmed hat, long moustache, frock coat, and flowing tie proclaimed it. Yet there was something indefinably familiar about him, too. It was Burke in another disguise. "Pretty good work, Kennedy," nodded Burke, shifting his tobacco from one side of his jaws to the other. "Now, tell me how your man escaped you this morning, when you can recognise me instantly in this rig." "You haven't altered your features," explained Kennedy simply. "Our pale-faced, snub-nosed peculiar-eared friend has. What do you think of the possibility of his going to the Lexington track, now that he finds it too dangerous to remain in New York?" Burke looked at Kennedy rather sharply. "Say, do you add telepathy to your other accomplishments?" "No," laughed Craig, "but I'm glad to see that two of us working independently have arrived at the same conclusion. Come, let us saunter over to Track 8--I guess the train is made up." The gate was just opened, and the crowd filed through. No one who seemed to satisfy either Burke or Kennedy appeared. The train-announcer made his last call. Just then a taxicab pulled up at the street-end of the platform, not far from Track 8. A man jumped out and assisted a heavily veiled lady, paid the driver, picked up the grips, and turned toward us. We waited expectantly. As he turned I saw a dark-skinned, hook-nosed man, and I exclaimed disgustedly to Burke: "Well, if they are going to Lexington they can't make this train. Those are the last people who have a chance." Kennedy, however, continued to regard the couple steadily. The man saw that he was being watched and faced us defiantly, "Such impertinence!" Then to his wife, "Come, my dear, we'll just make it." "I'm afraid I'll have to trouble you to show us what's in that grip," said Kennedy, calmly laying his hand on the man's arm. "Well, now, did you ever hear of such blasted impudence? Get out of my way, sir, this instant, or I'll have you arrested." "Come, come, Kennedy," interrupted Burke. "Surely you are getting in wrong here. This can't be the man." Craig shook his head decidedly. "You can make the arrest or not, Burke, as you choose. If not, I am through. If so--I'll take all the responsibility." Reluctantly Burke yielded. The man protested; the woman cried; a crowd collected. The train-gate shut with a bang. As it did so the man's demeanour changed instantly. "There," he shouted angrily, "you have made us miss our train. I'll have you in jail for this. Come on now to the nearest magistrate's court. I'll have my rights as an American citizen. You have carried your little joke too far. Knight is my name--John Knight, of Omaha, pork-packer. Come on now. I'll see that somebody suffers for this if I have to stay in New York a year. It's an outrage--an outrage." Burke was now apparently alarmed--more at the possibility of the humorous publicity that would follow such a mistake by the secret service than at anything else. However, Kennedy did not weaken, and on general principles I stuck to Kennedy. "Now," said the man surlily while he placed "Mrs. Knight" in as easy a chair as he could find in the judge's chambers, "what is the occasion of all this row? Tell the judge what a bad man from Bloody Gulch I am." O'Connor had arrived, having broken all speed laws and perhaps some records on the way up from headquarters. Kennedy laid the Scotland Yard finger-prints on the table. Beside them he placed those taken by O'Connor and Burke in New York. "Here," he began, "we have the finger-prints of a man who was one of the most noted counterfeiters in Great Britain. Beside them are those of a man who succeeded in passing counterfeits of several kinds recently in New York. Some weeks later this third set of prints was taken from a man who was believed to be the same person." The magistrate was examining the three sets of prints. As he came to the third, he raised his head as if about to make a remark, when Kennedy quickly interrupted. "One moment, sir. You were about to say that finger-prints never change, never show such variations as these. That is true. There are fingerprints of people taken fifty years ago that are exactly the same as their finger-prints of to-day. They don't change--they are permanent. The fingerprints of mummies can be deciphered even after thousands of years. But," he added slowly, "you can change fingers." The idea was so startling that I could scarcely realise what he meant at first. I had read of the wonderful work of the surgeons of the Rockefeller Institute in transplanting tissues and even whole organs, in grafting skin and in keeping muscles artificially alive for days under proper conditions. Could it be that a man had deliberately amputated his fingers and grafted on new ones? Was the stake sufficient for such a game? Surely there must be some scars left after such grafting. I picked up the various sets of prints. It was true that the third set was not very clear, but there certainly were no scars there. "Though there is no natural changeability of finger-prints," pursued Kennedy, "such changes can be induced, as Dr. Paul Prager of Vienna has shown, by acids and other reagents, by grafting and by injuries. Now, is there any method by which lost finger-tips can be restored? I know of one case where the end of a finger was taken off and only one-sixteenth inch of the nail was left. The doctor incised the edges of the granulating surface and then led the granulations on by what is known in the medical profession as the 'sponge graft.' He grew a new finger-tip. "The sponge graft consists in using portions of a fine Turkish surgical sponge, such I have here. I found these pieces in a desk at Riverwood. The patient is anaesthetised. An incision is made from side to side in the stump of the finger and flaps of skin are sliced off and turned up for the new end of the finger to develop in--a sort of shell of living skin. Inside this, the sponge is placed, not a large piece, but a very thin piece sliced off and cut to the shape of the finger-stump. It is perfectly sterilised in water and washed in green soap after all the stony particles are removed by hydrochloric acid. Then the finger is bound up and kept moist with normal salt solution. "The result is that the end of the finger, instead of healing over, grows into the fine meshes of the pieces of sponge, by capillary attraction. Of course even this would heal in a few days, but the doctor does not let it heal. In three days he pulls the sponge off gently. The end of the finger has grown up just a fraction of an inch. Then a new thin layer of sponge is added. Day after day this process is repeated, each time the finger growing a little more. A new nail develops if any of the matrix is left, and I suppose a clever surgeon by grafting up pieces of epidermis could produce on such a stump very passable finger-prints." No one of us said anything, but Kennedy seemed to realise the thought in our minds and proceeded to elaborate the method. "It is known as the 'education sponge method,' and was first described by Dr. D. J. Hamilton, of Edinburgh, in 1881. It has frequently been used in America since then. The sponge really acts in a mechanical manner to support the new finger-tissue that is developed. The meshes are filled in by growing tissue, and as it grows the tissue absorbs part of the sponge, which is itself an animal tissue and acts like catgut. Part of it is also thrown off. In fact, the sponge imitates what happens naturally in the porous network of a regular blood-clot. It educates the tissue to grow, stimulates it--new blood-vessels and nerves as well as flesh. "In another case I know of, almost the whole of the first joint of a finger was crushed off, and the doctor was asked to amputate the stump of bone that protruded. Instead, he decided to educate the tissue to grow out to cover it and appear like a normal finger. In these cases the doctors succeeded admirably in giving the patients entire new finger-tips, without scars, and, except for the initial injury and operation, with comparatively little inconvenience except that absolute rest of the hands was required. "That is what happened, gentlemen," concluded Kennedy. "That is why Mr. Forbes, alias Williams, made a trip to Philadelphia to be treated--for crushed finger-tips, not for the kick of an automobile engine. He may have paid the doctors in counterfeits. In reality this man was playing a game in which there was indeed a heavy stake at issue. He was a counterfeiter sought by two governments with the net closing about him. What are the tips of a few fingers compared with life, liberty, wealth, and a beautiful woman? The first two sets of prints are different from the third because they are made by different finger-tips--on the same man. The very core of the prints was changed. But the finger-print system is vindicated by the very ingenuity of the man who so cleverly has contrived to beat it." "Very interesting--to one who is interested," remarked the stranger, "but what has that to do with detaining my wife and myself, making us miss our train, and insulting us?" "Just this," replied Craig. "If you will kindly oblige us by laying your fingers on this inking-pad and then lightly on this sheet of paper, I think I can show you an answer." Knight demurred, and his wife grew hysterical at the idea, but there was nothing, to do but comply. Kennedy glanced at the fourth set of prints, then at the third set taken a week ago, and smiled. No one said a word. Knight or Williams, which was it? He nonchalantly lit a cigarette. "So you say I am this Williams, the counterfeiter?" he asked superciliously. "I do," reiterated Kennedy. "You are also Forbes." "I don't suppose Scotland Yard has neglected to furnish you with photographs and a description of this Forbes?" Burke reluctantly pulled out a Bertillon card from his pocket and laid it on the table. It bore the front face and profile of the famous counterfeiter, as well as his measurements. The man picked it up as if indeed it was a curious thing. His coolness nearly convinced me. Surely he should have hesitated in actually demanding this last piece of evidence. I had heard, however, that the Bertillon system of measurements often depended on the personal equation of the measurer as well as on the measured. Was he relying on that, or on his difference in features? I looked over Kennedy's shoulder at the card on the table. There was the concave nose of the "portrait parle" of Forbes, as it had first been described to us. Without looking further I involuntarily glanced at the man, although I had no need to do so. I knew that his nose was the exact opposite of that of Forbes. "Ingenious at argument as you are," he remarked quietly, "you will hardly deny that Knight, of Omaha, is the exact opposite of Forbes, of London. My nose is almost Jewish--my complexion is dark as an Arab's. Still, I suppose I am the sallow, snub-nosed Forbes described here, inasmuch as I have stolen Forbes's fingers and lost them again by a most preposterous method." "The colour of the face is easily altered," said Kennedy. "A little picric acid will do that. The ingenious rogue Sarcey in Paris eluded the police very successfully until Dr. Charcot exposed him and showed how he changed the arch of his eyebrows and the wrinkles of his face. Much is possible to-day that would make Frankenstein and Dr. Moreau look clumsy and antiquated." A sharp feminine voice interrupted. It was the woman, who had kept silent up to this time. "But I have read in one of the papers this morning that a Mr. Williams was found dead in an automobile accident up the Hudson yesterday. I remember reading it, because I am afraid of accidents myself." All eyes were now fixed on Kennedy. "That body," he answered quickly, "was a body purchased by you at a medical school, brought in your car to Riverwood, dressed in Williams's clothes with a watch that would show he was Forbes, placed on the track in front of the auto, while you two watched the Buffalo express run it down, and screamed. It was a clever scheme that you concocted, but these facts do not agree." He laid the measurements of the corpse obtained by Burke and those from the London police card side by side. Only in the roughest way did they approximate each other. "Your honour, I appeal to your sense of justice," cried our prisoner impatiently. "Hasn't this farce been allowed to go far enough? Is there any reason why this fake detective should make fools out of us all and keep my wife longer in this court? I'm not disposed to let the matter drop. I wish to enter a charge against him of false arrest and malicious prosecution. I shall turn the whole thing over to my attorney this afternoon. The deuce with the races--I'll have justice." The man had by this time raised himself to a high pitch of apparently righteous wrath. He advanced menacingly toward Kennedy, who stood with his shoulders thrown back, and his hands deep in his pockets, and a half amused look on his face. "As for you, Mr. Detective," added the man, "for eleven cents I'd lick you to within an inch of your life. 'Portrait parle,' indeed! It's a fine scientific system that has to deny its own main principles in order to vindicate itself. Bah! Take that, you scoundrel!" Harriet Wollstone threw her arms about him, but he broke away. His fist shot out straight. Kennedy was too quick for him, however. I had seen Craig do it dozens of times with the best boxers in the "gym." He simply jerked his head to one side, and the blow passed just a fraction of an inch from his jaw, but passed it as cleanly as if it had been a yard away. The man lost his balance, and as he fell forward and caught himself, Kennedy calmly and deliberately slapped him on the nose. It was an intensely serious instant, yet I actually laughed. The man's nose was quite out of joint, even from such a slight blow. It was twisted over on his face in the most ludicrous position imaginable. "The next time you try that, Forbes," remarked Kennedy, as he pulled the piece of paraffin from his pocket and laid it on the table with the other exhibits, "don't forget that a concave nose built out to hook-nose convexity by injections of paraffin, such as the beauty-doctors everywhere advertise, is a poor thing for a White Hope." Both Burke and O'Connor had seized Forbes, but Kennedy had turned his attention to the larger of Forbes's grips, which the Wollstone woman vociferously claimed as her own. Quickly he wrenched it open. As he turned it up on the table my eyes fairly bulged at the sight. Forbes' suit-case might have been that of a travelling salesman for the Kimberley, the Klondike, and the Bureau of Engraving, all in one. Craig dumped the wealth out on the table--stacks of genuine bills, gold coins of two realms, diamonds, pearls, everything portable and tangible all heaped up and topped off with piles of counterfeits awaiting the magic touch of this Midas to turn them into real gold. "Forbes, you have failed in your get-away," said Craig triumphantly. "Gentlemen, you have here a master counterfeiter, surely--a master counterfeiter of features and fingers as well as of currency." VI THE SAND-HOG "Interesting story, this fight between the Five-Borough and the Inter-River Transit," I remarked to Kennedy as I sketched out the draft of an expose of high finance for the Sunday Star. "Then that will interest you, also," said he, throwing a letter down on my desk. He had just come in and was looking over his mail. The letterhead bore the name of the Five-Borough Company. It was from Jack Orton, one of our intimates at college, who was in charge of the construction of a new tunnel under the river. It was brief, as Jack's letters always were. "I have a case here at the tunnel that I am sure will appeal to you, my own case, too," it read. "You can go as far as you like with it, but get to the bottom of the thing, no matter whom it hits. There is some deviltry afoot, and apparently no one is safe. Don't say a word to anybody about it, but drop over to see me as soon as you possibly can." "Yes," I agreed, "that does interest me. When are you going over?" "Now," replied Kennedy, who had not taken off his hat. "Can you come along?" As we sped across the city in a taxicab, Craig remarked: "I wonder what is the trouble? Did you see in the society news this morning the announcement of Jack's engagement to Vivian Taylor, the daughter of the president of the Five-Borough?" I had seen it, but could not connect it with the trouble, whatever it was, at the tunnel, though I did try to connect the tunnel mystery with my expose. We pulled up at the construction works, and a strapping Irishman met us. "Is this Professor Kennedy?" he asked of Craig. "It is. Where is Mr. Orton's office?" "I'm afraid, sir, it will be a long time before Mr. Orton is in his office again, sir. The doctor have just took him out of the medical lock, an' he said if you was to come before they took him to the 'orspital I was to bring you right up to the lock." "Good heavens, man, what has happened?" exclaimed Kennedy. "Take us up to him quick." Without waiting to answer, the Irishman led the way up and across a rough board platform until at last we came to what looked like a huge steel cylinder, lying horizontally, in which was a floor with a cot and some strange paraphernalia. On the cot lay Jack Orton, drawn and contorted, so changed that even his own mother would scarcely have recognised him. A doctor was bending over him, massaging the joints of his legs and his side. "Thank you, Doctor, I feel a little better," he groaned. "No, I don't want to go back into the lock again, not unless the pain gets worse." His eyes were closed, but hearing us he opened them and nodded. "Yes, Craig," he murmured with difficulty, "this is Jack Orton. What do you think of me? I'm a pretty sight. How are you? And how are you, Walter? Not too vigorous with the hand-shakes, fellows. Sorry you couldn't get over before this happened." "What's the matter?" we asked, glancing blankly from Orton to the doctor. Orton forced a half smile. "Just a touch of the 'bends' from working in compressed air," he explained. We looked at him, but could say nothing. I, at least, was thinking of his engagement. "Yes," he added bitterly, "I know what you are thinking about, fellows. Look at me! Do you think such a wreck as I am now has any right to be engaged to the dearest girl in the world?" "Mr. Orton," interposed the doctor, "I think you'll feel better if you'll keep quiet. You can see your friends in the hospital to-night, but for a few hours I think you had better rest. Gentlemen, if you will be so good as to postpone your conversation with Mr. Orton until later it would be much better." "Then I'll see you to-night," said Orton to us feebly. Turning to a tall, spare, wiry chap, of just the build for tunnel work, where fat is fatal, he added: "This is Mr. Capps, my first assistant. He will show you the way down to the street again." "Confound it!" exclaimed Craig, after we had left Capps. "What do you think of this? Even before we can get to him something has happened. The plot thickens before we are well into it. I think I'll not take a cab, or a car either. How are you for a walk until we can see Orton again?" I could see that Craig was very much affected by the sudden accident that had happened to our friend, so I fell into his mood, and we walked block after block scarcely exchanging a word. His only remark, I recall, was, "Walter, I can't think it was an accident, coming so close after that letter." As for me, I scarcely knew what to think. At last our walk brought us around to the private hospital where Orton was. As we were about to enter, a very handsome girl was leaving. Evidently she had been visiting some one of whom she thought a great deal. Her long fur coat was flying carelessly, unfastened in the cold night air; her features were pale, and her eyes had the fixed look of one who saw nothing but grief. "It's terrible, Miss Taylor," I heard the man with her say soothingly, "and you must know that I sympathise with you a great deal." Looking up quickly, I caught sight of Capps and bowed. He returned our bows and handed her gently into an automobile that was waiting. "He might at least have introduced us," muttered Kennedy, as we went on into the hospital. Orton was lying in bed, white and worn, propped up by pillows which the nurse kept arranging and rearranging to ease his pain. The Irishman whom we had seen at the tunnel was standing deferentially near the foot of the bed. "Quite a number of visitors, nurse, for a new patient," said Orton, as he welcomed us. "First Capps and Paddy from the tunnel, then Vivian"--he was fingering some beautiful roses in a vase on a table near him--"and now, you fellows. I sent her home with Capps. She oughtn't to be out alone at this hour, and Capps is a good fellow. She's known him a long time. No, Paddy, put down your hat. I want you to stay. Paddy, by the way, fellows, is my right-hand man in managing the 'sandhogs' as we call the tunnel-workers. He has been a sand-hog on every tunnel job about the city since the first successful tunnel was completed. His real name is Flanagan, but we all know him best as Paddy." Paddy nodded. "If I ever get over this and back to the tunnel," Orton went on, "Paddy will stick to me, and we will show Taylor, my prospective father-in-law and the president of the railroad company from which I took this contract, that I am not to blame for all the troubles we are having on the tunnel. Heaven knows that--" "Oh, Mr. Orton, you ain't so bad," put in Paddy without the faintest touch of undue familiarity. "Look what I was when ye come to see me when I had the bends, sir." "You old rascal," returned Orton, brightening up. "Craig, do you know how I found him? Crawling over the floor to the sink to pour the doctor's medicine down." "Think I'd take that medicine," explained Paddy, hastily. "Not much. Don't I know that the only cure for the bends is bein' put back in the 'air' in the medical lock, same as they did with you, and bein' brought out slowly? That's the cure, that, an' grit, an' patience, an' time. Mark me wurds, gintlemen, he'll finish that tunnel an' beggin' yer pardon, Mr. Orton, marry that gurl, too. Didn't I see her with tears in her eyes right in this room when he wasn't lookin', and a smile when he was? Sure, ye'll be all right," continued Paddy, slapping his side and thigh. "We all get the bends more or less--all us sand-hogs. I was that doubled up meself that I felt like a big jack-knife. Had it in the arm, the side, and the leg all at once, that time he was just speakin' of. He'll be all right in a couple more weeks, sure, an' down in the air again, too, with the rest of his men. It's somethin' else he has on his moind." "Then the case has nothing to do with your trouble, nothing to do with the bends?" asked Kennedy, keenly showing his anxiety to help our old friend. "Well, it may and it may not," replied Orton thoughtfully. "I begin to think it has. We have had a great many cases of the bends among the men, and lots of the poor fellows have died, too. You know, of course, how the newspapers are roasting us. We are being called inhuman; they are going to investigate us; perhaps indict me. Oh, it's an awful mess; and now some one is trying to make Taylor believe it is my fault. "Of course," he continued, "we are working under a high air-pressure just now, some days as high as forty pounds. You see, we have struck the very worst part of the job, a stretch of quicksand in the river-bed, and if we can get through this we'll strike pebbles and rock pretty soon, and then we'll be all right again." He paused. Paddy quietly put in: "Beggin' yer pardon again, Mr. Orton, but we had intirely too many cases of the bends even when we were wurkin' at low pressure, in the rock, before we sthruck this sand. There's somethin' wrong, sir, or ye wouldn't be here yerself like this. The bends don't sthrike the ingineers, them as don't do the hard work, sir, and is careful, as ye know--not often." "It's this way, Craig," resumed Orton. "When I took this contract for the Five-Borough Transit Company, they agreed to pay me liberally for it, with a big bonus if I finished ahead of time, and a big penalty if I exceeded the time. You may or may not know it, but there is some doubt about the validity of their franchise after a certain date, provided the tunnel is not ready for operation. Well, to make a long story short, you know there are rival companies that would like to see the work fail and the franchise revert to the city, or at least get tied up in the courts. I took it with the understanding that it was every man for himself and the devil take the hindmost." "Have you yourself seen any evidences of rival influences hindering the work?" asked Kennedy. Orton carefully weighed his reply. "To begin with," he answered at length, "while I was pushing the construction end, the Five-Borough was working with the state legislature to get a bill extending the time-limit of the franchise another year. Of course, if it had gone through it would have been fine for us. But some unseen influence blocked the company at every turn. It was subtle; it never came into the open. They played on public opinion as only demagogues of high finance can, very plausibly of course, but from the most selfish and ulterior motives. The bill was defeated." I nodded. I knew all about that part of it, for it was in the article which I had been writing for the Star. "But I had not counted on the extra year, anyhow," continued Orton, "so I wasn't disappointed. My plans were laid for the shorter time from the start. I built an island in the river so that we could work from each shore to it, as well as from the island to each shore, really from four points at once. And then, when everything was going ahead fine, and we were actually doubling the speed in this way, these confounded accidents"--he was leaning excitedly forward--"and lawsuits and delays and deaths began to happen." Orton sank back as a paroxysm of the bends seized him, following his excitement. "I should like very much to go down into the tunnel," said Kennedy simply. "No sooner said than done," replied Orton, almost cheerfully, at seeing Kennedy so interested. "We can arrange that easily. Paddy will be glad to do the honours of the place in my absence." "Indade I will do that same, sor," responded the faithful Paddy, "an' it's a shmall return for all ye've done for me." "Very well, then," agreed Kennedy. "Tomorrow morning we shall be on hand. Jack, depend on us. We will do our level best to get you out of this scrape." "I knew you would, Craig," he replied. "I've read of some of your and Walter's exploits. You're a pair of bricks, you are. Good-bye, fellows," and his hands mechanically sought the vase of flowers which reminded him of their giver. At home we sat for a long time in silence. "By George, Craig," I exclaimed at length, my mind reverting through the whirl of events to the glimpse of pain I had caught on the delicate face of the girl leaving the hospital, "Vivian Taylor is a beauty, though, isn't she?" "And Capps thinks so, too," he returned, sinking again into his shell of silence. Then he suddenly rose and put on his hat and coat. I could see the old restless fever for work which came into his eyes whenever he had a case which interested him more than usual. I knew there would be no rest for Kennedy until he had finished it. Moreover, I knew it was useless for me to remonstrate with him, so I kept silent. "Don't wait up for me," he said. "I don't know when I'll be back. I'm going to the laboratory and the university library. Be ready early in the morning to help me delve into this tunnel mystery." I awoke to find Kennedy dozing in a chair, partly dressed, but just as fresh as I was after my sleep. I think he had been dreaming out his course of action. At any rate, breakfast was a mere incident in his scheme, and we were over at the tunnel works when the night shift were going off. Kennedy carried with him a moderate-sized box of the contents of which he seemed very careful. Paddy was waiting for us, and after a hasty whispered conversation, Craig stowed the box away behind the switchboard of the telephone central, after attaching it to the various wires. Paddy stood guard while this was going on so that no one would know about it, not even the telephone girl, whom he sent off on an errand. Our first inspection was of that part of the works which was above ground. Paddy, who conducted us, introduced us first to the engineer in charge of this part of the work, a man named Shelton, who had knocked about the world a great deal, but had acquired a taciturnity that was Sphinx-like. If it had not been for Paddy, I fear we should have seen very little, for Shelton was not only secretive, but his explanations were such that even the editor of a technical journal would have had to blue pencil them considerably. However, we gained a pretty good idea of the tunnel works above ground--at least Kennedy did. He seemed very much interested in how the air was conveyed below ground, the tank for storing compressed air for emergencies, and other features. It quite won Paddy, although Shelton seemed to resent his interest even more than he despised my ignorance. Next Paddy conducted us to the dressing-rooms. There we put on old clothes and oilskins, and the tunnel doctor examined us and extracted a written statement that we went down at our own risk and released the company from all liability--much to the disgust of Paddy. "We're ready now, Mr. Capps," called Paddy, opening an office door on the way out. "Very well, Flanagan," answered Capps, barely nodding to us. We heard him telephone some one, but could not catch the message, and in a minute he joined us. By this time I had formed the opinion, which I have since found to be correct, that tunnel men are not as a rule loquacious. It was a new kind of thrill to me to go under the "air," as the men called it. With an instinctive last look at the skyline of New York and the waves playing in the glad sunlight, we entered a rude construction elevator and dropped from the surface to the bottom of a deep shaft. It was like going down into a mine. There was the air-lock, studded with bolts, and looking just like a huge boiler, turned horizontally. The heavy iron door swung shut with a bang as Paddy and Capps, followed by Kennedy and myself, crept into the air-lock. Paddy turned on a valve, and compressed air from the tunnel began to rush in with a hiss as of escaping steam. Pound after pound to the square inch the pressure slowly rose until I felt sure the drums of my ears would burst. Then the hissing noise began to dwindle down to a wheeze, and then it stopped all of a sudden. That meant that the air-pressure in the lock was the same as that in the tunnel. Paddy pushed open the door in the other end of the lock from that by which we had entered. Along the bottom of the completed tube we followed Paddy and Capps. On we trudged, fanned by the moist breath of the tunnel. Every few feet an incandescent light gleamed in the misty darkness. After perhaps a hundred paces we had to duck down under a semicircular partition covering the upper half of the tube. "What is that?" I shouted at Paddy, the nasal ring of my own voice startling me. "Emergency curtain," he shouted back. Words were economised. Later, I learned that should the tunnel start to flood, the other half of the emergency curtain could be dropped so as to cut off the inrushing water. Men passed, pushing little cars full of "muck" or sand taken out from before the "shield"--which is the head by which this mechanical mole advances under the river-bed. These men and others who do the shovelling are the "muckers." Pipes laid along the side of the tunnel conducted compressed air and fresh water, while electric light and telephone wires were strung all about. These and the tools and other things strewn along the tunnel obstructed the narrow passage to such an extent that we had to be careful in picking our way. At last we reached the shield, and on hands and knees we crawled out into one of its compartments. Here we experienced for the first time the weird realisation that only the "air" stood between us and destruction from the tons and tons of sand and water overhead. At some points in the sand we could feel the air escaping, which appeared at the surface of the river overhead in bubbles, indicating to those passing in the river boats just how far each tunnel heading below had proceeded. When the loss of air became too great, I learned, scows would dump hundreds of tons of clay overhead to make an artificial river bed for the shield to stick its nose safely through, for if the river bed became too thin overhead the "air" would blow a hole in it. Capps, it seemed to me, was unusually anxious to have the visit over. At any rate, while Kennedy and Paddy were still crawling about the shield, he stood aside, now and then giving the men an order and apparently forgetful of us. My own curiosity was quickly satisfied, and I sat down on a pile of the segments out of which the successive rings of the tunnel were made. As I sat there waiting for Kennedy, I absently reached into my pocket and pulled out a cigarette and lighted it. It burned amazingly fast, as if it were made of tinder, the reason being the excess of oxygen in the compressed air. I was looking at it in astonishment, when suddenly I felt a blow on my hand. It was Capps. "You chump!" he shouted as he ground the cigarette under his boot. "Don't you know it is dangerous to smoke in compressed air?" "Why, no," I replied, smothering my anger at his manner. "No one said anything about it." "Well, it is dangerous, and Orton's a fool to let greenhorns come in here." "And to whom may it be dangerous?" I heard a voice inquire over my shoulder. It was Kennedy. "To Mr. Jameson or the rest of us?" "Well," answered Capps, "I supposed everybody knew it was reckless, and that he would hurt himself more by one smoke in the air than by a hundred up above. That's all." He turned on Kennedy sullenly, and started to walk back up the tunnel. But I could not help thinking that his manner was anything but solicitude for my own health. I could just barely catch his words over the tunnel telephone some feet away. I thought he said that everything was going along all right and that he was about to start back again. Then he disappeared in the mist of the tube without even nodding a farewell. Kennedy and I remained standing, not far from the outlet of the pipe by which the compressed air was being supplied in the tunnel from the compressors above, in order to keep the pressure up to the constant level necessary. I saw Kennedy give a hurried glance about, as if to note whether any one were looking at us. No one was. With a quick motion he reached down. In his hand was a stout little glass flask with a tight-fitting metal top. For a second he held it near the outlet of the pipe; then he snapped the top shut and slipped it back into his pocket as quickly as he had produced it. Slowly we commenced to retrace our steps to the air-lock, our curiosity satisfied by this glimpse of one of the most remarkable developments of modern engineering. "Where's Paddy?" asked Kennedy, stopping suddenly. "We've forgotten him." "Back there at the shield, I suppose," said I. "Let's whistle and attract his attention." I pursed up my lips, but if I had been whistling for a million dollars I couldn't have done it. Craig laughed. "Walter, you are indeed learning many strange things. You can't whistle in compressed air." I was too chagrined to answer. First it was Capps; now it was my own friend Kennedy chaffing me for my ignorance. I was glad to see Paddy's huge form looming in the semi-darkness. He had seen that we were gone and hurried after us. "Won't ye stay down an' see some more, gintlemen?" he asked. "Or have ye had enough of the air? It seems very smelly to me this mornin'--I don't blame ye. I guess them as doesn't have to stay here is satisfied with a few minutes of it." "No, thanks, I guess we needn't stay down any longer," replied Craig. "I think I have seen all that is necessary--at least for the present. Capps has gone out ahead of us. I think you can take us out now, Paddy. I would much rather have you do it than to go with anybody else." Coming out, I found, was really more dangerous than going in, for it is while coming out of the "air" that men are liable to get the bends. Roughly, half a minute should be consumed in coming out from each pound of pressure, though for such high pressures as we had been under, considerably more time was required in order to do it safely. We spent about half an hour in the air-lock, I should judge. Paddy let the air out of the lock by turning on a valve leading to the outside, normal atmosphere. Thus he let the air out rapidly at first until we had got down to half the pressure of the tunnel. The second half he did slowly, and it was indeed tedious, but it was safe. There was at first a hissing sound when he opened the valve, and it grew colder in the lock, since air absorbs heat from surrounding objects when it expands. We were glad to draw sweaters on over our heads. It also grew as misty as a London fog as the water-vapour in the air was condensed. At last the hiss of escaping air ceased. The door to the modern dungeon of science grated open. We walked out of the lock to the elevator shaft and were hoisted up to God's air again. We gazed out across the river with its waves dancing in the sunlight. There, out in the middle, was a wreath of bubbles on the water. That marked the end of the tunnel, over the shield. Down beneath those bubbles the sand-hogs were rooting. But what was the mystery that the tunnel held in its dark, dank bosom? Had Kennedy a clue? "I think we had better wait around a bit," remarked Kennedy, as we sipped our hot coffee in the dressing-room and warmed ourselves from the chill of coming out of the lock. "In case anything should happen to us and we should get the bends, this is the place for us, near the medical lock, as it is called--that big steel cylinder over there, where we found Orton. The best cure for the bends is to go back under the air--recompression they call it. The renewed pressure causes the gas in the blood to contract again, and thus it is eliminated--sometimes. At any rate, it is the best-known cure and considerably reduces the pain in the worst cases. When you have a bad case like Orton's it means that the damage is done; the gas has ruptured some veins. Paddy was right. Only time will cure that." Nothing happened to us, however, and in a couple of hours we dropped in on Orton at the hospital where he was slowly convalescing. "What do you think of the case?" he asked anxiously. "Nothing as yet," replied Craig, "but I have set certain things in motion which will give us a pretty good line on what is taking place in a day or so." Orton's face fell, but he said nothing. He bit his lip nervously and looked out of the sun-parlour at the roofs of New York around him. "What has happened since last night to increase your anxiety, Jack?" asked Craig sympathetically. Orton wheeled his chair about slowly, faced us, and drew a letter from his pocket. Laying it flat on the table he covered the lower part with the envelope. "Read that," he said. "Dear Jack," it began. I saw at once that it was from Miss Taylor. "Just a line," she wrote, "to let you know that I am thinking about you always and hoping that you are better than when I saw you this evening. Papa had the chairman of the board of directors of the Five-Borough here late to-night, and they were in the library for over an hour. For your sake, Jack, I played the eavesdropper, but they talked so low that I could hear nothing, though I know they were talking about you and the tunnel. When they came out, I had no time to escape, so I slipped behind a portiere. I heard father say: 'Yes, I guess you are right, Morris. The thing has gone on long enough. If there is one more big accident we shall have to compromise with the Inter-River and carry on the work jointly. We have given Orton his chance, and if they demand that this other fellow shall be put in, I suppose we shall have to concede it.' Mr. Morris seemed pleased that father agreed with him and said so. Oh, Jack, can't you DO something to show them they are wrong, and do it quickly? I never miss an opportunity of telling papa it is not your fault that all these delays take place." The rest of the letter was covered by the envelope, and Orton would not have shown it for worlds. "Orton," said Kennedy, after a few moments' reflection, "I will take a chance for your sake--a long chance, but I think a good one. If you can pull yourself together by this afternoon, be over at your office at four. Be sure to have Shelton and Capps there, and you can tell Mr. Taylor that you have something very important to set before him. Now, I must hurry if I am to fulfil my part of the contract. Good-bye, Jack. Keep a stiff upper lip, old man. I'll have something that will surprise you this afternoon." Outside, as he hurried uptown, Craig was silent, but I could see his features working nervously, and as we parted he merely said: "Of course, you'll be there, Walter. I'll put the finishing touches on your story of high finance." Slowly enough the few hours passed before I found myself again in Orton's office. He was there already, despite the orders of his physician, who was disgusted at this excursion from the hospital. Kennedy was there, too, grim and silent. We sat watching the two indicators beside Orton's desk, which showed the air pressure in the two tubes. The needles were vibrating ever so little and tracing a red-ink line on the ruled paper that unwound from the drum. From the moment the tunnels were started, here was preserved a faithful record of every slightest variation of air pressure. "Telephone down into the tube and have Capps come up," said Craig at length, glancing at Orton's desk clock. "Taylor will be here pretty soon, and I want Capps to be out of the tunnel by the time he comes. Then get Shelton, too." In response to Orton's summons Capps and Shelton came into the office, just as a large town car pulled up outside the tunnel works. A tall, distinguished-looking man stepped out and turned again toward the door of the car. "There's Taylor," I remarked, for I had seen him often at investigations before the Public Service Commission. "And Vivian, too," exclaimed Orton excitedly. "Say, fellows, clear off these desks. Quick, before she gets up here. In the closet with these blueprints, Walter. There, that's a little better. If I had known she was coming I would at least have had the place swept out. Puff! look at the dust on this desk of mine. Well, there's no help for it. There they are at the door now. Why, ivian, what a surprise." "Jack!" she exclaimed, almost ignoring the rest of us and quickly crossing to his chair to lay a restraining hand on his shoulder as he vainly tried to stand up to welcome her. "Why didn't you tell me you were coming?" he asked eagerly. "I would have had the place fixed up a bit." "I prefer it this way," she said, looking curiously around at the samples of tunnel paraphernalia and the charts and diagrams on the walls. "Yes, Orton," said President Taylor, "she would come--dropped in at the office and when I tried to excuse myself for a business appointment, demanded which way I was going. When I said I was coming here, she insisted on coming, too." Orton smiled. He knew that she had taken this simple and direct means of being there, but he said nothing, and merely introduced us to the president and Miss Taylor. An awkward silence followed. Orton cleared his throat. "I think you all know why we are here," he began. "We have been and are having altogether too many accidents in the tunnel, too many cases of the bends, too many deaths, too many delays to the work. Well--er--I--er--Mr. Kennedy has something to say about them, I believe." No sound was heard save the vibration of the air-compressors and an occasional shout of a workman at the shaft leading down to the air-locks. "There is no need for me to say anything about caisson disease to you, gentlemen, or to you, Miss Taylor," began Kennedy. "I think you all know how it is caused and a good deal about it already. But, to be perfectly clear, I will say that there are five things that must, above all others, be looked after in tunnel work: the air pressure, the amount of carbon dioxide in the air, the length of the shifts which the men work, the state of health of the men as near as physical examination can determine it, and the rapidity with which the men come out of the 'air,' so as to prevent carelessness which may cause the bends. "I find," he continued, "that the air pressure is not too high for safety. Proper examinations for carbon dioxide are made, and the amount in the air is not excessive. The shifts are not even as long as those prescribed by the law. The medical inspection is quite adequate and as for the time taken in coming out through the locks the rules are stringent." A look of relief crossed the face of Orton at this commendation of his work, followed by a puzzled expression that plainly indicated that he would like to know what was the matter, if all the crucial things were all right. "But," resumed Kennedy, "the bends are still hitting the men, and there is no telling when a fire or a blow-out may occur in any of the eight headings that are now being pushed under the river. Quite often the work has been delayed and the tunnel partly or wholly flooded. Now, you know the theory of the bends. It is that air--mostly the nitrogen in the air--is absorbed by the blood under the pressure. In coming out of the 'air' if the nitrogen is not all eliminated, it stays in the blood and, as the pressure is reduced, it expands. It is just as if you take a bottle of charged water and pull the cork suddenly. The gas rises in big bubbles. Cork it again and the gas bubbles cease to rise and finally disappear. If you make a pin-hole in the cork the gas will escape slowly, without a bubble. You must decompress the human body slowly, by stages, to let the super-saturated blood give up its nitrogen to the lungs, which can eliminate it. Otherwise these bubbles catch in the veins, and the result is severe pains, paralysis, and even death. Gentlemen, I see that I am just wasting time telling you this, for you know it all well. But consider." Kennedy placed an empty corked flask on the table. The others regarded it curiously, but I recalled having seen it in the tunnel. "In this bottle," explained Kennedy, "I collected some of the air from the tunnel when I was down there this morning. I have since analysed it. The quantity of carbon dioxide is approximately what it should be--not high enough of itself to cause trouble. But," he spoke slowly to emphasise his words, "I found something else in that air beside carbon dioxide." "Nitrogen?" broke in Orton quickly, leaning forward. "Of course; it is a constituent of air. But that is not what I mean." "Then, for Heaven's sake, what did you find?" asked Orton. "I found in this air," replied Kennedy, "a very peculiar mixture--an explosive mixture." "An explosive mixture?" echoed Orton. "Yes, Jack, the blow-outs that you have had at the end of the tunnel were not blow-outs at all, properly speaking. They were explosions." We sat aghast at this revelation. "And, furthermore," added Kennedy, "I should, if I were you, call back all the men from the tunnel until the cause for the presence of this explosive mixture is discovered and remedied." Orton reached mechanically for the telephone to give the order, but Taylor laid his hand on his arm. "One moment, Orton," he said. "Let's hear Professor Kennedy out. He may be mistaken, and there is no use frightening the men, until we are certain." "Shelton," asked Kennedy, "what sort of flash oil is used to lubricate the machinery?" "It is three-hundred-and-sixty-degree Fahrenheit flash test," he answered tersely. "And are the pipes leading air down into the tunnel perfectly straight?" "Straight?" "Yes, straight--no joints, no pockets where oil, moisture, and gases can collect." "Straight as lines, Kennedy," he said with a sort of contemptuous defiance. They were facing each other coldly, sizing each other up. Like a skilful lawyer, Kennedy dropped that point for a moment, to take up a new line of attack. "Capps," he demanded, turning suddenly, "why do you always call up on the telephone and let some one know when you are going down in the tunnel and when you are coming out?" "I don't," replied Capps, quickly recovering his composure. "Walter," said Craig to me quietly, "go out in the outer office. Behind the telephone switchboard you will find a small box which you saw me carry in there this morning and connect with the switchboard. Detach the wires, as you saw me attach them, and bring it here." No one moved, as I placed the box on a drafting-table before them. Craig opened it. Inside he disclosed a large disc of thin steel, like those used by some mechanical music-boxes, only without any perforations. He connected the wires from the box to a sort of megaphone. Then he started the disc revolving. Out of the little megaphone horn, sticking up like a miniature talking-machine, came a voice: "Number please. Four four three o, Yorkville. Busy, I'll call you. Try them again, Central. Hello, hello, Central--" Kennedy stopped the machine. "It must be further along on the disc," he remarked. "This, by the way, is an instrument known as the telegraphone, invented by a Dane named Poulsen. It records conversations over a telephone on this plain metal disc by means of localised, minute electric charges." Having adjusted the needle to another place on the disc he tried again. "We have here a record of the entire day's conversations over the telephone, preserved on this disc. I could wipe out the whole thing by pulling a magnet across it, but, needless to say, I wouldn't do that--yet. Listen." This time it was Capps speaking. "Give me Mr. Shelton. Oh, Shelton, I'm going down in the south tube with those men Orton has sent nosing around here. I'll let you know when I start up again. Meanwhile--you know--don't let anything happen while I am there. Good-bye." Capps sat looking defiantly at Kennedy, as he stopped the telegraphone. "Now," continued Kennedy suavely, "what COULD happen? I'll answer my own question by telling what actually did happen. Oil that was smoky at a lower point than its flash was being used in the machinery--not really three-hundred-and-sixty-degree oil. The water-jacket had been tampered with, too. More than that, there is a joint in the pipe leading down into the tunnel, where explosive gases can collect. It is a well-known fact in the use of compressed air that such a condition is the best possible way to secure an explosion. "It would all seem so natural, even if discovered," explained Kennedy rapidly. "The smoking oil--smoking just as an automobile often does--is passed into the compressed-air pipe. Condensed oil, moisture, and gases collect in the joint, and perhaps they line the whole distance of the pipe. A spark from the low-grade oil--and they are ignited. What takes place is the same thing that occurs in the cylinder of an automobile where the air is compressed with gasoline vapour. Only here we have compressed air charged with vapour of oil. The flame proceeds down the pipe--exploding through the pipe, if it happens to be not strong enough. This pipe, however, is strong. Therefore, the flame in this case shoots out at the open end of the pipe, down near the shield, and if the air in the tunnel happens also to be surcharged with oil-vapour, an explosion takes place in the tunnel--the river bottom is blown out--then God help the sand-hogs! "That's how your accidents took place, Orton," concluded Kennedy in triumph, "and that impure air--not impure from carbon dioxide, but from this oil-vapour mixture--increased the liability of the men for the bends. Capps knew about it. He was careful while he was there to see that the air was made as pure as possible under the circumstances. He was so careful that he wouldn't even let Mr. Jameson smoke in the tunnel. But as soon as he went to the surface, the same deadly mixture was pumped down again--I caught some of it in this flask, and--" "My God, Paddy's down there now," cried Orton, suddenly seizing his telephone. "Operator, give me the south tube--quick--what--they don't answer?" Out in the river above the end of the heading, where a short time before there had been only a few bubbles on the surface of the water, I could see what looked like a huge geyser of water spouting up. I pulled Craig over to me and pointed. "A blow-out," cried Kennedy, as he rushed to the door, only to be met by a group of blanched-faced workers who had come breathless to the office to deliver the news. Craig acted quickly. "Hold these men," he ordered, pointing to Capps and Shelton, "until we come back. Orton, while we are gone, go over the entire day's record on the telegraphone. I suspect you and Miss Taylor will find something there that will interest you." He sprang down the ladder to the tunnel air-lock, not waiting for the elevator. In front of the closed door of the lock, an excited group of men was gathered. One of them was peering through the dim, thick, glass porthole in the door. "There he is, standin' by the door with a club, an' the men's crowdin' so fast that they're all wedged so's none can get in at all. He's beatin' 'em back with the stick. Now, he's got the door clear and has dragged one poor fellow in. It's Jimmy Rourke, him with the eight childer. Now he's dragged in a Polack. Now he's fightin' back a big Jamaica nigger who's tryin' to shove ahead of a little Italian." "It's Paddy," cried Craig. "If he can bring them all out safely without the loss of a life he'll save the day yet for Orton. And he'll do it, too, Walter." Instantly I reconstructed in my mind the scene in the tunnel--the explosion of the oil-vapour, the mad race up the tube, perhaps the failure of the emergency curtain to work, the frantic efforts of the men, in panic, all to crowd through the narrow little door at once; the rapidly rising water--and above all the heroic Paddy, cool to the last, standing at the door and single-handed beating the men back with a club, so that they could go through one at a time. Only when the water had reached the level of the door of the lock, did Paddy bang it shut as he dragged the last man in. Then followed an interminable wait for the air in the lock to be exhausted. When, at last, the door at our end of the lock swung open, the men with a cheer seized Paddy and, in spite of his struggles, hoisted him on to their shoulders, and carried him off, still struggling, in triumph up the construction elevator to the open air above. The scene in Orton's office was dramatic as the men entered with Paddy. Vivian Taylor was standing defiantly, with burning eyes, facing Capps, who stared sullenly at the floor before him. Shelton was plainly abashed. "Kennedy," cried Orton, vainly trying to rise, "listen. Have you still that place on the telegraphone record, Vivian?" Miss Taylor started the telegraphone, while we all crowded around leaning forward eagerly. "Hello. Inter-River? Is this the president's office? Oh, hello. This is Capps talking. How are you? Oh, you've heard about Orton, have you? Not so bad, eh? Well, I'm arranging with my man Shelton here for the final act this afternoon. After that you can compromise with the Five-Borough on your own terms. I think I have argued Taylor and Morris into the right frame of mind for it, if we have one more big accident. What's that? How is my love affair? Well, Orton's in the way yet, but you know why I went into this deal. When you put me into his place after the compromise, I think I will pull strong with her. Saw her last night. She feels pretty bad about Orton, but she'll get over it. Besides, the pater will never let her marry a man who's down and out. By the way, you've got to do something handsome for Shelton. All right. I'll see you to-night and tell you some more. Watch the papers in the meantime for the grand finale. Good-bye." An angry growl rose from one or two of the more quick-witted men. Kennedy reached over and pulled me with him quickly through the crowd. "Hurry, Walter," he whispered hoarsely, "hustle Shelton and Capps out quick before the rest of the men wake up to what it's all about, or we shall have a lynching instead of an arrest." As we shoved and pushed them out, I saw the rough and grimy sand-hogs in the rear move quickly aside, and off came their muddy, frayed hats. A dainty figure flitted among them toward Orton. It was Vivian Taylor. "Papa," she cried, grasping Jack by both hands and turning to Taylor, who followed her closely, "Papa, I told you not to be too hasty with Jack." VII THE WHITE SLAVE Kennedy and I had just tossed a coin to decide whether it should be a comic opera or a good walk in the mellow spring night air and the opera had won, but we had scarcely begun to argue the vital point as to where to go, when the door buzzer sounded--a sure sign that some box-office had lost four dollars. It was a much agitated middle-aged couple who entered as Craig threw open the door. Of our two visitors, the woman attracted my attention first, for on her pale face the lines of sorrow were almost visibly deepening. Her nervous manner interested me greatly, though I took pains to conceal the fact that I noticed it. It was quickly accounted for, however, by the card which the man presented, bearing the name "Mr. George Gilbert" and a short scribble from First Deputy O'Connor: Mr. and Mrs. Gilbert desire to consult you with regard to the mysterious disappearance of their daughter, Georgette. I am sure I need say nothing further to interest you than that the M. P. Squad is completely baffled. O'CONNOR. "H-m," remarked Kennedy; "not strange for the Missing Persons Squad to be baffled--at least, at this case." "Then you know of our daughter's strange--er--departure?" asked Mr. Gilbert, eagerly scanning Kennedy's face and using a euphemism that would fall less harshly on his wife's ears than the truth. "Indeed, yes," nodded Craig with marked sympathy: "that is, I have read most of what the papers have said. Let me introduce my friend, Mr. Jameson. You recall we were discussing the Georgette Gilbert case this morning, Walter?" I did, and perhaps before I proceed further with the story I should quote at least the important parts of the article in the morning Star which had occasioned the discussion. The article had been headed, "When Personalities Are Lost," and with the Gilbert case as a text many instances had been cited which had later been solved by the return of the memory of the sufferer. In part the article had said: Mysterious disappearances, such as that of Georgette Gilbert, have alarmed the public and baffled the police before this, disappearances that in their suddenness, apparent lack of purpose, and inexplicability, have had much in common with the case of Miss Gilbert. Leaving out of account the class of disappearances such as embezzlers, blackmailers, and other criminals, there is still a large number of recorded cases where the subjects have dropped out of sight without apparent cause or reason and have left behind them untarnished reputations. Of these a small percentage are found to have met with violence; others have been victims of a suicidal mania; and sooner or later a clue has come to light, for the dead are often easier to find than the living. Of the remaining small proportion there are on record a number of carefully authenticated cases where the subjects have been the victims of a sudden and complete loss of memory. This dislocation of memory is a variety of aphasia known as amnesia, and when the memory is recurrently lost and restored it is an "alternating personality." The psychical researchers and psychologists have reported many cases of alternating personality. Studious efforts are being made to understand and to explain the strange type of mental phenomena exhibited in these cases, but no one has as yet given a final, clear, and comprehensive explanation of them. Such cases are by no means always connected with disappearances, but the variety known as the ambulatory type, where the patient suddenly loses all knowledge of his own identity and of his past and takes himself off, leaving no trace or clue, is the variety which the present case calls to popular attention. Then followed a list of a dozen or so interesting cases of persons who had vanished completely and had, some several days and some even years later, suddenly "awakened" to their first personality, returned, and taken up the thread of that personality where it had been broken. To Kennedy's inquiry I was about to reply that I recalled the conversation distinctly, when Mr. Gilbert shot an inquiring glance from beneath his bushy eyebrows, quickly shifting from my face to Kennedy's, and asked, "And what was your conclusion--what do you think of the case? Is it aphasia or amnesia, or whatever the doctors call it, and do you think she is wandering about somewhere unable to recover her real personality?" "I should like to have all the facts at first hand before venturing an opinion," Craig replied with precisely that shade of hesitancy that might reassure the anxious father and mother, without raising a false hope. Mr. and Mrs. Gilbert exchanged glances, the purport of which was that she desired him to tell the story. "It was day before yesterday," began Mr. Gilbert, gently touching his wife's trembling hand that sought his arm as he began rehearsing the tragedy that had cast its shadow across their lives, "Thursday, that Georgette--er--since we have heard of Georgette." His voice faltered a bit, but he proceeded: "As you know, she was last seen walking on Fifth Avenue. The police have traced her since she left home that morning. It is known that she went first to the public library, then that she stopped at a department store on the avenue, where she made a small purchase which she had charged to our family account, and finally that she went to a large book-store. Then--that is the last." Mrs. Gilbert sighed, and buried her face in a lace handkerchief as her shoulders shook convulsively. "Yes, I have read that," repeated Kennedy gently, though with manifest eagerness to get down to facts that might prove more illuminating. "I think I need hardly impress upon you the advantage of complete frankness, the fact that anything you may tell me is of a much more confidential nature than if it were told to the police. Er--r, had Miss Gilbert any--love affair, any trouble of such a nature that it might have preyed on her mind?" Kennedy's tactful manner seemed to reassure both the father and the mother, who exchanged another glance. "Although we have said no to the reporters," Mrs. Gilbert replied bravely in answer to the nod of approval from her husband, and much as if she herself were making a confession for them both, "I fear that Georgette had had a love affair. No doubt you have heard hints of Dudley Lawton's name in connection with the case? I can't imagine how they could have leaked out, for I should have said that that old affair had long since been forgotten even by the society gossips. The fact is that shortly after Georgette 'came out,' Dudley Lawton, who is quite on the road to becoming one of the rather notorious members of the younger set, began to pay her marked attentions. He is a fascinating, romantic sort of fellow, one that, I imagine, possesses much attraction for a girl who has been brought up as simply as Georgette was, and who has absorbed a surreptitious diet of modern literature such as we now know Georgette did. I suppose you have seen portraits of Georgette in the newspapers and know what a dreamy and artistic nature her face indicates?" Kennedy nodded. It is, of course, one of the cardinal tenets of journalism that all women are beautiful, but even the coarse screen of the ordinary newspaper half-tone had not been able to conceal the rather exceptional beauty of Miss Georgette Gilbert. If it had, all the shortcomings of the newspaper photographic art would have been quickly glossed over by the almost ardent descriptions by those ladies of the press who come along about the second day after an event of this kind with signed articles analysing the character and motives, the life and gowns of the latest actors in the front-page stories. "Naturally both my husband and myself opposed his attentions from the first. It was a hard struggle, for Georgette, of course, assumed the much-injured air of some of the heroines of her favourite novels. But I, at least, believed that we had won and that Georgette finally was brought to respect and, I hoped, understand our wishes in the matter. I believe so yet. Mr. Gilbert in a roundabout way came to an understanding with old Mr. Dudley Lawton, who possesses a great influence over his son, and--well, Dudley Lawton seemed to have passed out of Georgette's life. I believed so then, at least, and I see no reason for not believing so yet. I feel that you ought to know this, but really I don't think it is right to say that Georgette had a love affair. I should rather say that she had HAD a love affair, but that it had been forgotten, perhaps a year ago." Mrs. Gilbert paused again, and it was evident that though she was concealing nothing she was measuring her words carefully in order not to give a false impression. "What does Dudley Lawton say about the newspapers bringing his name into the case?" asked Kennedy, addressing Mr. Gilbert. "Nothing," replied he. "He denies that he has even spoken to her for nearly a year. Apparently he has no interest in the case. And yet I cannot quite believe that Lawton is as uninterested as he seems. I know that he has often spoken about her to members of the Cosmos Club where he lives, and that he reads practically everything that the newspapers print about the case." "But you have no reason to think that there has ever been any secret communication between them? Miss Georgette left no letters or anything that would indicate that her former infatuation survived?" "None whatever," repeated Mr. Gilbert emphatically. "We have gone over her personal effects very carefully, and I can't say they furnish a clue. In fact, there were very few letters. She rarely kept a letter. Whether it was merely from habit or for some purpose, I can't say." "Besides her liking for Dudley Lawton and her rather romantic nature, there are no other things in her life that would cause a desire for freedom?" asked Kennedy, much as a doctor might test the nerves of a patient. "She had no hobbies?" "Beyond the reading of some books which her mother and I did not altogether approve of, I should say no--no hobbies." "So far, I suppose, it is true that neither you nor the police have received even a hint as to where she went after leaving the book-store?" "Not a hint. She dropped out as completely as if the earth had swallowed her." "Mrs. Gilbert," said Kennedy, as our visitors rose to go, "you may rest assured that if it is humanly possible to find your daughter I shall leave no stone unturned until I have probed to the bottom of this mystery. I have seldom had a case that hung on more slender threads, yet if I can weave other threads to support it I feel that we shall soon find that the mystery is not so baffling as the Missing Persons Squad has found it so far." Scarcely had the Gilberts left when Kennedy put on his hat, remarking: "We'll at least get our walk, if not the show. Let's stroll around to the Cosmos Club. Perhaps we may catch Lawton in." Luckily we chanced to find him there in the reading-room. Lawton was, as Mrs. Gilbert had said, a type that is common enough in New York and is very fascinating to many girls. In fact, he was one of those fellows whose sins are readily forgiven because they are always interesting. Not a few men secretly admire though publicly execrate the Lawton type. I say we chanced to find him in. That was about all we found. Our interview was most unsatisfactory. For my part, I could not determine whether he was merely anxious to avoid any notoriety in connection with the case or whether he was concealing something that might compromise himself. "Really, gentlemen," he drawled, puffing languidly on a cigarette and turning slowly toward the window to watch the passing throng under the lights of the avenue, "really I don't see how I can be of any assistance. You see, except for a mere passing acquaintance Miss Gilbert and I had drifted entirely apart--entirely apart--owing to circumstances over which I, at least, had no control." "I thought perhaps you might have heard from her or about her, through some mutual friend," remarked Kennedy, carefully concealing under his nonchalance what I knew was working in his mind--a belief that, after all, the old attachment had not been so dead as the Gilberts had fancied. "No, not a breath, either before this sad occurrence or, of course, after. Believe me, if I could add one fact that would simplify the search for Georgette--ah, Miss Gilbert--ah--I would do so in a moment," replied Lawton quickly, as if desirous of getting rid of us as soon as possible. Then perhaps as if regretting the brusqueness with which he had tried to end the interview, he added, "Don't misunderstand me. The moment you have discovered anything that points to her whereabouts, let me know immediately. You can count on me--provided you don't get me into the papers. Good-night, gentlemen. I wish you the best of success." "Do you think he could have kept up the acquaintance secretly?" I asked Craig as we walked up the avenue after this baffling interview. "Could he have cast her off when he found that in spite of her parents' protests she was still in his power?" "It's impossible to say what a man of Dudley Lawton's type could do," mused Kennedy, "for the simple reason that he himself doesn't know until he has to do it. Until we have more facts, anything is both possible and probable." There was nothing more that could be done that night, though after our walk we sat up for an hour or two discussing probabilities. It did not take me long to reach the end of my imagination and give up the case, but Kennedy continued to revolve the matter in his mind, looking at it from every angle and calling upon all the vast store of information that he had treasured up in that marvellous brain of his, ready to be called on almost as if his mind were card-indexed. "Murders, suicides, robberies, and burglaries are, after all, pretty easily explained," he remarked, after a long period of silence on my part, "but the sudden disappearance of people out of the crowded city into nowhere is something that is much harder to explain. And it isn't so difficult to disappear as some people imagine, either. You remember the case of the celebrated Arctic explorer whose picture had been published scores of times in every illustrated paper. He had no trouble in disappearing and then reappearing later, when he got ready. "Yet experience has taught me that there is always a reason for disappearances. It is our next duty to discover that reason. Still, it won't do to say that disappearances are not mysterious. Disappearances except for money troubles are all mysterious. The first thing in such a case is to discover whether the person has any hobbies or habits or fads. That is what I tried to find out from the Gilberts. I can't tell yet whether I succeeded." Kennedy took a pencil and hastily jotted down something on a piece of paper which he tossed over to me. It read: 1. Love, family trouble. 2. A romantic disposition. 3. Temporary insanity, self-destruction. 4. Criminal assault. 5. Aphasia. 6. Kidnapping. "Those are the reasons why people disappear, eliminating criminals and those who have financial difficulties. Dream on that and see if you can work out the answer in your subliminal consciousness. Good-night." Needless to say, I was no further advanced in the morning than at midnight, but Kennedy seemed to have evolved at least a tentative programme. It started with a visit to the public library, where he carefully went over the ground already gone over by the police. Finding nothing, he concluded that Miss Gilbert had not found what she wanted at the library and had continued the quest, even as he was continuing the quest of herself. His next step was to visit the department-store. The purchase had been an inconsequential affair of half a dozen handkerchiefs, to be sent home. This certainly did not look like a premeditated disappearance; but Craig was proceeding on the assumption that this purchase indicated nothing except that there had been a sale of handkerchiefs which had caught her eye. Having stopped at the library first and a book-shop afterward, he assumed that she had also visited the book-department of the store. But here again nobody seemed to recall her or that she had asked for anything in particular. Our last hope was the book-shop. We paused for a moment to look at the display in the window, but only for a moment, for Craig quickly pulled me along inside. In the window was a display of books bearing the sign: BOOKS ON NEW THOUGHT, OCCULTISM, CLAIRVOYANCE, MESMERISM Instead of attempting to go over the ground already traversed by the police, who had interrogated the numerous clerks without discovering which one, if any, had waited on Miss Gilbert, Kennedy asked at once to see the record of sales of the morning on which she had disappeared. Running his eye quickly down the record, he picked out a work on clairvoyance and asked to see the young woman who had made the sale. The clerk was, however, unable to recall to whom she had sold the book, though she finally admitted that she thought it might have been a young woman who had some difficulty in making up her mind just which one of the numerous volumes she wanted. She could not say whether the picture Kennedy showed her of Miss Gilbert was that of her customer, nor was she sure that the customer was not escorted by some one. Altogether it was nearly as hazy as our interview with Lawton. "Still," remarked Kennedy cheerfully, "it may furnish a clue, after all. The clerk at least was not positive that it was NOT Miss Gilbert to whom she sold the book. Since we are down in this neighbourhood, let us drop in and see Mr. Gilbert again. Perhaps something may have happened since last night." Mr. Gilbert was in the dry-goods business in a loft building in the new dry-goods section on Fourth Avenue. One could almost feel that a tragedy had invaded even his place of business. As we entered, we could see groups of clerks, evidently discussing the case. It was no wonder, I felt, for the head of the firm was almost frantic, and beside the loss of his only daughter the loss of his business would count as nothing, at least until the keen edge of his grief was worn off. "Mr. Gilbert is out," replied his secretary, in answer to our inquiry. "Haven't you heard? They have just discovered the body of his daughter in a lonely spot in the Croton Aqueduct. The report came in from the police just a few minutes ago. It is thought that she was murdered in the city and carried there in an automobile." The news came with a stinging shock. I felt that, after all, we were too late. In another hour the extras would be out, and the news would be spread broadcast. The affair would be in the hands of the amateur detectives, and there was no telling how many promising clues might be lost. "Dead!" exclaimed Kennedy, as he jammed his hat on his head and bolted for the door. "Hurry, Walter. We must get there before the coroner makes his examination." I don't know how we managed to do it, but by dint of subway, elevated, and taxicab we arrived on the scene of the tragedy not very long after the coroner. Mr. Gilbert was there, silent, and looking as if he had aged many years since the night before; his hand shook and he could merely nod recognition to us. Already the body had been carried to a rough shanty in the neighbourhood, and the coroner was questioning those who had made the discovery, a party of Italian labourers on the water improvement near by. They were a vicious looking crew, but they could tell nothing beyond the fact that one of them had discovered the body in a thicket where it could not possibly have lain longer than overnight. There was no reason, as yet, to suspect any of them, and indeed, as a much travelled automobile road ran within a few feet of the thicket, there was every reason to believe that the murder, if murder it was, had been committed elsewhere and that the perpetrator had taken this means of getting rid of his unfortunate victim. Drawn and contorted were the features of the poor girl, as if she had died in great physical agony or after a terrific struggle. Indeed, marks of violence on her delicate throat and neck showed only too plainly that she had been choked. As Kennedy bent over the form of the once lovely Georgette, he noted the clenched hands. Then he looked at them more closely. I was standing a little behind him, for though Craig and I had been through many thrilling adventures, the death of a human being, especially of a girl like Miss Gilbert, filled me with horror and revulsion. I could see, however, that he had noted something unusual. He pulled out a little pocket magnifying glass and made an even more minute examination of the hands. At last he rose and faced us, almost as if in triumph. I could not see what he had discovered--at least it did not seem to be anything tangible, like a weapon. Quickly he opened the pocketbook which she had carried. It seemed to be empty, and he was about to shut it when something white, sticking in one corner, caught his eye. Craig pulled out a clipping from a newspaper, and we crowded about him to look at it. It was a large clipping from the section of one of the metropolitan journals which carries a host of such advertisements as "spirit medium," "psychic palmist," "yogi mediator," "magnetic influences," "crystal gazer," "astrologer," "trance medium," and the like. At once I thought of the sallow, somewhat mystic countenance of Dudley, and the idea flashed, half-formed, in my mind that somehow this clue, together with the purchase of the book on clairvoyance, might prove the final link necessary. But the first problem in Kennedy's mind was to keep in touch with what the authorities were doing. That kept us busy for several hours, during which Craig was in close consultation with the coroner's physician. The physician was of the opinion that Miss Gilbert had been drugged as well as strangled, and for many hours, down in his laboratory, his chemists were engaged in trying to discover from tests of her blood whether the theory was true. One after another the ordinary poisons were eliminated, until it began to look hopeless. So far Kennedy had been only an interested spectator, but as the different tests failed, he had become more and more keenly alive. At last it seemed as if he could wait no longer. "Might I try one or two reactions with that sample?" he asked of the physician who handed him the test tube in silence. For a moment or two Craig thoughtfully regarded it, while with one hand he fingered the bottles of ether, alcohol, distilled water, and the many reagents standing before him. He picked up one and poured a little liquid into the test tube. Then, removing the precipitate that was formed, he tried to dissolve it in water. Not succeeding, he tried the ether and then the alcohol. Both were successful. "What is it?" we asked as he held the tube up critically to the light. "I can't be sure yet," he answered slowly. "I thought at first that it was some alkaloid. I'll have to make further tests before I can be positive just what it is. If I may retain this sample I think that with other clues that I have discovered I may be able to tell you something definite soon." The coroner's physician willingly assented, and Craig quickly dispatched the tube, carefully sealed, to his laboratory. "That part of our investigation will keep," he remarked as we left the coroner's office. "To-night I think we had better resume the search which was so unexpectedly interrupted this morning. I suppose you have concluded, Walter, that we can be reasonably sure that the trail leads back through the fortune-tellers and soothsayers of New York,--which one, it would be difficult to say. The obvious thing, therefore, is to consult them all. I think you will enjoy that part of it, with your newspaperman's liking for the bizarre." The fact was that it did appeal to me, though at the moment I was endeavouring to formulate a theory in which Dudley Lawton and an accomplice would account for the facts. It was early in the evening as we started out on our tour of the clairvoyants of New York. The first whom Kennedy selected from the advertisements in the clipping described himself as "Hata, the Veiled Prophet, born with a double veil, educated in occult mysteries and Hindu philosophy in Egypt and India." Like all of them his advertisement dwelt much on love and money: The great questions of life are quickly solved, failure turned to success, sorrow to joy, the separated are brought together, foes made friends. Truths are laid bare to his mysterious mind. He gives you power to attract and control those whom you may desire, tells you of living or dead, your secret troubles, the cause and remedy. Advice on all affairs of life, love, courtship, marriage, business, speculations, investments. Overcomes rivals, enemies, and all evil influences. Will tell you how to attract, control, and change the thought, intentions, actions, or character of any one you desire. Hata was a modest adept who professed to be able to explain the whole ten stages of Yoga. He had established himself on a street near Times Square, just off Broadway, and there we found several automobiles and taxicabs standing at the curb, a mute testimony to the wealth of at least some of his clientele. A solemn-faced coloured man ushered us into a front parlour and asked if we had come to see the professor. Kennedy answered that we had. "Will you please write your names and addresses on the outside sheet of this pad, then tear it off and keep it?" asked the attendant. "We ask all visitors to do that simply as a guarantee of good faith. Then if you will write under it what you wish to find out from the professor I think it will help you concentrate. But don't write while I am in the room, and don't let me see the writing." "A pretty cheap trick," exclaimed Craig when the attendant had gone. "That's how he tells the gullible their names before they tell him. I've a good notion to tear off two sheets. The second is chemically prepared, with paraffin, I think. By dusting it over with powdered charcoal you can bring out what was written on the first sheet over it. Oh, well, let's let him get something across, anyway. Here goes, our names and addresses, and underneath I'll write, 'What has become of Georgette Gilbert?'" Perhaps five minutes later the negro took the pad, the top sheet having been torn off and placed in Kennedy's pocket. He also took a small fee of two dollars. A few minutes later we were ushered into the awful presence of the "Veiled Prophet," a tall, ferret-eyed man in a robe that looked suspiciously like a brocaded dressing-gown much too large for him. Sure enough, he addressed us solemnly by name and proceeded directly to tell us why we had come. "Let us look into the crystal of the past, present, and future and read what it has to reveal," he added solemnly, darkening the room, which was already only dimly lighted. Then Hata, the crystal-gazer, solemnly seated himself in a chair. Before him, in his hands, reposing on a bag of satin, lay a huge oval piece of glass. He threw forward his head and riveted his eyes on the milky depths of the crystal. In a moment he began to talk, first ramblingly, then coherently. "I see a man, a dark man," he began. "He is talking earnestly to a young girl. She is trying to avoid him. Ah--he seizes her by both arms. They struggle. He has his hand at her throat. He is choking her." I was thinking of the newspaper descriptions of Lawton, which the fakir had undoubtedly read, but Kennedy was leaning forward over the crystal-gazer, not watching the crystal at all, nor with his eyes on the clairvoyant's face. "Her tongue is protruding from her mouth, her eyes are bulging---" "Yes, yes," urged Kennedy. "Go on." "She falls. He strikes her. He flees. He goes to---" Kennedy laid his hand ever so lightly on the arm of the clairvoyant, then quickly withdrew it. "I cannot see where he goes. It is dark, dark. You will have to come back to-morrow when the vision is stronger." The thing stung me by its crudity. Kennedy, however, seemed elated by our experience as we gained the street. "Craig," I remonstrated, "you don't mean to say you attach any importance to vapourings like that? Why, there wasn't a thing the fellow couldn't have imagined from the newspapers, even the clumsy description of Dudley Lawton." "We'll see," he replied cheerfully, as we stopped under a light to read the address of the next seer, who happened to be in the same block. It proved to be the psychic palmist who called himself "the Pandit." He also was "born with a strange and remarkable power--not meant to gratify the idle curious, but to direct, advise, and help men and women"--at the usual low fee. He said in print that he gave instant relief to those who had trouble in love, and also positively guaranteed to tell your name and the object of your visit. He added: Love, courtship, marriage. What is more beautiful than the true unblemished love of one person for another? What is sweeter, better, or more to be desired than perfect harmony and happiness? If you want to win the esteem, love, and everlasting affection of another, see the Pandit, the greatest living master of the occult science. Inasmuch as this seer fell into a passion at the other incompetent soothsayers in the next column (and almost next door) it seemed as if we must surely get something for our money from the Pandit. Like Hata, the Pandit lived in a large brownstone house. The man who admitted us led us into a parlour where several people were seated about as if waiting for some one. The pad and writing process was repeated with little variation. Since we were the latest comers we had to wait some time before we were ushered into the presence of the Pandit, who was clad in a green silk robe. The room was large and had very small windows of stained glass. At one end of the room was an altar on which burned several candles which gave out an incense. The atmosphere of the room was heavy with a fragrance that seemed to combine cologne with chloroform. The Pandit waved a wand, muttering strange sounds as he did so, for in addition to his palmistry, which he seemed not disposed to exhibit that night, he dealt in mysteries beyond human ken. A voice, quite evidently from a phonograph buried in the depths of the altar, answered in an unknown language which sounded much like "Al-ya wa-aa haal-ya waa-ha." Across the dim room flashed a pale blue light with a crackling noise, the visible rays from a Crookes tube, I verily believe. The Pandit, however, said it was the soul of a saint passing through. Then he produced two silken robes, one red, which he placed on Kennedy's shoulders, and one violet, which he threw over me. From the air proceeded strange sounds of weird music and words. The Pandit seemed to fall asleep, muttering. Apparently, however, Kennedy and I were bad subjects, for after some minutes of this he gave it up, saying that the spirits had no revelation to make to-night in the matter in which we had called. Inasmuch as we had not written on the pad just what that matter was, I was not surprised. Nor was I surprised when the Pandit laid off his robe and said unctuously, "But if you will call to-morrow and concentrate, I am sure that I can secure a message that will be helpful about your little matter." Kennedy promised to call, but still he lingered. The Pandit, anxious to get rid of us, moved toward the door. Kennedy sidled over toward the green robe which the Pandit had laid on a chair. "Might I have some of your writings to look over in the meantime?" asked Craig as if to gain time. "Yes, but they will cost you three dollars a copy--the price I charge all my students," answered the Pandit with just a trace of a gleam of satisfaction at having at last made an impression. He turned and entered a cabinet to secure the mystic literature. The moment he had disappeared Kennedy seized the opportunity he had been waiting for. He picked up the green robe and examined the collar and neck very carefully under the least dim of the lights in the room. He seemed to find what he wished, yet he continued to examine the robe until the sound of returning footsteps warned him to lay it down again. He had not been quite quick enough. The Pandit eyed us suspiciously, then he rang a bell. The attendant appeared instantly, noiselessly. "Show these men into the library," he commanded with just the faintest shade of trepidation. "My servant will give you the book," he said to Craig. "Pay him." It seemed that we had suddenly been looked upon with disfavour, and I half suspected he thought we were spies of the police, who had recently received numerous complaints of the financial activities of the fortune tellers, who worked in close harmony with certain bucket-shop operators in fleecing the credulous of their money by inspired investment advice. At any rate, the attendant quickly opened a door into the darkness. Treading cautiously I followed Craig. The door closed behind us. I clenched my fists, not knowing what to expect. "The deuce!" exclaimed Kennedy. "He passed us out into an alley. There is the street not twenty feet away. The Pandit is a clever one, all right." It was now too late to see any of the other clairvoyants on our list, so that with this unceremonious dismissal we decided to conclude our investigations for the night. The next morning we wended our way up into the Bronx, where one of the mystics had ensconced himself rather out of the beaten track of police protection, or persecution, one could not say which. I was wondering what sort of vagary would come next. It proved to be "Swami, the greatest clairvoyant, psychic palmist, and Yogi mediator of them all." He also stood alone in his power, for he asserted: Names friends, enemies, rivals, tells whom and when you will marry, advises you upon love, courtship, marriage, business, speculation, transactions of every nature. If you are worried, perplexed, or in trouble come to this wonderful man. He reads your life like an open book; he overcomes evil influences, reunites the separated, causes speedy and happy marriage with the one of your choice, tells how to influence any one you desire, tells whether wife or sweetheart is true or false. Love, friendship, and influence of others obtained and a greater share of happiness in life secured. The key to success is that marvellous, subtle, unseen power that opens to your vision the greatest secrets of life. It gives you power which enables you to control the minds of men and women. The Swami engaged to explain the "wonderful Karmic law," and by his method one could develop a wonderful magnetic personality by which he could win anything the human heart desired. It was therefore with great anticipation that we sought out the wonderful Swami and, falling into the spirit of his advertisement, posed as "come-ons" and pleaded to obtain this wonderful magnetism and a knowledge of the Karmic law--at a ridiculously low figure, considering its inestimable advantages to one engaged in the pursuit of criminal science. Naturally the Swami was pleased at two such early callers, and his narrow, half-bald head, long slim nose, sharp grey eyes, and sallow, unwholesome complexion showed his pleasure in every line and feature. Rubbing his hands together as he motioned us into the next room, the Swami seated us on a circular divan with piles of cushions upon it. There were clusters of flowers in vases about the room, which gave it the odour of the renewed vitality of the year. A lackey entered with a silver tray of cups of coffee and a silver jar in the centre. Talking slowly and earnestly about the "great Karmic law," the Swami bade us drink the coffee, which was of a vile, muddy, Turkish variety. Then from the jar he took a box of rock crystal containing a sort of greenish compound which he kneaded into a little gum--gum tragacanth, I afterward learned,--and bade us taste. It was not at all unpleasant to the taste, and as nothing happened, except the suave droning of the mystic before us, we ate several of the gum pellets. I am at a loss to describe adequately just the sensations that I soon experienced. It was as if puffs of hot and cold air were alternately blown on my spine, and I felt a twitching of my neck, legs, and arms. Then came a subtle warmth. The whole thing seemed droll; the noise of the Swami's voice was most harmonious. His and Kennedy's faces seemed transformed. They were human faces, but each had a sort of animal likeness back of it, as Lavater has said. The Swami seemed to me to be the fox, Kennedy the owl. I looked in the glass, and I was the eagle. I laughed outright. It was sensuous in the extreme. The beautiful paintings on the walls at once became clothed in flesh and blood. A picture of a lady hanging near me caught my eye. The countenance really smiled and laughed and varied from moment to moment. Her figure became rounded and living and seemed to stir in the frame. The face was beautiful but ghastly. I seemed to be borne along on a sea of pleasure by currents of voluptuous happiness. The Swami was affected by a profound politeness. As he rose and walked about the room, still talking, he salaamed and bowed. When I spoke it sounded like a gun, with an echo long afterward rumbling in my brain. Thoughts came to me like fury, bewildering, sometimes as points of light in the most exquisite fireworks. Objects were clothed in most fantastic garbs. I looked at my two animal companions. I seemed to read their thoughts. I felt strange affinities with them, even with the Swami. Yet it was all by the psychological law of the association of ideas, though I was no longer master but the servant of those ideas. As for Kennedy, the stuff seemed to affect him much differently than it did myself. Indeed, it seemed to rouse in him something vicious. The more I smiled and the more the Swami salaamed, the more violent I could see Craig getting, whereas I was lost in a maze of dreams that I would not have stopped if I could. Seconds seemed to be years; minutes ages. Things at only a short distance looked much as they do when looked at through the inverted end of a telescope. Yet it all carried with it an agreeable exhilaration which I can only describe as the heightened sense one feels on the first spring day of the year. At last the continued plying of the drug seemed to be too much for Kennedy. The Swami had made a profound salaam. In an instant Kennedy had seized with both hands the long flowing hair at the back of the Swami's bald forehead, and he tugged until the mystic yelled with pain and the tears stood in his eyes. With a leap I roused myself from the train of dreams and flung myself between them. At the sound of my voice and the pressure of my grasp, Craig sullenly and slowly relaxed his grip. A vacant look seemed to steal into his face, and seizing his hat, which lay on a near-by stool, he stalked out in silence, and I followed. Neither of us spoke for a moment after we had reached the street, but out of the corner of my eye I could see that Kennedy's body was convulsed as if with suppressed emotion. "Do you feel better in the air?" I asked anxiously, yet somewhat vexed and feeling a sort of lassitude and half regret at the reality of life and not of the dreams. It seemed as if he could restrain himself no longer. He burst out into a hearty laugh. "I was just watching the look of disgust on your face," he said as he opened his hand and showed me three or four of the gum lozenges that he had palmed instead of swallowing. "Ha, ha! I wonder what the Swami thinks of his earnest effort to expound the Karmic law." It was beyond me. With the Swami's concoction still shooting thoughts like sky rockets through my brain I gave it up and allowed Kennedy to engineer our next excursion into the occult. One more seer remained to be visited. This one professed to "hold your life mirror" and by his "magnetic monochrome," whatever that might be, he would "impart to you an attractive personality, mastery of being, for creation and control of life conditions." He described himself as the "Guru," and, among other things, he professed to be a sun-worshipper. At any rate, the room into which we were admitted was decorated with the four-spoked wheel, or wheel and cross, the winged circle, and the winged orb. The Guru himself was a swarthy individual with a purple turban wound around his head. In his inner room were many statuettes, photographs of other Gurus of the faith, and on each of the four walls were mysterious symbols in plaster representing a snake curved in a circle, swallowing his tail, a five-pointed star, and in the centre another winged sphere. Craig asked the Guru to explain the symbols, to which he replied with a smile: "The snake represents eternity, the star involution and evolution of the soul, while the winged sphere--eh, well, that represents something else. Do you come to learn of the faith?" At this gentle hint Craig replied that he did, and the utmost amicability was restored by the purchase of the Green Book of the Guru, which seemed to deal with everything under the sun, and particularly the revival of ancient Asiatic fire-worship with many forms and ceremonies, together with posturing and breathing that rivalled the "turkey trot," the "bunny hug," and the "grizzly bear." The book, as we turned over its pages, gave directions for preparing everything from food to love-philtres and the elixir of life. One very interesting chapter was devoted to "electric marriage," which seemed to come to those only who, after searching patiently, at last found perfect mates. Another of the Guru's tenets seemed to be purification by eliminating all false modesty, bathing in the sun, and while bathing engaging in any occupation which kept the mind agreeably occupied. On the first page was the satisfying legend, "There is nothing in the world that a disciple can give to pay the debt to the Guru who has taught him one truth." As we talked, it seemed quite possible to me that the Guru might exert a very powerful hypnotic influence over his disciples or those who came to seek his advice. Besides this indefinable hypnotic influence, I also noted the more material lock on the door to the inner sanctuary. "Yes," the Guru was saying to Kennedy, "I can secure you one of the love-pills from India, but it will cost you--er--ten dollars." I think he hesitated, to see how much the traffic would bear, from one to one hundred, and compromised with only one zero after the unit. Kennedy appeared satisfied, and the Guru departed with alacrity to secure the specially imported pellet. In a corner was a sort of dressing-table on which lay a comb and brush. Kennedy seemed much interested in the table and was examining it when the Guru returned. Just as the door opened he managed to slip the brush into his pocket and appear interested in the mystic symbols on the wall opposite. "If that doesn't work," remarked the Guru in remarkably good English, "let me know, and you must try one of my charm bottles. But the love-pills are fine. Good-day." Outside Craig looked at me quizzically. "You wouldn't believe it, Walter, would you?" he said. "Here in this twentieth century in New York, and in fact in every large city of the world--love-philtres, love-pills, and all the rest of it. And it is not among the ignorant that these things are found, either. You remember we saw automobiles waiting before some of the places." "I suspect that all who visit the fakirs are not so gullible, after all," I replied sententiously. "Perhaps not. I think I shall have something interesting to say to-night as a result of our visits, at least." During the remainder of the day Kennedy was closely confined in his laboratory with his microscopes, slides, chemicals, test-tubes, and other apparatus. As for myself, I put in the time speculating which of the fakirs had been in some mysterious way connected with the case and in what manner. Many were the theories which I had formed and the situations I conjured up, and in nearly all I had one central figure, the young man whose escapades had been the talk of even the fast set of a fast society. That night Kennedy, with the assistance of First Deputy O'Connor, who was not averse to taking any action within the law toward the soothsayers, assembled a curiously cosmopolitan crowd in his laboratory. Besides the Gilberts were Dudley Lawton and his father, Hata, the Pandit, the Swami, and the Guru--the latter four persons in high dudgeon at being deprived of the lucrative profits of a Sunday night. Kennedy began slowly, leading gradually up to his point: "A new means of bringing criminals to justice has been lately studied by one of the greatest scientific detectives of crime in the world, the man to whom we are indebted for our most complete systems of identification and apprehension." Craig paused and fingered the microscope before him thoughtfully. "Human hair," he resumed, "has recently been the study of that untiring criminal scientist, M. Bertillon. He has drawn up a full, classified, and graduated table of all the known colours of the human hair, a complete palette, so to speak, of samples gathered in every quarter of the globe. Henceforth burglars, who already wear gloves or paint their fingers with a rubber composition for fear of leaving finger-prints, will have to wear close-fitting caps or keep their heads shaved. Thus he has hit upon a new method of identification of those sought by the police. For instance, from time to time the question arises whether hair is human or animal. In such cases the microscope tells the answer truthfully. "For a long time I have been studying hair, taking advantage of those excellent researches by M. Bertillon. Human hair is fairly uniform, tapering gradually. Under the microscope it is practically always possible to distinguish human hair from animal. I shall not go into the distinctions, but I may add that it is also possible to determine very quickly the difference between all hair, human or animal, and cotton with its corkscrew-like twists, linen with its jointed structure, and silk, which is long, smooth, and cylindrical." Again Kennedy paused as if to emphasise this preface. "I have here," he continued, "a sample of hair." He had picked up a microscope slide that was lying on the table. It certainly did not look very thrilling--a mere piece of glass, that was all. But on the glass was what appeared to be merely a faint line. "This slide," he said, holding it up, "has what must prove an unescapable clue to the identity of the man responsible for the disappearance of Miss Gilbert. I shall not tell you yet who he is, for the simple reason that, though I could make a shrewd guess, I do not yet know what the verdict of science is, and in science we do not guess where we can prove. "You will undoubtedly remember that when Miss Gilbert's body was discovered, it bore no evidence of suicide, but on the contrary the marks of violence. Her fists were clenched, as if she had struggled with all her power against a force that had been too much for her. I examined her hands, expecting to find some evidence of a weapon she had used to defend herself. Instead, I found what was more valuable. Here on this slide are several hairs that I found tightly grasped in her rigid hands." I could not help recalling Kennedy's remark earlier in the case--that it hung on slender threads. Yet how strong might not those threads prove! "There was also in her pocketbook a newspaper clipping bearing the advertisements of several clairvoyants," he went on. "Mr. Jameson and myself had already discovered what the police had failed to find, that on the morning of the day on which she disappeared Miss Gilbert had made three distinct efforts, probably, to secure books on clairvoyance. Accordingly, Mr. Jameson and myself have visited several of the fortune-tellers and practitioners of the occult sciences in which we had reason to believe Miss Gilbert was interested. They all, by the way, make a specialty of giving advice in money matters and solving the problems of lovers. I suspect that at times Mr. Jameson has thought that I was demented, but I had to resort to many and various expedients to collect the specimens of hair which I wanted. From the police, who used Mr. Lawton's valet, I received some hair from his head. Here is another specimen from each of the advertisers, Hata, the Swami, the Pandit, and the Guru. There is just one of these specimens which corresponds in every particular of colour, thickness, and texture with the hair found so tightly grasped in Miss Gilbert's hand." As Craig said this I could feel a sort of gasp of astonishment from our little audience. Still he was not quite ready to make his disclosure. "Lest I should be prejudiced," he pursued evenly, "by my own rather strong convictions, and in order that I might examine the samples without fear or favour, I had one of my students at the laboratory take the marked hairs, mount them, number them, and put in numbered envelopes the names of the persons who furnished them. But before I open the envelope numbered the same as the slide which contains the hair which corresponds precisely with that hair found in Miss Gilbert's hand--and it is slide No. 2---" said Kennedy, picking out the slide with his finger and moving it on the table with as much coolness as if he were moving a chessman on a board instead of playing in the terrible game of human life, "before I read the name I have still one more damning fact to disclose." Craig now had us on edge with excitement, a situation which I sometimes thought he enjoyed more keenly than any other in his relentless tracing down of a criminal. "What was it that caused Miss Gilbert's death?" asked Kennedy. "The coroner's physician did not seem to be thoroughly satisfied with the theory of physical violence alone. Nor did I. Some one, I believe, exerted a peculiar force in order to get her into his power. What was that force? At first I thought it might have been the hackneyed knockout drops, but tests by the coroner's physician eliminated that. Then I thought it might be one of the alkaloids, such as morphine, cocaine, and others. But it was not any of the usual things that was used to entice her away from her family and friends. From tests that I have made I have discovered the one fact necessary to complete my case, the drug used to lure her and against which she fought in deadly struggle." He placed a test tube in a rack before us. "This tube," he continued, "contains one of the most singular and, among us, least known of the five common narcotics of the world--tobacco, opium, coca, betel nut, and hemp. It can be smoked, chewed, used as a drink, or taken as a confection. In the form of a powder it is used by the narghile smoker. As a liquid it can be taken as an oily fluid or in alcohol. Taken in any of these forms, it literally makes the nerves walk, dance, and run. It heightens the feelings and sensibilities to distraction, producing what is really hysteria. If the weather is clear, this drug will make life gorgeous; if it rains, tragic. Slight vexation becomes deadly revenge; courage becomes rashness; fear, abject terror; and gentle affection or even a passing liking is transformed into passionate love. It is the drug derived from the Indian hemp, scientifically named Cannabis Indica, better known as hashish, or bhang, or a dozen other names in the East. Its chief characteristic is that it has a profound effect on the passions. Thus, under its influence, natives of the East become greatly exhilarated, then debased, and finally violent, rushing forth on the streets with the cry, 'Amok, amok,'--'Kill, kill'--as we say, 'running amuck.' An overdose of this drug often causes insanity, while in small quantities our doctors use it as a medicine. Any one who has read the brilliant Theophile Gautier's 'Club des Hachichens' or Bayard Taylor's experience at Damascus knows something of the effect of hashish, however. "In reconstructing the story of Georgette Gilbert, as best I can, I believe that she was lured to the den of one of the numerous cults practised in New York, lured by advertisements offering advice in hidden love affairs. Led on by her love for a man whom she could not and would not put out of her life, and by her affection for her parents, she was frantic. This place offered hope, and to it she went in all innocence, not knowing that it was only the open door to a life such as the most lurid disorderly resorts of the metropolis could scarcely match. There her credulity was preyed upon, and she was tricked into taking this drug, which itself has such marked and perverting effect. But, though she must have been given a great deal of the drug, she did not yield, as many of the sophisticated do. She struggled frantically, futilely. Will and reason were not conquered, though they sat unsteadily on their thrones. The wisp of hair so tightly clasped in her dead hand shows that she fought bitterly to the end." Kennedy was leaning forward earnestly, glaring at each of us in turn. Lawton was twisting uneasily in his chair, and I could see that his fists were doubled up and that he was holding himself in leash as if waiting for something, eyeing us all keenly. The Swami was seized with a violent fit of trembling, and the other fakirs were staring in amazement. Quickly I stepped between Dudley Lawton and Kennedy, but as I did so, he leaped behind me, and before I could turn he was grappling wildly with some one on the floor. "It's all right, Walter," cried Kennedy, tearing open the envelope on the table. "Lawton has guessed right. The hair was the Swami's. Georgette Gilbert was one victim who fought and rescued herself from a slavery worse than death. And there is one mystic who could not foresee arrest and the death house at Sing Sing in his horoscope." VIII THE FORGER We were lunching with Stevenson Williams, a friend of Kennedy's, at the Insurance Club, one of the many new downtown luncheon clubs, where the noon hour is so conveniently combined with business. "There isn't much that you can't insure against nowadays," remarked Williams when the luncheon had progressed far enough to warrant a tentative reference to the obvious fact that he had had a purpose in inviting us to the club. "Take my own company, for example, the Continental Surety. We have lately undertaken to write forgery insurance." "Forgery insurance?" repeated Kennedy. "Well, I should think you'd be doing a ripping business--putting up the premium rate about every day in this epidemic of forgery that seems to be sweeping over the country." Williams, who was one of the officers of the company, smiled somewhat wearily, I thought. "We are," he replied drily. "That was precisely what I wanted to see you about." "What? The premiums or the epidemic?" "Well--er--both, perhaps. I needn't say much about the epidemic, as you call it. To you I can admit it; to the newspapers, never. Still, I suppose you know that it is variously estimated that the forgers of the country are getting away with from ten to fifteen million dollars a year. It is just one case that I was thinking about--one on which the regular detective agencies we employ seem to have failed utterly so far. It involves pretty nearly one of those fifteen millions." "What? One case? A million dollars?" gasped Kennedy, gazing fixedly at Williams as if he found it difficult to believe. "Exactly," replied Williams imperturbably, "though it was not done all at one fell swoop, of course, but gradually, covering a period of some months. You have doubtless heard of the By-Products Company of Chicago?" Craig nodded. "Well, it is their case," pursued Williams, losing his quiet manner and now hurrying ahead almost breathlessly. "You know they own a bank out there also, called the By-Products Bank. That's how we come to figure in the case, by having insured their bank against forgery. Of course our liability runs up only to $50,000. But the loss to the company as well as to its bank through this affair will reach the figure I have named. They will have to stand the balance beyond our liability and, well, fifty thousand is not a small sum for us to lose, either. We can't afford to lose it without a fight." "Of course not. But you must have some suspicions, some clues. You must have taken some action in tracing the thing out, whatever is back of it." "Surely. For instance, only the other day we had the cashier of the bank, Bolton Brown, arrested, though he is out on bail now. We haven't anything directly against him, but he is suspected of complicity on the inside, and I may say that the thing is so gigantic that there must have been some one on the inside concerned with it. Among other things we have found that Bolton Brown has been leading a rather fast life, quite unknown to his fellow-officials. We know that he has been speculating secretly in the wheat corner that went to pieces, but the most significant thing is that he has been altogether too intimate with an adventuress, Adele De-Mott, who has had some success as a woman of high finance in various cities here and in Europe and even in South America. It looks bad for him from the commonsense standpoint, though of course I'm not competent to speak of the legal side of the matter. But, at any rate, we know that the insider must have been some one pretty close to the head of the By-Products Company or the By-Products Bank." "What was the character of the forgeries?" asked Kennedy. "They seem to have been of two kinds. As far as we are concerned it is the check forgeries only that interest the Surety Company. For some time, apparently, checks have been coming into the bank for sums all the way from a hundred dollars to five thousand. They have been so well executed that some of them have been certified by the bank, all of them have been accepted when they came back from other banks, and even the officers of the company don't seem to be able to pick any flaws in them except as to the payee and the amounts for which they were drawn. They have the correct safety tint on the paper and are stamped with rubber stamps that are almost precisely like those used by the By-Products Company. "You know that banking customs often make some kinds of fraud comparatively easy. For instance no bank will pay out a hundred dollars or often even a dollar without identification, but they will certify a check for almost any office boy who comes in with it. The common method of forgers lately has been to take such a certified forged check, deposit it in another bank, then gradually withdraw it in a few days before there is time to discover the forgery. In this case they must have had the additional advantage that the insider in the company or bank could give information and tip the forger off if the forgery happened to be discovered." "Who is the treasurer of the company?" asked Craig quickly. "John Carroll--merely a figurehead, I understand. He's in New York now, working with us, as I shall tell you presently. If there is any one else besides Brown in it, it might be Michael Dawson, the nominal assistant but really the active treasurer. There you have another man whom we suspect, and, strangely enough, can't find. Dawson was the assistant treasurer of the company, you understand, not of the bank." "You can't find him? Why?" asked Kennedy, considerably puzzled. "No, we can't find him. He was married a few days ago, married a pretty prominent society girl in the city, Miss Sibyl Sanderson. It seems they kept the itinerary of their honeymoon secret, more as a joke on their friends than anything else, they said, for Miss Sanderson was a well-known beauty and the newspapers bothered the couple a good deal with publicity that was distasteful. At least that was his story. No one knows where they are or whether they'll ever turn up again. "You see, this getting married had something to do with the exposure in the first place. For the major part of the forgeries consists not so much in the checks, which interest my company, but in fraudulently issued stock certificates of the By-Products Company. About a million of the common stock was held as treasury stock--was never issued. "Some one has issued a large amount of it, all properly signed and sealed. Whoever it was had a little office in Chicago from which the stock was sold quietly by a confederate, probably a woman, for women seem to rope in the suckers best in these get-rich-quick schemes. And, well, if it was Dawson the honeymoon has given him a splendid chance to make his get-away, though it also resulted in the exposure of the forgeries. Carroll had to take up more or less active duty, with the result that a new man unearthed the--but, say, are you really interested in this case?" Williams was leaning forward, looking anxiously at Kennedy and it would not have taken a clairvoyant to guess what answer he wanted to his abrupt question. "Indeed I am," replied Craig, "especially as there seems to be a doubt about the guilty person on the inside." "There is doubt enough, all right," rejoined Williams, "at least I think so, though our detectives in Chicago who have gone over the thing pretty thoroughly have been sure of fixing something on Bolton Brown, the cashier. You see the blank stock certificates were kept in the company's vault in the bank to which, of course, Brown had access. But then, as Carroll argues, Dawson had access to them, too, which is very true--more so for Dawson than for Brown, who was in the bank and not in the company. I'm all at sea. Perhaps if you're interested you'd better see Carroll. He's here in the city and I'm sure I could get you a good fee out of the case if you cared to take it up. Shall I see if I can get him on the wire?" We had finished luncheon and, as Craig nodded, Williams dived into a telephone booth outside the dining-room and in a few moments emerged, perspiring from the closeness. He announced that Carroll requested that we call on him at an office in Wall Street, a few blocks away, where he made his headquarters when he was in New York. The whole thing was done with such despatch that I could not help feeling that Carroll had been waiting to hear from his friend in the insurance company. The look of relief on Williams's face when Kennedy said he would go immediately showed plainly that the insurance man considered the cost of the luncheon, which had been no slight affair, in the light of a good investment in the interest of his company, which was "in bad" for the largest forgery insurance loss since they had begun to write that sort of business. As we hurried down to Wall Street, Kennedy took occasion to remark, "Science seems to have safeguarded banks and other institutions pretty well against outside robbery. But protection against employees who can manipulate books and records does not seem to have advanced as rapidly. Sometimes I think it may have lessened. Greater temptations assail the cashier or clerk with greater opportunity for speculation, and the banks, as many authorities will agree, have not made enough use of the machinery available to put a stop to embezzlement. This case is evidently one of the results. The careless fellows at the top, like this man Carroll whom we are going to see, generally put forward as excuse the statement that the science of banking and of business is so complex that a rascal with ingenuity enough to falsify the books is almost impossible of detection. Yet when the cat is out of the bag as in several recent cases the methods used are often of the baldest and most transparent sort, fictitious names, dummies, and all sorts of juggling and kiting of checks. But I hardly think this is going to prove one of those simple cases." John Carroll was a haggard and unkempt sort of man. He looked to me as if the defalcations had preyed on his mind until they had become a veritable obsession. It was literally true that they were all that he could talk about, all that he was thinking about. He was paying now a heavy penalty for having been a dummy and honorary officer. "This thing has become a matter of life and death with me," he began eagerly, scarcely waiting for us to introduce ourselves, as he fixed his unnaturally bright eyes on us anxiously. "I've simply got to find the man who has so nearly wrecked the By-Products Bank and Company. Find him or not, I suppose I am a ruined man, myself, but I hope I may still prove myself honest." He sighed and his eyes wandered vacantly out of the window as if he were seeking rest and could not find it. "I understand that the cashier, Bolton Brown, has been arrested," prompted Kennedy. "Yes, Bolton Brown, arrested," he repeated slowly, "and since he has been out on bail he, too, seems to have disappeared. Now let me tell you about what I think of that, Kennedy. I know it looks bad for Brown. Perhaps he's the man. The Surety Company says so, anyway. But we must look at this thing calmly." He was himself quite excited, as he went on, "You understand, I suppose, just how much Brown must have been reasonably responsible for passing the checks through the bank? He saw personally about as many of them as--as I did, which was none until the exposure came. They were deposited in other banks by people whom we can't identify but who must have opened accounts for the purpose of finally putting through a few bad checks. Then they came back to our bank in the regular channels and were accepted. By various kinds of juggling they were covered up. Why, some of them looked so good that they were even certified by our bank before they were deposited in the other banks. Now, as Brown claims, he never saw checks unless there was something special about them and there seemed at the time to be nothing wrong about these. "But in the public mind I know there is prejudice against any bank official who speculates or leads a fast life, and of course it is warranted. Still, if Brown should clear himself finally the thing will come back to Dawson and even if he is guilty, it will make me the--er--the ultimate goat. The upshot of it all will be that I shall have to stand the blame, if not the guilt, and the only way I can atone for my laxity in the past is by activity in catching the real offender and perhaps by restoring to the company and the bank whatever can yet be recovered." "But," asked Kennedy sympathetically, "what makes you think that you will find your man, whoever he proves to be, in New York?" "I admit that it is only a very slight clue that I have," he replied confidentially. "It is just a hint Dawson dropped once to one of the men with whom he was confidential in the company. This clerk told me that a long time ago Dawson said he had always wanted to go to South America and that perhaps on his honeymoon he might get a chance. This is the way I figured it out. You see, he is clever and some of these South American countries have no extradition treaties with us by which we could reach him, once he got there." "Perhaps he has already arrived in one of them with his wife. What makes you think he hasn't sailed yet?" "No, I don't think he has. You see, she wanted to spend a part of the honeymoon at Atlantic City. I learned that indirectly from her folks, who profess to know no better than we do where the couple are. That was an additional reason why I wanted to see if by coming to New York I might not pick up some trace of them, either here or in Atlantic City." "And have you?" "Yes, I think I have." He handed us a letter-gram which he had just received from Chicago. It read: "Two more checks have come in to-day from Atlantic City and New York. They seem to be in payment of bills, as they are for odd amounts. One is from the Lorraine at Atlantic City and the other from the Hotel Amsterdam of New York. They were dated the 19th and 20th." "You see," he resumed as we finished reading, "it is now the 23rd, so that there is a difference of three days. He was here on the 20th. Now the next ship that he could take after the 20th sails from Brooklyn on the 25th. If he's clever he won't board that ship except in a disguise, for he will know that by that time some one must be watching. Now I want you to help me penetrate that disguise. Of course we can't arrest the whole shipload of passengers, but if you, with your scientific knowledge, could pick him out, then we could hold him and have breathing space to find out whether he is guilty alone or has been working with Bolton Brown." Carroll was now pacing the office with excitement as he unfolded his scheme which meant so much for himself. "H--m," mused Kennedy. "I suppose Dawson was a man of exemplary habits? They almost always are. No speculating or fast living with him as with Brown?" Carroll paused in his nervous tread. "That's another thing I've discovered. On the contrary, I think Dawson was a secret drug fiend. I found that out after he left. In his desk at the By-Products office we discovered hypodermic needles and a whole outfit--morphine, I think it was. You know how cunningly a real morphine fiend can cover up his tracks." Kennedy was now all attention. As the case unrolled it was assuming one new and surprising aspect after another. "The lettergram would indicate that he had been stopping at the Lorraine in Atlantic City," remarked Kennedy. "So I would infer, and at the Amsterdam in New York. But you can depend on it that he has not been going under his own name nor, I believe as far as I can find out, even under his own face. I think the fellow has already assumed a disguise, for nowhere can I find any description that even I could recognise." "Strange," murmured Kennedy. "I'll have to look into it. And only two days in which to do it, too. You will pardon me if I excuse myself now? There are certain aspects of the case that I hope I shall be able to shed some light on by going at them at once." "You'll find Dawson clever, clever as he can be," said Carroll, not anxious to have Kennedy go as long as he would listen to the story which was bursting from his overwrought mind. "He was able to cover up the checks by juggling the accounts. But that didn't satisfy him. He was after something big. So he started in to issue the treasury stock, forging the signatures of the president and the treasurer, that is, my signature. Of course that sort of game couldn't last forever. Some one was going to demand dividends on his stock, or transfer it, or ask to have it recorded on the books, or something that would give the whole scheme away. From each person to whom he sold stock I believe he demanded some kind of promise not to sell it within a certain period, and in that way we figure that he gave himself plenty of time to realise several hundred thousand dollars quietly. It may be that some of the forged checks represented fake interest payments. Anyhow, he's at the end of his rope now. We've had an exciting chase. I had followed down several false clues before the real significance of the hint about South America dawned on me. Now I have gone as far as I dare with it without calling in outside assistance. I think now We are up with him at last--with your help." Kennedy was anxious to go, but he paused long enough to ask another question. "And the girl?" he broke in. "She must be in the game or her letters to some of her friends would have betrayed their whereabouts. What was she like?" "Miss Sanderson was very popular in a certain rather flashy set in Chicago. But her folks were bounders. They lived right up to the limit, just as Dawson did, in my opinion. Oh, you can be sure that if a proposition like this were put up to her she'd take a chance to get away with it. She runs no risks. She didn't do it anyhow, and as for her part, after the fact, why, a woman is always pretty safe--more sinned against than sinning, and all that. It's a queer sort of honeymoon, hey?" "Have you any copies of the forged certificates?" asked Craig. "Yes, plenty of them. Since the story has been told in print they have been pouring in. Here are several." He pulled several finely engraved certificates from his pocket and Kennedy scrutinised them minutely. "I may keep these to study at my leisure?" he asked. "Certainly," replied Carroll, "and if you want any more I can wire to Chicago for them." "No, these will be sufficient for the present, thank you," said Craig. "I shall keep in touch with you and let you know the moment anything develops." Our ride uptown to the laboratory was completed in silence which I did not interrupt, for I could see that Kennedy was thinking out a course of action. The quick pace at which he crossed the campus to the Chemistry Building told me that he had decided on something. In the laboratory Craig hastily wrote a note, opened a drawer of his desk, and selected one from a bunch of special envelopes which he seemed to be saving for some purpose. He sealed it with some care, and gave it to me to post immediately. It was addressed to Dawson at the Hotel Amsterdam. On my return I found him deeply engrossed in the examination of the forged shares of stock. Having talked with him more or less in the past about handwriting I did not have to be told that he was using a microscope to discover any erasures and that photography both direct and by transmitted light might show something. "I can't see anything wrong with these documents," he remarked at length. "They show no erasures or alterations. On their face they look as good as the real article. Even if they are tracings they are remarkably fine work. It certainly is a fact, however, that they superimpose. They might all have been made from the same pair of signatures of the president and treasurer. "I need hardly to say to you, Walter, that the microscope in its various forms and with its various attachments is of great assistance to the document examiner. Even a low magnification frequently reveals a drawing, hesitating method of production, or patched and reinforced strokes as well as erasures by chemicals or by abrasion. The stereoscopic microscope, which is of value in studying abrasions and alterations since it gives depth, in this case tells me that there has been nothing of that sort practised. My colour comparison microscope, which permits the comparison of the ink on two different documents or two places on one document at the same time, tells me something. This instrument with new and accurately coloured glasses enables me to measure the tints of the ink of these signatures with the greatest accuracy and I can do what was hitherto impossible--determine how long the writing has been on the paper. I should say it was all very recent, approximately within the last two months or six weeks, and I believe that whenever the stock may have been issued it at least was all forged at the same time. "There isn't time now to go into the thing more deeply, but if it becomes necessary I can go back to it with the aid of the camera lucida and the microscopic enlarger, as well as this specially constructed document camera with lenses certified by the government. If it comes to a show-down I suppose I shall have to prove my point with the micrometer measurements down to the fifty-thousandth part of an inch. "There is certainly something very curious about these signatures," he concluded. "I don't know what measurements would show, but they are really too good. You know a forged signature may be of two kinds--too bad or too good. These are, I believe, tracings. If they were your signature and mine, Walter, I shouldn't hesitate to pronounce them tracings. But there is always some slight room for doubt in these special cases where a man sits down and is in the habit of writing his signature over and over again on one stock or bond after another. He may get so used to it that he does it automatically and his signatures may come pretty close to superimposing. If I had time, though, I think I could demonstrate that there are altogether too many points of similarity for these to be genuine signatures. But we've got to act quickly in this case or not at all, and I see that if I am to get to Atlantic City to-night I can't waste much more time here. I wish you would keep an eye on the Hotel Amsterdam while I am gone, Walter, and meet me here, to-morrow. I'll wire when I'll be back. Good-bye." It was well along in the afternoon when Kennedy took a train for the famous seaside resort, leaving me in New York with a roving commission to do nothing. All that I was able to learn at the Hotel Amsterdam was that a man with a Van Dyke beard had stung the office with a bogus check, although he had seemed to come well recommended. The description of the woman with him who seemed to be his wife might have fitted either Mrs. Dawson or Adele DeMott. The only person who had called had been a man who said he represented the By-Products Company and was the treasurer. He had questioned the hotel people rather closely about the whereabouts of the couple who had paid their expenses with the worthless slip of paper. It was not difficult to infer that this man was Carroll who had been hot on the trail, especially as he said that he personally would see the check paid if the hotel people would keep a sharp watch for the return of the man who had swindled them. Kennedy wired as he promised and returned by an early train the next day. He seemed bursting with news. "I think I'm on the trail," he cried, throwing his grip into a corner and not waiting for me to ask him what success he had had. "I went directly to the Lorraine and began frankly by telling them that I represented the By-Products Company in New York and was authorised to investigate the bad check which they had received. They couldn't describe Dawson very well--at least their description would have fitted almost any one. One thing I think I did learn and that was that his disguise must include a Van Dyke beard. He would scarcely have had time to grow one of his own and I believe when he was last seen in Chicago he was clean-shaven." "But," I objected, "men with Van Dyke beards are common enough." Then I related my experience at the Amsterdam. "The same fellow," ejaculated Kennedy. "The beard seems to have covered a multitude of sins, for while every one could recall that, no one had a word to say about his features. However, Walter, there's just one chance of making his identification sure, and a peculiar coincidence it is, too. It seems that one night this man and a lady who may have been the former Miss Sanderson, though the description of her like most amateur descriptions wasn't very accurate, were dining at the Lorraine. The Lorraine is getting up a new booklet about its accommodations and a photographer had been engaged to take a flashlight of the dining-room for the booklet. "No sooner had the flash been lighted and the picture taken than a man with a Van Dyke beard--your friend of the Amsterdam, no doubt, Walter,--rushed up to the photographer and offered him fifty dollars for the plate. The photographer thought at first it was some sport who had reasons for not wishing to appear in print in Atlantic City, as many have. The man seemed to notice that the photographer was a little suspicious and he hastened to make some kind of excuse about 'wanting the home folks to see how swell he and his wife were dining in evening dress.' It was a rather lame excuse, but the fifty dollars looked good to the photographer and he agreed to develop the plate and turn it over with some prints all ready for mailing the next day. The man seemed satisfied and the photographer took another flashlight, this time with one of the tables vacant. "Sure enough, the next day the man with a beard turned up for the plate. The photographer tells me that he had it all wrapped up ready to mail, just to call the fellow's bluff. The man was equal to the occasion, paid the money, wrote an address on the package which the photographer did not see, and as there was a box for mailing packages right at the door on the boardwalk there was no excuse for not mailing it directly. Now if I could get hold of that plate or a print from it I could identify Dawson in his disguise in a moment. I've started the post-office trying to trace that package both at Atlantic City and in Chicago, where I think it must have been mailed. I may hear from them at any moment--at least, I hope." The rest of the afternoon we spent in canvassing the drug stores in the vicinity of the Amsterdam, Kennedy's idea being that if Dawson was a habitual morphine fiend he must have replenished his supply of the drug in New York, particularly if he was contemplating a long journey where it might be difficult to obtain. After many disappointments we finally succeeded in finding a shop where a man posing as a doctor had made a rather large purchase. The name he gave was of course of no importance. What did interest us was that again we crossed the trail of a man with a Van Dyke beard. He had been accompanied by a woman whom the druggist described as rather flashily dressed, though her face was hidden under a huge hat and a veil. "Looked very attractive," as the druggist put it, "but she might have been a negress for all I could tell you of her face." "Humph," grunted Kennedy, as we were leaving the store. "You wouldn't believe it, but it is the hardest thing in the world to get an accurate description of any one. The psychologists have said enough about it, but you don't realise it until you are up against it. Why, that might have been the DeMott woman just as well as the former Miss Sanderson, and the man might have been Bolton Brown as well as Dawson, for all we know. They've both disappeared now. I wish we could get some word about that photograph. That would settle it." In the last mail that night Kennedy received back the letter which he had addressed to Michael Dawson. On it was stamped "Returned to sender. Owner not found." Kennedy turned the letter over slowly and looked at the back of it carefully. "On the contrary," he remarked, half to himself, "the owner was found. Only he returned the letter back to the postman after he had opened it and found that it was just a note of no importance which I scribbled just to see if he was keeping in touch with things from his hiding-place, wherever it is." "How do you know he opened it?" I asked. "Do you see those blots on the back? I had several of these envelopes prepared ready for use when I needed them. I had some tannin placed on the flap and then covered thickly with gum. On the envelope itself was some iron sulphate under more gum. I carefully sealed the letter, using very little moisture. The gum then separated the two prepared parts. Now if that letter were steamed open the tannin and the sulphate would come together, run, and leave a smudge. You see the blots? The inference is obvious." Clearly, then, our chase was getting warmer. Dawson had been in Atlantic City at least within a few days. The fruit company steamer to South America on which Carroll believed he was booked to sail under an assumed name and with an assumed face was to sail the following noon. And still we had no word from Chicago as to the destination of the photograph, or the identity of the man in the Van Dyke beard who had been so particular to disarm suspicion in the purchase of the plate from the photographer a few days before. The mail also contained a message from Williams of the Surety Company with the interesting information that Bolton Brown's attorney had refused to say where his client had gone since he had been released on bail, but that he would be produced when wanted. Adele DeMott had not been seen for several days in Chicago and the police there were of the opinion that she had gone to New York, where it would be pretty easy for her to pass unnoticed. These facts further complicated the case and made the finding of the photograph even more imperative. If we were going to do anything it must be done quickly. There was no time to lose. The last of the fast trains for the day had left and the photograph, even though it were found, could not possibly reach us in time to be of use before the steamer sailed from Brooklyn. It was an emergency such as Kennedy had never yet faced, apparently physically insuperable. But, as usual, Craig was not without some resource, though it looked impossible to me to do anything but make a hit or miss arrest at the boat. It was late in the evening when he returned from a conference with an officer of the Telegraph and Telephone Company to whom Williams had given him a card of introduction. The upshot had been that he had called up Chicago and talked for a long time with Professor Clark, a former classmate of ours who was now in the technology school of the university out there. Kennedy and Clark had been in correspondence for some time, I knew, about some technical matters, though I had no idea what it was they concerned. "There's one thing we can always do," I remarked as we walked slowly over to the laboratory from our apartment. "What's that?" he asked absent-mindedly, more from politeness than anything else. "Arrest every one with a Van Dyke beard who goes on the boat to-morrow," I replied. Kennedy smiled. "I don't feel prepared to stand a suit for false arrest," he said simply, "especially as the victim would feel pretty hot if we caused him to miss his boat. Men with beards are not so uncommon, after all." We had reached the laboratory. Linemen were stringing wires under the electric lights of the campus from the street to the Chemistry Building and into Kennedy's sanctum. That night and far into the morning Kennedy was working in the laboratory on a peculiarly complicated piece of mechanism consisting of electromagnets, rolls, and a stylus and numerous other contrivances which did not suggest to my mind anything he had ever used before in our adventures. I killed time as best I could watching him adjust the thing with the most minute care and precision. Finally I came to the conclusion that as I was not likely to be of the least assistance, even if I had been initiated into what was afoot, I had as well retire. "There is one thing you can do for me in the morning, Walter," said Kennedy, continuing to work over a delicate piece of clockwork which formed a part of the apparatus. "In case I do not see you then, get in touch with Williams and Carroll and have them come here about ten o'clock with an automobile. If I am not ready for them then I'm afraid I never shall be, and we shall have to finish the job with the lack of finesse you suggested by arresting all the bearded men." Kennedy could not have slept much during the night, for though his bed had been slept in he was up and away before I could see him again. I made a hurried trip downtown to catch Carroll and Williams and then returned to the laboratory, where Craig had evidently just finished a satisfactory preliminary test of his machine. "Still no message," he began in reply to my unspoken question. He was plainly growing restless with the inaction, though frequent talks over long-distance with Chicago seemed to reassure him. Thanks to the influence of Williams he had at least a direct wire from his laboratory to the city which was now the scene of action. As nearly as I could gather from the one-sided conversations I heard and the remarks which Kennedy dropped, the Chicago post-office inspectors were still searching for a trace of the package from Atlantic City which was to reveal the identity of the man who had passed the bogus checks and sold the forged certificates of stock. Somewhere in that great city was a photograph of the promoter and of the woman who was aiding him to escape, taken in Atlantic City and sent by mail to Chicago. Who had received it? Would it be found in time to be of use? What would it reveal? It was like hunting for a needle in a haystack, and yet the latest reports seemed to encourage Kennedy with the hope that the authorities were at last on the trail of the secret office from which the stock had been sold. He was fuming and wishing that he could be at both ends of the line at once. "Any word from Chicago yet?" appealed an anxious voice from the doorway. We turned. There were Carroll and Williams who had come for us with an automobile to go over to watch at the wharf in Brooklyn for our man. It was Carroll who spoke. The strain of the suspense was telling on him and I could readily imagine that he, like so many others who had never seen Kennedy in action, had not the faith in Craig's ability which I had seen tested so many times. "Not yet," replied Kennedy, still busy about his apparatus on the table. "I suppose you have heard nothing?" "Nothing since my note of last night," returned Williams impatiently. "Our detectives still insist that Bolton Brown is the man to watch, and the disappearance of Adele DeMott at this time certainly looks bad for him." "It does, I admit," said Carroll reluctantly. "What's all this stuff on the table?" he asked, indicating the magnets, rolls, and clockwork. Kennedy did not have time to reply, for the telephone bell was tinkling insistently. "I've got Chicago on the wire," Craig informed us, placing his hand over the transmitter as he waited for long-distance to make the final connection. '"I'll try to repeat as much of the conversation as I can so that you can follow it. Hello--yes--this is Kennedy. Is that you, Clark? It's all arranged at this end. How's your end of the line? Have you a good connection? Yes? My synchroniser is working fine here, too. All right. Suppose we try it. Go ahead." As Kennedy gave a few final touches to the peculiar apparatus on the table, the cylindrical drum before us began slowly to revolve and the stylus or needle pressed down on the sensitised paper with which the drum was covered, apparently with varying intensity as it turned. Round and round the cylinder revolved like a graphophone. "This," exclaimed Kennedy proudly, "is the 'electric eye,' the telelectrograph invented by Thorne Baker in England. Clark and I have been intending to try it out for a long time. It at last makes possible the electric transmission of photographs, using the telephone wires because they are much better for such a purpose than the telegraph wires." Slowly the needle was tracing out a picture on the paper. It was only a thin band yet, but gradually it was widening, though we could not guess what it was about to reveal as the ceaseless revolutions widened the photographic print. "I may say," explained Kennedy as we waited breathlessly, "that another system known as the Korn system of telegraphing pictures has also been in use in London, Paris, Berlin, and other cities at various times for some years. Korn's apparatus depends on the ability of the element selenium to vary the strength of an electric current passing through it in proportion to the brightness with which the selenium is illuminated. A new field has been opened by these inventions which are now becoming more and more numerous, since the Korn system did the pioneering. "The various steps in sending a photograph by the Baker telelectrograph are not so difficult to understand, after all. First an ordinary photograph is taken and a negative made. Then a print is made and a wet plate negative is printed on a sheet of sensitised tinfoil which has been treated with a single-line screen. You know a halftone consists of a photograph through a screen composed of lines running perpendicular to each other--a coarse screen for newspaper work, and a fine screen for better work, such as in magazines. Well, in this case the screen is composed of lines running parallel in one direction only, not crossing at right angles. A halftone is composed of minute points, some light, some dark. This print is composed of long shaded lines, some parts light, others dark, giving the effect of a picture, you understand?" "Yes, yes," I exclaimed, thoroughly excited. "Go on." "Well," he resumed as the print widened visibly, "this tinfoil negative is wrapped around a cylinder at the other end of the line and a stylus with a very delicate, sensitive point begins passing over it, crossing the parallel lines at right angles, like the other lines of a regular halftone. Whenever the point of the stylus passes over one of the lighter spots on the photographic print it sends on a longer electrical vibration, over the darker spots a shorter vibration. The ever changing electrical current passes up through the stylus, vibrates with ever varying degrees of intensity over the thousand miles of telephone wire between Chicago and this instrument here at the other end of the line. "In this receiving apparatus the current causes another stylus to pass over a sheet of sensitised chemical paper such as we have here. The receiving stylus passes over the paper here synchronously with the transmitting stylus in Chicago. The impression which each stroke of the receiving stylus makes on the paper is black or light, according to the length of the very quickly changing vibrations of the electric current. White spots on the photographic print come out as black spots here on the sensitised paper over which this stylus is passing, and vice versa. In that way you can see the positive print growing here before your very eyes as the picture is transmitted from the negative which Clark has prepared and is sending from Chicago." As we bent over eagerly we could indeed now see what the thing was doing. It was reproducing faithfully in New York what could be seen by the mortal eye only in Chicago. "What is it?" asked Williams, still half incredulous in spite of the testimony of his eyes. "It is a photograph which I think may aid us in deciding whether it is Dawson or Brown who is responsible for the forgeries," answered Kennedy, "and it may help us to penetrate the man's disguise yet, before he escapes to South America or wherever he plans to go." "You'll have to hurry," interposed Carroll, nervously looking at his watch. "She sails in an hour and a half and it is a long ride over to the pier even with a fast car." "The print is almost ready," repeated Kennedy calmly. "By the way, it is a photograph which was taken at Atlantic City a few days ago for a booklet which the Lorraine was getting out. The By-Products forger happened to get in it and he bribed the photographer to give him the plate and take another picture for the booklet which would leave him out. The plate was sent to a little office in Chicago, discovered by the post-office inspectors, where the forged stock certificates were sold. I understood from what Clark told me over the telephone before he started to transmit the picture that the woman in it looked very much like Adele DeMott. Let us see." The machine had ceased to revolve. Craig stripped a still wet photograph off the telelectrograph instrument and stood regarding it with intense satisfaction. Outside, the car which had been engaged to hurry us over to Brooklyn waited. "Morphine fiends," said Kennedy as he fanned the print to dry it, "are the most unreliable sort of people. They cover their tracks with almost diabolical cunning. In fact they seem to enjoy it. For instance, the crimes committed by morphinists are usually against property and character and based upon selfishness, not brutal crimes such as alcohol and other drugs induce. Kleptomania, forgery, swindling, are among the most common. "Then, too, one of the most marked phases of morphinism is the pleasure its victims take in concealing their motives and conduct. They have a mania for leading a double life, and enjoy the deception and mask which they draw about themselves. Persons under the influence of the drug have less power to resist physical and mental impressions and they easily succumb to temptations and suggestions from others. Morphine stands unequalled as a perverter of the moral sense. It creates a person whom the father of lies must recognise as kindred to himself. I know of a case where a judge charged a jury that the prisoner, a morphine addict, was mentally irresponsible for that reason. The judge knew what he was talking about. It subsequently developed that he had been a secret morphine fiend himself for years." "Come, come," broke in Carroll impatiently, "we're wasting time. The ship sails in an hour and unless you want to go down the bay on a tug you've got to catch Dawson now or never. The morphine business explains, but it does not excuse. Come on, the car is waiting. How long do you think it will take us to get over to---" "Police headquarters?" interrupted Craig. "About fifteen minutes. This photograph shows, as I had hoped, the real forger. John Carroll, this is a peculiar case. You have forged the name of the president of your company, but you have also traced your own name very cleverly to look like a forgery. It is what is technically known as auto-forgery, forging one's own handwriting. At your convenience we'll ride down to Centre Street directly." Carroll was sputtering and almost frothing at the mouth with rage which he made no effort to suppress. Williams was hesitating, nonplussed, until Kennedy reached over unexpectedly and grasped Carroll by the arm. As he shoved up Carroll's sleeve he disclosed the forearm literally covered with little punctures made by the hypodermic needle. "It may interest you," remarked Kennedy, still holding Carroll in his vise-like grip, while the drug fiend's shattered nerves caused him to cower and tremble, "to know that a special detective working for me has located Mr. and Mrs. Dawson at Bar Harbor, where they are enjoying a quiet honeymoon. Brown is safely in the custody of his counsel, ready to appear and clear himself as soon as the public opinion which has been falsely inflamed against him subsides. Your plan to give us the slip at the last moment at the wharf and board the steamer for South America has miscarried. It is now too late to catch it, but I shall send a wireless that will cause the arrest of Miss DeMott the moment the ship touches an American port at Colon, even if she succeeds in eluding the British authorities at Kingston. The fact is, I don't much care about her, anyway. Thanks to the telelectrograph here we have the real criminal." Kennedy slapped down the now dry print that had come in over his "seeing over a wire" machine. Barring the false Van Dyke beard, it was the face of John Carroll, forger and morphine fiend. Next him in the picture in the brilliant and fashionable dining-room of the Lorraine was sitting Adele DeMott who had used her victim, Bolton Brown, to shield her employer, Carroll. IX THE UNOFFICIAL SPY "Craig, do you see that fellow over by the desk, talking to the night clerk?" I asked Kennedy as we lounged into the lobby of the new Hotel Vanderveer one evening after reclaiming our hats from the plutocrat who had acquired the checking privilege. We had dined on the roof garden of the Vanderveer apropos of nothing at all except our desire to become acquainted with a new hotel. "Yes," replied Kennedy, "what of him?" "He's the house detective, McBride. Would you like to meet him? He's full of good stories, an interesting chap. I met him at a dinner given to the President not long ago and he told me a great yarn about how the secret service, the police, and the hotel combined to guard the President during the dinner. You know, a big hotel is the stamping ground for all sorts of cranks and crooks." The house detective had turned and had caught my eye. Much to my surprise, he advanced to meet me. "Say,--er--er--Jameson," he began, at last recalling my name, though he had seen me only once and then for only a short time. "You're on the Star, I believe?" "Yes," I replied, wondering what he could want. "Well--er--do you suppose you could do the house a little--er--favour?" he asked, hesitating and dropping his voice. "What is it?" I queried, not feeling certain but that it was a veiled attempt to secure a little free advertising for the Vanderveer. "By the way, let me introduce you to my friend Kennedy, McBride." "Craig Kennedy?" he whispered aside, turning quickly to me. I nodded. "Mr. Kennedy," exclaimed the house man deferentially, "are you very busy just now?" "Not especially so," replied Craig. "My friend Jameson was telling me that you knew some interesting yarns about hotel detective life. I should like to hear you tell some of them, if you are not yourself too---" "Perhaps you'd rather see one instead?" interrupted the house detective, eagerly scanning Craig's face. "Indeed, nothing could please me more. What is it--a 'con' man or a hotel 'beat'?" McBride looked about to make sure that no one was listening. "Neither," he whispered. "It's either a suicide or a murder. Come upstairs with me. There isn't a man in the world I would rather have met at this very instant, Mr. Kennedy, than yourself." We followed McBride into an elevator which he stopped at the fifteenth floor. With a nod to the young woman who was the floor clerk, the house detective led the way down the thickly carpeted hall, stopping at a room which, we could see through the transom, was lighted. He drew a bunch of keys from his pocket and inserted a pass key into the lock. The door swung open into a sumptuously fitted sitting-room. I looked in, half fearfully, but, although all the lights were turned on, the room was empty. McBride crossed the room quickly, opened a door to a bedroom, and jerked his head back with a quick motion, signifying his desire for us to follow. Stretched lifeless on the white linen of the immaculate bed lay the form of a woman, a beautiful woman she had been, too, though not with the freshness which makes American women so attractive. There was something artificial about her beauty, the artificiality which hinted at a hidden story of a woman with a past. She was a foreigner, apparently of one of the Latin races, although at the moment in the horror of the tragedy before us I could not guess her nationality. It was enough for me that here lay this cold, stony, rigid beauty, robed in the latest creations of Paris, alone in an elegantly furnished room of an exclusive hotel where hundreds of gay guests were dining and chatting and laughing without a suspicion of the terrible secret only a few feet distant from them. We stood awestruck for the moment. "The coroner ought to be here any moment," remarked McBride and even the callousness of the regular detective was not sufficient to hide the real feelings of the man. His practical sense soon returned, however, and he continued, "Now, Jameson, don't you think you could use a little influence with the newspaper men to keep this thing off the front pages? Of course something has to be printed about it. But we don't want to hoodoo the hotel right at the start. We had a suicide the other day who left an apologetic note that was played up by some of the papers. Now comes this affair. The management are just as anxious to have the crime cleared up as any one--if it is a crime. But can't it be done with the soft pedal? We will stop at nothing in the way of expense--just so long as the name of the Vanderveer is kept in the background. Only, I'm afraid the coroner will try to rub it in and make the thing sensational." "What was her name?" asked Kennedy. "At least, under what name was she registered?" "She was registered as Madame de Nevers. It is not quite a week now since she came here, came directly from the steamer Tripolitania. See, there are her trunks and things, all pasted over with foreign labels, not an American label among them. I haven't the slightest doubt that her name was fictitious, for as far as I can see all the ordinary marks of identification have been obliterated. It will take time to identify her at the best, and in the meantime, if a crime has been committed, the guilty person may escape. What I want now, right away, is action." "Has nothing in her actions about the hotel offered any clue, no matter how slight?" asked Kennedy. "Plenty of things," replied McBride quickly. "For one thing, she didn't speak very much English and her maid seemed to do all the talking for her, even to ordering her meals, which were always served here. I did notice Madame a few times about the hotel, though she spent most of her time in her rooms. She was attractive as the deuce, and the men all looked at her whenever she stirred out. She never even noticed them. But she was evidently expecting some one, for her maid had left word at the desk that if a Mr. Gonzales called, she was at home; if any one else, she was out. For the first day or two she kept herself closely confined, except that at the end of the second day she took a short spin through the park in a taxicab--closed, even in this hot weather. Where she went I cannot say, but when they returned the maid seemed rather agitated. At least she was a few minutes later when she came all the way downstairs to telephone from a booth, instead of using the room telephone. At various times the maid was sent out to execute certain errands, but always returned promptly. Madame de Nevers was a genuine woman of mystery, but as long as she was a quiet mystery, I thought it no business of ours to pry into the affairs of Madame." "Did she have any visitors? Did this Mr. Gonzales call?" asked Kennedy at length. "She had one visitor, a woman who called and asked if a Madame de Nevers was stopping at the hotel," answered McBride. "That was what the clerk was telling me when I happened to catch sight of you. He says that, obedient to the orders from the maid, he told the visitor that Madame was not at home." "Who was this visitor, do you suppose?" asked Craig. "Did she leave any card or message? Is there any clue to her?" The detective looked at him earnestly for a time as if he hesitated to retail what might be merely pure gossip. "The clerk does not know this absolutely, but from his acquaintance with society news and the illustrated papers he is sure that he recognised her. He says that he feels positive that it was Miss Catharine Lovelace." "The Southern heiress," exclaimed Kennedy. "Why, the papers say that she is engaged---" "Exactly," cut in McBride, "the heiress who is rumoured to be engaged to the Duc de Chateaurouge." Kennedy and I exchanged glances. "Yes," I added, recollecting a remark I had heard a few days before from our society reporter on the Star, "I believe it has been said that Chateaurouge is in this country, incognito." "A pretty slender thread on which to hang an identification," McBride hastened to remark. "Newspaper photographs are not the best means of recognising anybody. Whatever there may be in it, the fact remains that Madame de Nevers, supposing that to be her real name, has been dead for at least a day or two. The first thing to be determined is whether this is a death from natural causes, a suicide, or a murder. After we have determined that we shall be in a position to run down this Lovelace clue." Kennedy said nothing and I could not gather whether he placed greater or less value on the suspicion of the hotel clerk. He had been making a casual examination of the body on the bed, and finding nothing he looked intently about the room as if seeking some evidence of how the crime had been committed. To me the thing seemed incomprehensible, that without an outcry being overheard by any of the guests a murder could have been done in a crowded hotel in which the rooms on every side had been occupied and people had been passing through the halls at all hours. Had it indeed been a suicide, in spite of McBride's evident conviction to the contrary? A low exclamation from Kennedy attracted our attention. Caught in the filmy lace folds of the woman's dress he had found a few small and thin pieces of glass. He was regarding them with an interest that was oblivious to everything else. As he turned them over and over and tried to fit them together they seemed to form at least a part of what had once been a hollow globe of very thin glass, perhaps a quarter of an inch or so in diameter. "How was the body discovered?" asked Craig at length, looking up at McBride quickly. "Day before yesterday Madame's maid went to the cashier," repeated the detective slowly as if rehearsing the case as much for his own information as ours, "and said that Madame had asked her to say to him that she was going away for a few days and that under no circumstances was her room to be disturbed in her absence. The maid was commissioned to pay the bill, not only for the time they had been here, but also for the remainder of the week, when Madame would most likely return, if not earlier. The bill was made out and paid. "Since then only the chambermaid has entered this suite. The key to that closet over in the corner was gone, and it might have hidden its secret until the end of the week or perhaps a day or two longer, if the chambermaid hadn't been a bit curious. She hunted till she found another key that fitted, and opened the closet door, apparently to see what Madame had been so particular to lock up in her absence. There lay the body of Madame, fully dressed, wedged into the narrow space and huddled up in a corner. The chambermaid screamed and the secret was out." "And Madame de Nevers's maid? What has become of her?" asked Kennedy eagerly. "She has disappeared," replied McBride. "From the moment when the bill was paid no one about the hotel has seen her." "But you have a pretty good description of her, one that you could send out in order to find her if necessary?" "Yes, I think I could give a pretty good description." Kennedy's eye encountered the curious gaze of McBride. "This may prove to be a most unusual case," he remarked in answer to the implied inquiry of the detective. "I suppose you have heard of the 'endormeurs' of Paris?" McBride shook his head in the negative. "It is a French word signifying a person who puts another to sleep, the sleep makers," explained Kennedy. "They are the latest scientific school of criminals who use the most potent, quickest-acting stupefying drugs. Some of their exploits surpass anything hitherto even imagined by the European police. The American police have been officially warned of the existence of the endormeurs and full descriptions of their methods and photographs of their paraphernalia have been sent over here. "There is nothing in their repertoire so crude as chloral or knock-out drops. All the derivatives of opium such as morphine, codeine, heroine, dionine, narceine, and narcotine, to say nothing of bromure d'etyle, bromoform, nitrite d'amyle, and amyline are known to be utilised by the endormeurs to put their victims to sleep, and the skill which they have acquired in the use of these powerful drugs establishes them as one of the most dangerous groups of criminals in existence. The men are all of superior intelligence and daring; the chief requisite of the women is extreme beauty as well as unscrupulousness. "They will take a little thin glass ball of one of these liquids, for instance, hold it in a pocket handkerchief, crush it, shove it under the nose of their victim, and--whiff!--the victim is unconscious. But ordinarily the endormeur does not kill. He is usually satisfied to stupefy, rob, and then leave his victim. There is something more to this case than a mere suicide or murder, McBride. Of course she may have committed suicide with the drugs of the endormeurs; then again she may merely have been rendered unconscious by those drugs and some other poison may have been administered. Depend on it, there is something more back of this affair than appears on the surface. Even as far as I have gone I do not hesitate to say that we have run across the work of one or perhaps a band of the most up-to-date and scientific criminals." Kennedy had scarcely finished when McBride brought his right fist down with a resounding smack into the palm of his left hand. "Say," he cried in great excitement, "here's another thing which may or may not have some connection with the case. The evening after Madame arrived, I happened to be walking through the cafe, where I saw a face that looked familiar to me. It was that of a dark-haired, olive-skinned man, a fascinating face, but a face to be afraid of. I remembered him, I thought, from my police experience, as a notorious crook who had not been seen in New York for years, a man who in the old days used to gamble with death in South American revolutions, a soldier of fortune. "Well, I gave the waiter, Charley, the wink and he met me in the rear of the cafe, around a corner. You know we have a regular system in the hotel by which I can turn all the help into amateur sleuths. I told him to be very careful about the dark-faced man and the younger man who was with him, to be particular to wait on them well, and to pick up any scraps of conversation he could. "Charley knows his business, and the barest perceptible sign from me makes him an obsequious waiter. Of course the dark man didn't notice it at the time, but if he had been more observant he would have seen that three times during his chat with his companion Charley had wiped off his table with lingering hand. Twice he had put fresh seltzer in his drink. Like a good waiter always working for a big tip he had hovered near, his face blank and his eyes unobservant. But that waiter was an important link in my chain of protection of the hotel against crooks. He was there to listen and to tip me off, which he did between orders. "There wasn't much that he overheard, but what there was of it was so suspicious that I did not hesitate to conclude that the fellow was an undesirable guest. It was something about the Panama Canal, and a coaling station of a steamship and fruit concern on the shore of one of the Latin American countries. It was, he said, in reality to be the coaling station of a certain European power which he did not name but which the younger man seemed to understand. They talked of wharves and tracts of land, of sovereignty and blue prints, the Monroe Doctrine, value in case of war, and a lot of other things. Then they talked of money, and though Charley was most assiduous at the time all he overheard was something about 'ten thousand francs' and 'buying her off,' and finally a whispered confidence of which he caught the words, 'just a blind to get her over here, away from Paris.' Finally the dark man in an apparent burst of confidence said something about 'the other plans being the real thing after all,' and that the whole affair would bring him in fifty thousand francs, with which he could afford to be liberal. Charley could get no inkling about what that other thing was. "But I felt sure that he had heard enough to warrant the belief that some kind of confidence game was being discussed. To tell the truth I didn't care much what it was, at the time. It might have been an attempt of the dark-visaged fellow to sell the Canal to a come-on. What I wanted was to have it known that the Vanderveer was not to be a resort of such gentry as this. But I'm afraid it was much more serious than I thought at the time. "Well, the dark man finally excused himself and sauntered into the lobby and up to the desk, with me after him around the opposite way. He was looking over the day's arrivals on the register when I concluded that it was about time to do something. I was standing directly beside him lighting a cigar. I turned quickly on him and deliberately trod on the man's patent leather shoe. He faced me furiously at not getting any apology. 'Sacre,' he exclaimed, 'what the--' But before he could finish I moved still closer and pinched his elbow. A dull red glow of suppressed anger spread over his face, but he cut his words short. He knew and I knew he knew. That is the sign in the continental hotels when they find a crook and quietly ask him to move on. The man turned on his heel and stalked out of the hotel. By and by the young man in the cafe, considerably annoyed at the sudden inattention of the waiter who acted as if he wasn't satisfied with his tip, strolled through the lobby and not seeing his dark-skinned friend, also disappeared. I wish to heaven I had had them shadowed. The young fellow wasn't a come-on at all. There was something afoot between these two, mark my words." "But why do you connect that incident with this case of Madame de Nevers?" asked Kennedy, a little puzzled. "Because the next day, and the day that Madame's maid disappeared, I happened to see a man bidding good-bye to a woman at the rear carriage entrance of the hotel. The woman was Madame's maid and the man was the dark man who had been seated in the cafe." "You said a moment ago that you had a good description of the maid or could write one. Do you think you could locate her?" The hotel detective thought a minute or two. "If she has gone to any of the other hotels in this city, I could," he answered slowly. "You know we have recently formed a sort of clearing house, we hotel detectives, and we are working together now very well, though secretly. It is barely possible that she has gone to another hotel. The very brazenness of that would be its safeguard, she might think." "Then I can leave that part of it to you, McBride?" asked Kennedy thoughtfully as if laying out a programme of action in his mind. "You will set the hotel detectives on the trail as well as the police of the city, and of other cities, will make the inquiries at the steamships and railroads, and all that sort of thing? Try to find some trace of the two men whom you saw in the cafe at the same time. But for the present I should say spare no effort to locate that girl." "Trust it to me," agreed McBride confidently. A heavy tap sounded at the door and McBride opened it. It was the coroner. I shall not go into the lengthy investigation which the coroner conducted, questioning one servant and employee after another without eliciting any more real information than we had already obtained so concisely from the house man. The coroner was, of course, angry at the removal of the body from the closet to the bed because he wanted to view it in the position in which it had been found, but as that had been done by the servants before McBride could stop them, there was nothing to do about it but accept the facts. "A very peculiar case," remarked the coroner at the conclusion of his examination, with the air of a man who could shed much light on it from his wide experience if he chose. "There is just one point that we shall have to clear up, however. What was the cause of the death of the deceased? There is no gas in the room. It couldn't have been illuminating gas, then. No, it must have been a poison of some kind. Then as to the motive," he added, trying to look confident but really shooting a tentative remark at Craig and the house detective, who said nothing. "It looks a good deal like that other suicide--at least a suicide which some one has endeavoured to conceal," he added, hastily recollecting the manner in which the body had been found and his criticisms of the removal from the closet. "Didn't I tell you?" rejoined McBride dolefully after we had left the coroner downstairs a few minutes later. "I knew he would think the hotel was hiding something from him." "We can't help what he thinks--yet," remarked Craig. "All we can do is to run down the clues which we have. I will leave the maid to be found by your organisation, McBride. Let me see, the theatres and roof gardens must be letting out by this time. I will see if I can get any information from Miss Lovelace. Find her address, Walter, and call a cab." The Southern heiress, who had attracted more attention by her beauty than by her fortune which was only moderate as American fortunes go nowadays, lived in an apartment facing the park, with her mother, a woman whose social ambitions it was commonly known had no bounds and were often sadly imposed upon. Fortunately we arrived at the apartment not very many minutes after the mother and daughter, and although it was late, Kennedy sent up his card with an urgent message to see them. They received us in a large drawing-room and were plainly annoyed by our visit, though that of course was susceptible of a natural interpretation. "What is it that you wished to see me about?" began Mrs. Lovelace in a tone which was intended to close the interview almost before it was begun. Kennedy had not wished to see her about anything, but of course he did not even hint as much in his reply which was made to her but directed at Miss Lovelace. "Could you tell me anything about a Madame de Nevers who was staying at the Vanderveer?" asked Craig, turning quickly to the daughter so as to catch the full effect of his question, and then waiting as if expecting the answer from her. The young lady's face blanched slightly and she seemed to catch her breath for an instant, but she kept her composure admirably in spite of the evident shock of Craig's purposely abrupt question. "I have heard of her," Miss Lovelace replied with forced calmness as he continued to look to her for an answer. "Why do you ask?" "Because a woman who is supposed to be Madame de Nevers has committed suicide at the Vanderveer and it was thought that perhaps you could identify her." By this time she had become perfect mistress of herself again, from which I argued that whatever knowledge she had of Madame was limited to the time before the tragedy. "I, identify her? Why, I never saw her. I simply know that such a creature exists." She said it defiantly and with an iciness which showed more plainly than in mere words that she scorned even an acquaintance with a demi-mondaine. "Do you suppose the Duc de Chateaurouge would be able to identify her?" asked Kennedy mercilessly. "One moment, please," he added, anticipating the blank look of amazement on her face. "I have reason to believe that the duke is in this country incognito--is he not?" Instead of speaking she merely raised her shoulders a fraction of an inch. "Either in New York or in Washington," pursued Kennedy. "Why do you ask me?" she said at length. "Isn't it enough that some of the newspapers have said so? If you see it in the newspapers, it's so--perhaps--isn't it?" We were getting nowhere in this interview, at least so I thought. Kennedy cut it short, especially as he noted the evident restlessness of Mrs. Lovelace. However, he had gained his point. Whether or not the duke was in New York or Washington or Spitzbergen, he now felt sure that Miss Lovelace knew of, and perhaps something about, Madame de Nevers. In some way the dead woman had communicated with her and Miss Lovelace had been the woman whom the hotel clerk had seen at the Vanderveer. We withdrew as gracefully as our awkward position permitted. As there was nothing else to be done at that late hour, Craig decided to sleep soundly over the case, his infallible method of taking a fresh start after he had run up a cul-de-sac. Imagine our surprise in the morning at being waited on by the coroner himself, who in a few words explained that he was far from satisfied with the progress his own office was making with the case. "You understand," he concluded after a lengthy statement of confession and avoidance, "we have no very good laboratory facilities of our own to carry out the necessary chemical, pathological, and bacteriological investigations in cases of homicide and suicide. We are often forced to resort to private laboratories, as you know in the past when I have had to appeal to you. Now, Professor Kennedy, if we might turn over that research part of the case to you, sir, I will engage to see that a reasonable bill for your professional services goes through the office of my friend the city comptroller promptly." Craig snapped at the opportunity, though he did not allow the coroner to gain that impression. "Very well," agreed that official, "I shall see that all the necessary organs for a thorough test as to the cause of the death of this woman are sent up to the Chemistry Building right away." The coroner was as good as his word, and we had scarcely breakfasted and arrived at Craig's scientific workshop before that official appeared, accompanied by a man who carried in uncanny jars the necessary materials for an investigation following an autopsy. Kennedy was now in his element. The case had taken an unexpected turn which made him a leading factor in its solution. Whatever suspicions he may have entertained unofficially the night before he could now openly and quickly verify. He took a little piece of lung tissue and with a sharp sterilised knife cut it up. Then he made it slightly alkaline with a little sodium carbonate, talking half to us and half to himself as he worked. The next step was to place the matter in a glass flask in a water bath where it was heated. From the flask a Bohemian glass tube led into a cool jar and on a part of the tube a flame was playing which heated it to redness for two or three inches. Several minutes we waited in silence. Finally when the process had gone far enough, Kennedy took a piece of paper which had been treated with iodised starch, as he later explained. He plunged the paper into the cool jar. Slowly it turned a strong blue tint. Craig said nothing, but it was evident that he was more than gratified by what had happened. He quickly reached for a bottle on the shelves before him, and I could see from the label on the brown glass that it was nitrate of silver. As he plunged a little in a test-tube into the jar a strong precipitate was gradually formed. "It is the decided reaction for chloroform," he exclaimed simply in reply to our unspoken questions. "Chloroform," repeated the coroner, rather doubtfully, and it was evident that he had expected a poison and had not anticipated any result whatever from an examination of the lungs instead of the stomach to which he had confined his own work so far. "Could chloroform be discovered in the lungs or viscera after so many days? There was one famous chloroform case for which a man is now serving a life term in Sing Sing which I have understood there was grave doubt in the minds of the experts. Mind, I am not trying to question the results of your work except as they might naturally be questioned in court. It seems to me that the volatility of chloroform might very possibly preclude its discovery after a short time. Then again, might not other substances be generated in a dead body which would give a reaction very much like chloroform? We must consider all these questions before we abandon the poison theory, sir. Remember, this is the summer time too, and chloroform would evaporate very much more rapidly now than in winter." Kennedy smiled, but his confidence remained unshaken. "I am in a position to meet all of your objections," he explained simply. "I think I could lay it down as a rule that by proper methods chloroform may be discovered in the viscera much longer after death than is commonly supposed--in summer from six days to three weeks, with a practical working range of say twelve days, while in winter it may be found even after several months--by the right method. Certainly this case comes within the average length of time. More than that, no substance is generated by the process of decomposition which will vitiate the test for chloroform which I have just made. Chloroform has an affinity for water and is also a preservative, and hence from all these facts I think it safe to conclude that sometimes traces of it may be found for two weeks after its administration, certainly for a few days." "And Madame de Nevers?" queried the coroner, as if the turn of events was necessitating a complete reconstruction of his theory of the case. "Was murdered," completed Kennedy in a tone that left nothing more to be said on the subject. "But," persisted the coroner, "if she was murdered by the use of chloroform, how do you account for the fact that it was done without a struggle? There were no marks of violence and I, for one, do not believe that under ordinary circumstances any one will passively submit to such an administration without a hard fight." From his pocket Kennedy drew a small pasteboard box filled with tiny globes, some bonbons and lozenges, a small hypodermic syringe, and a few cigars and cigarettes. He held it out in the palm of his hand so that we could see it. "This," he remarked, "is the standard equipment of the endormeur. Whoever obtained admittance to Madame's rooms, either as a matter of course or secretly, must have engaged her in conversation, disarmed suspicion, and then suddenly she must have found a pocket handkerchief under her nose. The criminal crushed a globe of liquid in the handkerchief, the victim lost consciousness, the chloroform was administered without a struggle, all marks of identification were obliterated, the body was placed in the closet, and the maid--either as principal or accessory--took the most likely means of postponing discovery by paying the bill in advance at the office, and then disappeared." Kennedy slipped the box back into his pocket. The coroner had, I think, been expecting Craig's verdict, although he was loath to abandon his own suicide theory and had held it to the last possible moment. At any rate, so far he had said little, apparently preferring to keep his own counsel as to his course of action and to set his own machinery in motion. He drew a note from his pocket, however. "I suppose," he began tentatively, shaking the note as he glanced doubtfully from it to us, "that you have heard that among the callers on this unfortunate woman was a lady of high social position in this city?" "I have heard a rumour to that effect," replied Kennedy as he busied himself cleaning up the apparatus he had just used. There was nothing in his manner even to hint at the fact that we had gone further and interviewed the young lady in question. "Well," resumed the coroner, "in view of what you have just discovered I don't mind telling you that I believe it was more than a rumour. I have had a man watching the woman and this is a report I received just before I came up here." We read the note which he now handed to us. It was just a hasty line: "Miss Lovelace left hurriedly for Washington this morning." What was the meaning of it? Clearly, as we probed deeper into the case, its ramifications grew wider than anything we had yet expected. Why had Miss Lovelace gone to Washington, of all places, at this torrid season of the year? The coroner had scarcely left us, more mystified than ever, when a telephone message came from McBride saying that he had some important news for us if we would meet him at the St. Cenis Hotel within an hour. He would say nothing about it over the wire. As Kennedy hung up the receiver he quietly took a pistol from a drawer of his desk, broke it quickly, and looked thoughtfully at the cartridges in the cylinder. Then he snapped it shut and stuck it into his pocket. "There's no telling what we may run up against before we get back to the laboratory," he remarked and we rode down to meet McBride. The description which the house man had sent out to the other hotel detectives the night before had already produced a result. Within the past two days a man answering the description of the younger man whom McBride had seen in the cafe and a woman who might very possibly have been Madame's maid had come to the St. Cenis as M. and Mme. Duval. Their baggage was light, but they had been at pains to impress upon the hotel that they were persons of some position and that it was going direct from the railroad to the steamer, after their tour of America. They had, as a matter of fact, done nothing to excite suspicion until the general request for information had been received. The house man of the St. Cenis welcomed us cordially upon McBride's introduction and agreed to take us up to the rooms of the strange couple if they were not in. As it happened it was the lunch hour and they were not in the room. Still, Kennedy dared not be too particular in his search of their effects, for he did not wish to arouse suspicion upon their return, at least not yet. "It seems to me, Craig," I suggested after we had nosed about for a few minutes, finding nothing, "that this is pre-eminently a case in which to use the dictograph as you did in that Black Hand case." He shook his head doubtfully, although I could see that the idea appealed to him. "The dictograph has been getting too much publicity lately," he said. "I'm afraid they would discover it, that is, if they are at all the clever people I think them. Besides, I would have to send up to the laboratory to get one and by the time the messenger returned they might be back from lunch. No, we've got to do something else, and do it quickly." He was looking about the room in an apparently aimless manner. On the side wall hung a cheap etching of a woodland scene. Kennedy seemed engrossed in it while the rest of us fidgeted at the delay. "Can you get me a couple of old telephone instruments?" he asked at length, turning to us and addressing the St. Cenis detective. The detective nodded and disappeared down the hall. A few minutes later he deposited the instruments on a table. Where he got them I do not know, but I suspect he simply lifted them from vacant rooms. "Now some Number 30 copper wire and a couple of dry cells," ordered Kennedy, falling to work immediately on the telephones. The detective despatched a bellboy down to the basement to get the wire from the house electrician. Kennedy removed the transmitters of the telephones, and taking the carbon capsules from them placed the capsules on the table carefully. Then he lifted down the etching from the wall and laid it flat on its face before us. Quickly he removed the back of the picture. Pressing the transmitter fronts with the carbon capsules against the paper and the glass on the picture he mounted them so that the paper and glass acted as a large diaphragm to collect all the sounds in the room. "The size of this glass diaphragm," he explained as we gathered around in intense interest at what he was doing, "will produce a strikingly sensitive microphone action and the merest whisper will be reproduced with startling distinctness." The boy brought the wire up and also the news that the couple in whose room we were had very nearly finished luncheon and might be expected back in a few minutes. Kennedy took the tiny wires, and after connecting them hung up the picture again and ran them up alongside the picture wires leading from the huge transmitter up to the picture moulding. Along the top of the moulding and out through the transom it was easy enough to run the wires and so down the hall to a vacant room, where Craig attached them quickly to one of the old telephone receivers. Then we sat down in this room to await developments from our hastily improvised picture frame microphone detective. At last we could hear the elevator door close on our floor. A moment later it was evident from the expression of Kennedy's face that some one had entered the room which we had just left. He had finished not a moment too soon. "It's a good thing that I didn't wait to put a dictograph there," he remarked to us. "I thought I wasn't reckoning without reason. The couple, whoever they are, are talking in undertones and looking about the room to see if anything has been disturbed in their absence." Kennedy alone, of course, could follow over his end of the telephone what they said. The rest of us could do nothing but wait, but from notes which Craig jotted down as he listened to the conversation I shall reproduce it as if we had all heard it. There were some anxious moments until at last they had satisfied themselves that no one was listening and that no dictograph or other mechanical eavesdropper, such as they had heard of, was concealed in the furniture or back of it. "Why are you so particular, Henri?" a woman's voice was saying. "Louise, I've been thinking for a long time that we are surrounded by spies in these hotels. You remember I told you what happened at the Vanderveer the night you and Madame arrived? I'm sure that waiter overheard what Gonzales and I were talking about." "Well, we are safe now anyhow. What was it that you would not tell me just now at luncheon?" asked the woman, whom Kennedy recognised as Madame de Nevers's maid. "I have a cipher from Washington. Wait until I translate it." There was a pause. "What does it say?" asked the woman impatiently. "It says," repeated the man slowly, "that Miss Lovelace has gone to Washington. She insists on knowing whether the death of Marie was a suicide or not. Worse than that the Secret Service must have wind of some part of our scheme, for they are acting suspiciously. I must go down there or the whole affair may be exposed and fall through. Things could hardly be worse, especially this sudden move on her part." "Who was that detective who forced his way to see her the night they discovered Marie's body?" asked the woman. "I hope that that wasn't the Secret Service also. Do you think they could have suspected anything?" "I hardly think so," the man replied. "Beyond the death of Madame they suspect nothing here in New York, I am convinced. You are sure that all her letters were secured, that all clues to connect her with the business in hand were destroyed, and particularly that the package she was to deliver is safe?" "The package? You mean the plans for the coaling station on the Pacific near the Canal? You see, Henri, I know." "Ha, ha,--yes," replied the man. "Louise, shall I tell you a secret? Can you keep it?" "You know I can, Henri." "Well, Louise, the scheme is deeper than even you think. We are playing one country against another, America against--you know the government our friend Schmidt works for in Paris. Now, listen. Those plans of the coaling station are a fake--a fake. It is just a commercial venture. No nation would be foolish enough to attempt such a thing, yet. We know that they are a fake. But we are going to sell them through that friend of ours in the United States War Department. But that is only part of the coup, the part that will give us the money to turn the much larger coups we have in the future. You can understand why it has all to be done so secretly and how vexatious it is that as soon as one obstacle is overcome a dozen new ones appear. Louise, here is the big secret. By using those fake plans as a bait we are going to obtain something which when we all return to Paris we can convert into thousands of francs. There, I can say no more. But I have told you so much to impress upon you the extreme need of caution." "And how much does Miss Lovelace know?" "Very little--I hope. That is why I must go to Washington myself. She must know nothing of this coup nor of the real de Nevers, or the whole scheme may fall through. It would have fallen through before, Louise, if you had failed us and had let any of de Nevers's letters slip through to Miss Lovelace. She richly deserved her fate for that act of treachery. The affair would have been so simple, otherwise. Luck was with us until her insane jealousy led her to visit Miss Lovelace. It was fortunate the young lady was out when Madame called on her or all would have been lost. Ah, we owe you a great deal, Louise, and we shall not forget it, never. You will be very careful while I am gone?" "Absolutely. When will you return to me, Henri?" "To-morrow morning at the latest. This afternoon the false coaling station plans are to be turned over to our accomplice in the War Department and in exchange he is to give us something else--the secret of which I spoke. You see the trail leads up into high circles. It is very much more important than you suppose and discovery might lead to a dangerous international complication just now." "Then you are to meet your friend in Washington to-night? When do you start, Henri? Don't let the time slip by. There must be no mistake this time as there was when we were working for Japan and almost had the blue prints of Corregidor at Manila only to lose them on the streets of Calcutta." "Trust me. We are to meet about nine o'clock and therefore I leave on the limited at three-thirty, in about an hour. From the station I am going straight to the house on Z Street--let me see, the cipher says the number is 101--and ask for a man named Gonzales. I shall use the name Montez. He is to appear, hand over the package--that thing I have told you about--then I am to return here by one of the midnight trains. At any cost we must allow nothing to happen which will reach the ears of Miss Lovelace. I'll see you early to-morrow morning, ma cherie, and remember, be ready, for the Aquitania sails at ten. The division of the money is to be made in Paris. Then we shall all go our separate ways." Kennedy was telephoning frantically through the regular hotel service to find out how the trains ran for Washington. The only one that would get there before nine was the three-thirty; the next, leaving an hour later, did not arrive until nearly eleven. He had evidently had some idea of causing some delay that would result in our friend down the hall missing the limited, but abandoned it. Any such scheme would simply result in a message to the gang in Washington putting them on their guard and defeating his purpose. "At all costs we must beat this fellow to it," exclaimed Craig, waiting to hear no more over his improvised dictograph. "Come, Walter, we must catch the limited for Washington immediately. McBride, I leave you and the regular house man to shadow this woman. Don't let her get out of your sight for a moment." As we rode across the city to the new railroad terminus Craig hastily informed me of what he had overheard. We took up our post so that we could see the outgoing travellers, and a few minutes later Craig spotted our man from McBride's description, and succeeded in securing chairs in the same car in which he was to ride. Taken altogether it was an uneventful journey. For five mortal hours we sat in the Pullman or toyed with food in the dining-car, never letting the man escape our sight, yet never letting him know that we were watching him. Nevertheless I could not help asking myself what good it did. Why did not Kennedy hire a special if the affair was so important as it appeared? How were we to get ahead of him in Washington better than in New York? I knew that some plan lurked behind the calm and inscrutable face of Kennedy as I tried to read and could not. The train had come to a stop in the Union Station. Our man was walking rapidly up the platform in the direction of the cab stand. Suddenly Kennedy darted ahead and for a moment we were walking abreast of him. "I beg your pardon," began Craig as we came to a turn in the shadow of the arc lights, "but have you a match?" The man halted and fumbled for his match-box. Instantly Kennedy's pocket handkerchief was at his nose. "Some of the medicine of your own gang of endormeurs," ground out Kennedy, crushing several of the little glass globes under his handkerchief to make doubly sure of their effect. The man reeled and would have fallen if we had not caught him between us. Up the platform we led him in a daze. "Here," shouted Craig to a cabman, "my friend is ill. Drive us around a bit. It will sober him up. Come on, Walter, jump in, the air will do us all good." Those who were in Washington during that summer will remember the suppressed activity in the State, War, and Navy Departments on a certain very humid night. Nothing leaked out at the time as to the cause, but it was understood later that a crisis was narrowly averted at a very inopportune season, for the heads of the departments were all away, the President was at his summer home in the North, and even some of the under-secretaries were out of town. Hasty messages had been sizzling over the wires in cipher and code for hours. I recall that as we rode a little out of our way past the Army Building, merely to see if there was any excitement, we found it a blaze of lights. Something was plainly afoot even at this usually dull period of the year. There was treachery of some kind and some trusted employee was involved, I felt instinctively. As for Craig he merely glanced at the insensible figure between us and remarked sententiously that to his knowledge there was only one nation that made a practice of carrying out its diplomatic and other coups in the hot weather, a remark which I understood to mean that our mission was more than commonly important. The man had not recovered when we arrived within several blocks of our destination, nor did he show signs of recovery from his profound stupor. Kennedy stopped the cab in a side street, pressed a bill into the cabman's hand, and bade him wait until we returned. We had turned the corner of Z Street and were approaching the house when a man walking in the opposite direction eyed us suspiciously, turned, and followed us a step or two. "Kennedy!" he exclaimed. If a fourteen-inch gun had exploded behind us I could not have been more startled. Here, in spite of all our haste and secrecy we were followed, watched, and beaten. Craig wheeled about suddenly. Then he took the man by the arm. "Come," he said quickly, and we three dove into the shadow of an alley. As we paused, Kennedy was the first to speak. "By Jove, Walter, it's Burke of the Secret Service," he exclaimed. "Good," repeated the man with some satisfaction. "I see that you still have that memory for faces." He was evidently referring to our experiences together some months before with the portrait parle and identification in the counterfeiting case which Craig cleared up for him. For a moment or two Burke and Kennedy spoke in whispers. Under the dim light from the street I could see Kennedy's face intent and working with excitement. "No wonder the War Department is a blaze of lights," he exclaimed as we moved out of the shadow again, leaving the Secret Service man. "Burke, I had no idea when I took up this case that I should be doing my country a service also. We must succeed at any hazard. The moment you hear a pistol shot, Burke, we shall need you. Force the door if it is not already open. You were right as to the street but not the number. It is that house over there. Come on, Walter." We mounted the low steps of the house and a negress answered the bell. "Is Mr. Gonzales in?" asked Kennedy. The hallway into which we were admitted was dark but it opened into a sitting-room, where a dim light was burning behind the thick portieres. Without a word the negress ushered us into this room, which was otherwise empty. "Tell him Mr. Montez is here," added Craig as we sat down. The negress disappeared upstairs, and in a few minutes returned with the message that he would be down directly. No sooner had the shuffle of her footsteps died away than Kennedy was on his feet, listening intently at the door. There was no sound. He took a chair and tiptoed out into the dark hall with it. Turning it upside down he placed it at the foot of the stairs with the four legs pointing obliquely up. Then he drew me into a corner with him. How long we waited I cannot say. The next I knew was a muffled step on the landing above, then the tread on the stairs. A crash and a deep volley of oaths in French followed as the man pitched headlong over the chair on the dark steps. Kennedy whipped out his revolver and fired pointblank at the prostrate figure. I do not know what the ethics are of firing on a man when he is down, nor did I have time to stop to think. Craig grasped my arm and pulled me toward the door. A sickening odour seemed to pervade the air. Upstairs there was shouting and banging of doors. "Closer, Walter," he muttered, "closer to the door, and open it a little, or we shall both be suffocated. It was the Secret Service gun I shot off--the pistol that shoots stupefying gas from its vapour-filled cartridges and enables you to put a criminal out of commission without killing him. A pull of the trigger, the cap explodes, the gunpowder and the force of the explosion unite some capsicum and lycopodium, producing the blinding, suffocating vapour whose terrible effect you see. Here, you upstairs," he shouted, "advance an inch or so much as show your heads over the rail and I pump a shot at you, too. Walter, take the gun yourself. Fire at a move from them. I think the gases have cleared away enough now. I must get him before he recovers consciousness." A tap at the door came, and without taking my eyes off the stairs I opened it. Burke slid in and gulped at the nauseous atmosphere. "What's up?" he gasped. "I heard a shot. Where's Kennedy?" I motioned in the darkness. Kennedy's electric bull's-eye flashed up at that instant and we saw him deftly slip a bright pair of manacles on the wrists of the man on the floor, who was breathing heavily, while blood flowed from a few slight cuts due to his fall. Dexterously as a pickpocket Craig reached into the man's coat, pulled out a packet of papers, and gazed eagerly at one after another. From among them he unfolded one written in French to Madame Marie de Nevers some weeks before. I translate: DEAR MARIE: Herr Schmidt informs me that his agent in the War Department at Washington, U. S. A., has secured some important information which will interest the Government for which Herr Schmidt is the agent--of course you know who that is. It is necessary that you should carry the packet which will be handed to you (if you agree to my proposal) to New York by the steamer Tripolitania. Go to the Vandeveer Hotel and in a few days, as soon as a certain exchange can be made, either our friend in Washington or myself will call on you, using the name Gonzales. In return for the package which you carry he will hand you another. Lose no time in bringing the second package back to Paris. I have arranged that you will receive ten thousand francs and your expenses for your services in this matter. Under no conditions betray your connection with Herr Schmidt. I was to have carried the packet to America myself and make the exchange but knowing your need of money I have secured the work for you. You had better take your maid, as it is much better to travel with distinction in this case. If, however, you accept this commission I shall consider you in honour bound to surrender your claim upon my name for which I agree to pay you fifty thousand francs upon my marriage with the American heiress of whom you know. Please let me know immediately through our mutual friend Henri Duval whether this proposal is satisfactory. Henri will tell you that fifty thousand is my ultimatum, CHATEAUROUGE. "The scoundrel," ground out Kennedy. "He lured his wife from Paris to New York, thinking the Paris police too acute for him, I suppose. Then by means of the treachery of the maid Louise and his friend Duval, a crook who would even descend to play the part of valet for him and fall in love with the maid, he has succeeded in removing the woman who stood between him and an American fortune." "Marie," rambled Chateaurouge as he came blinking, sneezing, and choking out of his stupor, "Marie, you are clever, but not too clever for me. This blackmailing must stop. Miss Lovelace knows something, thanks to you, but she shall never know all--never--never. You--you--ugh!--Stop. Do you think you can hold me back now with those little white hands on my wrists? I wrench them loose--so--and--ugh!--What's this? Where am I?" The man gazed dazedly at the manacles that held his wrists instead of the delicate hands he had been dreaming of as he lived over the terrible scene of his struggle with the woman who was his wife in the Vanderveer. "Chateaurouge," almost hissed Kennedy in his righteous wrath, "fake nobleman, real swindler of five continents. Marie de Nevers alive stood in the way of your marriage to the heiress Miss Lovelace. Dead, she prevents it absolutely." Craig continued to turn over the papers in his hand, as he spoke. At last he came to a smaller packet in oiled silk. As he broke the seal he glanced at it in surprise, then hurriedly exclaimed, "There, Burke. Take these to the War Department and tell them they can turn out their lights and stop their telegrams. This seems to be a copy of our government's plans for the fortification of the Panama Canal, heights of guns, location of searchlights, fire control stations, everything from painstaking search of official and confidential records. That is what this fellow obtained in exchange for his false blue prints of the supposed coaling station on the Pacific. "I leave the Secret Service to find the leak in the War Department. What I am interested in is not the man who played spy for two nations and betrayed one of them. To me this adventurer who calls himself Chateaurouge is merely the murderer of Madame de Nevers." X THE SMUGGLER It was a rather sultry afternoon in the late summer when people who had calculated by the calendar rather than by the weather were returning to the city from the seashore, the mountains, and abroad. Except for the week-ends, Kennedy and I had been pretty busy, though on this particular day there was a lull in the succession of cases which had demanded our urgent attention during the summer. We had met at the Public Library, where Craig was doing some special research at odd moments in criminology. Fifth Avenue was still half deserted, though the few pedestrians who had returned or remained in town like ourselves were, as usual, to be found mostly on the west side of the street. Nearly everybody, I have noticed, walks on the one side of Fifth Avenue, winter or summer. As we stood on the corner waiting for the traffic man's whistle to halt the crush of automobiles, a man on the top of a 'bus waved to Kennedy. I looked up and caught a glimpse of Jack Herndon, an old college mate, who had had some political aspirations and had recently been appointed to a position in the customs house of New York. Herndon, I may add, represented the younger and clean-cut generation which is entering official life with great advantage to both themselves and politics. The 'bus pulled up to the curb, and Jack tore down the breakneck steps hurriedly. "I was just thinking of you, Craig," he beamed as we all shook hands, "and wondering whether you and Walter were in town. I think I should have come up to see you to-night, anyhow." "Why, what's the matter--more sugar frauds?" laughed Kennedy. "Or perhaps you have caught another art dealer red-handed?" "No, not exactly," replied Herndon, growing graver for the moment. "We're having a big shake-up down at the office, none of your 'new broom' business, either. Real reform it is, this time." "And you--are you going or coming?" inquired Craig with an interested twinkle. "Coming, Craig, coming," answered Jack enthusiastically. "They've put me in charge of a sort of detective force as a special deputy surveyor to rout out some smuggling that we know is going on. If I make good it will go a long way for me--with all this talk of efficiency and economy down in Washington these days." "What's on your mind now?" asked Kennedy observantly. "Can I help you in any way?" Herndon had taken each of us by an arm and walked us over to a stone bench in the shade of the library building. "You have read the accounts in the afternoon papers of the peculiar death of Mademoiselle Violette, the little French modiste, up here on Forty-sixth Street?" he inquired. "Yes," answered Kennedy. "What has that to do with customs reform?" "A good deal, I fear," Herndon continued. "It's part of a case that has been bothering us all summer. It's the first really big thing I've been up against and it's as ticklish a bit of business as even a veteran treasury agent could wish." Herndon looked thoughtfully at the passing crowd on the other side of the balustrade and continued. "It started, like many of our cases, with the anonymous letter writer. Early in the summer the letters began to come in to the deputy surveyor's office, all unsigned, though quite evidently written in a woman's hand, disguised of course, and on rather dainty notepaper. They warned us of a big plot to smuggle gowns and jewellery from Paris. Smuggling jewellery is pretty common because jewels take up little space and are very valuable. Perhaps it doesn't sound to you like a big thing to smuggle dresses, but when you realise that one of those filmy lacy creations may often be worth several hundred, if not thousand, dollars, and that it needs only a few of them on each ship that comes in to run up into the thousands, perhaps hundreds of thousands in a season, you will see how essential it is to break up that sort of thing. We've been getting after the individual private smugglers pretty sharply this summer and we've had lots of criticism. If we could land a big fellow and make an object-lesson of the extent of the thing I believe it would leave our critics of the press without a leg to stand on. "At least that was why I was interested in the letters. But it was not until a few days ago that we got a tip that gave us a real working clue, for the anonymous letters had been very vague as to names, dates, and places, though bold enough as to general charges, as if the writer were fearful of incriminating herself--or himself. Strange to say, this new clue came from the wife of one of the customs men. She happened to be in a Broadway manicure shop one day when she heard a woman talking with the manicurist about fall styles, and she was all attention when she heard the customer say, 'You remember Mademoiselle Violette's--that place that had the exquisite things straight from Paris, and so cheaply, too? Well, Violette says she'll have to raise her prices so that they will be nearly as high as the regular stores. She says the tariff has gone up, or something, but it hasn't, has it?' "The manicurist laughed knowingly, and the next remark caught the woman's attention. 'No, indeed. But then, I guess she meant that she had to pay the duty now. You know they are getting much stricter. To tell the truth, I imagine most of Violette's goods were--well--' "'Smuggled?' supplied the customer in an undertone. "The manicurist gave a slight shrug of the shoulders and a bright little yes of a laugh. "That was all. But it was enough. I set a special customs officer to watch Mademoiselle, a clever fellow. He didn't have time to find out much, but on the other hand I am sure he didn't do anything to alarm Mademoiselle. That would have been a bad game. His case was progressing favourably and he had become acquainted with one of the girls who worked in the shop. We might have got some evidence, but suddenly this morning he walked up to my desk and handed me an early edition of an afternoon paper. Mademoiselle Violette had been discovered dead in her shop by the girls when they came to work this morning. Apparently she had been there all night, but the report was quite indefinite and I am on my way up there now to meet the coroner, who has agreed to wait for me." "You think there is some connection between her death and the letters?" put in Craig. "Of course I can't say, yet," answered Herndon dubiously. "The papers seem to think it was a suicide. But then why should she commit suicide? My man found out that among the girls it was common gossip that she was to marry Jean Pierre, the Fifth Avenue jeweller, of the firm of Lang goods by Americans abroad. Well, the chief of our men in Paris cables me that Pierre is known to have made extraordinarily heavy purchases of made-up jewellery this season. For one thing, we believe he has acquired from a syndicate a rather famous diamond necklace which it has taken years to assemble and match up, worth about three hundred thousand. You know the duty on made-up jewellery is sixty per cent., and even if he brought the stones in loose it would be ten per cent., which on a valuation of, say, two hundred thousand, means twenty thousand dollars duty alone. Then he has a splendid 'dog collar' of pearls, and, oh, a lot of other stuff. I know because we get our tips from all sorts of sources and they are usually pretty straight. Some come from dealers who are sore about not making sales themselves. So you see there is a good deal at stake in this case and it may be that in following it out we shall kill more than one bird. I wish you'd come along with me up to Mademoiselle Violette's and give me an opinion." Craig had already risen from the bench and we were walking up the Avenue. The establishment of Mademoiselle Violette consisted of a three-story and basement brownstone house in which the basement and first floor had been remodelled for business purposes. Mademoiselle's place, which was on the first floor, was announced to the world by a neat little oval gilt sign on the handrailing of the steps. We ascended and rang the bell. As we waited I noticed that there were several other modistes on the same street, while almost directly across was a sign which proclaimed that on September 15 Mademoiselle Gabrielle would open with a high class exhibition of imported gowns from Paris. We entered. The coroner and an undertaker were already there, and the former was expecting Herndon. Kennedy and I had already met him and he shook hands cordially. Mademoiselle Violette, it seemed, had rented the entire house and then had sublet the basement to a milliner, using the first floor herself, the second as a workroom for the girls whom she employed, while she lived on the top floor, which had been fitted for light housekeeping with a kitchenette. It was in the back room of the shop itself on the first floor that her body had been discovered, lying on a davenport. "The newspaper reports were very indefinite," began Herndon, endeavouring to take in the situation. "I suppose they told nearly all the story, but what caused her death? Have you found that out yet? Was it poison or violence?" The coroner said nothing, but with a significant glance at Kennedy he drew a peculiar contrivance from his pocket. It had four round holes in it and through each hole he slipped a finger, then closed his hand, and exhibited his clenched fist. It looked as if he wore a series of four metal rings on his fingers. "Brass knuckles?" suggested Herndon, looking hastily at the body, which showed not a sign of violence on the stony face. The coroner shook his head knowingly. Suddenly he raised his fist. I saw him press hard with his thumb on the upper end of the metal contrivance. From the other end, just concealed under his little finger, there shot out as if released by a magic spring a thin keen little blade of the brightest and toughest steel. He was holding, instead of a meaningless contrivance of four rings, a most dangerous kind of stiletto or dagger upraised. He lifted his thumb and the blade sprang back into its sheath like an extinguished spark of light. "An Apache dagger, such as is used in the underworld of Paris," broke out Kennedy, his eyes gleaming with interest. The coroner nodded. "We found it," he said, "clasped loosely in her hand. But it is only by expert medical testimony that we can determine whether it was placed on her fingers before or after this happened. We have photographed it, and the prints are being developed." He had now uncovered the slight figure of the little French modiste. On the dress, instead of the profuse flow of blood which we had expected to see, there was a single round spot. And in the white marble skin of her breast was a little, nearly microscopic puncture, directly over the heart. "She must have died almost instantly," commented Kennedy, glancing from the Apache weapon to the dead woman and back again. "Internal hemorrhage. I suppose you have searched her effects. Have you found anything that gives a hint among them?" "No," replied the coroner doubtfully, "I can't say we have--unless it is the bundle of letters from Pierre, the jeweller. They seem to have been engaged, and yet the letters stopped abruptly, and, well, from the tone of the last one from him I should say there was a quarrel brewing." An exclamation from Herndon followed. "The same notepaper and the same handwriting as the anonymous letters," he cried. But that was all. Go over the ground as Kennedy might he could find nothing further than the coroner and Herndon had already revealed. "About these people, Lang & Pierre," asked Craig thoughtfully when we had left Mademoiselle's and were riding downtown to the customs house with Herndon. "What do you know about them? I presume that Lang is in America, if his partner is abroad." "Yes, he is here in New York. I believe the firm has a rather unsavoury reputation; they have to be watched, I am told. Then, too, one or the other of the partners makes frequent trips abroad, mostly Pierre. Pierre, as you see, was very intimate with Mademoiselle, and the letters simply confirm what the girls told my detective. He was believed to be engaged to her and I see no reason now to doubt that. The fact is, Kennedy, it wouldn't surprise me in the least to learn that it was he who engineered the smuggling for her as well as himself." "What about the partner? What role does he play in your suspicions?" "That's another curious feature. Lang doesn't seem to bother much with the business. He is a sort of silent partner, although nominally the head of the firm. Still, they both seem always to be plentifully supplied with money and to have a good trade. Lang lives most of the time up on the west shore of the Hudson, and seems to be more interested in his position as commodore of the Riverledge Yacht Club than in his business down here. He is quite a sport, a great motor-boat enthusiast, and has lately taken to hydroplanes." "I meant," repeated Kennedy, "what about Lang and Mademoiselle Violette. Were they--ah--friendly?" "Oh," replied Herndon, seeming to catch the idea. "I see. Of course--Pierre abroad and Lang here. I see what you mean. Why, the girl told my man that Mademoiselle Violette used to go motor-boating with Lang, but only when her fiance, Pierre, was along. No, I don't think she ever had anything to do with Lang, if that's what you are driving at. He may have paid attentions to her, but Pierre was her lover, and I haven't a doubt but that if Lang made any advances she repelled them. She seems to have thought everything of Pierre." We had reached Herndon's office by this time. Leaving word with his stenographer to get the very latest reports from La Montaigne, he continued talking to us about his work. "Dressmakers, milliners, and jewellers are our worst offenders now," he remarked as we stood gazing out of the window at the panorama of the bay off the sea-wall of the Battery. "Why, time and again we unearth what looks for all the world like a 'dressmakers' syndicate,' though this case is the first I've had that involved a death. Really, I've come to look on smuggling as one of the fine arts among crimes. Once the smuggler, like the pirate and the highwayman, was a sort of gentleman-rogue. But now it has become a very ladylike art. The extent of it is almost beyond belief, too. It begins with the steerage and runs right up to the absolute unblushing cynicism of the first cabin. I suppose you know that women, particularly a certain brand of society women, are the worst and most persistent offenders. Why, they even boast of it. Smuggling isn't merely popular--it's aristocratic. But we're going to take some of the flavour out of it before we finish." He tore open a cable message which a boy had brought in. "Now, take this, for instance," he continued. "You remember the sign across the street from Mademoiselle Violette's, announcing that a Mademoiselle Gabrielle was going to open a salon or whatever they call it? Well, here's another cable from our Paris Secret Service with a belated tip. They tell us to look out for a Mademoiselle Gabrielle--on La Montaigne, too. That's another interesting thing. You know the various lines are all ranked, at least in our estimation, according to the likelihood of such offences being perpetrated by their passengers. We watch ships from London, Liverpool, and Paris most carefully. Scandinavian ships are the least likely to need watching. Well, Miss Roberts?" "We have just had a wireless about La Montaigne" reported his stenographer, who had entered while he was speaking, "and she is three hundred miles east of Sandy Hook. She won't dock until to-morrow." "Thank you. Well, fellows, it is getting late and that means nothing more doing to-night. Can you be here early in the morning? We'll go down the bay and 'bring in the ship,' as our men call it when the deputy surveyor and his acting deputies go down to meet it at Quarantine. I can't tell you how much I appreciate your kindness in helping me. If my men get anything connecting Lang with Mademoiselle Violette's case I'll let you know immediately." It was a bright clear snappy morning, in contrast with the heat of the day before, when we boarded the revenue tug at the Barge Office. The waters of the harbour never looked more blue as they danced in the early sunlight, flecked here and there by a foaming whitecap as the conflicting tides eddied about. The shores of Staten Island were almost as green as in the spring, and even the haze over the Brooklyn factories had lifted. It looked almost like a stage scene, clear and sharp, new and brightly coloured. Perhaps the least known and certainly one of the least recognised of the government services is that which includes the vigilant ships of the revenue service. It was not a revenue cutter, however, on which we were ploughing down the bay. The cutter lay, white and gleaming in the morning sun, at anchor off Stapleton, like a miniature warship, saluting as we passed. The revenue boats which steam down to Quarantine and make fast to the incoming ocean greyhounds are revenue tugs. Down the bay we puffed and buffeted for about forty minutes before we arrived at the little speck of an island that is Quarantine. Long before we were there we sighted the great La Montaigne near the group of buildings on the island, where she had been waiting since early morning for the tide and the customs officials. The tug steamed alongside, and quickly up the high ladders swarmed the boarding officer and the deputy collectors. We followed Herndon straight to the main saloon, where the collectors began to receive the declarations which had been made out on blanks furnished to the passengers on the voyage over. They had had several days to write them out--the less excuse for omissions. Glancing at each hastily the collector detached from it the slip with the number at the bottom and handed the number back, to be presented at the inspector's desk at the pier, where customs inspectors were assigned in turn. "Number 140 is the one we want to watch," I heard Herndon whisper to Kennedy. "That tall dark fellow over there." I followed his direction cautiously and saw a sparely built, striking looking man who had just filed his declaration and was chatting vivaciously with a lady who was just about to file hers. She was a clinging looking little thing with that sort of doll-like innocence that deceives nobody. "No, you don't have to swear to it," he said. "You used to do that, but now you simply sign your name--and take a chance," he added, smiling and showing a row of perfect teeth. "Number 156," Herndon noted as the collector detached the stub and handed it to her. "That was Mademoiselle Gabrielle." The couple passed out to the deck, still chatting gaily. "In the old days, before they got to be so beastly particular," I heard him say, "I always used to get the courtesy of the port, an official expedite. But that is over now." The ship was now under way, her flags snapping in the brisk coolish breeze that told of approaching autumn. We had passed up the lower bay and the Narrows, and the passengers were crowded forward to catch the first glimpse of the skyscrapers of New York. On up the bay we ploughed, throwing the spray proudly as we went Herndon employed the time in keeping a sharp watch on the tall, thin man. Incidentally he sought out the wireless operator and from him learned that a code wireless message had been received for Pierre, apparently from his partner, Lang. "There is no mention of anything dutiable in this declaration by 140 which corresponds with any of the goods mentioned in the first cable from Paris," a collector remarked unobtrusively to Herndon, "nor in 156 corresponding to the second cable." "I didn't suppose there would be," was his laconic reply. "That's our job--to find the stuff." At last La Montaigne was warped into the dock. The piles of first-class baggage on the ship were raucously deposited on the wharf and slowly the passengers filed down the plank to meet the line of white-capped uniformed inspectors and plain-clothes appraisers. The comedy and tragedy of the customs inspection had begun. We were among the first to land. Herndon took up a position from which he could see without being seen. In the semi-light of the little windows in the enclosed sides of the pier, under the steel girders of the arched roof like a vast hall, there was a panorama of a huge mass of open luggage. At last Number 140 came down, alone, to the roped-off dock. He walked nonchalantly over to the little deputy surveyor's desk, and an inspector was quickly assigned to him. It was all done neatly in the regular course of business apparently. He did not know that in the orderly rush the sharpest of Herndon's men had been picked out, much as a trick card player will force a card on his victim. Already the customs inspection was well along. One inspector had been assigned to about each five passengers, and big piles of finery were being remorselessly tumbled out in shapeless heaps and exposed to the gaze of that part of the public which was not too much concerned over the same thing as to its own goods and chattels. Reticules and purses were being inspected. Every trunk was presumed to have a false bottom, and things wrapped up in paper were viewed suspiciously and unrolled. Clothes were being shaken and pawed. There did not seem to be much opportunity for concealment. Herndon now had donned the regulation straw hat of the appraiser, and accompanied by us, posing as visitors, was sauntering about. At last we came within earshot of the spot where the inspector was going through the effects of 140. Out of the corner of my eyes I could see that a dispute was in progress over some trifling matter. The man was cool and calm. "Call the appraiser," he said at last, with the air of a man standing on his rights. "I object to this frisking of passengers. Uncle Sam is little better than a pickpocket. Besides, I can't wait here all day. My partner is waiting for me uptown." Herndon immediately took notice. But it was quite evidently, after all, only an altercation for the benefit of those who were watching. I am sure he knew he was being watched, but as the dispute proceeded he assumed the look of a man keenly amused. The matter, involving only a few dollars, was finally adjusted by his yielding gracefully and with an air of resignation. Still Herndon did not go and I am sure it annoyed him. Suddenly he turned and faced Herndon. I could not help thinking, in spite of all that he must be so expert, that, if he really were a smuggler, he had all the poise and skill at evasion that would entitle him to be called a cast master of the art. "You see that woman over there?" he whispered. "She says she is just coming home after studying music in Paris." We looked. It was the guileless ingenue, Mademoiselle Gabrielle. "She has dutiable goods, all right. I saw her declaration. She is trying to bring in as personal effects of a foreign resident gowns which, I believe, she intends to wear on the stage. She's an actress." There was nothing for Herndon to do but to act on the tip. The man had got rid of us temporarily, but we knew the inspector would be, if anything, more vigilant. I think he took even longer than usual. Mademoiselle Gabrielle and her maid pouted and fussed over the renewed examination which Herndon ordered. According to the inspector everything was new and expensive; according to her, old, shabby, and cheap. She denied everything, raged and threatened. But when, instead of ordering the stamp "Passed" to be placed on her half dozen trunks and bags which contained in reality only a few dutiable articles, Herndon threatened to order them to the appraiser's stores and herself to go to the Law Division if she did not admit the points in dispute, there was a real scene. "Generally, madame," he remonstrated, though I could see he was baffled at finding nothing of the goods he had really expected to find, "generally even for a first offence the goods are confiscated and the court or district attorney is content to let the person off with a fine. If this happens again we'll be more severe. So you had better pay the duty on these few little matters, without that." If he had been expecting to "throw a scare" into her, it did not succeed. "Well, I suppose if I must, I must," she said, and the only result of the diversion was that she paid a few dollars more than had been expected and went off in a high state of mind. Herndon had disappeared for a moment, after a whisper from Kennedy, to instruct two of his men to shadow Mademoiselle Gabrielle and, later, Pierre. He soon rejoined us and we casually returned to the vicinity of our tall friend, Number 140, for whom I felt even less respect than ever after his apparently ungallant action toward the lady he had been talking with. He seemed to notice my attitude and he remarked defensively for my benefit, "Only a patriotic act." His inspector by this time had finished a most minute examination. There was nothing that could be discovered, not a false book with a secret spring that might disclose instead of reading matter a heap of almost priceless jewels, not a suspicious bulging of any garment or of the lining of a trunk or grip. Some of the goods might have been on his person, but not much, and certainly there was no excuse for ordering a personal examination, for he could not have hidden a tenth part of what we knew he had, even under the proverbial porous plaster. He was impeccable. Accordingly there was nothing for the inspector to do but to declare a polite armistice. "So you didn't find 'Mona Lisa' in a false bottom, and my trunks were not lined with smuggled cigars after all," he rasped savagely as the stamp "Passed" was at last affixed and he paid in cash at the little window with its sign, "Pay Duty Here: U. S. Custom House," some hundred dollars instead of the thousands Herndon had been hoping to collect, if not to seize. All through the inspection, an extra close scrutiny had been kept on the other passengers as well, to prevent any of them from being in league with the smugglers, though there was no direct or indirect evidence to show that any of the others were. We were about to leave the wharf, also, when Craig's attention was called to a stack of trunks still remaining. "Whose are those?" he asked as he lifted one. It felt suspiciously light. "Some of them belong to a Mr. Pierre and the rest to a Miss Gabrielle," answered an inspector. "Bonded for Troy and waiting to be transferred by the express company." Here, perhaps, at last was an explanation, and Craig took advantage of it. Could it be that the real seat of trouble was not here but at some other place, that some exchange was to be made en route or perhaps an attempt at bribery? Herndon, too, was willing to run a risk. He ordered the trunks opened immediately. But to our disappointment they were almost empty. There was scarcely a thing of value in them. Most of the contents consisted of clothes that had plainly been made in America and were being brought back here. It was another false scent. We had been played with and baffled at every turn. Perhaps this had been the method originally agreed on. At any rate it had been changed. "Could they have left the goods in Paris, after all?" I queried. "With the fall and winter trade just coming on?" Kennedy replied, with an air of finality that set at rest any doubts about his opinion on that score. "I thought perhaps we had a case of--what do you call it, Herndon, when they leave trunks that are to be secretly removed by dishonest expressmen from the wharf at night?" "'Sleepers.' Oh, we've broken that up, too. No expressman would dare try it now. I must confess this thing is beyond me, Craig." Kennedy made no answer. Evidently there was nothing to do but to await developments and see what Herndon's men reported. We had been beaten at every turn in the game. Herndon seemed to feel that there was a bitter sting in the defeat, particularly because the smuggler or smugglers had actually been in our grasp so long to do with as we pleased, and had so cleverly slipped out again, leaving us holding the bag. Kennedy was especially thoughtful as he told over the facts of the case in his mind. "Of course," he remarked, "Mademoiselle Gabrielle wasn't an actress. But we can't deny that she had very little that would justify Herndon in holding her, unless he simply wants a newspaper row." "But I thought Pierre was quite intimate with her at first," I ventured. "That was a dirty trick of his." Craig laughed. "You mean an old one. That was simply a blind, to divert attention from himself. I suspect they talked that over between themselves for days before." It was plainly more perplexing than ever. What had happened? Had Pierre been a prestidigitator and had he merely said presto! when our backs were turned and whisked the goods invisibly into the country? I could find no explanation for the little drama on the pier. If Herndon's men had any genius in detecting smuggling, their professional opponent certainly had greater genius in perpetrating it. We did not see Herndon again until after a hasty luncheon. He was in his office and inclined to take a pessimistic view of the whole affair. He brightened up when a telephone message came in from one of his shadows. The men trailing Pierre and Mademoiselle Gabrielle had crossed trails and run together at a little French restaurant on the lower West Side, where Pierre, Lang, and Mademoiselle Gabrielle had met and were dining in a most friendly spirit. Kennedy was right. She had been merely a cog in the machinery of the plot. The man reported that even when a newsboy had been sent in by him with the afternoon papers displaying in big headlines the mystery of the death of Mademoiselle Violette, they had paid no attention. It seemed evident that whatever the fate of the modiste, Mademoiselle Gabrielle had quite replaced her in the affections of Pierre. There was nothing for us to do but to separate and await developments. It was late in the afternoon when Craig and I received a hurried message from Herndon. One of his men had just called him up over long distance from Riverledge. The party had left the restaurant hurriedly, and though they had taken the only taxicab in sight he had been able to follow them in time to find out that they were going up to Riverledge. They were now preparing to go out for a sail in one of Lang's motor-boats and he would be unable, of course, to follow them further. For the remainder of the afternoon Kennedy remained pondering the case. At last an idea seemed to dawn on him. He found Herndon still at his office and made an appointment to meet on the waterfront near La Montaigne's pier, after dinner. The change in Kennedy's spirits was obvious, though it did not in the least enlighten my curiosity. Even after a dinner which was lengthened out considerably, I thought, I did not get appreciably nearer a solution, for we strolled over to the laboratory, where Craig loaded me down with a huge package which was wrapped up in heavy paper. We arrived on the corner opposite the wharf just as it was growing dusk. The neighbourhood did not appeal to me at night, and even though there were two of us I was rather glad when we met Herndon, who was waiting in the shadow of a fruit stall. But instead of proceeding across to the pier by the side of which La Montaigne was moored, we cut across the wide street and turned down the next pier, where a couple of freighters were lying. The odour of salt water, sewage, rotting wood, and the night air was not inspiring. Nevertheless I was now carried away with the strangeness of our adventure. Halfway down the pier Kennedy paused before one of the gangways that was shrouded in darkness. The door was opened and we followed gingerly across the dirty deck of the freight ship. Below we could hear the water lapping the piles of the pier. Across a dark abyss lay the grim monster La Montaigne with here and there a light gleaming on one of her decks. The sounds of the city seemed miles away. "What a fine place for a murder," laughed Kennedy coolly. He was unwrapping the package which he had taken from me. It proved to be a huge reflector in front of which was placed a little arrangement which, under the light of a shaded lantern carried by Herndon, looked like a coil of wire of some kind. To the back of the reflector Craig attached two other flexible wires which led to a couple of dry cells and a cylinder with a broadened end, made of vulcanised rubber. It might have been a telephone receiver, for all I could tell in the darkness. While I was still speculating on the possible use of the enormous parabolic reflector, a slight commotion on the opposite side of the pier distracted my attention. A ship was coming in and was being carefully and quietly berthed alongside the other big iron freighter on that side. Herndon had left us. "The Mohican is here," he remarked as he rejoined us. To my look of inquiry he added, "The revenue cutter." Kennedy had now finished and had pointed the reflector full at La Montaigne. With a whispered hasty word of caution and advice to Herndon, he drew me along with him down the wharf again. At the little door which was cut in the barrier guarding the shore end of La Montaigne's wharf Kennedy stopped. The customs service night watchman--there is always a watchman of some kind aboard every ship, passenger or freighter, all the time she is in port--seemed to understand, for he admitted us after a word with Kennedy. Threading our way carefully among the boxes, and bales, and crates which were piled high, we proceeded down the wharf. Under the electric lights the longshoremen were working feverishly, for the unloading and loading of a giant trans-Atlantic vessel in the rush season is a long and tedious process at best, requiring night work and overtime, for every moment, like every cubic foot of space, counts. Once within the door, however, no one paid much attention to us. They seemed to take it for granted that we had some right there. We boarded the ship by one of the many entrances and then proceeded down to a deck where apparently no one was working. It was more like a great house than a ship, I felt, and I wondered whether Kennedy's search was not more of a hunt for a needle in a haystack than anything else. Yet he seemed to know what he was after. We had descended to what I imagined must be the quarters of the steward. About us were many large cases and chests, stacked up and marked as belonging to the ship. Kennedy's attention was attracted to them immediately. All at once it flashed on me what his purpose was. In some of those cases were the smuggled goods! Before I could say a word and before Kennedy had a chance even to try to verify his suspicions, a sudden approach of footsteps startled us. He drew me into a cabin or room full of shelves with ship's stores. "Why didn't you bring Herndon over and break into the boxes, if you think the stuff is hidden in one of them?" I whispered. "And let those higher up escape while their tools take all the blame?" he answered. "Sh-h." The men who had come into the compartment looked about as if expecting to see some one. "Two of them came down," a gruff voice said. "Where are they?" From the noise I inferred that there must be four or five men, and from the ease with which they shifted the cases about some of them must have been pretty husky stevedores. "I don't know," a more polished but unfamiliar voice answered. The door to our hiding-place was opened roughly and then banged shut before we realised it. With a taunting laugh, some one turned a key in the lock and before we could move a quick shift of packing cases against the door made escape impossible. Here we were marooned, shanghaied, as it were, within sight if not call of Herndon and our friends. We had run up against professional smugglers, of whom I had vaguely read, disguised as stewards, deckhands, stokers, and other workers. The only other opening to the cabin was a sort of porthole, more for ventilation than anything else. Kennedy stuck his head through it, but it was impossible for a man to squeeze out. There was one of the lower decks directly before us while a bright arc light gleamed tantalisingly over it, throwing a round circle of light into our prison. I reflected bitterly on our shipwreck within sight of port. Kennedy remained silent, and I did not know what was working in his mind. Together we made out the outline of the freighter at the next wharf and speculated as to the location where we had left Herndon with the huge reflector. There was no moon and it was as black as ink in that direction, but if we could have got out I would have trusted to luck to reach it by swimming. Below us, from the restless water lapping on the sides of the hulk of La Montaigne, we could now hear muffled sounds. It was a motor-boat which had come crawling up the river front, with lights extinguished, and had pushed a cautious nose into the slip where our ship lay at the quay. None of your romantic low-lying, rakish craft of the old smuggling yarns was this, ready for deeds of desperation in the dark hours of midnight. It was just a modern little motor-boat, up-to-date, and swift. "Perhaps we'll get out of this finally," I grumbled as I understood now what was afoot, "but not in time to be of any use." A smothered sound as of something going over the vessel's side followed. It was one of the boxes which we had seen outside in the storeroom. Another followed, and a third and a fourth. Then came a subdued parley. "We have two customs detectives locked in a cabin here. We can't stay now. You'll have to take us and our things off, too." "Can't do it," called up another muffled voice. "Make your things into a little bundle. We'll take that, but you'll have to get past the nightwatchman yourselves and meet us at Riverledge." A moment later something else went over the side, and from the sound we could infer that the engine of the motor-boat was being started. A voice sounded mockingly outside our door. "Bon soir, you fellows in there. We're going up the dock. Sorry to leave you here till morning, but they'll let you out then. Au revoir." Below I could hear just the faintest well-muffled chug-chug. Kennedy in the meantime had been coolly craning his neck out of our porthole under the rays of the arc light overhead. He was holding something in his hand. It seemed like a little silver-backed piece of thin glass with a flaring funnel-like thing back of it, which he held most particularly. Though he heard the parting taunt outside he paid no attention. "You go to the deuce, whoever you are," I cried, beating on the door, to which only a coarse laugh echoed back down the passageway. "Be quiet, Walter," ordered Kennedy. "We have located the smuggled goods in the storeroom of the steward, four wooden cases of them. I think the stuff must have been brought on the ship in the trunks and then transferred to the cases, perhaps after the code wireless message was received. But we have been overpowered and locked in a cabin with a port too small to crawl through. The cases have been lowered over the side of the ship to a motor-boat that was waiting below. The lights on the boat are out, but if you hurry you can get it. The accomplices who locked us in are going to disappear up the wharf. If you could only get the night watchman quickly enough you could catch them, too, before they reach the street." I had turned, half expecting to see Kennedy talking to a ship's officer who might have chanced on the deck outside. There was no one. The only thing of life was the still sputtering arc light. Had the man gone crazy? "What of it?" I growled. "Don't you suppose I know all that? What's the use of repeating it now? The thing to do is to get out of this hole. Come, help me at this door. Maybe we can batter it down." Kennedy paid no attention to me, however, but kept his eyes glued on the Cimmerian blackness outside the porthole. He had done nothing apparently, yet a long finger of light seemed to shoot out into the sky from the pier across from us and begin waving back and forth as it was lowered to the dark waters of the river. It was a searchlight. At once I thought of the huge reflector which I had seen set up. But that had been on our side of the next pier and this light came from the far side where the Mohican lay. "What is it?" I asked eagerly. "What has happened?" It was as if a prayer had been answered from our dungeon on La Montaigne. "I knew we should need some means to communicate with Herndon," he explained simply, "and the wireless telephone wasn't practicable. So I have used Dr. Alexander Graham Bell's photophone. Any of the lights on this side of La Montaigne, I knew, would serve. What I did, Walter, was merely to talk into the mouthpiece back of this little silvered mirror which reflects light. The vibrations of the voice caused a diaphragm in it to vibrate and thus the beam of reflected light was made to pulsate. In other words, this little thing is just a simple apparatus to transform the air vibrations of the voice into light vibrations. "The parabolic reflector over there catches these light vibrations and focuses them on the cell of selenium which you perhaps noticed in the centre of the reflector. You remember doubtless that the element selenium varies its electrical resistance under light? Thus there are reproduced similar variations in the cell to those vibrations here in this transmitter. The cell is connected with a telephone receiver and batteries over there--and there you are. It is very simple. In the ordinary carbon telephone transmitter a variable electrical resistance is produced by pressure, since carbon is not so good a conductor under pressure. Then these variations are transmitted along two wires. This photophone is wireless. Selenium even emits notes under a vibratory beam of light, the pitch depending on the frequency. Changes in the intensity of the light focused by the reflector on the cell alter its electrical resistance and vary the current from the dry batteries. Hence the telephone receiver over there is affected. Bell used the photophone or radiophone over several hundred feet, Ruhmer over several miles. When you thought I was talking to myself I was really telling Herndon what had happened and what to do--talking to him literally over a beam of light." I could scarcely believe it, but an exclamation from Kennedy as he drew his head in quickly recalled my attention. "Look out on the river, Walter," he cried. "The Mohican has her searchlight sweeping up and down. What do you see?" The long finger of light had now come to rest. In its pathway I saw a lightless motor-boat bobbing up and down, crowding on all speed, yet followed relentlessly by the accusing finger. The river front was now alive with shouting. Suddenly the Mohican shot out from behind the pier where she had been hidden. In spite of Lang's expertness it was an unequal race. Nor would it have made much difference if it had been otherwise, for a shot rang out from the Mohican which commanded instant respect. The powerful revenue cutter rapidly overhauled the little craft. A hurried tread down the passageway followed. Cases were being shoved aside and a key in the door of our compartment turned quickly. I waited with clenched fists, prepared for an attack. "You're all right?" Herndon's voice inquired anxiously. "We've got that steward and the other fellows all right." "Yes, come on," shouted Craig. "The cutter has made a capture." We had reached the stern of the ship, and far out in the river the Mohican was now headed toward us. She came alongside, and Herndon quickly seized a rope, fastened it to the rail, and let himself down to the deck of the cutter. Kennedy and I followed. "This is a high-handed proceeding," I heard a voice that must have been Lang's protesting. "By what right do you stop me? You shall suffer for this." "The Mohican," broke in Herndon, "has the right to appear anywhere from Southshoal Lightship off Nantucket to the capes of the Delaware, demand an inspection of any vessel's manifest and papers, board anything from La Montaigne to your little motor-boat, inspect it, seize it, if necessary put a crew on it." He slapped the little cannon. "That commands respect. Besides, you were violating the regulations--no lights." On the deck of the cutter now lay four cases. A man broke one of them open, then another. Inside he disclosed thousands of dollars' worth of finery, while from a tray he drew several large chamois bags of glittering diamonds and pearls. Pierre looked on, crushed, all his jauntiness gone. "So," exclaimed Kennedy, facing him, "you have your jilted fiancee, Mademoiselle Violette, to thank for this--her letters and her suicide. It wasn't as easy as you thought to throw her over for a new soul mate, this Mademoiselle Gabrielle whom you were going to set up as a rival in business to Violette. Violette has her revenge for making a plaything of her heart, and if the dead can take any satisfaction she--" With a quick movement Kennedy anticipated a motion of Pierre's. The ruined smuggler had contemplated either an attack on himself or his captor, but Craig had seized him by the wrist and ground his knuckles into the back of Pierre's clenched fist until he winced with pain. An Apache dagger similar to that which the little modiste had used to end her life tragedy clattered to the deck of the ship, a mute testimonial to the high class of society Pierre and his associates must have cultivated. "None of that, Pierre," Craig muttered, releasing him. "You can't cheat the government out of its just dues even in the matter of punishment." XI THE INVISIBLE RAY "I won't deny that I had some expectations from the old man myself." Kennedy's client was speaking in a low, full-chested, vibrating voice, with some emotion, so low that I had entered the room without being aware that any one was there until it was too late to retreat. "As his physician for over twelve years," the man pursued, "I certainly had been led to hope to be remembered in his will. But, Professor Kennedy, I can't put it too strongly when I say that there is no selfish motive in my coming to you about the case. There is something wrong--depend on that." Craig had glanced up at me and, as I hesitated, I could see in an instant that the speaker was a practitioner of a type that is rapidly passing away, the old-fashioned family doctor. "Dr. Burnham, I should like to have you know Mr. Jameson," introduced Craig. "You can talk as freely before him as you have to me alone. We always work together." I shook hands with the visitor. "The doctor has succeeded in interesting me greatly in a case which has some unique features," Kennedy explained. "It has to do with Stephen Haswell, the eccentric old millionaire of Brooklyn. Have you ever heard of him?" "Yes, indeed," I replied, recalling an occasional article which had appeared in the newspapers regarding a dusty and dirty old house in that part of the Heights in Brooklyn whence all that is fashionable had not yet taken flight, a house of mystery, yet not more mysterious than its owner in his secretive comings and goings in the affairs of men of a generation beyond his time. Further than the facts that he was reputed to be very wealthy and led, in the heart of a great city, what was as nearly like the life of a hermit as possible, I knew little or nothing. "What has he been doing now?" I asked. "About a week ago," repeated the doctor, in answer to a nod of encouragement from Kennedy, "I was summoned in the middle of the night to attend Mr. Haswell, who, as I have been telling Professor Kennedy, had been a patient of mine for over twelve years. He had been suddenly stricken with total blindness. Since then he appears to be failing fast, that is, he appeared so the last time I saw him, a few days ago, after I had been superseded by a younger man. It is a curious case and I have thought about it a great deal. But I didn't like to speak to the authorities; there wasn't enough to warrant that, and I should have been laughed out of court for my pains. The more I have thought about it, however, the more I have felt it my duty to say something to somebody, and so, having heard of Professor Kennedy, I decided to consult him. The fact of the matter is, I very much fear that there are circumstances which will bear sharp looking into, perhaps a scheme to get control of the old man's fortune." The doctor paused, and Craig inclined his head, as much as to signify his appreciation of the delicate position in which Burnham stood in the case. Before the doctor could proceed further, Kennedy handed me a letter which had been lying before him on the table. It had evidently been torn into small pieces and then carefully pasted together. The superscription gave a small town in Ohio and a date about a fortnight previous. Dear Father [it read]: I hope you will pardon me for writing, but I cannot let the occasion of your seventy-fifth birthday pass without a word of affection and congratulation. I am alive and well--Time has dealt leniently with me in that respect, if not in money matters. I do not say this in the hope of reconciling you to me. I know that is impossible after all these cruel years. But I do wish that I could see you again. Remember, I am your only child and even if you still think I have been a foolish one, please let me come to see you once before it is too late. We are constantly travelling from place to place, but shall be here for a few days. Your loving daughter, GRACE HASWELL MARTIN. "Some fourteen or fifteen years ago," explained the doctor as I looked up from reading the note, "Mr. Haswell's only daughter eloped with an artist named Martin. He had been engaged to paint a portrait of the late Mrs. Haswell from a photograph. It was the first time that Grace Haswell had ever been able to find expression for the artistic yearning which had always been repressed by the cold, practical sense of her father. She remembered her mother perfectly since the sad bereavement of her girlhood and naturally she watched and helped the artist eagerly. The result was a portrait which might well have been painted from the subject herself rather than from a cold photograph. "Haswell saw the growing intimacy of his daughter and the artist. His bent of mind was solely toward money and material things, and he at once conceived a bitter and unreasoning hatred for Martin, who, he believed, had 'schemed' to capture his daughter and an easy living. Art was as foreign to his nature as possible. Nevertheless they went ahead and married, and, well, it resulted in the old man disinheriting the girl. The young couple disappeared bravely to make their way by their chosen profession and, as far as I know, have never been heard from since until now. Haswell made a new will and I have always understood that practically all of his fortune is to be devoted to founding the technology department in a projected university of Brooklyn." "You have never seen this Mrs. Martin or her husband?" asked Kennedy. "No, never. But in some way she must have learned that I had some influence with her father, for she wrote to me not long ago, enclosing a note for him and asking me to intercede for her. I did so. I took the letter to him as diplomatically as I could. The old man flew into a towering rage, refused even to look at the letter, tore it up into bits, and ordered me never to mention the subject to him again. That is her note, which I saved. However, it is the sequel about which I wish your help." The physician folded up the patched letter carefully before he continued. "Mr. Haswell, as you perhaps know, has for many years been a prominent figure in various curious speculations, or rather in loaning money to many curious speculators. It is not necessary to go into the different schemes which he has helped to finance. Even though most of them have been unknown to the public they have certainly given him such a reputation that he is much sought after by inventors. "Not long ago Haswell became interested in the work of an obscure chemist over in Brooklyn, Morgan Prescott. Prescott claims, as I understand, to be able to transmute copper into gold. Whatever you think of it offhand, you should visit his laboratory yourselves, gentlemen. I am told it is wonderful, though I have never seen it and can't explain it. I have met Prescott several times while he was trying to persuade Mr. Haswell to back him in his scheme, but he was never disposed to talk to me, for I had no money to invest. So far as I know about it the thing sounds scientific and plausible enough. I leave you to judge of that. It is only an incident in my story and I will pass over it quickly. Prescott, then, believes that the elements are merely progressive variations of an original substance or base called 'protyle,' from which everything is derived. But this fellow Prescott goes much further than any of the former theorists. He does not stop with matter. He believes that he has the secret of life also, that he can make the transition from the inorganic to the organic, from inert matter to living protoplasm, and thence from living protoplasm to mind and what we call soul, whatever that may be." "And here is where the weird and uncanny part of it comes in," commented Craig, turning from the doctor to me to call my attention particularly to what was about to follow. "Having arrived at the point where he asserts that he can create and destroy matter, life, and mind," continued the doctor, as if himself fascinated by the idea, "Prescott very naturally does not have to go far before he also claims a control over telepathy and even a communication with the dead. He even calls the messages which he receives by a word which he has coined himself, 'telepagrams.' Thus he says he has unified the physical, the physiological, and the psychical--a system of absolute scientific monism." The doctor paused again, then resumed. "One afternoon, about a week ago, apparently, as far as I am able to piece together the story, Prescott was demonstrating his marvellous discovery of the unity of nature. Suddenly he faced Mr. Haswell. "'Shall I tell you a fact, sir, about yourself?' he asked quickly. 'The truth as I see it by means of my wonderful invention? If it is the truth, will you believe in me? Will you put money into my invention? Will you share in becoming fabulously rich?' "Haswell made some noncommittal answer. But Prescott seemed to look into the machine through a very thick plate-glass window, with Haswell placed directly before it. He gave a cry. 'Mr. Haswell,' he exclaimed, 'I regret to tell you what I see. You have disinherited your daughter; she has passed out of your life and at the present moment you do not know where she is.' "'That's true,' replied the old man bitterly, 'and more than that I don't care. Is that all you see? That's nothing new.' "'No, unfortunately, that is not all I see. Can you bear something further? I think you ought to know it. I have here a most mysterious telepagram.' "'Yes. What is it? Is she dead?' "'No, it is not about her. It is about yourself. To-night at midnight or perhaps a little later,' repeated Prescott solemnly, 'you will lose your sight as a punishment for your action.' "'Pouf!' exclaimed the old man in a dudgeon, 'if that is all your invention can tell me, good-bye. You told me you were able to make gold. Instead, you make foolish prophecies. I'll put no money into such tomfoolery. I'm a practical man,' and with that he stamped out of the laboratory. "Well, that night, about one o'clock, in the silence of the lonely old house, the aged caretaker, Jane, whom he had hired after he banished his daughter from his life, heard a wild shout of 'Help! Help!' Haswell, alone in his room on the second floor, was groping about in the dark. "'Jane,' he ordered, 'a light--a light.' "'I have lighted the gas, Mr. Haswell,' she cried. "A groan followed. He had himself found a match, had struck it, had even burnt his fingers with it, yet he saw nothing. "The blow had fallen. At almost the very hour which Prescott, by means of his weird telepagram had predicted, old Haswell was stricken. "'I'm blind,' he gasped. 'Send for Dr. Burnham.' "I went to him immediately when the maid roused me, but there was nothing I could do except prescribe perfect rest for his eyes and keeping in a dark room in the hope that his sight might be restored as suddenly and miraculously as it had been taken away. "The next morning, with his own hand, trembling and scrawling in his blindness, he wrote the following on a piece of paper: "'MRS. GRACE MARTIN.--Information wanted about the present whereabouts of Mrs. Grace Martin, formerly Grace Haswell of Brooklyn." STEPHEN HASWELL,----Pierrepont St., Brooklyn. "This advertisement he caused to be placed in all the New York papers and to be wired to the leading Western papers. Haswell himself was a changed man after his experience. He spoke bitterly of Prescott, yet his attitude toward his daughter was completely reversed. Whether he admitted to himself a belief in the prediction of the inventor, I do not know. Certainly he scouted such an idea in telling me about it. "A day or two after the advertisements appeared a telegram came to the old man from a little town in Indiana. It read simply: 'Dear Father: Am starting for Brooklyn to-day. Grace.' "The upshot was that Grace Haswell, or rather Grace Martin, appeared the next day, forgave and was forgiven with much weeping, although the old man still refused resolutely to be reconciled with and receive her husband. Mrs. Martin started in to clean up the old house. A vacuum cleaner sucked a ton or two of dust from it. Everything was changed. Jane grumbled a great deal, but there was no doubt a great improvement. Meals were served regularly. The old man was taken care of as never before. Nothing was too good for him. Everywhere the touch of a woman was evident in the house. The change was complete. It even extended to me. Some friend had told her of an eye and ear specialist, a Dr. Scott, who was engaged. Since then, I understand, a new will has been made, much to the chagrin of the trustees of the projected school. Of course I am cut out of the new will, and that with the knowledge at least of the woman who once appealed to me, but it does not influence me in coming to you." "But what has happened since to arouse suspicion?" asked Kennedy, watching the doctor furtively. "Why, the fact is that, in spite of all this added care, the old man is failing more rapidly than ever. He never goes out except attended and not much even then. The other day I happened to meet Jane on the street. The faithful old soul poured forth a long story about his growing dependence on others and ended by mentioning a curious red discoloration that seems to have broken out over his face and hands. More from the way she said it than from what she said I gained the impression that something was going on which should be looked into." "Then you perhaps think that Prescott and Mrs. Martin are in some way connected in this case?" I hazarded. I had scarcely framed the question before he replied in an emphatic negative. "On the contrary, it seems to me that if they know each other at all it is with hostility. With the exception of the first stroke of blindness"--here he lowered his voice earnestly--"practically every misfortune that has overtaken Mr. Haswell has been since the advent of this new Dr. Scott. Mind, I do not wish even to breathe that Mrs. Martin has done anything except what a daughter should do. I think she has shown herself a model of forgiveness and devotion. Nevertheless the turn of events under the new treatment has been so strange that almost it makes one believe that there might be something occult about it--or wrong with the new doctor." "Would it be possible, do you think, for us to see Mr. Haswell?" asked Kennedy, when Dr. Burnham had come to a full stop after pouring forth his suspicions. "I should like to see this Dr. Scott. But first I should like to get into the old house without exciting hostility." The doctor was thoughtful. "You'll have to arrange that yourself," he answered. "Can't you think up a scheme? For instance, go to him with a proposal like the old schemes he used to finance. He is very much interested in electrical inventions. He made his money by speculation in telegraphs and telephones in the early days when they were more or less dreams. I should think a wireless system of television might at least interest him and furnish an excuse for getting in, although I am told his daughter discourages all tangible investment in the schemes that used to interest his active mind." "An excellent idea," exclaimed Kennedy. "It is worth trying anyway. It is still early. Suppose we ride over to Brooklyn with you. You can direct us to the house and we'll try to see him." It was still light when we mounted the high steps of the house of mystery across the bridge. Mrs. Martin, who met us in the parlour, proved to be a stunning looking woman with brown hair and beautiful dark eyes. As far as we could see the old house plainly showed the change. The furniture and ornaments were of a period long past, but everything was scrupulously neat. Hanging over the old marble mantel was a painting which quite evidently was that of the long since deceased Mrs. Haswell, the mother of Grace. In spite of the hideous style of dress of the period after the war, she had evidently been a very beautiful woman with large masses of light chestnut hair and blue eyes which the painter had succeeded in catching with almost life-likeness for a portrait. It took only a few minutes for Kennedy, in his most engaging and plausible manner, to state the hypothetical reason of our call. Though it was perfectly self-evident from the start that Mrs. Martin would throw cold water on anything requiring an outlay of money Craig accomplished his full purpose of securing an interview with Mr. Haswell. The invalid lay propped up in bed, and as we entered he heard us and turned his sightless eyes in our direction almost as if he saw. Kennedy had hardly begun to repeat and elaborate the story which he had already told regarding his mythical friend who had at last a commercial wireless "televue," as he called it on the spur of the moment, when Jane, the aged caretaker, announced Dr. Scott. The new doctor was a youthfully dressed man, clean-shaven, but with an undefinable air of being much older than his smooth face led one to suppose. As he had a large practice, he said, he would beg our pardon for interrupting but would not take long. It needed no great powers of observation to see that the old man placed great reliance on his new doctor and that the visit partook of a social as well as a professional nature. Although they talked low we could catch now and then a word or phrase. Dr. Scott bent down and examined the eyes of his patient casually. It was difficult to believe that they saw nothing, so bright was the blue of the iris. "Perfect rest for the present," the doctor directed, talking more to Mrs. Martin than to the old man. "Perfect rest, and then when his health is good, we shall see what can be done with that cataract." He was about to leave, when the old man reached up and restrained him, taking hold of the doctor's wrist tightly, as if to pull him nearer in order to whisper to him without being overheard. Kennedy was sitting in a chair near the head of the bed, some feet away, as the doctor leaned down. Haswell, still holding his wrist, pulled him closer. I could not hear what was said, though somehow I had an impression that they were talking about Prescott, for it would not have been at all strange if the old man had been greatly impressed by the alchemist. Kennedy, I noticed, had pulled an old envelope from his pocket and was apparently engaged in jotting down some notes, glancing now and then from his writing to the doctor and then to Mr. Haswell. The doctor stood erect in a few moments and rubbed his wrist thoughtfully with the other hand, as if it hurt. At the same time he smiled on Mrs. Martin. "Your father has a good deal of strength yet, Mrs. Martin," he remarked. "He has a wonderful constitution. I feel sure that we can pull him out of this and that he has many, many years to live." Mr. Haswell, who caught the words eagerly, brightened visibly, and the doctor passed out. Kennedy resumed his description of the supposed wireless picture apparatus which was to revolutionise the newspaper, the theatre, and daily life in general. The old man did not seem enthusiastic and turned to his daughter with some remark. "Just at present," commented the daughter, with an air of finality, "the only thing my father is much interested in is a way in which to recover his sight without an operation. He has just had a rather unpleasant experience with one inventor. I think it will be some time before he cares to embark in any other such schemes." Kennedy and I excused ourselves with appropriate remarks of disappointment. From his preoccupied manner it was impossible for me to guess whether Craig had accomplished his purpose or not. "Let us drop in on Dr. Burnham since we are over here," he said when we had reached the street. "I have some questions to ask him." The former physician of Mr. Haswell lived not very far from the house we had just left. He appeared a little surprised to see us so soon, but very interested in what had taken place. "Who is this Dr. Scott?" asked Craig when we were seated in the comfortable leather chairs of the old-fashioned consulting-room. "Really, I know no more about him than you do," replied Burnham. I thought I detected a little of professional jealousy in his tone, though he went on frankly enough, "I have made inquiries and I can find out nothing except that he is supposed to be a graduate of some Western medical school and came to this city only a short time ago. He has hired a small office in a new building devoted entirely to doctors and they tell me that he is an eye and ear specialist, though I cannot see that he has any practice. Beyond that I know nothing about him." "Your friend Prescott interests me, too," remarked Kennedy, changing the subject quickly. "Oh, he is no friend of mine," returned the doctor, fumbling in a drawer of his desk. "But I think I have one of his cards here which he gave me when we were introduced some time ago at Mr. Haswell's. I should think it would be worth while to see him. Although he has no use for me because I have neither money nor influence, still you might take this card. Tell him you are from the university, that I have interested you in him, that you know a trustee with money to invest--anything you like that is plausible. When are you going to see him?" "The first thing in the morning," replied Kennedy. "After I have seen him I shall drop in for another chat with you. Will you be here?" The doctor promised, and we took our departure. Prescott's laboratory, which we found the next day from the address on the card, proved to be situated in one of the streets near the waterfront under the bridge approach, where the factories and warehouses clustered thickly. It was with a great deal of anticipation of seeing something happen that we threaded our way through the maze of streets with the cobweb structure of the bridge carrying its endless succession of cars arching high over our heads. We had nearly reached the place when Kennedy paused and pulled out two pairs of glasses, those huge round tortoiseshell affairs. "You needn't mind these, Walter," he explained. "They are only plain glass, that is, not ground. You can see through them as well as through air. We must be careful not to excite suspicion. Perhaps a disguise might have been better, but I think this will do. There--they add at least a decade to your age. If you could see yourself you wouldn't speak to your reflection. You look as scholarly as a Chinese mandarin. Remember, let me do the talking and do just as I do." We had now entered the shop, stumbled up the dark stairs, and presented Dr. Burnham's card with a word of explanation along the lines which he had suggested. Prescott, surrounded by his retorts, crucibles, burettes, and condensers, received us much more graciously than I had had any reason to anticipate. He was a man in the late forties, his face covered with a thick beard, and his eyes, which seemed a little weak, were helped out with glasses almost as scholarly as ours. I could not help thinking that we three bespectacled figures lacked only the flowing robes to be taken for a group of mediaeval alchemists set down a few centuries out of our time in the murky light of Prescott's sanctum. Yet, though he accepted us at our face value, and began to talk of his strange discoveries there was none of the old familiar prating about matrix and flux, elixir, magisterium, magnum opus, the mastery and the quintessence, those alternate names for the philosopher's stone which Paracelsus, Simon Forman, Jerome Cardan, and the other mediaeval worthies indulged in. This experience at least was as up-to-date as the Curies, Becquerel, Ramsay, and the rest. "Transmutation," remarked Prescott, "was, as you know, finally declared to be a scientific absurdity in the eighteenth century. But I may say that it is no longer so regarded. I do not ask you to believe anything until you have seen; all I ask is that you maintain the same open mind which the most progressive scientists of to-day exhibit in regard to the subject." Kennedy had seated himself some distance from a curious piece or rather collection of apparatus over which Prescott was working. It consisted of numerous coils and tubes. "It may seem strange to you, gentlemen," Prescott proceeded, "that a man who is able to produce gold from, say, copper should be seeking capital from other people. My best answer to that old objection is that I am not seeking capital, as such. The situation with me is simply this. Twice I have applied to the patent office for a patent on my invention. They not only refuse to grant it, but they refuse to consider the application or even to give me a chance to demonstrate my process to them. On the other hand, suppose I try this thing secretly. How can I prevent any one from learning my trade secret, leaving me, and making gold on his own account? Men will desert as fast as I educate them. Think of the economic result of that; it would turn the world topsy-turvy. I am looking for some one who can be trusted to the last limit to join with me, furnish the influence and standing while I furnish the brains and the invention. Either we must get the government interested and sell the invention to it, or we must get government protection and special legislation. I am not seeking capital; I am seeking protection. First let me show you something." He turned a switch, and a part of the collection of apparatus began to vibrate. "You are undoubtedly acquainted with the modern theories of matter," he began, plunging into the explanation of his process. "Starting with the atom, we believe no longer that it is indivisible. Atoms are composed of thousands of ions, as they are called,--really little electric charges. Again, you know that we have found that all the elements fall into groups. Each group has certain related atomic weights and properties which can be and have been predicted in advance of the discovery of missing elements in the group. I started with the reasonable assumption that the atom of one element in a group could be modified so as to become the atom of another element in the group, that one group could perhaps be transformed into another, and so on, if only I knew the force that would change the number or modify the vibrations of these ions composing the various atoms. "Now for years I have been seeking that force or combination of forces that would enable me to produce this change in the elements--raising or lowering them in the scale, so to speak. I have found it. I am not going to tell you or any other man whom you may interest the secret of how it is done until I find some one I can trust as I trust myself. But I am none the less willing that you should see the results. If they are not convincing, then nothing can be." He appeared to be debating whether to explain further, and finally resumed: "Matter thus being in reality a manifestation of force or ether in motion, it is necessary to change and control that force and motion. This assemblage of machines here is for that purpose. Now a few words as to my theory." He took a pencil and struck a sharp blow on the table. "There you have a single blow," he said, "just one isolated noise. Now if I strike this tuning fork you have a vibrating note. In other words, a succession of blows or wave vibrations of a certain kind affects the ear and we call it sound, just as a succession of other wave vibrations affects the retina and we have sight. If a moving picture moves slower than a certain number of pictures a minute you see the separate pictures; faster it is one moving picture. "Now as we increase the rapidity of wave vibration and decrease the wave length we pass from sound waves to heat waves or what are known as the infra-red waves, those which lie below the red in the spectrum of light. Next we come to light, which is composed of the seven colours as you know from seeing them resolved in a prism. After that are what are known as the ultra-violet rays, which lie beyond the violet of white light. We also have electric waves, the waves of the alternating current, and shorter still we find the Hertzian waves, which are used in wireless. We have only begun to know of X-rays and the alpha, beta, and gamma rays from them, of radium, radioactivity, and finally of this new force which I have discovered and call 'protodyne,' the original force. "In short, we find in the universe Matter, Force, and Ether. Matter is simply ether in motion, is composed of corpuscles, electrically charged ions, or electrons, moving units of negative electricity about one one-thousandth part of the hydrogen atom. Matter is made up of electricity and nothing but electricity. Let us see what that leads to. You are acquainted with Mendeleeff's periodic table?" He drew forth a huge chart on which all the eighty or so elements were arranged in eight groups or octaves and twelve series. Selecting one, he placed his finger on the letters "Au," under which was written the number, 197.2. I wondered what the mystic letters and figures meant. "That," he explained, "is the scientific name for the element gold and the figure is its atomic weight. You will see," he added, pointing down the second vertical column on the chart, "that gold belongs to the hydrogen group--hydrogen, lithium, sodium, potassium, copper, rubidium, silver, caesium, then two blank spaces for elements yet to be discovered to science, then gold, and finally another unknown element." Running his finger along the eleventh, horizontal series, he, continued: "The gold series--not the group--reads gold, mercury, thallium, lead, bismuth, and other elements known only to myself. For the known elements, however, these groups and series are now perfectly recognised by all scientists; they are determined by the fixed weight of the atom, and there is a close approximation to regularity. "This twelfth series is interesting. So far only radium, thorium, and uranium are generally known. We know that the radioactive elements are constantly breaking down, and one often hears uranium, for instance, called the 'parent' of radium. Radium also gives off an emanation, and among its products is helium, quite another element. Thus the transmutation of matter is well known within certain bounds to all scientists to-day like yourself, Professor Kennedy. It has even been rumoured but never proved that copper has been transformed into lithium--both members of the hydrogen-gold group, you will observe. Copper to lithium is going backward, so to speak. It has remained for me to devise this protodyne apparatus by which I can reverse that process of decay and go forward in the table, so to put it--can change lithium into copper and copper into gold. I can create and destroy matter by protodyne." He had been fingering a switch as he spoke. Now he turned it on triumphantly. A curious snapping and crackling noise followed, becoming more rapid, and as it mounted in intensity I could smell a pungent odour of ozone which told of an electric discharge. On went the machine until we could feel heat radiating from it. Then came a piercing burst of greenish-blue light from a long tube which looked like a curious mercury vapour lamp. After a few minutes of this Prescott took a small crucible of black lead. "Now we are ready to try it," he cried in great excitement. "Here I have a crucible containing some copper. Any substance in the group would do, even hydrogen if there was any way I could handle the gas. I place it in the machine--so. Now if you could watch inside you would see it change; it is now rubidium, now silver, now caesium. Now it is a hitherto unknown element which I have named after myself, presium, now a second unknown element, cottium--ah!--there we have gold." He drew forth the crucible, and there glowed in it a little bead or globule of molten gold. "I could have taken lead or mercury and by varying the process done the same thing with the gold series as well as the gold group," he said, regarding the globule with obvious pride. "And I can put this gold back and bring it out copper or hydrogen, or better yet, can advance it instead of cause it to decay, and can get a radioactive element which I have named morganium--after my first name, Morgan Prescott. Morganium is a radioactive element next in the series to radium and much more active. Come closer and examine the gold." Kennedy shook his head as if perfectly satisfied to accept the result. As for me I knew not what to think. It was all so plausible and there was the bead of gold, too, that I turned to Craig for enlightenment. Was he convinced? His face was inscrutable. But as I looked I could see that Kennedy had been holding concealed in the palm of his hand a bit of what might be a mineral. From my position I could see the bit of mineral glowing, but Prescott could not. "Might I ask," interrupted Kennedy, "what that curious greenish or bluish light from the tube is composed of?" Prescott eyed him keenly for an instant through his thick glasses. Craig had shifted his gaze from the bit of mineral in his own hand, but was not looking at the light. He seemed to be indifferently contemplating Prescott's hand as it rested on the switch. "That, sir," replied Prescott slowly, "is an emanation due to this new force, protodyne, which I use. It is a manifestation of energy, sir, that may run changes not only through the whole gamut of the elements, but is capable of transforming the ether itself into matter, matter into life, and life into mind. It is the outward sign of the unity of nature, the--" "The means by which you secure the curious telepagrams I have heard of?" inquired Kennedy eagerly. Prescott looked at him sharply, and for a moment I thought his face seemed to change from a livid white to an apoplectic red, although it may have been only the play of the weird light. When he spoke it was with no show of even suppressed surprise. "Yes," he answered calmly. "I see that you have heard something of them. I had a curious case a few days ago. I had hoped to interest a certain capitalist of high standing in this city. I had showed him just what I have showed you, and I think he was impressed by it. Then I thought to clinch the matter by a telepagram, but for some reason or other I failed to consult the forces I control as to the wisdom of doing so. Had I, I should have known better. But I went ahead in self-confidence and enthusiasm. I told him of a long banished daughter with whom, in his heart, he was really wishing to become reconciled but was too proud to say the word. He resented it. He started to stamp out of this room, but not before I had another telepagram which told of a misfortune that was soon to overtake the old man himself. If he had given me a chance I might have saved him, at least have flashed a telepagram to that daughter myself, but he gave me no chance. He was gone. "I do not know precisely what happened after that, but in some way this man found his daughter, and to-day she is living with him. As for my hopes of getting assistance from him, I lost them from the moment when I made my initial mistake of telling him something distasteful. The daughter hates me and I hate her. I have learned that she never ceases advising the old man against all schemes for investment except those bearing moderate interest and readily realised on. Dr. Burnham--I see you know him--has been superseded by another doctor, I believe. Well, well, I am through with that incident. I must get assistance from other sources. The old man, I think, would have tricked me out of the fruits of my discovery anyhow. Perhaps I am fortunate. Who knows?" A knock at the door cut him short. Prescott opened it, and a messenger boy stood there. "Is Professor Kennedy here?" he inquired. Craig motioned to the boy, signed for the message, and tore it open. "It is from Dr. Burnham," he exclaimed, handing the message to me. "Mr. Haswell is dead," I read. "Looks to me like asphyxiation by gas or some other poison. Come immediately to his house. Burnham." "You will pardon me," broke in Craig to Prescott, who was regarding us without the slightest trace of emotion, "but Mr. Haswell, the old man to whom I know you referred, is dead, and Dr. Burnham wishes to see me immediately. It was only yesterday that I saw Mr. Haswell and he seemed in pretty good health and spirits. Prescott, though there was no love lost between you and the old man, I would esteem it a great favour if you would accompany me to the house. You need not take any responsibility unless you desire." His words were courteous enough, but Craig spoke in a tone of quiet authority which Prescott found it impossible to deny. Kennedy had already started to telephone to his own laboratory, describing a certain suitcase to one of his students and giving his directions. It was only a moment later that we were panting up the sloping street that led from the river front. In the excitement I scarcely noticed where we were going until we hurried up the steps to the Haswell house. The aged caretaker met us at the door. She was in tears. Upstairs in the front room where we had first met the old man we found Dr. Burnham working frantically over him. It took only a minute to learn what had happened. The faithful Jane had noticed an odour of gas in the hall, had traced it to Mr. Haswell's room, had found him unconscious, and instinctively, forgetting the new Dr. Scott, had rushed forth for Dr. Burnham. Near the bed stood Grace Martin, pale but anxiously watching the efforts of the doctor to resuscitate the blue-faced man who was stretched cold and motionless on the bed. Dr. Burnham paused in his efforts as we entered. "He is dead, all right," he whispered, aside. "I have tried everything I know to bring him back, but he is beyond help." There was still a sickening odour of illuminating gas in the room, although the windows were now all open. Kennedy, with provoking calmness in the excitement, turned from and ignored Dr. Burnham. "Have you summoned Dr. Scott?" he asked Mrs. Martin. "No," she replied, surprised. "Should I have done so?" "Yes. Send Jame immediately. Mr. Prescott, will you kindly be seated for a few moments." Taking off his coat, Kennedy advanced to the bed where the emaciated figure lay, cold and motionless. Craig knelt down at Mr. Haswell's head and took the inert arms, raising them up until they were extended straight. Then he brought them down, folded upward at the elbow at the side. Again and again he tried this Sylvester method of inducing respiration, but with no more result than Dr. Burnham had secured. He turned the body over on its face and tried the new Schaefer method. There seemed to be not a spark of life left. "Dr. Scott is out," reported the maid breathlessly, "but they are trying to locate him from his office, and if they do they will send him around immediately." A ring at the doorbell caused us to think that he had been found, but it proved to be the student to whom Kennedy had telephoned at his own laboratory. He was carrying a heavy suitcase and a small tank. Kennedy opened the suitcase hastily and disclosed a little motor, some long tubes of rubber fitting into a small rubber cap, forceps, and other paraphernalia. The student quickly attached one tube to the little tank, while Kennedy grasped the tongue of the dead man with the forceps, pulled it up off the soft palate, and fitted the rubber cap snugly over his mouth and nose. "This is the Draeger pulmotor," he explained as he worked, "devised to resuscitate persons who have died of electric shock, but actually found to be of more value in cases of asphyxiation. Start the motor." The pulmotor began to pump. One could see the dead man's chest rise as it was inflated with oxygen forced by the accordion bellows from the tank through one of the tubes into the lungs. Then it fell as the oxygen and the poisonous gas were slowly sucked out through the other tube. Again and again the process was repeated, about ten times a minute. Dr. Burnham looked on in undisguised amazement. He had long since given up all hope. The man was dead, medically dead, as dead as ever was any gas victim at this stage on whom all the usual methods of resuscitation had been tried and had failed. Still, minute after minute, Kennedy worked faithfully on, trying to discover some spark of life and to fan it into flame. At last, after what seemed to be a half-hour of unremitting effort, when the oxygen had long since been exhausted and only fresh air was being pumped into the lungs and out of them, there was a first faint glimmer of life in the heart and a touch of colour in the cheeks. Haswell was coming to. Another half-hour found him muttering and rambling weakly. "The letter--the letter," he moaned, rolling his glazed eyes about. "Where is the letter? Send for Grace." The moan was so audible that it was startling. It was like a voice from the grave. What did it all mean? Mrs. Martin was at his side in a moment. "Father, father,--here I am--Grace. What do you want?" The old man moved restlessly, feverishly, and pressed his trembling hand to his forehead as if trying to collect his thoughts. He was weak, but it was evident that he had been saved. The pulmotor had been stopped. Craig threw the cap to his student to be packed up, and as he did so he remarked quietly, "I could wish that Dr. Scott had been found. There are some matters here that might interest him." He paused and looked slowly from the rescued man lying dazed on the bed toward Mrs. Martin. It was quite apparent even to me that she did not share the desire to see Dr. Scott, at least not just then. She was flushed and trembling with emotion. Crossing the room hurriedly she flung open the door into the hall. "I am sure," she cried, controlling herself with difficulty and catching at a straw, as it were, "that you gentlemen, even if you have saved my father, are no friends of either his or mine. You have merely come here in response to Dr. Burnham, and he came because Jane lost her head in the excitement and forgot that Dr. Scott is now our physician." "But Dr. Scott could not have been found in time, madame," interposed Dr. Burnham with evident triumph. She ignored the remark and continued to hold the door open. "Now leave us," she implored, "you, Dr. Burnham, you, Mr. Prescott, you, Professor Kennedy, and your friend Mr. Jameson, whoever you may be." She was now cold and calm. In the bewildering change of events we had forgotten the wan figure on the bed still gasping for the breath of life. I could not help wondering at the woman's apparent lack of gratitude, and a thought flashed over my mind. Had the affair come to a contest between various parties fighting by fair means or foul for the old man's money--Scott and Mrs. Martin perhaps against Prescott and Dr. Burnham? No one moved. We seemed to be waiting on Kennedy. Prescott and Mrs. Martin were now glaring at each other implacably. The old man moved restlessly on the bed, and over my shoulder I could hear him gasp faintly, "Where's Grace? Send for Grace." Mrs. Martin paid no attention, seemed not to hear, but stood facing us imperiously as if waiting for us to obey her orders and leave the house. Burnham moved toward the door, but Prescott stood his ground with a peculiar air of defiance. Then he took my arm and started rather precipitately, I thought, to leave. "Come, come," said somebody behind us, "enough of the dramatics." It was Kennedy, who had been bending down, listening to the muttering of the old man. "Look at those eyes of Mr. Haswell," he said. "What colour are they?" We looked. They were blue. "Down in the parlour," continued Kennedy leisurely, "you will find a portrait of the long deceased Mrs. Haswell. If you will examine that painting you will see that her eyes are also a peculiarly limpid blue. No couple with blue eyes ever had a black-eyed child. At least, if this is such a case, the Carnegie Institution investigators would be glad to hear of it, for it is contrary to all that they have discovered on the subject after years of study of eugenics. Dark-eyed couples may have light-eyed children, but the reverse, never. What do you say to that, madame?" "You lie," screamed the woman, rushing frantically past us. "I AM his daughter. No interlopers shall separate us. Father!" The old man moved feebly away from her. "Send for Dr. Scott again," she demanded. "See if he cannot be found. He must be found. You are all enemies, villains." She addressed Kennedy, but included the whole room in her denunciation. "Not all," broke in Kennedy remorselessly. "Yes, madame, send for Dr. Scott. Why is he not here?" Prescott, with one hand on my arm and the other on Dr. Burnham's, was moving toward the door. "One moment, Prescott," interrupted Kennedy, detaining him with a look. "There was something I was about to say when Dr. Burnham's urgent message prevented it. I did not take the trouble even to find out how you obtained that little globule of molten gold from the crucible of alleged copper. There are so many tricks by which the gold could have been 'salted' and brought forth at the right moment that it was hardly worth while. Besides, I had satisfied myself that my first suspicions were correct. See that?" He held out the little piece of mineral I had already seen in his hand in the alchemist's laboratory. "That is a piece of willemite. It has the property of glowing or fluorescing under a certain kind of rays which are themselves invisible to the human eye. Prescott, your story of the transmutation of elements is very clever, but not more clever than your real story. Let us piece it together. I had already heard from Dr. Burnham how Mr. Haswell was induced by his desire for gain to visit you and how you had most mysteriously predicted his blindness. Now, there is no such thing as telepathy, at least in this case. How then was I to explain it? What could cause such a catastrophe naturally? Why, only those rays invisible to the human eye, but which make this piece of willemite glow--the ultraviolet rays." Kennedy was speaking rapidly and was careful not to pause long enough to give Prescott an opportunity to interrupt him. "These ultra-violet rays," he continued, "are always present in an electric arc light though not to a great degree unless the carbons have metal cores. They extend for two octaves above the violet of the spectrum and are too short to affect the eye as light, although they affect photographic plates. They are the friend of man when he uses them in moderation as Finsen did in the famous blue light treatment. But they tolerate no familiarity. To let them--particularly the shorter of the rays--enter the eye is to invite trouble. There is no warning sense of discomfort, but from six to eighteen hours after exposure to them the victim experiences violent pains in the eyes and headache. Sight may be seriously impaired, and it may take years to recover. Often prolonged exposure results in blindness, though a moderate exposure acts like a tonic. The rays may be compared in this double effect to drugs, such as strychnine. Too much of them may be destructive even to life itself." Prescott had now paused and was regarding Kennedy contemptuously. Kennedy paid no attention, but continued: "Perhaps these mysterious rays may shed some light on our minds, however. Now, for one thing, ultra-violet light passes readily through quartz, but is cut off by ordinary glass, especially if it is coated with chromium. Old Mr. Haswell did not wear glasses. Therefore he was subject to the rays--the more so as he is a blond, and I think it has been demonstrated by investigators that blonds are more affected by them than are brunettes. "You have, as a part of your machine, a peculiarly shaped quartz mercury vapour lamp, and the mercury vapour lamp of a design such as that I saw has been invented for the especial purpose of producing ultra-violet rays in large quantity. There are also in your machine induction coils for the purpose of making an impressive noise, and a small electric furnace to heat the salted gold. I don't know what other ingenious fakes you have added. The visible bluish light from the tube is designed, I suppose, to hoodwink the credulous, but the dangerous thing about it is the invisible ray that accompanies that light. Mr. Haswell sat under those invisible rays, Prescott, never knowing how deadly they might be to him, an old man. "You knew that they would not take effect for hours, and hence you ventured the prediction that he would be stricken at about midnight. Even if it was partial or temporary, still you would be safe in your prophecy. You succeeded better than you hoped in that part of your scheme. You had already prepared the way by means of a letter sent to Mr. Haswell through Dr. Burnham. But Mr. Haswell's credulity and fear worked the wrong way. Instead of appealing to you he hated you. In his predicament he thought only of his banished daughter and turned instinctively to her for help. That made necessary a quick change of plans." Prescott, far from losing his nerve, turned on us bitterly. "I knew you two were spies the moment I saw you," he shouted. "It seemed as if in some way I knew you for what you were, as if I knew you had seen Mr. Haswell before you came to me. You, too, would have robbed an inventor as I am sure he would. But have a care, both of you. You may be punished also by blindness for your duplicity. Who knows?" A shudder passed over me at the horrible thought contained in his mocking laugh. Were we doomed to blindness, too? I looked at the sightless man on the bed in alarm. "I knew that you would know us," retorted Kennedy calmly. "Therefore we came provided with spectacles of Euphos glass, precisely like those you wear. No, Prescott, we are safe, though perhaps we may have some burns like those red blotches on Mr. Haswell, light burns." Prescott had fallen back a step and Mrs. Martin was making an effort to appear stately and end the interview. "No," continued Craig, suddenly wheeling, and startling us by the abruptness of his next exposure, "it is you and your wife here--Mrs. Prescott, not Mrs. Martin--who must have a care. Stop glaring at each other. It is no use playing at enemies longer and trying to get rid of us. You overdo it. The game is up." Prescott made a rush at Kennedy, who seized him by the wrist and held him tightly in a grasp of steel that caused the veins on the back of his hands to stand out like whipcords. "This is a deep-laid plot," he went on calmly, still holding Prescott, while I backed up against the door and cut off his wife; "but it is not so difficult to see it after all. Your part was to destroy the eyesight of the old man, to make it necessary for him to call on his daughter. Your wife's part was to play the role of Mrs. Martin, whom he had not seen for years and could not see now. She was to persuade him, with her filial affection, to make her the beneficiary of his will, to see that his money was kept readily convertible into cash. "Then, when the old man was at last out of the way, you two could decamp with what you could realise before the real daughter, cut off somewhere across the continent, could hear of the death of her father. It was an excellent scheme. But Haswell's plain, material newspaper advertisement was not so effective for your purposes, Prescott, as the more artistic 'telepagram,' as you call it. Although you two got in first in answering the advertisement, it finally reached the right person after all. You didn't get away quickly enough. "You were not expecting that the real daughter would see it and turn up so soon. But she has. She lives in California. Mr. Haswell in his delirium has just told of receiving a telegram which I suppose you, Mrs. Prescott, read, destroyed, and acted upon. It hurried your plans, but you were equal to the emergency. Besides, possession is nine points in the law. You tried the gas, making it look like a suicide. Jane, in her excitement, spoiled that, and Dr. Burnham, knowing where I was, as it happened, was able to summon me immediately. Circumstances have been against you from the first, Prescott." Craig was slowly twisting up the hand of the inventor, which he still held. With his other hand he pulled a paper from his pocket. It was the old envelope on which he had written upon the occasion of our first visit to Mr. Haswell when we had been so unceremoniously interrupted by the visit of Dr. Scott. "I sat here yesterday by this bed," continued Craig, motioning toward the chair he had occupied, as I remembered. "Mr. Haswell was telling Dr. Scott something in an undertone. I could not hear it. But the old man grasped the doctor by the wrist to pull him closer to whisper to him. The doctor's hand was toward me and I noticed the peculiar markings of the veins. "You perhaps are not acquainted with the fact, but the markings of the veins in the back of the hand are peculiar to each individual--as infallible, indestructible, and ineffaceable as finger prints or the shape of the ear. It is a system invented and developed by Professor Tamassia of the University of Padua, Italy. A superficial observer would say that all vein patterns were essentially similar, and many have said so, but Tamassia has found each to be characteristic and all subject to almost incredible diversities. There are six general classes--in this case before us, two large veins crossed by a few secondary veins forming a V with its base near the wrist. "Already my suspicions had been aroused. I sketched the arrangement of the veins standing out on that hand. I noted the same thing just now on the hand that manipulated the fake apparatus in the laboratory. Despite the difference in make-up Scott and Prescott are the same. "The invisible rays of the ultra-violet light may have blinded Mr. Haswell, even to the recognition of his own daughter, but you can rest assured, Prescott, that the very cleverness of your scheme will penetrate the eyes of the blindfolded goddess of justice. Burnham, if you will have the kindness to summon the police, I will take all the responsibility for the arrest of these people." XII THE CAMPAIGN GRAFTER "What a relief it will be when this election is over and the newspapers print news again," I growled as I turned the first page of the Star with a mere glance at the headlines. "Yes," observed Kennedy, who was puzzling over a note which he had received in the morning mail. "This is the bitterest campaign in years. Now, do you suppose that they are after me in a professional way or are they trying to round me up as an independent voter?" The letter which had called forth this remark was headed, "The Travis Campaign Committee of the Reform League," and, as Kennedy evidently intended me to pass an opinion on it, I picked it up. It was only a few lines, requesting him to call during the morning, if convenient, on Wesley Travis, the candidate for governor and the treasurer of his campaign committee, Dean Bennett. It had evidently been written in great haste in longhand the night before. "Professional," I hazarded. "There must be some scandal in the campaign for which they require your services." "I suppose so," agreed Craig. "Well, if it is business instead of politics it has at least this merit--it is current business. I suppose you have no objection to going with me?" Thus it came about that not very much later in the morning we found ourselves at the campaign headquarters, in the presence of two nervous and high-keyed gentlemen in frock coats and silk hats. It would have taken no great astuteness, even without seeing the surroundings, to deduce instantly that they were engaged in the annual struggle of seeking the votes of their fellow-citizens for something or other, and were nearly worn out by the arduous nature of that process. Their headquarters were in a tower of a skyscraper, whence poured forth a torrent of appeal to the moral sense of the electorate, both in printed and oral form. Yet there was a different tone to the place from that which I had ordinarily associated with political headquarters in previous campaigns. There was an absence of the old-fashioned politicians and of the air of intrigue laden with tobacco. Rather, there was an air of earnestness and efficiency which was decidedly prepossessing. Maps of the state were hanging on the walls, some stuck full of various coloured pins denoting the condition of the canvass. A map of the city in colours, divided into all sorts of districts, told how fared the battle in the stronghold of the boss, Billy McLoughlin. Huge systems of card indexes, loose leaf devices, labour-saving appliances for getting out a vast mass of campaign "literature" in a hurry, in short a perfect system, such as a great, well-managed business might have been proud of, were in evidence everywhere. Wesley Travis was a comparatively young man, a lawyer who had early made a mark in politics and had been astute enough to shake off the thraldom of the bosses before the popular uprising against them. Now he was the candidate of the Reform League for governor and a good stiff campaign he was putting up. His campaign manager, Dean Bennett, was a business man whose financial interests were opposed to those usually understood to be behind Billy McLoughlin, of the regular party to which both Travis and Bennett might naturally have been supposed to belong in the old days. Indeed the Reform League owed its existence to a fortunate conjunction of both moral and economic conditions demanding progress. "Things have been going our way up to the present," began Travis confidentially, when we were seated democratically with our campaign cigars lighted. "Of course we haven't such a big 'barrel' as our opponents, for we are not frying the fat out of the corporations. But the people have supported us nobly, and I think the opposition of the vested interests has been a great help. We seem to be winning, and I say 'seem' only because one can never be certain how anything is going in this political game nowadays. "You recall, Mr. Kennedy, reading in the papers that my country house out on Long Island was robbed the other day? Some of the reporters made much of it. To tell the truth, I think they had become so satiated with sensations that they were sure that the thing was put up by some muckrakers and that there would be an expose of some kind. For the thief, whoever he was, seems to have taken nothing from my library but a sort of scrap-book or album of photographs. It was a peculiar robbery, but as I had nothing to conceal it didn't worry me. Well, I had all but forgotten it when a fellow came into Bennett's office here yesterday and demanded--tell us what it was, Bennett. You saw him." Bennett cleared his throat. "You see, it was this way. He gave his name as Harris Hanford and described himself as a photographer. I think he has done work for Billy McLoughlin. At any rate, his offer was to sell us several photographs, and his story about them was very circumstantial. He hinted that they had been evidently among those stolen from Mr. Travis and that in a roundabout way they had come into the possession of a friend of his without his knowing who the thief was. He said that he had not made the photographs himself, but had an idea by whom they were made, that the original plates had been destroyed, but that the person who made them was ready to swear that the pictures were taken after the nominating convention this fall which had named Travis. At any rate the photographs were out and the price for them was $25,000." "What are they that he should set such a price on them?" asked Kennedy, keenly looking from Bennett quickly to Travis. Travis met his look without flinching. "They are supposed to be photographs of myself," he replied slowly. "One purports to represent me in a group on McLoughlin's porch at his farm on the south shore of the island, about twenty miles from my place. As Hanford described it, I am standing between McLoughlin and J. Cadwalader Brown, the trust promoter who is backing McLoughlin to save his investments. Brown's hand is on my shoulder and we are talking familiarly. Another is a picture of Brown, McLoughlin, and myself riding in Brown's car, and in it Brown and I are evidently on the best of terms. Oh, there are several of them, all in the same vein. Now," he added, and his voice rose with emotion as if he were addressing a cart-tail meeting which must be convinced that there was nothing criminal in riding in a motor-car, "I don't hesitate to admit that a year or so ago I was not on terms of intimacy with these men, but at least acquainted with them. At various times, even as late as last spring, I was present at conferences over the presidential outlook in this state, and once I think I did ride back to the city with them. But I know that there were no pictures taken, and even if there had been I would not care if they told the truth about them. I have frankly admitted in my speeches that I knew these men, that my knowledge of them and breaking from them is my chief qualification for waging an effective war on them if I am elected. They hate me cordially. You know that. What I do care about is the sworn allegation that now accompanies these--these fakes. They were not, could not have been taken after the independent convention that nominated me. If the photographs were true I would be a fine traitor. But I haven't even seen McLoughlin or Brown since last spring. The whole thing is a--" "Lie from start to finish," put in Bennett emphatically. "Yes, Travis, we all know that. I'd quit right now if I didn't believe in you. But let us face the facts. Here is this story, sworn to as Hanford says and apparently acquiesced in by Billy McLoughlin and Cad. Brown. What do they care anyhow as long as it is against you? And there, too, are the pictures themselves--at least they will be in print or suppressed, according as we act. Now, you know that nothing could hurt the reform ticket worse than to have an issue like this raised at this time. We were supposed at least to be on the level, with nothing to explain away. There may be just enough people to believe that there is some basis for this suspicion to turn the tide against us. If it were earlier in the campaign I'd say accept the issue, fight it out to a finish, and in the turn of events we should really have the best campaign material. But it is too late now to expose such a knavish trick of theirs on the Friday before election. Frankly, I believe discretion is the better part of valour in this case and without abating a jot of my faith in you, Travis, well, I'd pay first and expose the fraud afterward, after the election, at leisure." "No, I won't," persisted Travis, shutting his square jaw doggedly. "I won't be held up." The door had opened and a young lady in a very stunning street dress, with a huge hat and a tantalising veil, stood in it for a moment, hesitated, and then was about to shut it with an apology for intruding on a conference. "I'll fight it if it takes my last dollar," declared Travis, "but I won't be blackmailed out of a cent. Good-morning, Miss Ashton. I'll be free in a moment. I'll see you in your office directly." The girl, with a portfolio of papers in her hand, smiled, and Travis quickly crossed the room and held the door deferentially open as he whispered a word or two. When she had disappeared he returned and remarked, "I suppose you have heard of Miss Margaret Ashton, the suffragette leader, Mr. Kennedy? She is the head of our press bureau." Then a heightened look of determination set his fine face in hard lines, and he brought his fist down on the desk. "No, not a cent," he thundered. Bennett shrugged his shoulders hopelessly and looked at Kennedy in mock resignation as if to say, "What can you do with such a fellow?" Travis was excitedly pacing the floor and waving his arms as if he were addressing a meeting in the enemy's country. "Hanford comes at us in this way," he continued, growing more excited as he paced up and down. "He says plainly that the pictures will of course be accepted as among those stolen from me, and in that, I suppose, he is right. The public will swallow it. When Bennett told him I would prosecute he laughed and said, 'Go ahead. I didn't steal the pictures. That would be a great joke for Travis to seek redress from the courts he is criticising. I guess he'd want to recall the decision if it went against him--hey?' Hanford says that a hundred copies have been made of each of the photographs and that this person, whom we do not know, has them ready to drop into the mail to the one hundred leading papers of the state in time for them to appear in the Monday editions just before Election Day. He says no amount of denying on our part can destroy the effect--or at least he went further and said 'shake their validity.' "But I repeat. They are false. For all I know, it is a plot of McLoughlin's, the last fight of a boss for his life, driven into a corner. And it is meaner than if he had attempted to forge a letter. Pictures appeal to the eye and mind much more than letters. That's what makes the thing so dangerous. Billy McLoughlin knows how to make the best use of such a roorback on the eve of an election, and even if I not only deny but prove that they are a fake, I'm afraid the harm will be done. I can't reach all the voters in time. Ten see such a charge to one who sees the denial." "Just so," persisted Bennett coolly. "You admit that we are practically helpless. That's what I have been saying all along. Get control of the prints first, Travis, for God's sake. Then raise any kind of a howl you want--before election or after. As I say, if we had a week or two it might be all right to fight. But we can make no move without making fools of ourselves until they are published Monday as the last big thing of the campaign. The rest of Monday and the Tuesday morning papers do NOT give us time to reply. Even if they were published to-day we should hardly have time to expose the plot, hammer it in, and make the issue an asset instead of a liability. No, you must admit it yourself. There isn't time. We must carry out the work we have so carefully planned to cap the campaign, and if we are diverted by this it means a let-up in our final efforts, and that is as good as McLoughlin wants anyhow. Now, Kennedy, don't you agree with me? Squelch the pictures now at any cost, then follow the thing up and, if we can, prosecute after election?" Kennedy and I, who had been so far little more than interested spectators, had not presumed to interrupt. Finally Craig asked, "You have copies of the pictures?" "No," replied Bennett. "This Hanford is a brazen fellow, but he was too astute to leave them. I saw them for an instant. They look bad. And the affidavits with them look worse." "H'm," considered Kennedy, turning the crisis over in his mind. "We've had alleged stolen and forged letters before, but alleged stolen and forged photographs are new. I'm not surprised that you are alarmed, Bennett,--nor that you want to fight, Travis." "Then you will take up the case?" urged the latter eagerly, forgetting both his campaign manager and his campaign manners, and leaning forward almost like a prisoner in the dock to catch the words of the foreman of the jury. "You will trace down the forger of those pictures before it is too late?" "I haven't said I'll do that--yet," answered Craig measuredly. "I haven't even said I'd take up the case. Politics is a new game to me, Mr. Travis. If I go into this thing I want to go into it and stay in it--well, you know how you lawyers put it, with clean hands. On one condition I'll take the matter up, and on only one." "Name it," cried Travis anxiously, "Of course, having been retained by you," continued Craig with provoking slowness, "it is not reasonable to suppose that if I find--how shall I put it--bluntly, yes?--if I find that the story of Hanford has some--er--foundation, it is not reasonable to suppose that I should desert you and go over to the other side. Neither is it to be supposed that I will continue and carry such a thing through for you regardless of truth. What I ask is to have a free hand, to be able to drop the case the moment I cannot proceed further in justice to myself, drop it, and keep my mouth shut. You understand? These are my conditions and no less." "And you think you can make good?" questioned Bennett rather sceptically. "You are willing to risk it? You don't think it would be better to wait until after the election is won?" "You have heard my conditions," reiterated Craig. "Done," broke in Travis. "I'm going to fight it out, Bennett. If we get in wrong by dickering with them at the start it may be worse for us in the end. Paying amounts to confession." Bennett shook his head dubiously. "I'm afraid this will suit McLoughlin's purpose just as well. Photographs are like statistics. They don't lie unless the people who make them do. But it's hard to tell what a liar can accomplish with either in an election." "Say, Dean, you're not going to desert me?" reproached Travis. "You're not offended at my kicking over the traces, are you?" Bennett rose, placed a hand on Travis's shoulder, and grasped his other. "Wesley," he said earnestly, "I wouldn't desert you even if the pictures were true." "I knew it," responded Travis heartily. "Then let Mr. Kennedy have one day to see what he can do. Then if we make no progress we'll take your advice, Dean. We'll pay, I suppose, and ask Mr. Kennedy to continue the case after next Tuesday." "With the proviso," put in Craig. "With the proviso, Kennedy," repeated Travis. "Your hand on that. Say, I think I've shaken hands with half the male population of this state since I was nominated, but this means more to me than any of them. Call on us, either Bennett or myself, the moment you need aid. Spare no reasonable expense, and--and get the goods, no matter whom it hits higher up, even if it is Cadwalader Brown himself. Good-bye and a thousand thanks--oh, by the way, wait. Let me take you around and introduce you to Miss Ashton. She may be able to help you." The office of Bennett and Travis was in the centre of the suite. On one side were the cashier and clerical force as well as the speakers' bureau, where spellbinders of all degrees were getting instruction, tours were being laid out, and reports received from meetings already held. On the other side was the press bureau with a large and active force in charge of Miss Ashton, who was supporting Travis because he had most emphatically declared for "Votes for Women" and had insisted that his party put this plank in its platform. Miss Ashton was a clever girl, a graduate of a famous woman's college, and had had several years of newspaper experience before she became a leader in the suffrage cause. I recalled having read and heard a great deal about her, though I had never met her. The Ashtons were well known in New York society, and it was a sore trial to some of her conservative friends that she should reject what they considered the proper "sphere" for women. Among those friends, I understood, was Cadwalader Brown himself. Travis had scarcely more than introduced us, yet already I scented a romance behind the ordinarily prosaic conduct of a campaign press bureau. It is far from my intention to minimise the work or the ability of the head of the press bureau, but it struck me, both then and later, that the candidate had an extraordinary interest in the newspaper campaign, much more than in the speakers' bureau, and I am sure that it was not solely accounted for by the fact that publicity is playing a more and more important part in political campaigning. Nevertheless such innovations as her card index system by election districts all over the state, showing the attitude of the various newspaper editors, of local political leaders, and changes of sentiment, were very full and valuable. Kennedy, who had a regular pigeon-hole mind for facts, was visibly impressed by this huge mechanical memory built up by Miss Ashton. Though he said nothing to me I knew he had also observed the state of affairs between the reform candidate and the suffrage leader. It was at a moment when Travis had been called back to his office that Kennedy, who had been eyeing Miss Ashton with marked approval, leaned over and said in a low voice. "Miss Ashton, I think I can trust you. Do you want to do a great favour for Mr. Travis?" She did not betray even by a fleeting look on her face what the true state of her feelings was, although I fancied that the readiness of her assent had perhaps more meaning than she would have placed in a simple "Yes" otherwise. "I suppose you know that an attempt is being made to blackmail Mr. Travis?" added Kennedy quickly. "I know something about it," she replied in a tone which left it for granted that Travis had told her before even we were called in. I felt that not unlikely Travis's set determination to fight might be traceable to her advice or at least to her opinion of him. "I suppose in a large force like this it is not impossible that your political enemies may have a spy or two," observed Kennedy, glancing about at the score or more clerks busily engaged in getting out "literature." "I have sometimes thought that myself," she agreed. "But of course I don't know. Still, I have to be pretty careful. Some one is always over here by my desk or looking over here. There isn't much secrecy in a big room like this. I never leave important stuff lying about where any of them could see it." "Yes," mused Kennedy. "What time does the office close?" "We shall finish to-night about nine, I think. To-morrow it may be later." "Well, then, if I should call here to-night at, say, half-past nine, Could you be here? I need hardly say that your doing so may be of inestimable value to--to the campaign." "I shall be here," she promised, giving her hand with a peculiar straight arm shake and looking him frankly in the face with those eyes which even the old guard in the legislature admitted were vote-winners. Kennedy was not quite ready to leave yet, but sought out Travis and obtained permission to glance over the financial end of the campaign. There were few large contributors to Travis's fund, but a host of small sums ranging from ten and twenty-five dollars down to dimes and nickels. Truly it showed the depth of the popular uprising. Kennedy also glanced hastily over the items of expense--rent, salaries, stenographer and office force, advertising, printing and stationery, postage, telephone, telegraph, automobile and travelling expenses, and miscellaneous matters. As Kennedy expressed it afterwards, as against the small driblets of money coming in, large sums were going out for expenses in lumps. Campaigning in these days costs money even when done honestly. The miscellaneous account showed some large indefinite items, and after a hasty calculation Kennedy made out that if all the obligations had to be met immediately the committee would be in the hole for several thousand dollars. "In short," I argued as we were leaving, "this will either break Travis privately or put his fund in hopeless shape. Or does it mean that he foresees defeat and is taking this way to recoup himself under cover of being held up?" Kennedy said nothing in response to my suspicions, though I could see that in his mind he was leaving no possible clue unnoted. It was only a few blocks to the studio of Harris Hanford, whom Kennedy was now bent on seeing. We found him in an old building on one of the side streets in the thirties which business had captured. His was a little place on the top floor, up three flights of stairs, and I noticed as we climbed up that the room next to his was vacant. Our interview with Hanford was short and unsatisfactory. He either was or at least posed as representing a third party in the affair, and absolutely refused to permit us to have even a glance at the photographs. "My dealings," he asserted airily, "must all be with Mr. Bennett, or with Mr. Travis, direct, not with emissaries. I don't make any secret about it. The prints are not here. They are safe and ready to be produced at the right time, either to be handed over for the money or to be published in the newspapers. We have found out all about them; we are satisfied, although the negatives have been destroyed. As for their having been stolen from Travis, you can put two and two together. They are out and copies have been made of them, good copies. If Mr. Travis wishes to repudiate them, let him start proceedings. I told Bennett all about that. To-morrow is the last day, and I must have Bennett's answer then, without any interlopers coming into it. If it is yes, well and good; if not, then they know what to expect. Good-bye." It was still early in the forenoon, and Kennedy's next move was to go out on Long Island to examine the library at Travis's from which the pictures were said to have been stolen. At the laboratory Kennedy and I loaded ourselves with a large oblong black case containing a camera and a tripod. His examination of the looted library was minute, taking in the window through which the thief had apparently entered, the cabinet he had forced, and the situation in general. Finally Craig set up his camera with most particular care and took several photographs of the window, the cabinet, the doors, including the room from every angle. Outside he snapped the two sides of the corner of the house in which the library was situated. Partly by trolley and partly by carriage we crossed the island to the south shore, and finally found McLoughlin's farm where we had no trouble in getting half a dozen photographs of the porch and house. Altogether the proceedings seemed tame to me, yet I knew from previous experience that Kennedy had a deep laid purpose. We parted in the city, to meet just before it was time to visit Miss Ashton. Kennedy had evidently employed the interval in developing his plates, for he now had ten or a dozen prints, all of exactly the same size, mounted on stiff cardboard in a space with scales and figures on all four sides. He saw me puzzling over them. "Those are metric photographs such as Bertillon of Paris takes," he explained. "By means of the scales and tables and other methods that have been worked out we can determine from those pictures distances and many other things almost as well as if we were on the spot itself. Bertillon has cleared up many crimes with this help, such as the mystery of the shooting in the Hotel Quai d'Orsay and other cases. The metric photograph, I believe, will in time rank with the portrait parle, finger prints, and the rest. "For instance, in order to solve the riddle of a crime the detective's first task is to study the scene topographically. Plans and elevations of a room or house are made. The position of each object is painstakingly noted. In addition, the all-seeing eye of the camera is called into requisition. The plundered room is photographed, as in this case. I might have done it by placing a foot rule on a table and taking that in the picture, but a more scientific and accurate method has been devised by Bertillon. His camera lens is always used at a fixed height from the ground and forms its image on the plate at an exact focus. The print made from the negative is mounted on a card in a space of definite size, along the edges of which a metric scale is printed. In the way he has worked it out the distance between any two points in the picture can be determined. With a topographical plan and a metric photograph one can study a crime as a general studies the map of a strange country. There were several peculiar things that I observed to-day, and I have here an indelible record of the scene of the crime. Preserved in this way it cannot be questioned. "Now the photographs were in this cabinet. There are other cabinets, but none of them has been disturbed. Therefore the thief must have known just what he was after. The marks made in breaking the lock were not those of a jimmy but of a screwdriver. No amazing command of the resources of science is needed so far. All that is necessary is a little scientific common sense, Walter. "Now, how did the robber get in? All the windows and doors were supposedly locked. It is alleged that a pane was cut from this window at the side. It was, and the pieces were there to show it. But take a glance at this outside photograph. To reach that window even a tall man must have stood on a ladder or something. There are no marks of a ladder or of any person in the soft soil under the window. What is more, that window was cut from the inside. The marks of the diamond which cut it plainly show that. Scientific common sense again." "Then it must have been some one in the house or at least some one familiar with it?" I exclaimed. Kennedy nodded. "One thing we have which the police greatly neglect," he pursued, "a record. We have made some progress in reconstructing the crime, as Bertillon calls it. If we only had those Hanford pictures we should be all right." We were now on our way to see Miss Ashton at headquarters, and as we rode downtown I tried to reason out the case. Had it really been a put-up job? Was Travis himself faking, and was the robbery a "plant" by which he might forestall exposure of what had become public property in the hands of another, no longer disposed to conceal it? Or was it after all the last desperate blow of the Boss? The whole thing began to assume a suspicious look in my mind. Although Kennedy seemed to have made little real progress, I felt that, far from aiding Travis, it made things darker. There was nothing but his unsupported word that he had not visited the Boss subsequent to the nominating convention. He admitted having done so before the Reform League came into existence. Besides it seemed tacitly understood that both the Boss and Cadwalader Brown acquiesced in the sworn statement of the man who said he had made the pictures. Added to that the mere existence of the actual pictures themselves was a graphic clincher to the story. Personally, if I had been in Kennedy's place I think I should have taken advantage of the proviso in the compact with Travis to back out gracefully. Kennedy, however, now started on the case, hung to it tenaciously. Miss Ashton was waiting for us at the press bureau. Her desk was at the middle of one end of the room in which, if she could keep an eye on her office force, the office force also could keep an eye on her. Kennedy had apparently taken in the arrangement during our morning visit, for he set to work immediately. The side of the room toward the office of Travis and Bennett presented an expanse of blank wall. With a mallet he quickly knocked a hole in the rough plaster, just above the baseboard about the room. The hole did not penetrate quite through to the other side. In it he placed a round disc of vulcanised rubber, with insulated wires leading down back of the baseboard, then out underneath it, and under the carpet. Some plaster quickly closed up the cavity in the wall, and he left it to dry. Next he led the wires under the carpet to Miss Ashton's desk. There they ended, under the carpet and a rug, eighteen or twenty huge coils several feet in diameter disposed in such a way as to attract no attention by a curious foot on the carpet which covered them. "That is all, Miss Ashton," he said as we watched for his next move. "I shall want to see you early to-morrow, and,--might I ask you to be sure to wear that hat which you have on?" It was a very becoming hat, but Kennedy's tone clearly indicated that it was not his taste in inverted basket millinery that prompted the request. She promised, smiling, for even a suffragette may like pretty hats. Craig had still to see Travis and report on his work. The candidate was waiting anxiously at his hotel after a big political mass meeting on the East Side, at which capitalism and the bosses had been hissed to the echo, if that is possible. "What success?" inquired Travis eagerly. "I'm afraid," replied Kennedy, and the candidate's face fell at the tone, "I'm afraid you will have to meet them, for the present. The time limit will expire to-morrow, and I understand Hanford is coming up for a final answer. We must have copies of those photographs, even if we have to pay for them. There seems to be no other way." Travis sank back in his chair and regarded Kennedy hopelessly. He was actually pale. "You--you don't mean to say that there is no other way, that I'll have to admit even before Bennett--and others that I'm in bad?" "I wouldn't put it that way," said Kennedy mercilessly, I thought. "It is that way," Travis asserted almost fiercely. "Why, we could have done that anyhow. No, no,--I don't mean that. Pardon me. I'm upset by this. Go ahead," he sighed. "You will direct Bennett to make the best terms he can with Hanford when he comes up to-morrow. Have him arrange the details of payment and then rush the best copies of the photographs to me." Travis seemed crushed. We met Miss Ashton the following morning entering her office. Kennedy handed her a package, and in a few words, which I did not hear, explained what he wanted, promising to call again later. When we called, the girls and other clerks had arrived, and the office was a hive of industry in the rush of winding up the campaign. Typewriters were clicking, clippings were being snipped out of a huge stack of newspapers and pasted into large scrap-books, circulars were being folded and made ready to mail for the final appeal. The room was indeed crowded, and I felt that there was no doubt, as Kennedy had said, that nothing much could go on there unobserved by any one to whose interest it was to see it. Miss Ashton was sitting at her desk with her hat on directing the work. "It works," she remarked enigmatically to Kennedy. "Good," he replied. "I merely dropped in to be sure. Now if anything of interest happens, Miss Ashton, I wish you would let me know immediately. I must not be seen up here, but I shall be waiting downstairs in the corridor of the building. My next move depends entirely on what you have to report." Downstairs Craig waited with growing impatience. We stood in an angle in which we could see without being readily seen, and our impatience was not diminished by seeing Hanford enter the elevator. I think that Miss Ashton would have made an excellent woman detective, that is, on a case in which her personal feelings were not involved as they were here. She was pale and agitated as she appeared in the corridor, and Kennedy hurried toward her. "I can't believe it. I won't believe it," she managed to say. "Tell me, what happened?" urged Kennedy soothingly. "Oh, Mr. Kennedy, why did you ask me to do this?" she reproached. "I would almost rather not have known it at all." "Believe me, Miss Ashton," said Kennedy, "you ought to know. It is on you that I depend most. We saw Hanford go up. What occurred?" She was still pale, and replied nervously, "Mr. Bennett came in about quarter to ten. He stopped to talk to me and looked about the room curiously. Do you know, I felt very uncomfortable for a time. Then he locked the door leading from the press bureau to his office, and left word that he was not to be disturbed. A few minutes later a man called." "Yes, yes," prompted Kennedy. "Hanford, no doubt." She was racing on breathlessly, scarcely giving one a chance to inquire how she had learned so much. "Why," she cried with a sort of defiant ring in her tone, "Mr. Travis is going to buy those pictures after all. And the worst of it is that I met him in the hall coming in as I was coming down here, and he tried to act toward me in the same old way--and that after all I know now about him. They have fixed it all up, Mr. Bennett acting for Mr. Travis, and this Mr. Hanford. They are even going to ask me to carry the money in a sealed envelope to the studio of this fellow Hanford, to be given to a third person who will be there at two o'clock this afternoon." "You, Miss Ashton?" inquired Kennedy, a light breaking on his face as if at last he saw something. "Yes, I," she repeated. "Hanford insisted that it was part of the compact. They--they haven't asked me openly yet to be the means of carrying out their dirty deals, but when they do, I--I won't----" "Miss Ashton," remonstrated Kennedy, "I beg you to be calm. I had no idea you would take it like this, no idea. Please, please. Walter, you will excuse us if we take a turn down the corridor and out in the air. This is most extraordinary." For five or ten minutes Kennedy and Miss Ashton appeared to be discussing the new turn of events earnestly, while I waited impatiently. As they approached again she seemed calmer, but I heard her say, "I hope you're right. I'm all broken up by it. I'm ready to resign. My faith in human nature is shaken. No, I won't expose Wesley Travis for his sake. It cuts me to have to admit it, but Cadwalader used always to say that every man has his price. I am afraid this will do great harm to the cause of reform and through it to the woman suffrage cause which cast its lot with this party. I--I can hardly believe----" Kennedy was still looking earnestly at her. "Miss Ashton," he implored, "believe nothing. Remember one of the first rules of politics is loyalty. Wait until----" "Wait?" she echoed. "How can I? I hate Wesley Travis for giving in--more than I hate Cadwalader Brown for his cynical disregard of honesty in others." She bit her lip at thus betraying her feelings, but what she had heard had evidently affected her deeply. It was as though the feet of her idol had turned to clay. Nevertheless it was evident that she was coming to look on it more as she would if she were an outsider. "Just think it over," urged Kennedy. "They won't ask you right away. Don't do anything rash. Suspend judgment. You won't regret it." Craig's next problem seemed to be to transfer the scene of his operations to Hanford's studio. He was apparently doing some rapid thinking as we walked uptown after leaving Miss Ashton, and I did not venture to question him on what had occurred when it was so evident that everything depended on being prepared for what was still to occur. Hanford was out. That seemed to please Kennedy, for with a brightening face, which told more surely than words that he saw his way more and more clearly, he asked me to visit the agent and hire the vacant office next to the studio while he went uptown to complete his arrangements for the final step. I had completed my part and was waiting in the empty room when he returned. He lost no time in getting to work, and it seemed to me as I watched him curiously in silence that he was repeating what he had already done at the Travis headquarters. He was boring into the wall, only this time he did it much more carefully, and it was evident that if he intended putting anything into this cavity it must be pretty large. The hole was square, and as I bent over I could see that he had cut through the plaster and laths all the way to the wallpaper on the other side, though he was careful to leave that intact. Then he set up a square black box in the cavity, carefully poising it and making measurements that told of the exact location of its centre with reference to the partitions and walls. A skeleton key took us into Hanford's well-lighted but now empty studio. For Miss Ashton's sake I wished that the photographs had been there. I am sure Kennedy would have found slight compunction in a larceny of them, if they had been. It was something entirely different that he had in mind now, however, and he was working quickly for fear of discovery. By his measurements I guessed that he was calculating as nearly as possible the centre of the box which he had placed in the hole in the wall on the other side of the dark wallpaper. When he had quite satisfied himself he took a fine pencil from his pocket and made a light cross on the paper to indicate it. The dot fell to the left of a large calendar hanging on the wall. Kennedy's appeal to Margaret Ashton had evidently had its effect, for when we saw her a few moments after these mysterious preparations she had overcome her emotion. "They have asked me to carry a note to Mr. Hanford's studio," she said quietly, "and without letting them know that I know anything about it I have agreed to do so." "Miss Ashton," said Kennedy, greatly relieved, "you're a trump." "No," she replied, smiling faintly, "I'm just feminine enough to be curious." Craig shook his head, but did not dispute the point. "After you have handed the envelope to the person, whoever it may be, in Hanford's studio, wait until he does something--er,--suspicious. Meanwhile look at the wall on the side toward the next vacant office. To the left of the big calendar you will see a light pencil mark, a cross. Somehow you must contrive to get near it, but don't stand in front of it. Then if anything happens stick this little number 10 needle in the wall right at the intersection of the cross. Withdraw it quickly, count fifteen, then put this little sticker over the cross, and get out as best you can, though we shan't be far away if you should need us. That's all." We did not accompany her to the studio for fear of being observed, but waited impatiently in the next office. We could hear nothing of what was said, but when a door shut and it was evident that she had gone, Kennedy quickly removed something from the box in the wall covered with a black cloth. As soon as it was safe Kennedy had sent me posting after her to secure copies of the incriminating photographs which were to be carried by her from the studio, while he remained to see who came out. I thought a change had come over her as she handed me the package with the request that I carry it to Mr. Bennett and get them from him. The first inkling I had that Kennedy had at last been able to trace back something in the mysterious doings of the past two days came the following evening, when Craig remarked casually that he would like to have me call on Billy McLoughlin if I had no engagement. I replied that I had none--and managed to squirm out of the one I really had. The Boss's office was full of politicians, for it was the eve of "dough day," when the purse strings were loosed and a flood of potent argument poured forth to turn the tide of election. Hanford was there with the other ward heelers. "Mr. McLoughlin," began Kennedy quietly, when we were seated alone with Hanford in the little sanctum of the Boss, "you will pardon me if I seem a little slow in coming to the business that has brought me here to-night. First of all, I may say, and you, Hanford, being a photographer will appreciate it, that ever since the days of Daguerre photography has been regarded as the one infallible means of portraying faithfully any object, scene, or action. Indeed a photograph is admitted in court as irrefutable evidence. For when everything else fails, a picture made through the photographic lens almost invariably turns the tide. However, such a picture upon which the fate of an important case may rest should be subjected to critical examination for it is an established fact that a photograph may be made as untruthful as it may be reliable. Combination photographs change entirely the character of the initial negative and have been made for the past fifty years. The earliest, simplest, and most harmless photographic deception is the printing of clouds into a bare sky. But the retoucher with his pencil and etching tool to-day is very skilful. A workman of ordinary skill can introduce a person taken in a studio into an open-air scene well blended and in complete harmony without a visible trace of falsity. "I need say nothing of how one head can be put on another body in a picture, nor need I say what a double exposure will do. There is almost no limit to the changes that may be wrought in form and feature. It is possible to represent a person crossing Broadway or walking on Riverside Drive, places he may never have visited. Thus a person charged with an offence may be able to prove an alibi by the aid of a skilfully prepared combination photograph. "Where, then, can photography be considered as irrefutable evidence? The realism may convince all, will convince all, except the expert and the initiated after careful study. A shrewd judge will insist that in every case the negative be submitted and examined for possible alterations by a clever manipulator." Kennedy bent his gaze on McLoughlin. "Now, I do not accuse you, sir, of anything. But a photograph has come into the possession of Mr. Travis in which he is represented as standing on the steps of your house with yourself and Mr. Cadwalader Brown. He and Mr. Brown are in poses that show the utmost friendliness. I do not hesitate to say that that was originally a photograph of yourself, Mr. Brown, and your own candidate. It is a pretty raw deal, a fake in which Travis has been substituted by very excellent photographic forgery." McLoughlin motioned to Hanford to reply. "A fake?" repeated the latter contemptuously. "How about the affidavits? There's no negative. You've got to prove that the original print stolen from Travis, we'll say, is a fake. You can't do it." "September 19th was the date alleged, I believe?" asked Kennedy quietly, laying down the bundle of metric photographs and the alleged photographs of Travis. He was pointing to a shadow of a gable on the house as it showed in the metric photographs and the others. "You see that shadow of the gable? Perhaps you never heard of it, Hanford, but it is possible to tell the exact time at which a photograph was taken from a study of the shadows. It is possible in principle and practice and can be trusted. Almost any scientist may be called on to bear testimony in court nowadays, but you would say the astronomer is one of the least likely. Well, the shadow in this picture will prove an alibi for some one. "Notice. It is seen very prominently to the right, and its exact location on the house is an easy matter. You could almost use the metric photograph for that. The identification of the gable casting the shadow is easy. To be exact it is 19.62 feet high. The shadow is 14.23 feet down, 13.10 feet east, and 3.43 feet north. You see I am exact. I have to be. In one minute it moved 0.080 feet upward, 0.053 feet to the right and 0.096 feet in its apparent path. It passes the width of a weatherboard, 0.37 foot, in four minutes and thirty-seven seconds." Kennedy was talking rapidly of data which he had derived from his metric photograph, from plumb line, level, compass, and tape, astronomical triangle, vertices, zenith, pole and sun, declination, azimuth, solar time, parallactic angles, refraction, and a dozen bewildering terms. "In spherical trigonometry," he concluded, "to solve the problem three elements must be known. I knew four. Therefore I could take each of the known, treat it as unknown, and have four ways to check my result. I find that the time might have been either three o'clock, twenty-one minutes and twelve seconds, in the afternoon, or 3:21:31, or 3:21:29, or 3:21:33. The average is 3:21:26, and there can therefore be no appreciable error except for a few seconds. For that date must have been one of two days, either May 22 or July 22. Between these two dates we must decide on evidence other than the shadow. It must have been in May, as the immature condition of the foliage shows. But even if it had been in July, that is far from being September. The matter of the year I have also settled. Weather conditions, I find, were favourable on all these dates except that in September. I can really answer, with an assurance and accuracy superior to that of the photographer himself--even if he were honest--as to the real date. The real picture, aside from being doctored, was actually taken last May. Science is not fallible, but exact in this matter." Kennedy had scored a palpable hit. McLoughlin and Hanford were speechless. Still Craig hurried on. "But, you may ask, how about the automobile picture? That also is an unblushing fake. Of course I must prove that. In the first place, you know that the general public has come to recognise the distortion of a photograph as denoting speed. A picture of a car in a race that doesn't lean is rejected--people demand to see speed, speed, more speed even in pictures. Distortion does indeed show speed, but that, too, can be faked. "Hanford knows that the image is projected upside down by the lens on the plate, and that the bottom of the picture is taken before the top. The camera mechanism admits light, which makes the picture, in the manner of a roller blind curtain. The slit travels from the top to the bottom and the image on the plate being projected upside down, the bottom of the object appears on the top of the plate. For instance, the wheels are taken before the head of the driver. If the car is moving quickly the image moves on the plate and each successive part is taken a little in advance of the last. The whole leans forward. By widening the slit and slowing the speed of the shutter, there is more distortion. "Now, this is what happened. A picture was taken of Cadwalader Brown's automobile, probably at rest, with Brown in it. The matter of faking Travis or any one else by his side is simple. If with an enlarging lantern the image of this faked picture is thrown on the paper like a lantern slide, and if the right hand side is a little further away than the left, the top further away than the bottom, you can print a fraudulent high speed ahead picture. True, everything else in, the picture, even if motionless, is distorted, and the difference between this faking and the distortion of the shutter can be seen by an expert. But it will pass. In this case, however, the faker was so sure of that that he was careless. Instead of getting the plate further from the paper on the right he did so on the left. It was further away on the bottom than on the top. He got distortion all right, enough still to satisfy the uninitiated. But it was distortion in the wrong way! The top of the wheel, which goes fastest and ought to be most indistinct, is, in the fake, as sharp as any other part. It is a small mistake, but fatal. That picture is really at high speed--backwards! It is too raw, too raw." "You don't think people are going to swallow all that stuff, do you?" asked Hanford coolly, in spite of the exposures. Kennedy paid no attention. He was looking at McLoughlin. The Boss was regarding him surlily. "Well," he said at length, "what of all this? I had nothing to do with it. Why do you come to me? Take it to the proper parties." "Shall I?" asked Kennedy quietly. He had uncovered another picture carefully. We could not see it, but as he looked at it McLoughlin fairly staggered. "Wh--where did you get that?" he gasped. "I got it where I got it, and it is no fake," replied Kennedy enigmatically. Then he appeared to think better of it. "This," he explained, "is what is known as a pinhole photograph. Three hundred years ago della Porta knew the camera obscura, and but for the lack of a sensitive plate would have made photographs. A box, thoroughly light-tight, slotted inside to receive plates, covered with black, and glued tight, a needle hole made by a number 10 needle in a thin sheet of paper--and you have the apparatus for lensless photography. It has a correctness such as no image-forming means by lenses can have. It is literally rectigraphic, rectilinear, it needs no focussing, and it takes a wide angle with equal effect. Even pinhole snapshots are possible where the light is abundant, with a ten to fifteen second exposure. "That picture, McLoughlin, was taken yesterday at Hanford's. After Miss Ashton left I saw who came out, but this picture shows what happened before. At a critical moment Miss Ashton stuck a needle in the wall of the studio, counted fifteen, closed the needle-hole, and there is the record. Walter, Hanford,--leave us alone an instant." When Kennedy passed out of the Boss's office there was a look of quiet satisfaction on his face which I could not fathom. Not a word could I extract from him either that night or on the following day, which was the last before the election. I must say that I was keenly disappointed by the lack of developments, however. The whole thing seemed to me to be a mess. Everybody was involved. What had Miss Ashton overheard and what had Kennedy said to McLoughlin? Above all, what was his game? Was he playing to spare the girl's feelings by allowing the election to go on without a scandal for Travis? At last election night arrived. We were all at the Travis headquarters, Kennedy, Travis, Bennett, and myself. Miss Ashton was not present, but the first returns had scarcely begun to trickle in when Craig whispered to me to go out and find her, either at her home or club. I found her at home. She had apparently lost interest in the election, and it was with difficulty that I persuaded her to accompany me. The excitement of any other night in the year paled to insignificance before this. Distracted crowds everywhere were cheering and blowing horns. Now a series of wild shouts broke forth from the dense mass of people before a newspaper bulletin board. Now came sullen groans, hisses, and catcalls, or all together with cheers as the returns swung in another direction. Not even baseball could call out such a crowd as this. Lights blazed everywhere. Automobiles honked and ground their gears. The lobster palaces were thronged. Police were everywhere. People with horns and bells and all manner of noise-making devices pushed up one side of the thoroughfares and down the other. Hungrily, ravenously they were feeding on the meagre bulletins of news. Yet back of all the noise and human energy I could only think of the silent, systematic gathering and editing of the news. High up in the League headquarters, when we returned, a corps of clerks was tabulating returns, comparing official and semi-official reports. As first the state swung one way, then another, our hopes rose and fell. Miss Ashton seemed cold and ill at ease, while Travis looked more worried and paid less attention to the returns than would have seemed natural. She avoided him and he seemed to hesitate to seek her out. Would the up-state returns, I had wondered at first, be large enough to overcome the hostile city vote? I was amazed now to see how strongly the city was turning to Travis. "McLoughlin has kept his word," ejaculated Kennedy as district after district showed that the Boss's pluralities were being seriously cut into. "His word? What do you mean?" we asked almost together. "I mean that he has kept his word given to me at a conference which Mr. Jameson saw but did not hear. I told him I would publish the whole thing, not caring whom or where or when it hit if he did not let up on Travis. I advised him to read his Revised Statutes again about money in elections, and I ended up with the threat, 'There will be no dough day, McLoughlin, or this will be prosecuted to the limit.' There was no dough day. You see the effect in the returns." "But how did you do it?" I asked, not comprehending. "The faked photographs did not move him, that I could see." The words, "faked photographs," caused Miss Ashton to glance up quickly. I saw that Kennedy had not told her or any one yet, until the Boss had made good. He had simply arranged one of his little dramas. "Shall I tell, Miss Ashton?" he asked, adding, "Before I complete my part of the compact and blot out the whole affair?" "I have no right to say no," she answered tremulously, but with a look of happiness that I had not seen since our first introduction. Kennedy laid down a print on a table. It was the pinhole photograph, a little blurry, but quite convincing. On a desk in the picture was a pile of bills. McLoughlin was shoving them away from him toward Bennett. A man who was facing forward in the picture was talking earnestly to some one who did not appear. I felt intuitively, even before Kennedy said so, that the person was Miss Ashton herself as she stuck the needle into the wall. The man was Cadwalader Brown. "Travis," demanded Kennedy, "bring the account books of your campaign. I want the miscellaneous account particularly." The books were brought, and he continued, turning the leaves, "It seemed to me to show a shortage of nearly twenty thousand dollars the other day. Why, it has been made up. How was that, Bennett?" Bennett was speechless. "I will tell you," Craig proceeded inexorably. "Bennett, you embezzled that money for your business. Rather than be found out, you went to Billy McLoughlin and offered to sell out the Reform campaign for money to replace it. With the aid of the crook, Hanford, McLoughlin's tool, you worked out the scheme to extort money from Travis by forged photographs. You knew enough about Travis's house and library to frame up a robbery one night when you were staying there with him. It was inside work, I found, at a glance. Travis, I am sorry to have to tell you that your confidence was misplaced. It was Bennett who robbed you--and worse. "But Cadwalader Brown, always close to his creature, Billy McLoughlin, heard of it. To him it presented another idea. To him it offered a chance to overthrow a political enemy and a hated rival for Miss Ashton's hand. Perhaps into the bargain it would disgust her with politics, disillusion her, and shake her faith in what he believed to be some of her 'radical' notions. All could be gained at one blow. They say that a check-book knows no politics, but Bennett has learned some, I venture to say, and to save his reputation he will pay back what he has tried to graft." Travis could scarcely believe it yet. "How did you get your first hint?" he gasped. Kennedy was digging into the wall with a bill file at the place where he had buried the little vulcanised disc. I had already guessed that it was a dictograph, though I could not tell how it was used or who used it. There it was, set squarely in the plaster. There also were the wires running under the carpet. As he lifted the rug under Miss Ashton's desk there also lay the huge circles of wire. That was all. At this moment Miss Ashton stepped forward. "Last Friday," she said in a low tone, "I wore a belt which concealed a coil of wire about my waist. From it a wire ran under my coat, connecting with a small dry battery in a pocket. Over my head I had an arrangement such as the telephone girls wear with a receiver at one ear connected with the battery. No one saw it, for I wore a large hat which completely hid it. If any one had known, and there were plenty of eyes watching, the whole thing would have fallen through. I could walk around; no one could suspect anything; but when I stood or sat at my desk I could hear everything that was said in Mr. Bennett's office." "By induction," explained Kennedy. "The impulses set up in the concealed dictograph set up currents in these coils of wire concealed under the carpet. They were wirelessly duplicated by induction in the coil about Miss Ashton's waist and so affected the receiver under her very becoming hat. Tell the rest, Miss Ashton." "I heard the deal arranged with this Hanford," she added, almost as if she were confessing something, "but not understanding it as Mr. Kennedy did, I very hastily condemned Mr. Travis. I heard talk of putting back twenty thousand into the campaign accounts, of five thousand given to Hanford for his photographic work, and of the way Mr. Travis was to be defeated whether he paid or not. I heard them say that one condition was that I should carry the purchase money. I heard much that must have confirmed Mr. Kennedy's suspicion in one way, and my own in an opposite way, which I know now was wrong. And then Cadwalader Brown in the studio taunted me cynically and-and it cut me, for he seemed right. I hope that Mr. Travis will forgive me for thinking that Mr. Bennett's treachery was his----" A terrific cheer broke out among the clerks in the outer office. A boy rushed in with a still unblotted report. Kennedy seized it and read: "McLoughlin concedes the city by a small majority to Travis, fifteen election districts estimated. This clinches the Reform League victory in the state." I turned to Travis. He was paying no attention except to the pretty apology of Margaret Ashton. Kennedy drew me to the door. "We might as well concede Miss Ashton to Travis," he said, adding gaily, "by induction of an arm about the waist. Let's go out and watch the crowd." 
5270	----	THE FILM MYSTERY BY ARTHUR B. REEVE AUTHOR OF "The Soul Scar" "The Adventuress" and Other Craig Kennedy Scientific Detective Stories CONTENTS CHAPTER I. A CAMERA CRIME II. THE TINY SCRATCH III. TANGLED MOTIVES IV. THE FATAL SCRIPT V. AN EMOTIONAL MAZE VI. THE FIRST CLUB VII. ENID FAYE VIII. LAWRENCE MILLARD IX. WHITE-LIGHT SHADOWS X. CHEMICAL RESEARCH XI. FORESTALLED XII. EMERY PHELPS XIII. MARILYN LORING XIV. ANOTHER CLUE XV. I BECOME A DETECTIVE XVI. ENID ASSISTS XVII. AN APPEAL XVIII. THE ANTIVENIN XIX. AROUND THE CIRCLE XX. THE BANQUET SCENE XXI. MERLE SHIRLEY OVERACTS XXII. THE STEM XXIII. BOTULIN TOXIN XXIV. THE INVISIBLE MENACE XXV. ITCHING SALVE XXVI. A CIGARETTE CASE XXVII. THE FILM FIRE XXVIII. THE PHOSPHORUS BOMB XXIX. MICROSCOPIC EVIDENCE XXX. THE BALLROOM SCENE XXXI. PHYSOSTIGMIN XXXII. CAMERA EVIDENCE THE FILM MYSTERY I A CAMERA CRIME "Camera!" Kennedy and I had been hastily summoned from his laboratory in the city by District-Attorney Mackay, and now stood in the luxurious, ornate library in the country home of Emery Phelps, the banker, at Tarrytown. "Camera!--you know the call when the director is ready to shoot a scene of a picture?--well--at the moment it was given and the first and second camera men began to grind--she crumpled--sank to the floor--unconscious!" Hot and excited, Mackay endeavored to reenact his case for us with all the histrionic ability of a popular prosecutor before a jury. "There's where she dropped--they carried her over here to this davenport--sent for Doctor Blake--but he couldn't do a thing for her. She died--just as you see her. Blake thought the matter so serious, so alarming, that he advised an immediate investigation. That's why I called you so urgently." Before us lay the body of the girl, remarkably beautiful even as she lay motionless in death. Her masses of golden hair, disheveled, added to the soft contours of her features. Her wonderfully large blue-gray eyes with their rare gift for delicate shades of expression were closed, but long curling lashes swept her cheeks still and it was hard to believe that this was anything more than sleep. It was inconceivable that Stella Lamar, idol of the screen, beloved of millions, could have been taken from the world which worshiped her. I felt keenly for the district attorney. He was a portly little man of the sort prone to emphasize his own importance and so, true to type, he had been upset completely by a case of genuine magnitude. It was as though visiting royalty had dropped dead within his jurisdiction. I doubt whether the assassination of a McKinley or a Lincoln could have unsettled him as much, because in such an event he would have had the whole weight of the Federal government behind him. There was no question but that Stella Lamar enjoyed a country-wide popularity known by few of our Presidents. Her sudden death was a national tragedy. Apparently Mackay had appealed to Kennedy the moment he learned the identity of Stella, the moment he realized there was any question about the circumstances surrounding the affair. Over the telephone the little man had been almost incoherent. He had heard of Kennedy's work and was feverishly anxious to enlist his aid, at any price. All we knew as we took the train on the New York Central was that Stella was playing a part in a picture to be called "The Black Terror," that the producer was Manton Pictures, Incorporated, and that she had dropped dead suddenly and without warning in the middle of a scene being photographed in the library at the home of Emery Phelps. I was singularly elated at the thought of accompanying Kennedy on this particular case. It was not that the tragic end of a film star whose work I had learned to love was not horrible to me, but rather because, for once, I thought Kennedy actually confronted a situation where his knowledge of a given angle of life was hardly sufficient for his usual analysis of the facts involved. "Walter," he had exclaimed, as I burst into the laboratory in response to a hurried message, "here's where I need your help. You know all about moving pictures, so--if you'll phone your city editor and ask him to let you cover a case for the Star we'll just about catch a train at One Hundred and Twenty-fifth Street." Because the film world had fascinated me always I had made a point of being posted on its people and their activities. I remembered the very first appearance of Stella Lamar back in the days of General Film, when pictures were either Licensed or Independent, when only two companies manufactured worth-while screen dramas, when any subject longer than a reel had to be of rare excellence, such as the art films imported from France for the Licensed program. In those days, Stella rose rapidly to prominence. Her large wistful eyes had set the hearts of many of us to beating at staccato rate. Then came Lloyd Manton, her present manager, and the first of a new type of business man to enter the picture field. Manton was essentially a promoter. His predecessors had been men carried to success by the growth of the new art. Old Pop Belman, for instance, had been a fifth-rate oculist who rented and sold stereopticons as a side line. With blind luck he had grasped the possibilities of Edison's new invention. Just before the break-up of General Film he had become many times a millionaire and it was then that he had sent a wave of laughter over the entire country by an actual cable to William Shakespeare, address London, asking for all screen rights to the plays written by that gentleman. Manton represented a secondary phase in film finance. Continent Films, his first corporation, was a stockjobbing concern. Grasping the immense popularity of Stella Lamar, he had coaxed her away from the old studio out in Flatbush where all her early successes had been photographed. With the magic of her name he sold thousands of shares of stock to a public already fed up on the stories of the fortunes to be made in moving pictures. When much of the money so raised had been dissipated, when Continent's quotation on the curb sank to an infinitesimal fraction, then it developed that Stella's contract was with Manton personally. Manton Pictures, Incorporated, was formed to exploit her. The stock of this company was not offered to outside investors. Stella's popularity had in no way suffered from the business methods of her manager. Manton, at the least, had displayed rare foresight in his estimation of public taste. Except for a few attempts with established stage favorites, photographed generally in screen versions of theatrical classics and backed by affiliations with the producers of the legitimate stage, Continent Films was the first concern to make the five-reel feature. Stella, as a Continent player, was the very first feature star. Under the banner of Manton Pictures, she had never surrendered her position of pre-eminence. Also, scandal somehow had failed to touch her. Those initiated to the inner gossip of the film world, like myself, were under no illusions. The relations between Stella and Manton were an open secret. Yet the picture fans, in their blind worship, believed her to be as they saw her upon the screen. To them the wide and wistful innocence of her remarkably large eyes could not be anything but genuine. The artlessness of the soft curves of her mouth was proof to them of the reality of an ingenuous and very girlish personality. Even her divorce had helped rather than harmed her. It seemed irony to me that she should have obtained the decree instead of her husband, and in New York, too, where the only grounds are unfaithfulness. The testimony in the case had been sealed so that no one knew whom she had named as corespondent. At the time, I wondered what pressure had been exerted upon Millard to prevent the filing of a cross suit. Surely he should have been able to substantiate the rumors of her association with Lloyd Manton. Lawrence Millard, author and playwright and finally scenario writer, had been as much responsible for the success of his wife as Manton, and in a much less spectacular way. It was Millard who had written her first great Continent success, who had developed the peculiar type of story best suited for her, back in the early days of the one reel and General Film. It is commonly known in picture circles that an actress who screens well, even if she is only a moderately good artist, can be made a star with one or two or three good stories and that, conversely, a star may be ruined by a succession of badly written or badly produced vehicles. Those of us not blinded by an idolatrous worship for the girl condemned her severely for throwing her husband aside at the height of her success. The public displayed their sympathy for her by a burst of renewed interest. The receipts at the box office whenever her films were shown probably delighted both Manton and Stella herself. I had wondered, as Kennedy and I occupied a seat in the train, and as he left me to my thoughts, whether there could be any connection between the tragedy and the divorce. The decree, I knew, was not yet final. Could it be possible that Millard was unwilling, after all, to surrender her? Could he prefer deliberate murder to granting her her freedom? I was compelled to drop that line of thought, since it offered no explanation of his previous failure to contest her suit or to start counter action. Then my reflections had strayed away from Kennedy's sphere, the solving of the mystery, to my own, the news value of her death and the events following. The Star, as always, had been only too glad to assign me to any case where Craig Kennedy was concerned; my phone message to the city editor, the first intimation to any New York paper of Stella's death, already had resulted without doubt in scare heads and an extra edition. The thought of the prominence given the personal affairs of picture players and theatrical folk had disgusted me. There are stars against whom there is not the slightest breath of gossip, even among the studio scandal-mongers. Any number of girls and men go about their work sanely and seriously, concerned in nothing but their success and the pursuit of normal pleasures. As a matter of fact it had struck me on the train that this was about the first time Craig Kennedy had ever been called in upon a case even remotely connected with the picture field. I knew he would be confronted with a tangled skein of idle talk, from everybody, about everybody, and mostly without justification. I hoped he would not fall into the popular error of assuming all film players bad, all studios schools of immorality. I was glad I was able to accompany him on that account. The arrival at Tarrytown had ended my reflections, and Kennedy's--whatever they may have been. Mackay himself had met us at the station and with a few words, to cover his nervousness, had whisked us out to the house. As we approached, Kennedy had taken quick note of the surroundings, the location of the home itself, the arrangement of the grounds. There was a spreading lawn on all four sides, unbroken by plant or bush or tree--sheer prodigality of space, the better to display a rambling but most artistic pile of gray granite. Masking the road and the adjoining grounds was thick, impenetrable shrubbery, a ring of miniature forest land about the estate. There was a garage, set back, and tennis courts, and a practice golf green. In the center of a garden in a far corner a summerhouse was placed so as to reflect itself in the surface of a glistening swimming pool. As we pulled up under the porte-cochere Emery Phelps, the banker, greeted us. Perhaps it was my imagination, but it seemed to me that there was a repressed animosity in his manner, as though he resented the intrusion of Kennedy and myself, yet felt powerless to prevent it. In contrast to his manner was the cordiality of Lloyd Manton, just inside the door. Manton was childishly eager in his welcome, so much so that I was able to detect a shade of suspicion in Kennedy's face. The others of the company were clustered in the living room, through which we passed to reach the library. I found small opportunity to study them in the rather dim light. Mackay beckoned to a man standing in a window, presenting him to Kennedy as Doctor Blake. Then we entered the long paneled chamber which had been the scene of the tragedy. Now I stood, rather awed, with the motionless figure of Stella Lamar before me in her last pitiable close-up. For I have never lost the sense of solemnity on entering the room of a tragedy, in spite of the long association I have had with Kennedy in the scientific detection of crime. Particularly did I have the feeling in this case. The death of a man is tragic, but I know nothing more affecting than the sudden and violent death of a beautiful woman--unless it be that of a child. I recalled a glimpse of Stella as I had seen her in her most recent release, as the diaphragm opened on her receiving a box of chocolates, sent by her lover, and playfully feeding one of them to her beautiful collie, "Laddie," as he romped about upon a divan and almost smothered her with affection. The vivacity and charm of the scene were in sad contrast with what lay before me. As I looked more carefully I saw now that her full, well-rounded face was contorted with either pain or fear--perhaps both. Even through the make-up one could see that her face was blotched and swollen. Also, the muscles were contorted; the eyes looked as if they might be bulging under the lids; and there was a bluish tinge to her skin. Evidently death had come quickly, but it had not been painless. "Even the coroner has not disturbed the body," Mackay hastened to explain to Kennedy. "The players, the camera men, all were sent out of the room the moment Doctor Blake was certain something more than a natural cause lay behind her death. Mr. Phelps telephoned to me, and upon my arrival I ordered the doors and windows closed, posted my deputies to prevent any interference with anything in the room, left my instructions that everyone was to be detained, then got in touch with you as quickly as I could." Kennedy turned to him. Something in the tone of his voice showed that he meant his compliment. "I'm glad, Mackay, to be called in by some one who knows enough not to destroy evidence; who realizes that perhaps the slightest disarrangement of a rug, for instance, may be the only clue to a murder. It's--it's rare!" The little district attorney beamed. If he had found it necessary to walk across the floor just then he would have strutted. I smiled because I wanted Kennedy to show again his marvelous skill in tracing a crime to its perpetrator. I was anxious that nothing should be done to hamper him. II THE TINY SCRATCH Kennedy, before his own examination of the body, turned to Doctor Blake. "Tell me just what you found when you arrived," he directed. The physician, whose practice embraced most of the wealthy families in and around Tarrytown, was an unusually tall, iron-gray-haired man of evident competency. It was very plain that he resented his unavoidable connection with the case. "She was still alive," he responded, thoughtfully, "although breathing with difficulty. Nearly everyone had clustered about her, so that she was getting little air, and the room was stuffy from the lights they had been using in taking the scene. They told me she dropped unconscious and that they couldn't revive her, but at first it did not occur to me that it might be serious. I thought perhaps the heat--" "You saw nothing suspicious," interrupted Kennedy, "nothing in the actions or manner of anyone in the room?" "No, when I first entered I didn't suspect anything out of the way. I had them send everyone into the next room, except Manton and Phelps, and had the doors and windows thrown open to give her air. Then when I examined her I detected what seemed to me to be both a muscular and nervous paralysis, which by that time had proceeded pretty far. As I touched her she opened her eyes, but she was unable to speak. She was breathing with difficulty; her heart action was weakening so rapidly that I had little opportunity to apply restorative measures." "What do you think caused the death?" "So far, I can make no satisfactory explanation." The doctor shrugged his shoulders very slightly. "That is why I advised an immediate investigation. I did not care to write a death certificate." "You have no hypothesis?" "If she died from any natural organic disorder, the signs were lacking by which I could trace it. Everything indicates the opposite, however. It would be hard for me to say whether the paralysis of respiration or of the heart actually caused her death. If it was due to poison--Well, to me the whole affair is shrouded in mystery. The symptoms indicated nothing I could recognize with any degree of certainty." Kennedy stooped over, making a superficial examination of the girl. I saw that some faint odor caught his nostrils, for he remained poised a moment, inhaling reflectively, his eyes clouded in thought. Then he went to the windows, raising the shades an additional few inches each, but that did not seem to give him the light he wished. In the room were the portable arcs used in the making of scenes in an actual interior setting. The connections ran to heavy insulated junction boxes at the ends of two lines of stiff black stage cable. Near the door the circuits were joined and a single lead of the big duplex cord ran out along the polished hardwood floor, carried presumably to the house circuit at a fuse box where sufficient amperage was available. Kennedy's eyes followed out the wires quickly. Then, motioning to me to help, he wheeled one of the heavy stands around and adjusted the hood so that the full strength of the light would be cast upon Stella. The arc in place, he threw the switch, and in the sputtering flood of illumination dropped to his knees, taking a powerful pocket lens from his waistcoat and beginning an inch by inch examination of her skin. I gained a fresh realization of the beauty of the star as she lay under the dazzling electric glow, and in particular I noticed the small amount of make-up she had used and the natural firmness of her flesh. She was dressed in a modish, informal dinner dress, of embroidered satin, cut fairly low at front and back and with sleeves of some gauzelike material reaching not halfway to her elbow, hardly sleeves at all, in fact. Kennedy with his glass went over her features with extreme care. I saw that he drew her hair back, and that then he parted it, to examine her scalp, and I wondered what infinitesimal clue might be the object of his search. I had learned, however, never to question him while he was at work. With his eye glued to his lens he made his way about and around her neck, and down and over her throat and chest so far as it remained unprotected by the silk of her gown. With the aid of Mackay he turned her over to examine her back. Next he returned the body to its former position and began to inspect the arms. Very suddenly something caught his eye on the inside of her right forearm. He grunted with satisfaction, straightened, pulled the switch of the arc, wiped his eyes, which were watering. "Find anything, Mr. Kennedy?" Doctor Blake seemed to understand, to some extent, the purpose of the examination. Kennedy did not answer, probably preoccupied with theories which I could see were forming in his mind. The library was a huge room of greater length than breadth. At one end were wide French windows looking out upon the garden and summer house. The door to the hallway and living room was very broad, with heavy sliding panels and rich portieres of a velours almost the tint of the wood-work. Between the door, situated in the side wall near the opposite end, and the windows, was a magnificent stone fireplace with charred logs testifying to its frequent use. The couch where Stella lay had been drawn back from its normal position before the fire, together with a huge table of carved walnut. The other two walls were an unbroken succession of shelves, reaching to the ceiling and literally packed with books. Facing the windows and the door, so as to include the fireplace and the wide sweep of the room within range, were two cameras still set up, the legs of their tripods nested, probably left exactly as they were at the moment of Stella's collapse. I touched the handle of one, a Bell & Howell, and saw that it was threaded, that the film had not been disturbed. The lights, staggered and falling away from the camera lines, were arranged to focus their illumination on the action of the scenes. There were four arcs and two small portable banks of Cooper-Hewitts, the latter used to cut the sharp shadows and give a greater evenness to the photography. Also there were diffusers constructed of sheets of white cloth stretched taut on frames. These reflected light upward upon the faces of the actors, softening the lower features, and so valuable in adding to the attractiveness of the women in particular. All this I had learned from visits to a studio with the Star's photoplay editor. I was anxious to impress my knowledge upon Kennedy. He gave me no opportunity, however, but wheeled upon Mackay suddenly. "Send in the electrician," he ordered. "Keep everyone else out until I'm ready to examine them." While the district attorney hurried to the sliding doors, guarded on their farther side by one of the amateur deputies he had impressed into service, Kennedy swung the stand of the arc he had used back into the place unaided. I noticed that Doctor Blake was nervously interested in spite of his professional poise. I certainly was bursting with curiosity to know what Kennedy had found. The electrician, a wizened veteran of the studios, with a bald head which glistened rather ridiculously, entered as though he expected to be held for the death of the star on the spot. "I don't know nothin'," he began, before anyone could start to question him. "I was outside when they yelled, honest! I was seeing whether m'lead was getting hot, and I heard 'em call to douse the glim, an'--" "Put on all your lights"--Kennedy was unusually sharp, although it was plain he held no suspicion of this man, as he added--"just as you had them." As the electrician went from stand to stand sulkily, there was a sputter from the arcs, almost deafening in the confines of the room, and quite a bit of fine white smoke. But in a moment the corner of the library constituting the set was brilliantly, dazzlingly lighted. To me it was quite like being transported into one of the big studios in the city. "Is this the largest portion of the room they used?" Kennedy asked. "Did you have your stands any farther back?" "This was the biggest lay-out, sir!" replied the man. "Were all the scenes in which Miss Lamar appeared before her death in this corner of the room?" "Yes, sir!" "And this was the way you had the scene lighted when she dropped unconscious?" "Yes, sir! I pulled m'lights an'--an' they lifted her up and put her right there where she is, sir!" Kennedy paid no attention to the last; in fact, I doubt whether he heard it. Dropping to hands and knees immediately, he began a search of the floor and carpet as minutely painstaking as the inspection he had given Stella's own person. Instinctively I drew back, to be out of his way, as did Doctor Blake and Mackay. The electrician, I noticed, seemed to grasp now the reason for the summons which undoubtedly had frightened him badly. He gave his attention to his lights, stroking a refractory Cooper-Hewitt tube for all the world as if some minor scene in the story were being photographed. It was hard to realize that it was not another picture scene, but that Craig Kennedy, in my opinion the founder of the scientific school of modern detectives, was searching out in this strange environment the clue to a real murder so mysterious that the very cause of death was as yet undetermined. I was hoping for a display of the remarkable brilliance Craig had shown in so many of the cases brought to his attention. I half expected to see him rise from the floor with some tiny something in his hand, some object overlooked by everyone else, some tangible evidence which would lead to the immediate apprehension of the perpetrator of the crime. That Stella Lamar had met her death by foul means I did not doubt for an instant, and so I waited feverishly for the conclusion of Kennedy's search. As it happened, this was not destined to be one of his cases cleared up in a brief few hours of intensive effort. He covered every inch of the floor within the illuminated area; then he turned his attention to the walls and furniture and the rest of the room in somewhat more perfunctory, but no less skillful manner. Fully fifteen minutes elapsed, but I knew from his expression that he had discovered nothing. In a wringing perspiration from the heat of the arcs, but nevertheless glad to have had the intense light at his disposal, he motioned to the electrician to turn them off and to leave the room. "Find anything, Mr. Kennedy?" queried the physician once more. Kennedy beckoned all of us to the side of the ill-fated actress. Lifting the right arm, finding the spot which had caused his exclamation before, he handed his pocket lens to Doctor Blake. After a moment a low whistle escaped the lips of the physician. Next it was my turn. As I stooped over I caught, above the faint scent of imported perfume which she affected, a peculiar putrescent odor. This it was which had caught Kennedy's nostrils. Then through the glass I could detect upon her forearm the tiniest possible scratch ending in an almost invisible puncture, such as might have been made by a very sharp needle or the point of an incredibly fine hypodermic syringe. Drawing back, I glanced again at her face, which I had already noted was blotched and somewhat swollen beneath the make-up. Again I thought that the muscles were contorted, that the eyes were bulging slightly, that there was a bluish tinge to her skin such as in cyanosis or asphyxiation. It may have been imagination, but I was now sure that her expression revealed pain or fear or both. When I looked at her first I had been unable to forget my impression of years. Before me there had been the once living form of Stella Lamar, whom I had dreamed of meeting and whom I had never viewed in actual life. I had lacked the penetration to see beneath the glamour. But to Kennedy there had been signs of the poisoning at once. Doctor Blake had searched merely for the evidences of the commoner drugs, or the usual diseases such as cause sudden death. I recalled the cyanides. I thought of curare, or woorali, the South American arrow poison with which Kennedy once had dealt. Had Stella received an injection of some new and curious substance? Mackay glanced up from his inspection of the mark on the arm. "It's an awfully tiny scratch!" he exclaimed. Kennedy smiled. "Yet, Mackay, it probably was the cause of her death." "How?" "That--that is the problem before us. When we learn just exactly how she scratched herself, or was scratched--" Kennedy paced up and down in front of the fireplace. Then he confronted each of us in turn, suddenly serious. "Not a word of what I have discovered," he warned. III TANGLED MOTIVES "Do you wish to examine the people now?" Mackay asked. Kennedy hesitated. "First I want to make sure of the evidence concerning her actual death. Can you arrange to have the clothes she has on, and those she brought with her, all of them bundled up and sent in to my laboratory, together with samples of her body fluids as soon as the coroner can supply you?" Mackay nodded. This pleased him. This seemed to be tangible action, promising tangible results. Again Kennedy glanced about in thought. I knew that the scratch was worrying him. "Did she change her clothes out here?" he inquired. The district attorney brightened. "She dressed in a small den just off the living room. I have a man posted and the door closed. Nothing has been disturbed." He started to lead the way without further word from Kennedy, proud to have been able once more to demonstrate his foresight. As we left the library, entering the living room, there was an appreciable hush. Here were grouped the others of the party brought out by the picture company, a constrained gathering of folk who had little in common beyond the highly specialized needs of the new art of the screen, an assembly of souls who had been forced to wait during all the time required for the trip of Kennedy and myself out from New York, who were compelled to wait now until he should be ready to examine them. I picked out the electrician in the semi-gloom and with him his fellow members of the technical staff needed in the taking of the scenes in the library. The camera men I guessed, and a property boy, and an assistant director. The last, at any event, of all those in the huge room, had summoned up sufficient nonchalance to bend his mind to details of his work. I saw that he was thumbing a copy of the scenario, or detailed working manuscript of the story, making notations in some kind of little book, and it was that which enabled me to establish his identity at a glance. In a different corner were the principals, two men and a girl still in make-up, and with them the director, and Manton and Phelps. Apart from everyone else, in a sort of social ostracism common to the studios, the two five-dollar-a-day extras waited, a butler and a maid, also in make-up. Oddly enough the total number of these material witnesses to the tragedy was just thirteen, and I wondered if they had noticed the fact. Doctor Blake turned to Kennedy the moment we left the library. "Do you feel it is necessary for me to remain any longer?" he asked. He was apologetic, yet distinctly impatient. "I have neglected several very important calls as it is." Kennedy and Mackay both hastened to assure the physician that they appreciated his co-operation and that they would spare him as much notoriety and inconvenience as possible. Then the three of us hurried across and to the little den which had been converted into a dressing room for Stella's use. Here were all the evidences of femininity, the little touches which a woman can impart to the smallest corner in a few brief moments of occupancy. It was a tiny alcove shut off from the rest of the living room by heavy silk hangings, drawn now and pinned together so as to assure her the privacy she wished. The one window was high and fitted with leaded glass, but it was raised and afforded the maximum of light. Stella's traveling bag sprawled wide open, with many of her effects strewn about in attractive disarray. Her suit, in which she had made the trip to Tarrytown, was thrown carelessly over the back of a chair. Her mirror was fastened up ruthlessly, upon a handsome woven Oriental hanging, with a long hatpin. Powder was spilled upon the couch cover, another Oriental fabric, and her little box of rouge lay face downward on the floor. As we pulled the curtains aside I caught the perfume which still clung to her clothes in the library beyond. As Mackay sniffed also, Kennedy smiled. "Coty's Jacqueminot rose," he remarked. With his usual swift and practiced certainty Kennedy then inspected the extemporized dressing room. He seemed to satisfy himself that no subtle attack had been made upon the girl here, although I doubt that he had held any such supposition seriously in the first place. In my association of several years with Kennedy, following our first intimacy of college days, I had learned that his success as a scientific detective was the result wholly of his thoroughness of method. To watch him had become a never-ending delight, even in the dull preliminary work of a case as baffling as this one. Mackay also seemed content just to enact the role of spectator. Kennedy thumbed through the delicate intimacies of her traveling bag with the keen, impersonal manner which always distinguished him; then he found her beaded handbag and proceeded to rummage through that. Suddenly he paused as he unfolded a piece of note paper, and we gathered around to read: MY DEAR STELLA: Have something very important to tell you. Will you lunch Tuesday at the P. G. tearoom? LARRY. "Tuesday--" murmured Kennedy. "And this is Monday. Who--who is Larry, I wonder?" I hastened to answer the question for him. It was my first opportunity to display my knowledge of the picture players. "Larry--that's Lawrence, Lawrence Millard!" I exclaimed. Then I went on to tell him of the divorce and the circumstances surrounding Stella's life as I knew it. "It--it looks," I concluded, "as if they might have been on the point of composing their differences, after all." Kennedy nodded. I could see, however, that he made a mental note of his intention to question the girl's former husband. All at once another thought struck me and I became eager. It was a possible explanation of the mystery. "Listen, Craig," I began. "Suppose Millard wanted to make up and she didn't. Suppose that she refused to see him or to meet him. Suppose that in a jealous fit he--" "No, Walter!" Kennedy headed me off with a smile. "This wasn't an ordinary murder of passion. This was well thought out and well executed. Not one medical examiner in a thousand would have found that tiny scratch. It may be very difficult yet to determine the exact cause of death. This, my dear Jameson"--it was playful irony--"is a scientific crime." "But Millard--" "Of course! Anyone may be the culprit. Yet you tell me Millard did not contest her divorce and that it would have been very easy for him to file a counter-suit because everyone knew of her relationship with Manton. That, offhand, shows no ill-will on his part. And now we find this note from him, which at least is friendly in tone--" I shrugged my shoulders. It was the same blind alley in which my thoughts had strayed upon the train on our way out. "It's too early to begin to try to fasten the guilt upon anyone," Kennedy added, as we returned to the library through the living room. Then he turned to Mackay. "Have you succeeded in gleaning any facts about the life of Miss Lamar?" he asked. "Anything which might point to a motive, so that I can approach the case from both directions?" "If you ask me," the little district attorney rejoined, "it's a matter of tangled motives throughout. I--I had no sword to cut the Gordian knot and so"--graciously--"I sent for you." "What do you mean by tangled motives?" Kennedy ignored the other's compliment. "Well!" Mackay indicated me. "Mr. Jameson explained about her divorce. No one heard whom she named as corespondent. That's an unknown woman in the case, although it may not mean anything at all. Then there's Lloyd Manton and all the talk about his affair with Miss Lamar. Some one told one of my men that Manton's wife has left him on that account." "Did you question Manton?" "No, I thought I ought to leave all that to you. I was afraid I might put them on their guard." "Good!" Kennedy was pleased. "Did you learn anything else?" "This deputy of mine obtained all these things by gossiping with the girl who plays the maid, and so they may not be reliable. But among the players it is reported that Werner, the director, was having an affair with Stella also, and that Merle Shirley, the 'heavy' man, was seen with her a great deal recently, and that Jack Gordon, the leading man, who was engaged to marry her as soon as her decree was final, was jealous as a consequence, and that Miss Loring, playing the vampire In the story and engaged to Shirley, was even more bitter against the deceased than Gordon, Miss Lamar's fiance. "That made eight people with possible motives for the crime. When I got that far I gave it up. In fact"--Mackay lowered his voice, suddenly--"I don't like the attitude of Emery Phelps. This is his house, you know, and he is the financial backer of Manton Pictures, yet there seems to be an undercurrent of friction between Manton and himself. I--I wanted him to show me some detail of the arrangement of things in the library, but he wouldn't come into the room. He said he didn't want to look at Miss Lamar. There--there was something--and, I don't know. If he is concerned in any way--that would make nine." "You think Miss Lamar and Phelps--" Mackay shook his head. "I don't know." Kennedy turned to me, expression really serious. "Is this the way they carry on in the picture world, Walter?" he asked. "Is this the usual thing or--or an exception?" I flushed. "It's very much an exception," I insisted. "The film people are just like other people, some good and some bad. Probably three-quarters of all this is gossip." "I hope so." He straightened. "The only thing to do is to go after them one at a time and disentangle all the conflicting threads. It looks as though there will be any number of possible false leads and so we must be careful and deliberate. I think I'll question each in turn--here." He walked over to the fireplace, stopping for just a moment to glance at the body of Stella. Then he pulled the blinds down halfway, so that the room seemed somber and gruesome. He drew a chair so that the different individuals as he examined them, would be unable to lose sight of the dead woman. His arrangements completed, he faced the district attorney. "Manton first," he directed. In an instant I caught the psychology of it--the now darkened library, the beautiful body still lying on the davenport, the quiet and quick arrival of ourselves. If anything could be extracted from these people, surely it would be betrayed under these surroundings. IV THE FATAL SCRIPT I had no real opportunity to study Manton when he greeted us upon our arrival, and at that time neither Kennedy nor I possessed even a passing realization of the problem before us. Now I felt that I was ready to grasp at any possible motive for the crime. I was prepared to suspect any or all of the nine people enumerated by Mackay, so far as I could speak for myself, and at the very least I was certain that this was one of the most baffling cases ever brought to Craig's attention. Yet I was sure he would solve it. I waited most impatiently for the outcome of his examination of Lloyd Manton. The producer-promoter was a well-set-up man just approaching middle age. About him was a certain impression of great physical strength, of bulk without flabbiness, and in particular I noticed the formation of his head, the square broad development which indicated his intellectual power, and I found, too, a fascinating quality about his eyes, deeply placed and of a warm dark gray-brown, which seemed to hold a fundamental sincerity which, I imagined, made the man almost irresistible in a business deal. His weakness, so far as I could ascertain it, was revealed by his mouth and chin, and by a certain nervousness of his hands, hands where a square, practical palm was belied by the slight tapering of his fingers, the mark of the dreamer. His mouth was unquestionably sensuous, with the lips full and now and then revealing out of the studied practiced calm of his face an almost imperceptible twitching, as though to betray a flash of emotion, or fear. His chin was feminine, softening his expression and showing that his feelings would overbalance the cool calculation denoted by his eyes and the rather heavy level brows above. As he entered the room, taking the chair indicated by Kennedy, he seemed perfectly cool and his glance, as it strayed to the lifeless form of Stella, revealed his iron self-control. The little signs which I have mentioned, which betrayed the real man beneath, were only disclosed to me little by little as Kennedy's questioning progressed. "Tell me just what happened?" Kennedy began. "Well--" Manton responded quickly enough, but then he stopped and proceeded as though he chose each word with care, as if he framed each sentence so that there would be no misunderstanding, no chance of wrong impression; all of which pleased Kennedy. "In the scene we were taking," he went on, "Stella was crouched down on the floor, bending over her father, who had just been murdered. She was sobbing. All at once the lights were to spring up. The young hero was to dash through the set and she was to see him and scream out in terror. The first part went all right. But when the lights flashed on, instead of looking up and screaming, Stella sort of crumpled and collapsed on top of Werner, who was playing the father. I yelled to stop the cameras and rushed in. We picked her up and put her on the couch. Some one sent for the doctor, but she died without saying a word. I--I haven't the slightest idea what happened. At first I thought it was heart trouble." "Did she have heart trouble?" "No, that is--not that I ever heard." Kennedy hesitated. "Why were you taking these scenes out here?" It was on the tip of my tongue to answer for Manton. I knew that at one time many fine interiors were actually taken in houses, to save expense. I was sorry that Kennedy should draw any conclusion from a fact which I thought was too well known to require explanation. Manton's answer, however, proved a distinct surprise to me. "Mr. Phelps asked us to use his library in this picture." "Wouldn't it have been easier and cheaper in the long run to reproduce it in the studio?" Manton glanced up at Kennedy, echoing my thought. Had Kennedy, after all, some knowledge of motion pictures stored away with his vast fund of general and unusual information? "Yes," replied the producer. "It would save the trip out here, the loss of time, the inconvenience--why, in an actual dollars and cents comparison, with overhead and everything taken into account, the building of a set like this is nothing nowadays." "Do you know Mr. Phelps's reason?" Manton shrugged his shoulders. "Just a whim, and we had to humor it." "Mr. Phelps is interested in the company?" "Yes. He recently bought up all the stock except my own. He is in absolute control, financially." "What is the story you are making? I mean, I want to understand just exactly what happened in the scenes you were photographing today. It is essential that I learn how everyone was supposed to act and how they did act. I must find out every trivial little detail. Do you follow me?" Manton's mouth set suddenly, showing that it possessed a latent quality of firmness. He glanced about the room, then rose, went to the farther end of the long table, and returned with a thick sheaf of manuscript bound at the side in stiff board covers. "This is the scenario, the script of the detailed action," he explained. As Kennedy took the binder, Manton opened it and turned past several sheets of tabulation and lists, the index to the sets and exterior locations, the characters and extras, the changes of clothes, and other technical detail. "The scenes we are taking here," he went on, "are the opening scenes of the story. We left them until now because it meant the long trip out to Tarrytown and because it would take us away from the studio while they were putting up the largest two sets, a banquet and a ballroom which need the entire floor space of the studio." He turned over two or three pages, pointing. "We had taken up to scene thirteen; from scenes one to thirteen just as you have them in order there. It--it was in the unlucky thirteenth that she"--was it my imagination or did he tremble, for just an instant, violently?--"that she died." Kennedy started to read the script. I hurried to his side, glancing over his shoulder. THE BLACK TERROR FEATURING STELLA LAMAH SCENE 1 LOCATION.--Remsen library. This is a modern, luxurious library set with a long table in the center of the room, books around the walls, French windows leading from the rear, and an entrance through a hallway to the right through a pair of portieres. Note: E. P. wishes us to use his library at Tarrytown. ACTION.--Open diaphragm slowly on darkened set as a spot of light is being played on the walls and French windows in the rear. As the diaphragm opens slowly the light vanishes, leaving the scene dark at times and then brightened until, as the diaphragm opens full, we discover that the light is that of a burglar's flash light, traveling over the walls of the library. When the diaphragm is fully opened we discover also a faint line of light streaming through the almost closed portieres leading to the hallway outside. This ray of light, striking along the floor, pauses by the library table, just disclosing the edge of it but not revealing anything else in the room. The spotlight in the hands of a shadowy figure roves across the wall and to the portieres. As it pauses there the portieres move and the fingers of a girl are seen on the edge of the silk. A bare and beautiful arm is thrust through the portieres almost to the shoulder, and it begins to move the portieres aside, reaching upward to pull the curtains apart at the rings. SCENE 2 LOCATION.--Remsen library. Close foreground of portieres. ACTION.--Our heroine parts the portieres and stands revealed in the spotlight's glare. She is in dinner gown and about her throat is a peculiar locket of flashing jewels. She cries out and backs away, closing the portieres. The spotlight retreats from the curtains, leaving them dark. SCENE 3 LOCATION.--Hallway, Remsen house. Close foreground of portieres leading to library. This hallway is lighted. ACTION.--The girl holding the portieres shut screams for help. SCENE 4 LOCATION.--Foot of stairway, Remsen house. ACTION.--The butler and maid are discovered talking. They hear the girl's scream and start running. SCENE 5 LOCATION.--Hallway, Remsen house. Close foreground of portieres. ACTION.--The girl hears help coming and glances off to indicate that she sees the butler and the maid. She continues to cling to the closed curtains. SCENE 6 LOCATION.--Remsen library. Full shot. ACTION.--The unknown drops the spotlight to the floor and we first see his legs crossing the rays of light on the floor. Then the spotlight rolls, revealing the body of an elderly man of the American millionaire type, lying crumpled against the table. Finally it rolls a little farther and stops, directing its rays into the fireplace. SCENE 7 LOCATION.--Remsen hallway, outside library. ACTION.--The girl indicates determined resolve. She throws apart the portieres with a quick motion of her arms and dashes inside. The portieres close after her. The butler and maid come on running and looking about. SCENE 8 LOCATION.--Remsen library. Full shot. ACTION.--The spotlight is showing into the fireplace when the girl crosses quickly into its rays. She stoops into the light, revealing her face and picking up the spotlight. She flashes it about the room, pausing as it strikes the French windows and reveals the murderer making his escape out on a balcony which is revealed in the background. When the rays of light reach the murderer he deliberately turns. SCENE 9 LOCATION.--Remsen library. Close foreground of French windows. ACTION.--The intruder, now in the close foreground, pauses as he is about to shut the window and blinks deliberately into the rays of light, then laughs and closes the French windows. SCENE 10 LOCATION.--Hallway, Remsen home. Close foreground of portieres to library. ACTION.--The butler and maid look around hopelessly. A young man, the exact counterpart of the man who in the previous scene looked into the spotlight at the French windows, comes up to the butler and demands to know what has happened. The butler explains hurriedly that he heard his mistress cry out for help. The young man steps to the portieres and pauses. SCENE 11 LOCATION.--Remsen library. Full shot. ACTION.--The girl, using the spotlight, flashes it about the room and down on the floor, seeing for the first time the body of the American millionaire. SCENE 12 LOCATION.--Exterior Remsen house. Night tint. ACTION.--The murderer scrambles down a column from the upper porch and leaps to the ground, darting across the lawn out of the picture. SCENE 13 LOCATION.--Remsen library. Full shot. ACTION.--The spotlight on the floor reveals the girl sobbing over the body of the millionaire and trying to revive him. She screams and cries out. The portieres are parted and from the lighted hallway we see the young man, the butler, and the maid, who enter. The young man switches on the lights and the room is revealed. The three cry out in horror. The young man, glancing about, leaps toward the partly opened French windows, drawing a revolver. As the girl sees him she screams again and denotes terror. Finishing the thirteenth scene, Kennedy closed the covers and handed the script to me. Then he confronted Manton once more. "What became of the locket about the girl's neck? In the manuscript Miss Lamar is supposed to have a peculiar pendant at her throat. There was none." "Oh yes!" The promoter remained a moment in thought. "The doctor took it off and gave it to Bernie, the prop. boy, who's helping the electrician." "Is he outside?" "Yes." "Now try to remember, Mr. Manton." Kennedy leaned over very seriously. "Just who approached closely to Miss Lamar in the making of that thirteenth scene? Who was near enough to have inflicted a wound, or to have subjected her, suppose we say, to the fumes of some subtle poison?" "You think that--" Manton started to question Kennedy, but was given no encouragement. "Gordon, the leading man, passed through the scene," he replied, after a pause, "but did not go very near her. Werner was playing the dead millionaire at her feet." "Who is Werner?" "He's my director. Because it was such a small part, he played it himself. He's only in the two or three scenes in the beginning and I was here to be at the camera." While Kennedy was questioning Manton I had been glancing through the script of the picture. My own connection with the movies had consisted largely of three attempts to sell stories of my own to the producers. Needless to remark I had not succeeded, in that regard falling in the class with some hundreds of thousands of my fellow citizens. For everybody thinks he has at least one motion picture in him. And so, though I had managed to visit studios and meet a few of the players, this was my very first shot at a manuscript actually in production. I took advantage of Kennedy's momentary preoccupation to turn to Manton. "Who wrote this script, Mr. Manton?" I asked. "Millard! Lawrence Millard." "Millard?" Kennedy and I exclaimed, simultaneously. "Why, yes! Millard is still under contract and he's the only man who ever could write scripts for Stella. We--we tried others and they all flivved." "Is Millard here?" Manton burst into laughter, somehow out of place in the room where we still were in the company of death. "An author on the lot at the filming of his picture, to bother the director and to change everything? Out! When the scenario's done he's through. He's lucky to get his name on the screen. It's not the story but the direction which counts, except that you've got to have a good idea to start with, and a halfway decent script to make your lay-outs from. Anyhow--" He sobered a bit, perhaps realizing that he was going counter to the tendency to have the author on the lot. "Millard and Stella weren't on speaking terms. She divorced him, you know." "Do you know much about the personal affairs of Miss Lamar?" "Well"--Manton's eyes sought the floor for a moment--"Like everyone else in pictures, Stella was the victim of a great deal of gossip. That's the experience of any girl who rises to a position of prominence and--" "How were the relations between Miss Lamar and yourself?" interrupted Kennedy. "What do you mean by that?" Manton flushed quickly. "You have had no trouble, no disagreements recently?" "No, indeed. Everything has been very friendly between us--in a strictly business way, of course--and I don't believe I've had an unpleasant word with her since I first formed Manton Pictures to make her a star." "You know nothing of her difficulties with her husband?" "Naturally not. I seldom saw her except at the studio, unless it was some necessary affair such as a screen ball here, or perhaps in Boston or Philadelphia or some near-by city where I would take her for effect--" Kennedy turned to Mackay. "Will you arrange to keep the people I have yet to question separate from the ones I have examined already?" As the district attorney nodded, Kennedy dismissed Manton rather shortly; then turned again to Mackay as the promoter drew out of earshot. "Bring in Bernie, the property-boy, before anyone can tell him to hide or destroy that locket." V AN EMOTIONAL MAZE Bernie proved to be as stupid a youth as any I had ever seen. He possessed frightened semi-liquid eyes and overshot ears and hair which might have been red beneath its accumulation of dust. Without doubt the boy had been coached by the electrician, because he began to affirm his innocence in similar fashion the moment he entered the door. "I don't know nothin', honest I don't," he pleaded. "I was out in the hall, I was, and I didn't come in at all until the doc. came." "I suppose you were anxious to see if the cable was becoming hot," Kennedy suggested, gravely. "That's it, sir! We was lookin' at it because it was on the varnish and the butler he says--" "Where's the locket?" interrupted Kennedy. "The one Miss Lamar wore in the scenes." "Oh!" in disdain, "that thing!" With some effort Bernie fished it from the capacious depths of a pocket, disentangling the sharp corners from the torn and ragged lining of his coat. I glanced at it as Kennedy turned it over and over in his hands, and saw that it was a palpable stage prop, with glass jewels of the cheapest sort. Concealing his disappointment, Kennedy dropped it into his own pocket, confronting the frightened Bernie once more. "Do you know anything about Miss Lamar's death?" "No! I don't know nothing, honest!" "All right!" Kennedy turned to Mackay. "Werner, the director." Of Stanley Werner I had heard a great deal, through interviews, character studies, and other press stuff in the photoplay journals and the Sunday newspaper film sections. Now I found him to be a high-strung individual, so extremely nervous that it seemed impossible for him to remain in one position in his chair or for him to keep his hands motionless for a single instant. Although he was of moderate build, with a fair suggestion of flesh, there were yet the marks of the artist and of the creative temperament in the fine sloping contours of his head and in his remarkably long fingers, which tapered to nails manicured immaculately. Kennedy seemed to pay particular attention to his eyes, which were dark, soft, and amazingly restless. "Who was in the cast, Mr. Werner? What were they playing and just exactly what was each doing at the time of Miss Lamar's collapse?" "Well"--Werner's eyes shifted to mine, then to Mackay's, and there was a subtle lack of ease in his manner which I was hardly prepared to classify as yet--"Stella Lamar was playing the part of Stella Remsen, the heroine, and--uh, I see your associate has the script--" He paused, glancing at me again. When Kennedy said nothing, Werner went on, growing more and more nervous. "Jack Gordon plays Jack Daring, the hero--the handsome young chap who runs down the steps and encounters the butler and the maid in the hall just outside the library--" "Wasn't it his face in the French windows of the library at the same time?" Kennedy asked. "Wasn't he the murderer of the father, also?" "No!" Werner smiled slightly, and there was an instant's flash of the man's personality, winning and, it seemed to me, calculated to inspire confidence. "That is the mystery; it is a mystery plot. While the parts are played by Jack in both cases now, we explain in a subtitle a little later that the criminal himself, the 'Black Terror,' is a master of scientific impersonation, and that he changes the faces of his emissaries by means of plastic surgery and such scientific things, so that they look like the characters against whom he wishes to throw suspicion. So while Jack plays the part it is really an accomplice of the 'Black Terror' who kills old Remsen." Kennedy turned to me. "A new idea in the application of science to crime!" he remarked, dryly. "Just suppose it were practicable!" "The 'Black Terror'" Werner continued, "is played by Merle Shirley. You've heard of him, the greatest villain ever known to the films? Then there's Marilyn Loring, the vampire, another good trouper, too. She plays Zelda, old Remsen's ward, and it's a question whether Zelda or Stella will be the Remsen heir. Marilyn herself is an awfully nice girl, but, oh, how the fans hate her!" The director chuckled. "No Millard story is ever complete without a vamp and Marilyn's been eating them up. She's been with Manton Pictures for nearly a year." "You played the millionaire yourself?" "Yes, I did old Remsen." I realized suddenly, for the first time, that Werner was still in the evening clothes he had donned for the part. On his face were streaks in the little make-up that remained after his frequent mopping of his features with his handkerchief. Too, his collar was melted. I could imagine his discomfort. "Did you have any business with Stella?" Kennedy asked, using the stage term for the minor bits of action in the playing of a scene. "Did you move at all while she was going through her part?" "No, Mr. Kennedy, I was 'dead man' in all the scenes." "Show me how you lay, if you will." Obligingly, Werner stretched out on the carpet, duplicating his positions even to the exact manner in which he had placed his hands and arms. Rather to my own distaste, Kennedy impressed me to represent, I am sure in clumsy fashion, the various positions of Stella Lamar. Most painstakingly Kennedy worked back from the thirteenth scene to the first, referring to the script and coaxing details of memory from the mind of Werner. I grasped Kennedy's purpose almost at once. He was endeavoring to reproduce the action which had been photographed, so as to determine just how the poison had been administered. Of course he made no reference to the tiny scratch and Mackay and I were careful to give no hint of it to Werner. The director, however, seemed most willing to assist us. I certainly felt no suspicion of him now. As for Kennedy, his face was unrevealing. "When the film in the camera is developed--" I suggested to Kennedy, suddenly. He silenced me with a gesture. "I haven't overlooked that, but the scenes will be from one angle only and in a darkened set. I can determine more this way." Somewhat crestfallen, I continued my impersonation of the slain star not altogether willingly. Soon Kennedy had completed his reconstruction of the action. "Who else entered the scene besides Gordon?" he asked. "The butler and the maid, after the lights were flashed on." "I'll question the camera men," he announced. "Who are they?" "Harry Watkins is the head photographer," Werner explained. "He's a crackerjack, too! One of the best lighting experts in the country. Al Penny's grinding the other box." "Let's have Watkins first." Kennedy nodded to Mackay to escort the director from the room. Neither Watkins nor Penny were able to add anything to the facts which Kennedy had gleaned from Manton and Werner. When he had finished his patient examination of the junior camera man he recalled Watkins and had both, under his eyes, close and seal the film cartridges which contained the photographic record of the thirteen scenes. Dismissing the men, he handed the two black boxes to Mackay. "Can you arrange to have these developed and printed, quickly, but in some way so neither negative nor positive will be out of your sight at any time?" Mackay nodded. "I know the owner of a laboratory in Yonkers." "Good! Now let's have the leading man." Jack Gordon immediately impressed me very unfavorably. There was something about him for which I could find no word but "sleek." Learning much from my long association with Kennedy I observed at once that he had removed the make-up from his face and that he had on a clean white collar. Since the linen worn before the camera is dyed a faint tint to prevent the halation caused by pure white, it was a sure sign to me that he had spruced up a bit. I knew that he was engaged to Stella. Here in this room she lay dead, under the most mysterious circumstances. There was little question, in fact, that she had been murdered. How could he, really loving her, think of such things as the make-up left on his face, or his clothes? I had to admit that he was a handsome individual. Perhaps slightly less than average in height, and very slender, he had the close-knit build of an athlete. The contour of his head and the perfect regularity of rather large features made him an ideal type for the screen at any angle; in close-ups and foregrounds as well as full shots. In actual life there were little things covered by make-up in his work, such as the cold gray tint of his eyes and the lines of dissipation about his mouth. Kennedy questioned him first about his movements in the different scenes, then asked him if he had seen or noticed anything suspicious during the taking of any of them or in the intervals between. "I had several changes, Mr. Kennedy," he replied. "Part of the time I was Jack Daring, my regular role, but I was also the emissary who looked like Daring. I went out each time because I make up the emissary to look hard. Werner wanted to fool the people a little bit, but he didn't want them to be positive the emissary was Daring, as would happen if both make-ups were the same." "Did you have any opportunity to talk to Miss Lamar?" "None at all. Werner was pushing us to the limit." "Did she seem her usual self at the start of the scene?" "No, she seemed a little out of sorts. But"--Gordon hesitated--"something had been troubling her all day. She hardly would talk to me in the car on the way out at all. It didn't strike me that she acted any different when she went in to take the scene." "You were engaged to her?" "Yes." Gordon's eyes caught the body on the davenport before him. He glanced away hastily, taking his lower lip between his teeth. "Had you been having any trouble?" "No--that is, nothing to amount to anything." "But you had a quarrel or a misunderstanding." His face flushed slowly. "She was to obtain her final decree early next week. I wanted her to marry me then at once. She refused. When I reproached her for not considering my wishes she pretended to be cool and began an elaborate flirtation with Merle Shirley." "You say she only pretended to be cool?" For a few moments Gordon hesitated. Then apparently his vanity loosened his tongue. He wished it to be understood that he had held the love of Stella to the last. "Last night," he volunteered, "we made everything up and she was as affectionate as she ever had been. This morning she was cool, but I could tell it was pretense and so I let her alone." "There has been no real trouble between you?" The leading man met Kennedy's gaze squarely. "Not a bit!" Kennedy turned to Mackay. "Mr. Shirley," he ordered. By a miscalculation on the part of the little district attorney the heavy man entered the room a moment before Gordon left. They came face to face just within the portieres. There was no mistaking the hostility, the open hate, between the two men. Both Kennedy and I caught the glances. Then Merle Shirley approached the fireplace, taking the chair indicated by Kennedy. "I wasn't in any of the opening scenes," he explained. "I remained out in the car until I got wind of the excitement. By that time Stella was dead." "Do you know anything of a quarrel between Miss Lamar and Gordon?" Shirley rose, clenching his fists. For several moments he stood gazing down at the star with an expression on his face which I could not analyze. The pause gave me an opportunity to study him, however, and I noticed that while he had heavier features than Gordon, and was a larger man in every way, ideally endowed for heavy parts, there was yet a certain boyish freshness clinging to him in subtle fashion. He wore his clothes in a loose sort of way which suggested the West and the open, in contrast to Gordon's metropolitan sophistication and immaculate tailoring. He was every inch the man, and a splendid actor--I knew. Yet there was the touch of youth about him. He seemed incapable of a crime such as this, unless it was in anger, or as the result of some deep-running hidden passion. Now, whether he was angry or in the clutch of a broad disgust, I could not tell. Perhaps it was both. Very suddenly he wheeled upon Kennedy. His voice became low and vibrant with feeling. Here was none of the steeled self-control of Manton, the deceptive outer mask which Werner used to cover his thoughts, the nonchalant, cold frankness of Gordon. "Mr. Kennedy," the actor exclaimed, "I've been a fool, a fool!" "How do you mean?" "I mean that I allowed Stella to flatter my vanity and lead me into a flirtation which meant nothing at all to her. God!" "You are responsible for the trouble between Miss Lamar and Gordon, then?" "Never!" Shirley indicated the body of the star with a quick, passionate sweep of his hand. Now I could not tell whether he was acting or in earnest. "She's responsible!" he exclaimed. "She's responsible for everything!" "Her death--" "No!" Shirley sobered suddenly, as if he had forgotten the mystery altogether. "I don't know anything at all about that, nor have I any idea unless--" But he checked himself rather than voice an empty suspicion. "Just what do you mean, then?" Kennedy was sharp, impatient. "She made a fool of me, and--and I was engaged to Marilyn Loring--" "Were engaged? The engagement--" "Marilyn broke it off last night and wouldn't listen to me, even though I came to my senses and saw what a fool I had been." "Was"--Kennedy framed his question carefully--"was your infatuation for Miss Lamar of long duration?" "Just a few weeks. I--I took her out to dinner and to the theater and--and that was all." "I see!" Kennedy walked away, nodding to Mackay. "Will you have Miss Loring next?" asked the district attorney. Kennedy nodded. Marilyn Loring was a surprise to me. Stella Lamar both on the screen and in real life was a beauty. In the films Marilyn was a beauty also, apparently of a cold, unfeeling type, but in the flesh she was disclosed as a person utterly different from all my preconceived notions. In the first place, she was not particularly attractive except when she smiled. Her coloring, hair frankly and naturally red, skin slightly mottled and pale, produced in photography the black hair and marble, white skin which distinguished her. But as I studied her, as she was now, before she had put on any make-up and while she was still dressed in a simple summer gown of organdie, she looked as though she might have stepped into the room from the main street of some mid-Western town. In repose she was shy, diffident in appearance. When she smiled, naturally, without holding the hard lines of her vampire roles, there was the slight suggestion of a dimple, and she was essentially girlish. When a trace of emotion or feeling came into her face the woman was evident. She might have been seventeen or thirty-seven. To my surprise, Kennedy made no effort to elicit further information concerning the personal animosities of these people. Perhaps he felt it too much of an emotional maze to be straightened out in this preliminary investigation. When he found Marilyn had watched the taking of the scenes he compared her account with those which he had already obtained. Then he dismissed her. In rapid succession, for he was impatient now to follow up other methods of investigation, he called in and examined the remaining possible witnesses of the tragedy. These were the two extra players--the butler and the maid, the assistant director, Phelps's house servants, and Emery Phelps himself. For some unknown reason he left the owner of the house to the very last. "Why did you wish these scenes photographed out here?" he asked. "Because I wanted to see my library in pictures." "Were you watching the taking of the scenes?" "Yes!" "Will you describe just what happened?" Phelps flushed. He was irritated and in no mood to humor us any more than necessary. A man of perhaps forty, with the portly flabbiness which often accompanies success in the financial markets, he was accustomed to obtaining rather than yielding obedience. A bachelor, he had built this house as a show place merely, according to the gossip among newspaper men, seldom living in it. "Haven't about a dozen people described it for you already?" he asked, distinctly petulant. Kennedy smiled. "Did you notice anything particularly out of the way, anything which might be a clue to the manner in which Miss Lamar met her death?" Phelps's attitude became frankly malicious. "If I had, or if any of us had, we wouldn't have found it necessary to send for Prof. Craig Kennedy, or"--turning to me--"the representative of the New York Star." Kennedy, undisturbed, walked to the side of Mackay. "I'll leave Mr. Phelps and his house in your care," he remarked, in a low voice. Mackay grinned. I saw that the district attorney had little love for the owner of this particular estate in Tarrytown. Kennedy led the way into the living room. Immediately the various people he had questioned clustered up with varying degrees of anxiety. Had the mystery been solved? He gave them no satisfaction, but singled out Manton, who seemed eager to get away. "Where is Millard? I would like to talk to him." "I'll try to get him for you. Suppose--" Manton looked at his watch. "I should be in at the studio," he explained. "Everything is at a standstill, probably, and--and so, suppose you and Mr. Jameson ride in with me in my car. Millard might be there." Kennedy brightened. "Good!" Then he looked back to catch the eye of Mackay. "Let everyone go now," he directed. "Don't forget to send me the samples of the body fluids and"--as an afterthought--"you'd better keep a watch on the house." VI THE FIRST CLUE Manton's car was a high-powered, expensive limousine, fitted inside with every luxury of which the mind of even a prima donna could conceive, painted a vivid yellow that must have made it an object of attention even on its familiar routes. It was quite characteristic of its owner, for Manton, as we learned, missed no chance to advertise himself. In the back with us was Werner, while the rest of the company were left to return to the city in the two studio cars which had brought them out in the morning. The director, however, seemed buried with his reflections. He took no part in the conversation; paid no attention to us upon the entire trip. Manton's mind seemed to dwell rather upon the problems brought up by the death of Stella than upon the tragedy itself. The Star's photoplay editor once had remarked to me that the promoter was 90 per cent "bull," and 10 per cent efficiency. I found that it was an unfair estimation. With all his self-advertisement and almost obnoxious personality, Manton was a more than capable executive in a business where efficiency and method are rare. "This has been a hoodoo picture from the start," he exclaimed, suddenly. "We have been jinxed with a vengeance. Some one has held the Indian sign on us for sure." Kennedy, I noticed, listened, studying the man cautiously from the corners of his eyes, but making no effort to draw him out. "First there were changes to be made in the script, and for those Millard took his own sweet time. Then we were handed a lot of negative which had been fogged in the perforator, a thing that doesn't happen once in a thousand years. But it caught us just as we sent the company down to Delaware Water Gap. A whole ten days' work went into the developer at once. Neither of the camera men caught the fog in their tests because it came in the middle of the rolls. Everything had to be done over again. "And accidents! We carefully registered the principal accomplice of the 'Black Terror,' a little hunchback with a face to send chills down your back. After we had him in about half the scenes of a sequence of action he was taken sick and died of influenza. First we waited a few days; then we had to take all that stuff over again. "Our payroll on this picture is staggering. Stella's three thousand a week is cheap for her, the old contract, but it's a lot of money to throw away. Two weeks when she was under the weather cost us six thousand dollars salary and there was half a week we couldn't do any work without her. Gordon and Shirley and Marilyn Loring draw down seventeen hundred a week between them. The director's salary is only two hundred short of that. All told 'The Black Terror' is costing us a hundred thousand dollars over our original estimate. "And now"--it seemed to me that Manton literally groaned--"with Stella Lamar dead--excuse me looking at it this way, but, after all, it is business and I'm the executive at the head of the company--now we must find a new star, Lord knows where, and we must retake every scene in which Stella appeared. It--it's enough to bankrupt Manton Pictures for once and all." "Can't you change the story about some way, so you won't lose the value of her work?" asked Kennedy. "Impossible! We've announced the release and we've got to go ahead. Fortunately, some of the biggest sets are not taken yet." The car pulled up with a flourish before the Manton studio, which was an immense affair of reinforced concrete in the upper Bronx. Then, in response to our horn, a great wide double door swung open admitting us through the building to a large courtyard around which the various departments were built. Here, there was little indication that the principal star of the company had just met her death under mysterious and suspicious circumstances. Perhaps, had I been familiar with the ordinary bustle of the establishment, I might have detected a difference. Indeed, it did strike me that there were little knots of people here and there discussing the tragedy, but everything was overshadowed by the aquatic scene being filmed in the courtyard for some other Manton picture. The cramped space about the concrete tank was alive with people, a mob of extras and stage hands and various employees, a sight which held Kennedy and me for some little time. I was glad when Manton led the way through a long hall to the comparative quiet of the office building. In the reception room there was a decided hush. "Is Millard here?" he asked of the boy seated at the information desk. "No, sir," was the respectful reply. "He was here this morning and for a while yesterday." "You see!" Manton confronted Kennedy grimly. "This is only one of the things with which we have to contend in this business. I give Millard an office but he's a law unto himself. It's the artistic temperament. If I interfere, then he says he cannot write and he doesn't produce any manuscript. Ordinarily he cannot be bothered to work at the studio. But"--philosophically--"I know where to get him as a general thing. He does most of his writing in his rooms downtown; says there's more inspiration in the confusion of Broadway than in the wilds of the Bronx. I'll phone him." We followed the promoter up the stairs to the second and top floor. Here a corridor gave access to the various executive offices. Its windows at frequent intervals looked down upon the courtyard and the present confusion. Werner, who had preceded us into the building, now came up. As Manton bustled into his own office to use the telephone the director turned to Kennedy, indicating the next doorway. "This is my place," he explained. "It connects with Manton, on one side, through his reception room. You see, in addition to directing Stella Lamar I have been in general charge of production and most of the casting is up to me." Kennedy entered after Werner, interested, and I followed. The door through to the reception room stood open and beyond was the one to Manton's quarters. I could see the promoter at his desk, receiver at his ear, an impatient expression upon his face. In the reception room a rather pretty girl, young and of a shallow-pated type I thought, was busy at a clattering typewriter. She rose and closed the door upon Manton, so as not to disturb him. "The next office on this side is Millard's," volunteered Werner. "He's the only scenario writer dignified with quarters in this building." "Manton has other writers, hasn't he?" Kennedy asked. "Yes, the scenario department is on the third floor across the court, above the laboratory and cutting rooms." "Who else is in the building here?" "There are six rooms on this floor," Werner replied. "Manton, the waiting room, myself, Millard, and the two other directors. Below is the general reception room, the cashier, the bookkeepers and stenographers." As Manton probably was having trouble obtaining his connection, and as Kennedy continued to question Werner concerning the general arrangement of the different floors in the different buildings about the quadrangle, all uninteresting to me, I determined to look about a bit on my own hook. I was still anxious to be of genuine assistance to Kennedy, for once, through my greater knowledge of the film world. Strolling out into the corridor, I went to the door of Millard's room. To my disappointment, it was locked. Continuing down the hall, I stole a glance into each of the two directors' quarters but saw nothing to awaken my suspicion or justify my intrusion. Beyond, I discovered a washroom, and, aware suddenly of the immense amount of dust I had acquired in the ride in from Tarrytown, I entered to freshen my hands and face at the least. It was a stroke of luck, a fortunate impulse. The amount of money to be made in the movies had resulted, in the case of Manton, in luxurious equipment for all the various departments of his establishment. I had noticed the offices, furnished with a richness worthy of a bank or some great downtown institution. Now, in the lavatory, immaculate with its white tile and modern appointments, I saw a shelf literally stacked, in this day of paper, with linen towels of the finest quality. As I drew the water, hot instantly, my eye caught, half in and half out of the wire basket beneath the stand, one of the towels covered with peculiar yellow spots. Immediately my suspicions were awakened. I picked it up gingerly. At close range I saw that the spots were only chrome yellow make-up, but there were also spots of a different nature. I did not stop to think of the unlikeliness of the discovery of a real clue under these circumstances, analyzed afterward by Kennedy. I folded the towel hastily and hurried to rejoin him, to show it to him. I found him with Werner, waiting for the results of Manton's efforts to locate Millard. Almost at the moment I rejoined the two a boy came to summon Werner to one of the sets out on the stage itself. Kennedy and I were alone. I showed him the towel. At first he laughed, "You'll never make a detective, Walter," he remarked. "This is only simple coloring matter-Chinese yellow, to be exact. And will you tell me, too"--he became ironical--"how do you expect to find clues of this sort here for a murder committed in Tarrytown when all the people present were held out there and examined, when we are the first to arrive back here? "Yellow, you know, photographs white. Chinese yellow is used largely in studios in place of white in make-up because it does not cause halation, which, to the picture people, is the bane of their existence. White is too glaring, reflects rays that blur the photography sometimes. "If you will notice, the next time you see them shooting a scene, you will find the actors' faces tinged with yellow. Even tablecloths and napkins and 'white' dresses are frequently colored a pale yellow, although pale blue has the actinic qualities of white for this purpose, and is now perhaps more frequently used than yellow." I was properly chastened. In fact, though I did not say much, I almost determined to let him conduct his case himself. Kennedy saw my crestfallen expression and understood. He was about to say something encouraging, as he handed back the towel, when his eye fell on the other end of it, which, indeed, I myself had noticed. He sobered instantly and studied the other spots. Indeed, I had not examined them closely myself. They were the very faint stains of some other yellow substance, a liquid which had dried and did not rub off as the make-up, and there were also some small round drops of dark red, almost hidden in the fancy red scrollwork of the lettering on the towel, "Manton Pictures, Inc." The latter had escaped me altogether. "Blood!" Kennedy exclaimed. Then, "Look here!" The marks of the pale yellow liquid trailed into a slender trace of blood. "It looks as if some one had cleaned a needle on it," he muttered, "and in a hurry." I remembered his previous remark. The murder had been in Tarrytown. We had just arrived here. "Would anyone have time to do it?" I asked. "Whoever used the towel did so in a hurry," he reiterated, seriously. "It may have been some one afraid to leave any sort of clue out there at Phelps's house. There were too many watchers about. It might have seemed better to have run the risk of a search. With no sign of a wound on Miss Lamar's person, it was pretty certain that neither Mackay nor I would attempt to frisk everyone. It was not as though we were looking for a revolver, if she were shot, or a knife, if she had been stabbed. And"--he could not resist another dig at me--"and that we should look in a washroom here for a towel was, well, an idea that wouldn't occur to anyone but the most amateur and blundering sort of sleuth. It's beginner's luck, Walter, beginner's luck." I ignored the uncomplimentary part of his remarks. "Who could have been in the washroom just before me?" I asked. Suddenly he hurried through the waiting room to the door to Manton's office, opening it without ceremony. Manton was gone. We exchanged glances. I remembered that Werner had preceded us upstairs. "It means Werner or Manton himself," I whispered, so the girl just behind us would not hear. Kennedy strode out to the hall, and to a window overlooking the court. After a moment he pointed. I recognized both the cars used to transport the company to the home of Emery Phelps. There was no sign that either had just arrived, for even the chauffeurs were out of sight, perhaps melted into the crowd about the tank in the corner. "They must have arrived immediately behind us," Kennedy remarked. "We wasted several valuable minutes looking at that water stuff ourselves." At that moment Werner's voice rose from the reception room below. It was probable that he would be up to rejoin us again. I remembered that he had not been at all at ease while Kennedy questioned him in Tarrytown; that here at the studio he had been palpably anxious to remain close at our heels. I felt a surge of suspicion within me. "Listen, Craig," I muttered, in low tones. "Manton had no opportunity to steal down the hall after the girl closed the door, and--" "Why not!" he interrupted, contradicting me. "We had our backs to the door while we were talking with Werner." "Well, anyhow, it narrows down to Manton and Werner because that is the washroom for these offices--" "'Sh!" Kennedy stopped me as Werner mounted the stairs. He turned to the director with assumed nonchalance. "How long have the other cars been here?" he asked. "I thought we came pretty fast." Werner smiled. "I guess those boys had enough of Tarrytown. They rolled into the yard, both of them, while you and Mr. Jameson and Manton were stopping to watch the people in the water." "I see!" Kennedy gave me a side glance. "Where are the dressing rooms?" he inquired. It was a random shot. Werner pointed to the end of the hall, toward the washroom. "In the next building, on this floor--that is, the principals'. It's a rotten arrangement," he added. "They come through sometimes and use our lavatory, because it's a little more fancy and because it saves a trip down a flight of stairs. Believe me, it gets old Manton on his ear." VII ENID FAYE Behind Werner was the assistant director, to whom I had given little attention at the time of the examination of the various people in the Phelps library. Even now he impressed me as one of those rare, unobtrusive types of individuals who seem, in spite of the possession of genuine ability and often a great deal of efficiency, to lack, nevertheless, any outstanding personal characteristics. As a class they are human machines, to be neither liked nor disliked, never intruding and yet always on hand when needed. "This is Carey Drexel, my assistant," Werner stated, forgetting that Kennedy had questioned him at Tarrytown, and so knew him. "There are a few people I simply must see and I'm tied up, therefore, for perhaps half an hour; and Manton's downstairs still trying to locate Millard for you. But Carey's at your disposal, Mr. Kennedy, to show you the arrangement of the studio and to cooperate with you in any way if you think there's any possible chance of finding anything to bear upon Stella's death here." If Werner was the man who had used the towel, I could see that he was an actor and a cool villain. Of course no one could know, yet, that we had discovered it, but the very nonchalance with which it had been thrown into the basket was a mark of the nerve of the guilty man. It was more than carelessness. Nothing about the crime had been haphazard. Kennedy thanked Werner and asked to be shown the studio floor used in the making of "The Black Terror." Carey led the way, explaining that there were actually two studios, one at each end of the quadrangle, connected on both sides by the other buildings; offices and dressing rooms and the costume and property departments at the side facing the street; technical laboratories and all the detail of film manufacture in a four-story structure to the rear. Most of Werner's own picture was being made in the so-called big studio, reached through the dressing rooms from the end of the corridor where we stood. I had been in film plants before, but when we entered the huge glass-roofed inclosure beyond the long hallway of dressing rooms I was impressed by the fact that here was a place of genuine magnitude, with more life and bustle than anything I had ever imagined. The glass had, however, been painted over, because of late years dark stages, with the even quality of artificial light, had come into vogue in the Manton studios in place of stages lighted by the uneven and undependable sunlight. The two big sets mentioned by Manton, a banquet hall and a ballroom, were being erected simultaneously. Carpenters were at work sawing and hammering. Werner's technical director was shouting at a group of stage hands putting a massive mirror in position at the end of the banquet hall, a clever device to give the room the appearance of at least double its actual length. In one corner several electricians and a camera man were experimenting with a strange-looking bank of lights. In the ballroom set, where the flats or walls were all in place, an unexcited paperhanger was busy with the paraphernalia of his craft, somehow looking out of his element in this reign of pandemonium. It seemed hard indeed to believe that any sort of order or system lay behind this heterogeneous activity, and the incident which took Carey Drexel away from us only added to the wonder in my mind, a wonder that anything tangible and definite could be accomplished. "Oh, Carey!" Another assistant director, or perhaps he was only a property boy, rushed up frantically the moment he saw Drexel. "Miss Miller's on a rampage because the grand piano you promised to get for her isn't at her apartment yet, and Bessie Terry's in tears because she left her parrot here overnight, as you suggested, and some one taught the bird to swear." The intruder, a youth of perhaps eighteen, was in deadly earnest. "For the love of Mike, Carey," he went on, "tell me how to unteach that screeching thing of Bessie's, or we won't get a scene today." Carey Drexel looked at Kennedy helplessly. With all these troubles, how could he pilot us about? Later we learned that this was nothing new, once one gets on the inside of picture making. Props., or properties, particularly the living ones, cause almost as much disturbance as the temperamental notions of the actors and actresses. Sometimes it is a question which may become the most ridiculous. Kennedy seemed to be satisfied with his preliminary visit to this studio floor. "We can get back to Manton's office alone," he told Drexel. "We will just keep on circling the quadrangle." Relieved, the assistant director pointed to the door of the manufacturing building, as the four-story structure in the rear was called. Then he bustled off with the other youth, quite unruffled himself. When we passed through the heavy steel fire door we found ourselves in another long hallway of fire-brick and reinforced-concrete construction. Unquestionably there was no danger of a serious conflagration in any part of Manton's plant, despite the high inflammability of the film itself, of the flimsy stage sets, of practically everything used in picture manufacture. Immediately we entered this building I detected a peculiar odor, at which I sniffed eagerly. I was reminded of the burnt-almond odor of the cyanides. Was this another clue? I turned to Kennedy but he smiled, anticipating me. "Banana oil, Walter," he explained, with rather a superior manner. "I imagine it's used a great deal in this industry. Anyway"--a chuckle--"don't expect chance to deliver clues to you in wholesale quantities. You have done very well for today." A sudden whirring noise, from an open door down the hall, attracted us, and we paused. This, I guessed, was a cutting room. There were a number of steel tables, with high steel chairs. At the walls were cabinets of the same material. Each table had two winding arrangements, a handle at the operator's right hand and one at his left, so that he could wind or unwind film from one reel to another, passing it forward or backward in front of his eyes. There were girls at the tables except nearest the hall. Here a man stopped now and then to glance at the ribbon of film, or to cut out a section, dropping the discarded piece into a fireproof can and splicing the two ends of the main strip together again with liquid film cement from a small bottle. He looked up as he sensed our presence. "Isn't it hell?" he remarked, in friendly fashion. "I've got to cut all of Stella Lamar out of 'The Black Terror,' so they can duplicate her scenes with another star, and meanwhile we had half the negative matched and marked for colors and spliced in rolls, all ready for the printer." Without waiting for an answer from us, or expecting one, he gave one of his reels a vicious spin, producing the whirring noise; then grasping both reels between his fingers and bringing them to an abrupt stop, so that I wondered he did not burn himself from the friction, he located the next piece to be eliminated. We followed the hall into the smaller studio and there found a comedy company at work. Without stopping to watch the players, ghastly under the light from the Cooper-Hewitts and Kliegel arcs, we found a precarious way back of the set around and under stage braces, to the covered bridge leading once more to the corridor outside Manton's office. Now the girl was absent from her place in the little waiting room. Manton's door stood open. Without ceremony Kennedy led the way in and dropped down at the side of the promoter's huge mahogany desk. "I'm tired, Walter," he said. "Furthermore, I think this picture world of yours is a bedlam. We face a hard task." "How do you propose to go about things?" I asked. "I'm afraid this is a case which will have to be approached entirely through psychological reactions. You and I will have to become familiar with the studio and home life of all the long list of possible suspects. I shall analyze the body fluids of the deceased and learn the cause of death, and I will find out what it is on the towel, but"--sighing--"there are so many different ramifications, so many--" Suddenly his eye caught the corner of a piece of paper slid under the glass of Manton's desk. He pulled it out; then handed it to me. MEMORANDUM FOR MR. MANTON Have learned Enid Faye is out of Pentangle and can be engaged for about twelve hundred if you act quickly. Why not cancel Lamar contract after "Black Terror," if she continues up-stage? WERNER. "I caught the name Lamar," Kennedy explained. Then an expression of gratification crept into his face. "Miss Lamar was 'up-stage'?" he mused. "That's a theatrical word for cussedness, isn't it?" I paid little attention. The name of Enid Faye had attracted my own interest. This was the little dare-devil who had breezed into the Pacific Coast film colony and had swept everything before her. Not only had she displayed amazing nerve for her sex and size, but she had been pretty and beautifully formed, had been as much at home in a ballroom as in an Annette Kellermann bathing suit. In less than six months she had learned to act and had been brought to the Eastern studios of Pentangle. Now it was possible that she would be captured by Manton, would be blazoned all over the country by that gentleman, would become another star of his making. "Let's go, Walter!" Kennedy, impatient, rose. I noticed that he folded the little note, slipping it into his pocket. Out in the hall voices came to us from Werner's office. After some little hesitation Kennedy opened the door unceremoniously. At the table, littered with blue prints and drawings and colored plates of famous home interiors, was the director. With him was Manton. Seated facing them, in rare good humor, was a fascinating little lady. The promoter rose. "Professor Kennedy, I want you to meet Miss Enid Faye, one of our real comers. And Mr. Jameson, Enid, of the New York Star." She acknowledged the introduction to Kennedy gracefully. Then she turned, rising, and rushed to me most effusively, leading me to a leather-covered couch and pulling me to a seat beside her. "Mr. Jameson," she purred. "I just love newspaper men; I think they're perfectly wonderful always. Tell me, do you like little Enid?" I nodded, confused and unhappy, and as red as a schoolboy. "That's fine," she went on, in the best modulated and most wonderful voice I thought I had ever heard. "I like you and I know we're going to be the best of friends. Tell me, what's your first name?" "Now, Enid," reproved Manton, in fatherly tones, "you'll have plenty of time to vamp your publicity later. For the present, please listen to me. We're talking business." "Shoot every hair of this old gray head!" she directed, pertly. She did not move away, however, I could feel the warmth of her, could catch the delicacy of the perfume she used. I noted the play of her slender fingers, the trimness of her ankle, the piquancy of a nose revealed to me in profile--and nothing else. "This is your chance, Enid," Manton continued, earnestly and rather eagerly. "You know the film will be the most talked about one this year. We've got the Merritt papers lined up and that's the best advertising in the world. Everyone will know you took Stella's place, and--well, you'll step right in." She studied the tips of her boots, stretching boyish limbs straight in front of her, then smoothing the soft folds of her skirt. "Talk money to me, Mr. Man!" she exclaimed. "Talk the shekels, the golden shekels." "We're broke," he protested. "A thousand--" She shook her head. Werner broke in, suddenly anxious. "Don't pass up the chance, Enid," he pleaded. "What can Pentangle do for you? And I've always wanted to direct you again--" "I'll make it twelve hundred," Manton interrupted, "if you'll make the contract personally with me. Then if Manton Pictures--" "All right!" She jumped to her feet, extending a hand straight forward to each, the right to Manton, the left to Werner. "You're on!" I thought that I was forgotten. A wave of jealousy swept over me. After all, she simply wanted me to write her up. In a daze I heard Manton. "You're a wise little girl, Enid," he told her. "Play the game right with me and you'll climb high. The sky's the limit, now. I'll make you--make you big!" With a full, warm smile she swung around to me and I knew I was not being slighted, after all. "That's what Longfellow said, isn't it, Mr. Jameson?" "What?" My heart began to beat like a trip hammer. "Excelsior! Excelsior! It packs them in!" She laughed so infectiously that we all joined in. Then Manton turned to Kennedy. "I've located Millard for you. He's to meet us at my apartment at seven. It's six-thirty now. And you, Enid"--facing her--"if you'll come, too, there's another man I want you to meet, and Larry, of course, will be there--" Enid studied Kennedy. He was hesitating as though not sure whether to accompany Manton or not. I never did learn what other course of action had occurred to him. But I did notice that the little star, with her pert, upturned face, seemed more anxious to have Kennedy go along than she was to meet the mysterious individual mentioned without name by Manton. For an instant she was on the point of addressing him, flippantly, no doubt. Then, I think she was rather awed at Craig's reputation. All at once she shrugged her shoulders and turned to me, plucking my sleeve, her expression brightening irresistibly. "You'll come, too"--dimpling--"Jamie!" VIII LAWRENCE MILLARD It struck me on the trip to Manton's apartment that the film people were wholly unfeeling, were even uninterested in the death of Stella Lamar except where it interfered with their business arrangements. Werner excused himself and did not accompany us, on the score of the complete realignment of production necessary to place Enid in Stella's part. It seemed to me that he felt a certain relish in the problem, that he was almost glad of the circumstances which brought Enid to him. His last words to Manton were, to be sure to have Millard recast the action of the scenes wherever possible, so as to give Enid the better chance to display her own personality. I marveled as I realized that the remains of Stella Lamar were scarcely cold before these people were figuring on the star to take her place. As Manton talked, the thought crossed my mind that such a man needed no publicity manager. I dismissed the idea that he might be capable even of murder for publicity. But at least it was an insight into some methods of the game. As our car mounted to the Concourse and turned Manhattanward I was distinctly unhappy. Manton monopolized Enid completely, insisting upon talking over everything under the sun, from the wardrobe she would need in Stella's part and the best sort of personal advertising campaign for her, to the first available evening when she could go to dinner with him. She sat in the rear seat, between Kennedy and the promoter, which did not add to my sense of comfort. The only consoling feature from my viewpoint was that I was admirably placed to study her, and that Manton held her so engrossed that I had every opportunity to do so unnoticed. Because she had overwhelmed me so completely I did nothing of the kind. I knew we were riding with the most beautiful woman in New York, but I did not know the color of her hair or eyes, or even the sort of hat or dress she wore. In short I was movie-struck. We stopped at last at a huge, ornate apartment house on Riverside Drive and Manton led the way through the wide Renaissance entrance and the luxurious marble hall to the elevator. His quarters, on the top floor, facing the river, were almost exotic in the lavishness and barbaric splendor of their furnishings. My first impression as we entered the place was that Manton had purposely planned the dim lights of rich amber and the clinging Oriental fragrance hovering about everything so as to produce an alluring and enticing atmosphere. The chairs and wide upholstered window seats, the soft, yielding divans in at least two corners, with their miniature mountains of tiny pillows, all were comfortable with the comfort one associates with lotus eating and that homeward journey soon to be forgotten. There was the smoke of incense, unmistakably. On a taboret were cigarettes and cigars and through heavy curtains I caught a glimpse of a sideboard and decanters, filled and set out very frankly. A Japanese butler, whom Manton called Huroki, took our hats and retreated with a certain emanating effluvium of subtlety such as I had known only once before, when the Oriental attendant left me on the occasion of my only visit to an opium den in Chinatown. A moment later Millard, who had been waiting, rose to greet us. I would have guessed him to be an author, I believe, had I met him at random anywhere in the city. He affected all the professional marks and mannerisms, and yet he did so gracefully. I noticed, in the little hall where Huroki placed our headgear, a single-jointed Malacca stick, a dark-colored and soft-brimmed felt hat, and a battered brief-case. That was Millard, unquestionably. The man himself was tall and loose-limbed, heavy with an appearance of slenderness. His face was handsome, rather intellectual in spite of rather than because of large horn-rimmed glasses. His mouth and chin showed strength and determination, which was a surprise to me. In fact, in no way did he seem to reveal the artist. Lawrence Millard was a commercial writer, a dreamer never. First he greeted Enid, taking both of her hands in his. In this one brief moment all my own little romance went glimmering, for I could not blind myself to the softening of his expression, the welcoming light in hers, the long interval in which their fingers remained interlaced. And then another thought came to me, hastened, fed and fattened upon my jealousy. The sealed testimony in the case of Millard vs. Millard! Could Enid, by any chance, be concerned in that? The next moment I dismissed the thought, or at least I thought I did so. I tried to picture Enid's work on the Coast, to remember the short time she had been in the East. It was possible Millard had known her before she went to Los Angeles, but unlikely. Millard next turned to Kennedy. "I just learned of the tragedy a short while ago, Professor," he exclaimed. "It is terrible, and so amazingly sudden, too! It--it has upset me completely. Tell me, have you found anything? Have you discovered any possible clue? Is there anything at all I can do to help?" "I would like to ask a few questions," Kennedy explained. "By all means!" He extended a hand to me and I found it damp and flabby, as though he were more concerned than his manner betrayed. He faced Kennedy again, however, immediately. "Stella and I didn't make a go of our married life at all," he went on, frankly enough. "I was very sorry, too, because I was genuinely fond of her." "How recently have you seen her?" "Stella? Not for over a month--perhaps longer than that." Manton took Enid by the arm. It was evidently her first visit to the apartment and he was anxious to show her his various treasures. Millard, Kennedy, and I found a corner affording a view out over the Hudson. After Kennedy had described, briefly, the circumstances of Stella's death, at Millard's insistence, he produced the note he had found in her handbag. The author recognized it at once, without reading it. "Yes, I wrote that!" Then just a trace of emotion crept into his voice. "I was too late," he murmured. "What was it you wanted to say?" Kennedy inquired. Millard's glance traveled to Manton and Enid, a troubled something in his expression. I could see that the promoter was making the most of his tete-a-tete with the girl, but she seemed perfectly at ease and quite capable of handling the man, and I, certainly, was more disturbed at the interest of Millard. "I thought there was something about the business I ought to tell Stella," he answered, finally. "Manton Pictures is pretty shaky." "Oh! Then Manton wasn't talking for effect when he told Miss Faye that the company was broke?" "No, indeed! In fact, didn't Enid make her agreement with Manton personally? That's what I advised her to do." Kennedy nodded. "But is Manton himself financially sound?" Millard laughed. "Lloyd Manton always has a dozen things up his sleeve. He may have a million or he may owe a million." In the author's voice was no respect for his employer. A touch of malice crept into his tone. "Manton will make money for anyone who can make money for him," he added, "that is, provided he has to do it." Kennedy and I exchanged glances. This was close to an assertion of downright dishonesty. At that moment Huroki stole in on padded feet, as noiseless as a wraith. "Yes, Huroki?" His master turned, inquiringly. "Mr. Leigh," was the butler's announcement. "Show him in," said Manton; then he hurried over to us. "Courtlandt Leigh, the banker, you know." I imagine I showed my surprise, for Kennedy smiled as he caught my face. Leigh was a bigger man than Phelps, of the highest standing in downtown financial circles. If Manton had interested Courtlandt Leigh in moving pictures he was a wizard indeed. It seemed to me that the banker was hardly in the apartment before he saw Enid, and from that moment the girl engrossed him to the exclusion of everything else. For Enid, I will say that she was a wonder. She seemed to grasp the man's instant infatuation and immediately she set about to complete the conquest, all without permitting him so much as to touch her. "You'll excuse us?" remarked Manton, easily, as he drew Phelps and Enid away. "See!" exclaimed Millard, in a low voice, frowning now as he watched the girl. "Manton's clever! I've never known him unable to raise money, and that's why I wanted Enid to have her contract with him personally. If Manton Pictures blows up he'd put her in some other company." "He has more than one?" This seemed to puzzle Kennedy. "He's been interested in any number on the side," Millard explained. "Now he's formed another, but it's a secret so far. You've heard of Fortune Features, perhaps?" Kennedy looked at me, but I shook my head. "What is 'Fortune Features'?" Kennedy asked the question of Millard. "Just another company in which Manton has an interest," he replied, casually. "That was why I said I advised that Enid make her contract personally with Manton. If Manton Pictures goes up, then he will have to swing her into Fortune Features--the other Manton enterprise, don't you see?" He paused, then added: "By the way, don't say anything outside about that. It isn't generally known--and as soon as anyone does hear it, everybody in the film game will hear it. You don't know how gossip travels in this business." Kennedy asked a few personal questions about Stella, but Millard's answers indicated that he had not contemplated or even hoped for a reconciliation, that his interest in his former wife had become thoroughly platonic. Just now, however, he seemed unable to keep Manton out of his mind. "Oh, Manton's clever!" he said, confidentially to Kennedy, as he watched the promoter deftly maneuvering Leigh and Enid into a position side by side. And indeed, as Millard talked, I began to get some inkling of how really clever was the game which Manton played. "Why," continued Millard, warming up to his story--for, to him, above all, a good story was something that had to be told, whatever might result from it--"I have known him to pay a visit some afternoon to Wall Street--go down there to beard the old lions in their den. He always used to show up about the closing time of the market. "I've known him to get into the office of some one like Leigh or Phelps. Then he'll begin to talk about his brilliant prospects in the company he happens to be promoting at the time. If you listen to Manton you're lost. I know it--I've listened," he added, whimsically. "Well," he continued, "the banker will begin to get restless after a bit--not at Manton, but at not getting away. 'My car is outside,' Manton will say. 'Let me drive you uptown.' Of course, there's nothing else for the banker to do but to accept, and when he gets into Manton's car he's glad he did. I don't know anyone who picks out such luxurious things as he does. Why, that man could walk right out along Automobile Row, broke, and some one would GIVE him a car." "How does he do it?" I put the question to him. "How does a fish swim?" said Millard, smiling. "He's clever, I tell you. Once he has the banker in the car, perhaps they stop for a few moments at a club. At any rate, Manton usually contrives it so that, as they approach his apartment, he has his talk all worked up to the point where the banker is genuinely interested. You know there's almost nothing people will talk to you longer about than moving pictures. "Well, on one pretext or another, Manton usually persuades the banker to step up here for a moment. Poor simp! It's all over with him then. I'll never forget how impressed Phelps was with this place the first time. There, now, watch this fellow, Leigh. He thinks this looks like a million dollars. We're all here, playing Manton's game. We're his menagerie--he's Barnum. I tell you, Leigh's lost, lost!" I did not know quite what to make of Millard's cynicism. Was he trying to be witty at Manton's expense? I noticed that he did not smile himself. Although he was talking to us, his attention was not really on us. He was still watching Enid. "Then, along would happen Stella, as if by chance." Millard paused bitterly, as though he did not quite relish the telling it, but felt that Kennedy would pry it out of him or some one else finally, and he might as well have it over with frankly. "Yes," he said, thoughtfully, "but it all wasn't really Manton's fault, after all. Stella liked the Bohemian sort of life too much--and Manton does the Bohemian up here wonderfully. It was too much for Stella. Then, when Phelps came along and was roped in, she fell for him. It was good-by, poor Millard! I wasn't rapid enough for that crowd." I almost began to sympathize with Millard in the association into which, for his living's sake, his art had forced him. I realized, too, that really the banker, the wise one from Wall Street, was the sucker. Indeed, as Millard told it, I could easily account for the temptation of Stella. To a degree, I suppose, it was really her fault, for she ought to have known the game, shown more sense than to be taken in by the thing. I wondered at the continued relations of Millard with Manton, under the circumstances. However, I reflected, if Stella had chosen to play the little fool, why should Millard have allowed that to ruin his own chances? What interested me now was that Millard did not seem to relish the attentions which the banker was paying to Enid. Was Manton framing up the same sort of game again on Leigh? However, when Enid shot a quick glance at Millard in an aside of the conversation, accompanied by a merry wink, I saw that Millard, though still doubtful, was much more at ease. Evidently there was a tacit understanding between the two. Kennedy glanced over at me. Bit by bit the checkered history of Stella Lamar's life was coming to light. I began to see more clearly. Deserting Millard and fascinated by Manton and his game, she had been used to interest Phelps in the company. In turn she had been dazzled by the glitter of the Phelps gold. She had not proved loyal even to the producer and promoter. Perhaps, I reflected, that was why Millard was so apparently complacent. One could not, under the circumstances, have expected him to display wild emotion. His attitude had been that of one who thought, "She almost broke me; let her break some one else." That, however, was not his attitude toward Enid now. Indeed, he seemed genuinely concerned that she should not follow in the same steps. Later, I learned that was not all of the history of Stella. Fifteen hundred dollars a week of her own money, besides lavish presents, had been too much for her. Even Phelps's money had had no over-burdening attraction for her. The world--at least that part of it which spends money on Broadway, had been open to her. Jack Daring had charmed her for a while--hence the engagement. Of Shirley, I did not even know. Perhaps the masterful crime roles he played might have promised some new thrill, with the possibility that they expressed something latent in his life. At any rate, she had dilettanted about him, to the amazement and dismay of Marilyn. That we knew. The dinner hour was approaching, and, in spite of the urgent invitation of Manton, Leigh was forced to excuse himself to keep a previous appointment. I felt, though, that he would have broken it if only Enid had added her urging. But she did not, much to the relief of Millard. Manton took it in good part. Perhaps he was wise enough to reflect that many other afternoons were in the lap of the future. "What is Manton up to?" Kennedy spoke to Millard. "Is it off with the old and on with the new? Is Phelps to be cast aside like a squeezed-out lemon, and Leigh taken on for a new citrus fruit?" Millard smiled. He said nothing, but the knowing glance was confirmation enough that in his opinion Kennedy had expressed the state of affairs correctly. Millard hastened to the side of Enid at once and we learned then that they had a theater engagement together and that Millard had the tickets in his pocket. Once more I realized it was no new or recent acquaintanceship between these two. Again I wondered what woman had been named in Stella Lamar's divorce suit, and again dismissed the thought that it could be Enid. Kennedy took his hat and handed me mine. "We must eat, Walter, as well as the rest of them," he remarked, when Manton led the way to the door. I was loath to leave and I suppose I showed it. The truth was that little Enid Faye had captivated me. It was hard to tear myself away. In the entrance I hesitated, wondering whether I should say good-by to her. She seemed engrossed with Millard. A second time she took me clean off my feet. While I stood there, foolishly, she left Millard and rushed up, extending her little hand and allowing it to rest for a moment clasped in mine. "We didn't have a single opportunity to get acquainted, Mr. Jameson," she complained, real regret in the soft cadences of her voice. "Won't you phone me sometime? My name's in the book, or I'll be at the studio--" I was tongue-tied. My glance, shifting from hers because I was suddenly afraid of myself, encountered the gaze of Millard from behind. Now I detected the unmistakable fire of jealousy in the eyes of the author. I presume I was never built to be a heavy lover. Up and down my spine went a shiver of fear. I dropped Enid's hand and turned away abruptly. IX WHITE-LIGHT SHADOWS "What do you think of it?" I asked Kennedy, when we were half through our meal at a tiny restaurant on upper Broadway. "We're still fumbling in the dark," he replied. "There's the towel--" "Yes, and almost any one on Mackay's list of nine suspects could have placed it in that washroom." "Well--" I was determined to draw him out. My own impressions, I must confess, were gloriously muddled. "Manton heads the list," I suggested. "Everyone says she was mixed up with him." "Manton may have philandered with her; undoubtedly he takes a personal interest in all his stars." Kennedy, I saw, remembered the promoter's close attentions to Enid Faye. "Nevertheless, Walter, he is first and foremost and all the time the man of business. His heart is in his dollars and Millard even suggests that he is none too scrupulous." "If he had an affair with Stella," I rejoined, "and she became up-stage--the note you found suggested trouble, you know--then Manton in a burst of passion--" "No!" Kennedy stopped me. "Don't forget that this was a cold-blooded, calculated crime. I'm not eliminating Manton yet, but until we find some tangible evidence of trouble between Stella and himself we can hardly assume he would kill the girl who's made him perhaps a million dollars. Every motive in Manton's case is a motive against the crime." "That eliminates Phelps, then, too. He nearly owned the company." "Yes, unless something happened to outweigh financial considerations in his mind also." "But, good heavens! Kennedy," I protested. "If you go on that way you'll not eliminate anyone." "I can't yet," he explained, patiently. "It's just as I said. We're fishing in the dark, absolutely. So far we haven't a single basic fact on which to build any structure of hypothesis. We must go on fishing. I expect you to dig up all the facts about these people; every odd bit of gossip or rumor or anything else. I'll bring my science to play, but there's nothing I can do except analyze Stella's stomach contents and the spots on the towel; that is, until we've got a much more tangible lead than any which have developed so far." "Is there anything I can do to-night?" "Yes!" He looked at his watch. "There are two men who were very close to Miss Lamar. Jack Gordon was engaged to her, Merle Shirley seemed to have been mixed up with her seriously. All the picture people have night haunts. See what you can find about these two men." "But I don't know where to find them offhand, and--" "Both belong to the Goats Club, probably. Try that as a start." I nodded and began to hurry my dessert. But I could not resist questioning him. "You think they are the most likely suspects?" "No, but they were intimately associated with Miss Lamar in her daily life and they are the two we have learned the least about." "Oh!" I was disappointed. Then I rallied to the attack for a final time. "Who is the most likely one. Just satisfy my curiosity, Craig." He took a folded note from his pocket, opening it. It was the memorandum from Manton's desk which I had mentioned. In a flash I understood. "Werner!" I exclaimed. "They said he was mixed up with her, too. He was the first back and out of the car and he had time to clean a needle on the towel, had a better opportunity than anyone else. More"--I began to get excited--"he was lying on the floor close to her in the scene and could have jabbed her with a needle very easily, and--and he was extremely nervous when you questioned him, the most nervous of all, and--and, finally, he had a motive, he wanted to get Enid Faye with Manton Pictures, as this note shows." "Very good, Walter." Kennedy's eyes were dancing in amusement. "It is true that Werner had the best motive, so far as we know now, but it's a fantastic one. Men don't commit cold-blooded murder just to create a vacancy for a movie star. If Werner was going to kill Miss Lamar he never would have written this note about Miss Faye." "Unless to divert suspicion," I suggested. He shook his head. "The whole thing's too bizarre." "Werner was close to her in the dark. All the other things point to him, don't they?" "It's too bad everyone wasn't searched, at that," Kennedy admitted. "Nevertheless, at the time I realized that Werner had had the best opportunity for the actual performance of the crime and I watched him very closely and made him go through every movement just so I could study him. I believe he's innocent--at least as far as I've gone in the case." I determined to stick to my opinion. "I believe it's Werner," I insisted. "By the time you've dug up all the gossip about Gordon and Shirley you won't be so sure, Walter." I was, however. Kennedy was not as familiar with the picture world as I. I had heard of too many actual happenings more strange and bizarre and wildly fantastic than anything conceivable in other walks of life. People in the film game, as they call it, live highly seasoned lives in which everything is exaggerated. The mere desire to make a place for Enid might not have actuated Werner, granting he was the guilty man. Nevertheless it could easily have contributed. And it struck me suddenly, an additional argument, that Werner, of all of them, was the most familiar with the script. He had been able to cast himself for the part of old Remsen. There was not a detail which he could not have arranged very skillfully. At the Goats Club I was lucky to discover a member whom I knew well enough to take into my confidence by stating my errand. He was one of the Star's former special writers and an older classman of the college which had graduated Kennedy and myself. "Merle Shirley is not a member here," he said. "As a matter of fact, I've only just heard the name. But Jack Gordon's a Goat, worse luck. That fellow's a bad actor--in real life--and a disgrace to us." "Tell me all you know about him?" I asked. "Well, to give you an example, he was in here just about a week ago. I was sitting in the grill, eating an after-theater supper, when I heard the most terrible racket. He and Emery Phelps, the banker, you know, were having an honest-to-goodness fight right out in the lobby. It took three of the men to separate them." "What was it all about." "Well, Gordon owes money right and left, not a few hundred or some little personal debts like that, but thousands and thousands of dollars. I got it from some of the other men here that he has been speculating on the curb downtown, losing consistently. More than that, he's engaged to Stella Lamar--you knew that?--and he's been blowing money on her. Then they tell me his professional work is suffering, that his recent screen appearances are terrible; the result of late hours and worry, I suppose." "The fight with Phelps was over money?" "Of course! I figure that he kept drawing against his salary at the studio until the film company shut down on him. Then probably he began to borrow from Phelps, who's Manton's backer now, until the banker shut down on him also. At any rate, Phelps had begun to dun him and it led to the fight." "That's all you know about Gordon?" "Lord! Isn't it enough?" I walked out of the club and toward Broadway, reflecting upon this information. Could Gordon's debts have any bearing upon the case? All at once one possibility struck me. He had been borrowing from Phelps. Perhaps he had borrowed from Stella also. Perhaps that was the cause of their quarrel. Perhaps she had threatened to make trouble--it was a slender motive, but worth bringing to the attention of Kennedy. My immediate problem, however, was to obtain some information about Merle Shirley. At first I thought I would make the rounds of some of the better-known cafes, but that seemed a hopeless task. Suddenly I remembered Belle Balcom, formerly with the Star. I recollected a previous case of Kennedy's where she and I had been great rivals in the quest of news. I recalled a trip we had made to Greenwich Village together. Belle knew more people about town than any other newspaper woman. Now, for some months, she had been connected with Screenings, a leading cinema "fan" magazine, and would unquestionably be posted upon the photoplayers. Luckily, I caught her at home. "Bless your soul," she told me over the phone, in delight, "I've just been aching for some one to take me out to-night. We'll go to the Midnight Fads and if Shirley isn't there the head waiter will tell you all I don't remember. It was a glorious fight." She wouldn't say any more over the phone, but I was hugely curious. Had there been another encounter with fists? And who had been involved? When she met me finally, at the Subway station, and when we obtained an out-of-the-way table at the Fads, she explained. It seemed that Shirley had met Stella there a number of times and that Gordon, at last, had got wind of it. Gordon first had come up himself, quietly, pleading with Stella. She had been in a high humor and had refused even to listen to him. Then he had become insulting. At that Shirley knocked him down. The head waiter, a witness of the affair, ordered Gordon put out, but did not request Shirley or Stella to leave, because the other man had been the aggressor without any question. After more than an hour Gordon returned, quietly and unobtrusively, with another girl. From Belle's description I knew it was Marilyn Loring. Taking another table, Marilyn had stared at Shirley reproachfully while Gordon had glared at Stella. Shirley put up with this for just about so long. As Belle described it, his face gradually became more and more red and he controlled himself with increasing difficulty. Stella, seeing the coming of the storm, tried to get him to go. He refused. She threatened to leave him. He paid no attention. All at once he boiled over and with great strides walked over to Gordon and mauled him all over the place. The leading man had no chance whatever in the hands of the irate Westerner. Several waiters, attempting to intervene, were flung aside. Only when Shirley began to cool off were they able to eject the two men. Both Stella and Marilyn had left, separately, before that. Neither of the men or women had been at the Fads since, or at least the head waiter, called over by Belle, so informed us. Unable to obtain any other facts of interest, I returned finally to the apartment shared by Kennedy and myself. First he listened to my account, plainly interested. Then, when I had concluded, he rose and faced me rather gravely. "It's getting more and more complicated, Walter," he exclaimed. "After you left I remembered that there was one point of investigation I had failed to cover--Miss Lamar's home here in the city. I got our old friend, First-Deputy O'Connor, on the wire and learned that at the request of Mackay, from Tarrytown, they had sent a man up to the place and that just an hour or less before I called they had located and were holding her colored maid. I hurried down to headquarters and questioned the girl." "Yes?" To me it sounded promising. "The negress didn't know a thing so far as the crime is concerned," Kennedy went on, "but I gained quite an insight into the private life of the star." "You mean--" "I mean I know the men who went to Miss Lamar's apartment, although beyond the fact of her receiving them I can tell nothing, for she sent the maid home at night; there were no maid's quarters." "Their visits may have been perfectly innocent?" "Of course! We can only draw conclusions." "Who were the various callers?" "Jack Gordon--" "Her fiance!" "Merle Shirley--" "Shirley admitted it when you questioned him." "Manton--" "Everyone knows that!" "Werner--" A side glance at me. I said nothing. My expression spoke for me. "And Emery Phelps!" At that I did show surprise. Although Mackay had hinted at something of the kind, I, for one, had not considered the banker seriously. "Good heavens! Kennedy," I exploded. "She was mixed up with just about every man connected with the company." "Exactly!" As usual, he seemed calm and unconcerned. I could regard the case only with increasing amazement--the bitter, conflicting emotions of Manton and Phelps, of Daring, Shirley, and Millard. With them all Stella had been the pretty trouble maker. "How do you suppose they could all remain in the same company?" I showed my surprise at the situation. Kennedy pondered a moment, then replied: "A moment's reflection ought to give you one answer. I think, Walter, they were either under contract or they had their money in the company. They couldn't break." "I suppose so. What I wonder is, was Marilyn as jealous of Stella as her screen character would make her in a story? She's the only one we don't hear much about." Kennedy did not seem, at least at present, to give this phase of it anything like the weight he credited to the frenzied financial relations the case was uncovering. It was true, as I learned later, that Manton was at that very moment doing perhaps as much as anyone else ever did to discredit the picture game in Wall Street. X CHEMICAL RESEARCH The following morning I found Kennedy up ahead of me, and I felt certain that he had gone to the laboratory. Sure enough, I found him at work in the midst of the innumerable scientific devices which he had gathered during years of crime detection of every sort. As usual, he was surrounded by a perfect litter of test tubes, beakers, reagents, microscopes, slides, and culture tubes. He had cut out the curious spots from the towel I had discovered and was studying them to determine their nature. From the mass of paraphernalia I knew he was neglecting no possibility which might lead to the hidden truth or produce a clue to the crime. "Have you learned anything yet?" I asked. "Those brownish spots were blood, of course," was his reply as he stopped a moment in his work. "In the blood I discovered some other substance, though I can't seem to identify it yet. It will take time. I thought it might be a drug or poison, but it doesn't seem to be--at least nothing one might ordinarily expect." "How about the other spots, not the Chinese yellow?" "Another problem I haven't solved. I dissolved enough of them so that I have plenty of material to study if I don't waste it. But so far I haven't been able to identify the substance with anything I know. There's a lot more work of elimination, Walter, before we're on the road to the solution of this case. Whatever stained the towel was very unusual. As near as I can make out the spots are of some protein composition. But it's not exactly a poison, although many proteins may be extremely poisonous and extremely difficult to identify because they are of organic nature." I was disappointed. It seemed to me that he had made comparatively little progress so far. "There's one thing," he added. "Samples of the body fluids of the victim have been sent down by the coroner at Tarrytown and I have analyzed them. While I haven't decided what it was that killed Stella Lamar, I am at least convinced that it has something to do with these towel spots. They are not exactly the same--in fact, I should say they were complementary, or, perhaps better, antithetical." "The mark wasn't made by the needle which scratched her, then?" "That's what I thought at first, that the point used had been wiped off on the towel. Then I decided that the spots had nothing to do with the case at all. Now I believe there is some connection, after all." "I--I don't understand it," I protested. "It's very baffling," he agreed, absent-mindedly. "If the towel wasn't used to clean the fatal needle," I went on, "then it may have been used before they went out instead of afterward." "Exactly. As a matter of fact, if I had not been so confused yesterday by all the details of the case, by the many people involved, I would have noticed at a glance that the blood spots on the towel could not come from some one using it to wipe the needle. And any hypothesis that it had been used out in Tarrytown was ridiculous, because Miss Lamar was only scratched faintly and lost no blood. If I had been a little more clever I might have been altogether too clever. I might possibly have thrown the towel away, because there certainly was no logical reason for connecting it with the crime." "Just when do you suppose Stella was pricked?" I asked. "That's a vital consideration. Just now I do not know the poison and so cannot tell how quickly it acted." He began to put aside his various paraphernalia. "Suppose we go at this thing by a process of deduction rather than from the end of scientific analysis." He sat on a corner of the bench. "What do we find?" he began. "While I've been working here with the test tubes and the microscope I've been trying to reconstruct what must have happened, trying to trace out every action of Stella Lamar as nearly as it is possible for us to do so. I don't think we need to go back of their arrival at the house, for the present. They seem to have been there a long while before the taking of the particular scene, since there were twelve other scenes preceding and since it requires time to put up the electric lights and make the connections, as well as to set the cameras, take tests, rearrange the furniture, and all the rest of it. "They arrived at the house in two automobiles; with the exception of Phelps, who was there already, and Manton, who came in his own limousine. That means that Miss Lamar had company on the trip out, the principals probably riding with each other in one car. At the house they were all more or less together. There were people about constantly and it would seem as if there was small opportunity for anyone to inflict the scratch which caused her death. I don't mean that it would have been impossible to prick her. I mean that she would have felt the jab of the point. In all likelihood she would have cried out and glanced around. Take a needle yourself, sometime, Walter, and try to duplicate the scratch on your own arm in such a way that you would not be aware of it. "So you see I'm counting upon some sort of exclamation from Miss Lamar. If she were inoculated with the poison with other folks about, it is sure some one would have remembered a cry, a questioning glance, a quick grasp of the forearm--for the nerves are very sensitive in the skin there--" "No one did recall anything of the kind," I interrupted. "It is from that fact that I hope to deduce something. Now let's follow her, figuratively, to her little dressing room. This was a part of the living room where the rest waited. It is not a certainty, but yet rather a sure guess, that if she had received a scratch behind those thin silk curtains her cry would have been heard. What is even more plausible is that she would have hurried out, or at least put her head out, to see who had pricked her. "I made a very careful examination of that little alcove with the idea that some artifice might have been used. It occurred to me that a poisoned point could have been inserted in her belongings in some way so that she would have brought about her own death, directly. To have caught herself on a needle point in her bag, for instance, would not have impressed her to the point of making a disturbance. She might have checked her exclamation, in that case, because she would be blaming herself. "But I found nothing in her things, nor did I discover anything in the library. It seems to me, therefore, that we must look for a direct human agency." A thought struck me and I hastened to suggest it. "Could some device have been arranged in her clothes, Craig; something like the poison rings of the Middle Ages, a tiny metal thing to spring open and expose its point when pressed against her in the action of the scenes?" "That occurred to me at the time. That's why I asked Mackay to send all her clothes down here, every stitch and rag of them. I've gone over everything already this morning. Not only have I examined the various materials for stains, but I've tested each hook and eye and button and pin. I've been very careful to cover that possibility." "You think, then, she was scratched deliberately by some one during the taking of the scenes?" "If you've followed my line of reasoning you will see that we are driven to that assumption. Perhaps later I will make tests on a given number of girls of Stella's general age and type and temperament to show that they will cry out at the unexpected prick of a fine needle. It's illogical to expect that a cry from Miss Lamar, even an exclamation, would have passed unnoticed except during the excitement of actual picture taking." Another inspiration came to me, but I was almost afraid to voice it. It seemed a daring theory. "Could death have resulted from poison administered in some other fashion, by something she had eaten, for instance?" I ventured. "Couldn't the scratch be coincidental?" Kennedy shook his head. "There's the value of our chemical analysis and scientific tests. Her stomach contents showed nothing except as they might have been affected by her weakened condition. From Doctor Blake's report--and he found no ordinary symptoms, remember--and from my own observation, too, I can easily prove in court that she was killed by the mark which was so small that it escaped the physician altogether." I turned away. Once more Kennedy's reasoning seemed to be leading into a maze of considerations beyond me. How could the deductive method produce results in a case as mysterious as this? "Having determined that Miss Lamar received the inoculation during the making of one of the scenes, as nearly as we can do so," Kennedy went on, "suppose we take the scenes in order, one at a time, from the last photographed to the first, analyzing each in turn. Remember that we seek a situation where there is not only an opportunity to jab her with a needle, but one in which an outcry would be muffled or inaudible." I now saw that Kennedy had brought in the bound script of the story, "The Black Terror," and I wondered again, as I had often before, at his marvelous capacity for attention to detail. "'The spotlight on the floor reveals the girl sobbing over the body of the millionaire,'" he read, aloud, musingly. "H'mm! 'She screams and cries out.' Then the others rush in." For several moments Kennedy paced the floor of the laboratory, the manuscript open in his hands. "We rehearsed that, with Werner; and we questioned everyone, too. And remember! Miss Lamar, instead of crying out as she was supposed to do, just crumpled up silently. So"--thumbing over a page--"we work back to scene twelve. She--she was not in that at all. Scene eleven--" Slowly, carefully, Kennedy went through each scene to the beginning. "Certainly a dramatic opening for a mystery picture," he remarked, suddenly, as though his mind had wandered from his problem to other things. "We must admit that Millard can handle a moving-picture scenario most beautifully." Whether it was professional jealousy or the thought of Enid, rather than the memory of my own poor attempts at screen writing, I certainly was in no mood to agree with Kennedy, for all that I knew he was correct. "Here!" He thrust the binder in my hands. "Read that first scene," he directed. "Meanwhile I am going to phone Mackay to make sure he has had the house guarded and to make double sure no one goes near the library. We're going out to Tarrytown again, Walter, and in the biggest kind of hurry." "What's the idea, Craig?" Kennedy's occasional bursts of mysteriousness, characteristic of him and often necessary when his theories were only half formed and too chaotic for explanations, always piqued me. He did not seem to hear. Already he was at the telephone, manipulating the receiver hook impatiently. "What a dummy I am!" he exclaimed, with genuine feeling. "What--what an awful dummy!" Knowing I would get nothing out of him just yet, I turned to the scene, reading as he told me. At first I could not see where the detail concerned Stella Lamar in any way. Then I came to the description of her introductory entrance, the initial view of her in the film. The lines of typewriting suddenly stood out before me in all their suggestive clearness. The spotlight in the hands of a shadowy figure roves across the wall and to the portieres. As it pauses there the portieres move and the fingers of a girl are seen on the edge of the silk. A bare and beautiful arm is thrust through almost to the shoulder and it begins to move the portieres aside, reaching upward to pull the curtains apart at the rings. "You think there's something about the portieres--" I began. Then I saw that Kennedy had his connection, that something disturbed him, that some intelligence from the other end had caught him by surprise. "You say you were just trying to get me, Mackay? You've something to tell me and you want me to come right out--you have summoned Phelps and he's on his way from the city also--?" "What happened?" I asked, as Kennedy hung up. "I don't know, Walter. Mackay said he didn't want to talk over the phone and that we had just time to catch the express." "But--" "Hurry!" He glanced about as if wondering whether any of his scientific instruments would help him. XI FORESTALLED On the train Kennedy left me, to look through the other cars, having the idea that Phelps might be aboard also. But there were no signs of the banker. We would reach Tarrytown first unless he had chosen to motor out. Mackay was waiting at the station to meet us and to take us to the house. The little district attorney was obviously excited. "Was the place guarded well last night?" asked Kennedy, almost before we had shaken hands. "Yes--that is, I thought it was. That's what I want to tell you. After you left with Manton and Werner the rest of the company packed up and pulled out in the two studio cars. I was a little in doubt what to do about Phelps, but he settled it himself by announcing that he was going to town. The coroner came and issued the permit to remove the body and that was taken away. I think the house and the presence of the dead girl and all the rest of it got on Phelps's nerves, because he was irritable and impatient, unwilling to wait for his own car, until finally I drove him to the station myself." "Was anyone, any of those on our list of possible suspects at least, alone in the room--or in the house?" "Not while I was there," Mackay replied. "I took good care of that. Then, when everyone was gone and while Phelps was waiting for me, I detailed two of my deputies to stay on guard--one inside and one outside--for the night. I thought it sufficient precaution, since you had made your preliminary examination." "And--" Kennedy nodded, seeking to hurry the explanation. "And yet," added Mackay, "some one entered the house last night in spite of us." Kennedy fairly swore under his breath. He seemed to blame himself for some omission in his investigation the previous afternoon. "How did it happen?" I asked, rather excitedly. "It was about three o'clock, the guards tell me. The man inside was dozing in a chair before the living-room fireplace. He was placed so he could command a view of the doorway to the library as well as the stairs and reception hall. All at once he was awakened by a shot and a cry from outside. He jumped up and ran toward the library. As he did so the portieres bellied in toward him, as if in stiff sudden draught, or as if some one had darted into their folds quickly, then out. With no hesitation he drew his own weapon, rushing the curtains. There was no one secreted about them. Then, with the revolver in one hand, he switched on the lights. The room was empty. But one pair of French windows at the farther end were wide open and it was that which had caused the current of air. He ran over and found the lock had been forced. It was not even an artistic job of jimmying." "What about the deputy posted outside?" prompted Kennedy. "That's the strange part of it. He was alert enough, but it's a big house to watch. He swears that the first thing he knew of any trouble was the sharp metallic click which he realized later was the sound made by the intruder in forcing the catch of the French window. It was pretty loud out in the quiet of a Tarrytown night. "He started around from the rear and then the next thing he caught was the outline of a shadowy slinking figure as a man dropped out of the library. He called. The intruder broke into a run, darting across the open space of lawn and crashing through the shrubbery without any further effort at concealment. My man called again and began to chase the stranger, finally firing and missing. In the shrubbery a sharp branch whipped him under the chin just as he obtained a clear view of the outlined figure of his quarry and as he raised his weapon to shoot again. The revolver was knocked from his hand and he was thrown back, falling to the ground and momentarily stunned. Whoever broke into the library got away, of course." "What did the intruder look like?" There was an eagerness in Kennedy's manner. I grasped that the case was beginning to clarify itself in his mind. Mackay shook his head. "There was no moon, you know, and everything happened swiftly. "But was he tall or short or slender or stout--the deputy must have got some vague idea of him at least." "It was one of my amateur deputies," Mackay admitted, reluctantly. "He thought the man was hatless, but couldn't even be sure of that." "Were there footprints, or fingerprints--" "No, Mr. Kennedy, we're out of luck again. When he jumped out he fell to his hands and knees in a garden bed. The foot marks were ruined because his feet slid and simply made two irregular gashes. The marks of his hands indicated to me, anyhow, that he wore heavy gloves, rubber probably." "Any disturbance in the library?" "Not that I could notice. That's why I phoned you at once. I'm hoping you'll discover something." "Well--" Kennedy sighed. "It was a wonderful opportunity to get to the bottom of this." "I haven't told you all yet, Mr. Kennedy," Mackay went on. "There was a second man, and--" "A second man?" Kennedy straightened, distinctly surprised. "I would swear this whole thing was a one-man job." "They weren't together," the district attorney explained. "That's why I didn't mention them both at once. But my deputy says that when he was thrown by the lash of the branch he was unable to move for a few seconds, on account of the nerve shock I suppose, and that while he was motionless, squatted in a sort of sitting position with hands braced behind him, just as he fell, he was aware of a second stranger concealed in the shrubbery. "The second fellow was watching the first, without the question of a doubt. While the deputy slowly rose to his feet this other chap started to follow the man who had broken into the house. But at that moment there was the sudden sound of a self-starter in a car, then the purr of a motor and the clatter of gears. Number one spun off in the darkness of the road as pretty as you please. Number two grunted, in plain disgust. "By this time my deputy had his wind. His revolver was gone, but he jumped the second stranger with little enough hesitation and they battled royally for several minutes in the dark. Unfortunately, it was an unequal match. The intruder apparently was a stocky man, built with the strength of a battleship. He got away also, without leaving anything behind him to serve for identification." "You have no more description than of the first man?" "Unfortunately not. Medium height, a little inclined to be stocky, strong as a longshoreman--that's all." "Are you sure your deputy isn't romancing?" "Positively! He's the son of one of our best families here, a sportsman and an athlete. I knew he loved a lark, or a chance for adventure, and so I impressed him and a companion as deputies when I met them on the street on my way up to Phelps's house just after the tragedy." Kennedy lapsed into thought. Who could the self-constituted watcher have been? Who was interested in this case other than the proper authorities? Apparently some one knew more than Mackay, more than Kennedy. Whoever it was had made no effort to communicate with any of us. This was a new angle to the mystery, a mystery which became deeper as we progressed. At the house Kennedy first made a careful tour of the exterior, but found nothing. Mackay had doubled his guards and had sent Phelps's servants away so that there could be no interference. Once inside, I noticed that Kennedy seemed indisposed to make another minute search of the library. He went over the frame of the French window with his lens carefully, for fingerprints. Finding nothing, he went back directly to the portieres. For several moments he stood regarding them in thought. Then he began a most painstaking inspection of the cloth with the pocket glass, beginning at the library side. I remembered that first scene in the manuscript which Kennedy had insisted I read. I recalled the suspicion which had flashed to me before the message from Mackay had disturbed both Kennedy's thoughts and mine. Stella Lamar had thrust her bare arm through this curtain. A needle, cleverly concealed in the folds, might easily have inflicted the fatal scratch. It was for a trace of the poison point that Kennedy searched. Of that I was sure, knowing his methods. I glanced up and down the heavy hanging silk, looking for the glint of fine sharp steel as Kennedy had done before starting his inspection with the glass. The color of the silk, a beautiful heavy velour, was a strange dark tint very close to the grained black-brown of the woodwork. Both the thickness of the material and its dull shade made the portieres serve ideally for the purpose assumed now both by Kennedy and myself. A tiny needle might remain secreted within their folds for days. Nothing, certainly, caught my naked eye. At last a little exclamation from Kennedy showed us that he had discovered something. I moved closer, as did Mackay. "It's lucky none of us toyed with these curtains yesterday," he remarked, with a slight smile of gratification. "There might have been more than one lying where Stella Lamar lies at the present moment." With wholesome respect neither Mackay nor myself touched the silk as Kennedy pointed. There were two small holes, almost microscopic, in the close-woven material. About the one there was the slightest discoloration. Not a fraction of an inch away I saw two infinitesimal spots of a dark brownish-red tinge. "What does it mean?" I asked, although I could guess. "The dark spots are blood, the discoloration the poison from the needle." "And the needle?" He shrugged his shoulders. "That's where our very scientific culprit has forestalled me, Walter! The needle was in these curtains all day yesterday. Unfortunately, I did not study the manuscript, did not attach any importance to Miss Lamar's scene at the portieres." "The man who broke in last night--" "Removed the needle, but"--almost amused--"not the traces of it. You see, Walter, after all, the scientific detective cannot be forestalled even by the most scientific criminal. There is nothing in the world which does not leave its unmistakable mark behind, provided you can read it. The hole in the cloth serves me quite as well as the needle itself." Very suddenly a voice from behind us interrupted. "Find something?" I turned, startled, to see Emery Phelps. There was a distinct eagerness in the banker's expression. "Yes!" Kennedy faced him, undisturbed, apparently not surprised. His scrutiny of Phelps's face was frank and searching. "Yes," he repeated, "bit by bit the guilty man is revealing himself to us." XII EMERY PHELPS "There--there is something the matter with the curtains?" Phelps suggested. Kennedy pointed to the two holes and the spots. "Miss Lamar met her death from poison introduced into her system through a tiny scratch from a prepared needle." "Yes?" Phelps was calm now, and cool. I wondered if it were pretense on his part. "What have these little marks to do with that?" "Don't you see?" rejoined Kennedy. "If some one had come here before the scene in the picture was played; had thrust a small needle, perhaps a hollow needle from a hypodermic syringe, through the heavy thickness of this silk--thrust it in here, the point sticking out here--well, there would be two holes left where the threads were forced apart, like this!" Kennedy took his stickpin, demonstrating. "How could that cause Stella's death?" Phelps, at first quite upset apparently by Kennedy's discovery, now was lapsing again into his hostile mood. His question was cynical. "Try to recall Miss Lamar's actions," Kennedy went on, patiently. "What was she supposed to do in the very first scene? 'The portieres move and the fingers of a girl are seen on the edge of the silk. A bare and beautiful arm is thrust through almost to the shoulder and it begins to move the portieres aside, reaching upward to pull the curtains apart at the rings.'" "Do you mean to tell me--" Phelps's eyes were very wide as he paused, grasping the scheme and yet disbelieving--unless it all were a bit of fine acting--"do you mean to tell me it is possible to calculate a thing like that? How would anyone know where her arm would be?" "It is simpler than it sounds, Mr. Phelps." Kennedy was suddenly harsh. "There is only one natural movement of an arm in that case. The culprit was undoubtedly familiar with Miss Lamar's height and with her manner of working. It is a bit of action which has to be repeated in both the long shot and close-up scenes. Jameson here can tell you how many times a scene is rehearsed. There probably were a dozen sure chances of the needle striking the girl's bare flesh. You will see from the position of the holes that it was arranged point downward and slightly turned in, and on a particular fold of the curtain, too; showing that some one placed it there only after a nice bit of calculation. Furthermore, it was high enough so that there was little chance of anyone being pricked except the star, whose death was intended." Phelps either seemed convinced, or else he felt it inadvisable to irritate Kennedy by a further pretense of skepticism. A point occurred to me, however. "Listen, Craig!" I spoke in a low voice. "Remember all the emphasis you placed upon the fact that she would cry out. She was not supposed to cry out in that first scene." "No, Walter, but if you'll read the second, the close-up, you'll see that the script actually calls for a cry. Now suppose she makes an exclamation in the first instead. Nobody would think anything of it. They would assume that she had played her action a little in advance, perhaps. "And then consider this, too! Miss Lamar, receiving the scratch, would cry out unquestionably. But she has been before the camera for years and she is trained in the idea that film must not be wasted uselessly. She would not interrupt her action for a little scratch because in these circumstances any little startled movement would fit in with the action. By the time the scene was over she would have forgotten the incident. It would mean very little to her in the preoccupation of bringing the mythical Stella Remsen into flesh-and-blood existence. The poison, however, would be putting in its deadly work." "Wouldn't it act before the thirteenth scene--" I began. "Not necessarily. As a matter of fact, an actress, in the excitement of her work, might resist the effects for a much longer period than some one who realizes he is sick. Some day I'm going to write a book on that. I'm going to collect hundreds of examples of people who keep plugging along because they refuse to admit anything's the matter with them. It's like Napoleon's courier who didn't drop until he'd delivered his message and made his last precise military salute." One other thought struck me. "The blood spots on the curtain cannot be Miss Lamar's if, as you say, the scratch brought no blood." "How about the nocturnal visitor who removed the needle in the dark? Can't you imagine him pricking himself beautifully in his hurry." "Good heavens!" I felt the chills travel up and down my spine. "There may be another fatality, then!" I exclaimed. Kennedy was noncommittal. "It would be too bad for justice to be cheated in that fashion," he remarked. Phelps meanwhile had been listening to us impatiently. Finally he turned to Mackay. "Was that all you called me out here for? Did you just want to show me the pinholes in those portieres?" "Not exactly," Mackay replied, eyeing him sharply. "Some one forced his way into this library last night. My guard saw him, and also saw a second man who remained out in the shrubbery and seemed to be watching the first. One shot was fired, but both men got away. An automobile was waiting, perhaps two of them." "How does this concern me?" Phelps's voice rose in anger. He strode into the library and over to the French windows, inspecting the damage to the fine woodwork with steadily rising color. Then he hurried back to the side of Mackay. "It's up to you, District-Attorney Mackay," he said, with a great show of his ill feeling. "You practically forced me out of my own house. You sent my servants away. You put your own guards in charge, young, inexperienced deputies who don't know enough to come in when it's wet. Now you have me make this trip out here in business hours just to show me where a needle has been stuck in a curtain and where a pair of imported window sashes have been ruined." Mackay was unruffled. "It is necessary, Mr. Phelps, that you look over this room and see that nothing else has been disturbed; that there is no further damage. Moreover, I thought you might be interested, might wish to help us determine the identity of the intruder." "If there's any way I can really help you to do that"--sarcastically--"I'll be delighted." "Were you here the night before the murder?" Mackay asked. "You know I seldom spend the night in Tarrytown. I have quarters in New York, at the club, and recently I have been spending all my time in New York, on account of the situation in the picture business." "You were not here the night before the murder, then?" "No!" "But you were out here yesterday before the actors arrived, before Manton or any of his technical staff and crew came?" "I was out very early, to make sure the servants had the house ready." Phelps was red now. "Are you insinuating anything, Mackay?" The little district attorney was demonstrating a certain quality of dogged perseverance. "Some one put the needle in the curtain before the company arrived. You probably were in the house at the time; or at the least your servants were. Whoever did was the one who murdered Stella Lamar." "And also," rejoined Phelps, tartly, "was the intruder who broke in here last night and ruined my window sash. If you had had better guards you might have caught him, too!" "Are you sure of your servants? Are they reliable--" "I never anticipated a murder and so I didn't question them as to their poisoning proclivities when I engaged them. But you know where they are and you can examine them. If I were you, Mackay--" "Gentlemen!" Kennedy hastened to stop the colloquy before it became an out-and-out quarrel. Then he faced the banker. "Mr. Phelps," Kennedy's voice was soft, coaxing, "I don't think Mr. Mackay quite understands. It would be a great service to me if you would give the house a quick general inspection. You are familiar with the things here, enough to state whether they have been disturbed to any appreciable degree. You see, we do not know the interior arrangements as they were before this unfortunate happening." With rather ill grace Phelps stalked up the steps, acceding to Kennedy's request, but disdaining to answer. Kennedy turned to Mackay as the banker disappeared out of earshot. "That's just to cool him off a bit. I have everything I came to get right here." Producing a pair of pocket scissors, he cut the pierced and spotted bit of silk from the portieres, ruthlessly. It was necessary vandalism. "What was the poison, Mr. Kennedy?" Mackay asked, in a low voice. "I think that it was closely allied to the cyanide groups in its rapacious activity." "But you haven't identified it yet?" "No. So far I haven't the slightest idea of its true nature. It seems to have a powerful affinity for important nerve centers of respiration and muscular co-ordination, as well as possessing a tendency to disorganize the blood. I should say that it produces death by respiratory paralysis and convulsions. To my mind it is an exact, though perhaps less active, counterpart of hydrocyanic acid. But that is not what it is or I would have been able to prove it before this." Mackay nodded, listening in silence. "You'll say nothing of this?" Kennedy added. "I'll be silent, of course." Heavy footsteps from the rear marked the return of Phelps, who had covered the upper floors, descending by the back stairs so as to have a look at the kitchen. "Everything seems to be all right," he remarked, half graciously. Kennedy led the way to the front porch. There he seemed more interested in the weather than in the case, for he studied the sky intently. Glancing up, I saw that the morning was still gray and cloudy, with no promise that the sun would be able to struggle through the overhanging moisture. "I don't think we'll go back to the city--that is, all the way in," he remarked, speaking for both of us. "I want to go to the Manton studio first. This is no day for exteriors and so they'll probably be working there." He smiled at Phelps. "I want to see if any of our possible suspects look as though they had been engaging in nocturnal journeys." Phelps had been rubbing his eyes. He dropped his hand so quickly that I wanted to smile; then to cover his confusion he promptly offered to drive us in. Mackay at the same time volunteered his car. Kennedy accepted the latter offer. As he thanked the banker I wondered if any suspicion of that individual lurked in the back of his mind. Phelps certainly had made a very bad impression upon me with his antagonistic attitude, with his readiness to transform every question into a personal affront. "Just one other thing, Mr. Phelps," exclaimed Kennedy, as we were about to descend to Mackay's car. "Why did you wish the scenes in 'The Black Terror' actually taken in your library?" Kennedy had asked the question before. Had he forgotten? I glanced at the banker and read the same thought in his expression. "I--I'm proud of my library and I wanted to see it in pictures," he replied, after some hesitation and with a little rancor. "Not to save money?" "It would be no appreciable saving." "I see." Kennedy was tantalizingly deliberate. "How long have you held the controlling interest in Manton Pictures, Mr. Phelps?" "Uh"--in surprise--"nearly a year." "You could have had your library photographed at any time, then, simply by stating your request as you did in this case. In that year there have been pictures which would have served the purpose as well as this; better, in fact, because in this picture the library seems to be dark almost altogether. In other stories there probably were infinitely better chances for the exhibition of the room. Why did you wait for 'The Black Terror'?" As a clear understanding of Kennedy's question and all it entailed filtered into the mind of Phelps he became so red and flushed with anger that I felt sure he was going to explode on the spot. "Because I didn't think of it before," he sputtered. "You said the situation in the picture business made it necessary for you to stay in town. Is there any trouble between Manton and yourself?" "Not a bit!" "Was Stella Lamar making any trouble, of a business nature, such as threatening to quit Manton Pictures?" "No!" Phelps' eyes now were narrowed to slits. "Are you sure?" With a great effort Phelps achieved a degree of self-control. He forced a smile. His remark, presumed to be a pleasantry, I knew masked the true state of his feelings. "As sure, Mr. Kennedy," he rejoined, awed by Kennedy's reputation even in the full flood of his anger, "as sure as I am that I'd like to throw you down these steps!" XIII MARILYN LORING The magic of Manton's name admitted us to the studio courtyard, and at once I was struck by the change since the day before. Now the tank was a dry, empty, shallow depression of concrete. The scenery, all the paraphernalia assembled for the taking of water stuff, was gone. Except for the parked automobiles in one corner and a few loitering figures here and there the big quadrangle seemed absolutely deserted. In the general reception room Kennedy asked for Millard, but was told he had not been out since the previous day. That was to be expected. But Manton, it developed, was away also. He had telephoned in that he would be detained until late afternoon on important business. I know that I, for one, wondered if it were connected with Fortune Features. "It's just as well," Kennedy remarked, after convincing the boy at the desk it was Manton's wish that we have the run of the place. "My real object in coming was to watch the cast at work." We found our way to the small studio, called so in comparison with the larger one where the huge ballroom and banquet sets were being built. In reality it possessed a tremendous floor space. Now all the other companies had been forced to make room for "The Black Terror" on account of the emergency created by the death of Stella Lamar, and there were any number of sets put up hastily for the retakes of the scenes in which Stella had appeared. The effect of the whole upon a strange beholder was weird. It was as though a cyclone had swept through a town and had gathered up and deposited slices and corners and sections of rooms and hallways and upper chambers, each complete with furniture and ornaments, curtains, rugs, and hangings. Except for the artistic harmony of things within the narrow lines of the camera's view, nothing in this great armory-like place had any apparent relation to anything else. Some of the sets were lighted, with actors and technical crews at work. Others were dark, standing ready for use. Still others were in varying states of construction or demolition. Rising above every other impression was the noise. It was pandemonium. We saw Werner at work in a distant corner and strolled over. The director was bustling about feverishly. I do not doubt that the grim necessity of preparing the picture for a release date which was already announced had resulted in this haste, without even a day of idleness in respect for the memory of the dead star, yet it seemed cold-blooded and mercenary to me. I thought that success was not deserved by an enterprise so callous of human life, so unappreciative of human effort. Most of the cast were standing about, waiting. The scenes were being taken in a small room, fitted as an office or private den, but furnished luxuriously. Later I learned it was in the home of the millionaire, Remsen, close off the library for which the actual room in Phelps's home was photographed. Shirley and Gordon, I noticed, kept as far apart as possible. It was quite intentional and I again caught belligerent glances between them. On the other hand, both Enid and Marilyn Loring were calm and self-possessed. Yet between these two I caught a coolness, a sort of armed truce, in which each felt it would be a sign of weakness to admit consciously even the near presence of the other. Werner was irascible, swearing roundly at the slightest provocation, raging up and down at every little error. "Come now," he shouted, as we approached, "let's get this scene now--number one twenty-six. Loring--Gordon! Shake a leg--here, I'll read it again. 'Daring enters. He is scarcely seated at the desk, examining papers, when Zelda enters in a filmy negligee. Daring looks up amazed and Zelda pretends great agitation. Daring is not unkind to her. He tells her he has not discovered the will as yet. Spoken title: "I am sure that I can find a will and that you are provided for." Continuing scene, Daring speaks the above. Zelda thanks him and undulates toward the door with the well-known swaying walk of the vampire. Daring turns to his papers and does not watch her further. She looks over her shoulder, then exits, registering that she will get him yet.'" Werner dropped his copy of the script. "Understand?" he barked. "Make it fast now. We shouldn't do this over, but you were lousy before, both of you!" Gordon extinguished a cigarette and entered the set with a scowl. Marilyn rose and slipped out of a dressing gown spotted with make-up and dark from its long service in the studios. Underneath the wrapper the finest of silken draperies clung to her, infinitely more intimate here in actuality and in the bright studio lights than it would be upon the screen. I noticed the slim trimness of her figure--could not help myself, in fact. And I saw also that she shrank back just the least little bit before stepping to her place at the door. It was modesty, a genuine girlish diffidence. In a moment I revised my conception of her. Before, I had not been able to decide whether Marilyn Loring was a woman with a gift for looking young, or a flapper with the baffling sophistication affected these days by so many of them. Now I knew somehow that she was just all girl, probably in her early twenties. The brief instant of shyness had betrayed her. In the scene she changed. Marilyn Loring was an actress. The moment she caught the click of the camera's turn there was a hardness about her mouth, a faint dishonest touch to the play of her eye, a shameless boldness to her movements concealed without concealment. In the flash of a second she was Marilyn no longer, but Zelda, the ward of old Remsen, an unscrupulous and willing ally of the "Black Terror." Werner damned the amount of footage used in the scene, then turned to the next, with Enid and Gordon, in the same set, one of the necessary retakes for which the room had been put up again. Enid had not noticed me and I somehow failed to shake off the feeling of fear that the glance of Millard had given me. Faint heart I was, and the answer was that I had yet to win the fair lady. To excuse myself I pretended she was different under the lights. It was really true that, as Zelda Remsen, Enid was not the fascinating creature I had met in Werner's office. There was too much Mascaro on her lashes, too great an amount of red and blue and even bright yellow in her make-up. In striking contrast was the little coloring used by Stella Lamar, or even Marilyn Loring. Enid's scene was a close-up in which the beginning of the love interest in the story was shown. I noticed that as the cameras turned upon the action the girl inch by inch shifted her position, almost imperceptibly, until she was practically facing the lens. The consequence was that Gordon, playing the lover, was forced to move also in order to follow her face, and so was brought with his back toward the camera. It was the pleasant little film trick known as "taking the picture away" from a fellow actor. Enid was a "lens hog." The moment the scene was over Gordon rushed to Werner to protest. The director, irritated and in a hurry, gave him small satisfaction. Both players were called back under the lights for the next "take." As Werner's back was turned Enid favored Gordon with a mischievous, malicious glance. The leading man possessed very few friends, from what I had heard. The new star evidently did not propose to become one of them. "Let's pay our respects, socially," suggested Kennedy, at my elbow. I followed his glance and saw that Marilyn was seated alone, away from the others, apparently forlorn. As we approached she drew her dressing robe about her, smiling. With the smile her face lighted. It was in the rare moments, just as her smile broke and spread, that she was pretty, strikingly so. "Professor Kennedy," she exclaimed. "And Mr. Jameson, too! Sit down and watch our new star." "What do you think of her?" Kennedy asked. "Enid?" Marilyn's expression became quizzical. "I think she's a clever girl." "You mean something by that, don't you?" prompted Kennedy. She sobered. "No! Honestly!" For an instant she studied him with a directness of gaze which I would have found disconcerting. "Don't tell me"--she teased, again allowing the flash of a smile to illuminate her features--"don't tell me the renowned and celebrated Professor Kennedy suspects Enid Faye of murdering poor Stella to get her position." Kennedy laughed, turning to me. "There's the woman," he remarked. "We may deduce and analyze and catalogue all the facts of science, but"--he spread his palms wide, expressly--"it is as nothing against a woman's intuition." Facing Marilyn again, he became frank. "You caught my thought exactly, although it was not as bad as all that. I simply wondered if Miss Faye might not have had something to do with the case." "Why?" I realized now that this Miss Loring, in addition to considerable skill as an actress, in addition to rare beauty on the screen, possessed a brain and the power to use it. She followed Kennedy with greater ease than I, who knew him. "Why?" she repeated. "Perhaps it's the intuition of the male," he began, hesitatingly. She shook her head. "A man's intuition is not dependable. You see, a woman gets her intuition first and fits her facts to it, while a man takes a fact and then has an intuitive burst of inspiration as a result. The woman puts her facts last and so is not thrown out when they're wrong, as they usually are. But the man--I think, Professor Kennedy, that you have some facts about Enid stored away and that that's why you put a double meaning in my remark. Am I right?" He smiled. "I surrender, Miss Loring. You are right." "What is the little fact? Perhaps I can help you." "Miss Faye and Lawrence Millard seem to be old friends." "Oh! Maybe you wonder at the contents of the sealed testimony in the case of Millard VS. Millard?" Kennedy nodded. "Do you want to know what I think?" she asked. "Please." "Well, I've worked with Stella nearly a year. It's my opinion she divorced Millard because he asked her to do so." "No, no!" I balked at that, interrupting. "He could have obtained the divorce himself if he had wanted it. Stella Lamar and Manton--" "That's talk!" she rejoined, with a show of feeling. "That's the thing I hate about pictures. It's always talk, talk, talk! I'm not saying Stella and old Papa Lloyd, as we used to call him, never were mixed up with each other, but it's one thing to repeat a bit of gossip and quite another thing to prove it. I'm not one to help give currency to any rumor of immoral relationship until I'm pretty dog-gone sure it's true." "You think Miss Lamar wasn't as bad as painted?" asked Kennedy. "I'm sure of it, Mr. Kennedy. I've known Stella and I've known others of her type. Fundamentally they're the kindest, truest, biggest-hearted people on earth. When Stella and I shared a dressing room I often caught her giving away this or that--frequently things she needed herself. I've known her to draw against her salary to lend money to some actor or actress whom she well knew would never repay her. Stella's biggest fault was an overbalancing quality of sympathy. If she ever did get mixed up with anyone you may bet it was because that person played upon her feelings." "Have you any theory as to who killed her?" It was a direct question. "No!" The answer was quick, but then an amazing thing happened. Marilyn suddenly colored, a flush which gathered up around her eyes above the make-up and made me think of a country girl. She started to say something else and then bit her tongue. Her confusion was surprising, due, probably, to the unexpectedness of Kennedy's query. Kennedy seemed to wish to spare her. Undoubtedly her prompt negative had been the truth. Some afterthought had robbed her of her self-control. "Tell me why you said Miss Faye was a clever girl," he directed. "Just because she puts her ambition above everything else and works hard and honestly and sincerely, and will get there. That's what people call being clever." "I see." Werner's voice, roaring through a megaphone, announced an interval for lunch. Marilyn rose, laughing now, but still in a high color, conscious perhaps that she had revealed some strong undercurrent of feeling. "If you'll escort me to my dressing room," she said, coaxingly, "and wait until I slip into a skirt and waist, I'll initiate both of you to McCann's across the street. We all eat there, players, stage hands, chauffeurs--all but the stars, who have machines to take them elsewhere." Kennedy glanced at me. "Delighted!" said I. "We haven't much time," she went on, leading the way. "Werner's on a rampage to-day." "He isn't usually that way?" "It's Stella's death, I guess." She opened one of the steel fire doors. "He's always that way, though, when he's been out the night before." I flashed a look at Kennedy. Could Werner have been at Tarrytown? In the long hallway of dressing rooms Marilyn stopped, grasping the knob of her door. "It'll only take me--" she began. Then her face went white as the concrete of the floor, and that was immaculate. An expression which might have been fear, or horror, or hate--or all three, spread over her features, transforming her. Following the direction of her stare, I saw Shirley down the hall, just as he stopped at his own door. He caught her glance suddenly, and his own face went red. I thought that his hands trembled. Marilyn wheeled about, lips pressed tightly together. Throwing open the door, she dashed into her room, slamming it with a bang which echoed and re-echoed up and down the little hall. She had forgotten our presence altogether. XIV ANOTHER CLUE Kennedy looked at me quizzically. "I guess we'd better not wait for Miss Loring to initiate us to McCann's," he remarked. We found our way to the courtyard, and were headed for the gate when a young man in chauffeur's cap and uniform intercepted us. I had noticed him start forward from one of the cars parked in the inclosure, but did not recognize him. "May I speak to you a moment, Professor Kennedy--alone?" "Mr. Jameson here is associated with me, is assisting me in this case, if it is something concerning the death of Miss Lamar." "It is, sir. I saw you out at Tarrytown yesterday. McGroarty is my name and I drove one of the cars the company went in. They were pointing you out to me, and I'd read about you, and just now I says to myself there's something I ought to tell you." "That's right." Kennedy lighted a cigar, offering one to the chauffeur. "I'm not supernatural and often I'm able to solve a mystery only with the help of all those who, like myself, want justice done." "Yes, sir! That's my way of looking at it. Well"--McGroarty blew a cloud of smoke, appreciatively--"I do a good bit of driving for these people, and this morning it was cloudy and dull, no good for exteriors, but yet sort of so it might clear at any moment, and so I was ordered. I brought my car and left it standing here in the yard while I went over to McCann's--the lunch room, you know--for a cup of coffee. When I came back"--again the cigar--"there still was nothing doing, and so I thought--you know how it is--I thought I'd clean up the back of the old boat, to kill time, not saying it wasn't needed. So I took out the cocoa mat to beat it and what do I find on the floor--between the mat and the rear seat it was, I guess--but this." He handed Kennedy some small object which glinted in the light. Looking closely, I saw that it was a peculiarly shaped little glass tube. "An ampulla," Kennedy explained. "It's the technical name the doctors have for such a container." "It must have been between the mat and the rear seat," the chauffeur repeated. Then he discovered that his cigar was out. He struck a match. Kennedy turned the bit of glass over and over in his hand, examining it carefully. I felt rather fearful, wondering if it might not contain some trace of the deadly poison which had so quickly killed Stella Lamar. I even half expected to see Kennedy find some infinitesimal jagged edge or point which could have inflicted the fatal scratch. Then I realized that McGroarty had handled the thing with impunity, perhaps had carried it about half a day. Kennedy took his scarf pin. On the outside of the little tube there was no trace of a label or marking of any sort. All about, on the inside, however, the glass was spotted with dried light-yellow incrustations, resembling crystals and at first apt to escape even the sharpest scrutiny. With the pin Kennedy scaled off one of these and put it under his pocket lens. But he came to no conclusion. Rather puzzled and nettled, he dropped the tiny bit of substance back into the tube, then replaced his pin in his scarf, and stowed this latest bit of possible evidence in his pocket carefully. "How do you suppose it got in the car?" he asked. "Some one must have dropped it and it must have rolled in that space by the edge of the mat," replied the chauffeur. "There was just room for it, too! I never would have noticed it without taking up the mat." "It couldn't be broken, by being trampled on?" "Nope! Not a chance!" "How long could it have been there?" "Two or three or four days--since I cleaned up last." I remembered the cleverness shown by the guilty person in placing the needle in the curtain. It seemed unlikely that this could be an accident. "Isn't it possible," I suggested, "that this is a plant; that the tube was put there deliberately, to throw us off the track?" "It's quite likely," he admitted. "On the other hand, Walter, the very smartest criminal will do some foolish little thing, enough to ruin the most careful plans and preparations." He turned to McGroarty. "Who rode in your car yesterday?" "Mine's the principals' car," boasted McGroarty. "Going out I had Miss Lamar, Miss Loring, Mr. Gordon, Mr. Shirley, and Mr. Werner. Coming back Mr. Werner was with you, and Miss Lamar--well, there was only Miss Loring and Mr. Gordon and Mr. Shirley." "Did you notice how they acted?" "They never says a word to each other on all the trip back, but I didn't think it strange after what happened, although usually they're always joking and laughing." "You brought the three to the studio here?" "Yes. They had to get out of make-up." "Did you leave the car then?" "No, I hit it right for the garage." "Were you away from the car at Tarrytown?" "Sure! That was a long wait. Peters, Manton's chauffeur, and I found a couple of horseshoes and we were throwing them most of the time." "How long was the machine alone here in the yard this morning?" "A couple of hours, maybe. I knew the old boiler was safe enough, and that if they wanted me they'd look over in McCann's." "Well," Kennedy extended his hand, "I thank you, and I won't forget you, McGroarty." As soon as the chauffeur was out of earshot I faced Kennedy rather eagerly, to forestall him if he had arrived at the same conclusion as myself. "See! It's just as I thought yesterday!" "How's that, Walter?" "Werner! He rode out in that machine, but not back. In Manton's car he was worried all the time. He probably knew he had dropped the tube. Then he hurried up ahead of us and wiped the needle--" I stopped, lamely. Kennedy smiled. "See, you're jumping at conclusions too fast. You remember now that we decided that the towel has nothing directly to do with the poison. In a way you cannot assume that this ampulla has, either, although I myself feel sure on that point. But in any case no one is eliminated. It is true Werner did not return in the same automobile. It is also true that he had little opportunity to drop it while others were in the car with him. When McGroarty was away from the car anyone could have lost it, or--as you suggested a moment ago--planted it there deliberately to divert suspicion." I felt the beginnings of a headache from all these confused threads of the mystery. "Can't--Isn't there anyone we can say is innocent, at least, even if we cannot begin to fasten the guilt upon somebody?" I pleaded. Kennedy shook his head. "At this stage the one is as hard as the other. I consider myself lucky to have collected as much material as I have for the analysis of the poison." He tapped his pocket significantly. "Yoo-hoo!" A frankly shrill call in a feminine voice interrupted. We both turned, to see Marilyn Loring hastening toward us. "Did you think I was going to forget you?" she asked, almost reproachfully and much out of breath. "Let's hurry," she added. "This is roast beef day." We started toward the gate once more, Marilyn between us, vivacious and rather charming. I noticed that she made no reference to the incident in the hallway, the precipitate manner in which she left us and the very evident confusion of Merle Shirley. Kennedy, too, seemed disposed to drop the matter, although it was obviously significant. For some reason his mind was elsewhere, so that the girl was thrown upon my hands. It struck me that, after all, she was attractive. At this moment I found her distinctly good-looking. "Why do you 'vamp'?" I asked, innocently. "You don't seem to me, if you'll pardon the personal remark, at all that type." She laughed. "It's all the fault of the public. They insist that I vamp. I want to play girly-girly parts, but the public won't stand for it; they won't come to see the picture. They tell the exhibitor, and he tells the producer, and back I am at the vamping again. Isn't it funny?" She paused a moment. "Take Gordon. Doesn't it make you laugh, what the public think he is--clean-cut, hero, and all that sort of thing? Little do they know!" All at once Kennedy stopped abruptly. We were close to the entrance, just where a smart little speedster of light blue lined with white was parked at the edge of the narrow sidewalk. The sun, after a morning of uncertainty, had just struck through the haze, and it illuminated Marilyn's face and hair most delightfully as we both turned, somewhat in surprise. "I know you'll never forgive me, Miss Loring," Kennedy began, "but the fact is that just before you came out we stumbled into a new bit of evidence in the case and I believe that Jameson and I will have to hurry in to the laboratory. Much as I would like to lunch with you, and perhaps chat some more during scene-taking this afternoon--" It seemed to me that her eyes widened a bit. Certainly there was a perceptible change in her face. It was interest, but it was also certainly more than that. I felt that she would have liked to penetrate the mask of Kennedy's expression, perhaps learn just what facts and theories rested in his mind. "Is it--" Suddenly she smiled, realizing that Kennedy would reveal only the little which suited his purpose. "Is it something you can tell me?" she finished. He shook his head. His answer was tantalizing, his glance searching and without concealment. "Only another detail concerning the chemical analysis of the poison." "I see!" If she knew of the ampulla the answer would have been intelligible to her. As it was, her face betrayed nothing. "I guess I'll hurry on over alone, then," she added. She extended a hand to each of us. Her grasp was warm and friendly and frank. "So long, and--and good luck, for Stella's sake!" "Hello, folks!" The dancing bantering voice from behind us, with silvery cadence to its laughter, could belong to no one but Enid Faye. I grasped that it was her car which Kennedy leaned upon. I gasped a bit as I saw her directly at my side, her dainty chamois motoring coat brushing my sleeve, the sun which grew in strength every moment casting mottled shadows upon her face through the transparent brim of her bobbing hat, in mocking answer to the mirth in her eyes. For an instant she gazed after the retreating Marilyn. "Good-by, Marilyn! DEAR," she called, mega-phoning her hands. The other girl made no response. Laughing, Enid slipped a hand under my arm, the firm pressure of her fingers thrilling me. She addressed Kennedy, however. "Do you want a ride in to the city, both of you?" Kennedy brightened. "That would be fine! How far are you going?" "The Burrage. I have a luncheon engagement. That's Forty-fourth." "Can you drop us off at the university?" "Surely! Climb in. It's a tight fit, three in the seat, but fun. And"--facing me--"I want Jamie between us, next to me!" As we rolled out of the studio inclosure she leaned forward on the wheel to question Kennedy. "What did Marilyn Loring want? You seemed in deep confab!" "She volunteered to initiate us to McCann's, across the street." "Oh!" She skidded about a corner skillfully. "And--" "Well, we bumped into an additional piece of evidence and I thought Jameson and I ought to hurry in to my laboratory instead." "I bet"--Enid giggled, readjusting her hat in the breeze--"I bet she wanted to know what you'd found, right away. Didn't she?" "Yes!" Kennedy's face was noncommittal, "Why do you say that?" "Because she came into my room, just as we were getting ready for work this morning. Perhaps I'm wrong, but from the way she kept asking me questions about everyone from Manton down I got the idea she was quizzing me, to see how much I knew. Of course this is only my first day, but it seems to me that Marilyn is talking a great deal, without saying very much. I've come to the conclusion she knows a good deal more than she is telling anyone, and that she'd like to find out just how much everyone else knows." Kennedy nodded almost absent-mindedly, without responding further. "Well"--Enid speeded up a bit--"not to change connections on the switchboard, I think I'm going to like it with Manton Pictures." "Will they do justice to your work," Kennedy inquired, "putting you in a partially finished picture in this way?" "That's where I'm in luck, real bang-up luck. Werner has directed me before and knows just exactly how to handle me." "What about the story? That was built for Stella, wasn't it?" "Yes, but they're changing it here and there to fit me. Larry knows my work, too! That's luck again for little Enid." "How long have you known Millard?" In a flash I realized Kennedy's cleverness. This was the fact he had wished to unearth. The question was as natural as could be. He had led up to it deliberately. I was sure of that. "Four, nearly five years," she replied, unsuspiciously. Then suddenly she bit her lip, although her expression was well masked. "That is," she added, somewhat lamely--"that is, in a casual way, like nearly everyone knows nearly everyone else in the film game." "Oh!" murmured Kennedy, lapsing into silence. XV I BECOME A DETECTIVE Important as it was to watch Enid and Marilyn, Werner and the rest, Kennedy decided that it was now much more important to hold to his expressed purpose of returning to the laboratory with our trophies of the day's crime hunt. "For people to whom emotion ought to be an old story in their everyday stage life, I must say they feel and show plenty of it in real life," I remarked, as Enid set us down and drove off. "It does not seem to pall." "I don't know why the movie people buy stories," remarked Craig, quaintly. "They don't need to do it--they live them." When we were settled in the laboratory once more Kennedy plunged with renewed vigor into the investigation he had dropped in the morning in order to make the hurried trip to the Phelps home in Tarrytown. I had hoped he would talk further of the probabilities of the connection of the various people with the crime, but he had no comment even upon the admission of Enid that she had known Millard for a period long antedating the trouble with Stella Lamar. It seemed that, after all, he was quite excited at the discovery of the ampulla and was anxious to begin the analysis of its scale-like contents. I was not sure, but it struck me that this might be the same substance which had spotted the towel or the portieres. If that were so, the finding of it in this form had given him a new and tangible clue to its nature, accounting for his eagerness. I watched his elaborate and thorough preparations, wishing I could be of assistance, but knowing the limitations of my own chemical and bacteriological knowledge. I grasped, however, that he was concentrating his study upon the spots he had cut from the portieres, in particular the stain where the point of the needle had been, and upon the incrustations on the inner surface of the tube. He made solutions of both of these and for some little time experimented with chemical reactions. Then he had recourse to several weighty technical books. Though bursting with curiosity, I dared not question him, nor distract him in any way. Finally he turned to a cage where he kept on hand, always, a few of those useful martyrs to science, guinea pigs. Taking one of the little animals and segregating him from the others, he prepared to inoculate him with a tiny bit of the solution made from the stain on the piece cut from the portiere. At that I knew it would be a long and tiresome analysis. It seemed a waste of time to wait idly for Kennedy to reach his conclusions, so I cast about in my mind for some sort of inquiry of my own which I could conduct meanwhile, perhaps collecting additional facts about those we were watching at the studio. Somehow I could not wholly lose my suspicions of the director, Werner; especially now as I marshaled the evidence against him. First of all he was the only person absolutely in control of the movements of Stella Lamar. If she did not bring up her arm against the curtains in a manner calculated to press the needle against her flesh it certainly would not seem out of the way for him to ask her to do it over again, or even for him to direct changes in her position. This he could do either in rehearsal or in retakes after the scene had actually been photographed. It was not proof, I knew. Practically all of them were familiar with the action of the scene, could guess how Werner would handle it. The point was that the director, next to Millard, was the most thoroughly conversant with the scenes in the script, had to figure out everything down to the very location and angles of the camera. Another matter, of course, was the placing of the needle in the silk. For that purpose some one had to go to Tarrytown ahead of the others, or at least had to precede the others into the living room. Offhand I was compelled to admit that this was easiest for Phelps--Phelps, the man who had insisted that the scene be taken in his library. At the same time, I knew it was quite possible for the director to have entered ahead of anyone else, possible for him to have issued orders to his people which would keep them out of the way for the brief moment he needed. A third consideration was the finding of the ampulla in McGroarty's car. Stella, Marilyn, Jack Gordon, Merle Shirley, and Werner had ridden out together. Werner had not returned. While this fact did not indicate definitely that he might have dropped it, coupled with the other considerations it pointed the suspicion of guilt at the director. Then there was the finding of the towel in the washroom of the office building at the studio. While Kennedy now said it was not used to wipe the needle, while we now knew that the needle remained in the portieres from the morning of Stella's death until late that night, yet Kennedy affirmed the connection of the towel with the crime in some subtle way. It was true that members of the cast sometimes used the washroom, yet it was evident that Manton, Millard, and Werner, who had rooms on the floor, were the more apt to be concerned in the attempt to dispose of it. Against Manton I could see no real grounds for suspicion. In a general way we had been compelled to eliminate Millard early in our investigation. Again I was brought, in this analysis of the mystery, to Werner. One other point remained--the identity of the nocturnal visitor to Tarrytown. In connection with that I remembered the remark of Marilyn. Werner was acting as he always acted when he was out late the night before, she had said. While my theories offered no explanation of the second man, the watcher, I saw--with an inner feeling of triumph--that everything again pointed to the director. I determined not to tell my conclusion to Kennedy, yet. I did not want to distract him. Besides, I felt he would disagree. "What do you think of this, Craig?" I suggested. "Suppose I start out while you're busy and try to dig up some more facts about these people?" "Excellent!" was his reply. "I can't say how much longer my analysis will keep me. By all means do so, Walter. I shall be here, or, if not, I'll leave a note so you can find me." Accordingly, I took up my search, determined to go slowly and carefully, not to be misled by any promising but fallacious clues. I knew that Werner would be working at the studio, from all we had heard in the morning. I determined upon a visit to his apartment in his absence. From the telephone book I discovered that he lived at the Whistler Studios, not far from Central Park on the middle West Side--a new building, I remembered, inhabited almost entirely by artists and writers. As I hurried down on the Subway, then turned and walked east toward the Park, I racked my brain for an excuse to get in. Entering the lower reception hall, I learned from the boy that the director had a suite on the top floor, high enough to look over the roofs of the adjoining buildings directly into the wide expanse of green and road, of pond and trees beyond. "Mr. Werner isn't in, though," the boy added, doubtfully, without ringing the apartment. "I know it," I rejoined, hastily. "I told him I'd meet him here this afternoon, however." On a chance I went on, with a knowing smile, "I guess it was pretty late when he came in last night?" "I'll say so," grinned the youth, friendly all of a sudden. He had interpreted the remark as I intended he should. He believed that Werner and I had been out together. "I remember," he volunteered, "because I had to do an extra shift of duty last night, worse luck. It must have been after four o'clock. I was almost asleep when I heard the taxi at the door." "I wonder what company he got the taxi from?" I remarked, casually. "I tried to get one uptown--" I paused. I didn't want to get into a maze of falsehood from which I would be unable to extricate myself. "I don't know," he replied. "It looked like one of the Maroon taxis, from up at the Central Park Hotel on the next block, but I'm not sure." "I think I won't go upstairs yet," I said, finally. "There's another call I ought to make. If Mr. Werner comes in, tell him I'll be back." I knew very well that Werner would not return, but I thought that the bluff might pave the way for getting upstairs and into the apartment a little later. Meanwhile I had another errand. The boy nodded a good-by as I passed out through the grilled iron doors to the street. Less than five minutes afterward I was at the booth of the Maroon Taxi Company, at the side of the main entrance of the Central Park Hotel. Here the starter proved to be a loquacious individual, and I caught him, fortunately, in the slowest part of the afternoon. Removing a pipe and pushing a battered cap to the back of a bald head, he pulled out the sheets of the previous day. Before me were recorded all the calls for taxicab service, with the names of drivers, addresses of calls, and destinations. Although the quarters in the booth were cramped and close and made villainous by the reek of the man's pipe, I began to scan the lists eagerly. It had been a busy night even down to the small hours of the morning and I had quite a job. As I came nearer and nearer to the end my hopes ebbed, however. When I was through I had failed to identify a single call that might have been Werner's. Several fares had been driven to and from the Grand Central Station, probably the means by which he made the trip to Tarrytown. In each case the record had shown the Central Park Hotel in the other column, not the Whistler Studios. I was forced to give up this clue, and it hurt. I was not built for a detective, I guess, for I almost quit then and there, prepared to return to the laboratory and Kennedy. But I remembered my first intention and made my way back to the Whistler Studios. Anyhow, I reflected, Werner would hardly have summoned a car from a place so near his home had he wished to keep his trip a secret. It was more important for me to gain access to his quarters. There it was quite possible I might find something valuable. I wondered if I would be justified in breaking in, or if I would succeed if I attempted it. Things proved easier than I expected. My first visit unquestionably had prepared the way. The hallboy took me up in the elevator himself without telephoning, took me to Werner's door, rang the bell, and spoke to the colored valet who opened it. As I grasped the presence of the servant in the little suite I was glad I had not tried my hand at forcing an entrance. I had quite anticipated an empty apartment. The darky, pleasant voiced, polite, and well trained, bowed me into a little den and proceeded to lay out a large box of cigarettes on the table beside me, as well as a humidor well filled with cigars of good quality. I took one of the latter, accepting a light and glancing about. Certainly this was in contrast with Manton's apartment. There was nothing garish, ornate, or spectacular here. Richly, lavishly furnished, everything was in perfect taste, revealing the hand of an artist. It might have been a bit bizarre, reflecting the nervous temperament of its owner. Even the servant showed the touch of his master, hovering about to make sure I was comfortable, even to bringing a stack of the latest magazines. I hope he didn't sense my thoughts, for I cursed him inwardly. I wanted to be alone. Ordinarily I would have enjoyed this, but now I had become a detective, and it was necessary to rummage about, and quickly. The sudden ringing of the telephone took the valet out into the tiny hall of the suite and gave me the opportunity I wished. Phelps apparently was calling up to leave some message for Werner, which I could not get, as the valet took it. What, I wondered, was Phelps telephoning here for? Why not at the studio? It looked strange. I lost no time in speculation over that, however. The moment I was left to myself I jumped up and rushed to a writing desk, a carved antique which had caught my eye upon my entrance, which I had studied from my place in the easy chair. It was unlocked, and I opened it without compunction. With an alert ear, to warn me the moment the colored boy hung up, I first gazed rather helplessly at a huge pile of literary litter. Clearly there was no time to go through all of that. I gave the papers a cursory inspection, without disturbing them, hoping to catch some name or something which might prove to be a random clue, but I was less lucky than Kennedy had been in his casual look at Manton's desk the afternoon before. Still able to hear the valet at the telephone, I reached down and opened the top drawer of the desk. Here perhaps I might be more fortunate. One glance and my heart gave a startled leap. There in a compartment of the drawer I saw a hypodermic needle--in fact, two of them--and a bottle. On the desk was a fountain pen ink dropper, a new one which had never been used. I reached over, pressed its little bulb, uncorked the bottle, inserted the glass point, sucked up some of the contents, placed the bulb right side up in my waistcoat pocket, and recorked the bottle. Next I took and pocketed one of the two needles, both of which were alike as far as I could see. Then I heard a good-by in the hall. I closed drawer and desk hastily. As I caught the click of the receiver of the telephone on its hook I was halfway across the floor. Before the colored boy could enter again I was back in my chair, my head literally in a whirl. What a stroke of good fortune! I had no expectation of proving Werner to be the guilty man by so simple a method as this, however. If he were the slayer of the star he would be too clever to leave anything so incriminating about. I have always quarreled with Poe's theory in The Purloined Letter, believing that the obvious is no place to hide anything outside of fiction. What I conceived, rather, was that Werner really was a dope fiend. The nature of the drug Kennedy would tell me very easily, from the sample. Establishing Werner's possession of the needles was another point in my chain of presumptions, showing that he was familiar with their use; and added to that was the psychological effect upon him of the habit, a habit responsible in many other cases for murders as skillfully carried out as that of Stella Lamar, often, too, without the slightest shred of real motive. I recalled Werner's habitually nervous manner and was sure now that the needles actually were used by him. Was it due to the high pressure of his profession? Had that constant high tension forced him to find relief in the most violent relaxation? Elated, I was tempted at first to crowd my luck. I wondered if I could not discover another ampulla such as the chauffeur, McGroarty, had picked up in his car. When Werner's servant, almost apologetically, explained that the telephone message was from a near-by shop and that he would have to leave me for a matter of ten or fifteen minutes, I assured him that it was all right and that I would occupy myself with a magazine. The moment he was out the door I sprang to action and began a minute search of every nook and cranny of the rooms. But gradually a sense of growing fear and trepidation took hold of me. Suppose, after all, Werner should return home unexpectedly? The colored boy did not seem surprised that I should wait, a slight indication that it was possible. Further, I could never tell when the darky might not return himself, breaking in upon me without warning and discovering me. At the best I was not a skillful investigator. I did not know just where to look for hidden evidences of poison, nor was I able to work fast, for fear of leaving too tangible marks of my actions behind me. A great perspiration stood out on my forehead. Gradually a trembling took hold of my limbs and communicated itself to my fingers. After all, it was essential that Werner be kept in ignorance of my suspicions, granting they were correct. It would be fatal if I should frighten him inadvertently, so that he would take to flight. Realizing my foolhardiness, I returned to my chair at last, picking up a magazine at random. I did so not a moment too soon. A slight sound caught my ear and I looked up to see the valet already halfway into the room. His tread was so soft I never would have heard him. "I don't think I'll wait any longer," I remarked, rising and stretching slightly, as though I had been seated all the time. "I'll ring up a little later; perhaps come back after I get in touch with Mr. Werner." "Who shall I say was here, sah?" the boy asked, with just a trace of darky dialect. Above all I didn't want to alarm Werner. I could not repeat the explanation I had allowed the attendant downstairs to assume from my remark, that I was a friend who had been out with the director the night before. I should have to take a chance that Werner's servant and the hallboy would not compare notes, and that the latter would say nothing to the director upon his arrival. "I'm an old friend from the Coast," I explained, with a show of taking the negro into my confidence. "I wanted to surprise him and so"--I slipped a half dollar into a willing palm--"if you'll say nothing until I've seen him--" He beamed. "Yes, sah! You jus' count on George, sah!" Downstairs I wondered if I could seal the tongue of the youth who had accommodated me before. Then I discovered that he had gone off duty. It would be extremely unlikely that he would be about until the following day. I smiled and hastened out to the street. Once in the open air again, I realized the full extent of the risk I had taken. All at once it struck me that no amount of explanation from either Kennedy or myself would serve to mollify Werner if he were innocent and learned of my visit. I doubted, in this moment of afterthought, that I would escape censure from Kennedy, who surely would not want his case jeopardized by precipitate actions upon my part. I began to run, to get away from the Whistler Studios as fast as possible. Then I saw I had grown panicky and I checked myself. But I hurried to the Subway and up to the university again, and to the laboratory, eager to compare notes with Kennedy. "If I were Alphonse Dupin," he remarked, calmly, grasping my excitement, "I would deduce that you have discovered something. I would also deduce that you believe it important and that you have no intention of withholding the information from me, whatever it is." "Correct," I answered, grinning in spite of myself. Then I handed him the needle, telling him in a few brief words of my visit to Werner's apartment, of the hallboy's confirmation of a nocturnal trip of some sort, of my search of the desk and some other parts of the suite. "I fixed it so that he won't hear of my visit, at least for some time. He won't suspect who it was, in any case." Kennedy examined the hypodermic. "Not like the one used," he murmured. "I thought that," I explained. "It simply indicates he is a dope fiend and is familiar with the use of a needle. Here!" I produced the ink filler which I had used to bring a sample of the contents of the bottle. "This seems to be what he uses. What is it?" Kennedy sniffed, then looked closely at the liquid through the glass of the tube. "It's a coca preparation," he explained. "If Werner uses this, he's unquestionably a regular drug addict." "Well," I paused, triumphantly, "the case against the chief director of Manton Pictures grows stronger all the time." "Not necessarily," contradicted Kennedy, perhaps to draw me out. "He's familiar with hypodermic syringes," I repeated. "Which doesn't prove that no one else would use one." "Anyhow, he was out until four A.M. last night and some one broke into Phelps's house to--" "You can't establish the fact that he went out there. There are plenty of other places he could have been until four in the morning." "But I can assume--" "If you are going to assume anything, Walter, why not assume he was the second man, the man who watched the actual intruder?" I turned away, despairing of my ability to convince Kennedy. As a matter of fact I had forgotten the other prowler at Tarrytown. Then I noticed that the one guinea pig in the separate cage was dead. In an instant I was all curiosity to know the results of Kennedy's investigations. "Did you make any progress?" I asked. "Yes!" Now I noticed for the first time that he was in fine humor. "I had quite finished the first stage of my analysis when you came in." "Then what was it? What was the poison that killed Stella Lamar?" I glanced at the stiff, prone figure of the little animal. Kennedy cleared his throat. "Well," he replied, "I began the study with the discovery I made, which I told you, that strange proteins were present." He picked up the ampulla and regarded it thoughtfully. Then he fingered the bit of silk cut from the portieres. "It is a poison more deadly, more subtle, than any ever concocted by man, Walter." "Yes?" I was painfully eager. "It is snake venom!" XVI ENID ASSISTS "A poison more subtle than any concocted by man!" repeated Kennedy. It was a startling declaration and left me quite speechless for the moment. "We know next to nothing of the composition of the protein bodies in the snake venoms which have such terrific and quick physiological effects on man," Kennedy went on. "They have been studied, it is true, and studied a great deal, but we cannot say that there are any adequate tests by which the presence of these proteins can be recognized. "However, everything points to the conclusion now that it was snake venom, and my physiological tests on the guinea pig seem to confirm it. I see no reason now to doubt that it was snake venom. The fact of the matter is that the snake venoms are about the safest of poisons for the criminal to use, for the reason of the difficulty they give in any chemical analysis. That is only another proof of the diabolical cleverness of our guilty person, whoever it may be. "Later I'll identify the particular kind of venom used. Just now I feel it is more important to discover the actual motive for the crime. In the morning I have a plan which may save me further work here in the laboratory, but for to-night I feel I have earned a rest and"--a smile--"I shall rest by searching out the motives of these temperamental movie folk a little more." As he spoke he slipped out of his acid-stained smock. "What do you mean?" As often, he rather baffled me. "It's nearly dinner time and we're going out together, Walter, down to Jacques'." "Why Jacques'?" "Because I phoned your friend Belle Balcom and she informed me that that was the place where we would be apt to find the elite of the film world dining." I acquiesced, of course. We hurried to the apartment first for a few necessary changes and preparations, then we started for the Times Square section in a taxi. "I never heard of the use of snake venom before," I remarked, settling back in the cushions--"that is, deliberately, by a criminal, to poison anyone." "There are cases," replied Craig, absently. "Just how does the venom act?" "I believe it is generally accepted that there are two agents present in the secretion. One is a peptone and the other a globulin. One is neurotoxic, the other hemolytic. Not only is the general nervous system attacked instantly, but the coagulability of the blood is destroyed. One agent in the venom attacks the nerve cells; the other destroys the red corpuscles." "You suspected something of this kind, then, when you first examined Stella Lamar?" "Exactly! You see, the victim of a snake bite often is unable to move or speak. Doctor Blake observed that in the case of the stricken star. Her nerves were affected, resulting in paralysis of the muscles of the heart and lungs and giving us some symptoms of suffocation. Then the blood, as a result of the attack of the venom, is always left dark and liquid. That, too, I observed in the sample sent me from Tarrytown. "The snake," Kennedy continued, "administers the poison by fangs more delicate than any hypodermic. Nature's apparatus is more precise than the finest appliances devised for the use of a surgeon by our instrument makers. The fangs are like needles with obliquely cut points and slit-like outlets. The poison glands correspond to the bulb of a syringe. They are, in reality, highly modified salivary glands. From them, when the serpent strikes, is ejected a pale straw-colored half-oleaginous fluid. You might swallow it with impunity. But once in the blood, through a cut or wound, it is deadly." "There could be no snake in this case," I remarked. "The fangs of a serpent make two punctures, don't they; while here there was just the one scratch--" "Of course there were no fangs when the deed was actually done," he rejoined, impatiently. "We've traced everything to the needle in the portieres and it is my belief that it was part of an all-glass hypodermic with a platinum-iridium point. It could hardly have been anything like the coarser syringe used by Werner, nor do I think it possible that the point of an ordinary needle would hold sufficient venom, since it would dry and form a coating like the incrustation on the inside of the ampulla McGroarty found." "That was the venom?" I asked. "Yes, I found it in the ampulla and in the stain on the portiere where the needle had pierced through." "The towel, though--" "Is something else. First thing in the morning we'll follow that up, as I promised you. Meanwhile let's concentrate on motives." A long line of private cars and taxicabs outside Jacques' testified to the popularity of the restaurant. At the door stood a huge, bulking negro resplendent in the glaring finery of his uniform. It seemed to me that people literally were thronging into the place, for it was cleverly advertised as a center of night life. Inside, the famous darky jazz band was in full swing. There was lilt and rhythm to the melody produced by the grinning blacks, and not a free arm or foot or shoulder or head of any of them but did not sway in time to their syncopated music. We were shown to a table on a sort of gallery or mezzanine floor which extended around three sides of the interior. Below, in the center, was the space for dancing, surrounded by groups and pairs of diners. Stairs led to the balcony on both sides, as though the management expected none of their guests to resist the lure of the dance between courses. The band, I noticed, was at the farther end, on an elevated dais, so that the contortions of the various players could be seen above the heads of those on the floor. We were at the rail so that we commanded a view of the entire place, a location I guessed had been maneuvered by Kennedy with a word to the head waiter. The only tables invisible to us were those directly beneath, but it would be a simple matter to cross around during any dance number to view them. As we took our seats the lights were dimmed suddenly. I realized that we had arrived in the midst of the cabaret and that it was the turn of one of the performers. Kennedy, however, seemed to enjoy the entertainment, an example of his ability to gain recreation whenever and however he wished, to find relaxation under the oddest or most casual circumstances, out of anything from people passing on the street to an impromptu concert of a street band. In scanty garments, in the glare of a multi-colored spotlight, the girl danced a hybrid of every dance from the earliest Grecian bacchanal to the latest alleged Apache importation from Paris. I have often wondered at Jacques' and places of the sort. The intermingling of eating and drinking and dancing was curious. What possible bearing this terpsichorean monstrosity might have upon the gastronomic inclinations of the audience it would have been difficult to fathom. The lights flashed bright again and Kennedy gave our order. Meanwhile I glanced about at the people below us. There was no one in sight I knew until I leaned well over the rail, but upon doing that I felt little chills of excitement run from the top to the bottom of my spine, for I discovered in a very prominent situation at the very edge of the dance floor a party of four, of whom three very much concerned us. Lloyd Manton, back to the polished space behind him, was unmistakable in evening clothes. These bunched at his neck and revealed his habitual stoop as impartially as his business suits. Across from him, lounging upon the table likewise, but more immaculately and skillfully tailored, was Lawrence Millard. The writer, I noticed, flourished his cigarette holder, fully a foot in length, and emphasized his remarks to the girl on his right with a rather characteristic gesture made with the second finger of his left hand. The girl was Enid, quite mistress of herself in a gown little more than no gown; and the remarks were obviously confidential. The other girl, engrossed in Manton, seemed a dangerously youthful and self-conscious young lady. Her hair flamed Titian red and her neck, of which she displayed not half as much as Enid, gave her much concern. "Kennedy! Look!" I reached over to attract his attention. "Who's the second girl, I wonder?" He became as interested as I was. With a blatant flourish of saxophone and cornet and traps the band began a jazzy fox-trot. Instantly there was a rush from the tables for the floor. Enid jumped to her feet, moving her bare shoulders in the rhythm of the music. Then Millard took firm hold of her and they wove their way into the crush. It seemed to me that the little star was the very incarnation of the dance. I envied her partner more than I dared admit to myself. Manton and his companion rose also, but more leisurely. On her feet the girl did not seem so young, although the second impression may have been the result of the length of her skirt and the long slim, lines of her gown. We watched both couples through the number, then gave our attention to the food we had ordered. Another dance, a modified waltz, revealed Enid in the arms of Manton. I tried to determine from her actions if she felt any preference for the producer, or for Millard when again she took the floor with him. It was an idle effort, of course. The people surged out perhaps three or four times while we were at our meal. Each time the party below jumped up in response to the music. At our cigars, finally, I took to observing the other diners, wondering what we had gained by coming here. Suddenly I realized that Kennedy was rising to greet some one approaching our table. Turning, rising also, I went through all the miseries of the bashful lover. It was Enid herself. "I caught sight of you looking over the rail while I was dancing," she told Kennedy, accepting a chair pulled around by the waiter. "I knew you saw me. Also I glanced up and found that you were perfectly well aware of the location of our table. So"--engagingly--"unsociable creature! Why didn't you come down and say 'Hello!' or ask me for a dance?" "Perhaps I intended to a little later." "Yes!" she exclaimed, in mockery. "You see, since Mecca won't go to the pilgrim, the pilgrim has to come to Mecca." "Did you ever hear of Mohammed and the mountain, Miss Faye?" Kennedy asked. "Of course! That's the regular expression. But I agree with Barnum. As he said, some people can be original some of the time and some people can be original all of the time, and I propose to be original always, like a baby with molasses." Kennedy laughed, for indeed she was irresistible. Then she turned to me, placing one of her warm little hands upon mine. "And Jamie!" she purred. "Have you forgotten little Enid altogether? Won't--won't YOU come down and dance?" "I--I can't!" I exploded, in agony. "I don't know how!" And I thought that I would never dare trust myself with her glistening shoulders clasped close to me, with her slim bare arm placed around my neck as I had watched it slip about the collar of Millard. "Now that the pilgrim is at Mecca--" Kennedy suggested, interrupting cruelly, as I thought. "Oh!" In an instant I sensed that I was forgotten, and I was hurt. "There's something which came out this afternoon at the studio," she began, "and I wonder if you know. Larry--that's Mr. Millard--assures me it is true, and--and I think you ought to hear about it. I--I want to assist all I can in solving the mystery of Stella Lamar's death, even though Stella's unfortunate end has meant my opportunity." "What is it, Miss Faye?" Kennedy was studying her. "It's about Jack Gordon. He's been trying to hold up the company for fifteen hundred a week, which would double his salary--perhaps you've heard that?" Kennedy nodded, although it was news to him. "I've been thinking about Gordon," he murmured. "Anyway," she went on, "it's gone around that he's desperately in need of money and that that is why he's so insistent upon the increase. It seems he owes everyone. In particular he owes Phelps some huge sums and old Phelps is on his tail, hollering and raising Ned. Phelps, you know, has uses for money himself just now. You had heard?" Again Kennedy evaded a direct answer. "Money is fearfully tight, of course," he remarked, encouraging her to continue. "Yes," she repeated, "Phelps is terribly hard up and after Gordon. And that's not all about our handsome leading man, Mr. Kennedy." She leaned forward. A certain intensity crept into her voice. She began to toy with his sleeve with the slender fingers of one hand, as though in that manner to compel his greater attention. "You know Stella Lamar really was in love with Jack Gordon. In fact she was daffy over him. And now I've found out that he was borrowing money from her, was taking nearly every cent she earned to sink in his speculations. Do you get that?" Enid's eyes snapped. Most certainly I understood. I knew well the type of Stella. She had made many men give up to her motor cars, expensive furs, jewelry, all manner of presents. But in the end she had found one man to whom she in turn was willing to yield all. But what of him? "In the last few weeks, they tell me, poor Stella disposed of many of her handsome presents from men like Manton and Phelps and others, all to get money to give to him. At the end she even raised money on her jewelry. I--I think you'll find it all in pawn now, if you'll investigate. I don't doubt but that poor Stella died without a penny to her name." I was so surprised at this information that I failed to study Kennedy's face. I was completely jolted from my own rapt contemplation of the very soft curves of Enid's back. For here was a motive at last! Gordon was a possible suspect I had failed to take even halfway seriously. Yet the leading man was desperately pressed for money, had had a disgraceful fight with Phelps as we already knew; and not only owed huge sums to his fiancee as Enid now explained, but had quarreled with her just prior to her death, according to his own admission in the investigation at Tarrytown. Suddenly the music struck up once more. Enid rose, adjusting the straps of her gown. "There!" she exclaimed, smiling abruptly. "I thought you ought to know that, though I hate to peddle gossip. Now I must hurry back. I've been away long enough. But come down later and dance." She swept off without further formality. An instant afterward we saw her in the clasp of Millard once again. We watched during the number and encore; then Kennedy called for the check. "Let's go up to the apartment," he suggested. "I'd like to talk some of these things out with you. It will help me clarify my own impressions." Underneath the balcony I noticed Kennedy turn for a last glance at Manton's party. I paused to look, also. Enid was leaning forward, talking to Millard earnestly, emphasizing what she had to say with characteristic movements of her head. "She's pumping Millard for more information about Stella Lamar," I remarked. Kennedy had no comment. XVII AN APPEAL We strolled up Broadway, resisting the attraction of a garish new motion-picture palace at which Manton's previous release with Stella Lamar was now showing to capacity--much to the delight of the exhibitor who greatly complimented himself on his good fortune in being able to take advantage of the newspaper sensation over the affair. On we walked, Kennedy mostly in silent deduction, I knew, until we came to the upper regions of the great thoroughfare, turned off, and headed toward our apartment on the Heights, not far from the university. We had scarcely settled ourselves for a quiet hour in our quarters when the telephone rang. I answered. To my amazement I found that it was Marilyn Loring. "Is Professor Kennedy in?" she asked. "Yes, Miss Loring. Just a--" "Never mind calling him to the phone, Mr. Jameson. I've been trying to find him all evening. He was not at the laboratory, although I waited over an hour. Just tell him that there's something I am very anxious to consult him about. Ask him if it will be all right for me to run up to see him just a few minutes." I explained to Kennedy. "Let her come along," he said, as surprised as I was. Then he added, humorously, "I seem to be father confessor to-night." After sinking back in my seat in comfort once more I observed a quiet elation in Kennedy's manner. All at once it struck me what he was doing. The multitude of considerations in this case, the many cross leads to be followed, had confused me. But now I realized that, after all, this was only the approved Kennedy method, the mode of procedure which had never failed to produce results for him. Without allowing himself to be disturbed by the great number of people concerned, he had calmly started to pit them one against the other, encouraging each to talk about the rest, making a show of his apparent inaction and lack of haste so that they, in turn, would shake off the excitement immediately following the death of the girl and thereby reveal their normal selves to his keen observation. Not five minutes passed before Marilyn was announced. Evidently she had been seeking us eagerly, for she had probably telephoned from a near-by pay station. "Mr. Kennedy," she began, "I am going to find this very hard to say." "Really," he assured her, "there is no reason why you should not repose your confidence in me. My only interest is to solve the mystery and to see that justice is satisfied. Beyond that nothing would give me greater happiness than to be of service to you." "It's--it's about Merle Shirley--" she started, bravely. Then all at once she broke down. The strain of two days had been too much for her. Kennedy lighted a fresh cigar, realizing that he could best aid her to recover her composure by making no effort to do so. For several moments she sobbed silently, a handkerchief at her eyes. Then she straightened, with a half smile, dabbing at the drops of moisture remaining. With her wet eyes and flushed cheeks she was revealed to me again as a very genuine girl, wholly unspoiled by her outward mask of sophistication. Furthermore, at this instant she was gloriously pretty. "Again--why do you play vampire roles, Miss Loring?" I asked, as quickly as the thought flashed to me. "I think you'd be an ideal ingenue!" "About a thousand people have told me that," she rejoined. As she replied her smile took full possession of her features. My idiotic repetition, entirely out of place, had served to restore her self-control to her. "No, the public won't stand for it. They've been trained to know me as a vamp, and a vamp I remain." Facing Kennedy, she sobered. "Merle Shirley and I were engaged," she went on. "That you know. Then poor Stella made a fool of him. She didn't mean any harm, any real harm, but I don't think she knew how deep he feels or just what a fiery temper he has. Finally he found out that she was only playing with him. He was perfectly terrible. At first I thought he had killed her in a burst of passion. I really thought that." "Yes?" Kennedy was interested. He needed no pretense. "When I asked him point blank he said he didn't." A very wonderful light came into Marilyn Loring's eyes at this instant. "Whatever else he would do, Professor Kennedy, he wouldn't lie to me; that I know. He would tell me the truth because he knows I would shield him, no matter what the cost." "You simply want to assure me of his innocence?" suggested Kennedy. "No!" There was a touch of scorn to the little negative. "You don't believe him guilty; you didn't even when I did." "Then--" "But he knows something--something about the murder of Stella--and he won't tell me what it is. I--I'm afraid for him. He isn't sleeping at night, and I believe he's watching somebody at the studio, and I know--it's the WOMAN'S intuition, Professor"--she emphasized the word, and paused--"he's in danger. He's in some great threatening danger!" "What do you wish me to do, Miss Loring?" "I want you to protect him and"--slowly she colored, up and around and about her eyes as she always did, until she wasn't unlike an Indian maid--"and no one must know I've been up to see you." Gravely Kennedy bowed her to the door, assuring her he would do all that lay in his power. When he returned I was ready for him. "Now!" I exclaimed. "Now say it isn't Werner! Here is Merle Shirley watching some one at the studio. Isn't that likely to be the director? And if Shirley is watching Werner you have the explanation for the second intruder at Tarrytown last night. Shirley is big enough and strong enough to have given the deputy a nice swift tussle." "A little tall, I'm afraid," Kennedy remarked. "You can't go by the deputy's impressions. He didn't really remember much of anything. Certainly he was unobserving." "Perhaps you're right, Walter." Kennedy smiled. "But how about Gordon?" he added. "There's genuine motive--money!" "Or Shirley himself!" I attempted to be sarcastic. "There's genuine motive. Stella made a fool out of him." "It wasn't a murder of passion," Kennedy reminded me. "No one in a white heat of rage would study up on snake venoms." "If it were a slow-smoldering--" "Shirley's anger wasn't that kind." "But good heavens!" As usual I arrived nowhere in an argument with Kennedy. "Circumstantial evidence points to Werner almost altogether--" "You've forgotten one point in your chain, Walter." "What's that?" "Whoever took the needle from the curtain last night scratched himself on it and left blood spots on the portieres, tiny ones, but real blood spots, nevertheless. That means the intruder inoculated himself with venom. I doubt that the poison was so dry as to be ineffectual. If it was Werner, how do you account for the fact that he is still alive?" "Do you"--I guess my eyes went wide--"do you expect to dig up a dead man somewhere? Is there some one we suspect and haven't seen since yesterday?" He didn't answer, preferring to tantalize me. "How do you account for it yourself?" I demanded, somewhat hotly. "Let's call it a day, Walter," he rejoined. "Let's go to bed!" XVIII THE ANTIVENIN I slept late in the morning, so that Kennedy had to wake me. When we had finished breakfast he led the way to the laboratory, all without making any effort to satisfy my curiosity. There he started packing up the tubes and materials he had been studying in the case, rather than resuming his investigations. "What's the idea?" I asked, finally, unable to contain myself any longer. "You carry this package," he directed. "I'll take the other." I obeyed, somewhat sulkily I'm afraid. "You see," he added, as we left the building and hurried to the taxi stand near the campus, "the next problem is to identify the particular kind of venom that was used. Besides, I want to know the nature of the spots on the towel you found. They certainly were not of venom. I have my suspicions what they really are." He paused while we selected a vehicle and made ourselves comfortable. "To save time," he went on, "I thought I'd just go over to the Castleton Institute. You know in their laboratories the famous Japanese investigator, Doctor Nagoya, has made some marvelous discoveries concerning the venom of snakes. It is his specialty, a matter to which he has practically devoted his life. Therefore I expect that he will be able to confirm certain suspicions of mine very quickly, or"--a shrug--"explode a theory which has slowly been taking form in the back of my head." When we dismissed the taxi in front of the institute I realized that this would be my first visit to this institution so lavishly endowed by the multi-millionaire, Castleton, for the advancement of experimental science. Kennedy's card, sent in to Doctor Nagoya, brought that eminent investigator out personally to see us. He was the very finest type of Oriental savant, a member of the intellectual nobility of the strange Eastern land only recently made receptive to the civilization of the West. When he and Kennedy chatted together in low tones for a few moments it was hard for me to grasp that each belonged to a basic race strain fundamentally different from the other. East and West had met, upon the plane of modern science. The two were simply men of specialized knowledge, the Japanese pre-eminent in one field, Kennedy in another. Carefully and thoroughly Kennedy and Nagoya went over the results which Kennedy had already obtained. After a moment Doctor Nagoya conducted us to his research room. "Now let me show you," said the Oriental. In a moment they were deep in the mysteries of an even more minute analysis than Kennedy had made before. I took a turn about the room, finding nothing more understandable than the study holding Kennedy's interest. Though I could not grasp it, curiosity kept me hovering close. "You see"--Nagoya spoke as he finished the test he was making at the moment--"without a doubt it is crotalin, the venom of the rattlesnake, Crotalus horridus." "There was no snake actually present," I hastened to explain, breaking in. Then at a glance from Kennedy I stopped, abashed, for all this had been made clear to the scientist. "It is not necessary," Nagoya replied, turning to me with the politeness characteristic of the East. "Crotalin can be obtained now with fair ease. It is a drug used in a new treatment of epilepsy which is being tried out at many hospitals." I nodded my thanks, not wanting to interrupt again. Kennedy pressed on to the next point he wished established. "That was the spot on the portieres. Now the ampulla." "Also crotalin." Doctor Nagoya spoke positively. "How about this solution?" Kennedy took from my package the tube with the liquid made from the faint spots on the towel which I had found and which had been our first clue. "It is not crotalin." The Japanese turned to his laboratory table. Kennedy muttered some vague suggestions which were too technical for me but which seemed to enable Nagoya to eliminate a great deal of work. The test progressed rapidly. Finally the savant stepped back, regarding the solution with a very satisfied smile. "It is," he explained, carefully, "some of the very anticrotalus venin which we have perfected right here in the institute." Kennedy nodded. "I suspected as much." There was great elation in his manner. "You see, I had heard all about your wonderful work." "Yes!" Nagoya waved his hand around at the wonderfully equipped room, only one detail in the many arrangements for medical research made possible by the generosity of Castleton. "Yes," he repeated, proud of his laboratory, as he well might be, "we have made a great deal of progress in the development of protective sera--antivenins, we call them." "Are they distributed widely?" Kennedy asked, thoughtfully. "All over the world. We are practically the only source of supply." "How do you obtain the serum in quantity?" "From horses treated with increasing doses of the snake venom." A question struck me as I remembered the peculiar double action of the poison. "Can you tell me just how the antivenin counteracts the effects of the venom?" I inquired of the savant. "Surely," he replied. "It neutralizes one of the two elements in the venom, the nervous poison, thus enabling the individual to devote all his vitality to overcoming the irritant poison. It is the nervous poison that is the chief death-dealing agent, producing paralysis of the heart and respiration. We advise all travelers to carry the protective serum if they are likely to be exposed to snake bites." Kennedy picked up the tube containing the solution made from the towel spots. "This antivenin was your product, doctor?" "Probably so," was the precise answer. "Then the purchasers can be identified," I suggested. "We have no record of ordinary purchasers," Nagoya explained, slowly. Kennedy was keenly disappointed at that, and showed it. However, he thanked the scientist cordially, and we departed. Outside, he turned to me. "Do you understand now why the night intruder at Tarrytown did not die--if he is one of our suspects--from the scratch of the needle?" "You mean he had taken an injection of antivenin before--" "Exactly! We are dealing with a criminal of diabolical cleverness. Not only did he make all his plans to kill Miss Lamar with the greatest possible care, but he prepared against accident to himself. He was taking no chances. He inoculated himself with a protective serum. The needle of the syringe he used for that purpose he wiped upon the towel you discovered in the washroom." XIX AROUND THE CIRCLE "I'd like to have another talk with Millard about that Fortune Features affair," remarked Kennedy. It was the third morning after the death of Stella Lamar, and I found him half through breakfast when I rose. About him were piled moving picture and theatrical publications, daily, weekly, and monthly. At the moment I caught him he had spread wide open the inner page of the Daily Metropolitan, a sheet devoted almost exclusively to sports and the amusement fields. I went around to glance over his shoulder. He pointed to a small item under a heading of recent plans and changes. FORTUNE FEATURES It is hinted to the Metropolitan Man-about-Broadway, by those in a position to know but who cannot yet be quoted, that Fortune Features is about to absorb a number of the largest competing companies. Rumors of great changes in the picture world have been current for some weeks, and this is the first reliable information to be given out. It is premature to give details of the new combination, or to mention names, but Fortune's strong backing in Wall Street will, we are assured, have a stabilizing influence at a critical time in the industry. "Seems to be a lot of hot air," I said. "There isn't a name mentioned. Everything is 'by those in a position to know' and 'rumors of and 'it is premature to give details... or mention names'--Bah!" Kennedy turned to places he had marked in several of the other periodicals and papers and I read them. Each was substantially to the effect of the note in the Metropolitan, although worded differently and generally printed as a news item. "It's a feeler," Kennedy stated. "There's something back of it. When I caught the reference to Fortune Features in the Metropolitan, which I've been reading the past two days, I sent the boy out for every movie publication he could find. Result: half a dozen repetitions of the hint that Fortune is expanding. That means that it is deliberate publicity." "You think this has something to do with the case?" "I don't see the name of Manton mentioned once. Manton is a man who seeks the front page on every opportunity. You remember, of course, what Millard told us. Somehow I smell a rat. If nothing else develops for this morning, I want to find Millard and talk to him again. I believe Manton is up to something." The sharp sound of our buzzer interrupted us. Because I was on my feet I went to the door. To my amazement I found it was Phelps who was our very early visitor. "I hope you'll excuse this intrusion," he apologized to Kennedy, pushing by me with the rudeness which seemed inherent in the man. Then he recognized the sheet still spread out on the table. "I see you, too, have been reading the Metropolitan." "Yes," Kennedy admitted, languidly. "There is nothing about Manton Pictures, though." "Manton Pictures, hell!" In an instant Phelps exploded and the thin veneer of politeness was gone. With a shaking finger he pointed to the item which we had just been reading and discussing. "Did you read that! Did you see the reference to stabilizing the industry? STABILIZING! It ought to be spelled stable-izing, for they lead all the donkeys into stalls and tie them up and let them kick." He stopped momentarily for sheer inability to continue. "I suppose you don't know Manton is behind this Fortune Features?" "We were aware of the fact," Kennedy told him, quietly. Phelps looked from one to the other of us keenly, as if he had thought to surprise us and had been disappointed. Nervously he began to pace the floor. "Perhaps you know also that things haven't been going just right with Manton Pictures?" Kennedy straightened. "When I asked you at Tarrytown, just two mornings ago, whether there was any trouble between Manton and yourself, you answered that there was not." Phelps flushed. "I didn't want to air my financial difficulties with Manton. My--my answer was truthful, the way you meant your question. Manton and I have had no words, no quarrel, no disagreement of a personal nature." "What is the trouble with Manton Pictures?" "They are wasting money--throwing it right and left. That pay roll of theirs is preposterous. The waste itself is beyond belief--sometimes four and five cameras on a scene, retakes upon the slightest provocation, even sets rebuilt because some minor detail fails to suit the artistic eye of the director. Werner, supposed to watch all the companies, doesn't half know his business. In the making of a five-reel film they will overtake sometimes as much as eighty or a hundred thousand feet of negative in each of two cameras, when twenty thousand is enough overtake for anyone. That alone is five to ten thousand dollars for negative stock, almost fifteen with the sample print and developing. And the cost of stock, Mr. Kennedy, is the smallest item. All the extra length is long additional weeks of pay roll and overhead expense. I put an auditor and a film expert on the accounts of Stella Lamar's last picture. By their figures just sixty-three thousand dollars was absolutely thrown away." Kennedy rose, folding the newspaper carefully while he collected his thoughts. "My dear Mr. Phelps," he stated, finally, "that is simply inefficiency. I doubt if it is anything criminal; certainly there is no connection with the death of Stella Lamar, my only interest in Manton Pictures." Phelps was very grave. "There is every connection with the death of Stella Lamar!" "What do you mean?" "Mr. Kennedy, what I'm going to say to you I cannot substantiate in any court of law. Furthermore I'm laying myself open to action for libel, so I must not be quoted. But I want you to understand that Stella was inescapably wound up with all of Manton's financial schemes. His money maneuvers determined her social life, her friends--everything. She was then, as Enid Faye will be now, his come-on, his decoy. Manton has no scruples of any sort whatsoever. He is dishonest, tricky, a liar, and a cheat. If I could prove it I would tell him so, but he's too clever for me. I do know, however, that he pulled the strings which controlled every move Stella Lamar ever made. When she went to dinner with me it was because Manton wished her to do so. She was his right hand, his ears, almost his mouth. I have no doubt but that her death is the direct result of some business deal of his--something directly to do with his financial necessities." Kennedy did not glance up. "Those are very serious assertions." "It is a very serious matter. To show how unscrupulous Manton is, I can demonstrate that he is wrecking Manton Pictures deliberately. I've told you of the waste. Only the other day I came into the studio. Werner was putting up a great ballroom set. You saw it? No, that isn't the one I mean. I mean the first one. He had it all up; then some little thing didn't suit him. The next day I came in again. All struck--sloughed--every bit of it--and a new one started. 'Lloyd,' I said, 'just think a minute--that's my money!' What good did it do? He even began to alter the new set! He would only go on, encouraging Werner and the other directors to change their sets, to lose time in trying for foolish effects, anything at all to pad the expense. "You think I am romancing, but you don't understand the film world," Phelps hurried on angrily. "Do you know that Enid Faye's contract is not with Manton Pictures but with Manton himself? That means he can take her away from me after he has made her a star with my money, at my expense. Why should he wreck Manton Pictures, you ask? Do you know that, bit by bit, on the pretext that he needed the funds for this that, or the other thing, Manton has sold out his entire interest in the company to me? It is all mine now. I tell you," complained Phelps, bitterly, "he couldn't seem to wreck the company fast enough. Why? Do you realize that there isn't room both for this older company and the new Fortune Features? Can you see that if Manton Pictures fails the Fortune company will be able to pick up the studio and all the equipment for a song? I'm the fall guy! "And yet, Kennedy, all the efforts to wreck Manton Pictures would have failed, because 'The Black Terror' was too sure a success. In spite of all the expense, in spite of every effort to wreck it, that picture would have made half a million dollars. Stella's acting and Millard's story and script would have put it over. But now Millard's contract has expired and Manton has signed him for Fortune Features. Enid Faye will be made a star by 'The Black Terror,' but she is not now the drawing power to put it over big, as Stella would have done. I tell you, Kennedy, the death of Stella Lamar has completed the wreck of Manton Pictures!" Kennedy jumped to his feet. There was a hard light in his eyes I had never seen before. "Do I understand you, Phelps?" he snapped. "Are you accusing Manton of the cold-blooded murder of Stella Lamar to further various financial schemes?" "Hardly!" Phelps blanched a bit, and I thought that a shudder swept over him. "I don't mean anything like that at all. What I mean is that Manton, in encouraging various sorts of dissension to wreck the company, inadvertently fanned the flames of passion of those about her, and it resulted in her death." "Who killed her?" "I don't know!" Grudgingly I admitted that this seemed open and frank. "At Tarrytown," Kennedy went on, "I asked you if Stella Lamar was making any trouble, had threatened to quit Manton Pictures, and you said no. Is that still your answer?" "For several months she had been up-stage. That was not because she wanted to make trouble, but because she had fallen in love. Manton found he couldn't handle her as he had previously." "Do you suspect Manton of killing her himself?" "I don't suspect anyone. That is an honest answer, Mr. Kennedy." "What do you know about Fortune Features?" The banker's eye fell on the newspaper again. "I know who this new Wall Street fellow is. I've got my scouts out working for me. It's Leigh--that's who it is. And I'm sore; I have a right to be." Phelps was getting more and more heated, by the moment. "I tell you," he almost shouted, "this fake movie business is the modern gold-brick game, all right. Never again!" I was amazed at the Machiavellian cleverness of Manton. Here he was, on one hand openly working with, yet secretly ruining, the Manton Pictures, while on the other hand he was covertly building up the competing Fortune Features. Kennedy paced out into the little hall of our suite and back. He faced our visitor once more. "Why did you come to see me this morning? At our last encounter, you may recall you said you wished you could throw me down the steps." Phelps smiled ruefully. "That was a mistake. It was the way I felt, but--I'm sorry." "Now--?" Again the black clouds overshadowed the features of the financier. "Now I want you to bring out and prove the things I've told you." The malice showed in his voice plainly, for the first time. "I want it proved in court that Manton is a cheap crook. When you uncover the murderer of Stella Lamar you will find that the moral responsibility for her death traces right back to Lloyd Manton. I want him driven out of the business." Kennedy's attitude changed. As he escorted Phelps to the door his tones were self-controlled. "Anything of the sort is beyond my province. My task is simply to find the person who killed the girl." When the financier was gone I turned to Kennedy eagerly. "What do you think?" I asked. "I think, more than ever, that we should investigate Fortune Features. Let's have a look at the telephone book." There was no studio of the new corporation in New York, but we did find one listed in New Jersey, just across the river, at Fort Lee. We walked from the university down the hill and over to the ferry. On the other side a ten minutes' street-car ride took us to our destination. Facing us was a huge barn-like structure set down in the midst of a little park. Inquiry for Manton brought no response whatever; rather, surprise that we should be asking for him here. However, I reflected that that was exactly what we ought to expect if Manton was working under cover. The girl at the telephone switchboard, smiling at Kennedy, had a suggestion. "They're taking a storm exterior down in the meadow," she explained. "Perhaps he's down there, among the visitors--or perhaps there's someone who will be able to give you some information." I glanced outdoors at the brightly shining sun. "A storm?" I repeated, incredulously. "Yes," she smiled. "It might interest you to see it." Following her directions, we started across country, leaving the studio building some distance behind and entering a broad expanse of meadow beyond a thin clump of trees. At the farther end we could see a large group of people and paraphernalia which, at the distance, we could not make out. However, it was not long after we emerged from the trees that we perceived they were photographing squarely in our direction. Several began waving their arms wildly at us and shouting. Kennedy and I, understanding, turned and advanced, keeping well out of the camera lines, along the edge of the field. "Hello!" a voice greeted us as we approached the group standing back and watching the action. To my surprise it was Millard, with the spectators. I looked about for Manton but did not see him, nor anyone else we knew. "It's a storm and cyclone," said Millard, his attention rather on what was going on than on us. For the moment we said nothing. The scene before us was indeed interesting. Half a dozen aeroplane engines and propellers had been set up outside the picture, and anchored securely in place. The wind from them was actually enough to knock a man down. Rain was furnished by hose playing water into the whirling blades, sending it driving into the scene with the fury of a tropical storm. Back of the propellers half a dozen men were frantically at work shoveling into them sand and dirt, creating an amazingly realistic cyclone. We arrived in the midst of the cyclone scene, as the dust storm was ending and the torrential rain succeeded. For the storm, a miniature village had been constructed in break-away fashion, partially sawed through and tricked for the proper moment. Many objects were controlled by invisible wires, including an actual horse and buggy which seemed to be lifted bodily and carried away. Roofs flew off, walls crashed in, actors and actresses were knocked flat as some few of them failed to gain their cyclone cellars. Altogether, it was a storm of such efficiency as Nature herself could scarcely have furnished, and all staged with the streaming sunlight which made photography possible. Pandemonium reigned. Cameras were grinding, directors were bawling through megaphones, all was calculated chaos. Yet it took only a glance to see that some marvelous effects were being caught here. At the conclusion I recognized suddenly the little leading lady, It was the girl we had seen with Manton at Jacques' cabaret. "That's the way to take a picture," exclaimed Millard. "Everything right--no expense spared. I came over to see it done. It's wonderful." "Yes," was Kennedy's answer, "but it must be very costly." "It is all of that," said Millard. "But what of it if the film makes a big clean-up? I wouldn't have missed this for anything. Werner never staged a spectacle like this in his life. Fortune Features are going to set a new mark in pictures." "But can they keep it up? Have they the money?" Millard shrugged his shoulders. "Manton Pictures can't--that's a cinch. Phelps has reached the end of his rope, I guess. I'm afraid the trouble with him was that he was thinking of too many things besides pictures." There was no mistaking the meaning of the remark. Millard was still cut by Stella's desertion of him for the broker. I caught Kennedy's glance, but neither of us cared to refer to her. "Where can I find Manton now?" Kennedy asked. "Did you try his office at seven hundred and twenty-nine?" was Millard's suggestion. "No; I wanted to see this place first." "Well, you'll most likely find him there. I've got to go back to the city myself-some scenes of 'The Black Terror' to rewrite to fit Enid better. I'll motor you across the ferry and to the Subway." At the Subway station, Millard left us and we proceeded to Manton's executive offices in a Seventh Avenue skyscraper, built for and devoted exclusively to the film business. Manton's business suite was lavishly furnished, but not quite as ornate and garish as his apartment. The promoter himself welcomed us, for no matter how busy he was at any hour, he always seemed to have time to stop and chat. "Well, how goes it?" He pushed over a box of expensive cigars. "Have you found out anything yet?" "Had a visit from Phelps this morning." Kennedy plunged directly into the subject, watching the effect. Manton did not betray anything except a quiet smile. "Poor old Phelps," he said. "I guess he's pretty uneasy. You know he has been speculating rather heavily in the market lately. There was a time when I thought Phelps had a bank roll in reserve. But it seems he has been playing the game on a shoestring, after all." Manton casually flicked the ashes from his cigar into a highly polished cuspidor as he leaned over. "I happen to have learned that, to make his bluff good, he has been taking money from his brokerage business"--here he nodded sagely--"his customers' accounts you know. Leigh knows the inside of everybody's affairs in Wall Street. They say a quarter of a million is short, at least. To tell you the truth, poor Stella took a good deal of Phelps's money. Certainly his Manton Pictures holdings wouldn't leave him in the hole as deep as all that." I reflected that this was quite the way of the world--first framing up something on a boob, then deprecating the ease with which he was trimmed. Was it blackmail Stella had levied on Phelps, I wondered? Was she taking from him to give to Gordon? Had Stella broken him? Was she the real cause of the tangle in his affairs? And had Phelps in insane passion revenged himself on her? In the conversation with Manton there was certainly no hint of answer to my queries. With all his ease, Manton was the true picture promoter. Seldom was he betrayed into a positive statement of his own. Always, when necessary, he gave as authority the name of some one else. But the effect was the same. A hurried call of some sort took Manton away from us. Kennedy turned to me with a whimsical expression. "Let's go!" he remarked. "What do you make of it, offhand?" I asked, outside. "We're going about in a circle," he remarked. "Strange group of people. Each apparently suspects the other." "And, to cover himself, talks of the other fellow," I added. Kennedy nodded, and we made our way toward the laboratory. "I'll bet something happens before the day is over," I hazarded, for no reason in particular. Kennedy shrugged. As we went, I cast up in my mind the facts we had learned. The information from Manton was disconcerting, coming on top of what had already been revealed about the inner workings of his game. If Phelps had secretly "borrowed" from the trust accounts in his charge a quarter of a million or so, I saw that his situation must indeed be desperate. To what lengths he might go it was difficult to determine. XX THE BANQUET SCENE For once I qualified as a prophet. We were hardly in our rooms when the telephone rang for Kennedy. It was District-Attorney Mackay, calling in from Tarrytown. "My men have positive identification of one of the visitors to the Phelps home the night after the murder," he reported. "Fine!" exclaimed Kennedy. "Who was it? How did you uncover his trail?" "You remember that my deputy heard the sound of a departing automobile? Well, we have been questioning everyone. A citizen here, who returned home late at just about that hour, remembers seeing a taxicab tearing through the street at a reckless rate. He came in to see me this morning. He made a mental note of the license number at the time, and while nothing stuck with him but the last three figures, three sixes, he was sure that it was a Maroon taxi. We got busy and have located the driver who made the trip, from a stand at Thirty-third all the way out and back. On the return he dropped his fare at the man's apartment. The identification is positive." "Who is it?" Kennedy became quite excited. "Werner, the director." "Werner!" in surprise. "What are you going to do?" "Arrest him first--examine him afterward. I've sworn out the warrant already, and I'm going to start in by car just as soon as we hang up. I thought I'd phone you first in case you wanted to accompany me to the studio." "We'll hurry there," Kennedy replied, "and meet you." "Outside?" "No, up on the floor." "You'll be there fifteen minutes to half an hour ahead of me. I hope there is no way for anyone to tip him off so he can escape." "We'll stop him if he attempts it." "Good!" The courtyard of the studio of Manton Pictures, Incorporated, was about the same as upon the occasions of our previous visits except that I detected a larger number of cars parked in the inclosure, including a number of very fine ones. Also, it seemed to me that there was a greater absence of life than usual, as though something of particular interest had taken everyone inside the buildings. The gateman informed us that Werner was working the large studio. We made our way up through the structure containing the dressing rooms and found the proper door without difficulty. When we passed through under the big glass roof we grasped the reason for the lack of interest in the other departments about the quadrangle. Here everyone was gathered to watch the taking of the banquet scene for "The Black Terror." The huge set was illuminated brightly, and packed, thronged with people. It was a marvelous set in many ways. To carry out the illusion of size and to aid in the deceptive additional length given by the mirrors at the farther end, Werner had decided against the usual one large table arranged horseshoe-like, but had substituted instead a great number of individual smaller tables, about which he had grouped the various guests. The placing of those nearest the mirrors had been so arranged as to give no double images, thus betraying the trick. The waiters, all the characters who walked about, were kept near the front toward the cameras for the same reason. It seemed as if the banquet hall was at least twice its actual size. I saw that Millard had arrived ahead of us. Either the changing of the scenes in his script to fit Enid had not taken him very long or else the photographing of this particular bit of action had proved sufficiently fascinating to draw him away from his work. I wondered at first if he had come to the studio to use his office here, an infrequent happening, from Manton's account. Then I realized that he was in evening dress. Without doubt he planned to play a minor part in the banquet. His presence was no accident. Then I picked out Manton himself from our point of observation in a quiet corner selected by Kennedy for that purpose. It was evident that the promoter had cleared up his business at the office rapidly since we had left him there to go to our quarters on the Heights and had departed immediately from the latter place so as to precede the District Attorney here. Manton as well as Millard was in evening dress. A moment later I recognized Phelps, and he, too, wore his formal clothes. In an instant I grasped that Werner actually was saving money. Not only were these officials of the company present to help fill up the tables, but I was able now to pick out a number of the guests who were uneasy in their make-up and more or less out of place in full-dress attire. They certainly were not actors. One girl I definitely placed as the stenographer from Manton's waiting room at the studio; then other things caught my attention. I could not help but doubt the stories of waste told us by Phelps as I looked over the scene before me. The use of the mirrors to avoid building the full length of the floor did not seem to fit in with the theory that Manton and Werner were making every effort to wreck the company deliberately. I watched the financier for several moments, but did not detect anything from his manner except that he seemed to feel ill at ease and awkward in make-up. I picked out Millard again and this time found him talking with Enid Faye and Gordon. Immediately I sensed a dramatic conflict, carefully suppressed, but having too many of the outward indications to fool anyone. In fact, a child would have observed that Lawrence Millard and the leading man needed little urging to engage in a scuffle then and there. Though Stella Lamar was dead, this was the heritage she had left. Her touch had embittered two men beyond the point of reconciliation--the husband who had been, and the husband who was to be. Of the two, Millard had far the better control of himself, however. After a brief word or so Gordon left them. At once I could see the relief in the expressions of both the others. Again I wondered just what might be between these two. It was an easy familiarity which might have been as casual as it seemed to be, no more, or which might have been a mask for something far deeper and more enduring, the schooled outer cloak of an inner perfect understanding. Werner was by far the busiest of those waiting in the stifling heat beneath the glass roof. He was in evening dress, prepared to take his own place before the camera, and in straight make-up, so that he looked nothing like the slain millionaire, the part he had played in the opening scenes. I saw that he was a master in the art of make-up. I was sure that he was more nervous than usual. It struck me that he needed the stimulus of the drug he used, although later I knew that he must have felt, intuitively, the coming of events which followed close upon the attempt to photograph the action. As more of the people hurried up from the offices and around from the manuscript and other departments, very conscious of their formal attire, and as the regular players changed and adjusted the make-ups of these amateurs, the banquet took on the proportions of a real affair. The members of the cast were placed at the table in the foreground. Enid, Gordon, Marilyn, and a fourth man were assigned locations; after which Werner proceeded to fill the seats in the rear. With the exception of Millard and Phelps, none of the inexperienced people were allowed to face the camera. Manton, whose features were familiar through published interviews in many publicity campaigns, was placed to one side opposite Phelps. Millard was given charge of a group containing a number of giddy extra girls in somewhat diaphanous costume, and seemed to be in his element. The tables themselves were prepared with perfect taste. I could see that real food was being used, in order to achieve a greater degree of realism, for a caterer had set up a buffet some distance out of the scene from which to serve the courses called for in the script. Many of the dishes were being kept hot, the steam curling from beneath the covers in appetizing wisps. The wine, supposed to be champagne, was sparkling apple juice of the best quality, and I don't doubt but that before the days of prohibition Werner would have insisted upon the real fizz water. In details such as these the director was showing no economy. "All ready now?" Werner called, stepping back to a place at a table which he had reserved for himself. "All set? Remember the action of the script?" Instantly the buzz of conversation died and everyone turned to him. "No, no, no!" he exclaimed in vexation. "Don't go dead on your feet. This is a banquet. You are having a good time. It's not a funeral! You were all in just the right state of mind before, and you don't have to stop and gape to listen to me. Keep right on talking and laughing. My voice will carry and you can hear without getting out of your parts." I turned to Kennedy, to see how the picture-making struck him. I saw that he was watching the two girls at the forward table closely and so I faced about to follow his glance. Marilyn's face was red with anger, while Enid, calm and rather malicious, was ignoring her to devote all attention to Gordon. The leading man, bored and irritated, made no effort to conceal a heavy scowl. In the momentary interval following Werner's instructions, Marilyn lost all control of herself. "If you will pardon me, MISS Faye," she cried out in a voice which carried over to us and with cutting accent upon the "Miss," "I think that in this scene at least we should BOTH be facing the camera. If I understand the scene in the script at all it is intended to show the conflict between the two women over the one man seated between them. Jack Daring is to be swayed first by Stella Remsen, then by Zelda. At least this once I think the daughter of old Remsen and his ward are playing roles of equal importance." For a moment I smiled, realizing that Marilyn was not going to let Enid "take the picture away" from her as we had seen the new star do in one of her first scenes with the leading man. Then I sobered, realizing that it was the outer reflection of the deep-running passion of these people. The cloud of Stella's death was over them still. Enid responded, but in tones too low for us to hear. A new flush of red in Marilyn's face, however, demonstrated the power in the lash of the other girl's tongue. Werner hurried over to them, not masking his own irritation any too well. Without a word he began rearranging the table, moving it slightly so that while there was no great difference in its position he had yet made a show of satisfying Marilyn. In effect he pleased neither. The two pretty faces closest to the camera were a study in discontent. "I don't wonder that moving-picture directors are nervous," Kennedy remarked. "Film manufacture must keep everyone under constant tension." "What do you make of the feeling between the different people?" I asked. "Did you notice Millard and Gordon, and now Enid and Marilyn?" "There's something under cover," he rejoined; "something behind all this. I get the impression that our suspects are watching one another, like as many hawks. At various times most of them have glanced over at us. They know we are here and are conscious they may be under suspicion. Therefore I particularly want to see how those two girls act when Mackay arrives to arrest Werner." The director, stepping back to his place, took a megaphone from his assistant for use in the rehearsal. "Now you must act just as though this were a real banquet," he shouted. "Try to forget that the Black Terror is lurking outside the window, that an attack is coming from him. Remember, when the shot is fired you must all leap up as though you meant it. Here! You--you--you--" designating certain extra girls, "faint when it happens. That's not until after the toast is proposed. I'll propose the toast from my table and it will be the cue for Shirley, outside. Now don't get ahead of the action. You amateurs, don't turn around to see if the camera is working. We'll go through the action up to the moment I propose the toast." The buzz of conversation rose slightly as though an effort was being put into the gayety. I glanced about at some of the people who were cast for only this one scene, wishing I could read lips, because I was sure many of them talked of matters wholly out of place in this setting. At the same time I kept an eye on the principals and upon Werner. Finally the director was satisfied, after a second rehearsal. "All right," he bellowed, throwing the megaphone from the scene. "Shoot!" At the same instant he dropped to his place and apparently was a guest with no interest but in the food and wine before him. At the cameras-there were three of them-the assistant director kept a careful watch of the general action. In actual time by the watch the whole was very short, a second measuring to sixteen pictures or a foot of film as I explained afterward to Kennedy. The entire scene perhaps ran one hundred or one hundred and fifty feet. But on the screen, even to the spectators in the studio, the illusion in a scene of the kind would be the duration of half an hour or even more. This would be helped by close-ups of the individual action, especially by the byplay between the principals, taken later and inserted into the long shot by the film cutter. I know I was carried away by a sense of reality. It seemed to me that waiters made endless trips to and fro, that here and there pretty girls broke into laughter constantly or that men leaned forward every other moment to make witty remarks; in fact I felt genuinely sorry I could not take part in the festivities. I knew that danger, in the person of the Black Terror as played by Shirley, lurked just out the window. I felt delicious anticipatory thrills of fear, so thoroughly was I in the spirit of the thing. Then I saw that Werner was about to propose the toast, about to give the cue for the big action. "Watch him" whispered Kennedy. "He's an actor. He's taking that drink just as though he meant every drop of it." Werner had raised his delicately stemmed glass as though to join his neighbor in some pledge when a new idea seemed to strike him. He leaped to his feet. "Let's drink together! Let's drink to our hero and heroine of the evening!" Other voices rose in acclamation. The wine had been poured lavishly. Glasses clinked and we could hear laughter. Suddenly at the window, back of everyone, appeared the evil, black-masked figure of Shirley, eyes glittering menacingly from their slits, two weapons glistening blue in his hands. At the same moment there was a terrible groan, followed by a scream of agony. Werner staggered back, his left hand clutched at his breast. From his right hand the glass which he had drained fell to the canvas covered floor with an ominous dull crash. This was not in the script! Practically everybody realized the fact, for the scene instantly was in an uproar. In the general consternation no one seemed to know just what to do. Shirley was the first to act, the first to realize what had happened. Dropping his weapons, reaching the side of the stricken director in one leap, he supported him as he reeled drunkenly, then eased him to the floor. Behind us, before I could look to Kennedy to see what he would do, there was the gasp of a man out of breath from hurrying upstairs. I turned, startled. It was Mackay. "Shall I make the collar?" he wheezed. At the same instant he saw the gathering crowd in the set. "What--what's happened?" he asked. Kennedy had bounded forward only a few seconds after Shirley. As I pushed through after him, Mackay following, I discovered him kneeling at the side of Werner. "Some one send for a doctor, quick," he commanded, taking charge of things as a matter of course. "Hurry!" he repeated. "He's gasping for air and it'll be too late in a minute." Then he saw us. "Walter--Mackay"--he raised Werner's head--"push everyone back, please! Give him a chance to breathe!" A thousand thoughts flashed through my head as politely but firmly I widened the space about Kennedy and the director. Was this a case of suicide? Had Werner known we were coming for him? Had he thought to bring about his own end in the most spectacular fashion possible? Was this the fancy of a drug-weakened brain? Suddenly I realized that Werner was trying to speak. One of the camera men had helped Kennedy lift him to the top of a table, swept of its dishes and linen, so as to make it easier for him to breathe. "Out in Tarrytown," he muttered, weakly, "that night--I suspected--and--saw--" His voice trailed off into nothingness. Even the motion of his lips was too feeble to follow. In an instant I grasped the cruel injustice I had done this man in my mind. It was now that I remembered, in a flash, Kennedy's attitude and was glad that Kennedy had not suspected him. "See!" I faced Mackay, speaking in quick, low tones so the others could not hear. "I--we--have been totally and absolutely wrong in suspecting Werner. Instead, it was he who has been playing our game--trying to confirm his own suspicions. I've been entirely wrong in my deductions from the discovery of his dope and needles." "What do you mean, Jameson?" The district attorney had been taken completely off his feet by the unexpected developments. His eyes were rather dazed, his expression baffled. "What do you mean?" "Why he was out at Tarrytown that night, all right, don't you see--but--but he was the second man, the man who watched!" Mackay still seemed unable to comprehend. "There were two men," I went on, excitedly; covering my own chagrin in my impatience at the little district attorney. "The one your deputy struggled with was short, rather than tall, and very strong. That's Werner! Can't you see it? Haven't you noticed how stockily and powerfully the director is built?" "Werner must really have had some clue," murmured Mackay, dazed. It left me wondering whether the stimulation of the dope might not have heightened Werner's imagination and urged him on in following something that our more sluggish minds had never even dreamed. Meanwhile I saw that the doctor had arrived and that Kennedy had helped carry Werner to a dressing room where first aid could be given more conveniently. Now Kennedy hurried back into the studio, glancing quickly this way and that, as though to catch signs of confusion or guilt upon the faces of those about us. I colored. Instead of making explanations to Mackay, explanations which could have waited, I might have used what faculties of observation I possessed to aid Kennedy while he was giving first consideration to the life of a man. As it was, I didn't know what had become of any of the various people upon our list of possible suspects. As far as I was concerned, any or every sign and clue to the attack upon Werner might have been removed or destroyed. A sudden hush caused all of us to turn toward the door leading to the dressing rooms. It was the physician. He raised a hand for attention. His voice was low, but it carried to every corner of the studio: "Mr. Werner is dead," he announced. XXI MERLE SHIRLEY OVERACTS Appalled, I wondered who it was who had, to cover up one crime, committed another? Who had struck down an innocent man to save a guilty neck? Kennedy hurried to the side of the physician and I followed. "What symptoms did you observe?" asked Kennedy, quickly, seeking confirmation of his own first impressions. "His mouth seemed dry and I should say he suffered from a quick prostration. There seemed to be a complete loss of power to swallow or speak. The pupils were dilated as though from paralysis of the eyes. Both pharynx and larynx were affected. There was respiration paralysis. It seemed also as though the cranial nerves were partially paralyzed. It was typically a condition due to some toxic substance which paralyzed and depressed certain areas of the body." Kennedy nodded. "That fits in with a theory I have." I thought quickly, then inquired; "Could it be the snake venom again?" "No," Kennedy replied, shaking his head; "there's a difference in the symptoms and there is no mark on any exposed part of the body, as near as I could see in a superficial examination." He turned to the physician. "Could you give me blood smears and some of the stomach contents, at once? Twice, now, some one has been stricken down before the very eyes of the actors. This thing has gone too far to trifle with or delay a moment." The doctor hurried off toward the dressing room, anxious to help Kennedy, and as excited, I thought, as any of us. Next Kennedy faced me. "Did you watch the people at all, Walter?" "I--I was too upset by the suddenness of it," I stammered. All seemed to have suspicion of some one else, and there was a general constraint, as though even the innocent feared to do or say something that might look or sound incriminating. I turned. All were now watching every move we made, though just yet none ventured to follow us. It was as though they felt that to do so was like crossing a dead line. I wondered which one of them might be looking at us with inward trepidation--or perhaps satisfaction, if there had been any chance to remove anything incriminating. Kennedy strode over toward the ill-fated set, Mackay and I at his heels. As we moved across the floor I noticed that everyone clustered as close as he dared, afraid, seemingly, of any action which might hinder the investigation, yet unwilling to miss any detail of Kennedy's method. In contrast with the clamor and racket of less than a half hour previously there was now a deathlike stillness beneath the arched ground-glass roof. The heat was more oppressive than ever before. In the faces and expressions of the awed witnesses of death's swift hand there was horror, and a growing fear. No one spoke, except in whispers. When anybody moved it was on tiptoe, cautiously. Millard's creation, "The Black Terror," could have inspired no dread greater than this. Of the people we wished to study, Phelps caught our eyes the first. Dejected, crushed, utterly discouraged, he was slouched down in a chair just at the edge of the supposed banquet hall. I had no doubt of the nature of his thoughts. There was probably only the most perfunctory sympathy for the stricken director. Without question his mind ran to dollars. The dollar-angle to this tragedy was that the death of Werner was simply another step in the wrecking of Manton Pictures. Kennedy, I saw, hardly gave him a passing glance. Manton we observed near the door. With the possible exception of Millard he seemed about the least concerned. The two, scenario writer and producer, had counterfeited the melodrama of life so often in their productions that even the second sinister chapter in this film mystery failed to penetrate their sang-froid. Inwardly they may have felt as deeply as any of the rest, but both maintained their outward composure. On Manton's shoulders was the responsibility for the picture. I could see that he was nervous, irritable; yet, as various employees approached for their instructions in this emergency he never lost his grasp of affairs. In the vibrant quiet of this studio chamber, still under the shadow of tragedy, we witnessed as cold-blooded a bit of business generalship as has ever come to my knowledge. We overheard, because Manton's voice carried across to us in the stillness. "Kauf!" The name I remembered as that of the technical, or art, director under Werner, responsible for the sets of "The Black Terror." "Yes, Mr. Manton!" Kauf was a slim, stoop-shouldered man, gray, and a dynamo of energy in a quiet, subservient way. He ran to Manton's side. "Remember once telling me you wanted to become a director, that you wanted to make pictures for me?" "Yes, sir!" "You are familiar with the script of 'The Black Terror,' aren't you? You know the people and how they work and you have sets lined up. How would you like to finish the direction?" "But--but--" To the credit of the little man he dabbed at his eyes. I guess he had been fond of his immediate superior. "Mr.--Mr. Werner is d-dead--" he stammered. "Of course!" Manton's voice rose slightly. "If Werner wasn't dead I wouldn't need another director at a moment's notice. Some one has to complete 'The Black Terror.' We have all these people on salary, and all the studio expense, and the release date's settled, so that we can't stop. It's your chance, Kauf! Do you want it?" "Y-yes, sir!" "Good! I'll double your salary, including all this week. Now can you finish this banquet set to-night, while you have the people--" "To-night!" Kauf's eyes went wide, then he started to flush. "Well, to-morrow, then! We simply can't lay off a day, Kauf!" "All--all right, sir!" It seemed to me that everyone in the place sensed the horror of this. Literally, actually, Werner's body could not be cold. Even the police, the medical examiner, had not had sufficient time to make the trip out for their investigation. Yet the director's successor had been appointed and told to hurry the production. I glanced at Phelps. He raised his head slowly, his expression lifting at the thought that production was to continue without interruption. In another moment, however, there was a change in his face. His eyes sought Manton and hardened. His mouth tightened. Hate, a deep, unreasoning hate, settled into his features. Kennedy, pausing just long enough to observe the promoter's appointment of Kauf to Werner's position, continued on toward the set. Now as I looked about I saw that Jack Gordon was missing, as well as Marilyn Loring. Presumably they had gone to their dressing rooms. All the other actors and actresses were waiting, ill at ease, wondering at the outcome of the tragedy. Suddenly Kennedy stopped and I grasped that it was the peculiar actions of Merle Shirley which had halted him. The heavy man was the only one of the company actually in the fabricated banquet hall itself. Clinging to him still were the grim flowing robes of the Black Terror. As though he were some old-fashioned tragedian, he was pacing up and down, hands behind his back, head bowed, eyes on the floor. More, he was mumbling to himself. It was evident, however, that it was neither a pose nor mental aberration. Shirley was searching for something, out in the open, without attempt at concealment, swearing softly at his lack of success. Kennedy pushed forward. "Did you lose something, Mr. Shirley?" "No!" The heavy man straightened. As he drew himself up in his sinister garb I thought again of the cheap actors of a day when moving pictures had yet to pre-empt the field of the lurid melodrama. It seemed to me that Merle Shirley was overacting, that it was impossible for him to be so wrought up over the slaying of a man who, after all, was only his director, certainly not a close nor an intimate relationship. "Mr. Kennedy," he stated, ponderously, "there has been a second death, and at the hand which struck down Stella Lamar in Tarrytown. Somewhere in this banquet hall interior there is a clue to the murderer. I have kept a careful watch so that nothing might be disturbed." "Do you suspect anyone?" Kennedy asked. Shirley glanced away and we knew he was lying. "No, not definitely." "Who has been in the set since I left with the doctor?" "No one except myself, that is"--Shirley wanted to make it clear--"no one has had any opportunity to hide or move or take or change a thing, because I have been right here all the time." "I see! Thanks, and"--Kennedy seemed genuinely apologetic--"if you don't mind--I would prefer to make my investigation alone." Shirley turned on his heel and made for his dressing room. Meanwhile I had noticed a bit of by-play between Enid Faye and Lawrence Millard, the only others of our possible suspects about. Enid first had caught my eye because she seemed to be pleading with the writer, trying to hold him. I gathered from the look of disgust on Millard's face that he wanted to get Shirley out of the set before Kennedy should observe the heavy man's odd reaction to the tragedy. While I had never seen Millard and Shirley together, so as to establish in mind the state of their feelings toward each other, this would seem to indicate that they were friendly. Certainly Shirley was making a fool of himself. Enid acted, I guessed, so as to prevent Millard's interference, probably with the idea that Millard in some fashion might bring suspicion upon himself. It struck me that Enid had a wholesome respect for Kennedy. At any rate, Millard watched the little scene between Kennedy and Shirley with a quizzical expression. As Shirley left he shrugged his shoulders, then he gave Enid's cheeks a playful pinch each and started out after the heavy man in leisurely fashion. Just about the same moment Kennedy called me to his side. "Walter," he pleaded, in a low voice, "will you hurry out to the dressing room where the doctor and I took Werner and get the blood smears and sample of the stomach contents? I don't want to leave this, because we must work fast and get all the data we need before the police arrive. With perhaps a hundred people to question they'll be apt to make a fine mess of everything. This is an outlying precinct where we'll draw the amateurs, you know." I saw that Mackay was helping him and so I left cheerfully, making my way as fast as I could toward the door through which both Shirley and Millard had passed. In the hallway of the building devoted to dressing rooms I found that I did not know which one contained Werner's body. This corridor was familiar. Here Kennedy and I had waited for Marilyn Loring and had witnessed the scene between Shirley and herself. Now I did not even remember the location of her room. At last, on a chance, I tried a door softly. From within came whispered voices of deep intensity. About to close it quickly, I realized suddenly that I recognized the speakers in spite of the whispers. It was Marilyn and Shirley. They were together. Now I recollected the figured chintz which covered the wall and was to be seen through the crack made by the open door. It was her room. They had not heard my hand on the knob, nor the catch, did not know that anyone could eavesdrop. "You see!" Her tones were the more vibrant "You waited!" "I had to!" "No! I advised you to act at once." "I couldn't! I can't even now!" "All right!" Her tone became bitter. "Go ahead, your own way. But you must count the cost. You may lose me again, Merle Shirley." "How do you mean?" Her answer, in the faintest of whispers, staggered me. "If you have the blood of another man on your hands I'm through." XXII THE STEM Though my hands trembled so that I could hardly control them, I managed to close the door softly and to back away down the hall without being discovered. My head was spinning and I was dizzy. With my own ears I had heard Marilyn Loring virtually betray the guilt of the man she loved and whom therefore she had tried to shield. "If you have the blood of another man on your hands--" What more could Kennedy want? I started to run toward the studio. Then recollection of my errand stopped me. Kennedy wished the blood smears and stomach contents and was anxious to get them before the arrival of the police. At first I thought that all such evidence would be unnecessary now, after the dialogue I had overheard, but it struck me as an afterthought that it might be necessary still to prove Shirley's guilt to the satisfaction of a court and jury, and so I rushed to the next dressing room and to another, until I located the doctor and the body of the dead man. With the little package for Kennedy safely in my pocket I hurried out again into the sweltering heat beneath the glass of the big studio, and to the side of Kennedy and Mackay in the banquet-hall set. "You have a sample of each article of food now?" he was asking the district attorney. "You are sure you have missed nothing?" "As far as possible I took my samples from the table where Werner sat," Mackay explained. "When the prop. boy gets here with an empty bottle and cork I'll have a sample of the wine. I think it's the wine," he added. Kennedy turned to me. "You've got--" "In my pocket!" I interrupted. Then, rather breathlessly, I repeated the conversation I had overheard. "Good Lord!" Mackay flushed. "There it is! Shirley's the man, and I'll take him now, quick, without waiting for a warrant." "See!" I ejaculated, to Kennedy. "He killed Stella because she made a fool of him and then, when Werner discovered that and followed him to Tarrytown the other night, it probably put him in a panic of fear, and so, to keep Werner from talking--" "Easy, Walter! Not so fast! What you overheard is insufficient ground for Shirley's conviction, unless you could make him confess, and I doubt you could make him do that." "Why?" This was Mackay. "Because I don't think he's guilty. At least"--Kennedy, as always, was cautious in his statements, "not so far as anything we now know would indicate." "But his anger at Stella," I protested, "and Marilyn's remark--"' "Miss Lamar's death was the result of a cool, unfeeling plan, not pique or anger. The same cruel, careful brain executed this second crime." Mackay, I saw, was three-quarters convinced by Kennedy. "How do you account for the dialogue Jameson overheard?" he asked. "Miss Loring told us that Shirley suspected some one and was watching, and would not tell her or anyone else who it was. It seems most likely to me that it is the truth, Mackay. In that case her remark means that she believes his silence in a way is responsible for Werner's death." "Oh! If Shirley had taken you into his confidence, for instance--?" "I might possibly have succeeded in gaining sufficient evidence for an arrest, thus averting this tragedy. But it is only a theory of mine." I scowled. It seemed to me that Kennedy was minimizing things in a way unusual for him. I wondered if he really thought the heavy man innocent. "It's still my belief that Shirley is guilty," I asserted. A sound of confusion from the courtyard beneath the heavy studio windows caught Kennedy's ear and ended the colloquy. From some of those near enough to look out we received the explanation. The police had arrived, fully three-quarters of an hour after Werner's death. "I'll get the little bottle of wine, sure," Mackay murmured, picking up the food samples he had wrapped and crowding the bulky package into a pocket. "I don't see why that would have been any easier to poison than the food," was my objection. "Everyone was looking." "Very simple. The food was brought in quite late. Besides, it was dished out by the caterer before the eyes of forty or fifty people or more and there was no telling which plate would go to Werner's place. The drinks were poured last of all. I remember seeing the bubbles rise and wondering whether they would register at the distance." Kennedy did not look at me. "Did it ever occur to you," he went on, casually, "that the glasses were all set out empty at the various places long before, and that there might easily have been a few drops of something, if it were colorless, placed in the bottom of Werner's glass, with scarcely a chance of its being discovered, especially by a man who had so much on his mind at the time as Werner had? He must have indicated where he would sit when he arranged the camera stands and the location of the tables." I had not thought of that. Kennedy frowned. "If only I could have located more of that broken glass!" As he faced me I could read his disappointment. "Walter, I've made a most careful search of his chair and the table and everything about the space where he dropped. The poison must have been in the wine, but there's not a tiny sliver of that glass left, nothing but a thousand bits ground into the canvas, too small to hold even a drop of the liquid. Just think, a dried stain of the wine, no matter how tiny, might have served me in a chemical analysis." Very suddenly there was a low exclamation from Mackay. "Look! Quick! Some one must have kicked it way over here!" Fully twenty feet from Werner's place in the glare of the lights was the hollow stem of a champagne glass, its base intact save for a narrow segment. In the stem still were a couple of drops of the wine, as if in a bulb or tube. "Can it be the director's glass?" Mackay asked, handing it to Kennedy. Kennedy slipped it into his pocket, fussing with his handkerchief so that the precious contents would not drip out. "I think so. I doubt whether any other glass was broken. Verify it quickly." The police were entering now with Manton. Following them was the physician. Mackay and I ascertained readily that no other glass had been shattered, while Kennedy searched the floor for possible signs that the stem was part of a glass broken where we had found it. Unquestionably we had a sample of the actual wine quaffed by the unfortunate Werner. Elated we strolled to a corner so as to give the police full charge. "They'll waste time questioning everyone," Kennedy remarked. "I have the real evidence." He tapped his pocket. The few moments that he had had to himself had been ample for him to obtain such evidence as was destroyed in so many cases by the time he was called upon the scene. A point occurred to me. "You don't think the poison was planted later during the excitement?" "Hardly! Our criminal is too clever to take a long chance. In such a case we would know it was some one near Werner and also there would be too many people watching. Foolhardiness is not boldness." I took to observing the methods of the police, which were highly efficient, but only in the minuteness of the examination of witnesses and in the care with which they recorded names and facts and made sure that no one had slipped away to avoid the notoriety. The actors and actresses who had stood rather in awe of Kennedy, both here and in Kennedy's investigation at Tarrytown, developed nimble tongues in their answers to the city detectives. The result was a perfect maze of conflicting versions of Werner's cry and fall. In fact, one scene shifter insisted that Shirley, as the Black Terror, had reached Werner's side and had struck him before the cry, while an extra girl with a faint lisp described with sobering accuracy the flight of a mysterious missile through the air. I realized then why Kennedy had made no effort to question them. Under the excitement of the scene, the glamour of the lights, the sense of illusion, and the stifling heat, it would have been strange for any of the people to have retained correct impressions of the event. The police sergeant knew Kennedy by reputation and approached him after a visit to the dead man's body with the doctor. His glance, including Mackay and myself, was frankly triumphant. "Well," he exclaimed, "I don't suppose it occurred to any of you SCIENTIFIC guys to search the fellow, now did it?" Kennedy smiled, in good humor. "Searching a man isn't always the scientific method. You won't find the word 'frisk' in any scientific dictionary." "No?" The police officer's eyes twinkled. There was enough of the Irish in him to enjoy an encounter of this kind. "Maybe not, but you might find things in a chap's pocket which is better." With a flourish he produced a hypodermic syringe, the duplicate of the one I had appropriated, and a tiny bottle. "The man's a dope," he added. "I knew that," replied Kennedy. "I examined his arm, where he usually took his shots, and found no fresh mark of the needle." "That doesn't prove anything. Wait until the medical examiner gets here. He'll find the fellow's heart all shot full of hop, or something. I guess it isn't so complicated, after all. He was a hop fiend, all right." "Still, there's nothing to indicate that he was a suicide." "Not suicide; accident-overdose," was the sergeant's reply. "How could he have died from an overdose of the drug, when he hasn't taken any recently?" "Well"--unabashed--"then he croaked because he hadn't had a shot--the same thing. Heart failure, either way. Excited, and all, you know, making the scene. Maybe he forgot to use the needle at that." "Perhaps you're right." Kennedy shrugged calmly. What was the use of disputing the matter? I started to protest against the detective's hypothesis. The idea of any drug addict ever forgetting to take his stimulant was too preposterous. But Kennedy checked me. All were now keenly listening to the argument. Better, perhaps, to let some one think that nothing was suspected than to disclose the cards in Craig's hand. I saw that he wished to get away and had not spoken seriously. He turned to Mackay. "Walter and I will have to hurry to the laboratory. Would you like to come along?" "You bet I would!" The district attorney showed his delight. "I was just going to ask if I might do so. There's nothing for me in Tarrytown to-day and this is out of my jurisdiction." As we turned away the police sergeant saw us and called across the floor, not quite concealing a touch of professional jealousy. "The three of you were here at the time, weren't you?" "No," Kennedy answered. "Mr. Jameson and myself." "Well, you two, then! You're witnesses and I'll ask you to hold yourself in readiness to appear at the hearing." I thought that the policeman was particularly delighted at his position to issue orders to Kennedy, and I was angered. Again Craig held me in check! "We'll be glad to tell anything we know," he replied, then added a little fling, a bit of sarcasm which almost went over the other's head. "That is," he amended, "as eye-witnesses!" XXIII BOTULIN TOXIN Mackay drove us to the laboratory in his little car and it was dark and we were dinnerless when we arrived. Knowing Kennedy's habits, I sent out for sandwiches and started in to make strong coffee upon an electric percolator. The aroma tingled in my nostrils, reminding me that I was genuinely hungry. The district attorney, too, seemed more or less similarly disposed. As for Kennedy, he was interested in nothing but the problem before him. He had been strangely quiet on the way, growing more and more impatient and nervous, as though the element of time had entered into the case, as though haste were suddenly imperative. Once the lights were on in the laboratory he hurried about his various preparations. The food samples he laid out, but he gave them no attention. The blood smears and stomach contents he put aside for future reference. His attack was upon the drop or two of liquid adhering to the stem of the broken champagne glass. The entire chemical procedure seemed to be incomprehensible to Mackay and he was fascinated, so that he had considerable trouble at times keeping out of the way of Kennedy's elbow. Kennedy first washed the stem out carefully with a few drops of distilled water, then he studied the resulting solution. One after another he tried the things that occurred to him, making tests wholly unproductive of results. Slowly the laboratory table became littered completely with chemicals and apparatus of all sorts, a veritable arsenal of glass. The sandwiches arrived, but Kennedy refused to drop his investigation for a moment. I did succeed in making him take a cup of strong coffee, and that was all. Over in a corner Mackay and I did full justice to the food, finishing the hot and welcome coffee and then refilling the percolator and starting it on the making of a second brew. The hours lengthened, and when Mackay grew tired of watching with intense admiration he joined me in the patient consumption of innumerable cigarettes. Kennedy was filled with the joy of discovery. I noticed that he did not stop even for the solace of tobacco. It seemed to me that at times his nostrils dilated exactly like those of a hound on the scent. Finally he held up a test tube and turned to us. "What is it?" I asked. "Some other poison as rare and little known as the snake venom?" "No--something much more curious. In the stem of the glass I find the toxin of the Bacillus botulinus." "Germs?" Mackay inquired. Kennedy shook his head. "Not germs, but the pure toxin, the poison secreted by this bacillus." "What does it do?" was my question. "Well," thoughtfully, "botulism may be ranked easily among the most serious diseases known to medical science. It is hard to understand why it is not a great deal more common. It is one of the most dangerous kinds of food poisoning." "Then the apple juice they used for the wine was bad, spoiled?" "No, not that. Werner was the only one stricken. Somebody put the pure toxin in his glass. It was, as I suspected, deliberate murder, as in the case of Miss Lamar. Bacillus botulinus produces a toxin that is extremely virulent. Hardly more than a ten-thousandth of a cubic centimeter would kill a guinea pig. This was botulin itself, the pure toxin, an alkaloid just like that which is formed in meat and other food products in cases of botulism. The idea might also have been to make the death seem natural--due solely to bad food." "Do you suppose it was used because it was quick and was colorless, so as not to be noticed in the glass?" I hazarded. Kennedy paced up and down the laboratory several times in thought. "To me, Walter, this is another indication of the satanic cleverness of the unknown criminal in the case. First Miss Lamar is to be killed. For that purpose something was sought, probably, which could not be traced easily to the perpetrator. In snake venom an agent was employed which may be said to be almost ideal for the grim business of murder. It is extremely difficult to identify in its results, it is comparatively unknown, yet it is swift in action and to be obtained with fair ease. "Differing from most poisons, it may be inflicted through a prick so slight as to be almost unnoticed by the victim. The scheme of fixing the needle in the curtain was so simple and yet so effective that the guilty person need never have feared its discovery under ordinary circumstances, or its association with the girl's death, if some one stumbled upon it accidentally. The idea of returning for the death-dealing point was only one of the many details of a precautionary measure upon which we have stumbled. Had I found it the next morning I would have been unable, in all probability, to identify it as belonging to or as obtained by any of our suspects. "You must realize, Walter, that with all the scientific aids I have been able to bring to bear we possess almost no direct evidence. There are no fingerprints, no cigarette stubs, no array of personal, intimate clues of any sort to this criminal. These are the threads which lead the detective to his quarry in fiction and on the stage. Here we lack even the faintest description of the man, or woman if that is her sex. It is murder from a distance, planned with almost meticulous care, executed coolly and without feeling or scruple. "After the death of Miss Lamar I was not so sure but that the selection of the snake venom was simply the inspiration of a perverted brain, the evolution of the detailed method of killing her--an outgrowth of someone's familiarity with studio life in general, with the script of 'The Black Terror' in particular. Now I realize that we are face to face with the studied handiwork of a skilled criminal. These two deaths may be his--or her--first departure into the realm of crime. But potentially we have a super-villain. "I make that statement because of the manner of Werner's demise. It is evident that the director stumbled on a clue to the murderer. If my first hypothesis had been correct, if the use of snake venom and the unlucky thirteenth scene had been largely a matter of blind chance in the selection of poison and method, then we might have expected Werner to be struck down in some dark street, or perhaps decoyed to his death--at the best, inoculated with the same crotalin which had killed Miss Lamar. "But let us analyze the method used in slaying the director. If he had been blackjacked there would be the clue of the weapon, always likely to turn up, the chance of witnesses, and also the likelihood in an extreme case that Werner might not die at once, but might talk and give a description of his assailant, or even survive. Much the same objections--from the criminal's standpoint--obtain in nearly all the accepted modes of killing a man. Even the use of venom a second time possesses the disadvantage of a certain alertness against the very thing on the part of the victim. Werner was a dope fiend, fully aware of the potency of a tiny skin puncture. I'll wager he was on constant guard against any sort of scratch. "On the other hand, the few drops of toxin in the glass possessed every advantage from the unknown's standpoint. It was invisible, and as sure in its action as the venom. Also it was as rare and as difficult to trace. For, remember this. Botulism is food poisoning. If I had not found the stem of that glass it would be absolutely impossible to show that Werner died from anything on earth but bad food. That is why I do not even take time to analyze the stomach contents. That is why I say we are confronted by an archscoundrel of highest intelligence and downright cleverness. More"--Kennedy paused for emphasis--"I realize now the presence of a grim, invisible menace. It has just now been driven home to me. The botulin, with its deadly paralyzing power, sealed Werner's tongue even while he tried to tell me what he knew." Mackay was tremendously impressed by Kennedy's explanation. "Does this mean," he asked, "that the guilty man or woman is some outsider? Those we have figured as possible suspects would hardly have this detailed knowledge of poisons." "There are two possibilities," Kennedy answered. "The real person behind the two murders may have employed some one else to carry out the actual killing, a hypothesis I do not take seriously, or"--again he paused--"this may be a case of some one with intelligence starting out upon his career of crime intelligently by reading up on his subject. It is as simple to learn how to use crotalin or botulin toxin or any number of hundreds of deadly substances as it is to obtain the majority of them. In fact, if people generally understood the ease with which whole communities could be wiped out, and grasped that it could be done so as to leave virtually no clue to the author of the horror, they might not sleep as soundly at night as they do. The saving grace is that the average criminal is often clever, but almost never truly scientific. Unfortunately, we have to combat one who possesses the latter quality to a high degree." "What is the invisible menace of which you spoke, Craig?" I inquired. "The possibility of another murder before we can apprehend the guilty person or gain the evidence we need." "Good heavens!" I imagine I blanched. "You mean--" "Werner was struck down, apparently, for no reason but that he had guessed the identity of the villain. There is a second man in the company who has certain suspicions and is acting upon them. If he is on the right trail, by any chance--" Kennedy shrugged his shoulders soberly. "Shirley?" "Exactly! And there is still another possibility." "What is that?" "Here in this laboratory I have blood spots made on the portieres at the house of Phelps by the man who removed the needle, probably the unknown himself, possibly his--or her--agent. In any case it is a clue and--THE ONLY DIRECT AND INFALLIBLE CLUE IN EXISTENCE TO THE CRIMINAL! Also I have the evidence of the snake venom and of the botulin toxin here. Sooner or later the person who killed Werner because he suspected things will wake up to the fact that we possess tangible proof against him." I grew pale. "You mean, then, that you may be attacked yourself? That even I--" Kennedy smiled, unafraid. But from the expression in his eyes I knew that he took the thought of our possible danger very seriously. XXIV THE INVISIBLE MENACE Mackay and I exchanged glances. Kennedy busied himself putting away some of the more important bits of evidence in the case, placing the tiny tubes of solution, the blood smears, and other items together in a cabinet at the farther corner of the laboratory. The vast bulk of his paraphernalia, the array of glass and chemicals and instruments, he left on the table for the morning. Then he faced us again, with a smile. "Suppose you start up the percolator once more, Walter!" He took a cigar and lighted it from the match I struck. "I believe I've earned another cup of coffee," he added. Mackay had been fidgeting considerably since Kennedy's explanation of the possible danger to Shirley, as well as to ourselves or even to others. "Isn't there something we can do, Kennedy?" he exclaimed, suddenly. "Is it necessary to sit back and wait for this unknown to strike again?" "Ordinarily," Kennedy replied, "on a case like this it has been my custom to permit the guilty parties to betray themselves, as they will do inevitably--especially when I call to my aid the recent discoveries of science for the detection and measurement of fine and almost imperceptible shades of emotion. But now that I realize the presence of this menace I shall become a detective of action; in fact, I shall not stop at any course to hurry matters. The very first thing in the morning I shall go to the studio and I want you and Jameson along. I"--his eyes twinkled; it was the excitement at the prospect--"I may need considerable help in getting the evidence I wish." "Which is--?" It was I who interposed the question. Kennedy blew a cloud of smoke. "There are three ways of tracing down a crime, aside from the police method of stool pigeons to betray the criminals and the detective bureau method of cross-examination under pressure, popularly known as the third degree." "What are they?" Mackay asked, unaware that Kennedy needed little prompting once he felt inclined to talk out some matter puzzling him. "One is the process of reasoning from the possible suspects to the act itself--in other words, putting the emphasis on the motive. A second is the reverse of the first, involving a study of the crime for clues and making deductions from the inevitable earmarks of the person for the purpose of discovering his identity. The third method, except for some investigations across the water, is distinctly my own, the scientific. "In all sciences," Kennedy went on, warming to his subject, "progress is made by a careful tabulation of proved facts. The scientific method is the method of exact knowledge. Thus, in crime, those things are of value to us which by an infinite series of empiric observations have been established and have become incontrovertible. The familiar example, of course, is fingerprints. Nearly everyone knows that no two men have the same markings; that the same man displays a pattern which is unchanging from birth to the grave. "No less certain is the fact that human blood differs from the blood of animals, that in faint variations the blood of no two people is alike, that the blood of any living thing, man or beast, is affected by various things--an infinite number almost--most of which are positively known to modern medical investigators. "In this case my principal scientific clue is the blood left upon the portiere by the man who took the needle the night following the murder. Next in importance is the fact, demonstrated by me, that some one at the studio wiped a hypodermic on a towel after inoculating himself with antivenin. Of course I am presuming that this latter man inoculated himself and not some one else, because it is obvious. If necessary I can prove it later, however, by analyzing the trace of blood. That is not the point. The point is that whoever removed the needle pricked himself and yet did not die of the venom--unless it was a person not under our observation, an unlikely premise. Therefore, because of this last fact, and because again it is obvious, I expect to find that the same individual inoculated himself with antivenin and removed the needle from the portiere; and I expect to prove it beyond possibility of doubt by an analysis of his blood. A sample of the blood from this person will be identical with the spot on the portiere, and--much the easier test--will contain traces of the antitoxin. "With that much accomplished, a little of the, well--third degree, will bring about a confession. It is circumstantial evidence of the strongest sort. Not only does a man take precautions against a given poison, but he is proved to be the one who removed the needle actually responsible for Miss Lamar's death. "My handicap, however, is that I have no justifiable excuse for taking a sample of blood from each of the people we suspect, or feel we might suspect. For that reason I was waiting until one of the other detective methods should narrow the field of suspicion. Now that there is the menace of another attempt to take a life I am forced to act. To-morrow we will get samples of blood from everyone by artifice--or force! "Meanwhile--" He hastened to continue, as though afraid we might interrupt to break his train of thought. "Meanwhile, to-night, let us see if it is possible to accomplish something by the deductive method. "Already I have gone into an analysis starting from the nature of the crime and reasoning to the type of criminal responsible. The guilty man--or woman--is a person of high intelligence, added to genuine cleverness. But for the results accomplished in this laboratory we would be without a clue; our hands would be tied completely. Both Miss Lamar and Werner were killed by unusual poisons; deadly, and almost impossible to trace. There was a crowd of people about in each case; yet we have no witnesses. Now who, out of all our people with possible motives, are intelligent enough and clever enough to be guilty?" Kennedy glanced first at me, then at Mackay. "Manton? Phelps?" suggested the district attorney. "The promoter," Kennedy rejoined, "is the typical man of the business world beneath the eccentricity of manner which seems to cling to everyone in the picture field. Ordinarily his type, thinking in millions of dollars and juggling nickel and dime admissions or other routine of commercial detail is apart from the finer subtle passions of life. When a business man commits murder he generally uses a pistol because he is sure it is efficient--he can see it work. The same applies to Phelps." "Millard?" Mackay hesitated now to face the logic of Kennedy's keen mind. "He was Stella Lamar's husband!" "Millard is a scenario writer and so apt to have a brain cluttered with all sorts of detail of crime and murder. At the same time an author is so used to counterfeiting emotion in his writings that he seldom takes things seriously. Life becomes a joke and Millard in particular is a butterfly, concerned more with the smiles of extra girls and the favor of Miss Faye than the fate of the woman whose divorce from him was not yet complete. A writer is the other extreme from the business man. The creator of stories is essentially inefficient because he tries to feel rather than reason. When an author commits murder he sets a stage for his own benefit. He is careful to avoid witnesses because they are inconvenient to dispose of. At the same time he wants the victim to understand thoroughly what is going to happen and so he is apt to accompany his crime with a speech worded very carefully indeed. Then he may start with an attempt to throttle a person and end up with a hatchet, or he may plan to use a razor and at the end brain his quarry with a chair. He lives too many lives to follow one through clearly--his own." "How about Shirley?" I put in. "At first glance Shirley and Gordon suggest themselves because both murders were highly spectacular, and the actor, above everything else, enjoys a big scene. After Werner's death, for instance, Shirley literally strutted up and down in that set. He was so full of the situation, so carried away by the drama of the occasion, that he failed utterly to realize how suspicious his conduct would seem to an observer. Unfortunately for our hypotheses, the use of venom and toxin is too cold-bloodedly efficient. The theatrical temperament must have emotion. An actor cruel and vicious enough to strike down two people as Miss Lamar and Werner were stricken, of sufficient dramatic make-up to conceive of the manner of their deaths, would want to see them writhe and suffer. He would select poisons equally rare and effective, but those more slow and painful in their operation. No, Walter, Shirley is not indicated by this method of reasoning. The arrangement of the scenes for the murders was simply another detail of efficiency, not due to a wish to be spectacular. The crowd about in each case has added greatly to the difficulty of investigation." "Do you include Gordon in that?" Mackay asked. "Yes, and in addition"--Kennedy smiled slightly--"I believe that Gordon is rather stupid. For one thing, he has had several fights in public, at the Goats Club and at the Midnight Fads and I suppose elsewhere. That is not the clever rogue. Furthermore, he had been speculating, not just now and then, but desperately, doggedly. Clever men speculate, but scientific men never. Our unknown criminal is both clever and intelligent." "That brings you to the girls, then," Mackay remarked. Kennedy's face clouded and I could see that he was troubled. "To be honest in this one particular method of deduction," he stated, "I must admit that both Miss Faye and Miss Loring are worthy of suspicion. The fact of their rise in the film world, the evidences of their popularity, is proof that they are clever. Miss Loring, in my few brief moments of contact with her on two occasions, showed a grasp of things and a quickness which indicate to me that she possesses a rare order of intelligence for a woman. As for Miss Faye"--again he hesitated--"one little act of hers demonstrated intelligence. When Shirley was standing guard in the set after Werner's death, and making a fool of himself, Millard evidently wanted to get over and speak to him, perhaps to tell him not to let me find him searching the scene as though his life depended upon it, perhaps something else. But Miss Faye stopped him. Unquestionably she saw that anyone taking an interest in the remains of the banquet just then would become an object of suspicion." "Do you really suspect Marilyn or Enid?" I inquired. "If this were half a generation ago I would say without hesitation that the crime was the handiwork of a man. But now the women are in everything. Young girls particularly--" He shrugged his shoulders. Mackay had one more suggestion. "The camera men, the extras, the technical and studio staffs--they are not worthy of consideration, are they?" Kennedy shook his head. The odor of coffee struck my nostrils and I turned to find the percolator steaming. Kennedy leaned over, to take a whiff. Mackay rose. At that moment there was a sudden crash and the window-pane was shattered. Simultaneously a flash of light and a deafening explosion took place in the room, scattering broadcast tiny bits of glass from the laboratory table, splashing chemicals, many of them dangerous, over everything. Kennedy hurried to the wreck of his paraphernalia. In an instant he held up a tiny bit of jagged metal. "An explosive bullet!" he exclaimed. "An attempt to destroy my evidence!" XXV ITCHING SALVE For once I rose with Kennedy. He preceded me to the laboratory after breakfast, however, leaving me to wait for Mackay. When the little district attorney arrived I noticed that he carried a package which looked as though it might contain a one-reel film can. "The negative we took from the cameras at Tarrytown," he explained. "Also a print from each roll, ready to run. I've been holding this as evidence. Mr. Kennedy wanted me to bring it with me to-day." "He's waiting for us at the laboratory," I remarked. "He'll straighten everything up in a hurry, won't he?" "Kennedy's the most high-handed individual I ever knew," I laughed, "if he sees a chance of getting his man." Then I became enthusiastic. "Often I've seen him gather a group of people in a room, perhaps without the faintest shred of legal right to do so, and there make the guilty person confess simply by marshaling the evidence, or maybe betray himself by some scientific device. It's wonderful, Mackay." "Do you think he plans something of that kind this morning?" I led the way to the door. "After what happened last night I know that Kennedy will resort to almost anything." The district attorney fingered the package under his arm. "He might get everyone in the projection room then, and make them watch the actual photographic record of Stella's death--the scene where she scratched herself--" "Let's hurry!" I interrupted. When we entered the laboratory we found Kennedy vigorously fanning a towel which he had hung up to dry. I recognized it as the one I had discovered in the studio washroom immediately following the first murder. "This will serve me better as bait than as evidence," he laughed. "I have impregnated it with a colorless chemical which will cling to the fibers and enable me to identify the most infinitesimal trace of it. We shall get up to the studio and start, well--I guess you could call it fishing for the guilty man." He fingered the folds, then jerked the towel down and flung it to me. "Here, Walter! It's dry enough. Now I want you to rub the contents of that tiny can of grease, open before you there, into the cloth." He hurried over to wash his hands. I spread the towel out on the table and began to work in the stuff indicated by Kennedy. There was no odor and it seemed like some patent ointment in color. At first I was puzzled. Then, absently, I touched the back of one hand with the greasy fingers of the other and immediately an itching set up so annoying that I had to abandon my task. Kennedy chuckled. "That's itching salve, Walter. The cuticle pads at your finger tips are too thick, but touch yourself anywhere else!--" He shrugged his shoulders. "You'd better use soap and water if you want any relief. Then you can start over again." At the basin I thought I grasped his little plot. "You're going to plant the towel," I asked, "so that the interested party will try to get hold of it?" Evidently he thought it unnecessary to reply to me. "Why couldn't you just put it somewhere without all the preparation," Mackay suggested, "and watch to see who came after it?" "Because our criminal's too clever," Kennedy rejoined. "Our only chance to get it stolen is to make it very plain that it is not being watched. Whoever steals it, however, possibly will reveal himself on account of the itching salve. In any case I expect to be able to trace the towel to the thief, no matter what efforts are made to destroy it." The towel was wrapped in a heavy bit of paper; then placed with a microscope and some other paraphernalia in a small battered traveling bag. Climbing into Mackay's little roadster, we soon were speeding toward the studio. "Will you be able to help me, to stay with Jameson and myself all day?" Kennedy asked the district attorney, after perhaps a mile of silence. "Surely! It's what I was hoping you'd allow me to do. I have no authority down here, though." "I understand. But the police, or an outsider, might allow some of my plans to become known." He paused a moment in thought. "The film you brought in with you consists of the scenes on the rolls of negative in use at the time of Miss Lamar's collapse. It may or may not include the action where she scratched herself. Now I want the scenes up to thirteen put together in proper order, first as photographed by one camera, then as caught by the other. I'll arrange for the services of a cutter, and for the delivery to me of any other negative or positive overlooked by us when we had the two boxes sealed and given into your custody at Tarrytown. Will you superintend the assembly of the scenes, so that you can be sure nothing is taken out or omitted?" "Of course! I want to do anything I can." Upon arrival at the studio we detected this time all the signs of a complete demoralization. The death of Werner, the fact that he had been stricken down during the taking of a scene and on the very stage, had served to bring the tragedy home to the people. More, it was a second murder in four days, apparently by the same hand as the first. A sense of dread, a nameless, intangible fear, had taken form and found its way under the big blackened glass roofs and around and through the corridors, into the dressing rooms, and back even to the manufacturing and purely technical departments. The gateman eyed us with undisguised uneasiness as we drove through the archway into the yard. In that inclosure there were only two cars--Manton's, and one we later learned belonged to Phelps. The sole human being to enter our range of vision was an office boy. He skirted the side of the building as though the menace of death were in the air, or likely to strike out of the very heavens without warning. We found Kauf in the large studio, obviously unhappy in the shoes of the unfortunate Werner. Probably from half-reasoned-out motives of efficiency in psychology the new director had made no attempt to resume work at once in the ill-fated banquet set, but had turned to the companion ballroom setting, since both had been prepared and made ready at the same time. Kennedy explained our presence so early in the morning very neatly, I thought. "I would appreciate it," he began, "if you could place a cutter at the disposal of Mr. Mackay. He has the scenes taken from the camera and sealed at the time of Miss Lamar's death. I would like to have any other film taken out there delivered to him and the whole joined in proper sequence. Then, Mr. Kauf, if you could arrange to have the same cutter take the film exposed yesterday when Mr. Werner--" "You think you might be able to see something, to discover something on the screen?" "Exactly!" Kauf beamed. "Mr. Manton gave me orders to assist you in every way I could, or to put any of my people at your disposal. More than that, Mr. Kennedy, he anticipated you. He thought you might want to look at the scenes taken yesterday and he rushed the laboratory and the printing room. We'll be able to fix you up very quickly." "Good!" Kennedy nodded to Mackay and the district attorney hurried off with Kauf. "Now, Walter!" he exclaimed, sobering. I picked up the traveling bag and together we strolled toward the ballroom set. There most of the players were gathered already--in make-up and evening clothes of a fancier sort even than those demanded for the banquet. I saw that Kennedy singled out Marilyn. "Good morning," she said, cheerfully, but with effort. It was obvious she had spent a nervous night. There were circles under her eyes ill concealed by the small quantity of cosmetic she used. Her hands, shifting constantly, displayed the loss of her usual poise. "You are out bright and early," she added. "We've stumbled into a very important clue," Kennedy told her, with a show of giving her his confidence. "In that bag in Walter's hand is one of the studio towels. It contains a hint of the poison used to kill Miss Lamar and--of utmost consequence--it has provided me with an infallible clue to the identity of the murderer himself--or herself." It seemed to me that Marilyn blanched. "Where--where did you find it?" she demanded, in a very awed voice. "In one of the studio washrooms." "It has been--it has been in the washroom ever since poor Stella's death?" "No, not that! Jameson discovered it the same day but"--the very slight pause was perceptible to me; Kennedy hated to lie--"I haven't realized its importance until just this morning." Enid Faye, seeing us from a distance, conquered her dislike of Marilyn sufficiently to join us. She was very erect and tense. Her eyes, wide and sober and searching, traveled from my face to Kennedy's and back. Then she dissembled, softening as she came close to me, laying a hand on my shoulder and allowing her skirt to brush my trousers. "Tell me, Jamie," she whispered, her warm breath thrilling me through and through. "Has the wonderful Craig Kennedy discovered something?" It was not sarcasm, but assumed playfulness, masking a throbbing curiosity. "I found a towel in one of the studio washrooms," I answered, "and Craig has demonstrated that it is a clue to the poison which killed Stella Lamar as well as to the person who did it." Enid gasped. Then she drew herself up and her eyes narrowed. Now she faced Kennedy. "How can the towel be a clue to the crime?" she protested. "Stella was--was murdered way out in Tarrytown! Mr. Jameson found the towel here!" Kennedy shrugged his shoulders. "I cannot tell you that--just yet." He paused deliberately. "You see," he lied. "I have yet to make my analysis." "But you know it's a clue to the--" "That towel"--he raised his voice, as though in elation--"that towel will lead me to the murderer--infallibly!" Merle Shirley had come up in time to hear most of the colloquy between Enid and Kennedy. At the last he flushed, clenching his fists. "If you can prove who the murderer is, Mr. Kennedy," he exploded, "why don't you apprehend him before some one else meets the fate of Werner?" "I can do nothing until I return to my laboratory this afternoon. I will not know the identity of the guilty person until I complete a chemical analysis." One by one the various people possibly concerned in the two crimes joined the group. This morning all the faces were serious; most of them showed the marks of sleeplessness following the second murder. Kennedy walked away, but I saw that Jack Gordon hastened to question both the girls, ignoring their evident dislike for him. Among the others I recognized Watkins, the camera man, and his associate. Lawrence Millard came in and hastened to the side of Enid. As he drew her away to ask the cause of the gathering I wondered at his early presence. The scenario writer was typical of them all. The strange and unusual nature of the crimes, the evident relationship between them, had drawn the employees of Manton Pictures to the studio as a crowd of baseball fans collects before a public bulletin board. Not one of them but was afraid of missing some development in the case. In no instance could the interest of a particular individual be taken as an indication of guilt. Phelps entered the studio from the door to the dressing rooms. Disdaining to join the other group, he approached us to ask the cause for the excitement. Kennedy explained, patiently, and I saw that Phelps looked at the black bag uneasily. "I hope the guilty party is not a member of the company," he muttered. "Why?" Kennedy's mouth tightened. The financier grew red. "Because this picture has been crippled enough. First a new star; now a new director--if it wasn't so preposterous I'd believe that it was all part of a deliberate--" He stopped as if realizing suddenly the inadvisability of vague accusations. "Don't you want justice done?" Kennedy inquired. "Of course!" Phelps tugged at his collar uncomfortably. "Of course, Mr. Kennedy." Then he turned and hurried away, out of the studio. Gordon and Millard detached themselves from the others, coming over. "In which washroom was the towel found, Mr. Kennedy?" Gordon put the question as though he felt himself specially delegated to obtain this information. I wondered how Kennedy would evade a direct answer. To my surprise he made no attempt at concealment. "The one on the second floor of the office building." Millard laughed, facing Gordon. "That puts it on myself--or the big boss!" It struck me that the leading man was uneasy as he hurried back to the others. Millard, still smiling, turned to say something to us, but we were joined by Manton, entering from the other end of the big inclosure. "Good morning," the promoter exclaimed, somewhat breathless. "I just learned you were here. Is--is there some new development. Is there something I can do?" "I see you are not allowing anything to interfere with the making of the picture," Kennedy remarked. "All the people seem to be here bright and early." A shadow crept into Manton's face. "It seems almost as cold-blooded as--as war," he admitted. "But I can't help myself, Mr. Kennedy. The company has no money and if we don't meet this release we're busted." All at once he lowered his voice eagerly. "Tell me, have you discovered something? Is there some clue to the guilty man?" "He's found a towel," Millard put in, an expression of half amusement on his face as he faced the promoter. "In some way it's a clue to the identity of the murderer, an infallible clue, he says. He found it in the washroom by our offices. Since Werner is dead, that points the finger of suspicion at you or me." Manton's jaw dropped. His expression became almost ludicrous, as if the thought that he could possibly be suspected himself was new to him. Millard's eyes sobered a bit at his superior's confusion. "There's a door from the dressing rooms," Kennedy suggested. "Any of the actors or actresses could have used the place." "Of course!" Manton grasped at the straw. "I had forgotten. There have been complaints to me about the players using that room." "I have the towel with me, wrapped up in a paper in this grip," Kennedy went on. "It's so very valuable as a bit of evidence--I wonder if I could borrow a locker so as to keep it under lock and key until we're ready to return to the laboratory?" "Sure! Of course!" Manton glanced about and saw the little knot of people still gathered in the set. "Millard! Go over and tell Kauf to get busy. He's losing time." Then he turned to us again. "Come on, Mr. Kennedy, we have some steel lockers out by the property room." As we started across the floor I could see that Kennedy was framing a question with great care. "Do you ever use snakes in films, Mr. Manton?" he asked. "Why, no!" The promoter stopped in his surprise. "That is, not if we ever can help it. The censorship won't pass anything with snakes." "You have used them, though?" "Yes. Once we made a short-length special subject, nothing but snakes." Manton became enthusiastic. "It was a wonder, too; a pet film of mine. We made it with the direct co-operation and supervision of the greatest authority on poisonous snakes in the country, Doctor Nagoya of Castleton Institute." XXVI A CIGARETTE CASE Kennedy's face betrayed only a remote interest. "Have you any copies of that particular film?" "Just the negative, I believe." "Could I have that for a few days?" "Of course!" Manton seemed to wish to give us every possible amount of co-operation; yet this request puzzled him. "Would you care to go down to the negative vaults with me?" Kennedy nodded. First we stopped in a lengthy corridor in the rear building, where there were no great signs of life. Through a door I could see a long room filled with ornaments, pictures, furniture, rugs, and all the vast freak collections of a property room. Along the side of the hallway itself was a line of steel lockers of recent design. Manton called out to an employee and he appeared after a long wait and unlocked one of them. At Kennedy's direction I put the traveling bag in the lower compartment, pocketing the key. Then we retraced our steps to broad steel stairs leading up and down. We descended to the basement and found ourselves in a high-ceilinged space immaculately clean and used generally for storage purposes. "The film vaults," Manton explained, "are at the corner of the west wing. They have to be ventilated specially, on account of the high inflammability of the celluloid composition. Since the greatest fire risk, otherwise, is the laboratory and printing departments, and next to that the studios themselves with the scenery, the heat of the lights, the wires, etc., we have located them in the most distant corner of the quadrangle. The negative, you see, represents our actual invested capital to a considerable extent. The prints wear out and frequently large sections are destroyed and have to be reprinted. Then sometimes we can reissue old subjects. All in all we guard the negative with the care a bank would give actual funds in its vaults." In our many visits to the Manton studios I had been struck by the scrupulous cleanliness of every part of the place. The impression of orderliness came back to me with redoubled force as we made our way around in the basement. Nothing seemed out of its proper position, although a vast amount of various material for picture making was stored here. We passed two projection rooms, one a miniature theater with quite a bit of comfort, the other small and bare for the use of directors and cutters. Finally we saw the vaults ahead of us. The walls were concrete, matching the actual walls of the basement. There were two entrances and the doors were double, of heavy steel, arranged so that an air space would give protection in case of fire. At a roll-top desk, arranged for the use of the clerk in charge of the negatives and prints, was a young boy. "Where's Wagnalls?" demanded Manton. "He went out, sir," the boy replied, respectfully enough. "Said he would be right back and for me to watch and not to let anything get out." The promoter led the way into the first room. Here on all four sides and in several rows down the center, like the racks in a public library, were shelves supporting stacks of square thin metal boxes or trays with handles and tightly fitting covers. Cards were secured to the front of each, by clamps, giving the name of the picture and the number under which the film was filed. I was surprised because I expected to find everything kept in ordinary round film cans. "These are the negatives," Manton explained. He pulled out a box at random, opening it. "The negative is not all spliced together, the same length as the reels of positive, because the printing machines are equipped to take two-hundred-foot pieces at a time, or approximate fifths of a reel, the size of a roll of raw positive film stock. Then whenever there is a change in color, as from amber daylight to blue tint for night, the negative is broken because pieces of different coloring have to go through different baths, and that also determines the size of the rolls. The prints, or positives, in the other vaults, are in reel lengths and so are kept in the round boxes in which they are shipped." Kennedy glanced about curiously. "The negative of that snake picture is here, you said?" Manton went to a little desk where there was a card index. Thumbing through the records, he found the number and led us to the proper place in the rack. In the box were only two rolls of negative, both were large. "This was a split reel," the promoter began. "It was approximately four hundred feet and we used it to fill out a short comedy, a release we had years ago, a reel the first part of which was educational and the last two-thirds or so a roaring slap-stick. We never made money on it. "But this stuff was mighty good, Mr. Kennedy. We practically wrote a scenario for those reptiles. Doctor Nagoya was down himself and for the better part of a day it wasn't possible to get a woman in the studio, for fear a rattler or something might get loose." "Were there rattlers in the film?" "Altogether, I think. The little Jap was interesting, too. Between scenes he told us all about the reptiles, and how their poison--" Manton checked himself, confused. Was it because the thought of poison reminded him of the two deaths so close to him, or was it from some more potent twinge of conscience? "You'll see it all in the film," he finished, lamely. "I may keep these for a little bit?" Kennedy asked. "Of course! I can have the two rolls printed and developed and dry sometime this afternoon, if you wish." "No, this will do very well." Kennedy slipped a roll in each pocket, straining the cloth to get them in. Manton opened a book on the little table, making an entry of the delivery of the rolls and adding his own initials. "I have to be very careful to avoid the loss of negative," he told us. "Nothing can be taken out of here except on my own personal order." I thought that Manton was very frank and accommodating. Surely he had made no effort to conceal his knowledge of this film made with Doctor Nagoya, and he had even mentioned the poison of the rattlesnakes. Though it had confused him for a brief moment, that had not struck me as a very decisive indication of guilty knowledge. After all, no one knew of the use of crotalin to kill Stella Lamar except the murderer himself, and Kennedy and those of us in his confidence. The murderer might not guess that Kennedy had identified the venom. Yet if Manton were that man he had covered his feelings wonderfully in telling us about the film. My thoughts strayed to the towel upstairs. Had an attempt been made yet to steal it from the locker? It seemed to me that we were losing too much time down here if we hoped to notice anyone with itching hands. I realized that Kennedy had been very clever in including all our suspects in hearing at the time he revealed the importance of the clue. Of the original nine listed by Mackay, Werner was dead and Mrs. Manton had never entered the case. Enid we had assumed to be the mysterious woman in Millard's divorce, however, and the other six had all been upon the floor in contact with Kennedy. First there was Marilyn, the woman. Then the five men in order had displayed a lively interest in the towel--Shirley, Gordon, Millard, Phelps, and Manton. Kennedy's voice roused me from my reverie. "Does this door lead through to the other vaults, Mr. Manton?" "Yes." The promoter straightened, after replacing the records of the negative. "I designed this system of storage myself and superintended every detail of construction. It is--" He checked himself with an exclamation, noticing that the door was open. With a flush of anger he slammed it shut. "I should think the connecting doors would be kept shut all the time," Kennedy remarked. "In case of fire only one compartment would be a loss." "That's the idea exactly! That's why I was on the point of swearing. The boys down here are getting lax and I'm going to make trouble." Manton turned back and called to the boy outside. "Where did you say Wagnalls went?" "I don't know, sir! Sometimes he goes across to McCann's for a cup of coffee, or maybe he went up to the printing department." Manton faced us once more. "If you'll excuse me just a moment I'm going to see who's responsible for this. Why," he sputtered, "if you hadn't called me around the rack I wouldn't have noticed that the door was open and then, if there had been a fire--I--I'll be right back!" As Manton stormed off Kennedy smiled slightly, then nodded for me to follow. We passed through into the rooms for positive storage. These in turn had fireproof connecting doors, all of which were open. In each case Kennedy closed them. Eventually we emerged into the main part of the basement through the farther vault door. Nothing of a suspicious nature had caught our attention. I guessed that Kennedy simply had wished to cover the carelessness of the vault man in leaving the inner doors wide open. At the entrance which had first admitted us to the negative room, however, Kennedy stooped suddenly. At the very moment he bent forward I caught the glint of something bright behind the heavy steel door, and in the shadow so that it had escaped us before. As he rose I leaned over. It was a cigarette case, a very handsome one with large initials engraved with deep skillful flourish. "Who is 'J. G.'?" Kennedy asked. I felt a quiver of excitement. "Jack Gordon, the leading man." "What's an actor doing down in the film vaults?" he muttered. Slipping the case into his pocket, he glanced about on the floor and something just within the negative room caught his eye. Once more he bent down. With a speculative expression he picked up the cork-tipped stub of a cigarette. At this instant Manton returned, breathing hard as though his pursuit of the missing Wagnalls had been very determined. The butt in Kennedy's fingers attracted his attention at once. "Did--did you find that here?" he demanded. Kennedy pointed. "Right there on the floor." "The devil!" Manton flushed red. "This is no place to smoke. By--by all the wives of Goodwin and all the stars of Griffith I'm going to start firing a few people!" he sputtered. "Here, sonny!" He jumped at the boy, frightening him. "Close all these doors and turn the combinations. Tell Wagnalls if he opens them before he sees me I'll commit battery on his nose." Kennedy continued to hold the stub, and as Manton preceded us up the stairs he hung back, comparing it with the few cigarettes left in the case. Unquestionably they were of the same brand. On the studio floor Mackay was waiting for us. Under his arm was a reel of film in a can. He clutched it almost fondly. "All ready!" he remarked, to Kennedy. Kennedy's face was unrevealing as he faced Manton. "This bit of film is valuable evidence also. I think perhaps it would be safer in that locker." "Anything at all we can do to help," stated Manton, promptly. "Shall I show you the way again?" I produced the key, handing it to Kennedy as the four of us arrived in the corridor by the property room. Kennedy slipped the bit of metal into the lock; then simulated surprise very well indeed. "The lock is broken!" he exclaimed. "Some one has been here." Apparently the traveling bag had been undisturbed as we took it out. Nevertheless, the paper containing the towel was gone. "This is no joke, Mr. Kennedy," protested Manton, in indignation. "Where can I hire about a dozen good men to hang around and watch--and--and help you get to the bottom of this?" Mackay, without releasing his grasp of the film, had been inspecting the broken lock. "Look at the way this was done!" he murmured, almost in admiration. "This wasn't the work of any roughneck. It--it was a dainty job!" XXVII THE FILM FIRE The bag lay open at my feet. The microscope and other paraphernalia brought by Kennedy were untouched. Taking the film from Mackay and placing the can in with the other things, Kennedy snapped the catch and turned to me as he straightened. "I think our evidence is safest in plain sight, Walter. We'll carry it about with us." Lloyd Manton seemed to be a genuinely unhappy individual. After some moments he excused himself, nervously anxious about the turn of affairs at the studio. Immediately I faced Kennedy and Mackay. "Manton's the only one who knew just where we put the bag," I remarked. "When he left us in the basement he had plenty of time to run up and steal the towel and return." "How about the itching salve?" "In his hurry he might have left the towel in the paper, intending to destroy it later." Kennedy frowned. "That's possible, Walter. I had not thought of that. Still"--he brightened--"I'm counting on human nature. I don't believe anyone guilty of the crime could have that towel in his possession, after the hints I have thrown out, without examining it so as to see what telltale mark or stain would be apt to betray his identity." "You can see that Manton's the logical man?" "It would be easy for anyone else to follow and observe us." "Then--?" "First of all we must keep an eye out for any person showing signs of the itching concoction. We must observe anyone with noticeably clean hands. Principally, however, another thing worries me." "What's that, Mr. Kennedy?" asked Mackay. "Walter and I found a cigarette case belonging to Jack Gordon in the basement; also a butt smoked three-quarters of the way down and left directly in the negative room. The fire doors between the different film vaults, which are arranged like the safety compartments in a ship, were all open. I want to know why Gordon was down there and--well, I seem to sense something wrong." "Good heavens! Craig," I interposed. "You don't attach any importance to the fact that those doors were open!" "Walter, in a case of real mystery the slightest derangement of matters of ordinary routine is a cause for suspicion." I had no answer, and as we re-entered the studio I devoted my attention to the various people we had tabulated as possible suspects, noticing that Kennedy and Mackay did likewise. Jack Gordon was in the ballroom scene in make-up. Kauf still was concerned with technical details of the set and lighting, and, although the cameras were set up, they were not in proper place, nor was either camera man in evidence. With Gordon was Enid. From a distance they seemed to be engaged in an argument of real magnitude. There was no mistaking the dislike on the part of each for the other. Marilyn was the most uneasy of all of the principals. She was pacing up and down, glancing about in frank distress of mind. I looked at her hands and saw that she had crushed a tube of grease paint in her nervousness. Not only her fingers were soiled, but there were streaks on her arms where she had smeared herself unconsciously. As we watched she left the studio, hurrying out the door without a backward glance. Marilyn, at least, showed no indications of the salve, nor of painfully recent acquaintance with water. Both Manton and Phelps were in evidence, decidedly so, I imagined, from, the viewpoint of poor Kauf. Manton, at the heels of his new director, was doing all he could to help. Phelps, following Manton about, seemed to be urging haste upon the promoter. The result was far from advantageous to picture making; it was concentrated distraction. Millard was poring over the manuscript, perched upon a chair the wrong way so that its back would serve as a desk, engaged busily in making changes here and there in the pages with a pencil. Like any author, it was never too late for minor improvements and suggestions. I don't doubt but that if Manton had permitted it, Millard would have been quite apt to interrupt a scene in the taking in order to add some little touch occurring to him as his action sprang to life in the interpretation of players and director. At any rate, his hands seemed more clean than those of either Manton or Phelps, proving nothing because he was at a task not so apt to bring him into contact with dirt. "Shirley is missing," observed the district attorney, in an undertone. Kennedy faced me. "Give the bag to Mackay, Walter. While he keeps an eye on the people up here we'll pay a visit to Shirley's dressing room, and after that go down to the basement again. I can't account for it--intuition, perhaps--but I'm sure something's wrong." The heavy man's dressing room, pointed out to us by some employee passing through the hall, was empty. I led the way into Marilyn's quarters, but again no one was about. In each case Kennedy made a quick visual search for the towel, without result. We did not dare linger and run the risk of giving away our trick; then, too, Kennedy was nervously anxious to look through the basement once more. "I don't understand your suspicion of the state of affairs in the film vaults," I confessed. "Why should Jack Gordon, the leading man, be down there?" he countered. "That--that really is a cause for suspicion, isn't it." "Now, Walter, think a bit!" We were crossing the yard, and so not apt to be overheard. "Granting that Gordon actually had been down there, why should the fact concern us? Manton explained that no negative or positive can be given out except upon order. There is nothing down there but film and so no other errand to bring the leading man to the vault except to get some scenes or pieces showing his own work, and that isn't likely." "Unless," I interrupted, "Gordon is the guilty man and wanted to get the snake film before we did." "How could that be? When we asked Manton about the Doctor Nagoya subject we went right down with him and procured it. I doubt anyone could have overheard us as we talked about it, in any case." "Remember, Craig, we went to the locker first and it was some little time before that fellow came out to unlock it and give us the key. And when you questioned Manton we were passing right by all of them. Any one could have heard the mention of the snake film." Kennedy frowned. "I believe you're right, Walter. Or it is possible that the guilty person believed that the scenes taken out at Tarrytown, or those taken when Werner died, revealed something and so would have to be stolen or destroyed, and that they were kept in the vault. It is even possible"--a gleam came into Kennedy's eyes--"it is even possible that the mind smart enough to reason out the damaging nature of the chemical analyses I was making, and clever enough to utilize an explosive bullet in an effort to destroy the fruits of my work, would also have the foresight to anticipate me and to realize that I might guess the existence of a film showing snakes and suggesting the use of venom." "It's damning to Gordon, all right," I said. "On the contrary, Walter." Kennedy lowered his voice as we entered the building across the quadrangle and descended stairs leading directly into the basement. "We have mentioned over and over again the cleverness of our unknown criminal. That man, or woman, never would drop a cigarette case with his or her initials and leave without it, nor smoke a cigarette in a place he, or she, was not supposed to be." "What then?" "It's a plant; a deliberate plant to throw suspicion upon Gordon." "Why upon Gordon?" "I don't know that, unless because Gordon is supposed to have the best possible motive for killing Miss Lamar--his money troubles--and so becomes the logical man to throw the guilt upon." "As a matter of fact, Craig, why should the finding of that cigarette case be a cause for suspicion at all? That's what I didn't understand before." "Ordinarily it wouldn't be. But those open inner doors, the absence of the man in charge--isn't it possible that we interrupted an attempt not only to search for the particular damaging pieces of film, but perhaps to destroy the whole? If some one acted between the time I asked Manton about the snake film and the moment we arrived in the basement to get it, that some one had to move very fast." "In which case it might have been Gordon, after all. The cigarette stub may have been thrown in lighted to start a fire. He may not have had time to pick up the case, not knowing just where he dropped it." Kennedy shrugged his shoulders. "It all shows the futility of trying to arrive at a conclusion without definite facts. That is where science is superior to deduction." "It's all a maze to me just now," I agreed. We made our way to the vaults in silence, and, to our surprise, found that they were closed and that even the boy was gone now. The cellar, as a whole, probably for the purpose of fire protection on a larger scale, was divided into sections corresponding to the units of the buildings above, and this time I noticed that the door through which we had arrived before was closed also. Had Manton taken fright in earnest at the possibility of fire, or had he given his employees a genuine scare? We retraced our steps to the yard, and there the alert eye of Kennedy detected a slinking figure just as a man darted into the protection of a doorway. It was Shirley. Had he been watching us? Was he connected in some way with the vague mystery Kennedy seemed to sense in connection with the basement and the film vaults? Kennedy led the way to the entrance where Shirley had disappeared. Here there was no sign of him; only steps leading up and down and the open door to a huge developing room. Returning to the yard, we caught a gesture from the chauffeur of a car standing near by and recognized McGroarty, the driver who had found the ampulla a few days previously. "Excuse me, Mr. Kennedy," he apologized, as we approached. "I should have come to you instead of making you two walk over to me, but it's less suspicious this way." "What do you mean?" "You recognize me, McGroarty, the chauffeur as found the little bottle?" Kennedy nodded. "Well, I says to myself I ought to tell you, but I don't like to because it might be nothing, you know!" "It might prove very valuable, McGroarty." Kennedy wanted to encourage him. "Well, I've been sitting here for an hour, I guess. One of the other directors is going out to-day and his people are late and so here I am. Well, I don't like the way the heavy man Mr. Werner had--" "Shirley? Merle Shirley?" I spoke up. "That's him! Well, he's been, hanging and snooping around that building over there, where you just saw him, for twenty minutes or more. I guess he's gone in and out of that basement a dozen times. I says to myself, maybe he's up to something. You know how it is?" Kennedy glanced at me significantly. Then he extended his hand to the chauffeur. "Again I thank you, McGroarty. As I said before, I won't forget you." "Now what?" I asked, as we drew away. "Shirley's dressing room, and the studio floor and Mackay." As we rather expected, the heavy man's quarters were deserted. I thought that Kennedy would stop now to make a careful search, but he seemed anxious to compare notes with the district attorney. "Nothing here," reported Mackay. "Shirley?" "Hasn't been a sign of him." I looked about the moment we arrived under the big glass roof. "Marilyn Loring?" I inquired. "She's been missing, too!" All at once Mackay grinned broadly. "You know, either there's no efficiency in making moving pictures at all, or these people have all gone more or less out of their heads as the result of the two tragedies. Look!" He pointed. "When you left me Phelps and Manton were stepping on each other's toes, trying to help that new director and about half driving him crazy; and now Millard seems to have figured out some new way of handling the action and he's over in the thick of it. It's worse than Bedlam, and better than a Chaplin comedy." I was compelled to smile, although I knew that this was not uncommon in picture studios. Manton, Phelps, Millard, and Kauf were in the center of the group, all talking at once. Clustered about I saw Enid and Gordon, both camera men, and a miniature mob of extra people. But as I looked little Kauf seemed to come to the end of his patience. In an instant or two he demonstrated real generalship. Shutting up Manton and the banker and Millard with a grin, but with sharp words and a quick gesture which showed that he meant it, he called to the others gathered about, clearing the set of all but Enid and Gordon. He sent the camera men to their places; then confronted Phelps and Manton and the scenario writer once more. We could not hear his words, but could see that he was asserting himself, was forcing a decision so that he could proceed with his work. This seemed uninteresting to me. I remembered my success in my visit to Werner's apartment, when I had essayed the role of detective. "Listen, Kennedy!" I suggested. "Suppose I go out by myself and see if I can locate Shirley or Marilyn. Everyone else is right here where you can--" At that instant a deafening explosion shook the studio and every building about the quadrangle, the sound echoing and re-echoing with the sharpness of a terrific thunderclap. Mixed with the reverberations, which were intensified by the high arch of the studio roof, were the screams of women and the frightened calls of men. Following immediately upon the first roar were the muffled sounds of additional explosions, persisting for a matter of ten to fifteen seconds. With every detonation the floor beneath our feet trembled and rocked. Several flats of scenery stacked against a wall at our rear toppled forward and struck the floor with a resounding whack, not unlike some gigantic slap-stick. One entire side of the banquet set, luckily unoccupied, fell inward and I caught the sound as the dainty gold chairs and fragile tables snapped and were crushed as so much kindling wood. Then--a fitting climax of destruction, withheld until this moment--there followed the terrifying snap of steel from above. An entire section of roof literally was popped from place, the result of false stresses in the beams created by the explosion. Upon the heads of the unlucky group in the center of the ballroom set came a perfect hailstorm of broken and shattered bits of heavy ground glass. For an instant, an exceedingly brief instant, there was the illusion of silence. The next moment the factory siren rose to a shrill shriek, with a full head of steam behind it--the fire call! Kennedy dashed over to the scene where those beneath the shower of glass lay, dazed and uncertain of the extent of their own injuries. "Where are the first-aid kits?" he shouted. "Bring cotton and bandages, and--and telephone for a doctor, an ambulance!" It seemed to me that Kennedy had never been so excited. Mackay and I, at his heels, and some of the others, unhurt, hurriedly helped the various victims to their feet. Then we realized that by some miracle, some freak of fate, no one had been hurt seriously. Already a property boy was at Kennedy's side with a huge box marked prominently with the red cross. Inside was everything necessary and Kennedy started to bind up the wounds with all the skill of a professional physician. "Mackay," he whispered, "hurry and get me some envelopes, or some sheets of paper, anything--quick!" And to me, before I could grasp the reason for that puzzling request: "Don't let anyone slip away, Walter. No matter what happens, I must bind up these wounds myself." A few moments later I understood what Kennedy was up to. As he finished with each victim he took some bit of cotton or gauze with which he had wiped their cuts, enough blood to serve him in chemical analysis, and handed it to Mackay. The district attorney, very unobtrusively, slipped each sample into a separate envelope, sealing it, and marking it with a hieroglyph which he would be able to identify later. In this fashion Kennedy secured blood smears of Manton and Phelps, Millard and Kauf and Enid, Gordon, the two camera men, and a scene shifter. I smiled to myself. Meanwhile a bitter, acrid odor penetrated through the windows and to every part of the structure, the odor of burning film, an odor one never forgets to fear. All those uninjured in the explosions had rushed out to see the fire, or else to escape from any further danger, the moment they recovered their wits. Manton, only cut at the wrist, and impatient as Kennedy cleaned, dusted, and bound the wound, was the first to receive attention. "The vaults!" he called, to the men who seemed disposed to linger about. "For God's sake get busy!" The next instant he was gone himself. Enid was cut on the head. Tears streamed from her eyes as she clung to Kennedy's coat, trembling. "Will it make a scar?" she sobbed. "Will I be unable to act before the camera any more?" He reassured her. In the case of Millard, who had several bad scalp wounds, he advised a trip to a doctor, but the scenario writer laughed. Phelps was yellow. It seemed to me that he whimpered a bit. Gordon was disposed to swear cheerfully, although a point of glass had penetrated deep in his shoulder and another piece had gashed him across the forehead. Finally Kennedy was through. He packed the little envelopes in the bag, still in the possession of Mackay, and added the two rolls of film from his pocket. Then, for the first time, he locked it. As he straightened, his eyes narrowed. "Now for Shirley," he muttered. "And Marilyn," I added. XXVIII THE PHOSPHORUS BOMB We rushed out into the courtyard, Kennedy in the lead, Mackay trailing with the bag. Here there were dense clouds of fine white suffocating smoke mixed with steam, and signs of the utmost confusion on every hand. Because Manton, fortunately, had trained the studio staff through frequent fire drills, there was a semblance of order among the men actually engaged in fighting the spread of the blaze. Any attempt to extinguish the conflagration in the vault itself was hopeless, however, and so the workers contented themselves with pouring water into the basement on either side, to keep the building and perhaps the other vaults cool, and with maintaining a constant stream of chemical mixture from a special apparatus down the ventilating system into and upon the smoldering film. The studio fire equipment seemed to be very complete. There was water at high pressure from a tank elevated some twenty to thirty feet above the uppermost roof of the quadrangle. In addition Manton had invested in the chemical engine and also in sand carts, because water aids rather than retards the combustion of film itself. I noticed that the promoter was in direct charge of the fire-fighters, and that he moved about with a zeal and a recklessness which ended for once and all in my mind the suspicion that Phelps might be correct and that Manton sought to wreck this company for the sake of Fortune Features. In an amazingly quick space of time the thing was over. When the city apparatus arrived, after a run of nearly three miles, there was nothing for them to do. The chief sought out Manton, to accompany him upon an inspection of the damage and to make sure that the fire was out. The promoter first beckoned to Kennedy. "This is unquestionably of incendiary origin," he explained to the chief. "I want Mr. Kennedy to see everything before it is disturbed, so that no clue may be lost or destroyed." The fire officer brightened. "Craig Kennedy?" he inquired. "Gee! there must be some connection between the blaze and the murder of Stella Lamar and her director. I've been reading about it every day in the papers." "Mr. Jameson of the Star," Kennedy said, presenting me. We found we could not enter the basement immediately adjoining the vaults--that is, directly from the courtyard--because it seemed advisable to keep a stream of water playing down the steps, and a resulting cloud of steam blocked us. Manton explained that we could get through from the next cellar if it was not too hot, and so we hurried toward another entrance. Mackay, who had remained behind to protect the bag from the heat, joined us there. "I've put the bag in charge of that chauffeur, McGroarty, and armed him with my automatic," he explained. He paused to wipe his eyes. The fumes from the film had distressed all of us. "Shirley and Marilyn Loring are both missing still," he added. "I've been asking everyone about them. No one has seen them." The fire chief looked up. "Everyone is out? You are sure everybody is safe?" "I had Wagnalls at my elbow with a hose," Manton replied. "I saw the boy around, also. No one else had any business down there and the vaults were closed and the cellar shut off." The door leading from the adjoining basement was hot yet, but not so that we were unable to handle it. However, the catch had stuck and it took considerable effort to force it in. As we did so a cloud of acrid vapor and steam drove us back. Then Kennedy seemed to detect something in the slowly clearing atmosphere. He rushed ahead without hesitation. The fire chief followed. In another instant I was able to see also. The form of a woman, dimly outlined in the vapor, struggled to lift the prone figure of a man. After one effort she collapsed upon him. I dashed forward, as did Mackay and Manton. Two of them carried the girl out to the air; the other three of us brought her unconscious companion. It was Marilyn and Shirley. The little actress was revived easily, but Shirley required the combined efforts of Kennedy and the chief, and it was evident that he had escaped death from suffocation only by the narrowest of margins. How either had survived seemed a mystery. Their clothes were wet, their faces and hands blackened, eyebrows and lashes scorched by the heat. But for the water poured into the basement neither would have been alive. They had been prisoners during the entire conflagration, the burning vault holding them at one end of the basement, the door in the partition resisting their efforts to open it. "Thank heaven he's alive!" were Marilyn's first words. "How did you get in the cellar?" Kennedy spoke sternly. "I thought he might be there." Now that the reaction was setting in, the girl was faint and she controlled herself with difficulty. "I was looking for him and as soon as I heard the first explosion I ran down the steps into the film-vault entrance--I was right near there--and I found him, stunned. I started to lift him, but there were other explosions almost before I got to his side. The flames shot out through the cracks in the vault door and I--I couldn't drag him to the steps; I had to pull him back where you found us." She began to tremble. "It--it was terrible!" "Was there anyone else about, anyone but Mr. Shirley?" "No. I--I remember I wondered about the vault man." "What was Mr. Shirley down there for, Miss Loring?" "He"--she hesitated--"he said he had seen some one hanging around and--and he didn't want to report anything until he was sure. He--he thought he could accomplish more by himself, although I told him he was--was wrong." "Whom did he see hanging around?" "He wouldn't tell me." Shirley was too weak to question and the girl too unstrung to stand further interrogation. In response to Manton's call several people came up and willingly helped the two toward the comfort of their dressing rooms. At the fire chief's suggestion the stream of water into the basement was cut off. Manton led the way, choking, eyes watering, to the front of the vaults. Feverishly he felt the steel doors and the walls. There was no mistaking the conclusion. The negative vault was hot, the others cold. "The devil!" Manton exclaimed. A deep poignancy in his voice made the expression childishly inadequate. "Why couldn't it have been the prints!" Suddenly he began to sob. "That's the finish. Not one of our subjects can ever be worked again. It's a loss of half a million dollars." "If you have positives," Kennedy asked, "can't you make new negatives?" "Dupes?" Manton looked up in scorn. "Did you ever see a print from a dupe negative? It's terrible. Looks like some one left it out in the wet overnight." "How about the 'Black Terror'?" I inquired. "All of that's in the safe in the printing room; that and the two current five reelers of the other companies. We won't lose our releases, but"--again there was a catch in his voice--"we could have cleared thousands and thousands of dollars on reissues. All--all of Stella's negative is gone, too!" To my amazement he began to cry, without attempt at concealment. It was something new to me in the way of moving-picture temperament. "First they kill her and now--now they destroy the photographic record which would have let her live for those who loved her. The"--his voice trailed away to the merest whisper as he seemed to collapse against the hot smoked wall--"the devil!" The fire chief took charge of the job of breaking into the vault. First Wagnalls attempted to open the combination of the farther door, but the heat had put the tumblers out of commission. Returning to the entrance of the negative vault itself, the thin steel, manufactured for fire rather than burglar protection, was punctured and the bolts driven back. A cloud of noxious fumes greeted the workers and delayed them, but they persisted. Finally the door fell out with a crash and men were set to fanning fresh air into the interior while a piece of chemical apparatus was held in readiness for any further outbreak of the conflagration. Manton regained control of himself in time to be one of the first to enter. Mackay held back, but the fire chief, the promoter, Kennedy, and myself fashioned impromptu gasmasks of wet handkerchiefs and braved the hot atmosphere inside the room. The damage was irremediable. The steel frames of the racks, the cheaper metal of the boxes, the residue of the burning film, all constituted a hideous, shapeless mass clinging against the sides and in the corners and about the floor. Only one section of the room retained the slightest suggestion of its original condition. The little table and the boxes of negative records, the edges of the racks which had stood at either side, showed something of their former shape and purpose. This was directly beneath the ventilating opening. Here the chemical mixture pumped in to extinguish the fire had preserved them to that extent. All at once Kennedy nudged the fire chief. "Put out your torch!" he directed, sharply. In the darkness there slowly appeared here and there on the walls a ghostly bluish glow persisting in spite of the coating of soot on everything. Kennedy's keen eye had caught the hint of it while the electric torch had been flashed into some corner and away for a moment. "Radium!" I exclaimed, entirely without thought. Kennedy laughed. "Hardly! But it is phosphorus, without question." "What do you make of that?" The fire chief was curious. "Let's get out!" was Kennedy's reply. Indeed, it was almost impossible for us to keep our eyes open, because of the smarting, and, more, the odor was nauseating. A guard was posted and in the courtyard, disregarding the curious crowd about, Kennedy asked for Wagnalls and began to question him. "When did you close the vaults?" "About two hours before the fire. Mr. Manton sent for me." "Was there anything suspicious at that time?" "No, sir! I went through each room myself and fixed the doors. That's why the fire was confined to the negatives." "Have you any idea why the doors were open when we went through?" "No, sir! I left them shut and the boy I put there while I went over to McCann's said no one was near. He"--Wagnalls hesitated. "Once he went to sleep when I left him there. Perhaps he dozed off again." "Why did you leave? Why go over to McCann's in business hours?" "We'd worked until after midnight the night before. I had to open up early and so I figured I'd have my breakfast in the usual morning slack time--when nothing's doing." "I see!" Kennedy studied the ground for several moments. "Do you suppose anyone could have left a package in there--a bomb, in other words?" Wagnalls's eyes widened, but he shook his head. "I'd notice it, sir! If I do say it, I'm neat. I generally notice if a can has been touched. They don't often fool me." "Well, has any regular stuff been brought to you to put away; anything which might have hidden an explosive?" Again Wagnalls shook his head. "I put nothing away or give nothing out except on written order from Mr. Manton. Anything coming in is negative and it's in rolls, and I rehandle them because they're put away in the flat boxes. I'd know in a minute if a roll was phony." "You're sure nothing special--" "Holy Jehoshaphat!" interrupted Wagnalls. "I'd forgotten!" He faced Manton. "Remember that can of undeveloped stuff, a two-hundred roll?" He turned to Kennedy, explaining. "When negative's undeveloped we keep it in taped cans. Take off the tape and you spoil it--the light, you know. Mr. Manton sent down this can with a regular order, marking on it that some one had to come to watch it being developed--in about a week. Of course I didn't open the can or look in it. I put it up on top of a rack." "When was this?" "About four days ago--the day Miss Lamar was killed." The expression on Manton's face was ghastly. "I didn't send down any can to you, Wagnalls," he insisted. "It was your writing, sir!" Kennedy rose. "What did you do with orders like that, such as the one you claim came with the can of undeveloped negative?" "Put them on the spindle on that table in the vault." "Wet your handkerchief and come show me." When they returned Kennedy had the spindle in his hand, the charred papers still in place. This was one of the items preserved in part by the chemical spray through the ventilating opening above. "Can you point out which one it is?" Kennedy asked. "Let's see!" Wagnalls scratched his head. "Next to the top," he replied, in a moment. "Miss Lamar's death upset everything. Only one order came down after that." With extreme care Kennedy took his knife and lifted the ashy flakes of the top order. "Get me some collodion, somebody!" he exclaimed. Wagnalls jumped up and hurried off. The fire chief leaned forward. "Do you think, Mr. Kennedy, that the little can he told you about started the fire?" "I'm sure of it, although I'll never be able to prove it." "How did it work?" "Well, I imagine a small roll of very dry film was put in to occupy a part of the space. Film is exceedingly inflammable, especially when old and brittle. In composition it is practically guncotton and so a high explosive. In this recent war, I remember, the Germans drained the neutral countries of film subjects until we woke up to what they were doing, while in this country scrap film commanded an amazing price and went directly into the manufacture of explosives. Then I figure that a quantity of wet phosphorus was added, to fill the can, and that then the can was taped. The tape, of course, is not moisture proof entirely. With the dampness from within it would soften, might possibly fall off. In a relatively short time the phosphorus would dry and burn. Immediately the film in the can would ignite. As happened, it blew up, a minor explosion, but enough to scatter phosphorus everywhere. That, in the fume-laden air of the vault--there are always fumes in spite of the best ventilation system made--caused the first big blast and started all the damage." Mackay had rejoined us in time to hear the explanation. "Ingenious," he murmured. "As ingenious as the methods used to murder the girl and her director." Breathless, Wagnalls returned with the collodion. We watched curiously as Kennedy poured it over the charred remains of the second order on the spindle. It seemed almost inconceivable that the remnants of the charred paper would even support the weight of the liquid, yet Kennedy used it with care, and slowly the collodion hardened before us, creating a tough transparent coating which held the tiny fibers of the slip together. At the same time the action of the collodion made the letters on the order faintly visible and readable. "A little-known bank trick!" Kennedy told us. Then he held the slip up to the light and the words were plain. Wagnalls had been correct. The order from Manton was unmistakable. The can was to be kept in the negative vault for a week without being opened, until a certain party unnamed was to come to watch the development of the film. The promoter wet his lips, uneasily. "I--I never wrote that! It--it's my writing, all right, and my signature, but it's a forgery!" XXIX MICROSCOPIC EVIDENCE Kennedy made some efforts to preserve the forged order which he had restored with the collodion, but I could see that he placed no great importance upon its possession. Gradually the yard of the studio had cleared of the employees, who had returned to their various tasks. Under the direction of one stout individual who seemed to possess authority the fire apparatus had been replaced in a portable steel garage arranged for the purpose in a farther corner, and now several men were engaged in cleaning up the dirt and litter caused in the excitement. Except in the basement there were few signs of the blaze. Manton accompanied the fire chief to his car, then hurried up into the building without further notice of us. Mackay went to McGroarty's machine to claim the traveling bag containing our evidence. Kennedy and I started for the dressing rooms. "I want to get blood smears of Shirley and Marilyn," he confided in a low voice. "I shall have to think of some pretext." Neither of the two we sought were in their quarters and so we continued on into the studio. Here we found Kauf at work; at least he was engaged in a desperate attempt to get something out of his people. "Ye gods, Gordon!" we heard him exclaim, as we made our way through the debris of the banquet set to the ballroom now dazzlingly bright under the lights. "What if you do have to wear a bandage around your head? It's a masked ball, isn't it? You've got a monk's cowl over everything but your features, haven't you?" It struck me that the faces had never been more ghastly, although my reason convinced me it was simply the usual effect of the Cooper-Hewitt tubes. But there was no question but that the explosion had given everyone a bad fright, that not an actress or actor but would have preferred to have been nearly anywhere else but under the heat of the glass roof, now a constant reminder of the accident because of the gaping hole directly above them. Marilyn was in the center of the revelers in the set, already in costume. Shirley I saw close to the camera men, standing uneasily on shaky legs, shielding his eyes with one hand while he clung to a massive sideboard for support with the other. He had not yet donned his carnival clothes, nor essayed to put on a make-up. Enid Faye, the only one in sight whose spirits seemed to have rallied at all, was offering him comfort of a sort. "You'll get by, all right, Merle, if you can keep on your pins, and I'll say you deserve credit for trying it. There's"--she stepped back a bit to study him--"there's just one thing. Your eyes show the result of all that smoke and vapor--no color or luster at all. I--I wonder if belladonna wouldn't brighten them up a bit and--well, get you by, for to-day?" "I'll go out and get some at lunch." He smiled weakly. "I'll try anything once." "That's the spirit!" She patted him on the shoulder, then danced on into the center of the set, stopping to direct some barbed remark at Marilyn. Kauf took his megaphone to call his people around him. There seemed to be a certain essential competence about the little man, now that Manton and Phelps and Millard were not about to bother him. While we watched he succeeded in photographing one of the full shots of the general action or atmosphere of the dance. Then he hurried to the side of Shirley, to see if the heavy man felt equal to the task of resuming his make-up once more. I found the time dragging heavy on my hands and I wished that Kennedy would return to the laboratory or decide upon some definite action. Though I racked my brain, I failed to think of a device whereby Kennedy could get blood smears of Shirley or Marilyn without their knowledge. Once more my reflections veered around to the matter of the stolen towel and I wondered if that had been wasted effort on Kennedy's part; if the fire had thrown out his carefully arranged plans to trap whoever took it. Suddenly I realized that Kennedy was following a very definite procedure, that his seeming indifference, his apparent idle curiosity concerning the scene taking, masked a settled purpose. When Phelps entered he approached him casually and turned to him with skilled nonchalance, holding up a finger. "Will you lend me a pocket knife for a moment?" he asked, "to get a hang-nail?" Phelps produced one, rather grudgingly. Kennedy promptly went over to the window, as though seeking better light. Thereafter he avoided Phelps. Soon the banker had forgotten the incident. Some time later Manton rushed in from the office. Kennedy maneuvered his way to the promoter's side and waited his chance to borrow that man's pocket knife under conditions when Manton would be the least apt to remember it. Then he made his way around to Mackay and I saw that both the acquisitions went into little envelopes of the sort used to take the blood smears after the explosion and falling glass. Kennedy now seemed rather elated. Millard entered and he borrowed the scenario writer's knife in exactly the same fashion as the others. No one of the three men noticed his loss. I thought it lucky that all three carried the article, and tried to guess how far Kennedy intended to carry this little scheme. Kauf's announcement of lunch gave me my answer. It seemed that there would be just half an hour and that the entire cast was expected to make shift at McCann's rather than attempt to go to any better place at a greater distance. Immediately Kennedy turned to me. "Hurry, Walter! Twenty minutes' quick work and then it's the laboratory and the solution of this mystery." With Mackay and the bag we stole to the dressing rooms, waiting until sure that everyone was downstairs. In Enid's chamber Kennedy glanced about carefully but swiftly. When nothing caught his attention he picked up her finger-nail file, gingerly, from the blunt end, slipping it into one of the little envelopes which Mackay held open. Thereupon the district attorney put his identifying mark upon the outside and we went to the next room. It proved to be Gordon's. The general search was barren of result, but the dressing table yielded another finger-nail file, handled in the same manner as before. Then we entered Marilyn's room and left with the file from her dressing stand. In Shirley's quarters, the last we visited, we were in greater luck, however. While Kennedy and Mackay abstracted the usual file, I discovered some bits of tissue paper used in shaving. There was caked soap left to dry just as it had been wiped from the razor. More, there was a blood stain of fair proportions. "Here's your smear, Kennedy," I exclaimed. "Good! Fine!" He faced Mackay. "Now I lack just one thing, a sample of the blood of Miss Loring." "Is that all?" The district attorney brightened. "Let me try to get it! I--I'll manage it in some way!" "All right!" Kennedy took the bag. "Explain your marks so I'll know--" He stopped suddenly. "No, don't tell me anything. I'll make my chemical analyses and microscopic examinations without knowing the identity in the case either of the blood samples or the finger-nail files. If I obtain results by both methods, and they agree, I'll return armed with double-barreled evidence. Meanwhile, Mackay, you get a smear from Miss Loring and follow us to the laboratory. I'll coax McGroarty to drive us down, so you'll have your car and you can bring us back." The district attorney nodded. "Me for McCann's," he muttered. "That's where she went to eat." He rushed off eagerly. Kennedy had no difficulty persuading McGroarty to put his particular studio car at our disposal without an order from Manton or from the director who had called him. In a very brief space of time we were at the laboratory. "You expect to find the blood of one of those people showing traces of the antivenin?" I grasped Kennedy's method of procedure, but wanted to make sure I understood it correctly. Already I was blocking out the detailed article for the Star, the big scoop which that paper should have as a result of my close association with Kennedy on the case. "One of those samples should correspond, I suppose, to the trace of blood on the portieres?" "Exactly!" He answered me rather absently, being concerned in setting out the apparatus he would need for a hasty series of tests. "Will the antivenin show in the blood after four, perhaps five days?" "I should say so, Walter. If it does not, by any chance, I will be able to identify the blood, but that is much more involved and tedious--a great deal more actual work." "I've got it straight, then. Now--" I paced up and down several times. "The finger-nail files should show a trace of the itching salve? Is that correct, Craig?" For a moment he didn't answer, as his mind was upon his paraphernalia. Then he straightened. "Hardly, Walter! The salve is soluble in water. What I shall find, if anything, is some of the fibers of the towel. You see, a person's finger nails are great little collectors of bits of foreign matter, and anyone handling that rag is sure to show some infinitesimal trace for a long while afterward. If the person stealing the towel filed or cleaned his nails there will be evidence of the fibers on his pocket knife or finger-nail file. I impregnated the towel with that chemical so that I would be able to identify the fibers positively." "The use of the itching salve was unnecessary?" A quizzical smile crept across Kennedy's face. "Did you think I expected some one to go walking around the studio scratching his hands? Did you imagine I thought the guilty party would betray his or her identity in such childish fashion, after all the cleverness displayed in the crimes themselves?" "But you were insistent that I rub in the--" "To force them to wash their hands after touching the towel, Walter." "Oh!" I felt rather chagrined. "Wouldn't some pigment, some color, have served the purpose better?" "No, because anyone would have understood that and would have taken the proper measures to remove all traces. But the itching salve served two purposes. It was misleading, because obviously a trap upon reflection, and so it would distract attention from the impregnated fibers, my real scheme. Then it was the best device of all I could think of, for it set up a local irritation of the sort most calculated to make a person clean his finger nails. The average man and woman is not very neat, Walter. I was not sure but a scientific prodding was necessary to transfer my evidence to some object I could borrow and examine under a microscope." Meanwhile Kennedy's long fingers were busy at the preliminary operations in his tests. He turned away and I asked no more questions, not wishing to delay him. I noticed that first he examined the blood samples under the microscope. Afterward he employed a spectroscope. But none of the operations took any great amount of time, since he seemed to anticipate his results. Mackay burst in upon us, very elated, and produced a handkerchief with a bit of blood upon it. "I scratched her deliberately with the sharp point of my ring," he chuckled. "I found her in the restaurant and the seat beside her was empty. I--I talked about everything under the sun and I guess she thinks I'm a clumsy boob! Anyhow she cried out when I did it, and got red in the face for a moment; but she suspects nothing." Kennedy cut the spot from the handkerchief, put it in an envelope, and turned back to his table. I drew Mackay into the corner. As the minutes sped by and Craig worked in absorbed concentration, Mackay grew more and more impatient to get back to the studio. "Did you find anything?" repeated Mackay, for the tenth time. With a gesture of annoyance, Kennedy reached out for the nail files. "This is a grave matter," he frowned. "I must check it up--and double check it--then I'm going back to the studio to triple check it. Let me see what the nail files reveal. It will be a bare ten minutes more." Insisting that we remain back in the corner, he spread out the four nail files and the open blades of the three pocket knives, setting each upon the envelope which identified it. The next quarter of an hour seemed interminable. Finally Kennedy started replacing the files and the pocket knives in their envelopes, his face still wearing the inscrutable frown. Next he packed the blood samples and other evidence in the traveling bag once more. Mackay was bursting with impatience, but Craig still refused to betray his suspicions. "I must get back there--quick," he hastened. "I want everybody in the projection room. In court, a jury might not grasp the infallibility of the methods I've used. There would be a great deal of medical and expert testimony required--and you know, Mackay, what that means." "Is it a man--or a woman you suspect?" persisted the district attorney. "Three of the men had pocket knives and--" Kennedy led the way to the door without answering, and Mackay cut short his hopeless quizzing as Craig nodded to me to carry the bag. XXX THE BALLROOM SCENE Sounds of music caught our ears as we entered the studio courtyard of Manton Pictures. Carrying the bag with its indisputable proof of some person's guilt, we made our way through the familiar corridor by the dressing rooms, out under the roof of the so-called large studio. There a scene of gayety confronted us, in sharp contrast with the gloomy atmosphere of the rest of the establishment. Kauf, however, had thoroughly demonstrated his genius as a director. To counteract the depression caused by all the recent melodramatic and tragic happenings, he had brought in an eight-piece orchestra, establishing the men in the set itself so as to get full photographic value from their jazz antics. Where Werner and Manton had dispensed with music, in a desperate effort at economy, Kauf had realized that money saved in that way was lost through time wasted with dispirited people. It was a lesson learned long before by other companies. In other studios I had seen music employed in the making of soberly dramatic scenes, solely as an aid to the actors, enabling them to get into the atmosphere of their work more quickly and naturally. Under the lights the entire set sparkled with a tawdry garishness apt to fool those uninitiated into the secrets of photography. On the screen, colors which now seemed dull and flat would take on a soft richness and a delicacy characteristic of the society in which Kauf's characters were supposed to move. Obviously fragile scenery would seem as heavy and substantial as the walls and beams of the finest old mansion. Even the inferior materials in the gowns of most of the girls would photograph as well as the most expensive silk; in fact, by long experience, many of the extra girls had learned to counterfeit the latest fashions at a cost ridiculous by comparison. Kennedy approached Kauf, then returned to us. "He asks us to wait until he gets this one big scene. It's the climax of the picture, really, the unmasking of the 'Black Terror.' If we interrupt now he loses the result of half a day of preparation." "He may lose more than that!" muttered Mackay; and I wondered just whom the district attorney suspected. "Is everyone here?" I asked. "All seven?" Gordon and Shirley, of the men, and Marilyn and Enid, of course, were out on the floor of the supposed ballroom. Gordon I recognized because I remembered that he was to wear the garb of a monk. Marilyn was easily picked out, although the vivacity she assumed seemed unnatural now that we knew her as well as we did. Her costume was a glorious Yama Yama creation, of a faint yellow which would photograph dazzling white, revealing trim stockinged ankles and slender bare arms, framing face and eyes dancing with merriment and maliciousness. Unquestionably she was the prettiest girl beneath the arcs, never to be suspected as the woman who had braved the terrors of a film fire to rescue the man she loved. Enid was stately and serene in the gown of Marie Antoinette. In the bright glare her features took on a round innocence and she was as successful in portraying sweetness as Marilyn was in the simulation of the mocking evil of the vampire. Shirley interested me the most, however. I wondered if Kennedy still eliminated him in guessing at the identity of the criminal. I called to mind the heavy man's presence in the basement at the time of the explosion and McGroarty's information that he had been hanging about that part of the studio for some time previously. Some one had planted a cigarette case and stub to implicate Gordon, according to Kennedy's theory. Shirley certainly had had opportunity to steal the towel from the locker as well as to point suspicion toward the leading man. In the midst of my reverie Shirley approached and passed us. He was in the garb of Mephisto. Like the others, he had not yet masked his face. A peculiar brightness in his eyes struck me and I nudged Kennedy. "Belladonna," Kennedy explained when he was beyond earshot. "Oh!" I remembered. "Enid told him to use it." "What?" I repeated the conversation as near as I could reconstruct it. "H-m! That's a new cure for smoke-burned eyes; no cure at all." I was unable to get any more out of Kennedy, however. Manton I detected in the background with Phelps. The two men were arguing, as always, and it was evident that the banker was accomplishing nothing by this constant hanging about the studio. Where previously my sympathy had been with Phelps entirely, now I realized that the promoter had won me. Indeed, Manton's interest in all the affairs of picture making at this plant had been far too sincere and earnest to permit the belief that he was seeking to wreck the company or to double-cross his backer. Millard entered the studio as I glanced about for him. He handed some sheets to Kauf, then turned to leave. I attracted Kennedy's attention. "You don't want Millard to get away," I whispered. Kennedy sent Mackay to stop him. The author accompanied the district attorney willingly. "Yes, Mr. Kennedy?" "As soon as this scene is over we're going down to the projection room; everyone concerned in the death of Miss Lamar and of Mr. Werner." The scenario writer looked up quickly. "Do you--do you know who it is?" he asked, soberly. "Not exactly, but I will identify the guilty person just as soon as we are assembled down in front of the screen." Shirley had left the studio floor, apparently to go to his dressing room. Now I noticed that he returned and passed close just in time to hear Millard's question and Kennedy's answer. His eyes dilated. As he turned away his face fell. He went on into the set, but his legs seemed to wabble beneath him. I was sure it was more than the weakness resulting from his experience in the fire. Kauf's voice, through the megaphone, echoed suddenly from wall to wall, reverberating beneath the roof. "All ready! Everyone in the set! Masks on! Take your places!" At a signal the orchestra struck up and the couples started to dance. It was a wonderfully colorful scene and I saw that Kauf proposed to rehearse it thoroughly, doing it over and over without the cameras until every detail reached a practiced perfection. In this I was certain he achieved results superior to Werner's slap, dash, and bang. Then came the call for action. "Camera!" Kauf began to bob up and down. "Into it, everybody!" For fascination and charm this far exceeded the banquet scene which we had witnessed in the taking previously. The music was surprisingly good, so that it was impossible for the people not to get into the swing, and the result was a riotous swirling of gracefully dancing pairs; the girls, selected for their beauty, flashing half-revealed faces toward the camera, displaying eyes which twinkled through their masks in mockery at a wholly ineffectual attempt at concealment. Enid maintained her stately carriage, but made full use of the dazzling whiteness of her teeth. Early she permitted the attentions of the cowled monk whom she knew to be her lover. Marilyn was everywhere, making mischief the best she could. Shirley stalked about in his satanic red, which would photograph black and appear even more somber on the screen. Of course the whole was not photographed in a continuous strip from one camera position. I saw that Kauf made several long shots to catch the general atmosphere. Then he made close-up scenes of all the principals and of some of the best appearing extras. At one time he ordered a panorama effect, in which the cameras "panned," swept from one side to the other, giving a succession of faces at close range. Finally everything was ready for the climax. Shirley had been playing a sort of Jekyll and Hyde role in which he was at once the young lawyer friend of Enid and the Black Terror. Unmasked and cornered at this function of a society terrified by the dread unknown menace, he was to make the transformation directly before the eyes of everyone, using the mythical drug which changed him from a young man of good appearance and family to the being who was a very incarnation of evil. For once Kauf did not rehearse the scene. Shirley was obviously weakened from his experience and the director wished to spare him. All the details were shouted out through the megaphone, however, and I grasped that the action of this part of the dance was familiar to everyone; it was the big scene of the story toward which all other events had built. Then came the familiar order. "Camera!" At the start of this episode the orchestra was playing and the dancers were in motion. Suddenly Gordon, as the hero, strode up to Shirley and unmasked him with a few bitter words which later would be flashed upon the screen in a spoken title. Instantly a crowd gathered about, but in such a way as not to obstruct the camera view. Cornered, seeing that flight was impossible unless he became the Black Terror and possessed the strength and fearlessness of that strange other self, Shirley drew a little vial from his breast pocket and drank the contents. Evidently he knew his Mansfield well. Slowly he began to act out the change in his appearance which corresponded with the assumption of control by the evil within. His body writhed, went through contortions which were horrible yet fascinating. It was almost as though a new fearful being was created within sight of the onlookers. Not only was the face altered, but the man's stature seemed to shrink, to lose actual inches. I thought it a wonderful exhibition. The very next instant there came a groan from Shirley, something which at once indicated pain and realization and fear. He lost all control of himself and in a moment pitched forward upon the floor, sputtering and clutching at the empty air. Another cry broke from between his lips, a ghastly contracted shriek as treble as though from the throat of a woman. This was no part of the story, no skillful bit of acting! It was real! Even before I had grasped the full significance of the happening Kennedy had dashed forward. The cameras still were grinding and they caught him as he kneeled at the side of the stricken man. Hardly a second afterward Mackay and I followed and were at Kennedy's side. Kauf and the others, their faces weirdly ashen, clustered about in fright. A third time the invisible hand had struck at a member of the company. "The Black Terror," with all the horror written into that story, contained nothing as fearful as the menace to the people engaged in its production. Shirley's skin was cold and clammy, his face almost rigid. While conscious, he was helpless. Kennedy found the little vial and examined it. "Atropin!" he ejaculated. "Walter!" He turned to me. "Get some physostigmin, quick! Have Mackay drive you! It's--it's life or death! Here--I'll write it down! Physostigmin!" As I raced madly out and down the stairs, Mackay at my heels, I heard a woman's scream. Marilyn! Did she think him dead? Once in the car, headed for the nearest drug store, grasping wildly at the side or at the back of the seat every few moments as the district attorney skidded around curves and literally hurdled obstacles, I remembered a forgotten fact. Atropin! That was belladonna, simply another name for the drug. Shirley had procured the stuff for use in his eyes. Nevertheless, he had been aware, undoubtedly, of its deadly nature. Passing by Kennedy and the rest of us, he had overheard Kennedy state that the murderer would be identified as soon as all could be assembled in the projection room. The heavy man had not cared to face justice in so prosaic a manner. With the same sense of the melodramatic which had led him to slay Stella Lamar in the taking of a scene, Werner in the photographing of another, he had preferred suicide and had selected the most spectacular moment possible for his last upon earth. Yes, Shirley was guilty. Rather than wait the slow processes of legal justice he had attempted suicide. Now we raced to save his life, to preserve it for a more fitting end in the electric chair. XXXI PHYSOSTIGMIN The first drug store we found was unable to supply us. At a second we had better luck. All in all, we were back at the Manton Pictures plant in a relatively few minutes, a remarkable bit of driving on the part of the district attorney. Shirley was still in the set. Kennedy at once administered the physostigmin, I thought with an air of great relief. "This is one of the rare cases in which two drugs, both highly poisonous, are definitely antagonistic," he explained. "Each, therefore, is an antidote for the other when properly administered." Marilyn was chafing Shirley's cold hands, tears resting shamelessly upon her lids, a look of deep inexpressible fear in her expression. "Will--will you be able to save him, Professor?" she asked, not once, but a dozen different times. None of the rest of us spoke. We waited anxiously for the first signs of hope, the first indication that the heavy man's life might be preserved. It was wholly a question whether the physostigmin had been given to him quickly enough. Kennedy straightened finally, and we knew that the crisis was over. Marilyn broke down completely and had to be supported to a chair. Strong, willing arms lifted Shirley to take him to his dressing room. At that moment Kennedy stood up, raising his voice so as to demand the attention of everyone, taking charge of matters through sheer force of personality. "I have come here this afternoon," he began, "to apprehend the man or woman responsible for the death of Miss Lamar and Mr. Werner, for the fire in the negative vault, and now for this attempt upon the life of Mr. Shirley." Not a sound was evident as he paused, no movement save a vague, uneasy shifting of position on the part of some of those who had been on the point of leaving. "I have indisputable evidence of the guilty person's identity, but, nevertheless, for reasons which I will explain to you I have not yet completed my identification. To do so it is necessary that certain photographed scenes be projected on the screen and that certain other matters be made perfectly clear. I am very anxious, you see, to eliminate the slightest possibility of error. "Mr. Mackay here"--Kennedy smiled, very slightly--"is the district attorney with jurisdiction at Tarrytown. At my request, since yesterday--or, to be exact, since the death of Mr. Werner warned us that no time could be lost--he has carried a 'John Doe' warrant. Immediately following my identification of the guilty person he--or she--will be placed under arrest. The charge will be the murder of Stella Lamar by the use of poison in a manner which I will explain to you. The trial will take place at White Plains, the county seat of Westchester County, where the murder occurred. Mr. Mackay informs me that the courts there are not crowded; in fact, he personally has been able to devote most of his time to this case. Therefore the trial will be speedy and I am sure that the cold-blooded methods used by this criminal will guarantee a quick sentence and an early trip to the electric chair at Ossining. Now"--suddenly grim--"if everyone will go down to the projection room, the larger one, we will bring matters to their proper conclusion." I imagined that Kennedy's speech was calculated to spread a little wholesome fear among the people we had considered suspects. In any case that was the result, for an outsider, from the expressions upon the various faces, might have concluded that several of them were guilty. Each seemed to start off across the studio floor reluctantly, as though afraid to obey Kennedy, yet unable to resist the fascination of witnessing the identification of the criminal, as though feeling that he or she individually might be accused, and yet unwilling to seek safety at the expense of missing Kennedy's revelation of his methods and explanation of their result. I drew him aside as quickly as I could. "Craig," I started, eagerly, "isn't this all unnecessary? Can't you see that Shirley is the guilty man? If you will hurry into his room with paper and pencil and get his confession before he recovers from his fright and regains his assurance--" "What on earth, Walter!" Kennedy interrupted me with a look of surprise which I did not miss even in my excitement. "What are you driving at, anyway?" "Why, Shirley is the criminal. He--" "Nonsense! Wasn't an attempt made to kill him just now? Wasn't it evident that he was considered as dangerous to the unknown as Werner, the director? Hasn't he been eliminated from our calculations as surely as the man slain yesterday?" "No!" I flushed. "Not at all, Craig! This was not an attempt at murder. There were none of the criminal's earmarks noticeable at Tarrytown or in the banquet scene." "How do you mean, Walter?" For once Kennedy regarded me seriously. "Why, you pointed out yourself that this unknown was exceptionally clever. The attempt on Shirley, if it were an attempt, was not clever at all." "Why?" "Why?" I was a little sarcastic, because I was sure of myself. "Because the poison was atropin--belladonna. That is common. I've read of any number of crimes where that was used. Do you think for a moment that the mind which figured out how to use snake venom, and botulin toxin, would descend to anything as ordinary as all this?" "Well, if it was not an attempt at murder, what was it?" "Suicide! It's as plain as the nose on your face. Shirley was passing us as we were standing with Millard and as you told Millard we all were to go to the projection room to identify the criminal. Therefore Shirley knew he was at the end of his rope. With the theatrical temperament, he took the poison just as he finished playing his last great scene. It--it was a sort of swan song." "Quite a theory, Walter!" Now I knew Kennedy was unimpressed. "But, where did he get the belladonna?" "For his eyes. After the smoke smart." "The drug is of no use against such inflammation." "No, but it served to brighten his eyes. Enid suggested it to him and he went out and got it. It helped him play his scenes. It gave him the glittering expression he needed in his characterization." Again Kennedy seemed to grasp my view. He hesitated for several moments. Finally he looked up. "If Shirley is the criminal, and if he is above using as common a drug as atropin for killing another man, then--then why isn't he above using it upon himself?" That struck me as easy to answer. "Because if he is killing himself it is not necessary for him to cover his tracks, or to do it cleverly, and besides"--it was my big point--"he probably didn't decide to try to do it until he overheard us and realized the menace. At that time he had the belladonna in his pocket. He did not have an opportunity to procure anything else." Kennedy grinned. "You're all wrong, Walter, and I'll show you where your reasoning is faulty. In the first place if this criminal was the type to commit suicide at the moment he thought he was about to be caught he would be the type who would reflect upon that idea beforehand. As his crimes show a great deal of previous preparation, so we may assume that he would prepare for suicide, or rather for the possibility that he might wish to attempt it. Therefore he would have something better for that purpose than atropin." I shook my head, but Kennedy continued. "As a matter of fact, the use of that drug is not less clever than the use of the venom or the toxin; it is more so. Stop and think a minute! The snake venom was employed in the case of Miss Lamar's death because it offered about the least possible chance of leaving telltale clues behind. The snake poison could be inflicted with a tiny scratch, and in such a way that an outcry from the girl would never be noticed. Nothing but my pocket lens caught the scratch; only the great care I used in my examination put us on the trail at all. "Now remember how Werner met his death. The toxin gave every symptom of food poisoning. Except that we discovered the broken stem of the wineglass we would never have been able to prove the tragedy anything but accident. Very possibly we have Shirley to thank for the fact that our one clue there was not removed or destroyed. "In both cases the selection of the poison was suited to the conditions. Therefore, if an attempt was made to kill Shirley--and of the fact I am sure--we might expect that the agent likewise would be one least apt to create suspicion. There are no portieres, no opportunity for the use of another venom; and besides, that has lost its novelty, and so its value. Similarly there is no use of food or wine in the scene, precluding something else along the toxin order. "Our unknown realizes that the safest place to commit murder is where there is a crowd. He has followed that principle consistently. In the case of the heavy man, who has a bit of business before the camera where he drinks the contents of a little bottle, the very cleverest thing is to use belladonna, because Shirley has employed it for his eyes, and because"--maliciously, almost--"it leads immediately to the hypothesis of suicide." "Ye gods, Craig!" A sudden thought struck me and rather terrified me. "Do you suppose Enid Faye suggested the use of the drug to Shirley as part of the scheme to kill him? Is she--" "I prefer," Kennedy interrupted--"I prefer to suppose that the guilty person overheard her, or perhaps saw him buy it or learned in some other way that he was going to use it." Completely taken up with this new line of thought, I failed to question Kennedy further, and it was just as well because most of the people were on their way down to the projection room, not only those we wished present, but practically everyone of sufficient importance about the studio to feel that he could intrude. Kennedy turned to Mackay, who had taken no part in our discussion, although an interested listener. "You have the bag and all the evidence?" "Yes!" Mackay picked it up. "Watkins, the camera man, watched it for me while Jameson and I went after that drug." Kennedy stooped down quickly, but it was locked and had not been tampered with. In the corridor by the dressing rooms we met Kauf, and Kennedy stopped him. "How long would it take to make a print from the scene where Shirley took the poison?" "We could have it ready in half an hour, in a case of grim necessity." "Half an hour?" I exclaimed at that, in disbelief. "You couldn't begin to dry the negative in that time, Kauf." He glanced at me tolerantly. "We make what is called a wet print; that is, we print from the negative while it is still wet and so we only have the positive to dry. Then we put it on drums in a forced draught of hot air. The result is not very good, but it's a fine thing sometimes to get a picture of a parade or some accident in a theater right after it happens." "Will you do it for me, Kauf?" Kennedy broke in, impatiently. "This is a case of grim necessity," he added. Kauf hurried off and we made our way across the yard to the stairs leading down into the basement and to the projection room specified by Kennedy. Here Manton was waiting, uneasy, flushed, his face gathered in a frown and his hands clenching and unclenching in his nervousness. "Do you--do you know who it is?" he demanded. "Not yet," Kennedy replied. "First I must marshal all my evidence." "Who--who do you want present in the projection room?" "Mr. Phelps, Mr. Millard, and--yourself, Mr. Manton. Miss Loring and Miss Faye. Mr. Gordon. Anyone else who wishes, if there is room." "Phelps, Millard, Gordon, and the two girls are inside already." "Good! We will start at once." Manton turned, to lead the way in. At that moment there was a call from the yard. We stopped, looking up. It was Shirley. "Wait just a minute," he cried. He was so weak that the two extra men who were helping him virtually supported his weight. On his face was a look of desperate determination. "I--I must see this too!" he gasped. XXXII CAMERA EVIDENCE Coming in from the bright light of open day, the projection room seemed a gloomy, forbidding place, certainly well calculated to break down the reserve of perhaps the cleverest criminal ever pitting his skill against the science of Craig Kennedy. It was a small room, long and not so wide, with a comparatively low ceiling. In order to obviate eye strain the walls were painted somberly and there were no light colors in evidence except for a nearly square patch of white at the farther end, the screen upon which the pictures were projected. The illumination was very dim. This was so that there would be no great contrast between the light reflected from the images cast upon the screen during pictures and the illumination in the room itself between reels; again designed to prevent strain upon the eyes of the employees whose work was the constant examination of film in various stages of its assembly. The chairs were fastened to the floor, arranged in tiny crescents and placed so as not to interfere with the throw of the pictures from behind. The projection machines themselves, two in number in order to provide continuous projection by alternating the reels and so threading one machine while running the other, were in a fireproof booth or separate room, connected with the tiny auditorium only by slits in the wall and a sort of porthole through which the operator could talk or take his instructions. Directly beneath the openings to the booth were a table equipped with a shaded lamp, a stand for manuscripts, and a signal button. Here the film cutters and editors sat, watching the subject upon which they worked and making notes for changes, for bits of superfluous action to be cut out, or for titles or spoken inserts to be moved. At a signal the operator could be instructed to stop at any point, or to start, or to wind back and run some given piece over again. The lights in the room were controlled from within the booth and also by a switch just at the side of the door. A telephone on the table offered a connection with any part of the studio or with the city exchanges, so that an official of the company could be reached while viewing a picture. As we entered I tried to study the different faces, but found it a hopeless task on account of the poor light. Kennedy took his place at the little table, switching on the little shaded lamp and motioning for Mackay to set the traveling bag so he could open it and view the contents. Then Mackay took post at the door, a hand in his pocket, and I realized that the district attorney clasped a weapon beneath the cover of his clothing, and was prepared for trouble. I moved over to be ready to help Kennedy if necessary. As Kennedy took his key, unlocking the bag, it would have been possible to have heard the slightest movement of a hand or foot, the faintest gasp of breath, so tense was the silence. First Kennedy took out the various rolls of film. Looking up, he caught the face of the operator at the opening in the wall and handed them to him one by one. "Here are two sections of the opening of the story, scenes one to thirteen of 'The Black Terror' put together in order, but without subtitles. One is printed from the negative of the head camera man, Watkins. The other is exactly the same action as taken by the other photographer. We will run both, but wait for my signal between each piece. Understand?" "Yes, sir!" "Now I am giving you two rolls which contain prints of the negative from both cameras of the action at the moment of Werner's death. Those are to be projected in the same way when I give you the signal. Following that there will be two very short pieces which show the attempt upon the life of Mr. Shirley. They are being rushed through the laboratory at this moment and will be brought to you by the time we are ready for them. Finally"--Kennedy paused and as he took the rolls of negative of the snake film I could see that he hesitated to allow them out of his hands even for a few moments--"here is some negative which will be my little climax. It--it is very valuable indeed, so please be careful." "You--you want to project the NEGATIVE?" queried the operator. "Yes. They tell me it can be done, even with negative as old and brittle as this, if you are careful." "I'll be careful, sir! You punch the button there once to stop and two to go. I'll be ready in a moment." As he spoke he disappeared and soon we heard the unmistakable hiss of the arcs in his machines. Kennedy stooped and from the bag produced the little envelopes with the pocket knives and nail files, the set of envelopes with the samples of blood, the piece of silk he had cut from the portiere at Tarrytown, the tiny bits he had cut from the towel found by me in the washroom of this studio, and a microscope--the last, I guessed, for effect. Around in the semidarkness I could see the faces as necks were craned to watch us. Kennedy's deliberateness, his air of certainty, must have struck terror home to some one person in the little audience. Often Kennedy depended upon hidden scientific instruments to catch the faint outward signs of the emotions of his people in a seance of this sort, to allow the comparison of their reactions in the course of his review of the evidence, to give him what amounted to a very sure proof of the one person's guilt. The very absence of some such preparation indicated to me the extent of his confidence. At length he began his little lecture, for all the world as though this were one of his classes at the University, as though there were at stake some matter of chemical reaction. "I need not tell you, ladies and gentlemen, that this is a highly scientific age in which we live." His tones were leisurely, businesslike, cool. "Your own profession, the moving picture, with all its detail of photography and electricity, its blending of art and drama and mechanics, is indicative of that, but"--a pause for emphasis--"it is of my own profession I wish to talk just now, the detection and prevention of crime. "Criminals as a whole were probably the very first class of society to realize the full benefit of modern science. Banks and business institutions, the various detective and police forces, all grades and walks of life have been put to it to keep abreast of the development of scientific crime. So true has this been that it is a matter of common belief with many people that the hand of the law may be defied with impunity, that justice may be cheated with absolute certainty, just so long as a guilty man or woman is sufficiently clever and sufficiently careful. "Fortunately, the real truth is quite the reverse. Science has extended itself in many dimensions of space. With the use of a microscope, for instance, a whole new world is opened up to the trained detective. "Everyone knows now that the examination of hands and fingers is an infallible aid in the identification of criminals and in the proof of the presence of a suspect at the scene of a crime--I refer to fingerprints, of course. But fingerprints are only one small detail in this department of investigation. Our criminals know that gloves must be worn, or any smooth surface wiped so as to remove the prints. In that way they believe they cheat the microscope or the pocket lens. "As a matter of fact few people have thought of another way of gaining evidence from the finger tips, but it is a method possible to the scientist, and is not only practicable but exceedingly effective. In time it will be recognized by all specialists in crime. Now I refer to the deposits under the finger nail. "Indeed, it is surprising how many things find their way under the nail and into the corners of the cuticle." Kennedy indicated the files and pocket knives visible in the shaded square of light before him. "The value of examining finger-nail deposits becomes evident when we realize that everyone carries away in that fashion a sample of every bit of material he handles. To touch a piece of cloth, even lightly, will result in the catching of a few of its fibers. Similarly, the finger nails will deposit either a small or large portion of their accumulation upon such things as the knife blades or files used to clean them; and there identification still is possible. Nothing in the world is too infinitesimal for use as evidence beneath the microscope. "In classifying these accumulations"--Kennedy paused and the silence in the little room was death-like--"we may say that there are some which are legitimate and some which are not. It is the latter which concern us now. The first day we were here at the studio, just four days ago now, and immediately following the murder of Miss Lamar, Mr. Jameson discovered a towel in the washroom on the second floor of the office building. On that towel there were spots of Chinese yellow, make-up, as though it had been used to wipe a face or hands by some actor or actress. Those spots were unimportant. There were others, however, of an entirely different nature, together with the mark of blood and a stain which showed that a hypodermic needle had been cleaned upon the towel before it was thrown in the basket." Kennedy leaned forward. His eyes traveled from face to face. "That towel was a dangerous clue." Now there was a new grim element in his voice. "That towel alone has given me the evidence on which I shall obtain a conviction in this case. To-day I let it be known that it was in my possession and the guilty man or woman understood at once the value it would be to me. In order to gain additional clues I purposely gave the impression that I had yet to analyze either the spots or the trace of blood. I wanted the towel stolen, and for that purpose I placed the bag containing it in a locker and left the locker unguarded. I coated the towel with a substance which would cause discomfort and alarm--itching salve--not with the idea that anyone would be foolish enough to go about scratching before my eyes, but with the idea of making that person believe that such was my purpose and with the idea of driving him--or her--to washing his hands at once and, more, with the idea of forcing him or scaring him into cleaning his fingernails. "I succeeded. On one of these files or knife blades I have found and identified the fibers of that towel. I do not yet know the person, but I know the mark placed by Mackay on the outside of the little envelope, and when I tell Mackay the mark he will name the guilty person." "Mr. Kennedy!" Manton spoke up, impulsively, "every towel in the studio is the same. I bought them all at the same time. The fibers would all be alike. You have named seven people to me, including myself, as possibly guilty of these--these murders. Your conclusions may be very unjust--and may lead to a serious miscarriage of justice." Kennedy was unperturbed. "This particular towel, in addition to the itching salve, was thoroughly impregnated with a colorless chemical which changed the composition of the fibers in a way easily distinguishing them from the others under the microscope. Do you see, Mr. Manton?" The promoter had no more to say. "Now what connection has the towel with the case? Simply this!" Kennedy picked up one of the tiny pieces he had cut out of it. "The poison used to kill Miss Lamar was snake venom." He paused while a little murmur went through his audience, the first sound I had detected. "These spots on the towel are antivenin. The venom itself is exceedingly dangerous to handle. The guilty man--or woman--took no chances, but inoculated himself with antivenin, protection against any chance action of the poison. The marks on the towel are the marks made by the needle used by that person in taking the inoculation. "If you will follow me closely you will understand the significance of this. Miss Lamar was killed by the scratch of a needle secreted in the portieres through which she came, playing the scene in Mr. Phelps's library. That I will prove to you when I show you the film. The night following her death some one broke into the room there at Tarrytown and removed the needle. In removing the needle that person scratched himself, or herself. On the portieres I found some tiny spots of blood." Kennedy paused to hold up the bit of heavy silk. "I analyzed them and found that the blood serum had changed in character very subtly. I demonstrated that the blood of the person who took the needle contained antivenin, and if necessary I can prove the blood to come from the same individual who wiped the needle on the towel in the studio." Kennedy pressed the button before him, twice. "Now I want you to see, actually see Miss Lamar meet her death." The lights went out, then the picture flashed on the screen before us, revealing the gloom and mystery of the opening scene of "The Black Terror." We saw the play of the flashlight, finally the fingers and next the arm of Stella as she parted the curtains. In the close-up we witnessed the repetition of her appearance, since the film was simply spliced together, not "matched" or trimmed. Following came all the action down to the point where she collapsed over the figure of Werner on the floor. Before the camera man stopped, Manton rushed in and was photographed bending over her. Kennedy's voice was dramatically tense, for not one of us but had been profoundly affected by the reproduction of the tragedy. "Did you notice the terror in her face when she cried out? Was that terror, really? If you were watching, you would have detected a slight flinch as she brushed her arm up against the silk. For just a moment she was not acting. It was pain, not pretended terror, which made her scream. The devilish feature to this whole plot was the care taken to cover just that thing-her inevitable exclamation. Now watch closely as I signal the operator to run the same action from the other camera. Notice the gradual effect of the poison, how she forces herself to keep going without realization of the fact that death is at hand, how she collapses finally through sheer inability to maintain her control of herself a moment longer." During the running of the second piece the tense silence in the room was ghastly. Who was the guilty person? Who possessed such amazing callousness that an exhibition of this sort brought no outcry? "Now"--Kennedy glanced around in the dim light, switched on between the running of the different strips--"I'm going to project the banquet scenes and show you the manner of Werner's death." Scene after scene of the banquet flashed before us. Here the cutter had not been sure just what Kennedy wanted and had spliced up everything. We saw the marvelous direction of Werner, who little realized that it was to be his last few moments on earth, and we grasped the beauty and illusion of the set caused by the mirrors and the man's skill in placing his people. Yet there was not a sound, because we knew that this was a tragedy, a grim episode in which there was no human justification whatever. Werner rose at his place. He proposed his toast. He drank the contents of his glass. Then, his expression changed to wonderment and from that to fear and realization, and he dropped to the floor. Kennedy's voice, interrupting, seemed to me to come from a great distance, so powerfully was I affected by the bit of film. "The poison used to kill Mr. Werner was botulin toxin, selected because its effects could not be diagnosed as anything other than ordinary food poisoning. When we look at the print from the second camera's negative you will notice how quickly it acted. It was the pure toxin, placed in his glass before the wine was poured." Once more the unfortunate director's death was reproduced before us. "Struck down," exclaimed Craig, "as though by some invisible lightning bolt, without mercy, without a chance, without the slightest bit of compunction! Why? I'll tell you. Because he suspected, in fact knew, who the guilty person was. Because he followed that person out to Tarrytown the night the needle was removed from the portieres. Because he was a menace to that person's life!" Kennedy turned to the operator. "Have those other scenes come down?" "Yes, sir!" "All right!" Kennedy faced the rest of us again. "There was, or rather is, another person who suspects the identity of the criminal. To-day an attempt was made upon the life of Shirley. Shirley will not tell whom he suspects because he has no definite proof, yet for the mere fact that he suspects he narrowly escaped the fate of Stella Lamar and Werner." Kennedy pressed the button. "Witness the effort to kill the man playing the part of the Black Terror." The print was terribly bad, in appearance almost a "dupe," due to the speed with which it had been made. Nevertheless the two very brief scenes rushed through for this showing were more absorbingly thrilling, more graphic than anything ever to be seen even in a news reel at a movie theater. "Notice!" Kennedy exclaimed. "He puts his hand in one pocket, he fumbles, hesitates, then finds the bottle in the other. Whoever put the poison in the vial replaced it in the wrong pocket. The film shows that very clearly. The camera proves that it was not an attempt at suicide. Yet the poison used was belladonna, selected because this victim had purchased some and because it would seem sure, therefore, that he had committed suicide." We sat in silence, listening, horrified. "There is still another matter," Kennedy went on, after a moment. "The fire in the negative vault this morning was incendiary. I have proved to the satisfaction of several of us that a bomb was constructed of wet phosphorus and old film and placed in the vault by trickery four days ago, the same day Stella Lamar was killed. Through a miscalculation the phosphorus was slow in drying and the fire did not occur until to-day. Thanks to that fact I have in my possession a bit of negative which the murderer very likely wished to have destroyed; in fact, I believe its destruction to be the motive in planning the fire in the vault." He faced the operator. "Ready to run the negative?" "Yes, sir!" Kennedy pressed the button and when the projection machine threw its picture upon the screen I saw something such as I had never imagined before. Everything was black which should have been white and everything white which should have been black. The two extremes shaded into each other in weird fashion. In fact it was uncanny to watch a negative projected and I followed, fascinated. "This is a film made with the co-operation of Doctor Nagoya of the Castleton Institute and I am told by Mr. Manton that it is one of the finest snake pictures ever made." Kennedy spoke fast, so that we would get the full benefit of his explanation and so that it would not be necessary to subject the negative to the wear and tear of the sprocket wheels in the projection machine again. "I am running this for you to show you the action of the rattlesnake, whose venom was used to kill Miss Lamar, and to give you an idea of the source of the murderer's knowledge of snake poison." At this moment Doctor Nagoya, whom I could barely recognize in the inverted photography, seized one of the rattlers. It was a close-up and we could see the reptile dart out its forked tongue, seeking to get at the hands of the Japanese, locked firmly about its neck. Then another man walked into the picture, holding a jar. At once the snake struck at the glass. As it did so it was possible to see drops of the venom projected into the jar. Other details followed and there were views of other sorts and breeds of snakes, from the poisonous to the most harmless. The principal scene, however, had been the one showing the venom. "Lights up!" The operator threw the switch again, stopping the film and at the same time lighting the projection room. Kennedy stepped forward and turned to face us. "There was this negative in the vaults." He spoke rapidly. "It bore a certain name on the film, as editor. Some one knew that proof of the possession of this knowledge of snakes might prove a powerful link in the chain against him. If that had been a positive instead of a negative, you would have recognized Doctor Nagoya's 'assistant.' There was a double motive in blowing that vault--to destroy the company and to protect himself. In fact, all the rest of the negative was destroyed. Only by chance I saved this piece--the very one that he wanted to destroy." Everyone waited breathlessly for Kennedy's next move. Suddenly Kennedy flushed. I could see that he became genuinely angry. "In this room," he exclaimed, "there sits the most unscrupulous, cold-blooded, inhuman being I have ever known. Yet he maintains silence, believing still that he can defy the scientific evidence of his crimes. I have not yet mentioned, however, the real proof of his guilt." Kennedy picked up one of the little envelopes, one which contained a blood smear. "During the explosion this morning a number of you were cut by falling glass. You will remember that I bound up your cuts, carefully cleansing each one and wiping away the blood. That gave me a sample of the blood of everyone but Miss Loring and Mr. Shirley. Subsequently, without their knowledge, I obtained a sample from each of them. Thus I have a specimen from everyone concerned, or possibly concerned in the murders." He glanced about, but even now there was no telltale revelation. "I have analyzed these and one shows that the person from whom I obtained the sample has been inoculated with antivenin. The mark on the envelope is the same as the mark on the envelope containing the towel fibers, a double proof. Furthermore, I am prepared to show that it is the same blood as the blood upon the portiere." He faced me. All at once his voice carried the sharpness of a whip. "Walter, relieve Mackay at the door and take his weapon. Let no one out. Mackay, come here!" An instant later the district attorney leaned over. He glanced at the mark indicated by Kennedy, then whispered a name. The next instant Kennedy rose. "I thought so," he muttered. Raising his voice, he addressed all of us. "Here is a man who thought crime so long that he believed he could get away with--murder! Not only did he commit a second murder and plan a third to cover the first, but he planted evidence against nearly all of you. He dropped the ampulla in McGroarty's car to implicate any one of four people. He coolly stole a cigarette case to put it where it would be found after the film fire and clinch suspicion. "For all this, what justification has he had? Jealousy, jealousy of the narrowest, most primitive, sort actuated him. Not only was he willing to kill Stella Lamar, but he sought to destroy every foot of negative in which she had appeared. He was jealous of her success, greater than his, jealous of her interest in other men, greater than her interest in him. Her divorce was maneuvered directly by him simply because he thought it would hurt and humiliate her, and for no other reason. "When nothing seemed to stop her, on her upward climb, when he realized that she was as ambitious as he was and that her position in the picture world alone interested her, he sought by devious means, by subtle schemes, by spreading dissatisfaction and encouraging dissension, to wreck the company which had made her. At the end--he killed her--waiting craftily until she was at the very climax of her finest piece of work, the opening scenes of 'The Black Terror.'" There was bitterness in Kennedy's tones. "Before, I would not believe that a man--" Suddenly the projection room was plunged into darkness. Some one had pushed the wall switch close by me. I backed into the doorway, raising my weapon to resist any attempt to escape. Almost at the same instant there were the sounds of a struggle. Kennedy had dashed forward in the darkness, sure of the position of his man, unafraid. A scream I recognized from the throat of Enid. I groped for the switch, but the operator in the booth anticipated me. In the first burst of illumination I saw that Kennedy had forced his antagonist back over the front row of chairs. Almost I heard the crack of the man's spine. I caught a glimpse of the man's face and gasped at the murderous rage as he struggled and strove to break Kennedy's iron grip. Enid was the first at Kennedy's side. With an expression I failed to analyze until long afterward she sought to claw at the murderer's unprotected features, twitching now in impotent fury. "You wrote that note for her to meet you at the tearoom," Kennedy muttered, eyes narrowing grimly, "knowing she would be dead before that time. You protected yourself against the poisoned needle in the portieres--but--your own blood convicts you--Millard!" THE END 
56902	----	TRANSCRIBER'S NOTE: Italics have been transcribed using _underscores_, bold with =equal signs=, and small capitals as ALL CAPITALS. Inconsistencies in punctuation have been silently corrected. A list of other corrections can be found at the end of the document. THE SOUL SCAR [Decoration] BOOKS BY ARTHUR B. REEVE _Craig Kennedy Detective Stories_ THE SOUL SCAR THE PANAMA PLOT THE ADVENTURESS THE TREASURE-TRAIN THE SILENT BULLET THE POISONED PEN THE DREAM DOCTOR THE EXPLOITS OF ELAINE THE ROMANCE OF ELAINE THE EAR IN THE WALL THE WAR TERROR GOLD OF THE GODS THE SOCIAL GANGSTER _Other Detective Stories_ GUY GARRICK CONSTANCE DUNLAP HARPER & BROTHERS, NEW YORK [ESTABLISHED 1817] [Illustration: HONORA WILFORD] THE SOUL SCAR A CRAIG KENNEDY SCIENTIFIC MYSTERY NOVEL BY ARTHUR B. REEVE AUTHOR OF _"The Treasure Train" "The Adventuress" "The Panama Plot" and other Craig Kennedy Stories_ [Logo] HARPER & BROTHERS PUBLISHERS NEW YORK AND LONDON THE SOUL SCAR Copyright, 1919, by Harper & Brothers Printed in the United States of America Published May, 1919 CONTENTS CHAP. PAGE I THE DEATH-DREAM 1 II THE MARBLE HEART 17 III THE FREUD THEORY 33 IV THE "HESITATION COMPLEX" 48 V THE PSYCHANALYSIS 63 VI THE "OTHER WOMAN" 78 VII THE CROOK DETECTIVE 93 VIII THE POISONED GLASS 108 IX THE ASSOCIATION TEST 123 X THE ORDEAL BEAN 138 XI THE RASCON REPORTS 153 XII THE "NEW MORALITY" 169 XIII THE MECHANICAL EAR 186 XIV THE "JUNG" METHOD 202 XV THE CONFLICTING CLUES 218 XVI THE FINESSE 234 XVII THE SUPPRESSED DESIRE 247 XVIII THE CONFESSION 261 XIX THE LIE-DETECTOR 274 XX THE SOUL SCAR 287 THE SOUL SCAR I THE DEATH-DREAM "It's the most perplexing case I've been up against, Kennedy, for a long time." Doctor Leslie, now medical adviser to the district attorney, had dropped in at the laboratory, and, to tell the truth, I was glad of the interruption. For from a retort Kennedy was evolving an olfactory offense which was particularly annoying to me, especially as I was struggling with an article on art for _The Star_. The things were incongruous, and the article suffered. "A case?" repeated Kennedy, mechanically. "Here--stick your foot up. That's fine," he added, as he scraped the sole and heel of Leslie's shoe, while Leslie fidgeted impatiently. "This is new." Apparently Leslie's case was forgotten before it was begun. "You know," Craig went on, eagerly, "the use of all these new leather substitutes is opening a new field for detectives in the study of foot marks. I've just been analyzing the composition of some of the products. I'll soon be able to identify them all. A case, you say--eh?" "Yes. You know the lawyer, Vail Wilford? Well, they found him in his office--this morning--dead--the lights on; a suicide--that is, it looked like a suicide at first. I don't know. The thing's a mystery to me." "Oh--a suicide?" Craig frowned, as though such a thing was entirely too trivial to interrupt his analysis of rubber heels. "He left this letter--to his wife," persisted Leslie. We read the note. HONORA [it began]--Don't think I am a coward to do this, but things cannot go on as they have been going. It is no use. I cannot work it out. This is the only way. So I shall drop out. You will find my will in the safe. Good-by forever. VAIL. The peculiarly pungent smell of burning rubber had by this time completely filled the laboratory. It was stifling, sickening. "There--you made me forget that test, with your confounded suicide," reproached Kennedy. "That sample's ruined." "Glad of it," I snorted. "Now I won't need a gas-mask." However, in curiosity I looked at the note again. It was, strangely enough, written on a typewriter. "Hm!" exclaimed Kennedy, with mild interest. "Suicides don't usually write on typewriters. A hasty scrawl--that's what you usually find." "But Wilford was an unusual man," I suggested. "You might look for almost anything from Wilford." I read the note again. And as I did so I asked myself whether it was a suicide note, after all. To me, now, it seemed too calmly composed and written for that, as Kennedy had suggested. I knew Wilford as a lawyer, still comparatively young and well known almost to the point of notoriety, for of late he had taken many society divorce cases. Altogether, his office had become a sort of fashionable court of domestic relations. "Here's the strange thing," hastened Leslie, taking advantage of Kennedy's momentary interest before he could return to another retort laden with some new material. "We found in the office, on the desk, two glasses. In one there seemed to be traces of nothing at all--but in the other I have discovered decided traces of atropin." "That looks promising," remarked Kennedy, his analysis now entirely forgotten. "That's why I decided to call you in. Will you help me?" "Craig," I interrupted, "I don't know much about Vail Wilford, but he has had such an unsavory reputation that--well, I'd hesitate. I've always considered him a sort of society rat." "What difference does that make, Walter?" argued Craig, turning on me suddenly. "If a crime has been committed, I must get at it. It is my duty--even if the man is a 'rat,' as you call him. Besides, this promises to be a very interesting case. Where is the body?" he asked, abruptly, in as matter-of-fact a tone as if it had been a wrecked car towed to a garage. "Removed to his apartment on the Drive," replied Doctor Leslie, now much encouraged and not concealing it. "I've just come from the place. That was where I saw Honora Wilford." "How did Mrs. Wilford take it?" asked Craig. "Has she been told all this yet?" "Not about the atropin, I think. That's just what I wanted to tell you about. She was grief-stricken, of course. But she did not faint or do anything like that." "Then what was it?" hastened Kennedy, impatiently. "When we told her," replied Leslie, "she exclaimed: 'I knew it! I knew it!' She stood at the side of the bed where the body had been placed. 'I felt it!' she cried. 'Only the other night I had such a horrible dream. I dreamed I saw him in a terrific struggle. I could not make out who or what it was with which he struggled. I tried to run to him. But something seemed to hold me back. I could not move. Then the scene shifted--like a motion picture. I saw a funeral procession and in the coffin I could see as though by a second sight, a face--his face! Oh, it was a warning to me--to him!' "I tried to calm her," went on Leslie. "But it was of no use. She kept crying out: 'It has come true--just as I saw in the dream. I feared it--even when I knew it was only a dream.' Strange, don't you think, Kennedy?" "Why didn't you tell me this before?" asked Craig, impatiently. "Didn't have a chance. You were studying my rubber heels." "Well--what then? Is there anything else?" "I questioned her," went on Leslie. "I asked her about her dreams. 'Yes,' she said, 'often I have had the dream of that funeral procession--and always I saw the same face--Vail's! Oh, it is horrible--horrible!'" Kennedy was studying Leslie now keenly, though he said nothing. "There's another thing, too," added Leslie, eagerly. "Although Mrs. Wilford seems to be perfectly normal, still I have learned that she was suffering from the usual society complaint--nervousness--nervous breakdown. She had been treated for some time by Doctor Lathrop--you know, the society physician they all run to?" Kennedy nodded. "Then, on a sort of docket, or, rather, calendar for private notes by dates, on the desk of Wilford, I discovered this entry, among others, 'Prepare papers in proposed case of Lathrop _vs._ Lathrop.' I turned back the calendar. Several times, on previous days, covering quite a period of time, I found entries like this: 'Vina at four,' 'Vina at six,' and other dates." I glanced over at Kennedy. Vina Lathrop! I knew also of Vina Lathrop, the beautiful wife of the society physician. It was certainly news that a divorce proceeding had even been contemplated. I could imagine how the newspapers would revel in it when they knew. "Then you'll go?" queried Doctor Leslie, anxiously. Kennedy completely ignored my earlier objection. "Certainly I'll go," he replied, pulling off his stained smock. Ten minutes later, with Doctor Leslie, we came to the Wilford apartment, one of those ornate and expensive multiple dwellings that front the river and command a rental that fixes a social station in certain sets. Following him, we rode up in the elevator, and had scarcely been admitted to the Wilford suite when we were greeted familiarly by a voice. It was Doyle, of the detective bureau, a sleuth of the old school, but for all that a capital fellow and one with whom we got along very nicely, so long as we flattered him and allowed him a generous share of credit when the rounding out of a case came about. "What do you really _know_ about her?" he whispered, finally, after a few moments' chat, jerking his thumb ominously as he pointed with it down the hall in the direction of a room where I supposed that Honora Wilford must be. "Very little, it's true," cut in Leslie. "I think our report said that her maiden name was Honora Chappelle, that her father, Honore Chappelle, made quite a fortune as an optician, that she was an only child and inherited--" "I don't mean her pedigree," scorned Doyle. "I mean modern history. Now, I've been making some inquiries, from the neighbors and others, and I've had a couple of men out picking up stray bits of information." Doyle leaned over patronizingly to Kennedy, as much as to say that, with all Craig's science, he couldn't beat the organization of the regular force, a contention Kennedy was always quite willing to admit. "I have just learned," informed Doyle, "that Wilford had been having her shadowed. They tell me, too, that she has been seen once or twice with an old friend of hers, Vance Shattuck, the broker. They tell me that before she married Wilford she was once engaged to Shattuck. Know him?" he asked, turning to me. "I've heard of him," I replied. "I guess he's well known on Wall Street--seems to get his name into the papers often enough, anyhow, in one scandal or another." "Well, I think that dream stuff is all camouflage, just between you and me," nodded Doyle, sagely, drawing a piece of paper from his pocket. "I've been going over things pretty carefully since I've been here. In her desk I found this thing." He held out the paper to Kennedy. It was a page torn out of a book of poetry, an anthology, I imagined, for on the page was printed the title of a sonnet, "Renouncement," and the name of the author, Alice Meynell. On the wide margin of the page was written in ink, in what Doyle assured us was Mrs. Wilford's own handwriting, the notation, "One of the greatest sonnets of pure emotion." We all read it and I am forced to admit that, whatever our opinion might have been of Honora Wilford before, we were convinced that her literary judgment was not at fault. I add the sonnet: I must not think of thee; and tired, yet strong, I shun the love that lurks in all delight-- The love of thee--and in the blue heaven's height And in the dearest passage of a song. Oh, just beyond the sweetest thoughts that throng This breast, the thought of thee waits hidden, yet bright; But must it never, never come in sight; I must stop short of thee the whole day long. But when sleep comes to close each difficult day, When night gives pause to the long watch I keep, And all my bonds I needs must loose apart, Must doff my will as raiment laid away-- With the first dream that comes, with the first sleep I run, I run, I am gathered to thy heart. Kennedy folded up the sonnet and its notation, and, without a word, turned from Doyle and looked about the room in which we were, a little reception-room. On the table before Doyle there were two glasses, as well as some other objects which Doyle had either collected or brought with him from the office. "I suppose those are the glasses you found at the office," ventured Kennedy. "In one of them I understand that traces of atropin were found." Doyle nodded. "What's that?" asked Craig, pointing to a cut-glass-stoppered bottle which was standing by the glasses, empty. "That? It was found with a vanity-case and some other things on her dressing-table. It once contained belladonna--atropin, you know. I've had her maid, Celeste, cross-examined. Mrs. Wilford used belladonna to brighten her eyes sometimes, as many society women do." I shot a glance of inquiry at Doyle, who nodded. "So far, we haven't been able to connect Mrs. Wilford directly with the mystery, but we're keeping the evidence," he confirmed. I must admit that both Doyle's information and his general attitude after what we had heard from Leslie came as a shock. Yet, try as I might, I had to admit that even if that were the purpose for which Honora Wilford had the belladonna, it need not have been the only use to which she put it. Doyle was raising a very serious presumption, at least. A poison like belladonna was a dangerous weapon, I reasoned, in the hands of a jealous woman. The mere possession of it and the traces of atropin in the glass did, I confessed, look badly. A moment later, with the physician and the detective, we entered the room where the body lay. Wilford had been a large and rather forceful figure in life. I knew him as a man of unusual ability, though I despised the direction in which his legal talents had been diverted. Perhaps, I thought, unusual talents had brought unusual temptations. For, whatever we may have thought of people in life, our judgments are necessarily softened by death. As I looked at him now, I could not escape the feeling that his peculiar kind of success somehow would afford the basic reason which would prove to be the solution of the mystery before us. At length Kennedy straightened up and turned to us, a peculiar look on his face. "What is it?" I queried, impatiently. "Have you discovered something already?" Without replying for the moment, Kennedy glanced down significantly at the eye of Wilford as he held the lid with his finger. "Atropin, you know, would dilate the pupil," he remarked, simply. We took a step closer and looked. The pupils of both eyes were contracted. "I know," remarked Doyle, wisely, "but there may have been something else. You remember the Buchanan case?" Before any one could answer, he went on: "Remember when the Carlyle Harris case was going on, the testimony showed that Helen Potts's eyes had been contracted to a pin-point? Well, at that time Doctor Buchanan, a dentist down on Staten Island, I think, was talking to a patient. He said that Harris was a fool--that all he needed to have done was to have put some atropin in the capsule with the morphine--and her pupils would have expanded--and thus covered up the morphine clue. Later, when he himself was accused of murder, the patient recollected what the doctor had said, and it was found that he had tried the very thing himself. It was proved against him. Perhaps there is something like that." Kennedy nodded sententiously at Doyle's wisdom, but did not betray what his real opinion was, if indeed he had formed any so soon. "You have examined the contents of the stomach?" asked Craig of Leslie. Doctor Leslie shook his head. "Not yet. I have not had time. Remember, it is only a couple of hours since this case was handed over to me and it has been only a matter of minutes since I learned that there was anything suspicious." "Then I suppose you have no objection to my sharing the examination with you?" "None whatsoever. In fact, I should welcome it. Leave it to me. I will arrange for samples of everything to be sent to you at your laboratory at the very first opportunity." "Very well, then," thanked Kennedy. "Now I should like to see Mrs. Wilford, if she is here." "You bet she's here," ejaculated Doyle. "You don't suppose I'd let her get away, do you?" He led the way down the hall to a sort of drawing-room. Honora Wilford was a tall, perfectly formed woman, a beautiful woman, too. At first glance she gave one an impression of youth, though soon one saw that she was mature. I think that for that very reason she was fascinating. There was something baffling about her. Remembering what Leslie had said about the dream, I was surprised to see she was of anything, apparently, but a hysterical nature. One would not have thought her to be the type subject to hallucinations of any nature. Honora had large, lustrous, gray-blue eyes. From her carefully dressed chestnut hair to her dainty, fashionable foot-gear she was "correct." Her face had what people call "character." Yet, as I studied it and the personality it expressed, I had an indefinable feeling that there was something wanting. It was some time before I was able to catch it, much less express it. But as she talked I realized what it was. Her beauty was that of a splendid piece of sculpture--cold, almost marble. There seemed to be something lacking. I could not at first define it, yet I felt that it was lacking, nevertheless. The very perfection I saw fell short of some quality. It was that elusive thing we call "heart." As we entered with Doyle, Honora seemed to ignore him. Once I saw her covertly eying Kennedy, after our introduction, as though estimating him. Doyle had glossed the introduction over by saying that we were a "couple of scientists." What idea it conveyed to Mrs. Wilford I do not know. It meant nothing to me, except that Doyle suffered from either secret jealously or contempt. "I understand," questioned Doyle, in his best third-degree, hammer-and-tongs method, "that some time ago you had a disagreement with Mr. Wilford and even threatened to leave him." "Yes?" parried Honora, without admitting a syllable. "I didn't leave him, though, did I?" I watched her closely. She did not flinch from the questioning, nor did she betray anything. Her face wore an expression of enforced calmness. Had she steeled herself for this ordeal, as merely the first of many? Try as he might, Doyle could not shake her calmness. Yet all the time he gave the impression that he was holding something in reserve against her. "We shall have to require you to stay here, for the present," added Doyle, ominously, as his man summoned him outside for some message from headquarters. I saw what his idea was. It was a refinement of torture for her--in the hope that, surrounded by things that would keep the tragedy constantly in her mind, she might break down. Honora, on the other hand, did not seem to me to be entirely frank with the detective. Was it that Doyle, by his manner, antagonized her? Or was there some deeper reason? For a moment we were alone with her. If I had expected any appeal to Kennedy, I was mistaken. "I understand that you have been under the care of Doctor Lathrop," hazarded Craig. "Yes," she replied; "I've been so run down and miserable this season in town that I needed some treatment." "I see," considered Kennedy. "Doctor Leslie has told me. He also told me about your dreams." She averted her eyes. "They have made me even more nervous," she murmured, and I now noticed that it was quite true that her apparent placid exterior was merely a matter of will-power. "Do you dream more--or less, lately?" Craig asked. "That is, I mean since you have been consulting Doctor Lathrop. Has his treatment done you any good?" I wondered whether, beneath her nervousness, she was on guard always. "I think I have been getting more and more nervous, instead of less," she answered, in a low tone. "So many dreams of Vail--and always dreams of warning--of death. My dreams are so peculiar, too. Why, last night I dreamed even of Doctor Lathrop. In the dream I seemed to be going along a path. It was narrow, and as I turned a corner there was a lion in the way. I was horribly frightened, of course--so frightened that I woke up. The strange part of it was that, as I recollected the dream, the face of the lion seemed to be that of Doctor Lathrop." "Have you told him? What does he say?" "I haven't had a chance to see him--though by the way I feel after this tragedy I shall need a physician--soon. He tells me that I am run down, that I need a complete change of surroundings." It was evident that, whatever the reason, her nervous condition was quite as she described it. Kennedy evidently considered that nothing was to be gained by questioning her further just at that moment, and we left her. Outside we were joined by Doctor Leslie. "What do you think of it?" he asked. "A most peculiar tangle, to say the least," remarked Kennedy. "Just consider it. Here are two couples--Wilford and Honora, Doctor Lathrop and his wife, Vina. We may suspect, from what you found at the office, something in the relations of Wilford and Vina. As to the doctor and Honora--we don't know. Then, into the case seems to have entered a fifth person, Vance Shattuck. Really, Leslie, I cannot say anything now. It seems as though it might be quite complicated. I shall have to visit them, talk with them, find out. You and Doyle will keep me informed?" "Certainly. And I will let you have the materials for your tests as soon as possible." As we left the apartment, Kennedy appeared preoccupied. "Those dreams were peculiar," he remarked, slowly, almost to himself. I glanced at him quickly. "You don't mean to say that you attach any importance to dreams?" I remarked. Kennedy merely shrugged. But I knew from his actions that he did. II THE MARBLE HEART "I'm going to get acquainted with the people in this case," remarked Kennedy, as he left the Wilford apartment, "and first of all it will be with Vance Shattuck." We found that Shattuck lived in a rather sumptuous bachelor apartment farther up the Drive, to which we were admitted by his Japanese valet, who led the way into a sort of den, then disappeared to summon his master. As we waited in the den I glanced about. It was a most attractive and fascinating place. There were innumerable curios that seemed to have been gathered from all over the world. Nor were they merely thrown together in a jumble. It was artistic, too, with a masculine art. From the manner of the valet, though he had said nothing, I somehow gathered that Shattuck had been waiting for something or somebody. It was no longer early in the morning and I knew that he must have been neglecting his business, that is, if he really had any to neglect. I wondered why he should be doing so. A few minutes later Shattuck himself appeared, a slim, debonair, youngish-old man, with dark hair of the sort that turns iron-gray in spots even in youth. Somehow he gave the impression of being a man of few words, of being on guard even thus early in our meeting. "You have evidently traveled considerably," commented Kennedy, as he entered and we introduced ourselves. "Yes, a great deal, before the war," replied Shattuck, guardedly watching. "In Africa, I see," added Kennedy, who had been examining some striking big-game photographs that hung on a side wall. "Once I was in Africa--yes. But I contracted a fever there. It has left me unable to stand the fatigue I used to stand. However, I'm all right--otherwise--and good for a great many years in this climate--so my doctor tells me." "Doctor Lathrop?" suggested Kennedy, quickly. Shattuck evaded replying. "To what am I indebted for the honor?" he queried, coldly now, still standing and not offering us seats. "I suppose you have heard of the death of Vail Wilford?" asked Kennedy, coming directly to the point. "Yes. I have just learned that he was found dead in his office, the lights turned on, and with a note left by him to his wife. It's very sudden." "You were acquainted with Honora Wilford, I believe?" Shattuck flashed a quick glance sidewise. "We went to school together." "And were engaged once, were you not?" Shattuck looked at Kennedy keenly. "Yes," he replied, hastily. "But what business of yours--or anybody's, for that matter--is that?" A moment later he caught himself. "That is," he added, "I mean--how did you know that? It was a sort of secret, I thought, between us. She broke it off--not I." "She broke off the engagement?" "Yes--a story about an escapade of mine, and all that sort of thing, that kind mutual friends do so well for one in repeating--but! by Jove, I like your nerve, sir, to talk about it--to me. The fact of the matter is, I prefer not to talk about it. There are some incidents in a man's life, particularly where a woman is concerned, that are a closed book." He said it with a mixture of defiance and finality. "Quite true," hastened Kennedy, briskly, "but a murder has been committed. The police have been called in. Everything must be gone over carefully. We can't stand on any ceremony now, you know--" At that moment the telephone rang and Shattuck turned quickly toward the hall as his valet padded in after having answered it softly. "You will excuse me a moment?" he begged. Was this call what he had been waiting for? I looked about, but there was no chance to get into the hall or near enough in the den to overhear. While Shattuck was at the telephone, Kennedy paced across the room to a bookcase. There he paused a moment and ran his eye over the titles of some of the books. They were of a most curious miscellaneous selection, showing that the reader had been interested in pretty nearly every serious subject and somewhat more than a mere dabbler. Kennedy bent down closer to be sure of one title, and from where I was standing behind him I could catch sight of it. It was a book on dreams translated from the works of Dr. Sigmund Freud. Kennedy continued to pace up and down. Out in the hall Shattuck was still at the telephone and we could just make out that he was talking in a very low tone, inaudible to us at a distance. I wondered with whom it might be. From his manner, which was about all we could observe, I gathered that it was a lady with whom he talked. Few of us ever get over the feeling that in some way we are in the presence of the person on the other end of the wire. Could it have been with Honora Wilford herself that he was talking? A few moments later Shattuck returned from the telephone. "Have you met Mrs. Wilford recently?" asked Kennedy, picking up the conversation where he had been interrupted by the call. Shattuck eyed Kennedy with hostility and grunted a surly negative. I felt that it was a lie. "I suppose you know that she has been suffering from nervous trouble for some time?" he continued, calmly ignoring Shattuck's answer, then adding, sarcastically, "I trust you won't consider it an impertinence, Mr. Shattuck, if I ask you whether you were aware that Doctor Lathrop was Mrs. Wilford's physician?" "Yes, I am aware of it," returned Shattuck. "What of it?" "He is yours, too, is he not?" asked Kennedy, pointedly. Shattuck was plainly nettled by the question, especially as he could not seem to follow whither Kennedy was drifting. "He was once," he answered, testily. "But I gave him up." "You gave him up?" It has always been a source of enjoyment to me to watch Kennedy badgering an unwilling and hostile witness. Shattuck was suddenly finding himself to be far from the man of few words he thought himself. It was not so much in what Kennedy asked as the manner in which he asked it. Shattuck was immediately placed on the defensive, much to his chagrin. "Yes. I most strenuously object to being the subject of--what shall I call it--perhaps--this mental vivisection, I suppose," he snapped, vexed at himself for answering at all, yet finding himself under the necessity of finishing what he had unwillingly begun under the lash of Kennedy's quizzing. Kennedy did not hesitate. "Why?" he asked. "Do you think that he sometimes oversteps his mark in trying to find out about the mental life of his patients?" Shattuck managed to control a sharp reply that was trembling on his tongue. "I would rather say nothing about it," he shrugged. "I see you are a student of Freud yourself," switched Kennedy, quickly, with a nod toward the bookcase. "And of many other things," retorted Shattuck. "You'll find about a ton of literature in that bookcase." "But it was about her dreams," persisted Kennedy, "that she consulted Doctor Lathrop, I believe. Are you acquainted with the nature of the dreams?" Shattuck eyed him in silence. It was evident that he realized that the only refuge from the quizzing lay in that direction. "Really, sir," he said, at last, "I don't care to discuss a thing I know nothing about any further." He turned, as though only by a studied insult could he find escape. I expected Kennedy to flare up, but he did not. Instead, he was ominously polite. "Thank you," he said, with a mocking sarcasm that angered Shattuck the more. "I suppose I may reach you at your place of business, later, if I need?" Shattuck nodded, but I knew there was a mental reservation back of it and that his switchboard operator would be given instructions to scrutinize every call carefully, and that, should we call up, Mr. Shattuck would have "just stepped out." As for Kennedy's tone, I was sure that it boded no good for Shattuck himself. Perhaps Kennedy reasoned that there would be plenty of other interviews later and that it was not worth while fighting on the first. On his part Shattuck could do no less than assume an equal politeness as he bowed us out, though I know that inwardly he was ready to consign us to the infernal regions. Kennedy was no sooner in the street than he hastened to a near-by telephone-booth. Evidently the same thought had been in his mind as had been in mine. He called up Doyle at the Wilford apartment immediately and inquired whether Honora Wilford had made any telephone calls recently. To my surprise, though I will not say to his own, he found out that she had not. "Then who was it called Shattuck?" I queried. "I could have sworn from his manner that he was talking to a woman. Could it have been to the maid?" He shook his head. "Celeste is watched, too, you know. No, it was not Celeste that called up. He would never have talked that long nor as deferentially to her. Never mind. We shall see." Back on the Drive again, we walked hastily up-town a few squares until we came to another apartment, where, in a first-floor window, I saw a little sign in black letters on white, "Dr. Irvin Lathrop." Fortunately it was at a time when Lathrop was just finishing his office hours, and we had not long to wait until the last patient had left after a consultation. As we waited I could see that even his waiting-room was handsomely furnished and I knew that it must be expensive, for our own small apartment, a little farther up-town and around the corner from the Drive, cost quite enough, though Kennedy insisted on keeping it because it was so close to the university where he had his laboratory and his class work. As Lathrop flung the door to his inner office open I saw that he was a tall and commanding-looking man with a Vandyke beard. One would instinctively have picked him out anywhere as a physician. Lathrop, I knew, was not only well known as a specialist in nervous diseases, but also as a man about town. In spite of his large and lucrative practice, he always seemed to have time enough to visit the many clubs to which he belonged and to hold a prominent place in the social life of the city. Not only was he well known as a club-man, but he was very popular with the ladies. In fact, it was probably due to the very life that he led that his practice as a physician to the many ills of society had grown. "I suppose you know of the suicide of Vail Wilford?" asked Kennedy, as he explained briefly, without telling too much, our connection with the case. Doctor Lathrop signified that he did know, but, like Shattuck, I could see that he was inclined to be cautious about it. "I've just been talking to Honora Wilford," went on Craig, when we were settled in the doctor's inner office. "I believe she was a patient of yours?" "Yes," he admitted, with some reluctance. "And that she had been greatly troubled by nervousness--insomnia--her dreams--and that sort of thing." The doctor nodded, but did not volunteer any information. However, his was not the hostility of Shattuck. I set it down to professional reticence and, as such, perhaps hard to overcome. "I understand, also," pursued Kennedy, affecting not to notice anything lacking in the readiness of the answer, "that Vance Shattuck was friendly with her." The doctor looked at him a moment, as though studying him. "What do you mean?" he asked, evasively. "What makes you say that?" "But he was, wasn't he? At least, she was friendly with him?" Kennedy repeated, reversing the form of the question to see what effect it might have. "I shouldn't say so," returned the doctor, slowly, though not frankly. Kennedy reached into his pocket and drew forth the sonnet which he had taken from Doyle back at the Wilford apartment. "You will recognize the handwriting in that notation on the margin," he remarked, quietly. "It is Mrs. Wilford's. Her sentiment, taken from the poem, is interesting." Lathrop read it and then reread it to gain time, for it was some moments before he could look up, as though he had to make up his mind just what to say. "Very pretty thought." He nodded, scarcely committing himself. Lathrop seemed a trifle uneasy. "I thought it a rather strange coincidence, taken with the bit I learned of her dreams," remarked Kennedy. Lathrop's glance at Kennedy was one of estimation, but I saw that Kennedy was carefully concealing just how much, or rather at present how little, he actually knew. "Ordinarily," remarked Lathrop, clearing his throat, "professional ethics would seal my lips, but in this instance, since you seem to think that you know so much, I will tell you--something. I don't like to talk about my patients, and I won't, but, in justice to Mrs. Wilford, I cannot let this pass." He cleared his throat again and leaned back in his chair, regarding Kennedy watchfully through his glasses as he spoke. "Some time ago," he resumed, slowly, "Mrs. Wilford came to me to be treated. She said that she suffered from sleeplessness--and then when she slept that her rest was broken by such horrible fantasies." Kennedy nodded, as though fully conversant already with what the doctor had said. "There were dreams of her husband," he continued, "morbid fears. One very frequent dream was of him engaged in what seemed to be a terrific struggle, although she has never been able to tell me just with what or whom he seemed to struggle. She told me she always had a feeling of powerlessness when in that dream, as though unable to run to him and help him. Then there were other dreams that she had, especially the dreams of a funeral procession, and always in the coffin she saw his face." Kennedy nodded again. "Yes, I know of those dreams," he remarked, casually. "And of some others." For a moment Kennedy's manner seemed to take the doctor off his professional guard--or did he intend it to seem so? "Only the other day," Lathrop went on, a moment later, "she told me of another dream. In it she seemed to be attacked by a bull. She fled from it, but as it pursued her it seemed to gain on her, and she said she could even feel its hot breath--it was so close. Then, in her dream, in fright, as she ran over the field, hoping to gain a clump of woods, she stumbled and almost fell. She caught herself and ran on. She expected momentarily to be gored by the bull, but, strangely enough, the dream went no farther. It changed. She seemed, she said, to be in the midst of a crowd and in place of the bull pursuing her was now a serpent. It crept over the ground after her and hissed, seemed to fascinate her, and she trembled so that she could no longer run. Her terror, by this time, was so great that she awoke. She tells me that as often as she dreamed them she never finished either dream." "Very peculiar," commented Kennedy. "You have records of what she has told you?" "Yes. I may say that I have asked her to make a record of her dreams, as well as other data which I thought might be of use in the diagnosis and treatment of her nervous troubles." "Might I see them?" Lathrop shook his head emphatically. "By no means. I consider that they are privileged, confidential communications between patient and physician--not only illegal, but absolutely unethical to divulge. There's one strange thing, though, that I may be at liberty to add, since you know something already. Always, she says, these animals in the dreams seemed to be endowed with a sort of human personality. Both the bull and the serpent seemed to have human faces." Kennedy nodded at the surprising information. If I had expected him to refer to the dream of Doctor Lathrop which she herself had told, I was mistaken. "What do you think is the trouble?" asked Kennedy, at length, quite as though he had no idea what to make of it. "Trouble? Nervousness, of course. I readily surmised that not the dreams were the cause of her nervousness, but that her nervousness was the cause of her dreams. As for the dreams, they are perfectly simple, I think you will agree. Her nervousness brought back into her recollection something that had once worried her. By careful questioning I think I discovered what was back of her dreams, at least in part. It's nothing you won't discover soon, if you haven't already discovered it. It was an engagement broken before her marriage to Wilford." "I see," nodded Kennedy. "In the dreams, you remember, she saw a half-human face on the animals. It was the face of Vance Shattuck." "I gathered as much," prompted Kennedy. "It seems that she was once engaged to him--that she broke the engagement because of reports she heard about his escapades. I do not say this to disparage Mr. Shattuck. Far from that. He is a fine fellow--an intimate friend of mine, fellow-clubmate, and all that sort of thing. That was all before he made his trips abroad--hunting, mostly, everywhere from the Arctic to Africa. The fact of the matter is, as I happen to know, that since he traveled abroad he has greatly settled down in his habits. And then, who of us has not sown his wild oats?" The doctor smiled indulgently at the easy-going doctrine that is now so rapidly passing, especially among medical men. "Well," he concluded, "that is the story. Make the most of it you can." "Very strange--very," remarked Kennedy, then, changing the angle of the subject, asked, "You are acquainted with the recent work and the rather remarkable dream theories of Doctor Freud?" Doctor Lathrop nodded. "Yes," he replied, slowly, "I am acquainted with them--and I dissent vigorously from most of Freud's conclusions." Kennedy was about to reply to this rather sweeping categorical manner of settling the question, when, as we talked, it became evident that there was some one just outside the partly open doors of the inner office. I had seen a woman anxiously hovering about, but had said nothing. "Is that you, Vina?" called Doctor Lathrop, also catching sight of her in the hall. "Yes," she replied, parting the portières and nodding to us. "I beg pardon for interrupting. I was waiting for you to get through, Irvin, but I've an appointment down-town. I'm sure you won't mind?" Vina Lathrop was indeed a striking woman; dark of hair, perhaps a bit artificial, but of the sort which is the more fascinating to study just because of that artificiality; perhaps not the type of woman most men might think of marrying, but one whom few would fail to be interested in. She seemed to be more of a man's woman than a woman's woman. "You will excuse me a moment?" begged the doctor, rising. "So, you see," he finished with us, "when you asked me whether she was friendly with Shattuck, it is quite the opposite, I should--" "You're talking of Honora?" interrupted the doctor's wife. Doctor Lathrop introduced us, as there seemed to be nothing else to do, but I do not think he was quite at ease. "I don't think I would have said that," she hastened, almost ignoring, except by an inclination of the head, the introduction in the eagerness to express an idea his words had suggested. "I don't think Honora is capable of either deep love or even deep hate." "A sort of marble woman?" suggested the doctor, at first biting his lips at having her in the conversation, then affecting to be amused, as though at one woman's spontaneous estimate of another. Vina shrugged her prettily rounded shoulders, but said no more on the subject. "I sha'n't be gone long," she nodded back. "Just a bit of business." She was gone before the doctor could say a word. Had the remark in some way been a shot at the doctor? All did not appear to be as serene between this couple as they might outwardly have us believe. I saw that the interruption had not been lost on Kennedy. Had it been really an interest in our visit that had prompted it? Somehow, I wondered whether it might not have been this woman who had called up Shattuck while we were there. But why? We left the doctor a few minutes later, more than ever convinced that the mystery in the strange death of Vail Wilford was not so simple as it seemed. III THE FREUD THEORY "Until I receive those materials from Doctor Leslie to make the poison tests," considered Kennedy, as we walked slowly the few blocks to the laboratory, "I can't see that there is much I can do but wait." In his laboratory, he paused before his well-stocked shelves with their miscellaneous collection of books on almost every conceivable subject. Absently he selected a volume. I could see that it was one of the latest translated treatises on this new psychology from the pen of the eminent scientist, Dr. Sigmund Freud, and that it bore the significant title, _The Interpretation of Dreams_. Craig glanced through it mechanically, then laid it aside. For a few moments he sat at his desk, hunched forward, staring straight ahead and drumming his fingers thoughtfully. I leaned over and my eye happened to fall on the following paragraphs: "To him who is tortured by physical and mental sufferings the dream accords what has been denied him by reality, to wit, physical well-being and happiness; so the insane, too, see the bright pictures of happiness, greatness, sublimity, and riches. The supposed possession of estates and the imaginary fulfilment of wishes, the denial or destruction of which has just served as the psychic cause of the insanity, often form the main content of the delirium. The woman who has lost a dearly beloved child, in her delirium experiences maternal joys; the man who has suffered reverses of fortune sees himself immensely wealthy, and the jilted girl pictures herself in the bliss of tender love." The above passage from Radestock reveals with the greatest clearness the wish-fulfilment as a characteristic of the imagination, common to the dream and the psychosis. It is easy to show that the character of wish-fulfilment in dreams is often undisguised and recognizable, so that one may wonder why the language of dreams has not long since been understood. I read this and more, but, as I merely skimmed it, I could not say that I understood it. I turned to Kennedy, still abstracted. "Then you really regard the dreams as important?" I asked, all thought of finishing my own article on art abandoned for the present in the fascination of the mysterious possibilities opened up by the Wilford case. "Important?" he repeated. "Immensely so--indispensable, as a matter of fact." I could only stare at him. The mere thought that anything so freakish, so uncontrollable as a dream might have a serious importance in a murder case had never entered my mind. "If I can get at the truth of the case," he explained, "it must be through these dreams." "But how are you going to do that?" I asked, voicing the thought that had been forming. "To me, dreams seem to be just disconnected phantasmagoria of ideas--arising nowhere and getting nowhere, as far as I can see--interesting, perhaps, but--still, well, just chaotic." "Quite the contrary, Walter," he corrected. "If you had kept abreast with the best recent work in psychology, you wouldn't say that." "Well, what is this wonderful Freud theory, anyhow?" I asked, a bit nettled at his positive tone. "What do we know now that we didn't know before?" "Very much," he replied, thoughtfully. "There's just this to be said about dreams to-day. A few years ago they were all but inexplicable. The accepted explanations, then, were positively misleading and productive of all sorts of misapprehension and downright charlatanry." "All right," I argued. "That's just my idea of dreams. Tell me what it is that the modern dream-books have to say about them, then." "Don't be frivolous, Walter," Craig frowned. "Dreams used to be treated very seriously, it is true, by the ancients. But, as I just said, until recently modern scientists, rejecting the beliefs of the dark ages, as they thought, scouted dreams as senseless jumbles of ideas, uncontrolled, in sleep. That's your class, Walter," he replied, witheringly, "with the scientists who thought that they had the last word, just because it was, to them, the latest." Though I resented his correction, I said nothing, for I saw that he was serious. Mindful of many previous encounters with Craig in his own fields in which I had come off a bad second, I waited prudently. "To-day, however," he continued, "we study dreams really scientifically. We believe that whatever is has a reason. Many students had had the idea that dreams meant something in mental life that was not just pure fake and nonsense. But until Freud came along with his theories little progress had been made in the scientific study of dreams." "Granted," I replied, now rather interested. "Then what is his theory?" "Not very difficult to explain, if you will listen carefully a moment," Craig went on. "Dreams, says Freud, are very important, instead of being mere nonsense. They give us the most reliable information concerning the individual. But that is possible only if the patient is in entire rapport with the investigator. Later, I may be able to give you a demonstration of what I mean by that. Now, however, I want you to understand just what it is that I am seeking to discover and the method it is my purpose to adopt to attain it." The farther Kennedy proceeded, the more I found myself interested, in spite of my assumption of skepticism. In fact, I had assumed the part more because I wanted to learn from him than for any other reason. "But how do you think dreams arise in the first place?" I asked, more sympathetically. "Surely, if they have a meaning that can be discovered by a scientist like yourself, they must come in some logical way--and that is the thing I can't understand, first of all." "Not so difficult. The dream is not an absurd and senseless jumble, as you seem to think. Really, when it is properly understood, it is a perfect mechanism and has definite meaning in penetrating the mind." He was drawing thoughtfully on a piece of paper, as he often did when his mind was working actively. "It is as though we had two streams of thought," he explained, "one of which we allow to flow freely, the other of which we are constantly repressing, pushing back into the subconscious or the unconscious, as you will. This matter of the evolution of our individual mental life is much too long a story for me to go into just at present. "But the resistances, as they are called, the psychic censors of our ideas, so to speak, are always active, except in sleep. It is then that the repressed material comes to the surface. Yet these resistances never entirely lose their power. The dream, therefore, shows the material distorted. "Seldom does one recognize his own repressed thoughts or unattained wishes. The dream is really the guardian of sleep, to satisfy the activity of the unconscious and repressed mental processes that would otherwise disturb sleep by keeping the censor busy. That's why we don't recognize the distortions. In the case of a nightmare the watchman, or censor, is aroused, finds himself over-powered, as it were, and calls for help. Consciousness must often come to the rescue--and we wake up." "Very neat," I admitted, now more than half convinced. "But what sort of dreams are there? I don't see how you can classify them, study them." "Easily enough. I should say that there are three kinds of dreams--those which represent an unrepressed wish as fulfilled, those that represent the realization of a repressed wish in an entirely concealed form, and those that represent the realization of a repressed wish, but in a form insufficiently or only partially concealed." "But what about these dream doctors who profess to be able to tell you what is going to happen--the clairvoyants?" Kennedy shrugged. "Cruel fakers, almost invariably," he replied. "This is something entirely different, on an entirely different plane. Dreams are not really of the future, even though they may seem to be. They are of the past--that is, their roots are in the past. Of course, they are of the future in the sense that they show striving after unfulfilled wishes. Whatever may be denied in reality, we can nevertheless realize in another way--in our dreams. It's a rather pretty thought." He paused a moment. "Perhaps the dream doctors were not so fundamentally wrong as we think, even about the future," he added, thoughtfully, "though for a different reason than they thought and a natural one. Probably more of our daily life, conduct, moods, beliefs, than we think could be traced to preceding dreams." I began vaguely now to see what he was driving at and to feel the fascination of the idea. "Then you think that you will be able to find out from Mrs. Wilford's dreams more than she'll ever tell you or any one else about the case?" "Exactly." "Well, that doesn't seem so unreasonable, after all," I admitted, going back in my mind over what we had learned so far. "Why did Doctor Lathrop say he dissented from the theory?" Kennedy smiled. "Many doctors do that. There's a side of it all that is distasteful to them, I suppose. It grates on minds of a certain type." "What's that?" "The sex aspect. Sex life possesses, according to Freud, a far higher significance in our mental household than traditional psychology is willing to admit. And I don't know as I would say I'd go the whole distance with Freud, either." He paused contemplatively. "Yet there is much that is true about his sex theories. Take an example. There's much about married life that can be learned from dreams. Thus, why John Doe doesn't get along with his wife has always been a matter of absorbing interest to the neighborhood. Conversation is taken up by it; yellow journalism is founded on it. Now, psychology--and mainly dream analysis--can solve the question--often right things for both John and Jane Doe and set the neighborhood tongues at rest. Sex and sex relations play a big rôle in life, whether we like to admit it or not." "I see," I nodded. "Then you think that that's what Lathrop meant when he said he strongly disagreed with the theory?" "Without a doubt. That is perhaps the part of the theory from which he reacted--or said he did. You see, Freud says that as soon as you enter the intimate life of a patient you begin to find sex in some form. In fact, he says, the best indication of abnormality would be its absence. "Sex is one of the strongest of human impulses," Craig continued, as impersonally as if he were classifying butterflies, "yet the one impulse subjected to the greatest repression. For that reason it is the weakest point in our cultural development. However, if everything is natural there ought to be no trouble. In a normal life, says Freud, there are no neuroses." "But how does that all apply in this case?" I asked. "You must mean that we have to deal with a life that is not normal, here in the Wilford case." He nodded. "I was convinced of it, the moment Leslie called on me here. That was why I was interested. Before that I thought it was just an ordinary case that had stumped him and I was not going to pull his chestnuts out of the fire for him. But what he said put it in a different light. So did what Doyle told me, especially that sonnet he found. They didn't know it--don't know it yet--won't know it until I tell them. That doesn't alter the fact that it promises to be a unique case." He paced the floor a few moments, as though trying to piece together the fragments he possessed. "Let me proceed now with a preliminary psychanalysis, as the Freudians call it," he resumed, still pacing thoughtfully, "the soul analysis of Honora Wilford, as it were. I do not claim that it is final. It is not. But on such information and belief, as the lawyers say, as we have already, we are warranted in drawing some preliminary conclusions. They will help us to go on. If any of them are wrong, all we need to do is throw them overboard. Later, I shall add to that stock of information, in one way or another, and it may very greatly modify those conclusions. But, until then, let's adopt them as a working hypothesis." I could only wonder at him. It was startling in the extreme to consider the possibilities to which this new science of dreams might lead, as he proceeded to illustrate it by applying it directly to a concrete case which I had seen. "You recall what Leslie told us, what Mrs. Wilford told us, and what Doctor Lathrop later confirmed--her dream of fear?" Craig went on. "At present, I should say that it was a dream of what we call the fulfilment of a repressed wish. Dreams of fear are always important. Just consider fear for a moment. Fear in such a dream as this nearly always denotes a sexual idea underlying the dream. In fact, morbid anxiety means surely unsatisfied love. The old Greeks knew it. Their gods of fear were born of the goddess of love. Consequently, in her dream, she feared the death of her husband because, unconsciously, she wished it." I was startled, to say the least. "But, Craig," I remonstrated, "the very idea is repulsive. I don't believe for a moment she is that kind of woman. It's impossible." "Take this idea of dream-death of one who is living," ignored Kennedy. "If there is sorrow felt, then there is some other cause for the dream. But if there is no sorrow felt, then the dreamer really desires the death or absence of the person dreamed about. Perhaps I did put it a little too sweepingly," he modified; "but when all the circumstances are considered, as I have considered them in this case already, I feel sure that the rule will apply here." "Better not tell that to Doyle," I remarked. "Judging by his attitude toward Honora Wilford, he'd arrest her on sight, if he knew what you just said." "I shall not tell Doyle. A little knowledge is a dangerous thing to Doyle. I haven't indicted her--yet." Turning the thing over in my mind, I found it even more and more distasteful, and I could not resist expressing myself rather strongly to that effect. "I expected to have you quarrel with that conclusion," smiled Kennedy, calmly. "People always do, until they understand. Let me explain more fully what I mean. Remember, first, that in childhood death is synonymous with being away. And many of our dreams are only survivals of childhood, like the falling dreams. Take the night-shirt dream. I suppose that, in common with some other millions of mortals, you have dreamed of traveling on the Subway, we'll say, lightly clad. No one noticed it." "Yes," I laughed. "Only, finally I knew it--and how I have sneaked back home by deserted streets, afraid to be seen. Yet, when I met any one, as you say, the person didn't seem to be embarrassed--not a tenth as much as I." "It speaks well for you," nodded Kennedy, with mock gravity. "If you had felt that others saw and knew your shame, it would mean something entirely different. As it is, it is simply one of those survivals of childhood in which there is no sense of shame over nakedness. Other people don't show it, either. But, later in life, you learned shame. That's where your psychic censor comes in and makes you sneak home by the byways and hedges. And, still, others don't feel as you do about it in the dream. If they did, I'm afraid it might show your moral sense a bit perverted. However, that's just an illustration of what I mean when I say that the death-dream may often be a childhood survival." I listened without comment, for Craig was interesting, now. "To get back to the case we have," he resumed. "Take, for example, a girl who sees in her dream that her mother is dead. It may mean many things. But perhaps it means only that she wishes her mother away so that she may enjoy some pleasure that her strict parent by her presence denies. That's a more or less parallel case, you see." Even though I was now more willing than before to admit the interpretation as applied to Honora Wilford, I was not prepared to admit the theory. Though I said nothing about it, I was afraid that such dream analysis was pointing too strongly to Honora herself as one who unconsciously wished her husband out of the way. The idea repelled me at the same time that it fascinated. I realized what wide possibilities it opened. "Of all dreams," continued Kennedy, "anxiety-dreams are among the most interesting and important. Anxiety may originate in psychosexual excitement--the repressed libido, or desire, as the Freudians call it. Neurotic fear has its origin in sexual life and corresponds to a libido, or desire, which has been turned away from its object and has not succeeded in being applied." "That may be true," I admitted, "but don't you think it's a bit raw to accuse Honora of desiring the death of Vail Wilford just because she didn't love him? I'd hate to be a juryman in a case like that!" "Raw? Is it?" repeated Kennedy. "That is, is it in a dream? Just dissociate dreams from facts, Walter. Take the case. You see, that fits splendidly so far with what we know of her--her secret regard for Shattuck surviving after the broken engagement; her apparent coldness; her very real lack of feeling for her husband; the superficiality of it all; love not really felt, but shown because the world must see and it was the proper thing for her to show--even if in her heart she did not feel it." "I know all that," I insisted. "But, perhaps, after all, Lathrop may have some right on his side. Must one incriminate oneself by dreams?" Kennedy shook his head. "Often dreams that are apparently most harmless turn out to be sinister, if we take the pains to interpret them. All have the mark of the beast. For instance, practically all so-called day dreams of women are erotic in their inception. Those of men may be so, but quite as often are likely to be dreams of ambition more than of love. One cannot say that this distinction will always be. It is hard to predict what may happen in the future. Perhaps modern social conditions may change the very nature of woman--perhaps her ambition for a 'career' may submerge her emotional life. But--well, I doubt it. A few years don't wipe out the evolution and instincts of countless ages. Besides, Nature can be trusted to take care of herself. Sexless women won't have children--then after whom will the next generation after them take?" "But is that all there is to the dream theory?" I asked, nodding agreement on Kennedy's prediction. "Not a bit of it. Even those brief dreams that she has told will bear hours of study and analysis. Building up her true, inward character is like laying mosaic. You add here a bit, there a bit, here a stone of one color, there of another. It takes patience and study. When the pieces are all fitted together the picture will be very different from what even an intimate friend thinks; yes, different from what she herself in her own inmost heart thinks herself to be." He paused a moment, as though turning the dreams over in his mind to see whither they led. "There's another feature of her dream I want to call your attention to," he went on, "and that is the crowd as she fled from the bull. Crowds in dreams usually denote a secret. Whatever her true feelings toward Shattuck, she believes them to be locked in her own heart. Again, when she was pursued across the field she said she could feel the hot breath of the beast as he pursued her. From that I would assume at least that she knows that Shattuck loves her. Then she stumbled and almost fell. That can have but one meaning--her fear of becoming a fallen woman. But she caught herself and ran on, in the dream. She escaped." "What of the dream about Lathrop?" I asked. "We'll take that up later and try to interpret it. I am not sure of that one, myself. As for the others, I don't mean to say that I've put a final interpretation on them, either. Some things, such as I've told you, I know. But there are others still to be discovered. Just now the important thing is to get an understanding of Honora herself." He took a turn up and down the floor of the laboratory. "Honora Wilford," he said, slowly, at last, "is what the specialists would call a consciously frigid, unconsciously passionate woman." He paused significantly, then went on: "I suppose there have been many cases where an intellectual woman has found herself attracted almost without reason toward a purely physical man. You find it in literature continually--in the caveman school of fiction, you know. As an intellectual woman, Honora may suppress her nature. But sometimes, we believe, Nature will and does assert herself." Kennedy considered the laboratory impatiently. "No package from Leslie yet. I hardly know what to do--unless--yes--that is the thing, now that I have had time to think this all out. I must see Mrs. Wilford again--and alone." IV THE "HESITATION COMPLEX" Honora Wilford was still in the apartment where we had left her under the watchful care of one of Doyle's men. Undoubtedly she felt no disposition to stir out, for if she went out it was certain that she would have gone under the most galling espionage. It must have been maddening to a woman of her temperament and station in life to find herself so hedged about by restriction. Doubtless it was just that that Doyle had intended, in the hope that the strain to which he subjected her by it would shake her poise. Nevertheless, she received us with at least outward graciousness. Perhaps it was that she recognized some difference in the treatment which Kennedy accorded her over that from those whom Doyle had seen fit to place in charge of the apartment where once she had been mistress. At any rate, I thought she acted a bit weary and I felt genuinely sorry for her as she received us and questioned us with her eyes. "I've been very much interested in those dreams of yours," remarked Kennedy, endeavoring not to betray too much of the source of his information, for obvious reasons. "Doctor Leslie has told me of some of them--and I tried to get Doctor Lathrop to tell me of the others." "Indeed?" she queried merely, her large eyes bent on Kennedy in doubt, although she did not betray any trepidation about the subject. "I wonder whether you would mind writing them down for me?" Craig asked, quickly. "I've already done so once for Doctor Lathrop," she answered, as though trying to avoid it. "Yes," agreed Kennedy, quickly; "but I can hardly expect him to let me see them--professional ethics and all that sort of thing, you know, forbid." "I suppose so," she replied, with a little nervous smile. "Oh, if you really want me to do so, I suppose I can write them out again, of course--write them the best I can recollect." "It would be of great assistance indeed, I can assure you," encouraged Kennedy. Honora, without another demur, walked over to a little writing-desk which seemed to be her own. Kennedy followed and placed a chair for her. Then he stepped back, though not so far but that he could watch her. A moment she paused, toying with her fountain-pen, then began to write. "My most frequent dream is a horrible one," she began, writing in a firm hand, although she knew that she was observed and was weighing every word and action. "I have dreamed ever so many times that I saw Vail in a terrific struggle. I could not make out who or what it was with which he struggled." At this point she seemed to hesitate and pause. I saw that Kennedy was carefully noting it and every mood and action she exhibited. Then, after a moment, gathering herself together again, she wrote on: "I tried to run to him. But something seemed to hold me back. I could not move." Again she paused, then very slowly began to write on another line. "Then the scene shifted like a motion picture. I saw a funeral procession and in the coffin I could see a face. In all my dreams it has been the face of Vail." As she finished, she seemed now to be struggling with her emotions. The more I saw of Honora Wilford, the more I was unable to resist the fascination of studying her. She was a woman well worth study--a woman of baffling temperament, high-strung, of keen perception, yet always in the face of even such circumstances as these keeping herself under seemingly perfect control. Always I found myself going back again to my original impression of her. Somehow, indefinably, I felt that there was something lacking in this woman's life. Was it, as I had believed at first, "heart"? I wondered whether, after all, there had been lacking in this woman's life some big experience, whether ever she had really loved. I knew well what would have been the answer one might have received if she had been questioned. She would have pointed immediately to her married life as proof that she had loved--at least once upon a time. And yet, was it proof? Had she loved Vail Wilford deeply? The fact was that I did not, could not feel entirely unsympathetic toward her. Somehow, I felt, it could not have been entirely her fault, that she must have been the victim of circumstances or prejudices over which she had no control. At any rate, I determined that whatever lay at the bottom of it all was well worth our study and discovery. I hoped that the case would last. I wanted to see its development, and, if by any chance it was possible, the development of Honora herself, for I felt that once the gap, whatever it was and however it had arisen in her life, was closed she would be a most wonderful woman. At times when I thought of the manner of Doyle and his men toward her, it made me boil over. As for Kennedy, it was different. I did not understand Craig in this matter. Yet I knew him better than perhaps any one else. Whatever lay back of Craig's actions, always I knew there was sympathy. Some may have thought him cold, but I knew better. Kennedy had always represented to me science with a heart. As for Doyle--he was neither. Kennedy's voice recalled me to the matter of immediate importance before us. "There was also that dream of Doctor Lathrop about which you told me, in which he appeared as a lion," suggested Kennedy, as she stopped writing and handed him what she had written. "This is very good--just what I want, as a matter of fact. Won't you write that other dream for me, also?" With an air of resignation, as though she felt she was in our hands and had determined that her acts would be above criticism, she turned again to her desk, picked up the pen she had laid down, and wrote on a fresh sheet of paper: "In the dream I seemed to be going along a rocky path. It was narrow, and as I turned a bend there was a bearded lion in the way. I was terribly frightened. I woke up." She began a new line and added: "The lion seemed to have a human face. It seemed to resemble Doctor Lathrop." I contrasted the writing of this dream with the other. At least there had been no hesitation in writing this, I observed, whatever that might mean. Already I was coming to have some respect for the dream theory which I would have ridiculed only a few hours before Kennedy began to convince me. Honora laid down the pen and glanced up rather wearily as Kennedy ran his eye over what she had written. Much as it all aroused her curiosity, plainly the whole proceeding on the part of Craig was a sealed book to her. "There's just another dream, or, rather, two dreams," he said, in a moment, "that interested me almost as much when I heard of them. Doctor Lathrop happened to mention them without telling them and I'd like to get them from you." She glanced at him covertly, as much as to say, "So, then, you have been talking about me to him?" but she controlled whatever remark was on her tongue and said nothing. Instead, obediently again, she picked up the pen and wrote, while we waited and the minutes passed. Only now it seemed that she was writing more carefully, both taking more time over the actual legibility and the choice of words. "I seemed to be attacked by a bull," she detailed. "It was in a great field and I fled from it over the field. But it pursued me. It seemed to gain on me." It was evident that she was not writing this dream with the facility with which she had set down the others. She paused as she came to the chase by the bull and seemed to think about what next to say. Then she wrote: "It was very close. Then, in my dream, in fright, I ran faster over the field. I remember I hoped to gain a clump of woods. As I ran I stumbled and would have fallen. But I managed to catch myself in time. I ran on. I expected momentarily to be gored by the bull. That seemed to be the end of the dream--with me running and the bull gaining on me." She did not pause, however, except to skip a line, but began writing again: "Then the dream changed. I seemed to be in the midst of a crowd. In the place of the bull pursuing me there was now a serpent. It reared its head angrily and crept over the ground after me and hissed. It seemed to fascinate me. I trembled and could not run. My terror was so great that I awoke." She was about to lay the pen down again, as though glad of the opportunity, when Kennedy asked, with no intention of stopping so soon, "Were there not faces on these animals?" "The faces seemed to be human," she murmured, evasively, still looking at what she had written for him, and making no effort to amend or correct it. "Human?" repeated Kennedy. "Did they bear a resemblance to any one you know?" She looked up from the writing and met his eyes directly in a perfectly innocent stare. "The faces seemed to be human," she repeated, "but I did not recognize them." What did it mean? I knew she was not telling the truth. Kennedy knew it. Did she know that he knew it? If she did, it had no outward effect on her. "It is all very hazy to me," she insisted. I wondered what had been the reason of her hesitation and her final decision not to tell us what she had evidently told Doctor Lathrop on the first telling of the dream. Surely, I reasoned, there must be some reason back of this concealment. I was forced to be content to wait in order to question Kennedy to learn what his own impressions were. Any betrayal now, before her, might entirely upset his nicely laid plans, whatever they were. She seemed to expect a further quizzing and to steel herself in preparation for it. Evidently Doyle's manner and methods had taught her that. "Are those all the dreams you can remember?" Craig asked. I fancied that there was an air of relief in her manner, though she would not, for the world, have betrayed it before us. For a moment she thought, as if glad to get away from something that had troubled her greatly. When she spoke her voice and manner were subdued. "There is one other," she replied. "Will you write it?" asked Kennedy, before she had time to change her mind. "If you really care to have it." "Very much," he urged. Again she turned as though escaping something and wrote: "I seemed to be walking through a forest with Vail. I don't know where we were going, but I seemed to have difficulty in getting there. Vail was helping me along. It was up-hill. Finally, when we got almost to the top of the hill, I stopped. I did not go any farther, though he did." Here again she hesitated, then wrote slowly, "Then I seemed to meet--" and stopped. Honora glanced up, saw Kennedy watching her, and turned hurriedly, adding, "--a woman." She did not pause after that, but wrote: "Just then she cried that there was a fire. I turned around and looked. There was a big explosion and everybody ran out of the houses, shrieking." "You say you saw a woman?" asked Craig, almost before she had finished writing. "Who was she?" "I do not know who she was--a--just a woman." By this time I, too, was narrowly watching Mrs. Wilford. She seemed to have a most remarkable composure, except for an almost imperceptible moment of hesitation now and then. In fact, the hesitation would have passed unnoticed had not one been on the lookout. I think it was now that she realized that there was something going on in Kennedy's mind and in his method of questioning her that she did not understand. It was as though in taking refuge from answering one question--about the faces on the bull and the serpent--she had run directly into another question which she was equally averse to answering frankly. I was now convinced that a large part of her frankness with us was mere pose, that she knew Kennedy had penetrated it, and that the discovery alarmed her. Kennedy also saw that she had understood. It was as though it had been a cue. Instantly he threw off the mask. "Are you sure that it was not Vina Lathrop?" he shot out quickly. For just a fraction of a second she was startled, almost disconcerted. But instantly she regained her control. "Yes," she answered, positively. "I am sure it was not. It was no one I know." Yet I was somehow more than ever convinced that she meant Vina Lathrop, after all--Vina, who was of quite a different type from herself. What it all meant was another question. I knew that we should have taken a long step toward the discovery if we could only have got her to admit it. But she was keenly on guard now. There was not a chance of a direct admission strong enough, though the indirect admission was. "No one?" pressed Kennedy. "Think!" "No, no one! Oh, why must I be badgered and hounded this way?" she burst forth. "What have I done? Am I not grief-stricken enough as it is?--I hate--you--all!" It was the first time that she had let this undercurrent of her feelings leap to the surface, beyond control. She seemed to realize it, and instantly to repress it, as she stood there, her great, lustrous eyes fixed upon us--with defiance mixed with fear and doubt. It was startling, dramatic, cruel, perhaps merciless--this dissecting of the soul of the handsome woman before us. But it had come to a point where it was absolutely necessary to get at the truth. At least Kennedy seemed convinced that locked in her heart was the key to the mystery. Honora, hitherto almost pallid, was now flushed and indignant. For the first time we saw a flash of real feeling and I knew that underneath her conventional exterior a woman existed--very real, capable of the heights of feeling and passion when once aroused. It made me more than ever sympathetic toward her. I longed to help her, yet there seemed no way to do so. Only Honora might work out Honora's salvation. It was then and later that I realized that the very manner of her indignation showed the truth of the new psychology of dreams, for, as I later learned, people often become indignant when the analyst strikes what is called by the new psychologists the "main complex" of ideas. Kennedy evidently concluded that his examination had gone far enough, that to pursue it would be only to antagonize her unnecessarily. That would never do so early in the case. Accordingly he apologized as gracefully as an inquisitor could, and we excused ourselves, though Honora's gaze followed him defiantly to the door. "Well--we're in bad with her now," I whispered, as we gained the outside, in the private hallway. "That's most unfortunate," he agreed, though it did not seem to worry him much. "But you know by this time, Walter, that man-hunting is not a popular occupation--and woman-hunting is even less so." He stopped a moment, looked back, sighed, and added, "It is the penalty I must pay." In the hall, Craig stopped a moment to speak to Doyle's man, McCabe, a thick-necked fellow, square-jawed and square-toed, of the "flatty" type. "Mr. Doyle isn't here, I suppose?" "No, sir. Gone down to Mr. Wilford's office. Telephone call that there's something new there." "I see. Is the maid, Celeste, here?" "Yes, sir. Queer girl--pretty--French--but I can't seem to 'make' her." Kennedy passed over the impertinence of the slang. Evidently McCabe considered flirtations with maids his prerogative. "I'd like to see her." McCabe led us down the hall, and soon we found Celeste, a young and remarkably beautiful girl. One could see traces of sorrow on her face, which was exceedingly, though not unpleasingly, pale. She was dressed in black, which heightened the pallor of her face and excited a feeling of mingled respect and interest. There was, however, a restless brilliancy of her eyes and a nervousness which was expressed by the constant motion of her slender fingers. She shrank from McCabe, and her confidence was not restored even after Kennedy had ordered him to leave us alone with her so that we might question her. "Oh, these horrible detectives!" she murmured. "It is terrible. They will drive me crazy. _Pauvre, pauvre madame!_" Kennedy had sought this opportunity to question her about Vail Wilford alone. But, as he plied her with questions, she had little to say either about him or about her mistress. She was evidently well trained. "Did you ever see Mr. Wilford or Mrs. Wilford with Mrs. Vina Lathrop?" asked Kennedy, suddenly. Celeste shook her head with a naïve stare. "Nevair." "But, madame--did she not know her?" Celeste merely shrugged. "Wasn't she jealous of Mr. Wilford--and some one?" Celeste regarded him a moment. Her quick mind seemed to race ahead toward the implication of the remark. "No--no--no!" cried Celeste, vehemently. "She was not jealous. She would never have done such a thing. She might have left monsieur--but--violence--nevair!" Kennedy continued with a few inconsequential questions. Then from a table in the room he picked up a magazine. As he ran over the pages he stopped before a picture of a dinner in a fashionable restaurant, such as delights the heart of the modern magazine illustrator to portray. He turned the picture around and held it before Celeste for just a few instants, perhaps ten seconds. Then he closed the magazine quickly. It seemed to me to be a purposeless action, but I was not surprised when Kennedy added, "Now tell me what you saw." Celeste by this time was quite overwhelming in her desire to please on anything but the quizzing about her mistress. Quickly she enumerated the objects, gradually slowing down as the number became exhausted. "Were there any flowers?" asked Kennedy. "Oh yes--and favors, too, you call them?" I could see no reason at all in the proceeding, yet I knew Kennedy too well to suppose that he had not some purpose. The questioning thus strangely over, Kennedy withdrew, leaving Celeste more mystified than ever. "Well," I exclaimed, "what was all that kindergarten stuff?" "That?" he explained. "It is known to criminologists as the 'Aussage test.' Just try it sometime when you get a chance. If there are, say, fifty objects in a picture, normally a person may recall perhaps twenty of them." "I see," I nodded. "A test of memory." "More than that," he replied. "You remember that, at the end, I suggested that she might have overlooked something? I mentioned an object--the flowers--likely to have been on the table. They were not there, as you might have observed if you had had the picture before you. That was a test of the susceptibility to suggestion of Celeste." By this time we were on the street and walking slowly back to the laboratory. "She may not mean to lie deliberately," concluded Kennedy, "but I'm afraid we'll have to get along without her in getting to the bottom of this case. There were no flowers there, yet in her anxiety to please she said there were, and even went farther and added favors, which were not there. You see, before we go any farther, we know that Celeste is unreliable, to say the least." V THE PSYCHANALYSIS Back at the laboratory again, we found that not even yet had the materials arrived from Doctor Leslie with which to make the examination that Craig desired. It seemed to me that Leslie was very slow, but it didn't worry Craig. Evidently there were other and even more absorbing problems on his mind, problems that pressed for solution even above the discovery of the poison. "What was your idea in having her write those dreams out again?" I asked. "Well"--he smiled--"I wanted to see whether she would make any changes. Changes in the telling of dreams over again are often very significant. They indicate what the psychanalysts call the 'complexes,' the root ideas, often hidden away, out of which many actions and feelings spring." "I see--and did you find anything?" "A great deal. There are some important changes, some variations between what she told and what she wrote which are very significant. Don't you see? It is one thing to tell a dream in conversation--quite another when you calmly sit down to write it on paper. The words take on an added weight. Now the next problem is to figure out in my psychanalysis just what it is that these changes may mean." He drew forth the writing she had done and began studying over it carefully for several minutes. Finally, with an air of satisfaction, he looked over at me. "First of all," he said, "I want to consider that dream of the death of her husband. Just recall for the moment how she told that dream to Leslie." He took the paper in his hand and began reading. "Just listen. 'My most frequent dream is a horrible one. I have dreamed ever so many times that I saw Vail in a terrific struggle. I could not make out who or what it was with which he struggled.' If you remember, it was at this point that she hesitated in writing. Why did she? "'I tried to run to him. But something seemed to hold me back. I could not move.' Why was she unable to go to him? What held her back? There is something strange about it. Could it have been because she did not really want to go to him? Could it have been because she did not love him?" I said nothing. It had been the thought in my own mind, yet I had not cared to express it. "At that point," he went on, "she paused again. 'Then the scene shifted, like a motion picture. I saw a funeral procession and in the coffin I could see a face. In all my dreams it has been the face of Vail.' There was no hesitation, practically no change in that. I noted that she exhibited considerable emotion--that is, considerable emotion for her. She did not hesitate, because she does not understand the dream. If she did, I think she would hesitate--even refuse to tell it. I think with that dream alone one might get a pretty good inkling of the state of affairs." I was about to interrupt, but Craig hurried right on and gave me no chance. "More important, perhaps, take that dream of the bull and the serpent. If you recall, she wrote that more slowly and carefully than the other dream, choosing her words. There's something significant about that fact in itself. Now, let's see. "'I seemed to be attacked by a bull. It was in a great field and I fled from it over the field. But it pursued me. It seemed to gain on me.' That's where the first hesitation came, and right there we come to a very important 'complex,' I think. There was practically no change until we come to this part where the bull chases her. Did you get that?" I was forced to confess that I had not understood. It made no difference to Kennedy. Very patiently he proceeded to enlighten me, as if I were one of his pupils. "She omitted something that may be very important. Don't you remember when Lathrop told us she had told him that the bull was so close to her that she could feel its hot breath?" "I remember now. What of it?" "Very much. For some reason--perhaps unknown to herself--she omits all mention of it in writing it for us. I think you'll understand better as we go on with the dream. 'It was very close,' he read, rapidly. 'Then in my dream, in fright I ran faster over the field. I remember I hoped to gain a clump of woods. As I ran, I stumbled and would have fallen. But I managed to catch myself in time. I ran on.' "I think we discussed that ourselves, once, the fear of being a fallen woman. We need not go over it again, except to point out that her dream shows that, perhaps unconsciously, something restrained her. 'I expected momentarily to be gored by the bull. That seemed to be the end of the dream,' and so forth. "Now, the next part. 'I seemed to be in the midst of a crowd.' We discussed that, too--about the crowd denoting a secret. Then comes the serpent. 'It reared its head angrily and crept over the ground after me and hissed.' That's a bit different, there, from the way she told it. 'It seemed to fascinate me. I trembled and could not run. My fear was so great that I awoke.' All right. Here's the point--when I questioned her about the faces, the human faces, on those animals. She told Lathrop that the face she saw was that of Shattuck. But to me she absolutely denied it. She said she did not recognize the face. There's the point. Why did she cut out that about the hot breath of the bull? Why did she deny absolutely the face of Shattuck?" He was pacing up and down as though he had either made or confirmed a discovery. "Just consider what I told you about the Freud theory again," he went on. "Fear, as I told you, is equivalent to a wish in this sort of dream. We threshed that all out over my interpretation of the first dream of all--the death-dream. I hope you are beginning to understand, by this time. "But morbid fear also, as I have said, denotes some sex feeling. Now take the last dreams. In dreams animals are usually symbols. In the two parts of this dream we find both the bull and the serpent. From time immemorial they have been the symbols of the continuing life-force. Such symbolism has been ingrained in literature and thinking, both mystical and otherwise. When she felt the hot breath of the bull, it meant the passion of love in Shattuck, who is pursuing her. Frankly, I do not think he has ever lost his love for her. And she knows it--at least, subconsciously. That's what that means. In her heart she knows it, although she may not openly admit it. Also, she fears it. "More than that. Dreams are always based on experiences or thoughts of the day preceding the dreams. One doesn't always realize how easy that is. A thing dreamed of may have happened years ago. But if one could recall all the thoughts immediately preceding sleep, one would be able to trace out some impelling thought, perhaps on the surface quite unrelated, which brought it up. The more unrelated, the more interesting and important the connecting link. There was every chance, in this case, of Shattuck having been suggested to her any day. Besides, she may be thinking a great deal of him--and not realize it--for her moral censorship is always pushing such thoughts back into the subconscious." Kennedy regarded me attentively, then added: "She dreamed of a man's face on those beasts--then denied it to me. What's the explanation?" I suppose Kennedy was handing the explanation to me, but I could not quite understand it, much less express it. "Easy," he answered to his own question. "She thinks that she hates him. Consciously she rejects. Unconsciously, though, she accepts him. Any of the new psychologists who know the intimate connection between love and hate could understand how that is possible. Love does not extinguish hate, nor hate, love. They repress each other. The opposite sentiment may very easily grow. A proper understanding of that would explain many of the anomalies of human nature--especially in the relations of men and women which sometimes seem to be inexplicable." Since our previous discussion on the subject, I had turned it over many times in my mind. It was surely a new situation to me which this application of the new psychology was unfolding. Yet, under the exposition of Kennedy, I was not so bitterly hostile to it now as I had been before. Plainly enough, nothing that I had been able to offer to myself had fitted in with what I saw in the character of Honora Wilford. At least this seemed to fit. "You would be surprised to learn how frequently such situations arise," defended Craig. "I suppose, to an analyst, they seem to be common, because it is only such cases that come to his attention. If one treated only red-haired men, one would, no doubt, soon get the idea that the community was composed mainly of the red-haired. That is just as foolish as to go to the other extreme and to deny that there are any red-haired people, just because one has never happened to see one." The remark was obviously intended for me. I said nothing, but I was really alarmed. For I could see that the case was actually growing very much blacker for Honora as he proceeded. Was not Kennedy practically taxing her with loving another man than her husband? Was he not building up motives? "The dreamer," he proceeded, "is always the principal actor in a dream, or the dream centers about the dreamer intimately. Dreams are personal. We never dream about matters that concern others primarily, but of matters that concern ourselves, either very directly or at least indirectly. So it has been with these dreams of Honora. They concern her intimately. "Years ago that woman suffered what the new psychologists call a psychic trauma--a soul wound. She was engaged to Shattuck. We know that. But her censored consciousness rejected the manner of life of her fiancé. In pique, perhaps, she married Wilford. It was a wound when she cast aside her first love, a deep wound. "But Nature always does her best to repair a wound--either a physical wound or a psychic wound. That underlies the psychology of forgetting. Honora thought she had found love again, in the advances of Wilford. But she had not, truly. She never lost her real, now subconscious, love for another--Shattuck. Day by day she tells herself that he is nothing to her, never really was, never again can be. She believes it. She lives it. Yet, when that censorship is raised in sleep, it is different. Then he pursues her, in her dreams. In actuality, too, I don't doubt that he pursues her, and she knows it. I'll wager Shattuck does not dream of her except frankly. He frankly thinks of her. He is still in love with her. It is a tough problem for Honora Wilford." "I begin to see it more and more clearly," I admitted. "Dreams are very wonderful experiences, when one understands them rightly." "Her dreams, especially," agreed Craig, fingering the papers. "Now there's that dream of Lathrop. I suspect she thinks of him somewhat as of a social lion. And I suppose he is--popular, a club-man, a lady-killer. Perhaps that is why she dreamed of him as a lion. But it wouldn't explain all. I recall he wore a beard. That may have suggested the tawny mane of a lion, too. The two ideas combined. There is the narrow path, too. A lion stands in the path. I don't quite fathom it yet. But, you see, Walter, of such stuff are dream lions made. This fantasy I must leave open for interpretation until we understand Lathrop himself better." "About Shattuck," I reverted, not quite prepared to pass that point without clearing it as much as possible in my own mind. "Plainly he cares a great deal for her. I remember seeing one of Freud's books in his library. Suppose he knew her dreams. Would he not be able to discover that secretly she cared really very deeply for him and not for Vail?" "He might," admitted Kennedy. "But the problem would be to prove that he did," I supposed, for I was catching at any straw that would save Honora Wilford from the logical outcome of Kennedy's analysis as I saw it. Craig had come to the last sheet of paper. "This is my new prize," he exclaimed, waving it. "I had some inkling of what it betrays, but not the certainty this gives. This is an entirely new dream. We have no hastily spoken description with which to compare it. However, that will make little difference. We'll have to treat it as new. Let's go over it very carefully. It may easily prove most important of all." Slowly he read it. "'I seemed to be walking through a forest with Vail. I don't know where we were going, but I seemed to have difficulty in getting there. Vail was helping me along. It was up-hill. Finally, when we got almost to the top of the hill, I stopped. I did not go any farther, though he did.' That's where her first hesitation-break in writing it occurred. So far, you see, this is a most intimate dream of their relations, as you yourself can interpret readily. "There were several hesitations grouped here. 'Then I seemed to meet'--there was one--'a woman'--there was another. 'Just then she cried there was a fire.' What does that mean, you ask? Ever hear love described as a fire? Well, next: 'I turned around and looked. There was a big explosion and everybody ran out of the houses, shrieking.'" "I recall vividly what took place when we reached that point," I put in. "At the time I thought of Vina Lathrop, of what a quite different type of woman Vina is. Vina is none of your consciously frigid, unconsciously passionate women. Vina Lathrop is throbbing with passion, as one can see who has ever met her or heard of her." "Quite so. In this dream there plainly appears the 'other woman' in the case, the woman who has the passion which Honora herself does not have. Or at least, so she thinks. She seems to recognize in this other woman a woman of a different nature from herself. And yet," added Craig--"and yet, you know, 'The Colonel's lady and Judy O'Grady--'" "Are not only the same under the skin, to you psychologists," I supplied, "but in the inner consciousness, too." "I suppose so," he laughed. I considered a moment. Was this all confirmation of the rumored relations between Vina Lathrop and Vail Wilford, as Doyle had dug the story up? I recalled the notations that Doctor Leslie had discovered on the desk calendar of Wilford about appointments with Vina and the contemplated divorce. Had a new scandal been brewing and had the sensational press of the city been deprived of it by some untoward circumstance? At least they had no complaint. A greater piece of news had been created to take its place--a murder case which, now, bade fair to become the celebrated case of the season when it "broke," as they say. "The reason I've spent so much time analyzing this new dream," Craig continued, "is that there's another very important thing in it--revealed in the hesitation and the changes, the gaps, and the additions. It helps us to reconstruct her inner life, as we could never have got it from herself, as she could never, even at this moment, construct it for herself. "Into her life--into her dream life, too--there has come 'another woman.' I believe that it is really Vina Lathrop. She betrays it. I hate to admit that either Doyle or Leslie may be right--about anything. But, really, once in a while Doyle does stumble on something--without knowing even remotely how important the thing may be." "I suppose also that that would account for Mrs. Lathrop's interest in us--and the case," I ventured. "When we were in the doctor's office I thought she was keenly alive to what we were doing and saying." Kennedy nodded. "It remains to be proved, however. I knew I was on the right track when we visited Lathrop, as you say, and his wife made that remark about Honora. You see, intuitively she knows Honora. She knows her cold nature. Before we get through we shall have some interesting passages at arms between these two, if I am not mistaken. Already their intuitions have given each an estimate of the other. They are opposing lines--between the two, it is No Man's Land." "Opposites--positive and negative," I tried to express it metaphorically. "And the wires are crossed. Oh, I know this will be a good case--it always is when there is conflict, like this, between two women." "Speaking of crossed wires reminds me of the telephone," exclaimed Kennedy, energetically. "We need not be inactive just because our good friends, Leslie and Doyle, don't feed grist to our mill. I'm going to see that woman again." Kennedy hunted up Doctor Lathrop's number in the book and called it. "The doctor is out just now," answered a woman's voice. "Is there anything I can do?" "Is this Mrs. Lathrop?" Craig asked. I saw that she replied in the affirmative. Kennedy deftly explained who we were and recalled our brief meeting of the morning. "I'm greatly interested in the Wilford case," he hurried on. "I would like to talk to you about it. May I?" There was a bit more of conversation, then he hung up with satisfaction. "She did not welcome it," he reported. "Yet she could scarcely refuse to see us under the circumstances. I have made an appointment to meet her." There was a noise at the door and I opened it upon Doyle, who entered, his face showing great perplexity. "What seems to be on your mind. Doyle?" greeted Craig. "Enough. We've been questioning the night watchman down at the building where Wilford's office is," he informed. "You remember the two glasses on the desk when they found him?" Kennedy nodded. "From them," continued Doyle, "I went on the assumption that somebody else had been there at the time. There _was_ a visitor.... We are convinced of it now. The fact is that the building is an old one, built before elevator days, not tall. One can walk up to the office of Wilford easily. People do. And the confounded watchman, a man they call Pete, confesses that he was off the job, at least part of the time, last night. There was plenty of chance for a visitor to have got in and got away." "Who?" I asked. Doyle shrugged. "We can't find out--at least, we haven't found out." "Was it a man or a woman?" asked Craig. "We don't even know that," confessed Doyle, in despair. "That fellow Pete is a dub." "How about your suspects?" prompted Kennedy. "You must have traces of their movements last night." "I have. I have been questioning Celeste, the maid, for instance. She swears that Mrs. Wilford was at home in the apartment all the evening of the murder. The worst of it is, I can't prove yet that she wasn't. But just give me time--give me time. I'll get something on that maid yet." I glanced significantly at Kennedy. He nodded back. His "Aussage test" had effectually disposed of any reliance that might be placed on what Celeste might say. However, Kennedy said nothing of that to Doyle. To have done so would have been to invite a tirade of laughter. The only way with Doyle was to let him go along his sweet way of being wrong--then let him in when we were right. Yet, I must say that I liked Doyle in his way, even if he was only a plugger. "Another thing," brightened Doyle. "I'm getting a line on that business of Wilford's having his wife watched. You know, he did that. He hired a private detective to watch her. If I can get that fellow I may learn something. But that Celeste is clever. She sticks to it that her mistress wasn't out. We'll see if the detective knows when we find him." "Where were Shattuck and Lathrop last night?" asked Craig, quickly. "Shattuck has given a detailed account of his doings last night. I'll tell you better about him when it's verified. Doctor Lathrop had two cases that night, which kept him out late. I believe they are bona fide. So far there's been no flaw in either story. That's what perplexes me. I thought I was on the trail of something." "And when you find yourself up against it, you come to me?" "Don't get peeved, Kennedy," mollified Doyle, though he himself had winced at the telling thrust of Kennedy. "What about Lathrop's wife, Vina?" asked Craig. "Is she clear for that night?" "I hadn't thought much about her," confessed Doyle. "Want me to find out?" "Never mind. I am going to see her soon. I'll attend to that." VI THE "OTHER WOMAN" Vina Lathrop received us a few moments later with a question in her eyes. Yet she discreetly did not hint at it in anything she said. I have said that she was a woman of quite opposite type from Honora. Like her, however, she was a woman of rare physical attraction. Yet it needed only a glance to see that men interested Vina, and in that respect she gave one a different impression from Honora. And I am quite sure, also, that few men could have withstood the spell of her interest if she chose to bestow it. There was, no doubt, much in her life that that accounted for. "I've been thinking of what you said about Mrs. Wilford this morning," began Kennedy, after a few remarks that explained our interest in the case, without telling her anything that would put her too much on guard. "My remark about Mrs. Wilford?" she repeated, naïvely. "Yes. You remember when you were talking to Doctor Lathrop about the case, you said, 'I don't think that Honora is capable of either deep love or even deep hate'? I've been wondering just what you meant by it." Vina seemed to be careful lest an unwary word might escape. "Why, really," she murmured, as though feeling that the question called for an answer she did not wish to give. "I don't think that Honora--well--understood Vail Wilford, if you get what I mean. He was not difficult to understand. He would have been devoted to her--if only--" She paused and stopped. "If only what?" "You wouldn't understand," she answered, quickly, shaking her head. To me it seemed as though the implication she wished to convey was the usual specious refuge of the "other woman," when cornered, that it was she, not the wife, who really understood the man in the case. "You see, I don't know Honora Wilford well," encouraged Kennedy. "I can't say that I do understand. I guess that's just it. I thought perhaps you might enlighten me." Vina gave a pretty little shrug to her attractive shoulders, then leaned forward, as if suddenly deciding to become confidential with Craig. "It's a long story," she replied. "I don't know how to tell it. Honora was like her father--in fact, her family are all the same--always seeking the main chance. You remember old Honore Chappelle? No? Out of even the business of an oculist he managed to make a tidy fortune. She was ambitious--ambitious in marriage, ambitious to get into 'society,' you know. Don't you see now what I mean? Besides, you know, daughters, they say, inherit from their fathers--and she seems to have been no exception. I think Mr. Wilford came to realize why it was she married him, only, of course, in such cases, it comes too late." I set the remark down as that of a "catty" woman. Yet there was something to think about in it. For, at the time of Wilford's marriage, the young lawyer was already wealthy and in the smart set, while Vance Shattuck had not inherited the fortune of his uncle, who had often threatened to cut him off without a penny as a reward for his numerous escapades. There could be no doubt that, at the time, Wilford was the greater "catch" of the two. As we talked with Vina about the death of Wilford, she spoke with ill-concealed emotion. I could not escape the impression that she seemed to be more deeply affected by it than even Honora herself had been. Was it due to her more emotional nature? I would have thought it strange, even though Kennedy had not already surmised from his psychanalysis of Honora that Vina was the "other woman" in the case. It was apparent that, whatever might be Vina's own story, she reacted sharply against the very type of woman that Honora was. There was plainly some rivalry between them, some point of contact at which there had been friction. It was most assuredly Kennedy's job to find out what that was. "I don't know whether you are aware," he suggested, taking a slightly different angle, "but in Mr. Wilford's office they found evidence that you yourself were preparing a divorce suit." The transition from Honora to herself was sudden. Yet Vina did not seem confused by it. She did not deny it, or even attempt to deny it. Perhaps she realized that it was of no use, that her best defense was, as the lawyers would say, confession and avoidance. "Oh," she replied, airily, "the suit was never started, you know--just talked about." I could not but wonder at her callousness. Evidently this woman was of a type all too common in a certain stratum of society, to whom marriage is a career to be entered into either for the sake of bettering oneself or for the sake of variety. "What, may I ask, were the grounds?" probed Kennedy, growing bolder as he saw how frankly she elected to discuss the subject when cornered. She colored a bit, as she strove to decide whether to get angry or to answer, then chose the latter course. "Incompatibility, I suppose you would call it--at least that's what I call it. I believe every woman should live her own life as she sees fit. I hadn't even decided what state I would acquire residence in, in order to bring the suit, if I decided to go on with it. Nothing was settled, you know." "And now you are going to--?" inquired Kennedy, stopping to let her fill out the answer. "Drop it, of course," she supplied. "I suppose the doctor and I shall continue to agree to disagree." "Had Mrs. Wilford contemplated similar action on her part, do you think?" Vina avoided answering, but Kennedy pressed for a reply, asserting that Vail Wilford must have given some hint of it, either by his words or actions. "I don't know," she repeated, firmly. "Did she know of your--er--acquaintance with Mr. Wilford?" If looks had been poisonous, Kennedy must have been inoculated with venom right there. He paid no attention to her scornful glances as, again, there was no avoidance of an answer, no matter how much she tried. "Why do you think you know so much?" Vina veiled her sarcastic reply. "Mrs. Wilford had been having her husband watched, I learn," prodded Kennedy, with brutal directness. I glanced covertly over at him. Doyle had told us Wilford was watching his wife. But no one, as I recalled, had given us an inkling of a reverse state of affairs. I realized that Kennedy had made it up out of whole cloth. He was trying it out to see its effect. At any rate, there was nothing unreasonable about it. It might have been true, whether it actually was or not. For a moment Vina was sorely tried to hold back a quick reply. Then she shrugged again. "Most women of the sort have to do that," she snapped. It was a mean remark, besides being glaringly untrue, except in the limited ken of certain New-Yorkese women. Moreover, I saw that Kennedy had slipped past her guard. Each sentence she replied betrayed the keen feeling between the two. Kennedy seemed to be observing Vina as he might a strange element in a chemical reaction. On her part she seemed intuitively to recognize that there was a challenge to her in Craig's very personality. Arts which she might have tried with success on another seemed not to impress this man. He seemed to penetrate the defenses which she had against most men. And I could not help seeing that she was piqued by it. While they were fencing in their verbal duel, Craig had casually drawn a pencil from his pocket. A moment later I saw that he had begun scribbling some figures, apparently aimlessly, on a piece of paper. From where I was sitting beside him I could see that he had written something like this: 5183 47395 654726 2964375 47293825 924783651 2146063859 For some time he regarded the figures that he had written as the conversation went on. "Here's a little puzzle," he remarked, offhand, breaking into the chat. "Did you ever try it?" Vina looked at him in surprise at this unexpected turn of the conversation. I am sure that she was in doubt as to the man's sanity. However, there was a certain relief in the new turn of the conversation. At least he was not treading on the dangerous ground which he had trod upon. "Er--no," she answered, doubtfully. "That is--I don't know what you mean. What are the numbers?" "Oh, it's nothing much," he disarmed. "It's simply a matter of seeing whether a person can repeat numbers. I've found it rather interesting at times." Without waiting for either comment or excuse from her he said, quickly: "For instance, take the first one--five, one, eight, three. See if you can repeat that." "Of course--five, one, eight, three," she replied, mechanically. "Fine--four, seven, three, nine, five," came in rapid succession. To it she replied, perhaps a little slower than before, "Why, four, seven, three, nine, five." "Good! Now, six, five, four, seven, two, six." "Er--six, five, four, seven, two, six," she repeated, I thought, with some hesitation. "Again--two, nine, six, four, three, seven, five," he shot out. "Two, nine, six"--she hesitated--"four, three, seven, five." "Try again--four, seven, two, nine, three, eight, two, five," he read. "Four--two--seven," she returned, slowly, then stopped, "three--nine--what was the next one?--er--two--two--" It was evident that she was hopelessly muddled. It was not because she had not tried, for the diversion had come as a welcome relief from the quizzing on delicate subjects and she had seized upon it. She had reached the limit. Kennedy had smiled and was about to go on, although it was evident that it was useless, when there was a noise in the hall, as though some one had been admitted by the maid and had entered. It seemed to be a man's voice that I heard and I wondered whether it was Doctor Lathrop himself. A moment later the door opened and disclosed, to my astonishment, not Lathrop, but Shattuck. If he was embarrassed at finding us there he did not betray it in the least. Quite the contrary. He greeted Vina Lathrop cordially, then turned to us. "Oh, by the way," he began, "you're just the man I wanted to see, Kennedy." I thought that there was a note of indignant protest in his voice as he said it, then, before Kennedy could make reply, went on, rapidly: "About Mrs. Wilford--it's an outrage. Doyle and McCabe and the rest of that precious crew are thugs--thugs. I called there to express my sympathy. Of course she couldn't say much--but I have eyes. I could see much, without being told. There she is, harassed and hounded and practically a prisoner in that place--no one to go to--her husband foully murdered--at least that's what _they_ say. I don't know. She's spied on, listened to--I tell you, it's a shame. They're driving that poor woman insane--nothing short of it." Shattuck was evidently genuinely angry and, indeed, I felt that he was making a good case of it. I looked toward Vina. She merely tossed her head. Evidently she was piqued that Shattuck should think so much of "that woman," as she doubtlessly would have liked to refer to her. I wondered what might have been the connection between Vina and Shattuck, and determined to watch. More than that, I wondered what could be his purpose in bringing up the name of Honora before Vina. Had he a reason? "Did you finally sell the stock?" inquired Vina of him, abruptly, as though wishing to change the subject. "Of course," he returned. "Only to complete the thing you will have to indorse this paper," he added, drawing a document from his pocket for her to sign. I wondered whether this reference to a business transaction was a blind to make us believe their relations were merely those of a broker and client. Shattuck excused himself to us while Vina signed with his fountain-pen and as they talked in a low tone I saw that she was appealing to him with all her feminine arts. Was Shattuck proof? Or was he dissembling so as not to betray anything to us? I remembered the old gossip about Shattuck. Was he still woman-crazy? Had Vail Wilford stood in his way with both women? It was a queer tangle at best. Anything, I felt, might prove to be the case. At any rate, I was sure that the transaction covered their embarrassment at meeting us. More than that, it convinced me that there was some connection between Shattuck and Vina all along. I had wondered whether it had been she who had telephoned to him while we were at his place that morning. I had not thought of the possibility at the time. But now I was sure of it. Kennedy rose to go, and at the same moment Shattuck also excused himself. We departed, leaving Vina, I am positive, still all at sea as to the purpose of our visit. We departed, and at the street corner stood talking for a moment with Shattuck. Again, as though taking the thing up just where he had left it off, he complained about the shame of the persecution of Honora. Kennedy was non-committal, as indeed he was forced to be over Doyle's work, and after promising nothing, we parted. In fact, Craig said very little even to me as we started around the corner for the laboratory. "What was all that rigmarole of the numbers?" I inquired, finally, my curiosity getting the better of me, as we entered the Chemistry Building and Craig turned the key in the lock of his private laboratory, admitting us. "Part of the Binet test," he answered. "It is seeing how many digits one can remember. You're not acquainted with the test? It's used commonly in schools and in many ways. Well, an adult ought to remember eight to ten digits, in any order. A child cannot, ordinarily. Between these, there are all grades. In this case, I do not think we have to deal with a mentality quite up to the intellectual standard." "It's well Vina Lathrop isn't here to hear you say it," I commented. Kennedy smiled. "True, nevertheless, whatever outward looks may show. To tell you the truth, Walter, here we have to deal with two quite opposite types of women. One, intellectual, as we know, does not yet know what love really is. In the other I fancy I see a wild, demi-mondaine instinct that slumbers at the back of her mind, all unknown to herself. She knows well what love is--too well. She has had many experiences and is always seeking others--perhaps the supreme experience." He paused a moment, then added, estimating: "Vina is beautiful, yet without the brain that Honora has. She is all woman--physical woman. That was what probably attracted Wilford, what she meant by saying that I wouldn't understand, although I did. In Wilford's case it may have been the reaction from the intellectual woman. She knows that power which her physical charms give her over men; Honora does not--yet." "But, Craig," I remonstrated, "you do not mean to tell me that you believe that you could sit here in a laboratory and analyze love as if it were a chemical in a test-tube." "Why not?" he replied. "Love is nothing but a scientific fact--after all." "Then explain it." He shrugged. "True, you ask me to explain love and I must tell you that I cannot. For the moment it looks as though you had me beaten. But think a moment. I cannot tell you why a stone falls or a Morse signal flashes over a wire. Still, they do. We know there is a law of gravitation, that electricity exists. We see the effects gravity and electricity produce. We study them. We name them--though we do not understand them. You would not say they were not scientific facts just because I cannot explain them." I nodded, catching his idea. "So with love," he went on. "We know that there is an attraction--that is a scientific fact, isn't it?--which two people feel for each other. Society may have set up certain external standards. But love knows nothing of them. Our education has taught us to respect them. But above this veneer every now and then crop out impulses, the repulsions and attractions which nature, millions of years back, implanted in human hearts as humanity developed. They have been handed down. Yes, Walter, I know nothing more interesting than to put this thing we call love under the microscope, as it were, and dissect it." I regarded Craig with amazement. Was he inhuman? Had he suddenly taken leave of his senses? "You mean it?" I queried. "Really?" "Certainly." "Why, Craig," I exclaimed, "some day you, too, will meet your fate--you, the cold, calm, calculating man of science who sits here so detached, analyzing other people's emotions!" "Perhaps," he nodded, absently. "Like as not she will be some fluffy little creature from the Midnight Frolic," I added, sarcastically. "It would be poetic justice if she were. And what a life she would lead you--with your confounded microscope and your test-tubes!" Kennedy smiled indulgently. "If it should be the case," he replied, coolly, "it would only prove my theory. It's very simple. Two atoms are attracted like the electrically charged pith-balls--or repulsed. In love very often like repels like and attracts unlike--the old law, you know, as you saw it in the physics laboratory. We see it in this case, with these very people. All your fine-spun theories and traditions of society and law do not count for the weight of a spider thread against nature. That is precisely what I mean by my theory. We are concerned with deep fundamental human forces." "You talk as though you had been reading some of the continental writers," I remarked. "Perhaps. It makes no difference. Often much of our own Puritanism in literature covers a multitude of facts, as Puritanism does in life. Here's a case in point. Facts may be ugly things, we may not like them. Just the same they have to be faced. It won't do just cavalierly to reject things as Doctor Lathrop does with the Freud theory, which he does not like, for instance. And who is he that he should set himself up to determine fact and fake? Maybe, if we studied him we'd find he was no different from anybody else. I'll warrant it." "I don't care about him," I hastened. "But it does rather jar on me to have you speak so positively on affairs of the heart," I protested. "You think I can't observe them without experiencing them? I don't have to commit a murder in order to study and understand the murderer, you know. The fact is I am perhaps a better judge of some subjects for the mere fact that I can observe them from the outside, as it were. I am not grinding my own ax." I shook my head at Kennedy's, to me, novel theories of love. In fact, the whole thing, from his dream interpretation down through each step he took in the case, seemed almost revolutionary. Convinced against my will, I was of half, at least, my own opinion still. Yet I did not feel in any position to combat him. The case would ultimately speak for itself, anyhow, I reflected. "Now," he concluded, before I could think of a retort, "to get back to the case. Here are two women who no more understand the impulses that sway them than do the moon and sun in their courses. As I said, fundamental forces of sex are at play here. Perhaps even if you were able to get the truth from the various actors in this little drama they themselves could not tell you. Therefore, it is for me to unravel what is a closed book, even to them. "And, strange as you may think it, Walter," he concluded, "the Freud theory will do it. Already I know more than even you suspect. There remains, however, the working out of the drama to its climax before I can be sure I have the truth, beyond mistake." VII THE CROOK DETECTIVE We were interrupted by the arrival of Doyle at the door. With him was a stranger whom he seemed to be virtually forcing along ahead of him. As they entered, I regarded the man carefully. He seemed to have a sort of hangdog look. Doyle led him over beside the laboratory table, near which Kennedy was standing, and Kennedy glanced at Doyle questioningly. "This is Mr. Rascon, a private detective," growled Doyle, stressing the Mister insultingly, and continuing to push the man forward. "Meet Mr. Kennedy, Rascon." Doyle had evidently the official contempt for the very breed of private detectives. The man bowed stiffly and nervously to Craig, who extended his hand, which the man took rather spiritlessly. Altogether I thought it a very peculiar circumstance. "Meet Mr. Jameson, of _The Star_," added Doyle. "It might be well for you to have a few newspaper friends. They might come in handy some day. They tell me a press agent's job is to keep things _out_ of the papers as well as to get them in." Rascon smiled weakly as he shook my hand, and by the clammy touch of his hand I knew that he was either very nervous or very ill--perhaps both. "Tell Mr. Kennedy what you've been doing, Rascon," commanded Doyle in his best gruff manner. Rascon hesitated, but Doyle repeated his command, and in the repetition there was a thinly veiled threat that at once aroused the interest of both of us. What could be the purpose of bringing the stranger to us now? Rascon cleared his throat. "I've been employed by Mr. Wilford," he remarked a bit huskily, "to watch Mrs. Wilford." "What--to trail her?" asked Kennedy with increased interest. "Yes," admitted the man, reluctantly. As I watched him I could see that he was of the type that is all too common. His shifty eye, never meeting yours for any considerable length of time, made a very unfavorable impression on me. It is not that all private detectives, or perhaps even a considerable number, in view of the many in the profession, are of this class. But there are altogether too many of his type and they are a decided menace to their branch of the profession and to society in general. I refer to the type that euphoniously "furnishes" evidence--but unscrupulously goes to the length, if necessary, of actually manufacturing it. They are to their profession what the yellow journalist is to mine, the quack doctor to the medical profession--pariahs. "Well," prodded Doyle, "tell us what you found." Again there was no answer. "Come--speak up. Tell us. You might as well tell now as to do it later." Still he said nothing. Slowly Rascon drew from his breast pocket a tissue-paper flimsy sheet, a carbon copy of some typewriting, such as some agencies frequently use on which to make their reports to their clients. "Read it!" demanded Doyle. Slowly Rascon read: "June 20. Wilford case. Operative No. 1. "I picked up Mrs. Wilford at the door of the apartment at 11:15 A.M. She took a taxi to the Piccadilly Hotel. "There she went in and I followed her to the telephone. I got into the next booth and tried to listen through the partition, but I was too late. She left immediately. "From the Piccadilly I trailed her to the Plaza, just above Fifty-ninth Street, on Fifth Avenue. There was a touring-car waiting by the curb. In it she met Mr. Shattuck. "I had time to hail a taxi as they were preparing to drive away and followed. They turned and went down-town. I followed through traffic across the Bridge and through Brooklyn. On the Parkway the touring-car pulled away from me, but not before I was convinced it was headed for the Beach. I had the number, 97531, and the description. "At the Beach House I picked the car up again. Located the parties at luncheon. I waited about. They did not start back until four o'clock. I followed and he left her at the Subway at the Grand Central. "She returned to the apartment, about quarter to six. "I waited outside until relieved by operative No. 6." "Was that all that happened?" I asked quickly. "They merely rode down to the beach and had lunch together?" Rascon again did not reply. I could not even catch his eye as I asked the question. "Just a moment, Jameson," interrupted Doyle. Then, leading the detective on, "Now, Rascon, what did your employer, Mr. Wilford, say when that report was presented to him?" Rascon colored at the question, as Doyle had evidently intended that he should. "He never saw it." Doyle glowed with satisfaction, as though he were a lawyer bringing out the facts by cross-examination. He nodded to Kennedy and me as if we were a jury. Doyle was merely getting his facts into the record, as it were. Already he had quizzed Rascon into a state of anger and resentment out of which the truth might be expected to slip unaware. "Never saw it?" thundered Doyle. "What do you mean?" There was only silence from Rascon. Then, as Doyle threatened, he answered, surlily, "Mrs. Wilford paid me for the report--that is, for the copy of it." A moment Doyle regarded him, then his virtuous ire rose into towering wrath, even as though he had just heard the thing now for the first time. "She paid you for it! You dirty hound--that's blackmail!" Kennedy interrupted. "Is it true?" he demanded, tapping the sheet of paper which he had taken and read hastily to make sure that nothing had been omitted in the first reading. "Did she meet Shattuck?" The detective scowled to himself. "Is it true--tell him," shouted Doyle, brandishing a menacing fist in Rascon's face. The detective, himself a bulldozer when he had the chance, was bulldozed, even as a German might be frightened by a taste of his own frightfulness. "N-no," he stammered. "But had you made similar reports to Mr. Wilford?" persisted Kennedy, with some purpose. "Oh yes--but not this one. She paid me for this. I played fair--I did," he almost whined. "Hm! I see," measured Kennedy. "Mr. Wilford got similar reports--and believed them?" Rascon nodded a deprecating acquiescence. "I suppose so. He never kicked or asked questions. I guess it was what he wanted to know--eh?" It was not the flash of the detective's cynical lying that surprised me, but Craig's remark and what might be implied in it by the narrowing of Craig's eyes as he asked it and received the answer that he had apparently expected. I glanced at Craig hastily. What did he mean by the inflection of his voice and by the look? Hastily I tried to make it out. If the report of this Rascon had been true, did it not seem to explain and motivate Honora? But, I reasoned immediately, even if it were untrue and if Wilford believed those reports he received and wanted to believe, was there not just as compelling a situation? The thing was important and dangerous for her, either way one looked at it. A few more questions and it was evident that Rascon, in spite of the baiting that Doyle had given him, was pretty well on guard and in control of himself and would admit nothing unless Doyle had documentary proof or something just as good. Doyle, not wishing to disclose the limit of his information, turned the interview short. "That'll do," dismissed Doyle. "You may go, Rascon. I'll have more from you later." Rascon backed out, sheepishly, eager to get away. "I'll have his license revoked," muttered Doyle, calming down after the stormy quizzing. Doyle's contempt for Rascon knew no bounds. As for Rascon, I knew the method he had adopted. Once Rascon, or any of that breed, had a case involving clients with money, he proceeded to nurse the case along, to play one party to the case against the other. But I had not often run across cases where the crooked detective, who is a pest despised by all honest detectives even more than by other people, had been so brazen about collecting all the traffic would bear from each side, indiscriminately. "Why not ask Mrs. Wilford herself about it?" I suggested, as neither Kennedy nor Doyle said anything. "Better not--yet," objected Doyle, hastily. "I want to watch her a little herself. I particularly bluffed Rascon into not telling her a word of this." "Oh, that's all right," acquiesced Craig. I understood. It was Doyle's clue. He had been honest about it. He had not held back the information from us. But it was his to pursue, he figured. As for Craig, I knew that he would gladly keep his hands off the thing. Besides, there was plenty for us to do in carrying out the line of action which Kennedy had adopted, leaving the less subtle things to Doyle. "How did you find out about this fellow?" asked Craig, after a little while. "You remember Celeste?" answered Doyle, as though he had not yet finished telling us what he had come to tell. "The maid? Yes?" "I saw Rascon hanging about the apartment--trying to see Celeste. I watched. The dirty dog was trying to sell some more of the stuff to Mrs. Wilford, the whole thing--make a final clean-up under threat of handing it over to me if she didn't come across. Well," he laughed, "I got it, anyhow. She ought to thank me. I saved her some money." I did not like his tone toward Honora. "Well," he went on, "as soon as I got the lead I investigated. Now I'm convinced that Celeste was the go-between in the transactions. I've made Celeste confess. She paid him the money for Mrs. Wilford. He handed her copies of the fake reports which he agreed to 'kill' if enough was paid for them. Oh, it was a slick game, taking advantage of a situation." I glanced at Kennedy. "Do you think Celeste can be relied on?" I asked. He saw that I meant the test of her susceptibility to suggestion and her inaccuracy. "Ah, very true, Walter," he remarked. "But the reports themselves are incontrovertible. True or false--they were made. Some of them Wilford must have seen. Others she must have paid for. But the fact remains, no matter what Celeste may be." Doyle had been waiting impatiently for us to finish. Finally he nodded mysteriously, then stepped to the door. He opened it, and there in the hall I saw Celeste herself, with McCabe. The detective and the girl entered. Celeste stared about, not quite knowing what to make of the whole affair. "Celeste," began Doyle, with an easy familiarity which I knew the French maid resented deeply, "you saw that man who was here and went away?" "Yes, sir." "Do you know him?" "I have met the gentleman--two or three times." "What happened on one of these occasions?" Celeste paused. But Doyle was a forceful persuader to those who hesitated. Celeste evidently considered that she had best say something. That I knew was the danger--her readiness to say something, no matter what, to follow out some purpose in her own mind. However, knowing her attachment to Honora, I felt sure, as she went on, that what she was telling us was wrung from her by compulsion and was not said merely as so many words. "Madame she asked me to hand him an envelope." "And what then?" "In return I was to get one." "Did you get one?" "Yes, sir." Celeste was saying no more than necessary. "What was in it?" The girl shrugged in her best Parisian. I may have been convinced that she did know what was in the return envelope. But there was clearly no way to prove it. We were forced to take her word on the matter. Doyle himself realized that handicap. "Now, Celeste," began Doyle again, passing over that uncompleted phase, as though there was much he could have said, only refrained from doing so to go on to the next point, "what about the belladonna?" "She used it to brighten her eyes," returned the maid, as glibly as if she had practised the reply. "I mean--when did she use it last? Be careful. I know more than you think." "Yesterday," she replied, in a low voice, somewhat startled at Doyle's assumption of omniscience. "Why?" "Her eyes were dull." "She had been crying the night before--eh?" There was no answer. "Ah--then there had been a quarrel between Mrs. Wilford and her husband the day before?" Doyle's assurance, like a clairvoyant having struck a profitable lead, overwhelmed Celeste. She said nothing, but it was evident that Doyle had hit upon something at least approximating the truth. "Did she threaten again to leave him?" persisted Doyle, now taking further advantage. "Oh--no--no--no! Madame would not quarrel. She would not leave monsieur--I know it." I glanced again at Kennedy. I saw that he placed no great reliance on what Celeste said, unless it were substantiated in some outside manner. It seemed to be about all we could get out of her, at least at this time. Moreover, following Doyle's wishes, we decided to let him handle both the Rascon affair and such watching and questioning of Celeste as may seem necessary. Kennedy was not unwilling. To tell the truth, the Rascon affair was indeed unsavory and a mess we could afford to let alone. "That's all, my girl, for the present," concluded Doyle. "Oh--by the way--not one syllable of this to Mrs. Wilford. And if you breathe a word I shall know it. It will go hard with you, you understand?" She bowed and McCabe took her away. It had been all right while she was with us. But the moment McCabe loomed up on the scene, it was different. She tossed her head with offended dignity and marched off. For some moments longer Doyle and we discussed the new phase of the case. It was greatly to Doyle's satisfaction that we allowed him to be unhampered in what he had unearthed. It had evidently worried him to think of having us two amateurs dragging across the trail he had uncovered. Finally he left us, satisfied that he had done a great stroke of work. For some moments after he was gone Kennedy was silent and in deep study. "What do you make of it all?" I asked, breaking in on his thoughts, for fear something might interrupt before I could obtain Craig's personal impression. "Very important, perhaps--not for any evidence it may furnish in itself regarding what happened, for Rascon confessed that it was all faked, but important for its effect upon the minds of those concerned." Somehow I was not pleased at Doyle's discovery. In my heart I was hoping for anything that would relieve the load of suspicion on Honora. This did not. "You see," went on Kennedy, "it's not always what people know, the facts, that are important. Quite as important, oftentimes, are the things that they think they know, what they believe. People act on beliefs, you know." Much as I hated to admit it in this instance, I was forced to grant that it was true. "That may be," I confessed, "but why did she pay? Isn't it likely that it was a frame-up against her?" Kennedy smiled as he realized I was defending her. "Quite the case," he argued. "I suppose you know that some of these private detectives are really scandalous in their operations?" "Indeed I do." "Then can't you understand how a woman who knows might be driven desperate by it? Honora was well informed in the ways of the world. She knew that people would say, 'Where there's so much smoke, there's fire.' I'll wager that you've said the same thing, yourself, about articles in your own paper." I nodded reluctantly. It was a fact. "Why, this private-detective evil is so bad," he went on, vehemently, "that judges ordinarily won't take the testimony of a private detective in this kind of case unless it is corroborated. And yet, in spite of that fact, you can always find some one to believe anything, especially in society, provided the tale is told circumstantially. She knew that, as I say. And it must have been exasperating. It must have preyed on her mind. No doubt, if you sift the matter down you'll find that it was just this move on the part of her husband that killed whatever spark of love there might have been glowing in her heart. Suspicion does that." I decided not to pursue my own argument. I felt that the more I attempted to defend or excuse Honora, the more Kennedy bent and twisted the thing to some other purpose of his own. I could only trust that something would come to the surface that would set things in a different light. Doyle had been gone some time and Kennedy was beginning to get a little nervous over what was delaying Doctor Leslie with the materials from the autopsy from which he expected to discover much that would straighten out the tangle of what it really was that had occurred in Wilford's office on that fatal night. We had about decided to take a run over to the city laboratories to find out, when the door opened and a hearty voice greeted us. It was no other than Doctor Leslie himself, with an assistant carrying the materials from the autopsy, as he had promised. The fact was that he had not been so very long. Events had crowded on one another so fast that we had not appreciated the passage of time. As the attendant laid the jars down on Craig's laboratory table, Leslie seemed to have almost forgotten about them himself. "I've made a discovery--I think," he announced, eagerly. "Perhaps it's gossip--but at any rate, it's interesting." "Fire away," encouraged Kennedy, listening, but at the same time preparing impatiently to plunge into the deferred analysis might now be made. "I stopped at the Medical Society," hastened Leslie. "Do you know, it seems to be the gossip of the profession, under cover, about Lathrop and his wife. News spreads fast--especially scandal, like the talk of her knowing Wilford, which, thanks to some of Mr. Jameson's enterprising fraternity, the papers have already printed. Well, from what I hear, I don't believe that she really cared for Vail Wilford at all. It seems that she was using him just because he was a clever lawyer. As nearly as I can make it out, she had set herself to secure the divorce and capture Shattuck--wealthy, fascinating, and all that, you know." "Shattuck--she!" I exclaimed. Kennedy, however, said nothing, but shot a quick glance at me, recalling by it our still fresh meeting with both Vina and Shattuck, as well as the visit from Rascon. I remembered also that it had been evident at our first meeting with Doctor Lathrop that he had shown a keen interest in what his wife was doing. Had it been really jealousy--or was it merely wounded pride? Kennedy still did not venture to comment, but I saw that he was very thoughtful and that his eyes were resting on the book of Freud which we had been discussing some time before. What was passing in his mind I could not guess, but would have hazarded that it had something to do with Honora's dreams. At least the recollection of them flashed over me. Had Doctor Lathrop been the lion in her path, in some way? What had that dream meant? So far it had not been explained. Little more was said, but after a few moments' chat with Doctor Leslie, Craig set determinedly to work, making up for the time that had passed without any laboratory addition to his knowledge of the case. Leslie waited awhile, then excused himself. He had hardly gone when Craig looked up from his work at me. "Walter," he said, briskly, "I wish that you would try to find out more about that story of Leslie's." Seeing that I was merely in the way, as he worked, now, I was delighted at the commission. I left him as he returned to the work of analyzing the materials Leslie had brought. For, I reasoned, here was a new angle of the case--Vina as the cause of all the trouble--and I was determined to find something bearing on it to add as my contribution to the ultimate solution. VIII THE POISONED GLASS I went out, at Craig's suggestion, eager to discover something more of the interesting bit of gossip which Leslie had hinted at about Vina and Doctor Lathrop. In fact, the relations of this pair interested me only slightly less than those of Honora and Vail Wilford. Just where to go I was in some doubt, for I had not an extensive acquaintance in the medical profession of the city, in which both Doctor Lathrop and Doctor Leslie stood high in their respective fields. However, I reasoned that Lathrop's social position offered a more promising approach than even his professional connections. Thus, I determined to reassume the rôle of reporter for _The Star_ which I had often used before with success in ferreting out odd bits of information of use to Kennedy. Accordingly, I soon found that the best point of departure was _The Star_ itself and to the office I went, hoping to find our society reporter, Belle Balcom, whom I knew to be a veritable Social Register and _Town Topics_ combined into one quick-witted personality. "I suppose, Miss Balcom," I began, as I found her finishing a spicy bit of copy in the reporters' room, while I sat on the edge of her typewriter table--"I suppose you're following this Wilford case closely?" She nodded vivaciously. "There hasn't been much to follow yet," she replied, eager to get whatever inside news she might for her society column. "Professor Kennedy is on the case, isn't he? You ought to know more about it than I do." "Yes, he's on it," I replied, trying to head off any inquiry on her part that might be embarrassing. "And already we know that it will be quite involved." "I know it," she asserted, and, as we chatted, I found, to my surprise, that she did know about the people concerned in the case. "You see," she explained, when I ventured to express my astonishment, "it's my business to be acquainted with what passes as 'news' to the readers of the society page. And then, too, you know that scandal and gossip constitute much of the small talk of the social set which figures in the society notes. By the way, I suppose you know about that little affair between Mrs. Wilford and Mrs. Lathrop out at the Brent Rock Country Club?" I was at once interested. It was exactly the sort of thing I had sought. "No," I confessed. "But I can quite appreciate that an encounter between Honora and Vina would be likely to be spirited--and add to our knowledge of the case. What was it?" Belle Balcom smiled breezily. For, whatever she might say about the smart set, she had been writing their gossip so long that she, too, quite appreciated a choice morsel of scandal. I have noticed that none of my profession ever gets so blasé that a new piece of "inside" news loses its charm--and I confess that in that respect I am quite like my fraternity. "It seems," she retailed, "that the Wilfords and the Lathrops were at the club at a Saturday-night dance two or three weeks ago. Of course, you know, the attentions that Mr. Wilford had been paying to Mrs. Lathrop had been noticeable for some time, then, and had been the source of a good deal of discussion and comment among various members of their set." "Of course," I encouraged. "Well, it was just a bit more noticeable that night than at other times. Mr. Wilford was with her practically all the time. Of course, Honora Wilford had noticed it, not only that night, but many times before. This time, though, she overheard one of the other women who didn't know that she was so near, talking about it and laughing with her partner." "That was the last straw," I anticipated. "Exactly. She waited until she saw Vail Wilford for a moment alone. As luck would have it, he was going for a sherbet for Mrs. Lathrop at the time. Mrs. Wilford was cutting. 'I suppose you realize that your wife is present to-night,' she said, icily. 'At least one dance is customary to let the world know that a husband and wife are on speaking terms.'" "What did he say to that?" "Oh, of course he mumbled that he had intended to dance with her next--but he went on and got the sherbet. The next dance he was too late." "Then Hades popped loose," I ventured. "You might say that. In the middle of the dance, Honora Wilford, who had declined more partners during the evening than most of the other women at the club had accepted, rose and deliberately walked across the dancing-floor, ostentatiously bowing good night to every one as she passed. You couldn't help noticing it. Even if any one had missed it, the summoning of her car would have been enough. It pulled up at the door of the club, with the cut-out open. It was scarcely eleven o'clock, too, and no one was thinking of going home at that time. Not a word was said. There was no scene. Yet that dance almost stopped." It was interesting, perhaps important for the case, yet not precisely what I had started out to find. "What of Doctor Lathrop?" I asked. "What did he do?" "He wasn't in the room at the time. He was down in the café. Wilford tried to brazen it out and Vina acted properly surprised. She can be quite an actress, too, when she wants to be. No, Doctor Lathrop didn't pay any attention to it--that is, not so any one saw it. But Vance Shattuck did. I remember him particularly that evening. Of course I know many of the stories back in his life--and a good deal of what they say about him now. He had been one of the partners Honora had persistently refused, but they did sit out a dance together and I'm sure it was she that ended the tête-à-tête, not he. He seemed to have very little interest in any one else there, and I saw him taking in the whole affair. Once he started forward, as if to offer to escort her home, then checked himself. I think he seemed to be rather pleased than otherwise at the turn of events in that little affair." "Playing a deep game?" I suggested. Belle Balcom shrugged. "I don't know--perhaps. Really, I thought at the time that this was not a triangle, but the making of a fine quadrangle--that is," she laughed breezily, "if you include Vance Shattuck, I guess you would call it a pentangle." "At any rate, all grist for the society-news mill," I smiled. "Doctor Lathrop really knew of the incident, didn't he?--at least, learned of it afterward?" "I imagine so." "You know the talk about the Lathrops?" I hinted. "I think I do--and I knew it long before this case started people's tongues wagging, too." "I understand it wasn't Wilford, after all, that Vina was interested in--but Shattuck himself." "So they say. Society gets its geometry pretty mixed in some of these angles," she laughed. "But do you think there is anything in the story about them?" I asked. "You're a very persistent interviewer," she returned. "Perhaps--but like the honest Japanese schoolboy, 'I ask to know.' It isn't interviewing for publication, you know. Really, I feel that if you do know anything, it is your duty to tell it. You can never know how valuable it may be to the case." "Of course--if you put it on a high ethical ground, that's different," she temporized. "I do. Listen. A crime has been committed. You have no more right to hold back one fact that may help to clear it up than you would to shield the person who committed it, in law, you know." "You're right. Yes--I'm convinced that it was the case--that she was merely playing with Vail Wilford, using him to get her freedom from the doctor, and that she was convinced that all she needed to do was to set herself to capture Vance Shattuck and he was as good as hers. That might be true of some men--sometimes," she added, "but Mr. Shattuck is too--too sophisticated to fall an easy prey to any one. You know, no woman can pursue him. He is a born pursuer." She paused a minute and nodded frankly at me. "No woman should trust him--yet many have. Some day, I really believe, such men always meet a woman who is more than a game-fish to an angler. Between you and me, I think Vance Shattuck has met her--and that there is nothing he would stop at to get her. But Vina is not that woman--nor can she understand. Yes, you are absolutely right in what you hinted at regarding Vina. I think you'll do well to watch the Lathrops--but mostly watch Vance Shattuck. There--I've said more than I intended to say, already. And remember, this is not a woman's intuition. I've been watching little things, here and there, and putting what I know together. Now--I've some more items to add to my column--it's short to-day." "Really, you ought to be a detective," I thanked her, as I turned from the desk. "You've helped me a great deal." "Flatterer," she returned, picking up a galley proof. "Come back again. If I hear anything more I'll let you know. I like Professor Kennedy." "Then it's to him you've been talking--not to me?" I asked, quizzically. "Or am I like John Alden--not speaking enough for myself, Priscilla?" "Please--I must read this proof. No--you're not talking for Miles Standish. Still, I consider you quite harmless. If you don't go now, I'll make you write the notes to take the place of these turned slugs in the proof." I departed in better humor, as I always was after a verbal encounter with Belle Balcom. More than that, she had given me enough to put some phases of the case in an entirely new light. As I hastened back to the laboratory I realized that the scheming of Vina had given an entirely new twist to the case, one which was beyond my own subtlety to interpret. On the way out of the city room I ran into Brooks, whose assignment was the Police Headquarters. "Great case your friend Kennedy's on now," he paused to comment, and I knew that he was hinting for information. "Yes. By the way," I replied, determined not to give it to him, but to sound him before he had a chance to do the same to me, "what do you fellows up at Headquarters know about the Rascon Detective Agency?" "Rascon?" he answered, quickly, and I could see his mind was working fast and that if we needed any assistance in hounding that gentleman, Brooks would give it voluntarily, hoping to get his own story out of it. "Why, Rascon has a reputation. They say he has pulled some pretty raw deals. The city force doesn't think much of him, I can tell you. Is he mixed up in it?" "Yes--indirectly," I admitted. "I thought perhaps you might keep an eye on him. There may be a story in him. Only, your word on one thing: Not a sentence is to go into _The Star_ about him until you've got my O. K." "I'll promise. What's he done? He does a good deal of shady business, I know." I was not averse to telling Brooks a bit, for I knew I could trust him. Besides, if the truth is to be told, on a big case it is the newspaper men who do quite as much of the digging out the facts as the police do. The most efficient detectives in the world are the newspaper men--and the regular detectives get a great deal of credit for what the newspaper men do. "He has been up to a fine piece of double crossing," I replied. "Now all I can tell you is that Wilford hired him to watch Mrs. Wilford. He faked a good deal--meetings with Vance Shattuck and that sort of thing. She gave up to him to suppress some of the fakes. But--well, I'd like to know more. Doyle, I think, has the fellow right. Now be careful. Don't let either of them know I tipped you off--and remember, your typewriter is broken until I tell you it's all right to go ahead." "Thanks for the tip, Jameson," said Brooks, as I bustled away. "I'll look it up--and let you know." "Have you found anything yet?" I inquired, half an hour later, as I entered the laboratory and found Kennedy still deeply engaged in the study of the materials which had been brought over by Doctor Leslie. As I watched him I saw that he was at work over a quantitative analysis, rather than searching blindly for something as yet unknown. "Yes," he replied, frankly, to my surprise, though, on second thought, I recalled that only when he was in doubt was Kennedy secretive. "I have. What about you?" "The hint from Leslie was right," I replied, and as briefly as I could I repeated what Miss Balcom had told me. Kennedy listened attentively, and when I had finished merely remarked, "That explains some things that I haven't cleared up yet." "Now tell me what you have found," I urged. "I'm very eager to know." "It was as I thought," he replied, slowly, "when I talked first with Leslie and Doyle. Wilford was not killed by atropin." "Then what was it?" I asked, mystified. "You remember, I found his pupils contracted almost to a pin-point?" he asked. "Yes. Was it morphine, as in the cases Doyle cited?" Craig shook his head. "No, it wasn't morphine, either. I had to go at it with practically no other hint. However, in this case the elimination of drugs was comparatively easy. I simply began testing for all I could recall that had the effect of contracting the pupils of the eyes. There was one thing that helped very much. The contraction was so marked in this case that I started off by looking for the drug which occurred to me next after morphine. I don't claim any uncanny intelligence for it, either. That part of it was all just pure luck." "Luck be hanged!" I exclaimed. "It's knowledge, preparedness. Would I ever have hit on it by luck?" "Still, I was as much surprised to find it so soon as you are to hear it." "I'll concede anything," I hastened. "I'm burning with curiosity. What was it?" "Wilford died of physostigmine poisoning," he answered. I suppose my face wrinkled with disappointment, for Craig laughed outright. "And--physostigmine--is what?" I inquired, quite willing to admit my ignorance if by that I might get ahead in understanding the mystery. "What does it do?" "It's a drug used by oculists, just as they use atropin, but for the precisely opposite effect. Atropin dilates the pupils; physostigmine contracts them. Both are pre-eminent in their respective properties." "Used by oculists!" I exclaimed, remembering suddenly that Honora Wilford's father, Honore Chappelle, had been an oculist. Kennedy apparently did not wish to encourage my quick deduction, for he paid no attention. "Yes," he repeated, thoughtfully, "it causes a contraction of the pupils more marked than that produced by any other drug I know. That was why I tried the test for it first--simply because it was at the top of the scale, so to speak." Interested as I was in physostigmine, which, by the way, now came tripping off my tongue like the name of an old friend, I could not forget our first acquaintance with the case. "But what about the atropin in the glass--and in the bottle?" I asked, hesitatingly. "I did not say that I had cleared up the case," cautioned Craig. "It is still a mystery. Atropin has not only the opposite effect on the eye from physostigmine, but there is a further most unusual fact about the relationship of these two drugs. This is one of the few cases where we find drugs mutually antagonistic. And they are antagonistic to a marked degree in this instance, too." He paused a moment and I tried to follow him, but was too bewildered to make an inch of progress. Here was a man killed, we knew, by a drug which Craig had recognized. Yet in the glass on his desk had been found unmistakable traces of another drug. Was it an elaborate camouflage? If so, it seemed to be utterly purposeless, for, even if Kennedy had not discovered the poison, the veriest tyro at the game must have done so comparatively soon. I gave it up. I could see no chance that the atropin might have been put in the glass either to point or to obscure suspicion. It was too clumsy and a brain clever enough to have conceived the whole thing would not have fallen into such an egregious error. It was too easy. But, if the obvious were rejected, what remained? By the grave look on Kennedy's face I was convinced that there was a depth of meaning to this apparent contradiction which even he himself had not fathomed yet. "Atropin is an antidote to physostigmine," he continued. "Three and a half times the quantity almost infallibly counteracts the poisonous dose." "But," I objected, "there was no trace of physostigmine in either glass, was there?" "No," he replied, "the glasses are here. I got them from Doyle's office while you were away. Not a trace in either. In fact, one of the glasses is really free from belladonna traces. The physostigmine I discovered was all in the stomach contents of Wilford--and there is a great deal of it, too. When you come right down to the point, we've taken a step forward--that's all. There's a long way to go yet." "But what of the physostigmine?" I queried. "How do you suppose it was given?" He shook his head in doubt. "I made a close examination. There were no marks on the body such as if a needle had been used. Besides, my investigations showed that a needle need not have been used. There are peculiar starch grains in the stomach associated with the poison. I admit I still have no explanation of that." For some minutes Kennedy worked along thoughtfully over his analysis, though I knew that he was merely endeavoring to determine in his own mind the next important move to make. "I think I'll vary my custom, in this case," he decided, finally. "I'm going to announce what I have discovered as I go along. If you tell it to one you may depend that it will spread to the others eventually. It will be interesting to see what happens. Often when you do that it's the quickest way to have the whole truth come out--especially if some one is trying to conceal it." There was a tap on the laboratory door and I rose to open it, admitting Doyle himself, quite excited. "What's the matter?" greeted Kennedy. "There's the deuce to pay up at the Wilford apartment," replied Doyle. "Shattuck called there to see Mrs. Wilford this afternoon and offer her his sympathy." I glanced over to Kennedy, who nodded to me. It was evidently the visit about which we already knew. "I wasn't there," went on Doyle, "but McCabe was, of course. I don't know just what happened, but McCabe and Shattuck had some kind of run-in--Shattuck protested against the way we're holding Mrs. Wilford, and all that. Some mess!" He shook his head dubiously. "Why?" prompted Kennedy. "What's the trouble?" "Trouble enough. Mrs. Wilford's almost in a state of hysteria. When I tried to smooth things over she ordered me out of the apartment, said she'd receive whom she pleased and when and where she pleased." Kennedy scowled. I could well imagine Doyle "smoothing" anything over. A road-roller would have been tactful by comparison. "I think she's breaking," he pursued. "I know I'm on the right track. I thought you might like to know it. If I don't get a confession--say, I'll eat my shield!" With difficulty I restrained myself. It was not policy to offend Doyle, I reasoned. "Say," pursued Doyle, with a knowing nod, "you remember I found out that some one had been at that office the night Wilford was murdered?" "Yes," agreed Kennedy. "Well--who was it?" demanded Doyle. "Who _must_ it have been? Who wanted her husband out of the way? Isn't it clear?" There was no mistake that he implied Honora. "By the way," interposed Kennedy, "I think I've found the poison that killed him." "Belladonna--eh?" "No. Just the opposite--physostigmine." Doyle stared. Yet he could not dispute. "Maybe it was. But it's a poison just the same--ain't it?" he hastened. Then he added, aggressively, "I know what I'm going to do. I'm going to put a dictagraph in that place." Kennedy smiled encouragingly. I knew what his thought was. This was the height to which Doyle's mind reached. Yet, I reasoned, perhaps it was not without its value, after all. IX THE ASSOCIATION TEST "I think I ought to visit Mrs. Wilford, after that," decided Kennedy, the moment Doyle had left. "This case is really resolving itself into a study of that woman, or rather of her hidden personality." Accordingly he doffed his acid-stained smock which he wore about the laboratory, and we set out for the Wilford apartment. When we arrived we were not surprised to find Honora in a highly nervous state, really bordering on hysteria, as we had been told by Doyle. McCabe had taken up a less conspicuous place in which to watch her, from a neighboring apartment in which he had got himself placed. As we met her, it actually seemed as if Honora had turned from Doyle and McCabe to Kennedy. "Were the dreams I wrote for you all right?" she asked, with a rather concealed anxiety. "Perfectly satisfactory," replied Kennedy, reassuringly. "I haven't finished with them yet. I'll tell you about them later. They were all right, but I never have enough of them. I suppose Doctor Lathrop used to say that too?" She nodded. Evidently Craig had won her confidence, in spite of what she must have known about us by this time. "Are there any other dreams that you have thought of since?" he inquired, pressing his advantage. She passed her hand over her forehead wearily and did not answer immediately. "You look tired," Craig remarked, sympathetically. "Why not rest while we talk?" "Thank you," she murmured. As he spoke, Kennedy had been arranging the pillows on a _chaise-longue_. When he finished, she sank into them, resting her head, slightly elevated. Having discussed the various phases of the psychanalysis before with Kennedy, I knew that he was placing her at her ease, so that nothing foreign might distract her from the free association of ideas. Kennedy placed himself near her head and motioned to me to stand farther back where she could not see me. "Avoid all muscular exertion and distraction," he continued. "I want you to concentrate your attention thoroughly. Tell me anything that comes into your mind. Tell all you know of your feelings. Concentrate. Repeat all you think about. Frankly express all the thoughts you have, even though they may be painful and perhaps embarrassing." He said this soothingly and she seemed to understand that much depended upon her answers and the fact that she did not try to force her ideas. "Tell me--of just what you are thinking," he pursued. Dreamily she closed her eyes, as though allowing her thoughts to wander. "I am thinking," she replied, slowly, still with her eyes closed, "of a time just after Vail and I were married." She choked back the trace of a sob in her voice. "It is a dream," she went on. "I seem to be alone, crossing the fields--it is at the country estate where we spent our honeymoon. I see a figure ahead of me. It is Vail. But each time that I get close to him--he has disappeared into the forest that skirts the field." She stopped. "Now--I see the figure--a figure--but--it is not Vail--no, it is another man--I do not know him--with another woman--not myself." She had opened her eyes as though the day-dream was at an end, but before she finished the sentence she had deliberately closed them again. From what I learned of the method of psychanalysis, I recalled that it was the gaps and hesitations which were considered most important in arriving at the truth regarding the cause of any nervous trouble. More than that, as she had said the words, it was easy to read into her remarks the fact that she knew there had been another woman in Wilford's life. It had wounded her deeply, in spite of the fact--as Kennedy had demonstrated by the Freud theory--that she really had not cared as greatly for Wilford as even she herself had thought. Even to me it was plain in this day-dream recollection that the man throughout it was really Vail. She knew it was Vail and she knew that woman with him was Vina. But in her wish that it should not be so, she had unconsciously changed the face on the "figure" she saw. It was her endeavor to preserve what she desired. She had unconsciously striven not to have it her husband, as it was not herself she saw in the vision with him. "Go on," urged Kennedy, gently. "Is there anything else that comes into your mind?" "Yes" she murmured, dreamily. "I am thinking about some of Vail's clients." "About any of them in particular?" hastened Kennedy, eager to catch the fleeting thought before she might either lose or conceal it. "About any one contemplating a suit for divorce?" "Y-yes," she replied before she realized it, her eyes opening as she came out of the half-relaxed state again, recalled by the sound of Kennedy's voice. "What were you thinking about that person?" "That he was devoting entirely too much time to that sort of practice," she answered, quickly, avoiding a direct reply. "I can remember when I first knew him that he was in a fair way to be a very successful corporation lawyer. But the money and the cases seemed to come to him--the divorce cases, I mean." Kennedy ignored the last, explanatory part of the remark, as though he penetrated that it disguised something. He did not wish to put her on guard. "Devoting too much time to the practice?" he queried, "or do you mean you think he was devoting too much time and attention to the particular client?" Honora was thoroughly on guard now, in spite of him. Had she known, she probably would never have allowed herself to be led along until Kennedy struck on such an important "complex." But, quite evidently, she knew nothing of the Freud theory and trusted that her own control of herself was sufficient. And, indeed, it would have been had it not been that the dreams betrayed so much, that even she did not realize, to one who understood the theory. She did not answer. "Who is it that you were thinking about?" persisted Craig, refusing to be turned aside. "Oh, no one in particular," she replied, quickly, with a petulant little shrug. Yet it was plain now that she had been thinking of some one, both in the last remarks and perhaps in the day-dreams she had repeated. She was now trying to hide the name from us. By this time, also, Honora was sitting bolt-up-right on the _chaise-longue_, staring straight at Kennedy, as though amazed at her own frankness and a bit afraid of what it had led her into. "Was it Vina Lathrop?" he asked, suddenly. "No--no!" she denied, emphatically. Yet to me it was evident that it most certainly had been Vina whom she had in mind. The association test of the waking state quite accorded with the results of the dream study which Kennedy had made. Moreover, it was now evident that Honora was holding back something, that she had taken refuge in silence. Vainly Kennedy now strove to restore the relaxed condition, in which she might let her thoughts wander at will. It was of no use. She simply would not let herself go. Deftly he changed his tactics altogether and the conversation drifted off quickly to inconsequential topics, such as would restore any shaken confidence in him. Clearly it was too early to come to an open break with her. Besides, I understood, Kennedy would rather have allowed her to believe that she had come off victor than to have pressed any minor advantage. "Please don't repeat this," he remarked, as we were leaving. "You can readily understand the reason. I quite appreciate the uncomfortable position in which the city detectives have placed you, Mrs. Wilford. Depend on me, I shall use every influence I have with them to mitigate the hardship of their presence. Besides, I know how brutally annoying they can be. You understand--my position is quite different. And if I can be of any assistance to you, no matter in what way, don't fail to command me." I had expected her to be a bit put out by our continued quizzing. On the contrary, however, she seemed to be actually grateful for Kennedy's sympathy, now that he had ceased treading upon dangerous ground. "Thank you," she sighed, as we rose to leave her. "I feel that you are always trying to be fair to me." Kennedy hastened to assure her that we were, and we left before the final good impression could be destroyed. "I consider you an artist, Craig," I complimented, as we left the elevator a few minutes later, after a brief talk with McCabe in which Kennedy urged him to keep a close watch, but to seem not to be watching. "We go to cross-examine; we leave, friends. But I don't yet understand what the idea was of trying the association test on her." "Couldn't you see that when we came there she was in a state verging on hysteria?" he replied. "No doubt, if McCabe had stayed she would have been quite over the verge, too. But it would not have done them any good. They always think that if any one 'blows up,' as they call it, they'll learn the truth. That's not the case with a woman as clever as Honora. If she gave way to hysteria, she would be infinitely more likely to mislead them than to lead them. Besides, in the study of hysteria a good deal of what we used to think and practise is out of date now." I nodded encouragingly, not so much that I cared about the subject of hysteria, either what was known of it now or long ago, as that I was deeply interested in anything whatever that might advance the case. "Perhaps," he went on, "you are not aware of the fact that Freud's contribution to the study of hysteria and even to insanity is really of greater scientific value than his theories of dreams, taken by themselves. Study of Freud, as you can see, has led us already to a better understanding of this very case." "But what sort of condition did you think her in before you reassured her at the start by the association test?" Kennedy thought a moment. "Here is, I feel, what is known as one of the so-called 'borderline cases,'" he answered, slowly. "It is clearly a case of hysteria--not the hysteria one hears spoken of commonly as such, but the condition which scientists to-day know as such. "By psychanalytical study of one sort or another we may trace the impulse from which hysterical conditions arise, penetrate the disguises which these repressed impulses or wishes must assume in order to appear in the consciousness. Such transformed impulses are found in normal people, too, sometimes. The hysteric suffers mostly from reminiscences which, paradoxically, may be completely forgotten. "Thus, obsessions and phobias have their origin, according to Freud, in sexual life. The obsession represents a compensation, a substitute for an unbearable sex idea, and takes its place in consciousness." "That is," I supplied, "in this case you mean that her husband's lack of interest in her was such an unbearable idea to her that in her mind she tried to substitute something to take its place?" "Precisely. In normal sex life, as you recall, the Freudists say that no neurosis is possible. Also recall what I said, that sex is one of the strongest of impulses, yet subject to the greatest repression--and hence is the weakest point in our cultural development. Often sex wishes may be consciously rejected, but unconsciously accepted. Well, now--hysteria arises through the conflict between libido--the uncontrollable desire--and sex repression. So, when they are understood, every hysterical utterance has a reason back of it. Do you catch the idea? There is really method in madness, after all. "Take an example," he continued. "When hysteria in a wife gains her the attention of an otherwise inattentive husband, it fills, from the standpoint of her deeper longing, an important place. In a sense it might even be said to be desirable for her. You see, the great point about the psychanalytic method, as discovered by Freud, is that certain symptoms of hysteria disappear when the hidden causes are brought to light and the repressed desires are gratified." "But," I interrupted, "how does this analysis apply to the case of Honora Wilford?" Kennedy considered a moment. "Very neatly," he answered. "Honora is suffering from what the psychanalysts call a psychic trauma--a soul wound, as it were. Recall, for instance, what our dream analysis has already shown us--the old love-affair with Shattuck. To her mind, that was precisely like a wound would have been to the body. It cut deeply. Seemingly it had healed. Yet the old scar remained--a repressed love. It could no more be taken away than could a scar be taken from the face." "Yet was not open and visible like a physical scar," I agreed. "Quite the case. Then," he pursued, "came a new wound--the neglect by her husband whom she thought she loved, and the discovery of Vina Lathrop as the trouble-maker." "I begin to see," I returned. "Those two sets of facts, the old scar and the new wound, are sufficient, you think, to explain much in her life." "At least they explain about the hysteria. In her dream, a wave of recollection swept over her and, so to speak, engulfed her mind. In other words, reason could no longer dominate the cravings for love so long repressed. The unconscious strain was too great. Hence the hysteria--not so much the hysteria and the isolated outburst which Doyle saw, as the condition back of it which must have continued for days, perhaps weeks, previous to the actual murder of Wilford." I frowned and objected inwardly. Was Craig, also, laying a foundation for the ultimate conviction of Honora? Before I could question him there was an interruption at the door and I sprang to open it. "Hello, Jameson!" greeted Doctor Leslie; then catching sight of Kennedy, he entered and asked, "Have you discovered anything yet, Professor?" "Yes," replied Craig, "I should say I have." Leslie was himself quite excited and did not wait for Craig to go on. "So have I," he exclaimed, searching Kennedy's face as he spoke. "Did you find physostigmine in the stomach contents I sent you? I did in what I retained." Kennedy nodded quietly. "What does it mean?" queried Leslie, puzzled. Kennedy shook his head gravely. "I can't say--yet," he replied. "It may mean much before we are through, but for the present I think we had better go slow with our deductions." Leslie evidently had hoped that Kennedy's active mind would have already figured out the explanation. But in cases such as this facts are more important than clever reasoning and Kennedy was not going to commit himself. "Doyle tells me that he has put in a dictagraph in the Wilford apartment," ventured Leslie, changing the subject unwillingly. "Has he learned anything yet?" "No, not yet. It's too soon, I imagine." Leslie paused and glanced about impatiently. Things were evidently not going fast enough to suit him. Yet, without Kennedy, he felt himself helpless. However, there was always one thing about Leslie which I was forced to like. He was no poser. Even when Doyle and the rest did not recognize Kennedy's genius, Leslie quite appreciated it. Although he was a remarkably good physician, he knew that the problems which many cases presented to him were such that only Kennedy could help him out. "You've heard nothing more about the gossip regarding Mrs. Lathrop and Shattuck?" I asked. "No, nothing about that. But there is something else that I have found out," he added, after a moment--"something that leads to Wilford's office." Kennedy was interested in a moment. We had been so occupied with the case that we had not even a chance to go down there yet, although that would have been one of the first things to do, ordinarily, unless, as in this case, we were almost certain that the ransacking of Doyle and Leslie had destroyed those first clues that come only when one is called immediately on a case. "I've been looking about the place," went on Leslie, encouraged by Kennedy's interest. "I knew you'd be busy with other things. Well, I've discovered one of the other tenants in the building who did not leave his office on the same floor until just after seven o'clock last night." "Yes?" inquired Craig. "Did he see or hear anything?" Leslie nodded. "Early in the evening there must have been a woman who visited Wilford," he hastened. "Who was she?" "The tenant doesn't know." "Did he see her?" "No. He remembers hearing a voice on the other side of the door to the hall. He didn't see any one, he says, and it is quite likely. When I asked him if he overheard anything, he replied that he could catch only a word here and there. There was one sentence he caught as he closed his own door." "And that was--?" "Rather loudly, the woman said: 'Give her up, Vail. Can't you see she really doesn't love you--never did--never could?'" Leslie paused to watch the effect of the sentence on us. I, too, studied Kennedy's face. "Did she leave soon?" asked Craig. Leslie shook his head. "I don't know. The tenant left and that was all I heard." "Well, Wilford was not dead then, we know," considered Craig. "Could she have been there when he died? Of course you don't know." "It's possible," replied Leslie. To myself, I repeated the words: "Give her up, Vail. Can't you see she really doesn't love you--never did--never could?" A few hours ago I should have been forced to conclude that only Vina might have said it, knowing as she did the peculiar nature of Honora and the relations between Wilford and his wife. But now, with the hints discovered by Leslie and amplified by Miss Balcom, I could not be so sure. The remark might have come equally well from Honora herself and have applied to Vina--for Honora, too, might have known that it was not love for Wilford that prompted Vina's interest in her husband, but the desire to make sure of her divorce for the purpose of being free to capture Vance Shattuck. Interesting and important as the discovery was, it did not help us, except that it added to the slender knowledge we had of what had taken place at the office. A woman had been there. Who it was, whether Honora or Vina, we did not know. Nor did we know how long she had stayed, whether she might merely have dropped in and have gone before the crime was committed. "You've told Doyle?" asked Kennedy. "Naturally. I had to tell him. Remember, it was much later that he found that some one else had been at the office, according to the janitor's story." "I do remember. That's just what I have been thinking about. I suppose he'll tell it all around--he usually does use such things in his third-degree manner." Leslie smiled, then sobered. "Quite likely. Does it make any difference?" "Not a bit. I'm rather hoping he does tell it around. I've decided in this case to play the game with the cards on the table. Then some one is sure to make a false move and expose his hand, I feel sure." Quickly I canvassed the situation. All might be involved, in one way or another--either Vina or Honora might have been the early visitor; later it might have been either Shattuck or even Lathrop, or perhaps neither, who had been there, as far as the janitor's vague observation was concerned. "There was something strange that went on at that office the night of the murder," ruminated Kennedy. "Maybe there is some clue down there, after all, that has been overlooked. You've searched, you say. Doyle has searched. The place must have been pretty well gone over. However, I can see nothing left but to search again," he decided, quickly. "We must go down there." X THE ORDEAL BEAN Wilford's office was in an old building of the days when a structure of five or six stories, with a cast-iron, ornamented front, was considered a wonderful engineering achievement. It was down-town, in the heart of the financial district, and had been chosen by Wilford, without a doubt, to convey an impression of solidity and conservatism, a useful camouflage to cover the essential character of his law practice as scandal attorney. We climbed the worn stairs with Leslie, and, as we mounted, I noticed that there was also, down the hall, a back stairway, evidently placed there in case of fire. Hence, it was possible, I reasoned, for a person to have slipped in or out practically unobserved from the front. We knew now that at least one person, probably two, had been there, though who they were we did not know. Nor was there yet any clue, except that certainly a woman had visited Wilford, at least early in the evening. Wilford's office was on the third floor, in the front. We entered and looked about. Past the outer railing and outer office was his own sanctum. It was furnished lavishly with divans and settees in mahogany and dark leather, with elaborate hangings over the windows and on the walls. There were law-books, but only, it seemed, for the purpose of giving a legal flavor to the place. Most of the legal library was outside. The office was rather like a den than a lawyer's office. Reflecting, I could see the reason. Society must be made welcome here, and at ease. Besides, the conservative surroundings were quite valuable in covering up the profession--I had almost said, business--of divorce made easy and pleasant. I recalled Rascon and the crook detectives who made little concealment of their business--"Evidence for divorce furnished." Doubtless many of these gentry had found occupation from this source. What stories these walls might have told! They would have made even Belle Balcom's ears tingle. At once Kennedy began his search of the office, going over everything minutely but quickly, while we waited, apart. "Not even a finger-print has been left unobscured!" he exclaimed, finally, almost ready in disgust to give it up. "It is shameful--shameful," he muttered. "When will they learn to let things alone until some one comes who knows the scientific importance of little things! If only I could have been first on the job." "There's the typewriter," suggested Leslie, trying to divert attention and smooth things over. "Have you the letter?" asked Craig. Leslie drew it eagerly from his pocket and unfolded it. Kennedy took it, spread it out and studied it a moment: HONORA: Don't think I am a coward to do this, but things cannot go on as they have been going. It is no use. I cannot work it out. This is the only way. So I shall drop out. You will find my will in the safe. Good-by forever. VAIL. Then Craig moved over and sat at the typewriter. Quickly he struck several keys, then made a hasty comparison of the note with what he had written. "The 's' and the 'r' are out of alignment, the 'e' battered--in both," he concluded, hurriedly, as though merely confirming what he was already convinced of. "There are enough marks to identify the writing as having been done on this machine, all right. No, there's nothing in this note--except what is back of it, and we do not know that yet. Did Wilford write that letter, or was it written for him? It could hardly have been done voluntarily." "It was in this desk chair that we found him sprawled--so," illustrated Doctor Leslie, dropping into the chair. Then, straightening up, he indicated the big flat-topped desk in the middle of the room. "The two glasses were on this desk--one of them here, the other over there." As he pointed the spots out, one of them near where he was, the other near the outer edge of the desk, Kennedy's eye fell on the desk calendar. "I removed the pages I told you about," supplied Leslie, noticing the direction of Craig's glance. "It's a loose-leaf affair, as you see. Here they are." Leslie drew from his pocket the leaves for the various days, and we looked at them again, with their notations--one reading, "Prepare papers in proposed case of Lathrop _vs._ Lathrop." Others read, "Vina at four," and other dates, with hours attached. There were several of them, more than would seem to have been necessary were the relation merely that of lawyer and client for so brief a time. There were none for the day of the murder however. Kennedy continued the search, now rummaging the papers, now directing either Leslie or myself to bring him objects. He had asked me for a letter-file, and I was turning from a cabinet to hand it to him when my foot kicked some small, soft object lying along the edge of the rug. The thing, whatever it was, flew over and hit the baseboard. Mechanically I reached down and picked the object up, holding it in the palm of my hand. It seemed to be a rough-coated, grayish-brown bean, of irregular, kidney shape, about an inch long and half an inch thick, with two margins, one short and concave, the other long and convex. The surfaces were rounded slightly, but flattened. The coat of the bean was glossy. Kennedy, with quick eye, had noted that I had picked up something and was over at my side in a moment. "What's that?" he asked quickly, taking the thing from my hand as I turned to him. He looked at it critically for a moment. Then he pressed the hard outer coat until it parted slightly, disclosing inside two creamy white cotyledons. He studied them for some time, then pressed the bean back into shape again as it had been before. I was about to ask what he thought it was, and where it came from, when there was a noise in the direction of the door. We turned to see that it was a man in overalls shuffling in, his cap in his hand. "Oh, beggin' your pardon, Doctor," he addressed Leslie, "I heard some one here. I didn't know it was you." It was the night watchman who had been off the job on perhaps the only occasion in years when it would have meant much for him to have been on it, but was making up for his laxity now by excessive vigilance. "Pete," demanded Leslie, sharply, "did you see a woman here that night?" "N-no, sir--that is, sir--I don't know. There was some one here--but Mr. Wilford, he kept such late hours and irregular that I thought nothing of it. I thought it was all right, sir. Later, when I didn't hear any voices, I thought they had gone home. I didn't see the lights burnin'--you wouldn't ha' noticed that, except from the other side of the street. I s'pose that's why they didn't discover the body till mornin'. But a woman here--no, sir, I can't say as I'd say that, sir." Whatever else there might have been said about Pete, it was evident that he was perfectly honest. He even confessed his lack of observation and his inefficiency with utter frankness. There did not seem to be a hope of obtaining anything by questioning Pete. He had told all he really knew. Others might have embellished the story had they been in his place, and so have led us astray. At least he had the merit of not doing that. "So--here you are," exclaimed a deep voice at the door. It was Doyle, flushed and excited. "You may go, Pete," nodded Leslie to the janitor, who backed out of the room, still pulling at his cap. Alone, Doyle turned to us. "Confound Shattuck!" he exclaimed. "That man is the limit. I'll get him, if he doesn't look out. He's a game bird--but he flies funny." "Why, what has he done now?" asked Kennedy. "Done?" fumed Doyle. "Done? Been threatening, I hear, to have me 'broke'--that's all. I don't care about that, not a whoop--even if he had the influence with the administration. What I care about is that he is putting every obstacle in the way of my finding out anything from that woman. She's hard enough to manage, Heaven knows, without his butting in." "What about that bean Jameson picked up here?" asked Leslie, impatiently, as Doyle paused. "Have you any idea what it may be?" "A bean?" inquired Doyle, looking from one of us to the other and not understanding. "A bean? Picked up here? Why, what do you mean?" I was inclined to be vexed at Leslie for having mentioned it, but I soon saw that Kennedy betrayed no traces of annoyance. On the contrary, he seemed rather eager to answer, as he drew the thing from his pocket, where he had placed it when Pete came in. "Just something Jameson happened to find on the very edge of the rug, quite by accident, over by the letter-files," Craig explained, with a certain gusto at showing Doyle a thing that he had overlooked. "Ever see anything like it?" Doyle took the bean, but it was evident that both it and its discovery meant nothing to him. "No," he admitted, reluctantly. "What is it?" "Without a doubt it is one of the famous so-called 'ordeal beans' of Calabar," replied Kennedy, offhand. "Calabar?" I repeated, in surprise. "Why, that's a place on the west coast of Africa, isn't it? What would a Calabar bean be lying on the floor here for?" "What do you mean--ordeal bean?" questioned Doyle, somewhat incredulously, while Leslie maintained a discreet silence. "In the Calabar, where these things grow," explained Kennedy, not put out for an instant, "as you perhaps know, they have a strange form of dueling with these seeds. Two opponents divide a bean. Each eats a half. It is some religious ceremony--voodoo, or some such thing, I suppose--a superstition. Sometimes both die--for the bean contains physostigmine and is the chief source from which this drug is obtained." "You mean they _eat_ it--a poison?" I asked. "Certainly. Over there, the natives believe that God will decide who is guilty and who is innocent, and that he will miraculously spare the innocent. I suppose that sometimes one gets a half a bean that doesn't contain so high a percentage of the poison--or else some people are not so susceptible to its toxin, or something like that. Anyhow, that's one way they use it." "Why," I exclaimed, "that is primitive justice, you might say--the duel by poison!" "Exactly," Craig nodded. Doyle stared, amazed and puzzled. "No worse than some of the things our ancestors did, not many centuries ago," reminded Craig. "They used to have all sorts of ordeals, by fire and water and what not. We haven't progressed so far over the savages, after all. Civilization is only a veneer, and pretty thin, sometimes. Underneath we're quite like the savage--only we substitute mechanical war for brute strength and high finance for highway robbery. The caveman and the cavewoman are in all of us--only we manage either to control them or conceal them--except when something happens that means calling in either Doyle or myself." "What's this--phy--physos--what you call it?" demanded Doyle, forgetting to conceal his ignorance in his curiosity. "A drug," replied Kennedy. "One effect it has is to contract the pupil of the eye. Both Leslie and I have discovered considerable traces of it in Wilford's stomach. In such quantities, it would be very poisonous. By the way, this bean would account also for those starch grains I found, Walter," added Kennedy. "Then you mean you think that Wilford ate one of these things?" queried Leslie. "That there was a--duel by poison?" demanded Doyle, hesitating over the words I had used. "I know he must have eaten one of those beans," asserted Kennedy. "What else could it have been? He certainly didn't eat this one, though. There must have been more. This one must have dropped on the floor in the excitement and have been overlooked. You didn't find any traces of others about, did you?" he added, looking from Doyle to Leslie. Leslie shook his head negatively. Doyle's puzzled face was answer enough from him. I considered a moment as an idea struck me, offering a refuge from an unpleasant implication of Kennedy's remarks which I foresaw and which I knew would occur to Doyle, if not directly, at least very soon. "Shattuck has traveled widely," I remarked, reflectively. "He himself told us, you recall, that he had hunted big game in Africa. Perhaps he has been in the Calabar, too--at any rate somewhere on that continent where he might have learned of these beans and the use to which the natives put them." Kennedy nodded again, cautiously. "A good many such beans are imported for medical purposes to obtain the physostigmine from them," Craig remarked, carefully. "It's the source of the drug. Don't jump too hastily at your conclusions, Walter. Remember, physostigmine is a drug that is known and used by oculists, too, for its effect on the pupil of the eye, the opposite of belladonna." I could have sworn at Kennedy for that. It was just the idea that I had wanted to keep away from Doyle. I had known that he would pounce on it like a hawk. Now I was sure that he would use it against Honora. "Oh--oculists use it, do they?" repeated Doyle, running true to form. "Ah--I see." He looked about, from one to the other of us, knowingly. No one said anything as he continued to gaze with superior slyness at us, regarding us as poor simpletons who were unable to see through a millstone with a hole in it. "I see--I see," he added. "Honora--Chappelle. That was her name before she was married. Her father was a Frenchman, Honore Chappelle--an oculist--well known in the city before he died. Oh, that's very important, then, that about this bean and the physostigmine, or whatever you call it. And, Leslie, you say you've discovered that some one--a woman--was here early in the evening. Can't we put two and two together? She's lying when she says she wasn't out of that house, she is. So is that Celeste, the hussy. Depend on it, she was here. I'm on the right track, all right," Doyle concluded with a cocksure shake of the head that was more irritating than any amount of ignorance on his part would have been. I did not reply. I understood the purport of the broad insinuation that Doyle was making. Also, I saw the real reason of Kennedy's remark to me, cautioning me to make haste slowly in deducing anything from the, as yet, slender facts of the case. I thought a moment. Far from eliminating anybody, the discovery of the Calabar bean left us scarcely a bit ahead of where we had been before. With a keen repulsion against the very idea and its implications as seen by the astute Doyle, I still was forced to admit that Honora Wilford's father had been an oculist and that it was perfectly true that she had every opportunity to have learned of the ordeal bean and its drug. Yet I kept asking myself what, after all, that might mean. Purposely Kennedy reverted to the Calabar bean and the remarks of Doyle that had started the conversation. "If Shattuck gets too brash," hinted Kennedy, "spring this information on him. Perhaps it might interest him." As he said it, I remembered what Craig had said in the laboratory only a short time before--that he was going to tell part of what he had found, as he went along, in the hope that the actions of each suspect who heard it might perhaps betray some thing. There was some crumb of comfort in that, I felt, as far as Honora herself was concerned. Yet I felt uncomfortable and misgiving. We parted from Leslie and Doyle, and as we went up-town again I could not help remarking that somehow the apparent effort of Shattuck to hamper us was suspicious. Kennedy said very little, but when we got off at the station on the Subway just before our own, I saw that he was not yet through. It did not take long to elicit from him the information that, while he felt he could trust Doyle to convey the information about the discovery and the drug to both Shattuck and Honora before long, the case was different as far as Vina and Doctor Lathrop were concerned. As we entered Doctor Lathrop's office, we found that not only was he there, but that his wife was there also. However, it was quite evident that they had been having words, and all was not as serene between them as they would have us wish, by the forced looks on their faces. In short, they had been quarreling. I could have guessed what it was about, but Kennedy affected not to notice that anything was wrong and I fancied that Vina, at least, wore a look of relief as she saw that he was not paying any attention to it. Briefly, Kennedy outlined what we had found--the physostigmine in the stomach, the poison, the bean itself, which he took particular pains to describe along with the circumstances under which it had been found. "Did you ever have any of these ordeal beans?" asked Kennedy, displaying the one we had found. "I have had them," admitted Lathrop. I thought I caught a covert look at his wife, as if to see how she was taking the discovery. As for Vina, I knew that she was far too clever to betray anything, especially before us. "They're comparatively easy to obtain in New York," went on Lathrop, with greater ease. "Drug importers get them in quantities to derive the drug from them. However, now I employ the drug itself, the few times I have any occasion to use it. I suppose I've got some in my medicine-chest." As we talked, I saw that Vina was really listening, keen and silent. If actions for which we had no immediate explanation had bearing on the question of guilt, I felt that her very manner was incriminatory in itself. Why should she try to conceal under a cloak of indifference her real interest in the thing? And yet, even with Vina, I was loath to jump at a conclusion. Somehow or other her preoccupied manner and the stress of her suppressed attention aroused my suspicions most strongly against her, after what other things I knew of her private affairs. As we left them and hurried toward the laboratory, I found myself wondering whether she might not have been the visitor to Wilford whom the tenant had overheard talking in Wilford's office. As for the why of such a visit, I was forced to admit I had no explanation. I reacted against the deduction that perhaps Honora had known of the properties of the Calabar bean and had been able to obtain some of them. Yet it was clearly that that was in Kennedy's mind as we approached his workshop. We had scarcely entered the hall when I saw that there was some one waiting for us near the door. It was Brooks, of _The Star_. Brooks wore a very important air of secrecy, as though he had been doing a bit of gumshoeing and was proud of it. "Something about Rascon?" I asked, jumping to the conclusion, after I had introduced Brooks to Craig. "Yes," he replied, eagerly, "I've got a clue." "A clue? Why, we've got Rascon--at least Doyle can get him whenever we want him. What do you mean?" I asked. "How about those reports?" answered Brooks, pointedly. "You know he did a good deal of work for Wilford and wrote a good many of them. The reports are gone--Doyle told me." "Where are they?" asked Kennedy, quickly appreciating the possible importance of the matter. "Is that what you've found out?" Brooks looked knowing. "Ah--that's just it. You see, I decided to trail the trailers, so to speak. There's one very trusted operative of Rascon's--he calls him Number Six--that's his denomination, I believe, in the Rascon records. Well, that fellow has double-crossed him. He has stolen the reports, I hear. Or perhaps it's part of Rascon's plan to cover himself. I don't know. At any rate, I've traced Number Six to a river-front saloon--you may know of the place, a tough joint called 'The Ship,' on Water Street. Without a doubt there's something there." Brooks was speaking earnestly and I looked questioningly at Kennedy. "I believe it's worth following up," decided Craig, not even stopping to unlock the laboratory door, as we turned away with Brooks. "If we had those records it might point up the case very closely." XI THE RASCON REPORTS We found The Ship Café, which Brooks had already investigated, on a river-front street in the outskirts of the Greenwich Village section of the city. "The Ship" was a disreputable-looking frame building, a tavern of several generations ago, once historically famous, but now, like a decayed man about town, relegated to the company of those whom formerly he would have scorned. Not many months ago it had been a saloon. Now a big sign declared that only soft drinks were sold in it. Even that change did not seem to have done much for the respectability of the place. The neighborhood was still quite as tough and squalid and "The Ship," itself, with a coat of paint, had not become even a whited sepulcher. Kennedy, Brooks, and myself entered and passed into a typical, low-ceilinged back room of the old days. There at a number of greasy, dirty round tables sat a miscellaneous collection of river-rats, some talking and smoking ill-favored pipes, others reading newspapers. I felt sure that they were drinking something other than soft drinks, and wondered whence the stuff had come. Had it been smuggled in on vessels from the near-by wharves? We sat down and for some moments Brooks and I did most of the talking, being careful to cover ourselves and pose neither as detectives nor even as newspaper men, lest the slightest slip might excite suspicion among the evil-looking customers of the den. We had been sitting thus for some time, Kennedy saying very little, when Brooks leaned over toward me and whispered, in reality to Kennedy: "The fellow I discovered--the one they call Number Six--has a room up-stairs. If we could only register here we might get a room--and a chance to search the other rooms." Kennedy nodded non-committally, but made no effort to put the suggestion into execution, and I saw that he was merely waiting for something to turn up. For almost an hour we remained talking at the table, endeavoring to ingratiate ourselves with the waiter of the place, a rather burly fellow, who seemed to regard us with suspicion as strangers. Yet, as long as we did nothing or asked nothing indiscreet our burly waiter seemed unable to do anything else than tolerate us. I was becoming impatient, when a furtive-looking individual entered from what had formerly been the bar. Brooks winked sidewise at us and I gathered that the new-comer was the redoubtable "Number 6," the operative of the Rascon Agency whom Brooks had located. He cast his furtive eyes around and his glance caught Brooks, who nodded, beckoning him over to the table. The former operative sidled over and sat down, eying us suspiciously, in spite of Brooks's effort to handle him with tact. We fell into conversation, beginning on the weather and progressing to the usual topic of the evil times into which prohibition was throwing us. Gradually Brooks led around to more intimate subjects and finally the name of Rascon was mentioned. At once the former operative flew into a towering rage. "Say," he ejaculated, "if I should tell you of all the crooked deals that fellow was in--" He checked himself in spite of his anger, and at once a look of suspicion crossed his face as he glanced doubtfully at us. At least I felt there could be no question that the operative had really double-crossed Rascon. As to whether we might profit by it or not, that was another matter. "Fair enough," interposed Kennedy, trying to reassure the fellow. "Now we're not friends of his exactly. To come right down to brass tacks," he added, lowering his voice, "this gentleman here tells me that you have something to sell. The question is--what do you want and how are you going to deliver the goods--I mean in the way that's safest for you, of course." Kennedy was leaning over frankly toward the fellow. The operative's eyes narrowed and a look of low cunning came over his face. He looked about at the other tables, as though not quite sure of even those about him. "How do I know you come from _her_?" he shot out. "Maybe you're bulls." Kennedy quickly reassured him. "You can arrange the matter any way that's safest to you," he repeated. I had been so intent on our own little affair that I had not noticed that a couple of new-comers had entered from the side door and were at a table not far from us. It had not escaped the shifty eyes of our customer. He gave a perceptible start and in an instant was as dumb as an oyster. Kennedy's cold steel eye seemed to bore right into the gaze of our man now as he leaned forward and whispered to him something I did not hear until, as Craig drew back, I could catch the last of it--"And as sure as the Lord made little apples, I'll shoot if you don't take me up to where you've got the goods. If you do--you get the money." I glanced about hastily and saw that Kennedy's hand was hidden in his pocket, which bulged as if something metallic were held there under cover. The fellow glanced sullenly from us to the new arrivals, as though in a quandary. "You got the money with you?" he asked, rather shakily. "Yes," Kennedy cut short. "'Cause I'll have to beat it the back way--and we got to work fast," he explained, his eyes roving from the burly bartender, who had just gone out to the couple at the other table, apparently oblivious to us. "The faster the better. You can make your get-away with the coin as soon as those reports are in my hands." "All right," he agreed, nervously, then added to me, "and if you fellows see any one try to follow us--you stop 'em. See?" I nodded for both myself and Brooks. "Come on," indicated the former crook detective to Kennedy. "Quick!" Kennedy rose and followed the fellow to a door to a hallway that looked as if it led up-stairs. No sooner had the two risen than our strangers at the other table were alert. I swung around in my chair suddenly toward them, and as I did so my hand went to my hip pocket, as though in search of a gun. For just an instant they paused in their attention to Kennedy. Out of the tail of my eye I caught sight of Kennedy and the operative at the hall door. Framed in the doorway now stood our burly waiter, snarling some remark. "What do youse want?" growled the waiter. Before there was a change for a reply a shot rang out from the other side of the room and the place was instantly in Cimmerian darkness as the bullet smashed the one light in the room. There was a rush and a scuffle. I flung one fellow off, only to be tackled in the blackness by some one else. Swiftly thoughts crowded through my mind as the place was in an uproar. Had we been followed here? Was it a trap? Was Rascon ready to risk anything rather than to have those reports pass into unfriendly hands? The moment the light winked out, Kennedy had swung on the burly waiter and had sprung back toward us as we fought our way toward where we had last seen him. I did not know whether my second assailant was one of the two strangers at the other table or not. Over and over we rolled, knocking down tables and chairs, the air torrid with oaths from all sides. What had become of Kennedy and Brooks I didn't know. I am sure that I would have mastered the situation in my own private little fight if, at that moment, there had not been the crash of glass from another door, followed by a shrill cry. "The bulls!" I heard some harsh voice growl. It seemed as if new men were coming from all directions. My man squirmed out from my grasp and before I knew it, in the darkness, I found myself in the anomalous position of being held firmly by the collar by a policeman, while all about I could hear the impact of billies on crass skulls, resounding in a manner that was awe-inspiring. My own captor needed only a word to bring his own club down on my head, and, needless to say, I was not going to say that word. An instant later some one found a wall light and turned it on. In the half-light, I could hear a laugh behind me. I turned. It was Doyle! "How did you come here?" I gasped, breathlessly, as Doyle released my collar and I stretched my neck to remove the kinks, in so doing catching sight of Kennedy standing over the unconscious form of the waiter in the doorway as he held the redoubtable No. 6 by the collar. "Kennedy thought it was a trap--tipped me off," laughed Doyle, swinging his club as he shouted orders to his men to dive into command of each door or window exit. "Did you locate Rascon?" panted Kennedy, twisting just a bit tighter the collar of the operative whom he was holding. "Sure," returned Doyle, already beginning to line up his prisoners against a blank wall on one side. "He'll be here in a minute. But don't wait for him, if that's your man. Search the place--and, see here, you," he menaced the former operative, "no monkey-shines. You give Mr. Kennedy them papers--or--" Doyle trailed off in one of his picturesque oaths. While Doyle's men completed the line-up against the wall, Kennedy led the now quaking No. 6 into the hall, followed by Doyle, Brooks, and myself. We mounted the stairs, looking into every closet and cranny. Hundreds of cases of "wet" goods must have been concealed in the place, which later we discovered was more than a "speak-easy," for it proved to be a veritable moonshine still almost in the heart of the city. Our search was not long. The stress of threat and circumstance broke down the former crook detective, who now was as keen to clear himself, gratis, and hang something on Rascon, as before he had been to collect his graft and get away with it. Directed by him, in a hall bedroom, under the worn carpet, we loosened a board of the floor and took from the lath and plaster of the ceiling below a flat packet done up in oiled silk. At last we had the purloined Rascon letters. Doyle's eyes widened at the sight of what Craig had uncovered. Here was a whole set of reports such as that which we had already obtained, only of far greater value. Kennedy was immersed in reading them already. "What's in them?" asked Doyle, reaching eagerly for the sheaf of precious tissue-paper carbon copies. Kennedy did not stop reading, but merely motioned to be let alone, as, quickly, he ran his eye over one after another. "Honora had evidently been trailed all over the city," he commented, as he read. It was a few moments later that Kennedy's eyes narrowed as he reached another of the reports. "Here's one that is very interesting," he muttered, half to himself. We crowded around and read the report that was rather lengthy, while Kennedy turned the pages slowly. I shall not attempt to quote it, but rather give the gist of it. "Starts out as though it were a report on Vina and Shattuck," commented Kennedy, "but as you read on, it seems more as though it were a report on Honora." It seemed that the events had happened, or were alleged to have happened, in a resort in Greenwich Village, known as the Orange and Blue Tea-room. As we read the name, Brooks nodded wisely. "I know the place," he remarked, "run by a young lady of very advanced ideas--Zona Dare." However, none of us paid much attention to the interruption at the time, but kept on reading. For, it seemed that one night, scarcely a fortnight before, Vina Lathrop had arrived at the Orange and Blue, according to Rascon's operative, when shortly afterward Shattuck had dropped in, saw her, and wandered over to her table. Later Honora Wilford came in, observed them, but did not sit with them. Instead, she remained alone at another table watching the couple very jealously. "There's a queer break in the report at this point," remarked Kennedy, turning the page. "Nothing further is said about this meeting, but see how it resumes." Apparently, Honora, as she watched, had become more and more nervous, for Rascon went on to detail a stormy meeting between the two women, in which Honora faced Vina with biting sarcasm and at which Vina replied in a manner usually described as "catty." Shattuck had tried to act as peacemaker and to smooth things over. But evidently explanations were useless and only made matters worse. It seemed that whatever it was he said pleased neither woman, and finally, after Honora, with a parting shot at Vina, had swept out of the tea-room, Shattuck very apologetically placed Vina in a cab, then took another himself, and all three had departed in separate ways. "Who is this Zona Dare, did you say?" asked Kennedy of Brooks, when we had all finished reading. "One of the well-known Villagers," returned Brooks. "I believe she has some reputation as an interpreter of Freud--you know, the dream doctor? They put on a one-act play down there last winter that she wrote." "Indeed?" returned Kennedy, interested, but non-committal. I could not help but think that we had struck pay dirt in this report, knowing, as I did, Washington Square and its fondness for whatever is "new," like Freud. Had Vina and Shattuck, as well, been dabbling in the new dream philosophy? I felt sure that Honora knew next to nothing about it. At least, so far, her actions had betrayed little knowledge and less suspicion. Or, it suddenly occurred to me, was Honora deeper than I suspected, and was her seeming ignorance only a pose? Did she know that Kennedy knew, know that to Doyle and the rest Freud was not even a name, and that she must play a clever game to match wits with Kennedy in this matter? Above all, was the report true? If so, judged by Village standards, was it a hint, a strange example of the so-called "new morality"? On the one side was Shattuck, seeking to break up the relations between Honora and her husband. At the same time was he playing a game with Vina Lathrop? As for Vina, her own relations with her husband were strained. Had she known of Shattuck's regard for Honora and had that aroused in her a desire to break it up, for her own advantage? To cap it all, what of Honora? Was this the jealous soul mate pursuing her affinity and finding him false? What, indeed, was the viewpoint--according to the "new morality"? I could not but reflect on what a tangle things had been brought into--once the old morality was thrown overboard and the old immorality renamed. Suddenly there flashed over my mind the recollection of some of the conversation that had been overheard in Wilford's office with the unknown woman visitor. "Give her up, Vail. Can't you see she really doesn't love you--never did--never could?" Had it been said by Vina of Honora--or by Honora of Vina? Either of them, according to her own philosophy of life, might have said it of the other. In the "new morality" there was surely scope for the play of mysterious excuses for passions. "It's easy to see," I remarked, "that Wilford, through these Rascon reports and in other ways, had been laying a foundation not only for Vina's divorce, but his own." Kennedy nodded sententiously. "But why did he have Vina shadowed here to the tea-room--that is, if that is the case? Had he some inkling that Vina was merely using him? And what's the reason for that break in the report? I believe there's something more in that three-cornered meeting than appears." These reports, I reflected, as now we awaited the arrival of Rascon himself, were giving quite another side to the characters of the people concerned in the case from that which had been exhibited hitherto. Were we getting down at last under the surface of their private life and finding it of the same sort as that of the "smart set" and the fringe that apes the smart set? There was a commotion in the hallway and a moment later Rascon himself entered, accompanied, in answer to the summons of Kennedy through Doyle, by one of Doyle's own men. At once Doyle took the affair in hand, and Kennedy did not interfere, deeming it best, apparently, to let Rascon gain the impression that the whole matter had originated with Doyle. Question after question Doyle flung at Rascon without getting an answer that was truly enlightening. Finally, exasperated, as Doyle always became when his rasping third degree did not produce results, Doyle picked up the tissue-paper, typewritten reports and shook them in Rascon's face. "Then you swear that these reports are true?" Doyle demanded. "Don't stop. The devil with how this fellow Number Six got away with them and we learned they were here. Are they true?" Rascon was sullenly silent. "Are they true? Come now, you'll have to answer that sometime, Rascon." "Yes," replied the crook detective, defiantly. Doyle turned to us with an air of triumph, as though he had gained a great admission, though I could not see, for the life of me, why he should be so elated at having merely begun. "I've just read this one," remarked Kennedy, quietly, picking up the report we had all glanced through. "It's true--you say--but it isn't the whole truth, Rascon." Rascon maintained his sullen silence, but there was a furtive cast in his glance that had not been present in the defiance of Doyle. Evidently in his mind was running the thought, "Just what is it that this man, Kennedy, may know, and how am I going to keep from being too clever and tripping myself up?" I knew it to be a situation in which Kennedy frankly reveled, this interplay of wits. "There's a break here," prompted Kennedy, with a positiveness that was palpably disconcerting to Rascon. Kennedy fixed his gaze on Rascon, who fidgeted and finally weakened. "Well, you see," he admitted, "Mr. Wilford came in at that point--said to watch them--and left. I didn't think that it was necessary to put that in the report--to him." "Did Mrs. Wilford see him there?" demanded Kennedy, quickly. "No--I don't think so." "Well--which were you following?" cut in Doyle, to the vexation of Kennedy, who, until then, had had things going pretty much his own way. "Was it Mrs. Lathrop or Shattuck--or--was it Mrs. Wilford herself?" Doyle modulated his voice in his craftiest manner, the manner which I hated, for it was so evident that he tended toward hanging the crime ultimately on Honora. "Why, it was Mr. Shattuck I was following," snapped Rascon, "Mr. Shattuck and Mr. Wilford's wife." The answer was indeed an answer. I felt that Doyle had furnished Rascon with what was, to the crook detective, a neat way to let himself out of a tight position, and I could see that it had given Rascon a relief from Kennedy's more subtle grilling. "We'll take that matter up later," was all Kennedy ventured, hiding his chagrin at the interruption of Doyle. On his part, Doyle seemed to insist on making it evident that he had scored. "Rascon," he added, extending his fist menacingly at the detective, who by this time seemed to have recovered some of his lost equilibrium as he realized the extent of our "find," due to the unexpected treachery of his operative--"Rascon, did you offer to sell these reports to Mrs. Wilford? I know about that Beach House report. Is that why you left Mr. Wilford's name out? Come--you might as well admit it." "No--I didn't try to sell them to Mrs. Wilford," defied Rascon, with assurance. "Why should I? Mr. Wilford paid me a bonus for that particular report--not to me, of course, but to the operative I had assigned to the case." Kennedy, by this time, had given up the further quizzing of Rascon at this time as hopeless, and was preparing to leave. As for myself, I cannot say that I was entirely uninfluenced by Doyle's apparent estimate of Honora Wilford, in the light of Rascon's report and his ready explanation. Though I would not have admitted it to any one else, I began to wonder whether, if the reports were true and Rascon's explanation held, I had been correct in my estimate of Honora. A word from Kennedy would have set me right. Why had he not spoken it? Moreover, had my own interpretation of his Freudian analysis of her been correct? Was she the marble woman he had made me think her? The more I thought of it, the more I felt that the "new morality" down-town was pretty much the same as the old immorality up-town. I began to wonder whether Honora, in her doubt of the lack of feeling for Wilford, had succeeded in keeping herself from being smirched by either standard. I was frankly at sea. We left alone, leaving Doyle to handle the product of his raid, including the now intractable Rascon. Craig thanked Brooks for his help and Brooks had scarcely left us. I was about to ask Kennedy his frank opinion of the case for Honora, when he himself forestalled me briskly. "Walter, I've an angle of this thing I want to go into immediately. Besides, I have some work I must get through at the laboratory. Suppose that, in the mean time, you trace down what truth there may be in that tea-room incident. I think you and your friend, Belle Balcom, could do that." XII THE "NEW MORALITY" I was rather glad of the commission Kennedy had given me. Belle Balcom had a keen and sprightly mind. She was the typical newspaper woman, it is true, who often would sacrifice accuracy to cleverness. Yet there was not much to condemn her in that, for she was so undeniably clever. Contact with her was stimulating. Besides, it was just on such a quest as this that a girl of her type was invaluable. Accordingly, I set out immediately down-town for _The Star_. Fortunately, I found Belle finishing her stint of society gossip for the day. I made a quick explanation of what Kennedy wanted and was pleased to see that she was interested. "I think it's a good idea to visit the tea-room," I explained, then added, doubtfully, "but how are you going to find out whether our people are remembered there--if they don't happen to be remembered by name?" "Nothing simpler," Belle replied. "Some one there will surely remember faces. We'll settle that in the art department." Thus, armed with photographs of Shattuck, Vina, Honora, and Wilford which _The Star_ already possessed in its files, Belle and I set out on our quest. The Orange and Blue Tea-room was not easy to find by one unfamiliar with the Village and its queer twists of streets. But Belle knew it well and I had some slight recollection of it. It was originally a low-ceilinged basement in an old house not far from Washington Square. The upper floors were now "studios." In the former basement, almost a cellar, were three rows of tables extending the length of the place and overrunning out into the little back yard where one dined in summer _al fresco_. At the far end, on one side, was a little raised platform, and on it was a piano strummed by a blind player. Opposite was the entrance to the kitchen, which was subterranean. Belle and I entered, and immediately the highbrow hold-up began, just as up-town, with a coat-and-hat check-boy. We made our way to one of the tables along the wall and seated ourselves. Everywhere orange and blue decorations, true to the name, smote the eye, on walls, on ceiling, on chintzes, on the floor, on everything, it seemed, but the table-cloths and the silverware. "You know, orange stands for temperament," chatted Belle, as she saw me marveling at the color riot. "New art, I guess." "Insanity art," I replied, with a smile. "Don't mistake me, I enjoy it, though. It's atmosphere--especially when that kitchen door is open." Belle looked about, as a woman will, at once attentive to our conversation, taking in whatever was happening within the range of two ordinary men's vision, now and then nodding to some acquaintance, sweeping a glance at the menu and tucking in a stray wisp of black hair, all at once and each without in the least interfering with the other. "I suppose the 'Villagers' are here in force," I suggested, noting as best I could all her simultaneous actions and probably missing the other half which I have not recorded. Belle smiled. "Villagers don't come here much. The place is too well known. Besides, there are not so many 'Villagers' as you would think. No doubt most of them are up-town. No, most of these people are skirmishers from the highbrow and curious up-town and out-of-town. You see, there's a sort of reciprocity about it." However that might have been, there was enough that was picturesque and one felt sure that one was really in an environment of the bobbed hair and maiden names for wives--that is, assuming that the words maiden and wives were still in the vocabulary. "All parlor socialists?" I inquired, looking about. "Have your little joke," frowned Belle. "We all have to, I suppose. But really, down here, after all, there are people who think, who _do_ things." I had been waiting for that expression, "do things." They all "do things" down in Greenwich Village, even if it is only to compose music for the zither or publish one's own amateur magazine on butcher paper from hand-set type. Evidently Belle took the Village more or less seriously, after all. "Besides," she faltered, "there are no parlor socialists, any more, anyhow. That belongs to the old muck-raking magazine days." "I see--limousine liberals now--or boudoir Bolsheviki." "Maybe you'd better eat," suggested Belle, sarcastically. "It's a tea-room," I parried, glancing down at the menu. "I suppose it's orange pekoe--although they don't seem to be drinking it. Perhaps they're all smoking it. Now that we're all supposed to be so good, I hear that tobacco will be replaced by dried powdered tea leaves and coffee grounds. They say a caffein jag or a thein jag has merits. Passing by the paraldehyde cocktail, what's good?" Belle's good humor was restored, and with her help I managed to order everything from soup to nuts--and I am sure that there were a good many fugitives from the squirrels in the room, whether from up or down town. I was really enjoying myself, so much so that for the moment I almost forgot the purpose of our visit, when it was recalled to me by Belle, who spoke in French to the waiter, rather gross and greasy but answering to the compensating name of Hyacinthe. "_Où est Ma'm'selle Zona?_" she asked. The waiter actually understood, and, though it would have been so much easier in English, Belle conveyed the idea that she would like to talk to Miss Dare and the waiter agreed to get her, though I felt he restrained himself with difficulty from replying in good Manhattanite, "Sure, miss, I'll dig her up"--meaning from the olfactory Hades beneath us. Zona Dare proved to be a slender youngish lady, with the conventional shock of dark bobbed hair--with a dilettante exterior but a very practical secret self, I am sure. Even a mere introduction to her told me she was a member of that curious "third sex" that evolution is giving us. I can't exactly describe it. It is not "she" or "he" exactly, neither he-woman nor she-man. Certainly it is not neuter. Maybe when nature, or whatever it is that is operating, gets through we may be able to classify it. Belle knew her, of course. Belle knew everybody. In fact she knew her so well that Zona, on urging, consented to sit down with us awhile and actually ordered tea--in a pot, too, though whether Russian, English or Scotch or Rye I am not sure. At any rate, it seemed to promote conversation and confidence and I covered my raillery with protective coloring. What I enjoyed was the utter freedom of the conversation. We had soon progressed to bolshevism and the government ownership and operation of women. Finally the conversation put into the ultimate port of the "new morality." "One must live one's life," seemed to be the burden of the philosophy, and I did not quarrel with the 1919 model of hedonism, for by this time I began to see a ray of hope that finally I might learn something about those whom Kennedy and I had been studying. I recalled Vina's remark to us over her contemplated divorce, "I believe every woman should live her own life as she sees fit." Doubtless she had absorbed it here. It was evident, however, that there could only be so many triangles a week--and besides, "the eternal triangle" was in itself condemned by its mere ancient origin. What next? I guessed right--bolshevism, of course. I found I had dropped right into the intelligenzia--the very sovietment of society, where _The Nation_ and _The New Republic_ were considered hide-bound conservatives. I did not quarrel even at the addition of red to the orange-and-blue color scheme, though I adopted the attitude of one mildly seeking the truth. "Perhaps Freud can explain," I suggested, after one passage at arms with Zona, ably seconded by Belle, "why it is that a prosperous aristocratic feminist should enjoy contemplating casting her rope of pearls before the proletariat. What do these comfortable nibblers at anarchy expect to get out of it?" There was an answer. I have forgotten it, but it was clever and convincing. It always is, just as glib sophistry and specious phrases are. The gist was that all psychology, science, the history of the human race, had been superseded by some quite indefinite idea originated in a land with problems about as much related to us as the dredging of Martian canals would relate to Suez and Panama. However, the purpose was accomplished, and Belle, with her human point of view, which one gets from seeing this corrupt old world from a newspaper office, saw it. Gradually, the conversation had drifted about to Freud. I was glad that I had learned so much about him from Kennedy, for I was surprised at the knowledge that Zona really had of him. Was it superficial--as so much of that little world into which Kennedy had plunged me? I am not sure. At least, Zona posed as a Freudian interpreter. I was sorry Kennedy was not present, for I was inclined to accept her as such. The fact was that it set me thinking that perhaps she had educated in the theory many to whom a little knowledge is dynamite. Belle's keen mind seemed to read my thoughts, even to leap ahead of me. She reached into her bag and drew forth some photographs. "Oh, Zona, by the way," she rattled on, "that reminds me. Did you ever see this man here--or this woman?" Zona took the photographs of Shattuck and Vina, and with just a glance answered, "Indeed I have!" "Do you recall a night when there was a scene here--another woman?" went on Belle, producing the photograph of Honora. "Yes--I remember her. I know them all. They're in this case that's in the papers now. The lawyer who was killed was that woman's husband," she added, pointing to Honora. "Why? Are you writing them into your column?" "Yes," confessed Belle. "That is, if I can get a good enough story out of the incident here." At once Zona's keen, practical mind leaped to the bait of publicity held out by Belle. What could be better advertising than for the celebrated case in the news to be connected with the tea-room? It would crowd the place. "What is it you want to know?" "Just what happened." "I didn't see it all. As nearly as I can recall that man--Mr. Shattuck, his name is--was at a table with Mrs. Lathrop when Mrs. Wilford approached. You see, I knew them all slightly. I know so many people who come here from up-town. It flatters them--and I have a good memory for names. I had seen Mrs. Wilford here several times before with Mr. Shattuck--and once I think with Mr. Wilford--I'm not sure. Anyhow, I knew her--I think I sold her a box for our Freud play last year--I'm not sure. I'd have to look that up. Well, there was quite a scene when Mrs. Wilford stopped and faced Mrs. Lathrop at her table. But here's the strange part of it. I don't know whether you know it or not. But just before that, while Mrs. Wilford was sitting at the table just back of us--the two were down there near the piano--Mr. Wilford himself came in. He was about to give his hat and stick to the check-boy when he caught sight of the back of his wife's head. She was alone--right there--then. He spoke a few words to a man near the street door. I don't know _him_. He never came here before and I haven't seen him since. But, at any rate, Mr. Wilford spoke to him, then turned and left in a great hurry. I wasn't here through it all. Just a moment, Pedro!" she called to a waiter who was passing at the moment. Pedro completed his service at another table, then came over to Zona. "Did you ever see these people here?" asked Zona, turning over the photographs of Vina and Shattuck. Pedro was at first suspicious, and, in fact, I do not believe that he would have told us a thing had it not been Zona herself who questioned him. "Yes," he admitted, finally, "I remember one night they were here." "Did you serve them?" asked Zona. "Yes," he replied, apparently reluctant to be drawn into anything. "Do you remember anything that happened?" "I was very busy," he evaded. "The woman came in first alone, I remember, and said she was waiting for a friend. Then the man came in. I thought she was surprised to see him--but I thought it was all right. She had said she was going to meet a friend." I shot a quick glance at Belle, who nodded. It was evident that Vina had not expected to meet this friend. "Do you remember anything that was said?" I ventured. Pedro looked at me suspiciously. "I was too busy serving," he replied. "It was the busy time." "What seems to be the trouble?" I asked, not cross-questioningly, but more as if merely for information. "You don't seem to want to answer. Are you afraid of something?" Pedro regarded me a moment, then looked at Zona. "It's all right," she reassured. "Well--you see--once I was in a divorce suit--in court--I lose t'ree, four days' pay--the boss he fire me. Are you detective?" I smiled and evaded the question, under cover of Zona's presence, and again reassured him. "There was another woman came in, wasn't there?" I asked, as Belle produced the photograph of Honora. "Yes--that's her." "She didn't sit with them," I prompted. "No," he replied, "over there," pointing to the table Zona had already indicated. "Did you wait on her?" "No--Louis." "But you saw her?" "But yes--every one did--one could not help. She came in as though she was looking for some one." "And then what?" "I was serving the fish. This woman, she get up quickly and come down to the table. Oh--but she was angry--at the man--at the woman." "Did she make a scene--I mean did every one see it?" "I should say! I had just left the table--but every one see it--yes--and hear, too, I think." "What did you hear?" "I? Nothing. I was by that time at the door to the kitchen. But she was angry--the color in her cheeks--the voice. I think she must be the wife of the man--she seem so angry at him, also." Discreet Pedro, I reflected. He was making everything as indefinite as possible to render himself less liable to be called to court in case of trouble. However, he was telling me just what I wanted to know. It was already sufficiently evident that Vina had actually had the appointment first with Wilford himself, that she had got there early, that he had been late, perhaps purposely, due to some suspicion, or perhaps to make sure of covering himself, for he must have provided for Rascon's operative in case of trouble. Piecing the thing together, I was convinced that, in some way, Honora had learned of the appointment and that Shattuck had learned of it, too--though it must have been independent, else why their encounter? Shattuck had come--perhaps to face Wilford. At any rate, he had been sitting with Honora when Wilford's wife, of all persons, came in and saw him with Vina. There my deductions broke down. What were her emotions? Was she jealous of Shattuck paying attentions to the woman who had so fascinated her own husband? How far was she piqued at the thought of not having hold enough over Shattuck, also, to keep him from Vina? As for Shattuck, was he really fascinated by Vina, after all? I did not try to pursue that line of analysis farther, yet. At any rate, Honora had seen them and in turn had herself been seen by her own husband, who had stopped only just long enough to give his detective instructions, then had departed unobserved by the other three as he entered. Whatever Shattuck's attempt at explanation, when faced by Honora, it had not been convincing, at least to her. They had left together, parted at the door. But I knew that the misunderstanding must have been patched up later, for they had been together since that time. A few more questions showed that Pedro had nothing to add, and I let him go. Zona told me what little she had observed. From the other waiter, Louis, I learned one thing, however, about Honora and her actions before she rose and made the little scene at the other table. She had come in rather pale and agitated. As she sat there, having ordered, but with her food untouched, she had seemed to get much calmer, though her face became more and more flushed and her eyes animated as she missed no movement of the other couple. It was that very absorption that probably had been the cause of her missing the very man she sought, her husband. But it meant more than that. It told me something of her nature, that this woman was of the sort that, when a crisis approached, instead of going to pieces, like many others, was able to keep such a grip on herself that she swept ahead through the crisis coolly and clearly, in spite of the suppressed excitement. That spoke volumes. No doubt when the relaxation came she was on the verge of collapse. But as long as the need lasted she had complete control. Did that mean that at the present moment, as she faced Kennedy, she was repeating the same performance? Louis had gone, and Zona turned to Belle and myself as if to ask whether there was anything else she might do for us, at the same time looking at her watch and fingering her cup as a hint that she was a busy woman and must get away. "Why did Shattuck meet her here?" I thought aloud, wondering if, perhaps, Zona herself might not know them and betray something. She shrugged, and I was morally certain that she did know them both, and well. But evidently, as to bringing herself personally or her theories directly into the case, there was a barrier. "Mr. Shattuck seemed to be interested--but--you can never tell. He is one of those men who have the faculty of making every woman think she is the only woman." "Did he ever discuss things with you--I mean Freud--current topics of conversation?" I ventured, covering my interest as best I could. "Oh yes, in a general way. Almost everybody who comes here does. They all know my hobbies. That's why they come here, I guess. Isn't it, Belle?" "To see you, dear--yes. I know _I_ do. Without Zona--there are a dozen places one might go. They lack something." "He seemed interested in Freud?" I pursued. "Y-yes--but so are we all down here, just now." Evidently Zona was hedging. I gathered that Shattuck's interest had been rather more than ordinary. "And Vina Lathrop--was she interested, too? You must have known her." "Yes, I knew her. Vina _was_ interested--of course. But, then, who is not, just now? A few years ago only a few had read Freud. Even after he was translated, still there were only a few. But now--since my play--we have other plays, books, stories, articles--even Freud doctors, who before were unknown to the public, have come outside of the medical press with their names and work. Of course Vina Lathrop was interested. All women are interested in Freud. Don't you think it concerns us--just a bit more intimately than it does men?" For the moment Zona had forgotten her haste to get away and was leaning forward earnestly over the empty tea-caddy. "Most assuredly," I agreed, realizing suddenly one reason why Freud is taken up so readily in a circle such as that which I was now tangent to. He offers an easy, scientific highroad to the discussion of intimate sex--and that is, after all, under the veneer, the middle name of Greenwich Village, as it is of all "highbrows" when one comes to get under their skins and truly understand what secretly is back of their "uplifts" and "reforms" in social evils and hygiene. "But what of Honora?" I asked, loath to lose the piquant assistance of Zona, once I had it. "Why was she here? Had she come to watch Shattuck? Or was it to watch Vina? Or was it really to watch her husband? Her husband or Shattuck--I wonder which?" "Suppose it was either?" shrugged Zona, nonchalantly. "What of it?" Evidently the spell of her interest in the Freud discussion had broken when she finished her last sentence. "In the former case she is merely old-fashioned," added Zona, "in the latter merely foolish." With this typical meaningless cleverness that in reality hides the shallowness of our advanced "thinkers" Zona bade us adieu. Belle and I chatted a few moments, when she suddenly discovered she was half an hour late for an engagement. I settled the check, and we tipped our way out and into a cab that whirled us up-town, while Belle poked fun at my benighted conservatism, which I did not mind in the least. I left her at her hotel, with hearty thanks for the great help she had been in the case, and sincerely happy, in addition to that, for a pleasant couple of hours at dinner with a girl with whom one might disagree yet still regard highly. A few minutes later I was at the laboratory, full of a new-born theory that Shattuck, down in the Village, had studied Freud more than we had suspected merely from finding Freud's books in his library--that he must have known Honora's dreams, interpreted them, and found out secretly she still loved him, as her open jealousy had, perhaps, showed in the incident I had unearthed. Craig was already there, and at work. He listened attentively and without comment to what I had to report. "What have _you_ found?" I asked, finally, when I had finished with my own facts and theories. "Oh, I've been down to Shattuck's office in Wall Street," he answered, rather absently. "And you saw him? How did he take it?" "He was very angry. Asked me if I was going to try my case in the newspapers--was very sarcastic. I was just about leaving when I met Doctor Lathrop coming in." "Doctor Lathrop--coming in!" I exclaimed. "How was that? How was Lathrop--and why there?" "I saw him alone first. He was very much upstage with me. I thought there was something brewing, so I stayed--that is, went back with him. I'm glad I did. I think I narrowly averted a fight. Lathrop threatened Shattuck--that is, I mean, all in a very polite way--but it practically amounted to telling him to stop seeing his wife, to have no more business relations with her, and all that. It was in the nature of serving notice. Shattuck is very high-spirited. I think if I had not been there there would have been trouble. But Lathrop was very suave and diplomatic." "I'm wondering about this man Shattuck," I put in. "Is he woman-crazy?" The laboratory door was suddenly flung open and Doyle burst in. "_Some_ news!" he exclaimed, excitedly. "The dictagraph works." "I should expect it to do so," calmed Kennedy. "It has never failed me yet, when properly used, like all science and invention, at the right time and place." "Say--you're a cold shower. Listen--I'm getting closer to her!" XIII THE MECHANICAL EAR "Then it was Honora you overheard over the dictagraph?" I asked, quickly. "Not at first," replied Doyle. "I'll come to that later. Let me give it all to you first." He pulled from his pocket a set of typewritten notes and excitedly began to condense what McCabe had just heard over the dictagraph in the Wilford apartment, sometimes giving it to us from memory, then refreshing his mind from what McCabe had transcribed. "It seems that the maid, Celeste, had a visitor," began Doyle. "Who was it?" hastened Kennedy, impatiently. "A man named Chase." "Who's he?" "Another detective." "Like Rascon?" Doyle nodded doubtfully. "I don't seem to know him," he remarked, sententiously, though in a tone that was prejudiced. To Doyle all private detective agencies were as the scum of the earth. I know Kennedy made mental note to look the man up, unprejudiced. "What do you know about him?" asked Craig. "Very little--except that from what Celeste said Mrs. Wilford herself must have employed him at one time or another--perhaps even now. I guess that woman knew more about what was going on than we think." I glanced from Doyle to Kennedy. Could it be possible that we ourselves, in turn, were being watched by her? And was Honora not the simple, unsophisticated woman I had thought? "Evidently," went on Doyle, "Celeste was trying to fasten the crime on Vina Lathrop." "How's that?" queried Kennedy, sharply. "Well," returned Doyle, running his eye over the transcribed conversation to pick out that part which substantiated the statement, "it seems as though Celeste was trying to tell Chase something that Chase didn't accept. Here it is. Chase's remark was lost--but it must have been about Mrs. Wilford's actions that night of the murder. "'No, no, no--she was not out of this apartment that night.' That was what Celeste said in answer to him. "'Come, come, now,' Chase said, 'what's the use of that? You might tell that to Doyle--but why tell me? Where was she?' "You see, they're all trying to put it over on me," interjected Doyle, apoplectically. "She might have been out--and still not have been near Mr. Wilford or his office," I returned. Doyle gave me a withering glance and did not even deign to reply to a mere reporter. "Here's the other thing, Kennedy," ignored Doyle. "I mean about trying to put it on Vina Lathrop--to save Mrs. Wilford. "'Wasn't _she_ at Mr. Wilford's office?' That's a return question from Celeste to Chase to divert attention, I tell you." "What was Chase's answer?" Doyle ran his eye down the page. "'I've traced pretty nearly everything Mrs. Lathrop did that night--except for a couple of hours after she left the Gorham Hotel, where she had dinner. If I could locate the driver of the cab that took her away, I'd get a clue. But it was a passing taxi the doorman hailed, and there doesn't seem to be any trace of him--yet.' There--don't you see? They're trying to get something on Mrs. Lathrop. It's plain. I ask you--why?" Doyle leaned back and regarded us with an air of conscious triumph. "Cost what it will," he added, "it's apparent that Celeste is devoted and loyal to Honora Wilford, too. I tell you they're covering up something," he emphasized, waving the notes, "and I intend to uncover it." However, Kennedy did not seem to attach much importance to what either Celeste or Chase had said. Evidently he had a pretty clear idea already of what had happened. I recalled Celeste and the "Aussage test." Was Celeste to be trusted--even over a dictagraph? Doyle seemed to read in Kennedy's face what I had already seen, and hastened on to new points in his arguments from the notes. "That's all very well about Celeste," he continued, excitedly, "but here's the real news, after all. The most important thing was what happened an hour or so later, after Chase had gone. McCabe picked up the voice of a woman. It was Mrs. Lathrop herself calling on Mrs. Wilford. How about that?" "What!" I exclaimed, involuntarily, I suppose, because of Kennedy's continued silence. "Vina called on Honora Wilford? Why, man, I should have thought the wires would have fused!" "Well, that's what she did," asserted Doyle, "and you'll be more surprised when I tell you what happened." Doyle was enjoying the suspense he himself had created. Still Kennedy said nothing, not so much, I think, because he would not give Doyle the satisfaction of observing his interest as because his mind was at work piecing into his own theories the new facts that were being brought out. For that has always been Kennedy's method--the gathering of facts, fitting them together, like a mosaic, with fragments missing, and then with endless patience fitting the new fragments as they are discovered into the whole picture of a crime until the case was completed and he was ready to act with relentless and unerring precision. As for myself, I listened to what Doyle had to reveal with amazement. Here was a meeting, separated only by hours, if not merely by minutes, from another in which Vina's own husband had called on Shattuck. "As nearly as I can make out from McCabe's notes," began Doyle, "Mrs. Lathrop must have been seeking this meeting and Mrs. Wilford avoiding it for some time. You see, the interview was so passionate that often the voices were indistinct and his notes are fragmentary in spots. However, there's enough to show what it was all about." Doyle turned a page. "It started with Mrs. Lathrop accusing Mrs. Wilford of avoiding seeing her. When Mrs. Wilford pleaded the tragedy and the surveillance she is under, Mrs. Lathrop hinted that she was using these things to shield herself. "Here's where Mrs. Lathrop began to let something out. 'Your maid, Celeste, I hear, has been talking about me. And I know, also, Honora, that you've had a private detective, a man named Chase. You've had him following me!' "McCabe tells me that the tone of this was very accusing, and that Mrs. Wilford did not make any attempt to answer. I only wish we had something like a dictagraph--detectavue, I'd call it--that would let us look at the faces of some of these people as we hear them over this mechanical ear--a mechanical eye, understand? I'll wager Mrs. Wilford's face was a study. She's a match for any man. But I'd like to see her matched against a woman like Mrs. Lathrop. She's clever, Kennedy, clever." Kennedy nodded, but without enthusiasm over the proposition. Rather it was an invitation to Doyle to go on. "There's a lot more," continued Doyle, hurriedly. "Here's what I want. Listen to this. If it's true, we've got something. Mrs. Wilford hadn't said much and it seemed to arouse Mrs. Lathrop to go farther. Listen. 'I hadn't intended to say this, Honora,' she burst out, 'but you were at his office--that night. Come--own up, dear.' Get that 'dear' at the end? I don't know where Mrs. Lathrop got her information. I wish I did. But at least she seems to me to know something." "Or else she's very clever at fishing for information," I interrupted, for I was not able to restrain it. Doyle was so cocksure of his deductions that it antagonized me. On his part, I am sure, while he may not have had much respect for my profession, he had a wholesome fear of it, as many detectives have. For, after all, we newspaper men have the key that unlocks the door to everything. On the other hand, I must admit that I was not at all positive in my own mind. Was Vina fishing--or did she really know something? Was that why Honora was silent? Or was Honora contemptuous of a woman of Vina's type and was silence without any admission her sweetest revenge? What was the purpose that lay back of this visit? For one thing, the silence of Honora, whether it spelled guilt or mere contempt, had its effect on Vina and made her more daring. "'Then this Professor Kennedy,' continued Doyle, reading from the notes. 'With that Mr. Jameson he has been finding out things at the Orange and Blue Tea-room and other places. They've got a woman working for them, too, I imagine. I tell you, Honora, _they know_.' "'Know what?' Honora answered, and McCabe thought she wasn't quite as cold and calm as usual. "Then Mrs. Lathrop went a little bit farther--oh, I'll say that these women are clever--both of them. On the whole, now I'm not so sure which of them carried off the honors. Come to think of it, Mrs. Wilford was clever, too. She has to be. Anyhow, Mrs. Lathrop went a step farther. 'They know about the Greenwich Village stuff, now.' What's that, Kennedy? You never told me that." There was something reproachful in Doyle's voice, assumed, no doubt, but still there, as much as to say that he was taking Kennedy into his confidence and expected a return. Kennedy stole a glance at me and I understood. It was just this that had impelled Doyle to come to us. He had not understood it himself and, in order to keep up with us, was obliged to take us into his own confidence. Briefly Kennedy related, with an occasional word from me, what had happened since the river-front-saloon raid. "Oh, I see," remarked Doyle, though any one could tell that he really did not see. "That's what she meant when she went on and said, 'About Freud and all that, Honora. Zona Dare told me, over the 'phone. That's why I came over.' "'Indeed, Vina, you needn't have troubled yourself,' was Mrs. Wilford's reply. 'It's a matter of perfect indifference to me how much or how little Professor Kennedy and Mr. Jameson know or find out.' "McCabe says she was very cutting in her remarks there. But he also says he thought she was weakening. Anyhow, it had its effect on Mrs. Lathrop. She flared right up. "'Don't care?' she cried. 'You don't care if Kennedy finds out about your interest in the play, about your life, about Freud, the "soul scar" theory, and all that? I may not know much about science and especially this new psychology, but I'm blessed, Honora, if I'd want any one raking up the past.' "'I should say not--Vina.' Pretty pointed, wasn't it? These two love each other like a German and a Frenchman." Doyle paused, then went on reading and summarizing. It was as I had been suspecting for several moments. In an instant the two women were on the dangerous ground of Honora's early engagement to Shattuck. What they said did not seem so very important and I omit this part of it. However, I knew it would lead to something. "'You broke off the engagement, Honora, because of his escapades,' finally hinted Mrs. Lathrop, with claws behind the velvety tone of the remark. 'And yet--' "Mrs. Wilford interrupted here. 'It is a far more important thing, Vina, that a woman should keep herself clean than for a man--far more important for the race. Not that I would excuse things in _any_ man.' McCabe says that remark went right home to Mrs. Lathrop. She flared up. "'Oh, tush, Honora--more of your highbrow philosophy. _You_ talking about the race! Where are _your_ children? I've been studying you, Honora. You may think you're a highbrow. I guess you are. They all--you--are like the rest of us, with the same passions--no better, no worse. Remember--it's you have the soul scar--you!'" "The cat," I could not help but mutter. Again, recalling Kennedy's instructions, I wondered whether consciously Honora had rejected Shattuck while at the same time she unconsciously accepted him as a lover? Evidently now each was accusing the other--and over Shattuck. I recalled Honora's dreams which she had told willingly. There was the dream of the bull and the serpent. That was sex. Again I recalled the dream of the forest and the hill she had been struggling to get up. In this dream I recalled the fire, the climbing, the explosion, and her dream of the other woman, with her unwillingness to admit to us that the other woman might be no other than Vina. Then there was the unexplained dream she had about Doctor Lathrop, the lion in the path. Evidently Honora had been betrayed into some dangerous admissions in her dreams, I thought. "What's next?" came Kennedy's voice. "I get the drift of what was really back of it all. Let's go on." Doyle eyed Kennedy quizzically for a moment. Kennedy's explanation of the psychology of the thing had been much over Doyle's head and had left him in doubt. He turned back to McCabe's notes. "It's Mrs. Lathrop speaking next, and she was very angry. 'If you don't leave him alone, Honora--I'll tell Kennedy all that I know.'" Doyle shot a glance of inquiry. "She hasn't told it yet," answered Kennedy. "What next?" "I guess it got under Mrs. Wilford's skin. 'I don't understand men,' she cried. 'But I understand you. It is revenge--revenge on me that you want, Vina.'" "She got back a thrust at Mrs. Lathrop, anyhow," I commented. Yet I wondered what Vina's motive might be. Was it merely due to her insane infatuation for Shattuck? As for Honora, was she, I kept wondering, after all, the consciously frigid, unconsciously passionate woman? At least, she was a most perplexing "complex." Doyle had closed his note-book with the remark that his little mechanical eavesdropper had made an excellent start, and now was looking inquiringly at Kennedy. "Where is Chase?" asked Kennedy. "Have you any idea?" "McCabe looked up the name and finds that there is a Chase agency on Forty-second Street. You might try it." Accordingly, we set out for the address of the detective which McCabe had located and found that it was a small office in a building near Fifth Avenue. Chase himself proved to be a rather frank-faced, energetic young fellow, not at all typical of the private detective. In fact, he had had some experience as an operative for one of the big agencies, and, having some money, had achieved the dream of every such operative--an agency of his own, small, but at least his own. It did not take much questioning to get the main facts out of Chase, who kept repeating that neither he nor Mrs. Wilford had anything to conceal. Anyhow, the mystery of Chase was solved. Chase was a detective whom Mrs. Wilford had retained for her own protection against the unprincipled operatives of her husband. He proved to be apparently honest and straightforward. Though he could shed very little light on the deeper problems that confronted us, there were many things we had already unearthed which his reports corroborated. It was apparent that Honora was perfectly aware of what had been going on between her husband and Vina Lathrop. Chase had kept her informed of that. Yet, no matter how accurate his reports, I reflected, it did not absolve Honora. In fact, the more she knew, the more likely Doyle was to say that the information constituted a motive that would have caused her to act. "What do you know about Mrs. Wilford's whereabouts on the night Mr. Wilford was killed?" questioned Kennedy, coming finally to the most important point that had been revealed by McCabe's dictagraph records. Chase looked him straight in the eye and considered a moment before answering. "It's true, I don't know much. That is one thing I'd rather not talk about until I do." "But she's your client. Hasn't she told you?" "There are some communications that are privileged," was Chase's enigmatical answer. "But can't you see that it's placing her in a wrong light--supposing everything she did that night was innocent? She ought to tell for her own sake--don't you think?" Chase shrugged. "Perhaps," he added, non-committally. Kennedy, I thought, had some respect for the young man who was not to be betrayed into dangerous admissions. "Then this other woman, Mrs. Lathrop," pursued Kennedy, shifting the subject. "There's a hiatus in the accounts of her doings that night, also." Chase was more disposed to talk. "Yes," he answered. "I've been trying to trace that out. Haven't succeeded--but have hopes. I tell you what I'll do. If I can reconstruct what _both_--see? _both_--of these women did, well, I was going to say I'd give it to you. But I'd have to ask Mrs. Wilford's permission. She's my client, after all." I tried to reason out what Chase was doing. Did he know something about his client that he must shield her from, or was he just a bit vexed at her himself for a certain lack of frankness? As far as Vina was concerned, I knew he would have no scruples in telling us everything he discovered. Evidently, Chase saw that he was losing his first good impression with Kennedy. To re-establish himself, he opened a locked steel compartment in his desk and pulled out a small box. "Here's something that might interest you," he remarked, handing the box to Kennedy. "Ever see one of those?" Kennedy opened the box. Inside reposed a single Calabar bean! Craig looked up quickly. "Yes. Where did you get it?" "If you'll promise to ask me no more--just yet--I'll tell you." Kennedy nodded and Chase took it as a gentleman. "I found it, with some other African souvenirs, in a little cabinet-museum in Mr. Shattuck's apartment. Now don't ask me why I was there or what else I found." Kennedy smiled, thanked him and handed back the box. It was a perplexing piece of information. If Shattuck was known to have had in his possession some of the fatal Calabar beans, what interpretation could be placed on it? Or was it that Chase was working to protect his client and save her--at any cost and in spite of her own wishes? We left Chase, and Kennedy hastened back to the laboratory, where at once he set to work with a paper and pencil, writing words that seemed utterly disconnected, while I stood about self-consciously, watching him. "Please, Walter," he exclaimed at length, a little bit nervously, "you are distracting me. You see," he added, briskly, "that interview with Chase has reminded me of something. Why was he in Shattuck's apartment? For what? When? I don't need his help, of course. But he has made me think that I can't afford to let Mrs. Wilford get out of my sight too long. If I ever get at the bottom of this thing, it must be through study of her, first. I think I shall be ready soon to visit her again. And this time, I'm sure, I shall find out what I want. I've a new plan. Don't disturb me for a few minutes." I turned my back and pretended to be busy over some work of my own, though out of the corner of my eye I watched him. Craig was at work over a sheet of paper and I saw him writing down one word after another, changing them, adding to them, taking away words and substituting others. Altogether, it was a strange performance and I had not the faintest idea what it was all about until he was willing to reveal it to me. Meanwhile a thousand ideas whirled through my head. Chase's revelation had put a new face on matters. One by one, we were finding out that each of our suspects knew first of all more about the Freud theory of dreams than we anticipated. Now it would appear that each was more or less familiar with the Calabar bean, or at least with its derivative, physostigmine. Even Vina, being a doctor's wife, might have known. Though we were getting more facts, they were not, so far as I could interpret them, pointing more definitely in any one direction. When Craig had finished, he copied the words off on my typewriter, in a long column, one word on each line, and, after the long vertical list, he left two columns blank: 1 2 3 foot gray dream struggle ship bean lion book false voyage money sad quarrel marry bull sleep foolish despise finger friend serpent face chair bottle glass "Now," he remarked, as he finished and saw my questioning look, "let me get my delicate split-second watch from this cabinet, and I'm ready for a new and final test of Honora Wilford. Let's go." XIV THE "JUNG" METHOD On the way to the Wilford apartment, which was not very far away, Craig explained briefly what it was that he wanted me to do for him. "You saw that list of words?" he asked. "Yes, and the columns opposite." "Precisely. I want you to write in them the answers that I get. You will understand as we go on. I'll hold this watch and note the time--and then we can put the two together, the answers and the reaction time." It seemed simple enough and we chatted about other things connected with the case as we walked along to the apartment. Honora Wilford showed some surprise at seeing us again, yet I fancied she was in a better mood than previously, since the obnoxious McCabe was no longer so much in evidence. "What is it that I can do for you now?" she asked, rather abruptly, though her manner showed that her surprise was, after all, very mild. Evidently Doyle had accustomed her to being quizzed and watched. It was not a pleasant situation, even to be watched and quizzed by Kennedy, yet she seemed to realize that he was making it as easy as possible. "Just another little psychological experiment," Craig explained, trying to gloss it over. "I thought you wouldn't mind." Honora looked at him a moment doubtfully. "Just why are you so interested in studying me, Professor Kennedy?" she asked, pointedly, yet without hostility in her tone. It was a rather difficult question to answer, and I must admit that I could scarcely have met it adequately myself. However, it took more than that to give Kennedy a poser. "Oh," he replied, quickly, with an engaging airiness, "as a psychologist I'm interested in all sorts of queer things--things that must often seem strange to other people. Perhaps it's highbrow stuff. But for a long time--and not in connection with you at all, Mrs. Wilford--I've been interested in dreams." He paused a moment, moving a chair for her, and I could see that he was observing the effect of the statement on her. She did not seem to show any emotion at all over it, and Kennedy went on. "Often I've studied my own dreams. I find that if, when I wake in the morning, I immediately try to recollect whether I have dreamed anything the night before or not, I invariably find that I have. But if I do something else--even as simple a thing as take a bath or shave--unless the dreams were especially vivid, they are all gone when I try to recollect them. I'm almost convinced that we dream continuously in sleep, that more often we don't recollect the dreams than we do. Your dreams interested me at the very start. I guess that was why Doctor Leslie repeated them to me. He knew that I was a crank, if you may call it that, on dreams. As for detective work of the old kind--that sort of thing Doyle does and--well--I leave that to Doyle." He shrugged. As Kennedy rattled on, I could see or fancy that Honora was becoming more reassured. "What is it you want me to do now?" she asked, her reluctance disappearing. "Nothing very difficult--for you," he flattered. "You see, I have here a list of words, selected at random. I don't suppose it will mean anything. Yet there are lots of things these strange people, the modern experimental psychologists, do that seem perfectly foolish until you understand them. If we can once get at the bottom of your dreams, find out what causes them, I mean, I feel sure that we can make that nervousness of yours vanish as a prestidigitator will cause a card to vanish into thin air." She nodded. At least on the surface, she seemed satisfied, though I could not be sure but that beneath the surface it was really that she was shrewdly convinced that it was necessary to make the best of a bad situation. "You see," Craig pursued, seizing whatever advantage he might have, "as I read off from the list of words, I wish that you would repeat the first word, anything," he emphasized, "that comes into your mind, no matter how trivial it may seem to you. Perhaps it is not so trivial, after all, as you think. It may be just the thing that will lead to helping you." She nodded dutifully, but her attitude did not seem to please Kennedy thoroughly. "Don't force yourself to think," he hastened. "Let your ideas flow naturally. It depends altogether on your paying attention to the words, undivided attention, and answering as quickly as you can. Remember--the first word that comes into your mind. Don't change it--no matter what it is, even if it seems trivial and of no consequence. It's very easy to do and it won't take long. Call it a game if you will. But take it seriously." "Suppose I refuse to do it?" she suggested. Kennedy merely shrugged. "I hardly think you will do that," he smiled quietly. "Besides, it will be over soon." She leaned back in the easy-chair in which she had been sitting, and Kennedy took it as a tacit consent to the test. From the paper, as I placed myself at a table, with the list of words and the blank columns before me, he read the first word, quickly and incisively, "Foot." "Shoe," countered Honora quickly, then gazed at him to see whether she had caught the idea of what it was he wanted her to do. "Very good," nodded Kennedy, reassuringly. "That's the thing." I wrote down the word and when I had finished I could see from the corner of my eye that Kennedy also had noted the time, marking down "2-5," which I took to mean two-fifths of a second. "Gray," he repeated next. "Black." Again I noted the answering word in the second column, while again I saw him put down another "2-5." I began to see dimly what his method was. Evidently Kennedy had chosen colorless words at the start to reassure her. And the fact was that they did reassure. She saw immediately that there was nothing very terrifying about what he wanted her to do. "Dream," Craig added, from the list. Flashed through my mind, as I prepared to write, the thought that he was now coming to the words more significant. "Lathrop," she answered. I saw that Kennedy had noted a longer reaction time by some fifths of a second than before. Was it because she had checked a first thought suggested by the word and had taken extra time to substitute something for it? And why had she made the substitution that she did? It was a natural thing to mention the doctor's name in that connection. Had she rejected one word to cast about for another equally natural? I scarcely think it necessary to follow the whole thing through, question and answer, word by word. Instead I have appended a list of the words and the answering words as we got them first, and suggest that they will bear careful study: 1 2 3 foot shoe gray black dream Lathrop struggle escape ship ocean bean baked lion path book newspaper false true voyage Europe money poor sad myself quarrel Vail marry Vail bull breath sleep dream foolish wise despise love finger hand friend none serpent hiss face man chair sit bottle stopper glass empty Kennedy finished and glanced hastily over the list of words that I had written, as well as the fractions of seconds which he had jotted down on his own sheet of paper. Honora, unable to make out quite what was the reason back of all these enigmatical proceedings, watched his face narrowly. "Did I do all right?" she asked, with just a trace of anxiety in her tone. "Very fine, thank you," assured Kennedy. "It wasn't such a terrible thing, after all, was it?" "N-no," she admitted, reluctantly. Craig continued to look over the list, talking about all sorts of perfectly unrelated subjects with her, as though to remove from her mind as much is possible the memory of what had been said and done. "There is just one other thing I want," he added, as he picked up the list again and handed it to me, his finger significantly on the third column that he had laid out. "It won't take long, Mrs. Wilford, now that you understand the game. Walter, take that other column. I am merely going through the list rapidly again. Don't try to recollect the answers you gave--but then, on the other hand, don't try to make them different. Do you get what I mean? Don't force your ideas. Just remain relaxed, easy, natural. Let me have just what comes into your mind, the moment it occurs to you--please don't try to change it." "I see," she murmured, but I thought in a manner that showed she was just a little bit on her guard, and determined, if she made any slips before, not to repeat them. In quick staccato Kennedy repeated the words from the list, beginning with "foot," to which again, almost mechanically, she responded with "shoe." I noted the answering words, as before, while he recorded the time. It did not take me long to see that what Kennedy was after was to discover whether, on the second trial, she would make any very significant changes in the words. Nor was he giving her a chance to cover up. The words came so fast that even I had no time to dwell on them. I shall not pause to do so here, for later Kennedy analyzed them carefully. Here is our third list, complete: 1 2 3 foot shoe shoe gray black black dream Lathrop Lathrop struggle escape escape ship ocean ocean bean baked white lion path beard book newspaper newspaper false true true voyage Europe Europe money poor poor sad myself myself quarrel Vail words marry Vail Vail bull breath field sleep dream dream foolish wise wise despise love like finger hand hand friend none none serpent hiss crowd face man stranger chair sit sit bottle stopper stopper glass empty empty Even as I was going along under Kennedy's high pressure, I mentally noted that there were some remarkable similarities in the answers that Honora gave, but, more particularly, that there were also some significant changes, although neither so far conveyed much information to me. I knew that even to Kennedy the process would most likely require analysis in the quiet of the laboratory and I refrained absolutely from comment, though I could see that Honora would have liked to appeal to me, had it not been for the restraining presence of Kennedy. "Thank you very much, Mrs. Wilford," said Kennedy, when he had finished with both his words and reaction times and was putting away the papers in his pocket. "Is that all?" she asked. "I think so." A look of relief passed over her face. Quite naturally, she was growing tired of always being forced to play a part, whether before Doyle and McCabe or before us. I had rather expected that Kennedy would take the occasion to make some reference to the recent discoveries we had made both in Greenwich Village and over the dictagraph, more especially as they concerned Shattuck and herself. But he did not. Nor did she show any anxiety or make any inquiry herself. It seemed to me that, perhaps, Honora and Kennedy were themselves playing a game, a war of wills, as it were. At any rate, the test over, there was a truce. Some time later we returned to the laboratory and there Kennedy set to work carefully comparing the lists of words and his own records of time. "What was that test?" I asked, at length, seeing that a question would not disturb him. "What do you call it and what was it really for?" "That," he explained, "was the Jung association word test. Doctor Jung, who developed it, was, I think, a Swiss. You'll notice that on the words of little or no significance there was no hesitation, and the second time practically no change, either. But when the significant words came out she took just a fraction of a second longer before she answered. I find that her average reaction time for the innocuous words was somewhere about two-fifths of a second. She answered very quickly. "But, take her reply when I said the word 'bean.' It was nearly a second--to be exact, four-fifths, or twice her average on the words of no consequence. Don't you think that significant?" I nodded reluctantly. "Y-yes. I suppose she knows--something." "The same thing was the case," he continued, "on such words as 'bull,' 'serpent,' and 'face,' all of which, you recollect from her dreams, were significant words. Even on the words which she did not change the second time there was frequently a marked hesitation. Thus, on the word 'dream' the first time she hesitated a fraction of a second before answering 'Lathrop,' whose name evidently was suggested to her by his treatment of her nervous troubles and asking her about her dreams. But the second time there was no hesitation when she answered 'Lathrop' to the word 'dream.' The same thing was true of other words which she did not change. She hesitated the first time, but not the second. They were such groups as 'money-poor-poor,' 'friend-none-none,' 'bottle-stopper-stopper,' and 'glass-empty-empty.'" "What do you think it indicates?" I asked. "From some you can draw your own conclusions," he replied. "They are perfectly evident. She feels alone, friendless, and almost penniless. As to the bean sequence, I am inclined to think she knows much about the Calabar bean--both before and after the use in this case. Perhaps even she knows of the drug from it. But whether that knowledge is such that it has given her a first-hand direct acquaintance with the use of it--well, that is another question. "So, also, she was guarded in her reply to the words 'bottle' and 'glass.' She remembered the belladonna bottle and eagerly seized on the innocuous word, 'stopper,' referring to the ground-glass stopper, no doubt. As to the glass, or glasses, found on Wilford's desk, which must have been in her mind, because by the words I was planting and leading up to that, she was equally guarded. To reply 'empty,' could certainly not be construed as anything but innocuous, she probably thought." "How about the changes?" I questioned. "Do they show anything that is evidential?" Craig considered a moment. "They are, of course, the most important of all, those changes," he replied, taking the list and checking off the words at the third column. "She actually changed her answers seven times, and there was hesitation each time, both on the original answer and the change in this third column." Kennedy studied the list before him for some minutes. "Let's run down this list," he said, finally. "Take the first--'foot-shoe-shoe.' Nothing there, of course. Wasn't intended to be. Here--'dream-Lathrop-Lathrop.' We have already discussed that. Consciously, she refuses to tell me anything in 'struggle-escape-escape' with reference to that dream of hers of her husband. 'Ship-ocean-ocean'--I put that word in for camouflage and she seizes it eagerly, falling over herself to answer in her best reaction time, thus helping me to locate her hesitations. "Now we come to the crucial word, 'bean.' She hesitated, and in that moment of hesitation she probably reasoned something like this: 'I must just get as far from the Calabar bean which they tell me he has discovered as I can.' So she answered 'baked.' Yet that did not satisfy her. It wasn't definite enough. Any bean could be baked. So to make it absolutely explicit she corrected that to 'white bean.' She knows, all right." I said nothing, and Kennedy resumed. "'Book' was also to disarm her and she quickly replied in both cases, 'newspaper.' But 'lion' was different. I'll wager she thought first of Doctor Lathrop, for she went right back to the dream and answered 'path'--then, the second time, perhaps before she knew it, she answered 'beard'--which Lathrop has--when in fact I'll bet that if we tried it over again the answer she would give to cover it up would be 'mane.' "'False-true-true' and 'voyage-Europe-Europe' need not be discussed. 'Money-poor-poor' we've already touched on and 'sad-myself-myself' falls into the same class--showing her despondency. With 'quarrel-Vail-words' her mind shows all is still fresh in her recollection. We know pretty well now what her inner feelings were toward him. However, quite naturally and stereotyped comes the next--'marry-Vail-Vail.' Of course. Consciously she would never think of herself marrying any one else--until there is a new deal, so to speak. "But now we come to the most significant parts of all--the 'bull' sequence. The moment she heard that she hesitated, realized that she must not hesitate, and in a sort of mental panic answered the thing that came crowding into her mind, the pursuit by the bull and its hot 'breath,' which, you remember, we have already discussed. She must have regretted allowing herself to say it. That was one reason why I wanted to try the test over. Sure enough, the second time she corrected it to something quite innocent connected with the dream--'field.' Whether she realized it or not, it confirms what the Freud analysis showed us. "Then," he went on, quite enthusiastic over the progress of his association test, "I reassured her by the next words and did not expect to obtain anything--'sleep-dream-dream' and 'foolish-wise-wise.' The next brings us squarely back to the subject that interests me most in my study of her, her real feelings toward Shattuck. I said 'despise.' At once, instead of associating, she sought the opposite--'love.' Yet that seemed, perhaps unconsciously, a bit strong. So she softened it next to 'like.' She did that for her own benefit. She herself would never betray to the world her own emotions. Therefore 'like' was a better word to use than 'love.' She has been trying to make them synonymous--with poor success." I nodded. Somehow I felt that in her heart of hearts Honora had found love, whether she admitted it to herself or not. But I realized that even if she had, she would be the last to betray it to the outside world if she could help it. "'Finger-hand-hand'--another of the off-guard words," continued Kennedy, quickly. "'Friend-none-none'--we have touched on this idea already. But now we come again to something very important--'serpent.' At once she answered 'hiss.' Then she changed it and the thought uppermost was the recollection of the 'crowd' in her dream. Remember Freud?--a crowd, something secret? "The most important change of all, though, is the next--'face.' She knew that already I had questioned her on that point in the dream--the attributing of human faces to the animals that appeared to her in her dreams. Perhaps she recollected that she had told Doctor Lathrop once that the face in the dream resembled that of Shattuck. But she never would admit that to me. I fenced about with her on that point, both in the spoken and written dream, without getting a bit of satisfaction from her. She simply would not admit a thing. Yet I'm convinced that she told the truth first, that the face was that of Shattuck. However, with that still in her mind, she hesitates in recalling the dream. I'm sure her first thought was 'Shattuck.' But she put that out of her mind in the fifths of a second that elapsed. Instead, she answered just as quickly as she could, in the hope she had betrayed nothing, the colorless, 'man.'" I said nothing. I was always fearful of whither Kennedy's psychanalysis was tending. "Even the general 'man' was not explicit enough for her," he proceeded. "She meant that there should be no mistake as far as I was concerned. 'Man' might include Shattuck. So, on the second questioning she became more particular in her identification of the 'face.' This time it was 'stranger.' Doubtless she felt that it would eliminate both herself and Shattuck from consideration. But she was mistaken," he concluded, triumphantly. "Instead, it really points to Shattuck--and to herself, too. Unconsciously now, she is really trying to eliminate both herself and her lover--and she knows that he is that." Kennedy flipped the list, as he added: "'Bottle-stopper-stopper' and 'glass-empty-empty.' An effort to get away from anything incriminating. Clever, too." I said nothing. What did it mean? Was she, after all, guilty--or at least a party to the crime? The very idea was repugnant to me. I knew it was of no use to quiz Craig. He was still non-committal and impartial. At least I hoped he was still impartial to her. XV THE CONFLICTING CLUES It was early the following morning that Doyle burst in on us, very excited and waving a morning paper. "Have you read the news?" he demanded, slapping the paper down in front of Kennedy. We read at the point where Doyle's forefinger indicated. It was a personal inserted among the advertisements by Doctor Lathrop himself. No longer, it announced, would he be responsible for the debts of Vina Lathrop, his wife. Lathrop had at last definitely broken with her. Kennedy and I exchanged glances. I recalled the quarrel we had interrupted on our last visit to them. Evidently that had been the climax. Nor was I surprised. It had seemed inconceivable to me, since my conversation with Belle Balcom, that ever Lathrop could be the kind of man to sit complacently under the growing gossip about Vina. How he had even waited so long was a mystery, unless to assure himself that what he heard was the truth. For men of Lathrop's stamp are the last to condone anything in a wife, no matter what may be their own standards for themselves. "Well, at any rate," conjectured Doyle, rather heartlessly, I thought, "I don't think people will waste a great deal of sympathy on her. It leaves Vina Lathrop no more than she deserves. The man she tried to use is dead. The man she sought to capture has turned her down cold. Now the husband she had no use for, except as a meal ticket, has left her. I can't see but what that dame had it all coming to her." Kennedy refrained from comment. "Where has she gone?" he asked merely. "Do you know?" Doyle shook his head. "This is the first that I knew that they were separated," he responded. "No, I haven't any idea where she is." "What of Doctor Lathrop?" "He seemed to have taken it very calmly. From what I hear, he hasn't even interrupted his practice. He stays there at the Drive address where he has his office. I suppose she has gone to a hotel, or perhaps out of town. I'll find out for you and have her watched, if you want." Kennedy nodded, but did not say anything, and I know Doyle's attitude had not raised that gentleman any higher in Craig's estimation. It all seemed very strange, and, I felt sure, however, well worth following up. "Of course, you know we haven't neglected the Wilford telephone wire," put in Doyle, sensing that all was not just as it should be, yet not knowing just why. "What did you do?" "Put in a tap. Then I had McCabe and others listening in in relays in another room." "Yes?" "Here's a report of what they got this morning." Doyle pulled out a sheet of thin paper on which had been typed some notes. "There was a call early this morning for her," he said, as he ran his eye down the sheet. "It was from Shattuck--without a doubt. He's suspicious. The first part of the conversation shows that, you see." "Let me read it, if you don't mind?" asked Kennedy. "Not at all," agreed, Doyle, handing the copy to Craig. Together we read it. "Good morning," it began. "Is this you, Honora?" "Oh, good morning," she replied. (It was apparent that Mrs. Wilford recognized the voice, but she was cautious about repeating the name.) "I've something very important to tell you--but--well, not over the telephone. Is anybody listening?" "I don't know. I suppose there is. Everything I do is spied on and watched. I can't write a letter. I can't go out--" "I suppose that's right. If you went out you'd be followed. There's no place that's safe. Probably somebody's getting an earful of this," came back the other voice. "Still, I've something very important to say to you. Hang it! I'm going to drop in and see you, Honora. This isn't an autocracy--yet. They can't prevent me talking to you in your own home. Though, I suppose, even that is an offense. However, I'll call. Keep a stiff upper lip. Don't let them put anything over on you." Mrs. Wilford must have tried to laugh it off, for the operative had drawn a line indicating a laugh and had added merely the repetition of the words, "Good-by." Doyle looked at our faces as we read. "I have a scheme," he announced, craftily. "See what you think of it. There's that dictagraph I put in, you know." Kennedy nodded. Although our opinion of Doyle was not of the highest, it was not impossible that here was a situation that called for no great amount of cleverness to surmount. "Want to use it?" he asked. Kennedy considered. "I put the thing in right. There's a receiver in every room, and I've got a sort of central office there. You can listen in on any room you please by just throwing a switch." Kennedy assumed a flattering manner. "Just the thing, Doyle," he acquiesced. "Now look here. This is the way to work it. You go there first--not to the room, but to the apartment. Stay around there a bit as though you were looking for something, then leave and take care to make it certain that they know you are going away some distance and will be gone some time." "I get you," agreed Doyle. "Then McCabe--" "Confound McCabe!" interrupted Kennedy. "He must clear out, too. He's buzzing around that maid, Celeste. Well, for once it may lead to something. Give McCabe something to do that will take him away, too. Then tell him to let Celeste know. Get it? Make it as plain as day to her that for once you are all off the job. Then she'll think it's safe--unless she's clever," added Kennedy. "Meanwhile Jameson and I will slip into that little listening post of yours. Maybe we'll get something. You can't tell." "It sounds all right," commented Doyle, loosening a key from a ring. "There's the key--it's Apartment K where the dictagraph is." "All right," remarked Kennedy, taking it. "Now go along and get your end of the plant working. Do everything you can to let her believe that you've relaxed. I'll get there in half an hour. We can't put this off too long." Doyle left with alacrity. For once he could understand Kennedy's method and approve it. Half an hour later we entered the Wilford apartment-house, taking care to do so at a time when the elevator was not down at the ground floor. As far as we knew, no one interested had seen us come in. That was the one chance we were forced to take. Its only disadvantage was that it made it necessary for us to walk up eight flights of stairs, and even then to go carefully, lest we meet some one in the hall. However, we found Apartment K at last without any difficulty, opened the door, and admitted ourselves quietly. Doyle had located the dictagraph in this room, two floors below the apartment of the Wilfords', in this vacant suite. As we entered, I saw that in the room were merely a deal table and a couple of chairs. On the table lay the box containing the receiving end of the dictagraph, to which already were fitted the head and ear pieces for listening. The switch on the table was marked, showing the various rooms in which the transmitters had been placed and arranged so that one might follow from one room to another, if necessary. There was paper for notes on the table, too, but otherwise the room was bare. Kennedy adjusted the ear-pieces over his head, much as a wireless operator might have done, and, noting how he did it, I followed suit. Then we waited. I could hear the clicks as he moved the switch past one connection after another, trying out the various rooms to see whether there was any one in them or not. There was no one in the living-room, but as we listened we could hear the striking of a small clock on the mantel. From room to room we went, in imagination, almost as if we had been there, but able to go about unobserved. Had Honora been clever enough to penetrate our ruse? Or had Doyle and McCabe executed their end of the scheme clumsily? We waited impatiently, wondering whether, after all, it was a fools' errand for us. Suddenly I could hear a dull, rhythmical noise above the mild buzzing of the dictagraph. "What's that?" I asked, almost in a whisper, which was involuntary. "Footsteps of some one coming down the hall into the library," replied Kennedy. "I fancied from slight noises which I heard that Honora was in there, alone, reading perhaps. I thought I caught the rustle of paper." I could now make out the vibrations more clearly, then the low, almost inaudible buzz of a voice. "Now it's plainer," I whispered. Kennedy frowned. "They can't hear you," he reminded. "Still--don't forget _I_ can." I took the broad hint and was silent. Kennedy adjusted the machine for loudness and gradually I could hear the lowered voices being caught and played up. It was Honora speaking to her maid, Celeste, who had just entered. "You've been down in Mrs. Smith's apartment?" we heard Honora ask. "Yes, madame." Kennedy shot a glance at me. Two, then, could play at the same game of watching. Evidently the maid had evolved the scheme of visiting some friendly maid in the building, and from that vantage-point watching the watchers. I trusted that she had seen nothing of us. It could hardly be that she had--or at least that they suspected the presence of the dictagraph, or they would not have talked even in whispers, when they might have written and thus have been safe from being overheard. I was beginning to be relieved. "Why did that McCabe tell you he had a day off?" asked Honora, thoughtfully. "Did he really go?" "Yes, madame. And the other man hasn't come in. Mr. Doyle was here, but he didn't stay long. I heard him telephone for a taxicab to take him to the Grand Central. He seemed to be catching a train and looked as if prepared to stay away overnight." "A train?" caught up Honora, eagerly. "Very well, Celeste. When Mr. Shattuck comes, let him in. Watch. Let me know if you see any one watching. It--it seems--I can't understand it." The maid murmured something soothing in French to Honora and departed. For some time--it seemed an hour--we waited in silence. Finally Kennedy reached over and touched my elbow. Again I could hear that low vibration, as of some one walking. "It's Shattuck--I'll bet," Craig cried, excitedly. Sure enough, it was, as we soon found out both by his voice and the conversation. "You've heard about Vina and the doctor?" he asked, almost as soon as he entered. "No," replied Honora. "What about them?" "They've separated. Lathrop has put a notice in the papers that he will no longer be responsible for his wife's debts." Honora uttered a quick exclamation of surprise. "Rather a nasty thing for the doctor to do, though," commented Shattuck, then added, hastily, "I mean the way he did it--publicly, in the papers, and all that sort of thing." "I suppose so," came reluctantly from Honora's lips. Kennedy smiled. It was very human, after all. Nor could one blame Honora for having scant sympathy with the woman who had caused her so much pain and anguish. There was silence for several moments, in which I trusted that Shattuck was duly chastened for having expressed any sympathy for Vina, even in a casual way. "Tell me, Vance," she asked, finally, with just a trace of eagerness showing in her voice in spite of herself. "You never really cared for her--did you?" Shattuck answered quickly. "Why, you poor foolish little girl--don't you understand yet? It was she--set out to capture me--not I who sought her. Ask anybody. They'll tell you. I begin to believe everybody knows it--knew it long before even I saw it. How Lathrop could have missed it so long is beyond me. Don't you see? It placed me in rather an awkward position. I wanted to warn him--yet how could I? Of course I never cared for her. The fact is that I have had to avoid her, even when she tried to make some business deals through me. Why, only yesterday Lathrop came to see me. It must have been just before he put that advertisement in the papers. I had the very deuce of a time to make him see the case. As luck would have it, though, Kennedy was there. I hope he got an eyeful. Once before he saw me with her. It was when she was trying to sell some stock." Honora said nothing, though apparently the explanation was just what she wanted to hear and it satisfied her. I looked over at Craig. If it was true, I felt that it was greatly to the credit of Shattuck, knowing his reputation. But was it true? Was it not what he would have said to Honora, anyway? Might it not be that he was laying the foundations for an alibi in case Kennedy or some one else retailed stories to her? "Are they still just as insolent up here to you?" he asked, solicitously, after another silence, changing the subject to one more intimate. "Oh, Vance, it's awful!" she confessed. "The deuce!" he exclaimed, hotly. "Sometimes I feel as though I could fight the whole crowd of them, Kennedy included. It's an outrage, this constant suspicion of you." "But, Vance," she murmured, "you know you must be careful for yourself, too." "And you, Honora?" he replied. "Have you no need of help, no need of a friend?" It was evident that each feared for the other, recognizing the suspicion under which both labored. More than that, there was genuine regard between them, it was evident, tempered with restraint. "I suppose you've heard that they've found a Calabar bean down in Vail's office, on the floor?" asked Shattuck, hesitating, but finally coming to a remark which evidently had been on his mind and cost him something to make. I was all ears, in hope that he would betray something about having some of the beans in his own possession, or that Honora would betray something about having Chase search Shattuck's apartment, if, indeed, she had ordered the young detective to do it. But neither of them said a word. Was it because they knew nothing, or was there a tacit understanding between them never to mention some mutual secret? "So I've been told," was the simple reply Honora made to Shattuck's inquiry. "Who told you?" "Mr. Doyle, himself," she replied. "Has Kennedy done anything?" he asked, quickly. "I had another visit from him yesterday." "What did he want this time?" "He had a list of words--more of his science. I can't refuse to do what he asks--and yet--I'm afraid. You know these scientists know so many things that aren't so about women." Kennedy nodded over at me. I knew what was passing in his mind. It was surely strange to hear oneself discussed and I recalled the old adage about eavesdroppers hearing nothing good of themselves. Besides, I knew that his Freud theory had struck home. Honora's very anger at the theory was proof enough that it struck home in one of her own "complexes." "Confound him!" muttered Shattuck. "I suppose you are right, though. You know this ordeal bean from the Calabar? Of course you remember the derivative from your father's place--the physostigmine. Well, the beans are used in a queer, primitive sort of dueling by the natives. They cut the beans in half. Each eats a half. It is a sort of a duel by ordeal." "Yes," she answered, quickly. "So I've been told." Kennedy nodded to me. Neither of them said more about it. Was it because they recognized it as a dangerous subject? Or had Honora really discovered the dictagraph in her own home? In that case, this very conversation was being held for our benefit, out of sheer bravado. Nothing more of importance was said and we figuratively followed them out into the hall and over a good-by that was considerably lengthened by Shattuck and threatened to become sentimental. Only Honora restrained it. "What next?" I asked, as we could hear the slam of the door in the Wilford apartment. "I don't think I shall stay and listen here," concluded Kennedy. "I can't see that we've found out a great deal, as it is. There are several things that must be done immediately. First of all, I want to see Lathrop. It may be that we'll find out something from him." We made our way out of the apartment, as we had entered, trusting that with our care we would not be observed. A few minutes later we were at the door of the waiting-room of Lathrop's office. "Evidently he doesn't take the affair any too deeply," commented Craig. I looked about. The office was as full of patients as ever, and he was going about his professional work much as though nothing at all had occurred to disturb his peace of mind. We waited until the last patient had gone and finally were able to see him alone. "I can guess what you are here for," he greeted, without a trace of embarrassment. "I suppose the afternoon papers will be full of it. Already I've had a string of reporters--one from your own paper, Mr. Jameson," he added, significantly--"a Miss Balcom. Do you know her?" "Yes," I answered, as offhand as possible, "she is a very clever writer. Did you--er--tell her any--" "Not a word to say," he interrupted, bruskly, "not a word to say. I refused to make any statement. What's the use? The fact stands for itself." In spite of what he said, it was evident that he would talk, at least a bit. "Then you knew all about--what was going on, all along?" inquired Kennedy. "I had my suspicions," the doctor replied, airily. "I cannot afford to be held up to ridicule. It was a matter of saving my very career. As for the Wilford story--pouf! I don't care a rap about it--that is, I didn't until the gossips added the Shattuck scandal to it." Whatever he might say, it was evident that his lips belied his real feelings. He was really bitter both toward the memory of Wilford and toward Shattuck as well, conceal it as much as he might try. "Then you credit the Shattuck rumors?" demanded Kennedy. "I won't say," snapped the doctor, testily. "Where has Mrs. Lathrop gone?" asked Kennedy, point-blank. "How do I know?" bridled Lathrop. "I've heard her talk about friends at the Sainte-Germaine--perhaps you might find her there. You're a detective," he added, coolly, then suddenly: "That's right. Get her side of the story. Play it up, if you like. You might as well. Yes, by all means. Then perhaps I can set you right on some points. Don't mind _me_. Good morning, gentlemen," he bustled, taking up his black doctor's bag. "I have a very serious case waiting for me." Kennedy did not comment as we left, but beckoned quickly to a vacant taxicab and we were whisked to the Sainte-Germaine. I knew it was of no use to try to see Mrs. Lathrop in the ordinary manner, and, therefore, adopted one of my many newspaper ruses to find out where her room was and then to get to it. As she opened the door to what seemed to be an innocent knock from a chambermaid or bell-hop, she exclaimed in surprise at seeing Kennedy and myself. Almost, I exclaimed also. Vina Lathrop seemed to be a changed woman. "Why have you followed me here?" she demanded. "Did _he_ send you--or was it that woman?" "Neither," returned Kennedy. "It's not so easy to hide away in New York." She did not move from the door, nor did she invite us in. Still, I could see that she was there alone, that the "friends" whom Lathrop had hinted at were either mythical or that she had not gone to them. "I thought that perhaps you might like to tell us what the real reason for the break was," hinted Kennedy. "Of course, Mrs. Lathrop, there's no use for me to beat about the bush. You know and we know just what the world is saying. If I might be of any assistance to you--putting things straight, you know--" He paused, endeavoring to see whether she showed any disposition to talk. For a moment she was silent, biting her lips. "I never want to speak to him again," she burst out, passionately, at length. "You will have to see Doctor Lathrop about that--at present," she added, sullenly. "Does Mr. Shattuck know where you are?" "I suppose every one will know--now," she cried, a look almost of alarm crossing her now pale face. "Really--I have nothing to say. You must see my--my lawyer." "And he is--?" "I shall let that be known--when I get ready," she blazed, turning. "Now, might I ask you to leave me? I don't see how you got past the floor clerk, anyhow. Good-by. I--I don't want to have a scene." She closed the door and we heard the bolt shoot. Somehow I could not help having my suspicions aroused by her very manner, as we turned away. Did she know something--and was she really afraid of us? XVI THE FINESSE "What's the next move?" I inquired of Kennedy as we entered the elevator. He did not answer, and I thought it was because he did not care to do so. "Didn't like to talk, even though we were alone with the elevator boy," he explained, with his usual caution, when we had arrived at the ground floor. "You never can tell who is listening in public places." "No," I answered, dryly. "That was how I found out where she was in the first place." Kennedy smiled. "Very good, Walter. Still, it just goes to prove what I said. Mrs. Lathrop might do the same thing to find out about us." We sauntered along a few steps through the lobby in silence. "I don't suppose Shattuck will be in his own apartment after that talk with Honora," Kennedy considered, glancing at his watch. "Guess we'd better try to see him at his office, if we want to see him anywhere." I saw what he was thinking about--the relations of Vina and Shattuck and the construction that Doctor Lathrop had put on them. "The finding of that Calabar bean in Shattuck's apartment has puzzled me," I confessed. "I've often wondered whether he ever missed it, whether he knows." "Just what I was thinking about," admitted Kennedy. "On the way down-town I'm going to drop in and see Mrs. Wilford's detective, Chase." "Why, Mr. Jameson, you've beaten me to it--and have you got the story?" I turned in surprise at hearing my name spoken by a woman whom I hadn't noticed. It was Belle Balcom, always enterprising and on the alert for a good story for her column of society gossip. "I thought I had a scoop," she pouted. "And I get here only to see you coming out." "Where did you find out?" I asked, in surprise, careful, however, not to admit that I knew what she meant, although I was certain that it must be to see Mrs. Lathrop that she had come. "Never mind," Belle tantalized. "Where did you find out?" "That would be telling," I begged the question, turning and introducing Craig. "Oh, I'm so glad to meet you," she smiled. "Of course I've heard a great deal about you from Mr. Jameson and I've always admired your wonderful work." "Indeed you've helped us a great deal in this case, yourself," returned Craig, ignoring the flattery, as he always did. "I'm so glad," thanked Belle, sincerely. "If there's anything I can do, ever, I hope you'll ask me. It isn't often that I feel that the stuff I do has any real importance. More often people think I'm a prying pest, I imagine. But then without that eternal curiosity, who could write? Isn't that so?" she appealed to me. "Quite," I agreed. "Especially in a woman," thrust Belle. "I'm sure that can't be so," remarked Craig. "Reporters and detectives have much in common. Women make good in both fields--very good." Belle smiled. Sophisticated she might be. Yet no woman can be said exactly to hate flattery of the right sort. "How does Mrs. Lathrop take the affair--with bravado?" inquired Belle. "You see, that expedition down to Greenwich Village with Mr. Jameson has made me look on this case with a sort of proprietary interest." Kennedy smiled seriously. "There, now," he nodded, "you're interviewing _me_." Belle smiled back in turn, taking the hint. "I'm sure you'd be hard to interview, if you didn't want to be interviewed, Professor Kennedy," she said. "How did you find out where she had gone--really?" I asked. "Tell us. It might help--and you remember what you said just a moment ago." Belle considered an instant. "Well," she thought, "I don't know as it would be violating any confidence, after all." Kennedy, always thoughtful, had gradually edged our way into a sort of alcove. "You see," she began, "first I tried to get at Doctor Lathrop himself. But I guess you must have been there first. He was barricaded, so to speak. I posed as a patient, tried to think up all kinds of ailments I could, just to get in. But he had an assistant who interviewed every patient. I think that fellow would make a medical detective. I thought I was clever, but he found me out and I was politely requested to step outside." I glanced at Kennedy. Evidently Lathrop did not intend to talk. Was it wholly natural reticence? "Then," resumed Belle to me, "I thought of our friend, Zona Dare. I remembered that she had been intimate with Vina Lathrop. Zona wouldn't say anything. But I didn't need that. From her I got the cue. I knew she was keeping something from me, just knew it--woman's intuition, I guess. I knew that Zona lived here at the Sainte-Germaine." "But Mrs. Lathrop is alone," I hastened. "Surely. You wouldn't see them together. Trust Zona. She's too clever for that." Again I glanced at Kennedy without getting anything from the expression of his face. Was it a clue? Did it mean anything, this immediate appeal by Vina for help from the Freudian interpreter of the Village? We chatted a few minutes longer, as Kennedy turned away further inquisitorial shafts of the clever reporter. However, somehow I felt that Belle still had something on her mind. "Then you aren't going to write it, after all?" she asked, eagerly, of me, as Kennedy showed signs of leaving. "Of course not," I assured. "It wouldn't look right--at this stage of the case--for me to write, do you think? However, that's no reason why _The Star_ shouldn't have the story." She beamed. "Very well, then. I'll try to get it," she replied, rather relieved at the thought that whatever clever work she had done to get the tip that had located Vina would not go for naught and would be credited to her. We bowed ourselves away, leaving Belle the difficult and unenviable job of getting at Mrs. Lathrop again, something I should not have wanted to do, judging by the fiery glance that had been shot at us from behind the slammed door. "That will be a last straw to Vina Lathrop--when she knows the newspapers have found her out here," I remarked, as we turned toward the street entrance. Kennedy drew me back and we sidled into the protection of the fronds of a thick clump of palms. I looked out cautiously. There was Doyle just coming up the steps of the hotel. Doyle bustled in, and we let him pass, unaccosted. "Where did _he_ get his information?" I wondered. "Not so difficult. If the police drag-net is out, a hotel like the Sainte-Germaine isn't at all safe," replied Craig. "I imagine we can leave Vina to their tender mercies--the police and the press." We left the hotel hurriedly lest we might encounter any one else, and a few minutes later found ourselves again at Chase's detective agency. Chase was in and regarded us inquiringly as we entered. "About this Lathrop case," introduced Kennedy. "You know that she was very intimate with Mr. Shattuck." Chase nodded. "It occurred to me," went on Kennedy, "that since you were working for Mrs. Wilford you might be able to help me. There were several things you told me the other day that I've been thinking about." Chase narrowed his eyes as if trying to fathom what Kennedy was thinking. "I admit breaking into Shattuck's apartment," he said. "Do you mean that?" "Partly. Why did you do it?" "It was to get some letters Mrs. Lathrop had written to him," returned Chase, without quizzing. "Did you get them?" "I did." "Where are they?" Chase balked. "Did you read them?" "Yes," he answered, reluctantly. "What was in them? Shattuck had been pursuing Mrs. Lathrop, hadn't he?" fenced Kennedy, keenly. "No--he had not. She had been pursuing him," snapped Chase, though why he was so evidently put out about it I could not make out at first. "How about that Calabar bean?" "I found it in a cabinet, while I was searching for the letters," he answered, his face betraying no expression. "Why did you tell me that in the first place?" demanded Kennedy, suddenly switching the subject. "Did you have any motive?" "Motive? I thought you ought to know--that's all. He's not _my_ client, you know." "But he's a _friend_ of your client and--" "Say, Kennedy, I know how Doyle has been hounding that poor little woman. If you want the truth, I didn't tell Doyle because it wouldn't do any good. I thought you could be _fair_." "Well, what's your opinion?" "I haven't any opinion. I know what I found. It's for you to have an opinion. Besides, I won't sacrifice a client for a friend of the client. Get me?" he asked, pointedly. "She has won you, hasn't she?" asked Kennedy, somewhat, I thought, in Doyle's style. Chase looked at him a minute. "Say, Kennedy," he returned, "I've always regarded you as something more than the rest of us." He stopped as though he would have said more, but considered he had said enough. What he meant by his cryptic remarks I could not make out. Was he determined to save his client, even at the cost of her lover? Kennedy's face was inscrutable. If he knew what Chase meant, I am sure Chase read no answer. We left immediately afterward and soon were back again in the Subway. As we waited for the train, Kennedy paced the platform. "I think I'm right, Walter," he remarked. "The thing is to prove it. I'm going to use a little more of Freud--to apply him to some detective work--in other words, I'm going to play upon suppressed desires. Just watch how it works." Somewhat less than half an hour later we found ourselves in the hurly-burly of the Wall Street district. Shattuck, I knew, had an office around the corner not very far from that which Vail Wilford had occupied. Kennedy, who had been there before, easily located it and called the floor from memory. "It's not a large office," I remarked, as I followed Craig down the hall and stopped before a single glass door that bore Shattuck's name, adding, "Banker & Broker." "But probably it's large enough for all the brokerage business that Shattuck really does," he returned. "I have an idea that it is just about enough to keep him from being classed as an idler. Besides, it gives him standing." Kennedy handed his card to the boy who presided over a sort of swinging gate in the outer office. The door to Shattuck's inner office happened to be open and we could see him. Consequently it was not possible for him to send out word that he was not in. It was a rather nettled office-boy who returned to us. "For what, may I ask, am I indebted to you for _this_ visit?" inquired Shattuck with almost insulting bruskness as the boy stood at the door, admitting us, then carefully closed the door to the outer office. I felt angry at the tone, but Kennedy kept his temper admirably. "I suppose," began Craig, clearing his throat and speaking as deliberately as ever Shattuck did, "that you know the story about Mrs. Lathrop?" "Some one on the street called my attention to it," Shattuck prevaricated, rather than admit interest. "I thought you might be in a position to explain it--at least to throw some light on it," pursued Kennedy, directly. "I'm quite interested, naturally." "Explain it?" flared Shattuck, eagerly seizing on something that would divert the main issue. "Explain it? Why, you and Doyle and the newspapers"--nodding insultingly at me--"ought to be able to do that best, don't you think? It's you all that have caused a great deal of trouble. Judging by what I read and hear, you know more about our affairs in this case than we do ourselves. I'd suggest that perhaps our positions should be reversed. I might appeal to you for information, rather than have you coming around here appealing to me." Not only was it what he said, but it was even more the tone and manner in which he said it that seemed to rub Kennedy the wrong way. As for myself, I must confess that I was boiling over at the bravado of the man. I would have come back with a quick remark--and probably have exposed my hand and done exactly what Shattuck expected, for there was no denying that he was clever with a gambler's cleverness and nerve. It was not so with Kennedy. For a moment he paused, as though checking a first remark; then he spoke in the same measured and considered tones as at the start. "I can tell you, Shattuck, that I don't like the attitude either you or Mrs. Wilford assume." Shattuck merely shrugged superciliously, and would have turned to some papers on his desk, had not Kennedy possessed one of those compelling personalities that demand that you hear them out, whether you like it or not. "Mrs. Wilford seems to have assumed a sort of passive attitude toward me," Kennedy resumed. "You don't expect her to help you?" inquired Shattuck. "As for yourself," continued Craig, unperturbed, "I am frankly of the opinion, Shattuck, that your attitude is quite one of open hostility. I would not presume to dictate to either of you how you should order your conduct--but--it seems to me that, under the circumstances, it might not be unwise to take care not to prejudice your cases, you know." Shattuck involuntarily shot a quick glance from under his heavy eyebrows at Kennedy. But not even Shattuck's cleverness could read anything in Craig's face. What is it that this man knows? Quite apparently that was the sudden thought working back of Shattuck's beetling brows. "For instance," continued Kennedy, as though determined to have his way in the matter and ram the words down Shattuck's throat, "I am sure you know of that Calabar bean which I--or rather Mr. Jameson--discovered in Mr. Wilford's office--not very far away from here, I see." Shattuck's face was a study. Not once did the man lose his poise. It was not that. "Well, it raises some interesting problems. I won't say that I haven't settled them. But, for the sake of argument, let us take the circumstance--just in itself." Shattuck calmly lighted a cigarette and deliberately inhaled it, bored. "Of course," Craig went on, after a pause, "we all know that Doctor Lathrop is a doctor and hence likely to dabble in almost anything relating to his profession. Perhaps he knew of the existence and the properties of the Calabar bean. Quite certainly, I should say. No doubt he has used the drug--physostigmine. In fact, he tells me he has. Very well, then. So much for that. "Take yourself, for example. I think I recall seeing many African trophies in that very cozy den of yours. Now, the Calabar bean is well known in Africa, not only in the Calabar, on the west coast, but in many other parts of the continent that travelers and tourists visit. So, you see, although at first sight such a bean might seem to have very little to do with a prosperous broker on Broad Street, it is not impossible that a judge or jury--or a detective--might see a connection." Kennedy paused to watch the effect of the home thrust. I cannot say that Shattuck even winced. He was a man with too much control over himself for that. I longed for some of the psychological laboratory instruments that will reveal, often, what a nerve-strong exterior hides. "But, quite more important still," continued Kennedy, "is the fact that the bean, or rather its derivative, physostigmine--which we know was the poison that killed Wilford--is known and used by oculists for its curious effect on the pupils. Now, from what I have learned on unimpeachable authority about Mrs. Wilford as a girl, her father, Honore Chappelle, a Frenchman, was a well-known oculist. He had no sons and often used to wish that his only child had not been a girl. For a time he had some vague idea, I believe, that his daughter might take up his place in the business. However, that was merely fanciful. As Honora grew to womanhood and tasted the advantages of the not small fortune her father had piled up, the social life appealed to her. And yet, in the girlhood days, who shall say she did not learn something of the Calabar bean, of the drug, and of its properties? It would be most unlikely if she did not." Kennedy paused for a moment, leaving Shattuck almost speechless and hiding a secret fear. "You can draw your own conclusions from what I have just said," finished Craig. "Sometimes, you know, actions speak louder than words." Shattuck had risen, almost angrily as two red spots of passion appeared on his face over the cheek-bones. "Don't you think you have done enough, hounding Mrs. Wilford with your confounded science?" he demanded. "I cannot say," replied Kennedy, coolly, reaching for his hat and deliberately turning away. "I am telling you this only for your own benefit. Good morning, sir." Just what Kennedy was attempting I began to understand as we closed the door to the hall and turned again to the elevator. The seeking out of Shattuck was quite in keeping with the plan of campaign Craig had mapped out at the start. I saw that he was counting on planting something that would make Shattuck fear for Honora, if not for himself. And, it was evident that behind his bravado Shattuck did have a fear for Honora. XVII THE SUPPRESSED DESIRE Even before Kennedy announced where he was going, I outguessed the next step in his scheme. He would end by planting something that would make Honora fearful for Shattuck, as well as for herself. The effect would be to bring to light her suppressed desires, to make the Freudian theory play detective for us. And then? Almost anything might happen. Looked at in this light, I could see that Craig would have done a very profitable day's work. It was, in short, merely playing one against the other--first Lathrop against Vina; now Honora against Shattuck. We rode back again up-town and prepared to make our daily excuse for visiting Mrs. Wilford. In spite of the distastefulness of our duty, I felt sure that still our position with her was superior to that of the other inquisitors who were always on her trail. "Before we go in," cautioned Kennedy, as we entered the main entrance to the apartment, "I want to see McCabe. He must be back on the job by this time." Careful to cover ourselves, we sought out the ostensibly empty apartment which Doyle had hired as a dictagraph room. McCabe was there and seemed to be glad to see us. Evidently he had some news to report. "What's on your mind, McCabe?" greeted Kennedy. "Why, sir, he's been calling her up again." "Who?" "Mr. Shattuck, I mean." Kennedy merely glanced at me. The virus had begun to work. "What did he say?" asked Kennedy, quickly. "I couldn't just make out what it was about. He wasn't very definite. Said he wanted to see her alone." "And Mrs. Wilford?" "Said she couldn't--that she was afraid--afraid for him, she said. I guess she knows pretty well how we're watching her." "What did Shattuck say to that?" "Well, I should say he was trying to warn _her_," replied McCabe, "without coming out too definitely. You see, they were both pretty careful in the words they used. There's something strange between that pair, you can be sure of that." "What were the exact words?" asked Kennedy. "Did you get them down?" McCabe nodded and referred to his notes. "When Mr. Shattuck called up, he asked her first, 'I suppose they're watching you yet, Honora?' "'Oh, Vance,' she answered, 'it gets worse every day.' "There's some more--and then he suddenly said, 'Honora, Kennedy has just been here to see me again.' "She seemed to be rather alarmed at that news. 'To see you again, Vance? What about?' "'I don't know what he's up to,' Shattuck replied. 'I wish I did. It's something about that poisoned bean--you know, the thing they've been talking about.'" "Pretending ignorance!" I exclaimed. "He knows. Go on." "They talked about that a little while, without saying anything important. The next was Honora: 'He keeps asking me all sorts of questions about dreams and trying psychological experiments. I don't dare refuse to answer. But what do you suppose it is all about, Vance?'" "What did Shattuck tell her?" asked Kennedy, interested. "Here, I'll read it, exactly. 'More of that Freud stuff, I guess, Honora, from what you've already told me. That may go all very well in a book--or in Greenwich Village. But it's a fake, I tell you. Don't believe it--too much.'" "That's a remarkably reassuring statement," commented Kennedy. "Don't believe it--and then he takes it all back by adding, 'too much.'" "Yes, sir," agreed McCabe, to whom this angle of the case was a mystery. "I don't know as he believed what he said himself. You see, he next asked her: 'Can't you see me? I _must_ try to help you.' And he meant it, too." "Did she say she would?" hastened Kennedy. "Not directly. 'Vance, I'm so afraid--afraid to drag you into this thing. You know they're watching me so closely. I don't see them around--yet they seem to know so much.'" "You don't suppose she suspects anything of this?" I interrupted, indicating the dictagraph and the tapped telephone. "Hardly," answered McCabe. "She wouldn't talk at all over the wire, if she did, would she? Here's how it ended. Shattuck said, finally, 'Well, I'm going to see you very soon, anyhow, to have a heart-to-heart talk, Honora.' He seemed to be quite worried. And so did she over him." "Have you told Doyle anything about it?" asked Craig. "Haven't had a chance yet. It just happened." Kennedy turned to go. "Oh, just before that that detective called her up, too." "Which one--Rascon or Chase?" "Chase." Kennedy smiled quietly. Everything was working. "What of him?" "He said you had been to see him. There was something about that poisonous bean he told her." "Did he mention Shattuck's name?" asked Kennedy. "Yes, he questioned her about Shattuck--about his travels--I thought it was pretty broadly hinting after he mentioned that Calabar bean." "But did he say anything definite about it? I mean, anything connecting it with Shattuck?" "No--nothing definite." Evidently Chase had never told Honora of his discovery in Shattuck's apartments. Why? Was it because he was sure that she would not believe it? Was he waiting for more conclusive evidence? What was the reason? It had not been revealed even yet. We thanked McCabe, made our exit, and arrived on Honora's floor in such a way that it would not be suspected that we had been anywhere else in the building. As we met Mrs. Wilford, I cannot say that we were quite as welcome as on some previous encounters with her. It seemed that she was repressing her excitement not quite as easily as on previous occasions. Yet she seemed not to dare to refuse to see us. Perhaps, too, there was an element of curiosity to know whether anything had been discovered beyond what Doyle had already told her. If that were the case, she had not long to wait. Kennedy did not plan this time to keep her in suspense long. In fact, it seemed as if it were part of his plan to fire the information he wished to impart as a broadside and watch the effect, both immediate and ultimate. "I suppose you have read in the newspapers about the troubles of the Lathrops and what has happened?" he opened fire. "Nothing about that woman interests me," Honora returned, coldly. "That's not exactly what I came to tell you, though," remarked Kennedy, briskly. Honora was on the alert in an instant, although she tried to hide it. "I've discovered just what it was that caused the death of your husband," hastened Craig. I watched her closely. She was trying to show just enough and not too much interest. "Indeed?" she replied, veiling her eyes as a matter of self-defense. "Was it belladonna?" "No, it was not atropin," returned Craig, giving the drug its more scientific name. "It was physostigmine." I was watching her narrowly. Evidently she had been expecting some repetition of the psychological tests and Kennedy's more direct attack almost swept away a defense as she tried to adjust herself to the unexpected. Before she could recover from the shock that the bald statement seemed to give her, Craig shot out, "Has Doyle told you?" "Yes," she replied, endeavoring to remain calm and at the same time appear frank, "something about a bean which either you or Mr. Jameson discovered down in the office." "Then why did you mention belladonna?" asked Craig. She avoided his gaze as she answered, quickly, "Because it was the first thing that the police mentioned--the first thing that came into my head--like some of your psychological tests, I suppose." The last sentence was uttered with a sort of sarcastic defiance which I did not relish in Honora. "So," she continued in the same defiant tone, "it's another poison, this time--this physostigmine?" "Yes," reiterated Kennedy, quietly. "The Calabar bean. I suppose Doyle described it to you--its devilish uses in the Calabar--the way the natives use it in ordeals--and all that sort of thing?" "Yes--briefly," she replied, evidently steeling herself into a nonchalance she did not feel. "Of course, the drug has a certain medical importance, too," continued Craig, as though eager to hammer home the information about it which he wished to have stick in her mind. "It is physostigmine." Honora was evidently about to ask some question about the drug, perhaps such a question as would have portrayed ignorance, but Kennedy caught her eye and she closed her parted lips. There was no use camouflaging before this man. She knew it--knew the drug, I decided, and knew he knew she knew of it. "But it wasn't the drug, physostigmine, in this case," went on Kennedy. "It was the Calabar bean itself. I found traces of it in Mr. Wilford's stomach--starch grains from the beans themselves. You know you can recognize various starch grains under the microscope by their size, formation, and so forth. I've clearly demonstrated that." "You did? Why--I--I--er--thought that was Doctor Leslie's work." Evidently she did not realize that Kennedy was anything more than a dilettante scientist, dabbling with his psychological tests. Kennedy was now coming into the open more and more with her and she could not place him. On her part she saw that she must be more and more on guard, yet with fewer weapons on which to rely. "Oh no," returned Kennedy, easily. "I mix up in all sorts of queer investigations. Toxicology is a hobby with me. Doctor Leslie did indeed confirm my results, working independently." He paused to let her get the full significance. "But about these beans. They come from Africa, you know. Travelers, people who have hunted over Africa, often bring them back as curios." Honora shot a covert glance at Craig. Did she know that Shattuck had possessed some, after all? I saw at once the trend of Kennedy's remarks. There was quite enough in what he had said to arouse in her the fear that Shattuck was suspected by him. And, as I studied Honora even more closely, I could see now that she was making a great effort to conceal her anxiety. If the anxiety concerned solely herself, I could have understood it better, perhaps. But was it about herself? Would she have acted in just this manner if it had been that she believed Kennedy to be making a direct accusation against her? I could not decide. But, as I thought of it, I saw how cleverly Kennedy was leading his trumps. If she were consumed with anxiety for Shattuck, the traveler in Africa, she must be heroically suppressing her own real feelings toward him, as she had done for so long. I felt sure that the added pressure, day by day, was having its effect on her. "I suppose you know," pursued Kennedy, deliberately, without letting up on the pressure, "that traces of belladonna were found in one glass on Mr. Wilford's desk at the office and that an almost empty bottle of belladonna was found by the police here in your apartment?" "It was mine," she asserted, calmly, as though prepared. "It had been nearly used up. Celeste knows all about how I used it for my eyes. Many women do. She can tell you that." She said it boldly, and yet, since Kennedy had mentioned the Calabar bean, I had an indefinable feeling that Honora was concealing something--perhaps not only a fact--but also a great fear. No longer, now, did Kennedy seem to care whether he antagonized her or not. More and more, it seemed, it was his purpose to drop the mask with her, to fight her with other weapons than those psychological. "Both physostigmine and belladonna are used by oculists, you know," hinted Kennedy, broadly. The face of Honora was a study as she listened to this direct insinuation. She bit her lips at the thought that she had betrayed her knowledge of the use of belladonna. For an instant Honora gazed at Kennedy, startled at the penetrating power of his eyes, as she realized that the finding of the bean had, in his mind, perhaps, some connection with herself. What must have been the conflicting emotions in her mind as, now, for the first time, she realized that Kennedy had gone deeper into the case than Doyle or Leslie, that, while she might be a match for them, she could not possibly hope to be a match against the new weapons of science that Kennedy had brought to bear? Even though she might not fully appreciate them, Honora was too clever a woman not to know, merely by intuition, that she was faced with a battle in which the old weapons were unavailing. I know the thoughts that were surging, by Kennedy's suggestion, through her mind--the past of her life, her father, Honore Chappelle; the old love-affair with Shattuck; the attainment of social ambitions with Wilford--and back again to the life of her girlhood and the profession of her father. I thought for the moment that Craig had broken through her reserve. I knew that Kennedy was in reality fishing--at least I thought so. But it was evident by her actions that Honora did not know it. "Why do you make these--these accusations?" she demanded. "You knew that my father was an optician--one of the best known in the city," she cried, searching Craig's face. Kennedy nodded implacably. "I haven't made any accusations," he returned, then added, directly, "But I assumed that you knew something of his business while he was alive." "I do not know by what right you assume that I knew anything of the sort," she fenced. "Girls were not supposed to learn trades or professions in those days." Honora, in spite of her assumption of a quiet tone, was almost hysterical. The mounting flush on her face showed that she was keen with emotion, that it was only by an almost superhuman effort that she controlled the volcano of her feelings. Kennedy could see that it was only by such an effort that she managed to maintain her composure. He must have known that to press the case would have resulted in a situation such as might have advanced us fairly far toward the truth. Yet he did not follow farther any advantage he might have. Evidently, Kennedy was content to let the seed which he had planted during this visit germinate. Or was he reluctant to allow McCabe over the dictagraph hear more that might be reported to Doyle on which Doyle might continue to base wrong conclusions? Desperately I clung to this last explanation. As far as Honora was concerned, now, there was no use in our staying longer. Kennedy had deliberately thrown away a chance to drive her into further admissions. The interval had given her the time she needed. Now she was keenly on guard and mistress again of herself. Secretly I was rather glad. It was better to let the information and suspicion that had been aroused work of itself. "You are not yourself, Mrs. Wilford," suddenly apologized Kennedy. "It is not fair to you. Think over some of the things I have been forced to say to you. Perhaps you will see matters in another light. Good-by." I do not know whether his keen questioning or this sudden quiet change of tone and the idea of leaving her at such a time had a greater effect. She shot him one startled look, then bowed in silence as we, in turn, bowed ourselves out. She even denied herself the final glance of curiosity, lest she might betray sudden relief changed to deep-seated fear at the sudden departure of Kennedy, with his cool assumption of power. Outside, we encountered Celeste, who had been hovering in the hall, apparently listening. Quietly Kennedy beckoned her down the hall, away from the door we had just left, while he paused a moment to question her. "I wish you would refresh your memory, mademoiselle," he began, suddenly. "Are you sure--absolutely sure that on the night Mr. Wilford was murdered madame was here--that she was not out--at all?" His tone was such as to imply, not suspicion, but certainty that Celeste had been lying, that Mrs. Wilford had been out. "Oh, but yes, monsieur," Celeste replied, glibly. "I was with madame all the evening. No--no--she was not out. She was here--all the evening--waiting for him. I can swear it. How many times must I swear it--to you--to those--those beasts!" Celeste nodded outside. Kennedy smiled. "Who should know better than I what madame was doing?" continued Celeste, vehemently. Kennedy did not pursue the subject. "You love madame, don't you, Celeste?" he asked, simply. "Why--yes!" replied the girl, startled by the unexpectedness of the question. "Good day," nodded Kennedy, simply, as a lawyer might dismiss a witness. "Methinks she doth protest too much," I quoted, as I remembered the "Aussage test" again and its proof of the unreliability of Celeste. Kennedy did not attempt further to shake the girl's story, and I was forced to conclude that he had another purpose in view. Perhaps it was that he knew that she would report to Honora what he had asked. Kennedy turned to go out. But he did not close the door tightly as we went out. Sure enough, no sooner had he seemed to shut the door than he could see that she had darted into the room we had just left. Kennedy smiled and closed the door softly. XVIII THE CONFESSION Little happened during the rest of the day, which I spent in the laboratory, while Craig checked up the results of his previous observations on the case. Toward the end of the afternoon I strolled out, uncertain just what to do. On the street I saw a boy selling papers and I called to him. As my eye fell on a black head-line I fairly jumped with surprise. I read it again, hardly able to believe it. It was a startling bit of news that stared me in the face. Vina Lathrop had committed suicide at the Sainte-Germaine! Practically the whole story was told in the head-lines--that is, all except what little we knew. I turned the pages quickly. Belle Balcom had got in her brief interview with Vina, but it contained nothing new, either. As I hastened back to the laboratory there ran through my mind the swift succession of events of the morning--our learning of the separation, the visit to the hotel, the meeting, the coming of Belle Balcom, and finally the appearance of Doyle. Without a doubt it was this succession of events that had convinced Vina that there was no escape from the social disgrace that awaited her after the action of Doctor Lathrop. "What do you think?" I almost shouted, as I burst into the laboratory and threw the paper before Craig, who was still at work in his acid-stained smock. "And, do you know, often I had almost come to regard Vina as a possible suspect in the case, too! Could I have been right? Is it a confession?" Kennedy read the news item, then tore off his smock and reached for his hat and coat. "I'll admit that suicide might be taken as a confession, as a general rule," he exclaimed. "But it's not so in this case. Come--we must get over to the hotel. I doubt whether half the story can be known, even by this time. I wish I had been informed of this earlier. However, maybe it won't make any difference." It did not take us many minutes to get down to the fashionable hotel, nor long to get up to the room from which, in spite of the demands of the hotel people, the body had not been removed. Leslie, already notified in the course of the city routine, had arrived perhaps five minutes before us. "I was out on a case," he explained. "When I got back to the office I saw the police notification. But you had already left when I tried to call you up." I looked about. There was great excitement among the guests and employees on the floor on which Vina had taken her rather cheap and unpretentious room. But in all the group I could not see one familiar face, except that of Doyle, who had arrived just a few moments before Leslie. "Has Doctor Lathrop been told?" asked Kennedy. "Yes, but he didn't show any emotion. He has given orders that everything necessary must be done. But he absolutely refuses to allow the funeral to take place from his apartment. He insists that it must be from a private establishment. Even in death he will not forgive her. Said he would be over--but he hasn't come yet. I doubt whether he will. Her relatives live in the Middle West. He did give orders that they were to be notified." "What was the cause of death?" asked Craig. Leslie looked at him significantly. "I wanted your advice on that," he remarked. "Look." He had led Kennedy over to the white bed on which the body of Vina lay. "The eyes show the characteristic contraction of the pupils that I have come to recognize as from physostigmine. In fact, I don't think there can be much doubt about it in this case. What do you think?" Kennedy bent over and examined the body. "I quite agree with you," he added, as he rose. "It is a case of the same poisoning--only I think not by the bean this time, but by the pure drug." "Where do you suppose she got it?" asked Doyle. "I'll try to trace it in some of the drugstores to make sure." "Craig," I exclaimed, "do you recall that Doctor Lathrop said he had no use for the bean itself, but that naturally in his medicine-chest he had the drug? She heard us talking the thing over that time when we visited them. Without a doubt it was where she got it--that is," I corrected, "where she might have got it." Kennedy nodded. "No doubt you are right. It's a case of suicide by suggestion. She heard of the drug--and tried it. It's the way they all do. Suicide is a sort of insanity. If one person uses bichloride tablets, you find that a dozen, learning of it, do the same. It's a curious bit of psychology." "I agree with you," chimed in Leslie. "This was a case of the use of the pure alkaloid. Nothing else could have acted so swiftly--and everything indicates swift action. The chambermaid had been in the room only a few minutes before. Then when she knocked on the door again she got no answer. She thought there was something strange about it, for she was sure that Mrs. Lathrop had not gone out. So she tried the door. It was locked. But through the keyhole she could see that Vina had fallen across the foot of the bed. She screamed and then they got the pass key and opened the door." Kennedy had gone over to the window and was looking out. On a little roof below he pointed out something gleaming. Even from where we were we could see that it was a plain little vial. "More than likely she took some of the drug from her husband's office," he commented. "By every indication the act was premeditated--or at least she contemplated doing it." We glanced at each other, then at the former lovely form on the lonely bed, as the undertaker, sent by her husband, prepared to carry out the last offices, now that Doctor Leslie had given his permission. "What about this new development?" asked Leslie at length of Kennedy. "Does it affect your plans at all?" "Very much," asserted Kennedy, energetically. "It forces my hand. Now I must act immediately." For a moment he stood, planning hastily just what to do. "I'm going to try a little piece of psychology," he decided, finally, turning to us. "There are many things I need to know yet. For one thing, I'm not exactly sure just how much Mrs. Wilford actually knew about her husband and Vina Lathrop--not what she suspected or guessed. Oh, there are innumerable points that must be cleared up. I know no better or quicker way than to get them all together at once at my laboratory. Then I am sure that we can straighten this thing out quickly." He paused and looked about us. "Now," he added, assuming direction of affairs, with the tacit consent of both Doyle and Leslie, "I want each of you to help me. You, Walter, perhaps will be the best one to go after Mrs. Wilford. But don't, for Heaven's sake, tell her anything--except that it has been discovered that Vina Lathrop is a suicide. "Doyle, you have worked some parts of the case up to a final point--in your own mind. I delegate you to go after Mr. Shattuck and bring him to the laboratory." "Very well," agreed Doyle, with alacrity. "I don't mind that duty." He almost grinned. Nor did I imagine that he did. Shattuck had made himself particularly obnoxious to Doyle and I fancied that Doyle would take a particular pleasure in this errand, especially as it might lead to the humiliation, or worse, of Shattuck. "You, Leslie, as a doctor, I think would be the best to go after Doctor Lathrop," ordered Kennedy. "And all of you are to remember you are not to talk of the case, but merely to compel the attendance of the persons you are sent after. If they refuse or resist, you know where to get the authority to coerce them. But I don't think any of them will. It would look badly." As we parted, I jumped into a taxicab. I felt sure now that something must break. In spite of all the discouragements, I saw that Kennedy had been biding his time. He had seemed to be quite willing to wait, much more so than either Doyle or Leslie. I had realized some time before what his game was. Anything might have happened to unmask some one. The death of Vina was that thing. Now was the time to follow up his surprise attack. While we were gone, Craig hurried to the laboratory and there completed some simple preparations for our reception. From his cabinet he took and adjusted several little instruments, with an attachment that could be placed about the wrist, like a cuff or strap. These cuffs were hollow and from each ran a tube attached to an indicator. Both the hollow cuffs and the tubes were filled with a colored liquid which registered on a scale on the indicator part. But I anticipate my story. I found my end of the duty far from pleasant, although under other circumstances, suspicion or not of Honora, I should have enjoyed an opportunity to meet her. In spite of her feeling against Vina, the first news as I broke it to her came as a shock which she could not conceal. Yet, I felt, it would have taken more than even the practised eye of Kennedy to determine just what underlay her feelings in the matter. When, however, I informed her that my orders were to take her to the laboratory, she demurred vigorously. It was more by threat than anything else that I managed to get her to go. She finally assented, nervously. Her whole attitude was one of not knowing what to expect this time. In silence I escorted her in the taxicab to the laboratory, arriving there last of all, due to the cajolery I had been compelled to use to avoid forcing the issue. Leslie and Lathrop were waiting already. As we entered, Honora bowed to Doctor Lathrop, who returned the bow courteously. Clearly, I thought, this is merely the relation of physician and patient. Doyle had returned, but McCabe was not with him. Shattuck had almost fought against coming, but only a direct threat of arrest on the part of Doyle had succeeded with him. Doyle was correspondingly watchful of his prey. Shattuck bowed to Honora, and I saw that she returned the bow, a slight flush spread over her face. What was it--fear for him or of him? Perhaps Shattuck misinterpreted the action. At any rate, he seemed not content with a mere bow. He stepped forward. "I hope, Honora," he remarked, in a low voice, but not so low that I could not catch it, "that you will not think this unpleasantness is in any way due to anything I've done." For a moment Honora stared at Shattuck, then at Doyle, and finally at Kennedy. "Not at all," she murmured. "It seems that I no longer have anything whatever to say about my own actions." She said it with a sarcasm that was cutting, and at the same time with a keen observation of the rest of us. It was as though she were trying to read our minds. Kennedy, at least, gave her no chance. As she entered, he greeted her blandly, and one would never have known from the look on his face or from his manner that it was he who had ordered them all assembled in his laboratory. He was the coolest of us all. "I am going to try a little affair here that may or may not yield some results," he remarked, picking up one of the cuff attachments that lay before him on the table. "It is a simple enough thing. You merely slip this cuff over the wrist--so," he illustrated. He drew the thing off again and turned to me. "I'm going to put the first one on you, Walter," he remarked. "You will be my 'control' in the experiment, as we call it." Carefully he adjusted the thing on my wrist, and as he did so I realized that his purpose had been rather to get them familiar with what he was going to do than for any reason directed at me as a control. I watched the liquid in the indicator pulsing minutely as he finished. Next he had turned and adjusted one after another of the instruments on the others, first Honora, then Shattuck, and finally Lathrop. When he came to Leslie and Doyle he paused and finally decided that as a "control" I was sufficient. It was interesting to see how each of them took it. Honora accepted it with her previous passivity. Naturally Shattuck rebelled and it was only after a lengthy argument in which Doyle moved over ominously that he accepted. Lathrop viewed it, naturally, with the interest of a man of science. "Of course, as you all realize," remarked Craig, as he finished adjusting the instruments, whatever they were, "there have been many very strange ramifications to this case. It began in tragedy and it seems to continue in tragedy. Crime is like the train of powder. When the match is touched to it the fire runs along rapidly until it reaches the magazine--which it will explode unless the fire is stamped out at some point along the line." As he said it he glanced about at the faces before him, as though to see what each indicated. Even Doctor Lathrop, in spite of the suicide of his wife, showed no emotion. "There is no use for me to rehearse the strange circumstances that root back into the past," Craig continued. "They are well known in general to all of you--the society gossip, the scandals that have been repeated widely. Motives enough for everybody have appeared in this case as I have delved into it. What we want now is _facts_." He paused and leaned forward earnestly. "It has always been a theorem with me that one might reason out by all sorts of logical means that a certain person could not have done a certain act at a certain time and place. And yet, when it has been reasoned out perfectly to the satisfaction of the reasoner--you may find that the person actually did it. Therefore, I am a sort of modern Gradgrind. What I want is facts--facts--facts." As he finished he turned toward the table. Nor did he seem disposed to add anything immediately. Still, we could see what he was doing and such was the attention riveted on him that I am sure none of us missed a movement of his. Casually he reached into the pocket of his waistcoat and drew forth the peculiar bean which I had picked up on the floor of Wilford's office. He stood there for a moment, as though absent-mindedly toying with it, his back toward us. I glanced about. The action was not lost on any of them, but I watched the face of Honora more especially. She started forward, then caught herself. For the moment I thought she might have fainted. But she did not. "What's the idea, Kennedy?" burst out Shattuck, impatiently, observing. "Is it just some little theatricals--or is it a little Spanish Inquisition stuff?" "Just a moment, Shattuck," interrupted Doyle, who needed not very much provocation to boil over. "Mrs. Wilford," he shot out, suddenly, before she had recovered her composure, "you have not been frank, either with the police or with Mr. Kennedy. Some one besides you and your husband was in that office that night." "I--in the office?" she repeated, blankly. "Yes--in the office. We know there was a woman there." "I was not there," she asserted, positively. "Some one besides you and your husband--a man--was there," reiterated Doyle, ignoring her denial. Kennedy was still half turned away. Nor did he show any disposition to interrupt Doyle. I looked at Doyle, wondering why Kennedy did not interrupt the detective's third degree. Remorselessly Doyle pressed home his questioning. "We know much more than you think, Mrs. Wilford," exclaimed Doyle, menacingly. "We have not been idle. There are more sources of information open to the police than maids that earn their pay from their mistresses," he hinted, darkly. "Celeste told the truth," returned Honora, quietly. "Surely you have had chance enough to have found out about me from her, if there had been anything to find out." Doyle was not to be placated by a soft answer. "There were other people about that office that night," he added, confidently. "Mr. Wilford was not the only tenant in that building. Much can be overheard in the stillness after business hours. Don't forget that. Why did you tell him to give her up--that she never had loved him, did not, and never could love him?" Honora flushed slightly at the reference implied by Doyle to Vina. She seemed about to reply hotly, then checked herself. She looked about the room as though seeking help from some one, but not finding it. "If you were really there," interrupted Kennedy, quietly, for the first time, "tell." I saw Shattuck scowl blackly at Kennedy for lending the weight of his support even thus mildly to Doyle's bulldozing. Almost I hated Craig for doing it, myself. Honora's friendlessness appealed to me as it had often before. However, I reasoned, sentiment is a dangerous thing in a murder case. "It is your duty to tell," urged Kennedy. "It is ours to find out. As Doyle says, we have found out much. _Some one_--two people--were in that office, besides your husband!" There was silence. "A man was there--came later--at the time when the murder must have been committed!" An instant she faltered and gazed wildly from one to the other of us beside her. The strain was too great. It was as though something snapped under it. "No!" she cried, half sobbing, half defiant. "There was no one in that office! I--" It was too much for Shattuck. Out of the corner of my eye I had seen his glance riveted on Kennedy's hands as Craig twirled the Calabar bean nonchalantly. He turned suddenly and looked at Honora--then strode a step forward. "Professor Kennedy," he exclaimed, in a husky voice, "she was not there. It was I who was in the office. I will tell all!" XIX THE LIE-DETECTOR I do not know whether Kennedy was as startled as I at the unexpected confession of Shattuck. At any rate, his face did not betray it. It was Honora, however, whom I watched most closely. Her color came and went. One moment she seemed as pale as death; the next her face was flushed and burning. Yet she said nothing, though I knew she could have shrieked. What did it mean? Had she told the truth? Or had she confessed to something, in the hope of saving him? For the moment Shattuck was the calmest in the room, as generally happens in a crisis of this nature with the principal actor in the scene. "Let me tell you exactly what happened," he began, deliberately, avoiding as much as possible the mocking gaze of Doyle, who seemed delighted at the course of events. Shattuck paused and cleared his throat, as though to gain time to think out the correct order of events. "I came to the office," he continued, slowly. "It was quite late, but I found Vail Wilford there and alone," he emphasized the word. "As I entered, he was sitting at his desk. He turned and spoke to me. I don't recall just what it was that he said, but that doesn't make any difference now. "I had thought the whole thing out before. I knew perfectly what I was there for. The situation--the wide scandal between himself and Vina Lathrop--had become intolerable. As for me, I may as well confess that the growing unhappiness of Mrs. Wilford preyed on my mind--until I was almost mad." I heard Honora take a sharp breath, as though to control her feelings. She was leaning forward now, her cheeks burning, her eyes fixed on the face of the man who was speaking. With every word, I could see her emotions rising higher. Never had I dreamed that it was in this woman to show such depth of feeling. It was as though she were passing through some transformation which she herself did not understand, but which was changing her own soul and making a new creature of her. "I cannot recall just what passed between us," went on Shattuck, as though eager to hasten on and have it over with. "It was about his wife and what I thought his duties were. Every moment I could see that he was growing more and more angry--which was what I intended. Finally he rose, threatening. Wilford was a powerful man and no mean antagonist--but I had come prepared. I had my gun at his breast before he knew it. I forced him back into his chair. "'Honora is being driven mad by the way things are going,' I remember I shouted at him. 'One or the other of us must get out of her life.' "I could have shot him as he sat there, facing me before his desk--but I did not." Shattuck was talking calmly now, and earnestly, though underneath there was a depth of passion. "Then what?" demanded Doyle, as though fearful that something might even yet arise to stop the story. "I took one of those things, those beans that Kennedy has been talking about," he answered, pointing at the bean Kennedy was still holding in his hand. "Where did you get it?" "In Africa, of course," he hastened. "Where else?" "Have you any more?" demanded Doyle. "Yes--I think so," came back quickly. "I may have used the last one, though--or rather two, that is. You see, I must have dropped one and lost it. Then I must have forgotten about it in the excitement--that one Kennedy has." "I see," nodded Doyle. "Always there is some loophole you people leave open, some place where the cleverest of you fall down and get caught." Shattuck suppressed a quick retort that was on his lips. "As I faced him," he went on, "I told him that I would not kill him outright. I would give him an equal chance. I am a sportsman. I told him what the thing was, of the duels I had seen in Africa, of the chance that each took. At the very point of the gun I forced him to take the bean that was lying on the desk and cut it in half with my knife. Then I took back the knife and pointed to the two parts that lay on the desk before him. "'Choose!' I ordered." "But the glasses," interrupted Doyle, before he could check himself. "You forgot about the two glasses on the desk." "Oh yes--the glasses--on the desk. There were two glasses--I got two glasses. I filled them with water. I placed one before him, the other before myself. 'Choose!' I ordered him, pointing to the halves of the bean before him. "One thing I can say. Vail Wilford was not yellow. He saw that I had him--that there was no escape. He looked from the gun to me, then at the halves of the bean. Outside there was silence. No place, you know, is more deserted than down-town late at night after business hours. If he shouted, he knew that I would fire--also if he moved. I gave him sixty seconds to choose which half he would take. At the point of the gun he chose. "'Now,' I said to him, taking the remaining half myself, 'put it in your mouth, chew it, swallow it. If you spit out so much as a fragment I will fire instantly.' "And I give him credit. He was a sportsman and a gentleman through it all. I watched him chew it, and when he started I reached over and took my half. I began to chew that, myself. Then, together, we drank the water from the glasses, so that we would have to swallow the parts of the bean. Though I had him in my power, I did not take advantage of him." Honora gasped at the picture Shattuck was drawing. The recital was deeply affecting to her. I saw her leaning forward, and her rapidly rising and falling breast told the suppressed emotion under which she labored. "All right," hurried Doyle, to whom the dramatic quality of the tale had little appeal. "But what about the note? You forget to tell us about the suicide note." "Oh yes," exclaimed Shattuck, "so I did--about the note. I made him write it before we ate the bean--while I had him covered. I made him sit down at his own typewriter and I dictated it to him--one for myself, the other for him--to be used in case either survived." "You made him write one for you?" "Yes." "What did you do with it?" "I destroyed it afterward--of course." Doyle was forced to accept the answer. "And you were alone?" "Absolutely alone with him. Let me tell it--listen to me--will you? We ate the halves of the bean. I still kept the gun on him. I was taking no chances. The minutes passed as I stood over him--five--ten. "On which of us would the thing take effect first? It was a terrible wait. I will admit it. But it was the ordeal. We were just primitive men. Besides," he added, still keeping his glance from the face of Honora, who was leaning forward, her lustrous eyes trying to catch his, "I was playing for a big stake--it was death or what is really more than life to me." He paused just a fraction of a second, but only a fraction, as though he himself were afraid of an interruption. "At last I saw that his heart and lungs were beginning to be affected. His eyes were narrowed, the pupils to a pin-point--am I right about that, Professor? Never mind. In myself I waited for the same symptoms to appear. And I began to feel them, too. I was dizzy--with a burning thirst--but--alive! Still, I kept the gun leveled at him--the best I could, for my hand shook. "He did not know that, could not see it. Consciousness was fast going from him. But I was determined. I _would_ live. I saw that I might have the--the woman--I would give my life for. Perhaps it was will-power that saved me. But--they cannot say I did not give him a fair chance for the woman and the life that he did not deserve!" Breathlessly now we were all listening. Honora was trembling. Doctor Lathrop bent forward, nervously pulling his beard, his eyes riveted on the speaker. Only Doyle seemed to take the thing as a matter of course. "And Honora Wilford?" Doyle interjected. "What was she doing at--" "No--no--no, she was not there, I tell you. No one but Wilford and I was there!" Shattuck had burst forth with the first words in quick staccato, slowing up the assertion until at the end he was speaking slowly and warily. I had an impression that he was not so certain of himself that he could trust himself to get excited. Once I caught sight of Kennedy. He was saying nothing at all. But he was not idle. Taking advantage of the rapt attention of the little audience, he had stolen softly behind them. I saw him looking carefully at the various indicators of the arrangements on the wrists and noting them carefully. Was Shattuck telling the truth about what happened--or was he coloring it to save himself? "But about the atropin--in one glass and nothing in the other?" shot out Kennedy, suddenly. It was as though a bombshell had exploded. "Oh yes--yes," he faltered, "the atropin--of course, of course. In his glass, also, I--I--" Shattuck stopped. What was the matter? Did he realize that he was getting hopelessly tangled? "It is a pretty story, this, about your duel, as you call it," interrupted Doyle. "But it was not atropin that killed him. It was physostigmine. Atropin is the antidote. Didn't you know that, when you planned this ordeal you speak about? Besides, the traces of atropin were not in the glass that was found nearest the body. They were in the other." For a moment Shattuck stared helplessly. Was he, after all, just a murderer? Had he framed this duel by poison, preparing safety for himself, death for Wilford? "Come now, Shattuck," exclaimed Doyle, adopting that confidential manner that worked so well often with underworld characters, but seemed so out of place here, "did you--honestly--fight such a duel? Didn't you really force Mr. Wilford to eat that bean? And weren't you protecting yourself? Aren't there motives enough that we know for you to have wanted him out of the way?" Before Shattuck could reply, there was a sudden exclamation from some one beside me. A figure in a filmy dress darted between Doyle and Shattuck. "No--no--wait!" We were all on our feet in an instant at this sudden interruption at such a tense moment. It was Honora, no longer the stately creature of dignity we had seen, no longer the passive person submitting to the tests of Kennedy's psychology, suppressing the emotions that lay in her heart. Her whole being seemed to be transformed. It was as though a new spirit had been instilled suddenly into her. She faced us, and as I looked into her burning eyes I saw that what had been the mere statue of a woman, as we had first known her, had become a throbbing soul of life and passion. Shattuck saw the change. In spite of the terrible situation, his face kindled. It was worth it, if only for the brief moments, to feel that he had aroused in her that which he saw. "Wait," she repeated, "let me tell." Doyle was about to interrupt, but Kennedy, who had not for a moment, even at this crisis, forgotten to glance quickly at one of the instrument dials after another, pulled him back and silenced him without a spoken word. "You say there was a woman there?" she swept on, taking up the story, as though seizing it from Shattuck. "There _was_ a woman there. It was I. I was with him." The thing came as another thunderbolt, as it were, before the reverberation of the first had ceased echoing. Not one of us but realized what it meant. Honora had cast reputation, all, to the winds, to save him! She looked about at us, and never have I seen a woman more appealing, not even in any of the great moments of great cases in court which it has been my fortune to have witnessed and to have written. Cynic though I am, and knowing, as I thought at the moment, the purpose of it all, to save the man she loved, I could not resist the appeal. Nor was it directed at me. So marvelous was she that she took in the whole group, at once appealing to each, as if a sudden power had become hers. Quickly she poured forth her story, as though she, too, feared interruption. "It is all true--all that he has told," she cried. "I saw it all--heard it. But there is more--more that he will not tell. He has not told the whole story. Listen." It seemed as if she realized for the first time the power of an emotional woman. And her very instinct told her how to play upon us. "I knew the Calabar bean," she explained. "I need not tell Professor Kennedy that. Of course, as he knows, I had seen them in my father's laboratory, at his shop. And so, when I knew what it was that was taking place--what was I to do?" She paused, as though her intuition told her that the playing up of a dramatic moment would cover a multitude of questions that might otherwise come awkwardly flocking and demanding an answer as to much that she had not explained. "Should I scream out for help? He might have fired the gun. Besides--" She stopped again and dropped her gaze. "There was my reputation," she added. Doyle smiled cynically. She saw it. There was nothing, no slightest facial change that she missed. "What do I care--for anything--now?" she defied, directing the remark full at Doyle, who winced. Shattuck's face was a study as she poured forth her story. There was admiration in every line of it--and surprise. I was convinced that she had swept him off his feet as she had all of us. What did it mean? "What was I to do?" she repeated, gazing about wildly. "It came to me in a flash, an inspiration," she raced on, "the atropin--belladonna. I remembered it from the old days when I was little more than a school-girl, in the store." Involuntarily she reached for her chatelaine, but did not open it, as she illustrated. "I had my belladonna bottle with me." Rapt, now, we watched and listened. "There were only a few drops left in the bottle, I knew. I never carried much--nor used it often." She paused and clasped her hands as though in an agony of recollection. Was she telling the truth--or was she really a great actress who had just found herself? "I tried to run between them--I pleaded--my name--my honor--everything. They would not listen." She stopped just long enough to allow our own now supersensitive minds to reconstruct the scene already described by Shattuck between the two men. "But I managed to get between them and the glasses on the desk. I held the bottle, in one hand behind me--so." She acted it out, placing herself between us and a table, her face toward us, but her hand holding an imaginary bottle behind her. It was real to her, at least. "Which would I save?" She paused in desperation as she reconstructed the scene. Almost she had me convinced already, as she played out the part, under the stress of her feelings. "Which? My husband--or the other man whom I--I--" She let her voice die away over the implied word "loved" and there was another tense moment of silence. "There was not enough for both," she added, quickly; then, as though sweeping us on to the finale: "I poured the few drops of belladonna into the glass nearest me. Vance--Mr. Shattuck, drank it!" She swayed as the words were wrung from her very soul. Shattuck sprang to her and caught her. "You're wonderful," he whispered. "Honora--why--why have you said this?" For answer she merely allowed herself to rest more closely in his arms. Doyle moved forward with a triumphant smile. It made no difference to him. It was a confession, either way. And confessions meant convictions and success to him. What was human emotion, compared to a good record and report in the files at Headquarters? Honora looked from Doyle to Kennedy fearfully. She shrank farther into Shattuck's arms, nor did Shattuck relax his embrace. "It's true," she cried. "It's true. I tell you--it was a duel--just as he said--really--and I saved him!" Not one of us moved as we realized the situation. She would sacrifice her reputation, everything. But she would save her lover. "It was not murder--it--" Doyle raged, as he realized that, after all, a clever lawyer, with this woman as a witness, the heart-throbbing hypothetical question, and the impressionable jury might quickly overturn all that Doyle might swear to. "I beg your pardon," interrupted Kennedy, looking up from his rounds of examination of the dials. "You know this little thing--the blood-pressure measurer that is used by the doctors? Many insurance companies use similar things in investigating risks." At once Kennedy had wrested from Shattuck and Honora the center of the stage. Nor did he intend to relinquish it. "I beg your pardon," he repeated, "but my sphygmograph--this little instrument--my lie-detector, if you please--tells me you are both lying!" XX THE SOUL SCAR "Let me go back a bit," began Kennedy, as in perplexity we turned to him. "Let me repeat how I first entered this case. You will remember it was because of my interest in the dreams of Honora Wilford. I have studied them ever since. My first clue came from them. From them I have worked out my leads." At the mention of the dreams Honora had drawn away from Shattuck. She was gazing at Kennedy, wide-eyed. Shattuck, too, was following tensely. No less were Doyle and Leslie. Doctor Lathrop leaned forward, his brow wrinkled, as he tugged at his beard, impatiently listening. "Let us take those dreams, without wasting any more time," continued Kennedy. "I do not know how many of you are acquainted with the Freud theory. Mr. Jameson is, by this time. Also Mr. Shattuck. We've seen some of Freud's books in his library. Doctor Leslie knows it, I am sure, and Doctor Lathrop has told me he reacts against many of Freud's theories seriously. "I shall not attempt to explain the theory, but shall touch on certain phases of my psychanalysis," he remarked, addressing the remark apparently to Honora. "Recall that Freud tells us that all dreams are primarily about self in some way or interests close to self. Your first dream and each succeeding dream which I learned, Mrs. Wilford, were, I take it then, about your own relations with your husband." Honora looked startled, not only at having been singled out, but at the mention of the dreams and the vague thought of what might, after all, have been derived from them by this man whom she did not understand. "The dream of death, the struggle dream, the bull-and-serpent dream, the dream of fire and explosion, all pointed to one thing among others, but one thing that was paramount. Really you did not love your husband--with that deep, passionate love which every woman yearns to possess. It was not your fault. You were the creature of forces, of circumstances, of feelings which were out of your control. I could have told you more about yourself than you would have admitted--half an hour ago," he qualified. It was a delicate and intimate subject, yet Kennedy handled it without a touch of morbidness. "From the study of your dreams," he resumed, "as I have already hinted, many other things might have been discovered. One of the next importance to your unconscious feeling toward your husband was shown clearly. It was that you knew that another woman had entered his life." Kennedy glanced from her to Doctor Lathrop, and back to Honora. "Of course, you did not know the whole story--that that woman was merely using your husband as a means to an end. But it would have made no difference if you had. In that she was equally in your way, whether you would have admitted it or not. We can speak frankly on this subject now. Vina Lathrop's death has put a different aspect on that phase of the case." "Oh, I see," interrupted Shattuck, who had been following carefully up to this point, when it suddenly dawned on him that Kennedy's remarks were converging on himself and the gossip that had flown far and wide regarding Vina and himself. "I see. You have been reading the French detective tales--eh?--_Cherchez la femme_?" Kennedy ignored the interruption. He did not intend to let any such aside destroy the thread of either his thought or his argument. "Let me delve a little deeper in the analysis," he proceeded, calmly. "There was something back of that lack of love, something even deeper than the hurt given by the discovery of his relations with the other woman." If Shattuck had been minded to pursue the guerrilla conversation in the hope of harassing Kennedy, this remark was like an explosion of shrapnel. He sought cover. Kennedy was talking rapidly and earnestly now. "In short," he concluded, "there is something which we call a soul scar here--a psychic wound--a mental trauma. It bears the same relation to the soul that a wound does to the body. And, as in the case of some wounds, muscles and limbs do not function and must be re-educated, so in these mental and moral cases feelings and emotions must be made to function again, must be re-educated. I need not refer to what caused that wound. I think we understand the reaction that almost any girl would experience against one whom she loved but considered unworthy. I saw it the moment I began to analyze the dreams." In spite of its intimate nature, Kennedy kept his analysis on almost an impersonal level. It was as though he were telling us the results of his study of some new substance that had been submitted to him for his opinion. "Mrs. Wilford," he went on, speaking rather to us generally now than to her, "married not for love--whatever she may say or even think about it. Yet love--romantic love--was open to her, if she would only let herself go." I saw that as he proceeded, Shattuck had colored deeply. He knew the origin of this soul wound in her disapproval of the life he had led at the time. He shifted restlessly. "All my psychanalysis, by whatever means I went at it, whether merely by study of the dreams or by having them written out a second time in order to compare the omissions and hesitations, whether by the association test, the day-dreaming when relaxed, or the Jung association word test, all the psychological expedients I resorted to, now paying out, as it were, a piece of information, now withholding another, and always watching what effect it had upon the various parties to this case, all, I say, tended toward one end--the discovery of the truth that was hidden from us. "Finally," he exclaimed, "came the time when I allowed Doyle to place a dictagraph in the apartment, where we might overhear the interplay of the forces let loose by the information which I was allowing to leak out in one way or another." Involuntarily, Honora turned and caught the eye of Shattuck leveled at her. Each looked startled. What had Craig overheard through that dictagraph? The thought was quite evident in both minds. Honora gripped her chair. Shattuck turned and stared sullenly at the man before him. "To return to the dreams," resumed Kennedy, apparently not noticing this interchange of looks and byplay. "From the hesitations in telling and retelling the dreams, from the changes that were made, from a somewhat similar process in tracing out the more controlled thoughts of the waking state, I found that everything confirmed and amplified my original conclusion. True, I did not know all. I may not know _all_ yet. But each time I added to my knowledge until there were so many things that joined up and corroborated one another that there was no human possibility left that I was on the wrong track." One might have heard a pin drop in the laboratory as Craig held his auditors and carried them along, even after the intensity of feeling that we had witnessed scarcely a few minutes before. "I wish I had time to go into the many phases of the dream theories of the modern scientists," he hastened. "For hours, with Mr. Jameson, I have patiently tried to interpret and fit together the strange and fantastic conceptions of the mind when the censorship of consciousness is raised in sleep, veiling things which are as little thought of in your philosophies as you could well imagine. "For example, nothing in modern psychological science is more amazing, more likely to cause violent dissent, than the intimate connection that exists between the fundamental passions of love and hate. There is no need of the injunction to love our enemies--in this sense. Very often it happens that those we love may arouse the most intense hate, and that those we hate may exercise a fascination over us that we ourselves hasten to repress and refuse to admit. It is curious, but more and more it is coming to be recognized. "And before I go a step farther," he added, "let me forestall what is going to happen in this case as certainly as if I were adding chlorin to sodium and were going to derive salt. When I touch the deep, true 'complex,' as we psychanalysts call it, I shall expect the very idea to be rejected with scorn and indignation. Thereby will the very theory itself be proved. Shattuck, your old rule may work well with the case of a man. But the new rule, the complementary rule, for woman is _Cherchez l'homme_." It was not said to Shattuck, however. With clever psychology Kennedy aimed the remark full at Honora. She flushed and her eyes blazed defiance. Scornfully and angrily she cast a withering glance at Craig as she drew herself up with dignity. "Then--you think, your science teaches--that a woman must be a fool--that she does not know with whom she really is in love--that she can really be in love with one whom she--hates?" There was a flash of satisfaction in Craig's eyes. "Complex," I read it. As for Shattuck, where a moment ago he had scoffed, he remained to pray, or rather to smile faintly. "I did not say exactly that," returned Kennedy, "although it may seem that way, if you choose to interpret the intimate relationship of love and hate so. Follow me just a moment. Consciously, she may hate. Education, society, morality, religion--this thing we call civilization--may exert restraints. Unconsciously, though, she may love. The veneer of modern society is very thin. I think the experiences the world is going through to-day demonstrate that. Underneath there are the deep, basic passions of millions of years. They must be reckoned with. It is better to reckon with them than to be wrecked by them. The wonder is, not that they are so strong--but that the veneer covers them so well!" Powerfully though as Kennedy was making the presentation of the case, Honora tenaciously refused to admit it. Like her sex, when a general proposition was made she immediately made a personal application, found it distasteful, and rejected the proposition. Still, Kennedy was not dismayed. Nor did he admit defeat, or even checkmating. For several seconds he paused, then added in a low tone that was almost inaudible, yet in a way that did not call for an answer. "Could you--be honest, now, with yourself, for you need not say a word aloud--could you always be sure of yourself, after this, in the face of any situation?" She looked startled at his sudden shift of the argument to the personal ground. Her ordinarily composed face betrayed everything, though it was averted from the rest of us and could be seen only fully by Kennedy. In the welter of passion, as one fact after another had been torn forth during the moments since she had come to the laboratory, much had happened to Honora which never before had entered her well-ordered, conservative life. She knew the truth that she strove to repress. She _was_ afraid of herself. And she knew that he knew. The defiance in her eyes died slowly. "It is dangerous," she murmured, "to be with a person who pays attention to such little things. If every one were like you, I would no longer breathe a syllable of my dreams!" She was sobbing now. What was back of it all? I had heard of the so-called resolution dreams. I had heard of dreams that kill, of unconscious murder, of terrible acts of the somnambulist, of temporary insanity, of many deeds of which the doer had no recollection in the waking state, until put under hypnotism. Could it be such a thing which Kennedy was driving at disclosing? I cast a hasty glance about at our little audience. Doyle was hushed, now. This was far beyond him. Leslie was deeply interested. Doctor Lathrop had moved closer to Honora on the other side of Shattuck, as if to reassure her. Kennedy, too, was studying attentively the effect of his revelation both on Honora and the others. Honora, her shoulders bent with the outpouring of the long-suppressed emotion of the examination, called for sympathy. Shattuck saw it, saw the distress she so plainly showed. "Kennedy," he exclaimed, unable to restrain himself longer, pushing aside Doctor Lathrop, as he placed himself between her and the man whom he regarded now as her tormentor, "Kennedy--you are a faker--nothing but a damned dream doctor--in scientific disguise." "Perhaps," smiled Kennedy, unaffected by the threat. "But let me finish. Then you may think differently." He turned deliberately from Shattuck to the rest of us. "What happened at that office the fatal night was this," he shot out. "There was a woman there. But from what I deduce, it was not Honora Wilford. It must have been Vina Lathrop!" I felt a shock of surprise. Yet, after all, I had to admit that there was nothing improbable about it. "Later," he resumed, "someone else did enter that office. In all probability that person did hold up Vail Wilford, with a gun perhaps, just about as we have heard described. The Calabar bean was cut in half, undoubtedly. You will see from the facts in the case that it must have been so. Probably, too, each wrote a suicide note--on the typewriter--either to save the survivor, or at the dictation of the person who survived. Each must have eaten half of the bean. "But," added Kennedy, impressively, "it was no duel by poison--really. That other person knew the antidote--knew that the antidote was atropin--came prepared. That other person deliberately put atropin in his own glass of water, knowing that it was the antidote. No, it was no duel. It was murder--plain murder!" As he finished, Kennedy's voice rang out sharply and decisively in a direct accusation. "As for you, Doyle," he added, catching the eye of the detective, "you put your money on the wrong horse, as you would say. You thought that in my constant examination of Mrs. Wilford I coincided with your superficial observation. But I had another purpose, a very different purpose." Kennedy stopped a moment to turn from Doyle to the woman Doyle had persecuted. Honora and Shattuck were again close together, watching Kennedy intently, oblivious of all but themselves and him. It gave me a start to see them as they were now. Honora and the man she really loved were united at last. In his face I could see a far different kind of Shattuck, as though the fire of the ordeal had purified him. I caught a look of satisfaction that crossed Craig's face. He had succeeded. Back of all, I now saw that Kennedy had had all along a very human intention. Quickly I sought to explain what had already taken place only a few moments before. Had Shattuck lied to save her, when he saw that Doyle was framing a case against her? If that were so, then had she, with her quick wit, come to the rescue, with a marvelously constructed story that fitted perfectly with that which he had told and had broken down in telling? Had Shattuck and Honora, cornered, as they thought by Doyle, leaped at any suggestion? But the truth--what was it? Kennedy was speaking again, and now all hung on each word. "The stuff that dreams are made of is very real, after all," he remarked. "Just take this case itself. Suppose some one, who understood better than Honora Wilford, learned of her dreams--interpreted them--found out the truth about her relations with another--found out, as I have done, what she herself did not know--and then acted on the information. "Suppose that person knew of the soul scar, the old wound, knew from the dreams the conflict between the various persons--and encouraged the dream actors--in real life. Suppose, too, that that person, learning of what Vail Wilford was doing, had a personal grievance--a spite--a desire for bitter revenge." As Kennedy built up his hypothetical case I became more and more enthralled by it. It was more than hypothesis now. "The sphygmograph," he resumed, "has told me just what I still needed to know, even while you all have been here, perhaps forgetful of the little telltale that has been attached to your wrists. It is a faithful recorder of emotions, if you know how to study it. What is hidden from the eye the heart reveals. This heart machine will record it, betray the inmost secrets." Kennedy drew himself up slowly, as though to impress forcefully what he was about to add. "Psychanalysis," he exclaimed, "has led through Honora's soul scar to the discovery of the truth by the aid of this little lie-detector. It was your revenge on Vail Wilford--Lathrop!" Harshly Lathrop laughed, as though he had sensed the coming of the accusation all along. I took a step toward him, and as I did so something about his eyes almost halted me. The pupils were strangely contracted. I did not recall having noticed it before, certainly not when he came in. Again he laughed harshly. With a shaking hand he reached into his pocket and drew forth something. I saw instantly that it was a Calabar bean. He was about to place it in his mouth when Craig leaped and struck it from his hand. Honora screamed as Lathrop reeled back into his chair. Instantly Shattuck's arm stole about her solicitously as she shrank from the shaking figure in the chair near by. Her hand stole into his. "No cheating justice, Lathrop!" exclaimed Kennedy, seizing his wrist, which was already clammy. He smiled faintly, and his lips moved with an effort. "I did--what I did. It's too late for atropin now!" THE END BOOKS BY SIR GILBERT PARKER _THE WORLD FOR SALE_ _THE MONEY MASTER_ _THE JUDGMENT HOUSE_ _THE RIGHT OF WAY_ _THE LADDER OF SWORDS_ _THE WEAVERS_ _THE BATTLE OF THE STRONG_ _WHEN VALMOND CAME TO PONTIAC_ _THE LANE THAT HAD NO TURNING_ _NORTHERN LIGHTS_ _PIERRE AND HIS PEOPLE_ _AN ADVENTURER OF THE NORTH_ _A ROMANY OF THE SNOWS_ _CUMNER'S SON, AND OTHER SOUTH SEA FOLK_ HARPER & BROTHERS NEW YORK ESTABLISHED 1817 LONDON BOOKS BY REX BEACH _THE WINDS OF CHANCE_ _TOO FAT TO FIGHT_ _LAUGHING BILL HYDE_ _RAINBOW'S END_ _THE AUCTION BLOCK_ _THE CRIMSON GARDENIA_ _THE IRON TRAIL_ _THE SPOILERS_ _THE BARRIER_ _THE SILVER HORDE_ _THE NET_ _THE NE'ER-DO-WELL_ _HEART OF THE SUNSET_ _GOING SOME_ HARPER & BROTHERS NEW YORK [ESTABLISHED 1817] LONDON NOVELS OF THOMAS HARDY The New Thin-Paper Edition of the greatest living English novelist is issued in two bindings: Red Limp-Leather and Red Flexible Cloth, 12mo. Frontispiece in each volume. _DESPERATE REMEDIES_ _FAR FROM THE MADDING CROWD_ _A GROUP OF NOBLE DAMES_ _THE HAND OF ETHELBERTA_ _JUDE THE OBSCURE_ _A LAODICEAN_ _LIFE'S LITTLE IRONIES_ _THE MAYOR OF CASTERBRIDGE_ _A PAIR OF BLUE EYES_ _THE RETURN OF THE NATIVE_ _TESS OF THE D'URBERVILLES_ _THE TRUMPET MAJOR_ _TWO ON A TOWER_ _UNDER THE GREENWOOD TREE_ _THE WELL-BELOVED_ _WESSEX TALES_ _THE WOODLANDERS_ HARPER & BROTHERS NEW YORK ESTABLISHED 1817 LONDON NOVELS OF WILL N. HARBEN "His people talk as if they had not been in books before, and they talk all the more interestingly because they have for the most part not been in society, or ever will be. They express themselves in the neighborly parlance with a fury of fun, of pathos, and profanity which is native to their region. Of all our localists, as I may call the type of American writers whom I think the most national, no one has done things more expressive of the life he was born to than Mr. Harben." WILLIAM DEAN HOWELLS. _THE HILLS OF REFUGE_ _THE INNER LAW_ _ABNER DANIEL_ _ANN BOYD. Illustrated_ _DIXIE HART. Frontispiece_ _GILBERT NEAL. Frontispiece_ _MAM' LINDA_ _JANE DAWSON. Frontispiece_ _PAUL RUNDEL. Frontispiece_ _POLE BAKER_ _SECOND CHOICE. Frontispiece_ _THE DESIRED WOMAN. Frontispiece._ _THE GEORGIANS_ _THE NEW CLARION. Frontispiece_ _THE REDEMPTION OF KENNETH GALT. Frontispiece_ _THE SUBSTITUTE_ _WESTERFELT_ _Post 8vo, Cloth_ HARPER & BROTHERS NEW YORK ESTABLISHED 1817 LONDON TRANSCRIBER'S CORRECTIONS page original text correction 212 she hestitated a fraction she hesitated a fraction 270 "They are well know "They are well known 272 sources of informaation sources of information 
5149	----	THE GOLD OF THE GODS BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER CONTENTS I THE PERUVIAN DAGGER II THE SOLDIER OF FORTUNE III THE ARCHAEOLOGICAL DETECTIVE IV THE TREASURE HUNTERS V THE WALL STREET PROMOTER VI THE CURSE OF MANSICHE VII THE ARROW POISON VIII THE ANONYMOUS LETTER IX THE PAPER FIBRES X THE X-RAY READER XI THE SHOE-PRINTS XII THE EVIL EYE XIII THE POISONED CIGARETTE XIV THE INTERFEROMETER XV THE WEED OF MADNESS XVI THE EAR IN THE WALL XVII THE VOICE FROM THE AIR XVIII THE ANTIDOTE XIX THE BURGLAR POWDER XX THE PULMOTOR XXI THE TELESCRIBE XXII THE VANISHER XXIII THE ACETYLENE TORCH XXIV THE POLICE DOG XXV THE GOLD OF THE GODS I THE PERUVIAN DAGGER "There's something weird and mysterious about the robbery, Kennedy. They took the very thing I treasure most of all, an ancient Peruvian dagger." Professor Allan Norton was very much excited as he dropped into Craig's laboratory early that forenoon. Norton, I may say, was one of the younger members of the faculty, like Kennedy. Already, however, he had made for himself a place as one of the foremost of South American explorers and archaeologists. "How they got into the South American section of the Museum, though, I don't understand," he hurried on. "But, once in, that they should take the most valuable relic I brought back with me on this last expedition, I think certainly shows that it was a robbery with a deep-laid, premeditated purpose." "Nothing else is gone?" queried Kennedy. "Nothing," returned the professor. "That's the strangest part of it--to me. It was a peculiar dagger, too," he continued reminiscently. "I say that it was valuable, for on the blade were engraved some curious Inca characters. I wasn't able to take the time to decipher them, down there, for the age of the metal made them almost illegible. But now that I have all my stuff unpacked and arranged after my trip, I was just about to try--when along comes a thief and robs me. We can't have the University Museum broken into that way, you know, Kennedy." "I should say not," readily assented Craig. "I'd like to look the place over." "Just what I wanted," exclaimed Norton, heartily delighted, and leading the way. We walked across the campus with him to the Museum, still chatting. Norton was a tall, spare man, wiry, precisely the type one would pick to make an explorer in a tropical climate. His features were sharp, suggesting a clear and penetrating mind and a disposition to make the most of everything, no matter how slight. Indeed that had been his history, I knew. He had come to college a couple of years before Kennedy and myself, almost penniless, and had worked his way through by doing everything from waiting on table to tutoring. To-day he stood forth as a shining example of self-made intellectual man, as cultured as if he had sprung from a race of scholars, as practical as if he had taken to mills rather than museums. We entered a handsome white-marble building in the shape of a rectangle, facing the University Library, a building, by the way, which Norton had persuaded several wealthy trustees and other donors to erect. Kennedy at once began examining the section devoted to Latin America, going over everything very carefully. I looked about, too. There were treasures from Mexico and Peru, from every romantic bit of the wonderful countries south of us--blocks of porphyry with quaint grecques and hieroglyphic painting from Mitla, copper axes and pottery from Cuzco, sculptured stones and mosaics, jugs, cups, vases, little gods and great, sacrificial stones, a treasure house of Aztec and Inca lore--enough to keep one occupied for hours merely to look at. Yet, I reflected, following Norton, in all this mass of material, the thief seemed to have selected one, apparently insignificant, dagger, the thing which Norton prized because, somehow, it bore on its blade something which he had not, as yet, been able to fathom. Though Kennedy looked thoroughly and patiently, it seemed as though there was nothing there to tell any story of the robbery, and he turned his attention at last to other parts of the Museum. As he made his way about slowly, I noted that he was looking particularly into corners, behind cabinets, around angles. What he expected to find I could not even guess. Further along and on the same side of the building we came to the section devoted to Egyptology. Kennedy paused. Standing there, upright against the wall, was a mummy case. To me, even now, the thing had a creepy look. Craig pushed aside the stone lid irreverently and gazed keenly into the uncanny depths of the stone sarcophagus. An instant later he was down on his hands and knees, carefully examining the interior by means of a pocket lens. "I think I have made a start," he remarked, rising to his feet and facing us with an air of satisfaction. We said nothing, and he pointed to some almost undiscernible marks in a thin layer of dust that had collected in the sarcophagus. "If I'm not mistaken," he went on, "your thief got into the Museum during the daytime, and, when no one was looking, hid here. He must have stayed until the place was locked up at night. Then he could rob at his leisure, only taking care to confine his operations to the time between the rather infrequent rounds of the night watchman." Kennedy bent down again. "Look," he indicated. "There are the marks of shoes in the dust, shoes with nails in the heels, of course. I shall have to compare the marks that I have found here with those I have collected, following out the method of the immortal Bertillon. Every make of shoes has its own peculiarities, both in the number and the arrangement of the nails. Offhand, however, I should say that these shoes were American-made--though that, of course, does not necessarily mean that an American wore them. I may even be able to determine which of a number of individual pairs of shoes made the marks. I cannot tell that yet, until I study them. Walter, I wish you'd go over to my laboratory. In the second right-hand drawer of my desk you'll find a package of paper. I'd like to have it." "Don't you think you ought to preserve the marks?" I heard Norton hint, as I left. He had been watching Kennedy in open-eyed amazement and interest. "Exactly what I am sending Walter to do," he returned. "I have some specially prepared paper that will take those dust marks up and give me a perfect replica." I hurried back as fast as I could, and Kennedy bent to the task of preserving the marks. "Have you any idea who might have an object in stealing the dagger?" Kennedy asked, when he had finished. Norton shrugged his shoulders. "I believe some weird superstitions were connected with it," he replied. "It had a three-sided blade, and, as I told you, both the blade and the hilt were covered with peculiar markings." There seemed to be nothing more that could be discovered from a further examination of the Museum. It was plain enough that the thief must have let himself out of a side door which had a spring lock on it and closed itself. Not a mark or scratch was to be found on any of the window or door locks; nothing else seemed to have been disturbed. Evidently the thief had been after that one, to him priceless, object. Having got it, he was content to get away, leaving untouched the other treasures, some of which were even intrinsically valuable for the metal and precious stones in them. The whole affair seemed so strange to me, however, that, somehow, I could not help wondering whether Norton had told us the whole or only half the story as he knew it about the dagger and its history. Still talking with the archaeologist, Kennedy and I returned to his laboratory. We had scarcely reached the door when we heard the telephone ringing insistently. I answered, and it happened to be a call for me. It was the editor of the Star endeavouring to catch me, before I started downtown to the office, in order to give me an assignment. "That's strange," I exclaimed, hanging up the receiver and turning to Craig. "I've got to go out on a murder case--" "An interesting case?" asked Craig, interrupting his own train of investigation with a flash of professional interest. "Why, a man has been murdered in his apartment on Central Park, West, I believe. Luis de Mendoza is the name, and it seems--" "Don Luis de Mendoza?" repeated Norton, with a startled exclamation. "Why, he was an influential Peruvian, a man of affairs in his country, and an accomplished scholar. I--I--if you don't mind, I'd like to go over with you. I know the Mendozas." Kennedy was watching Norton's face keenly. "I think I'll go, too, Walter," he decided. "You won't lack assistants on this story, apparently." "Perhaps you can be of some assistance to them, also," put in Norton to Kennedy, as we left. It was only a short ride downtown, and our cab soon pulled up before a rather ornate entrance of a large apartment in one of the most exclusive sections of the city. We jumped out and entered, succeeding in making our way to the sixth floor, where Mendoza lived, without interference from the hallboy, who had been completely swamped by the rush that followed the excitement of finding one of the tenants murdered. There was no missing the place. The hall had been taken over by the reporters, who had established themselves there, terrible as an army with concealed pads and pencils. From one of the morning men already there I learned that our old friend Dr. Leslie, the coroner, was already in charge. Somehow, whether it was through Kennedy's acquaintance with Dr. Leslie or Norton's acquaintance with the Mendozas and the Spanish tongue, we found ourselves beyond the barrier of the door which shut out my rivals. As we stood for a moment in a handsome and tastefully furnished living room a young lady passed through hurriedly. She paused in the middle of the room as she saw us and eyed us tremulously, as though to ask us why we had intruded. It was a rather awkward situation. Quickly Norton came to the rescue. "I hope you will pardon me, Senorita," he bowed in perfect Spanish, "but--" "Oh, Professor Norton, it is you!" she cried in English, recognizing him. "I'm so nervous that I didn't see you at first." She glanced from him to us, inquiringly. I recollected that my editor had mentioned a daughter who might prove to be an interesting and important figure in the mystery. She spoke in an overwrought, agitated tone. I studied her furtively. Inez de Mendoza was unmistakably beautiful, of the dark Spanish type, with soft brown eyes that appealed to one when she talked, and a figure which at any less tragic moment one might have been pardoned for admiring. Her soft olive skin, masses of dark hair, and lustrous, almost voluptuous, eyes contrasted wonderfully with the finely chiselled lines of her nose, the firm chin, and graceful throat and neck. Here one recognized a girl of character and family in the depths of whose soul smouldered all the passion of a fiery race. "I hope you will pardon me for intruding," Norton repeated. "Believe me, it is not with mere idle curiosity. Let me introduce my friend, Professor Kennedy, the scientific detective, of whom you have heard, no doubt. This is his assistant, Mr. Jameson, of the Star. I thought perhaps they might stand between you and that crowd in the hall," he added, motioning toward the reporters on the other side of the door. "You can trust them absolutely. I'm sure that if there is anything any of us can do to aid you in--in your trouble, you may be sure that we are at your service." She looked about a moment in the presence of three strangers who had invaded the quietness of what had been, at least temporarily, home. She seemed to be seeking some one on whom to lean, as though some support had suddenly been knocked from under her, leaving her dazed at the change. "Oh, madre de Dios!" she cried. "What shall I do? Oh, my father--my poor father!" Inez Mendoza was really a pathetic and appealing figure as she stood there in the room, alone. Quickly she looked us over, as if, by some sort of occult intuition of woman, she were reading our souls. Then, instinctively almost, she turned to Kennedy. Kennedy seemed to recognize her need. Norton and I retired, somewhat more than figuratively. "You--you are a detective?" she queried. "You can read mystery--like a book?" Kennedy smiled encouragingly. "Hardly as my friend Walter here often paints me," he returned. "Still, now and then, we are able to use the vast knowledge of wise men the world over to help those in trouble. Tell me--everything," he soothed, as though knowing that to talk would prove a safety-valve for her pent-up emotions. "Perhaps I can help you." For a moment she did not know what to do. Then, almost before she knew it, apparently, she began to talk to him, forgetting that we were in the room. "Tell me how the thing happened, all that you know, how you found it out," prompted Craig. "Oh, it was midnight, last night; yes, late," she returned wildly. "I was sleeping when my maid, Juanita, wakened me and told me that Mr. Lockwood was in the living room and wanted to see me, must see me. I dressed hurriedly, for it came to me that something must be the matter. I think I must have come out sooner than they expected, for before they knew it I had run across the living room and looked through the door into the den, you call it, over there." She pointed at a heavy door, but did not, evidently could not, let her eyes rest on it. "There was my father, huddled in a chair, and blood had run out from an ugly wound in his side. I screamed and fell on my knees beside him. But," she shuddered, "it was too late. He was cold. He did not answer." Kennedy said nothing, but let her weep into her dainty lace handkerchief, though the impulse was strong to do anything to calm her grief. "Mr. Lockwood had come in to visit him on business, had found the door into the hall open, and entered. No one seemed to be about; but the lights were burning. He went on into the den. There was my father--" She stopped, and could not go on at all for several minutes. "And Mr. Lockwood, who is he?" asked Craig gently. "My father and I, we have been in this country only a short time," she replied, trying to speak in good English in spite of her emotion, "with his partner in a--a mining venture--Mr. Lockwood." She paused again and hesitated, as though in this strange land of the north she had no idea of which way to turn for help. But once started, now, she did not stop again. "Oh," she went on passionately, "I don't know what it was that came over my father. But lately he had been a changed man. Sometimes I thought he was--what you call--mad. I should have gone to see a doctor about him," she added wildly, her feelings getting the better of her. "But it is no longer a case for a doctor. It is a case for a detective--for some one who is more than a detective. You cannot bring him back, but--" She could not go on. Yet her broken sentence spoke volumes, in her pleading, soft, musical voice, which was far more pleasing to the ear than that of the usual Latin-American. I had heard that the women of Lima were famed for their beauty and melodious voices. Senorita Inez surely upheld their reputation. There was an appealing look now in her soft deep-brown eyes, and her thin, delicate lips trembled as she hurried on with her strange story. "I never saw my father in such a state before," she murmured. "For days all he had talked about was the 'big fish,' the peje grande, whatever that might mean--and the curse of Mansiche." The recollection of the past few days seemed to be too much for her. Almost before we knew it, before Norton, who had started to ask her a question, could speak, she excused herself and fled from the room, leaving only the indelible impression of loveliness and the appeal for help that was irresistible. Kennedy turned to Norton. But just then the door to the den opened and we saw our friend Dr. Leslie. He saw us, too, and took a few steps in our direction. "What--you here, Kennedy?" he greeted in surprise as Craig shook hands and introduced Norton. "And Jameson, too? Well, I think you've found a case at last that will baffle you." As we talked he led the way across the living room and into the den from which he had just come. "It is very strange," he said, telling at once all that he had been able to discover. "Senor Mendoza was discovered here about midnight last night by his partner, Mr. Lockwood. There seem to be no clues to how or by whom he was murdered. No locks had been broken. I have examined the hall-boy who was here last night. He seems to be off his post a good deal when it is late. He saw Mr. Lockwood come in, and took him in the elevator up to the sixth floor. After that we can find nothing but the open door into the apartment. It is not at all impossible that some one might have come in when the boy was off his post, have walked up, even have walked down, the stairs again. In fact, it must have been that way. No windows, not even on the fire-escape, have been tampered with. In fact, the murder must have been done by some one admitted to the apartment late by Mendoza himself." We walked over to the couch on which lay the body covered by a sheet. Dr. Leslie drew down the sheet. On the face was a most awful look, a terrible stare and contortion of the features, and a deep, almost purple, discoloration. The muscles were all tense and rigid. I shall never forget that face and its look, half of pain, half of fear, as if of something nameless. Mendoza had been a heavy-set man, whose piercing black eyes beetled forth, in life, from under bushy brows. Even in death, barring that horrible look, he was rather distinguished-looking, and his close-cropped hair and moustache set him off as a man of affairs and consequence in his own country. "Most peculiar, Kennedy," reiterated Dr. Leslie, pointing to the breast. "You see that wound? I can't quite determine whether that was the real cause of death or not. Of course, it's a bad wound, it's true. But there seems to be something else here, too. Look at the pupils of his eyes, how contracted they are. The lungs seem congested, too. He has all the marks of having been asphyxiated. Yet there are no indications on his throat of violence such as would be necessary if that were the case. There could have been no such thing as illuminating gas, nor have we found any trace of any receptacles which might have held poison. I can't seem to make it out." Kennedy bent over the body and looked at it attentively for several minutes, while we stood back of him, scarcely uttering a word in the presence of this terrible thing. Deftly Kennedy managed to extract a few drops of blood from about the wound and transfer them to a very small test-tube which he carried in a little emergency pocket-case in order to preserve material for future study. "You say the dagger was triangular, Norton?" he asked finally, without looking up from his minute examination. "Yes, with another blade that shot out automatically when you knew the secret of pressing the hilt in a certain way. The outside triangular blade separated into three to allow an inner blade to shoot out." Kennedy had risen and, as Norton described the Inca dagger, looked from one to the other of us keenly. "That blade was poisoned," he concluded quietly. "We have a clue to your missing dagger. Mendoza was murdered by it!" II THE SOLDIER OF FORTUNE "I should like to have another talk with Senorita Inez," remarked Kennedy, a few minutes later, as with Dr. Leslie and Professor Norton we turned into the living room and closed the door to the den. While Norton volunteered to send one of the servants in to see whether the young lady was able to stand the strain of another interview, Dr. Leslie received a hurry call to another case. "You'll let me know, Kennedy, if you discover anything?" he asked, shaking hands with us. "I shall keep you informed, also, from my end. That poison completely baffles me--so far. You know, we might as well work together." "Assuredly," agreed Craig, as the coroner left. "That," he added to me, as the door closed, "was one word for me and two for himself. I can do the work; he wants to save his official face. He never will know what that poison was--until I tell him." Inez had by this time so far recovered her composure that she was able to meet us again in the living room. "I'm very sorry to have to trouble you again," apologized Kennedy, "but if I am to get anywhere in this case I must have the facts." She looked at him, half-puzzled, and, I fancied, half-frightened, too. "Anything I can tell you--of course, ask me," she said. "Had your father any enemies who might desire his death?" shot out Kennedy, almost without warning. "No," she answered slowly, still watching him carefully, then adding hastily: "Of course, you know, no one who tries to do anything is absolutely without enemies, though." "I mean," repeated Craig, carefully noting a certain hesitation in her tone, "was there any one who, for reasons best known to himself, might have murdered him in a way peculiarly likely under the circumstances, say, with a dagger?" Inez flashed a quick glance at Kennedy, as if to inquire just how much or how little he really knew. I got the impression from it, at least, that she was holding back some suspicion for a reason that perhaps she would not even have admitted to herself. I saw that Norton was also following the line of Kennedy's questioning keenly, though he said nothing. Before Kennedy could take up the lead again, her maid, Juanita, a very pretty girl of Spanish and Indian descent, entered softly. "Mr. Lockwood," she whispered, but not so low that we could not hear. "Won't you ask him to come in, Nita?" she replied. A moment later a young man pushed open the door--a tall, clean-cut young fellow, whose face bore the tan of a sun much stronger than any about New York. As I took his appraisal, I found him unmistakably of the type of American soldier of fortune who has been carried by the wander-spirit down among the romantic republics to the south of our own. "Professor Kennedy," began Senorita Mendoza, presenting us all in turn, "let me introduce Mr. Lockwood, my father's partner in several ventures which brought us to New York." As we shook hands I could not help feeling that the young mining engineer, for such he proved to be by ostensible profession, was something more to her than a mere partner in her father's schemes. "I believe I've met Professor Norton," he remarked, as they shook hands. "Perhaps he remembers when we were in Lima." "Perfectly," replied Norton, returning the penetrating glance in kind. "Also in New York," he added. Lockwood turned abruptly. "Are you quite sure you are able to stand the strain of this interview?" he asked Inez in a low tone. Norton glanced at Kennedy and raised his eyebrows just the fraction of an inch, as if to call attention to the neat manner in which Lockwood had turned the subject. Inez smiled sadly. "I must," she said, in a forced tone. I fancied that Lockwood noted and did not relish an air of restraint in her words. "It was you, I believe, Mr. Lockwood, who found Senor Mendoza last night?" queried Kennedy, as if to read the answer into the record, although he already knew it. "Yes," replied Lockwood, without hesitation, though with a glance at the averted head of Inez, and choosing his words very carefully, as if trying hard not to say more than she could bear. "Yes. I came up here to report on some financial matters which interested both of us, very late, perhaps after midnight. I was about to press the buzzer on the door when I saw that the door was slightly ajar. I opened it and found lights still burning. The rest I think you must already know." Even that tactful reference to the tragedy was too much for Inez. She suppressed a little convulsive sob, but did not, this time, try to flee from the room. "You saw nothing about the den that aroused any suspicions?" pursued Kennedy. "No bottle, no glass? There wasn't the odour of any gas or drug?" Lockwood shook his head slowly, fixing his eyes on Kennedy's face, but not looking at him. "No," he answered; "I have told Dr. Leslie just what I found. If there had been anything else I'm sure I would have noticed it while I was waiting for Miss Inez to come in." His answers seemed perfectly frank and straight-forward. Yet somehow I could not get over the feeling that he, as well as Inez, was not telling quite all he knew--perhaps not about the murder, but about matters that might be related to it. Norton evidently felt the same way. "You saw no weapon--a dagger?" he interrupted suddenly. The young man faced Norton squarely. To me it seemed as if he had been expecting the question. "Not a thing," he said deliberately. "I looked about carefully, too. Whatever weapon was used must have been taken away by the murderer," he added. Juanita entered again, and Inez excused herself to answer the telephone, while we stood in the living room chatting for a few minutes. "What is this 'curse of Mansiche' which the Senorita has mentioned?" asked Kennedy, seeing a chance to open a new line of inquiry with Lockwood. "Oh, I don't know," he returned, impatiently flicking the ashes of a cigarette which he had lighted the moment Inez left the room, as though such stories had no interest for the practical mind of an engineer. "Some old superstition, I suppose." Lockwood seemed to regard Norton with a sort of aversion, if not hostility, and I fancied that Norton, on his part, neglected no opportunity to let the other know that he was watching him. "I don't know much about the story," resumed Lockwood a moment later as no one said anything. "But I do know that there is treasure in that great old Chimu mound near Truxillo. Don Luis has the government concession to bore into the mound, too, and we are raising the capital to carry the scheme through to success." He had come to the end of a sentence. Yet the inflection of his voice showed plainly that it was not the end of the idea that had been in his mind. "If you knew where to dig," suddenly supplied Norton, gazing keenly into the eyes of the soldier of fortune. Lockwood did not answer, though it was evident that that had been the thought unexpressed in his remarks. The return of the Senorita to the room seemed to break the tension. "It was the house telephone," she said, in a quiet voice. "The hall-boy didn't know whether to admit a visitor who comes with his sympathy." Then she turned from us to Lockwood. "You must know him," she said, somewhat embarrassed. "Senor Alfonso de Moche." Lockwood suppressed a frown, but said nothing, for, a moment later, a young man came in. Almost in silence he advanced to Inez and took her hand in a manner that plainly showed his sympathy in her bereavement. "I have just heard," he said simply, "and I hastened around to tell you how much I feel your loss. If there is anything I can do--" He stopped, and did not finish the sentence. It was unnecessary. His eyes finished it for him. Alfonso de Moche was, I thought, a very handsome fellow, though not of the Spanish type at all. His forehead was high, with a shock of straight black hair, his skin rather copper-coloured, nose slightly aquiline, chin and mouth firm; in fact, the whole face was refined and intellectual, though tinged with melancholy. "Thank you," she murmured, then turned to us. "I believe you are acquainted with Mr. de Moche, Professor Norton?" she asked. "You know he is taking post-graduate work at the University." "Slightly," returned Norton, gazing at the young man in a manner that plainly disconcerted him. "I believe I have met his mother in Peru." Senorita Mendoza seemed to colour at the mention of Senora de Moche. It flashed over me that, in his greeting Alfonso had said nothing of his mother. I wondered if there might be a reason for it. Could it be that Senorita Mendoza had some antipathy which did not include the son? Though we did not seem to be making much progress in this way in solving the mystery, still I felt that before we could go ahead we must know the little group about which it centred. There seemed to be currents and cross-currents here which we did not understand, but which must be charted if we were to steer a straight course. "And Professor Kennedy?" she added, turning to us. "I think I have seen Mr. de Moche about the campus," said Craig, as I, too, shook hands with him, "although you are not in any of my classes." "No, Professor," concurred the young man, who was, however, considerably older than the average student taking courses like his. I found it quite enough to watch the faces of those about me just then. Between Lockwood and de Moche it seemed that there existed a latent hostility. The two eyed each other with decided disfavour. As for Norton, he seemed to be alternately watching each of them. An awkward silence followed, and de Moche seemed to take the cue, for after a few more remarks to Inez he withdrew as gracefully as he could, with a parting interchange of frigid formalities with Lockwood. It did not take much of a detective to deduce that both of the young men might have agreed on one thing, though that caused the most serious of differences between them--their estimation of Inez de Mendoza. Inez, on her part, seemed also to be visibly relieved at his departure, though she had been cordial enough to him. I wondered what it all meant. Lockwood, too, seemed to be ill at ease still. But it was a different uneasiness, rather directed at Norton than at us. Once before I had thought he was on the point of excusing himself, but the entrance of de Moche seemed to have decided him to stay at least as long as his rival. "I beg your pardon, Senorita," he now apologized, "but I really must go. There are still some affairs which I must attend to in order to protect the interests we represent." He turned to us. "You will excuse me, I know," he added, "but I have a very important appointment. You know Don Luis and I were assisting in organizing the campaign of Stuart Whitney to interest American manufacturers, and particularly bankers, in the chances in South America which lie at hand, if we are only awake to take advantage of them. I shall be at your service, Senorita, as soon as the meeting is over. I presume I shall see you again?" he nodded to Kennedy. "Quite likely," returned Kennedy drily. "If there is any assistance I can render in clearing up this dreadful thing," went on Lockwood, in a lower tone to us, "you may count on me absolutely." "Thank you," returned Craig, with a significant glance. "I may have to take up that offer." "Do so, by all means," he reiterated, bowing to Norton and backing out of the door. Alone again with Inez Mendoza, Kennedy turned suddenly. "Who is this Senor de Moche?" he asked. "I gather that you must have known him in Peru." "Yes," she agreed. "I knew him in Lima"; then adding, as if by way of confession, "when he was a student at the University." There was something in both her tone and manner that would lead one to believe that she had only the kindliest feelings toward de Moche, whatever might be the case, as it seemed, with his mother. For a moment Kennedy now advanced and took Senorita Inez by the hand. "I must go now," he said simply. "If there is anything which you have not told me, I should like to know." "No--nothing," she answered. He did not take his eyes from hers. "If you should recall anything else," he persisted, "don't hesitate to tell me. I will come here, or you may come to the laboratory, whichever is more convenient." "I shall do so," she replied. "And thank you a thousand times for the trouble you are going to in my behalf. You may be sure that I appreciate it." Norton also bade her farewell, and she thanked him for having brought us over. I noticed also that Norton, though considerably older than any of us, had apparently succumbed to the spell of her wonderful eyes and face. "I also would be glad to help you," he promised. "You can usually find me at the Museum." "Thank you all," she murmured. "You are all so kind to me. An hour ago I felt that I had not a friend in all this big city--except Mr. Lockwood. Now I feel that I am not quite all alone." She said it to Norton, but it was really meant for Kennedy. I know Craig shared my own feelings. It was a rare pleasure to work for her. She seemed most appreciative of anything that was done for her in her defenceless position. As we passed out of the apartment house and sought our cab again, Kennedy was the first to speak, and to Norton. "Do you know anything more about these men, Lockwood and de Moche?" he queried, as we sped uptown. "I don't know a thing," he replied cautiously. "I--I'd much prefer not to talk of suspicions." "But the dagger," insisted Kennedy. "Have you no suspicions of what became of it and who took it?" "I'd prefer not to talk of mere suspicions," he repeated. Little was said as we turned in at the campus and at last drew up before Norton's wing of the Museum. "You will let me know of any development, no matter how trivial?" asked Kennedy, as we parted. "Your dagger seems to have stirred up more trouble than there was any reason to suppose when you came to me first." "I should say so," he agreed. "I don't know how to repay the interest you have shown in its recovery. If anything else materializes, I shall surely get word to you immediately." As we turned to leave, I could not help thinking of the manner of Lockwood and Norton toward each other. The name Stuart Whitney ran through my head. Stuart Whitney was a trustee of the University who had contributed heavily, among other things, to Norton's various expeditions to South America. Was it that Norton felt a peculiar loyalty to Whitney, or was he jealous that any one else should succeed in interesting his patron in things South American? The actions of the two young men, Lockwood and de Moche, recurred to me. "Well," I remarked, as we walked along, "what do you think it is--a romance or a simple crime-hunt?" "Both, I suspect," replied Craig abstractedly. "Only not simple." III THE ARCHAEOLOGICAL DETECTIVE "I think I'll go into the University Library," Craig remarked, as we left Norton before his building. "I want to refresh my mind on some of those old Peruvian antiquities and traditions. What the Senorita hinted at may prove to be very important. I suppose you will have to turn in a story to the Star soon?" "Yes," I agreed, "I'll have to turn in something, although I'd prefer to wait." "Try to get an assignment to follow the case to the end," suggested Craig. "I think you'll find it worth while. Anyhow, this will give you a chance for a breathing space, and, if I have this thing doped out right, you won't get another for some time. I'll meet you over in the laboratory in a couple of hours." Craig hurried up the long flight of white-marble steps to the library and disappeared, while I jumped on the subway and ran downtown to the office. It took me, as I knew it would, considerably over a couple of hours to clear things up at the Star, so that I could take advantage of a special arrangement which I had made, so that I could, when a case warranted it, co-operate with Kennedy. My story was necessarily brief, but that was what I wanted just now. I did not propose to have the whole field of special-feature writers camping on my preserve. Uptown I hurried again, afraid that Kennedy had finished and might have been called away. But when I reached the laboratory he was not there, and I found that he had not been. Up and down I paced restlessly. There was nothing else to do but wait. If he was unable to keep his appointment here with me, I knew that he would soon telephone. What was it, I wondered, that kept him delving into the archaeological lore of the library? I had about given him up, when he hurried into the laboratory in a high state of excitement. "What did you find?" I queried. "Has anything happened?" "Let me tell you first what I found in the library," he replied, tilting his hat back on his head and alternately thrusting and withdrawing his fingers in his waistcoat pockets, as if in some way that might help him to piece together some scattered fragments of a story which he had just picked up. "I've been looking up that hint that the Senorita dropped when she used those words peje grande, which mean, literally, 'big fish,'" he resumed. "Walter, it fires the imagination. You have read of the wealth that Pizarro found in Peru, of course." Visions of Prescott flashed through my mind as he spoke. "Well, where are the gold and silver of the conquistadores? Gone to the melting-pot, centuries ago. But is there none left? The Indians in Peru believe so, at any rate. And, Walter, there are persons who would stop at nothing to get at the secret. "It is a matter of history that soon after the conquest a vast fortune was unearthed of which the King of Spain's fifth amounted to five million dollars. That treasure was known as the peje chica--the little fish. One version of the story tells that an Inca ruler, the great Cacique Mansiche, had observed with particular attention the kindness of a young Spaniard toward the people of the conquered race. Also, he had observed that the man was comparatively poor. At any rate, he revealed the secret of the hiding-place of the peje chica, on condition that a part of the wealth should be used to advance the interests of the Indians. "The most valuable article discovered was in the form of a fish of solid gold and so large that the Spaniards considered it a rare prize. But the Cacique assured his young friend that it was only the little fish, that a much greater treasure existed, worth many times the value of this one. "The sequel of the story is that the Spaniard forgot his promise, went off to Spain, and spent all his gold. He was returning for the peje grande, of which he had made great boasts, but before he could get it he was killed. Prescott, I believe, gives another version, in which he says that the Spaniard devoted a large part of his wealth to the relief of the Indians and gave large sums to the Peruvian churches. Other stories deny that it was Mansiche who told the first secret, but that it was another Indian. One may, I suppose, pay his money and take his choice. But the point, as far as we are concerned in this case, is that there is still believed to be the great fish, which no one has found. Who knows? Perhaps, somehow, Mendoza had the secret of the peje grande?" Kennedy paused, and I could feel the tense interest with which his delving into the crumbling past had now endowed this already fascinating case. "And the curse?" I put in. "About that we do not know," he replied. "Except that we do know that Mansiche was the great Cacique or ruler of northern Peru. The natives are believed to have buried a far greater treasure than even that which the Spaniards carried off. Mansiche is said to have left a curse on any native who ever divulged the whereabouts of the treasure, and the curse was also to fall on any Spaniard who might discover it. That is all we know--yet. Gold was used lavishly in the temples. That great hoard is really the Gold of the Gods. Surely, as we have seen it so far in this case, it must be cursed." There was a knock on the laboratory door, and I sprang to open it, expecting to find that it was something for Kennedy. Instead there stood one of the office boys of the Star. "Why, hello, Tommy," I greeted him. "What seems to be the matter now?" "A letter for you, Mr. Jameson," he replied, handing over a plain envelope. "It came just after you left. The Boss thought it might be important--something about that story, I guess. Anyhow, he told me to take it up to you on my way home, sir." I looked at it again. It bore simply my name and the address of the Star, not written, but, strange to say, printed in ungainly, rough characters, as though some one were either not familiar with writing English or desired to conceal his handwriting. "Where did it come from--and how?" I asked, as I tore the envelope open. "I don't know where, sir," replied Tommy. "A boy brought it. Said a man uptown gave him a quarter to deliver it to you." I looked at the contents in blank amazement. There was nothing in the letter except a quarter sheet of ordinary size note paper such as that used in typewritten correspondence. Printed on it, in characters exactly like those on the outside of the envelope, were the startling words: "BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS." Underneath this inscription appeared the rude drawing of a dagger in which some effort had evidently been made to make it appear three-sided. "Well, of all things, what do you think of that?" I cried, tossing the thing over to Kennedy. He took it and read it; his face puckered deeply. "I'm not surprised," he said, a moment later, looking up. "Do you know, I was just about to tell you what happened at the library. I had a feeling all the time I was there of being watched. I don't know why or how, but, somehow, I felt that some one was interested in the books I was reading. It made me uncomfortable. I was late, anyhow, and I decided not to give them the satisfaction of seeing me any more--at least in the library. So I have had a number of the books on Peru which I wanted reserved, and they'll be sent over later, here. No, I'm not surprised that you received this. Would you remember the boy?" he asked of Tommy. "I think so," replied Tommy. "He didn't have on a uniform, though. It wasn't a messenger." There was no use to question him further. He had evidently told all that he knew, and finally we had to let him go, with a parting injunction to keep his eyes open and his mouth shut. Kennedy continued to study the note on the quarter sheet of paper long after the boy had gone. "You know," he remarked thoughtfully, after a while, "as nearly as I can make the thing out with the slender information that we have so far, the weirdest superstitions seem to cluster about that dagger which Norton lost. I wouldn't be surprised if it took us far back into the dim past of the barbaric splendour of the lost Inca civilization of Peru." He waved the sheet of paper for emphasis. "You see, some one has used it here as a sign of terror. Perhaps somehow it bore the secret of the big fish--who knows? None of the writers and explorers have ever found it. The most they can say is that it may be handed down from father to son through a long line. At any rate, the secret of the hiding-place seems to have been safely kept. No one has ever found the treasure. It would be strange, wouldn't it, if it remained for some twentieth-century civilized man to unearth the thing and start again the curse that historians say was uttered and seems always to have followed the thing?" "Kennedy, this affair is getting on my nerves already." While Craig was speaking the door of the laboratory had opened without our hearing it, and there stood Norton again. He had waited until Craig had finished before he had spoken. We looked at him, startled, ourselves. "I had some work to do after I left you," went on Norton, without stopping. "In my letter-box were several letters, but I forgot to look at them until just now, when I was leaving. Then I picked them up--and--look at this thing that was among them." Norton laid down on the laboratory table a plain envelope and a quarter sheet of paper on which were printed, except for his own name instead of mine, an almost exact replica of the note which I had received. "BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS." Kennedy and I looked at him. Already, evidently, he had seen that Kennedy held in his hand the note that had come to me. "I can't make anything out of it," went on Norton, evidently much worried. "First I lose the dagger. Next you say it was used to murder Mendoza. Then I get this. Now, if any one can get into the Museum to steal the dagger, they could get in to carry out any threat of revenge, real or fancied." Looked at in that respect, I felt that it was indeed a real cause of worry for Norton. But, then, it flashed over me, was not my own case worse? I was to be responsible for telling the story. Might not some unseen hand strike at me, perhaps sooner than at him? Kennedy had taken the two notes and was scanning them eagerly. Just then an automobile drew up outside, and a moment later we heard a tap at the door which Kennedy had closed after the entrance of Norton. I opened it. "Is Professor Kennedy here?" I heard a voice inquire. "I'm one of the orderlies at the City Hospital, next to the Morgue, where Dr. Leslie has his laboratory. I've a message for Professor Kennedy, if he's in." Kennedy took the envelope, which bore the stamp of Dr. Leslie's department, and tore it open. "My dear Kennedy," he read, in an undertone. "I've been engaged in investigating that poison which probably surrounds the wound in the Mendoza case, but as yet have nothing to report. It is certainly none of the things which we ordinarily run up against. Enclosed you will find a slip of paper and the envelope which it came in--something, I take it, that has been sent me by a crank. Would you treat it seriously or disregard it? Leslie." As Kennedy had unfolded Leslie's own letter a piece of paper had fluttered to the floor. I picked it up mechanically, and only now looked at it, as Craig finished reading. On it was another copy of the threat that had been sent to both Norton and myself! The hospital orderly had scarcely gone when another tap came at the door. "Your books from the library, Professor," announced a student who was employed in the library as part payment of his tuition. "I've signed the slip for them, sir." He deposited the books on a desk, a huge pile of them, which reached from his outstretched arms to his chin. As he did so the pressure of his arms released the pile of books and the column collapsed. From a book entitled "New and Old Peru," which fell with the pile, slipped a plain white envelope. Kennedy saw it before either of us, and seized it. "Here's one for me," he said, tearing it open. Sure enough, in the same rude printing on a quarter sheet were the words: "BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS." We could only stare at each other and at that tell-tale sign of the Inca dagger underneath. What did it mean? Who had sent the warnings? Kennedy alone seemed to regard the affair as if with purely scientific interest. He took the four pieces of paper and laid them down before him on the table. Then he looked up suddenly. "They match perfectly," he said quietly, gathering them up and placing them in a wallet which he carried. "All the indentures of the tearing correspond. Four warnings seem to have been sent to those who are likely to find out something of the secret." Norton seemed to have gained somewhat of his composure now that he had been able to talk to some one. "What are you going to do--give it up?" he asked tensely. "Nothing could have insured my sticking to it harder," answered Craig grimly. "Then we'll all have to stick together," said Norton slowly. "We all seem to be in the same boat." As he rose to go he extended a hand to each of us. "I'll stick," repeated Kennedy, with that peculiar bulldog look of intensity on his face which I had come to know so well. IV THE TREASURE HUNTERS Norton had scarcely gone, and Kennedy was still studying the four pieces of paper on which the warning had been given, when our laboratory door was softly pushed open again. It was Senorita Mendoza, looking more beautiful than ever in her plain black mourning dress, the unnatural pallor of her face heightening the wonderful lustrous eyes that looked about as though half frightened at what she was doing. "I hope nothing has happened," greeted Kennedy, placing an easy-chair for her. "But I'm glad to see that you have confidence enough to trust me." She looked about doubtfully at the vast amount of paraphernalia which Craig had collected in his scientific warfare on crime. Though she did not understand it, it seemed to impress her. "No," she murmured, "nothing new has happened. You told me to call on you if I should think of anything else." She said it with an air as if confessing something. It was apparent that, whatever it was, she had known it all the time and only after a struggle had brought herself to telling it. "Then you have thought of something?" prompted Craig. "Yes," she replied in a low tone. Then with an effort she went on: "I don't know whether you know it or not, but my family is an old one, one of the oldest in Peru." Kennedy nodded encouragingly. "Back in the old days, after Pizarro," she hurried on, no longer able to choose her words, but blurting the thing out directly, "an ancestor of mine was murdered by an Inca dagger." She stopped again and looked about, actually frightened at her own temerity, evidently. Kennedy and his twentieth-century surroundings seemed again to reassure her. "I can't tell you the story," she resumed. "I don't know it. My father knew it. But it was some kind of family secret, for he never told me. Once when I asked him he put me off; told me to wait until I was a little older." "And you think that may have something to do with the case?" asked Kennedy, trying to draw out anything more that she knew. "I don't know," she answered frankly. "But don't you think that it is strange--an ancestor of mine murdered and now, hundreds of years afterward, my father, the last of his line in direct descent, murdered in the same way, by an Inca dagger that has disappeared?" "Then you were listening while I was talking to Professor Norton?" shot out Kennedy, not unkindly, but rather as a surprise test to see what she would say. "You cannot blame me for that," she returned simply. "Hardly," smiled Kennedy. "And I appreciate your reticence--as well as your coming here finally to tell me. Indeed, it is strange. Surely you must have some other suspicions," he persisted, "something that you feel, even though you do not know?" Kennedy was leaning forward, looking deeply into her eyes, as if he would read what was passing in her mind. She met his gaze for a moment, then looked away. "You heard Mr. Lockwood say that he had become associated with a Mr. Whitney, Mr. Stuart Whitney, down in Wall Street?" she ventured. Kennedy did not take his eyes from her face as he sought to extract the reluctant words from her. "Mr. Whitney has been largely interested in Peru, in business and in mining," she went on slowly. "He has given large sums to scholars down there, to Professor Norton's expeditions from New York. I--I'm afraid of that Mr. Whitney!" Her quiet tone had risen to a pitch of tremulous excitement. Her face, which had been pale from the strain of the tragedy, was now full of colour, and her breast rose and fell with suppressed emotion. "Afraid of him--why?" asked Kennedy. There was no more reticence. Once having said so much, she seemed to feel that she must go on and tell her fears. "Because," she went on, "he--he knows a woman--whom my father knew." A sudden flash of fire seemed to light up her dark eyes. "A woman of Truxillo," she continued, "Senora de Moche." "De Moche," repeated Kennedy, recalling the name and a still unexplained incident of our first interview. "Who is this Senora de Moche?" he asked, studying her as if she had been under a lens. "A Peruvian of an old Indian family," she replied, in a low tone, as if the words were forced from her. "She has come to New York with her son, Alfonso. You remember--you met him. He is studying here at the University." Again I noted the different manner in which she spoke the two names of mother and son. Evidently there was some feud, some barrier between her and the elder woman, which did not extend to Alfonso. Kennedy reached for the University catalogue and found the name, "Alfonso de Moche." He was, as he had told us, a post-graduate student in the engineering school and, therefore, not in any of Kennedy's own classes. "You say your father knew the Senora?" asked Kennedy. "Yes," she replied, in a low voice, "he had had some dealings with her. I cannot say just what they were; I do not know. Socially, of course, it was different. They did not belong to the same circle as ours in Lima." From her tone I gathered that there existed a race prejudice between those of old Spanish descent and the descendants of the Indians. That, however, could not account for her attitude. At least with her the prejudice did not extend to Alfonso. "Senora de Moche is a friend of Mr. Whitney?" queried Kennedy. "Yes, I believe she has placed some of her affairs in his hands. The de Moches live at the Prince Edward Albert Hotel, and Mr. Whitney lives there, too. I suppose they see more or less of each other." "H-m," mused Kennedy. "You know Mr. Whitney, I suppose?" "Not very well," she answered. "Of course, I have met him. He has been to visit my father, and my father has been down at his office, with Mr. Lockwood. But I do not know much about him, except that he is what you Americans call a promoter." Apparently, Inez was endeavouring to be frank in telling her suspicions, much more so even than Norton had been. But I could not help feeling that she was trying to shield some one, though not to the extent of consciously putting us on a wrong scent. "I shall try to see Mr. Whitney as soon as possible," said Kennedy, as she rose to go. "And Senora de Moche, too." I fancied that Senorita Inez, although she had not told us much, felt relieved. Again she murmured her thanks as she left and again Kennedy repeated his injunction to tell everything that happened that could possibly have any bearing on the case. "That's a rather peculiar phase," he considered, when we were alone, "this de Moche affair." "Yes," I agreed. "Do you suppose that woman could be using Whitney for some purpose?" "Or Whitney using her," suggested Kennedy. "There's so much to be done at once that I hardly know where to begin. We must see both of them as soon as possible. Meanwhile, that message from Dr. Leslie about the poison interests me. I must at least start my tests of the blood samples that I extracted. Walter, may I ask you to leave me here in the laboratory undisturbed?" I had some writing on my news story to do, and went into the room next to the laboratory, where I was soon busily engaged tapping my typewriter. Suddenly I became conscious of that feeling, which Kennedy had hinted at, of being watched. Perhaps I had heard a footstep outside and was not consciously aware of it. But, at any rate, I had the feeling. I stopped tapping the keys and wheeled unexpectedly about in my chair. I am sure that I caught just a fleeting glimpse of a face dodging back from the window, which was on the first floor. Whose face it was I am not prepared to assert exactly. But there was a face, and the fleeting glimpse of the eyes and forehead was just enough to give me the impression that they were familiar, without enabling me to identify them. At any rate, the occurrence made me feel decidedly uncomfortable, especially after the warning letters that we had all received. I sprang to my feet and ran to the door. But it was too late. The intruder had disappeared. Still, the more I thought about it, the more determined I was to try to verify an indistinct suspicion, if possible. I put on my hat and walked hurriedly over to the office of the registrar. Sure enough, I found that Alfonso de Moche had been at the University that day, must have attended a lecture an hour or so before. Having nothing else to do, I hunted up some of his professors and tried to quiz them about him. As I had expected, they told me that he was an excellent student, though very quiet and reserved. His mind seemed to run along the line of engineering, and particularly mining. I could not help coming to the conclusion that undoubtedly he, too, was infected by the furore for treasure hunting, in spite of his Indian ancestry. Yet there seemed to be surprisingly little known about him outside of the lecture room and laboratory. The professors knew that he lived with his mother at a hotel downtown. He seemed to have little or nothing to do with the other students outside of class work. Altogether he was an enigma, as far as the social life of the University went. It looked very much as though he had come to New York quietly to prepare himself for the search for the buried treasure. Had the Gold of the Gods lured him into its net, too? Reflecting on the tangle of events, the strange actions of Lockwood and the ambitions of Whitney, I retraced my steps in the direction of the laboratory, convinced that de Moche had employed at least a part of his time lately in spying on us. Perhaps he had seen Inez going in and out. Suddenly it flashed over me that the interchange of glances between de Moche and Lockwood indicated that she was more to him than a mere acquaintance. Perhaps it had been jealousy as well as treasure hunting that had prompted his eavesdropping. Still reflecting, I decided to turn in at the Museum and have a chat with Norton. I found him nervously pacing up and down the little office that had been accorded him in his section of the building. "I can't rid my mind of that warning," he remarked anxiously, pausing in his measured tread. "It seems inconceivable to me that any one would take the trouble to send four such warnings unless he meant it." "Quite so," I agreed, relating to him what had just happened. "I thought of something like that," he acquiesced, "and I have already taken some precautions." Norton waved his hand at the windows, which I had not noticed before. Though they were some distance above the ground, I saw now that he had closed and barred them at the expense of ventilation. The warnings seemed to have made more of an impression on him than on any of the rest of us. "One never can tell where or when a blow will fall with these people," he explained. "You see, I've lived among them. They are a hot-blooded race. Besides, as you perhaps have read, they have some queer poisons down in South America. I mean to run no unnecessary chances." "I suppose you suspected all along that the dagger had something to do with the Gold of the Gods, did you not?" I hinted. Norton paused before answering, as though to weigh his words. "Suspected--yes," he replied. "But, as I told you, I have had no chance to read the inscription on it. I can't say that I took it very seriously--until now." "It's not possible that Stuart Whitney, who, I understand, is deeply interested in South America, may have had some inkling of the value of the dagger, is it?" I asked thoughtfully. For a full minute Norton gazed at me. "I hadn't thought of that," he admitted at length. "That's a new idea to me." Yet somehow I knew that Norton had thought of it, though he had not yet spoken about it. Was it through loyalty to the man who had contributed to financing his expeditions to South America? "Do you know Senora de Moche well?" I ventured, a moment later. "Fairly well," he replied. "Why?" "What do you think of her?" "Rather a clever woman," he replied noncommittally. "I suppose all the people in New York who were interested in Peru knew her," I pursued, adding, "Mr. Whitney, Mendoza, Lockwood." Norton hesitated, as though he was afraid of saying too much. While I could not help admiring his caution, I found that it was most exasperating. Still, I was determined to get at his point of view, if possible. "Alfonso seems to be a worthy son, then," I remarked. "I can't quite make out, though, why the Senorita should have such an obvious prejudice against her. It doesn't seem to extend to him." "I believe," replied Norton reluctantly, "that Mendoza had been on rather intimate terms with her. At least, I think you'll find the woman very ambitious for her son. I don't think she would have stopped at much to advance his interests. You must have noticed how much Alfonso thinks of the Senorita. But I don't think there was anything that could have overcome the old Castilian's prejudice. You know they pride themselves on never intermarrying. With Lockwood it would have been different." I thought I began to get some glimmering of how things were. "Whitney knows her pretty well now, doesn't he?" I shot out. Norton shrugged his shoulders. But he could not have acquiesced better than by his very manner. "Mr. Lockwood and Mr. Whitney know best what they are doing," he remarked, at length. "Why don't you and Kennedy try to see Senora de Moche? I'm a scientist, you know. I dislike talking about speculations. I'd prefer only to express opinions about things that are certainties." Perhaps Norton wished to convey the impression that the subjects I had broached were worth looking into. At least it was the impression I derived. "Still," he continued slowly, "I think I am justified in saying this much: I myself have been interested in watching both Alfonso de Moche and Lockwood when it comes to the case of the Senorita. All's fair, they say, in love and war. If I am any judge, there are both in this case, somewhere. I think you had better see the Senora and judge for yourself. She's a clever woman, I know. But I'm sure that Kennedy could make her out, even if the rest of us can't." I thanked Norton for the hint that he had given, and after chatting a few moments more left him alone in his office. In my room again, I went back to finish my writing. Nothing further occurred, however, to excite my suspicions, and at last I managed to finish it. I was correcting what I had written when the door opened from the laboratory and Craig entered. He had thrown off his old, acid-stained laboratory smock and was now dressed to venture forth. "Have you found out anything about the poison?" I asked. "Nothing definite yet," he replied. "That will take some time now. It's a strange poison--an alkaloid, I'm sure, but not one that one ordinarily encounters. Still, I've made a good beginning. It won't take long to determine it now." Craig listened with deep interest, though without comment, when I related what had happened, both Norton's conversation and about the strange visitor whom we had had peering into our windows. "Some one seems to be very much interested in what we are doing, Walter," he concluded simply. "I think we'd better do a little more outside work now, while we have a chance. If you are ready, so am I. I want to see what sort of treasure hunter this Stuart Whitney is. I'd like to know whether he is in on this secret of the Gold of the Gods, too." V THE WALL STREET PROMOTER Lockwood, as we now knew, had become allied in some way with a group of Wall Street capitalists, headed by Stuart Whitney. Already I had heard something of Whitney. In the Street he was well known as an intensely practical man, though far above the average exploiter both in cleverness and education. As a matter of fact, Whitney had been far-sighted enough to see that scholarship could be capitalized, not only as an advertisement, but in more direct manners. Just at present one of his pet schemes was promoting trade through the canal between the east coast of North America and the west coast of South America. He had spent a good deal of money promoting friendship between men of affairs and wealth in both New York and Lima. It was a good chance, he figured, for his investments down in Peru were large, and anything that popularized the country in New York could not but make them more valuable. "Norton seemed rather averse to talking about Whitney," I ventured to Craig, as we rode downtown. "That may be part of Whitney's cleverness," he returned thoughtfully. "As a patron of art and letters, you know, a man can carry through a good many things that otherwise would be more critically examined." Kennedy did not say it in a way that implied that he knew anything very bad about Whitney. Still, I reflected, it was astute in the man to insure the cooperation of such people as Norton. A few thousand dollars judiciously spent on archaeology might cover up a multitude of sins of high finance. Nothing more was said by either of us, and at last we reached the financial district. We entered a tall skyscraper on Wall Street just around the corner from Broadway and shot up in the elevator to the floor where Whitney and his associates had a really palatial suite of offices. As we opened the door we saw that Lockwood was still there. He greeted us with a rather stiff bow. "Professor Kennedy and Mr. Jameson," he said simply, introducing us to Whitney, "friends of Professor Norton, I believe. I met them to-day up at Mendoza's." "That is a most incomprehensible affair," returned Whitney, shaking hands with us. "What do you make out of it?" Kennedy shrugged his shoulders and turned the remark aside without committing himself. Stuart Whitney was a typical promoter, a large, full-blooded man, with a face red and inclined to be puffy from the congested veins. His voice alone commanded respect, whether he said anything worth while or not. In fact, he had but to say that it was a warm day and you felt that he had scored a telling point in the conversation. "Professor Norton has asked me to look into the loss of an old Peruvian dagger which he brought back from his last expedition," explained Kennedy, endeavouring to lead the conversation in channels which might arrive somewhere. "Yes, yes," remarked Whitney, with a nod of interest. "He has told me of it. Very strange, very strange. When he came back he told me that he had it, along with a lot of other important finds. But I had no idea he set such a value on it--or, rather, that any one else might do so. It would have been easy to have safeguarded it here, if we had known," he added, with a wave of his hand in the direction of a huge chrome steel safe of latest design in the outer office. Lockwood, I noted, was listening intently, quite in contrast with his former cavalier manner of dismissing all consideration of ancient Inca lore as academic or unpractical. Did he know something of the dagger? "I'm very much interested in old Peruvian antiquities myself," remarked Kennedy, a few minutes later, "though not, of course, a scholar like our friend Norton." "Indeed?" returned Whitney; and I noticed for the first time that his eyes seemed fairly to glitter with excitement. They were prominent eyes, a trifle staring, and I could not help studying them. "Then," he exclaimed, rising, "you must know of the ruins of Chan-Chan, of Chima--those wonderful places?" Kennedy nodded. "And of Truxillo and the legend of the great fish and the little fish," he put in. Whitney seemed extraordinarily pleased that any one should be willing to discuss his hobby with him. His eyes by this time were apparently starting from their sockets, and I noticed that the pupils were dilated almost to the size of the iris. "We must sit down and talk about Peru," he continued, reaching for a large box of cigarettes in the top drawer of his big desk. Lockwood seemed to sense a long discussion of archaeology. He rose and mumbled an excuse about having something to do in the outer office. "Oh, it is a wonderful country, Professor Kennedy," went on Whitney, throwing himself back in his chair. "I am deeply interested in it--its mines, its railroads, as well as its history. Let me show you a map of our interests down there." He rose and passed into the next room to get the map. The moment his back was turned, Kennedy reached over to a typewriter desk that stood in a corner of the office, left open by the stenographer, who had gone. He took two thin second sheets of paper and a new carbon sheet. A hasty dab or two of the library paste completed his work. Carefully Craig laid the prepared paper on the floor just a few inches from the door into the outer office and scattered a few other sheets about, as though the wind had blown them off the desk. As Whitney returned, a big map unrolled in his hands, I saw his foot fall on the double sheet that Craig had laid by the door. Kennedy bent down and began picking up the papers. "Oh, that's all right," remarked Whitney brusquely. "Never mind that. Here's where some of our interests lie, in the north." I don't think I paid much more attention to the map than did Kennedy as we three bent over it. His real attention was on the paper which he had placed on the floor, as though fixing in his mind the exact spot on which Whitney had stepped. As Whitney talked rapidly about the country, we lighted the cigarettes. They seemed to be of a special brand. I puffed mine for a moment. There was a peculiar taste about it, however, which I did not exactly like. In fact, I think that the Latin-American cigarettes do not seem to appeal to most Americans very much, anyhow. While we talked, I noticed that Kennedy evidently shared my own tastes, for he allowed his cigarette to go out, and, after a puff or two, I did the same. For the sake of my own comfort, I drew one of my own from my case as soon as I could do so politely, and laid the stub of the other in an ash-tray on Whitney's desk. "Mr. Lockwood and Senor Mendoza had some joint interests in the country, too, didn't they?" queried Kennedy, his eye still on the pieces of paper near the door. "Yes," returned Whitney. "Lockwood!" "What is it?" came Lockwood's voice from outside. "Show Professor Kennedy where you and Mendoza have those concessions." The young engineer strode into the room, and I saw a smile of gratification cross Kennedy's face as his foot, also, fell on the paper by the door. Unlike Whitney, however, Lockwood bent over to gather up the sheets. But before he could actually do so Kennedy reached down and swept them just out of his reach. "Quite breezy," Kennedy covered up his action, turning to restore the paper to the desk. Craig had his back to them, but not to me, and I saw him fumble for an instant with the papers. Quickly he pressed his thumb-nail on one side, as though making a rough "W," while on the other side he made what might be an "L." Then he shoved the two sheets and the carbon into his pocket. I glanced up hastily. Fortunately, neither Whitney nor Lockwood had noted his action. For the first time, now, I noticed as I watched him that Lockwood's eyes, too, were a trifle stary, though not so noticeable as Whitney's. "Let me see," continued Whitney, "your concessions are all about here, in the north, aren't they?" Lockwood drew a pencil from his pocket and made several cross-marks over the names of some towns on the large map. "Those are the points that we had proposed to work," he said simply, "before this terrible tragedy to Mendoza." "Mining, you understand," explained Whitney. Then, after a pause, he resumed quickly. "Of course, you know that much has been said about the chances for mining investments and about the opportunities for fortunes for persons in South America. Peru has been the Mecca for fortune hunters since the days of Pizarro. But where one person has been successful thousands have failed because they don't know the game. Why, I know of one investment of hundreds of thousands that hasn't yielded a cent of profit just because of that." Lockwood said nothing, evidently not caring to waste time or breath on any one who was not a possible investor. But Whitney had the true promoter's instinct of booming his scheme on the chance that the interest inspired might be carried to some third party. "American financiers, it is true," he went on excitedly, taking out a beautifully chased gold cigarette case, "have lost millions in mining in Peru. But that is not the scheme that our group, including Mr. Lockwood now, has. We are going to make more millions than they ever dreamed of--because we are simply going to mine for the products of centuries of labour already done--for the great treasure of Truxillo." One could not help becoming infected by Whitney's enthusiasm. Kennedy was following him closely, while a frown of disapproval spread over Lockwood's face. "Then you know the secret of the hiding-place of the treasure?" queried Kennedy abruptly. Whitney shook his head in the negative. "It is my idea that we don't have to know it," he answered. "With the hints that we have collected from the natives, I think we can locate it with the expenditure of comparatively little time and money. Senor Mendoza has obtained the concession from the government to hunt for it on a large scale in the big mounds about Truxillo. We know it is there. Is not that enough?" If it had been any one less than Whitney, we should probably have said it was not. But it took more than that to deny anything he asserted. Lockwood's face was a study. I cannot say that it betrayed anything except disapproval of the mere discussion of the subject. In fact, it left me in doubt as to whether Whitney himself might not have been bluffing, in the certainty of finding the treasure--perhaps had already the secret he denied having and was preparing to cover it up by stumbling on it, apparently, in some other way. I recognized in Stuart Whitney as smooth an individual as ever we had encountered. His was all the sincerity of a crook. Yet he contrived to leave the whole matter in doubt. Perhaps in this case he actually knew what he was talking about. The telephone rang and Lockwood answered it. Though he did not mention her name, I knew from his very tone and manner that it was Senorita de Mendoza who was calling up. Evidently his continued absence had worried her. "There's absolutely nothing to worry about," we heard him say. "Nothing has changed. I shall be up to see you as soon as I can get away from the office." There was an air of restraint about Lockwood's remarks, not as though he were keeping anything from the Senorita, but as though he were reluctant for us to overhear anything about his affairs. Lockwood had been smoking, too, and he added the stubs of his cigarettes to the pile in the ash-tray on Whitney's desk. Once I saw Craig cast a quick glance at the tray, and I understood that in some way he was anxious to have a chance to investigate those cigarettes. "You saw the dagger which Norton brought back, did you not?" asked Kennedy of Whitney. "Only as I saw the rest of the stuff after it was unpacked," he replied easily. "He brought back a great many interesting objects on this last trip." It was apparent that whether he actually knew anything about the secret of the Inca dagger or not, Whitney was not to be trapped into betraying it. I had an idea that Lockwood was interested in knowing that fact, too. At any rate, one could not be sure whether these two were perfectly frank with each other, or were playing a game for high stakes between themselves. Lockwood seemed eager to get away and, with a hasty glance at his watch, rose. "If you wish to find me, I shall be with Senorita de Mendoza," he said, taking his hat and stick, and bowing to us. Whitney rose and accompanied him to the door in the outer office, his arm on his shoulder, conversing in a low tone that was inaudible to us. No sooner, however, had the two passed through the door, with their backs toward us, than Kennedy reached over quickly and swept the contents of the ash-tray, cigarette stubs, ashes, and all, into an empty envelope which was lying with some papers. Then he sealed it and shoved it into his pocket, with a sidelong glance of satisfaction at me. "Evidently Mr. Lockwood and the Senorita are on intimate terms," hazarded Kennedy, as Whitney rejoined us. "Poor little girl," soliloquized the promoter. "Yes, indeed. And Lockwood is a lucky dog, too. Such eyes, such a figure--did you ever see a more beautiful woman?" One could not help recognizing that whatever else Whitney might have said that did not ring true his admiration for the unfortunate girl was genuine. That was not so remarkable, however. It could hardly have been otherwise. "You are acquainted, I suppose, with a Senora de Moche?" ventured Kennedy again, taking a chance shot. Whitney looked at him keenly. "Yes," he agreed, "I have had some dealings with her. She was an acquaintance of old Mendoza's--a woman of the world, clever, shrewd. I think she has but one ambition--her son. You have met her?" "Not the Senora," admitted Craig, "but her son is a student at the University." "Oh, yes, to be sure," said Whitney. "A fine fellow--but not of the type of Lockwood." Why he should have coupled the names was not clear for the moment. But he had risen, and was moving deliberately up and down the office, his thumbs in his waistcoat pockets, as though he were thinking of something very perplexing. "If I were younger," he remarked finally, of a sudden, "I would give both of them a race for that girl. She is the greatest treasure that has ever come out of the country. Ah, well--as it is, I would not place my money on young de Moche!" Kennedy had risen to go. "I trust you will be able to unearth some clue regarding that dagger," said Whitney, as we moved toward the door. "It seems to have worried Norton considerably, especially since you told him that Mendoza was undoubtedly murdered with it." Evidently Norton kept in close touch with his patron, but Kennedy did not appear to be surprised at it. "I am doing my best," he returned. "I suppose I may count on your help as the case develops?" "Absolutely," replied Whitney, accompanying us out into the hall to the elevator. "I shall back Norton in anything he wants to keep the Peruvian collection intact and protected." Our questions were as yet unanswered. Not only had we no inkling as to the whereabouts of the dagger, but the source of the four warnings that had been sent us was still as much shrouded in mystery. Kennedy beckoned to a passing taxicab. "The Prince Edward Albert," he directed briefly. VI THE CURSE OF MANSICHE We entered the Prince Edward Albert a few minutes later, one of the new and beautiful family hotels uptown. Before making any inquiries, Craig gave a hasty look about the lobby. Suddenly I felt him take my arm and draw me over to a little alcove on one side. I followed the direction of his eyes. There I could see young Alfonso de Moche talking to a woman much older than himself. "That must be his mother," whispered Craig. "You can see the resemblance. Let's sit here awhile behind these palms and watch." They seemed to be engaged in an earnest conversation about something. Even as they talked, though we could not guess what it was about, it was evident that Alfonso was dearer than life to the woman and that the young man was a model son. Though I felt that I must admire them each for it, still, I reflected, that was no reason why we should not suspect them--perhaps rather a reason for suspecting. Senora de Moche was a woman of well-preserved middle age, a large woman, with dark hair and contrasting full, red lips. Her face, in marked contradiction to her Parisian costume and refined manners, had a slight copper swarthiness about it which spoke eloquently of her ancestry. But it was her eyes that arrested and held one's attention most. Whether it was in the eyes themselves or in the way that she used them, there could be no mistake about the almost hypnotic power that their owner possessed. I could not help wondering whether she might not have exercised it on Don Luis, perhaps was using it in some way to influence Whitney. Was that the reason why the Senorita so evidently feared her? Fortunately, from our vantage point, we could see without being in any danger of being seen. "There's Whitney," I heard Craig mutter under his breath. I looked up and saw the promoter enter from his car. At almost the same instant the roving eyes of the Senora seemed to catch sight of him. He came over and spoke to the de Moches, standing with them several minutes. I fancied that not for an instant did she allow the gaze of any one else to distract her in the projection of whatever weird ocular power nature had endowed her with. If it were a battle of eyes, I recollected the strange look that I had noted about those of both Whitney and Lockwood. That, however, was different from the impression one got of the Senora's. I felt that she would have to be pretty clever to match the subtlety of Whitney. Whatever it was they were talking about, one could see that Whitney and Senora de Moche were on very familiar terms. At the same time, young de Moche appeared to be ill at ease. Perhaps he did not approve of the intimacy with Whitney. At any rate, he seemed visibly relieved when the promoter excused himself and walked over to the desk to get his mail and then out into the cafe. "I'd like to get a better view of her," remarked Kennedy, rising. "Let us take a turn or two along the corridor and pass them." We sauntered forth from our alcove and strolled down among the various knots of people chatting and laughing. As we passed the woman and her son, I was conscious again of that strange feeling, which psychologists tell us, however, has no real foundation, of being stared at from behind. At the lower end of the lobby Kennedy turned suddenly and we started to retrace our steps. Alfonso's back was toward us now. Again we passed them, just in time to catch the words, in a low tone, from the young man, "Yes, I have seen him at the University. Every one there knows that he is--" The rest of the sentence was lost. But it was not difficult to reconstruct. It referred undoubtedly to the activities of Kennedy in unravelling mysteries. "It's quite evident," I suggested, "that they know that we are interested in them now." "Yes," he agreed. "There wasn't any use of watching them further from under cover. I wanted them to see me, just to find out what they would do." Kennedy was right. Indeed, even before we turned again, we found that the Senora and Alfonso had risen and were making their way slowly to the elevators, still talking earnestly. The lifts were around an angle, and before we could place ourselves so that we could observe them again they were gone. "I wish there was some way of adding Alfonso's shoe-prints to my collection," observed Craig. "The marks that I found in the dust of the sarcophagus in the Museum were those of a man's shoes. However, I suppose I must wait to get them." He walked over to the desk and made inquiries about the de Moches and Whitney. Each had a suite on the eighth floor, though on opposite sides and at opposite ends of the hall. "There's no use wasting time trying to conceal our identity now," remarked Kennedy finally, drawing a card from his case. "Besides, we came here to see them, anyhow." He handed the card to the clerk. "Senora de Moche, please," he said. The clerk took the card and telephoned up to the de Moche suite. I must say that it was somewhat to my surprise that the Senora telephoned down to say that she would receive us in her own sitting room. "That's very kind," commented Craig, as I followed him into the elevator. "It saves planning some roundabout way of meeting her and comes directly to the point." The elevator whisked us up directly to the eighth floor and we stepped out into the heavily carpeted hallway, passing down to Room 810, which was the number of her suite. Further on, in 825, was Whitney's. Alfonso was not there. Evidently he had not ridden up with his mother, after all, but had gone out through another entrance on the ground floor. The Senora was alone. "I hope that you will pardon me for intruding," began Craig, with as plausible an explanation as he could muster, "but I have become interested in an opportunity to invest in a Peruvian venture, and I have heard that you are a Peruvian. Your son, Alfonso, I have already met, once. I thought that perhaps you might be able to give me some advice." She looked at us keenly, but said nothing. I fancied that she detected the subterfuge. Yet she had not tried, and did not try now to avoid us. Either she had no connection with the case we were investigating or she was an adept actress. On closer view, her eyes were really even more remarkable than I had imagined at a distance. They were those of a woman endowed with an abundance of health and energy, eyes that were full of what the old character readers used to call "amativeness," denoting a nature capable of intense passion, whether of love or hate. Yet I confess that I could not find anything especially abnormal about them, as I had about the eyes of Lockwood and Whitney. It was some time before she replied, and I gave a hasty glance about the apartment. Of course, it had been rented furnished, but she had rearranged it, adding some touches of her own which gave it quite a Peruvian appearance, due perhaps more to the pictures and the ornaments which she had introduced rather than anything else. "I suppose," she replied, at length, slowly, and looking at us as if she would bore right through into our minds, "I suppose you mean the schemes of Mr. Lockwood--and Mr. Whitney." Kennedy was not to be taken by surprise. "I have heard of their schemes, too," he replied noncommittally. "Peru seems to be a veritable storehouse of tales of buried treasure." "Let me tell you about it," she hastened, nodding at the very words "buried treasure." "I suppose you know that the old Chimu tribes in the north were the wealthiest at the time of the coming of the Spaniards?" Craig nodded, and a moment later she resumed, as if trying to marshal her thoughts in a logical order. "They had a custom then of burying with their dead all their movable property. Graves were not dug separately. Therefore, you see, sometimes a common grave, or huaca, as it is called, would be given to many. That huaca would become a cache of treasure in time. It was sacred to the dead, and hence it was wicked to touch it." The Senora's face betrayed the fact that, whatever modern civilization had done for her, it had not yet quite succeeded in eliminating the old ideas. "Back in the early part of the seventeenth century," she continued, leaning forward in her chair eagerly as she talked, "a Spaniard opened a Chimu huaca and found gold that is said to have been worth more than a million dollars. An Indian told him about it. Who the Indian was does not matter. But the Spaniard was an ancestor of Don Luis de Mendoza, who was found murdered to-day." She stopped short, seeming to enjoy the surprised look on our faces at finding that she was willing to discuss the matter so intimately. "After the Indian had shown the Spaniard the treasure in the mound," she pursued, "the Indian told the Spaniard that he had given him only the little fish, the peje chica, but that some day he would give him the big fish, the peje grande. I see that you already know at least a part of the story, anyhow." "Yes," admitted Kennedy, "I do know something of it. But I should rather get it more accurately from your lips than from the hearsay of any one else." She smiled quietly to herself. "I don't believe," she added, "that you know that the _peje grande_ was not ordinary treasure. It was the temple gold. Why, some of the temples were literally plated over heavily with pure gold. That gold, as well as what had been buried in the huacas, was sacred. Mansiche, the supreme ruler, laid a curse on it, on any Indian who would tell of it, on any Spaniard who might learn of it. A curse lies on the finding--yes, even on the searching for the sacred Gold of the Gods. It is one of the most awful curses that have ever been uttered, that curse of Mansiche." Even as she spoke of it she lowered her voice. I felt that no matter how much education she had, there lurked back in her brain some of the primitive impulses, as well as beliefs. Either the curse of Mansiche on the treasure was as real to her as if its mere touch were poisonous, or else she was going out of her way to create that impression with us. "Somehow," she continued, in a low tone, "that Spaniard, the ancestor of Don Luis Mendoza, obtained some idea of the secret. He died," she said solemnly, flashing a glance at Craig from her wonderful eyes to stamp the idea indelibly. "He was stabbed by one of the members of the tribe. On the dagger, so I have heard, was marked the secret of the treasure." I felt that in a bygone age she might have made a great priestess of the heathen gods. Now, was she more than a clever actress? She paused, then added, "That is my tribe--my family." Again she paused. "For centuries the big fish was a secret, is still a secret--or, at least, was until some one got it from my brother down in Peru. The tradition and the dagger had been intrusted to him. I don't know how it happened. Somehow he seemed to grow crazy--until he talked. The dagger was stolen from him. How it happened, how it came into Professor Norton's hands, I do not know. "But, at any rate," she continued, in the same solemn tone, "the curse has followed it. After my brother had told the secret of the dagger and lost it, his mind left him. He threw himself one day into Lake Titicaca." Her voice broke dramatically in her passionate outpouring of the tragedies that had followed the hidden treasure and the Inca dagger. "Now, here in New York, comes this awful death of Senor Mendoza," she cried. "I don't know, no one knows, whether he had obtained the secret of the gold or not. At any rate, he must have thought he had it. He has been killed suddenly, in his own home. That is my answer to your inquiry about the treasure-hunting company you mentioned, whatever it may be. I need say no more of the curse of Mansiche. Is the Gold of the Gods worth it?" There could be no denying that it was real to her, whatever we might think of the story. I recollected the roughly printed warnings that had been sent to Norton, Leslie, Kennedy, and myself. Had they, then, some significance? I had not been able to convince myself that they were the work of a crank, alone. There must be some one to whom the execution of vengeance of the gods was an imperative duty. Unsuperstitious as I was, I saw here a real danger. If some one, either to preserve the secret for himself or else called by divine mandate to revenge, should take a notion to carry out the threats in the four notes, what might not happen? "I cannot tell you much more of fact than you probably already know," she remarked, watching our faces intently and noting the effect of every word. "You know, I suppose, that the treasure has always been believed to be in a large mound, a tumulus I think you call it, visible from our town of Truxillo. Many people have tried to open it, but the mass of sand pours down on them and they have been discouraged." "No one has ever stumbled on the secret?" queried Kennedy. She shook her head. "There have been those who have sought, there are even those who are seeking, the point just where to bore into the mounds. If they could find it, they plan to construct a well-timbered tunnel to keep back the sand and to drive it at the right point to obtain this fabulous wealth." She vouchsafed the last information with a sort of quiet assurance that conveyed the idea, without her saying it directly, that any such venture was somehow doomed to failure, that desecrators were merely toying with fate. All through her story one could see that she felt deeply the downfall and betrayal of her brother, followed by the tragedy to him after the age-old secret had slipped from his grasp. Was there still to be vengeance for his downfall? Surely, I thought to myself, Don Luis de Mendoza could not have been in possession of the secret, unless he had arrived at it, with Lockwood, in some other way than by deciphering the almost illegible marks of the dagger. I thought of Whitney. Had he perhaps had something to do with the nasty business? I happened to glance at a huge pile of works on mining engineering on the table, the property of Alfonso. She saw me looking at them, and her eyes assumed a far-away, dreamy impression as she murmured something. "You must know that we real Peruvians have been so educated that we never explore ruins for hidden treasure, not even if we have the knowledge of engineering to do so. It is a sort of sacrilege to us to do that. The gold was not our gold, you see. Some of it belongs to the spirits of the departed. But the big treasure belonged to the gods themselves. It was the gold which lay in sheets over the temple walls, sacred. No, we would not touch it." I wondered cynically what would happen if some one at that moment had appeared with the authenticated secret. She continued to gaze at the books. "There are plenty of rare chances for a young mining engineer in Peru without that." Apparently she was thinking of her son and his studies at the University as they affected his future career. One could follow her thoughts, even, as they flitted from the treasure, to the books, to her son, and, finally, to the pretty girl for whom both he and Lockwood were struggling. "We are a peculiar race," she ruminated. "We seldom intermarry with other races. We are as proud as Senor Mendoza was of his Castilian descent, as proud of our unmixed lineage as any descendant of a 'belted earl.'" Senora de Moche made the remarks with a quiet dignity which left no doubt in my mind that the race feeling cut deeply. She had risen now, and in place of the awesome fear of the curse and tragedy of the treasure her face was burning and her eyes flashed. "Old Don Luis thought I was good enough to amuse his idle hours," she cried. "But when he saw that Alfonso was in love with his daughter, that she might return that love, then I found out bitterly that he placed us in another class, another caste." Kennedy had been following her closely, and I could see now that the cross-currents of superstition, avarice, and race hatred in the case presented a tangle that challenged him. There was nothing more that we could extract from her just then. She had remained standing, as a gentle reminder that the interview had already been long. Kennedy took the hint. "I wish to thank you for the trouble you have gone to," he bowed, after we, too, had risen. "You have told me quite enough to make me think seriously before I join in any such undertaking." She smiled enigmatically. Whether it was that she had enjoyed penetrating our rather clumsy excuse for seeing her, or that she felt that the horror of the curse had impressed us, she seemed well content. We bowed ourselves out, and, after waiting a few moments about the hotel without seeing Whitney anywhere, Craig called a car. "They were right," was his only comment. "A most baffling woman, indeed." VII THE ARROW POISON Back again in the laboratory, Kennedy threw off his coat and plunged again into his investigation of the blood sample he had taken from the wound in Mendoza's body. We had scarcely been back half an hour before the door opened and Dr. Leslie's perplexed face looked in on us. He was carrying a large jar, in which he had taken away the materials which he wished to examine. "Well," asked Kennedy, pausing with a test-tube poised over a Bunsen burner, "have you found anything yet? I haven't had time to get very far with my own tests yet." "Not a blessed thing," returned the coroner. "I'm desperate. One of the chemists suggested cyanide, another carbon monoxide. But there is no trace of either. Then he suggested nux vomica. It wasn't nux vomica; but my tests show that it must have been something very much like it. I've looked for all the ordinary known poisons and some of the little-known alkaloids, but, Kennedy, I always get back to the same point. There must have been a poison there. He did not die primarily of the wound. It was asphyxia due to a poison that really killed him, though the wound might have done so, but not quite so quickly." I could tell by the look that crossed Kennedy's face that at last a ray of light had pierced the darkness. He reached for a bottle on the shelf labelled spirits of turpentine. Then he poured a little of the blood sample from the jar which the coroner had brought into a clean tube and added a few drops of the spirits of turpentine. A cloudy, dark precipitate formed. He smiled quietly, and said, half to himself, "I thought so." "What is it?" asked the coroner eagerly, "nux vomica?" Craig shook his head as he stared at the black precipitate. "You were perfectly right about the asphyxiation, Doctor," he remarked slowly, "but wrong as to the cause. It was a poison--one you would never dream of." "What is it?" Leslie and I asked simultaneously. "Let me take all these samples and make some further tests," he said. "I am quite sure of it, but it is new to me. By the way, may I trouble you and Leslie to go over to the Museum of Natural History with a letter?" It was evident that he wanted to work uninterrupted, and we agreed readily, especially because by going we might also be of some use in solving the mystery of the poison. He sat down and wrote a hasty note to the director of the Museum, and a few moments later we were speeding over in Leslie's car. At the big building we had no trouble in finding the director and presenting the note. He was a close friend of Kennedy's and more than willing to aid him in any way. "You will excuse me a moment?" he apologized. "I will get from the South American exhibit just what he wants." We waited several minutes in the office until finally he returned carrying a gourd, incrusted on its hollow inside surface with a kind of blackish substance. "That is what he wants, I think," the director remarked, wrapping it up carefully in a box. "I don't need to ask you to tell Professor Kennedy to watch out how he handles the thing. He understands all about it." We thanked the director and hurried out into the car again, carrying the package, after his warning, as though it were so much dynamite. Altogether, I don't suppose that we could have been gone more than an hour. We burst into the laboratory, but, to my surprise, I did not see Kennedy at his table. I stopped short and looked around. There he was over in the corner, sprawled out in a chair, a tank of oxygen beside him, from which he was inhaling laboriously copious draughts. He rose as he saw us and walked unsteadily toward the table. "Why--what's the matter?" I cried, certain that m our absence an attempt had been made on his life, perhaps to carry out the threat of the curse. "N-nothing," he gasped, with an attempt at a smile. "Only I--think I was right--about the poison." I did not like the way he looked. His hand was unsteady and his eyes looked badly. But he seemed quite put out when I suggested that he was working too hard over the case and had better take a turn outdoors with us and have a bite to eat. "You--you got it?" he asked, seizing the package that contained the gourd and unwrapping it nervously. He laid the gourd on the table, on which were also several jars of various liquids and a number of other chemicals. At the end of the table was a large, square package, from which sounds issued, as if it contained something alive. "Tell me," I persisted, "what has happened. Has any one been here since we have been gone?" "Not a soul," he answered, working his arms and shoulders as if to get rid of some heavy weight that oppressed his chest. "Then what has happened that makes you use the oxygen?" I repeated, determined to get some kind of answer from him. He turned to Leslie. "It was no ordinary asphyxiation, Doctor," he said quickly. Leslie nodded. "I could see that," he admitted. "We have to deal in this case," continued Kennedy, his will-power overcoming his weakness, "with a poison which is apparently among the most subtle known. A particle of matter so minute as to be hardly distinguishable by the naked eye, on the point of a lancet or needle, a prick of the skin not anything like that wound of Mendoza's, were necessary. But, fortunately, more of the poison was used, making it just that much easier to trace, though for the time the wound, which might itself easily have been fatal, threw us off the scent. But given these things, not all the power in the world--unless one was fully prepared--could save the life of the person in whose flesh the wound was made." Craig paused a moment, and we listened breathlessly. "This poison, I find, acts on the so-called endplates of the muscles and nerves. It produces complete paralysis, but not loss of consciousness, sensation, circulation, or respiration until the end approaches. It seems to be one of the most powerful agents of which I have ever heard. When introduced in even a minute quantity it produces death finally by asphyxiation--by paralyzing the muscles of respiration. This asphyxia is what puzzled you, Leslie." He reached over and took a white mouse from the huge box on the corner of the table. "Let me show you what I have found," he said. "I am now going to inject a little of the blood serum of the murdered man into this white mouse." He took a needle and injected some of a liquid which he had isolated. The mouse did not even wince, so lightly did he touch it. But as we watched, its life seemed gently to ebb away, without pain, without struggle. Its breath simply seemed to stop. Next he took the gourd which we had brought and with a knife scraped off just the minutest particle of the black, licorice-like stuff that incrusted it. He dissolved the particle in some alcohol, and with a sterilized needle repeated his experiment on a second mouse. The effect was precisely similar to that produced by the blood on the first. I was intent on what Craig was doing when Dr. Leslie broke in with a question. "May I ask," he queried, "whether, admitting that the first mouse died at least apparently in the same manner as the second, you have proved that the poison is the same in both cases? And if it is the same, can you show that it affects human beings in the same way, that enough of it has been discovered in the blood of Mendoza to have caused his death? In other words, I want the last doubt set aside." If ever Craig startled me, it was by his quiet reply: "I've isolated it in his blood, extracted it, sterilized it, and I've tried it on myself." In breathless amazement, with eyes riveted on him, we listened. "Then that was what was the matter?" I blurted out. "You had been trying the poison on YOURSELF?" He nodded unconcernedly. "Altogether," he explained, as Leslie and I listened, speechless, "I was able to recover from both blood samples six centigrams of the poison. It is almost unknown. I could only be sure of what I discovered by testing the physiological effects. I was very careful. What else was there to do? I couldn't ask you fellows to try it, if I was afraid." "Good heavens!" gasped Leslie, "and alone, too." "You wouldn't have let me do it, if I hadn't got rid of you," he smiled quietly. Leslie shook his head. "Tried it on the dog and made himself the dog!" exclaimed Leslie. "I need the credit of a successful case--but I'll not take this one." Kennedy laughed. "Starting with two centigrams of the stuff as a moderate dose," he pursued, while I listened, stunned at his daring, "I injected it into my right arm subcutaneously. Then I slowly worked my way up to three and then four centigrams. You see what I had recovered was far from the real thing. They did not seem at first to produce any very appreciable results other than to cause some dizziness, slight vertigo, a considerable degree of lassitude, and an extremely painful headache of rather unusual duration." "Good night!" I exclaimed. "Didn't that satisfy you?" "Five centigrams considerably improved on it," he continued, paying no attention to me. "It caused a degree of lassitude and vertigo that was most distressing, and six centigrams, the whole amount which I had recovered from the samples of blood, gave me the fright of my life right here in this laboratory a few minutes before you came in." Leslie and I looked at each other and shook our heads. "Perhaps I was not wise in giving myself so large an injection on a day when I was overheated and below par otherwise, because of the strain I have been under in handling this case, as well as other work. However that may be, the added centigram produced so much more on top of the five centigrams I had previously taken that for a time I had reason to fear that that additional centigram was just the amount needed to bring my experiments to a permanent close. "Within three minutes of the time of injection the dizziness and vertigo had become so great as to make walking seem impossible. In another minute the lassitude rapidly crept over me, and the serious disturbance of my breathing made it apparent to me that walking, waving my arms, anything, was imperative. My lungs felt glued up, and the muscles of my chest refused to work. Everything swam before my eyes, and I was soon reduced to walking up and down the laboratory floor with halting steps, only preventing falling on the floor by holding fast to the edge of the table. "I thought of the tank of oxygen, and managed to crawl over and turn it on. I gulped at it. It seemed to me that I spent hours gasping for breath. It reminded me of what I once experienced in the Cave of the Winds of Niagara, where water is more abundant in the atmosphere than air. Yet my watch afterward indicated only about twenty minutes of extreme distress. But that twenty minutes is one period I shall never forget. I advise you, Leslie, if you are ever so foolish as to try the experiment, to remain below the five-centigram limit." "Believe me, I'd rather lose my job," returned Leslie. "How much of the stuff was administered to Mendoza," went on Kennedy, "I cannot say. But it must have been a good deal more than I took. Six centigrams which I recovered from these small samples are only nine-tenths of a grain. You see what effect that much had. I trust that answers your question?" Dr. Leslie was too overwhelmed to reply. "What is this deadly poison that was used on Mendoza?" I managed to ask. "You have been fortunate enough to obtain a sample of it from the Museum of Natural History," returned Craig. "It comes in a little gourd, or often a calabash. This is in a gourd. It is a blackish, brittle stuff, incrusting the sides of the gourd just as if it was poured in in the liquid state and left to dry. Indeed, that is just what has been done by those who manufacture it after a lengthy and somewhat secret process." He placed the gourd on the edge of the table, where we could see it closely. I was almost afraid even to look at it. "The famous traveller, Sir Robert Schomburgk, first brought it into Europe, and Darwin has described it. It is now an article of commerce, and is to be found in the United States Pharmacoepia as a medicine, though, of course, it is used in only very minute quantities, as a heart stimulant." Craig opened a book to a place he had marked. "Here's an account of it," he said. "Two natives were one day hunting. They were armed with blow-pipes and quivers full of poisoned darts made of thin, charred pieces of bamboo, tipped with this stuff. One of them aimed a dart. It missed the object overhead, glanced off the tree, and fell down on the hunter himself. This is how the other native reported the result: "'Quacca takes the dart out of his shoulder. Never a word. Puts it in his quiver and throws it in the stream. Gives me his blow-pipe for his little son. Says to me good-bye for his wife and the village. Then he lies down. His tongue talks no longer. No sight in his eyes. He folds his arms. He rolls over slowly. His mouth moves without sound. I feel his heart. It goes fast and then slow. It stops. Quacca has shot his last woorali dart.'" Leslie and I looked at Kennedy, and the horror of the thing sank deep into our minds. Woorali. What was it? "Woorali, or curare," explained Craig slowly, "is the well-known poison with which the South American Indians of the upper Orinoco tip their arrows. Its principal ingredient is derived from the Strychnos toxifera tree, which yields also the drug nux vomica, which you, Dr. Leslie, have mentioned. On the tip of that Inca dagger must have been a large dose of the dread curare, this fatal South American Indian arrow poison." "Say," ejaculated Leslie, "this thing begins to look eerie to me. How about that piece of paper that I sent to you with the warning about the curse of Mansiche and the Gold of the Gods. What if there should be something in it? I'd rather not be a victim of this curare, if it's all the same to you, Kennedy." Kennedy was thinking deeply. Who could have sent the messages to us all? Who was likely to have known of curare? I confess that I had not even an idea. All of them, any of them, might have known. The deeper we got into it, the more dastardly the crime against Mendoza seemed. Involuntarily, I thought of the beautiful little Senorita, about whom these terrible events centred. Though I had no reason for it, I could not forget the fear that she had for Senora de Moche, and the woman as she had been revealed to us in our late interview. "I suppose a Peruvian of average intelligence might know of the arrow poison of Indians of another country," I ventured to Craig. "Quite possible," he returned, catching immediately the drift of my thoughts. "But the shoe-prints indicated that it was a man who stole the dagger from the Museum. It may be that it was already poisoned, too. In that case the thief would not have had to know anything of curare, would not have needed to stab so deeply if he had known." I must confess that I was little further along in the solution of the mystery than I had been when I first saw Mendoza's body. Kennedy, however, did not seem to be worried. Leslie had long since given up trying to form an opinion and, now that the nature of the poison was finally established, was glad to leave the case in our hands. As for me, I was inclined to agree with Dr. Leslie, and, long after he had left, there kept recurring to my mind those words: BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS. VIII THE ANONYMOUS LETTER "I think I will drop in to see Senorita Mendoza," considered Kennedy, as he cleared up the materials which he had been using in his investigation of the arrow poison. "She is a study to me--in fact, the reticence of all these people is hard to combat." As we entered the apartment where the Mendozas lived, it was difficult to realize that only a few hours had elapsed since we had first been introduced to this strange affair. In the hall, however, were still some reporters waiting in the vain hope that some fragment of a story might turn up. "Let's have a talk with the boys," suggested Craig, before we entered the Mendoza suite. "After all, the newspaper men are the best detectives I know. If it wasn't for them, half our murder cases wouldn't ever be solved. As a matter of fact, 'yellow journals' are more useful to a city than half the detective force." Most of the newspaper men knew Craig intimately, and liked him, possibly because he was one of the few people to-day who realized the very important part these young men played in modern life. They crowded about, eager to interview him. But Craig was clever. In the rapid fire of conversation it was really he who interviewed them. "Lockwood has been here a long time," volunteered one of the men. "He seems to have constituted himself the guardian of Inez. No one gets a look at her while he's around." "Well, you can hardly blame him for that," smiled Craig. "Jealousy isn't a crime in that case." "Say," put in another, "there'd be an interesting quarter of an hour if he were here now. That other fellow--de Mooch--whatever his name is, is here." "De Moche--with her, now?" queried Kennedy, wheeling suddenly. The reporter smiled. "He's a queer duck. I was coming up to relieve our other man, when I saw him down on the street, hanging about the corner, his eyes riveted on the entrance to the apartment. I suppose that was his way of making love. He's daffy over her, all right. I stopped to watch him. Of course, he didn't know me. Just then Lockwood left. The Spaniard dived into the drug store on the corner as though the devil was after him. You should have seen his eyes. If looks were bullets, I wouldn't give much for Lockwood's life. With two such fellows about, you wouldn't catch me making goo-goo eyes at that chicken--not on your life." Kennedy passed over the flippant manner in view of the importance of the observation. "What do you think of Lockwood?" he asked. "Pretty slick," replied another of the men. "He's the goods, all right." "Why, what has he done?" asked Kennedy. "Nothing in particular. But he came out to see us once. You can't blame him for being a bit sore at us fellows hanging about. But he didn't show it. Instead he almost begged us to be careful of how we asked questions of the girl. Of course, all of us could see how completely broken up she is. We haven't bothered her. In fact, we'd do anything we could for her. But Lockwood talks straight from the shoulder. You can see he's used to handling all kinds of situations." "But did he say anything, has he done anything?" persisted Kennedy. "N-no," admitted the reporter. "I can't say he has." Craig frowned a bit. "I thought not," he remarked. "These people aren't giving away any hints, if they can help it." "It's my idea," ventured another of the men, "that when this case breaks, it will break all of a sudden. I shouldn't wonder if we are in for one of the sensations of the year, when it comes." Kennedy looked at him inquiringly. "Why?" he asked simply. "No particular reason," confessed the man. "Only the regular detectives act so chesty. They haven't got a thing, and they know it, only they won't admit it to us. O'Connor was here." "What did he say?" "Nothing. He went through all the motions--'Now, pens lifted, boys,' and all that--talked a lot--and after it was all over he might have been sure no one would publish a line of his confidences. There wasn't a stick of copy in the whole thing." Kennedy laughed. "O'Connor's all right," he replied. "We may need him sorely before we get through. After all, nothing can take the place of the organization the police have built up. You say de Moche is in there yet?" "Yes. He seemed very anxious to see her. We never get a word out of him. I've been thinking what would happen if we tried to get him mad. Maybe he'd talk." "More likely he'd pull a gun," cautioned another. "Excuse ME." Kennedy said nothing, evidently content to let the newspaper men go their own sweet way. He nodded to them, and pressed the buzzer at the Mendoza door. "Tell Senorita Mendoza that it is Professor Kennedy," he said to Juanita, who opened the door, keeping it on the chain, to be sure it was no unwelcome intruder. Evidently she had had orders to admit us, for a second later we found ourselves again in the little reception room. We sat down, and I saw that Craig's attention had at once been fixed on something. I listened intently, too. On the other side of the heavy portieres that cut us off from the living room I could distinguish low voices. It was de Moche and Inez. Whatever the ethics of it, we could not help listening. Besides there was more at stake than ethics. Evidently the young man was urging her to do something that she did not agree with. "No," we heard her say finally, in a quiet tone, "I cannot believe it, Alfonso. Mr. Whitney is Mr. Lockwood's associate now. My father and Mr. Lockwood approved of him. Why should I do otherwise?" De Moche was talking earnestly but in a very muffled voice. We could not make out anything except a few scattered phrases which told us nothing. Once I fancied he mentioned his mother. Whatever it was that he was urging, Inez was firm. "No, Alfonso," she repeated, her voice a little higher and excited. "It cannot be. You must be mistaken." She had risen, and now moved toward the hall door, evidently forgetting that the folding doors behind the portieres were open. "Professor Kennedy and Mr. Jameson are here," she said. "Would you care to meet them?" He replied in the negative. Yet as he passed the reception room he could not help seeing us. As Inez greeted us, I saw that Alfonso was making a desperate effort to control his expression. He seemed to be concealing a bitter disappointment. Seeing us, he bowed stiffly, and, with just the murmur of a greeting, excused himself. He had no sooner closed the door to run the gauntlet of the sharp eyes in the hall than the Senorita faced us fully. She was pale and nervous. Evidently something that he had said to her had greatly agitated her. Yet with all her woman's skill she managed to hide all outward traces of emotion that might indicate what it was that racked her mind. "You have something to report?" she asked, a trifle anxiously. "Nothing of any great importance," admitted Craig. Was it actually a look of relief that crossed her face? Try as I could, it seemed to me to be an anomalous situation. She wanted the murderer of her father caught, naturally. Yet she did not seem to be offering us the natural assistance that was to be expected. Could it be that she suspected some one perhaps near and dear to her of having some knowledge, which, now that the deed was done, would do more harm than good if revealed? It was the only conclusion to which I could come. I was surprised at Kennedy's next question. Was the same idea in his mind, also? "We have seen Mr. Whitney," he ventured. "Just what are Mr. Lockwood's relations with him--and yours?" "Merely that Mr. Lockwood and my father were partners," she answered hastily. "They had decided that their interests would be more valuable by some arrangement with Mr. Whitney, who controls so much down in Peru." "Do you think that Senora de Moche exercises a very great influence on Mr. Whitney?" asked Craig, purposely introducing the name of the Indian woman to see what effect it might have on her. "Oh," she cried, with a little exclamation of alarm, "I hope not." Yet it was evident that she feared so. "Why is it that you fear it?" insisted Kennedy. "What has she done to make you fear it?" "I don't like her," returned Inez, with a frown. "My father knew her--too well. She is a schemer, an adventuress. Once she has a hold on a man, one cannot say--" She paused, then went on in a different tone. "But I would rather not talk about the woman. I am afraid of her. Never does she talk to me that she does not get something out of me that I do not wish to tell her. She is uncanny." Personally, I could not blame Inez for her opinion. I could understand it. Those often baleful eyes had a penetrating power that one might easily fall a victim to. "But you can trust Mr. Lockwood," he returned. "Surely he is proof against her, against any woman." Inez flushed. It was evident that of all the men who were interested in the little beauty, Lockwood was first in her mind. Yet when Kennedy put the question thus she hesitated. "Yes," she replied, "of course, I trust him. It is not that woman whom I fear with him." She said it with an air almost of defiance. There was some kind of struggle going on in her mind, and she was too proud to let us into the secret. Kennedy rose and bowed. For the present he had come to the conclusion that if she would not let us help her openly the only thing to do was to help her blindly. Half an hour later we were at Norton's apartment, not far from the University campus. He listened intently as Kennedy told such parts of what we had done as he chose. At the mention of the arrow poison, he seemed startled beyond measure. "You are sure of it?" he asked anxiously. "Positive, now," reiterated Kennedy. Norton's face was drawn in deep lines. "If some one has the secret," he cried hastily, "who knows when and on whom next he may employ it?" Coming from him so soon after the same idea had been hinted at by the coroner, I could not but be impressed by it. "The very novelty of the thing is our best protection," asserted Kennedy confidently. "Once having discovered it, if Walter gives the thing its proper value in the Star, I think the criminal will be unlikely to try it again. If you had had as much experience in crime as I have had, you would see that it is not necessarily the unusual that is baffling. That may be the surest way to trace it. Often it is because a thing is so natural that it may be attributed to any person among several, equally well." Norton eyed us keenly, and shook his head. "You may be right," he said doubtfully. "Only I had rather that this person, whoever he may be, had fewer weapons." "Speaking of weapons," broke in Kennedy, "you have had no further idea of why the dagger might have been taken?" "There seems to have been so much about it that I did not know," he returned, "that I am almost afraid to have an opinion. I knew that its three-sided sheath inclosed a sharp blade, yet who would have dreamed that that blade was poisoned?" "You are lucky not to have scratched yourself with it by accident while you were studying it." "Possibly I might have done it, if I had had it in my possession longer. It was only lately that I had leisure to study it." "You knew that it might offer some clue to the hidden treasure of Truxillo?" suggested Kennedy. "Have you any recollection of what the inscriptions on it said?" "Yes," returned Norton, "I had heard the rumours about it. But Peru is a land of tales of buried treasure. No, I can't say that I paid much more attention to it than you might have done if some one asserted that he had another story of the treasure of Captain Kidd. I must confess that only when the thing was stolen did I begin to wonder whether, after all, there might not be something in it. Now it is too late to find out. From the moment when I found that it was missing from my collection I have heard no more about it than you have found out. It is all like a dream to me. I cannot believe even yet that a mere bit of archaeological and ethnological specimen could have played so important a part in the practical events of real life." "It does seem impossible," agreed Kennedy. "But it is even more remarkable than that. It has disappeared without leaving a trace, after having played its part." "If it had been a mere robbery," considered Norton, "one might look for its reappearance, I suppose, in the curio shops. For to-day thieves have a keen appreciation of the value of such objects. But, now that you have unearthed its use against Mendoza--and in such a terrible way--it is not likely that that will be what will happen to it. No, we must look elsewhere." "I thought I would tell you," concluded Kennedy, rising to go. "Perhaps after you have considered it over night some idea may occur to you." "Perhaps," said Norton doubtfully. "But I haven't your brilliant faculty of scientific analysis, Kennedy. No, I shall have to lean on you, in that, not you on me." We left Norton, apparently now more at sea than ever. At the laboratory Kennedy plunged into some microphotographic work that the case had suggested to him, while I dashed off, under his supervision, an account of the discovery of curare, and telephoned it down to the Star in time to catch the first morning edition, in the hope that it might have some effect in apprising the criminal that we were hard on his trail, which he had considered covered. I scanned the other papers eagerly in the morning for Kennedy, hoping to glean at least some hints that others who were working on the case might have gathered. But there was nothing, and, after a hasty bite of breakfast, we hurried back to take up the thread of the investigation where we had laid it down. To our surprise, on the steps of the Chemistry Building, as we approached, we saw Inez Mendoza already waiting for us in a high state of agitation. Her face was pale, and her voice trembled as she greeted us. "Such a dreadful thing has come to me," she cried, even before Kennedy could ask her what the trouble was. From her handbag she drew out a crumpled, dirty piece of paper in an envelope. "It came in the first mail," she explained. "I could not wait to send it to you. I brought it myself. What can it mean?" Kennedy unfolded the paper. Printed in large characters, in every way similar to the four warnings that had been sent to us, was just one ominous line. We read: "Beware the man who professes to be a friend of your father." I glanced from the note to Kennedy, then to Inez. One name was in my mind, and before I knew it I had spoken it. "Lockwood?" I queried inadvertently. Her eyes met mine in sharp defiance. "Impossible," she exclaimed. "It is some one trying to injure him with me. Beware of Mr. Lockwood? How absurd!" Yet it must have meant Lockwood. No one else could have been meant. It was he, most of all, who might be called a friend of her father. She seemed to see the implication without a word from us. I could not help sympathizing with the brave girl in her struggle between the attack against Lockwood and her love and confidence in him. It did not need words to tell me that evidence must be overwhelming to convince her that her lover might be involved in any manner. IX THE PAPER FIBRES Kennedy examined the anonymous letter carefully for several minutes, while we watched him in silence. "Too clever to use a typewriter," he remarked, still regarding the note through the lens of a hand-glass. "Almost any one would have used a machine. That would have been due to the erroneous idea that typewriting cannot be detected. The fact is that the typewriter is perhaps a worse means of concealing identity than is disguised handwriting, especially printing like this. It doesn't afford the effective protection to the criminal that one supposes. On the contrary, the typewriting of such a note may be the direct means by which it can be traced to its source. We can determine what kind of machine it was done with, then what particular machine was used can be identified." He paused and indicated a number of little instruments which he had taken from a drawer and laid on the table, as he tore off a bit of the corner of the sheet of paper and examined it. "There is one thing I can do now, though," he continued. "I can study the quality of the paper in this sheet. If it were only torn like those warnings we have already received, it might perhaps be mated with another piece as accurately as if the act had been performed before our eyes." He picked up a little instrument with a small curved arm and a finely threaded screw that brought the two flat surfaces of the arm and the end of the screw together. "There is no such good fortune in this case, however," he resumed, placing the paper between the two small arms. "But by measurements made by this vernier micrometer caliper I can find the precise thickness of the paper as compared to the other samples." He turned to a microscope and placed the corner of the paper under it. Then he drew from the drawer the four scraps of paper which had already been sent to us, as well as a pile of photographs. "Under ordinary circumstances," he explained, "I should think that what I am doing would be utterly valueless as a clue to anything. But we are reduced to the minutiae in this affair. And to-day science is not ready to let anything pass as valueless." He continued to look at the various pieces of paper under the microscope. "I find under microscopic examination," he went on, addressing Inez, but not looking up from the eye-piece as he shifted the papers, "that the note you have received, Senorita Mendoza, is written on a rather uncommon linen bond paper. Later I shall take a number of microphotographs of it. I have here, also, about a hundred microphotographs of the fibres in other kinds of paper, many of them bonds. These I have accumulated from time to time in my study of the subject. None of them, as you can see, shows fibres resembling this one in question, so that we may conclude that it is of uncommon quality. "Here I have the fibres, also, of four pieces of paper that have already figured in the case. These four correspond, as well as the indentures of the torn edges. As for the fibres, lest you should question the accuracy of the method, I may say that I know of a case where a man in Germany was arrested, charged with stealing a government bond. He was not searched until later. There was no evidence, save that after the arrest a large number of spitballs were found around the courtyard under his cell window. This method of comparing the fibres of the regular government paper was used, and by it the man was convicted of stealing the bond. I think it is unnecessary to add that in the present case I can see definitely that not only the four pieces of paper that bore warnings to us were the same kind, but that this whole sheet, with its anonymous warning to you, is also the same." Inez Mendoza looked at Kennedy as though he possessed some weird power. Her face, which had already been startled into an expression of fear at his mention of Lockwood, now was pale. "Other warnings?" she repeated tremulously. Quickly Kennedy explained what had already happened to us, watching the effect on her as he read of the curse of Mansiche and the Gold of the Gods. "Oh," she cried, mastering her emotion with a heroic effort, "I wish my father had never become mixed up in the business. Ever since I was a little girl I have heard these vague stories of the big fish and the little fish, the treasure, and the curse. But I never thought they were anything but fairy tales. You remember, when I first saw you, I did not even tell them to you." "Yes," returned Kennedy. "I remember. But had you no other reason? Did you, down in your heart, think them really fairy tales?" She shuddered. "Perhaps not," she murmured. "But I have heard enough of you detectives to know that you do not think a woman's fears exactly evidence." "Still they might lead to evidence," suggested Kennedy. She looked at him, more startled than ever, for already he had given her a slight exhibition of his powers. "Mr. Kennedy," she exclaimed, "I am positively afraid of you, afraid that every little thing I do may lead to something I don't intend." There was a frankness about the remark that would have been flattering from a man, but from her excited sympathy. "No," she went on, "I have nothing tangible--only my feelings. I fear I must admit that my father had enemies, though who they are I cannot tell you. No, it is all in my heart--not in my head. There are those whom I dislike--and there are those whom I like and trust. You may call me foolish, but I cannot help trusting--Mr. Lockwood." She had not meant to say his name, and Kennedy and I looked at her in surprise. "You see?" she continued. "Every time I talk I say something, convey some impression that is the opposite of what I wish. Oh--what shall I do? Have I no one to trust?" She was crying. "You may trust me, Senorita," said Kennedy, in a low tone, pausing before her. "At least I have no other interest than finding the truth and helping you. There--there. We have had enough to-day. I cannot ask you to try to forget what has happened. That would be impossible. But I can ask you, Senorita, to have faith--faith that it will all turn out better, if you will only trust me. When you feel stronger--then come to me. Tell me your fears--or not--whichever does you the most good. Only keep your mind from brooding. Face it all as you know your father would have you do." Kennedy's words were soothing. He seemed to know that tears were the safety-valve she needed. "Mr. Jameson will see that you get home safely in a taxicab," he continued. "You can trust him as you would myself." I can imagine circumstances under which I would have enjoyed escorting Inez to her home, but today was not one of the times. Yet she seemed so helpless, so grateful for everything we did for her that I did not need even the pressure of her little hand as she hurried into the apartment from the car with a hasty word of thanks. "You will tell Mr. Kennedy--you will both be--so careful?" she hesitated before leaving me. I assured her that we would, wondering what she might fear for us, as I drove away again. There did not happen to be any of the newspaper men about at the time, and I did not stop. Back in the laboratory, I found Kennedy arranging something under the rug at the door as I came up the hall. "Don't step there, Walter," he cautioned. "Step over the rug. I'm expecting visitors. How was she when she arrived home?" I told him of her parting injunction. "Not bad advice," he remarked. "I think there's a surprise back of those warnings. They weren't sent just for effect." He had closed the door, and we were standing by the table, looking at the letters, when we heard a noise at the door. It was Norton again. "I've been thinking of what you told me last night," he explained, before Kennedy had a chance to tell him to step over the rug. "Has anything else happened?" Kennedy tossed over the anonymous letter, and Norton read it eagerly. "Whom does it mean?" he asked, quickly glancing up, then adding, "It might mean any of us who are trying to help her." "Exactly," returned Kennedy. "Or it might be Lockwood, or even de Moche. By the way, you know the young man pretty well, don't you? I wonder if you could find him anywhere about the University this morning and persuade him to visit me?" "I will try," agreed Norton. "But these people are so very suspicious just now that I can't promise." Norton went out a few minutes later to see what he could do to locate Alfonso, and Kennedy replaced another blank sheet of paper for that under the rug on which Norton had stepped before we could warn him. No sooner had he gone than Kennedy reached for the telephone and called Whitney's office. Lockwood was there, as he had hoped, and, after a short talk, promised to drop in on us later in the morning. It was fully half an hour before Norton returned, having finally found Alfonso. De Moche entered the laboratory with a suspicious glance about, as though he thought something might have been planted there for him. "I had a most interesting talk with your mother yesterday," began Kennedy, endeavouring by frankness to put the young man at ease. "And this morning, already, Senorita Mendoza has called on me." De Moche was all attention at the words. But before he could say anything Kennedy handed him the anonymous letter. He read it, and his face clouded as he handed it back. "You have no idea who could have sent such a note?" queried Craig, "or to whom it might refer?" He glanced at Norton, then at us. It was clear that some sort of suspicion had flashed over him. "No," he said quickly, "I know no one who could have sent it." "But whom does it mean?" asked Kennedy, holding him to the part that he avoided. The young man shrugged his shoulders. "She has many friends," he answered simply. "Yes," persisted Kennedy, "but few against whom she might be warned in this way. You do not think it is Professor Norton, for instance--or myself?" "Oh, no, no--hardly," he replied, then stopped, realizing that he had eliminated all but Lockwood, Whitney, and himself. "It could not be Mr. Lockwood?" demanded Craig. "Who sent it?" he asked, looking up. "No--whom it warns against." De Moche had known what Kennedy meant, but had preferred to postpone the answer. It was native never to come to the point unless he was forced to do so. He met our eyes squarely. He had not the penetrating power that his mother possessed, yet his was a sharp faculty of observation. "Mr. Lockwood is very friendly with her," he admitted, then seemed to think something else necessary to round out the idea. "Mr. Kennedy, I might have told her the same myself. Senorita Mendoza has been a very dear friend--for a long time." I had been so used to having him evasive that now I did not exactly know what to make of such a burst of confidence. It was susceptible of at least two interpretations. Was he implying that it was sent to cast suspicion on him, because he felt that way himself or because he himself was her friend? "There have been other warnings," pursued Kennedy, "both to myself and Mr. Jameson, as well as Professor Norton and Dr. Leslie. Surely you must have some idea of the source." De Moche shook his head. "None that I can think of," he replied. "Have you asked my mother?" "Not yet," admitted Kennedy. De Moche glanced at his watch. "I have a lecture at this hour," he remarked, evidently glad of an excuse to terminate the interview. As he left, Kennedy accompanied him to the door, careful himself to step over the mat. "Hello, what's new?" we heard a voice in the hall. It was Lockwood, who had come up from downtown. Catching sight of de Moche, however, he stopped short. The two young men met face to face. Between them passed a glance of unconcealed hostility, then each nodded stiffly. De Moche turned to Kennedy as he passed down the hall. "Perhaps it may have been sent to divert suspicion--who can tell?" he whispered. Kennedy nodded appreciatively, noting the change. At the sound of Lockwood's voice both Norton and I had taken a step further after them out into the hall, Norton somewhat in advance. As de Moche disappeared for his lecture, Kennedy turned to me from Lockwood and caught my eye. I read in his glance that fell from me to the mat that he wished me quietly to abstract the piece of paper which he had placed under it. I bent down and did so without Lockwood seeing me. "Why was he here?" demanded Lockwood, with just a trace of defiance in his voice, as though he fancied the meeting had been framed. "I have been showing this to every one who might help me," returned Kennedy, going back into the laboratory after giving me an opportunity to dispose of the shoe-prints. He handed the anonymous letter and the other warnings to the young soldier of fortune, with a brief explanation. "Why don't they come out into the open, whoever they are?" commented Lockwood, laying the papers down carelessly again on the table. "I'll meet them--if they mean me." "Who?" asked Kennedy. Lockwood faced Norton and ourselves. "I'm not a mind reader," he said significantly. "But it doesn't take much to see that some one wants to throw a brick at me. When I have anything to say I say it openly. Inez Mendoza without friends just now would be a mark, wouldn't she?" His strong face and powerful jaw were set in a menacing scowl. He would be a bold man who would have come between Lockwood and the lady under the circumstances. "You are confident of Mr. Whitney?" inquired Kennedy. "Ask Norton," replied Lockwood briefly. "He knew him long before I did." Norton smiled quietly. "Mr. Kennedy should know what my opinion of Mr. Whitney is, I think," replied Norton confidently. "I trust that you will succeed in running these blackmailers down," pursued Lockwood, still standing. "If I did not have more than I can attend to already since the murder of Mendoza I'd like to take a hand myself. It begins to look to me, after reading that letter, as though there was nothing too low for them to attempt. I shall keep this latest matter in mind. If either Mr. Whitney or myself get any hint, we'll turn it over to you." Norton left shortly after Lockwood, and Kennedy again picked up the letter and scanned it. "I could learn something, I suppose, if I analyzed this printing," he considered, "but it is a tedious process. Let me see that envelope again. H-m, postmarked by the uptown sub-station, mailed late last night. Whoever sent it must have done so not very far from us here. Lockwood seemed to take it as though it applied to himself very readily, didn't he? Much more so than de Moche. Only for the fact that the fibres show it to be on paper similar to the first warnings, I might have been inclined to doubt whether this was bona fide. At least, the sender must realize now that it has produced no appreciable effect--if any was intended." Kennedy's last remark set me thinking. Could some one have sent the letter not to produce the effect apparently intended, but with the ultimate object of diverting suspicion from himself? Lockwood, at least, had not seemed to take the letter very seriously. X THE X-RAY READER "I think I'll pay another visit to Whitney, in spite of all that Norton and Lockwood say about him," remarked Kennedy, considering the next step he would take in his investigation. Accordingly, half an hour later we entered his Wall Street office, where we were met by a clerk, who seemed to remember us. "Mr. Whitney is out just at present," he said, "but if you will be seated I think I can reach him by telephone." As we sat in the outer office while the clerk telephoned from Whitney's own room the door opened and the postman entered and laid some letters on a table near us. Kennedy could not help seeing the letter on top of the pile, and noticed that it bore a stamp from Peru. He picked it up and read the postmark, "Lima," and the date some weeks previous. In the lower corner, underscored, were the words "Personal--Urgent." "I'd like to know what is in that," remarked Craig, turning it over and over. He appeared to be considering something, for he rose suddenly, and with a nod of his head to himself, as though settling some qualm of conscience, shoved the letter into his pocket. A moment later the clerk returned. "I've just had Mr. Whitney on the wire," he reported. "I don't think he'll be back at least for an hour." "Is he at the Prince Edward Albert?" asked Craig. "I don't know," returned the clerk, oblivious to the fact that we must have seen that in order to know the telephone number he must have known whether Mr. Whitney was there or elsewhere. "I shall come in again," rejoined Kennedy, as we bowed ourselves out. Then to me he added, "If he is with Senora de Moche and they are at the Edward Albert, I think I can beat him back with this letter if we hurry." A few minutes later, in his laboratory, Kennedy set to work quickly over an X-ray apparatus. As I watched him, I saw that he had placed the letter in it. "These are what are known as 'low tubes,'" he explained. "They give out 'soft rays.'" He continued to work for several minutes, then took the letter out and handed it to me. "Now, Walter," he said brusquely, "if you will just hurry back down there to Whitney's office and replace that letter, I think I will have something that will astonish you--though whether it will have any bearing on the case remains to be seen. At least I can postpone seeing Whitney himself for a while." I made the trip down again as rapidly as I could. Whitney was not back when I arrived, but the clerk was there, and I could not very well just leave the letter on the table again. "Mr. Kennedy would like to know when he can see Mr. Whitney," I said, on the spur of the moment. "Can't you call him up again?" The clerk, as I had anticipated, went into Whitney's office to telephone. Instead of laying the letter on the table, which might have excited suspicion, I stuck it in the letter slot of the door, thinking that perhaps they might imagine that it had caught there when the postman made his rounds. A moment later the clerk returned. "Mr. Whitney is on his way down now," he reported. I thanked him, and said that Kennedy would call him up when he arrived, congratulating myself on the good luck I had had in returning the letter. "What is it?" I asked, a few minutes later, when I had rejoined Craig in the laboratory. He was poring intently over what looked like a negative. "The possibility of reading the contents of documents inclosed in a sealed envelope," he replied, still studying the shadowgraph closely, "has already been established by the well-known English scientist, Dr. Hall Edwards. He has been experimenting with the method of using X-rays recently discovered by a German scientist, by which radiographs of very thin substances, such as a sheet of paper, a leaf, an insect's body, may be obtained. These thin substances, through which the rays used formerly to pass without leaving an impression, can now be easily radiographed." I looked carefully as he traced out something on the queer negative. On it, it was easily possible, following his guidance, to read the words inscribed on the sheet of paper inside. So admirably defined were all the details that even the gum on the envelope and the edges of the sheet of paper inside the envelope could be distinguished. "It seems incredible," I exclaimed, scarcely believing what I actually saw. "It is almost like second sight." Kennedy smiled. "Any letter written with ink having a mineral base can be radiographed," he added. "Even when the sheet is folded in the usual way, it is possible, by taking a radiograph, as I have done, stereoscopically. Then every detail can be seen standing out in relief. Besides, it can be greatly magnified, which aids in deciphering it if it is indistinct or jumbled up. Some of it looks like mirror-writing. Ah," he continued, "here's something interesting." Together we managed to trace out the contents of several paragraphs laboriously, the gist of which I give here: "LIMA, PERU. "DEAR WHITNEY: "Matters are progressing very favorably here, considering the stoppage of business due to the war. I am doing everything in my power to conserve our interests, and now and then, owing to the scarcity of money, am able to pick up a concession cheaply, which will be of immense value to us later. "However, it is not so much of business that I wish to write you at the present time. You know that my friend Senora de Moche, with her son, Alfonso, is at present in New York. Doubtless she has already called on you and tried to interest you in her own properties here. I need not advise you to be very careful in dealing with her. "The other day I heard a rumour that may prove interesting to you, regarding Norton and his work here on his last trip. As we know, he has succeeded in finding and getting out of the country an Inca dagger which, I believe, bears a very important inscription. I do not know anything definite about it, as these people are very reticent. But no doubt he has told you all about it by this time. If it should prove of value, I depend on you to let me know, so that I may act at this end accordingly. "What I am getting at is this: I understand that from rumours and remarks of the Senora she believes that Norton took an unfair advantage during her absence. What the inscription is I don't know, but from the way these people down here act one would think that they all had a proprietary interest in the relic. What it is all about I don't know. But you will find the Senora both a keen business woman and an accomplished antiquarian, if you have not already discovered it. "In regard to Lockwood and Mendoza, if we can get them in on our side, it ought to prove a winning combination. There are stories here of how de Moche has been playing on Mendoza's passions--she's thoroughly unscrupulous and Don Luis is somewhat of a Don Juan. I write this to put you on guard. Her son, Alfonso, whom you perhaps have met also, is of another type, though I have heard it said that he laid siege to Inez Mendoza in the hope of becoming allied with one of the oldest families. "Such, at least, is the gossip down here. I cannot presume to keep you posted at such a distance, but thought I had better write what is in every one's mouth. As for the inscribed dagger which Norton has taken with him, I rely on you to inform me. There seems to be a great deal of mystery connected with it, and I am unable even to hazard a guess as to its nature. Fortunately, you are on the spot "Very sincerely yours, "HAGGERTY." "So," remarked Kennedy, as he read over the translation of the skiagraph which he had jotted down as we picked out the letters and words, "that's how the land lies. Everybody seems to have appreciated the importance of the dagger." "Except Norton," I could not help putting in in disgust. "And now it's gone," he continued, "just as though some one had dropped it overboard. I believe I will keep that appointment you made for me with Whitney, after all." Thus it happened that I found myself a third time entering Whitney's building. I was about to step into the elevator, when Kennedy tugged at my arm and pulled me back. "Hello, Norton," I heard him say, as I turned and caught sight of the archaeologist just leaving an elevator that had come down. Norton's face plainly showed that he was worried. "What the matter?" asked Kennedy, putting the circumstances together. "What has Whitney been doing?" Norton seemed reluctant to talk, but having no alternative motioned to us to step aside in the corridor. "It's the first time I've talked with him since the dagger was stolen--that is, about the loss," he said nervously. "He called me up half an hour ago and asked me to come down." I looked at Kennedy significantly. Evidently it must have been just after his return to the office and receipt of the letter which I had stuck in the letter slot. "He was very angry over something," continued Norton. "I'm sure it was not my fault if the dagger was stolen, and I'm sure that managing an expedition in that God-forsaken country doesn't give you time to read every inscription, especially when it is almost illegible, right on the spot. There was work enough for months that I brought back, along with that. Sometimes Whitney's unreasonable." "You don't think he could have known something about the dagger all along?" ventured Craig. Norton puckered his eyes. "He never said anything," he replied. "If he had asked me to drop other things for that, why, of course, I would have done so. We can't afford to lose him as a contributor to the exploration fund. Confound it--I'm afraid I've put my foot in it this time." Kennedy said nothing, and Norton continued, growing more excited: "Everybody's been talking to Whitney, telling him all kinds of things--Lockwood, the de Moches, heaven knows who else. Why don't they come out and face me? I've a notion to try to carry on my work independently. Nothing plays hob with scholarship like money. You'd think he owned me body and soul, and the collection, too, if you heard him talk. Why, he accused me of carelessness in running the Museum, and heaven knows I'm not the curator--I'm not even the janitor!" Norton was excited, but I could not help feeling that he was also relieved. "I've been preparing for the time when I'd have to cut loose," he went on finally. "Now, I suppose it is coming. Ah, well, perhaps it will be better--who can tell? I may not do so much, but it will all be mine, with no strings attached. Perhaps, after all, it is for the best." Talking over his troubles seemed to do Norton some good, for I am sure that he left us in a better frame of mind than we had found him. Kennedy wished him good-luck, and we again entered the lift. We found Whitney in an even greater state of excitement than Norton had been. I am sure that if it had been any one else than Kennedy he would have thrown him out, but he seemed to feel that he must control himself in our presence. "What do you know about that fellow Norton, up at your place?" he demanded, almost before we had seated ourselves. "A very hard-working, ambitious man his colleagues tell me," returned Kennedy, purposely I thought, as if it had been a red rag flaunted before a bull. "Hard-working--yes," bellowed Whitney. "He has worked me hard. I send him down to Peru--yes, I put up most of the money. Then what does he do? Just kids me along, makes me think he's accomplishing a whole lot--when he's actually so careless as to let himself be robbed of what he gets with my money. I tell you, you can't trust anybody. They all double-cross you. I swear, I think Lockwood and I ought to go it alone. I'm glad I found that fellow out. Let himself be robbed--a fine piece of work! Why, that fellow couldn't see through a barn door--after the horse was stolen," he concluded, mixing his metaphors in his anger. "Evidently some one has been telling you something," remarked Kennedy. "We tried to see you twice this morning, but couldn't find you." His tone was one calculated to impress Whitney with the fact that he had been watching and had some idea of where he really was. Whitney shot a sharp glance at Craig, whose face betrayed nothing. "Ambitious--I should say so," repeated Whitney, reverting to Norton to cover up this new change of the subject. "Well--let him be ambitious. We can get along without him. I tell you, Kennedy, no one is indispensable. There is always some way to get along--if you can't get over an obstacle, you can get around it. I'll dispense with Mr. Norton. He's an expensive luxury, anyhow. I'm just as well satisfied." There was real vexation in Whitney's voice, yet as he talked he, too, seemed to cool down. I could not help thinking that both Norton and Whitney were perhaps just a bit glad at the break. Had both of them got out of each other all that they wanted--Norton his reputation and Whitney--what? He cooled down so rapidly now that almost I began to wonder whether his anger had been genuine. Did he know more about the dagger than appeared? Was this his cover--to disown Norton? "It seems to me that Senora de Moche is ambitious for her son, too," remarked Kennedy, tenaciously trying to force the conversation into the channel he chose. "How's that?" demanded Whitney, narrowing his eyes down into a squint at Kennedy's face, a proceeding that served by contrast to emphasize the abnormal condition of the pupils which I had already noticed both in his eyes and Lockwood's. "I don't think she'd object to having him marry into one of the leading families in Peru," ventured Kennedy, paraphrasing what we had already read in the letter. "Perhaps Senorita Mendoza herself can be trusted to see to that," Whitney replied with a quick laugh. "To say nothing of Mr. Lockwood," suggested Craig. Whitney looked at him quizzically, as though in doubt just how much this man knew. "Senora de Moche puzzles me," went on Kennedy. "I often wonder whether superstition or greed would rule her if it came to the point in this matter of the Gold of the Gods, as they all seem to call the buried treasure at Truxillo. She's a fascinating woman, but I can't help feeling that with her one is always playing with fire." Whitney eyed us knowingly. I had long ago taken his measure as a man quite susceptible to a pretty face, especially if accompanied by a well-turned ankle. "I never discuss politics during business hours," he laughed, with a self-satisfied air. "You will excuse me? I have some rather important letters that I must get off." Kennedy rose, and Whitney walked to the door with us, to call his stenographer. We had scarcely said good-bye and were about to open the outer door when it was pushed open from outside, and Lockwood bustled in. "No more anonymous letters, I hope?" he queried, in a tone which I could not determine whether serious or sarcastic. Kennedy answered in the negative. "Not unless you have one." "I? I rather think the ready letter-writers know better than to waste time on me. That little billet doux seems to have quite upset the Senorita, though. I don't know how many times she has called me up to see if I was all right. I begin to think that whoever wrote it has done me a good turn, after all." Lockwood did not say it in a boastful way, but one could see that he was greatly pleased at the solicitude of Inez. "She thinks it referred to you, then?" asked Kennedy. "Evidently," he replied; then added, "I won't say but that I have taken it seriously, too." He slapped his hip pocket. Under the tail of his coat bulged a blue-steel automatic. "You still have no idea who could have sent it, or why?" Lockwood shook his head. "Whoever he is, I'm ready," he replied grimly, bowing us out. XI THE SHOE-PRINTS "I'm afraid we've neglected the Senorita a bit, in our efforts to follow up what clues we have in the case," remarked Kennedy, as we rode uptown again. "She needs all the protection we can give her. I think we'd better drop around there, now that she is pretty likely to be left alone." Accordingly, instead of going back to the laboratory, we dropped off near the apartment of the Mendozas and walked over from the subway. As we turned the corner, far down the long block I could see the entrance to the apartment. "There she is now," I said to Kennedy, catching sight of her familiar figure, clad in sombre black, as she came down the steps. "I wonder where she can be going." She turned at the foot of the steps and, as chance would have it, started in the opposite direction from us. "Let us see," answered Kennedy, quickening his pace. She had not gone very far before a man seemed to spring up from nowhere and meet her. He bowed, and walked along beside her. "De Moche," recognized Kennedy. Alfonso had evidently been waiting in the shadow of an entrance down the street, perhaps hoping to see her, perhaps as our newspaper friend had seen before, to watch whether Lockwood was among her callers. As we walked along, we could see the little drama with practically no fear of being seen, so earnestly were they talking. Even during the few minutes that the Senorita was talking with him no one would have needed to be told that she really had a great deal of regard for him, whatever might be her feelings toward Lockwood. "I should say that she wants to see him, yet does not want to see him," observed Kennedy, as we came closer. She seemed now to have become restive and impatient, eager to cut the conversation short. It was quite evident at the same time that Alfonso was deeply in love with her, that though she tried to put him off he was persistent. I wondered whether, after all, some of the trouble had not been that during his lifetime the proud old Castilian Don Luis could never have consented to the marriage of his daughter to one of Indian blood. Had he left a legacy of fear of a love forbidden by race prejudice? In any event, the manner of Alfonso's actions about the Mendoza apartment was such that one could easily imagine his feelings toward Lockwood, whom he saw carrying off the prize under his very eyes. As for his mother, the Senora, we had already seen that Peruvians of her caste were also a proud old race. Her son was the apple of her eye. Might not some of her feelings be readily accounted for? Who were these to scorn her race, her family? We had walked along at a pace that finally brought us up with them. As Kennedy and I bowed, Alfonso seemed at first to resent our intrusion, while Inez seemed rather to welcome it as a diversion. "Can we not expect you?" the young man repeated. "It will be only for a few minutes this afternoon, and my mother has something of very great importance to tell." He was half pleading, half apologizing. Inez glanced hastily around at Kennedy, uncertain what to say, and hoping that he might indicate some course. Surreptitiously, Kennedy nodded an affirmative. "Very well, then," she replied reluctantly, not to seem to change what had been her past refusal too suddenly. "I may ask Professor Kennedy, too?" He could scarcely refuse before us. "Of course," he agreed, quickly turning to us. "We were speaking about meeting this afternoon at four in the tea room of the Prince Edward. You can come?" Though the invitation was not over-gracious, Kennedy replied, "We should be delighted to accompany Miss Inez, I am sure. We happened to be passing this way and thought we would stop in to see if anything new had happened. Just as we turned the corner we saw you disappearing down the street, and followed. I trust everything is all right?" "Nothing more has happened since this morning," she returned, with a look that indicated she understood that Kennedy referred to the anonymous letter. "I had a little shopping to do. If you will excuse me, I think I will take a car. This afternoon--at four." She nodded brightly as we assisted her into a taxicab and left us three standing there on the curb. For a moment it was rather awkward. To Alfonso her leaving was somewhat as though the sun had passed under a cloud. "Are you going up toward the University?" inquired Kennedy. "Yes," responded the young man reluctantly. "Then suppose we walk. It would take only a few more minutes," suggested Kennedy. Alfonso could not very well refuse, but started off at a brisk pace. "I suppose these troubles interfere seriously with your work," pursued Craig, as we fell into his stride. "Yes," he admitted, "although much of my work just now is only polishing off what I have already learned--getting your American point of view and methods. You see, I have had an idea that the canal will bring both countries into much closer relations than before. And if you will not learn of us, we must learn of you." "It is too bad we Americans don't take more interest in the countries south of us," admitted Craig. "I think you have the right idea, though. Such men as Mr. Whitney are doing their best to bring the two nations closer together." I watched the effect of the mention of Whitney's name. It seemed distasteful, only in a lesser degree than Lockwood's. "We do not need to be exploited," he ventured. "My belief is that we should not attract capital in order to take things out of the country. If we might keep our own earnings and transform them into capital, it would be better. That is why I am doing what I am at the University." I could not believe that it explained the whole reason for his presence in New York. Without a doubt the girl who had just left us weighed largely in his mind, as well as his and his mother's ambitions, both personal and for Peru. "Quite reasonable," accepted Kennedy. "Peru for the Peruvians. Yet there seems to be such untold wealth in the country that taking out even quite large sums would not begin to exhaust the natural resources." "But they are ours, they belong to us," hastened de Moche, then caught the drift of Kennedy's remarks, and was on his guard. "Buried treasure, like that which you call the Gold of the Gods, is always fascinating," continued Kennedy. "The trouble with such easy money, however, is that it tends to corrupt. In the early days history records its taint. And I doubt whether human nature has changed much under the veneer of modern civilization. The treasure seems to leave its trail even as far away as New York. It has at least one murder to its credit already." "There has been nothing but murder and robbery from the time that the peje chica was discovered," asserted the young man sadly. "You are quite right." "Truly it would seem to have been cursed," added Craig. "The spirit of Mansiche must, indeed, watch over it. I suppose you know of the loss of the old Inca dagger from the University Museum and that it was that with which Don Luis was murdered?" It was the first time Kennedy had broached the subject to de Moche, and I watched closely to see what was its effect. "Perhaps it was a warning," commented Alfonso, in a solemn tone, that left me in doubt whether it was purely superstitious dread or in the nature of a prophecy of what might be expected from some quarter of which we were ignorant. "You have known of the existence of the dagger always, I presume," continued Kennedy. "Have you or any one you know ever sought to discover its secret and search it out?" "I think my mother told you we never dig for treasure," he answered. "It would be sacrilegious. Besides, there is more treasure buried by nature than that dedicated to the gods. There is only one trouble that may hurt our natural resources--the get-rich-quick promoter. I would advise looking out for him. He flourishes in a newly opened country like Peru. That curse, I suppose, is much better understood by Americans than the curse of Mansiche. But as for me, you must remember that the curse is part of my religion, as it were." We had reached the campus by this time, and parted at the gate, each to go his way. "You will drop in on me if you hear anything?" invited Craig. "Yes," promised Alfonso. "We shall see you at four." With this parting reminder he turned toward the School of Mines while we debouched off toward the Chemistry Building. "The de Moches are nobody's tools," I remarked. "That young man seems to have a pretty definite idea of what he wants to do." "At least he puts it so before us," was all that Kennedy would grant. "He seems to be as well informed of what passed at that visit to the Senora as though he had been there too." We had scarcely opened the laboratory door when the ringing of the telephone told us that some one had been trying to get in touch for some time. "It was Norton," said Kennedy, hanging up the receiver. "I imagine he wants to know what happened after we left him and went up to see Whitney." That was, in fact, just what Norton wanted, as well as to make clear to us how he felt on the subject. "Really, Kennedy," he remarked, "it must be fine to feel that your chair in the University is endowed rather than subsidized. You saw how Whitney acted, you say. Why, he makes me feel as if I were his hired man, instead of head of the University's expedition. I'm glad it's over. Still, if you could find that dagger and have it returned it might look better for me. You have no clue, I suppose?" "I'm getting closer to one," replied Craig confidently, though on what he could base any optimism I could not see. The same idea seemed to be in Norton's mind. "You think you will have something tangible soon?" he asked eagerly. "I've had more slender threads than these to work on," reassured Kennedy. "Besides, I'm getting very little help from any of you. You yourself, Norton, at the start left me a good deal in the dark over the history of the dagger." "I couldn't do otherwise," he defended. "You understand now, I guess, how I have always been tied, hand and foot, by the Whitney influence. You'll find that I can be of more service, now." "Just how did you get possession of the dagger?" asked Kennedy, and there flashed over me the recollection of the story told by the Senora, as well as the letter which we had purloined. "Just picked it up from an Indian who had an abnormal dislike to work. They said he was crazy, and I guess perhaps he was. At any rate, he later drowned himself in the lake, I have heard." "Could he have been made insane, do you think?" ruminated Craig. "It's possible that he was the victim of somebody, I understand. The insanity might have been real enough without the cause being natural." "That's an interesting story," returned Norton. "Offhand, I can't seem to recall much about the fellow, although some one else might have known him very well." Evidently he either did not know the tale as well as the Senora, or was not prepared to take us entirely into his confidence. "Who is Haggerty?" asked Craig, thinking of the name signed to the letter we had read. "An agent of Whitney and his associates, who manages things in Lima," explained Norton. "Why?" "Nothing--only I have heard the name and wondered what his connection might be. I understand better now." Kennedy seemed to be anxious to get to work on something, and, after a few minutes, Norton left us. No sooner had the door closed than he took the glass-bell jar off his microscope and drew from a table drawer several scraps of paper on which I recognized the marks left by the carbon sheets. He set to work on another of those painstaking tasks of examination, and I retired to my typewriter, which I had moved into the next room, in order to leave Kennedy without anything that might distract attention from his work. One after another he examined the sheets which he had marked, starting with a hand-lens and then using one more powerful. At the top of the table lay the specially prepared paper on which he had caught and preserved the marks in the dust of the Egyptian sarcophagus in the Museum. Besides these things, I noticed that he had innumerable photographs, many of which were labelled with the stamp of the bureau in the Paris Palais de Justice, over which Bertillon had presided. One after another he looked at the carbon prints, comparing them point by point with the specially prepared copy of the shoe-prints in the sarcophagus. It was, after all, a comparatively simple job. We had the prints of de Moche and Lockwood, as well as Whitney, all of them crossed by steps from Norton. "Well, what do you think of that?" I heard him mutter. I quit my typewriter, with a piece of paper still in it, and hurried into the main room. "Have you found anything?" "I should say I had," he replied, in a tone that betrayed his own astonishment at the find. "Look at that," he indicated to me, handing over one of the sheets. "Compare it with this Museum foot-print." With his pencil Kennedy rapidly indicated the tell-tale points of similarity on the two shoe-prints. I looked up at him, convinced now of some one's identity. "Who was it?" I asked, unable to restrain myself longer. Kennedy paused a minute, to let the importance of the surprise be understood. "The man who entered the Museum and concealed himself in the sarcophagus in the Egyptian section adjoining Norton's treasures," replied Kennedy slowly, "was Lockwood himself!" XII THE EVIL EYE Completely at sea as a result of the unexpected revelation of the shoe-prints we had found in the Museum, and with suspicions now thoroughly aroused against Lockwood, I accompanied Kennedy to keep our appointment with the Senorita at the Prince Edward Albert. We were purposely a bit early, in order to meet Inez, so that she would not have to be alone with the Senora, and we sat down in the lobby in a little angle from which we could look into the tea room. We had not been sitting there very long when Kennedy called my attention to Whitney, who had just come in. Almost at the same time he caught sight of us, and walked over. "I've been thinking a good deal of your visit to me just now," he began, seating himself beside us. "Perhaps I should not have said what I did about your friend Norton. But I couldn't help it. I guess you know something about that dagger he lost, don't you?" "I have heard of the 'great fish' and the 'little fish' and the 'curse of Mansiche,'" replied Kennedy, "if that is what you mean. Somehow the Inca dagger seems to have been mixed up with them." "Yes--with the peje grande, I believe," went on Whitney. Beneath his exterior of studied calm I could see that he was very much excited. If I had not already noted a peculiar physical condition in him, I might have thought he had stopped in the cafe with some friends too long. But his eyes were not those of a man who has had too much to drink. Just then Senorita Mendoza entered, and Kennedy rose and went forward to greet her. She saw Whitney, and flashed an inquiring glance at us. "We were waiting for Senorita Mendoza," explained Kennedy to both Whitney and her, "when Mr. Whitney happened along. I don't see Senora de Moche in the tea room. Perhaps we may as well sit out here in the corridor until she comes." It was evidently his desire to see how Whitney and Inez would act, for this was the first time we had ever seen them together. "We were talking of the treasure," resumed Whitney, omitting to mention the dagger. "Kennedy, we are not the only ones who have sought the peje grande, or rather are seeking it. But we are, I believe, the only ones who are seeking it in the right place, and," he added, leaning over confidentially, "your father, Senorita, was the only one who could have got the concession, the monopoly, from the government to seek in what I am convinced will be the right place. Others have found the 'little fish.' We shall find the 'big fish.'" He had raised his voice from the whisper, and I caught Inez looking anxiously at Kennedy, as much as to say, "You see? He is like the rest. His mind is full of only one subject." "We shall find it, too," he continued, still speaking in a high-pitched key, "no matter what obstacles man or devil put in our way. It shall be ours--for a simple piece of engineering--ours! The curse of Mansiche--pouf!" He snapped his fingers defiantly as he said it. There was an air of bravado about his manner. I could not help feeling that perhaps in his heart he was not so sure of himself as he would have others think. I watched him closely, and could see that he had suddenly become even more excited than before. It was as though some diabolical force had taken possession of his brain, and he fought it off, but was unable to conquer. Kennedy followed the staring glance of Whitney's eyes, which seemed almost to pop out of his head, as though he were suffering from the disease exophthalmic goitre. I looked also. Senora de Moche had come from the elevator, accompanied by Alfonso, and was walking slowly down the corridor. As she looked to the right and left, she had caught sight of our little group, all except Whitney, with our backs toward her. She was now looking fixedly in our direction, paying no attention to anything else. Whitney was a study. I wondered what could be the relations between these two, the frankly voluptuous woman and the calculating full-blooded man. Whitney, for his part, seemed almost fascinated by her gaze. He rose as she bowed, and, for a moment, I thought that he was going over to speak to her, as if drawn by that intangible attraction which Poe has so cleverly expressed in his "Imp of the Perverse." For, clearly, one who talked as Whitney had just been talking would have to be on his guard with that woman. Instead, however, he returned her nod and stood still, while Kennedy bowed at a distance and signalled to her that we would be in the tea room directly. I glanced up in time to see the anxious look on the face of Inez change momentarily into a flash of hatred toward the Senora. At the same moment Alfonso, who was on the other side of his mother, turned from looking at a newsstand which had attracted his attention and caught sight of us. There was no mistaking the ardent glance which he directed at the fair Peruvian at my side. I fancied, too, that her face softened a bit. It was only for a moment, and then Inez resumed her normal composure. "I won't detain you any longer," remarked Whitney. "Somehow, when I start to talk about my--our plans down there at Truxillo I could go on all night. It is marvellous, marvellous. We haven't any idea of what the future holds in store. No one else in all this big city has anything like the prospect which is before us. Gradually we are getting everything into shape. When we are ready to go ahead, it will be the sensation of Wall Street--and, believe me, it takes much to arouse the Street." He may have been talking wildly, but it was worth while to listen to him. For, whatever else he was, Whitney was one of the most persuasive promoters of the day. More than that, I could well imagine how any one possessed of an imagination susceptible to the influence of mystery and tradition would succumb to the glittering charm of the magic words, peje chica, and feel all the gold-hunter's enthusiasm when Whitney brought him into the atmosphere of the peje grande. As he talked, visions of hidden treasure seemed to throw a glamour over everything. One saw golden. "You will excuse us?" apologized Kennedy, taking Inez by the arm. "If you are about, Mr. Whitney, I shall stop to chat with you again on the way out." "Remember--she is a very remarkable woman," said Whitney, as we left him and started for the tea room. His tone was not exactly one of warning, yet it seemed to have cost him an effort to say it. I could not reconcile it with any other idea than that he was trying to use her in his own plans, but was still in doubt of the outcome. We parted from him and entered the darkened tea room, with its wicker tables and chairs, and soft lights, glowing pinkly, to simulate night in the broad light of afternoon outside. A fountain splashed soothingly in the centre. Everything was done to lend to the place an exotic air of romance. Alfonso and his mother had chosen a far corner, deeper than the rest in the shadows, where two wicker settees were drawn up about a table, effectually cutting off inquisitive eyes and ears. Alfonso rose as we approached and bowed deeply. I could not help watching the two women as they greeted each other. "Won't you be seated?" he asked, pulling around one of the wicker chairs. It was then that I saw how he had contrived to sit next to Inez, while Kennedy manoeuvred to sit on the end, where he could observe them all best. It was a rather delicate situation, and I wondered how Kennedy would handle it, for, although Alfonso had done the inviting, it was really Craig who was responsible for allowing Inez to accept. The Senora seemed to recognize it, also, for, although she talked to Inez, it was plain she had him in mind. "I have heard from Alfonso about the cruel death of your father," she began, in a softened tone, "and I haven't had a chance to tell you how deeply I sympathize with you. Of course, I am a much older woman than you, have seen much more trouble. But I know that never in life do troubles seem keener than when life is young. And yours has been so harsh. I could not let it pass without an opportunity to tell you how deeply I feel." She said it with an air of sincerity that was very convincing, so convincing, in fact, that it shook for the moment the long chain of suspicion that I had been forging both of her and her son. Could she be such a heartless woman as to play on the very heartstrings of one whom she had wronged? I was shaken, moreover, by the late discovery by Kennedy of the foot-prints. The Senorita murmured her thanks for the condolences in a broken voice. It was evident that whatever enmity she bore against the Senora it was not that of suspicion that she was the cause of her father's death. "I can sympathize with you the more deeply," she went on, "because only lately I have lost a very dear brother myself. Already I have told Professor Kennedy something about it. It was a matter of which I felt I must speak to you, for it may concern you, in the venture in which Mr. Lockwood and your father were associated, and into which now Mr. Whitney has entered." Inez said nothing, and Craig bowed, as though he, too, wished her to go on. "It is about the 'big fish' and the concession which your father has obtained from the government to search for it." The Senorita started and grew a bit pale at the reference, but she seemed to realize that it was something she ought to hear, and steeled herself to it. "Yes," she murmured, "I understand." "As you no doubt know," resumed the Senora, "no one has had the secret of the hiding-place. It has been by mere tradition that they were going to dig. That secret, you may know or may not know now, was in reality contained in the inscriptions on an old Inca dagger." Inez shuddered at the mention of the weapon, a shudder that was not lost on the Senora. "I have already told Professor Kennedy that both the tradition and the dagger were handed down in my own family, coming at last to my brother. As I said, I don't know how it happened, but somehow he seemed to be getting crazy, until he talked, and the dagger was stolen from him. It came finally into Professor Norton's hands, from whom it was in turn stolen." She looked at Inez searchingly, as if to discover just what she knew. I wondered whether the Senora suspected the presence of Lockwood's footprints in the sarcophagus in the Museum--what she would do if she did. "After he lost it," she continued reminiscently, "my brother threw himself one day into Lake Titicaca. Everywhere the trail of that dagger, of the secret of the Gold of the Gods has been stained by blood. To-day the world scoffs at curses. But surely that gold must be cursed. It has been cursed for us and ours." She spoke bitterly; yet might she not mean that the loss of the dagger, the secret, was a curse, too? "There is one other thing I wish to say, and then I will be through. Far back, when your ancestors came into the country of mine, an ancestor of your father lost his life over the treasure. It seems as if there were a strange fatality over it, as if the events of to-day were but living over the events of yesterday. It is something that we cannot escape--fate." She paused a moment, then added, "Yet it might be possible that the curse could be removed if somehow we, who were against each other then, might forget and be for each other now." "But Senorita Mendoza has not the dagger," put in Kennedy, watching her face keenly, to read the effect of his remark. "She has no idea where it may be." "Then it is pure tradition on which Mr. Lockwood and Mr. Whitney depend in their search for the treasure?" flashed back the Senora quickly. Kennedy did not know, but he did not confess it. "Until we know differently, we must take their word for it," he evaded. "It was not that that I meant, however," replied Senora de Moche. "I meant that we might stop the curse by ceasing to hunt for the treasure. It has never done any one good; it never will. Why tempt fate, then? Why not pause before it is too late?" I could not quite catch the secondary implication of her plan. Did it mean that the treasure would then be left for her family? Or was she hinting at Inez accepting Alfonso's suit? Somehow I could not take the Senora at her face value. I constantly felt that there was an ulterior motive back of her actions and words. I saw Craig watching the young man's face, and followed his eyes. There was no doubt of how he took the remark. He was gazing ardently at Inez. If there had ever been any doubt of his feelings, which, of course, there had not, this would have settled it. "One thing more," added the Senora, as though she had had an afterthought, "and that is about Mr. Lockwood and Mr. Whitney. Let me ask you to think it over. Suppose they have not the dagger. Then are their chances better than others? And if they have"--she paused to emphasize it--"what does that mean?" Kennedy had turned his attention to the Senorita. It was evident that the dilemma proposed by de Moche was not without weight. She had now coloured a flaming red. The woman had struck her in a vital spot. "Mr. Lockwood is not here to defend himself," Inez said quietly. "I will not have him attacked by innuendo." She had risen. Neither the ardour of Alfonso nor the seeds of doubt of the Senora had shaken her faith. It was a test that Kennedy evidently was glad to have witnessed. For some day she might learn the truth about the foot-prints. He understood her character better. The Senora, too, had learned that if she were to bring pressure on the girl she might break her, but she would not bend. Without another word Inez, scarcely bowing stiffly, moved out of the tea room, and we followed, leaving the mother and son there, baffled. "I hope you will pardon me for allowing you to come here," said Kennedy, in a low voice. "I did it because there are certain things that you ought to hear. It was in fairness to you. I would not have you delude yourself about Mr. Whitney, about--Mr. Lockwood, even. I want you to feel that, no matter what you hear or see, you can come to me and know that I will tell you the truth. It may hurt, but it will be best." I thought he was preparing the way for a revelation about the foot-prints, but he said nothing more. "Oh, that woman!" she exclaimed, as if to change the subject. "I do not know, I cannot say, why she affects me so. I saw a change in my father, when he knew her. I have told you how he was, how sometimes I thought he was mad. Did you notice a change in Mr. Whitney, or haven't you known him long enough? And lately I have fancied that I see the same sort of change beginning in Mr. Lockwood. At times they become so excited, their eyes seem staring, as if some fever were wasting them away. Father seemed to see strange visions, and hear voices, was worse when he was alone than when he was in a crowd. Oh, what is it? I could think of nothing else, not even what she was saying, all the time I was with her." "Then you fear that in some way she may be connected with these strange changes?" asked Kennedy. "I don't know," she temporized; but the tone of her answer was sufficient to convey the impression that in her heart she did suspect something, she knew not what. "Oh, Professor Kennedy," she cried finally, "can't you see it? Sometimes--when she looks out of those eyes of hers--she almost makes people do as she pleases." We had come to the taxicab stand before the hotel, and Kennedy had already beckoned to a cab to take her home. As he handed her in she turned with a little shiver. "Don't please, think me foolish," she added, with bated breath, "but often I fear that it is, as we call it, the mal de ojo--the evil eye!" XIII THE POISONED CIGARETTE There was not a grain of superstition in Kennedy, yet I could see that he was pondering deeply what Inez Mendoza had just said. Was it possible that there might be something in it--not objectively, but subjectively? Might that very fear which the Senorita had of the Senora engender a feeling that would produce the very result that she feared? I knew that there were strange things that modern psychology was discovering. Could there be some scientific explanation of the evil eye? Kennedy turned and went back into the hotel, to keep his appointment with Whitney, and as he did so I reflected that, whatever credence might be given the evil-eye theory, there was something now before us that was a fact--the physical condition which Inez had observed in her father before his death, saw now in Whitney, and foresaw in Lockwood. Surely that in itself constituted enough of a problem. We found Whitney in the cafe, sitting alone in a leather-cushioned booth, and smoking furiously. I observed him narrowly. His eyes had even more than before that peculiar, staring look. By the manner in which his veins stood out I could see that his heart action must be very rapid. "Well," he remarked, as we seated ourselves, "how did you come out in your tete-a-tete?" "About as I expected," answered Kennedy nonchalantly. "I let it go on merely because I wanted Senorita Mendoza to hear certain things, and I thought that the Senora could tell them best. One of them related to the history of that dagger." I thought Whitney's eyes would pop out of his head. "What about it?" he asked. "Well," replied Kennedy briefly, "there was the story of how her brother had it and was driven crazy until he gave it up to somebody, then committed suicide by throwing himself into Titicaca. The other was the tradition that in the days after Pizarro a Mendoza was murdered by it, just as her father has now been murdered." Whitney was listening intently, and seemed to be thinking deeply of something. "Do you know," he said finally, with a nod to indicate that he knew what it was that Kennedy referred to, "I've been thinking of that de Moche woman a good deal since I left you with her. I've had some dealings with her." He looked at Kennedy shrewdly, as though he would have liked to ask whether she had said anything about him, but did not because he knew Kennedy would not tell. He was trying to figure out some other way of finding out. "Sometimes I think she is trying to double-cross me," he said, at length. "I know that when she talks to others about me she says many things that aren't so. Yet when she is with me everything is fine, and she is ready soon to join us, use her influence with influential Peruvians; in fact, there isn't anything she won't do--manana, to-morrow." All that Whitney said we now knew to be true. "She has one interesting dilemma, however, which I do not mind telling you," remarked Kennedy at length. "She cannot expect me to keep secret what she said before all of us. Inez Mendoza would mention it, anyhow." "What was that?" queried Whitney, dissembling his interest. "Why," replied Kennedy slowly, "it was that, with the plans for digging for the treasure which you say you have, suppose you and Lockwood and your associates have not the dagger--how are you better off than previous hunters? And supposing you have it--what does that imply?" Whitney thought a moment over the last proposition of the dilemma. "Imply?" he repeated slowly. Then the significance of it seemed to dawn on him, the possession of the dagger and its implication in regard to the murder of Mendoza. "Well," he answered, "we haven't the dagger. You know that. But, on the other hand, we think our plans for getting at the treasure are better than any one else has ever had, more certain of success." "Yet the possession of the dagger, with its inscription, is the only thing that absolutely insures success," observed Kennedy. "That's true enough," agreed Whitney. "Confound that man Norton. How could he be such a boob as to let the chance slip through his fingers?" "He never told you of it?" asked Kennedy. "Yes, he told me of the dagger, but hadn't read the inscription, he said," answered Whitney. "I was so busy at the time with Lockwood and Mendoza, who had the concession to dig for the treasure, that I didn't pay much attention to what Norton brought back. I thought that could wait until Lockwood had been persuaded to join the interests I represent." "Did Lockwood or Mendoza know about the dagger and its importance?" suggested Craig. "If they did, they never said anything about it," returned Whitney promptly. "Mendoza is dead. Lockwood tells me he knew nothing about it until very lately--since the murder, I suppose." "You suppose?" persisted Kennedy. "Are you sure that he knew nothing about it before?" "No," confessed Whitney, "I'm not sure. Only I say that he told me nothing of it." "Then he might have known?" "Might have. But I don't think it very probable." Whitney seemed to be turning something over in his mind. Suddenly he brought his fist down on the little round table before us, rattling the glasses. "Do you know," he exclaimed, "the more I think about it, the more convinced I am that Norton ought to be held to account for that loss! He ought to have known. Then the presumption is that he did know. By heaven, I'm going to have that fellow watched. I'm going to do it to-day, too. I don't trust him. He shall not double-cross me--even if that woman does!" I wondered whether Whitney was bluffing. If he was, he was making a lot of fuss over it. He talked more and more wildly, as he grew more excited over his latest idea. "I'll have detectives put on his trail," he blustered. "I'll talk it over with Lockwood. He never liked the man." "What did Lockwood say about Norton?" asked Kennedy casually. Whitney eyed us a moment. "Say," he ejaculated, "it was Norton brought you into this case, wasn't it?" "I cannot deny that," returned Kennedy quietly, meeting his eyes. "But it is Inez Mendoza now that keeps me in it." "So--you're another rival, are you?" purred Whitney sarcastically. "Lockwood and de Moche aren't enough. I have a sneaking suspicion that Norton himself is one of them. Now it's you, too. I suppose Mr. Jameson is another. Well, if I was ten years younger, I'd cut you all out, or know the reason why. Oh, YES, I think I will NOT tell you what Mr. Lockwood suspects." With every sentence the veins of Whitney's forehead stood out further, until now they were like whipcords. His eyes and face were fairly apoplectic. Slowly the conviction was forced on me. The man acted for all the world like one affected by a drug. "Well," he went on, "you may tell Norton for me that I am going to have him watched. That will throw a scare into him." At least it showed that the breach between Whitney and Norton was deep. Kennedy listened without saying much, but I knew that he was gratified. He was playing Lockwood against de Moche, the Senora against Inez. Now if Whitney would play himself against Norton, out of the tangle might emerge just the clues he needed. For when people get fighting among themselves the truth comes out. "Very well," remarked Craig, rising, with a hurried glance at Whitney's apoplectic face, "go as far as you like. I think we understand each other better, now." Whitney said nothing, but, rising also, turned on his heel and walked deliberately out of the cafe into the corridor of the Prince Edward Albert, leaving us standing there. Kennedy leaned over and swept up the ashes of Whitney's cigarettes which lay in the ash-tray, placing them, stubs and all, in an envelope, as he had done before. "We have one sample, already," he said. "Another won't hurt. You can never have too much material to work with. Let us see where he is going." Slowly we followed in the direction which Whitney had taken from the cafe. There was Whitney standing by the cigar-stand, gazing intently down the corridor. Kennedy and I moved over so that we could see what he was gazing at. Just then he started to walk hurriedly in the direction in which he was looking. "Senora de Moche!" exclaimed Craig, drawing me toward a palm. It was indeed she. She had left the tea room and gone to her own room. Now she was alighting from the elevator, and had started toward the main dining-room, when her eyes had rested on Whitney. In spite of all that he had said to us about her, he had received the glance as a signal and was fluttering over to her like a moth to a flame. What was the reason back of it all, I asked, as I thought of those wonderful eyes of hers? Was it a sort of auto-hypnotism? There was, I knew, a form of illusion known as ophthalmophobia--fear of the eye. It ranged from mere aversion at being gazed at all the way to the subjective development of real physical action from an otherwise trivial objective cause. Perhaps Inez was right about the eyes. One might fear them, and that fear might cause the precise thing to happen which the owner of the eyes intended. Still, as I reflected before, there was a much more important problem regarding eyes before us, that of the drug that was evidently being used in the cigarettes. What was it? There was no chance of our gleaning anything now from these two who made such a strange pair. Kennedy turned and went out of the nearest entrance of the hotel. "Central Park, West," he directed a cab driver, as we climbed in his machine; then to me, after giving the number, "I must see Inez Mendoza again before I can go ahead." Inez was not expecting us so soon after leaving her at the hotel, yet I think was just a little glad that we had come. "Did anything happen after I left?" she asked eagerly. "We went back and saw Mr. Whitney," returned Craig. "I believe you are right. He is acting queerly." "Alfonso called me up," she volunteered. "Was it about anything I should know?" queried Craig. "Well," she hesitated, "he said he hoped that nothing that had taken place would change our own relations. That was about all. He was the dutiful son, and made no attempt to explain anything that was said." Kennedy smiled. "You have not seen Mr. Lockwood since, I suppose?" he asked. "You always make me tell what I hadn't intended," she confessed, smiling back. "Yes, I couldn't help it. At least, I didn't see him. I called him up. I wanted to tell him what she had said and that it hadn't made any difference to me." "What did he say?" "I can't remember just how he put it, but I think he meant that it was something very much like that anonymous letter I received. We both feel that there is some one who wants to make trouble between us, and we are not going to let it happen." If she had known of Kennedy's discovery of the shoe-prints, I feel sure that, as far as we were concerned, the case would have ended there. She was in no mood to be convinced by such a thing, would probably have insisted that some one was wearing a second-hand pair of his shoes. Kennedy's eye had been travelling around the room as though searching for something. "May I have a cigarette out of that case over there?" he asked, indicating a box of them on a table. "Why--that is Mr. Lockwood's," she replied. "He left it here the last time he was here and I forgot to send it to him. Wait a minute. Let me get you some of father's." She left the room. The moment the door closed Kennedy reached over and took one from the case. "I have some of Lockwood's already, but another won't matter, as long as I can get it," he said. "I thought it was her father's. When she brings them, smoke one with me, and be careful to save the stub. I want it." A moment later she entered with a metal box that must have held several hundred. Kennedy and I each took one and lighted it, then for several minutes chatted as an excuse for staying. As for myself, I was glad enough to leave a pretty large stub, for I did not like it. These cigarettes, like those Whitney had offered us, had a peculiar flavour which I had not acquired a liking for. "You must let me know whether anything else develops from the meeting in the tea room," said Kennedy finally, rising. "I shall be at the laboratory some time, I think." XIV THE INTERFEROMETER Norton was waiting for us at the laboratory when we returned, evidently having been there some time. "I was on my way to my apartment," he began, "when I thought I'd drop in to see how things are progressing." "Slowly," returned Kennedy, throwing off his street clothes and getting into his laboratory togs. "Have you seen Whitney since I had the break with him?" asked Norton, a trifle anxiously. I wondered whether Kennedy would tell Norton what to expect from Whitney. He did not, however. "Yes," he replied, "just now we had an appointment with Senora de Moche and some others and ran into him at the hotel for a few moments." "What did he say about me?" queried Norton. "He hadn't changed his mind," evaded Kennedy. "Have you heard anything from him?" "Not a syllable. The break is final. Only I was wondering what he was telling people about me. He'll tell them something--his side of the case." "Well," considered Kennedy, as though racking his brain for some remark which he remembered, while Norton watched him eagerly, "I do recall that he was terribly sore about the loss of the dagger, and seemed to think that it was your fault." "I thought so, I knew it," replied Norton bitterly. "I can see it coming. All the trustees will hear of my gross negligence in letting the Museum be robbed. I suppose I ought to sit up there all night. Oh, by the way, there's another thing I wanted to ask you. Have you ever done anything with those shoe-prints you found in the dust of the mummy case?" I glanced at Kennedy, wondering whether he felt that the time had come to reveal what he had discovered. He said nothing for a moment, but reached into a drawer and pulled out the papers, which I recognized. "Here they are," he said, picking out the original impression which he had taken. "Yes," repeated Norton, "but have you been able to do anything toward identifying them?" "I found it rather hard to collect prints of the shoes of all of those I wished to compare. But I have them at last." "And?" demanded Norton, leaning forward tensely. "I find that there is one person whose shoe-prints are precisely the same as those we found in the Museum," went on Kennedy, tossing over the impression he had taken. Norton scanned the two carefully. "I'm not a criminologist," he said excitedly, "but to my untrained eye it does seem as though you had here a replica of the first prints, all right." He laid them down and looked squarely at Kennedy. "Do you mind telling me whose feet made these prints?" "Turn the second over. You will see the name written on it." "Lockwood!" exclaimed Norton in a gasp as he read the name. "No--you don't mean it." "I mean nothing less," repeated Kennedy firmly. "I do not say what happened afterwards, but Lockwood was in the Museum, hiding in the mummy case, that night." Norton's mind was evidently working rapidly. "I wish I had your power of deduction, Kennedy," he said, at length. "I suppose you realize what this means?" "What does it mean to you?" asked Kennedy, changing front. Norton hesitated. "Well," he replied, "it means to me, I suppose, what it means to any one who stops to think. If Lockwood was there, he got the dagger. If he had the dagger--it was he who used it!" The inference was so strong that Craig could not deny it. Whether it was his opinion or not was another matter. "It fits in with other facts, too," continued Norton. "For instance, it was Lockwood who discovered the body of Mendoza." "But the elevator boy took Lockwood up himself," objected Craig, more for the sake of promoting the discussion than to combat Norton. "Yes--when he 'discovered' the thing. But it must have been done long before. Who knows? He may have entered. The deed might have been done. He may have left. No one saw him come or go. What then more likely to cover himself up than to return when he knew that his entrance would be known, and find the thing himself?" Norton's reasoning was clever and plausible. Yet Kennedy scarcely nodded his head, one way or the other. "You were acquainted with Lockwood?" he asked finally. "I mean to say, of course, before this affair." "Yes, I met him in Lima just as I was starting out on my expedition. He was preparing to come to New York." "What did you think of him then?" "Oh, he was all right, I suppose. He wasn't the sort who would care much for an archaeologist. He cared more for a prospector going off into the hills than he did for me. And I--I admit that I am impossible. Archaeology is my life." Norton continued to study the prints. "I can hardly believe my eyes," he murmured; then he looked up suddenly. "Does Whitney know about this--or Lockwood?" Kennedy shook his head negatively. "Because," pursued Norton, "an added inference to that I spoke of would be that the reason why they are so sure that they will find the treasure is that they are not going on tradition, as they say, but on the fact itself." "A fair conclusion," agreed Craig. "I wish the break could have been postponed," continued Norton. "Then I might have been of some service in my relation to Whitney. It's too late for me to be able to help you in that direction now, however." "There is something you can do, though," said Craig. "I shall be delighted," hastened Norton. "What is it?" "You know Senora de Moche and Alfonso?" "Yes." "I wish that you would cultivate their acquaintance. I feel that they are very suspicious of me. Perhaps they may not be so with you." "Is there any special thing you want to find out?" "Yes--only I have slight hopes of doing so. You know that she is on most intimate terms with Whitney." "I'm afraid I can't do much for you, then. She'll fight shy of me. He'll tell her his story." "That will make no difference. She has already warned me against him. He has warned against her. It's a most remarkable situation. He is trying to get her into some kind of deal, yet all the time he is afraid she is double-crossing him. And at the same time he obeys her--well, like Alfonso would Inez if she'd only let him." Norton frowned. "I don't like the way they hover about Inez Mendoza," he remarked. "Perhaps the Senora is after Whitney, while her son is after Inez. Lockwood seems to be impervious to her. Yes, I'll undertake that commission for you, only I can't promise what success I'll have." Kennedy restored the shoe-prints to the drawer. "I think that's gratifying progress," went on Norton. "First we know who stole the dagger. We know that the dagger killed Mendoza. You have even determined what the poison on the blade was. It seems to me that it remains only to determine who struck the actual blow. I tell you, Kennedy, Whitney will regret the day that he ever threw me over on so trivial a pretext." Norton was pacing up and down excitedly now. "My only fear is," he went on, "what the shock of such a thing will be on that poor little girl. First her father, then Lockwood. Why--the blow will be terrible. You must be careful, Kennedy." "Never fear about that," reassured Craig. "Not a word of this has been breathed to her yet. We are a long way from fixing the guilt of the murder; inference is one thing, fact another. We must have facts. And the facts I want, which you may be able to get, relate to the strange actions of the de Moches." Norton scanned Kennedy's face for some hint of what was back of the remark. But there was nothing there. "They will bear watching, all right," he said, as he rose to go. "Old Mendoza was never quite the same after he became so intimate with her. And I think I can see a change in Whitney." "What do you attribute it to?" asked Kennedy, without admitting that it had attracted his attention, too. "I haven't the slightest idea," confessed Norton. "Inez is as afraid of her as any of the rest," remarked Kennedy thoughtfully. "She says it is the evil eye." "Not an uncommon belief among Latin-Americans," commented Norton. "In fact, I suppose there are people among us who believe in the evil eye yet. Still, you can hardly blame that little girl for believing it is almost anything. Well, I won't keep you any longer. I shall let you know of anything I find out from the de Moches. I think you are getting on remarkably." Norton left us, his face much brighter than it had been when we met him at the door. Kennedy, alone at last in the laboratory, went over to a cabinet and took out a peculiar-looking apparatus, which seemed, as nearly as I can describe it, to consist of a sort of triangular prism, set with its edge vertically on a rigid platform attached to a massive stand of brass. "Norton seems to have suddenly become quite solicitous of the welfare of Senorita Mendoza," I hazarded, as he worked over the adjustment of the thing. Kennedy smiled. "Every one seems to be--even Whitney," he returned, twisting a set-screw until he had the alignment of the various parts as he wanted it. The telephone bell rang. "Do you want to answer it?" I asked Craig. "No," he replied, not even looking up from his work. "Find out who it is. Unless it is something very important say I am out on an investigation and that you have heard from me; that I shall not be either at the laboratory or the apartment until tomorrow morning. I must get this done to-night." I took down the receiver. "Hello, is this Professor Kennedy?" I recognized a voice. "No," I replied. "Is there any message I can take?" "This is Mr. Lockwood," came back the information I had already guessed. "When do you expect him?" "It's Lockwood," I whispered to Craig, my hand over the transmitter. "See what he wants," returned Craig. "Tell him what I told you." I repeated Kennedy's message. "Well, that's too bad," replied Lockwood. "I've just seen Mr. Whitney, and he tells me that Kennedy and you are pretty friendly with Norton, Of course, I knew that. I saw you at the Mendozas' together the first time. I'd like to have a talk with him about that man. I suppose he has told you all his side of the story of his relations with Whitney." I am, if anything, a good listener, and so I said nothing, not even that he had better tell it to Kennedy in the morning, for it was such a novelty to have any of these people talk voluntarily that I really didn't much care whether I believed what they said or not. "I used to know him down in Lima, you know," went on Lockwood. "What I want to say has to do with that dagger he says was stolen. I want to tell what I know of how he got it. There was an Indian mixed up in it who committed suicide--well, you tell Kennedy I'll see him in the morning." Lockwood rang off, and I repeated what he had told me, as Kennedy continued to adjust the apparatus. "Say," I exclaimed, as I finished. "That was a harry's of a commission you gave Norton just now, watching the de Moches. Why, they'd eat him alive if they got a chance, and I don't know that all's like a Sunday school on his part. Lockwood doesn't seem to think so." Kennedy smiled quietly. "That was why I asked him to do it," he returned. "I thought that he wouldn't let much escape him. They all seem so down on him, he'll have to watch out. It will keep him busy, too, and that means a chance for us to work." He had finished setting up the machine, and now went over to another drawer, from which he took the envelope of stubs which we had taken down at Whitney's office first. Then from the pocket of his street coat he drew both the second envelope of ashes and stubs, the whole cigarette from Lockwood's case, and the stubs which both of us had saved from the cigarettes that had once belonged to Mendoza. Carefully he separated and labelled them all, so that there would be no chance for them to get mixed up. Then he picked up one of the stubs and lighted it. The smoke curled up in wreaths between a powerful light and the peculiar instrument, while Craig peered through a lens, manipulating the thing with exhaustless patience and skill. I watched him curiously, but said nothing, for he was studying something carefully, and I did not want to interrupt his train of thought. Finally he beckoned me over. "Can you make anything out of that?" he asked. I looked through the eye-piece, also. On a sort of fine grating all I could see was a number of strange lines. "If you want an opinion from me," I said, with a laugh, "you'll have to tell me first what I am looking at." "That," he explained, as I continued to gaze, "is one of the latest forms of the spectroscope, known as the interferometer, with delicately ruled gratings in which power to resolve the straight, close lines in the spectrum is carried to the limit of possibility. A small watch is delicate. But it bears no comparison to the delicacy of these defraction spectroscopes. "Every substance, you know, is, when radiating light, characterized by what at first appears to be almost haphazard sets of spectral bands without relation to one another. But they are related by mathematical laws, and the apparent haphazard character is only the result of our lack of knowledge of how to interpret the results." He resumed his place at the eye-piece to check over his results. "Walter," he said finally, looking up at me with a twinkle in his eye, "I wish that you'd go out and find me a cat." "A cat?" I repeated. "Yes, a cat--felis domesticus, if it sounds better that way--a plain, ordinary cat." I jammed on my hat and, late as it was, sallied forth on this apparently ridiculous mission. Several belated passers-by and a policeman watched me as though I were a house-breaker, and I felt like a fool, but at last, by perseverance and tact, I managed to capture a fairly good specimen of the species, and carried it in my arms to the laboratory with some profanity and many scratches. XV THE WEED OF MADNESS In my absence Craig had set to work on a peculiar apparatus, as though he were distilling something from several of the cigarette stubs which he had been studying by means of the interferometer. "Here's your confounded cat," I ejaculated, as I placed the unhappy feline in a basket and waited patiently until finally he seemed to be rewarded for his patient labours. It was well along toward morning when he obtained in a test-tube a few drops of a colourless, odourless liquid. "My interferometer gave me a clue," he remarked, as he held the tube up with satisfaction. "Without the tell-tale line in the spectrum which I was able to discover by its use I might have been hunting yet for it. It is so rare that no one would ever have thought, offhand, I suppose, to look for it. But here it is, I'm sure, only I wanted to be able to test it." "So you are not going to try it on yourself," I said sarcastically, referring to his last experiment with a poison. "This time you are going to make the cat the dog." "The cat will be better to test it on than a human being," he replied, with a glance that made me wince, for, after his performance with the curare, I felt that once the scientific furore was on him I might be called upon to become an unwilling martyr to science. It was with an air of relief, both for himself and my own peace and safety, that I saw him take the cat out of the basket and hold her in his arms, smoothing her fur gently, to quiet the feelings that I had severely ruffled. Then with a dropper he sucked up a bit of the liquid from the test-tube. I watched him intently as he let a small drop fall into the eye of the cat. The cat blinked a moment, and I bent over to observe it more closely. "It won't hurt the cat," he explained, "and it may help us." As I looked at the cat's eye it seemed to enlarge, even under the glare of a light, shining forth, as it were, like the proverbial cat's eye under a bed. What did it mean? Was there such a thing, I wondered hastily, as the drug of the evil eye? "What have you found?" I queried. "Something very much like the so-called 'weed of madness,' I think," he replied slowly. "The weed of madness?" I repeated. "Yes. It is similar to the Mexican toloache and the Hindu datura, which you must have heard about." I had heard of these weird drugs, but they had always seemed to be so far away and to belong rather to the atmosphere of civilizations different from New York. Yet, I reflected, what was to prevent the appearance of anything in such a cosmopolitan city, especially in a case so unusual as that which had so far baffled even Kennedy's skill? "You know the jimson weed--the Jamestown weed, as it is so often called?" he continued, explaining. "It grows almost everywhere in the world, but most thrivingly in the tropics. All the poisons that I have mentioned are related to it in some way, I believe." "I've seen the thing in lots and fields," I replied, "but I never thought it was of much importance." "Well," he resumed, "the jimson weed on the Pacific coast, in some parts of the Andes, has large white flowers which exhale a faint, repulsive odour. It is a harmless-looking plant, with its thick tangle of leaves, a coarse green growth, with trumpet-shaped flowers. But to one who knows its properties it is quite too dangerously convenient for safety." "But what has that to do with the evil eye?" I asked. "Nothing; but it has much to do with the cigarettes that Whitney is smoking," he went on positively. "Those cigarettes have been doped!" "Doped?" I interrogated, in surprise. "With this weed of madness, as you call it?" "No, it isn't toloache that was used," he corrected. "I think it must be some particularly virulent variety of the jimson weed that was used, though that same weed in Mexico is, I am sure, what there they call toloache. Perhaps its virulence in this case lies in the method of concentration in preparing it. For instance, the seeds of the stramonium, which is the same thing, contain a much higher percentage of poison than the leaves and flowers. Perhaps the seeds were used. I can't say. But, then, that isn't at all necessary. It is the fact of its use that concerns us most now." He took a drop of the liquid which he had isolated and added a drop of nitric acid. Then he evaporated it by gentle heat and it left a residue slightly yellow. Next he took from the shelf over his table a bottle marked "Alcoholic Solution--Potassium Hydrate." He opened it and let a drop fall on the place where the liquid had evaporated. Instantly the residue became a beautiful purple, turning rapidly to violet, then to dark red, and, finally, it disappeared altogether. "Stramonium, all right," he nodded, with satisfaction at the achievement of his night's labours. "That was known as Vitali's test. Yes, there was stramonium in those cigarettes--datura stramonium--perhaps a trace of hyoscyamine." I tried to look wise, but all I could think of was that, whatever his science showed me now, my instinct had been enough to prompt me not to smoke those cigarettes, though, of course, only Kennedy's science could tell what it was that caused that instinctive aversion. "They are all like atropine, mydriatic alkaloids," he proceeded, "so called from the effect they have on the eye. Why, one-one hundred thousandth of a grain will affect the eye of a cat. You saw how it acted on our subject. It is more active in that way than atropine. Better yet, you remember how Whitney's eyes looked, how Inez said her father stared, and how she feared for Lockwood?" "I remember," I said, still not able to detach the evil-eye idea quite from my mind. "How about the Senora's eyes? What makes them so--well, effective?" "Oh," Craig answered quickly, "her pupils were normal enough. Didn't you notice that? It was the difference in Whitney's and the others' that first suggested making some tests." "What is the effect?" I asked, wondering whether it might have contributed to the cause of Mendoza's death. "The concentrated poison which has been used in these cigarettes does not kill--at least not outright. It is worse than that. Slowly it accumulates in the system. It acts on the brain." I was listening, spellbound, as he made his disclosure. No wonder, I thought, even a scientific criminal stood in awe of Craig. "Of all the dangers to be met with in superstitious countries, these mydratic alkaloids are among the worst. They offer a chance for crimes of the most fiendish nature--worse than with the gun or the stiletto. They are worse because there is so little fear of detection. That crime is the production of insanity!" Horrible though the idea, and repulsive, I could not doubt it in the face of Craig's investigations and what I had already seen with my own eyes. In fact, it was necessary for me only to recall the mild sensations I myself had experienced, in order to be convinced of the possible effect intended by the insidious poison contained in the many cigarettes which Whitney, for instance, had smoked. "But don't you suppose they know it?" I wondered. "Can't they tell it?" "I suppose they have gradually become accustomed to it," Craig ventured. "If you have ever smoked one particular brand of cigarette you must have noticed how the manufacturer can gradually substitute a cheaper grade of tobacco without any large number of his patrons knowing anything about it. I imagine it might have been done in some way like that." "But you would think they'd feel the effect and attribute it to smoking." "Perhaps they do feel the effect. But when it comes to tracing causes, some people are loath to admit that tobacco and liquor can be the root of the evil. No, some one is slipping these cigarettes in on them, perhaps substituting the doped brand for those that are ordered. If you will notice, both Whitney and Lockwood have cigarettes that are made especially for them. So had Mendoza. It is a circumstance which some one has turned to account, though how and by whom the substitution has been made I cannot say yet. I wish I had time to follow out this one line, to the exclusion of everything else. But I've got to keep my fingers on every rope at once, else the thing will pull away from me. It is enough for the present that we know what the poison is. I shall take up the tracing of the person who is administering it the moment I get a hint." It was almost daylight before Craig and I left the laboratory after his discovery of the manner of the cigarette poisoning by stramonium. But that was the only way in which he was able to make progress--taking time for each separate point by main force. I was thoroughly tired, though not so much so that my dreams were not haunted by a succession of baleful eyes peering at me from the darkness. I slept late, but was awakened by a knocking on the door. As I rose to answer it I saw through the open door of Kennedy's room that he had been about early and must already be at the laboratory. How he did it I don't know. My own newspaper experience had made me considerable of a nighthawk. But I always paid for it by sleeping the next day. With Kennedy, when he was on a case, even five hours of sleep was more than he seemed able to stand. "Hello, Jameson," greeted a voice, as I opened the door. "Is Kennedy in--oh, he hasn't come back yet?" It was Lockwood, at first eager to see Craig, then naturally crestfallen because he saw that he was not there. "Yes," I replied, rubbing my eyes. "He must be at the laboratory. If you'll wait a minute while I slip on my clothes, I'll walk over there with you." While I completed my hasty toilet, Lockwood sat in our living room, gazing about with fascination at the collection of trophies of the chase of criminals. "This is positively a terrifying array of material, Jameson," he declared, as at last I emerged. "Between what Kennedy has here and what he has stowed away in that laboratory of his, I wonder that any one dares be a crook." I could not help eying him keenly. Could he have spoken so heartily if he had known what it was, damning to himself, that Kennedy had tucked away in the laboratory? If he knew, he must have been a splendid actor, one of those whom only the minute blood-pressure test of the sphygmograph could induce to give up a secret, and then only in spite of himself. "It is wonderful," I agreed. "Are you ready?" We left the apartment and walked along in the bracing morning air toward the campus and the Chemistry Building. Sure enough, as I had expected, Kennedy was in his laboratory. As we entered he was verifying his experiments and checking over his results, carefully endeavouring to isolate any of the other closely related mydriatic alkaloids that might be contained in the noxious fumes of the poisoned tobacco. Though Craig was already convinced of what was going on, I knew that he always considered it a matter of considerable medico-legal importance to be exact, for if the affair ever came to the stage of securing an indictment the charge could be sustained only by specific proof. As we appeared in the door, however, he laid aside his work, and greeted us. "I suppose Jameson has already told you that I called you up last night--and what I said?" began Lockwood. Kennedy nodded. "It was something about Norton, wasn't it?" Lockwood leaned over impressively and almost whispered: "Of course, you are in no position to know, but there are ugly rumours current down in Lima among the natives regarding that dagger." Kennedy did not appear to be particularly impressed. "Is that so?" he said merely. "What are they?" "Well," resumed Lockwood, "I wasn't in Lima at the time. I was up here. But they tell me that there was something crooked about the way that that dagger was got away from an Indian--a brother of Senora de Moche." "Yes," replied Kennedy, "I know something about it. He committed suicide. But what has that to do with Norton?" Lockwood hesitated, then shrugged his shoulders. "I should think the inference was plain," he insinuated. Then, looking at Craig fixedly, as though to take his measure, he added, "We are not out of touch with what is going on down there, even if we are several thousand miles away." I wondered whether he had any information more than we had already obtained by X-raying the letter to Whitney signed "Haggerty." If he had, it was not his purpose, evidently, yet to disclose it. I felt from his manner that he was not playing a trump-card, but was just feeling us out by this lead. "There was some crooked business about that dagger down there as well as here," he pursued. "There are many interests connected with it. Don't you think that it would be worth while watching Norton?" he paused, then added: "We do--and we're going to do it." "Thank you very much," returned Kennedy quietly. "Mr. Whitney has already told me he intended to do so." Lockwood eyed us critically, as though not quite sure what to make of the cool manner in which Craig took it. "I think if I were you," he said at length, "I'd keep a close watch on the de Moches, both of them, too." "Exactly," agreed Craig, without showing undue interest. Lockwood had risen. "Well," he snapped, "you may not think much of what I am telling you now. But just wait until OUR detectives begin to dig up facts." No sooner had he left than I turned to Craig. "What was that?" I asked. "A plant?" "Perhaps," he returned, clearing up the materials which he had been using. The telephone rang. "Hello, Norton," I heard Craig answer. "What's that? You are shadowed by some one--you think it is by Whitney?" I had been expecting something of the sort, and listened attentively, but it was impossible to gather the drift of the one-sided conversation. As Kennedy hung up the receiver I remarked, "So it was not a bluff, after all." "I think my plan is working," he remarked thoughtfully. "You heard what he said? He guesses right the first time, that it is Whitney. The last thing he said was, 'I'll get even! I'll take some action!' and then he rang off. I think we'll hear something soon." Instead of going out, Kennedy pulled out the several unsigned letters we had collected, and began the laborious process of studying the printing, analyzing it, in the hope that he might discover some new clue. XVI THE EAR IN THE WALL Perhaps an hour later our laboratory door was flung open suddenly, and both Kennedy and I leaped to our feet. There was Inez Mendoza, alone, pale and agitated. "Tell me, Professor Kennedy," she cried, her hands clasped before her in frantic appeal, "tell me--it isn't true--is it? He wasn't there--no--no--no!" She would have fainted if Craig had not sprung forward and caught her in time to place her in our only easy-chair. "Walter," he said, "quick--that bottle of aromatic spirits of ammonia over there--the second from the left." I handed it to him, and threw open the window to allow the fresh air to blow in. As I did so one of the papers Kennedy had been studying blew off the table, and, as luck would have it, fell almost before her. She saw it, and in her hypersensitive condition recognized it instantly. "Oh--that anonymous letter!" she cried. "Tell me--you do not think that--the friend of my father's that it warned me to beware of--was--" She did not finish the sentence. She did not need to do so. "Please, Senorita," pleaded and soothed Kennedy, "try to be calm. What has happened? Tell me. What is it?" The ammonia and the fresh air seemed to have done their work, for she managed to brace herself, gripping the arms of the chair tightly and looking up searchingly into Craig's face. "It's about Chester," she managed to gasp; then seemed unable to go on. It was the first time I had ever heard her use Lockwood's first name, and I knew that something had stirred her emotions more deeply than at any time since the death of her father. "Yes," prompted Kennedy. "Go on." "I have heard that you found foot-prints, shoe-prints, in the dust in the Museum after the dagger was stolen," she said, speaking rapidly, suppressing her feelings heroically. "Since then you have been collecting prints of shoes--and I've heard that the shoe-prints that were found are those of--of Mr. Lockwood. Oh, Professor Kennedy, it cannot be--there must be some mistake." For a moment Kennedy did not say anything. He was evidently seeking some way in which to lead up to the revelation of the truth without too much shock. "You remember that time in the tea room when we were sitting with Senora de Moche?" he asked finally. "Yes," she said shortly, as though the very recollection were disagreeable to her. Kennedy, however, had a disagreeable task, and he felt that it must be performed in the kindest manner. "You remember then that she said she had one thing more to say, that it was about Mr. Whitney and Mr. Lockwood." She was about to interrupt, but he hurried on, giving her no chance to do so. "She asked you to think it over. Suppose they did not have the dagger, she said. Then were their chances of finding the treasure any better than any one else had? And if they did have it, she asked what that meant. It is a dilemma, my dear Senorita, which you must meet some time. Why not meet it now?" Her face was set. "You will remember, also, Professor Kennedy," she said, with a great effort controlling her voice, "that I said that Mr. Lockwood was not there to defend himself and I would not have him attacked by innuendo. I meant it to the Senora--I mean it to you!" She had also meant it to defy him; but as she proceeded her voice broke, and before she knew it her nature had triumphed, and she was alternately sobbing and pleading. For a minute or two Kennedy let her give vent to her emotions. "It cannot be. It cannot be," she sobbed over and over. "He could not have been there. He could not have done it." It was a terrible thing to have to disillusion her, but it was something now that had to be done. Kennedy had not sought to do so. He had postponed it in the hope of finding some other way. But now the thing was forced upon him. "Who told you?" he asked finally. "I was trying to read, to keep my mind occupied, as you asked me, when Juanita told me that there was some one in the living room who wanted to see me--a man. I thought it was either you or Mr. Jameson. But it was--Professor Norton--" Kennedy and I exchanged glances. That was the action in revenge to Lockwood and Whitney which he had contemplated over the telephone. It was so cruel and harsh that I could have hated him for it, the more so as I recollected that it was he himself who had cautioned us against doing the very thing which now he had done in the heat of passion. "Oh," she wailed, "he was very kind and considerate about it. He said he felt that it was his duty to tell me, that he would be anything, like an older brother, to me; that he could not see me blinded any longer to what was going on, and everybody knew, but had not love enough for me to tell. It was such a shock. I could not even speak. I simply ran from the room without another word to him, and Juanita found me lying on the bed. Then--I decided--I would come to you." She paused, and her great, deep eyes looked up pathetically. "And you," she added bitterly, "you are going to tell me that he was right, that it is true. You can't prove it. Show me what it is that you have. I defy you!" Somehow, as she rested and relieved her feelings, a new strength seemed to come to her. It was what Kennedy had been waiting for, the reaction that would leave her able for him to go on and plan for the future. He reached into a drawer of a cabinet and pulled out the various shoe-prints which he had already shown Norton, and which he had studied and restudied so carefully. "That is the print of the shoe in the dust of the Egyptian sarcophagus of the Museum," he said quietly. "Some one got in during the daytime and hid there until the place was locked. That is the print of Alfonso de Moche's shoe, that of Mr. Whitney's, and that of Mr. Lockwood's." He said it quickly, as though trying to gloss it over. But she would not have it that way. She felt stronger, and she was going to see just what there was there. She took the prints and studied them, though her hand trembled. Hers was a remarkable mind. It took only seconds to see what others would have seen only in minutes. But it was not the reasoning faculty that was aroused by what she saw. It sank deep into her heart. She flung the papers down. "I don't believe it!" she defied. "There is some mistake. No--it cannot be true!" It was a noble exhibition of faith. I think I have never seen any instant more tense than that in Kennedy's laboratory. There stood the beautiful girl declaring her faith in her lover, rejecting even the implication that it might have been he who had taken the dagger, perhaps murdered her father to insure the possession of her father's share of the treasure as well as the possession of herself. Kennedy did not try to combat it. Instead he treated her very intuitions with respect. In him there was room for both fact and feeling. "Senorita," he said finally, in a voice that was deep and thrilling with feeling, "have I ever been other than a friend to you? Have I ever given you cause to suspect even one little motive of mine?" She faced him, and they looked into each other's eyes an instant. But it was long enough for the man to understand the woman and she to understand him. "No," she murmured, glancing down again. "Then trust me just this once. Do as I ask you." For an instant she struggled with herself. What would he ask? "What is it?" she questioned, raising her eyes to him again. "Have you seen Mr. Lockwood?" "No." "Then, I want you to see him. Surely you wish to have no secrets from him any more than you would wish him to have anything secret from you. See him. Ask him frankly about it all. It is the only fair thing to him--it is only fair to yourself." Senorita Mendoza was no coward. "I--I will," she almost whispered. "Splendid!" exclaimed Kennedy in admiration. "I knew that you would. You are not the woman who could do otherwise. May I see that you get home safely? Walter, call a taxicab." Senorita Mendoza was calmer, though pale and still nervous, when I returned. Kennedy handed her into the car and then returned to the laboratory for two rather large packages, which he handed to me. "You must come along with us, Walter," he said. "We shall need you." Scarcely a word was spoken as we jolted over the city pavements and at last reached the apartment. Inez and Craig entered and I followed, carrying just one of the packages as Craig had indicated by dumb show, leaving the other in the car, which was to wait. "I think you had better write him a note," suggested Craig, as we entered the living room. "I don't want you to see him until you feel better--and, by the way, see him here." She nodded with a wan smile, as though thinking how unusual it was for a meeting of lovers to be an ordeal, then excused herself to write the note. She had no sooner disappeared than Kennedy unwrapped the package which I had brought. From it he took a cedar box, oblong, with a sort of black disc fixed to an arm on the top. In the face of the box were two little square holes, with sides of cedar which converged inward into the box, making a pair of little quadrangular pyramidal holes which ended in a small black circle in the interior. He looked about the room quickly. Beside a window that opened out over a house several stories below stood a sectional bookcase. Into this bookcase, back of the books, in the shadow, he shoved the little box, to which he had already attached a spool of twisted wires. Then he opened the window and dropped the spool out, letting it unwind of its own weight until it fell on the roof far below. He shut the window and rejoined me without a word. A moment later she returned with the dainty note which she had written. "Shall I send it by a messenger?" she asked. "Yes, please," answered Kennedy, rising. As he moved a step to the door he held out his hand to her. "Senorita Mendoza," he said simply, in a tone that meant more than words, "you are a wonderful woman." She took his hand without a word, and a moment later we were whisked down in the elevator. "I must get on that roof on some pretext," remarked Kennedy, as we reached the street and he got his bearings. "Let me see, that house which backs up to the apartment is around the corner. Have the man drive us around there." We located the house and mounted the steps. On the wall beside the brownstone door was pasted a little slip of paper, "Furnished Rooms." "Splendid!" exclaimed Kennedy, as he read it. "Dismiss the taxi and meet me inside with the other package." By the time I had paid the man and come up the steps again Kennedy had made a dicker with the landlady for a double room on the third floor for both of us, and, by payment of a week's rent, we were to have immediate possession. "Our baggage will follow to-day," he explained, as we mounted the stairs to the room. I thought the landlady would never get through expatiating upon what a select place she ran, and thus leave us alone in our room, but at last even her flood of words was stilled by demands from a servant downstairs who must be instructed if the selectness of the establishment were to be maintained. No sooner were we alone than Kennedy tiptoed into the hall and made sure that we were not watched. It was then the work of only a few seconds to mount a ladder to a scuttle, unhook it, and gain the roof. There, dangling down from the dizzy height above, swayed the twisted wire. He seized it, unrolled it some more, and sent me downstairs to catch it, as he swung it over the edge of the roof to one of our own windows. Then he rejoined me. The other package, which had been heavier, consisted of another of those mysterious boxes, as well as several dry cells. Quickly he attached the wires to the box, placing the dry cells in the circuit. Then he began adjusting the mechanism of the box. So far I had only a vague idea of just what he had in mind, but gradually it began to dawn on me. It was perhaps half an hour, perhaps longer, after we had left the Senorita, before, sure that everything was all right with his line and the batteries which he had brought, Kennedy turned a little lever that moved in a semicircle, touching one after another of a series of buttons on the face of the cedar box, meanwhile holding a little black disc from the back of the box to his ear as he adjusted the thing. Nothing seemed to happen, but I could tell by the look of intentness on his face that he was getting along all right and was not worrying. Suddenly the look on his face changed to one of extreme satisfaction. He dropped the disc he was holding to his ear back into its compartment and turned to me. All at once it seemed as if the room in which we were was peopled by spirits. There was the sound of voices, loud, clear, distinct. It was uncanny. "He has just come in," remarked Craig. "Who?" I asked. "Lockwood--can't you recognize his voice? Listen." I did listen intently, and the more my ears became adjusted, the more plainly I could distinguish two voices, that of a man and that of a woman. It was indeed Lockwood and the Senorita, far above us. I would have uttered an exclamation of amazement, but I could not miss what they were saying. "Then you--you believe what he says?" asked Lockwood earnestly. "Professor Kennedy has the prints," replied Inez tremulously. "You saw them?" "Yes." "And you believe what HE says, too?" There was a silence. "What is it?" I asked, tapping the box lightly. "A vocaphone," replied Kennedy. "The little box that hears and talks." "Can they hear us?" I asked, in an awestruck whisper. "Not unless I want them to hear," he replied, indicating a switch. "You remember, of course, the various mechanical and electrical ears, such as the detectaphone, which we have used for eavesdropping in other cases?" I nodded. "Well, this is a new application which has been made of the detectaphone. When I was using that disc from the compartment there, I had really a detectaphone. But this is even better. You see how neat it all is? This is the detective service, and more. We can 'listen in' and we don't have to use ear-pieces, either, for this is a regular loud-speaking telephone--it talks right out in meeting. Those square holes with the converging sides act as a sort of megaphone to the receivers, those little circles back there inside magnifying the sound and throwing it out here in the room, so that we can hear just as well as if we were up there in the room where they are talking. Listen--I think they are talking again." "I suppose you know that Whitney and I have placed detectives on the trail of Norton," we could hear Lockwood say. "You have?" came back the answer in a voice which for the first time sounded cold. Lockwood must have recognized it. He had made a mistake. It was no sufficient answer to anything that he had done to assert that some one else had also done something. "Inez," he said, and we could almost hear his feet as he moved over the floor in her direction in a last desperate appeal, "can't you trust me, when I tell you that everything is all right, that they are trying to ruin me--with you?" There was a silence, during which we could almost hear her quick breath come and go. "Women--not even Peruvian women are like the women of the past, Chester," she said at length. "We are not playthings. Perhaps we have hearts--but we also have heads. We are not to be taken up and put down as you please. We may love--but we also think. Chester, I have been to see Professor Kennedy, and--" She stopped. It hurt too much to repeat what she had seen. "Inez," he implored. There was evidently a great struggle of love and suspicion going on in her, her love of him, her memory of her father, the recollection of what she had heard and seen. No one could have been as we were without wishing to help her. Yet no one could help her. She must work out her own life herself. "Yes," she said finally, the struggle ended. "What is it?" "Do you want me to tell you the truth?" "Yes," she murmured. His voice was low and tense. "I was there--yes--but the dagger was gone!" XVII THE VOICE FROM THE AIR "Do you believe it?" I asked Kennedy, as the voices died away, leaving us with a feeling that some one had gone out of the very room in which we were. He shrugged his shoulders and said nothing. But I cannot say that he seemed ill pleased at the result of the interview. "We'll just keep this vocaphone in," he remarked. "It may come in handy some time. Now, I think we had better go back to the laboratory! Things have begun to move." On the way back he stopped to telephone Norton to meet us and a few minutes after we arrived, the archaeologist entered. Kennedy lost no time in coming directly to the point, and Norton could see, in fact seemed to expect and be prepared for what was coming. "Well," exclaimed Kennedy, "you've done it, this time!" "I know what you are going to ask," returned Norton. "You are going to ask me why I did it. And I'm going to tell you. After I left you, the other day, I thought about it a long time. The more I thought, the more of a shame it seemed to me that a girl like that should be made a victim of her feelings. It wasn't so much what they have done to me that made me do it. I would have acted the same if it had been de Moche instead of Lockwood who was playing on her heart. I was afraid, to tell the truth, that you wouldn't tell her until it was too late. And she's too good to throw herself away and allow her fortune to be wasted by a couple of speculators." "Very well," said Craig. "For the sake of argument, let us admit all that. What did you expect to accomplish by it?" "Why--put an end to it, of course." "But do you think she was going to accept as truth what you told her? Would that be natural for one so high-strung?" "Perhaps not--right away. But I supposed she would come to you--as I see she has, for you know about it. After that, it was only a question of time. It may have been a heroic remedy, but the disease was critical." "Suppose," suggested Craig, "that, after all, he told her that he was there in the Museum, but that he did not get the dagger. And suppose that she believed it. What then?" Norton looked up quickly. "Did he tell her that?" "I am supposing that he did," repeated Craig, declining to place himself in a position which might lead to disclosing how he found out. "Then I should say that he was a great deal cleverer than I gave him credit for being," returned Norton. "Well, it's done now, and can't be undone. Have you found out anything about the de Moches?" "Not very much, I must admit. Of course, you know I'm not on the best of terms with them, for some reason or other. But I've been around the Prince Edward Albert a good deal, and I don't think they've been able to do much that I haven't some kind of line on. Alfonso seems to be moping. His professors here tell me that he has been neglecting his work sadly for the past few days. The Senora and Whitney seem to be as friendly as ever. I should say that they were going the pace fast, and it shows on him." I glanced significantly at Kennedy, but he betrayed nothing that might lead one to suppose he had discovered the cause. Evidently he was not ready yet to come out into the open and expected further developments on the poisoned cigarette clue. The telephone rang and Craig took down the receiver. "Yes, this is Kennedy," he answered. "Oh, hello, Lockwood. What's that? You've been trying to get me all day? I just came in. Why, yes, I can see you in about half an hour." "I guess I'd better clear out," said Norton with a bitter laugh, as Kennedy hung up the receiver. "There have been enough crimes committed without adding another murder to the list." "Keep on watching the de Moches," requested Kennedy as Norton made his way to the door. "Yes," agreed Norton. "They will bear it--particularly Alfonso. They are hot-blooded. You never know what they are going to do, and they keep their own counsel. I might hope that Lockwood would forget; but a de Moche--never." I cannot say that I envied him very much, for doubtless what he said was true, though his danger might be mitigated by the fact that the dagger was no longer in his Museum. Still, it would never have left Peru, I reflected, if it had not been for him, and there is, even in the best of us, a smouldering desire for revenge. Lockwood was more than prompt. I had expected that he would burst into the laboratory prepared to clean things out. Instead he came in as though nothing at all had happened. "There's no use mincing words, Kennedy," he began. "You know that I know what has happened. That scoundrel, Norton, has told Inez that you had shoe-prints of some one who was in the Museum the night of the robbery and that those shoe-prints correspond with mine. As a matter of fact, Kennedy, I was there. I was there to get the dagger. But before I could get it, some one else must have done so. It was gone." I wanted to believe Lockwood. As for Craig he said nothing. "Then, when I did have a chance to get away that night," he continued, "I went over to Mendoza's. The rest you know." "You have told Inez that?" asked Kennedy in order to seem properly surprised. "Yes--and I think she believes me. I can't say. Things are strained with her. It will take time. I'm not one of those who can take a girl by main force and make her do what she won't do. I wish I could smooth things over. Let me see the prints." Kennedy handed them over to him. He looked at them, long and closely, then handed back the damning evidence against himself. "I know it would be no use to destroy these," he remarked. "In the first place that would really incriminate me. And in the second I suppose you have copies." Craig smiled blandly. "But I can tell you," he exclaimed, bringing his fist down on the laboratory table with a bang, "that before I lose that girl, somebody will pay for it--and there won't be any mistakes made, either." The scowl on his face and the menacing look in his eye showed that now, with his back up against the wall, he was not bluffing. He seemed to get little satisfaction out of his visit to us, and in fact I think he made it more in a spirit of bravado than anything else. Lockwood had scarcely gone before Kennedy pulled out the University schedule, and ran his finger down it. "Alfonso ought to be at a lecture in the School of Mines," he said finally, folding up the paper. "I wish you'd go over and see if he is there, and, if he is, ask him to step into the laboratory." The lecture was in progress all right, but when I peered into the room it was evident that de Moche was not there. Norton was right. The young man was neglecting his work. Evidently the repeated rebuffs of Inez had worked havoc with him. Nor was he at the hotel, as we found out by calling up. There was only one other place that I could think of where he would be likely to be and that was at the apartment of Inez. Apparently the same idea occurred to Kennedy, for he suggested going back to our observation point in the boarding-house and finding out. All the rest of the day we listened through the vocaphone, but without finding out a thing of interest. Now and then we would try the detective instrument, the little black disc in the back, but with no better success. Then we determined to listen in relays, one listening, while the other went out for dinner. It must have been just a bit after dark that we could hear Inez talking in a low tone with Juanita. A buzzing noise indicated that there was some one at the hall door. "If it's any one for me," we heard Inez say, "tell them that I will be out directly. I'm not fit to be seen now." The door was opened and a voice which we could not place asked for the senorita. A moment later Juanita returned and asked the visitor to be seated a few moments. It was not long before we were suddenly aware that there was another person in the room. We could hear whispers. The faithful little vocaphone even picked them up and shot them down to us. "Is everything all right?" whispered one, a new voice which was somewhat familiar I thought, but disguised beyond recognition. "Yes. She'll be out in a minute." "Now, remember what I told you. If this thing works you get fifty dollars more. I'd better put this mask on--damn it!--the slit's torn. It'll do. I'll hide here as soon as we hear her. That's a pretty nice private ambulance you have down there. Did you tell the elevator boy that she had suddenly been taken ill? That's all fixed, then. I've got the stuff--amyl nitrite--she'll go off like a shot. But we'll have to work quick. It only keeps her under a few minutes. I can't wear this mask down and I'm afraid some one will recognize me. Oh, you brought a beard. Good. I'll give you the signal. There must be no noise. Yes, I saw the stretcher where you left it in the hall." "All right, Doc," returned the first and unfamiliar voice. It all happened so quickly that we were completely bowled over for the moment. Who was the man addressed as "Doc"? There was no time to find out, no time to do anything, apparently, so quickly had the plot been sprung. I looked at Kennedy, aghast, not knowing what to do in this unexpected crisis. A moment later we heard a voice, "I'm sorry to have had to keep you waiting, but what is it that I can do for you?" "Good God!" exclaimed Kennedy. "It is Inez herself!" It was altogether too late to get over there to warn her, perhaps even to rescue her. What could we do? If we could only shout for help. But what good would that do, around a corner and so far away? The vocaphone itself! Quickly Kennedy turned another switch, of a rheostat, which accentuated a whisper to almost a shout. "Don't be alarmed, Senorita," he cried. "This is Kennedy talking. Look under the bookcase by the window. You will find a cedar box. It is a detective vocaphone through which I can hear you and which is talking out to you. I have heard something just there just now--" "Yes, yes. Go on!" "You are threatened. Shout! Shout!" Just then there came a sound of a scuffle and a muffled cry which was not much above a whisper, as though a strong hand was clapped over her mouth. What could we do? "Juanita--Juanita--help!--police!" shouted Craig himself through the vocaphone. An instant later we could hear other screams as Juanita heard and spread the alarm, not a second too soon. "Come on, Walter," shouted Kennedy dashing out of the room, now that he was assured the alarm had been given. We hurried around the corner, and into the apartment. One of the elevators was up, and no one was running the other, but we opened the gates and Kennedy ran it up by himself. In the Mendoza apartment all was a babel of voices, every one talking at once. "Did you get them?" Craig asked, looking about. "No, sir," replied the elevator boy. "One of them came in from the ambulance and told me Miss Mendoza was suddenly taken sick. He rode up with the stretcher. The other one must have walked up." "Do you know him? Has he ever been here before?" "I can't say, sir. I didn't see him. At least, sir, when I heard the screams I ran in from the elevator, which the other one told me to wait with--left the door open. Just as I ran in, they dodged out past me, jumped into the car and rode down. I guess they must have had the engine of the ambulance motor running, sir, if they got away without you seeing them." We were too late to head them from speeding off. But, at least, we had saved the Senorita. She was terribly upset by the attack, much shaken, but really all right. "Have you any idea who it could be?" asked Craig as the faithful Juanita cared for her. "I don't know the man who was waiting and 'Nita never saw him, either," she replied. "The one who jumped out from behind the portieres had on a mask and a false beard. But I didn't recognize anything about him." Sudden as the attack had been and serious as might have been the outcome, we could not but feel happy that it had been frustrated. Yet it seemed that some one ought to be delegated to see that such a thing could not occur again. "We must think up some means of protecting you," soothed Kennedy. "Let me see, Mr. Lockwood and Mr. Whitney seem to be the closest to you. If you don't mind I'll call them up. I wonder if you'd object if we had a little luncheon up here, to-morrow? I have a special reason for asking it. I want to insure your safety and we may as well meet on common ground." "There isn't the slightest objection in the world," she replied, as Kennedy reached for the telephone. We had some little difficulty in locating both Lockwood and Whitney, but finally after a time managed to find them and arrange for the conference on the Senorita's safety for the next day. Outside Kennedy gave instructions to the officer on the beat to watch the apartment particularly, and there was no reason now to fear a repetition of the attempt, at least that night. XVIII THE ANTIDOTE Early the following morning Kennedy left me alone in the laboratory and made a trip downtown, where he visited a South American tobacco dealer and placed a rush order for a couple of hundred cigarettes exactly similar in shape and quality to those which Mendoza had smoked and which the others seemed also to prefer, except, however, that the deadly drug was left out. While he was gone, it occurred to me to take up again the hunt for Alfonso. Norton was not in his little office, nor could I find Alfonso anywhere about the campus. In fact he seemed to have almost dropped out of his University work for the time. Accordingly, I turned my steps toward the Prince Edward Albert Hotel, in the hope that he might be there. Inquiries of the clerk at the desk told me that he had been there, but was out just at that moment. I did not see Whitney around, nor the Senora, so I sat down to wait, having nothing better to do until Kennedy's return. I was about to give it up and go, when I heard a cab drive up to the door and, looking up, I saw Alfonso get out. He saw me about the same time and we bowed. I do not think he even tried to avoid me. "I haven't seen you for some time," I remarked, searching his face, which seemed to me to be paler than it had been. "No," he replied. "I haven't been feeling very well lately and I've been running up into the country now and then to a quiet hotel--a sort of rest cure, I suppose you would call it. How are you? How is Senorita Inez?" "Very well," I replied, wondering whether he had said what he did in the hope of establishing a complete alibi for the events of the night before. Briefly I told him what had happened, omitting reference to the vocaphone and our real part in it. "That is terrible," he exclaimed. "Oh, if she would only allow me to take care of her--I would take her back to our own country, where she would be safe, far away from these people who seek to prey on all of us." He paced up and down nervously, and I could see that my information had added nothing to his peace of mind, though, at the same time, he had betrayed nothing on his part. "I was just passing through," I said finally, looking at my watch, "and happened to see you. I hope your mother is well?" "As well as is to be expected, surrounded by people who watch every act," he replied, I thought with a rap at us for having Norton about and so active, though I could not be sure. We separated, and I hastened back to the laboratory to report to Craig that Alfonso was rusticating for his health. Kennedy, on his part, had had an experience, though it was no more conclusive than my own. After he had left the tobacco district, he had walked up Wall Street to the subway. In the crowd he had seen Senora de Moche, although she had not seen him. He had turned and followed her until she entered the building in which Whitney and his associates had their offices. Whether it indicated that she was still leading them a chase, or they her, was impossible to determine, but it at least showed that they were still on friendly terms with each other. In the laboratory he could always find something to do on the case, either in perfecting his chemical tests of the various drugs we had discovered, or in trying to decipher some similarities in the rough printing of the four warnings and the anonymous letter with the known handwriting of those connected with the case, many specimens of which he bad been quietly collecting. That in itself was a tremendously minute job, entailing not only a vast amount of expert knowledge such as he had collected in his years of studying crime scientifically, but the most exact measurements and careful weighing and balancing of trifles, which to the unscientific conveyed no meanings at all. Still, he seemed to be forging ahead, though he never betrayed what direction the evidence seemed to be taking. The package of cigarettes which he had ordered downtown was delivered about an hour after his return and seemed to be the signal for him to drop work, for the meeting with Lockwood and Whitney had been set early. He stowed the package in his pockets and then went over to a cabinet in which he kept a number of rather uncommon drugs. From it he took a little vial which he shoved into his waistcoat pocket. "Are you ready, Walter?" he asked. "Whenever you are," I said, laying aside my writing. Together we made our way down to the Mendoza apartment which had been the scene of the near-tragedy the night before. Outside, he paused for several moments to make inquiries about any suspicious persons that might have been seen lurking about the neighbourhood. None of the attendants in the apartment remembered having seen any, and they were now very alert after the two events, the murder and the attempted abduction. Not a clue seemed to have been left by the villain who had been called "Doc." "How do you feel after your thrilling experience?" greeted Craig pleasantly, as Juanita admitted us and Inez came forward. "Oh, Mr. Kennedy," she answered, with a note of sadness in her tone. "It makes me feel so alone in the world. If it were not for 'Nita--and you, I don't know what I should do." "Doesn't Mr. Lockwood count?" asked Kennedy observantly. "Of course--everything," she answered hastily. "But he has to be away so much on business, and--" She paused and sighed. I could not help wondering whether, after all, his explanation of the dagger episode had been enough to satisfy her. Had she really accepted it? Neither Lockwood nor Whitney had arrived, and Kennedy improved the opportunity to have a quiet talk aside with her, at which, I imagine, he was arranging a programme of what was to happen at this meeting and her part in it to co-operate with him. She had left the room for a moment and we were alone. It was evidently a part of his plan, for no sooner was she gone than he opened the package of cigarettes which he had ordered and took out from the box in which Mendoza had kept his cigarettes those that were there, substituting those he had brought. We had not long to wait, now. Lockwood and Whitney came together. I was interested to see the greeting of Inez and her lover. Was it pure fancy, or did I detect a trace of coldness as though there had sprung up something between them? As far as Lockwood was concerned, I felt sure that he was eager to break down any barrier that kept them from being as they had been. Whitney took her hand and held it, in a playful sort of way. "I wish I were a young buck," he smiled. "No one would dare look at you--much less try to carry you off. Yes, we must be more careful of our little beauty, or we shall lose her." They turned to greet us. I felt, as we shook hands, that it was much the same sort of handshake that one sees in the prize ring--to be followed by the clang of a bell, then all going to it, in battle royal, with the devil after the hindmost. There was scarcely a chance for a preliminary bout before luncheon was announced, and we entered the cozy little dining-room to seat ourselves at the daintiest of tables. One could feel the hostess radiating hospitality, even on such a cross-current set of guests as we were, and for the time, I almost felt that it had been Kennedy's purpose to promote a love-feast instead of an armed truce. Nothing was said about the main cause of our being together for some time, and the small talk almost lifted for a time the incubus that had settled down on all our lives since the tragedy in the den at the other end of the suite. But the fact could not be blinked. Tacitly every one seemed to wait on Kennedy to sound the gong. Finally he did so. "Of course," he began, clearing his throat, "there is no use making believe about anything. I think we all understand each other better now than we have ever done before. As for me, I am in this case under a promise to stick to it and fight it to the end. I suppose the rest of you are, also. But that need not prevent us agreeing on one thing. We can work together to protect Senorita Mendoza, at least, from such danger as threatened her last night." "It's a dastardly shame," Lockwood exclaimed angrily, "that a man who would attempt a thing like that should go unpunished." "Show me how to trace him and I'll guarantee the punishment," rejoined Craig drily. "I am not a detective," replied Lockwood. Kennedy forebore to reply in kind, though I knew there was a ready answer on his tongue for the lover. Ever since they had arrived, the Senorita had seen that they were well supplied with cigarettes from the case in which she and they supposed were the genuine South American brand of her father. Kennedy and I smoked them, too, although neither of us liked them very much. The others were smoking furiously. "However," resumed Kennedy, "I do not feel that I want to intrude myself in this matter without being perfectly frank and having the approval of Senorita Mendoza. She has known both of you longer and more intimately than she has known me, although she has seen fit to place certain of her affairs in my hands, for which I trust I shall render a good account of my stewardship. It seems to me, though, that if there is, as we now know there is, some one whom we do not know"--he paused--"who has sunk so low as to wish to carry her off, apparently where she shall be out of the influence of her friends, it is only right that precautions should be taken to prevent it." "What is your suggestion?" demanded Whitney, rather contentiously. "Would there be any objection," asked Kennedy, "if I should ask my old friend,--or any of you may do it,--Deputy Commissioner O'Connor to detail a plainclothesman to watch this house and neighbourhood, especially at night?" We watched the faces of the others. But it was really of no use. "I think that is an excellent plan," decided Inez herself. "I shall feel much safer and surely none of you can be jealous of the city detectives." Kennedy smiled. She had cut the Gordian knot with a blow. Neither Lockwood nor Whitney could object. The purpose of the luncheon was accomplished. In fact he did not wait for further consideration, but excused himself from the table for a moment to call up our old friend O'Connor and tell him how gravely his man was needed. It was a matter of only a few minutes when he returned from the other room. "He will detail Burke for this special service as long as we want him," reported Craig, sitting down again. Inez was delighted, naturally, for the affair had been a terrific shock to her. I could see how relieved she felt, for I was sitting directly next to her. The maid had, meanwhile brought in the coffee and Inez had been waiting to pour until Kennedy returned. She did not do so, now, either, however. It seemed as if she were waiting for some kind of signal from Kennedy. "What a splendid view of the park you get here," remarked Kennedy turning toward the long, low windows that opened on a balustraded balcony. "Just look at that stream of automobiles passing on the west drive." Common politeness dictated that all should turn and look, although there was no novelty in the sight for any of us. As I have said, I was sitting next to Inez. To me she was a far more attractive sight than any view of the park. I barely looked out of the window. Imagine my surprise, then, at seeing her take advantage of the diversion to draw from the folds of her dress a little vial and pour a bit of yellowish, syrupy liquid into the cup of coffee which she was preparing for Whitney. I could not help looking at her quickly. She saw that I had seen her and raised her other hand with a finger to her lips and an explanatory glance at Kennedy who was keeping the others interested. Instantly, I recognized the little vial which Craig had shoved into his waistcoat pocket. That had been the purpose of his whispered conference with her when we arrived. I said nothing, but determined to observe more closely. More coffee and more cigarettes followed, always from the same box which was now on the table. The luncheon developed almost a real conversation. For the time, under the spell of our hostess, we nearly forgot that we were in reality bitter enemies. My real interest, as time passed, centred in Whitney and I could not help watching him closely. Was it a fact, or was it merely my imagination? He seemed quite different. The pupils of his eyes did not seem to be quite so dilated as they had been at other times, or even when he arrived. Even his heart action appeared to be more normal. I think Inez noticed it, too. There was none of the wildness in his conversation, such as there often had been at other times. Our party was prolonged beyond the time we had expected, but, although he had much on his mind, Kennedy made no move to break it up. In fact he did everything to encourage it. At last, however, the others did notice the time, and I think it was with sincere regret that the truce was broken. Even then, no parting shots were indulged in. As we left, Inez thanked Kennedy for his consideration, and I am sure that that in itself was reward enough. We parted from Lockwood, who wished to remain a little while, and rode down in the elevator with Whitney, a changed man. "I'll walk over to the elevated with you," he said. "I was going to my hotel, but I think I'll go down to the office instead." Evidently he had got Senora de Moche out of his mind, at least temporarily, I thought. Then for the first time I recalled that during the whole luncheon there had been no reference to either the Senora or Alfonso, though both must have been in our minds often. "What was it you had Inez drop into Whitney's coffee?" I asked Craig as we parted from him and rode uptown. "You saw that?" he smiled. "It was pilocarpine, jaborandi, a plant found largely in Brazil, one of the antidotes for stramonium poisoning. It doesn't work with every one. But it seems to have done so with him. Besides, the caffeine in the coffee probably aided the pilocarpine. Then, too, I made them smoke cigarettes without the dope that is being fed them. Lockwood's case, for some reason, hasn't gone far. But did you notice how the treatment contracted the pupils of Whitney's eyes almost back to normal again?" I had and said so, adding, "But what was your idea?" "I think I've got at the case from a brand-new angle," he replied. "Unless I am greatly mistaken, when the person who is doing the doping sees that Whitney is getting better--why, I think you all noticed it, Inez and Lockwood as well as you--it will mean another attempt to substitute more cigarettes doped with that drug. I think it's by substitution that it's being done. We'll see." At the laboratory, Kennedy called Norton and described briefly what had happened, especially to Whitney. "Now is your chance, Norton," he added, "to do some real good work. I want some one to watch the Senora, see if she, too, notes the difference in him. Understand?" "Perfectly," returned Norton. "That is something I think I can do." XIX THE BURGLAR POWDER It was not until after dinner that we heard again from Norton. He had evidently spent the time faithfully hanging about the Prince Edward Albert, but Whitney had not come in, although the Senora and Alfonso were about. "I saw them leaving the dining-room," he reported to us in the laboratory directly afterward, "just as Whitney came in. They could not see me. I took good care of that. But, say, there is a change in Whitney, isn't there? I wonder what caused it?" "It's as noticeable as that?" asked Kennedy. "And did she notice it?" "I'm sure of it," replied Norton confidently. "She couldn't help it. Besides, after he left her and went into the dining-room himself she and Alfonso seemed to be discussing something. I'm sure it was that." Kennedy said nothing, except to thank Norton and compliment him on his powers of observation. Norton took the praise with evident satisfaction, and after a moment excused himself, saying that he had some work to do over in the Museum. He had no sooner gone than Kennedy took from a drawer a little packet of powder and an atomizer full of liquid, which he dropped into his pocket. "I think the Prince Edward Albert will be the scene of our operations, to-night, Walter," he announced, reaching for his hat. He seemed to be in a hurry and it was not many minutes before we entered. As he passed the dining-room he glanced in. There was Whitney, not half through a leisurely dinner. Neither of the de Moches seemed to be downstairs. Kennedy sauntered over to the desk and looked over the register. We already knew that Whitney and the Senora had suites on the eighth floor, on opposite sides and at opposite ends of the hall. The de Moche suite was under the number 810. That of Whitney was 825. "Is either 823 or 827 vacant?" asked Kennedy as the clerk came over to us. He turned to look over his list. "Yes, 827 is vacant," he found. "I'd like to have it," said Kennedy, making some excuse about our luggage being delayed, as he paid for it for the night. "Front!" called the clerk, and a moment later we found ourselves in the elevator riding up. The halls were deserted at that time in the evening except for a belated theatre-goer, and in a few minutes there would ensue a period in which there was likely to be no one about. We entered the room next to Whitney's without being observed by any one of whom we cared. The boy left us, and it was a simple matter after that to open a rather heavy door that communicated between the two suites and was not protected by a Yale lock. Instead of switching on the lights, Kennedy first looked about carefully until he was assured that there was no one there. It seemed to me to be an unnecessary caution, for we knew Whitney was down-stairs and would probably be there a long time. But he seemed to think it necessary. Positive that we were alone, he made a hasty survey of the rooms. Then he seemed to select as a starting-point a table in one corner of the sitting-room on which lay a humidor and a heavy metal box for cigarettes. Quickly he sprinkled on the floor, from the hall door to the table on which the case of cigarettes lay, some of the powder which I had seen him wrap up in the laboratory before we left. Then, with the atomizer, he sprayed over it something that had a pungent, familiar odour--walking backwards from the hall door to the table, as he sprayed. "Don't you want more light?" I asked, starting to cross to a window to let the moonlight stream in. "Don't walk on it, Walter," he whispered, pushing me back. "No, I don't need any more light." "What are you doing?" I asked, mystified at his actions. "First I sprinkled some powdered iodine on the floor," he replied, "and then sprayed over just enough ammonia to moisten it. It will evaporate quickly, leaving what I call my anti-burglar powder." "I'm sure I wouldn't be thought one of the fraternity for the world," I observed, stepping aside to give him all the room he wanted in which to operate. He had finished his work by this time and now the evening wind was blowing away the slight fumes that had arisen. For a few moments he left our door into Whitney's room open, in order to insure clearing away the odour. Then he quietly closed it, but did not lock it again. We waited a few minutes, then Craig leaned over to me. "I wish you'd go down and see how near Whitney is through dinner," he said. "If he is through, do something, anything to keep him down there. Only be as careful as you can not to be seen by any one who knows us." I rode down in an empty elevator and cautiously made my way to the dining-room. Whitney had finished much sooner than I had expected and was not there. Much as I wanted not to be seen, I found that it was necessary to make a tour of the hotel to find him and I did so, wondering what expedient I would adopt to keep him down there if I found him. I did not have to adopt any, however. Whitney was almost alone in the writing-room, and a big pile of letters beside him showed me that he would be busy for some time. I rode back to the room to tell Craig, flattering myself that I had not been seen. "Good," he exclaimed. "I don't think we'll have to wait much longer, if anything at all is going to happen." In the darkness we settled ourselves for another vigil that was to last we knew not how long. Neither of us spoke as we half crouched in the shadow of our room, listening. Slowly the time passed. Would any one take advantage of the opportunity to tamper with the box of cigarettes on the table? I fell to speculating. Who could it possibly have been that had conceived this devilish plot? What was back of it all? I wondered whether it were possible that Lockwood, now that Mendoza was out of the way, could desire to remove Whitney, the sole remaining impediment to possessing the whole of the treasure as well as Inez? Then there were the Senora and Alfonso, the one with a deep race and family grievance, the other a rejected suitor. What might not they do with some weird South American poison? Once or twice we heard the elevator door clang and waited expectantly, but nothing happened. I began to wonder whether, even if some one had a pass-key to the suite, we could hear him enter if he was quiet. The outside hall was thickly carpeted, and deadened every footfall if one exercised only reasonable care. The rooms themselves were much the same. "Don't you think we might have the door ajar a little?" I suggested anxiously. "Sh!" was Kennedy's only comment in the negative. I glanced now and then at my watch and by straining my eyes was surprised to see how early it was yet. The minutes were surely leaden-footed. In the darkness, I fell again to reviewing the weird succession of events. I am not by nature superstitious, but in the black silence I could well imagine a staring succession of eyes, beginning with the dilated pupils of Whitney and passing on to the corpse-like expression of Mendoza, but always ending with the remarkable, piercing, black eyes of the Indian woman with the melancholy-visaged son, as they had impressed me the first time I saw them and, in fact, ever since. Was it a freak of my mind, or was there some reason for it? Suddenly I heard in the next room what sounded like a series of little explosions, as though some one were treading on match heads. "My burglar powder works," muttered Craig to me in a hoarse whisper. "Every step, even those of a mouse running across, sets it off!" He rose quickly and threw open the door into Whitney's suite. I sprang after him. There, in the shadows, I saw a dark form, starting back in quick retreat. But we were too late. He was cat-like, too quick for us. In the dim light of the little explosions we could catch a glimpse of the person who had been craftily working with the dread drug to drive Whitney and others insane. But the face was masked! He banged shut the door after him and fled down the hall, making a turn to a flight of steps. We followed, and at the steps paused a moment. "You go up, Walter," shouted Kennedy. "I'll go down." It was fifteen minutes later before we met downstairs, neither of us with a trace of the intruder. He seemed to have vanished like smoke. "Must have had a room, like ourselves," remarked Craig somewhat chagrined at the outcome of his scheme. "And if he was clever enough to have a room, he is clever enough to have a disguise that would fool the elevator boys for a minute. No, he has gone. But I'll wager he won't try any more substitutions of stramonium-poisoned cigarettes for a while. It was too close to be comfortable." We were baffled again, and this time by a mysterious masked man. Could it be the same whom we heard over the vocaphone addressed as "Doc"? Perhaps it was, but that gave us no hint as to his identity. He seemed just as far away as ever. We waited around the elevators for some time, but nothing happened. Kennedy even sought out the manager of the hotel, and after telling who he was, had a search made of the guests who might be suspected. The best we could do was to leave word that the employees might be put on the lookout for anything of a suspicious nature. Whitney, the innocent cause of all this commotion, was still in the writing-room with his letters. "I think I ought to tell him," decided Kennedy as we passed down the lobby. He seemed surprised to see us, as we strolled up to his writing desk, but pushed aside the few letters which he had not finished and asked us to sit down. "I don't know whether you have noticed it," began Craig, "but I wonder how you feel?" Whitney had expected something else rather than his health as the subject of a quiz. "Pretty good now," he answered before he knew it, "although I must admit that for the past few days I have wondered whether I wasn't slowing up a bit--or rather going too fast." "Would you like to know why you feel that way?" asked Craig. Whitney was now genuinely puzzled. It was perfectly evident, as it had been all the time, that he had not the slightest inkling of what was going on. As Craig briefly unfolded what we had discovered and the reason for it, Whitney watched him aghast. "Poisoned cigarettes," he repeated slowly. "Well, who would ever have thought it. You can bet your last jitney I'll be careful what I smoke in the future, if I have to smoke only original packages. And it was that, partly, that ailed Mendoza?" Kennedy nodded. "Don't take any pilocarpine, just because I told you that was what I used. You have given yourself the best prescription, just now. Be careful what you smoke. And, don't get excited if you seem to be stepping on matches up there in your room for a little while, either. It's nothing." Whitney's only known way of thanking anybody was to invite them to adjourn to the cafe, and accordingly we started across the hall, after he had gathered up his correspondence. The information had made more work that night impossible for him. As we crossed from the writing-room, we saw Alfonso de Moche coming in from the street. He saw us and came over to speak. Was it a coincidence, or was it merely a blind? Was he the one who had got away and now calculated to come back and throw us off guard? Whitney asked him where he had been, but he replied quickly that his mother had not been feeling very well after dinner and had gone to bed, while he strolled out and had dropped into a picture show. That, I felt, was at least clever. The intruder had been a man. De Moche excused himself, and we continued our walk to the cafe, where Whitney restored his shattered peace of mind somewhat. "What's the result of your detective work on Norton?" ventured Kennedy at last, seeing that Whitney was in a more expansive frame of mind, and taking a chance. "Oh," returned Whitney, "he's scared, all right. Why, he has been hanging around this hotel--watching me. He thinks I don't know it, I suppose, but I do." Kennedy and I exchanged glances. "But he's slippery," went on Whitney. "He knows that he is being shadowed and the men tell me that they lose him, now and then. To tell the truth I don't trust most of these private detectives. I think their little tissue paper reports are half-faked, anyhow." He seemed to want to say no more on the subject, from which I took it that he had discovered nothing of importance. "One thing, though," he recollected, after a moment. "He has been going to see Inez Mendoza, they tell me." "Yes?" queried Kennedy. "Confound him. He pretty nearly got Lockwood in bad with her, too," said Whitney, then leaning over confidentially added, "Say, Kennedy, honestly, now, you don't believe that shoe-print stuff, do you?" "I see no reason to doubt it," returned Kennedy with diplomatic firmness. "Why?" "Well," continued Whitney, still confidential, "we haven't got the dagger--that's all. There--I never actually asserted that before, though I've given every one to understand that our plans are based on something more than hot-air. We haven't got it, and we never had it." "Then who has it?" asked Kennedy colourlessly. Whitney shook his head. "I don't know," he said merely. "And these attacks on you--this cigarette business--how do you explain that," asked Craig, "if you haven't the dagger?" "Jealousy, pure jealousy," replied Whitney quickly. "They are so afraid that we will find the treasure. That's my dope." "Who is afraid?" "That's a serious matter," he evaded. "I wouldn't say anything that I couldn't back up in a case of that kind. I'd get into trouble." There was nothing to be gained by prolonging the conversation and Kennedy made a move as though to go. "Just give us a square deal," said Whitney as we left. "That's all we want--a square deal." Kennedy and I walked out of the Prince Edward Albert and turned down the block. "Well, have you found out anything more?" asked a voice in the shadow beside us. We turned. It was Norton. "I saw you talking to Whitney in the writing-room," he said, with a laugh, "then in the cafe, and I saw Alfonso come in. He still has those shadows on me. I wouldn't be surprised if there was one of them around in a doorway, now." "No," returned Kennedy, "he didn't say anything that was important. They still say they haven't the dagger." "Of course," said Norton. "You'll wait around a little longer?" asked Kennedy as we came to a corner and stopped. "I think so," returned Norton. "I'll keep you posted." Kennedy and I walked on a bit. "I'm going around to see how Burke, O'Connor's man, is getting on watching the Mendoza apartment, Walter," he said at length. "Then I have two or three other little outside matters to attend to. You look tired. Why don't you go home and take a rest? I shan't be working in the laboratory to-night, either." "I think I will," I agreed, for the strain of the case was beginning to tell on me. XX THE PULMOTOR I went directly to our apartment after Craig left me and for a little while sat up, speculating on the probabilities of the case. Senora de Moche had told us of her ancestor who had been intrusted with the engraved dagger, of how it had been handed down, of the death of her brother; she had told us of the murder of the ancestor of Inez Mendoza, of the curse of Mansiche. Was this, after all, but a reincarnation of the bloody history of the Gold of the Gods? There were the shoe-prints in the mummy case. They were Lockwood's. How about them? Was he telling the truth? Now had come the poisoned cigarettes. All had followed the threats: BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS. Several times I had been forced already to revise my theories of the case. At first I had felt that it pointed straight toward Lockwood. But did it seem to do so now? Suppose Lockwood had stolen the dagger from the Museum, although he denied even that. Did that mean, necessarily that he committed the murder with it, that he now had it? Might he not have lost it? Might not some one else--the Senora, or Alfonso, or both--have obtained it? Might not Mendoza have been murdered with it by some other hand to obtain or to hide the secret on its bloody blade? I went to bed, still thinking, no nearer a conclusion than before, prepared to dream over it. That is the last I remember. When I regained consciousness, I was lying on the bed still, but Craig was bending over me. He had just taken a rubber cap off my face, to which was attached a rubber tube that ran to a box perhaps as large as a suitcase, containing a pump of some kind. I was too weak to notice these things right away, too weak to care much about them, or about anything else. "Are you all right now, old man?" he asked, bending over me. "Y-Yes," I gasped, clutching at the choking sensation in my throat. "What has happened?" Perhaps I had best tell it as though I were not the chief actor; for it came to me in such disjointed fragmentary form, that it was some time before I could piece it together. Craig had seen Burke, and had found that everything was all right. Then he had made the few little investigations that he intended. But he had not been to the laboratory. There had been no light there that night. At last when he arrived home, he had found a peculiar odour in the hall, but had thought nothing of it, until he opened our door. Then there rushed out such a burst of it that he had to retreat, almost fainting, choking and gasping for breath. His first thought was for me; and protecting himself as best he could he struggled through to my room, to find me lying on the bed, motionless, almost cold. He was by this time too weak to carry me. But he managed to reach the window and throw it wide open. As the draught cleared the air, he thought of the telephone and with barely strength enough left called up one of the gas companies and had a pulmotor sent over. Now that the danger was past for me, and he felt all right, his active mind began at once on the reconstruction of what had happened. What was it--man or devil? Could a human fly have scaled the walls, or an aeroplane have dropped an intruder at the window ledge? The lock on the door did not seem to have been tampered with. Nor was there any way by which entrance could have been gained from a fire escape. It was not illuminating gas. Every one agreed on that. No, it was not an accident. It was an attempt at murder. Some one was getting close to us. Every other weapon failing, this was desperation. I had been made comfortable, and he was engaged in one of his characteristic searches, with more than ordinary eagerness, because this was his own apartment, and it was I who had been the victim. I followed him languidly as he went over everything, the furniture, the walls, the windows, the carpets--there looking for finger-prints, there for some trace of the poisonous gas that had filled the room. But he did not have the air of one who was finding anything. I was too tired to reason. This was but another of the baffling mysteries that confronted us. A low exclamation caused me to open my eyes and try to discover what was the cause. He was bending over the lock of the door looking at it intently. "Broken?" I managed to say. "No--corroded," he replied. "You keep still. Save your energy. I've got strength enough for two, for a while." He came over to the bed and bent over me. "I won't hurt you," he encouraged, "but just let me get a drop of your blood." He took a needle and ran it gently into my thumb beside the nail. A drop or two of blood oozed out and he soaked it up with a piece of sterile gauze. "Try to sleep," he said finally. "And you?" I asked. "It's no use. I'm going over to the laboratory. I can't sleep. There's a cop down in front of the house. You're safe enough. By George, if this case goes much further we'll have half the force standing guard. Here--drink that." I had made up my mind not to go to sleep, if he wouldn't, but I slipped up when I obeyed him that time. I thought it was a stimulant but it turned out to be a sedative. I did not wake up until well along in the morning, but when I did I was surprised to find myself so well. Before any one could stop me, I was dressed and had reached the door. A friend of ours who had volunteered to stay with me was dozing on a couch as I came out. "Too late, Johnson," I called, trying hard to be gay, though I felt anything but like it. "Thank you, old man, for staying with me. But I'm afraid to stop. You're stronger than I am this morning--and besides you can run faster. I'm afraid you'll drag me back." He did try to do it, but with a great effort of will-power I persuaded him to let me go. Out in the open air, too, it seemed to do me good. The policeman who had been stationed before the house gazed at me as though he saw a ghost, then grinned encouragingly. Still, I was glad that the laboratory was only a few blocks away, for I was all in by the time I got there, and hadn't even energy enough to reply to Kennedy's scolding. He was working over a microscope, while by his side stood in racks, innumerable test-tubes of various liquids. On the table before him lay the lock of our door which he had cut out after he gave me the sleeping draught. "What was it?" I asked. "I feel as if I had been on a bust, without the recollection of a thing." He shook his head as if to discourage conversation, without taking his eyes off the microscope through which he was squinting. His lips were moving as if he were counting. I waited in impatient silence until he seemed to have finished. Then, still without a word, he took up a test-tube and dropped into it a little liquid from a bottle on a shelf above the table. His face lighted up, and he regarded the reaction attentively for some time. Then he turned to me, still holding the tube. "You have been on a bust," he said with a smile as if the remark of a few minutes before were still fresh. "Only it was a laughing gas jag--nitrous oxide." "Nitrous oxide?" I repeated. "How--what do you mean?" "I mean simply that a test of your blood shows that you were poisoned by nitrous oxide gas. You remember the sample of blood which I squeezed from your thumb? I took it because I knew that a gas--and it has proved to be nitrous oxide--is absorbed through the lungs into the circulation and its presence can be told for a considerable period after administration." He paused a moment, then went on: "To be specific in this case I found by microscopic examination that the number of corpuscles in your blood was vastly above the normal, something like between seven and eight million to a drop that should have had somewhat more than only half that number. You were poisoned by gas that--" "Yes," I interrupted, "but how, with all the doors locked?" "I was coming to that," he said quietly, picking up the lock and looking at it thoughtfully. He had already placed it in a porcelain basin, and in this basin he had poured some liquids. Then he passed the liquids through a fine screen and at last took up a tube containing some of the resulting liquid. "I have already satisfied myself," he explained, "but for your benefit, seeing that you're the chief sufferer, I'll run over a part of the test. You saw the reaction which showed the gas a moment ago. I have proved chemically as well as microscopically that it is present in your blood. Now if I take this test-tube of liquid derived from my treatment of the lock and then test it as you saw me do with the other, isn't that enough for you? See--it gives the same reaction." It did, indeed, but my mind did not react with it. "Nitrous oxide," he continued, "in contact with iron, leaves distinct traces of corrosion, discernible by chemical and microscopic tests quite as well as the marks it leaves in the human blood. Manifestly, if no one could have come in by the windows or doors, the gas must have been administered in some way without any one coming into the room. I found no traces of an intruder." It was a tough one. Never much good at answering his conundrums when I was well, I could not even make a guess now. "The key-hole, of course!" he explained. "I cut away the entire lock, and have submitted it to these tests which you see." "I don't see it all yet," I said. "Some one came to our door in the night, after gaining entrance to the hall--not a difficult thing to do, we know. That person found our door locked, knew it would be locked, knew that I always locked it. Knowing that such was the case, this person came prepared, bringing perhaps, a tank of compressed nitrous oxide, certainly the materials for making the gas expeditiously." I began to understand how it had been done. "Through the keyhole," he resumed, "a stream of the gas was injected. It soon rendered you unconscious, and that would have been all, if the person had been satisfied. A little bit would have been harmless enough. But the person was not satisfied. The intention was not to overcome, but to kill. The stream of gas was kept up until the room was full of it. "Only my return saved you, for the gas was escaping very slowly. Even then, you had been under it so long that we had to resort to the wonderful little pulmotor after trying both the Sylvester and Schaefer methods and all other manual means to induce respiration. At any rate we managed to undo the work of this fiend." I looked at him in surprise, I, who didn't think I had an enemy in the world. "But who could it have been?" I asked. "We are pretty close to that criminal," was the only reply he would give, "providing we do not spread the net in sight of the quarry." "Why should he have wanted to get me?" I repeated. "Don't flatter yourself," replied Craig. "He wanted me, too. There wasn't any light in the laboratory last night. There was a light in our apartment. What more natural than to think that we were both there? You were caught in the trap intended for both of us." I looked at him, startled. Surely this was a most desperate criminal. To cover up one murder--perhaps two--he did not hesitate to attempt a third, a double murder. The attack had been really aimed at Kennedy. It had struck me alone. But it had miscarried and Craig had saved my life. As I reflected bitterly, I had but one satisfaction. Wretched as I felt, I knew that it had spared Craig from slowing up on the case at just the time when he was needed. The news of the attempt spread quickly, for it was a police case and got into the papers. It was not half an hour after I reached the laboratory that the door was pushed open by Inez Mendoza, followed by a boy spilling with fruit and flowers like a cornucopia. "I drove to the apartment," she cried, greatly excited and sympathetic, "but they told me you had gone out. Oh, I was glad to hear it. Then I knew it wasn't so serious. For, somehow, I feel guilty about it. It never would have happened if you hadn't met me." "I'm sure it's worth more than it cost," I replied gallantly. She turned toward Kennedy. "I'm positively frightened," she exclaimed. "First they direct their attacks against my father--then against me--now against you. What will it be next? Oh--it is that curse--it is that curse!" "Never fear," encouraged Kennedy, "we'll get you out--we'll get all of us out, now, I should say. It's just because they are so desperate that we have these things. As long as there is nothing to fear a criminal will lie low. When he gets scared he does things. And it's when he does things that he begins to betray himself." She shuddered. "I feel as though I was surrounded by enemies," she murmured. "It is as if an unseen evil power was watching over me all the time--and mocking me--striking down those I love and trust. Where will it end?" Kennedy tried his best to soothe her, but it was evident that the attack on us could not have had more effect, if it had been levelled direct at her. "Please, Senorita," he pleaded, "stand firm. We are going to win. Don't give in. The Mendozas are not the kind to stop defeated." She looked at him, her eyes filled with tears. "It was my father's way," she choked back her emotion. "How could you, a stranger, know?" "I didn't know," returned Kennedy. "I gathered it from his face. It is also his daughter's way." "Yes," she said, straightening up and the fire flashing from her eyes, "we are a proud, old, unbending race. Good-bye. I must not interrupt your work any longer. We are also a race that never forgets a friend." A moment later she was gone. "A wonderful woman," repeated Kennedy absently. Then he turned again to his table of chemicals. The telephone had begun to tinkle almost continuously by this time, as one after another of our friends called us up to know how we were getting on and be assured of our safety. In fact I didn't know that it was possible to resuscitate so many of them with a pulmotor. "By George, I'm glad it wasn't any more serious," came Norton's voice from the doorway a moment later. "I didn't see a paper this morning. The curator of the Museum just told me. How did it happen?" Kennedy tried to pass it off lightly, and I did the same, for as I was up longer I really did feel better. Norton shook his head gravely, however. "No," he said, "there were four of us got warnings. They are a desperate, revengeful people." I looked at him quickly. Did he mean the de Moches? XXI THE TELESCRIBE I decided that discretion was the better part of valour and that I had better go slow that day and regain my strength, a fortunate decision, as it turned out. Kennedy, also, spent most of the time in the laboratory, so that, after all, I did not feel that I was missing very much. It was along in the afternoon that the telephone began acting strangely, as it will do sometimes when a long distance connection is being made. Twice Kennedy answered, without getting any response. "Confound that central," he muttered. "What do you suppose is the matter?" Again the bell rang. "Hello," shouted Kennedy, exasperated. "Who's this?" There was a pause. "Just a minute," he replied. Quickly he jammed the receiver down on a little metal base which he had placed near the instrument. Three prongs reaching upward from the base engaged the receiver tightly, fitting closely about it. Then he took up a watch-case receiver to listen through in place of the regular receiver. "Who is it?" he answered. Apparently the voice at the other end of the wire replied rather peevishly, for Kennedy endeavoured to smooth over the delay. I wondered what was going on, why he was so careful. His face showed that, whatever it was, it was most important. As he restored the telephone to its normal condition, he looked at me puzzled. "I wonder whether that was a frame-up!" he exclaimed, pulling a little cylinder off the instrument into which he had inserted the telephone receiver. "I thought it might be and I have preserved the voice. This is what is known as the telescribe--a recent invention of Edison which records on a specially prepared phonograph cylinder all that is said--both ways--over a telephone wire." "What was it about?" I asked eagerly. He shoved the cylinder on a phonograph and started the instrument. "Professor Kennedy?" called an unfamiliar voice. "Yes," answered a voice that I recognized as Craig's. "This is the detective agency employed by Mr. Whitney. He has instructed us to inform you that he has obtained the Peruvian dagger for which you have been searching. That's all. Good-bye." I looked at Kennedy in blank surprise. "They rang off before I could ask them a question," said Craig. "Central tells me it was a pay station call. There doesn't seem to be any way of tracing it. But, at least I have a record of the voice." "What are you going to do?" I queried. "It may be a fake." "Yes, but I'm going to investigate it. Do you feel strong enough to go down to Whitney's with me?" The startling news had been like a tonic. "Of course," I replied, seizing my hat. Kennedy paused only long enough to call Norton. The archaeologist was out, and we hurried on downtown to Whitney's. Whitney was not there and his clerk was just about to close the office. All the books were put away in the safe and the desks were closed. Now and then there echoed up the hall the clang of an elevator door. "Where is Mr. Whitney?" demanded Craig of the clerk. "I can't say. He went out a couple of hours ago." "Did he have a visit from one of his detectives?" shot out Craig suddenly. The clerk looked up suspiciously at us. "No," he replied defiantly. "Walter--stand by that door," shouted Craig. "Let no one in until they break it down." His blue-steel automatic gleamed a cold menace at the clerk. A downtown office after office hours is not exactly the place to which one can get assistance quickly. The clerk started back. "Did he have a visit from one of his detectives?" "Yes." "What was it about?" The clerk winced. "I don't know," he replied, "honest--I don't." Craig waved the gun for emphasis. "Open the safe," he said. Reluctantly the clerk obeyed. Under the point of the gun he searched every compartment and drawer of the big chrome steel strong-box which Whitney had pointed out as the safest place for the dagger on our first visit to him. But there was absolutely no trace of it. Had we been hoaxed and was all this risk in vain? "Where did Mr. Whitney go?" demanded Craig, as he directed the clerk to shut the door and lock the safe again, baffled. "If I should try to tell you," returned the man, very much frightened, "I would be lying. You would soon find out. Mr. Whitney doesn't make a confidant of me, you know." It was useless. If he had the dagger, at least we knew that it was not at the office. We had learned only one thing. He had had a visit from one of his detectives. As fast as the uptown trend of automobiles and surface cars during the rush hour would permit, Kennedy and I hurried in a taxicab to the Prince Edward Albert in the hope of surprising him there. "It's no use to inquire for him," decided Craig as we entered the hotel. "I still have the key to that room, 827, next to his. We'll ride right up in the elevator boldly and get in." No one said anything to us, as we let ourselves into the room next to Whitney's. A new lock had been placed on the door between the suites, but, aside from the additional time it took to force it, it presented no great difficulty. "He wouldn't leave the dagger here, of course," remarked Kennedy, as at last we stepped into Whitney's suite. "But we may as well satisfy ourselves. Hello--what's this?" The room was all upset, as though some one had already gone through it. For a moment I thought we had been forestalled. "Packed a grip hastily," Craig remarked, pointing to the marks on the bedspread where it had rested while he must literally have thrown things into it. We made a hasty search ourselves, but we knew it was hopeless. Two things we had learned. Whitney had had a visit from his detectives, and he had gone away hurriedly. An anonymous telephone message had been sent to Kennedy. Had it been for the purpose of throwing us off the track? The room telephone rang. Quickly Craig jumped to it and took down the receiver. "Hello," he called. "Yes, this is Mr. Whitney." A silence ensued during which, of course, I could not gather any idea of what was going on over the wire. "The deuce!" exclaimed Kennedy, working the hook up and down but receiving no response. "The fellow caught on. Something must have happened to Norton, too." "How's that?" I asked. "Why," he replied, "some one just called up Whitney and said that Norton had got away from him." "Perhaps they're trying to keep him out of the way just as they are with us," I suggested. "I think the thing is a plant." Down the hall, Kennedy stopped and tapped lightly at the door of 810, the de Moche suite. I think he was surprised when the Senora's maid opened it. "Tell Senora de Moche it is Professor Kennedy," he said quickly, "and that I must see her." The maid admitted us into the sitting-room where we had had our first interview with her and a moment later she appeared. She was evidently not dressed for dinner, although it was almost time, and I saw Kennedy's eye travel from her to a chair in the corner over which was draped a linen automobile coat and a heavy veil. Had she been preparing to go somewhere, too? The door to Alfonso's room was open and he clearly was not there. What did it all mean? "Have you heard anything of a report that the dagger has been found?" demanded Kennedy abruptly. "Why--no," she replied, greatly surprised, apparently. "You were going out?" asked Kennedy with a significant glance at the coat and veil. "Only for a little ride with Alfonso, who has gone to hire a car," she answered quickly. I felt sure that she had heard something about the dagger. We had no further excuse for staying and on the way out, now that he had satisfied himself that Whitney was not there, Craig inquired at the office for him. They could tell us nothing of his whereabouts, except that he had left in his car late in the afternoon in a great hurry. Kennedy stepped into a telephone booth and called up Lockwood, but no one answered. Inquiry in the garages in the neighbourhood finally located that at which Lockwood kept his car. There, all that they could tell us was that the car had been filled with gas and oil as if for a trip. Lockwood was gone, too. Kennedy hastily ordered a touring car himself and placed it at a corner of the Prince Edward Albert where he could watch two of the entrances, while I waited on the next corner where I could see the entrance on the other street. For some time we waited and still she did not come out. Had she telephoned to Alfonso and had he gone alone? Perhaps she had already been out and had taken this method of detaining us, knowing that we would wait to watch her. It must have been a mixture of both motives, for at length I was rewarded by seeing her come cautiously out of the rear entrance of the hotel alone and start to walk hurriedly up the street. I signalled to Craig who shot down and picked me up. By this time the Senora had reached a public cab stand and had engaged a hack. Sinking back in the shadows of the top, which was up, Craig directed our driver to follow the hack cautiously, keeping a couple of blocks behind. There was some satisfaction, though slight, in it, at least. We felt the possibility of the trail leading somewhere, now. On uptown the hack went, while we kept discreetly in the rear. We had reached a part of the city where it was sparsely populated, when the hack suddenly turned and doubled back on us. There was not time for us to turn and we trusted that by shrinking back in the shadow we might not be observed. As the hack passed us, however, the Senora leaned out until it was perfectly evident that she must recognize us. She said nothing but I fancied I saw a smile of satisfaction as she settled back into the cushions. She was deliberately going back along the very road by which she had led us out. It had been an elaborate means of wasting our time. She did not have the satisfaction, however, of shaking us off, for we followed all the way back to the hotel and saw her go in. Then Kennedy placed the car where we had it before and left the driver with instructions to follow her regardless of time if she should come out again. Surely, I reasoned, there must be something very queer going on, if they were all in it to eliminate us and Norton. What had happened to him? Kennedy hastened back to the campus, late as it was, there to start anew. Norton was not in his quarters and, on the chance that he might have sought to elude Whitney's detectives by doing the unexpected and going to the Museum, Kennedy walked over that way. There was nothing to indicate that anybody had been at the Museum, but, as we passed our laboratory, we could hear the telephone ringing inside, as though some one had been trying to get us for a long time. Kennedy opened the door and switched on the lights. Waiting only long enough to jam the receiver down into place on the telescribe, he answered the call. "The deuce you will!" I heard him exclaim, then apparently whoever was talking rang off and he could not get them back. "Another of those confounded telephone messages," he said, turning to me and taking the cylinder off. "It looks as though the ready-letter writer who used to send warnings had learned his lesson and taken to the telephone as leaving fewer clues than handwriting." He placed the record on the phonograph so that I could hear it. It was brief and to the point, as had been the first. "Hello, is that you, Kennedy? We've got Norton. Next we'll get you. Good-bye." Kennedy repeated the first message. It was evident that both had been spoken by the same voice. "Whose is it?" I asked blankly. "What does it mean?" Before Craig could answer there was a knock at our door and he sprang to open it. XXII THE VANISHER It was Juanita, Inez Mendoza's maid, frantic and almost speechless. "Why, Juanita," encouraged Kennedy, "what's the matter?" "The Senorita!" she gasped, breaking down now and sobbing over and over again. "The Senorita!" "Yes, yes," repeated Kennedy, "but what about her? Is there anything wrong?" "Oh, Mr. Kennedy," sobbed the poor girl, "I don't know. She is gone. I have had no word from her since this afternoon." "Gone!" we exclaimed together. "Where was Burke--that man that the police sent up to protect her?" "He is gone, too--now," replied Juanita in her best English, sadly broken by the excitement. Kennedy and I looked at each other aghast. This was the hardest blow of all. We had thought that, at least, Inez would be safe with a man like Burke, whom we could trust, detailed to watch her. "Tell me," urged Kennedy, "how did it happen? Did they carry her off--as they tried to do the other time?" "No, no," sobbed Juanita. "I do not know. I do not know even whether she is gone. She went out this afternoon for a little walk. But she did not come back. After it grew dark, I was frightened. I remembered that you were here and called up, but you were out. Then I saw that policeman. I told him. He has others working with him now. But I could not find you--until now I saw a light here. Oh, my poor, little girl, what has become of her? Where have they taken her? Oh, MADRE DE DIOS, it is terrible!" Had that been the purpose for which we had been sent on wild-goose chases? Was Inez really kidnapped this time? I knew not what to think. It seemed hardly possible that all of them could have joined in it. If she were kidnapped, it must have been on the street in broad daylight. Such things had happened. It would not be the first disappearance of the kind. Quickly Kennedy called up Deputy O'Connor. It was only too true. Burke had reported that she had disappeared and the police, especially those at the stations and ferries and in the suburbs had been notified to look for her. All this seemed to have taken place in those hours when the mysterious telephone calls had sent us on the wrong trail. Kennedy said nothing, but I could see that he was doing some keen thinking. Just then the telephone rang again. It was from the man whom we had left at the Prince Edward Albert. Senora de Moche had gone out and driven rapidly to the Grand Central. He had not been able to find out what ticket she bought, but the train was just leaving. Kennedy paced up and down, muttering to himself. "Whitney first--then Lockwood--and Alfonso. The Senora takes a train. Suppose the first message were true? Gas and oil for a trip." He seized the telephone book and hastily turned the pages over. At last his finger rested on a name in the suburban section. I read: "Whitney, Stuart. Res. 174-J Rockledge." Quickly he gave central the number, then shoved the receiver again into the telescribe. "Hello, is Mr. Whitney there?" I heard later as he placed the record again in the phonograph for repetition. "No--who is this?" "His head clerk. Tell him I must see him. Kennedy has been to the office and--" "Say--get off the line. We had that story once." "That's it!" exclaimed Craig. "Don't you see--they've all gone up to Whitney's country place. That clerk was faking. He has already telephoned. And listen. Do you see anything peculiar?" He was running all three records which we had on the telescribe. As he did so, I saw unmistakably that it was the same voice on all three. Whitney must have had a servant do the telephoning for him. "Don't fret, Juanita," reassured Kennedy. "We shall find your mistress for you. She will be all right. You had better go back to the apartment and wait. Walter look up the next train to Rockledge while I telephone O'Connor." We had an hour to wait before the next train left and in the meantime we drove Juanita back to the Mendoza apartment. It was a short run to Rockledge by railroad, but it seemed to me that it took hours. Kennedy sat in silence most of the time, his eyes closed, as if he were trying to place himself in the position of the others and figure out what they would do. At last we arrived, the only passengers to get off at the little old station. Which way to turn we had not the slightest idea. We looked about. Even the ticket office was closed. It looked as though we might almost as well have stayed in New York. Down the railroad we could see that a great piece of engineering was in progress, raising the level of the tracks and building a steel viaduct, as well as a new station, and at the same time not interrupting the through traffic, which was heavy. "Surely there must be some one down there," observed Kennedy, as we picked our way across the steel girders, piles of rails, and around huge machines for mixing concrete. We came at last to a little construction house, a sort of general machine-and work-shop, in which seemed to be everything from a file to a pneumatic riveter. "Hello!" shouted Craig. There came a sound from a far corner of a pile of ties and a moment later a night-watchman advanced suspiciously swinging his lantern. "Hello yourself," he growled. "Which way to Stuart Whitney's estate?" asked Craig. My heart sank as he gave the directions. It seemed miles away. Just then the blinding lights of a car flashed on us as it came down the road parallel to the tracks. He waved his light and the car stopped. It was empty, except for a chauffeur evidently returning from a joy ride. "Take these gentlemen as far as Smith's corner, will you?" asked the watchman. "Then show 'em the turn up to Whitney's." The chauffeur was an obliging chap, especially as it cost him nothing to earn a substantial tip with his master's car. However, we were glad enough to ride in anything on wheels, and not over-particular at that hour about the ownership. "Mr. Whitney hasn't been out here much lately," he volunteered as he sped along the beautiful oiled road, and the lights cast shadows on the trees that made driving as easy as in daylight. "No, he has been very busy," returned Craig glad to turn to account the opportunity to talk with a chauffeur, for it is the chauffeur in the country who is the purveyor of all knowledge and gossip. "His car passed us when I was driving up from the city. My boss won't let me speed or I wouldn't have taken his dust. Gee, but he does wear out the engines in his cars, Whitney." "Was he alone?" asked Craig. "Yes--and then I saw him driving back again when I went down, to the station for some new shoes we had expressed up. Just a flying trip, I guess--or does he expect you?" "I don't think he does," returned Craig truthfully. "I saw a couple of other cars go up there. House party?" "Maybe you'd call it that," returned Craig with a twinkle of the eye. "Did you see any ladies?" "No," returned the chauffeur. "Just a man driving his own car and another with a driver." "There wasn't a lady with Mr. Whitney?" asked Craig, now rather anxious. "Neither time." I saw what he was driving at. The Senora might have got up there in any fashion without being noticed. But for Inez not to be with Whitney, nor with the two who must evidently have been Lockwood and Alfonso, was indeed strange. Could it be that we were only half right--that they had gathered here but that Inez had really disappeared? The young man set us down at Smith's Corner and it proved to be only about an eighth of a mile up the road and up-hill when Whitney's house burst in sight, silhouetted against the sky. There were lights there and it was evident that several people had gathered for some purpose. We made our way up the path and paused a moment to look through the window before springing the little surprise. There we could see Lockwood, Alfonso, and Senora de Moche, who had arrived, after all and probably been met at the station by her son. They seemed like anything but a happy party. Never on the best of terms, they could not be expected to be happy. But now, if ever, one would have thought they might do more than tolerate each other, assuming that some common purpose had brought them here. Kennedy rang the bell and we could see that all looked surprised, for they had heard no car approach. A servant opened the door and before he knew it, Kennedy had pushed past him, taking no chances at a rebuff after the experience over the wire. "Kennedy!" exclaimed Lockwood and Alfonso together. "Where is Inez Mendoza?" demanded Craig, without returning the greeting. "Inez?" they repeated blankly. Kennedy faced them squarely. "Come, now. Where is she? This is a show-down. You may as well lay your cards on the table. Where is she--what have you done with her?" The de Moches looked at Lockwood and he looked at them, but neither spoke for a moment. "Walter," ordered Kennedy, "there's the telephone. Get the managing editor of the Star and tell him where we are. Every newspaper in the United States, every police officer in every city will have the story, in twelve hours, if you precious rascals don't come across. There--I give you until central gets die Star." "Why--what has happened?" asked Lockwood, who was the first to recover his tongue. "Don't stand there asking me what has happened," cried Kennedy impatiently. "Tickle that hook again, Walter. You know as well as I do that you have planned to get Inez Mendoza away from my influence--to kidnap her, in other words--" "We kidnap her?" gasped Lockwood. "What do you mean, man? I know nothing of this. Is she gone?" He wheeled on the de Moches. "This is some of your work. If anything happens to that girl--there isn't an Indian feud can equal the vengeance I will take!" Alfonso was absolutely speechless. Senora de Moche started to speak, but Kennedy interrupted her. "That will do from you," he cut short. "You have passed beyond the bounds of politeness when you deliberately went out of your way to throw me on a wrong trail while some one was making off with a young and innocent girl. You are a woman of the world. You will take your medicine like a man, too." I don't think I have ever seen Kennedy in a more towering rage than he was at that moment. "When it was only a matter of a paltry poisoned dagger at stake and a fortune that may be mythical or may be like that of Croesus, for all I care, we could play the game according to rules," he exclaimed. "But when you begin to tamper with a life like that of Inez de Mendoza--you have passed the bounds of all consideration. You have the Star? Telephone the story anyhow. We'll arbitrate afterward." I think, as I related the facts to my editor, it sobered us all a great deal. "Kennedy," appealed Lockwood at last, as I hung up the receiver, "will you listen to my story?" "It is what I am here for," replied Craig grimly. "Believe it or not, as far as I am concerned," asserted Lockwood, "this is all news to me. My God--where is she?" "Then how came you here?" demanded Craig. "I can speak only for myself," hastened Lockwood. "If you had asked where Whitney was, I could have understood, but--" "Well, where is he?" "We don't know. Early this afternoon I received a hurried message from him--at least I suppose it was from him--that he had the dagger and was up here. He said--I'll be perfectly frank--he said that he was arranging a conference at which all of us were to be present to decide what to do." "Meanwhile I was to be kept away at any cost," supplied Kennedy sarcastically. "Where did he get it?" "He didn't say." "And you didn't care, as long as he had it," added Craig, then, turning to the de Moches, "And what is your tale?" Senora de Moche did not lose her self-possession for an instant. "We received the same message. When you called, I thought it would be best for Alfonso to go alone, so I telephoned and caught him at the garage and when my train arrived here, he was waiting." "None of you have seen Whitney here?" asked Kennedy, to which all nodded in the negative. "Well, you seem to agree pretty well in your stories, anyhow. Let me take a chance with the servants." It is no easy matter to go into another's household and without any official position quiz and expect to get the truth out of the servants. But Kennedy's very wrath seemed to awe them. They answered in spite of themselves. It seemed clear that as far as they went both guests and servants were telling the truth. Whitney had made the run up from the city earlier in the afternoon, had stayed only a short time, then had gone back, leaving word that he would be there again before his guests arrived. They all professed to be as mystified as ourselves now over the outcome of the whole affair. He had not come back and there had been no word from him. "One thing is certain," remarked Craig, watching the faces before him as he spoke. "Inez is gone. She has been spirited away without even leaving a trace. Her maid Juanita told me that. Now if Whitney is gone, too, it looks as if he had planned to double-cross the whole crowd of you and leave you safely marooned up here with nothing left but your common hatred of me. Much good may it do you." Lockwood clenched his fists savagely, not at Kennedy but at the thought that Craig had suggested. His face set itself in tense lines as he swore vengeance on all jointly and severally if any harm came to Inez. I almost forgot my suspicions of him in admiration. "Nothing like this would ever have happened if she had stayed in Peru," exclaimed Alfonso bitterly. "Oh, why did her father ever bring her here to this land of danger?" The idea seemed novel to me to look on America as a lawless, uncultured country, until I reflected on the usual Latin-American opinion of us as barbarians. Lockwood frowned but said nothing, for a time. Then he turned suddenly to the Senora, "You were intimate enough with him," he said. "Did he tell you any more than he told us?" It was clear that Lockwood felt now that every man's hand was against him. I thought I could discover a suppressed gleam of satisfaction in her wonderful eyes as she answered, "Nothing more. It was only that I carried out what he asked me." Could it be that she was taking a subtle delight in the turn of events--the working out of a curse on the treasure-secret which the fatal dagger bore? I could not say. But it would not have needed much superstition to convince any one that the curse on the Gold of the Gods was as genuine as any that had ever been uttered, as it heaped up crime on crime. We waited in silence, the more hopeless as the singing of the night insects italicized our isolation from the organized instruments of man for the righting of wrong. Here we were, each suspecting the other, in the home of a man whom all mistrusted. "There's no use sitting here doing nothing," exclaimed Lockwood in whose mind was evidently the same thought, "not so long as we have the telephone and the automobiles." These, at least, were our last bonds with the great world that had wrapped a dark night about a darker mystery. "There are many miles of wire--many miles of road. Which way shall we turn?" Senora de Moche seemed to take a fiendish delight in the words as she said them. It was as though she challenged our helplessness in the face of a power that was greater than us all. Lockwood flashed a look of suspicion in her direction. As for myself, I had never been able to make the woman out. To-night she seemed like a sort of dea ex machina, who sat apart, playing on the passions of a group of puppet men whom she set against each other until all should be involved in a common ruin. It was impossible, in the silence of this far-off lonely place in the country, not to feel the weirdness of it all. Once I closed my eyes and was startled by the uncanny vividness of a mind-picture that came unbidden. It was of a scrap of paper on which, in rough capitals was printed: BEWARE THE CURSE OF MANSICHE ON THE GOLD OF THE GODS. XXIII THE ACETYLENE TORCH Do you suppose he really had the dagger, or was that a lie?" I asked, with an effort shaking off the fateful feeling that had come over me as if some one were casting a spell. "There is one way to find out," returned Craig, as though glad of the suggestion. Though they hated him, they seemed forced to admit, for the time, his leadership. He rose and the rest followed as he went into Whitney's library. He switched on the lights. There in a corner back of the desk stood a safe. Somehow or other it seemed to defy us, even though its master was gone. I looked at it a moment. It was a most powerful affair, companion to that in the office of which Whitney was so proud, built of layer on layer of chrome steel, with a door that was air tight and soup-proof, bidding defiance to all yeggmen and petermen. Lockwood fingered the combination hopelessly. There were some millions of combinations and permutations that only a mathematician could calculate. Only one was any good. That one was locked in the mind of the man who now seemed to baffle us as did his strong-box. I placed my hand on the cold, defiant surface. It would take hours to drill a safe like that, and even then it might turn the points of the drills. Explosives might sooner wreck the house and bring it down over the head of the man who attacked this monster. "What can we do?" asked Senora de Moche, seeming to mock us, as though the safe itself were an inhuman thing that blocked our path. "Do?" repeated Kennedy decisively, "I'll show you what we can do. If Lockwood will drive me down to the railroad station in his car, I'll show you something that looks like action. Will you do it?" The request was more like a command. Lockwood said nothing, but moved toward the porte-cochere, where he had left his car parked just aside from the broad driveway. "Walter, you will stay here," ordered Kennedy. "Let no one leave. If any one comes, don't let him get away. We shan't be gone long." I sat awkwardly enough, scarcely speaking a word, as Kennedy dashed down to the railroad station. Neither Alfonso nor his mother betrayed either by word or action a hint of what was passing in their minds. Somehow, though I did not understand it, I felt that Lockwood might square himself. But I could not help feeling that these two might very possibly be at the bottom of almost anything. It was with some relief that I heard the car approaching again. I had no idea what Kennedy was after, whether it was dynamite or whether he contemplated a trip to New York. I was surprised to see him, with Lockwood, hurrying up the steps to the porch, each with a huge tank studded with bolts like a boiler. "There," ordered Craig, "set the oxygen there," as he placed his own tank on the opposite side. "That watchman thought I was bluffing when I said I'd get an order from the company, if I had to wake up the president of the road. It was too good a chance to miss. One doesn't find such a complete outfit ready to hand every day." Out of the tanks stout tubes led, with stop-cocks and gauges at the top. From a case under his arm Kennedy produced a curious arrangement like a huge hook, with a curved neck and a sharp beak. Really it consisted of two metal tubes which ran into a sort of cylinder, or mixing chamber, above the nozzle, while parallel to them ran a third separate tube with a second nozzle of its own. Quickly he joined the ends of the tubes from the tanks to the metal hook, the oxygen tank being joined to two of the tubes of the hook, and the second tank being joined to the other. With a match he touched the nozzle gingerly. Instantly a hissing, spitting noise followed, and an intense, blinding needle of flame. "Now we'll see what an oxyacetylene blow-pipe will do to you, old stick-in-the-mud," cried Kennedy, as he advanced toward the safe, addressing it as though it had been a thing of life that stood in his way. "I think this will make short work of you." Almost as he said it, the steel beneath the blow-pipe became incandescent. For some time he laboured to get a starting-point for the flame of the high-pressure torch. It was a brilliant sight. The terrific heat from the first nozzle caused the metal to glow under the torch as if in an open-hearth furnace. From the second nozzle issued a stream of oxygen, under which the hot metal of the door was completely consumed. The force of the blast, as the compressed oxygen and acetylene were expelled, carried a fine spray of the disintegrated metal visibly before it. And yet it was not a big hole that it made--scarcely an eighth of an inch wide, but clean and sharp as if a buzz-saw were eating its way through a plank of white-pine. With tense muscles Kennedy held this terrific engine of destruction and moved it as easily as if it had been a mere pencil of light. He was the calmest of all of us as we crowded about him, but at a respectful distance. "I suppose you know," he remarked hastily, never pausing for a moment in his work, "that acetylene is composed of carbon and hydrogen. As it burns at the end of the nozzle it is broken into carbon and hydrogen--the carbon gives the high temperature and the hydrogen forms a cone that protects the end of the blow-pipe from being itself burnt up." "But isn't it dangerous?" I asked, amazed at the skill with which he handled the blow-pipe. "Not particularly--when you know how to do it. In that tank is a porous asbestos packing saturated with acetone, under pressure. Thus they carry acetylene safely, for it is dissolved and the possibility of explosion is minimized. "This mixing chamber, by which I am holding the torch, where the oxygen and acetylene mix, is also designed in such a way as to prevent a flash-back. The best thing about this style of blow-pipe is the ease with which it can be transported and the curious purposes--like this--to which it can be put." He paused a moment to test what had been burnt. The rest of the safe seemed as firm as ever. "Humph!" I heard one of them, I think it was Alfonso, mutter. I resented it, but Kennedy affected not to hear. "When I shut off the oxygen in this second jet," he resumed, "you see the torch merely heats the steel. I can get a heat of approximately sixty-three hundred degrees Fahrenheit, and the flame will exert a pressure of fifty pounds to the square inch." "Wonderful!" exclaimed Lockwood, who had not heard the suppressed disapproval of Alfonso, and was watching, in undisguised admiration at the thing itself, regardless of consequences. "Kennedy, how did you ever think of such a thing?" "Why, it's used for welding, you know," answered Craig, as he continued to work calmly in the growing excitement. "I first saw it in actual use in mending a cracked cylinder in an automobile. The cylinder was repaired without being taken out at all. I've seen it weld new teeth and build up worn teeth on gearing, as good as new." He paused to let us see the terrifically heated metal under the flame. "You remember when we were talking to the watchman down there at the station, Walter?" he asked. "I saw this thing in that complete little shop of theirs. It interested me. See. I turn on the oxygen now in the second nozzle. The blow-pipe is no longer an instrument for joining metals together, but for cutting them asunder. "The steel burns just as you, perhaps, have seen a watch-spring burn in a jar of oxygen. Steel, hard or soft, tempered, annealed, chrome, or Harveyized, it all burns just about as fast, and just about as easily under this torch. And it's cheap, too. This attack--aside from what it costs to the safe--may amount to a couple of dollars as far as the blow-pipe is concerned--quite a difference from the thousands of dollars' loss that would follow an attempt to blow a safe like this one." We had nothing to say. We stood in awe-struck amazement as the torch slowly, inexorably traced a thin line along the edge of the combination. Minute after minute sped by, as the line burned by the blow-pipe cut around the lock. It seemed hours, but really it was minutes. I wondered when he would have cut about the whole lock. He was cutting clear through and around it, severing it as if with a superhuman knife. With something more than half his work done, he paused a moment to rest. "Walter," he directed, mopping his forehead, for it was real work directing that flaming knife, "get New York on the wire. See if O'Connor is at his office. If he has any report, I want to talk to him." It was getting late and the service was slackening up. I had some trouble, especially in getting a good connection, but at last I got headquarters and was overjoyed to hear O'Connor's bluff, Irish voice boom back at me. "Hello, Jameson," he called. "Where on earth are you? I've been trying to get hold of Kennedy for a couple of hours. Rockledge? Well, is Kennedy there? Put him on, will you?" I called Craig and, as I did so, my curiosity got the better of me and I sought out an extension of the wire in a den across the hall from the library, where I could listen in on what was said. "Hello, O'Connor," answered Craig. "Anything from Burke yet?" "Yes," came back the welcome news. "I think he has a clue. We found out from here that she received a long distance message during the afternoon. Where did Jameson say you were--Rockledge?--that's the place. Of course we don't know what the message was, but anyhow she went out to meet some one right after that. The time corresponds with what the maid says." "Anything else?" asked Craig. "Have you found any one who saw her?" "Yes. I think she went over to your laboratory. But you were out." "Confound it!" interrupted Craig. "Some one saw a woman there." "It wasn't the maid?" "No, this was earlier--in the afternoon. She left and walked across the campus to the Museum." "Oh, by the way, any word of Norton?" "I'm coming to that. She inquired for Norton. The curator has given a good description. But he was out--hadn't been there for some time. She seemed to be very much upset over something. She went away. After that we've lost her." "Not another trace?" "Wait a minute. We had this Rockledge call to work on. So we started backward on that. It was Whitney's place, I found out. We could locate the car at the start and at the finish. He left the Prince Edward Albert and went up there first. Then he must have come back to the city again. No one at the hotel saw him the second time. "What then?" hastened Craig. "She may have met him somewhere, though it's not likely she had any intention of going away. All the rest of those people you have up there seem to have gone prepared. We got something on each of them. Also you'll be interested to know I've got a report of your own doings. It was right, Kennedy, I don't blame you. I'd have done the same with Burke on the job. How are you making out? What? You're cracking a crib? With what?" O'Connor whistled as Kennedy related the story of the blow-pipe. "I think you're on the right track," he commended. "There's nothing to show it, but I believe Whitney told her something that changed her mind about going up there. Probably met her in some tea room, although we can't find anything from the tea rooms. Anyhow, Burke's out trailing along the road from New York to Rockledge and I'm getting reports from him whenever he hits a telephone." "I wish you'd ask him to call me, here, if he gets anything." "Sure I will. The last call was from the Chateau Rouge,--that's about halfway. There was a car with a man and a woman who answers her description. Then, there was another car, too." "Another car?" "Yes--that's where Norton crosses the trail again. We searched his apartment. It was upset--like Whitney's. I haven't finished with that. But we have a list of all the private hacking places. I've located one that hired a car to a man answering Norton's description. I think he's on the trail. That's what I meant by another car." "What's he doing?" "Maybe he has a hunch. I'm getting superstitious about this case. You know Luis de Mendoza has thirteen letters in it. Leslie told me something about a threat he had--a curse. You better look out for those two greasers you have up there. They may have another knife for you." Kennedy glanced over at the de Moches, not in fear but in amusement at what they would think if they could hear O'Connor's uncultured opinion. "All right, O'Connor," said Craig, "everything seems to be going as well as we can expect. Don't forget to tell Burke I'm here." "I won't. Just a minute. He's on another wire for me." Kennedy waited impatiently. He wanted to finish his job on the safe before some one came walking in and stopped it, yet there was always a chance that Burke might turn up something. "Hello," called O'Connor a few minutes later. "He's still following the two cars. He thinks the one with the woman in it is Whitney's, all right. But they've got off the main road. They must think they're being followed. "Or else have changed their destination," returned Craig. "Tell him that. Maybe Whitney had no intention of coming up here. He may have done this thing just to throw these people off up here, too. I can't say. I can tell better whether he intended to come back after I've got this safe open. I'll let you know." Kennedy rang off. "Any news of Inez?" asked Lockwood who had been fuming with impatience. "She's probably on her way up here," returned Craig briefly, taking up the blow-pipe again. Alfonso remained silent. The Senora could scarcely hide her excitement. If there were anything in telepathy, I am sure that she read everything that was said over the wire. Quickly Craig resumed his work, biting through the solid steel as if it had been mere pasteboard, the blow-pipe showering on each side a brilliant spray of sparks, a gaudy, pyrotechnic display. Suddenly, with a quick motion, Kennedy turned off the acetylene and oxygen. The last bolt had been severed, the lock was useless. A gentle push of the hand, and he swung the once impregnable door on its delicately poised hinges as easily as if he had merely said, "Open sesame." Craig reached in and pulled open a steel drawer directly in front of him. There in the shadow lay the dagger--with its incalculably valuable secret, a poor, unattractive piece of metal, but with a fascination such as no other object, I had ever seen, possessed. There was a sudden cry. The Senora had darted ahead, as if to clasp its handle and unloose the murderous blade that nestled in its three-sided sheath. Before she could reach it, Kennedy had seized her hand in his iron grasp, while with the other he picked up the dagger. They stood there gazing into each other's eyes. Then the Senora burst into a hysterical laugh. "The curse is on all who possess it!" "Thank you," smiled Kennedy quietly, releasing her wrist as he dropped the dagger into his pocket, "I am only the trustee." XXIV THE POLICE DOG Craig faced us, but there was no air of triumph in his manner. I knew what was in his mind. He had the dagger. But he had lost Inez. What were we to do? There seemed to be no way to turn. We knew something of the manner of her disappearance. At first she had, apparently, gone willingly. But it was inconceivable that she stayed willingly, now. I recalled all the remarks that Whitney had ever made about her. Had the truth come out in his jests? Was it Inez, not the dagger, that he really wanted? Or was he merely the instrument of one or all of these people before us, and was this an elaborate plan to throw Kennedy off and prove an alibi for them? He had been the partner of Lockwood, the intimate of de Moche. Which was he working for, now--or was he working for himself alone? No answer came to my questions, and I reflected that none would ever come, if we sat here. Yet there seemed to be no way to turn, without risking putting ourselves in a worse position than before. At least, until we had some better plan of campaign, we occupied a strategic advantage in Whitney's own house. The hours of the night wore on. Midnight came. This inaction was killing. Anything would be better than that. Suddenly the telephone startled us. We had wanted it to ring, yet when it rang we were afraid of it. What was its message? It was with palpitating hearts that we listened, while Craig answered. "Yes, Burke," we heard him reply, "this is Kennedy." There came a pause during which we could scarcely wait. "Where are you now? Cold Stream. That is about twelve miles from Rockledge--not on the New York road--the other road. I see. All right. We'll be there. Yes, wait for us." As Craig hung up the receiver, we crowded forward. "Have they found her?" asked Lockwood hoarsely. "It was from Burke," replied Kennedy deliberately. "He is at a place called Cold Stream, twelve miles from here. He tells me that we can find it easily--on a state road, at a sharp curve that has been widened out, just this side of the town. There has been an accident--Whitney's car is wrecked." Lockwood seized his elbow. "My God," he exclaimed, "tell me--she isn't--hurt, is she? Quick!" "So far Burke has not been able to discover a trace of a thing, except the wrecked car," replied Kennedy. "I told him I would be over directly. Lockwood, you may take Jameson and Alfonso. I will go with the Senora and their driver." I saw instantly why he had divided the party. Neither mother nor son was to have a chance to slip away from us. Surely both Lockwood and I should be a match for Alfonso. Senora de Moche he would trust to none but himself. Eagerly now we prepared for the journey, late though it was. No one now had a thought of rest. There could be no rest with that mystery of Inez challenging us. We were off at last, Lockwood's car leading, for although he did not know the roads exactly, he had driven much about the country. I should have liked to have sat in front with him, but it seemed safer to stay in the back with Alfonso. In fact, I don't think Lockwood would have consented, otherwise, to have his rival back of him. Kennedy and the Senora made a strange pair, the ancient order and the ultra-modern. There was a peculiar light in her eyes that gleamed forth at the mere mention of the words, "wreck." Though she said nothing, I knew that through her mind was running the one tenacious thought. It was the working out of the curse! As for Craig, he was always seeking the plausible, natural reason for what to the rest of us was inexplicable, often supernatural. To him she was a fascinating study. On we sped, for Lockwood was a good driver and now was spurred on by an anxiety that he could not conceal. Yet his hand never faltered at the wheel. He seemed to read the signs at the cross-roads without slackening speed. In spite of all that I knew, I found myself compelled to admire him. Alfonso sat back, for the most part silent. The melancholy in his face seemed to have deepened. He seemed to feel that he was but a toy in the hands of fate. Yet I knew that underneath must smoulder the embers of a bitter resentment. It seemed an interminable ride even at the speed which we were making. Twelve miles in the blackness of a country night can seem like a hundred. At last as we turned a curve, and Lockwood's headlights shone on the white fence that skirted the outer edge of the road as it swung around a hill that rose sharply to our left and dropped off in a sort of ravine at the right beyond the fence, I felt the car tremble as he put on the brakes. A man was waving his arms for us to stop, and as we did, he ran forward. He peered in at us and I recognized Burke. "Whe-where's Kennedy?" he asked, disappointed, for the moment fearing he had made a mistake and signalled the wrong car. "Coming," I replied, as we heard the driver of the other car sounding his horn furiously as he approached the curve. Burke jumped to the safe side of the road and ran on back to signal to stop. It was then for the first time that I paid particular attention to the fence ahead of us on which now both our own and the lights of the other car shone. At one point it was torn and splintered, as though something had gone through it. "Great heavens, you don't mean to say that they went over that?" muttered Lockwood, jumping down and running forward. Kennedy had joined us by this time and we all hurried over. Down in the ravine we could see a lantern which Burke had brought and which was now resting on the overturned chassis of the car. Lockwood was down there ahead of us all, peering under the heavy body fearfully, as if he expected to see two forms of mangled flesh. He straightened up, then took the lantern and flashed it about. There was nothing except cushions and a few parts of the car within the radius of its gleam. "Where are they?" he demanded, turning to us. "It's Whitney's car, all right." Burke shook his head. "I've traced the car so far. They were getting ahead of me, when this happened." Together we managed to right the car which was on a hillock. It sank a little further down the hill, but at least we could look inside it. "Bring the lantern," ordered Kennedy. Minutely, part by part, he went over the car. "Something went wrong," he muttered. "It is too much wrecked to tell what it was. Flash the light over here," he directed, stepping over the seat into the back of the tonneau. A moment later he took the light himself and held it close to the rods that supported the top. I saw him reach down and pull from them a few strands of dark hair that had caught between the rods and had been pulled out or broken. "No need of Bertillon's palette of human hair to identify that," he exclaimed. "There isn't time to study it and if there were it would be unnecessary. She was with him, all right." "Yes," agreed Lockwood. "But where is she now--where is he? Could they have been hurt, picked up by some one and carried where they could get aid?" Burke shook his head. "I inquired at the nearest house ahead. I had to do it in order to telephone. They knew nothing." "But they are gone," persisted Lockwood. "There is the bottom of the bank. You can see that they are not here." Kennedy had taken the light and climbed the bank again and was now going over the road as minutely as if he were searching for a lost diamond. "Look!" he exclaimed. Where the Whitney car had skidded and gone over the bank, the tires had dug deep into the top dressing, making little mounds. Across them now we could see the tracks of other tires that had pressed down the mounds. "Some one else has been here," reconstructed Kennedy. "He passed, then stopped and backed up. Perhaps they were thrown out, unconscious, and he picked them up." It seemed to be the only reasonable supposition. "But they knew nothing at the next house," persisted Burke. "Is there a road leading off before you get to the house?" asked Kennedy. "Yes--it crosses the line into Massachusetts." "It is worth trying--it is the only thing we can do," decided Kennedy. "Drive slowly to the crossroads. Perhaps we can pick out the tire-prints there. They certainly won't show on the road itself. It is too hard." At the crossing we stopped and Kennedy dropped down on his hands and knees again with the light. "There it is," he exclaimed. "The same make of anti-skid tire, at least. There was a cut in the rear tire--just like this. See? It is the finger-print of the motor car. I think we are right. Turn up here and run slowly." On we went slowly, Kennedy riding on the running-board of the car ahead. Suddenly he raised his hand to stop, and jumped down. We gathered about him. Had he found a continuation of the tire-tracks? There were tracks but he was not looking at them. He was looking between them. There ran a thin line. He stuck his finger in it and sniffed. "Not gas," he remarked. "It must have been the radiator, leaking. Perhaps he ran his car into Whitney's--forced it too far to the edge of the road. We can't tell. But he couldn't have gone far with that leak without finding water--or cracked cylinders." With redoubled interest now we resumed the chase. We had mounted a hill and had run down into the shadows of a valley when, following in the second car, we heard a shout from Kennedy in the first. Halfway up the hill across the valley, he had come upon an abandoned car. It had evidently reached its limit, the momentum of the previous hill had carried it so far up the other, then the driver had stopped it and let it back slowly off the road into a clump of bushes that hid a little gully. But that was all. There was not a sign of a person about. Whatever had happened here had happened some hours before. We looked about. All was Cimmerian darkness. Not a house or habitation of man or beast was in sight, though they might not be far away. We beat about the under-brush, but succeeded in stirring up nothing but mosquitoes. What were we to do? We were wasting valuable time. Where should we go? "I doubt whether they would have kept on the road," reasoned Kennedy. "They must have known they would be followed. The hardest place to follow them would be across country." "With a lantern?" I objected. "We can't do it." Kennedy glanced at his watch. "It will be three hours before there is light enough to see anything by," he considered. "They have had at least a couple of hours. Five hours is too good a start. Burke--take one of the cars. Go ahead along the road. We mustn't neglect that. I'll take the other. I want to get back to that house and call O' Connor. Walter, you stay here with the rest." We separated and I felt that, although I was doing nothing, I had my hands full watching these three. Lockwood was restless and could not help beating around in the under-brush, in the hope of turning up something. Now and then he would mutter to himself some threat if anything happened to Inez. I let him occupy himself, for our own, as much as his, peace of mind. Alfonso had joined his mother in the car and they sat there conversing in low tones in Spanish, while I watched them furtively. Of a sudden, I became aware that I missed the sound of Lockwood beating about the under-brush. I called, but there was no answer. Then we all called. There came back nothing but a mocking echo. I could not follow him. If I did, I would lose the de Moches. Had he been laying low, waiting his opportunity to get away? Or was he playing a lone hand? Much as I suspected about him, during the past few hours I had come to admire him. I sent the de Moche driver out to look for him, but he seemed afraid to venture far, and, of course, returned and said that he could not find him. Even in his getaway, Lockwood had been characteristic. He had been strong enough to bide his time, clever enough to throw every one off guard. It put a new aspect on the case for me. Had Whitney intended the capture of Inez for Lockwood? Had our coming so unexpectedly into the case thrown the plans awry and was it the purpose to leave them marooned at Rockledge while we were shunted off in the city? That, too, was plausible. I wished Kennedy would return before anything else happened. It was not long by the clock before Kennedy did return. But it seemed ages to me. He was not alone. With him was a man in a uniform, and a powerful dog, for all the world like a huge wolf. "Down, Searchlight," he ordered, as the dog began to show an uncanny interest in me. "Let me introduce my new dog detective," he chuckled. "She has a wonderful record as a police dog. I got O'Connor out of bed and he telephoned out to the nearest suburban station. That saved a good deal of time in getting her up here." I mustered up courage to tell Kennedy of the defection of Lockwood. He did not seem to mind it especially. "He won't get far, with the dog after him, if we want to take the time," he said. "She's a German sheep dog, a Schaeferhund." Searchlight seemed to have many of the characteristics of the wild, prehistoric animal, among them the full, upright ears of the wild dog, which are such a great help to it. She was a fine, alert, upstanding dog, hardy, fierce, and literally untiring, of a tawny light brown like a lioness, about the same size and somewhat of the type of the smooth-coated collie, broad of chest and with a full brush of tail. Untamed as she seemed, she was perfectly under Kennedy's control and rendered him absolute and unreasoning obedience. They took her over to the abandoned car. There they let her get a good whiff of the bottom of the car about the driver's feet, and a moment later she started off. Alfonso and his mother insisted on going with us and that made our progress across country slow. On we went over the rough country, through a field, then skirting a clump of woods until at last we came to a lane. We stopped in the shadow of a thicket. There was an empty summer home. Was there some intruder there? Was it really empty? Now and then we could hear Searchlight scouting about in the under-brush, crouching and hiding, watching and guarding. We paused and waited in the heavily-laden night air, wondering. The soughing of the night wind in the evergreens was mournful. Did it betoken a further tragedy? There was a slight noise from the other side of the house. Craig reached out and drew us back into the shadow of the thicket, deeper. "Some one is prowling about, I think. Leave it to the dog." Searchlight, who had been near us, was sniffing eagerly. From our hiding-place we could just see her. She had heard the sounds, too, even before we had, and for an instant stood with every muscle tense. Then, like an arrow, she darted into the underbrush. An instant later, the sharp crack of a revolver rang out. Searchlight kept right on, never stopping a second, except, perhaps, in surprise. "Crack!" almost in her face came a second spit of fire in the darkness, and a bullet crashed through the leaves and buried itself in a tree with a ping. The intruder's marksmanship was poor, but the dog paid no attention to it. "One of the few animals that show no fear of gun-fire," muttered Kennedy, in undisguised admiration. "G-r-r-r," we heard from the police dog. "She has made a leap at the hand that holds the gun," cried Kennedy, now rising and moving rapidly in the same direction. "She has been taught that a man once badly bitten in the hand is nearly out of the fight." We followed also. As we approached we were just in time to see Searchlight running in and out between the legs of a man who had heard us approach and was hastily making tracks away. As he tripped, the officer who brought her blew shrilly on a police whistle just in time to stop a fierce lunge at his back. Reluctantly, Searchlight let go. One could see that with all her canine instinct she wanted to "get" that man. Her jaws were open, as, with longing eyes, she stood over the prostrate form in the grass. The whistle was a signal, and she had been taught to obey unquestioningly. "Don't move until we get to you, or you are a dead man," shouted Kennedy, pulling an automatic as he ran. "Are you hurt?" There was no answer, but, as we approached, the man moved, ever so little, through curiosity to see his pursuers. Searchlight shot forward. Again the whistle sounded and she dropped back. We bent over to seize him, as Kennedy secured the dog. "She's a devil," ground out the prone figure on the grass. "Lockwood!" exclaimed Kennedy. XXV THE GOLD OF THE GODS "What are you doing here?" demanded Craig, astonished. "I couldn't wait for you to get back. I thought I'd do a little detective work on my own account. I kept getting further and further away, knew you'd find me, anyhow. But I didn't think you'd have a brute like that," he added, binding up his hand ruefully. "Is there any trace of Inez?" "Not yet. Why did you pick out this house?" asked Kennedy, still suspicious. "I saw a light here, I thought," answered Lockwood frankly. "But as I approached, it went out. Maybe I imagined it." "Let us see." Kennedy spoke a few words to the man with the dog. He slipped the leash, with a word that we did not catch, and the dog bounded off, around the house, as she was accustomed to do when out on duty with an officer in the city suburbs, circling about the backs of houses as the man on the beat walked the street. She made noise enough about it, too, tumbling over a tin pail that had been standing on the back porch steps. "Bang!" Some one was in the house and was armed. In the darkness he had not been able to tell whether an attack was being made or not, but had taken no chances. At any rate, now we knew that he was desperate. I thought of all the methods Kennedy had adopted to get into houses in which the inmates were desperate. But always they had been about the city where he could call upon the seemingly exhaustless store of apparatus in his laboratory. Here we were faced by the proposition with nothing to rely on but our native wit and a couple of guns. Besides, I did not know whether to count on Lockwood as an ally or not. My estimation of him had been rising and falling like the barometer in a summer shower. I had been convinced that he was against us. But his manner and plausibility now equally convinced me that I had been mistaken. I felt that it would take some supreme action on his part to settle the question. That crisis was coming now. I think all of us would willingly have pushed Alfonso forward. But the relations of the de Moches with Whitney had been so close that I no more trusted him than I did Lockwood. And if I could not make out Lockwood, a man at least of our own race and education, how could I expect to fathom Alfonso? It seemed, then, to rest with Kennedy and myself. At least so Craig appraised the situation. "You have a gun, Walter," he directed, "Lockwood, give yours to Jameson." Lockwood hesitated. Could he trust being unarmed, while Kennedy and I had all the weapons? Craig had not stopped to ask Alfonso. As he laid out the attack he merely tapped the young man's pockets to see whether he was armed or not, and finding nothing faced us again, Lockwood still hesitating. "I want Walter," explained Craig, "to go around back of the house. It is there they must be expecting an attack. He can take up his position behind that oak. It will be safe enough. By firing one gun on each side of the tree he can make enough noise for half a dozen. Then you and I can rush the front of the house." Lockwood had nothing better to suggest. Reluctantly he handed over his revolver. I dropped back from them and skirted the house at a safe distance so as not to be seen, then came up back of the tree. Carefully I aimed at the glass of a window on the first floor, as offering the greatest opportunity for making a racket, which was the object I had in mind. I fired from the right and the glass was shattered in a thousand bits. Another shot from the left broke the light out of another window on the opposite side. The house was a sort of bungalow, with most of the rooms on the first floor, and a small second story or attic window. That went next. Altogether I felt that I was giving a splendid account of myself. From the house came a rapid volley in reply. Whoever was in there was not going to surrender without a fight. One after another I plugged away with my shots, now bent on making the most of them. With the answering shots it made quite a merry little fusillade, and I was glad enough to have the shelter of the staunch oak which two or three times was hit squarely at about the level of my shoulders. I had never before heard the whirr of so many bullets about me, and I cannot say that I enjoyed it. But my attack was what Craig wanted. I heard a noise in the front of the house, as of feet running, and then I knew that in spite of all he had given me the least dangerous part of the attack. I plugged away valiantly with what shots I had left, then leaving just one more in the chamber of each gun, I hurried around in the shadow, my blood up, to help them. With the aid of the officer, they had just forced the light door and Searchlight had been allowed to leap in ahead of them, as I came up. "Here," I said to Lockwood, handing him back his gun, "take it, there is just one shot left." I, at least, had expected to find one, perhaps two desperate men waiting for us. Evidently our ruse had worked. The room was dark, but there seemed to be no one in it, though we could hear sounds as though some one were hastily barricading the door that led from the front to the room at which I had been firing. Lockwood struck a match. "Confound it, don't!" muttered Craig, knocking it from his hand. "They can see us well enough without helping them." "Chester!" We stood transfixed. It was a woman's voice. Where did it come from? Could she be in the room? "Chester--is that you?" "Yes, Inez. Where are you?" "I ran up here--in this attic--when I heard the shots." "Come down, then. All is right, now." She came down a half ladder, half flight of steps. At the foot she paused just a moment and hesitated. Then, like a frightened bird, she flew to the safety of Lockwood's arms. "Mr. Whitney," she sobbed, "called me up and told me that he had something very important to say, a message from you. He said that he had the dagger, in his safe, up in the country. He told me you'd be there and that you expected me to come up with him in his car. I went. We had some trouble with the engine. And then that other car--the one that followed us, came up behind and forced us off the bank. Mr. Whitney and I were both stunned. I don't remember a thing after that, until I woke up here. Where is it?" I listened, with one eye on that door that had been barricaded. Was Lockwood really innocent, after all? I could not think that Inez Mendoza could make such a mistake, if he were not. Lockwood clenched his fists. "Some one shall pay for this," he exclaimed. There was the problem--the inner room. Who would go in? We looked at each other a moment. The room in which we were was a living room, and perhaps, when there were visitors in the little house, was a guest-room. At any rate, on one side was a huge davenport by day which could be transformed into a folding bed at night. Lockwood looked about hastily and his eye fell on the door, then on this folding bed. With a wrench, he opened it and seized the cotton mattress from the inside. With his gun ready he advanced toward the barricaded door, holding the mattress as a shield, for his experience in wild countries had taught him that a cotton mattress is about as good a thing to stop bullets as one could find on the spur of the moment. Kennedy and the officer followed just behind, and the three threw their weights on the door almost before we knew what they were about. "Chester--don't!" cried Inez in alarm, too late. "He'll--kill you!" The excitement had been too much for her. She reeled, fainting, and I caught her. Before I could restore the davenport to something like its original condition so that we could take care of her, the first onslaught was over. Three guns were sticking their blue noses into the darkness of the next room. "Hands up!" shouted Craig, "Drop your gun! Let me hear it fall!" There followed a thud and Kennedy, followed by Lockwood and the officer entered. As they fumbled to strike a light, I managed to open a window and let in some fresh air, while the Senora, for once human, loosened the throat of Inez' dress and fanned her. Through the open door, now, I could hear what was going on in the next room, but could not see. "It was you, Lockwood," I heard a familiar voice accusing, "who was in the Museum the night the dagger disappeared." "Yes," replied Lockwood, a bit disdainfully. "I suspected something crooked about that dagger. I thought that if I made a copy of the inscription on the blade, I might decipher it myself, or get some one to do it for me. I went in and, when a chance came, I hid in the sarcophagus. There I waited until the Museum was closed. Then, when finally I got to the place where I thought the dagger was--it was gone!" "The point is," cut in Craig, interrupting, "who was the mysterious visitor to Mendoza the night of his murder?" He paused. No one seemed to be disposed to answer and he went on, "Who else than the man who sought to sell the secret on its blade, in return for Inez for whom he had a secret passion? I have reasoned it all out--the offer, the quarrel, the stabbing with the dagger itself, and the escape down the stairs, instead of by the elevator." "And I," put in Lockwood, "coming to report to Mendoza my failure to find the dagger, found him dead--and at once was suspected of being the murderer!" Inez had revived and her quick ears had caught her lover's voice and the last words. Weak as she was, she sprang up and fairly ran into the next room. "No--Chester--No!" she cried. "I never suspected--not even when I saw the shoe-prints. No--that is the man,--there--I know it--I know it!" I hurried after her, as she flung herself again between Lockwood and the rest of us, as if to shield him, while Lockwood proudly caressed the stray locks of dark hair that fluttered on his shoulder. I looked in the direction all were looking. Before us stood, unmasked at last, the scientific villain who had been plotting and scheming to capture both the secret and Inez--well knowing that suspicion would rest either on Lockwood, the soldier of fortune, or on the jealous Indian woman whose son had been rejected and whose brother he had himself already, secretly, driven to an insane suicide in his unscrupulous search for the treasure of Truxillo. It was Professor Norton, himself--first thief of the dagger which later he had hidden but which Whitney's detectives had stolen in turn from him; writer of anonymous letters, even to himself to throw others off the trail; maker of stramonium cigarettes with which to confuse the minds of his opponents, Whitney, Mendoza, and the rest; secret lover of Inez whom he demanded as the price of the dagger; and murderer of Don Luis. Senora de Moche and Alfonso, behind me, could only gasp their astonishment. Much as she would have liked to have the affair end in a general vindication of the curse she could not control a single, triumphant thrust. "His blood," she cried, transfixing Norton with her stern eyes, "has cried out of Titicaca for vengeance from that day to this!" "Want any help?" We all turned toward the door as Burke, dust-covered and tired, stamped in, followed by a man whose face was bandaged and bloody. "I heard shots. Is it all over?" But we paid no attention to Burke. There was Whitney, considerably banged up by the fall, but lucky to be alive. "I tried to shake him," he explained, catching sight of Norton. "But he stuck to us, even on our detours. Finally he grew desperate--forced my car off the road. What happened after that, I don't know. He must have carried me some miles, insensible, and dumped me in the bushes again. I was several miles up the hill, tramping along, looking for a road-house, when this gentleman found me and said I had gone too far." Senora de Moche turned from Lockwood and Inez who were standing, oblivious to the rest of us, and stared at Whitney's bruised and battered face. "It is the curse," she muttered. "It will never--" "Just a moment," interrupted Craig, drawing the dagger from his pocket, and turning toward Inez. "It was to your ancestor that the original possessor of the secret promised to give the 'big fish,' when he was killed." He paused and handed the dagger to her. She touched it shuddering, but as though it were a duty. "Take it," he said simply. "The secret is yours. Only love can destroy the curse on the Gold of the Gods." THE END 
5150	----	THE EAR IN THE WALL BY ARTHUR B. REEVE FRONTISPIECE BY WILL FOSTER CONTENTS CHAPTER I THE VANISHER II THE BLACK BOOK III THE SAFE ROBBERY IV THE ANONYMOUS LETTER V THE SUFFRAGETTE SECRETARY VI THE WOMAN DETECTIVE VII THE GANG LEADER VIII THE SHYSTER LAWYER IX THE JURY FIXER X THE AFTERNOON DANCE XI THE TYPEWRITER CLUE XII THE "PORTRAIT PARLE" XIII THE CONVICTION XIV THE BEAUTY PARLOUR XV THE PHANTOM CIRCUIT XVI THE SANITARIUM XVII THE SOCIETY SCANDAL XVIII THE WALL STREET WOLF XIX THE ESCAPE XX THE METRIC PHOTOGRAPH XXI THE MORGUE XXII THE CANARD XXIII THE CONFESSION XXIV THE DEBACLE OF DORGAN XXV THE BLOOD CRYSTALS XXVI THE WHITE SLAVE XXVII THE ELECTION NIGHT I THE VANISHER "Hello, Jameson, is Kennedy in?" I glanced up from the evening papers to encounter the square-jawed, alert face of District Attorney Carton in the doorway of our apartment. "How do you do, Judge?" I exclaimed. "No, but I expect him any second now. Won't you sit down?" The District Attorney dropped, rather wearily I thought, into a chair and looked at his watch. I had made Carton's acquaintance some years before as a cub reporter on the Star while he was a judge of an inferior court. Our acquaintance had grown through several political campaigns in which I had had assignments that brought me into contact with him. More recently some special writing had led me across his trail again in telling the story of his clean-up of graft in the city. At present his weariness was easily accounted for. He was in the midst of the fight of his life for re-election against the so-called "System," headed by Boss Dorgan, in which he had gone far in exposing evils that ranged all the way from vice and the drug traffic to bald election frauds. "I expect a Mrs. Blackwell here in a few minutes," he remarked, glancing again at his watch. His eye caught the headline of the news story I had been reading and he added quickly, "What do the boys on the Star think of that Blackwell case, anyhow?" It was, I may say, a case deeply shrouded in mystery--the disappearance without warning of a beautiful young girl, Betty Blackwell, barely eighteen. Her family, the police, and now the District Attorney had sought to solve it in vain. Some had thought it a kidnaping, others a suicide, and others had even hinted at murder. All sorts of theories had been advanced without in the least changing the original dominant note of mystery. Photographs of the young woman had been published broadcast, I knew, without eliciting a word in reply. Young men whom she had known and girls with whom she had been intimate had been questioned without so much as a clue being obtained. Reports that she had been seen had come in from all over the country, as they always do in such cases. All had been investigated and had turned out to be based on nothing more than imagination. The mystery remained unsolved. "Well," I replied, "of course there's a lot of talk now in the papers about aphasia and amnesia and all that stuff. But, you know, we reporters are a sceptical lot. We have to be shown. I can't say we put much faith in THAT." "But what is your explanation? You fellows always have an opinion. Sometimes I think the newspapermen are our best detectives." "I can't say that we have any opinion in this case--yet," I returned frankly. "When a girl just simply disappears on Fifth Avenue and there isn't even the hint of a clue as to any place she went or how, well--oh, there's Kennedy now. Put it up to him." "We were just talking of that Betty Blackwell disappearance case," resumed Carton, when the greetings were over. "What do you think of it?" "Think of it?" repeated Kennedy promptly with a keen glance at the District Attorney; "why, Judge, I think of it the same as you evidently do. If you didn't think it was a case that was in some way connected with your vice and graft investigation, you wouldn't be here. And if I didn't feel that it promised surprising results, aside from the interest I always have naturally in solving such mysteries, I wouldn't be ready to take up the offer which you came here to make." "You're a wizard, Kennedy," laughed Carton, though it was easily seen that he was both pleased and relieved to think that he had enlisted Craig's services so easily. "Not much of a wizard. In the first place, I know the fight you're making. Also, I know that you wouldn't go to the police in the present state of armed truce between your office and Headquarters. You want someone outside. Well, I'm more than willing to be that person. The whole thing, in its larger aspects, interests me. Betty Blackwell in particular, arouses my sympathies. That's all." "Exactly, Kennedy. This fight I'm in is going to be the fight of my life. Just now, in addition to everything else, people are looking to me to find Betty Blackwell. Her mother was in to see me today; there isn't much that she could add to what has already been said. Betty was a most attractive girl. The family is an excellent one, but in reduced circumstances. She had been used to a great deal as a child, but now, since the death of her father, she has had to go to work--and you know what that means to a girl like that." Carton laid down a new photograph which the newspapers had not printed yet. Betty Blackwell was slender, petite, chic. Her dark hair was carefully groomed, and there was an air with which she wore her clothes and carried herself, even in a portrait, which showed that she was no ordinary girl. Her soft brown eyes had that magnetic look which is dangerous to their owner if she does not know how to control it, eyes that arrested one's gaze, invited notice. Even the lens must have felt the spell. It had caught, also, the soft richness of the skin of her oval face and full throat and neck. Indeed one could not help remarking that she was really the girl to grace a fortune. Only a turn of the hand of that fickle goddess had prevented her from doing so. I had picked up one of the evening papers and was looking at the newspaper half-tone which more than failed to do justice to her. Just then my eye happened on an item which I had been about to discuss with Carton when Kennedy entered. "As a scientist, does the amnesia theory appeal to you, Craig?" I asked. "Now, here is an explanation by one of the special writers, headed, 'Personalities Lost Through Amnesia.' Listen." The article was brief: Mysterious disappearances, such as that of Betty Blackwell, have alarmed the public and baffled the police before this--disappearances that have in their suddenness, apparent lack of purpose, and inexplicability much in common with her case. Leaving out of account the class of disappearances for their own convenience--embezzlers, blackmailers, and so forth--there is still a large number of recorded cases where the subjects have dropped out of sight without apparent cause or reason and have left behind them untarnished reputations and solvent back accounts. Of these, a small percentage are found to have met with violence; others have been victims of suicidal mania, and sooner or later a clue has come to light which has established the fact. The dead are often easier to find than the living. Of the remaining small proportion, there are on record, however, a number of carefully authenticated cases where the subject has been the victim of a sudden and complete loss of memory. This dislocation of memory is a variety of aphasia known as amnesia, and when the memory is recurrently lost and restored, we have alternating personality. The Society for Psychical Research and many eminent psychologists, among them the late William James, Dr. Weir Mitchell, Dr. Hodgson of Boston, and Dr. A. E. Osborn of San Francisco, have reported many cases of alternating personality. Studious efforts are being made to understand and to explain the strange type of mental phenomena exhibited in these cases, but as yet no one has given a clear and comprehensive explanation of them. Such cases are by no means always connected with disappearances, and exhaustive studies have been made of types of alternating personality that have from first to last been carefully watched by scientists of the first rank. The variety known as the ambulatory type, where the patient suddenly loses all knowledge of his own identity and of the past and takes himself off, leaving no trace or clue, is the variety which the present case of Miss Blackwell seems to suggest. There followed a number of most interesting cases and an elaborate argument by the writer to show that Betty Blackwell was a victim of this psychological aberration, that she was, in other words, "a vanisher." I laid down the paper with a questioning look at Kennedy. "As a scientist," he replied deliberately, "the theory, of course, does appeal to me, especially in the ingenious way in which that writer applied it. However, as a detective"--he shook his head slowly--"I must deal with facts--not speculations. It leaves much to be explained, to say the least." Just then the door buzzer sounded and Carton himself sprang to answer it. "That's Mrs. Blackwell now--her mother. I told her that I was going to take the case to you, Kennedy, and took the liberty of asking her to come up here to meet you. Good-afternoon, Mrs. Blackwell. Let me introduce Professor Kennedy and Mr. Jameson, of whom I spoke to you." She bowed and murmured a tremulous greeting. Kennedy placed a chair for her and she thanked him. Mrs. Blackwell was a slender little woman in black, well past middle age. Her face and dress spoke of years of economy, even of privation, but her manner was plainly that of a woman of gentle breeding and former luxury. She was precisely of the type of decayed gentlewoman that one meets often in the city, especially at some of the middle-class boarding-houses. Deeply as the disappearance of her daughter had affected her, Mrs. Blackwell was facing it bravely. That was her nature. One could imagine that only when Betty was actually found would this plucky little woman collapse. Instinctively, one felt that she claimed his assistance in the unequal fight she was waging against the complexities of modern life for which she had been so ill prepared. "I do hope you will be able to find my daughter," she began, controlling her voice with an effort. "Mr. Carton has been so kind, more than kind, I am sure, in getting your aid. The police seem to be able to do nothing. They make out reports, put me off, tell me they are making progress--but they don't find Betty." There was a tragic pathos in the way she said it. "Betty was such a good girl, too," she went on, her emotions rising. "Oh, I was so proud of her when she got her position down in Wall Street, with the broker, Mr. Langhorne." "Tell Mr. Kennedy just what you told me of her disappearance," put in Carton. Again Mrs. Blackwell controlled her feelings. "I don't know much about it," she faltered, "but last Saturday, when she left the office early, she said she was going to do some shopping on Fifth Avenue. I know she went there, did shop a bit, then walked on the Avenue several blocks. But after that there is no trace of her." "You have heard nothing, have no idea where she might have gone--even for a time?" queried Kennedy. He asked it with a keen look at the face of Mrs. Blackwell. I recalled one case where a girl had disappeared in which Kennedy had always asserted that if the family had been perfectly frank at the start much more might have been accomplished in unravelling the mystery. There was evident sincerity in Mrs. Blackwell as she replied quickly, "Absolutely none. Another girl from the office was with her part of the time, then left her to take the subway. We don't live far uptown. It wouldn't have taken Betty long to get home, even if she had walked, after that, through a crowded street, too." "Of course, she may have met a friend, may have gone somewhere with the friend," put in Kennedy, as if trying out the remark to see what effect it might have. "Where could she go?" asked Mrs. Blackwell in naive surprise, looking at him with a counterpart of the eyes we had seen in the picture. "I hope you don't think that Betty---" The little widow was on the verge of tears again at the mere hint that her daughter might have had friends that were not all, perhaps, that they should be. Carton came to the rescue. "Miss Blackwell," he interposed, "was a very attractive girl, very. She had hosts of admirers, as every attractive girl must have. Most of them, all of them, as far as Mrs. Blackwell knows and I have been able to find out, were young men at the office where she worked, or friends of that sort--not the ordinary clerk, but of the rising, younger, self-made generation. Still, they don't seem to have interested her particularly as far as I have been able to discover. She merely liked them. There is absolutely nothing known to point to the fact that she was any different from thousands of girls in that respect. She was vivacious, full of fun and life, a girl any fellow would have been more than proud to take to a dance. She was ambitious, I suppose, but nothing more." "Betty was not a bad girl," asserted Mrs. Blackwell vehemently. "She was a good girl. I don't believe there was much, in fact anything important, on which she did not make me her confidante. Yes, she was ambitious. So am I. I have always hoped that Betty would bring our family--her younger sister--back to the station where we were before the panic wiped out our fortune and killed my husband. That is all." "Yes," added Carton, "nothing at all is known that would make one think that she was what young men call a 'good fellow' with them." Kennedy looked up, but said nothing. I thought I could read the unspoken word on his lips, as he glanced from Carton to Mrs. Blackwell, "known." She had risen and was facing us. "Is there no one in all this great city," appealed the distracted little woman with outstretched arms, "who can find my daughter? Is it possible that a girl can disappear in broad daylight in the streets and never be heard of again? Oh, won't you find her? Tell me she is safe--that she is still the little girl I---" Her voice failed and she was crying softly in her lace handkerchief. It was touching and I saw that Kennedy was deeply moved, although at once to his practical mind the thought must have occurred that nothing was to be gained by further questions of Mrs. Blackwell. "Believe me, Mrs. Blackwell," he said in a low tone, taking her hand, "I will do all that is in my power to find her." "Thank you," murmured the mother, overcome. A moment later, however, she had recovered her composure to some degree and rose to go. There was a flattering look of relief on her face which in itself must have been ample reward to Craig, a retainer worth more to him in a case like this than money. "I'm going back to my office," remarked Carton. "If I learn anything, I shall let you know." The District Attorney went out with Mrs. Blackwell. Busy as he was, he had time to turn aside to help this bereaved woman, and I admired him for it. "Do you think it is one of those cases like some that Carton has uncovered on the East Side and among girls newly arrived in the city?" I asked Craig when the door was shut. "Can't say," he returned, in an abstracted study. "It's awful if it is," I pursued. "And if it is, I suppose all that will result from it will be a momentary thrill of the newspaper-readers, and then they will fall back on the old saying that after all it is only a result of human nature that such things happen--they always have happened and always will--that old line of talk." "That sort of thing is NOT a result of human nature," returned Kennedy earnestly. "It's a System. I mean to say that if it should turn out to be connected with the vice investigations of Carton, and not a case of aphasia, such a disappearance you would find to be due to the persistent, cunning, and unprincipled exploitation of young girls. "No, Walter, it is not that women are weak or that men are inherently vicious. That doesn't account for a case like this. Then, too, some mawkish people to-day are fond of putting the whole evil on low wages as a cause. It isn't that--alone. It isn't even lack of education or of moral training. Human nature is not so bad in the mass as some good people think. No, don't you, as a reporter, see it? It is big business, in its way, that Carton is fighting--big business in the commercialized ruin of girls, such, perhaps, as Betty Blackwell--a vicious system that enmeshes even those who are its tools. I'm glad if I can have a chance to help smash it. "Now, I'll tell you what I want you to do, just so that we can start this thing with a clear understanding of what it amounts to. I want you to look up just what the situation is. I know there is an army of 'vanishers' in New York. I want to know something about them in the mass. Can't you dig up something from your Star connections?" Kennedy had some matters concerning other cases to clear up before he felt free to devote his whole time to this. As there was nothing we could do immediately, I spent some time getting at the facts he wanted. Indeed, it did not take me long to discover that the disappearance of Betty Blackwell, in spite of the prominence it had been given, was by no means an isolated case. I found that the Star alone had chronicled scores of such disappearances during the past few months, cases of girls who had simply been swallowed up in the big city. They were the daughters of neither the rich nor of the poor, most of them, but girls rather in ordinary circumstances. Even the police records showed upward of a thousand missing young girls, ranging in age from fourteen to twenty-one years and I knew that the police lists scarcely approximated the total number of missing persons in the great city, especially in those cases where a hesitancy on the part of parents and relatives often concealed the loss from public records. I came away with the impression that there were literally hundreds of cases every bit as baffling as that of Betty Blackwell, of young girls who had left absolutely no trace behind, who had made no preparations for departure and of whom few had been heard from since they disappeared. Many from homes of refinement and even high financial standing had disappeared, leaving no clues behind. It was not alone the daughters of the poor that were affected--it was all society. Many reasons, I found, had been assigned for the disappearances. I knew that there must be many causes at work, that no one cause could be responsible for all or perhaps a majority of the cases. There were suicides and murders and elopements, family troubles, poverty, desire for freedom and adventure; innumerable complex causes, even down to kidnapping. The question was, however, which of these causes had been in operation in the case of Betty Blackwell? Where had she gone? Where had this whole army of vanishers disappeared? Were these disappearances merely accidents--or was there an epidemic of amnesia? I could bring myself to no such conclusions, but was forced to answer my own queries in lieu of an answer from Kennedy, by propounding another. Was there an organized band? And, after I had tried to reason it all out, I still found myself back at the original question, as I rejoined Kennedy at the laboratory, "Where had they all--where had Betty Blackwell gone?" II THE BLACK BOOK I had scarcely finished pouring out my suspicions to Kennedy when the telephone rang. It was Carton on the wire, in a state of unsuppressed excitement. Kennedy answered the call himself, but the conversation was brief and, to me, unenlightening, until he hung up the receiver. "Dorgan--the Boss," he exclaimed, "has just found a detectaphone in his private dining-room at Gastron's." At once I saw the importance of the news and for the moment it obscured even the case of Betty Blackwell. Dorgan was the political boss of the city at that time, apparently entrenched, with an organization that seemed impregnable. I knew him as a big, bullnecked fellow, taciturn to the point of surliness, owing his influence to his ability to "deliver the goods" in the shape of graft of all sorts, the archenemy of Carton, a type of politician who now is rapidly passing. "Carton wants to see us immediately at his office," added Craig, jamming his hat on his head. "Come on." Without waiting for further comment or answer from me, Kennedy, caught by the infectious excitement of Carton's message, dashed from our apartment and a few minutes later we were whirling downtown on the subway. "You know, I suppose," he whispered rather hoarsely above the rumble and roar of the train, but so as not to be overheard, "that Dorgan always has kept a suite of rooms at Gastron's, on Fifth Avenue, for dinners and conferences." I nodded. Some of the things that must have gone on in the secret suite in the fashionable restaurant I knew would make interesting reading, if the walls had ears. "Apparently he must have found out about the eavesdropping in time and nipped it," pursued Kennedy. "What do you mean?" I asked, for I had not been able to gather much from the one-sided conversation over the telephone, and the lightning change from the case of Betty Blackwell to this had left me somewhat bewildered. "What has he done?" "Smashed the transmitter of the machine," replied Kennedy tersely. "Cut the wires." "Where did it lead?" I asked. "How do you know?" Kennedy shook his head. Either he did not know, yet, or he felt that the subway was no place in which to continue the conversation beyond the mere skeleton that he had given me. We finished the ride in comparative silence and hurried into Carton's office down in the Criminal Courts Building. Carton greeted us cordially, with an air of intense relief, as if he were glad to have been able to turn to Kennedy in the growing perplexities that beset him. What surprised me most, however, was that, seated beside his desk, in an easy chair, was a striking looking woman, not exactly young, but of an age that is perhaps more interesting than youth, certainly more sophisticated. She, too, I noticed, had a tense, excited expression on her face. As Kennedy and I entered she had looked us over searchingly. "Let me present Mr. Kennedy and Mr. Jameson, Mrs. Ogleby," said Carton quickly. "Both of them know as much about how experts use those little mechanical eavesdroppers as anyone--except the inventor." We bowed and waited for an explanation. "You understand," continued Carton slowly to us in a tone that enjoined secrecy, "Mrs. Ogleby, who is a friend of Mr. Murtha, Dorgan's right-hand man, naturally is alarmed and doesn't want her name to appear in this thing." "Oh--it is terrible--terrible," Mrs. Ogleby chimed in in great agitation. "I don't care about anything else. But, my reputation--it will be ruined if they connect my name with the case. As soon as I heard of it--I thought of you, Mr. Carton. I came here immediately. There must be some way in which you can protect me--some way that you can get along without using--" "But, my dear Mrs. Ogleby," interrupted the District Attorney, "I have told you half a dozen times, I think, that I didn't put the detectaphone in--" "Yes, but you will get the record," she persisted excitedly. "Can't you do something?" she pleaded. I fancied that she said it with the air of one who almost had some right in the matter. "Mrs. Ogleby," reiterated Carton earnestly, "I will do all I can--on my word of honour--to protect your name, but--" He paused and looked at us helplessly. "What was it that was overheard?" asked Craig point-blank, watching Mrs. Ogleby's face carefully. "Why," she replied nervously, "there was a big dinner last night which Mr. Dorgan gave at Gastron's. Mr. Murtha took me and--oh--there were lots of others--" She stopped suddenly. "Yes," prompted Kennedy. "Who else was there?" She was on her guard, however. Evidently she had come to Carton for one purpose and that was solely to protect herself against the scandal which she thought might attach to having been present at one of the rather notorious little affairs of the Boss. "Really," she answered, colouring slightly, "I can't tell you. I mustn't say a word about who was there--or anything about it. Good heavens--it is bad enough as it is--to think that my name may be dragged into politics and all sorts of false stories set in motion about me. You must protect me, Mr. Carton, you must." "How did you find out about the detectaphone being there?" asked Kennedy. "Why," she replied evasively, "I thought it was just an ordinary little social dinner. That's what Mr. Murtha told me it was. I didn't think anyone outside was interested in it or in who was there or what went on. But, this morning, a--a friend--called me up and told me--something that made me think others besides those invited knew of it, knew too much." She paused, then resumed hastily to forestall questioning, "I began to think it over myself, and the more I thought of it, the stranger it seemed that anyone else, outside, should know. I began to wonder how it leaked out, for I understood that it was a strictly private affair. I asked Mr. Murtha and he told Mr. Dorgan. Mr. Dorgan at once guessed that there had been something queer. He looked about his rooms there, and, sure enough, they found the detectaphone concealed in the wall. I can't tell any more," she added, facing Carton and using her bewitching eyes to their best advantage. "I can't ask you to shield Mr. Dorgan and Mr. Murtha. They are your opponents. But I have done nothing to you, Mr. Carton. You must suppress--that part of it--about me. Why, it would ruin---" She cut her words short. But I knew what she meant, and to a certain extent I could understand, if not sympathize with her. Her husband, Martin Ogleby, club-man and man about town, had a reputation none too savoury. But, man-like, I knew, he would condone not even the appearance of anything that caused gossip in his wife's actions. I could understand how desperate she felt. "But, my dear lady," repeated Carton, in a manner that showed that he felt keenly, for some reason or other, the appeal she was making to him, "must I say again that I had nothing whatever to do with it? I have sent for Mr. Kennedy and---" "Nothing--on your honour?" she asked, facing him squarely. "Nothing--on my honour," he asserted frankly. She appeared to be dazed. Apparently all along she had assumed that Carton must be the person to see, that he alone could do anything for her, would do something. Her face paled as she met his earnest look. She had risen and now, half chagrined, half frightened, she stood irresolute. Her lips quivered and tears stood in her eyes as she realized that, instead of protecting herself by her confidence, she had, perhaps, made matters worse by telling an outsider. Carton, too, had risen and in a low voice which we could not overhear was trying to reassure her. In her confusion she was moving toward the door, utterly oblivious, now, to us. Carton tactfully took her arm and led her to a private entrance that opened from his office down the corridor and out of sight of the watchful eyes of the reporters and attendants in the outer hall. I did not understand just what it was all about, but I could see Kennedy's eye following Carton keenly. "What was that--a plant?" he asked, still trying to read Carton's face, as he returned to us alone a moment later. "Did she come to see whether you got the record?" "No--I don't think so," replied Carton quickly. "No, I think that was all on the level--her part of it." "But who did put in the instrument, really--did you?" asked Kennedy, still quizzing. "No," exclaimed Carton hastily, this time meeting Craig's eye frankly. "No. I wish I had. Why--the fact is, I don't know who did--no one seems to know, yet, evidently. But," he added, leaning forward and speaking rapidly, "I think I could give a shrewd guess." Kennedy said nothing, but nodded encouragingly. "I think," continued Carton impressively, "that it must have been Langhorne and the Wall Street crowd he represents." "Langhorne," repeated Kennedy, his mind working rapidly. "Why, it was his stenographer that Miss Blackwell was. Why do you suspect Langhorne?" "Because," exclaimed Carton, more excited than ever at Kennedy's quick deduction, bringing his fist down on the desk to emphasize his own suspicion, "because they aren't getting their share of the graft that Dorgan is passing out--probably are sore, and think that if they can get something on the Boss or some of those who are close to him, they may force him to take them into partnership in the deals." Carton looked from Kennedy to me, to see what impression his theory made. On me at least it did make an impression. Hartley Langhorne, I knew, was a Wall Street broker and speculator who dealt in real estate, securities, in fact in anything that would appeal to a plunger as promising a quick and easy return. Kennedy made no direct comment on the theory. "In what shape is the record, do you suppose?" he asked merely. "I gathered from Mrs. Ogleby," returned Carton watchfully, "that it had been taken down by a stenographer at the receiving end of the detectaphone, transcribed in typewriting, and loosely bound in a book of limp black leather. Oh," he concluded, "Dorgan would give almost anything to find out what is in that little record, you may be sure. Perhaps even, rather than have such a thing out, he would come to terms with Langhorne." Kennedy said nothing. He was merely absorbing the case as Carton presented it. "Don't you see?" continued the District Attorney, pacing his office and gazing now and then out of the window, "here's this record hidden away somewhere in the city. If I could only get it--I'd win my fight against Dorgan--and Mrs. Ogleby need not suffer for her mistake in coming to me, at all." He was apparently thinking aloud. Kennedy did not attempt to quiz him. He was considering the importance of the situation. For, as I have said, it was at the height of the political campaign in which Carton had been renominated independently by the Reform League--of which, more later. "You don't think that Langhorne is really in the inner ring, then?" questioned Craig. "No, not yet." "Well, then," I put in hastily, "can't you approach him or someone close to him, and get---" "Say," interrupted Carton, "anything that took place in that private dining-room at Gastron's would be just as likely to incriminate Langhorne and some of his crowd as not. It is a difference in degree of graft--that is all. They don't want an open fight. It was just a piece of finesse on Langhorne's part. You may be sure of that. No, neither of them wants a fight. That's the last thing. They're both afraid. What Langhorne wanted was a line on Dorgan. And we should never have known anything about this Black Book, if some of the women, I suppose, hadn't talked too much. Mrs. Ogleby added two and two and got five. She thought it must be I who put the instrument in." Carton was growing more and more excited again, "It's exasperating," he continued. "There's the record--somewhere--if I could only get it. Think of it, Kennedy--an election going on and never so much talk about graft and vice before!" "What was in the book--mostly, do you imagine?" asked Craig, still imperturbable. Carton shrugged his shoulders. "Oh, almost anything. For instance, you know, Dorgan has just put through a new scheme of city planning--with the able assistance of some theoretical reformers. That will be a big piece of real estate graft, unless I am mistaken. Langhorne and his crowd know it. They don't want to be frozen out." As they talked, I had been revolving the thing over in my head. Dorgan's little parties, as reported privately among the men on the Star whom I knew, were notorious. The more I considered, the more possible phases of the problem I thought of. It was not even impossible that in some way it might bear on the Betty Blackwell case. "Do you think Dorgan and Murtha are hunting the book as anxiously as--some others?" I ventured. "You have heard of the character of some of those dinners?" answered Carton by asking another question, then went on: "Why, Dorgan has had some of our leading lawyers, financiers, and legislators there. He usually surrounds them with brilliant, clever women, as unscrupulous as himself, and--well--you can imagine the result. Poor little Mrs. Ogleby," he added sympathetically. "They could twist her any way they chose for their purposes." My own impression had been that Mrs. Ogleby was better able to take care of herself than his words gave her credit for, but I said nothing. Carton paused before the window and gazed out at the Bridge of Sighs that led from his building across to the city prison. "What a record that Black Book must hold!" he exclaimed meditatively. "Why, if it was only that I could 'get' Murtha--I'd be happy," he added, turning to us. Murtha, as I have said, was Boss Dorgan's right bower, a clever and unscrupulous politician and leader in a district where he succeeded somehow or other in absolutely crushing opposition. I had run across him now and then in the course of my newspaper career and, aside from his well-known character in delivering the "goods" to the organization whenever it was necessary, I had found him a most interesting character. It was due to such men as Murtha that the organization kept its grip, though one wave of reform after another lashed its fury on it. For Murtha understood his people. He worked at politics every hour--whether it was patting the babies of the district on the head, or bailing their fathers out of jail, handing out shoes to the shiftless or judiciously distributing coal and ice to the deserving. Yet I had seen enough to know the inherent viciousness of the circle--of how the organization took dollars from the people with one concealed hand and distributed pennies from the other hand, held aloft and in the spotlight. Again and again, Kennedy and I in our excursions into scientific warfare on crime in the underworld had run squarely up against the refined as well as the debased creatures of the "System." Pyramided on what looked like open-handed charity and good-fellowship we had seen vice and crime of all degrees. And yet, somehow or other, I must confess to a sort of admiration for Murtha and his stamp--if for nothing else than because of the frankness with which he did what he sought to do. Neither Kennedy nor I could be accused of undue sympathy with the System, yet, like many who had been brought in close contact with it, it had earned our respect in many ways. And so, I contemplated the situation with more than ordinary interest. Carton wanted the Black Book to use in order to win his political fight for a clean city and to prosecute the grafters. Dorgan wanted it in order to suppress and thus protect himself and Murtha. Mrs. Ogleby wanted it to save her good name and prevent even the appearance of scandal. Langhorne wanted it in order to coerce Dorgan to share in the graft, yet was afraid of Carton also. Was ever a situation of such peculiar, mixed motives? "I would move heaven and earth for that Black Book!" exclaimed Carton finally, turning from the window and facing us. Kennedy, too, had risen. "You can count on me, then, Carton," he said simply, as the recollection of the many fights in which we had stood shoulder to shoulder with the young District Attorney came over him. A moment later Carton had us each by the hand. "Thank you," he cried. "I knew you fellows would be with me." III THE SAFE ROBBERY It was late that night that Kennedy and I left Carton after laying out a campaign and setting in motion various forces, official and unofficial, which might serve to keep us in touch with what Dorgan and the organization were doing. Not until the following morning, however, did anything new develop in such a way that we could work on it. Kennedy had picked up the morning papers which had been left at the door of our apartment and was hastily running his eye over the headlines on the first page, as was his custom. "By Jove, Walter," I heard him exclaim. "What do you think of that--a robbery below the deadline--and in Langhorne's office, too." I hurried out of my room and glanced at the papers, also. Sure enough, there it was: SAFE ROBBED IN WALL ST. OFFICE Door Into Office of Langhorne & Westlake, Brokers, Forced and Safe Robbed. One of the strangest robberies ever perpetrated was pulled off last night in the office of Langhorne & Westlake, the brokers, at-----Wall Street, some time during the regular closing time of the office and eight o'clock. Mr. Langhorne had returned to his office after dining with some friends in order to work on some papers. When he arrived, about eight o'clock, he found that the door had been forced. The office was in darkness, but when he switched on the lights it was discovered that the office safe had been entered. Nothing was said about the manner in which the safe robbery was perpetrated, but it is understood to have been very peculiar. So far no details have been announced and the robbery was not reported to the police until a late hour. Mr. Langhorne, when seen by the reporters, stated positively that nothing of great value had been taken and that the firm would not suffer in any way as a result of the robbery. One of the stenographers in the office, Miss Betty Blackwell, who acted as private secretary to Mr. Langhorne, is missing and the case has already attracted wide attention. Whether or not her disappearance had anything to do with the robbery is not known. "Naturally he would not report it to the police," commented Kennedy; "that is, if it had anything to do with that Black Book, as I am sure that it must have had." "It was certainly a most peculiar affair if it did not," I remarked. "There must be some way of finding that out. It's strange about Betty Blackwell." Kennedy was turning something over in his mind. "Of course," he remarked, "we don't want to come out into the open just yet, but it would be interesting to know what happened down there at Langhorne's. Have you any objection to going down with me and posing as a reporter from the Star?" "None whatever," I returned. We stopped at the laboratory on the campus of the University where Craig still retained his professorship. Kennedy secured a rather bulky piece of apparatus, which, as nearly as I can describe, consisted of a steel frame, which could be attached by screws to any wooden table. It contained a lower plate which could move forward and back, two lateral uprights stiffened by curved braces, and a cross piece of steel attached by strong bolts to the tops of the posts. In the face of the machine was a dial with a pointer. Kennedy quickly took the apparatus apart and made it up into two packages so that between us we could carry it easily, and at about the time that Wall Street offices were opening we were on our way downtown. Langhorne proved to be a tall, rather slim, man of what might be called youngish middle age. One did not have to be introduced to him to read his character or his occupation. Every line of his faultlessly fitting clothes and every expression of his keen and carefully cared-for face betokened the plunger, the man who lived by his wits and found the process both fascinating and congenial. "Mr. Langhorne," began Kennedy, after I had taken upon myself the duty of introducing ourselves as reporters, "we are preparing an article for our paper about a new apparatus which the Star has imported especially from Paris. It is a machine invented by Monsieur Bertillon just before he died, for the purpose of furnishing exact measurements of the muscular efforts exerted in the violent entry of a door or desk by making it possible to reproduce the traces of the work that a burglar has left on doors and articles of furniture. We've been waiting for a case that the instrument would fit into and it seemed to us that perhaps it might be of some use to you in getting at the real robber of your office. Would you mind if we made an attempt to apply it?" Langhorne could not very well refuse to allow us to try the thing, though it was plainly evident that he did not want to talk and did not relish the publicity that the news of the morning had brought him. Kennedy had laid the apparatus down on a table as he spoke and was assembling the parts which he had separated in order to carry it. "These are the marks on the door, I presume?" he continued, examining some indentations of the woodwork near the lock. Langhorne assented. "The door was open when you returned?" asked Kennedy. "Closed," replied Langhorne briefly. "Before I put the key into the lock, I turned the knob, as I have a habit of doing. Instead of catching, it yielded and the door swung open without any trouble." He repeated the story substantially as we had already read it in the papers. Kennedy had taken a step or two into the office, and was now facing the safe. It was not a large safe, but was one of the most modern construction and was supposed to be burglar proof. "And you say you lost practically nothing?" persisted Craig. "Nothing of importance," reiterated Langhorne. Kennedy had been watching him closely. The man was at least baffling. There was nothing excited or perturbed about his manner. Indeed, one might easily have thought that it was not his safe at all that had been robbed. I wondered whether, after all, he had had the Black Book. Certainly, I felt, if he had lost it he was very cool about the loss. Craig had by this time reached the safe itself. In spite of Langhorne's reluctance, his assurance had taken Kennedy even up to the point which he wished. He was examining the safe. On the front it showed no evidence of having been "souped" or drilled. There was not a mark on it. Nor, as we learned later from the police, was there any evidence of a finger-print having been left by the burglar. Langhorne now but ill concealed his interest. It was natural, too, for here he had one of the most modern of small strong-boxes, built up of the latest chrome steel and designed to withstand any reasonable assault of cracksman or fire. I was on the point of inquiring how on earth it had been possible to rob the safe, when Kennedy, standing on a chair, as Langhorne directed, uttered a low exclamation. I craned my neck to look also. There, in the very top of the safe, yawned a huge hole large enough to thrust one's arm through, with something to spare. As I looked at the yawning dark hole in the top of what had been only a short time ago a safe worthy of the latest state of the art, it seemed incomprehensible. Try as I could to reason it out, I could find no explanation. How it had been possible for a burglar to make such an opening in the little more than two hours between closing and the arrival of Langhorne after dinner, I could not even guess. As far as I knew it would have taken many long hours of patient labour with the finest bits to have made anything at all comparable to the destruction which we saw before us. A score of questions were on my lips, but I said nothing, although I could not help noticing the strange look on Langhorne's face. It plainly showed that he would like to have known what had taken place during the two or more hours when his office had been unguarded, yet was averse to betraying any such interest. Mystified as I was by what I saw, I was even more amazed at the cool manner in which Kennedy passed it all by. He seemed merely to be giving the hole in the top of the safe a passing glance, as though it was of no importance that someone should have in such an incredibly short time made a hole through which one might easily reach his arm and secure anything he wanted out of the interior of the powerful little safe. Langhorne, too, seemed surprised at Kennedy's matter of fact passing by of what was almost beyond the range of possibility. "After all," remarked Kennedy, "it is not the safe that we care to study so much as the door. For one thing, I want to make sure whether the marks show a genuine breaking and entering or whether they were placed there afterwards merely to cover the trail, supposing someone had used a key to get into the office." The remark suggested many things to me. Was it that he meant to imply that, after all, the missing Betty Blackwell had had something to do with it? In fact, could the thing have been done by a woman? "Most persons," remarked Craig, as he studied the marks on the door, "don't know enough about jimmies. Against them an ordinary door-lock or window-catch is no protection. With a jimmy eighteen inches long, even an anemic burglar can exert a pressure sufficient to lift two tons. Not one door-lock in ten thousand can stand this strain. It's like using a hammer to kill a fly. Really, the only use of locks is to keep out sneak thieves and to compel the modern, scientific educated burglar to make a noise. This fellow, however, was no sneak thief." He continued to adjust the machine which he had brought. Langhorne watched minutely, but did not say anything. "Bertillon used to call this his mechanical burglar detector," continued Kennedy. "As you see, this frame carries two dynamometers of unequal power. The stronger, which has a high maximum capacity of several tons, is designed for the measurement of vertical efforts. The other measures horizontal efforts. The test is made by inserting the end of a jimmy or other burglar's tool and endeavouring to produce impressions similar to those which have been found on doors or windows. The index of the dynamometer moves in such a way as to make a permanent record of the pressure exerted. The horizontal or traction dynamometer registers the other component of pressure." He pressed down on the machine. "There was a pressure here of considerably over two tons," he remarked at length, "with a very high horizontal traction of over four hundred pounds. What I wanted to get at was whether this could have been done by a man, woman, or child, or perhaps by several persons. In this case, it was clearly no mere fake to cover up the opening of the door by a key. It was a genuine attempt. Nor could it have been done by a woman. No, that is the work of a man, a powerful man, too, accustomed to the use of the jimmy." I fancied that a shade of satisfaction crossed the otherwise impassive face of Langhorne. Was it because the Bertillon dynamometer appeared at first sight to exonerate Betty Blackwell, at least so far, from any connection with the crime? It was difficult to say. Important though it was, however, to clear up at the start just what sort of person was connected with the breaking of the door I could not but feel that Kennedy had some purpose in deferring and minimizing for the present what, to me at least, was the greater mystery, the entering of the safe itself. He was still studying and comparing the marks on the door and the record made on the dynamometer, when the office telephone rang and Langhorne was summoned to answer it. Instead of taking the call in his own office, he chose to answer it at the switchboard, perhaps because that would allow him to keep an eye also on us. Whatever his purpose, it likewise enabled us to keep an ear on him, and it was with surprise which both Kennedy and I had great difficulty in concealing, that we heard him reply, "Hello--yes--oh, Mrs. Ogleby, good-morning. How are you? That's good. So you, too, read the papers. No, I haven't lost anything of importance, thank you. Nothing serious, you know. The papers like to get hold of such things and play them up. I have a couple of reporters here now. Heaven knows what they are doing, but I can foresee some more unpaid advertising for the firm in it. Thank you again for your interest. You haven't forgotten the studio dance I'm giving on the twelfth? No--that's fine. I hope you'll come, even if Martin has another engagement. Fine. Well-good-bye." He hung up the receiver with a mingled air of gratification and exasperation, I fancied. "Haven't you fellows finished yet?" he asked finally, coming over to us, a little brusquely. "Just about," returned Kennedy, who had by this time begun slowly to dismember and pack up the dynamometer, determined to take advantage of every minute both to observe Langhorne and to fix in his mind the general lay-out of the office. "Everybody seems to be interested in me this morning," he observed, for the moment forgetting the embargo he had imposed on his own words. As for myself, I saw at once that others besides ourselves were keenly interested in this robbery. "There," remarked Kennedy when at last he had finished packing up the dynamometer into two packages. "At least, Mr. Langhorne, you have the satisfaction of knowing that it was in all probability a man, a strong man, and one experienced in forcing doors who succeeded in entering your office during your brief absence last night." Langhorne shrugged his shoulders non-committally, but it was evident that he was greatly relieved and he could not conceal his interest in what Kennedy was doing, even though he had succeeded in conveying the impression that it was a matter of indifference to him. "I suppose you keep a great many of your valuable papers in safety deposit vaults," ventured Kennedy, finishing up the wrapping of the two packages, "as well as your personal papers perhaps at home." He made the remark in a casual manner, but Langhorne was too keen to fall into the trap. "Really," he said with an air of finality, "I must decline to be interviewed at present. Good-day, gentlemen." "A slippery customer," was Craig's comment when we reached the street outside the office. "By the way, evidently Mrs. Ogleby is leaving no stone unturned in her effort to locate that Black Book and protect herself." I said nothing. Langhorne's manner, self-confident to the point of bravado, had baffled me. I began to feel that even if he had lost the detectaphone record, his was the nature to carry out the bluff of still having it, in much the same manner that he would have played the market on a shoestring or made the most of an unfilled four-card flush in a game of poker. Kennedy was far from being discouraged, however. Indeed, it seemed as if he really enjoyed matching his wit against the subtlety of a man like Langhorne, even more than against one the type of Dorgan and Murtha. "I want to see Carton and I don't want to carry these bundles all over the city," he remarked, changing the subject for the moment, as he turned into a public pay station. "I'll ring him up and have him meet us at the laboratory, if I can." A moment later he emerged, excited, perspiring from the closeness of the telephone booth. "Carton has some news--a letter--that's all he would say," he exclaimed. "He'll meet us at the laboratory." We hastily resumed our uptown journey. "What do you think it is?" I asked. "About Betty Blackwell?" Kennedy shook his head non-committally. "I don't know. But he has some of his county detectives watching Dorgan and Murtha in that Black Book case, I know. They are worried. It doesn't look as though they, at least, had the record--that is, if Langhorne has really lost it." I wondered whether Langhorne might not, after all, as Kennedy had hinted, have concealed it elsewhere. The activity of Dorgan and Murtha might indicate that they knew more about the robbery than appeared yet on the surface. Had they failed in it? Had they been double-crossed by the man they had chosen for the work, assuming that they knew of and had planned the "job"? The safe-breaking and the way Langhorne took it had served to complicate the case even further. While we had before been reasonably sure that Langhorne had the book, now we were sure of nothing. IV THE ANONYMOUS LETTER "What do you make of that?" inquired Carton half an hour later as he met us breathlessly at the laboratory. He unfolded a letter over which he had evidently been puzzling considerably. It was written, or rather typewritten, on plain paper. The envelope was plain and bore no marks of identification, except possibly that it had been mailed uptown. The letter ran: DEAR SIR: Although this is an anonymous letter, I beg that you will not consider it such, since it will be plain to you that there is good reason for my wishing to remain nameless. I want to tell you of some things that have taken place recently at a little hotel in the West Fifties. No doubt you know of the place already--the Little Montmartre. There are several young and wealthy men who frequent this resort. I do not dare tell you their names, but one is a well-known club-man and man about town, another is a banker and broker, also well known, and a third is a lawyer. I might also mention an intimate friend of theirs, though not of their position in society--a doctor who has somewhat of a reputation among the class of people who frequent the Little Montmartre, ready to furnish them with anything from a medical certificate to drugs and treatment. I have read a great deal in the newspapers lately of the disappearance of Betty Blackwell, and her case interests me. I think you will find that it will repay you to look into the hint I have given. I don't think it is necessary to say any more. Indeed it may be dangerous to me, and I beg that you will not even show this letter to anyone except those associated with you and then, please, only with the understanding that it is to go no farther. Betty Blackwell is not at this hotel, but I am sure that some of those whose wild orgies have scandalized even the Little Montmartre know something about her. Yours truly, AN OUTCAST. Kennedy looked up quickly at Carton as he finished reading the letter. "Typical," he remarked. "Anonymous letters occasionally are of a friendly nature, but usually they reflect with more or less severity upon the conduct or character of someone. They usually receive little attention, but sometimes they are of the most serious character. In many instances they are most important links in chains of evidence pointing to grave crimes. "It is possible to draw certain conclusions from such letters at once. For instance, it is a surprising fact that in a large number of cases the anonymous letter writer is a woman, who may write what it does not seem possible she could write. Such letters often by their writing, materials used, composition and general form indicate at once the sex of the writer and frequently show nationality, age, education, and occupation. These facts may often point to the probable author. "Now in this case the writer evidently was well educated. Assumed illiteracy is a frequent disguise, but it is impossible for an author to assume a literacy he or she does not possess. Then, too, women are more apt to assume the characteristics of men than men of women. There are many things to be considered. Too bad it wasn't in ordinary handwriting. That would have shown much more. However, we shall try our best with what we have here. What impressed you about it?" "Well," remarked Carton, "the thing that impressed me was that as usual and as I fully expected, the trail leads right back to protected vice and commercialized graft. This Little Montmartre is one of the swellest of such resorts in the city, the legitimate successor to the scores and hundreds of places which the authorities and the vice investigators have closed recently. In fact, Kennedy, I consider it more dangerous, because it is run, on the surface at least, just like any of the first-class hotels. There's no violation of law there, at least not openly." Craig had continued to examine the letter closely. "So, you have already investigated the Little Montmartre?" he queried, drawing from his pocket a little strip of glass and laying it down carefully over the letter. "Indeed I have," returned the District Attorney, watching Kennedy curiously. "It is a place with a very unsavoury reputation. And yet I have been able to get nothing on it. They are so confounded clever. There is never any outward violation of law; they adhere strictly to the letter of the rule of outward decency." Over the typewritten characters Kennedy had placed the strip of glass and I could see that it was ruled into little oblongs, into each of which one of the type of the typewritten sheet seemed to fall. Apparently he had forgotten the contents of the letter in his interest in the text itself. He held the paper up to the light and seemed to study its texture and thickness. Then he examined the typed characters more closely with a little pocket magnifying glass, his lips moving as if he were counting something. Next he seized a mass of correspondence on his desk and began comparing the letter with others, apparently to determine just the shade of writing of the ribbon. Finally he gave it up and leaned back in his chair regarding us. "It is written in the regular pica type," he remarked thoughtfully, "and on a machine that has seen considerable rough usage, although it is not an old machine. It will take me a little time to identify the make, but after I have done that, I think I could identify the particular machine itself the moment I saw it. You see, it is only a clue that would serve to fix it once you found that machine. The point is, after all, to find it. But once found, I am sure we shall be close to the source of the letter. I may keep this and study it at my leisure?" "Certainly." For a moment Carton was silent. Then it seemed as though the matter of Betty Blackwell brought to mind what he had read in the morning papers. "That robbery of Langhorne's safe was a most peculiar thing, wasn't it?" he meditated. "I suppose you know what Miss Blackwell was?" "Langhorne's stenographer and secretary, of course," I replied quickly. "Yes, I know. But I mean what she had actually done? I don't believe you do. My county detectives found out only last night." Kennedy paused in his rummaging among some bottles to which he had turned at the mention of the safe robbery. "No--what was it?" he asked. Carton bent forward as if our own walls might have ears and said in a low voice: "She was the operator who took down the detectaphone conversations at the other end of the wire in a furnished room in the house next to Gastron's." He drew back to see what effect the intelligence had on us, then resumed slowly: "Yes, I've had my men out on the case. That is what they think. I believe she often executed little confidential commissions for Langhorne, sometimes things that took her on short trips out of town. There is a possibility that she may be on a mission of that sort. But I think--it's this Black Book case that involves her now." "Langhorne wouldn't talk much about anything," I put in, hastily remembering his manner. "He may not be responsible--but from his actions I'd wager he knows more about her than appears." "Just so," agreed Carton. "If my men can find out that she was the operator who 'listened in' and got the notes and the transcript of the Black Book, then she becomes a person of importance in the case and the fact must be known to others who are interested. Why," he pursued, "don't you see what it means? If she is out of the way, there is no one to swear to the accuracy of the notes in the record, no one to identify the voices--even if we do manage finally to locate the thing." "Dorgan and the rest are certainly leaving nothing undone to shake the validity of the record," ruminated Kennedy, accepting for the moment at least Carton's explanation of the disappearance of Miss Blackwell. "Have you any idea what might have happened to her?" Carton shook his head negatively. "There are several explanations," he replied slowly. "As far as we have been able to find out she led a model life, at home with her mother and sister. Except for the few commissions for Langhorne and lately when she was out rather late taking the detectaphone notes, she was very quiet,--in fact devoted to her mother and the education of her younger sister." "What sort of place was it in which the receivers of the detectaphone were located--do you know?" asked Kennedy quickly. "Yes, it seems to be a very respectable boardinghouse," answered Carton. "She came there with a grip about a week ago and hired a room, saying she was out of town a great deal. Just about the same time a young man, who posed as a student in electrical engineering at some school uptown, left. It must have been he who installed the detectaphone--perhaps with the aid of a waiter in Gastron's. At any rate, she seems to have been alone in the boarding-house--that is, I mean, not acquainted with any of the other guests--during the time when she was taking down the record. Dorgan traced the wires, outside the two buildings, to her rooms, but she was not there. In fact there was nothing there but a grip with a few articles that give no clue to anything. Somehow she must have heard of it, for no one knows anything about her, since then." "Perhaps Langhorne is keeping her out of the way so that no one can tamper with her testimony," I suggested. "It's possible," said Carton in a tone that showed that he did not believe in that explanation. "How about that safe robbery, Kennedy? Some of the papers hinted that she might have known something of that. I had a man down there watching, afterwards, but I had cautioned him to be careful and keep under cover. One of the elevator boys told him that the robbers had made a hole in the safe. What did he mean? Did you see it?" Rapidly Kennedy sketched what we had done, telling the story of how the dynamometer had at least partly exonerated Betty Blackwell. When he reached the description of the hole in the safe, Carton was absolutely incredulous. As for myself, it presented a mystery which I found absolutely inexplicable. How it was possible in such a short time to make a hole in a safe by any known means, I could not understand. In fact, if I had not seen it myself, I should have been even more sceptical than Carton. Kennedy, however, made no reply immediately to our expressions of doubt. He had found and set apart from the rest a couple of little glass bottles with ground glass stoppers. Then he took a thick piece of steel and laid it across a couple of blocks of wood, under which was a second steel plate. Without a word of explanation, he took the glass stopper out of the larger bottle and poured some of the contents on the upper plate of steel. There it lay, a little mound of reddish powder. Then he took a little powder of another kind from the other bottle. He lighted a match and ignited the second pile of powder. "Stand back--close to the wall--shield your eyes," he called to us. He had dropped the burning mass on the red powder and in two or three leaps he joined us at the far end of the room. Almost instantly a dazzling, intense flame broke out. It seemed to sizzle and crackle. With bated breath we waited and, as best we could, shielding our eyes from the glare, watched. It was almost incredible, but that glowing mass of powder seemed literally to be sinking, sinking right down into the cold steel. In tense silence we waited. On the ceiling we could see the reflection of the molten mass in the cup which it had burned for itself in the cold steel plate. At last it fell through to the lower piece of steel, on which it burnt itself out--fell through as the burning roof of a frame building might have fallen into the building. Neither Carton nor I spoke a word, but as we now cautiously advanced with Kennedy and peered over the steel plate we instinctively turned to Craig for an explanation. Carton seemed to regard him as if he were some uncanny mortal. For, there in the steel plate, was a hole. As I looked at the clean-cut edges, I saw that it was smaller but identical in nature with that which we had seen in the safe in Langhorne's office. "Wonderful!" ejaculated Carton. "What is it?" "Thermit," was all Kennedy said, as just a trace of a smile of satisfaction flitted over his face. "Thermit?" echoed Carton, still as mystified as before. "Yes, an invention of a chemist named Goldschmidt, of Essen, Germany. It is composed of iron oxide, such as conies off a blacksmith's anvil or the rolls of a rolling-mill, and powdered metallic aluminum. You could thrust a red-hot bar into it without setting it off, but when you light a little magnesium powder and drop it on thermit, a combustion is started that quickly reaches fifty-four hundred degrees Fahrenheit. It has the peculiar property of concentrating its heat to the immediate spot on which it is placed. It is one of the most powerful oxidizing agents known, and it doesn't even melt the rest of the steel surface. You see how it ate its way directly through this plate. Steel, hard or soft, tempered, annealed, chrome, or Harveyized--it all burns just as fast and just as easily. And it's comparatively inexpensive, also. This is an experiment Goldschmidt it fond of showing his students--burning holes in one--and two-inch steel plates. It is the same with a safe--only you need more of the stuff. Either black or red thermit will do the trick equally well, however." Neither of us said anything. There was nothing to say except to feel and express amazement. "Someone uncommonly clever or instructed by someone uncommonly clever, must have done that job at Langhorne's," added Craig. "Have you any idea who might pull off such a thing for Dorgan or Murtha?" he asked of Carton. "There's a possible suspect," answered Carton slowly, "but since I've seen this wonderful exhibition of what thermit can do, I'm almost ashamed to mention his name. He's not in the class that would be likely to use such things." "Oh," laughed Kennedy, "never think it. Don't you suppose the crooks read the scientific and technical papers? Believe me, they have known about thermit as long as I have. Safes are constructed now that are proof against even that, and other methods of attack. No indeed, your modern scientific cracksman keeps abreast of the times in his field better than you imagine. Our only protection is that fortunately science always keeps several laps ahead of him in the race--and besides, we have organized society to meet all such perils. It may be that the very cleverness of the fellow will be his own undoing. The unusual criminal is often that much the easier to run down. It narrows the number of suspects." "Well," rejoined Carton, not as confident now as when he had first met us in the laboratory, "then there is a possible suspect--a fellow known in the underworld as 'Dopey' Jack--Jack Rubano. He's a clever fellow--no doubt. But I hardly think he's capable of that, although I should call him a rather advanced yeggman." "What makes you suspect him?" asked Kennedy eagerly. "Well," temporized Carton, "I haven't anything 'on' him in this connection, it's true. But we've been trying to find him and can't seem to locate him in connection with primary frauds in Murtha's own district. Dopey Jack is the leader of a gang of gunmen over there and is Murtha's first lieutenant whenever there is a tough political battle of the organization either at the primaries or on Election Day." "Has a record, I suppose?" prompted Kennedy. "Would have--if it wasn't for the influence of Murtha," rejoined Carton. I had heard, in knocking about the city, of Dopey Jack Rubano. That was the picturesque title by which he was known to the police and his enemies as well as to his devoted followers. A few years before, he had begun his career fighting in "preliminaries" at the prize fight clubs on the lower East Side. He had begun life with a better chance than most slum boys, for he had rugged health and an unusually sturdy body. His very strength had been his ruin. Working decently for wages, he had been told by other petty gang leaders that he was a "sucker," when he could get many times as much for boxing a few rounds at some "athletic" club. He tried out the game with many willing instructors and found that it was easy money. Jack began to wear better clothes and study the methods of other young men who never worked but always seemed to have plenty of money. They were his pals and showed him how it was done. It wasn't long before he learned that he could often get more by hitting a man with a blackjack than by using his fists in the roped ring. Then, too, there were various ways of blackmail and extortion that were simple, safe, and lucrative. He might be arrested, but he early found that by making himself useful to some politicians, they could fix that minor difficulty in the life. Thus because he was not only strong and brutal, but had a sort of ability and some education, Dopey Jack quickly rose to a position of minor leadership--had his own incipient "gang," his own "lobbygows." His following increased as he rose in gangland, and finally he came to be closely associated with Murtha himself on one hand and the "guns" and other criminals of the underworld who frequented the stuss games, where they gambled away the products of their crimes, on the other. Everyone knew Dopey Jack. He had been charged with many crimes, but always through the aid of "the big fellows" he avoided the penitentiary and every fresh and futile attempt to end his career increased the numbers and reverence of his followers. His had been the history and he was the pattern now of practically every gang leader of consequence in the city. The fight club had been his testing ground. There he had learned the code, which can be summarized in two words, "Don't squeal." For gangland hates nothing so much as a "snitch." As a beginner he could be trusted to commit any crime assigned to him and go to prison, perhaps the chair, rather than betray a leader. As a leader he had those under him trained in the same code. That still was his code to those above him in the System. "We want him for frauds at the primaries," repeated Carton, "at least, if we can find him, we can hold him on that for a time. I thought perhaps he might know something of the robbery--and about the disappearance of the girl, too. "Oh," he continued, "there are lots of things against him. Why, only last week there was a dance of a rival association of gang leaders. Against them Dopey Jack led a band of his own followers and in the ensuing pistol battle a passer-by was killed. Of course we can't connect Dopey Jack with his death, but--then we know as well as we know anything in gangland that he was responsible." "I suppose it isn't impossible that he may know something about the disappearance of Miss Blackwell," remarked Kennedy. "No," replied Carton, "not at all, although, so far, there is absolutely no clue as far as I can figure out. She may have been bought off or she may have been kidnapped." "In either case the missing girl must be found," said Craig. "We must get someone interested in her case who knows something about what may happen to a girl in New York." Carton had been revolving the matter in his mind. "By George," he exclaimed suddenly, "I think I know just the person to take up that case for us--it's quite in her line. Can you spare the time to run down to the Reform League headquarters with me?" "Nothing could be more important, just at the minute," replied Craig. The telephone buzzed and he answered it, a moment later handing the receiver to Carton. "It's your office," he said. "One of the assistant district attorneys wants you on the wire." As Carton hung up the receiver he turned to us with a look of great satisfaction. "Dopey Jack has just been arrested," he announced. "He has shut up like an oyster, but we think we can at least hold him for a few days this time until we sift down some of these clues." V THE SUFFRAGETTE SECRETARY Carton took us directly to the campaign headquarters of the Reform League, where his fight for political life was being conducted. We found the offices in the tower of a skyscraper, whence was pouring forth a torrent of appeal to the people, in printed and oral form of every kind, urging them to stand shoulder to shoulder for good government and vote the "ring" out of power. There seemed to me to be a different tone to the place from that which I had ordinarily associated with political headquarters in previous campaigns. There was a notable absence of the old-fashioned politicians and of the air of intrigue laden with tobacco. Rather, there was an air of earnestness and efficiency, which was decidedly encouraging and hopeful. It seemed to speak of a new era in politics when things were to be done in the open instead of at secret meetings and scandalous dinners, as Dorgan did them at Gastron's. Maps of the city were hanging on the walls, some stuck full of various coloured pins, denoting the condition of the canvass. Other maps of the city in colours, divided into all sorts of districts, told how fared the battle in the various strongholds of Boss Dorgan and Sub-boss Murtha. Huge systems of card indexes, loose leaf devices, labour-saving appliances for getting out a vast amount of campaign "literature" in a hurry; in short, a perfect system, such as a great, well-managed business might have been proud of, were in evidence everywhere one looked. Work was going ahead in every department under high pressure, for the campaign, which had been more than usually heated, was now drawing to a close. Indeed, it would have taken no great astuteness, even without one's being told, to deduce merely from the surroundings that the people here were engaged in the annual struggle of seeking the votes of their fellow-citizens for reform and were nearly worn out by the arduous endeavour. It had been, as I have said, the bitterest campaign in years. Formerly the reformers had been of the "silk-stocking" type, but now a new and younger generation was coming upon the stage, a generation which had been trained to achieve results, ambitious to attain what in former years had been considered impossible. The Reform League was making a stiff campaign and the System was, by the same token, more frightened than ever before. Carton was fortunate in having shaken off the thralldom of the old bosses even before the popular uprising against them had assumed such proportions as to warrant anyone in taking his political life in his hands by defying the powers that ruled behind the scenes. In fact, the Reform League itself owed its existence to a fortunate conjunction of both moral and economic conditions which demanded progress. Of course, the League did not have such a big "barrel" as their opponents under Dorgan. But, at least they did have many willing workers, men and women, who were ready to sacrifice something for the advancement of the principles for which they stood. In one part of the suite of offices which had been leased by the League, Carton had had assigned to him an office of his own, and it was to this office that he led us, after a word with the boy who guarded the approach to the door, and an exchange of greetings with various workers and visitors in the outside office. We seated ourselves while Carton ran his eye through some letters that had been left on his desk for his attention. A moment later the door of his office opened and a young lady in a very stunning street dress, with a pretty little rakish hat and a tantalizing veil, stood a moment, hesitated, and then was about to turn back with an apology for intruding on what looked like a conference. "Good-morning, Miss Ashton," greeted Carton, laying down the letters instantly. "You're just the person I want to see." The girl, with a portfolio of papers in her hand, smiled and he quickly crossed the room and held the door open, as he whispered a word or two to her. She was a handsome girl, something more than even pretty. The lithe gracefulness of her figure spoke of familiarity with both tennis and tango, and her face with its well-chiselled profile denoted intellectuality from which no touch of really feminine charm had been removed by the fearsome process of the creation of the modern woman. Sincerity as well as humour looked out from the liquid depths of her blue eyes beneath the wavy masses of blonde hair. She was good to look at and we looked, irresistibly. "Let me introduce Professor Kennedy and Mr. Jameson, Miss Ashton," began Carton, adding: "Of course you have heard of Miss Margaret Ashton, the suffragist leader? She is the head of our press bureau, you know. She's making a great fight for us here--a winning fight." It seemed from the heightened look of determination which set Carton's face in deeper lines that Miss Ashton had that indispensable political quality of inspiring both confidence and enthusiasm in those who worked with her. "It is indeed a great pleasure to meet you," remarked Kennedy. "Both Mr. Jameson and myself have heard and read a great deal about your work, though we seem never before to have had the pleasure of meeting you." Miss Ashton, I recalled, was a very clever girl, a graduate of a famous woman's college, and had had several years of newspaper experience before she became a leader in the cause of equal suffrage. The Ashtons were well known in society and it was a sore trial to some of her conservative friends that she should reject what they considered the proper "sphere" for women and choose to go out into life and devote herself to doing something that was worth while, rather than to fritter her time and energy away on the gaiety and inconsequentiality of social life. Among those friends, I had understood, was Hartley Langhorne himself. He was older than Miss Ashton, but had belonged to the same social circle and had always held her in high regard. In fact the attentions he paid her had long been noticeable, the more so as she seemed politely unaffected by them. Carton had scarcely more than introduced us, yet already I felt sure that I scented a romance behind the ordinarily prosaic conduct of a campaign press bureau. It is far from my intention even to hint that the ability or success of the head of the press bureau were not all her own or were in any degree overrated. But it struck me, both then and often later, that the candidate for District Attorney had an extraordinary interest in the newspaper campaign, much more, for instance, than in the speakers' bureau. I am sure that it was not wholly accounted for by the fact that publicity is playing a more and more important part in political campaigning. Nevertheless, as we came to know afterwards such innovations as her card index system by election districts all over the city, showing the attitude of the various newspaper editors, local leaders, and other influential citizens, recording changes of sentiment and possible openings for future work, all were very full and valuable. Kennedy, who had a regular pigeon-hole mind for facts himself, was visibly impressed by the huge mechanical memory built up by Miss Ashton. Though he said nothing to me, I knew that Craig also had observed the state of affairs between the reform candidate and the suffrage leader. "You see, Miss Ashton," explained Carton, "someone has placed a detectaphone in the private dining-room of Dorgan at Gastron's. I heard of it first through Mrs. Ogleby, who attended one of the dinners and was terribly afraid her name would be connected with them if the record should ever be published." "Mrs. Ogleby?" cried Miss Ashton quickly. "She--at a dinner--with Mr. Murtha? I--I can't believe it." Carton said nothing. Whether he knew more about Mrs. Ogleby than he cared to tell, I could not even guess. As he went on briefly summarizing the story, Miss Ashton shot a quick glance or two at him. Carton noticed it, but appeared not to do so. "I suppose," he concluded, "that she thought I was the only person capable of eavesdropping. As a matter of fact, I think the instrument was put in by Hartley Langhorne as part of the fight that is going on fiercely under the surface in the organization." It was Carton's turn now, I fancied, to observe Miss Ashton more closely. As far as I could see, the information was a matter of perfect indifference to her. Carton did not say it in so many words, but one could not help gathering that rather than seem to be pursuing a possible rival and using his official position in order to do it, he was not considering Langhorne in any other light than as a mere actor in the drama between himself and Dorgan and Murtha. "Now," he concluded, "the point of the whole thing is this, Miss Ashton. We have learned that Betty Blackwell--you know the case--who took the notes over the detectaphone for the Black Book, has suddenly and mysteriously disappeared. If she is gone, it may be difficult to prove anything, even if we get the book. Miss Blackwell happens to be a stenographer in the office of Langhorne & Westlake." For the first time, Miss Ashton seemed to show a sign of embarrassment. Evidently she would just as well have had Miss Blackwell in some other connection. "Perhaps you would rather have nothing to do with it," suggested Carton, "but I know that you were always interested in things of the sort that happen to girls in the city and thought perhaps you could advise us, even if you don't feel like personally taking up the case." "Oh, it doesn't--matter," she murmured. "Of course, the first thing for us to do is, as you say, to find what has become of Betty Blackwell." Carton turned suddenly at the word "us," but Miss Ashton was still studying the pattern of the rug. "Do you know any more about her?" she asked at length. As fully as possible the District Attorney repeated what he had already told us. Miss Ashton seemed to be more than interested in the story of the disappearance of Langhorne's stenographer. As Carton unfolded the meagre details of what we knew so far, Miss Ashton appeared to be torn by conflicting opinions. The more she thought of what might possibly have happened to the unfortunate girl, the more aroused about the case she seemed to become. Carton had evidently calculated on enlisting her sympathies, knowing how she felt toward many of the social and economic injustices toward women, and particularly girls. "If Mr. Murtha or Mr. Dorgan is responsible in any way for any harm to her," she said finally, her earnest eyes now ablaze with indignation, "I shall not rest until someone is punished." Kennedy had been watching her emotions keenly, I suspect, to see whether she connected Langhorne in any way with the disappearance. I could see it interested him that she did not seem even to consider that Langhorne might be responsible. Whether her intuition was correct or not, it was at least better at present than any guess that we three might have made. "They control so many forces for evil," she went on, "that there is no telling what they might command against a defenceless girl like her when it is a question of their political power." "Then," pursued Kennedy, pacing the floor thoughtfully, "the next question is, How are we to proceed? The first step naturally will be the investigation of this Little Montmartre. How is it to be done? I presume you don't want to go up there and look the place over yourself, do you, Carton?" "Most certainly not," said Carton emphatically. "Not if you want this case to go any further. Why, I can't walk around a corner now without a general scurry for the cyclone cellars. They all know me, and those who don't are watching for me. On the contrary, if you are going to start there I had better execute a flank movement in Queens or Jersey to divert attention. Really, I mean it. I had better keep in the background. But I'll tell you what I would like to do." Carton hesitated and came to a full stop. "What's the matter?" asked Kennedy quickly, noticing the hesitation. "Why--I--er--didn't know just how you'd take a suggestion--that's all." "Thankfully. What is it?" "You know young Haxworth?" "You mean the son of the millionaire who is investigating vice and whom the newspapers are poking fun at?" "Yes. Those papers make me tired. He has been working, you know, with me in this matter. He is really serious about it, too. He has a corps of investigators of his own already. Well, there is one of them, a woman detective named Clare Kendall, who is the brains of the whole Haxworth outfit. If you would be willing to have them--er--to have her co-operate with you, I think I could persuade Haxworth---" "Oh," broke in Kennedy with a laugh. "I see. You think perhaps there might be some professional jealousy? On the contrary, it solves a problem I was already considering. Of course we shall need a woman in this case, one with a rare amount of discretion and ability. Yes, by all means let us call in Miss Kendall, and let us take every advantage we can of what she has already accomplished." Carton seized the telephone. "Tell her to meet us at my laboratory in half an hour," interposed Kennedy. "You will come along?" "I can't. Court opens in twenty minutes and there is a motion I must argue myself." Miss Ashton appeared to be greatly gratified at Craig's reception of the suggestion, and Carton noticed it. "Oh, yes," recollected Carton, "by the way, as I was on my way down here, my office called up and told me that they had succeeded in locating and arresting Dopey Jack. That ought to please you,--it will mean cutting down the number of those East Side 'rackets' considerably if we succeed with him." "Good!" she exclaimed. "Yes, I don't think there were any worse affairs than the dances of that Jack Rubano Association. They have got hold of more young girls and caused more tragedies than any other gang. If you need any help in getting together evidence, Mr. Carton, I shall be only too glad to help you. I have several old scores myself to settle with that young tough." "Thank you," said Carton. "I shall need your help, if we are to do anything. Of course, we can hold him only for primary frauds just now, but I may be able to do something about that dance that he broke up as a shooting affray." Miss Ashton nodded encouragingly. "And," he went on, "it's barely possible that he may know something, or some of his followers may, about the robbery of Mr. Langhorne's safe,--if not about the complete and mysterious disappearance of Betty Blackwell." "They'd stop at nothing to save their precious skins," commented Miss Ashton. "Perhaps that is a good lead. At any rate I can suggest that to the various societies and other agencies which I intend to set in motion trying to trace what has happened to her. You can have him held until they have time to report?" "I shall make it a point to do so at any cost," he returned, "and I can say only this, that we are all deeply indebted to you for the interest you have shown in the case." "Not at all," she replied enthusiastically, evidently having overcome the first hesitation which had existed because Miss Blackwell had been Langhorne's stenographer. Miss Ashton had quickly jotted down in her notebook the best description we could give of the missing girl, her address, and other facts about her, and a list of those whom she meant to start at work on the case. For a moment she hesitated over one name, then with a sudden resolution wrote it down. "I intend to see Hartley Langhorne about it, too," she added frankly. "Perhaps he may tell something of importance, after all." I am sure that this final resolution cost her more than all the rest. Carton would never have asked it of her, yet was gratified that she saw it to be her duty to leave nothing undone in tracing the girl, not even considering the possibility of offending Langhorne. "Decent people don't seem to realize," she remarked as she shut her little notebook and slipped it back into her chatelaine, "how the System and the underworld really do affect them. They think it is all something apart from the rest of us, and never consider how closely we are all bound together and how easy it is for the lowest and most vicious stratum in the social order to pass over and affect the highest." "That's exactly the point," agreed Carton. "Take this very case. It goes from Wall Street to gangland, from Gastron's down to the underworld gambling joints of Dopey Jack and the rest." "Society--gambling," mused Miss Ashton, taking out her notebook again. "That reminds me of Martin Ogleby. I must see Mary and try to warn her against some of those sporty friends of her husband's." "Please, Miss Ashton," put in Carton quickly, "don't mention that I have told you of the detectaphone record. It might do more harm than good, just at present. For a time at least, I think we should try to keep under cover." Whether or not that was his real reason, he turned now to Kennedy for support. We had been, for the most part, silent spectators of what had been happening. "I think so--for the present--at least as far as our knowledge of the Black Book goes," acquiesced Craig. He had turned to Miss Ashton and made no effort to conceal the admiration which he felt for her, after even so brief an acquaintance. "I think Miss Ashton can be depended upon to play her part in the game perfectly. I, for one, want to thank her most heartily for the way in which she has joined us." "Thank you," she smiled, as she rose to go to her own office. "Oh, you can always depend on me," she assured us as she gathered up her portfolio of papers, "where there are the interests of a girl like Betty Blackwell involved!" VI THE WOMAN DETECTIVE Half an hour later, a tall, striking, self-reliant young woman with an engaging smile opened the laboratory door and asked for Professor Kennedy. "Miss Kendall?" Craig inquired, coming forward to meet her. She was dark-haired, with regular features and an expression which showed a high degree of intelligence. Her clear grey eyes seemed to penetrate and tear the mask off you. It was not only her features and eyes that showed intelligence, but her gown showed that without sacrificing neatness she had deliberately toned down the existing fashions which so admirably fitted in with her figure in order that she might not appear noticeable. It was clever, for if there is anything a good detective must do it is to prevent people from looking twice. I knew something of her history already. She had begun on a rather difficult case for one of the large agencies and after a few years of experience had decided that there was a field for an independent woman detective who would appeal particularly to women themselves. Unaided she had fought her way to a position of keen rivalry now with the best men in the profession. Narrowly I watched Kennedy. Here, I felt instinctively, were the "new" woman and the "new" man, if there are such things. I wondered just how they would hit it off together. For the moment, at least, Clare Kendall was an absorbing study, as she greeted us with a frank, jerky straight-arm handshake. "Mr. Carton," she said directly, "has told me that he received an anonymous letter this morning. May I see it?" There are times when the so-called "new" woman's assumed masculine brusqueness is a trifle jarring, as well as often missing the point. But with Clare Kendall one did not feel that she was eternally trying to assert that she was the equal or the superior of someone else, although she was, as far as the majority of detectives I have met are concerned. It was rather that she was different; in fact, almost from the start I felt that she was indispensable. She seemed to have that ability to go straight to the point at issue, a sort of faculty of intuition which is often more valuable than anything else, the ability to feel or sense things for which at first there was no actual proof. No good detective ever lacks that sort of instinct, and Clare Kendall, being a woman, had it in large degree. But she had more. She had the ability to go further and get the facts and actual proof; for, as she often said during the course of a case, "Woman's intuition may not be good evidence in a court of law, but it is one of the best means to get good evidence that will convince a court of law." "My investigators have been watching that place for some time," she remarked as she finished the letter. "Of course, having been closely in touch with this sort of thing for several months in my work, I have had all the opportunity in the world to observe and collect information. The letter does not surprise me." "Then you think it is a good tip?" asked Kennedy. "Decidedly, although without the letter I should not have started there, I think. Still, as nearly as I can gather, there is a rather nondescript crowd connected in one way or another with the Montmartre. For instance, there is a pretty tough character who seems to be connected with the people there, my investigators tell me. It is a fellow named 'Ike the Dropper,' one of those strong-arm men who have migrated up from the East Side to the White Light District. At least my investigators have told me they have seen him there, for I have never bothered with the place myself. There has been plenty of work elsewhere which promised immediate results. I'm glad to have a chance to tackle this place, though, with your help." "What do you think of the rest of the letter?" asked Craig. "I think I could make a pretty shrewd guess from what I have heard, as to the identity of some of those hinted at. I'm not sure, but I think the lawyer may be a Mr. Kahn, a clever enough attorney who has a large theatrical clientele and none too savoury a reputation as a local politician. The banker may be Mr. Langhorne, although he is not exactly a young man. Still, I know he has been associated with the place. As for the club-man I should guess that that was Martin Ogleby." Kennedy and I exchanged glances of surprise. "As a first step," said Kennedy, at length, "I am going to write a letter to Betty Blackwell, care of the Little Montmartre--or perhaps you had better do the actual writing of it, Miss Kendall. A woman's hand will look less suspicious." "What shall I write?" she asked. "Just a few lines. Tell her that you are one of the girls in the office, that you have heard she was at the Montmartre--anything. The actual writing doesn't make any difference. I merely want to see what happens." Miss Kendall quickly wrote a little note and handed it to him. "Then direct this envelope," he said, reaching into a drawer of his desk and bringing out a plain white one. "And let me seal it." Carefully he sealed and stamped the letter and handed it to me to post. "You will dine with us, Miss Kendall?" he asked. "Then we will plan the next step in our campaign." "I shall be glad to do so," she replied. Fifteen minutes later I had dropped the letter in the drop of a branch of the general post-office to ensure its more prompt delivery, and it was on its way through the mails to accomplish the purpose Kennedy may have contemplated. "Just now it is more important for us to become acquainted with this Little Montmartre," he remarked. "I suppose, Miss Kendall, we may depend on you to join us?" "Indeed you may," she replied energetically. "There is nothing that we would welcome more than evidence that would lead to the closing of that place." Kennedy seemed to be impressed by the frankness and energy of the young woman. "Perhaps if we three should go there, hire a private dining-room, and look about without making any move against the place that would excite suspicion, we might at least find out what it is that we are fighting. Of course we must dine somewhere, and up there at the same time we can plan our campaign." "I think that would be ripping," she laughed, as the humour of the situation dawned on her. "Why, we shall be laying our plans right in the heart of the enemy's country and they will never realize it. Perhaps, too, we may get a glimpse of some of those people mentioned in the anonymous letter." To Clare Kendall it was simply another phase of the game which she had been playing against the forces of evil in the city. The Little Montmartre was, as I already knew, one of the smaller hotels in a side street just off Broadway, eight or ten stories in height, of modern construction, and for all the world exactly like a score of other of the smaller hostelries of the famous city of hotels. Clare, Craig, and myself pulled up before the entrance in a taxicab, that seeming to be the accepted method of entering with eclat. A boy opened the door. I jumped out and settled with the driver without a demur at the usual overcharge, while Craig assisted Clare. Laughing and chatting, we entered the bronze plate-glass doors and walked slowly down a richly carpeted corridor. It was elegantly furnished and decorated with large palms set at intervals, quite the equal in luxuriousness, though on a smaller scale, of any of the larger and well-known hotels. Beautifully marked marbles and expensive hangings greeted the eye at every turn. Faultlessly liveried servants solicitously waited about for tips. Craig and Clare, who were slightly ahead of me, turned quickly into a little alcove, or reception room and Craig placed a chair for her. Farther down the corridor I could see the office, and beyond a large main dining-room from which strains of music came and now and then the buzz of conversation and laughter from gay parties at the immaculately white tables. "Boy," called Kennedy quietly, catching the eye of a passing bell hop and unostentatiously slipping a quarter into his hand, which closed over the coin almost automatically, "the head waiter, please. Oh--er--by the way--what is his name?" "Julius," returned the boy, to whom the proceeding seemed to present nothing novel, although the whole atmosphere of the place was beyond his years. "I'll get him in a minute, sir. He's in the main dining-room. He's having some trouble with the cabaret singers. One of them is late--as usual." We sat in the easy chairs watching the people passing and repassing in the corridor. There was no effort at concealment here. A few minutes later Julius appeared, a young man, tall and rather good-looking, suave and easy. A word or two with Kennedy followed, during which a greenback changed hands--in fact that seemed to be the open sesame to everything here--and we were in the elevator decorously escorted by the polished Julius. The door of the elevator shut noiselessly and it shot up to the next floor. Julius preceded us down the thickly carpeted corridor leading the way to a large apartment, or rather a suite of rooms, as handsomely furnished as any in other hotels. He switched on the lights and left us, with the remark, "When you want the waiter or anything, just press the button." In the largest of the rooms was a dining-table and several chairs of Jacobean oak. A heavy sideboard and serving-table stood against opposite walls. Another, smaller room was furnished very attractively as a sitting-room. Deep, easy chairs stood in the corners and a wide, capacious davenport stretched across one wall. In another nook was a little divan or cosy corner. Electric bulbs burned pinkly in the chandeliers and on silver candelabra on the table, giving a half light that was very romantic and fascinating. From a curtained window that opened upon an interior court we could catch strains from the cabaret singers below in the main dining-room. Everything was new and bright. Kennedy pressed the button and a waiter brought a menu, imposing in length and breath-taking in rates. "The cost of vice seems to have gone up with the cost of living," remarked Miss Kendall, as the waiter disappeared as silently as he had responded to the bell. It was a phrase that stuck in my head, so apt was it in describing the anomalous state of things we found as the case unrolled. Craig ordered, now and then consulting Clare about some detail. The care and attention devoted to us could not have been more punctilious if it had been an elaborate dinner party. "Well," he remarked, as the waiter at last closed the door of the private dining-room to give the order in downstairs in the kitchen, "the Little Montmartre makes a brave showing. I suppose it will be some time before the dinner arrives, though. There is certainly some piquancy to this," he added, looking about at the furnishings. "Yes," remarked Miss Kendall, "risque from the moment you enter the door." She said it with an impersonal tone as if there were complete detachment between herself as an observer and as a guest of the Montmartre. "Miss Kendall," asked Kennedy, "did you notice anything particularly downstairs? I'd like to check up my own impressions by yours." "I noticed that Titian beauty in the hotel office as we left the reception room and entered the elevator." Craig smiled. "So did I. I thought you would be both woman enough and detective enough to notice her. Well, I suppose if a man likes that sort of girl that's the sort of girl he likes. That's point number one. But did you notice anything else--as we came in, for instance?" "No--except that everything seems to be a matter of scientific management here to get the most out of the suckers. This is no place for a piker. It all seems to run so smoothly, too. Still, I'm sure that our investigators might get something on the place if they kept right after it, although on the surface it doesn't look as if any law was being openly violated here. What do you mean? What is your point number two?" "In the front window," resumed Craig, "just as you enter, I noticed one of those little oblong signs printed neatly in black on white--'Dr. Vernon Harris, M. D.' You recall that the letter said something about a doctor who was very friendly with that clique the writer mentioned? It's even money that this Harris is the one the writer meant. I suppose he is the 'house physician' of this gilded palace." Clare nodded appreciatively. "Quite right," she agreed. "Just how do you think he might be involved?" "Of course I can't say. But I think, without going any further, that a man like that in a place like this will bear watching anyway, without our needing more than the fact that he is here. Naturally we don't know anything about him as a doctor, but he must have some training; and in an environment like this--well, a little training may be a dangerous thing." "The letter said something about drugs," mused Clare. "Yes," added Kennedy. "As you know, alcohol is absolutely necessary to a thing like this. Girls must keep gay and attractive; they must meet men with a bright, unfaltering look, and alcohol just dulls the edge of conscience. Besides, look over that wine list--it fills the till of the Montmartre, judging by the prices. But then, alcohol palls when the pace is as swift as it seems to be here. Even more essential are drugs. You know, after all, it is no wonder so many drug fiends and drunkards are created by this life. Now, a doctor who is not over-scrupulous, and he would have to be not over-scrupulous to be here at all, would find a gold mine in the dispensing of drugs and the toning up of drug fiends and others who have been going the pace too rapidly." "Yes," she said. "We have found that some of these doctors are a great factor in the life of various sections of the city where they hang out. I know one who is deeply in the local politics and boasts that any resort that patronizes him is immune. Yes, that's a good point about Dr. Harris." "I suppose your investigators have had more or less to do with watching the progress of drug habits?" ventured Craig. "Very much," she replied, catching the drift of his remarks. "We have found, for instance, that there are a great many cases where it seems that drugs have been used in luring young and innocent girls. Not the old knockout drops--chloral, you know--but modern drugs, not so powerful, perhaps, but more insidious, and in that respect, I suppose, more dangerous. There are cocaine fiends, opium smokers; oh, lots of them. But those we find in the slums mostly. Still, I suppose there are all kinds of drugs up here in the White Light District--belladonna to keep the eyes bright, arsenic to whiten the complexion, and so on." "Yes," asserted Craig. "This section of the city may not be so brutal in its drug taking as others, but it is here--yes, and it is over on Fifth Avenue, too, right in society. Before we get through I'm sure we'll both learn much more than we even dream of now." The door opened after a discreet tap from the waiter and the lavish dinner which Craig had ordered appeared. The door stayed open for a moment as the bus boy carried in the dishes. A rustle of skirts and low musical laughter was wafted in to us and we caught a glimpse of another gay party passing down the hall. "How many private dining-rooms are there?" asked Craig of the waiter. "Just this one, sir, and the next one, which is smaller," replied the model waiter, with the air of one who could be blind and deaf and dumb if he chose. "Oh, then we were lucky to get this." "Yes, sir. It is really best to telephone first to Julius to make sure and have one of the rooms reserved, sir." Craig made a mental note of the information. The party in the next room were hilariously ordering, mostly from the wine list. None of us had recognized any of them, nor had they paid much attention to us. Craig had eaten little, although the food was very good. "It's a shame to come here and not see the whole place," he remarked. "I wonder if you would excuse me while I drop downstairs to look over things there--perhaps ingratiate myself with that Titian? Tell Miss Kendall about our visit to Langhorne's office while I am gone, Walter." There was not much that I could tell except the bare facts, but I thought that Miss Kendall seemed especially interested in the broker's reticence about his stenographer. I had scarcely finished when Craig returned. A glance at his face told me that even in this brief time something had happened. "Did you meet the Titian?" I asked. "Yes. She is the stenographer and sometimes works the switchboard of the telephone. I happened to strike the office while the clerk was at dinner and she was alone. While I was talking to her I was looking about and my eye happened to fall on one of the letter boxes back of the desk, marked 'Dr. Harris.' Well, at once I had an overwhelming desire to get a note which I saw sticking in it. So I called up a telephone number, just as a blind, and while she was at the switchboard I slipped the note into my pocket. Here it is." He had laid an envelope down before us. It was in a woman's hand, written hastily. "I'd like to know what was in it without Dr. Harris knowing it," he remarked. "Now, the secret service agents abroad have raised letter-opening to a fine art. Some kinds of paper can be steamed open without leaving a trace, and then they follow that simple operation by reburnishing the flap with a bone instrument. But that won't do. It might make this ink run." Among the ornaments were several with flat wooden bases. Kennedy took one and placed it on the edge of the table, which was perfectly square. Then he placed the envelope between the table and the base. "When other methods fail," he went on, "they place the envelope between two pieces of wood with the edges projecting about a thirty-second of an inch." He had first flattened the edge of the envelope, then roughened it, and finally slit it open. "Scientific letter-opening," he remarked, as he pulled out a little note written on the hotel paper. It read: DEAR HARRY: Called you up twice and then dropped into the hotel, but you seem to be out all the time. Have something VERY IMPORTANT to tell you. Shall be busy to-night and in the morning, but will be at the dansant at the Futurist Tea Room to-morrow afternoon about four. Be sure to be there. MARIE. "I shall," commented Kennedy. "Now the question is, how to seal up this letter so that he won't know it has been opened. I saw some of this very strong mucilage in the office. Ring the bell, Walter. I'll get that impervious waiter to borrow it for a moment." Five minutes later he had applied a hair line of the strong, colourless gum to the inside of the envelope and had united the edges under pressure between the two pieces of wood. As soon as it was dry he excused himself again and went back to the office, where he managed to secure an opportunity to stick the letter back in the box and chat for a few minutes longer with the Titian. "There's a wild cabaret down in the main dining-room," he reported on his return. "I think we might just as well have a glimpse of it before we go." Kennedy paid the cheque, which by this time had mounted like a taximeter running wild, and we drifted into the dining-room, a rather attractive hall, panelled in Flemish oak with artificial flowers and leaves about, and here and there a little bird concealed in a cage in the paper foliage. As cabarets go, it was not bad, although I could imagine how wild it might become in the evening or on special occasion. "That Dr. Harris interests me," remarked Kennedy across the table at us. "We must get something in writing from him in some way. And then there's that girl in the office, too. She seems to be right in with all these people here." Evidently the cabaret had little of interest to Miss Kendall, who, after a glance that took in the whole dining-room and disclosed none there in the gay crowd who, as far as we could see, had any relation to the case, seemed bored. Craig noticed it and at once rose to go. As we passed out and into the corridor, Miss Kendall turned and whispered, "Look over at the desk--Dr. Harris." Sure enough, chatting with the stenographer was a man with one of those black bags which doctors carry. He was a young man in appearance, one of those whom one sees in the White Light District, with unnaturally bright eyes which speak of late hours and a fast pace. He wore a flower in his buttonhole--a very fetching touch with some women. Debonair, dapper, dashing, his face was not one readily forgotten. As we passed hurriedly I observed that he had torn open the note and had thrown the envelope, unsuspectingly, into the basket. VII THE GANG LEADER With the arrest of Dopey Jack, it seemed as if all the forces of the gang world were solidified for the final battle. Carton had been engaged in a struggle with the System so long that he knew just how to get action, the magistrates he could depend on, the various pitfalls that surrounded the snaring of one high in gangland, the judges who would fix bail that was prohibitively high. As he had anticipated and prepared for, every wire was pulled to secure the release of Rubano. But Carton was fortunate in having under him a group of young and alert assistants. It took the combined energies of his office, however, to carry the thing through and Kennedy and I did not see Carton again for some time. Meanwhile we were busy gathering as much information as we could about those who were likely to figure in the case. It was remarkable, but we found that the influence of Dorgan and Murtha was felt in the most unexpected quarters. People who would have talked to us on almost any other subject, absolutely refused to become mixed up in this affair. It was as though the System practised terrorism on a large scale. Late in the afternoon we met in Carton's office, to compare notes on the progress made during the day. The District Attorney greeted us enthusiastically. "Well," he exclaimed as he dropped into his big office chair, "this has been a hard day for me--but I've succeeded." "How?" queried Kennedy. "Of course the newspapers haven't got it yet," pursued Carton, "but it happened that there was a Grand Jury sitting and considering election cases. It went hard, but I made them consider this case of Dopey Jack. I don't know how it happened, but I seem to have succeeded in forcing action in record time. They have found an indictment on the election charges, and if that falls through, we shall have time to set up other charges against him. In fact we are 'going to the mat,' so to speak, with this case." The office telephone rang and after a few sentences of congratulation, Carton turned to us, his spirits even higher than before. "That was one of my assistants," he explained, "one of the cleverest. The trial will be before Judge Pomeroy in General Sessions and it will be an early trial. Pomeroy is one of the best of them, too--about to retire, and wants to leave a good record on the bench behind him. Things are shaping up as well as we could wish for." The door opened and one of Carton's clerks started to announce the name of a visitor. "Mr. Carton, Mr.--" "Murtha," drawled a deep voice, as the owner of the name strode in, impatiently brushing aside the clerk. "Hello, Carton," greeted the Sub-boss aggressively. "Hello, Murtha," returned Carton, retaining his good temper and seeing the humour of the situation, where the practice of years was reversed and the mountain was coming to Mahomet. "This is a little--er--informal--but I'm glad to see you, nevertheless," he added quietly. "Won't you sit down? By the way, meet Mr. Kennedy and Mr. Jameson. Is there anything I can do for you?" Murtha shook hands with us suspiciously, but did not sit down. He continued to stand, his hat tilted back over his head and his huge hands jammed down into his trousers pockets. "What's this I hear about Jack Rubano, Carton?" he opened fire. "They tell me you have arrested him and secured an indictment." "They tell the truth," returned Carton shortly. "The Grand Jury indicted Dopey Jack this afternoon. The trial---" "Dopey Jack," quoted Murtha in disgusted tones. "That's the way it is nowadays. Give a dog a bad name--why,--I suppose this bad name's going to stick to him all his life, now. It ain't right. You know, Carton, as well as I do that if they charged him with just plain fighting and got him before a jury, all you would have to say would be, 'Gentlemen, the defendant at the bar is the notorious gangster, Dopey Jack.' And the jurors wouldn't wait to hear any more, but'd say, 'Guilty!' just like that. And he'd go up the river for the top term. That's what a boy like that gets once the papers give him such an awful reputation. It's fierce!" Carton shook his head. "Oh, Murtha," he remonstrated with just a twinkle in his eye, "you don't think I believe that sort of soft stuff, do you? I've had my eye on this 'boy'--he's twenty-eight, by the way--too long. You needn't tell me anything about his respectable old father and his sorrowing mother and weeping sister. Murtha, I've been in this business too long for that heart throb stuff. Leave that to the lawyers the System will hire for him. Let's cut that out, between ourselves, and get down to brass tacks." It was a new and awkward role for Murtha as suppliant, and he evidently did not relish it. Aside from his own interest in Dopey Jack, who was one of his indispensables, it was apparent that he came as an emissary from Dorgan himself to spy out the land and perhaps reach some kind of understanding. He glanced about at us, with a look that broadly hinted that he would prefer to see Carton alone. Carton made no move to ask us to leave and Kennedy met the boss's look calmly. Murtha smothered his rage, although I knew he would with pleasure have had us stuck up or blackjacked. "See here, Carton." he blurted out at length, approaching the desk of the District Attorney and lowering his big voice as much as he was capable, "can't we reach some kind of agreement between ourselves? You let up on Rubano--and--well, I might be able to get some of my friends to let up on Carton. See?" He was conveying as guardedly as he could a proposal that if the District Attorney would consent to turn his back while the law stumbled in one of the numerous pitfalls that beset a criminal prosecution, the organization would deliver the goods, quietly pass the word along to knife its own man and allow Carton to be re-elected. I studied Carton's face intently. To a man of another stripe, the proposal might have been alluring. It meant that although the organization ticket won, he would, in the public eye at least, have the credit of beating the System, of going into office unhampered, of having assured beyond doubt what was at best only problematical with the Reform League. Carton did not hesitate a moment. I thought I saw in his face the same hardening of the lines of his features in grim determination that I had seen when he had been talking to Miss Ashton. I knew that, among other things, he was thinking how impossible it would be for him ever to face her again in the old way, if he sold out, even in a negative way, to the System. Murtha had shot his huge face forward and was peering keenly at the man before him. "You'll--think it over?" he asked. "I will not--I most certainly will not," returned Carton, for the first time showing exasperation, at the very assumption of Murtha. "Mr. Murtha," he went on, rising and leaning forward over the desk, "we are going to have a fair election, if I can make it. I may be beaten--I may win. But I will be beaten, if at all, by the old methods. If I win--it will be that I win--honestly." A half sneer crossed Murtha's face. He neither understood nor cared to understand the kind of game Carton played. "You'll never get anything on that boy," blustered Murtha. "Do you suppose I'm fool enough to come here and make a dishonest proposition--here--right in front of your own friends?" he added, turning to us. "--I ain't asking any favours, or anything dishonest. His lawyers know what they can do and what you can do. It ain't because I care a hang about you, Carton, that I'm here. If you want to know the truth, it's because you can make trouble, Carton,--that's all. You can't convict him, in the end, because--you can't. There's nothing 'on' him. But you can make trouble. We'll win out in the end, of course." "In other words, you think the Reform League has you beaten?" suggested Carton quietly. "No," ejaculated Murtha with an oath. "We don't know--but maybe YOU have us beaten. But not the League. We don't want you for District Attorney, Carton. You know it. But here's a practical proposition. All you have to do is just to let this Rubano case take its natural course. That's all I ask." He dwelt on the word "natural" as if it were in itself convincing. "Why," he resumed, "what foolishness it is for you to throw away all your chances just for the sake of hounding one poor fellow from the East Side. It ain't right, Carton,--you, powerful, holding an important office, and he a poor boy that never had a chance and has made the most of what little nature gave him. Why, I've known that boy ever since he hardly came up to my waist. I tell you, there ain't a judge on the bench that wouldn't listen to what we can show about him--hounded by police, hounded by the District Attorney, driven from pillar to post, and---" "You will have a chance to tell the story in court," cut in Carton. "Pomeroy will try the case." "Pomeroy?" repeated Murtha in a tone that quite disguised the anger he felt that it should come up before the one judge the System feared and could not control. "Now, look here, Carton. We're all practical men. Your friend--er--Kennedy, here, he's practical." Murtha had turned toward us. He was now the Murtha I had heard of before, the kind that can use a handshake or a playful slap on the back, as between man and man, to work wonders in getting action or carrying a point. Far from despising such men as Murtha, I think we all rather admired his good qualities. It was his point of view, his method, his aim that were wrong. As for the man himself he was human--in fact, I often thought far more human than some of the reformers. "I'll leave it to Kennedy," he resumed. "Suppose you were running a race. You knew you were going to win. Would you deliberately stop and stick your foot out, in order to trip up the man who was coming in second?" "I don't know that the cases are parallel," returned Kennedy with an amused smile. Murtha kept his good nature admirably. "Then you would stick your foot out--and perhaps lose the race yourself?" persisted Murtha. "I'll relieve Kennedy of answering that," interrupted Carton, "not because I don't think he can do it better than I can, perhaps, but because this is my fight--my race." "Well," asked Murtha persuasively, "you'll think it over, first, won't you?" Carton was looking at his opponent keenly, as if trying to take his measure. He had some scheme in mind and Kennedy was watching the faces of both men intently. "This race," began Carton slowly, in a manner that showed he wanted to change the subject, "is different from any other in the politics of the city as either of us have ever known it, Murtha." Murtha made as though he would object to the proposition, but Carton hurried on, giving him no chance to inject anything into the conversation. "It may be possible--it is possible," shot out the young District Attorney, "to make use of secret records--conversations--at conferences--dinners--records that have been taken by a new invention that seems to be revolutionizing politics all over the country." The look that crossed Murtha's face was positively apoplectic. The veins in his forehead stood out like whipcords. He started to speak, but choked off the words before he had uttered them. I could almost read his mind. Carton had said nothing directly about the Black Book, and Murtha had caught himself just in time not to betray anything about it. "So," he shouted at last, "you are going to try some of those fine little scientific tricks on us, are you?" He was pacing up and down the room, storming and threatening by turns. "I want to tell you, Carton," pursued Murtha, "that you're up against a crowd who were playing this game before you were born. You reformers think you are pretty smooth. But we know a thing or two about you and what you are doing. Besides," he leaned over the desk again, "Carton, there ain't many men that can afford to throw stones. I admit my life hasn't been perfect--but, then I ain't posing as any saint. I don't mind telling you that the organization, as you call it, is looking into some of the things that you reformers have done. It may be that some of your people--some of the ladies," he insinuated, "don't look on life in the broad-minded way that some of the rest do. Mind you--I ain't making any threats, but when it comes to gossip and scandal and mud-slinging--look out for the little old organization--that's all!" Carton had set his tenacious jaw. "You can go as far as you like, Murtha," was all he said, with a grim smile. Murtha looked at him a moment, then his manner changed. "Carton," he said in a milder tone, at length, "what's the use of all this bluffing? You and I understand each other. These men understand--life. It's a game--that's what it is--a game. Sometimes one move is right, sometimes another. You know what you want to accomplish here in this city. I show you a way to do it. Don't answer me," persisted Murtha, raising a hand, "just--think it over." Carton had taken a step forward, the tense look on his face unchanged. "No," he exclaimed, and we could almost hear his jaw snap as if it had been a trap. "No--I'll not think it over. I'll not yield an inch. Dopey Jack goes to trial before election." As Carton bit off the words, Murtha became almost beside himself with rage and chagrin. He was white and red by turns. For a moment I feared that he might do Carton personal violence. "Carton," he ground out, as he reached the door, "you will regret this." "I hope not," returned the other summoning with a mighty effort at least the appearance of suavity. "Good-bye." The only answer was the vicious slam which Murtha gave the door. As the echo died, the District Attorney turned to us. "Apparently, then, Dorgan did not secure the Black Book," was all he said, "even supposing Dopey Jack planned and executed that robbery of Langhorne." VIII THE SHYSTER LAWYER That's a declaration of war," remarked Kennedy, as Carton resumed his seat at the desk unconcernedly after the stormy ending of the interview with Murtha. "I suppose it is," agreed the District Attorney, "and I can't say that I am sorry." "Nor I," added Craig. "But it settles one thing. We are now out in what I call the 'open' investigation. They have forced us from cover. We shall have to be prepared to take quick action now, whatever move they may make." Together we were speculating on the various moves that the System might make and how we might prepare in advance for them. Evidently, however, we were not yet through with these indirect dealings with the Boss. The System was thorough, if nothing else, and prompt. We had about decided to continue our conference over the dinner table in some uptown restaurant, when the officer stationed in the hall poked his head in the door and announced another visitor for the District Attorney. This time the entrance was exactly the opposite to the bluster of Murtha. The man who sidled deferentially into the room, a moment after Carton had said he would see him, was a middle-sized fellow, with a high, slightly bald forehead, a shifty expression in his sharp ferret eyes, and a nervous, self-confident manner that must have been very impressive before the ignorant. "My name is Kahn," he introduced himself. "I'm a lawyer." Carton nodded recognition. Although I had never seen the man before, I recollected the name which Miss Kendall had mentioned. He was one of the best known lawyers of the System. He had begun his career as an "ambulance chaser," had risen later to the dignity of a police court lawyer, and now was of the type that might be called, for want of a better name, a high class "shyster"--unscrupulous, sharp, cunning. Shyster, I believe, has been defined as a legal knave, a lawyer who practises in an unprofessional or tricky manner. Kahn was all that--and still more. If he had been less successful, he would have been the black sheep of the overcrowded legal flock. Ideals he had none. His claws reached out to grab the pittance of the poverty-stricken client as well as the fee of the wealthy. He had risen from hospitals to police courts, coroner's court, and criminal courts, at last attaining the dignity of offices opposite an entrance to the criminal courts building, from which vantage point his underlings surveyed the scene of operations like vultures hovering over bewildered cattle. Carton knew him. Kahn was the leader among some score of men more or less well dressed, of more or less evil appearance, who are constantly prowling from one end to the other of the broad first floor of the criminal courts building during the hours of the day that justice is being administered there. These are the shyster lawyers and their runners and agents who prey upon the men and women whom misfortune or crime have delivered into the hands of the law. Others of the same species are wandering about the galleries on other floors of the building, each with a furtive eye for those who may be in trouble themselves or those who seem to be in need of legal assistance for a relative or friend in trouble. Perhaps the majority of lawyers practising in the courts are reputable to the highest degree, and many of the rest merely to a safe degree. Many devote themselves to philanthropic work whenever a prisoner is penniless. But the percentage of shysters is high. Kahn belonged in the latter class, although his days of doing dirty work himself were passed. He had a large force of incipient shysters for that purpose. As for himself, he handled only the big cases in which he veneered the dirty work by a sort of finesse. Kahn bowed and smiled ingratiatingly. "Mr. Carton," he began in a conciliatory tone, "I have intruded on your valuable time in the interest of my client, Mr. Jack Rubano." "Huh!" grunted Carton. "So they've retained you, have they, Ike?" he mused familiarly, closely regarding the visitor. Kahn, far from resenting the familiarity, seemed rather to enjoy it and take it as his due measure of fame. "Yes, Mr. Carton, they have retained me. I have just had a talk with the prisoner in the Tombs and have gone over his case very carefully, sir." Carton nodded, but said nothing, willing to let Kahn do the talking for the present until he exposed his hand. "He has told me all about his case," pursued Kahn evenly. "It is not such a bad case. I can tell you that, Mr. Carton, because I didn't have to resort to the 'friend of the judge' gag in order to show him that he had a good chance." Kahn looked knowingly at Carton. At least he was frank about his own game before us; in fact, utterly shameless, it seemed to me. Probably it was because he knew it was no use, that Carton had no illusions about him. Still, there was an uncanny bravado about it all. Kahn was indeed very successful in making the worst appear the better reason. He knew it and knew that Carton knew it. That was his stock in trade. He had seated himself in a chair by the District Attorney's desk and as he talked was hitching it closer and closer, for men of Kahn's stamp seem unable to talk without getting into almost personal contact with those with whom they are talking. Carton drew back and folded his hands back of his head as he listened, still silent. "You know, Mr. Carton," he insinuated, "it is a very different thing to be sure in your own mind that a man is guilty from being able to prove it in court. There are all sorts of delays that may be granted, witnesses are hard to hold together, in fact there are many difficulties that arise in the best of cases." "You don't need to tell me that, Kahn," replied Carton quietly. "I know it, Mr. Carton," rejoined the other apologetically. "I was just using that as a preface to what I have to say." He took another hitch of the chair nearer Carton and lowered his voice impressively. "The point, sir, at which I am driving is simply this. There must be some way in which we can reach an agreement, compromise this case, satisfactorily to the people with a minimum of time and expense--some way in which the indictment or the pleadings can be amended so that it can be wound up and--you understand--both of us win--instead of dragging it out and perhaps you losing the case in the end." Carton shook his head. "No, Kahn," he said in a low tone, but firmly, "no compromise." Kahn bent his ferret eyes on Carton's face as if to bore through into his very mind. "No," added the District Attorney, "Murtha was just here, and I may as well repeat what I said to him--although I might fairly assume that he went from this room directly across the street to your office and that you know it already. This case has gone too far, it has too many other ramifications for me to consent to relax on it one iota." Kahn was baffled, but he was cleverer than Murtha and did not show it. "Surely," he urged, "you must realize that it is not worth your while at such a critical time for yourself to waste energies on a case when there are so many more profitable things that you could do. The fact is that I would be the last one to propose anything that was not open and above board and to our mutual advantage. There must be some way in which we can reach an agreement which will be satisfactory to all parties in interest, sir." "Kahn," repeated Carton a little testily, "how often must I repeat to you and your people that I am NOT going to compromise this case in any shape, form, or manner? I am going to fight it out on the lines I have indicated if I have to disrupt this entire office to get men to do it. I have plenty to do seeking re-election, but my first duty is to act as public prosecutor in the office to which I have been already elected. Otherwise, it would be a poor recommendation to the people to return me to the same position. No, you are merely wasting your time and ours talking compromise." Kahn had been surveying Carton keenly, now and then taking a shifty glance at Kennedy and myself. As Carton rapped out the last words, as if in the nature of an ultimatum, Kahn gazed at him in amazement. Here was a man whom he knew he could neither bribe, bully, or bulldoze. "You must consider this, too," he added pointedly. "There has been a good deal of mud-slinging in this campaign. We may find it necessary to go back into the antecedents and motives of those who represent the people in this case." It was a subtle threat. Just what it implied I could not even guess, nor did Carton betray anything by look or word. Carton had voluntarily placed himself in the open and in a position from which he could not retreat. Evidently, now, he was willing to force the fight, if the other side would accept the issue. It meant much to him but he did not balk at it. "No, Kahn," he repeated firmly, "no compromise." Kahn drew back a bit and hastily scanned the face of the prosecutor. Evidently he saw nothing in it to encourage him. Yet he was too smooth to let his temper rise, as Murtha had. By the same token I fancied him a more dangerous opponent. There was something positively uncanny about his assurance. Kahn rose slowly. "Then it is war--without quarter?" asked Kahn shrewdly. "War--without quarter," repeated Carton positively. He withdrew quietly, with an almost feline tread, quite in contrast with the bluster of Murtha. I felt for the first time a sort of sinking sensation, as I began to realize the varied character of the assault that was preparing. Not so, Carton and Kennedy. It seemed that every event that more clearly defined our position and that of our opponents added zest to the fight for them. And I had sufficient confidence in the combination to know that their feelings were justified. Carton silently pulled down and locked the top of his desk, then for a moment we debated where we should dine. We decided on a quiet hotel uptown and, leaving word where we could be found, hurried along for the first real relaxation and refreshment after a crowded day's work. If, however, we thought we could escape even for a few minutes we were mightily mistaken. We had not fairly done justice to the roast when a boy in buttons came down the line of tables. "Mr. Carton--please." The District Attorney crooked his finger at the page. "You're wanted at the telephone, sir." Carton rose and excused himself. The message must have given him food of another kind, for when he returned after a long absence, he pushed aside the now cold roast and joined us in the coffee and cigars. "One of my men," he announced, "has been doing some shadowing for me. Evidently, both Murtha and Kahn having failed, they are resorting to other tactics. It looks as if they had in some way, probably from some corrupt official of the court or employee in charge of the jury list, obtained a copy of the panel which Justice Pomeroy has summoned for the case." "It ought to be a simple thing to empanel another set of talesmen and let these fellows serve in some other part of the court," I suggested, considering the matter hastily. "Much better to let it rest as it is," cut in Craig quickly, "and try to catch Kahn with the goods. It would be great to catch one of these clever fellows trying to 'fix' the jury, as well as intimidate witnesses, as he already hinted himself." "Just the thing," exclaimed Carton, whose keen sense of proportion showed what a valuable political asset such a coup would make in addition to its effect on the case. "We'll get Kahn right, if we have a chance," planned Craig. "You are acquainted more or less with his habits, I suppose. Where does Kahn hang out? Most fellows like him have a sort of Amen Corner where they meet their henchmen, issue orders, receive reports and carry on business that wouldn't do for an office downtown." "Why, I believe he goes to Farrell's--has an interest in the place, I think." Farrell's, we recognized, as a rather well-known all-night cafe which managed to survive the excise vicissitudes by dint of having no cabaret or entertainment. We finished the dinner in silence, Kennedy turning various schemes over in his mind, and rejecting them one after another. "There's nothing we can do immediately, I suppose," he remarked at length. "But if you and Carton care to come up to the laboratory with me, I might in time of peace prepare for war. I have a little apparatus up there which I think may fit in somehow and if it does, Mr. Kahn's days of jury fixing are numbered." A few minutes later, we found ourselves in Kennedy's laboratory, where he had gathered together an amazing collection of paraphernalia in the warfare of science against crime which he had been waging during the years that I had known him. Carton looked about in silent admiration. As for myself, although one might have thought it was an old story with me, I had found that no sooner had I become familiar with one piece of apparatus to perform one duty, than another situation, entirely different and unprecedented in our cases arose which called for another, entirely new. I had learned to have implicit confidence in Kennedy's ability to meet each new emergency with something fully capable of solving the problem. From a cabinet, Kennedy took out what looked like the little black leather box of a camera, with, however, a most peculiar looking lens. IX THE JURY FIXER "Let's visit Farrell's," remarked Craig, after looking over the apparatus and slinging it over his shoulder. It was early yet, and the theatres were not out, so that there were comparatively few people in the famous all-night cafe. We entered the bar cautiously and looked about. Kahn at least was not there. In the back of this part of the cafe were several booths, open to conform to the law, yet sufficiently screened so that there was at least a little privacy. Above the booths was a line of transoms. "What's back there?" asked Kennedy, under his breath. "A back room," returned Carton. "Perhaps Kahn is there," Craig suggested. "Walter, you're the one whom he would least likely recognize. Suppose you just stick your head in the door and look about as quietly as you can." I lounged back, glanced at the records of sporting events posted on the wall at the end of the bar, then, casually, as if looking for someone, swung the double-hinged door that led from the bar into the back room. The room was empty except for one man, turned sidewise to the door, reading a paper, but in a position so that he could see anyone who entered. I had not opened the door widely enough to be noticed, but I now let it swing back hastily. It was Kahn, pompously sipping something he had ordered. "He's back there," I whispered to Kennedy, as I returned, excitedly motioning toward one of the transoms over the booths back of which Kahn was seated. "Right there?" he queried. "Just about," I answered. A moment later Kennedy led the way over to the booth under the transom and we sat down. A waiter hovered near us. Craig silenced him quickly with a substantial order and a good-sized tip. From our position, if we sat well within the booth, we were effectually hidden unless someone purposely came down and looked in on us. We watched Kennedy curiously. He had unslung the little black camera-like box and to it attached a pair of fine wires and a small pocket storage battery which he carried. Then he looked up at the transom. It was far too high for us to hear through, even if those in the back room talked fairly loud. Standing on the leather wall seats of the booth to listen or even to look over was out of the question, for it would be sure to excite suspicion among the waiters, or the customers who were continually passing in and out of the place. Kennedy was watching his chance, and when the cafe emptied itself after being deluged between the acts from a neighbouring theatre, he jumped up quickly in the seat, stood on his toes and craned his neck through the diagonally opened transom. Before any of the waiters, who were busy clearing up the results of the last theatre raid, had a chance to notice him, Craig had slipped the little black box into the shadow of the corner. From it dangled down the fine wires, not noticeable. "He's sitting just back of us yet," reported Kennedy. "I don't know about that flaming arc light in the middle of the room, but I think it will be all right. Anyhow, we shall have to take a chance. It looks to me as if he were waiting for someone--didn't it to you, Walter?" I nodded acquiescence. "He has wasted no time in getting down to work," put in Carton, who had been a silent spectator of the preparations of Kennedy. "What's that thing you put on the ledge up there--a detectaphone?" Kennedy smiled. "No--they're too clever to do any talking, at least in a place like this, I'm afraid," he said, carefully hiding the wires and the battery beside him in the shadow of the corner of the booth. "It may be that nothing will happen, anyhow, but if it does we can at least have the satisfaction of having tried to get something. Carton, you had better sit as far back in the booth as I am. The longer we can stay here unnoticed the better. Let Walter sit on the outside." We changed places. "Lawyers have been complaining to me lately," remarked Carton in a well modulated voice, "about jury fixing. Some of them say it has been going on on a large scale and I have had several of my county detectives working on it. But they haven't landed anything yet,--except rumours, like this one about the Dopey Jack jury. I've had them out posing as jurymen who could be 'approached' and would arrange terms for other bribable jurymen." "And you mean to say that that's going on right here in this city?" I asked, scenting a possible newspaper story. "This campaign I have started," he replied, "is only the beginning of our work in breaking up the organized business of jury bribing. I mean to put an end to the work of what I have reason to believe is a secret ring of jury fixers. Why, I understand that the prices for 'hanging' a jury range all the way from five to five hundred dollars, or even higher in an important case. The size of the jury fixer's 'cut' depends upon the amount the client is willing to pay for having his case made either a disagreement or a dismissal. Usually a bonus is demanded for a dismissal in criminal cases. But such things are very difficult to--" "Sh!" I cautioned, for from my vantage point I saw two men approaching. They saw me in the booth, but not the rest of us, and turned to enter the next one. Though they were talking in low tones, we could catch words and phrases now and then, which told us that we ourselves would have to be very careful about being overheard. "We've got to be careful," one of them remarked in a scarcely audible undertone. "Carton has detectives mingling with the talesmen in every court of importance in the city." The reply of the other was not audible, but Carton leaned over to us and whispered, "One of Kahn's runners, I think." Apparently Kahn was taking extreme precautions and wanted everything in readiness so that whatever was to be done would go off smoothly. Kennedy glanced up at the little black leather box perched high above on the sill of the partition. "The chief says that a thousand dollars is the highest price that he can afford for 'hanging' this jury--providing you get on it, or any of your friends." The other man, whose voice was not of the vibrating, penetrating quality of the runner, seemed to hesitate and be inclined to argue. "We've had 'em as low as five dollars," went on the runner, at which Carton exchanged a knowing glance with us. "But in a special case, like this, we realize that they come high." The other man grumbled a bit and we could catch the word, "risky." Back and forth the argument went. The runner, however, was a worthy representative of his chief, for at last he succeeded in carrying both his point and his price. "All right," we heard him say at last, "the chief is in the back room. Wait until I see whether he is alone." The runner rose and went around to the swinging door. From the other side of the transom we could, as we had expected, hear nothing. A moment later the runner returned. "Go in and see him," he whispered. The man rose and made his way through the swinging door into the back room. None of us said a word, but Kennedy was literally on his toes with excitement. He was holding the little battery in his hand and after waiting a few moments pressed what looked like a push button. He could not restrain his impatience longer, but had jumped up on the leather seat and for a moment looked at the black leather box, then through the half open transom, as best he could. "Press it--press it!" he whispered to Carton, pointing at the push button, as he turned a little handle on the box, then quickly dropped down and resumed his seat. "Craig--one of the waiters," I cried hurriedly. The outside bar had been filling up as the evening advanced and the sight of a man standing on one of the seats had attracted the attention of a patron. A waiter had followed his curious gaze and saw Kennedy. With a quick pull on the wire, Kennedy jerked the black leather box from its high perch and deftly caught it as it fell. "Say--what are youse guys doin', huh?" demanded the waiter pugnaciously. Carton and I had risen and stood between the man and Craig. The sound of voices in high pitch was enough to attract a crowd ever ready to watch a scrap. Mindful of the famous "flying wedge" of waiters at Farrell's for the purpose of hustling objectionable and obstreperous customers with despatch to the sidewalk, I was prepared for anything. The runner who was sitting alone in the next booth, leaned out and gazed around the corner into ours. "Carton!" he shouted in a tone that could have been heard on the street. The effect of the name of the District Attorney was magical. For the moment, the crowd fell back. Before the tough waiters or anyone else could make up their minds just what to do, Kennedy, who had tucked the box into his capacious side pocket, took each of us by the arm and we shoved our way through the crowd. The head waiter followed us to the door, but offered no resistance. In fact no one seemed to know just what to do and it was all over so quickly that even Kahn himself had not time to get a glimpse of us through the swinging door. A moment later we had piled into a taxicab at the curb and were speeding through the now deserted streets uptown to the laboratory. Kennedy was jubilant. "I may have almost precipitated a riot," he chortled, "but I'm glad I stood up. I think it must have been at the psychological moment." At the laboratory he threw off his coat and prepared to plunge into work with various mysterious pans of chemicals, baths, jars, and beakers. "What is it?" asked Carton, as Kennedy carefully took out the dark leather box, shielding it from the glare of a mercury vapour light. "A camera with a newly-invented electrically operated between-lens shutter of great illumination and efficiency," he explained. "It has always been practically impossible to get such pictures as I wanted, but this new shutter has so much greater speed than anything else ever invented before, that it is possible to use it in this sort of detective work. I've proved its speed up to one two-thousandth of a second. It may or may not have worked, but if it has we've caught someone, right in the act." Kennedy had a "studio" of his own which was quite equal to the emergency of developing the two pictures which he had taken with the new camera. Late as it was, we waited for him to finish, just as we would have waited down in the Star office if one of our staff photographers had come in with something important. At last Kennedy emerged from his workshop. As he did so, he slapped down two untoned prints. Both were necessarily indistinct owing to the conditions under which they had had to be taken. But they were quite sufficient for the purpose. As Carton bent over the second one, which showed Kahn in the very act of handing over a roll of bills to the rather anemic man whom his runner had brought to him, Carton addressed the photograph as if it had been Kahn himself. "I have you at last," he cried. "This is the end of your secret ring of jury fixers. I think that will about settle the case of Kahn, if not of Dopey Jack, when we get ready to spring it. Kennedy, make another set of prints and let me lock them in a safe deposit vault. That's as precious to me as if it were the Black Book itself!" Craig laughed. "Not such a bad evening's work, after all," he remarked, clearing things up. "Do you realize what time it is?" Carton glanced perfunctorily at his watch. "I had forgotten time," he returned. "Yes," agreed Craig, "but to-morrow is another day, you know. I don't object to staying up all night, or even several nights, but there doesn't seem to be anything more that we can do now, and it may be that we shall need our strength later. This is, after all, only a beginning in getting at the man higher up." "The man highest up," corrected Carton, with elation as we parted on the campus, Kennedy and I to go to our apartment. "See you in the morning, Carton," bade Kennedy. "By that time, no doubt, there will be some news of the Black Book." We arrived at our apartment a few minutes later. On the floor was some mail which Kennedy quickly ran over. It did not appear to be of any importance--that is, it had no bearing on the case which was now absorbing our attention. "Well, what do you think of that?" he exclaimed as he tore open one diminutive letter. "That was thoughtful, anyhow. She must have sent us that a few minutes after we left headquarters." He handed me an engraved card. It was from Miss Ashton, inviting us to a non-partisan suffrage evening at her studio in her home, to be followed by a dance. Underneath she had written a few words of special invitation, ending, "I shall try to have some people there who may be able to help us in the Betty Blackwell matter." X THE AFTERNOON DANCE It was early the following morning that I missed Kennedy from our apartment. Naturally I guessed from my previous experiences with that gentleman that he would most likely be found at his laboratory, and I did not worry, but put the finishing touches on a special article for the Star which I had promised for that day and had already nearly completed. Consequently it was not until the forenoon that I sauntered around to the Chemistry Building. Precisely as I had expected, I found Kennedy there at work. I had been there scarcely a quarter of an hour when the door opened and Clare Kendall entered with a cheery greeting. It was evident that she had something to report. "The letter to Betty Blackwell which you sent to the Montmartre has come back, unopened," she announced, taking from her handbag a letter stamped with the post-office form indicating that the addressee could not be found and that the letter was returned to the sender. The stamped hand of the post-office pointed to the upper left-hand corner where Clare had written in a fictitious name and used an address to which she frequently had mail sent when she wanted it secret. "Only on the back," she pursued, turning the letter over, "there are some queer smudges. What are they? They don't look like dirt." Kennedy glanced at it only casually, as if he had fully expected the incident to turn out as it did. "Not unopened, Miss Kendall," he commented. "We have already had a little scientific letter-opening. This was a case of scientific letter-sealing. That was a specially prepared envelope." He reached down into his desk and pulled out another, sealed it carefully, dried it, then held it over a steaming pan of water until the gum was softened and it could be opened again. On the back were smudges just like those on the letter that had been returned. "On the thin line of gum on the flap of the envelope," he explained, "I have placed first a coating of tannin, over which is the gum. Then on the part of the envelope to which the flap adheres when it is sealed I placed some iron sulphate. When I sealed the envelope so carefully I brought the two together separated only by the thin film of gum. Now when steam is applied to soften the gum, the usual method of the letter-opener, the tannin and the sulphate are brought together. They run and leave these blots or dark smudges. So, you see, someone has been found at the Montmartre, even if it is not Betty Blackwell herself, who has interest enough in the case to open a letter to her before handing it back to the postman. That shows us that we are on the right trail at least, even if it does not tell us who is at the end of the trail. Here's another thing; This 'Marie' is a new one. We must find out about her." "At the Futurist Tea Room at four this afternoon, when she meets our good friend, young Dr. Harris," reminded Clare. "Between cabarets and tea rooms I don't know whether this is work or play." "It's work, all right," smiled Kennedy, adding, "at least it would be if it weren't lightened by your help." It was the middle of the afternoon when Craig and I left the laboratory to keep our appointment with Miss Kendall at the Futurist Tea Room, where we hoped to find Dr. Harris's friend "Marie," who seemed to want to see him so badly. A long line of touring and town cars as well as taxicabs bore eloquent testimony not only to the popularity of this tea room and cabaret, but to the growth of afternoon dancing. One never realizes how large a leisure class there is in the city until after a visit to anything from a baseball game to a matinee--and a dance. People seemed literally to be flocking to the Futurist. They seemed to like its congeniality, its tone, its "atmosphere." As we left our hats to the tender mercies of the "boys" who had the checking concession we could see that the place was rapidly filling up. "If we are to get a table that we want here, we'd better get it now," remarked Kennedy, slipping the inevitable piece of change to the head waiter. "If we sit over there in that sort of little bower we can see when Miss Kendall arrives and we shall not be so conspicuous ourselves, either." The Futurist was not an especially ornate place, although a great deal of money had evidently been expended in fitting it up to attract a recherche clientele. Our table, which Kennedy had indicated, was, as he had said, in a sort of little recess, where we could see without being much observed ourselves, although that seemed almost an impossibility in such a place. In fact, I noticed before we had had time to seat ourselves that we had already attracted the attention of two show girls who sat down the aisle and were amusing themselves at watching us by means of a mirror. It would not have been very difficult to persuade them to dispense with the mirror. A moment later Clare Kendall entered and paused at the door an instant, absorbing the gay scene as only a woman and a detective could. Craig rose and advanced to meet her, and as she caught sight of us her face brightened. The show girls eyed her narrowly and with but slight approval. "We feel more at ease with a lady in the party," remarked Craig, as they reached the table and I rose to greet her. "Two men alone here are quite as noticeable as two ladies. Walter, I know, was quite uncomfortable." "To say nothing of the fact which you omitted," I retaliated, "that it is a pleasure to be with Miss Kendall--even if we must talk shop all the time." Clare smiled, for her quick intuition had already taken in and dismissed as of no importance the two show girls. We ordered as a matter of course, then settled back for a long interval until the waiter out of the goodness of his heart might retrieve whatever was possible from the mob of servitors where refreshments were dispensed. "Opposite us," whispered Clare, resting her chin on her interlocked fingers and her elbows on the tip-edge of the table, "do you see that athletic-looking young lady, who seems to be ready for anything from tea to tango? Well, the man with her is Martin Ogleby." Ogleby was of the tall, sloping-shouldered variety, whom one can see on the Avenue and in the clubs and hotels in such numbers that it almost seems that there must be an establishment for turning them out, even down to a trademark concealed somewhere about them, "Made in England." Only Ogleby seemed a little different in the respect that one felt that if all the others were stamped by the same die, he was the die, at least. Compared to him many of the others took on the appearance of spurious counterfeits. "Dr. Harris," Craig whispered, indicating to us the direction with his eyes. Outside on a settee, we could see in the corridor a man waiting, restless and ill at ease. Now and then he looked covertly at his watch as if he expected someone who was late and he wondered if anything could be amiss. Just then a superbly gowned woman alighted from a cab. The starter bowed as if she were familiar. It was evident that this was the woman for whom Harris waited, the "Marie" of the letter. She was a carefully groomed woman, as artificial as French heels. Yet indeed it was that studied artificiality which constituted her chief attraction. As Harris greeted her I noted that Clare was amazed at the daring cut of her gown, which excited comment even at the Futurist. Her smooth, full, well-rounded face with its dark olive skin and just a faint trace of colour on either cheek, her snappy hazel eyes whose fire was heightened by the penciling of the eyebrows, all were a marvel of the dexterity of her artificial beautifier. And yet in spite of all there was an air of unextinguishable coarseness about her which it was difficult to describe, but easy to feel. "Her lips are too thick and her mouth too large," remarked Clare, "and yet in some incomprehensible way she gives you the impression of daintiness. What is it?" "The woman is frankly deceptive from the tip of her aigrette to the toes of her shoes," observed Craig. "And yet," smiled Clare, watching with interest the little stir her arrival had made among the revellers, "you can see that she is the envy of every woman here who has slaved and toiled for that same effect without approaching within miles of it or attracting one quarter the notice for her pains that this woman receives." Dr. Harris was evidently in his element at the attention which his companion attracted. They seemed to be on very good terms indeed, and one felt that Bohemianism could go no further. They paused, fortunately, at a just vacated table around an "L" from us and sat down. For once waiters seemed to vie in serving rather than in neglecting. By this time I had gained the impression that the Futurist was all that its name implied--not up to the minute, but decidedly ahead of it. There was an exotic flavour to the place, a peculiar fascination, that was foreign rather than American, at seeing demi-monde and decency rubbing elbows. I felt sure that a large percentage of the women there were really young married women, whose first step downward was truly nothing worse than saying they had been at their whist clubs when in reality it was tango and tea. What the end might be to one who let the fascination blind her perspective I could imagine. Dr. Harris and "Marie" were nearer the dancing floor than we were, but seemed oblivious to it. Now and then as the music changed we could catch a word or two. He was evidently making an effort to be gay, to counteract the feeling which she had concealed as she came in, but which had the upper hand now that they were seated. "Won't you dance?" I heard him say. "No, Harry. I came here to tell you about how things are going." There was a harshness about her voice which I recognized as belonging exclusively to one class of women in the city. She lowered it as she went on talking earnestly. "It looks as though someone has squealed, but who--" I caught in the fragmentary lulls of the revelry. "I didn't know it was as bad as that," Dr. Harris remarked. They talked almost in whispers for several moments while I strained my ears to catch a syllable, but without success. What were they talking about? Was it about Dopey Jack? Or did they know something about Betty Blackwell? Perhaps it was about the Black Book. Even when the music stopped they talked without dropping a word. The music started again. There was no mistaking the appeal that the rocking whirl of the rhythmic dance made. From the side of the table where Kennedy was seated he could catch an occasional glimpse of the face of Marie. I noticed that he had torn a blank page off the back of the menu and with a stub of a pencil was half idly writing. At the top he had placed the word, "Nose," followed by "straight, with nostrils a trifle flaring," and some other words I could not quite catch. Beneath that he had written "Ears," which in turn was followed by some words which he was setting down carefully. Eyes, chin, and mouth followed, until I began to realize that he was making a sort of scientific analysis of the woman's features. "I shall need some more--" I caught as the music softened unexpectedly. A singer on the little platform was varying the programme now by a solo and I shifted my chair so as to get a better view and at the same time also a look at the table around the corner from us. As I did so I saw Dr. Harris reach into his breast pocket and take out a little package which he quickly handed to Marie. As their hands met, their eyes met also. I fancied that the doctor struggled to demagnetize, so to speak, the look which she gave him. "You'll come to see me--afterwards?" she asked, dropping the little package into her handbag of gold mesh and rattling the various accoutrements of beautification which tinkled next to it. Harris nodded. "You're a life saver to some--" floated over to me from Marie. The solo had been completed and the applause was dying away. "... tells me he needs ... badly off ... don't forget to see ..." The words came in intervals. What they meant I did not know, but I strove to remember them. Evidently Marie and a host of others were depending on Harris for something. At any rate, it seemed, now that she had talked she felt easier in mind, as one does after carrying a weight a long time in secret. "Tanguez-vous?" he asked as the orchestra struck up again. "Yes--thank you, Harry--just one." We watched the couple attentively as they were alternately lost and found in the dizzy swaying mass. The music became wilder and they threw themselves into the abandon of the dance. They had been absorbed so much in each other and the unburdening of whatever it was she had wanted to tell him, that neither had noticed the other couple on the other side of the floor whose presence had divided our own attention. Martin Ogleby and his partner were not dancing. It was warm and they were among the lucky ones who had succeeded in getting something besides a cheque from the waiters. Two tall glasses of ginger ale with a long curl of lemon peel sepentining through the cracked ice stood before them. The dance had brought Dr. Harris and Marie squarely around to within a few feet of where Ogleby was sitting. As Harris swung around she faced Ogleby in such a way that he could not avoid her, nor could she have possibly missed seeing him. For a moment their eyes met. Not a muscle in either face moved. It was as if they were perfect strangers. She turned and murmured something to her partner. Ogleby leaned over, without the least confusion, and made a witty remark to his partner. It was over in a minute. The acting of both could not have been better if they had deliberately practised their parts. What did it mean? As the dance concluded I saw Ogleby glance hastily over in the direction of Marie. He gave a quick smile of recognition, as much as to say "Thank you." It was evident now that both Dr. Harris and Marie, whoever she was, were getting ready to leave. As they rose to move to the door, Kennedy quickly paid our own cheque, leaving the change to the waiter, and without seeming to do so we followed them. Harris was standing near the starter with his hat off, apparently making his adieux. Deftly Kennedy managed to slip in behind so as to be next in line for a cab. "Walter and I will follow Harris if they separate," he whispered to Clare Kendall. "You follow the woman." The afternoon was verging toward dinner and people were literally bribing the taxicab starter. Our own cab stood next in line behind that which Harris had called. "I have certainly enjoyed this little glimpse of Bohemia," commented Kennedy to Miss Kendall as we waited. "I shouldn't mind if detective work took me more often to afternoon dances. There, they are going down the steps. Here's the cab I called. Let me know how things turn out. Goodbye. Here--chauffeur, around that way--where that other cab is going--the lady will tell you where to drive." Harris hesitated a moment as if considering whether to take a cab himself, then slowly turned and strolled down the street. We followed, slowly also. There was something unreal about the bright afternoon sunshine after the atmosphere of the Futurist Tea Room, where everything had been done to promote the illusion of night. Harris walked along meditatively, crossing one street after another, not as if debating where he was going, but rather in no great hurry to get there. Instead of going down Broadway he swerved into Seventh Avenue, then after a few blocks turned into a side street, quickened his pace, and at last dived down into a basement under a saloon. It was a wretched neighbourhood, one of those which reminds one of the life of an animal undergoing a metamorphosis. Once it had evidently been a rather nice residential section. The movement of population uptown had left it stranded to the real estate speculators, less desirable to live in, but more valuable for the future. The moving in of anyone who could be got to live there had led to rapid deterioration and a mixed population of whites and negroes against the day when the upward sweep of business should bring the final transformation into office and loft buildings. But for the present it was decaying, out of repair, a mass of cheap rooming-houses, tenements, and mixed races. The joint into which Harris had gone was the only evidence of anything like prosperity on the block, and that evidence was confined to the two entrances on the street, one leading into the ground floor and the other down a flight of steps to the basement. "Do you want to go in?" asked Kennedy in a tone that indicated that he himself was going. Just then a negro, dazzling in the whiteness of his collar and the brilliancy of his checked suit, came up the stairs accompanied by a light mulatto. "It's a black and tan joint," Craig went on, "at least downstairs--negro cabaret, and all that sort of thing." "I'm game," I replied. We stumbled down the worn steps, past a swinging door near which stood the proprietor with a careful eye on arrivals and departures. The place was deceiving from the outside. It really extended through two houses, and even at this early hour it was fairly crowded. There were negroes of all degrees of shading, down to those who were almost white. Scattered about at the various tables were perhaps half a dozen white women, tawdry imitations of the faster set at the Futurist which we had just left, the leftovers of a previous generation in the Tenderloin. There was also a fair sprinkling of white men, equally degraded. White men and coloured women, white women and coloured men, chatted here and there, but for the most part the habitues were negroes. At any rate the levelling down seemed to have produced something like an equality of races in viciousness. As we sat down at a table, Kennedy remarked: "They used to drift down to Chinatown, a good many of these relics. You used to see them in the old 'suicide halls' of the Bowery, too. But that is all passing away now. Reform and agitation have closed up those old dives. Now they try to veneer it over with electric lights and bright varnish, but I suppose it comes to the same thing. After they are cast off Broadway, the next step lower is the black and tan joint. After that it is suicide, unless it is death." "I don't think this is any improvement over the--the bad old days," I ventured. Kennedy shook his head in agreement. "There's Harris, down there in the back, talking to someone, a white man, alone." A waiter came over to us grinning, for we had assumed the role of sightseers. "Who is that, 'way back there, with his chair tipped to the wall, talking to the man with his back to us?" asked Kennedy. "Ike the Dropper, sah," informed the waiter with obvious pride that such a celebrity should be harboured here. I looked with a feeling akin to awe at the famous character who, in common with many others of his type, had migrated uptown from the proverbial haunts of the gunmen on the East Side in search of pastures new and untroubled. Ike the Dropper may have once been a strong-arm man, but at present I knew that he was chiefly noted for the fact, and he and his kind were reputed to be living on the earnings of women to whom they were supposed to afford "protection." I reflected on the passing glories of brutality which had sunk so low. There were noise and life a plenty here. At a discordant box of a piano a negro performer was playing with a keen appreciation of time if of nothing else, and two others with voices that might not have been unpopular in a decent minstrel show were rendering a popular air. They wore battered straw hats and a make-up which was intended to be grotesque. From time to time, as the pianist was moved, he played snatches of the same music as that which we had heard at the Futurist, and between us and Harris and Ike the Dropper several couples were one-stepping, each in their own sweet way. As the music became more lively their dancing came more and more to resemble some of the almost brutal Apache dances of Paris, in that the man seemed to exert sheer force and the woman agility in avoiding him. It was an entirely new phase of afternoon dancing, an entirely new "leisure class," this strange combination of Bohemia and Senegambia. At a table next to us, so near that we could almost rub elbows with them, sat a white man and a white woman. They had been talking in low tones, but I could catch whole sentences now and then, for they seemed to be making no extraordinary effort at concealment. "He was framing a sucker to get away with a whole front," I heard the man say, "or with a poke or a souper, but instead he got dropped by a flatty and was canned for a sleep." "Two dips--pickpockets," whispered Craig. "Someone was trying to take everything a victim had, or at least his pocketbook or watch, but instead he was arrested by a detective and locked up over night." "Good work," I laughed. "You are 'some' translator." I looked at our neighbours with a certain amount of respect. Were they framing up something themselves? At any rate I felt that I would rather see them here and know what they were than to be jostled by them in a street car. The sleek proprietor kept a careful eye on them and I knew that a sort of unwritten law would prevent them from trying on anything that would endanger their welcome in a joint none too savoury already. Nevertheless I was quite interested in the bits of pickpocket argot that floated across to us, expressions like "crossing the mit," "nipping a slang," a "mouthpiece," "making a holler" and innumerable other choice bits as unintelligible to me as "Beowulf." After a few minutes the woman got up and went out, leaving the man still sitting at the table. Of course it was none of my business what they were doing, I suppose, but I could not help being interested. That diversion being ended, I joined Kennedy in his scrutiny of Harris and his choice friend. Of course at our distance it was absolutely impossible to gain any idea of what they were talking about, and indeed our chief concern was not to attract any attention. Whatever it was, they were very earnest about it and paid no attention to us. The dancing had ceased and the two "artists" were entertaining the select audience with some choice bits of ragtime. We could see Ike the Dropper and Dr. Harris still talking. Suddenly Kennedy nudged me. I looked up in time to see Dr. Harris reach into his inside breast pocket again and quietly slip out a package much like that which we had already seen him hand to Marie at the Futurist. Ike took it, looked at it a moment with some satisfaction, then stuffed it down carefully into the right-hand outside pocket of his coat. "I wonder what that is that Harris seems to be passing out to them?" mused Craig. "Drugs, perhaps," I ventured offhand. "Maybe. I'd like to know for certain." Just then Harris and Ike rose and walked down on the other side of the place toward the door. Kennedy turned his head so that even if they should look in our direction they would not see his face. I did the same. Fortunately neither seemed interested in the other occupants. Harris having evidently fulfilled his mission, whether of delivering the package or receiving news which Ike seemed to be pouring into his ear, had but one thought, to escape from a place which was evidently distasteful to him. At the door they paused for a moment and spoke with the proprietor. He nodded reassuringly once or twice to Dr. Harris, much to the relief, I thought, of that gentleman. Kennedy was chafing under the restraint which kept him in the background and prevented any of his wizardry of mechanical eavesdropping. I fancied that his roving eye was considering various means of utilizing his seemingly inexhaustible ingenuity if occasion should arise. At last Harris managed to shake hands good-bye and disappeared up the steps to the sidewalk still followed by Ike. Kennedy leaned over and looked the "dip" sitting alone back of us squarely in the face. "Would you like to make twenty-five dollars--just like that?" he asked with a quick gesture that accorded very well with the slang. The man looked at him very suspiciously, as if considering what kind of new game this was. "That was your gun moll who just went out, wasn't it?" pursued Kennedy with assurance. "Aw, come off. Whatyer givin' us?" responded the man half angrily. "Don't stall. I know. I'm not one of the bulls, either. It's just a plain proposition. Will you or won't you take twenty-five of easy money?" Kennedy's manner seemed to mystify him. For a moment he looked us over, then seemed to decide that we were all right. "How?" he asked in a harsh but not wholly ungracious whisper. "I'll tip yer off if the boss is lookin'. He don't like no frame-ups in here." "You saw Ike the Dropper go out with that man?" "The guy with the glasses?" "Yes." "Well?" "The guy with the glasses gave Ike a little package which Ike put into the right-hand outside pocket of his coat. Now it's worth twenty-five beans to me to get that package--get me?" "I gotyer. Slip me a five now and the other twenty if I get it." Kennedy appeared to consider. "I'm on the level," pursued the dip. "Me and the goil is in hard luck with a mouthpiece who wants fifty bucks to beat the case for one of the best tools we ever had in our mob that they got right to-day." "From that I take it that one of your pals needs fifty dollars for a lawyer to get him out of jail. Well, I'll take a chance. Bring the package to me at--well, the Prince Henry cafe. I'll be there at seven o'clock." The pickpocket nodded, slid from his place and sidled out of the joint without attracting any attention. "What's the lay?" I asked. "Oh, I just want that package, that's all. Come on, Walter. We might as well go before any of these yellow girls speak to us and frame up something on us." The proprietor bowed as much as to say, "Come again and bring your friends." XI THE TYPEWRITER CLUE Ike was nowhere to be seen when we reached the street, but down the block we caught sight of Dr. Harris on the next corner. Kennedy hastened our pace until we were safely in his wake, then managed to keep just a few paces behind him. Instead of turning into the street where the Futurist was, Harris kept on up Broadway. It was easy enough to follow him in the crowd now without being perceived. He turned into the street where the Little Montmartre was preparing for a long evening of entertainment. We turned, and to cover ourselves got into a conversation with a hack driver who seemed suddenly to have sprung from nowhere with the cryptic whisper, "Drive you to the Ladies' Club, gents?" Out of the tail of his eye Kennedy watched Harris. Instead of turning into the Montmartre and his office, he went past to a high-stooped brownstone house, two doors away, climbed the steps and entered. We sauntered down the street and looked quickly at the house. A brass sign on the wall beside the door read, "Mme. Margot's Beauty Shop." "I see," commented Kennedy. "You know women of the type who frequent the Futurist and the Montmartre are always running to the hairdressing and manicure parlours. They make themselves 'beautiful' under the expert care of the various specialists and beauty doctors. Then, too, they keep in touch that way with what is going on in the demi-monde. That is their club, so to speak. It is part of the beauty shop's trade to impart such information--at least of a beauty shop in this neighbourhood." I regarded the place curiously. "Come, Walter, don't stare," nudged Kennedy. "Let's take a turn down to the Prince Henry and wait. We can get a bite to eat, too." I had hardly expected that the pickpocket would play fair, but evidently the lure of the remaining twenty dollars was too strong. We had scarcely finished our dinner when he came in. "Here it is," he whispered. "The house man here at the Prince Henry knows me. Slip me the twenty." Kennedy leisurely tore the wrappings from the packet. "I suppose you have already looked at this first and found that it isn't worth anything to you compared to twenty dollars. Anyhow, you kept your word. Hello--what is it?" He had disclosed several small packets. Inside each, sealed, was a peculiar glistening whitish powder. "H'm," mused Kennedy, "another job for the chemist. Here's the bankroll." "Thanks," grinned the dip as he disappeared through the revolving door. We had returned to the laboratory that night where Kennedy was preparing to experiment on the white powder which he had secured in the packet that came from Dr. Harris. The door opened and Clare Kendall entered. "I've been calling you up all over town," she said, "and couldn't find you. I have something that will interest you, I think. You said you wanted something written by Dr. Harris. Well, there it is." She laid a sheet of typewriting on the laboratory table. "How did you get it?" asked Kennedy in eager approbation. "When I left you at the Futurist Tea Room to follow that woman Marie in the cab, I had a good deal of trouble. I guess people thought I was crazy, the way I was ordering that driver about, but he was so stupid and he would get tangled up in the traffic on Fifth Avenue. Still, I managed to hang on, principally because I had a notion already that she was going to the Montmartre. Sure enough, she turned down that block, but she didn't go into the hotel after all. She stopped and went into a place two doors down--Mme. Margot's Beauty Parlour." "Just where we finally saw Harris go," exclaimed Kennedy. "I beg your pardon for interrupting." "Of course I couldn't go in right after her, so I drove around the corner. Then it occurred to me that it would be a good time to stop in to see Dr. Harris--when he was out. You know my experience with the fakers has made me pretty good at faking up ailments. Then, too, I knew that it would be easy when he was not there. I said I was an old patient and had an appointment and that I'd wait, although I knew those were not his regular office hours. He has an alleged trained nurse there all the time. She let me into his waiting-room on the second floor in front--you remember the private dining-rooms are in back. I waited in momentary fear that he WOULD come back. You see, I had a scheme of my own. Well, I waited until at last the nurse had to leave the office for a short time. "That was my chance. I tiptoed over to his desk in the next room. On it were a lot of letters. I looked over them but could find nothing that seemed to be of interest. They were all letters from other people. But they showed that he must have quite an extensive practice, and that he is not over-scrupulous. I didn't want to take anything that would excite suspicion unless I had to. Just then I heard someone coming down the corridor from the elevator. I had just time to get back to a chair in the waiting-room when the door opened and there was that Titian from the office, you remember. She saw me without recognizing me, went in and laid some papers on his desk. As soon as she was gone, I went in again and looked them over. Here was one that she had copied for him." Kennedy had been carefully scrutinizing the sheet of paper as she told how she obtained it. "It couldn't be better as far as our purposes are concerned," he congratulated. "It seems to consist of some notes he had made and wished to preserve about drugs." I leaned over and read: VERONAL.--Diethylmalonyl or diethylbarbituric acid. A hypnotic used extensively. White, crystalline, odourless, slightly bitter. Best in ten to fifteen grain cachets. Does not affect circulatory or respiratory systems or temperature. Toxicity low: 135 gr. taken with no serious result. Unreasonable use for insomnia, however, may lead to death. HEROIN.--Constant use of heroin has been known to lead to-- I looked inquiringly at Kennedy. "Just some fragmentary notes which he had evidently been making. Rather interesting in themselves as showing perhaps something of his practice, but not necessarily incriminating." While we were discussing the contents of the notes, Kennedy had laid over the typewritten sheet the rules and graduated strip of glass which he had used in examining the strange letter signed "An Outcast." A moment later he pulled the letter itself from a drawer and laid the two pieces of writing side by side, comparing them, going from one to the other successively. "People generally, who have not investigated the subject," he remarked as he worked, "hold the opinion that the typewriter has no individuality. Fortunately that is not true. The typewriting machine does not always afford an effective protection to the criminal. On the contrary, the typewriting may be a direct means of tracing a document to its source and showing it to be what it really is. This is especially true of typewritten anonymous letters. Without careful investigation it is impossible to say what can be determined from the examination of any particular piece of typewriting, but typewriting can often be positively identified as being the work of a certain particular typewriting machine and even the date of writing can sometimes be found out." He had been carefully counting something under the lens of a pocket glass. "Even the number of threads to the inch in the ribbon, as shown in the type impression, plainly seen and accurately measured by the microscope or in an enlarged photograph, may show something about the identity of a disputed writing." He was pointing to a letter "r." Under the glass I noticed that there was a break in the little curl at the top. "Now if you find such a break in the same letter in another piece of typewriting, what would you think?" "That they were from the same machine," I replied. "Not so fast," he cautioned. "True, it might raise a presumption that it was from the same machine. But the laws of chance would be against your enthusiasm, Walter." "Of course," I admitted on second thought. "It's just like the finger-print theory. There must be a sort of summation of individual characteristics. Now here's a broken 'l' and there is an 'a' that is twisted. Now, if the same defects are found in another piece of writing, that makes the presumption all the stronger, and when you have massed together a number of such characteristics it raises the presumption to a mathematical certainty, does it not?" I nodded and he went on. "The faces of many letters inevitably become broken, worn, or battered. Not only does that tend to identify a particular machine, but it is sometimes possible, if you have certain admitted standard specimens of writing covering a long period, to tell just when a disputed writing was made. There are two steps in such an inquiry, the first the determination of the fact that a document was written on a certain particular kind of machine and the second that it was written on a certain individual machine of that make. I have here specimens of the writing of all the leading machines. It is easy to pick out the make used, say in the 'Outcast' letter. Moreover, as I said when I first saw that letter, it is in the regular pica type. So are they all, but as ninety-five per cent, use the pica style that in itself proved nothing." "What is that bit of ruled glass?" asked Clare, bending over the letters in deep interest. "In ordinary typewriting," replied Craig, "each letter occupies an imaginary square, ten to the inch horizontally and six to the inch vertically. Typewriting letters are in line both ways. This ruled glass plate is an alinement test plate for detecting defects in alinement. I have also here another glass plate in which the lines diverge each at a very slightly different angle--a typewriting protractor for measuring the slant of divergence of various letters that have become twisted, so to speak. "When it is in perfect alinement the letter occupies the middle of each square and when out of alinement it may be in any of the four corners, or either side of the middle position or at the top or bottom above or below the middle. That, you see, makes nine positions in all--or eight possible divergences from normal in this particular alone." Clare had been using the protractor herself, quickly familiarizing herself with it. "Another possible divergence," went on Kennedy, "is the perpendicular position of the letter in relation to the line. That is of great value in individualizing a machine. It is very seldom that machines, even when they are new, are perfect in this particular. It does not seem much until you magnify it. Then anyone can see it, and it is a characteristic that is fixed, continuous, and not much changed by variations in speed or methods of writing. "Here's another thing. Typewriter faces are not flat like printing type, but are concaved to conform to the curve of the printing surface of the roller. When they are properly adjusted all portions should print uniformly. But when they are slightly out of position in any direction the two curved surfaces of type and roller are not exactly parallel and therefore don't come together with uniform pressure. The result is a difference in intensity in different parts of the impression." It was fascinating to see Craig at work over such minute points which we had never suspected in so common a thing as ordinary typewriting. "Then you can identify these letters positively?" asked Clare. "Positively," answered Craig. "If two machines of the same make were perfect to begin with and in perfect condition--which is never found to be the case when they are critically examined--the work from one would be theoretically indistinguishable from that of another until actual use had affected them differently. The work of any number of machines begins inevitably to diverge as soon as they are used. Since there are thousands of possible particulars in which differences may develop, it very soon becomes possible to identify positively the work of a particular typewriting machine." "How about the operator?" I asked curiously. "Different habits of touch, spacing, speed, arrangement, and punctuation all may also tend to show that a particular piece of writing was or was not done by one operator. In other words, typewriting individuality in many cases is of the most positive and convincing character and reaches a degree of certainty which may almost be described as absolute proof. The identification of a typewritten document in many cases is exactly parallel to the identification of an individual who precisely answers a general description as to features, complexion, size, and in addition matches a long detailed list of scars, birthmarks, deformities, and individual peculiarities." Together we three began an exhaustive examination of the letters, and as Kennedy called off the various characteristics of each type on the standard keyboard we checked them up. It did not take long to convince us, nor would it have failed to convince the most sceptical, that both had come from the same source and the same writer. "You see," concluded Kennedy triumphantly, "we have advanced a long step nearer the solution of at least one of the problems of this case." Miss Kendall had evidently been thinking quickly and turning the matter over in her mind. "But," she spoke up quickly, "even that does not point to the same person as the author--not the writer, but the author--of the three pieces of writing." "No indeed," agreed Craig. "There is much left to be done. As a matter of fact, there might have been one author, or there might have been two, although all the mechanical work was done by one person. But we are at least sure that we have localized the source of the writing. We know that it is from the Montmartre that the letter came. We know that it is in some way that that place and some of the people who frequent it are connected with the disappearance of Betty Blackwell." "In other words," supplied Clare, "we are going to get at the truth through that Titian-haired stenographer." "Exactly." Clare had risen to go. "It quite takes my breath away to think that we are really making such progress against the impregnable Montmartre. At various times my investigators have been piecing together little bits of information about that place. I shall have the whole record put together to-night. I shall let you know about it the first thing in the morning." The door had scarcely closed when Kennedy turned quickly to me and remarked, "That girl has something on her mind. I wonder what it is?" XII THE "PORTRAIT PARLE" What it was that Clare Kendall had on her mind, appeared the following day. "There's something I want to try," she volunteered, evidently unable to repress it any longer. "I have a plan--or half a plan. Don't you think it would be just the thing, under the circumstances, to ring up District Attorney Carton, tell him what we have accomplished and take him into our confidence? Perhaps he can suggest something. At any rate we have all got to work together, for there is going to be a great fight when they find out how far we have gone." "Bully idea," agreed Craig. Twenty minutes later we were seated in the District Attorney's office in the Criminal Courts Building, pouring into his sympathetic ear the story of our progress so far. Carton seemed to be delighted, as Kennedy proceeded to outline the case, at the fact that he and Miss Kendall had found it possible to co-operate. His own experience in trying to get others to work with the District Attorney's office, particularly the police, had been quite the reverse. "I wish to heaven you could get the right kind of evidence against the Montmartre gang," he sighed. "It is a gang, too--a high-class gang. In fact--well, it must be done. That place is a blot on the city. The police never have really tried to get anything on it. Miss Kendall never could, could you? I admit I never have. It seems to be understood that it is practically impossible to prove anything against it. They openly defy us. The thing can't go on. It demoralizes all our other work. Just one good blow at the Montmartre and we could drive every one of these vile crooks to cover." He brought his fist down with a thud on the desk, swung around in his chair, and emphasized his words with his forefinger. "And yet, I know as well as I know that you are all in this room that graft is being paid to the police and the politicians by that place and in fact by all those places along there. If we are to do anything with them, that must be proved. That is the first step and I'm glad the whole thing hinges on the Blackwell case. People always sit up and take notice when there is something personal involved, some human interest which even the newspapers can see. That Montmartre crowd, whoever they are, must be made to feel the strong arm of the law. That's what I am in this office to do. Now, Kennedy, there must be some way to catch those crooks with the goods." "They aren't ordinary crooks, you know," ruminated Kennedy. "I know they are not. But you and Miss Kendall and Jameson ought to be able to think out a scheme." "But you see, Mr. Carton," put in Clare, "this is a brand new situation. Your gambling and vice and graft exposures have made all of them so wary that they won't pass a bill from their right to their left pockets for fear it is marked." Carton laughed. "Well, you are a brand new combination against them. Let me see; you want suggestions. Why don't you use the detectaphone--get our own little Black Book?" Kennedy shook his head. "The detectaphone is all right, as Dorgan knows. It might work again. But I don't think I'll take any chances. No, these grafters wouldn't say 'Thank you' in an open boat in mid-ocean, for fear of wireless, now. They've been educated up to a lot of things lately. No, it must be something new. What do you know about graft up there?" "The people who are running those places in the fifties are making barrels of money," summarized Carton quickly. "No one ever interferes with them, either. I know from reliable sources, too, that the police are 'getting theirs.' But although I know it I can't prove it; I can't even tell who is getting it. But once a week a collector for the police calls around in that district and shakes them all down. By Jove, to-day is the day. The trouble with it all is that they have made the thing so underground that no one but the principals know anything about it--not even the agents. I guess you are right about the detectaphone." "To-day's the day, is it?" mused Craig. "So I understand." "I think I can get them with a new machine they never dreamed of," exclaimed Kennedy, who had been turning something over in his mind. He reached for the telephone and called the Montmartre. "Julius, please," he said when they answered; then, placing his hand over the transmitter, he turned to Clare. "That was your friend the Titian, Miss Kendall." "No friend of mine if she happens to remember seeing me in Dr. Harris's office the other day. Still, I doubt if she would." "Hello--Julius? Good morning. How about a private dining-room for three, Julius?" We could not hear the reply, but Craig added quickly, "I thought there were two?" Evidently the answer was in the affirmative, for Craig asked next, "Well, can't we have the small one?" He hung up the receiver with a satisfied smile after closing with "That's the way to talk. Thank you, Julius. Good-bye." "What was the difficulty?" I asked. "Why, I thought I'd take a chance--and it took. Now figure it out for yourself. Carton says it's dough day, so to speak, up there. What is more natural than that the money for all those places leased to various people should be passed over in a place that is public and yet is not public? For instance, there is the Montmartre itself. Now think it out. Where would that be done in the Montmartre? Why, in one of the private dining-rooms, of course." "That seems reasonable," agreed Carton. "That was the way I doped it," pursued Craig. "I thought I'd confirm it if I could. You remember they told us to call up always if I wanted a private dining-room and it would be reserved for me. So it was the most natural thing in the world for me to call up. If they had said yes, I should have been disappointed. But they said no, and straightway I wanted one of those rooms the worst way. One seems to be engaged--the large one. He said nothing about the other, so I asked him. Since I knew about it, he could hardly say no. Well, I have engaged it for lunch--an early luncheon, too." "It sounds all right, as though you were on the right trail," remarked Carton. "But, remember, only the best sort of evidence will go against those people. They can afford to hire the best lawyers that money can retain. And be careful not to let them get anything on you, for they are fearful liars, and they'll go the limit to discredit you." "Trust us," assured Craig. "Now, Miss Kendall, if you will give us the pleasure of lunching with you at the Montmartre again, I think we may be able to get the Judge just the sort of open and shut evidence he is after." "I shall be glad to do it. I'm ready now." Kennedy glanced at his watch. "It's a little early yet. If we take a taxicab we shall have plenty of time to stop at the laboratory on our way." Arriving at the laboratory, he went to a drawer, from which he took a little box which contained a long tube, and carefully placed it in the breast pocket of his coat. Then from a chest of tools he drew several steel sections that apparently fitted together, and began stuffing the parts into various pockets. "Here, Walter," he said, "these make me bulge like a yeggman with his outfit under his coat. Can't you help me with some of these parts?" I jammed several into various pockets--heavy pieces of metal--and we were ready. Our previous visits to the Montmartre seemed to have given us the entree and the precaution of telephoning made it even easier. Indeed, it appeared that about all that was necessary there was to be known and to be thought "right." We carefully avoided the office, where the stenographer might possibly have recognized Clare, and entered the elevator. "Is Dr. Harris in?" asked Craig, both by way of getting information and showing that he was no stranger. The black elevator boy gave an ivory grin. "No, sah. He done gone on one o' them things." Another question developed the fact that whenever Harris was away it was generally assumed that he was tinting the metropolis vermilion from the Battery to the Bronx. We passed down the hall to the smaller of the two dining-rooms, and as we went by the larger we could see the door open and that no one was there. We had ordered and the waiter had scarcely shut the door before Kennedy had divested himself of the heavy steel sections which he had hidden in his pockets. I did the same. With a quick glance he seemed to be observing just how the furniture was placed. The smaller dining-room was quite as elaborately furnished as the larger, though of course the furniture was more crowded. He moved the settee and was on his knees in a corner. "Let me see," he considered. "There was nothing on this side of the larger room except the divan in the centre." As nearly as he could judge he was measuring off just where the divan stood on the opposite side of the wall, and its height. Then he began fitting together the pieces of steel. As he added one to another, I saw that they made a sectional brace and bit of his own design, a long, vicious-looking affair such as a burglar might have been glad to own. Carefully he started to bore through the plaster and lath back of the settee and to one side of where the divan must have been. He was making just as small a hole as possible, now and then stopping to listen. There was no noise from the next room, but a tap on the door announced the waiter with luncheon. He shoved the settee back and joined us. The discreet waiter placed the food on the table and departed without a word or look. Kennedy resumed his work and we left the luncheon still untasted. The bit seemed to have gone through as Kennedy, turning it carefully, withdrew it now and then to make sure. At last he seemed to be satisfied with the opening he had made. From the package in his breast pocket he drew a long brass tube which looked as if it might be a putty-blower. Slowly he inserted it into the hole he had bored. "What is it?" I asked, unable to restrain my curiosity longer. "I felt sure that there would be no talking done in that room, especially as we are in this one and anyone knows that even if you can't put a detectaphone in a room, it will often work if merely placed against a wall or door, on the other side, in the next room. So I thought I'd use this instead. Put your eye down here." I did so and was amazed to find that through a hole less than a quarter of an inch in diameter the brass tube enabled me to see the entire room next to us. I looked up at Kennedy in surprise. "What do you think of this, Miss Kendall?" I asked, moving the settee out of her way. "What do you call it?" "That is a detectascope," he replied, "a little contrivance which makes use of the fish-eye lens. "Yes. The detectascope enables you to see what is going on in another room. The focus may be altered in range so that the faces of those in the room may be recognized and the act of passing money or signing cheques, for instance, may be detected. The instrument is fashioned somewhat after the cytoscope of the doctors, with which the human interior may be seen." "Very remarkable," exclaimed Clare. "But I can't understand how it is possible to see so much through such a little tube. Why, I almost fancy I can see more in that room than I could with my own eyes if I were placed so that I could not move my head." Kennedy laughed. "That's the secret," he went on. "For instance, take a drop of water. Professor Wood of Johns Hopkins has demonstrated recently the remarkable refracting power of a drop of water, using the camera and the drop of water as a lens. It is especially interesting to scientists because it illustrates the range of vision of some fishes. They have eyes that see over half a circle. Hence the lens gets its name--'the fish-eye lens.' A globe refracts the light that reaches it from all directions, and if it is placed as the lens is in the detectascope so that one half of it catches the light, all this light will be refracted through it. Ordinary lenses, because of their flatness, have a range of only a few degrees, the widest in use, I believe, taking in only ninety-six degrees, or a little over a quarter of a circle. So you see my detectascope has a range almost twice as wide as that of any other lens." The little tube was fascinating, and although there was no one in the next room yet, I could not resist the desire to keep on looking through it. "Since you are so interested, Walter," laughed Craig, "we'll appoint you to take the first shift at watching. Meanwhile we may as well eat since we shall certainly have to pay. When you are tired or hungry I'll take a turn." Kennedy and I had been taking turns at watching through the detectascope while Miss Kendall told us more about how she had come to be associated with the organization to clean up New York. "We have struck some delicate situations before," she was saying, "times when it meant either that we must surrender and compromise the work of the investigation or offend an interest that might turn out to be more powerful than we realized. Our rule from the start was, 'No Compromise.' You know the moment you compromise with one, all the others hear it and it weakens your position. We've made some powerful enemies, but our idea is that as long as we keep perfectly straight and honest they will never be able to beat us. We shall win in the end, because so far it has never come to a show-down, when we appealed to the public itself, that the public had not risen and backed us strongly." I had come to have the utmost confidence in Clare Kendall and her frank way of handling a ticklish yet most important subject without fear or prudishness. There was a refreshing newness about her method. It was neither the holier-than-thou attitude of many religionists, nor the smug monopoly of all knowledge of the social worker, nor the brutal wantonness of the man or woman of the world who excuses everything "because it is human nature, always has been and always will be." "We have no illusions on the subject," she pursued. "We don't expect to change human nature until the individual standard changes. But we are convinced of this--and it is as far as we go and is what we are out to accomplish--and that is that we can, and are going to, smash protected, commercialized vice as one of the big businesses of New York." "Sh-h," cautioned Kennedy, whose turn it happened to be just then to watch. "Someone has just entered the room." "Who is it?" I whispered eagerly. "A man. I can't see his face. His back is toward me, but there is something familiar about him. There--he is turning around. For Heaven's sake--it's Ike the Dropper!" We had already recounted to Miss Kendall our experiences in following Dr. Harris to the black and tan joint and the meeting with Ike the Dropper. "Then Ike the Dropper is the collector for the police or the politicians higher up," she exclaimed under her breath. "If we learned nothing more, that would be enough. It would tell us whom to watch." Hastily we took turns at getting a good look at Ike through the wonderful little detectascope. Then Kennedy resumed his watch, whispering now and then what he saw. Apparently Ike had proceeded to make himself comfortable in the luxurious surroundings of the private dining-room, against the arrival of the graft payers. "I wonder who the man higher up is," whispered Miss Kendall. "Someone is coming in," reported Kennedy. "By George, it is that stenographer from the office downstairs. She is handing him an envelope. Good for her! He tried to kiss her and she backed away in disgust. The scoundrel! "Isn't it clever, though? Not a word is said by anyone. I don't suppose she could swear to knowing anything about what is in the envelope. There she goes out. He is opening the envelope and counting out the money--ten one-hundred-dollar bills. There they go into the fob pocket of his trousers. I imagined he learned something from my pick-pocket. That is the safest pocket a man has. That little contribution, I take it, was from the Montmartre itself." Then followed an interval in which Ike puffed away on his cigar in silent state. "Here's another now," announced Craig. "Another woman. I never saw her before." Both Miss Kendall and I looked and neither of us recognized her. She was slim and would have been young-looking if she had not made such obvious efforts to imitate the healthy colour of the cheeks which she probably would have had if she had lived sensibly and left cosmetics alone. Kennedy was hastily jotting down some notes on the back of an envelope. "They are going through the same proceedings again. I guess Ike doesn't like her. There she goes. Only two hundred this time." Another wait followed, during which Ike smoked down his cigar and lighted another from the stub. Then the door opened again. Kennedy motioned quickly to Clare to look through the detectascope. Meanwhile he pulled from his pocket the piece of paper he had written on and torn from the back of the menu at the Futurist. "Marie!" exclaimed Clare under her breath. "The same," whispered Kennedy. "Miss Kendall, you have the true 'camera eye' of the born detective. Now--please--let me see if I can get what occurs." She yielded her place to him. "Three hundred more," he murmured. "Marie must be in the game, though. He didn't wait for her to leave before he tore open the envelope. Now they are burning the envelopes in the ash tray. And still not a word. This is clever, clever. Think of it--fifteen hundred dollars of easy money like that! I wonder how much of it sticks to Ike's hands on the way up. He must have a capacious fob pocket for that. Say, he's a regular fellow with the ladies, Ike is. Only this one doesn't seem to resent it. By George, I wonder if this fellow Ike isn't giving the police or the politicians the double-cross. He couldn't be on such intimate terms with one who was paying graft to him as collector otherwise; do you think so?" Craig looked up without waiting for an answer. "You will excuse any levity, but that was some kiss she just gave him." Kennedy resumed his position for looking through the detectascope, occasionally glancing down at the notes he had made the day before and now and then making a slight alteration. "There. She is going away now. Well, I guess the collection is all over. He has his hat on and a third cigar, ready to go as soon as somebody signals that the coast is clear. That was a good day's work for Ike and the man higher up, whoever he is. Ah--there he goes. It was a signal from the waiter he was after. Now we may as well finish this luncheon. It cost enough." For several minutes we ate in silence. "I wish I could have followed Ike," observed Craig. "But of course it would have been of no use. To go out right after him would have given the whole thing away." "Who is that dark-haired, dark-skinned woman, Marie, do you suppose?" asked Clare. "Sometimes I almost think she is part negro." "I don't know. I wouldn't be surprised, though, if you were right. If you have any investigators to spare, they might try to find out who she is and something of her history. I will give them a copy of these notes which I intend to turn over to the Department of Justice men who have been making the white slave investigation for the Federal Government." Kennedy had laid the notes which he had made on the menu before us and was copying them. Both Clare and I leaned over to read them. It was Greek to me: Nose--straight, base elevated, nostrils thick, slightly flaring. Ears--lobe descending oval, traversed by a hollow, antitragus concave; lobe separated from cheek. Lips--large. Mouth--large. Chin--receding. There was much more that he had jotted down and added to the description. "Oh," exclaimed Clare, as she ran through the writing, "that is this new portrait parle, the spoken picture, isn't it?" "Yes," replied Kennedy. "You may know that the Government has been using it in its white slave inquiry and has several thousands of such descriptions. Under the circumstances, I understand that the Government agents find it superior to finger-prints. Finger-prints are all right for identification, as we have found right here, for instance, in the Night Court. But Bertillon's new portrait parle is the thing for apprehension." "What is it?" I asked. "Well, take the case before us. We have had no chance to finger-print that woman and what good would it do if we had? No one could recognize her that way until she was arrested or some means had been taken to get the prints again. "But the portrait parle is scientific apprehension, the step that comes before scientific identification by finger-prints. It means giving the detective an actual portrait of the person he is sent after without burdening him with a photograph. As descriptions are now given, together with a photograph, a person is described as of such a weight, height, general appearance, and so on. A clever crook knows that. He knows how to change his appearance so that there are few even of the best detectives who can recognize him. This new system describes the features so that a man can carry them in his mind systematically, features that cannot be changed. "Take the nose, for example," explained Kennedy. "There are only three kinds, as Bertillon calls them--convex, straight, and concave. A detective, we will say, is sent out after a man with a concave nose or, as in this case a woman with a straight nose. Thus he is freed from the necessity of taking a second glance at two-thirds of the women, roughly, that he meets--that is, theoretically. He passes by all with convex and concave noses. "There are four classes of ears--triangular, square, oval, and round, as they may be called. Having narrowed his search to women with straight noses, the detective needs to concern himself with only one-fourth of the women with straight noses. Having come down to women with straight noses and, say, oval ears, he will eliminate all those that do not have the mouth, lips, chin, eyes, forehead, and so on that have been given him. Besides that, there are other striking differences in noses and ears that make his work much easier than you would imagine, once he has been trained to observe such things quickly." "It sounds all right," I agreed haltingly. "It is all right, too," he argued warmly. "The proof of it is its use in Paris and other cities abroad and the fact that it has been imported here to New York in the Police Department and has been used by the Government. I could tell you many interesting stories about how it has succeeded where photographs would have failed." I had been reading over the description again and trying to apply it. "For instance," Craig resumed thoughtfully. "I believe that this woman is a mulatto, but that is a long way from proving it. Still, I hope that by using the portrait parle and other things we may be able to draw the loose threads together into a net that will catch her--providing, of course, that she ought to be caught." He had finished making copies of the portrait parle and had called for a cheque for the lunch. "So you see," he concluded, "this is without any doubt the woman we saw at the Futurist, whom Miss Kendall followed to Madame Margot's Beauty Shop, two doors down." Kennedy handed a copy to Miss Kendall. "Using that and whatever other means you may have, Miss Kendall," he said, "I wish that you would try to find this woman and all you can about her. Walter, take this other copy and see Carton. I think he has a county detective who knows the system. I shall spend the rest of the day getting in touch with the Federal authorities in this city and in Washington trying to find out whether they know anything about her." We left the Montmartre with as much care as we had entered and seemingly without having yet aroused any suspicion. The rest of the day was spent in setting to work those whom we felt we could trust to use the portrait parle to locate the mysterious dark-haired Marie who seemed to cross our trail at every turn, yet who proved so elusive. XIII THE CONVICTION Meanwhile, the organization was using every effort to get possession of the Black Book, as Kennedy had suspected. Miss Ashton had been busy on the case of the missing Betty Blackwell, but as yet there was no report from any of the agencies which she had set in motion to locate the girl. She had seen Langhorne, and, although she did not say much about the result of the interview, I felt sure that it had resulted in a further estrangement between them, perhaps a suspicion on the part of Langhorne that Carton had been responsible for it. In as tactful a way as possible, Miss Ashton had also warned Mrs. Ogleby of the danger she ran, but, as I had already supposed, the warning had been unnecessary. The rumours about the detectaphone record of the dinner had been quite enough. As for the dinner itself, what happened, and who were present, it remained still a mystery, perhaps only to be explained when at last we managed to locate the book. Since the visit of Kahn, we had had no direct or indirect communications with either Dorgan or Murtha. They were, however, far from inactive, and I felt that their very secrecy, which had always been the strong card of the organization, boded no good. Although both Carton and Kennedy were straining every nerve to make progress in the case, there was indeed very little to report, either the next day or for some time after the episode which had placed Kahn in our power. Carton was careful not to say anything about the graphic record we had taken of Kahn's attempt to throw the case. It was better so, he felt. The jury fixing evidence would keep and it would prove all the stronger trump to play when the right occasion arose. That time rapidly approached, now, with the day set for the trial of Dopey Jack. The morning of the trial found both Kennedy and myself in the part of General Sessions to which the case had been assigned to be tried under Justice Pomeroy. To one who would watch the sieve through which justice vigorously tries to separate the wheat from the chaff, the innocent from the guilty, a visit to General Sessions is the best means. For it is fed through the channels that lead through the police courts, the Grand Jury chambers, and the District Attorney's office. There one can study the largest assortment of criminals outside of a penal institution, from the Artful Dodger and Bill Sykes, Fagin and Jim the Penman, to the most modern of noted crooks of fact or fiction, all done here in real flesh and blood. It is the busiest of criminal courts. More serious offenders against the law are sentenced here than in any other court in New York. The final chapter in nearly every big crime is written there, sooner or later. As we crowded in, thanks to the courtesy of Carton, we found a roomy chamber, with high ceiling, and grey, impressive walls in the southeast corner of the second floor of the Criminal Courts Building. Heavy carved oaken doors afforded entrance and exit for the hundreds of lawyers, witnesses, friends, and relatives of defendants and complainants who flocked thither. Rows upon rows of dark-brown stained chairs filled the west half of the courtroom, facing a three-foot railing that enclosed a jury box and space reserved for counsel tables, the clerk and the District Attorney representing the people. At the extreme east rose in severe dignity the dais or bench above which ascended a draped canopy of rich brown plush. Here Justice Pomeroy presided, in his robes of silk, a striking, white-haired figure of a man, whose face was seamed and whose eyes were keen with thought and observation. Across the street, reached by the famous Bridge of Sighs, loomed the great grey hulk of stone and steel bars, the city prison, usually referred to as "The Tombs." As if there had been some cunning design in the juxtaposition, the massive jail reared itself outside the windows as an object lesson. It was a perpetual warning to the lawbreaker. Its towers and projections jutted out as so many rocks on a dangerous shore where had been wrecked thousands of promising careers just embarked on the troublesome seas of life. Skirting the line of southern windows through which The Tombs was visible, ran a steel wire screen, eight feet high, marking off a narrow chute that hugged the walls to a door at the rear of the courtroom leading to the detention pen. Ordinarily prisoners were brought over the Bridge of Sighs in small droves and herded in the detention pens just outside the courtroom until their cases were called. The line-up of prisoners at such times awaiting their turn at the bar of justice affords ample opportunity for study to the professional or the amateur criminalist. Almost daily in this court one might look upon murderers, bank looters, clever forgers, taxicab robbers, safe crackers, highwaymen, second-story men, shoplifters, pickpockets, thieves, big and little--all sorts and conditions of crooks come to pay the price. The court was crowded, for the gang leaders knew that this was a show-down for them. Carton himself, not one of his assistants, was to conduct the case. If Dopey Jack, who had violated almost every law in the revised statutes and had never suffered anything worse than a suspended sentence, could not get off, then no one could. And it was unthinkable that Dopey should not only be arrested and held in jail without bail, but even be convicted on such a trivial matter as slight irregularities that swung the primaries in a large section of the city for his superior, "higher up." Rubano's father, a decent, sorrowing old man, sat in the rear of the courtroom, probably wondering how it had all happened, for he came evidently of a clean, law-abiding family. But there was nothing in the appearance of the insolent criminal at the bar to show that he was of the same breed. He was no longer the athlete, whom "prize fighting" had inculcated with principles of manliness and fair play as well as a strong body. All that, as I had seen often before, was a pitiful lie. He was rat-eyed and soft-handed. His skin had the pastiness that comes of more exposure to the glare of vile dance halls than the sunlight of day. His black hair was slicked down; he was faultlessly tailored and his shoes had those high, bulging toes which are the extreme of Fourteenth Street fashion. Outside, overflowing into the corridor, were gangsters, followers and friends of Dopey Jack. Only an overpowering show of force preserved the orderliness of the court from their boasting, bragging, and threats. The work of selecting the jury began, and we watched it carefully. Kahn, cool and cunning, had evidently no idea of what Carton was holding out against him. In the panel I could see the anemic-looking fellow whom we had caught with the goods up at Farrell's. Carton's men had shadowed him and had learned of every man with whom he had spoken. As each, for some reason or other, was objected to by Carton, Kahn began to show exasperation. At last the anemic fellow came up for examination. Kahn accepted him. For a moment Carton seemed to fumble among his papers, without even looking at the prospective juror. Then he drew out the print which Kennedy had made. Quietly, without letting anyone else see it, he deliberately walked to Kahn's table and showed it to the lawyer, without a word, in fact without anyone else in the court knowing anything about it. Kahn's face was a study, as he realized for the first time what it was that Carton and Kennedy had been doing that night at Farrell's. He paled. His hand shook. It was with the utmost effort that he could control his voice. He had been cornered and the yellow streak in him showed through. In a husky voice he withdrew the juror, and Carton, in the same cold, self-possessed manner resumed his former position, not even a trace of a smile on his features. It was all done so quickly that scarcely a soul in the court besides ourselves realized that anything had happened. "Isn't he going to say anything about it?" I whispered to Craig. "That will come later," was all that Kennedy replied, his eyes riveted still on Carton. Though no one besides ourselves realized it, Carton had thrown a bombshell that had demolished the defence. Others noticed it, but as yet did not know the cause. Kahn, the great Kahn by whom all the forces of the underworld had conjured, was completely unnerved. Carton had fixed it so that he could not retreat and leave the case to someone else. He had knocked the props from under his defence by uncannily turning down every man whom he had any reason of suspecting of having been approached. Then he had given Kahn just a glimpse of the evidence that hinted at what was in store for himself personally. Kahn was never the same after that. Judge Pomeroy, who had been following the progress of the case attentively, threw another bombshell when he announced that he would direct that the names of the jurors be kept secret until it was absolutely necessary to disclose them, a most unusual proceeding designed to protect them from reprisals of gangmen. At last the real trial began. Carton had been careful to see that none of the witnesses for the people should be "stiffened" as the process was elegantly expressed by those of Dopey Jack's class--in other words, intimidated, bribed, or otherwise rendered innocuous. One after another, Carton rammed home the facts of the case, the fraudulent registration and voting, the use of the names of dead men to pad the polling lists, the bribery of election officials at the primaries--the whole sordid, debasing story of how Dopey Jack had intimidated and swung one entire district. It was clever, as he presented it, with scarcely a reference to the name of Murtha, the beneficiary of such tactics--as though, perhaps, Murtha's case was in his mind separate and would be attended to later when his turn came. Rapidly, concisely, convincingly, Carton presented the facts. Now and then Kahn would rise to object to something as incompetent, irrelevant, and immaterial. But there was lacking something in his method. It was not the old Kahn. In fact, one almost felt that Carton was disappointed in his adversary, that he would have preferred a stiff, straight from the shoulder, stand-up fight. Now and then we could hear a whisper circulating about among the spectators. What was the matter with Kahn? Was he ill? Gangdom was in a daze itself, little knowing the smooth stone that Carton had slung between the eyes of the great underworld Goliath of the law. At last Carton's case was all in, and Kahn rose to present his own, a forced smile on his face. There was an attempt at a demonstration, but Judge Pomeroy rapped sharply for order, and alert court attendants were about to nip effectively any such outburst. Still, it was enough to show the undercurrent of open defiance of the court, of law, of the people. What it was no one but ourselves knew but Kahn was not himself. Others saw it, but did not understand. They had waited patiently through the sledge-hammer pounding of Carton, waiting expectantly for Kahn to explode a mine that would demolish the work of the District Attorney as if it had been so much paper. Carton had figuratively dampened the fuse. It sputtered, but the mine did not explode. Once or twice there were flashes of the old Kahn, but for the most part he seemed to have crumpled up. Often I thought he was not the equal of even a police court lawyer. The spectators seemed to know that something was wrong, though they could not tell just what it was. Kahn's colleagues whispered among themselves. He made his points, but they lacked the fire and dash and audacity that once had caused the epigram that Kahn's appearance in court indicated two things--the guilt of the accused and a verdict of acquittal. Even Justice Pomeroy seemed to notice it. Kahn had tried many a case before him and the old judge had a wholesome respect for the wiley lawyer. But to-day the court found nothing so grave as the strange dilatoriness of the counsel. Once the judge had to interfere with the remark, "I may remind the learned counsel for the defence that the court intends to finish this case before adjournment for the day, if possible; if not, then we shall sit to-night." Kahn seemed not to grasp the situation, as he had of old. He actually hurried up the presentation of the case, oblivious to the now black looks that were directed at him by his own client. If he had expected to recover his old-time equanimity as the case proceeded, he failed. For no one better than he knew what that little photograph of Carton's meant--disgrace, disbarment, perhaps prison itself. What was this Dopey Jack when ruin stared himself so relentlessly in the face in the person of Carton, calm and cool? At last the summing up was concluded and both sides rested. Judge Pomeroy charged the jury, I thought with eminent fairness and impartiality, even, perhaps, glossing over some points which Kahn's weak presentation might have allowed him to make more of if Kahn had been bolder and stronger in pressing them. The jury filed out and the anxious waiting began. On all sides was the buzz of conversation. Kahn himself sat silent, gazing for the most part at the papers before him. There must have been some wrangling of the jury, for twice hope of the gangsters revived when they sent in for the record. But it was not over an hour later when the jury finally filed back again into their box. As Judge Pomeroy faced them and asked the usual question, the spectators hung, breathless, on the words of the foreman as the jurors stood up silently in their places. There was a tense hush in the courtroom, as every eye was fastened on the face of the foreman. The hush seemed to embarrass him. But finally he found his voice. Nervously, as if he were taking his own life in his hands he delivered the verdict. "We find the defendant guilty as charged in the indictment!" Instantly, before anyone could move, the dignified judge faced the prisoner deliberately. "You have heard the verdict," he said colourlessly. "I shall sentence you Friday." Three court attendants were at Dopey Jack's side in a moment, but none too soon. The pent-up feeling of the man idolized by blackmailers, and man-killers, and batteners on street-women, who held nothing as disgrace but a sign of respect for law or remorse for capture, burst forth. He cast one baleful look at Kahn as they hurried him to the wire-screened passageway. "It's all a frame-up--a damned frame-up!" he shouted. As he disappeared a murmer of amazement ran through the room. The unthinkable had happened. An East Side idol had fallen. XIV THE BEAUTY PARLOUR "It seems strange," remarked Kennedy the following morning when we had met in his laboratory for our daily conference to plan our campaign, "that although we seem to be on the right trail we have not a word yet about Betty Blackwell herself. Carton has just telephoned that her mother, poor woman, is worrying her heart out and is a mere shadow of her former self." "We must get some word," asserted Miss Kendall. "This silence is almost like the silence of death." "I'm afraid I shall have to impose on you that task," said Kennedy thoughtfully to her. "There seems to be no course open to us but to transfer our watch from Dr. Harris to this Marie. Of course it is too early to hear from our search by means of the portrait parle. But we have both seen Dr. Harris and Marie enter the beauty parlour of Madame Margot. Now, I don't mean to cast aspersions on your own good looks, Miss Kendall. They are of the sort with which no beauty parlour except Nature can compete." A girl of another type than Clare would probably have read a half dozen meanings into his sincere compliment. But then, I reflected that a man of another type than Craig could not have made the remark without expecting her to do so. There was a frankness between them which, I must confess, considerably relieved me. I was not prepared to lose Kennedy, even to Miss Kendall. She smiled. "You want me to try a course in artificial beautification, don't you?" "Yes. Walter doesn't need it, and as for me, nothing could make me a modern Adonis. Seriously, though, a man couldn't get in there, I suppose. At least that is one of the many things I want you to find out. Under the circumstances, you are the only person in whom I have confidence enough to believe that she can get at the facts there. Find out all you can about the character of the place and the people who frequent it. And if you can learn anything about that Madame Margot who runs the place, so much the better." "I'll try," she said simply. Kennedy resumed his tests of the powder in the packets which Dr. Harris had been distributing, and I endeavoured to make myself as little in the way as possible. It was not until the close of the afternoon that a taxicab drove up and deposited Miss Kendall at the door. "What luck?" greeted Kennedy eagerly, as she entered. "Do you feel thoroughly beautified?" "Don't make me smile," she replied, as she swept in with an air that would have done credit to the star in a comic opera. "I'd hate to crack or even crease the enamel on my face. I've been steamed and frozen, beaten and painted and---" "I'm sorry to have been the cause of such cruel and unusual punishment," apologized Craig. "No, indeed. Why, I enjoyed it. Let me tell you about the place." She leaned against the laboratory table, certainly an incongruous picture in her new role as contrasted with the stained and dirty background of paraphernalia of medico-legal investigation. I could not help feeling that if Clare Kendall ever had decided to go in for such things, Marie herself would have had to look sharp to her laurels. "As you enter the place," she began, "you feel a delightful warmth and there is an odour of attar of roses in the air. There are thick half-inch carpets that make walking a pleasure and dreamy Sleepy Hollow rockers that make it an impossibility. It is all very fascinating. "There are dull-green lattices, little gateways with roses, white enamel with cute little diamond panes of glass for windows, inviting bowers of artificial flowers and dim yellow lights. It makes you feel like a sybarite just to see it. It's a cosmetic Arcadia for that fundamental feminine longing for beauty. "Well, first there are the little dressing-rooms, each with a bed, a dresser and mirror, and everything in such good taste. After you leave them you go to a white, steamy room and there they bake you. It's a long process of gentle showers, hot and cold, after that, and massage. "I thought I was through. But it seems that I had only just started. There was a battery of white manicure tables, and then the hairdressers and the artists who lay on these complexions--what do you think of mine? I can't begin to tell all the secrets of the curls and puffs, and reinforcements, hygienic rolls, transformations, fluffy puffers, and all that, or of the complexions. Why, you can choose a complexion, like wall-paper or upholstery. They can make you as pale as a sickly heroine or they can make you as yellow as a bathing girl. There is nothing they can't do. I asked just for fun. I could have come out as dusky as a gipsy. "They tried electrolysis on my eyebrows, and one attendant suggested a hypodermic injection of perfume. Ever hear of that? She thought 'new mown hay' was the best to saturate the skin with. Then another suggested, as long as I had chosen this moonbeam make-up, that perhaps I'd like a couple of dimples. They could make them permanent or lasting only a few hours. I declined. But there is nothing so wild that they haven't either thought of themselves or imported from Paris or somewhere else. I heard them discussing someone who wanted odd eyes--made by pouring in certain liquids. They don't seem to care how they affect sight, hearing, skin, or health. It is decoration run mad." "How about the people there?" asked Kennedy. "Oh, I must tell you about that. There's so much to tell, I hardly know where to begin--or stop. I saw some flashy people. You know one customer attracts her friends and so on. There is every class there from the demi-monde up to actresses and really truly society. And they have things for all prices from the comparatively cheap to the most extravagant. They're very accommodating and, in a way, democratic." "Did it seem--straight?" asked Kennedy. "On the surface, yes, as far as I could judge. But I'll have to go back again for that. For instance, there was one thing that seemed queer to me. I had finished the steaming and freezing and was resting. A maid brought a tray of cigarettes, those dainty little thin ones with gilt tips. There seemed to be several kinds. I managed to try some of them. One at least I know was doped, although I only had a whiff of it. I think after they got to know you they'd serve anything from a cocktail in a teacup to the latest fads. I am sure that I saw one woman taking some veronal in her coffee." "Veronal?" commented Craig. "Then that may be where Dr. Harris comes in." "Partly, I think. I've got to find out more about what is hidden there. Once I heard a man's voice and I know it was Dr. Harris's." "Harris! Why, the elevator boy at the Montmartre said he was painting the town," I observed. "I don't believe it. I think he has all he can do keeping up with the beauty shop. You see, it is more than a massage parlour. They do real decorative surgery, as it is called. They'll engage to give you a new skin as soft and pink as a baby's. Or they will straighten a nose, or turn an ear. They have light treatment for complexions--the ruby ray, the violet ray, the phosphorescent ray. "You would laugh at the fake science that is being handed out to those gullible fools. They can get rid of freckles and superfluous hair, of course. But they'll even tell you that they can change your mouth and chin, your eyes, your cheeks. I should be positively afraid of some of their electrical appliances there. They sweat down your figure or build it up--just as you please. "Oh, no one need be plain in these days, not as long as Madame Margot's exists. That is where I think Dr. Harris comes in. He can pose as a full-fledged, blown-in-the-bottle cosmetic surgeon. I'll bet there is no limit to the agonized beautification that they can put you through if they think they can play you for a sucker." "By the way, did you see Madame Margot herself?" asked Craig. "No. I made all sorts of discreet inquiries after her, but they seemed to know nothing. The nearest I could get was a hint from one of the girls that she was away. But I'll tell you whom I think I heard, talking to the man whose voice sounded like Dr. Harris's, and that was Marie. Of course I couldn't see, but in the part of the shop that looks like a fake hospital I heard two voices and I would wager that Marie is going through some of this beautification herself. Of course she is. You remember how artificial she looked?" "Did you see anyone else?" "Oh, yes. You know the place is two doors from the Montmartre. Well, I think they have some connection with that place between them and the Montmartre. Anyhow it looks as if they did, for after I had been there a little while a girl came in, apparently from nowhere. She was the girl we saw paying money to Ike the Dropper, you remember--the one none of us recognized? There's something in that next house, and she seems to have charge of it." "Well, you have done a good day's work," complimented Kennedy. "I feel that I have made a start, anyhow," she admitted. "There is a lot yet to be learned of Margot's. You remember it was early in the day that I was there. I want to go back sometime in the afternoon or evening." "Dr. Harris is apparently the oracle on beauty," mused Kennedy. "Yes. He must make a lot of money there." "They must have some graft, though, besides the beauty parlour," went on Kennedy. "They wouldn't be giving up money to Ike the Dropper if that was all there was." "No, and that is where the doped cigarette comes in. That is why I want to go again. I imagine it's like the Montmartre. They have to know you and think you are all right before you get the real inside of the place." "I don't doubt it." "I can't go around looking like a chorus girl," remarked Miss Kendall finally, with a glance at a little mirror she carried in her bag. "I'm afraid you'll have to excuse me until I get rid of this beautification." The telephone rang sharply. As Kennedy answered, we gathered that it was Carton. A few minutes of conversation, mostly on Carton's part, followed. Kennedy hung up the receiver with an exclamation of vexation. "I'm afraid I did wrong to start anything with the portrait parle yet," he said. "Why, this thing we are investigating has so many queer turns that you hardly know whom to trust." "What do you mean?" "I don't know who could have given the thing away, but Carton says it wasn't an hour after the inquiries began about Marie that it became known in the underworld that she was being looked for in this way. Oh, they are clever, those grafters. They have all sorts of ways of keeping in touch. I suppose they remember they had one experience with the portrait parle and it has made them as wary as a burglar is over finger-prints. Carton tells me that Marie has disappeared." "I could swear I heard her or someone at Margot's," said Clare. "And Harris has disappeared. Of course you thought you overheard him, too. But you may have been mistaken." "Why?" "As nearly as Carton can find out," said Kennedy quickly, "Marie is Madame Margot herself." XV THE PHANTOM CIRCUIT "I want to go to Margot's again to-day," volunteered Miss Kendall the following morning, adding with a smile, "You see, I've got the habit. Really, though, there is a mystery about that place that fascinates me. I want to find out more about this Marie, or Margot, or whoever it was that I thought I heard there. And then those doped cigarettes interest me. You see, I haven't forgotten what you said about dope the first time we talked about Dr. Harris. They will be more free with me, too, now that I am no longer a stranger." "That is a good idea," agreed Kennedy, who was now chafing under the enforced inaction of the case. "I hope that this time they will let you into some of the secrets. There is one thing, though, I wish you'd look out for especially." "What do you mean?" she asked. "I should like to know what ways there are of communicating with the outside. You realize, of course, that it is very easy for them, if they come to suspect you, to frame up something in a place like that. There are strong-arm women as well as men, and I'm not at all sure that there may not be some men besides Dr. Harris who are acquainted with that place. At any rate Dr. Harris is unscrupulous enough himself." "I shall make it a point to observe that," she said as she left us. "I hope I'll have something to tell you when I come back." "Walter," remarked Craig as the door closed, "that is one of the gamest girls I ever knew." I looked across at him inquiringly. "Don't worry, my boy," he added, reading my expression. "She's not of the marrying kind, any more than I am." The morning passed and half of the afternoon without any word from Miss Kendall. Kennedy was plainly becoming uneasy, when a hurried footstep in the hall was followed by a more hurried opening of the door. "Let me sit down, just a minute, to collect myself," panted Miss Kendall, pressing her hands to her temples where the blue veins stood out and literally throbbed. "I'm all in." "Why, what is the matter?" asked Kennedy, placing a chair and switching on an electric fan, while he quickly found a bottle of restorative salts which was always handy for emergencies in the laboratory. "Oh--such a time as I've had! Wait--let me see whether I can recollect it in order." A few minutes later she resumed. "I went in, as before. There seemed to be quite a change in the way they treated me. I must have made a good impression the first time. A second visit seemed to have opened the way for everything. Evidently they think I am all right. "Well, I went through much the same thing as I did before, only I tried to make it not quite so elaborate, down to the point where several of us were sitting in loose robes in the lounging-room. That was the part, you know, that interested me before. "The maid came in with the cigarettes and I smoked one of the doped ones. They watch everything that you do so closely there, and the moment I smoked one they offered me another. I don't know what was in them, but I fancy there must be just a trace of opium. They made me feel exhilarated, then just a bit drowsy. I managed to make away with the second without inhaling much of the smoke, for my head was in a whirl by this time. It wasn't so much that I was afraid I couldn't take care of myself as it was that I was afraid that it would blunt the keenness of my observation and I might miss something." "Besides the cigarettes, was there anything else?" asked Craig. "Yes, indeed. I didn't see anyone there I recognized, but I heard some of them talk. One was taking a little veronal; another said something about heroin. It was high-toned hitting the pipe, if you call it that--a Turkish bath, followed by massage, and then a safe complement of anything you wanted, taken leisurely by these aristocratic dope fiends. "There was one woman there who I am sure was snuffing cocaine. She had a little gold and enamelled box like a snuff box beside her from which she would take from time to time a pinch of some white crystals and inhale it vigorously, now and then taking a little sip of a liqueur that was brought in to her." "That's the way," observed Kennedy. "There are always a considerable number of inhuman beings who are willing to make capital out of the weaknesses of others. This illicit sale of cocaine is one example. Such conditions have existed with the opium products a long time. Now it seems to be the 'coke fiend.'" "I was glad I did just as I did," resumed Clare, "because it wasn't long before I saw that the thing to do was to feign drowsiness. A maid came over to me and in a most plausible and insinuating way hinted that perhaps I might feel like resting and that if the noise in the beauty parlour annoyed me, they had the entire next house--the one next to the Montmartre, you know--which had been fitted up as a dormitory." "You didn't go?" cut in Craig immediately. "I did not. I pleaded an engagement. Why, the place is a regular dope joint." "Exactly. I suspected as much as you went along. Everything seems to have moved uptown lately, to have been veneered over to meet the fastidious second decade of the twentieth century. But underneath it all are the same old vices. I'm glad you didn't attempt to go into the next house. Anyhow, now we are certain about the character of the place. Did you notice anything about the means of communicating with the outside--the telephones, for instance?" Miss Kendall was evidently feeling much better now. "Oh, yes," she answered. "I took particular care to observe that. They have a telephone, but there is a girl who attends to it, although they don't really need one. She listens to everything. Then, too, in the other house--You remember I spoke about the girl whom we saw paying Ike the Dropper? It seems that she has a similar position at the telephone over there." "So they have two telephones," repeated Craig. "Yes." "Good. There are always likely to be some desperate characters in places like that. If we ever have anyone go into that dope joint we must have some way of keeping in touch and protecting the person." Miss Kendall had gone home for a few hours of rest after her exciting experience. Craig was idly tapping with his fingers on the broad arm of his chair. Suddenly he jumped up. "I'm going up there to look that joint over from the outside," he announced. We walked past the front of it without seeing anything in particular, then turned the corner and were on the Avenue. Kennedy paused and looked at a cheap apartment house on which was a sign, "Flats to Let." "I think I'll get the janitor to show me one of them," he said. One was on the first floor in the rear. Kennedy did not seem to be very much interested in the rent. A glance out of the window sufficed to show him that he could see the back of the Montmartre and some of the houses. It took only a minute to hire it, at least conditionally, and a bill to the janitor gave us a key. "What are you going to do?" "We can't do anything just yet, but it will be dark by the time I get over to the laboratory and back and then we can do something." That night we started prowling over the back fences down the street. Fortunately it was a very black night and Craig was careful not to use even the electric bull's-eye which he had brought over from the laboratory together with some wire and telephone instruments. As we crouched in the shadow of one of the fences, he remarked: "Just as I expected; the telephone wires run along the tops of the fences. Here's where they run into 72--that's the beauty parlour. These run into 70--that's the dope joint. Then next comes the Montmartre itself, reaching all the way back as far as the lot extends." We had come up close to the backs of the houses by this time. The shades were all drawn and the blinds were closed in both of them, so that we had really nothing to fear provided we kept quiet. Besides the back yards looked unkempt, as if no one cared much about them. Kennedy flashed the electric bull's-eye momentarily on the wires. They branched off from the back fence down the party fence to the houses, both sets on one fence. "Good!" he exclaimed. "It is better than I hoped. The two sets go on up to the first floor together, then separate. One set goes into the beauty parlour; the other into the dope joint." Craig had quietly climbed up on a shed over the basements of both the houses. He was working quickly with all the dexterity of a lineman. To two of the four wires he had attached one other. Then to two others he attached another, all the connections being made at exactly corresponding points. The next step was to lead these two newly connected wires to a window on the first floor of the house next to the Montmartre. He fastened them lightly to the closed shutter, let himself down to the yard again and we beat a slow and careful retreat to our flat. In one of the yards down near the corner, however, he paused. Here was an iron box fastened to one of the fences, a switch box or something of the sort belonging to the telephone company. To it were led all the wires from the various houses on the block and to each wire was fastened a little ticket on which was scrawled in indelible pencil the number of the house to which the wire ran. Kennedy found the two pairs that ran to 70 and 72, cut in on them in the same way that he had done before and fastened two other wires, one to each pair. This pair he led along and into the flat. "I've fixed it," he explained, "so that anyone who can get into that room on the back of the first floor of the dope joint can communicate with the outside very easily over the telephone, without being overheard, either." "How?" I asked completely mystified by the apparent simplicity of the proceeding. "I have left two wires sticking on the outside shutter of that room," he replied. "All that anyone who gets into that room has to do is to open the window softly, reach out and secure them. With them fastened to a transmitter which I have, he can talk to me in the flat around the corner and no one will ever know it." There was nothing more that we could do that night and we waited impatiently until Clare Kendall came to make her daily report in the morning. "The question is, whom are we going to get whom we can trust to go to that dope joint and explore it?" remarked Kennedy, after we had finished telling Miss Kendall about our experiences of the night before. "Carton must have someone who can take a course in beauty and dope," I replied. "Or perhaps Miss Kendall has one of her investigators whom she can trust." "If the thing gets too rough," added Craig, "whoever is in there can telephone to us, if she will only be careful first to get that back room in the 'dormitory,' as they call it. Then all we'll have to do will be to jump in there and---" "I'll do it," interrupted Clare. "No, Miss Kendall," denied Kennedy firmly. "Let me do it. There is no one whom I can trust more than myself. Besides, I know the places now." She said it with an air of quiet determination, as if she had been thinking it over ever since she returned from her visit of the day before. Kennedy and Miss Kendall faced each other for a moment. It was evident that it was against just this that he had been trying to provide. On her part it was equally evident that she had made up her mind. "Miss Kendall," said Kennedy, meeting her calm eye, "you are the most nervy detective, barring none, that it has ever been my pleasure to meet. I yield under protest." I must say that it was with a great deal of misgiving that I saw Clare enter Margot's. We had gone as far as the corner with her, had watched her go in, and then hurried into the unfurnished apartment which Craig had rented on the Avenue. As we sat on the rickety chairs which we had borrowed from the janitor under pretence of wanting to reach something, the minutes that passed seemed like hours. I wondered what had happened to the plucky girl in her devotion to the cause in which she had enlisted, and several times I could see from the expression of Craig's face that he more and more regretted that he had given in to her and had allowed her to go, instead of adhering to his original plan. From what she had told us about the two places, I tried to imagine what she was doing, but each time I ended by having an increased feeling of apprehension. Kennedy sat grimly silent with the receiver of the telephone glued to his ear, straining his hearing to catch even the faintest sound. At last his face brightened. "She's there all right," he exclaimed to me. "Managed to make them think in the beauty parlour that she was a dope fiend and pretty far gone. Insisted that she must have the back room on the first floor because she was afraid of fire. She kept the door open so that she would not miss anything, but it was a long time before she got a chance to reach out of the window and get the wires and connect them with the instruments I gave her. But it's all right now. "Yes, Miss Kendall, right here, listening to everything you get a chance to say. Only be careful. There is no use spoiling the game by trying to talk to me until you have all that you think you can obtain in the way of evidence. Don't let them think you have any means of communication with the outside or they'll go to any length to silence you. We'll be here all the time and the moment you think there is any danger, call us." Kennedy seemed visibly relieved by the message. "She says that she has found out a great deal already, but didn't dare take the time to tell it just yet," he explained. "By the way, Walter, while we are waiting, I wish you would go out and see whether there is a policeman on fixed post anywhere around here." Five minutes later when I returned, having located the nearest peg post a long block away on Broadway, Kennedy raised a warning hand. She was telephoning again. "She says that attendants come and go in her room so often that it's hard to get a chance to say anything, but she is sure that there is someone hidden there, perhaps Marie or Madame Margot, whoever she is, or it may even be Betty Blackwell. They watch very closely." "But," I asked, almost in a whisper, as if someone over there might hear me, "isn't this a very dangerous proceeding, Craig? It seems to me you are taking long chances. Suppose one of the telephone girls in either house, whom she told us keep such sharp watch over the wires, should happen to be calling up or answering a call. She would hear someone else talking over the wire and it wouldn't be difficult for her to decide who it was. Then there'd be a row." "Not a chance," smiled Kennedy. "No one except ourselves, not even Central, can hear a word of what is said over these connections I have made. This is what is called a phantom circuit." "A phantom circuit?" I repeated. "What kind of a weird thing is that?" "It is possible to superimpose another circuit over the four telephone wires of two existing circuits, making a so-called phantom line," he explained, as we waited for the next message. "It seems fantastic at first, but it is really in accordance with the laws of electricity. You use each pair of wires as if it were one wire and do not interfere in the least with them, but are perfectly independent of both. The current for the third circuit enters the two wires of one of the first circuits, divides, reunites, so to speak, at the other end, then returns through the wires of the second circuit, dividing and reuniting again, thus just balancing the two divisions of the current and not causing any effect on either of the two original circuits. Rather wonderful, isn't it?" "I should say that it was," I marvelled. "I am glad I see it actually working rather than have to believe it second hand." "It's all due to a special repeating coil of high efficiency absolutely balanced as to resistances, number of turns of wire, and so on which I have used--Yes--Miss Kendall--we are here. Now please don't let things go on too far. At the first sign of danger, call. We can get in all right. You have the evidence now that will hold in any court as far as closing up that joint goes, and I'll take a chance of breaking into--well, Hades, to get to you. Good-bye. "I guess it is Hades there," he resumed to me. "She has just telephoned that one of the dope fiends upstairs--a man, so that you see they admit both men and women there, after all--had become violent and Harris had to be called to quiet him before he ran amuck. She said she was absolutely sure, this time at least, that it was Harris. As I was saying about this phantom circuit, it is used a good deal now. Sometimes they superimpose a telephone conversation over the proper arrangement of telegraph messages and vice versa. "What's that?" cried Craig, suddenly breaking off. "They heard you talking that last time, and you have locked the door against them? They are battering it down? Move something heavy, if you can, up against it--the bureau, anything to brace it. We'll be there directly. Come on, Walter. There isn't time to get around Broadway for that fixed post cop. We must do it ourselves. Hurry." Craig dashed breathlessly out on the street. I followed closely. "Hurry," he panted. "Those people haven't any use for anyone that they think will snitch on them." As we turned the corner, we ran squarely into a sergeant slowly going his rounds with eyes conveniently closed to what he was paid not to see. Kennedy stopped and grabbed his arm. "There's a girl up here in 72 who is being mistreated," he cried. "Come. You must help us get her out." "Aw, g'wan. Whatyer givin' us? 72? That's a residence." "Say--look here. I've got your number. You'll be up on the most serious charges of your whole career if you don't act on the information I have. All of Ike the Dropper's money'll go for attorney's fees and someone will land in Sing Sing. Now, come!" We had gained the steps of the house. Outside all was dark, blank, and bare. There was every evidence of the most excessive outward order and decency--not a sign of the conflict that was raging within. Before the policeman could pull the bell, which would have been a first warning of trouble to the inmates, Kennedy had jumped from the high stoop to a narrow balcony running along the front windows of the first story, had smashed the glass into splinters with a heavy object which he had carried concealed under his coat, and was engaged in a herculean effort to wrench apart some iron bars which had been carefully concealed behind the discreetly drawn shades. As one yielded, he panted, "No use to try the door. The grill work inside guards that too well. There goes another." Inside now we could hear cries that told us that the whole house was roused, that even the worst of the drug fiends had come at least partly to his senses and begun to realize his peril. From Margot's beauty parlour a couple of girls and a man staggered forth in a vain effort to seem to leave quietly. "Close that place, too, officer," cried Kennedy to the now astounded policeman. "We'll attend to this house." The sergeant slowly lumbered across in time to let two more couples escape. It was evident that he hated the job; indeed, would have arrested Kennedy in the old days before Carton had thrown such a scare into the grafters. But Kennedy's assurance had flabbergasted him and he obeyed. Another bar yielded, and another. Together we squeezed in and found ourselves in a dark front parlour. There was nothing to distinguish it from any ordinary reception room in the blackness. Hurried footsteps were heard as if several people were retreating into the next house. Down the hall we hastened to the back room. A second we listened. All was silent. Was Clare safe? It looked ominous. Still the door, partly battered in, was closed. "Miss Kendall!" called Craig, bending down close to the door. "Is it you, Professor Kennedy?" came back a faint voice from the other side. "Yes. Are you all right?" There was no answer, but she was evidently tugging at something which appeared to be a heavy piece of furniture braced against the door. At last the bolt was slipped back, and there in the doorway she swayed, half exhausted but safe. "Yes, all right," murmured Clare, bracing herself against the chiffonier which she had moved away from the door, "just a little shaky from the drugs--but all right. Don't bother about me, now. I can take care of myself. I'll feel better in a minute. Upstairs--that is where I think that woman is. Please, please don't--I'm all right--truly. Upstairs." Kennedy had taken her gently by the arm and she sank down in an easy chair. "Please hurry," she implored. "You may be too late." She had risen again in spite of us and was out in the lower hall. We could hear a footstep on the stairs. "There she goes, the woman who has been hiding up there, Madame--" Clare cut the words short. A woman had hastily descended the steps, evidently seeing her opportunity to escape while we were in the back of the house. She had reached the street door, which now was open, and the flaming arc light in front of the house shone brightly on her. I looked, expecting to see our dark-haired, olive-skinned Marie. I stared in amazement. Instead, this woman was fair, her hair was flaxen, her figure more slim, even her features were different. She was a stranger. I could not recollect ever having seen her. Again I strained my eyes, thinking it might be Betty Blackwell at last, but this woman bore no resemblance apparently to her. She looked older, more mature. In my haste I noted that she had a bandage about her face, as if she had been injured recently, for there seemed to be blood on it where it had worked itself loose in her flight. She gave one glance at us, and quickened her pace at seeing us so close. The bandage, already loose, slipped off her face and fell to the floor. Still she did not seem other than a stranger to me, though I had a half-formed notion that I had seen that face somewhere before. She did not stop to pick the bandage up. She had gained the door and was down the front step on the sidewalk before we could stop her. Taxicabs in droves seemed to have collected, like buzzards over a dead body. They were doing a thriving business carrying away those who sought to escape. Into one by which a man was waiting in the shadow the woman hurried. The man looked for all the world like Dr. Harris. An instant later the chauffeur was gone. The policeman had the front door of Madame Margot's covered all right, so efficiently that he was neglecting everything else. From the basement now and then a scurrying figure catapulted itself out and was lost in the curious crowd that always collects at any time of day or night on a New York street when there is any excitement. "It is of no use to expect to capture anyone now," exclaimed Craig, as we hurried back into the dope joint. "I hardly expected to do it. All I panted was to protect Miss Kendall. But we have the evidence against this joint that will close it for good." He stooped and picked up the bandage. "I think I'll keep that," he remarked thoughtfully. "I wonder what that blonde woman wore that for?" "She MUST be up there," reiterated Clare, who had followed us. "I heard them talking, it seemed to me only the moment before I heard you in the hall." The excitement seemed now to have the effect of quieting her unstrung nerves and carrying her through. "Let us go upstairs," said Kennedy. From room to room we hurried in the darkness, lighting the lights. They were all empty, yet each one gave its mute testimony to the character of its use and its former occupants. There were opium lay-outs with pipes, lamps, yen haucks, and other paraphernalia in some. In others had been cocaine snuffers. There seemed to be everything for drug users of every kind. At last in a small room in front on the top floor we came upon a girl, half insensible from a drug. She was vainly trying to make herself presentable for the street, ramblingly talking to herself in the meantime. Again my hopes rose that we had found either the mysterious Marie Margot or Betty Blackwell. A second glance caused us all to pause in surprise and disappointment. It was the Titian-haired girl from the Montmartre office. Miss Kendall, recovering from the effects of the drugs which she had been compelled to take in her heroic attempt to get at the dope joint, was endeavouring to quiet the girl from the Montmartre, who, now vaguely recollecting us, seemed to realize that something had gone wrong and was trembling and crying pitifully. "What's the matter with her?" I asked. "Chloral," replied Miss Kendall in a low voice aside. "I suppose she has had a wild night which she has followed by chloral to quiet her nerves, with little effect. Didn't you ever see them? They will go into a drug store in this part of the city where such things are sold, weak, shaky, nervous wrecks. The clerk will sell them the stuff and they will retire for a moment into the telephone booth. Sometimes they will come out looking as though they had never felt a moment's effect from their wild debauches. But there are other times when they are too weakened to get over it so quickly. That is her case, poor girl." The soothing hand which she laid on the girl's throbbing head was quite in contrast with the manner in which I recalled her to have spoken of the girl when first we saw her at the Montmartre. She must have seen the look of surprise on my face. "I can't condemn these girls too strongly when I see them themselves," she remarked. "It would be so easy for them to stop and lead a decent life, if they only would forget the white lights and the gay life that allures them. It is when they are so down and out that I long to give them a hand to help them up again and show them how foolish it is to make slaves of themselves." "Call a cab, Walter," said Kennedy, who had been observing the girl closely. "There is nothing more that we can expect to accomplish here. Everybody has escaped by this time. But we must get this poor girl in a private hospital or sanitarium where she can recover." Clare had disappeared. A moment later she returned from the room she had had downstairs with her hat on. "I'm going with her," she announced simply. "What--you, Miss Kendall?" "Yes. If a girl ever needed a friend, it is this girl now. There is nothing I can do for the moment. I will take care of her in my apartment until she is herself again." The girl seemed to half understand, and to be grateful to Clare. Kennedy watched her hovering over the drug victim without attempting to express the admiration which he felt. Just as the cab was announced, he drew Miss Kendall aside. "You're a trump," he said frankly. "Most people would pass by on the other side from such as she is." They talked for a moment as to the best place to go, then decided on a quiet little place uptown where convalescents were taken in. "I think you can still be working on the case, if you care to do so," suggested Craig as Miss Kendall and her charge were leaving. "How?" she asked. "When you get her to this sanitarium, try to be with her as much as you can. I think if anyone can get anything out of her, you can. Remember it is more than this girl's rescue that is at stake. If she can be got to talk she may prove an important link toward piecing together the solution of the mystery of Betty Blackwell. She must know many of the inside secrets of the Montmartre," he added significantly. They had gone, and Craig and I had started to go also when we came across a negro caretaker who seemed to have stuck by the place during all the excitement. "Do you know that girl who just went out?" asked Craig. "No, sah," she replied glibly. "Look here," demanded Craig, facing her. "You know better than that. She has been here before, and you know it. I've a good mind to have you held for being in charge of this place. If I do, all the Marie Margots and Ike the Droppers can't get you out again." The negress seemed to understand that this was no ordinary raid. "Who is she?" demanded Craig. "I dunno, sah. She come from next door." "I know she did. She's the girl in the office of the Montmartre. Now, you know her. What is her name?" The negress seemed to consider a moment, then quickly answered, "Dey always calls her Miss Sybil here, sah, Sybil Seymour, sah." "Thank you. I knew you had some name for her. Come, Walter. This is over for the present. A raid without arrests, too! It will be all over town in half an hour. If we are going to do anything it must be done quickly." We called on Carton and lost no time in having the men he could spare placed in watching the railroads and steamship lines to prevent if we could any of the gang from getting out of the city that way. It was a night of hard work with no results. I began to wonder whether they might not have escaped finally after all. There seemed to be no trace. Harris had disappeared, there was no clue to Marie Margot, no trace of the new blonde woman, not a syllable yet about Betty Blackwell. XVI THE SANITARIUM "It seems as if the forces of Dorgan are demoralized," I remarked the afternoon after the raid on Margot's. "We have them on the run--that's true," agreed Kennedy, "but there's plenty of fight in them, yet. We're not through, by any means." Still, the lightning swiftness of Carton's attack had taken their breath away, temporarily, at least. Already he had started proceedings to disbar Kahn, as well as to prosecute him in the courts. According to the reports that came to us Murtha himself seemed dazed at the blow that had fallen. Some of our informants asserted that he was drinking heavily; others denied it. Whatever it was, however, Murtha was changed. As for Dorgan, he was never much in the limelight anyhow and was less so now than ever. He preferred to work through others, while he himself kept in the background. He had never held any but a minor office, and that in the beginning of his career. Interviews and photographs he eschewed as if forbidden by his political religion. Since the discovery of the detectaphone in his suite at Gastron's he had had his rooms thoroughly overhauled, lest by any chance there might be another of the magic little instruments concealed in the very walls, and having satisfied himself that there was not, he instituted a watch of private detectives to prevent a repetition of the unfortunate incident. Whoever it was who had obtained the Black Book was keeping very quiet about it, and I imagined that it was being held up as a sort of sword of Damocles, dangling over his head, until such time as its possessor chose to strike the final blow. Of course, we did not and could not know what was going on behind the scenes with the Silent Boss, what drama was being enacted between Dorgan and the Wall Street group, headed by Langhorne. Langhorne himself was inscrutable. I had heard that Dorgan had once in an unguarded moment expressed a derogatory opinion of the social leanings of Langhorne. But that was in the days before Dorgan had acquired a country place on Long Island and a taste for golf and expensive motors. Now, in his way, Dorgan was quite as fastidious as any of those he had once affected to despise. It amused Langhorne. But it had not furthered his ambitions of being taken into the inner circle of Dorgan's confidence. Hence, I inferred, this bitter internecine strife within the organization itself. Whatever was brewing inside the organization, I felt that we should soon know, for this was the day on which Justice Pomeroy had announced he would sentence Dopey Jack. It was a very different sort of crowd that overflowed the courtroom that morning from that which had so boldly flocked to the trial as if it were to make a Roman holiday of justice. The very tone was different. There was a tense look on many a face, as if the owner were asking himself the question, "What are we coming to? If this can happen to Dopey Jack, what might not happen to me?" Even the lawyers were changed. Kahn, as a result of the proceedings that Carton had instituted, had yielded the case to another, perhaps no better than himself, but wiser, after the fact. Instead of demanding anything, as a sort of prescriptive right, the new attorney actually adopted the unheard of measure of appealing to the clemency of the court. The shades of all the previous bosses and gangsters must have turned in disgust at the unwonted sight. But certain it was that no one could see the relaxation of a muscle on the face of Justice Pomeroy as the lawyer proceeded with his specious plea. He heard Carton, also, in the same impassive manner, as in a few brief and pointed sentences he ripped apart the sophistries of his opponent. The spectators fairly held their breath as the prisoner now stood before the tribune of justice. "Jack Rubano," he began impressively, "you have been convicted by twelve of your peers--so the law looks on them, although the fact is that any honest man is immeasurably your superior. Even before that, Rubano, the District Attorney having looked into all the facts surrounding this charge had come to the conclusion that the evidence was sufficiently strong to convict you. You were convicted in his mind. In my mind, of course, there could be no prejudgment. But now that a jury has found you guilty, I may say that you have a record that is more than enough to disgrace a man twice your age. True, you have never been punished. But this is not the time or place for me to criticise my colleagues on the bench for letting you off. Others of your associates have served terms in prison for things no whit worse than you have done repeatedly. I shall be glad to meet some of them at this bar in the near future." The justice paused, then extended a long, lean accusatory finger out from the rostrum at the gangster. "Rubano," he concluded, "your crime is particularly heinous--debauching the very foundations of the state--the elections. I sentence you to not less than three nor more than five years in State's prison, at hard labour." There was an audible gasp in the big courtroom, as the judge snapped shut his square jaw, bull-dog fashion. It was as though he had snapped the backbone of the System. The prisoner was hurried from the room before there was a chance for a demonstration. It was unnecessary, however. It seemed as if all the jaunty bravado of the underworld was gone out of it. Slowly the crowd filed out, whispering. Dopey Jack, Murtha's right-hand man, had been sentenced to State's prison! Outside the courtroom Carton received an ovation. As quickly as he could, he escaped from the newspapermen, and Kennedy was the first to grasp his hand. But the most pleasing congratulation came from Miss Ashton, who had dropped in with two or three friends from the Reform League. "I'm so glad, Mr. Carton--for your sake," she added very prettily, with just a trace of heightened colour in her cheeks and eyes that showed her sincere pleasure at the outcome of the case. "And then, too," she went on, "it may have some bearing on the case of that girl who has disappeared. So far, no one seems to have been able to find a trace of her. She just seems to have dropped out as if she had been spirited away." "We must find her," returned Carton, thanking her for her good wishes in a manner which he had done to none of the rest of us, and in fact forgetful now that any of us were about. "I shall start right in on Dopey Jack to see if I can get anything out of him, although I don't think he is one that will prove a squealer in any way. I hope we can have something to report soon." Others were pressing around him and Miss Ashton moved away, although I thought his handshakes were perhaps a little less cordial after she had gone. I turned once to survey the crowd and down the gallery, near a pillar I saw Langhorne, his eyes turned fixedly in our direction, and a deep scowl on his face. Evidently he had no relish for the proceedings, at least that part in which Carton had just figured, whatever his personal feelings may have been toward the culprit. A moment later he saw me looking at him, turned abruptly and walked toward the stone staircase that led down to the main floor. But I could not get that scowl out of my mind as I watched his tall, erect figure stalking away. Neither Murtha, nor, of course, Dorgan, were there, though I knew that they had many emissaries present who would report to them every detail of what had happened, down perhaps to the congratulations of Miss Ashton. Somehow, I could not get out of my head a feeling that she would afford them, in some way, a point of attack on Carton and that the unscrupulous organization would stop at nothing in order to save its own life and ruin his. Carton had not only his work at the District Attorney's office to direct, but some things to clear up at the Reform League headquarters, as well as a campaign speech to make. "I'm afraid I shan't be able to see much of you, to-day," he apologized to Kennedy, "but you're going to Miss Ashton's suffrage evening and dance, aren't you?" "I should like to go," temporized Kennedy. Carton glanced about to see whether there was anyone in earshot. "I think you had better go," he added. "She has secured a promise from Langhorne to be there, as well as several of the organization leaders. It is a thoroughly non-partisan affair--and she can get them all together. You know the organization is being educated. When people of the prominence of the Ashtons take up suffrage and make special requests to have certain persons come to a thing like that, they can hardly refuse. In fact, no one commits himself to anything by being present, whereas, absence might mean hostility, and there are lots of the women in the organization that believe in suffrage, now. Yes, we'd better go. It will be a chance to observe some people we want to watch." "We'll go," agreed Kennedy. "Can't we all go together?" "Surely," replied Carton, gratified, I could see, by having succeeded in swelling the crowd that would be present and thus adding to the success of Miss Ashton's affair. "Drop into the office here, and I'll be ready. Good-bye--and thanks for your aid, both of you." We left the Criminal Courts Building with the crowd that was slowly dispersing, still talking over the unexpected and unprecedented end of the trial. As we paused on the broad flight of steps that led down to the street on this side, Kennedy jogged my elbow, and, following his eyes, I saw a woman, apparently alone, just stepping into a town car at the curb. There was something familiar about her, but her face was turned from me and I could not quite place her. "Mrs. Ogleby," Kennedy remarked. "I didn't see her in the courtroom. She must have been there, though, or perhaps outside in the corridor. Evidently she felt some interest in the outcome of the case." He had caught just a glimpse of her face and now that he pronounced her name I recognized her, though I should not have otherwise. The car drove off with the rattle of the changing gears into high speed, before we had a chance to determine whether it was otherwise empty or not. "Why was she here?" I asked. Kennedy shook his head, but did not venture a reply to the question that was in his own mind. I felt that it must have something to do with her fears regarding the Black Book. Had she, too, surmised that Murtha had employed his henchman, Dopey Jack, to recover the book from Langhorne? Had she feared that Dopey Jack might in some moment of heat, for revenge, drop some hint of the robbery--whether it had been really successful or not? It was my turn to call Kennedy's attention to something, now, for standing sidewise as I was, I could see the angles of the building back of him. "Don't turn--yet," I cautioned, "but just around the corner back of you, Langhorne is standing. Evidently he has been watching Mrs. Ogleby, too." Kennedy drew a cigarette from his case, tried to light it, let the match go out, and then as if to shield himself from the wind, stepped back and turned. Langhorne, however, had seen us, and an instant later had disappeared. Without a word further Kennedy led the way around the corner to the subway and we started uptown, I knew this time, for the laboratory. He made no comment on the case, but I knew he had in mind some plan or other for the next move and that it would probably involve something at the suffrage meeting at Miss Ashton's that evening. During the rest of the day, Craig was busy testing and re-testing a peculiar piece of apparatus, while now and then he would despatch me on various errands which I knew were more as an outlet for my excitement than of any practical importance. The apparatus, as far as I could make it out, consisted of a simple little oaken box, oblong in shape, in the face of which were two square little holes with side walls of cedar, converging pyramid-like in the interior of the box and ending in what looked to be little round black discs. I had just returned with a hundred feet or so of the best silk-covered flexible wire, when he had evidently completed his work. Two of the boxes were already wrapped up. I started to show him the wire, but after a glance he accepted it as exactly what he had wanted and made it into a smaller package, which he handed to me. "I think we might be journeying down to Carton's office," he added, looking impatiently at his watch. It was still early and we did not hurry. Carton, however, was waiting for us anxiously. "I've called you at the laboratory and the apartment--all over," he cried. "Where have you been?" "Just on the way down," returned Kennedy. "Why, what has happened?" "Then you haven't heard it?" asked Carton excitedly, without waiting for Craig's answer. "Murtha has been committed to a sanitarium." Kennedy and I stared at him. "Pat Murtha," ejaculated Craig, "in a sanitarium?" "Exactly. Paresis--they say--absolutely irresponsible." Coming as it did as a climax to the quick and unexpected succession of events of the past few days, it was no wonder that it seemed impossible. What did it mean? Was it merely a sham? Or was it a result of his excesses? Or had Carton's relentless pursuit, the raid of Margot's, and the conviction of Dopey Jack, driven the Smiling Boss really insane? XVII THE SOCIETY SCANDAL Nothing else was talked about at the suffrage reception at Miss Ashton's that evening, not even suffrage, as much as the strange fate that seemed to have befallen Murtha. And, as usual with an event like that, stories of all sorts, even the wildest improbabilities, were current. Some even went so far as to insinuate that Dorgan had purposely quickened the pace of life for Murtha by the dinners at Gastron's in order to get him out of the way, fearing that with his power within the organization Murtha might become a serious rival to himself. Whether there was any truth in the rumour or not, it was certain that Dorgan was of the stamp that could brook no rivals. In fact, that had been at the bottom of the warfare between himself and Langhorne. Certain also was it that the dinners and conferences at the now famous suite of the Silent Boss were reputed to have been often verging on, if not actually crossing, the line of the scandalous. Miss Ashton's guests assembled in force, coming from all classes of society, all parties in politics, and all religions. Her object had been to show that, although she personally was working with the Reform League, suffrage itself was a broad general issue. The two or three hundred guests of the evening surely demonstrated it and testified to the popularity of Miss Ashton personally, as well. She had planned to hold the meeting in the big drawing-room of the Ashton mansion, but the audience overflowed into the library and other rooms. As the people assembled, it was interesting to see how for the moment at least they threw off the bitterness of the political campaign and met each other on what might be called neutral ground. Dorgan himself had been invited, but, in accordance with his custom of never appearing in public if he could help it, did not come. Langhorne was present, however, and I saw him once talking to a group of labour union leaders and later to Justice Pomeroy, an evidence of how successful the meeting was in hiding, if not burying, the hatchet. Carton, naturally, was the lion of the evening, though he tried hard to keep in the background. I was amused to see his efforts. In fleeing from the congratulations of some of his own and Miss Ashton's society friends, he would run into a group of newspaper men and women who were lying in wait for him. Shaking himself loose from them would result in finding himself the centre of an enthusiastic crowd of Reform Leaguers. Mrs. Ogleby was there, also, and both Kennedy and I watched her curiously. I wondered whether she might not feel just a little relieved to think that Murtha was seemingly out of the way for the present. Her knowledge of the Black Book which had first given the tip to Carton had always been a mystery to Kennedy and was one of the problems which I knew he would like to solve to-night. She was keenly observant of Carton, which led us to suppose that she had not yet got out of her mind the idea that somehow it was he who had been responsible for the detectaphone record which so many of those present were struggling to obtain. Though Langhorne studiously avoided her, I noticed that each kept an eye on the other, and I felt that there was something common to both of them. It was with an unexpressed air of relief to several members of the party that Miss Ashton at last rapped for order and after a short, pithy, pointed speech of introduction presented the several speakers of the evening. It was, like the audience, a well-balanced programme, which showed the tactfulness and political acumen of Miss Ashton. I shall pass over the speeches, however, as they had no direct bearing on the mystery which Kennedy and I found so engrossing. The meeting had been cleverly planned so that in spite of its accomplishing much for the propaganda work of the "cause," it did not become tiresome and the speaking was followed by the entrance of one of the best little orchestras for dance music in the city. Instantly, the scene transformed itself from a suffrage meeting to a social function that was unique. Leaders of the smart set rubbed elbows, and seemed to enjoy it, with working girls and agitators. Conservative and radical, millionaire and muckraker succumbed to the spell of the Ashton hospitality and the lure of the new dances. It was a novel experience for all, a levelling-up of society, as contrasted to some of the levelling-down that we had recently seen. Kennedy and I, having no mood as things stood for the festivities, drew aside and watched the kaleidoscopic whirl of the dancers. Across from us was a wide doorway that opened into a spacious conservatory, a nook of tropical and temperate beauty. Several couples had wandered in there to rest and, as the orchestra struck up something new that seemed to have the "punch" to its timeful measures, they gradually rejoined the dancers. It had evidently suggested an idea to Kennedy, for a moment later he led me toward the coat room and uncovered the package which he had brought consisting of the two oaken boxes I had seen him adjusting in the laboratory. We managed to reach the conservatory and found in a corner a veritable bower with a wide rustic seat under some palms. Quickly Kennedy deposited in the shadow of one of them an oaken box, sticking into it the plugs on the ends of the wires that I had brought. It was an easy matter here in the dim half light to conceal the wire behind the plants and a moment later he tossed the end through a swinging window in the glass and closed the window. Casually we edged our way out among the dancers and around to the room into which he had thrown the wire. It was a breakfast room, I think, but at any rate we could not remain there for it was quite easy to see into it through the crystal walls of the conservatory. There was, however, what seemed to be a little pantry at the other end, and to this Kennedy deftly led the wires and then plugged them in on the other oaken box. He turned a lever. Instantly from the wizard-like little box issued forth the strains of the dance music of the orchestra and the rhythmic shuffle of feet. Now and then a merry laugh or a snatch of gay conversation floated in to us. Though we were effectually cut off from both sight and hearing in the pantry, it was as though we had been sitting on the rustic bench in the conservatory. "What is it?" I asked in amazement, gazing at the wonderful little instrument before us. "A vocaphone," he explained, moving the switch and cutting off the sound instantly, "an improved detectaphone--something that can be used both in practical business, professional, and home affairs as a loud speaking telephone, and, as I expect to use it here, for special cases of detective work. You remember the detectaphone instruments which we have used?" Indeed I did. It had helped us out of several very tight situations--and seemed now to have been used to get the organization into a very tight political place. "Well, the vocaphone," went on Kennedy, "does even more than the detectaphone. You see, it talks right out. Those little apertures in the face act like megaphone horns increasing the volume of sound." He indicated the switch with his finger and then another point to which it could be moved. "Besides," he went on enthusiastically, "this machine talks both ways. I have only to turn the switch to that point and a voice will speak out in the conservatory just as if we were there instead of talking here." He turned the switch so that it carried the sounds only in our direction. The last strains of the dance music were being followed by the hearty applause of the dancers. As the encore struck up again, a voice, almost as if it were in the little room alongside us, said, "Why, hello, Maty, why aren't you dancing?" There was an unmistakable air of familiarity about it and about the reply, "Why aren't you, Hartley?" "Because I've been looking for a chance to have a quiet word with you," the man rejoined. "Langhorne and Mrs. Ogleby," cried Craig excitedly. "Sh!" I cautioned, "they might hear us." He laughed. "Not unless I turn the switch further." "I saw you down at the Criminal Courts Building this morning," went on the man, "but you didn't see me. What did you think of Carton?" I fancied there was a trace of sarcasm or jealousy in his tone. At any rate, woman-like, she did not answer that question, but went on to the one which it implied. "I didn't go to see Carton. He is nothing to me, has not been for months. I was only amusing myself when I knew him--leading him on, playing with him, then." She paused, then turned the attack on him. "What did you think of Miss Ashton? You thought I didn't see you, but you hardly took your eyes off her while I was in the hallway waiting to hear the verdict." It was Langhorne's turn to defend himself. "It wasn't so much Margaret Ashton as that fellow Carton I was watching," he answered hastily. "Then you--you haven't forgotten poor little me?" she inquired with a sincere plaintiveness in her voice. "Mary," he said, lowering his voice, "I have tried to forget you--tried, because I had no right to remember you in the old way--not while you and Martin remained together. Margaret and I had always been friends--but I think Carton and this sort of thing,"--he waved his hand I imagined at the suffrage dancers--"have brought us to the parting of the ways. Perhaps it is better. I'm not so sure that it isn't best." "And yet," she said slowly, "you are piqued--piqued that another should have won where you failed--even if the prize isn't just what you might wish." Langhorne assented by silence. "Hartley," she went on at length, "you said a moment ago you had tried to forget me--" "But can't," he cut in with almost passionate fierceness. "That was what hurt me when I--er--heard that you had gone with Murtha to that dinner of Dorgan's. I couldn't help trying to warn you of it. I know Martin neglects you. But I was mad--mad clean through when I saw you playing with Carton a few months ago. I don't know anything about it--don't want to. Maybe he was innocent and you were tempting him. I don't care. It angered me--angered me worse than ever when I saw later that he was winning with Margaret Ashton. Everywhere, he seemed to be crossing my trail, to be my nemesis. I--I wish I was Dorgan--I wish I could fight." Langhorne checked himself before he said too much. As it was I saw that it had been he who had told Mrs. Ogleby that the Black Book existed. He had not told her that he had made it, if in fact he had, and she had let the thing out, never thinking Langhorne had been the eavesdropper, but supposing it must be Carton. "Why--why did you go to that dinner with Murtha?" he asked finally, with a trace of reproach in his tone. "Why? Why not?" she answered defiantly. "What do I care about Martin? Why should I not have my--my freedom, too? I went because it was wild, unconventional, perhaps wrong. I felt that way. If--if I had felt that you cared--perhaps--I could have been--more discreet." "I do care," he blurted out. "I--I only wish I had known you as well as I do now--before you married--that's all." "Is there no way to correct the mistake?" she asked softly. "Must marriage end all--all happiness?" Langhorne said nothing, but I could almost hear his breathing over the vocaphone, which picked up and magnified even whispers. "Mary," he said in a deep, passionate voice, "I--I will defend you--from this Murtha thing--if it ever gets out. I know it is always on your mind--that you couldn't keep away from that trial for fear that Carton, or Murtha, or SOMEBODY might say something by chance or drop some hint about it. Trust me." "Then we can be--friends?" "Lovers!" he cried fiercely. There was a half-smothered exclamation over the faithful little vocaphone, a little flurried rustle of silk and a long, passionate sigh. "Hartley," she whispered. "What is it, Mary?" he asked tensely. "We must be careful. Carton MUST be defeated. He must not have the power--to use that--record." "No," ground out Langhorne. "Wait--he shall not. By the way, aren't those orchids gorgeous?" The encore had ceased and over the vocaphone we could hear gaily chatting couples wandering into the conservatory. The two conspirators rose and parted silently, without exciting suspicion. For several minutes we listened to snatches of the usual vapid chatter that dancing seems to induce. Then the orchestra blared forth with another of the seductive popular pieces. Kennedy and I looked at each other, amazed. From the underworld up to the smart set, the trail of graft was the same, debauching and blunting all that it touched. Here we saw the making of a full-fledged scandal in one of the highest circles. We had scarcely recovered from our surprise at the startling disclosures of the vocaphone, when we heard two voices again above the music, two men this time. "What--you here?" inquired a voice which we recognized immediately as that of Langhorne. "Yes," replied the other voice, evidently of a young man. "I came in with the swells to keep my eye peeled on what was going on." The voice itself was unfamiliar, yet it had a tough accent which denoted infallibly the section of the city where it was acquired. It was one of the gangsters. "What's up, Ike?" demanded Langhorne suspiciously. Craig looked at me significantly. It was Ike the Dropper! The other lowered his voice. "I don't mind telling you, Mr. Langhorne. You're in the organization and we ain't got no grudge against you. It's Carton." "Carton?" repeated Langhorne, and one could feel the expectant catch in his breath, as he added quickly: "You mean you fellows are going to try to get him right?" "Bet your life," swaggered Ike, believing himself safe. "How?" The gangster hesitated, then reassured by Langhorne, said: "He's ordered a taxicab. We got it for him--a driver who is a right guy and'll drive him down where there's a bunch of the fellows. They ain't goner do nothing serious--but--well, he won't campaign much from a hospital cot," he added sagely. "Say--here he comes now with that girl. I better beat it." Langhorne also managed to get away apparently, or else Carton and Miss Ashton were too engrossed in one another to notice him, for we heard no word of greeting. A moment later Carton's and Miss Ashton's voices were audible. "Must you go?" she was saying. "I'm afraid so," he apologized. "I've a speech to prepare for to-morrow and I've had several hard days. It's been a splendid evening, Miss Ashton--splendid. I've enjoyed it ever so much and I think it has accomplished more than a hundred meetings--besides the publicity it will get for the cause. Shall I see you to-morrow at headquarters?" "I shall make it a point to drop in," she answered in a tone as unmistakable. "Mr. Carton--your cab is waiting, sir," announced a servant with an apology for intruding. "At the side entrance, sir, so that you can get away quietly, sir." Carton thanked him. I looked at Kennedy anxiously. If Carton slipped away in this fashion before we could warn him, what might not happen? We could hardly expect to get around and through the press of the dancers in time. "I hate to go, Miss Ashton," he was adding. "I'd stay--if I saw any prospect of the others going. But--you see--this is the first time to-night--that I've had a word with you--alone." It was not only an emergency, but there were limits to Kennedy's eavesdropping propensities, and spying on Carton's love affairs was quite another thing from Langhorne's. Quickly Craig turned the lever all the way over. "Carton--Miss Ashton--this is Kennedy," he called. "Back of the big palm you'll find a vocaphone. Don't take that cab! They are going to stick you up. Wait--I'll explain all in a moment!" XVIII THE WALL STREET WOLF It was a startled couple that we found when we reached the conservatory. As we made our hasty explanation, Carton overwhelmed us with thanks for the prompt and effective manner in which Kennedy had saved him from the machinations of the defeated gangsters. Miss Ashton, who would have kept her nerves under control throughout any emergency, actually turned pale as she learned of the danger that had been so narrowly averted. I am sure that her feelings, which she made no effort to conceal, must have been such as to reassure Carton if he had still any doubt on that score. The delay in his coming out, however, had been just enough to arouse suspicion, and by the time that we reached the side entrance to the house both Ike and the night-hawk taxicab which had evidently been drafted into service had disappeared, leaving no clue. The result of the discovery over the vocaphone was that none of us left Miss Ashton's until much later than we had expected. Langhorne, apparently, had gone shortly after he left the conservatory the last time, and Mrs. Ogleby had preceded him. When at last we managed to convince Miss Ashton that it was perfectly safe for Carton to go, nothing would suffice except that we should accompany him as a sort of bodyguard to his home. We did so, without encountering any adventure more thrilling than seeing an argument between a policeman and a late reveller. "I can't thank you fellows too much," complimented Carton as we left him. "I was hunting around for you, but I thought you had found a suffrage meeting too slow and had gone." "On the contrary," returned Kennedy, equivocally, "we found it far from slow." Carton did not appreciate the tenor of the remark and Craig was not disposed to enlighten him. "What do you suppose Mrs. Ogleby meant in her references to Carton?" mused Kennedy when we reached our own apartment. "I can't say," I replied, "unless before he came to really know Miss Ashton, they were intimate." Kennedy shook his head. "Why will men in a public capacity get mixed up with women of the adventuress type like that, even innocently?" he ruminated. "Mark my words, she or someone else will make trouble for him before we get through." It was a thought that had lately been in my own mind, for we had had several hints of that nature. Kennedy said no more, but he had started my mind on a train of speculative thought. I could not imagine that a woman of Mrs. Ogleby's type could ever have really appealed to Carton, but that did not preclude the possibility that some unscrupulous person might make use of the intimacy for base purposes. Then, too, there was the threat that I had heard agreed on by both Langhorne and herself over the vocaphone. What would be the next step of the organization now in its sworn warfare on Carton, I could not imagine. But we did not have long to wait. Early the following forenoon an urgent message came to Kennedy from Carton to meet him at his office. "Kennedy," he said, "I don't know how to thank you for the many times you have pulled me through, and I'm almost ashamed to keep on calling on you." "It's a big fight," hastened Craig. "You have opponents who know the game in its every crooked turn. If I can be only a small cog on a wheel that crushes them, I shall be only too glad. Your face tells me that something particularly unpleasant has happened." "It has," admitted Carton, smoothing out some of the wrinkles at the mere sight of Craig. He paused a moment, as if he were himself in doubt as to just what the trouble was. "Someone has been impersonating me over the telephone," he began. "All day long there have been reports coming into my office asking me whether it was true that I had agreed to accept the offer of Dorgan that Murtha made, you know,--that is, practically to let up on the organization if they would let up on me." "Yes," prompted Kennedy, "but, impersonation--what do you mean by that?" "Why, early to-day someone called me up, said he was Dorgan, and asked if I would have any objection to meeting him. I said I would meet him--only it would do no good. Then, apparently, the same person called up Dorgan and said he was myself, asking if he had any objection to meeting me. Dorgan said he'd see. Whoever it was, he almost succeeded in bringing about the fool thing--would have done it, if I hadn't got wise to the fact that there was something funny about it. I called up Dorgan. He said he'd meet me, as long as I had approached him first. I said I hadn't. We swore a little and called the fake meeting off. But it was too late. It got into the papers. Now, you'd think it wouldn't make any difference to either of us. It doesn't to him. People will think he tried to slip one over on ME. But it does make a difference to me. People will think I'm trying to sell out." Carton showed plainly his vexation at the affair. "The old scheme!" exclaimed Kennedy. "That's the plan that has been used by a man down in Wall Street that they call, 'the Wolf.' He is a star impersonator--will call up two sworn enemies and put over something on them that double-crosses both." "Wall Street," mused Carton. "That reminds me of another batch of rumours that have been flying around. They were that I had made a deal with Langhorne by which I agreed to support him in his fight to get something in the contracts of the new city planning scheme in return for his support of the part of the organization he could swing to me in the election,--another lie." "It might have been Langhorne himself, playing the wolf," I suggested. Kennedy had reached for the telephone book. "Also, it might have been Kahn," he added. "I see he has an office in Wall Street, too. He has been the legal beneficiary of several shady transactions down there." "Oh," put in Carton, "it might have been any of them--they're all capable of it from Dorgan down. If Murtha was only out, I'd be inclined to suspect him." He tossed over a typewritten sheet of paper. "That's the statement I gave out to the press," he explained. It read: "My attention has been called to the alleged activities of some person or persons who through telephone calls and underground methods are seeking to undermine confidence in my integrity. A more despicable method of attempting to arouse distrust I cannot imagine. It is criminal and if anyone can assist me in placing the responsibility where it belongs I shall be glad to prosecute to the limit." "That's all right," assented Kennedy, "but I don't think it will have any effect. You see, this sort of thing is too easy for anyone to be scared off from. All he has to do is to go to a pay station and call up there. You couldn't very well trace that." He stopped abruptly and his face puckered with thought. "There ought to be some way, though," I murmured, without knowing just what the way might be, "to tell whether it is Dorgan and the organization crowd, or Langhorne and his pool, or Kahn and the other shysters." "There IS a way," cried Kennedy at last. "You fellows wait here while I make a flying trip up to the laboratory. If anyone calls us, just put him off--tell him to call up later." Carton continued to direct the work of his office, of which there had been no interruptions even during the stress of the campaign. Now and then the telephone rang and each time Carton would motion to me, and say, "You take it, Jameson. If it seems perfectly regular then pass it over to me." Several routine calls came in, this way, followed by one from Miss Ashton, which Carton prolonged much beyond the mere time needed to discuss a phase of the Reform League campaign. He had scarcely hung up the receiver, when the bell tinkled insistently, as though central had had an urgent call which the last conversation had held up. I took down the receiver, and almost before I could answer the inquiry, a voice began, "This is the editor of the Wall Street Record, Mr. Carton. Have you heard anything of the rumours about Hartley Langhorne and his pool being insolvent? The Street has been flooded with stories--" "One moment," I managed to interrupt. "This is not Mr. Carton, although this is his office. No--he's out. Yes, he'll certainly be back in half an hour. Ring up then." I repeated the scrap of gossip that had filtered through to me, which Carton received in quite as much perplexity as I had. "Seems as if everybody was getting knocked," he commented. "That may be a blind, though," I suggested. He nodded. I think we both realized how helpless we were when Kennedy was away. In fact we made even our guesses with a sort of lack of confidence. It was therefore with a sense of relief that we welcomed him a few minutes later as he hurried into the office, almost breathless from his trip uptown and back. "Has anyone called up?" he inquired unceremoniously, unwrapping a small parcel which he carried. I told him as briefly as I could what had happened. He nodded, without making any audible comment, but in a manner that seemed to show no surprise. "I want to get this thing installed before anyone else calls," he explained, setting to work immediately. "What is it?" I asked, regarding the affair, which included something that looked like a phonograph cylinder. "An invention that has just been perfected," he replied without delaying his preparations, "by which it is possible for messages to be sent over the telephone and automatically registered, even in the absence of anyone at the receiving end. Up to the present it has been practicable to take phonograph records only by the direct action of the human voice upon the diaphragm of the instrument. Not long ago there was submitted to the French Academy of Sciences an apparatus by which the receiver of the telephone can be put into communication with a phonograph and a perfect record obtained of the voice of the speaker at the other end of the wire, his message being reproduced at will by merely pressing a button." "Wouldn't the telegraphone do?" I asked, remembering our use of that instrument in other cases. "It would record," he replied, "but I want a phonograph record. Nothing else will do in this case. You'll see why, before I get through. Besides, this apparatus isn't complicated. Between the diaphragm of the telephone receiver and that of the phonographic microphone is fitted an air chamber of adjustable size, open to the outer atmosphere by a small hole to prevent compression. I think," he added with a smile, "it will afford a pretty good means of collecting souvenirs of friends by preserving the sound of their voices through the telephone." For several minutes we waited. "I don't think I ever heard of such effrontery, such open, bare-faced chicanery," fumed Carton impatiently. "We'll catch the fellow yet," replied Kennedy confidently. "And I think we'll find him a bad lot." XIX THE ESCAPE At last the telephone rang and Carton answered it eagerly. As he did so, he quickly motioned to us to go to the outside office where we, too, could listen on extensions. "Yes, this is Mr. Carton," we heard him say. "This is the editor of the Wall Street Record," came back the reply in a tone that showed no hesitation or compunction if it was lying. "I suppose you have heard the rumours that are current downtown that Hartley Langhorne and the people associated with him have gone broke in the pool they formed to get control of the public utilities that would put them in a position to capture the city betterment contracts?" "No--I hadn't heard it," answered Carton, with difficulty restraining himself from quizzing the informant about himself. Kennedy was motioning to him that that was enough. "I'm sure I can't express any opinion at all for publication on the subject," he concluded brusquely, jamming down the receiver on the hook before his interlocutor had a chance to ask another question. The bell continued to ring, but Craig seized the receiver off its hook again and called back, "Mr. Carton has gone for the day," hanging it up again with a bang. "Call up the Record now," advised Craig, disconnecting the recording instrument he had brought. "See what the editor has to say." "This is the District Attorney's office," said Carton a moment later when he got the number. "You just called me." "I called you?" asked the editor, non-plussed. "About a rumour current in Wall Street." "Rumour? No, sir. It must be some mistake." "I guess so. Sorry to have troubled you. Good-bye." Carton looked from one to the other of us. "You see," he said in disgust, "there it is again. That's the sort of thing that has been going on all day. How do I know what that fellow is doing now--perhaps using my name?" I had no answer to his implied query as to who was the "wolf" and what he might be up to. As for Kennedy, while he showed plainly that he had his suspicions which he expected to confirm absolutely, he did not care to say anything about them yet. "Two can play at 'wolf,'" he said quietly, calling up the headquarters of Dorgan's organization. I wondered what he would say, but was disappointed to find that it was a merely trivial conversation about some inconsequential thing, as though Kennedy had merely wished to get in touch with the "Silent Boss." Next he called up the sanitarium to which Murtha had been committed, and after posing as Murtha's personal physician managed to have the rules relaxed to the extent of exchanging a few sentences with him. "How did he seem--irrational?" asked Carton with interest, for I don't think the District Attorney had complete confidence in the commonly announced cause of Murtha's enforced retirement. Kennedy shook his head doubtfully. "Sounded pretty far gone," was all he said, turning over the pages of the telephone book as he looked for another number. This time it was Kahn whom he called up, and he had some difficulty locating him, for Kahn had two offices and was busily engaged in preparing a defence to the charges preferred against him for the jury fixing episode. Among others whom he called up was Langhorne, and the conversation with him was as perfunctory as possible, consisting merely in repeating his name, followed by an apology from Kennedy for "calling the wrong number." In each case, Craig was careful to have his little recording instrument working, taking down every word that was uttered and when he had finished he detached it, looking at the cylinder with unconcealed satisfaction. "I'm going up to the laboratory again," he announced, as Carton looked at him inquiringly. "The investigation that I have in mind will take time, but I shall hurry it along as fast as I possibly can. I don't want any question about the accuracy of my conclusions." We left Carton, who promised to meet us late in the afternoon at the laboratory, and started uptown. Instead, however, of going up directly, Craig telephoned first to Clare Kendall to shadow Mrs. Ogleby. The rest of the day he spent in making microphotographs of the phonograph cylinder and studying them very attentively under his high-powered lens. Toward the close of the afternoon the first report of Miss Kendall, who had been "trailing" Mrs. Ogleby, came in. We were not surprised to learn that she had met Langhorne in the Futurist Tea Room in the middle of the afternoon and that they had talked long and earnestly. What did surprise us, though, was her suspicion that she had crossed the trail of someone else who was shadowing Mrs. Ogleby. Kennedy made no comment, though I could see that he was vitally interested. What was the significance of the added mystery? Someone else had an interest in watching her movements. At once I thought of Dorgan. Could he have known of the intimacy of his guest at the Gastron dinner with Langhorne, rather than with Murtha, with whom she had gone? Suddenly another explanation occurred to me. What was more likely than that Martin Ogleby should have heard of his wife's escapade? He would certainly learn now to his surprise of her meeting with Langhorne. What would happen then? Kennedy had about finished with his microphotographic work and was checking it over to satisfy himself of the results, when Carton, as he had promised, dropped in on us. "What are you doing now?" he asked curiously, looking at the prints and paraphernalia scattered about. "By the way, I've been inquiring into the commitment of Murtha to that sanitarium for the insane. On the surface it all seems perfectly regular. It appears that, unknown even to many of his most intimate friends, he has been suffering from a complication of diseases, the result of his high life, and they have at last affected his brain, as they were bound to do in time. Still, I don't like his 'next friends' in the case. One is his personal physician--I don't know much about him. But Dorgan is one of the others." "We'll have to look into it," agreed Kennedy. "Meanwhile, would you like to know who your 'wolf' is that has been spreading rumours about broadcast?" "I would indeed," exclaimed Carton eagerly. "You were right about the statement I issued. It had no more effect than so many unspoken words. The fellow has kept right on. He even had the nerve to call up Miss Ashton in my name and try to find out whether she had any trace of the missing Betty Blackwell. How do you suppose they found out that she was interested?" "Not a very difficult thing," replied Kennedy. "Miss Ashton must have told several organizations, and the grafters always watch such societies pretty closely. What did she say?" "Nothing," answered Carton. "I had thought that they might try something of the sort and fortunately I warned her to disregard any telephone messages unless they came certainly from me. We agreed on a little secret formula, a sort of password, to be used, and I flatter myself that the 'wolf' won't be able to accomplish much in that direction. You say you have discovered a clue? How did you get it?" Kennedy picked up one of the microphotographs which showed an enlargement of the marks on the phonograph cylinder. He showed it to us and we gazed curiously at the enigmatic markings, greatly magnified. To me, it looked like a collection of series of lines. By close scrutiny I was able to make out that the lines were wavy and more or less continuous, being made up of collections of finer lines,--lines within lines, as it were. An analysis of their composition showed that the centre of larger lines was composed of three continuous series of markings which looked, under the lens, for all the world like the impressions of an endless straight series of molar teeth. Flanking these three tooth-like impressions were other lines--varying in width and in number--I should say, about four, both above and below the tooth-like impressions. When highly magnified one could distinguish roughly parallel parts of what at even a low magnification looked like a single line. "I have been studying voice analysis lately," explained Kennedy, "particularly with reference to the singing voice. Mr. Edison has made thousands and thousands of studies of voices to determine which are scientifically perfect for singing. That side of it did not interest me particularly. I have been seeking to use the discovery rather for detective purposes." He paused and with a fine needle traced out some of the lines on the photographs before us. "That," he went on, "is a highly magnified photograph of a minute section of the phonographic record of the voice that called you up, Carton, as editor of the Wall Street Record. The upper and lower lines, with long regular waves, are formed by a voice with no overtones. Those three broader lines in the middle, with rhythmic ripples, show the overtones." Carton and I followed, fascinated by the minuteness of his investigation and knowledge. "You see," he explained, "when a voice or a passage of music sounds or is sung before a phonograph, its modulations received upon the diaphragm are written by the needle point upon the surface of the cylinder or disc in a series of fine waving or zig-zag lines of infinitely varying depth and breadth. "Close familiarity with such records for about forty years has taught Mr. Edison the precise meaning of each slightest variation in the lines. I have taken up and elaborated his idea. By examining them under the microscope one can analyze each tone with mathematical accuracy and can almost hear it--just as a musician reading the score of a song can almost hear the notes." "Wonderful," ejaculated Carton. "And you mean to say that in that way you can actually identify a voice?" Kennedy nodded. "By examining the records in the laboratory, looking them over under a microscope--yes. I can count the overtones, say, in a singing voice, and it is on the overtones that the richness depends. I can recognize a voice--mathematically. In short," Craig concluded enthusiastically, "it is what you might call the Bertillon measurement, the finger-print, the portrait parle of the human voice!" Incredible as it seemed, we were forced to believe, for there on the table lay the graphic evidence which he had just so painstakingly interpreted. "Who was it?" asked Carton breathlessly. Kennedy picked up another microphotograph. "That is the record I took of one of the calls I made--merely for the purpose of obtaining samples of voices to compare with this of the impersonator. The two agree in every essential detail and none of the others could be confounded by an expert who studied them. Your 'wolf' was your old friend Kahn!" "Fighting back at me by his usual underhand methods," exclaimed Carton in profound disgust. "Or else trying himself to get control of the Black Book," added Kennedy. "If you will stop to think a moment, his shafts have been levelled quite as much at discrediting Langhorne as yourself. He might hope to kill two birds with one stone--and incidentally save himself." "You mean that he wants to lay a foundation now for questioning the accuracy of the Black Book if it ever comes to light?" "Perhaps," assented Kennedy carefully. "Surely we should take some steps to protect ourselves from his impostures," hastened Carton. "I have no objections to your calling him up and telling him that we know what he is up to and can trace it to him--provided you don't tell him how we did it--yet." Carton had seized the telephone and was hastily calling every place in which Kahn was likely to be. He was not at either of his offices, nor at Farrell's, but at each place successively Carton left a message which told the story and which he could hardly fail to receive soon. As Carton finished, Kennedy seemed to be emerging from a brown study. He rose slowly and put on his hat. "Your story about Murtha's commitment interests me," he remarked, "particularly since you mentioned Dorgan's name in connection with it. I've been thinking about Murtha myself a good deal since I heard about his condition. I want to see him myself." Carton hesitated a minute. "I can break an engagement I had to speak to-night," he said. "Yes, I'll go with you. It's more important to look to the foundations than to the building just now." A few minutes later we were all on our way in a touring car to the private sanitarium up in Westchester, where it had been announced that Murtha had been taken. I had apprehended that we would have a great deal of difficulty either in getting admitted at all or in seeing Murtha himself. We arrived at the sanitarium, a large building enclosed by a high brick wall, and evidently once a fine country estate, at just about dusk. To my surprise, as we stopped at the entrance, we had no difficulty in being admitted. For a moment, as we waited in the richly furnished reception room, I listened to the sounds that issued from other parts of the building. Something was clearly afoot, for things were in a state of disorder. I had not an extensive acquaintance with asylums for the care and treatment of the insane, but the atmosphere of excitement which palpably pervaded the air was not what one would have expected. I began to think of Poe's Dr. Tarr and Professor Fether, and wonder whether there might not have been a revolution in the place and the patients have taken charge of their keepers. At last one of the attendants passed the door. No one had paid any attention to us since our admission and this man, too, was going to pass us without notice. "I beg your pardon," interrupted Kennedy, who had heard his footsteps approaching and had placed himself in the hallway so that the attendant could not pass, "but we have called to see Mr. Murtha." The attendant eyed us curiously. I expected him to say that it was against the rules, or to question our right to see the patient. "I'm afraid you're too late," he said briefly, instead. "Too late?" queried Kennedy sharply. "What do you mean?" The man answered promptly as if that were the quickest way to get back to his own errand. "Mr. Murtha escaped from his keepers this evening, just after dinner, and there is no trace of him." XX THE METRIC PHOTOGRAPH Murtha's escape from the sanitarium had again thrown our calculations into chaos. We rode back to the city in silence, and even Kennedy had no explanation to offer. Even at a late hour that night, although a widespread alarm had been sent out for him, no trace of the missing man could be found. The next morning's papers, of course, were full of the strange disappearance, but gave no hint of his discovery. In fact, all day the search was continued by the authorities, but without result. On the face of it, it seemed incredible that a man who was so well known, especially to the thousands of police and others in the official and political life of the city, could remain at large unrecognized. Still, I recalled other cases where prominent men had disappeared. The facts in Murtha's case spoke for themselves. Comparatively little occurred during the day, although the political campaign which had begun with the primaries many weeks before was now drawing nearer its close and the campaigners were getting ready for the final spurt to the finish. With Kennedy's unmasking of the unprincipled activities of Kahn, that worthy changed his tactics, or at least dropped out of our sight. Mrs. Ogleby lunched with Langhorne and I began to suspect that the shadow that had been placed on her could not have been engaged by Martin Ogleby, for he was not the kind who would take reports of the sort complaisantly. Someone else must be interested. As for the Black Book itself, I wondered more as time went on that no one made use of it. Even though we gained no hint from Langhorne after the peculiar robbery of his safe, it was impossible to tell whether or not he still retained the detectaphone record. On the other hand, if Dorgan had obtained it by using the services of someone in the criminal hierarchy that Murtha had built up, it would not have been likely that we would have heard anything about it. We were in the position of men fighting several adversaries in the dark without knowing exactly whom we fought. We had just finished dinner, that night, Kennedy and I, and, as had been the case in most of the waking hours of the previous twenty-four, had been speculating on the possible solution of the mysterious dropping out of sight of Murtha. The evening papers had contained nothing that the morning papers had not already published and Kennedy had tossed the last of an armful into the scrap basket when the buzzer on the door of our apartment sounded. A young man stood there as I opened the door, and handed me a note, as he touched his hat. "A message for Professor Kennedy from Mr. Carton, sir," he announced. I recognized him as Carton's valet as he stood impatiently waiting for Craig to read the letter. "It's all right--there's no answer--I'll see him immediately," nodded Kennedy, tossing the hasty scrawl over to me as the valet disappeared. "My study at home has been robbed, probably by sneak thieves," read the note. "Would you like to look it over? I can't find anything missing except a bundle of old and valueless photographs. Carton." "Looks as if someone thought Carton might have got that Black Book from Langhorne," I commented, following the line on which I had been thinking at the time. "And the taking of the photographs was merely a blind, after not finding it?" Kennedy queried, I cannot say much impressed by my theory. "Perhaps," I acquiesced weakly, as we went out. Instead of turning in the direction of Carton's immediately, Kennedy walked across the campus toward the Chemistry Building. At the laboratory we loaded ourselves with a large and heavy oblong case containing a camera and a tripod. The Cartons lived in an old section of the city which still retained something of its aristocratic air, having been passed by, as it were, like an eddy in the stream of business that swirled uptown, engulfing everything. It was an old four-story brownstone house which had been occupied by his father and grandfather before him, and now was the home of Carton, his mother, and his sister. "I'm glad to see you," Carton met us at the door. "This isn't quite as classy a robbery as Langhorne's--but it's just as mysterious. Must have happened while the family were at dinner. That's why I said it was a robbery by a sneak thief." He was leading the way to his study, which was in an extension of the house, in the rear. "I hope you've left things as they were," ventured Craig. "I did," assured Carton. "I know your penchant for such things and almost the first thought I had was that you'd prefer it that way. So I shut the door and sent William after you. By the way, what have you done with him?" "Nothing," returned Craig. "Isn't he back yet?" "No--oh, well I don't need him right away." "And nothing was taken except some old photographs?" asked Craig, looking intently at Carton's face. "That is all I can find missing," he returned frankly. Kennedy's examination of the looted study was minute, taking in the window through which the thief had apparently entered, the cabinet he had forced, and the situation in general. Finally he set up his camera with most particular care and took several flashlight pictures of the window, the cabinet, the doors--including the study--from every angle. Outside he examined the extension and back of the house carefully, noting possible ways of getting from the side street across the fences into the Carton yard. With Carton we returned to Craig's splendidly equipped photographic studio and while Carton and I made the best of our time by discussing various phases of the case, Kennedy employed the interval in developing his plates. He had ten or a dozen prints, all of exactly the same size, mounted on stiff cardboard in a space with scales and figures on all four margins. Carton and I puzzled over them. "Those are metric photographs, such as Bertillon of Paris used to take," Craig explained. "By means of the scales and tables and other methods that have been worked out, we can determine from those pictures distances and many other things almost as well as if we were on the spot ourselves. Bertillon cleared up many crimes with this help, such as the mystery of the shooting in the Hotel Quai d'Orsay and other cases. The metric photograph, I believe, will in time rank with other devices in the study of crime." He was going over the photographs carefully. "For instance," he continued, "in order to solve the riddle of a crime, the detective's first task is to study the scene topographically. Plans and elevations of a room or house are made. The position of each object is painstakingly noted. In addition, the all-seeing eye of the camera is called into requisition. The plundered room is photographed, as in this case. I might have done it by placing a foot rule on a table and taking that in the picture. But a more scientific and accurate method has been devised by Bertillon. His camera lens is always used at a fixed height from the ground and forms its image on the plate at an exact focus. The print made from the negative is mounted on a card in a space of definite size, along the edges of which a metric scale is printed. In the way he has worked it out, the distance between any two points in the picture can be determined. With a topographical plan and a metric photograph one can study a crime, as a general studies the map of a strange country. There were several peculiar things that I observed at your house, Carton, and I have here an indelible record of the scene of the crime. Preserved in this way, it cannot be questioned. You are sure that the only thing missing is the photographs?" Carton nodded, "I never keep anything valuable lying around." "Well," resumed Kennedy, "the photographs were in this cabinet. There are other cabinets, but none of them seems to have been disturbed. Therefore the thief must have known just what he was after. The marks made in breaking the lock were not those of a jimmy, but of a screwdriver. No amazing command of the resources of science is needed so far. All that is necessary is a little scientific common sense." Carton glanced at me, and I smiled, for it always did seem so easy, when Craig did it, and so impossible when we tried to go it alone. "Now, how did the robber get in?" he continued, thoroughly engrossed in his study. "All the windows were supposedly locked. I saw that a pane had been partly cut from this window at the side--and the pieces were there to show it. But consider the outside, a moment. To reach that window even a tall man must have stood on a ladder or something. There were no marks of a ladder or even of any person in the soft soil of the garden under the window. What is more, that window was cut from the inside. The marks of the diamond which cut it plainly show that. Scientific common sense again." "Then it must have been someone in the house or at least familiar with it?" I exclaimed. Kennedy shook his head affirmatively. I had been wondering who it could be. Certainly this was not the work of Dopey Jack, even if the far cleverer attempt on Langhorne's safe had been. But it might have been one of his gang. I had not got as far as trying to reason out the why of the crime. "Call up your house, Carton," asked Craig. "See if William, your valet, has returned." Carton did so, and a moment later turned to us with a look of perplexity on his face. "No," he reported, "he hasn't come back yet. I can't imagine where he is." "He won't come back," asserted Kennedy positively. "It was an inside job--and he did it." Carton gasped astonishment. "At any rate," pursued Kennedy, "one thing we have which the police greatly neglect--a record. We have made some progress in reconstructing the crime, as Bertillon used to call it." "Strange that he should take only photographs," I mused. "What were they?" asked Kennedy, and again I saw that he was looking intently at Carton's face. "Nothing much," returned Carton unhesitatingly, "just some personal photographs--of no real value except to me. Most of them were amateur photographs, too, pictures of myself in various groups at different times and places that I kept for the associations." "Nothing that might be used by an enemy for any purpose?" suggested Kennedy. Carton laughed. "More likely to be used by friends," he replied frankly. Still, I felt that there must have been some sinister purpose back of the robbery. In that respect it was like the scientific cracking of Langhorne's safe. Langhorne, too, though he had been robbed, had been careful to disclaim the loss of anything of value. I frankly had not believed Langhorne, yet Carton was not of the same type and I felt that his open face would surely have disclosed to us any real loss that he suffered or apprehension that he felt over the robbery. I was forced to give it up, and I think Kennedy, too, had decided not to worry over the crossing of any bridges until at least we knew that there were bridges to be crossed. Carton was worried more by the discovery that one he had trusted even as a valet had proved unfaithful. He knew, however, as well as we did that one of the commonest methods of the underworld when they wished to pull off a robbery was to corrupt one of the servants of a house. Still, it looked strange, for the laying of such an elaborate plan usually preceded only big robberies, such as jewelery or silver. For myself, I was forced back on my first theory that someone had concluded that Carton had the Black Book, had concocted this elaborate scheme to get what was really of more value than much jewelry, and had found out that Carton did not have the precious detectaphone record, after all. I knew that there were those who would have gone to any length to get it. A general alarm was given, through the police, for the apprehension of William, but we had small hope that anything would result from it, for at that time Carton's enemies controlled the police and I am not sure but that they would have been just a little more dilatory in apprehending one who had done Carton an injury than if it had been someone else. It was too soon, that night, of course, to expect to learn anything, anyhow. It was quite late, but it had been a confining day for Kennedy who had spent the hours while not working on Carton's case in some of the ceaseless and recondite investigations of his own to which he was always turning his restless mind. "Suppose we walk a little way downtown with Carton?" he suggested. I was not averse, and by the time we arrived in the white light belt of Broadway the theatres were letting out. Above the gaiety of the crowds one could hear the shrill cry of some belated newsboys, calling an "Extra Special"--the only superlative left to one of the more enterprising papers whose every issue was an "Extra." Kennedy bought one, with the laughing remark, "Perhaps it's about your robbery, Carton." It was only a second before the smile on his face changed to a look of extreme gravity. We crowded about him. In red ink across the head of the paper were the words: "BODY OF MURTHA, MISSING, FOUND IN MORGUE" Down in a lower corner, in a little box into which late news could be dropped, also in red ink, was the brief account: This morning the body of an unknown man was found in The Bronx near the Westchester Railroad tracks. He had been run over and badly mutilated. After lying all day in the local morgue, it was transferred, still unidentified, to the city Morgue downtown. Early this evening one of the night attendants recognized the unidentified body as that of Murtha, "the Smiling Boss," whose escape day before yesterday from an asylum in Westchester has remained a mystery until now. "Well--what do you--think of that!" ejaculated Carton. "Murtha--dead--and I thought the whole thing was a job they were putting up on me!" Kennedy crooked his finger at a cabby who was alertly violating the new ordinance and soliciting fares away from a public cab stand. "The Morgue--quick!" he ordered, not even noticing the flabbergasted look on the jehu's face, who was not accustomed to carrying people thither from the primrose path of Broadway quite so rapidly. XXI THE MORGUE There had come a lull in the activities which never entirely cease, night or day, in the dingy building at the foot of East Twenty-sixth Street. Across the street in the municipal lodging-house the city's homeless were housed for the night. Even ever wakeful Bellevue Hospital nearby was comparatively quiet. The last "dead boat" which carries the city's unclaimed corpses away for burial had long ago left, when we arrived. The anxious callers who pass all day through the portals of the mortuary chamber seeking lost friends and relatives had disappeared. Except for the night keeper and one or two assistants, the Morgue was empty save of the overcrowded dead. Years before, as a cub reporter on the Star, I had had the gruesome assignment once of the Morgue. It was the same old place after all these years and it gave me the same creepy sensations now as it did then. Even the taxicab driver seemed glad to set down his fares and speed away. It was ghoulish. I felt then and I did still that instead of contributing to the amelioration of conditions that could not be otherwise than harrowing, everything about the old Morgue lent itself to the increase of the horror of the surroundings. As Kennedy, Carton, and I entered, we found that the principal chamber in the place was circular. Its walls were lined with the ends of caskets, which, fitting close into drawer-like apertures were constantly enveloped in the refrigerated air. It seemed, even at that hour, that if these receptacles were even adequate to contain all of the daily tenants of the Morgue, much of the anguish and distress inseparable from such a place might be spared those who of necessity must visit the place seeking their dead. As it was, even for those bound by no blood ties to the unfortunates who found their way to the city Morgue, the room was a veritable chamber of horror. We stood in horrified amazement at what we saw. On the floor, which should be kept clear, lay the overflow of the day's intake. Bodies for which there was no room in the cooling boxes, others which were yet awaiting claimants, and still more awaiting transfer to the public burying ground, lay about in their rough coffins, many of them brutally exposed. It seemed, too, that if ever there was a time when conditions might have been expected to have halfway adjusted themselves to the pressure which by day brought out all too clearly the hopeless inadequacy of the facilities provided by the city to perform one of its most important and inevitable functions, it was at that early morning hour of our visit. Presumably preparation had been completed for the busy day about to open by setting all into some semblance of respectful order. But such was not the case. It was impossible. In one group, I recall, which an attendant said had been awaiting his removal for a couple of days, the rough board coffins, painted the uniform brown of the city's institutions, lay open, without so much as face coverings over the dead. They lay as they had been sent in from various hospitals. Most of them were bereft of all the decencies usual with the dead, in striking contrast, however, with the bodies from Bellevue, which were all closely swathed in bandages and shrouds. One body, that of a negro, which had been sent in to the Morgue from a Harlem hospital, lay just as it came, utterly bare, exposing to public view all the gruesome marks of the autopsy. I wondered whether anything like that might be found to be the fate of the once jovial and popular Murtha, when we found him. I almost forgot our mission in the horror of the place, for, nearby was an even more heartrending sight. Piled in several heaps much higher than a man's head and as carelessly as cordwood were the tiny coffins holding the babies which the authorities are called on by the poor of the city to bury in large numbers--far too poor to meet the cost of the cheapest decent burial. Atop the stack of regulation coffins were the nondescript receptacles made use of by the very poor--the most pathetic a tiny box from the corner grocery. The bodies, some dozens of them, lay like so much merchandise, awaiting shipment. "What a barbarity!" I heard Craig mutter, for even he, though now and then forced to visit the place when one of his cases took him there, especially when it was concerned with an autopsy, had never become hardened to it. Often I had heard him denounce the primitive appointments, especially in the autopsy rooms. The archaic attempts to utilize the Morgue for scientific investigation were the occasion for practices that shocked even the initiated. For the lack of suitable depositories for the products of autopsies, these objects were plainly visible in rude profusion when a door was opened to draw out a body for inspection. About and around the slabs whereon the human bodies lay, in bottles and in plates, this material which had no place except in the cabinets of a laboratory was inhumanly displayed in profusion, close to corpses for which a morgue is expected to provide some degree of reverential care. "You see," apologized the keeper, not averse to throwing the blame on someone else, for it indeed was not his but the city's fault, "one reason why so many bodies have to remain uncared for is that I could show you cooling box after cooling box with some subject which figured during the past few months in the police records. Why victims of murders committed long ago should be held indefinitely, and their growing numbers make it impossible to give proper places to each day's temporary bodies, I can't say. Sometimes," he added with a sly dig at Carton, "the only explanation seems to be that the District Attorney's office has requested the preservation of the grisly relics." I could see that Carton was making a mental note that the practice would be ended as far as his office was concerned. "So--you saw the story in the newspapers about Mr. Murtha," repeated the keeper, not displeased to see us and at the publicity it gave him. "It was I that discovered him--and yet many's the times some of the boys that must have handled the body since it was picked up beside the tracks must have seen him. It was too late to get anyone to take the body away to-night, but the arrangements have all been made, and it will be done early in the morning before anyone else sees Pat Murtha here, as he shouldn't be. We've done what we could for him ourselves--he was a fine gentleman and many's the boy that owes a boost up in life to him." Reverentially even the hardened keeper drew out one of the best of the drawer-like boxes. On the slab before us lay the body. Carton drew back, excitedly, shocked. "It IS Murtha!" he exclaimed. I, too, looked at it quickly. The name as Carton pronounced it, in such a place, had, to me at least, an unpleasant likeness to "murder." Kennedy had bent down and was examining the mutilated body minutely. "How do you suppose such a thing is possible--that he could lie about the city, even here until the night keeper came on,--unknown?" asked Carton, aghast. "I don't know," I said, "but I imagine that in connection with the actual inadequacy of the equipment one would find reflected the same makeshift character in the attitude and actions of those who handle the city's dead. It used to be the case, at least, that the facilities for keeping records were often almost totally neglected, and not through the fault of the Morgue keepers, entirely. But, I understand it is better now." "This is terrible," repeated Carton, averting his face. "Really, Jameson, it makes me feel like a hound, for ever thinking that Murtha might have been putting up a game on me. Poor old Murtha--I should have preferred to remember him as the 'Smiling Boss' as everyone always called him!" I called to mind the last time we had seen Murtha, in Carton's office as the bearer of an offer which had made Carton almost beside himself with anger at the thought of the insult that he would compromise with the organization. What a contrast, this, with the Murtha who, in turn, had been trembling with passion at Carton's refusal! And yet I could not but reflect on the strangeness of it all--the fact that the organization, of which Murtha was a part, had by its neglect and failure to care for the human side of government when there was graft to be collected, brought about the very conditions which had made possible such neglect of the district leader's body, as it had been bandied back and forth, unwittingly by many who owed their very positions to the organization. I could not help but think that if he had served humanity with one-half the zeal which he had served graft, this could not have happened. The more I contemplated the case, the more tragic did it seem to me. I longed for the assignment of writing the story for the Star--the chance I would have had in the old days to bring in a story that would have got me a nod of approval from my superior. I determined, as soon as possible, to get the Star on the wire and try to express some of the thoughts that were surging through my brain in the face of this awful and unexpected occurrence. There he lay, alone, uncared for except by such rude hands as those of the Morgue attendants. I could not help reflecting on the strange vicissitudes of human life, and death, which levelled all distinctions between men of high and low degree. Murtha had almost literally sprung from the streets. His career had been one possible only in the social and political conditions of his times. And now he had only by the narrowest chance escaped a burial in a pauper's grave at the hands of the city which he had helped Dorgan to debauch. Carton, too, I could see was overwhelmed. For the moment he did not even think of how this blow to the System might affect his own chances. It was only the pitiful wreck of a human being before us that he saw. I was not an expert on study of wounds, such as was Kennedy, who was examining Murtha's body with minute care, now and then muttering under his breath at the rough and careless handling it had received in its various transfers about the city. But there were some terrible wounds and disfigurements on the body, which added even more to the horror of the case. One thing, I felt, was fortunate. Murtha had had no family. There had been plenty of scandal about him, but as far as I knew there was no one except his old cronies in the organization to be shocked by his loss, no living tragedy left in the wake of this. "How do you suppose it happened?" I asked the night keeper. He shook his head doubtfully. "No one knows, of course," he replied slowly. "But I think the big fellow got worse up there in that asylum. He wasn't used to anything but having his own way, you know. They say he must have waited his chance, after the dinner hour, when things were quiet, and then slipped out while no one was looking. He may have been crazy, but you can bet your life Pat Murtha was the smartest crazy man they ever had up there. THEY couldn't hold him." "I see," I said, struck by the faith which the man had inspired even in those who held the lowest of city positions. "But I meant how do you suppose he was killed?" The attendant looked at me thoughtfully a while. "Young man," he answered, "I ain't saying nothing and it may have been an accident after all. Have you ever been up in that part of town?" I had not and said so. "Well," he continued, "those electric trains do sneak up on a fellow fast. It may have been an accident, all right. The coroner up there said so, and I guess he ought to know. It must have been late at night--perhaps he was wandering away from the ordinary roads for fear of being recaptured. No one knows--I guess no one will know, ever. But it's a sad day for many of the boys. He helped a lot of 'em. And Mr. Dorgan--he knows what a loss it is, too. I hear that it's hit the Chief hard." The attendant, rough though he was and hardened by the daily succession of tragedies, could not restrain an honest catch in his voice over the passing of the "big fellow," as some of them called the "Smiling Boss." It was a pretty good object lesson on the power of the system which the organization had built up, how Murtha, and even the more distant Dorgan himself, had endeared himself to his followers and henchmen. Perhaps it was corrupt, but it was at least human, and that was a great deal in a world full of inhumanities. In the face of what had happened, one felt that much might be forgiven Murtha for his shortcomings, especially as the era of the Murthas and Dorgans was plainly passing. "Here at least," whispered Carton, as we withdrew to a corner to escape the palling atmosphere, "is one who won't worry about what happens to that Black Book any more. I wonder what he really knew about it--what secrets he carried away with him?" "I can't say," I returned. "But, one thing it does. It must relieve Mrs. Ogleby's fears a bit. With Murtha out of the way there is one less to gossip about what went on at Gastron's that night of the dinner." He said nothing and just then Kennedy straightened up, as though he had finished his examination. We hurried over to him. I thought the look on Craig's face was peculiar. "What is it--what did you find?" both Carton and I asked. Kennedy did not answer immediately. "I--I can't say," he answered slowly at length, as we thanked the Morgue keeper for his courtesy and left the place. "In fact I'd rather not say--until I know." I knew from previous experiences that it was of no use to try to quiz Kennedy. He was a veritable Gradgrind for facts, facts, facts. As for myself, I could not help wondering whether, after all, Murtha might not have been the victim of foul play--and, if so, by whom? XXII THE CANARD We did not have to wait long for the secret of the robbery of Carton to come out. It was not in any "extras," or in the morning papers the next day, but it came through a secret source of information to the Reform League. "A clerk in the employ of the organization who is really a detective employed by the Reform League," groaned Carton, as he told us the story himself the next morning at his office, "has just given us the information that they have prepared a long and circumstantial story about me--about my intimacy with Mrs. Ogleby and Murtha and some others. The story of the robbery of my study is in the papers this morning. To-morrow they plan to publish some photographs--alleged to have been stolen." "Photographs--Mrs. Ogleby," repeated Kennedy. "Real ones?" "No," exclaimed Carton quickly, "of course not--fakes. Don't you see the scheme? First they lay a foundation in the robbery, knowing that the public is satisfied with sensations, and that they will be sure to believe that the robbery was put up by some muckrakers to obtain material for an expose. I wasn't worried last night. I knew I had nothing to conceal." "Then what of it?" I asked naively. "A good deal of it," returned Carton excitedly, "The story is to be, as I understand it, that the fake pictures were among those stolen from me and that in a roundabout way they came into the possession of someone in the organization, without their knowing who the thief was. Of course they don't know who took them and the original plates or films are destroyed, but they've concocted some means of putting a date on them early in the spring." "What are they that they should take such pains with them?" persisted Kennedy, looking fixedly at Carton. Carton met his look without flinching. "They are supposed to be photographs of myself," he repeated. "One purports to represent me in a group composed of Mrs. Ogleby, Murtha, another woman whom I do not even know, and myself. I am standing between Murtha and Mrs. Ogleby and we look very familiar. Another is a picture of the same four riding in a car, owned by Murtha. Oh, there are several of them, of that sort." He paused as a dozen unspoken questions framed themselves in my mind. "I don't hesitate to admit," he added, "that a few months ago I knew Mrs. Ogleby--socially. But there was nothing to it. I never knew Murtha well, and the other woman I never saw. At various times I have been present at affairs where she was, but I know that no pictures were ever taken, and even if there had been, I would not care, provided they told the truth about them. What I do care about is the sworn allegation that, I understand, is to accompany these--these fakes." His voice broke. "It's a lie from start to finish, but just think of it, Kennedy," he went on. "Here is the story, and here, too, are the pictures--at least they will be, in print, to-morrow. Now, you know nothing could hurt the reform ticket worse than to have a scandal like this raised at this time. There may be just enough people to believe that there is some basis for the suspicion to turn the tide against me. If it were earlier in the campaign, I might accept the issue, fight it out to a finish, and in the turn of events I should have really the best sort of campaign material. But it is too late now to expose such a knavish trick on the Saturday before election." "Can't we buy them off?" I ventured, perplexed beyond measure at this new and unexpected turn of events. "No, I won't," persisted Carton, shutting his square jaw doggedly. "I won't be held up--even if that is possible." "Miss Ashton on the wire," announced a boy from the outer office. The look on Carton's face was a study. I saw directly what was the trouble--far more important to him than a mere election. "Tell her--I'm out--will be back soon," he muttered, for the first time hesitating to speak to her. "You see," he continued blackly, "I'll fight if it takes my last dollar, but I won't allow myself to be blackmailed out of a cent--no, not a cent," he thundered, a heightened look of determination fixing the lines on his face as he brought his fist down with a rattling bang on the desk. Kennedy was saying nothing. He was letting Carton ease his mind of the load which had been suddenly thrust upon it. Carton was now excitedly pacing the floor. "They believe plainly," he continued, growing more excited as he paced up and down, "that the pictures will of course be accepted by the public as among those stolen from me, and in that, I suppose, they are right. The public will swallow it. If I say I'll prosecute, they'll laugh and tell me to go ahead, that they didn't steal the pictures. Our informant tells us that a hundred copies have been made of each and that they have them ready to drop into the mail to the leading hundred papers, not only of this city but of the state, in time for them to appear Sunday. They think that no amount of denying on our part can destroy the effect." "That's it," I persisted. "The only way is to buy them off." "But, Jameson," argued Carton, "I repeat--they are false. It is a plot of Dorgan's, the last fight of a boss, driven into a corner, for his life. And it is meaner than if he had attempted to forge a letter. Pictures appeal to the eye much more than letters. That's what makes the thing so dangerous. Dorgan knows how to make the best use of such a roorback on the eve of an election and even if I not only deny but prove that they are a fake, I'm afraid the harm will be done. I can't reach all the voters in time. Ten see such a charge to one who sees the denial." He looked from one to the other of us helplessly. "If we had a week or two, it might be all right. But I can't make any move to-day without making a fool of myself, nothing until they are published, as the last big thing of the campaign. Monday and Tuesday morning do not give me time to reply in the papers and hammer it in. Even if they were out now, it would not give me time to make of it an asset instead of a liability. And then, too, it means that I am diverted by this thing, that I let up in the final efforts that we have so carefully planned to cap the campaign. That in itself is as much as Dorgan wants, anyway." Kennedy had been, so far, little more than an interested listener, but now he asked pointedly, "You have copies of the pictures?" "No--but I've been promised them this morning." "H'm," mused Craig, turning the crisis over in his mind. "We've had alleged stolen and forged letters before, but alleged stolen and forged photographs are new. I'm not surprised that you are alarmed, Carton,--nor that Walter suggests buying them off. But I agree with you, Carton--it's best to fight, to admit nothing, as you would imply by any other method." "Then you think you can trace down the forger of those pictures before it is too late?" urged Carton, leaning forward almost like a prisoner in the dock to catch the words of the foreman of the jury. "I haven't said I can do that--yet," measured Craig with provoking slowness. "Say, Kennedy, you're not going to desert me?" reproached Carton. Kennedy laughed as he put his hand on Carton's shoulder. "I've been afraid of something like this," he said, "ever since I began to realize that you had once been--er--foolish enough to become even slightly acquainted with that adventuress, Mrs. Ogleby. My advice is to fight, not to get in wrong by trying to dicker, for that might amount to confession, and suit Dorgan's purpose just as well. Photographs," he added sententiously, "are like statistics. They don't lie unless the people who make them do. But it's hard to tell what a liar can accomplish with either, in an election. I--I don't know that I'd desert you--if the pictures were true. I'd be sure there was some other explanation." "I knew it," responded Carton heartily. "Your hand on that, Kennedy. Say, I think I've shaken hands with half the male population of this city since I was nominated, but this means more than any of them. Spare no reasonable expense and--get the goods, no matter whom it hits higher up--Langhorne--anybody. And, for God's sake get it in time--there's more than an election that hangs on it!" Carton looked Kennedy squarely in the eye again, and we all understood what it was he meant that was at stake. It might be possible after all to gloss over almost anything and win the election, but none of us dared to think what it might mean if Miss Ashton not only suspected that Carton had been fraternizing with the bosses but also that there had been or by some possibility could be anything really in common between him and Mrs. Ogleby. That, after all, I saw was the real question. How would Miss Ashton take it? Could she ever forgive him if it were possible for Langhorne to turn the tables and point with scorn at the man who had once been his rival for her hand? What might be the effect on her of any disillusionment, of any ridicule that Langhorne might artfully heap up? As we left Carton, I shared with Kennedy his eagerness to get at the truth, now, and win the fight--the two fights. "I want to see Miss Ashton, first," remarked Kennedy when we were outside. Personally I thought that it was a risky business, but felt that Kennedy must know best. When we arrived at the Reform League headquarters, the clerks and girls had already set to work, and the office was a hive of industry in the rush of winding up the campaign. Typewriters were clicking, clippings were being snipped out of a huge stack of newspapers and pasted into large scrapbooks, circulars were being folded and made ready to mail for the final appeal. Carton's office there had been in the centre of the suite. On one side were the cashier and bookkeeper, the clerical force and the speakers' bureau, where spellbinders of all degrees were getting instructions, final tours were being laid out, and reports received of meetings already held. On the other side was the press bureau, with its large and active force, in charge of Miss Ashton. As we entered we saw Miss Ashton very busy over something. Her back was toward us, but the moment she turned at hearing us we could see that something was the matter. Kennedy wasted no time in coming to the point of his visit. We had scarcely seated ourselves beside her desk when he leaned over and said in a low voice, "Miss Ashton, I think I can trust you. I have called to see you about a matter of vital importance to Mr. Carton." She did not betray even by a fleeting look on her proud face what the true state of her feelings was. "I don't know whether you know, but an attempt is being made to slander Mr. Carton," went on Kennedy. Still she said nothing, though it was evident that she was thinking much. "I suppose in a large force like this that it is not impossible that your political enemies may have a spy or two," observed Kennedy, glancing about at the score or more clerks busily engaged in getting out the "literature." "I have sometimes thought that myself," she murmured, "but of course I don't know. There isn't anything for them to discover in THIS office, though." Kennedy looked up quickly at the significant stress on the word "this." She saw that Kennedy was watching. Margaret Ashton might have made a good actress, that is, in something in which her personal feelings were not involved, as they were in this case. She was now pale and agitated. "I--I can't believe it," she managed to say. "Oh, Mr. Kennedy--I would almost rather not have known it at all,--only I suppose I must have known it sooner or later." "Believe me, Miss Ashton," soothed Kennedy, "you ought to know. It is on you that I depend for many things. But, tell me, how do you know already? I didn't think--it was known." She was still pale, and replied nervously, "Our detective in the organization brought the pictures up here--one of the girls opened them by mistake--it got about the office--I couldn't help but know." "Miss Ashton," remonstrated Kennedy soothingly, "I beg you to be calm. I had no idea you would take it like this, no idea. Please, please. Remember pictures can lie--just like words." "I--I hope you're right," she managed to reply slowly. "I'm all broken up by it. I'm ready to resign. My faith in human nature is shaken. No, I won't say anything about Mr. Carton to anyone. But it cuts me to have to think that Hartley Langhorne may have been right. He always used to say that every man had his price. I am afraid this will do great harm to the cause of reform and through it to the woman suffrage cause which made me cast myself in with the League. I--I can hardly believe--" Kennedy was still looking earnestly at her. "Miss Ashton," he implored, "believe nothing. Remember one of the first rules of politics in the organization you are fighting is loyalty. Wait until--" "Wait?" she echoed. "How can I? I hate Mr. Carton for--for even knowing--" she paused just in time to substitute Mr. Murtha for Mrs. Ogleby--"such men as Mr. Murtha--secretly." She bit her lip at thus betraying her feelings, but what she had seen had evidently affected her deeply. It was as though the feet of her idol had turned to clay. "Just think it over," urged Kennedy. "Don't be too harsh. Don't do anything rash. Suspend judgment. You won't regret it." Kennedy was apparently doing some rapid thinking. "Let me have the photographs," he asked at length. "They are in Mr. Carton's office," she answered, as if she would not soil her hands by touching the filthy things. We excused ourselves and went into Carton's office. There they were wrapped up, and across the package was written by one of the clerks, "Opened by mistake." Kennedy opened the package again. Sure enough, there were the photographs--as plain as they could be, the group including Carton, Mrs. Ogleby, Murtha, and another woman, standing on the porch of a gabled building in the sunshine, again the four speeding in a touring car, of which the number could be read faintly, and other less interesting snapshots. As I looked at them I said nothing, but I must admit that the whole thing began to assume a suspicious look in my mind in connection with various hints I had heard dropped by organization men about probing into the past, and other insinuations. I felt that far from aiding Carton, things were now getting darker. There was nothing but his unsupported word that he had not been in such groups to counterbalance the existence of the actual pictures themselves, on the surface a graphic clincher to Dorgan's story. Kennedy, however, after an examination of the photographs clung no less tenaciously to a purpose he already had in mind, and instead of leaving them for Carton, took them himself, leaving a note instead. He stopped again to speak to Margaret Ashton. I did not hear all of the conversation, but one phrase struck me, "And the worst of it is that he called me up a little while ago and tried to act toward me in the same old way--and that after I know what I know. I--I could detect it in his voice. He knew he was concealing something from me." What Kennedy said to her, I do not know, but I don't think it had much effect. "That's the most difficult and unfortunate part of the whole affair," he sighed as we left. "She believes it." I had no comment that was worth while. What was to be done? If people believed it generally, Carton was ruined. XXIII THE CONFESSION Dorgan was putting up a bold fight, at any rate. Everyone, and most of all his opponents who had once thought they had him on the run, was forced to admit that. Moreover, one could not help wondering at his audacity, whatever might be the opinion of his dishonesty. But I was quite as much struck by the nerve of Carton. In the face of gathering misfortunes many a man of less stern mettle might have gone to pieces. Not so with the fighting District Attorney. It seemed to spur him on to greater efforts. It was a titanic struggle, this between Carton and Dorgan, and had reached the point where quarter was given or asked by neither. Kennedy had retired to his laboratory with the photographs and was studying them with an increasing interest. It was toward the close of the afternoon when the telephone rang and Kennedy motioned to me to answer it. "If it's Carton," he said quickly, "tell him I'm not here. I'm not ready for him yet and I can't be interrupted." I took down the receiver, prepared to perjure my immortal soul. It was indeed Carton, bursting with news and demanding to see Kennedy immediately. Almost before I had finished with the carefully framed, glib excuse that I was to make, he shouted to me over the wire, "What do you think, Jameson? Tell him to come down right away. The impossible has happened. I have got under Dopey Jack's guard--he has confessed. It's big. Tell Kennedy I'll wait here at my office until he comes." He had hung up the receiver before I could question him further. I think it cured Kennedy, temporarily of asking me to fib for him over the telephone. He was as anxious as I to see Carton, now, and plunged into the remaining work on the photographs eagerly. He finished much sooner than he would, otherwise, and only to preserve the decency of the excuse that I had made did not hasten down to the Criminal Courts Building before a reasonable time had elapsed. As we entered Carton's office we could tell from the very atmosphere of the halls that something was happening. The reporters in their little room outside were on the qui vive and I heard a whisper and a busy scratching of pencils as we passed in and the presence of someone else in the District Attorney's office was noted. Carton met us in a little ante-room. He was all excitement himself, but I could see that it was a clouded triumph. His mind was really elsewhere than on the confession that he was getting. Although he did not ask us, I knew that he was thinking only of Margaret Ashton and how to regain the ground that he had apparently lost with her. Still, he said nothing about the photographs. I wondered whether it was because of his confidence that Kennedy would pull him through. "You know," he whispered, "I have been working with my assistants on Dopey Jack ever since the conviction, hoping to get a confession from him, holding out all sorts of promises if he would turn state's evidence and threats if he didn't. It all had no effect. But Murtha's death seems to have changed all that. I don't know why--whether he thinks it was due to foul play or not, for he won't say anything about that and evidently doesn't know--but it seems to have changed him." Carton said it as though at last a ray of light had struck in on an otherwise black situation, and that was indeed the case. "I suppose," suggested Craig, "that as long as Murtha was alive he would rather have died than say anything that would incriminate him. That's the law of the gang world. But with Murtha no longer to be shielded, perhaps he feels released. Besides, it must begin to look to him as though the organization had abandoned him and was letting him shift pretty much for himself." "That's it," agreed Carton. "He has never got it out of his head that Kahn swung the case against him and I've been careful not to dwell on the truth of that Kahn episode." Carton led us into his main office, where Rubano was seated with two of Carton's assistants who were quizzing him industriously and obtaining an amazing amount of information about gang life and political corruption. In fact, like most criminals when they do confess, Dopey Jack was in danger of confessing too much, in sheer pride at his own prowess as a bad man. Outside, I knew that it was being well noised abroad, in fact I had nodded to an old friend on the Star who had whispered to me that the editor had already called him up and offered to give Rubano any sum for a series of articles for the Sunday supplement on life in the underworld. I knew, then, that the organization had heard of it, by this time--too late. Most of the confession was completed by the time we arrived, but as it had all been carefully taken down we knew we had missed nothing. "You see, Mr. Carton," Rubano was saying as we three entered and he turned from the assistant who was quizzing him, "it's like this. I can't tell you all about the System. No one can. You understand that. All any of us know is the men next to us--above and below. We may have opinions, hear gossip, but that's no good as evidence." "I understand," reassured Carton. "I don't expect that. You must tell me the gossip and rumours, but all I am bartering a pardon for is what you really know, and you've got to make good, or the deal is off, see?" He said it in a tone that Dopey Jack could understand and the gangster protested. "Well, Mr. Carton, haven't I made good?" "You have so far," grudgingly admitted Carton who was greedy for everything down to the uttermost scrap that might lead to other things. "Now, who was the man above you, to whom you reported?" "Mr. Murtha, of course," replied Jack, surprised that anyone should ask so simple a question. "That's all right," explained Carton. "I knew it, but I wanted you on record as saying it. And above Murtha?" "Why, you know it is Dorgan," replied Dopey, "only, as I say, I can't prove that for you any better than you can." "He has already told about his associates and those he had working under him," explained Carton, turning to us. "Now Langhorne--what do you know about him?" "Know about Langhorne--the fellow that was--that I robbed?" repeated Jack. "You robbed?" cut in Kennedy. "So you knew about thermit, then?" Dopey smiled with a sort of pride in his work, much as if he had received a splendid recommendation. "Yes," he replied. "I knew about it--got it from a peterman who has studied safes and all that sort of thing. I heard he had some secret, so one night I takes him up to Farrell's and gets him stewed and he tells me. Then when I wants to use it, bingo! there I am with the goods." "And the girl--Betty Blackwell--what did she have to do with it?" pursued Craig. "Did you get into the office, learn Langhorne's habits, and so on, from her?" Dopey Jack looked at us in disgust. "Say," he replied, "if I wanted a skirt to help me in such a job, believe me I know plenty that could put it all over that girl. Naw, I did it all myself. I picked the lock, burnt the safe with that powder the guy give me, and took out something in soft leather, a lot of typewriting." We were all on our feet in unrestrained excitement. It was the Black Book at last! "Yes," prompted Carton, "and what then--what did you do with it?" "Gave it to Mr. Murtha, of course," came back the matter-of-fact answer of the young tough. "What did he do with it?" demanded Carton. Dopey Jack shook his head dubiously. "It ain't no use trying to kid you, Mr. Carton. If I told you a fake you'd find it out. I'd tell you what he did, if I knew, but I don't--on the level. He just took it. Maybe he burnt it--I don't know. I did my work." Unprincipled as the young man was, I could not help the feeling that in this case he was telling only the truth as he knew it. We looked at each other aghast. What if Murtha had got it and had destroyed it before his death? That was an end of the dreams we had built on its capture. On the other hand, if he had hidden it there was small likelihood now of finding it. The only chance, as far as I could see, was that he had passed it along to someone else. And of that Dopey Jack obviously knew nothing. Still, his information was quite valuable enough. He had given us the first definite information we had received of it. Carton, his assistants, and Kennedy now vigorously proceeded in a sort of kid glove third degree, without getting any further than convincing themselves that Rubano genuinely did not know. "But the stenographer," reiterated Carton, returning to the line of attack which he had temporarily abandoned. "Something became of her. She disappeared and even her family haven't a trace of her, nor any other institutions in the city. We've got something on you, there, Rubano." Jack laughed. "Mr. Carton," he answered easily, "the police put me through the mill on that without finding anything, and I don't believe you have anything. But just to show you that I'm on the square with you, I don't mind telling you that I got her away." It was dramatic, the off-hand way in which the gangster told of this mystery that had perplexed us. "Got her away--how--where?" demanded Carton fiercely. "Mr Murtha gave me some money--a wad. I don't know who gave it to him, but it wasn't his money. It was to pay her to stay away till this all blew over. Oh, they made it worth her while. So I dolled up and saw her--and she fell for it--a pretty good sized wad," he repeated, as though he wished some of it had stuck to his own hands. We fairly gasped at the ease and simplicity with which the fellow bandied facts that had been beyond our discovery for days. Here was another link in our chain. We could not prove it, but in all probability it was Dorgan who furnished the money. Even if the Black Book were lost, it was possible that in the retentive memory of this girl there might be much that would take its place. She had seen a chance for providing for the future of herself and her family. All she had to do was to take it and keep quiet. "You know where she is, then?" shot out Kennedy suddenly. "No--not now," returned Dopey. "She was told to meet me at the Little Montmartre. She did. I don't think she knew what kind of place it was, or she wouldn't have come." He paused, as though he had something on his mind. "Go on," urged Kennedy. "Tell all. You must tell all." "I was just thinking," he hesitated. "I remember I saw Ike the Dropper and Marie Margot there that day, too, with Martin Ogleby--" "Martin Ogleby!" interrupted Carton in surprise. "Yes, Martin Ogleby. He hangs about the Montmartre and the Futurist, all those joints. Say--I've been thinking a heap since this case of mine came up. I wonder whether it was all on the level--with me. I gave the money. But was that a stall? Perhaps they tried to get back. Perhaps she played into their hands--I saw her watching the sports, there, and believe me, there are some swell lookers. Oh well, _I_ don't know. All I know is my part. I don't know anything that happened after that. I can't tell what I don't know, can I, Mr. Carton?" "Not very well," smiled the prosecutor. "But you can tell us anything you suspect." "I don't know what I suspect. I was only a part of the machine. Only after I read that she disappeared, I began to think there might have been some funny business--I don't know." Eager as we were, we could only accept this unsatisfactory explanation of the whereabouts of Betty. "After all, I was only a part," reiterated Jack. "You better ask Ike--that's all." Just then the telephone buzzed. Carton was busy and Kennedy, who happened to be nearest, answered it. I fancied that there was a puzzled expression on his face, as he placed his hand over the transmitter and said to Carton, "Here--it's for you. Take it. By the way, where's that thing I left down here for recording voices?" "Here in my desk. But you took the cylinder with you." "Haven't you got another? Don't you ever use them for dictating letters?" Carton nodded and sent his stenographer to get a new one. "Just a minute, please," cut in Kennedy. "Mr. Carton will be here in a few moments, now." Carton took the telephone and placed his hand over it, until, with a nod from Kennedy as he affixed the machine, he answered. "Yes--this is the District Attorney," we heard him answer. "What? Rubano? Why you can't talk to him. He's a convicted man. Here? How do you know he's here? No--I wouldn't let you talk to him if he was. Who are you, anyway? What's that--you threaten him--you threaten me? You'll get us both, will you? Well, I want to tell you, you can go plumb--the deuce! The fellow's cut himself off!" As Carton finished, a peculiar smile played about Rubano's features. "I expected that, but not so soon," he said quietly. "New York'll be no place for me, Mr. Carton, after this. You've got to keep your word and smuggle me out. South Africa, you know--you promised." "I'll keep my word, Rubano, too," assured Carton. "The nerve of that fellow. Where's Kennedy?" We looked about. Craig had slipped out quietly during the telephone conversation. Before we could start a search for him, he returned. "I thought there was something peculiar about the voice," he explained. "That was why I wanted a record of it. While you were talking I got your switchboard operator to connect me with central on another wire. The call was from a pay station on the west side. There wasn't a chance to get the fellow, of course--but I have the voice record, anyhow." Dopey Jack's confession occupied most of the evening and it was late when we got away. Carton was overjoyed at the result of his pressure, and eager to know, on the other hand, whether Kennedy had made any progress yet with his study of the photographs. I could have told him beforehand, however, that Craig would say nothing and he did not. Besides, he had the added mystery of the new phonograph cylinder to engross him, with the result that we parted from Carton, a little piqued at being left out of Craig's confidence, but helpless. As for me, I knew it was useless to trail after Kennedy and when he announced that he was going back to the laboratory, I balked and, in spite of my interest in the case, went home to our apartment to bed, while Kennedy made a night of it. What he discovered I knew no better in the morning than when I left him, except that he seemed highly elated. Leisurely he dressed, none the worse for his late work and after devouring the papers as if there were nothing else in the world so important, he waited until the middle of the morning before doing anything further. "I merely wanted to give Dorgan a chance to get to his office," he surprised me with, finally. "Come, Walter, I think he must be there now." Amazed at his temerity in bearding Dorgan in his very den, I could do nothing but accompany him, though I much feared it was almost like inviting homicide. The Boss's office was full of politicians, for it was now approaching "dough day," when the purse strings of the organization were loosed and a flood of potent argument poured forth to turn the tide of election by the force of the only thing that talks loud enough for some men to hear. Somehow, Kennedy managed to see the Boss. "Mr. Dorgan," began Kennedy quietly, when we were seated alone in the little Sanctum of the Boss, "you will pardon me if I seem to be a little slow in coming to the business that has brought me here this morning. First of all I may say that you probably share the idea that ever since the days of Daguerre photography has been regarded as the one infallible means of portraying faithfully any object, scene, or action. Indeed, a photograph is admitted in court as irrefutable evidence. For, when everything else fails, a picture made through the photographic lens almost invariably turns the tide. However, such a picture upon which the fate of an important case may rest should be subjected to critical examination, for it is an established fact that a photograph may be made as untruthful as it may be reliable." He paused. Dorgan was regarding him keenly, but saying nothing. Kennedy did not mind, as he resumed. "Combination photographs change entirely the character of the initial negative and have been made for the past fifty years. The earliest, simplest, and most harmless photographic deception is the printing of clouds in a bare sky. But the retoucher with his pencil and etching tool to-day is very skilful. A workman of ordinary ability can introduce a person taken in a studio into an open-air scene well blended and in complete harmony without a visible trace of falsity." Dorgan was growing interested. "I need say nothing of how one head can be put on another body in a picture," pursued Craig, "nor need I say what a double exposure will do. There is almost no limit to the changes that may be wrought in form and feature. It is possible to represent a person crossing Broadway or walking on Riverside Drive, places he may never have visited. Thus a person charged with an offence may be able to prove an alibi by the aid of a skilfully prepared combination photograph. "Where, then," asked Kennedy, "can photography be considered as irrefutable evidence? The realism may convince all, except the expert and the initiated after careful study. A shrewd judge will be careful to insist that in every case the negative be submitted and examined for possible alterations by a clever manipulator." Kennedy bent his gaze on Dorgan. "Now, I do not accuse you, sir, of anything. But a photograph has come into my possession in which Mr. Carton is represented as standing in a group on a porch, with Mr. Murtha, Mrs. Ogleby, and an unknown woman. The first three are in poses that show the utmost friendliness. I do not hesitate to say that was originally a photograph of yourself, Mr. Murtha, Mrs. Ogleby, and a woman whom you know well. It is a pretty raw deal, a fake in which Carton has been substituted by very excellent photographic forgery." "A fake--huh!" repeated Dorgan, contemptuously. "How about the story of them? There's no negative. You've got to show me that the original print stolen from Carton, we'll say, is a fake. You can't do it. No, sir, those pictures were taken this summer." Kennedy quietly laid down the bundle of photographs copied from those alleged to have been stolen from Carton. He was pointing to a shadow of a gable on the house. "You see that shadow of the gable, Dorgan?" he asked. "Perhaps you never heard of it, but it is possible to tell the exact time at which a photograph was taken from a study of the shadows. It is possible in theory and practice, and it can be trusted absolutely. Almost any scientist, Dorgan, may be called in to bear testimony in court nowadays, but you probably think the astronomer is one of the least likely. "Well, the shadow in this picture can be made to prove an alibi for someone. Notice. It is seen prominently to the right, and its exact location on the house is an easy matter. The identification of the gable casting the shadow ought to be easy. To be exact, I have figured it out as 19.62 feet high. The shadow is 14.23 feet down, 13.10 feet east, and 3.43 feet north. You see, I am exact. I have to be. In one minute it moves 0.080 feet upward, 0.053 feet to the right, and 0.096 feet in its apparent path. It passes the width of a weatherboard, 0.37 foot, in four minutes and thirty-seven seconds." Kennedy was talking rapidly of data which he had derived from the study of the photograph as from plumb line, level, compass, and tape, astronomical triangle, vertices, zenith, pole, and sun, declination, azimuth, solar time, parallactic angles, refraction, and a dozen other bewildering terms. "In spherical trigonometry," he concluded, "to solve the problem three elements must be known. I know four. Therefore, I can take each of the known, treat it as unknown, and have four ways to check my result. I find that the time might have been either three o'clock, twenty-one minutes and twelve seconds in the afternoon, or 3:21:31 or 3:21:29, or 3:21:33. The average is 3: 21:26 and there can be no appreciable error except for a few seconds. I tell you that to show you how close I can come. The important thing, however, is that the date must have been one of two days, either May 22 or July 22. Between these two dates we must decide on evidence other than the shadow. It must have been in May, as the immature condition of the foliage shows. But even if it had been in July, that would be far from the date you allege. Why, I could even tell you the year. Then, too, I could look up the weather records and tell something from them. I can really answer, with an assurance and accuracy superior to the photographer himself, if you could produce him and he were honest, as to the real date. The original picture, aside from being doctored, was actually taken last May. Science is not fallible, but exact in this matter." Kennedy felt that he had scored a palpable hit. Dorgan was speechless. Still, Craig hurried on. "But, you may ask, how about the automobile picture? That also is an unblushing fake. Of course I must prove that. In the first place you know that the general public has come to recognize the distortion of a photograph as denoting speed. A picture of a car in a race that doesn't lean is rejected. People demand to see speed, speed, more speed, even in pictures. Distortion does indeed show speed, but that, too, can be faked. "Almost everyone knows that the image is projected upside down by the lens on the plate, and that the bottom of the picture is taken before the top. The camera mechanism admits light, which makes the picture, in the manner of a roller blind curtain. The slit travels from the top to the bottom and, the image on the plate being projected upside down, the bottom of the object appears on the top of the plate. For instance, the wheels are taken before the head of the driver. If the car is moving quickly, the image moves on the plate and each successive part is taken a little in advance of the last. The whole leans forward. By widening the slit and slowing the speed of the shutter, there is more distortion. "Now, that is just what has been done. A picture has been taken of a car owned once by Murtha, probably at rest, with perhaps yourself, Murtha, Mrs. Ogleby, and your friend in it. The matter of faking Carton or anyone else is simple. If, with an enlarging lantern, the image of this faked picture is thrown on the printing paper like a lantern slide, and if the right-hand side is moved a little further away than the left, the top further away than the bottom, you can in that way print a fraudulent high-speed picture ahead. "True, everything else in the picture, even if motionless, is distorted, and the difference between this faking and the distortion of the shutter can be seen by an expert. But it will pass with most people. In this case, however," added Kennedy suddenly, "the faker was so sure of it that he was careless. Instead of getting the plate further from the paper on the right, he did so on the left. It was further away on the bottom than on the top. He got the distortion, all right, enough to satisfy anyone. But it is distortion in the wrong direction! The top of the wheel, which goes fastest and ought to be most indistinct, is, in the fake, as sharp as any other part. It is a small mistake that was made, but fatal. Your picture is not of a joy ride at all. It is really high speed--backwards! It is too raw, too raw." "You don't think people are going to swallow all that stuff, do you?" asked Dorgan coolly, in spite of the exposures. "What of it all?" he asked surlily. "I have nothing to do with it, anyhow. Why do you come to me? Take it to the proper authorities." "Shall I?" asked Kennedy quietly, leaning over and whispering a few words in Dorgan's ear. I could not hear what he said, but Dorgan appeared to be fairly staggered. When Kennedy passed out of the Boss's office there was a look of quiet satisfaction on his face which I could not fathom. Not a word could I extract from him on the subject, either. I was still in the dark as to the result of his visit. XXIV THE DEBACLE OF DORGAN Sunday morning came and with it the huge batch of papers which we always took. I looked at them eagerly, though Kennedy did not seem to evince much interest, to see whether the Carton photographs had been used. There were none. Kennedy employed the time in directing some work of his own and had disappeared, I knew not where, though I surmised it was on one of his periodic excursions into the underworld in which he often knocked about, collecting all sorts of valuable and interesting bits of information to fit together in the mosaic of a case. Monday came, also, the last day before the election, with its lull in the heart-breaking activities of the campaign. There were still no pictures published, but Kennedy was working in the laboratory over a peculiar piece of apparatus. "I've been helping out my own shadows," was all the explanation he vouchsafed of his disappearances, as he continued to work. "Watching Mrs. Ogleby?" I hinted. "No, I didn't interfere any more with Miss Kendall. This was someone else--in another part of the city." He said it with an air that seemed to imply that I would learn all about it shortly and I did not pursue the subject. Meanwhile, he was arranging something on the top of a large, flat table. It seemed to be an instrument in two parts, composed of many levers and discs and magnets, each part with a roll of paper about five inches wide. On one was a sort of stylus with two silk cords attached at right angles to each other near the point. On the other was a capillary glass tube at the junction of two aluminum arms, also at right angles to each other. It was quite like old times to see Kennedy at work in his laboratory again, and I watched him curiously. Two sets of wires were attached to each of the instruments, and they led out of the window to some other wires which had been strung by telephone linemen only a few hours before. Craig had scarcely completed his preparations when Carton arrived. Things were going all right in the campaign again, I knew, at least as far as appeared on the surface. But his face showed that Carton was clearly dissatisfied with what Craig had apparently accomplished, for, as yet, he had not told Carton about his discovery after studying the photographs, and matters between Carton and Margaret Ashton stood in the same strained condition that they had when last we saw her. I must say that I, too, was keenly disappointed by the lack of developments in this phase of the case. Aside from the fact that the photographs had not actually been published, the whole thing seemed to me to be a mess. What had Craig said to Dorgan? Above all, what was his game? Was he playing to spare the girl's feelings merely by allowing the election to go on without a scandal to Carton? I knew the result of the election was now the least of Carton's worries. Carton did not say much, but he showed that he thought it high time for Kennedy to do something. We were seated about the flat table, wondering when Kennedy would break his silence, when suddenly, as if by a spirit hand, the stylus before us began to move across one of the rolls of paper. We watched it uncomprehendingly. At last I saw that it was actually writing the words. "How is it working?" Quickly Craig seized the stylus on the lower part of the instrument and wrote in his characteristic scrawl, "All right, go ahead." "What is the thing?" asked Carton, momentarily forgetting his own worries at the new marvel before us. "An instrument that was invented many years ago, but has only recently been perfected for practical, every-day use, the telautograph, the long-distance writer," replied Kennedy, as we waited. "You see, with what amounts to an ordinary pencil I have written on the paper of the transmitter. The silk cord attached to the pencil regulates the current which controls another capillary glass tube-pen at the other end of the line. The receiving pen moves simultaneously with my stylus. It is the same principle as the pantagraph, cut in half as it were, one half here, the other half at the other end of the line, two telephone wires in this case connecting the halves. Ah,--that's it. The pencil of the receiving instrument is writing again. Just a moment. Let us see what it is." I almost gasped in astonishment at the words that I saw. I looked again, for I could not believe my eyes. Still, there it was. My first glance had been correct, impossible as it was. "I, Patrick Murtha," wrote the pen. "What is it?" asked Carton, awestruck. "A dead hand?" "Stop a minute," wrote Kennedy hastily. We bent over him closely. Craig had drawn from a packet several letters, which he had evidently secured in some way from the effects of Murtha. Carefully, minutely, he compared the words before us with the signatures at the bottom of the letters. "It is genuine!" he cried excitedly. "Genuine!" Carton and I echoed. What did he mean? Was this some kind of spiritism? Had Kennedy turned medium and sought a message from the other world to solve the inexplicable problems of this? It was weird, uncanny, unthinkable. We turned to him blankly for an explanation of the mystery. "That wasn't Murtha at all whose body we saw at the Morgue," he hurried to explain. "That was all a frame-up. I thought as soon as I saw it that there was something queer." I recalled now the peculiar look on his face which I had interpreted as indicating that he thought Murtha had been the victim of foul play. "And the other night, when we were in Carton's office and someone called up threatening you, Carton, and Dopey Jack, I saw at once that the voice was concealed. Yet there was something about it that was familiar, though I couldn't quite place it. I had heard that voice before, perhaps while we were getting the records to discover the 'wolf.' It occurred to me that if I had a record of it I might identify it by comparing it with those we had already taken. I got the record. I studied it. I compared it with what I already had, line, and wave, and overtone. You can imagine how I felt when I found there was only one voice with which it corresponded, and that man was supposed to be dead. Something more than intuition as I looked at the body that night had roused my suspicions. Now they were confirmed. Fancy how that information must have burned in my mind, during these days while I knew that Murtha was alive, but could say nothing!" Neither Carton nor I could say a word as we thought of this voice from the dead, as it almost seemed. "I hadn't found him," continued Craig, "but I knew he had used a pay station on the West Side. I began shadowing everyone who might have helped him, Dorgan, Kahn, Langhorne, all. I didn't find him. They were too clever. He was hiding somewhere in the city, a changed personality, waiting for the thing to blow over. He knew that of all places a city is the best to hide in, and of all cities New York is safest. "But, though I didn't actually find his hiding place, I had enough on some of his friends so that I could get word to him that his secret was known to me, at least. I made him an offer of safety. He need not come out of his hiding place and I would agree to let him go where and when he pleased without further pursuit from me, if he would let me install a telautograph in a neutral place which he could select and the other end in this laboratory. I myself do not know where the other place is. Only a mechanic sworn to secrecy knows and neither Murtha nor myself know him. If Murtha comes across, I have given my word of honour that before the world he shall remain a dead man, free to go where he pleases and enjoy such of his fortune as he was able to fix so that he could carry it with him into his new life." Carton and I were entranced by the romance of the thing. Murtha was alive! The commitment to the asylum, the escape, the search, the finding of a substitute body, mutilated beyond ordinary recognition, the mysterious transfers, and finally the identification in the Morgue--all had been part of an elaborately staged play! We saw it all, now. Carton had got too close to him in the conviction of Dopey Jack and the proceedings against Kahn. He had seen the handwriting on the wall for himself. In Carton's gradual climbing, step by step, for the man higher up, he would have been the next to go. Murtha had decided that it was time to get out, to save himself. Suddenly, I saw another aspect of it. By dropping out as though dead, he destroyed a link in the chain that would reach Dorgan. There was no way of repairing that link if he were dead. It was missing and missing for good. Dorgan had known it. Had it been a hint as to that which had finally clinched whatever it was that Kennedy had whispered to the Silent Boss that morning when we had seen him in his office? All these thoughts and more flashed through my head with lightning-like rapidity. The telautograph was writing again, obedient to Kennedy's signal that he was satisfied with the signature. "... in consideration of Craig Kennedy's agreement to destroy even this record, agree to give him such information as he has asked for, after which no further demands are to be made and the facts as already publicly recorded are to stand." "Just witness it," asked Kennedy of us. "It is a gentleman's agreement among us all." Nervously we set our names to the thing, only too eager to keep the secret if we could further the case on which we had been almost literally sweating blood so long. Prepared though we were for some startling disclosures, it was, nevertheless, with a feeling almost of faintness that we saw the stylus above moving again. "The Black Book, as you call it," it wrote, "has been sent by messenger to be deposited in escrow with the Gotham Trust Company to be delivered, Tuesday, the third of November, on the written order of Craig Kennedy and John Carton. An officer of the trust company will notify you of its receipt immediately, which will close the entire transaction as far as I am concerned." Kennedy could not wait. He had already seized his own telephone and was calling a number. "They have it," he announced a moment later, scrawling the information on the transmitter of the telautograph. A moment it was still, then it wrote again. "Good-bye and good luck," it traced. "Murtha!" The Smiling Boss could not resist his little joke at the end, even now. "Can--we--get it?" asked Carton, almost stunned at the unexpected turn of events. "No," cautioned Kennedy, "not yet. To-morrow. I made the same promise to Murtha that I made to Dorgan, when I went to him with Walter, although Walter did not hear it. This is to be a fair fight, for the election, now." "Then," said Carton earnestly, "I may as well tell you that I shall not sleep to-night. I can't, even if I can use the book only after election in the clean-up of the city!" Kennedy laughed. "Perhaps I can entertain you with some other things," he said gleefully, adding, "About those photographs." Carton was as good as his word. He did not sleep, and the greater part of the night we spent in telling him about what Craig had discovered by his scientific analysis of the faked pictures. At last morning came. Though Kennedy and I had slept soundly in our apartment, Carton had in reality only dozed in a chair, after we closed the laboratory. Slowly the hours slipped away until the trust company opened. We were the first to be admitted, with our order ready signed and personally delivered. As the officer handed over the package, Craig tore the wrapper off eagerly. There, at last, was the Black Book! Carton almost seized it from Kennedy, turning the pages, skimming over it, gloating like a veritable miser. It was the debacle of Dorgan--the end of the man highest up! XXV THE BLOOD CRYSTALS Much as we had accomplished, we had not found Betty Blackwell. Except for her shadowing of Mrs. Ogleby, Clare Kendall had devoted her time to winning the confidence of the poor girl, Sybil Seymour, whom we had rescued from Margot's. Meanwhile, the estrangement of Carton and Margaret Ashton threw a cloud over even our success. During the rest of the morning Craig was at work again in the laboratory. He was busily engaged in testing something through his powerful microscopes and had a large number of curious microphotographs spread out on the table. As I watched him, apparently there was nothing but the blood-stained gauze bandage which had been fastened to the face of the strange, light-haired woman, and on the stains on this bandage he was concentrating his attention. I could not imagine what he expected to discover from it. I waited for Kennedy to speak, but he was too busy more than to notice that I had come in. I fell to thinking of that woman. And the more I thought of the fair face, the more I was puzzled by it. I felt somehow or other that I had seen it somewhere before, yet could not place it. A second time I examined the unpublished photograph of Betty Blackwell as well as the pictures that had been published. The only conclusion that I could come to was that it could not be she, for although she was light-haired and of fair complexion, the face as I remembered it was that of a mature woman who was much larger than the slight Betty. I was sure of that. Every time I reasoned it out I came to the same contradictory conclusion that I had seen her, and I hadn't. I gave it up, and as Kennedy seemed indisposed to enlighten me, I went for a stroll about the campus, returning as if drawn back to him by a lodestone. About him was still the litter of test tubes, the photographs, the microscopes; and he was more absorbed in his delicate work than ever. He looked up from his examination of a little glass slide and I could see by the crow's feet in the corners of his eyes that he was not looking so much at me as through me at a very puzzling problem. "Walter," he remarked at length, "did you notice anything in particular about that blonde woman who dashed down the steps into the taxicab and escaped from the dope joint?" "I should say that I did," I returned, glad to ease my mind of what had been perplexing me ever since. "I don't want to appear to be foolish, but, frankly, I thought I had seen her before, and then when I tried to place her I found that I could not recognize her at all. She seemed to be familiar, and yet when I tried to place her I could think of no one with just those features. It was a foolish impression, I suppose." "That's exactly it," he exclaimed. "I thought at first it was just a foolish impression, too, an intuition which my later judgment rejected. But often those first impressions put you on the track of the truth. I reconsidered. You remember she had dropped that bandage from her face with the blood-stain on it. I picked it up and it occurred to me to try a little experiment with these blood-stains which might show something." He paused a moment and fingered some of the microphotographs. "What would you say," he went on, "if I should tell you that a pronounced blonde, with a fair complexion and thin, almost hooked, nose, was in reality a negress?" "If it were anyone but you, Craig," I replied frankly, "I'd be tempted to call him something. But you--well, what's the answer? How do you know?" "I wonder if you have ever heard of the Reichert blood test? Well, the Carnegie Institution has recently published an account of it. Professor Edward Reichert of the University of Pennsylvania has discovered that the blood crystals of all animals and men show characteristic differences. "It has even been suggested that before the studies are over photographs of blood corpuscles may be used to identify criminals, almost like fingerprints. There is much that can be discovered already by the use of these hemoglobin clues. That hemoglobin, or red colouring matter of the blood, forms crystals has been known for a long time. These crystals vary in different animals, as they are studied under the polarizing microscope, both in form and molecular structure. That is of immense importance for the scientific criminologist. "A man's blood is not like the blood of any other living creature, either fish, flesh, or fowl. Further, it is said that the blood of a woman or a man and of different individuals shows differences that will reveal themselves under certain tests. You can take blood from any number of animals and the scientists to-day can tell that it is not human blood, but the blood, say, of an animal. "The scientists now can go further. They even hope soon to be able to tell the difference between individuals so closely that they can trace parentage by these tests. Already they can actually distinguish among the races of men, whether a certain sample of blood, by its crystals, is from a Chinaman, a Caucasian, or a negro. Each gives its own characteristic crystal. The Caucasian shows that he is more closely related to one group of primates; the negro to another. It is scientific proof of evolution. "It is all the more wonderful, Walter, when you consider that these crystals are only 1-2250th of an inch in length and 1-9000th of an inch in width." "How do you study them?" I asked. "The method I employed was to take a little of the blood and add some oxalate of ammonium to it, then shake it up thoroughly with ether to free the hemoglobin from the corpuscles. I then separated the ether carefully from the rest of the blood mixture and put a few drops of it on a slide, covered them with a cover slip and sealed the edges with balsam. Gradually the crystals appear and they can be studied and photographed in the usual way--not only the shapes of the crystals, but also the relation that their angles bear to each other. So it is impossible to mistake the blood of one animal for another or of one race, like the white race, for that of another, like the black. In fact the physical characteristics by which some physicians profess to detect the presence of negro blood are held by other authorities to be valueless. But not so with this test." "And you have discovered in this case?" I asked. "That the blood on the bandage from the face of that woman who escaped was not the blood of a pure Caucasian. She shows traces of negro blood, in fact exactly what would have been expected of a mulatto." It dawned on me that the woman must have been Marie, after all; at least that that was what he meant. "But," I objected, "one look at her face was enough to show that she was not the dark-skinned Marie with her straight nose, her dark hair and other features. This woman was fair, had a nose that was almost hooked and hair that was almost flaxen. Remember the portrait parle." "Just so--the portrait parle. That is what I am remembering. You recall Carton discovered that in some way these people found out that we were using it? What would they do? Why, they have thought out the only possible way in which to beat it, don't you see? "Marie, Madame Margot, whatever you call her, had a beauty parlour. Oh, they are clever, these people. They reasoned it all out. What was a beauty parlour, a cosmetic surgery, for, if it could not be used to save them? They knew we had her scientific description. What was the thing to do, then? Why, change it, of course, change her!" Kennedy was quite excited now. "You know what Miss Kendall said of decorative surgery, there? They change noses, ears, foreheads, chins, even eyes. They put the thing up to Dr. Harris with his knives and bandages and lotions. He must work quickly. It would take all his time. So he disappeared into Margot's and stayed there. Marie also stayed there until such time as she might be able to walk out, another person entirely. Harris must have had charge of her features. The attendants in Margot's had charge of her complexion and hair--those were the things in which they specialized. "Don't you see it all now? She could retire a few days into the dope joint next door and she would emerge literally a new woman ready to face us, even with Bertillon's portrait parle against her." It was amazing how quickly Kennedy pieced the facts together into an explanation. "Yes," he concluded triumphantly, "that blonde woman was our dark-skinned mulatto made over--Marie. But they can't escape the power of science, even by using science themselves. She might change her identity to our eyes, but she could not before the Reichert test and the microscope. No, the Ethiopian could not change her skin before the eye of science." It was late in the afternoon that Kennedy received a hurried telephone call from Miss Kendall. I could tell by the scraps of conversation which I overheard that it was most important. "That girl, Sybil Seymour, has broken down," was all he said as he turned from the instrument. "She will be here to-day with Miss Kendall. You must see Carton immediately. Tell him not to fail to be here, at the laboratory, this afternoon at three, sharp." He was gone before I could question him further and there was nothing for me to do but to execute the commission he had laid on me. I met Carton at his club, relating to him all that I could about the progress of the case. He seemed interested but I could see that his mind was really not on it. The estrangement between him and Margaret Ashton outweighed success in this case and even in the election. Half an hour before the appointed time, however, we arrived at the laboratory in Carton's car, to find Kennedy already there, putting the finishing touches on the preparations he was making to receive his "guests." "Dorgan will be here," he answered, evading Carton's question as to what he had discovered. "Dorgan?" we repeated in surprise. "Yes. I have made arrangements to have Martin Ogleby, too. They won't dare stay away. Ike the Dropper, Dr. Harris, and Marie Margot have not been found yet, but Miss Kendall will bring Sybil Seymour. Then we shall see." The door opened. It was Ogleby. He bowed stiffly, but before he could say anything, a noise outside heralded the arrival of someone else. It proved to be Dorgan, who had come from an opposite direction. Dorgan seemed to treat the whole affair with contempt, which he took pleasure in showing. He was cool and calm, master of himself, in any situation no matter how hostile. As we waited, the strained silence, broken only by an occasional whisper between Carton and Kennedy, was relieved even by the arrival of Miss Kendall and Sybil Seymour in a cab. As they entered I fancied that a friendship had sprung up between the two, that Miss Kendall had won her fight for the girl. Indeed, I suspect that it was the first time in years that the girl had had a really disinterested friend of either sex. I thought Ogleby visibly winced as he caught sight of Miss Seymour. He evidently had not expected her, and I thought that perhaps he had no relish for the recollection of the Montmartre which her presence suggested. Miss Seymour, now like herself as she had appeared first behind the desk at the hotel, only subdued and serious, seemed ill at ease. Dorgan, on the other hand, bowed to her brazenly and mockingly. He was evidently preparing against any surprises which Craig might have in store, and maintained his usual surly silence. "Perhaps," hemmed Ogleby, clearing his throat and looking at his watch ostentatiously, "Professor Kennedy can inform us regarding the purpose of this extra-legal proceeding? Some of us, I know, have other engagements. I would suggest that you begin, Professor." He placed a sarcastic emphasis on the word "professor," as the two men faced each other--Craig tall, clean-cut, earnest; Ogleby polished, smooth, keen. "Very well," replied Craig with that steel-trap snap of his jaws which I knew boded ill for someone. "It is not necessary for me to repeat what has happened at the Montmartre and the beauty parlour adjoining it," began Kennedy deliberately. "One thing, however, I want to say. Twice, now, I have seen Dr. Harris handing out packets of drugs--once to Ike the Dropper, agent for the police and a corrupt politician, and once to a mulatto woman, almost white, who conducted the beauty parlour and dope joint which I have mentioned, a friend and associate of Ike the Dropper, a constant go-between from Ike to the corrupt person higher up. "This woman, whom I have just mentioned, we have been seeking by use of Bertillon's new system of the portrait parle. She has escaped, for the time, by a very clever ruse, by changing her very face in the beauty parlour. She is Madame Margot herself!" Not a word was breathed by any of the little audience as they hung on Kennedy's words. "Why was it necessary to get Betty Blackwell out of the way?" he asked suddenly, then without waiting for an answer, "You know and District Attorney Carton knows. Someone was afraid of Carton and his crusade. Someone wanted to destroy the value of that Black Book, which I now have. The only safety lay in removing the person whose evidence would be required in court to establish it--Betty Blackwell. And the manner? What more natural than to use the dope fiends and the degenerates of the Montmartre gang?" "That's silly," interrupted Ogleby contemptuously. "Silly? You can say that--you, the tool of that--that monster?" It was a woman's voice that interrupted. I turned. Sybil Seymour, her face blazing with resentment, had risen and was facing Ogleby squarely. "You lie!" exclaimed the Silent Boss, forgetting both his silence and his superciliousness. The situation was tense as the girl faced him. "Go on, Sybil," urged Clare. "Be careful, woman," cried Dorgan roughly. Sybil Seymour turned quickly to her new assailant. "You are the man for whom we were all coined into dollars," she scorned, "Dorgan--politician, man higher up! You reaped the profits through your dirty agent, Ike the Dropper, and those over him, even the police you controlled. Dr. Harris, Marie Margot, all are your tools--and the worst of them all is this man Martin Ogleby!" Dorgan's face was livid. For once in his life he was speechless rather than silent, as the girl poured out the inside gossip of the Montmartre which Kennedy had now stamped with the earmarks of legal proof. She had turned from Dorgan, as if from an unclean animal and was now facing Ogleby. "As for you, Martin Ogleby, they call you a club-man and society leader. Do you want to know what club I think you really belong to--you who have involved one girl after another in the meshes of this devilish System? You belong to the Abduction Club--that is what I would call it--you--you libertine!" XXVI THE WHITE SLAVE Carton had sprung to his feet at the direct charge and was facing Ogleby. "Is that true--about the Montmartre?" he demanded. Ogleby fairly sputtered. "She lies," he almost hissed. "Just a moment," interrupted Dorgan. "What has that to do with Miss Blackwell, anyhow?" Sybil Seymour did not pause. "It is true," she reiterated. "This is what it has to do with Betty Blackwell. Listen. He is the man who led me on, who would have done the same to Betty Blackwell. I yielded, but she fought. They could not conquer her--neither by drugs nor drink, nor by clothes, nor a good time, nor force. I saw it all in the Montmartre and the beauty parlour--all." "Lies--all lies," hissed Ogleby, beside himself with anger. "No, no," cried Sybil. "I do not lie. Mr. Carton and this good woman, Miss Kendall, who is working for him, are the first people I have seen since you, Martin Ogleby, brought me to the Montmartre, who have ever given me a chance to become again what I was before you and your friends got me." "Have a care, young woman," interrupted Dorgan, recovering himself as she proceeded. "There are laws and--" "I don't care a rap about laws such as yours. As for gangs--that was what you were going to say--I'd snap my fingers in the face of Ike the Dropper himself if he were here. You could kill me, but I would tell the truth. "Let me tell you my case," she continued, turning in appeal to the rest of us, "the case of a poor girl in a small city near New York, who liked a good time, liked pretty clothes, a ride in an automobile, theatres, excitement, bright lights, night life. I liked them. He knew that. He led me on, made me like him. And when I began to show the strain of the pace--we all show it more than the men--he cast me aside, like a squeezed-out lemon." Sybil Seymour was talking rapidly, but she was not hysterical. "Already you know Betty Blackwell's story--part of it," she hurried on. "Miss Kendall has told me--how she was bribed to disappear. But beyond that--what?" For a moment she paused. No one said a word. Here at last was the one person who held the key to the mystery. "She did disappear. She kept her word. At last she had money, the one thing she had longed for. At last she was able to gratify those desires to play the fashionable lady which her family had always felt. What more natural, then, than while she must keep in hiding to make one visit to the beauty parlour to which so many society women went--Margot's? It was there that she went on the day that she disappeared." We were hanging breathlessly now on the words of the girl as she untangled the sordid story. "And then?" prompted Kennedy. "Then came into play another arm of the System," she replied. "They tried to make sure that she would disappear. They tried the same arts on her that they had on me--this man and the gang about him. He played on her love of beauty and Madame Margot helped him. He used the Montmartre and the Futurist to fascinate her, but still she was not his. She let herself drift along, perhaps because she knew that her family was every bit the equal socially of his own. Madame Margot tried drugs; first the doped cigarette, then drugs that had to be forced on her. She kept her in that joint for days by force; and there where I went for relief day after day from my own bitter thoughts I saw her, in that hell which Miss Kendall now by her evidence will close forever. Still she would not yield. "I saw it all. Maybe you will say I was jealous because I had lost him. I was not. I hated him. You do not know how close hate can be to love in the heart of a woman. I could not help it. I had to write a letter that might save her. "Miss Kendall has told me about the typewritten letters; how you, Professor Kennedy, traced them to the Montmartre. I wrote them, I admit, for these people. I wrote that stuff about drugs for Dr. Harris. And I wrote the first letter of all to the District Attorney. I wrote it for myself and signed it as I am--God forgive me--'An Outcast.'" The poor girl, overwrought by the strain of the confession that laid bare her very soul, sank back in her chair and cried, as Miss Kendall gently tried to soothe her. Dorgan and Ogleby listened sullenly. Never in their lives had they dreamed of such a situation as this. There was no air of triumph about Kennedy now over the confession, which with the aid of Miss Kendall, he had staged so effectively. Rather it was a spirit of earnestness, of retribution, justice. "You know all this?" he inquired gently of the girl. "I saw it," she said simply, raising her bowed head. Dorgan had been doing some quick thinking. He leaned over and whispered quickly to Ogleby. "Why was she not discovered then when these detectives broke into the private house--an act which they themselves will have to answer for when the time comes?" demanded Ogleby. It seemed as if the mere sound of his voice roused the girl. "Because it was dangerous to keep her there any longer," she replied. "I heard the talk about the hotel, the rumour that someone was using this new French detective scheme. I heard them blame the District Attorney--who was clever enough to have others working on the case whom you did not know. While you were watching his officers, Mr. Kennedy and Miss Kendall were gathering evidence almost under your very eyes. "But you were panic-stricken. You and your agents wanted to remove the danger of discovery. Dr. Harris and Marie Margot had a plan which you grasped at eagerly. There was Ike the Dropper, that scoundrel who lives on women. Between them you would spirit her away. You were glad to have them do it, little realizing that, with every step, they had you involved deeper and worse. You forgot everything, all honour and manhood in your panic; you were ready to consent, to urge any course that would relieve you--and you have taken the course that involves you worse than any other." "Who will believe a story like that?" demanded Ogleby. "What are you--according to your own confession? Am I to be charged with everything this gang, as you call it, does? You are their agent, perhaps working for this blackmailing crew. But I tell you, I will fight, I will not be blackened by--" Sybil laughed, half hysterically. "Blackened?" she repeated. "You who would put this thing all off on others who worked for you, who played on your vices and passions, not because you were weak, but because you thought you were above the law! "You did not care what became of that girl, so long as she was where she could not accuse you. You left her to that gang, to Ike, to Marie, to Harris." She paused a moment, and flashed a quick glance of scorn at him. "Do you want to know what has become of her, what you are responsible for? "I will tell you. They had other ideas than just getting her out of the way of your selfish career. They are in this life for money. Betty Blackwell to them was a marketable article, a piece of merchandise in the terrible traffic which they carry on. If she had been yielding, like the rest of us, she might now be apparently free, yet held by a bondage as powerful and unescapable as if it were of iron, a life from which she could not escape. But she was not yielding. They would break her. Perhaps you have tried to ease your conscience, if you have any, by the thought that it is they, not you, who have her hidden away somewhere now. You cannot escape that way; it was you who made her, who made others of us, what we are." "Let her rave, Ogleby," sneered Dorgan. "Yes--raving, that's it," echoed Ogleby. But his expression belied him. "There it is," she continued. "You have not even an opinion of your own. You repeat even the remarks of others. They have you in their power. You have put yourself there." "All very pretty," remarked Dorgan with biting sarcasm. "All very cleverly thought out. So nice here! Wait until you have to tell that story in court. You know the first rule of equity? Do you go into court with clean hands? There is a day of reckoning coming to you, young woman, and to these other meddlers here--whether they are playing politics or meddling just because they are old-maidish busy-bodies." She was facing the politician with burning cheeks. "You," she scorned, "belong to an age that is passing away. You cannot understand these people like Miss Kendall, like Mr. Carton, who cannot be bought and controlled like your other creatures. You do not know how the underworld can turn on the upperworld. You would not pull us up--you shoved us down deeper, in your greed. But if we go down, we shall drag you, too. What have we to lose? You and your creatures, like Martin Ogleby, have taken everything from us. We--" "Come, Ogleby," interposed Dorgan, deliberately turning his back on her and slowly placing his hat on his half-bald head. "We are indebted to Professor Kennedy for a pleasant entertainment. When he has another show equally original we trust he will not forget the first-nighters who have enjoyed this farce." Dorgan had reached the door and had his hand on the knob. I had expected Kennedy to reply. But he said nothing. Instead his hand stole along the edge of the table beside which he was standing. "Good-night," bowed Dorgan with mock solemnity. "Thank you for laying the cards on the table. We shall know how to play--" Dorgan cut the words short. Kennedy had touched the button of an electric attachment which was under the table by which he could lock every door and window of the laboratory instantly and silently. "Well?" demanded Dorgan fiercely, though there was a tremble in his voice that had never been heard before. "Where is Betty Blackwell?" demanded Craig, turning to Sybil Seymour. "Where did they take her?" We hung breathlessly on the answer. Was she being held as a white slave in some obscure den? I knew that that did not mean that she was necessarily imprisoned behind locked doors and barred windows, although even that might be the case. I knew that the restraint might be just as effective, even though it was not actually or wholly physical. An ordinary girl, I reasoned, with little knowledge of her rights or of the powers which she might call to her aid if she knew how to summon them, might she not be so hemmed in by the forces into whose hands she had fallen as to be practically held in bonds which she could not break? Here was Sybil herself! Once she had been like Betty Blackwell. Indeed, when she seemed to have every chance to escape she did not. She knew how she could be pursued, hounded at every turn, forced back, and her only course was to sink deeper into the life. The thought of what might be accomplished by drugs startled me. Clare bent over the poor girl reassuringly. What was it that seemed to freeze her tongue now? Was it still some vestige of the old fear under which she had been held so long? Clare strove, although we could not hear what she was saying, to calm her. At last Sybil raised her head, with a wild cry, as if she were sealing her own doom. "It was Ike. He kept us all in terror. Oh, if he hears he will kill me," she blurted out. "Where did he take her?" asked Clare. She had broken down the girl's last fear. "To that place on the West Side--that black and tan joint, where Marie Margot came from before the gang took her in." "Carton," called Kennedy. "You and Walter will take Miss Kendall and Miss Seymour. Let me see. Dorgan, Ogleby, and myself will ride in the taxicab." Carton was toying ostentatiously with a police whistle as Dorgan hesitated, then entered the cab. I think at the joint, as we pulled up with a rush after our wild ride downtown, they must have thought that a party of revellers had dropped in to see the sights. It was perhaps just as well that they did, for there was no alarm at first. As we entered the black and tan joint, I took another long look at its forbidding exterior. Below, it was a saloon and dance hall; above, it was a "hotel." It was weatherbeaten, dirty, and unsightly, without, except for the entrance; unsanitary, ramshackle, within, except for the tawdry decorations. At every window were awnings and all were down, although it was on the shady side of the street in the daytime and it was now getting late. That was the mute sign post to the initiated of the character of the place. Instead of turning downstairs where we had gone on our other visit, Kennedy led the way up through a door that read, "Hotel Entrance--Office." A clerk at a desk in a little alcove on the second floor mechanically pushed out a register at us, then seeming to sense trouble, pulled it back quickly and with his foot gave a sharp kick at the door of a little safe, locking the combination. "I'm looking for someone," was all Kennedy said. "This is the District Attorney. We'll go through--" "Yes, you will!" It was Ike the Dropper. He had heard the commotion, and, seeing ladies, came to the conclusion that it was not a police plainclothes raid, but some new game of the reformers. He stopped short in amazement at the sight of Dorgan and Ogleby. "Well--I'll be--" "Carton! Walter!" shouted Kennedy. "Take care of him. Watch out for a knife or gun. He's soft, though. Carton--the whistle!" Our struggle with the redoubtable Ike was short and quickly over. Sullen, and with torn clothes and bleeding face, we held him until the policeman arrived, and turned him over to the law. At a room on the same floor Craig knocked. "Come in," answered a woman's voice. He pushed open the door. There was the woman who had fled so precipitately from the dope joint. Evidently she did not recognize us. "You are under arrest," announced Kennedy. The blonde woman laughed mockingly. "Under arrest? For what?" "You are Marie Margot. Never mind about your alias. All the arts of your employees and Dr. Harris himself cannot change you so that I cannot recognize you. You may feel safe from the portrait parle, but there are other means of detection that you never dreamed of. Where is Betty Blackwell? Marie, it's all off!" All the brazen assurance with which she had met us was gone. She looked from one to the other and read that it was the end. With a shriek, she suddenly darted past us, out of the door. Down the hall was Ike the Dropper with the policeman and Carton. Beside her was a stairway leading to the upper floors. She chose the stairs. Following Kennedy we hurried through the hotel, from one dirty room to another, with their loose and creaking floors, rotten and filthy, sagging as we walked, covered with matting that was rotting away. Damp and unventilated, the air was heavy and filled with foul odours of tobacco, perfumery, and cheap disinfectants. There seemed to have been no attempt to keep the place clean. The rooms were small and separated by thin partitions through which conversations in even low tones could be heard. The furniture was cheap and worn with constant use. Downstairs we could hear the uproar as the news spread that the District Attorney was raiding the place. As fast as they could the sordid crowd in the dance hall and cabaret was disappearing. Now and then we could hear a door bang, a hasty conference, and then silence as some of the inmates realized that upstairs all escape was cut off. On the top floor we came to a door, locked and bolted. With all the force that he could gather in the narrow hall, Kennedy catapulted himself against it. It yielded in its rottenness with a crash. A woman, in all her finery, lay across the foot of a bed, a formless heap. Kennedy turned her over. It was Marie, motionless, but still breathing faintly. In an armchair, with his hands hanging limply down almost to the floor, his head sagging forward on his chest, sprawled Harris. Kennedy picked up a little silver receptacle on the floor where it lay near his right hand. It was nearly empty, but as he looked from it quickly to the two insensible figures before us he muttered: "Morphine. They have robbed the law of its punishment." He bent over the suicides, but it was too late to do anything for them. They had paid the price. "My heavens!" he exclaimed suddenly, as a thought flashed over his mind. "I hope they have not carried the secret of Betty Blackwell with them to the grave. Where is Miss Kendall?" Down the hall, cut off from the rest of the hotel into a sort of private suite, Clare had entered one of the rooms and was bending over a pale, wan shadow of a girl, tossing restlessly on a bed. The room was scantily furnished with a dilapidated bureau in one corner and a rickety washstand equipped with a dirty washbowl and pitcher. A few cheap chromos on the walls were the only decorations, and a small badly soiled rug covered a floor innocent for many years of soap. I looked sharply at the girl lying before us. Somehow it did not occur to me who she was. She was so worn that anyone might safely have transported her through the streets and never have been questioned, in spite of the fact that every paper in the country which prints pictures had published her photograph, not once but many times. It was Betty Blackwell at last, struggling against the drugs that had been forced on her, half conscious, but with one firm and acute feeling left--resistance to the end. Kennedy had dropped on his knees before her and was examining her closely. "Open the windows--more air," he ordered. "Walter, see if you can find some ice water and a little stimulant." While Craig was taking such restorative measures as were possible on the spur of the moment, Miss Kendall gently massaged her head and hands. She seemed to understand that she was in the hands of friends, and though she did not know us her mute look of thanks was touching. "Don't get excited, my dear," breathed Miss Kendall into her ear. "You will be all right soon." As the wronged girl relaxed from her constant tension of watching, it seemed as if she fell into a stupor. Now and then she moaned feebly, and words, half-formed, seemed to come to her lips only to die away. Suddenly she seemed to have a vision more vivid than the rest. "No--no--Mr. Ogleby--leave me. Where--my mother--oh, where is mother?" she cried hysterically, sitting bolt upright and staring at us without seeing us. Kennedy passed the broad palm of his hand over her forehead and murmured, "There, there, you are all right now." Then he added to us: "I did not send for her mother because I wasn't sure that we might find her even as well as this. Will someone find Carton? Get the address and send a messenger for Mrs. Blackwell." Sybil was on her knees by the bedside of the girl, holding Betty's hand in both of her own. "You poor, poor girl," she cried softly. "It is--dreadful." She had sunk her head into the worn and dirty covers of the bed. Kennedy reached over and took hold of her arm. "She will be all right, soon," he said reassuringly. "Miss Kendall will take good care of her." As we descended the stairs, we could see Carton at the foot. A patrol wagon had been backed up to the curb in front and the inmates of the place were being taken out, protesting violently at being detained. Further down the hall, by the "office," Dorgan and Ogleby were storming, protesting that "influence" would "break" everyone concerned, from Carton down to the innocent patrolmen. Kennedy listened a moment, then turned to Clare Kendall. "I will leave Miss Blackwell in your care," he said quietly. "It is on her we must rely to prove the contents of the Black Book." Clare nodded, as, with a clang, Carton drove off with his prisoners to see them safely entered on the "blotter." "Our work is over," remarked Kennedy, turning again to Miss Kendall, in a tone as if he might have said more, but refrained. Looking Craig frankly in the eye, she extended her hand in that same cordial straight-arm shake with which she had first greeted us, and added, "But not the memory of this fight we have won." XXVII THE ELECTION NIGHT It was election night. Kennedy and Carton had arranged between them that we were all to receive the returns at the headquarters of the Reform League, where one of the papers which was particularly interested, had installed several special wires. The polls had scarcely closed when Kennedy and I, who had voted early, if not often, in spite of our strenuous day, hastened up to the headquarters. Already it was a scene of activity. The first election district had come in, one on the lower East Side, which was a stronghold of Dorgan, where the count could be made quickly, for there were no split tickets there. Dorgan had drawn first blood. "I hope it isn't an omen," smiled Carton, like a good sport. Kennedy smiled quietly. We looked about, but Miss Ashton was not there. I wondered why not and where she was. The first returns had scarcely begun to filter in, though, when Craig leaned over and whispered to me to go out and find her, either at her home, or if not there, at a woman's club of which she was one of the leading members. I found her at home and sent up my card. She had apparently lost interest in the election and it was with difficulty that I could persuade her to accompany me to the League headquarters. However, I argued the case with what ability I had and finally she consented. The other members of the Ashton family had monopolized the cars and we were obliged to take a taxicab. As our driver threaded his way slowly and carefully through the thronged streets it gave us a splendid chance to see some of the enthusiasm. I think it did Margaret Ashton good, too, to get out, instead of brooding over the events of the past few days, as she had seen them. Her heightened colour made her more attractive than ever. The excitement of any other night in the year paled to insignificance before this. Distracted crowds everywhere were cheering and blowing horns. Now a series of wild shouts broke forth from the dense mass of people before a newspaper bulletin board. Now came sullen groans, hisses, and catcalls, or all together, with cheers, as the returns swung in another direction. Not even baseball could call out such a crowd as this. Enterprising newspapers had established places at which they flashed out the returns on huge sheets on every prominent corner. Some of them had bands, and moving pictures, and elaborate forms of entertainment for the crowds. Now and then, where the crowd was more than usually dense, we had to make a wide detour. Even the quieter streets seemed alive. On some boys had built huge bonfires from barrels and boxes that had been saved religiously for weeks or surreptitiously purloined from the grocer or the patient house-holder. About the fires, they kept an ever watchful eye for the descent of their two sworn enemies--the policeman and the rival gang privateering in the name of a hostile candidate. Boys with armfuls of newspapers were everywhere, selling news that in the rapid-fire change of the statistics seemed almost archeologically old. Lights blazed on every side. Automobiles honked and ground their gears. The lobster palaces, where for weeks, Francois, Carl, and William had been taking small treasury notes for tables reserved against the occasion, were thronged. In theatres people squirmed uneasily until the ends of acts, in order to listen to returns read from the stage before the curtain. Police were everywhere. People with horns, and bells, and all manner of noise-making devices, with confetti and "ticklers" pushed up on one side of Broadway and down on the other. At every square they congested foot and vehicle traffic, as they paused ravenously to feed on the meagre bulletins of news. Yet back of all the noise and human energy, as a newspaperman, I could think only of the silent, systematic gathering and editing of the news, of the busy scenes that each journal's office presented, the haste, the excitement, the thrill in the very smell of the printer's ink. Miss Ashton, I was glad to note, as we proceeded downtown, fell more and more into the spirit of the adventure. High up in the League headquarters in the tower, when we arrived, it was almost like a newspaper office, to me. A corps of clerks was tabulating returns, comparing official and semi-official reports. As first the city swung one way, then another, our hopes rose and fell. I could not help noticing, however, after a while that Miss Ashton seemed cold and ill at ease. There was such a crowd there of Leaguers and their friends that it was easily possible for her not to meet Carton. But as I circulated about in the throng, I came upon him. Carton looked worried and was paying less attention to the returns than seemed natural. It was evident that, in spite of the crowd, she had avoided him and he hesitated to seek her out. There were so many things to think of thrusting themselves into one's attention that I could follow none consistently. First I found myself wondering about Carton and Miss Ashton. Before I knew it I was delivering a snap judgment on whether the uptown residence district returns would be large enough to overcome the hostile downtown vote. I was frankly amazed, now, to see how strongly the city as a whole was turning to the Reform League. A boy, pushing through the crowd, came upon Kennedy and myself, talking to Miss Ashton. He shoved a message quickly into Craig's hand and disappeared. "For heaven's sake!" he exclaimed as he tore open the envelope and read. "What do you think of that? My shadows report that Martin Ogleby has been arrested and his confession will be enough, with the Black Book and Betty Blackwell, to indict Dorgan. Kahn has committed suicide! Hartley Langhorne has sailed for Paris on the French line, with Mrs. Ogleby!" "Mary Ogleby--eloped?" repeated Miss Ashton, aghast. The very name seemed to call up unpleasant associations and her face plainly showed it. Kennedy had said nothing to her since the day when he had pleaded with her to suspend judgment. "By the way," he said in a low voice, leaning over toward her, "have you heard that those pictures of her were faked? It was really Dorgan, and some crook photographer cut out his face and substituted Carton's. We got the Black Book, this morning, too, and it tells the story of Mrs. Ogleby's misadventures--as well as a lot of much more important things. We got it from Mr. Murtha and---" "Mr. Murtha?" she inquired, in surprise. "It is a secret, but I think I can violate it to a certain extent for Mr. Carton is a party to it and--" Kennedy paused. He was speaking with the assurance of one who assumed that John Carton and Margaret Ashton had no secrets. She saw it, and coloured deeply. Then he lowered his voice further to a whisper and when he finished, her face was even a deeper scarlet. But her eyes had a brightness they had lacked for days. And I could see the emotion she felt as her slight form quivered with excitement. Kennedy excused himself and we worked our way through the press toward Carton. "Dorgan has lost his nerve!" ejaculated Craig as we came up with him, watching district after district which showed that the Boss's usual pluralities were being seriously reduced. "Lost his nerve?" repeated Carton. "Yes. I told him I would publish the whole affair of the photographs just as I knew it, not caring whom it hit. I advised him to read his revised statutes again about money in elections and I added the threat, 'There will be no "dough day" or it will be carried to the limit, Dorgan, and I will resurrect Murtha in an hour!' You should have seen his face! There was no dough day. That's what I meant when I said it was to be a fair fight. You see the effect on the returns." Carton was absolutely speechless. The tears stood in his eyes as he grasped Kennedy's hand, then swung around to me. A terrific cheer broke out among the clerks in the outer office. One of them rushed in with a still unblotted report. Kennedy seized it and read: "Dorgan concedes the city by a safe plurality to Carton, fifty-two election districts estimated. This clinches the Reform League victory." I turned to Carton. Behind us, through the crowd, had followed a young lady and now Carton had no ears for anything except the pretty apology of Margaret Ashton. Kennedy pulled me toward the door. "We might as well concede Miss Ashton to Carton," he beamed. "Let's go out and watch the crowd." THE END 
51326	----	available by Internet Archive (https://archive.org) Note: Project Gutenberg also has an HTML version of this file which includes the original illustrations. See 51326-h.htm or 51326-h.zip: (http://www.gutenberg.org/files/51326/51326-h/51326-h.htm) or (http://www.gutenberg.org/files/51326/51326-h.zip) Images of the original pages are available through Internet Archive. See https://archive.org/details/cu31924012367441 Transcriber's note: Text enclosed by underscores is in italics (_italics_). A carat character is used to denote superscription. A single character following the carat is superscripted (example: 0·01717_t_^2). Multiple superscripted characters are enclosed by curly brackets (example: V_{_0_}(1-K_t_)^{-1}). The ligature oe has been transcribed as [oe]. The dagger sign has been transcribed as [+]. The infinity sign has been transcribed as [oo]. THE PRINCIPLES OF CHEMISTRY by D. MENDELÉEFF Translated from the Russian (Sixth Edition) by George Kamensky, A.R.S.M. of the Imperial Mint, St Petersburg: Member of the Russian Physico-Chemical Society Edited by T. A. Lawson, B.Sc. PH.D. Examiner in Coal-Tar Products to the City and Guilds of London Institute Fellow of the Institute of Chemistry In Two Volumes VOLUME I. Longmans, Green, and Co 39 Paternoster Row, London New York and Bombay 1897 All rights reserved PREFACE TO THE ENGLISH TRANSLATION The first English edition of this work was published in 1891, and that a second edition is now called for is, we think, a sufficient proof that the enthusiasm of the author for his science, and the philosophical method of his teaching, have been duly appreciated by English chemists. In the scientific work to which Professor Mendeléeff's life has been devoted, his continual endeavour has been to bring the scattered facts of chemistry within the domain of law, and accordingly in his teaching he endeavours to impress upon the student the _principles_ of the science, the generalisations, so far as they have been discovered, under which the facts naturally group themselves. Of those generalisations the periodic law is perhaps the most important that has been put forward since the establishment of the atomic theory. It is therefore interesting to note that Professor Mendeléeff was led to its discovery in preparing the first Russian edition of this book. It is natural, too, that the further application and development of that generalisation should be the principal feature of this, the latest edition. There are special difficulties in rendering the Russian language into good English, and we are conscious that these have not been entirely overcome. Doubtless also there are errors of statement which have escaped correction, but we believe that the present edition will be found better in both respects than its predecessor. We have thought it our duty as translators to give as far as possible a faithful reproduction of Professor Mendeléeff's work--the sixth Russian edition--without amplifying or modifying his statements, and in this we have the author's approval. Although other duties have prevented Mr. Greenaway from undertaking the care of the present edition, he has been kind enough to give us the benefit of his suggestions on several points. We also wish to thank the Managers of the Royal Institution for permission to reprint the lecture delivered at the Royal Institution by Professor Mendeléeff (Appendix I.), and to the Council of the Chemical Society for permission to reprint the Faraday lecture which forms Appendix II. In conclusion, we are indebted to Mr. F. Evershed, who has given us much valuable assistance in revising the sheets for the press. G. K. T. A. L. _August 1897_ AUTHOR'S PREFACE TO THE SIXTH RUSSIAN EDITION This work was written during the years 1868-1870, its object being to acquaint the student not only with the methods of observation, the experimental facts, and the laws of chemistry, but also with the insight given by this science into the unchangeable substratum underlying the varying forms of matter. If statements of fact themselves depend upon the person who observes them, how much more distinct is the reflection of the personality of him who gives an account of methods and of philosophical speculations which form the essence of science! For this reason there will inevitably be much that is subjective in every objective exposition of science. And as an individual production is only significant in virtue of that which has preceded and that which is contemporary with it, it resembles a mirror which in reflecting exaggerates the size and clearness of neighbouring objects, and causes a person near it to see reflected most plainly those objects which are on the side to which it is directed. Although I have endeavoured to make my book a true mirror directed towards the whole domain of chemical changes, yet involuntarily those influences near to me have been the most clearly reflected, the most brightly illuminated, and have tinted the entire work with their colouring. In this way the chief peculiarity of the book has been determined. Experimental and practical data occupy their place, but the philosophical principles of our science form the chief theme of the work. In former times sciences, like bridges, could only be built up by supporting them on a few broad buttresses and long girders. In addition to the exposition of the principles of chemistry, it has been my desire to show how science has now been built up like a suspension bridge, supported by the united strength of a number of slender, but firmly-fixed, chains, which individually are of little strength, and has thus been carried over difficulties which before appeared insuperable. In comparing the science of the past, the present, and the future, in placing the particulars of its restricted experiments side by side with its aspirations after unbounded and infinite truth, and in restraining myself from yielding to a bias towards the most attractive path, I have endeavoured to incite in the reader a spirit of inquiry, which, dissatisfied with speculative reasonings alone, should subject every idea to experiment, encourage the habit of stubborn work, and excite a search for fresh chains of evidence to complete the bridge over the bottomless unknown. History proves that it is possible by this means to avoid two equally pernicious extremes, the Utopian--a visionary contemplation which proceeds from a current of thought only--and the stagnant realism which is content with bare facts. Sciences like chemistry, which deal with ideas as well as with material substances, and create a possibility of immediately verifying that which has been or may be discovered or assumed, demonstrate at every step that the work of the past has availed much, and that without it it would be impossible to advance into the ocean of the unknown. They also show the possibility of becoming acquainted with fresh portions of this unknown, and compel us, while duly respecting the teachings of history, to cast aside classical illusions, and to engage in a work which not only gives mental satisfaction but is also practically useful to all our fellow-creatures.[1] [1] Chemistry, like every other science, is at once a means and an end. It is a means of attaining certain practical results. Thus, by its assistance, the obtaining of matter in its various forms is facilitated; it shows new possibilities of availing ourselves of the forces of nature, indicates the methods of preparing many substances, points out their properties, &c. In this sense chemistry is closely connected with the work of the manufacturer and the artisan, its sphere is active, and is a means of promoting general welfare. Besides this honourable vocation, chemistry has another. With it, as with every other elaborated science, there are many lofty aspirations, the contemplation of which serves to inspire its workers and adherents. This contemplation comprises not only the principal data of the science, but also the generally-accepted deductions, and also hypotheses which refer to phenomena as yet but imperfectly known. In this latter sense scientific contemplation varies much with times and persons, it bears the stamp of creative power, and embraces the highest forms of scientific progress. In that pure enjoyment experienced on approaching to the ideal, in that eagerness to draw aside the veil from the hidden truth, and even in that discord which exists between the various workers, we ought to see the surest pledges of further scientific progress. Science thus advances, discovering new truths, and at the same time obtaining practical results. The edifice of science not only requires material, but also a plan, and necessitates the work of preparing the materials, putting them together, working out the plans and the symmetrical proportions of the various parts. To conceive, understand, and grasp the whole symmetry of the scientific edifice, including its unfinished portions, is equivalent to tasting that enjoyment only conveyed by the highest forms of beauty and truth. Without the material, the plan alone is but a castle in the air--a mere possibility; whilst the material without a plan is but useless matter. All depends on the concordance of the materials with the plan and execution, and the general harmony thereby attained. In the work of science, the artisan, architect, and creator are very often one and the same individual; but sometimes, as in other walks of life, there is a difference between them; sometimes the plan is preconceived, sometimes it follows the preparation and accumulation of the raw material. Free access to the edifice of science is not only allowed to those who devised the plan, worked out the detailed drawings, prepared the materials, or piled up the brickwork, but also to all those who are desirous of making a close acquaintance with the plan, and wish to avoid dwelling in the vaults or in the garrets where the useless lumber is stored. Knowing how contented, free, and joyful is life in the realm of science, one fervently wishes that many would enter its portals. On this account many pages of this treatise are unwittingly stamped with the earnest desire that the habits of chemical contemplation which I have endeavoured to instil into the minds of my readers will incite them to the further study of science. Science will then flourish in them and by them, on a fuller acquaintance not only with that little which is enclosed within the narrow limits of my work, but with the further learning which they must imbibe in order to make themselves masters of our science and partakers in its further advancement. Those who enlist in the cause of science have no reason to fear when they remember the urgent need for practical workers in the spheres of agriculture, arts, and manufacture. By summoning adherents to the work of theoretical chemistry, I am confident that I call them to a most useful labour, to the habit of dealing correctly with nature and its laws, and to the possibility of becoming truly practical men. In order to become actual chemists, it is necessary for beginners to be well and closely acquainted with three important branches of chemistry--analytical, organic, and theoretical. That part of chemistry which is dealt with in this treatise is only the groundwork of the edifice. For the learning and development of chemistry in its truest and fullest sense, beginners ought, in the first place, to turn their attention to the practical work of analytical chemistry; in the second place, to practical and theoretical acquaintance with some special chemical question, studying the original treatises of the investigators of the subject (at first, under the direction of experienced teachers), because in working out particular facts the faculty of judgment and of correct criticism becomes sharpened; in the third place, to a knowledge of current scientific questions through the special chemical journals and papers, and by intercourse with other chemists. The time has come to turn aside from visionary contemplation, from platonic aspirations, and from classical verbosity, and to enter the regions of actual labour for the common weal, to prove that the study of science is not only air excellent education for youth, but that it instils the virtues of industry and veracity, and creates solid national wealth, material and mental, which without it would be unattainable. Science, which deals with the infinite, is itself without bounds. Thus the desire to direct those thirsting for truth to the pure source of the science of the forces acting throughout nature forms the first and most important aim of this book. The time has arrived when a knowledge of physics and chemistry forms as important a part of education as that of the classics did two centuries ago. In those days the nations which excelled in classical learning stood foremost, just as now the most advanced are those which are superior in the knowledge of the natural sciences, for they form the strength and characteristic of our times. In following the above and chief aim, I set myself a second object: to furnish a text-book for an elementary knowledge of chemistry and so satisfy a want which undoubtedly exists among students and those who have recourse to chemistry either as a source of truth or welfare.[2] Hence, although the fundamental object of this work was to express and embrace the general chemical teaching of the present day from a personal point of view, I have nevertheless striven throughout to maintain such a level as would render the 'Principles of Chemistry' accessible to the beginner. Many aspects of this work are determined by this combination of requirements which frequently differ widely. An issue was only possible under one condition, _i.e._ not to be carried away by what appears to be a plausible theory in explaining individual facts and to always endeavour to transmit the simple truth of a given fact, extracting it from the vast store of the literature of the subject and from tried personal experience. In publishing a new edition of this work I have striven to add any facts of importance recently discovered[3] and to revise the former edition in the above spirit. With this object I have entirely gone over this edition, and a comparison of it with the former one will show that the additions and alterations have cost as much labour as many chapters of the work. I also wished to show in an elementary treatise on chemistry the striking advantages gained by the application of the periodic law, which I first saw in its entirety in the year 1869 when I was engaged in writing the first edition of this book, in which, indeed, the law was first enunciated. At that time, however, this law was not established so firmly as now, when so many of its consequences have been verified by the researches of numerous chemists, and especially by Roscoe, Lecoq de Boisbaudran, Nilson, Brauner, Thorpe, Carnelley, Laurie, Winkler, and others. The, to me, unexpectedly rapid success with which the teaching of the periodicity of the elements has spread in our science, and perhaps also, the perseverance with which I collected in this work, and upon a new plan, the most important data respecting the elements and their mutual relations, explained sufficiently the fact that the former (5th, 1889) edition of my work has been translated into English[4] and German[5] and is being translated into French.[6] Deeply touched by the favourable opinions expressed by English men of science upon my book, I ascribe them chiefly to the periodic law placed at the basis of my treatise and especially of the second part of the book, which contains a large amount of data having a special and sometimes quite unexpected, bearing from the point of view of this law. As the entire scheme of this work is subordinated to the law of periodicity, which may be illustrated in a tabular form by placing the elements in series, groups, and periods, two such tables are given at the end of this preface. [2] I recommend those who are commencing the study of chemistry with my book _to first read only what is printed in the large type_, because in that part I have endeavoured to concentrate all the fundamental, indispensable knowledge required for that study. In the footnotes, printed in small type (which should be read only after the large text has been mastered), certain details are discussed; they are either further examples, or debatable questions on existing ideas which I thought useful to lay before those entering into the sphere of science, or certain historical and technical details which might be withdrawn from the fundamental portion of the book. Without intending to attain in my treatise to the completeness of a work of reference, I have still endeavoured to express the principal developments of science as they concern the chemical elements viewed in that aspect in which they appeared to me after long continued study of the subject and participation in the contemporary advance of knowledge. I have also placed my personal views, suppositions, and arguments in the footnotes, which are chiefly designed for details and references. But I have endeavoured to avoid here, as in the text, not only all that I consider doubtful, but also those details which belong either to special branches of chemistry (for instance, to analytical, organic, physical, theoretical, physiological, agricultural, or technical chemistry), or to different branches of natural science which are more and more coming into closer and closer contact with chemistry. Chemistry, I am convinced, must occupy a place among the natural sciences side by side with mechanics; for mechanics treats of matter as a system of ponderable points having scarcely any individuality and only standing in a certain state of mobile equilibrium. For chemistry, matter is an entire world of life, with an infinite variety of individuality both in the elements and in their combinations. In studying the general uniformity from a mechanical point of view, I think that the highest point of knowledge of nature cannot be attained without taking into account the individuality of things in which chemistry is set to seek for general higher laws. Mechanics may be likened to the science of statesmanship, chemistry to the sciences of jurisprudence and sociology. The general universe could not be built up without the particular individual universe, and would be a dry abstract were it not enlivened by the real variety of the individual world. Mechanics forms the classical basis of natural philosophy, while chemistry, as a comparatively new and still young science, already strives to--and will, in the future introduce a new, living aspect into the philosophy of nature; all the more as chemistry alone is never at rest or anywhere dead--its vital action has universal sway, and inevitably determines the general aspect of the universe. Just as the microscope and telescope enlarge the scope of vision, and discover life in seeming immobility, so chemistry, in discovering and striving to discern the life of the invisible world of atoms and molecules and their ultimate limit of divisibility, will clearly introduce new and important problems into our conception of nature. And I think that its _rôle_, which is now considerable, will increase more and more in the future; that is, I think that in its further development it will occupy a place side by side with mechanics for the comprehension of the secrets of nature. But here we require some second Newton; and I have no doubt that he will soon appear. [3] I was much helped in gathering data from the various chemical journals of the last five years by the abstracts made for me by Mr. Y. V. Kouriloff, to whom I tender my best thanks. [4] The English translation was made by G. Kamensky, and edited by A. J. Greenaway; published by Longmans, Green & Co. [5] The German translation was made by L. Jawein and A. Thillot; published by Ricker (St. Petersburg). [6] The French translation has been commenced by E. Achkinasi and H. Carrion from the fifth edition, and is published by Tignol (Paris). In this the sixth edition I have not altered any essential feature of the original work, and have retained those alterations which were introduced into the fifth edition.[7] I have, however, added many newly discovered facts, and in this respect it is necessary to say a few words. Although all aspects of the simplest chemical relations are as far as possible equally developed in this book, yet on looking back I see that I have, nevertheless, given most attention to the so-called indefinite compounds examples of which may be seen in solutions. I recur repeatedly to them, and to all the latest data respecting them, for in them I see a starting point for the future progress of our science and to them I affiliate numerous instances of definite compounds, beginning with alloys and silicates and ending with complex acids. There are two reasons for this. In the first place, this subject has deeply interested me from my youth; I have devoted a portion of my own researches to it, and therefore it occupied an important position even in the first edition of my book; besides which all that has been subsequently accomplished in our science, especially during the last five or six years, shows that at the present day an interest in these questions plays an important part in the minds of a large circle of contemporary workers in chemistry. This personal attachment, if I may so call it, to the question of solutions and such indefinite compounds, must involuntarily have impressed itself upon my work, and in the later editions I have even had to strive not to give this subject a greater development than previously, so great was the material accumulated, which however does not yet give us the right to consider even the most elementary questions respecting solutions as solved. Thus, we cannot yet say what a solution really is. My own view is that a solution is a homogeneous liquid system of unstable dissociating compounds of the solvent with the substance dissolved. But although such a theory explains much to me, I cannot consider my opinion as proved, and therefore give it with some reserve as one of several hypotheses.[8] As a subject yet far from solved, I might naturally have ignored it, or only mentioned it cursorily, but such a treatment of solutions, although usual in elementary treatises on chemistry, would not have answered my views upon the subject of our science, and I wished that the reader might find in my book beyond everything an expression of all that a study of the subject built up for me. If in solutions I see and can frequently prove distinct evidences of the existence of those definite compounds which form the more generalised province of chemical data, I could not refrain from going into certain details respecting solutions; otherwise, there would have remained no trace of that general idea, that in them we have only a certain instance of ordinary definite or atomic compounds, subject to Dalton's laws. Having long had this idea, I wished to impress it upon the reader of my book, and it is this desire which forms the second of those chief reasons why I recur so frequently to solutions in this work. At present, my ideas respecting solutions are shared by few, but I trust that by degrees the instances I give will pave the way for their general recognition, and it is my hope that they may find adherents among those of my readers who are in a position to work out by experiment this difficult but highly interesting problem. [7] The fifth edition was not only considerably enlarged, compared with the preceding, but also the foundations of the periodic system of the elements were placed far more firmly in it than in the former editions. The subject-matter was also divided into text and footnotes, which contained details unnecessary for a first acquaintance with chemistry. The fifth edition sold out sooner than I expected, so that instead of issuing supplements (containing the latest discoveries in chemistry), as I had proposed, I was obliged to publish the present entirely new edition of the work. [8] This hypothesis is not only mentioned in different parts of this book, but is partly (from the aspect of the specific gravity of solutions) developed in my work, _The Investigation of Solutions from their Specific Gravity_, 1887. In conclusion, I desire to record my thanks to V. D. Sapogenikoff, who has corrected the proofs of the whole of this edition and compiled the indexes which greatly facilitate the search for those details which are scattered throughout the work. D. MENDELÉEFF. TABLE I _Distribution of the Elements in Groups and Series_ +--------+-------+----------+----------+----------+----------+ | Group | I. | II. | III. | IV. | V. | +--------+-------+----------+----------+----------+----------+ |Series 1| H | -- | -- | -- | -- | | | | | | | | | " 2| Li | Be | B | C | N | | | | | | | | | " 3| Na | Mg | Al | Si | P | | | | | | | | | " 4| K | Ca | Sc | Ti | V | | | | | | | | | " 5| (Cu)| Zn | Ga | Ge | As | | | | | | | | | " 6| Rb | Sr | Y | Zr | Nb | | | | | | | | | " 7| (Ag)| Cd | In | Sn | Sb | | | | | | | | | " 8| Cs | Ba | La | Ce | Di? | | | | | | | | | " 9| -- | -- | -- | -- | -- | | | | | | | | | " 10| -- | -- | Yb | -- | Ta | | | | | | | | | " 11| (Au)| Hg | Tl | Pb | Bi | | | | | | | | | " 12| -- | -- | -- | Th | -- | | | | | | | | +--------+-------+----------+----------+----------+----------+ | |R_{2}O |R_{2}O_{2}|R_{2}O_{3}|R_{2}O_{4}|R_{2}O_{5}| | | | | | | | | | -- |RO | -- |RO_{2} | -- | | | | | | | | | | -- | -- | -- |RH_{4} |RH_{3} | | | | | | | | +--------+-------+----------+----------+----------+----------+ +---------+----------+----------+--------------------+ | Group | VI. | VII. | VIII. | +---------+----------+----------+--------------------+ | Series 1| -- | -- | | | | | | | | " 2| O | F | | | | | | | | " 3| S | Cl | | | | | | | | " 4| Cr | Mn | Fe Co Ni Cu | | | | | | | " 5| Se | Br | | | | | | | | " 6| Mo | -- | Ru Rh Pd Ag | | | | | | | " 7| Te | I | | | | | | | | " 8| -- | -- | -- -- -- -- | | | | | | | " 9| -- | -- | | | | | | | | " 10| W | -- | Os Ir Pt Au | | | | | | | " 11| -- | -- | | | | | | | | " 12| U | -- | | | | | | | +---------+----------+----------+--------------------+ | |R_{2}O_{6}|R_{2}O_{7}| Higher oxides | | | | | | | |RO_{3} | -- | RO_{4} | | | | | | | |RH_{2} | RH | Hydrogen compounds | +---------+----------+----------+--------------------+ TABLE II _Periodic System and Atomic Weights of the Elements_ (_Giving the pages on which they are described_) +---------------------+--------------+--------------+--------------+ | | 2nd Series, | | | | | Typical | 4th | 6th | | | elements | Series | Series | +-------+-------------+--------------+--------------+--------------+ | I. | | Li 7 | K 39 | Rb 86 | | | | | ==== | | | | | vol. i. 574 | vol. i. 558 | vol. i. 576 | | | | | | | | II. | | Be 9 | Ca 40 | Sr 88 | | | | | ----- | | | | | vol. i. 618 | vol. i. 590 | vol. i. 614 | | | | | | | | III. | | B 11 | Sc 44 | Y 89 | | | | ---- | | | | | | vol. ii. 60 | vol. ii. 94 | vol. ii. 93 | | | | | | | | IV. | | C 12 | Ti 48 | Zr 91 | | | | ==== | | | | | | vol. i. 338 | vol. ii. 144 | vol. ii. 93 | | | | | | | | V. | | N 14 | V 51 | Nb 94 | | | | ==== | | | | | | vol. i. 223 | vol. ii. 194 | vol. ii. 197 | | | | | | | | VI. | | O 16 | Cr 52 | Mo 96 | | | | ---- | ----- | | | | | vol. i. 155 | vol. ii. 276 | vol. ii. 290 | | | | | | | | VII. | | F 19 | Mn 55 | ? 99 | | | | | ===== | | | | | vol. i. 489 | vol. ii. 303 | | | | | | | | | | | | Fe 56 | Ru 102 | | | | | ===== | | | | | | vol. ii. 317 | vol. ii. 369 | | | | | | | | VIII. | | | Co 59 | Rh 103 | | | | | vol. ii. 353 | vol. ii. 369 | | | | | | | | | | | Ni 59·5 | Pd 106 | | | | | vol. ii. 353 | vol. ii. 369 | | | | | | | | | | 3rd Series | 5th Series | 7th Series | | | | | | | | I. | H 1 | Na 23 | Cu 64 | Ag 108 | | | ---- | | | | | | vol. i. 129 | vol. i. 533 | vol. ii. 398 | vol. ii. 415 | | | | | | | | II. | | Mg 24 | Zn 65 | Cd 112 | | | | vol. i. 590 | vol. ii. 39 | vol. ii. 47 | | | | | | | | III. | | Al 27 | Ga 70 | In 114 | | | | vol. ii. 70 | vol. ii. 90 | vol. ii. 91 | | | | | | | | IV. | | Si 28 | Ge 72 | Sn 119 | | | | vol. ii. 99 | vol. ii. 124 | vol. ii. 125 | | | | | | | | V. | | P 31 | As 75 | Sb 120 | | | | | ----- | | | | | vol. ii. 149 | vol. ii. 179 | vol. ii. 186 | | | | | | | | VI. | | S 32 | Se 79 | Te 125 | | | | vol. ii. 200 | vol. ii. 270 | vol. ii. 270 | | | | | | | | VII. | | Cl 35·5 | Br 80 | I 127 | | | | | ----- | | | | | vol. i. 459 | vol. i. 494 | vol. i. 496 | +-------+-------------+--------------+--------------+--------------+ +-------+-------------+--------------+--------------+ | | | | | | | 8th | 10th | 12th | | | Series | Series | Series | +---- --+-------------+--------------+--------------+ | I. | Cs 133 | -- | -- | | | vol. i. 576 | | | | | | | | | II. | Ba 137 | -- | -- | | | ------ | | | | | vol. i. 614 | | | | | | | | | III. | La 138 | Yb 173 | -- | | | vol. ii. 93 | vol. ii. 93 | | | | | | | | IV. | Ce 140 | ? 178 | Th 232 | | | vol. ii. 93 | | vol. ii. 148 | | | | | | | V. | ? Di 142 | Ta 183 | -- | | | vol. ii. 93 | vol. ii. 197 | | | | | | | | VI. | -- | W 184 | U 239 | | | | vol. ii. 290 | vol. ii. 297 | | | | | | | VII. | -- | -- | -- | | | | | | | | -- | Os 192 | | | | | vol. ii. 369 | | | | | | | | VIII. | -- | Ir 193 | | | | | vol. ii. 369 | | | | | | | | | -- | Pt 196 | | | | | ------ | | | | | vol. ii. 369 | | | | | | | | | 9th | 11th | | | | Series | Series | | | | | | | | I. | -- | Au 197 | | | | | vol. ii. 442 | | | | | | | | II. | -- | Hg 200 | | | | | vol. ii. 48 | | | | | | | | III. | -- | Tl 204 | | | | | vol. ii. 91 | | | | | | | | IV. | -- | Pb 207 | | | | | vol. ii. 134 | | | | | | | | V. | -- | Bi 209 | | | | | vol. ii. 189 | | | | | | | | VI. | -- | -- | | | | | | | | VII. | -- | -- | | +-------+-------------+--------------+--------------+ _Note._--Two lines under the elements indicate those which are very widely distributed in nature; one line indicates those which, although not so frequently met with, are of general use in the arts and manufactures. CONTENTS OF THE FIRST VOLUME PAGE TRANSLATORS' PREFACE v AUTHOR'S PREFACE TO THE SIXTH RUSSIAN EDITION vii TABLE OF THE DISTRIBUTION OF THE ELEMENTS IN GROUPS AND SERIES xv TABLE OF THE PERIODIC SYSTEM AND ATOMIC WEIGHTS OF THE ELEMENTS xvi INTRODUCTION 1 CHAP. I. ON WATER AND ITS COMPOUNDS 40 II. THE COMPOSITION OF WATER. HYDROGEN 113 III. OXYGEN AND THE CHIEF ASPECTS OF ITS SALINE COMBINATIONS 152 IV. OZONE AND HYDROGEN PEROXIDE. DALTON'S LAW 198 V. NITROGEN AND AIR 223 VI. THE COMPOUNDS OF NITROGEN WITH HYDROGEN AND OXYGEN 246 VII. MOLECULES AND ATOMS. THE LAWS OF GAY-LUSSAC AND AVOGADRO-GERHARDT 299 VIII. CARBON AND THE HYDROCARBONS 338 IX. COMPOUNDS OF CARBON WITH OXYGEN AND NITROGEN 379 X. SODIUM CHLORIDE. BERTHOLLET'S LAWS. HYDROCHLORIC ACID 417 XI. THE HALOGENS: CHLORINE, BROMINE, IODINE AND FLUORINE 459 XII. SODIUM 513 XIII. POTASSIUM, RUBIDIUM, CÆSIUM AND LITHIUM. SPECTRUM ANALYSIS 543 XIV. THE VALENCY AND SPECIFIC HEAT OF THE METALS. MAGNESIUM, CALCIUM, STRONTIUM, BARIUM, AND BERYLLIUM 581 PRINCIPLES OF CHEMISTRY INTRODUCTION The study of natural science, whose rapid development dates from the days of Galileo ([+]1642) and Newton ([+]1727), and its closer application to the external universe[1] led to the separation of Chemistry as a particular branch of natural philosophy, not only owing to the increasing store of observations and experiments relating to the mutual transformations of substances, but also, and more especially, because in addition to gravity, cohesion, heat, light and electricity it became necessary to recognise the existence of particular internal forces in the ultimate parts of all substances, forces which make themselves manifest in the transformations of substances into one another, but remain hidden (latent) under ordinary circumstances, and whose existence cannot therefore be directly apprehended, and so for a long time remained unrecognised. The primary object of chemistry is the study of the homogeneous substances[2] of which all the objects of the universe are made up, with the transformations of these substances into each other, and with the phenomena[3] which accompany such transformations. Every chemical change or reaction,[4] as it is called, can only take place under a condition of most intimate and close contact of the re-acting substances,[5] and is determined by the forces proper to the smallest invisible particles (molecules) of matter. We must distinguish three chief classes of chemical transformations. [1] The investigation of a substance or a natural phenomenon consists (_a_) in determining the relation of the object under examination to that which is already known, either from previous researches, or from experiment, or from the knowledge of the common surroundings of life--that is, in determining and expressing the quality of the unknown by the aid of that which is known; (_b_) in measuring all that which can be subjected to measurement, and thereby denoting the quantitative relation of that under investigation to that already known and its relation to the categories of time, space, temperature, mass, &c.; (_c_) in determining the position held by the object under investigation in the system of known objects guided by both qualitative and quantitative data; (_d_) in determining, from the quantities which have been measured, the empirical (visible) dependence (function, or 'law,' as it is sometimes termed) of variable factors--for instance, the dependence of the composition of the substance on its properties, of temperature on time, of time on locality, &c.; (_e_) in framing hypotheses or propositions as to the actual cause and true nature of the relation between that studied (measured or observed) and that which is known or the categories of time, space, &c.; (_f_) in verifying the logical consequences of the hypotheses by experiment; and (_g_) in advancing a theory which shall account for the nature of the properties of that studied in its relations with things already known and with those conditions or categories among which it exists. It is certain that it is only possible to carry out these investigations when we have taken as a basis some incontestable fact which is self-evident to our understanding; as, for instance, number, time, space, motion, or mass. The determination of such primary or fundamental conceptions, although not excluded from the possibility of investigation, frequently does not subject itself to our present mode of scientific generalisation. Hence it follows that in the investigation of anything, there always remains something which is accepted without investigation, or admitted as a known factor. The axioms of geometry may be taken as an example. Thus in the science of biology it is necessary to admit the faculty of organisms for multiplying themselves, as a conception whose meaning is as yet unknown. In the study of chemistry, too, the notion of elements must be accepted almost without any further analysis. However, by first investigating that which is visible and subject to direct observation by the organs of the senses, we may hope that in the first place hypotheses will be arrived at, and afterwards theories of that which has now to be placed at the basis of our investigations. The minds of the ancients strove to seize at once the very fundamental categories of investigation, whilst all the successes of recent knowledge are based on the above-cited method of investigation without the determination of 'the beginning of all beginnings.' By following this inductive method, the _exact sciences_ have already succeeded in becoming accurately acquainted with much of the invisible world, which directly is imperceptible to the organs of sense (for example, the molecular motion of all bodies, the composition of the heavenly luminaries, the paths of their motion, the necessity for the existence of substances which cannot be subjected to experiment, &c.), and have verified the knowledge thus obtained, and employed it for increasing the interests of humanity. It may therefore be safely said that _the inductive method of investigation_ is a more perfect mode of acquiring knowledge than the deductive method alone (starting from a little of the unknown accepted as incontestable to arrive at the much which is visible and observable) by which the ancients strove to embrace the universe. By investigating the universe by an inductive method (endeavouring from the much which is observable to arrive at a little which may be verified and is indubitable) the new science refuses to recognise dogma as truth, but through _reason_, by a slow and laborious method of investigation, strives for and attains to true deductions. [2] A substance or material is that which occupies space and has weight; that is, which presents a mass attracted by the earth and by other masses of material, and of which the _objects_ of nature are composed, and by means of which the motions and _phenomena_ of nature are accomplished. It is easy to discover by examining and investigating, by various methods, the objects met with in nature and in the arts, that some of them are homogeneous, whilst others are composed of a mixture of several homogeneous substances. This is most clearly apparent in solid substances. The metals used in the arts (for example, gold, iron, copper) must be homogeneous, otherwise they are brittle and unfit for many purposes. Homogeneous matter exhibits similar properties in all its parts. By breaking up a homogeneous substance we obtain parts which, although different in form, resemble each other in their properties. Glass, pure sugar, marble, &c., are examples of homogeneous substances. Examples of non-homogeneous substances are, however, much more frequent in nature and the arts. Thus the majority of the rocks are not homogeneous. In porphyries bright pieces of a mineral called 'orthoclase' are often seen interspersed amongst the dark mass of the rock. In ordinary red granite it is easy to distinguish large pieces of orthoclase mixed with dark semi-transparent quartz and flexible laminæ of mica. Similarly, plants and animals are non-homogeneous. Thus, leaves are composed of a skin, fibre, pulp, sap, and a green colouring matter. As an example of those non-homogeneous substances which are produced artificially, gunpowder may be cited, which is prepared by mixing together known proportions of sulphur, nitre, and charcoal. Many liquids, also, are not homogeneous, as may be observed by the aid of the microscope, when drops of blood are seen to consist of a colourless liquid in which red corpuscles, invisible to the naked eye owing to their small size, are floating about. It is these corpuscles which give blood its peculiar colour. Milk is also a transparent liquid, in which microscopical drops of fat are floating, which rise to the top when milk is left at rest, forming cream. It is possible to extract from every non-homogeneous substance those homogeneous substances of which it is made up. Thus orthoclase may he separated from porphyry by breaking it off. So also gold is extracted from auriferous sand by washing away the mixture of clay and sand. Chemistry deals only with the homogeneous substances met with in nature, or extracted from natural or artificial non-homogeneous substances. The various mixtures found in nature form the subjects of other natural sciences--as geognosy, botany, zoology, anatomy, &c. [3] All those events which are accomplished by substances in time are termed 'phenomena.' Phenomena in themselves form the fundamental subject of the study of physics. Motion is the primary and most generally understood form of phenomenon, and therefore we endeavour to reason about other phenomena as clearly as when dealing with motion. For this reason mechanics, which treats of motion, forms the fundamental science of natural philosophy, and all other sciences endeavour to reduce the phenomena with which they are concerned to mechanical principles. Astronomy was the first to take to this path of reasoning, and succeeded in many cases in reducing astronomical to purely mechanical phenomena. Chemistry and physics, physiology and biology are proceeding in the same direction. One of the most important questions of all natural science, and one which has been handed down from the philosophers of classic times, is, whether the comprehension of all that is visible can be reduced to motion? Its participation in all, from the 'fixed' stars to the most minute parts of the coldest bodies (Dewar, in 1894 showed that many substances cooled to -180° fluoresce more strongly than at the ordinary temperature; _i.e._ that there is a motion in them which produces light) must now be recognised as undoubtable from direct experiment and observation, but it does not follow from this that by motion alone can all be explained. This follows, however, from the fact that we cannot apprehend motion otherwise than by recognising matter in a state of motion. If light and electricity be understood as particular forms of motion, then we must inevitably recognise the existence of a peculiar luminiferous (universal) ether as a material, transmitting this form of motion. And so, under the present state of knowledge, it is inevitably necessary to recognise the particular categories, motion and matter, and as chemistry is more closely concerned with the various forms of the latter, it should, together with mechanics or the study of motion, lie at the basis of natural science. [4] The verb 'to react' means to act or change chemically. [5] If a phenomenon proceeds at visible or measurable distances (as, for instance, magnetic attraction or gravity), it cannot be described as chemical, since these phenomena only take place at distances immeasurably small and undistinguishable to the eye or the microscope; that is to say, they are purely molecular. 1. _Combination_ is a reaction in which the union of two substances yields a new one, or in general terms, from a given number of substances, a lesser number is obtained. Thus, by heating a mixture of iron and sulphur[6] a single new substance is produced, iron sulphide, in which the constituent substances cannot be distinguished even by the highest magnifying power. Before the reaction, the iron could be separated from the mixture by a magnet, and the sulphur by dissolving it in certain oily liquids;[7] in general, before combination they might be mechanically separated from each other, but after combination both substances penetrate into each other, and are then neither mechanically separable nor individually distinguishable. As a rule, reactions of direct combination are accompanied by an evolution of heat, and the common case of combustion, evolving heat, consists in the combination of combustible substances with a portion (oxygen) of the atmosphere, the gases and vapours contained in the smoke being the products of combination. 2. Reactions of _decomposition_ are cases the reverse of those of combination, that is, in which one substance gives two--or, in general, a given number of substances a greater number. Thus, by heating wood (and also coal and many animal or vegetable substances) without access to air, a combustible gas, a watery liquid, tar, and carbon are obtained. It is in this way that tar, illuminating gas, and charcoal are prepared on a large scale.[8] All limestones, for example, flagstones, chalk, or marble, are decomposed by heating to redness into lime and a peculiar gas called carbonic anhydride. A similar decomposition, taking place, however, at a much lower temperature, proceeds with the green copper carbonate which is contained in natural malachite. This example will be studied more in detail presently. Whilst heat is evolved in the ordinary reactions of combination, it is, on the contrary, absorbed in the reactions of decomposition. 3. The third class of chemical reactions--where the number of re-acting substances is equal to the number of substances formed--may be considered as a simultaneous decomposition and combination. If, for instance, two compounds A and B are taken and they react on each other to form the substances C and D, then supposing that A is decomposed into D and E, and that E combines with B to form C, we have a reaction in which two substances A, or D E, and B were taken and two others C, or E B, and D were produced. Such reactions ought to be placed under the general term of reactions of '_rearrangement_,' and the particular case where two substances give two fresh ones, reactions of '_substitution_.'[9] Thus, if a piece of iron be immersed in a solution of blue vitriol (copper sulphate), copper is formed--or, rather, separated out, and green vitriol (iron sulphate, which only differs from the blue vitriol in that the iron has replaced the copper) is obtained in solution. In this manner iron may be coated with copper, so also copper with silver; such reactions are frequently made use of in practice. [6] For this purpose a piece of iron may be made red hot in a forge, and then placed in contact with a lump of sulphur, when iron sulphide will be obtained as a molten liquid, the combination being accompanied by a visible increase in the glow of the iron. Or else iron filings are mixed with powdered sulphur in the proportion of 5 parts of iron to 3 parts of sulphur, and the mixture placed in a glass tube, which is then heated in one place. Combination does not commence without the aid of external heat, but when once started in any portion of the mixture it extends throughout the entire mass, because the portion first heated evolves sufficient heat in forming iron sulphide to raise the adjacent parts of the mixture to the temperature required for starting the reaction. The rise in temperature thus produced is so high as to soften the glass tube. [7] Sulphur is slightly soluble in many thin oils; it is very soluble in carbon bisulphide and in some other liquids. Iron is insoluble in carbon bisulphide, and the sulphur therefore can be dissolved away from the iron. [8] Decomposition of this kind is termed 'dry distillation,' because, as in distillation, the substance is heated and vapours are given off which, on cooling, condense into liquids. In general, decomposition, in absorbing heat, presents much in common to a physical change of state--such as, for example, that of a liquid into a gas. Deville likened complete decomposition to boiling, and compared partial decomposition, when a portion of a substance is not decomposed in the presence of its products of decomposition (or dissociation), to evaporation. [9] A reaction of rearrangement may in certain cases take place with one substance only; that is to say, a substance may by itself change into a new isomeric form. Thus, for example, if hard yellow sulphur be heated to a temperature of 250° and then poured into cold water it gives, on cooling, a soft, brown variety. Ordinary phosphorus, which is transparent, poisonous, and phosphorescent in the dark (in the air), gives, after being heated at 270° (in an atmosphere incapable of supporting combustion, such as steam), an opaque, red, and non-poisonous isomeric variety, which is not phosphorescent. Cases of isomerism point out the possibility of an internal rearrangement in a substance, and are the result of an alteration in the grouping of the same elements, just as a certain number of balls may be grouped in figures and forms of different shapes. The majority of the chemical changes which occur in nature and are made use of technically are very complicated, as they consist of an association of many separate and simultaneous combinations, decompositions, and replacements. It is chiefly due to this natural complexity of chemical phenomena that for so many centuries chemistry did not exist as an exact science; that is so say, that although many chemical changes were known and made use of,[10] yet their real nature was unknown, nor could they be predicted or directed at will. Another reason for the tardy progress of chemical knowledge is the participation of gaseous substances, especially air, in many reactions. The true comprehension of air as a ponderable substance, and of gases in general as peculiar elastic and dispersive states of matter, was only arrived at in the sixteenth and seventeenth centuries, and it was only after this that the transformations of substances could form a science. Up to that time, without understanding the invisible and yet ponderable gaseous and vaporous states of substances, it was impossible to obtain any fundamental chemical evidence, because gases escaped from notice between the reacting and resultant substances. It is easy from the impression conveyed to us by the phenomena we observe to form the opinion that matter is created and destroyed: a whole mass of trees burn, and there only remains a little charcoal and ash, whilst from one small seed there grows little by little a majestic tree. In one case matter seems to be destroyed, and in the other to be created. This conclusion is arrived at because the formation or consumption of gases, being under the circumstances invisible to the eye, is not observed. When wood burns it undergoes a chemical change into gaseous products, which escape as smoke. A very simple experiment will prove this. By collecting the smoke it may be observed that it contains gases which differ entirely from air, being incapable of supporting combustion or respiration. These gases may be weighed, and it will then be seen that their weight exceeds that of the wood taken. This increase in weight arises from the fact that, in burning, the component parts of the wood combine with a portion of the air; in like manner iron increases in weight by rusting. In burning gunpowder its substance is not destroyed, but only converted into gases and smoke. So also in the growth of a tree; the seed does not increase in mass of itself and from itself, but grows because it absorbs gases from the atmosphere and sucks water and substances dissolved therein from the earth through its roots. The sap and solid substances which give plants their form are produced from these absorbed gases and liquids by complicated chemical processes. The gases and liquids are converted into solid substances by the plants themselves. Plants not only do not increase in size, but die, in a gas which does not contain the constituents of air. When moist substances dry they decrease in weight; when water evaporates we know that it does not disappear, but will return from the atmosphere as rain, dew, and snow. When water is absorbed by the earth, it does not disappear there for ever, but accumulates somewhere underground, from whence it afterwards flows forth as a spring. Thus matter does not disappear and is not created, but only undergoes various physical and chemical transformations--that is to say, changes its locality and form. Matter remains on the earth in the same quantity as before; in a word it is, so far as we are concerned, everlasting. It was difficult to submit this simple and primary truth of chemistry to investigation, but when once made clear it rapidly spread, and now seems as natural and simple as many truths which have been acknowledged for ages. Mariotte and other savants of the seventeenth century already suspected the existence of the law of the indestructibility of matter, but they made no efforts to express it or to apply it to the requirements of science. The experiments by means of which this simple law was arrived at were made during the latter half of the last century by the founder of modern chemistry, LAVOISIER, the French Academician and tax farmer. The numerous experiments of this savant were conducted with the aid of the balance, which is the only means of directly and accurately determining the quantity of matter. [10] Thus the ancients knew how to convert the juice of grapes containing the saccharine principle (glucose) into wine or vinegar, how to extract metals from the ores which are found in the earth's crust, and how to prepare glass from earthy substances. Lavoisier found, by weighing all the substances, and even the apparatus, used in every experiment, and then weighing the substances obtained after the chemical change, that the sum of the weights of the substances formed was always equal to the sum of the weights of the substances taken; or, in other words: MATTER IS NOT CREATED AND DOES NOT DISAPPEAR, or that, _matter is everlasting_. This expression naturally includes a hypothesis, but our only aim in using it is to concisely express the following lengthy period--That in all experiments, and in all the investigated phenomena of nature, it has never been observed that the weight of the substances formed was less or greater (as far as accuracy of weighing permits[11]) than the weight of the substances originally taken, and as weight is proportional to mass[11 bis] or quantity of matter, it follows that no one has ever succeeded in observing a disappearance of matter or its appearance in fresh quantities. The law of the indestructibility of matter endows all chemical investigations with exactitude, as, on its basis, an equation may be formed for every chemical reaction. If in any reaction the weights of the substances taken be designated by the letters A, B, C, &c., and the weights of the substances formed by the letters M, N, O, &c., then A + B + C + ... ... ... = M + N + O + ... ... ... Therefore, should the weight of one of the re-acting or resultant substances be unknown, it may be determined by solving the equation. The chemist, in applying the law of the indestructibility of matter, and in making use of the chemical balance, must never lose sight of any one of the re-acting or resultant substances. Should such an over-sight be made, it will at once be remarked that the sum of the weights of the substances taken is unequal to the sum of the weights of the substances formed. All the progress made by chemistry during the end of the last, and in the present, century is entirely and immovably founded on the law of the indestructibility of matter. It is absolutely necessary in beginning the study of chemistry to become familiar with the simple truth which is expressed by this law, and for this purpose several examples elucidating its application will now be cited. [11] The experiments conducted by Staas (described in detail in Chap. XXIV. on Silver) form some of the accurate researches, proving that the weight of matter is not altered in chemical reactions, because he accurately weighed (introducing all the necessary corrections) the reacting and resultant substances. Landolt (1893) carried on various reactions in inverted and sealed glass U-tubes, and on weighing the tubes before reaction (when the reacting solutions were separated in each of the branches of the tubes), and after (when the solutions had been well mixed together by shaking), found that either the weight remained perfectly constant or that the variation was so small (for instance, 0·2 milligram in a total weight of about a million milligrams) as to be ascribed to the inevitable errors of weighing. [11 bis] The idea of the mass of matter was first shaped into an exact form by Galileo (died 1642), and more especially by Newton (born 1643, died 1727), in the glorious epoch of the development of the principles of inductive reasoning enunciated by Bacon and Descartes in their philosophical treatises. Shortly after the death of Newton, Lavoisier, whose fame in natural philosophy should rank with that of Galileo and Newton, was born on August 26, 1743. The death of Lavoisier occurred during the Reign of Terror of the French Revolution, when he, together with twenty-six other chief farmers of the revenue, was guillotined on May 8, 1794, at Paris; but his works and ideas have made him immortal. 1. It is well known that iron rusts in damp air,[12] and that when heated to redness in air it becomes coated with scoria (oxide), having, like rust, the appearance of an earthy substance resembling some of the iron ores from which metallic iron is extracted. If the iron is weighed before and after the formation of the scoria or rust, it will be found that the metal has increased in weight during the operation.[13] It can easily be proved that this increase in weight is accomplished at the expense of the atmosphere, and mainly, as Lavoisier proved, at the expense of that portion which is called oxygen. In fact, in a vacuum, or in gases which do not contain oxygen, for instance, in hydrogen or nitrogen, the iron neither rusts nor becomes coated with scoria. Had the iron not been weighed, the participation of the oxygen of the atmosphere in its transformation into an earthy substance might have easily passed unnoticed, as was formerly the case, when phenomena like the above were, for this reason, misunderstood. It is evident from the law of the indestructibility of matter that as the iron increases in weight in its conversion into rust, the latter must be a more complex substance than the iron itself, and its formation is due to a reaction of combination. We might form an entirely wrong opinion about it, and might, for instance, consider rust to be a simpler substance than iron, and explain the formation of rust as the removal of something from the iron. Such, indeed, was the general opinion prior to Lavoisier, when it was held that iron contained a certain unknown substance called 'phlogiston,' and that rust was iron deprived of this supposed substance. [12] By covering iron with an enamel, or varnish, or with unrustable metals (such as nickel), or a coating of paraffin, or other similar substances, it is protected from the air and moisture, and so kept from rusting. [13] Such an experiment may easily be made by taking the finest (unrusted) iron filings (ordinary filings must be first washed in ether, dried, and passed through a very fine sieve). The filings thus obtained are capable of burning directly in air (by oxidising or forming rust), especially when they hang (are attracted) on a magnet. A compact piece of iron does not burn in air, but spongy iron glows and smoulders like tinder. In making the experiment, a horse-shoe magnet is fixed, with the poles downwards, on one arm of a rather sensitive balance, and the iron filings are applied to the magnet (on a sheet of paper) so as to form a beard about the poles. The balance pan should be exactly under the filings on the magnet, in order that any which might fall from it should not alter the weight. The filings, having been weighed, are set light to by applying the flame of a candle; they easily take fire, and go on burning by themselves, forming rust. When the combustion is ended, it will be clear that the iron has increased in weight; from 5-1/2 parts by weight of iron filings taken, there are obtained, by complete combustion, 7-1/2 parts by weight of rust. [Illustration: FIG. 1.--Apparatus for the decomposition of red mercury oxide.] 2. Copper carbonate (in the form of a powder, or as the well-known green mineral called 'malachite,' which is used for making ornaments, or as an ore for the extraction of copper) changes into a black substance called 'copper oxide' when heated to redness.[14] This black substance is also obtained by heating copper to redness in air--that is, it is the scoria or oxidation product of copper. The weight of the black oxide of copper left is less than that of the copper carbonate originally taken, and therefore we consider the reaction which occurred to have been one of decomposition, and that by it something was separated from the green copper carbonate, and, in fact, by closing the orifice of the vessel in which the copper carbonate is heated with a well-fitting cork, through which a gas delivery tube[15] passes whose end is immersed under water, it will be observed that on heating, a gas is formed which bubbles through the water. This gas can be easily collected, as will presently be described, and it will be found to essentially differ from air in many respects; for instance, a burning taper is extinguished in it as if it had been plunged into water. If weighing had not proved to us that some substance had been separated, the formation of the gas might easily have escaped our notice, for it is colourless and transparent like air, and is therefore evolved without any striking feature. The carbonic anhydride evolved may be weighed,[16] and it will be seen that the sum of the weights of the black copper oxide and carbonic anhydride is equal to the weight of the copper carbonate[17] originally taken, and thus by carefully following out the various stages of all chemical reactions we arrive at a confirmation of the law of the indestructibility of matter. [14] For the purpose of experiment, it is most convenient to take copper carbonate, which may be prepared by the experimenter himself, by adding a solution of sodium carbonate to a solution of copper sulphate. The precipitate (deposit) so formed is collected on a filter, washed, and dried. The decomposition of copper carbonate into copper oxide is effected by so moderate a heat that it may be performed in a glass vessel heated by a lamp. For this purpose a thin glass tube, closed at one end, and called a 'test tube,' may be employed, or else a vessel called a 'retort.' The experiment is carried on, as described in example three on p. 11, by collecting the carbonic anhydride over water, as will be afterwards explained. [15] Gas delivery tubes are usually made of glass tubing of various diameters and thicknesses. If of small diameter and thickness, a glass tube is easily bent by heating in a gas jet or the flame of a spirit lamp, and it may also be easily divided at a given point by making a deep scratch with a file and then breaking the tube at this point with a sharp jerk. These properties, together with their impermeability, transparency, hardness, and regularity of bore, render glass tubes most useful in experiments with gases. Naturally they might be replaced by straws, india-rubber, metallic, or other tubes, but these are more difficult to fix on to a vessel, and are not entirely impervious to gases. A glass gas delivery tube may be hermetically fixed into a vessel by fitting it into a perforated cork, which should be soft and free from flaws, and fixing the cork into the orifice of the vessel. To protect the cork from the action of gases it is sometimes previously soaked in paraffin, or it may be replaced by an india-rubber cork. [16] Gases, like all other substances, may be weighed, but, owing to their extreme lightness and the difficulty of dealing with them in large masses, they can only be weighed by very sensitive balances; that is, in such as, with a considerable load, indicate a very small difference in weight--for example, a centigram or a milligram with a load of 1,000 grams. In order to weigh a gas, a glass globe furnished with a tight-fitting stop-cock is first of all exhausted of air by an air-pump (a Sprengel pump is the best). The stop-cock is then closed, and the exhausted globe weighed. If the gas to be weighed is then let into the globe, its weight can be determined from the increase in the weight of the globe. It is necessary, however, that the temperature and pressure of the air about the balance should remain constant for both weighings, as the weight of the globe in air will (according to the laws of hydrostatics) vary with its density. The volume of the air displaced, and its weight, must therefore be determined by observing the temperature, density, and moisture of the atmosphere during the time of experiment. This will be partly explained later, but may be studied more in detail by physics. Owing to the complexity of all these operations, the mass of a gas is usually determined from its volume and density, or from the weight of a known volume. [17] The copper carbonate should be dried before weighing, as otherwise--besides copper oxide and carbonic anhydride--water will be obtained in the decomposition. Water forms a part of the composition of malachite, and has therefore to be taken into consideration. The water produced in the decomposition may be all collected by absorbing it in sulphuric acid or calcium chloride, as will be described further on. In order to dry a salt it must be heated at about 100° until its weight remains constant, or be placed under an air pump over sulphuric acid, as will also be presently described. As water is met with almost everywhere, and as it is absorbed by many substances, the possibility of its presence should never be lost sight of. 3. Red mercury oxide (which is formed as mercury rust by heating mercury in air) is decomposed like copper carbonate (only by heating more slowly and at a somewhat higher temperature), with the formation of the peculiar gas, oxygen. For this purpose the mercury oxide is placed in a glass tube or retort,[18] to which a gas delivery tube is attached by means of a cork. This tube is bent downwards, as shown in the drawing (Fig. 1). The open end of the gas delivery tube is immersed in a vessel filled with water, called a pneumatic trough.[19] When the gas begins to be evolved in the retort it is obliged, having no other outlet, to escape through the gas delivery tube into the water in the pneumatic trough, and therefore its evolution will be rendered visible by the bubbles coming from this tube. In heating the retort containing the mercury oxide, the air contained in the apparatus is first partly expelled, owing to its expansion by heat, and then the peculiar gas called 'oxygen' is evolved, and may be easily collected as it comes off. For this purpose a vessel (an ordinary cylinder, as in the drawing) is filled quite full with water and its mouth closed; it is then inverted and placed in this position under the water in the trough; the mouth is then opened. The cylinder will remain full of water--that is, the water will remain at a higher level in it than in the surrounding vessel, owing to the atmospheric pressure. The atmosphere presses on the surface of the water in the trough, and prevents the water from flowing out of the cylinder. The mouth of the cylinder is placed over the end of the gas delivery tube,[20] and the bubbles issuing from it will rise into the cylinder and displace the water contained in it. Gases are generally collected in this manner. When a sufficient quantity of gas has accumulated in the cylinder it can be clearly shown that it is not air, but another gas which is distinguished by its capacity for vigorously supporting combustion. In order to show this, the cylinder is closed, under water, and removed from the bath; its mouth is then turned upwards, and a smouldering taper plunged into it. As is well known, a smouldering taper will be extinguished in air, but in the gas which is given off from red mercury oxide it burns clearly and vigorously, showing the property possessed by this gas for supporting combustion more energetically than air, and thus enabling it to be distinguished from the latter. It may be observed in this experiment that, besides the formation of oxygen, metallic mercury is formed, which, volatilising at the high temperature required for the reaction, condenses on the cooler parts of the retort as a mirror or in globules. Thus two substances, mercury and oxygen, are obtained by heating red mercury oxide. In this reaction, from one substance, two new substances are produced--that is, a decomposition has taken place. The means of collecting and investigating gases were known before Lavoisier's time, but he first showed the real part they played in the processes of many chemical changes which before his era were either wrongly understood (as will be afterwards explained) or were not explained at all, but only observed in their superficial aspects. This experiment on red mercury oxide has a special significance in the history of chemistry contemporary with Lavoisier, because the oxygen gas which is here evolved is contained in the atmosphere, and plays a most important part in nature, especially in the respiration of animals, in combustion in air, and in the formation of rusts or scoriæ (earths, as they were then called) from metals--that is, of earthy substances, like the ores from which metals are extracted. [18] As the decomposition of red oxide of mercury requires so high a temperature, near redness, as to soften ordinary glass, it is necessary for this experiment to take a retort (or test tube) made of hard glass, which is able to stand high temperatures without softening. For the same reason, the lamp used must give a strong heat and a large flame, capable of embracing the whole bottom of the retort, which should be as small as possible for the convenience of the experiment. [19] [Illustration: FIG. 2.--Apparatus for distilling under a diminished pressure liquids which decompose at their boiling points under the ordinary pressure. The apparatus in which the liquid is distilled is connected with a large globe from which the air is pumped out; the liquid is heated, and the receiver cooled.] The pneumatic trough may naturally be made of any material (china, earthenware, or metal, &c.), but usually a glass one, as shown in the drawing, is used, as it allows the progress of the experiment to be better observed. For this reason, as well as the ease with which they are kept clean, and from the fact also that glass is not acted on by many substances which affect other materials (for instance, metals), glass vessels of all kinds--such as retorts, test tubes, cylinders, beakers, flasks, globes, &c.--are preferred to any other for chemical experiments. Glass vessels may be heated without any danger if the following precautions be observed: 1st, they should be made of thin glass, as otherwise they are liable to crack from the bad heat-conducting power of glass; 2nd, they should be surrounded by a liquid or with sand (Fig. 2), or sand bath as it is called; or else should stand in a current of hot gases without touching the fuel from which they proceed, or in the flame of a smokeless lamp. A common candle or lamp forms a deposit of soot on a cold object placed in their flames. The soot interferes with the transmission of heat, and so a glass vessel when covered with soot often cracks. And for this reason spirit lamps, which burn with a smokeless flame, or gas burners of a peculiar construction, are used. In the Bunsen burner the gas is mixed with air, and burns with a non-luminous and smokeless flame. On the other hand, if an ordinary lamp (petroleum or benzine) does not smoke it may be used for heating a glass vessel without danger, provided the glass is placed well above the flame in the current of hot gases. In all cases, the heating should be begun very carefully by raising the temperature by degrees. [20] In order to avoid the necessity of holding the cylinder, its open end is widened (and also ground so that it may be closely covered with a ground-glass plate when necessary), and placed on a stand below the level of the water in the bath. This stand is called 'the bridge.' It has several circular openings cut through it, and the gas delivery tube is placed under one of these, and the cylinder for collecting the gas over it. 4. In order to illustrate by experiment one more example of chemical change and the application of the law of the indestructibility of matter, we will consider the reaction between common table salt and lunar caustic, which is well known from its use in cauterising wounds. By taking a clear solution of each and mixing them together, it will at once be observed that a solid white substance is formed, which settles to the bottom of the vessel, and is insoluble in water. This substance may be separated from the solution by filtering; it is then found to be an entirely different substance from either of those taken originally in the solutions. This is at once evident from the fact that it does not dissolve in water. On evaporating the liquid which passed through the filter, it will be found to contain a new substance unlike either table salt or lunar caustic, but, like them, soluble in water. Thus table salt and lunar caustic, two substances soluble in water, produced, by their mutual chemical action, two new substances, one insoluble in water, and the other remaining in solution. Here, from two substances, two others are obtained, consequently there occurred a reaction of substitution. The water served only to convert the re-acting substances into a liquid and mobile state. If the lunar caustic and salt be dried[21] and weighed, and if about 58-1/2 grams[22] of salt and 170 grams of lunar caustic be taken, then 143-1/2 grams of insoluble silver chloride and 85 grams of sodium nitrate will be obtained. The sum of the weights of the re-acting and resultant substances are seen to be similar and equal to 228-1/2 grams, which necessarily follows from the law of the indestructibility of matter. [21] Drying is necessary in order to remove any water which may be held in the salts (_see_ Note 17, and Chapter I., Notes 13 and 14). [22] The exact weights of the re-acting and resulting substances are determined with the greatest difficulty, not only from the possible inexactitude of the balance (every weighing is only correct within the limits of the sensitiveness of the balance) and weights used in weighing, not only from the difficulty in making corrections for the weight of air displaced by the vessels holding the substances weighed and by the weights themselves, but also from the hygroscopic nature of many substances (and vessels) causing absorption of moisture from the atmosphere, and from the difficulty in not losing any of the substance to be weighed in the several operations (filtering, evaporating, and drying, &c.) which have to be performed before arriving at a final result. All these circumstances have to be taken into consideration in exact researches, and their elimination requires very many special precautions which are impracticable in preliminary experiments. Accepting the truth of the above law, the question naturally arises as to whether there is any limit to the various chemical transformations, or are they unrestricted in number--that is to say, is it possible from a given substance to obtain an equivalent quantity of any other substance? In other words, does there exist a perpetual and infinite change of one kind of material into every other kind, or is the cycle of these transformations limited? This is the second essential problem of Chemistry, a question of quality of matter, and one, it is evident, which is more complicated than the question of quantity. It cannot be solved by a mere superficial glance at the subject. Indeed, on seeing how all the varied forms and colours of plants are built up from air and the elements of the soil, and how metallic iron can be transformed into colours such as inks and Prussian blue, we might be led to think that there is no end to the qualitative changes to which matter is susceptible. But, on the other hand, the experiences of everyday life compel us to acknowledge that food cannot be made out of a stone, or gold out of copper. Thus a definite answer can only be looked for in a close and diligent study of the subject, and the problem has been resolved in different way at different times. In ancient times the opinion most generally held was that everything visible was composed of four elements--Air, Water, Earth, and Fire. The origin of this doctrine can be traced far back into the confines of Asia, whence it was handed down to the Greeks, and most fully expounded by Empedocles, who lived before 460 B.C. This doctrine was not the result of exact research, but apparently owes its origin to the clear division of bodies into gases (like air), liquids (like water), and solids (like the earth). The Arabs appear to have been the first who attempted to solve the question by experimental methods, and they introduced, through Spain, the taste for the study of similar problems into Europe, where from that time there appear many adepts in chemistry, which was considered as an unholy art, and called 'alchemy.' As the alchemists were ignorant of any exact law which could guide them in their researches, they obtained most anomalous results. Their chief service to chemistry was that they made a number of experiments, and discovered many new chemical transformations; but it is well known how they solved the fundamental problem of chemistry. Their view may be taken as a positive acknowledgment of the infinite transmutability of matter, for they aimed at discovering the Philosopher's Stone, capable of converting everything into gold and diamonds, and of making the old young again. This solution of the question was afterwards completely overthrown, but it must not, for this reason, be thought that the hopes held by the alchemists were only the fruit of their imaginations. The first chemical experiments might well lead them to their conclusions. They took, for instance, the bright metallic mineral galena, and extracted metallic lead from it. Thus they saw that from a metallic substance which is unfitted for use they could obtain another metallic substance which is ductile and valuable for many technical purposes. Furthermore, they took this lead and obtained silver, a still more valuable metal, from it. Thus they might easily conclude that it was possible to ennoble metals by means of a whole series of transmutations--that is to say, to obtain from them those which are more and more precious. Having got silver from lead, they assumed that it would be possible to obtain gold from silver. The mistake they made was that they never weighed or measured the substances used or produced in their experiments. Had they done so, they would have learnt that the weight of the lead was much less than that of the galena from which it was obtained, and the weight of the silver infinitesimal compared with that of the lead. Had they looked more closely into the process of the extraction of the silver from lead (and silver at the present time is chiefly obtained from the lead ores) they would have seen that the lead does not change into silver, but that it only contains a certain small quantity of it, and this amount having once been separated from the lead it cannot by any further operation give more. The silver which the alchemists extracted from the lead was in the lead, and was not obtained by a chemical change of the lead itself. This is now well known from experiment, but the first view of the nature of the process was very likely to be an erroneous one.[23] The methods of research adopted by the alchemists could give but little success, for they did not set themselves clear and simple questions whose answers would aid them to make further progress. Thus though they did not arrive at any exact law, they left nevertheless numerous and useful experimental data as an inheritance to chemistry; they investigated, in particular, the transformations proper to metals, and for this reason chemistry was for long afterwards entirely confined to the study of metallic substances. [23] Besides which, in the majority of cases, the first explanation of most subjects which do not repeat themselves in everyday experience under various aspects, but always in one form, or only at intervals and infrequently, is usually wrong. Thus the daily evidence of the rising of the sun and stars evokes the erroneous idea that the heavens move and the earth stands still. This apparent truth is far from being the real truth, and, as a matter of fact, is contradictory to it. Similarly, an ordinary mind and everyday experience concludes that iron is incombustible, whereas it burns not only as filings, but even as wire, as we shall afterwards see. With the progress of knowledge very many primitive prejudices have been obliged to give way to true ideas which have been verified by experiment. In ordinary life we often reason at first sight with perfect truth, only because we are taught a right judgment by our daily experience. It is a necessary consequence of the nature of our minds to reach the attainment of truth through elementary and often erroneous reasoning and through experiment, and it would be very wrong to expect a knowledge of truth from a simple mental effort. Naturally, experiment itself cannot give truth, but it gives the means of destroying erroneous representations whilst confirming those which are true in all their consequences. In their researches, the alchemists frequently made use of two chemical processes which are now termed 'reduction' and 'oxidation.' The rusting of metals, and in general their conversion from a metallic into an earthy form, is called 'oxidation,' whilst the extraction of a metal from an earthy substance is called 'reduction.' Many metals--for instance, iron, lead, and tin--are oxidised by heating in air alone, and may be again reduced by heating with carbon. Such oxidised metals are found in the earth, and form the majority of metallic ores. The metals, such as tin, iron, and copper, may be extracted from these ores by heating them together with carbon. All these processes were well studied by the alchemists. It was afterwards shown that all earths and minerals are formed of similar metallic rusts or oxides, or of their combinations. Thus the alchemists knew of two forms of chemical changes: the oxidation of metals and the reduction of the oxides so formed into metals. The explanation of the nature of these two classes of chemical phenomena was the means for the discovery of the most important chemical laws. The first hypothesis on their nature is due to Becker, and more particularly to Stahl, a surgeon to the King of Prussia. Stahl writes in his 'Fundamenta Chymiæ,' 1723, that all substances consist of an imponderable fiery substance called 'phlogiston' (materia aut principium ignis non ipse ignis), and of another element having particular properties for each substance. The greater the capacity of a body for oxidation, or the more combustible it is, the richer it is in phlogiston. Carbon contains it in great abundance. In oxidation or combustion phlogiston is emitted, and in reduction it is consumed or enters into combination. Carbon reduces earthy substances because it is rich in phlogiston, and gives up a portion of its phlogiston to the substance reduced. Thus Stahl supposed metals to be compound substances consisting of phlogiston and an earthy substance or oxide. This hypothesis is distinguished for its very great simplicity, and for this and other reasons it acquired many supporters.[24] [24] It is true that Stahl was acquainted with a fact which directly disproved his hypothesis. It was already known (from the experiments of Geber, and more especially of Ray, in 1630) that metals increase in weight by oxidation, whilst, according to Stahl's hypothesis, they should decrease in weight, because phlogiston is separated by oxidation. Stahl speaks on this point as follows:--'I am well aware that metals, in their transformation into earths, increase in weight. But not only does this fact not disprove my theory, but, on the contrary, confirms it, for phlogiston is lighter than air, and, in combining with substances, strives to lift them, and so decreases their weight; consequently, a substance which has lost phlogiston must be heavier.' This argument, it will be seen, is founded on a misconception of the properties of gases, regarding them as having no weight and as not being attracted by the earth, or else on a confused idea of phlogiston itself, since it was first defined as imponderable. The conception of imponderable phlogiston tallies well with the habit and methods of the last century, when recourse was often had to imponderable fluids for explaining a large number of phenomena. Heat, light, magnetism, and electricity were explained as being peculiar imponderable fluids. In this sense the doctrine of Stahl corresponds entirely with the spirit of his age. If heat be now regarded as motion or energy, then phlogiston also should be considered in this light. In fact, in combustion, of coals for instance, heat and energy are evolved, and not combined in the coal, although the oxygen and coal do combine. Consequently, the doctrine of Stahl contains the essence of a true representation of the evolution of energy, but naturally this evolution is only a consequence of the combination occurring between the coal and oxygen. As regards the history of chemistry prior to Lavoisier, besides Stahl's work (to which reference has been made above), Priestley's _Experiments and Observations on Different Kinds of Air_, London, 1790, and also Scheele's _Opuscula Chimica et Physica_, Lips., 1788-89, 2 vols., must be recommended as the two leading works of the English and Scandinavian chemists showing the condition of chemical learning before the propagation of Lavoisier's views, and containing also many important observations which lie at the basis of the chemistry of our times. A most interesting memoir on the history of phlogiston is that of Rodwell, in the _Philosophical Magazine_, 1868, in which it is shown that the idea of phlogiston dates very far back, that Basil Valentine (1394-1415), in the _Cursus Triumphalis Antimonii_, Paracelsus (1493-1541), in his work, _De Rerum Natura_, Glauber (1604-1668), and especially John Joachim Becher (1625-1682), in his _Physica Subterranea_, all referred to phlogiston, but under different names. [Illustration: FIG. 3.--Lavoisier's apparatus for determining the composition of air and the reason of metals increasing in weight when they are calcined in air.] Lavoisier proved by means of the balance that every case of rusting of metals or oxidation, or of combustion, is accompanied by an increase in weight at the expense of the atmosphere. He formed, therefore, the natural opinion that the heavier substance is more complex than the lighter one.[25] Lavoisier's celebrated experiment, made in 1774, gave indubitable support to his opinion, which in many respects was contradictory to Stahl's doctrine. Lavoisier poured four ounces of pure mercury into a glass retort (fig. 3), whose neck was bent as shown in the drawing and dipped into the vessel R S, also full of mercury. The projecting end of the neck was covered with a glass bell-jar P. The weight of all the mercury taken, and the volume of air remaining in the apparatus, namely, that in the upper portion of the retort, and under the bell-jar, were determined before beginning the experiment. It was most important in this experiment to know the volume of air in order to learn what part it played in the oxidation of the mercury, because, according to Stahl, phlogiston is emitted into the air, whilst, according to Lavoisier, the mercury in oxidising absorbs a portion of the air; and consequently it was absolutely necessary to determine whether the amount of air increased or decreased in the oxidation of the metal. It was, therefore, most important to measure the volume of the air in the apparatus both before and after the experiment. For this purpose it was necessary to know the total capacity of the retort, the volume of the mercury poured into it, the volume of the bell-jar above the level of the mercury, and also the temperature and pressure of the air at the time of its measurement. The volume of air contained in the apparatus and isolated from the surrounding atmosphere could be determined from these data. Having arranged his apparatus in this manner, Lavoisier heated the retort holding the mercury for a period of twelve days at a temperature near the boiling point of mercury. The mercury became covered with a quantity of small red scales; that is, it was oxidised or converted into an earth. This substance is the same mercury oxide which has already been mentioned (example 3). After the lapse of twelve days the apparatus was cooled, and it was then seen that the volume of the air in the apparatus had diminished during the time of the experiment. This result was in exact contradiction to Stahl's hypothesis. Out of 50 cubic inches of air originally taken, there only remained 42. Lavoisier's experiment led to other equally important results. The weight of the air taken decreased by as much as the weight of the mercury increased in oxidising; that is, the portion of the air was not destroyed, but only combined with mercury. This portion of the air may be again separated from the mercury oxide and has, as we saw (example 3), properties different from those of air. It is called 'oxygen.' That portion of the air which remained in the apparatus and did not combine with the mercury does not oxidise metals, and cannot support either combustion or respiration, so that a lighted taper is immediately extinguished if it be dipped into the gas which remains in the bell-jar. 'It is extinguished in the residual gas as if it had been plunged into water,' writes Lavoisier in his memoirs. This gas is called 'nitrogen.' Thus air is not a simple substance, but consists of two gases, oxygen and nitrogen, and therefore the opinion that air is an elementary substance is erroneous. The oxygen of the air is absorbed in combustion and the oxidation of metals, and the earths produced by the oxidation of metals are substances composed of oxygen and a metal. By mixing the oxygen with the nitrogen the same air as was originally taken is re-formed. It has also been shown by direct experiment that on reducing an oxide with carbon, the oxygen contained in the oxide is transferred to the carbon, and gives the same gas that is obtained by the combustion of carbon in air. Therefore this gas is a compound of carbon and oxygen, just as the earthy oxides are composed of metals and oxygen. [25] An Englishman, named Mayow, who lived a whole century before Lavoisier (in 1666), understood certain phenomena of oxidation in their true aspect, but was not able to develop his views with clearness, or support them by conclusive experiments; he cannot therefore be considered, like Lavoisier, as the founder of contemporary chemical learning. Science is a universal heritage, and therefore it is only just to give the highest honour in science, not to those who first enunciate a certain truth, but to those who are first able to convince others of its authenticity and establish it for the general welfare. But scientific discoveries are rarely made all at once; as a rule, the first teachers do not succeed in convincing others of the truth they have discovered; with time, however, a true herald comes forward, possessing every means for making the truth apparent to all, but it must not be forgotten that such are entirely indebted to the labours and mass of data accumulated by many others. Such was Lavoisier, and such are all the great founders of science. They are the enunciators of all past and present learning, and their names will always be revered by posterity. The many examples of the formation and decomposition of substances which are met with convince us that the majority of substances with which we have to deal are compounds made up of several other substances. By heating chalk (or else copper carbonate, as in the second example) we obtain lime and the same carbonic acid gas which is produced by the combustion of carbon. On bringing lime into contact with this gas and water, at the ordinary temperature, we again obtain the compound, carbonate of lime, or chalk. Therefore chalk is a compound. So also are those substances from which it may be built up. Carbonic anhydride is formed by the combination of carbon and oxygen; and lime is produced by the oxidation of a certain metal called 'calcium.' By resolving substances in this manner into their component parts, we arrive at last at such as are indivisible into two or more substances by any means whatever, and which cannot be formed from other substances. All we can do is to make such substances combine together to act on other substances. Substances which cannot be formed from or decomposed into others are termed _simple substances_ (elements). Thus all homogeneous substances may be classified into simple and compound substances. This view was introduced and established as a scientific fact during the lifetime of Lavoisier. The number of these elements is very small in comparison with the number of compound substances which are formed by them. At the present time, only seventy elements are known with certainty to exist. Some of them are very rarely met with in nature, or are found in very small quantities, whilst the existence of others is still doubtful. The number of elements with whose compounds we commonly deal in everyday life is very small. Elements cannot be transmuted into one another--at least up to the present not a single case of such a transformation has been met with; it may therefore be said that, as yet, it is impossible to transmute one metal into another. And as yet, notwithstanding the number of attempts which have been made in this direction, no fact has been discovered which could in any way support the idea of the complexity of such well-known elements[26] as oxygen, iron, sulphur, &c. Therefore, from its very conception, an element is not susceptible to reactions of decomposition.[27] [26] Many of the ancient philosophers assumed the existence of one elementary form of matter. This idea still appears in our times, in the constant efforts which are made to reduce the number of the elements; to prove, for instance, that bromine contains chlorine or that chlorine contains oxygen. Many methods, founded both on experiment and theory, have been tried to prove the compound nature of the elements. All labour in this direction has as yet been in vain, and the assurance that elementary matter is not so homogeneous (single) as the mind would desire in its first transport of rapid generalisation is strengthened from year to year. All our knowledge shows that iron and other elements remain, even at such a high temperature as there exists in the sun, as different substances, and are not converted into one common material. Admitting, even mentally, the possibility of one elementary form of matter, a method must be imagined by which it could give rise to the various elements, as also the _modus operandi_ of their formation from one material. If it be said that this diversitude only takes place at low temperatures, as is observed with isomerides, then there would be reason to expect, if not the transition of the various elements into one particular and more stable form, at least the mutual transformation of some into others. But nothing of the kind has as yet been observed, and the alchemist's hope to manufacture (as Berthollet puts it) elements has no theoretical or practical foundation. [27] The weakest point in the idea of elements is the negative character of the determinative signs given them by Lavoisier, and from that time ruling in chemistry. They do _not_ decompose, they do _not_ change into one another. But it must be remarked that elements form the limiting horizon of our knowledge of matter, and it is always difficult to determine a positive side on the borderland of what is known. Besides, there is no doubt (from the results of spectrum analysis) that the elements are distributed as far as the most distant stars, and that they support the highest attainable temperatures without decomposing. The quantity, therefore, of each element remains constant in all chemical changes: a fact which may be deduced as a consequence of the law of the indestructibility of matter, and of the conception of elements themselves. Thus the equation expressing the law of the indestructibility of matter acquires a new and still more important signification. If we know the quantities of the elements which occur in the re-acting substances, and if from these substances there proceed, by means of chemical changes, a series of new compound substances, then the latter will together contain the same quantity of each of the elements as there originally existed in the re-acting substances. The essence of chemical change is embraced in the study of how, and with what substances, each element is combined before and after change. In order to be able to express various chemical changes by equations, it has been agreed to represent each element by the first or some two letters of its (Latin) name. Thus, for example, oxygen is represented by the letter O; nitrogen by N; mercury (hydrargyrum) by Hg; iron (ferrum) by Fe; and so on for all the elements, as is seen in the tables on page 24. A compound substance is represented by placing the symbols representing the elements of which it is made up side by side. For example, red mercury oxide is represented by HgO, which shows that it is composed of oxygen and mercury. Besides this, the symbol of every element corresponds with a certain relative quantity of it by weight, called its 'combining' weight, or the weight of an atom; so that the chemical formula of a compound substance not only designates the nature of the elements of which it is composed, but also their quantitative proportion. Every chemical process may be expressed by an equation composed of the formulæ corresponding with those substances which take part in it and are produced by it. The amount by weight of the elements in every chemical equation must be equal on both sides of the equation, since no element is either formed or destroyed in a chemical change. On pages 24, 25, and 26 a list of the elements, with their symbols and combining or atomic weights, is given, and we shall see afterwards on what basis the atomic weights of elements are determined. At present we will only point out that a compound containing the elements A and B is designated by the formula A_n_ B_m_, where _m_ and _n_ are the coefficients or multiples in which the combining weights of the elements enter into the composition of the substance. If we represent the combining weight of the substance A by _a_ and that of the substance B by _b_, then the composition of the substance A_n_ B_m_ will be expressed thus: it contains _na_ parts by weight of the substance A and _mb_ parts by weight of the substance B, and consequently 100 parts of our compound contain _na_ 100/_na_ + _mb_ percentage parts by weight of the substance A and _mb_ 100/_na_ + _mb_ of the substance B. It is evident that as a formula shows the relative amounts of all the elements contained in a compound, the actual weights of the elements contained in a given weight of a compound may be calculated from its formula. For example, the formula NaCl of table salt shows (as Na = 23 and Cl = 35·5) that 58·5 lbs. of salt contain 23 lbs. of sodium and 35·5 lbs. of chlorine, and that 100 parts of it contain 39·3 per cent. of sodium and 60·7 per cent. of chlorine. What has been said above clearly limits the province of chemical changes, because from substances of a given kind there can be obtained only such as contain the same elements. Even with this limitation, however, the number of possible combinations is infinitely great. Only a comparatively small number of compounds have yet been described or subjected to research, and any one working in this direction may easily discover new compounds which had not before been obtained. It often happens, however, that such newly-discovered compounds were foreseen by chemistry, whose object is the apprehension of that uniformity which rules over the multitude of compound substances, and whose aim is the comprehension of those laws which govern their formation and properties. The conception of elements having been established, the next objects of chemistry were: the determination of the properties of compound substances on the basis of the determination of the quantity and kind of elements of which they are composed; the investigation of the elements themselves; the determination of what compound substances can be formed from each element and the properties which these compounds show; and the apprehension of the nature of the connection between the elements in different compounds. An element thus serves as the starting point, and is taken as the primary conception on which all other substances are built up. When we state that a certain element enters into the composition of a given compound (when we say, for instance, that mercury oxide contains oxygen) we do not mean that it contains oxygen as a gaseous substance, but only desire to express those transformations which mercury oxide is capable of making; that is, we wish to say that it is possible to obtain oxygen from mercury oxide, and that it can give up oxygen to various other substances; in a word, we desire only to express those transformations of which mercury oxide is capable. Or, more concisely, it may be said that the _composition_ of a compound is the expression of those transformations of which it is capable. It is useful in this sense to make a clear distinction between the conception of an element as a _separate_ homogeneous substance, and as a _material_ but invisible _part_ of a compound. Mercury oxide does not contain two simple bodies, a gas and a metal, but two elements, mercury and oxygen, which, when free, are a gas and a metal. Neither mercury as a metal nor oxygen as a gas is contained in mercury oxide; it only contains the substance of these elements, just as steam only contains the substance of ice, but not ice itself, or as corn contains the substance of the seed, but not the seed itself. The existence of an element may be recognised without knowing it in the uncombined state, but only from an investigation of its combinations, and from the knowledge that it gives, under all possible conditions, substances which are unlike other known combinations of substances. Fluorine is an example of this kind. It was for a long time unknown in a free state, and nevertheless was recognised as an element because its combinations with other elements were known, and their difference from all other similar compound substances was determined. In order to grasp the difference between the conception of the visible form of an element as we know it in the free state, and of the intrinsic element (or 'radicle,' as Lavoisier called it) contained in the visible form, it should be remarked that compound substances also combine together forming yet more complex compounds, and that they evolve heat in the process of combination. The original compound may often be extracted from these new compounds by exactly the same methods as elements are extracted from their corresponding combinations. Besides, many elements exist under various visible forms whilst the intrinsic element contained in these various forms is something which is not subject to change. Thus carbon appears as charcoal, graphite, and diamond, but yet the element carbon alone, contained in each, is one and the same. Carbonic anhydride contains carbon, and not charcoal, or graphite, or the diamond. Elements alone, although not all of them, have the peculiar lustre, opacity, malleability, and the great heat and electrical conductivity which are proper to metals and their mutual combinations. But elements are far from all being _metals_. Those which do not possess the physical properties of metals are called _non-metals_ (or _metalloids_). It is, however, impossible to draw a strict line of demarcation between metals and non-metals, there being many intermediary substances. Thus graphite, from which pencils are manufactured, is an element with the lustre and other properties of a metal; but charcoal and the diamond, which are composed of the same substance as graphite, do not show any metallic properties. Both classes of elements are clearly distinguished in definite examples, but in particular cases the distinction is not clear and cannot serve as a basis for the exact division of the elements into two groups. The conception of elements forms the basis of chemical knowledge, and in giving a list of them at the very beginning of our work, we wish to tabulate our present knowledge on the subject. Altogether about seventy elements are now authentically known, but many of them are so rarely met with in nature, and have been obtained in such small quantities, that we possess but a very insufficient knowledge of them. The substances most widely distributed in nature contain a very small number of elements. These elements have been more completely studied than the others, because a greater number of investigators have been able to carry on experiments and observations on them. The elements most widely distributed in nature are:-- Hydrogen, H = 1. In water, and in animal and vegetable organisms. Carbon, C = 12. In organisms, coal, limestones. Nitrogen, N = 14. In air and in organisms. Oxygen, O = 16. In air, water, earth. It forms the greater part of the mass of the earth. Sodium, Na = 23. In common salt and in many minerals. Magnesium, Mg = 24. In sea-water and in many minerals. Aluminium, Al = 27. In minerals and clay. Silicon, Si = 28. In sand, minerals, and clay. Phosphorus, P = 31. In bones, ashes of plants, and soil. Sulphur, S = 32. In pyrites, gypsum, and in sea-water. Chlorine, Cl = 35·5. In common salt, and in the salts of sea-water. Potassium, K = 39. In minerals, ashes of plants, and in nitre. Calcium, Ca = 40. In limestones, gypsum, and in organisms. Iron, Fe = 56. In the earth, iron ores, and in organisms. Besides these, the following elements, although not very largely distributed in nature, are all more or less well known from their applications to the requirements of everyday life or the arts, either in a free state or in their compounds:-- Lithium, Li = 7. In medicine (Li_{2}CO_{3}), and in photography (LiBr). Boron, B = 11. As borax, B_{4}Na_{2}O_{7}, and as boric anhydride, B_{2}O_{3}. Fluorine, F = 19. As fluor spar, CaF_{2}, and as hydrofluoric acid, HF. Chromium, Cr = 52. As chromic anhydride, CrO_{3}, and potassium dichromate, K_{2}Cr_{2}O_{7}. Manganese, Mn = 55. As manganese peroxide, MnO_{2}, and potassium permanganate, MnKO_{4}. Cobalt, Co = 59·5 In smalt and blue glass. Nickel, Ni = 59·5 For electro-plating other metals. Copper, Cu = 63. The well-known red metal. Zinc, Zn = 65. Used for the plates of batteries, roofing, &c. Arsenic, As = 75. White arsenic (poison), As_{2}O_{3}. Bromine, Br = 80. A brown volatile liquid; sodium bromide, NaBr. Strontium, Sr = 87. In coloured fires (SrN_{2}O_{6}). Silver, Ag = 109. The well-known white metal. Cadmium, Cd = 112. In alloys. Yellow paint (CdS). Tin, Sn = 119. The well-known metal. Antimony, Sb = 120. In alloys such as type metal. Iodine, I = 127. In medicine and photography; free, and as KI. Barium, Ba = 137. "Permanent white," and as an adulterant in white lead, and in heavy spar, BaSO_{4}. Platinum, Pt = 196.} Gold, Au = 197.} Mercury, Hg = 200.} Well-known metals. Lead, Pb = 207.} Bismuth, Bi = 209. In medicine and fusible alloys. Uranium, U = 239. In green fluorescent glass. The compounds of the following metals and semi-metals have fewer applications, but are well known, and are somewhat frequently met with in nature, although in small quantities:-- Beryllium, Be = 9. Palladium, Pd = 107. Titanium, Ti = 48. Cerium, Ce = 140. Vanadium, V = 51. Tungsten, W = 184. Selenium, Se = 79. Osmium, Os = 192. Zirconium, Zr = 91. Iridium, Ir = 193. Molybdenum, Mo = 96. Thallium, Tl = 204. The following rare metals are still more seldom met with in nature, but have been studied somewhat fully:-- Scandium, Sc = 44. Germanium, Ge = 72. Gallium, Ga = 70. Rubidium, Rb = 86. Yttrium, Y = 89. Cæsium, Cs = 133. Niobium, Nb = 94. Lanthanum, La = 138. Ruthenium, Ru = 102. Didymium, Di = 142. Rhodium, Rh = 103. Ytterbium, Yb = 173. Indium, In = 114. Tantalum, Ta = 183. Tellurium, Te = 125. Thorium, Th = 232. Besides these 66 elements there have been discovered:--Erbium, Terbium, Samarium, Thullium, Holmium, Mosandrium, Phillipium, and several others. But their properties and combinations, owing to their extreme rarity, are very little known, and even their existence as independent substances[28] is doubtful. [28] Possibly some of their compounds are compounds of other already-known elements. Pure and incontestably independent compounds of these substances are unknown, and some of them have not even been separated, but are only supposed to exist from the results of spectroscopic researches. There can be no mention of such contestable and doubtful elements in a short general handbook of chemistry. It has been incontestably proved from observations on the spectra of the heavenly bodies that many of the commoner elements (such as H, Na, Mg, Fe) occur on the far distant stars. This fact confirms the belief that those forms of matter which appear on the earth as elements are widely distributed over the entire universe. But we do not yet know why, in nature, the mass of some elements should be greater than that of others.[28 bis] [28 bis] Clark in America made an approximate calculation of the amount of the different elements contained in the earth's crust (to a depth of 15 kilometres), and found that the chief mass (over 50 per cent.) is composed of oxygen; then comes silicon, &c.; while the amount of hydrogen is less than 1 per cent., carbon scarcely 0·25 per cent., nitrogen even less than 0·03 per cent. The relative masses of such metals as Cu, Ni, Au is minute. Judging from the density (see Chapter VIII.) of the earth, a large proportion of its mass must be composed of iron. The capacity of each element to combine with one or another element, and to form compounds with them which are in a greater or less degree prone to give new and yet more complex substances, forms the fundamental character of each element. Thus sulphur easily combines with the metals, oxygen, chlorine, or carbon, whilst gold and silver enter into combinations with difficulty, and form unstable compounds, which are easily decomposed by heat. The cause or force which induces the elements to enter into chemical change must be considered, as also the cause which holds different substances in combination--that is, which endues the substances formed with their particular degree of stability. This cause or force is called _affinity_ (_affinitas_, _affinité_, _Verwandtschaft_), or chemical affinity.[29] Since this force must be regarded as exclusively an attractive force, like gravity, many writers (for instance, Bergmann at the end of the last, and Berthollet at the beginning of this, century) supposed affinity to be essentially similar to the universal force of gravity, from which it only differs in that the latter acts at observable distances whilst affinity only evinces itself at the smallest possible distances. But chemical affinity cannot be entirely identified with the universal attraction of gravity, which acts at appreciable distances and is dependent only on mass and distance, and not on the quality of the material on which it acts, whilst it is by the quality of matter that affinity is most forcibly influenced. Neither can it be entirely identified with cohesion, which gives to homogeneous solid substances their crystalline form, elasticity, hardness, ductility, and other properties, and to liquids their surface tension, drop formation, capillarity, and other properties, because affinity acts between the component parts of a substance and cohesion on a substance in its homogeneity, although both act at imperceptible distances (by contact) and have much in common. Chemical force, which makes one substance penetrate into another, cannot be entirely identified with even those attracting forces which make different substances adhere to each other, or hold together (as when two plane-polished surfaces of solid substances are brought into close contact), or which cause liquids to soak into solids, or adhere to their surfaces, or gases and vapours to condense on the surfaces of solids. These forces must not be confounded with chemical forces, which cause one substance to penetrate into the substance of another and to form a new substance, which is never the case with cohesion. But it is evident that the forces which determine cohesion form a connecting-link between mechanical and chemical forces, because they only act by intimate contact. For a long time, and especially during the first half of this century, chemical attraction and chemical forces were identified with electrical forces. There is certainly an intimate relation between them, for electricity is evolved in chemical reactions, and has also a powerful influence on chemical processes--for instance, compounds are decomposed by the action of an electrical current. And the exactly similar relation which exists between chemical phenomena and the phenomena of heat (heat being developed by chemical phenomena, and heat being able to decompose compounds) only proves the unity of the forces of nature, the capability of one force to produce and to be transformed into others. For this reason the identification of chemical force with electricity will not bear experimental proof.[30] As of all the (molecular) phenomena of nature which act on substances at immeasurably small distances, the phenomena of heat are at present the best (comparatively) known, having been reduced to the simplest fundamental principles of mechanics (of energy, equilibrium, and movement), which, since Newton, have been subjected to strict mathematical analysis, it is quite natural that an effort, which has been particularly pronounced during recent years, should have been made to bring chemical phenomena into strict correlation with the already investigated phenomena of heat, without, however, aiming at any identification of chemical with heat phenomena. The true nature of chemical force is still a secret to us, just as is the nature of the universal force of gravity, and yet without knowing what gravity really is, by applying mechanical conceptions, astronomical phenomena have been subjected not only to exact generalisation but to the detailed prediction of a number of particular facts; and so, also, although the true nature of chemical affinity may be unknown, there is reason to hope for considerable progress in chemical science by applying the laws of mechanics to chemical phenomena by means of the mechanical theory of heat. As yet this portion of chemistry has been but little worked at, and therefore, while forming a current problem of the science, it is treated more fully in that particular field which is termed either 'theoretical' or 'physical' chemistry, or, more correctly, _chemical mechanics_. As this province of chemistry requires a knowledge not only of the various homogeneous substances which have yet been obtained and of the chemical transformations which they undergo, but also of the phenomena (of heat and other kinds) by which these transformations are accompanied, it is only possible to enter on the study of chemical mechanics after an acquaintance with the fundamental chemical conceptions and substances which form the subject of this book.[31] [29] This word, first introduced, if I mistake not, into chemistry by Glauber, is based on the idea of the ancient philosophers that combination can only take place when the substances combining have something in common--a medium. As is generally the case, another idea evolved itself in antiquity, and has lived until now, side by side with the first, to which it is exactly contradictory; this considers union as dependent on contrast, on polar difference, on an effort to fill up a want. [30] Especially conclusive are those cases of so-called metalepsis (Dumas, Laurent). Chlorine, in combining with hydrogen, forms a very stable substance called 'hydrochloric acid,' which is split up by the action of an electrical current into chlorine and hydrogen, the chlorine appearing at the positive and the hydrogen at the negative pole. Hence electro-chemists considered hydrogen to be an electro-positive and chlorine an electro-negative element, and that they are held together in virtue of their opposite electrical charges. It appears, however, from metalepsis, that chlorine can replace hydrogen (and, inversely, hydrogen can replace chlorine) in its compounds without in any way changing the grouping of the other elements, or altering their chief chemical properties. For instance, acetic acid in which hydrogen has been replaced by chlorine is still capable of forming salts. It must be observed, whilst considering this subject, that the explanation suggesting electricity as the origin of chemical phenomena is unsound, since it attempts to explain one class of phenomena whose nature is almost unknown by another class which is no better known. It is most instructive to remark that together with the electrical theory of chemical attraction there arose and survives a view which explains the galvanic current as being a transference of chemical action through the circuit--_i.e._, regards the origin of electricity as being a chemical one. It is evident that the connection is very intimate, although both phenomena are independent and represent different forms of molecular (atomic) motion, whose real nature is not yet understood. Nevertheless, the connection between the phenomena of both categories is not only in itself very instructive, but it extends the applicability of the general idea of the unity of the forces of nature, conviction of the truth of which has held so important a place in the science of the last ten years. [31] I consider that in an elementary text-book of chemistry, like the present, it is only possible and advisable to mention, in reference to chemical mechanics, a few general ideas and some particular examples referring more especially to gases, whose mechanical theory must be regarded as the most complete. The molecular mechanics of liquids and solids is as yet in embryo, and contains much that is disputable; for this reason, chemical mechanics has made less progress in relation to these substances. It may not be superfluous here to remark, with respect to the conception of chemical affinity, that up to the present time gravity, electricity, and heat have all been applied to its elucidation. Efforts have also been made to introduce the luminiferous ether into theoretical chemistry, and should that connection between the phenomena of light and electricity which was established by Maxwell be worked out more in detail, doubtless these efforts to elucidate all or a great deal by the aid of luminiferous ether will again appear in theoretical chemistry. An independent chemical mechanics of the material particles of matter, and of their internal (atomic) changes, would, in my opinion, arise as the result of these efforts. Two hundred years ago Newton laid the foundation of a truly scientific theoretical mechanics of external visible motion, and on this foundation erected the edifice of celestial mechanics. One hundred years ago Lavoisier arrived at the first fundamental law of the internal mechanics of invisible particles of matter. This subject is far from having been developed into a harmonious whole, because it is much more difficult, and, although many details have been completely investigated, it does not possess any starting points. Newton only came after Copernicus and Kepler, who had discovered empirically the exterior simplicity of celestial phenomena. Lavoisier and Dalton may, in respect to the chemical mechanics of the molecular world, be compared to Copernicus and Kepler. But a Newton has not yet appeared in the molecular world; when he does, I think that he will find the fundamental laws of the mechanics of the invisible motions of matter more easily and more quickly in the chemical structure of matter than in physical phenomena (of electricity, heat, and light); for these latter are accomplished by particles of matter already arranged, whilst it is now clear that the problem of chemical mechanics mainly lies in the apprehension of those motions which are invisibly accomplished by the smallest atoms of matter. As the chemical changes to which substances are liable proceed from internal forces proper to these substances, as chemical phenomena certainly consist of motions of material parts (from the laws of the indestructibility of matter and of elements), and as the investigation of mechanical and physical phenomena proves the law of the _indestructibility of forces_, or the conservation of energy--that is, the possibility of the transformation of one kind of motion into another (of visible or mechanical into invisible or physical)--we are inevitably obliged to acknowledge the presence in substances (and especially in the elements of which all others are composed) of a store of _chemical energy_ or invisible motion inducing them to enter into combinations. If heat be evolved in a reaction, it means that a portion of chemical energy is transformed into heat;[32] if heat be absorbed in a reaction,[33] that it is partly transformed (rendered latent) into chemical energy. The store of force or energy going to the formation of new compounds may, after several combinations, accomplished with an absorption of heat, at last diminish to such a degree that indifferent compounds will be obtained, although these sometimes, by combining with energetic elements or compounds, give more complex compounds, which may be capable of entering into chemical combination. Among elements, gold, platinum, and nitrogen have but little energy, whilst potassium, oxygen, and chlorine have a very marked degree of energy. When dissimilar substances enter into combination they often form substances of diminished energy. Thus sulphur and potassium when heated easily burn in air, but when combined together their compound is neither inflammable nor burns in air like its component parts. Part of the energy of the potassium and of the sulphur was evolved in their combination in the form of heat. Just as in the passage of substances from one physical state into another a portion of their store of heat is absorbed or evolved, so in combinations or decompositions and in every chemical process, there occurs a change in the store of chemical energy, and at the same time an evolution or absorption of heat.[34] [32] The theory of heat gave the idea of a store of internal motion or energy, and therefore with it, it became necessary to acknowledge chemical energy, but there is no foundation whatever for identifying heat energy with chemical energy. It may be supposed, but not positively affirmed, that heat motion is proper to molecules and chemical motion to atoms, but that as molecules are made up of atoms, the motion of the one passes to the other, and that for this reason heat strongly influences reaction and appears or disappears (is absorbed) in reactions. These relations, which are apparent and hardly subject to doubt on general lines, still present much that is doubtful in detail, because all forms of molecular and atomic motion are able to pass into each other. [33] The reactions which take place (at the ordinary or at a high temperature) directly between substances may be clearly divided into exothermal, which are accompanied by an evolution of heat, and endothermal, which are accompanied by an absorption of heat. It is evident that the latter require a source of heat. They are determined either by the directly surrounding medium (as in the formation of carbon bisulphide from charcoal and sulphur, or in decompositions which take place at high temperatures), or else by a secondary reaction proceeding simultaneously, or by some other form of energy (light, electricity). So, for instance, hydrogen sulphide is decomposed by iodine in the presence of water at the expense of the heat which is evolved by the solution in water of the hydrogen iodide produced. This is the reason why this reaction, as exothermal, only takes place in the presence of water; otherwise it would be accompanied by a cooling effect. As in the combination of dissimilar substances, the bonds existing between the molecules and atoms of the homogeneous substances have to be broken asunder, whilst in reactions of rearrangement the formation of any one substance proceeds simultaneously with the formation of another, and, as in reactions, a series of physical and mechanical changes take place, it is impossible to separate the heat directly depending on a given reaction from the total sum of the observed heat effect. For this reason, thermochemical data are very complex, and cannot by themselves give the key to many chemical problems, as it was at first supposed they might. They ought to form a part of chemical mechanics, but alone they do not constitute it. [34] As chemical reactions are effected by heating, so the heat absorbed by substances before decomposition or change of state, and called 'specific heat,' goes in many cases to the preparation, if it may be so expressed, of reaction, even when the limit of the temperature of reaction is not attained. The molecules of a substance A, which is not able to react on a substance B below a temperature _t_, by being heated from a somewhat lower temperature to _t_, undergoes that change which had to be arrived at for the formation of A B. For the comprehension of chemical phenomena as mechanical processes--_i.e._, the study of the _modus operandi_ of chemical phenomena--it is most important to consider: (1) the facts gathered from stoïchiometry, or that part of chemistry which treats of the quantitative relation, by weight or volume, of the reacting substances; (2) the distinction between the different forms and classes of chemical reactions; (3) the study of the changes in properties produced by alteration in composition; (4) the study of the phenomena which accompany chemical transformation; (5) a generalisation of the conditions under which reactions occur. As regards stoïchiometry, this branch of chemistry has been worked out most thoroughly, and comprises laws (of Dalton, Avogadro-Gerhardt, and others) which bear so deeply on all parts of chemistry that at the present time the chief problem of chemical research consists in the application of general stoïchiometrical laws to concrete examples, _i.e._, the quantitative (volumetric or gravimetric) composition of substances. All other branches of chemistry are clearly subordinate to this most important portion of chemical knowledge. Even the very signification of reactions of combination, decomposition, and rearrangement, acquired, as we shall see, a particular and new character under the influence of the progress of exact ideas concerning the quantitative relations of substances entering into chemical changes. Furthermore, in this sense there arose a new--and, till then, unknown--division of compound substances into _definite_ and _indefinite_ compounds. Even at the beginning of this century, Berthollet had not made this distinction. But Prout showed that a number of compounds contain the substances of which they are they break up, in exact definite proportions by weight, which are unalterable under any conditions. Thus, for example, red mercury oxide always contains sixteen parts by weight of oxygen for every 200 parts by weight of mercury, which is expressed by the formula HgO. But in an alloy of copper and silver one or the other metal may be added at will, and in an aqueous solution of sugar, the relative proportion of the sugar and water may be altered and nevertheless a homogeneous whole with the sum of the independent properties will be obtained--_i.e._, in these cases there was indefinite chemical combination. Although in nature and chemical practice the formation of indefinite compounds (such as alloys and solutions) plays as essential a part as the formation of definite chemical compounds, yet, as the stoïchiometrical laws at present apply chiefly to the latter, all facts concerning indefinite compounds suffer from inexactitude, and it is only during recent years that the attention of chemists has been directed to this province of chemistry. In chemical mechanics it is, from a qualitative point of view, very important to clearly distinguish at the very beginning between _reversible_ and _non-reversible reactions_. Substances capable of reacting on each other at a certain temperature produce substances which at the same temperature either can or cannot give back the original substances. For example, salt dissolves in water at the ordinary temperature, and the solution so obtained is capable of breaking up at the same temperature, leaving salt and separating the water by evaporation. Carbon bisulphide is formed from sulphur and carbon at about the same temperature at which it can be resolved into sulphur and carbon. Iron, at a certain temperature, separates hydrogen from water, forming iron oxide, which, in contact with hydrogen at the same temperature, is able to produce iron and water. It is evident that if two substances, A and B, give two others C and D, and the reaction be reversible, then C and D will form A and B, and, consequently, by taking a definite mass of A and B, or a corresponding mass of C and D, we shall obtain, in each case, all four substances--that is to say, there will be a state of _chemical equilibrium_ between the reacting substances. By increasing the mass of one of the substances we obtain a new condition of equilibrium, so that reversible reactions present a means of studying the _influence of mass_ on the _modus operandi_ of chemical changes. Many of those reactions which occur with very complicated compounds or mixtures may serve as examples of non-reversible reactions. Thus many of the compound substances of animal and vegetable organisms are broken up by heat, but cannot be re-formed from their products of decomposition at any temperature. Gunpowder, as a mixture of sulphur, nitre, and carbon, on being exploded, forms gases from which the original substances cannot be re-formed at any temperature. In order to obtain them, recourse must be had to an indirect method _of combination at the moment of separation_. If A does not under any circumstances combine directly with B, it does not follow that it cannot give a compound A B. For A can often combine with C and B with D, and if C has a great affinity for D, then the reaction of A C or B D produces not only C D, but also A B. As on the formation of C D, the substances A and B (previously in A C and B D) are left in a peculiar state of separation, it is supposed that their mutual combination occurs because they meet together in this _nascent state_ at the moment of separation (_in statu nascendi_). Thus chlorine does not directly combine with charcoal, graphite, or diamond; there are, nevertheless, compounds of chlorine with carbon, and many of them are distinguished by their stability. They are obtained in the action of chlorine on hydrocarbons, as the separation products from the direct action of chlorine on hydrogen. Chlorine takes up the hydrogen, and the carbon liberated at the moment of its separation, enters into combination with another portion of the chlorine, so that in the end the chlorine is combined with both the hydrogen and the carbon.[35] [35] It is possible to imagine that the cause of a great many of such reactions is, that substances taken in a separate state, for instance, charcoal, present a complex molecule composed of separate atoms of carbon which are fastened together (united, as is usually said) by a considerable affinity; for atoms of the same kind, just like atoms of different kinds, possess a mutual affinity. The affinity of chlorine for carbon, although unable to break this bond asunder, may be sufficient to form a stable compound with atoms of carbon, which are already separate. Such a view of the subject presents a hypothesis which, although dominant at the present time, is without sufficiently firm foundation. It is evident, however, that not only does chemical reaction itself consist of motions, but that in the compound formed (in the molecules) the elements (atoms) forming it are in harmonious stable motion (like the planets in the solar system), and this motion will affect the stability and capacity for reaction, and therefore the mechanical side of chemical action must be exceedingly complex. Just as there are solid, physically constant non-volatile substances like rock, gold, charcoal, &c., so are there stable and chemically constant bodies; while corresponding to physically volatile substances there are bodies like camphor, which are chemically unstable and variable. As regards those phenomena which accompany chemical action, the most important circumstance in reference to chemical mechanics is that not only do chemical processes produce a mechanical displacement (a motion of particles), heat, light, electrical potential and current; but that all these agents are themselves capable of changing and governing chemical transformations. This reciprocity or reversibility naturally depends on the fact that all the phenomena of nature are only different kinds and forms of visible and invisible (molecular) motions. First sound, and then light, was shown to consist of vibratory motions, as the laws of physics have proved and developed beyond a doubt. The connection between heat and mechanical motion and work has ceased to be a supposition, but has become an accepted fact, and the mechanical equivalent of heat (425 kilogrammetres of mechanical work correspond with one kilogram unit of heat or Calorie) gives a mechanical measure for thermal phenomena. Although the mechanical theory of electrical phenomena cannot be considered so fully developed as the theory of heat, both statical and dynamical electricity are produced by mechanical means (in common electrical machines or in Gramme or other dynamos), and conversely, a current (in electric motors) can produce mechanical motion. Thus by connecting a current with the poles of a Gramme dynamo it may be made to revolve, and, conversely, by rotating it an electrical current is produced, which demonstrates the reversibility of electricity into mechanical motion. Accordingly chemical mechanics must look for the fundamental lines of its advancement in the correlation of chemical with physical and mechanical phenomena. But this subject, owing to its complexity and comparative novelty, has not yet been expressed by a harmonious theory, or even by a satisfactory hypothesis, and therefore we shall avoid lingering over it. A chemical change in a certain direction is accomplished not only by reason of the difference of masses, the composition of the substances concerned, the distribution of their parts, and their affinity or chemical energy, but also by reason of the _conditions_ under which the substances occur. In order that a certain chemical reaction may take place between substances which are capable of reacting on each other, it is often necessary to have recourse to conditions which are sometimes very different from those in which the substances usually occur in nature. For example, not only is the presence of air (oxygen) necessary for the combustion of charcoal, but the latter must also be heated to redness. The red-hot portion of the charcoal burns--_i.e._ combines with the oxygen of the atmosphere--and in so doing evolves heat, which raises the temperature of the adjacent parts of charcoal, so that they burn. Just as the combustion of charcoal is dependent on its being heated to redness, so also every chemical reaction only takes place under certain physical, mechanical, or other conditions. The following are the chief conditions which exert an influence on the progress of chemical reactions. (_a_) _Temperature._--Chemical reactions of combination only take place within certain definite limits of temperature, and cannot be accomplished outside these limits. We may cite as examples not only that the combustion of charcoal begins at a red heat, but also that chlorine and salt only combine with water at a temperature below 0°. These compounds cannot be formed at a higher temperature, for they are then wholly or partially broken up into their component parts. A certain rise in temperature is necessary to start combustion. In certain cases the effect of this rise may be explained as causing one of the reacting bodies to change from a solid into a liquid or gaseous form. The transference into a fluid form facilitates the progress of the reaction, because it aids the intimate contact of the particles reacting on each other. Another reason, and to this must be ascribed the chief influence of heat in exciting chemical action, is that the physical cohesion, or the internal chemical union, of homogeneous particles is thereby weakened, and in this way the separation of the particles of the original substances, and their transference into new compounds, is rendered easier. When a reaction absorbs heat--as in decomposition--the reason why heat is necessary is self-evident. At the present day it may be asserted upon the basis of existing data, respecting the action of high temperature, that all compound bodies are decomposed at a more or less high temperature. We have already seen examples of this in describing the decomposition of mercury oxide into mercury and oxygen, and the decomposition of wood under the influence of heat. Many substances are decomposed at a very moderate temperature; for instance, the fulminating salt which is employed in cartridges is decomposed at a little above 120°. The majority of those compounds which make up the mass of animal and vegetable tissues are decomposed at 200°. On the other hand, there is reason to think that at a very low temperature no reaction whatever can take place. Thus plants cease to carry on their chemical processes during the winter. Raoul Pictet (1892), employing the very low temperatures (as low as -200°C.) obtained by the evaporation of liquefied gases (_see_ Chap. II.), has recently again proved that at temperatures below -120°, even such reactions as those between sulphuric acid and caustic soda or metallic sodium do not take place, and even the coloration of litmus by acids only commences at temperatures above -80°. If a given reaction does not take place at a certain low temperature, it will at first only proceed slowly with a rise of temperature (even if aided by an electric discharge), and will only proceed rapidly, with the evolution of heat, when a certain definite temperature has been reached. Every chemical reaction requires certain limits of temperature for its accomplishment, and, doubtless, many of the chemical changes observed by us cannot take place in the sun, where the temperature is very high, or on the moon, where it is very low. The influence of heat on reversible reactions is particularly instructive. If, for instance, a compound which is capable of being reproduced from its products of decomposition be heated up to the temperature at which decomposition begins, the decomposition of a mass of the substance contained in a definite volume is not immediately completed. Only a certain fraction of the substance is decomposed, the other portion remaining unchanged, and if the temperature be raised, the quantity of the substance decomposed increases; furthermore, for a given volume, the ratio between the part decomposed and the part unaltered corresponds with each definite rise in temperature until it reaches that at which the compound is entirely decomposed. This partial decomposition under the influence of heat is called _dissociation_. It is possible to distinguish between the temperatures at which dissociation begins and ends. Should dissociation proceed at a certain temperature, yet should the product or products of decomposition not remain in contact with the still undecomposed portion of the compound, then decomposition will go on to the end. Thus limestone is decomposed in a limekiln into lime and carbonic anhydride, because the latter is carried off by the draught of the furnace. But if a certain mass of limestone be enclosed in a definite volume--for instance, in a gun barrel--which is then sealed up, and heated to redness, then, as the carbonic anhydride cannot escape, a certain proportion only of the limestone will be decomposed for every increment of heat (rise in temperature) higher than that at which dissociation begins. Decomposition will cease when the carbonic anhydride evolved presents a maximum _dissociation pressure_ corresponding with each rise in temperature. If the pressure be increased by increasing the quantity of gas, then combination begins afresh; if the pressure be diminished decomposition will recommence. Decomposition in this case is exactly similar to evaporation; if the steam given off by evaporation cannot escape, its pressure will reach a maximum corresponding with the given temperature, and then evaporation will cease. Should steam be added it will be condensed in the liquid; if its quantity be diminished--_i.e._ if the pressure be lessened, the temperature being constant--then evaporation will go on. We shall afterwards discuss more fully these phenomena of dissociation, which were first discovered by Henri St. Claire Deville. We will only remark that the products of decomposition re-combine with greater facility the nearer their temperature is to that at which dissociation begins, or, in other words, that the initial temperature of dissociation is near to the initial temperature of combination. (_b_) _The influence of an electric current_, and of electricity in general, on the progress of chemical transformations is very similar to the influence of heat. The majority of compounds which conduct electricity are decomposed by the action of a galvanic current, and as there is great similarity in the conditions under which decomposition and combination proceed, combination often proceeds under the influence of electricity. Electricity, like heat, must be regarded as a peculiar form of molecular motion, and all that refers to the influence of heat also refers to the phenomena produced by the action of an electrical current, with this difference, only that a substance can be separated into its component parts with much greater ease by electricity, since the process goes on at the ordinary temperature. The most stable compounds may be decomposed by this means, and a most important fact is then observed--namely, that the component parts appear at the different poles of electrodes by which the current passes through the substance. Those substances which appear at the positive pole (anode) are called 'electro-negative,' and those which appear at the negative pole (cathode, that in connection with the zinc of an ordinary galvanic battery) are called 'electro-positive.' The majority of non-metallic elements, such as chlorine, oxygen, &c., and also acids and substances analogous to them, belong to the first group, whilst the metals, hydrogen, and analogous products of decomposition appear at the negative pole. Chemistry is indebted to the decomposition of compounds by the electric current for many most important discoveries. Many elements have been discovered by this method, the most important being potassium and sodium. Lavoisier and the chemists of his time were not able to decompose the oxygen compounds of these metals, but Davy showed that they might be decomposed by an electric current, the metals sodium and potassium appearing at the negative pole. Now that the dynamo gives the possibility of producing an electric current by the combustion of fuel, this method of Sir H. Davy is advantageously employed for obtaining metals, &c. on a large scale, for instance, sodium from fused caustic soda or chlorine from solutions of salt. (_c_) Certain unstable compounds are also decomposed by _the action of light_. Photography is based on this property in certain substances (for instance, in the salts of silver). The mechanical energy of those vibrations which determine the phenomena of light is very small, and therefore only certain, and these generally unstable, compounds can be decomposed by light--at least under ordinary circumstances. But there is one class of chemical phenomena dependent on the action of light which forms as yet an unsolved problem in chemistry--these are the processes accomplished in plants under the influence of light. Here there take place most unexpected decompositions and combinations, which are often unattainable by artificial means. For instance, carbonic anhydride, which is so stable under the influence of heat and electricity, is decomposed and evolves oxygen in plants under the influence of light. In other cases, light decomposes unstable compounds, such as are usually easily decomposed by heat and other agents. Chlorine combines with hydrogen under the influence of light, which shows that combination, as well as decomposition, can be determined by its action, as was likewise the case with heat and electricity. (_d_) _Mechanical causes_ exert, like the foregoing agents, an action both on the process of chemical combination and of decomposition. Many substances are decomposed by friction or by a blow--as, for example, the compound called iodide of nitrogen (which is composed of iodine, nitrogen, and hydrogen), and silver fulminate. Mechanical friction causes sulphur to burn at the expense of the oxygen contained in potassium chlorate. Pressure affects both the physical and chemical state of the reacting substances, and, together with the temperature, determines the state of a substance. This is particularly evident when the substance occurs in an elastic-gaseous form since the volume, and hence also the number of points of encounter between the reacting substances is greatly altered by a change of pressure. Thus, under equal conditions of temperature, hydrogen when compressed acts more powerfully upon iodine and on the solutions of many salts. (_e_) Besides the various conditions which have been enumerated above, the progress of chemical reactions is accelerated or retarded by the _condition of contact_ in which the reacting bodies occur. Other conditions remaining constant, the rate of progress of a chemical reaction is accelerated by increasing the number of points of contact. It will be enough to point out the fact that sulphuric acid does not absorb ethylene under ordinary conditions of contact, but only after continued shaking, by which means the number of points of contact is greatly increased. To ensure complete action between solids, it is necessary to reduce them to very fine powder and to mix them as thoroughly as possible. M. Spring, the Belgian chemist, has shown that finely powdered solids which do not react on each other at the ordinary temperature may do so under an increased pressure. Thus, under a pressure of 6,000 atmospheres, sulphur combines with many metals at the ordinary temperature, and mixtures of the powders of many metals form alloys. It is evident that an increase in the number of points or surfaces must be regarded as the chief cause producing reaction, which is doubtless accomplished in solids, as in liquids and gases, in virtue of an internal motion of the particles, which motion, although in different degrees and forms, must exist in all the states of matter. It is very important to direct attention to the fact that the internal motion or condition of the parts of the particles of matter must be different on the surface of a substance from what it is inside; because in the interior of a substance similar particles are acting on all sides of every particle, whilst at the surface they act on one side only. Therefore, the condition of a substance at its surfaces of contact with other substances must be more or less modified by them--it may be in a manner similar to that caused by an elevation of temperature. These considerations throw some light on the action in the large class of _contact reactions_; that is, such as appear to proceed from the mere presence (contact) of certain special substances. Porous or powdery substances are very prone to act in this way, especially spongy platinum and charcoal. For example, sulphurous anhydride does not combine directly with oxygen, but this reaction takes place in the presence of spongy platinum.[36] [36] Contact phenomena are separately considered in detail in the work of Professor Konovaloff (1884). In my opinion, it must be held that the state of the internal motions of the atoms in molecules is modified at the points of contact of substances, and this state determines chemical reactions, and therefore, that reactions of combination, decomposition, and rearrangement are accomplished by contact. Professor Konovaloff showed that a number of substances, under certain conditions of their surfaces, act by contact; for instance, finely divided silica (from the hydrate) acts just like platinum, decomposing certain compound ethers. As reactions are only accomplished under close contact, it is probable that those modifications in the distribution of the atoms in molecules which come about by contact phenomena prepare the way for them. By this the _rôle_ of contact phenomena is considerably extended. Such phenomena should explain the fact why a mixture of hydrogen and oxygen yields water (explodes) at different temperatures, according to the kind of heated substance which transmits this temperature. In chemical mechanics, phenomena of this kind have great importance, but as yet they have been but little studied. It must not be forgotten that contact is a necessary condition for every chemical reaction. The above general and introductory chemical conceptions cannot be thoroughly grasped in their true sense without a knowledge of the particular facts of chemistry to which we shall now turn our attention. It was, however, absolutely necessary to become acquainted on the very threshold with such fundamental principles as the laws of the indestructibility of matter and of the conservation of energy, since it is only by their acceptance, and under their direction and influence, that the examination of particular facts can give practical and fruitful results. CHAPTER I ON WATER AND ITS COMPOUNDS Water is found almost everywhere in nature, and in all three physical states. As vapour, water occurs in the atmosphere, and in this form it is distributed over the entire surface of the earth. The vapour of water in condensing, by cooling, forms snow, rain, hail, dew, and fog. One cubic metre (or 1,000,000 cubic centimetres, or 1,000 litres, or 35·316 cubic feet) of air can contain at 0° only 4·8 grams of water, at 20° about 17·0 grams, at 40° about 50·7 grams; but ordinary air only contains about 60 per cent. of this maximum. Air containing less than 40 per cent. is felt to be dry, whilst air which contains more than 80 per cent. of the same maximum is considered as distinctly damp.[1] Water in the liquid state, in falling as rain and snow, soaks into the soil and collects together into springs, lakes, rivers, seas, and oceans. It is absorbed from the soil by the roots of plants, which, when fresh, contain from 40 to 80 per cent. of water by weight. Animals contain about the same amount of water. In a solid state, water appears as snow, ice, or in an intermediate form between these two, which is seen on mountains covered with perpetual snow. The water of rivers,[2] springs, oceans and seas, lakes, and wells contains various substances in solution mostly salt,--that is, substances resembling common table salt in their physical properties and chief chemical transformations. Further, the quantity and nature of these salts differ in different waters.[3] Everybody knows that there are salt, fresh, iron, and other waters. The presence of about 3-1/2 per cent. of salts renders sea-water[4] bitter to the taste and increases its specific gravity. Fresh water also contains salts, but only in a comparatively small quantity. Their presence may be easily proved by simply evaporating water in a vessel. On evaporation the water passes away as vapour, whilst the salts are left behind. This is why a crust (incrustation), consisting of salts, previously in solution, is deposited on the insides of kettles or boilers, and other vessels in which water is boiled. Running water (rivers, &c.) is charged with salts, owing to its being formed from the collection of rain water percolating through the soil. While percolating, the water dissolves certain parts of the soil. Thus water which filters or passes through saline or calcareous soils becomes charged with salts or contains calcium carbonate (chalk). Rain water and snow are much purer than river or spring water. Nevertheless, in passing through the atmosphere, rain and snow succeed in catching the dust held in it, and dissolve air, which is found in every water. The dissolved gases of the atmosphere are partly disengaged, as bubbles from water on heating, and water after long boiling is quite freed from them. [1] In practice, the chemist has to continually deal with gases, and gases are often collected over water; in which case a certain amount of water passes into vapour, and this vapour mixes with the gases. It is therefore most important that he should be able to calculate the amount of water or of _moisture in air and other gases_. Let us imagine a cylinder standing in a mercury bath, and filled with a dry gas whose volume equals _v_, temperature _t_°, and pressure or tension _h_ mm. (_h_ millimetres of the column of mercury at 0°). We will introduce water into the cylinder in such a quantity that a small part remains in the liquid state, and consequently that the gas will be saturated with aqueous vapour; the volume of the gas will then increase (if a larger quantity of water be taken some of the gas will he dissolved in it, and the volume may therefore he diminished). We will further suppose that, after the addition of the water, the temperature remains constant; then since the volume increases, the mercury in the cylinder falls, and therefore the pressure as well as the volume is increased. In order to investigate the phenomenon we will artificially increase the pressure, and reduce the volume to the original volume _v_. Then the pressure or tension will be greater than _h_, namely _h_ + _f_, which means that by the introduction of aqueous vapour the pressure of the gas is increased. The researches of Dalton, Gay-Lussac, and Regnault showed that this increase is equal to the maximum pressure which is proper to the aqueous vapour at the temperature at which the observation is made. The maximum pressure for all temperatures may be found in the tables made from observations on the pressure of aqueous vapour. The quantity _f_ will be equal to this maximum pressure of aqueous vapour. This may be expressed thus: the maximum tension of aqueous vapour (and of all other vapours) saturating a space in a vacuum or in any gas is the same. This rule is known as _Dalton's law_. Thus we have a volume of dry gas _v_, under a pressure _h_, and a volume of moist gas, saturated with vapour, under a pressure _h_ + _f_. The volume _v_ of the dry gas under a pressure _h_ + _f_ occupies, from Boyle's law, a volume _vh_/_h_ + _f_; consequently the volume occupied by the aqueous vapour under the pressure _h_ + _f_ equals _v_-_vh_/(_h_ + _f_), or _vf_/(_h_ + _f_). Thus the volumes of the dry gas and of the moisture which occurs in it, at a pressure _h_ + _f_, are in the ratio _f_ : _h_. And, therefore, if the aqueous vapour saturates a space at a pressure _n_, the volumes of the dry air and of the moisture which is contained in it are in the ratio (_n_-_f_) : _f_, where _f_ is the pressure of the vapour according to the tables of vapour tension. Thus, if a volume N of a gas saturated with moisture be measured at a pressure H, then the volume of the gas, when dry, will be equal to N[(H-f)/H]. In fact, the entire volume N must be to the volume of dry gas _x_ as H is to H-_f_; therefore, N : _x_ = H : H-_f_, from which _x_ = N[(H-f)/H]. Under any other pressure--for instance, 760 mm.--The volume of dry gas will be _x_H/760, or (H-_f_)/760, and we thus obtain the following practical rule: If a volume of a gas saturated with aqueous vapour be measured at a pressure H mm., then the volume of dry gas contained in it will be obtained by finding the volume corresponding to the pressure H, less the pressure due to the aqueous vapour at the temperature observed. For example, 37·5 cubic centimetres of air saturated with aqueous vapour were measured at a temperature of 15·3°, and under a pressure of 747·3 mm. of mercury (at 0°). What will be the volume of dry gas at 0° and 760 mm.? The pressure of aqueous vapour corresponding to 15·3° is equal to 12·9 mm., and therefore the volume of dry gas at 15·3° and 747·3 mm. is equal to 37·5 × (747·3-12·9)/747·3; at 760 mm. it will be equal to 37·5 × (734·4/760); and at 0° the volume of dry gas will be 37·5 × (734·4/760) × 273/(273 + 15·3) = 34·31 c.c. From this rule may also be calculated what fraction of a volume of gas is occupied by moisture under the ordinary pressure at different temperatures; for instance, at 30° C. _f_ = 31·5, consequently 100 volumes of a moist gas or air, at 760 mm., contain a volume of aqueous vapour 100 × (31·5/760), or 4·110; it is also found that at 0° there is contained 0·61 p.c. by volume, at 10° 1·21 p.c., at 20° 2·29 p.c., and at 50° up to 12·11 p.c. From this it may be judged how great an error might be made in the measurement of gases by volume if the moisture were not taken into consideration. From this it is also evident how great are the variations in volume of the atmosphere when it loses or gains aqueous vapour, which again explains a number of atmospheric phenomena (winds, variation of pressure, rainfalls, storms, &c.) If a gas is not saturated, then it is indispensable that the degree of moisture should be known in order to determine the volume of dry gas from the volume of moist gas. The preceding ratio gives the maximum quantity of water which can be held in a gas, and the degree of moisture shows what fraction of this maximum quantity occurs in a given case, when the vapour does not saturate the space occupied by the gas. Consequently, if the degree of moisture equals 50 p.c.--that is, half the maximum--then the volume of dry gas at 760 mm. is equal to the volume of dry gas at 760 mm. multiplied by (_h_-0·5_f_)/760, or, in general, by (_h_-_rf_)/760 where _r_ is the degree of moisture. Thus, if it is required to measure the volume of a moist gas, it must either be thoroughly dried or quite saturated with moisture, or else the degree of moisture determined. The first and last methods are inconvenient, and therefore recourse is usually had to the second. For this purpose water is introduced into the cylinder holding the gas to be measured; it is left for a certain time so that the gas may become saturated, the precaution being taken that a portion of the water remains in a liquid state; then the volume of the moist gas is determined, from which that of the dry gas may be calculated. In order to find the _weight of the aqueous vapour_ in a gas it is necessary to know the weight of a cubic measure at 0° and 760 mm. Knowing that one cubic centimetre of air in these circumstances weighs 0·001293 gram, and that the density of aqueous vapour is 0·62, we find that one cubic centimetre of aqueous vapour at 0° and 760 mm. weighs 0·0008 gram, and at a temperature _t_° and pressure _h_ the weight of one cubic centimetre will be 0·0008 × _h_/760 × 273/(273 + _t_). We already know that _v_ volumes of a gas at a temperature _t_° pressure _h_ contain _v_ × _f_/_h_ volumes of aqueous vapour which saturate it, therefore the weight of the aqueous vapour held in _v_ volumes of a gas will be _v_ x 0·0008 × _f_/760 × 273/(273 + _t_). Accordingly, the weight of water which is contained in one volume of a gas depends only on the temperature and not on the pressure. This also signifies that evaporation proceeds to the same extent in air as in a vacuum, or, in general terms (this is _Dalton's law_), vapours and gases diffuse into each other as if into a vacuum. In a given space, at a given temperature, a constant quantity of vapour enters, whatever be the pressure of the gas filling that space. From this it is clear that if the weight of the vapour contained in a given volume of a gas be known, it is easy to determine the degree of moisture _r_ = _p_/(_v_ × 0·0008) × 760/_t_ × (273 + _t_)/273. On the is founded the very exact determination of the degree of moisture of air by the weight of water contained in a given volume. It is easy to calculate from the preceding formula the number of grams of water contained at any pressure in one cubic metre or million cubic centimetres of air saturated with vapour at various temperatures; for instance, at 30° _f_ = 31·5, hence _p_ = 29·84 grams. The laws of Mariotte, Dalton, and Gay-Lussac, which are here applied to gases and vapours, are not entirely exact, but are approximately true. If they were quite exact, a mixture of several liquids, having a certain vapour pressure, would give vapours of a very high pressure, which is not the case. In fact the pressure of aqueous vapour is slightly less in a gas than in a vacuum, and the weight of aqueous vapour held in a gas is slightly less than it should be according to Dalton's law, as was shown by the experiments of Regnault and others. This means that the tension of the vapour is less in air than in a vacuum. The difference does not, however, exceed 5 per cent. of the total pressure of the vapours. This _decrement in vapour tension_ which occurs in the intermixture of vapours and gases, although small, indicates that there is then already, so to speak, a beginning of chemical change. The essence of the matter is that in this case there occurs, as on contact (see preceding footnote), an alteration in the motions of the atoms in the molecules, and therefore also a change in the motion of the molecules themselves. In the uniform intermixture of air and other gases with aqueous vapour, and in the capacity of water to pass into vapour and form a uniform mixture with air, we may perceive an instance of a physical phenomenon which is analogous to chemical phenomena, forming indeed a transition from one class of phenomena to the other. Between water and dry air there exists a kind of affinity which obliges the water to saturate the air. But such a homogeneous mixture is formed (almost) independently of the nature of the gas in which evaporation takes place; even in a vacuum the phenomenon occurs in exactly the same way as in a gas, and therefore it is not the property of the gas, nor its relation to water, but the property of the water itself, which compels it to evaporate, and therefore in this case chemical affinity is not yet operative--at least its action is not clearly pronounced. That it does, however, play a certain part is seen from the deviation from Dalton's law. [2] In falling through the atmosphere, water dissolves the gases of the atmosphere, nitric acid, ammonia, organic compounds, salts of sodium, magnesium, and calcium, and mechanically washes out a mixture of dust and microbes which are suspended in the atmosphere. The amount of these and certain other constituents is very variable. Even in the beginning and end of the same rainfall a variation which is often very considerable may be remarked. Thus, for example, Bunsen found that rain collected at the beginning of a shower contained 3·7 grams of ammonia per cubic metre, whilst that collected at the end of the same shower contained only O·64 gram. The water of the entire shower contained an average of 1·47 gram of ammonia per cubic metre. In the course of a year rain supplies an acre of ground with as much as 5-1/2 kilos of nitrogen in a combined form. Marchand found in one cubic metre of snow water 15·63, and in one cubic metre of rain water 10·07, grams of sodium sulphate. Angus Smith showed that after a thirty hours' fall at Manchester the rain still contained 34·3 grams of salts per cubic metre. A considerable amount of organic matter, namely 25 grams per cubic metre, has been found in rain water. The total amount of solid matter in rain water reaches 50 grams per cubic metre. Rain water generally contains very little carbonic acid, whilst river water contains a considerable quantity of it. In considering the nourishment of plants it is necessary to keep in view the substances which are carried into the soil by rain. _River water_, which is accumulated from springs and sources fed by atmospheric water, contains from 50 to 1,600 parts by weight of salts in 1,000,000 parts. The amount of solid matter, per 1,000,000 parts by weight, contained in the chief rivers is as follows:--the Don 124, the Loire 135, the St. Lawrence 170, the Rhone 182, the Dnieper 187, the Danube from 117 to 234, the Rhine from 158 to 317, the Seine from 190 to 432, the Thames at London from 400 to 450, in its upper parts 387, and in its lower parts up to 1,617, the Nile 1,580, the Jordan 1,052. The Neva is characterised by the remarkably small amount of solid matter it contains. From the investigations of Prof. G. K. Trapp, a cubic metre of Neva water contains 32 grams of incombustible and 23 grams of organic matter, or altogether about 55 grams. This is one of the purest waters which is known in rivers. The large amount of impurities in river water, and especially of organic impurity produced by pollution with putrid matter, makes the water of many rivers unfit for use. The chief part of the soluble substances in river water consists of the calcium salts. 100 parts of the solid residues contain the following amounts of calcium carbonate--from the water of the Loire 53, from the Thames about 50, the Elbe 55, the Vistula 65, the Danube 65, the Rhine from 55 to 75, the Seine 75, the Rhone from 82 to 94. The Neva contains 40 parts of calcium carbonate per 100 parts of saline matter. The considerable amount of calcium carbonate which river water contains is very easily explained from the fact that water which contains carbonic acid in solution easily dissolves calcium carbonate, which occurs all over the earth. Besides calcium carbonate and sulphate, river water contains magnesium, silica, chlorine, sodium, potassium, aluminium, nitric acid, iron and manganese. The presence of salts of phosphoric acid has not yet been determined with exactitude for all rivers, but the presence of nitrates has been proved with certainty in almost all kinds of well-investigated river water. The quantity of calcium phosphate does not exceed 0·4 gram in the water of the Dnieper, and the Don does not contain more than 5 grams. The water of the Seine contains about 15 grams of nitrates, and that of the Rhone about 8 grams. The amount of ammonia is much less; thus in the water of the Rhine about 0·5 gram in June, and 0·2 gram in October; the water of the Seine contains the same amount. This is less than in rain water. Notwithstanding this insignificant quantity, the water of the Rhine alone, which is not so very large a river, carries 16,245 kilograms of ammonia into the ocean every day. The difference between the amount of ammonia in rain and river water depends on the fact that the soil through which the rain water passes is able to retain the ammonia. (Soil can also absorb many other substances, such as phosphoric acid, potassium salts, &c.) The waters of springs, rivers, wells, and in general of those localities from which it is taken for drinking purposes, may be injurious to health if it contains much organic pollution, the more so as in such water the lower organisms (bacteria) may rapidly develop, and these organisms often serve as the carriers or causes of infectious diseases. For instance, certain pathogenic (disease-producing) bacteria are known to produce typhoid, the Siberian plague, and cholera. Thanks to the work of Pasteur, Metchnikoff, Koch, and many others, this province of research has made considerable progress. It is possible to investigate the number and properties of the germs in water. In bacteriological researches a gelatinous medium in which the germs can develop and multiply is prepared with gelatin and water, which has previously been heated several times, at intervals, to 100° (it is thus rendered sterile--that is to say, all the germs in it are killed). The water to be investigated is added to this prepared medium in a definite and small quantity (sometimes diluted with sterilised water to facilitate the calculation of the number of germs), it is protected from dust (which contains germs), and is left at rest until whole families of lower organisms are developed from each germ. These families (colonies) are visible to the naked eye (as spots), they may be counted, and by examining them under the microscope and observing the number of organisms they produce, their significance may be determined. The majority of bacteria are harmless, but there are decidedly pathogenic bacteria, whose presence is one of the causes of malady and of the spread of certain diseases. The number of bacteria in one cubic centimetre of water sometimes attains the immense figures of hundreds of thousands and millions. Certain well, spring, and river waters contain very few bacteria, and are free from disease-producing bacteria under ordinary circumstances. By boiling water, the bacteria in it are killed, but the organic matter necessary for their nourishment remains in the water. The best kinds of water for drinking purposes do not contain more than 300 bacteria in a cubic centimetre. The amount of gases dissolved in river water is much more constant than that of its solid constituents. One litre, or 1,000 c.c., of water contains 40 to 55 c.c. of gas measured at normal temperature and pressure. In winter the amount of gas is greater than in summer or autumn. Assuming that a litre contains 50 c.c. of gases, it may be admitted that these consist, on an average, of 20 vols. of nitrogen, 20 vols of carbonic anhydride (proceeding in all likelihood from the soil and not from the atmosphere), and of 10 vols. of oxygen. If the total amount of gases be less, the constituent gases are still in about the same proportion; in many cases, however, carbonic anhydride predominates. The water of many deep and rapid rivers contains less carbonic anhydride, which shows their rapid formation from atmospheric water, and that they have not succeeded, during a long and slow course, in absorbing a greater quantity of carbonic anhydride. Thus, for instance, the water of the Rhine, near Strasburg, according to Deville, contains 8 c.c. of carbonic anhydride, 16 c.c. of nitrogen, and 7 c.c. of oxygen per litre. From the researches of Prof. M. R. Kapoustin and his pupils, it appears that in determining the quality of a water for drinking purposes, it is most important to investigate the composition of the dissolved gases, more especially oxygen. [3] _Spring water_ is formed from rain water percolating through the soil. Naturally a part of the rain water is evaporated directly from the surface of the earth and from the vegetation on it. It has been shown that out of 100 parts of water falling on the earth only 36 parts flow to the ocean; the remaining 64 are evaporated, or percolate far underground. After flowing underground along some impervious strata, water comes out at the surface in many places as springs, whose temperature is determined by the depth from which the water has flowed. Springs penetrating to a great depth may become considerably heated, and this is why hot mineral springs, with a temperature of up to 30° and higher, are often met with. When a spring water contains substances which endow it with a peculiar taste, and especially if these substances are such as are only found in minute quantities in river and other flowing waters, then the spring water is termed a _mineral water_. Many such waters are employed for medicinal purposes. Mineral waters are classed according to their composition into--(_a_) saline waters, which often contain a large amount of common salt; (_b_) alkaline waters, which contain sodium carbonate; (_c_) bitter waters, which contain magnesia; (_d_) chalybeate waters, which hold iron carbonate in solution; (_e_) aërated waters, which are rich in carbonic anhydride; (_f_) sulphuretted waters, which contain hydrogen sulphide. Sulphuretted waters may be recognised by their smell of rotten eggs, and by their giving a black precipitate with lead salts, and also by their tarnishing silver objects. Aërated waters, which contain an excess of carbonic anhydride, effervesce in the air, have a sharp taste, and redden litmus paper. Saline waters leave a large residue of soluble solid matter on evaporation, and have a salt taste. Chalybeate waters have an inky taste, and are coloured black by an infusion of galls; on being exposed to the air they usually give a brown precipitate. Generally, the character of mineral waters is mixed. In the table below the analyses are given of certain mineral springs which are valued for their medicinal properties. The quantity of the substances is expressed in millionths by weight. Column Headings: A: Calcium salts B: Sodium chloride C: Sodium sulphate D: Sodium carbonate E: Potassium iodide and bromide +-------+-------+--------+-------+-------+-----+------+ | | | | | | | | | | [A] | [B] | [C] | [D] | [E] | [F] | | | | | | | | | +-------+-------+--------+-------+-------+-----+------+ | | | | | | | | | I. | 1,928 | -- | 152 | -- | -- | 24 | | II. | 816 | 386 | 1,239 | 26 | -- | 43 | | III. | 1,085 | 1,430 | 1,105 | -- | 4 | 90 | | IV. | 343 | 3,783 | 16 | 3,431 | -- | 14 | | V. | 3,406 | 15,049 | -- | -- | 2 | -- | | VI. | 352 | 3,145 | -- | 95 | 35 | 50 | | VII. | 308 | 1,036 | 2,583 | 1,261 | 4 | 178 | | VIII. | 1,726 | 9,480 | -- | -- | 40 | 120 | | IX. | 551 | 2,040 | 1,150 | 999 | -- | 1 | | X. | 285 | 558 | 279 | 3,813 | -- | -- | | | | | | | | | | XI. | 340 | 910 | Iron and aluminium {1,020 | | | | | sulphates: {1,660 | +-------+-------+--------+----------------------------+ Column Headings: G: Iron carbonate H: Magnesium salts I: Silica J: Carbonic anhydride K: Sulphuretted hydrogen L: Total solid contents +-------+------+-------+-----+-------+-----+-----------+ | | | | | | | | | | [G] | [H] | [I] | [J] | [K] | [L] | +-------+------+-------+-----+-------+-----+-----------+ | | | | | | | | | I. | -- | 448 | 152 | 1,300 | 80 | 2,609 | | II. | 9 | 257 | 46 | 1,485 | -- | 2,812 | | III. | -- | 187 | 65 | 1,326 | 11 | 3,950 | | IV. | -- | 251 | 112 | 2,883 | -- | 7,950 | | V. | 17 | 1,587 | 229 | -- | 76 | 20,290 | | VI. | 1 | 260 | 11 | 20 | -- | 3,970 | | VII. | 4 | 178 | 75 | -- | -- | 5,451 | | VIII. | 26 | 208 | 40 | -- | -- | 11,790 | | IX. | 30 | 209 | 50 | 2,740 | -- | 4,070 | | X. | 7 | 45 | 45 | 2,268 | -- | 5,031 | | | | | | {Sulphuric | | XI. | | 940 | 190 | 2,550 {and hydrochloric | | | | | | 330 {acids | +-------+------+-------+-----+-------------------------+ I. Sergieffsky, a sulphur water, Gov. of Samara (temp. 8° C.), analysis by Clause. II. Geléznovodskya water source No. 10, near Patigorsk, Caucasus (temp. 22·5°), analysis by Fritzsche. III. Aleksandroffsky, alkaline-sulphur source, Patigorsk (temp. 46·5°), average of analyses by Herman, Zinin and Fritzsche. IV. Bougountouksky, alkaline source, No. 17, Essentoukah, Caucasus (temp. 21·6°), analysis by Fritzsche. V. Saline water, Staro-Russi, Gov. of Novgorod, analysis by Nelubin. VI. Water from artesian well at the factory of state papers, St. Petersburg, analysis by Struve. VII. Sprüdel, Carlsbad (temp. 83·7°), analysis by Berzelius. VIII. Kreuznach spring (Elisenquelle), Prussia (temp. 8·8°), analysis by Bauer. IX. Eau de Seltz, Nassau, analysis by Henry. X. Vichy water, France, analysis by Berthier and Puvy. XI. Paramo de Ruiz, New Granada, analysis by Levy; it is distinguished by the amount of free acids. [4] _Sea water_ contains more non-volatile saline constituents than the usual kinds of fresh water. This is explained by the fact that the waters flowing into the sea supply it with salts, and whilst a large quantity of vapour is given off from the surface of the sea, the salts remain behind. Even the specific gravity of sea water differs considerably from that of pure water. It is generally about 1·02, but in this and also in respect of the amount of salts contained, samples of sea water from different localities and from different depths offer rather remarkable variations. It will be sufficient to point out that one cubic metre of water from the undermentioned localities contains the following quantity in grams of solid constituents:--Gulf of Venice, 19,122; Leghorn Harbour 24,312; Mediterranean, near Cetta, 37,665; the Atlantic Ocean from 32,585 to 35,695,; the Pacific Ocean from 35,233 to 34,708. In closed seas which do not communicate, or are in very distant communication, with the ocean, the difference is often still greater. Thus the Caspian Sea contains 6,300 grams; the Black Sea and Baltic 17,700. Common salt forms the chief constituent of the saline matter of sea or ocean water; thus in one cubic metre of sea water there are 25,000-31,000 grams of common salt, 2,600-6,000 grams of magnesium chloride, 1,200-7,000 grams of magnesium sulphate, 1,500-6,000 grams of calcium sulphate, and 10-700 grams of potassium chloride. The small amount of organic matter and of the salts of phosphoric acid in sea water is very remarkable. Sea water (the composition of which is partially discussed in Chapter X.) contains, in addition to salts of common occurrence, a certain and sometimes minute amount of the most varied elements, even gold and silver, and as the mass of water of the oceans is so enormous these 'traces' of rare substances amount to large quantities, so that it may be hoped that in time methods will be found to extract even gold from sea water, which by means of the rivers forms a vast reservoir for the numerous products of the changes taking place on the earth's surface. The works of English, American, German, Russian, Swedish, and other navigators and observers prove that a study of the composition of sea water not only explains much in the history of the earth's life, but also gives the possibility (especially since the researches of C. O. Makaroff of the St. Petersburg Academy) of fixing one's position in the ocean in the absence of other means, for instance, in a fog, or in the dark. In general terms water is called pure when it is clear and free from insoluble particles held in suspension and visible to the naked eye, from which it may be freed by filtration through charcoal, sand, or porous (natural or artificial) stones, and when it possesses a clean fresh taste. It depends on the absence of any taste, decomposing organic matter, on the quantity of air[5] and atmospheric gases in solution, and on the presence of mineral substances to the amount of about 300 grams per ton (or 1000 kilograms per cubic metre, or, what is the same, 300 milligrams to a kilogram or a litre of water), and of not more than 100 grams of organic matter.[6] Such water is suitable for drinking and every practical application, but evidently it is not pure in a chemical sense. A _chemically pure water_ is necessary not only for scientific purposes, as an independent substance having constant and definite properties, but also for many practical purposes--for instance, in photography and in the preparation of medicines--because many properties of substances in solution are changed by the impurities of natural waters. Water is usually purified by distillation, because the solid substances in solution are not transformed into vapours in this process. Such _distilled_ water is prepared by chemists and in laboratories by boiling water in closed metallic boilers or stills, and causing the steam produced to pass into a condenser--that is, through tubes (which should be made of tin, or, at all events, tinned, as water and its impurities do not act on tin) surrounded by cold water, and in which the steam, being cooled, condenses into water which is collected[7] in a receiver. By standing exposed to the atmosphere, however, the water in time absorbs air, and dust carried in the air. Nevertheless, in distillation, water retains, besides air, a certain quantity of volatile impurities (especially organic) and the walls of the distillation apparatus are partly corroded by the water, and a portion, although small, of their substance renders the water not entirely pure, and a residue is left on evaporation.[8] [5] The taste of water is greatly dependent on the quantity of dissolved gases it contains. These gases are given off on boiling, and it is well known that, even when cooled, boiled water has, until it has absorbed gaseous substances from the atmosphere, quite a different taste from fresh water containing a considerable amount of gas. The dissolved gases, especially oxygen and carbonic anhydride, have an important influence on the health. The following instance is very instructive in this respect. The Grenelle artesian well at Paris, when first opened, supplied a water which had an injurious effect on men and animals. It appeared that this water did not contain oxygen, and was in general very poor in gases. As soon as it was made to fall in a cascade, by which it absorbed air, it proved quite fit for consumption. In long sea voyages fresh water is sometimes not taken at all, or only taken in a small quantity, because it spoils by keeping, and becomes putrid from the organic matter it contains undergoing decomposition. Fresh water may he obtained directly from sea-water by distillation. The distilled water no longer contains sea salts, and is therefore fit for consumption, but it is very tasteless and has the properties of boiled water. In order to render it palatable certain salts, which are usually held in fresh water, are added to it, and it is made to flow in thin streams exposed to the air in order that it may become saturated with the component parts of the atmosphere--that is, absorb gases. [6] _Hard water_ is such as contains much mineral matter, and especially a large proportion of calcium salts. Such water, owing to the amount of lime it contains, does not form a lather with soap, prevents vegetables boiled in it from softening properly, and forms a large amount of incrustation on vessels in which it is boiled. When of a high degree of hardness, it is injurious for drinking purposes, which is evident from the fact that in several large cities the death-rate has been found to decrease after introducing a soft water in the place of a hard water. _Putrid water_ contains a considerable quantity of decomposing organic matter, chiefly vegetable, but in populated districts, especially in towns, chiefly animal remains. Such water acquires an unpleasant smell and taste, by which stagnant bog water and the water of certain wells in inhabited districts are particularly characterised. Water of this kind is especially injurious at a period of epidemic. It may be partially purified by being passed through charcoal, which retains the putrid and certain organic substances, and also certain mineral substances. Turbid water may be purified to a certain extent by the addition of alum, which aids, after standing some time, the formation of a sediment. Condy's fluid (potassium permanganate) is another means of purifying putrid water. A solution of this substance, even if very dilute, is of a red colour; on adding it to a putrid water, the permanganate oxidises and destroys the organic matter. When added to water in such a quantity as to impart to it an almost imperceptible rose colour it destroys much of the organic substances it contains. It is especially salutary to add a small quantity of Condy's fluid to impure water in times of epidemic. The presence in water of one gram per litre, or 1,000 grams per cubic metre, of any substance whatsoever, renders it unfit and even injurious for consumption by animals, and this whether organic or mineral matter predominates. The presence of 1 p.c. of chlorides makes water quite salt, and produces thirst instead of assuaging it. The presence of magnesium salts is most unpleasant; they have a disagreeable bitter taste, and, in fact, impart to sea water its peculiar taste. A large amount of nitrates is only found in impure water, and is usually injurious, as they may indicate the presence of decomposing organic matter. [7] [Illustration: FIG. 4.--Distillation by means of a metallic still. The liquid in C is heated by the fire F. The vapours rise through the head A and pass by the tube T to the worm S placed in a vessel R, through which a current of cold water flows by means of the tubes D and P.] Distilled water may be prepared, or distillation in general carried on, either in a metal still with worm condenser (fig. 4) or on a small scale in the laboratory in a glass retort (fig. 5) heated by a lamp. Fig. 5 illustrates the main parts of the usual glass laboratory apparatus used for distillation. The steam issuing from the retort (on the right-hand side) passes through a glass tube surrounded by a larger tube, through which a stream of cold water passes, by which the steam is condensed, and runs into a receiver (on the left-hand side). [Illustration: FIG. 5.--Distillation from a glass retort. The neck of the retort fits into the inner tube of the Liebig's condenser. The space between the inner and outer tube of the condenser is filled with cold water, which enters by the tube _g_ and flows out at _f_.] [8] One of Lavoisier's first memoirs (1770) referred to this question. He investigated the formation of the earthy residue in the distillation of water in order to prove whether it was possible, as was affirmed, to convert water into earth, and he found that the residue was produced by the action of water on the sides of the vessel containing it, and not from the water itself. He proved this to be the case by direct weighing. For certain physical and chemical researches, however, it is necessary to have perfectly pure water. To obtain it, a solution of potassium permanganate is added to distilled water until the whole is a light rose colour. By this means the organic matter in the water is destroyed (converted into gases or non-volatile substances). An excess of potassium permanganate does no harm, because in the next distillation it is left behind in the distillation apparatus. The second distillation should take place in a platinum retort with a platinum receiver. Platinum is a metal which is not acted on either by air or water, and therefore nothing passes from it into the water. The water obtained in the receiver still contains air. It must then be boiled for a long time, and afterwards cooled in a vacuum under the receiver of an air pump. Pure water does not leave any residue on evaporation; does not in the least change, however long it be kept; does not decompose like water only once distilled or impure; and it does not give bubbles of gas on heating, nor does it change the colour of a solution of potassium permanganate. Water, purified as above described, has constant _physical_ and _chemical properties_. For instance, it is of such water only that one cubic centimetre weighs one gram at 4° C.--_i.e._ it is only such pure water whose specific gravity equals 1 at 4° C.[9] Water in a solid state forms crystals of the hexagonal system[10] which are seen in snow, which generally consists of star-like clusters of several crystals, and also in the half-melted scattered ice floating on rivers in spring time. At this time of the year the ice splits up into spars or prisms, bounded by angles proper to substances crystallising in the hexagonal system. [9] Taking the generally-accepted specific gravity of water at its greatest density--_i.e._ at 4° as one--it has been shown by experiment that the specific gravity of water at different temperatures is as follows: At 0° 0·99987 | At 30° 0·99574 " +10° 0·99974 | " 40° 0·99233 " 15° 0·99915 | " 50° 0·98817 " 20° 0·99827 | " 100° 0·95859 A comparison of all the data at present known shows that the variation of the specific gravity S_{t} with the temperature _t_ (determined by the mercurial thermometer) maybe expressed (Mendeléeff 1891) by the formula S_{t} = 1 - (_t_-4)^{2}/(94·1 + _t_) (703·51-_t_) 1·9 +-----------+-------------+---------------------------+-----------+ | t° C. | | Variation of sp. gr. with | | | according |Sp. gr. S_{t}| a rise of | Volume | | to the |(at 4° = +--------------+------------+taking vol.| | mercurial | 1,000,000) |Temp. per 1°C.|Pressure per| at 4° = 1 | |thermometer| | or ds/dt |1 atmosphere| | | | | | or ds/dp | | +-----------+-------------+--------------+------------+-----------+ | -10 | 998,281 | +264 | +54 | 1,001,722 | | 0 | 999,873 | +65 | +50 | 1,000,127 | | 10 | 999,738 | -85 | +47 | 1,000,262 | | 20 | 998,272 | -203 | +45 | 1,001,731 | | 30 | 995,743 | -299 | +43 | 1,004,276 | | 50 | 988,174 | -450 | +40 | 1,011,967 | | 70 | 977,948 | -569 | +39 | 1,022,549 | | 90 | 965,537 | -670 | +41 | 1,035,692 | | 100 | 958,595 | -718 | +42 | 1,043,194 | | 120 | 943,814 | -810 | +43 | 1,060,093 | | 160 | 907,263 | -995 | +55 | 1,102,216 | | 200 | 863,473 | -1,200 | +73 | 1,158,114 | +-----------+-------------+--------------+------------+-----------+ If the temperature be determined by the hydrogen thermometer, whose indications between 0° and 100° are slightly lower than the mercurial (for example, about 0·1° C. at 20°), then a slightly smaller sp. gr. will be obtained for a given _t_. Thus Chappuis (1892) obtained 0·998233 for 20°. Water at 4° is taken as the basis for reducing measures of length to measures of weight and volume. The _metric, decimal, system_ of measures of weights and volumes is generally employed in science. The starting point of this system is the metre (39·37 inches) divided into decimetres (= 0·1 metre), centimetres (= 0·01 metre), millimetres (= 0·001 metre), and micrometres (= one millionth of a metre). A cubic decimetre is called a _litre_, and is used for the measurement of volumes. The weight of a litre of water at 4° in a vacuum is called a kilogram. One thousandth part of a kilogram of water weighs one _gram_. It is divided into decigrams, centigrams, and milligrams (= 0·001 gram). An English pound equals 453·59 grams. The great advantage of this system is that it is a decimal one, and that it is universally adopted in science and in most international relations. _All the measures cited in this work are metrical._ The units most often used in science are:--Of length, the centimetre; of weight, the gram; of time, the second; of temperature, the degree Celsius or Centigrade. According to the most trustworthy determinations (Kupfer in Russia 1841, and Chaney in England 1892), the weight of a c. dcm. of water at 4° in vacuo is about 999·9 grms. For ordinary purposes the weight of a c. dcg. may be taken as equal to a kg. Hence the litre (determined by the weight of water it holds) is slightly greater than a cubic decimetre. [10] As solid substances appear in independent, regular, crystalline forms which are dependent, judging from their cleavage or lamination (in virtue of which mica breaks, up into laminae, and Iceland spar, &c., into pieces bounded by faces inclined to each other at angles which are definite for each substance), on an inequality of attraction (cohesion, hardness) in different directions which intersect at definite angles the determination of crystalline form therefore affords one of the most important characteristics for identifying definite chemical compounds. The elements of crystallography which comprise a special science should therefore he familiar to all who desire to work in scientific chemistry. In this work we shall only have occasion to speak of a few crystalline forms, some of which are shown in figs. 6 to 12. [Illustration: FIG. 6.--Example of the form belonging to the regular system. Combination of an octahedron and a cube. The former predominates. Alum, fluor spar, suboxide of copper, and others.] [Illustration: FIG. 7.--Rhombic Dodecahedron of the regular system. Garnet.] [Illustration: FIG. 8.--Hexagonal prism terminated by hexagonal pyramids. Quartz, &c.] [Illustration: FIG. 9.--Rhombohedron. Calc spar, &c.] [Illustration: FIG. 10.--Rhombic system. Desmine.] [Illustration: FIG. 11.--Triclinic pyramid.] [Illustration: FIG. 12.--Triclinic system. Albite, &c.] The temperatures at which water passes from one state to another are taken as fixed points on the thermometer scale; namely, the zero corresponds with the temperature of melting ice, and the temperature of the steam disengaged from water boiling at the normal barometric pressure (that is 760 millimetres measured at 0°, at the latitude of 45°, at the sea level) is taken as 100° of the Celsius scale. Thus, the fact that water liquefies at 0° and boils at 100° is taken as one of its properties as a definite chemical compound. The weight of a litre of water at 4° is 1,000 grams, at 0° it is 999·8 grams. The weight of a litre of ice at 0° is less--namely, 917 grams; the weight of the same cubic measure of water vapour at 760 mm. pressure and 100° is only 0·60 gram; the density of the vapour compared with air = 0·62, and compared with hydrogen = 9. These data briefly characterise the physical properties of water as a separate substance. To this may be added that water is a mobile liquid, colourless, transparent, without taste or smell, &c. Its latent heat of vaporisation is 534 units, of liquefaction 79 units of heat.[11] The large amount of heat stored up in water vapour and also in liquid water (for its specific heat is greater than that of other liquids) renders it available in both forms for heating purposes. The chemical reactions which water undergoes, and by means of which it is formed, are so numerous, and so closely allied to the reactions of many other substances, that it is impossible to describe the majority of them at this early stage of chemical exposition. We shall become acquainted with many of them afterwards, but at present we shall only cite certain compounds formed by water. In order to see clearly the nature of the various kinds of compounds formed by water we will begin with the most feeble, which are determined by purely mechanical superficial properties of the reacting substances.[12] [11] Of all known liquids, water exhibits the greatest _cohesion_ of particles. Indeed, it ascends to a greater height in capillary tubes than other liquids; for instance, two and a half times as high as alcohol, nearly three times as high as ether, and to a much greater height than oil of vitriol, &c. In a tube one mm. in diameter, water at 0° ascends 15·3 mm., measuring from the height of the liquid to two-thirds of the height of the meniscus, and at 100° it rises 12·5 mm. The cohesion varies very uniformly with the temperature; thus at 50° the height of the capillary column equals 13·9 mm.--that is, the mean between the columns at 0° and 100°. This uniformity is not destroyed even at temperatures near the freezing point, and hence it may be assumed that at high temperatures cohesion will vary as uniformly as at ordinary temperatures; that is, the difference between the columns at 0° and 100° being 2·8 mm., the height of the column at 500° should be 15·2-(5 × 2·8) = 1·2 mm.; or, in other words, at these high temperatures the cohesion between the particles of water would he almost _nil_. Only certain solutions (sal ammoniac and lithium chloride), and these only with a great excess of water, rise higher than pure water in capillary tubes. The great cohesion of water doubtless determines many of both its physical and chemical properties. The quantity of heat required to raise the temperature of one part by weight of water from 0° to 1°, _i.e._ by 1° C., is called the _unit of heat_ or calorie; the _specific heat of liquid water_ at 0° is taken as equal to unity. The variation of this specific heat with a rise in temperature is inconsiderable in comparison with the variation exhibited by the specific heats of other liquids. According to Ettinger, the specific heat of water at 20° = 1·016, at 50° = 1·039, and at 100° = 1·073. The specific heat of water is greater than that of any other known liquid; for example, the specific heat of alcohol at 0° is 0·55--_i.e._ the quantity of heat which raises 55 parts of water 1° raises 100 parts of alcohol 1°. The specific heat of oil of turpentine at 0° is 0·41, of ether 0·53, of acetic acid 0·5274, of mercury 0·033. Hence water is the best condenser or absorber of heat. This property of water has an important significance in practice and in nature. Water prevents rapid cooling or heating, and thus tempers cold and heat. The specific heats of ice and aqueous vapour are much less than that of water; namely, that of ice is 0·504, and of steam 0·48. With an increase in pressure equal to one atmosphere, the compressibility of water (_see_ Note 9) is 0·000047, of mercury 0·00000352, of ether 0·00012 at 0°, of alcohol at 13° 0·000095. The addition of various substances to water generally decreases both its compressibility and cohesion. The compressibility of other liquids increases with a rise of temperature, but for water it decreases up to 53° and then increases like other liquids. The _expansion of water_ by heat (Note 9) also exhibits many peculiarities which are not found in other liquids. The expansion of water at low temperatures is very small compared with other liquids; at 4° it is almost zero, and at 100° it is equal to 0·0008; below 4° it is negative--_i.e._ water on cooling then expands, and does not decrease in volume. In passing into a solid state, the specific gravity of water decreases; at 0° one c.c. of water weighs 0·999887 gram, and one c.c. of ice at the same temperature weighs only 0·9175 gram. The ice formed, however, contracts on cooling like the majority of other substances. Thus 100 volumes of ice are produced from 92 volumes of water--that is, water expands considerably on freezing, which fact determines a number of natural phenomena. The freezing point of water falls with an increase in pressure (0·007° per atmosphere), because in freezing water expands (Thomson), whilst with substances which contract in solidifying the melting point rises with an increase in pressure; thus, paraffin under one atmosphere melts at 46°, and under 100 atmospheres at 49°. When liquid water passes into vapour, the cohesion of its particles must be destroyed, as the particles are removed to such a distance from each other that their mutual attraction no longer exhibits any influence. As the cohesion of aqueous particles varies at different temperatures, the quantity of heat which is expended in overcoming this cohesion--or the _latent heat of evaporation_--will for this reason alone be different at different temperatures. The quantity of heat which is consumed in the transformation of one part by weight of water, at different temperatures, into vapour was determined by Regnault with great accuracy. His researches showed that one part by weight of water at 0°, in passing into vapour having a temperature _t_°, consumes 606·5 + 0·305_t_ units of heat, at 50° 621·7, at 100° 637·0, at 150° 652·2, and at 200° 667·5. But this quantity includes also the quantity of heat required for heating the water from 0° to _t_°--_i.e._ besides the latent heat of evaporation, also that heat which is used in heating the water in a liquid state to a temperature _t_°. On deducting this amount of heat, we obtain the latent heat of evaporation of water as 606·5 at 0°, 571 at 50°, 534 at 100°, 494 at 150°, and only 453 at 200°, which shows that the conversion of water at different temperatures into vapour at a constant temperature requires very different quantities of heat. This is chiefly dependent on the difference of the cohesion of water at different temperatures; the cohesion is greater at low than at high temperatures, and therefore at low temperatures a greater quantity of heat is required to overcome the cohesion. On comparing these quantities of heat, it will be observed that they decrease rather uniformly, namely their difference between 0° and 100° is 72, and between 100° and 200° is 81 units of heat. From this we may conclude that this variation will be approximately the same for high temperatures also, and therefore that no heat would be required for the conversion of water into vapour at a temperature of about 400°. At this temperature, water passes into vapour whatever be the pressure (see Chap. II. The absolute boiling point of water, according to Dewar, is 370°, the critical pressure 196 atmospheres). It must here be remarked that water, in presenting a greater cohesion, requires a larger quantity of heat for its conversion into vapour than other liquids. Thus alcohol consumes 208, ether 90, turpentine 70, units of heat in their conversion into vapour. The whole amount of heat which is consumed in the conversion of water into vapour is not used in overcoming the cohesion--that is, in internal accomplished in the liquid. A part of this heat is employed in moving the aqueous particles; in fact, aqueous vapour at 100° occupies a volume 1,659 times greater than that of water (at the ordinary pressure), consequently a portion of the heat or work is employed in lifting the aqueous particles, in overcoming pressure, or in external work, which may be usefully employed, and which is so employed in steam engines. In order to determine this work, let us consider the variation of the maximum _pressure_ or _vapour tension of steam_ at different temperatures. The observations of Regnault in this respect, as on those preceding, deserve special attention from their comprehensiveness and accuracy. The pressure or tension of aqueous vapour at various temperatures is given in the adjoining table, and is expressed in millimetres of the barometric column reduced to 0°. +------------+---------+-------------+----------+ |Temperature | Tension | Temperature | Tension | +------------+---------+-------------+----------+ | -20° | 0·9 | 70° | 233·3 | | -10° | 2·1 | 90° | 525·4 | | 0° | 4·6 | 100° | 760·0 | | +10° | 9·1 | 105° | 906·4 | | 15° | 12·7 | 110° | 1075·4 | | 20° | 17·4 | 115° | 1269·4 | | 25° | 23·5 | 120° | 1491·3 | | 30° | 31·5 | 150° | 3581·0 | | 50° | 92·0 | 200° | 11689·0 | +------------+---------+-------------+----------+ The table shows the boiling points of water at different pressures. Thus on the summit of Mont Blanc, where the average pressure is about 424 mm., water boils at 84·4°. In a rarefied atmosphere water boils even at the ordinary temperature, but in evaporating it absorbs heat from the neighbouring parts, and therefore it becomes cold and may even freeze if the pressure does not exceed 4·6 mm., and especially if the vapour be rapidly absorbed as it is formed. Oil of vitriol, which absorbs the aqueous vapour, is used for this purpose. Thus ice may be obtained artificially at the ordinary temperature with the aid of an air-pump. This table of the tension of aqueous vapour also shows the temperature of water contained in a closed boiler if the pressure of the steam formed be known. Thus at a pressure of five atmospheres (a pressure of five times the ordinary atmospheric pressure--_i.e._ 5 × 760 = 3,800 mm.) the temperature of the water would be 152°. The table also shows the pressure produced on a given surface by steam on issuing from a boiler. Thus steam having a temperature of 152° exerts a pressure of 517 kilos on a piston whose surface equals 100 sq. cm., for the pressure of one atmosphere on one sq. cm. equals 1,033 kilos, and steam at 152° has a pressure of five atmospheres. As a column of mercury 1 mm. high exerts a pressure of 1·35959 grams on a surface of 1 sq. cm., therefore the pressure of aqueous vapour at 0° corresponds with a pressure of 6·25 grams per square centimetre. The pressures for all temperatures may be calculated in a similar way, and it will be found that at 100° it is equal to 1,033·28 grams. This means that if a cylinder be taken whose sectional area equals 1 sq. cm., and if water be poured into it and it be closed by a piston weighing 1,033 grams, then on heating it in a vacuum to 100° no steam will be formed, because the steam cannot overcome the pressure of the piston; and if at 100° 534 units of heat be transmitted to each unit of weight of water, then the whole of the water will be converted into vapour having the same temperature; and so also for every other temperature. The question now arises, to what height does the piston rise under these circumstances? that is, in other words, What is the volume occupied by the steam under a known pressure? For this we must know the weight of a cubic centimetre of steam at various temperatures. It has been shown by experiment that the density of steam, which does not saturate a space, varies very inconsiderably at all possible pressures, and is nine times the density of hydrogen under similar conditions. Steam which saturates a space varies in density at different temperatures, but this difference is very small, and its average density with reference to air is 0·64. We will employ this number in our calculation, and will calculate what volume the steam occupies at 100°. One cubic centimetre of air at 0° and 760 mm. weighs 0·001293 gram, at 100° and under the same pressure it will weigh 0·001293/1·368 or about 0·000946 gram, and consequently one cubic centimetre of steam whose density is 0·64 will weigh 0·000605 gram at 100°, and therefore one gram of aqueous vapour will occupy a volume of about 1·653 c.c. Consequently, the piston in the cylinder of 1 sq. cm. sectional area, and in which the water occupied a height of 1 cm., will be raised 1,653 cm. on the conversion of this water into steam. This piston, as has been mentioned, weighs 1,033 grams, therefore the _external work of the steam_--that is, that work which the water does in its conversion into steam at 100°--is equal to lifting a piston weighing 1,033 grams to a height of 1,653 cm., or 17·07 kilogram-metres of work--_i.e._ is capable of lifting 17 kilograms 1 metre, or 1 kilogram 17 metres. One gram of water requires for its conversion into steam 534 gram units of heat or 0·534 kilogram unit of heat--_i.e._ the quantity of heat absorbed in the evaporation of one gram of water is equal to the quantity of heat which is capable of heating 1 kilogram of water 0·534°. Each unit of heat, as has been shown by accurate experiment, is capable of doing 424 kilogram-metres of work. Hence, in evaporating, one gram of water expends 424 × 0·534 = (almost) 227 kilogram-metres of work. The external work was found to be only 17 kilogram-metres, therefore 210 kilogram-metres are expended in overcoming the internal cohesion of the aqueous particles, and consequently about 92 p.c. of the total heat or work is consumed in overcoming the internal cohesion. The following figures are thus calculated approximately:-- +------------+----------------+-----------------+--------------+ | | Total work of |External work of | | |Temperature | evaporation in | vapour in | Internal | | |kilogram-metres |kilogram-metres |work of vapour| +------------+----------------+-----------------+--------------+ | 0° | 255 | 13 | 242 | | 50° | 242 | 15 | 227 | | 100° | 226 | 17 | 209 | | 150° | 209 | 19 | 190 | | 200° | 192 | 20 | 172 | +------------+----------------+-----------------+--------------+ The work necessary for overcoming the internal cohesion of water in its passage into vapour decreases with the rise in temperature--that is, corresponds with the decrease of cohesion; and, in fact, the variations which take place in this case are very similar to those which are observed in the heights to which water rises in capillary tubes at different temperatures. It is evident, therefore, that the amount of external--or, as it is termed, useful--work which water can supply by its evaporation is very small compared with the amount which it expends in its conversion into vapour. In considering certain physico-mechanical properties of water, I had in view not only their importance for theory and practice, but also their purely chemical significance; for it is evident from the above considerations that even in a physical change of state the greatest part of the work done is employed in overcoming cohesion, and that an enormous amount of internal energy must be expended in overcoming chemical cohesion or affinity. [12] When it is necessary to heat a considerable mass of liquid in different vessels, it would be very uneconomical to make use of metallic vessels and to construct a separate furnace for each; such cases are continually met with in practice. Steam from a boiler is introduced into the liquid, or, in general, into the vessel which it is required to heat. The steam, in condensing and passing into a liquid state, parts with its latent heat, and as this is very considerable a small quantity of steam will produce a considerable heating effect. If it be required, for instance, to heat 1,000 kilos of water from 20° to 50°, which requires approximately 30,000 units of heat, steam at 100° is passed into the water from a boiler. Each kilogram of water at 50° contains about 50 units of heat, and each kilogram of steam at 100° contains 637 units of heat; therefore, each kilogram of steam in cooling to 50° gives up 587 units of heat, and consequently 52 kilos of steam are capable of heating 1,000 kilos of water from 20° to 50°. Water is very often applied for heating in chemical practice. For this purpose metallic vessels or pans, called 'water-baths,' are made use of. They are closed by a cover formed of concentric rings lying on each other. The vessels--such as beakers, evaporating basins, retorts, &c.--containing liquids, are placed on these rings, and the water in the bath is heated. The steam given off heats the bottom of the vessels to be heated, and thus effects the evaporation or distillation. Water is mechanically attracted by many substances; it adheres to their surfaces just as dust adheres to objects, or one piece of polished glass adheres to another. Such attraction is termed 'moistening,' 'soaking,' or 'absorption of water.' Thus water moistens clean glass and adheres to its surface, is absorbed by the soil, sand, and clay, and does not flow away from them, but lodges itself between their particles. Similarly, water soaks into a sponge, cloth, hair, or paper, &c., but fat and greasy substances in general are not moistened. Attraction of this kind does not alter the physical or chemical properties of water. For instance, under these circumstances water, as is known from everyday experience, may be expelled from objects by drying. Water which is in any way held mechanically may be dislodged by mechanical means, by friction, pressure, centrifugal force, &c. Thus water is squeezed from wet cloth by pressure or centrifugal machines. But objects which in practice are called dry (because they do not feel wet) often still contain moisture, as may be proved by heating the object in a glass tube closed at one end. By placing a piece of paper, dry earth, or any similar object (especially porous substances) in such a glass tube, and heating that part of the tube where the object is situated, it will be remarked that water condenses on the cooler portions of the tube. The presence of such absorbed, or 'hygroscopic,' water is generally best detected in non-volatile substances by drying them at 100°, or under the receiver of an air-pump and over substances which attract water chemically. By weighing a substance before and after drying, it is easy to determine the amount of hygroscopic water from the loss in weight.[13] Only in this case the amount of water must be judged with care, because the loss in weight may sometimes proceed from the decomposition of the substance itself, with disengagement of gases or vapour. In making exact weighings the hygroscopic capacity of substances--that is, their capacity to absorb moisture--must be continually kept in view, as otherwise the weight will be untrue from the presence of moisture. The quantity of moisture absorbed depends on the degree of moisture of the atmosphere (that is, on the tension of the aqueous vapour in it) in which a substance is situated. In an entirely dry atmosphere, or in a vacuum, the hygroscopic water is expelled, being converted into vapour; therefore, substances containing hygroscopic water may be completely dried by placing them in a dry atmosphere or in a vacuum. The process is aided by heat, as it increases the tension of the aqueous vapour. Phosphoric anhydride (a white powder), liquid sulphuric acid, solid and porous calcium chloride, or the white powder of ignited copper sulphate, are most generally employed in drying gases. They absorb the moisture contained in air and all gases to a considerable, but not unlimited, extent. Phosphoric anhydride and calcium chloride deliquesce, become damp, sulphuric acid changes from an oily thick liquid into a more mobile liquid, and ignited copper sulphate becomes blue; after which changes these substances partly lose their capacity of holding water, and can, if it be in excess, even give up their water to the atmosphere. We may remark that the order in which these substances are placed above corresponds with the order in which they stand in respect to their capacity for absorbing moisture. Air dried by calcium chloride still contains a certain amount of moisture, which it can give up to sulphuric acid. The most complete desiccation takes place with phosphoric anhydride. Water is also removed from many substances by placing them in a dish over a vessel containing a substance absorbing water under a glass bell jar.[14] The bell jar, like the receiver of an air pump, should be hermetically closed. In this case desiccation takes place; because sulphuric acid, for instance, first dries the air in the bell jar by absorbing its moisture, the substance to be dried then parts with its moisture to the dry air, from which it is again absorbed by the sulphuric acid, &c. Desiccation proceeds still better under the receiver of an air pump, for then the aqueous vapour is formed more quickly than in a bell jar full of air. [13] [Illustration: FIG. 13.--Drying oven, composed of brazed copper. It is heated by a lamp. The object to be dried is placed on the gauze inside the oven. The thermometer indicates the temperature.] In order to dry any substance at about 100°--that is, at the boiling point of water (hygroscopic water passes off at this temperature)--an apparatus called a 'drying-oven' is employed. It consists of a double copper box; water is poured into the space between the internal and external boxes, and the oven is then heated over a stove or by any other means, or else steam from a boiler is passed between the walls of the two boxes. When the water boils, the temperature inside the inner box will be approximately 100° C. The substance to be dried is placed inside the oven, and the door is closed. Several holes are cut in the door to allow the free passage of air, which carries off the aqueous vapour by the chimney on the top of the oven. Often, however, desiccation is carried on in copper ovens heated directly over a lamp (fig. 13). In this case any desired temperature may be obtained, which is determined by a thermometer fixed in a special orifice. There are substances which only part with their water at a much higher temperature than 100°, and then such air baths are very useful. In order to determine directly the amount of water in a substance which does not part with anything except water at a red heat, the substance is placed in a bulb tube. By first weighing the tube empty and then with the substance to be dried in it, the weight of the substance taken may be found. The tube is then connected on one side with a gas-holder full of air, which, on opening a stop-cock, passes first through a flask containing sulphuric acid, and then into a vessel containing lumps of pumice stone moistened with sulphuric acid. In passing through these vessels the air is thoroughly dried, having given up all its moisture to the sulphuric acid. Thus dry air will pass into the bulb tube, and as hygroscopic water is entirely given up from a substance in dry air even at the ordinary temperature, and still more rapidly on heating, the moisture given up by the substance in the tube will be carried off by the air passing through it. This damp air then passes through a U-shaped tube full of pieces of pumice stone moistened with sulphuric acid, which absorbs all the moisture given off from the substance in the bulb tube. Thus all the water expelled from the substance will collect in the [U] tube, and so, if this be weighed before and after, the difference will show the quantity of water expelled from the substance. If only water (and not any gases) come over, the increase of the weight of the [U] tube will be equal to the decrease in the weight of the bulb tube. [14] Instead of under a glass bell jar, drying over sulphuric acid is often carried on in a desiccator consisting of a shallow wide-mouthed glass vessel, closed by a well-fitting ground-glass cover. Sulphuric acid is poured over the bottom of the desiccator, and the substance to be dried is placed on a glass stand above the acid. A lateral glass tube with a stop-cock is often fused into the desiccator in order to connect it with an air pump, and so allow drying under a diminished pressure, when the moisture evaporates more rapidly. The fact that in the usual form of desiccator the desiccating substance (sulphuric acid) is placed beneath the substance to be dried has the disadvantage that the moist air being lighter than dry air distributes itself in the upper portion of the desiccator and not below. Hempel, in his desiccator (1891), avoids this by placing the absorbent above the substance to be dried. The process of desiccation can be further accelerated by cooling the upper portion of the desiccator, and so inducing ascending and descending currents of air within the apparatus. From what has been said above, it is evident that the transference of moisture to gases and the absorption of hygroscopic moisture present great resemblance to, but still are not, chemical combinations with water. Water, when combined as hygroscopic water, does not lose its properties and does not form new substances.[15] [15] Chappuis, however, determined that in wetting 1 gram of charcoal with water 7 units of heat are evolved, and on pouring carbon bisulphide over 1 gram of charcoal as much as 24 units of heat are evolved. Alumina (1 gram), when moistened with water, evolves 2-1/2 calories. This indicates that in respect to evolution of heat moistening already presents a transition towards exothermal combinations (those evolving heat in their formation). The attraction of water for substances which dissolve in it is of a different character. In the solution of substances in water there proceeds a peculiar kind of indefinite combination; a new homogeneous substance is formed from the two substances taken. But here also the bond connecting the substances is very unstable. Water containing different substances in solution boils at a temperature near to its usual boiling point. From the solution of substances which are lighter than water itself, there are obtained solutions of a less density than water--as, for example, in the solution of alcohol in water; whilst a heavier substance in dissolving in water gives it a higher specific gravity. Thus salt water is heavier than fresh.[16] [16] Strong acetic acid (C_{2}H_{4}O_{2}), whose specific gravity at 15° is 1·055, does not become lighter on the addition of water (a lighter substance, sp. gr. = 0·999), but heavier, so that a solution of 80 parts of acetic acid and 20 parts of water has a specific gravity of 1·074, and even a solution of equal parts of acetic acid and water (50 p.c.) has a sp. gr. of 1·065, which is still greater than that of acetic acid itself. This shows the high degree of contraction which takes place on solution. In fact, solutions--and, in general, liquids--on mixing with water, decrease in volume. We will consider _aqueous solutions_ somewhat fully, because, among other reasons, solutions are constantly being formed on the earth and in the waters of the earth, in plants and in animals, in chemical processes and in the arts, and these solutions play an important part in the chemical transformations which are everywhere taking place, not only because water is everywhere met with, but chiefly because a substance in solution presents the most favourable conditions for the process of chemical changes, which require a mobility of parts and a possible distension of parts. In dissolving, a solid substance acquires a mobility of parts, and a gas loses its elasticity, and therefore reactions often take place in solutions which do not proceed in the undissolved substances. Further, a substance, distributed in water, evidently breaks up--that is, becomes more like a gas and acquires a greater mobility of parts. All these considerations require that in describing the properties of substances, particular attention should be paid to their relation to water as a solvent. [Illustration: FIG. 14.--Method of transferring a gas into a cylinder filled with mercury and whose open end is immersed under the mercury in a bath having two glass sides. The apparatus containing the gas is represented on the right. Its upper extremity is furnished with a tube extending under the cylinder. The lower part of the vessel communicates with a vertical tube. If mercury be poured into this tube, the pressure of the gas in the apparatus is increased, and it passes through the gas-conducting tube into the cylinder, where it displaces the mercury, and can be measured or subjected to the action of absorbing agents, such as water.] It is well known that water dissolves many substances. Salt, sugar, alcohol, and a number of other substances, dissolve in water and form homogeneous liquids with it. To demonstrate the solubility of gases in water, a gas should be taken which has a high co-efficient of solubility--for instance, ammonia. This is introduced into a bell jar (or cylinder, as in fig. 14), which is previously filled with mercury and stands in a mercury bath. If water be then introduced into the cylinder, the mercury will rise, owing to the water dissolving the ammonia gas. If the column of mercury be less than the barometric column, and if there be sufficient water to dissolve the gas, all the ammonia will be absorbed by the water. The water is introduced into the cylinder by a glass pipette, with a bent end. The bent end is put into water, and the air is sucked out from the upper end. When full of water, its upper end is closed with the finger, and the bent end placed in the mercury bath under the orifice of the cylinder. On blowing into the pipette the water will rise to the surface of the mercury in the cylinder owing to its lightness. The solubility of a gas like ammonia may be demonstrated by taking a flask full of the gas, and closed by a cork with a tube passing through it. On placing the tube under water, the water will rise into the flask (this may be accelerated by previously warming the flask), and begin to play like a fountain inside it. Both the rising of the mercury and the fountain clearly show the considerable affinity of water for ammonia gas, and the force acting in this dissolution is rendered evident. A certain period of time is required both for the homogeneous intermixture of gases (diffusion) and the process of solution, which depends, not only on the surface of the participating substances, but also on their nature. This is seen from experiment. Solutions of different substances heavier than water, such as salt or sugar, are poured into tall jars. Pure water is then very carefully poured into these jars (through a funnel) on to the top of the solutions, so as not to disturb the lower stratum, and the jars are then left undisturbed. The line of demarcation between the solution and the pure water will be visible, owing to their different co-efficients of refraction. Notwithstanding that the solutions taken are heavier than water, after some time complete intermixture will ensue. Gay Lussac convinced himself of this fact by this particular experiment, which he conducted in the cellars under the Paris Astronomical Observatory. These cellars are well known as the locality where numerous interesting researches have been conducted, because, owing to their depth under ground, they have a uniform temperature during the whole year; the temperature does not change during the day, and this was indispensable for the experiments on the diffusion of solutions, in order that no doubt as to the results should arise from a daily change of temperature (the experiment lasted several months), which would set up currents in the liquids and intermix their strata. Notwithstanding the uniformity of the temperature, the substance in solution in time ascended into the water and distributed itself uniformly through it, proving that there exists between water and a substance dissolved in it a particular kind of attraction or striving for mutual interpenetration in opposition to the force of gravity. Further, this effort, or rate of diffusion, is different for salt or sugar or for various other substances.[16 bis] It follows therefore that a peculiar force acts in solution, as in actual chemical combinations, and solution is determined by a particular kind of motion (by the chemical energy of a substance) which is proper to the substance dissolved and to the solvent. [16 bis] Graham, in the jelly formed by gelatine, and De Vries in gelatinous silica (Chapter XVIII.) most frequently employed coloured (tinted) substances, for instance, K_{2}Cr_{2}O_{7}, which showed the rate of diffusion with very great clearness. Prof. Oumoff employed the method described in Chapter X., Note 17, for this purpose. Graham made a series of experiments similar to those above described, and showed that the _rate of diffusion_[17] in water is very variable--that is, a uniform distribution of a substance in the water dissolving it is attained in different periods of time with different solutions. Graham compared diffusive capacity with volatility. There are substances which diffuse easily, and there are others which diffuse with difficulty, just as there are more or less volatile substances. Seven hundred cubic centimetres of water were poured into a jar, and by means of a syphon (or a pipette) 100 cub. centimetres of a solution containing 10 grams of a substance were cautiously poured in so as to occupy the lower portion of the jar. After a lapse of several days, successive layers of 50 cubic centimetres were taken from the top downwards, and the quantity of substance dissolved in the different layers determined. Thus, common table salt, after fourteen days, gave the following amounts (in milligrams) in the respective layers, beginning from the top: 104, 120, 126, 198, 267, 340, 429, 535, 654, 766, 881, 991, 1,090, 1,187, and 2,266 in the remainder; whilst albumin in the same time gave, in the first seven layers, a very small amount, and beginning from the eighth layer, 10, 15, 47, 113, 343, 855, 1,892, and in the remainder 6,725 milligrams. Thus, the diffusive power of a solution depends on time and on the nature of the substance dissolved, which fact may serve, not only for explaining the process of solution, but also for distinguishing one substance from another. Graham showed that substances which rapidly diffuse through liquids are able to rapidly pass through membranes and crystallise, whilst substances which diffuse slowly and do not crystallise are _colloids_, that is, resemble glue, and penetrate through a membrane slowly, and form jellies; that is, occur in insoluble forms,[18] as will be explained in speaking of silica. [17] The researches of Graham, Fick, Nernst, and others showed that the quantity of a dissolved substance which is transmitted (rises) from one stratum of liquid to another in a vertical cylindrical vessel is not only proportional to the time and to the sectional area of the cylinder, but also to the amount and nature of the substance dissolved in a stratum of liquid, so that each substance has its corresponding co-efficient of diffusion. The cause of the diffusion of solutions must be considered as essentially the same as the cause of the diffusion of gases--that is, as dependent on motions which are proper to their molecules; but here most probably those purely chemical, although feebly-developed, forces, which incline the substances dissolved to the formation of definite compounds, also play their part. [18] [Illustration: FIG. 15.--Dialyser. Apparatus for the separation of substances which pass through a membrane from those which do not. Description in text.] The rate of diffusion--like the rate of transmission--through membranes, or _dialysis_ (which plays an important part in the vital processes of organisms and also in technical processes), presents, according to Graham's researches, a sharply defined change in passing from such crystallisable substances as the majority of salts and acids to substances which are capable of giving jellies (gum, gelatin, &c.) The former diffuse into solutions and pass through membranes much more rapidly than the latter, and Graham therefore distinguishes between _crystalloids_, which diffuse rapidly, and _colloids_, which diffuse slowly. On breaking solid colloids into pieces, a total absence of cleavage is remarked. The fracture of such substances is like that of glue or glass. It is termed a 'conchoidal' fracture. Almost all the substances of which animal and vegetable bodies consist are colloids, and this is, at all events, partly the reason why animals and plants have such varied forms, which have no resemblance to the crystalline forms of the majority of mineral substances. The colloid solid substances in organisms--that is, in animals and plants--almost always contain water, and take most peculiar forms, of networks, of granules, of hairs, of mucous, shapeless masses, &c., which are quite different from the forms taken by crystalline substances. When colloids separate out from solutions, or from a molten state, they present a form which is similar to that of the liquid from which they were formed. Glass may he taken as the best example of this. Colloids are distinguishable from crystalloids, not only by the absence of crystalline form, but by many other properties which admit of clearly distinguishing both these classes of solids, as Graham showed. Nearly all colloids are capable of passing, under certain circumstances, from a soluble into an insoluble state. The best example is shown by white of eggs (albumin) in the raw and soluble form, and in the hard-boiled and insoluble form. The majority of colloids, on passing into an insoluble form in the presence of water, give substances having a gelatinous appearance, which is familiar to every one in starch, solidified glue, jelly, &c. Thus gelatin, or common carpenter's glue, when soaked in water, swells up into an insoluble jelly. If this jelly be heated, it melts, and is then soluble in water, but on cooling it again forms a jelly which is insoluble in water. One of the properties which distinguish colloids from crystalloids is that the former pass very slowly through a membrane, whilst the latter penetrate very rapidly. This may be shown by taking a cylinder, open at both ends, and by covering its lower end with a bladder or with vegetable parchment (unsized paper immersed for two or three minutes in a mixture of sulphuric acid and half its volume of water, and then washed), or any other membranous substance (all such substances are themselves colloids in an insoluble form). The membrane must be firmly tied to the cylinder, so as not to leave any opening. Such an apparatus is called a _dialyser_ (fig. 15), and the process of separation of crystalloids from colloids by means of such a membrane is termed _dialysis_. An aqueous solution of a crystalloid or colloid, or a mixture of both, is poured into the dialyser, which is then placed in a vessel containing water, so that the bottom of the membrane is covered with water. Then, after a certain period of time, the crystalloid passes through the membrane, whilst the colloid, if it does pass through at all, does so at an incomparably slower rate. The crystalloid naturally passes through into the water until the solution attains the same strength on both sides of the membrane. By replacing the outside water with fresh water, a fresh quantity of the crystalloid may be separated from the dialyser. While a crystalloid is passing through the membrane, a colloid remains almost entirely in the dialyser, and therefore a mixed solution of these two kinds of substances may be separated from each other by a dialyser. The study of the properties of colloids, and of the phenomena of their passage through membranes, should elucidate much respecting the phenomena which are accomplished in organisms. Hence, if it be desired to increase the rate of solution, recourse must be had to stirring, shaking, or some such mechanical motion. But if once a uniform solution is formed, it will remain uniform, no matter how heavy the dissolved substance is, or how long the solution be left at rest, which fact again shows the presence of a force holding together the particles of the body dissolved and of the solvent.[19] [19] The formation of solutions may be considered in two aspects, from a physical and from a chemical point of view, and it is more evident in solutions than in any other department of chemistry how closely these provinces of natural science are allied together. On the one hand solutions form a particular case of a physico-mechanical interpenetration of homogeneous substances, and a juxtaposition of the molecules of the substance dissolved and of the solvent, similar to the juxtaposition which is exhibited in homogeneous substances. From this point of view this diffusion of solutions is exactly similar to the diffusion of gases, with only this difference, that the nature and store of energy are different in gases from what they are in liquids, and that in liquids there is considerable friction, whilst in gases there is comparatively little. The penetration of a dissolved substance into water is likened to evaporation, and solution to the formation of vapour. This resemblance was clearly expressed even by Graham. In recent years the Dutch chemist, Van't Hoff, has developed this view of solutions in great detail, having shown (in a memoir in the _Transactions of the Swedish Academy of Science_, Part 21, No. 17, 'Lois de l'équilibre chimique dans l'état dilué, gazeux ou dissous,' 1886), that for dilute solutions the _osmotic pressure_ follows the same laws of Boyle, Mariotte, Gay-Lussac, and Avogadro-Gerhardt as for gases. The osmotic pressure of a substance dissolved in water is determined by means of membranes which allow the passage of water, but not of a substance dissolved in it, through them. This property is found in animal protoplasmic membranes and in porous substances covered with an amorphous precipitate, such as is obtained by the action of copper sulphate on potassium ferrocyanide (Pfeffer, Traube). If, for instance, a one p.c. solution of sugar he placed in such a vessel, which is then closed and placed in water, the water passes through the walls of the vessel and increases the pressure by 50 mm. of the barometric column. If the pressure be artificially increased inside the vessel, then the water will be expelled through the walls. De Vries found a convenient means of determining _isotonic_ solutions (those presenting a similar osmotic pressure) in the cells of plants. For this purpose a portion of the soft part of the leaves of the _Tradescantis discolor_, for instance, is cut away and moistened with the solution of a given salt and of a given strength. If the osmotic pressure of the solution taken be less than that of the sap contained in the cells they will change their form or shrink; if, on the other hand, the osmotic pressure be greater than that of the sap, then the cells will expand, as can easily be seen under the microscope. By altering the amount of the different salts in solution it is possible to find for each salt the strength of solution at which the cells begin to swell, and at which they will consequently have an equal osmotic pressure. As it increases in proportion to the amount of a substance dissolved per 100 parts of water, it is possible, knowing the osmotic pressure of a given substance--for instance, sugar at various degrees of concentration of solution--and knowing the composition of isotonic solutions compared with sugar, to determine the osmotic pressure of all the salts investigated. The osmotic pressure of dilute solutions determined in this manner directly or indirectly (from observations made by Pfeffer and De Vries) was shown to follow the same laws as those of the pressure of gases; for instance, by doubling or increasing the quantity of a salt (in a given volume) _n_ times, the pressure is doubled or increases _n_ times. So, for example, in a solution containing one part of sugar per 100 parts of water the osmotic pressure (according to Pfeffer) = 58·5 cm. of mercury, if 2 parts of sugar = 101·6, if 4 parts = 208·2 and so on, which proves that the ratio is true within the limits of experimental error. (2) Different substances for equal strengths of solutions, show very different osmotic pressures, just as gases for equal parts by weight in equal volumes show different tensions. (3) If, for a given dilute solution at 0°, the osmotic pressure equal _p_°, then at _t_° it will be greater and equal to _p_°(1 + 0·00367_t_), _i.e._ it increases with the temperature in exactly the same manner as the tension of gases increases. (4) If in dilute solutions of such substances as do not conduct an electric current (for instance, sugar, acetone, and many other organic bodies) the substances be taken in the ratio of their molecular weights (expressed by their formulæ, see Chapter VII.), then not only will the osmotic pressure be equal, but its magnitude will be determined by that tension which would be proper to the vapours of the given substances when they would be contained in the space occupied by the solution, just as the tension of the vapours of molecular quantities of the given substances will be equal, and determined by the laws of Gay-Lussac, Mariotte, and Avogadro-Gerhardt. Those formulæ (Chapter VII., Notes 23 and 24) by which the gaseous state of matter is determined, may also be applied in the present case. So, for example, the osmotic pressure _p_, in centimetres of mercury, of a one per cent. solution of sugar, may be calculated according to the formula for gases: M_p_ = 6200_s_(273 + _t_), where M is the molecular weight, _s_ the weight in grams of a cubic centimetre of vapour, and _t_ its temperature. For sugar M = 342 (because its molecular composition is C_{12}H_{22}O_{11}). The specific gravity of the solution of sugar is 1·003, hence the weight of sugar _s_ contained in a 1 per cent. solution = 0·01003 gram. The observation was made at _t_ = 14°. Hence, according to the formula, we find _p_ = 52·2 centimetres. And experiments carried on at 14° gave 53·5 centimetres, which is very near to the above. (5) For the solutions of salts, acids, and similar substances, which conduct an electric current, the calculated pressure is usually (but not always in a definite or multiple number of times) less than the observed by _i_ times, and this _i_ for dilute solutions of MgSO_{4} is nearly 1, for CO_{2} = 1, for KCl, NaCl, KI, KNO_{3} greater than 1, and approximates to 2, for BaCl_{2}, MgCl_{2}, K_{2}CO_{3}, and others between 2 and 3, for HCl, H_{2}SO_{4}, NaNO_{3}, CaN_{2}O_{6}, and others nearly 2 and so on. It should be remarked that the above deductions are only applicable (and with a certain degree of accuracy) to dilute solutions, and in this respect resemble the generalisations of Michel and Kraft (see Note 44). Nevertheless, the arithmetical relation found by Van't Hoff between the formation of vapours and the transition into dilute solutions forms an important scientific discovery, which should facilitate the explanation of the nature of solutions, while the osmotic pressure of solutions already forms a very important aspect of the study of solutions. In this respect it is necessary to mention that Prof. Konovaloff (1891, and subsequently others also) discovered the dependence (and it may be a sufficient explanation) of the osmotic pressure upon the differences of the tensions of aqueous vapours and aqueous solutions; this, however, already enters into a special province of physical chemistry (certain data are given in Note 49 and following), and to this physical side of the question also belongs one of the extreme consequences of the resemblance of osmotic pressure to gaseous pressure, which is that the concentration of a uniform solution varies in parts which are heated or cooled. Soret (1881) indeed observed that a solution of copper sulphate containing 17 parts of the salt at 20° only contained 14 parts after heating the upper portion of the tube to 80° for a long period of time. This aspect of solution, which is now being very carefully and fully worked out, may be called the _physical_ side. Its other aspect is purely _chemical_, for solution does not take place between any two substances, but requires a special and particular attraction or affinity between them. A vapour or gas permeates any other vapour or gas, but a salt which dissolves in water may not be in the least soluble in alcohol, and is quite insoluble in mercury. In considering solutions as a manifestation of chemical force (and of chemical energy), it must be acknowledged that they are here developed to so feeble an extent that the definite compounds (that is, those formed according to the law of multiple proportions) formed between water and a soluble substance dissociate even at the ordinary temperature, forming a homogeneous system--that is, one in which both the compound and the products into which it decomposes (water and the aqueous compound) occur in a liquid state. The chief difficulty in the comprehension of solutions depends on the fact that the mechanical theory of the structure of liquids has not yet been so fully developed as the theory of gases, and solutions are liquids. The conception of solutions as liquid dissociated definite chemical compounds is based on the following considerations: (1) that there exist certain undoubtedly definite chemical crystallised compounds (such as H_{2}SO_{4},H_{2}O; or NaCl,2H_{2}O; or CaCl_{2},6H_{2}O; &c.) which melt on a certain rise of temperature, and then form true solutions; (2) that metallic alloys in a molten condition are real solutions, but on cooling they often give entirely distinct and definite crystallised compounds, which are recognised by the properties of alloys; (3) that between the solvent and the substance dissolved there are formed, in a number of cases, many undoubtedly definite compounds, such as compounds with water of crystallisation; (4) that the physical properties of solutions, and especially their specific gravities (a property which can be very accurately determined), vary with a change in composition, and in such a manner as would be required by the formation of one or more definite but dissociating compounds. Thus, for example, on adding water to fuming sulphuric acid its density is observed to decrease until it attains the definite composition H_{2}SO_{4}, or SO_{3} + H_{2}O, when the specific gravity increases, although on further diluting with water it again falls. Moreover (Mendeléeff, _The Investigation of Aqueous Solutions from their Specific Gravities_, 1887), the increase in specific gravity (_ds_), varies in all well-known solutions with the proportion of the substance dissolved (_dp_), and this dependence can be expressed by a formula (_ds_/_dp_ = A + B_p_) between the limits of definite compounds whose existence in solutions must be admitted, and this is in complete accordance with the dissociation hypothesis. Thus, for instance, from H_{2}SO_{4} to H_{2}SO_{4} + H_{2}O (both these substances exist as definite compounds in a free state), the fraction _ds_/_dp_ = 0·0729-0·000749_p_ (where _p_ is the percentage amount of H_{2}SO_{4}). For alcohol C_{2}H_{6}O, whose aqueous solutions have been more accurately investigated than all others, the definite compound C_{2}H_{6}O + 3H_{2}O, and others must be acknowledged in its solutions. The two aspects of solution above mentioned, and the hypotheses which have as yet been applied to the examination of solutions, although they have somewhat different starting points, will doubtless in time lead to a general theory of solutions, because the same common laws govern both physical and chemical phenomena, inasmuch as the properties and motions of molecules, which determine physical properties, depend on the motions and properties of atoms, which determine chemical reactions. For details of the questions dealing with theories of solution, recourse must now be had to special memoirs and to works on theoretical (physical) chemistry; for this subject forms one of special interest at the present epoch of the development of our science. In working out chiefly the chemical side of solutions, I consider it to be necessary to reconcile the two aspects of the question; this seems to me to be all the more possible, as the physical side is limited to dilute solutions only, whilst the chemical side deals mainly with strong solutions. In the consideration of the process of solution, besides the conception of diffusion, another fundamental conception is necessary--namely, that of the _saturation of solutions_. Just as moist air may be diluted with any desired quantity of dry air, so also an indefinitely large quantity of a liquid solvent may be taken, and yet a uniform solution will be obtained. But more than a definite quantity of aqueous vapour cannot be introduced into a certain volume of air at a certain temperature. The excess above the point of saturation will remain in the liquid state.[20] The relation between water and substances dissolved in it is similar. More than a definite quantity of a substance cannot, at a certain temperature, dissolve in a given quantity of water; the excess does not unite with the water. Just as air or a gas becomes saturated with vapour, so water becomes saturated with a substance dissolved in it. If an excess of a substance be added to water which is already saturated with it, it will remain in its original state, and will not diffuse through the water. The quantity of a substance (either by volume with gases, or by weight with solids and liquids) which is capable of saturating 100 parts of water is called the _co-efficient of solubility_ or the _solubility_. In 100 grams of water at 15°, there can be dissolved not more than 35·86 grams of common salt. Consequently, its solubility at 15° is equal to 35·86.[21] It is most important to turn attention to the _existence of the solid insoluble substances of nature_, because on them depends the shape of the substances of the earth's surface, and of plants and animals. There is so much water on the earth's surface, that were the surface of substances formed of soluble matters it would constantly change, and however substantial their forms might be, mountains, river banks and sea shores, plants and animals, or the habitations and coverings of men, could not exist for any length of time.[22] [20] A system of (chemically or physically) re-acting substances in different states of aggregation--for instance, some solid, others liquid or gaseous--is termed a heterogeneous system. Up to now it is only systems of this kind which can be subjected to detailed examination in the sense of the mechanical theory of matter. Solutions (_i.e._ unsaturated ones) form fluid homogeneous systems, which at the present time can only be investigated with difficulty. In the case of limited solution of liquids in liquids, _the difference between the solvent and the substance dissolved_ is clearly seen. The former (that is, the solvent) may be added in an unlimited quantity, and yet the solution obtained will always be uniform, whilst only a definite saturating proportion of the substance dissolved can be taken, We will take water and common (sulphuric) ether. On shaking the ether with the water, it will be remarked that a portion of it dissolves in the water. If the ether be taken in such a quantity that it saturates the water and a portion of it remains undissolved, then this remaining portion will act as a solvent, and water will diffuse through it and also form a saturated solution of water in the ether taken. Thus two saturated solutions will be obtained. One solution will contain ether dissolved in water, and the other solution will contain water dissolved in ether. These two solutions will arrange themselves in two layers, according to their density; the ethereal solution of water will be on the top. If the upper ethereal solution be poured off from the aqueous solution, any quantity of ether may be added to it; this shows that the dissolving substance is ether. If water be added to it, it is no longer dissolved in it; this shows that water saturates the ether--here water is the substance dissolved. If we act in the same manner with the lower layer, we shall find that water is the solvent and ether the substance dissolved. By taking different amounts of ether and water, the degree of solubility of ether in water, and of water in ether, may be easily determined. Water approximately dissolves 1/10 of its volume of ether, and ether dissolves a very small quantity of water. Let us now imagine that the liquid poured in dissolves a considerable amount of water, and that water dissolves a considerable amount of the liquid. Two layers could not be formed, because the saturated solutions would resemble each other, and therefore they would intermix in all proportions. This is, consequently, a case of a phenomenon where two liquids present considerable co-efficients of solubility in each other, but where it is impossible to say what these co-efficients are, because it is impossible to obtain a saturated solution. [21] The solubility, or co-efficient of solubility, of a substance is determined by various methods. Either a solution is expressly prepared with a clear excess of the soluble substance and saturated at a given temperature, and the quantity of water and of the substance dissolved in it determined by evaporation, desiccation, or other means; or else, as is done with gases, definite quantities of water and of the soluble substance are taken and the amount remaining undissolved is determined. [Illustration: FIG. 16.--Bunsen's absorptiometer. Apparatus for determining the solubility of gases in liquids.] The solubility of a gas in water is determined by means of an apparatus called an _absorptiometer_ (fig. 16). It consists of an iron stand _f_, on which an india-rubber ring rests. A wide glass tube is placed on this ring, and is pressed down on it by the ring _h_ and the screws _i i_. The tube is thus firmly fixed on the stand. A cock _r_, communicating with a funnel _r_, passes into the lower part of the stand. Mercury can be poured into the wide tube through this funnel, which is therefore made of steel, as copper would be affected by the mercury. The upper ring _h_ is furnished with a cover _p_, which can be firmly pressed down on to the wide tube, and hermetically closes it by means of an india-rubber ring. The tube _r r_ can be raised at will, and so by pouring mercury into the funnel the height of the column of mercury, which produces pressure inside the apparatus, can be increased. The pressure can also be diminished at will, by letting mercury out through the cock _r_. A graduated tube _e_, containing the gas and liquid to be experimented on, is placed inside the wide tube. This tube is graduated in millimetres for determining the pressure, and it is calibrated for volume, so that the number of volumes occupied by the gas and liquid dissolving it can be easily calculated. This tube can also be easily removed from the apparatus. The lower portion of this tube when removed from the apparatus is shown to the right of the figure. It will be observed that its lower end is furnished with a male screw _b_, fitting in a nut _a_. The lower surface of the nut _a_ is covered with india-rubber, so that on screwing up the tube its lower end presses upon the india-rubber, and thus hermetically closes the whole tube, for its upper end is fused up. The nut _a_ is furnished with arms _c c_, and in the stand _f_ there are corresponding spaces, so that when the screwed-up internal tube is fixed into stand _f_, the arms _c c_ fix into these spaces cut in _f_. This enables the internal tube to be fixed on to the stand _f_. When the internal tube is fixed in the stand, the wide tube is put into its right position, and mercury and water are poured into the space between the two tubes, and communication is opened between the inside of the tube _e_ and the mercury between the interior and exterior tubes. This is done by either revolving the interior tube _e_, or by a key turning the nut about the bottom part of _f_. The tube _e_ is filled with gas and water as follows: the tube is removed from the apparatus, filled with mercury, and the gas to be experimented on is passed into it. The volume of the gas is measured, the temperature and pressure determined, and the volume it would occupy at 0° and 760 mm. calculated. A known volume of water is then introduced into the tube. The water must be previously boiled, so as to be quite freed from air in solution. The tube is then closed by screwing it down on to the india-rubber on the nut. It is then fixed on to the stand _f_, mercury and water are poured into the intervening space between it and the exterior tube, which is then screwed up and closed by the cover _p_, and the whole apparatus is left at rest for some time, so that the tube _e_, and the gas in it, may attain the same temperature as that of the surrounding water, which is marked by a thermometer _k_ tied to the tube _e_. The interior tube is then again closed by turning it in the nut, the cover _p_ again shut, and the whole apparatus is shaken in order that the gas in the tube _e_ may entirely saturate the water. After several shakings, the tube _e_ is again opened by turning it in the nut, and the apparatus is left at rest for a certain time; it is then closed and again shaken, and so on until the volume of gas does not diminish after a fresh shaking--that is, until saturation ensues. Observations are then made of the temperature, the height of the mercury in the interior tube, and the level of the water in it, and also of the level of the mercury and water in the exterior tube. All these data are necessary in order to calculate the pressure under which the solution of the gas takes place, and what volume of gas remains undissolved, and also the quantity of water which serves as the solvent. By varying the temperature of the surrounding water, the amount of gas dissolved at various temperatures may be determined. Bunsen, Carius, and many others determined the solution of various gases in water, alcohol, and certain other liquids, by means of this apparatus. If in a determination of this kind it is found that _n_ cubic centimetres of water at a pressure _h_ dissolve _m_ cubic centimetres of a given gas, measured at 0° and 760 mm., when the temperature under which solution took place was _t_°, then it follows that at the temperature _t the co-efficient of solubility of the gas_ in 1 volume of the liquid will be equal to _m_/_n_ × 760/_h_. This formula is very clearly understood from the fact that the co-efficient of solubility of gases is that quantity measured at 0° and 760 mm., which is absorbed at a pressure of 760 mm. by one volume of a liquid. If _n_ cubic centimetres of water absorb _m_ cubic centimetres of a gas, then one cubic centimetre absorbs _m_/_n_. If _m_/_n_ c.c. of a gas are absorbed under a pressure of _h_ mm., then, according to the law of the variation of solubility of a gas with the pressure, there would he dissolved, under a pressure of 760 mm., a quantity varying in the same ratio to _m_/_n_ as 760 : _h_. In determining the residual volume of gas its moisture (note 1) must be taken into consideration. Below are given the number of grams of several substances saturating 100 grams of water--that is, their co-efficients of solubility by weight at three different temperatures:-- +----------------------------------------------+--------+---------+ | | | | | At 0° | At 20° | At 100° | +----------------------------------------------+--------+---------+ | {Oxygen, O_{2} 6/1000 | 4/1000 | -- | |Gases {Carbonic anhydride, CO_{2} 35/100 | 18/100 | -- | | {Ammonia, NH_{3} 90·0 | 51·8 | 7·3 | | {Phenol, C_{6}H_{6}O 4·9 | 5·2 | [oo] | |Liquids {Amyl alcohol, C_{5}H_{12}O 4·4 | 2·9 | -- | | {Sulphuric acid, H_{2}SO_{4} [oo] | [oo] | [oo] | | {Gypsum, CaSO_{4},2H_{2}O 1/5 | 1/4 | 1/5 | | {Alum, AlKS_{2}O_{8},12H_{2}O 3·3 | 15·4 | 357·5 | |Solids {Anhydrous sodium sulphate, 4·5 | 20 | 43 | | { Na_{2}SO_{4} | | | | {Common Salt, NaCl 35·7 | 36·0 | 39·7 | | {Nitre, KNO_{3} 13·3 | 31·7 | 246·0 | +----------------------------------------------+--------+---------+ Sometimes a substance is so slightly soluble that it may be considered as insoluble. Many such substances are met with both in solids and liquids, and such a gas as oxygen, although it does dissolve, does so in so small a proportion by weight that it might be considered as zero did not the solubility of even so little oxygen play an important part in nature (as in the respiration of fishes) and were not an infinitesimal quantity of a gas by weight so easily measured by volume. The sign [oo], which stands on a line with sulphuric acid in the above table, indicates that it intermixes with water in all proportions. There are many such cases among liquids, and everybody knows, for instance, that spirit (absolute alcohol) can be mixed in any proportion with water. [22] Just as the existence must he admitted of substances which are completely undecomposable (chemically) at the ordinary temperature--and of substances which are entirely non-volatile at such a temperature (as wood and gold), although capable of decomposing (wood) or volatilising (gold) at a higher temperature--so also the existence must be admitted of substances which are totally insoluble in water without some degree of change in their state. Although mercury is partially volatile at the ordinary temperature, there is no reason to think that it and other metals are soluble in water, alcohol, or other similar liquids. However, mercury forms solutions, as it dissolves other metals. On the other hand, there are many substances found in nature which are so very slightly soluble in water, that in ordinary practice they may be considered as insoluble (for example, barium sulphate). For the comprehension of that general plan according to which a change of state of substances (combined or dissolved, solid, liquid, or gaseous) takes place, it is very important to make a distinction at this boundary line (on approaching zero of decomposition, volatility, or solubility) between an insignificant amount and zero, but the present methods of research and the data at our disposal at the present time only just touch such questions (by studying the electrical conductivity of dilute solutions and the development of micro-organisms in them). It must be remarked, besides, that water in a number of cases does not dissolve a substance as such, but acts on it chemically and forms a soluble substance. Thus glass and many rocks, especially if taken as powder, are chemically changed by water, but are not directly soluble in it. Substances which are easily soluble in water bear a certain resemblance to it. Thus sugar and salt in many of their superficial features remind one of ice. Metals, which are not soluble in water, have no points in common with it, whilst on the other hand they dissolve each other in a molten state, forming alloys, just as oily substances dissolve each other; for example, tallow is soluble in petroleum and in olive oil, although they are all insoluble in water. From this it is evident that the _analogy of substances forming a solution_ plays an important part, and as aqueous and all other solutions are liquids, there is good reason to believe that in the process of solution solid and gaseous substances change in a physical sense, passing into a liquid state. These considerations elucidate many points of solution--as, for instance, the variation of the co-efficient of solubility with the temperature and the evolution or absorption of heat in the formation of solutions. The solubility--that is, the quantity of a substance necessary for saturation--_varies with the temperature_, and, further, with an increase in temperature the solubility of solid substances generally increases, and that of gases decreases; this might be expected, as solid substances by heating, and gases by cooling, approach to a liquid or dissolved state.[23] A graphic method is often employed to express the variation of solubility with temperature. On the axis of abscissæ or on a horizontal line, temperatures are marked out and perpendiculars are raised corresponding with each temperature, whose length is determined by the solubility of the salt at that temperature--expressing, for instance, one part by weight of a salt in 100 parts of water by one unit of length, such as a millimetre. By joining the summits of the perpendiculars, a curve is obtained which expresses the degree of solubility at different temperatures. For solids, the curve is generally an ascending one--_i.e._ recedes from the horizontal line with the rise in temperature. These curves clearly show by their inclination the degree of rapidity of increase in solubility with the temperature. Having determined several points of a curve--that is, having made a determination of the solubility for several temperatures--the solubility at intermediary temperatures may be determined from the form of the curve so obtained; in this way the empirical law of solubility may be examined.[24] The results of research have shown that the solubility of certain salts--as, for example, common table salt--varies comparatively little with the temperature; whilst for other substances the solubility increases by equal amounts for equal increments of temperature. Thus, for example, for the saturation of 100 parts of water by potassium chloride there is required at 0°, 29·2 parts, at 20°, 34·7, at 40°, 40·2, at 60°, 45·7; and so on, for every 10° the solubility increases by 2·75 parts by weight of the salt. Therefore the solubility of the potassium chloride in water may be expressed by a direct equation: _a_ = 29·2 + 0·275_t_, where _a_ represents the solubility at _t_°. For other salts, more complicated equations are required. For example, for nitre: _a_ = 13·3 + 0·574_t_ + 0·01717_t_^2 + 0·0000036_t_^3, which shows that when _t_ = 0° _a_ = 13·3, when _t_ = 10° _a_ = 20·8, and when _t_ = 100° _a_ = 246·0. [23] Beilby (1883) experimented on paraffin, and found that one litre of solid paraffin at 21° weighed 874 grams, and when liquid, at its melting-point 38°, 783 grams, at 49°, 775 grams, and at 60°, 767 grams, from which the weight of a litre of liquefied paraffin would be 795·4 grams at 21° if it could remain liquid at that temperature. By dissolving solid paraffin in lubricating oil at 21° Beilby found that 795·6 grams occupy one cubic decimetre, from which he concluded that the solution contained liquefied paraffin. [24] Gay-Lussac was the first to have recourse to such a graphic method of expressing solubility, and he considered, in accordance with the general opinion, that by joining up the summits of the ordinates in one harmonious curve it is possible to express the entire change of solubility with the temperature. Now, there are many reasons for doubting the accuracy of such an admission, for there are undoubtedly critical points in curves of solubility (for example, of sodium sulphate, as shown further on), and it may be that definite compounds of dissolved substances with water, in decomposing within known limits of temperature, give critical points more often than would be imagined; it may even be, indeed, that instead of a continuous curve, solubility should be expressed--if not always, then not unfrequently--by straight or broken lines. According to Ditte, the solubility of sodium nitrate, NaNO_{3}, is expressed by the following figures per 100 parts of water:-- 0° 4° 10° 15° 21° 29° 36° 51° 68° 66·7 71·0 76·3 80·6 85·7 92·9 99·4 113·6 125·1 In my opinion (1881) these data should be expressed with exactitude by a straight line, 67·5 + 0·87_t_, which entirely agrees with the results of experiment. According to this the figure expressing the solubility of salt at 0° exactly coincides with the composition of a definite chemical compound--NaNO_{3},7H_{2}O. The experiments made by Ditte showed that all saturated solutions between 0° and -15·7° have such a composition, and that at the latter temperature the solution completely solidifies into one homogeneous whole. Between 0° and -15·7° the solution NaNO_{3},7H_{2}O does not deposit either salt or ice. Thus the solubility of sodium nitrate is expressed by a broken straight line. In recent times (1888) Étard discovered a similar phenomenon in many of the sulphates. Brandes, in 1830, shows a diminution in solubility below 100° for manganese sulphate. The percentage by weight (_i.e._ per 100 parts of the solution, and not of water) of saturation for ferrous sulphate, FeSO_{4}, from -2° to +65° = 13·5 + 0·3784_t_--that is, the solubility of the salt increases. The solubility remains constant from 65° to 98° (according to Brandes the solubility then increases; this divergence of opinion requires proof), and from 98° to 150° it falls as = 104·35 - 0·6685_t_. Hence, at about +156° the solubility should = 0, and this has been confirmed by experiment. I observe, on my part, that Étard's formula gives 38·1 p.c. of salt at 65° and 38·8 p.c. at 92°, and this maximum amount of salt in the solution very nearly corresponds with the composition FeSO_{4},14H_{2}O, which requires 37·6 p.c. From what has been said, it is evident that the data concerning solubility require a new method of investigation, which should have in view the entire scale of solubility--from the formation of completely solidified solutions (cryohydrates, which we shall speak of presently) to the separation of salts from their solutions, if this is accomplished at a higher temperature (for manganese and cadmium sulphates there is an entire separation, according to Étard), or to the formation of a constant solubility (for potassium sulphate the solubility, according to Étard, remains constant from 163° to 220° and equals 24·9 p.c.) (See Chapter XIV., note 50, solubility of CaCl_{2}.) Curves of solubility give the means of estimating the _amount of salt separated_ by the cooling to a known extent of a solution saturated at a given temperature. For instance, if 200 parts of a solution of potassium chloride in water saturated at a temperature of 60° be taken, and it be asked how much of the salt will be separated by cooling the solution to 0°, if its solubility at 60° = 45·7 and at 0° = 29·2? The answer is obtained in the following manner: At 60° a saturated solution contains 45·7 parts of potassium chloride per 100 parts by weight of water, consequently 145·7 parts by weight of the solution contain 45·7 parts, or, by proportion, 200 parts by weight of the solution contain 62·7 parts of the salt. The amount of salt remaining in solution at 0° is calculated as follows; In 200 grams taken there will be 137·3 grams of water; consequently, this amount of water is capable of holding only 40·1 grams of the salt, and therefore in lowering the temperature from 60° to 0° there should separate from the solution 62·7-40·1 = 22·6 grams of the dissolved salt. The difference in the solubility of salts, &c., with a rise or fall of temperature is often taken advantage of, especially in technical work, for the separation of salts, in intermixture from each other. Thus a mixture of potassium and sodium chlorides (this mixture is met with in nature at Stassfurt) is separated from a saturated solution by subjecting it alternately to boiling (evaporation) and cooling. The sodium chloride separates out in proportion to the amount of water expelled from the solution by boiling, and is removed, whilst the potassium chloride separates out on cooling, as the solubility of this salt rapidly decreases with a lowering in temperature. Nitre, sugar, and many other soluble substances are purified (refined) in a similar manner. Although in the majority of cases the solubility of solids increases with the temperature, yet there are some solid substances whose solubilities decrease on heating. Glauber's salt, or sodium sulphate, forms a particularly instructive example of the case in question. If this salt be taken in an ignited state (deprived of its water of crystallisation), then its solubility in 100 parts of water varies with the temperature in the following manner: at 0°, 5 parts of the salt form a saturated solution; at 20°, 20 parts of the salt, at 33° more than 50 parts. The solubility, as will be seen, increases with the temperature, as is the case with nearly all salts; but starting from 33° it suddenly diminishes, and at a temperature of 40°, less than 50 parts of the salt dissolve, at 60° only 45 parts of the salt, and at 100° about 43 parts of the salt in 100 parts of water. This phenomenon may be traced to the following facts: Firstly, that this salt forms various compounds with water, as will be afterwards explained; secondly, that at 33° the compound Na_{2}SO_{4} + 10H_{2}O formed from the solution at lower temperatures, melts; and thirdly, that on evaporation at a temperature above 33° an anhydrous salt, Na_{2}SO_{4} separates out. It will be seen from this example how complicated such an apparently simple phenomenon as solution really is; and all data concerning solutions lead to the same conclusion. This complexity becomes evident in investigating the _heat of solution_. If solution consisted of a physical change only, then in the solution of gases there would be evolved--and in the solution of solids, there would be absorbed--just that amount of heat corresponding to the change of state; but in reality a large amount of heat is always evolved in solution, depending on the fact that in the process of solution chemical combination takes place accompanied by an evolution of heat. Seventeen grams of ammonia (this weight corresponds with its formula NH_{3}), in passing from a gaseous into a liquid state, evolve 4,400 units of heat (latent heat); that is, the quantity of heat necessary to raise the temperature of 4,400 grams of water 1°. The same quantity of ammonia, in dissolving in an excess of water, evolves twice as much heat--namely 8,800 units--showing that the combination with water is accompanied by the evolution of 4,400 units of heat. Further, the chief part of this heat is separated in dissolving in small quantities of water, so that 17 grams of ammonia, in dissolving in 18 grams of water (this weight corresponds with its composition H_{2}O), evolve 7,535 units of heat, and therefore the formation of the solution NH_{3} + H_{2}O evolves 3,135 units of heat beyond that due to the change of state. As in the solution of gases, the heat of liquefaction (of physical change of state) and of chemical combination with water are both positive (+), therefore in the _solution of gases_ in water a _heat effect_ is always observed. This phenomenon is different in the solution of solid substances, because their passage from a solid to a liquid state is accompanied by an absorption of heat (negative,-heat), whilst their chemical combination with water is accompanied by an evolution of heat (+ heat); consequently, their sum may either be a cooling effect, when the positive (chemical) portion of heat is less than the negative (physical), or it may be, on the contrary, a heating effect. This is actually the case. 124 grams of sodium thiosulphate (employed in photography) Na_{2}S_{2}O_{3},5H_{2}O in melting (at 48°) absorbs 9,700 units of heat, but in dissolving in a large quantity of water at the ordinary temperature it absorbs 5,700 units of heat, which shows the evolution of heat (about + 4,000 units), notwithstanding the cooling effect observed in the process of solution, in the act of the chemical combination of the salt with water.[25] But in most cases solid substances in dissolving in water evolve heat, notwithstanding the passage into a liquid state, which indicates so considerable an evolution of (+) heat in the act of combination with water that it exceeds the absorption of (-) heat dependent on the passage into a liquid state, Thus, for instance, calcium chloride, CaCl_{2}, magnesium sulphate, MgSO_{4}, and many other salts evolve heat in dissolving; for example, 60 grams of magnesium sulphate evolve about 10,000 units of heat. Therefore, _in the solution of solid bodies_ either a cooling[26] or a heating[27] effect is produced, according to the difference of the reacting affinities. When they are considerable--that is, when water is with difficulty separated from the resultant solution, and only with a rise of temperature (such substances absorb water vapour)--then much heat is evolved in the process of solution, just as in many reactions of direct combination, and therefore a considerable heating of the solution is observed. Of such a kind, for instance, is the solution of sulphuric acid (oil of vitriol H_{2}SO_{4}), and of caustic soda (NaHO), &c., in water.[28] [25] The latent heat of fusion is determined at the temperature of fusion, whilst solution takes place at the ordinary temperature, and one must think that at this temperature the latent heat would be different, just as the latent heat of evaporation varies with the temperature (see Note 11). Besides which, in dissolving, disintegration of the particles of both the solvent and the substance dissolved takes place, a process which in its mechanical aspect resembles evaporation, and therefore must consume much heat. The heat emitted in the solution of a solid must therefore be considered (Personne) as composed of three factors--(1) positive, the effect of combination; (2) negative, the effect of transference into a liquid state; and (3) negative, the effect of disintegration. In the solution of a liquid by a liquid the second factor is removed; and therefore, if the heat evolved in combination is greater than that absorbed in disintegration a heating effect is observed, and in the reverse case a cooling effect; and, indeed, sulphuric acid, alcohol, and many liquids evolve heat in dissolving in each other. But the solution of chloroform in carbon bisulphide (Bussy and Binget), or of phenol (or aniline) in water (Alexéeff), produces cold. In the solution of a small quantity of water in acetic acid (Abasheff), or hydrocyanic acid (Bussy and Binget), or amyl alcohol (Alexéeff), cold is produced, whilst in the solution of these substances in an excess of water heat is evolved. The relation existing between the solubility of solid bodies and the heat and temperature of fusion and solution has been studied by many investigators, and more recently (1893) by Schröder, who states that in the solution of a solid body in a solvent which does not act chemically upon it, a very simple process takes place, which differs but little from the intermixture of two gases which do not react chemically upon each other. The following relation between the heat of solution _Q_ and the heat of fusion _p_ may then be taken: _P_/_T__{0} = _Q_/_T_ = constant, where _T__{0} and _T_ are the absolute (from -273°) temperatures of fusion and saturation. Thus, for instance, in the case of naphthalene the calculated and observed magnitudes of the heat of solution differ but slightly from each other. The fullest information concerning the solution of liquids in liquids has been gathered by W. T. Alexéeff (1883-1885); these data are, however, far from being sufficient to solve the mass of problems respecting this subject. He showed that two liquids which dissolve in each other, intermix together in all proportions at a certain temperature. Thus the solubility of phenol, C_{6}H_{6}O, in water, and the converse, is limited up to 70°, whilst above this temperature they intermix in all proportions. This is seen from the following figures, where p is the percentage amount of phenol and _t_ the temperature at which the solution becomes turbid--that is, that at which it is saturated:-- _p_ = 7·12 10·20 15·31 26·15 28·55 36·70 48·86 61·15 71·97 _t_ = 1° 45° 60° 67° 67° 67° 65° 53° 20° It is exactly the same with the solution of benzene, aniline, and other substances in molten sulphur. Alexéeff discovered a similar complete intermixture for solutions of secondary butyl alcohol in water at about 107°; at lower temperatures the solubility is not only limited, but between 50° and 70° it is at its minimum, both for solutions of the alcohol in water and for water in the alcohol; and at a temperature of 5° both solutions exhibit a fresh change in their scale of solubility, so that a solution of the alcohol in water which is saturated between 5° and 40° will become turbid when heated to 60°. In the solution of liquids in liquids, Alexéeff observed a lowering in temperature (an absorption of heat) and an absence of change in specific heat (calculated for the mixture) much more frequently than had been done by previous observers. As regards his hypothesis (in the sense of a mechanical and not a chemical representation of solutions) that substances in solution preserve their physical states (as gases, liquids, or solids), it is very doubtful, for it would necessitate admitting the presence of ice in water or its vapour. From what has been said above, it will be clear that even in so very simple a case as solution, it is impossible to calculate the heat emitted by chemical action alone, and that the chemical process cannot be separated from the physical and mechanical. [26] The cooling effect produced in the solution of solids (and also in the expansion of gases and in evaporation) is applied to the _production of low temperatures_. Ammonium nitrate is very often used for this purpose; in dissolving in water it absorbs 77 units of heat per each part by weight. On evaporating the solution thus formed, the solid salt is re-obtained. The application of the various _freezing mixtures_ is based on the same principle. Snow or broken ice frequently enters into the composition of these _mixtures_, advantage being taken of its latent heat of fusion in order to obtain the lowest possible temperature (without altering the pressure or employing heat, as in other methods of obtaining a low temperature). For laboratory work recourse is most often had to a mixture of three parts of snow and one part of common salt, which causes the temperature to fall from 0° to -21° C. Potassium thiocyanate, KCNS, mixed with water (3/4 by weight of the salt) gives a still lower temperature. By mixing ten parts of crystallised calcium chloride, CaCl_{2},6H_{2}O, with seven parts of snow, the temperature may even fall from 0° to -55°. [27] The heat which is evolved in solution, or even in the dilution of solutions, is also sometimes made use of in practice. Thus caustic soda (NaHO), in dissolving or on the addition of water to a strong solution of it, evolves so much heat that it can replace fuel. In a steam boiler, which has been previously heated to the boiling point, another boiler is placed containing caustic soda, and the exhaust steam is made to pass through the latter; the formation of steam then goes on for a somewhat long period of time without any other heating. Norton makes use of this for smokeless street locomotives. [28] [Illustration: FIG. 17.--Curves expressing the contraction, quantity of heat, and rises of temperature produced by mixing sulphuric acid with water. Percentage of H_{2}SO_{4} is given along the axis of abscissae.] The temperatures obtained by mixing monohydrated sulphuric acid, H_{2}SO_{4}, with different quantities of water, are shown on the lowest curve in fig. 17, the relative proportions of both substances being expressed in percentages by weight along the horizontal axis. The greatest rise of temperature is 149°. It corresponds with the greatest evolution of heat (given on the middle curve) corresponding with a definite volume (100 c.c.) of the solution produced. The top curve expresses the degree of contraction, which also corresponds with 100 volumes of the solution produced. The greatest contraction, as also the greatest rise of temperature, corresponds with the formation of a trihydrate, H_{2}SO_{4},2H_{2}O (= 73·1 p.c. H_{2}SO_{4}), which very likely repeats itself in a similar form in other solutions, although all the phenomena (of contraction, evolution of heat, and rise of temperature) are very complex and are dependent on many circumstances. One would think, however, judging from the above examples, that all other influences are feebler in their action than chemical attraction, especially when it is so considerable as between sulphuric acid and water. Solution is a reversible reaction; for, if the water be expelled from a solution, the substance originally taken is obtained again. But it must be borne in mind that the expulsion of the water taken for solution is not always accomplished with equal facility, because water has different degrees of chemical affinity for the substance dissolved. Thus, if a solution of sulphuric acid, which mixes with water in all proportions, be heated, it will be found that very different degrees of heat are required to expel the water. When it is in a large excess, water is given off at a temperature slightly above 100°, but if it be in but a small proportion there is such an affinity between it and the sulphuric acid that at 120°, 150°, 200°, and even at 300°, water is still retained by the sulphuric acid. The bond between the remaining quantity of water and the sulphuric acid is evidently stronger than the bond between the sulphuric acid and the excess of water. The force acting in solutions is consequently of different intensity, starting from so feeble an attraction that the properties of water--as, for instance, its power of evaporation--are but very little changed, and ending with cases of strong attraction between the water and the substance dissolved in or chemically combined with it. In consideration of the very important significance of the phenomena, and of the cases of the breaking up of solutions with separation of water or of the substance dissolved from them, we shall further discuss them separately, after having acquainted ourselves with certain peculiarities of the solution of gases and of solid bodies. The solubility of gases, which is usually measured by the volume of gas[29] (at 0° and 760 mm. pressure) per 100 volumes of water, varies not only with the nature of the gas (and also of the solvent), and with the temperature, but also with the pressure, because gases themselves change their volume considerably with the pressure. As might be expected, (1) gases which are easily liquefied (by pressure and cold) are more soluble than those which are liquefied with difficulty. Thus, in 100 volumes of water only two volumes of hydrogen dissolve at 0° and 760 mm., three volumes of carbonic oxide, four volumes of oxygen, &c., for these are gases which are liquefied with difficulty; whilst there dissolve 180 volumes of carbonic anhydride, 130 of nitrous oxide, and 437 of sulphurous anhydride, for these are gases which are rather easily liquefied. (2) The solubility of a gas is diminished by heating, which is easily intelligible from what has been said previously--the elasticity of a gas becomes greater, it is removed further from a liquid state. Thus 100 volumes of water at 0° dissolve 2·5 volumes of air, and at 20° only 1·7 volume. For this reason cold water, when brought into a warm room, parts with a portion of the gas dissolved in it.[30] (3) The quantity of the gas dissolved varies directly with the pressure. This rule is called the _law of Henry and Dalton_, and is applicable to those gases which are little soluble in water. Therefore a gas is separated from its solution in water in a vacuum, and water saturated with a gas under great pressure parts with it if the pressure be diminished. Thus many mineral springs are saturated underground with carbonic anhydride under the great pressure of the column of water above them. On coming to the surface, the water of these springs boils and foams on giving up the excess of dissolved gas. Sparkling wines and aërated waters are saturated under pressure with the same gas. They hold the gas so long as they are in a well-corked vessel. When the cork is removed and the liquid comes in contact with air at a lower pressure, part of the gas, unable to remain in solution at a lower pressure, is separated as froth with the hissing sound familiar to all. It must be remarked that the law of Henry and Dalton belongs to the class of _approximate laws_, like the laws of gases (Gay-Lussac's and Mariotte's) and many others--that is, it expresses only a portion of a complex phenomenon, the limit towards which the phenomenon aims. The matter is rendered complicated from the influence of the degree of solubility and of affinity of the dissolved gas for water. Gases which are little soluble--for instance, hydrogen, oxygen, and nitrogen--follow the law of Henry and Dalton the most closely. Carbonic anhydride exhibits a decided deviation from the law, as is seen from the determinations of Wroblewski (1882). He showed that at 0° a cubic centimetre of water absorbs 1·8 cubic centimetre of the gas under a pressure of one atmosphere; under 10 atmospheres, 16 cubic centimetres (and not 18, as it should be according to the law); under 20 atmospheres, 26·6 cubic centimetres (instead of 36), and under 30 atmospheres, 33·7 cubic centimetres.[31] However, as the researches of Sechenoff show, the absorption of carbonic anhydride within certain limits of change of pressure, and at the ordinary temperature, by water--and even by solutions of salts which are not chemically changed by it, or do not form compounds with it--very closely follows the law of Henry and Dalton, so that the chemical bond between this gas and water is so feeble that the breaking up of the solution with separation of the gas is accomplished by a decrease of pressure alone.[32] The case is different if a considerable affinity exists between the dissolved gas and water. Then it might even be expected that the gas would not be entirely separated from water in a vacuum, as should be the case with gases according to the law of Henry and Dalton. Such gases--and, in general, all those which are very soluble--exhibit a distinct deviation from the law of Henry and Dalton. As examples, ammonia and hydrochloric acid gas may be taken. The former is separated by boiling and decrease of pressure, while the latter is not, but they both deviate distinctly from the law. +---------------+-----------------+--------------------+ |Pressure in mm.|Ammonia dissolved| Hydrochloric acid | | of mercury | in 100 grams of |gas dissolved in 100| | | water at 0° |grams of water at 0°| +---------------+-----------------+--------------------+ | | Grams | Grams | | 100 | 28·0 | 65·7 | | 500 | 69·2 | 78·2 | | 1,000 | 112·6 | 85·6 | | 1,500 | 165·6 | -- | +---------------+-----------------+--------------------+ [29] If a volume of gas _v_ be measured under a pressure of _h_ mm. of mercury (at 0°) and at a temperature _t_° Centigrade, then, according to the combined laws of Boyle, Mariotte, and of Gay-Lussac, its volume at 0° and 760 mm. will equal the product of _v_ into 760 divided by the product of _h_ into 1 + _a__t_°, where _a_ is the co-efficient of expansion of gases, which is equal to 0·00367. The weight of the gas will be equal to its volume at 0° and 760 mm. multiplied by its density referred to air and by the weight of one volume of air at 0° and 760 mm. The weight of one litre of air under these conditions being = 1·293 gram. If the density of the gas be given in relation to hydrogen this must be divided by 14·4 to bring it in relation to air. If the gas be measured when saturated with aqueous vapour, then it must be reduced to the volume and weight of the gas when dry, according to the rules given in Note 1. If the pressure be determined by a column of mercury having a temperature _t_, then by dividing the height of the column by 1 + 0·00018_t_ the corresponding height at 0° is obtained. If the gas be enclosed in a tube in which a liquid stands above the level of the mercury, the height of the column of the liquid being = H and its density = D, then the gas will be under a pressure which is equal to the barometric pressure less HD/13·59, where 13·59 is the density of mercury. By these methods the _quantity of a gas_ is determined, and its observed volume reduced to normal conditions or to parts by weight. The physical data concerning vapours and gases must be continually kept in sight in dealing with and measuring gases. The student must become perfectly familiar with the calculations relating to gases. [30] According to Bunsen, Winkler, Timofeeff, and others, 100 vols. of water under a pressure of one atmosphere absorb the following volumes of gas (measured at 0° and 760 mm.):-- 1 2 3 4 5 6 7 8 9 10 11 0° 4·82 2·35 2·15 179·7 3·54 130·5 437·1 688·6 5·4 104960 7·38 20° 3·10 1·54 1·83 90·1 2·32 67·0 290·5 362·2 3·5 65400 4·71 1, oxygen; 2, nitrogen; 3, hydrogen; 4, carbonic anhydride; 5, carbonic oxide; 6, nitrous oxide; 7, hydrogen sulphide; 8, sulphurous anhydride; 9, marsh gas; 10, ammonia; 11, nitric oxide. The decrease of solubility with a rise of temperature varies for different gases; it is greater, the greater the molecular weight of the gas. It is shown by calculation that this decrease varies (Winkler) as the cube root of the molecular weight of the gas. This is seen from the following table: +--------------+-------------+---------------+ | Decrease of | Cube root of| Ratio between | | solubility | molecular | decrease and | | per 20° in | weight. | cube root of | | per cent. | | mol. wt. | +--------------+-------------+---------------+ | H_{2} 15·32 | 1·259 | 12·17 | | N_{2} 34·33 | 3·037 | 11·30 | | CO 34·44 | 3·037 | 11·34 | | NO 36·24 | 3·107 | 11·66 | | O_{2} 36·55 | 3·175 | 11·51 | +--------------+-------------+---------------+ The decrease in the coefficient of absorption with the temperature must be connected with a change in the physical properties of the water. Winkler (1891) remarked a certain relation between the internal friction and the coefficient of absorption at various temperatures. [31] These figures show that the co-efficient of solubility decreases with an increase of pressure, notwithstanding that the carbonic anhydride approaches a liquid state. As a matter of fact, liquefied carbonic anhydride does not intermix with water, and does not exhibit a rapid increase in solubility at its temperature of liquefaction. This indicates, in the first place, that solution does not consist in liquefaction, and in the second place that the solubility of a substance is determined by a peculiar attraction of water for the substance dissolving. Wroblewski even considered it possible to admit that a dissolved gas retains its properties as a gas. This he deduced from experiments, which showed that the rate of diffusion of gases in a solvent is, for gases of different densities, inversely proportional to the square roots of their densities, just as the velocities of gaseous molecules (see Note 34). Wroblewski showed the affinity of water, H_{2}O, for carbonic anhydride, CO_{2}, from the fact that on expanding moist compressed carbonic anhydride (compressed at 0° under a pressure of 10 atmospheres) he obtained (a fall in temperature takes place from the expansion) a very unstable definite crystalline compound, CO_{2} + 8H_{2}O. [32] As, according to the researches of Roscoe and his collaborators, ammonia exhibits a considerable deviation at low temperatures from the law of Henry and Dalton, whilst at 100° the deviation is small, it would appear that the dissociating influence of temperature affects all gaseous solutions; that is, at high temperatures, the solutions of all gases will follow the law, and at lower temperatures there will in all cases be a deviation from it. It will be remarked, for instance, from this table that whilst the pressure increased 10 times, the solubility of ammonia only increased 4-1/2 times. A number of examples of such cases of the absorption of gases by liquids might be cited which do not in any way, even approximately, agree with the laws of solubility. Thus, for instance, carbonic anhydride is absorbed by a solution of caustic potash in water, and if sufficient caustic potash be present it is not separated from the solution by a decrease of pressure. This is a case of more intimate chemical combination. A correlation less completely studied, but similar and clearly chemical, appears in certain cases of the solution of gases in water, and we shall afterwards find an example of this in the solution of hydrogen iodide; but we will first stop to consider a remarkable application of the law of Henry and Dalton[33] in the case of the solution of a mixture of two gases, and this we must do all the more because the phenomena which there take place cannot be foreseen without a clear theoretical representation of the nature of gases.[34] [33] The ratio between the pressure and the amount of gas dissolved was discovered by Henry in 1805, and Dalton in 1807 pointed out the adaptability of this law to cases of gaseous mixtures, introducing the conception of partial pressures which is absolutely necessary for a right comprehension of Dalton's law. The conception of partial pressures essentially enters into that of the diffusion of vapours in gases (footnote 1); for the pressure of damp air is equal to the sum of the pressures of dry air and of the aqueous vapour in it, and it is admitted as a corollary to Dalton's law that evaporation in dry air takes place as in a vacuum. It is, however, necessary to remark that the volume of a mixture of two gases (or vapours) is only approximately equal to the sum of the volumes of its constituents (the same, naturally, also refers to their pressures)--that is to say, in mixing gases a change of volume occurs, which, although small, is quite apparent when carefully measured. For instance, in 1888 Brown showed that on mixing various volumes of sulphurous anhydride (SO_{2}) with carbonic anhydride (at equal pressures of 760 mm. and equal temperatures) a decrease of pressure of 3·9 millimetres of mercury was observed. The possibility of a chemical action in similar mixtures is evident from the fact that equal volumes of sulphurous and carbonic anhydrides at -19° form, according to Pictet's researches in 1888, a liquid which may be regarded as an unstable chemical compound, or a solution similar to that given when sulphurous anhydride and water combine to an unstable chemical whole. [34] The origin of the kinetic theory of gases now generally accepted, according to which they are animated by a rapid progressive motion, is very ancient (Bernouilli and others in the last century had already developed a similar representation), but it was only generally accepted after the mechanical theory of heat had been established, and after the work of Krönig (1855), and especially after its mathematical side had been worked out by Clausius and Maxwell. The pressure, elasticity, diffusion, and internal friction of gases, the laws of Boyle, Mariotte, and of Gay-Lussac and Avogadro-Gerhardt are not only explained (deduced) by the kinetic theory of gases, but also expressed with perfect exactitude; thus, for example, the magnitude of the internal friction of different gases was foretold with exactitude by Maxwell, by applying the theory of probabilities to the impact of gaseous particles. The kinetic theory of gases must therefore be considered as one of the most brilliant acquisitions of the latter half of the present century. The velocity of the progressive motion of the particles of a gas, one cubic centimetre of which weighs _d_ grams, is found, according to the theory, to be equal to the square root of the product of 3_pDq_ divided by _d_, where _p_ is the pressure under which _d_ is determined expressed in centimetres of the mercury column, _D_ the weight of a cubic centimetre of mercury in grams (_D_ = 13·59, _p_ = 76, consequently the normal pressure = 1,033 grams on a sq. cm.), and _g_ the acceleration of gravity in centimetres (_g_ = 980·5, at the sea level and long. 45° = 981·92 at St. Petersburg; in general it varies with the longitude and altitude of the locality). Therefore, at 0° the velocity of hydrogen is 1,843, and of oxygen 461, metres per second. This is the average velocity, and (according to Maxwell and others) it is probable that the velocities of individual particles are different; that is, they occur in, as it were, different conditions of temperature, which it is very important to take into consideration in investigating many phenomena proper to matter. It is evident from the above determination of the velocity of gases, that different gases at the same temperature and pressure have average velocities, which are inversely proportional to the square roots of their densities; this is also shown by direct experiment on the flow of gases through a fine orifice, or through a porous wall. This _dissimilar velocity of flow_ for different gases is frequently taken advantage of in chemical researches (see Chap. II. and also Chap. VII.) in order to separate two gases having different densities and velocities. The difference of the velocity of flow of gases also determines the phenomenon cited in the following footnote for demonstrating the existence of an internal motion in gases. If for a certain mass of a gas which fully and exactly follows the laws of Mariotte and Gay-Lussac the temperature _t_ and the pressure _p_ be changed simultaneously, then the entire change would be expressed by the equation _pv_ = _C_(1 + _at_), or, what is the same, _pv_ = _RT_, where _T_ = _t_ + 273 and _C_ and _R_ are constants which vary not only with the units taken but with the nature of the gas and its mass. But as there are discrepancies from both the fundamental laws of gases (which will be discussed in the following chapter), and as, on the one hand, a certain attraction between the gaseous molecules must be admitted, while on the other hand the molecules of gases themselves must occupy a portion of a space, hence for ordinary gases, within any considerable variation of pressure and temperature, recourse should be had to Van der Waal's formula-- (_p_ + _a_/_v_^2)(_v_-_p_) = R(1 + _at_) where _a_ is the true co-efficient of expansion of gases. The formula of Van der Waals has an especially important significance in the case of the passage of a gas into a liquid state, because the fundamental properties of both gases and liquids are equally well expressed by it, although only in their general features. The further development of the questions referring to the subjects here touched on, which are of especial interest for the theory of solutions, must be looked for in special memoirs and works on theoretical and physical chemistry. A small part of this subject will be partially considered in the footnotes of the following chapter. _The law of partial pressures_ is as follows:--The solubility of gases in intermixture with each other does not depend on the influence of the total pressure acting on the mixture, but on the influence of that portion of the total pressure which is due to the volume of each given gas in the mixture. Thus, for instance, if oxygen and carbonic anhydride were mixed in equal volumes and exerted a pressure of 760 millimetres, then water would dissolve so much of each of these gases as would be dissolved if each separately exerted a pressure of half an atmosphere, and in this case, at 0° one cubic centimetre of water would dissolve 0·02 cubic centimetre of oxygen and 0·90 cubic centimetre of carbonic anhydride. If the pressure of a gaseous mixture equals _h_, and in _n_ volumes of the mixture there be _a_ volumes of a given gas, then its solution will proceed as though this gas were dissolved under a pressure (_h_ × _a_)/_n_. That portion of the pressure under influence of which the solution proceeds is termed the 'partial' pressure. In order to clearly understand the cause of the law of partial pressures, an explanation must be given of the fundamental properties of gases. Gases are elastic and disperse in all directions. We are led from what we know of gases to the assumption that these fundamental properties of gases are due to a rapid progressive motion, in all directions, which is proper to their smallest particles (molecules).[35] These molecules in impinging against an obstacle produce a pressure. The greater the number of molecules impinging against an obstacle in a given time, the greater the pressure. The pressure of a separate gas or of a gaseous mixture depends on the sum of the pressures of all the molecules, on the number of blows in a unit of time on a unit of surface, and on the mass and velocity (or the _vis viva_) of the impinging molecules. The nature of the different molecules is of no account; the obstacle is acted on by a pressure due to the sum of their _vis viva_. But, in a chemical action such as the solution of gases, the nature of the impinging molecules plays, on the contrary, the most important part. In impinging against a liquid, a portion of the gas enters into the liquid itself, and is held by it so long as other gaseous molecules impinge against the liquid--exert a pressure on it. As regards the solubility of a given gas, for the number of blows it makes on the surface of a liquid, it is immaterial whether other molecules of gases impinge side by side with it or not. Hence, the solubility of a given gas will be proportional, not to the total pressure of a gaseous mixture, but to that portion of it which is due to the given gas separately. Moreover, the saturation of a liquid by a gas depends on the fact that the molecules of gases that have entered into a liquid do not remain at rest in it, although they enter in a harmonious kind of motion with the molecules of the liquid, and therefore they throw themselves off from the surface of the liquid (just like its vapour if the liquid be volatile). If in a unit of time an equal number of molecules penetrate into (leap into) a liquid and leave (or leap out of) a liquid, it is saturated. It is a case of mobile equilibrium, and not of rest. Therefore, if the pressure be diminished, the number of molecules departing from the liquid will exceed the number of molecules entering into the liquid, and a fresh state of mobile equilibrium only takes place under a fresh equality of the number of molecules departing from and entering into the liquid. In this manner the main features of the solution are explained, and furthermore of that special (chemical) attraction (penetration and harmonious motion) of a gas for a liquid, which determines both the measure of solubility and the degree of stability of the solution produced. [35] Although the actual motion of gaseous molecules, which is accepted by the kinetic theory of gases, cannot be seen, yet its existence may be rendered evident by taking advantage of the difference in the velocities undoubtedly belonging to different gases which are of different densities under equal pressures. The molecules of a light gas must move more rapidly than the molecules of a heavier gas in order to produce the same pressure. Let us take, therefore, two gases--hydrogen and air; the former is 14·4 times lighter than the latter, and hence the molecules of hydrogen must move almost four times more quickly than air (more exactly 3·8, according to the formula given in the preceding footnote). Consequently, if a porous cylinder containing air is introduced into an atmosphere of hydrogen, then in a given time the volume of hydrogen which succeeds in entering the cylinder will be greater than the volume of air leaving the cylinder, and therefore the pressure inside the cylinder will rise until the gaseous mixture (of air and hydrogen) attains an equal density both inside and outside the cylinder. If now the experiment be reversed and air surround the cylinder, and hydrogen be inside the cylinder, then more gas will leave the cylinder than enters it, and hence the pressure inside the cylinder will be diminished. In these considerations we have replaced the idea of the number of molecules by the idea of volumes. We shall learn subsequently that equal volumes of different gases contain an equal number of molecules (the law of Avogadro-Gerhardt), and therefore instead of speaking of the number of molecules we can speak of the number of volumes. If the cylinder be partially immersed in water the rise and fall of the pressure can be observed directly, and the experiment consequently rendered self-evident. The consequences of the law of partial pressures are exceedingly numerous and important. All liquids in nature are in contact with the atmosphere, which, as we shall afterwards see more fully, consists of an intermixture of gases, chiefly four in number--oxygen, nitrogen, carbonic anhydride, and aqueous vapour. 100 volumes of air contain, approximately, 78 volumes of nitrogen, and about 21 volumes of oxygen; the quantity of carbonic anhydride, by volume, does not exceed 0·05. Under ordinary circumstances, the quantity of aqueous vapour is much greater than this, but it varies of course with climatic conditions. We conclude from these numbers that the solution of nitrogen in a liquid in contact with the atmosphere will proceed under a partial pressure of (78/100) × 760 mm. if the atmospheric pressure equal 760 mm.; similarly, under a pressure of 600 mm. of mercury, the solution of oxygen will proceed under a partial pressure of about 160 mm., and the solution of carbonic anhydride only under the very small pressure of 0·4 mm. As, however, the solubility of oxygen in water is twice that of nitrogen, the ratio of O to N dissolved in water will be greater than the ratio in air. It is easy to calculate what quantity of each of the gases will be contained in water, and taking the simplest case we will calculate what quantity of oxygen, nitrogen, and carbonic anhydride will be dissolved from air having the above composition at 0° and 760 mm. pressure. Under a pressure of 760 mm. 1 cubic centimetre of water dissolves 0·0203 cubic centimetre of nitrogen or under the partial pressure of 600 mm. it will dissolve 0·0203 × 600/760, or 0·0160 cubic centimetre; of oxygen 0·0411 × 160/760, or 0·0086 cubic centimetre; of carbonic anhydride 1·8 × 0·4/760 or 0·00095 cubic centimetre: hence, 100 cubic centimetres of water will contain at 0° altogether 2·55 cubic centimetres of atmospheric gases, and 100 volumes of air dissolved in water will contain about 62 p.c. of nitrogen, 34 p.c. of oxygen, and 4 p.c. of carbonic anhydride. The water of rivers, wells, &c. usually contains more carbonic anhydride. This proceeds from the oxidation of organic substances falling into the water. The amount of oxygen, however, dissolved in water appears to be actually about 1/3 the dissolved gases, whilst air contains only 1/5 of it by volume. According to the law of partial pressures, whatever gas be dissolved in water will be expelled from the solution in an atmosphere of another gas. This depends on the fact that gases dissolved in water escape from it in a vacuum, because the pressure is nil. An atmosphere of another gas acts like a vacuum on a gas dissolved in water. Separation then proceeds, because the molecules of the dissolved gas no longer impinge upon the liquid, are not dissolved in it, and those previously held in solution leave the liquid in virtue of their elasticity.[36] For the same reason a gas may be entirely expelled from a gaseous solution by boiling--at least, in many cases when it does not form particularly stable compounds with water. In fact the surface of the boiling liquid will be occupied by aqueous vapour, and therefore all the pressure acting on the gas will be due to the aqueous vapour. On this account, the partial pressure of the dissolved gas will be very inconsiderable, and this is the sole reason why _a gas separates from a solution on boiling the liquid containing it_. At the boiling point of water the solubility of gases in water is still sufficiently great for a considerable quantity of a gas to remain in solution. The gas dissolved in the liquid is carried away, together with the aqueous vapour; if boiling be continued for a long time, all the gas will finally be separated.[37] [36] Here two cases occur; either the atmosphere surrounding the solution may be limited, or it may be proportionally so vast as to be unlimited, like the earth's atmosphere. If a gaseous solution be brought into an atmosphere of another gas which is limited--for instance, as in a closed vessel--then a portion of the gas held in solution will be expelled, and thus pass over into the atmosphere surrounding the solution, and will produce its partial pressure. Let us imagine that water saturated with carbonic anhydride at 0° and under the ordinary pressure is brought into an atmosphere of a gas which is not absorbed by water; for instance, that 10 c.c. of an aqueous solution of carbonic anhydride is introduced into a vessel holding 10 c.c. of such a gas. The solution will contain 18 c.c. of carbonic anhydride. The expulsion of this gas proceeds until a state of equilibrium is arrived at. The liquid will then contain a certain amount of carbonic anhydride, which is retained under the partial pressure of that gas which has been expelled. Now, how much gas will remain in the liquid and how much will pass over into the surrounding atmosphere? In order to solve this problem, let us suppose that _x_ cubic centimetres of carbonic anhydride are retained in the solution. It is evident that the amount of carbonic anhydride which passed over into the surrounding atmosphere will be 18-_x_, and the total volume of gas will be 10 + 18-_x_ or 28-_x_ cubic centimetres. The partial pressure under which the carbonic anhydride is then dissolved will be (supposing that the common pressure remains constant the whole time) equal to (18-_x_)/(28-_x_), hence there is not in solution 18 c.c. of carbonic anhydride (as would be the case were the partial pressure equal to the atmospheric pressure), but only 18(18-_x_)/(28-_x_), which is equal to _x_, and we therefore obtain the equation 18(18-_x_)/(28-_x_) = _x_, hence _x_ = 8·69. Again, where the atmosphere into which the gaseous solution is introduced is not only that of another gas but also unlimited, then the gas dissolved will, on passing over from the solution, diffuse into this atmosphere, and produce an infinitely small pressure in the unlimited atmosphere. Consequently, no gas can be retained in solution under this infinitely small pressure, and it will be entirely expelled from the solution. For this reason water saturated with a gas which is not contained in air, will be entirely deprived of the dissolved gas if left exposed to the air. Water also passes off from a solution into the atmosphere, and it is evident that there might be such a case as a constant proportion between the quantity of water vaporised and the quantity of a gas expelled from a solution, so that not the gas alone, but the entire gaseous solution, would pass off. A similar case is exhibited in solutions which are not decomposed by heat (such as those of hydrogen chloride and iodide), as will afterwards be considered. [37] However, in those cases when the variation of the co-efficient of solubility with the temperature is not sufficiently great, and when a known quantity of aqueous vapour and of the gas passes off from a solution at the boiling point, an atmosphere may be obtained having the same composition as the liquid itself. In this case the amount of gas passing over into such an atmosphere will not be greater than that held by the liquid, and therefore such a gaseous solution will distil over unchanged. The solution will then represent, like a solution of hydriodic acid in water, a liquid which is not altered by distillation, while the pressure under which this distillation takes place remains constant. Thus in all its aspects solution presents gradations from the most feeble affinities to examples of intimate chemical combination. The _amount of heat_ evolved in the solution of equal volumes of different gases is in distinct relation with these variations of stability and solubility of different gases. 22·3 litres of the following gases (at 760 mm. pressure) evolve the following number of (gram) units of heat in dissolving in a large mass of water; carbonic anhydride 5,600, sulphurous anhydride 7,700, ammonia 8,800, hydrochloric acid 17,400, and hydriodic acid 19,400. The two last-named gases, which are not expelled from their solution by boiling, evolve approximately twice as much heat as gases like ammonia, which are separated from their solutions by boiling, whilst gases which are only slightly soluble evolve very much less heat. It is evident that the conception of the partial pressures of gases should be applied not only to the formations of solutions, but also to all cases of chemical action of gases. Especially numerous are its applications to the physiology of respiration, for in these cases it is only the oxygen of the atmosphere that acts.[38] [38] Among the numerous researches concerning this subject, certain results obtained by Paul Bert are cited in Chapter III., and we will here point out that Prof. Sechenoff, in his researches on the absorption of gases by liquids, very fully investigated the phenomena of the solution of carbonic anhydride in solutions of various salts, and arrived at many important results, which showed that, on the one hand, in the solution of carbonic anhydride in solutions of salts on which it is capable of acting chemically (for example, sodium carbonate, borax, ordinary sodium phosphate), there is not only an increase of solubility, but also a distinct deviation from the law of Henry and Dalton; whilst, on the other hand, that solutions of salts which are not acted on by carbonic anhydride (for example, the chlorides, nitrates, and sulphates) absorb less of it, owing to the 'competition' of the salt already dissolved, and follow the law of Henry and Dalton, but at the same time show undoubted signs of a chemical action between the salt, water, and carbonic anhydride. Sulphuric acid (whose co-efficient of absorption is 92 vols. per 100), when diluted with water, absorbs less and less carbonic anhydride, until the hydrate H_{2}SO_{4},H_{2}O (co-eff. of absorption then equals 66 vols.) is formed; then on further addition of water the solubility again rises until a solution of 100 p.c. of water is obtained. The solution of _solids_, whilst depending only in a small measure on the pressure under which solution takes place (because solids and liquids are almost incompressible), is very clearly dependent on the temperature. In the great majority of cases the solubility of solids in water increases with the temperature; and further, the rapidity of solution increases also. The latter is determined by the rapidity of diffusion of the solution formed into the remainder of the water. The solution of a solid in water, although it is as with gases, a physical passage into a liquid state, is determined, however, by its chemical affinity for water; this is clearly shown from the fact that in solution there occurs a diminution in volume, a change in the boiling point of water, a change in the tension of its vapour, in the freezing point, and in many similar properties. If solution were a physical, and not a chemical, phenomenon, it would naturally be accompanied by an increase and not by a diminution of volume, because generally in melting a solid increases in volume (its density diminishes). _Contraction_ is the usual phenomenon accompanying solution and takes place even in the addition of solutions to water,[39] and in the solution of liquids in water,[40] just as happens in the combination of substances when evidently new substances are produced.[41] The contraction which takes place in solution is, however, very small, a fact which depends on the small compressibility of solids and liquids, and on the insignificance of the compressing force acting in solution.[42] The change of volume which takes place in the solution of solids and liquids, or the alteration in specific gravity[43] corresponding with it, depends on peculiarities of the dissolving substances, and of water, and, in the majority of cases, is not proportional to the quantity of the substance dissolved,[44] showing the existence of a chemical force between the solvent and the substance dissolved which is of the same nature as in all other forms of chemical reaction.[45] [39] Kremers made this observation in the following simple form:--He took a narrow-necked flask, with a mark on the narrow part (like that on a litre flask which is used for accurately measuring liquids), poured water into it, and then inserted a funnel, having a fine tube which reached to the bottom of the flask. Through this funnel he carefully poured a solution of any salt, and (having removed the funnel) allowed the liquid to attain a definite temperature (in a water bath); he then filled the flask up to the mark with water. In this manner two layers of liquid were obtained, the heavy saline solution below and water above. The flask was then shaken in order to accelerate diffusion, and it was observed that the volume became less if the temperature remained constant. This can be proved by calculation, if the specific gravity of the solutions and water be known. Thus at 15° one c.c. of a 20 p.c. solution of common salt weighs 1·1500 gram, hence 100 grams occupy a volume of 86·96 c.c. As the sp. gr. of water at 15° = 0·99916, therefore 100 grams of water occupy a volume of 100·08 c.c. The sum of the volumes is 187·04 c.c. After mixing, 200 grams of a 10 p.c. solution are obtained. Its specific gravity is 1·0725 (at 15° and referred to water at its maximum density), hence the 200 grams will occupy a volume of 186·48 c.c. The contraction is consequently equal to 0·56 c.c. [40] The contractions produced in the case of the solution of sulphuric acid in water are shown in the diagram Fig. 17 (page 77). Their maximum is 10·1 c.c. per 100 c.c. of the solution formed. A maximum contraction of 4·15 at 0°, 3·78 at 15°, and 3·50 at 30°, takes place in the solution of 46 parts by weight of anhydrous alcohol in 54 parts of water. This signifies that if, at 0°, 46 parts by weight of alcohol be taken per 54 parts by weight of water, then the sum of their separate volumes will he 104·15, and after mixing their total volume will be 100. [41] This subject will be considered later in this work, and we shall then see that the contraction produced in reactions of combination (of solids or liquids) is very variable in its amount, and that there are, although rarely, reactions of combination in which contraction does not take place, or when an increase of volume is produced. [42] The compressibility of solutions of common salt is less, according to Grassi, than that of water. At 18° the compression of water per million volumes = 48 vols. for a pressure of one atmosphere; for a 15 p.c. solution of common salt it is 32, and for a 24 p.c. solution 26 vols. Similar determinations were made by Brown (1887) for saturated solutions of sal ammoniac (38 vols.), alum (46 vols.), common salt (27 vols.), and sodium sulphate at +1°, when the compressibility of water = 47 per million volumes. This investigator also showed that substances which dissolve with an evolution of heat and with an increase in volume (as, for instance, sal ammoniac) are partially separated from their saturated solutions by an increase of pressure (this experiment was particularly conclusive in the case of sal ammoniac), whilst the solubility of substances which dissolve with an absorption of heat or diminution in volume increases, although very slightly, _with an increase of pressure_. Sorby observed the same phenomenon with common salt (1863). [43] The most trustworthy data relating to the variation of the specific gravity of solutions with a change of their composition and temperature, are collected and discussed in my work cited in footnote 19. The practical (for the amount of a substance in solution is determined by the aid of the specific gravities of solutions, both in works and in laboratory practice) and the theoretical (for specific gravity can be more accurately observed than other properties, and because a variation in specific gravity governs the variation of many other properties) interest of this subject, besides the strict rules and laws to which it is liable, make one wish that this province of data concerning solutions may soon be enriched by further observations of as accurate a nature as possible. Their collection does not present any great difficulty, although requiring much time and attention. Pickering in London and Tourbaba in Kharkoff must be ranked first among those who have pursued problems of this nature during recent years. [44] Inasmuch as the degree of change exhibited in many properties on the formation of solutions is not large, so, owing to the insufficient accuracy of observations, a proportionality between this change and a change of composition may, in a first rough approximation and especially within narrow limits of change of composition, easily be imagined in cases where it does not even exist. The conclusion of Michel and Kraft is particularly instructive in this respect; in 1854, on the basis of their incomplete researches, they supposed that the increment of the specific gravity of solutions was proportional to the increment of a salt in a given volume of a solution, which is only true for determinations of specific gravity which are exact to the second decimal place--an accuracy insufficient even for technical determinations. Accurate measurements do not confirm a proportionality either in this case or in many others where a ratio has been generally accepted; as, for example, for the rotatory power (with respect to the plane of polarisation) of solutions, and for their capillarity, &c. Nevertheless, such a method is not only still made use of, but even has its advantages when applied to solutions within a limited scope--as, for instance, very weak solutions, and for a first acquaintance with the phenomena accompanying solution, and also as a means for facilitating the application of mathematical analysis to the investigation of the phenomenon of solution. Judging by the results obtained in my researches on the specific gravity of solutions, I think that in many cases it would be nearer the truth to take the change of properties as proportional, not to the amount of a substance dissolved, but to the product of this quantity and the amount of water in which it is dissolved; the more so since many chemical relations vary in proportion to the reacting masses, and a similar ratio has been established for many phenomena of attraction studied by mechanics. This product is easily arrived at when the quantity of water in the solutions to be compared is constant, as is shown in investigating the fall of temperature in the formation of ice (_see_ footnote 49, p. 91). [45] All the different forms of chemical reaction may be said to take place in the process of solution. (1) _Combinations_ between the solvent and the substance dissolved, which are more or less stable (more or less dissociated). This form of reaction is the most probable, and is that most often observed. (2) Reactions of _substitution_ or of _double decomposition_ between the molecules. Thus it may be supposed that in the solution of sal ammoniac, NH_{4}Cl, the action of water produces ammonia, NH_{4}HO, and hydrochloric acid, HCl, which are dissolved in the water and simultaneously attract each other. As these solutions and many others do indeed exhibit signs, which are sometimes indisputable, of similar double decompositions (thus solutions of sal-ammoniac yield a certain amount of ammonia), it is probable that this form of reaction is more often met with than is generally thought. (3) Reactions of _isomerism_ or _replacement_ are also probably met with in solution, all the more as here molecules of different kinds come into intimate contact, and it is very likely that the configuration of the atoms in the molecules under these influences is somewhat different from what it was in its original and isolated state. One is led to this supposition especially from observations made on solutions of substances which rotate the plane of polarisation (and observations of this kind are very sensitive with respect to the atomic structure of molecules), because they show, for example (according to Schneider, 1881), that strong solutions of malic acid rotate the plane of polarisation to the right, whilst its ammonium salts in all degrees of concentration rotate the plane of polarisation to the left. (4) Reactions of _decomposition_ under the influences of solution are not only rational in themselves, but have in recent years been recognised by Arrhenius, Ostwald, and others, particularly on the basis of electrolytic determinations. If a portion of the molecules of a solution occur in a condition of decomposition, the other portion may occur in a yet more complex state of combination, just as the velocity of the motion of different gaseous molecules may be far from being the same (_see_ Note 34, p. 81). It is, therefore, very probable that the reactions taking place in solution vary both quantitatively and qualitatively with the mass of water in the solution, and the great difficulty in arriving at a definite conclusion as to the nature of the chemical relations which take place in the process of solution will be understood, and if besides this the existence of a physical process, like the sliding between and interpenetration of two homogeneous liquids, be also recognised in solution, then the complexity of the problem as to the actual nature of solutions, which is now to the fore, appears in its true light. However, the efforts which are now being applied to the solution of this problem are so numerous and of such varied aspect that they will afford future investigators a vast mass of material towards the construction of a complete theory of solution. For my part, I am of opinion that the study of the physical properties of solutions (and especially of weak ones) which now obtains, cannot give any fundamental and complete solution of the problem whatever (although it should add much to both the provinces of physics and chemistry), but that, parallel with it, should be undertaken the study of the influence of temperature, and especially of low temperatures, the application to solutions of the mechanical theory of heat, and the comparative study of the chemical properties of solutions. The beginning of all this is already established, but it is impossible to consider in so short an exposition of chemistry the further efforts of this kind which have been made up to the present date. The feeble development of the chemical affinities acting in solutions of solids becomes evident from those multifarious methods by which _their solutions are decomposed_, whether they be saturated or not. On heating (absorption of heat), on cooling, and by internal forces alone, aqueous solutions in many cases separate into their components or their definite compounds with water. The water contained in solutions is removed from them as vapour, or, by freezing, in the form of ice,[46] but the _tension of the vapour of water_[47] held in solution is less than that of water in a free state, and the _temperature of the formation of ice_ from solutions is lower than 0°. Further, both the diminution of vapour tension and the lowering of the freezing point proceed, in dilute solutions, almost in proportion to the amount of a substance dissolved.[48] Thus, if per 100 grams of water there be in solution 1, 5, 10 grams of common salt (NaCl), then at 100° the vapour tension of the solutions decreases by 4, 21, 43 mm. of the barometric column, against 760 mm., or the vapour tension of water, whilst the freezing points are -0·58°, -2·91°, and -6·10° respectively. The above figures[49] are almost proportional to the amounts of salt in solution (1, 5, and 10 per 100 of water). Furthermore, it has been shown by experiment that the ratio of the diminution of vapour tension to the vapour tension of water at different temperatures in a given solution is an almost constant quantity,[50] and that for every (dilute) solution the ratio between the diminution of vapour tension and of the freezing point is also a tolerably constant quantity.[51] [46] If solutions are regarded as being in a state of dissociation (_see_ footnote 19, p. 64) it would be expected that they would contain free molecules of water, which form one of the products of the decomposition of those definite compounds whose formation is the cause of solution. In separating as ice or vapour, water makes, with a solution, a heterogeneous system (made up of substances in different physical states) similar, for instance, to the formation of a precipitate or volatile substance in reactions of double decomposition. [47] If the substance dissolved is non-volatile (like salt or sugar), or only slightly volatile, then the whole of the tension of the vapour given off is due to the water, but if a solution of a volatile substance--for instance, a gas or a volatile liquid--evaporates, then only a portion of the pressure belongs to the water, and the whole pressure observed consists of the sum of the pressures of the vapours of the water and of the substance dissolved. The majority of researches bear on the first case, which will be spoken of presently, and the observations of D. P. Konovaloff (1881) refer to the second case. He showed that in the case of two volatile liquids, mutually soluble in each other, forming two layers of saturated solutions (for example, ether and water, Note 20, p. 67), both solutions have an equal vapour tension (in the case in point the tension of both is equal to 431 mm. of mercury at 19·8°). Further, he found that for solutions which are formed in all proportions, the tension is either greater (solutions of alcohol and water) or less (solutions of formic acid) than that which answers to the rectilinear change (proportional to the composition) from the tension of water to the tension of the substance dissolved; thus, the tension, for example, of a 70 p.c. solution of formic acid is less, at all temperatures, than the tension of water and of formic acid itself. In this case the tension of a solution is never equal to the sum of the tensions of the dissolving liquids, as Regnault already showed when he distinguished this case from that in which a mixture of liquids, which are insoluble in each other, evaporates. From this it is evident that a mutual action occurs in solution, which diminishes the vapour tensions proper to the individual substances, as would be expected on the supposition of the formation of compounds in solutions, because the elasticity then always diminishes. [48] This amount is usually expressed by the weight of the substance dissolved per 100 parts by weight of water. Probably it would be better to express it by the quantity of the substance in a definite volume of the solution--for instance, in a litre--or by the ratios of the number of molecules of water and of the substance dissolved. [49] The variation of the vapour tension of solutions has been investigated by many. The best known researches are those of Wüllner in Germany (1858-1860) and of Tamman in Russia (1887). The researches on the temperature of the formation of ice from various solutions are also very numerous; Blagden (1788), Rüdorff (1861), and De Coppet (1871) established the beginning, but this kind of investigation takes its chief interest from the work of Raoult, begun in 1882 on aqueous solutions, and afterwards continued for solutions in various other easily frozen liquids--for instance, benzene, C_{6}H_{6} (melts at 4·96°), acetic acid, C_{2}H_{4}O_{2} (16·75°), and others. An especially important interest is attached to these cryoscopic investigations of Raoult in France on the depression of the freezing point, because he took solutions of many well-known carbon-compounds and discovered a simple relation between the molecular weight of the substances and the temperature of crystallisation of the solvent, which enabled this kind of research to be applied to the investigation of the nature of substances. We shall meet with the application of this method later on (_see also_ Chapter VII.), and at present will only cite the deduction arrived at from these results. The solution of one-hundredth part of that molecular gram weight which corresponds with the formula of a substance dissolved (for example, NaCl = 58·5, C_{2}H_{6}O = 46, &c.) in 100 parts of a solvent lowers the freezing point of its solution in water 0·185°, in benzene 0·49°, and in acetic acid O·39°, or twice as much as with water. And as in weak solutions the depression or fall of freezing point is proportional to the amount of the substance dissolved, it follows that the fall of freezing point for all other solutions may be calculated from this rule. So, for instance, the weight which corresponds with the formula of acetone, C_{3}H_{6}O is 58; a solution containing 2·42, 6·22, and 12·35 grams of acetone per 100 grams of water, forms ice (according to the determinations of Beckmann) at 0·770°, 1·930°, and 3·820°, and these figures show that with a solution containing 0·58 gram of acetone per 100 of water the fall of the temperature of the formation of ice will be 0·185°, 0·180°, and 0·179°. It must be remarked that the law of proportionality between the fall of temperature of the formation of ice, and the composition of a solution, is in general only approximate, and is only applicable to weak solutions (Pickering and others). We will here remark that the theoretical interest of this subject was strengthened on the discovery of the connection existing between the fall of tension, the fall of the temperature of the formation of ice, of osmotic pressure (Van't Hoff, Note 19), and of the electrical conductivity of solutions, and we will therefore supplement what we have already said on the subject by some short remarks on the method of cryoscopic investigations, although the details of the subject form the subject of more special works on physical chemistry (such as Ostwald's _Lehrbuch der allgemeinen Chemie_, 1891-1894, 2 vols.) In order to determine the _temperature of the formation of ice_ (or of crystallisation of other solvents), a solution of known strength is prepared and poured into a cylindrical vessel surrounded by a second similar vessel, leaving a layer of air between the two, which, being a bad conductor, prevents any rapid change of temperature. The bulb of a sensitive and corrected thermometer is immersed in the solution, and also a bent platinum wire for stirring the solution; the whole is then cooled (by immersing the apparatus in a freezing mixture), and the temperature at which ice begins to separate observed. If the temperature at first falls slightly lower, it nevertheless becomes constant when ice begins to form. By then allowing the liquid to get just warm, and again observing the temperature of the formation of ice, an exact determination may be arrived at. It is still better to take a large mass of solution, and induce the formation of the first crystals by dropping a small lump of ice into the solution already partially over-cooled. This only imperceptibly changes the composition of the solution. The observation should be made at the point of formation of only a very small amount of crystals, as otherwise the composition of the solution will become altered from their separation. Every precaution must be taken to prevent the access of moisture to the interior of the apparatus, which might also alter the composition of the solution or properties of the solvent (for instance, when using acetic acid). With respect to the depression of dilute solutions it is known--(1) That the depression increases in almost direct proportion to the amount of the substance in solution (always per 100 parts of water), for example, for KCl when the solution contains 1 part of salt (per 100 parts of water) the depression = 0·45°, when the solution contains 2 parts of salt = 0·90°, with 10 parts of salt = 4·4°. (2) The greater the molecular weight expressed by the formula (see Chapter VII.), and designated by M, the less, under other similar conditions, will be the depression _d_, and therefore if the concentration of a solution (the amount by weight of substance dissolved per 100 parts of water) be designated by _p_, then the fraction M_d_/_p_ or the molecular depression for a given class of substances will be a constant quantity; for example, in the case of methyl alcohol in water 17·3, for acetone about 18·0, for sugar about 18·5. (3) In general the molecular depression for substances whose solutions do not conduct an electric current is about 18·5, while for acids, salts, and such like substances whose solutions do conduct electricity, it is _i_ times greater; for instance, for HCl, KI, HNO_{3}, KHO, &c., about 36 (_i_ is nearly 2), for borax about 66, and so on where _i_ varies in the same manner as it does in the case of the osmotic pressure of solutions (Note 19). (4) Different solvents (water, acetic acid, benzene, &c.) have each their corresponding constants of molecular depression (which have a certain remote connection with their molecular weight); for example, for acetic acid the molecular depression is about 39 and not 19 (as it is for water), for benzene 49, for methyl alcohol about 17, &c. (5) If the molecular weight M of a substance be unknown, then in the case of non-conductors of electricity or for a given group, it may be found by determining the depression, _d_, for a given concentration, _p_; for example, in the case of peroxide of hydrogen, which is a non-conductor of electricity, the molecular weight, M, was found to be nearly 34, _i.e._ equal to H_{2}O_{2}. Similar results have also been found for the fall in the vapour tension of solutions (Note 51), and for the rise of their boiling points (hence these data may also serve for determining the molecular weight of a substance in solution, as is shortly described in Chapter VII., Note 27 bis). And as these conclusions are also applicable in the case of osmotic pressure (Note 19), and a variation in the magnitude of _i_, in passing from solutions which do not conduct an electric current to those which do conduct electricity is everywhere remarked, so it was natural to here seek that causal connection which Arrhenius (1888), Ostwald, and others expected to find in the supposition that a portion of the substance of the electrolyte is already decomposed in the very act of solution, into its ions (for example, NaCl into Na and Cl), or into the atoms of those individual substances which make their appearance in electrolysis, and in this way to explain the fact that _i_ is greater for those bodies which conduct an electric current. We will not consider here this supposition, known as the hypothesis of 'electrolytic dissociation,' not only because it wholly belongs to that special branch--physical chemistry, and gives scarcely any help towards explaining the chemical relations of solutions (particularly their passage into definite compounds, their reactions, and their very formation), but also because--(1) all the above data (for constant depression, osmotic pressure, &c.) only refer to dilute solutions, and are not applicable to strong solutions; whilst the chemical interest in strong solutions is not less than in dilute solutions, and the transition from the former into the latter is consecutive and inevitable; (2) because in all homogeneous bodies (although it may be insoluble and not an electrolyte) a portion of the atoms may he supposed (Clausius) to be passing from one particle to another (Chapter X., Note 28), and as it were dissociated, but there are no reasons for believing that such a phenomenon is proper to the solutions of electrolytes only; (3) because no essential mark of difference is observed between the solution of electrolytes and non-conductors, although it might be expected there would be according to Arrhenius' hypothesis; (4) because it is most reasonable to suppose the formation of new, more complex, but unstable and easily dissociated compounds in the act of solution, than a decomposition, even partial, of the substances taken; (5) because if Arrhenius' hypothesis be accepted it becomes necessary to admit the existence in solutions of free ions, like the atoms Cl or Na, without any apparent expenditure of the energy necessary for their disruption, and if in this case it can be explained why _i_ then = 2, it is not at all clear why solutions of MgSO_{4} give _i_ = 1, although the solution does conduct an electric current; (6) because in dilute solutions, the approximative proportionality between the depression and concentration may be recognised, while admitting the formation of hydrates, with as much right as in admitting the solution of anhydrous substances, and if the formation of hydrates be recognised it is easier to admit that a portion of these hydrates is decomposed than to accept the breaking-up into ions; (7) because the best conductors of electricity are solutions like the sulphates in which it is necessary to recognise the formation of associated systems or hydrates; (8) because the cause of electro-conductivity can be sooner looked for in this affinity and this combination of the substance dissolved with the solvent, as is seen from the fact, that (D. P. Konovaloff) neither aniline nor acetic acid alone conduct an electric current, a solution of aniline in water conducts it badly (and here the affinity is very small), while a solution of aniline in acetic acid forms a good electrolyte, in which, without doubt, chemical forces are acting, bringing aniline, like ammonia, into combination with the acetic acid; which is evident from the researches made by Prof. Konovaloff upon mixtures (solutions) of aniline and other amines; and, lastly, (9) because I, together with many of the chemists of the present day, cannot regard the hypothesis of electrolytic dissociation in the form given to it up to now by Arrhenius and Ostwald, as answering to the sum total of the chemical data respecting solutions and dissociation in general. Thus, although I consider it superfluous to discuss further the evolution of the above theory of solutions, still I think that it would he most useful for students of chemistry to consider all the data referring to this subject, which can be found in the _Zeitschrift für physikalische Chemie_, 1888-1894. [50] This fact, which was established by Gay-Lussac, Pierson, and v. Babo, is confirmed by the latest observations, and enables us to express not only the fall of tension (_p_-_p_´) itself, but its ratio to the tension of water (_p_-_p_´)/_p_. It is to be remarked that in the absence of any chemical action, the fall of pressure is either very small, or does not exist at all (note 33), and is not proportional to the quantity of the substance added. As a rule, the tension is then equal, according to the law of Dalton, to the sum of the tensions of the substances taken. Hence liquids which are insoluble in each other (for example, water and chloride of carbon) present a tension equal to the sum of their individual tensions, and therefore such a mixture boils at a lower temperature than the more volatile liquid (Magnus, Regnault). [51] If, in the example of common salt, the fall of tension be divided by the tension of water, a figure is obtained which is nearly 105 times less than the magnitude of the fall of temperature of formation of ice. This correlation was theoretically deduced by Goldberg, on the basis of the application of the mechanical theory of heat, and is repeated by many investigated solutions. The diminution of the vapour tension of solutions explains the rise in boiling point due to the solution of solid non-volatile bodies in water. The temperature of a vapour is the same as that of the solution from which it is generated, and therefore it follows that the aqueous vapour given off from a solution will be superheated. A saturated solution of common salt boils at 108·4°, a solution of 335 parts of nitre in 100 parts of water at 115·9°, and a solution of 325 parts of potassium chloride in 100 parts of water at 179°, if the temperature of ebullition be determined by immersing the thermometer bulb in the liquid itself. This is another proof of the bond which exists between water and the substance dissolved. And this bond is seen still more clearly in those cases (for example, in the solution of nitric or formic acid in water) where the solution boils at a higher temperature than either water or the volatile substance dissolved in it. For this reason the solutions of certain gases--for instance, hydriodic or hydrochloric acid--boil above 100°. The separation of ice from solutions[52] explains both the phenomenon, well known to sailors, that the ice formed from salt water gives fresh water, and also the fact that by freezing, just as by evaporation, a solution is obtained which is richer in salts than before. This is taken advantage of in cold countries for obtaining a liquor from sea water, which is then evaporated for the extraction of salt. [52] Fritzsche showed that solutions of certain colouring matters yield colourless ice, which clearly proves the passage of water only into a solid state, without any intermixture of the substance dissolved, although the possibility of the admixture in certain other cases cannot be denied. On the removal of part of the water from a solution (by evaporation or the separation of ice), a saturated solution should be obtained, and then the solid substance dissolved should separate out. Solutions saturated at a certain temperature should also separate out a corresponding portion of the substance dissolved if they be reduced, by cooling,[53] to a temperature at which the water can no longer hold the former quantity of the substance in solution. If this separation, by cooling a saturated solution or by evaporation, take place slowly, _crystals_ of the substance dissolved are in many cases formed; and this is the method by which crystals of soluble salts are usually obtained. Certain solids very easily separate out from their solutions in perfectly formed crystals, which may attain very large dimensions. Such are nickel sulphate, alum, sodium carbonate, chrome-alum, copper sulphate, potassium ferricyanide, and a whole series of other salts. The most remarkable circumstance in this is that many solids in separating out from an aqueous solution retain a portion of water, forming crystallised solid substances which contain water. A portion of the water previously in the solution remains in the separated crystals. The water which is thus retained is called the _water of crystallisation_. Alum, copper sulphate, Glauber's salt, and magnesium sulphate contain such water, but neither sal-ammoniac, table salt, nitre, potassium chlorate, silver nitrate, nor sugar, contains any water of crystallisation. One and the same substance may separate out from a solution with or without water of crystallisation, according to the temperature at which the crystals are formed. Thus common salt in crystallising from its solution in water at the ordinary or at a higher temperature does not contain water of crystallisation. But if its separation from the solution takes place at a low temperature, namely below -5°, then the crystals contain 38 parts of water in 100 parts. Crystals of the same substance which separate out at different temperatures may contain different amounts of water of crystallisation. This proves to us that a solid dissolved in water may form various compounds with it, differing in their properties and composition, and capable of appearing in a solid separate form like many ordinary definite compounds. This is indicated by the numerous properties and phenomena connected with solutions, and gives reason for thinking that there exist in solutions themselves such compounds of the substance dissolved, and the solvent or compounds similar to them, only in a liquid partly decomposed form. Even the _colour of solutions_ may often confirm this opinion. Copper sulphate forms crystals having a blue colour and containing water of crystallisation. If the water of crystallisation be removed by heating the crystals to redness, a colourless anhydrous substance is obtained (a white powder). From this it may be seen that the blue colour belongs to the compound of the copper salt with water. Solutions of copper sulphate are all blue, and consequently they contain a compound similar to the compound formed by the salt with its water of crystallisation. Crystals of cobalt chloride when dissolved in an anhydrous liquid--like alcohol, for instance--give a blue solution, but when they are dissolved in water a red solution is obtained. Crystals from the aqueous solution, according to Professor Potilitzin, contain six times as much water (CoCl_{2},6H_{2}O) for a given weight of the salt, as those violet crystals (CoCl_{2},H_{2}O) which are formed by the evaporation of an alcoholic solution. [53] As the solubility of certain substances (for example, coniine, cerium sulphate, and others) decreases with a rise of temperature (between certain limits--see, for example, note 24), so these substances do not separate from their saturated solutions on cooling but on heating. Thus a solution of manganese sulphate, saturated at 70°, becomes cloudy on further heating. The point at which a substance separates from its solution with a change of temperature gives an easy means of determining the co-efficient of solubility, and this was taken advantage of by Prof. Alexéeff for determining the solubility of many substances. The phenomenon and method of observation are here essentially the same as in the determination of the temperature of formation of ice. If a solution of a substance which separates out on heating be taken (for example, the sulphate of calcium or manganese), then at a certain fall of temperature ice will separate out from it, and at a certain rise of temperature the salt will separate out. From this example, and from general considerations, it is clear that the separation of a substance dissolved from a solution should present a certain analogy to the separation of ice from a solution. In both cases, a heterogeneous system of a solid and a liquid is formed from a homogeneous (liquid) system. That solutions contain particular compounds with water is further shown by the phenomena of supersaturated solutions, of so-called cryohydrates, of solutions of certain acids having constant boiling points, and the properties of compounds containing water of crystallisation whose data it is indispensable to keep in view in the consideration of solutions. Supersaturated solutions exhibit the following phenomena:--On the refrigeration of a saturated solution of certain salts,[54] if the liquid be brought under certain conditions, the excess of the solid may sometimes remain in solution and not separate out. A great number of substances, and more especially sodium sulphate, Na_{2}SO_{4}, or Glauber's salt, easily form supersaturated solutions. If boiling water be saturated with this salt, and the solution be poured off from any remaining undissolved salt, and, the boiling being still continued, the vessel holding the solution be well closed by cotton wool, or by fusing up the vessel, or by covering the solution with a layer of oil, then it will he found that this saturated solution does not separate out any Glauber's salt whatever on cooling down to the ordinary or even to a much lower temperature; although without the above precautions a salt separates out on cooling, in the form of crystals, which contain Na_{2}SO_{4},10H_{2}O--that is, 180 parts of water for 142 parts of anhydrous salt. The supersaturated solution may be moved about or shaken inside the vessel holding it, and no crystallisation will take place; the salt remains in the solution in as large an amount as at a higher temperature. If the vessel holding the supersaturated solution be opened and a crystal of Glauber's salt be thrown in, crystallisation suddenly takes place.[55] A considerable rise in temperature is noticed during this rapid separation of crystals, which is due to the fact that the salt, previously in a liquid state, passes into a solid state. This bears some resemblance to the fact that water maybe cooled below 0° (even to -10°) if it be left at rest, under certain circumstances, and evolves heat in suddenly crystallising. Although from this point of view there is a resemblance, yet in reality the phenomenon of supersaturated solutions is much more complicated. Thus, on cooling, a saturated solution of Glauber's salt deposits crystals containing Na_{2}SO_{4},7H_{2}0,[56] or 126 parts of water per 142 parts of anhydrous salt, and not 180 parts of water, as in the above-mentioned salt. The crystals containing 7H_{2}O are distinguished for their instability; if they stand in contact not only with crystals of Na_{2}SO_{4},10H_{2}O, but with many other substances, they immediately become opaque, forming a mixture of anhydrous and deca-hydrated salts. It is evident that between water and a soluble substance there may be established different kinds of greater or less stable equilibrium, of which solutions form a particular case.[57] [54] Those salts which separate out with water of crystallisation and give several crystallohydrates form supersaturated solutions with the greatest facility, and the phenomenon is much more common than was previously imagined. The first data were given in the last century by Loewitz, in St. Petersburg. Numerous researches have proved that supersaturated solutions do not differ from ordinary solutions in any of their essential properties. The variations in specific gravity, vapour tension, formation of ice, &c., take place according to the ordinary laws. [55] Inasmuch as air, as has been shown by direct experiment, contains, although in very small quantities, minute crystals of salts, and among them sodium sulphate, air can bring about the crystallisation of a supersaturated solution of sodium sulphate in an open vessel, but it has no effect on saturated solutions of certain other salts; for example, lead acetate. According to the observations of De Boisbaudran, Gernez, and others, isomorphous salts (analogous in composition) are capable of inducing crystallisation. Thus, a supersaturated solution of nickel sulphate crystallises by contact with crystals of sulphates of other metals analogous to it, such as those of magnesium, cobalt, copper, and manganese. The crystallisation of a supersaturated solution, set up by the contact of a minute crystal, starts from it in rays with a definite velocity, and it is evident that the crystals as they form propagate the crystallisation in definite directions. This phenomenon recalls the evolution of organisms from germs. An attraction of similar molecules ensues, and they dispose themselves in definite similar forms. [56] At the present time a view is very generally accepted, which regards supersaturated solutions as homogeneous systems, which pass into heterogeneous systems (composed of a liquid and a solid substance), in all respects exactly resembling the passage of water cooled below its freezing point into ice and water, or the passage of crystals of rhombic sulphur into monoclinic crystals, and of the monoclinic crystals into rhombic. Although many phenomena of supersaturation are thus clearly understood, yet the spontaneous formation of the unstable hepta-hydrated salt (with 7H_{2}O), in the place of the more stable deca-hydrated salt (with mol. 10H_{2}O), indicates a property of a saturated solution of sodium sulphate which obliges one to admit that it has a different structure from an ordinary solution. Stcherbacheff asserts, on the basis of his researches, that a solution of the deca-hydrated salt gives, on evaporation, without the aid of heat, the deca-hydrated salt, whilst after heating above 33° it forms a supersaturated solution and the hepta-hydrated salt. But in order that this view should be accepted, some facts must be discovered distinguishing solutions (which are, according to this view, isomeric) containing the hepta-hydrated salt from those containing the deca-hydrated salt, and all efforts in this direction (the study of the properties of the solutions) have given negative results. As some crystallohydrates of salts (alums, sugar of lead, calcium chloride) melt straightway (without separating out anything), whilst others (like Na_{2}SO_{4},10H_{2}O) are broken up, then it may be that the latter are only in a state of equilibrium at a higher temperature than their melting point. It may here be observed that in melting crystals of the deca-hydrated salt, there is formed, besides the solid anhydrous salt, a saturated solution giving the hepta-hydrated salt, so that this passage from the deca-to the hepta-hydrated salt, and the reverse, takes place with the formation of the anhydrous (or, it may be, monohydrated) salt. Moreover, supersaturation (Potilitzin, 1889) only takes place with those substances which are capable of giving several modifications or several crystallohydrates, _i.e._ supersaturated solutions separate out, besides the stable normal crystallohydrate, hydrates containing less water and also the anhydrous salt. This degree of saturation acts upon the substance dissolved in a like manner to heat. Sulphate of nickel in a solution at 15° to 20° separates out rhombic crystals with 7H_{2}O, at 30° to 40° cubical crystals, with 6H_{2}O, at 50° to 70° monoclinic crystals, also containing 6H_{2}O. Crystals of the same composition separate out from supersaturated solutions at one temperature (17° to 19°), but at different degrees of saturation, as was shown by Lecoq de Boisbaudran. The capacity to voluntarily separate out slightly hydrated or anhydrous salts by the introduction of a crystal into the solution is common to all supersaturated solutions. If a salt forms a supersaturated solution, then one would expect, according to this view, that it should exist in the form of several hydrates or in several modifications. Thus Potilitzin concluded that chlorate of strontium, which easily gives supersaturated solutions, should be capable of forming several hydrates, besides the anhydrous salt known; and he succeeded in discovering the existence of two hydrates, Sr(ClO_{3})_{2},3H_{2}O and apparently Sr(ClO_{3})_{2},8H_{2}O. Besides this, three modifications of the common anhydrous salt were obtained, differing from each other in their crystalline form. One modification separated out in the form of rhombic octahedra, another in oblique plates, and a third in long brittle prisms or plates. Further researches showed that salts which are not capable of forming supersaturated solutions such as the bromates of calcium, strontium, and barium, part with their water of hydration with difficulty (they crystallise with 1H_{2}O), and decompose very slowly in a vacuum or in dry air. In other words the tension of dissociation is very small in this class of hydrates. As the hydrates characterised by a small dissociation tension are incapable of giving supersaturated solutions, so conversely supersaturated solutions give hydrates whose tension of dissociation is great (Potilitzin, 1893). [57] _Emulsions_, like milk, are composed of a solution of glutinous or similar substances, or of oily liquids suspended in a liquid in the form of drops, which are clearly visible under a microscope, and form an example of a mechanical formation which resembles solution. But the difference from solutions is here evident. There are, however, solutions which approach very near to emulsions in the facility with which the substance dissolved separates from them. It has long been known, for example, that a particular kind of Prussian blue, KFe_{2}(CN)_{6}, dissolves in pure water, but, on the addition of the smallest quantity of either of a number of salts, it coagulates and becomes quite insoluble. If copper sulphide (CuS), cadmium sulphide (CdS), arsenic sulphide (As_{2}S_{5}) (the experiments with these substances proceed with great ease, and the solution obtained is comparatively stable), and many other metallic sulphides, be obtained by a method of double decomposition (by precipitating salts of these metals by hydrogen sulphide), and be then carefully washed (by allowing the precipitate to settle, pouring off the liquid, and again adding sulphuretted hydrogen water), then, as was shown by Schulze, Spring, Prost, and others, the previously insoluble sulphides pass into transparent (for mercury, lead, and silver, reddish brown; for copper and iron, greenish brown; for cadmium and indium, yellow; and for zinc, colourless) solutions, which may be preserved (the weaker they are the longer they keep) and even boiled, but which, nevertheless, in time coagulate--that is, separate in an insoluble form, and then sometimes become crystalline and quite incapable of re-dissolving. Graham and others observed the power shown by colloids (_see_ note 18) of forming similar _hydrosols or solutions of gelatinous colloids_, and, in describing alumina and silica, we shall again have occasion to speak of such solutions. In the existing state of our knowledge concerning solution, such solutions may be looked on as a transition between emulsion and ordinary solutions, but no fundamental judgment can be formed about them until a study has been made of their relations to ordinary solutions (the solutions of even soluble colloids freeze immediately on cooling below 0°, and, according to Guthrie, do not form cryohydrates), and to supersaturated solutions, with which they have certain points in common. Solutions of salts on refrigeration below 0° deposit ice or crystals (which then frequently contain water of crystallisation) of the salt dissolved, and on reaching a certain degree of concentration they solidify in their entire mass. These solidified masses are termed _cryohydrates_. My researches on solutions of common salt (1868) showed that its solution solidifies when it reaches a composition NaCl + 10H_{2}O (180 parts of water per 58·5 parts of salt), which takes place at about -23°. The solidified solution melts at the same temperature, and both the portion melted and the remainder preserve the above composition. Guthrie (1874-1876) obtained the cryohydrates of many salts, and he showed that certain of them are formed like the above at comparatively low temperatures, whilst others (for instance, corrosive sublimate, alums, potassium chlorate, and various colloids) are formed on a slight cooling, to -2° or even before.[58] In the case of common salt, the cryohydrate with 10 molecules of water, and in the case of sodium nitrate, the cryohydrate[59] with 7 molecules of water (_i.e._ 126 parts of water per 85 of salt) should be accepted as established substances, capable of passing from a solid to a liquid state and conversely; and therefore it may be thought that in cryohydrates we have solutions which are not only undecomposable by cold, but also have a definite composition which would present a fresh case of definite equilibrium between the solvent and the substance dissolved. [58] Offer (1880) concludes, from his researches on cryohydrates, that they are simple mixtures of ice and salts, having a constant melting point, just as there are alloys having a constant point of fusion, and solutions of liquids with a constant boiling point (_see_ note 60). This does not, however, explain in what form a salt is contained, for instance, in the cryohydrate NaCl + 10H_{2}O. At temperatures above -10° common salt separates out in anhydrous crystals, and at temperatures near -10°, in combination with water of crystallisation, NaCl + 2H_{2}O, and, therefore, it is very improbable that at still lower temperatures it would separate without water. If the possibility of the solidified cryohydrate containing NaCl + 2H_{2}O and ice be admitted, then it is not clear why one of these substances does not melt before the other. If alcohol does not extract water from the solid mass, leaving the salt behind, this does not prove the presence of ice, because alcohol also takes up water from the crystals of many hydrated substances (for instance, from NaCl + 2H_{2}O) at about their melting-points. Besides which, a simple observation on the cryohydrate, NaCl + 10H_{2}O, shows that with the most careful cooling it does not on the addition of ice deposit ice, which would occur if ice were formed on solidification intermixed with the salt. I may add with regard to cryohydrates that many of the solutions of acids solidify completely on prolonged cooling (for example, H_{2}SO_{4},H_{2}O), and then form perfectly definite compounds. For the solutions of sulphuric acid (_see_ Chapter XX.) Pickering obtained, for instance, a hydrate, H_{2}SO_{4},4H_{2}O at -25°. Hydrochloric, nitric, and other acids also give similar crystalline hydrates, melting at low temperatures and presenting many similarities with the cryohydrates. [59] _See_ note 24. The formation of definite but unstable compounds in the process of solution becomes evident from the phenomena of a marked decrease of vapour tension, or from the rise of the temperature of ebullition which occurs in the solution of certain volatile liquids and gases in water. As an example, we will take hydriodic acid, HI, a gas which liquefies, giving a liquid which boils at -20°. A solution of it containing 57 p.c. of hydriodic acid is distinguished by the fact that if it be heated the hydriodic acid volatilises together with the water in the same proportions as they occur in the solution, therefore such a solution may be distilled unchanged. The solution boils at a higher temperature than water, at 127°. A portion of the physical properties of the gas and water have in this case already disappeared--a new substance is formed, which has its definite boiling point. To put it more correctly, this is not the temperature of ebullition, but the temperature at which the compound formed decomposes, forming the vapours of the products of dissociation, which, on cooling, re-combine. Should a less amount of hydriodic acid be dissolved in water than the above, then, on heating such a solution, water only at first distils over, until the solution attains the above-mentioned composition; it will then distil over unaltered. If more hydriodic acid be passed into such a solution a fresh quantity of the gas will dissolve, but it passes off with great ease, like air from water. It must not, however, be thought that those forces which determine the formation of ordinary gaseous solutions play no part whatever in the formation of a solution having a definite boiling point; that they do react is shown from the fact that such constant gaseous solutions vary in their composition under different pressures.[60] It is not, therefore, at every, but only at the ordinary, atmospheric pressure that a constant boiling solution of hydriodic acid will contain 57 p.c. of the gas. At another pressure the proportion of water and hydriodic acid will be different. It varies, however, judging from observations made by Roscoe, very little for considerable variations of pressure. This variation in composition directly indicates that pressure exerts an influence on the formation of unstable chemical compounds which are easily dissociated (with formation of a gas), just as it influences the solution of gases, only the latter is influenced to a more considerable degree than the former.[61] Hydrochloric, nitric, and other acids form _solutions having definite boiling points_, like that of hydriodic acid. They show further the common property, if containing but a small proportion of water, that they _fume in air_. Strong solutions of nitric, hydrochloric, hydriodic, and other gases are even termed 'fuming acids.' The fuming liquids contain a definite compound whose temperature of ebullition (decomposition) is higher than 100°, and contain also an excess of the volatile substance dissolved, which exhibits a capacity to combine with water and form a hydrate, whose vapour tension is less than that of aqueous vapour. On evaporating in air, this dissolved substance meets the atmospheric moisture and forms a visible vapour (fumes) with it, which consists of the above-mentioned compound. The attraction or affinity which binds, for instance, hydriodic acid with water is evinced not only in the evolution of heat and the diminution of vapour tension (rise of boiling point), but also in many purely chemical relations. Thus hydriodic acid is produced from iodine and hydrogen sulphide in the presence of water, but unless water is present this reaction does not take place.[62] [60] For this reason (the want of entire constancy of the composition of constant boiling solutions with a change of pressure), the existence of definite hydrates formed by volatile substances--for instance, by hydrochloric acid and water--is frequently denied. It is generally argued as follows: If there did exist a constancy of composition, then it would be unaltered by a change of pressure. But the distillation of constant boiling hydrates is undoubtedly accompanied (judging by the vapour densities determined by Bineau), like the distillation of sal ammoniac, sulphuric acid, &c., by a complete decomposition of the original compound--that is, these substances do not exist in a state of vapour, but their products of decomposition (hydrochloric acid and water) are gases at the temperature of volatilisation, which dissolve in the volatilised and condensed liquids; but the solubility of gases in liquids depends on the pressure, and, therefore, the composition of constant boiling solutions may, and even ought to, vary with a change of pressure, and, further, the smaller the pressure and the lower the temperature of volatilisation, the more likely is a true compound to be obtained. According to the researches of Roscoe and Dittmar (1859), the constant boiling solution of hydrochloric acid proved to contain 18 p.c. of hydrochloric acid at a pressure of 3 atmospheres, 20 p.c. at 1 atmosphere, and 23 p.c. at 1/10 of an atmosphere. On passing air through the solution until its composition became constant (_i.e._ forcing the excess of aqueous vapour or of hydrochloric acid to pass away with the air), then acid was obtained containing about 20 p.c. at 100°, about 23 p.c. at 50°, and about 25 p.c. at 0°. From this it is seen that by decreasing the pressure and lowering the temperature of evaporation one arrives at the same limit, where the composition should be taken as HCl + 6H_{2}O, which requires 25·26 p.c. of hydrochloric acid. Fuming hydrochloric acid contains more than this. In the case already considered, as in the case of formic acid in the researches of D. P. Konovaloff (note 47), the constant boiling solution corresponds with a minimum tension--that is, with a boiling point higher than that of either of the component elements. But there is another case of constant boiling solutions similar to the case of the solution of propyl alcohol, C_{3}H_{8}O, when a solution, undecomposed by distillation, boils at a lower point than that of the more volatile liquid. However, in this case also, if there be solution, the possibility of the formation of a definite compound in the form C_{3}H_{8}O + H_{2}O cannot be denied, and the tension of the solution is not equal to the sum of tensions of the components. There are possible cases of constant boiling mixtures even when there is no solution nor any loss of tension, and consequently no chemical action, since the amount of liquids that are volatilised is determined by the product of the vapour densities into their vapour tensions (Wanklyn), in consequence of which liquids whose boiling point is above 100°--for instance, turpentine and ethereal oils in general--when distilled with aqueous vapour, pass over at a temperature below 100°. Consequently, it is not in the constancy of composition and boiling point (temperature of decomposition) that evidence of a distinct chemical action is to be found in the above-described solutions of acids, but in the great loss of tension, which completely resembles the loss of tension observed, for instance, in the perfectly-definite combinations of substances with water of crystallisation (see later, note 65). Sulphuric acid, H_{2}SO_{4}, as we shall learn later, is also decomposed by distillation, like HCl + 6H_{2}O, and exhibits, moreover, all the signs of a definite chemical compound. The study of the variation of the specific gravities of solutions as dependent on their composition (see note 19) shows that phenomena of a similar kind, although of different dimensions, take place in the formation of both H_{2}SO_{4} from H_{2}O and SO_{3}, and of HCl + 6H_{2}O (or of aqueous solutions analogous to it) from HCl and H_{2}O. [61] The essence of the matter may he thus represented. A gaseous or easily volatile substance _A_ forms with a certain quantity of water, _n_H_{2}O, a definite complex compound _An_H_{2}O, which is stable up to a temperature t° higher than 100°. At this temperature it is decomposed into two substances, _A_ + H_{2}O. Both boil below _t_° at the ordinary pressure, and therefore at _t_° they distil over and re-combine in the receiver. But if a part of the substance _An_H_{2}O is decomposed or volatilised, a portion of the undecomposed liquid still remains in the vessel, which can partially dissolve one of the products of decomposition, and that in quantity varying with the pressure and temperature, and therefore the solution at a constant boiling point will have a slightly different composition at different pressures. [62] For solutions of hydrochloric acid in water there are still greater differences in reactions. For instance, strong solutions decompose antimony sulphide (forming hydrogen sulphide, H_{2}S), and precipitate common salt from its solutions, whilst weak solutions do not act thus. Many compunds containing water of crystallisation are solid substances (when melted they are already solutions--_i.e._ liquids); furthermore, they are capable of being formed from solutions, like ice or aqueous vapour. They may be called _crystallo-hydrates_. Inasmuch as the direct presence of ice or aqueous vapour cannot be admitted in solutions (for these are liquids), although the presence of water may be, so also there is no basis for acknowledging the presence in solutions of crystallo-hydrates, although they are obtained from solutions as such.[63] It is evident that such substances present one of the many forms of equilibrium between water and a substance dissolved in it. This form, however, reminds one, in all respects, of solutions--that is, aqueous compounds which are more or less easily decomposed, with separation of water and the formation of a less aqueous or an anhydrous compound. In fact, there are not a few crystals containing water which lose a part of their water at the ordinary temperature. Of such a kind, for instance, are the crystals of soda, or sodium carbonate, which, when separated from an aqueous solution at the ordinary temperature, are quite transparent; but when left exposed to air, lose a portion of their water, becoming opaque, and, in the process, lose their crystalline appearance, although preserving their original form. This process of the separation of water at the ordinary temperature is termed the _efflorescence_ of crystals. Efflorescence takes place more rapidly under the receiver of an air pump, and especially at a gentle heat. This breaking up of a crystal is dissociation at the ordinary temperature. Solutions are decomposed in exactly the same manner.[64] The tension of the aqueous vapour which is given off from crystallo-hydrates is naturally, as with solutions, less than the vapour tension of water itself[65] at the same temperature, and therefore many anhydrous salts which are capable of combining with water absorb aqueous vapour from moist air; that is, they act like a cold body on which water is deposited from steam. It is on this that the desiccation of gases is based, and it must further be remarked in this respect that certain substances--for instance, potassium carbonate (K_{2}CO_{3}) and calcium chloride (CaCl_{2})--not only absorb the water necessary for the formation of a solid crystalline compound, but also give solutions, or _deliquesce_, as it is termed, in moist air. Many crystals do not effloresce in the least at the ordinary temperature; for example, copper sulphate, which may be preserved for an indefinite length of time without efflorescing, but when placed under the receiver of an air pump, if efflorescence be once started, it goes on at the ordinary temperature. The temperature at which the complete separation of water from crystals takes place varies considerably, not only for different substances, but also for different portions of the contained water. Very often the temperature at which dissociation begins is very much higher than the boiling point of water. So, for example, copper sulphate, which contains 36 p.c. of water, gives up 28·8 p.c. at 100°, and the remaining quantity, namely 7·2 p.c., only at 240°. Alum, out of the 45·5 p.c. of water which it contains, gives up 18·9 p.c. at 100°, 17·7 p.c. at 120°, 7·7 p.c. at 180°, and 1 p.c. at 280°; it only loses the last quantity (1 p.c.) at its temperature of decomposition. These examples clearly show that the annexation of water of crystallisation is accompanied by a rather profound, although, in comparison with instances which we shall consider later, still inconsiderable, change of its properties. In certain cases the water of crystallisation is only given off when the solid form of the substance is destroyed: when the crystals melt on heating. The crystals are then said _to melt in their water of crystallisation_. Further, after the separation of the water, a solid substance remains behind, so that by further heating it acquires a solid form. This is seen most clearly in crystals of sugar of lead or lead acetate, which melt in their water of crystallisation at a temperature of 56·25°, and in so doing begin to lose water. On reaching a temperature of 100° the sugar of lead solidifies, having lost all its water; and then at a temperature of 280°, the anhydrous and solidified salt again melts.[65 bis] [63] Supersaturated solutions give an excellent proof in this respect. Thus a solution of copper sulphate generally crystallises in penta-hydrated crystals, CuSO_{4} + 5H_{2}O, and its saturated solution gives such crystals if it be brought into contact with the minutest possible crystal of the same kind. But, according to the observations of Lecoq de Boisbaudran, if a crystal of ferrous sulphate (an isomorphous salt, _see_ note 55), FeSO_{4} + 7H_{2}O, be placed in a saturated solution of copper sulphate, then crystals of hepta-hydrated salt, CuSO_{4} + 7H_{2}O, are obtained. It is evident that neither the penta-nor the hepta-hydrated salt is contained as such in the solution. The solution presents its own particular liquid form of equilibrium. [64] Efflorescence, like every evaporation, proceeds from the surface. In the interior of crystals which have effloresced there is usually found a non-effloresced mass, so that the majority of effloresced crystals of washing soda show, in their fracture, a transparent nucleus coated by an effloresced, opaque, powdery mass. It is a remarkable circumstance in this respect that efflorescence proceeds in a completely regular and uniform manner, so that the angles and planes of similar crystallographic character effloresce simultaneously, and in this respect the crystalline form determines those parts of crystals where efflorescence starts, and the order in which it continues. In solutions evaporation also proceeds from the surface, and the first crystals which appear on its reaching the required degree of saturation are also formed at the surface. After falling to the bottom the crystals naturally continue to grow (_see_ Chapter X.). [65] According to Lesc[oe]ur (1883), at 100° a concentrated solution of barium hydroxide, BaH_{2}O_{2}, on first depositing crystals (with + H_{2}O) has a tension of about 630 mm. (instead of 760 mm., the tension of water), which decreases (because the solution evaporates) to 45 mm., when all the water is expelled from the crystals, BaH_{2}O_{2} + H_{2}O, which are formed, but they also lose water (dissociate, effloresce at 100°), leaving the hydroxide, BaH_{2}O_{2}, which is perfectly undecomposable at 100°--that is, does not part with water. At 73° (the tension of water is then 265 mm.) a solution, containing 33H_{2}O, on crystallising has a tension of 230 mm.; the crystals, BaH_{2}O_{2} + 8H_{2}O, which separate out, have a tension of 160 mm.; on losing water they give BaH_{2}O_{2} + H_{2}O. This substance does not decompose at 73°, and therefore its tension = 0. In those crystallohydrates which effloresce at the ordinary temperature, the tension of dissociation nearly approximates to that of the aqueous vapour, as Lesc[oe]ur (1891) showed. To this category of compounds belong B_{2}O_{3}(3 + _x_)H_{2}O, C_{2}O_{4}H_{2}(2 + _x_)H_{2}O, BaO(9 + _x_)H_{2}O, and SrO(9 + _x_)H_{2}O. And a still greater tension is possessed by Na_{2}SO_{4}10H_{2}O, Na_{2}CO_{3}10H_{2}O, and MgSO_{4}(7 + _x_)H_{2}O. Müller-Erzbach (1884) determines the tension (with reference to liquid water) by placing tubes of the same length with water and the substances experimented with in a desiccator, the rate of loss of water giving the relative tension. Thus, at the ordinary temperature, crystals of sodium phosphate, Na_{2}HPO_{4} + 12H_{2}O, present a tension of 0·7 compared with water, until they lose 5H_{2}O, then 0·4 until they lose 5H_{2}O more, and on losing the last equivalent of water the tension falls to 0·04 compared with water. It is clear that the different molecules of water are held by an unequal force. Out of the five molecules of water in copper sulphate the two first are comparatively easily separated even at the ordinary temperature (but only after several days in a desiccator, according to Latchinoff); the next two are more difficultly separated, and the last equivalent is retained even at 100°. This is another indication of the capacity of CuSO_{4} to form three hydrates, CuSO_{4}5H_{2}O, CuSO_{4}3H_{2}O, and CuSO_{4}H_{2}O. The researches of Andreae on the tension of dissociation of hydrated sulphate of copper showed (1891) the existence of three provinces, characterised at a given temperature by a constant tension: (1) between 3-5, (2) between 1-3, and lastly (3) between 0-1 molecule of water, which again confirms the existence of three hydrates of the above composition for this salt. [65 bis] Sodium acetate (C_{2}H_{3}O_{2}Na,3H_{2}O) melts at 58°, but re-solidifies only on contact with a crystal, otherwise it may remain liquid even at 0°, and may be used for obtaining a constant temperature. According to Jeannel, the latent heat of fusion is about 28 calories, and according to Pickering the heat of solution 35 calories. When melted this salt boils at 123°--that is, the tension of the vapour given off at that temperature equals the atmospheric pressure. It is most important to recognise in respect to the water of crystallisation that its ratio to the quantity of the substance with which it is combined is always a constant quantity. However often we may prepare copper sulphate, we shall always find 36·14 p.c. of water in its crystals, and these crystals always lose four-fifths of their water at 100°, and one-fifth of the whole amount of the water contained remains in the crystals at 100°, and is only expelled from them at a temperature of about 240°. What has been said about crystals of copper sulphate refers also to crystals of every other substance, which contain water of crystallisation. It is impossible in any of these cases to increase either the relative proportion of the salt or of the water, without changing the homogeneity of the substance. If once a portion of the water be lost--for instance, if once efflorescence takes place--a mixture is obtained, and not a homogeneous substance, namely a mixture of a substance deprived of water with a substance which has not yet lost water--_i.e._ decomposition has already commenced. This constant ratio is an example of the fact that in chemical compounds the quantity of the component parts is quite definite; that is, it is an example of the so-called _definite chemical compounds_. They may be distinguished from solutions, and from all other so-called indefinite chemical compounds, in that at least one, and sometimes both, of the component parts may be added in a large quantity to an indefinite chemical compound, without destroying its homogeneity, as in solutions, whilst it is impossible to add any one of the component parts to a definite chemical compound without destroying the homogeneity of the entire mass. Definite chemical compounds only decompose at a certain rise in temperature; on a lowering in temperature they do not, at least with very few exceptions, yield their components like solutions which form ice or compounds with water of crystallisation. This leads to the assumption that solutions contain water as water,[66] although it may sometimes be in a very small quantity. Therefore solutions which are capable of solidifying completely (for instance, crystallo-hydrates capable of melting) such as the compound of 84-1/2 parts of sulphuric acid, H_{2}SO_{4}, with 15-1/2 parts of water, H_{2}O, or H_{2}SO_{4},H_{2}O (or H_{4}SO_{5}), appear as true definite chemical compounds. If, then, we imagine such a definite compound in a liquid state, and admit that it partially decomposes in this state, separating water--not as ice or vapour (for then the system would be heterogeneous, including substances in different physical states), but in a liquid form, when the system will be homogeneous--we shall form an idea of a solution as an unstable, dissociating fluid state of equilibrium between water and the substance dissolved. Moreover, it should be remarked that, judging by experiment, many substances give with water not one but _diverse_ compounds,[67] which is seen in the capacity of one substance to form with water many various _crystallo-hydrates_, or compounds with water of crystallisation, showing diverse and independent properties. From these considerations, _solutions[68] may be regarded as fluid, unstable, definite chemical compounds in a state of dissociation_.[69] [66] Such a phenomenon frequently presents itself in purely chemical action. For instance, let a liquid substance _A_ give, with another liquid substance _B_, under the conditions of an experiment, a mere minute quantity of a solid or gaseous substance _C_. This small quantity will separate out (pass away from the sphere of action, as Berthollet expressed it), and the remaining masses of _A_ and _B_ will again give _C_; consequently, under these conditions action will go on to the end. Such, it seems to me, is the action in solutions when they yield ice or vapour indicating the presence of water. [67] Certain substances are capable of forming together only one compound, others several, and these of the most varied degrees of stability. The compounds of water are instances of this kind. In solutions the existence of several different definite compounds must be acknowledged, but many of these have not yet been obtained in a free state, and it may be that they cannot be obtained in any other but a liquid form--that is, dissolved; just as there are many undoubted definite compounds which only exist in one physical state. Among the hydrates such instances occur. The compound CO_{2} + 8H_{2}O (_see_ note 31), according to Wroblewski, only occurs in a solid form. Hydrates like H_{2}S + 12H_{2}O (De Forcrand and Villard), HBr + H_{2}O (Roozeboom), can only be accepted on the basis of a decrease of tension, but present themselves as very transient substances, incapable of existing in a stable free state. Even sulphuric acid, H_{2}SO_{4}, itself, which undoubtedly is a definite compound, fumes in a liquid form, giving off the anhydride, SO_{3}--that is, it exhibits a very unstable equilibrium. The crystallo-hydrates of chlorine, Cl_{2} + 8H_{2}O, of hydrogen sulphide, H_{2}S + 12H_{2}O (it is formed at 0°, and is completely decomposed at +1°, as then 1 vol. of water only dissolves 4 vols. of hydrogen sulphide, while at 0·1° it dissolves about 100 vols.), and of many other gases, are instances of hydrates which are very unstable. [68] Of such a kind are also other indefinite chemical compounds; for example, metallic alloys. These are solid substances or solidified solutions of metals. They also contain definite compounds, and may contain an excess of one of the metals. According to the experiments of Laurie (1888), the alloys of zinc with copper in respect to the electro-motive force in galvanic batteries behave just like zinc if the proportion of copper in the alloy does not exceed a certain percentage--that is, until a definite compound is attained--for in that case particles of free zinc are present; but if a copper surface be taken, and it be covered by only one-thousandth part of its area of zinc, then only the zinc will act in a galvanic battery. [69] According to the above supposition, the condition of solutions in the sense of the kinetic hypothesis of matter (that is, on the supposition of an internal motion of molecules and atoms) may be represented in the following form:--In a homogeneous liquid--for instance, water--the molecules occur in a certain state of, although mobile, still stable, equilibrium. When a substance _A_ dissolves in water, its molecules form with several molecules of water, systems _An_H_{2}O, which are so unstable that when surrounded by molecules of water they decompose and re-form, so that _A_ passes from one mass of molecules of water to another, and the molecules of water which were at this moment in harmonious motion with _A_ in the form of the system _An_H_{2}O, in the next instant may have already succeeded in getting free. The addition of water or of molecules of _A_ may either only alter the number of free molecules, which in their turn enter into systems _An_H_{2}O, or they may introduce conditions for the possibility of building up new systems _Am_H_{2}O, where _m_ is either greater or less than _n_. If in the solution the relation of the molecules be the same as in the system _Am_H_{2}O, then the addition of fresh molecules of water or of _A_ would be followed by the formation of new molecules _An_H_{2}O. The relative quantity, stability, and composition of these systems or definite compounds will vary in one or another solution. I adopted this view of solutions (1887, Pickering subsequently put forward a similar view) after a most intimate study of the variation of their specific gravities, to which my book, cited in note 19, is devoted. Definite compounds, _An__{1}H_{2}O and _Am__{1}H_{2}O, existing in a free--for instance, solid--form, may in certain cases be held in solutions in a dissociated state (although but partially); they are similar in their structure to those definite substances which are formed in solutions, but it is not necessary to assume that such systems as Na_{2}SO_{4} + 10H_{2}O, or Na_{2}SO_{4} + 7H_{2}O, or Na_{2}SO_{4}, are contained in solutions. The comparatively more stable systems _An__{1}H_{2}O which exist in a free state and change their physical state must present, although within certain limits of temperature, an entirely harmonious kind of motion of _A_ with _n__{1}H_{2}O; the property also and state of systems _An_H_{2}O and _Am_H_{2}O, occurring in solutions, is that they are in a liquid form, although partially dissociated. Substances _A__{1}, which give solutions, are distinguished by the fact that they can form such unstable systems _An_H_{2}O, but besides them they can give other much more stable systems _An__{1}H_{2}O. Thus ethylene, C_{2}H_{4}, in dissolving in water, probably forms a system C_{2}H_{4}_n_H_{2}O, which easily splits up into C_{2}H_{4} and H_{2}O, but it also gives the system of alcohol, C_{2}H_{4},H_{2}O or C_{2}H_{6}O, which is comparatively stable. Thus oxygen can dissolve in water, and it can combine with it, forming peroxide of hydrogen. Turpentine, C_{10}H_{16}, does not dissolve in water, but it combines with it as a comparatively stable hydrate. In other words, the chemical structure of hydrates, or of the definite compounds which are contained in solutions, is distinguished not only by its original peculiarities but also by a diversity of stability. A similar structure to hydrates must be acknowledged in crystallo-hydrates. On melting they give actual (real) solutions. As substances which give crystallo-hydrates, like salts, are capable of forming a number of diverse hydrates, and as the greater the number of molecules of water (_n_) they (_An_H_{2}O) contain, the lower is the temperature of their formation, and as the more easily they decompose the more water they hold, therefore, in the first place, the isolation of hydrates holding much water existing in aqueous solutions may be soonest looked for at low temperatures (although, perhaps, in certain cases they cannot exist in the solid state); and, secondly, the stability also of such higher hydrates will be at a minimum under the ordinary circumstances of the occurrence of liquid water. Hence a further more detailed investigation of cryohydrates may help to the elucidation of the nature of solutions. But it may be foreseen that certain cryohydrates will, like metallic alloys, present solidified mixtures of ice with the salts themselves and their more stable hydrates, and others will be definite compounds. In regarding solutions from this point of view they come under the head of those definite compounds with which chemistry is mainly concerned.[70] [70] The above representation of solutions, &c., considering them as a particular state of definite compounds, excludes the independent existence of indefinite compounds; by this means that unity of chemical conception is obtained which cannot be arrived at by admitting the physico-mechanical conception of indefinite compounds. The gradual transition from typical solutions (as of gases in water, and of weak saline solutions) to sulphuric acid, and from it and its definite, but yet unstable and liquid, compounds, to clearly defined compounds, such as salts and their crystallo-hydrates, is so imperceptible, that in denying that solutions pertain to the number of definite but dissociating compounds, we risk denying the definiteness of the atomic composition of such substances as sulphuric acid or of molten crystallo-hydrates. I repeat, however, that for the present the theory of solutions cannot be considered as firmly established. The above opinion about them is nothing more than a hypothesis which endeavours to satisfy those comparatively limited data which we have for the present about solutions, and of those cases of their transition into definite compounds. By submitting solutions to the Daltonic conception of atomism, I hope that we may not only attain to a general harmonious chemical doctrine, but also that new motives for investigation and research will appear in the problem of solutions, which must either confirm the proposed theory or replace it by another fuller and truer one; and I for my part cannot consider this to be the case with any of the other present doctrines of solutions (note 49). We saw above that copper sulphate loses four-fifths of its water at 100° and the remainder at 240°. This means that there are two definite compounds of water with the anhydrous salt. Washing soda or carbonate of sodium, Na_{2}CO_{3} separates out as crystals, Na_{2}CO_{3},10H_{2}O, containing 62·9 p.c. of water by weight, from its solutions at the ordinary temperature. When a solution of the same salt deposits crystals at a low temperature, about -20°, then these crystals contain 71·8 parts of water per 28·2 parts of anhydrous salt. Further, the crystals are obtained together with ice, and are left behind when it melts. If ordinary soda, with 62·9 p.c. of water, be cautiously melted in its own water of crystallisation, there remains a salt, in a solid state, containing only 14·5 p.c. of water, and a liquid is obtained which contains the solution of a salt which separates out crystals at 34°, which contain 46 p.c. of water and do not effloresce in air. Lastly, if a supersaturated solution of soda be prepared, then at temperatures below 8° it deposits crystals containing 54·3 p.c. of water. Thus as many as five compounds of anhydrous soda with water are known; and they are dissimilar in their properties and crystalline form, and even in their solubility. It is to be observed that the greatest amount of water in the crystals corresponds with a temperature of -20°, and the smallest to the highest temperature. There is apparently no relation between the above quantities of water and the salts, but this is only because in each case the amount of water and anhydrous salt was given in percentages; but if it be calculated for one and the same quantity of anhydrous salt, or of water, a great regularity will be observed in the amounts of the component parts in all these compounds. It appears that for 106 parts of anhydrous salt in the crystals separated out at -20° there are 270 parts of water; in the crystals obtained at 15° there are 180 parts of water; in the crystals obtained from a supersaturated solution 126 parts, in the crystals which separate out at 34°, 90 parts, and the crystals with the smallest amount of water, 18 parts. On comparing these quantities of water it may easily be seen that they are in simple proportion to each other, for they are all divisible by 18, and are in the ratio 15 : 10 : 7 : 5 : 1. Naturally, direct experiment, however carefully it be conducted, is hampered with errors, but taking these unavoidable experimental errors into consideration, it will be seen that for a given quantity of an anhydrous substance there occur, in several of its compounds with water, quantities of water which are in very simple multiple proportion. This is observed in, and is common to, all definite chemical compounds. This rule is called _the law of multiple proportions_. It was discovered by Dalton, and will be evolved in further detail subsequently in this work. For the present we will only state that the law of definite composition enables the composition of substances to be expressed by formulæ, and the law of multiple proportions permits the application of whole numbers as coefficients of the symbols of the elements in these formulæ. Thus the formula Na_{2}CO_{3},10H_{2}O shows directly that in this crystallo-hydrate there are 180 parts of water to 106 parts by weight of the anhydrous salt, because the formula of soda, Na_{2}CO_{3}, directly answers to a weight of 106, and the formula of water to 18 parts, by weight, which are here taken 10 times. In the above examples of the combinations of water, we saw the gradually increasing intensity of the bond between water and a substance with which it forms a homogeneous compound. There is a series of such compounds with water, in which the water is held with very great force, and is only given up at a very high temperature, and sometimes cannot be separated by any degree of heat without the entire decomposition of the substance. In these compounds there is generally no outward sign whatever of their containing water. A perfectly new substance is formed from an anhydrous substance and water, in which sometimes the properties of neither one nor the other substance are observable. In the majority of cases, a considerable amount of heat is evolved in the formation of such compounds with water. Sometimes the heat evolved is so intense that a red heat is produced and light is emitted. It is hardly to be wondered at, after this, that stable compounds are formed by such a combination. Their decomposition requires great heat; a large amount of work is necessary to separate them into their component parts. All such compounds are definite, and, generally, completely and clearly definite. The number of such definite compounds with water or _hydrates_, in the narrow sense of the word, is generally inconsiderable for each anhydrous substance; in the greater number of cases, there is formed only one such combination of a substance with water, one hydrate, having so great a stability. The water contained in these compounds is often called _water of constitution_--_i.e._ water which enters into the structure or composition of the given substance. By this it is desired to express, that in other cases the molecules of water are, as it were, separate from the molecules of that substance with which it is combined. It is supposed that in the formation of hydrates this water, even in the smallest particles, forms one complete whole with the anhydrous substance. Many examples of the formation of such hydrates might be cited. The most familiar example in practice is the hydrate of lime, or so-called 'slaked' lime. Lime is prepared by burning limestone, by which the carbonic anhydride is expelled from it, and there remains a white stony mass, which is dense, compact, and rather tenacious. Lime is usually sold in this form, and bears the name of 'quick' or 'unslaked' lime. If water be poured over such lime, a great rise in temperature is remarked either directly, or after a certain time. The whole mass becomes hot, part of the water is evaporated, the stony mass in absorbing water crumbles into powder, and if the water be taken in sufficient quantity and the lime be pure and well burnt, not a particle of the original stony mass is left--it all crumbles into powder. If the water be in excess, then naturally a portion of it remains and forms a solution. This process is called 'slaking' lime. Slaked lime is used in practice in intermixture with sand as mortar. Slaked lime is a definite hydrate of lime. If it is dried at 100° it retains 24·3 p.c. of water. This water can only be expelled at a temperature above 400°, and then quicklime is re-obtained. The heat evolved in the combination of lime with water is so intense that it can set fire to wood, sulphur, gunpowder, &c. Even on mixing lime with ice the temperature rises to 100°. If lime be moistened with a small quantity of water in the dark, a luminous effect is observed. But, nevertheless, water may still be separated from this hydrate.[71] If phosphorus be burnt in dry air, a white substance called 'phosphoric anhydride' is obtained. It combines with water with such energy, that the experiment must be conducted with great caution. A red heat is produced in the formation of the compound, and it is impossible to separate the water from the resultant hydrate at any temperature. The hydrate formed by phosphoric anhydride is a substance which is totally undecomposable into its original component parts by the action of heat. Almost as energetic a combination occurs when sulphuric anhydride, SO_{3}, combines with water, forming its hydrate, sulphuric acid, H_{2}SO_{4}. In both cases definite compounds are produced, but the latter substance, as a liquid, and capable of decomposition by heat, forms an evident link with solutions. If 80 parts of sulphuric anhydride retain 18 parts of water, this water cannot be separated from the anhydride, even at a temperature of 300°. It is only by the addition of phosphoric anhydride, or by a series of chemical transformations, that this water can be separated from its compound with sulphuric anhydride. Oil of vitriol, or sulphuric acid, is such a compound. If a larger proportion of water be taken, it will combine with the H_{2}SO_{4}; for instance, if 36 parts of water per 80 parts of sulphuric anhydride be taken, a compound is formed which crystallises in the cold, and melts at +8°, whilst oil of vitriol does not solidify even at -30°. If still more water be taken, the oil of vitriol will dissolve in the remaining quantity of water. An evolution of heat takes place, not only on the addition of the water of constitution, but in a less degree on further additions of water.[72] And therefore there is no distinct boundary, but only a gradual transition, between those chemical phenomena which are expressed in the formation of solutions and those which take place in the formation of the most stable hydrates.[73] [71] In combining with water one part by weight of lime evolves 245 units of heat. A high temperature is obtained, because the specific heat of the resulting product is small. Sodium oxide, Na_{2}O, in reacting on water, H_{2}O, and forming caustic soda (sodium hydroxide), NaHO, evolves 552 units of heat for each part by weight of sodium oxide. [72] The diagram given in note 28 shows the evolution of heat on the mixture of sulphuric acid, or monohydrate (H_{2}SO_{4}, _i.e._ SO_{3} + H_{2}O), with different quantities of water per 100 vols. of the resultant solution. Every 98 grams of sulphuric acid (H_{2}SO_{4}) evolve, on the addition of 18 grams of water, 6,379 units of heat; with twice or three times the quantity of water 9,418 and 11,137 units of heat, and with an infinitely large quantity of water 17,860 units of heat, according to the determinations of Thomsen. He also showed that when H_{2}SO_{4} is formed from SO_{3} (= 80) and H_{2}O (= 18), 21,308 units of heat are evolved per 98 parts by weight of the resultant sulphuric acid. [73] Thus, for different hydrates the stability with which they hold water is very dissimilar. Certain hydrates hold water very loosely, and in combining with it evolve little heat. From other hydrates the water cannot be separated by any degree of heat, even if they are formed from anhydrides (_i.e._ anhydrous substances) and water with little evolution of heat; for instance, acetic anhydride in combining with water evolves an inconsiderable amount of heat, but the water cannot then be expelled from it. If the hydrate (acetic acid) formed by this combination be strongly heated it either volatilises without change, or decomposes into new substances, but it does not again yield the original substances--_i.e._, the anhydride and water, at least in a liquid form. Here is an instance which gives the reason for calling the water entering into the composition of the hydrate, water of constitution. Such, for example, is the water entering into the so-called caustic soda or sodium hydroxide (_see_ note 71). But there are hydrates which easily part with their water; yet this water cannot be considered as water of crystallisation, not only because sometimes such hydrates have no crystalline form, but also because, in perfectly analogous cases, very stable hydrates are formed, which are capable of particular kinds of chemical reactions, as we shall subsequently learn. Such, for example, is the unstable hydrated oxide of copper, which is not formed from water and oxide of copper, but which is obtained just like far more stable hydrates, for example, the hydrated oxide of barium BaH_{2}O_{2} equal to BaO + H_{2}O, by the double decomposition of the solution of salts with alkalies. In a word, there is no distinct boundary either between the water of hydrates and of crystallisation, or between solution and hydration. It must be observed that in separating from an aqueous solution, many substances, without having a crystalline form, hold water in the same unstable state as in crystals; only this water cannot be termed 'water of crystallisation' if the substance which separates out has no crystalline form. The hydrates of alumina and silica are examples of such unstable hydrates. If these substances are separated from an aqueous solution by a chemical process, then they always contain water. The formation of a new chemical compound containing water is here particularly evident, for alumina and silica in an anhydrous state have chemical properties differing from those they show when combined with water, and do not combine directly with it. The entire series of colloids on separating from water form similar compounds with it, which have the aspect of solid gelatinous substances. Water is held in a considerable quantity in solidified glue or boiled albumin. It cannot be expelled from them by pressure; hence, in this case there has ensued some kind of combination of the substance with water. This water, however, is easily separated on drying; but not the whole of it, a portion being retained, and this portion is considered to belong to the hydrate, although in this case it is very difficult, if not impossible, to obtain definite compounds. The absence of any distinct boundary lines between solutions, crystallo-hydrates, and ordinary hydrates above referred to, is very clearly seen in such examples. We have thus considered many aspects and degrees of combination of various substances with water, or instances of the compounds of water, when it and other substances form new homogeneous substances, which in this case will evidently be complex--_i.e._ made up of different substances--and although they are homogeneous, yet it must be admitted that in them there exist those component parts which entered into their composition, inasmuch as these parts may be re-obtained from them. It must not be imagined that water really exists in hydrate of lime, any more than that ice or steam exists in water. When we say that water occurs in the composition of a certain hydrate, we only wish to point out that there are chemical transformations in which it is possible to obtain that hydrate by means of water, and other transformations in which this water may be separated out from the hydrate. This is all simply expressed by the words, that water enters into the composition of this hydrate. If a hydrate be formed by feeble bonds, and be decomposed even at the ordinary temperature, and be a liquid, then the water appears as one of the products of dissociation, and this gives an idea of what solutions are, and forms the fundamental distinction between them and other hydrates in which the water is combined with greater stability. CHAPTER II THE COMPOSITION OF WATER, HYDROGEN The question now arises, Is not _water_ itself a _compound substance_? Cannot it be formed by the mutual combination of some component parts? Cannot it be broken up into its component parts? There cannot be the least doubt that if it does split up, and if it is a compound, then it is a _definite_ one characterised by the stability of the union between those component parts from which it is formed. From the fact alone that water passes into all physical states as a homogeneous whole, without in the least varying chemically in its properties and without splitting up into its component parts (neither solutions nor many hydrates can be distilled--they are split up), we must conclude, from this fact alone, that if water is a compound then it is a stable and definite chemical compound capable of entering into many other combinations. Like many other great discoveries in the province of chemistry, it is to the end of the last century that we are indebted for the important discovery that water is not a simple substance, that it is composed of two substances like a number of other compound substances. This was proved by two of the methods by which the compound nature of bodies may be directly determined; by analysis and by synthesis--that is, by a method of the decomposition of water into, and of the formation of water from, its component parts. In 1781 Cavendish first obtained water by burning hydrogen in oxygen, both of which gases were already known to him. He concluded from this that water was composed of two substances. But he did not make more accurate experiments, which would have shown the relative quantities of the component parts in water, and which would have determined its complex nature with certainty. Although his experiments were the first, and although the conclusion he drew from them was true, yet such novel ideas as the complex nature of water are not easily recognised so long as there is no series of researches which entirely and indubitably proves the truth of such a conclusion. The fundamental experiments which proved the complexity of water by the method of synthesis, and of its formation from other substances, were made in 1789 by Monge, Lavoisier, Fourcroy, and Vauquelin. They obtained four ounces of water by burning hydrogen, and found that water consists of 15 parts of hydrogen and 85 parts of oxygen. It was also proved that the weight of water formed was equal to the sum of the weights of the component parts entering into its composition; consequently, water contains all the matter entering into oxygen and hydrogen. The complexity of water was proved in this manner by a method of synthesis. But we will turn to its analysis--_i.e._ to its decomposition into its component parts. The analysis may be more or less complete. Either both component parts may be obtained in a separate state, or else only one is separated and the other is converted into a new compound in which its amount may be determined by weighing. This will be a reaction of substitution, such as is often taken advantage of for analysis. The first analysis of water was thus conducted in 1784 by Lavoisier and Meusnier. The apparatus they arranged consisted of a glass retort containing water previously purified, and of which the weight had been determined. The neck of the retort was inserted into a porcelain tube, placed inside an oven, and heated to a red heat by charcoal. Iron filings, which decompose water at a red heat, were placed inside this tube. The end of the tube was connected with a worm, for condensing any water which might pass through the tube undecomposed. This condensed water was collected in a separate flask. The gas formed by the decomposition was collected over water in a bell jar. The aqueous vapour in passing over the red-hot iron was decomposed, and a gas was formed from it whose weight could be determined from its volume, its density being known. Besides the water which passed through the tube unaltered, a certain quantity of water disappeared in the experiment, and this quantity, in the experiments of Lavoisier and Meusnier, was equal to the weight of gas which was collected in the bell jar plus the increase in weight of the iron filings. Hence the water was decomposed into a gas, which was collected in the bell jar, and a substance, which combined with the iron; consequently, it is composed of these two component parts. This was the first analysis of water ever made; but here only one (and not both) of the gaseous component parts of water was collected separately. Both the component parts of water can, however, be simultaneously obtained in a free state. For this purpose the decomposition is brought about by a galvanic current or by heat, as we shall learn directly.[1] [1] The first experiments of the synthesis and decomposition of water did not afford, however, an entirely convincing proof that water was composed of hydrogen and oxygen only. Davy, who investigated the decomposition of water by the galvanic current, thought for a long time that, besides the gases, an acid and alkali were also obtained. He was only convinced of the fact that water contains nothing but hydrogen and oxygen by a long series of researches, which showed him that the appearance of an acid and alkali in the decomposition of water proceeds from the presence of impurities (especially from the presence of ammonium nitrate) in water. A final comprehension of the composition of water is obtained from the accurate determination of the quantities of the component parts which enter into its composition. It will be seen from this how many data are necessary for proving the composition of water--that is, of the transformations of which it is capable. What has been said of water refers to all other compounds; the investigation of each one, the entire proof of its composition, can only be obtained by the accumulation of a large mass of data referring to it. Water is a bad conductor of electricity--that is, pure water does not transmit a feeble current; but if any salt or acid be dissolved in it, then its conductivity increases, and _on the passage of a current_ through acidified water _it is decomposed_ into its component parts. Some sulphuric acid is generally added to the water. By immersing platinum plates (electrodes) in this water (platinum is chosen because it is not acted on by acids, whilst many other metals are chemically acted on by acids), and connecting them with a galvanic battery, it will be observed that bubbles of gas appear on these plates. The gas which separates is called _detonating gas_,[2] because, on ignition, it very easily explodes.[3] What takes place is as follows:--First, the water, by the action of the current, is decomposed into two gases. The mixture of these gases forms detonating gas. When detonating gas is brought into contact with an incandescent substance--for instance, a lighted taper--the gases re-combine, forming water, the combination being accompanied by a great evolution of heat, and therefore the vapour of the water formed expands considerably, which it does very rapidly, and as a consequence, an explosion takes place--that is, sound and increase of pressure, and atmospheric disturbance, as in the explosion of gunpowder. [2] This gas is collected in a voltameter. [3] In order to observe this explosion without the slightest danger, it is best to proceed in the following manner. Some soapy water is prepared, so that it easily forms soap bubbles, and it is poured into an iron trough. In this water, the end of a gas-conducting tube is immersed. This tube is connected with any suitable apparatus, in which detonating gas is evolved. Soap bubbles, full of this gas, are then formed. If the apparatus in which the gas is produced be then removed (otherwise the explosion might travel into the interior of the apparatus), and a lighted taper be brought to the soap bubbles, a very sharp explosion takes place. The bubbles should be small to avoid any danger; ten, each about the size of a pea, suffice to give a sharp report, like a pistol shot. In order to discover what gases are obtained by the decomposition of water, the gases which separate at each electrode must be collected separately. For this purpose a V-shaped tube is taken; one of its ends is open and the other fused up. A platinum wire, terminating inside the tube in a plate, is fused into the closed end; the closed end is entirely filled with water[4] acidified with sulphuric acid, and another platinum wire, terminating in a plate, is immersed in the open end. If a current from a galvanic battery be now passed through the wires an evolution of gases will be observed, and the gas which is obtained in the open branch passes into the air, while that in the closed branch accumulates above the water. As this gas accumulates it displaces the water, which continues to descend in the closed and ascend into the open branch of the tubes. When the water, in this way, reaches the top of the open end, the passage of the current is stopped, and the gas which was evolved from one of the electrodes only is obtained in the apparatus. By this means it is easy to prove that a particular gas appears at each electrode. If the closed end be connected with the negative pole--_i.e._ with that joined to the zinc--then the gas collected in the apparatus is capable of burning. This may be demonstrated by the following experiment:--The bent tube is taken off the stand, and its open end stopped up with the thumb and inclined in such a manner that the gas passes from the closed to the open end. It will then be found, on applying a lighted lamp or taper, that the gas burns. This combustible gas is _hydrogen_. If the same experiment be carried on with a current passing in the opposite direction--that is, if the closed end be joined up with the positive pole (_i.e._ with the carbon, copper, or platinum), then the gas which is evolved from it does not itself burn, but it supports combustion very vigorously, so that a smouldering taper in it immediately bursts into flame. This gas, which is collected at the anode or positive pole, is _oxygen_, which is obtained, as we saw before (in the Introduction), from mercury oxide and is contained in air. [4] In order to fill the tube with water, it is turned up, so that the closed end points downwards and the open end upwards, and water acidified with sulphuric acid is poured into it. Thus in the decomposition of water oxygen appears at the positive pole and hydrogen at the negative pole,[4 bis] so that detonating gas will be a mixture of both. Hydrogen burns in air from the fact that in doing so it re-forms water, with the oxygen of the air. Detonating gas explodes from the fact that the hydrogen burns in the oxygen mixed with it. It is very easy to measure the relative quantities of one and the other gas which are evolved in the decomposition of water. For this purpose a funnel is taken, whose orifice is closed by a cork through which two platinum wires pass. These wires are connected with a battery. Acidified water is poured into the funnel, and a glass cylinder full of water is placed over the end of each wire (fig. 18). On passing a current, hydrogen and oxygen collect in these cylinders, and it will easily be seen that two volumes of hydrogen are evolved for every one volume of oxygen. This signifies that, in decomposing, water gives two volumes of hydrogen and one volume of oxygen. [4 bis] Owing to the gradual but steady progress made during the last twenty-five years in the production of an electric current from the dynamo and its transmission over considerable distances, the electrolytic decomposition of many compound bodies has acquired great importance, and the use of the electric current is making its way into many chemical manufactures. Hence, Prof. D. A. Lachinoff's proposal to obtain hydrogen and oxygen (both of which have many applications) by means of electrolysis (either of a 10 to 15 per cent. solution of caustic soda or a 15 per cent. solution of sulphuric acid) may find a practical application, at all events in the future. In general, owing to their simplicity, electrolytic methods have a great future, but as yet, so long as the production of an electric current remains so costly, their application is limited. And for this reason, although certain of these methods are mentioned in this work, they are not specially considered, the more so since a profitable and proper use of the electric current for chemical purposes requires special electro-technical knowledge which beginners cannot he assumed to have, and therefore, an exposition of the principles of electrotechnology as applied, to the production of chemical transformations, although referred to in places, does not come within the scope of the present work. [Illustration: FIG. 18.--Decomposition of water by the galvanic current, for determining the relation between the volumes of hydrogen and oxygen.] Water is also decomposed into its component parts by _the action of heat_. At the melting point of silver (960°), and in its presence, water is decomposed and the oxygen absorbed by the molten silver, which dissolves it so long as it is liquid. But directly the silver solidifies the oxygen is expelled from it. However, this experiment is not entirely convincing; it might be thought that in this case the decomposition of the water did not proceed from the action of heat, but from the action of the silver on water--that silver decomposes water, taking up the oxygen. If steam be passed through a red-hot tube, whose internal temperature attains 1,000°, then a portion[5] of the water decomposes into its component parts, forming detonating gas. But on passing into the cooler portions of the apparatus this detonating gas again reunites and forms water. The hydrogen and oxygen obtained combine together at a lower temperature.[6] Apparently the problem--to show the decomposability of water at high temperatures--is unattainable. It was considered as such before Henri Sainte-Claire Deville (in the fifties) introduced the conception of dissociation into chemistry, as of a change of chemical state resembling evaporation, if decomposition be likened to boiling, and before he had demonstrated the decomposability of water by the action of heat in an experiment which will presently be described. In order to demonstrate clearly the _dissociation_ of water, or its decomposability by heat, at a temperature approaching that at which it is formed, it was necessary to separate the hydrogen from the oxygen at a high temperature, without allowing the mixture to cool. Deville took advantage of the difference between the densities of hydrogen and oxygen. [5] As water is formed by the combination of oxygen and hydrogen, with a considerable evolution of heat, and as it can also be decomposed, this reaction is a reversible one (_see_ Introduction), and consequently at a high temperature the decomposition of water cannot be complete--it is limited by the opposite reaction. Strictly speaking, it is not known how much water is decomposed at a given temperature, although many efforts (Bunsen, and others) have been made in various directions to solve this question. Not knowing the coefficient of expansion, and the specific heat of gases at such high temperatures, renders all calculations (from observations of the pressure on explosion) doubtful. [6] Grove, in 1847, observed that a platinum wire fused in the oxyhydrogen flame--that is, having acquired the temperature of the formation of water--and having formed a molten drop at its end which fell into water, evolved detonating gas--that is, decomposed water. It therefore follows that water already decomposes at the temperature of its formation. At that time, this formed a scientific paradox; this we shall unravel only with the development of the conceptions of dissociation, introduced into science by Henri Sainte-Claire Deville, in 1857. These conceptions form an important epoch in science, and their development is one of the problems of modern chemistry. The essence of the matter is that, at high temperatures, water exists but also decomposes, just as a volatile liquid, at a certain temperature, exists both as a liquid and as a vapour. Similarly as a volatile liquid saturates a space, attaining its maximum tension, so also the products of dissociation have their maximum tension, and once that is attained decomposition ceases, just as evaporation ceases. Under like conditions, if the vapour be allowed to escape (and therefore its partial pressure be diminished), evaporation recommences, so also if the products of decomposition be removed, decomposition again continues. These simple conceptions of dissociation introduce infinitely varied consequences into the mechanism of chemical reactions, and therefore we shall have occasion to return to them very often. We may add that Grove also concluded that water was decomposed at a white heat, from the fact that he obtained detonating gas by passing steam through a tube with a wire heated strongly by an electric current, and also by passing steam over molten oxide of lead, he obtained, on the one hand, litharge (= oxide of lead and oxygen), and on the other, metallic lead formed by the action of hydrogen. [Illustration: FIG. 19.--Decomposition of water by the action of heat, and the separation of the hydrogen formed by its permeating through a porous tube.] A wide porcelain tube P (fig. 19) is placed in a furnace, which can be raised to a high temperature (it should be heated with small pieces of good coke). In this tube there is inserted a second tube T, of smaller diameter, made of unglazed earthenware and therefore porous. The ends of the tube are luted to the wide tube, and two tubes, C and C', are inserted into the ends, as shown in the drawing. With this arrangement it is possible for a gas to pass into the annular space between the walls of the two tubes, from whence it can be collected. Steam from a retort or flask is passed through the tube D, into the inner porous tube T. This steam on entering the red-hot space is decomposed into hydrogen and oxygen. The densities of these gases are very different, hydrogen being sixteen times lighter than oxygen. Light gases, as we saw above, penetrate through porous surfaces very much more rapidly than denser gases, and therefore the hydrogen passes through the pores of the tube into the annular space very much more rapidly than the oxygen. The hydrogen which separates out into the annular space can only be collected when this space does not contain any oxygen. If any air remains in this space, then the hydrogen which separates out will combine with its oxygen and form water. For this reason a gas incapable of supporting combustion--for instance, nitrogen or carbonic anhydride--is previously passed into the annular space. Thus the carbonic anhydride is passed through the tube C, and the hydrogen, separated from the steam, is collected through the tube C', and will be partly mixed with carbonic anhydride. A certain portion of the carbonic anhydride will penetrate through the pores of the unglazed tube into the interior of the tube T. The oxygen will remain in this tube, and the volume of the remaining oxygen will be half that of the volume of hydrogen which separates out from the annular space.[6 bis] [6 bis] Part of the oxygen will also penetrate through the pores of the tube; but, as was said before, a much smaller quantity than the hydrogen, and as the density of oxygen is sixteen times greater than that of hydrogen, the volume of oxygen which passes through the porous walls will be four times less than the volume of hydrogen (the quantities of gases passing through porous walls are inversely proportional to the square roots of their densities). The oxygen which separates out into the annular space will combine, at a certain fall of temperature, with the hydrogen; but as each volume of oxygen only requires two volumes of hydrogen, whilst at least four volumes of hydrogen will pass through the porous walls for every volume of oxygen that passes, therefore, part of the hydrogen will remain free, and can be collected from the annular space. A corresponding quantity of oxygen remaining from the decomposition of the water can be collected from the internal tube. The decomposition of water is effected much more easily by a method of substitution, taking advantage of the affinity of substances for the oxygen or the hydrogen of water. If a substance be added to water, which takes up the oxygen and replaces the hydrogen--then we shall obtain the latter gas from the water. Thus with sodium, water gives hydrogen, and with chlorine, which takes up the hydrogen, oxygen is obtained. Hydrogen is evolved from water by many metals, which are capable of forming oxides in air--that is, which are capable of burning or combining with oxygen. The capacity of metals for combining with oxygen, and therefore for decomposing water, or for the evolution of hydrogen, is very dissimilar.[7] Among metals, potassium and sodium exhibit considerable energy in this respect. The first occurs in potash, the second in soda. They are both lighter than water, soft, and easily change in air. By bringing one or the other of them in contact with water at the ordinary temperature,[8] a quantity of hydrogen, corresponding with the amount of the metal taken, may be directly obtained. One gram of hydrogen, occupying a volume of 11·16 litres at 0° and 760 mm., is evolved from every 39 grams of potassium, or 23 grams of sodium. The phenomenon may be observed in the following way: a solution of sodium in mercury--or 'sodium amalgam,' as it is generally called--is poured into a vessel containing water, and owing to its weight sinks to the bottom; the sodium held in the mercury then acts on the water like pure sodium, liberating hydrogen. The mercury does not act here, and the same amount of it as was taken for dissolving the sodium is obtained in the residue. The hydrogen is evolved gradually in the form of bubbles, which pass through the liquid. [7] In order to demonstrate the difference of the affinity of oxygen for different elements, it is enough to compare the amounts of heats which are evolved in their combination with 16 parts by weight of oxygen; in the case of sodium (when Na_{2}O is formed, or 46 parts of Na combine with 16 parts of oxygen, according to Beketoff) 100,000 calories (or units of heat), are evolved, for hydrogen (when water, H_{2}O, is formed) 69,000 calories, for iron (when the oxide FeO is formed) 69,000, and if the oxide Fe_{2}O_{3} is formed, 64,000 calories, for zinc (ZnO is formed) 86,000 calories, for lead (when PbO is formed) 51,000 calories, for copper (when CuO is formed) 38,000 calories, and for mercury (HgO is formed) 31,000 calories. These figures cannot correspond directly with the magnitude of the affinities, for the physical and mechanical side of the matter is very different in the different cases. Hydrogen is a gas, and, in combining with oxygen, gives a liquid; consequently it changes its physical state, and, in doing so, evolves heat. But zinc and copper are solids, and, in combining with oxygen, give solid oxides. The oxygen, previously a gas, now passes into a solid or liquid state, and, therefore, also must have given up its store of heat in forming oxides. As we shall afterwards see, the degree of contraction (and consequently of mechanical work) was different in the different cases, and therefore the figures expressing the heat of combination cannot directly depend on the affinities, on the loss of internal energy previously in the elements. Nevertheless, the figures above cited correspond, in a certain degree, with the order in which the elements stand in respect to their affinity for oxygen, as may be seen from the fact that the mercury oxide, which evolves the least heat (among the above examples), is the least stable is easily decomposed, giving up its oxygen; whilst sodium, the formation of whose oxide is accompanied by the greatest evolution of heat, is able to decompose all the other oxides, taking up their oxygen. In order to generalise the connection between affinity and the evolution and the absorption of heat, which is evident in its general features, and was firmly established by the researches of Favre and Silbermann (about 1840), and then of Thomsen (in Denmark) and Berthelot (in France), many investigators, especially the one last mentioned, established the _law of maximum work_. This states that only those chemical reactions take place of their own accord in which the greatest amount of chemical (latent, potential) energy is transformed into heat. But, in the first place, we are not able, judging from what has been said above, to distinguish that heat which corresponds with purely chemical action from the sum total of the heat observed in a reaction (in the calorimeter); in the second place, there are evidently endothermal reactions which proceed under the same circumstances as exothermal (carbon burns in the vapour of sulphur with absorption of heat, whilst in oxygen it evolves heat); and, in the third place, there are reversible reactions, which when taking place in one direction evolve heat, and when taking place in the opposite direction absorb it; and, therefore, the principle of maximum work in its elementary form is not supported by science. But the subject continues to be developed, and will probably lead to a general law, such as thermal chemistry does not at present possess. [8] If a piece of metallic sodium be thrown into water, it floats on it (owing to its lightness), keeps in a state of continual motion (owing to the evolution of hydrogen on all sides), and immediately decomposes the water, evolving hydrogen, which can be lighted. This experiment may, however, lead to an explosion should the sodium stick to the walls of the vessel, and begin to act on the limited mass of water immediately adjacent to it (probably in this case NaHO forms with Na, Na_{2}O, which acts on the water, evolving much heat and rapidly forming steam), and the experiment should therefore be carried on with caution. The decomposition of water by sodium may he better demonstrated, and with greater safety, in the following manner. Into a glass cylinder filled with mercury, and immersed in a mercury bath, water is first introduced, which will, owing to its lightness, rise to the top, and then a piece of sodium wrapped in paper is introduced with forceps into the cylinder. The metal rises through the mercury to the surface of the water, on which it remains, and evolves hydrogen, which collects in the cylinder, and may be tested after the experiment has been completed. The safest method of making this experiment is, however, as follows. The sodium (cleaned from the naphtha in which it is kept) is either wrapped in fine copper gauze and held by forceps, or else held in forceps at the end of which a small copper cage is attached, and is then held under water. The evolution of hydrogen goes on quietly, and it may he collected in a bell jar and then lighted. Beyond the hydrogen evolved and a solid substance, which remains in solution (it may be obtained by evaporating the resultant solution) no other products are here obtained. Consequently, from the two substances (water and sodium) taken, the same number of new substances (hydrogen and the substance dissolved in water) have been obtained, from which we may conclude that the reaction which here takes place is a reaction of double decomposition or of substitution. The resultant solid is nothing else but the so-called caustic soda (sodium hydroxide), which is made up of sodium, oxygen, and half of the hydrogen contained in the water. Therefore, the substitution took place between the hydrogen and the sodium, namely half of the hydrogen in the water was replaced by the sodium, and was evolved in a free state. Hence the reaction which takes place here may be expressed by the equation H_{2}O + Na = NaHO + H; the meaning of this is clear from what has already been said.[9] [9] This reaction is vigorously exothermal, _i.e._ it is accompanied by the evolution of heat. If a sufficient quantity of water be taken the whole of the sodium hydroxide, NaHO, formed is dissolved, and about 42,500 units of heat are evolved per 23 grams of sodium taken. As 40 grams of sodium hydroxide are produced, and they in dissolving, judging from direct experiment, evolve about 10,000 calories; therefore, without an excess of water, and without the formation of a solution, the reaction would evolve about 32,500 calories. We shall afterwards learn that hydrogen contains in its smallest isolable particles H_{2} and not H, and therefore it follows that the reaction should be written thus--2Na + 2H_{2}O = H_{2} + 2NaOH, and it then corresponds with an evolution of heat of +65,000 calories. And as N. N. Beketoff showed that Na_{2}O, or anhydrous oxide of sodium, forms the hydrate, or sodium hydroxide (caustic soda), 2NaHO, with water, evolving about 35,500 calories, therefore the reaction 2Na + H_{2}O = H_{2} + Na_{2}O corresponds to 29,500 calories. This quantity of heat is less than that which is evolved in combining with water, in the formation of caustic soda, and therefore it is not to be wondered at that the hydrate, NaHO, is always formed and not the anhydrous substance Na_{2}O. That such a conclusion, which agrees with facts, is inevitable is also seen from the fact that, according to Beketoff, the anhydrous sodium oxide, Na_{2}O, acts directly on hydrogen, with separation of sodium, Na_{2}O + H = NaHO + Na. This reaction is accompanied by an evolution of heat equal to about 3,000 calories, because Na_{2}O + H_{2}O gives, as we saw, 35,500 calories and Na + H_{2}O evolves 32,500 calories. However, an opposite reaction also takes place--NaHO + Na = Na_{2}O + H (both with the aid of heat)--consequently, in this case heat is absorbed. In this we see an example of calorimetric calculations and the limited application of the law of maximum work for the general phenomena of reversible reactions, to which the case just considered belongs. But it must be remarked that all reversible reactions evolve or absorb but little heat, and the reason of the law of maximum work, not being universal must first of all be looked for in the fact that we have no means of separating the heat which corresponds with the purely chemical process from the sum total of the heat observed, and as the structure of a number of substances is altered by heat and also by contact, we can scarcely hope that the time approaches when such a distinction will be possible. A heated substance, in point of fact, has no longer the original energy of its atoms--that is, the act of heating not only alters the store of motion of the molecules but also of the atoms forming the molecules, in other words, it makes the beginning of or preparation for chemical change. From this it must be concluded that thermochemistry, or the study of the heat accompanying chemical transformations, cannot he identified with chemical mechanics. Thermo-chemical data form a part of it, but they alone cannot give it. Sodium and potassium act on water at the ordinary temperature. Other heavier metals only act on it with a rise of temperature, and then not so rapidly or vigorously. Thus magnesium and calcium only liberate hydrogen from water at its boiling point, and zinc and iron only a red heat, whilst a whole series of heavy metals, such as copper, lead, mercury, silver, gold, and platinum, do not in the least decompose water at any temperature, and do not replace its hydrogen. From this it is clear that hydrogen may be obtained by the decomposition of steam by the action of iron (or zinc) with a rise of temperature. The experiment is conducted in the following manner: pieces of iron (filings, nails, &c.), are placed in a porcelain tube, which is then subjected to a strong heat and steam passed through it. The steam, coming into contact with the iron, gives up its oxygen to it, and thus the hydrogen is set free and passes out at the other end of the tube together with undecomposed steam. This method, which is historically very significant,[10] is practically inconvenient, as it requires a rather high temperature. Further, this reaction, as a reversible one (a red-hot mass of iron decomposes a current of steam, forming oxide and hydrogen; and a mass of oxide of iron, heated to redness in a stream of hydrogen, forms iron and steam), does not proceed in virtue of the comparatively small difference between the affinity of oxygen for iron (or zinc) and for hydrogen, but only because the hydrogen escapes, as it is formed, in virtue of its elasticity.[11] If the oxygen compounds--that is, the oxides--which are obtained from the iron or zinc, be able to pass into solution, then the affinity acting in solution is added, and the reaction may become non-reversible, and proceed with comparatively much greater facility.[12] As the oxides of iron and zinc, by themselves insoluble in water, are capable of combining with (have an affinity for) acid oxides (as we shall afterwards fully consider), and form saline and soluble substances, with acids, or hydrates having acid properties, hence by the action of such hydrates, or of their aqueous solutions,[13] iron and zinc are able to liberate hydrogen with great ease at the ordinary temperature--that is, they act on solutions of acids just as sodium acts on water.[14] Sulphuric acid, H_{2}SO_{4}, is usually chosen for this purpose; the hydrogen is displaced from it by many metals with much greater facility than directly from water, and such a displacement is accompanied by the evolution of a large amount of heat.[15] When the hydrogen in sulphuric acid is replaced by a metal, a substance is obtained which is called a salt of sulphuric acid or a sulphate. Thus, by the action of zinc on sulphuric acid, hydrogen and zinc sulphate ZnSO_{4},[15 bis] are obtained. The latter is a solid substance, soluble in water. In order that the action of the metal on the acid should go on regularly, and to the end, it is necessary that the acid should be diluted with water, which dissolves the salt as it is formed; otherwise the salt covers the metal, and hinders the acid from attacking it. Usually the acid is diluted with from three to five times its volume of water, and the metal is covered with this solution. In order that the metal should act rapidly on the acid, it should present a large surface, so that a maximum amount of the reacting substances may come into contact in a given time. For this purpose the zinc is used as strips of sheet zinc, or in the granulated form (that is, zinc which has been poured from a certain height, in a molten state, into water). The iron should be in the form of wire, nails, filings, or cuttings. [Illustration: FIG. 20.--Apparatus for the preparation of hydrogen from zinc and sulphuric acid.] [10] The composition of water, as we saw above, was determined by passing steam over red-hot iron; the same method has been used for making hydrogen for filling balloons. An oxide having the composition Fe_{3}O_{4} is formed in the reaction, so that it is expressed by the equation 3Fe + 4H_{2}O = Fe_{3}O_{4} + 8H. [11] The reaction between iron and water (note 10) is reversible. By heating the oxide in a current of hydrogen, water and iron are obtained. From this it follows, from the principle of chemical equilibria, that if iron and hydrogen be taken, and also oxygen, but in such a quantity that it is insufficient for combination with both substances, then it will divide itself between the two; part of it will combine with the iron and the other part with the hydrogen, but a portion of both will remain in an uncombined state. Therefore, if iron and water be placed in a closed space, decomposition of the water will proceed on heating to the temperature at which the reaction 3Fe + 4H_{2}O = Fe_{3}O_{4} + 8H commences; but it ceases, does not go on to the end, because the conditions for a reverse reaction are attained, and a state of equilibrium will ensue after the decomposition of a certain quantity of water. Here again (_see_ note 9) the reversibility is connected with the small heat effect, and again both reactions (direct and reverse) proceed at a red heat. But if, in the above-described reaction, the hydrogen escapes as it is evolved, then its partial pressure does not increase with its formation, and therefore all the iron can he oxidised by the water. In this we see the elements of that influence of mass to which we shall have occasion to return later. With copper and lead there will be no decomposition, either at the ordinary or at a high temperature, because the affinity of these metals for oxygen is much less than that of hydrogen. [12] In general, if reversible as well as non-reversible reactions can take place between substances acting on each other, then, judging by our present knowledge, the non-reversible reactions take place in the majority of cases, which obliges one to acknowledge the action, in this case, of comparatively strong affinities. The reaction, Zn + H_{2}SO_{4} = H_{2} + ZnSO_{4}, which takes place in solutions at the ordinary temperature, is scarcely reversible under these conditions, but at a certain high temperature it becomes reversible, because at this temperature zinc sulphate and sulphuric acid split up, and the action must take place between the water and zinc. From the preceding proposition results proceed which are in some cases verified by experiment. If the action of zinc or iron on a solution of sulphuric acid presents a non-reversible reaction, then we may by this means obtain hydrogen in a very compressed state, and compressed hydrogen will not act on solutions of sulphates of the above-named metals. This is verified in reality as far as was possible in the experiments to keep up the compression or pressure of the hydrogen. Those metals which do not evolve hydrogen with acids, on the contrary, should, at least at an increase of pressure, be displaced by hydrogen. And in fact Brunner showed that gaseous hydrogen displaces platinum and palladium from the aqueous solutions of their chlorine compounds, but not gold, and Beketoff succeeded in showing that silver and mercury, under a considerable pressure, are separated from the solutions of certain of their compounds by means of hydrogen. Reaction already commences under a pressure of six atmospheres, if a weak solution of silver sulphate be taken; with a stronger solution a much greater pressure is required, however, for the separation of the silver. [13] For the same reason, many metals in acting on solutions of the alkalis displace hydrogen. Aluminium acts particularly clearly in this respect, because its oxide gives a soluble compound with alkalis. For the same reason tin, in acting on hydrochloric acid, evolves hydrogen, and silicon does the same with hydrofluoric acid. It is evident that in such cases the sum of all the affinities plays a part; for instance, taking the action of zinc on sulphuric acid, we have the affinity of zinc for oxygen (forming zinc oxide, ZnO), the affinity of its oxide for sulphuric anhydride, SO_{3} (forming zinc sulphate, ZnSO_{4}), and the affinity of the resultant salt, ZnSO_{4}, for water. It is only the first-named affinity that acts in the reaction between water and the metal, if no account is taken of those forces (of a physico-mechanical character) which act between the molecules (for instance, the cohesion between the molecules of the oxide) and those forces (of a chemical character) which act between the atoms forming the molecule, for instance, between the atoms of hydrogen giving the molecule H_{2} containing two atoms. I consider it necessary to remark, that the hypothesis of the affinity or endeavour of heterogeneous atoms to enter into a common system and in harmonious motion (_i.e._ to form a compound molecule) must inevitably be in accordance with the hypothesis of forces including homogeneous atoms to form complex molecules (for instance, H_{2}), and to build up the latter into solid or liquid substances, in which the existence of an attraction between the homogeneous particles must certainly be admitted. Therefore, those forces which bring about solution must also be taken into consideration. These are all forces of one and the same series, and in this may be seen the great difficulties surrounding the study of molecular mechanics and its province--chemical mechanics. [14] It is acknowledged that zinc itself acts on water, even at the ordinary temperature, but that the action is confined to small masses and only proceeds at the surface. In reality, zinc, in the form of a very fine powder, or so-called 'zinc dust,' is capable of decomposing water with the formation of oxide (hydrated) and hydrogen. The oxide formed acts on sulphuric acid, water then dissolves the salt produced, and the action continues because one of the products of the action of water on zinc, zinc oxide, is removed from the surface. One might naturally imagine that the reaction does not proceed directly between the metal and water, but between the metal and the acid, but such a simple representation, which we shall cite afterwards, hides the mechanism of the reaction, and does not permit of its actual complexity being seen. [15] According to Thomsen the reaction between zinc and a very weak solution of sulphuric acid evolves about 38,000 calories (zinc sulphate being formed) per 65 parts by weight of zinc; and 56 parts by weight of iron--which combine, like 65 parts by weight of zinc, with 16 parts by weight of oxygen--evolve about 25,000 calories (forming ferrous sulphate, FeSO_{4}). Paracelsus observed the action of metals on acids in the seventeenth century; but it was not until the eighteenth century that Lémery determined that the gas which is evolved in this action is a particular one which differs from air and is capable of burning. Even Boyle confused it with air. Cavendish determined the chief properties of the gas discovered by Paracelsus. At first it was called 'inflammable air'; later, when it was recognised that in burning it gives water, it was called hydrogen, from the Greek words for water and generator. [15 bis] If, when the sulphuric acid is poured over the zinc, the evolution of the hydrogen proceed too slowly, it may be greatly accelerated by adding a small quantity of a solution of CuSO_{4} or PtCl_{4} to the acid. The reason of this is explained in Chap. XVI., note 10 bis. The usual method of obtaining hydrogen is as follows:--A certain quantity of granulated zinc is put into a double-necked, or Woulfe's, bottle. Into one neck a funnel is placed, reaching to the bottom of the bottle, so that the liquid poured in may prevent the hydrogen from escaping through it. The gas escapes through a special gas conducting tube, which is firmly fixed, by a cork, into the other neck, and ends in a water bath (fig. 20), under the orifice of a glass cylinder full of water.[16] If sulphuric acid be now poured into the Woulfe's bottle it will soon be seen that bubbles of a gas are evolved, which is hydrogen. The first part of the gas evolved should not be collected, as it is mixed with the air originally in the apparatus. This precaution should be taken in the preparation of all gases. Time must be allowed for the gas evolved to displace all the air from the apparatus, otherwise in testing the combustibility of the hydrogen an explosion may occur from the formation of detonating gas (the mixture of the oxygen of the air with the hydrogen).[17] [16] As laboratory experiments with gases require a certain preliminary knowledge, we will describe certain _practical methods for the collection and preparation of gases_. When in laboratory practice an intermittent supply of hydrogen (or other gas which is evolved without the aid of heat) is required the apparatus represented in fig. 21 is the most convenient. It consists of two bottles, having orifices at the bottom, in which corks with tubes are placed, and these tubes are connected by an india-rubber tube (sometimes furnished with a spring clamp). Zinc is placed in one bottle, and dilute sulphuric acid in the other. The neck of the former is closed by a cork, which is fitted with a gas-conducting tube with a stopcock. If the two bottles are connected with each other and the stopcock be opened, the acid will flow to the zinc and evolve hydrogen. If the stopcock be closed, the hydrogen will force out the acid from the bottle containing the zinc, and the action will cease. Or the vessel containing the acid may be placed at a lower level than that containing the zinc, when all the liquid will flow into it, and in order to start the action the acid vessel may be placed on a higher level than the other, and the acid will flow to the zinc. It can also be employed for collecting gases (as an aspirator or gasometer). [Illustration: FIG. 21.--A very convenient apparatus for the preparation of gases obtained without heat. It may also replace an aspirator or gasometer.] In laboratory practice, however, other forms of apparatus are generally employed for exhausting, collecting, and holding gases. We will here cite the most usual forms. An _aspirator_ usually consists of a vessel furnished with a stopcock at the bottom. A stout cork, through which a glass tube passes, is fixed into the neck of this vessel. If the vessel be filled up with water to the cork and the bottom stopcock is opened, then the water will run out and draw gas in. For this purpose the glass tube is connected with the apparatus from which it is desired to pump out or exhaust the gas. [Illustration: FIG. 22.--Continuous aspirator. The tube _d_ should be more than 32 feet long.] The aspirator represented in fig. 22 may be recommended for its continuous action. It consists of a tube _d_ which widens out at the top, the lower part being long and narrow. In the expanded upper portion _c_, two tubes are sealed; one, _e_, for drawing in the gas, whilst the other, _b_, is connected to the water supply _w_. The amount of water supplied through the tube _b_ must be less than the amount which can be carried off by the tube _d_. Owing to this the water in the tube _d_ will flow through it in cylinders alternating with cylinders of gas, which will be thus carried away. The gas which is drawn through may be collected from the end of the tube _d_, but this form of pump is usually employed where the air or gas aspirated is not to be collected. If the tube _d_ is of considerable length, say 40 ft. or more, a very fair vacuum will be produced, the amount of which is shown by the gauge _g_; it is often used for filtering under reduced pressure, as shown in the figure. If water be replaced by mercury, and the length of the tube _d_ be greater than 760 mm., the aspirator may be employed as an air-pump, and all the air may be exhausted from a limited space; for instance, by connecting _g_ with a hollow sphere. [Illustration: FIG. 23.--Gasholder.] _Gasholders_ are often used for collecting and holding gases. They are made of glass, copper, or tin plate. The usual form is shown in fig. 23. The lower vessel _B_ is made hermetically tight--_i.e._, impervious to gases--and is filled with water. A funnel is attached to this vessel (on several supports). The vessel _B_ communicates with the bottom of the funnel by a stopcock _b_ and a tube _a_, reaching to the bottom of the vessel _B_. If water be poured into the funnel and the stopcocks _a_ and _b_ opened, the water will run through _a_, and the air escape from the vessel _B_ by _b_. A glass tube _f_ runs up the side of the vessel _B_, with which it communicates at the top and bottom, and shows the amount of water and gas the gasholder contains. In order to fill the gasholder with a gas, it is first filled with water, the cocks _a_, _b_ and _e_ are closed, the nut _d_ unscrewed, and the end of the tube conducting the gas from the apparatus in which it is generated is passed into _d_. As the gas fills the gasholder, the water runs out at _d_. If the pressure of a gas be not greater than the atmospheric pressure and it be required to collect it in the gasholder, then the stopcock _e_ is put into communication with the space containing the gas. Then, having opened the orifice _d_, the gasholder acts like an aspirator; the gas will pass through _e_, and the water run out at _d_. If the cocks be closed, the gas collected in the gasholder may be easily preserved and transported. If it be desired to transfer this gas into another vessel, then a gas-conducting tube is attached to _e_, the cock _a_ opened, _b_ and _d_ closed, and the gas will then pass out at _e_, owing to its pressure in the apparatus being greater than the atmospheric pressure, due to the pressure of the water poured into the funnel. If it be required to fill a cylinder or flask with the gas, it is filled with water and inverted in the funnel, and the stopcocks _b_ and _a_ opened. Then water will run through _a_, and the gas will escape from the gasholder into the cylinder through _b_. [17] When it is required to prepare hydrogen in large quantities for filling balloons, copper vessels or wooden casks lined with lead are employed; they are filled with scrap iron, over which dilute sulphuric acid is poured. The hydrogen generated from a number of casks is carried through lead pipes into special casks containing water (in order to cool the gas) and lime (in order to remove acid fumes). To avoid loss of gas all the joints are made hermetically tight with cement or tar. In order to fill his gigantic balloon (of 25,000 cubic metres capacity), Giffard, in 1878, constructed a complicated apparatus for giving a continuous supply of hydrogen, in which a mixture of sulphuric acid and water was continually run into vessels containing iron, and from which the solution of iron sulphate formed was continually drawn off. When coal gas, extracted from coal, is employed for filling balloons, it should be as light, or as rich in hydrogen, as possible. For this reason, only the last portions of the gas coming from the retorts are collected, and, besides this, it is then sometimes passed through red-hot vessels, in order to decompose the hydrocarbons as much as possible; charcoal is deposited in the red-hot vessels, and hydrogen remains as gas. Coal gas may be yet further enriched in hydrogen, and consequently rendered lighter, by passing it over an ignited mixture of charcoal and lime. L. Mond (London) proposes to manufacture hydrogen on a large scale from water gas (_see infra_, and Chapters VIII. and IX.), which contains a mixture of oxide of carbon (CO) and hydrogen, and is produced by the action of steam upon incandescent coke (C + H_{2}O = CO + H_{2}). He destroys the oxide of carbon by converting it into carbon and carbonic anhydride (2CO = C + CO_{2}), which is easily done by means of incandescent, finely-divided metallic nickel; the carbon then remains with the nickel, from which it may be removed by burning it in air, and the nickel can then be used over again (_see_ Chapter IX., Note 24 bis). The CO_{2} formed is removed from the hydrogen by passing it through milk of lime. This process should apparently give hydrogen on a large scale more economically than any of the methods hitherto proposed. Hydrogen, besides being contained in water, is also contained in many other substances,[18] and may be obtained from them. As examples of this, it may be mentioned (1) that a mixture of formate of sodium, CHNaO_{2}, and caustic soda, NaHO, when heated to redness, forms sodium carbonate, Na_{2}CO_{3}, and hydrogen, H_{2};[19] (2) that a number of organic substances are decomposed at a red heat, forming hydrogen, among other gases, and thus it is that hydrogen is contained in ordinary coal gas. [18] Of the metals, only a very few combine with hydrogen (for example, sodium), and give substances which are easily decomposed. Of the non-metals, the halogens (fluorine, chlorine, bromine, and iodine) most easily form hydrogen compounds; of these the hydrogen compound of chlorine, and still more that of fluorine, is stable, whilst those of bromine and iodine are easily decomposed, especially the latter. The other non-metals--for instance, sulphur, carbon, and phosphorus--give hydrogen compounds of different composition and properties, but they are all less stable than water. The number of the carbon compounds of hydrogen is enormous, but there are very few among them which are not decomposed, with separation of the carbon and hydrogen, at a red heat. [19] The reaction expressed by the equation CNaHO_{2} + NaHO = CNa_{2}O_{3} + H_{2} may be effected in a glass vessel, like the decomposition of copper carbonate or mercury oxide (_see_ Introduction); it is non-reversible, and takes place without the presence of water, and therefore Pictet (_see_ later) made use of it to obtain hydrogen under great pressure. Charcoal itself liberates hydrogen from steam at a high temperature;[20] but the reaction which here takes place is distinguished by a certain complexity, and will therefore be considered later. [20] The reaction between charcoal and superheated steam is a double one--that is, there may be formed either carbonic oxide, CO (according to the equation H_{2}O + C = H_{2} + CO), or carbonic anhydride CO_{2} (according to the equation 2H_{2}O + C = 2H_{2} + CO_{2}), and the resulting mixture is called _water-gas_; we shall speak of it in Chapter IX. _The properties of hydrogen._--Hydrogen presents us with an example of a gas which at first sight does not differ from air. It is not surprising, therefore, that Paracelsus, having discovered that an aëriform substance is obtained by the action of metals on sulphuric acid, did not determine exactly its difference from air. In fact, hydrogen, like air, is colourless, and has no smell;[21] but a more intimate acquaintance with its properties proves it to be entirely different from air. The first sign which distinguishes hydrogen from air is its combustibility. This property is so easily observed that it is the one to which recourse is usually had in order to recognise hydrogen, if it is evolved in a reaction, although there are many other combustible gases. But before speaking of the combustibility and other chemical properties of hydrogen, we will first describe the physical properties of this gas, as we did in the case of water. It is easy to show that it is one of the lightest gases.[22] If passed into the bottom of a flask full of air, hydrogen will not remain in it, but, owing to its lightness, rapidly escapes and mixes with the atmosphere. If, however, a cylinder whose orifice is turned downwards be filled with hydrogen, it will not escape, or, more correctly, it will only slowly mix with the atmosphere. This may be demonstrated by the fact that a lighted taper sets fire to the hydrogen at the orifice of the cylinder, and is itself extinguished inside the cylinder. Hence, hydrogen, being itself combustible, does not support combustion. The great lightness of hydrogen is taken advantage of for balloons. Ordinary coal gas, which is often also used for the same purpose, is only about twice as light as air, whilst hydrogen is 14-1/2 times lighter than air. A very simple experiment with soap bubbles very well illustrates the application of hydrogen for filling balloons. Charles, of Paris, showed the lightness of hydrogen in this way, and constructed a balloon filled with hydrogen almost simultaneously with Montgolfier. One litre of pure and dry hydrogen[23] at 0° and 760 mm. pressure weighs 0·08986 gram; that is, hydrogen is almost 14-1/2 (more exactly, 14·39) times lighter than air. It is the lightest of all gases. The small density of hydrogen determines many remarkable properties which it shows; thus, hydrogen passes exceedingly rapidly through fine orifices, its molecules (Chapter I.) being endued with the greatest velocity.[24] At pressures somewhat higher than the atmospheric pressure, all other gases exhibit a greater compressibility and co-efficient of expansion than they should according to the laws of Mariotte and Gay-Lussac; whilst hydrogen, on the contrary, is compressed to a less degree than it should be from the law of Mariotte,[25] and with a rise of pressure it expands slightly less than at the atmospheric pressure.[26] However, hydrogen, like air and many other gases which are permanent at the ordinary temperature, does not pass into a liquid state under a very considerable pressure,[27] but is compressed into a lesser volume than would follow from Mariotte's law.[28] From this it may be concluded that the absolute boiling point of hydrogen, and of gases resembling it,[29] lies very much below the ordinary temperature; that is, that the liquefaction of this _gas_ is only possible at low temperatures, and under great pressures.[30] This conclusion was verified (1877) by the experiments of Pictet and Cailletet.[31] They compressed gases at a very low temperature, and then allowed them to expand, either by directly decreasing the pressure or by allowing them to escape into the air, by which means the temperature fell still lower, and then, just as steam when rapidly rarefied[32] deposits liquid water in the form of a fog, hydrogen in expanding forms a fog, thus indicating its passage into a liquid state. But as yet it has been impossible to preserve this liquid, even for a short time, to determine its properties, notwithstanding the employment of a temperature of -200° and a pressure of 200 atmospheres,[33] although by these means the gases of the atmosphere may be kept in a liquid state for a long time. This is due to the fact that the absolute boiling point of hydrogen lies lower than that of all other known gases, which also depends on the extreme lightness of hydrogen.[34] [21] Hydrogen obtained by the action of zinc or iron on sulphuric acid generally smells of hydrogen sulphide (like rotten eggs), which it contains in admixture. As a rule such hydrogen is not so pure as that obtained by the action of an electric current or of sodium on water. The impurity of the hydrogen depends on the impurities contained in the zinc, or iron, and sulphuric acid, and on secondary reactions which take place simultaneously with the main reaction. Impure hydrogen may be easily freed from the impurities it contains: some of them--namely, those having acid properties--are absorbed by caustic soda, and therefore may be removed by passing the hydrogen through a solution of this substance; another series of impurities is absorbed by a solution of mercuric chloride; and, lastly, a third series is absorbed by a solution of potassium permanganate. If absolutely _pure hydrogen_ be required, it is sometimes obtained by the decomposition of water (previously boiled to expel all air, and mixed with pure sulphuric acid) by the galvanic current. Only the gas evolved at the negative electrode is collected. Or else, an apparatus like that which gives detonating gas is used, the positive electrode, however, being immersed under mercury containing zinc in solution. The oxygen which is evolved at this electrode then immediately, at the moment of its evolution, combines with the zinc, and this compound dissolves in the sulphuric acid and forms zinc sulphate, which remains in solution, and therefore the hydrogen generated will be quite free from oxygen. [22] An inverted beaker is attached to one arm of the beam of a tolerably sensitive balance, and its weight counterpoised by weights in the pan attached to the other arm, If the beaker be then filled with hydrogen it rises, owing to the air being replaced by hydrogen. Thus, at the ordinary temperature of a room, a litre of air weighs about 1·2 gram, and on replacing the air by hydrogen a decrease in weight of about 1 gram per litre is obtained. Moist hydrogen is heavier than dry--for aqueous vapour is nine times heavier than hydrogen. In filling balloons it is usually calculated that (it being impossible to have perfectly dry hydrogen or to obtain it quite free from air) the lifting force due to the difference between the weights of equal volumes of hydrogen and air is equal to 1 kilogram (= 1,000 grams) per cubic metre (= 1,000 litres). [23] The density of hydrogen in relation to the air has been repeatedly determined by accurate experiments. The first determination, made by Lavoisier, was not very exact; taking the density of air as unity, he obtained 0·0769 for that of hydrogen--that is, hydrogen as thirteen times lighter than air. More accurate determinations are due to Thomsen, who obtained the figure 0·0693; Berzelius and Dulong, who obtained 0·0688; and Dumas and Boussingault, who obtained 0·06945. Regnault, and more recently Le Duc (1892), took two spheres of considerable capacity, which contained equal volumes of air (thus avoiding the necessity of any correction for weighing them in air). Both spheres were attached to the scale pans of a balance. One was sealed up, and the other first weighed empty and then full of hydrogen. Thus, knowing the weight of the hydrogen filling the sphere, and the capacity of the sphere, it was easy to find the weight of a litre of hydrogen; and, knowing the weight of a litre of air at the same temperature and pressure, it was easy to calculate the density of hydrogen. Regnault, by these experiments, found the average density of hydrogen to be 0·06926 in relation to air; Le Duc, 0·06948 (with a possible error of ±0·00001), and this latter figure must now be looked upon as near to the truth. In this work I shall always refer the densities of all gases to hydrogen, and not to air; I will therefore give, for the sake of clearness, the weight of a litre of dry pure hydrogen in grams at a temperature _t_° and under a pressure _H_ (measured in millimetres of mercury at 0°, in lat. 45°). The weight of a litre of hydrogen = 0·08986 × (_H_/760) × 1/(1 + 0·00367_t_) gram. For aëronauts it is very useful to know, besides this, the weight of the air at different heights, and I therefore insert the adjoining table, constructed on the basis of Glaisher's data, for the temperature and moisture of the atmospheric strata in clear weather. All the figures are given in the metrical system--1,000 millimetres = 39·37 inches, 1,000 kilograms = 2204·3375 lbs., 1,000 cubic metres = 35,316·6 cubic feet. The starting temperature at the earth's surface is taken as = 15° C., its moisture 60 p.c., pressure 760 millimetres. The pressures are taken as indicated by an _aneroid barometer_, assumed to be corrected at the sea level and at lat. 45° C. If the height above the level of the sea equal _z_ kilometres, then the weight of 1 cubic metre of air may be approximately taken as 1·222- 0·12_z_ + 0·00377_z_^2 kilogram. +--------+-----------+--------+--------+--------------------+ |Pressure|Temperature|Moisture| Height | Weight of the air | | | | |(metres)|(1,000 cubic metres)| |--------+-----------+--------+--------+--------------------+ | 760 mm.| 15° C. | 60 p.c.| 0 | 1222 kilos. | | 700 " | 11·0° " | 64 " | 690 | 1141 " | | 650 " | 7·6° " | 64 " | 1300 | 1073 " | | 600 " | 4·3° " | 63 " | 1960 | 1003 " | | 550 " | -1·0° " | 62 " | 2660 | 931 " | | 500 " | -2·4° " | 58 " | 3420 | 857 " | | 450 " | -5·8° " | 52 " | 4250 | 781 " | | 400 " | -9·1° " | 44 " | 5170 | 703 " | | 350 " | -12·5° " | 36 " | 6190 | 624 " | | 300 " | -15·9° " | 27 " | 7360 | 542 " | | 250 " | -19·2° " | 18 " | 8720 | 457 " | +--------+-----------+--------+--------+--------------------+ Although the figures in this table are calculated with every possible care from average data, yet they can only be taken approximately, for in every separate case the conditions, both at the earth's surface and in the atmosphere, will differ from those here taken. In calculating the height to which a balloon can ascend, it is evident that the density of gas in relation to air must be known. This density for ordinary coal gas is from 0·6 to 0·35, and for hydrogen with its ordinary contents of moisture and air from 0·1 to 0·15. Hence, for instance, it may be calculated that a balloon of 1,000 cubic metres capacity filled with pure hydrogen, and weighing (the envelope, tackle, people, and ballast) 727 kilograms, will only ascend to a height of about 4,250 metres. [24] If a cracked flask be filled with hydrogen and its neck immersed under water or mercury, then the liquid will rise up into the flask, owing to the hydrogen passing through the cracks about 3·8 times quicker than the air is able to pass through these cracks into the flask. The same phenomenon may be better observed if, instead of a flask, a tube be employed, whose end is closed by a porous substance, such as graphite, unglazed earthenware, or a gypsum plate. [25] According to Boyle and Mariotte's law, for a given gas at a constant temperature the volume decreases by as many times as the pressure increases; that is, this law requires that the product of the volume _v_ and the pressure _p_ for a given gas should be a constant quantity: _pv_ = _C_, a constant quantity which does not vary with a change of pressure. This equation does very nearly and exactly express the observed relation between the volume and pressure, but only within comparatively small variations of pressure, density, and volume. If these variations be in any degree considerable, the quantity _pv_ proves to be dependent on the pressure, and it either increases or diminishes with an increase of pressure. In the former case the compressibility is less than it should he according to Mariotte's law, in the latter case it is greater. We will call the first case a positive discrepancy (because then _d(pv)/d(p)_ is greater than zero), and the second case a negative discrepancy (because then _d(pv)/d(p)_ is less than zero). Determinations made by myself (in the seventies), M. L. Kirpicheff, and V. A. Hemilian showed that all known gases at low pressures--_i.e._ when considerably rarefied--present positive discrepancies. On the other hand, it appears from the researches of Cailletet, Natterer, and Amagat that all gases under great pressures (when the volume obtained is 500-1,000 times less than under the atmospheric pressure) also present positive discrepancies. Thus under a pressure of 2,700 atmospheres air is compressed, not 2,700 times, but only 800, and hydrogen 1,000 times. Hence the positive kind of discrepancy is, so to say, normal to gases. And this is easily intelligible. If a gas followed Mariotte's law, or if it were compressed to a greater extent than is shown by this law, then under great pressures it would attain a density greater than that of solid and liquid substances, which is in itself improbable and even impossible by reason of the fact that solid and liquid substances are themselves but little compressible. For instance, a cubic centimetre of oxygen at 0° and under the atmospheric pressure weighs about 0·0014 gram, and at a pressure of 3,000 atmospheres (this pressure is attained in guns) it would, if it followed Mariotte's law, weigh 4·2 grams--that is, would be about four times heavier than water--and at a pressure of 10,000 atmospheres it would be heavier than mercury. Besides this, positive discrepancies are probable because the molecules of a gas themselves must occupy a certain volume. Considering that Mariotte's law, strictly speaking, applies only to the intermolecular space, we can understand the necessity of positive discrepancies. If we designate the volume of the molecules of a gas by _b_ (like van der Waals, _see_ Chap. I., Note 34), then it must be expected that _p(v-b) = C_. Hence _pv = C + bp_, which expresses a positive discrepancy. Supposing that for hydrogen _pv_ = 1,000, at a pressure of one metre of mercury, according to the results of Regnault's, Amagat's, and Natterer's experiments, we obtain _b_ as approximately 0·7 to 0·9. Thus the increase of _pv_ with the increase of pressure must be considered as the normal law of the compressibility of gases. Hydrogen presents such a positive compressibility at all pressures, for it presents positive discrepancies from Mariotte's law, according to Regnault, at all pressures above the atmospheric pressure. Hence hydrogen is, so to say, a perfect gas. No other gas behaves so simply with a change of pressure. All other gases at pressures from 1 to 30 atmospheres present negative discrepancies--that is, they are then compressed to a greater degree than should follow from Mariotte's law, as was shown by the determinations of Regnault, which were verified when repeated by myself and Boguzsky. Thus, for example, on changing the pressure from 4 to 20 metres of mercury--that is, on increasing the pressure five times--the volume only decreased 4·93 times when hydrogen was taken, and 5·06 when air was taken. The positive discrepancies from the law at low pressures are of particular interest, and, according to the above-mentioned determinations made by myself, Kirpicheff, and Hemilian, and verified (by two methods) by K. D. Kraevitch and Prof. Ramsay (London, 1894), they are proper to all gases (even to those which are easily compressed into a liquid state, such as carbonic and sulphurous anhydrides). These discrepancies approach the case of a very high rarefaction of gases, where a gas is near to a condition of maximum dispersion of its molecules, and perhaps presents a passage towards the substance termed 'luminiferous ether' which fills up interplanetary and interstellar space. If we suppose that gases are rarefiable to a definite limit only, having attained which they (like solids) do not alter in volume with a decrease of pressure, then on the one hand the passage of the atmosphere at its upper limits into a homogeneous ethereal medium becomes comprehensible, and on the other hand it would be expected that gases would, in a state of high rarefaction (_i.e._ when small masses of gases occupy large volumes, or when furthest removed from a liquid state), present positive discrepancies from Boyle and Mariotte's law. Our present acquaintance with this province of highly rarefied gases is very limited (because direct measurements are exceedingly difficult to make, and are hampered by possible errors of experiment, which may be considerable), and its further development promises to elucidate much in respect to natural phenomena. To the three states of matter (solid, liquid, and gaseous) it is evident a fourth must yet be added, the ethereal or ultra-gaseous (as Crookes proposed), understanding by this, matter in its highest possible state of rarefaction. [26] The law of Gay-Lussac states that all gases in all conditions present one coefficient of expansion 0·00367; that is, when heated from 0° to 100° they expand like air; namely, a thousand volumes of a gas measured at 0° will occupy 1367 volumes at 100°. Regnault, about 1850, showed that Gay-Lussac's law is not entirely correct, and that different gases, and also one and the same gas at different pressures, have not quite the same coefficients of expansion. Thus the expansion of air between 0° and 100° is 0·367 under the ordinary pressure of one atmosphere, and at three atmospheres it is 0·371, the expansion of hydrogen is 0·366, and of carbonic anhydride 0·37. Regnault, however, did not directly determine the change of volume between 0° and 100°, but measured the variation of tension with the change of temperature; but since gases do not entirely follow Mariotte's law, the change of volume cannot be directly judged by the variation of tension. The investigations carried on by myself and Kayander, about 1870, showed the variation of volume on heating from 0° to 100° under a constant pressure. These investigations confirmed Regnault's conclusion that Gay-Lussac's law is not entirely correct, and further showed (1) that the expansion per volume from 0° to 100° under a pressure of one atmosphere, for air = 0·368, for hydrogen = 0·367, for carbonic anhydride = 0·373, for hydrogen bromide = 0·386, &c.; (2) that for gases which are more compressible than should follow from Mariotte's law the expansion by heat increases with the pressure--for example, for air at a pressure of three and a half atmospheres, it equals 0·371, for carbonic anhydride at one atmosphere it equals 0·373, at three atmospheres 0·389, and at eight atmospheres 0·413; (3) that for gases which are less compressible than should follow from Mariotte's law, the expansion by heat decreases with an increase of pressure--for example, for hydrogen at one atmosphere 0·367, at eight atmospheres 0·369, for air at a quarter of an atmosphere 0·370, at one atmosphere 0·368; and hydrogen like _air_ (and all gases) is less compressed _at low pressures_ than should follow from Mariotte's law (_see_ Note 25). Hence, hydrogen, starting from zero to the highest pressures, exhibits a gradually, although only slightly, varying coefficient of expansion, whilst for air and other gases at the atmospheric and higher pressures, the coefficient of expansion increases with the increase of pressure, so long as their compressibility is greater than should follow from Mariotte's law. But when at considerable pressures, this kind of discrepancy passes into the normal (_see_ Note 25), then the coefficient of expansion of all gases decreases with an increase of pressure, as is seen from the researches of Amagat. The difference between the two coefficients of expansion, for a constant pressure and for a constant volume, is explained by these relations. Thus, for example, for air at a pressure of one atmosphere the true coefficient of expansion (the volume varying at constant pressure) = 0·00368 (according to Mendeléeff and Kayander) and the variation of tension (at a constant volume, according to Regnault) = 0·00367. [27] Permanent gases are those which cannot be liquefied by an increase of pressure alone. With a rise of temperature, all gases and vapours become permanent gases. As we shall afterwards learn, carbonic anhydride becomes a permanent gas at temperatures above 31°, and at lower temperatures it has a maximum tension, and may be liquefied by pressure alone. _The liquefaction_ of gases, accomplished by Faraday (_see_ Ammonia, Chapter VI.) and others, in the first half of this century, showed that a number of substances are capable, like water, of taking all three physical states, and that there is no essential difference between vapours and gases, the only distinction being that the boiling points (or the temperature at which the tension = 760 mm.) of liquids lie above the ordinary temperature, and those of liquefied gases below, and consequently a gas is a superheated vapour, or vapour heated above the boiling point, or removed from saturation, rarefied, having a lower tension than that maximum which is proper to a given temperature and substance. We will here cite the _maximum tensions_ of certain liquids and gases _at various temperatures_, because they may be taken advantage of for obtaining constant temperatures by changing the pressure at which boiling or the formation of saturated vapours takes place. (I may remark that the dependence between the tension of the saturated vapours of various substances and the temperature is very complex, and usually requires three or four independent constants, which vary with the nature of the substance, and are found from the dependence of the tension _p_ on the temperature _t_ given by experiment; but in 1892 K. D. Kraevitch showed that this dependence is determined by the properties of a substance, such as its density, specific heat, and latent heat of evaporation.) The temperatures (according to the air thermometer) are placed on the left, and the tension in millimetres of mercury (at 0°) on the right-hand side of the equations. Carbon bisulphide, CS_{2}, 0° = 127·9; 10° = 198·5; 20° = 298·1; 30° = 431·6; 40° = 617·5; 50° = 857·1. Chlorobenzene, C_{6}H_{5}Cl, 70° = 97·9; 80° = 141·8; 90° = 208·4; 100° = 292·8; 110° = 402·6; 120° = 542·8; 130° = 719·0. Aniline, C_{6}H_{7}N, 150° = 283·7; 160° = 387·0; 170° = 515·6; 180° = 677·2; 185° = 771·5. Methyl salicylate, C_{8}H_{8}O_{3}, 180° = 294·4; 190° = 330·9; 200° = 432·4; 210° = 557·5; 220° = 710·2; 224° = 779·9. Mercury, Hg, 300° = 246·8; 310° = 304·9; 320° = 373·7; 330° = 454·4; 340° = 548·6; 350° = 658·0; 359° = 770·9. Sulphur, S, 395° = 300; 423° = 500; 443° = 700; 452° = 800; 459° = 900. These figures (Ramsay and Young) show the possibility of obtaining constant temperatures in the vapours of boiling liquids by altering the pressure. We may add the following boiling points under a pressure of 760 mm. (according to the air thermometer by Collendar and Griffiths, 1891): aniline, 184° = 13; naphthalene, 217° = 94; benzophenone, 305° = 82; mercury, 356° = 76; triphenyl-methane, 356° = 44; sulphur, 444° = 53. And melting points: tin, 231° = 68; bismuth, 269° = 22; lead, 327° = 69; and zinc, 417° = 57. These data may be used for obtaining a constant temperature and for verifying thermometers. The same object may be attained by the melting points of certain salts, determined according to the air thermometer by V. Meyer and Riddle (1893): NaCl, 851°; NaBr, 727°; NaI, 650°; KCl, 760°; KBr, 715°; KI, 623°; K_{2}CO_{3}, 1045°; Na_{2}CO_{3}, 1098°; Na_{2}B_{4}O_{7}, 873°; Na_{2}SO_{4}, 843°; K_{2}SO_{4}, 1073°. The tension of liquefied gases is expressed in atmospheres. Sulphurous anhydride, SO_{2},-30° = 0·4;-20° = 0·6;-10° = 1; 0° = 1·5; +10° = 2·3; 20° = 3·2; 30° = 5·3. Ammonia, NH_{3},-40° = 0·7;-30° = 1·1;-20° = 1·8; -10° = 2·8; 0° = 4·2; +10° = 6·0; 20° = 8·4. Carbonic anhydride, CO_{2},-115° = 0·033; -80° = 1;-70° = 2·1;-60° = 3·9;-50° = 6·8;-40° = 10;-20° = 23; 0° = 35; +10° = 46; 20° = 58. Nitrous oxide, N_{2}O,-125° = 0·033;-92° = 1;-80° = 1·9;-50° = 7·6; -20° = 23·1; 0° = 36·1; +20° = 55·3. Ethylene, C_{2}H_{4},-140° = 0·033;-130° = 0·1; -103° = 1;-40° = 13;-1° = 42. Air,-191° = 1;-158° = 14;-140° = 39. Nitrogen, N_{2},-203° = 0·085;-193° = 1;-160° = 14;-146° = 32. The methods of liquefying gases (by pressure and cold) will be described under ammonia, nitrous oxide, sulphurous anhydride, and in later footnotes. We will now turn our attention to the fact that the evaporation of volatile liquids, under various, and especially under low, pressures, gives an easy means for obtaining _low temperatures_. Thus liquefied carbonic anhydride, under the ordinary pressure, reduces the temperature to -80°, and when it evaporates in a rarefied atmosphere (under an air-pump) to 25 mm. (= 0·033 atmosphere) the temperature, judging by the above-cited figures, falls to -115° (Dewar). Even the evaporation of liquids of common occurrence, under low pressures easily attainable with an air-pump, may produce low temperatures, which may be again taken advantage of for obtaining still lower temperatures. Water boiling in a vacuum becomes cold, and under a pressure of less than 4·5 mm. it freezes, because its tension at 0° is 4·5 mm. A sufficiently low temperature may be obtained by forcing fine streams of air through common ether, or liquid carbon bisulphide, CS_{2}, or methyl chloride, CH_{3}Cl, and other similar volatile liquids. In the adjoining table are given, for certain gases, (1) the number of atmospheres necessary for their liquefaction at 15°, and (2) the boiling points of the resultant liquids under a pressure of 760 mm. C_{2}H_{4} N_{2}O CO_{2}, H_{2}S (1) 42 31 52 10 (2) -103° -92° -80° -74° AsH_{3}, NH_{3} HCl CH_{3}Cl C_{2}N_{2} SO_{2} (1) 8 7 25 4 4 3 (2) -58° -38° -35° -24° -21° -10° [28] Natterer's determinations (1851-1854), together with Amagat's results (1880-1888), show that the compressibility of hydrogen, under high pressures, may be expressed by the following figures:-- _p_ = 1 100 1000 2500 _v_ = 1 0·0107 0·0019 0·0013 _pv_ = 1 1·07 1·9 3·25 _s_ = 0·11 10·3 58 85 where _p_ = the pressure in metres of mercury, _v_ = the volume, if the volume taken under a pressure of 1 metre = 1, and _s_ the weight of a litre of hydrogen at 20° in grams. If hydrogen followed Mariotte's law, then under a pressure of 2,500 metres, one litre would contain not 85, but 265 grams. It is evident from the above figures that the weight of a litre of the gas approaches a limit as the pressure increases, which is doubtless the density of the gas when liquefied, and therefore the weight of a litre of liquid hydrogen will probably be near 100 grams (density about 0·1, being less than that of all other liquids). [29] Cagniard de Latour, on heating ether in a closed tube to about 190°, observed that at this temperature the liquid is transformed into vapour occupying the original volume--that is, having the same density as the liquid. The further investigations made by Drion and myself showed that every liquid has such an _absolute boiling point_, above which it cannot exist as a liquid and is transformed into a dense gas. In order to grasp the true signification of this absolute boiling temperature, it must be remembered that the liquid state is characterised by a cohesion of its particles which does not exist in vapours and gases. The cohesion of liquids is expressed in their capillary phenomena (the breaks in a column of liquid, drop formation, and rise in capillary tubes, &c.), and the product of the density of a liquid into the height to which it rises in a capillary tube (of a definite diameter) may serve as the measure of the magnitude of cohesion. Thus, in a tube of 1 mm. diameter, water at 15° rises (the height being corrected for the meniscus) 14·8 mm., and ether at _t°_ to a height 5·35-0·028_t°_ mm. The cohesion of a liquid is lessened by heating, and therefore the capillary heights are also diminished. It has been shown by experiment that this decrement is proportional to the temperature, and hence by the aid of capillary observations we are able to form an idea that at a certain rise of temperature the cohesion may become = 0. For ether, according to the above formula, this would occur at 191°. If the cohesion disappear from a liquid it becomes a gas, for cohesion is the only point of difference between these two states. A liquid in evaporating and overcoming the force of cohesion absorbs heat. Therefore, the absolute boiling point was defined by me (1861) as that temperature at which (_a_) a liquid cannot exist as a liquid, but forms a gas which cannot pass into a liquid state under any pressure whatever; (_b_) cohesion = 0; and (_c_) the latent heat of evaporation = 0. This definition was but little known until Andrews (1869) explained the matter from another aspect. Starting from gases, he discovered that carbonic anhydride cannot be liquefied by any degree of compression at temperatures above 31°, whilst at lower temperatures it can be liquefied. He called this temperature the _critical temperature_. It is evident that it is the same as the absolute boiling point. We shall afterwards designate it by _tc_. At low temperatures a gas which is subjected to a pressure greater than its maximum tension (Note 27) is transformed into a liquid, which, in evaporating, gives a saturated vapour possessing this maximum tension; whilst at temperatures above tc the pressure to which the gas is subjected may increase indefinitely. However, under these conditions the volume of the gas does not change indefinitely but approaches a definite limit (_see_ Note 28)--that is, it resembles in this respect a liquid or a solid which is altered but little in volume by pressure. The volume which a liquid or gas occupies at _tc_ is termed the _critical volume_, and corresponds with the _critical pressure_, which we will designate by _pc_ and express in atmospheres. It is evident from what has been said that the discrepancies from Mariotte and Boyle's law, the absolute boiling point, the density in liquid and compressed gaseous states, and the properties of liquids, must all he intimately connected together. We will consider these relations in one of the following notes. At present we will supplement the above observations by the values of _tc_ and _pc_ for certain liquids and gases which have been investigated in this respect-- +---------------------+------++----------------------+------+ | _tc_ | _pc_ || _tc_ | _pc_ | +---------------------+------++----------------------+------+ | N_{2} -146° | 33 || H_{2}S +108° | 92 | | CO -140° | 39 || C_{2}N_{2} +124° | 62 | | O_{2} -119° | 50 || NH_{3} +131° | 114 | | CH_{4} -100° | 50 || CH_{3}Cl +141° | 73 | | NO -93° | 71 || SO_{2} +155° | 79 | | C_{2}H_{4} +10° | 51 || C_{5}H_{10} +192° | 34 | | CO_{2} +32° | 77 || C_{4}H_{10}O +193° | 40 | | N_{2}O +53° | 75 || CHCl_{3} +268° | 55 | | C_{2}H_{2} +37° | 68 || CS_{2} +278° | 78 | | HCl +52° | 86 || C_{6}H_{6} +292° | 60 | | H_{2}O +365° | 200 || C_{6}H_{5}F +287° | 45 | | CH_{3}OH +240° | 79 || C_{6}H_{5}Cl +360° | 45 | | C_{2}H_{5}OH +243° | 63 || C_{6}H_{5}Br +397° | 45 | | CH_{3}COOH +322° | 57 || C_{6}H_{5}I +448° | 45 | +---------------------+------++----------------------+------+ Young and Guy (1891) showed that _tc_ and _pc_ clearly depend upon the composition and molecular weight. [30] I came to this conclusion in 1870 (_Ann. Phys. Chem._ 141, 623). [31] Pictet, in his researches, effected the direct liquefaction of many gases which up to that time had not been liquefied. He employed the apparatus used for the manufacture of ice on a large scale, employing the vaporisation of liquid sulphurous anhydride, which may be liquefied by pressure alone. This anhydride is a gas which is transformed into a liquid at the ordinary temperature under a pressure of several atmospheres (_see_ Note 27), and boils at -10° at the ordinary atmospheric pressure. This liquid, like all others, boils at a lower temperature under a diminished pressure, and by continually pumping out the gas which comes off by means of a powerful air-pump its boiling point falls as low as -75°. Consequently, if on the one hand we force liquid sulphurous anhydride into a vessel, and on the other hand pump out the gas from the same vessel by powerful air-pumps, then the liquefied gas will boil in the vessel, and cause the temperature in it to fall to -75°. If a second vessel is placed inside this vessel, then another gas may be easily liquefied in it at the low temperature produced by the boiling liquid sulphurous anhydride. Pictet in this manner easily liquefied carbonic anhydride, CO_{2} (at -60° under a pressure of from four to six atmospheres). This gas is more refractory to liquefaction than sulphurous anhydride, but for this reason it gives on evaporating a still lower temperature than can be attained by the evaporation of sulphurous anhydride. A temperature of -80° may be obtained by the evaporation of liquid carbonic anhydride at a pressure of 760 mm., and in an atmosphere rarefied by a powerful pump the temperature falls to -140°. By employing such low temperatures, it was possible, with the aid of pressure, to liquefy the majority of the other gases. It is evident that special pumps which are capable of rarefying gases are necessary to reduce the pressure in the chambers in which the sulphurous and carbonic anhydride boil; and that, in order to re-condense the resultant gases into liquids, special force pumps are required for pumping the liquid anhydrides into the refrigerating chamber. Thus, in Pictet's apparatus (fig. 24), the carbonic anhydride was liquefied by the aid of the pumps E F, which compressed the gas (at a pressure of 4-6 atmospheres) and forced it into the tube K, vigorously cooled by being surrounded by boiling liquid sulphurous anhydride, which was condensed in the tube C by the pump B, and rarefied by the pump A. The liquefied carbonic anhydride flowed down the tube K into the tube H, in which it was subjected to a low pressure by the pump E, and thus gave a very low temperature of about -140°. The pump E carried off the vapour of the carbonic anhydride, and conducted it to the pump F, by which it was again liquefied. The carbonic anhydride thus made an entire circuit--that is, it passed from a rarefied vapour of small tension and low temperature into a compressed and cooled gas, which was transformed into a liquid, which again vaporised and produced a low temperature. [Illustration: FIG. 24.--General arrangement of the apparatus employed by Pictet for liquefying gases.] Inside the wide inclined tube H, where the carbonic acid evaporated, was placed a second and narrow tube M containing hydrogen, which was generated in the vessel L from a mixture of sodium formate and caustic soda (CHO_{2}Na + NaHO = Na_{2}CO_{3} + H_{2}). This mixture gives hydrogen on heating the vessel L. This vessel and the tube M were made of thick copper, and could withstand great pressures. They were, moreover, hermetically connected together and closed up. Thus the hydrogen which was evolved had no outlet, accumulated in a limited space, and its pressure increased in proportion to the amount of it evolved. This pressure was recorded on a metallic manometer R attached to the end of the tube M. As the hydrogen in this tube was submitted to a very low temperature and a powerful pressure, all the necessary conditions were present for its liquefaction. When the pressure in the tube H became steady--_i.e._ when the temperature had fallen to -140° and the manometer R indicated a pressure of 650 atmospheres in the tube M--then this pressure did not rise with a further evolution of hydrogen in the vessel L. This served as an indication that the tension of the vapour of the hydrogen had attained a maximum corresponding with -140°, and that consequently all the excess of the gas was condensed to a liquid. Pictet convinced himself of this by opening the cock N, when the liquid hydrogen rushed out from the orifice. But, on leaving a space where the pressure was equal to 650 atmospheres, and coming into contact with air under the ordinary pressure, the liquid or powerfully compressed hydrogen expanded, began to boil, absorbed still more heat, and became still colder. In doing so a portion of the liquid hydrogen, according to Pictet, passed into a solid state, and did not fall in drops into a vessel placed under the outlet N, but as pieces of solid matter, which struck against the sides of the vessel like shot and immediately vaporised. Thus, although it was impossible to see and keep the liquefied hydrogen, still it was clear that it passed not only into a liquid, but also into a solid state. Pictet in his experiments obtained other gases which had not previously been liquefied, especially oxygen and nitrogen, in a liquid and solid state. Pictet supposed that liquid and solid hydrogen has the properties of a metal, like iron. [32] At the same time (1879) as Pictet was working on the liquefaction of gases in Switzerland, Cailletet, in Paris, was occupied on the same subject, and his results, although not so convincing as Pictet's, still showed that the majority of gases, previously unliquefied, were capable of passing into a liquid state. Cailletet subjected gases to a pressure of several hundred atmospheres in narrow thick-walled glass tubes (fig. 25); he then cooled the compressed gas as far as possible by surrounding it with a freezing mixture; a cock was then rapidly opened for the outlet of mercury from the tube containing the gas, which consequently rapidly and vigorously expanded. This rapid expansion of the gas would produce great cold, just as the rapid compression of a gas evolves heat and causes a rise in temperature. This cold was produced at the expense of the gas itself, for in rapidly expanding its particles were not able to absorb heat from the walls of the tube, and in cooling a portion of the expanding gas was transformed into liquid. This was seen from the formation of cloud-like drops like a fog which rendered the gas opaque. Thus Cailletet proved the possibility of the liquefaction of gases, but he did not isolate the liquids. The method of Cailletet allows the passage of gases into liquids being observed with greater facility and simplicity than Pictet's method, which requires a very complicated and expensive apparatus. [Illustration: FIG. 25.--Cailletet's apparatus for liquefying gases.] The methods of Pictet and Cailletet were afterwards improved by Olszewski, Wroblewski, Dewar, and others. In order to obtain a still lower temperature they employed, instead of carbonic acid gas, liquid ethylene or nitrogen and oxygen, whose evaporation at low pressures produces a much lower temperature (to -200°). They also improved on the methods of determining such low temperatures, but the methods were not essentially altered; they obtained nitrogen and oxygen in a liquid, and nitrogen even in a solid, state, but no one has yet succeeded in seeing hydrogen in a liquid form. The most illustrative and instructive results (because they gave the possibility of maintaining a very low temperature and the liquefied gas, even air, for a length of time) were obtained in recent years by Prof. Dewar in the Royal Institution of London, which is glorified by the names of Davy, Faraday, and Tyndall. Dewar, with the aid of powerful pumps, obtained many kilograms of oxygen and air (the boiling point under the atmospheric pressure =-190°) in a liquid state and kept them in this state for a length of time by means of open glass vessels with double walls, having a vacuum between them, which prevented the rapid transference of heat, and so gave the possibility of maintaining very low temperatures inside the vessel for a long period of time. The liquefied oxygen or air can be poured from one vessel into another and used for any investigations. Thus in June 1894, Prof. Dewar showed that at the low temperature produced by liquid oxygen many substances become phosphorescent (become self-luminous; for instance, oxygen on passing into a vacuum) and fluoresce (emit light after being illuminated; for instance, paraffin, glue, &c.) much more powerfully than at the ordinary temperature; also that solids then greatly alter in their mechanical properties, &c. I had the opportunity (1894) at Prof. Dewar's of seeing many such experiments in which open vessels containing pounds of liquid oxygen were employed, and in following the progress made in researches conducted at low temperatures, it is my firm impression that the study of many phenomena at low temperatures should widen the horizon of natural science as much as the investigation of phenomena made at the highest temperatures attained in the voltaic arc. [33] The investigations of S. Wroblewski in Cracow give reason to believe that Pictet could not have obtained liquid hydrogen in the interior of his apparatus, and that if he did obtain it, it could only have been at the moment of its outrush due to the fall in temperature following its sudden expansion. Pictet calculated that he obtained a temperature of -140°, but in reality it hardly fell below -120°, judging from the latest data for the vaporisation of carbonic anhydride under low pressure. The difference lies in the method of determining low temperatures. Judging from other properties of hydrogen (_see_ Note 34), one would think that its absolute boiling point lies far below -120°, and even -140° (according to the calculation of Sarrau, on the basis of its compressibility, at -174°). But even at -200° (if the methods of determining such low temperatures be correct) hydrogen does not give a liquid even under a pressure of several hundred atmospheres. However, on expansion a fog is formed and a liquid state attained, but the liquid does not separate. [34] After the idea of the absolute temperature of ebullition (_tc_, Note 29) had been worked out (about 1870), and its connection with the deviations from Mariotte's law had become evident, and especially after the liquefaction of permanent gases, general attention was turned to the development of the fundamental conceptions of the gaseous and liquid states of matter. Some investigators directed their energies to the further study of vapours (for instance, Ramsay and Young), gases (Amagat), and liquids (Zaencheffsky, Nadeschdin, and others), especially to liquids near _tc_ and _pc_; others (Konovaloff and De Heen) endeavoured to discover the relation between liquids under ordinary conditions (removed from _tc_ and _pc_) and gases, whilst a third class of investigators (van der Waals, Clausius, and others), starting from the generally-accepted principles of the mechanical theory of heat and the kinetic theory of gases, and assuming in gases the existence of those forces which certainly act in liquids, deduced the connection between the properties of one and the other. It would be out of place in an elementary handbook like the present to enunciate the whole mass of conclusions arrived at by this method, but it is well to give an idea of the results of van der Waals' considerations, for they explain the gradual uninterrupted passage from a liquid into a gaseous state in the simplest manner, and, although the deduction cannot be considered as complete and decisive (_see_ Note 25), nevertheless it penetrates so deeply into the essence of the matter that its signification is not only reflected in a great number of physical investigations, but also in the province of chemistry, where instances of the passage of substances from a gaseous to a liquid state are so common, and where the very processes of dissociation, decomposition, and combination must be identified with a change of physical state of the participating substances, which has been elaborated by Gibbs, Lavenig, and others. For a _given quantity_ (weight, mass) _of a definite substance_, its state is expressed by three variables--volume _v_, pressure (elasticity, tension) _p_, and temperature _t_. Although the compressibility--[_i.e._, _d(v)_/_d(p)_]--of liquids is small, still it is clearly expressed, and varies not only with the nature of liquids but also with their pressure and temperature (at _tc_ the compressibility of liquids is very considerable). Although gases, according to Mariotte's law, with small variations of pressure, are uniformly compressed, nevertheless the dependence of their volume _v_ on _t_ and _p_ is very complex. This also applies to the coefficient of expansion [= _d(v)_/_d(t)_, or _d(p)_/_d(t)_], which also varies with _t_ and _p_, both for gases (_see_ Note 26), and for liquids (at _tc_ it is very considerable, and often exceeds that of gases, 0·00367). Hence, the _equation of condition_ must include three variables, _v_, _p_, and _t_. For a so-called perfect (ideal) gas, or for inconsiderable variations of density, the elementary expression _pv_ = _R_[Greek: a](1 + [Greek: a]_t_), or _pv_ = _R_(273 + _t_) should be accepted, where _R_ is a constant varying with the mass and nature of a gas, as expressing this dependence, because it includes in itself the laws of Gay-Lussac and Mariotte, for at a constant pressure the volume varies proportionally to 1 + [Greek: a]_t_, and when _t_ is constant the product of _tv_ is constant. In its simplest form the equation may be expressed thus: _pv_ = _RT_; where _T_ denotes what is termed the absolute temperature, or the ordinary temperature + 273--that is, _T_ = _t_ + 273. Starting from the supposition of the existence of an attraction or internal pressure (expressed by _a_) proportional to the square of the density (or inversely proportional to the square of the volume), and of the existence of a real volume or diminished length of path (expressed by _b_) for each gaseous molecule, van der Waals gives for gases the following more complex equation of condition:-- (_p_ + _a_/_v_^2)(_v_-_b_) = 1 + 0·00367_t_; if at 0° under a pressure _p_ = 1 (for example, under the atmospheric pressure), the volume (for instance, a litre) of a gas or vapour he taken as 1, and therefore _v_ and _b_ be expressed by the same units as _p_ and _a_. The deviations from both the laws of Mariotte and Gay-Lussac are expressed by the above equation. Thus, for hydrogen _a_ must be taken as infinitely small, and _b_ = 0·0009, judging by the data for 1,000 and 2,500 metres pressure (Note 28). For other permanent gases, for which (Note 28) I showed (about 1870) from Regnault's and Natterer's data, a decrement of _pv_, followed by an increment, which was confirmed (about 1880) by fresh determinations made by Amagat, this phenomena may be expressed in definite magnitudes of _a_ and _b_ (although van der Waals' formula is not applicable in the case of very small pressures) with sufficient accuracy for contemporary requirements. It is evident that van der Waals' formula can also express the difference of the coefficients of expansion of gases with a change of pressure, and according to the methods of determination (Note 26). Besides this, van der Waals' formula shows that at temperatures above 273(8_a_/27_b_-1) only one actual volume (gaseous) is possible, whilst at lower temperatures, by varying the pressure, three different volumes--liquid, gaseous, and partly liquid, partly saturated-vaporous--are possible. It is evident that the above temperature is the absolute boiling point--that is (_tc_) = 273(8_a_/27_b_-1). It is found under the condition that all three possible volumes (the three roots of van der Waals' cubic equation) are then similar and equal (_vc_ = 3_b_). The pressure in this case (_pc_) = _a_/(27_b_^2). These ratios between the constants _a_ and _b_ and the conditions of _critical state_--_i.e._ (_tc_) and (_pc_)--give the possibility of determining the one magnitude from the other. Thus for ether (Note 29), (_tc_) = 193°, (_tp_) = 40, hence _a_ = 0·0307, _b_ = 0·00533, and (_vc_) = 0·016. That mass of ether which at a pressure of one atmosphere at 0° occupies one volume--for instance, a litre--occupies, according to the above-mentioned condition, this critical volume. And as the density of the vapour of ether compared with hydrogen = 37, and a litre of hydrogen at 0° and under the atmospheric pressure weighs 0·0896 gram, then a litre of ether vapour weighs 3·32 grams; therefore, in a critical state (at 193° and 40 atmospheres) 3·32 grams occupy 0·016 litre, or 16 c.c.; therefore 1 gram occupies a volume of about 5 c.c., and the weight of 1 c.c. of ether will then be 0·21. According to the investigations of Ramsay and Young (1887), the critical volume of ether was approximately such at about the absolute boiling point, but the compressibility of the liquid is so great that the slightest change of pressure or temperature has a considerable effect on the volume. But the investigations of the above savants gave another indirect demonstration of the truth of van der Waals' equation. They also found for ether that the isochords, or the lines of equal volumes (if both _t_ and _p_ vary), are generally straight lines. Thus the volume of 10 c.c. for 1 gram of ether corresponds with pressures (expressed in metres of mercury) equal to 0·135_t_-3·3 (for example, at 180° the pressure = 21 metres, and at 280° it = 34·5 metres). The rectilinear form of the isochord (when _v_ = _a_ constant quantity) is a direct result of van der Waals' formula. When, in 1883, I demonstrated that the specific gravity of liquids decreases in proportion to the rise of temperature [S_{_t_} = S_{_0_}-K_t_ or S_{_t_} = S_{_0_}(1-K_t_)], or that the volumes increase in inverse proportion to the binomial 1-K_t_, that is, V_{_t_} = V_{_0_}(1-K_t_)^{-1}, where K is the modulus of expansion, which varies with the nature of the liquid, then, in general, not only does a connection arise between gases and liquids with respect to a change of volume, but also it would appear possible, by applying van der Waals' formula, to judge, from the phenomena of the expansion of liquids, as to their transition into vapour, and to connect together all the principal properties of liquids, which up to this time had not been considered to be in direct dependence. Thus Thorpe and Rücker found that 2(_tc_) + 273 = 1/K, where K is the modulus of expansion in the above-mentioned formula. For example, the expansion of ether is expressed with sufficient accuracy from 0° to 100° by the equation S_{_t_} = 0·736/(1-0·00154_t_), or V_{_t_} = 1/(1-0·00154_t_), where 0·00154 is the modulus of expansion, and therefore (_tc_) = 188°, or by direct observation 193°. For silicon tetrachloride, SiCl_{4}, the modulus equals 0·00136, from whence (_tc_) = 231°, and by experiment 230°. On the other hand, D. P. Konovaloff, admitting that the external pressure _p_ in liquids is insignificant when compared with the internal (_a_ in van der Waals' formula), and that the work in the expansion of liquids is proportional to their temperature (as in gases), directly deduced, from van der Waals' formula, the above-mentioned formula for the expansion of liquids, V_{t} = 1/(1-K_t_), and also the magnitude of the latent heat of evaporation, cohesion, and compressibility under pressure. In this way van der Waals' formula embraces the gaseous, critical, and _liquid states_ of substances, and shows the connection between them. On this account, although van der Waals' formula cannot be considered as perfectly general and accurate, yet it is not only very much more exact than _pv_ = _RT_, but it is also more comprehensive, because it applies both to gases and liquids. Further research will naturally give a closer proximity to truth, and will show the connection between composition and the constants (_a_ and _b_); but a great scientific progress is seen in this form of the equation of state. Clausius (in 1880), taking into consideration the variability of _a_, in van der Waals' formula, with the temperature, gave the following equation of condition:-- (_p_ + _a_/(_T_(_v_ + _c_)^2)) (_v_-_b_) = _RT_. Sarrau applied this formula to Amagat's data for hydrogen, and found _a_ = 0·0551, _c_ =-0·00043, _b_ = 0·00089, and therefore calculated its absolute boiling point as -174°, and (_pc_) = 99 atmospheres. But as similar calculations for oxygen (-105°), nitrogen (-124°), and marsh gas (-76°) gave _tc_ higher than it really is, the absolute boiling point of hydrogen must lie below -174°. Although a substance which passes with great difficulty into a liquid state by the action of physico-mechanical forces, hydrogen loses its gaseous state (that is, its elasticity, or the physical energy of its molecules, or their rapid progressive motion) with comparative ease under the influence of chemical attraction,[35] which is not only shown from the fact that hydrogen and oxygen (two permanent gases) form liquid water, but also from many phenomena of the absorption of hydrogen. [35] This and a number of similar cases clearly show how great are the internal chemical forces compared with physical and mechanical forces. Hydrogen is vigorously condensed by certain solids; for example, by charcoal and by spongy platinum. If a piece of freshly ignited charcoal be introduced into a cylinder full of hydrogen standing in a mercury bath, then the charcoal absorbs as much as twice its volume of hydrogen. Spongy platinum condenses still more hydrogen. But _palladium_, a grey metal which occurs with platinum, absorbs more hydrogen than any other metal. Graham showed that when heated to a red heat and cooled in an atmosphere of hydrogen, palladium retains as much as 600 volumes of hydrogen. When once absorbed it retains the hydrogen at the ordinary temperature, and only parts with it when heated to a red heat.[36] This capacity of certain dense metals for the absorption of hydrogen explains the property of hydrogen of passing through metallic tubes.[37] It is termed _occlusion_, and presents a similar phenomenon to solution; it is based on the capacity of metals of forming unstable easily dissociating compounds[38] with hydrogen, similar to those which salts form with water. [36] The property of palladium of absorbing hydrogen, and of increasing in volume in so doing, may be easily demonstrated by taking a sheet of palladium varnished on one side, and using it as a cathode. The hydrogen which is evolved by the action of the current is retained by the unvarnished surface, as a consequence of which the sheet curls up. By attaching a pointer (for instance, a quill) to the end of the sheet this bending effect is rendered strikingly evident, and on reversing the current (when oxygen will be evolved and combine with the absorbed hydrogen, forming water) it may be shown that on losing the hydrogen the palladium regains its original form. [37] Deville discovered that iron and platinum become pervious to hydrogen at a red heat. He speaks of this in the following terms:--'The permeability of such homogeneous substances as platinum and iron is quite different from the passage of gases through such non-compact substances as clay and graphite. The permeability of metals depends on their expansion, brought about by heat, and proves that metals and alloys have a certain porosity.' However, Graham proved that it is only hydrogen which is capable of passing through the above-named metals in this manner. Oxygen, nitrogen, ammonia, and many other gases, only pass through in extremely minute quantities. Graham showed that at a red heat about 500 c.c. of hydrogen pass per minute through a surface of one square metre of platinum 1·1 mm. thick, but that with other gases the amount transmitted is hardly perceptible. Indiarubber has the same capacity for allowing the transference of hydrogen through its substance (_see_ Chapter III.), but at the ordinary temperature one square metre, 0·014 mm. thick, transmits only 127 c.c. of hydrogen per minute. In the experiment on the decomposition of water by heat in porous tubes, the clay tube may be exchanged for a platinum one with advantage. Graham showed that by placing a platinum tube containing hydrogen under these conditions, and surrounding it by a tube containing air, the transference of the hydrogen may be observed by the decrease of pressure in the platinum tube. In one hour almost all the hydrogen (97 p.c.) had passed from the tube, without being replaced by air. It is evident that the occlusion and passage of hydrogen through metals capable of occluding it are not only intimately connected together, but are dependent on the capacity of metals to form compounds of various degrees of stability with hydrogen--like salts with water. [38] It appeared on further investigation that palladium gives a definite compound, Pd_{2}H (_see_ further) with hydrogen; but what was most instructive was the investigation of sodium hydride, Na_{2}H, which clearly showed that the origin and properties of such compounds are in entire accordance with the conceptions of dissociation. Since hydrogen is a gas which is difficult to condense, it is little soluble in water and other liquids. At 0° a hundred volumes of water dissolve 1·9 volume of hydrogen, and alcohol 6·9 volumes measured at 0° and 760 mm. Molten iron absorbs hydrogen, but in solidifying, it expels it. The solution of hydrogen by metals is to a certain degree based on its affinity for metals, and must be likened to the solution of metals in mercury and to the formation of alloys. In its chemical properties hydrogen, as we shall see later, has much of a metallic character. Pictet (_see_ Note 31) even affirms that liquid hydrogen has metallic properties. The metallic properties of hydrogen are also evinced in the fact that it is a good conductor of heat, which is not the case with other gases (Magnus). At the ordinary temperature hydrogen very feebly and rarely enters into chemical reaction. The capacity of gaseous hydrogen for reaction becomes evident only under a change of circumstances--by compression, heating, or the action of light, or at the moment of its evolution. However, under these circumstances it _combines_ directly with only a very few of the elements. Hydrogen combines directly with oxygen, sulphur, carbon, potassium, and certain other elements, but it does not combine directly with either the majority of the metals or with nitrogen, phosphorus, &c. Compounds of hydrogen with certain elements on which it does not act directly are, however, known; they are not obtained by a direct method, but by reactions of decomposition, or of double decomposition, of other hydrogen compounds. The property of hydrogen of combining with oxygen at a red heat determines its combustibility. We have already seen that hydrogen easily takes fire, and that it then burns with a pale--that is, non-luminous--flame.[39] Hydrogen does not combine with the oxygen of the atmosphere at the ordinary temperature; but this combination takes place at a red heat,[40] and is accompanied by the evolution of much heat. The product of this combination is water--that is, a compound of oxygen and hydrogen. This is the _synthesis of water_, and we have already noticed its analysis or decomposition into its component parts. The synthesis of water may be very easily observed if a cold glass bell jar be placed over a burning hydrogen flame, and, better still, if the hydrogen flame be lighted in the tube of a condenser. The water will condense in drops as it is formed on the walls of the condenser and trickle down.[41] [39] If it be desired to obtain a perfectly colourless hydrogen flame, it must issue from a platinum nozzle, as the glass end of a gas-conducting tube imparts a yellow tint to the flame, owing to the presence of sodium in the glass. [40] Let us imagine that a stream of hydrogen passes along a tube, and let us mentally divide this stream into several parts, consecutively passing out from the orifice of the tube. The first part is lighted--that is, brought to a state of incandescence, in which state it combines with the oxygen of the atmosphere. A considerable amount of heat is evolved in the combination. The heat evolved then, so to say, ignites the second part of hydrogen coming from the tube, and, therefore, when once ignited, the hydrogen continues to burn, if there be a continual supply of it, and if the atmosphere in which it burns be unlimited and contains oxygen. [41] The combustibility of hydrogen may be shown by the direct decomposition of water by sodium. If a pellet of sodium be thrown into a vessel containing water, it floats on the water and evolves hydrogen, which may be lighted. The presence of sodium imparts a yellow tint to the flame. If potassium be taken, the hydrogen bursts into flame spontaneously, because sufficient heat is evolved in the reaction to ignite the hydrogen. The flame is coloured violet by the potassium. If sodium be thrown not on to water, but on to an acid, it will evolve more heat, and the hydrogen will then also burst into flame. These experiments must be carried on with caution, as, sometimes towards the end, a mass of sodium oxide (Note 8) is produced, and flies about; it is therefore best to cover the vessel in which the experiment is carried on. Light does not aid the combination of hydrogen and oxygen, so that a mixture of these two gases does not change when exposed to the action of light; but an electric spark acts just like a flame, and this is taken advantage of for inflaming a mixture of oxygen and hydrogen, or detonating gas, inside a vessel, as will be explained in the following chapters. As hydrogen (and oxygen also) is condensed by spongy platinum, by which a rise of temperature ensues, and as platinum acts by contact (Introduction), therefore hydrogen also combines with oxygen, under the influence of platinum, as Döbereiner showed. If spongy platinum be thrown into a mixture of hydrogen and oxygen, an explosion takes place. If a mixture of the gases be passed over spongy platinum, combination also ensues, and the platinum becomes red-hot.[42] [42] This property of spongy platinum is made use of in the so-called hydrogen cigar-lighter. It consists of a glass cylinder or beaker, inside which there is a small lead stand (which is not acted on by sulphuric acid), on which a piece of zinc is laid. This zinc is covered by a bell, which is open at the bottom and furnished with a cock at the top. Sulphuric acid is poured into the space between the bell and the sides of the outer glass cylinder, and will thus compress the gas in the bell. If the cock of the cylinder be opened the gas will escape by it, and will be replaced by the acid, which, coming into contact with the zinc, evolves hydrogen, and it will escape through the cock. If the cock be closed, then the hydrogen evolved will increase the pressure of the gas in the bell, and thus again force the acid into the space between the bell and the walls of the outer cylinder. Thus the action of the acid on the zinc may be stopped or started at will by opening or shutting the cock, and consequently a stream of hydrogen may be always turned on. Now, if a piece of spongy platinum be placed in this stream, the hydrogen will take light, because the spongy platinum becomes hot in condensing the hydrogen and inflames it. The considerable rise in temperature of the platinum depends, among other things, on the fact that the hydrogen condensed in its pores comes into contact with previously absorbed and condensed atmospheric oxygen, with which hydrogen combines with great facility in this form. In this manner the hydrogen cigar-lighter gives a stream of burning hydrogen when the cock is open. In order that it should work regularly it is necessary that the spongy platinum should be quite clean, and it is best enveloped in a thin sheet of platinum foil, which protects it from dust. In any case, after some time it will be necessary to clean the platinum, which may be easily done by boiling it in nitric acid, which does not dissolve the platinum, but clears it of all dirt. This imperfection has given rise to several other forms, in which an electric spark is made to pass before the orifice from which the hydrogen escapes. This is arranged in such a manner that the zinc of a galvanic element is immersed when the cock is turned, or a small coil giving a spark is put into circuit on turning the hydrogen on. Although gaseous hydrogen does not act directly[43] on many substances, yet in a _nascent state_ reaction often takes place. Thus, for instance, water on which sodium amalgam is acting contains hydrogen in a nascent state. The hydrogen is here evolved from a liquid, and at the first moment of its formation must be in a condensed state.[44] In this condition it is capable of reacting on substances on which it does not act in a gaseous state.[44 bis] Reactions of substitution or displacement of metals by hydrogen at the moment of its formation are particularly numerous.[45] [43] Under conditions similar to those in which hydrogen combines with oxygen it is also capable of combining with chlorine. A mixture of hydrogen and chlorine explodes on the passage of an electric spark through it, or on contact with an incandescent substance, and also in the presence of spongy platinum; but, besides this, the action of light alone is enough to bring about the combination of hydrogen and chlorine. If a mixture of equal volumes of hydrogen and chlorine be exposed to the action of sunlight, complete combination rapidly ensues, accompanied by a report. Hydrogen does not combine directly with carbon, either at the ordinary temperature or by the action of heat and pressure. But if an electric current be passed through carbon electrodes at a short distance from each other (as in the electric light or voltaic arc), so as to form an electric arc in which the particles of carbon are carried from one pole to the other, then, in the intense heat to which the carbon is subjected in this case, it is capable of combining with hydrogen. A gas of peculiar smell called acetylene, C_{2}H_{2}, is thus formed from carbon and hydrogen. [44] There is another explanation of the facility with which hydrogen reacts in a nascent state. We shall afterwards learn that the molecule of hydrogen contains two atoms, H_{2}, but there are elements the molecules of which only contain one atom--for instance, mercury. Therefore, every reaction of gaseous hydrogen must be accompanied by the disruption of that bond which exists between the atoms forming a molecule. At the moment of evolution, however, it is supposed that free atoms exist, and in this condition, according to the hypothesis, act energetically. This hypothesis is not based upon facts, and the idea that hydrogen is condensed at the moment of its evolution is more natural, and is in accordance with the fact (Note 12) that compressed hydrogen displaces palladium and silver (Brunner, Beketoff)--that is, acts as at the moment of its liberation. [44 bis] There is a very intimate and evident relation between the phenomena which take place in the action of spongy platinum and the phenomena of the action in a nascent state. The combination of hydrogen with aldehyde may be taken as an example. Aldehyde is a volatile liquid with an aromatic smell, boiling at 21°, soluble in water, and absorbing oxygen from the atmosphere, and in this absorption forming acetic acid--the substance which is found in ordinary vinegar. If sodium amalgam be thrown into an aqueous solution of aldehyde, the greater part of the hydrogen evolved combines with the aldehyde, forming alcohol--a substance also soluble in water, which forms the principle of all spirituous liquors, boils at 78°, and contains the same amount of oxygen and carbon as aldehyde, but more hydrogen. The composition of aldehyde is C_{2}H_{4}O, that of alcohol C_{2}H_{6}O. [45] When, for instance, an acid and zinc are added to a salt of silver, the silver is reduced; but this may be explained as a reaction of the zinc, and not of the hydrogen at the moment of its formation. There are, however, examples to which this explanation is entirely inapplicable; thus, for instance, hydrogen, at the moment of its liberation easily takes up oxygen from its compounds with nitrogen if they be in solution, and converts the nitrogen into its hydrogen-compound. Here the nitrogen and hydrogen, so to speak, meet at the moment of their liberation, and in this state combine together. It is evident from this that the elastic gaseous state of hydrogen fixes the limit of its energy: prevents it from entering into those combinations of which it is capable. In the nascent state we have hydrogen which is not in a gaseous state, and its action is then much more energetic. At the moment of evolution that heat, which would be latent in the gaseous hydrogen, is transmitted to its molecules, and consequently they are in a state of strain, and can hence act on many substances. Metals, as we shall afterwards see, are in many cases able to replace each other; they also, and in some cases still more easily, replace and are replaced by hydrogen. We have already seen examples of this in the formation of hydrogen from water, sulphuric acid, &c. In all these cases the metals sodium, iron, or zinc displace the hydrogen which occurs in these compounds. Hydrogen may be displaced from many of its compounds by metals in exactly the same manner as it is displaced from water; so, for example, hydrochloric acid, which is formed directly by the combination of hydrogen with chlorine, gives hydrogen by the action of a great many metals, just as sulphuric acid does. Potassium and sodium also displace hydrogen from its compounds with nitrogen; it is only from its compounds with carbon that hydrogen is not displaced by metals. Hydrogen, in its turn, is able to replace metals; this is accomplished most easily on heating, and with those metals which do not themselves displace hydrogen. If hydrogen be passed over the compounds of many metals with oxygen at a red heat, it takes up the oxygen from the metals and displaces them just as it is itself displaced by metals. If hydrogen be passed over the compound of oxygen with copper at a red heat, then metallic copper and water are obtained--CuO + H_{2} = H_{2}O + Cu. This kind of double decomposition is called _reduction_ with respect to the metal, which is thus reduced to a metallic state from its combination with oxygen. But it must be recollected that all metals do not displace hydrogen from its compound with oxygen, and, conversely, hydrogen is not able to displace all metals from their compounds with oxygen; thus it does not displace potassium, calcium, or aluminium from its compounds with oxygen. If the metals be arranged in the following series: K, Na, Ca, Al ... Fe, Zn, Hg ... Cu, Pb, Ag, Au, then the first are able to take up oxygen from water--that is, displace hydrogen--whilst the last do not act thus, but are, on the contrary, reduced by hydrogen--that is, have, as is said, a less affinity for oxygen than hydrogen, whilst potassium, sodium, and calcium have more. This is also expressed by the amount of heat evolved in the act of combination with oxygen (_see_ Note 7), and is shown by the fact that potassium and sodium and other similar metals evolve heat in decomposing water; but copper, silver, and the like do not do this, because in combining with oxygen they evolve less heat than hydrogen does, and therefore it happens that when hydrogen reduces these metals heat is evolved. Thus, for example, if 16 grams of oxygen combine with copper, 38,000 units of heat are evolved; and when 16 grams of oxygen combine with hydrogen, forming water, 69,000 units of heat are evolved; whilst 23 grams of sodium, in combining with 16 grams of oxygen, evolve 100,000 units of heat. This example clearly shows that chemical reactions which proceed directly and unaided evolve heat. Sodium decomposes water and hydrogen reduces copper, because they are _exothermal_ reactions, or those which evolve heat; copper does not decompose water, because such a reaction would be accompanied by an absorption (or secretion) of heat, or belongs to the class of _endothermal_ reactions in which heat is absorbed; and such reactions do not generally proceed directly, although they may take place with the aid of energy (electrical, thermal, &c.) borrowed from some foreign source.[46] [46] Several numerical data and reflections bearing on this matter are enumerated in Notes 7, 9, and 11. It must be observed that the action of iron or zinc on water is reversible. But the reaction CuO + H_{2} = Cu + H_{2}O is not reversible; the difference between the degrees of affinity is very great in this case, and, therefore, so far as is at present known, no hydrogen is liberated even in the presence of a large excess of water. It is to be further remarked, that under the conditions of the dissociation of water, copper is not oxidised by water, because the oxide of copper is reduced by free hydrogen. If a definite amount of a metal and acid be taken and their reaction be carried on in a closed space, then the evolution of hydrogen will cease, when its tension equals that at which compressed hydrogen displaces the metal. The result depends upon the nature of the metal and the strength of the solution of acid. Tammann and Nernst (1892) found that the metals stand in the following order in respect to this limiting tension of hydrogen:--Na, Mg, Zn, Al, Cd, Fe, Ni. [Illustration: FIG. 26.--Apparatus employed by Dumas for determining the composition of water. Described in text.] The reduction of metals by hydrogen is taken advantage of for _determining the exact composition of water by weight_. Copper oxide is usually chosen for this purpose. It is heated to redness in hydrogen, and the quantity of water thus formed is determined, when the quantity of oxygen which occurs in it is found from the loss of weight of the copper oxide. The copper oxide must be weighed immediately before and after the experiment. The difference shows the weight of the oxygen which entered into the composition of the water formed. In this manner only solids have to be weighed, which is a very great gain in the accuracy of the results obtained.[47] Dulong and Berzelius (1819) were the first to determine the composition of water by this method, and they found that water contains 88·91 of oxygen and 11·09 of hydrogen in 100 parts by weight, or 8·008 parts of oxygen per one part of hydrogen. Dumas (1842) improved on this method,[48] and found that water contains 12·575 parts of hydrogen per 100 parts of oxygen--that is, 7·990 parts of oxygen per 1 part of hydrogen--and therefore it is usually accepted that _water contains eight parts by weight of oxygen to_ one _part by weight of hydrogen_. By whatever method water be obtained, it will always present the same composition. Whether it be taken from nature and purified, or whether it be obtained from hydrogen by oxidation, or whether it be separated from any of its compounds, or obtained by some double decomposition--it will in every case contain one part by weight of hydrogen and eight parts of oxygen. This is because water is a definite chemical compound. Detonating gas, from which it may be formed, is a simple mixture of oxygen and hydrogen, although a mixture of the same composition as water. All the properties of both constituent gases are preserved in detonating gas. Either one or the other gas may be added to it without destroying its homogeneity. The fundamental properties of oxygen and hydrogen are not found in water, and neither of the gases can be directly combined with it. But they may be evolved from it. In the formation of water there is an evolution of heat; for the decomposition of water heat is required. All this is expressed by the words, _Water is a definite chemical compound of hydrogen with oxygen_. Taking the symbol of hydrogen, H, as expressing a unit quantity by weight of this substance, and expressing 16 parts by weight of oxygen by O, we can formulate all the above statements by the chemical symbol of water, H_{2}O. As only definite chemical compounds are denoted by formulæ, having denoted the formula of a compound substance we express by it the entire series of properties which go to make up our conception of a definite compound, and at the same time the quantitative composition of the substance by weight. Further, as we shall afterwards see, formulæ express the volume of the gases contained in a substance. Thus the formula of water shows that it contains two volumes of hydrogen and one volume of oxygen. Besides which, we shall learn that the formula expresses the density of the vapour of a compound, and on this many properties of substances depend, and, as we shall learn, determine the quantities of the bodies entering into reactions. This vapour density we shall find also determines the quantity of a substance entering into a reaction. Thus the letters H_{2}O tell the chemist the entire history of the substance. This is an international language, which endows chemistry with a simplicity, clearness, stability, and trustworthiness founded on the investigation of the laws of nature. [47] This determination may be carried on in an apparatus like that mentioned in Note 13 of Chapter I. [48] We will proceed to describe Dumas' method and results. For this determination pure and dry copper oxide is necessary. Dumas took a sufficient quantity of copper oxide for the formation of 50 grams of water in each determination. As the oxide of copper was weighed before and after the experiment, and as the amount of oxygen contained in water was determined by the difference between these weights, it was essential that no other substance besides the oxygen forming the water should be evolved from the oxide of copper during its ignition in hydrogen. It was necessary, also, that the hydrogen should be perfectly pure, and free not only from traces of moisture, but from any other impurities which might dissolve in the water or combine with the copper and form some other compound with it. The bulb containing the oxide of copper (fig. 26), which was heated to redness, should be quite free from air, as otherwise the oxygen in the air might, in combining with the hydrogen passing through the vessel, form water in addition to that formed by the oxygen of the oxide of copper. The water formed should be entirely absorbed in order to accurately determine its quantity. The hydrogen was evolved in the three-necked bottle. The sulphuric acid, for acting on the zinc, is poured through funnels into the middle neck. The hydrogen evolved in the Woulfe's bottle passes through [U] tubes, in which it is purified, to the bulb, where it comes into contact with the copper oxide, forms water, and reduces the oxide to metallic copper; the water formed is condensed in the second bulb, and any passing off is absorbed in the second set of [U] tubes. This is the general arrangement of the apparatus. The bulb with the copper oxide is weighed before and after the experiment. The loss in weight shows the quantity of oxygen which entered into the composition of the water formed, the weight of the latter being shown by the gain in weight of the absorbing apparatus. Knowing the amount of oxygen in the water formed, we also know the quantity of hydrogen contained in it, and consequently we determine the composition of water by weight. This is the essence of the determination. We will now turn to certain particulars. In one neck of the three-necked bottle a tube is placed dipping under mercury. This serves as a safety-valve to prevent the pressure inside the apparatus becoming too great from the rapid evolution of hydrogen. If the pressure rose to any considerable extent, the current of gases and vapours would be very rapid, and, as a consequence, the hydrogen would not be perfectly purified, or the water entirely absorbed in the tubes placed for this purpose. In the third neck of the Woulfe's bottle is a tube conducting the hydrogen to the purifying apparatus, consisting of eight [U] tubes, destined for the purification and testing of the hydrogen. The hydrogen, evolved by zinc and sulphuric acid, is purified by passing it first through a tube full of pieces of glass moistened with a solution of lead nitrate next through silver sulphate; the lead nitrate retains sulphurette hydrogen, and arseniuretted hydrogen is retained by the tube with silver sulphate. Caustic potash in the next [U] tube retains any acid which might come over. The two following tubes are filled with lumps of dry caustic potash in order to absorb any carbonic anhydride and moisture which the hydrogen might contain. The next two tubes, to remove the last traces of moisture, are filled with phosphoric anhydride, mixed with lumps of pumice-stone. They are immersed in a freezing mixture. The small [U] tube contains hygroscopic substances, and is weighed before the experiment: this is in order to know whether the hydrogen passing through still retains any moisture. If it does not, then the weight of this tube will not vary during the whole experiment, but if the hydrogen evolved still retains moisture, the tube will increase in weight. The copper oxide is placed in the bulb, which, previous to the experiment, is dried with the copper oxide for a long period of time. The air is then exhausted from it, in order to weigh the oxide of copper in a vacuum and to avoid the need of a correction for weighing in air. The bulb is made of infusible glass, that it may be able to withstand a lengthy (20 hours) exposure to a red heat without changing in form. The weighed bulb is only connected with the purifying apparatus after the hydrogen has passed through for a long time, and after experiment has shown that the hydrogen passing from the purifying apparatus is pure and does not contain any air. On passing from the condensing bulb the gas and vapour enter into an apparatus for absorbing the last traces of moisture. The first [U] tube contains pieces of ignited potash, the second and third tubes phosphoric anhydride or pumice-stone moistened with sulphuric acid. The last of the two is employed for determining whether all the moisture is absorbed, and is therefore weighed separately. The final tube only serves as a safety-tube for the whole apparatus, in order that the external moisture should not penetrate into it. The glass cylinder contains sulphuric acid, through which the excess of hydrogen passes; it enables the rate at which the hydrogen is evolved to be judged, and whether its amount should be decreased or increased. When the apparatus is fitted up it must be seen that all its parts are hermetically tight before commencing the experiment. When the previously weighed parts are connected together and the whole apparatus put into communication, then the bulb containing the copper oxide is heated with a spirit lamp (reduction does not take place without the aid of heat), and the reduction of the copper oxide then takes place, and water is formed. When nearly all the copper oxide is reduced the lamp is removed and the apparatus allowed to cool, the current of hydrogen being kept up all the time. When cool, the drawn-out end of the bulb is fused up, and the hydrogen remaining in it is exhausted, in order that the copper may be again weighed in a vacuum. The absorbing apparatus remains full of hydrogen, and would therefore present a less weight than if it were full of air, as it was before the experiment, and for this reason, having disconnected the copper oxide bulb, a current of dry air is passed through it until the gas passing from the glass cylinder is quite free from hydrogen. The condensing bulb and the two tubes next to it are then weighed, in order to determine the quantity of water formed. Dumas repeated this experiment many times. The average result was that water contains 1253·3 parts of hydrogen per 10,000 parts of oxygen. Making a correction for the amount of air contained in the sulphuric acid employed for producing the hydrogen, Dumas obtained the average figure 1251·5, between the extremes 1247·2 and 1256·2. This proves that per 1 part of hydrogen water contains 7·9904 parts of oxygen, with a possible error of not more than 1/250, or 0·03, in the amount of oxygen per 1 part of hydrogen. Erdmann and Marchand, in eight determinations, found that per 10,000 parts of oxygen water contains an average of 1,252 parts of hydrogen, with a difference of from 1,258·5 to 1,248·7; hence per 1 part of hydrogen there would be 7·9952 of oxygen, with an error of at least 0·05. Keiser (1888), in America by employing palladium hydride, and by introducing various fresh precautions for obtaining accurate results, found the composition of water to be 15·95 parts of oxygen per 2 of hydrogen. Certain of the latest determinations of the composition of water, as also those made by Dumas, always give less than 8, and on the average 7·98, of oxygen per 1 part of hydrogen. However, not one of these figures is to be entirely depended on, and for ordinary accuracy it may be considered that O = 16 when H = 1. CHAPTER III OXYGEN AND THE CHIEF ASPECTS OF ITS SALINE COMBINATIONS On the earth's surface there is no other element which is so widely distributed as oxygen in its various compounds.[1] It makes up eight-ninths of the weight of water, which occupies the greater part of the earth's surface. Nearly all earthy substances and rocks consist of compounds of oxygen with metals and other elements. Thus, the greater part of sand is formed of silica, SiO_{2}, which contains 53 p.c. of oxygen; clay contains water, alumina (formed of aluminium and oxygen), and silica. It may be considered that earthy substances and rocks contain up to one-third of their weight of oxygen; animal and vegetable substances are also very rich in oxygen. Without counting the water present in them, plants contain up to 40, and animals up to 20 p.c. by weight of oxygen. Thus, oxygen compounds predominate on the earth's surface. Besides this, a portion exists in a free state, and is contained in admixture with nitrogen in the atmosphere, forming about one-fourth of its mass, or one-fifth of its volume. [1] As regards the interior of the earth, it probably contains far less oxygen compounds than the surface, judging by the accumulated evidences of the earth's origin, of meteorites, of the earth's density, &c. (_see_ Chapter VIII., Note 58, and Chapter XXII., Note 2). Being so widely distributed in nature, oxygen plays a very important part in it, for a number of the phenomena which take place before us are mainly dependent on it. _Animals breathe_ air in order to obtain only _oxygen_ from it, the oxygen entering into their respiratory organs (the lungs of human beings and animals, the gills of fishes, and the trachæ of insects); they, so to say, drink in air in order to absorb the oxygen. The oxygen of the air (or dissolved in water) passes through the membranes of the respiratory organs into the blood, is retained in it by the blood corpuscles, is transmitted by their means to all parts of the body, aids their transformations, bringing about chemical processes in them, and chiefly extracting carbon from them in the form of carbonic anhydride, the greater part of which passes into the blood, is dissolved by it, and is thrown off by the lungs during the absorption of the oxygen. Thus, in the process of respiration carbonic anhydride (and water) is given off, and the oxygen of the air absorbed, by which means the blood is changed from a red venous to a dark-red arterial blood. The cessation of this process causes death, because then all those chemical processes, and the consequent heat and work which the oxygen introduced into the system brought about, cease. For this reason suffocation and death ensue in a vacuum, or in a gas which does not contain free oxygen, _i.e._ which does not support combustion. If an animal be placed in an atmosphere of free oxygen, at first its movements are very active and a general invigoration is remarked, but a reaction soon sets in, and death may ensue. The oxygen of the air when it enters the lungs is diluted with four volumes of nitrogen, which is not absorbed into the system, so that the blood absorbs but a small quantity of oxygen from the air, whilst in an atmosphere of pure oxygen a large quantity of oxygen would be absorbed, and would produce a very rapid change of all parts of the organism, and destroy it. From what has been said, it will be understood that oxygen may be employed in respiration, at any rate for a limited time, when the respiratory organs suffer under certain forms of suffocation and impediment to breathing.[2] [2] It is evident that the partial pressure (_see_ Chapter I.) acts in respiration. The researches of Paul Bert showed this with particular clearness. Under a pressure of one-fifth of an atmosphere consisting of oxygen only, animals and human beings remain under the ordinary conditions of the partial pressure of oxygen, but organisms cannot support air rarefied to one-fifth, for then the partial pressure of the oxygen falls to one-twenty-fifth of an atmosphere. Even under a pressure of one-third of an atmosphere the regular life of human beings is impossible, by reason of the impossibility of respiration (because of the decrease of solubility of oxygen in the blood), owing to the small partial pressure of the oxygen, and not from any mechanical effect of the decrease of pressure. Paul Bert illustrated all this by many experiments, some of which he conducted on himself. This explains, among other things, the discomfort felt in the ascent of high mountains or in balloons when the height reached exceeds eight kilometres, and at pressures below 250 mm. (Chapter II., Note 23). It is evident that an artificial atmosphere has to be employed in the ascent to great heights, just as in submarine work. The cure by compressed and rarefied air which is practised in certain illnesses is based partly on the mechanical action of the change of pressure, and partly on the alteration in the partial pressure of the respired oxygen. The combustion of organic substances--that is, substances which make up the composition of plants and animals--proceeds in the same manner as the combustion of many inorganic substances, such as sulphur, phosphorus, iron, &c., from the combination of these substances with oxygen, as was described in the Introduction. The decomposition, rotting, and similar transformations of substances, which proceed around us, are also very often dependent on the action of the oxygen of the air, and also reduce it from a free to a combined state. The majority of the compounds of oxygen are, like water, very stable, and do not give up their oxygen under the ordinary conditions of nature. As these processes are taking place everywhere, it might be expected that the amount of free oxygen in the atmosphere should decrease, and this decrease should proceed somewhat rapidly. This is, in fact, observed where combustion or respiration proceeds in a closed space. Animals suffocate in a closed space because in consuming the oxygen the air remains unfit for respiration. In the same manner combustion, after a time, ceases in a closed space, which may be proved by a very simple experiment. An ignited substance--for instance, a piece of burning sulphur--has only to be placed in a glass flask, which is then closed with a stout cork to prevent the access of the external air; combustion will proceed for a certain time, so long as the flask contains any free oxygen, but it will cease when the oxygen of the enclosed air has combined with the sulphur. From what has been said, it is evident that regularity of combustion or respiration requires a constant renewal of air--that is, that the burning substance or respiring animal should have access to a fresh supply of oxygen. This is attained in dwellings by having many windows, outlets, and ventilators, and by the current of air produced by fires and stoves. As regards the air over the entire earth's surface its amount of oxygen hardly decreases, because in nature there is a process going on which renews the supply of free oxygen. _Plants_, or rather their leaves, during daytime,[3] under the influence of light, absorb carbonic anhydride CO_{2}, and _evolve free oxygen_. Thus the loss of oxygen which occurs in consequence of the respiration of animals and of combustion is made good by plants. If a leaf be placed in a bell jar containing water, and carbonic anhydride (because this gas is absorbed and oxygen evolved from it by plants) be passed into the bell, and the whole apparatus placed in sunlight, then oxygen will accumulate in the bell jar. This experiment was first made by Priestley at the end of the last century. Thus the life of plants on the earth not only serves for the formation of food for animals, but also for keeping up a constant percentage of oxygen in the atmosphere. In the long period of the life of the earth an equilibrium has been attained between the processes absorbing and evolving oxygen, by which a definite quantity of free oxygen is preserved in the entire mass of the atmosphere.[4] [3] At night, without the action of light, without the absorption of that energy which is required for the decomposition of carbonic anhydride into free oxygen and carbon (which is retained by the plants) they breathe like animals, absorbing oxygen and evolving carbonic anhydride. This process also goes on side by side with the reverse process in the daytime, but it is then far feebler than that which gives oxygen. [4] The earth's surface is equal to about 510 million square kilometres, and the mass of the air (at a pressure of 760 mm.) on each kilometre of surface is about 10-1/3 thousand millions of kilograms, or about 10-1/3 million tons; therefore the whole weight of the atmosphere is about 5,100 million million (= 51 × 10^{14}) tons. Consequently there are about 2 × 10^{15} tons of free oxygen in the earth's atmosphere. The innumerable series of processes which absorb a portion of this oxygen are compensated for by the plant processes. Assuming that 100 million tons of vegetable matter, containing 40 p.c. of carbon, formed from carbonic acid, are produced (and the same process proceeds in water) per year on the 100 million square kilometres of dry land (ten tons of roots, leaves, stems, &c., per hectare, or 1/100 of a square kilometre), we find that the plant life of the dry land gives about 100,000 tons of oxygen, which is an insignificant fraction of the entire mass of the oxygen of the air. Oxygen was obtained as an independent gas in 1774 by Priestley in England and in the same year by Scheele in Sweden, but its nature and great importance were only perfectly elucidated by Lavoisier. Free oxygen may be obtained by one or other method from all the substances in which it occurs. Thus, for instance, the oxygen of many substances may be transferred into water, from which, as we have already seen, oxygen may be obtained.[5] We will first consider the methods of extracting oxygen from air as being a substance everywhere distributed. The separation of oxygen from it is, however, hampered by many difficulties. [5] The extraction of oxygen from water may be effected by two processes: either by the decomposition of water into its constituent parts by the action of a galvanic current (Chapter II.), or by means of the removal of the hydrogen from water. But, as we have seen and already know, hydrogen enters into direct combination with very few substances, and then only under special circumstances; whilst oxygen, as we shall soon learn, combines with nearly all substances. Only gaseous chlorine (and, especially, fluorine) is capable of decomposing water, taking up the hydrogen from it, without combining with the oxygen. Chlorine is soluble in water, and if an aqueous solution of chlorine, so-called chlorine water, be poured into a flask, and this flask be inverted in a basin containing the same chlorine water, then we shall have an apparatus by means of which oxygen may be extracted from water. At the ordinary temperature, and in the dark, chlorine does not act on water, or only acts very feebly; but under the action of direct sunlight chlorine decomposes water, with the evolution of oxygen. The chlorine then combines with the hydrogen, and gives hydrochloric acid, which dissolves in the water, and therefore free oxygen only will be separated from the liquid, and it will only contain a small quantity of chlorine in admixture, which can be easily removed by passing the gas through a solution of caustic potash. From air, which contains a _mixture_ of oxygen and nitrogen, the nitrogen alone cannot be removed, because it has no inclination to combine directly or readily with any substance; and although it does combine with certain substances (boron, titanium), these substances combine simultaneously with the oxygen of the atmosphere.[6] However, oxygen may be separated from air by causing it to combine with substances which may be easily decomposed by the action of heat, and, in so doing, give up the oxygen absorbed--that is, by making use of reversible reactions. Thus, for instance, the oxygen of the atmosphere may be made to oxidise sulphurous anhydride, SO_{2} (by passing directly over ignited spongy platinum), and to form sulphuric anhydride, or sulphur trioxide, SO_{3}; and this substance (which is a solid and volatile, and therefore easily separated from the nitrogen and sulphurous anhydride), on further heating, gives oxygen and sulphurous anhydride. Caustic soda or lime extracts (absorbs) the sulphurous anhydride from this mixture, whilst the oxygen is not absorbed, and thus it is isolated from the air. On a large scale in works, as we shall afterwards see, sulphurous anhydride is transformed into hydrate of sulphuric trioxide, or sulphuric acid, H_{2}SO_{4}; if this is allowed to drop on to red-hot flagstones, water, sulphurous anhydride, and oxygen are obtained. The oxygen is easily isolated from this mixture by passing the gases over lime. The extraction of oxygen from oxide of mercury (Priestley, Lavoisier), which is obtained from mercury and the oxygen of the atmosphere, is also a reversible reaction by which oxygen may be obtained from the atmosphere. So also, by passing dry air through a red-hot tube containing barium oxide, it is made to combine with the oxygen of the air. In this reaction the so-called barium peroxide, BaO_{2}, is formed from the barium oxide, BaO, and at a higher temperature the former evolves the absorbed oxygen, and leaves the barium oxide originally taken.[7] [6] A difference in the physical properties of both gases cannot be here taken advantage of, because they are very similar in this respect. Thus the density of oxygen is 16 times and of nitrogen 14 times greater than the density of hydrogen, and therefore porous vessels cannot be here employed--the difference between the times of their passage through a porous surface would be too insignificant. [Illustration: FIG. 27.--Graham's apparatus for the decomposition of air by pumping it through india-rubber.] Graham, however, succeeded in enriching air in oxygen by passing it through india-rubber. This may be done in the following way:--A common india-rubber cushion, E (Fig. 27), is taken, and its orifice hermetically connected with an air-pump, or, better still, a mercury aspirator (the Sprengel pump is designated by the letters A, C, B). When the aspirator (Chapter II., Note 16) has pumped out the air, which will be seen by the mercury running out in an almost uninterrupted stream, and from its standing approximately at the barometric height, then it may be clearly observed that gas passes through the india-rubber. This is also seen from the fact that bubbles of gas continually pass along with the mercury. A minus pressure may be constantly maintained in the cushion by pouring mercury into the funnel A, and screwing up the pinchcock C, so that the stream flowing from it is small, and then a portion of the air passing through the india-rubber will be carried along with the mercury. This air may be collected in the cylinder, R. Its composition proves to be about 42 volumes of oxygen with 57 volumes of nitrogen, and one volume of carbonic anhydride, whilst ordinary air contains only 21 volumes of oxygen in 100 volumes. A square metre of india-rubber surface (of the usual thickness) passes about 45 c.c. of such air per hour. This experiment clearly shows that india-rubber is permeable to gases. This may, by the way, be observed in common toy balloons filled with coal-gas. They fall after a day or two, not because there are holes in them, but because air penetrates into, and the gas from, their interior, through the surface of the india-rubber of which they are made. The rate of the passage of gases through india-rubber does not, as Mitchell and Graham showed, depend on their densities, and consequently its permeability is not determined by orifices. It more resembles dialysis--that is, the penetration of liquids through colloid surfaces. Equal volumes of gases penetrate through india-rubber in periods of time which are related to each other as follows:--carbonic anhydride, 100; hydrogen, 247; oxygen, 532; marsh gas, 633; carbonic oxide, 1,220; nitrogen, 1,358. Hence nitrogen penetrates more slowly than oxygen, and carbonic anhydride more quickly than other gases. 2·556 volumes of oxygen and 13·585 volumes of carbonic anhydride penetrate in the same time as one volume of nitrogen. By multiplying these ratios by the amounts of these gases in air, we obtain figures which are in almost the same proportion as the volumes of the gases penetrating from air through india-rubber. If the process of dialysis be repeated on the air which has already passed through india-rubber, then a mixture containing 65 p.c. by volume of oxygen is obtained. It may be thought that the cause of this phenomenon is the absorption or occlusion (_see_ Chap. II., Note 37) of gases by india-rubber and the evolution of the gas dissolved in a vacuum; and, indeed, india-rubber does absorb gases, especially carbonic anhydride. Graham called the above method of the decomposition of air _atmolysis_. [7] The preparation of oxygen by this method, which is due to Boussingault, is conducted in a porcelain tube, which is placed in a stove heated by charcoal, so that its ends project beyond the stove. Barium oxide (which may be obtained by igniting barium nitrate, previously dried) is placed in the tube, one end of which is connected with a pair of bellows, or a gas-holder, for keeping up a current of air through it. The air is previously passed through a solution of caustic potash, to remove all traces of carbonic anhydride, and it is very carefully dried (for the hydrate BaH_{2}O_{2} does not give the peroxide). At a _dark-red heat_ (500-600°) the oxide of barium absorbs oxygen from the air, so that the gas leaving the tube consists almost entirely of nitrogen. When the absorption ceases, the air will pass through the tube unchanged, which may be recognised from the fact that it supports combustion. The barium oxide is converted into peroxide under these circumstances, and eleven parts of barium oxide absorb about one part of oxygen by weight. When the absorption ceases, one end of the tube is closed, a cork with a gas-conducting tube is fixed into the other end, and the heat of the stove is increased to a _bright-red heat_ (800°). At this temperature the barium peroxide gives up all that oxygen which it acquired at a dark-red heat--_i.e._ about one part by weight of oxygen is evolved from twelve parts of barium peroxide. After the evolution of the oxygen there remains the barium oxide which was originally taken, so that air may be again passed over it, and thus the preparation of oxygen from one and the same quantity of barium oxide may be repeated many times. Oxygen has been produced one hundred times from one mass of oxide by this method; all the necessary precautions being taken, as regards the temperature of the mass and the removal of moisture and carbonic acid from the air. Unless these precautions be taken, the mass of oxide soon spoils. As oxygen may become of considerable technical use, from its capacity for giving high temperatures and intense light in the combustion of substances, its preparation directly from air by practical methods forms a problem whose solution many investigators continue to work at up to the present day. The most practical methods are those of Tessié du Motay and Kassner. The first is based on the fact that a mixture of equal weights of manganese peroxide and caustic soda at an incipient red heat (about 350°) absorbs oxygen from air, with the separation of water, according to the equation MnO_{2} + 2NaHO + O = Na_{2}MnO_{4} + H_{2}O. If superheated steam, at a temperature of about 450°, be then passed through the mixture, the manganese peroxide and caustic soda originally taken are regenerated, and the oxygen held by them is evolved, according to the reverse equation Na_{2}MnO_{4} + H_{2}O = MnO_{2} + 2NaHO + O. This mode of preparing oxygen may be repeated for an infinite number of times. The oxygen in combining liberates water, and steam, acting on the resultant substance, evolves oxygen. Hence all that is required for the preparation of oxygen by this method is fuel and the alternate cutting off the supply of air and steam. In Kassner's process (1891) a mixture of oxide of lead and lime (PbO + 2CaO) is heated to redness in the presence of air, oxygen is then absorbed and calcium plumbate, Ca_{2}PbO_{4}, formed. The latter is of a chocolate colour, and on further heating evolves oxygen and gives the original mixture PbO + 2CaO--that is, the phenomenon is essentially the same as in Boussingault's process (with BaO), but according to Le Chatelier (1893) the dissociation tension of the oxygen evolved from Ca_{2}PbO_{4} is less than with BaO_{2} at equal temperatures; for instance, at 940°, 112 mm. of mercury for the first, and for the latter 210 mm. at 720°, and 670 mm. at 790°, while for Ca_{2}PbO_{4} this tension is only reached at 1,080°. However, in Kassner's process the oxygen is absorbed more rapidly, and the influence of the presence of moisture and CO_{2} in the air is not so marked, so that this process, like that of Tessié du Motay, deserves consideration. Oxygen is evolved with particular ease by a whole series of unstable oxygen compounds, of which we shall proceed to take a general survey, remarking that many of these reactions, although not all, belong to the number of reversible reactions;[8] so that in order to obtain many of these substances (for instance, potassium chlorate) rich in oxygen, recourse must be had to indirect methods (see Introduction) with which we shall become acquainted in the course of this book. [8] Even the decomposition of manganese peroxide is reversible, and it may be re-obtained from that suboxide (or its salts), which is formed in the evolution of oxygen (Chap. XI., Note 6). The compounds of chromic acid containing the trioxide CrO_{3} in evolving oxygen give chromium oxide, Cr_{2}O_{3}, but they re-form the salt of chromic acid when heated to redness in air with an alkali. 1. _The compounds of oxygen_ with certain metals, and especially with the so-called noble metals--that is, mercury, silver, gold, and platinum--having once been obtained, retain their oxygen at the ordinary temperature, but part with it at a red heat. The compounds are solids, generally amorphous and infusible, and are easily decomposed by heat into the metal and oxygen. We have seen an example of this in speaking of the decomposition of mercury oxide. Priestley, in 1774, obtained pure oxygen for the first time by heating mercury oxide by means of a burning-glass, and clearly showed its difference from air. He showed its characteristic property of supporting combustion 'with remarkable vigour,' and named it dephlogisticated air. 2. The substances called _peroxides_[9] evolve oxygen at a greater or less heat (and also by the action of many acids). They usually contain metals combined with a large quantity of oxygen. Peroxides are the highest oxides of certain metals; those metals which form them generally give several compounds with oxygen. Those of the lowest degrees of oxidation, containing the least amount of oxygen, are generally substances which are capable of easily reacting with acids--for instance, with sulphuric acid. Such low oxides are called bases. Peroxides contain more oxygen than the bases formed by the same metals. For example, lead oxide contains 7·1 parts of oxygen in 100 parts, and is basic, but lead peroxide contains 13·3 parts of oxygen in 100 parts. _Manganese peroxide_ is a similar substance, and is a solid of a dark colour, which occurs in nature. It is employed for technical purposes under the name of black oxide of manganese (in German, 'Braunstein,' the pyrolusite of the mineralogist). Peroxides are able to evolve oxygen at a more or less elevated temperature. They do not then part with all their oxygen, but with only a portion of it, and are converted into a lower oxide or base. Thus, for example, lead peroxide, on heating, gives oxygen and lead oxide. The decomposition of this peroxide proceeds tolerably easily on heating, even in a glass vessel, but manganese peroxide only evolves oxygen at a strong red heat, and therefore oxygen can only be obtained from it in iron, or other metallic, or clay vessels. This was formerly the method for obtaining oxygen. Manganese peroxide only parts with one-third of its oxygen (according to the equation 3MnO_{2} = Mn_{3}O_{4} + O_{2}), whilst two-thirds remain in the solid substance which forms the residue after heating. Metallic peroxides are also capable of evolving oxygen on heating with sulphuric acid. They then evolve just that amount of oxygen which is in excess of that necessary for the formation of the base, the latter reacting on the sulphuric acid forming a compound (salt) with it. Thus barium peroxide, when heated with sulphuric acid, forms oxygen and barium oxide, which gives a compound with sulphuric acid termed barium sulphate (BaO_{2} + H_{2}SO_{4} = BaSO_{4} + H_{2}O + O).[9 bis] This reaction usually proceeds with greater ease than the decomposition of peroxides by heat alone. For the purposes of experiment powdered manganese peroxide is usually taken and mixed with strong sulphuric acid in a flask, and the apparatus set up as shown in Fig. 28. The gas which is evolved is passed through a Woulfe's bottle containing a solution of caustic potash, to purify it from carbonic anhydride and chlorine, which accompany the evolution of oxygen from commercial manganese peroxide, and the gas is not collected until a thin smouldering taper placed in front of the escape orifice bursts into flame, which shows that the gas coming off is oxygen. By this method of decomposition of the manganese peroxide by sulphuric acid there is evolved, not, as in heating, one-third, but one-half of the oxygen contained in the peroxide (MnO_{2} + H_{2}SO_{4} = MnSO_{4} + H_{2}O + O)--that is, from 50 grams of peroxide about 7-1/5 grams, or about 5-1/2 litres, of oxygen,[10] whilst by heating only about 3-1/2 litres are obtained. The chemists of Lavoisier's time generally obtained oxygen by heating manganese peroxide. At the present time more convenient methods are known. [Illustration: FIG. 28.--Preparation of oxygen from manganese peroxide and sulphuric acid. The gas evolved is passed through a Woulfe's bottle containing caustic potash.] [9] We shall afterwards see that it is only substances like barium peroxide (which give hydrogen peroxide) which should be counted as true peroxides, and that MnO_{2}, PbO_{2}, &c., should be distinguished from them (they do not give hydrogen peroxide with acids), and therefore it is best to call them dioxides. [9 bis] Peroxide of barium also gives oxygen at the ordinary temperature in the presence of the solutions of many substances in a higher degree of oxidation. In this respect we may mention that Kassner (1890) proposes to obtain oxygen for laboratory purposes by mixing BaO_{2} with FeK_{3}(CN)_{6} (red prussiate of potash, Chapter XXII.): the reaction proceeds with the evolution of oxygen even on the addition of a very small quantity of water. In order to ensure a gradual evolution of gas the author proposes to introduce both substances into the reaction, little by little, instead of all at once, which may be done with the following arrangement (Gavaloffsky): finely powdered peroxide of barium is placed in an ordinary flask and sufficient water is added to fill the flask one-third full. The cork closing the flask has three holes; (1) for the gas-conducting tube; (2) for a rod to stir the BaO_{2}; and (3) for a glass rod terminating in a perforated glass vessel containing crystals of FeK_{3}(CN)_{6}. When it is desired to start the evolution of the oxygen, the vessel is lowered until it is immersed in the liquid in the flask, and the BaO_{2} is stirred with the other rod. The reaction proceeds according to the equation, BaO_{2} + 2FeK_{3}(CN)_{6} = FeK_{4}(CN)_{6} + FeK_{2}Ba(CN)_{6} + O_{2}. The double salt, FeBa_{2}(CN)_{6}, crystallises out from the mother liquor. To understand the course of the reaction, it must be remembered BaO_{2} is of a higher degree of oxidation, and that it parts with oxygen and gives the base BaO which enters into the complex salt FeK_{2}Ba(CN)_{6} = Fe(CN)_{2} + 2KCN + Ba(CN)_{2}, and this latter = BaO + 2HCN-H_{2}O. Moreover, FeK_{3}(CN)_{6} contains the salt Fe_{2}(CN)_{6} which also corresponds to the higher degree of oxidation of iron, Fe_{2}O_{3}, whilst after the reaction a salt is obtained which contains Fe(CN)_{2}, and corresponds to the lower degree of oxidation, FeO, so that (in the presence of water) oxygen is also set free on this side also, _i.e._ the reaction gives lower degrees of oxidation and oxygen. [10] Scheele, in 1785, discovered the method of obtaining oxygen by treating manganese peroxide with sulphuric acid. 3. A third source to which recourse may be had for obtaining oxygen is represented in _acids_ and _salts_ containing much oxygen, which are capable, by parting with a portion or all of their oxygen, of being converted into other compounds (lower products of oxidation) which are more difficultly decomposed. These acids and salts (like peroxides) evolve oxygen either on heating alone, or only when in the presence of some other substance. Sulphuric acid may be taken as an example of an acid which is decomposed by the action of heat alone,[11] for it breaks up at a red heat into water, sulphurous anhydride, and oxygen, as was mentioned before. Priestley, in 1772, and Scheele, somewhat later, obtained oxygen by heating nitre to a red heat. The best examples of the formation of oxygen by the heating of salts is given in _potassium chlorate_, or Berthollet's salt, so called after the French chemist who discovered it. Potassium chlorate is a salt composed of the elements potassium, chlorine, and oxygen, KClO_{3}. It occurs as transparent colourless plates, is soluble in water, especially in hot water, and resembles common table salt in some of its reactions and physical properties; it melts on heating, and in melting begins to decompose, evolving oxygen gas. This decomposition ends in all the oxygen being evolved from the potassium chlorate, potassium chloride being left as a residue, according to the equation KClO_{3} = KCl + O_{3}.[12] This decomposition proceeds at a temperature which allows of its being conducted in a glass vessel. However, in decomposing, the molten potassium chlorate swells up and boils, and gradually solidifies, so the evolution of the oxygen is not regular, and the glass vessel may crack. In order to overcome this inconvenience, the potassium chlorate is crushed and mixed with a powder of a substance which is infusible, incapable of combining with the oxygen evolved, and is a good conductor of heat. Usually it is mixed with manganese peroxide.[13] The decomposition of the potassium chlorate is then considerably facilitated, and proceeds at a lower temperature (because the entire mass is then better heated, both externally and internally), without swelling up, and this method is therefore more convenient than the decomposition of the salt alone. This method for the preparation of oxygen is very convenient; it is generally employed when a small quantity of oxygen is required. Further, potassium chlorate is easily obtained pure, and it evolves much oxygen. 100 grams of the salt give as much as 39 grams, or 30 litres, of oxygen. This method is so simple and easy,[14] that a course of practical chemistry is often commenced by the preparation of oxygen by this method, and of hydrogen by the aid of zinc and sulphuric acid, since by means of these gases many interesting and striking experiments may be performed.[15] [11] All acids rich in oxygen, and especially those whose elements form lower oxides, evolve oxygen either directly at the ordinary temperature (for instance, ferric acid), or on heating (nitric, manganic, chromic, chloric, and others), or if basic lower oxides are formed from them, by heating with sulphuric acid. Thus the salts of chromic acid (for example, potassium dichromate, K_{2}Cr_{2}O_{7}) give oxygen with sulphuric acid; first potassium sulphate, K_{2}SO_{4}, is formed, and then the chromic acid set free gives a sulphuric acid salt of the lower oxide, Cr_{2}O_{3}. [12] This reaction is not reversible, and is exothermal--that is, it does not absorb heat, but, on the contrary, evolves 9,713 calories per molecular weight KClO_{3}, equal to 122 parts of salt (according to the determination of Thomsen, who burnt hydrogen in a calorimeter either alone or with a definite quantity of potassium chlorate mixed with oxide of iron). It does not proceed at once, but first forms perchlorate, KClO_{4} (_see_ Chlorine and Potassium). It is to be remarked that potassium chloride melts at 766°, potassium chlorate at 359°, and potassium perchlorate at 610°. (Concerning the decomposition of KClO_{3}, _see_ Chapter II., Note 47.) [13] The peroxide does not evolve oxygen in this case. It may be replaced by many oxides--for instance, by oxide of iron. It is necessary to take the precaution that no combustible substances (such as bits of paper, splinters, sulphur, &c.) fall into the mixture, as they might cause an explosion. [14] The decomposition of a mixture of fused and well-crushed potassium chlorate with powdered manganese peroxide proceeds at so low a temperature (the salt does not melt) that it may be effected in an ordinary glass flask. The apparatus is arranged in the same manner as in the decomposition of mercury oxide (Introduction), or as shown in the last drawing. As the reaction is exothermal, the decomposition of potassium chlorate with the formation of oxygen may probably be accomplished, under certain conditions (for example, under contact action), at very low temperatures. Substances mixed with the potassium chlorate probably act partially in this manner. [15] Many other salts evolve oxygen by heat, like potassium chlorate, but they only part with it either at a very high temperature (for instance, common nitre) or else are unsuited for use on account of their cost (potassium manganate), or evolve impure oxygen at a high temperature (zinc sulphate at a red heat gives a mixture of sulphurous anhydride and oxygen), and are not therefore used in practice. A solution of _bleaching powder_, which contains calcium hypochlorite, CaCl_{2}O_{2}, evolves oxygen on gently heating when a small quantity of certain oxides is added--for instance, cobalt oxide, which in this case acts by contact (_see_ Introduction). When heated by itself, a solution of bleaching powder does not evolve oxygen, but it oxidises the cobalt oxide to a higher degree of oxidation; this higher oxide of cobalt in contact with the bleaching powder decomposes into oxygen and lower oxidation products, and the resultant lower oxide of cobalt with bleaching powder again gives the higher oxide, which again gives up its oxygen, and so on.[16] The calcium hypochlorite is here decomposed according to the equation CaCl_{2}O_{2} = CaCl_{2} + O_{2}. In this manner a small quantity of cobalt oxide[17] is sufficient for the decomposition of an indefinitely large quantity of bleaching powder. [16] Such is, at present, the only possible method of explaining the phenomenon of contact action. In many cases, such as the present one, it is supported by observations based on facts. Thus, for instance, it is known, as regards oxygen, that often two substances rich in oxygen retain it so long as they are separate, but directly they come into contact free oxygen is evolved from both of them. Thus, an aqueous solution of hydrogen peroxide (containing twice as much oxygen as water) acts in this manner on silver oxide (containing silver and oxygen). This reaction takes place at the ordinary temperature, and the oxygen is evolved from both compounds. To this class of phenomena may be also referred the fact that a mixture of barium peroxide and potassium manganate with water and sulphuric acid evolves oxygen at the ordinary temperature (Note 9 bis). It would seem that the essence of phenomena of this kind is entirely and purely a property of contact; the distribution of the atoms is changed by contact, and if the equilibrium be unstable it is destroyed. This is more especially evident in the case of those substances which change exothermally--that is, for those reactions which are accompanied by an evolution of heat. The decomposition CaCl_{2}O_{2} = CaCl_{2} + O_{2} belongs to this class (like the decomposition of potassium chlorate). [17] Generally a solution of bleaching powder is alkaline (contains free lime), and therefore, a solution of cobalt chloride is added directly to it, by which means the oxide of cobalt required for the reaction is formed. _The properties of oxygen._[18]--It is a permanent _gas_--that is, it cannot be liquefied by pressure at the ordinary temperature, and further, is only liquefied with difficulty (although more easily than hydrogen) at temperatures below -120°, because this is its absolute boiling point. As its critical pressure[19] is about 50 atmospheres, it can be easily liquefied under pressures greater than 50 atmospheres at temperatures below -120°. According to Dewar, the density of oxygen in a critical state is 0·65 (water = 1), but, like all other substances in this state,[20] it varies considerably in density with a change of pressure and temperature, and therefore many investigators who made their observations under high pressures give a greater density, as much as 1·1. Liquefied oxygen is an exceedingly mobile transparent liquid, with a faint blue tint and boiling (tension = 1 atmosphere) about -180°. Oxygen, like all gases, is transparent, and like the majority of gases, colourless. It has no smell or taste, which is evident from the fact of its being a component of air. The weight of one litre of oxygen gas at 0° and 760 mm. pressure is 1·4298 gram; it is therefore slightly denser than air. Its density in respect to air = 1·1056 and in respect to hydrogen = 16.[21] [18] It must be remarked that in all the reactions above mentioned the formation of oxygen may be prevented by the admixture of substances capable of combining with it--for example, charcoal, many carbon (organic) compounds, sulphur, phosphorus, and various lower oxidation products, &c. These substances absorb the oxygen evolved, combine with it, and a compound containing oxygen is formed. Thus, if a mixture of potassium chlorate and charcoal be heated, no oxygen is obtained, but an explosion takes place from the rapid formation of gases resulting from the combination of the oxygen of the potassium chlorate with the charcoal and the evolution of gaseous CO_{2}. The oxygen obtained by any of the above-described methods is rarely pure. It generally contains aqueous vapour, carbonic anhydride, and very often small traces of chlorine. The oxygen may be freed from these impurities by passing it through a solution of caustic potash, and by drying it. If the potassium chlorate be dry and pure, it gives almost pure oxygen. However, if the oxygen be required for respiration in cases of sickness, it should be washed by passing it through a solution of caustic alkali and through water. The best way to obtain pure oxygen directly is to take potassium perchlorate (KClO_{4}), which can be well purified and then evolves pure oxygen on heating. [19] With regard to the absolute boiling point, critical pressure, and the critical state in general, _see_ Chapter II., Notes 29 and 34. [20] Judging from what has been said in Note 34 of the last chapter, and also from the results of direct observation, it is evident that all substances in a critical state have a large coefficient of expansion, and are very compressible. [21] As water consists of 1 volume of oxygen and 2 volumes of hydrogen, and contains 16 parts by weight of oxygen per 2 parts by weight of hydrogen, it therefore follows directly that oxygen is 16 times denser than hydrogen. Conversely, the composition of water by weight may be deduced from the densities of hydrogen and oxygen, and the volumetric composition of water. This method of mutual and reciprocal correction strengthens the practical data of the exact sciences, whose conclusions require the greatest possible exactitude and variety of corrections. It must he observed that the specific heat of oxygen at constant pressure is 0·2175, consequently it is to the specific heat of hydrogen (3·409) as 1 is to 15·6. Hence, the specific heats are inversely proportional to the weights of equal volumes. This signifies that equal volumes of both gases have (nearly) equal specific heats--that is, they require an equal quantity of heat for raising their temperature by 1°. We shall afterwards consider the specific heat of different substances more fully in Chap. XIV. Oxygen, like the majority of difficultly-liquefiable gases, is but slightly soluble in water and other liquids. The solubility is given in Note 30, Chap. I. From this it is evident that water standing in air must absorb--_i.e._ dissolve--oxygen. This oxygen serves for the respiration of fishes. Fishes cannot exist in boiled water, because it does not contain the oxygen necessary for their respiration (_see_ Chap. I.) [Illustration: FIG. 29.--Mode of burning sulphur, phosphorus, sodium, &c., in oxygen.] In its chemical properties oxygen is remarkable from the fact that it very easily--and, in a chemical sense, vigorously--reacts on a number of substances, forming oxygen compounds. However, only a few substances and mixtures of substances (for example, phosphorus, copper with ammonia, decomposing organic matter, aldehyde, pyrogallol with an alkali, &c.) combine directly with oxygen at the ordinary temperature, whilst many substances easily combine with oxygen at a red heat, and often this combination presents a rapid chemical reaction accompanied by the evolution of a large quantity of heat. Every reaction which takes place rapidly, if it be accompanied by so great an evolution of heat as to produce incandescence, is termed _combustion_. Thus combustion ensues when many metals are plunged into chlorine, or oxide of sodium or barium into carbonic anhydride, or when a spark falls on gunpowder. A great many substances are combustible in oxygen, and, owing to its presence, in air also. In order to start combustion it is generally necessary[22] that the combustible substance should be brought to a state of incandescence. The continuation of the process does not require the aid of fresh external heat, because sufficient heat[23] is evolved to raise the temperature of the remaining parts of the combustible substance to the required degree. Examples of this are familiar to all from every-day experience. Combustion proceeds in oxygen with greater rapidity, and is accompanied by a more powerful incandescence, than in ordinary air. This may be demonstrated by a number of very convincing experiments. If a piece of charcoal, attached to a wire and previously brought to red-heat, be plunged into a flask full of oxygen, it burns rapidly at a white heat--_i.e._ it combines with the oxygen, forming a gaseous product of combustion called carbonic anhydride, or carbonic acid gas, CO_{2}. This is the same gas that is evolved in the act of respiration, for charcoal is one of the substances which is obtained by the decomposition of all organic substances which contain it, and in the process of respiration part of the constituents of the body, so to speak, slowly burn. If a piece of burning sulphur be placed in a small cup attached to a wire and introduced into a flask full of oxygen, then the sulphur, which burns in air with a very feeble flame, burns in the oxygen with a violet flame, which, although pale, is much larger than in air. If the sulphur be exchanged for a piece of phosphorus,[24] then, unless the phosphorus be heated, it combines very slowly with the oxygen; but, if heated, although on only one spot, it burns with an exceedingly brilliant white flame. In order to heat the phosphorus inside the flask, the simplest way is to bring a red-hot wire into contact with it. Before the charcoal can burn, it must be brought to a state of incandescence. Sulphur also will not burn under 100°, whilst phosphorus inflames at 40°. Phosphorus which has been already lighted in air cannot so well be introduced into the flask, because it burns very rapidly and with a large flame in air. If a small lump of metallic _sodium_ be put in a small cup made of lime,[25] melted, and ignited,[26] it burns very feebly in air. But if burning sodium be introduced into oxygen, the combustion is invigorated and is accompanied by a brighter yellow flame. Metallic _magnesium_, which burns brightly in air, continues to burn with still greater vigour in oxygen, forming a white powder, which is a compound of magnesium with oxygen (magnesium oxide; magnesia). A strip of _iron_ or steel does not burn in air, but an iron wire or steel spring may be easily burnt in oxygen.[27] The combustion of steel or iron in oxygen is not accompanied by a flame, but sparks of oxide fly in all directions from the burning portions of the iron.[28] [22] Certain substances (with which we shall afterwards become acquainted), however, ignite spontaneously in air; for example, impure phosphuretted hydrogen, silicon hydride, zinc ethyl, and pyrophorus (very finely divided iron, &c.) [23] If so little heat is evolved that the adjacent parts are not heated to the temperature of combustion, then combustion will cease. [24] The phosphorus must be dry; it is usually kept in water, as it oxidises in air. It should be cut under water, as otherwise the freshly-cut surface oxidises. It must be dried carefully and quickly by wrapping it in blotting-paper. If damp, it splutters on burning. A small piece should be taken, as otherwise the iron spoon will melt. In this and the other experiments on combustion, water should be poured over the bottom of the vessel containing the oxygen, to prevent it from cracking. The cork closing the vessel should not fit tightly, in order to allow for the expansion of the gas due to the heat of the combustion. [25] An iron cup will melt with sodium in oxygen. [26] In order to rapidly heat the lime crucible containing the sodium, it is heated in the flame of a blowpipe described in Chap. VIII. [27] In order to burn a watch spring, a piece of tinder (or paper soaked in a solution of nitre, and dried) is attached to one end. The tinder is lighted, and the spring is then plunged into the oxygen. The burning tinder heats the end of the spring, the heated part burns, and in so doing heats the further portions of the spring, which then burns completely if sufficient oxygen be present. [28] The sparks of rust are produced, owing to the fact that the volume of the oxide of iron is nearly twice that of the volume of the iron, and as the heat evolved is not sufficient to entirely melt the oxide or the iron, the particles must be torn off and fly about. Similar sparks are formed in the combustion of iron, in other cases also. We saw the combustion of iron filings in the Introduction. In the welding of iron small iron splinters fly off in all directions and burn in the air, as is seen from the fact that whilst flying through the air they remain red hot, and also because, on cooling, they are seen to be no longer iron, but a compound of it with oxygen. The same thing takes place when the hammer of a gun strikes against the flint. Small scales of steel are heated by the friction, and glow and burn in the air. The combustion of iron is still better seen by taking it as a very fine powder, such as is obtained by the decomposition of certain of its compounds--for instance, by heating Prussian blue, or by the reduction of its compounds with oxygen by hydrogen; when this fine powder is strewn in air, it burns by itself, even without being previously heated (it forms a pyrophorus). This obviously depends on the fact that the powder of iron presents a larger surface of contact with air than an equal weight in a compact form. [Illustration: FIG. 30.--Mode of burning a steel spring in oxygen.] In order to demonstrate by experiment the _combustion of hydrogen_ in oxygen, a gas-conducting tube, bent so as to form a convenient jet, is led from the vessel evolving hydrogen. The hydrogen is first set light to in air, and then the gas-conducting tube is let down into a flask containing oxygen. The combustion in oxygen will be similar to that in air; the flame remains pale, notwithstanding the fact that its temperature rises considerably. It is instructive to remark that oxygen may burn in hydrogen, just as hydrogen in oxygen. In order to show the combustion of oxygen in hydrogen, a tube bent vertically upwards and ending in a fine orifice is attached to the stopcock of a gas-holder full of oxygen. Two wires, placed at such a distance from each other as to allow the passage of a constant series of sparks from a Ruhmkorff's coil, are fixed in front of the orifice of the tube. This is in order to ignite the oxygen, which may also be done by attaching tinder round the orifice, and burning it. When the wires are arranged at the orifice of the tube, and a series of sparks passes between them, then an inverted (because of the lightness of the hydrogen) jar full of hydrogen is placed over the gas-conducting tube. When the jar covers the orifice of the gas-conducting tube (and not before, as otherwise an explosion might take place) the cock of the gasometer is opened, and the oxygen flows into the hydrogen and is set light to by the sparks. The flame obtained is similar to that formed by the combustion of hydrogen in oxygen.[29] From this it is evident that the flame is the locality where the oxygen combines with the hydrogen, therefore a flame of burning oxygen can be obtained as well as a flame of burning hydrogen. [29] The experiment may be conducted without the wires, if the hydrogen be lighted in the orifice of an inverted cylinder, and at the same time the cylinder be brought over the end of a gas-conducting tube connected with a gas-holder containing oxygen. Thomsen's method may be adopted for a lecture experiment. Two glass tubes, with platinum ends, are passed through orifices, about 1-1-1/2 centimetre apart, in a cork. One tube is connected with a gas-holder containing oxygen, and the other with a gas-holder full of hydrogen. Having turned on the gases, the hydrogen is lighted, and a common lamp glass, tapering towards the top, is placed over the cork. The hydrogen continues to burn inside the lamp glass, at the expense of the oxygen. If the current of oxygen be then decreased little by little, a point is reached when, owing to the insufficient supply of oxygen, the flame of the hydrogen increases in size, disappears for several moments, and then reappears at the tube supplying the oxygen. If the flow of oxygen be again increased, the flame reappears at the hydrogen tube. Thus the flame may be made to appear at one or the other tube at will, only the increase or decrease of the current of gas must take place by degrees and not suddenly. Further, air may be taken instead of oxygen, and ordinary coal-gas instead of hydrogen, and it will then be shown how air burns in an atmosphere of coal-gas, and it can easily be proved that the lamp glass is full of a gas combustible in air, because it may be lighted at the top. If, instead of hydrogen, any other combustible gas be taken--for example, ordinary coal gas--then the phenomenon of combustion will be exactly the same, only a bright flame will be obtained, and the products of combustion will be different. However, as coal gas contains a considerable amount of free and combined hydrogen, it will also form a considerable quantity of water in its combustion. If hydrogen be mixed with oxygen in the proportion in which they form water--_i.e._ if two volumes of hydrogen be taken for each volume of oxygen--then the mixture will be the same as that obtained by the decomposition of water by a galvanic current--detonating gas. [Illustration: FIG. 31.--Cavendish's apparatus for exploding detonating gas. The bell jar standing in the bath is filled with a mixture of two volumes of hydrogen and one volume of oxygen, and the thick glass vessel A is then screwed on to it. The air is first pumped out of this vessel, so that when the stopcock C is opened, it becomes filled with detonating gas. The stopcock is then re-closed, and the explosion produced by means of a spark from a Leyden jar. After the explosion has taken place the stopcock is again opened, and the water rises into the vessel A.] We have already mentioned in the last chapter that the combination of these gases, or their explosion, may be brought about by the action of an electric spark, because the spark heats the space through which it passes, and acts consequently in a manner similar to ignition by means of contact with an incandescent or burning substance.[29 bis] Cavendish made this experiment on the ignition of detonating gas, at the end of the last century, in the apparatus shown in fig. 31. Ignition by the aid of the electric spark is convenient, for the reason that it may then be brought about in a closed vessel, and hence chemists still employ this method when it is required to ignite a mixture of oxygen with a combustible gas in a closed vessel. For this purpose, especially since Bunsen's time,[30] an _eudiometer_ is employed. It consists of a thick glass tube graduated along its length in millimetres (for indicating the height of the mercury column), and calibrated for a definite volume (weight of mercury). Two platinum wires are fused into the upper closed end of the tube, as shown in fig. 32.[31] By the aid of the eudiometer we may not only determine the volumetric composition of water,[32] and the quantitative contents of oxygen in air,[33] but also make a number of experiments explaining the phenomenon of combustion. [Illustration: FIG. 32.--Eudiometer] [29 bis] In fact, instead of a spark a fine wire may be taken, and an electric current passed through it to bring it to a state of incandescence; in this case there will be no sparks, but the gases will inflame if the wire be fine enough to become red hot by the passage of the current. [30] Now, a great many other different forms of apparatus, sometimes designed for special purposes, are employed in the laboratory for the investigation of gases. Detailed descriptions of the methods of gas analysis, and of the apparatus employed, must be looked for in works on analytical and applied chemistry. [31] They must be sealed into the tube in such a manner as to leave no aperture between them and the glass. In order to test this, the eudiometer is filled with mercury, and its open end inverted into mercury. If there be the smallest orifice at the wires, the external air will enter into the cylinder and the mercury will fall, although not rapidly if the orifice be very fine. [32] The eudiometer is used for determining the composition of combustible gases. A detailed account of _gas analysis_ would be out of place in this work (_see_ Note 30), but, as an example, we will give a short description of the determination of the composition of water by the eudiometer. Pure and dry oxygen is first introduced into the eudiometer. When the eudiometer and the gas in it acquire the temperature of the surrounding atmosphere--which is recognised by the fact of the meniscus of the mercury not altering its position during a long period of time--then the heights at which the mercury stands in the eudiometer and in the bath are observed. The difference (in millimetres) gives the height of the column of mercury in the eudiometer. It must be reduced to the height at which the mercury would stand at 0° and deducted from the atmospheric pressure, in order to find the pressure under which the oxygen is measured (_see_ Chap. I. Note 29). The height of the mercury also shows the volume of the oxygen. The temperature of the surrounding atmosphere and the height of the barometric column must also be observed, in order to know the temperature of the oxygen and the atmospheric pressure. When the volume of the oxygen has been measured, pure and dry hydrogen is introduced into the eudiometer, and the volume of the gases in the eudiometer again measured. They are then exploded. This is done by a Leyden jar, whose outer coating is connected by a chain with one wire, so that a spark passes when the other wire, fused into the eudiometer, is touched by the terminal of the jar. Or else an electrophorus is used, or, better still, a Ruhmkorff's coil, which has the advantage of working equally well in damp or dry air, whilst a Leyden jar or electrical machine does not act in damp weather. Further, it is necessary to close the lower orifice of the eudiometer before the explosion (for this purpose the eudiometer, which is fixed in a stand, is firmly pressed down from above on to a piece of india-rubber placed at the bottom of the bath), as otherwise the mercury and gas would be thrown out of the apparatus by the explosion. It must also be remarked that to ensure complete combustion the proportion between the volumes of oxygen and hydrogen must not exceed twelve of hydrogen to one volume of oxygen, or fifteen volumes of oxygen to one volume of hydrogen, because no explosion will take place if one of the gases be in great excess. It is best to take a mixture of one volume of hydrogen with several volumes of oxygen. The combustion will then be complete. It is evident that water is formed, and that the volume (or tension) is diminished, so that on opening the end of the eudiometer the mercury will rise in it. But the tension of the aqueous vapour is now added to the tension of the gas remaining after the explosion. This must be taken into account (Chap. I. Note 1). If but little gas remain, the water which is formed will be sufficient for its saturation with aqueous vapour. This may be learnt from the fact that drops of water are visible on the sides of the eudiometer after the mercury has risen in it. If there be none, a certain quantity of water must be introduced into the eudiometer. Then the number of millimetres expressing the pressure of the vapour corresponding with the temperature of the experiment must be subtracted from the atmospheric pressure at which the remaining gas is measured, otherwise the result will be inaccurate (Chap. I. Note 1). This is essentially the method of the determination of the composition of water which was made for the first time by Gay-Lussac and Humboldt with sufficient accuracy. Their determinations led them to the conclusion that water consists of two volumes of hydrogen (more exactly 2·003, Le Duc 1892), and one volume of oxygen. Every time they took a greater quantity of oxygen, the gas remaining after the explosion was oxygen. When they took an excess of hydrogen, the remaining gas was hydrogen; and when the oxygen and hydrogen were taken in exactly the above proportion, neither one nor the other remained. The composition of water was thus definitely confirmed. [33] Concerning this application of the eudiometer, see the chapter on Nitrogen. It may be mentioned as illustrating the various uses of the eudiometer that Prof. Timeraseeff employed microscopically small eudiometers to analyse the bubbles of gas given off from the leaves of plants. Thus, for example, it may be demonstrated, by the aid of the eudiometer, that for the ignition of detonating gas, a _definite temperature_ is required. If the temperature be below that required, combination will not take place, but if at any spot within the tube it rises to the temperature of inflammation, then combination will ensue at that spot, and evolve enough heat for the ignition of the adjacent portions of the detonating mixture. If to 1 volume of detonating gas there be added 10 volumes of oxygen, or 4 volumes of hydrogen, or 3 volumes of carbonic anhydride, then we shall not obtain an explosion by passing a spark through the diluted mixture. This depends on the fact that the temperature falls with the dilution of the detonating gas by another gas, because the heat evolved by the combination of the small quantity of hydrogen and oxygen brought to incandescence by the spark is not only transmitted to the water proceeding from the combination, but also to the foreign substance mixed with the detonating gas.[34] The necessity of a definite temperature for the ignition of detonating gas is also seen from the fact that pure detonating gas explodes in the presence of a red-hot iron wire, or of charcoal heated to 275°, but with a lower degree of incandescence there is not any explosion. It may also be brought about by rapid compression, when, as is known, heat is evolved.[35] Experiments made in the eudiometer showed that the ignition of detonating gas takes place at a temperature between 450° and 560°.[36] [34] Thus 1/4 volume of carbonic oxide, an equal volume of marsh gas, two volumes of hydrogen chloride or of ammonia, and six volumes of nitrogen or twelve volumes of air added to one volume of detonating gas, prevent its explosion. [35] If the compression be brought about slowly, so that the heat evolved succeeds in passing to the surrounding space, then the combination of the oxygen and hydrogen does not take place, even when the mixture is compressed by 150 times; for the gases are not heated. If paper soaked with a solution of platinum (in aqua regia) and sal ammoniac be burnt, then the ash obtained contains very finely-divided platinum, and in this form it is best fitted for igniting hydrogen and detonating gas. Platinum wire requires to be heated, but platinum in so finely divided a state as it occurs in this ash inflames hydrogen, even at -20°. Many other metals, such as palladium (175°), iridium, and gold, act with a slight rise of temperature, like platinum; but mercury, at its boiling point, does not inflame detonating gas, although the slow formation of water then begins at 305°. All data of this kind show that the explosion of detonating gas presents one of the many cases of contact phenomena. This conclusion is further confirmed by the researches of V. Meyer (1892). He showed that only a very slow formation of steam begins at 448°, and that it only proceeds more rapidly at 518°. The temperature of the explosion of detonating gas, according to the same author, varies according as to whether the explosion is produced in open vessels or in closed tubes. In the first case the temperature of explosion lies between 530°-606°, and in the second between 630°-730°. In general it may be remarked that the temperature of explosion of gaseous mixtures is always lower in closed vessels than when the detonating mixture flows freely through tubes. According to Freyer and V. Meyer, the following gases when mixed with the requisite amount of oxygen explode at the following temperatures: +----------------+---------------------+-------------------+ | -- | When flowing freely | In closed vessels | +----------------+---------------------+-------------------+ | H_{2} | 630°-730° | 530°-606° | | CH_{4} | 650°-730° | 606°-650° | | C_{2}H_{6} | 606°-650° | 530°-606° | | C_{2}H_{4} | 606°-650° | 530°-606° | | CO | 650°-730° | 650°-730° | | H_{2}S | 315°-320° | 250°-270° | | H_{2} + Cl_{2} | 430°-440° | 240°-270° | +----------------+---------------------+-------------------+ The velocity of the transmission of explosion in gaseous mixtures is as characteristic a quantity for gaseous systems as the velocity of the transmission of sound. Berthelot showed that this velocity depends neither upon the pressure nor upon the size of the tubes in which the gaseous mixture is contained, nor upon the material out of which the tube is made. Dixon (1891) determined the magnitude of these velocities for various mixtures, and his results proved very near to those previously given by Berthelot. For comparison we give the velocities expressed in metres per second: +-----------------+-------+-----------+ | -- | Dixon | Berthelot | +-----------------+-------+-----------+ | H_{2} + O | 2,821 | 2,810 | | H_{2} + N_{2}O | 2,305 | 2,284 | | CH_{4} + 4O | 2,322 | 2,287 | | C_{2}H_{2} + 6O | 2,364 | 2,210 | | C_{2}H_{2} + 5O | 2,391 | 2,482 | | C_{2}N_{2} + 4O | 2,321 | 2,195 | +-----------------+-------+-----------+ The addition of oxygen to detonating gas lowers the velocity of the transmission of explosion almost as much as the introduction of nitrogen. An excess of hydrogen on the contrary raises the velocity of transmission. It is remarked that the explosion of mixtures of oxygen with marsh gas, ethylene and cyanogen is transmitted more quickly if the oxygen be taken in such a proportion that the carbon should burn to oxide of carbon, _i.e._ the velocity of the explosion is less if the oxygen be taken in sufficient quantity to form carbonic anhydride. Observations upon liquid and solid explosives (Berthelot) show that in this case the velocity of transmission of explosion is dependent upon the material of the tube. Thus the explosion of liquid nitro-methyl ether in glass tubes travels at the rate (in dependence upon the diam., from 1 mm.-45 mm.) of from 1,890 to 2,482 metres, and in tubes of Britannia metal (3 mm. in diam) at the rate of 1,230 metres. The harder the tube the greater the velocity of transmission of explosion. The following are the velocities for certain bodies: metres Nitro-glycerine 1,300 Dynamite 2,500 Nitro-mannite 7,700 Picric acid 6,500 In conclusion we may add that Mallard and Le Chatelier (1882) observed that in the explosion of a mixture of 1 volume of detonating gas with _n_ volumes of an inert gas, the pressure is approximately equal to 9·2-0·9_n_ atmospheres. [36] From the very commencement of the promulgation of the idea of dissociation, it might have been imagined that reversible reactions of combination (the formation of H_{2} and O belongs to this number) commence at the same temperature as that at which dissociation begins. And in many cases this is so, but not always, as may be seen from the facts (1) that at 450-560°, when detonating gas explodes, the density of aqueous vapour not only does not vary (and it hardly varies at higher temperatures, probably because the amount of the products of dissociation is small), but there are not, as far as is yet known, any traces of dissociation; (2) that under the influence of contact the temperature at which combination takes place falls even to the ordinary temperature, when water and similar compounds naturally are not dissociated and, judging from the data communicated by D. P. Konovaloff (Introduction, Note 39) and others, it is impossible to escape the phenomena of contact; all vessels, whether of metal or glass, show the same influence as spongy platinum, although to a much less degree. The phenomena of contact, judging from a review of the data referring to it, must be especially sensitive in reactions which are powerfully exothermal, and the explosion of detonating gas is of this kind. The combination of hydrogen with oxygen is accompanied by the evolution of a very considerable amount of heat; according to the determinations of _Favre_ and _Silbermann_,[37] 1 part by weight of hydrogen in forming water evolves 34,462 units of heat. Many of the most recent determinations are very close to this figure, so that it may be taken that in the formation of 18 parts of water (H_{2}O) there are evolved 69 major calories, or 69,000 units of heat.[38] _If the specific heat of aqueous vapour_ (0·48) _remained constant from the ordinary temperature to that at which the combustion of detonating gas takes place_ (but there is now no doubt that it increases), were the combustion concentrated at one point[39] (but it occurs in the whole region of a flame), were there no loss from radiation and heat conduction, and _did dissociation not take place_--that is, did not a state of equilibrium between the hydrogen, oxygen, and water come about--_then it would be possible to calculate the temperature of the flame of detonating gas_. It would then be 8,000°.[40] In reality it is very much lower, but it is nevertheless higher than the temperature attained in furnaces and flames, and is as high as 2,000°. The explosion of detonating gas is explained by this high temperature, because the aqueous vapour formed must occupy a volume at least 5 times greater than that occupied by the detonating gas at the ordinary temperature. Detonating gas emits a sound, not only as a consequence of the commotion which occurs from the rapid expansion of the heated vapour, but also because it is immediately followed by a cooling effect, the conversion of the vapour into water, and a rapid contraction.[41] [37] [Illustration: FIG. 33.--Favre and Silbermann's calorimeter for determining the heat evolved in combustion.] The amount of heat evolved in the combustion of a known weight (for instance, 1 gram) of a given substance is determined by the rise in temperature of water, to which the whole of the heat evolved in the combustion is transmitted. A _calorimeter_, for example that shown in fig. 33, is employed for this purpose. It consists of a thin (in order that it may absorb less heat), polished (that it should transmit a minimum of heat) metallic vessel, surrounded by down (_c_), or some other bad conductor of heat, and an outer metallic vessel. This is necessary in order that the least possible amount of heat should be lost from the vessels; nevertheless, there is always a certain loss, whose magnitude is determined by preliminary experiment (by taking warm water, and determining its fall in temperature after a definite period of time) as a correction for the results of observations. The water to which the heat of the burning substance is transmitted is poured into the vessel. The stirrer _g_ allows of all the layers of water being brought to the same temperature, and the thermometer serves for the determination of the temperature of the water. The heat evolved passes, naturally, not to the water only, but to all the parts of the apparatus. The quantity of water corresponding to the whole amount of those objects (the vessels, tubes, &c.) to which the heat is transmitted is previously determined, and in this manner another most important correction is made in the calorimetric determinations. The combustion itself is carried on in the vessel _a_. The ignited substance is introduced through the tube at the top, which closes tightly. In fig. 33 the apparatus is arranged for the combustion of a gas, introduced by a tube. The oxygen required for the combustion is led into _a_ by the tube _e_, and the products of combustion either remain in the vessel _a_ (if liquid or solid), or escape by the tube _f_ into an apparatus in which their quantity and properties can easily be determined. Thus the heat evolved in combustion passes to the walls of the vessel _a_, and to the gases which are formed in it, and these transmit it to the water of the calorimeter. [38] This quantity of heat corresponds with the formation of liquid water at the ordinary temperature from detonating gas at the same temperature. If the water be as vapour the heat evolved = 58 major calories; if as ice = 70·4 major calories. A portion of this heat is due to the fact that 2 vols. of hydrogen and 1 vol. of oxygen give 2 vols. of aqueous vapour--that is to say, contraction ensues--and this evolves heat. This quantity of heat may be calculated, but it cannot be said how much is expended in the separation of the atoms of oxygen from each other, and, therefore, strictly speaking, we do not know the quantity of heat which is evolved in the reaction alone, although the number of units of heat evolved in the combustion of detonating gas is accurately known. The construction of the calorimeter and even the method of determination vary considerably in different cases. Since the beginning of the nineties, a large number of determinations of the heat of combustion have been conducted in closed bombs containing compressed oxygen. The greatest number of calorimetric determinations were made by Berthelot and Thomsen. They are given in their works _Essai de mécanique chimique fondée sur la thermochimie_, by M. Berthelot, 1879 (2 vols.), and _thermochemische Untersuchungen_, by J. Thomsen, 1886 (4 vols.) The most important methods of recent thermochemistry, and all the trustworthy results of experiment, are given in Prof. P. F. Louginin's _Description of the Different Modes of Determining the Heat of Combustion of Organic Compounds_, Moscow, 1894. The student must refer to works on theoretical and physical chemistry for a description of the elements and methods of _thermochemistry_, into the details of which it is impossible to enter in this work. One of the originators of thermochemistry, Hess, was a member of the St. Petersburg Academy of Sciences. Since 1870 a large amount of research has been carried out in this province of chemistry, especially in France and Germany, after the investigations of the French Academician, Berthelot, and Professor Thomsen, of Copenhagen. Among Russians, Beketoff, Louginin, Cheltzoff, Chroustchoff, and others are known by their thermochemical researches. The present epoch of thermochemistry must be considered rather as a collective one, wherein the material of facts is amassed, and the first consequences arising from them are noticed. In my opinion two essential circumstances prevent the possibility of deducing any exact consequences, of importance to chemical mechanics, from the immense store of thermochemical data already collected: (1) The majority of the determinations are conducted in weak aqueous solutions, and, the heat of solution being known, are referred to the substances in solution; yet there is much (Chapter I.) which leads to the conclusion that in solution water does not play the simple part of a diluting medium, but of itself acts independently in a chemical sense on the substance dissolved. (2) Physical and mechanical changes (decrease of volume, diffusion, and others) invariably proceed side by side with chemical changes, and for the present it is impossible, in a number of cases, to distinguish the thermal effect of the one and the other kind of change. It is evident that the one kind of change (chemical) is essentially inseparable and incomprehensible without the other (mechanical and physical); and therefore it seems to me that thermochemical data will only acquire their true meaning when the connection between the phenomena of both kinds (on the one hand chemical and atomic, and on the other hand mechanical and molecular or between entire masses) is explained more clearly and fully than is at present the case. As there is no doubt that the simple mechanical contact, or the action of heat alone, on substances sometimes causes an evident and always a latent (incipient) chemical change--that is, a different distribution or motion of the atoms in the molecules--it follows that purely chemical phenomena are inseparable from physical and mechanical phenomena. A mechanical change may be imagined without a physical change, and a physical without a chemical change, but it is impossible to imagine a chemical change without a physical and mechanical one, for without the latter we should not be able to recognise the former, and it is by their means that we are enabled to do so. [39] The flame, or locality where the combustion of gases and vapours takes place, is a complex phenomenon, 'an entire factory,' as Faraday says, and therefore we will consider flame in some detail in one of the following notes. [40] If 34,500 units of heat are evolved in the combustion of 1 part of hydrogen, and this heat is transmitted to the resulting 9 parts by weight of aqueous vapour, then we find that, taking the specific heat of the latter as 0·475, each unit of heat raises the temperature of 1 part by weight of aqueous vapour 2°·1 and 9 parts by weight (2·1 ÷ 9) O°·23; hence the 34,500 units of heat raise its temperature 7,935°. If detonating gas is converted into water in a closed space, then the aqueous vapour formed cannot expand, and therefore, in calculating the temperature of combustion, the specific heat at a constant volume must be taken into consideration; for aqueous vapour it is 0·36. This figure gives a still higher temperature for the flame. In reality it is much lower, but the results given by different observers are very contradictory (from 1,700° to 2,400°), the discrepancies depending on the fact that flames of different sizes are cooled by radiation to a different degree, but mainly on the fact that the methods and apparatus (pyrometers) for the determination of high temperatures, although they enable relative changes of temperature to be judged, are of little use for determining their absolute magnitude. By taking the temperature of the flame of detonating gas as 2,000°, I give, I think, the average of the most trustworthy determinations and calculations based upon the determination of the variation of the specific heat of aqueous vapour and other gases (_see_ Chapter XLI.) [41] It is evident that not only hydrogen, but every other combustible gas, will give an explosive mixture with oxygen. For this reason coal-gas mixed with air explodes when the mixture is ignited. The pressure obtained in the explosions serves as the _motive power of gas engines_. In this case advantage is taken, not only of the pressure produced by the explosion, but also of that contraction which takes place after the explosion. On this is based the construction of several motors, of which Lenoir's was formerly, and Otto's is now, the best known. The explosion is usually produced by coal-gas and air, but of late the vapours of combustible liquids (kerosene, benzene) are also being employed in place of gas (Chapter IX.) In Lenoir's engine a mixture of coal-gas and air is ignited by means of sparks from a Ruhmkorff's coil, but in the most recent machines the gases are ignited by the direct action of a gas jet, or by contact with the hot walls of a side tube. [Illustration: FIG. 34.--Safety burner for detonating gas, described in text.] Mixtures of hydrogen and of various other gases with oxygen are taken advantage of for obtaining high temperatures. By the aid of such high temperatures metals like platinum may be melted on a large scale, which cannot be performed in furnaces heated with charcoal and fed by a current of air. The burner, shown in fig. 34, is constructed for the application of detonating gas to the purpose. It consists of two brass tubes, one fixed inside the other, as shown in the drawing. The internal central tube C C conducts oxygen, and the outside, enveloping, tube E' E' conducts hydrogen. Previous to their egress the gases do not mix together, so that there can be no explosion inside the apparatus. When this burner is in use C is connected with a gas-holder containing oxygen, and E with a gas-holder containing hydrogen (or sometimes coal-gas). The flow of the gases can be easily regulated by the stopcocks O H. The flame is shortest and evolves the greatest heat when the gases burning are in the proportion of 1 volume of oxygen to 2 volumes of hydrogen. The degree of heat may be easily judged from the fact that a thin platinum wire placed in the flame of a properly proportioned mixture easily melts. By placing the burner in the orifice of a hollow piece of lime, a crucible A B is obtained in which the platinum may be easily melted, even in large quantities if the current of oxygen and hydrogen be sufficiently great (Deville). The flame of detonating gas may also be used for illuminating purposes. It is by itself very pale, but owing to its high temperature it may serve for rendering infusible objects incandescent, and at the very high temperature produced by the detonating gas the incandescent substance gives a most intense light. For this purpose lime, magnesia, or oxide of zirconium are used, as they are not fusible at the very high temperature evolved by the detonating gas. A small cylinder of lime placed in the flame of detonating gas, if regulated to the required point, gives a very brilliant white light, which was at one time proposed for illuminating lighthouses. At present in the majority of cases the electric light, owing to its constancy and other advantages, has replaced it for this purpose. The light produced by the incandescence of lime in detonating gas is called the _Drummond light_ or _limelight_. The above cases form examples of the combustion of elements in oxygen, but exactly similar phenomena are observed in the _combustion of compounds_. So, for instance, the solid, colourless, shiny substance, naphthalene, C_{10}H_{8}, burns in the air with a smoky flame, whilst in oxygen it continues to burn with a very brilliant flame. Alcohol, oil, and other substances burn brilliantly in oxygen on conducting the oxygen by a tube to the flame of lamps burning these substances. A high temperature is thus evolved, which is sometimes taken advantage of in chemical practice. In order to understand why combustion in oxygen proceeds more rapidly, and is accompanied by a more intense heat effect, than combustion in air, it must be recollected that air is oxygen diluted with nitrogen, which does not support combustion, and therefore fewer particles of oxygen flow to the surface of a substance burning in air than when burning in pure oxygen, besides which the reason of the intensity of combustion in oxygen is the high temperature acquired by the substance burning in it.[41 bis] [41 bis] Let us consider as an example the combustion of sulphur in air and in oxygen. If 1 gram of sulphur burns in air or oxygen it evolves in either case 2250 units of heat--_i.e._ evolves sufficient heat for heating 2,250 grams of water 1° C. This heat is first of all transmitted to the sulphurous anhydride, SO_{2}, formed by the combination of sulphur with oxygen. In its combustion 1 gram of sulphur forms 2 grams of sulphurous anhydride--_i.e._ the sulphur combines with 1 gram of oxygen. In order that 1 gram of sulphur should have access to 1 gram of oxygen in air, it is necessary that 3·4 grams of nitrogen should simultaneously reach the sulphur, because air contains seventy-seven parts of nitrogen (by weight) per twenty-three parts of oxygen. Thus in the combustion of 1 gram of sulphur, the 2,250 units of heat are transmitted to 2 grams of sulphurous oxide and to at least 3·4 grams of nitrogen. As 0·155 unit of heat is required to raise 1 gram of sulphurous anhydride 1° C., therefore 2 grams require 0·31 unit. So also 3·4 grams of nitrogen require 3·4 × 0·244 or 0·83 unit of heat, and therefore in order to raise both gases 1° C. 0·31 + 0·83 or 1·14 unit of heat is required; but as the combustion of the sulphur evolves 2,250 units of heat, therefore the gases might be heated (if their specific heats remained constant) to 2250/1·14 or 1,974° C. That is, the maximum possible temperature of the flame of the sulphur burning in air will be 1,974° C. In the combustion of the sulphur in oxygen the heat evolved (2,250 units) can only pass to the 2 grams of sulphurous anhydride, and therefore the highest possible temperature of the flame of the sulphur in oxygen will be = 2250/0·31 or 7258°. In the same manner it may be calculated that the temperature of charcoal burning in air cannot exceed 2,700°, while in oxygen it may attain 10,100° C. For this reason the temperature in oxygen will always be higher than in air, although (judging from what has been said respecting detonating gas) neither one temperature nor the other will ever approximate to the theoretical amount. [Illustration: FIG. 35.--Faraday's experiment for investigating the different parts of a candle flame.] Among the phenomena accompanying the combustion of certain substances, the _phenomenon of flame_ attracts attention. Sulphur, phosphorus, sodium, magnesium, naphthalene, &c., burn like hydrogen with a flame, whilst in the combustion of other substances no flame is observed, as, for instance, in the combustion of iron and of charcoal. The appearance of flame depends on the capacity of the combustible substance to yield gases or vapours at the temperature of combustion. At the temperature of combustion, sulphur, phosphorus, sodium, and naphthalene pass into vapour, whilst wood, alcohol, oil, &c., are decomposed into gaseous and vaporous substances. The combustion of gases and vapours forms flames, and therefore _a flame is composed of the hot and incandescent gases and vapours produced by combustion_. It may easily be proved that the flames of such non-volatile substances as wood contain volatile and combustible substances formed from them, by placing a tube in the flame connected with an aspirator. Besides the products of combustion, combustible gases and liquids, previously in the flame as vapours, collect in the aspirator. For this experiment to succeed--_i.e._ in order to really extract combustible gases and vapours from the flame it is necessary that the suction tube should be placed _inside_ the flame. The combustible gases and vapours can only remain unburnt inside the flame, for at the surface of the flame they come into contact with the oxygen of the air and burn.[42] Flames are of different degrees of _brilliancy_, according to whether _solid_ incandescent particles occur in the combustible gas or vapour, or not. Incandescent gases and vapours emit but little light by themselves, and therefore give a paler flame.[43] If a flame does not contain solid particles it is transparent, pale, and emits but little light.[44] The flames of burning alcohol, sulphur, and hydrogen are of this kind. A pale flame may be rendered luminous by placing fine particles of solid matter in it. Thus, if a very fine platinum wire be placed in the pale flame of burning alcohol--or, better still, of hydrogen--the flame emits a bright light. This is still better seen by sifting the powder of an incombustible substance, such as fine sand, into the flame, or by placing a bunch of asbestos threads in it. Every brilliant flame always contains some kind of solid particles, or at least some very dense vapour. The flame of sodium burning in oxygen has a brilliant yellow colour, from the presence of particles of solid sodium oxide. The flame of magnesium is brilliant from the fact that in burning it forms solid magnesia, which becomes white hot, and similarly the brilliancy of the Drummond light is due to the heat of the flame raising the solid non-volatile lime to a state of incandescence. The flames of a candle, wood, and similar substances are brilliant, because they contain particles of charcoal or soot. It is not the flame itself which is luminous, but the incandescent soot it contains. These particles of charcoal which occur in flames may be easily observed by introducing a cold object, like a knife, into the flame.[45] The particles of charcoal burn at the outer surface of the flame if the supply of air be sufficient, but if the supply of air--that is, of oxygen--be insufficient for their combustion the flame smokes, because the unconsumed particles of charcoal are carried off by the current of air.[46] [42] Faraday proved this by a very convincing experiment on a candle flame. If one arm of a bent glass tube be placed in a candle flame above the wick in the dark portion of the flame, then the products of the partial combustion of the stearin will pass up the tube, condense in the other arm, and collect in a flask placed under it (fig. 35) as heavy white fumes which burn when lighted. If the tube be raised into the upper luminous portion of the flame, then a dense black smoke which will not inflame accumulates in the flask. Lastly, if the tube be let down until it touches the wick, then little but stearic acid condenses in the flask. [43] All transparent substances which transmit light with great ease (that is, which absorb but little light) are but little luminous when heated; so also substances which absorb but few heat rays, when heated transmit few rays of heat. [44] There is, however, no doubt but that very heavy dense vapours or gases under pressure (according to the experiments of Frankland) are luminous when heated, because, as they become denser they approach a liquid or solid state. Thus detonating gas when exploded under pressure gives a brilliant light. [45] If hydrogen gas be passed through a volatile liquid hydrocarbon--for instance, through benzene (the benzene may be poured directly into the vessel in which hydrogen is generated)--then its vapour burns with the hydrogen and gives a very bright flame, because the resultant particles of carbon (soot) become incandescent. Benzene, or platinum gauze, introduced into a hydrogen flame may be employed for illuminating purposes. [46] In _flames_ the separate parts may be distinguished with more or less distinctness. That portion of the flame whither the combustible vapours or gases flow, is not luminous because its temperature is still too low for the process of combustion to take place in it. This is the space which in a candle surrounds the wick, or in a gas jet is immediately above the orifice from which the gas escapes. In a candle the combustible vapours and gases which are formed by the action of heat on the melted tallow or stearin rise in the wick, and are heated by the high temperature of the flame. By the action of the heat, the solid or liquid substance is here, as in other cases, decomposed, forming products of dry distillation. These products occur in the central portion of the flame of a candle. The air travels to it from the outside, and is not able to intermix at once with the vapours and gases in all parts of the flame equally; consequently, in the outer portion of the flame the amount of oxygen will be greater than in the interior portions. But, owing to diffusion, the oxygen, of course mixed with nitrogen, flowing towards the combustible substance, does finally penetrate to the interior of the flame (when the combustion takes place in ordinary air). The combustible vapours and gases combine with this oxygen, evolve a considerable amount of heat, and bring about that state of incandescence which is so necessary both for keeping up the combustion and also for the uses to which the flame is applied. Passing from the colder envelope of air through the interior of the flame, to the source of the combustible vapours (for instance, the wick), we evidently first traverse layers of higher and higher temperature, and then portions which are less and less hot, in which the combustion is less complete, owing to the limited supply of oxygen. [Illustrationtion: FIG. 36.--In the candle flame the portion C contains the vapours and products of decomposition; in the bright zone A the combustion has commenced, and particles of carbon are emitted; and in the pale zone B the combustion is completed.] Thus unburnt products of the decomposition of organic substances occur in the interior of the flame. But there is always free hydrogen in the interior of the flame, even when oxygen is introduced there, or when a mixture of hydrogen and oxygen burns, because the temperature evolved in the combustion of hydrogen or the carbon of organic matter is so high that the products of combustion are themselves partially decomposed--that is, dissociated--at this temperature. Hence, in a flame a portion of the hydrogen and of the oxygen which might combine with the combustible substances must always be present in a free state. If a hydrocarbon burns, and we imagine that a portion of the hydrogen is in a free state, then a portion of the carbon must also occur in the same form in the flame, because, other conditions being unchanged, carbon burns after hydrogen, and this is actually observed in the combustion of various hydrocarbons. Charcoal, or the soot of a common flame, arises from the dissociation of organic substances contained in the flame. The majority of hydrocarbons, especially those containing much carbon--for instance, naphthalene--burn, even in oxygen, with separation of soot. In that portion of the flame where the hydrogen burns the carbon remains unburnt, or at least partly so. It is this free carbon which causes the brilliancy of the flame. That the interior of the flame contains a mixture which is still capable of combustion may be proved by the following experiment: A portion of the gases may be withdrawn by an aspirator from the central portion of the flame of carbonic oxide, which is combustible in air. For this purpose Deville passed water through a metallic tube having a fine lateral orifice, which is placed in the flame. As the water flows along the tube portions of the gases of the flame enter, and, passing along the tube alternately with cylinders of water, are carried away into an apparatus where they can be investigated. It appears that all portions of the flame obtained by the combustion of a mixture of carbonic oxide and oxygen contain a portion of this mixture still unburnt. The researches of Deville and Bunsen showed that in the explosion of a mixture of hydrogen and of carbonic oxide with oxygen in a closed space, complete combustion does not ever take place immediately. If two volumes of hydrogen and one volume of oxygen be confined in a closed space, then on explosion the pressure does not attain that magnitude which it would were there immediate and complete combustion. It may be calculated that the pressure should attain twenty-six atmospheres. In reality, it does not exceed nine and a half atmospheres. Hence the admixture of the products of combustion with an explosive mixture prevents the combustion of the remaining mass, although capable of burning. The admixture of carbonic anhydride prevents carbonic oxide from burning. The presence of any other foreign gas interferes in the same manner. This shows that every portion of a flame must contain combustible, burning, and already burnt substances--_i.e._ oxygen, carbon, carbonic oxide, hydrogen, hydrocarbons, carbonic anhydride, and water. Consequently, _it is impossible to attain instantaneous complete combustion_, and this is one of the reasons of the phenomenon of flame. A certain space is required, and the temperature must be unequal in different parts of it. In this space different quantities of the component parts are successively subjected to combustion, or are cooled under the influence of adjacent objects, and combustion only ends where the flame ends. If the combustion could be concentrated at one spot, then the temperature would be incomparably higher than it is under the actual circumstances. The various regions of the flame have formed the frequent subject of experimental research, and the experiments conducted by Smithells and Ingle (1892) are particularly instructive; they show that the reducing (interior) and oxidising (exterior) portions of the flame of a burning gas may be divided by taking a Bunsen burner and surrounding the flame of the gas burnt in it, by another wider tube (without the access of air to the annular space or allowing only a small current of air to pass), when a gaseous mixture, containing oxide of carbon and capable of further combustion, will issue from this enveloping tube, so that a second flame, corresponding to the exterior (oxidising) portion of an ordinary flame, may be obtained above the enveloping tube. This division of the flame into two portions is particularly clear when cyanogen C_{2}N_{2} is burnt, because the interior portion (where CO is chiefly formed according to the equation C_{2}N_{2} + O_{2} = 2CO + N_{2}, but a portion of the nitrogen is oxidised) is of a rose colour, while the exterior portion (where the CO burns into CO_{2} at the expense of a fresh quantity of oxygen and of the oxides of nitrogen proceeding from the interior portions) is of a bluish-grey colour. The combination of various substances with oxygen may not present any signs of combustion--that is, the temperature may rise but inconsiderably. This may either proceed from the fact that the reaction of the substance (for example, tin, mercury, lead at a high temperature, or a mixture of pyrogallol with caustic potash at the ordinary temperature) evolves but little heat, or that the heat evolved is transmitted to good conductors of heat, like metals, or that the combination with oxygen takes place so slowly that the heat evolved succeeds in passing to the surrounding objects. Combustion is only a particular, intense, and evident case of combination with oxygen. Respiration is also an act of combination with oxygen; it also serves, like combustion, for the development of heat by those chemical processes which accompany it (the transformation of oxygen into carbonic anhydride). Lavoisier enunciated this in the lucid expression, 'respiration is slow combustion.' Reactions involving slow combination of substances with oxygen are termed _oxidations_. Combination of this kind (and also combustion) often results in the formation of acid substances, and hence the name _oxygen_ (_Sauerstoff_). Combustion is only rapid oxidation. Phosphorus, iron, and wine may be taken as examples of substances which slowly oxidise in air at the ordinary temperature. If such a substance be left in contact with a definite volume of air or oxygen, it absorbs the oxygen little by little, as may be seen by the decrease in volume of the gas. This slow oxidation is not often accompanied by a sensible evolution of heat; an evolution of heat really does occur, only it is not apparent to our senses owing to the small rise in temperature which takes place; this is owing to the slow rate of the reaction and to the transmission of the heat formed as radiant heat, &c. Thus, in the oxidation of wine and its transformation into vinegar by the usual method of preparation of the latter, the heat evolved cannot be observed because it extends over several weeks, but in the so-called rapid process of the manufacture of vinegar, when a large quantity of wine is comparatively rapidly oxidised, the evolution of heat is quite apparent. Such slow processes of oxidation are always taking place in nature by the action of the atmosphere. Dead organisms and the substances obtained from them--such as bodies of animals, wood, wool, grass, &c.--are especially subject to this action. They _rot_ and _decompose_--that is, their solid matter is transformed into gases, under the influence of moisture and atmospheric oxygen, and generally under the influence of other organisms, such as moulds, worms, micro-organisms (bacteria), and the like. These are processes of slow combustion, of slow combination with oxygen. It is well known that manure rots and develops heat, that stacks of damp hay, damp flour, straw, &c., become heated and are changed in the process.[47] In all these transformations the same chief products of combustion are formed as those which are contained in smoke; the carbon gives carbonic anhydride, and the hydrogen water. Hence these processes require oxygen just like combustion. This is the reason why the entire prevention of access of air hinders these transformations,[48] and an increased supply of air accelerates them. The mechanical treatment of arable lands by the plough, harrow, and other similar means has not only the object of facilitating the spread of roots in the ground, and of making the soil more permeable to water, but it also serves to facilitate the access of the air to the component parts of the soil; as a consequence of which the organic remains of soil rot--so to speak, breathe air and evolve carbonic anhydride. One acre of good garden land in the course of a summer evolves more than sixteen tons of carbonic anhydride. [47] Cotton waste (used in factories for cleaning machines from lubricating oil) soaked in oil and lying in heaps is self-combustible, being oxidised by the air. [48] When it is desired to preserve a supply of vegetable and animal food, the access of the oxygen of the atmosphere (and also of the germs of organisms present in the air) is often prevented. With this object articles of food are often kept in hermetically closed vessels, from which the air has been withdrawn; vegetables are dried and soldered up while hot in tin boxes; sardines are immersed in oil, &c. The removal of water from substances is also sometimes resorted to with the same object (the drying of hay, corn, fruits), as also is saturation with substances which absorb oxygen (such as sulphurous anhydride), or which hinder the growth of organisms forming the first cause of putrefaction, as in processes of smoking, embalming, and in the keeping of fishes and other animal specimens in spirit, &c. It is not only vegetable and animal substances which are subject to slow oxidation in the presence of water. Some metals even rust under these conditions. Copper very easily absorbs oxygen in the presence of acids. Many metallic sulphides (for example, pyrites) are very easily oxidised with access of air and moisture. Thus processes of slow oxidation proceed throughout nature. However, there are many elements which do not under any circumstances combine directly with gaseous oxygen; nevertheless their compounds with oxygen may be obtained. Platinum, gold, iridium, chlorine, and iodine are examples of such elements. In this case recourse is had to a so-called _indirect method_--_i.e._ the given substance is combined with another element, and by a method of double decomposition this element is replaced by oxygen. Substances which do not directly combine with oxygen, but form compounds with it by an indirect method, often readily lose the oxygen which they had absorbed by double decomposition or at the moment of its evolution. Such, for example, are the compounds of oxygen with chlorine, nitrogen, and platinum, which evolve oxygen on heating--that is, they may be used as oxidising agents. In this respect _oxidising agents_, or those compounds of oxygen which are employed in chemical and technical practice for transferring oxygen to other substances, are especially remarkable. The most important among these is nitric acid or _aqua fortis_--a substance rich in oxygen, and capable of evolving it when heated, which easily oxidises a great number of substances. Thus nearly all metals and organic substances containing carbon and hydrogen are more or less oxidised when heated with nitric acid. If strong nitric acid be taken, and a piece of burning charcoal be immersed in the acid, it continues to burn. Chromic acid acts like nitric acid; alcohol burns when mixed with it. Although the action is not so marked, even water may oxidise with its oxygen. Sodium is not oxidised in perfectly dry oxygen at the ordinary temperature, but it burns very easily in water and aqueous vapour. Charcoal can burn in carbonic anhydride--a product of combustion--forming carbonic oxide. Magnesium burns in the same gas, separating carbon from it. Speaking generally, combined oxygen can pass from one compound to another. The products of combustion or oxidation--and in general the definite compounds of oxygen--are termed _oxides_. Some oxides are not capable of combining with other oxides--or combine with only a few, and then with the evolution of very little heat; others, on the contrary, enter into combination with very many other oxides, and in general have remarkable chemical energy. The oxides incapable of combining with others, or only showing this quality in a small degree, are termed _indifferent oxides_. Such are the peroxides, of which mention has before been made. The class of oxides capable of entering into mutual combination we will term _saline oxides_. They fall into two chief groups--at least, as regards the most extreme members. The members of one group combine with the members of the other group with particular ease. As representative of one group may be taken the oxides of the metals, magnesium, sodium, calcium, &c. Representatives of the other group are the oxides formed by the non-metals, sulphur, phosphorus, carbon. Thus, if we take the oxide of calcium, or lime, and bring it into contact with oxides of the second group, combination very readily ensues. For instance, if we mix calcium oxide with oxide of phosphorus they combine with great facility and with the evolution of much heat. If we pass the vapour of sulphuric anhydride, obtained by the combination of sulphurous oxide with oxygen, over pieces of lime heated to redness, the sulphuric anhydride is absorbed by the lime with the formation of a substance called calcium sulphate. The oxides of the first kind, which contain metals, are termed _basic oxides_ or _bases_. Lime is a familiar example of this class. The oxides of the second group, which are capable of combining with the bases, are termed _anhydrides of the acids_ or _acid oxides_. Sulphuric anhydride, SO_{3}, may be taken as a type of the latter group. It is a compound of sulphur with oxygen formed not directly but by the addition of a fresh quantity of oxygen to sulphurous anhydride, SO_{2}, by passing it together with oxygen over incandescent spongy platinum. Carbonic anhydride (often termed 'carbonic acid'), CO_{2}, phosphoric anhydride, sulphurous anhydride, are all acid oxides, for they can combine with such oxides as lime or calcium oxide, magnesia or magnesium oxide, MgO, soda or sodium oxide, Na_{2}O, &c. If a given element form but one basic oxide, it is termed the _oxide_; for example, calcium oxide, magnesium oxide, potassium oxide. Some indifferent oxides are also called 'oxides' if they have not the properties of peroxides, and at the same time do not show the properties of acid anhydrides--for example, carbonic oxide, of which mention has already been made. If an element forms two basic oxides (or two indifferent oxides not having the characteristics of a peroxide) then that of the lower degree of oxidation is called a _suboxide_--that is, suboxides contain less oxygen than oxides. Thus, when copper is heated to redness in a furnace it increases in weight and absorbs oxygen, until for 63 parts of copper there is absorbed not more than 8 parts of oxygen by weight, forming a red mass, which is suboxide of copper; but if the roasting be prolonged, and the draught of air increased, 63 parts of copper absorb 16 parts of oxygen, and form black oxide of copper. Sometimes to distinguish between the degrees of oxidation a change of suffix is made in the oxidised element, _-ic_ oxide denoting the higher degree of oxidation, and _-ous_ oxide the lower degree. Thus ferrous oxide and ferric oxide are the same as suboxide of iron and oxide of iron. If an element forms one anhydride only, then it is named by an adjective formed from the name of the element made to end in _-ic_ and the word _anhydride_. When an element forms two anhydrides, then the suffixes _-ous_ and _-ic_ are used to distinguish them: _-ous_ signifying less oxygen than _-ic_; for example, sulphurous and sulphuric anhydrides.[49] When several oxides are formed from the same element, the prefixes _mon_, _di_, _tri_, _tetra_ are used, thus: chlorine monoxide, chlorine dioxide, chlorine trioxide, and chlorine tetroxide or chloric anhydride. [49] It must be remarked that certain elements form oxides of all three kinds--_i.e._ indifferent, basic, and acid; for example, manganese forms manganous oxide, manganic oxide, peroxide of manganese, red oxide of manganese, and manganic anhydride, although some of them are not known in a free state but only in combination. The basic oxides contain less oxygen than the peroxides, and the peroxides less than the acid anhydrides. Thus they must be placed in the following general normal order with respect to the amount of oxygen entering into their composition--(1) basic oxides, suboxides, and oxides; (2) peroxides; (3) acid anhydrides. The majority of elements, however, do not give all three kinds of oxides, some giving only one degree of oxidation. It must further be remarked that there are oxides formed by the combination of acid anhydrides with basic oxides, or, in general, of oxides with oxides. For every oxide having a higher and a lower degree of oxidation, it might be said that the intermediate oxide was formed by the combination of the higher with the lower oxide. But this is not true in all cases--for instance, when the oxide under consideration forms a whole series of independent compounds--for oxides which are really formed by the combination of two other oxides do not give such independent compounds, but in many cases decompose into the higher and lower oxides. The oxides themselves rarely undergo chemical transformations, and in the few cases where they are subject to such changes a particularly important part is played by their combinations with water. The majority of, if not all, basic and acid oxides combine with water, either by a direct or an indirect method forming _hydrates_--that is, compounds which split up into water and an oxide of the same kind only. It is well known that many substances are capable of combining with water. Oxides possess this property in the highest degree. We have already seen examples of this (Chapter I.) in the combination of lime, and of sulphuric and phosphoric anhydrides, with water. The resulting combinations are basic and acid hydrates. Acid hydrates are called _acids_ because they have an acid taste when dissolved in water (or saliva), for then only can they act on the palate. Vinegar, for example, has an acid taste because it contains acetic acid dissolved in water. Sulphuric acid, to which we have frequently referred, because it is the acid of the greatest importance both in practical chemistry and for its technical applications, is really a hydrate formed by the combination of sulphuric anhydride with water. Besides their acid taste, dissolved acids or acid hydrates have the property of changing the blue colour of certain vegetable dyes to red. Of these dyes _litmus_ is particularly remarkable and much used. It is the blue substance extracted from certain lichens, and is used for dyeing tissues blue; it gives a blue infusion with water. This infusion, on the addition of an acid, _changes from blue to red_.[50] [50] Blotting or unsized paper, soaked in a solution of litmus, is usually employed for detecting the presence of acids. This paper is cut into strips, and is called _test paper_; when dipped into acid it immediately turns red. This is a most sensitive reaction, and may be employed for testing for the smallest traces of acids. If 10,000 parts by weight of water be mixed with 1 part of sulphuric acid, the coloration is distinct, and it is even perceptible on the addition of ten times more water. Certain precautions must, however, be taken in the preparation of such very sensitive litmus paper. Litmus is sold in lumps. Take, say, 100 grams of it; powder it, and add it to cold pure water in a flask; shake and decant the water. Repeat this three times. This is done to wash away easily-soluble impurities, especially alkalis. Transfer the washed litmus (it is washed with absolute alcohol to remove the non-sensitive reddish colouring matter) to a flask, and pour in 600 c.c. of water, heat, and allow the hot infusion to remain for some hours in a warm place. Then filter, and divide the filtrate into two parts. Add a few drops of nitric acid to one portion, so that a faint red tinge is obtained, and then mix the two portions. Add spirit to the mixture, and keep it in a stoppered bottle (it soon spoils if left open to the air). This infusion may be employed directly; it reddens in the presence of acids, and turns blue in the presence of alkalis. If evaporated, a solid mass is obtained which is soluble in water, and may be kept unchanged for any length of time. The test paper may be prepared as follows:--Take a strong infusion of litmus, and soak blotting-paper with it; dry it, and cut it into strips, and use it as test-paper for acids. For the detection of alkalis, the paper must be soaked in a solution of litmus just reddened by a few drops of acid; if too much acid be taken, the paper will not be sensitive. Such acids as sulphuric acid colour litmus, and especially its infusion, a brick-red colour, whilst more feeble acids, such as carbonic, give a faint red-wine tinge. Test-paper of a yellow colour is also employed; it is dyed by an infusion of turmeric roots in spirit. In alkalis it turns brown, but regains its original hue in acids. Many blue and other vegetable colouring matters may be used for the detection of acids and alkalis; for example, infusions of cochineal, violets, log-wood, &c. Certain artificially prepared substances and dyes may also be employed. Thus rosolic acid, C_{20}H_{16}O_{3} and phenolphthaleïn, C_{20}H_{14}O_{4} (it is used in an alcoholic solution, and is not suitable for the detection of ammonia), are colourless in an acid, and red in an alkaline, solution. Cyanine is also colourless in the presence of acids, and gives a blue coloration with alkalis. Methyl-orange (yellow in an aqueous solution) is not altered by alkalis but becomes pink with acids (weak acids have no action), &c. These are very sensitive tests. Their behaviour in respect to various acids, alkalis, and salts sometimes give the means of distinguishing substances from each other. Basic oxides, in combining with water, form hydrates, of which, however, very few are soluble in water. Those which are soluble in water have an alkaline taste like that of soap or of water in which wood ashes have been boiled, and are called _alkalis_. Further, alkalis have the property of restoring the blue colour to litmus which has been reddened by the action of acids. The hydrates of the oxides of sodium and potassium, NaHO and KHO, are examples of basic hydrates easily soluble in water. They are true alkalis, and are termed _caustic_, because they act very powerfully on the skin of animals and plants. Thus NaHO is called 'caustic' soda. The saline oxides are capable of combining together and with water. Water itself is an oxide, and not an indifferent one, for it can, as we have seen, combine with basic and acid oxides; it is a representative of a whole series of saline oxides, _intermediate oxides_, capable of combining with both basic and acid oxides. There are many such oxides, which, like water, combine with basic and acid anhydrides--for instance, the oxides of aluminium and tin, &c. From this it may be concluded that all oxides might be placed, in respect to their capacity for combining with one another, in one uninterrupted series, at one extremity of which would stand those oxides which do not combine with the bases--that is, the alkalis--while at the other end would be the acid oxides, and in the interval those oxides which combine with one another and with both the acid and basic oxides. The further apart the members of this series are, the more stable are the compounds they form together, the more energetically do they act on each other, the greater the quantity of heat evolved in their reaction, and the more marked is their saline chemical character. We said above that basic and acid oxides combine together, but rarely react on each other; this depends on the fact that the majority of them are solids or gases--that is, they occur in the state least prone to chemical reaction. The gaseo-elastic state is with difficulty destroyed, because it necessitates overcoming the elasticity proper to the gaseous particles. The solid state is characterised by the immobility of its particles; whilst chemical action requires contact, and hence a displacement and mobility. If solid oxides be heated, and especially if they be melted, then reaction proceeds with great ease. But such a change of state rarely occurs in nature or in practice. Only in a few furnace processes is this the case. For example; in the manufacture of glass, the oxides contained in it combine together in a molten state. But when oxides combine with water, and especially when they form hydrates soluble in water, then the mobility of their particles increases to a considerable extent, and their reaction is greatly facilitated. Reaction then takes place at the ordinary temperature--easily and rapidly; so that this kind of reaction belongs to the class of those which take place with unusual facility, and are, therefore, very often taken advantage of in practice, and also have been and are going on in nature at every step. We will now consider the reactions of oxides in the state of hydrates, not losing sight of the fact that water is itself an oxide with definite properties, and has, therefore, no little influence on the course of those changes in which it takes part. If we take a definite quantity of an acid, and add an infusion of litmus to it, it turns red; the addition of an alkaline solution does not immediately alter the red colour of the litmus, but on adding more and more of the alkaline solution a point is reached when the red colour changes to violet, and then the further addition of a fresh quantity of the alkaline solution changes the colour to blue. This change of the colour of the litmus is a consequence of the formation of a new compound. This reaction is termed the _saturation_ or _neutralisation_ of the acid by the base, or _vice versâ_. The solution in which the acid properties of the acid are saturated by the alkaline properties of the base is termed a _neutral_ solution. Such a solution, although derived from the mixture of a base with an acid, does not exhibit either the acid or basic reaction on litmus, yet it preserves many other signs of the acid and alkali. It is observed that in such a definite admixture of an acid with an alkali, besides the changes in the colour of litmus there is a heating effect--_i.e._ an evolution of heat--which is alone sufficient to prove that there was chemical action. And, indeed, if the resultant violet solution be evaporated, there separates out, not the acid or the alkali originally taken, but a substance which has neither acid nor alkaline properties, but is usually solid and crystalline, having a saline appearance; this is a _salt_ in the chemical sense of the word. Hence a salt is derived from the reaction of an acid on an alkali, in a certain definite proportion. The water here taken for solution plays no other part than merely facilitating the progress of the reaction. This is seen from the fact that the anhydrides of the acids are able to combine with basic oxides, and give the same salts as do the acids with the alkalis or hydrates. Hence, a salt is a compound of definite quantities of an acid with an alkali. In the latter reaction, water is separated out if the substance formed be the same as is produced by the combination of anhydrous oxides together.[51] Examples of the formation of salts from acids and bases are easily observed, and are very often applied in practice. If we take, for instance, insoluble magnesium oxide (magnesia) it is easily dissolved in sulphuric acid, and on evaporation gives a saline substance, bitter, like all the salts of magnesium, and familiar to all under the name of Epsom salts, used as a purgative. If a solution of caustic soda--which is obtained, as we saw, by the action of water on sodium oxide--be poured into a flask in which charcoal has been burnt; or if carbonic anhydride, which is produced under so many circumstances, be passed through a solution of caustic soda, then sodium carbonate or soda, Na_{2}CO_{3}, is obtained, of which we have spoken several times, and which is prepared on a large scale and often used in manufactures. This reaction is expressed by the equation, 2NaHO + CO_{2} = Na_{2}CO_{3} + H_{2}O. Thus, the various bases and acids form an innumerable number of different salts.[52] Salts constitute an example of definite chemical compounds, and both in the history and practice of science are most often cited as confirming the conception of definite chemical compounds. Indeed, all the indications of a definite chemical combination are clearly seen in the formation and properties of salts. Thus, they are produced with a definite proportion of oxides, heat is evolved in their formation,[53] and the chemical character of the oxides and many of the physical properties become hidden in their salts. For example, when gaseous carbonic anhydride combines with a base to form a solid salt, the elasticity of the gas quite disappears in its passage into the salt.[54] [51] That water really is separated in the reaction of acid on alkaline hydrates, may be shown by taking some other intermediate hydrate--for example, alumina--instead of water. Thus, if a solution of alumina in sulphuric acid be taken, it will have, like the acid, an acid reaction, and will therefore colour litmus red. If, on the other hand, a solution of alumina in an alkali--say, potash--be taken, it will have an alkaline reaction, and will turn red litmus blue. On adding the alkaline to the acid solution until neither an alkaline nor an acid reaction is produced, a salt is formed, consisting of sulphuric anhydride and potassium oxide. In this, as in the reaction of hydrates, an intermediate oxide is separated out--namely, alumina. Its separation will be very evident in this case, as alumina is insoluble in water. [52] The mutual interaction of hydrates, and their capacity of forming salts, may be taken advantage of for determining the character of those hydrates which are insoluble in water. Let us imagine that a given hydrate, whose chemical character is unknown, is insoluble in water. It is therefore impossible to test its reaction on litmus. It is then mixed with water, and an acid--for instance, sulphuric acid--is added to the mixture. If the hydrate taken be basic, reaction will take place, either directly or by the aid of heat, with the formation of a salt. In certain cases, the resultant salt is soluble in water, and this will at once show that combination has taken place between the insoluble basic hydrate and the acid, with the formation of a soluble saline substance. In those cases where the resultant salt is insoluble, still the water loses its acid reaction, and therefore it may he ascertained, by the addition of an acid, whether a given hydrate has a basic character, like the hydrates of oxide of copper, lead, &c. If the acid does not act on the given insoluble hydrate (at any temperature), then it has not a basic character, and it should be tested as to whether it has an acid character. This is done by taking an alkali, instead of the acid, and by observing whether the unknown hydrate then dissolves, or whether the alkaline reaction disappears. Thus it may he proved that hydrate of silica is acid, because it dissolves in alkalis and not in acids. If it be a case of an insoluble intermediate hydrate, then it will be observed to react on both the acid and alkali. Hydrate of alumina is an instance in question, which is soluble both in caustic potash and in sulphuric acid. The _degree of affinity_ or chemical _energy_ proper to oxides and their hydrates is very dissimilar; some extreme members of the series possess it to a great extent. When acting on each other they evolve a large quantity of heat, and when acting on intermediate hydrates they also evolve heat to a considerable degree, as we saw in the combination of lime and sulphuric anhydride with water. When extreme oxides combine they form stable salts, which are decomposed with difficulty, and often show characteristic properties. The compounds of the intermediate oxides with each other, or even with basic and acid oxides, present a very different case. However much alumina we may dissolve in sulphuric acid, we cannot saturate the acid properties of the sulphuric acid, the resulting solution will always have an acid reaction. So also, whatever quantity of alumina is dissolved in an alkali, the resulting solution will always present an alkaline reaction. [53] In order to give an idea of the quantity of heat evolved in the formation of salts I append a table of data for _very dilute aqueous solutions_ of acids and alkalis, according to the determinations of Berthelot and Thomsen. The figures are given in major calories--that is, in thousands of units of heat. For example, 49 grams of sulphuric acid, H_{2}SO_{4}, taken in a dilute aqueous solution, when mixed with such an amount of a weak solution of caustic soda, NaHO, that a neutral salt is formed (when all the hydrogen of the acid is replaced by the sodium), evolves 15,800 units of heat. 49 parts of 63 parts of H_{2}SO_{4} HNO_{3} NaHO 15·8 13·7 KHO 15·7 13·8 NH_{3} 14·5 12·5 CaO 15·6 13·9 BaO 18·4 13·9 MgO 15·6 13·8 FeO 12·5 10·7 (?) ZnO 11·7 9·8 Fe_{2}O_{3} 5·7 5·9 These figures cannot be considered as the heat of neutralisation, because the water here plays an important part. Thus, for instance, sulphuric acid and caustic soda in dissolving in water evolve very much heat, and the resultant sodium sulphate very little; consequently, the amount of heat evolved in an anhydrous combination will be different from that evolved in a hydrated combination. Those acids which are not energetic in combining with the same quantity of alkalis required for the formation of normal salts of sulphuric or nitric acids always, however, give less heat. For instance, with caustic soda: carbonic acid gives 10·2, hydrocyanic, 2·9, hydrogen sulphide, 3·9 major calories. And as feeble bases (for example, Fe_{2}O_{3}) also evolve less heat than those which are more powerful, so a certain general correlation between thermochemical data and the degree of affinity shows itself here, as in other cases (_see_ Chapter II., Note 7); this does not, however, give any reason for measuring the affinity which binds the elements of salts by the heat of their formation in dilute solutions. This is very clearly demonstrated by the fact that water is able to decompose many salts, and is separated in their formation. [54] Carbonic anhydride evolves heat in dissolving in water. The solution easily dissociates and evolves carbonic anhydride, according to the law of Henry and Dalton (_see_ Chapter I.) In dissolving in caustic soda, it either gives a normal salt, Na_{2}CO_{3}, which does not evolve carbonic anhydride, or an acid salt, NaHCO_{3} which easily evolves carbonic anhydride when heated. The same gas, when dissolved in solutions of salts, acts in one or the other manner (_see_ Chapter II., Note 38). Here it is seen what a successive series of relations exists between compounds of a different order, between substances of different degrees of stability. By making a distinction between the phenomena of solutions and chemical compounds, we overlook those natural transitions which in reality exist. Judging from the above, a salt is a compound of basic and acid oxides, or the result of the action of hydrates of these classes on each other with separation of water. But salts may be obtained by other methods. It must not be forgotten that basic oxides are formed by metals, and acid oxides usually by non-metals. But metals and non-metals are capable of combining together, and a salt is frequently formed by the oxidation of such a compound. For example, iron very easily combines with sulphur, forming iron sulphide FeS (as we saw in the Introduction); this in air, and especially moist air, absorbs oxygen, with the formation of the same salt FeSO_{4}, that may be obtained by the combination of the oxides of iron and sulphur, or of the hydrates of these oxides. Hence, it cannot be said or supposed that a salt has the properties of the oxides, or must necessarily contain two kinds of oxides in itself. The derivation of salts from oxides is merely one of the methods of their preparation. We saw, for instance, that in sulphuric acid it was possible to replace the hydrogen by zinc, and that by this means zinc sulphate was formed; so likewise the hydrogen in many other acids may be replaced by zinc, iron, potassium, sodium, and a whole series of similar metals, corresponding salts being obtained. The hydrogen of the acid, in all these cases, is exchanged for a metal, and a salt is obtained from the hydrate. Regarding a salt from this point of view, it may be said that _a salt is an acid in which hydrogen is replaced by a metal_. This definition shows that a salt and an acid are essentially compounds of the same series, with the difference that the latter contains hydrogen and the former a metal. Such a definition is more exact than the first definition of salts, inasmuch as it likewise includes those acids which do not contain oxygen, and, as we shall afterwards learn, there is a series of such acids. Such elements as chlorine and bromine form compounds with hydrogen in which the hydrogen may be replaced by a metal, forming substances which, in their reactions and external characters, resemble the salts formed from oxides. Table salt, NaCl, is an example of this. It may be obtained by the replacement of hydrogen in hydrochloric acid, HCl, by the metal sodium, just as sulphate of sodium, Na_{2}SO_{4}, may be obtained by the replacement of hydrogen in sulphuric acid, H_{2}SO_{4}, by sodium. The exterior appearance of the resulting products, their neutral reaction, and even their saline taste, show their resemblance to one another. To the fundamental properties of salts yet another must be added--namely, that they are more or less _decomposed by the action of a galvanic current_. The results of this decomposition are very different according to whether the salt be taken in a fused or dissolved state. But the decomposition may generally be so represented, that the metal appears at the electro-negative pole or cathode (like hydrogen in the decomposition of water, or its mixture with sulphuric acid), and the remaining parts of the salt appear at the electro-positive pole or anode (where the oxygen of water appears). If, for instance, an electric current acts on an aqueous solution of sodium sulphate, then the sodium appears at the negative pole, and oxygen and the anhydride of sulphuric acid at the positive pole. But in the solution itself the result is different, for sodium, as we know, decomposes water with evolution of hydrogen, forming caustic soda; consequently hydrogen will be evolved, and caustic soda appear at the negative pole: while at the positive pole the sulphuric anhydride immediately combines with water and forms sulphuric acid, and therefore oxygen will be evolved and sulphuric acid formed round this pole.[55] In other cases, when the metal separated is not able to decompose water, it will be deposited in a free state. Thus, for example, in the decomposition of copper sulphate, copper separates out at the cathode, and oxygen and sulphuric acid appear at the anode, and if a copper plate be attached to the positive pole, then the oxygen evolved will oxidise the copper, and the oxide of copper will dissolve and be deposited at the negative pole--that is, a transfer of copper from the positive to the negative pole ensues. The galvanoplastic art (electro-typing) is based on this principle.[56] Therefore the most radical and general properties of salts (including also such salts as table salt, which contain no oxygen) may be expressed by representing the salt as composed of a metal M and a haloid X--that is, by expressing the salt by MX. In common table salt the metal is sodium, and the haloid an elementary body, chlorine. In sodium sulphate, Na_{2}SO_{4}, sodium is again the metal, but the complex group, SO_{4}, is the haloid. In sulphate of copper, CuSO_{4}, the metal is copper and the haloid the same as in the preceding salt. Such a representation of salts expresses with great simplicity the _capacity of every salt to enter into saline double decompositions with other salts_; consisting in the mutual replacement of the metals in the salts. This exchange of their metals is the fundamental property of salts. In the case of two salts with different metals and haloids, which are in solution or fusion, or in any other manner brought into contact, the metals of these salts will always partially or wholly exchange places. If we designate one salt by MX, and the other by NY, then we either partially or wholly obtain from them new salts, MY and NX. Thus we saw in the Introduction, that on mixing solutions of table salt, NaCl, and silver nitrate, AgNO_{3}, a white insoluble precipitate of silver chloride, AgCl, is formed and a new salt, sodium nitrate, NaNO_{3}, is obtained in solution. If the metals of salts exchange places in reactions of double decomposition, it is clear that metals themselves, taken in a separate state, are able to act on salts, as zinc evolves hydrogen from acids, and as iron separates copper from copper sulphate. When, to what extent, and which metals displace each other, and how the metals are distributed between the haloids, will be discussed in Chapter X., where we shall be guided by those reflections and deductions which Berthollet introduced into the science at the beginning of this century. [55] This kind of decomposition may be easily observed by pouring a solution of sodium sulphate into a U-shaped tube and inserting electrodes in the two branches. If the solution be coloured with an infusion of litmus, it will easily be seen that it turns blue at the cathode, owing to the formation of sodium hydroxide, and red at the electro-positive pole, from the formation of sulphuric acid. [56] In other cases the decomposition of salts by the electric current may be accompanied by much more complex results. Thus, when the metal of the salt is capable of a higher degree of oxidation, such a higher oxide may be formed at the positive pole by the oxygen which is evolved there. This takes place, for instance, in the decomposition of salts of silver and manganese by the galvanic current, peroxides of these metals being formed. Thus in the electrolysis of a solution of KCl, KClO_{3} is formed, and of sulphuric acid (corresponding to SO_{3}) persulphuric acid, corresponding to S_{2}O_{7}. But all the phenomena as yet known may be expressed by the above law--that the current decomposes salts into metals, which appear at the negative pole, and into the remaining component parts, which appear at the positive pole. According to the above observations, an acid is nothing more than a salt of hydrogen. Water itself may be looked on as a salt in which the hydrogen is combined with either oxygen or the aqueous radicle, OH; water will then be HOH, and alkalis or basic hydrates, MOH. The group OH, or the _aqueous radicle_, otherwise called _hydroxyl_, may be looked on as a haloid like the chlorine in table salt, not only because the element Cl and the group OH very often change places, and combine with one and the same element, but also because free chlorine is very similar in many properties and reactions to peroxide of hydrogen, which is the same in composition as the aqueous radicle, as we shall afterwards see in Chapter IV. Alkalis and basic hydrates are also salts consisting of a metal and hydroxyl--for instance, caustic soda, NaOH; this is therefore termed _sodium hydroxide_. According to this view, _acid salts_ are those in which a portion only of the hydrogen is replaced by a metal, and a portion of the hydrogen of the acid remains. Thus sulphuric acid (H_{2}SO_{4}) not only gives the normal salt Na_{2}SO_{4}, with sodium, but also an acid salt, NaHSO_{4}. A _basic salt_ is one in which the metal is combined not only with the haloids of acids, but also with the aqueous radicale of basic hydrates--for example, bismuth gives not only a normal salt of nitric acid, Bi(NO_{3})_{3}, but also basic salts like Bi(OH)_{2}(NO_{3}). As basic and acid salts of the oxygen acids contain hydrogen and oxygen, they are able to part with these as water and to give anhydro-salts, which it is evident will be compounds of normal salts with anhydrides of the acids or with bases. Thus the above-mentioned acid sodium sulphate corresponds with the anhydro-salt, Na_{2}S_{2}O_{7}, equal to 2NaHSO_{4}, less H_{2}O. The loss of water is here, and frequently in other cases, brought about by heat alone, and therefore such salts are frequently termed _pyro-salts_--for instance, the preceding is sodium pyrosulphate (Na_{2}S_{2}O_{7}), or it may be regarded as the normal salt Na_{2}SO_{4} + sulphuric anhydride, SO_{3}. _Double_ salts are those which contain either two metals, KAl(SO_{4})_{2}, or two haloids.[57] [57] The above-enunciated generalisation of the conception of salts as compounds of the metals (simple, or compound like ammonium, NH_{4}), with the haloids (simple, like chlorine, or compound, like cyanogen, CN, or the radical of sulphuric acid, SO_{4}), capable of entering into double saline decomposition, which is in accordance with the general data respecting salts, was only formed little by little after a succession of most varied propositions as to the chemical structure of salts. Salts belong to the class of substances which have been known since very early times, and have long been investigated in many directions. At first, however, no distinction was made between salts, acids, and bases. Glauber prepared many artificial salts during the latter half of the seventeenth century. Up to that time the majority of salts were obtained from natural sources, and that salt which we have referred to several times--namely, sodium sulphate--was named Glauber's salt after this chemist. Rouelle distinguished normal, acid, and basic salts, and showed their action on vegetable dyes, still he confounded many salts with acids (even now every acid salt ought to be regarded as an acid, because it contains hydrogen, which may be replaced by metals--that is, it is the hydrogen of an acid). Baumé disputed Rouelle's opinion concerning the subdivision of salts, contending that normal salts only are true salts, and that basic salts are simple mixtures of normal salts with bases and acid salts with acids, considering that washing alone could remove the base or acid from them. Rouelle, in the middle of the last century, however, rendered a great service to the study of salts and the diffusion of knowledge respecting this class of compounds in his attractive lectures. He, like the majority of the chemists of that period, did not employ the balance in his researches, but satisfied himself with purely qualitative data. The first quantitative researches on salts were carried on about this time by Wenzel, who was the director of the Freiburg mines, in Saxony. Wenzel studied the double decomposition of salts, and observed that in the double decomposition of neutral salts a neutral salt was always obtained. He proved, by a method of weighing, that this is due to the fact that the saturation of a given quantity of a base requires such relative quantities of different acids as are capable of saturating every other base. Having taken two neutral salts--for example, sodium sulphate and calcium nitrate--let us mix their solutions together. Double decomposition takes place, because calcium sulphate is formed, which is almost insoluble. However much we might add of each of the salts, the neutral reaction will still be preserved, consequently the neutral character of the salts is not destroyed by the interchange of metals; that is to say, that quantity of sulphuric acid which saturated the sodium is sufficient for the saturation of the calcium, and that amount of nitric acid which saturated the calcium is enough to saturate the sodium contained in combination with sulphuric acid in sodium sulphate. Wenzel was even convinced that matter does not disappear in nature, and on this principle he corrects, in his _Doctrine of Affinity_, the results of his experiments when he found that he obtained less than he had originally taken. Although Wenzel deduced the law of the double decomposition of salts quite correctly, he did not determine those quantities in which acids and bases act on each other. This was carried out at the end of the last century by Richter. He determined the quantities by weight of the bases which saturate acids and of the acids which saturate bases, and obtained comparatively correct results, although his conclusions were not correct, for he states that the quantity of a base saturating a given acid varies in arithmetical progression, and the quantity of an acid saturating a given base in geometrical progression. Richter studied the deposition of metals from their salts by other metals, and observed that the neutral reaction of the solution is not destroyed by this exchange. He also determined the quantities by weight of the metals replacing one another in salts. He showed that copper displaces silver from its salt, and that zinc displaces copper and a whole series of other metals. Those quantities of metals which were capable of replacing one another were termed equivalents. Richter's teaching found no followers, because, although he fully believed in the discoveries of Lavoisier, yet he still held to the phlogistic reasonings which rendered his expositions very obscure. The works of the Swedish savant Berzelius freed the facts discovered by Wenzel and Richter from the obscurity of former conceptions, and led to their being explained in accordance with Lavoisier's views, and in the sense of the law of multiple proportions which had already been discovered by Dalton. On applying to salts those conclusions which Berzelius arrived at by a whole series of researches of remarkable accuracy, we arrive at the following law of equivalents--_one part by weight of hydrogen in an acid is replaced by the corresponding equivalent weight of any metal_; and, therefore, when metals replace each other their weights are in the same ratio as their equivalents. Thus, for instance, one part by weight of hydrogen is replaced by 23 parts of sodium, 39 parts of potassium, 12 parts of magnesium, 20 parts of calcium, 28 parts of iron, 108 parts of silver, 33 parts of zinc, &c.; and, therefore, if zinc replaces silver, then 33 parts of zinc will take the place of 108 parts of silver, or 33 parts of zinc will he substituted by 23 parts of sodium, &c. The doctrine of equivalents would be precise and simple did every metal only give one oxide or one salt. It is rendered complicated from the fact that many metals form several oxides, and consequently offer different equivalents in their different degrees of oxidation. For example, there are oxides containing iron in which its equivalent is 28--this is in the salts formed by the suboxide; and there is another series of salts in which the equivalent of iron equals 18-2/3--which contain less iron, and consequently more oxygen, and correspond with a higher degree of oxidation--ferric oxide. It is true that the former salts are easily formed by the direct action of metallic iron on acids, and the latter only by a further oxidation of the compound formed already; but this is not always so. In the case of copper, mercury, and tin, under different circumstances, salts are formed which correspond with different degrees of oxidation of these metals, and many metals have two equivalents in their different salts--that is, in salts corresponding with the different degrees of oxidation. Thus it is impossible to endow every metal with one definite equivalent weight. Hence the conception of equivalents, while playing an important part from an historical point of view, appears, with a fuller study of chemistry, to be but subordinate to a higher conception, with which we shall afterwards become acquainted. The fate of the theoretical views of chemistry was for a long time bound up with the history of salts. The clearest representation of this subject dates back to Lavoisier, and was systematically developed by Berzelius. This representation is called the _binary_ theory. All compounds, and especially salts, are represented as consisting of two parts. Salts are represented as compounds of a basic oxide (a base) and an acid (that is, an anhydride of an acid, then termed an acid), whilst hydrates are represented as compounds of anhydrous oxides with water. Such an expression was employed not only to denote the most usual method of formation of these substances (where it would be quite true), but also to express that internal distribution of the elements by which it was proposed to explain all the properties of these substances. Copper sulphate was supposed to contain two most intimate component parts--copper oxide and sulphuric anhydride. This is an hypothesis. It arose from the so-called _electro-chemical hypothesis_, which supposed the two component parts to be held in mutual union, because one component (the anhydride of the acid) has electro-negative properties, and the other (the base in salts) electro-positive. The two parts are attracted together, like substances having opposite electrical charges. But as the decomposition of salts in a state of fusion by an electric current always gives a metal, that representation of the constitution and decomposition of salts called the _hydrogen theory_ of acids is nearer the truth than that which considers salts as made up of a base and an anhydride of an acid. But the hydrogen theory of acids is also a binary hypothesis, and does not contradict the electro-chemical hypothesis, but is rather a modification of it. The binary theory dates from Rouelle and Lavoisier, the electro-chemical aspect was zealously developed by Berzelius, and the hydrogen theory of acids is due to Davy and Liebig. These hypothetical views simplified and generalised the study of a complicated subject, and served to support further arguments, but when salts were in question it was equally convenient to follow one or the other of these hypotheses. But these theories were brought to bear on all other substances, on all compound substances. Those holding the binary and electro-chemical hypotheses searched for two anti-polar component parts, and endeavoured to express the process of chemical reactions by electro-chemical and similar differences. If zinc replaces hydrogen, they concluded that it is more electro-positive than hydrogen, whilst they forgot that hydrogen may, under different circumstances, displace zinc--for instance, at a red heat. Chlorine and oxygen were considered as being of opposite polarity to hydrogen because they easily combine with it, nevertheless both are capable of replacing hydrogen, and, what is very characteristic, in the replacement of hydrogen by chlorine in carbon compounds not only does the chemical character often remain unaltered, but even the external form may remain unchanged, as Laurent and Dumas demonstrated. These considerations undermine the binary, and more especially the electro-chemical theory. An explanation of known reactions then began to be sought for not in the difference of the polarity of the different substances, but in the joint influences of all the elements on the properties of the compound formed. This is the reverse of the preceding hypothesis. This reversal was not, however, limited to the destruction of the tottering foundations of the preceding theory; it proposed a new doctrine, and laid the foundation for the modern course of our science. This doctrine may be termed the unitary theory--that is, it strictly acknowledges the joint influences of the elements in a compound substance, denies the existence of separate and contrary components in them, regards copper sulphate, for instance, as a strictly definite compound of copper, sulphur, and oxygen; then seeks for compounds which are analogous in their properties, and, placing them side by side, endeavours to express the influence of each element in determining the united properties of its compound. In the majority of cases it arrives at conclusions similar to those which are obtained by the above-mentioned hypotheses, but in certain special cases the conclusions of the unitary theory are in entire opposition to those of the binary theory and its corollaries. Cases of this kind are most often met with in the consideration of compounds of a more complex nature than salts, especially organic compounds containing hydrogen. But it is not in this change from an artificial to a natural system, important as it is, that the chief service and strength of the unitary doctrine lies. By a simple review of the vast store of data regarding the reactions of typical substances, it succeeded from its first appearance in establishing a new and important law, it introduced a new conception into science--namely, the conception of molecules, with which we shall soon become acquainted. The deduction of the law and of the conception of molecules has been verified by facts in a number of cases, and was the cause of the majority of chemists of our times deserting the binary theory and accepting the unitary theory, which forms the basis of the present work. Laurent and Gerhardt must be considered as the founders of this doctrine. Inasmuch as oxygen compounds predominate in nature, it should be expected from what has been said above, that salts, rather than acids or bases, would occur most frequently in nature, for these latter would always tend to combine forming salts, especially through the medium of the all-pervading water. And, as a matter of fact, salts are found everywhere in nature. They occur in animals and plants, although in but small quantity, because, as forming the last stage of chemical reaction, they are capable of only a few chemical transformations. And organisms are bodies in which a series of uninterrupted, varied, and active chemical transformations proceed, whilst salts, which only enter into double decompositions between each other, are little prone to such changes. But organisms always contain salts. Thus, for instance, bones contain calcium phosphate, the juice of grapes potassium tartrate (cream of tartar), certain lichens calcium oxalate, and the shells of mollusca calcium carbonate, &c. As regards water and soil, portions of the earth in which the chemical processes are less active, they are full of salts. Thus the waters of the oceans, and all others (Chap. I.), abound in salts, and in the soil, in the rocks of the earth's crust, in the upheaved lavas, and in the falling meteorites the salts of silicic acid, and especially its double salts, predominate. Saline substances also make up the composition of those limestones which often form mountain chains and whole thicknesses of the earth's strata, these consisting of calcium carbonate, CaCO_{3}. Thus we have seen oxygen in a free state and in various compounds of different degrees of stability, from the unstable salts, like Berthollet's salt and nitre, to the most stable silicon compounds, such as exist in granite. We saw an entirely similar gradation of stability in the compounds of water and of hydrogen. In all its aspects oxygen, as an element, or single substance, remains the same however varied its chemical states, just as a substance may appear in many different physical states of aggregation. But our notion of the immense variety of the chemical states in which oxygen can occur would not be completely understood if we did not make ourselves acquainted with it in the form in which it occurs in ozone and peroxide of hydrogen. In these it is most active, its energy seems to have increased. They illustrate fresh aspects of chemical correlations, and the variety of the forms in which matter can appear stand out clearly. We will therefore consider these two substances somewhat in detail. CHAPTER IV OZONE AND HYDROGEN PEROXIDE--DALTON'S LAW VAN MARUM, during the last century, observed that oxygen in a glass tube, when subjected to the action of a series of electric sparks, acquired a peculiar smell, and the property of combining with mercury at the ordinary temperature. This was afterwards confirmed by a number of fresh experiments. Even in the simple revolution of an electrical machine, when electricity diffuses into the air or passes through it, the peculiar and characteristic smell of ozone, proceeding from the action of the electricity on the oxygen of the atmosphere, is recognised. In 1840 Prof. Schönbein, of Basle, turned his attention to this odoriferous substance, and showed that it is also formed, with the oxygen evolved at the positive pole, in the decomposition of water by the action of a galvanic current; in the oxidation of phosphorus in damp air, and also in the oxidation of a number of substances, although it is distinguished for its instability and capacity for oxidising other substances. The characteristic smell of this substance gave it its name, from the Greek [Greek: ozô], 'I emit an odour.' Schönbein pointed out that _ozone_ is capable of oxidising many substances on which oxygen does not act at the ordinary temperature. It will be sufficient to point out for instance that it oxidises silver, mercury, charcoal, and iron with great energy at the ordinary temperature. It might be thought that ozone was some new compound substance, as it was at first supposed to be; but careful observations made in this direction have long led to the conclusion that ozone is nothing but oxygen altered in its properties. This is most strikingly proved by the complete transformation of oxygen containing ozone into ordinary oxygen when it is passed through a tube heated to 250°. Further, at a low temperature pure oxygen gives ozone when electric sparks are passed through it (Marignac and De la Rive). Hence it is proved both by synthesis and analysis that ozone is that same oxygen with which we are already acquainted, only endowed with particular properties and in a particular state. However, by whatever method it be obtained, the amount of it contained in the oxygen is inconsiderable, generally only a few fractions per cent., rarely 2 per cent., and only under very propitious circumstances as much as 20 per cent. The reason of this must be looked for first in the fact that _ozone in its formation from oxygen absorbs heat_. If any substance be burnt in a calorimeter at the expense of ozonised oxygen, then more heat is evolved than when it is burnt in ordinary oxygen, and Berthelot showed that this difference is very large--namely, 29,600 heat units correspond with every forty-eight parts by weight of ozone. This signifies that the transformation of forty-eight parts of oxygen into ozone is accompanied by the absorption of this quantity of heat, and that the reverse process evolves this quantity of heat. Therefore the passage of ozone into oxygen should take place easily and fully (as an exothermal reaction), like combustion; and this is proved by the fact that at 250° ozone entirely disappears, forming oxygen. Any rise of temperature may thus bring about the breaking up of ozone, and as a rise of temperature takes place in the action of an electrical discharge, there are in an electric discharge the conditions both for the preparation of ozone and for its destruction. Hence it is clear that the transformation of oxygen into ozone _as a reversible reaction_ has a limit when a state of equilibrium is arrived at between the products of the two opposite reactions, that the phenomena of this transformation accord with the phenomena of _dissociation_, and that a fall of temperature should aid the formation of a large quantity of ozone.[1] Further, it is evident, from what has been said, that the best way of preparing ozone is not by electric sparks,[2] which raise the temperature, but by the employment of a continual discharge or flow of electricity--that is, by the action of a _silent discharge_.[3] For this reason all _ozonisers_ (which are of most varied construction), or forms of apparatus for the preparation of ozone from oxygen (or air) by the action of electricity, now usually consist of sheets of metal--for instance, tinfoil--a solution of sulphuric acid mixed with chromic acid, &c. separated by thin glass surfaces placed at short distances from each other, and between which the oxygen or air to be ozonised is introduced and subjected to the action of a silent discharge.[4] Thus in Siemens' apparatus (fig. 37) the exterior of the tube _a_ and the interior of the tube _b c_ are coated with tinfoil and connected with the poles of a source of electricity (with the terminals of a Ruhmkorff's coil). A silent discharge passes through the thin walls of the glass cylinders _a_ and _b c_ over all their surfaces, and consequently, if oxygen be passed through the apparatus by the tube _d_, fused into the side of _a_, it will be ozonised in the annular space between _a_ and _b c_. The ozonised oxygen escapes by the tube _e_, and may be introduced into any other apparatus.[5] [Illustration: FIG. 37.--Siemens' apparatus for preparing ozone by means of a silent discharge.] [1] This conclusion, deduced by me as far back as 1878 (_Moniteur Scientifique_) by conceiving the molecules of ozone (see later) as more complex than those of oxygen, and ozone as containing a greater quantity of heat than oxygen, has been proved experimentally by the researches of Mailfert (1880), who showed that the passage of a silent discharge through a litre of oxygen at 0° may form up to 14 milligrams of ozone, and at -30° up to 60 milligrams; but best of all in the determinations of Chappuis and Hautefeuille (1880), who found that at a temperature of -25° a silent discharge converted 20 p.c. of oxygen into ozone, whilst at 20° it was impossible to obtain more than 12 p.c., and at 100° less than 2 p.c. of ozone was obtained. [2] A series of electric sparks may be obtained by an ordinary electrical machine, the electrophorus machines of Holtz and Teploff, &c., Leyden jars, Ruhmkorff coils, or similar means, when the opposite electricities are able to accumulate at the terminals of conductors, and a discharge of sufficient electrical intensity passes through the non-conductors air or oxygen. [3] A silent discharge is such a combination of opposite statical (potential) electricities as takes place (generally between large surfaces) regularly, without sparks, slowly, and quietly (as in the dispersion of electricity). The discharge is only luminous in the dark; there is no observable rise of temperature, and therefore a larger amount of ozone is formed. But, nevertheless, on continuing the passage of a silent discharge through ozone it is destroyed. For the action to be observable a large surface is necessary, and consequently a source of electricity at a high potential. For this reason the silent discharge is best produced by a Ruhmkorff coil, as the most convenient means of obtaining a considerable potential of statical electricity with the employment of the comparatively feeble current of a galvanic battery. [4] _v. Babo's apparatus_ was one of the first constructed for ozonising oxygen by means of a silent discharge (and it is still one of the best). It is composed of a number (twenty and more) of long, thin capillary glass tubes closed at one end. A platinum wire, extending along their whole length, is introduced into the other end of each tube, and this end is then fused up round the wire, the end of which protrudes outside the tube. The protruding ends of the wires are arranged alternately in two sides in such a manner that on one side there are ten closed ends and ten wires. A bunch of such tubes (forty should make a bunch of not more than 1 c.m. diameter) is placed in a glass tube, and the ends of the wires are connected with two conductors, and are fused to the ends of the surrounding tube. The discharge of a Ruhmkorff coil is passed through these ends of the wires, and the dry air or oxygen to be ozonised is passed through the tube. If oxygen be passed through, ozone is obtained in large quantities, and free from oxides of nitrogen, which are partially formed when air is acted on. At low temperatures ozone is formed in large quantities. As ozone acts on corks and india-rubber, the apparatus should be made entirely of glass. With a powerful Ruhmkorff coil and forty tubes the ozonation is so powerful that the gas when passed through a solution of iodide of potassium not only sets the iodine free, but even oxidises it to potassium iodate, so that in five minutes the gas-conducting tube is choked up with crystals of the insoluble iodate. [5] In order to connect the ozoniser with any other apparatus it is impossible to make use of india-rubber, mercury, or cements, &c., because they are themselves acted on by, and act on, ozone. All connections must, as was first proposed by Brodie, be hermetically closed by sulphuric acid, which is not acted on by ozone. Thus, a cork is passed over the vertical end of a tube, over which a wide tube passes so that the end of the first tube protrudes above the cork; mercury is first poured over the cork (to prevent its being acted on by the sulphuric acid), and then sulphuric acid is poured over the mercury. The protruding end of the first tube is covered by the lower end of a third tube immersed in the sulphuric acid. _The properties of ozone_ obtained by such a method[6] distinguish it in many respects from oxygen. Ozone very rapidly decolorises indigo, litmus, and many other dyes by oxidising them. Silver is oxidised by it at the ordinary temperature, whilst oxygen is not able to oxidise silver even at high temperatures; a bright silver plate rapidly turns black (from oxidation) in ozonised oxygen. It is rapidly absorbed by mercury, forming oxide; it transforms the lower oxides into higher--for instance, sulphurous anhydride into sulphuric, nitrous oxide into nitric, arsenious anhydride (As_{2}O_{3}) into arsenic anhydride (As_{2}O_{5}) &c.[7] But what is especially characteristic in ozone is the decomposing action it exerts on potassium iodide. Oxygen does not act on it, but ozone passed into a solution of potassium iodide _liberates iodine_, whilst the potassium is obtained as caustic potash, which remains in solution, 2KI + H_{2}O + O = 2KHO + I_{2}. As the presence of minute traces of free iodine may be discovered by means of starch paste, with which it forms a very dark blue-coloured substance, a mixture of potassium iodide with starch paste will detect the presence of very small traces of ozone.[8] Ozone is destroyed or converted into ordinary oxygen not only by heat, but also by long keeping, especially in the presence of alkalis, peroxide of manganese, chlorine, &c. [6] The method above described is the only one which has been well investigated. The admixture of nitrogen, or even of hydrogen, and especially of silicon fluoride, appears to aid the formation and preservation of ozone. Amongst other methods for preparing ozone we may mention the following: 1. In the action of oxygen on phosphorus at the ordinary temperature a portion of the oxygen is converted into ozone. At the ordinary temperature a stick of phosphorus, partially immersed in water and partially in air in a large glass vessel, causes the air to acquire the odour of ozone. It must further be remarked that if the air be left for long in contact with the phosphorus, or without the presence of water, the ozone formed is destroyed by the phosphorus. 2. By the action of sulphuric acid on peroxide of barium. If the latter be covered with strong sulphuric acid (the acid, if diluted with only one-tenth of water, does not give ozone), then at a low temperature the oxygen evolved contains ozone, and in much greater quantities than in that ozone is obtained by the action of electric sparks or phosphorus. 3. Ozone may also be obtained by decomposing strong sulphuric acid by potassium manganate especially with the addition of barium peroxide. [7] Ozone takes up the hydrogen from hydrochloric acid; chlorine is liberated, and can dissolve gold. Iodine is directly oxidised by ozone, but not by oxygen. Ammonia, NH_{3}, is oxidised by ozone into ammonium nitrite (and nitrate), 2NH_{3} + O_{3} = NH_{4}NO_{2} + H_{2}O, and therefore a drop of ammonia, on falling into the gas, gives a thick cloud of the salts formed. Ozone converts lead oxide into peroxide, and suboxide of thallium (which is colourless) into oxide (which is brown), so that this reaction is made use of for detecting the presence of ozone. Lead sulphide, PbS (black), is converted into sulphate, PbSO_{4} (colourless), by ozone. A neutral solution of manganese sulphate gives a precipitate of manganese peroxide, and an acid solution may be oxidised into permanganic acid, HMnO_{4}. With respect to the oxidising action of ozone on organic substances, it may be mentioned that with ether, C_{4}H_{10}O, ozone gives ethyl peroxide, which is capable of decomposing with explosion (according to Berthelot), and is decomposed by water into alcohol, 2C_{2}H_{6}O, and hydrogen peroxide, H_{2}O_{2}. [8] This reaction is the one usually made use of for detecting the presence of ozone. In the majority of cases paper is soaked in solutions of potassium iodide and starch. Such _ozonometrical_ or iodised starch-paper when damp turns blue in the presence of ozone, and the tint obtained varies considerably, according to the length of time it is exposed and to the amount of ozone present. The amount of ozone in a given gas may even to a certain degree he judged by the shade of colour acquired by the paper, if preliminary tests be made. Test-paper for ozone is prepared in the following manner:--One gram of neutral potassium iodide is dissolved in 100 grams of distilled water; 10 grams of starch are then shaken up in the solution, and the mixture is boiled until the starch is converted into a jelly. This jelly is then smeared over blotting-paper and left to dry. It must always he remembered, however, that the colour of iodised starch-paper is changed not only by the action of ozone, but of many other oxidisers; for example, by the oxides of nitrogen (especially N_{2}O_{3}) and hydrogen peroxide. Houzeau proposed soaking common litmus-paper with a solution of potassium iodide, which in the presence of iodine would turn blue, owing to the formation of KHO. In order to determine if the blue colour is not produced by an alkali (ammonia) in the gas, a portion of the paper is not soaked in the potassium iodide, but moistened with water; this portion will then also turn blue if ammonia be present. A reagent for distinguishing ozone from hydrogen peroxide with certainty is not known, and therefore these substances in very small quantities (for instance, in the atmosphere) may easily he confounded. Until recent years the mistake has frequently been made of ascribing the alteration of iodised starch-paper in the air to the presence of ozone; at the present time there is reason to believe that it is most often due to the presence of nitrous acid (Ilosva, 1889). Hence _ozone_, although it has the same _composition as oxygen_, differs from it in stability, and by the fact that it oxidises a number of substances very energetically at the ordinary temperature. In this respect ozone resembles the oxygen of certain unstable compounds, or oxygen at the moment of its liberation.[8 bis] [8 bis] Fluorine (Chap. XI.), acting upon water at the ordinary temperature, takes up the hydrogen, and evolves the oxygen in the form of ozone (Moissan, 1889), and therefore the reaction must be expressed thus:--3H_{2}O + 3F_{2} = 6HF + O_{3}. In ordinary oxygen and ozone we see an example of one and the same substance, in this case an element, appearing in two states. This indicates that the properties of a substance, and even of an element, may vary without its composition varying. Very many such cases are known. Such cases of a chemical transformation which determine a difference in the properties of one and the same element are termed cases of isomerism. The cause of isomerism evidently lies deep within the essential conditions of a substance, and its investigation has already led to a number of results of unexpected importance and of immense scientific significance. It is easy to understand the difference between substances containing different elements or the same elements in different proportions. That a difference should exist in these cases necessarily follows, if, as our knowledge compels us, we admit that there is a radical difference in the simple bodies or elements. But when the composition--_i.e._ the quality and quantity of the elements in two substances is the same and yet their properties are different, then it becomes clear that the conceptions of diverse elements and of the varying composition of compounds, alone, are insufficient for the expression of all the diversity of properties of matter in nature. Something else, still more profound and internal than the composition of substances, must, judging from isomerism, determine the properties and transformation of substances. On what are the isomerism of ozone and oxygen, and the peculiarities of ozone, dependent? In what, besides the extra store of energy, which is one of the peculiarities of ozone, resides the cause of its difference from oxygen? These questions for long occupied the minds of investigators, and were the motive for the most varied, exact, and accurate researches, which were chiefly directed to the study of the volumetric relations exhibited by ozone. In order to acquaint the reader with the previous researches of this kind, I cite the following from a memoir by Soret, in the 'Transactions of the French Academy of Sciences' for 1866: 'Our present knowledge of the volumetric relations of ozone may be expressed in the following manner: '1. "Ordinary oxygen in changing into ozone under the action of electricity shows a diminution in volume." This was discovered by Andrews and Tait. '2. "In acting on ozonised oxygen with potassium iodide and other substances capable of being oxidised, we destroy the ozone, but the volume of the gas remains unchanged." For the researches of Andrews, Soret, v. Babo, and others showed that the proportion of ozonised oxygen absorbed by the potassium iodide is equal to the original contraction of volume of the oxygen--that is, in the absorption of the ozone the volume of the gas remains unchanged. From this it might be imagined that ozone, so to say, does not occupy any space--is indefinitely dense. '3. "By the action of heat ozonised oxygen increases in volume, and is transformed into ordinary oxygen. This increase in volume corresponds with the quantity of ozonised oxygen which is given up to the potassium iodide in its decomposition" (the same observers). '4. These unquestionable experimental results lead to the conclusion that ozone is denser than oxygen, and that in its oxidising action it gives off that portion of its substance to which is due its extra density distinguishing it from ordinary oxygen.' If we imagine (says Weltzien) that _n_ volumes of ozone consist of _n_ volumes of oxygen combined with _m_ volumes of the same substance, and that ozone in oxidising gives up _m_ volumes of oxygen and leaves _n_ volumes of ordinary oxygen gas, then all the above facts can be explained; otherwise it must be supposed that ozone is infinitely dense. 'In order to determine the density of ozone' (we again cite Soret) 'recourse cannot be had to the direct determination of the weight of a given volume of the gas, because ozone cannot be obtained in a pure state. It is always mixed with a very large quantity of oxygen. It was necessary, therefore, to have recourse to such substances as would absorb ozone without absorbing oxygen and without destroying the ozone. Then the density might be deduced from the decrease of volume produced in the gas by the action of this solvent in comparison with the quantity of oxygen given up to potassium iodide. Advantage must also be taken of the determination of the increase of volume produced by the action of heat on ozone, if the volume occupied by the ozone before heating be known.' Soret found two such substances, turpentine and oil of cinnamon. 'Ozone disappears in the presence of turpentine. This is accompanied by the appearance of a dense vapour, which fills a vessel of small capacity (0·14 litre) to such an extent that it is impenetrable to direct solar-rays. On leaving the vessel at rest, it is observed that the cloud of vapour settles; the clearing is first remarked at the upper portion of the vessel, and the brilliant colours of the rainbow are seen on the edge of a cloud of vapour.' Oil of cinnamon--that is, the volatile or essential oil of the well-known spice, cinnamon--gives under similar circumstances the same kind of vapours, but they are much less voluminous. On measuring the gaseous volume before and after the action of both volatile oils, a considerable decrease is remarked. On applying all the necessary corrections (for the solubility of oxygen in the oily liquids named above, for the tension of their vapour, for the change of pressure, &c.) and making a series of comparative determinations, Soret obtained the following result: two volumes of ozone capable of being dissolved, when changed to ordinary (by heating a wire to a red-heat by a galvanic current) increase by one volume. Hence it is evident that in the formation of ozone three volumes of oxygen give two volumes of ozone--that is, its density (referred to hydrogen) = 24. The observations and determinations of Soret showed that ozone is heavier than oxygen, and even than carbonic anhydride (because ozonised oxygen passes through fine orifices more slowly than oxygen and than its mixtures with carbonic anhydride), although lighter than chlorine (it flows more rapidly through such orifices than chlorine), and they indicated that _ozone is one and a half times denser than oxygen_, which may be expressed by designating a molecule of oxygen by O_{2} and of ozone by O_{3}, and hence ozone OO_{2} is comparable with compound substances[9] formed by oxygen, as for instance CO_{2}, SO_{2}, NO_{2}, &c. This explains the chief differences between ozone and oxygen and the cause of the isomerism, and at the same time leads one to expect[10] that ozone, being a gas which is denser than oxygen, would be liquefied much more easily. This was actually shown to be the case in 1880, by Chappuis and Hautefeuille in their researches on the _physical properties of ozone_. Its boiling point under a pressure of 760 mm. is about -106°, and consequently compressed and refrigerated ozone when rapidly expanded forms drops, _i.e._ is liquefied. Liquid and compressed[11] ozone is blue. In dissolving in water ozone partly passes into oxygen. It explodes violently when suddenly compressed and heated, changing into ordinary oxygen and evolving, like all explosive substances,[12] that extra heat which distinguishes it from oxygen. [9] Ozone is, so to say, an oxide of oxygen, just as water is an oxide of hydrogen. Just as aqueous vapour is composed of two volumes of hydrogen and one volume of oxygen, which on combining condense into two volumes of aqueous vapour, so also two volumes of oxygen are combined in ozone with one volume of oxygen to give two volumes of ozone. In the action of ozone on different substances it is only that additional portion of its molecule by which it differs from ordinary oxygen that combines with other bodies, and that is why, under these circumstances, the volume of the ozonised oxygen does not change. Starting with two volumes of ozone, one-third of its weight is parted with, and two volumes of oxygen remain. The above observations of Soret on the capacity of turpentine for dissolving ozone, together with Schönbein's researches on the formation of ozone in the oxidation of turpentine and of similar volatile vegetable oils (entering into the composition of _perfumes_), also explain the action of this ethereal oil on a great many substances. It is known that turpentine oil, when mixed with many substances, promotes their oxidation. In this case it probably not only itself promotes the formation of ozone, but also dissolves ozone from the atmosphere, and thus acquires the property of oxidising many substances. It bleaches linen and cork, decolorises indigo, promotes the oxidation and hardening of boiled linseed oil, &c. These properties of turpentine oil are made use of in practice. Dirty linen and many stained materials are easily cleaned by turpentine, not only because it dissolves the grease, but also because it oxidises it. The admixture of turpentine with drying (boiled) oil, oil-colours, and lacs aids their rapid drying because it attracts ozone. Various oils occurring in plants, and entering into the composition of perfumes and certain scent extracts, also act as oxidisers. They act in the same manner as oil of turpentine and oil of cinnamon. This perhaps explains the refreshing influence they have in scents and other similar preparations, and also the salubrity of the air of pine forests. Water upon which a layer of turpentine oil has been poured acquires, when left standing in the light, the disinfecting and oxidising properties in general of ozonised turpentine (is this due to the formation of H_{2}O_{2}?). [10] The densest, most complex, and heaviest particles of matter should, under equal conditions, evidently be less capable of passing into a state of gaseous motion, should sooner attain a liquid state, and have a greater cohesive force. [11] The blue colour proper to ozone may be seen through a tube one metre long, filled with oxygen, containing 10 p.c. of ozone. The density of liquid ozone has not, so far as I am aware, been determined. [12] All explosive bodies and mixtures (gunpowder, detonating gas, &c.) evolve heat in exploding--that is, the reactions which accompany explosions are exothermal. In this manner ozone in decomposing evolves latent heat, although generally heat is absorbed in decomposition. This shows the meaning and cause of explosion. Thus, judging by what has been said above, ozone should he formed in nature not only in the many processes of oxidation which go on, but also by the condensation of atmospheric oxygen. The significance of ozone in nature has often arrested the attention of observers. There is a series of ozonometrical observations which show the different amounts of ozone in the air at different localities, at different times of the year, and under different circumstances. But the observations made in this direction cannot be considered as sufficiently exact, because the methods in use for determining ozone were not quite accurate. It is however indisputable[13] that the amount of ozone in the atmosphere is subject to variation; that the air of dwellings contains no ozone (it disappears in oxidising organic matter); that the air of fields and forests always contains ozone, or substances (peroxide of hydrogen) which act like it (on iodised starch paper &c.)[13 bis]; that the amount of ozone increases after storms; and that miasms, &c., are destroyed by ozonising the atmosphere. It easily oxidises organic substances, and miasms are produced by organic substances and the germs of organisms, all of which are easily changed and oxidised. Indeed, many miasms--for instance, the volatile substance of decomposing organisms--are clearly destroyed or changed not only by ozone, but also by many other powerfully oxidising substances, such as chlorine water, potassium permanganate, and the like.[14] All that is now known respecting the presence of ozone in the air may be summed up in the following words: A small quantity of an oxidising substance, resembling ozone in its reactions, has undoubtedly been observed and determined in the atmosphere, especially in fresh air, for instance after a storm, and it is very likely that this substance contains a mixture of such oxidising substances as ozone, peroxide of hydrogen, and the lower oxides of nitrogen (especially nitrous acid and its ammonia salt) produced from the elements of the atmosphere by oxidation and by the action of electrical discharges. [13] In Paris it has been found that the further from the centre of the town the greater the amount of ozone in the air. The reason of this is evident: in a city there are many conditions for the destruction of ozone. This is why we distinguish country air as being fresh. In spring the air contains more ozone than in autumn; the air of fields more than the air of towns. [13 bis] The question of the presence of ozone in the air has not yet been fully elucidated, as those reactions by which ozone is generally detected are also common to nitrous acid (and its ammonia salt). Ilosvay de Ilosva (1889), in order to exclude the influence of such bodies, passed air through a 40 per cent. solution of caustic soda, and then through a 20 per cent. solution of sulphuric acid (these solutions do not destroy ozone), and tested the air thus purified for the presence of ozone. As no ozone was then detected the author concludes that all the effects which were formerly ascribed to ozone should be referred to nitrous acid. But this conclusion requires more careful verification, since the researches of Prof. Schönbein on the presence of peroxide of hydrogen in the atmosphere. [14] The oxidising action of ozone may be taken advantage of for technical purposes; for instance, for destroying colouring matters. It has even been employed for bleaching tissues and for the rapid preparation of vinegar, although these methods have not yet received wide application. Thus in ozone we see (1) the capacity of elements (and it must be all the more marked in compounds) of changing in properties without altering in composition; this is termed isomerism;[15] (2) the capacity of certain elements for condensing themselves into molecules of different densities; this forms a special case of isomerism called _polymerism_; (3) the capacity of oxygen for appearing in a still more active and energetic chemical state than that in which it occurs in ordinary gaseous oxygen; and (4) the formation of unstable equilibria, or chemical states, which are illustrated both by the ease with which ozone acts as an oxidiser and by its capacity for decomposing with explosion.[16] [15] Isomerism in elements is termed _allotropism_. [16] A number of substances resemble ozone in one or other of these respects. Thus cyanogen, C_{2}N_{2}, nitrogen chloride, &c., decompose with an explosion and evolution of heat. Nitrous anhydride, N_{2}O_{3}, forms a blue liquid like ozone, and in a number of cases oxidises like ozone. _Hydrogen peroxide._--Many of those properties which we have seen in ozone belong also to a peculiar substance containing oxygen and hydrogen and called hydrogen peroxide or oxygenated water. This substance was discovered in 1818 by Thénard. When heated it is decomposed into water and oxygen, evolving as much oxygen as is contained in the water remaining after the decomposition. That portion of oxygen by which hydrogen peroxide differs from water behaves in a number of cases just like the active oxygen in ozone, which distinguishes it from ordinary oxygen. In H_{2}O_{2}, and in O_{3}, one atom of oxygen acts as a powerful oxidiser, and on separating out it leaves H_{2}O or O_{2}, which do not act so energetically, although they still contain oxygen.[17] Both H_{2}O_{2} and O_{3} contain the oxygen in a compressed state, so to speak, and when freed from pressure by the forces (internal) of the elements in another substance, this oxygen is easily evolved, and therefore acts as oxygen does at the moment of its liberation. Both substances in decomposing, with the separation of a portion of their oxygen, _evolve_ heat, whilst decomposition is usually accompanied by an absorption of heat. [17] It is evident that there is a want of words here for distinguishing oxygen, O, as an ultimate _element_, from oxygen, O_{2}, as a _free element_. The latter should be termed oxygen gas, did not custom and the length of the expression render it inconvenient. Hydrogen peroxide is formed under many circumstances by combustion and oxidation, but in very limited quantities; thus, for instance, it is sufficient to shake up zinc with sulphuric acid, or even with water, to observe the formation of a certain quantity of hydrogen peroxide in the water.[18] From this cause, probably, a series of diverse oxidation processes are accomplished in nature, and according to Prof. Schöne of Moscow, hydrogen peroxide occurs in the atmosphere, although in variable and small quantities, and probably its formation is connected with ozone, with which it has much in common. The usual mode of the formation of hydrogen peroxide, and the method by which it may be indirectly obtained,[19] is by the double decomposition of an acid and the peroxides of certain metals, especially those of potassium, calcium, and barium.[20] We saw when speaking of Oxygen (Chap. III.) that it is only necessary to heat the anhydrous oxide of barium to a red heat in a current of air or oxygen (or, better still, to heat it with potassium chlorate, and then to wash away the potassium chloride formed) to obtain peroxide of barium.[21] Barium peroxide gives hydrogen peroxide by the action of acids in the cold.[22] The process of decomposition is very clear in this case; the hydrogen of the acid replaces the barium of the peroxide, a barium salt of the acid being formed, while the hydrogen peroxide formed in the reaction remains in solution.[23] [18] Schönbein states that the formation of hydrogen peroxide is to be remarked in every oxidation in water or in the presence of aqueous vapour. According to Struve, hydrogen peroxide is contained in snow and in rain-water, and its formation, together with ozone and ammonium nitrate, is even probable in the processes of respiration and combustion. A solution of tin in mercury, or liquid tin amalgam, when shaken up in water containing sulphuric acid, produces hydrogen peroxide, whilst iron under the same circumstances does not give rise to its formation. The presence of small quantities of hydrogen peroxide in these and similar cases is recognised by many reactions. Amongst them, its action on _chromic acid_ in the presence of ether is very characteristic. Hydrogen peroxide converts the chromic acid into a higher oxide, Cr_{2}O_{7}, which is of a dark-blue colour and dissolves in ether. This ethereal solution is to a certain degree stable, and therefore the presence of hydrogen peroxide may be recognised by mixing the liquid to be tested with ether and adding several drops of a solution of chromic acid. On shaking the mixture the ether dissolves the higher oxide of chromium which is formed, and acquires a blue colour. The formation of hydrogen peroxide in the combustion and oxidation of substances containing or evolving hydrogen must be understood in the light of the conception, to be considered later, of molecules occupying equal volumes in a gaseous state. At the moment of its evolution a molecule H_{2} combines with a molecule O_{2}, and gives H_{2}O_{2}. As this substance is unstable, a large proportion of it is decomposed, a small amount only remaining unchanged. If it is obtained, water is easily formed from it; this reaction evolves heat, and the reverse action is not very probable. Direct determinations show that the reaction H_{2}O_{2} = H_{2}O + O evolves 22,000 heat units. From this it will be understood how easy is the decomposition of hydrogen peroxide, as well as the fact that a number of substances which are not directly oxidised by oxygen are oxidised by hydrogen peroxide and by ozone, which also evolves heat on decomposition. Such a representation of the origin of hydrogen peroxide has been developed by me since 1870. Recently (1890) Traube has pronounced a similar opinion, stating that Zn under the action of water and air gives, besides ZnH_{2}O_{2}, also H_{2}O_{2}. [19] The formation of hydrogen peroxide from barium peroxide by a method of double decomposition is an instance of a number of _indirect methods of preparation_. A substance A does not combine with B, but A B is obtained from A C in its action on B D (see Introduction) when C D is formed. Water does not combine with oxygen, but as a hydrate of acids it acts on the compound of oxygen with barium oxide, because this oxide gives a salt with an acid anhydride; or, what is the same thing, hydrogen with oxygen does not directly form hydrogen peroxide, but when combined with a haloid (for example, chlorine), under the action of barium peroxide, BaO_{2}, it leads to the formation of a salt of barium and H_{2}O_{2}. It is to be remarked that the passage of barium oxide, BaO, into the peroxide, BaO_{2}, is accompanied by the _evolution_ of 12,100 heat units per 16 parts of oxygen by weight combined, and the passage of H_{2}O into the peroxide H_{2}O_{2} does not proceed directly, because it would be accompanied by the _absorption_ of 22,000 units of heat by 16 parts by weight of oxygen combined. Barium peroxide, in acting on an acid, evidently evolves less heat than the oxide, and it is this difference of heat that is absorbed in the hydrogen peroxide. Its energy is obtained from that evolved in the formation of the salt of barium. [20] Peroxides of lead and manganese, and other analogous peroxides (see Chap. III., Note 9), do not give hydrogen peroxide under these conditions, but yield chlorine with hydrochloric acid. [21] The impure barium peroxide obtained in this manner may be easily purified. For this purpose it is dissolved in a dilute solution of nitric acid. A certain quantity of an insoluble residue always remains, from which the solution is separated by filtration. The solution will contain not only the compound of the barium peroxide, but also a compound of the barium oxide itself, a certain quantity of which always remains uncombined with oxygen. The acid compounds of the peroxide and oxide of barium are easily distinguishable by their stability. The peroxide gives an unstable compound, and the oxide a stable salt. By adding an aqueous solution of barium oxide to the resultant solution, the whole of the peroxide contained in the solution may be precipitated as a pure aqueous compound (Kouriloff, 1889, obtained the same result by adding an excess of BaO_{2}). The first portions of the precipitate will consist of impurities--for instance, oxide of iron. The barium peroxide then separates out, and is collected on a filter and washed; it forms a substance having a definite composition, BaO_{2},8H_{2}O, and is very pure. Pure hydrogen peroxide should always be prepared from such purified barium peroxide. [22] In the cold, strong sulphuric acid with barium peroxide gives ozone; when diluted with a certain amount of water it gives oxygen (see Note 6), and hydrogen peroxide is only obtained by the action of very weak sulphuric acid. Hydrochloric, hydrofluoric, carbonic, and hydrosilicofluoric acids, and others, when diluted with water also give hydrogen peroxide with barium peroxide. Professor Schöne, who very carefully investigated hydrogen peroxide, showed that it is formed by the action of many of the above-mentioned acids on barium peroxide. In preparing peroxide of hydrogen by means of sulphuric acid, the solution must be kept cold. A solution of maximum concentration may be obtained by successive treatments with sulphuric acid of increasing strength. In this manner a solution containing 2 to 3 grams of pure peroxide in 100 c.c. of water may be obtained (V. Kouriloff). [23] With the majority of acids, that salt of barium which is formed remains in solution; thus, for instance, by employing hydrochloric acid, hydrogen peroxide and barium chloride remain in solution. Complicated processes would be required to obtain pure hydrogen peroxide from such a solution. It is much more convenient to take advantage of the action of carbonic anhydride on the pure hydrate of barium peroxide. For this purpose the hydrate is stirred up in water, and a rapid stream of carbonic anhydride is passed through the water. Barium carbonate, insoluble in water, is formed, and the hydrogen peroxide remains in solution, so that it may be separated from the carbonate by filtering only. On a large scale hydrofluosilicic acid is employed, its barium salt being also insoluble in water. The reaction is expressed by the equation BaO_{2} + H_{2}SO_{4} = H_{2}O_{2} + BaSO_{4}. It is best to take a weak cold solution of sulphuric acid and to almost saturate it with barium peroxide, so that a small excess of acid remains; insoluble barium sulphate is formed. A more or less dilute aqueous solution of hydrogen peroxide is obtained. This solution may be concentrated in a vacuum over sulphuric acid. In this way the water may even be entirely evaporated from the solution of the hydrogen peroxide; only in this case it is necessary to work at a low temperature, and not to keep the peroxide for long in the rarefied atmosphere, as otherwise it decomposes.[23 bis] A solution of peroxide of hydrogen (mixed with the solution of a salt of sodium NaX) is used for bleaching (especially silk and wool) on a large scale, and is now usually prepared from peroxide of sodium Na_{2}O_{2} by the action of acids. Na_{2}O_{2} + 2HX = 2NaX + H_{2}O_{2}[24]. [23 bis] Hydrogen peroxide may be extracted from very dilute solutions by means of ether, which dissolves it, and when mixed with it the hydrogen peroxide may even be distilled. A solution of hydrogen peroxide in water may be strengthened by cooling it to a low temperature, when the water crystallises out--that is, is converted into ice--whilst the hydrogen peroxide remains in solution, as it only freezes at very low temperatures. It must be observed that hydrogen peroxide, in a strong solution in a pure state, is exceedingly unstable even at the ordinary temperature, and therefore it must be preserved in vessels always kept cold, as otherwise it evolves oxygen and forms water. [24] Peroxide of sodium (Chap. XII., Note 49) is prepared by burning sodium in dry air. When pure, hydrogen peroxide is a colourless liquid, without smell, and having a very unpleasant taste--such as belongs to the salts of many metals--the so-called 'metallic' taste. Water stored in zinc vessels has this taste, which is probably due to its containing hydrogen peroxide. The tension of the vapour of hydrogen peroxide is less than that of aqueous vapour; this enables its solutions to be concentrated in a vacuum. The specific gravity of anhydrous hydrogen peroxide is 1·455. Hydrogen peroxide decomposes, with the evolution of oxygen, when heated even to 20°. But the more dilute its aqueous solution the more stable it is. Very weak solutions may be distilled without decomposing the hydrogen peroxide. It decolorises solutions of litmus and turmeric, and acts in a similar manner on many colouring matters of organic origin (for which reason it is employed for bleaching tissues).[24 bis] [24 bis] Peroxide of hydrogen should apparently find an industrial application in the arts, for instance, (1) as a bleaching agent, it having the important advantage over chloride of lime, SO_{2}, &c., of not acting upon the material under treatment. It may be used for bleaching feathers, hair, silk, wool, wood, &c., it also removes stains of all kinds, such as wine, ink, and fruit stains; (2) it destroys bacteria like ozone without having any injurious effect upon the human body. It can also be used for washing all kinds of wounds, for purifying the air in the sick room, &c., and (3) as a preserving agent for potted meats, &c. _Many substances decompose hydrogen peroxide_, forming water and oxygen, without apparently suffering any change. In this case substances in a state of fine division show a much quicker action than compact masses, from which it is evident that the action is here based on contact (_see_ Introduction). It is sufficient to bring hydrogen peroxide into contact with charcoal, gold, the peroxide of manganese or lead, the alkalis, metallic silver, and platinum, to bring about the above decomposition.[25] Besides which, hydrogen peroxide forms water and parts with its oxygen with great ease to a number of substances which are capable of being oxidised or of combining with oxygen, and in this respect is very like ozone and other _powerful oxidisers_.[26] To the class of contact phenomena, which are so characteristic of hydrogen peroxide as a substance which is unstable and easily decomposable with the evolution of heat, must be referred the following--that in the presence of many substances containing oxygen it evolves, not only its own oxygen, but also that of the substances which are brought into contact with it--that is, _it acts in a reducing manner_. It behaves thus with ozone, the oxides of silver, mercury, gold and platinum, and lead peroxide. The oxygen in these substances is not stable, and therefore the feeble influence of contact is enough to destroy its position. Hydrogen peroxide, especially in a concentrated form, in contact with these substances, evolves an immense quantity of oxygen, so that an explosion takes place and an exceedingly powerful evolution of heat is observed if hydrogen peroxide in a concentrated form be made to drop upon these substances in dry powder. Slow decomposition also proceeds in dilute solutions.[27] [25] As the result of careful research, certain of the _catalytic_ or contact phenomena have been subjected to exact explanation, which shows the participation of a substance present in the process of a reaction, whilst, however, it does not alter the series of changes proceeding from mechanical actions only. Professor Schöne, of the Petroffsky Academy, has already explained a number of reactions of hydrogen peroxide which previously were not understood. Thus, for instance, he showed that with hydrogen peroxide, alkalis give peroxides of the alkaline metals, which combine with the remaining hydrogen peroxide, forming unstable compounds which are easily decomposed, and therefore alkalis evince a decomposing (catalytic) influence on solutions of hydrogen peroxide. Only acid solutions of hydrogen peroxide, and then only dilute ones, can be preserved well. [26] _Hydrogen peroxide_, as a substance containing much oxygen (namely, 16 parts to one part by weight of hydrogen), exhibits many _oxidising reactions_. Thus, it oxidises arsenic, converts lime into calcium peroxide, the oxides of zinc and copper into peroxides; it parts with its oxygen to many sulphides, converting them into sulphates, &c. So, for example, it converts black lead sulphide, PbS, into white lead sulphate, PbSO_{4}, copper sulphide into copper sulphate, and so on. The restoration of old oil paintings by hydrogen peroxide is based on this action. Oil colours are usually admixed with white lead, and in many cases the colour of oil-paints becomes darker in process of time. This is partly due to the sulphuretted hydrogen contained in the air, which acts on white lead, forming lead sulphide, which is black. The intermixture of the black colour darkens the rest. In cleaning a picture with a solution of hydrogen peroxide, the black lead sulphide is converted into white sulphate, and the colours brighten owing to the disappearance of the black substance which previously darkened them. Hydrogen peroxide oxidises with particular energy substances containing hydrogen and capable of easily parting with it to oxidising substances. Thus it decomposes hydriodic acid, setting the iodine free and converting the hydrogen it contains into water; it also decomposes sulphuretted hydrogen in exactly the same manner, setting the sulphur free. Starch paste with potassium iodide is not, however, directly coloured by peroxide of hydrogen in the entire absence of free acids; but the addition of a small quantity of iron sulphate (green vitriol) or of lead acetate to the mixture is enough to entirely blacken the paste. This is a very sensitive reagent (test) for peroxide of hydrogen, like the test with chromic acid and ether (_see_ Note 8). [27] To explain the phenomenon, an hypothesis has been put forward by Brodie, Clausius, and Schönbein which supposes ordinary oxygen to be an electrically neutral substance, composed, so to speak, of two electrically opposite kinds of oxygen--positive and negative. It is supposed that hydrogen peroxide contains one kind of such polar oxygen, whilst in the oxides of the above-named metals the oxygen is of opposite polarity. It is supposed that in the oxides of the metals the oxygen is electro-negative, and in hydrogen peroxide electro-positive, and that on the mutual contact of these substances ordinary neutral oxygen is evolved as a consequence of the mutual attraction of the oxygens of opposite polarity. Brodie admits the polarity of oxygen in combination, but not in an uncombined state, whilst Schönbein supposes uncombined oxygen to be polar also, considering ozone as electro-negative oxygen. The supposition that the oxygen of ozone is different from that of hydrogen peroxide is contradicted by the fact that in acting on barium peroxide strong sulphuric acid forms ozone, and dilute acid forms hydrogen peroxide. Just as a whole series of metallic compounds, and especially the oxides and their hydrates, correspond with water, so also there are many substances analogous to hydrogen peroxide. Thus, for instance, calcium peroxide is related to hydrogen peroxide in exactly the same way as calcium oxide or lime is related to water. In both cases the hydrogen is replaced by a metal--namely, by calcium.[27 bis] But it is most important to remark that the nearest approach to the properties of hydrogen peroxide is afforded by a non-metallic element, chlorine; its action on colouring matters, its capacity for oxidising, and for evolving oxygen from many oxides, is analogous to that exhibited by hydrogen peroxide. Even the very formation of chlorine is closely analogous to the formation of peroxide of hydrogen; chlorine is obtained from manganese peroxide, MnO_{2}, and hydrochloric acid, HCl, and hydrogen peroxide from barium peroxide, BaO_{2}, and the same acid. The result in one case is essentially water, chlorine, and manganese chloride; and in the other case barium chloride and hydrogen peroxide are produced. Hence water + chlorine corresponds with hydrogen peroxide, and the action of chlorine in the presence of water is analogous to the action of hydrogen peroxide. This analogy between chlorine and hydrogen peroxide is expressed in the conception of an aqueous radicle, which (Chapter III.) has been already mentioned. _This aqueous radicle_ (or hydroxyl) is that which is left from water if it be imagined as deprived of half of its hydrogen. According to this method of expression, caustic soda will be a compound of sodium with the aqueous radicle, because it is formed from water with the evolution of half the hydrogen. This is expressed by the following formulæ: water, H_{2}O, caustic soda, NaHO, just as hydrochloric acid is HCl and sodium chloride NaCl. Hence the aqueous radicle HO is a compound radicle, just as chlorine, Cl, is a simple radicle. They both give hydrogen compounds, HHO, water, and HCl, hydrochloric acid; sodium compounds, NaHO and NaCl, and a whole series of analogous compounds. Free chlorine in this sense will be ClCl, and hydrogen peroxide HOHO, which indeed expresses its composition, because it contains twice as much oxygen as water does.[28] [27 bis] It should be mentioned that Schiloff (1893) on taking a 3 per cent. solution of H_{2}O_{2}, adding soda to it, and then extracting the peroxide of hydrogen from the mixture by shaking it with ether, obtained a 50 per cent. solution of H_{2}O_{2}, which, although perfectly free from other acids, gave a distinctly acid reaction with litmus. And here attention should first of all be turned to the fact that the peroxides of the metals correspond to H_{2}O_{2}, like salts to an acid, for instance, Na_{2}O_{2} and BaO_{2}, &c. Furthermore, it must be remembered that O is an analogue of S (Chapters XV. and XX.), and sulphur gives H_{2}S, H_{2}SO_{3}, and H_{2}SO_{4}. And sulphurous acid, H_{2}SO_{3}, is unstable as a hydrate, and gives water and the anhydride SO_{2}. If the sulphur be replaced by oxygen, then instead of H_{2}SO_{3} and SO_{2}, we have H_{2}OO_{3} and OO_{2}. The latter is ozone, while the salt K_{2}O_{4} (peroxide of potassium) corresponds to the hydrate H_{2}O_{4} as to an acid. And between H_{2}O and H_{2}O_{4} there may exist intermediate acid compounds, the first of which would be H_{2}O_{2}, in which, from analogy to the sulphur compounds, one would expect acid properties. Besides which we may mention that for sulphur, besides H_{2}S (which is a feeble acid), H_{2}S_{2}, H_{2}S_{3}, H_{2}S_{5} are known. Thus in many respects H_{2}O_{2} offers points of resemblance to acid compounds, and as regards its qualitative (reactive) analogies, it not only resembles Na_{2}O_{2}, BaO_{2}, &c., but also persulphuric acid HSO_{4} (to which the anhydride S_{2}O_{7} corresponds) and Cu_{2}O_{7}, &c., which will be subsequently described. [28] Tamman and Carrara (1892) showed by determining the depression (fall of the temperature of the formation of ice, Chapters I. and VII.) that the molecule of peroxide of hydrogen contains H_{2}O_{2}, and not HO or H_{3}O_{3}. Thus in ozone and hydrogen peroxide we see examples of very unstable, easily decomposable (by time, spontaneously, and on contact) substances, full of the energy necessary for change,[28 bis] capable of being easily reconstituted (in this case decomposing with the evolution of heat); they are therefore examples of _unstable chemical equilibria_. If a substance exists, it signifies that it already presents a certain form of equilibrium between those elements of which it is built up. But chemical, like mechanical, equilibria exhibit different degrees of stability or solidity.[29] [28 bis] The lower oxides of nitrogen and chlorine and the higher oxides of manganese are also formed with the absorption of heat, and therefore, like hydrogen peroxide, act in a powerfully oxidising manner, and are not formed by the same methods as the majority of other oxides. It is evident that, being endowed with a richer store of energy (acquired in combination or by absorption of heat), such substances, compared with others poorer in energy, will exhibit a greater diversity of cases of chemical action with other substances. [29] If the point of support of a body lies in a vertical line below the centre of gravity, it is in unstable equilibrium. If the centre of gravity lies below the point of support; the state of equilibrium is very stable, and a vibration may take place about this position of stable equilibrium, as in a pendulum or balance, when finally the body assumes a position of stable equilibrium. But if, keeping to the same mechanical example, the body be supported not on a point, in the geometrical sense of the word, but on a small plane, then the state of unstable equilibrium may be preserved, unless destroyed by external influences. Thus a man stands upright supported on the plane, or several points of the surfaces of his feet, having the centre of gravity above the points of support. Vibration is then possible, but it is limited, otherwise on passing outside the limit of possible equilibrium another more stable position is attained about which vibration becomes more possible. A prism immersed in water may have several more or less stable positions of equilibrium. The same is also true with the atoms in molecules. Some molecules present a state of more stable equilibrium than others. Hence from this simple comparison it will be at once evident that the stability of molecules may vary considerably, that one and the same elements, taken in the same number, may give isomerides of different stability, and, lastly, that there may exist states of equilibria which are so unstable, so ephemeral, that they will only arise under particularly special conditions--such, for example, as certain hydrates mentioned in the first chapter (_see_ Notes 57, 67, and others). And if in one case the instability of a given state of equilibrium is expressed by its instability with a change of temperature or physical state, then in other cases it is expressed by the facility with which it decomposes under the influence of contact or of the chemical influence of other substances. Besides this, hydrogen peroxide presents another side of the subject which is not less important, and is much clearer and more general. Hydrogen unites with oxygen in two degrees of oxidation: water or hydrogen oxide, and oxygenated water or hydrogen peroxide; for a given quantity of hydrogen, the peroxide contains twice as much oxygen as does water. This is a fresh example confirming the correctness of the law of multiple proportions, to which we have already referred in speaking of the water of crystallisation of salts. We can now formulate this law--_the law of multiple proportions_. _If two substances A and B (either simple or compound), unite together to form several compounds, A_{n}B_{m}, A_{q}B_{r} ..., then having expressed the compositions of all these compounds in such a way that the quantity (by weight or volume) of one of the component parts will be a constant quantity_ A, _it will be observed that in all the compounds_ AB_{a}, AB_{b} _... the quantities of the other component part,_ B, _will always be in commensurable relation: generally in simple multiple proportion--that is, that a : b ..., or m/n is to r/q as whole numbers, for instance as 2 : 3 or 3 : 4...._ The analysis of water shows that in 100 parts by weight it contains 11·112 parts by weight of hydrogen and 88·888 of oxygen, and the analysis of peroxide of hydrogen shows that it contains 94·112 parts of oxygen to 5·888 parts of hydrogen. In this the analysis is expressed, as analyses generally are, in percentages; that is, it gives the amounts of the elements in a hundred parts by weight of the substance. The direct comparison of the percentage compositions of water and hydrogen peroxide does not give any simple relation. But such a relation is immediately apparent if we calculate the composition of water and of hydrogen peroxide, having taken either the quantity of oxygen or the quantity of hydrogen as a constant quantity--for instance, as unity. The most simple proportions show that in water there are contained eight parts of oxygen to one part of hydrogen, and in hydrogen peroxide sixteen parts of oxygen to one part of hydrogen; or one-eighth part of hydrogen in water and one-sixteenth part of hydrogen in hydrogen peroxide to one part of oxygen. Naturally, the analysis does not give these figures with absolute exactness--it gives them within a certain degree of error--but they approximate, as the error diminishes, to that limit which is here given. The comparison of the quantities of hydrogen and oxygen in the two substances above named, taking one of the components as a constant quantity, gives an example of the application of the law of multiple proportions, because water contains eight parts and hydrogen peroxide sixteen parts of oxygen to one part of hydrogen, and these figures are commensurable and are in the simple proportion of 1 : 2. An exactly similar multiple proportion is observed in the composition of all other well-investigated definite chemical compounds,[30] and therefore the law of multiple proportions is accepted in chemistry as the starting point from which other considerations proceed. [30] When, for example, any element forms several oxides, they are subject to the law of multiple proportions. For a given quantity of the non-metal or metal the quantities of oxygen in the different degrees of oxidation will stand as 1 : 2, or as 1 : 3, or as 2 : 3, or as 2 : 7, and so on. Thus, for instance, copper combines with oxygen in at least two proportions, forming the oxides found in nature, and called the suboxide and the oxide of copper, Cu_{2}O and CuO; the oxide contains twice as much oxygen as the suboxide. Lead also presents two degrees of oxidation, the oxide and peroxide, and in the latter there is twice as much oxygen as in the former, PbO and PbO_{2}. When a base and an acid are capable of forming several kinds of salts, normal, acid, basic, and anhydro-, it is found that they also clearly exemplify the law of multiple proportions. This was demonstrated by Wollaston soon after the discovery of the law in question. We saw in the first chapter that salts show different degrees of combination with water of crystallisation, and that they obey the law of multiple proportions. And, more than this, the indefinite chemical compounds existing as solutions may, as we saw in the same chapter, be brought under the law of multiple proportions by the hypothesis that solutions are unstable hydrates formed according to the law of multiple proportions, but occurring in a state of dissociation. By means of this hypothesis the law of multiple proportions becomes still more general, and all the aspects of chemical compounds are subject to it. The direction of the whole contemporary state of chemistry was determined by the discoveries of Lavoisier and Dalton. By endeavouring to prove that in solutions we have nothing else than the liquid products of the dissociation of definite hydrates, it is my aim to bring also this category of indefinite compounds under the general principle enunciated by Dalton; just as astronomers have discovered a proof and not a negation of the laws of Newton in perturbations. The law of multiple proportions was discovered at the beginning of this century by John Dalton, of Manchester, in investigating the compounds of carbon with hydrogen. It appeared that two gaseous compounds of these substances--marsh gas, CH_{4}, and olefiant gas, C_{2}H_{4}, contain for one and the same quantity of hydrogen, quantities of carbon which stand in multiple proportion; namely, marsh gas contains relatively half as much carbon as olefiant gas. Although the analysis of that time was not exact, still the accuracy of this law, recognised by Dalton, was further confirmed by more accurate investigations. On establishing the law of multiple proportions, Dalton gave a hypothetical explanation for it. This explanation is based on the atomic theory of matter. In fact, the law of multiple proportions may be very easily understood by admitting the atomic structure of matter. The essence of the atomic theory is that matter is supposed to consist of an agglomeration of small and indivisible parts--atoms--which do not fill up the whole space occupied by a substance, but stand apart from each other, as the sun, planets, and stars do not fill up the whole space of the universe, but are at a distance from each other. The form and properties of substances are determined by the position of their atoms in space and by their state of motion, whilst the reactions accomplished by substances are understood as redistributions of the relative positions of atoms and changes in their motion. The atomic representation of matter arose in very ancient times,[31] and up to recent times was at variance with the dynamical hypothesis, which considers matter as only a manifestation of forces. At the present time, however, the majority of scientific men uphold the atomic hypothesis, although the present conception of an atom is quite different from that of the ancient philosophers. An atom at the present day is regarded rather as an individual or unit which is indivisible by physical[32] and chemical forces, whilst the atom of the ancients was actually mechanically and geometrically indivisible. When Dalton (1804) discovered the law of multiple proportions, he pronounced himself in favour of the atomic doctrine, because it enables this law to be very easily understood. If the divisibility of every element has a limit, namely the atom, then the atoms of elements are the extreme limits of all divisibility, and if they differ from each other in their nature, the formation of a compound from elementary matter must consist in the aggregation of several different atoms into one whole or system of atoms, now termed _particles or molecules_. As atoms can only combine in their entire masses, it is evident that not only the law of definite composition, but also that of multiple proportions, must apply to the combination of atoms with one another; for one atom of a substance can combine with one, two, or three atoms of another substance, or in general one, two, three atoms of one substance are able to combine with one, two, or three atoms of another; this being the essence of the law of multiple proportions. Chemical and physical data are very well explained by the aid of the atomic theory. The displacement of one element by another follows the law of equivalency. In this case one or several atoms of a given element take the place of one or several atoms of another element in its compounds. The atoms of different substances can be mixed together in the same sense as sand can be mixed with clay. They do not unite into one whole--_i.e._ there is not a perfect blending in the one or other case, but only a juxtaposition, a homogeneous whole being formed from individual parts. This is the first and most simple method of applying the atomic theory to the explanation of chemical phenomena.[33] [31] Leucippus, Democritus, and especially Lucretius, in the classical ages, represented matter as made up of atoms--that is, of parts incapable of further division. The geometrical impossibility of such an admission, as well as the conclusions which were deduced by the ancient atomists from their fundamental propositions, prevented other philosophers from following them, and the atomic doctrine, like very many others, lived, without being ratified by fact, in the imaginations of its followers. Between the present atomic theory and the doctrine of the above-named ancient philosophers there is naturally a remote historical connection, as between the doctrine of Pythagoras and Copernicus, but they are essentially different. For us the atom is indivisible, not in the geometrical abstract sense, but only in a physical and chemical sense. It would be better to call the atoms indivisible _individuals_. The Greek atom = the Latin individual, both according to the etymology and original sense of the words, but in course of time these two words have acquired a different meaning. The individual is mechanically and geometrically divisible, and only indivisible in a special sense. The earth, the sun, a man or a fly are individuals, although geometrically divisible. Thus the 'atoms' of contemporary science, indivisible in a chemical sense, form those units with which we are concerned in the investigation of the natural phenomena of matter, just as a man is an indivisible unit in the investigation of social relations, or as the stars, planets, and luminaries serve as units in astronomy. The formation of the vortex hypothesis, in which, as we shall afterwards see, atoms are entire whirls mechanically complex, although physico-chemically indivisible, clearly shows that the scientific men of our time in holding to the atomic theory have only borrowed the word and form of expression from the ancient philosophers, and not the essence of their atomic doctrine. It is erroneous to imagine that the contemporary conceptions of the atomists are nothing but the repetition of the metaphysical reasonings of the ancients. To show the true meaning of the atomism of the ancient philosophers, and the profound difference between their points of argument and those of contemporary men of science, I cite the following fundamental propositions of Democritus (B.C. 470-380) as the best expounder of the atomic doctrine of the ancients:--(1) Nothing can proceed from nothing, nothing that exists can disappear or be destroyed (and hence matter), and every change only consists of a combination or separation. (2) Nothing is accidental, there is a reason and necessity for everything. (3) All except atoms and vacua is reason and not existence. (4) The atoms, which are infinite in number and form, constitute the visible universe by their motion, impact, and consequent revolving motion. (5) The variety of objects depends only upon a difference in the number, form, and order of the atoms of which they are formed, and not upon a qualitative difference of their atoms, which only act upon each other by pressure and impact. (6) The spirit, like fire, consists of minute, spherical, smooth, and very mobile and all-penetrating atoms, whose motion forms the phenomenon of life. These Democritian, chiefly metaphysical, principles of atomism are so essentially different from the principles of the present atomic doctrine, which is exclusively applied to explaining the phenomena of the external world, that it may be useful to mention the essence of the atomic propositions of Boscovitch, a Slav who lived in the middle of the eighteenth century, and who is regarded as the founder of the modern atomic doctrines which, however, did not take hold upon the minds of scientific men, and were rarely applied prior to Dalton--_i.e._ until the beginning of the nineteenth century. The doctrine of Boscovitch was enunciated by him in 1758-1764 in his '_Philosophiæ naturalis theoria reducta ad unicam legem virium in natura existentium_.' Boscovitch considers matter to be composed of atoms, and the atoms to be the points or centres of forces (just as the stars and planets may be considered as points of space), acting between bodies and their parts. These forces vary with the distance, so that beyond a certain very small distance all atoms, and hence also their aggregates, are attracted according to Newton's law, but at less distances, there alternate wave-like spheres of gradually decreasing attraction and increasing (as the distance decreases) repulsion, until at last at a minimum distance only the repellent action remains. Atoms, therefore, cannot merge into each other. Consequently, the atoms are held at a certain distance from each other, and therefore occupy space. Boscovitch compares the sphere of repulsion surrounding the atoms to the spheres of action of firing of a detachment of soldiers. According to his doctrine, atoms are indestructible, do not merge into each other, have mass, are everlasting and mobile under the action of the forces proper to them. Maxwell rightly calls this hypothesis the 'extreme' among those existing to explain matter, but many aspects of Boscovitch's doctrine repeat themselves in the views of our day, with this essential difference, that instead of a mathematical point furnished with the properties of mass, the atoms are endowed with a corporality, just as the stars and planets are corporal, although in certain aspects of their interaction they may be regarded as mathematical points. In my opinion, the atomism of our day must first of all be regarded merely as a convenient method for the investigation of ponderable matter. As a geometrician in reasoning about curves represents them as formed of a succession of right lines, because such a method enables him to analyse the subject under investigation, so the scientific man applies the atomic theory as a method of analysing the phenomena of nature. Naturally there are people now, as in ancient times, and as there always will be, who apply reality to imagination, and therefore there are to be found atomists of extreme views; but it is not in their spirit that we should acknowledge the great services rendered by the atomic doctrine to all science, which, while it has been essentially independently developed, is, if it be desired to reduce all ideas to the doctrines of the ancients, a union of the ancient dynamical and atomic doctrines. [32] Dalton and many of his successors distinguished the atoms of elements and compounds, in which they clearly symbolised the difference of their opinion from the representations of the ancients. Now only the individuals of the elements, indivisible by physical and chemical forces, are termed atoms, and the individuals of compounds indivisible under physical changes are termed molecules; these are divisible into atoms by chemical forces. [33] In the present condition of science, either the atomic or the dynamical hypothesis is inevitably obliged to admit the existence of an invisible and imperceptible motion in matter, without which it is impossible to understand either light or heat, or gaseous pressure, or any of the mechanical, physical, or chemical phenomena. The ancients saw vital motion in animals only, but to us the smallest particle of matter, endued with _vis viva_, or energy in some degree or other, is incomprehensible without self-existent motion. Thus motion has become a conception inseparably knit with the conception of matter, and this has prepared the ground for the revival of the dynamical hypothesis of the constitution of matter. In the atomic theory there has arisen that generalising idea by which the world of atoms is constructed, like the universe of heavenly bodies, with its suns, planets, and meteors, endued with everlasting force of motion, forming molecules as the heavenly bodies form systems, like the solar system, which molecules are only relatively indivisible in the same way as the planets of the solar system are inseparable, and stable and lasting as the solar system is lasting. Such a representation, without necessitating the absolute indivisibility of atoms, expresses all that science can require for an hypothetical representation of the constitution of matter. In closer proximity to the dynamical hypothesis of the constitution of matter is the oft-times revived _vortex hypothesis_. Descartes first endeavoured to raise it; Helmholtz and Thomson (Lord Kelvin) gave it a fuller and more modern form; many scientific men applied it to physics and chemistry. The idea of vortex rings serves as the starting point of this hypothesis; these are familiar to all as the rings of tobacco smoke, and may be artificially obtained by giving a sharp blow to the sides of a cardboard box having a circular orifice and filled with smoke. Phosphuretted hydrogen, as we shall see later on, when bubbling from water always gives very perfect vortex rings in a still atmosphere. In such rings it is easy to observe a constant circular motion about their axes, and to notice the stability the rings possess in their motion of translation. This unchangeable mass, endued with a rapid internal motion, is likened to the atom. In a medium deprived of friction, such a ring, as is shown by theoretical considerations of the subject from a mechanical point of view, would be perpetual and unchangeable. The rings are capable of grouping together, and in combining, without being absolutely indivisible, remain indivisible. The vortex hypothesis has been established in our times, but it has not been fully developed; its application to chemical phenomena is not clear, although not impossible; it does not satisfy a doubt in respect to the nature of the space existing between the rings (just as it is not clear what exists between atoms, and between the planets), neither does it tell us what is the nature of the moving substance of the ring, and therefore for the present it only presents the germ of an hypothetical conception of the constitution of matter; consequently, I consider that it would be superfluous to speak of it in greater detail. However, the thoughts of investigators are now (and naturally will be in the future), as they were in the time of Dalton, often turned to the question of the limitation of the mechanical division of matter, and the atomists have searched for an answer in the most diverse spheres of nature. I select one of the methods attempted, which does not in any way refer to chemistry, in order to show how closely all the provinces of natural science are bound together. Wollaston proposed the investigation of the _atmosphere of the heavenly bodies_ as a means for confirming the existence of atoms. If the divisibility of matter be infinite, then air must extend throughout the entire space of the heavens as it extends all over the earth by its elasticity and diffusion. If the infinite divisibility of matter be admitted, it is impossible that any portion of the whole space of the universe can be entirely void of the component parts of our atmosphere. But if matter be divisible up to a certain limit only--namely, up to the atom--then there _can exist_ a heavenly body void of an atmosphere; and if such a body be discovered, it would serve as an important factor for the acceptation of the validity of the atomic doctrine. The moon has long been considered as such a luminary and this circumstance, especially from its proximity to the earth, has been cited as the best proof of the validity of the atomic doctrine. This proof is apparently (Poisson) deprived of some of its force from the possibility of the transformation of the component parts of our atmosphere into a solid or liquid state at immense heights above the earth's surface, where the temperature is exceedingly low; but a series of researches (Pouillet) has shown that the temperature of the heavenly space is comparatively not so very low, and is attainable by experimental means, so that at the low existing pressure the liquefaction of the gases of the atmosphere cannot he expected even on the moon. Therefore the absence of an atmosphere about the moon, if it were not subject to doubt, would be counted as a forcible proof of the atomic theory. As a proof of the absence of a lunar atmosphere, it is cited that the moon, in its independent motion between the stars, when eclipsing a star--that is, when passing between the eye and the star--does not show any signs of refraction at its edge; the image of the star does not alter its position in the heavens on approaching the moon's surface, consequently there is no atmosphere on the moon's surface capable of refracting the rays of light. Such is the conclusion by which the absence of a lunar atmosphere is acknowledged. But this conclusion is most feeble, and there are even facts in exact contradiction to it, by which the existence of a lunar atmosphere may be proved. The entire surface of the moon is covered with a number of mountains, having in the majority of cases the conical form natural to volcanoes. The volcanic character of the lunar mountains was confirmed in October 1866, when a change was observed in the form of one of them (the crater Linnea). These mountains must be on the edge of the lunar disc. Seen in profile, they screen one another and interfere with observations on the surface of the moon, so that when looking at the edge of the lunar disc we are obliged to make our observations not on the moon's surface, but at the summits of the lunar mountains. These mountains are higher than those on our earth, and consequently at their summits the lunar atmosphere must he exceedingly rarefied even if it possess an observable density at the surface. Knowing the mass of the moon to be eighty-two times less than the mass of the earth, we are able to determine approximately that our atmosphere at the moon's surface would be about twenty-eight times lighter than it is on the earth, and consequently at the very surface of the moon the refraction of light by the lunar atmosphere must he very slight, and at the heights of the lunar mountains it must be imperceptible, and would be lost within the limits of experimental error. Therefore the absence of refraction of light at the edge of the moon's disc cannot yet be urged in favour of the absence of a lunar atmosphere. There is even a series of observations obliging us to admit the existence of this atmosphere. These researches are due to Sir John Herschel. This is what he writes: 'It has often been remarked that during the eclipse of a star by the moon there occurs a peculiar optical illusion; it seems as if the star before disappearing passed over the edge of the moon and is seen through the lunar disc, sometimes for a rather long period of time. I myself have observed this phenomenon, and it has been witnessed by perfectly trustworthy observers. I ascribe it to optical illusion, but it must be admitted that the star might have been seen on the lunar disc through some deep ravine on the moon.' Geniller, in Belgium (1856), following the opinion of Cassini, Eiler, and others, gave an explanation of this phenomenon: he considers it due to the refraction of light in the valleys of the lunar mountains which occur on the edge of the lunar disc. In fact, although these valleys do not probably present the form of straight ravines, yet it may sometimes happen that the light of a star is so refracted that its image might he seen, notwithstanding the absence of a direct path for the light-rays. He then goes on to remark that the density of the lunar atmosphere must be variable in different parts, owing to the very long nights on the moon. On the dark, or non-illuminated portion, owing to these long nights, which last thirteen of our days and nights, there must be excessive cold, and hence a denser atmosphere, while, on the contrary, on the illuminated portion the atmosphere must be much more rarefied. This variation in the temperature of the different parts of the moon's surface explains also the absence of clouds, notwithstanding the possible presence of air and aqueous vapour, on the visible portion of the moon. The presence of an atmosphere round the sun and planets, judging from astronomical observations, may be considered as fully proved. On Jupiter and Mars even bands of clouds may be distinguished. Thus the atomic doctrine, admitting a finite mechanical divisibility only, must he, as yet at least, only accepted as a means, similar to that means which a mathematician employs when he breaks up a continuous curvilinear line into a number of straight lines. There is a simplicity of representation in atoms, but there is no absolute necessity to have recourse to them. The conception of the individuality of the parts of matter exhibited in chemical elements only is necessary and trustworthy. A certain number of atoms _n_ of an element A in combining with several atoms _m_ of another element B give a compound A_{_n_} B_{_m_}, each molecule of which will contain the atoms of the elements A and B in this ratio, and therefore the compound will present a _definite composition_, expressed by the formula A_{_n_}B_{_m_}, where A and B are the weights of the atoms and _n_ and _m_ their relative number. If the same elements A and B, in addition to A_{_n_}B_{_m_}, also yield another compound A_{_r_}B_{_q_}, then by expressing the composition of the first compound by A_{_nr_}B_{_mr_} (and this is the same composition as A_{_n_}B_{_m_}), and of the second compound by A_{_rn_}B_{_qn_}, we have the law of multiple proportions, because for a given quantity of the first element, A_{_rn_}, there occur quantities of the second element bearing the same ratio to each other as _mr_ is to _qn_; and as _m_, _r_, _q_, and _n_ are whole numbers, their products are also whole numbers, and this is expressed by the law of multiple proportion. Consequently the atomic theory is in accordance with and evokes the first laws of definite chemical compounds: the law of definite composition and the law of multiple proportions. So, also, is the relation of the atomic theory to the third law of definite chemical compounds, the _law of reciprocal combining weights_, which is as follows:--If a certain weight of a substance C combine with a weight _a_ of a substance A, and with a weight _b_ of a substance B, then, also, the substances A and B will combine together in quantities _a_ and _b_ (or in multiples of them). This should be the case from the conception of atoms. Let A, B, and C be the weights of the atoms of the three substances, and for simplicity of reasoning suppose that combination takes place between single atoms. It is evident that if the substance gives AC and BC, then the substances A and B will give a compound AB, or their multiple, A_{_n_}B_{_m_}. And so it is in reality in nature. Sulphur combines with hydrogen and with oxygen. Sulphuretted hydrogen contains thirty-two parts by weight of sulphur to two parts by weight of hydrogen; this is expressed by the formula H_{2}S. Sulphur dioxide, SO_{2}, contains thirty-two parts of sulphur and thirty-two parts of oxygen, and therefore we conclude, from the law of combining weights, that oxygen and hydrogen will combine in the proportion of two parts of hydrogen and thirty-two parts of oxygen, or multiple numbers of them. And we have seen this to be the case. Hydrogen peroxide contains thirty-two parts of oxygen, and water sixteen parts, to two parts of hydrogen; and so it is in all other cases. This consequence of the atomic theory is in accordance with nature, with the results of analysis, and is one of the most important laws of chemistry. It is a law, because it indicates the _relation between_ the weights of substances entering into chemical combination. Further, it is an eminently exact law, and not an approximate one. The law of combining weights is a law of nature, and by no means an hypothesis, for even if the entire theory of atoms be refuted, still the laws of multiple proportions and of combining weights will remain, inasmuch as they deal with facts. They may be guessed at from the sense of the atomic theory, and historically the law of combining weights is intimately connected with this theory; but they are not identical, but only connected, with it. The law of combining weights is formulated with great ease, and is an immediate consequence of the atomic theory; without it, it is even difficult to understand. Data for its evolution existed previously, but it was not formulated until those data were interpreted by the atomic theory, an hypothesis which up to the present time has contradicted neither experiment nor fact, and is useful and of general application. Such is the nature of hypotheses. They are indispensable to science; they bestow an order and simplicity which are difficultly attainable without their aid. The whole history of science is a proof of this. And therefore it may be truly said that it is better to hold to an hypothesis which may afterwards prove untrue than to have none at all. Hypotheses facilitate scientific work and render it consistent. In the search for truth, like the plough of the husbandman, they help forward the work of the labourer. CHAPTER V NITROGEN AND AIR Gaseous _nitrogen_ forms about four-fifths (by volume) of the atmosphere; consequently the air contains an exceedingly large mass of it. Whilst entering in so considerable a quantity into the composition of air, nitrogen does not seem to play any active part in the atmosphere, the chemical action of which is mainly dependent on the oxygen it contains. But this is not an entirely correct idea, because animal life cannot exist in pure oxygen, in which animals pass into an abnormal state and die; and the nitrogen of the air, although slowly, forms diverse compounds, many of which play a most important part in nature, especially in the life of organisms. However, neither plants[1] nor animals directly absorb the nitrogen of the air, but take it up from already prepared nitrogenous compounds; further, plants are nourished by the nitrogenous substances contained in the soil and water, and animals by the nitrogenous substances contained in plants and in other animals. Atmospheric electricity is capable of aiding the passage of gaseous nitrogen into nitrogenous compounds, as we shall afterwards see, and the resultant substances are carried to the soil by rain, where they serve for the nourishment of plants. Plentiful harvests, fine crops of hay, vigorous growth of trees--other conditions being equal--are only obtained when the soil contains _ready prepared nitrogenous compounds_, consisting either of those which occur in air and water, or of the residues of the decomposition of other plants or animals (as in manure). The nitrogenous substances contained in animals have their origin in those substances which are formed in plants. Thus the nitrogen of the atmosphere is the origin of all the nitrogenous substances occurring in animals and plants, although not directly so, but after first combining with the other elements of air. [1] See Note 15 bis. The nitrogenous compounds which enter into the composition of plants and animals are of primary importance; no vegetable or animal cell--that is, the elementary form of organism--exists without containing a nitrogenous substance, and moreover organic life manifests itself primarily in these nitrogenous substances. The germs, seeds, and those parts by which cells multiply themselves abound in nitrogenous substances; the sum total of the phenomena which are proper to organisms depend primarily on the chemical properties of the nitrogenous substances which enter into their composition. It will be sufficient, for instance, to point out the fact that vegetable and animal organisms, clearly distinguishable as such, are characterised by a different degree of energy in their nature, and at the same time by a difference in the amount of nitrogenous substances they contain. In plants, which compared with animals possess but little activity, being incapable of independent movement, &c., the amount of nitrogen is very much less than in animals, whose tissues are almost exclusively formed of nitrogenous substances. It is remarkable that the nitrogenous parts of plants, chiefly of the lower orders, sometimes present both forms and properties which approach to those of animal organisms; for example, the zoospores of sea-weeds, or those parts by means of which the latter multiply themselves. These zoospores on leaving the sea-weed in many respects resemble the lower orders of animal life, having, like the latter, the property of moving. They also approach the animal kingdom in their composition, their outer coating containing nitrogenous matter. Directly the zoospore becomes covered with that non-nitrogenous or cellular coating which is proper to all the ordinary cells of plants, it loses all resemblance to an animal organism and becomes a small plant. It may be thought from this that the cause of the difference in the vital processes of animals and plants is the different amount of nitrogenous substances they contain. The nitrogenous substances which occur in plants and animals appertain to a series of exceedingly complex and very changeable chemical compounds; their elementary composition alone shows this; besides nitrogen, they contain carbon, hydrogen, oxygen, and sulphur. Being distinguished by a very great instability under many conditions in which other compounds remain unchanged, these substances are fitted for those perpetual changes which form the first condition of vital activity. These complex and changeable nitrogenous substances of the organism are called _proteïd substances_. The white of eggs is a familiar example of such a substance. They are also contained in the flesh of animals, the curdy elements of milk, the glutinous matter of wheaten flour, or so-called gluten, which forms the chief component of macaroni, &c. Nitrogen occurs in the earth's crust, in compounds either forming the remains of plants and animals, or derived from the nitrogen of the atmosphere as a consequence of its combination with the other component parts of the air. It is not found in other forms in the earth's crust; so that nitrogen must be considered, in contradistinction to oxygen, as an element which is purely superficial, and does not extend to the depths of the earth.[1 bis] [1 bis] The reason why there are no other nitrogenous substances within the earth's mass beyond those which have come there with the remains of organisms, and from the air with rain-water, must be looked for in two circumstances. In the first place, in the instability of many nitrogenous compounds, which are liable to break up with the formation of gaseous nitrogen; and in the second place in the fact that the salts of nitric acid, forming the product of the action of air on many nitrogenous and especially organic compounds, are very soluble in water, and on penetrating into the depths of the earth (with water) give up their oxygen. The result of the changes of the nitrogenous organic substances which fall into the earth is without doubt frequently, if not invariably, the formation of gaseous nitrogen. Thus the gas evolved from coal always contains much nitrogen (together with marsh gas, carbonic anhydride, and other gases). _Nitrogen is liberated_ in a free state in the decomposition of the _nitrogenous organic substances_ entering into the composition of organisms--for instance, on their combustion. All organic substances burn when heated to redness with oxygen (or substances readily yielding it, such as oxide of copper); the oxygen combines with the carbon, sulphur, and hydrogen, and the nitrogen is evolved in a free state, because at a high temperature it does not form any stable compound, but remains uncombined. Carbonic anhydride and water are formed from the carbon and hydrogen respectively, and therefore to obtain pure nitrogen it is necessary to remove the carbonic anhydride from the gaseous products obtained. This may be done very easily by the action of alkalis--for instance, caustic soda. The amount of nitrogen in organic substances is determined by a method founded on this. It is also very easy to obtain _nitrogen from air_, because oxygen combines with many substances. Either phosphorus or metallic copper is usually employed for removing the oxygen from air, but, naturally, a number of other substances may also be used. If a small saucer on which a piece of phosphorus is laid be placed on a cork floating on water, and the phosphorus be lighted, and the whole covered with a glass bell jar, then the air under the jar will be deprived of its oxygen, and nitrogen only will remain, owing to which, on cooling, the water will rise to a certain extent in the bell jar. The same object (procuring nitrogen from air) is attained much more conveniently and perfectly by passing air through a red-hot tube containing copper filings. At a red heat, metallic copper combines with oxygen and gives a black powder of copper oxide. If the layer of copper be sufficiently long and the current of air slow, all the oxygen will be absorbed, and nitrogen alone will pass from the tube.[2] [2] Copper (best as turnings, which present a large surface) absorbs oxygen, forming CuO, at the ordinary temperature in the presence of solutions of acids, or, better still, in the presence of a solution of ammonia, when it forms a bluish-violet solution of oxide of copper in ammonia. Nitrogen is very easily procured by this method. A flask filled with copper turnings is closed with a cork furnished with a funnel and stopcock. A solution of ammonia is poured into the funnel, and caused to drop slowly upon the copper. If at the same time a current of air be slowly passed through the flask (from a gasholder), then all the oxygen will be absorbed from it and the nitrogen will pass from the flask. It should be washed with water to retain any ammonia that may be carried off with it. Nitrogen may also be procured from many of its _compounds with oxygen[3] and hydrogen_,[4] but the best fitted for this purpose is a saline mixture containing, on the one hand, a compound of nitrogen with oxygen, termed nitrous anhydride, N_{2}O_{3}, and on the other hand, ammonia, NH_{3}--that is, a compound of nitrogen with hydrogen. By heating such a mixture, the oxygen of the nitrous anhydride combines with the hydrogen of the ammonia, forming water, and gaseous nitrogen is evolved, 2NH_{3} + N_{2}O_{3} = 3H_{2}O + N_{4}. Nitrogen is procured by this method in the following manner:--A solution of caustic potash is saturated with nitrous anhydride, by which means potassium nitrite is formed. On the other hand, a solution of hydrochloric acid saturated with ammonia is prepared; a saline substance called sal-ammoniac, NH_{4}Cl, is thus formed in the solution. The two solutions thus prepared are mixed together and heated. Reaction takes place according to the equation KNO_{2} + NH_{4}Cl = KCl + 2H_{2}O + N_{2}. This reaction proceeds in virtue of the fact that potassium nitrite and ammonium chloride are salts which, on interchanging their metals, give potassium chloride and ammonium nitrite, NH_{4}NO_{2}, which breaks up into water and nitrogen. This reaction does not take place without the aid of heat, but it proceeds very easily at a moderate temperature. Of the resultant substances, the nitrogen only is gaseous. Pure nitrogen may be obtained by drying the resultant gas and passing it through a solution of sulphuric acid (to absorb a certain quantity of ammonia which is evolved in the reaction).[4 bis] [3] The oxygen compounds of nitrogen (for example, N_{2}O, NO, NO_{2}) are decomposed at a red heat by themselves, and under the action of red-hot copper, iron, sodium, &c., they give up their oxygen to the metals, leaving the nitrogen free. According to Meyer and Langer (1885), nitrous oxide, N_{2}O, decomposes below 900°, although not completely. [4] Chlorine and bromine (in excess), as well as bleaching powder (hypochlorites), take up the hydrogen from ammonia, NH_{3}, leaving nitrogen. Nitrogen is best procured from ammonia by the action of a solution of sodium hypobromite on solid sal-ammoniac. [4 bis] Lord Rayleigh in 1894, when determining the weight of a volume of carefully purified nitrogen by weighing it in one and the same globe, found that the gas obtained from air, by the action of incandescent copper (or iron or by removing the oxygen by ferrous oxide) was always 1/200 heavier than the nitrogen obtained from its compounds, for instance, from the oxide or suboxide of nitrogen, decomposed by incandescent pulverulent iron or from the ammonia salt of nitrous acid. For the nitrogen procured from air, he obtained, at 0° and 760·4 mm. pressure, a weight = 2·310 grms., while for the nitrogen obtained from its compounds, 2·299 grms. This difference of about 1/200 could not be explained by the nitrogen not having been well purified, or by inaccuracy of experiment, and was the means for the remarkable discovery of the presence of a heavy gas in air, which will be mentioned in Note 16 bis. Nitrogen is a gaseous substance which does not differ much in physical properties from air; its density, referred to hydrogen, is approximately equal to 14--that is, it is slightly lighter than air, its density referred to air being 0·972; one litre of nitrogen weighs 1·257 gram. Nitrogen mixed with oxygen, which is slightly heavier than air, forms air. It is a gas which, like oxygen and hydrogen, is liquefied with difficulty, and is but little soluble in water and other liquids. Its absolute boiling point[5] is about -140°; above this temperature it is not liquefiable by pressure, and at lower temperatures it remains a gas at a pressure of 50 atmospheres. Liquid nitrogen boils at -193°, so that it may be employed as a source of great cold. At about -203°, in vaporising under a decrease of pressure, nitrogen solidifies into a colourless snow-like mass. Nitrogen does not burn,[5 bis] does not support combustion, is not absorbed by any of the reagents used in gas analysis, at least at the ordinary temperature--in a word, it presents a whole series of negative chemical properties; this is expressed by saying that this element has no energy for combination. Although it is capable of forming compounds both with oxygen and hydrogen as well as with carbon, yet these compounds are only formed under particular circumstances, to which we will directly turn our attention. At a red heat nitrogen combines with boron, titanium, and silicon, barium, magnesium, &c., forming very stable nitrogenous compounds,[6] whose properties are entirely different from those of nitrogen with hydrogen, oxygen and carbon. However, the combination of nitrogen with carbon, although it does not take place directly between the elements at a red heat, yet proceeds with comparative ease by heating a mixture of charcoal with an alkaline carbonate, especially potassium carbonate or barium carbonate, to redness, carbo-nitrides or cyanides of the metals being formed; for instance, K_{2}CO_{3} + 4C + N_{2} = 2KCN + 3CO.[7] [5] See Chapter II. Note 29. [5 bis] See Note 11 bis. [6] The combination of boron with nitrogen is accompanied by the evolution of sufficient heat to raise the mass to redness; titanium combines so easily with nitrogen that it is difficult to obtain it free from that element; magnesium easily absorbs nitrogen at a red heat. It is a remarkable and instructive fact that these compounds of nitrogen are very stable and non-volatile. Carbon (C = 12) with nitrogen gives cyanogen, C_{2}N_{2}, which is gaseous and very unstable, and whose molecule is not large, whilst boron (B = 11) forms a nitrogenous compound which is solid, non-volatile, and very stable. Its composition, BN, is similar to that of cyanogen, but its molecular weight, B_{n}N_{n}, is probably greater. Its composition, like that of N_{2}Mg_{3}, NNa_{3}, N_{2}Hg_{3} and of many of the metallic nitrides, corresponds to ammonia with the substitution of all its hydrogen by a metal. In my opinion, a detailed study of the transformations of the nitrides now known, should lead to the discovery of many facts in the history of nitrogen. [7] This reaction, so far as is known, does not proceed beyond a certain limit, probably because cyanogen, CN, itself breaks up into carbon and nitrogen. Nitrogen is found with oxygen in the air, but they do not readily combine. Cavendish, however, in the last century, showed that _nitrogen combines with oxygen under the influence of a series of electric sparks_. Electric sparks in passing through a moist[8] mixture of nitrogen and oxygen cause these elements to combine, forming reddish-brown fumes of oxides of nitrogen,[9] which form nitric acid,[10] NHO_{3}. The presence of the latter is easily recognised, not only from its reddening litmus paper, but also from its acting as a powerful oxidiser even of mercury. Conditions similar to these occur in nature, during a thunderstorm or in other electrical discharges which take place in the atmosphere; whence it may be taken for granted that air and rain-water always contain traces of nitric and nitrous acids.[11] Besides which Crookes (1892) showed that under certain circumstances and when electricity of high potential[11 bis] passes through the air, the combination of nitrogen with oxygen is accompanied by the formation of a true flame. This was also observed previously (1880) during the passage of electrical discharges through the air. [8] Frémy and Becquerel took dry air, and observed the formation of brown vapours of oxides of nitrogen on the passage of sparks. [9] If a mixture of one volume of nitrogen and fourteen volumes of hydrogen be burnt, then water and a considerable quantity of nitric acid are formed. It may be partly due to this that a certain quantity of nitric acid is produced in the slow oxidation of nitrogenous substances in an excess of air. This is especially facilitated by the presence of an alkali with which the nitric acid formed can combine. If a galvanic current be passed through water containing the nitrogen and oxygen of the air in solution, then the hydrogen and oxygen set free combine with the nitrogen, forming ammonia and nitric acid. When copper is oxidised at the expense of the air at the ordinary temperature in the presence of ammonia, oxygen is absorbed, not only for combination with the copper, but also for the formation of nitric acid. The combination of nitrogen with oxygen, even, for example, by the action of electric sparks, is not accompanied by an explosion or rapid combination, as in the action of a spark on a mixture of oxygen and hydrogen. This is explained by the fact that heat is not evolved in the combination of nitrogen with oxygen, but is absorbed--an expenditure of energy is required, there is no evolution of energy. In fact, there will not be the transmission of heat from particle to particle which occurs in the explosion of detonating gas. Each spark will aid the formation of a certain quantity of the compound of oxygen and nitrogen, but will not excite the same in the neighbouring particles. In other words, the combination of hydrogen with oxygen is an exothermal reaction, and the combination of nitrogen with oxygen an endothermal reaction. A condition particularly favourable for the oxidation of nitrogen is the explosion of detonating gas and air if the former be _in excess_. If a mixture of two volumes of detonating gas and one volume of air be exploded, then one-tenth of the air is converted into nitric acid, and consequently after the explosion has taken place there remain only nine-tenths of the volume of air originally taken. If a large proportion of air be taken--for instance, four volumes of air to two volumes of detonating gas--then the temperature of the explosion is lowered, the volume of air taken remains unchanged, and no nitric acid is formed. This gives a rule to be observed in making use of the eudiometer--namely that to weaken the force of the explosion not less than an equal volume of air should be added to the explosive mixture. On the other hand a large excess must not be taken as no explosion would then ensue (_see_ Chapter III. Note 34). Probably in the future means will be found for obtaining compounds of nitrogen on a large industrial scale by the aid of electric discharges, and by making use of the inexhaustible mass of nitrogen in the atmosphere. [10] In reality nitric oxide, NO, is first formed, but with oxygen and water it gives (brown fumes) nitrous anhydride, which, as we shall afterwards learn, in the presence of water and oxygen gives nitric acid. [11] The nitric acid contained in the soil, river water (Chapter I., Note 2), wells, &c., proceeds (like carbonic anhydride) from the oxidation of organic compounds which have fallen into water, soil, &c. [11 bis] Crookes employed a current of 15 ampères and 65 volts, and passed it through an induction coil with 330 vibrations per second, and obtained a flame between the poles placed at a distance of 46 mm. which after the appearance of the arc and flame could be increased to 200 mm. A platinum wire fused in the flame. Further observations showed that under the influence of electrical discharges,[12] silent as well as with sparks, nitrogen is able to enter into many reactions with hydrogen and with many hydrocarbons; although these reactions cannot be effected by exposure to a red heat. Thus, for instance, a series of electric sparks passed through a mixture of nitrogen and hydrogen causes them to combine and _form ammonia_[13] or nitrogen hydride, NH_{3}, composed of one volume of nitrogen and three volumes of hydrogen. This combination is limited to the formation of 6 per cent. of ammonia, because ammonia is decomposed, although not entirely (94/100) by electric sparks. This signifies that under the influence of an electrical discharge the reaction NH_{3} = N + 3H is reversible, consequently it is a dissociation, and in it a state of equilibrium is arrived at. The equilibrium may be destroyed by the addition of gaseous hydrochloric acid, HCl, because with ammonia it forms a solid saline compound, sal-ammoniac, NH_{4}Cl, which (being formed from a gaseous mixture of 3H, N, and HCl) fixes the ammonia. The remaining mass of nitrogen and hydrogen, under the action of the sparks, again forms ammonia, and in this manner _solid sal-ammoniac is obtained to the end by the action of a series of electric sparks on a mixture of gaseous_ N, H_{3}, _and_ HCl.[14] Berthelot (1876) showed that under the action of a silent discharge many non-nitrogenous organic substances (benzene, C_{6}H_{6}, cellulose in the form of paper, resin, glucose, C_{6}H_{10}O_{5}, and others) absorb nitrogen and form complex nitrogenous compounds, which are capable, like albuminous substances, of evolving their nitrogen as ammonia when heated with alkalis.[15] [12] This property of nitrogen, which under normal conditions is inactive, leads to the idea that under the influence of an electric discharge gaseous nitrogen changes in its properties; if not permanently like oxygen (electrolysed oxygen or ozone does not react on nitrogen, according to Berthelot), it may be temporarily at the moment of the action of the discharge, just as some substances under the action of heat are permanently affected (that is, when once changed remain so--for instance, white phosphorus passes into red, &c.), whilst others are only temporarily altered (the dissociation of S_{6} into S_{2} or of sal-ammoniac into ammonia and hydrochloric acid). Such a proposition is favoured by the fact that nitrogen gives two kinds of spectra, with which we shall afterwards become acquainted. It may be that the molecules N_{2} then give less complex molecules, N containing one atom, or form a complex molecule N_{3}, like oxygen in passing into ozone. Probably under a silent discharge the molecules of oxygen, O_{2}, are partly decomposed and the individual atoms O combine with O_{2}, forming ozone, O_{3}. [13] This reaction, discovered by Chabrié and investigated by Thénard, was only rightly understood when Deville applied the principles of dissociation to it. [14] The action of nitrogen on acetylene (Berthelot) resembles this reaction. A mixture of these gases under the influence of a silent discharge gives hydrocyanic acid, C_{2}H_{2} + N_{2} = 2CNH. This reaction cannot proceed beyond a certain limit because it is reversible. [15] Berthelot successfully employed electricity of even feeble potential in these experiments, which fact led him to think that in nature, where the action of electricity takes place very frequently, a part of the complex nitrogenous substances may proceed from the gaseous nitrogen of the air by this method. As the nitrogenous substances of organisms play a very important part in them (organic life cannot exist without them), and as the nitrogenous substances introduced into the soil are capable of invigorating its crops (of course in the presence of the other nourishing principles required by plants), the question of the means of converting the atmospheric nitrogen into the nitrogenous compounds of the soil, or into _assimilable nitrogen_ capable of being absorbed by plants and of forming complex (albuminous) substances in them, is one of great theoretical and practical interest. The artificial (technical) conversion of the atmospheric nitrogen into nitrogenous compounds, notwithstanding repeated attempts, cannot yet be considered as fulfilled in a practical remunerative manner although its possibility is already evident. Electricity will probably aid in solving this very important practical problem. When the theoretical side of the question is further advanced, then without doubt an advantageous means will be found for the manufacture of nitrogenous substances from the nitrogen of the air; and this is needed, before all, for the agriculturist, to whom nitrogenous fertilisers form an expensive item, and are more important than all other manures. One thousand tons of farmyard manure do not generally contain more than four tons of nitrogen in the form of complex nitrogenous substances, and this amount of nitrogen is contained in twenty tons of ammonium sulphate, therefore the effect of a mass of farmyard manure in respect to the introduction of nitrogen may be produced by small quantities of artificial nitrogenous fertilisers (_see_ Note 15 bis). By such indirect methods does the gaseous nitrogen of the atmosphere yield its primary compounds, in which form it enters into plants, and is elaborated in them into complex albuminous substances.[15 bis] But, starting from a given compound of nitrogen with hydrogen or oxygen, we may, without the aid of organisms, obtain, as will afterwards be partially indicated, most diverse and complex nitrogenous substances, which cannot by any means be formed directly from gaseous nitrogen. In this we see an example not only of the difference between an element in the free state and an intrinsic element, but also of those circuitous or _indirect methods_ by which substances are formed in nature. The discovery, prognostication, and, in general, the study of such indirect methods of the preparation and formation of substances forms one of the existing problems of chemistry. From the fact that A does not act at all on B, it must not be concluded that a compound AB is not to be formed. The substances A and B contain atoms which occur in AB, but their state or the nature of their motion may not be at all that which is required for the formation of AB, and in this substance the chemical state of the elements may be as different as the state of the atoms of oxygen in ozone and in water. Thus free nitrogen is inactive; but in its compounds it very easily enters into changes and is distinguished by great activity. An acquaintance with the compounds of nitrogen confirms this. But, before entering on this subject, let us consider air as a mass containing free nitrogen. [15 bis] Although the numerous, and as far as possible accurate and varied researches made in the physiology of plants have proved that the higher forms of plants are not capable of directly absorbing the nitrogen of the atmosphere and converting it into complex albuminous substances, still it has been long and repeatedly observed that the amount of nitrogenous substances in the soil is increased by the cultivation of plants of the bean (leguminous) family such as pea, acacia, &c. A closer study of these plants has shown that this is connected with the formation of peculiar nodular swellings in their roots caused by the growth of peculiar micro-organisms (bacteria) which cohabit the soil with the roots, and are capable of absorbing nitrogen from the air, _i.e._ of converting it into assimilated nitrogen. This branch of plant physiology, which forms another proof of the important part played by micro-organisms in nature, cannot be discussed in this work, but it should be mentioned, since it is of great theoretical and practical interest, and, moreover, phenomena of this kind, which have recently been discovered, promise to explain, to some extent at least, certain of the complex problems concerning the development of life on the earth. Judging from what has been already stated, it will be evident that _atmospheric air_[16] contains a mixture of several gases and vapours. Some of them are met with in it in nearly constant proportions, whilst others, on the contrary, are very variable in their amount. The chief component parts of air, placed in the order of their relative amounts, are the following: nitrogen,[16 bis] oxygen, aqueous vapour, carbonic anhydride, nitric acid, salts of ammonia, oxides of nitrogen, and also ozone, hydrogen peroxide, and complex organic nitrogenous substances. Besides these, air generally contains water, as spray, drops, and snow, and particles of solids, perhaps of cosmic origin in certain instances, but in the majority of cases proceeding from the mechanical translation of solid particles from one locality to another by the wind. These small solid and liquid particles (having a large surface in proportion to their weight) are suspended in air as solid matter is suspended in turbid water; they often settle on the surface of the earth, but the air is never entirely free from them because they are never in a state of complete rest. Then, air not unfrequently contains incidental traces of various substances as everyone knows by experience. These incidental substances sometimes belong to the order of those which act injuriously, the germs of lower organisms--for instance of moulds--and the class of carriers of infectious diseases. [16] Under the name of atmospheric air the chemist and physicist understand ordinary air containing nitrogen and oxygen only, notwithstanding that the other component parts of air have a very important influence on the living matter of the earth's surface. That air is so represented in science is based on the fact that only the two components above-named are met with in air in a constant quantity, whilst the others are variable. The solid impurities may be separated from air required for chemical or physical research by simple filtration through a long layer of cotton-wool placed in a tube. Organic impurities are removed by passing the air through a solution of potassium permanganate. The carbonic anhydride contained in air is absorbed by alkalis--best of all, soda-lime, which in a dry state in porous lumps absorbs it with exceeding rapidity and completeness. Aqueous vapour is removed by passing the air over calcium chloride, strong sulphuric acid, or phosphoric anhydride. Air thus purified is accepted as containing only nitrogen and oxygen, although in reality it still contains a certain quantity of hydrogen and hydrocarbons, from which it may be purified by passing over copper oxide heated to redness. The copper oxide then oxidises the hydrogen and hydrocarbons--it burns them, forming water and carbonic anhydride, which may be removed as above described. When it is said that in the determination of the density of gases the weight of air is taken as unity, it is understood to be such air, containing only nitrogen and oxygen. [16 bis] Thanks to the remarkable discovery made in the summer of 1894 by Lord Rayleigh and Prof. Ramsay, the well-known component elements of air must now he supplemented by 1 p.c. (by volume) of a heavy gas (density about 19, H = 1), inactive like nitrogen, which was discovered in the researches made by Lord Rayleigh on the density of nitrogen as mentioned in note 4 bis. Up to the present time this gas has been always determined together with nitrogen, because it combines with neither the hydrogen in the eudiometer nor with the copper in the gravimetric method of determining the composition of air, and therefore has always remained with the nitrogen. It has been possible to separate it from nitrogen since magnesium absorbs nitrogen at a red heat, while this gas remains unabsorbed, and was found to have a density nearly one and a half time greater than that of nitrogen (is it not a polymer of nitrogen, N_{3}?). It is now known also that this gas gives a luminous spectrum, which contains the bright blue line observed in the spectrum of nitrogen. Owing to the fact that it is an exceedingly inert substance, even more so than nitrogen, it has been termed Argon. Further reference will be made to it in the Appendix. In the air of the various countries of the earth, at different longitudes and at different altitudes above its surface, on the ocean or on the dry land--in a word, in the air of most diverse localities of the earth--the oxygen and nitrogen are found everywhere to be in a constant ratio. This is, moreover, self-evident from the fact that the air constantly diffuses (intermixes by virtue of the internal motion of the gaseous particles) and is also put into motion and intermixed by the wind, by which processes it is equalised in its composition over the entire surface of the earth. In those localities where the air is subject to change, and is in a more or less enclosed space, or, at any rate, in an unventilated space, it may alter very considerably in its composition. For this reason the air in dwellings, cellars, and wells, in which there are substances absorbing oxygen, contains less of this gas, whilst the air on the surface of standing water, which abounds in the lower orders of plant life evolving oxygen, contains an excess of this gas.[17] The constant composition of air over the whole surface of the earth has been proved by a number of most careful researches.[18] [17] As a further proof of the fact that certain circumstances may change the composition of air, it will be enough to point out that the air contained in the cavities of glaciers contains only up to 10 p.c. of oxygen. This depends on the fact that at low temperatures oxygen is much more soluble in snow-water and snow than nitrogen. When shaken up with water the composition of air should change, because the water dissolves unequal quantities of oxygen and nitrogen. We have already seen (Chapter I.) that the air boiled off from water saturated at about 0° contains about thirty-five volumes of oxygen and sixty-five volumes of nitrogen, and we have considered the reason of this. [18] The analysis of air by weight conducted by Dumas and Boussingault in Paris, which they repeated many times between April 27 and September 22, 1841, under various conditions of weather, showed that the amount by weight of oxygen only varies between 22·89 p.c. and 23·08 p.c., the average amount being 23·07 p.c. Brunner, at Bern in Switzerland, and Bravais, at Faulhorn in the Bernese Alps, at a height of two kilometres above the level of the sea, Marignac at Geneva, Lewy at Copenhagen, and Stas at Brussels, have analysed the air by the same methods, and found that its composition does not exceed the limits determined for Paris. The most recent determinations (with an accuracy of ±0·05 p.c.) confirm the conclusion that the composition of the atmosphere is constant. As there are some grounds (which will be mentioned shortly) for considering that the composition of the air at great altitudes is slightly different from that at attainable heights--namely, that it is richer in the lighter nitrogen--several fragmentary observations made at Munich (Jolly, 1880) gave reason for thinking that in the upward currents (that is in the region of minimum barometric pressure or at the centres of meteorological cyclones) the air is richer in oxygen than in the descending currents of air (in the regions of anticyclones or of barometric maxima); but more carefully conducted observations showed this supposition to be incorrect. Improved methods for the analysis of air have shown that certain slight variations in its composition do actually occur, but in the first place they depend on incidental local influences (on the passage of the air over mountains and large surfaces of water, regions of forest and herbage, and the like), and in the second place are limited to quantities which are scarcely distinguishable from possible errors in the analyses. The researches made by Kreisler in Germany (1885) are particularly convincing. The considerations which lead to the supposition that the atmosphere at great altitudes contains less oxygen than at the surface of the earth are based on the law of partial pressures (Chapter I.) According to this law, the equilibrium of the oxygen in the strata of the atmosphere is not dependent on the equilibrium of the nitrogen, and the variation in the densities of both gases with the height is determined by the pressure of each gas separately. Details of the calculations and considerations here involved are contained in my work _On Barometric Levellings_, 1876, p. 48. On the basis of the law of partial pressure and of hypsometrical formulæ, expressing the laws of the variation of pressures at different altitudes, the conclusion may be deduced that at the upper strata of the atmosphere the proportion of the nitrogen with respect to the oxygen increases, but the increase will not exceed a fraction per cent., even at altitudes of four and a half to six miles, the greatest height within the reach of men either by climbing mountains or by means of balloons. This conclusion is confirmed by the analyses of air collected by Welch in England during his aëronautic ascents. _The analysis of air_ is effected by converting the oxygen into a non-gaseous compound, so as to separate it from the air. The original volume of the air is first measured, and then the volume of the remaining nitrogen. The quantity of oxygen is calculated either from the difference between these volumes or by the weight of the oxygen compound formed. All the volumetric measurements have to be corrected for pressure, temperature, and moisture (Chapters I. and II.) The medium employed for converting the oxygen into a non-gaseous substance should enable it to be taken up from the nitrogen to the very end without evolving any gaseous substance. So, for instance,[19] a mixture of pyrogallol, C_{6}H_{6}O_{3}, with a solution of a caustic alkali absorbs oxygen with great ease at the ordinary temperature (the solution turns black), but it is unsuited for accurate analysis because it requires an aqueous solution of an alkali, and it alters the composition of the air by acting on it as a solvent.[20] However, for approximate determinations this simple method gives results which are entirely satisfactory. [19] The complete absorption of the oxygen may be attained by introducing moist phosphorus into a definite volume of air; the occurrence of this is recognised by the fact of the phosphorus becoming non-luminous in the dark. The amount of oxygen may be determined by measuring the volume of nitrogen remaining. This method however cannot give accurate results, owing to a portion of the air being dissolved in the water, to the combination of some of the nitrogen with oxygen and to the necessity of introducing and withdrawing the phosphorus, which cannot be accomplished without introducing bubbles of air. [20] For rapid and approximate analyses (technical and hygienic), such a mixture is very suitable for determining the amount of oxygen in mixtures of gases from which the substances absorbed by alkalis have first been removed. According to certain observers, this mixture evolves a certain (small) quantity of carbonic oxide after absorbing oxygen. The determinations in a eudiometer (Chapter III.) give more exact results, if all the necessary corrections for changes of pressure, temperature, and moisture be taken into account. This determination is carried out essentially as follows:--A certain amount of air is introduced into the eudiometer, and its volume is determined. About an equal volume of dry hydrogen is then passed into the eudiometer, and the volume again determined. The mixture is then exploded, in the way described for the determination of the composition of water. The remaining volume of the gaseous mixture is again measured; it will be less than the second of the previously measured volumes. Out of three volumes which have disappeared, one belonged to the oxygen and two to the hydrogen, consequently one-third of the loss of volume indicates the amount of oxygen contained in the air.[21] [21] Details of eudiometrical analysis must, as was pointed out in Chap. III., Note 32, be looked for in works on analytical chemistry. The same remark applies to the other analytical methods mentioned in this work. They are only described for the purpose of showing the diversity of the methods of chemical research. The most complete method for the analysis of air, and one which is accompanied by the least amount of error, consists in the direct weighing, as far as is possible, of the oxygen, nitrogen, water, and carbonic anhydride contained in it. For this purpose the air is first passed through an apparatus for retaining the moisture and carbonic anhydride (which will be considered presently), and is then led through a tube which contains shavings of metallic copper and has been previously weighed. A long layer of such copper heated to redness absorbs all the oxygen from the air, and leaves pure nitrogen, whose weight must be determined. This is done by collecting it in a weighed and exhausted globe, while the amount by weight of oxygen is shown by the increase in weight of the tube with the copper after the experiment. [Illustration: FIG. 38.--Dumas and Boussingault's apparatus for the analysis of air by weight. The globe B contains 10-15 litres. The air is first pumped out of it, and it is weighed empty. The tube T connected with it is filled with copper, and is weighed empty of air. It is heated in a charcoal furnace. When the copper has become red-hot, the stopcock _r_ (near R) is slightly opened, and the air passes through the vessels L, containing a solution of potash, _f_, containing solutions and pieces of caustic potash, which remove the carbonic anhydride from the air, and then through _o_ and _t_, containing sulphuric acid (which has been previously boiled to expel dissolved air) and pumice-stone, which removes the moisture from the air. The pure air then gives up its oxygen to the copper in T. When the air passes into T the stopcock R of the globe B is opened, and it becomes filled with nitrogen. When the air ceases to flow in, the stopcocks are closed, and the globe B and tube T weighed. The nitrogen is then pumped out of the tube and it is weighed again. The increase in weight of the tube shows the amount of oxygen, and the difference of the second and third weighings of the tube, with the increase in weight of the globe, gives the weight of the nitrogen.] Air free from moisture and carbonic anhydride[22] contains 20·95 to 20·88[23] parts by volume of oxygen; the mean amount of oxygen will therefore be 20·92 ± 0·05 per cent. Taking the density of air = 1 and of oxygen = 1·105 and nitrogen 0·972 the composition of air by weight will be 23·12 per cent. of oxygen and 76·88 per cent. of nitrogen.[24] [22] Air free from carbonic anhydride indicates after explosion the presence of a small quantity of carbonic anhydride, as De Saussure remarked, and air free from moisture, after being passed over red-hot copper oxide, appears invariably to contain a small quantity of water, as Boussingault has observed. These observations lead to the assumption that air always contains a certain quantity of gaseous hydrocarbons, like marsh gas, which, as we shall afterwards learn, is evolved from the earth, marshes, &c. Its amount, however, does not exceed a few hundredths per cent. [23] The analyses of air are accompanied by errors, and there are variations of composition attaining hundredths per cent.; the average normal composition of air is therefore only correct to the first decimal place. [24] These figures express the mean composition of air from an average of the most accurate determinations; they are accurate within ±0·05 p.c. [Illustration: FIG. 39.--Apparatus for the absorption and washing of gases, known as Liebig's bulbs. The gas enters _m_, presses on the absorptive liquid, and passes from m into _b_, _c_, _d_, and _e_ consecutively, and escapes through _f_.] [Illustration: FIG. 40.--Geisler's potash bulbs. The gas enters at _a_, and passes through a solution of potash in the lower bulbs, where the carbonic anhydride is absorbed, and the gas escapes from _b_. The lower bulbs are arranged in a triangle, so that the apparatus can stand without support.] The possibility of the composition of air being altered by the mere action of a solvent very clearly shows that the component parts of air are in a state of mixture, in which any gases may occur; they do not in this case form a definite compound, although the composition of the atmosphere does appear constant under ordinary conditions. The fact that its composition varies under different conditions confirms the truth of this conclusion, and therefore the constancy of the composition of air must not be considered as in any way dependent on the nature of the gases entering into its composition, but only as proceeding from cosmic phenomena co-operating towards this constancy. It must be admitted, therefore, that the processes evolving oxygen, and chiefly the processes of the respiration of plants, are of equal force with those processes which absorb oxygen over the entire surface of the earth.[25] [25] In Chapter III., Note 4, an approximate calculation is made for the determination of the balance of oxygen in the entire atmosphere; it may therefore he supposed that the composition of air will vary from time to time, the relation between vegetation and the oxygen absorbing processes changes; but as the atmosphere of the earth can hardly have a definite limit and we have already seen (Chapter IV., Note 33) that there are observations confirming this, it follows that our atmosphere should vary in its component parts with the entire heavenly space, and therefore it must he supposed that any variation in the composition by weight of the air can only take place exceedingly slowly, and in a manner imperceptible by experiment. [Illustration: FIG. 41.--Tube for the absorption of carbonic acid. A plug of cotton wool is placed in the bulb to prevent the powder of soda-lime being carried off by the gas. The tube contains soda-lime and chloride of calcium.] Air always contains more or less moisture[26] and _carbonic anhydride_ produced by the respiration of animals and the combustion of carbon and carboniferous compounds. The latter shows the properties of an acid anhydride. In order to determine the amount of carbonic anhydride in air, substances are employed which absorb it--namely, alkalis either in solution or solid. A solution of caustic potash, KHO, is poured into light glass vessels, through which the air is passed, and the amount of carbonic anhydride is determined by the increase in weight of the vessel. But it is best to take a solid porous alkaline mass such as soda-lime.[27] With a slow current of air a layer of soda-lime 20 cm. in length is sufficient to completely deprive 1 cubic metre of air of the carbonic anhydride it contains. A series of tubes containing calcium chloride for absorbing the moisture[28] is placed before the apparatus for the absorption of the carbonic anhydride, and a measured mass of air is passed through the whole apparatus by means of an aspirator. In this manner the determination of the moisture is combined with the absorption of the carbonic anhydride. The arrangement shown in fig. 38 is such a combination. [26] The amount of moisture contained in the air is considered in greater detail in the study of physics and meteorology and the subject has been mentioned above, in Chapter I., Note 1, where the methods of absorbing moisture from gases were pointed out. [27] Soda-lime is prepared in the following manner:--Unslaked lime is finely powdered and mixed with a slightly warmed and very strong solution of caustic soda. The mixing should be done in an iron dish, and the materials should be well stirred together until the lime begins to slake. When the mass becomes hot, it boils, swells up, and solidifies, forming a porous mass very rich in alkali and capable of rapidly absorbing carbonic anhydride. A lump of caustic soda or potash presents a much smaller surface for absorption and therefore acts much less rapidly. It is necessary to place an apparatus for absorbing water after the apparatus for absorbing the carbonic anhydride, because the alkali in absorbing the latter gives off water. [28] It is evident that the calcium chloride employed for absorbing the water should be free from lime or other alkalis in order that it may not retain carbonic anhydride. Such calcium chloride may be prepared in the following manner: A perfectly neutral solution of calcium chloride is prepared from lime and hydrochloric acid; it is then carefully evaporated first on a water-bath and then on a sand-bath. When the solution attains a certain strength a scum is formed, which solidifies at the surface. This scum is collected, and will be found to be free from caustic alkalis. It is necessary in any case to test it before use, as otherwise a large error may be introduced into the results, owing to the presence of free alkali (lime). It is best to pass carbonic anhydride through the tube containing the calcium chloride for some time before the experiment, in order to saturate any free alkali that may remain from the decomposition of a portion of the calcium chloride by water, CaCl_{2} + 2H_{2}O = CaOH_{2}O + 2HCl. The amount of carbonic anhydride[29] in free air is incomparably more constant than the amount of moisture. The average amount in 100 volumes of dry air is approximately 0·03 volume--that is, 10,000 volumes of air contain about three volumes of carbonic anhydride, most frequently about 2·95 volumes. As the specific gravity of carbonic anhydride referred to air = 1·52, it follows that 100 parts by weight of air contain 0·045 part by weight of carbonic anhydride. This quantity varies according to the time of year (more in winter), the altitude above the level of the sea (less at high altitudes), the proximity to forests and fields (less) or cities (greater), &c. But the variation is small and rarely exceeds the limits of 2-1/2 to 4 ten-thousandths by volume.[30] As there are many natural local influences which either increase the amount of carbonic anhydride in the air (respiration, combustion, decomposition, volcanic eruptions, &c.), or diminish it (absorption by plants and water), the reason of the great constancy in the amount of this gas in the air must be looked for, in the first place, in the fact that the wind mixes the air of various localities together, and, in the second place, in the fact that the waters of the ocean, holding carbonic acid in solution,[31] form an immense reservoir for regulating the amount of this gas in the atmosphere. Immediately the partial pressure of the carbonic anhydride in the air decreases, the water evolves it, and when the partial pressure increases, it absorbs it, and thus nature supplies the conditions for a natural state of moving equilibrium in this as in so many other instances.[32] [29] Recourse is had to special methods when the determination only takes note of the carbonic anhydride of the air. For instance, it is absorbed by an alkali which does not contain carbonates (by a solution of baryta or caustic soda mixed with baryta), and then the carbonic anhydride is expelled by an excess of an acid, and its amount determined by the volume given off. A rapid method of determining CO_{2} (for hygienic purposes) is given by the fall of tension produced by the introduction of an alkali (the air having been either brought to dryness or saturated with moisture). Dr. Schidloffsky's apparatus is based upon this principle. The question as to the amount of carbonic anhydride present in the air has been submitted to many voluminous and exact researches, especially those of Reiset, Schloesing, Müntz, and Aubin, who showed that the amount is not subject to such variations as at first announced on the basis of incomplete and insufficiently accurate determinations. [30] It is a different case in enclosed spaces, in dwellings, cellars, wells, caves, and mines, where the renewal of air is impeded. Under these circumstances large quantities of carbonic anhydride may accumulate. In cities, where there are many conditions for the evolution of carbonic anhydride (respiration, decomposition, combustion), its amount is greater than in free air, yet even in still weather the difference does not often exceed one ten-thousandth (that is, rarely attains 4 instead of 2·9 vols. in 10000 vols. of air). [31] In the sea as well as in fresh water, carbonic acid occurs in two forms, directly dissolved in the water, and combined with lime as calcium bicarbonate (hard waters sometimes contain very much carbonic acid in this form). The tension of the carbonic anhydride in the first form varies with the temperature, and its amount with the partial pressure, and that in the form of acid salts is under the same conditions, for direct experiments have shown a similar dependence in this case, although the quantitative relations are different in the two cases. [32] In studying the phenomena of nature the conclusion is arrived at that the universally reigning state of mobile equilibrium forms the chief reason for that harmonious order which impresses all observers. It not unfrequently happens that we do not see the causes regulating the order and harmony; in the particular instance of carbonic anhydride, it is a striking circumstance that in the first instance a search was made for an harmonious and strict uniformity, and in incidental (insufficiently accurate and fragmentary) observations conditions were even found for concluding it to be absent. When, later, the rule of this uniformity was confirmed, then the causes regulating such order were also discovered. The researches of Schloesing were of this character. Deville's idea of the dissociation of the acid carbonates of sea-water is suggested in them. In many other cases also, a correct interpretation can only follow from a detailed investigation. Besides nitrogen, oxygen, moisture, and carbonic acid, all the other substances occurring in air are found in infinitesimally small quantities by weight, and therefore the _weight of a cubic measure of air_ depends, to a sensible degree, on the above-named components alone. We have already mentioned that at 0° and 760 mm. pressure the weight of a cubic litre of air is 1·293 gram. This weight varies with the acceleration of gravity, _g_, so that if _g_ be expressed in metres the weight of a litre of air, _e_ = _g_ × 0·131844 gram. For St. Petersburg _g_ is about 9·8188, and therefore _e_ is about 1·2946,[33] the air being understood to be dry and free from carbonic anhydride. Taking the amount of the latter as 0·03 per 100 volumes, we obtain a greater weight; for example, for St. Petersburg _e_ = 1·2948 instead of 1·2946 gram. The weight of one litre of moist air in which the tension[34] of the aqueous vapour (partial pressure) = _f_ mm., at a pressure (total) of air of H millimetres, at a temperature _t_, will be (_i.e._, if at 0° and 760 mm. the weight of dry air = _e_) equal to _e_/(1 + 0·00367_t_) × (H - 0·38_f_)/760. For instance, if H = 730 mm., _t_ = 20°, and _f_ = 10 mm. (the moisture is then slightly below 60 p.c.), the weight of a litre of air at St. Petersburg = 1·1527 gram.[35] [33] The difference of the weight of a litre of dry air (free from carbonic anhydride) at 0° and 760 mm., at different longitudes and altitudes, depends on the fact that the force of gravity varies under these conditions, and with it the pressure of the barometrical column also varies. This is treated in detail in my works _On the Elasticity of Gases_ and _On Barometric Levellings_, and 'The Publications of the Weights and Measures Department' (_Journal of the Russian Physico-Chemical Society_, 1894). In reality the weight is not measured in absolute units of weight (in pressure--refer to works on mechanics and physics), but in relative units (grams, scale weights) whose mass is invariable, and therefore the variation of the weight of the weights itself with the change of gravity must not be here taken into account, for we are here dealing with weights proportional to masses, since with a change of locality the weight of the weights varies as the weight of a given volume of air does. In other words: the mass of a substance always remains constant, but the pressure produced by it varies with the acceleration of gravity: the gram, pound, and other units of weight are really units of mass. [34] The tension of the aqueous vapour in the air is determined by hygrometers and other similar methods. It may also be determined by analysis (_see_ Chapter I., Note 1). [35] For rapid calculation the weight of a litre of air (in a room) in St. Petersburg, may under these conditions (H, _t_, and _f_) be obtained by the formula _e_ = 1·20671 + 0·0016 [H_{1}-755 + 2·6(18°-_t_°)] where H_{1} = H-0·38_f_. In determining the weight of small and heavy objects (crucibles, &c. in analysis, and in determining the specific gravities of liquids, &c.) _a correction may be introduced for the loss of weight_ in the air of the room, by taking the weight of a litre of air displaced as 1·2 gram, and consequently 0·0012 gram for every cubic centimetre. But if gases or, in general, large vessels are weighed, and the weighings require to be accurate, it is necessary to take into account all the data for the determination of the density of the air (_t_, H, and _f_), because sensitive balances can determine the possible variations of the weight of air, as in the case of a litre the weight of air varies in centigrams, even at a constant temperature, with variations of H and _f_. Some time ago (1859) I proposed the following method and applied it for this purpose. A large light and closed vessel is taken, and its volume and weight in a vacuum are accurately determined, and verified from time to time. On weighing it we obtain the weight in air of a given density, and by subtracting this weight from its absolute weight and dividing by its volume we obtain the density of the air. The presence of ammonia, a compound of nitrogen and hydrogen, in the air, is indicated by the fact that all acids exposed to the air absorb ammonia from it after a time. De Saussure observed that aluminium sulphate is converted by air into a double sulphate of ammonium and aluminium, or the so-called ammonia alum. Quantitative determinations have shown that the amount of ammonia[36] contained in air varies at different periods. However, it may be accepted that 100 cubic metres of air do not contain less than 1 or more than 5 milligrams of ammonia. It is remarkable that mountain air contains more ammonia than the air of valleys. The air in those places where animal substances undergoing change are accumulated, and especially that of stables, generally contains a much greater quantity of this gas. This is the reason of the peculiar pungent smell noticed in such places. Moreover ammonia, as we shall learn in the following chapter, combines with acids, and should therefore be found in air in the form of such combinations, since air contains carbonic and nitric acids. [36] Schloesing studied the equilibrium of the ammonia of the atmosphere and of the rivers, seas, &c., and showed that the amount of the gas is interchangeable between them. The ratio between the amount of ammonia in a cubic metre of air and a litre of water at 0° = 0·004, at 10° = 0·010, at 25° = 0·040 to 1, and therefore in nature there is a state of equilibrium in the amount of ammonia in the atmosphere and waters. The presence of nitric acid in air is proved without doubt by the fact that rain-water contains an appreciable amount of it. Further (as already mentioned in Chapter IV.), air contains ozone and hydrogen peroxide and nitrous acid (and its ammonia salt), _i.e._ substances having a direct oxidising action (for instance, upon iodized starch-paper), but they are present in very small quantities.[37] [37] Whilst formed in the air these oxidising substances (N_{2}O_{3}, ozone and hydrogen peroxide) at the same time rapidly disappear from it by oxidising those substances which are capable of being oxidised. Owing to this instability their amounts vary considerably, and, as would be expected, they are met with to an appreciable amount in pure air, whilst their amount decreases to zero in the air of cities, and especially in dwellings where there is a maximum of substances capable of oxidisation and a minimum of conditions for the formation of such bodies. There is a causal connection between the amount of these substances present in the air and its purity--that is, the amount of foreign residues of organic origin liable to oxidation present in the air. Where there is much of such residues their amount must be small. When they are present the amount of organic substances must be small, as otherwise they would be destroyed. For this reason efforts have been made to apply ozone for purifying the air by evolving it by artificial means in the atmosphere; for instance, by passing a series of electrical sparks through the ventilating pipes conveying air into a building. Air thus ozonised destroys by oxidation--that is, brings about the combustion of--the organic residues present in the air, and thus will serve for purifying it. For these reasons the air of cities contains less ozone and such like oxidising agents than country air. This forms the distinguishing feature of country air. However, animal life cannot exist in air containing a comparatively large amount of ozone. Besides substances in a gaseous or vaporous state,[38] there is always found a more or less considerable quantity of substances which are not known in a state of vapour. These substances are present in the air as _dust_. If a linen surface, moistened with an acid, be placed in perfectly pure air, then the washings are found to contain sodium, calcium, iron, and potassium.[39] Linen moistened with an alkali absorbs carbonic, sulphuric, phosphoric, and hydrochloric acids. Further, the presence of organic substances in air has been proved by a similar experiment. If a glass globe be filled with ice and placed in a room where are a number of people, then the presence of organic substances, like albuminous substances, may be proved in the water which condenses on the surface of the globe. It may be that the miasmas causing infection in marshy localities, hospitals, and in certain epidemic illnesses proceed from the presence of such substances in the air (and especially in water, which contains many micro-organisms), as well as from the presence of germs of lower organisms in the air as a minute dust. Pasteur proved the existence of such germs in the air by the following experiment:--He placed gun-cotton (pyroxylin), which has the appearance of ordinary cotton, in a glass tube. Gun-cotton is soluble in a mixture of ether and alcohol, forming the so-called collodion. A current of air was passed through the tube for a long period of time, and the gun-cotton was then dissolved in a mixture of ether and alcohol. An insoluble residue was thus obtained which actually contained the germs of organisms, as was shown by microscopical observations, and by their capacity to develop into organisms (mould, &c.) under favourable conditions. The presence of these germs determines the property of air of bringing about the processes of putrefaction and fermentation--that is the fundamental alteration of organic substances, which is accompanied by an entire change in their properties. The appearance of lower organisms, both vegetable and animal, is always to be remarked in these processes. Thus, for instance, in the process of fermentation, when, for example, wine is procured from the sweet juice of grapes, a sediment separates out which is known under the name of lees, and contains peculiar yeast organisms. Germs are required before these organisms can appear.[40] They are floating in the air, and fall into the sweet fermentable liquid from it. Finding themselves under favourable conditions, the germs develop into organisms; they are nourished at the expense of the organic substance, and during growth change and destroy it, and bring about fermentation and putrefaction. This is why, for instance, the juice of the grape when contained in the skin of the fruit, which allows access of the air but is impenetrable to the germs, does not ferment, does not alter so long as the skin remains intact. This is also the reason why animal substances when kept from the access of air may be preserved for a great length of time. Preserved foods for long sea voyages are kept in this way.[41] Hence it is evident that however infinitesimal the quantity of germs carried in the atmosphere may be, still they have an immense significance in nature.[42] [38] Amongst them we may mention iodine and alcohol, C_{2}H_{6}O, which Müntz found to be always present in air, the soil, and water, although in minute traces only. [39] A portion of the atmospheric dust is of cosmic origin; this is undoubtedly proved by the fact of its containing metallic iron as do meteorites. Nordenskiöld found iron in the dust covering snow, and Tissandier in every kind of air, although naturally in very small quantities. [40] The idea of the spontaneous growth of organisms in a suitable medium, although still upheld by many, has since the work of Pasteur and his followers (and to a certain extent of his predecessors) been discarded, because it has been proved how, when, and whence (from the air, water, &c.) the germs appear; that fermentation as well as infectious diseases cannot take place without them; and chiefly because it has been shown that any change accompanied by the development of the organisms introduced may be brought about at will by the introduction of the germs into a suitable medium. [41] In further confirmation of the fact that putrefaction and fermentation depend on germs carried in the air, we may cite the circumstance that poisonous substances destroying the life of organisms stop or hinder the appearance of the above processes. Air which has been heated to redness or passed through sulphuric acid no longer contains the germs of organisms, and loses the faculty of producing fermentation and putrefaction. [42] Their presence in the air is naturally due to the diffusion of germs into the atmosphere, and owing to their microscopical dimensions, they, as it were, hang in the air in virtue of their large surfaces compared to their weight. In Paris the amount of dust suspended in the air equals from 6 (after rain) to 23 grams per 1,000 c.m. of air. Thus we see that air contains a great variety of substances. The nitrogen, which is found in it in the largest quantity, has the least influence on those processes which are accomplished by the action of air. The oxygen, which is met with in a lesser quantity than the nitrogen, on the contrary takes a very important part in a number of reactions; it supports combustion and respiration, it brings about decomposition and every process of slow oxidation. The part played by the moisture of air is well known. The carbonic anhydride, which is met with in still smaller quantities, has an immense significance in nature, inasmuch as it serves for the nourishment of plants. The importance of the ammonia and nitric acid is very great, because they are the sources of the nitrogenous substances comprising an indispensable element in all living organisms. And, lastly, the infinitesimal quantity of germs also have a great significance in a number of processes. Thus it is not the quantitative but the qualitative relations of the component parts of the atmosphere which determine its importance in nature.[43] [43] We see similar cases everywhere. For example, the predominating mass of sand and clay in the soil takes hardly any chemical part in the economy of the soil in respect to the nourishment of plants. The plants by their roots search for substances which are diffused in comparatively small quantities in the soil. If a large quantity of these nourishing substances are removed, then the plants will not develop in the soil, just as animals die in oxygen. Air, being a mixture of various substances, may suffer considerable _changes_ in consequence of incidental circumstances. It is particularly necessary to remark those changes in the composition of air which take place in dwellings and in various localities where human beings have to remain during a lengthy period of time. The respiration of human beings and animals alters the air.[44] A similar deterioration of air is produced by the influence of decomposing organic substances, and especially of substances burning in it.[45] Hence it is necessary to have regard to the purification of the air of dwellings. The renewal of air, the replacing of respired by fresh air, is termed 'ventilation,'[46] and the removal of foreign and injurious admixtures from the air is called 'disinfection.'[47] The accumulation of all kinds of impurities in the air of dwellings and cities is the reason why the air of mountains, forests, seas, and non-marshy localities, covered with vegetation or snow, is distinguished for its freshness, and, in all respects, beneficial action. [44] A man in breathing burns about 10 grams of carbon per hour--that is, he produces about 880 grams, or (as 1 cub.m. of carbonic anhydride weighs about 2,000 grams) about 5/12 c.m. of carbonic anhydride. The air coming from the lungs contains 4 p.c. of carbonic anhydride by volume. The exhaled air acts as a direct poison, owing to this gas and to other impurities. [45] For this reason candles, lamps, and gas change the composition of air almost in the same way as respiration. In the burning of 1 kilogram of stearin candles, 50 cubic metres of air are changed as by respiration--that is, 4 p.c. of carbonic anhydride will be formed in this volume of air. The respiration of animals and exhalations from their skins, and especially from the intestines and the excrements and the transformations taking place in them, contaminate the air to a still greater extent, because they introduce other volatile substances besides carbonic anhydride into the air. At the same time that carbonic anhydride is formed the amount of oxygen in the air decreases, and there is noticed the appearance of miasmata which occur in but small quantity, but which are noticeable in passing from fresh air into a confined space full of such adulterated air. The researches of Schmidt and Leblanc and others show that even with 20·6 p.c. of oxygen (instead of 20·9 p.c.), when the diminution is due to respiration, air becomes noticeably less fit for respiration, and that the heavy feeling experienced in such air increases with a lesser percentage of oxygen. It is difficult to remain for a few minutes in air containing 17·2 p.c. of oxygen. These observations were chiefly obtained by observations on the air of different mines, at different depths below the surface. The air of theatres and buildings full of people also proves to contain less oxygen; it was found on one occasion that at the end of a theatrical representation the air in the stalls contained 20·75 p.c. of oxygen, whilst the air at the upper part of the theatre contained only 20·36 p.c. The amount of carbonic anhydride in the air may be taken as a measure of its purity (Pettenkofer). When it reaches 1 p.c. it is very difficult for human beings to remain long in such air, and it is necessary to set up a vigorous ventilation for the removal of the adulterated air. In order to keep the air in dwellings in a uniformly good state, it is necessary to introduce at least 10 cubic metres of fresh air per hour per person. We saw that a man exhales about five-twelfths of a cubic metre of carbonic anhydride per day. Accurate observations have shown that air containing one-tenth p.c. of exhaled carbonic anhydride (and consequently also a corresponding amount of the other substances evolved together with it) is not felt to be oppressive; and therefore the five-twelfth cubic metres of carbonic anhydride should be diluted with 420 cubic metres of fresh air if it be desired to keep not more than one-tenth p.c. (by volume) of carbonic anhydride in the air. Hence a man requires 420 cubic metres of air per day, or 18 cubic metres per hour. With the introduction of only 10 cubic metres of fresh air per person, the amount of carbonic anhydride may reach one-fifth p.c., and the air will not then be of the requisite freshness. [46] The _ventilation_ of inhabited buildings is most necessary, and is even indispensable in hospitals, schools, and similar buildings. In winter it is carried on by the so-called calorifiers or stoves heating the air before it enters. The best kind of calorifiers in this respect are those in which the fresh cold air is led through a series of pipes heated by the hot gases coming from a stove. In ventilation, particularly during winter, care is taken that the incoming air shall be moist, because in winter the amount of moisture in the air is very small. Ventilation, besides introducing fresh air into a dwelling-place, must also withdraw the air already spoilt by respiration and other causes--that is, it is necessary to construct channels for the escape of the bad air, besides those for the introduction of fresh air. In ordinary dwelling-places, where not many people are congregated, the ventilation is conducted by natural means, in the heating by fires, through crevices, windows, and various orifices in walls, doors, and windows. In mines, factories, and workrooms ventilation is of the greatest importance. Animal vitality may still continue for a period of several minutes in air containing up to 30 p.c. of carbonic anhydride, if the remaining 70 p.c. consist of ordinary air; but respiration ceases after a certain time, and death may even ensue. The flame of a candle is very easily extinguished in an atmosphere containing from 5 to 6 p.c. of carbonic anhydride, but animal vitality can be sustained in it for a somewhat long time, although the effect of such air is exceedingly painful even to the lower animals. There are mines in which a lighted candle easily goes out from the excess of carbonic anhydride, but in which the miners have to remain for a long time. The presence of 1 p.c. of carbonic oxide is deadly even to cold-blooded animals. The air in the galleries of a mine where blasting has taken place, is known to produce a state of insensibility resembling that produced by charcoal fumes. Deep wells and vaults not unfrequently contain similar substances, and their atmosphere often causes suffocation. The atmospheres of such places cannot be tested by lowering a lighted candle into it, as these poisonous gases would not extinguish the flame. This method only suffices to indicate the amount of carbonic anhydride. If a candle keeps alight, it signifies that there is less than 6 p.c. of this gas. In doubtful cases it is best to lower a dog or other animal into the air to be tested. If CO_{2} be very carefully added to air, the flame of a candle is not extinguished (although it becomes very much smaller) even when the gas amounts to 12 p.c. of air. Researches made by F. Clowes (1894) show that the flames (in every case 3/4 in. long) of different combustible substances are extinguished by the gradual addition of different percentages of nitrogen and carbonic acid to the air; the percentage sufficient to extinguish the flame being as follows (the percentage of oxygen is given in parenthesis): p.c. CO_{2} p.c. N. Absolute alcohol 14 (18·1) 21 (16·6) Candle 14 (18·1) 22 (16·4) Hydrogen 58 ( 8·8) 70 ( 6·3) Coal gas 33 (14·1) 46 (11·3) Carbonic oxide 24 (16·0) 28 (15·1) Methane 10 (18·9) 17 (17·4) The flames of all solid and liquid substances is extinguished by almost the same percentage of CO_{2} or N_{2}, but the flames of different gases vary in this respect, and hydrogen continues to burn in mixtures which are far poorer in oxygen than those in which the flames of other combustible gases are extinguished; the flame of methane CH_{4} is the most easily extinguished. The percentage of nitrogen may be greater than that of CO_{2}. This, together with the fact that, under the above circumstances, the flame of a gas before going out becomes fainter and increases in size, seems to indicate that the chief reason for the extinction of the flame is the fall in its temperature. [47] Different so-called disinfectants purify the air, and prevent the injurious action of certain of its components by changing or destroying them. Disinfection is especially necessary in those places where a considerable amount of volatile substances are evolved into the air, and where organic substances are decomposed; for instance, in hospitals, closets, &c. The numerous disinfectants are of the most varied nature. They may be divided into oxidising, antiseptic, and absorbent substances. To the oxidising substances used for disinfection belong chlorine, and various substances evolving it, because chlorine in the presence of water oxidises the majority of organic substances, and this is why chlorine is used as a disinfectant for Siberian plagues. Further, to this class belong the permanganates of the alkalis and peroxide of hydrogen, as substances easily oxidising matters dissolved in water; these salts are not volatile like chlorine, and therefore act much more slowly, and in a much more limited sphere. Antiseptic substances are those which convert organic substances into such as are little prone to change, and prevent putrefaction and fermentation. They most probably kill the germs of organisms occurring in miasmata. The most important of these substances are creosote and phenol (carbolic acid), which occur in tar, and act in preserving smoked meat. Phenol is a substance little soluble in water, volatile, oily, and having the characteristic smell of smoked objects. Its action on animals in considerable quantities is injurious, but in small quantities, used in the form of a weak solution, it prevents the change of animal matter. The smell of privies, which depends on the change of excremental matter, may be easily removed by means of chlorine or phenol. Salicylic acid, thymol, common tar, and especially its solution in alkalis as proposed by Nensky, &c., are also substances having the same property. Absorbent substances are of no less importance, especially as preventatives, than the preceding two classes of disinfectants, inasmuch as they are innocuous. They are those substances which absorb the odoriferous gases and vapours emitted during putrefaction, which are chiefly ammonia, sulphuretted hydrogen, and other volatile compounds. To this class belong charcoal, certain salts of iron, gypsum, salts of magnesia, and similar substances, as well as peat, mould, and clay. Questions of disinfection and ventilation appertain to the most serious problems of common life and hygiene. These questions are so vast that we are here able only to give a short outline of their nature. CHAPTER VI THE COMPOUNDS OF NITROGEN WITH HYDROGEN AND OXYGEN [Illustration: FIG. 42.--The dry distillation of bones on a large scale. The bones are heated in the vertical cylinders C (about 1-1/2 metre high and 30 centimetres in diameter). The products of distillation pass through the tubes T, into the condenser B, and receiver F. When the distillation is completed the trap H is opened, and the burnt bones are loaded into trucks V. The roof M is then opened, and the cylinders are charged with a fresh quantity of bones. The ammonia water is preserved, and goes to the preparation of ammoniacal salts, as described in the following drawing.] In the last chapter we saw that nitrogen does not directly combine with hydrogen, but that a mixture of these gases in the presence of hydrochloric acid gas, HCl, forms ammonium chloride, NH_{4}Cl, on the passage of a series of electric sparks.[1] In ammonium chloride, HCl is combined with NH_{3}, consequently N with H_{3} forms ammonia.[2] Almost all the _nitrogenous substances of plants and animals_ evolve ammonia when heated with an alkali. But even without the presence of an alkali the majority of nitrogenous substances, when decomposed or heated with a limited supply of air, evolve their nitrogen, if not entirely, at all events partially, in the form of ammonia. When animal substances such as skins, bones, flesh, hair, horns, &c., are heated without access of air in iron retorts--they undergo what is termed dry distillation. A portion of the resultant substances remains in the retort and forms a carbonaceous residue, whilst the other portion, in virtue of its volatility, escapes through the tube leading from the retort. The vapours given off, on cooling, form a liquid which separates into two layers; the one, which is oily, is composed of the so-called animal oils (_oleum animale_): the other, an aqueous layer, contains a solution of ammonia salts. If this solution be mixed with lime and heated, the lime takes up the elements of carbonic acid from the ammonia salts, and ammonia is evolved as a gas.[3] In ancient times ammonia compounds were imported into Europe from Egypt, where they were prepared from the soot obtained in the employment of camels' dung as fuel in the locality of the temple of Jupiter Ammon (in Lybia), and therefore the salt obtained was called 'sal-ammoniacale,' from which the name of ammonia is derived. At the present time ammonia is obtained exclusively, on a large scale, either from the products of the dry distillation of animal or vegetable refuse, from urine, or from the ammoniacal liquors collected in the destructive distillation of coal for the preparation of coal gas. This ammoniacal liquor is placed in a retort with lime and heated; the ammonia is then evolved together with steam.[4] In the arts, only a small amount of ammonia is used in a free state--that is, in an aqueous solution; the greater portion of it is converted into different salts having technical uses, especially sal-ammoniac, NH_{4}Cl, and ammonium sulphate, (NH_{4})_{2}SO_{4}. They are saline substances which are formed because ammonia, NH_{3}, combines with all acids, HX, forming ammonia salts, NH_{4}X. Sal-ammoniac, NH_{4}Cl, is a compound of ammonia with hydrochloric acid. It is prepared by passing the vapours of ammonia and water, evolved, as above described, from ammoniacal liquor, into an aqueous solution of hydrochloric acid, and on evaporating the solution sal-ammoniac is obtained in the form of soluble crystals[5] resembling common salt in appearance and properties. Ammonia may be very easily prepared _from_ this _sal-ammoniac_, NH_{4}Cl, as from any other ammoniacal salt, by heating it with lime. Calcium hydroxide, CaH_{2}O_{2}, as an alkali takes up the acid and sets free the ammonia, forming calcium chloride, according to the equation 2NH_{4}Cl + CaH_{2}O_{2} = 2H_{2}O + CaCl_{2} + 2NH_{3}. In this reaction the ammonia is evolved as a gas.[6] [Illustration: FIG. 43.--Method of abstracting ammonia, on a large scale, from ammonia water obtained at gas works by the dry distillation of coal, or by the fermentation of urine, &c. This water is mixed with lime and poured into the boiler C´´, and from thence into C´ and C consecutively. The last boiler is heated directly over a furnace, and hence no ammonia remains in solution after the liquid has been boiled in it. The liquid is therefore then thrown away. The ammonia vapour and steam pass from the boiler C, through the tube T, into the boiler C´, and then into C´´, so that the solution in C´ becomes stronger than that in C, and still stronger in C´´. The boilers are furnished with stirrers A, A´, and A´´ to prevent the lime settling. From C´´ the ammonia and steam pass through the tube T´´ into worm condensers surrounded with cold water, thence into the Woulfe's bottle P, where the solution of ammonia is collected, and finally the still uncondensed ammonia vapour is led into the flat vessel R, containing acid which absorbs the last traces of ammonia.] [1] The ammonia in the air, water, and soil proceeds from the decomposition of the nitrogenous substances of plants and animals, and also probably from the reduction of nitrates. Ammonia is always formed in the rusting of iron. Its formation in this case depends in all probability on the decomposition of water, and on the action of the hydrogen at the moment of its evolution on the nitric acid contained in the air (Cloez), or on the formation of ammonium nitrite, which takes place under many circumstances. The evolution of vapours of ammonia compounds is sometimes observed in the vicinity of volcanoes. At a red heat nitrogen combines directly with B Ca Mg, and with many other metals, and these compounds, when heated with a caustic alkali, or in the presence of water, give ammonia (_see_ Chapter XIV., Note 14, and Chapter XVII., Note 12). These are examples of the indirect combination of nitrogen with hydrogen. [2] If a silent discharge or a series of electric sparks be passed through ammonia gas, it is decomposed into nitrogen and hydrogen. This is a phenomenon of dissociation; therefore, a series of sparks do not totally decompose the ammonia, but leave a certain portion undecomposed. One volume of nitrogen and three volumes of hydrogen are obtained from two volumes of ammonia decomposed. Ramsay and Young (1884) investigated the decomposition of NH_{3} under the action of heat, and showed that at 500°, 1-1/2 p.c. is decomposed, at 600° about 18 p.c., at 800° 65 p.c., but these results were hardly free from the influence of 'contact.' The _presence_ of free ammonia--that is, ammonia not combined with acids--in a gas or aqueous solution may be recognised by its characteristic smell. But many ammonia salts do not possess this smell. However, on the addition of an alkali (for instance, caustic lime, potash, or soda), they evolve ammonia gas, especially when heated. The presence of ammonia may be made visible by introducing a substance moistened with strong hydrochloric acid into its neighbourhood. A white cloud, or visible white vapour, then makes its appearance. This depends on the fact that both ammonia and hydrochloric acid are volatile, and on coming into contact with each other produce solid sal-ammoniac, NH_{4}Cl, which forms a cloud. This test is usually made by dipping a glass rod into hydrochloric acid, and holding it over the vessel from which the ammonia is evolved. With small amounts of ammonia this test is, however, untrustworthy, as the white vapour is scarcely observable. In this case it is best to take paper moistened with mercurous nitrate, HgNO_{3}. This paper turns black in the presence of ammonia, owing to the formation of a black compound of ammonia with mercurous oxide. The smallest traces of ammonia (for instance, in river water) may be detected by means of the so-called Nessler's reagent, containing a solution of mercuric chloride and potassium iodide, which forms a brown coloration or precipitate with the smallest quantities of ammonia. It will be useful here to give the thermochemical data (in thousands of units of heat, according to Thomsen), or the quantities of heat _evolved_ in the formation of ammonia and its compounds in quantities expressed by their formulæ. Thus, for instance, (N + H_{3}) 26·7 indicates that 14 grams of nitrogen in combining with 3 grams of hydrogen develop sufficient heat to raise the temperature of 26·7 kilograms of water 1°. (NH_{3} + nH_{2}O) 8·4 (heat of solution); (NH_{3},nH_{2}O + HCl,nH_{2}O) 12·3; (N + H_{4} + Cl) 90·6; (NH_{3} + HCl) 41·9. [3] The same ammonia water is obtained, although in smaller quantities, in the dry distillation of plants and of coal, which consists of the remains of fossil plants. In all these cases the ammonia proceeds from the destruction of the complex nitrogenous substances occurring in plants and animals. The ammonia salts employed in the arts are prepared by this method. [4] The technical methods for the preparation of ammonia water, and for the extraction of ammonia from it, are to a certain extent explained in the figures accompanying the text. [5] Usually these crystals are sublimed by heating them in crucibles or pots, when the vapours of sal-ammoniac condense on the cold covers as a crust, in which form the salt comes into the market. [6] On a small scale ammonia may be prepared in a glass flask by mixing equal parts by weight of slaked lime and finely-powdered sal-ammoniac, the neck of the flask being connected with an arrangement for drying the gas obtained. In this instance neither calcium chloride nor sulphuric acid can be used for drying the gas, since both these substances absorb ammonia, and therefore solid caustic potash, which is capable of retaining the water, is employed. The gas-conducting tube leading from the desiccating apparatus is introduced into a mercury bath, if dry gaseous ammonia be required, because water cannot be employed in collecting ammonia gas. Ammonia was first obtained in this dry state by Priestley, and its composition was investigated by Berthollet at the end of the last century. Oxide of lead mixed with sal-ammoniac (Isambert) evolves ammonia with still greater ease than lime. The cause and process of the decomposition are almost the same, 2PbO + 2NH_{4}Cl = Pb_{2}OCl_{2} + H_{2}O + 2NH_{3}. Lead oxychloride is (probably) formed. It must be observed that all the complex nitrogenous substances of plants, animals, and soils are decomposed when heated with an excess of sulphuric acid, the whole of their nitrogen being converted into ammonium sulphate, from which it may be liberated by treatment with an excess of alkali. This reaction is so complete that it forms the basis of Kjeldahl's method for estimating the amount of nitrogen in its compounds. Ammonia is a colourless gas, resembling those with which we are already acquainted in its outward appearance, but clearly distinguishable from any other gas by its very characteristic and pungent smell. It irritates the eyes, and it is positively impossible to inhale it. Animals die in it. Its density, referred to hydrogen, is 8·5; hence it is lighter than air. It belongs to the class of gases which are easily liquefied.[7] Faraday employed the following method for liquefying ammonia. Ammonia when passed over dry silver chloride, AgCl, is absorbed by it to a considerable extent, especially at low temperatures.[8] The solid compound AgCl,3NH_{3} thus obtained is introduced into a bent tube (fig. 45), whose open end c is then fused up. The compound is then slightly heated at _a_, and the ammonia comes off, owing to the easy dissociation of the compound. The other end of the tube is immersed in a freezing mixture. The pressure of the gas coming off, combined with the low temperature at one end of the tube, causes the ammonia evolved to condense into a liquid, in which form it collects at the cold end of the tube. If the heating be stopped, the silver chloride again absorbs the ammonia. In this manner one tube may serve for repeated experiments. Ammonia may also be liquefied by the ordinary methods--that is, by means of pumping dry ammonia gas into a refrigerated space. Liquefied ammonia is a colourless and very mobile liquid,[9] whose specific gravity at 0° is 0·63 (E. Andréeff). At the temperature (about -70°) given by a mixture of liquid carbonic anhydride and ether, liquid ammonia crystallises, and in this form its odour is feeble, because at so low a temperature its vapour tension is very inconsiderable. The boiling point (at a pressure of 760 mm.) of liquid ammonia is about -32°. Hence this temperature may be obtained at the ordinary pressure by the evaporation of liquefied ammonia. [Illustration: FIG. 45.--The liquefaction of ammonia in a thick bent glass tube. A compound of chloride of silver and ammonia is placed in the end _a_, and the end _c_ is then sealed up.] [7] [Illustration: FIG. 44.--Carré's apparatus. Described in text.] This is evident from the fact that its absolute boiling point lies at about +130° (Chapter II., Note 29). It may therefore be liquefied by pressure alone at the ordinary, and even at much higher temperatures. The latent heat of evaporation of 17 parts by weight of ammonia equals 4,400 units of heat, and hence liquid ammonia may be employed for the production of cold. Strong aqueous solutions of ammonia, which in parting with their ammonia act in a similar manner, are not unfrequently employed for this purpose. Suppose a saturated solution of ammonia to be contained in a closed vessel furnished with a receiver. If the ammoniacal solution be heated, the ammonia, with a small quantity of water, will pass off from the solution, and in accumulating in the apparatus will produce a considerable pressure, and will therefore liquefy in the cooler portions of the receiver. Hence liquid ammonia will be obtained in the receiver. The heating of the vessel containing the aqueous solution of ammonia is then stopped. After having been heated it contains only water, or a solution poor in ammonia. When once it begins to cool the ammonia vapours commence dissolving in it, the space becomes rarefied, and a rapid vaporisation of the liquefied ammonia left in the receiver takes place. In evaporating in the receiver it will cause the temperature in it to fall considerably, and will itself pass into the aqueous solution. In the end, the same ammoniacal solution as originally taken is re-obtained. Thus, in this case, on heating the vessel the pressure increases by itself, and on cooling it diminishes, so that here heat directly replaces mechanical work. This is the principle of the simplest forms of _Carré's ice-making machines_, shown in fig. 44. C is a vessel made of boiler plates into which the saturated solution of ammonia is poured; m is a tube conducting the ammonia vapour to the receiver A. All parts of the apparatus should be hermetically joined together, and should be able to withstand a pressure reaching ten atmospheres. The apparatus should be freed from air, which would otherwise hinder the liquefaction of the ammonia. The process is carried on as follows:--The apparatus is first so inclined that any liquid remaining in A may flow into C. The vessel C is then placed upon a stove F, and heated until the thermometer _t_ indicates a temperature of 130° C. During this time the ammonia has been expelled from C, and has liquefied in A. In order to facilitate the liquefaction, the receiver A should be immersed in a tank of water R (_see_ the left-hand drawing in fig. 44). After about half an hour, when it may be supposed that the ammonia has been expelled, the fire is removed from under C, and this is now immersed in the tank of water R. The apparatus is represented in this position in the right-hand drawing of fig. 44. The liquefied ammonia then evaporates, and passes over into the water in C. This causes the temperature of A to fall considerably. The substance to be refrigerated is placed in a vessel G, in the cylindrical space inside the receiver A. The refrigeration is also kept on for about half an hour, and with an apparatus of ordinary dimensions (containing about two litres of ammonia solution), five kilograms of ice are produced by the consumption of one kilogram of coal. In industrial works more complicated types of Carré's machines are employed. [8] Below 15° (according to Isambert), the compound AgCl,3NH_{3} is formed, and above 20° the compound 2AgCl,3NH_{3}. The tension of the ammonia evolved from the latter substance is equal to the atmospheric pressure at 68°, whilst for AgCl,3NH_{3} the pressures are equal at about 20°; consequently, at higher temperatures it is greater than the atmospheric pressure, whilst at lower temperatures the ammonia is absorbed and forms this compound. Consequently, all the phenomena of dissociation are here clearly to be observed. Joannis and Croisier (1894) investigated similar compounds with AgBr, AgI, AgCN and AgNO_{3}, and found that they all give definite compounds with NH_{3}, for instance AgBr,3NH_{3}, 2AgBr,3NH_{3} and AgBr,2NH_{3}; they are all colourless, solid substances which decompose under the atmospheric pressure at +3·5, +34° and +51°. [9] The liquefaction of ammonia may be accomplished without an increase of pressure, by means of refrigeration alone, in a carefully prepared mixture of ice and calcium chloride (because the absolute boiling point of NH_{3} is high, about +130°). It may even take place in the severe frosts of a Russian winter. The application of liquid ammonia as a motive power for engines forms a problem which has to a certain extent been solved by the French engineer Tellier. Ammonia, containing, as it does, much hydrogen, is _capable of combustion_; it does not, however, burn steadily, and sometimes not at all, in ordinary atmospheric air. In pure oxygen it burns with a greenish-yellow flame,[10] forming water, whilst the nitrogen set free gives its oxygen compounds--that is, oxides of nitrogen. The decomposition of ammonia into hydrogen and nitrogen not only takes place at a red heat and under the action of electric sparks, but also by means of many oxidising substances; for instance, by passing ammonia through a tube containing red-hot copper oxide. The water thus formed may be collected by substances absorbing it, and the quantity of nitrogen may be measured in a gaseous form, and thus the composition of ammonia determined. In this manner it is very easy to prove that ammonia contains 3 parts by weight of hydrogen to 14 parts by weight of nitrogen; and, by volume, 3 vols. of hydrogen and 1 vol. of nitrogen form 2 vols. of ammonia.[11] [10] The combustion of ammonia in oxygen may be effected by the aid of platinum. A small quantity of an aqueous solution of ammonia, containing about 20 p.c. of the gas, is poured into a wide-necked beaker of about one litre capacity. A gas-conducting tube about 10 mm. in diameter, and supplying oxygen, is immersed in the aqueous solution of ammonia. But before introducing the gas an incandescent platinum spiral is placed in the beaker; the ammonia in the presence of the platinum is oxidised and burns, whilst the platinum wire becomes still more incandescent. The solution of ammonia is heated, and oxygen passed through the solution. The oxygen, as it bubbles off from the ammonia solution, carries with it a part of the ammonia, and this mixture explodes on coming into contact with the incandescent platinum. This is followed by a certain cooling effect, owing to the combustion ceasing, but after a short interval this is renewed, so that one feeble explosion follows after another. During the period of oxidation without explosion, white vapours of ammonium nitrite and red-brown vapours of oxides of nitrogen make their appearance, while during the explosion there is complete combustion and consequently water and nitrogen are formed. [11] This may be verified by their densities. Nitrogen is 14 times denser than hydrogen, and ammonia is 8-1/2 times. If 3 volumes of hydrogen with 1 volume of nitrogen gave 4 volumes of ammonia, then these 4 volumes would weigh 17 times as much as 1 volume of hydrogen; consequently 1 volume of ammonia would be 4-1/4 times heavier than the same volume of hydrogen. But if these 4 volumes only give 2 volumes of ammonia, the latter will be 8-1/2 times as dense as hydrogen, which is found to be actually the case. Ammonia is capable of combining with a number of substances, forming, like water, substances of various degrees of stability. It is more soluble than any of the gases yet described, both in water and in many aqueous solutions. We have already seen, in the first chapter, that one volume of water, at the ordinary temperature, dissolves about 700 vols. of ammonia gas. The great solubility of ammonia enables it to be always kept ready for use in the form of an aqueous solution,[12] which is commercially known as _spirits of hartshorn_. Ammonia water is continually evolving ammoniacal vapour, and so has the characteristic smell of ammonia itself. It is a very characteristic and important fact that ammonia has an alkaline reaction, and colours litmus paper blue, just like caustic potash or lime; it is therefore sometimes called _caustic ammonia_ (volatile alkali). Acids may be saturated by ammonia water or gas in exactly the same way as by any other alkali. In this process _ammonia combines directly with acids_, and this forms the most essential chemical reaction of this substance. If sulphuric, nitric, acetic, or any other acid be brought into contact with ammonia it absorbs it, and in so doing evolves a large amount of heat and forms a compound having all the properties of a salt. Thus, for example, sulphuric acid, H_{2}SO_{4}, in absorbing ammonia, forms (on evaporating the solution) two salts, according to the relative quantities of ammonia and acid. One salt is formed from NH_{3} + H_{2}SO_{4}, and consequently has the composition NH_{5}SO_{4}, and the other is formed from 2NH_{3} + H_{2}SO_{4}, and its composition is therefore N_{2}H_{8}SO_{4}. The former has an acid reaction and the latter a neutral reaction, and they are called respectively acid ammonium sulphate (ammonium hydrogen sulphate), and normal ammonium sulphate, or simply ammonium sulphate. The same takes place in the action of all other acids; but certain of them are able to form normal ammonium salts only, whilst others give both acid and normal ammonium salts. This depends on the nature of the acid and not on the ammonia, as we shall afterwards see. Ammonium salts are very similar in appearance and in many of their properties to metallic salts; for instance, sodium chloride, or table salt, resembles sal-ammoniac, or ammonium chloride, not only in its outward appearance but even in crystalline form, in its property of giving precipitates with silver salts, in its solubility in water, and in its evolving hydrochloric acid when heated with sulphuric acid--in a word, a most perfect analogy is to be remarked in an entire series of reactions. An analogy in composition is seen if sal-ammoniac, NH_{4}Cl, be compared with table salt, NaCl; and the ammonium hydrogen sulphate, NH_{4}HSO_{4}, with the sodium hydrogen sulphate, NaHSO_{4}; or ammonium nitrate, NH_{4}NO_{3}, with sodium nitrate, NaNO_{3}.[13] It is seen, on comparing the above compounds, that the part which sodium takes in the sodium salts is played in ammonium salts by a group NH_{4}, which is called _ammonium_. If table salt be called 'sodium chloride,' then sal-ammoniac should be and is called 'ammonium chloride.' [12] Aqueous solutions of ammonia are lighter than water, and at 15°, taking water at 4° = 10,000, their specific gravity, as dependent on _p_, or the percentage amount (by weight) of ammonia, is given by the expression _s_ = 9,992-42·5_p_ + 0·21_p_^2; for instance, with 10 p.c. _s_ = 9,587. If _t_ represents the temperature between the limits of +10° and +20°, then the expression (15-_t_)(1·5 + 0·14_p_) must be added to the formula for the specific gravity. Solutions containing more than 24 p.c. have not been sufficiently investigated in respect to the variation of their specific gravity. It is, however, easy to obtain more concentrated solutions, and at 0° solutions approaching NH_{3},H_{2}O (48·6 p.c. NH_{3}) in their composition, and of sp. gr. 0·85, may be prepared. But such solutions give up the bulk of their ammonia at the ordinary temperature, so that more than 24 p.c. NH_{3} is rarely contained in solution. Ammoniacal solutions containing a considerable amount of ammonia give ice-like crystals which seem to contain ammonia at temperatures far below 0° (for instance, an 8 p.c. solution at -14°, the strongest solutions at -48°). The whole of the ammonia may be expelled from a solution by heating, even at a comparatively low temperature; hence on heating aqueous solutions containing ammonia a very strong solution of ammonia is obtained in the distillate. Alcohol, ether, and many other liquids are also capable of dissolving ammonia. Solutions of ammonia, when exposed to the atmosphere, give off a part of their ammonia in accordance with the laws of the solution of gases in liquids, which we have already considered. But the ammoniacal solutions at the same time absorb carbonic anhydride from the air, and ammonium carbonate remains in the solution. [Illustration: FIG. 46.--Apparatus for preparing solutions of ammonia.] Solutions of ammonia are required both for laboratory and factory operations, and have therefore to be frequently prepared. For this purpose the arrangement shown in fig. 46 is employed in the laboratory. In works the same arrangement is used, only on a larger scale (with earthenware or metallic vessels). The gas is prepared in the retort, from whence it is led into the two-necked globe A, and then through a series of Woulfe's bottles, B, C, D, E. The impurities spurting over collect in A, and the gas is dissolved in B, but the solution soon becomes saturated, and a purer (washed) ammonia passes over into the following vessels, in which only a pure solution is obtained. The bent funnel tube in the retort preserves the apparatus from the possibility both of the pressure of the gas evolved in it becoming too great (when the gas escapes through it into the air), and also from the pressure incidentally falling too low (for instance, owing to a cooling effect, or from the reaction stopping). If this takes place, the air passes into the retort, otherwise the liquid from B would be drawn into A. The safety tubes in each Woulfe's bottle, open at both ends, and immersed in the liquid, serve for the same purpose. Without them, in case of an accidental stoppage in the evolution of so soluble a gas as ammonia, the solution would be sucked from one vessel to another--for instance, from E into D, &c. In order to clearly see the necessity for _safety tubes_ in a gas apparatus, it must be remembered that the _gaseous pressure_ in the interior of the arrangement must exceed the atmospheric pressure by the height of the sum of the columns of liquid through which the gas has to pass. [13] The analogy between the ammonium and sodium salts might seem to be destroyed by the fact that the latter are formed from the alkali or oxide and an acid, with the separation of water, whilst the ammonium salts are directly formed from ammonia and an acid, without the separation of water; but the analogy is restored if we compare soda to ammonia water, and liken caustic soda to a compound of ammonia with water. Then the very preparation of ammonium salts from such a hydrate of ammonia will completely resemble the preparation of sodium salts from soda. We may cite as an example the action of hydrochloric acid on both substances. NaHO + HCl = H_{2}O + NaCl Sodium hydroxide Hydrochloric acid Water Table salt NH_{4}HO + HCl = H_{2}0 + NH_{4}Cl Ammonium hydroxide Hydrochloric acid Water Sal-ammoniac Just as in soda the hydroxyl or aqueous radicle OH is replaced by chlorine, so it is in ammonia hydrate. The hypothesis that ammoniacal salts correspond with a complex metal ammonium bears the name of the _ammonium theory_. It was enunciated by the famous Swedish chemist Berzelius after the proposition made by Ampère. The analogy admitted between ammonium and metals is probable, owing to the fact that mercury is able to form an amalgam with ammonium similar to that which it forms with sodium or many other metals. The only difference between ammonium amalgam and sodium amalgam consists in the instability of the ammonium, which easily decomposes into ammonia and hydrogen.[14] Ammonium amalgam may be prepared from sodium amalgam. If the latter be shaken up with a strong solution of sal-ammoniac, the mercury swells up violently and loses its mobility whilst preserving its metallic appearance. In so doing, the mercury dissolves ammonium--that is, the sodium in the mercury is replaced by the ammonium, and replaces it in the sal-ammoniac, forming sodium chloride, NH_{4}Cl + HgNa = NaCl + HgNH_{4}. Naturally, the formation of ammonium amalgam does not entirely prove the existence of ammonium itself in a separate state; but it shows the possibility of this substance existing, and its analogy with the metals, because only metals dissolve in mercury.[15] Ammonium amalgam crystallises in cubes, three times heavier than water; it is only stable in the cold, and particularly at very low temperatures. It begins to decompose at the ordinary temperature, evolving ammonia and hydrogen in the proportion of two volumes of ammonia and one volume of hydrogen, NH_{4} = NH_{3} + H. By the action of water, ammonium amalgam gives hydrogen and ammonia water, just as sodium amalgam gives hydrogen and sodium hydroxide; and therefore, in accordance with the ammonium theory, ammonia water must be looked on as containing ammonium hydroxide, NH_{4}OH,[16] just as an aqueous solution of sodium hydroxide, contains NaOH. The ammonium hydroxide, like ammonium itself, is an unstable substance, which easily dissociates, and can only exist in a free state at low temperatures.[17] Ordinary solutions of ammonia must be looked on as the products of the dissociation of this hydroxide, inasmuch as NH_{4}OH = NH_{3} + H_{2}O. [14] Weyl (1864) by subjecting sodium to the action of ammonia at the ordinary temperature and under considerable pressures, obtained a liquid, which was subsequently investigated by Joannis (1889), who confirmed the results obtained by Weyl. At 0° and the atmospheric pressure the composition of this substance is Na + 5·3NH_{3}. The removal (at 0°) of ammonia from the liquid gives a solid copper-red body having the composition NH_{3}Na. The determination of the molecular weight of this substance by the fall of the tension of liquid ammonia gave N_{2}H_{6}Na_{2}. It is, therefore, free ammonium in which one H is replaced by Na. The compound with potassium, obtained under the same conditions, proved to have an analogous composition. By the decomposition of NH_{3}Na at the ordinary temperature, Joannis (1891) obtained hydrogen and sodium-amide NH_{2}Na in small colourless crystals which were soluble in water. The addition of liquid ammonia to metallic sodium and a saturated solution of sodium chloride, gives NH_{2}Na_{2}Cl, and this substance is sal-ammoniac, in which H_{2} is replaced by Na_{2}. If pure oxygen be passed through a solution of these compounds in ammonia at a temperature of about -50°, it is seen that the gas is rapidly absorbed. The liquid gradually loses its dark red colour and becomes lighter, and when it has become quite colourless a gelatinous precipitate is thrown down. After the removal of the ammonia, this precipitate dissolves easily in water with a considerable evolution of heat, but without giving off any gaseous products. The composition of the sodium compound thus obtained is NH_{2}Na_{2}HO, which shows that it is a hydrate of bisodium-ammonium. Thus, although free ammonium has not been obtained, still a sodium substitution product of it is known which corresponds to it as a salt to a hydrate. Ammonium amalgam was originally obtained in exactly the same way as sodium amalgam (Davy); namely, a piece of sal-ammoniac was taken, and moistened with water (in order to render it a conductor of electricity). A cavity was made in it, into which mercury was poured, and it was laid on a sheet of platinum connected with the positive pole of a galvanic battery, while the negative pole was put into connection with the mercury. On passing a current the mercury increased considerably in volume, and became plastic, whilst preserving its metallic appearance, just as would be the case were the sal-ammoniac replaced by a lump of a sodium salt or of many other metals. In the analogous decomposition of common metallic salts, the metal contained in a given salt separates out at the negative pole, immersed in mercury, by which the metal is dissolved. A similar phenomenon is observed in the case of sal-ammoniac; the elements of ammonium, NH_{4}, in this case are also collected in the mercury, and are retained by it for a certain time. [15] We may mention, however, that under particular conditions hydrogen is also capable of forming an amalgam resembling the amalgam of ammonium. If an amalgam of zinc be shaken up with an aqueous solution of platinum chloride, without access of air, then a spongy mass is formed which easily decomposes, with the evolution of hydrogen. [16] We saw above that the solubility of ammonia in water at low temperatures attains to the molecular ratio NH_{3} + H_{2}O, in which these substances are contained in caustic ammonia, and perhaps it may be possible at exceedingly low temperatures to obtain ammonium hydroxide, NH_{4}HO, in a solid form. Regarding solutions as dissociated definite compounds, we should see a confirmation of this view in the property shown by ammonia of being extremely soluble in water, and in so doing of approaching to the limit NH_{4}HO. [17] In confirmation of the truth of this conclusion we may cite the remarkable fact that there exist, in a free state and as comparatively stable compounds, a series of alkaline hydroxides, NR_{4}HO, which are perfectly analogous to ammonium hydroxide, and present a striking resemblance to it and to sodium hydroxide, with the only difference that the hydrogen in NH_{4}HO is replaced by complex groups, R = CH_{3}, C_{2}H_{5}, &c., for instance N(CH_{3})_{4}HO. Details will be found in organic chemistry. All ammoniacal salts _decompose at a red heat_ into ammonia and an acid, which, on cooling in contact with each other, re-combine together. If the acid be non-volatile, the ammoniacal salt, when heated, evolves the ammonia, leaving the non-volatile acid behind; if the acid be volatile, then, on heating, both the acid and ammonia volatilise together, and on cooling re-combine into the salt which originally served for the formation of their vapours.[18] [18] The fact that ammoniacal salts are decomposed when ignited, and not simply sublimed, may be proved by a direct experiment with sal-ammoniac, NH_{4}Cl, which in a state of vapour is decomposed into ammonia, NH_{3}, and hydrochloric acid, HCl, as will be explained in the following chapter. The readiness with which ammonium salts decompose is seen from the fact that a solution of ammonium oxalate is decomposed with the evolution of ammonia even at -1°. Dilute solutions of ammonium salts, when boiled give aqueous vapour having an alkaline reaction, owing to the presence of free ammonia given off from the salt. Ammonia is not only capable of combining with acids, but also with many salts, as was seen from its forming definite compounds, AgCl,3NH_{3} and 2AgCl,3NH_{3}, with silver chloride. Just as ammonia is absorbed by various oxygen salts of the metals, so also is it absorbed by the chlorine, iodine, and bromine compounds of many metals, and in so doing evolves heat. Certain of these compounds part with their ammonia even when left exposed to the air, but others only do so at a red heat; many give up their ammonia when dissolved, whilst others dissolve without decomposition, and when evaporated separate from their solutions unchanged. All these facts only indicate that ammoniacal, like aqueous, compounds dissociate with greater or lesser facility.[19] Certain metallic oxides also absorb ammonia and are dissolved in ammonia water. Such are, for instance, the oxides of zinc, nickel, copper, and many others; the majority of such compounds are unstable. The property of ammonia of combining with certain oxides explains its action on certain metals.[20] By reason of such action, copper vessels are not suitable for holding liquids containing ammonia. Iron is not acted on by such liquids. [19] Isambert studied the dissociation of ammoniacal compounds, as we have seen in Note 8, and showed that at low temperatures many salts are able to combine with a still greater amount of ammonia, which proves an entire analogy with hydrates; and as in this case it is easy to isolate the definite compounds, and as the least possible tension of ammonia is greater than that of water, therefore the ammoniacal compounds present a great and peculiar interest, as a means for explaining the nature of aqueous solutions and as a confirmation of the hypothesis of the formation of definite compounds in them; for these reasons we shall frequently refer to these compounds in the further exposition of this work. [20] Chapter V., Note 2. The similarity between the relation of ammonia and water to salts and other substances is more especially marked in those cases in which the salt is capable of combining with both ammonia and water. Take, for example, copper sulphate, CuSO_{4}. As we saw in Chapter I., it gives with water blue crystals, CuSO_{4},5H_{2}O; but it also absorbs ammonia in the same molecular proportion, forming a blue substance, CuSO_{4},5NH_{3}, and therefore the ammonia combining with salts may be termed _ammonia of crystallisation_. Such are the _reactions of combination_ proper to ammonia. Let us now turn our attention to the reactions of substitution proper to this substance. If ammonia be passed through a heated tube containing metallic sodium, hydrogen is evolved, and a compound is obtained containing ammonia in which one atom of hydrogen is replaced by an atom of sodium, NH_{2}Na (according to the equation NH_{3} + Na = NH_{2}Na + H). This body is termed sodium amide. We shall afterwards see that iodine and chlorine are also capable of directly displacing hydrogen from ammonia, and of replacing it. In fact, the hydrogen of ammonia may be replaced in many ways by different elements. If in this replacement NH_{2} remains, the resultant substances NH_{2}R are called _amides_, whilst the substitution products, NHR_{2}, in which only NH remains, are called _imides_,[20 bis] and those in which none of the ammoniacal hydrogen remains, NR_{3}, are known as _nitrides_. Free amidogen, N_{2}H_{4}, is now known in a state of hydration under the name of hydrazine;[21] it combines with acids and resembles ammonia in this respect. In the action of different substances on ammonia it is the _hydrogen that is substituted_, whilst the nitrogen remains in the resultant compound, so to say, untouched. The same phenomenon is to be observed in the action of various substances on water. In the majority of cases the reactions of water consist in the hydrogen being evolved, and in its being replaced by different elements. This also takes place, as we have seen, in acids in which the hydrogen is easily displaced by metals. This chemical mobility of hydrogen is perhaps connected with the great lightness of the atoms of this element. [20 bis] Imide, NH, has not been obtained in a free state, but its hydrochloric acid salt, NHHCl, has apparently been obtained (1890) by Maumené by igniting the double bichloride of platinum and ammonium chloride, PtCl_{2}NH_{4}Cl = Pt + 2HCl + NHHCl. It is soluble in water, and crystallises from its solution in hexagonal rhombic prisms. It gives a double salt with FeCl_{3} of the composition FeCl_{3}3NHHCl. The salt NHHCl is similar (isomeric) with the first possible product of the metalepsis of ammonia, NH_{2}Cl, although it does not resemble it in any of its properties. [21] Free _amidogen_ or _hydrazine_, N_{2}H_{4}, or 2NH_{2}, was prepared by Curtius (1887) by means of ethyl diazoacetate, or triazoacetic acid. Curtius and Jay (1889) showed that triazoacetic acid, CHN_{2}.COOH (the formula should be tripled), when heated with water or a mineral acid, gives (quantitatively) oxalic acid and amidogen (hydrazine), CHN_{2}.COOH + 2H_{2}O = C_{2}O_{2}(OH)_{2} + N_{2}H_{4}--_i.e._ (empirically), the oxygen of the water replaces the nitrogen of the azoacetic acid. The amidogen is thus obtained in the form of a salt. With acids, amidogen forms very stable salts of the two types N_{2}H_{4}HX and N_[2]H_{4}H_{2}X_{2}, as, for example, with HCl, H_{2}SO_{4}, &c. These salts are easily crystallised; in acid solutions they act as powerful reducing agents, evolving nitrogen; when ignited they are decomposed into ammoniacal salts, nitrogen, and hydrogen; with nitrites they evolve nitrogen. The sulphate N_{2}H_{4},H_{2}SO_{4} is sparingly soluble in cold water (3 parts in 100 of water), but is very soluble in hot water; its specific gravity is 1·378, it fuses at 254° with decomposition. The hydrochloride N_{2}H_{4},2HCl crystallises in octahedra, is very soluble in water, but not in alcohol; it fuses at 198°, evolving hydrogen chloride and forming the salt N_{2}H_{4}HCl; when rapidly heated it decomposes with an explosion; with platinic chloride it immediately evolves nitrogen, forming platinous chloride. By the action of alkalis the salts N_{2}H_{4},2HX give _hydrate of amidogen_, N_{2}H_{4},H_{2}O, which is a fuming liquid (specific gravity 1·03), boiling at 119°, almost without odour, and whose aqueous solution corrodes glass and india-rubber, has an alkaline taste and poisonous properties. The reducing capacities of the hydrate are clearly seen from the fact that it reduces the metals platinum and silver from their solutions. With mercuric oxide it explodes. It reacts directly with the aldehydes RO, forming N_{2}R_{2} and water; for example, with benzaldehydes it gives the very stable insoluble _benzalazine_ (C_{6}H_{5}CHN)_{2} of a yellow colour. We may add that hydrazine often forms double salts; for example, MgSO_{4}N_{2}H_{4}H_{2}SO_{4} or KClN_{2}H_{4}HCl, and that it is also formed by the action of nitrous acid upon aldehyde-ammonia. The products of the substitution of the hydrogen in hydrazine by hydrocarbon groups R (R = CH_{3}, C_{2}H_{5}, C_{6}H_{5}, &c.) were obtained before hydrazine itself; for example, NHRNH_{2}, NR_{2}NH_{2}, and (NRH)_{2}. The heat of solution of the sulphuric acid salt (1 part in 200 and 300 parts of water at 10°·8) is equal to -8·7 C. According to Berthelot and Matigon (1892), the heat of neutralisation of hydrazine by sulphuric acid is +5·5 C and by hydrochloric acid +5·2 C. Thus hydrazine is a very feeble base, for its heat of saturation is not only lower than that of ammonia (+12·4 C. for HCl), but even below that of hydroxylamine (+9·3 C.) The heat of formation from the elements of hydrated hydrazine -9·5 C was deduced from the heat of combustion, determined by burning N_{2}H_{4}H_{2}SO_{4} in a calorimetric bomb, +127·7 C. Thus hydrazine is an endothermal compound; its passage into ammonia by the combination of hydrogen is accompanied by the evolution of 51·5 C. In the presence of an acid these figures were greater by +14·4 C. Hence the direct converse passage from ammonia into hydrazine is impossible. As regards the passage of hydroxylamine into hydrazine, it would be accompanied by the evolution of heat (+21·5 C.) in an aqueous solution. Amidogen must be regarded as a compound which stands to ammonia in the same relation as hydrogen peroxide stands to water. Water, H(OH), gives, according to the law of substitution, as was clearly to be expected, (OH)(OH)--that is, peroxide of hydrogen is the free radicle of water (hydroxyl). So also ammonia, H(NH_{2}), forms hydrazine, (NH_{2})(NH_{2})--that is, the free radicle of ammonia, NH_{2}, or amidogen. In the case of phosphorus a similar substance, as we shall afterwards see, has long been known under the name of liquid phosphuretted hydrogen, P_{2}H_{4}. In practical chemistry[21 bis] ammonia is often employed, not only for saturating acids, but also for effecting reactions of double decomposition with salts, and especially for separating insoluble basic hydroxides from soluble salts. Let MHO stand for an insoluble basic hydroxide and HX for an acid. The salt formed by them will have a composition MHO + XH-H_{2}O = MX. If aqueous ammonia, NH_{4}OH, be added to a solution of this salt, the ammonia will change places with the metal M, and thus form the insoluble basic hydroxide, or, as it is said, give a precipitate. MX + NH_{4}(OH) = NH_{4}X + MHO Salt of the metal. Aqueous ammonia. Ammonium salt. Basic hydrate. In solution In solution In solution As precipitate [21 bis] In practice, the applications of ammonia are very varied. The use of ammonia as a stimulant, in the forms of the so-called 'smelling salts' or of spirits of hartshorn, in cases of faintness, &c., is known to everyone. The volatile carbonate of ammonium, or a mixture of an ammonium salt with an alkali, is also employed for this purpose. Ammonia also produces a well-known stimulating effect when rubbed on the skin, for which reason it is sometimes employed for external applications. Thus, for instance, the well-known volatile salve is prepared from any liquid oil shaken up with a solution of ammonia. A portion of the oil is thus transformed into a soapy substance. The solubility of greasy substances in ammonia, which proceeds from the formation both of emulsions and soaps, explains its use in extracting grease spots. It is also employed as an external application for stings from insects, and for bites from poisonous snakes, and in general in medicine. It is also remarkable that in cases of drunkenness a few drops of ammonia in water taken internally rapidly renders a person sober. A large quantity of ammonia is used in dyeing, either for the solution of certain dyes--for example, carmine--or for changing the tints of others, or else for neutralising the action of acids. It is also employed in the manufacture of artificial pearls. For this purpose the small scales of a peculiar small fish are mixed with ammonia, and the liquid so obtained is blown into small hollow glass beads shaped like pearls. In nature and the arts, however, ammonium salts, and not free ammonia, are most frequently employed. In this form a portion of that _nitrogen_ which is necessary for the formation of albuminous substances is _supplied to plants_. Owing to this, a large quantity of ammonium sulphate is now employed as a fertilising substance. But the same effect may be produced by nitre, or by animal refuse, which in decomposing gives ammonia. For this reason, an ammoniacal (hydrogen) compound may be introduced into the soil in the spring which will be converted into a nitrate (oxygen salt) in the summer. Thus, for instance, if aqueous ammonia is added to a solution of a salt of aluminium, then alumina hydrate is separated out as a colourless gelatinous precipitate.[22] [22] As certain basic hydrates form peculiar compounds with ammonia, in some cases it happens that the first portions of ammonia added to a solution of a salt produce a precipitate, whilst the addition of a fresh quantity of ammonia dissolves this precipitate if the ammoniacal compound of the base be soluble in water. This, for example, takes place with the copper salts. But alumina does not dissolve under these circumstances. In order to grasp the relation between ammonia and the oxygen compounds of nitrogen it is necessary to recognise the general _law of substitution_, applicable to all cases of substitution between elements,[23] and therefore showing what may be the cases of substitution between oxygen and hydrogen as component parts of water. The law of substitution may be deduced from mechanical principles if the molecule be conceived as a system of elementary atoms occurring in a certain chemical and mechanical equilibrium. By likening the molecule to a system of bodies in a state of motion--for instance, to the sum total of the sun, planets, and satellites, existing in conditions of mobile equilibrium--then we should expect the action of one part, in this system, to be equal and opposite to the other, according to Newton's third law of mechanics. Hence, given a molecule of a compound, for instance, H_{2}O, NH_{3}, NaCl, HCl, &c., its every two parts must in a chemical sense represent two things somewhat alike in force and properties, and therefore _every two parts into which a molecule of a compound may be divided are capable of replacing each other_. In order that the application of the law should become clear it is evident that among compounds the most stable should be chosen. We will therefore take hydrochloric acid and water as the most stable compounds of hydrogen.[24] According to the above law of substitution, if the elements H and Cl are able to form a molecule, HCl, and a stable one, they are able to replace each other. And, indeed, we shall afterwards see (Chapter XI.) that in a number of instances a substitution between hydrogen and chlorine can take place. Given RH, then RCl is possible, because HCl exists and is stable. The molecule of water, H_{2}O, may be divided in two ways, because it contains 3 atoms: into H and (HO) on the one hand, and into H_{2} and O on the other. Consequently, being given RH, its substitution products will be R(HO) according to the first form, and R_{2}O according to the second; being given RH_{2}, its corresponding substitution products will be RH(OH), R(OH)_{2}, RO, (RH)_{2}O, &c. The group (OH) is the same hydroxyl or aqueous radicle which we have already mentioned in the third chapter as a component part of hydroxides and alkalis--for instance, Na(OH), Ca(OH)_{2}, &c. It is evident, judging from H(HO) and HCl, that (OH) can be substituted by Cl, because both are replaceable by H; and this is of common occurrence in chemistry, because metallic chlorides--for example, NaCl and NH_{4}Cl--correspond with hydroxides of the alkalis Na(OH) or NH_{4}(OH). In hydrocarbons--for instance, C_{2}H_{6}--the hydrogen is replaceable by chlorine and by hydroxyl. Thus ordinary alcohol is C_{2}H_{6}, in which one atom of H is replaced by (OH); that is, C_{2}H_{5}(OH). It is evident that the replacement of hydrogen by hydroxyl essentially forms the phenomenon of oxidation, because RH gives R(OH), or RHO. Hydrogen peroxide may in this sense be regarded as water in which the hydrogen is replaced by hydroxyl; H(OH) gives (OH)_{2} or H_{2}O_{2}. The other form of substitution--namely, that of O in the place of H_{2}--is also a common chemical phenomenon. Thus alcohol, C_{2}H_{6}O, or C_{2}H_{5}(OH), when oxidising in the air, gives acetic acid, C_{2}H_{4}O_{2}, or C_{2}H_{3}O(OH), in which H_{2} is replaced by O. [23] When the element chlorine, as we shall afterwards more fully learn, replaces the element hydrogen, the reaction by which such an exchange is accomplished proceeds as a substitution, AH + Cl_{2} = ACl + HCl, so that two substances, AH and chlorine, react on each other, and two substances, ACl and HCl, are formed; and further, two molecules react on each other, and two others are formed. The reaction proceeds very easily, but the substitution of one element, _A_, by another, _X_, does not always proceed with such ease, clearness, or simplicity. The substitution between oxygen and hydrogen is very rarely accomplished by the reaction of the free elements, but the substitution between these elements, one for another, forms the most common case of oxidation and reduction. In speaking of the law of substitution, I have in view the substitution of the elements one by another, and not the direct reaction of substitution. The law of substitution determines the cycle of the combinations of a given element, if a few of its compounds (for instance, the hydrogen compounds) be known. A development of the conceptions of the law of substitution may be found in my lecture given at the Royal Institution in London, 1889. [24] If hydrogen peroxide be taken as a starting point, then still higher forms of oxidation than those corresponding with water should be looked for. They should possess the properties of hydrogen peroxide, especially that of parting with their oxygen with extreme ease (even by contact). Such compounds are known. Pernitric, persulphuric, and similar acids present these properties, as we shall see in describing them. In the further course of this work we shall have occasion to refer to the law of substitution for explaining many chemical phenomena and relations. We will now apply these conceptions to ammonia in order to see its relation to the oxygen compounds of nitrogen. It is evident that many substances should be obtainable from ammonia, NH_{3}, or aqueous ammonia, NH_{4}(OH), by substituting their hydrogen by hydroxyl, or H_{2} by oxygen. And such is the case. The two extreme cases of such substitution will be as follows: (1) One atom of H in NH_{3} is substituted by (OH), and NH_{2}(OH) is produced. Such a substance, still containing much hydrogen, should have many of the properties of ammonia. It is known under the name of _hydroxylamine_,[25] and, in fact, is capable, like ammonia, of giving salts with acids; for example, with hydrochloric acid, NH_{3}(OH)Cl--which is a substance corresponding to sal-ammoniac, in which one atom of hydrogen is replaced by hydroxyl.[25 bis] (2) The other extreme case of substitution is that given by ammonium hydroxide, NH_{4}(OH), when the whole of the hydrogen of the ammonium is replaced by oxygen; and, as ammonium contains 4 atoms of hydrogen, the highest oxygen compound should be NO_{2}(OH), or NHO_{3}, as we find to be really the case, for NHO_{3} is nitric acid, exhibiting the highest degree of oxidation of nitrogen.[26] If instead of the two extreme aspects of substitution we take an intermediate one, we obtain the intermediate oxygen compounds of nitrogen. For instance, N(OH)_{3} is orthonitrous acid,[27] to which corresponds nitrous acid, NO(OH), or NHO_{2}, equal to N(OH)_{3}-H_{2}O, and nitrous anhydride, N_{2}O_{3} = 2N(OH)_{3}-3H_{2}O. Thus nitrogen gives a series of oxygen compounds, which we will proceed to describe. We will, however, first show by two examples that in the first place the passage of ammonia into the oxygen compounds of nitrogen up to nitric acid, as well as the converse preparation of ammonia (and consequently of the intermediate compounds also) from nitric acid, are reactions which proceed directly and easily under many circumstances, and in the second place that the above general principle of substitution gives the possibility of understanding many, at first sight unexpected and complex, relations and transformations, such as the preparation of hydronitrous acid, HN_{3}. In nature the matter is complicated by a number of influences and circumstances, but in the law the relations are presented in their simplest aspect. [25] The compound of hydroxylamine with hydrochloric acid has the composition NH_{2}(OH)HCl = NH_{4}ClO--that is, it is as it were oxidised sal-ammoniac. It was prepared by Lossen in 1865 by the action of tin and hydrochloric acid in the presence of water on a substance called ethyl nitrate, in which case the hydrogen liberated from the hydrochloric acid by the tin acts upon the elements of nitric acid-- C_{2}H_{5}·NO_{3} + 6H + HCl = NH_{4}OCl + H_{2}O + C_{2}H_{5}·OH Ethyl nitrate Hydrogen Hydroxylamine Water Alcohol from + HCl HCl and Sn Thus in this case the nitric acid is deoxidised, not directly into nitrogen, but into hydroxylamine. Hydroxylamine is also formed by passing nitric oxide, NO, into a mixture of tin and hydrochloric acid--that is, by the action of the hydrogen evolved on the nitric oxide, NO + 3H + HCl = NH_{4}OCl--and in many other cases. According to Lossen's method, a mixture of 30 parts of ethyl nitrate, 120 parts of tin, and 40 parts of a solution of hydrochloric acid of sp. gr. 1·06 are taken. After a certain time the reaction commences spontaneously. When the reaction has ceased the tin is separated by means of hydrogen sulphide, the solution is evaporated, and a large amount of sal-ammoniac is thus obtained (owing to the further action of hydrogen on the hydroxylamine compound, the hydrogen taking up oxygen from it and forming water); a solution ultimately remains containing the hydroxylamine salt; this salt is dissolved in anhydrous alcohol and purified by the addition of platinum chloride, which precipitates any ammonium salt still remaining in the solution. After concentrating the alcoholic solution the hydroxylamine hydrochloride separates in crystals. This substance melts at about 150°, and in so doing decomposes into nitrogen, hydrogen chloride, water, and sal-ammoniac. A sulphuric acid compound of hydroxylamine may be obtained by mixing a solution of the above salt with sulphuric acid. The sulphate is also soluble in water like the hydrochloride; this shows that hydroxylamine, like ammonia itself, forms a series of salts in which one acid may be substituted for another. It might he expected that by mixing a strong solution of a hydroxylamine salt with a solution of a caustic alkali hydroxylamine itself would be liberated, just as an ammonia salt under these circumstances evolves ammonia; but the liberated hydroxylamine is immediately decomposed with the formation of nitrogen and ammonia (and probably nitrous oxide), 3NH_{3}O = NH_{3} + 3H_{2}O + N_{2}. Dilute solutions give the same reaction, although very slowly, but by decomposing a solution of the sulphate with barium hydroxide a certain amount of hydroxylamine is obtained in solution (it is partly decomposed). Hydroxylamine in aqueous solution, like ammonia, precipitates basic hydrates, and it deoxidises the oxides of copper, silver, and other metals. Free hydroxylamine was obtained by Lobry de Bruyn (1891). It is a solid, colourless, crystalline substance, without odour, which does not melt below 27°. It has the property of dissolving metallic salts; for instance, sodium chloride. Hydroxylamine, when rapidly heated with platinum, decomposes with a flash and the formation of a yellow flame. It is almost insoluble in ordinary solvents like chloroform, benzine, acetic ether, and carbon bisulphide. Its aqueous solutions are tolerably stable, contain up to 60 per cent. (sp. gr. 1·15 at 20°), and may be kept for many weeks without undergoing any change. Lobry de Bruyn used the hydrochloric salt to prepare pure hydroxylamine. The salt was first treated with sodium methylate (CH_{3}NaO), and then methyl alcohol was added to the mixture. The precipitated sodium chloride was separated from the solution by filtration. (The methyl alcohol is added to prevent the precipitated chloride of sodium from coating the insoluble hydrochloric salt of hydroxylamine.) The methyl alcohol was driven off under a pressure 150-200 mm., and after extracting a further portion of methyl alcohol by ether and several fractional distillations, a solution was obtained containing 70 per cent. of free hydroxylamine, 8 per cent. water, 9·9 per cent. chloride of sodium, and 12·1 per cent. of the hydrochloric salt of hydroxylamine. Pure free hydroxylamine, NH_{3}O, is obtained by distilling under a pressure of 60 mm.; it then boils at 70°, and solidifies in a condenser cooled to 0° in the form of long needles. It melts at 33°, boils at 58° under a pressure of 22 mm., and has a sp. gr. of about 1·235 (Brühl). Under the action of NaHO it gives NH_{3} and NHO_{2} or N_{2}O, and forms nitric acid (Kolotoff, 1893) under the action of oxidising agents. Hydroxylamine is obtained in a great number of cases, for instance by the action of tin on dilute nitric acid, and also by the action of zinc on ethyl nitrate and dilute hydrochloric acid, &c. The relation between hydroxylamine, NH_{2}(OH), and nitrous acid, NO(OH), which is so clear in the sense of the law of substitutions, becomes a reality in those cases when reducing agents act on salts of nitrous acid. Thus Raschig (1888) proposed the following method for the preparation of the hydroxylamine sulphate. A mixture of strong solutions of potassium nitrite, KNO_{2}, and hydroxide, KHO, in molecular proportions, is prepared and cooled. An excess of sulphurous anhydride is then passed into the mixture, and the solution boiled for a long time. A mixture of the sulphates of potassium and hydroxylamine is thus obtained: KNO_{2} + KHO + 2SO_{2} + 2H_{2}O = NH_{2}(OH),H_{2}SO_{4} + K_{2}SO_{4}. The salts may be separated from each other by crystallisation. [25 bis] In order to illustrate the application of the law of substitution to a given case, and to show the connection between ammonia and the oxides of nitrogen, let us consider the possible products of an oxygen and hydroxyl substitution in caustic ammonia, NH_{4}(OH). It is evident that the substitution of H by OH can give: (1) NH_{3}(OH)_{2}; (2) NH_{2}(OH)_{3}; (3) NH(OH)_{4}; and (4) N(OH)_{5}. They should all, like caustic ammonia itself, easily part with water and form products (hydroxylic) of the oxidation of ammonia. The first of them is the hydrate of hydroxylamine, NH_{2}(OH) + H_{2}O; the second, NH(OH)_{2} + H_{2}O (and also the substance NH(OH)_{4} or NH_{3}O_{2}), containing, as it does, both hydrogen and oxygen, is able to part with all its hydrogen in the form of water (which could not be done by the first product, since it contained too little oxygen), forming, as the ultimate product, 2NH_{2}(OH)_{3}-5H_{2}O = N_{2}O--that is, it corresponds with nitrous oxide, or the lower degree of the oxidation of nitrogen. So, also, nitrous anhydride corresponds with the third of the above products, 2NH(OH)_{4}-5H_{2}O = N_{2}O_{3}, and nitric anhydride with the fourth, 2N(OH)_{5}-5H_{2}O = N_{2}O_{5}. As, in these three equations, two molecules of the substitution products (-5H_{2}O) are taken, it is also possible to combine two different products in one equation. For instance, the third and fourth products: NH(OH)_{4} + N(OH)_{5}-5H_{2}O corresponds to N_{2}O_{4} or 2NO_{2}, that is, to peroxide of nitrogen. Thus all the five (see later) oxides of nitrogen, N_{2}O, NO, N_{2}O_{3}, NO_{2}, and N_{2}O_{5}, may be deduced from ammonia. The above may be expressed in a general form by the equation (it should be remarked that the composition of all the substitution products of caustic ammonia may be expressed by NH_{3}O{5-_a_}, where _a_ varies between 0 and 4): NH_{5}O_{5 - _a_} + NH_{5}O{5 - _b_} - 5H_{2}O = N_{2}O_{5 - (_a_ + _b_)}, where _a_ + _b_ can evidently be not greater than 5; when _a_ + _b_ = 5 we have N_{2}--nitrogen, when = 4 we have N_{2}O nitrous oxide; when _a_ + _b_ = 3 we have N_{2}O_{2} or NO--nitric oxide, and so on to N_{2}O_{5}, when _a_ + _b_ = 0. Besides which it is evident that intermediate products may correspond with (and hence also break up into) different starting points; for instance, N_{2}O is obtained when _a_ + _b_ = 2, and this may occur either when _a_ = 0 (nitric acid), and _b_ = 2 (hydroxylamine), or when _a_ = _b_ = 1 (the third of the above substitution products). [26] Nitric acid corresponds with the anhydride N_{2}O_{5}, which will afterwards be described, but which must be regarded as the highest saline oxide of nitrogen, just as Na_{2}O (and the hydroxide NaHO) in the case of sodium, although sodium forms a peroxide possessing the property of parting with its oxygen with the same ease as hydrogen peroxide, if not on heating, at all events in reactions--for instance, with acids. So also nitric acid has its corresponding peroxide, which may be called pernitric acid. Its composition is not well known--probably NHO_{4}--so that its corresponding anhydride would be N_{2}O_{7}. It is formed by the action of a silent discharge on a mixture of nitrogen and oxygen, so that a portion of its oxygen is in a state similar to that in ozone. The instability of this substance (obtained by Hautefeuille, Chappuis, and Berthelot), which easily splits up with the formation of nitric peroxide, and its resemblance to persulphuric acid, which we shall afterwards describe, will permit our passing over the consideration of the little that is further known concerning it. [27] Phosphorus (Chapter XIX.) gives the hydride PH_{3}, corresponding with ammonia, NH_{3}, and forms phosphorous acid, PH_{3}O_{3}, which is analogous to nitrous acid, just as phosphoric acid is to nitric acid; but phosphoric (or, better, orthophosphoric) acid, PH_{3}O_{4}, is able to lose water and give pyro-and meta-phosphoric acids. The latter is equal to the ortho-acid minus water = PHO_{3}, and therefore nitric acid, NHO_{3}, is really meta-nitric acid. So also nitrous acid, HNO_{2}, is meta-nitrous (anhydrous) acid, and thus the ortho-acid is NH_{3}O_{3} = N(OH)_{3}. Hence for nitric acid we should expect to find, besides the ordinary or meta-nitric acid, HNO_{3} (= 1/2N_{2}O_{3},H_{2}O), and ortho-nitric acid, H_{3}NO_{4} (= 1/2N_{2}O_{3},3H_{2}O), an intermediate pyro-nitric acid, N_{2}H_{4}O_{7}, corresponding to pyrophosphoric acid, P_{2}H_{4}O_{7}. We shall see (for instance, in Chapter XVI., Note 21) that in nitric acid there is indeed an inclination of the ordinary salts (of the meta-acid), MNO_{3}, to combine with bases M_{2}O, and to approximate to the composition of ortho-compounds which are equal to meta-compound and bases (MNO_{3} + M_{2}O = M_{3}NO_{4}). 1. It is easy to prove the possibility of the oxidation of ammonia into nitric acid by passing a mixture of ammonia and air over heated spongy platinum. This causes the oxidation of the ammonia, nitric acid being formed, which partially combines with the excess of ammonia. The converse passage of nitric acid into ammonia is effected by the action of hydrogen at the moment of its evolution.[28] Thus metallic aluminium, evolving hydrogen from a solution of caustic soda, is able to completely convert nitric acid added to the mixture (as a salt, because the alkali gives a salt with the nitric acid) into ammonia, NHO_{3} + 8H = NH_{3} + 3H_{2}O. 2. In 1890 Curtius in Germany obtained a gaseous substance of the composition HN_{3} (hydrogen trinitride), having the distinctive properties of an acid, and giving, like hydrochloric acid, salts; for example, a sodium salt, NaN_{3}; ammonium salt, NH_{4}N_{3} = N_{4}H_{4}; barium salt, Ba(N_{3})_{2}, &c., which he therefore named hydronitrous acid, _HN__{3}.[28 bis] The extraordinary composition of the compound (ammonia, NH_{3}, contains one N atom and three H atoms; in HN_{3}, on the contrary, there are three N atoms and one H atom), the facile decomposition of its salts with an explosion, and above all its distinctly acid character (an aqueous solution shows a strong acid reaction to litmus), not only indicated the importance of this unexpected discovery, but at first gave rise to some perplexity as to the nature of the substance obtained, for the relations in which HN_{3} stood to other simple compounds of nitrogen which had long been known was not at all evident, and the scientific spirit especially requires that there should be a distinct bond between every innovation, every fresh discovery, and that which is already firmly established and known, for upon this basis is founded that apparently paradoxical union in science of a conservative stability with an irresistible and never-ceasing improvement. This missing, connection between the newly discovered hydronitrous acid, HN_{3}, and the long known ammonia, NH_{3}, and nitric acid, HNO_{3}, may be found in the law of substitution, starting from the well-known properties and composition of nitric acid and ammonia, as I mentioned in the 'Journal of the Russian Physico-Chemical Society' (1890). The essence of the matter lies in the fact that to the hydrate of ammonium, or caustic ammonia, NH_{4}OH, there should correspond, according to the law of substitution, an ortho-nitric acid (_see_ Note 27), H_{3}NO_{4} = NO(OH)_{3}, which equals NH_{4}(OH) with the substitution in it of (_a_) two atoms of hydrogen by oxygen (O--H_{2}) and (_b_) two atoms of hydrogen by the aqueous radicle (OH--H). Ordinary or meta-nitric acid is merely this ortho-nitric acid minus water. To ortho-nitric acid there should correspond the ammoniacal salts: mono-substituted, H_{2}NH_{4}NO_{4}; bi-substituted, H(NH_{4})_{2}NO_{4}; and tri-substituted, (NH_{4})_{3}NO_{4}. These salts, containing as they do hydrogen and oxygen, like many similar ammoniacal salts (see, for instance, Chapter IX.--Cyanides), are able to part with them in the form of water. Then from the first salt we have H_{2}NH_{4}NO_{4}-4H_{2}O = N_{2}O--nitrous oxide, and from the second H(NH_{4})_{2}NO4-4H_{2}O = HN_{3}--hydronitrous acid, and from the third (NH_{4})_{3}NO-4H_{2}O = N_{4}H_{4}--the ammonium salt of the same acid. The composition of HN_{3} should be thus understood, whilst its acid properties are explained by the fact that the water (4H_{2}O) from H(NH_{4})_{2}N_O{4} is formed at the expense of the hydrogen of the ammonium and oxygen of the nitric acid, so that there remains the same hydrogen as in nitric acid, or that which may be replaced by metals and give salts. Moreover, nitrogen undoubtedly belongs to that category of metalloids which give acids, like chlorine and carbon, and therefore, under the influence of three of its atoms, one atom of hydrogen acquires those properties which it has in acids, just as in HCN (hydrocyanic acid) the hydrogen has received these properties under the influence of the carbon and nitrogen (and HN_{3} may be regarded as HCN where C has been replaced by N_{2}). Moreover, besides explaining the composition and acid properties of HN_{3}, the above method gives the possibility of foretelling the closeness of the bond between hydronitrous acid and nitrous oxide, for N_{2}O + NH_{3} = HN_{3} + H_{2}O. This reaction, which was foreseen from the above considerations, was accomplished by Wislicenus (1892) by the synthesis of the sodium salt, by taking the amide of sodium, NH_{2}Na (obtained by heating Na in a current of NH_{3}), and acting upon it (when heated) with nitrous oxide, N_{2}O, when 2NH_{2}Na + N_{2}O = NaN_{3} + NaHO + NH_{3}. The resultant salt, NaN_{3}, gives hydronitrous acid when acted upon by sulphuric acid, NaN_{3} + H_{2}SO_{4} = NaHSO_{4} +HN_{3}. The latter gives, with the corresponding solutions of their salts, the insoluble (and easily explosive) salts of silver, AgN_{3} (insoluble, like AgCl or AgCN), and lead, Pb(N_{3})_{2}. [28] The formation of ammonia is observed in many cases of oxidation by means of nitric acid. This substance is even formed in the action of nitric acid on tin, especially if dilute acid be employed in the cold. A still more considerable amount of ammonia is obtained if, in the action of nitric acid, there are conditions directly tending to the evolution of hydrogen, which then reduces the acid to ammonia; for instance, in the action of zinc on a mixture of nitric and sulphuric acids. [28 bis] Curtius started with benzoylhydrazine, C_{6}H_{5}CONHNH_{2} (hydrazine, see Note 20 bis). (This substance is obtained by the action of hydrated hydrazine on the compound ether of benzoic acid). Benzoylhydrazine under the action of nitrous acid gives benzoylazoimide and water: C_{6}H_{5}CONHNH_{2} + NO_{2}H = C_{6}H_{5}CON_{3} + 2H_{2}O. Benzoylazoimide when treated with sodium alcoholate gives the sodium salt of hydronitrous acid: C_{6}H_{5}CON_{3} + C_{2}H_{3}ONa = C_{6}H_{5}O_{2}C_{2}H_{3} + NaN_{3}. The addition of ether to the resultant solution precipitates the NaN_{3}, and this salt when treated with sulphuric acid gives gaseous hydronitrous acid, HN_{3}. It has an acrid smell, and is easily soluble in water. The aqueous solution exhibits a strongly acid reaction. Metals dissolve in this solution and give the corresponding salts. With hydronitrous acid gaseous ammonia forms a white cloud, consisting of the salt of ammonium, NH_{4}N_{3}. This salt separates out from an alcoholic solution in the form of white lustrous scales. The salts of hydronitrous acid are obtained by a reaction of substitution with the sodium or ammonium salts. In this manner Curtius obtained and studied the salts of silver (AgN_{3}), mercury (HgN_{3}), lead (PbN_{6}), barium (BaN_{6}). With hydrazine, N_{2}H_{4}, hydronitrous acid forms saline compounds in the composition of which there are one or two particles of N_{3}H per one particle of hydrazine; thus N_{5}H_{5} and N_{8}H_{6}. The first was obtained in an almost pure form. It crystallises from an aqueous solution in dense, volatile, lustrous prisms (up to 1 in. long), which fuse at 50°, and deliquesce in the air; from a solution in boiling alcohol it separates out in bright crystalline plates. This salt, N_{5}H_{5}, has the same empirical composition, NH, as the ammonium salt of hydronitrous acid, N_{4}H_{4}, and imide; but their molecules and structure are different. Curtius also obtained (1893) hydronitrous acid by passing the vapour of N_{2}O_{5} (evolved by the action of HNO_{3} on As_{2}O_{3}) into a solution of hydrazine, N_{2}H_{4}. Similarly Angeli, by acting upon a saturated solution of silver nitrite with a strong solution of hydrazine, obtained the explosive AgN_{3} in the form of a precipitate, and this reaction, which is based upon the equation N_{2}H_{4} + NHO_{2} = HN_{3} + 2H_{2}O, proceeds so easily that it forms an experiment for the lecture table. A thermal investigation of hydronitrous acid by Berthelot and Matignon gave the following figures for the heat of solution of the ammonium salt N_{3}HNH_{3} (1 grm. in 100 parts of water)-708 C., and for the heat of neutralisation by barium hydrate +10·0 C., and by ammonia +8·2 C. The heat of combustion of N_{4}H_{4} (+163·8 C. at a constant vol.) gives the heat of formation of the salt N_{4}H_{4} (solid) as -25·3 C. and (solution)-32·3 C.; this explains the explosive nature of this compound. In its heat of formation from the elements N_{3}H =-62·6 C., this compound differs from all the hydrogen compounds of nitrogen in having a maximum absorption of heat, which explains its instability. The compounds of nitrogen with oxygen present an excellent example of the law of multiple proportions, because they contain, for 14 parts by weight of nitrogen, 8, 16, 24, 32, and 40 parts respectively by weight of oxygen. The composition of these compounds is as follows:-- N_{2}O, nitrous oxide; hydrate NHO. N_{2}O_{2}, nitric oxide, NO. N_{2}O_{3}, nitrous anhydride; hydrate NHO_{2}. N_{2}O_{4}, peroxide of nitrogen, NO_{2}. N_{2}O_{5}, nitric anhydride; hydrate NHO_{3}. Of these compounds,[29] nitrous and nitric oxides, peroxide of nitrogen, and nitric acid, NHO_{3}, are characterised as being the most stable. _The lower oxides, when coming into contact with the higher, may give the intermediate forms_; for instance, NO and NO_{2} form N_{2}O_{3}, _and the intermediate oxides may, in splitting up, give a higher and lower oxide_. So N_{2}O_{4} gives N_{2}O_{3} and N_{2}O_{5}, or, in the presence of water, their hydrates. [29] According to the thermochemical determinations of Favre, Thomsen, and more especially of Berthelot, it follows that, in the formation of such quantities of the oxides of nitrogen as express their formulæ, if gaseous nitrogen and oxygen be taken as the starting points, and if the compounds formed be also gaseous, the following amounts of heat, expressed in thousands of heat units, are _absorbed_ (hence a minus sign):-- N_{2}O N_{2}O_{2} N_{2}O_{3} N_{2}O_{4} N_{2}O_{5} -21 -43 -22 -5 -1 -22 +21 +17 +4 The difference is given in the lower line. For example, if N_{2}, or 28 grams of nitrogen, combine with O--that is, with 16 grams of oxygen--then 21,000 units of heat are absorbed, that is, sufficient heat to raise 21,000 grams of water through 1°. Naturally, direct observations are impossible in this case; but if charcoal, phosphorus, or similar substances are burnt both in nitrous oxide and in oxygen, and the heat evolved is observed in both cases, then the difference (more heat will be evolved in burning in nitrous oxide) gives the figures required. If N_{2}O_{2}, by combining with O_{2}, gives N_{2}O_{4}, then, as is seen from the table, heat should be developed, namely, 38,000 units of heat, or NO + O = 19,000 units of heat. The differences given in the table show that the maximum absorption of heat corresponds with nitric oxide, and that the higher oxides are formed from it with evolution of heat. If liquid nitric acid, NHO_{3}, were decomposed into N + O_{3} + H, then 41,000 heat units would be required; that is, an evolution of heat takes place in its formation from the gases. It should be observed that the formation of ammonia, NH_{3}, from the gases N + H_{3} evolves 12·2 thousand heat units. We have already seen that, under certain conditions, nitrogen combines with oxygen, and we know that ammonia may he oxidised. In these cases various oxidation products of nitrogen are formed, but in the presence of water and an excess of oxygen they always give nitric acid. Nitric acid, as corresponding with the highest oxide, is able, in deoxidising, to give the lower oxides; it is the only nitrogen acid whose salts occur somewhat widely in nature, and it has many technical uses, for which reason we will begin with it. _Nitric acid_, NHO_{3}, is likewise known as aqua fortis. In a free state it is only met with in nature in small quantities, in the air and in rain-water after storms; but even in the atmosphere nitric acid does not long remain free, but combines with ammonia, traces of which are always found in air. On falling on the soil and into running water, &c., the nitric acid everywhere comes into contact with bases (or their carbonates), which easily act on it, and therefore it is converted into the nitrates of these bases. Hence nitric acid is always met with in the form of salts in nature. The soluble salts of nitric acid are called _nitres_. This name is derived from the Latin _sal nitri_. The potassium salt, KNO_{3}, is common nitre, and the sodium salt, NaNO_{3}, Chili saltpetre, or cubic nitre. Nitres are formed in the soil when a nitrogenous substance is slowly oxidised in the presence of an alkali by means of the oxygen of the atmosphere. In nature there are very frequent instances of such oxidation. For this reason certain soils and rubbish heaps--for instance, lime rubbish (in the presence of a base)--lime contain a more or less considerable amount of nitre. One of these nitres--sodium nitrate--is extracted from the earth in large quantities in Chili, where it was probably formed by the oxidation of animal refuse. This kind of nitre is employed in practice for the manufacture of nitric acid and the other oxygen compounds of nitrogen. Nitric acid is obtained from _Chili saltpetre_ by heating it with _sulphuric acid_. The hydrogen of the sulphuric acid replaces the sodium in the nitre. The sulphuric acid then forms either an acid salt, NaHSO_{4}, or a normal salt, Na_{2}SO_{4}, whilst nitric acid is formed from the nitre and is volatilised. The decomposition is expressed by the equations: (1) NaNO_{3} + H_{2}SO_{4} = HNO_{3} + NaHSO_{4}, if the acid salt be formed, and (2) 2NaNO_{3} + H_{2}SO_{4} = Na_{2}SO_{4} + 2HNO_{3}, if the normal sodium sulphate is formed. With an excess of sulphuric acid, at a moderate heat, and at the commencement of the reaction, the decomposition proceeds according to the first equation; and on further heating with a sufficient amount of nitre according to the second, because the acid salt NaHSO_{4} itself acts like an acid (its hydrogen being replaceable as in acids), according to the equation NaNO_{3} + NaHSO_{4} = Na_{2}SO_{4} + HNO_{3}. [Illustration: FIG. 47.--Method of preparing nitric acid on a large scale. A cast-iron retort, C, is fixed into the furnace, and heated by the fire, B. The flame and products of combustion are at first led along the flue, M (in order to heat the receivers), and afterwards into L. The retort is charged with Chili saltpetre and sulphuric acid, and the cover is luted on with clay and gypsum. A clay tube, _a_, is fixed into the neck of the retort (in order to prevent the nitric acid from corroding the cast iron), and a bent glass tube, D, is luted on to it. This tube carries the vapours into a series of earthenware receivers, E. Nitric acid mixed with sulphuric acid collects in the first. The purest nitric acid is procured from the second, whilst that which condenses in the third receiver contains hydrochloric acid, and that in the fourth nitrous oxide. Water is poured into the last receiver in order to condense the residual vapours.] The sulphuric acid, as it is said, here displaces the nitric acid from its compound with the base.[29 bis] Thus, in the reaction of sulphuric acid on nitre there is formed a non-volatile salt of sulphuric acid, which remains, together with an excess of this acid, in the distilling apparatus, and nitric acid, which is converted into vapour, and may be condensed, because it is a liquid and volatile substance. On a small scale, this reaction may be carried on in a glass retort with a glass condenser. On a large scale, in chemical works, the process is exactly similar, only iron retorts are employed for holding the mixture of nitre and sulphuric acid, and earthenware three-necked bottles are used instead of a condenser,[30] as shown in fig. 47. [29 bis] This often gives rise to the supposition that sulphuric acid possesses a considerable degree of affinity or energy compared with nitric acid, but we shall afterwards see that the idea of the relative degree of affinity of acids and bases is, in many cases, exceedingly unbiassed; it need not be accepted so long as it is possible to explain the observed phenomena without admitting any supposition whatever of the degree of the force of affinity, because the latter cannot be measured. The action of sulphuric acid upon nitre may be explained by the fact alone that the resultant nitric acid is volatile. The nitric acid is the only one of all the substances partaking in the reaction which is able to pass into vapour; it alone is volatile, while the remainder are non-volatile, or, more strictly speaking, exceedingly difficultly volatile substances. Let us imagine that the sulphuric acid is only able to set free a small quantity of nitric acid from its salt, and this will suffice to explain the decomposition of the whole of the nitre by the sulphuric acid, because once the nitric acid is separated it passes into vapour when heated, and passes away from the sphere of action of the remaining substances; then the free sulphuric acid will set free a fresh small quantity of nitric acid, and so on until it drives off the entire quantity. It is evident that, in this explanation, it is essential that the sulphuric acid should be in excess (although not greatly) throughout the reaction; according to the equation expressing the reaction, 98 parts of sulphuric acid are required per 85 parts of Chili nitre; but if this proportion be maintained in practice the nitric acid is not all disengaged by the sulphuric acid; an excess of the latter must be taken, and generally 80 parts of Chili nitre are taken per 98 parts of acid, so that a portion of the sulphuric acid remains free to the very end of the reaction. [30] It must be observed that sulphuric acid, at least when undiluted (60° Baumé), corrodes cast iron with difficulty, so that the acid may be heated in cast-iron retorts. Nevertheless, both sulphuric and nitric acids have a certain action on cast iron, and therefore the acid obtained will contain traces of iron. In practice sodium nitrate (Chili saltpetre) is usually employed because it is cheaper, but in the laboratory it is best to take potassium nitrate, because it is purer and does not froth up so much as sodium nitrate when heated with sulphuric acid. In the action of an excess of sulphuric acid on nitre and nitric acid a portion of the latter is decomposed, forming lower oxides of nitrogen, which are dissolved in the nitric acid. A portion of the sulphuric acid itself is also carried over as spray by the vapours of the nitric acid. Hence sulphuric acid occurs as an impurity in commercial nitric acid. A certain amount of hydrochloric acid will also be found to be present in it, because sodium chloride is generally found as an impurity in nitre, and under the action of sulphuric acid it forms hydrochloric acid. Commercial acid further contains a considerable excess of water above that necessary for the formation of the hydrate, because water is first poured into the earthenware vessels employed for condensing the nitric acid in order to facilitate its cooling and condensation. Further, the acid of composition HNO_{3} decomposes with great ease, with the evolution of oxides of nitrogen. Thus the commercial acid contains a great number of impurities, and is frequently purified in the following manner:--Lead nitrate is first added to the acid because it forms non-volatile and almost insoluble (precipitated) substances with the free sulphuric and hydrochloric acids, and liberates nitric acid in so doing, according to the equations Pb(NO_{3})_{2} + 2HCl = PbCl_{2} + 2NHO_{3} and Pb(NO_{3})_{2} + H_{2}SO_{4} = PbSO_{4} + 2NHO_{3}. Potassium chromate is then added to the impure nitric acid, by which means oxygen is liberated from the chromic acid, and this oxygen, at the moment of its evolution, oxidises the lower oxides of nitrogen and converts them into nitric acid. A pure nitric acid, containing no impurities other than water, may be then obtained by carefully distilling the acid, treated as above described, and particularly if only the middle portions of the distillate are collected. Such acid should give no precipitate, either with a solution of barium chloride (a precipitate shows the presence of sulphuric acid) or with a solution of silver nitrate (a precipitate shows the presence of hydrochloric acid), nor should it, after being diluted with water, give a coloration with starch containing potassium iodide (a coloration shows the admixture of other oxides of nitrogen). The oxides of nitrogen may be most easily removed from impure nitric acid by heating for a certain time with a small quantity of pure charcoal. By the action of nitric acid on the charcoal carbonic anhydride is evolved, which carries off the lower oxides of nitrogen. On redistilling, pure acid is obtained. The oxides of nitrogen occurring in solution may also be removed by passing air through the nitric acid. Nitric acid so obtained always contains water. It is extremely difficult to deprive it of all the admixed water without destroying a portion of the acid itself and partially converting it into lower oxides, because without the presence of an excess of water it is very unstable. When rapidly distilled a portion is decomposed, and there are obtained free oxygen and lower oxides of nitrogen, which, together with the water, remain in solution with the nitric acid. Therefore it is necessary to work with great care in order to obtain a pure hydrate of nitric acid, HNO_{3}, and especially to mix the nitric acid obtained from nitre, as above described, with sulphuric acid, which takes up the water, and to distil it at the lowest possible temperature--that is, by placing the retort holding the mixture in a water or oil bath and carefully heating it. The first portion of the nitric acid thus distilled boils at 86°, has a specific gravity at 15° of 1·526, and solidifies at -50°; it is very unstable at higher temperatures. This is the normal hydrate, HNO_{3}, which corresponds with the salts, NMO_{3}, of nitric acid. When diluted with water nitric acid presents a higher boiling point, not only as compared with that of the nitric acid itself, but also with that of water; so that, if very dilute nitric acid be distilled, the first portions passing over will consist of almost pure water, until the boiling point in the vapours reaches 121°. At this temperature a compound of nitric acid with water, containing about 70 p.c. of nitric acid,[31] distils over; its specific gravity at 15° = 1·421. If the solution contain less than 25 p.c. of water, then, the specific gravity of the solution being above 1·44, HNO_{3} evaporates off and fumes in the air, forming the above hydrate, whose vapour tension is less than that of water. Such solutions form _fuming nitric acid_. On distilling it gives monohydrated acid,[32] HNO_{3}; it is a hydrate boiling at 121°, so that it is obtained from both weak and strong solutions. Fuming nitric acid, under the action not only of organic substances, but even of heat, loses a portion of its oxygen, forming lower oxides of nitrogen, which impart a _red-brown colour_ to it;[33] the pure acid is colourless. [31] Dalton, Smith, Bineau, and others considered that the hydrate of constant boiling point (see Chapter I., Note 60) for nitric acid was the compound 2HNO_{3},3H_{2}O, but Roscoe showed that its composition changes with a variation of the pressure and temperature under which the distillation proceeds. Thus, at a pressure of 1 atmosphere the solution of constant boiling point contains 68·6 p.c., and at one-tenth of an atmosphere 66·8 p.c. Judging from what has been said concerning solutions of hydrochloric acid, and from the variation of specific gravity, I think that the comparatively large decrease in the tensions of the vapours depends on the formation of a hydrate, NHO_{3},2H_{2}O (= 63·6 p.c.). Such a hydrate may be expressed by N(HO)_{5}, that is, as NH_{4}(HO), in which all the equivalents of hydrogen are replaced by hydroxyl. The constant boiling point will then be the temperature of the decomposition of this hydrate. The variation of the specific gravity at 15° from water (_p_ = 0) to the hydrate NHO_{3},5H_{2}O (41·2 p.c. HNO_{3}) is expressed by _s_ = 9992 + 57·4_p_ + 0·16_p^2_, if water = 10,000 at 4°. For example, when _p_ = 30 p.c., _s_ = 11,860. For more concentrated solutions, at least, the above-mentioned hydrate, HNO_{3},2H_{2}O, must be taken, up to which the specific gravity _s_ = 9570 + 84·18_p_-0·240_p_^2; but perhaps (since the results of observations of the specific gravity of the solutions are not in sufficient agreement to arrive at a conclusion) the hydrate HNO_{3},3H_{2}O should be recognised, as is indicated by many nitrates (Al, Mg, Co, &c.), which crystallise with this amount of water of crystallisation. From HNO_{3},2H_{2}O to HNO_{3} the specific gravity of the solutions (at 15°) _s_ = 10,652 + 62·08_p_-0·160_p_^2. The hydrate HNO_{3},2H_{2}O is recognised by Berthelot on the basis of the thermochemical data for solutions of nitric acid, because on approaching to this composition there is a rapid change in the amount of heat evolved by mixing nitric acid with water. Pickering (1892) by refrigeration obtained the crystalline hydrates: HNO_{3},H_{2}O, melting at -37° and HNO_{3},3H_{2}O, melting at -18°. A more detailed study of the reactions of hydrated nitric acid would no doubt show the existence of change in the process and rapidity of reaction in approaching these hydrates. [32] The normal hydrate HNO_{3}, corresponding with the ordinary salts, may be termed the monohydrated acid, because the anhydride N_{2}O_{5} with water forms this normal nitric acid. In this sense the hydrate HNO_{3},2H_{2}O is the pentahydrated acid. [33] For technical and laboratory purposes recourse is frequently had to _red fuming nitric acid_--that is, the normal nitric acid, HNO_{3}, containing lower oxides of nitrogen in solution. This acid is prepared by decomposing nitre with half its weight of strong sulphuric acid, or by distilling nitric acid with an excess of sulphuric acid. The normal nitric acid is first obtained, but it partially decomposes, and gives the lower oxidation products of nitrogen, which are dissolved by the nitric acid, to which they impart its usual pale-brown or reddish colour. This acid fumes in the air, from which it attracts moisture, forming a less volatile hydrate. If carbonic anhydride be passed through the red-brown fuming nitric acid for a long period of time, especially if, assisted by a moderate heat, it expels all the lower oxides, and leaves a colourless acid free from these oxides. It is necessary, in the preparation of the red acid, that the receivers should be kept quite cool, because it is only when cold that nitric acid is able to dissolve a large proportion of the oxides of nitrogen. The strong red fuming acid has a specific gravity 1·56 at 20°, and has a suffocating smell of the oxides of nitrogen. When the red acid is mixed with water it turns green, and then of a bluish colour, and with an excess of water ultimately becomes colourless. This is owing to the fact that the oxides of nitrogen in the presence of water and nitric acid are changed, and give coloured solutions. Markleffsky (1892) showed that the green solutions contain (besides HNO_{3}) HNO_{2} and N_{2}O_{4}, whilst the blue solutions only contain HNO_{2} (_see_ Note 48). The action of red fuming nitric acid (or a mixture with sulphuric acid) is in many cases very powerful and rapid, and it sometimes acts differently from pure nitric acid. Thus iron becomes covered with a coating of oxides, and insoluble in acids; it becomes, as is said, passive. Thus chromic acid (and potassium dichromate) gives oxide of chromium in this red acid--that is, it is deoxidised. This is owing to the presence of the lower oxides of nitrogen, which are capable of being oxidised--that is, of passing into nitric acid like the higher oxides. But, generally, the action of fuming nitric acid, both red and colourless, is powerfully oxidising. Nitric acid, as an _acid hydrate_, enters into reactions of double decomposition with bases, basic hydrates (alkalis), and with salts. In all these cases a salt of nitric acid is obtained. An alkali and nitric acid give water and a salt; so, also, a basic oxide with nitric acid gives a salt and water; for instance, lime, CaO + 2HNO_{3} = Ca(NO_{3})_{2} + H_{2}O. Many of these salts are termed nitres.[34] The composition of the ordinary salts of nitric acid may be expressed by the general formula M(NO_{3})_{_n_}, where M indicates a metal replacing the hydrogen in one or several (_n_) equivalents of nitric acid. We shall find afterwards that the atoms M of metals are equivalent to one (K, Na, Ag) atom of hydrogen, or two (Ca, Mg, Ba), or three (Al, In), or, in general, _n_ atoms of hydrogen. _The salts of nitric acid_ are especially characterised by being all _soluble in water_.[35] From the property common to all these salts of entering into double decompositions, and owing to the volatility of nitric acid, they evolve nitric acid when heated with sulphuric acid. They all, like the acid itself, are capable of evolving oxygen when heated, and consequently of acting as oxidising substances; they therefore, for instance, deflagrate with ignited carbon, the carbon burning at the expense of the oxygen of the salt and forming gaseous products of combustion.[36] [34] Hydrogen is not evolved in the action of nitric acid (especially strong) on metals, even with those metals which evolve hydrogen under the action of other acids. This is because the hydrogen at the moment of its separation reduces the nitric acid, with formation of the lower oxides of nitrogen, as we shall afterwards see. [35] Certain basic salts of nitric acid, however (for example, the basic salt of bismuth), are insoluble in water; whilst, on the other hand, all the normal salts are soluble, and this forms an exceptional phenomenon among acids, because all the ordinary acids form insoluble salts with one or another base. Thus, for sulphuric acid the salts of barium, lead, &c., for hydrochloric acid the salts of silver, &c., are insoluble in water. However, the normal salts of acetic and certain other acids are all soluble. [36] _Ammonium nitrate_, NH_{4}NO_{3}, is easily obtained by adding a solution of ammonia or of ammonium carbonate to nitric acid until it becomes neutral. On evaporating this solution, crystals of the salt are formed which contain no water of crystallisation. It crystallises in prisms like those formed by common nitre, and has a refreshing taste; 100 parts of water at _t_° dissolve 54 + 0·61_t_ parts by weight of the salt. It is soluble in alcohol, melts at 160°, and is decomposed at about 180°, forming water and nitrous oxide, NH_{4}NO_{3} = 2H_{2}O + N_{2}O. If ammonium nitrate be mixed with sulphuric acid, and the mixture be heated to about the boiling point of water, then nitric acid is evolved, and ammonium hydrogen sulphate remains in solution; but if the mixture be heated rapidly to 16O°, then nitrous oxide is evolved. In the first case the sulphuric acid takes up ammonia, and in the second place water. Ammonium nitrate is employed in practice for the artificial production of cold, because in dissolving in water it lowers the temperature very considerably. For this purpose it is best to take equal parts by weight of the salt and water. The salt must first be reduced to a powder and then rapidly stirred up in the water, when the temperature will fall from +15° to -10°, so that the water freezes. Ammonium nitrate absorbs ammonia, with which it forms unstable compounds resembling compounds containing water of crystallisation. (Divers 1872, Raoult 1873.) At -10° NH_{4}NO_{3},2NH_{3} is formed: it is a liquid of sp. gr. 1·15, which loses all its ammonia under the influence of heat. At +28° NH_{4}NO_{3},NH_{3} is formed: it is a solid which easily parts with its ammonia when heated, especially in solution. Troost (1882) investigated the tension of the dissociation of the compounds formed, and came to the conclusion that a definite compound corresponding to the formula 2NH_{4}NO_{3},3NH_{3} is formed, because the tension of dissociation remains constant in the decomposition of such a compound at 0°. Y. Kouriloff (1893), however, considers that the constancy of the tension of the ammonia evolved is due to the decomposition of a saturated solution, and not of a definite compound. During decomposition the system is composed of a liquid and a solid; the tension only becomes constant from the moment the solid falls down. The composition 2NH_{4}NO_{3},3NH_{3} corresponds to a saturated solution at 0°, and the solubility of NH_{4}NO_{3} in NH_{3} increases with a rise of temperature. Nitric acid also enters into double decompositions with a number of hydrocarbons not in any way possessing alkaline characters and not reacting with other acids. Under these circumstances the nitric acid gives water and a new substance termed a _nitro-compound_. The chemical character of the nitro-compound is the same as that of the original substance; for example, if an indifferent substance be taken, then the nitro compound obtained from it will also be indifferent; if an acid be taken, then an acid is obtained also.[36 bis] Benzene, C_{6}H_{6}, for instance, acts according to the equation C_{6}H_{6} + HNO_{3} = H_{2}O + C_{6}H_{5}NO_{2}. Nitrobenzene is produced. The substance taken, C_{6}H_{6}, is a liquid hydrocarbon having a faint tarry smell, boiling at 80°, and lighter than water; by the action of nitric acid nitrobenzene is obtained, which is a substance boiling at about 210°, heavier than water, and having an almond-like odour: it is employed in large quantities for the preparation of aniline and aniline dyes.[37] As the nitro-compounds contain both combustible elements (hydrogen and carbon), as well as oxygen in unstable combination with nitrogen, in the form of the radicle NO_{2} of nitric acid, they decompose with an explosion when ignited or even struck, owing to the pressure of the vapours and gases formed--free nitrogen, carbonic anhydride, CO_{2}, carbonic oxide, CO, and aqueous vapour. In the explosion of nitro compounds[37 bis] much heat is evolved, as in the combustion of gunpowder or detonating gas, and in this case the force of explosion in a closed space is great, because from a solid or liquid nitro-compound occupying a small space there proceed vapours and gases whose elasticity is great not only from the small space in which they are formed, but owing to the high temperature corresponding to the combustion of the nitro-compound.[38] [36 bis] This is explained by saying that in true nitro-compounds the residue of nitric acid NO_{2} takes the place of the hydrogen in the hydrocarbon group. For example, if C_{6}H_{5}OH be given, then C_{6}H_{4}(NO_{2})OH will be a true nitro-compound having the radical properties of C_{6}H_{5}OH. If, on the other hand, the NO_{2} replace the hydrogen of the aqueous radicle (C_{6}H_{5}ONO_{2}), then the chemical character varies, as in the passage of KOH into KONO_{2} (nitre) (_see_ Note 37 and Organic Chemistry). [37] The compound ethers of nitric acid in which the hydrogen of the aqueous radicle (OH) is replaced by the residue of nitric acid (NO_{2}) are frequently called nitro-compounds. But in their chemical character they differ from true nitro-compounds (for details _see_ Organic Chemistry) and do not burn like them. The action of nitric acid on cellulose, C_{6}H_{10}O_{5}, is an example. This substance, which forms the outer coating of all plant cells, occurs in an almost pure state in cotton, in common writing-paper, and in flax, &c.; under the action of nitric acid it forms water and nitrocellulose (like water and KNO_{3} from KHO), which, although it has the same appearance as the cotton originally taken, differs from it entirely in properties. It explodes when struck, bursts into flame very easily under the action of sparks, and acts like gunpowder, whence its name of pyroxylin, or gun-cotton. The composition of gun-cotton is C_{6}H_{7}N_{3}O_{11} = C_{6}H_{10}O_{5} + 3NHO_{3}-3H_{2}O. The proportion of the group NO_{2} in nitrocellulose may be decreased by limiting the action of the nitric acid and compounds obtained with different properties; for instance, the (impure) well-known _collodion cotton_, containing from 11 to 12 per cent. of nitrogen, and _pyro-collodion_ (Mendeléeff, 1890), containing 12·4 per cent. of nitrogen. Both these products are soluble in a mixture of alcohol and ether (in collodion a portion of the substance is soluble in alcohol), and the solution when evaporated gives a transparent film, which is insoluble in water. A solution of collodion is employed in medicine for covering wounds, and in wet-plate photography for giving on glass an even coating of a substance into which the various reagents employed in the process are introduced. Extremely fine threads (obtained by forcing a gelatinous mixture of collodion, ether, and alcohol through capillary tubes in water) of collodion form artificial silk. [37 bis] The property possessed by nitroglycerin (occurring in dynamite), nitrocellulose, and the other nitro-compounds, of burning with an explosion, and their employment for smokeless powder and as explosives in general, depends on the reasons in virtue of which a mixture of nitre and charcoal deflagrates and explodes; in both cases the elements of the nitric acid occurring in the compound are decomposed, the oxygen in burning unites with the carbon, and the nitrogen is set free; thus a very large volume of gaseous substances (nitrogen and oxides of carbon) is rapidly formed from the solid substances originally taken. These gases occupy an incomparably larger volume than the original substance, and therefore produce a powerful pressure and explosion. It is evident that in exploding with the development of heat (that is, in decomposing, not with the absorption of energy, as is generally the case, but with the evolution of energy) the nitro-compounds form stores of energy which are easily set free, and that consequently their elements occur in a state of particularly energetic motion, which is especially strong in the group NO_{2}: this group is common to all nitro-compounds, and all the oxygen compounds of nitrogen are unstable, easily decomposable, and (Note 29) absorb heat in their formation. On the other hand, the nitro-compounds are instructive as an example and proof of the fact that the elements and groups forming compounds are united in definite order in the molecules of a compound. A blow, concussion, or rise of temperature is necessary to bring the combustible elements C and H into the most intimate contact with NO_{2}, and to distribute the elements in a new order in new compounds. As regards the composition of the nitro-compounds, it will be seen that the hydrogen of a given substance is replaced by the complex group NO_{2} of the nitric acid. The same is observed in the passage of alkalis into nitrates, so that the reactions of substitution of nitric acid--that is, the formation of salts and nitro-compounds--may be expressed in the following manner. In these cases the hydrogen is replaced by the so-called _radicle of nitric acid_ NO_{2}, as is evident from the following table:-- {Caustic potash KHO. {Nitre K(NO_{2})O. {Hydrate of lime CaH_{2}O_{2}. {Calcium nitrate Ca(NO_{2})_{2}O_{2}. {Glycerin C_{3}H_{5}H_{3}O_{3}. {Nitroglycerin C_{3}H_{5}(NO_{2})_{3}O_{3}. {Phenol C_{6}H_{5}OH. {Picric acid C_{6}H_{2}(NO_{2})_{3}OH, &c. The difference between the salts formed by nitric acid and the nitro-compounds consists in the fact that nitric acid is very easily separated from the salts of nitric acid by means of sulphuric acid (that is, by a method of double saline decomposition), whilst nitric acid is not displaced by sulphuric acid from true nitro-compounds; for instance, nitrobenzene, C_{6}H_{5}·NO_{2}. As nitro-compounds are formed exclusively from hydrocarbons, they are described with them in organic chemistry. The group NO_{2} of nitro-compounds in many cases (like all the oxidised compounds of nitrogen) passes into the ammonia group or into the ammonia radicle NH_{2}. This requires the action of reducing substances evolving hydrogen: RNO_{2} + 6H = RNH_{3} + 2H_{2}O. Thus Zinin converted nitrobenzene, C_{6}H_{5}·NO_{2}, into aniline, C_{6}H_{5}·NH_{2}, by the action of hydrogen sulphide. Admitting the existence of the group NO_{2}, as replacing hydrogen in various compounds, then nitric acid may be considered as water in which half the hydrogen is replaced by the radical of nitric acid. In this sense nitric acid is nitro-water, NO_{2}OH, and its anhydride dinitro-water, (NO_{2})_{2}O. In nitric acid the radical of nitric acid is combined with hydroxyl, just as in nitrobenzene it is combined with the radical of benzene. It should here be remarked that the group NO_{3} may be recognised in the salts of nitric acid, because the salts have the composition M(NO_{3})_{n}, just as the metallic chlorides have the composition MCl_{n}. But the group NO_{3} does not form any other compounds beyond the salts, and therefore it should he considered as hydroxyl, HO, in which H is replaced by NO_{2}. [38] The nitro-compounds play a very important part in mining and artillery. Detailed accounts of them must be looked for in special works, among which the works of A. R. Shuliachenke and T. M. Chelletsoff occupy an important place in the Russian literature on this subject, although historically the scientific works of Abel in England and Berthelot in France stand pre-eminent. The latter elucidated much in connection with explosive compounds by a series of both experimental and theoretical researches. Among explosives a particularly important place from a practical point of view is occupied by ordinary or black gunpowder (Chapter XIII., Note 16), fulminating mercury (Chapter XVI., Note 26), the different forms of gun-cotton (Chapter VI., Note 37), and nitro-glycerine (Chapter VIII., Note 45, and Chapter XII., Note 33). The latter when mixed with solid pulverulent substances, like magnesia, tripoli, &c., forms dynamite, which is so largely used in quarries and mines in driving tunnels, &c. We may add that the simplest true nitro-compound, or marsh gas, CH_{4}, in which all the hydrogens are replaced by NO_{2} groups has been obtained by L. N. Shishkoff, C(NO_{2})_{4}, as well as nitroform, CH(NO_{2})_{3}. [Illustration: FIG. 48.--The method of decomposition of nitrous anhydride, also applicable to the other oxides of nitrogen, and to their analysis. NO_{2} is generated from nitrate of lead in the retort A. Nitric acid and other less volatile products are condensed in B. The tube C C contains copper, and is heated from below. Undecomposed volatile products (if any are formed) are condensed in D, which is cooled. If the decomposition be incomplete, brown fumes make their appearance in this receiver. The gaseous nitrogen is collected in the cylinder E.] If the vapour of nitric acid is passed through an even moderately heated glass tube, the formation of dark-brown fumes of the lower oxides of nitrogen and the separation of free oxygen may be observed, 2NHO_{3} = H_{2}O + 2NO_{2} + O. The decomposition is complete at a white heat--that is, nitrogen is formed, 2NHO_{3} = H_{2}O + N_{2} + O_{5}. Hence it is easily understood that nitric acid may part with its oxygen to a number of substances capable of being oxidised.[39] It is consequently an _oxidising agent_. Charcoal, as we have already seen, burns in nitric acid; phosphorus, sulphur, iodine, and the majority of metals also decompose nitric acid, some on heating and others even at the ordinary temperature: the substances taken are oxidised and the nitric acid is deoxidised, yielding compounds containing less oxygen. Only a few metals, such as gold and platinum, do not act on nitric acid, but the majority decompose it; in so doing, an oxide of the metal is formed, which, if it has the character of a base, acts on the remaining nitric acid; hence, with the majority of metals the result of the reaction is usually not an oxide of the metal, but the corresponding salt of nitric acid, and, at the same time, one of the lower oxides of nitrogen. The resulting salts of the metals are soluble, and hence it is said that nitric acid _dissolves_ nearly all metals.[40] This case is termed the solution of metals by acids, although it is not a case of simple solution, but a complex chemical change of the substances taken. When treated with this acid, those metals whose oxides do not combine with nitric acid yield the oxide itself, and not a salt; for example, tin acts in this manner on nitric acid, forming a hydrated oxide, SnH_{2}O_{3}, which is obtained in the form of a white powder, Sn + 4NHO_{3} = H_{2}SnO_{3} + 4NO_{2} + H_{2}O. Silver is able to take up still more oxygen, and to convert a large portion of nitric acid into nitrous anhydride, 4Ag + 6HNO_{3} = 4AgNO_{3} + N_{2}O_{3} + 3H_{2}O. Copper takes up still more oxygen from nitric acid, converting it into nitric oxide, and, by the action of zinc, nitric acid is able to give up a still further quantity of nitrogen, forming nitrous oxide, 4Zn + 10NHO_{3} = 4Zn(NO_{3})_{2} + N_{2}O + 5H_{2}O.[41] Sometimes, and especially with dilute solutions of nitric acid, the deoxidation proceeds as far as the formation of hydroxylamine and ammonia, and sometimes it leads to the formation of nitrogen itself. The formation of one or other nitrogenous substance from nitric acid is determined, not only by the nature of the reacting substances, but also by the relative mass of water and nitric acid, and also by the temperature and pressure, or the sum total of the conditions of reaction; and as in a given mixture even these conditions vary (the temperature and the relative mass vary), it not unfrequently happens that a mixture of different products of the deoxidation of nitric acid is formed. [39] [Illustration: FIG. 49.--Decomposition of nitrous oxide by sodium.] Nitric acid may be entirely decomposed by passing its vapour over highly incandescent copper, because the oxides of nitrogen first formed give up their oxygen to the red-hot metallic copper, so that water and nitrogen gas alone are obtained. This forms a means for determining the composition both of nitric acid and of all the other compounds of nitrogen with oxygen, because by collecting the gaseous nitrogen formed it is possible to calculate, from its volume, its weight and consequently its amount in a given quantity of a nitrogenous substance, and by weighing the copper before and after the decomposition it is possible to determine the amount of oxygen by the increase in weight. The complete decomposition of nitric acid is also accomplished by passing a mixture of hydrogen and nitric acid vapours through a red-hot tube. Sodium also decomposes the oxides of nitrogen at a red-heat, taking up all the oxygen. This method is sometimes used for determining the composition of the oxides of nitrogen. [40] The application of this acid for etching copper or steel in engraving is based on this fact. The copper is covered with a coating of wax, resin, &c. (etching ground), on which nitric acid does not act, and then the ground is removed in certain parts with a needle, and the whole is washed in nitric acid. The parts coated remain untouched, whilst the uncovered portions are eaten into by the acid. Copper plates for etchings, aquatints, &c., are prepared in this manner. [41] The formation of such complex equations as the above often presents some difficulty to the beginner. It should be observed that if the reacting and resultant substances be known, it is easy to form an equation for the reaction. Thus, if we wish to form an equation expressing the reaction that nitric acid acting on zinc gives nitrous oxide, N_{2}O, and zinc nitrate, Zn(NO_{3})_{2}, we must reason as follows:--Nitric acid contains hydrogen, whilst the salt and nitrous oxide do not; hence water is formed, and therefore it is as though anhydrous nitric acid, N_{2}O_{5}, were acting. For its conversion into nitrous oxide it parts with four equivalents of oxygen, and hence it is able to oxidise four equivalents of zinc and to convert it into zinc oxide, ZnO. These four equivalents of zinc oxide require for their conversion into the salt four more equivalents of nitric anhydride; consequently five equivalents in all of the latter are required, or ten equivalents of nitric acid. Thus ten equivalents of nitric acid are necessary for four equivalents of zinc in order to express the reaction in whole equivalents. It must not be forgotten, however, that there are very few such reactions which can be entirely expressed by simple equations. The majority of equations of reactions only express the chief and ultimate products of reaction, and thus none of the three preceding equations express all that in reality occurs in the action of metals on nitric acid. In no one of them is only one oxide of nitrogen formed, but always several together or consecutively--one after the other, according to the temperature and strength of the acid. And this is easily intelligible. The resulting oxide is itself capable of acting on metals and of being deoxidised, and in the presence of the nitric acid it may change the acid and be itself changed. The equations given must be looked on as a systematic expression of the main features of reactions, or as a limit towards which they tend, but to which they only attain in the absence of disturbing influences. Thus the action of nitric acid on metals consists in their being oxidised, whilst the acid itself is converted, according to the temperature, concentration in which it is taken, and the nature of the metal, &c., into lower oxides, ammonia, or even into nitrogen.[42] Many compounds are oxidised by nitric acid like metals and other elements; for instance, lower oxides are converted into higher oxides. Thus, arsenious acid is converted into arsenic acid, suboxide of iron into oxide, sulphurous acid into sulphuric acid, the sulphides of the metals, M_{2}S, into sulphates, M_{2}SO_{4}, &c.; in a word, nitric acid brings about oxidation, its oxygen is taken up and transferred to many other substances. Certain substances are oxidised by strong nitric acid so rapidly and with so great an evolution of heat that they deflagrate and burst into flame. Thus turpentine, C_{10}H_{16}, bursts into flame when poured into fuming nitric acid. In virtue of its oxidising property, nitric acid _removes the hydrogen_ from many substances. Thus it decomposes hydriodic acid, separating the iodine and forming water; and if fuming nitric acid be poured into a flask containing gaseous hydriodic acid, then a rapid reaction takes place, accompanied by flame and the separation of violet vapours of iodine and brown fumes of oxides of nitrogen.[43] [42] Montemartini endeavours to show that the products evolved in the action of nitric acid upon metals (and their amount) is in direct connection with both the concentration of the acid and the capacity of the metals to decompose water. Those metals which only decompose water at a high temperature give, under the action of nitric acid, NO_{2}, N_{2}O_{4}, and NO; whilst those metals which decompose water at a lower temperature give, besides the above products, N_{2}O, N, and NH_{3}; and, lastly, the metals which decompose water at the ordinary temperature also evolve hydrogen. It is observed that concentrated nitric acid oxidises many metals with much greater difficulty than when diluted with water; iron, copper, and tin are very easily oxidised by dilute nitric acid, but remain unaltered under the influence of monohydrated nitric acid or of the pure hydrate NHO_{3}. Nitric acid diluted with a large quantity of water does not oxidise copper, but it oxidises tin; dilute nitric acid also does not oxidise either silver or mercury; but, on the addition of nitrous acid, even dilute acid acts on the above metals. This naturally depends on the smaller stability of nitrous acid, and on the fact that after the commencement of the action the nitric acid is itself converted into nitrous acid, which continues to act on the silver and mercury. Veley (Oxford 1891) made detailed researches on the action of nitric acid upon Cu, Hg, and Bi, and showed that nitric acid of 30 p.c. strength does not act upon these metals at the ordinary temperature if nitrous acid (traces are destroyed by urea) and oxidising agents such as H_{2}O_{2}, KClO_{3}, &c. be entirely absent; but in the presence of even a small amount of nitrous acid the metals form nitrites, which, with HNO_{3}, form nitrates and the oxides of nitrogen, which re-form the nitrous acid necessary for starting the reaction, because the reaction 2NO + HNO_{3} + H_{2}O = 3HNO_{2} is reversible. The above metals are quickly dissolved in a 1 p.c. solution of nitrous acid. Moreover, Veley observed that nitric acid is partially converted into nitrous acid by gaseous hydrogen in the presence of the nitrates of Cu and Pb. [43] When nitric acid acts on many organic substances it often happens that not only is hydrogen removed, but also oxygen is combined; thus, for example, nitric acid converts toluene, C_{7}H_{8}, into benzoic acid, C_{7}H_{6}O_{2}. In certain cases, also, a portion of the carbon contained in an organic substance burns at the expense of the oxygen of the nitric acid. So, for instance, phthalic acid, C_{8}H_{6}O_{4}, is obtained from naphthalene, _{10}H_{8}. Thus the action of nitric acid on the hydrocarbons is often most complex; not only does nitrification take place, but also separation of carbon, displacement of hydrogen, and combination of oxygen. There are few organic substances which can withstand the action of nitric acid, and it causes fundamental changes in a number of them. It leaves a yellow stain on the skin, and in a large quantity causes a wound and entirely eats away the membranes of the body. The membranes of plants are eaten into with the greatest ease by strong nitric acid in just the same manner. One of the most durable blue vegetable dyes employed in dyeing tissues is _indigo_; yet it is easily _converted into a yellow substance_ by the action of nitric acid, and small traces of free nitric acid may be recognised by this means. As nitric acid is very easily decomposed with the separation of oxygen, it was for a long time supposed that it was not capable of forming the corresponding _nitric anhydride_, N_{2}O_{5}; but Deville first and subsequently Weber and others, discovered the methods of its formation. Deville obtained nitric anhydride by decomposing silver nitrate by chlorine under the influence of a moderate heat. Chlorine acts on the above salt at a temperature of 95° (2AgNO_{3} + Cl_{2} = 2AgCl + N_{2}O_{5} + O), and when once the reaction is started, it continues by itself without further heating. Brown fumes are given off, which are condensed in a tube surrounded by a freezing-mixture. A portion condenses in this tube and a portion remains in a gaseous state. The latter contains free oxygen. A crystalline mass and a liquid substance are obtained in the tube; the liquid is poured off, and a current of dry carbonic acid gas is passed through the apparatus in order to remove all traces of volatile substances (liquid oxides of nitrogen) adhering to the crystals of nitric anhydride. These form a voluminous mass of rhombic crystals (density 1·64), which sometimes are of rather large size; they melt at about 30° and distil at about 47°. In distilling, a portion of the substance is decomposed. With water these crystals give nitric acid. Nitric anhydride is also obtained by the action of phosphoric anhydride, P_{2}O_{5}, on cold pure nitric acid (below 0°). During the very careful distillation of equal parts by weight of these two substances a portion of the acid decomposes, giving a liquid compound, H_{2}O,2N_{2}O_{5} = N_{2}O_{5},2HNO_{3}, whilst the greater part of the nitric acid gives the anhydride according to the equation 2NHO_{3} + P_{2}O_{5} = 2PHO_{3} + N_{2}O_{5}. On heating, nitric anhydride decomposes with an explosion, or gradually, into nitric peroxide and oxygen, N_{2}O_{5} = N_{2}O_{4} + O. _Nitrogen peroxide_, N_{2}O_{4}, and _nitrogen dioxide_, NO_{2}, express one and the same composition, but they should be distinguished like ordinary oxygen and ozone, although in this case their mutual conversion is more easily effected and takes place on vaporisation; also, O_{3} loses heat in passing into O_{2}, whilst N_{2}O_{4} absorbs heat in forming NO_{2}. Nitric acid in acting on tin and on many organic substances (for example, starch) gives brown vapours, consisting of a mixture of N_{2}O_{3} and NO_{2}. A purer product is obtained by the decomposition of lead nitrate by heat, Pb(NO_{3})_{2} = 2NO_{2} + O + PbO, when non-volatile lead oxide, oxygen gas, and nitrogen peroxide are formed. The latter condenses, in a well-cooled vessel, to a brown liquid, which boils at about 22°. The purest peroxide of nitrogen, solidifying at -9°, is obtained by mixing dry oxygen in a freezing-mixture with twice its volume of dry nitric oxide, NO, when transparent prisms of nitrogen peroxide are formed in the receiver: they melt into a colourless liquid at about -10°. When the temperature of the receiver is above -9°, the crystals melt,[44] and at 0° give a reddish yellow liquid, like that obtained in the decomposition of lead nitrate. The vapours of nitrogen peroxide have a characteristic odour, and at the ordinary temperature are of a dark-brown colour, but at lower temperatures the colour of the vapour is much fainter. When heated, especially above 50°, the colour becomes a very dark brown, so that the vapours almost lose their transparency. [44] According to certain investigations, if a brown liquid is formed from the melted crystals by beating above -9°, then they no longer solidify at -10°, probably because a certain amount of N_{2}O_{3} (and oxygen) is formed, and this substance remains liquid at -30°, or it may be that the passage from 2NO_{2} into N_{2}O_{4} is not so easily accomplished as the passage from N_{2}O_{4} into 2NO_{2}. Liquid nitrogen peroxide (that is, a mixture of NO_{2} and N_{2}O_{4}) is employed in admixture with hydrocarbons as an explosive. The causes of these peculiarities of nitrogen peroxide were not clearly understood until Deville and Troost determined the density and dissociation of the vapour of this substance at different temperatures, and showed that the density varies. If the density be referred to that of hydrogen at the same temperature and pressure, then it is found to vary from 38 at the boiling point, or about 27°, to 23 at 135°, after which the density remains constant up to those high temperatures at which the oxides of nitrogen are decomposed. As on the basis of the laws enunciated in the following chapter, the density 23 corresponds with the compound NO_{2} (because the weight corresponding with this molecular formula = 46, and the density referred to hydrogen as unity is equal to half the molecular weight); therefore at temperatures above 135° the existence of nitrogen dioxide only must be recognised. It is this gas which is of a brown colour. At a lower temperature it forms nitrogen peroxide, N_{2}O_{4}, whose molecular weight, and therefore density, is twice that of the dioxide. This substance, which is isomeric with nitrogen dioxide, as ozone is isomeric with oxygen, and has twice as great a vapour density (46 referred to hydrogen), is formed in greater quantity the lower the temperature, and crystallises at -10°. The reasons both of the variation of the colour of the gas (N_{2}O_{4} gives colourless and transparent vapours, whilst those of NO_{2} are brown and opaque) and the variation of the vapour density with the variation of temperature are thus made quite clear; and as at the boiling point a density 38 was obtained, therefore at that temperature the vapours consist of a mixture of 79 parts by weight of N_{2}O_{4} with 21 parts by weight of NO_{2}.[45] It is evident that a decomposition here takes place the peculiarity of which consists in the fact that the product of decomposition, NO_{2}, is polymerised (_i.e._ becomes denser, combines with itself) at a lower temperature; that is, the reaction N_{2}O_{4} = NO_{2} + NO_{2} is a reversible reaction, and consequently the whole phenomenon represents a _dissociation_ in a homogeneous gaseous medium, where the original substance, N_{2}O_{4}, and the resultant, NO_{2}, are both gases. The _measure of dissociation_ will be expressed if we find the proportion of the quantity of the substance decomposed to the whole amount of the substance. At the boiling point, therefore, the measure of the decomposition of nitrogen peroxide will be 21 p.c.; at 135° it = 1, and at 10° it = 0; that is, the N_{2}O_{4} is not then decomposable. Consequently the limits of dissociation here are -10° and 135° at the atmospheric pressure.[46] Within the limits of these temperatures the vapours of nitrogen peroxide have not a constant density, but, on the other hand, above and below these limits definite substances exist. Thus above 135° N_{2}O_{4} has ceased to exist and NO_{2} alone remains. It is evident that at the ordinary temperature there is a partially dissociated system or mixture of nitrogen peroxide, N_{2}O_{4}, and nitrogen dioxide, NO_{2}. In the brown liquid boiling at 22° probably a portion of the N_{2}O_{4} has already passed into NO_{2}, and it is only the colourless liquid and crystalline substance at -10° that can be considered as pure nitrogen peroxide.[47] [45] Because if _x_ equal the amount by weight of N_{2}O_{4}, its volume will = _x_/46, and the amount of NO_{2} will = 100-_x_, and consequently its volume will = (100-_x_)/23. But the mixture, having a density 38, will weigh 100; consequently its volume will = 100/38. Hence _x_/46 + (100-_x_)/23 = 100/38, or _x_ = 79·O. [46] The phenomena and laws of dissociation, which we shall consider only in particular instances, are discussed in detail in works on theoretical chemistry. Nevertheless, in respect to nitrogen peroxide, as an historically important example of dissociation in a homogeneous gaseous medium, we will cite the results of the careful investigations (1885-1880) of E. and L. Natanson, who determined the densities under various conditions of temperature and pressure. The degree of dissociation, expressed as above (it may also he expressed otherwise--for example, by the ratio of the quantity of substance decomposed to that unaltered), proves to increase at all temperatures as the pressure diminishes, which would he expected for a homogeneous gaseous medium, as a decreasing pressure aids the formation of the lightest product of dissociation (that having the least density or largest volume). Thus, in the Natansons' experiments the degree of dissociation at 0° increases from 10 p.c. to 30 p.c., with a decrease of pressure of from 251 to 38 mm.; at 49°·7 it increases from 49 p.c. to 93 p.c., with a fall of pressure of from 498 to 27 mm., and at 100° it increases from 89·2 p.c. to 99·7 p.c., with a fall of pressure of from 732·5 to 11·7 mm. At 130° and 150° the decomposition is complete--that is, only NO_{2} remains at the low pressures (less than the atmospheric) at which the Natansons made their determinations; but it is probable that at higher pressures (of several atmospheres) molecules of N_{2}O_{4} would still be formed, and it would be exceedingly interesting to trace the phenomena under the conditions of both very considerable pressures and of relatively large volumes. [47] Liquid nitrogen peroxide is said by Geuther to boil at 22°-26°, and to have a sp. gr. at 0° = 1·494 and at 15° = 1·474. It is evident that, in the liquid as in the gaseous state, the variation of density with the temperature depends, not only on physical, but also on chemical changes, as the amount of N_{2}O_{4} decreases and the amount of NO_{2} increases with the temperature, and they (as polymeric substances) should have different densities, as we find, for instance, in the hydrocarbons C_{5}H_{10} and C_{10}H_{20}. It may not be superfluous to mention here that the measurement of the specific heat of a mixture of the vapours of N_{2}O_{4} and NO_{2} enabled Berthelot to determine that the transformation of 2NO_{2} into N_{2}O_{4} is accompanied by the evolution of about 13,000 units of heat, and as the reaction proceeds with equal facility in either direction, it will be exothermal in the one direction and endothermal in the other; and this clearly demonstrates the possibility of reactions taking place in either direction, although, as a rule, reactions evolving heat proceed with greater ease. The above explains the action of nitrogen peroxide on water at low temperatures. N_{2}O_{4} then acts on water like a mixture of the anhydrides of nitrous and nitric acids. The first, N_{2}O_{3}, may be looked on as water in which each of the two atoms of hydrogen is replaced by the radicle NO, while in the second each hydrogen is replaced by the radicle NO_{2}, proper to nitric acid; and in nitrogen peroxide one atom of the hydrogen of water is replaced by NO and the other by NO_{2}, as is seen from the formulæ-- H} NO} NO } NO_{2}} H} O; NO} O; NO_{2}} O; NO_{2}} O; or H_{2}O; N_{2}O{3}; N_{2}O_{4}; N_{2}O_{5}. In fact, nitrogen peroxide at low temperatures gives with water (ice) both nitric, HNO_{3}, and nitrous, HNO_{2}, acids. The latter, as we shall afterwards see, splits up into water and the anhydride, N_{2}O_{3}. If, however, warm water act on nitrogen peroxide, only nitric acid and monoxide of nitrogen are formed: 3NO_{2} + H_{2}O = NO + 2NHO_{3}. Although NO_{2} is not decomposed into N and O even at 500°, still in many cases it acts as an oxidising agent. Thus, for instance, it oxidises mercury, converting it into mercurous nitrate, 2NO_{2} + Hg = HgNO_{3} + NO, being itself deoxidised into nitric oxide, into which the dioxide in many other instances passes, and from which it is easily formed.[48] [48] Nitric acid of sp. gr. 1·51 in dissolving nitrogen peroxide becomes brown, whilst nitric acid of sp. gr. 1·32 is coloured greenish blue, and acid of sp. gr. below 1·15 remains colourless after absorbing nitrogen peroxide (Note 33). _Nitrous anhydride_, N_{2}O_{3}, corresponds[49] to nitrous acid, NHO_{2}, which forms a series of salts, the nitrites--for example, the sodium salt NaNO_{2}, the potassium salt KNO_{2}, the ammonium salt (NH_{4})NO_{2},[50] the silver salt AgNO_{2},[51] &c. Neither the anhydride nor the hydrate of the acid is known in a perfectly pure state. The anhydride has only been obtained as a very unstable substance, and has not yet been fully investigated; and on attempting to obtain the acid NHO_{2} from its salts, it always gives water and the anhydride, whilst the latter, as an intermediate oxide, partially or wholly splits up into NO + NO_{2}. But the salts of nitrous acid are distinguished for their great stability. Potassium nitrate, KNO_{3}, may be converted into potassium nitrite by depriving it of a portion of its oxygen; for instance, by fusing it (at not too high a temperature) with metals, such as lead, KNO_{3} + Pb = KNO_{2} + PbO.[51 bis] The resultant salt is soluble in water, whilst the oxide of lead is insoluble. With sulphuric and other acids the solution of potassium nitrite[52] immediately evolves a brown gas, nitrous anhydride: 2KNO_{2} + H_{2}SO_{4} = K_{2}SO_{4} + N_{2}O_{3} + H_{2}O. The same gas (N_{2}O_{3}) is obtained by passing nitric oxide at 0° through liquid peroxide of nitrogen,[53] or by heating starch with nitric acid of sp. gr. 1·3. At a very low temperature it condenses into a blue liquid boiling below 0°,[54] but then partially decomposing into NO + NO_{2}. Nitrous anhydride possesses a remarkable capacity for oxidising. Ignited bodies burn in it, nitric acid absorbs it, and then acquires the property of acting on silver and other metals, even when diluted. _Potassium iodide_ is oxidised by this gas just as it is by ozone (and by peroxide of hydrogen, chromic and other acids, but not by dilute nitric acid nor by sulphuric acid), with the _separation of iodine_. This iodine may he recognised (_see_ Ozone, Chapter IV.) by its turning starch blue. Very small traces of nitrites may be easily detected by this method. If, for example, starch and potassium iodide are added to a solution of potassium nitrite (at first there will be no change, there being no free nitrous acid), and then sulphuric acid be added, the nitrous acid (or its anhydride) immediately set free liberates iodine, which produces a blue colour with the starch. Nitric acid does not act in this manner, but in the presence of zinc the coloration takes place, which proves the formation of nitrous acid in the deoxidation of nitric acid.[55] Nitrous acid acts directly on ammonia, forming nitrogen and water, HNO_{2} + NH_{3} = N_{2} + 2H_{2}O.[56] [49] Nitrogen peroxide as a mixed substance has no corresponding independent salts, but Sabatier and Senderens (1892) showed that under certain conditions NO_{2} combines directly with some metals--for instance, copper and cobalt--forming Cu_{2}NO_{2} and CoNO_{2} as dark brown powders, which do not, however, exhibit the reactions of salts. Thus by passing gaseous nitrogen dioxide over freshly reduced (from the oxides by heating with hydrogen) copper at 25°-30°, Cu_{2}NO_{2} is directly formed. With water it partly gives off NO_{2} and partly forms nitrite of copper, leaving metallic copper and its suboxide. The nature of these compounds has not yet been sufficiently investigated. [50] Ammonium nitrite may be easily obtained in solution by a similar method of double decomposition (for instance, of the barium salt with ammonium sulphate) to the other salts of nitrous acid, but it decomposes with great ease when evaporated, with evolution of gaseous nitrogen, as already mentioned (Chapter V.) If the solution, however, be evaporated at the ordinary temperature under the receiver of an air-pump, a solid saline mass is obtained, which is easily decomposed when heated. The dry salt even decomposes with an explosion when struck, or when heated to about 70°--NH_{4}NO_{2} = 2H_{2}O + N_{2}. It is also formed by the action of aqueous ammonia on a mixture of nitric oxide and oxygen, or by the action of ozone on ammonia, and in many other instances. Zörensen (1894) prepared NH_{4}NO_{2} by the action of a mixture of N_{2}O_{3} and other oxides of nitrogen on lumps of ammonium carbonate, extracting the nitrite of ammonium formed with absolute alcohol, and precipitating it from this solution by ether. This salt is crystalline, dissolves in water with absorption of heat, and attracts moisture from the air. The solid salt and its concentrated solutions decompose with an explosion when heated to 50°-80°, especially in the presence of traces of foreign acids. Decomposition also proceeds at the ordinary temperature, but more slowly; and in order to preserve the salt it should be covered with a layer of pure dry ether. [51] Silver nitrite, AgNO_{2}, is obtained as a very slightly soluble substance, as a precipitate, on mixing solutions of silver nitrate, AgNO_{3}, and potassium nitrite, KNO_{2}. It is soluble in a large volume of water, and this is taken advantage of to free it from silver oxide, which is also present in the precipitate, owing to the fact that potassium nitrite always contains a certain amount of oxide, which with water gives the hydroxide, forming oxide of silver with silver nitrate. The solution of silver nitrite gives, by double decomposition with metallic chlorides (for instance, barium chloride), insoluble silver chloride and the nitrite of the metal taken (in this case, barium nitrite, Ba(NO_{2})_{2}). [51 bis] Leroy (1889) obtained KNO_{2} by mixing powdered KNO_{3} with BaS, igniting the mixture in a crucible and washing the fused salts; BaSO_{4} is then left as an insoluble residue, and KNO_{2} passes into solution: 4KNO_{3} + BaS = 4KNO_{2} + BaSO_{4}. [52] Probably potassium nitrite, KNO_{2}, when strongly heated, especially with metallic oxides, evolves N and O, and gives potassium oxide, K_{2}O, because nitre is liable to such a decomposition; but it has, as yet, been but little investigated. [53] There are many researches which lead to the conclusion that the reaction N_{2}O_{3} = NO_{2}-NO is reversible, _i.e._ resembles the conversion of N_{2}O_{4} into NO_{2}. The brown colour of the fumes of N_{2}O_{3} is due to the formation of NO_{2}. If nitrogen peroxide be cooled to -20°, and half its weight of water be added to it drop by drop, then the peroxide is decomposed, as we have already said, into nitrous and nitric acids; the former does not then remain as a hydrate, but straightway passes into the anhydride, and, hence, if the resultant liquid be slightly warmed vapours of nitrous anhydride, N_{2}O_{3}, are evolved, and condense into a blue liquid, as Fritzsche showed. This method of preparing nitrous anhydride apparently gives the purest product, but it easily dissociates, forming NO and NO_{2} (and therefore also nitric acid in the presence of water). [54] According to Thorpe, N_{2}O_{3} boils at +18°. According to Geuther, at +3°·5, and its sp. gr. at 0° = 1·449. [55] In its oxidising action nitrous anhydride gives nitric oxide, N_{2}O_{3} = 2NO + O. Thus its analogy to ozone becomes still more marked, because in ozone it is only one-third of the oxygen that acts in oxidising; from O_{3} there is obtained O, which acts as an oxidiser, and common oxygen O_{2}. In a physical aspect the relation between N_{2}O_{3} and O_{3} is revealed in the fact that both substances are of a blue colour when in the liquid state. [56] This reaction is taken advantage of for converting the amides, NH_{2}R (where R is an element or a complex group) into hydroxides, RHO. In this case NH_{2}R + NHO_{2} forms 2N + H_{2}O + RHO; NH_{2}, is replaced by HO, the radicle of ammonia by the radicle of water. This reaction is employed for transforming many nitrogenous organic substances having the properties of amides into their corresponding hydroxides. Thus aniline, C_{6}H_{5}·NH_{2}, which is obtained from nitrobenzene, C_{6}H_{5}·NO_{2} (Note 37), is converted by nitrous anhydride into phenol, C_{6}H_{5}·OH, which occurs in the creosote extracted from coal tar. Thus the H of the benzene is successively replaced by NO_{2}, NH_{2}, and HO; a method which is suitable for other cases also. As nitrous anhydride easily splits up into NO_{2} + NO, so, like NO_{2}, with warm water it gives nitric acid and nitric oxide, according to the equation 3N_{2}O_{3} + H_{2}O = 4NO + 2NHO_{3}. Being in a lower degree of oxidation than nitric acid, nitrous acid and its anhydride are oxidised in solutions by many oxidising substances--for example, by potassium permanganate--into nitric acid.[57] [57] The action of a solution of potassium permanganate, KMnO_{4}, on nitrous acid in the presence of sulphuric acid is determined by the fact that the higher oxide of manganese, Mn_{2}O_{7}, contained in the permanganate is converted into the lower oxide, MnO, which as a base forms manganese sulphate, MnSO_{4}, and the oxygen serves for the oxidation of the N_{2}O_{3} into N_{2}O_{5}, or its hydrate. As the solution of the permanganate is of a red colour, whilst that of manganese sulphate is almost colourless, this reaction is clearly seen, and may be employed for the detection and determination of nitrous acid and its salts. _Nitric oxide_, NO.--This permanent gas[58] (that is, unliquefiable by pressure without the aid of cold) may be obtained from all the above-described compounds of nitrogen with oxygen. The deoxidation of nitric acid by metals is the usual method employed for its preparation. Dilute nitric acid (sp. gr. 1·18, but not stronger, as then N_{2}O_{3} and NO_{2} are produced) is poured into a flask containing metallic copper.[59] The reaction commences at the ordinary temperature. Mercury and silver also give nitric oxide with nitric acid. In these reactions with metals one portion of the nitric acid is employed in the oxidation of the metal, whilst the other, and by far the greater, portion combines with the metallic oxide so obtained, with formation of the nitrate corresponding with the metal taken. The first action of the copper on the nitric acid is thus expressed by the equation 2NHO_{3} + 3Cu = H_{2}O + 3CuO + 2NO. The second reaction consists in the formation of copper nitrate-- 6NHO_{3} + 3CuO = 3H_{2}O + 3Cu(NO_{3})_{2}. [58] The absolute boiling point = -93° (_see_ Chapter II., Note 29). [59] Kammerer proposed preparing nitric oxide, NO, by pouring a solution of sodium nitrate over copper shavings, and adding sulphuric acid drop by drop. The oxidation of ferrous salts by nitric acid also gives NO. One part of strong hydrochloric acid is taken and iron is dissolved in it (FeCl_{2}), and then an equal quantity of hydrochloric acid and nitre is added to the solution. On heating, nitric oxide is evolved. In the presence of an excess of sulphuric acid and mercury the conversion of nitric acid into nitric oxide is complete (that is, the reaction proceeds to the end and the nitric oxide is obtained without other products), and upon this is founded one of the methods for determining nitric acid (in nitrometers of various kinds, described in text-books of analytical chemistry), as the amount of NO can be easily and accurately measured volumetrically. The amount of nitrogen in gun-cotton, for instance, is determined by dissolving it in sulphuric acid. Nitrous acid acts in the same manner. Upon this property Emich (1892) founds his method for preparing pure NO. He pours mercury into a flask, and then covers it with sulphuric acid, in which a certain amount of NaNO_{2} or other substance corresponding to HNO_{2} or HNO_{3} has been dissolved. The evolution of NO proceeds at the ordinary temperature, being more rapid as the surface of the mercury is increased (if shaken, the reaction proceeds very rapidly). If the gas be passed over KHO, it is obtained quite pure, because KHO does not act upon NO at the ordinary temperature (if heated, KNO_{2} and N_{2}O or N_{2}, are formed). Nitric oxide is a colourless gas which is only slightly soluble in water (1/20 of a volume at the ordinary temperature). Reactions of double decomposition in which nitric oxide readily takes part are not known--that is to say, it is an indifferent, not a saline, oxide. Like the other oxides of nitrogen, it is decomposed into its elements at a red heat (starting from 900°, at 1,200° 60 per cent. give N_{2} and 2N_{2}O_{3}, but complete decomposition into N_{2} and O_{2} only takes place at the melting point of platinum, Emich 1892). The most characteristic property of nitric oxide is its capacity for directly and easily combining with oxygen (owing to the evolution of heat in the combination). With oxygen it forms nitrous anhydride and nitrogen peroxide, 2NO + O = N_{2}O_{3}, 2NO + O_{2} = 2NO_{2}. If nitric oxide is mixed with oxygen and immediately shaken up with caustic potash, it is almost entirely converted into potassium nitrite; whilst after a certain time, when the formation of nitric peroxide has already commenced, a mixture of potassium nitrite and nitrate is obtained. If oxygen is passed into a bell jar filled with nitric oxide, brown fumes of nitrous anhydride and nitric peroxide are formed, even in the absence of moisture; these in the presence of water give, as we already know, nitric acid and nitric oxide, so that in the presence of an excess of water and oxygen the whole of the nitric oxide is easily and directly converted into nitric acid. This reaction of the re-formation of nitric acid from nitric oxide, air, and water, 2NO + H_{2}O + O_{3} = 2HNO_{3}, is frequently made use of in practice. The experiment showing the conversion of nitric oxide into nitric acid is very striking and instructive. As the intermixture of the oxygen with the oxide of nitrogen proceeds, the nitric acid formed dissolves in water, and if an excess of oxygen has not been added the whole of the gas (nitric oxide), being converted into HNO_{3}, is absorbed, and the water entirely fills the bell jar previously containing the gas.[60] It is evident that nitric oxide[61] in combining with oxygen has a strong tendency to give the higher types of nitrogen compounds, which we see in nitric acid, HNO_{3} or NO_{2}(OH), in nitric anhydride, N_{2}O_{5} or (NO_{2})_{2}O, and in ammonium chloride, NH_{4}Cl. If X stand for an atom of hydrogen, or its equivalents, chlorine, hydroxyl, &c., and if O, which is, according to the law of substitution, equivalent to H_{2}, be indicated by X_{2}, then the three compounds of nitrogen above named should be considered as compounds of the type or form NX_{5}. For example, in nitric acid X_{5} = O_{2} + (OH), where O_{2} = X_{4}, and OH = X; whilst nitric oxide is a compound of the form NX_{2}. Hence this lower form, like lower forms in general, strives by combination to attain to the higher forms proper to the compounds of a given element. NX_{2} passes consecutively into NX_{3}--namely, into N_{2}O_{3} and NHO_{2}, NX_{4} (for instance NO_{2}) and NX_{5}. [60] This transformation of the permanent gases nitric oxide and oxygen into liquid nitric acid in the presence of water, and with the evolution of heat, presents a most striking instance of liquefaction produced by the action of chemical forces. They perform with ease the work which physical (cooling) and mechanical (pressure) forces effect with difficulty. In this the motion, which is so distinctively the property of the gaseous molecules, is apparently destroyed. In other cases of chemical action it is apparently created, arising, no doubt, from latent energy--that is, from the internal motion of the atoms in the molecules. [61] Nitric oxide is capable of entering into many characteristic combinations; it is absorbed by the solutions of many acids, for instance, tartaric, acetic, phosphoric, sulphuric, and metallic chlorides (for example, SbCl_{5}, BiCl_{3}, &c., with which it forms definite compounds; Besson 1889), and also by the solutions of many salts, especially those formed by suboxide of iron (for instance, ferrous sulphate). In this case a brown compound is formed which is exceedingly unstable, like all the analogous compounds of nitric oxide. The amount of nitric oxide combined in this manner is in atomic proportion with the amount of the substance taken; thus ferrous sulphate, FeSO_{4}, absorbs it in the proportion of NO to 2FeSO_{4}. Ammonia is obtained by the action of a caustic alkali on the resultant compound, because the oxygen of the nitric oxide and water are transferred to the ferrous oxide, forming ferric oxide, whilst the nitrogen combines with the hydrogen of the water. According to the investigations of Gay (1885), the compound is formed with the evolution of a large quantity of heat, and is easily dissociated, like a solution of ammonia in water. It is evident that oxidising substances (for example, potassium permanganate, KMnO_{4}, Note 57) are able to convert it into nitric acid. If the presence of a radicle NO_{2}, composed like nitrogen peroxide, must be recognised in the compounds of nitric acid, then a radicle NO, having the composition of nitric oxide, may be admitted in the compounds of nitrous acid. The compounds in which the radicle NO is recognised are called _nitroso-compounds_. These substances are described in Prof. Bunge's work (Kief, 1868). As the decomposition of nitric oxide begins at temperatures above 900°, many substances burn in it; thus, ignited phosphorus continues to burn in nitric oxide, but sulphur and charcoal are extinguished in it. This is due to the fact that the heat evolved in the combustion of these two substances is insufficient for the decomposition of the nitric oxide, whilst the heat developed by burning phosphorus suffices to produce this decomposition. That nitric oxide really supports combustion, owing to its being decomposed by the action of heat, is proved by the fact that strongly ignited charcoal continues to burn in the same nitric oxide[62] in which a feebly incandescent piece of charcoal is extinguished. [62] A mixture of nitric oxide and hydrogen is inflammable. If a mixture of the two gases be passed over spongy platinum the nitrogen and hydrogen even combine, forming ammonia. A mixture of nitric oxide with many combustible vapours and gases is very inflammable. A very characteristic flame is obtained in burning a mixture of nitric oxide and the vapour of the combustible carbon bisulphide, CS_{2}. The latter substance is very volatile, so that it is sufficient to pass the nitric oxide through a layer of the carbon bisulphide (for instance, in a Woulfe's bottle) in order that the gas escaping should contain a considerable amount of the vapours of this substance. This mixture continues to burn when ignited, and the flame emits a large quantity of the so-called ultra-violet rays, which are capable of inducing chemical combinations and decompositions, and therefore the flame may be employed in photography in the absence of sufficient daylight (magnesium light and electric light have the same property). There are many gases (for instance, ammonia) which when mixed with nitric oxide explode in a eudiometer. The compounds of nitrogen with oxygen which we have so far considered may all be prepared from nitric oxide, and may themselves be converted into it. Thus nitric oxide stands in intimate connection with them.[63] The passage of nitric oxide into the higher degrees of oxidation and the converse reaction is employed in practice as a means for _transferring_ the oxygen of the air to substances capable of being oxidised. Starting with nitric oxide, it may easily be converted, with the aid of the oxygen of the atmosphere and water, into nitric acid, nitrous anhydride, and nitric peroxide, and by their means employed to oxidise other substances. In this oxidising action nitric oxide is again formed, and it may again be converted into nitric acid, and so on continuously, if only oxygen and water be present. Hence the fact, which at first appears to be a paradox, that by means of a small quantity of nitric oxide in the presence of oxygen and water it is possible to oxidise an indefinitely large quantity of substances which cannot be directly oxidised either by the action of the atmospheric oxygen or by the action of nitric oxide itself. The sulphurous anhydride, SO_{2}, which is obtained in the combustion of sulphur and in roasting many metallic sulphides in the air is an example of this kind. In practice this gas is obtained by burning sulphur or iron pyrites, the latter being thereby converted into oxide of iron and sulphurous anhydride. In contact with the oxygen of the atmosphere this gas does not pass into the higher degree of oxidation, sulphuric anhydride, SO_{3}, and if it does form sulphuric acid with water and the oxygen of the atmosphere, SO_{2} + H_{2}O + O = H_{2}SO_{4}, it does so very slowly. With nitric acid (and especially with nitrous acid, but not with nitrogen peroxide) and water, sulphurous anhydride, on the contrary, very easily forms sulphuric acid, and especially so when slightly heated (about 40°), the nitric acid (or, better still, nitrous acid) being converted into nitric oxide-- 3SO_{2} + 2NHO_{3} + 2H_{2}O = 2H_{2}SO_{4} + 2NO. [63] The oxides of nitrogen naturally do not proceed directly from oxygen and nitrogen by contact alone, because their formation is accompanied by the absorption of a large quantity of heat, for (_see_ Note 29) about 21,500 heat units are absorbed when 16 parts of oxygen and 14 parts of nitrogen combine; consequently the decomposition of nitric oxide into oxygen and nitrogen is accompanied by the evolution of this amount of heat; and therefore with nitric oxide, as with all explosive substances and mixtures, the reaction once started is able to proceed by itself. In fact, Berthelot remarked the decomposition of nitric oxide in the explosion of fulminate of mercury. This decomposition does not take place spontaneously; substances even burn with difficulty in nitric oxide, probably because a certain portion of the nitric oxide in decomposing gives oxygen, which combines with another portion of nitric oxide, and forms nitric peroxide, a somewhat more stable compound of nitrogen and oxygen. The further combinations of nitric oxide with oxygen all proceed with the evolution of heat, and take place spontaneously by contact with air alone. It is evident from these examples that the application of thermochemical data is limited. The presence of water is absolutely indispensable here, otherwise sulphuric anhydride is formed, which combines with the oxides of nitrogen (nitrous anhydride), forming a crystalline substance containing oxides of nitrogen (_chamber crystals_, which will be described in Chapter XX.) Water destroys this compound, forming sulphuric acid and separating the oxides of nitrogen. The water must be taken in a greater quantity than that required for the formation of the hydrate H_{2}SO_{4}, because the latter absorbs oxides of nitrogen. With an excess of water, however, solution does not take place. If, in the above reaction, only water, sulphurous anhydride, and nitric or nitrous acid be taken in a definite quantity, then a definite quantity of sulphuric acid and nitric oxide will be formed, according to the preceding equation; but there the reaction ends and the excess of sulphurous anhydride, if there be any, will remain unchanged. But if we add air and water, then the nitric oxide will unite with the oxygen to form nitrogen peroxide, and the latter with water to form nitric and nitrous acids, which again give sulphuric acid from a fresh quantity of sulphurous anhydride. Nitric oxide is again formed, which is able to start the oxidation afresh if there be sufficient air. Thus it is possible with a definite quantity of nitric oxide to convert an indefinitely large quantity of sulphurous anhydride into sulphuric acid, water and oxygen only being required.[64] This may be easily demonstrated by an experiment on a small scale, if a certain quantity of nitric oxide be first introduced into a flask, and sulphurous anhydride, steam, and oxygen be then continually passed in. Thus the above-described reaction may be expressed in the following manner:-- _n_SO_{2} + _n_O + (_n_ + _m_)H_{2}O + NO = _n_H_{2}SO_{4},_m_H_{2}O + NO if we consider only the original substances and those finally formed. In this way a definite quantity of nitric oxide may serve for the conversion of an indefinite quantity of sulphurous anhydride, oxygen, and water into sulphuric acid. In reality, however, there is a limit to this, because air, and not pure oxygen, is employed for the oxidation, so that it is necessary to remove the nitrogen of the air and to introduce a fresh quantity of air. A certain quantity of nitric oxide will pass away with this nitrogen, and will in this way be lost.[65] [64] The instance of the action of a small quantity of NO in inducing a definite chemical reaction between large masses (SO_{2} + O + H_{2}O = H_{2}SO_{4}) is very instructive, because the particulars relating to it have been studied, and show that intermediate forms of reaction may be discovered in the so-called contact or catalytic phenomena. The essence of the matter here is that A (= SO_{2}) reacts upon B (= O and H_{2}O) in the presence of C, because it gives BC, a substance which forms AB with A, and again liberates C. Consequently C is a medium, a transferring substance, without which the reaction does not proceed. Many similar phenomena may be found in other departments of life. Thus the merchant is an indispensable medium between the producer and the consumer; experiment is a medium between the phenomena of nature and the cognisant faculties, and language, customs, and laws are media which are as necessary for the exchanges of social intercourse as nitric oxide for those between sulphurous anhydride and oxygen and water. [65] If the sulphurous anhydride be prepared by roasting iron pyrites, FeS_{2}, then each equivalent of pyrites (equivalent of iron, 56, of sulphur 32, of pyrites 120) requires six equivalents of oxygen (that is 96 parts) for the conversion of its sulphur into sulphuric acid (for forming 2H_{2}SO_{4} with water), besides 1-1/2 equivalents (24 parts) for converting the iron into oxide, Fe_{2}O_{3}; hence the combustion of the pyrites for the formation of sulphuric acid and ferric oxide requires the introduction of an equal weight of oxygen (120 parts of oxygen to 120 parts of pyrites), or five times its weight of air, whilst four parts by weight of nitrogen will remain inactive, and in the removal of the exhausted air will carry off the remaining nitric oxide. If not all, at least a large portion of the nitric oxide may be collected by passing the escaping air, still containing some oxygen, through substances which absorb oxides of nitrogen. Sulphuric acid itself may be employed for this purpose if it be used in the form of the hydrate H_{2}SO_{4}, or containing only a small amount of water, because such sulphuric acid dissolves the oxides of nitrogen. They may be easily expelled from this solution by heating or by dilution with water, as they are only slightly soluble in aqueous sulphuric acid. Besides which, sulphurous anhydride acts on such sulphuric acid, being oxidised at the expense of the nitrous anhydride, and forming nitric oxide from it, which again enters into the cycle of action. For this reason the sulphuric acid which has absorbed the oxides of nitrogen escaping from the chambers in the tower K (_see_ fig. 50) is led back into the first chamber, where it comes into contact with sulphurous anhydride, by which means the oxides of nitrogen are reintroduced into the reaction which proceeds in the chambers. This is the use of the towers (Gay-Lussac's and Glover's) which are erected at either end of the chambers. The preceding series of changes serve as the basis of the _manufacture of sulphuric acid_ or so-called _chamber acid_. This acid is prepared on a very large scale in chemical works because it is the cheapest acid whose action can be applied in a great number of cases. It is therefore used in immense quantities. [Illustration: FIG. 50.--Section of sulphuric acid chambers, the first and last chambers only being represented. The tower to the left is called the Glover's tower, and that on the right the Gay-Lussac's tower. Less than 1/10th of the natural size.] The process is carried on in a series of chambers (or in one divided by partitions as in fig. 50, which shows the beginning and end of a chamber) constructed of sheet lead. These chambers are placed one against the other, and communicate by tubes or special orifices so placed that the inlet tubes are in the upper portion of the chamber, and the outlet in the lower and opposite end. The current of steam and gases necessary for the preparation of the sulphuric acid passes through these chambers and tubes. The acid as it is formed falls to the bottom of the chambers or runs down their walls, and flows from chamber to chamber (from the last towards the first), to permit of which the partitions do not reach to the bottom. The floor and walls of the chambers should therefore be made of a material on which the sulphuric acid will not act. Among the ordinary metals lead is the only one suitable.[65 bis] [65 bis] Other metals, iron, copper, zinc, are corroded by it; glass and china are not acted upon, but they crack from the variations of temperature taking place in the chambers, and besides they are more difficult to join properly than lead; wood, &c., becomes charred. For the formation of the sulphuric acid it is necessary to introduce sulphurous anhydride, steam, air, and nitric acid, or some oxide of nitrogen, into the chambers. The sulphurous anhydride is produced by burning sulphur or iron pyrites. This is carried on in the furnace with four hearths to the left of the drawing. Air is led into the chambers and furnace through orifices in the furnace doors. The current of air and oxygen is regulated by opening or closing these orifices to a greater or less extent. The ingoing draught in the chambers is brought about by the fact that heated gases and vapours pass into the chambers, whose temperature is further raised by the reaction itself, and also by the remaining nitrogen being continually withdrawn from the outlet (above the tower K) by a tall chimney situated near the chambers. Nitric acid is prepared from a mixture of sulphuric acid and Chili saltpetre, in the same furnaces in which the sulphurous anhydride is evolved (or in special furnaces). Not more than 8 parts of nitre are taken to 100 parts of sulphur burnt. On leaving the furnace the vapours of nitric acid and oxides of nitrogen mixed with air and sulphurous anhydride first pass along the horizontal tubes T into the receiver B B, which is partially cooled by water flowing in on the right-hand side and running out on the left by _o_, in order to reduce the temperature of the gases entering the chamber. The gases then pass up a tower filled with coke, and shown to the left of the drawing. In this tower are placed lumps of coke (the residue from the dry distillation of coal), over which sulphuric acid trickles from the reservoir M. This acid has absorbed in the end tower K the oxides of nitrogen escaping from the chamber. This end tower is also filled with coke, over which a stream of strong sulphuric acid trickles from the reservoir M. The acid spreads over the coke, and, owing to the large surface offered by the latter, absorbs the greater part of the oxides of nitrogen escaping from the chambers. The sulphuric acid in passing down the tower becomes saturated with the oxides of nitrogen, and flows out at _h_ into a special receiver (in the drawing situated by the side of the furnaces), from which it is forced up the tubes _h´ h´_ by steam pressure into the reservoir M, situated above the first tower. The gases passing through this tower (hot) from the furnace on coming into contact with the sulphuric acid take up the oxides of nitrogen contained in it, and these are thus returned to the chamber and again participate in the reaction. The sulphuric acid left after their extraction flows into the chambers. Thus, on leaving the first coke tower the sulphurous anhydride, air, and vapours of nitric acid and of the oxides of nitrogen pass through the upper tube _m_ into the chamber. Here they come into contact with steam introduced by lead tubes into various parts of the chamber. The reaction takes place in the presence of water, the sulphuric acid falls to the bottom of the chamber, and the same process takes place in the following chambers until the whole of the sulphurous anhydride is consumed. A somewhat greater proportion of air than is strictly necessary is passed in, in order that no sulphurous anhydride should be left unaltered for want of sufficient oxygen. The presence of an excess of oxygen is shown by the colour of the gases escaping from the last chamber. If they be of a pale colour it indicates an insufficiency of air (and the presence of sulphurous anhydride), as otherwise peroxide of nitrogen would be formed. A very dark colour shows an excess of air, which is also disadvantageous, because it increases the inevitable loss of nitric oxide by increasing the mass of escaping gases.[66] [66] By this means as much as 2,500,000 kilograms of chamber acid, containing about 60 per cent. of the hydrate H_{2}SO_{4} and about 40 per cent. of water, may be manufactured per year in one plant of 5,000 cubic metres capacity (without stoppages). This process has been brought to such a degree of perfection that as much as 300 parts of the hydrate H_{2}SO_{4} are obtained from 100 parts of sulphur, whilst the theoretical amount is not greater than 306 parts. The acid parts with its excess of water on heating. For this purpose it is heated in lead vessels. However, the acid containing about 75 per cent. of the hydrate (60° Baumé) already begins to act on the lead when heated, and therefore the further removal of water is conducted by evaporating in glass or platinum vessels, as will he described in Chapter XX. The aqueous acid (50° Baumé) obtained in the chambers is termed chamber acid. The acid concentrated to 60° Baumé is more generally employed, and sometimes the hydrate (66° Baumé) termed vitriol acid is also used. In England alone more than 1,000 million kilograms of chamber acid are produced by this method. The formation of sulphuric acid by the action of nitric acid was discovered by Drebbel, and the first lead chamber was erected by Roebuck, in Scotland, in the middle of the last century. The essence of the process was only brought to light at the beginning of this century, when many improvements were introduced into practice. _Nitrous oxide_, N_{2}O,[67] is similar to water in its volumetric composition. Two volumes of nitrous oxide are formed from two volumes of nitrogen and one volume of oxygen, which may be shown by the ordinary method for the analysis of the oxides of nitrogen (by passing them over red-hot copper or sodium). In contradistinction to the other oxides of nitrogen, it is not directly oxidised by oxygen, but it may be obtained from the higher oxides of nitrogen by the action of certain deoxidising substances; thus, for example, a mixture of two volumes of nitric oxide and one volume of sulphurous anhydride if left in contact with water and spongy platinum is converted into sulphuric acid and nitrous oxide, 2NO + SO_{2} + H_{2}O = H_{2}SO_{4} + N_{2}O. Nitric acid, also, under the action of certain metals--for instance, of zinc[68]--gives nitrous oxide, although in this case mixed with nitric oxide. The usual method of preparing nitrous oxide consists in the decomposition of ammonium nitrate by the aid of heat, because in this case only water and nitrous oxide are formed, NH_{4}NO_{3} = 2H_{2}O + N_{2}O (a mixture of NH_{4}Cl and KNO_{3} is sometimes taken). The decomposition[69] proceeds very easily in an apparatus like that used for the preparation of ammonia or oxygen--that is, in a retort or flask with a gas-conducting tube. The decomposition must, however, be carried on carefully, as otherwise nitrogen is formed from the decomposition of the nitrous oxide.[70] [67] If the hydrate HNO_{3} corresponds to N_{2}O_{4}, the hydrate HNO, _hyponitrous acid_, corresponds to N_{2}O, and in this sense N_{2}O is _hyponitrous anhydride_. Hyponitrous acid, corresponding with nitrous oxide (as its anhydride), is not known in a pure state, but its salts (Divers) are known. They are prepared by the reduction of nitrous (and consequently of nitric) salts by sodium amalgam. If this amalgam he added to a cold solution of an alkaline nitrite until the evolution of gas ceases, and the excess of alkali saturated with acetic acid, an insoluble yellow precipitate of silver hyponitrite, NAgO, will he obtained on adding a solution of silver nitrate. This hyponitrite is insoluble in cold acetic acid, and decomposes when heated, with the evolution of nitrous oxide. If rapidly heated it decomposes with an explosion. It is dissolved unchanged by weak mineral acids, whilst the stronger acids (for example, sulphuric and hydrochloric acids) decompose it, with the evolution of nitrogen, nitric and nitrous acids remaining in solution. Among the other salts of hyponitrous acid, HNO, the salts of lead, copper, and mercury are insoluble in water. Judging by the bond between hyponitrous acid and the other compounds of nitrogen, there is reason for thinking that its formula should he doubled, N_{2}H_{2}O_{2}. For instance, Thoune (1893) on gradually oxidising hydroxylamine, NH_{2}(OH), into nitrous acid, NO(OH) (Note 25), by means of an alkaline solution of KMnO_{4}, first obtained hyponitrous acid, N_{2}H_{2}O_{2}, and then a peculiar intermediate acid, N_{2}H_{2}O_{3}, which, by further oxidation, gave nitrous acid. On the other hand, Wislicenus (1893) showed that in the action of the sulphuric acid salt of hydroxylamine upon nitrite of sodium, there is formed, besides, nitrous oxide (according to V. Meyer, NH_{3}O,H_{2}SO_{4} + NaNO_{2} = NaHSO_{4} + 2H_{2}O + N_{2}O), a small amount of hyponitrous acid which may be precipitated in the form of the silver salt; and this reaction is most simply expressed by taking the doubled formula of hyponitrous acid, NH_{2}(OH) + NO(OH) = H_{2}O + N_{2}H_{2}O_{2}. The best argument in favour of the doubled formula is the property possessed by hyponitrous acid of forming acid salts, HNaN_{2}O_{2} (Zorn). According to Thoune, the following are the properties of hyponitrous acid. When liberated from the dry silver salt by the action of dry sulphuretted hydrogen, hyponitrous acid is unstable, and easily explodes even at low temperatures. But when dissolved in water (having been formed by the action of hydrochloric acid upon the silver salt), it is stable even when boiled with dilute acids and alkalis. The solution is colourless and has a strongly acid reaction. In the course of time, however, the aqueous solution also decomposes into nitrous oxide and water. The complete oxidation by permanganate of potash proceeds according to the following equation: 5H_{2}N_{2}O_{2} + 8KMnO_{4} + 12H_{2}SO_{4} = 10HNO_{3} + 4K_{2}SO_{4} + 8MnSO_{4} + 12H_{2}O. In an alkaline solution, KMnO_{4} only oxidises hyponitrous acid into nitrous and not into nitric acid. Nitrous acid has a decomposing action upon hyponitrous acid, and if the aqueous solutions of the two acids be mixed together they immediately give off oxides of nitrogen. Hyponitrous acid does not liberate CO_{2} from its salts, but on the other hand it is not displaced by CO_{2}. [68] It is remarkable that electro-deposited copper powder gives nitrous oxide with a 10 p.c. solution of nitric acid, whilst ordinary copper gives nitric oxide. It is here evident that the physical and mechanical structure of the substance affects the course of the reaction--that is to say, it is a case of contact-action. [69] This decomposition is accompanied by the evolution of about 25,000 calories per molecular quantity, NH_{4}NO_{3}, and therefore takes place with ease, and sometimes with an explosion. [70] In order to remove any nitric oxide that might be present, the gas obtained is passed through a solution of ferrous sulphate. As nitrous oxide is very soluble in cold water (at 0°, 100 volumes of water dissolve 130 volumes of N_{2}O; at 20°, 67 volumes), it must be collected over warm water. The nitrous oxide is much more soluble than nitric oxide, which is in agreement with the fact that nitrous oxide is much more easily liquefied than nitric oxide. Villard obtained a crystallohydrate, N_{2}O,6H_{2}O, which was tolerably stable at 0°. [Illustration: FIG. 51.--Natterer's apparatus for the preparation of liquid nitrous oxide and carbonic anhydride. The gas first passes though the vessel V, for drying, and then into the pump (a section of the upper part of the apparatus is given on the left). The piston _t_ of the force pump is moved by the crank E and fly-wheel turned by hand. The gas is pumped into the iron chamber A, where it is liquefied. The valve S allows the gas to enter A, but not to escape from it. The chamber and pump are cooled by the jacket B, filled with ice. When the gas is liquefied the vessel A is unscrewed from the pump, and the liquid may be poured from it by inverting it and unscrewing the valve _v_, when the liquid runs out of the tube _x_.] Nitrous oxide is not a permanent gas (absolute boiling point +36°); it is easily liquefied by the action of cold under a high pressure; at 15° it may be liquefied by a pressure of about 40 atmospheres. This gas is usually liquefied by means of the force pump[71] shown in fig. 51. As it is liquefied with comparative ease, and as the cold produced by its vaporisation is very considerable,[72] it (as also liquid carbonic anhydride) is often employed in investigations requiring a low temperature. Nitrous oxide forms a very mobile, colourless liquid, which acts on the skin, and is incapable in a cold state of oxidising either metallic potassium, phosphorus, or carbon; its specific gravity is slightly less than that of water (0° = 0·910, 10° = 0·856, 35° = 0·60, 39° = 0·45, Villard, 1894). When evaporated under the receiver of an air-pump, the temperature falls to -100°, and the liquid solidifies into a snow-like mass, and partially forms transparent crystals. Both these substances are solid nitrous oxide. Mercury is immediately solidified in contact with evaporating liquid nitrous oxide.[73] [71] Faraday obtained liquid nitrous oxide by the same method as liquid ammonia, by beating dry ammonium nitrate in a closed bent tube, one arm of which was immersed in a freezing mixture. In this case two layers of liquid are obtained at the cooled end, a lower layer of water and an upper layer of nitrous oxide. This experiment should be conducted with great care, as the pressure of the nitrous oxide in a liquid state is considerable, namely (according to Regnault), at +10° = 45 atmospheres, at 0° = 36 atmospheres, at -10° = 29 atmospheres, and at -20° = 23 atmospheres. It boils at -92°, and the pressure is then therefore = 1 atmosphere (_see_ Chapter II., Note 27). [72] Liquid nitrous oxide, in vaporising at the same pressure as liquid carbonic anhydride, gives rise to almost equal or even slightly lower temperatures. Thus at a pressure of 25 mm. carbonic anhydride gives a temperature as low as -115°, and nitrous oxide of -125° (Dewar). The similarity of these properties and even of the absolute boiling point (CO_{2} + 32°, N_{2}O +36°) is all the more remarkable because these gases have the same molecular weight = 44 (Chapter VII.) [73] A very characteristic experiment of simultaneous combustion and intense cold may be performed by means of liquid nitrous oxide; if liquid nitrous oxide be poured into a test tube containing some mercury the mercury will solidify, and if a piece of red-hot charcoal be thrown upon the surface of the nitrous oxide it will continue to burn very brilliantly, giving rise to a high temperature. When introduced into the respiratory organs (and consequently into the blood also) nitrous oxide produces a peculiar kind of intoxication accompanied by spasmodic movements, and hence this gas, discovered by Priestley in 1776, received the name of 'laughing gas.' On a prolonged respiration it produces a state of insensibility (it is an anæsthetic like chloroform), and is therefore employed in dental and surgical operations. Nitrous oxide is easily decomposed into nitrogen and oxygen by the action of heat, or a series of electric sparks; and this explains why a number of substances which cannot burn in nitric oxide do so with great ease in nitrous oxide. In fact, when nitric oxide gives some oxygen on decomposition, this oxygen immediately unites with a fresh portion of the gas to form nitric peroxide, whilst nitrous oxide does not possess this capacity for further combination with oxygen.[74] A mixture of nitrous oxide with hydrogen explodes like detonating gas, gaseous nitrogen being formed, N_{2}O + H_{2} = H_{2}O + N_{2}. The volume of the remaining nitrogen is equal to the original volume of nitrous oxide, and is equal to the volume of hydrogen entering into combination with the oxygen; hence in this reaction equal volumes of nitrogen and hydrogen replace each other. Nitrous oxide is also very easily decomposed by red-hot metals; and sulphur, phosphorus, and charcoal burn in it, although not so brilliantly as in oxygen. A substance in burning in nitrous oxide evolves more heat than an equal quantity burning in oxygen; which most clearly shows that in the formation of nitrous oxide by the combination of nitrogen with oxygen there was not an evolution but an absorption of heat, there being no other source for the excess of heat in the combustion of substances in nitrous oxide (_see_ Note 29). If a given volume of nitrous oxide be decomposed by a metal--for instance, sodium--then there remains, after cooling and total decomposition, a volume of nitrogen, exactly equal to that of the nitrous oxide taken; consequently the oxygen is, so to say, distributed between the atoms of nitrogen without producing an increase in the volume of the nitrogen. [74] In the following chapter we shall consider the volumetric composition of the oxides of nitrogen. It explains the difference between nitric and nitrous oxide. Nitrous oxide is formed with a diminution of volumes (contraction), nitric oxide without contraction, its volume being equal to the sum of the volumes of the nitrogen and oxygen of which it is composed. By oxidation, if it could be directly accomplished, two volumes of nitrous oxide and one volume of oxygen would not give three but four volumes of nitric oxide. These facts must be taken into consideration in comparing the calorific equivalents of formation, the capacity for supporting combustion, and other properties of nitrous and nitric oxides, N_{2}O and NO. CHAPTER VII MOLECULES AND ATOMS. THE LAWS OF GAY-LUSSAC AND AVOGADRO-GERHARDT Hydrogen combines with oxygen in the proportion of two volumes to one. The composition by volume of nitrous oxide is exactly similar--it is composed of two volumes of nitrogen and one volume of oxygen. By decomposing ammonia by the action of an electric spark it is easy to prove that it contains one volume of nitrogen to three volumes of hydrogen. So, similarly, it is found, whenever a compound is decomposed and the volumes of the gases proceeding from it are measured, that the volumes of the gases or vapours entering into combination are in a very simple proportion to one another. With water, nitrous oxide, &c., this may be proved by direct observation; but in the majority of cases, and especially with substances which, although volatile--that is, capable of passing into a gaseous (or vaporous) state--are liquid at the ordinary temperature, such a direct method of observation presents many difficulties. But, then, if the densities of the vapours and gases be known, the same simplicity in their ratio is shown by calculation. The volume of a substance is proportional to its weight, and inversely proportional to its density, and therefore by dividing the amount by weight of each substance entering into the composition of a compound by its density in the gaseous or vaporous state we shall obtain factors which will be in the same proportion as the volumes of the substances entering into the composition of the compound.[1] So, for example, water contains eight parts by weight of oxygen to one part by weight of hydrogen, and their densities are 16 and 1, consequently their volumes (or the above-mentioned factors) are 1 and 1/2, and therefore it is seen without direct experiment that water contains two volumes of hydrogen for every one volume of oxygen. So also, knowing that nitric oxide contains fourteen parts of nitrogen and sixteen parts of oxygen, and knowing that the specific gravities of these last two gases are fourteen and sixteen, we find that the volumes in which nitrogen and oxygen combine for the formation of nitric oxide are in the proportion of 1 : 1. We will cite another example. In the last chapter we saw that the density of NO_{2} only becomes constant and equal to twenty-three (referred to hydrogen) above 135°, and as a matter of fact a method of direct observation of the volumetric composition of this substance would be very difficult at so high a temperature. But it may be easily calculated. NO_{2}, as is seen from its formula and analysis, contains thirty-two parts by weight of oxygen to fourteen parts by weight of nitrogen, forming forty-six parts by weight of NO_{2}, and knowing the densities of these gases we find that one volume of nitrogen with two volumes of oxygen gives two volumes of nitrogen peroxide. Therefore, knowing the amounts by weight of the substances participating in a reaction or forming a given substance, and knowing the density of the gas or vapour,[2] the volumetric relations of the substances acting in a reaction or entering into the composition of a compound, may be also determined. [1] If the weight be indicated by P, the density by D, and the volume by V, then P/D = _K_V where _K_ is a coefficient depending on the system of the expressions P, D, and V. If D be the weight of a cubic measure of a substance referred to the weight of the same measure of water--if, as in the metrical system (Chapter I., Note 9), the cubic measure of one part by weight of water be taken as a unit of volume--then _K_ = 1. But, whatever it be, it is cancelled in dealing with the comparison of volumes, because comparative and not absolute measures of volumes are taken. In this chapter, as throughout the book, the weight P is given in grams in dealing with absolute weights; and if comparative, as in the expression of chemical composition, then the weight of an atom is taken as unity. The density of gases, D, is also taken in reference to the density of hydrogen, and the volume V in metrical units (cubic centimetres), if it be a matter of absolute magnitudes of volumes, and if it be a matter of chemical transformations--that is, of relative volumes--then the volume of an atom of hydrogen, or of one part by weight of hydrogen, is taken as unity, and all volumes are expressed according to these units. [2] As the volumetric relations of vapours and gases, next to the relations of substances by weight, form the most important province of chemistry, and a most important means for the attainment of chemical conclusions, and inasmuch as these volumetric relations are determined by the densities of gases and vapours, necessarily the methods of determining the densities of vapours (and also of gases) are important factors in chemical research. These methods are described in detail in works on physics and physical and analytical chemistry, and therefore we here only touch on the general principles of the subject. If we know the weight _p_ and volume _v_, occupied by the vapour of a given substance at a temperature _t_ and pressure _h_, then its density may be directly obtained by dividing _p_ by the weight of a volume _v_ of hydrogen (if the density be expressed according to hydrogen, _see_ Chapter II., Note 23) at _t_ and _h_. Hence, the methods of determining the density of vapours and gases are based on the determination of _p_, _v_, _t_, and _h_. The two last data (the temperature _t_ and pressure _h_) are given by the thermometer and barometer and the heights of mercury or other liquid confining the gas, and therefore do not require further explanation. It need only be remarked that: (1) In the case of easily volatile liquids there is no difficulty in procuring a bath with a constant temperature, but that it is nevertheless best (especially considering the inaccuracy of thermometers) to have a medium of absolutely constant temperature, and therefore to take either a bath in which some substance is melting--such as melting ice at 0° or crystals of sodium acetate, melting at +56°--or, as is more generally practised, to place the vessel containing the substance to be experimented with in the vapour of a liquid boiling at a definite temperature, and knowing the pressure under which it is boiling, to determine the temperature of the vapour. For this purpose the boiling points of water at different pressures are given in Chapter I., Note 11, and the boiling points of certain easily procurable liquids at various pressures are given in Chapter II., Note 27. (2) With respect to temperatures above 300° (below which mercurial thermometers may be conveniently employed), they are most simply obtained constant (to give time for the weight and volume of a substance being observed in a given space, and to allow that space to attain the calculated temperature _t_) by means of substances boiling at a high temperature. Thus, for instance, at the ordinary atmospheric pressure the temperature _t_ of the vapour of sulphur is about 445°, of phosphorus pentasulphide 518°, of tin chloride 606°, of cadmium 770°, of zinc 930° (according to Violle and others), or 1040° (according to Deville), &c. (3) The indications of the hydrogen thermometer must be considered as the most exact (but as hydrogen diffuses through incandescent platinum, nitrogen is usually employed). (4) The temperature of the vapours used as the bath should in every case be several degrees higher than the boiling point of the liquid whose density is to be determined, in order that no portion should remain in a liquid state. But even in this case, as is seen from the example of nitric peroxide (Chapter VI.), the vapour density does not always remain constant with a change of _t_, as it should were the law of the expansion of gases and vapours absolutely exact (Chapter II., Note 26). If variations of a chemical and physical nature similar to that which we saw in nitric peroxide take place in the vapours, the main interest is centred in _constant_ densities, which do not vary with _t_, and therefore the possible effect of _t_ on the density must always be kept in mind in having recourse to this means of investigation. (5) Usually, for the sake of convenience of observation, the vapour density is determined at the atmospheric pressure which is read on the barometer; but in the case of substances which are volatilised with difficulty, and also of substances which decompose, or, in general, vary at temperatures near their boiling points, it is best or even indispensable to conduct the determination at low pressures, whilst for substances which decompose at low pressures the observations have to be conducted under a more or less considerably increased pressure. (6) In many cases it is convenient to determine the vapour density of a substance in admixture with other gases, and consequently under the partial pressure, which may be calculated from the volume of the mixture and that of the intermixed gas (_see_ Chapter I., Note 1). This method is especially important for substances which are easily decomposable, because, as shown by the phenomena of dissociation, a substance is able to remain unchanged in the atmosphere of one of its products of decomposition. Thus, Wurtz determined the density of phosphoric chloride, PCl_{5}, in admixture with the vapour of phosphorous chloride, PCl_{3}. (7) It is evident, from the example of nitric peroxide, that a change of pressure may alter the density and aid decomposition, and therefore identical results are sometimes obtained (if the density be variable) by raising _t_ and lowering _h_; but if the density does not vary under these variable conditions (at least, to an extent appreciably exceeding the limits of experimental error), then this _constant_ density indicates the _gaseous_ and _invariable_ state of a substance. The laws hereafter laid down refer only to such vapour densities. But the majority of volatile substances show such a constant density at a certain degree above their boiling points up to the starting point of decomposition. Thus, the density of aqueous vapour does not vary for _t_ between the ordinary temperature and 1000° (there are no trustworthy determinations beyond this) and for pressures varying from fractions of an atmosphere up to several atmospheres. If, however, the density does vary considerably with a variation of _h_ and _t_, the fact may serve as a guide for the investigation of the chemical changes which are undergone by the substance in a state of vapour, or at least as an indication of a deviation from the laws of Boyle, Mariotte, and Gay-Lussac (for the expansion of gases with _t_). In certain cases the separation of one form of deviation from the other may be explained by special hypotheses. With respect to the means of determining _p_ and _v_, with a view to finding the vapour density, we may distinguish three chief methods: (_a_) by weight, by ascertaining the weight of a definite volume of vapour; (_b_) by volume, by measuring the volume occupied by the vapour of a definite weight of a substance; and (_c_) by displacement. The last-mentioned is essentially volumetric, because a known weight of a substance is taken, and the volume of the air displaced by the vapour at a given _t_ and _h_ is determined. [Illustration: FIG. 52.--Apparatus for determining the vapour density by Dumas' method. A small quantity of the liquid whose vapour density is to be determined is placed in the glass globe, and heated in a water or oil bath to a temperature above the boiling point of the liquid. When all the liquid has been converted into vapour and has displaced all the air from the globe, the latter is sealed up and weighed. The capacity of the globe is then measured, and in this manner the volume occupied by a known weight of vapour at a known temperature is determined.] [Illustration: FIG. 53.--Deville and Troost's apparatus for determining the vapour densities, according to Dumas' method, of substances which boil at high temperatures. A porcelain globe containing the substance whose vapour density is to be determined is heated in the vapour of mercury (350°), sulphur (410°), cadmium (850°), or zinc (1,040°). The globe is sealed up in an oxyhydrogen flame.] The method by weight (_a_) is the most trustworthy and historically important. _Dumas' method_ is typical. An ordinary spherical glass or porcelain vessel, like those shown respectively in figs. 52 and 53, is taken, and an excess of the substance to be experimented upon is introduced into it. The vessel is heated to a temperature _t_ higher than the boiling point of the liquid: this gives a vapour which displaces the air, and fills the spherical space. When the air and vapour cease escaping from the sphere, it is fused up or closed by some means; and when cool, the weight of the vapour remaining in the sphere is determined (either by direct weighing of the vessel with the vapour and introducing the necessary corrections for the weight of the air and of the vapour itself, or the weight of the volatilised substance is determined by chemical methods), and the volume of the vapour at _t_ and the barometric pressure _h_ are then calculated. _The volumetric method_ (_b_) originally employed by Gay-Lussac and then modified by Hofmann and others is based on the principle that a weighed quantity of the liquid to be experimented with (placed in a small closed vessel, which is sometimes fused up before weighing, and, if quite full of the liquid, breaks when heated in a vacuum) is introduced into a graduated cylinder heated to _t_, or simply into a Torricellian vacuum, as shown in fig. 54, and the number of volumes occupied by the vapour noted when the space holding it is heated to the desired temperature _t_. [Illustration: FIG. 54.--Hofmann's apparatus for determining vapour densities. The internal tube, about one metre long, which is calibrated and graduated, is filled with mercury and inverted in a mercury bath. A small bottle (depicted in its natural size on the left) containing a weighed quantity of the liquid whose vapour density is to be determined, is introduced into the Torricellian vacuum. Steam, or the vapour of amyl alcohol, &c., is passed through the outer tube, and heats the internal tube to the temperature _t_, at which the volume of vapour is measured.] [Illustration: FIG. 55.--Victor Meyer's apparatus for determining vapour densities. The tube _b_ is heated in the vapour of a liquid of constant boiling point. A glass tube, containing the liquid to be experimented upon, is caused to fall from _d_. The air displaced is collected in the cylinder _e_, in the trough _f_.] _The method of displacement_ (_c_) proposed by Victor Meyer is based on the fact that a space _b_ is heated to a constant temperature _t_ (by the surrounding vapours of a liquid of constant boiling point), and the air (or other gas enclosed in this space) is allowed to attain this temperature, and when it has done so a glass bulb containing a weighed quantity of the substance to be experimented with is dropped into the space. The substance is immediately converted into vapour, and displaces the air into the graduated cylinder _e_. The amount of this air is calculated from its volume, and hence the volume at _t_, and therefore also the volume occupied by the vapour, is found. The general arrangement of the apparatus is given in fig. 55. Such an investigation (either direct, or by calculation from the densities and composition) of every chemical reaction, resulting in the formation of definite chemical compounds, shows that the volumes of the reacting substances in a gaseous or vaporous state are either equal or are in simple multiple proportion.[3] This forms the _first law_ of those discovered by _Gay-Lussac_. It may be formulated as follows: _The amounts of substances entering into chemical reaction occupy under similar physical conditions, in a gaseous or vaporous state, equal or simple multiple volumes._ This law refers not only to elements, but also to compounds entering into mutual chemical combination; thus, for example, one volume of ammonia gas combines with one volume of hydrogen chloride. For in the formation of sal-ammoniac, NH_{4}Cl, there enter into reaction 17 parts by weight of ammonia, NH_{3}, which is 8·5 times denser than hydrogen, and 36·5 parts by weight of hydrogen chloride, whose vapour density is 18·25 times that of hydrogen, as has been proved by direct experiment. By dividing the weights by the respective densities we find that the volume of ammonia, NH_{3}, is equal to two, and so also the volume of hydrogen chloride. Hence the volumes of the compounds which here combine together are equal to each other. Taking into consideration that the law of Gay-Lussac holds good, not only for elements, but also for compounds, it should be expressed as follows: _Substances interact with one another in commensurable volumes of their vapours._[4] [3] Vapours and gases, as already explained in the second chapter, are subject to the same laws, which are, however, only approximate. It is evident that for the deduction of the laws which will presently be enunciated it is only possible to take into consideration a perfect gaseous state (far removed from the liquid state) and chemical invariability in which the _vapour density is constant_--that is, the volume of a given gas or vapour varies like a volume of hydrogen, air, or other gas, with the pressure and temperature. It is necessary to make this statement in order that it may be clearly seen that the laws of gaseous volumes, which we shall describe presently, are in the most intimate connection with the laws of the variations of volumes with pressure and temperature. And as these latter laws (Chapter II.) are not infallible, but only approximately exact, the same, therefore, applies to the laws about to be described. And as it is possible to find more exact laws (a second approximation) for the variation of _v_ with _p_ and _t_ (for example, van der Waals' formula, Chapter II., Note 33), so also a more exact expression of the relation between the composition and the density of vapours and gases is also possible. But to prevent any doubt arising at the very beginning as to the breadth and general application of the laws of volumes, it will be sufficient to mention that the density of such gases as oxygen, nitrogen, and carbonic anhydride is already known to _remain constant_ (within the limits of experimental error) between the ordinary temperature and a white heat; whilst, judging from what is said in my work on the 'Tension of Gases' (vol. i. p. 9), it may be said that, as regards pressure, the relative density remains very constant, even when the deviations from Mariotte's law are very considerable. However, in this respect the number of data is as yet too small to arrive at an exact conclusion. [4] We must recollect that this law is only approximate, like Boyle and Mariotte's law, and that, therefore, like the latter, a more exact expression may be found for the exceptions. The law of combining volumes and the law of multiple proportion were discovered independently of each other--the one in France by Gay-Lussac, the other in England by Dalton--almost simultaneously. In the language of the atomic hypothesis it may be said that atomic quantities of elements occupy equal or multiple volumes. The first law of Gay-Lussac expresses the relation between the volumes of the component parts of a compound. Let us now consider the relation existing between the volumes of the component parts and of the compounds which proceed from them. This may sometimes be determined by direct observation. Thus the volume occupied by water, formed by two volumes of hydrogen and one volume of oxygen, may be determined by the aid of the apparatus shown in fig. 56. The long glass tube is closed at the top and open at the bottom, which is immersed in a cylinder containing mercury. The closed end is furnished with wires like a eudiometer. The tube is filled with mercury, and then a certain volume of detonating gas is introduced. This gas is obtained from the decomposition of water, and therefore in every three volumes contains two volumes of hydrogen and one volume of oxygen. The tube is surrounded by a second and wider glass tube, and the vapour of a substance boiling above 100°--that is, whose boiling point is higher than that of water--is passed through the annular space between them. Amyl alcohol, whose boiling point is 132°, may be taken for this purpose. The amyl alcohol is boiled in the vessel to the right hand and its vapour passed between the walls of the two tubes. In the case of amyl alcohol the outer glass tube should be connected with a condenser to prevent the escape into the air of the unpleasant-smelling vapour. The detonating gas is thus heated up to a temperature of 132°. When its volume becomes constant it is measured, the height of the column of mercury in the tube above the level of the mercury in the cylinder being noted. Let this volume equal _v_; it will therefore contain 1/3 _v_ of oxygen and 2/3 _v_ of hydrogen. The current of vapour is then stopped, and the gas exploded; water is formed, which condenses into a liquid. The volume occupied by the vapour of the water formed has now to be determined. For this purpose the vapour of the amyl alcohol is again passed between the tubes, and thus the whole of the water formed is converted into vapour at the same temperature as that at which the detonating gas was measured; and the cylinder of mercury being raised until the column of mercury in the tube stands at the same height above the surface of the mercury in the cylinder as it did before the explosion, it is found that the volume of the water formed is equal to 2/3 _v_--that is, it is equal to the volume of the hydrogen contained in it. Consequently the volumetric composition of water is expressed in the following terms: Two volumes of hydrogen combine with one volume of oxygen to form two volumes of aqueous vapour. For substances which are gaseous at the ordinary temperature, this direct method of observation is sometimes very easily conducted; for instance, with ammonia, nitric and nitrous oxides. Thus to determine the composition by volume of nitrous oxide, the above-described apparatus may be employed. Nitrous oxide is introduced into the tube, and after measuring its volume electric sparks are passed through the gas; it is then found that two volumes of nitrous oxide have given three volumes of gases--namely, two volumes of nitrogen and one volume of oxygen. Consequently the composition of nitrous oxide is similar to that of water; two volumes of nitrogen and one volume of oxygen give two volumes of nitrous oxide. By decomposing ammonia it is found to be composed in such a manner that two volumes give one volume of nitrogen and three volumes of hydrogen; also two volumes of nitric oxide are formed by the union of one volume of oxygen with one volume of nitrogen. The same relations may be proved by calculation from the vapour densities, as was described above. [Illustration: FIG. 56.--Apparatus for demonstrating the volume occupied by the steam formed from the explosion of detonating gas.] Comparisons of various results made by the aid of direct observations or calculation, an example of which has just been cited, led Gay-Lussac to the conclusion that _the volume of a compound in a gaseous or vaporous state is always in simple multiple proportion to the volume of each of the component parts of which it is formed_ (and consequently to the sum of the volumes of the elements of which it is formed). This is the _second law of Gay-Lussac_; it extends the simplicity of the volumetric relations to compounds, and is of the same nature as that presented by the elements entering into mutual combination. Hence not only the substances forming a given compound, but also the substances formed, exhibit a simple relation of volume when measured as vapour or gas.[5] [5] This second law of volumes may be considered as a consequence of the first law. The first law requires simple ratios between the volumes of the combining substances _A_ and _B_. A substance _AB_ is produced by their combination. It may, according to the law of multiple proportion, combine, not only with substances _C_, _D_, &c., but also with _A_ and with _B_. In this new combination the volume of _AB_, combining with the volume of _A_, should be in simple multiple proportion with the volume of _A_; hence the volume of the compound _AB_ is in simple proportion to the volume of its component parts. Therefore only one law of volumes need be accepted. We shall afterwards see that there is a third law of volumes embracing also the two first laws. When a compound is formed from two or more components, there may or may not be a contraction; the volume of the reacting substances is in this case either equal to or greater than the volume of the resultant compound. The reverse is naturally observed in the case of decompositions, when from one substance there are produced several of simpler nature. Therefore in the future we shall term _combination_ a reaction in which a contraction is observed--that is, a diminution in the volume of the component bodies in a state of vapour or gas; and we shall term _decomposition_ a reaction in which an expansion is produced; while those reactions in which the volumes in a gaseous or vaporous state remain constant (the volumes being naturally compared at the same temperature and pressure) we shall term reactions of _substitution_ or of double decomposition. Thus the transition of oxygen into ozone is a reaction of combination, the formation of nitrous oxide from oxygen and nitrogen will also be a combination, the formation of nitric oxide from the same will be a reaction of substitution, the action of oxygen on nitric oxide a combination, and so on. The degree of contraction produced in the formation of chemical compounds not unfrequently leads to the possibility of distinguishing the degree of change which takes place in the chemical character of the components when combined. In those cases in which a contraction occurs, the properties of the resultant compound are very different from the properties of the substances of which it is composed. Thus ammonia bears no resemblance in its physical or chemical properties to the elements from which it is derived; a contraction takes place in a state of vapour, indicating a proximation of the elements--the distance between the atoms is diminished, and from gaseous substances there is formed a liquid substance, or at any rate one which is easily liquefied. For this reason nitrous oxide formed by the condensation of two permanent gases is a substance which is somewhat easily converted into a liquid; again, nitric acid, which is formed from elements which are permanent gases, is a liquid, whilst, on the contrary, nitric oxide, which is formed without contraction and is decomposed without expansion, remains a gas which is as difficult to liquefy as nitrogen and oxygen. In order to obtain a still more complete idea of the dependence of the properties of a compound on the properties of the component substances, it is further necessary to know the quantity of heat which is developed in the formation of the compound. If this quantity be large--as, for example, in the formation of water--then the amount of energy in the resultant compound will be considerably less than the energy of the elements entering into its composition; whilst, on the contrary, if the amount of heat evolved in the formation of a compound be small, or if there even be an absorption of heat, as in the formation of nitrous oxide, then the energy of the elements is not destroyed, or is only altered to a slight extent; hence, notwithstanding the contraction (compression) involved in its formation, nitrous oxide supports combustion. The preceding laws were deduced from purely experimental and empirical data and as such evoke further consequences, as the law of multiple proportions gave rise to the atomic theory and the law of equivalents (Chapter IV.) In view of the atomic conception of the constitution of substances, the question naturally arises as to what, then, are the relative volumes proper to those physically indivisible molecules which chemically react on each other and consist of the atoms of elements. The simplest possible hypothesis in this respect would be that the volumes of the molecules of substances are equal; or, what is the same thing, to suppose that equal volumes of vapours and gases contain an equal number of molecules. This proposition was first enunciated by the Italian savant _Avogadro_ in 1810. It was also admitted by the French physico-mathematician _Ampère_ (1815) for the sake of simplifying all kinds of physico-mathematical conceptions respecting gases. But Avogadro and Ampère's propositions were not generally received in science until Gerhardt in the forties had applied them to the generalisation of chemical reactions, and had demonstrated, by aid of a series of phenomena, that the reactions of substances actually take place with the greatest simplicity, and more especially that such reactions take place between those quantities of substances which occupy equal volumes, and until he had stated the hypothesis in an exact manner and deduced the consequences that necessarily follow from it. Following Gerhardt, Clausius, in the fifties, placed this hypothesis of the equality of the number of molecules in equal volumes of gases and vapours on the basis of the kinetic theory of gases. At the present day the hypothesis of Avogadro and Gerhardt lies at the basis of contemporary physical, mechanical, and chemical conceptions; the consequences arising from it have often been subject to doubt, but in the end have been verified by the most diverse methods; and now, when all efforts to refute those consequences have proved fruitless, the hypothesis must be considered as verified,[6] and the _law of Avogadro-Gerhardt_ must be spoken of as fundamental, and as of great importance for the comprehension of the phenomena of nature. The law may now be formulated from two points of view. In the first place, from a physical aspect: _equal volumes of gases_ (or vapours) at equal temperatures and pressures _contain the same number of molecules_--or of particles of matter which are neither mechanically nor physically divisible--previous to chemical change. In the second place, from a chemical aspect, the same law may be expressed thus: _the quantities of substances entering into chemical reactions occupy, in a state of vapour, equal volumes_. For our purpose the chemical aspect is the most important, and therefore, before developing the law and its consequences, we will consider the chemical phenomena from which the law is deduced or which it serves to explain. [6] It must not be forgotten that Newton's law of gravity was first a hypothesis, but it became a trustworthy, perfect theory, and acquired the qualities of a fundamental law owing to the concord between its deductions and actual facts. All laws, all theories, of natural phenomena, are at first hypotheses. Some are rapidly established by their consequences exactly agreeing with facts; others only take root by slow degrees; and there are many which are destined to be refuted owing to their consequences being found to be at variance with facts. When two isolated substances interact with each other directly and easily--as, for instance, an alkali and an acid--then it is found that the reaction is accomplished between quantities which in a gaseous state occupy equal volumes. Thus ammonia, NH_{3}, reacts directly with hydrochloric acid, HCl, forming sal-ammoniac, NH_{4}Cl, and in this case the 17 parts by weight of ammonia occupy the same volume as the 36·5 parts by weight of hydrochloric acid.[7] Ethylene, C_{2}H_{4}, combines with chlorine, Cl_{2}, in only one proportion, forming ethylene dichloride, C_{2}H_{4}Cl_{2}, and this combination proceeds directly and with great facility, the reacting quantities occupying equal volumes. Chlorine reacts with hydrogen in only one proportion, forming hydrochloric acid, HCl, and in this case equal volumes interact with each other. If an equality of volumes is observed in cases of combination, it should be even more frequently encountered in cases of decomposition, taking place in substances which split up into two others. Indeed, acetic acid breaks up into marsh gas, CH_{4}, and carbonic anhydride, CO_{2}, and in the proportions in which they are formed from acetic acid they occupy equal volumes. Also from phthalic acid, C_{8}H_{6}O_{4}, there may be obtained benzoic acid, C_{7}H_{6}O_{2}, and carbonic anhydride, CO_{2}, and as all the elements of phthalic acid enter into the composition of these substances, it follows that, although they cannot re-form it by their direct action on each other (the reaction is not reversible), still they form the direct products of its decomposition, and they occupy equal volumes. But benzoic acid, C_{7}H_{6}O_{2}, is itself composed of benzene, C_{6}H_{6}, and carbonic anhydride, CO_{2}, which also occupy equal volumes.[8] There is an immense number of similar examples among those organic substances to whose study Gerhardt consecrated his whole life and work, and he did not allow such facts as these to escape his attention. Still more frequently in the phenomena of substitution, when two substances react on one another, and two are produced without a change of volume, it is found that the two substances acting on each other occupy equal volumes as well as each of the two resultant substances. Thus, in general, reactions of substitution take place between volatile acids, HX, and volatile alcohols, R(OH), with the formation of ethereal salts, RX, and water, H(OH), and the volume of the vapour of the reacting quantities, HX, R(OH), and RX, is the same as that of water H(OH), whose weight, corresponding with the formula, 18, occupies 2 volumes, if 1 part by weight of hydrogen occupy 1 volume and the density of aqueous vapour referred to hydrogen is 9. Such general examples, of which there are many,[9] show that the reaction of equal volumes forms a chemical phenomenon of frequent occurrence, indicating the necessity for acknowledging the law of Avogadro-Gerhardt. [7] This is not only seen from the above calculations, but may be proved by experiment. A glass tube, divided in the middle by a stopcock, is taken and one portion filled with _dry_ hydrogen chloride (the dryness of the gases is very necessary, because ammonia and hydrogen chloride are both very soluble in water, so that a small trace of water may contain a large amount of these gases in solution) and the other with dry ammonia, under the atmospheric pressure. One orifice (for instance, of that portion which contains the ammonia) is firmly closed, and the other is immersed under mercury, and the cock is then opened. Solid sal-ammoniac is formed, but if the volume of one gas be greater than that of the other, some of the first gas will remain. By immersing the tube in the mercury in order that the internal pressure shall equal the atmospheric pressure, it may easily be shown that the volume of the remaining gas is equal to the difference between the volumes of the two portions of the tube, and that this remaining gas is part of that whose volume was the greater. [8] Let us demonstrate this by figures. From 122 grams of benzoic acid there are obtained (_a_) 78 grams of benzene, whose density referred to hydrogen = 39, hence the relative volume = 2; and (_b_) 44 grams of carbonic anhydride, whose density = 22, and hence the volume = 2. It is the same in other cases. [9] A large number of such generalised reactions, showing reaction by equal volumes, occur in the case of the hydrocarbon derivatives, because many of these compounds are volatile. The reactions of alkalis on acids, or anhydrides on water, &c., which are so frequent between mineral substances, present but few such examples, because many of these substances are not volatile and their vapour densities are unknown. But essentially the same is seen in these cases also; for instance, sulphuric acid, H_{2}SO_{4}, breaks up into the anhydride, SO_{3}, and water, H_{2}O, which exhibit an equality of volumes. Let us take another example where three substances combine in equal volumes: carbonic anhydride, CO_{2}, ammonia, NH_{3}, and water, H_{2}O (the volumes of all are equal to 2), form acid ammonium carbonate, (NH_{4})HCO_{3}. But the question arises, What is the relation of volumes if the reaction of two substances takes place in more than one proportion, according to the law of multiple proportions? A definite answer can only be given in cases which have been very thoroughly studied. Thus chlorine, in acting on marsh gas, CH_{4}, forms four compounds, CH_{3}Cl, CH_{2}Cl_{2}, CHCl_{3}, and CCl_{4}, and it may be established by direct experiment that the substance CH_{3}Cl (methylic chloride) precedes the remainder, and that the latter proceed from it by the further action of chlorine. And this substance, CH_{3}Cl, is formed by the reaction of equal volumes of marsh gas, CH_{4}, and chlorine, Cl_{2}, according to the equation CH_{4} + Cl_{2} = CH_{3}Cl + HCl. A great number of similar cases are met with amongst organic--that is, carbon--compounds. Gerhardt was led to the discovery of his law by investigating many such reactions, and by observing that in them the reaction of equal volumes precedes all others. But if nitrogen or hydrogen give several compounds with oxygen, the question proposed above cannot be answered with complete clearness, because the successive formations of the different combinations cannot be so strictly defined. It may be supposed, but neither definitely affirmed nor experimentally confirmed, that nitrogen and oxygen first give nitric oxide, NO, and only subsequently the brown vapours N_{2}O_{3} and NO_{2}. Such a sequence in the combination of nitrogen with oxygen can only be supposed on the basis of the fact that NO forms N_{2}O_{3} and NO_{2} directly with oxygen. If it be admitted that NO (and not N_{2}O or NO_{2}) be first formed, then this instance would also confirm the law of Avogadro-Gerhardt, because nitric oxide contains equal volumes of nitrogen and oxygen. So, also, it may be admitted that, in the combination of hydrogen with oxygen, hydrogen peroxide is first formed (equal volumes of hydrogen and oxygen), which is decomposed by the heat evolved into water and oxygen. This explains the presence of traces of hydrogen peroxide (Chapter IV.) in almost all cases of the combustion or oxidation of hydrogenous substances; for it cannot be supposed that water is first formed and then the peroxide of hydrogen, because up to now such a reaction has not been observed, whilst the formation of H_{2}O from H_{2}O_{2} is very easily reproduced.[10] [10] This opinion which I have always held (since the first editions of this work), as to the primary origin of hydrogen peroxide and of the formation of water by means of its decomposition, has in latter days become more generally accepted, thanks more especially to the work of Traube. Probably it explains most simply the necessity for the presence of traces of water in many reactions, as, for instance, in the explosion of carbonic oxide with oxygen, and perhaps the theory of the explosion of detonating gas itself and of the combustion of hydrogen will gain in clearness and truth if we take into consideration the preliminary formation of hydrogen peroxide and its decomposition. We may here point out the fact that Ettingen (at Dorpat, 1888) observed the existence of currents and waves in the explosion of detonating gas by taking photographs, which showed the periods of combustion and the waves of explosion, which should be taken into consideration in the theory of this subject. As the formation of H_{2}O_{2} from O_{2} and H_{2} corresponds with a less amount of heat than the formation of water from H_{2} and O, it may be that the temperature of the flame of detonating gas depends on the pre-formation of hydrogen peroxide. Thus a whole series of phenomena show that the chemical reaction of substances actually takes place, as a rule, between equal volumes, but this does not preclude the possibility of the frequent reaction of unequal volumes, although, in this case, it is often possible to discover a preceding reaction between equal volumes.[11] [11] The possibility of reactions between unequal volumes, notwithstanding the general application of the law of Avogadro-Gerhardt, may, in addition to what has been said above, depend on the fact that the participating substances, at the moment of reaction, undergo a preliminary modification, decomposition, isomeric (polymeric) transformation, &c. Thus, if NO_{2}, seems to proceed from N_{2}O_{4}, if O_{2} is formed from O_{3}, and the converse, then it cannot be denied that the production of molecules containing only one atom is also possible--for instance, of oxygen--as also of higher polymeric forms--as the molecule N from N_{2}, or H_{3} from H_{2}. In this manner it is obviously possible, by means of a series of hypotheses, to explain the cases of the formation of ammonia, NH_{3}, from 3 vols. of hydrogen and 1 vol. of nitrogen. But it must be observed that perhaps our information in similar instances is, as yet, far from being complete. If hydrazine or diamide N_{2}H_{4} (Chapter VI. Note 20 bis) is formed and the imide N_{2}H_{2} in which 2 vols. of hydrogen are combined with 2 vols. of nitrogen, then the reaction here perhaps first takes place between equal volumes. If it be shown that diamide gives nitrogen and ammonia (3N_{2}H_{4} = N_{2} + 4NH_{3}) under the action of sparks, heat, or the silent discharge, &c., then it will be possible to admit that it is formed before ammonia. And perhaps the still less stable imide N_{2}H_{2}, which may also decompose with the formation of ammonia, is produced before the amide N_{2}H_{4}. I mention this to show that the fact of apparent exceptions existing to the law of reactions between equal volumes does not prove the impossibility of their being included under the law on further study of the subject. Having put forward a certain law or hypothesis, consequences must be deduced from it, and if by their means clearness and consistency are attained--and especially, if by their means that which could not otherwise be known can be predicted--then the consequences verify the hypothesis. This was the case with the law now under discussion. The mere simplicity of the deduction of the weights proper to the atoms of the elements, or the mere fact that having admitted the law it follows (as will afterwards be shown) that the _vis viva_ of the molecules of all gases is a constant quantity, is quite sufficient reason for retaining the hypothesis, if not for believing in it as a fact beyond doubt. And such is the whole doctrine of atoms. And since by the acceptance of the law it became possible to foretell even the properties and atomic weights of elements which had not yet been discovered, and these predictions afterwards proved to be in agreement with the actual facts, it is evident that the law of Avogadro-Gerhardt penetrates deeply into the nature of the chemical relation of substances. This being granted, it is possible at the present time to exhibit and deduce the truth under consideration in many ways, and in every case, like all that is highest in science (for example, the laws of the indestructibility of matter, of the conservation of energy, of gravity, &c.), it proves to be not an empirical conclusion from direct observation and experiment, not a direct result of analysis, but a creation, or instinctive penetration, of the inquiring mind, guided and directed by experiment and observation--a synthesis of which the exact sciences are capable equally with the highest forms of art. Without such a synthetical process of reasoning, science would only be a mass of disconnected results of arduous labour, and would not be distinguished by that vitality with which it is really endowed when once it succeeds in attaining a synthesis, or concordance of outward form with the inner nature of things, without losing sight of the diversities of individual parts; in short, when it discovers by means of outward phenomena, which are apparent to the sense of touch, to observation, and to the common mind, the internal signification of things--discovering simplicity in complexity and uniformity in diversity. And this is the highest problem of science. The law of Avogadro-Gerhardt may also be easily expressed in an algebraical form. If the weight of a molecule, or of that quantity of a substance which enters into chemical reaction and occupies in a state of vapour, according to the law, a volume equal to that occupied by the molecules of other bodies, be indicated by the letters M_{1}, M_{2} ... or, in general, M, and if the letters D_{1}, D_{2}, ... or, in general, D, stand for the density or weight of a given volume of the gases or vapours of the corresponding substances under certain definite conditions of temperature and pressure, then the law requires that M_{1}/D_{1} = M_{2}/D_{2} ... = M/D = C where C is a certain constant. This expression shows directly that the volumes corresponding with the weights M_{1}, M_{2} ... M, are equal to a certain constant, because the volume is proportional to the weight and inversely proportional to the density. The magnitude of C is naturally conditioned by and dependent on the units taken for the expression of the weights of the molecules and the densities. The weight of a molecule (equal to the sum of the atomic weights of the elements forming it) is usually expressed by taking the weight of an atom of hydrogen as unity, and hydrogen is now also chosen as the unit for the expression of the densities of gases and vapours; it is therefore only necessary to find the magnitude of the constant for any one compound, as it will be the same for all others. Let us take water. Its reacting mass is expressed (conditionally and relatively) by the formula or molecule H_{2}O, for which M = 18, if H = 1, as we already know from the composition of water. Its vapour density, or D, compared to hydrogen = 9, and consequently for water C = 2, and therefore and in general for the molecules of all substances M/D = 2. Consequently the weight of a molecule is equal to twice its vapour density expressed in relation to hydrogen, and conversely _the density of a gas is equal to half the molecular weight referred to hydrogen_. The truth of this may be seen from a very large number of observed vapour densities by comparing them with the results obtained by calculation. As an illustration, we may point out that for ammonia, NH_{3}, the weight of the molecule or quantity of the reacting substance, as well as the composition and weight corresponding with the formula, is expressed by the figures 14 + 3 = 17. Consequently M = 17. Hence, according to the law, D = 8·5. And this result is also obtained by experiment. The density, according to both formula and experiment, of nitrous oxide, N_{2}O, is 22, of nitric acid 15, and of nitric peroxide 23. In the case of nitrous anhydride, N_{2}O_{3}, as a substance which dissociates into NO + NO_{2}, the density should vary between 38 (so long as the N_{2}O_{3} remains unchanged) and 19 (when NO + NO_{2} is obtained). There are no figures of constant density for H_{2}O_{2}, NHO_{3}, N_{2}O_{4}, and many similar compounds which are either wholly or partially decomposed in passing into vapour. Salts and similar substances either have no vapour density because they do not pass into vapour (for instance, potassium nitrate, KNO_{3}) without decomposition, or, if they pass into vapour without decomposing, their vapour density is observed with difficulty only at very high temperatures. The practical determination of the vapour density at these high temperatures (for example, for sodium chloride, ferrous chloride, stannous chloride, &c.) requires special methods which have been worked out by Sainte-Claire Deville, Crafts, Nilson and Pettersson, Meyer, Scott, and others. Having overcome the difficulties of experiment, it is found that the law of Avogadro-Gerhardt holds good for such salts as potassium iodide, beryllium chloride, aluminium chloride, ferrous chloride, &c.--that is, the density obtained by experiment proves to be equal to half the molecular weight--naturally within the limits of experimental error or of possible deviation from the law. Gerhardt deduced his law from a great number of examples of volatile carbon compounds. We shall become acquainted with certain of them in the following chapters; their entire study, from the complexity of the subject, and from long-established custom, forms the subject of a special branch of chemistry termed 'organic' chemistry. With all these substances the observed and calculated densities are very similar. When the consequences of a law are verified by a great number of observations, it should be considered as confirmed by experiment. But this does not exclude the possibility of _apparent_ deviations. They may evidently be of two kinds: the fraction M/D may be found to be either greater or less than 2--that is, the calculated density may be either greater or less than the observed density. When the difference between the results of experiment and calculation falls within the possible errors of experiment (for example, equal to hundredths of the density), or within a possible error owing to the laws of gases having an only approximate application (as is seen from the deviations, for instance, from the law of Boyle and Mariotte), then the fraction M/D proves but slightly different from 2 (between 1·9 and 2·2), and such cases as these may be classed among those which ought to be expected from the nature of the subject. It is a different matter if the quotient of M/D be several times, and in general a multiple, _greater_ or less than 2. The application of the law must then be explained or it must be laid aside, because the laws of nature admit of no exceptions. We will therefore take two such cases, and first one in which the _quotient_ M/D _is greater than 2, or the density obtained by experiment is less than is in accordance with the law_. It must be admitted, as a consequence of the law of Avogadro-Gerhardt, that there is a decomposition in those cases where the volume of the vapour corresponding with the weight of the amount of a substance entering into reaction is greater than the volume of two parts by weight of hydrogen. Suppose the density of the vapour of water to be determined at a temperature above that at which it is decomposed, then, if not all, at any rate a large proportion of the water will be decomposed into hydrogen and oxygen. The density of such a mixture of gases, or of detonating gas, will be less than that of aqueous vapour; it will be equal to 6 (compared with hydrogen), because 1 volume of oxygen weighs 16, and 2 volumes of hydrogen 2; and, consequently, 3 volumes of detonating gas weigh 18 and 1 volume 6, while the density of aqueous vapour = 9. Hence, if the density of aqueous vapour be determined after its decomposition, the quotient M/D would be found to be 3 and not 2. This phenomenon might be considered as a deviation from Gerhardt's law, but this would not be correct, because it may be shown by means of diffusion through porous substances, as described in Chapter II., that water is decomposed at such high temperatures. In the case of water itself there can naturally be no doubt, because its vapour density agrees with the law at all temperatures at which it has been determined.[12] But there are many substances which decompose with great ease directly they are volatilised, and therefore only exist as solids or liquids, and not in a state of vapour. There are, for example, many salts of this kind, besides all definite solutions having a constant boiling point, all the compounds of ammonia for example, all ammonium salts--&c. Their vapour densities, determined by Bineau, Deville, and others, show that they do not agree with Gerhardt's law. Thus the vapour density of sal-ammoniac, NH_{4}Cl, is nearly 14 (compared with hydrogen), whilst its molecular weight is not less than 53·5, whence the vapour density should be nearly 27, according to the law. The molecule of sal-ammoniac cannot be less than NH_{4}Cl, because it is formed from the molecules NH_{3} and HCl, and contains single atoms of nitrogen and chlorine, and therefore cannot be divided; it further never enters into reactions with the molecules of other substances (for instance, potassium hydroxide, or nitric acid) in quantities of less than 53·5 parts by weight, &c. The calculated density (about 27) is here double the observed density (about 13·4); hence M/D = 4 and not 2. For this reason the vapour density of sal-ammoniac for a long time served as an argument for doubting the truth of the law. But it proved otherwise, after the matter had been fully investigated. The low density depends on the decomposition of sal-ammoniac, on volatilising, into ammonia and hydrogen chloride. The observed density is not that of sal-ammoniac, but of a mixture of NH_{3} and HCl, which should be nearly 14, because the density of NH_{3} = 8·5 and of HCl = 18·2, and therefore the density of their mixture (in equal volumes) should be about 13·4.[13] The actual decomposition of the vapours of sal-ammoniac was demonstrated by Pebal and Than by the same method as the decomposition of water, by passing the vapour of sal-ammoniac through a porous substance. The experiment demonstrating the decomposition during volatilisation of sal-ammoniac may be made very easily, and is a very instructive point in the history of the law of Avogadro-Gerhardt, because without its aid it would never have been imagined that sal-ammoniac decomposed in volatilising, as this decomposition bears all the signs of simple sublimation; consequently the knowledge of the decomposition itself was forestalled by the law. The whole aim and practical use of the discovery of the laws of nature consists in, and is shown by, the fact that they enable the unknown to be foretold, the unobserved to be foreseen. The arrangement of the experiment is based on the following reasoning.[14] According to the law and to experiment, the density of ammonia, NH_{3}, is 8-1/2, and of hydrochloric acid, HCl, 18-1/4, if the density of hydrogen = 1. Consequently, in a mixture of NH_{3} and HCl, the ammonia will penetrate much more rapidly through a porous mass, or a fine orifice, than the heavier hydrochloric acid, just as in a former experiment the hydrogen penetrated more rapidly than the oxygen. Therefore, if the vapour of sal-ammoniac comes into contact with a porous mass, the ammonia will pass through it in greater quantities than the hydrochloric acid, and this excess of ammonia may be detected by means of moist red litmus paper, which should be turned blue. If the vapour of sal-ammoniac were not decomposed, it would pass through the porous mass as a whole, and the colour of the litmus paper would not be altered, because sal-ammoniac is a neutral salt. Thus, by testing with litmus the substances passing through the porous mass, it may be decided whether the sal-ammoniac is decomposed or not when passing into vapour. Sal-ammoniac volatilises at so moderate a temperature that the experiment may be conducted in a glass tube heated by means of a lamp, an asbestos plug being placed near the centre of the tube.[15] The asbestos forms a porous mass, which is unaltered at a high temperature. A piece of dry sal-ammoniac is placed at one side of the asbestos plug, and is heated by a Bunsen burner. The vapours formed are driven by a current of air forced from a gasometer or bag through two tubes containing pieces of moist litmus paper, one blue and one red paper in each. If the sal-ammoniac be heated, then the ammonia appears on the opposite side of the asbestos plug, and the litmus there turns blue. And as an excess of hydrochloric acid remains on the side where the sal-ammoniac is heated, it turns the litmus at that end red. This proves that the sal-ammoniac, when converted into vapour, splits up into ammonia and hydrochloric acid, and at the same time gives an instance of the possibility of correctly conjecturing a fact on the basis of the law of Avogadro-Gerhardt.[15 bis] [12] As the density of aqueous vapour remains constant within the limits of experimental accuracy, even at 1,000°, when dissociation has certainly commenced, it would appear that only a very small amount of water is decomposed at these temperatures. If even 10 p.c. of water were decomposed, the density would be 8·57 and the quotient M/D = 2·1, but at the high temperatures here concerned the error of experiment is not greater than the difference between this quantity and 2. And probably at 1,000° the dissociation is far from being equal to 10 p.c. _Hence the variation in the vapour density of water does not give us the means of ascertaining the amount of its dissociation._ [13] This explanation of the vapour density of sal-ammoniac, sulphuric acid, and similar substances which decompose in being distilled was the most natural to resort to as soon as the application of the law of Avogadro-Gerhardt to chemical relations was begun; it was, for instance, given in my work on _Specific Volumes_, 1856, p. 99. The formula, M/D = 2, which was applied later by many other investigators, had already been made use of in that work. [14] The beginner must remember that an experiment and the mode in which it is carried out must be determined by the principle or fact which it is intended to illustrate, and not _vice versa_, as some suppose. The idea which determines the necessity of an experiment is the chief consideration. [15] It is important that the tubes, asbestos, and sal-ammoniac should be dry, as otherwise the moisture retains the ammonia and hydrogen chloride. [15 bis] Baker (1894) showed that the decomposition of NH_{4}Cl in the act of volatilising only takes place in the presence of water, traces of which are amply sufficient, but that in the total absence of moisture (attained by carefully drying with P_{2}O_{5}) there is no decomposition, and the vapour density of the sal-ammoniac is found to be normal, _i.e._, nearly 27. It is not yet quite clear what part the trace of moisture plays here, and it must be presumed that the phenomenon belongs to the category of electrical and contact phenomena, which have not yet been fully explained (_see_ Chapter IX., Note 29). So also the fact of a decomposition may be proved in the other instances where M/D proved greater than 2, and hence the apparent deviations appear in reality as an excellent proof of the general application and significance of the law of Avogadro-Gerhardt. In those cases where the _quotient_ M/D proves to be _less_ than 2, or the observed density _greater_ than that calculated, by a multiple number of times, the matter is evidently more simple, and the fact observed only indicates that the weight of the molecule is as many times greater as that taken as the quotient obtained is less than 2. So, for instance, in the case of ethylene, whose composition is expressed by CH_{2}, the density was found by experiment to be 14, and in the case of amylene, whose composition is also CH_{2}, the density proved to be 35, and consequently the quotient for ethylene = 1, and for amylene = 2/5. If the molecular weight of ethylene be taken, not as 14, as might be imagined from its composition, but as twice as great--namely, as 28--and for amylene as five times greater--that is as 70--then the molecular composition of the first will be C_{2}H_{4}, and of the second C_{5}H_{10}, and for both of them M/D will be equal to 2. This application of the law, which at first sight may appear perfectly arbitrary, is nevertheless strictly correct, because the amount of ethylene which reacts--for example, with sulphuric and other acids--is not equal to 14, but to 28 parts by weight. Thus with H_{2}SO_{4}, Br_{2}, or HI, &c., ethylene combines in a quantity C_{2}H_{4}, and amylene in a quantity C_{5}H_{10}, and not CH_{2}. On the other hand, ethylene is a gas which liquefies with difficulty (absolute boiling point = +10°), whilst amylene is a liquid boiling at 35° (absolute boiling point = +192°), and by admitting the greater density of the molecules of amylene (M = 70) its difference from the lighter molecules of ethylene (M = 28) becomes clear. Thus, the smaller quotient M/D is _an indication of polymerisation_, as the larger quotient is of decomposition. The difference between the densities of oxygen and ozone is a case in point. On turning to the elements, it is found in certain cases, especially with metals--for instance, mercury, zinc, and cadmium--that that weight of the atoms which must be acknowledged in their compounds (of which mention will be afterwards made) appears to be also the molecular weight. Thus, the atomic weight of mercury must be taken as = 200, but the vapour density = 100, and the quotient = 2. Consequently the _molecule of mercury contains one atom_, Hg. It is the same with sodium, cadmium, and zinc. This is the simplest possible molecule, which necessarily is only possible in the case of elements, as the molecule of a compound must contain at least two atoms. However, the molecules of many of the elements prove to be complex--for instance, the weight of an atom of oxygen = 16, and its density = 16, so that its molecule must contain two atoms, O_{2}, which might already be concluded by comparing its density with that of ozone, whose molecule contains O_{3} (Chapter IV.) So also the molecule of hydrogen equals H_{2}, of chlorine Cl_{2}, of nitrogen N_{2}, &c. If chlorine react with hydrogen, the volume remains unaltered after the formation of hydrochloric acid, H_{2} + Cl_{2} = HCl + HCl. It is a case of substitution between the one and the other, and therefore the volumes remain constant. There are elements whose molecules are much more complex--for instance, sulphur, S_{6}--although, by heating, the density is reduced to a third, and S_{2} is formed. Judging from the vapour density of phosphorus (D = 62) the molecule contains four atoms P_{4}. Hence many elements when polymerised appear in molecules which are more complex than the simplest possible. In carbon, as we shall afterwards find, a very complex molecule must be admitted, as otherwise its non-volatility and other properties cannot be understood. And if compounds are decomposed by a more or less powerful heat, and if polymeric substances are depolymerised (that is, the weight of the molecule diminishes) by a rise of temperature, as N_{2}O_{4} passes into NO_{2}, or ozone, O_{3}, into ordinary oxygen, O_{2}, then we might expect to find the splitting-up of the complex molecules of elements into the simplest molecule containing a single atom only--that is to say, if O_{2} be obtained from O_{3}, then the formation of O might also be looked for. The possibility but not proof of such a proposition is indicated by the vapour of iodine. Its normal density = 127 (Dumas, Deville, and others), which corresponds with the molecule I_{2}. At temperatures above 800° (up to which the density remains almost constant), this density distinctly decreases, as is seen from the verified results obtained by Victor Meyer, Crafts, and Troost. At the ordinary pressure and 1,000° it is about 100, at 1,250° about 80, at 1,400° about 75, and apparently it strives to reduce itself to one-half--that is, to 63. Under a reduced pressure this splitting-up, or depolymerisation, of iodine vapour actually reaches a density[16] of 66, as Crafts demonstrated by reducing the pressure to 100 mm. and raising the temperature to 1,500°. From this it may be concluded that at high temperatures and low pressures the molecule I_{2} gradually passes into the molecule I containing one atom like mercury, and that something similar occurs with other elements at a considerable rise of temperature, which tends to bring about the disunion of compounds and the decomposition of complex molecules.[17] [16] Just as we saw (Chapter VI. Note 46) an increase of the dissociation of N_{2}O_{4} and the formation of a large proportion of NO_{2}, with a decrease of pressure. The decomposition of I_{2} into I + I is a similar dissociation. [17] Although at first there appeared to be a similar phenomenon in the case of chlorine, it was afterwards proved that if there is a decrease of density it is only a small one. In the case of bromine it is not much greater, and is far from being equal to that for iodine. As in general we very often involuntarily confuse chemical processes with physical, it may be that a physical process of change in the coefficient of expansion with a change of temperature participates with a change in molecular weight, and partially, if not wholly, accounts for the decrease of the density of chlorine, bromine, and iodine. Thus, I have remarked (Comptes Rendus, 1876) that the coefficient of expansion of gases increases with their molecular weight, and (Chapter II., Note 26) the results of direct experiment show the coefficient of expansion of hydrobromic acid (M = 81) to be 0·00386 instead of 0·00367, which is that of hydrogen (M = 2). Hence, in the case of the vapour of iodine (M = 254) a very large coefficient of expansion is to be expected, and from this cause alone the relative density would fall. As the molecule of chlorine Cl_{2} is lighter (= 71) than that of bromine (= 160), which is lighter than that of iodine (= 254), we see that the order in which the decomposability of the vapours of these haloids is observed corresponds with the expected rise in the coefficient of expansion. Taking the coefficient of expansion of iodine vapour as 0·004, then at 1,000° its density would be 116. Therefore the dissociation of iodine may be only an apparent phenomenon. However, on the other hand, the heavy vapour of mercury (M = 200, D = 100) scarcely decreases in density at a temperature of 1,500° (D = 98, according to Victor Meyer); but it must not be forgotten that the molecule of mercury contains only one atom, whilst that of iodine contains two, and this is very important. Questions of this kind which are difficult to decide by experimental methods must long remain without a certain explanation, owing to the difficulty, and sometimes impossibility, of distinguishing between physical and chemical changes. Besides these cases of apparent discrepancy from the law of Avogadro-Gerhardt there is yet a third, which is the last, and is very instructive. In the investigation of separate substances they have to be isolated in the purest possible form, and their chemical and physical properties, and among them the vapour density, then determined. If it be normal--that is, if D = M/2--it often serves as a proof of the purity of the substance, _i.e._ of its freedom from all foreign matter. If it be abnormal--that is, if D be not equal to M/2--then for those who do not believe in the law it appears as a new argument against it and nothing more; but to those who have already grasped the important significance of the law it becomes clear that there is some error in the observation, or that the density was determined under conditions in which the vapour does not follow the laws of Boyle or Gay-Lussac, or else that the substance has not been sufficiently purified, and contains other substances. The law of Avogadro-Gerhardt in that case furnishes convincing evidence of the necessity of a fresh and more exact research. And as yet the causes of error have always been found. There are not a few examples in point in the recent history of chemistry. We will cite one instance. In the case of pyrosulphuryl chloride, S_{2}O_{5}Cl_{2}, M = 215, and consequently D should = 107·5, instead of which Ogier and others obtained 53·8--that is, a density half as great; and further, Ogier (1882) demonstrated clearly that the substance is not dissociated by distillation into SO_{3} and SO_{2}Cl_{2}, or any other two products, and thus the abnormal density of S_{2}O_{5}Cl_{2} remained unexplained until D. P. Konovaloff (1885) showed that the previous investigators were working with a mixture (containing SO_{3}HCl), and that pyrosulphuryl chloride has a normal density of approximately 107. Had not the law of Avogadro-Gerhardt served as a guide, the impure liquid would have still passed as pure; the more so since the determination of the amount of chlorine could not aid in the discovery of the impurity. Thus, by following a true law of nature we are led to true deductions. All cases which have been studied confirm the law of Avogadro-Gerhardt, and as by it a deduction is obtained, from the determination of the vapour density (a purely physical property), as to the weight of the molecule or quantity of a substance entering into chemical reaction, this law links together the two provinces of learning--physics and chemistry--in the most intimate manner. Besides which, the law of Avogadro-Gerhardt places the conceptions of _molecules_ and _atoms_ on a firm foundation, which was previously wanting. Although since the days of Dalton it had become evident that it was necessary to admit the existence of the elementary atom (the chemical individual indivisible by chemical or other forces), and of the groups of atoms (or molecules) of compounds, indivisible by mechanical and physical forces; still the relative magnitude of the molecule and atom was not defined with sufficient clearness. Thus, for instance, the atomic weight of oxygen might be taken as 8 or 16, or any multiple of these numbers, and nothing indicated a reason for the acceptation of one rather than another of these magnitudes;[18] whilst as regards the weights of the molecules of elements and compounds there was no trustworthy knowledge whatever. With the establishment of Gerhardt's law the idea of the molecule was fully defined, as well as the relative magnitude of the elementary atom. [18] And so it was in the fifties. Some took O = 8, others O = 16. Water in the first case would be HO and hydrogen peroxide HO_{2}, and in the second case, as is now generally accepted, water H_{2}O and hydrogen peroxide H_{2}O_{2} or HO. Disagreement and confusion reigned. In 1860 the chemists of the whole world met at Carlsruhe for the purpose of arriving at some agreement and uniformity of opinion. I was present at this Congress, and well remember how great was the difference of opinion, and how a compromise was advocated with great acumen by many scientific men, and with what warmth the followers of Gerhardt, at whose head stood the Italian professor, Canizzaro, followed up the consequences of the law of Avogadro. In the spirit of scientific freedom, without which science would make no progress, and would remain petrified as in the middle ages, and with the simultaneous necessity of scientific conservatism, without which the roots of past study could give no fruit, a compromise was not arrived at, nor ought it to have been, but instead of it truth, in the form of the law of Avogadro-Gerhardt, received by means of the Congress a wider development, and soon afterwards conquered all minds. Then the new so-called Gerhardt atomic weights established themselves, and in the seventies they were already in general use. The chemical particle or _molecule must be considered as the quantity of a substance which enters into chemical reaction with other molecules, and occupies in a state of vapour the same volume as two parts by weight of hydrogen_. The molecular weight (which has been indicated by M) of a substance is determined by its composition, transformations, and vapour density. The molecule is not divisible by the mechanical and physical changes of substances, but in chemical reaction it is either altered in its properties, or quantity, or structure, or in the nature of the motion of its parts. An agglomeration of molecules, which are alike in all chemical respects, makes up the masses of homogeneous substances in all states.[19] [19] A bubble of gas, a drop of liquid, or the smallest crystal, presents an agglomeration of a number of molecules, in a state of continual motion (like the stars of the Milky Way), distributing themselves evenly or forming new systems. If the aggregation of all kinds of heterogeneous molecules be possible in a gaseous state, where the molecules are considerably removed from each other, then in a liquid state, where they are already close together, such an aggregation becomes possible only in the sense of the mutual reaction between them which results from their chemical attraction, and especially in the aptitude of heterogeneous molecules for combining together. Solutions and other so-called indefinite chemical compounds should be regarded in this light. According to the principles developed in this work we should regard them as containing both the compounds of the heterogeneous molecules themselves and the products of their decomposition, as in peroxide of nitrogen, N_{2}O_{4} and NO_{2}. And we must consider that those molecules A, which at a given moment are combined with B in AB, will in the following moment become free in order to again enter into a combined form. The laws of chemical equilibrium proper to dissociated systems cannot be regarded in any other light. Molecules consist of atoms in a certain state of distribution and motion, just as the solar system[20] is made up of inseparable parts (the sun, planets, satellites, comets, &c.) The greater the number of atoms in a molecule, the more complex is the resultant substance. The equilibrium between the dissimilar atoms may be more or less stable, and may for this reason give more or less stable substances. Physical and mechanical transformations alter the velocity of the motion and the distances between the individual molecules, or of the atoms in the molecules, or of their sum total, but they do not alter the original equilibrium of the system; whilst chemical changes, on the other hand, alter the molecules themselves, that is, the velocity of motion, the relative distribution, and the quality and quantity of the atoms in the molecules. [20] This strengthens the fundamental idea of the unity and harmony of type of all creation and is one of those ideas which impress themselves on man in all ages, and give rise to a hope of arriving in time, by means of a laborious series of discoveries, observations, experiments, laws, hypotheses, and theories, at a comprehension of the internal and invisible structure of concrete substances with that same degree of clearness and exactitude which has been attained in the visible structure of the heavenly bodies. It is not many years ago since the law of Avogadro-Gerhardt took root in science. It is within the memory of many living scientific men, and of mine amongst others. It is not surprising, therefore, that as yet little progress has been made in the province of molecular mechanics; but the theory of gases alone, which is intimately connected with the conception of molecules, shows by its success that the time is approaching when our knowledge of the internal structure of matter will be defined and established. _Atoms are the smallest quantities_ or chemically indivisible masses _of the elements forming the molecules_ of elements and compounds. Atoms have weight, the sum of their weights forms the weight of the molecule, and the sum of the weights of the molecules forms the weight of masses, and is the cause of gravity, and of all the phenomena which depend on the mass of a substance. The elements are characterised, not only by their independent existence, their incapacity of being converted into each other, &c., but also by the weight of their atoms. Chemical and physical properties depend on the weight, composition, and properties of the molecules forming a substance, and on the weight and properties of the atoms forming the molecules. This is the substance of those principles of molecular mechanics which lie at the basis of all contemporary physical and chemical constructions since the establishment of the law of Avogadro-Gerhardt. The fecundity of the principles enunciated is seen at every step in all the particular cases forming the present store of chemical data. We will here cite a few examples of the application of the law. As the weight of an atom must be understood as the minimum quantity of an element entering into the composition of all the molecules formed by it, therefore, in order to find the weight of an atom of oxygen, let us take the molecules of those of its compounds which have already been described, together with the molecules of certain of those carbon compounds which will be described in the following chapter: Molecular Amount of Molecular Amount of Weight Oxygen Weight Oxygen H_{2}O 18 16 HNO_{3} 63 48 N_{2}O 44 16 CO 28 16 NO 30 16 CO_{2} 44 32 NO_{2} 46 32 The number of substances taken might be considerably increased, but the result would be the same--that is, the molecules of the compounds of oxygen would never be found to contain less than 16 parts by weight of this element, but always _n_16, where _n_ is a whole number. The molecular weights of the above compounds are found either directly from the density of their vapour or gas, or from their reactions. Thus, the vapour density of nitric acid (as a substance which easily decomposes above its boiling point) cannot be accurately determined, but the fact of its containing one part by weight of hydrogen, and all its properties and reactions, indicate the above molecular composition and no other. In this manner it is very easy to find the atomic weight of all the elements, knowing the molecular weight and composition of their compounds. It may, for instance, be easily proved that less than _n_12 parts of carbon never enters into the molecules of carbon compounds, and therefore C must be taken as 12, and not as 6 which was the number in use before Gerhardt. In a similar manner the atomic weights now accepted for the elements oxygen, nitrogen, carbon, chlorine, sulphur, &c., were found and indubitably established, and they are even now termed the Gerhardt atomic weights. As regards the metals, many of which do not give a single volatile compound, we shall afterwards see that there are also methods by which their atomic weights may be established, but nevertheless the law of Avogadro-Gerhardt is here also ultimately resorted to, in order to remove any doubt which may be encountered. Thus, for instance, although much that was known concerning the compounds of beryllium necessitated its atomic weight being taken as Be = 9--that is, the oxide as BeO and the chloride BeCl_{2}--still certain analogies gave reason for considering its atomic weight to be Be = 13·5, in which case its oxide would be expressed by the composition Be_{2}O_{3}, and the chloride by BeCl_{3}.[21] It was then found that the vapour density of beryllium chloride was approximately 40, when it became quite clear that its molecular weight was 80, and as this satisfies the formula BeCl_{2}, but does not suit the formula BeCl_{3}, it therefore became necessary to regard the atomic weight of Be as 9 and not as 13-1/2. [21] If Be = 9, and beryllium chloride be BeCl_{2}, then for every 9 parts of beryllium there are 71 parts of chlorine, and the molecular weight of BeCl_{2} = 80; hence the vapour density should be 40 or _n_{4}0. If Be = 13·5, and beryllium chloride be BeCl_{3}, then to 13·5 of beryllium there are 106·5 of chlorine; hence the molecular weight would be 120, and the vapour density 60 or _n_60. The composition is evidently the same in both cases, because 9 : 71 :: 13·5 : 106·5. Thus, if the symbol of an element designate different atomic weights, apparently very different formulæ may equally well express both the percentage composition of compounds, and those properties which are required by the laws of multiple proportions and equivalents. The chemists of former days accurately expressed the composition of substances, and accurately applied Dalton's laws, by taking H = 1, O = 8, C = 6, Si = 14, &c. The Gerhardt equivalents are also satisfied by them, because O = 16, C = 12, Si = 28, &c., are multiples of them. The choice of one or the other multiple quantity for the atomic weight is impossible without a firm and concrete conception of the molecule and atom, and this is only obtained as a consequence of the law of Avogadro-Gerhardt, and hence the modern atomic weights are the results of this law (_see_ Note 28). With the establishment of a true conception of molecules and atoms, chemical formulæ became direct expressions, not only of composition,[22] but also of molecular weight or _vapour density_, and consequently of a series of fundamental chemical and physical data, inasmuch as a number of the properties of substances are dependent on their vapour density, or molecular weight and composition. The vapour density D = M/2. For instance, the formula of ethyl ether is C_{4}H_{10}O, corresponding with the molecular weight 74, and the vapour density 37, which is the fact. Therefore, the density of vapours and gases has ceased to be an empirical magnitude obtained by experiment only, and has acquired a rational meaning. It is only necessary to remember that 2 grams of hydrogen, or the molecular weight of this primary gas in grams, occupies, at 0° and 760 mm. pressure, a volume of 22·3 litres (or 22,300 cubic centimetres), in order to directly determine the weights of cubical measures of gases and vapours from their formulæ, because _the molecular weights in grams of all other vapours at 0° and 760 mm. occupy the same volume, 22·3 litres_. Thus, for example, in the case of carbonic anhydride, CO_{2}, the molecular weight M = 44, hence 44 grams of carbonic anhydride at 0° and 760 mm. occupy a volume of 22·3 litres--consequently, a litre weighs 1·97 gram. By combining the laws of gases--Gay-Lussac's, Mariotte's, and Avogadro-Gerhardt's--we obtain[23] a general formula for gases 6200_s_(273 + _t_) = M_p_ where _s_ is the weight in grams of a cubic centimetre of a vapour or gas at a temperature _t_ and pressure _p_ (expressed in centimetres of mercury) if the molecular weight of the gas = M. Thus, for instance, at 100° and 760 millimetres pressure (_i.e._ at the atmospheric pressure) the weight of a cubic centimetre of the vapour of ether (M = 74) is _s_ = 0·0024.[24] [22] The percentage amounts of the elements contained in a given compound may be calculated from its formula by a simple proportion. Thus, for example, to find the percentage amount of hydrogen in hydrochloric acid we reason as follows:--HCl shows that hydrochloric acid contains 35·5 of chlorine and 1 part of hydrogen. Hence, in 36·5 parts of hydrochloric acid there is 1 part by weight of hydrogen, consequently 100 parts by weight of hydrochloric acid will contain as many more units of hydrogen as 100 is greater than 36·5; therefore, the proportion is as follows--_x_ : 1 :: 100 : 36·5 or _x_ = 100/36·5 = 2·739. Therefore 100 parts of hydrochloric acid contain 2·739 parts of hydrogen. In general, when it is required to transfer a formula into its percentage composition, we must replace the symbols by their corresponding atomic weights and find their sum, and knowing the amount by weight of a given element in it, it is easy by proportion to find the amount of this element in 100 or any other quantity of parts by weight. If, on the contrary, it be required to find the formula from a given percentage composition, we must proceed as follows: Divide the percentage amount of each element entering into the composition of a substance by its atomic weight, and compare the figures thus obtained--they should be in simple multiple proportion to each other. Thus, for instance, from the percentage composition of hydrogen peroxide, 5·88 of hydrogen and 94·12 of oxygen, it is easy to find its formula; it is only necessary to divide the amount of hydrogen by unity and the amount of oxygen by 16. The numbers 5·88 and 5·88 are thus obtained, which are in the ratio 1 : 1, which means that in hydrogen peroxide there is one atom of hydrogen to one atom of oxygen. The following is a proof of the practical rule given above _that to find the ratio of the number of atoms from the percentage composition, it is necessary to divide the percentage amounts by the atomic weights of the corresponding substances, and to find the ratio which these numbers bear to each other_. Let us suppose that two radicles (simple or compound), whose symbols and combining weights are A and B, combine together, forming a compound composed of _x_ atoms of A and _y_ atoms of B. The formula of the substance will be A_x_B_y_. From this formula we know that our compound contains _x_A parts by weight of the first element, and _y_B of the second. In 100 parts of our compound there will be (by proportion) (100. _x_A)/(_x_A + _y_B) of the first element, and (100. _y_B)/(_x_A + _y_B) of the second. Let us divide these quantities, expressing the percentage amounts by the corresponding combining weights; we then obtain 100_x_/(_x_A + _y_B) for the first element and 100_y_/(_x_A + _y_B) for the second element. And these numbers are in the ratio _x_ : _y_--that is, in the ratio of the number of atoms of the two substances. It may be further observed that even the very language or nomenclature of chemistry acquires a particular clearness and conciseness by means of the conception of molecules, because then the names of substances may directly indicate their composition. Thus the term 'carbon dioxide' tells more about and expresses CO_{2} better than carbonic acid gas, or even carbonic anhydride. Such nomenclature is already employed by many. But expressing the composition without an indication or even hint as to the properties, would be neglecting the advantageous side of the present nomenclature. Sulphur dioxide, SO_{2}, expresses the same as barium dioxide, BaO_{2}, but sulphurous anhydride indicates the acid properties of SO_{2}. Probably in time one harmonious chemical language will succeed in embracing both advantages. [23] This formula (which is given in my work on 'The Tension of Gases,' and in a somewhat modified form in the 'Comptes Rendus,' Feb. 1876) is deduced in the following manner. According to the law of Avogadro-Gerhardt, M = 2D for all gases, where M is the molecular weight and D the density referred to hydrogen. But it is equal to the weight _s__{0} of a cubic centimetre of a gas in grams at 0° and 76 cm. pressure, divided by 0·0000898, for this is the weight in grams of a cubic centimetre of hydrogen. But the weight _s_ of a cubic centimetre of a gas at a temperature _t_ and under a pressure _p_ (in centimetres) is equal to _s__{0}_p_/76(1 + _at_). Therefore, _s__{0} = _s_.76(1 + _at_)/_p_; hence D = 76._s_(1 + _at_)/0·0000898_p_, whence M = 152_s_(1 + _at_)/0·0000898_p_, which gives the above expression, because 1/_a_ = 273, and 152 multiplied by 273 and divided by 0·0000898 is nearly 6200. In place of _s_, _m/v_ may be taken, where _m_ is the weight and _v_ the volume of a vapour. [24] The above formula may be directly applied in order to ascertain the molecular weight from the data; weight of vapour _m_ grms., its volume _v_ c.c., pressure _p_ cm., and temperature _t_°; for _s_ = the weight of vapour _m_, divided by the volume _v_, and consequently M = 6,200_m_(273 + _t_)/_pv_. Therefore, instead of the formula (_see_ Chapter II., Note 34), _pv_ = R(273 + _t_), where R varies with the mass and nature of a gas, we may apply the formula _pv_ = 6,200(_m_/M)(273 + _t_). These formulæ simplify the calculations in many cases. For example, required the volume _v_ occupied by 5 grms. of aqueous vapour at a temperature _t_ = 127° and under a pressure _p_ = 76 cm. According to the formula M = 6,200_m_(273 + _t_)/_pv_, we find that _v_ = 9,064 c.c., as in the case of water M = 18, _m_ in this instance = 5 grms. (These formulæ, however, like the laws of gases, are only approximate.) As the molecules of many elements (hydrogen, oxygen, nitrogen, chlorine, bromine, sulphur--at least at high temperatures) are of uniform composition, the formulæ of the compounds formed by them directly indicate the composition by volume. So, for example, the formula HNO_{3} directly shows that in the decomposition of nitric acid there is obtained 1 vol. of hydrogen, 1 vol. of nitrogen, and 3 vols. of oxygen. And since a great number of mechanical, physical, and chemical properties are directly dependent on the elementary and volumetric composition, and on the vapour density, the accepted system of atoms and molecules gives the possibility of simplifying a number of most complex relations. For instance, it may be easily demonstrated _that the vis viva of the molecules of all vapours and gases is alike_. For it is proved by mechanics that the _vis viva_ of a moving mass = (1/2) _mv_^2, where _m_ is the mass and _v_ the velocity. For a molecule, _m_ = M, or the molecular weight, and the velocity of the motion of gaseous molecules = a constant which we will designate by C, divided by the square root of the density of the gas[25] = C/[sqrt]D, and as D = M/2, the _vis viva_ of molecules = C^2--that is, a constant for all molecules. _Q.E.D._[26] The specific heat of gases (Chapter XIV.), and many other of their properties, are determined by their density, and consequently by their molecular weight. Gases and vapours in passing into a liquid state evolve the so-called _latent heat_, which also proves to be in connection with the molecular weight. The observed latent heats of carbon bisulphide, CS_{2} = 90, of ether, C_{4}H_{10}O, = 94, of benzene, C_{6}H_{6}, = 109, of alcohol, C_{2}H_{6}O, = 200, of chloroform, CHCl_{3}, = 67, &c., show the amount of heat expended in converting one part by weight of the above substances into vapour. A great uniformity is observed if the measure of this heat he referred to the weight of the molecule. For carbon bisulphide the formula CS_{2} expresses a weight 76, hence the latent heat of evaporation referred to the molecular quantity CS_{2} = 76 x 90 = 6,840, for ether = 9,656, for benzene = 8,502, for alcohol = 9,200, for chloroform = 8,007, for water = 9,620, &c. That is, for molecular quantities, the latent heat varies comparatively little, from 7,000 to 10,000 heat units, whilst for equal parts by weight it is ten times greater for water than for chloroform and many other substances.[27] [25] Chapter I., Note 34. [26] _The velocity of the transmission of sound through gases and vapours_ closely bears on this. It = [sqrt](_Kpg_)/D(1 + [Greek: a]_t_), where _K_ is the ratio between the two specific heats (it is approximately 1·4 for gases containing two atoms in a molecule), _p_ the pressure of the gas expressed by weight (that is, the pressure expressed by the height of a column of mercury multiplied by the density of mercury), _g_ the acceleration of gravity, D the weight of a cubic measure of the gas, [Greek: a] = 0·00367, and _t_ the temperature. Hence, if _K_ be known, and as D can he found from the composition of a gas, we can calculate the velocity of the transmission of sound in that gas. Or if this velocity be known, we can find _K_. The relative velocities of sound in two gases can he easily determined (Kundt). If a horizontal glass tube (about 1 metre long and closed at both ends) be full of a gas, and be firmly fixed at its middle point, then it is easy to bring the tube and gas into a state of vibration, by rubbing it from centre to end with a damp cloth. The vibration of the gas is easily rendered visible, if the interior of the tube be dusted with lycopodium (the yellow powder-dust or spores of the lycopodium plant is often employed in medicine), before the gas is introduced and the tube fused up. The fine lycopodium powder arranges itself in patches, whose number depends on the velocity of sound in the gas. If there be 10 patches, then the velocity of sound in the gas is ten times slower than in glass. It is evident that this is an easy method of comparing the velocity of sound in gases. It has been demonstrated by experiment that the velocity of sound in oxygen is four times less than in hydrogen, and the square roots of the densities and molecular weights of hydrogen and oxygen stand in this ratio. [27] If the conception of the molecular weights of substances does not give an exact law when applied to the latent heat of evaporation, at all events it brings to light a certain uniformity in figures, which otherwise only represent the simple result of observation. Molecular quantities of liquids appear to expend almost equal amounts of heat in their evaporation. It may be said that the latent heat of evaporation of molecular quantities is approximately constant, because the _vis viva_ of the motion of the molecules is, as we saw above, a constant quantity. According to thermodynamics the latent heat of evaporation is equal to ((_t_ + 273)/E)(_n_´-_n_)_dp_/_d_T × 13·59, where _t_ is the boiling point, _n_´ the specific volume (_i.e._ the volume of a unit of weight) of the vapour, and _n_ the specific volume of the liquid, _dp_/_d_T the variation of the tension with a rise of temperature per 1°, and 13·89 the density of the mercury according to which the pressure is measured. Thus the latent heat of evaporation increases not only with a decrease in the vapour density (_i.e._ the molecular weight), but also with an increase in the boiling point, and therefore depends on different factors. Generalising from the above, the weight of the molecule determines the properties of a substance _independently of its composition_--_i.e._ of the number and quality of the atoms entering into the molecule--whenever the substance is in a gaseous state (for instance, the density of gases and vapours, the velocity of sound in them, their specific heat, &c.), or passes into that state, as we see in the latent heat of evaporation. This is intelligible from the point of view of the atomic theory in its present form, for, besides a rapid motion proper to the molecules of gaseous bodies, it is further necessary to postulate that these molecules are dispersed in space (filled throughout with the luminiferous ether) like the heavenly bodies distributed throughout the universe. Here, as there, it is only the degree of removal (the distance) and the masses of substances which take effect, while those peculiarities of a substance which are expressed in chemical transformations, and only come into action on near approach or on contact, are in abeyance by reason of the dispersal. Hence it is at once obvious, in the first place, that in the case of solids and liquids, in which the molecules are closer together than in gases and vapours, a greater complexity is to be expected, _i.e._ a dependence of all the properties not only upon the weight of the molecule but also upon its composition and quality, or upon the properties of the individual chemical atoms forming the molecule; and, in the second place, that, in the case of a small number of molecules of any substance being disseminated through a mass of another substance--for example, in the formation of weak (dilute) solutions (although in this case there is an act of chemical reaction--_i.e._ a combination, decomposition, or substitution)--the dispersed molecules will alter the properties of the medium in which they are dissolved, almost in proportion to the molecular weight and almost independently of their composition. The greater the number of molecules disseminated--_i.e._ the stronger the solution--the more clearly defined will those properties become which depend upon the composition of the dissolved substance and its relation to the molecules of the solvent, for the distribution of one kind of molecules in the sphere of attraction of others cannot but be influenced by their mutual chemical reaction. These general considerations give a starting point for explaining why, since the appearance of Van't Hoff's memoir (1886), 'The Laws of Chemical Equilibrium in a Diffused Gaseous or Liquid State' (_see_ Chapter I., Note 19), it has been found more and more that _dilute_ (weak) solutions exhibit such variations of properties as depend wholly upon the weight and number of the molecules and not upon their composition, and even give the means of determining the weight of molecules by studying the variations of the properties of a solvent on the introduction of a small quantity of a substance passing into solution. Although this subject has been already partially considered in the first chapter (in speaking of solutions), and properly belongs to a special (physical) branch of chemistry, we touch upon it here because the meaning and importance of molecular weights are seen in it in a new and peculiar light, and because it gives a method for determining them whenever it is possible to obtain dilute solutions. Among the numerous properties of dilute solutions which have been investigated (for instance, the osmotic pressure, vapour tension, boiling point, internal friction, capillarity, variation with change of temperature, specific heat, electroconductivity, index of refraction, &c.) we will select one--the 'depression' or fall of the temperature of freezing (Raoult's cryoscopic method), not only because this method has been the most studied, but also because it is the most easily carried out and most frequently applied for determining the weight of the molecules of substances in solution, although here, owing to the novelty of the subject there are also many experimental discrepancies which cannot as yet be explained by theory.[27 bis] [27 bis] The osmotic pressure, vapour tension of the solvent, and several other means applied like the cryoscopic method to dilute solutions for determining the molecular weight of a substance in solution, are more difficult to carry out in practice, and only the method of _determining the rise of the boiling point_ of dilute solutions can from its facility be placed parallel with the cryoscopic method, to which it bears a strong resemblance, as in both the solvent changes its state and is partially separated. In the boiling point method it passes off in the form of a vapour, while in cryoscopic determinations it separates out in the form of a solid body. Van't Hoff, starting from the second law of thermodynamics, showed that the dependence of the rise of pressure (_dp_) upon a rise of temperature (_d_T) is determined by the equation _dp_ = (_kmp_/2T^2)_d_T, where _k_ is the latent heat of evaporation of the solvent, _m_ its molecular weight, _p_ the tension of the saturated vapour of the solvent at T, and T the absolute temperature (T = 273 + _t_), while Raoult found that the quantity (_p_-_p´_)/_p_ (Chapter I., Note 50) or the measure of the relative fall of tension (_p_ the tension of the solvent or water, and _p´_ of the solution) is found by the ratio of the number of molecules, _n_ of the substance dissolved, and N of the solvent, so that (_p_-_p´_)/_p_ = C_n_/(N + _n_) where C is a constant. With very dilute solutions _p_ _-p´_ may be taken as equal to _dp_, and the fraction _n_/(N + _n_) as equal to _n_/N (because in that case the value of N is very much greater than _n_), and then, judging from experiment, C is nearly unity--hence: _dp/p_ = _n_/N or _dp_ = _np_/N, and on substituting this in the above equation we have (_kmp_/2T^2)_d_T = _np_/N. Taking a weight of the solvent _m_/N = 100, and of the substance dissolved (per 100 of the solvent) _q_, where _q_ evidently = _n_M, if M be the molecular weight of the substance dissolved, we find that _n_/N = _qm_/100M, and hence, according to the preceding equation, we have M = (0·02T^2/_k_)·(_q_/_d_T), that is, by taking a solution of _q_ grms. of a substance in 100 grms. of a solvent, and determining by experiment the rise of the boiling point _d_T, we find the molecular weight M of the substance dissolved, because the fraction 0·02T^2/_k_ is (for a given pressure and solvent) a constant; for water at 100° (T = 373°) when _k_ = 534 (Chapter I., Note 11), it is nearly 5·2, for ether nearly 21, for bisulphide of carbon nearly 24, for alcohol nearly 11·5, &c. As an example, we will cite from the determinations made by Professor Sakurai, of Japan (1893), that when water was the solvent and the substance dissolved, corrosive sublimate, HgCl_{2}, was taken in the quantity _q_ = 8·978 and 4·253 grms., the rise in the boiling point _d_T was = O°·179 and 0°·084, whence M = 261 and 263, and when alcohol was the solvent, _q_ = 10·873 and 8·765 and _d_T = 0°·471 and 0°·380, whence M = 266 and 265, whilst the actual molecular weight of corrosive sublimate = 271, which is very near to that given by this method. In the same manner for aqueous solutions of sugar (M = 342), when _q_ varied from 14 to 2·4, and the rise of the boiling point from 0°·21 to 0°·035, M was found to vary between 339 and 364. For solutions of iodine I_{2} in ether, the molecular weight was found by this method to be between 255 and 262, and I_{2} = 254. Sakurai obtained similar results (between 247 and 262) for solutions of iodine in bisulphide of carbon. We will here remark that in determining M (the molecular weight of the substance dissolved) at small but increasing concentrations (per 100 grms. of water), the results obtained by Julio Baroni (1893) show that the value of M found by the formula may either increase or decrease. An increase, for instance, takes place in aqueous solutions of HgCl_{2} (from 255 to 334 instead of 271), KNO_{3} (57-66 instead of 101), AgNO_{3} (104-107 instead of 170), K_{2}SO_{4} (55-89 instead of 174), sugar (328-348 instead of 342), &c. On the contrary the calculated value of M decreases as the concentration increases, for solutions of KCl (40-39 instead of 74·5), NaCl (33-28 instead of 58·5), NaBr (60-49 instead of 103), &c. In this case (as also for LiCl, NaI, C_{2}H_{3}NaO_{2}, &c.) the value of _i_ (Chapter I., Note 49), or the ratio between the actual molecular weight and that found by the rise of the boiling point, was found to increase with the concentration, _i.e._ to be greater than 1, and to differ more and more from unity as the strength of the solution becomes greater. For example, according to Schlamp (1894), for LiCl, with a variation of from 1·1 to 6·7 grm. LiCl per 100 of water, _i_ varies from 1·63 to 1·89. But for substances of the first series (HgCl_{2}, &c.), although in very dilute solutions _i_ is greater than 1, it approximates to 1 as the concentration increases, and this is the normal phenomenon for solutions which do not conduct an electric current, as, for instance, of sugar. And with certain electrolytes, such as HgCl_{2}, MgSO_{4}, &c., _i_ exhibits a similar variation; thus, for HgCl_{2} the value of M is found to vary between 255 and 334; that is, _i_ (as the molecular weight = 271) varies between 1·06 and 0·81. Hence I do not believe that the difference between _i_ and unity (for instance, for CaCl_{2}, _i_ is about 3, for KI about 2, and decreases with the concentration) can at present be placed at the basis of any general chemical conclusions, and it requires further experimental research. Among other methods by which the value of _i_ is now determined for dilute solutions is the study of their electroconductivity, admitting that _i_ = 1 + _a_(_k_-1), where _a_ = the ratio of the molecular conductivity to the limiting conductivity corresponding to an infinitely large dilution (_see_ Physical Chemistry), and _k_ is the number of ions into which the substance dissolved can split up. Without entering upon a criticism of this method of determining _i_, I will only remark that it frequently gives values of _i_ very close to those found by the depression of the freezing point and rise of the boiling point; but that this accordance of results is sometimes very doubtful. Thus for a solution containing 5·67 grms. CaCl_{2} per 100 grms. of water, _i_, according to the vapour tension = 2·52, according to the boiling point = 2·71, according to the electroconductivity = 2·28, while for solutions in propyl alcohol (Schlamp 1894) _i_ is near to 1·33. In a word, although these methods of determining the molecular weight of substances in solution show an undoubted progress in the general chemical principles of the molecular theory, there are still many points which require explanation. We will add certain general relations which apply to these problems. Isotonic (Chapter I., Note 19) solutions exhibit not only similar osmotic pressures, but also the same vapour tension, boiling point and freezing temperature. The osmotic pressure bears the same relation to the fall of the vapour tension as the specific gravity of a solution does to the specific gravity of the vapour of the solvent. The general formulæ underlying the whole doctrine of the influence of the molecular weight upon the properties of solutions considered above, are: 1. Raoult in 1886-1890 showed that ((_p_-_p_´)/_p_) × (100/_a_) × (M/_m_) = a constant C where _p_ and _p_´ are the vapour tensions of the solvent and substance dissolved, _a_ the amount in grms. of the substance dissolved per 100 grms. of solvent, M and _m_ the molecular weights of the substance dissolved and solvent. 2. Raoult and Recoura in 1890 showed that the constant above C = the ratio of the actual vapour density _d_´ of the solvent to the theoretical density _d_ calculated according to the molecular weight. This deduction may now be considered proved, because both the fall of tension and the ratio of the vapour densities _d_´/_d_ give, for water 1·03, for alcohol 1·02, for ether 1·04, for bisulphide of carbon 1·00, for benzene 1·02, for acetic acid 1·63. 3. By applying the principles of thermodynamics and calling L_{1} the latent heat of fusion and T_{1} the absolute (= _t_ + 273) temperature of fusion of the solvent, and L_{2} and T_{2} the corresponding values for the boiling point, Van't Hoff in 1886-1890 deduced:-- (Depression of freezing point)/(Rise of boiling point) = (L_{2}/L_{1}) × (T_{1}^2/T_{2}^2) Depression of freezing point = (AT_{1}^{2}_a_)/(L_{1}M_{1}) Rise of boiling point = (AT_{2}^{2}_a_)/(L_{2}M_{1}) where A = 0·01988 (or nearly 0·02 as we took it above), _a_ is the weight in grms. of the substance dissolved per 100 grms. of the solvent, M_{1} the molecular weight of the dissolved substance (in the solution), and M the molecular weight of this substance according to its composition and vapour density, then _i_ = M/M_{1}. The experimental data and theoretical considerations upon which these formulæ are based will be found in text-books of physical and theoretical chemistry. If 100 gram-molecules of water, _i.e._ 1,800 grms, be taken and _n_ gram-molecules of sugar, C_{12}H_{22}O_{11}, _i.e._ _n_ 342 grms., be dissolved in them, then the depression _d_, or fall (counting from 0°) of the temperature of the formation of ice will be (according to Pickering) _n_ = 0 0·010 0·025 0·100 0·250 1·000 _d_ = 0° 0°·0103 0°·0280 0°·1115 0°·2758 1°·1412 which shows that for high degrees of dilution (up to 0·25_n_) _d_ approximately (estimating the possible errors of experiment at ±0°·005) = _n_1·10, because then _d_ = 0°, 0°·0110, 0°·0275, 0°·1100, 0°·2750, 1°·1000, and the difference between these figures and the results of experiment for very dilute solutions is less than the possible errors of experiment (for _n_ = 1 the difference is already greater) and therefore for dilute solutions of sugar it may be said that _n_ molecules of sugar in dissolving in 100 molecules of water give a depression of about 1°·1_n_. Similar data for acetone (Chapter I., Note 49) give a depression of 1°·006_n_ for _n_ molecules of acetone per 100 molecules of water. And in general, for indifferent substances (the majority of organic bodies) the depression per 100H_{2}O is _nearly n_1°·1 to _n_1°·0 (ether, for instance, gives the last number), and consequently in dissolving in 100 grms. of water it is about 18°·0_n_ to 19°·0_n_, taking this rule to apply to the case of a small number of _n_ (not over 0·2_n_). If instead of water, other liquid or fused solvents (for example, benzene, acetic acid, acetone, nitrobenzene or molten naphthaline, metals, &c.) be taken and in the proportion of 100 molecules of the solvent to _n_ molecules of a dissolved indifferent (neither acid nor saline) substance, then the depression is found to be equal to from 0°·62_n_ to 0°·65_n_ and in general K_n_. If the molecular weight of the solvent = _m_, then 100 gram-molecules will weigh 100_m_ grms., and the depression will be approximately (taking 0·63_n_) equal to _m_0·63_n_ degrees for _n_ molecules of the substance dissolved in 100 grms. of the solvent, or in general the depression for 100 grms. of a given solvent = _kn_ where _k_ is almost a constant quantity (for water nearly 18, for acetone nearly 37, &c.) for all dilute solutions. Thus, having found a convenient solvent for a given substance and prepared a definite (by weight) solution (_i.e._ knowing how many grms. _r_ of the solvent there are to _q_ grms. of the substance dissolved) and having determined the depression _d_--_i.e._ the fall in temperature of freezing for the solvent--it is possible to determine the molecular weight of the substance dissolved, because _d_ = _kn_ where _d_ is found by experiment and _k_ is determined by the nature of the solvent, and therefore _n_ or the number of molecules of the substance dissolved can be found. But if _r_ grms. of the solvent and _q_ grms. of the substance dissolved are taken, then there are 100_q_/_r_ of the latter per 100 grms. of the former, and this quantity = _n_X, where _n_ is found from the depression and = _d_/_k_ and X is the molecular weight of the substance dissolved. Hence X = 100_qk_/_rd_, which gives the molecular weight, naturally only approximately, but still with sufficient accuracy to easily indicate, for instance, whether in peroxide of hydrogen the molecule contains HO or H_{2}O_{2} or H_{3}O_{3}, &c. (H_{2}O_{2} is obtained). Moreover, attention should be drawn to the fact that a great many substances taken as solvents give per 100 molecules a depression of about 0·63_n_, whilst water gives about 1·05_n_, _i.e._ a larger quantity, as though the molecules of liquid water were more complex than is expressed by the formula H_{2}O.[28] A similar phenomenon which repeats itself in the osmotic pressure, vapour tension of the solvent, &c. (_see_ Chapter I., Notes 19 and 49), _i.e._ a variation of the constant (_k_ for 100 grms. of the solvent or K for 100 molecules of it), is also observed in passing from indifferent substances to saline (to acids, alkalis and salts) both in aqueous and other solutions as we will show (according to Pickering's data 1892) for solutions of NaCl and CuSO_{4} in water. For _n_ = 0·01 0·03 0·05 0·1 0·5 molecules of NaCl the depression is _d_ = 0°·0177 0°·0598 0°·0992 0°·1958 0°·9544 which corresponds to a depression per molecule K = 1·77 1·96 1·98 1·96 1·91 _i.e._ here in the most dilute solutions (when _n_ is nearly 0) _d_ is obtained about 1·7_n_, while in the case of sugar it was about 1·1_n_. For CuSO_{4} for the same values of _n_, experiment gave: _d_ = 0°·0164 0°·0451 0°·0621 0°·1321 0°·5245 K = 1·64 1·50 1·44 1·32 1·05 _i.e._ here again _d_ for very dilute solutions is nearly 1·7_n_, but the value of K falls as the solution becomes more concentrated, while for NaCl it at first increased and only fell for the more concentrated solutions. The value of K in the solution of _n_ molecules of a body in 100H_{2}O, when _d_ = K_n_, for very dilute solutions of CaCl_{2} is nearly 2·6, for Ca(NO_{3})_{2} nearly 2·5, for HNO_{3}, KI and KHO nearly 1·9-2·O, for borax Na_{2}B_{4}O_{7} nearly 3·7, &c., while for sugar and similar substances it is, as has been already mentioned, nearly 1·0-1·1. Although these figures are very different[28 bis] still _k_ and K may be considered constant for analogous substances, and therefore the weight of the molecule of the body in solution can be found from _d_. And as the vapour tension of solutions and their boiling points (_see_ Note 27 bis and Chapter I., Note 51) vary in the same manner as the freezing point depression, so they also may serve as means for determining the molecular weight of a substance in solution.[29] [28] A similar conclusion respecting the molecular weight of liquid water (_i.e._ that its molecule in a liquid state is more complex than in a gaseous state, or polymerized into H_{8}O_{4}, H_{6}O_{3} or in general into _n_H_{2}O) is frequently met in chemico-physical literature, but as yet there is no basis for its being fully admitted, although it is possible that a polymerization or aggregation of several molecules into one takes place in the passage of water into a liquid or solid state, and that there is a converse depolymerization in the act of evaporation. Recently, particular attention has been drawn to this subject owing to the researches of Eötvös (1886) and Ramsay and Shields (1893) on the variation of the surface tension N with the temperature (N = the capillary constant _a_^2 multiplied by the specific gravity and divided by 2, for example, for water at 0° and 100° the value of _a_^2 = 15·41 and 12·58 sq. mm., and the surface tension 7·92 and 6·04). Starting from the absolute boiling point (Chapter II., Note 29) and adding 6°, as was necessary from all the data obtained, and calling this temperature T, it is found that AS = _k_T, where S is the surface of a gram-molecule of the liquid (if M is its weight in grams, _s_ its sp. gr., then its sp. volume = M/_s_, and the surface S = [3root](M/_s_)^2), A the surface tension (determined by experiment at T), and _k_ a constant which is independent of the composition of the molecule. The equation AS = _k_T is in complete agreement with the well-known equation for gases _vp_ = RT (p. 140) which serves for deducing the molecular weight from the vapour density. Ramsay's researches led him to the conclusion that the liquid molecules of CS_{2}, ether, benzene, and of many other substances, have the same value as in a state of vapour, whilst with other liquids this is not the case, and that to obtain an accordance, that is, that _k_ shall be a constant, it is necessary to assume the molecular weight in the liquid state to be _n_ times as great. For the fatty alcohols and acids _n_ varies from 1-1/2 to 3-1/2, for water from 2-1/4 to 4, according to the temperature (at which the depolymerization takes place). Hence, although this subject offers a great theoretical interest, it cannot be regarded as firmly established, the more so since the fundamental observations are difficult to make and not sufficiently numerous; should, however, further experiments confirm the conclusions arrived at by Professor Ramsay, this will give another method of determining molecular weights. [28 bis] Their variance is expressed in the same manner as was done by Van't Hoff (Chapter I., Notes 19 and 49) by the quantity _i_, taking it as = 1 when _k_ = 1·05, in that case for KI, _i_ is nearly 2, for borax about 4, &c. [29] We will cite one more example, showing the direct dependence of the properties of a substance on the molecular weight. If one molecular part by weight of the various chlorides--for instance, of sodium, calcium, barium, &c.--be dissolved in 200 molecular parts by weight of water (for instance, in 3,600 grams) then it is found that the greater the molecular weight of the salt dissolved, the greater is the specific gravity of the resultant solution. Molecular Sp. gr. Molecular Sp. gr. weight at 15° weight at 15° HCl 36·5 1·0041 CaCl_{2} 111 1·0236 NaCl 58·5 1·0106 NiCl_{2} 130 1·0328 KCl 74·5 1·0121 ZnCl_{2} 136 1·0331 BeCl_{2} 80 1·0138 BaCl_{2} 208 1·0489 MgCl_{2} 95 1·0203 Thus not only in vapours and gases, but also in dilute solutions of solid and liquid substances, we see that if not all, still many properties are wholly dependent upon the molecular weight and not upon the quality of a substance, and that this gives the possibility of determining the weight of molecules by studying these properties (for instance, the vapour density, depression of the freezing point, &c.) It is apparent from the foregoing that the physical and even more so the chemical properties of homogeneous substances, more especially solid and liquid, do not depend exclusively upon the weights of their molecules, but that many are in definite (_see_ Chapter XV.) dependence upon the weights of the atoms of the elements entering into their composition, and are determined by their quantitative and individual peculiarities. Thus the density of solids and liquids (as will afterwards be shown) is chiefly determined by the weights of the atoms of the elements entering into their composition, inasmuch as dense elements (in a free state) and compounds are only met with among substances containing elements with large atomic weights, such as gold, platinum, and uranium. And these elements themselves, in a free state, are the heaviest of all elements. Substances containing such light elements as hydrogen, carbon, oxygen and nitrogen (like many organic substances) never have a high specific gravity; in the majority of cases it scarcely exceeds that of water. The density generally decreases with the increase of the amount of hydrogen, as the lightest element, and a substance is often obtained lighter than water. The refractive power of substances also entirely depends on the composition and the properties of the component elements.[29 bis] The history of chemistry presents a striking example in point--Newton foresaw from the high refractive index of the diamond that it would contain a combustible substance since so many combustible oils have a high refractive power. We shall afterwards see (Chapter XV.) that many of those properties of substances which are in direct dependence not upon the weight of the molecules but upon their composition, or, in other words, upon the properties and quantities of the elements entering into them, stand in a peculiar (periodic) dependence upon the atomic weight of the elements; that is, the mass (of molecules and atoms), proportional to the weight, determines the properties of substances as it also determines (with the distance) the motions of the heavenly bodies. [29 bis] With respect to the optical refractive power of substances, it must first be observed that the coefficient of refraction is determined by two methods: (_a_) either all the data are referred to one definite ray--for instance, to the Fraunhofer (sodium) line D of the solar spectrum--that is, to a ray of definite wave length, and often to that red ray (of the hydrogen spectrum) whose wave length is 656 millionths of a millimetre; (_b_) or Cauchy's formula is used, showing the relation between the coefficient of refraction and dispersion to the wave length _n_ = A + (B/([Greek: l]^2)), where A and B are two constants varying for every substance but constant for all rays of the spectrum, and [Greek: l] is the wave length of that ray whose coefficient of refraction is _n_. In the latter method the investigation usually concerns the magnitudes of A, which are independent of dispersion. We shall afterwards cite the data, investigated by the first method, by which Gladstone, Landolt, and others established the conception of the refraction equivalent. It has long been known that the _coefficient of refraction n_ for a given substance decreases with the density of a substance D, so that the magnitude (_n_-1) ÷ D = C is almost constant for a given ray (having a definite wave length) and for a given substance. This constant is called the _refractive energy_, and its product with the atomic or molecular weight of a substance the _refraction equivalent_. The coefficient of refraction of oxygen is 1·00021, of hydrogen 1·00014, their densities (referred to water) are 0·00143 and 0·00009, and their atomic weights, O = 16, H = 1; hence their refraction equivalents are 3 and 1·5. Water contains H_{2}O, consequently the sum of the equivalents of refraction is (2 × 1·5) + 3 = 6. But as the coefficient of refraction of water = 1·331, its refraction equivalent = 5·958, or nearly 6. Comparison shows that, approximately, the sum of the refraction equivalents of the atoms forming compounds (or mixtures) is equal to the refraction equivalent of the compound. According to the researches of Gladstone, Landolt, Hagen, Brühl and others, the refraction equivalents of the elements are--H = 1·3, Li = 3·8, B = 4·0, C = 5·0, N = 4·1 (in its highest state of oxidation, 5·3), O = 2·9, F = 1·4, Na = 4·8, Mg = 7·0, Al = 8·4, Si = 6·8, P = 18·3, S = 16·0, Cl = 9·9, K = 8·1, Ca = 10·4, Mn = 12·2, Fe = 12·0 (in the salts of its higher oxides, 20·1), Co = 10·8, Cu = 11·6, Zn = 10·2, As = 15·4, Bi = 15·3, Ag = 15·7, Cd = 13·6, I = 24·5, Pt = 26·0, Hg = 20·2, Pb = 24·8, &c. The refraction equivalents of many elements could only be calculated from the solutions of their compounds. The composition of a solution being known it is possible to calculate the refraction equivalent of one of its component parts, those for all its other components being known. The results are founded on the acceptance of a law which cannot be strictly applied. Nevertheless the representation of the refraction equivalents gives an easy means for directly, although only approximately, obtaining the coefficient of refraction from the chemical composition of a substance. For instance, the composition of carbon bisulphide is CS_{2} = 76, and from its density, 1·27, we find its coefficient of refraction to be 1·618 (because the refraction equivalent = 5 + 2 × 16 = 37), which is very near the actual figure. It is evident that in the above representation compounds are looked on as simple mixtures of atoms, and the physical properties of a compound as the sum of the properties present in the elementary atoms forming it. If this representation of the presence of simple atoms in compounds had not existed, the idea of combining by a few figures a whole mass of data relating to the coefficient of refraction of different substances could hardly have arisen. For further details on this subject, see works on _Physical Chemistry_. CHAPTER VIII CARBON AND THE HYDROCARBONS It is necessary to clearly distinguish between the two closely-allied terms, charcoal and carbon. Charcoal is well known to everybody, although it is no easy matter to obtain it in a chemically pure state. Pure charcoal is a simple, insoluble, infusible, combustible substance produced by heating organic matter, and has the familiar aspect of a black mass, devoid of any crystalline structure, and completely insoluble. Charcoal is a substance possessing a peculiar combination of physical and chemical properties. This substance, whilst in a state of ignition, combines directly with oxygen; in organic substances it is found in combination with hydrogen, oxygen, nitrogen, and sulphur. But in all these combinations there is no real charcoal, as in the same sense there is no ice in steam. What is found in such combinations is termed 'carbon'--that is, an element common to charcoal, to those substances which can be formed from it, and also to those substances from which it can be obtained. Carbon may take the form of charcoal, but occurs also as diamond and as graphite. Truly no other element has such a wide terminology. Oxygen is always called 'oxygen,' whether it is in a free gaseous state, or in the form of ozone, or oxygen in water, or in nitric acid or in carbonic anhydride. But here there is some confusion. In water it is evident that there is no oxygen in a gaseous form, such as can be obtained in a free state, no oxygen in the form of ozone, but a substance which is capable of producing both oxygen, ozone, and water. As an element, oxygen possesses a known chemical individuality, and an influence on the properties of those combinations into which it enters. Hydrogen gas is a substance which reacts with difficulty, but the element hydrogen represents in its combinations an easily displaceable component part. Carbon may be considered as an atom of carbon matter, and charcoal as a collection of such atoms forming a whole substance, or mass of molecules of the substance. The accepted atomic weight of carbon is 12, because that is the least quantity of carbon which enters into combination in molecules of its compounds; but the weight of the molecules of charcoal is probably very much greater. This weight remains unknown because charcoal is capable of but few direct reactions and those only at a high temperature (when the weight of its molecules probably changes, as when ozone changes into oxygen), and it does not turn into vapour. Carbon exists in nature, both in a free and combined state, in most varied forms and aspects. Carbon in a free state is found in at least three different forms, as charcoal, graphite, and the diamond. In a combined state it enters into the composition of what are called organic substances--a multitude of substances which are found in all plants and animals. It exists as carbonic anhydride both in air and in water, and in the soil and crust of the earth as salts of carbonic acid and as organic remains. The variety of the substances of which the structure of plants and animals is built up is familiar to all. Wax, oil, turpentine, and tar, cotton and albumin, the tissue of plants and the muscular fibre of animals, vinegar and starch, are all vegetable and animal matters, and all carbon compounds.[1] The class of carbon compounds is so vast that it forms a separate branch of chemistry, known under the name of organic chemistry--that is, the chemistry of carbon compounds, or, more strictly, of the hydrocarbons and their derivatives. [1] Wood is the non-vital part of ligneous plants: the vital part of ordinary trees is situated between the bark and the lignin. Every year a layer of lignin is deposited on this part by the juices which are absorbed by the roots and drawn up by the leaves; for this reason the age of trees may be determined by the number of lignin layers deposited. The woody matter consists principally of fibrous tissue on to which the lignin or so-called incrusting matter has been deposited. The tissue has the composition C_{6}H_{10}O_{5}, the substance deposited on it contains more carbon and hydrogen and less oxygen. This matter is saturated with moisture when the wood is in a fresh state. Fresh birch wood contains about 31 p.c. of water, lime wood 47 p.c., oak 35 p.c., pine and fir about 37 p.c. When dried in the air the wood loses a considerable quantity of water and not more than 19 p.c. remains. By artificial means this loss of water may be increased. If water be driven into the pores of wood the latter becomes heavier than water, as the lignin of which it is composed has a density of about 1·6. One cubic centimetre of birch wood does not weigh more than 0·901 gram, fir 0·894, lime tree 0·817, poplar 0·765 when in a fresh state; when in a dry state birch weighs 0·622, pine 0·550, fir 0·355, lime 0·430, guaiacum 1·342, ebony 1·226. On one hectare (2·7 acres) of woodland the yearly growth averages the amount of 3,000 kilograms (or about 3 tons) of wood, but rarely reaches as much as 5,000 kilos. The average chemical composition of wood dried in air may be expressed as follows:--Hygroscopic water 15 p.c., carbon 42 p.c., hydrogen 5 p.c., oxygen and nitrogen 37 p.c., ash 1 p.c. Wood parts with its hygroscopic water at 150°, and decomposes at about 300°, giving a brown, brittle, so-called red charcoal; above 350° black charcoal is produced. As the hydrogen contained in wood requires for its combustion about forty parts by weight of oxygen, which is present to the amount of about 36 p.c., all that burns of the wood is the carbon which it contains, 100 parts of wood only giving out as much heat as forty parts of charcoal, and therefore it would be far more profitable to use charcoal for heating purposes than wood, if it were possible to obtain it in such quantities as correspond with its percentage ratio--that is forty parts per 100 parts of wood. Generally, however, the quantity produced is far less, not more than 30 p.c., because part of the carbon is given off as gas, tar, &c. If wood has to be transported great distances, or if it is necessary to obtain a very high temperature by burning it, then even as little as 25 p.c. of charcoal from 100 parts of wood may be advantageous. Charcoal (from wood) develops on burning 8,000 heat units, whilst wood dried in air does not develop more than 2,800 units of heat; therefore seven parts of charcoal give as much heat as twenty parts of wood. As regards the temperature of combustion, it is far higher with charcoal than with wood, because twenty parts of burning wood give, besides the carbonic anhydride which is also formed together with charcoal, eleven parts of water, the evaporation of which requires a considerable amount of heat. [Illustration: FIG. 57.--Apparatus for the dry distillation of wood. The retort _a_ containing the wood is heated by the flues _c e_. The steam and volatile products of distillation pass along the tube g through the condenser _m_, where they are condensed. The form, distribution, and dimensions of the apparatus vary.] The composition of the growing parts of plants, the leaves, young branches, shoots, &c., differs from the composition of the wood in that these vital parts contain a considerable quantity of sap which contains much nitrogenous matter (in the wood itself there is very little), mineral salts, and a large amount of water. Taking, for example, the composition of clover and pasture hay in the green and dry state; in 100 parts of green clover there is about 80 p.c. of water and 20 p.c. of dry matter, in which there are about 3·5 parts of nitrogenous albuminous matter, about 9·5 parts of soluble and about 5 parts of insoluble non-nitrogenous matter, and about 2 p.c. of ash. In dry clover or clover-hay there is about 15 p.c. of water, 13 p.c. of nitrogenous matter, and 7 p.c. of ash. This composition of grassy substances shows that they are capable of forming the same sort of charcoal as wood itself. It also shows the difference of nutritive properties existing between wood and the substances mentioned. These latter serve as food for animals, because they contain those substances which are capable of being dissolved (entering into the blood) and forming the body of animals; such substances are proteids, starch, &c. Let us remark here that with a good harvest an acre of land gives in the form of grass as much organic substance as it yields in the form of wood. One hundred parts of dry wood are capable of giving, on dry distillation, besides 25 p.c. of charcoal and 10 p.c. or more of tar, 40 p.c. of watery liquid, containing acetic acid and wood spirit, and about 25 p.c. of gases, which may be used for heating or lighting purposes, because they do not differ from ordinary illuminating gas, which can indeed be obtained from wood. As wood-charcoal and tar are valuable products, in some cases the dry distillation of wood is carried on principally for producing them. For this purpose those kinds of woods are particularly advantageous which contain resinous substances, especially coniferous trees, such as fir, pine, &c.; birch, oak, and ash give much less tar, but on the other hand they yield more aqueous liquor. The latter is used for the manufacture of wood spirit, CH_{4}O, and acetic acid, C_{2}H_{4}O_{2}. In such cases, the dry distillation is carried on in stills. The stills are nothing more than horizontal or vertical cylindrical retorts, made of boiler plate, heated with fuel and having apertures at the top and sometimes also at the bottom for the exit of the light and heavy products of distillation. The dry distillation of wood in stoves is carried on in two ways, either by burning a portion of the wood inside the stove in order to submit the remainder to dry distillation by means of the heat obtained in this manner, or by placing the wood in a stove the thin sides of which are surrounded with a flue leading from the fuel, placed in a space below. The first method does not give such a large amount of liquid products of the dry distillation as the latter. In the latter process there is generally an outlet below for emptying out the charcoal at the close of the operation. For the dry distillation of 100 parts of wood from forty to twenty parts of fuel are used. In the north of Russia wood is so plentiful and cheap that this locality is admirably fitted to become the centre of a general trade in the products of its dry distillation. Coal (Note 6), sea-weed, turf, animal substances (Chapter VI.), &c., are also submitted to the process of dry distillation. If any one of these organic compounds be strongly heated without free access of air--or, better still, in a vacuum--it decomposes with more or less facility. If the supply of air be insufficient, or the temperature be too low for combustion (_see_ Chapter III.), and if the first volatile products of transformation of the organic matter are subjected to condensation (for example, if the door of a stove be opened), an imperfect combustion takes place, and smoke, with charcoal or soot, is formed.[2] The nature of the phenomenon, and the products arising from it, are the same as those produced by heating alone, since that part which is in a state of combustion serves to heat the remainder of the fuel. The decomposition which takes place on heating a compound composed of carbon, hydrogen, and oxygen is as follows:--A part of the hydrogen is separated in a gaseous state, another part in combination with oxygen, and a third part separates in combination with carbon, and sometimes in combination with carbon and oxygen in the form of gaseous or volatile products, or, as they are also called, the products of dry distillation. If the vapours of these products are passed through a strongly heated tube, they are changed again in a similar manner and finally resolve themselves into hydrogen and charcoal. Altogether these various products of decomposition contain a smaller amount of carbon than the original organic matter; part of the carbon remains in a free state, forming charcoal.[3] It remains in that space where the decomposition took place, in the shape of the black, infusible, non-volatile charcoal familiar to all. The earthy matter and all non-volatile substances (ash) forming a part of the organic matter, remain behind with the charcoal. The tar-like substances, which require a high temperature in order to decompose them, also remain mixed with charcoal. If a volatile organic substance, such as a gaseous compound containing oxygen and hydrogen, be taken, the carbon separates on passing the vapour through a tube heated to a high temperature. Organic substances when burning with an insufficient supply of air give off soot--that is, charcoal--proceeding from carbon compounds in a state of vapour, the hydrogen of which has, by combustion, been converted into water; so, for instance, turpentine, naphthalene, and other hydrocarbons which are with difficulty decomposed by heat, easily yield carbon in the form of soot during combustion. Chlorine and other substances which, like oxygen, are capable of taking up hydrogen, and also substances which are capable of taking up water, can also separate carbon from (or char) most organic substances. [2] The result of imperfect combustion is not only the loss of a part of the fuel and the production of smoke, which in some respects is inconvenient and injurious to health, but also a low flame temperature, which means that a less amount of heat is transmitted to the object heated. Imperfect combustion is not only always accompanied by the formation of soot or unburnt particles of charcoal, but also by that of carbonic oxide, CO, in the smoke (Chapter IX.) which burns, emitting much heat. In works and factories where large quantities of fuel are consumed, many appliances are adopted to ensure perfect combustion, and to combat against such a ruinous practice as the imperfect combustion of fuel. The most effective and radical means consists in employing combustible gases (producer and water gases), because by their aid perfect combustion can be easily realised without a loss of heat-producing power and the highest temperature can be reached. When solid fuel is used (such as coal, wood, and turf), imperfect combustion is most liable to occur when the furnace doors are opened for the introduction of fresh fuel. The step furnace may often prove a remedy for this defect. In the ordinary furnace fresh fuel is placed on the burning fuel, and the products of dry distillation of the fresh fuel have to burn at the expense of the oxygen remaining uncombined with the burnt fuel. Imperfect combustion is observed in this case also from the fact that the dry distillation and evaporation of the water of the fresh fuel lying on the top of that burnt, lowers the temperature of the flame, because part of the heat becomes latent. On this account a large amount of smoke (imperfect combustion) is observed when a fresh quantity of fuel is introduced into the furnace. This may be obviated by constructing the furnace (or managing the stoking) in such a way that the products of distillation pass through the red-hot charcoal remaining from the burnt fuel. It is only necessary in order to ensure this to allow a sufficient quantity of air for perfect combustion. All this may be easily attained by the use of step fire-bars. The fuel is fed into a hopper and falls on to the fire-bars, which are arranged in the form of a staircase. The burning charcoal is below, and hence the flame formed by the fresh fuel is heated by the contact of the red-hot burning charcoal. An air supply through the fire grate, an equal distribution of the fuel on the fire-bars (otherwise the air will blow through empty spaces and lower the temperature), a proper proportion between the supply of air and the chimney draught, and a perfect admixture of air with the flame (without an undue excess of air), are the means by which we can contend against the imperfect combustion of such kinds of fuel as wood, peat, and ordinary (smoky) coal. Coke, charcoal, anthracite, burn without smoke, because they do not contain hydrogenous substances which furnish the products of dry distillation, but imperfect combustion may occur with them also; in that case the smoke contains carbonic oxide. [3] Under the action of air, organic substances are capable of oxidising to such an extent that all the carbon and all the hydrogen they contain will be transformed into carbonic anhydride and water. The refuse of plants and that of animals are subjected to such a change whether they slowly decompose and putrefy, or rapidly burn with direct access of air. But if the supply of air be limited, there can be no complete transformation into water and carbonic anhydride, there will be other volatile matters (rich in hydrogen), while charcoal must remain as a non-volatile substance. All organic substances are unstable, they do not resist heat, and change even at ordinary temperatures, particularly if water be present. It is therefore easy to understand that charcoal may in many cases be obtained through the transformation of substances entering into the composition of organisms, but that it is never found in a pure state. However, water and carbonic anhydride are not the only products separated from organic substances. Carbon, hydrogen, and oxygen are capable of giving a multitude of compounds; some of these are volatile compounds, gaseous, soluble in water--they are carried off from organic matter, undergoing change without access of air. Others, on the contrary, are non-volatile, rich in carbon, unaffected by heat and other agents. The latter remain in admixture with charcoal in the place where the decomposition takes place; such, for example, are tarry substances. The quantity of those bodies which are found mixed with the charcoal is very varied, and depends on the energy and duration of the decomposing agent. The annexed table shows, according to the data of Violette, those changes which wood undergoes at various temperatures when submitted to dry distillation by means of superheated steam:-- +----------------------------+------------------------------+ | Residue | | |Temperature from 100 parts | In 100 parts of the residual | | of alder wood | charcoal | +----------------------------+---------------------+--------+ | | C H O and N | Ash | | 150° 100·0 | 47·5 6·1 46·3 | 0·1 | | 350° 29·7 | 76·6 4·1 18·4 | 0·6 | | 1032° 18·7 | 81·9 2·3 14·1 | 1·6 | | 1500° 17·3 | 95·0 0·7 3·8 | 1·7 | +----------------------------+---------------------+--------+ Wood charcoal is prepared in large quantities in a similar manner--that is, by the partial combustion of wood.[4] In nature a similar process of carbonisation of vegetable refuse takes place in its transformation under water, as shown by the marshy vegetation which forms peat.[5] In this manner doubtless the enormous masses of coal were formed[6] which, following the example set by England, are now utilised everywhere as the principal material for heating steam boilers, and in general for all purposes of heating and burning.[7] Russia possesses many very rich coalfields, amongst which the Donetz district is most worthy of remark.[8] [4] The object of producing charcoal from wood has been explained in Note 1. _Wood charcoal_ is obtained in so-called stacks by partially burning the wood, or by means of dry distillation (Note 1) without the access of air. It is principally manufactured for metallurgical processes, especially for smelting and forging iron. The preparation of charcoal in stacks has one advantage, and that is that it may be done on any spot in the forest. But in this way all the products of dry distillation are lost. For charcoal burning, a pile or stack is generally built, in which the logs are placed close together, either horizontally, vertically, or inclined, forming a stack of from six to fifty feet in diameter and even larger. Under the stack are several horizontal air passages, and an opening in the middle to let out the smoke. The surface of the stack is covered with earth and sods to a considerable thickness, especially the upper part, in order to hinder the free passage of air and to concentrate the heat inside. When the stack is kindled, the pile begins to settle down by degrees, and it is then necessary to look after the turf casing and keep it in repair. As the combustion spreads throughout the whole pile, the temperature rises and real dry distillation commences. It is then necessary to stop the air holes, in order as much as possible to prevent unnecessary combustion. The nature of the process is, that part of the fuel burns and develops the heat required for subjecting the remainder to dry distillation. The charring is stopped when the products of dry distillation, which are emitted, no longer burn with a brilliant flame, but the pale blue flame of carbonic oxide appears. Dry wood in stacks yields about one-fourth of its weight of charcoal. [5] When dead vegetable matter undergoes transformation in air, in the presence of moisture and lower organisms, there remains a substance much richer in carbon--namely, humus, black earth or mould. 100 parts of humus in a dry state contain about 70 p.c. of carbon. The roots, leaves, and stems of plants which wither and fall to the ground form a soil rich in humus. The non-vital vegetable substances (ligneous tissue) first form brown matter (ulmic compounds), and then black matter (humic substances), which are both insoluble in water; after this a brown acid is produced, which is soluble in water (apocrenic acid), and lastly a colourless acid also soluble in water (crenic acid). Alkali dissolves a part of the original brown and black substances, forming solutions of a brown tint (ulmic and humic acids) which sometimes communicate their colour to springs and rivers. The proportion of humus in soil generally has a direct influence on its fertility; firstly, because putrefying plants develop carbonic anhydride and ammonia, and yield the substances forming the ashes of plants, which are necessary to vegetation; secondly, because humus is capable of attracting the moisture of the air and of absorbing water (twice its weight) and in this way keeps the soil in a damp condition, which is indispensable for nourishment; thirdly, humus renders the soil porous, and, fourthly, it renders it more capable of absorbing the heat of the sun's rays. On this account black earth is often most remarkable for its fertility. One object of manuring is to increase the quantity of humus in the soil, and any easily changeable vegetable or any animal matter (composts) may be used. The boundless tracts of black earth soil in Russia are capable of bestowing countless wealth on the country. The origin and extent of black earth soil are treated in detail in Professor Dokouchaeff's works. If those substances which produce humus undergo decomposition under water, less carbonic anhydride is formed, a quantity of marsh gas, CH_{4}, is evolved, and the solid residue forms an acid humus found in great quantities in marshy places and called _peat_. Peat is especially abundant in the lowlands of Holland, North Germany, Ireland, and Bavaria. In Russia it is likewise found in large quantities, especially in the North-West districts. The old hard forms of peat resemble in composition and properties brown coal; the newest formations, as yet unhardened by pressure, form very porous masses which retain traces of the vegetable matter from which they have been formed. Dried (and sometimes pressed) peat is used as fuel. The composition of peat varies considerably with the locality in which it is found. When dried in air it does not contain less than 15 p.c. of water and 8 p.c. of ash; the remainder consists of 45 p.c. of carbon, 4 p.c. of hydrogen, 1 p.c. of nitrogen, and 28 p.c. of oxygen. Its heating power is about equivalent to that of wood. The brown earthy varieties of coal were probably formed from peat. In other cases they have a marked woody structure, and are then known as lignites. The composition of the brown sorts of coal resembles in a marked degree that of peat--namely, in a dried state brown coal contains on an average 60 p.c. of carbon, 5 p.c. of hydrogen, 26 p.c. of oxygen and nitrogen, and 9 p.c. of ash. In Russia brown coal is met with in many districts near Moscow, in the Governments of Toula and Tver and the neighbourhood; it is very usually used as fuel, particularly when found in thick seams. The brown coals usually burn with a flame like wood and peat, and are akin to them in heating power, which is half or a third that of the best coal. [6] Grass and wood, the vegetation of primæval seas and similar refuse of all geological periods, must have been in many cases subjected to the same changes they now undergo--that is, under water they formed peat and lignites. Such substances, preserved or a long time underground, subjected to the action of water, compressed by the new strata formed above them, transformed by the separation of their more volatile component parts (peat and lignites, even in their last condition, still continue to evolve nitrogen, carbonic anhydride, and marsh gases) form _coal_. Coal is a dense homogeneous mass, black, with an oily or glassy lustre, or more rarely dull without any evident vegetable structure; this distinguishes it in appearance from the majority of lignites. The density of coal (not counting the admixture of pyrites, &c.) varies from 1·25 (dry bituminous coal) to 1·6 (anthracite, flameless), and even reaches 1·9 in the very dense variety of coal found in the Olonetzky government (termed shungite), which according to the investigations of Professor Inostrantzeff may be regarded as the extreme member of the various forms of coal. In order to explain the formation of coal from vegetable matter, Cagniard de la Tour enclosed pieces of dried wood in a tube and heated them to the boiling point of mercury, when the wood was changed into a semi-liquid black mass from which a substance exceedingly like coal separated. In this manner some kinds of wood formed coal which on being heated left caking coke, others non-caking; precisely as we find with the natural varieties of coal. Violette repeated these experiments with wood dried at 150°, and showed that when wood is decomposed in this way, a gas, an aqueous liquor, and a residue are formed. The latter at a temperature of 200° has the properties of wood charcoal incompletely burnt; at 300° and higher a homogeneous mass like coal is formed which at 340° is dense and without cavities. At 400° the residue resembles anthracite. In nature probably the decomposition was in rare cases effected by heat alone; more generally it was effected by means of water and heat, but in either case the result ought to be almost the same. The average composition of coal compiled from many analyses, disregarding the ash, is as follows: 84 parts of carbon, 5 parts of hydrogen, 1 part of nitrogen, 8 parts of oxygen, 2 of sulphur. The quantity of ash is on an average 5 p.c., but there are coals which contain a larger quantity, and naturally they are not so advantageous for use as fuel. The amount of water does not usually exceed more than 10 p.c. The _anthracites_ form a remarkable variety of coals, they do not give any volatile products, or but a very small amount, as they contain but little hydrogen compared to oxygen. In the average composition of coal we saw that for 5 parts of hydrogen there were 8 parts of oxygen; therefore 4 parts by weight of hydrogen are capable of forming hydrocarbons, because 1 part of hydrogen is necessary in order to form water with the 8 parts of oxygen. These 4 parts by weight of hydrogen can convert 48 parts of carbon into volatile products, because 1 part of hydrogen by weight in these substances combines with 12 parts of carbon. The anthracites differ essentially from this: neglecting the ash, their average composition is as follows: 94 parts of carbon, 3 of hydrogen, and 3 of oxygen and nitrogen. According to the analyses of A. A. Voskresensky, the Grousheffsky anthracite (Don district) contains: C = 93·8, H = 1·7, ash = 1·5. Therefore the anthracites contain but little hydrogen capable of combining with the carbon to form hydrocarbons which burn with a flame. Anthracites are the oldest forms of coal. The newest and least transformed coals, which resemble some of the brown varieties, are the _dry_ coals. They burn with a flame like wood, and leave a coke having the appearance of lumps of coal, half their component parts being absorbed by the flame (they contain much hydrogen and oxygen). The remaining varieties of coal (gas coal, smithy coal, coking, and anthracite) according to Grüner in all respects form connecting links between the _dry_ coals and the anthracites. These coals burn with a very smoky flame, and on being heated leave _coke_, which bears the same relation to coal that charcoal does to wood. The quantity and quality of coke vary considerably with the different sorts of coal from which it is formed. In practice coals are most often distinguished by the properties and quantity of the coke which they give. In this particular the so-called bituminous coals are especially valuable, as even the slack of this kind gives on dry distillation large spongy masses of coke. If large pieces of these kinds of coal are subjected to dry distillation, they, as it were, melt, flow together, and form caking masses of coke. The best coking coals give 65 p.c. of dense caking coke. Such coal is very valuable for metallurgical purposes (_see_ Note 8). Besides coke, the dry distillation of coal produces gas (_see_ further, illuminating gas, p. 361), coal-tar (which gives benzene, carbolic acid, naphthalene, tar for artificial asphalt, &c.) and also an aqueous alkaline liquor (with wood and lignites the liquid is acid from acetic acid) which contains ammonium carbonate (_see_ Note 6). [7] In England in 1850 the output of coal was as much as 48 million tons, and in latter years it has risen to about 190 millions. Besides this other countries contribute 300 millions--Russia about 6 millions. The United States of America come next to England with an output of 160 million tons, then Germany 90 millions; France produces but little (25 millions), and takes about 5 million tons from England. Thus the world consumes about 500 million tons of coal yearly. Besides household purposes, coal is chiefly used as fuel for steam-engines. As every horse-power (= 75 kilogrammetres per second) of a steam-engine expends on the average more than 25 kilograms in 24 hours, or in a year (counting stoppages) not less than 5 tons per horse-power, and there are not less than 40 million horse-power at work in the world, the consumption of coal for motive-power is at least equal to half the whole production. For this reason coal serves as a criterion of the industrial development of a country. About 15 p.c. of coal is used for the manufacture of cast iron, wrought iron, steel, and articles made of them. [8] The principal coal beds of Russia under exploitation are: The Don basin (150 million poods per annum, 62 poods = 1 ton), the Polish basin (Dombrovo and others 120 million poods per annum), the Toula and Riazan beds of the Moscow basin (up to 25 million poods), the Ural basin (10 million poods), the Caucasian (Kviboul, near Kutais), the Khirjhis steppes, the smithy coal basin (Gov. of Tomsk), the Sahaline, &c. The Polish and Moscow basins do not give any coking coals. The presence of every variety of coal (from the dry coal near Lisichansk on the Donetz to the anthracites of the entire south-east basin), the great abundance of excellent metallurgical coal (coking, _see_ Note 6) in the western part of the basin, its vast extent (as much as 25,000 sq. versts), the proximity of the seams to the surface (the shafts are now from 20 to 100 fathoms deep, and in England and Belgium as deep as 500 fathoms), the fertility of the soil (black earth), the proximity of the sea (about 100 versts from the Sea of Azoff) and of the rivers Donetz, Don, and Dneiper, the most abundant seams of excellent iron ore (Korsan Mogila, Krivoy Rog, Soulin, &c., &c.), copper ore, mercury ore (near Nikitovka, in the Bakhmouth district of the Ekaterinoslav Gov.), and other ores, the richest probably in the whole world, the beds of rock-salt (near the stations of the Stoupka and Brianzovka) the excellent clay of all kinds (china, fire-clay), gypsum, slate, sandstone, and other _wealth of the Don coal basin_, give complete assurance of the fact that with the growth of industrial activity in Russia this bountiful land of the Cossacks and New Russia will become the centre of the most extensive productive enterprise, not for the requirements of Russia alone, but of the whole world, because in no other place can be found such a concentration of favourable conditions. The growth of enterprise and knowledge, together with the extinction of the forests which compels Russia to foster the production of coal, will help to bring about this desired result. England with a whole fleet of merchant vessels exports annually about 25 million tons of coal, the price of which is higher than on the Donetz (where a pood of worked coal costs less than 5 copecks on the average), where anthracites and semi-anthracites (like Cardiff or steam coal, which burns without smoke) and coking and metallurgical coals are able both in quantity and quality to satisfy the most fastidious requirements of the industry already existing and rapidly increasing everywhere. The coal mines of England and Belgium are approaching a state of exhaustion, whilst in those of the Don basin, only at a depth of 100 fathoms, 1,200,000 million poods of coal lie waiting to be worked. During the imperfect combustion of volatile substances containing carbon and hydrogen, the hydrogen and part of the carbon first burn, and the remainder of the carbon forms soot. Tar, pitch, and similar substances for this reason burn with a smoky flame. Thus soot is finely-divided charcoal separated during the imperfect combustion of the vapours and gases of carbonaceous substances rich in carbon. Specially-prepared soot (lampblack) is very largely used as a black paint and a large quantity goes for the manufacture of printers' ink. It is prepared by burning tar, oil, natural gas, naphtha, &c. The quantity of organic matter remaining undecomposed in the charcoal depends on the temperature to which it has been submitted. Charcoal prepared at the lowest temperature still contains a considerable quantity of hydrogen and oxygen--even as much as 4 p.c. of hydrogen and 20 p.c. of oxygen. Such charcoal still preserves the structure of the substance from which it was obtained. Ordinary charcoal, for instance, in which the structure of the tree is still visible, is of this kind. On submitting it to further heating, a fresh quantity of hydrogen with carbon and oxygen (in the form of gases or volatile matter) may be separated, and the purest charcoal will be obtained on submitting it to the greatest heat.[9] If it be required to prepare pure charcoal from soot it is necessary first to wash it with alcohol and ether in order to remove the soluble tarry products, and then submit it to a powerful heat to drive off the impurities containing hydrogen and oxygen. Charcoal however when completely purified does not change in appearance. Its porosity,[10] bad conducting power for heat, capability of absorbing the luminous rays (hence its blackness and opacity), and many other qualities, are familiar from everyday experience.[11] The specific gravity of charcoal varies from 1·4 to 1·9, and that it floats on water is due to the air contained in its pores. If charcoal is reduced to a powder and moistened with spirit, it immediately sinks in water. It is _infusible_ in the furnace and even at the temperature of the oxyhydrogen flame. In the heat generated by means of a powerful galvanic current charcoal only softens but does not completely melt, and on cooling it is found to have undergone a complete change both in properties and appearance, and is more or less transformed into graphite. The physical stability of charcoal is without doubt allied to its chemical stability. It is evidently a substance devoid of energy, for it is insoluble in all known liquids, and _at an ordinary temperature does not combine with anything_; it is an inactive substance, like nitrogen.[12] But these properties of charcoal change with a rise of temperature; thus, unlike nitrogen, charcoal, at a high temperature, combines directly with oxygen. This is well known, as charcoal burns in air. Indeed, not only does oxygen _combine with charcoal at a red heat_, but sulphur, hydrogen, silicon, and also iron and some other metals[12 bis] do so at a very high temperature--that is, when the molecules of the charcoal have reached a state of great instability--whilst at ordinary temperatures neither oxygen, sulphur, nor metals act on charcoal in any way. When burning in oxygen, charcoal forms carbonic anhydride, CO_{2}, whilst in the vapours of sulphur, carbon bisulphide, CS_{2}, is formed, and wrought iron, when acted on by carbon, becomes cast iron. At the great heat obtained by passing the galvanic current through carbon electrodes, charcoal combines with hydrogen, forming acetylene, C_{2}H_{2}. Charcoal does not combine directly with nitrogen, but in the presence of metals and alkaline oxides, nitrogen is absorbed, forming a metallic cyanide, as, for instance, potassium cyanide, KCN. From these few direct combinations which charcoal is capable of entering into, may be derived those numerous carbonaceous compounds which enter into the composition of plants and animals, and can be thus obtained artificially. Certain substances containing oxygen give up a part of it to charcoal at a relatively low temperature. For instance, nitric acid when boiled with charcoal gives carbonic anhydride and nitric peroxide. Sulphuric acid is reduced to sulphurous anhydride when heated with carbon. When heated to redness charcoal absorbs oxygen from a large number of the oxides. Even such oxides as those of sodium and potassium, when heated to redness, yield their oxygen to charcoal although they do not part with it to hydrogen. Only a few of the oxides, like silica (oxide of silicon) and lime (calcium oxide) resist the reducing action of charcoal. Charcoal is capable of changing its physical condition without undergoing any alteration in its essential chemical properties--that is, it passes into _isomeric_ or _allotropic forms_. The two other particular forms in which carbon appears are the _diamond_ and _graphite_. The identity of composition of these with charcoal is proved by burning an equal quantity of all three separately in oxygen (at a very high temperature), when each gives the same quantity of carbonic anhydride--namely, 12 parts of charcoal, diamond, or graphite in a pure state, yield on burning 44 parts by weight of carbonic anhydride. The physical properties present a marked contrast; the densest sorts of charcoal have a density of only 1·9, whilst the density of graphite is about 2·3, and that of the diamond 3·5. A great many other properties depend on the density, for instance combustibility. The lighter charcoal is, the more easily it burns; graphite burns with considerable difficulty even in oxygen, and the diamond burns only in oxygen and at a very high temperature. On burning, charcoal, the diamond, and graphite develop different quantities of heat. One part by weight of wood charcoal converted by burning into carbonic anhydride develops 8,080 heat units; dense charcoal separated in gas retorts develops 8,050 heat units; natural graphite, 7,800 heat units; and the diamond 7,770. The greater the density the less the heat evolved by the combustion of the carbon.[13] [9] As it is difficult to separate from the charcoal the admixture of ash--that is, the earthy matter contained in the vegetable substance used for producing charcoal--in order to obtain it in its purest condition it is necessary to use such organic substances as do not contain any ash, for example completely refined or purified crystallised sugar, crystallised tartaric acid, &c. [10] The cavities in charcoal are the passages through which those volatile products formed at the same time as the charcoal have passed. The degree of porosity of charcoal varies considerably, and has a technical significance, in different kinds of charcoal. The most porous charcoal is very light; a cubic metre of wood charcoal weighs about 200 kilograms. Many of the properties of charcoal which depend exclusively on its porosity are shared by many other porous substances, and vary with the density of the charcoal and depend on the way it was prepared. The property which charcoal has of absorbing gases, liquids, and many substances in solution, is a case in point. The densest kind of charcoal is formed by the action of great heat on sugar and other fusible substances. The lustrous grey dense coke formed in gas retorts is also of this character. This dense coke collects on the internal walls of the retorts subjected to great heat, and is produced by the vapours and gases separated from the heated coal in the retorts. In virtue of its density such coke becomes a good conductor of the galvanic current and approaches graphite. It is principally used in galvanic batteries. Coke, or the charcoal remaining from the imperfect combustion of coal and tarry substances, is also but slightly porous, brilliant, does not soil or mark paper, is dense, almost devoid of the faculty of retaining liquids and solids, and does not absorb gases. The light sorts of charcoal produced from charred wood, on the other hand, show this absorptive power in a most marked degree. This property is particularly developed in that very fine and friable charcoal prepared by heating animal substances such as hides and bones. _The absorptive power of charcoal_ for gases is similar to the condensation of gases in spongy platinum. Here evidently there is a case of the adherence of gases to a solid, precisely as liquids have the property of adhering to various solids. One volume of charcoal will absorb the following volumes of gases (charcoal is capable of absorbing an immense amount of chlorine, almost equal to its own weight):-- -------------------------------------------------------- Saussure. Favre. Heat emitted Boxwood Charcoal Cocoanut Charcoal per gram of gas ------------------------------------------------------- NH_{3} 90 172 vols. 494 units CO_{2} 35 97 " 158 " N_{2}O 40 99 " 169 " HCl 85 165 " 274 " ------------------------------------------------------- The quantity of gas absorbed by the charcoal increases with the pressure, and is approximately proportional to it. The quantity of heat given out by the absorption nearly approaches that set free on dissolving, or passing into a liquid condition. Charcoal absorbs not only gases, but a number of other substances. For instance, alcohol which contains disagreeably smelling fusel oil, on being mixed with charcoal or filtered through it, loses most of the fusel oil. The practice of filtering substances through charcoal in order to get rid of foreign matters is often applied in chemical and manufacturing processes. Oils, spirits, various extracts, and vegetable and other solutions are filtered through charcoal in order to purify them. The bleaching power of charcoal may be tested by using various coloured solutions--such as aniline dyes, litmus, &c. Charcoal, which has absorbed one substance to saturation is still capable of absorbing certain other substances. Animal charcoal, produced in a very finely-divided state, especially by heating bones, makes the best sort for the purposes of absorption. Bone charcoal is used in large quantities in sugar works for filtering syrups and all saccharine solutions, in order to purify them, not only from colouring and odorous matter, but also from the lime which is mixed with the syrups in order to render them less unstable during boiling. The absorption of lime by animal charcoal depends, in all probability, in a great degree on the mineral component parts of bone charcoal. [11] Charcoal is a very bad conductor of heat, and therefore forms an excellent insulator or packing to prevent the transmission of heat. A charcoal lining is often used in crucibles for heating many substances, as it does not melt and resists a far greater heat than many other substances. [12] The unalterability of charcoal under the action of atmospheric agencies, which produce changes in the majority of stony and metallic substances, is often made use of in practice. For example, charcoal is frequently strewn in boundary ditches. The surface of wood is often charred to render it durable in those places where the soil is damp and wood itself would soon rot. The chambers (or in some works towers) through which acids pass (for example, sulphuric and hydrochloric) in order to bring them into contact with gases or liquids, are filled with charcoal or coke, because at ordinary temperatures it resists the action of even the strongest acids. [12 bis] Maquenne (1892) discovered that carbon is capable of combining with the alkali metals. A 20 p.c. amalgam of the metals was heated to a red heat with charcoal powder in a stream of hydrogen. The compounds so obtained possessed, after the mercury had been driven off, the compositions BaC_{2}, SrC_{2}, CaC_{2}. All these compounds react with water forming acetylene, for example: BaC_{2} + 2H_{2}O = C_{2}H_{2} + Ba(OH)_{2} Maquenne proposes the barium carbide as a source of acetylene. He obtained this compound by heating carbonate of barium, magnesium powder, and retort carbon in a Perreau furnace (BaCO_{3} + 3Mg + C = 3MgO + BaC_{2}). One hundred grams of BaC_{2} evolve 5,200 to 5,400 c.c. of acetylene, mixed with about 2-3 p.c. of hydrogen. The relation of acetylene, C_{2}H_{2}, to these metallic carbides is evident from the fact that these metals (Ca, Sr, Ba) replace 2 atoms of hydrogen, and therefore C_{2}Ba corresponds to C_{2}H_{2}, so that they may be regarded as metallic derivatives of acetylene. Moissan (1893) obtained similar carbides directly from the oxides by subjecting them to the action of the voltaic arc, in the presence of carbon, for instance, BaO + 3C = CO + C_{2}Ba, although at a furnace heat carbon has no action on the oxides CaO, BaO, SrO. Concerning Al_{4}C_{5}, _see_ Chapter XVII. Note 38. [13] When subjected to pressure, charcoal loses heat, hence the densest form stands to the less dense as a solid to a liquid, or as a compound to an element. From this the conclusion may be drawn that the molecules of graphite are more complex than those of charcoal, and those of the diamond still more so. The specific heat shows the same variation, and as we shall see further on, the increased complexity of a molecule leads to a diminution of the specific heat. At ordinary temperatures the specific heat of charcoal is 0·24, graphite 0·20, the diamond 0·147. For retort carbon Le Chatelier (1893) found that the product of the sp. heat and atomic weight varies, between 0° and 250°, according to the formula: = 1·92 + 0·0077_t_, and between 250° and 1000°, = 3·54 + 0·00246_t_ (_see_ Chapter XIV. Note 4). By means of intense heat charcoal may be transformed into graphite. If a charcoal rod 4 mm. in diameter and 5 mm. long be enclosed in an exhausted receiver and the current from 600 Bunsen's elements, placed in parallel series of 100, be passed through it, the charcoal becomes strongly incandescent, partially volatilises, and is deposited in the form of graphite. If sugar be placed in a charcoal crucible and a powerful galvanic current passed through it, it is baked into a mass similar to graphite. If charcoal be mixed with wrought iron and heated, cast iron is formed, which contains as much as five per cent. of charcoal. If molten cast iron be suddenly chilled, the carbon remains in combination with the iron, forming so called white cast iron; but if the cooling proceeds slowly, the greater part of the carbon separates in the form of graphite, and if such cast iron (so called grey cast iron) be dissolved in acid, the carbon remains in the form of graphite. Graphite is met with in nature, sometimes in the form of large compact masses, sometimes permeating rocky formations like the schists or slates, and in fact is met with in those places which, in all probability, have been subjected to the action of subterranean heat.[14] The graphite in cast iron, and sometimes also natural graphite, occasionally appears in a crystalline form in the shape of six-sided plates, but more often it occurs as a compact amorphous mass having the characteristic properties of the familiar black-lead pencil.[15] [14] There are places where anthracite gradually changes into graphite as the strata sink. I myself had the opportunity of observing this gradual transformation in the valley of Aosta. [15] Pencils are made of graphite worked up into a homogeneous mass by disintegrating, powdering, and cleansing it from earthy impurities; the best kinds are made of completely homogeneous graphite sawn up into the requisite sticks. Graphite is found in many places. In Russia the so-called Aliberoffsky graphite is particularly renowned; it is found in the Altai mountains near the Chinese frontier; in many places in Finland and likewise on the banks of the Little Tungouska, Sidoroff also found a considerable quantity of graphite. When mixed with clay, graphite is used for making crucibles and pots for melting metals. Graphite, like most forms of charcoal, still contains a certain quantity of hydrogen, oxygen, and ash, so that in its natural state it does not contain more than 98 _p.c._ of carbon. In practice, graphite is purified simply by washing it when in a finely-ground state, by which means the bulk of the earthy matter may be separated. The following process, proposed by Brodie, consists in mixing the powdered graphite with 1/14 part of its weight of potassium chlorate. The mixture is then heated with twice its weight of strong sulphuric acid until no more odoriferous gases are emitted; on cooling, the mixture is thrown into water and washed; the graphite is then dried and heated to a red heat; after this it shrinks considerably in volume and forms a very fine powder, which is then washed. By acting on graphite several times with a mixture of potassium chlorate and nitric acid heated up to 60°, Brodie transformed it into a yellow insoluble acid substance which he called graphitic acid, C_{11}H_{4}O_{5}. The diamond remains unchanged when subjected to this treatment, whilst amorphous charcoal is completely oxidised. Availing himself of this possibility of distinguishing graphite from the diamond or amorphous charcoal, Berthelot showed that when compounds of carbon and hydrogen are decomposed by heat, amorphous charcoal is mainly formed, whilst when compounds of carbon with chlorine, sulphur, and boron are decomposed, graphite is principally deposited. The diamond is a crystalline and transparent form of carbon. It is of rare occurrence in nature, and is found in the alluvial deposits of the diamond mines of Brazil, India, South Africa, &c. It has also been found in meteorites.[15 bis] It crystallises in octahedra, dodecahedra, cubes, and other forms of the regular system.[16] The efforts which have been made to produce diamonds artificially, although they have not been fruitless, have not as yet led to the production of large-sized crystals, because those means by which crystals are generally formed are inapplicable to carbon. Indeed, carbon in all its forms being insoluble and infusible does not pass into a liquid condition by means of which crystallisation could take place. Diamonds have several times been successfully produced in the shape of minute crystals having the appearance of a black powder, but when viewed under the microscope appearing transparent, and possessing that hardness which is the peculiar characteristic of the diamond. This diamond powder is deposited on the negative electrode, when a weak galvanic current is passed through liquid chloride of carbon.[16 bis] [15 bis] Diamonds are found in a particular dense rock, known by the name of itacolumite, and are dug out of the _débris_ produced by the destruction of the itacolumite by water. When the _débris_ is washed the diamonds remain behind; they are principally found in Brazil, in the provinces of Rio and Bahia, and at the Cape of Good Hope. The _débris_ gives the black or amorphous diamond, carbonado, and the ordinary colourless or yellow translucent diamond. As the diamond possesses a very marked cleavage, the first operation consists in splitting it, and then roughly and finely polishing it with diamond powder. It is very remarkable that Professors P. A. Latchinoff and Eroféeff found (1887) diamond powder in a meteoric stone which fell in the Government of Penza, in the district of Krasnoslobodsk, near the settlement of Novo Urei (Sept. 10, 1886). Up to that time charcoal and graphite (a special variety, cliftonite) had been found in meteorites and the diamond only conjectured to occur therein. The Novo Urei meteorite was composed of siliceous matter and metallic iron (with nickel) like many other meteorites. [16] Diamonds are sometimes found in the shape of small balls, and in that case it is impossible to cut them because directly the surface is ground or broken they fall into minute pieces. Sometimes minute diamond crystals form a dense mass like sugar, and this is generally reduced to diamond powder and used for grinding. Some known varieties of the diamond are almost opaque and of a black colour. Such diamonds are as hard as the ordinary ones, and are used for polishing diamonds and other precious stones, and also for rock boring and tunnelling. [16 bis] Hannay, in 1880, obtained diamonds by heating a mixture of heavy liquid hydrocarbons (paraffin oils) with magnesium in a thick iron tube. This investigation, however, was not repeated. Moissan (Paris, 1893) produced diamonds artificially by means of the high temperature attained in the electrical furnace[17] by dissolving carbon in molten cast iron, and allowing the solution with an excess of carbon, to cool under the powerful pressure exerted by rapidly cooling the metal.[17 bis] K. Chroustchoff attained the same end by means of silver, which dissolves carbon to the extent of 6 p.c. at a high temperature. Rousseau, for the same purpose, heated carbide of calcium in the electric furnace. There is no doubt that all these investigators obtained the diamond as a transparent body, which burnt into CO_{2}, and possessed an exceptional hardness, but only in the form of a fine powder. [17] The _electrical furnace_ is an invention of recent times, and gives the possibility of obtaining a temperature of 3,500°, which is not only not obtainable in ordinary furnaces, but even in the oxyhydrogen flame, whose temperature does not exceed 2,000°. The electrical furnace consists of two pieces of lime, laid one on the other. A cavity is made in the lower piece for the reception of the substance to be melted between two thick electrodes of dense carbon. On passing a current of 70 volts and 450 ampères a temperature of 3,000° is easily obtained. At a temperature of 2,500° (100 ampères and 40 volts) not only do all metals melt, but even lime and magnesia (when placed in the space between the carbon electrodes, _i.e._ in the voltaic arc) become soft and crystallise on cooling. At 3,000° lime becomes very fluid, metallic calcium partially separates out and a carbon compound, which remains liquid for a long time. At this temperature oxide of uranium is reduced to the suboxide and metal, zirconia and rock crystal fuse and partially volatilise, as also does alumina; platinum, gold, and even carbon distinctly volatilise; the majority of the metals form carbides. At such a temperature also cast iron and carbon give graphite, while according to Rousseau, between 2,000° and 3,000° the diamond passes into graphite and conversely graphite into the diamond, so that this is a kind of reversible reaction. [17 bis] Moissan first investigated the solution of carbon in molten metals (and the formation of the carbides) such as magnesium, aluminium, iron, manganese, chromium, uranium, silver, platinum, and silicon. At the same time Friedel, owing to the discovery of the diamond in meteoric iron, admitted that the formation of the diamond is dependent upon the influence of iron and sulphur. With this object, that is to obtain the diamond, Friedel caused sulphur to react upon samples of cast iron rich in carbon, in a closed vessel at a maximum temperature of 500°, and after dissolving the sulphide of iron formed, he obtained a small quantity of a black powder which scratched corundum, i.e. diamond. Moissan's experiments (1893) were more successful, probably owing to his having employed the electrical furnace. If iron be saturated with carbon at a temperature between 1,100° and 3,000°, then at 1,100°-1,200° a mixture of amorphous carbon and graphite is formed, while at 3,000° graphite alone is obtained in very beautiful crystals. Thus under these conditions the diamond is not formed, and it can only be obtained if the high temperature be aided by powerful pressures. For this purpose Moissan took advantage of the pressure produced in the passage of a mass of molten cast iron from a liquid into a solid state. He first melted 150-200 grams of iron in the electrical furnace, and quickly introduced a cylinder of carbon into the molten iron. He then removed the crucible with the molten iron from the furnace and plunged it into a reservoir containing water. After treating with boiling hydrochloric acid, three varieties of carbon were obtained: (1) a small amount of graphite (if the cooling be rapid); (2) carbon of a chestnut colour in very fine twisted threads, showing that it had been subjected to a very high pressure (a similar variety was met with in various samples of the Canon Diabolo), and lastly (3) an inconsiderable quantity of an exceeding dense mass which was freed from the admixture of the lighter modifications by treatment with _aqua regia_, sulphuric and hydrofluoric acids, and from which Moissan, by means of liquid bromoform (sp. gr. 2·900), succeeded in separating some small pieces, having a greater density than bromoform, which scratched the ruby and had the properties of the diamond. Some of these pieces were black, others were transparent and refracted light strongly. The dark grey tint of the former resembled that of the black diamonds (carbonado). Their density was between 3 and 3·5. The transparent specimens had a greasy appearance and seemed to be, as it were, surrounded by an envelope of carbon. At 1,050° they did not burn entirely in a current of air, so that the imperfectly burnt particles, and a peculiar form of grains of a light ochre colour, which retained their crystalline form, could be examined under the microscope. Similar grains also remain after the imperfect combustion of the ordinary diamond. Moissan obtained the same results by rapidly cooling in a stream of coal gas a piece of cast iron, saturated with carbon obtained from sugar and first heated to 2,000°. In this instance he obtained small crystals of diamonds. K. Chroustchoff showed that at its boiling point silver dissolves 6 p.c. of carbon. This silver was rapidly cooled, so that a crust formed on the surface and prevented the metal expanding, and so produced a powerful pressure. A portion of the carbon which separates out under these conditions exhibits the properties of the diamond. Judging from the fact that carbon forms a number of gaseous bodies (carbonic oxide, carbonic anhydride, methane, ethylene, acetylene, &c.) and volatile substances (for example, many hydrocarbons and their most simple derivatives), and considering that the atomic weight of carbon, C = 12, approaches that of nitrogen, N = 14, and that of oxygen, O = 16, and that the compounds CO (carbonic oxide) and N_{2}C_{2} (cyanogen) are gases, it may be argued that if carbon formed the molecule C_{2}, like N_{2} and O_{2}, it would be a gas. And as through polymerism or the combination of like molecules (as O_{2} passes into O_{3} or NO_{2} into N_{2}O_{4}) the temperatures of ebullition and fusion rise (which is particularly clearly proved with the hydrocarbons of the C_{n}H_{2n} series), it ought to be considered that _the molecules of charcoal, graphite, and the diamond are very complex_, seeing that they are insoluble, non-volatile, and infusible. The aptitude which the atoms of carbon show for combining together and forming complex molecules appears in all carbon compounds. Among the volatile compounds of carbon many are well known the molecules of which contain C_{5} ... C_{10} ... C_{20} ... C_{30}, &c., in general C_{n} where n may be very large, and in none of the other elements is this faculty of complexity so developed as in carbon.[18] Up to the present time there are no grounds for determining the degree of polymerism of the charcoal, graphite, or diamond molecules, and it can only be supposed that they contain C_{n} where n is a large quantity. Charcoal and those complex non-volatile organic substances which represent the gradual transitions to charcoal[19] and form the principal solid substances of organisms, contain a store or accumulation of internal power in the form of the energy binding the atoms into complex molecules. When charcoal or complex compounds of carbon burn, the energy of the carbon and oxygen is turned into heat, and this fact is taken advantage of at every turn for the generation of heat from fuel.[20] [18] The existence of a molecule S_{6} is known (up to 600°), and it must he beld that this accounts for the formation of hydrogen persulphide, H_{2}S_{5}. Phosphorus appears in the molecule P_{4} and gives P_{4}H_{2}. When expounding the data on specific heat we shall have occasion to return to the question of the complexity of the carbon molecule. [19] The hydrocarbons poor in hydrogen and containing many atoms of carbon, like chrysene and carbopetrocene, &c., C_{_n_}H_{2(_n_-_m_)}, are solids, and less fusible as _n_ and _m_ increase. They present a marked approach to the properties of the diamond. And in proportion to the diminution of the water in the carbohydrates C_{_n_}H_{2_m_}O_{_m_}--for example in the humic compounds (Note 5)--the transition of complex organic substances to charcoal is very evident. That residue resembling charcoal and graphite which is obtained by the separation (by means of copper sulphate and sodium chloride) of iron from white cast-iron containing carbon chemically combined with the iron, also seems, especially after the researches of G. A. Zaboudsky, to be a complex substance containing C_{12}H_{6}O_{3}. The endeavours which have been directed towards determining the measure of complexity of the molecules of charcoal, graphite, and the diamond will probably at some period lead to the solution of this problem and will most likely prove that the various forms of charcoal, graphite, and the diamond contain molecules of different and very considerable complexity. The constancy of the grouping of benzene, C_{6}H_{6}, and the wide diffusion and facility of formation of the carbohydrates containing C_{6} (for example, cellulose, C_{6}H_{10}O_{5}, glucose, C_{6}H_{12}O_{6}) give reason for thinking that the group C_{6} is the first and simplest of those possible to free carbon, and it may be hoped that some time or other it may be possible to get carbon in this form. Perhaps in the diamond there may be found such a relation between the atoms as in the benzene group, and in charcoal such as in carbohydrates. [20] When charcoal burns, the complex molecule C_{_n_} is resolved into the simple molecules _n_CO_{2}, and therefore part of the heat--probably no small amount--is expended in the destruction of the complex molecule C_{_n_}. Perhaps by burning the most complex substances, which are the poorest as regards hydrogen, it may be possible to form an idea of the work required to split up C_{_n_} into separate atoms. No other two elements are capable of combining together in such variety as carbon and hydrogen. The hydrocarbons of the C_{_n_}H_{2_m_} series in many cases differ widely from each other, although they have some properties in common. All hydrocarbons, whether gaseous, liquid or solid, are combustible substances sparingly soluble or insoluble in water. The liquefied gaseous hydrocarbons, as well as those which are liquid at ordinary temperatures, and those solid hydrocarbons which have been liquefied by fusion, have the appearance and property of oily liquors, more or less viscid, or fluid.[21] The solid hydrocarbons more or less resemble wax in their properties, although ordinary oils and wax generally contain oxygen in addition to carbon and hydrogen, but in relatively small proportion. There are also many hydrocarbons which have the appearance of tar--as, for instance, metacinnamene and gutta-percha. Those liquid hydrocarbons which boil at a high temperature are like oils, and those which have a low boiling point resemble ether, whilst the gaseous hydrocarbons in many of their properties are akin to hydrogen. All this tends to show that in hydrocarbons physically considered the properties of solid non-volatile charcoal are strongly modified and hidden, whilst those of the hydrogen predominate. All hydrocarbons are neutral substances (neither basic nor acid), but under certain conditions they enter into peculiar reactions. It has been seen in those hydrogen compounds which have been already considered (water, nitric acid, ammonia) that the hydrogen in almost all cases enters into reaction, being displaced by metals. The hydrogen of the hydrocarbons, it may be said, has no metallic character that is to say, it is not directly[22] displaced by metals, even by such as sodium and potassium. On the application of more or less heat all hydrocarbons decompose[23] forming charcoal and hydrogen. The majority of hydrocarbons do not combine with the oxygen of the air or oxidise at ordinary temperatures, but under the action of nitric acid and many other oxidising substances most of them undergo oxidation, in which either a portion of the hydrogen and carbon is separated, or the oxygen enters into combination, or else the elements of hydrogen peroxide enter into combination with the hydrocarbon.[24] When heated in air, hydrocarbons burn, and, according to the amount of carbon they contain, their combustion is attended more or less with a separation of soot--that is, finely divided charcoal--which imparts great brilliancy to the flame, and on this account many of them are used for the purposes of illumination--as, for instance, kerosene, coal gas, oil of turpentine. As hydrocarbons contain reducing elements (that is, those capable of combining with oxygen), they often act as reducing agents--as, for instance, when heated with oxide of copper, they burn, forming carbonic anhydride and water, and leave metallic copper. Gerhardt proved that all hydrocarbons contain an even number of hydrogen atoms. Therefore, the general formula for all hydrocarbons is C_{_n_}H_{2_m_} where _n_ and _m_ are whole numbers. This fact is known as _the law of even numbers_. Hence, the simplest possible hydrocarbons ought to be: CH_{2}, CH_{4}, CH_{6} ... C_{2}H_{2}, C_{2}H_{4}, C_{2}H_{6}, C_{2}H_{8} ... but they do not all exist, since the quantity of H which can combine with a certain amount of carbon is limited, as we shall learn directly. [21] The viscosity, or degree of mobility, of liquids is determined by their internal friction. It is estimated by passing the liquids through narrow (capillary) tubes, the mobile liquids passing through with greater facility and speed than the viscid ones. The viscosity varies with the temperature and nature of the liquids, and in the case of solutions changes with the amount of the substance dissolved, but is not proportional to it. So that, for example, with alcohol at 20° the viscosity will be 69, and for a 50 p.c. solution 160, the viscosity of water being taken as 100. The volume of the liquid which passes through by experiment (Poiseuille) and theory (Stokes) is proportional to the time, the pressure, and the fourth power of the diameter of the (capillary) tube, and inversely proportional to the length of the tube; this renders it possible to form comparative estimates of the coefficients of internal friction and viscosity. As the complexity of the molecules of hydrocarbons and their derivatives increases by the addition of carbon (or CH_{2}), so does the degree of viscosity also rise. The extensive series of investigations referring to this subject still await the necessary generalisation. That connection which (already partly observed) ought to exist between the viscosity and the other physical and chemical properties, forces us to conclude that the magnitude of internal friction plays an important part in molecular mechanics. In investigating organic compounds and solutions, similar researches ought to stand foremost. Many observations have already been made, but not much has yet been done with them; the bare facts and some mechanical data exist, but their relation to molecular mechanics has not been cleared up in the requisite degree. It has already been seen from existing data that the viscosity at the temperature of the absolute boiling point becomes as small as in gases. [22] In a number of hydrocarbons and their derivatives such a substitution of metals for the hydrogen may be attained by indirect means. The property shown by acetylene, C_{2}H_{2}, and its analogues, of forming metallic derivatives is in this respect particularly characteristic. Judging from the fact that carbon is an acid element (that is, gives an acid anhydride with oxygen), though comparatively slightly acid (for carbonic acid is not at all a strong acid and compounds of chlorine and carbon, even CCl_{4}, are not decomposed by water as is the case with phosphorus chloride and even silicic chloride and boric chloride, although they correspond with acids of but little energy), one might expect to find in the hydrogen of hydrocarbons this faculty for being substituted by metals. The metallic compounds which correspond with hydrocarbons are known under the name of organo-metallic compounds. Such, for instance, is zinc ethyl, Zn(C_{2}H_{5})_{2}, which corresponds with ethyl hydride or ethane, C_{2}H_{6}, in which two atoms of hydrogen have been exchanged for one of zinc. [23] Gaseous and volatile hydrocarbons decompose when passed through a heated tube. When hydrocarbons are decomposed by heating, the primary products are generally other more stable hydrocarbons, among which are acetylene, C_{2}H_{2}, benzene, C_{6}H_{6}, naphthalene, C_{10}H_{8}, &c. [24] Wagner (1888) showed that when unsaturated hydrocarbons are shaken with a weak (1 p.c.) solution of potassium permanganate, KMnO_{4}, at ordinary temperatures, they form glycols--for example, C_{2}H_{4} yields C_{2}H_{6}O_{2}. Some of the hydrocarbons are capable of combination, whilst others do not show that power. Those which contain less hydrogen belong to the former category, and those which, for a given quantity of carbon, contain the maximum amount of hydrogen, belong to the latter. The composition of those last mentioned is expressed by the general formula C_{_n_}H_{2_n_ + 2}. These so-called _saturated hydrocarbons_ are incapable of combination.[25] The hydrocarbons CH_{6}, C_{2}H_{8}, C_{3}H_{10}, &c.... do not exist. Those containing the maximum amount of hydrogen will be represented by CH_{4} (_n_ = 1, 2_n_ + 2 = 4), C_{2}H_{6} (_n_ = 2), C_{3}H_{8} (n = 3), C_{4}H_{10}, &c. This may be termed the _law of limits_. Placing this in juxtaposition with the law of even numbers, it is easy to perceive that the possible hydrocarbons can be ranged in series, the terms of which may be expressed by the general formulæ C_{_n_}H_{2_n_+2}, C_{_n_}H_{2_n_}, C_{_n_}H_{2_n_-2}, &c.... Those hydrocarbons which belong to any one of the series expressible by a general formula are said to be _homologous_0 with one another. Thus, the hydrocarbons CH_{4}, C_{2}H_{6}, C_{3}H_{8}, C_{4}H_{10}, &c.... are members of the limiting (saturated) homologous series C_{_n_}H_{2_n_+2}. That is, the difference between the members of the series is CH_{2}.[26] Not only the composition but also the properties of the members of a series tend to classification in one group. For instance, the members of the series C_{_n_}H_{2_n_+2} are not capable of forming additive compounds, whilst those of the series C_{_n_}H_{2_n_} are capable of combining with chlorine, sulphuric anhydride, &c.; and the members of the C_{_n_}H_{2_n_-6} group, belonging to the coal tar series, are easily nitrated (give nitro-compounds, Chapter VI.), and have other properties in common. The physical properties of the members of a given homologous series vary in some such manner as this; the boiling point generally rises and the internal friction increases as _n_ increases[27]--that is, with an increase in the relative amount of carbon and the atomic weight; the specific gravity also regularly changes as _n_ becomes greater.[28] [25] My article on this subject appeared in the Journal of the St. Petersburg Academy of Sciences in 1861. Up to that time, although many additive combinations with hydrocarbons and their derivatives were known, they had not been generalised, and were even continually quoted as cases of substitution. Thus the combination of ethylene, C_{2}H_{4}, with chlorine, Cl_{2}, was often regarded as a formation of the products of the substitution of C_{2}H_{5}Cl and HCl, which it was supposed were held together as the water of crystallisation is in salts. Even earlier than this (1857, _Journal of the Petroffsky Academy_) I considered similar cases as true compounds. In general, according to the law of limits, an unsaturated hydrocarbon, or its derivative, on combining with _r_X_{2}, gives a substance which is saturated or else approaching the limit. The investigations of Frankland with many organo-metallic compounds clearly showed the limit in the case of metallic compounds, which we shall constantly refer to later on. [26] The conception of homology has been applied by Gerhardt to all organic compounds in his classical work, 'Traité de Chimie Organique,' finished in 1855 (4 vols.), in which he divided all organic compounds into _fatty_ and _aromatic_, which is in principle still adhered to at the present time, although the latter are more often called benzene derivatives, on account of the fact that Kekulé, in his beautiful investigations on the structure of aromatic compounds, showed the presence in them all of the 'benzene nucleus,' C_{6}H_{6}. [27] This is always true for hydrocarbons, but for derivatives of the lower homologues the law is sometimes different; for instance, in the series of saturated alcohols, C_{_n_}H_{2_n_+1}(OH), when _n_ = 0, we obtain water, H(OH), which boils at 100°, and whose specific gravity at 15° = 0·9992; when _n_ = 1, wood spirit CH_{3}(OH), which boils at 66°, and at 15° has a specific gravity = 0·7964; when _n_ = 2, ordinary alcohol, C_{2}H_{5}(OH), boiling at 78°, specific gravity at 15° = 0·7936, and with further increase of CH_{2} the specific gravity increases. For the glycols C_{_n_}H_{2_n_}(OH)_{2} the phenomenon of a similar kind is still more striking; at first the temperature of the boiling point and the density increase, and then for higher (more complex) members of the series diminish. The reason for this phenomenon, it is evident, must be sought for in the influence and properties of water, and that strong affinity which, acting between hydrogen and oxygen, determines many of the exceptional properties of water (Chapter I.). [28] As, for example, in the saturated series of hydrocarbons C_{_n_}H_{2_n_+2}, the lowest member (_n_ = 0) must be taken as hydrogen H_{2}, a gas which (_t.c._ below -190°) is liquefied with great difficulty, and when in a liquid state has doubtless a very small density. Where _n_ = 1, 2, 3, the hydrocarbons CH_{4}, C_{2}H_{6}, C_{3}H_{8} are gases, more and more readily liquefiable. The temperature of the absolute boiling point for CH_{4} =-100°, and for ethane C_{2}H_{6}, and in the higher members it rises. The hydrocarbon C_{4}H_{10}, liquefies at about 0°. C_{5}H_{12} (there are several isomers) boils at from +9° (Lvoff) to 37°, C_{6}H_{14} from 58° to 78°, &c. The specific gravities in a liquid state at 15° are:-- C_{5}H_{12} C_{6}H_{14} C_{7}H_{16} C_{10}H_{22} C_{16}H_{34} 0·63 0·66 0·70 0·75 0·85 Many of the hydrocarbons met with in nature are the products of organisms, and do not belong to the mineral kingdom. A still greater number are produced artificially. These are formed by what is termed the combination of residues. For instance, if a mixture of the vapours of hydrogen sulphide and carbon bisulphide be passed through a tube in which copper is heated, this latter absorbs the sulphur from both the compounds, and the liberated carbon and hydrogen combine to form a hydrocarbon, methane. If carbon be combined with any metal and this compound MC_{_n_} be treated with an acid HX, then the haloid X will give a salt with the metal and the residual carbon and hydrogen will give a hydrocarbon. Thus cast iron which contains a compound of iron and carbon gives liquid hydrocarbons like naphtha under the action of acids. If a mixture of bromo-benzene, C_{6}H_{5}Br, and ethyl bromide, C_{2}H_{5}Br, be heated with metallic sodium, the sodium combines with the bromine of both compounds, forming sodium bromide, NaBr. From the first combination the group C_{6}H_{5} remains, and from the second C_{2}H_{5}. Having an odd number of hydrogen atoms, they, in virtue of the law of even numbers, cannot exist alone, and therefore combine together forming the compound C_{6}H_{5}.C_{2}H_{5} or C_{8}H_{10} (ethylbenzene). Hydrocarbons are also produced by the breaking up of more complex organic or hydrocarbon compounds, especially by heating--that is, by dry distillation. For instance, gum-benzoin contains an acid called benzoic acid, C_{7}H_{6}O_{2}, the vapours of which, when passed through a heated tube, split up into carbonic anhydride, CO_{2}, and benzene, C_{6}H_{6}. Carbon and hydrogen only unite directly in one ratio of combination--namely, to form acetylene, having the composition C_{2}H_{2}, which, as compared with other hydrocarbons, exhibits a very great stability at a somewhat high temperature.[29] [29] If, at the ordinary temperature (assuming therefore that the water formed will be in a liquid state) a gram molecule (26 grams) of acetylene, C_{2}H_{2}, be burnt, 310 thousand calories will be emitted (Thomsen), and as 12 grams of charcoal produce 97 thousand calories, and 2 grams of hydrogen 69 thousand calories, it follows that, if the hydrogen and carbon of the acetylene were burnt there would be only 2 × 97 + 69, or 263 thousand calories produced. It is evident, then, that acetylene in its formation absorbs 310-263, or 47 thousand calories. For considerations relative to the combustion of carbon compounds, we will first enumerate the quantity of heat separated by the combustion of definite chemical carbon compounds, and then give a few figures bearing on the kinds of fuel used in practice. For molecular quantities in perfect combustion the following amounts of heat are given out (when gaseous carbonic anhydride and liquid water are formed), according to Thomsen's data (1) for gaseous C_{_n_}H_{2_n_ + 2}: 52·8 + 158·8_n_ thousand calories; (2) for C_{_n_}H_{2_n_}: 17·7 + 158·1_n_ thousand calories; (3) according to Stohmann (1888) for liquid saturated alcohols, C_{_n_}H_{2_n_ + 2}O: 11·8 + 156·3_n_, and as the latent heat of evaporation = about 8·2 + 0·6_n_, in a gaseous state, 20·0 + 156·9_n_; (4) for monobasic saturated liquid acids, C_{_n_}H_{2_n_}O_{2}:--95·3 + 154·3_n_, and as their latent heat of evaporation is about 5·0 + 1·2_n_, in a gaseous form, about--90 + 155_n_; (5) for solid saturated bibasic acids, C_{_n_}H_{2_n_-2}O_{4}:--253·8 + 152·6_n_, if they are expressed as C_{_n_}H_{2_n_}C_{2}H_{2}O_{4}, then 51·4 + 152·6_n_; (6) for benzene and its liquid homologues (still according to Stohmann) C_{_n_}H_{2_n_-6}:--158·6 + 156·3_n_, and in a gaseous form about--155 + 157_n_; (7) for the gaseous homologues of acetylene, C_{_n_}H_{2_n_-2} (according to Thomsen)--5 + 157_n_. It is evident from the preceding figures that the group CH_{2}, or CH_{3} substituted for H, on burning gives out from 152 to 159 thousand calories. This is less than that given out by C + H_{2}, which is 97 + 69 or 166 thousand; the reason for this difference (it would be still greater if carbon were gaseous) is the amount of heat separated during the formation of CH_{2}. According to Stohmann, for dextroglucose, C_{6}H_{12}O_{6}, it is 673·7; for common sugar, C_{12}H_{22}O_{11}, 1325·7; for cellulose, C_{6}H_{10}O_{5}, 678·0; starch, 677·5; dextrin, 666·2; glycol, C_{2}H_{6}O_{2}, 281·7; glycerine, 397·2, &c. The heat of combustion of the following solids (determined by Stohmann) is expressed per unit of weight: naphthalene, C_{10}H_{8}, 9,621; urea, CN_{2}H_{4}O, 2,465; white of egg, 5,579; dry rye bread, 4,421; wheaten bread, 4,302; tallow, 9,365; butter, 9,192; linseed oil, 9,323. The most complete collection of arithmetical data for the heats of combustion will be found in V. F. Longinin's work, 'Description of the Various Methods of Determining the Heats of Combustion of Organic Compounds' (Moscow, 1894). The number of units of heat given out by _unit weight_ during the complete combustion and cooling of the following ordinary kinds of fuel in their usual state of dryness and purity are:--(1) for wood charcoal, anthracite, semi-anthracite, bituminous coal and coke, from 7,200 to 8,200; (2) dry, long flaming coals, and the best brown coals, from 6,200 to 6,800; (3) perfectly dry wood, 3,500; hardly dry, 2,500; (4) perfectly dry peat, best kind, 4,500; compressed and dried, 3,000; (5) petroleum refuse and similar liquid hydrocarbons, about 11,000; (6) illuminating gas of the ordinary composition (about 45 vols. H, 40 vols. CH_{4}, 5 vols. CO, and 5 vols. N), about 12,000; (7) producer gas (_see_ next Chapter), containing 2 vols. carbonic anhydride, 30 vols. carbonic oxide, and 68 vols. nitrogen _for one part by weight of the whole carbon burnt_, 5,300, and for one part by weight of the gas, 910, units of heat; and (8) water gas (_see_ next chapter) containing 4 vols. carbonic anhydride, 8 vols. N_{2}, 24 vols. carbonic oxide, and 46 vols. H_{2}, for one part by weight of the carbon consumed in the _generator_ 10,900, and for one part by weight of the gas, 3,600 units of heat. In these figures, as in all calorimetric observations, the water produced by the combustion of the fuel is supposed to be liquid. As regards the temperature reached by the fuel, it is important to remark that for solid fuel it is indispensable to admit (to ensure complete combustion) twice the amount of air required, but liquid, or pulverised fuel, and especially gaseous fuel, does not require an excess of air; therefore, a kilogram of charcoal, giving 8,000 units of heat, requires about 24 kilograms of air (3 kilograms of air per thousand calories) and a kilogram of producer gas requires only 0·77 kilogram of air (0·85 kilo. of air per 1,000 calories), 1 kilogram of water gas about 4·5 of air (1·25 kilo. of air per 1,000 calories). There is one substance known among the saturated hydrocarbons composed of 1 atom of carbon and 4 atoms of hydrogen; this is a compound containing the highest percentage of hydrogen (CH_{4} contains 25 per cent. of hydrogen), and at the same time it is the only hydrocarbon whose molecule contains but a single atom of carbon. This saturated hydrocarbon, CH_{4}, is called _marsh gas_ or _methane_. If vegetable or animal refuse suffers decomposition in a space where the air has not free access, or no access at all, then the decomposition is accompanied with the formation of marsh gas, and this either at the ordinary temperature, or at a comparatively much higher one. On this account _plants_, when decomposing under water in _marshes_, give out this gas.[29 bis] It is well known that if the mud in bogs be stirred up, the act is accompanied with the evolution of a large quantity of gas bubbles; these may, although slowly, also separate of their own accord. The gas which is evolved consists principally of marsh gas.[30] If wood, coal, or many other vegetable or animal substances are decomposed by the _action of heat_ without access of air--that is, are subjected to dry distillation--they, in addition to many other gaseous products of decomposition (carbonic anhydride, hydrogen, and various other substances), evolve a great deal of methane. Generally the gas which is used for lighting purposes is obtained by this means and therefore always contains marsh gas, mixed with dry hydrogen and other vapours and gases, although it is subsequently purified from many of them.[31] As the decomposition of the organic matter, which forms coal, is still going on underground, the evolution of large quantities of marsh gas frequently occurs in coal-mines.[32] When mixed with air it forms an explosive mixture, which forms one of the great dangers of coal mining, as subterranean work has always to be carried on by lamp-light. This danger is, however, overcome by the use of Humphry Davy's safety lamp.[33] Sir Humphry Davy observed that on introducing a piece of wire gauze into a flame, it absorbs so much heat that combustion does not proceed beyond it (the unburnt gases which pass through it may be ignited on the other side). In accordance with this, the flame of the Davy lamp is surrounded with a thick glass (as shown in the drawing), and has no communication whatever with the explosive mixture except through a wire gauze which prevents it igniting the mixture of the marsh-gas issuing from the coal with air. In some districts, particularly in those where petroleum is found--as, for instance, near Baku, where a temple of the Indian fire-worshippers was built, and in Pennsylvania, and other places--marsh gas in abundance issues from the earth, and it is used, like coal gas, for the purposes of lighting and warming.[34] Tolerably pure marsh gas[35] may be obtained by heating a mixture of an acetate with an alkali. Acetic acid, C_{2}H_{4}O_{2}, on being heated is decomposed into marsh gas and carbonic anhydride, C_{2}H_{4}O_{2} = CH_{4} + CO_{2}. [29 bis] Manure which decomposes under the action of bacteria gives off CO_{2} and CH_{4}. [30] It is easy to collect the gas which is evolved in marshy places if a glass bottle be inverted in the water and a funnel put into it (both filled with water); if the mud of the bottom be now agitated, the bubbles which rise may be easily caught by the inverted funnel. [31] [Illustration: FIG. 58.--General view of gas works. _B_, retorts; _f_, hydraulic main; _H_ and _I_, tar well; _i_, condensers; _L_, purifiers; _P_, gasholder.] Illuminating gas is generally prepared by heating gas coal (_see_ Note 6) in oval cylindrical horizontal cast-iron or clay retorts. Several such retorts _BB_ (fig. 58) are disposed in the furnace _A_, and heated together. When the retorts are heated to a red heat, lumps of coal are thrown into them, and they are then closed with a closely fitting cover. The illustration shows the furnace, with five retorts. Coke (_see_ Note 1, dry distillation) remains in the retorts, and the volatile products in the form of vapours and gases travel along the pipe _d_, rising from each retort. These pipes branch above the stove, and communicate with the receiver _f_ (hydraulic main) placed above the furnace. Those products of the dry distillation which most easily pass from the gaseous into the liquid and solid states collect in the hydraulic main. From the hydraulic main the vapours and gases travel along the pipe _g_ and the series of vertical pipes _j_ (which are sometimes cooled by water trickling over the surface), where the vapours and gases cool from the contact of the colder surface, and a fresh quantity of vapour condenses. The condensed liquids pass from the pipes _g_ and _j_ and into the troughs _H_. These troughs always contain liquid at a constant level (the excess flowing away) so that the gas cannot escape, and thus they form, as it is termed, a hydraulic joint. In the state in which it leaves the condensers the gas consists principally of the following vapours and gases: (1) vapour of water, (2) ammonium carbonate, (3) liquid hydrocarbons, (4) hydrogen sulphide, H_{2}S, (5) carbonic anhydride, CO_{2}, (6) carbonic oxide, CO, (7) sulphurous anhydride, SO_{2}, but a great part of the illuminating gas consists of (8) hydrogen, (9) marsh gas, (10) olefiant gas, C_{2}H_{4}, and other gaseous hydrocarbons. The hydrocarbons (3, 9, and 10), the hydrogen, and carbonic oxide are capable of combustion, and are useful component parts, but the carbonic anhydride, the hydrogen sulphide, and sulphurous anhydride, as well as the vapours of ammonium carbonate, form an injurious admixture, because they do not burn (CO_{2}, SO_{2}) and lower the temperature and brilliancy of the flame, or else, although capable of burning (for example, H_{2}S, CS_{2}, and others), they give out during combustion sulphurous anhydride which has a disagreeable smell, is injurious when inhaled, and spoils many surrounding objects. In order to separate the injurious products, the gas is washed with water, a cylinder (not shown in the illustration) filled with coke continually moistened with water serving for this purpose. The water coming into contact with the gas dissolves the ammonium carbonate; hydrogen sulphide, carbonic anhydride, and sulphurous anhydride, being only partly soluble in water, have to be got rid of by a special means. For this purpose the gas is passed through moist lime or other alkaline liquid, as the above-mentioned gases have acid properties and are therefore retained by the alkali. In the case of lime, calcium carbonate, sulphite and sulphide, all solid substances, are formed. It is necessary to renew the purifying material as its absorbing power decreases. A mixture of lime and sulphate of iron, FeSO_{4}, acts still better, because the latter, with lime, Ca(HO)_{2}, forms ferrous hydroxide, Fe(HO)_{2} and gypsum, CaSO_{4}. The suboxide (partly turning into oxide) of iron absorbs H_{2}S, forming FeS and H_{2}O, and the gypsum retains the remainder of the ammonia, the excess of lime absorbing carbonic anhydride and sulphuric anhydride. [In English works a native hydrated ferric hydroxide is used for removing hydrogen sulphide.] This purification of the gas takes place in the apparatus _L_, where the gas passes through perforated trays _m_, covered with sawdust mixed with lime and sulphate of iron. It is necessary to remark that in the manufacture of gas it is indispensable to draw off the vapours from the retorts, so that they should not remain there long (otherwise the hydrocarbons would in a considerable degree be resolved into charcoal and hydrogen), and also to avoid a great pressure of gas in the apparatus, otherwise a quantity of gas would escape at all cracks such as must inevitably exist in such a complicated arrangement. For this purpose there are special pumps (exhausters) so regulated that they only pump off the quantity of gas formed (the pump is not shown in the illustration). The purified gas passes through the pipe _n_ into the gasometer (gasholder) _P_, a dome made of iron plate. The edges of the dome dip into water poured into a ring-shaped channel _g_, in which the sides of the dome rise and fall. The gas is collected in this holder, and distributed to its destination by pipes communicating with the pipe _o_, issuing from the dome. The pressure of the dome on the gas enables it, on issuing from a long pipe, to penetrate through the small aperture of the burner. A hundred kilograms of coal give about 20 to 30 cubic metres of gas, having a density from four to nine times greater than that of hydrogen. A cubic metre (1,000 litres) of hydrogen weighs about 87 grams; therefore 100 kilograms of coal give about 18 kilograms of gas, or about one-sixth of its weight. Illuminating gas is generally lighter than marsh gas, as it contains a considerable amount of hydrogen, and is only heavier than marsh gas when it contains much of the heavier hydrocarbons. Thus olefiant gas, C_{2}H_{4}, is fourteen times, and the vapours of benzene thirty-nine times, heavier than hydrogen, and illuminating gas sometimes contains 15 p.c. of its volume of them. The brilliancy of the flame of the gas increases with the quantity of olefiant gas and similar heavy hydrocarbons, as it then contains more carbon for a given volume and a greater number of carbon particles are separated. Gas usually contains from 35 to 60 p.c. of its volume of marsh gas, from 30 to 50 p.c. of hydrogen, from 3 to 5 p.c. of carbonic oxide, from 2 to 10 p.c. heavy hydrocarbons, and from 3 to 10 p.c. of nitrogen. Wood gives almost the same sort of gas as coal and almost the same quantity, but the wood gas contains a great deal of carbonic anhydride, although on the other hand there is an almost complete absence of sulphur compounds. Tar, oils, naphtha, and such materials furnish a large quantity of good illuminating gas. An ordinary burner of 8 to 12 candle-power burns 5 to 6 cubic feet of coal gas per hour, but only 1 cubic foot of naphtha gas. One pood (36 lbs. Eng.) of naphtha gives 500 cubic feet of gas--that is, one kilogram of naphtha produces about one cubic metre of gas. The formation of combustible gas by heating coal was discovered in the beginning of the last century, but only put into practice towards the end by Le-Bon in France and Murdoch in England. In England, Murdoch, together with the renowned Watt, built the first gas works in 1805. [Illustration: FIG. 59.--Blowpipe. Air is blown in at the trumpet-shaped mouthpiece, and escapes in a fine stream from the platinum jet placed at the extremity of the side tube.] [Illustration: FIG. 60.--Davy safety-lamp. [Modern form.]] In practice illuminating gas is not only used for lighting (electricity and kerosene are cheaper in Russia), but also as the motive power for gas engines (_see_ p. 175), which consume about half a cubic metre per horse-power per hour; gas is also used in laboratories for heating purposes. When it is necessary to concentrate the heat, either the ordinary blowpipe (fig. 59) is applied, placing the end in the flame and blowing through the mouthpiece; or, in other forms, gas is passed through the blowpipe; when a large, hot, smokeless flame is required for heating crucibles or glass-blowing, a foot-blower is used. High temperatures, which are often required for laboratory and manufacturing purposes, are most easily attained by the use of gaseous fuel (illuminating gas, producer gas, and water gas, which will be treated of in the following chapter), because complete combustion may be effected without an access of air. It is evident that in order to obtain high temperatures means must be taken to diminish the loss of heat by radiation, and to ensure perfect combustion. [32] The gas which is set free in coal mines contains a good deal of nitrogen, some carbonic anhydride, and a large quantity of marsh gas. The best means of avoiding an explosion consists in efficient ventilation. It is best to light coal mines with electric lamps. [33] The Davy lamp, of which an improved form is represented in the accompanying figure, is used for lighting coal and other mines where combustible gas is found. The wick of the lamp is enclosed in a thick glass cylinder which is firmly held in a metallic holder. Over this a metallic cylinder and the wire gauze are placed. The products of combustion pass through the gauze, and the air enters through the space between the cylinder and the wire gauze. To ensure greater safety the lamp cannot be opened without extinguishing the flame. [34] In Pennsylvania (beyond the Alleghany mountains) many of the shafts sunk for petroleum only emitted gas, but many useful applications for it were found and it was conducted in metallic pipes to works hundreds of miles distant, principally for metallurgical purposes. [35] The purest gas is prepared by mixing the liquid substance called zinc methyl, Zn(CH_{3})_{2}, with water, when the following reaction occurs: Zn(CH_{3})_{2} + 2HOH = Zn(HO)_{2} + 2CH_{3}H. An alkali--for instance, NaHO--gives with acetic acid a salt, C_{2}H_{3}NaO_{2}, which on decomposition retains carbonic anhydride, forming a carbonate, Na_{2}CO_{3}, and marsh gas is given off: C_{2}H_{3}NaO_{2} + NaHO = Na_{2}CO_{3} + CH_{4} Marsh gas is difficult to liquefy; it is almost insoluble in water, and is without taste or smell. The most important point in connection with its chemical reactions is that it does not combine directly with anything, whilst the other hydrocarbons which contain less hydrogen than expressed by the formula C_{_n_}H_{2_n_ + 2} are capable of combining with hydrogen, chlorine, certain acids, &c. If the law of substitution gives a very simple explanation of the formation of hydrogen peroxide as a compound containing two aqueous residues (OH)(OH), then on the basis of this law all hydrocarbons ought to be derived from methane, CH_{4}, as being the simplest hydrocarbon.[36] The increase in complexity of a molecule of methane is brought about by the faculty of mutual combination which exists in the atoms of carbon, and, as a consequence of the most detailed study of the subject, much that might have been foreseen and conjectured from the law of substitution has been actually brought about in such a manner as might have been predicted, and although this subject on account of its magnitude really belongs, as has been already stated, to the sphere of organic chemistry, it has been alluded to here in order to show, although only in part, the best investigated example of the application of the law of substitution. According to this law, a molecule of methane, CH_{4}, is capable of undergoing substitution in the four following ways:--(1) Methyl substitution, when the radicle, equivalent to hydrogen, called _methyl_ CH_{3}, replaces hydrogen. In CH_{4} this radicle is combined with H and therefore can replace it, as (OH) replaces H because with it it gives water; (2) methylene substitution, or the exchange between H_{2} and CH_{2} (this radicle is called methylene), is founded on a similar division of the molecule CH_{4} into two equivalent parts, H_{2} and CH_{2}; (3) acetylene substitution, or the exchange between CH on the one hand and H_{3} on the other; and (4) carbon substitution--that is, the substitution of H_{4} by an atom of carbon C, which is founded on the law of substitution just as is the methyl substitution. These four cases of substitution render it possible to understand the principal relations of the hydrocarbons. For instance, the _law of even numbers_ is seen from the fact that in all the cases of substitution mentioned the hydrogen atoms increase or decrease by an even number; but as in CH_{4} they are likewise even, it follows that no matter how many substitutions are effected there will always be obtained an even number of hydrogen atoms. When H is replaced by CH_{3} there is an increase of CH_{2}; when H_{2} is replaced by CH_{2} there is no increase of hydrogen; in the acetylene substitution CH replaces H_{3}, therefore there is an increase of C and a decrease of H_{2}; in the carbon substitution there is a decrease of H_{4}. In a similar way the _law of limit_ may be deduced as a corollary of the law of substitution. For the largest possible quantity of hydrogen is introduced by the methyl substitution, since it leads to the addition of CH_{2}; starting from CH_{4} we obtain C_{2}H_{6}, C_{3}H_{8}, and in general, C_{_n_}H_{2_n_+2}, and these contain the greatest possible amount of hydrogen. Unsaturated hydrocarbons, containing less hydrogen, are evidently only formed when the increase of the new molecule derived from methane proceeds from one of the other forms of substitution. When the methyl substitution alone takes place in methane, CH_{4}, it is evident that the saturated hydrocarbon formed is C_{2}H_{6} or (CH_{3})(CH_{3}).[37] This is called _ethane_. By means of the methylene substitution alone, _ethylene_, C_{2}H_{4}, or (CH_{2})(CH_{2}) may be directly obtained from CH_{4}, and by the acetylene substitution C_{2}H_{2} or (CH)(CH), or _acetylene_, both the latter being unsaturated hydrocarbons. Thus we have all the possible hydrocarbons with two atoms of carbon in the molecule, C_{2}H_{6}, ethane, C_{2}H_{4}, ethylene, and C_{2}H_{2}, acetylene. But in them, according to the law of substitution, the same forms of substitution may be repeated--that is, the methyl, methylene, acetylene, and even carbon substitutions (because C_{2}H_{6} will still contain hydrogen when C replaces H_{4}) and therefore further substitutions will serve as a source for the production of a fresh series of saturated and unsaturated hydrocarbons, containing more and more carbon in the molecule and, in the case of the acetylene substitution and carbon substitution, containing less and less hydrogen. Thus _by means of the law of substitution we can foresee_ not only the limit C_{_n_}H_{2_n_+2}, but an unlimited number of unsaturated hydrocarbons, C_{_n_}H_{2_n_}, C_{_n_}H_{2_n_-2} ... C_{_n_}H_{2(_n-m_)}, where _m_ varies from 0 to _n_-1,[38] and where _n_ increases indefinitely. From these facts not only does the existence of a multitude of polymeric hydrocarbons, differing in molecular weight, become intelligible, but it is also seen that there is a possibility of cases of isomerism with the same molecular weight. This _polymerism_ so common to hydrocarbon compounds is already apparent in the first unsaturated series C_{_n_}H_{2_n_}, because all the terms of this series C_{2}H_{4}, C_{3}H_{6}, C_{4}H_{8} ... C_{30}H_{60} ... have one and the same composition CH_{2}, but different molecular weights, as has been already explained in Chapter VII. The differences in the vapour density, boiling points, and melting points, of the quantities entering into reactions,[39] and the methods of preparation[40] also so clearly tally with the conception of polymerism, that this example will always be the clearest and most conclusive for the illustration of polymerism and molecular weight. Such a case is also met with among other hydrocarbons. Thus benzene, C_{6}H_{6}, and cinnamene, C_{8}H_{8}, correspond with the composition of acetylene or to a compound of the composition CH.[41] The first boils at 81°, the second at 144°; the specific gravity of the first is 0·899; that of the second, 0·925, at 0°--that is, here also the boiling point rises with the increase of molecular weight, and so also, as might be expected, does the density. [36] Methylene, CH_{2}, does not exist. When attempts are made to obtain it (for example, by removing X_{2} from CH_{2}X_{2}), C_{2}H_{4} or C_{3}H_{6} are produced--that is to say, it undergoes polymerisation. [37] Although the methods of formation and the reactions connected with hydrocarbons are not described in this work, because they are dealt with in organic chemistry, yet in order to clearly show the mechanism of those transformations by which the carbon atoms are built up into the molecules of the carbon compounds, we here give a general example of reactions of this kind. From marsh gas, CH_{4}, on the one hand the substitution of chlorine or iodine, CH_{3}Cl, CH_{3}I, for the hydrogen may be effected, and on the other hand such metals as sodium may be substituted for the hydrogen, _e.g._ CH_{3}Na. These and similar products of substitution serve as a means of obtaining other more complex substances from given carbon compounds. If we place the two above-named products of substitution of marsh gas (metallic and haloid) in mutual contact, the metal combines with the halogen, forming a very stable compound--namely, common salt, NaCl, and the carbon groups which were in combination with them separate in mutual combination, as shown by the equation: CH_{3}Cl + CH_{3}Na = NaCl + C_{2}H_{6}. This is the most simple example of the formation of a complex hydrocarbon from these radicles. The cause of the reaction must be sought for in the property which the haloid (chlorine) and sodium have of entering into mutual combination. [38] When _m_ = _n_-1, we have the series C_{_n_}H_{2}. The lowest member is acetylene, C_{2}H_{2}. These are hydrocarbons containing a minimum amount of hydrogen. [39] For instance, ethylene, C_{2}H_{4}, combines with Br_{2}, HI, H_{2}SO_{4}, as a whole molecule, as also does amylene, C_{5}H_{10}, and, in general, C_{_n_}H_{2_n_}. [40] For instance, ethylene is obtained by removing the water from ethyl alcohol, C_{2}H_{5}(OH), and amylene, C_{5}H_{10}, from amyl alcohol, C_{5}H_{11}(OH), or in general C_{_n_}H_{2_n_}, from C_{_n_}H_{2_n_+1}(OH). [41] Acetylene and its polymerides have an empirical composition CH, ethylene and its homologues (and polymerides) CH_{2}, ethane CH_{3}, methane CH_{4}. This series presents a good example of the law of multiple proportions, but such diverse proportions are met with between the number of atoms of the carbon and hydrogen in the hydrocarbons already known that the accuracy of Dalton's law might be doubted. Thus the substances C_{30}H_{62} and C_{30}H_{60} differ so slightly in their composition by weight as to be within the limits of experimental error, but their reactions and properties are so distinct that they can be distinguished beyond a doubt. Without Dalton's law chemistry could not have been brought to its present condition, but it cannot alone express all those gradations which are quite clearly understood and predicted by the law of Avogadro-Gerhardt. Cases of isomerism in the restricted sense of the word--that is, when with an identity of composition and of molecular weight, the properties of the substances are different--are very numerous among the hydrocarbons and their derivatives. Such cases are particularly important for the comprehension of molecular structure and they also, like the polymerides, may be predicted from the above-mentioned conceptions, expressing the principles of the structure of the carbon compounds[42] based on the law of substitution. According to it, for example, it is evident that there can be no isomerism in the cases of the saturated hydrocarbons C_{2}H_{6} and C_{3}H_{8}, because the former is CH_{4}, in which methyl has taken the place of H, and as all the hydrogen atoms of methane must be supposed to have the same relation to the carbon, it is all the same which of them be subjected to the methyl substitution--the resulting product can only be ethane, CH_{3}CH_{3};[43] the same argument also applies in the case of propane, CH_{3}CH_{2}CH_{3}, where one compound only can be imagined. It is to be expected, however, that there should be two butanes, C_{4}H_{10}, and this is actually the case. In one, methyl may be considered as replacing the hydrogen of one of the methyls, CH_{3}CH_{2}CH_{2}CH_{3}; and in the other CH_{3} may be considered as substituted for H in /CH_{3} CH_{2}, and there it will consist of CH_{3}CH. The latter may \CH_{3} also be regarded as methane in which three of hydrogen are exchanged for three of methyl. On going further in the series it is evident that the number of possible isomerides will be still greater, but we have limited ourselves to the simplest examples, showing the possibility and actual existence of isomerides. C_{2}H_{4} and CH_{2}CH_{2} are, it is evident, identical; but there ought to be, and are, two hydrocarbons of the composition C_{3}H_{6}, propylene and trimethylene; the first is ethylene, CH_{2}CH_{2}, in which one atom of hydrogen is exchanged for methyl, CH_{2}CHCH_{3}, and trimethylene is ethane, CH_{3}CH_{3}, with the substitution of methylene for two hydrogen atoms from two methyl groups--that /CH_{2} is, CH_{2},[44] where the methylene introduced is united to both \CH_{2} the atoms of carbon in CH_{3}CH_{3}. It is evident that the cause of isomerism here is, on the one hand, the difference of the amount of hydrogen in union with the particular atoms of carbon, and, on the other, the different connection between the several atoms of carbon. In the first case they may be said to be chained together (more usually to form an 'open chain'), and in the second case, to be locked together (to form a 'closed chain' or 'ring'). Here also it is easily understood that on increasing the quantity of carbon atoms the number of possible and existing isomerides will greatly increase. If, at the same time, in addition to the substitution of one of the radicles of methane for hydrogen a further exchange of part of the hydrogen for some of the other groups of elements X, Y ... occurs, the quantity of possible isomerides still further increases in a considerable degree. For instance, there are even two possible isomerides for the derivatives of ethane, C_{2}H_{6}: if two atoms of the hydrogen be exchanged for X_{2}, one will have the ethylene structure, CH_{2}XCH_{2}X, and the other an ethylidene structure, CH_{3}CHX_{2}; such are, for instance, ethylene chloride, CH_{2}ClCH_{2}Cl, and ethylidene chloride, CH_{3}CHCl_{2}. And as in the place of the first atom of hydrogen not only metals may be substituted, but Cl, Br, I, OH (the water radicle), NH_{2} (the ammonia radicle), NO_{2} (the radicle of nitric acid), &c., so also in exchange for two atoms of hydrogen O, NH, S, &c., may be substituted; hence it will be understood that the quantity of isomerides is sometimes very great. It is impossible here to describe how the isomerides are distinguished from each other, in what reactions they occur, how and when one changes into another, &c.; for this, taken together with the description of the hydrocarbons already known, and their derivatives, forms a very extensive and very thoroughly investigated branch of chemistry, called _organic chemistry_. Enriched with a mass of closely observed phenomena and strictly deduced generalisations, this branch of chemistry has been treated separately for the reason that in it the hydrocarbon groups are subjected to transformations which are not met with in such quantity in dealing with any of the other elements or their hydrogen compounds. It was important for us to show that notwithstanding the great variety of the hydrocarbons and their products,[45] they are all of them governed by the law of substitution, and referring our readers for detailed information to works on organic chemistry, we will limit ourselves to a short exposition of the properties of the two simplest unsaturated hydrocarbons: ethylene, CH_{2}CH_{2}, and acetylene, CHCH, and a short acquaintance with petroleum as the natural source of a mass of hydrocarbons. _Ethylene, or olefiant gas_, C_{2}H_{4}, is the lowest known member of the unsaturated hydrocarbon series of the composition C_{_n_}H_{2_n_}. As in composition it is equal to two molecules of marsh gas deprived of two molecules of hydrogen, it is evident that it might be, and it actually can be, produced, although but in small quantities, together with hydrogen, by heating marsh gas. On being heated, however, olefiant gas splits up, first into acetylene and methane (3C_{2}H_{4} = 2C_{2}H_{2} + 2CH_{4}, Lewes, 1894), and at a higher temperature into carbon and hydrogen; and therefore in those cases where marsh gas is produced by heating, olefiant gas, hydrogen, and charcoal will also be formed, although only in small quantities. The lower the temperature at which complex organic substances are heated, the greater the quantity of olefiant gas found in the gases given off; at a white heat it is entirely decomposed into charcoal and marsh gas. If coal, wood, and more particularly petroleum, tars, and fatty substances, are subjected to dry distillation, they give off illuminating gas, which contains more or less olefiant gas. [42] The conception of the structure of carbon compounds--that is, the expression of those unions and correlations which their atoms have in the molecules--was for a long time limited to the representation that organic substances contained complex radicles (for instance, ethyl C_{2}H_{5}, methyl CH_{3}, phenyl C_{6}H_{5}, &c.); then about the year 1840 the phenomena of substitution and the correspondence of the products of substitution with the primary bodies (nuclei and types) were observed, but it was not until about the year 1860 and later when on the one hand the teaching of Gerhardt about molecules was spreading, and on the other hand the materials had accumulated for discussing the transformations of the simplest hydrocarbon compounds, that conjectures began to appear as to the mutual connection of the atoms of carbon in the molecules of the complex hydrocarbon compounds. Then Kekulé and A. M. Butleroff began to formulate the connection between the separate atoms of carbon, regarding it as a quadrivalent element. Although in their methods of expression and in some of their views they differ from each other and also from the way in which the subject is treated in this work, yet the essence of the matter--namely, the comprehension of the causes of isomerism and of the union between the separate atoms of carbon--remains the same. In addition to this, starting from the year 1870, there appears a tendency which from year to year increases to discover the actual spacial distribution of the atoms in the molecules. Thanks to the endeavours of Le-Bel (1874), Van't Hoff (1874), and Wislicenus (1887) in observing cases of isomerism--such as the effect of different isomerides on the direction of the rotation of the plane of polarisation of light--this tendency promises much for chemical mechanics, but the details of the still imperfect knowledge in relation to this matter must be sought for in special works devoted to organic chemistry. [43] Direct experiment shows that however CH_{3}X is prepared (where X = for instance Cl, &c.) it is always one and the same substance. If, for example, in CX_{4}, X is gradually replaced by hydrogen until CH_{3}X is produced, or in CH_{4}, the hydrogen by various means is replaced by X, or else, for instance, if CH_{3}X be obtained by the decomposition of more complex compounds, the same product is always obtained. This was shown in the year 1860, or thereabout, by many methods, and is the fundamental conception of the structure of hydrocarbon compounds. If the atoms of hydrogen in methyl were not absolutely identical in value and position (as they are not, for instance, in CH_{3}CH_{2}CH_{3} or CH_{3}CH_{2}X), then there would be as many different forms of CH_{3}X as there were diversities in the atoms of hydrogen in CH_{4}. The scope of this work does not permit of a more detailed account of this matter. It is given in works on organic chemistry. [44] The union of carbon atoms in closed chains or rings was first suggested by Kekulé as an explanation of the structure and isomerism of the derivatives of benzene, C_{6}H_{6}, forming aromatic compounds (Note 26). [45] The following are the most generally known of the oxygenised but non-nitrogenous hydrocarbon derivatives. (1) the alcohols. These are hydrocarbons in which hydrogen is exchanged for hydroxyl (OH). The simplest of these is methyl alcohol, CH_{3}(OH), or wood spirit obtained by the dry distillation of wood. The common spirits of wine or ethyl alcohol, C_{2}H_{3}(OH), and glycol, C_{2}H_{4}(OH)_{2}, correspond with ethane. Normal propyl alcohol, CH_{3}CH_{2}CH_{2}(OH), and isopropyl alcohol, CH_{3}CH(OH)CH_{3}, propylene-glycol, C_{3}H_{6}(OH)_{2}, and glycerol, C_{3}H_{3}(OH)_{3} (which, with stearic and other acids, forms fatty substances), correspond with propane, C_{3}H_{8}. All alcohols are capable of forming water and ethereal salts with acids, just as alkalis form ordinary salts. (2) Aldehydes are alcohols minus hydrogen; for instance, acetaldehyde, C_{2}H_{4}O, corresponds with ethyl alcohol. (3) It is simplest to regard organic acids as hydrocarbons in which hydrogen has been exchanged for carboxyl (CO_{2}H), as will be explained in the following chapter. There are a number of intermediate compounds; for example, the aldehyde-alcohols, alcohol-acids (or hydroxy-acids), &c. Thus the hydroxy-acids are hydrocarbons in which some of the hydrogen has been replaced by hydroxyl, and some by carboxyl; for instance, lactic acid corresponds with C_{2}H_{6}, and has the constitution C_{2}H_{4}(OH)(CO_{2}H). If to these products we add the haloid salts (where H is replaced by Cl, Br, I), the nitro-compounds containing NO_{2} in place of H, the amides, cyanides, ketones, and other compounds, it will be readily seen what an immense number of organic compounds there are and what a variety of properties these substances have; this we see also from the composition of plants and animals. Olefiant gas, almost free from other gases,[46] may be obtained from ordinary alcohol (if possible, free from water) if it be mixed with five parts of strong sulphuric acid and the mixture heated to slightly above 100°. Under these conditions, the sulphuric acid removes the elements of water from the alcohol, C_{2}H_{5}(OH), and gives olefiant gas; C_{2}H_{6}O = H_{2}O + C_{2}H_{4}. The greater molecular weight of olefiant gas compared with marsh gas indicates that it may be comparatively easily converted into a liquid by means of pressure or great cold; this may be effected, for example, by the evaporation of liquid nitrous oxide. Its absolute boiling point is +10°, it boils at -103° (1 atmosphere), liquefies at 0°, at a pressure of 43 atmospheres, and solidifies at -160°. Ethylene is colourless, has a slight ethereal smell, is slightly soluble in water, and somewhat more soluble in alcohol and in ether (in five volumes of spirit and six volumes of ether).[47] [46] Ethylene bromide, C_{2}H_{4}Br_{2}, when gently heated in alcoholic solution with finely divided zinc, yields pure ethylene, the zinc merely taking up the bromine (Sabaneyeff). [47] Ethylene decomposes somewhat easily under the influence of the electric spark, or a high temperature. In this case the volume of the gas formed may remain the same when olefiant gas is decomposed into carbon and marsh gas, or may increase to double its volume when hydrogen and carbon are formed, C_{2}H_{4} = CH_{4} + C = 2C + 2H_{2}. A mixture of olefiant gas and oxygen is highly explosive; two volumes of this gas require six volumes of oxygen for its perfect combustion. The eight volumes thus taken then resolve themselves into eight volumes of the products of combustion, a mixture of water and carbonic anhydride, C_{2}H_{4} + 3O_{2} = 2CO_{2} + 2H_{2}O. On cooling after the explosion diminution of volume occurs because the water becomes liquid. For two volumes of the olefiant gas taken, the diminution will be equal to four volumes, and the same for marsh gas. The quantity of carbonic anhydride formed by both gases is not the same. Two volumes of marsh gas give only two volumes of carbonic anhydride, and two volumes of ethylene give four volumes of carbonic anhydride. Like other unsaturated hydrocarbons, olefiant gas readily enters into combination with certain substances, such as chlorine, bromine, iodine, fuming sulphuric acid, or sulphuric anhydride, &c. If olefiant gas be sealed up with a small quantity of sulphuric acid in a glass vessel, and constantly agitated (as, for instance, by attaching it to the moving part of a machine), the prolonged contact and repeated mixing causes the olefiant gas, little by little, to combine with the sulphuric acid, forming C_{2}H_{4}H_{2}SO_{4}. If, after this absorption, the sulphuric acid be diluted with water and distilled, alcohol separates, which is produced in this case by the olefiant gas combining with the elements of water, C_{2}H_{4} + H_{2}O = C_{2}H_{6}O. In this reaction (Berthelot) we see an excellent example of the fact that if a given substance, like olefiant gas, is produced by the decomposition of another, then in the reverse way this substance, entering into combination, is capable of forming the original substance--in our example, alcohol. In combination with various molecules, X_{2}, ethylene gives saturated compounds, C_{2}H_{4}X_{2} or CH_{2}XCH_{2}X (for example, C_{2}H_{4}Cl_{2}), which correspond with ethane, CH_{3}CH_{3} or C_{2}H_{6}.[48] [48] The homologues of ethylene, C_{_n_}H_{2_n_}, are also capable of direct combination with halogens, &c., but with various degrees of facility. The composition of these homologues can be expressed thus: (CH_{3})__x_(CH_{2})_{_y_}(CH)_{_z_}C_{_r_}, where the sum of _x_ + _z_ is always an even number, and the sum of _x_ + _z_ + _r_ is equal to half the sum of 3_x_ + _z_, whence _z_ + 2_r_ = _x_; by this means the possible isomerides are determined. For example, for butylenes, C_{4}H_{8}, (CH_{3})_{2}(CH)_{2}, (CH_{3})_{2}(CH_{2})C, (CH_{2})(CH_{2})_{2}CH, and (CH_{2})_{4} are possible. _Acetylene_, C_{2}H_{2} = CHCH, is a gas; it was first prepared by Berthelot (1857). It has a very pungent smell, is characterised by its great stability under the action of heat, and is obtained as the only product of the direct combination of carbon with hydrogen when a luminous arc (voltaic) is formed between carbon electrodes. This arc contains particles of carbon passing from one pole to the other. If the carbons be surrounded with an atmosphere of hydrogen, the carbon in part combines with the hydrogen, forming C_{2}H_{2}.[48 bis] Acetylene may be formed from olefiant gas if two atoms of hydrogen be taken from it. This may be effected in the following way: the olefiant gas is first made to combine with bromine, giving C_{2}H_{4}Br_{2}; from this the hydrobromic acid is removed by means of an alcoholic solution of caustic potash, leaving the volatile product C_{2}H_{3}Br; and from this yet another part of hydrobromic acid is withdrawn by passing it through anhydrous alcohol in which metallic sodium has been dissolved, or by heating it with a strong alcoholic solution of caustic potash. Under these circumstances (Berthelot, Sawitsch, Miasnikoff) the alkali takes up the hydrobromic acid from C_{_n_}H_{2_n_-1}Br, forming C_{_n_}H_{2_n_-2}. [48 bis] _See_ also method of preparing C_{2}H_{2} in Note 12 bis. Acetylene is also produced in all those cases where organic substances are decomposed by the action of a high temperature--for example, by dry distillation. On this account a certain quantity is always found in coal gas, and gives to it, at all events in part, its peculiar smell, but the quantity of acetylene in coal gas is very small. If the vapour of alcohol be passed through a heated tube a certain quantity of acetylene is formed. It is also produced by the imperfect combustion of olefiant and marsh gas--for example, if the flame of coal gas has not free access to air.[49] The inner part of every flame contains gases in imperfect combustion, and in them some amount of acetylene. [49] This is easily accomplished with those gas burners which are used in laboratories and mentioned in the Introduction. In these burners the gas is first mixed with air in a long tube, above which it is kindled. But if it be lighted inside the pipe it does not burn completely, but forms acetylene, on account of the cooling effect of the walls of the metallic tube; this is detected by the smell, and may be shown by passing the issuing gas (by aid of an aspirator) into an ammoniacal solution of cuprous chloride. Acetylene, being further removed than ethylene from the limit C_{_n_}H_{2_n_+2} of hydrocarbon compounds, has a still greater faculty of combination than is shown by olefiant gas, and therefore can be more readily separated from any mixture containing it. Actually, acetylene not only combines with one and two molecules of I_{2}, HI, H_{2}SO_{4}, Cl_{2}, Br_{2}, &c.... (many other unsaturated hydrocarbons combine with them), but also with cuprous chloride, CuCl, forming a red precipitate. If a gaseous mixture containing acetylene be passed through an ammoniacal solution of cuprous chloride (or silver nitrate), the other gases do not combine, but the acetylene gives a red precipitate (or grey with silver), which detonates when struck with a hammer. This red precipitate gives off acetylene under the action of acids. In this manner pure acetylene may be obtained. Acetylene and its homologues also readily react with corrosive sublimate, HgCl_{2} (Koucheroff, Favorsky). Acetylene burns with a very brilliant flame, which is accounted for by the comparatively large amount of carbon it contains.[50] [50] Amongst the homologues of acetylene C_{_n_}H_{2_n_-2}, the lowest is C_{3}H_{4}; allylene, CH_{3}CCH, and allene, CH_{2}CCH_{2}, are known, but the closed structure, CH_{2}(CH)_{2}, is little investigated. The formation and existence in nature of large masses of petroleum or a mixture of liquid hydrocarbons, principally of the series C_{_n_}H_{2_n_ +2} and C_{_n_}H_{2_n_} is in many respects remarkable.[51] In some mountainous districts--as, for instance, by the slopes of the Caucasian chain, on inclines lying in a direction parallel to the range--an oily liquid issues from the earth together with salt water and hot gases (methane and others); it has a tarry smell and dark brown colour, and is lighter than water. This liquid is called naphtha or rock oil (petroleum) and is obtained in large quantities by sinking wells and deep bore-holes in those places where traces of naphtha are observed, the naphtha being sometimes thrown up from the wells in fountains of considerable height.[52] The evolution of naphtha is always accompanied by salt water and marsh gas. Naphtha has from ancient times been worked in Russia in the Apsheron peninsula near Baku, and is also now worked in Burmah (India), in Galicia near the Carpathians, and in America, especially in Pennsylvania and Canada, &c. Naphtha does not consist of one definite hydrocarbon, but of a mixture of several, and its density, external appearance, and other qualities vary with the amount of the different hydrocarbons of which it is composed. The light kinds of naphtha have a specific gravity about 0·8 and the heavy kinds up to 0·98. The former are very mobile liquids, and more volatile; the latter contain less of the volatile hydrocarbons and are less mobile. When the light kinds of naphtha are distilled, the boiling point taken in the vapours constantly changes, beginning at 0° and going up to above 350°. That which passes over first is a very mobile, colourless ethereal liquid (forming gazolene, ligroin, benzoline, &c.), from which the hydrocarbons whose boiling points start from 0° may be extracted--namely, the hydrocarbons C_{4}H_{10}, C_{5}H_{12} (which boils at 30°), C_{6}H_{14} (boils at 62°), C_{7}H_{16} (boils about 90°), &c. Those fractions of the naphtha distillate which boil above 130°, and contain hydrocarbons with C_{9}, C_{10}, C_{11}, &c., enter into the composition of the oily substance, universally used for lighting, called kerosene or photogen or photonaphthalene, and by other names. The specific gravity of kerosene is from 0·78 to 0·84, and it smells like naphtha. Those products of the distillation of naphtha which pass off below 130° and have a specific gravity below 0·75, enter into the composition of light petroleum (benzoline, ligroin, petroleum spirit, &c.); which is used as a solvent for india-rubber, for removing grease spots, &c. Those portions of naphtha (which can only be distilled without change by means of superheated steam, otherwise they are largely decomposed) which boil above 275° and up to 300° and have a specific gravity higher than 0·85, form an excellent oil,[53] safe as regards inflammability (which is very important as diminishing the risks of fire), and may be used in lamps as an effective substitute for kerosene.[54] Those portions of naphtha which pass over at a still higher temperature and have a higher specific gravity than 0·9, which are found in abundance (about 30 p.c.) in the Baku naphtha, make excellent lubricating or machine oils. Naphtha has many important applications, and the naphtha industry is now of great commercial importance, especially as naphtha and its refuse may be used as fuel.[55] Whether naphtha was formed from organic matter is very doubtful, as it is found in the most ancient Silurian strata which correspond with epochs of the earth's existence when there was little organic matter; it could not penetrate from the higher to the lower (more ancient) strata as it floats on water (and water penetrates through all strata). It therefore tends to rise to the surface of the earth, and it is always found in highlands parallel to the direction of the mountains.[56] Much more probably its formation may be attributed to the action of water penetrating through the crevasses formed on the mountain slopes and reaching to the heart of the earth, to that kernel of heated metallic matter which must be accepted as existing in the interior of the earth. And as meteoric iron often contains carbon (like cast iron), so, accepting the existence of such carburetted iron at unattainable depths in the interior of the earth, it may be supposed that naphtha was produced by the action of water penetrating through the crevices of the strata during the upheaval of mountain chains,[57] because water with iron carbide ought to give iron oxide and hydrocarbons.[58] Direct experiment proves that the so-called _spiegeleisen_ (manganiferous iron, rich in chemically combined carbon) when treated with acids gives liquid hydrocarbons[59] which in composition, appearance, and properties are completely identical with naphtha.[60] [51] The saturated hydrocarbons predominate in American petroleum, especially in its more volatile parts; in Baku naphtha the hydrocarbons of the composition C_{_n_}H_{2_n_} form the main part (Lisenko, Markovnikoff, Beilstein) but doubtless (Mendeléeff) it also contains saturated ones, C_{_n_}H_{2_n_+2}. The structure of the naphtha hydrocarbons is only known for the lower homologues, but doubtless the distinction between the hydrocarbons of the Pennsylvanian and Baku naphthas, boiling at the same temperature (after the requisite refining by repeated fractional distillation, which can be very conveniently done by means of steam rectification--that is, by passing the steam through the dense mass), depends not only on the predominance of saturated hydrocarbons in the former, and naphthenes, C_{_n_}H_{2_n_}, in the latter, but also on the diversity of composition and structure of the corresponding portions of the distillation. The products of the Baku naphtha are richer in carbon (therefore in a suitably constructed lamp they ought to give a brighter light), they are of greater specific gravity, and have greater internal friction (and are therefore more suitable for lubricating machinery) than the American products collected at the same temperature. [52] The formation of naphtha fountains (which burst forth after the higher clay strata covering the layers of sands impregnated with naphtha have been bored through) is without doubt caused by the pressure or tension of the combustible hydrocarbon gases which accompany the naphtha, and are soluble in it under pressure. Sometimes these naphtha fountains reach a height of 100 metres--for instance, the fountain of 1887 near Baku. Naphtha fountains generally act periodically and their force diminishes with the lapse of time, which might be expected, because the gases which cause the fountains find an outlet, as the naphtha issuing from the bore-hole carries away the sand which was partially choking it up. [53] This is a so-called intermediate oil (between kerosene and lubricating oils), solar oil, or pyronaphtha. Lamps are already being manufactured for burning it but still require improvement. Above all, however, it requires a more extended market, and this at present is wanting, owing to the two following reasons: (1) Those products of the American petroleum which are the most widely spread and almost universally consumed contain but little of this intermediate oil, and what there is is divided between the kerosene and the lubricating oils; (2) the Baku naphtha, which is capable of yielding a great deal (up to 30 p.c.) of intermediate oil, is produced in enormous quantities, about 300 million poods, but has no regular markets abroad, and for the consumption in Russia (about 25 million poods of kerosene per annum) and for the limited export (60 million poods per annum) into Western Europe (by the Trans-Caucasian Railway) those volatile and more dangerous parts of the naphtha which enter into the composition of the American petroleum are sufficient, although Baku naphtha yields about 25 p.c. of such kerosene. For this reason pyronaphtha is not manufactured in sufficient quantities, and the whole world is consuming the unsafe kerosene. When a pipe line has been laid from Baku to the Black Sea (in America there are many which carry the raw naphtha to the sea-shore, where it is made into kerosene and other products) then the whole mass of the Baku naphtha will furnish safe illuminating oils, which without doubt will find an immense application. A mixture of the intermediate oil with kerosene or Baku oil (specific gravity 0·84 to 0·85) may be considered (on removing the benzoline) to be the best illuminating oil, because it is safe (flashing point from 40° to 60°), cheaper (Baku naphtha gives as much as 60 p.c. of Baku oil), and burns perfectly well in lamps differing but little from those made for burning American kerosene (unsafe, flashing point 20° to 30°). [54] The substitution of Baku pyronaphtha, or intermediate oil, or Baku oil (_see_ Note 53), would not only be a great advantage as regards safety from fire, but would also be highly economical. A ton (62 poods) of American crude petroleum costs at the coast considerably more than 24_s._ (12 roubles), and yields two-thirds of a ton of kerosene suitable for ordinary lamps. A ton of raw naphtha in Baku costs less than 4_s._ (1 rouble 80 copecks), and with a pipe line to the shore of the Black Sea would not cost more than 8 roubles, or 16_s._ Moreover, a ton of Baku naphtha will yield as much as two-thirds of a ton of kerosene, Baku oil, and pyronaphtha suitable for illuminating purposes. [55] Naphtha has been applied for heating purposes on a large scale in Russia, not only on account of the low cost of naphtha itself and of the residue from the preparation of kerosene, but also because the products of all the Baku naphtha do not find an outlet for general consumption. Naphtha itself and its various residues form excellent fuel, burning without smoke and giving a high temperature (steel and iron may be easily melted in the flame). A hundred poods of good coal (for instance, Don coal) used as fuel for heating boilers are equivalent to 36 cubic feet (about 250 poods) of dry wood, while only 70 poods of naphtha will be required; and moreover there is no need for stoking, as the liquid can be readily and evenly supplied in the required quantity. The economic and other questions relating to American and Baku petroleums have been discussed more in detail in some separate works of mine (D. Mendeléeff): (1) 'The Naphtha Industry of Pennsylvania and the Caucasus,' 1870; (2) 'Where to Build Naphtha Works,' 1880; (3) 'On the Naphtha Question,' 1883; (4) 'The Baku Naphtha Question,' 1886; (5) the article on the naphtha industry in the account of the Russian industries printed for the Chicago Exhibition. [56] As during the process of the dry distillation of wood, sea-weed, and similar vegetable _débris_, and also when fats are decomposed by the action of heat (in closed vessels), hydrocarbons similar to those of naphtha are formed, it was natural that this fact should have been turned to account to explain the formation of the latter. But the hypothesis of the formation of naphtha from vegetable _débris_ inevitably assumes coal to be the chief element of decomposition, and naphtha is met with in Pennsylvania and Canada, in the Silurian and Devonian strata, which do not contain coal, and correspond to an epoch not abounding in organic matter. Coal was formed from the vegetable _débris_ of the Carboniferous, Jurassic, and other recent strata, but judging more from its composition and structure, it has been subjected to the same kind of decomposition as peat; nor could liquid hydrocarbons have been thus formed to such an extent as we see in naphtha. If we ascribe the derivation of naphtha to the decomposition of fat (adipose, animal fat) we encounter three almost insuperable difficulties: (1) Animal remains would furnish a great deal of nitrogenous matter, whilst there is but very little in naphtha; (2) the enormous quantity of naphtha already discovered as compared with the insignificant amount of fat in the animal carcase; (3) the sources of naphtha always running parallel to mountain chains is completely inexplicable. Being struck with this last-mentioned circumstance in Pennsylvania, and finding that the sources in the Caucasus surround the whole Caucasian range (Baku, Tiflis, Gouria, Kouban, Tamman, Groznoe, Dagestan), I developed in 1876 the hypothesis of the mineral origin of naphtha expounded further on. [57] During the upheaval of mountain ranges crevasses would be formed at the peaks with openings upwards, and at the foot of the mountains with openings downwards. These cracks in course of time fill up, but the younger the mountains the fresher the cracks (the Alleghany mountains are, without doubt, more ancient than the Caucasian, which were formed during the tertiary epoch); through them water must gain access deep into the recesses of the earth to an extent that could not occur on the level (on plains). The situation of naphtha at the foot of mountain chains is the principal argument in my hypothesis. Another fundamental reason is the consideration of the mean density of the earth. Cavendish, Airy, Cornu, Boys, and many others who have investigated the subject by various methods, found that, taking water = 1, the mean density of the earth is nearly 5·5. As at the surface water and all rocks (sand, clay, limestone, granite, &c.) have a density less than 3, it is evident (as solid substances are but slightly compressible even under the greatest pressure) that inside the earth there are substances of a greater density--indeed, not less than 7 or 8. What conclusion, then, can be arrived at? Anything heavy contained in the bosom of the earth must be distributed not only on its surface, but throughout the whole solar system, for everything tends to show that the sun and planets are formed from the same material, and according to the hypothesis of Laplace and Kant it is most probable, and indeed must necessarily be held, that the earth and planets are but fragments of the solar atmosphere, which have had time to cool considerably and become masses semi-liquid inside and solid outside, forming both planets and satellites. The sun amongst other heavy elements contains a great deal of iron, as shown by spectrum analysis. There is also much of it in an oxidised condition on the surface of the earth. Meteoric stones, carried as fragmentary planets in the solar system and sometimes falling upon the earth, consisting of siliceous rocks similar to terrestrial ones, often contain either dense masses of iron (for example, the Pallosovo iron preserved in the St. Petersburg Academy of Sciences) or granular masses (for instance, the Okhansk meteorite of 1886). It is therefore possible that the interior of the earth contains much iron in a metallic state. This might be anticipated from the hypothesis of Laplace, for the iron must have been compressed into a liquid at that period when the other component parts of the earth were still strongly heated, and oxides of iron could not then have been formed. The iron was covered with slags (mixtures of silicates like glass fused with rocky matter) which did not allow it to burn at the expense of the oxygen of the atmosphere or of water, just at that time when the temperature of the earth was very high. Carbon was in the same state; its oxides were also capable of dissociation (Deville); it is also but slightly volatile, and has an affinity for iron, and iron carbide is found in meteoric stones (as well as carbon and even the diamond). Thus the supposition of the existence of iron carbides in the interior of the earth was derived by me from many indications, which are to some extent confirmed by the fact that granular pieces of iron have been found in some basalts (ancient lava) as well as in meteoric stones. The occurrence of iron in contact with carbon during the formation of the earth is all the more probable because those elements predominate in nature which have small atomic weights, and among them the most widely diffused, the most difficultly fusible, and therefore the most easily condensed (Chapter XV.) are carbon and iron. They passed into the liquid state when all compounds were at a temperature of dissociation. [58] The following is the typical equation for this formation: 3Fe_{_m_}C_{_n_} + 4_{_m_}H_{2}O = _m_Fe_{3}O_{4} (magnetic oxide) + C_{5_n_}H_{8_m_} (_see_ Chapter XVII., Note 38). [59] Cloez investigated the hydrocarbons formed when cast-iron is dissolved in hydrochloric acid, and found C_{_n_}H_{2_n_} and others. I treated crystalline manganiferous cast-iron with the same acid, and obtained a liquid mixture of hydrocarbons exactly similar to natural naphtha in taste, smell, and reaction. [60] Probably naphtha was produced during the upheaval of all mountain chains, but only in some cases were the conditions favourable to its being preserved underground. The water penetrating below formed there a mixture of naphtha and watery vapours, and this mixture issued through fissures to the cold parts of the earth's crust. The naphtha vapours, on condensing, formed naphtha, which, if there were no obstacles, appeared on the surface of land and water. Here part of it soaked through formations (possibly the bituminous slates, schists, dolomites, &c., were thus formed), another part was carried away on the water, became oxidised, evaporated, and was driven to the shores (the Caucasian naphtha probably in this way, during the existence of the Aralo-Caspian sea, was carried as far as the Sisran banks of the Volga, where many strata are impregnated with naphtha and products of its oxidation resembling asphalt and pitch); a great part of it was burnt in one way or another--that is, gave carbonic anhydride and water. If the mixture of vapours, water, and naphtha formed inside the earth had no free outlet to the surface, it nevertheless would find its way through fissures to the superior and colder strata, and there become condensed. Some of the formations (clays) which do not absorb naphtha were only washed away by the warm water, and formed mud, which we also now observe issuing from the earth in the form of mud volcanoes. The neighbourhood of Baku and the whole of the Caucasus near the naphtha districts are full of such volcanoes, which from time to time are in a state of eruption. In old naphtha beds (such as the Pennsylvanian) even these blow-holes are closed, and the mud volcanoes have had time to be washed away. The naphtha and the gaseous hydrocarbons formed with it under the pressure of the overlying earth and water impregnated the layers of sand, which are capable of absorbing a great quantity of such liquid, and if above this there were strata impermeable to naphtha (dense, clayey, damp strata) the naphtha would accumulate in them. It is thus preserved from remote geological periods up to the present day, compressed and dissolved under the pressure of the gases which burst out in places forming naphtha fountains. If this be granted, it may be thought that in the comparatively new (geologically speaking) mountain chains, such as the Caucasian, naphtha is even now being formed. Such a supposition may explain the remarkable fact that, in Pennsylvania, localities where naphtha had been rapidly worked for five years have become exhausted, and it becomes necessary to constantly have recourse to sinking new wells in fresh places. Thus, from the year 1859, the workings were gradually transferred along a line running parallel to the Alleghany mountains for a distance of more than 200 miles, whilst in Baku the industry dates from time immemorial (the Persians worked near the village of Ballaghana) and up to the present time keeps to one and the same place. The amounts of the Pennsylvanian and Baku annual outputs are at present equal--namely, about 250 million poods (4 million tons). It may be that the Baku beds, as being of more recent geological formation, are not so exhausted by nature as those of Pennsylvania, and perhaps in the neighbourhood of Baku naphtha is still being formed, which is partially indicated by the continued activity of the mud volcanoes. As many varieties of naphtha contain in solution solid slightly volatile hydrocarbons like paraffin and mineral wax, the production of ozocerite, or mountain wax, is accounted for in conjunction with the formation of naphtha. Ozocerite is found in Galicia, also in the neighbourhood of Novorossisk, in the Caucasus, and on the islands of the Caspian Sea (particularly in the Chileken and Holy Islands); it is met with in large masses, and is used for the production of paraffin and _ceresene_, for the manufacture of candles, and similar purposes. As the naphtha treasures of the Caucasus have hardly been exploited (near Baku and near Kouban and Grosnyi), and as naphtha finds numerous uses, the subject presents most interesting features to chemists and geologists, and is worthy of the close attention of practical men. CHAPTER IX COMPOUNDS OF CARBON WITH OXYGEN AND NITROGEN [Illustration: FIG. 61.--Dumas and Stas' apparatus for determining the composition of carbonic anhydride. Carbon, graphite, or a diamond is placed in the tube E in the furnace, and heated in a stream of oxygen displaced from the bottle by water flowing from A. The oxygen is purified from carbonic anhydride and water in the tubes B, C, D. Carbonic anhydride, together with a certain amount of carbon monoxide, is formed in E. The latter is converted into carbonic acid by passing the products of combustion through a tube F, containing cupric oxide heated in a furnace. The cupric oxide oxidises this CO into CO_{2}, forming metallic copper. The potash bulbs H and tubes I, J, K retain the carbonic anhydride. Thus, knowing the weight of carbon taken and the weight of the resultant carbonic anhydride (by weighing H, I, J, K before and after the experiment), the composition of carbonic anhydride and the equivalent of carbon may be determined.] Carbonic anhydride (or carbonic acid or carbon dioxide, CO_{2}) was the first of all gases distinguished from atmospheric air. Paracelsus and Van Helmont, in the sixteenth century, knew that on heating limestone a particular gas separated, which is also formed during the alcoholic fermentation of saccharine solutions (for instance, in the manufacture of wine); they knew that it was identical with the gas which is produced by the combustion of charcoal, and that in some cases it is found in nature. In course of time it was found that this gas is absorbed by alkali, forming a salt which, under the action of acid, again yields this same gas. Priestley found that this gas exists in air, and Lavoisier determined its formation during respiration, combustion, putrefaction, and during the reduction of the oxides of metals by charcoal; he determined its composition, and showed that it only contains oxygen and carbon. Berzelius, Dumas with Stas, and Roscoe, determined its composition, showing that it contains twelve parts of carbon to thirty-two of oxygen. The composition by volume of this gas is determined from the fact that during the combustion of charcoal in oxygen, the volume remains unchanged; that is to say, _carbonic anhydride occupies the same volume as the oxygen which it contains_--that is, the atoms of the carbon are, so to speak, squeezed in between the atoms of the oxygen. O_{2} occupies two volumes and is a molecule of ordinary oxygen; CO_{2} likewise occupies two volumes, and expresses the composition and molecular weight of the gas. Carbonic anhydride exists _in nature_, both in a free state and in the most varied compounds. In a free state it is always contained (Chapter V.) in the air, and in solution is in all kinds of water. It is evolved from volcanoes, from mountain fissures, and in some caves. The well-known Dog grotto, near Agnano on the bay of Baiæ, near Naples, furnishes the best known example of such an evolution. Similar sources of carbonic anhydride are also found in other places. In France, for instance, there is a well-known poisonous fountain in Auvergne. It is a round hole, surrounded with luxurious vegetation and constantly evolving carbonic anhydride. In the woods surrounding the Lacher See near the Rhine, in the neighbourhood of extinct volcanoes, there is a depression constantly filled with this same gas. The insects which fly to this place perish, animals being unable to breathe this gas. The birds chasing the insects also die, and this is turned to profit by the local peasantry. Many mineral springs carry into the air enormous quantities of this gas. Vichy in France, Sprüdel in Germany, and Narzan in Russia (in Kislovodsk near Piatigorsk) are known for their carbonated gaseous waters. Much of this gas is also evolved in mines, cellars, diggings, and wells. People descending into such places are suffocated. The combustion, putrefaction, and fermentation of organic substances give rise to the formation of carbonic anhydride. It is also introduced into the atmosphere during the respiration of animals at all times and during the respiration of plants in darkness and also during their growth. Very simple experiments prove the formation of carbonic anhydride under these circumstances; thus, for example, if the air expelled from the lungs be passed through a glass tube into a transparent solution of lime (or baryta) in water a white precipitate will soon be formed consisting of an insoluble compound of lime and carbonic anhydride. By allowing the seeds of plants to grow under a bell jar, or in a closed vessel, the formation of carbonic anhydride may be similarly confirmed. By confining an animal, a mouse, for instance, under a bell jar, the quantity of carbonic acid which it evolves may be exactly determined, and it will he found to be many grams per day for a mouse. Such experiments on the respiration of animals have been also made with great exactitude with large animals, such as men, bulls, sheep, &c. By means of enormous hermetically closed bell receivers and the analysis of the gases evolved during respiration it was found that a man expels about 900 grams (more than two pounds) of carbonic anhydride per diem, and absorbs during this time 700 grams of oxygen.[1] It must be remarked that the carbonic anhydride of the air constitutes the fundamental food of plants (Chapters III., V., and VIII.) Carbonic anhydride in a state of combination with a variety of other substances is perhaps even more widely distributed in nature than in a free state. Some of these substances are very stable and form a large portion of the earth's crust. For instance, limestones, calcium carbonate, CaCO_{3}, were formed as precipitates in the seas existing previously on the earth; this is proved by their stratified structure and the number of remains of sea animals which they frequently contain. Chalk, lithographic stone, limestone, marls (a mixture of limestone and clay), and many other rocks are examples of such sedimentary formations. Carbonates with various other bases--such as, for instance, magnesia, ferrous oxide, zinc oxide, &c.--are often found in nature. The shells of molluscs also have the composition CaCO_{3} and many limestones were exclusively formed from the shells of minute organisms. As carbonic anhydride (together with water) is produced during the combustion of all organic compounds in a stream of oxygen or by heating them with substances which readily part with their oxygen--for instance, with copper oxide--this method is employed for estimating the amount of carbon in organic compounds, more especially as the CO_{2} can be easily collected and the amount of carbon calculated from its weight. For this purpose a hard glass tube, closed at one end, is filled with a mixture of the organic substance (about 0·2 gram) and copper oxide. The open end of the tube is fitted with a cork and tube containing calcium chloride for absorbing the water formed by the oxidation of the substance. This tube is hermetically connected (by a caoutchouc tube) with potash bulbs or other weighing apparatus (Chapter V.) containing alkali destined to absorb the carbonic anhydride. The increase in weight of this apparatus shows the amounts of carbonic anhydride formed during the combustion of the given substance, and the quantity of carbon may be determined from this, because three parts of carbon give eleven parts of carbonic anhydride. [Illustration: FIG.--62. Apparatus for the combustion of organic substances by igniting them with oxide of copper.] [1] The quantity of carbonic acid gas exhaled by a man during the twenty-four hours is not evenly produced; during the night more oxygen is taken in than during the day (by night, in twelve hours, about 450 grams), and more carbonic anhydride is separated by day than during night-time and repose; thus, of the 900 grams produced during the twenty-four hours about 375 are given out during the night and 525 by day. This depends on the formation of carbonic anhydride during the work performed by the man in the day. Every movement is the result of some change of matter, for force cannot be self-created (in accordance with the law of the conservation of energy). Proportionally to the amount of carbon consumed an amount of energy is stored up in the organism and is consumed in the various movements performed by animals. This is proved by the fact that during work a man exhales 525 grams of carbonic anhydride in twelve hours instead of 375, absorbing the same amount of oxygen as before. After a working day a man exhales by night almost the same amount of carbonic anhydride as after a day of rest, so that during a total twenty-four hours a man exhales about 900 grams of carbonic anhydride and absorbs about 980 grams of oxygen. Therefore during work the change of matter increases. The carbon expended on the work is obtained from the food; on this account the food of animals ought certainly to contain carbonaceous substances capable of dissolving under the action of the digestive fluids, and of passing into the blood, or, in other words, capable of being digested. Such food for man and all other animals is formed of vegetable matter, or of parts of other animals. The latter in every case obtain their carbonaceous matter from plants, in which it is formed by the separation of the carbon from the carbonic anhydride taken up during the day by the respiration of the plants. The volume of the oxygen exhaled by plants is almost equal to the volume of the carbonic anhydride absorbed; that is to say, nearly all the oxygen entering into the plant in the form of carbonic anhydride is liberated in a free state, whilst the carbon from the carbonic anhydride remains in the plant. At the same time the plant absorbs moisture by its leaves and roots. By a process which is unknown to us, this absorbed moisture and the carbon obtained from the carbonic anhydride enter into the composition of the plants in the form of so-called carbohydrates, composing the greater part of the vegetable tissues, starch and cellulose of the composition C_{6}H_{10}O_{5} being representatives of them. They may be considered like all carbohydrates as compounds of carbon and water, 6C + 5H_{2}O. In this way a _circulation_ of the carbon goes on in nature by means of vegetable and animal organisms, in which changes the principal factor is the carbonic anhydride of the air. _For the preparation of carbonic anhydride_ in laboratories and often in manufactories, various kinds of calcium carbonate are used, being treated with some acid; it is, however, most usual to employ the so-called muriatic acid--that is, an aqueous solution of hydrochloric acid, HCl--because, in the first place, the substance formed, calcium chloride. CaCl_{2}, is soluble in water and does not hinder the further action of the acid on the calcium carbonate, and secondly because, as we shall see further on, muriatic acid is a common product of chemical works and one of the cheapest. For calcium carbonate, either limestone, chalk, or marble is used.[2] CaCO_{3} + 2HCl = CaCl_{2} + H_{2}O + CO_{2}. The nature of the reaction in this case is the same as in the decomposition of nitre by sulphuric acid; only in the latter case a hydrate is formed, and in the former an anhydride of the acid, because the hydrate, carbonic acid, H_{2}CO_{3}, is unstable and as soon as it separates decomposes into water and its own anhydride. It is evident from the explanation of the cause of the action of sulphuric acid on nitre that not every acid can be employed for obtaining carbonic anhydride; namely, those will not set it free which chemically are but slightly energetic, or those which are insoluble in water, or are themselves as volatile as carbonic anhydride.[3] But as many acids are soluble in water and are less volatile than carbonic anhydride, the latter is evolved by the action of most acids on its salts, and this reaction takes place at ordinary temperatures.[4] [2] Other acids may be used instead of hydrochloric; for instance, acetic, or even sulphuric, although this latter is not suitable, because it forms as a product insoluble calcium sulphate (gypsum) which surrounds the untouched calcium carbonate, and thus prevents a further evolution of gas. But if porous limestone--for instance, chalk--be treated with sulphuric acid diluted with an equal volume of water, the liquid is absorbed and acting on the mass of the salt, the evolution of carbonic anhydride continues evenly for a long time. Instead of calcium carbonate other carbonates may of course be used; for instance, washing-soda, Na_{2}CO_{3}, which is often chosen when it is required to produce a rapid stream of carbonic anhydride (for example, for liquefying it). But natural crystalline magnesium carbonate and similar salts are with difficulty decomposed by hydrochloric and sulphuric acids. When for manufacturing purposes--for instance, in precipitating lime in sugar-works--a large quantity of carbonic acid gas is required, it is generally obtained by burning charcoal, and the products of combustion, rich in carbonic anhydride, are pumped into the liquid containing the lime, and the carbonic anhydride is thus absorbed. Another method is also practised, which consists in using the carbonic anhydride separated during fermentation, or that evolved from limekilns. During the fermentation of sweet-wort, grape-juice, and other similar saccharine solutions, the glucose C_{6}H_{12}O_{6} changes under the influence of the yeast organism, forming alcohol (2C_{2}H_{6}O), and carbonic anhydride (2CO_{2}) which separates in the form of gas; if the fermentation proceeds in closed bottles sparkling wine is obtained. When carbonic acid gas is prepared for saturating water and other beverages it is necessary to use it in a pure state. Whilst in the state in which it is evolved from ordinary limestones by the aid of acids it contains, besides a certain quantity of acid, the organic matters of the limestone; in order to diminish the quantity of these substances the densest kinds of dolomites are used, which contain less organic matter, and the gas formed is passed through various washing apparatus, and then through a solution of potassium permanganate, which absorbs organic matter and does not take up carbonic anhydride. [3] Hypochlorous acid, HClO, and its anhydride, Cl_{2}O, do not displace carbonic acid, and hydrogen sulphide has the same relation to carbonic acid as nitric acid to hydrochloric--an excess of either one displaces the other. [4] Thus, in preparing the ordinary effervescing powders, sodium bicarbonate (or acid carbonate of soda) is used, and mixed with powdered citric or tartaric acid. In a dry state these powders do not evolve carbonic anhydride, but when mixed with water the evolution takes place briskly, which is due to the substances passing into solution. The salts of carbonic acid may be recognised from the fact that they evolve carbonic acid with a hissing noise when treated with acids. If vinegar, which contains acetic acid, be poured upon limestone, marble, malachite (containing copper carbonate), &c., carbonic anhydride is evolved with a hissing noise. It is noteworthy that neither hydrochloric acid, nor even sulphuric acid nor acetic acid, acts on limestone except in presence of water. We shall refer to this later on. For the preparation of carbonic anhydride in laboratories, marble is generally used. It is placed in a Woulfe's bottle and treated with hydrochloric acid in an apparatus similar to the one used for the production of hydrogen. The gas evolved carries away through the tube part of the volatile hydrochloric acid, and it is therefore necessary to wash the gas by passing it through another Woulfe's bottle containing water. If it be necessary to obtain dry carbonic anhydride, it must be passed through chloride of calcium.[5] [5] The direct observations made (1876) by Messrs. Bogouski and Kayander lead to the conclusion that the quantity of carbonic anhydride evolved by the action of acids on marble (as homogeneous as possible) is directly proportional to the time of action, the extent of surface, and the degree of concentration of the acid, and inversely proportional to the molecular weight of the acid. If the surface of a piece of Carrara marble be equal to one decimetre, the time of action one minute, and one cubic decimetre or litre contains one gram of hydrochloric acid, then about 0·02 gram of carbonic anhydride will be evolved. If the litre contains _n_ grams of hydrochloric acid, then by experiment the amount will be _n_ × 0·02 of carbonic anhydride. Therefore, if the litre contains 36·5 (= HCl) grams, about 0·73 gram of carbonic anhydride (about half a litre) would he evolved per minute. If nitric acid or hydrobromic acid be used instead of hydrochloric, then, with a combining proportion of the acid, the same quantity of carbonic anhydride will be evolved; thus, if the litre contains 63 (= HNO_{3}) grams of nitric acid, or 81 (= HBr) grams of hydrobromic acid, the quantity of carbonic anhydride evolved will still be 0·73 gram. Spring, in 1890, made a series of similar determinations. Carbonic anhydride may also be prepared by heating many of the salts of carbonic acid; for instance, by heating magnesium carbonate, MgCO_{3} (_e.g._, in the form of dolomite), the separation is easily effected, particularly in the presence of the vapours of water. The acid salts of carbonic acid (for instance, NaHCO_{3}, see further on) readily and abundantly give carbonic anhydride when heated. Carbonic anhydride is colourless, has a slight smell and a faint acid taste; its density in a gaseous state is twenty-two times as great as that of hydrogen, because its molecular weight is forty-four.[6] It is an example of those gaseous substances which have been long ago transformed into all the three states. In order to obtain liquid carbonic anhydride, the gas must be submitted to a pressure of thirty-six atmospheres at 0°.[7] Its absolute boiling point = +32°.[8] Liquid carbonic anhydride is colourless, does not mix with water, but is soluble in alcohol, ether, and oils; at 0° its specific gravity is 0·83.[8 bis] The boiling point of this liquid lies at -80°--that is to say, the pressure of carbonic acid gas at that temperature does not exceed that of the atmosphere. At the ordinary temperature the liquid remains as such for some time under ordinary pressure, on account of its requiring a considerable amount of heat for its evaporation. If the evaporation takes place rapidly, especially if the liquid issues in a stream, such a decrease of temperature occurs that a part of the carbonic anhydride is transformed into a solid snowy mass. Water, mercury, and many other liquids freeze on coming into contact with snow-like carbonic anhydride.[9] In this form carbonic anhydride may be preserved for a long time in the open air, because it requires still more heat to turn it into a gas than when in a liquid state.[9 bis] [6] As carbonic anhydride is one and a half times heavier than air, it diffuses with difficulty, and therefore does not easily mix with air, but sinks in it. This may be shown in various ways; for instance, the gas may be carefully poured from one vessel into another containing air. If a lighted taper be plunged into the vessel containing carbonic anhydride it is extinguished, and then, after pouring the gas into the other cylinder, it will burn in the former and be extinguished in the latter. If a certain quantity of carbonic anhydride be poured into a vessel containing air, and soap-bubbles be introduced, they will only sink as far as the stratum where the atmosphere of carbonic anhydride commences, as this latter is heavier than the soap-bubbles filled with air. Naturally, after a certain lapse of time, the carbonic anhydride will be diffused throughout the vessel, and form a uniform mixture with the air, just as salt in water. [7] This liquefaction was first observed by Faraday, who sealed up in a tube a mixture of a carbonate and sulphuric acid. Afterwards this method was very considerably improved by Thilorier and Natterer, whose apparatus is given in Chapter VI. in describing N_{2}O. It is, however, necessary to remark that the preparation of liquid carbonic anhydride requires good liquefying apparatus, constant cooling, and a rapid preparation of large masses of carbonic anhydride. [8] Carbonic anhydride, having the same molecular weight as nitrous oxide, very much resembles it when in a liquid state. [8 bis] When poured into a tube, which is then sealed up, liquefied carbonic anhydride can be easily preserved, because a thick tube easily supports the pressure (about 50 atmospheres) exerted by the liquid at the ordinary temperature. [9] When a fine stream of liquid carbonic anhydride is discharged into a closed metallic vessel, about one-third of its mass solidifies and the remainder evaporates. In employing solid carbonic anhydride for making experiments at low temperatures, it is best to use it mixed with ether, otherwise there will be few points of contact. If a stream of air be blown through a mixture of liquid carbonic anhydride and ether, the evaporation proceeds rapidly, and great cold is obtained. At present in some special manufactories (and for making artificial mineral waters) carbonic anhydride is liquefied on the large scale, filled into wrought-iron cylinders provided with a valve, and in this manner it can be transported and preserved safely for a long time. It is used, for instance, in breweries. [9 bis] Solid carbonic anhydride, notwithstanding its very low temperature, can be safely placed on the hand, because it continually evolves gas which prevents its coming into actual contact with the skin, but if a piece be squeezed between the fingers, it produces a severe frost bite similar to a burn. If the snow-like solid be mixed with ether, a semi-liquid mass is obtained, which is employed for artificial refrigeration. This mixture may be used for liquefying many other gases--such as chlorine, nitrous oxide, hydrogen sulphide, and others. The evaporation of such a mixture proceeds with far greater rapidity under the receiver of an air-pump, and consequently the refrigeration is more intense. By this means many gases may be liquefied which resist other methods--namely, olefiant gas, hydrochloric acid gas, and others. Liquid carbonic anhydride in this case congeals in the tube into a glassy transparent mass. Pictet availed himself of this method for liquefying many permanent gases (_see_ Chapter II.) Bleekrode, by compressing solid CO_{2} in a cylinder by means of a piston, obtained a semi-transparent stick, which contained as much as 1·3 and even 1·6 gram of CO_{2} per cubic centimetre. In this form the CO_{2} slowly evaporated, and could be kept for a long time. The capacity which carbonic anhydride has of being liquefied stands in connection with its _considerable solubility in water_, alcohol, and other liquids. Its solubility in water has been already spoken of in the first chapter. Carbonic anhydride is still more soluble in alcohol than in water, namely at 0° one volume of alcohol dissolves 4·3 volumes of this gas, and at 20° 2·9 volumes. Aqueous solutions of carbonic anhydride, under a pressure of several atmospheres, are now prepared artificially, because water saturated with this gas promotes digestion and quenches thirst. For this purpose the carbonic anhydride is pumped by means of a force-pump into a closed vessel containing the liquid, and then bottled off, taking special means to ensure rapid and air-tight corking. Various effervescing drinks and artificially effervescing wines are thus prepared. The presence of carbonic anhydride has an important significance in nature, because by its means water acquires the property of decomposing and dissolving many substances which are not acted on by pure water; for instance, calcium phosphates and carbonates are soluble in water containing carbonic acid. If the water in the interior of the earth is saturated with carbonic acid under pressure, the quantity of calcium carbonate in solution may reach three grams per litre, and on issuing at the surface, as the carbonic anhydride escapes, the calcium carbonate will be deposited.[10] Water charged with carbonic anhydride brings about the destruction of many rocky formations by removing the lime, alkali, &c., from them. This process has been going on and continues on an enormous scale. Rocks contain silica and the oxides of various metals; amongst others, the oxides of aluminium, calcium, and sodium. Water charged with carbonic acid dissolves both the latter, transforming them into carbonates. The waters of the ocean ought, as the evolution of the carbonic anhydride proceeds, to precipitate salts of lime; these are actually found everywhere on the surface of the ground in those places which previously formed the bed of the ocean. The presence of carbonic anhydride in solution in water is essential to the nourishment and growth of water plants. [10] If such water trickles through crevices and enters a cavern, the evaporation will be slow, and therefore in those places from which the water drips growths of calcium carbonate will be formed, just like the icicles formed on the roof-gutters in winter-time. Similar conical and cylindrical stony growths form the so-called stalactites or pendants hanging from above and stalagmites formed on the bottom of caves. Sometimes these two kinds meet together, forming entire columns filling the cave. Many of these caves are remarkable for their picturesqueness; for instance, the cave of Antiparos, in the Grecian Archipelago. This same cause also forms spongy masses of calcium carbonate in those places where the springs come to the surface of the earth. It is therefore very evident that a calcareous solution is sometimes capable of penetrating plants and filling the whole of their mass with calcium carbonate. This is one of the forms of petrified plants. Calcium phosphate in solution in water containing carbonic acid plays an important part in the nourishment of plants, because all plants contain both lime and phosphoric acid. Although carbonic anhydride is soluble in water, yet no definite hydrate is formed;[11] nevertheless an idea of the composition of this hydrate may be formed from that of the salts of carbonic acid, because a hydrate is nothing but a salt in which the metal is replaced by hydrogen. As carbonic anhydride forms salts of the composition K_{2}CO_{3}, Na_{2}CO_{3}, HNaCO_{3}, &c., therefore carbonic acid ought to have the composition H_{2}CO_{3}--that is, it ought to contain CO_{2} + H_{2}O. Whenever this substance is formed, it decomposes into its component parts--that is, into water and carbonic anhydride. _The acid properties_ of carbonic anhydride[11 bis] are demonstrated by its being directly absorbed by alkaline solutions and forming salts with them. In distinction from nitric, HNO_{3}, and similar monobasic acids which with univalent metals (exchanging one atom for one atom of hydrogen) give salts such as those of potassium, sodium, and silver containing only one atom of the metal (NaNO_{3}, AgNO_{3}), and with bivalent[12] metals (such as calcium, barium, lead) salts containing two acid groups--for example, Ca(NO_{3})_{2}, Pb(NO_{3})_{2}--carbonic acid, H_{2}CO_{3}, _is bibasic_, that is contains two atoms of hydrogen in the hydrate or two atoms of univalent metals in their salts: for example, Na_{2}CO_{3} is washing soda, a normal salt; NaHCO_{3} is the bicarbonate, an acid salt. Therefore, if M´ be a univalent metal, its carbonates in general are the normal carbonate M´_{2}CO_{3} and the acid carbonate, M´HCO_{3}; or if M´´ be a bivalent metal (replacing H_{2}) its normal carbonate will be M´´CO_{3}; these metals do not usually form acid salts, as we shall see further on. The bibasic character of carbonic acid is akin to that of sulphuric acid, H_{2}SO_{4},[13] but the latter, in distinction from the former, is an example of the energetic or strong acids (such as nitric or hydrochloric), whilst in carbonic acid we observe but feeble development of the acid properties; hence carbonic acid must be considered _a weak acid_. This conception must, however, be taken as only comparative, as up to this time there is no definitely established rule for measuring the energy[14] of acids. The feeble acid properties of carbonic acid may, however, be judged from the joint evidence of many properties. With such energetic alkalis as soda and potash, carbonic acid forms normal salts, soluble in water, but having an alkaline reaction and in many cases themselves acting as alkalis.[15] The acid salts of these alkalis, NaHCO_{3} and KHCO_{3}, have a neutral reaction on litmus, although they, like acids, contain hydrogen, which may be exchanged for metals. The acid salts of such acids--as, for instance, of sulphuric acid, NaHSO_{4}--have a clearly defined acid reaction, and therefore carbonic acid is unable to neutralise the powerful basic properties of such alkalis as potash or soda. Carbonic acid does not even combine at all with feeble bases, such as alumina, Al_{2}O_{3}, and therefore if a strong solution of sodium carbonate, Na_{2}CO_{3}, be added to a strong solution of aluminium sulphate, Al_{2}(SO_{4})_{3}, although according to double saline decompositions aluminium carbonate, Al_{2}(CO_{3})_{3}, ought to be formed, the carbonic acid separates, for this salt splits up in the presence of water into aluminium hydroxide and carbonic anhydride: Al_{2}(CO_{3})_{3} + 3H_{2}O = Al_{2}(OH)_{6} + 3CO_{2}. Thus feeble bases are unable to retain carbonic acid even at ordinary temperatures. For the same reason, in the case of bases of medium energy, although they form carbonates, the latter are comparatively easily decomposed by heating, as is shown by the decomposition of copper carbonate, CuCO_{3} (_see_ Introduction), and even of calcium carbonate, CaCO_{3}. Only the normal (not the acid) salts of such powerful bases as potassium and sodium are capable of standing a red heat without decomposition. The acid salts--for instance, NaHCO_{3}--decompose even on heating their solutions (2NaHCO_{3} = Na_{2}CO_{3} + H_{2}O + CO_{2}), evolving carbonic anhydride. The amount of heat given out by the combination of carbonic acid with bases also shows its feeble acid properties, being considerably less than with energetic acids. Thus if a weak solution of forty grams of sodium hydroxide be saturated (up to the formation of a normal salt) with sulphuric or nitric acid or another powerful acid, from thirteen to fifteen thousand calories are given out, but with carbonic acid only about ten thousand calories.[16] The majority of carbonates are insoluble in water, and therefore such solutions as sodium, potassium, or ammonium carbonates form in solutions of most other salts, MX or M´´X_{2}, insoluble precipitates of carbonates, M_{2}CO_{3} or M´´CO_{3}. Thus a solution of barium chloride gives with sodium carbonate a precipitate of barium carbonate, BaCO_{3}. For this reason rocks, especially those of aqueous origin, very often contain carbonates; for example, calcium, ferrous, or magnesium carbonates, &c. [11] The crystallohydrate, CO_{2},8H_{2}O of Wroblewski (Chapter 1., Note 67), in the first place, is only formed under special conditions; in the second place, its existence still requires confirmation; and in the third place, it does not correspond with that hydrate H_{2}CO_{3} which should occur, judging from the composition of the salts. [11 bis] It is easy to demonstrate the acid properties of carbonic anhydride by taking a long tube, closed at one end, and filling it with this gas; a test-tube is then filled with a solution of an alkali (for instance, sodium hydroxide), which is then poured into the long tube and the open end is corked. The solution is then well shaken in the tube, and the corked end plunged into water. If the cork be now withdrawn under water, the water will fill the tube. The vacuum obtained by the absorption of the carbonic anhydride by an alkali is so complete that even an electric discharge will not pass through it. This method is often applied to produce a vacuum. [12] The reasons for distinguishing the uni-, bi-, tri-, and quadrivalent metals will be explained hereafter on passing from the univalent metals (Na, K, Li) to the bivalent (Mg. Ca, Ba), Chapter XIV. [13] Up to the year 1840, or thereabout, acids were not distinguished by their basicity. Graham, while studying phosphoric acid, H_{3}PO_{4}, and Liebig, while studying many organic acids, distinguished mono-, bi-, and tribasic acids. Gerhardt and Laurent generalised these relations, showing that this distinction extends over many reactions (for instance, to the faculty of bibasic acids of forming acid salts with alkalis, KHO or NaHO, or with alcohols, RHO, &c.); but now, since a definite conception as to atoms and molecules has been arrived at, _the basicity of an acid is determined by the number of hydrogen atoms,_ contained in a molecule of the acid, which can be exchanged for metals. If carbonic acid forms acid salts, NaHCO_{3}, and normal salts, Na_{2}CO_{3}, it is evident that the hydrate is H_{2}CO_{3}, a bibasic acid. Otherwise it is at present impossible to account for the composition of these salts. But when C = 6 and O = 8 were taken, then the formula CO_{2} expressed the composition, but not the molecular weight, of carbonic anhydride; and the composition of the normal salt would be Na_{2}C_{2}O_{6} or NaCO_{3}, therefore carbonic acid might have been considered as a monobasic acid. Then the acid salt would have been represented by NaCO_{3},HCO_{3}. Such questions were the cause of much argument and difference of opinion among chemists about forty years ago. At present there cannot be two opinions on the subject if the law of Avogadro-Gerhardt and its consequences be strictly adhered to. It may, however, be observed here that the monobasic acids R(OH) were for a long time considered to be incapable of being decomposed into water and anhydride, and this property was ascribed to the bibasic acids R(OH)_{2} as containing the elements necessary for the separation of the molecule of water, H_{2}O. Thus H_{2}SO_{4} or SO_{2}(OH)_{2}, H_{2}CO_{3}, or CO(OH)_{2}, and other bibasic acids decompose into an anhydride, RO, and water, H_{2}O. But as nitrous, HNO_{2}, iodic, HIO_{3}, hypochlorous, HClO, and other monobasic acids easily give their anhydrides N_{2}O_{3}, I_{2}O_{5}, Cl_{2}O, &c., that method of distinguishing the basicity of acids, although it fairly well satisfies the requirements of organic chemistry, cannot be considered correct. It may also be remarked that up to the present time not one of the bibasic acids has been found to have the faculty of being distilled without being decomposed into anhydride and water (even H_{2}SO_{4}, on being evaporated and distilled, gives SO_{3} + H_{2}O), and the decomposition of acids into water and anhydride proceeds particularly easily in dealing with feebly energetic acids, such as carbonic, nitrous, boric, and hypochlorous. Let us add that carbonic acid, as a hydrate corresponding to marsh gas, C(HO)_{4} = CO_{2} + 2H_{2}O, ought to be tetrabasic. But in general it does not form such salts. Basic salts, however, such as CuCO_{3}CuO, may be regarded in this sense, for CCu_{2}O_{4} corresponds with CH_{4}O_{4}, as Cu corresponds with H_{2}. Amongst the ethereal salts (alcoholic derivatives) of carbonic acid corresponding cases are, however, observed; for instance, ethylic orthocarbonate, C(C_{2}H_{5}O)_{4} (obtained by the action of chloropicrin, C(NO_{2})Cl_{3}, on sodium ethoxide, C_{2}H_{5}ONa; boiling point 158°; specific gravity, 0·92). The name _orthocarbonic acid_ for CH_{4}O_{4} is taken from _orthophosphoric acid_, PH_{3}O_{4}, which corresponds with PH_{3} (_see_ Chapter on Phosphorus). [14] Long ago endeavours were made to find a _measure of affinity_ of acids and bases, because some of the acids, such as sulphuric or nitric, form comparatively stable salts, decomposed with difficulty by heat and water, whilst others, like carbonic and hypochlorous acids, do not combine with feeble bases, and with most of the other bases form salts which are easily decomposed. The same may be said with regard to bases, among which those of potassium, K_{2}O, sodium, Na_{2}O, and barium, BaO, may serve as examples of the most powerful, because they combine with the most feeble acids and form a mass of salts of great stability, whilst as examples of the feeblest bases alumina, Al_{2}O_{3}, or bismuth oxide, Bi_{2}O_{3}, may be taken, because they form salts easily decomposed by water and by heat if the acid be volatile. Such a division of acids and bases into the feeblest and most powerful is justified by all evidence concerning them, and is quoted in this work. But the teaching of this subject in certain circles has acquired quite a new tone, which, in my opinion, cannot be accepted without certain reservations and criticisms, although it comprises many interesting features. The fact is that Thomsen, Ostwald, and others proposed to express the measure of affinity of acids to bases by figures drawn from data of the measure of displacement of acids in aqueous solutions, judging (1) from the amount of heat developed by mixing a solution of the salt with a solution of another acid (the avidity of acids, according to Thomsen); (2) from the change of the volumes accompanying such a mutual action of solutions (Ostwald); (3) from the change of the index of refraction of solutions (Ostwald), &c. Besides this there are many other methods which allow us to form an opinion about the distribution of bases among various acids in aqueous solutions. Some of these methods will be described hereafter. It ought, however, to be remarked that in making investigations in aqueous solutions the affinity to water is generally left out of sight. If a base N, combining with acids X and Y in presence of them both, divides in such a way that one-third of it combines with X and two-thirds with Y, a conclusion is formed that the affinity, or power of forming salts, of the acid Y is twice as great as that of X. But the presence of the water is not taken into account. If the acid X has an affinity for water and for N it will be distributed between them; and if X has a greater affinity for water than Y, then less of X will combine with N than of Y. If, in addition to this, the acid X is capable of forming an acid salt NX_{2}, and Y is not, the conclusion of the relative strength of X and Y will be still more erroneous, because the X set free will form such a salt on the addition of Y to NX. We shall see in Chapter X. that when sulphuric and nitric acids in weak aqueous solution act on sodium, they are distributed exactly in this way: namely, one-third of the sodium combines with the sulphuric and two-thirds with the nitric acid; but, in my opinion, this does not show that sulphuric acid, compared with nitric acid, possesses but half the degree of affinity for bases like soda, and only demonstrates the greater affinity of sulphuric acid for water compared with that of nitric acid. In this way the methods of studying the distribution in aqueous solutions probably only shows the difference of the relation of the acid to a base and to water. In view of these considerations, although the teaching of the distribution of salt-forming elements in _aqueous solutions_ is an object of great and independent interest, it can hardly serve to determine the measure of affinity between bases and acids. Similar considerations ought to be kept in view when determining the energy of acids by means of the _electrical conductivity of their weak solutions_. This method, proposed by Arrhenius (1884), and applied on an extensive scale by Ostwald (who developed it in great detail in his _Lehrbuch d. allgemeinen Chemie_, v. ii., 1887), is founded on the fact that the relation of the so-called molecular electrical-conductivity of weak solutions of various acids (I) coincides with the relation in which the same acids stand according to the distribution, (II) found by one of the above-mentioned methods, and with the relation deduced for them from observations upon the velocity of reaction, (III) for instance, according to the rate of the splitting up of an ethereal salt (into alcohol and acid), or from the rate of the so-called inversion of sugar--that is, its transformation into glucose--as is seen by comparing the annexed figures, in which the energy of hydrochloric acid is taken as equal to 100:-- I II III Hydrochloric acid, HCl 100 100 100 Hydrobromic acid, HBr 101 98 105 Nitric acid, HNO_{3} 100 100 96 Sulphuric acid, H_{2}SO_{4} 65 49 74 Formic acid, CH_{2}O_{2} 2 4 1 Acetic acid, C_{2}H_{4}O_{2} 1 2 1 Oxalic acid, C_{2}H_{2}O_{4} 20 24 18 Phosphoric acid, PH_{3}O_{4} 7 -- 6 The coincidence of these figures, obtained by so many various methods, presents a most important and instructive relation between phenomena of different kinds, but in my opinion it does not permit us to assert that the degree of affinity existing between bases and various acids is determined by all these various methods, because the influence of the water must be taken into consideration. On this account, until the theory of solution is more thoroughly worked out, this subject (which for the present ought to be treated of in special treatises on chemical mechanics) must be treated with great caution. But now we may hope to decide this question guided by a study of the rate of reaction, the influence of acids and bases upon indicators, &c., all of which are treated fully in works on physical and theoretical chemistry. [15] Thus, for instance, in the washing of fabrics the caustic alkalis, such as sodium hydroxide, in weak solutions, act in removing the fatty matter just in the same way as carbonate solutions; for instance, a solution of soda crystals, Na_{2}CO_{3}. Soap acts in the same way, being composed of feeble acids, either fatty or resinous, combined with alkali. On this account all such substances are applied in manufacturing processes, and answer equally well in practice for bleaching and washing fabrics. Soda crystals or soap are preferred to caustic alkali, because an excess of the latter may have a destructive effect on the fabrics. It may be supposed that in aqueous solutions of soap or soda crystals, part of the base will form caustic alkali; that is to say, the water will compete with the weak acids, and the alkali will be distributed between them and the water. [16] Although carbonic acid is reckoned among the feeble acids, yet there are evidently many others still feebler--for instance, prussic acid, hypochlorous acid, many organic acids, &c. Bases like alumina, or such feeble acids as silica, when in combination with alkalis, are decomposed in aqueous solutions by carbonic acid, but on fusion--that is, without the presence of water--they displace it, which clearly shows in phenomena of this kind how much depends upon the conditions of reaction and the properties of the substances formed. These relations, which at first sight appear complex, may be best understood if we represent that two salts, MX and NY, in general always give more or less of two other salts, MY and NX, and then examine the properties of the derived substances. Thus, in solution, sodium silicate, Na_{2}SiO_{3}, with carbonic anhydride will to some extent form sodium carbonate and silica, SiO_{2}; but the latter, being colloid, separates, and the remaining mass of sodium silicate is again decomposed by carbonic anhydride, so that finally silica separates and sodium carbonate is formed. In a fused state the case is different; sodium carbonate will react with silica to form carbonic anhydride and sodium silicate, but the carbonic anhydride will be separated as a gas, and therefore in the residue the same reaction will again take place, and ultimately the carbonic anhydride is entirely eliminated and sodium silicate remains. If, on the other hand, nothing is removed from the sphere of the reaction, distribution takes place. Therefore, although carbonic anhydride is a feeble acid, still not for this reason, but only in virtue of its gaseous form, do all soluble acids displace it in saline solutions (_see_ Chapter X.) Carbonic anhydride--which, like water, is formed with the development of a large amount of heat--is very stable. Only very few substances are capable of depriving it of its oxygen. However, certain metals, such as magnesium, potassium and the like, on being heated, burn in it, depositing carbon and forming oxides. If a mixture of carbonic anhydride and hydrogen be passed through a heated tube, the formation of water and carbonic oxide will be observed; CO_{2} + H_{2} = CO + H_{2}O. But only a portion of the carbonic acid gas undergoes this change, and therefore the result will be a mixture of carbonic anhydride, carbonic oxide, hydrogen, and water, which does not suffer further change under the action of heat.[17] Although, like water, carbonic anhydride is exceedingly stable, still on being heated it partially decomposes into carbonic oxide and oxygen. Deville showed that such is the case if carbonic anhydride be passed through a long tube containing pieces of porcelain and heated to 1,300°. If the products of decomposition--namely, the carbonic oxide and oxygen--be suddenly cooled, they can be collected separately, although they partly reunite together. A similar decomposition of carbonic anhydride into carbonic oxide and oxygen takes place on passing a series of electric sparks through it (for instance, in the eudiometer). Under these conditions an increase of volume occurs, because two volumes of CO_{2} give two volumes of CO and one volume of O. The decomposition reaches a certain limit (less than one-third) and does not proceed further, so that the result is a mixture of carbonic anhydride, carbonic oxide, and oxygen, which is not altered in composition by the continued action of the sparks. This is readily understood, as it is a reversible reaction. If the carbonic anhydride be removed, then the mixture explodes when a spark is passed and forms carbonic anhydride.[17 bis] If from an identical mixture the oxygen (and not the carbonic anhydride) be removed, and a series of sparks be again passed, the decomposition is renewed, and terminates with the complete dissociation of the carbonic anhydride. Phosphorus is used in order to effect the complete absorption of the oxygen. In these examples we see that a definite mixture of changeable substances is capable of arriving at a state of stable equilibrium, destroyed, however, by the removal of one of the substances composing the mixture. This is one of the instances of the influence of mass. [17] Hydrogen and carbon are near akin to oxygen as regards affinity, but it ought to be considered that the affinity of hydrogen is slightly greater than that of carbon, because during the combustion of hydrocarbons the hydrogen burns first. Some idea of this similarity of affinity may be formed by the quantity of heat evolved. Gaseous hydrogen, H_{2}, on combining with an atom of oxygen, O = 16, develops 69,000 heat-units if the water formed be condensed to a liquid state. If the water remains in the form of a gas (steam) the latent heat of evaporation must be subtracted, and then 58,000 calories will be developed. Carbon, C, as a solid, on combining with O_{2} = 32 develops about 97,000 calories, forming gaseous CO_{2}. If it were gaseous like hydrogen, and only contained C_{2} in its molecule, much more heat would be developed, and judging by other substances, whose molecules on passing from the solid to the gaseous state absorb about 10,000 to 15,000 calories, it must be held that gaseous carbon on forming gaseous carbonic anhydride would develop not less than 110,000 calories--that is, approximately twice as much as is developed in the formation of water. And since there is twice as much oxygen in a molecule of carbonic anhydride as in a molecule of water, the oxygen develops approximately the same quantity of heat on combining with hydrogen as with carbon. That is to say, that here we find the same close affinity (_see_ Chapter II., Note 7) determined by the quantity of heat as between hydrogen, zinc, and iron. For this reason here also, as in the case of hydrogen and iron, we ought to expect an equal distribution of oxygen between hydrogen and carbon, if they are both in excess compared with the amount of oxygen; but if there be an excess of carbon, it will decompose water, whilst an excess of hydrogen will decompose carbonic anhydride. Even if these phenomena and similar ones have been explained in isolated cases, a complete theory of the whole subject is still wanting in the present condition of chemical knowledge. [17 bis] The degree or relative magnitude of the dissociation of CO_{2} varies with the temperature and pressure--that is, it increases with the temperature and as the pressure decreases. Deville found that at a pressure of 1 atmosphere in the flame of carbonic oxide burning in oxygen, about 40 per cent. of the CO_{2}, is decomposed when the temperature is about 3,000°, and at 1,500° less than 1 per cent. (Krafts); whilst under a pressure of 10 atmospheres about 34 per cent. is decomposed at 3,300° (Mallard and Le Chatelier). It follows therefore that, under very small pressures, the dissociation of CO_{2} will be considerable even at comparatively moderate temperatures, but at the temperature of ordinary furnaces (about 1,000°) even under the small partial pressure of the carbonic acid, there are only small traces of decomposition which may be neglected in a practical estimation of the combustion of fuels. We may here cite the molecular specific heat of CO_{2} (_i.e._ the amount of heat required to raise 44 units of weight of CO_{2} 1°), according to the determinations and calculations of Mallard and Le Chatelier, for a constant volume C_{v} = 6·26 + 0·0037_t_; for a constant pressure C_{p} = C_{v} + 2 (_see_ Chapter XIV., Note 7), _i.e._ the specific heat of CO_{2} increases rapidly with a rise of temperature: for example, at 0° (per 1 part by weight), it is, at a constant pressure = 0·188, at 1,000° = 0·272, at 2,000°, about 0·356. A perfectly distinct rise of the specific heat (for example, at 2,000°, 0·409), is given by a comparison of observations made by the above-mentioned investigators and by Berthelot and Vieille (Kournakoff). The cause of this must be looked for in dissociation. T. M. Cheltzoff, however, considers upon the basis of his researches upon explosives that it must be admitted that a maximum is reached at a certain temperature (about 2,500°), beyond which the specific heat begins to fall. Although carbonic anhydride is decomposed on heating, yielding oxygen, it is nevertheless, like water, an unchangeable substance at ordinary temperatures. Its decomposition, as effected by plants, is on this account all the more remarkable; in this case the whole of the oxygen of the carbonic anhydride is separated in the free state. The mechanism of this change is that the heat and light absorbed by the plants are expended in the decomposition of the carbonic anhydride. This accounts for the enormous influence of temperature and light on the growth of plants. But it is at present not clearly understood how this takes place, or by what separate intermediate reactions the whole process of decomposition of carbonic anhydride in plants into oxygen and the carbohydrates (Note 1) remaining in them, takes place. It is known that sulphurous anhydride (in many ways resembling carbonic anhydride) under the action of light (and also of heat) forms sulphur and sulphuric anhydride, SO_{3}, and in the presence of water, sulphuric acid. But no similar decomposition has been obtained directly with carbonic anhydride, although it forms an exceedingly easily decomposable higher oxide--percarbonic acid;[18] and perhaps that is the reason the oxygen separates. On the other hand, it is known that plants always form and contain _organic acids_, and these must be regarded as derivatives of carbonic acid, as is seen by all their reactions, of which we will shortly treat. For this reason it might be thought that the carbonic acid absorbed by the plants first forms (according to Baeyer) formic aldehyde, CH_{2}O, and from it organic acids, and that these latter in their final transformation form all the other complex organic substances of the plants. Many organic acids are found in plants in considerable quantity; for instance, tartaric acid, C_{4}H_{6}O_{6}, found in grape-juice and in the acid juice of many plants; malic acid, C_{4}H_{6}O_{5}, found not only in unripe apples but in still larger quantities in mountain ash berries; citric acid, C_{6}H_{8}O_{7}, found in the acid juice of lemons, in gooseberries, cranberries, &c.; oxalic acid, C_{2}H_{2}O_{4}, found in wood-sorrel and many other plants. Sometimes these acids exist in a free state in the plants, and sometimes in the form of salts; for instance, tartaric acid is met with in grapes as the salt known as cream of tartar, but in the impure state called argol, or tartar, C_{4}H_{5}KO_{6}. In sorrel we find the so-called salts of sorrel, or acid potassium oxalate, C_{2}HKO_{4}. There is a very clear connection between carbonic anhydride and the above-mentioned organic acids--namely, they all, under one condition or another, yield carbonic anhydride, and can all be formed by means of it from substances destitute of acid properties. The following examples afford the best demonstration of this fact: if acetic acid, C_{2}H_{4}O_{2}, the acid of vinegar, be passed in the form of vapour through a heated tube, it splits up into carbonic anhydride and marsh gas = CO_{2} + CH_{4}. But conversely it can also be obtained from those components into which it decomposes. If one equivalent of hydrogen in marsh gas be replaced (by indirect means) by sodium, and the compound CH_{3}Na is obtained, this directly absorbs carbonic anhydride, forming a salt of acetic acid, CH_{3}Na + CO_{2} = C_{2}H_{3}NaO_{2}; from this acetic acid itself may be easily obtained. Thus acetic acid decomposes into marsh gas and carbonic anhydride, and conversely is obtainable from them. The hydrogen of marsh gas does not, like that in acids, show the property of being directly replaced by metals; _i.e._ CH_{4} does not show any acid character whatever, but on combining with the elements of carbonic anhydride it acquires the properties of an acid. The investigation of all other organic acids shows similarly that their acid character depends on their containing the elements of carbonic anhydride. For this reason there is no organic acid containing less oxygen in its molecule than there is in carbonic anhydride; every organic acid contains in its molecule at least two atoms of oxygen. In order to express the relation between carbonic acid, H_{2}CO_{3}, and organic acids, and in order to understand the reason of the acidity of these latter, it is simplest to turn to that law of substitution which shows (Chapter VI.) the relation between the hydrogen and oxygen compounds of nitrogen, and permits us (Chapter VIII.) to regard all hydrocarbons as derived from methane. If we have a given organic compound, A, which has not the properties of an acid, but contains hydrogen connected to carbon, as in hydrocarbons, then ACO_{2} will be a monobasic organic acid, A2CO_{2} a bibasic, A3CO_{2} a tribasic, and so on--that is, each molecule of CO_{2} transforms one atom of hydrogen into that state in which it may be replaced by metals, as in acids. This furnishes a direct proof that in organic acids it is necessary to recognise the group HCO_{2}, or carboxyl. If the addition of CO_{2} raises the basicity, the removal of CO_{2} lowers it. Thus from the bibasic oxalic acid, C_{2}H_{2}O_{4}, or phthalic acid, C_{8}H_{6}O_{4}, by eliminating CO_{2} (easily effected experimentally) we obtain the monobasic formic acid, CH_{2}O_{2}, or benzoic acid, C_{7}H_{6}O_{2}, respectively. The nature of carboxyl is directly explained by the law of substitution. Judging from what has been stated in Chapters VI. and VIII. concerning this law, it is evident that CO_{2} is CH_{4} with the exchange of H_{4} for O_{2}, and that the hydrate of carbonic anhydride, H_{2}CO_{3}, is CO(OH)_{2}, that is, methane, in which two parts of hydrogen are replaced by two parts of the water radical (OH, hydroxyl) and the other two by oxygen. Therefore the group CO(OH), or carboxyl, HCO_{2}, is a part of carbonic acid, and is equivalent to (OH), and therefore also to H. That is, it is a univalent residue of carbonic acid capable of replacing one atom of hydrogen. Carbonic acid itself is a bibasic acid, both hydrogen atoms in it being replaceable by metals, therefore carboxyl, which contains one of the hydrogen atoms of carbonic acid, represents a group in which the hydrogen is exchangeable for metals. And therefore if 1, 2 ... _n_ atoms of non-metallic hydrogen are exchanged 1, 2 ... _n_ times for carboxyl, we ought to obtain 1, 2 ... _n_-basic acids. _Organic acids are the products of the carboxyl substitution in hydrocarbons._[18 bis] If in the saturated hydrocarbons, C_{n}H_{2n + 2}, one part of hydrogen is replaced by carboxyl, the monobasic saturated (or fatty) acids, C_{n}H_{2n + 1}(CO_{2}H), will be obtained, as, for instance, formic acid, HCO_{2}H, acetic acid, CH_{2}CO_{2}H, ... stearic acid, C_{17}H_{35}CO_{2}H, &c. The double substitution will give bibasic acids, C_{n}H_{2n}(CO_{2}H)(CO_{2}H); for instance, oxalic acid _n_ = 0, malonic acid _n_ = 1, succinic acid _n_ = 2, &c. To benzene, C_{6}H_{6} correspond benzoic acid, C_{6}H_{5}(CO_{2}H), phthalic acid (and its isomerides), C_{6}H_{4}(CO_{2}H)_{2}, up to mellitic acid, C_{6}(CO_{2}H)_{6}, in all of which the basicity is equal to the number of carboxyl groups. As many isomerides exist in hydrocarbons, it is readily understood not only that such can exist also in organic acids, but that their number and structure may be foreseen. This complex and most interesting branch of chemistry is treated separately in organic chemistry. [18] Percarbonic acid, H_{2}CO_{4} (= H_{2}CO_{3} + O) is supposed by A. Bach (1893) to be formed from carbonic acid in the action of light upon plants, (in the same manner as, according to the above scheme, sulphuric acid from sulphurous) with the formation of carbon, which remains in the form of hydrates of carbon: 3H_{2}CO_{3} = 2H_{2}CO_{4} + CH_{2}O. This substance CH_{2}O expresses the composition of formic aldehyde which, according to Baeyer, by polymerisation and further changes, gives other hydrates of carbon and forms the first product which is formed in plants from CO_{2}. And Berthelot (1872) had already, at the time of the discovery of persulphuric (Chapter XX.) and pernitric (Chapter VI., Note 26) acids pointed out the formation of the unstable percarbonic anhydride, CO_{3}. Thus, notwithstanding the hypothetical nature of the above equation, it may be admitted all the more as it explains the comparative abundance of peroxide of hydrogen (Schöne, Chapter IV.) in the air, and this also at the period of the most energetic growth of plants (in July), because percarbonic acid should like all peroxides easily give H_{2}O_{2}. Besides which Bach (1894) showed that, in the first place, traces of formic aldehyde and oxidising agents (CO_{3} or H_{2}O_{2}) are formed under the simultaneous action of CO_{2} and sunlight upon a solution containing a salt of uranium (which is oxidised), and diethylaniline (which reacts with CH_{2}O), and secondly, that by subjecting BaO_{2}, shaken up in water, to the action of a stream of CO_{2} in the cold, extracting (also in the cold) with ether, and then adding an alcoholic solution of NaHO, crystalline plates of a sodium salt may be obtained, which with water evolve oxygen and leave sodium carbonate; they are therefore probably the per-salt. All these facts are of great interest and deserve further verification and elaboration. [18 bis] If CO_{2} is the anhydride of a bibasic acid, and carboxyl corresponds with it, replacing the hydrogen of hydrocarbons, and giving them the character of comparatively feeble acids, then SO_{3} is the anhydride of an energetic bibasic acid, and _sulphoxyl_, SO_{2}(OH), corresponds with it, being capable of replacing the hydrogen of hydrocarbons, and forming comparatively energetic _sulphur oxyacids_ (_sulphonic acids_); for instance, C_{6}H_{5}(COOH), benzoic acid, and C_{6}H_{5}(SO_{2}OH), benzenesulphonic acid, are derived from C_{6}H_{6}. As the exchange of H for methyl, CH_{3}, is equivalent to the addition of CH_{2}, the exchange of carboxyl, COOH, is equivalent to the addition of CO_{2}; so the exchange of H for sulphoxyl is equivalent to the addition of SO_{3}. The latter proceeds directly, for instance: C_{6}H_{6} + SO_{3} = C_{6}H_{5}(SO_{2}OH). As accordingding to the determinations of Thomsen, the heat of combustion of the _vapours_ of acids RCO_{2} is known where R is a hydrocarbon, and the heat of combustion of the hydrocarbons R themselves, it may be seen that the formation of acids, RCO_{2}, from R + CO_{2}, is always accompanied by a _small_ absorption or development of heat. We give the heats of combustion in thousands of calories, referred to the molecular weights of the substances:-- R = H_{2} CH_{4} C_{2}H_{6} C_{6}H_{6} 68·4 212 370 777 RCO_{2} = 69·4 225 387 766 Thus H_{2}, corresponds with formic acid, CH_{2}O_{2}; benzene, C_{6}H_{6}, with benzoic acid, C_{7}H_{6}O_{2}. The data for the latter are taken from Stohmann, and refer to the solid condition. For formic acid Stohmann gives the heat of combustion as 59,000 calories in a liquid state, but in a state of vapour, 64·6 thousand units, which is much less than according to Thomsen. _Carbonic Oxide._--This gas is formed whenever the combustion of organic substances takes place in the presence of a large excess of incandescent charcoal; the air first burns the carbon into carbonic anhydride, but this in penetrating through the red-hot charcoal is transformed into carbonic oxide, CO_{2} + C = 2CO. By this reaction carbonic oxide is prepared by passing carbonic anhydride through charcoal at a red heat. It may be separated from the excess of carbonic anhydride by passing it through a solution of alkali, which does not absorb carbonic oxide. This reduction of carbonic anhydride explains why carbonic oxide is formed in ordinary clear fires, where the incoming air passes over a large surface of heated coal. A blue flame is then observed burning above the coal; this is the burning carbonic oxide. When charcoal is burnt in stacks, or when a thick layer of coal is burning in a brazier, and under many similar circumstances, carbonic oxide is also formed. In metallurgical processes, for instance when iron is smelted from the ore, very often the same process of conversion of carbonic anhydride into carbonic oxide occurs, especially if the combustion of the coal be effected in high, so-called blast, furnaces and ovens, where the air enters at the lower part and is compelled to pass through a thick layer of incandescent coal. In this way, also, combustion with flame may be obtained from those kinds of fuel which under ordinary conditions burn without flame: for instance, anthracite, coke, charcoal. Heating by means of a gas-producer--that is, an apparatus producing combustible carbonic oxide from fuel--is carried on in the same manner.[19] In transforming one part of charcoal into carbonic oxide 2,420 heat units are given out, and on burning to carbonic anhydride 8,080 heat units. It is evident that on transforming the charcoal first into carbonic oxide we obtain a gas which in burning is capable of giving out 5,660 heat units for one part of charcoal. This preparatory transformation of fuel into carbonic oxide, or producer gas containing a mixture of carbonic oxide (about 1/3 by volume) and nitrogen (2/3 volume), in many cases presents most important advantages, as it is easy to completely burn gaseous fuel without an excess of air, which would lower the temperature.[20] In stoves where solid fuel is burnt it is impossible to effect the complete combustion of the various kinds of fuel without admitting an excess of air. Gaseous fuel, such as carbonic oxide, is easily completely mixed with air and burnt without excess of it. If, in addition to this, the air and gas required for the combustion be previously heated by means of the heat which would otherwise be uselessly carried off in the products of combustion (smoke)[21] it is easy to reach a high temperature, so high (about 1,800°) that platinum may be melted. Such an arrangement is known as a _regenerative furnace_.[22] By means of this process not only may the high temperatures indispensable in many industries be obtained (for instance, glass-working, steel-melting, &c.), but great advantage also[23] is gained as regards the quantity of fuel, because the transmission of heat to the object to be heated, other conditions being equal, is determined by the difference of temperatures. [19] [Illustration: FIG. 63.--Gas-producer for the formation of carbon monoxide for heating purposes.] In gas-producers all carbonaceous fuels are transformed into inflammable gas. In those which (on account of their slight density and large amount of water, or incombustible admixtures which absorb heat) are not as capable of giving a high temperature in ordinary furnaces--for instance, fir cones, peat, the lower kinds of coal, &c.--the same gas is obtained as with the best kinds of coal, because the water condenses on cooling, and the ashes and earthy matter remain in the gas-producer. The construction of a gas-producer is seen from the accompanying drawing. The fuel lies on the fire-bars O, the air enters through them and the ash-hole (drawn by the draught of the chimney of the stove where the gas burns, or else forced by a blowing apparatus), the quantity of air being exactly regulated by means of valves. The gases formed are then led by the tube V, provided with a valve, into the gas main U. The addition of fuel ought to proceed in such a way as to prevent the generated gas escaping; hence the space A is kept filled with the combustible material and covered with a lid. [20] An excess of air lowers the temperature of combustion, because it becomes heated itself, as explained in Chapter III. In ordinary furnaces the excess of air is three or four times greater than the quantity required for perfect combustion. In the best furnaces (with fire-bars, regulated air supply, and corresponding chimney draught) it is necessary to introduce twice as much air as is necessary, otherwise the smoke contains much carbonic oxide. [21] If in manufactories it is necessary, for instance, to maintain the temperature in a furnace at 1,000°, the flame passes out at this or a higher temperature, and therefore much fuel is lost in the smoke. For the draught of the chimney a temperature of 100° to 150° is sufficient, and therefore the remaining heat ought to be utilised. For this purpose the flues are carried under boilers or other heating apparatus. The preparatory heating of the air is the best means of utilisation when a high temperature is desired (_see_ Note 22). [22] Regenerative furnaces were introduced by the Brothers Siemens about the year 1860 in many industries, and mark a most important progress in the use of fuel, especially in obtaining high temperatures. The principle is as follows: The products of combustion from the furnace are led into a chamber, I, and heat up the bricks in it, and then pass into the outlet flue; when the bricks are at a red heat the products of combustion are passed (by altering the valves) into another adjoining chamber, II, and air requisite for the combustion of the generator gases is passed through I. In passing round about the incandescent bricks the air is heated, and the bricks are cooled--that is, the heat of the smoke is returned into the furnace. The air is then passed through II, and the smoke through I. The regenerative burners for illuminating gas are founded on this same principle, the products of combustion heat the incoming air and gas, the temperature is higher, the light brighter, and an economy of gas is effected. Absolute perfection in these appliances has, of course, not yet been attained; further improvement is still possible, but dissociation imposes a limit because at a certain high temperature combinations do not ensue, possible temperatures being limited by reverse reactions. Here, as in a number of other cases, the further investigation of the matter must prove of direct value from a practical point of view. [23] At first sight it appears absurd, useless, and paradoxical to lose nearly one-third of the heat which fuel can develop, by turning it into gas. Actually the advantage is enormous, especially for producing high temperatures, as is already seen from the fact that fuels rich in oxygen (for instance, wood) when damp are unable, with any kind of hearth whatever, to give the temperature required for glass-melting or steel-casting, whilst in the gas-producer they furnish exactly the same gas as the driest and most carbonaceous fuel. In order to understand the principle which is here involved, it is sufficient to remember that a large amount of heat, but having a low temperature, is in many cases of no use whatever. We are unable here to enter into all the details of the complicated matter of the application of fuel, and further particulars must be sought for in special technical treatises. The following footnotes, however, contain certain fundamental figures for calculations concerning combustion. The transformation of carbonic anhydride, by means of charcoal, into carbonic oxide (C + CO_{2} = CO + CO) is considered a reversible reaction, because at a high temperature the carbonic oxide splits up into carbon and carbonic anhydride, as Sainte-Claire Deville showed by using the method of the 'cold and hot tube.' Inside a tube heated in a furnace another thin metallic (silvered copper) tube is fitted, through which a constant stream of cold water flows. The carbonic oxide coming into contact with the heated walls of the exterior tube forms charcoal, and its minute particles settle in the form of lampblack on the lower side of the cold tube, and, since they are cooled, do not act further on the oxygen or carbonic anhydride formed.[24] A series of electric sparks also decomposes carbonic oxide into carbonic anhydride and carbon, and if the carbonic anhydride be removed by alkali complete decomposition may be obtained (Deville).[24 bis] Aqueous vapour, which is so similar to carbonic anhydride in many respects, acts, at a high temperature, on charcoal in an exactly similar way, C + H_{2}O = H_{2} + CO. From 2 volumes of carbonic anhydride with charcoal 4 volumes of carbonic oxide (2 molecules) are obtained, and precisely the same from 2 volumes of water vapour with charcoal 4 volumes of a gas consisting of hydrogen and carbonic oxide (H_{2} + CO) are formed. This mixture of combustible gases is called _water gas_.[25] But aqueous vapour (and only when strongly superheated, otherwise it cools the charcoal) only acts on charcoal to form a large amount of carbonic oxide at a very high temperature (at which carbonic anhydride dissociates); it begins to react at about 500°, forming carbonic anhydride according to the equation C + 2H_{2}O = CO_{2} + 2H_{2}. Besides this, carbonic oxide on splitting up forms carbonic anhydride, and therefore water gas always contains a mixture[26] in which hydrogen predominates, the volume of carbonic oxide being comparatively less, whilst the amount of carbonic anhydride increases as the temperature of the reaction decreases (generally it is more than 3 per cent.) [24] The first product of combustion of charcoal is always carbonic anhydride, and not carbonic oxide. This is seen from the fact that with a shallow layer of charcoal (less than a decimetre if the charcoal be closely packed) carbonic oxide is not formed at all. It is not even produced with a deep layer of charcoal if the temperature is not above 500°, and the current of air or oxygen is very slow. With a rapid current of air the charcoal becomes red-hot, and the temperature rises, and then carbonic oxide appears (Lang 1888). Ernst (1891) found that below 995° carbonic oxide is always accompanied by CO_{2}, and that the formation of CO_{2} begins about 400°. Naumann and Pistor determined that the reaction of carbonic anhydride with carbon commences at about 550°, and that between water and carbon at about 500°. At the latter temperature carbonic anhydride is formed, and only with a rise of temperature is carbonic oxide formed (Lang) from the action of the carbonic anhydride on the carbon, and from the reaction CO_{2} + H_{2} = CO + H_{2}O. Rathke (1881) showed that at no temperature whatever is the reaction as expressed by the equation CO_{2} + C = 2CO_{2}, complete; a part of the carbonic anhydride remains, and Lang determined that at about 1,000° not less than 3 p.c. of the carbonic anhydride remains untransformed into carbonic oxide, even after the action has been continued for several hours. The endothermal reactions, C + 2H_{2}O = CO_{2} +2H_{2}, and CO + H_{2}O = CO_{2} + H_{2}, are just as incomplete. This is made clear if we note that on the one hand the above-mentioned reactions are all reversible, and therefore bounded by a limit; and, on the other hand, that at about 500° oxygen begins to combine with hydrogen and carbon, and also that the lower limits of dissociation of water, carbonic anhydride, and carbonic oxide lie near one another between 500° and 1,200°. For water and carbonic oxide the lower limit of the commencement of dissociation is unknown, but judging from the published data (according to Le Chatelier, 1888) that of carbonic anhydride may be taken as about 1,050°. Even at about 200° half the carbonic anhydride dissociates if the pressure be small, about 0·001 atmosphere. At the atmospheric pressure, not more than 0·05 p.c. of the carbonic anhydride decomposes. The reason of the influence of pressure is here evidently that the splitting up of carbonic anhydride into carbonic oxide and oxygen is accompanied by an increase in volume (as in the case of the dissociation of nitric peroxide. _See_ Chapter VI., Note 46). As in stoves and lamps, and also with explosive substances, the temperature is not higher than 2,000° to 2,500°, it is evident that although the partial pressure of carbonic anhydride is small, still its dissociation cannot here be considerable, and probably does not exceed 5 p.c. [24 bis] Besides which L. Mond (1890) showed that the powder of freshly reduced metallic nickel (obtained by heating the oxide to redness in a stream of hydrogen) is able, when heated even to 350°, to completely decompose carbonic oxide into CO_{2} and carbon, which remains with the nickel and is easily removed from it by heating in a stream of air. Here 2CO = CO_{2} + C. It should be remarked that heat is evolved in this reaction (Note 25), and therefore that the influence of 'contact' may here play a part. Indeed, this reaction must be classed among the most remarkable instances of the influence of contact, especially as metals analogous to Ni (Fe and Co) do not effect this reaction (_see_ Chapter II., Note 17). [25] A molecular weight of this gas, or 2 volumes CO (28 grams), on combustion (forming CO_{2}) gives out 68,000 heat units (Thomsen 67,960 calories). A molecular weight of hydrogen, H_{2} (or 2 volumes), develops on burning into _liquid_ water 69,000 heat units (according to Thomsen 68,300), but if it forms aqueous vapour 58,000 heat units. Charcoal, resolving itself by combustion into the molecular quantity of CO_{2} (2 volumes), develops 97,000 heat units. From the data furnished by these exothermal reactions it follows: (1) that the oxidation of charcoal into carbonic oxide develops 29,000 heat units; (2) that the reaction C + CO_{2} = 2CO _absorbs_ 39,000 heat units; (3) C + H_{2}O = H_{2} + CO _absorbs_ (if the water be in a state of vapour) 29,000 calories, but if the water be liquid 40,000 calories (almost as much as C + CO_{2}); (4) C + H_{2}O = CO_{2} + 2H_{2} _absorbs_ (if the water be in a state of vapour) 19,000 heat units; (5) the reaction CO + H_{2}O = CO_{2} + H_{2} _develops_ 10,000 heat units if the water be in the state of vapour; and (6) the decomposition expressed by the equation 2CO = C + CO_{2} (Note 24 bis) is accompanied by the _evolution_ of 39,000 units of heat. Hence it follows that 2 volumes of CO or H_{2} burning into CO_{2} or H_{2}O develop almost the same amount of heat, just as also the heat effects corresponding with the equations C + H_{2}O = CO + H_{2} C + CO_{2} = CO + CO are nearly equal. [26] _Water gas_, obtained from steam and charcoal at a white heat, contains about 50 p.c. of hydrogen, about 40 p.c. of carbonic oxide, about 5 p.c. of carbonic anhydride, the remainder being nitrogen from the charcoal and air. Compared with producer gas, which contains much nitrogen, this is a gas much richer in combustible matter, and therefore capable of giving high temperatures, and is for this reason of the greatest utility. If carbonic anhydride could be as readily obtained in as pure a state as water, then CO might be prepared directly from CO_{2} + C, and in that case the utilisation of the heat of the carbon would be the same as in water gas, because CO evolves as much heat as H_{2}, and even more if the temperature of the smoke be over 100°, and the water remains in the form of vapour (Note 25). But producer gas contains a large proportion of nitrogen, so that its effective temperature is below that given by water gas; therefore in places where a particularly high temperature is required (for instance, for lighting by means of incandescent lime or magnesia, or for steel melting, &c.), and where the gas can be easily distributed through pipes, water gas is at present held in high estimation, but when (in ordinary furnaces, re-heating, glass-melting, and other furnaces) a very high temperature is not required, and there is no need to convey the gas in pipes, producer gas is generally preferred on account of the simplicity of its preparation, especially as for water gas such a high temperature is required that the plant soon becomes damaged. There are numerous systems for making water gas, but the American patent of T. Lowe is generally used. The gas is prepared in a cylindrical generator, into which hot air is introduced, in order to raise the coke in it to a white heat. The products of combustion containing carbonic oxide are utilised for superheating steam, which is then passed over the white hot coke. Water gas, or a mixture of hydrogen and carbonic oxide, is thus obtained. Water gas is sometimes called '_the fuel of the future_,' because it is applicable to all purposes, develops a high temperature, and is therefore available, not only for domestic and industrial uses, but also for gas-motors and for lighting. For the latter purpose platinum, lime, magnesia, zirconia, and similar substances (as in the Drummond light, Chapter III.), are rendered incandescent in the flame, or else the gas is _carburetted_--that is, mixed with the vapours of volatile hydrocarbons (generally benzene or naphtha, naphthalene, or simply naphtha gas), which communicate to the pale flame of carbonic oxide and hydrogen a great brilliancy, owing to the high temperature developed by the combustion of the non-luminous gases. As water gas, possessing these properties, may be prepared at central works and conveyed in pipes to the consumers, and as it may be produced from any kind of fuel, and ought to be much cheaper than ordinary gas, it may as a matter of fact be expected that in course of time (when experience shall have determined the cheapest and best way to prepare it) it will not only supplant ordinary gas, but will with advantage everywhere replace the ordinary forms of fuel, which in many respects are inconvenient. At present its consumption spreads principally for lighting purposes, and for use in gas-engines instead of ordinary illuminating gas. In some cases Dowson gas is prepared in producers. This is a mixture of water and producer gases obtained by passing steam into an ordinary producer (Note 19), when the temperature of the carbon has become sufficiently high for the reaction C + H_{2}O = CO + H_{2}. Metals like iron and zinc which at a red heat are capable of decomposing water with the formation of hydrogen, also decompose carbonic anhydride with the formation of carbonic oxide; so both the ordinary products of complete combustion, water and carbonic anhydride, are very similar in their reactions, and we shall therefore presently compare hydrogen and carbonic oxide. The metallic oxides of the above-mentioned metals, when reduced by charcoal, also give carbonic oxide. Priestley obtained it by heating charcoal with zinc oxide. As free carbonic anhydride may be transformed into carbonic oxide, so, in precisely the same way, may that carbonic acid which is in a state of combination; hence, if magnesium or barium carbonates (MgCO_{3} or BaCO_{3}) be heated to redness with charcoal, or iron or zinc, carbonic oxide will be produced--for instance, it is obtained by heating an intimate mixture of 9 parts of chalk and 1 part of charcoal in a clay retort. Many organic substances[27] on being heated, or under the action of various agents, yield carbonic oxide; amongst these are many organic or carboxylic acids. The simplest are formic and oxalic acids. Formic acid, CH_{2}O_{2}, on being heated to 200°, easily decomposes into carbonic oxide and water, CH_{2}O_{2} = CO + H_{2}O.[27 bis] Usually, however, carbonic oxide is prepared in laboratories, not from formic but from oxalic acid, C_{2}H_{2}O_{4}, the more so as formic acid is itself prepared from oxalic acid. The latter acid is easily obtained by the action of nitric acid on starch, sugar, &c.; it is also found in nature. Oxalic acid is easily decomposed by heat; its crystals first lose water, then partly volatilise, but the greater part is decomposed. The decomposition is of the following nature: it splits up into water, carbonic oxide, and carbonic anhydride,[28] C_{2}H_{2}O_{4} = H_{2}O + CO_{2} + CO. This decomposition is generally practically effected by mixing oxalic acid with strong sulphuric acid, because the latter assists the decomposition by taking up the water. On heating a mixture of oxalic and sulphuric acids a mixture of carbonic oxide and carbonic anhydride is evolved. This mixture is passed through a solution of an alkali in order to absorb the carbonic anhydride, whilst the carbonic oxide passes on.[28 bis] [27] The so-called yellow prussiate, K_{4}FeC_{6}N_{6}, on being heated with ten parts of strong sulphuric acid forms a considerable quantity of very pure carbonic oxide quite free from carbonic anhydride. [27 bis] To perform this reaction, the formic acid is mixed with glycerine, because when heated alone it volatilises much below its temperature of decomposition. When heated with sulphuric acid the salts of formic acid yield carbonic oxide. [28] The decomposition of formic and oxalic acids, with the formation of carbonic oxide, considering these acids as carboxyl derivatives, may be explained as follows:--The first is H(COOH) and the second (COOH)_{2}, or H_{2} in which one or both halves of the hydrogen are exchanged for carboxyl; therefore they are equal to H_{2} + CO_{2} and H_{2} + 2CO_{2}; but H_{2} reacts with CO_{2}, as has been stated above, forming CO and H_{2}O. From this it is also evident that oxalic acid on losing CO_{2} forms formic acid, and also that the latter may proceed from CO + H_{2}O, as we shall see further on. [28 bis] Greshoff (1888) showed that with a solution of nitrate of silver, iodoform, CHI_{3}, forms CO according to the equation CHI_{3} + 3AgNO_{3} + H_{2}O = 3AgI + 3HNO_{3} + CO. The reaction is immediate and is complete. In its physical _properties_ carbonic oxide resembles nitrogen; this is explained by the equality of their molecular weights. The absence of colour and smell, the low temperature of the absolute boiling point, -140° (nitrogen, -146°), the property of solidifying at -200° (nitrogen, -202°), the boiling point of -190° (nitrogen, -203°), and the slight solubility (Chapter I., Note 30), of carbonic oxide are almost the same as in those of nitrogen. The chemical properties of both gases are, however, very different, and in these carbonic oxide resembles hydrogen. Carbonic oxide burns with a blue flame, giving 2 volumes of carbonic anhydride from 2 volumes of carbonic oxide, just as 2 volumes of hydrogen give 2 volumes of aqueous vapour. It explodes with oxygen, in the eudiometer, like hydrogen.[29] When breathed it acts as a strong poison, being absorbed by the blood;[30] this explains the action of charcoal fumes, the products of the incomplete combustion of charcoal and other carbonaceous fuels. Owing to its faculty of combining with oxygen, carbonic oxide acts as a powerful reducing agent, taking up the oxygen from many compounds at a red heat, and being itself transformed into carbonic anhydride. The reducing action of carbonic oxide, however, is (like that of hydrogen, Chapter II.) naturally confined to those oxides which easily part with their oxygen--as, for instance, copper oxide--whilst the oxides of magnesium or potassium are not reduced. Metallic iron itself is capable of reducing carbonic anhydride to carbonic oxide, just as it liberates the hydrogen from water. Copper, which does not decompose water, does not decompose carbonic oxide. If a platinum wire heated to 300°, or spongy platinum at the ordinary temperature, be plunged into a mixture of carbonic oxide and oxygen, or of hydrogen and oxygen, the mixture explodes. These reactions are very similar to those peculiar to hydrogen. The following important distinction, however, exists between them--namely: the molecule of hydrogen is composed of H_{2}, a group of elements divisible into two like parts, whilst, as the molecule of carbonic oxide, CO, contains unlike atoms of carbon and oxygen, in none of its reactions of combination can it give two molecules of matter containing its elements. This is particularly noticeable in the action of chlorine on hydrogen and on carbonic oxide respectively; with the former chlorine forms hydrogen chloride, and with the latter it produces the so-called carbonyl chloride, COCl_{2}: that is to say, the molecule of hydrogen, H_{2}, under the action of chlorine divides, forming two molecules of hydrochloric acid, whilst the molecule of carbonic oxide enters in its entirety into the molecule of carbonyl chloride. This characterises the so-called _diatomic_ or _bivalent_ reactions of radicles or _residues_. H is a monatomic residue or radicle, like K, Cl, and others, whilst carbonic oxide, CO, is an indivisible (undecomposable) bivalent radicle, equivalent to H_{2} and not to H, and therefore combining with X_{2} and interchangeable with H_{2}. This distinction is evident from the annexed comparison: HH, hydrogen. CO, carbonic oxide. HCl, hydrochloric acid. COCl_{2}, carbonyl chloride. HKO, potash. CO(KO)_{2}, potassium carbonate. HNH_{2}, ammonia. CO(NH_{2})_{2}, urea. HCH_{3}, methane. CO(CH_{3})_{2}, acetone. HHO, water. CO(HO)_{2}, carbonic acid. [29] It is remarkable that, according to the investigations of Dixon, perfectly dry carbonic oxide does not explode with oxygen when a spark of low intensity is used, but an explosion takes place if there is the slightest admixture of moisture. L. Meyer, however, showed that sparks of an electric discharge of considerable intensity produce an explosion. N. N. Beketoff demonstrated that combustion proceeds and spreads slowly unless there be perfect dryness. I think that this may he explained by the fact that water with carbonic oxide gives carbonic anhydride and hydrogen, but hydrogen with oxygen gives hydrogen peroxide (Chapter VII.), which with carbonic oxide forms carbonic anhydride and water. The water, therefore, is renewed, and again serves the same purpose. But it may be that here it is necessary to acknowledge a simple contact influence. After Dixon had shown the influence of traces of moisture upon the reaction CO + O, many researches were made of a similar nature. The fullest investigation into the influence of moisture upon the course of many chemical reactions was made by Baker in 1894. He showed that with perfect dryness, many chemical transformations (for example, the formation of ozone from oxygen, the decomposition of AgO, KClO_{3} under the action of heat, &c.) proceeds in exactly the same manner as in the presence of moisture; but that in many cases traces of moisture have an evident influence. We may mention the following instances: (1) Dry SO_{3} does not act upon dry CaO or CuO; (2) perfectly dry sal-ammoniac does not give NH_{3} with dry CaO, but simply volatilises; (3) dry NO and O do not react; (4) perfectly dry NH_{3} and HCl do not combine; (5) perfectly dry sal-ammoniac does not dissociate at 350° (Chapter VII., Note 15 bis); and (6) perfectly dry chlorine does not act upon metals, &c. [30] Carbonic oxide is very rapid in its action, because it is absorbed by the blood in the same way as oxygen. In addition to this, the absorption spectrum of the blood changes so that by the help of blood it is easy to detect the slightest traces of carbonic oxide in the air. M. A. Kapoustin found that linseed oil and therefore oil paints, are capable of giving off carbonic oxide while drying (absorbing oxygen). Such monatmic (univalent) residues, X, as H, Cl, Na, NO_{2}, NH_{4}, CH_{3}, CO_{2}H (carboxyl), OH, and others, in accordance with the law of substitution, combine together, forming compounds, XX'; and with oxygen, or in general with diatomic (bivalent) residues, Y--for instance, O, CO, CH_{2}, S, Ca, &c. forming compounds XX´Y; but diatomic residues, Y, sometimes capable of existing separately may combine together, forming YY´ and with X_{2} or XX´, as we see from the transition of CO into CO_{2} and COCl_{2}. This combining power of carbonic oxide appears in many of its reactions. Thus it is very easily absorbed by cuprous chloride, CuCl, dissolved in fuming hydrochloric acid, forming a crystalline compound, COCu_{2}Cl_{2},2H_{2}O, decomposable by water; it combines directly with potassium (at 90°), forming (KCO)_{_n_}[31] with platinum dichloride, PtCl_{2}, with chlorine, Cl_{2}, &c. [31] The molecule of metallic potassium (Scott, 1887), like that of mercury, contains only one atom, and it is probably in virtue of this that the molecules CO and K combine together. But as in the majority of cases potassium acts as a univalent radicle, the polymeride K_{2}C_{2}O_{2} is formed, and probably K_{10}C_{10}O_{10}, because products containing C_{10} are formed by the action of hydrochloric acid. The black mass formed by the combination of carbonic oxide with potassium explodes with great ease, and oxidises in the air. Although Brodie, Lerch, and Joannis (who obtained it in 1873 in a colourless form by means of NH_{3}K, described in Chapter VI., Note 14) have greatly extended our knowledge of this compound, much still remains unexplained. It probably exists in various polymeric and isomeric forms, having the composition (KCO)_{_n_} and (NaCO)_{_n_}. But the most remarkable compounds are (1) the compound of CO with metallic nickel, a colourless volatile liquid, Ni(CO)_{4}, obtained by L. Mond (described in Chapter XXII.) and (2) the compounds of carbonic oxide with the alkalis, for instance with potassium or barium hydroxide, &c.--although it is not directly absorbed by them, as it has no acid properties. Berthelot (1861) showed that potash in the presence of water is capable of absorbing carbonic oxide, but the absorption takes place slowly, little by little, and it is only after being heated for many hours that the whole of the carbonic oxide is absorbed by the potash. The salt CHKO_{2} is obtained by this absorption; it corresponds with an acid found in nature--namely, the simplest organic (carboxylic) acid, _formic acid_, CH_{2}O_{2}. It can be extracted from the potassium salt by means of distillation with dilute sulphuric acid, just as nitric acid is prepared from sodium nitrate. The same acid is found in ants and in nettles (when the stings of the nettles puncture the skin they break, and the corrosive formic acid enters into the body); it is also obtained during the action of oxidising agents on many organic substances; it is formed from oxalic acid, and under many conditions splits up into carbonic oxide and water. In the formation of formic acid from carbonic oxide we observe an example of the synthesis of organic compounds, such as are now very numerous, and are treated of in detail in works on organic chemistry. Formic acid, H(CHO_{2}), carbonic acid, HO(CHO_{2}), and oxalic acid, (CHO_{2})_{2}, are the simple organic or carboxylic acids, R(CHO_{2}) corresponding with HH and HOH. Commencing with carbonic oxide, CO, the formation of carboxylic acids is clearly seen from the fact that CO is capable of combining with X_{2}, that is of forming COX_{2}. If, for instance, one X is an aqueous residue, OH (hydroxyl), and the other X is hydrogen, then the simplest organic acid--formic acid, H(COOH)--is obtained. As all hydrocarbons (Chapter VIII.) correspond with the simplest, CH_{4}, so all organic acids may be considered to proceed from formic acid. In a similar way it is easy to explain the relation to other compounds of carbon of those compounds which contain nitrogen. By way of an example, we will take one of the carboxyl acids, R(CO_{2}H), where R is a hydrocarbon radicle (residue). Such an acid, like all others, will give by combination with NH_{3} an ammoniacal salt, R(CO_{2}NH_{4}). This salt contains the elements for the formation of two molecules of water, and under suitable conditions by the action of bodies capable of taking it up, water may in fact be separated from R(CO_{2}NH_{4}), forming by the loss of one molecule of water, _amides_, RCONH_{2}, and by the loss of two molecules of water, _nitriles_, RCN, otherwise known as _cyanogen compounds_ or _cyanides_.[32] If all the carboxyl acids are united not only by many common reactions but also by a mutual conversion into each other (an instance of which we saw above in the conversion of oxalic acid into formic and carbonic acids) one would expect the same for all the cyanogen compounds also. The common character of their reactions, and the reciprocity of their transformation, were long ago observed by Gay-Lussac, who recognised a common group or radicle (residue) cyanogen, CN, in all of them. The simplest compounds are _hydrocyanic_ or _prussic acid_, HCN, cyanic acid, OHCN, and free cyanogen, (CN)_{2}, which correspond to the three simplest carboxyl acids: formic, HCO_{2}H, carbonic, OHCO_{2}H, and oxalic, (CO_{2}H)_{2}. Cyanogen, like carboxyl, is evidently a monatomic residue and acid, similar to chlorine. As regards the amides RCONH_{2}, corresponding to the carboxyl acids, they contain the ammoniacal residue NH_{2}, and form a numerous class of organic compounds met with in nature and obtained in many ways,[33] but not distinguished by such characteristic peculiarities as the cyanogen compounds. [32] The connection of the cyanogen compounds with the rest of the hydrocarbons by means of carboxyl was enunciated by me, about the year 1860, at the first Annual Meeting of the Russian Naturalists. [33] Thus, for instance, _oxamide_, or the amide of oxalic acid, (CNH_{2}O)_{2}, is obtained in the form of an insoluble precipitate on adding a solution of ammonia to an alcoholic solution of ethyl oxalate, (CO_{2}C_{2}H_{5})_{2}, which is formed by the action of oxalic acid on alcohol: (CHO_{2})_{2} + 2(C_{2}H_{5})OH = 2HOH + (CO_{2}C_{2}H_{5})_{2}. As the nearest derivatives of ammonia, the amides treated with alkalis yield ammonia and form the salt of the acid. The nitriles do not, however, give similar reactions so readily. The majority of amides corresponding to acids have a composition RNH_{2}, and therefore recombine with water with great ease even when simply boiled with it, and with still greater facility in presence of acids or alkalis. Under the action of alkalis the amides naturally give off ammonia, through the combination of water with the amide, when a salt of the acid from which the amide was derived is formed: RNH_{2} + KHO = RKO + NH_{3}. The same reaction takes place with acids, only an ammoniacal salt of the acid is of course formed whilst the acid held in the amide is liberated: RNH_{2} + HCl + H_{2}O = RHO + NH_{4}Cl. Thus in the majority of cases amides easily pass into ammoniacal salts, but they differ essentially from them. No ammoniacal salt sublimes or volatilises unchanged, and generally when heated it gives off water and yields an amide, whilst many amides volatilise without alteration and frequently are volatile crystalline substances which may be easily sublimed. Such, for instance, are the amides of benzoic, formic, and many other organic acids. The reactions and properties of the amides and nitriles of the organic acids are described in detail in books on organic chemistry; we will here only touch upon the simplest of them, and to clearly explain the derivative compounds will first consider the ammoniacal salts and amides of carbonic acid. As carbonic acid is bibasic, its ammonium salts ought to have the following composition: _acid carbonate of ammonium_, H(NH_{4})CO_{3}, and _normal carbonate_, (NH_{4})_{2}CO_{3}; they represent compounds of one or two molecules of ammonia with carbonic acid. The acid salt appears in the form of a non-odoriferous and (when tested with litmus) neutral substance, soluble at the ordinary temperature in six parts of water, insoluble in alcohol, and obtainable in a crystalline form either without water of crystallisation or with various proportions of it. If an aqueous solution of ammonia be saturated with an excess of carbonic anhydride, and then evaporated over sulphuric acid in the bell jar of an air-pump, crystals of this salt are separated. Solutions of all other ammonium carbonates, when evaporated under the air-pump, yield crystals of this salt. A solution of this salt, even at the ordinary temperature, gives off carbonic anhydride, as do all the acid salts of carbonic acid (for instance, NaHCO_{3}), and at 38° the separation of carbonic anhydride takes place with great rapidity. _On losing carbonic anhydride_ and water, the acid salt is converted into the normal salt, 2(NH_{4})HCO_{3} = H_{2}O + CO_{2} + (NH_{4})2CO_{3}; the latter, however, decomposes in solution, and can therefore only be obtained in crystals, (NH_{4})_{2}CO_{3},H_{2}O, at low temperatures, and from solutions containing _an excess of ammonia_ as the product of dissociation of this salt: (NH_{4})_{2}CO_{3} = NH_{3} + (NH_{4})HCO_{3}. But the normal salt,[34] according to the general type, is capable of decomposing _with separation of water_, and forming _ammonium carbamate_, NH_{4}O(CONH_{2}) = (NH_{4})_{2}CO_{3}-H_{2}O; this still further complicates the chemical transformations of the carbonates of ammonium. It is in fact evident that, by changing the ratios of water, ammonia, and carbonic acid, various intermediate salts will be formed containing mixtures or combinations of those mentioned above. Thus the ordinary commercial _carbonate of ammonia_ is obtained by heating a mixture of chalk and sulphate of ammonia (Chapter VI.), or sal-ammoniac, 2NH_{4}Cl + CaCO_{3} = CaCl_{2} + (NH_{4})_{2}CO_{3}. The normal salt, however, through loss of part of the ammonia, partly forms the acid salt, and, partly through loss of water, forms carbamate, and most frequently presents the composition NH_{4}O(CONH_{2}) + 2OH(CO_{2}NH_{4}) = 4NH_{3} + 3CO_{2} + 2H_{2}O. This salt, in parting under various conditions with ammonia, carbonic anhydride, and water, does not present a constant composition, and ought rather to be regarded as a mixture of acid salt and amide salt. The latter must be recognised as entering into the composition of the ordinary carbonate of ammonia, because it contains less water than is required for the normal or acid salt;[35] but on being dissolved in water this salt gives a mixture of acid and normal salts. [34] The acid salt, (NH_{4})HCO_{3}, on losing water ought to form the _carbamic acid_, OH(CNH_{2}O); but it is not formed, which is accounted for by the instability of the acid salt itself. Carbonic anhydride is given off and ammonia is produced, which gives ammonium carbamate. [35] In the normal salt, 2NH_{3} + CO_{2} + H_{2}O, in the acid salt, NH_{3} + CO_{2} + H_{2}O, but in the commercial salt only 2H_{2}O to 3CO_{2}. Each of the two ammoniacal salts of carbonic acid has its corresponding amide. That of the acid salt should be acid, if the water given off takes up the hydrogen of the ammonia, as it should according to the common type of formation of the amides, so that OHCONH_{2}, or _carbamic acid_, is formed from OHCO_{3}NH_{4}. This acid is not known in a free state, but its corresponding ammoniacal salt or _ammonium carbamate_ is known. The latter is easily and immediately formed by mixing 2 volumes of _dry_ ammonia with 1 volume of dry carbonic anhydride, 2NH_{3} + CO_{2} = NH_{4}O(CONH_{2}); it is a solid substance, smells strongly of ammonia, attracts moisture from the air, and decomposes completely at 60°. The fact of this decomposition may be proved[36] by the density of its vapour, which = 13 (H = 1); this exactly corresponds with the density of a mixture of 2 volumes of ammonia and 1 volume of carbonic anhydride. It is easily understood that such a combination will take place with any ammonium carbonate under the action of salts which take up the water--for instance, sodium or potassium carbonate[37]--as in an anhydrous state ammonia and carbonic anhydride only form one compound, CO_{2}2NH_{3}.[38] As the normal ammonium carbonate contains two ammonias, and as the amides are formed with the separation of water at the expense of the hydrogen of the ammonias, so this salt has its symmetrical amide, CO(NH_{2})_{2}. This must be termed carbamide. It is identical with urea, CN_{2}H_{4}O, which, contained in the urine (about 2 per cent. in human urine), is for the higher animals (especially the carnivorous) the ordinary product of excretion[39] and oxidation of the nitrogenous substances found in the organism. If ammonium carbamate be heated to 140° (in a sealed tube, Bazaroff), or if carbonyl chloride, COCl_{2}, be treated with ammonia (Natanson), urea will be obtained, which shows its direct connection with carbonic acid--that is, the presence of carbonic acid and ammonia in it. From this it will be understood how urea during the putrefaction of urine is converted into ammonium carbonate, CN_{2}H_{4}O + H_{2}O = CO_{2} + 2NH_{3}. [36] Naumann determined the following dissociation tensions of the vapour of ammonium carbamate (in millimetres of mercury):-- -10° 0° +10° 20° 30° 40° 50° 60° 5 12 30 62 124 248 470 770 Horstmann and Isambert studied the tensions corresponding to excess of NH_{3} or CO_{2}, and found, as might have been expected, that with such excess the mass of the salt formed (in a solid state) increases and the decomposition (transition into vapour) decreases. [37] Calcium chloride enters into double decomposition with ammonium carbamate. Acids (for instance, sulphuric) take up ammonia, and set free carbonic anhydride; whilst alkalis (such as potash) take up carbonic anhydride and set free ammonia, and therefore, in this case for removing water only sodium or potassium carbonate can be taken. An aqueous solution of ammonium carbamate does not entirely precipitate a solution of CaCl_{2}, probably because calcium carbamate is soluble in water, and all the (NH_{3})_{2}CO_{2} is not converted by dissolving into the normal salt, (NH_{4}O)_{2}CO_{3}. [38] It must be imagined that the reaction takes place at first between equal volumes (Chapter VII.); but then carbamic acid, HO(CNH_{2}O), is produced, which, as an acid, immediately combines with the ammonia, forming NH_{4}O(CNH_{2}O). [39] Urea is undoubtedly a product of the oxidation of complex nitrogenous matters (albumin) of the animal body. It is found in the blood. It is absorbed from the blood by the kidneys. A man excretes about 30 grams of urea per day. As a derivative of carbonic anhydride, into which it is readily converted, urea is in a sense a product of oxidation. Thus urea, both by its origin and decomposition, is an amide of carbonic acid. Representing as it does ammonia (two molecules) in which hydrogen (two atoms) is replaced by the bivalent radicle of carbonic acid, urea retains the property of ammonia of entering into combination, with acids (thus nitric acid forms CN_{2}H_{4}O,HNO_{3}), with bases (for instance, with mercury oxide), and with salts (such as sodium chloride, ammonium chloride), but containing an acid residue it has no alkaline properties. It is soluble in water without change, but at a red heat loses ammonia and forms _cyanic acid_, CNHO,[39 bis] which is a nitrile of carbonic acid--that is to say, is a cyanogen compound, corresponding to the acid ammonium carbonate, OH(CNH_{4}O_{2}), which on parting with 2H_{2}O ought to form cyanic acid, CNOH. Liquid cyanic acid, exceedingly unstable at the ordinary temperatures, gives its stable solid polymer cyanuric acid, O_{3}H_{3}C_{3}N_{3}. Both have the same composition, and they pass one into another at different temperatures. If crystals of cyanuric acid be heated to a temperature, _t_°, then the vapour tension, _p_, in millimetres of mercury (Troost and Hautefeuille) will be: _t._ 160°, 170°, 200°, 250°, 300°, 350° _p._ 56, 68, 130, 220, 430, 1,200 The vapour contains cyanic acid, and, if it be rapidly cooled, it condenses into a mobile volatile liquid (specific gravity at 0° = 1·14). If the liquid cyanic acid be gradually heated, it passes into a new amorphous polymeride (cyamelide), which, on being heated, like cyanuric acid, forms vapours of cyanic acid. If these fumes are heated above 150° they pass directly into cyanuric acid. Thus at a temperature of 350°, the pressure does not rise above 1,200 mm. on the addition of vapours of cyanic acid, because the whole excess is transformed into cyanuric acid. Hence, the above-mentioned figures give the tension of dissociation of cyanuric acid, or the greatest pressure which the vapours of HOCN are able to attain at a given temperature, whilst at a greater pressure, or by the introduction of a larger mass of the substance into a given volume, the whole of the excess is converted into cyanuric acid. The properties of cyanic acid which we have described were principally observed by Wöhler, and clearly show the _faculty of polymerisation of cyanogen compounds_. This is observed in many other cyanogen derivatives, and is to be regarded as the consequence of the above-mentioned explanation of their nature. All cyanogen compounds are ammonium salts, R(CNH_{4}O_{2}), deprived of water, 2H_{2}O; therefore the molecules, RCN, ought to possess the faculty of combining with two molecules of water or with other molecules in exchange for it (for instance, with H_{2}S, or HCl, or 2H_{2}, &c.), and are therefore capable of combining together. The combination of molecules of the same kind to form more complex ones is what is meant by polymerisation.[40] [39 bis] Its polymer, C_{3}N_{3}H_{3}O_{3}, is formed together with it. Cyanic acid is a very unstable, easily changeable liquid, while cyanuric acid is a crystalline solid which is very stable at the ordinary temperature. [40] Just as the aldehydes (such as C_{2}H_{4}O) are alcohols (like C_{2}H_{6}O) which have lost hydrogen and are also capable of entering into combination with many substances, and of polymerising, forming slightly volatile polymerides, which depolymerise on heating. Although there are also many similar phenomena (for instance, the transformation of yellow into red phosphorus, the transition of cinnamene into metacinnamene, &c.) of polymerisation, in no other case are they so clearly and simply expressed as in cyanic acid. The details relating to this must be sought for in treatises on organic and theoretical chemistry. If we touch on certain sides of this question it is principally with the view of showing the phenomenon of polymerisation by typical examples, for it is of more frequent occurrence than was formerly supposed among compounds of several elements. Besidea being a substance very prone to form polymerides, cyanic acid presents many other features of interest, expounded in greater detail in organic chemistry. However we may mention here the production of the cyanates by the oxidation of the metallic cyanides. Potassium cyanate, KCNO, is most often obtained in this way. Solutions of cyanates by the addition of sulphuric acid yield cyanic acid, which, however, immediately decomposes: CNHO + H_{2}O = CO_{2} + NH_{3}. A solution of ammonium cyanate, CN(NH_{4})O, behaves in the same manner, but only in the cold. On being heated it completely changes because it is transformed into urea. The composition of both substances is identical, CN_{2}H_{4}O, but the structure, or disposition of, and connection between, the elements is different: in the ammonium cyanate one atom of nitrogen exists in the form of cyanogen, CN--that is, united with carbon--and the other as ammonium, NH_{4}, but, as cyanic acid contains the hydroxyl radicle of carbonic acid, OH(CN), the ammonium in this salt is united with oxygen. The composition of this salt is best expressed by supposing one atom of the hydrogen in water to be replaced by ammonium and the other by cyanogen--_i.e._ that its composition is not symmetrical--whilst in urea both the nitrogen atoms are symmetrically and uniformly disposed as regards the radicle CO of carbonic acid: CO(NH_{2})_{2}. For this reason, urea is much more stable than ammonium cyanate, and therefore the latter, on being slightly heated in solution, is converted into urea. This remarkable isomeric transformation was discovered by Wöhler in 1828.[41] Formamide, HCONH_{2}, and _hydrocyanic acid_, HCN, as a nitrile, correspond with formic acid, HCOOH, and therefore ammonium formate, HCOONH_{4}, and formamide, when acted on by heat and by substances which take up water (phosphoric anhydride) form hydrocyanic acid, HCN, whilst, under many conditions (for instance, on combining with hydrochloric acid in presence of water), this hydrocyanic acid forms formic acid and ammonia. Although containing hydrogen in the presence of two acid-forming elements--namely, carbon and nitrogen[42]--hydrocyanic acid does not give an acid reaction with litmus (cyanic acid has very marked acid properties); _but it forms salts_, _MCN_, thus presenting the properties of a feeble acid, and for this reason is called an _acid_. The small amount of energy which it has is shown by the fact that the cyanides of the alkali metals--for instance, potassium cyanide (KHO + HCN = H_{2}0 + KCN) in solution have a strongly alkaline reaction.[43] If ammonia be passed over charcoal at a red heat, especially in the presence of an alkali, or if gaseous nitrogen be passed through a mixture of charcoal and an alkali (especially potash, KHO), and also if a mixture of nitrogenous organic substances and alkali be heated to a red heat, in all these cases the alkali metal combines with the carbon and nitrogen, forming a metallic cyanide, MCN--for example, KCN.[43 bis] Potassium cyanide is much used in the arts, and is obtained, as above stated, under many circumstances--as, for instance, in iron smelting, especially with the assistance of wood charcoal, the ash of which contains much potash. The nitrogen of the air, the alkali of the ash, and the charcoal are brought into contact at a high temperature during iron smelting, and therefore, under these conditions, a considerable quantity of potassium cyanide is formed. In practice it is not usual to prepare potassium cyanide directly, but a peculiar compound of it containing potassium, iron, and cyanogen. This compound is potassium ferrocyanide, and is also known as _yellow prussiate of potash_. This saline substance (_see_ Chapter XXII) has the composition K_{4}FeC_{6}N_{6} + 2H_{2}O. The name of cyanogen ([Greek: kuanos]) is derived from the property which this yellow prussiate possesses of forming, with a solution of a ferric salt, FeX_{3}, the familiar pigment Prussian blue. The yellow prussiate is manufactured on a large scale, and is generally used as the source of the other cyanogen compounds. [41] It has an important historical interest, more especially as at that time such an easy preparation of substances occurring in organisms without the aid of organic life was quite unexpected, for they were supposed to be formed under the influence of the forces acting in organisms, and without the latter their formation was considered impossible. And in addition to destroying this illusion, the easy transition of NH_{4}OCN into CO(NH_{2})_{2} is the best example of the passage of one system of equilibrium of atoms into another more stable system. [42] If ammonia and methane (marsh gas) do not show any acid properties, that is in all probability due to the presence of a large amount of hydrogen in both; but in hydrocyanic acid one atom of hydrogen is under the influence of two acid-forming elements. Acetylene, C_{2}H_{2}, which contains but little hydrogen, presents acid properties in certain respects, for its hydrogen is easily replaced by metals. Hydronitrous acid, HN_{3}, which contains little hydrogen, also has the properties of an acid. [43] Solutions of cyanides--for instance, those of potassium or barium--are decomposed by carbonic acid. Even the carbonic anhydride of the air acts in a similar way, and for this reason these solutions do not keep, because, in the first place, free hydrocyanic acid itself decomposes and polymerises, and, in the second place, with alkaline liquids it forms ammonia and formic acid. Hydrocyanic acid does not liberate carbonic anhydride from solutions of sodium or potassium carbonates. But a mixture of solutions of potassium carbonate and hydrocyanic acid yields carbonic anhydride on the addition of oxides like zinc oxide, mercuric oxide, &c. This is due to the great inclination which the cyanides exhibit of forming double salts. For instance, ZnK_{2}(CN)_{4} is formed, which is a soluble double salt. [43 bis] The conversion of the atmospheric nitrogen into cyanogen compounds, although possible, has not yet been carried out on a large scale, and one of the problems for future research should be the discovery of a practical and economical means of converting the atmospheric nitrogen into metallic cyanides, not only because potassium cyanide has found a vast and important use for the extraction of gold from even the poorest ores, but more especially because the cyanides furnish the means for effecting the synthesis of many complex carbon compounds, and the nitrogen contained in cyanogen easily passes into other forms of combination such as ammonia, which is of great importance in agriculture. If four parts of yellow prussiate be mixed with eight parts of water and three parts of sulphuric acid, and the mixture be heated, it decomposes, volatile hydrocyanic acid separating. This was obtained for the first time by Scheele in 1782, but it was only known to him in solution. In 1809 Ittner prepared anhydrous prussic acid, and in 1815 Gay-Lussac finally settled its properties and showed that it contains only hydrogen, carbon, and nitrogen, CNH. If the distillate (a weak solution of HCN) be redistilled, and the first part collected, the anhydrous acid may be prepared from this stronger solution. In order to do this, pieces of calcium chloride are added to the concentrated solution, when the anhydrous acid floats as a separate layer, because it is not soluble in an aqueous solution of calcium chloride. If this layer be then distilled over a new portion of calcium chloride at the lowest temperature possible, the prussic acid may be obtained completely free from water. It is, however, necessary to use the greatest caution in work of this kind, because prussic acid, besides being extremely poisonous, is exceedingly volatile.[44] [44] The mixture of the vapours of water and hydrocyanic acid, evolved on heating yellow prussiate with sulphuric acid, may be passed directly through vessels or tubes filled with calcium chloride. These tubes must be cooled, because, in the first place, hydrocyanic acid easily changes on being heated, and, in the second place, the calcium chloride when warm would absorb less water. The mixture of hydrocyanic acid and aqueous vapour on passing over a long layer of calcium chloride gives up water, and hydrocyanic acid alone remains in the vapour. It ought to be cooled as carefully as possible in order to bring it into a liquid condition. The method which Gay-Lussac employed for obtaining pure hydrocyanic acid consisted in the action of hydrochloric acid gas on mercuric cyanide. The latter may he obtained in a pure state if a solution of yellow prussiate be boiled with a solution of mercuric nitrate, filtered, and crystallised by cooling; the mercuric cyanide is then obtained in the form of colourless crystals, Hg(CN)_{2}. If a strong solution of hydrochloric acid be poured upon these crystals, and the mixture of vapours evolved, consisting of aqueous vapour, hydrochloric acid, and hydrocyanic acid, be passed through a tube containing, first, marble (for absorbing the hydrochloric acid), and then lumps of calcium chloride, on cooling the hydrocyanic acid will be condensed. In order to obtain the latter in an anhydrous form, the decomposition of heated mercury cyanide by hydrogen sulphide may be made use of. Here the sulphur and cyanogen change places, and hydrocyanic acid and mercury sulphide are formed: Hg(CN)_{2} + H_{2}S = 2HCN + HgS. Anhydrous prussic acid is a very mobile and volatile liquid; its specific gravity is 0·697 at 18°; at lower temperatures, especially when mixed with a small quantity of water, it easily congeals; it boils at 26°, and therefore very easily evaporates, and at ordinary temperatures may be regarded as a gas. An insignificant amount, when inhaled or brought into contact with the skin, causes death. It is soluble in all proportions in water, alcohol, and ether: weak aqueous solutions are used in medicine.[45] [45] A weak (up to 2 p.c.) aqueous solution of hydrocyanic acid is obtained by the distillation of certain vegetable substances. The so-called laurel water in particular enjoys considerable notoriety from its containing hydrocyanic acid. It is obtained by the steeping and distillation of laurel leaves. A similar kind of water is formed by the infusion and distillation of bitter almonds. It is well known that bitter almonds are poisonous, and have a peculiar characteristic taste. This bitter taste is due to the presence of a certain substance called amygdalin, which can be extracted by alcohol. This amygdalin decomposes in an infusion of bruised almonds, forming the so-called bitter almond oil, glucose, and hydrocyanic acid: C_{10}H_{27}NO_{11} + H_{2}O = C_{7}H_{6}O + CNH + 2C_{6}H_{12}O_{6} Amygdalin in Water Bitter Hydrocyanic Glucose bitter almonds almond acid oil If after this the infusion of bitter almonds be distilled with water, the hydrocyanic acid and the volatile bitter almond oil are carried over with the aqueous vapour. The oil is insoluble in water, or only sparingly soluble, while the hydrocyanic acid remains as an aqueous solution. Bitter almond water is similar to laurel water, and is used like the former in medicine, naturally only in small quantities because any considerable amount has poisonous effects. Perfectly pure anhydrous hydrocyanic acid keeps without change, just like the weak solutions, but the strong solutions only keep in the presence of other acids. In the presence of many admixtures these solutions easily give a brown polymeric substance, which is also formed in a solution of potassium cyanide. The salts MCN--for instance, potassium, sodium, ammonium--as well as the salts M´´(CN)_{2}--for example, barium, calcium, mercury--are soluble in water, but the cyanides of manganese, zinc, lead, and many others are insoluble in water. They form double salts with potassium cyanide and similar metallic cyanides, an example of which we will consider in a further description of the yellow prussiate. Not only are some of the double salts remarkable for their constancy and comparative stability, but so also are the soluble salt HgC_{2}N_{2}, the insoluble silver cyanide AgCN, and even potassium cyanide in the absence of water. The last salt,[46] when fused, acts as a reducing agent with its elements K and C, and oxidises when fused with lead oxide, forming potassium cyanate, KOCN, which establishes the connection between HCN and OHCN--that is, between the nitriles of formic and carbonic acids--and this connection is the same as that between the acids themselves, since formic acid, on oxidation, yields carbonic acid. Free cyanogen, (CN)_{2} or CNCN, corresponds to hydrocyanic acid in the same manner as free chlorine, Cl_{2} or ClCl, corresponds to hydrochloric acid. This composition, judging from what has been already stated, exactly expresses that of the nitrile of oxalic acid, and, as a matter of fact, oxalate of ammonia and the amide corresponding with it (oxamide, Note 33), on being heated with phosphoric anhydride, which takes up the water, yield _cyanogen_, (CN)_{2}. This substance is also produced by simply heating some of the metallic cyanides. Mercuric cyanide is particularly adapted for this purpose, because it is easily obtained in a pure state and is then very stable. If mercuric cyanide be heated, it decomposes, in like manner to mercury oxide, into metallic mercury and cyanogen: HgC_{2}N_{2} = Hg + C_{2}N_{2}.[47] When cyanogen is formed, part of it always polymerises into a dark brown insoluble substance called _paracyanogen_, capable of forming cyanogen when heated to redness.[48] Cyanogen is a colourless, poisonous gas, with a peculiar smell and easily condensed by cooling into a colourless liquid, insoluble in water and having a specific gravity of 0·86. It boils at about -21°, and therefore cyanogen may be easily condensed into a liquid by a strong freezing mixture. At -35° liquid cyanogen solidifies. The gas is soluble in water and in alcohol to a considerable extent--namely, 1 volume of water absorbs as much as 4-1/2 volumes, and alcohol 23 volumes. Cyanogen resists the action of a tolerably high temperature without decomposing, but under the action of the electric spark the carbon is separated, leaving a volume of nitrogen equal to the volume of the gas taken. As it contains carbon it burns, and the colour of the flame is reddish-violet, which is due to the presence of nitrogen, all compounds of which impart more or less of this reddish-violet hue to the flame. During the combustion of cyanogen, carbonic anhydride and nitrogen are formed. The same products are obtained in the eudiometer with oxygen or by the action of cyanogen on many oxides at a red heat. [46] This salt will be described in Chapter XIII. [47] For the preparation it is necessary to take completely dry mercuric cyanide, because when heated in the presence of moisture it gives ammonia, carbonic anhydride, and hydrocyanic acid. Instead of mercuric cyanide, a mixture of perfectly dry yellow prussiate and mercuric chloride may be used, then double decomposition and the formation of mercuric cyanide take place in the retort. Silver cyanide also disengages cyanogen, on being heated. [47] _Paracyanogen_ is a brown substance (having the composition of cyanogen) which is formed during the preparation of cyanogen by all methods, and remains as a residue. Silver cyanide, on being slightly heated, fuses, and on being further heated evolves a gas; a considerable quantity of paracyanogen remains in the residue. Here it is remarkable that exactly half the cyanogen becomes gaseous, and the other half is transformed into paracyanogen. Metallic silver will be found in the residue with the paracyanogen; it may be extracted with mercury or nitric acid, which does not act on paracyanogen. If paracyanogen be heated in a vacuum it decomposes, forming cyanogen; but here the pressure _p_ for a given temperature _t_ cannot exceed a certain limit, so that the phenomenon presents all the external appearance of a physical transformation into vapour; but, nevertheless, it is a complete change in the nature of the substance, though limited by the _pressure of dissociation_, as we saw before in the transformation of cyanuric into hydrocyanic acid, and as would be expected from the fundamental principles of dissociation. Troost and Hautefeuille (1868) found that for paracyanogen, _t_ = 530° 581° 600° 635° _p_ = 90 143 296 1,089 mm. However, even at 550° part of the cyanogen decomposes into carbon and nitrogen. The reverse transition of cyanogen into paracyanogen commences at 350°, and at 600° proceeds rapidly. And if the transition of the first kind is likened to evaporation, then the reverse transition, or polymerisation, presents a likeness to the transition of vapours into the solid state. The relation of cyanogen to the metallic cyanides is seen not only in the fact that it is formed from mercuric cyanide, but also by its forming cyanide of sodium or potassium on being heated with either of those metals, the sodium or potassium taking fire in the cyanogen. On heating a mixture of hydrogen and cyanogen to 500° (Berthelot),[49] or under the action of the silent discharge (Boilleau), hydrocyanic acid is formed, so that the reciprocity of the transitions does not leave any doubt in the matter that all the nitriles of the organic acids contain cyanogen, just as all the organic acids contain carboxyl and in it the elements of carbonic anhydride. Besides the amides,[50] the nitriles (or cyanogen compounds, RCN), and nitro-compounds (containing the radicle of nitric acid, RNO_{2}), there are a great number of other substances containing at the same time carbon and nitrogen, particulars of which must be sought for in special works on organic chemistry. [49] Cyanogen (like chlorine) is absorbed by a solution of sodium hydroxide, sodium cyanide and cyanate being produced: C_{2}N_{2} + 2NaHO = NaCN + CNNaO + H_{2}O. But the latter salt decomposes relatively easily, and moreover part of the cyanogen liberated by heat from its compounds undergoes a more complex transformation. [50] If, in general, compounds containing the radicle NH_{2} are called amides, some of the _amines_ ought to be ranked with them; namely, the hydrocarbons C_{_n_}H_{2_m_}, in which part of the hydrogen is replaced by NH_{2}; for instance, methylamine, CH_{3}NH_{2}, aniline, C_{6}H_{5}NH_{2}, &c. In general the amines may be represented as ammonia in which part or all of the hydrogen is replaced by hydrocarbon radicles--as, for example, trimethylamine, N(CH_{3})_{3}. They, like ammonia, combine with acids and form crystalline salts. Analogous substances are sometimes met with in nature, and bear the general name of _alkaloids_; such are, for instance, quinine in cinchona bark, nicotine in tobacco, &c. CHAPTER X SODIUM CHLORIDE--BERTHOLLET'S LAWS--HYDROCHLORIC ACID In the preceding chapters we have become acquainted with the most important properties of the four elements, hydrogen, oxygen, nitrogen, and carbon. They are sometimes termed the _organogens_, because they enter into the composition of organic substances. Their mutual combinations may serve as types for all other chemical compounds--that is, they present the same atomic relations (types, forms, or grades of combinations) as those in which the other elements also combine together. Hydrogen, HH, or, in general, HR. Water, H_{2}O, " " H_{2}R. Ammonia, H_{3}N, " " H_{3}R. Marsh gas, H_{4}C, " " H_{4}R. One, two, three, and four atoms of hydrogen enter into these molecules for one atom of another element. No compounds of one atom of oxygen with three or four atoms of hydrogen are known; hence the atom of oxygen does not possess certain properties which are found in the atoms of carbon and nitrogen. The faculty of an element to form a compound of definite composition with hydrogen (or an element analogous to it) gives the possibility of foretelling the composition of many other of its compounds. Thus, if we know that an element, M, combines with hydrogen, forming, by preference, a gaseous substance such as HM, but not forming H_{2}M, H_{3}M, H_{n}M_{m}, then we must conclude, on the basis of the law of substitution, that this element will give compounds M_{2}O, M_{3}N, MHO, MH_{3}C, &c. Chlorine is an example of this kind. If we know that another element, R, like oxygen, gives with hydrogen a molecule H_{2}R, then we may expect that it will form compounds similar to hydrogen peroxide, the metallic oxides, carbonic anhydride, or carbonic oxide, and others. Sulphur is an instance of this kind. Hence the elements may be classified according to their resemblance to hydrogen, oxygen, nitrogen, and carbon, and in conformity with this analogy it is possible to foretell, if not the properties (for example, the acidity or basicity), at any rate the composition,[1] of some of their compounds. This forms the substance of _the conception of the valency or atomicity of the elements_. Hydrogen is taken as the representative of the univalent elements, giving compounds, RH, R(OH), R_{2}O, RCl, R_{3}N, R_{4}C, &c. Oxygen, in that form in which it gives water, is the representative of the bivalent elements, forming RH_{2}, RO, RCl_{2}, RHCl, R(OH)Cl, R(OH)_{2}, R_{2}C, RCN, &c. Nitrogen in ammonia is the representative of the trivalent elements, giving compounds RH_{3}, R_{2}O_{3}, R(OH)_{3}, RCl_{3}, RN, RHC, &c. In carbon are exemplified the properties of the quadrivalent elements, forming RH_{4}, RO_{2}, RO(OH)_{2}, R(OH)_{4}, RHN, RCl_{4}, RHCl_{3}, &c. We meet with these _forms of combination_, or degrees of union of atoms, in all other elements, some being analogous to hydrogen, others to oxygen, and others to nitrogen or to carbon. But besides these quantitative analogies or resemblances, which are foretold by the law of substitution (Chapter VI.), there exist among the elements qualitative analogies and relations which are not fully seen in the compounds of the elements which have been considered, but are most distinctly exhibited in the formation of bases, acids, and salts of different types and properties. Therefore, for a complete study of the nature of the elements and their compounds it is especially important to become acquainted with the salts, as substances of a peculiar character, and with the corresponding acids and bases. Common table salt, or sodium chloride, NaCl, may in every respect be taken as a type of salts in general, and we will therefore pass to the consideration of this substance, and of hydrochloric acid, and of the base sodium hydroxide, formed by the non-metal chlorine and the metal sodium, which correspond with it. [1] But it is impossible to foretell all the compounds formed by an element from its atomicity or valency, because the atomicity of the elements is variable, and furthermore this variability is not identical for different elements. In CO_{2}, COX_{2}, CH_{4}, and the multitude of carbon compounds corresponding with them, the C is quadrivalent, but in CO either the carbon must be taken as bivalent or the atomicity of oxygen be accounted as variable. Moreover, carbon is an example of an element which preserves its atomicity to a greater degree than most of the other elements. Nitrogen in NH_{3}, NH_{2}(OH), N_{2}O_{3}, and even in CNH, must be considered as trivalent, but in NH_{4}Cl, NO_{2}(OH), and in all their corresponding compounds it is necessarily pentavalent. In N_{2}O, if the atomicity of oxygen = 2, nitrogen has an uneven atomicity (1, 3, 5), whilst in NO it is bivalent. If sulphur be bivalent, like oxygen, in many of its compounds (for example, H_{2}S, SCl_{2}, KHS, &c.), then it could not be foreseen from this that it would form SO_{2}, SO_{3}, SCl_{4}, SOCl_{2}, and a series of similar compounds in which its atomicity must be acknowledged as greater than 2. Thus SO_{2}, sulphurous anhydride, has many points in common with CO_{2}, and if carbon be quadrivalent then the S in SO_{2} is quadrivalent. Therefore the principle of atomicity (valency) of the elements cannot be considered established as the basis for the study of the elements, although it gives an easy method of grasping many analogies. I consider the four following as the chief obstacles to acknowledging the atomicity of the elements as a primary conception for the consideration of the properties of the elements: 1. Such univalent elements as H, Cl, &c., appear in a free state as molecules H_{2}, Cl_{2}, &c., and are consequently like the univalent radicles CH_{3}, OH, CO_{2}H, &c., which, as might be expected, appear as C_{2}H_{6}, O_{2}H_{2}, C_{2}O_{4}H_{2} (ethane, hydrogen peroxide, oxalic acid), whilst on the other hand, potassium and sodium (perhaps also iodine at a high temperature) contain only one atom, K, Na, in the molecule in a free state. Hence it follows that _free affinities_ may exist. Granting this, nothing prevents the assumption that free affinities exist in all unsaturated compounds; for example, two free affinities in NH_{3}. If such instances of free affinities be admitted, then all the possible advantages to be gained by the application of the doctrine of atomicity (valency) are lost. 2. There are instances--for example, Na_{2}H--where univalent elements are combined in molecules which are more complex than R_{2}, and form molecules, R_{3}, R_{4}, &c.; this may again be either taken as evidence of the existence of free affinities, or else necessitates such primary univalent elements as sodium and hydrogen being considered as variable in their atomicity. 3. The periodic system of the elements, with which we shall afterwards become acquainted, shows that there is a law or rule for the variation of the forms of oxygen and hydrogen compounds; chlorine is univalent with respect to hydrogen, and septavalent with respect to oxygen; sulphur is bivalent to hydrogen, and sexavalent to oxygen; phosphorus is trivalent to hydrogen and pentavalent in respect to oxygen--the sum is in every case equal to 8. Only carbon and its analogues (for example, silicon) are quadrivalent to both hydrogen and oxygen. Hence the power of the elements to change their atomicity is an essential part of their nature, and therefore constant valency cannot he considered as a fundamental property. 4. Crystallo-hydrates (for instance, NaCl,2H_{2}O, or NaBr,2H_{2}O), double salts (such as PtCl_{4},2KCl,H_{2}SiF_{6}, &c.), and similar complex compounds (and, according to Chap. I., solutions also) demonstrate the capacity not only of the elements themselves, but also of their saturated and limiting compounds, of entering into further combination. Therefore the admission of a definite limited atomicity of the elements includes in itself an admission of limitation which is not in accordance with the nature of chemical reactions. _Sodium chloride_, NaCl, the familiar table salt, occurs, although in very small quantities, in all the primary formations of the earth's crust,[2] from which it is washed away by the atmospheric waters; it is contained in small quantities in all waters flowing through these formations, and is in this manner conveyed to the oceans and seas. The immense mass of salt in the oceans has been accumulated by this process from the remote ages of the earth's creation, because the water has evaporated from them while the salt has remained in solution. The salt of sea water serves as the source not only for its direct extraction, but also for the formation of other masses of workable salt, such as rock salt, and of saline springs and lakes.[2 bis] [2] The primary formations are those which do not bear any distinct traces of having been deposited from water (have not a stratified formation and contain no remains of animal or vegetable life), occur under the sedimentary formations of the earth, and are everywhere uniform in composition and structure, the latter being generally distinctly crystalline. If it be assumed that the earth was originally in a molten condition, the first primary formations are those which formed the first solid crust of the earth. But even with this hypothesis of the earth's origin, it is necessary to admit that the first aqueous deposits must have caused a change in the original crust of the earth, and therefore under the head of primary formations must be understood the most ancient of the products of decomposition (mostly by atmospheric, aqueous, and organic agency, &c.), from which all the rocks and substances of the earth's surface have arisen. In speaking of the origin of one or another substance, we can only, on the basis of facts, descend to the primary formations, of which granite, gneiss, and trachyte may be taken as examples. [2 bis] Chloride of sodium has been found to occur in the atmosphere in the form of a fine dust; in the lower strata it is present in larger quantities than in the upper, so that the rain water falling on mountains contains less NaCl than that falling in valleys. Müntz (1891) found that a litre of rain water collected on the summit of the Pic du Midi (2,877 metres above the sea level) contained 0·34 milligram of chloride of sodium, while a litre of rain collected from the valley contained 2·5-7·6 milligrams. The extraction of salt _from sea water_ is carried on in several ways. In southern climes, especially on the shores of the Atlantic Ocean and the Mediterranean and Black Seas, the summer heats are taken advantage of. A convenient low-lying sea shore is chosen, and a whole series of basins, communicating with each other, are constructed along it. The upper of these basins are filled with sea water by pumping, or else advantage is taken of high tides. These basins are sometimes separated from the sea by natural sand-banks (limans) or by artificial means, and in spring the water already begins to evaporate considerably. As the solution becomes more concentrated, it is run into the succeeding basins, and the upper ones are supplied with a fresh quantity of sea water, or else an arrangement is made enabling the salt water to flow by degrees through the series of basins. It is evident that the beds of the basins should be as far as possible impervious to water, and for this purpose they are made of beaten clay. The crystals of salt begin to separate out when the concentration attains 28 p.c. of salt (which corresponds to 28° of Baumé's hydrometer). They are raked off, and employed for all those purposes to which table salt is applicable. In the majority of cases only the first half of the sodium chloride which can be separated from the sea water is extracted, because the second half has a bitter taste from the presence of magnesium salts which separate out together with the sodium salt. But in certain localities--as, for instance, in the estuary of the Rhone, on the island of Camarga[3]--the evaporation is carried on to the very end, in order to obtain those magnesium and potassium salts which separate out at the end of the evaporation of sea water. Various salts are separated from sea water in its evaporation. From 100 parts of sea water there separates out, by natural and artificial evaporation, about one part of tolerably pure table salt at the very commencement of the operation; the total amount held in solution being about 2-1/2 p.c. The remaining portion separates out intermixed with the bitter salts of magnesium which, owing to their solubility and the small amount in which they are present (less than 1 p.c.), only separate out, in the first crystallisations, in traces. Gypsum, or calcium sulphate, CaSO_{4},2H_{2}O, because of its sparing solubility, separates together with or even before the table salt. When about half of the latter has separated, then a mixture of table salt and magnesium sulphate separates out, and on still further evaporation the chlorides of potassium and magnesium begin to separate in a state of combination, forming the double salt KMgCl_{3},6H_{2}O, which occurs in nature as _carnallite_.[4] After the separation of this salt from sea water, there remains a mother liquor containing a large amount of magnesium chloride in admixture with various other salts.[5] The extraction of sea salt is usually carried on for the purpose of procuring table salt, and therefore directly it begins to separate mixed with a considerable proportion[6] of magnesium salts (when it acquires a bitter taste) the remaining liquor is run back into the sea. [3] The extraction of the potassium salts (or so-called summer salts) was carried on at the Isle of Camarga about 1870, when I had occasion to visit that spot. At the present time the deposits of Stassfurt provide a much cheaper salt, owing to the evaporation and separation of the salt being carried on there by natural means and only requiring a treatment and refining, which is also necessary in addition for the 'summer salt' obtained from sea-water. [4] The double salt KCl,MgCl_{2} is a crystallohydrate of KCl and MgCl_{2}, and is only formed from solutions containing an excess of magnesium chloride, because water decomposes this double salt, extracting the more soluble magnesium chloride from it. [5] Owing to the fundamental property of salts of interchanging their metals, it cannot be said that sea water contains this or that salt, but only that it contains certain amounts of certain metals M (univalent like Na and K, and bivalent like Mg and Ca), and haloids X (univalent like Cl, Br, and bivalent like SO_{4}, CO_{3}), which are disposed in every possible kind of grouping; for instance, K as KCl, KBr, K_{2}SO_{4}, Mg as MgCl_{2}, MgBr_{2}, MgSO_{4}, and so on for all the other metals. In evaporation different salts separate out consecutively only because they reach saturation. A proof of this may be seen in the fact that a solution of a mixture of sodium chloride and magnesium sulphate (both of which salts are obtained from sea water, as was mentioned above), when evaporated, deposits crystals of these salts, but when refrigerated (if the solution be sufficiently saturated) the salt Na_{2}SO_{4},10H_{2}O is first deposited because it is the first to arrive at saturation at low temperatures. Consequently this solution contains MgCl_{2} and Na_{2}SO_{4}, besides MgSO_{4} and NaCl. So it is with sea water. [6] The salt extracted from water is piled up in heaps and left exposed to the action of rain water, which purifies it, owing to the water becoming saturated with sodium chloride and then no longer dissolving it, but washing out the impurities. The same process which is employed for artificially obtaining salt in a crystalline form from sea water has been repeatedly accomplished during the geological evolution of the earth on a gigantic scale; upheavals of the earth have cut off portions of the sea from the remainder (as the Dead Sea was formerly a part of the Mediterranean, and the Sea of Aral of the Caspian), and their water has evaporated and formed (if the mass of the inflowing fresh water were less than that of the mass evaporated) deposits of _rock salt_. It is always accompanied by gypsum, because the latter is separated from sea water with or before the sodium chloride. For this reason rock salt may always be looked for in those localities where there are deposits of gypsum. But inasmuch as the gypsum remains on the spot where it has been deposited (as it is a sparingly soluble salt), whilst the rock salt (as one which is very soluble) may be washed away by rain or fresh running water, it may sometimes happen that although gypsum is still found there may be no salt; but, on the other hand, where there is rock salt there will always be gypsum. As the geological changes of the earth's surface are still proceeding at the present day, so in the midst of the dry land salt lakes are met with, which are sometimes scattered over vast districts formerly covered by seas now dried up. Such is the origin of many of the salt lakes about the lower portions of the Volga and in the Kirghiz steppes, where at a geological epoch preceding the present the Aralo-Caspian Sea extended. Such are the Baskunchaksky (in the Government of Astrakhan, 112 square kilometres superficial area), the Eltonsky (140 versts from the left bank of the Volga, and 200 square kilometres in superficial area), and upward of 700 other salt lakes lying about the lower portions of the Volga. In those in which the inflow of fresh water is less than that yearly evaporated, and in which the concentration of the solution has reached saturation, the _self-deposited_ salt is found already deposited on their beds, or is being yearly deposited during the summer months. Certain limans, or sea-side lakes, of the Azoff Sea are essentially of the same character--as, for instance, those in the neighbourhood of Henichesk and Berdiansk. The saline soils of certain Central Asian steppes, which suffer from a want of atmospheric fresh water, are of the same origin. Their salt originally proceeded from the salt of seas which previously covered these localities, and has not yet been washed away by fresh water. The main result of the above-described process of nature is the formation of masses of rock salt, which are, however, being gradually washed away by the subsoil waters flowing in their neighbourhood, and afterwards rising to the surface in certain places as _saline springs_, which indicate the presence of masses of deposited rock salt in the depths of the earth. If the subsoil water flows along a stratum of salt for a sufficient length of time it becomes saturated; but in flowing in its further course along an impervious stratum (clay) it becomes diluted by the fresh water leaking through the upper soil, and therefore the greater the distance of a saline spring from the deposit of rock salt, the poorer will it be in salt. A perfectly saturated brine, however, may be procured from the depths of the earth by means of bore-holes. The deposits of rock salt themselves, which are sometimes hidden at great depths below the earth's strata, may be discovered by the guidance of bore-holes and the direction of the strata of the district. Deposits of rock salt, about 35 metres thick and 20 metres below the surface, were discovered in this manner in the neighbourhood of Brianstcheffky and Dekonoffky, in the Bakhmut district of the Government of Ekaterinoslav. Large quantities of most excellent rock salt are now (since 1880) obtained from these deposits, whose presence was indicated by the neighbouring salt springs (near Slaviansk and Bakhmut) and by bore-holes which had been sunk in these localities for procuring strong (saturated) brines. But the Stassfurt deposits of rock salt near Magdeburg in Germany are celebrated as being the first discovered in this manner, and for their many remarkable peculiarities.[7] The plentiful distribution of saline springs in this and the neighbouring districts suggested the presence of deposits of rock salt in the vicinity. Deep bore-holes sunk in this locality did in fact give a richer brine--even quite saturated with salt. On sinking to a still greater depth, the deposits of salt themselves were at last arrived at. But the first deposit which was met with consisted of a bitter salt unfit for consumption, and was therefore called refuse salt (_Abraumsalz_). On sinking still deeper vast beds of real rock salt were struck. In this instance the presence of these upper strata containing salts of potassium, magnesium, and sodium is an excellent proof of the formation of rock salt from sea water. It is very evident that not only a case of evaporation to the end--as far, for instance, as the separation of carnallite--but also the preservation of such soluble salts as separate out from sea water after the sodium chloride, must be a very exceptional phenomenon, which is not repeated in all deposits of rock salt. The Stassfurt deposits therefore are of particular interest, not only from a scientific point of view, but also because they form a rich source of potassium salts which have many practical uses.[7 bis] [7] When the German savants pointed out the exact locality of the Stassfurt salt-beds and their depth below the surface, on the basis of information collected from various quarters respecting bore-holes and the direction of the strata, and when the borings, conducted by the Government, struck a salt-bed which was bitter and unfit for use, there was a great outcry against science, and the doubtful result even caused the cessation of the further work of deepening the shafts. It required a great effort to persuade the Government to continue the work. Now, when the pure salt encountered below forms one of the important riches of Germany, and when those 'refuse salts' have proved to be most valuable (as a source of potassium and magnesium), we should see in the utilisation of the Stassfurt deposits one of the conquests of science for the common welfare. [7 bis] In Western Europe, deposits of rock salt have long been known at Wieliczka, near Cracow, and at Cardona in Spain. In Russia the following deposits are known: (_a_) the vast masses of rock salt (3 square kilometres area and up to 140 metres thick) lying directly on the surface of the earth at Iletzky Zastchit, on the left bank of the river Ural, in the Government of Orenburg; (_b_) the Chingaksky deposit, 90 versts from the river Volga, in the Enotaeffsky district of the Government of Astrakhan; (_c_) the Kulepinsky (and other) deposits (whose thickness attains 150 metres), on the Araks, in the Government of Erivan in the Caucasus; (_d_) the Katchiezmansky deposit in the province of Kars; (_e_) the Krasnovodsky deposit in the Trans-Caspian province; and (_f_) the Bardymkulsky salt mines in Kokhand. A saturated brine, formed by the continued contact of subsoil water with rock salt, is extracted by means of bore-holes, as, for instance, in the Governments of Perm, Kharkoff, and Ekaterinoslav. Sometimes, as at Berchtesgaden (and at Hallein) in Austria, spring water is run on to underground beds of rock salt containing much clay. [Illustration: FIG. 64.--Graduator for the evaporation of the water of saline springs.] If a saline spring, or the salt water pumped from bore-holes, contains but little salt, then the first concentration of the natural solution is not carried on by the costly consumption of fuel, but by the cheaper method of evaporation by means of the wind. For this purpose so-called graduators are constructed: they consist of long and lofty sheds, which are sometimes several versts long, and generally extend in a direction at right angles to that of the usual course of the wind in the district. These sheds are open at the sides, and are filled with brushwood as shown in fig. 64. Troughs, A B, C D, into which the salt water is pumped, run along the top. On flowing from these troughs, through the openings, _a_, the water spreads over the brushwood and distributes itself in a thin layer over it, so that it presents a very large surface for evaporation, in consequence of which it rapidly becomes concentrated in warm or windy weather. After trickling over the brushwood, the solution collects in a reservoir under the graduator, whence it is usually pumped up by the pumps P P´, and again run a second and third time through the graduator, until the solution reaches a degree of concentration at which it becomes profitable to extract the salt by direct heating. Generally the evaporation in the graduator is not carried beyond a concentration of 12 to 15 parts of salt in 100 parts of solution. Strong natural solutions of salt, and also the graduated solutions, are evaporated in large shallow metallic vessels, which are either heated by the direct action of the flame from below or from above. These vessels are made of boiler plate, and are called salt-pans. Various means are employed for accelerating the evaporation and for economising fuel, which are mainly based on an artificial draught to carry off the steam as it is formed, and on subjecting the saline solution to a preliminary heating by the waste heat of the steam and furnace gases. Furthermore, the first portions of the salt which crystallise out in the salt-pans are invariably contaminated with gypsum, since the waters of saline springs always contain this substance. It is only the portions of the salt which separate later that are distinguished by their great purity. The salt is ladled out as it is deposited, left to drain on inclined tables and then dried, and in this manner the so-called bay salt is obtained. Since it has become possible to discover the saline deposits themselves, the extraction of table salt from the water of saline springs by evaporation, which previously was in general use, has begun to be disused, and is only able to hold its ground in places where fuel is cheap. In order to understand the full importance of the extraction of salt, it need only be mentioned that on the average 20 lbs. of table salt are consumed yearly per head of population, directly in food or for cattle. In those countries where common salt is employed in technical processes, and especially in England, almost an equal quantity is consumed in the production of substances containing chlorine and sodium, and especially in the manufacture of washing soda, &c., and of chlorine compounds (bleaching powder and hydrochloric acid). The yearly production of salt in Europe amounts to as much as 7-1/2 million tons. Although certain lumps of rock salt and crystals of bay salt sometimes consist of almost pure sodium chloride, still the ordinary commercial salt contains various impurities, the most common of which are magnesium salts. If the salt be pure, its solution gives no precipitate with sodium carbonate, Na_{2}CO_{3}, showing the absence of magnesium salts, because magnesium carbonate, MgCO_{3}, is insoluble in water. Rock salt, which is ground for use, generally contains also a considerable admixture of clay and other insoluble impurities.[8] For ordinary use the bulk of the salt obtained can be employed directly without further purification; but some salts are purified by solution and crystallisation of the solution after standing, in which case the evaporation is not carried on to dryness, and the impurities remain in the _mother liquor_ or in the sediment. When perfectly pure salt is required for chemical purposes it is best obtained as follows: a saturated solution of table salt is prepared, and hydrochloric acid gas is passed through it; this precipitates the sodium chloride (which is not soluble in a strong solution of hydrochloric acid), while the impurities remain in solution. By repeating the operation and fusing the salt (when adhering hydrochloric acid is volatilised) a pure salt is obtained, which is again crystallised from its solution by evaporation.[9] [8] The fracture of rock salt generally shows the presence of interlayers of impurities which are sometimes very small in weight, but visible owing to their refraction. In the excellently laid out salt mines of Briansk I counted (1888), if my memory does not deceive me, on an average ten interlayers per metre of thickness, between which the salt was in general very pure, and in places quite transparent. If this be the case, then there would be 350 interlayers for the whole thickness (about 35 metres) of the bed. They probably correspond with the yearly deposition of the salt. In this case the deposition would have extended over more than 300 years. This should be observable at the present day in lakes where the salt is saturated and in course of deposition. [9] My own investigations have shown that not only the sulphates, but also the potassium salts, are entirely removed by this method. Pure sodium chloride, in well-defined crystals (slowly deposited at the bottom of the liquid) or in compact masses (in which form rock salt is sometimes met with), is a colourless and transparent substance resembling, but more brittle and less hard than, glass.[10] Common salt always crystallises in the cubic system, most frequently in _cubes_, and more rarely in octahedra. Large transparent cubes of common salt, having edges up to 10 centimetres long, are sometimes found in masses of rock salt.[11] When evaporated in the open the salt often separates out on the surface[12] as cubes, which grow on to each other in the form of pyramidal square funnels. In still weather, these clusters are able to support themselves on the surface of the water for a long time, and sometimes go on increasing to a considerable extent, but they sink directly the water penetrates inside them. Salt fuses to a colourless liquid (sp. gr. 1·602, according to Quincke) at 851° (V. Meyer); if pure it solidifies to a non-crystalline mass, and if impure to an opaque mass whose surface is not smooth. In fusing, sodium chloride commences to volatilise (its weight decreases) and at a white heat it volatilises with great ease and completely; but at the ordinary temperature it may, like all ordinary salts, be considered as non-volatile, although as yet no exact experiments have been made in this direction. [10] According to the determinations of Klodt, the Briansk rock salt withstands a pressure of 340 kilograms per square centimetre, whilst glass withstands 1,700 kilos. In this respect salt is twice as secure as bricks, and therefore immense masses may be extracted from underground workings with perfect safety, without having recourse to brickwork supports, merely taking advantage of the properties of the salt itself. [11] To obtain well-formed crystals, a saturated solution is mixed with ferric chloride, several small crystals of sodium chloride are placed at the bottom, and the solution is allowed to evaporate slowly in a vessel with a loose-fitting cover. Octahedral crystals are obtained by the addition of borax, urea, &c., to the solution. Very fine crystals are formed in a mass of gelatinous silica. [12] If a solution of sodium chloride be slowly heated from above, where the evaporation takes place, then the upper layer will become saturated before the lower and cooler layers, and therefore crystallisation will begin on the surface, and the crystals first formed will float, having also dried from above, on the surface until they become quite soaked. Being heavier than the solution the crystals are partially immersed under it, and the following crystallisation, also proceeding on the surface, will only form crystals along the side of the original crystals. A funnel is formed in this manner. It will be borne on the surface like a boat (if the liquid be quiescent), because it will grow more from the upper edges. We can thus understand this at first sight strange funnel form of crystallisation of salt. In explanation why the crystallisation under the above conditions begins at the surface and not at the lower layers, it must be mentioned that the specific gravity of a crystal of sodium chloride = 2·16, and that of a solution saturated at 25° contains 26·7 p.c. of salt and has a specific gravity at 25°/4° of 1·2004; at 15° a saturated solution contains 26·5 p.c. of salt and has a sp. gr. 1·203 at 15°/4°. Hence a solution saturated at a higher temperature is specifically lighter, notwithstanding the greater amount of salt it contains. With many substances _surface crystallisation_ cannot take place because their solubility increases more rapidly with the temperature than their specific gravity decreases. In this case the saturated solution will always be in the lower layers, where also the crystallisation will take place. Besides which it may be added that as a consequence of the properties of water and solutions, when they are heated from above (for instance, by the sun's rays), the warmer layers being the lightest remain above, whilst when heated from below they rise to the top. For this reason the water at great depths below the surface is always cold, which has long been known. These circumstances, as well as those observed by Soret (Chapter I., Note 19), explain the great differences of density and temperature, and in the amount of salts held in the oceans at different latitudes (in polar and tropical climes) and at various depths. A saturated[13] solution of table salt (containing 26·4 p.c.) has at the ordinary temperature a specific gravity of about 1·2. The specific gravity of the crystals is 2·167 (17°). The salt which separates out at the ordinary and higher temperatures contains no water of crystallisation;[14] but if the crystals are formed at a low temperature, especially from a saturated solution cooled to -12°, then they present a prismatic form, and contain two equivalents of water, NaCl,2H_{2}O. At the ordinary temperature these crystals split up into sodium chloride and its solution.[15] Unsaturated solutions of table salt when cooled below 0° give[16] crystals of ice, but when the solution has a composition NaCl,10H_{2}O it solidifies completely at a temperature of -23°. A solution of table salt saturated at its boiling point boils at about 109°, and contains about 42 parts of salt per 100 parts of water. [13] By combining the results of Poggiale, Müller, and Karsten (they are evidently more accurate than those of Gay-Lussac and others) I found that a saturated solution at _t_°, from 0° to 108°, contains 35·7 + 0·024_t_ + 0·0002_t_^2 grams of salt per 100 grams of water. This formula gives a solubility at 0° = 35·7 grams (= 26·3 p.c.), whilst according to Karsten it is 36·09, Poggiale 35·5, and Müller 35·6 grams. [14] Perfectly pure _fused_ salt is not hygroscopic, according to Karsten, whilst the crystallised salt, even when quite pure, attracts as much as 0·6 p.c. of water from moist air, according to Stas. (In the Briansk mines, where the temperature throughout the whole year is about +10°, it may be observed, as Baron Klodt informed me, that in the summer during damp weather the walls become moist, while in winter they are dry). If the salt contain impurities--such as magnesium sulphate, &c.--it is more hygroscopic. If it contain any magnesium chloride, it partially deliquesces in a damp atmosphere. The crystallised and not perfectly pure salt decrepitates when heated, owing to its containing water. The pure salt, and also the transparent rock salt, or that which has been once fused, does not decrepitate. Fused sodium chloride shows a faint alkaline reaction to litmus, which has been noticed by many observers, and is due to the presence of sodium oxide (probably by the action of the oxygen of the atmosphere). According to A. Stcherbakoff very sensitive litmus (washed in alcohol and neutralised with oxalic acid) shows an alkaline reaction even with the crystallised salt. It may be observed that rock salt sometimes contains cavities filled with a colourless liquid. Certain kinds of rock salt emit an odour like that of hydrocarbons. These phenomena have as yet received very little attention. [15] By cooling a solution of table salt saturated at the ordinary temperature to -15°, I obtained first of all well-formed tabular (six-sided) crystals, which when warmed to the ordinary temperature disintegrated (with the separation of anhydrous sodium chloride), and then prismatic needles up to 20 mm. long were formed from the same solution. I have not yet investigated the reason of the difference in crystalline form. It is known (Mitscherlich) that NaI,2H_{2}O also crystallises either in plates or prisms. Sodium bromide also crystallises with 2H_{2}O at the ordinary temperature. [16] Notwithstanding the great simplicity (Chapter I., Note 49) of the observations on the formation of ice from solution, still even for sodium chloride they cannot yet be considered as sufficiently harmonious. According to Blagden and Raoult, the temperature of the formation of ice from a solution containing _c_ grams of salt per 100 grams of water =-0·6_c_ to _c_ = 10, according to Rosetti =-0·649_c_ to _c_ = 8·7, according to De Coppet (to _c_ = 10) =-0·55_c_-0·006_c_^2, according to Karsten (to _c_ = 10)-0·762_c_ + 0·0084_c_^2, and according to Guthrie a much lower figure. By taking Rosetti's figure and applying the rule given in Chapter I., Note 49 we obtain-- _i_ - 0·649 × 58·5/18·5 = 2·05. Pickering (1893) gives for _c_ = 1-0·603, for _c_ = 2-1·220; that is (_c_ up to 2·7) about -(0·600 + 0·005_c_)_c_. The data for strong solutions are not less contradictory. Thus with 20 p.c. of salt, ice is formed at -14·4° according to Karsten,-17° according to Guthrie,-17·6° according to De Coppet. Rüdorff states that for strong solutions the temperature of the formation of ice descends in proportion to the contents of the compound, NaCl,2H_{2}O (per 100 grams of water) by 0°·342 per 1 gram of salt, and De Coppet shows that there is no proportionality, in a strict sense, for either a percentage of NaCl or of NaCl,2H_{2}O. Of all its physical properties the specific gravity of solutions of sodium chloride is the one which has been the most fully investigated. A comparison of all the existing determinations of the specific gravity of solutions of NaCl[17] at 15° (in vacuo, taking water at 4° as 10,000), with regard to _p_ (the percentage amount of the salt in solution), show that it is expressed by the equation S_{15} = 9991·6 + 71·17_p_ + 0·2140_p_^2. For instance, for a solution 200H_{2}O + NaCl, in which case _p_ = 1·6, S_{15} = 1·0106. It is seen from the formula that the addition of water produces a contraction.[18] The specific gravity[19] at certain temperatures and concentrations in vacuo referred to water at 4° = 10,000[20] is here given for 0° 15° 30° 100° _p_ = 5 10372 10353 10307 9922 10 10768 10728 10669 10278 15 11164 11107 11043 10652 20 11568 11501 11429 11043 It should be remarked that Baumé's hydrometer is graduated by taking a 10 p.c. solution of sodium chloride as 10° on the scale, and therefore it gives approximately the percentage amount of the salt in a solution. Common salt is somewhat soluble in alcohol,[21] but it is insoluble in ether and in oils. [17] A collection of observations on the specific gravity of solutions of sodium chloride is given in my work cited in Chapter I., Note 50. Solutions of common salt have also been frequently investigated as regards rate of _diffusion_ (Chapter I.), but as yet there are no complete data in this respect. It may be mentioned that Graham and De Vries demonstrated that diffusion in gelatinous masses (for instance, gelatin jelly, or gelatinous silica) proceeds in the same manner as in water, which may probably lead to a convenient and accurate method for the investigation of the phenomena of diffusion. N. Umoff (Odessa, 1888) investigated the diffusion of common salt by means of glass globules of definite density. Having poured water into a cylinder over a layer of a solution of sodium chloride, he observed during a period of several months the position (height) of the globules, which floated up higher and higher as the salt permeated upwards. Umoff found that at a constant temperature the distances of the globules (that is, the length of a column limited by layers of definite concentration) remain constant; that at a given moment of time the concentration, _q_, of different layers situated at a depth _z_ is expressed by the equation B-K_z_ = log.(A-_q_), where A, B, and K are constants; that at a given moment the rate of diffusion of the different layers is proportional to their depth, &_c._ [18] If _S__{0} be the specific gravity of water, and _S_ the specific gravity of a solution containing _p_ p.c. of salt, then by mixing equal weights of water and the solution, we shall obtain a solution containing 1/2_p_ of the salt, and if it be formed without contraction, then its specific gravity _x_ will be determined by the equation 2/_x_ = 1/S_{0} + 1/S, because the volume is equal to the weight divided by the density. In reality, the specific gravity is always found to be greater than that calculated on the supposition of an absence of contraction. [19] Generally the specific gravity is observed by weighing in air and dividing the weight in grams by the volume in cubic centimetres, the latter being found from the weight of water displaced, divided by its density at the temperature at which the experiment is carried out. If we call this specific gravity S_{1}, then as a cubic centimetre of air under the usual conditions weighs about 0·0012 gram, the sp. gr. in a vacuum S = S_{1} + 0·0012 (S_{1} - 1), if the density of water = 1. [20] If the sp. gr. S_{2} be found directly by dividing the weight of a solution by the weight of water at the same temperature and in the same volume, then the true sp. gr. _S_ referred to water at 4° is found by multiplying S_{2} by the sp. gr. of water at the temperature of observation. [21] According to Schiff 100 grams of alcohol, containing _p_ p.c. by weight of C_{2}H_{6}O, dissolves at 15°-- _p_ = 10 20 40 60 80 28·5 22·6 13·2 5·9 1·2 grams NaCl. Common salt gives very few compounds[22] (double salts) and these are very readily decomposed: it is also decomposed with great difficulty and its dissociation is unknown.[23] But it is easily decomposed, both when fused and in solution, by the action of a galvanic current. If the dry salt be fused in a crucible and an electric current be passed through it by immersing carbon or platinum electrodes in it (the positive electrode is made of carbon and the negative of platinum or mercury), it is _decomposed_: the suffocating gas, chlorine, is liberated at the positive pole and metallic sodium at the negative pole. Both of them act on the excess of water at the moment of their evolution; the sodium evolves hydrogen and forms caustic soda, and the chlorine evolves oxygen and forms hydrochloric acid, and therefore on passing a current through a solution of common salt metallic sodium will not be obtained--but oxygen, chlorine, and hydrochloric acid will appear at the positive pole, and hydrogen and caustic soda at the negative pole.[23 bis] Thus salt, like other salts, is decomposed by the action of an electric current into a metal and a haloid (Chapter III.) Naturally, like all other salts, it may be formed from the corresponding base and acid with the separation of water. In fact if we mix caustic soda (base) with hydrochloric acid (acid), table salt is formed, NaHO + HCl = NaCl + H_{2}O. [22] Amongst the double salts formed by sodium chloride that obtained by Ditte (1870) by the evaporation of the solution remaining after heating sodium iodate with hydrochloric acid until chlorine ceases to be liberated, is a remarkable one. Its composition is NaIO_{3},NaCl,14H_{2}O. Rammelsberg obtained a similar (perhaps the same) salt in well-formed crystals by the direct reaction of both salts. [23] But it gives sodium in the flame of a Bunsen's burner (see Spectrum Analysis), doubtless under the reducing action of the elements carbon and hydrogen. In the presence of an excess of hydrochloric acid in the flame (when the sodium would form sodium chloride), no sodium is formed in the flame and the salt does not communicate its usual coloration. [23 bis] There is no doubt, however, but that chloride of sodium is also decomposed in its aqueous solutions with the separation of sodium, and that it does not simply enter into double decomposition with the water (NaCl + H_{2}O = NaHO + HCl). This is seen from the fact that when a saturated solution of NaCl is rapidly decomposed by an electric current, a large amount of chlorine appears at the anode and a sodium amalgam forms at the mercury cathode, which acts but slowly upon the strong solution of salt. Castner's process for the electrolysis of brine into chlorine and caustic soda is an application of this method which has been already worked in England on an industrial scale. With resspect to the double decompositions of sodium chloride it should be observed that they are most varied, and serve as means of obtaining nearly all the other compounds of sodium and chlorine. _The double decompositions of sodium chloride_ are almost exclusively based on the possibility of the metal sodium being exchanged for hydrogen and other metals. But neither hydrogen nor any other metal can directly displace the sodium from sodium chloride. This would result in the separation of metallic sodium, which itself displaces hydrogen and the majority of other metals from their compounds, and is not, so far as is known, ever separated by them. The replacement of the sodium in sodium chloride by hydrogen and various metals can only take place by the transference of the sodium into some other combination. If hydrogen or a metal, M, be combined with an element X, then the double decomposition NaCl + MX = NaX + MCl takes place. Such double decompositions take place under special conditions, sometimes completely and sometimes only partially, as we shall endeavour to explain. In order to acquaint ourselves with the double decompositions of sodium chloride, we will follow the methods actually employed in practice to procure compounds of sodium and of chlorine from common salt. For this purpose we will first describe the treatment of sodium chloride with sulphuric acid for the preparation of hydrochloric acid and sodium sulphate. We will then describe the substances obtained from hydrochloric acid and sodium sulphate. Chlorine itself, and nearly all the compounds of this element, may be procured from hydrochloric acid, whilst sodium carbonate, caustic soda, metallic sodium itself and all its compounds, may be obtained from sodium sulphate. Even in the animal organism salt undergoes similar changes, furnishing the sodium, alkali, and hydrochloric acid which take part in the processes of animal life. Its necessity as a constituent in the food both of human beings and of animals becomes evident when we consider that both hydrochloric acid and salts of sodium are found in the substances which are separated out from the blood into the stomach and intestines. Sodium salts are found in the blood and in the bile which is elaborated in the liver and acts on the food in the alimentary canal, whilst hydrochloric acid is found in the acid juices of the stomach. Chlorides of the metals are always found in considerable quantities in the urine, and if they are excreted they must be replenished in the organism; and for the replenishment of the loss, substances containing chlorine compounds must be taken in food. Not only do animals consume those small amounts of sodium chloride which are found in drinking water or in plants or other animals, but experience has shown that many wild animals travel long distances in search of salt springs, and that domestic animals which in their natural condition do not require salt, willingly take it, and that the functions of their organisms become much more regular from their doing so. _The action of sulphuric acid on sodium chloride._--If sulphuric acid be poured over common salt, then even at the ordinary temperature, as Glauber observed, an odorous gas, hydrochloric acid, is evolved. The reaction which takes place consists in the sodium of the salt and the hydrogen of the sulphuric acid changing places. NaCl + H_{2}SO_{4} = HCl + NaHSO_{4} Sodium Sulphuric Hydrochloric Acid sodium chloride acid acid sulphate At the ordinary temperature this reaction is not complete, but soon ceases. When the mixture is heated, the decomposition proceeds until, if there be sufficient salt present, all the sulphuric acid taken is converted into acid sodium sulphate. Any excess of acid will remain unaltered. If 2 molecules of sodium chloride (117 parts) be taken per molecule of sulphuric acid (98 parts), then on heating the mixture to a moderate temperature only one-half (58·5) of the salt will suffer change. Complete decomposition, after which neither hydrogen nor chlorine is left in the residue, proceeds (when 117 parts of table salt are taken per 98 parts of sulphuric acid) _at a red heat only_. Then-- 2NaCl + H_{2}SO_{4} = 2HCl + Na_{2}SO_{4} Table Sulphuric Hydrochloric Sodium salt acid acid sulphate This double decomposition is the result of the action of the acid salt, NaHSO_{4}, first formed, on sodium chloride, for the acid salt, since it contains hydrogen, itself acts like an acid, NaCl + NaHSO_{4} = HCl + Na_{2}SO_{4}. By adding this equation to the first we obtain the second, which expresses the ultimate reaction. Hence in the above reaction, non-volatile or sparingly volatile table salt and sparingly volatile sulphuric acid are taken, and as the result of their reaction, after the hydrogen and sodium have exchanged places, there is obtained non-volatile sodium sulphate and gaseous hydrochloric acid. The fact of the latter being a gaseous substance forms the main reason for the reaction proceeding to the very end. The mechanism of this kind of double decomposition, and the cause of the course of the reaction, are exactly the same as those we saw in the decomposition of nitre (Chapter VI.) by the action of sulphuric acid. The sulphuric acid in each case displaces the other, volatile, acid. Not only in these two instances, but in every instance, if a volatile acid can be formed by the substitution of the hydrogen of sulphuric acid for a metal, then this volatile acid will be formed. From this it may be concluded that the volatility of the acid should be considered as the cause of the progress of the reaction; and indeed if the acid be soluble but not volatile, or if the reaction take place in an enclosed space where the resulting acid cannot volatilise, or at the ordinary temperature when it does not pass into the state of elastic vapour--then the decomposition does not proceed to the end, but only up to a certain limit. In this respect the explanations given at the beginning of this century by the French chemist Berthollet in his work 'Essai de Statique Chimique' are very important. _The doctrine of Berthollet_ starts from the supposition that the chemical reaction of substances is determined not only by the degrees of affinity between the different parts, but also by the relative masses of the reacting substances and by those physical conditions under which the reaction takes place. Two substances containing the elements MX and NY, being brought into contact with each other, form by double decomposition the compounds MY and NX; but the formation of these two new compounds will not proceed to the end unless one of them is removed from the sphere of action. But it can only be removed if it possesses different physical properties from those of the other substances which are present with it. Either it must be a gas while the others are liquid or solid, or an insoluble solid while the others are liquid or soluble. The relative amounts of the resultant substances, if nothing separates out from their intermixture, depend only on the relative quantities of the substances MX and NY, and upon the degrees of attraction existing between the elements M, N, X, and Y; but however great their mass may be, and however considerable the attractions, still in any case if nothing separates out from the sphere of action the decomposition will presently cease, a state of equilibrium will be established, and instead of two there will remain four substances in the mass: namely, a portion of the original bodies MX and NY, and a certain quantity of the newly formed substances MY and NX, if it be assumed that neither MN or XY nor any other substances are produced, and this may for the present[24] be admitted in the case of the double decomposition of salts in which M and X are metals and X and Y haloids. As the ordinary double decomposition here consists merely in the exchange of metals, the above simplification is applicable. The sum total of existing data concerning the double decomposition of salts leads to the conclusion that from salts MX + NY there always arises a certain quantity of NX and MY, as should be the case according to Berthollet's doctrine. A portion of the historical data concerning this subject will be afterwards mentioned, but we will at once proceed to point out the observations made by Spring (1888) which show that _even in a solid state_ salts are subject to a similar interchange of metals if in a condition of sufficiently close contact (it requires time, a finely divided state, and intimate mixture). Spring took two non-hygroscopic salts, potassium nitrate, KNO_{3}, and well-dried sodium acetate, C_{2}H_{3}NaO_{2}, and left a mixture of their powders for several months in a desiccator. An interchange of metals took place, as was seen from the fact that the resultant mass rapidly attracted the moisture of the air, owing to the formation of sodium nitrate, NaNO_{3}, and potassium acetate, C_{2}H_{3}KO_{2}, both of which are highly hygroscopic.[24 bis] [24] If MX and NY represent the molecules of two salts, and if there be _no third substance_ present (such as water in a solution), the formation of XY would also be possible; for instance, cyanogen, iodine, &c. are capable of combining with simple haloids, as well as with the complex groups which in certain salts play the part of haloids. Besides which the salts MX and NY or MY with NX may form double salts. If the number of molecules be unequal, or if the valency of the elements or groups contained in them be different, as in NaCl + H_{2}SO_{4}, where Cl is a univalent haloid and SO_{4} is bivalent, then the matter may be complicated by the formation of other compounds besides MY and NX, and when a solvent participates in the action, and especially if present in large proportion, the phenomena must evidently become still more complex; and this is actually the case in nature. Hence while placing before the reader a certain portion of the existing store of knowledge concerning the phenomena of double saline decompositions, I cannot consider the theory of the subject as complete, and have therefore limited myself to a few data, the completion of which must be sought in more detailed works on the subject of theoretical chemistry, without losing sight of what has been said above. [24 bis] When the mixture of potassium nitrate and sodium acetate was heated by Spring to 100°, it was completely fused into one mass, although potassium nitrate fuses at about 340° and sodium nitrate at about 320°. When Berthollet enunciated his doctrine the present views of atoms and molecules had yet to be developed, and it is now necessary to submit the matter to examination in the light of these conceptions; we will therefore consider the reaction of salts, taking M and N, X and Y as equivalent to each other--that is, as capable of replacing each other 'in toto,' as Na or K,, 1/2Ca or 1/2Mg (bivalent elements) replace hydrogen. And since, according to Berthollet's doctrine, when _m_MX of one salt comes into contact with _n_NY of another salt, a certain quantity _x_MY and _x_NX is formed, there remains _m_-_x_ of the salt MX, and _n_-_x_ of the salt NY. If _m_ be greater than _n_, then the maximum interchange could lead to _x_ = _n_, whilst from the salts taken there would be formed _n_MY + _n_NX + (_m_-_n_)MX--that is, a portion of one only of the salts taken would remain unchanged because the reaction could only proceed between _n_MX and _n_NY. If _x_ were actually equal to _n_, the mass of the salt MX would not have any influence on the _modus operandi_ of the reaction, which is equally in accordance with the teaching of Bergmann, who supposed double reactions to be independent of the mass and determined by affinity only. If M had more affinity for X than for Y, and N more affinity for Y than for X, then according to Bergmann there would be no decomposition whatever, and _x_ would equal 0. If the affinity of M for Y and of N for X were greater than those in the original grouping, then the affinity of M for X and of N for Y would be overcome, and, according to Bergmann's doctrine, complete interchange would take place--_i.e._ _x_ would equal _n_. According to Berthollet's teaching, a distribution of M and N between X and Y will take place in every case, not only in proportion to the degrees of affinity, but also in proportion to the masses, so that with a small affinity and a large mass the same action can be produced as with a large affinity and a small mass. Therefore, (1) _x_ will always be less than _n_ and their ratio _x_/_n_ less than unity--that is, the decomposition will be expressed by the equation, _m_MX + _n_NY = (_m_-_x_)MX + (_n_-_x_)NY + _x_MY + _x_NX; (2) by increasing the mass _m_ we increase the decomposition--that is, we increase _x_ and the ratio _x_/(_n_-_x_), until with an infinitely large quantity m the fraction _x_/_n_ will equal 1, and the decomposition will be complete, however small the affinities uniting MY and NX may be; and (3) if _m_ = _n_, by taking MX + NY or MY + NX we arrive at one and the same system _in either case_: (_n_-_x_)MX + (_n_-_x_)NY + _x_MY + _x_NX. These direct consequences of Berthollet's teaching are verified by experience. Thus, for example, a mixture of solutions of sodium nitrate and potassium chloride in all cases has entirely the same properties as a mixture of solutions of potassium nitrate and sodium chloride, of course on condition that the mixed solutions are of identical elementary composition. But this identity of properties might either proceed from one system of salts passing entirely into the other (Bergmann's hypothesis) in conformity with the predominating affinities (for instance, from KCl + NaNO_{3} there might arise KNO_{3} + NaCl, if it be admitted that the affinities of the elements as combined in the latter system are greater than in the former); or, on the other hand, it might be because both systems by the interchange of a portion of their elements give one and the same state of equilibrium, as according to Berthollet's teaching. Experiment proves the latter hypothesis to be the true one. But before citing the most historically important experiments verifying Berthollet's doctrine, we must stop to consider the conception _of the mass_ of the reacting substances. Berthollet understood by mass the actual relative quantity of a substance; but now it is impossible to understand this term otherwise than as the number of molecules, for they act as chemical units, and in the special case of double saline decompositions it is better to take it as the number of equivalents. Thus in the reaction NaCl + H_{2}SO_{4} the salt is taken in one equivalent and the acid in two. If 2NaCl + H_{2}SO_{4} act, then the number of equivalents are equal, and so on. The _influence of mass_ on the amount of decomposition _x_/_n_ forms the root of Berthollet's doctrine, and therefore we will first of all turn our attention to the establishment of this principle in relation to the double decomposition of salts. About 1840 H. Rose[25] showed that water decomposes metallic sulphides like calcium sulphide, CaS, forming hydrogen sulphide, H_{2}S, notwithstanding the fact that the affinity of hydrogen sulphide, as an acid, for lime, CaH_{2}O_{2}, as a base, causes them to react on each other, forming calcium sulphide and water, CaS + 2H_{2}O. Furthermore, Rose showed that the greater the amount of water acting on the calcium sulphide, the more complete is the decomposition. The results of this reaction are evident from the fact that the hydrogen sulphide formed may be expelled from the solution by heating, and that the resulting lime is sparingly soluble in water. Rose clearly saw from this that such feeble agents, in a chemical sense, as carbonic anhydride and water, by acting in a mass and for long periods of time in nature on the durable rocks, which resist the action of the most powerful acids, are able to bring about chemical change--to extract, for example, from rocks the bases, lime, soda, potash. The influence of the mass of water on antimonious chloride, bismuth nitrate, &c., is essentially of the same character. These substances give up to the water a quantity of acid which is greater in proportion as the mass of the water acting on them is greater.[25 bis] [25] H. Rose is more especially known for his having carefully studied and perfected several methods for the exact chemical analysis of many mineral substances. His predecessor in this branch of research was Berzelius, and his successor Fresenius. [25 bis] Historically the influence of the mass of water was the first well-observed phenomenon in support of Berthollet's teaching, and it should not now be forgotten. In double decompositions taking place in dilute solutions where the mass of water is large, its influence, notwithstanding the weakness of affinities, must he great, according to the very essence of Berthollet's doctrine. As explaining the action of the mass of water, the experiments of Pattison Muir (1879) are very instructive. These experiments demonstrate that the decomposition of bismuth chloride is the more complete the greater the relative quantity of water, and the less the mass of hydrochloric acid forming one of the products of the reaction. Barium sulphate, BaSO_{4}, which is insoluble in water, when fused with sodium carbonate, Na_{2}CO_{3}, gives, but not completely, barium carbonate, BaCO_{3}, (also insoluble), and sodium sulphate, Na_{2}SO_{4}. If a solution of sodium carbonate acts on precipitated barium sulphate, the same decomposition is also effected (Dulong, Rose), but it is restricted by a limit and requires time. A mixture of sodium carbonate and sulphate is obtained in the solution and a mixture of barium carbonate and sulphate in the precipitate. If the solution be decanted off and a fresh solution of sodium carbonate be poured over the precipitate, then a fresh portion of the barium sulphate passes into barium carbonate, and so by increasing the mass of sodium carbonate it is possible to entirely convert the barium sulphate into barium carbonate. If a definite quantity of sodium sulphate be added to the solution of sodium carbonate, then the latter will have no action whatever on the barium sulphate, because then a system in equilibrium determined by the reverse action of the sodium sulphate on the barium carbonate and by the presence of both sodium carbonate and sulphate in the solution, is at once arrived at. On the other hand, if the mass of the sodium sulphate in the solution be great, then the barium carbonate is reconverted into sulphate until a definite state of equilibrium is attained between the two opposite reactions, producing barium carbonate by the action of the sodium carbonate and barium sulphate by the action of the sodium sulphate. Another most important principle of Berthollet's teaching is the existence of _a limit of exchange decomposition_, or _the attainment of a state of equilibrium_. In this respect the determinations of Malaguti (1857) are historically the most important. He took a mixture of solutions of equivalent quantities of two salts, MX and NY, and judged the amount of the resulting exchange from the composition of the precipitate produced by the addition of alcohol. When, for example, zinc sulphate and sodium chloride (ZnSO_{4} and 2NaCl) were taken, there were produced by exchange sodium sulphate and zinc chloride. A mixture of zinc sulphate and sodium sulphate was precipitated by an excess of alcohol, and it appeared from the composition of the precipitate that 72 per cent. of the salts taken had been decomposed. When, however, a mixture of solutions of sodium sulphate and zinc chloride was taken, the precipitate presented the same composition as before--that is, about 28 per cent. of the salts taken had been subjected to decomposition. In a similar experiment with a mixture of sodium chloride and magnesium sulphate, 2NaCl + MgSO_{4} or MgCl_{2} + Na_{2}SO_{4}, about half of the metals underwent the decomposition, which may be expressed by the equation 4NaCl + 2MgSO_{4} = 2NaCl + MgSO_{4} + Na_{2}SO_{4} + MgCl_{2} = 2Na_{2}SO_{4} + 2MgCl_{2}. A no less clear limit expressed itself in another of Malaguti's researches when he investigated the above-mentioned reversible reactions of the insoluble salts of barium. When, for example, barium carbonate and sodium sulphate (BaCO_{3} + Na_{2}SO_{4}) were taken, then about 72 per cent. of the salts were decomposed, that is, were converted into barium sulphate and sodium carbonate. But when the two latter salts were taken, then about 19 per cent. of them passed into barium carbonate and sodium sulphate. Probably the end of the reaction was not reached in either case, because this would require a considerable time and a uniformity of conditions attainable with difficulty. Gladstone (1855) took advantage of the colour of solutions of different ferric salts for determining the measure of exchange between metals. Thus a solution of ferric thiocyanate has a most intense red colour, and by making a comparison between the colour of the resulting solutions and the colour of solutions of known strength it was possible to judge to a certain degree the quantity of the thiocyanate formed. This colorimetric method of determination has an important significance as being the first in which a method was applied for determining the composition of a solution without the removal of any of its component parts. When Gladstone took equivalent quantities of ferric nitrate and potassium thiocyanate--Fe(NO_{3})_{3} + 3KCNS--only 13 per cent. of the salts underwent decomposition. On increasing the mass of the latter salt the quantity of ferric thiocyanate formed increased, but even when more than 300 equivalents of potassium thiocyanate were taken a portion of the iron still remained as nitrate. It is evident that the affinity acting between Fe and NO_{3} and between K and CNS on the one hand, is greater than the affinity acting between Fe and CNS, together with the affinity of K for NO_{3}, on the other hand. The investigation of the variation of the fluorescence of quinine sulphate, as well as the variation of the rotation of the plane of polarisation of nicotine, gave in the hands of Gladstone many proofs of the entire applicability of Berthollet's doctrine, and in particular demonstrated the influence of mass which forms the chief distinctive feature of the teaching of Berthollet, teaching little appreciated in his own time. At the beginning of the year 1860, the doctrine of the limit of reaction and of the influence of mass on the process of chemical transformations received a very important support in the researches of Berthelot and P. de Saint-Gilles on the formation of the ethereal salts RX from the alcohols ROH and acids HX, when water is also formed. This conversion is essentially very similar to the formation of salts, but differs in that it proceeds slowly at the ordinary temperature, extending over whole years, and is not complete--that is, it has a distinct limit determined by a reverse reaction; thus an ethereal salt RX with water gives an alcohol ROH and an acid HX--up to that limit generally corresponding with two-thirds of the alcohol taken, if the action proceed between molecular quantities of alcohol and acid. Thus common alcohol, C_{2}H_{5}OH, with acetic acid, HC_{2}H_{3}O_{2}, gives the following system rapidly when heated, or slowly at the ordinary temperature, ROH + HX + 2RX + 2H_{2}O, whether we start from 3RHO + 3HX or from 3RX + 3H_{2}O. The process and completion of the reaction in this instance are very easily observed, because the quantity of free acid is easily determined from the amount of alkali requisite for its saturation, as neither alcohol nor ethereal salt acts on litmus or other reagent for acids. Under the influence of an increased mass of alcohol the reaction proceeds further. If two molecules of alcohol, RHO, be taken for every one molecule of acetic acid, HX, then instead of 66 p.c., 83 p.c. of the acid passes into ethereal salt, and with fifty molecules of RHO nearly all the acid is etherised. The researches of Menschutkin in their details touched on many important aspects of the same subject, such as the influence of the composition of the alcohol and acid on the limit and rate of exchange--but these, as well as other details, must be looked for in special treatises on organic and theoretical chemistry. In any case the study of etherification has supplied chemical mechanics with clear and valuable data, which directly confirm the two fundamental propositions of Berthollet; the influence of mass, and the limit of reaction--that is, the equilibrium between opposite reactions. The study of numerous instances of dissociation which we have already touched on, and shall again meet with on several occasions, gave the same results. With respect to double saline decompositions, it is also necessary to mention the researches of Wiedemann on the decomposing action of a mass of water on the ferric salts, which could be determined by measuring the magnetism of the solutions, because the ferric oxide (soluble colloid) set free by the water is less magnetic than the ferric salts. A very important epoch in the history of Berthollet's doctrine was attained when, in 1867, the Norwegian chemists, Guldberg and Waage, expressed it as an algebraical formula. They defined the active mass as the number of molecules contained in a given volume, and assumed, as follows from the spirit of Berthollet's teaching, that the action between the substances was equal to the product of the masses of the reacting substances. Hence if the salts MX and NY be taken in equivalent quantities (_m_ = 1 and _n_ = 1) and the salts MY and NX are not added to the mixture but proceed from it, then if _k_ represent the coefficient of the rate of the action of MX on NY and if _k_´ represent the same coefficient for the pair MY and NX, then we shall have at the moment when the decomposition equals x a measure of action for the first pair: _k_(1-_x_)(1-_x_) and for the second pair _k´xx_, and a state of equilibrium or limit will be reached when _k_(1-_x_)^2 = _k_´_x_^2, whence the ratio _k_/_k_´ = [_x_/(1-_x_)]^2. Therefore in the case of the action of alcohol on an acid, when _x_ = 2/3, the magnitude _k_/_k_´ = 4, that is, the reaction of the alcohol on the acid is four times as fast as that of the ethereal salt on water. If the ratio _k_/_k_´ be known, then the influence of mass may be easily determined from it. Thus if instead of one molecule of alcohol two be taken, then the equation will be _k_(2-_x_)(1-_x_) = _k´xx_, whence _x_ = 0·85 or 85 percent., which is close to the result of experiment. If 300 molecules of alcohol be taken, then x proves to be approximately 100 per cent., which is also found to be the case by experiment.[26] [26] From the above it follows that an excess of acid should influence the reaction like an excess of alcohol. It is in fact shown by experiment that if two molecules of acetic acid be taken to one molecule of alcohol, 84 p.c. of alcohol is etherified. If with a large preponderance of acid or of alcohol certain discrepancies are observed, their cause must be looked for in the incomplete correspondence of the conditions and external influences. But it is impossible to subject the formation of salts to any process directly analogous to that which is so conveniently effected in etherification. Many efforts have, however, been made to solve the problem of the measure of reaction in this case also. Thus, for example, Khichinsky (1866), Petrieff (1885), and many others investigated the distribution of metals and haloid groups in the case of one metal and several haloids taken in excess, as acids; or conversely with an excess of bases, the distribution of these bases with relation to an acid; in cases where a portion of the substances forms a precipitate and a portion remains in solution. But such complex cases, although they in general confirm Berthollet's teaching (for instance, a solution of silver nitrate gives some silver oxide with lead oxide, and a solution of nitrate of lead precipitates some lead oxide under the action of silver oxide, as Petrieff demonstrated), still, owing to the complexity of the phenomena (for instance, the formation of basic and double salts), they cannot give simple results. But much more instructive and complete are researches like those made by Pattison Muir (1876), who took the simple case of the precipitation of calcium carbonate, CaCO_{3}, from the mixture of solutions of calcium chloride and sodium or potassium carbonate, and found in this case that not only was the rate of action (for example, in the case of CaCl_{2} + Na_{2}CO_{3}, 75 per cent. of CaCO_{3} was precipitated in five minutes, 85 per cent. in thirty minutes, and 94 per cent. in two days) determined by the temperature, relative mass, and amount of water (a large mass of water decreases the rate), but that the limit of decomposition was also dependent on these influences. However, even in researches of this kind the conditions of reaction are complicated by the non-uniformity of the media, inasmuch as a portion of the substance is obtained or remains in the form of a precipitate, so that the system is heterogeneous. The investigation of double saline decompositions offers many difficulties which cannot be considered as yet entirely overcome. Although many efforts have long since been made, the majority of the researches were carried on in aqueous solutions, and as water is itself a saline compound and able to combine with salts and enter into double decomposition with them, such reactions taking place in solutions in reality present very complex cases.[27] In this sense the reaction between alcohols and acids is much more simple, and therefore its significance in confirmation of Berthollet's doctrine is of particular importance. The only cases which can be compared with these reactions for simplicity are those exchange decompositions investigated by G. G. Gustavson, which take place between CCl_{4} and RBr_{n} on the one hand, and CBr_{4} and RCl_{n} on the other. This case is convenient for investigation inasmuch as the RCl_{n} and RBr_{n} taken (such as BCl_{3}, SiCl_{4}, TiCl_{4}, POCl_{3}, and SnCl_{4}) belong to those substances which are decomposed by water, whilst CCl_{4} and CBr_{4} are not decomposed by water; and therefore, by heating, for instance, a mixture of CCl_{4} + SiBr_{4} it is possible to arrive at a conclusion as to the amount of interchange by treating the product with water, which decomposes the SiBr_{4} left unchanged and the SiCl_{4} formed by the exchange, and therefore by determining the composition of the product acted on by the water it is possible to form a conclusion as to the amount of decomposition. The mixture was always formed with equivalent quantities--for instance, 4BCl_{3} + 3CBr_{4}. It appeared that there was no exchange whatever on simple intermixture, but that it proceeded slowly, when the mixture was heated (for example, with the mixture above mentioned at 123° 4·86 per cent. of Cl was replaced by Br after 14 days' heating, and 6·83 per cent. after 28 days, and 10·12 per cent. when heated at 150° for 60 days). A limit was always reached which corresponded with that of the complemental system; in the given instance the system 4BBr_{3} + 3CCl_{4}. In this last 89·97 per cent. of bromine in the BBr_{3} was replaced by chlorine; that is, there were obtained 89·97 molecules of BCl_{3} and there remained 10·02 molecules of BBr_{3}, and therefore the same state of equilibrium was reached as that given by the system 4BCl_{3} + 3CBr_{4}. Both systems gave one and the same state of equilibrium at the limit, which is in agreement with Berthollet's doctrine.[28] [27] As an example two methods may be mentioned, Thomsen's and Ostwald's. Thomsen (1869) applied a thermochemical method to exceedingly dilute solutions without taking the water into further consideration. He took solutions of caustic soda containing 100H_{2}O per NaHO, and sulphuric acid containing 1/2H_{2}SO_{4} + 100H_{2}O. In order that these solutions may be mixed in such quantities that atomic proportions of acid and alkali would act, for forty grams of caustic soda (which answers to its equivalent) there should be employed 49 grams of sulphuric acid, and then +15,689 heat units would be evolved. If the normal sodium sulphate so formed be mixed with _n_ equivalents of sulphuric acid, a certain amount of heat is absorbed, namely a quantity equal to (_n_.1650)/(_n_ + 0·8) heat units. An equivalent of caustic soda, in combining with an equivalent of nitric acid, evolves +13,617 units of heat, and the augmentation of the amount of nitric acid entails an absorption of heat for each equivalent equal to -27 units; so also in combining with hydrochloric acids +13,740 heat units are absorbed, and for each equivalent of hydrochloric acid beyond this amount there are absorbed -32 heat units. Thomsen mixed each one of three neutral salts, sodium sulphate, sodium chloride and sodium nitrate, with an acid which is not contained in it; for instance, he mixed a solution of sodium sulphate with a solution of nitric acid and determined the number of heat units then absorbed. An absorption of heat ensued because a normal salt was taken in the first instance, and the mixture of all the above normal salts with acid produces an absorption of heat. The amount of heat absorbed enabled him to obtain an insight into the process taking place in this mixture, for sulphuric acid added to sodium sulphate absorbs a considerable quantity of heat, whilst hydrochloric and nitric acids absorb a very small amount of heat in this case. By mixing an equivalent of sodium sulphate with various numbers of equivalents of nitric acid, Thomsen observed that the amount of heat absorbed increased more and more as the amount of nitric acid was increased; thus when HNO_{3} was taken per 1/2Na_{2}SO_{4}, 1,752 heat units were absorbed per equivalent of soda contained in the sodium sulphate. When twice as much nitric acid was taken, 2,026 heat units, and when three times as much, 2,050 heat units were absorbed. Had the double decomposition been complete in the case where one equivalent of nitric acid was taken per equivalent of Na_{2}SO_{4} then according to calculation from similar data there should have been absorbed -2,989 units of heat, while in reality only -1,752 units were absorbed. Hence Thomsen concluded that a displacement of only about two-thirds of the sulphuric acid had taken place--that is, the ratio _k_ : _k_´ for the reaction 1/2Na_{2}SO_{4} + HNO_{3} and NaNO_{3} + 1/2H_{2}SO_{4} is equal, as for ethereal salts, to 4. By taking this figure and admitting the above supposition, Thomsen found that for all mixtures of soda with nitric acid, and of sodium nitrate with sulphuric acid, the amounts of heat followed Guldberg and Waage's law; that is, the limit of decomposition reached was greater the greater the mass of acid added. The relation of hydrochloric to sulphuric acid gave the same results. Therefore the researches of Thomsen fully confirm the hypotheses of Guldberg and Waage and the doctrine of Berthollet. Thomson concludes his investigation with the words: (_a_) 'When equivalent quantities of NaHO, HNO_{3} (or HCl) and 1/2H_{2}SO_{4} react on one another in an aqueous solution, then two-thirds of the soda combines with the nitric and one-third with the sulphuric acid; (_b_) this subdivision repeats itself, whether the soda be taken combined with nitric or with sulphuric acid; (_c_) and therefore nitric acid has double the tendency to combine with the base that sulphuric acid has, and hence in an aqueous solution it is a stronger acid than the latter.' 'It is therefore necessary,' Thomsen afterwards remarks, 'to have an expression indicating the tendency of an acid for the saturation of bases. This idea cannot be expressed by the word _affinity_, because by this term is most often understood that force which it is necessary to overcome in order to decompose a substance into its component parts. This force should therefore be measured by the amount of work or heat employed for the decomposition of the substance. The above-mentioned phenomenon is of an entirely different nature,' and Thomsen introduces the term _avidity_, by which he designates the tendency of acids for neutralisation. 'Therefore the avidity of nitric acid with respect to soda is twice as great as the avidity of sulphuric acid. An exactly similar result is obtained with hydrochloric acid, so that its avidity with respect to soda is also double the avidity of sulphuric acid. Experiments conducted with other acids showed that not one of the acids investigated had so great an avidity as nitric acid; some had a greater avidity than sulphuric acid, others less, and in some instances the avidity = 0.' The reader will naturally see clearly that the path chosen by Thomsen deserves to be worked out, for his results concern important questions of chemistry, but great faith cannot be placed in the deductions he has already arrived at, because great complexity of relations is to be seen in the very method of his investigation. It is especially important to turn attention to the fact that all the reactions investigated are reactions of double decomposition. In them A and B do not combine with C and distribute themselves according to their affinity or avidity for combination, but reversible reactions are induced. MX and NY give MY and NX, and conversely; therefore the affinity or avidity for combination is not here directly determined, but only the difference or relation of the affinities or avidities. The affinity of nitric acid not only for the water of constitution, but also for that serving for solution, is much less than that of sulphuric acid. This is seen from thermal data. The reaction N_{2}O_{5} + H_{2}O gives +3,600 heat units, and the solution of the resultant hydrate, 2NHO_{3}, in a large excess of water evolves +14,986 heat units. The formation of SO_{3} + H_{2}O evolves +21,308 heat units, and the solution of H_{2}SO_{4} in an excess of water 17,860--that is, sulphuric acid gives more heat in both cases. The interchange between Na_{2}SO_{4} and 2HNO_{3} is not only accomplished at the expense of the production of NaNO_{3}, but also at the expense of the formation of H_{2}SO_{4}, hence the affinity of sulphuric acid for water plays its part in the phenomena of displacement. Therefore in determinations like those made by Thomsen the water does not form a medium which is present without participating in the process; it also takes part in the reaction. (Compare Chapter IX., Note 14.) Whilst retaining essentially the methods of Thomsen, Ostwald (1876) determined the variation of the sp. gr. (and afterwards of volume), proceeding in the same dilute solutions, on the saturation of acids by bases, and in the decomposition of the salts of one acid by the other, and arrived at conclusions of just the same nature as Thomsen's. Ostwald's method will be clearly understood from an example. A solution of caustic soda containing an almost molecular (40 grams) weight per litre had a specific gravity of 1·04051. The specific gravities of solutions of equal volume and equivalent composition of sulphuric and nitric acids were 1·02970 and 1·03084 respectively. On mixing the solutions of NaHO and H_{2}SO_{4} there was formed a solution of Na_{2}SO_{4} of sp. gr. 1·02959; hence there ensued a decrease of specific gravity which we will term Q, equal to 1·04051 + 1·02970-2(1·02959) = 0·01103. So also the specific gravity after mixture of the solutions of NaHO and HNO_{3} was 1·02633, and therefore Q = 0·01869. When one volume of the solution of nitric acid was added to two volumes of the solution of sodium sulphate, a solution of sp. gr. 1·02781 was obtained, and therefore the resultant decrease of sp. gr. Q_{1} = 2(1·02959) + 1·03084-3(1·02781) = 0·00659. Had there been no chemical reaction between the salts, then according to Ostwald's reasoning the specific gravity of the solutions would not have changed, and if the nitric acid had entirely displaced the sulphuric acid Q_{2} would be = 0·01869-0·01103 = 0·00766. It is evident that a portion of the sulphuric acid was displaced by the nitric acid. But the measure of displacement is not equal to the ratio between Q_{1} and Q_{2}, because a decrease of sp. gr. also occurs on mixing the solution of sodium sulphate with sulphuric acid, whilst the mixing of the solutions of sodium nitrate and nitric acid only produces a slight variation of sp. gr. which falls within the limits of experimental error. Ostwald deduces from similar data the same conclusions as Thomsen, and thus reconfirms the formula deduced by Guldberg and Waage, and the teaching of Berthollet. The participation of water is seen still more clearly in the methods adopted by Ostwald than in those of Thomsen, because in the saturation of solutions of acids by alkalis (which Kremers, Reinhold, and others had previously studied) there is observed, not a contraction, as might have been expected from the quantity of heat which is then evolved, but an expansion, of volume (a decrease of specific gravity, if we calculate as Ostwald did in his first investigations). Thus by mixing 1,880 grams of a solution of sulphuric acid of the composition SO_{3} + 100H_{2}O, occupying a volume of 1,815 c.c., with a corresponding quantity of a solution 2(NaHO + 5H_{2}O), whose volume = 1,793 c.c., we obtain not 3,608 but 3,633 c.c., an expansion of 25 c.c. per gram molecule of the resulting salt, Na_{2}SO_{4}. It is the same in other cases. Nitric and hydrochloric acids give a still greater expansion than sulphuric acid, and potassium hydroxide than sodium hydroxide, whilst a solution of ammonia gives a contraction. The relation to water must be considered as the cause of these phenomena. When sodium hydroxide and sulphuric acid dissolve in water they develop heat and give a vigorous contraction; the water is separated from such solutions with great difficulty. After mutual saturation they form the salt Na_{2}SO_{4}, which retains the water but feebly and evolves but little heat with it, i.e., in other words, has little affinity for water. In the saturation of sulphuric acid by soda the water is, so to say, displaced from a stable combination and passes into an unstable combination; hence an expansion (decrease of sp. gr.) takes place. It is not the reaction of the acid on the alkali, but the reaction of water, that produces the phenomenon by which Ostwald desires to measure the degree of salt formation. The water, which escaped attention, itself has affinity, and influences those phenomena which are being investigated. Furthermore, in the given instance its influence is very great because its mass is large. When it is not present, or only present in small quantities, the attraction of the base to the acid leads to contraction, and not expansion. Na_{2}O has a sp. gr. 2·8, hence its molecular volume = 22; the sp. gr. of SO_{3} is 1·9 and volume 41, hence the sum of their volumes is 63; for Na_{2}SO_{4} the sp. gr. is 2·65 and volume 53·6, consequently there is a contraction of 10 c.c. per gram-molecule of salt. The volume of H_{2}SO_{4} = 53·3, that of 2NaHO = 37·4; there is produced 2H_{2}O, volume = 36, + Na_{2}SO_{4}, volume = 53·6. There react 90·7 c.c., and on saturation there result 89·6 c.c.; consequently contraction again ensues, although less, and although this reaction is one of substitution and not of combination. Consequently the phenomena studied by Ostwald depend but little on the measure of the reaction of the salts, and more on the relations of the dissolved substances to water. In substitutions, for instance 2NaNO_{3} + H_{2}SO_{4} = 2HNO_{3} + Na_{2}SO_{4}, the volumes vary but slightly: in the above example they are 2(38·8) + 53·3 and 2(41·2) + 53·6; hence 131 volumes act, and 136 volumes are produced. It may be concluded, therefore, on the basis of what has been said, that on taking water into consideration the phenomena studied by Thomsen and Ostwald are much more complex than they at first appear, and that this method can scarcely lead to a correct interpretation as to the distribution of acids between bases. We may add that P. D. Chroustcheff (1890) introduced a new method for this class of research, by investigating the electro-conductivity of solutions and their mixtures, and obtained remarkable results (for example, that hydrochloric acid almost entirely displaces formic acid and only 2/3 of sulphuric acid), but details of these methods must be looked for in text-books of theoretical chemistry. [28] G. G. Gustavson's researches, which were conducted in the laboratory of the St. Petersburg University in 1871-72, are among the first in which the measure of the affinity of the elements for the halogens is recognised with perfect clearness in the limit of substitution and in the rate of reaction. The researches conducted by A. L. Potilitzin (of which mention will be made in Chapter XI., Note 66) in the same laboratory touch on another aspect of the same problem which has not yet made much progress, notwithstanding its importance and the fact that the theoretical side of the subject (thanks especially to Guldberg and Van't Hoff) has since been rapidly pushed forward. If the researches of Gustavson took account of the influence of mass, and were more fully supplied with data concerning velocities and temperatures, they would be very important, because of the great significance which the case considered has for the understanding of double saline decompositions in the absence of water. Furthermore Gustavson showed that the greater the atomic weight of the element (B, Si, Ti, As, Sn) combined _with chlorine_ the greater the amount of chlorine replaced by bromine by the action of CBr_{4}, and consequently the less the amount of bromine replaced by chlorine by the action of CCl_{4} on bromine compounds. For instance, for chlorine compounds the percentage of substitution (at the limit) is-- BCl_{3} SiCl_{4} TiCl_{4} AsCl_{3} SnCl_{4} 10·1 12·5 43·6 71·8 77·5 It should he observed, however, that Thorpe, on the basis of his experiments, denies the universality of this conclusion. I may mention one conclusion which it appears to me may be drawn from the above-cited figures of Gustavson, if they are subsequently verified even within narrow limits. If CBr_{4} be heated with RCl_{4}, then an exchange of the bromine for chlorine takes place. But what would be the result if it were mixed with CCl_{4}? Judging by the magnitude of the atomic weights, B = 11, C = 12, Si = 28, about 11 p.c. of the chlorine would be replaced by bromine. But to what does this point? I think that this shows the existence of a motion of the atoms in the molecule. The mixture of CCl_{4} and CBr_{4} does not remain in a condition of static equilibrium; not only are the molecules contained in it in a state of motion, but also the atoms in the molecules, and the above figures show the measure of their translation under these conditions. The bromine in the CBr_{4} is, _within the limit_, substituted by the chlorine of the CCl_{4} in a quantity of about 11 out of 100: that is, a portion of the atoms of bromine previously to this moment in combination with one atom of carbon pass over to the other atom of carbon, and the chlorine passes over from this second atom of carbon to replace it. Therefore, also, in the homogeneous mass CCl_{4} all the atoms of Cl do not remain constantly combined with the same atoms of carbon, and _there is on exchange of atoms between different molecules in a homogeneous medium also_. This hypothesis may in my opinion explain certain phenomena of dissociation, but though mentioning it I do not consider it worth while to dwell upon it. I will only observe that a similar hypothesis suggested itself to me in my researches on solutions, and that Pfaundler enunciated an essentially similar hypothesis, and in recent times a like view is beginning to find favour with respect to the electrolysis of saline solutions. Thus we now find ample confirmation from various quarters for the following rules of Berthollet, applying them to double saline decompositions: 1. From two salts MX and NY containing different haloids and metals there result from their reaction two others, MY and NX, but such a substitution will not proceed to the end unless one product passes from the sphere of action. 2. This reaction is limited by the existence of an equilibrium between MX, NY, MY, and NX, because a reverse reaction is quite as possible as the direct reaction. 3. This limit is determined both by the measure of the active affinities and by the relative masses of the substances as measured by the number of the reacting molecules. 4. Other conditions being constant, the chemical action is proportional to the product of the chemical masses in action.[29] [29] Berthollet's doctrine is hardly at all affected in principle by showing that there are cases in which there is no decomposition between salts, because the affinity may be so small that even a large mass would still give no observable displacements. The fundamental condition for the application of Berthollet's doctrine, as well as Deville's doctrine of dissociation, lies in the reversibility of reactions. There are practically irreversible reactions (for instance, CCl_{4} + 2H_{2}O = CO_{2} + 4HCl), just as there are non-volatile substances. But while accepting the doctrine of reversible reactions and retaining the theory of the evaporation of liquids, it is possible to admit the existence of non-volatile substances, and in just the same way of reactions, without any visible conformity to Berthollet's doctrine. This doctrine evidently comes nearer than the opposite doctrine of Bergmann to solving the complex problems of chemical mechanics for the successful solution of which at the present time the most valuable help is to be expected from the working out of data concerning dissociation, the influence of mass, and the equilibrium and velocity of reactions. But it is evident that from this point of view we must not regard a solvent as a non-participant space, but must take into consideration the chemical reactions accompanying solution, or else bring about reactions without solution. Thus if the salts MX and NY after reaction partly formed salts MY and NX, then a state of equilibrium is reached and the reaction ceases; but if one of the resultant compounds, in virtue of its physical properties, passes from the sphere of action of the remaining substances, then the reaction will continue. This exit from the sphere of action depends on the physical properties of the substance and on the conditions under which the reaction takes place. Thus, for instance, the salt NX may, in the case of reaction between solutions, separate as a precipitate, an insoluble substance, while the other three substances remain in solution, or it may pass into vapour, and in this manner also pass away from the sphere of action of the remaining substances. Let us now suppose that it passes away in some form or other from the sphere of action of the remaining substances--for instance, that it is transformed into a precipitate or vapour--then a fresh reaction will set in and a re-formation of the salt NX. If this be removed, then, although the quantity of the elements N and X in the mass will be diminished, still, according to Berthollet's law, a certain amount of NX should be again formed. When this substance is again formed, then, owing to its physical properties, it will again pass away; hence the reaction, in consequence of the physical properties of the resultant substances, is able to proceed to completion notwithstanding the possible weakness of the attraction existing between the elements entering into the composition of the resultant substance NX. Naturally, if the resultant substance is formed of elements having a considerable degree of affinity, then the complete decomposition is considerably facilitated. Such a representation of the _modus operandi_ of chemical transformations is applicable with great clearness to a number of reactions studied in chemistry, and, what is especially important, the application of this aspect of Berthollet's teaching does not in any way require the determination of the measure of affinity acting between the substances present. For instance, the action of ammonia on solutions of salts; the displacement, by its means, of basic hydrates insoluble in water; the separation of volatile nitric acid by the aid of non-volatile sulphuric acid, as well as the decomposition of common salt by means of sulphuric acid, when gaseous hydrochloric acid is formed--may be taken as examples of reactions which proceed to the end, inasmuch as one of the resultant substances is entirely removed from the sphere of action, but they in no way indicate the measure of affinity.[30] [30] Common salt not only enters into double decomposition with acids but also _with every salt_. However, as clearly follows from Berthollet's doctrine, this form of decomposition will only in a few cases render it possible for new metallic chlorides to be obtained, because the decomposition will not be carried on to the end unless the metallic chloride formed separates from the mass of the active substances. Thus, for example, if a solution of common salt be mixed with a solution of magnesium sulphate, double decomposition ensues, but not completely, because all the substances remain in the solution. In this case the decomposition must result in the formation of sodium sulphate and magnesium chloride, substances which are soluble in water; nothing is disengaged, and therefore the decomposition 2NaCl + MgSO_{4} = MgCl_{2} + Na_{2}SO_{4} cannot proceed to the end. However, the sodium sulphate formed in this manner may be separated by freezing the mixture. The complete separation of the sodium sulphate will naturally not take place, owing to a portion of the salt remaining in the solution. Nevertheless, this kind of decomposition is made use of for the preparation of sodium sulphate from the residues left after the evaporation of sea-water, which contain a mixture of magnesium sulphate and common salt. Such a mixture is found at Stassfurt in a natural form. It might be said that this form of double decomposition is only accomplished with a change of temperature; but this would not be true, as may be concluded from other analogous cases. Thus, for instance, a solution of copper sulphate is of a blue colour, while a solution of copper chloride is green. If we mix the two salts together the green tint is distinctly visible, so that by this means the presence of the copper chloride in the solution of copper sulphate is clearly seen. If now we add a solution of common salt to a solution of copper sulphate, a green coloration is obtained, which indicates the formation of copper chloride. In this instance it is not separated, but it is immediately formed on the addition of common salt, as it should be according to Berthollet's doctrine. The complete formation of a metallic chloride from common salt can only occur, judging from the above, when it separates from the sphere of action. The salts of silver are instances in point, because the silver chloride is insoluble in water; and therefore if we add a solution of sodium chloride to a solution of a silver salt, silver chloride and the sodium salt of that acid which was in the silver salt are formed. As a proof that double decompositions like the above are actually accomplished in the sense of Berthollet's doctrine, the fact may be cited that common salt may be entirely decomposed by nitric acid, and nitre may be completely decomposed by hydrochloric acid, just as they are decomposed by sulphuric acid; but this only takes place when, in the first instance, an excess of nitric acid is taken, and in the second instance, an excess of hydrochloric acid, for a given quantity of the sodium salt, and when the resultant acid passes off. If sodium chloride be put into a porcelain evaporating basin, nitric acid added to it, and the mixture heated, then both hydrochloric and nitric acids are expelled by the heat. Thus the nitric acid partially acts on the sodium chloride, but on heating, as both acids are volatile, they are both converted into vapour; and therefore the residue will contain a mixture of a certain quantity of the sodium chloride taken and of the sodium nitrate formed. If a fresh quantity of nitric acid be then added, reaction will again set in, a certain portion of hydrochloric acid is again evolved, and on heating is expelled together with nitric acid. If this be repeated several times, it is possible to expel all the hydrochloric acid, and to obtain sodium nitrate only in the residue. If, on the contrary, we take sodium nitrate and add hydrochloric acid to it in an aqueous solution, a certain quantity of the hydrochloric acid displaces a portion of the nitric acid, and on heating the excess of hydrochloric acid passes away with the nitric acid formed. On repeating this process, it is possible to displace the nitric acid with an excess of hydrochloric acid, just as it was possible to displace the hydrochloric acid by an excess of nitric acid. The influence of the mass of the substance in action and the influence of volatility are here very distinctly seen. Hence it may be affirmed that sulphuric acid does not displace hydrochloric acid because of an especially high degree of affinity, but that this reaction is only carried on to the end because the sulphuric acid is not volatile, whilst the hydrochloric acid which is formed is volatile. The preparation of hydrochloric acid in the laboratory and on a large scale is based upon these data. In the first instance, an excess of sulphuric acid is employed in order that the reaction may proceed easily at a low temperature, whilst on a large scale, when it is necessary to economise every material, equivalent quantities are taken in order to obtain the normal salt Na_{2}SO_{4} and not the acid salt, which would require twice as much acid. The hydrochloric acid evolved is a gas which is very soluble in water. It is most frequently used in practice in this state of solution under the name of _muriatic acid_.[31] [31] The apparatus shown in fig. 46 (Chapter VI., Note 12) is generally employed for the preparation of small quantities of hydrochloric acid. Common salt is placed in the retort; the salt is generally previously fused, as it otherwise froths and boils over in the apparatus. When the apparatus is placed in order sulphuric acid mixed with water is poured down the thistle funnel into the retort. Strong sulphuric acid (about half as much again as the weight of the salt) is usually taken, and it is diluted with a small quantity of water (half) if it be desired to retard the action, as in using strong sulphuric acid the action immediately begins with great vigour. The mixture, at first without the aid of heat and then at a moderate temperature (in a water-bath), evolves hydrochloric acid. Commercial hydrochloric acid contains many impurities; it is usually purified by distillation, the middle portions being collected. It is purified from arsenic by adding FeCl_{2}, distilling, and rejecting the first third of the distillate. If free hydrochloric acid gas be required, it is passed through a vessel containing strong sulphuric acid to dry it, and is collected over a mercury hath. Phosphoric anhydride absorbs hydrogen chloride (Bailey and Fowler, 1888; 2P_{2}O_{3} + 3HCl = POCl_{3} + 3HPO_{3}) at the ordinary temperature, and therefore the gas cannot he dried by this substance. [Illustration: FIG. 65.--Section of a salt-cake furnace. B, pan in which the sodium chloride and sulphuric acid are first mixed and heated. C, muffle for the ultimate decomposition.] In chemical works the decomposition of sodium chloride by means of sulphuric acid is carried on on a very large scale, chiefly with a view to the preparation of normal sodium sulphate, the hydrochloric acid being a bye-product.[31 bis] The furnace employed is termed a _salt cake furnace_. It is represented in fig. 65, and consists of the following two parts: the pan B and the roaster C, or enclosed space built up of large bricks _a_ and enveloped on all sides by the smoke and flames from the fire grate, F. The ultimate decomposition of the salt by the sulphuric acid is accomplished in the roaster. But the first decomposition of sodium chloride by sulphuric acid does not require so high a temperature as the ultimate decomposition, and is therefore carried on in the front and cooler portion, B, whose bottom is heated by gas flues. When the reaction in this portion ceases and the evolution of hydrochloric acid stops, then the mass, which contains about half of the sodium chloride still undecomposed, and the sulphuric acid in the form of acid sodium sulphate, is removed from B and thrown into the roaster C, where the action is completed. Normal sodium sulphate, which we shall afterwards describe, remains in the roaster. It is employed both directly in the manufacture of glass, and in the preparation of other sodium compounds--for instance, in the preparation of soda ash, as will afterwards be described. For the present we will only turn our attention to the hydrochloric acid evolved in B and C. [31 bis] In chemical works where sulphuric acid of 60° Baumé (22 p.c. of water) is employed, 117 parts of sodium chloride are taken to about 125 parts of sulphuric acid. The hydrochloric acid gas evolved is subjected to condensation by dissolving it in water.[32] If the apparatus in which the decomposition is accomplished were hermetically closed, and only presented one outlet, then the escape of the hydrochloric acid would only proceed through the escape pipe intended for this purpose. But as it is impossible to construct a perfectly hermetically closed furnace of this kind, it is necessary to increase the draught by artificial means, or to oblige the hydrochloric acid gas to pass through those arrangements in which it is to be condensed. This is done by connecting the ends of the tubes through which the hydrochloric acid gas escapes from the furnace with high chimneys, where a strong draught is set up from the combustion of the fuel. This causes a current of hydrochloric acid gas to pass through the absorbing apparatus in a definite direction. Here it encounters a current of water flowing in the opposite direction, by which it is absorbed. It is not customary to cause the acid to pass through the water, but only to bring it into contact with the surface of the water. The absorption apparatus consists of large earthenware vessels having four orifices, two above and two lateral ones in the wide central portion of each vessel. The upper orifices serve for connecting the vessels together, and the hydrochloric acid gas escaping from the furnace passes through these tubes. The water for absorbing the acid enters at the upper, and flows out from the lower, vessel, passing through the lateral orifices in the vessels. The water flows from the chimney towards the furnace and it is therefore evident that the outflowing water will be the most saturated with acid, of which it actually contains about 20 per cent. The absorption in these vessels is not complete. The ultimate absorption of the hydrochloric acid is carried on in the so-called _coke towers_, which usually consist of two adjacent chimneys. A lattice-work of bricks is laid on the bottom of these towers, on which coke is piled up to the top of the tower. Water, distributing itself over the coke, trickles down to the bottom of the tower, and in so doing absorbs the hydrochloric acid gas rising upwards. [32] As in works which treat common salt in order to obtain sodium sulphate, the hydrochloric acid is sometimes held to be of no value, it might be allowed to escape with the waste furnace gases into the atmosphere, which would greatly injure the air of the neighbourhood and destroy all vegetation. In all countries, therefore, there are laws forbidding the factories to proceed in this manner, and requiring the absorption of the hydrochloric acid by water at the works themselves, and not permitting the solution to be run into rivers and streams, whose waters it would spoil. It may be remarked that the absorption of hydrochloric acid presents no particular difficulties (the absorption of sulphurous acid is much more difficult) because hydrochloric acid has a great affinity for water and gives a hydrate which boils above 100°. Hence, even steam and hot water, as well as weaker solutions, can be used for absorbing the acid. However, Warder (1888) showed that weak solutions of composition H_{2}O + _n_HCl when boiled (the residue will be almost HCl,8H_{2}O) evolve (not water but) a solution of the composition H_{2}O + 445_n_^{4}HCl; for example, on distilling HCl,10H_{2}O, HCl,23H_{2}O is first obtained in the distillate. As the strength of the residue becomes greater, so also does that of the distillate, and therefore in order to completely absorb hydrochloric acid it is necessary in the end to have recourse to water. As in Russia the manufacture of sodium sulphate from sodium chloride has not yet been sufficiently developed, and as hydrochloric acid is required for many technical purposes (for instance, for the preparation of zinc chloride, which is employed for soaking railway sleepers), therefore salt is often treated mainly for the manufacture of hydrochloric acid. It will be readily understood that hydrochloric acid may be obtained from all other metallic chlorides.[33] It is frequently formed in other reactions, many of which we shall meet with in the further course of this work. It is, for instance, formed by the action of water on sulphur chloride, phosphorus chloride, antimony chloride, &c. [33] Thus the metallic chlorides, which are decomposed to a greater or less degree by water, correspond with feeble bases. Such are, for example, MgCl_{2}, AlCl_{3}, SbCl_{3}, BiCl_{3}. The decomposition of magnesium chloride (and also carnallite) by sulphuric acid proceeds at the ordinary temperature; water decomposes MgCl_{2} to the extent of 50 p.c. when aided by heat, and _may be employed_ as a convenient _method for the production of hydrochloric acid_. Hydrochloric acid is also produced by the ignition of certain metallic chlorides in a stream of hydrogen, especially of those metals which are easily reduced and difficultly oxidised--for instance, silver chloride. Lead chloride, when heated to redness in a current of steam, gives hydrochloric acid and lead oxide. The multitude of the cases of formation of hydrochloric acid are understood from the fact that it is a substance which is comparatively very stable, resembling water in this respect, and even most probably more stable than water, because, at a high temperature and even under the action of light, chlorine decomposes water, with the formation of hydrochloric acid. The combination of chlorine and hydrogen also proceeds by their direct action, as we shall afterwards describe. _Hydrochloric acid_ is a colourless gas having a pungent suffocating odour and an acid taste. This gas fumes in air and attracts moisture, because it forms vapour containing a compound of hydrochloric acid and water. Hydrochloric acid is liquefied by cold, and under a pressure of 40 atmospheres, into a colourless liquid of sp. gr. 0·908 at 0°,[34] boiling point -35° and absolute boiling point +52°. We have already seen (Chapter I.) that hydrochloric acid combines very energetically _with water_, and in so doing evolves a considerable amount of heat. The solution saturated in the cold attains a density 1·23. On heating such a solution containing about 45 parts of acid per 100 parts, the hydrochloric acid gas is expelled with only a slight admixture of aqueous vapour. But it is impossible to entirely separate the whole of the hydrochloric acid from the water by this means, as could be done in the case of an ammoniacal solution. The temperature required for the evolution of the gas rises and reaches 110°-111°, and after this remains constant--that is, a solution having a constant boiling point is obtained (as with HNO_{3}), which, however, does not (Roscoe and Dittmar) present a constant composition under different pressures, because the hydrate is decomposed in distillation, as is seen from the determinations of its vapour density (Bineau). Judging from the facts (1) that with decrease of the pressure under which the distillation proceeds the solution of constant boiling point approaches to a composition of 25 p.c. of hydrochloric acid,[35] (2) that by passing a stream of dry air through a solution of hydrochloric acid there is obtained in the residue a solution which also approaches to 25 p.c. of acid, and more nearly as the temperature falls,[36] (3) that many of the properties of solutions of hydrochloric acid vary distinctly according as they contain more or less than 25 p.c. of hydrochloric acid (for instance, antimonious sulphide gives hydrogen sulphide with a stronger acid, but is not acted on by a weaker solution, also a stronger solution fumes in the air, &c.), and (4) that the composition HCl,6H_{2}O corresponds with 25·26 p.c. HCl--judging from all these data, and also from the loss of tension which occurs in the combination of hydrochloric acid with water, it may be said that they form a _definite hydrate_ of the composition HCl,6H_{2}O. Besides this hydrate there exists also a crystallo-hydrate, HCl,2H_{2}O,[37] which is formed by the absorption of hydrochloric acid by a saturated solution at a temperature of -23°. It crystallises and melts at -18°.[38] [34] According to Ansdell (1880) the sp. gr. of liquid hydrochloric acid at 0° = 0·908, at 11·67° = 0·854, at 22·7° = 0·808, at 33° = 0·748. Hence it is seen that the expansion of this liquid is greater than that of gases (Chapter II., Note 34). [35] According to Roscoe and Dittmar at a pressure of three atmospheres the solution of constant boiling point contains 18 p.c. of hydrogen chloride, and at a pressure of one-tenth atmosphere 23 p.c. The percentage is intermediate at medium pressures. [36] At 0° 25 p.c., at 100° 20·7 p.c.; Roscoe and Dittmar. [37] This crystallo-hydrate (obtained by Pierre and Puchot, and investigated by Roozeboom) is analogous to NaCl,2H_{2}O. The crystals HCl,2H_{2}O at -22° have a specific gravity 1·46; the vapour tension (under dissociation) of the solution having a composition HCl,2H_{2}O at -24° = 760, at -19° = 1,010, at -18° = 1,057, at -17° = 1,112 mm. of mercury. In a solid state the crystallo-hydrate at -17·7° has the same tension, whilst at lower temperatures it is much less: at -24° about 150, at -19° about 580 mm. A mixture of fuming hydrochloric acid with snow reduces the temperature to -38°. If another equivalent of water be added to the hydrate HCl,2H_{2}O at -18°, the temperature of solidification falls to -25°, and the hydrate HCl,3H_{2}O is formed (Pickering, 1893). [38] According to Roscoe at 0° one _hundred_ grams of water at a pressure _p_ (in millimetres of mercury) dissolves-- _p_ = 100 200 300 500 700 1,000 Grams HCl 65·7 70·7 73·8 78·2 81·7 85·6 At a pressure of 760 millimetres and temperature _t_, one _hundred_ grams of water dissolves _t_ = 0 8° 16° 24° 40° 60° Grams HCl 82·5 78·3 74·2 70·0 63·3 56·1 Roozeboom (1886) showed that at _t_° solutions containing _c_ grams of hydrogen chloride per 100 grams of water may (with the variation of the pressure _p_) be formed together with the crystallo-hydrate HCl,2H_{2}O: _t_ = -28°·8 -21° -19° -18° -17°·7 _c_ = 84·2 86·8 92·6 98·4 101·4 _p_ = -- 334 580 900 1,073 mm. The last combination answers to the melted crystallo-hydrate HCl,2H_{2}O, which splits up at temperatures above -17°·7, and at a constant atmospheric pressure when there are no crystals-- _t_ = -24° -21° -18° -10° 0° _c_ = 101·2 98·3 95·7 89·8 84·2 From these data it is seen that the hydrate HCl,2H_{2}O can exist in a liquid state, which is not the case for the hydrates of carbonic and sulphurous anhydrides, chlorine, &c. According to Marignac, the specific heat _c_ of a solution HCl + _m_H_{2}O (at about 30°, taking the specific heat of water = 1) is given by the expression-- C(36·5 + _m_18) = 18_m_ - 28·39 + 140/_m_ - 268/_m_^2 if _m_ be not less than 6·25. For example, for HCl + 25H_{2}O, C = 0·877. According to Thomsen's data, the amount of heat _Q_, expressed in thousands of calories, evolved in the solution of 36·5 grams of gaseous hydrochloric acid in _m_H_{2}O or 18_m_ grams of water is equal to-- _m_ = 2 4 10 50 400 _Q_ = 11·4 14·3 16·2 17·1 17·3 In these quantities the latent heat of liquefaction is included, which must be taken as 5-9 thousand calories per molecular quantity of hydrogen chloride. The researches of Scheffer (1888) on the rate of diffusion (in water) of solutions of hydrochloric acid show that the coefficient of diffusion _k_ decreases with the amount of water _n_, if the composition of the solution is HCl,_n_H_{2}O at 0°:-- _n_ = 5 6·9 9·8 14 27·1 129·5 _k_ = 2·31 2·08 1·86 1·67 1·52 1·39 It also appears that strong solutions diffuse more rapidly into dilute solutions than into water. The mean specific gravities at 15°, taking water at its maximum density (4°) as 10,000, for solutions containing _p_ per cent. of hydrogen chloride are-- _p_ _S_ _p_ _S_ 5 10,242 25 11,266 10 10,490 30 11,522 15 10,744 35 11,773 20 11,001 40 11,997 The formula _S_ = 9,991·6 + 49·43_p_ + 0·0571_p_^2, up to _p_ = 25·26, which answers to the hydrate HCl,6H_{2}O mentioned above, gives the specific gravity. Above this percentage _S_ = 9,785·1 + 65·10_p_-0·240_p_^2. The rise of specific gravity with an increase of percentage (or the differential _ds/dp_) reaches a maximum at about 25 p.c.[39] The intermediate solution, HCl,6H_{2}O, is further distinguished by the fact that the variation of the specific gravity with the variation of temperature is a constant quantity, so that the specific gravity of this solution is equal to 11,352·7(1-0·000447_t_), where 0·000447 is the coefficient of expansion of the solution.[40] In the case of more dilute solutions, as with water, the specific gravity per 1° (or the differential _ds_/_dt_) rises with a rise of temperature.[41] _p_ = 0 5 10 15 20 _S__{0} - _S__{15} = 7·2 23 38 52 64 _S__{15} - _S__{30} = 34·1 42 50 59 67 Whilst for solutions which contain a greater proportion of hydrogen chloride than HCl,6H_{2}O, these coefficients _decrease_ with a rise of temperature; for instance, for 30 p.c. of hydrogen chloride _S__{0}-_S__{15} = 88 and _S__{15}-_S__{30} = 87 (according to Marignac's data). In the case of HCl,6H_{2}O these differences are constant, and equal 76. [39] If it be admitted that the maximum of the differential corresponds with HCl,6H_{2}O, then it might be thought that the specific gravity is expressed by a parabola of the third order; but such an admission does not give expressions in accordance with fact. This is all more fully considered in my work mentioned in Chapter I., Note 19. [40] As in water, the coefficient of expansion (or the quantity _k_ in the expression S_{_t_} = S_{_0_}-_k_S_{_0_}_t_, or V_t_ = 1/(1-_kt_)) attains a magnitude 0·000447 at about 48°, it might be thought that at 48° all solutions of hydrochloric acid would have the same coefficient of expansion, but in reality this is not the case. At low and at the ordinary temperatures the coefficient of expansion of aqueous solutions is greater than that of water, and increases with the amount of substance dissolved. [41] The figures cited above may serve for the direct determination of that variation of the specific gravity of solutions of hydrochloric acid with the temperature. Thus, knowing that at 15° the specific gravity of a 10 p.c. solution of hydrochloric acid = 10,492, we find that at _t_° it = 10,530-_t_(2·13 + 0·027_t_). Whence also may be found the coefficient of expansion (Note 40). Thus the formation of two definite hydrates, HCl,2H_{2}O and HCl,6H_{2}O, between hydrochloric acid and water may be accepted upon the basis of many facts. But both of them, if they occur in a liquid state, dissociate with great facility into hydrogen chloride and water, and are completely decomposed when distilled. All solutions of hydrochloric acid present the properties of an energetic acid. They not only transform blue vegetable colouring matter into red, and disengage carbonic acid gas from carbonates, &c., but they also entirely saturate bases, even such energetic ones as potash, lime, &c. In a dry state, however, hydrochloric acid does not alter vegetable dyes, and does not effect many double decompositions which easily take place in the presence of water. This is explained by the fact that the gaso-elastic state of the hydrochloric acid prevents its entering into reaction. However, incandescent iron, zinc, sodium, &c., act on gaseous hydrochloric acid, displacing the hydrogen and leaving half a volume of hydrogen for each volume of hydrochloric acid gas; this reaction may serve for determining the composition of hydrochloric acid. Combined with water hydrochloric acid acts as an acid much resembling nitric acid[42] in its energy and in many of its reactions; however, the latter contains oxygen, which is disengaged with great ease, and so very frequently acts as an oxidiser, which hydrochloric acid is not capable of doing. The majority of metals (even those which do not displace the H from H_{2}SO_{4}, but which, like copper, decompose it to the limit of SO_{2}) displace the hydrogen from hydrochloric acid. Thus hydrogen is disengaged by the action of zinc, and even of copper and tin.[42 bis] Only a few metals withstand its action; for example, gold and platinum. Lead in compact masses is only acted on feebly, because the lead chloride formed is insoluble and prevents the further action of the acid on the metal. The same is to be remarked with respect to the feeble action of hydrochloric acid on mercury and silver, because the compounds of these metals, AgCl and HgCl, are insoluble in water. Metallic chlorides are not only formed by the action of hydrochloric acid on the metals, but also by many other methods; for instance, by the action of hydrochloric acid on the carbonates, oxides, and hydroxides, and also by the action of chlorine on metals and certain of their compounds. Metallic chlorides have a composition MCl; for example, NaCl, KCl, AgCl, HgCl, if the metal replaces hydrogen equivalent for equivalent, or, as it is said, if it be monatomic or univalent. In the case of bivalent metals, they have a composition MCl_{2}; for example, CaCl_{2}, CuCl_{2}, PbCl_{2}, HgCl_{2}, FeCl_{2}, MnCl_{2}. The composition of the haloid salts of other metals presents a further variation; for example, AlCl_{3}, PtCl_{4}, &c. Many metals, for instance Fe, give several degrees of combination with chlorine (FeCl_{2}, FeCl_{3}) as with hydrogen. In their composition the metallic chlorides differ from the corresponding oxides, in that the O is replaced by Cl_{2}, as should follow from the law of substitution, because oxygen gives OH_{2}, and is consequently bivalent, whilst chlorine forms HCl, and is therefore univalent. So, for instance, ferrous oxide, FeO, corresponds with ferrous chloride, FeCl_{2}, and the oxide Fe_{2}O_{3} with ferric chloride, which is also seen from the origin of these compounds, for FeCl_{2} is obtained by the action of hydrochloric acid on ferrous oxide or carbonate and FeCl_{3} by its action on ferric oxide. In a word, all the typical properties of acids are shown by hydrochloric acid, and all the typical properties of salts in the metallic chlorides derived from it. Acids and salts composed like HCl and M_{n}Cl_{2m} without any oxygen bear the name of haloid salts; for instance, HCl is a haloid acid, NaCl a haloid salt, chlorine a halogen. The capacity of hydrochloric acid to give, by its action on bases, MO, a metallic chloride, MCl_{2}, and water, is limited at high temperatures by the reverse reaction MCl_{2} + H_{2}O = MO + 2HCl, and the more pronounced are the basic properties of MO the feebler is the reverse action, while for feebler bases such as Al_{2}O_{3}, MgO, &c., this reverse reaction proceeds with ease. Metallic chlorides corresponding with the peroxides either do not exist, or are easily decomposed with the disengagement of chlorine. Thus there is no compound BaCl_{4} corresponding with the peroxide BaO_{2}. Metallic chlorides having the general aspect of salts, like their representative sodium chloride, are, as a rule, easily fusible, more so than the oxides (for instance, CaO is infusible at a furnace heat, whilst CaCl_{2} is easily fused) and many other salts. Under the action of heat many chlorides are more stable than the oxides, some can even be converted into vapour; thus corrosive sublimate, HgCl_{2}, is particularly volatile, whilst the oxide HgO decomposes at a red heat. Silver chloride, AgCl, is fusible and is decomposed with difficulty, whilst Ag_{2}O is easily decomposed. The majority of the metallic chlorides are soluble in water, but silver chloride, cuprous chloride, mercurous chloride, and lead chloride are sparingly soluble in water, and are therefore easily obtained as precipitates when a solution of the salts of these metals is mixed with a solution of any chloride or even with hydrochloric acid. The metal contained in a haloid salt may often be replaced by another metal, or even by hydrogen, just as is the case with a metal in an oxide. Thus copper displaces mercury from a solution of mercuric chloride, HgCl_{2} + Cu = CuCl_{2} + Hg, and hydrogen at a red heat displaces silver from silver chloride, 2AgCl + H_{2} = Ag_{2} + 2HCl. These, and a whole series of similar reactions, form the typical methods of double saline decompositions. The measure of decomposition and the conditions under which reactions of double saline decompositions proceed in one or in the other direction are determined by the properties of the compounds which take part in the reaction, and of those capable of formation at the temperature, &c., as was shown in the preceding portions of this chapter, and as will be frequently found hereafter. [42] Thus, for instance, with feeble bases they evolve in dilute solutions (Chapter III., Note 53) almost equal amounts of heat; their relation to sulphuric acid is quite identical. They both form fuming solutions as well as hydrates; they both form solutions of constant boiling point. [42 bis] Pybalkin (1891) found that copper begins to disengage hydrogen at 100°, and that chloride of copper begins to give up its chlorine to hydrogen gas at 230°; for silver these temperatures are 117° and 260°--that is, there is less difference between them. If hydrochloric acid enters into double decomposition with basic oxides and their hydrates, this is only due to its acid properties; and for the same reason it rarely enters into double decomposition with acids and acid anhydrides. Sometimes, however, it combines with the latter, as, for instance, with the anhydride of sulphuric acid, forming the compound SO_{3}HCl; and in other cases it acts on acids, giving up its hydrogen to their oxygen and forming chlorine, as will be seen in the following chapter. Hydrochloric acid, as may already be concluded from the composition of its molecule, belongs to the monobasic acids, and does not, therefore, give true acid salts (like HNaSO_{4} or HNaCO_{3}); nevertheless many metallic chlorides, formed from powerful bases, are capable of _combining with hydrochloric acid_, just as they combine with water, or with ammonia, or as they give double salts. Compounds have long been known of hydrochloric acid with auric, platinic, and antimonious chlorides, and other similar metallic chlorides corresponding with very feeble bases. But Berthelot, Engel, and others have shown that the capacity of HCl for combining with M_{_n_}Cl_{_m_} is much more frequently encountered than was previously supposed. Thus, for instance, dry hydrochloric acid when passed into a solution of zinc chloride (containing an excess of the salt) gives in the cold (0°) a compound HCl,ZnCl_{2},2H_{2}O, and at the ordinary temperature HCl,2ZnCl_{2},2H_{2}O, just as it is able at low temperatures to form the crystallo-hydrate ZnCl_{2},3H_{2}O (Engel, 1886). Similar compounds are obtained with CdCl_{2},CuCl_{2}, HgCl_{2},Fe_{2}Cl_{6}, &c. (Berthelot, Ditte, Cheltzoff, Lachinoff, and others). These compounds with hydrochloric acid are generally more soluble in water than the metallic chlorides themselves, so that whilst hydrochloric acid decreases the solubility of M_{_n_}Cl_{_m_}, corresponding with energetic bases (for instance, sodium or barium chlorides), it increases the solubility of the metallic chlorides corresponding with feeble bases (cadmium chloride, ferric chloride, &c.) Silver chloride, which is insoluble in water, is soluble in hydrochloric acid. Hydrochloric acid also combines with certain unsaturated hydrocarbons (for instance, with turpentine, C_{10}H_{16},2HCl) and their derivatives. _Sal-ammoniac_, or ammonia hydrochloride, NH_{4}Cl = NH_{3},HCl, also belongs to this class of compounds.[43] If hydrogen chloride gas be mixed with ammonia gas a solid compound consisting of equal volumes of each is immediately formed. The same compound is obtained on mixing solutions of the two gases. It is also produced by the action of hydrochloric acid on ammonium carbonate. Sal-ammoniac is usually prepared, in practice, by the last method.[44] The specific gravity of sal-ammoniac is 1·55. We have already seen (Chapter VI.) that sal-ammoniac, like all other ammonium salts, easily decomposes; for instance, by volatilisation with alkalis, and even partially when its solution is boiled. The other properties and reactions of sal-ammoniac, especially in solution, fully recall those already mentioned in speaking of sodium chloride. Thus, for instance, with silver nitrate it gives a precipitate of silver chloride; with sulphuric acid it gives hydrochloric acid and ammonium sulphate, and it forms double salts with certain metallic chlorides and other salts.[45] [43] When an unsaturated hydrocarbon, or, in general, an unsaturated compound, assimilates to itself the molecules Cl_{2}, HCl, SO_{3}, H_{2}SO_{4}, &c., the cause of the reaction is most simple. As nitrogen, besides the type NX_{3} to which NH_{3}, belongs, gives compounds of the type NX_{5}--for example, NO_{2}(OH)--the formation of the salts of ammonium should be understood in this way. NH_{3} gives NH_{4}Cl because NX_{3} is capable of giving NX_{5}. But as saturated compounds--for instance, SO_{3},H_{2}O, NaCl, &c.--are also capable of combination even between themselves, it is impossible to deny the capacity of HCl also for combination. SO_{3} combines with H_{2}O, and also with HCl and the unsaturated hydrocarbons. It is impossible to recognise the distinction formerly sought to be established between atomic and molecular compounds, and regarding, for instance, PCl_{3} as an atomic compound and PCl_{5} as a molecular one, only because it easily splits up into molecules PCl_{3} and Cl_{2}. [44] Sal-ammoniac is prepared from ammonium carbonate, obtained in the dry distillation of nitrogenous substances (Chapter VI.), by saturating the resultant solution with hydrochloric acid. A solution of sal-ammoniac is thus produced, which is evaporated, and in the residue a mass is obtained containing a mixture of various other, especially tarry, products of dry distillation. The sal-ammoniac is generally purified by sublimation. For this purpose iron vessels covered with hemispherical metallic covers are employed, or else simply clay crucibles covered by other crucibles. The upper portion, or head, of the apparatus of this kind will have a lower temperature than the lower portion, which is under the direct action of the flame. The sal-ammoniac volatilises when heated, and settles on the cooler portion of the apparatus. It is thus freed from many impurities, and is obtained as a crystalline crust, generally several centimetres thick, in which form it is commonly sold. The solubility of sal-ammoniac rises rapidly with the temperature: at 0°, 100 parts of water dissolve about 28 parts of NH_{4}Cl, at 50° about 50 parts, and at the ordinary temperature about 35 parts. This is sometimes taken advantage of for separating NH_{4}Cl from solutions of other salts. [45] The solubility of sal-ammoniac in 100 parts of water (according to Alluard) is-- 0° 10° 20° 30° 40° 60° 80° 100° 110° 28·40 32·48 37·28 41·72 46 55 64 73 77 A saturated solution boils at 115°·8. The specific gravity at 15°/4° of solutions of sal-ammoniac (water 4° = 10,000) = 9,991·6-31·26_p_-0·085_p_^2, where _p_ is the amount by weight of ammonium chloride in 100 parts of solution. With the majority of salts the differential _ds_/_dp_ increases, but here it decreases with the increase of _p_. For (unlike the sodium and potassium salts) a solution of the alkali _plus_ a solution of acid occupy a greater volume than that of the resultant ammonium salt. In the solution of _solid_ ammonium chloride a contraction, and not expansion, generally takes place. It may further be remarked that solutions of sal-ammoniac have an acid reaction even when prepared from the salt remaining after prolonged washing of the sublimed salt with water (A. Stcherbakoff). CHAPTER XI THE HALOGENS: CHLORINE, BROMINE, IODINE, AND FLUORINE Although hydrochloric acid, like water, is one of the most stable substances, it is nevertheless decomposed not only by the action of a galvanic current,[1] but also by a high temperature. Sainte-Claire Deville showed that decomposition already occurs at 1,300°, because a cold tube (as with CO, Chapter IX.) covered with an amalgam of silver absorbs chlorine from hydrochloric acid in a red-hot tube, and the escaping gas contains hydrogen. V. Meyer and Langer (1885) observed the decomposition of hydrochloric acid at 1,690° in a platinum vessel; the decomposition in this instance was proved not only from the fact that hydrogen diffused through the platinum (p. 142), owing to which the volume was diminished, but also from chlorine being obtained in the residue (the hydrogen chloride was mixed with nitrogen), which liberated iodine from potassium iodide.[2] The usual method for the preparation of chlorine consists in the abstraction of the hydrogen by oxidising agents.[2 bis] [1] The decomposition of fused sodium chloride by an electric current has been proposed in America and Russia (N. N. Beketoff) as a means for the preparation of chlorine and sodium. A strong solution of hydrochloric acid is decomposed into equal volumes of chlorine and hydrogen by the action of an electric current. If sodium chloride and lead be melted in a crucible, the former being connected with the cathode and a carbon anode immersed in the lead, then the lead dissolves sodium and chlorine is disengaged as gas. This electrolytic method has not yet been practised on a large scale, probably because gaseous chlorine has not many applications, and because of the difficulty there is in dealing with it. [2] To obtain so high a temperature (at which the best kinds of porcelain soften) Langer and Meyer employed the dense graphitoidal carbon from gas retorts, and a powerful blast. They determined the temperature by the alteration of the volume of nitrogen in the platinum vessel, for this gas does not permeate through platinum, and is unaltered by heat. [2 bis] The acid properties of hydrochloric acid were known when Lavoisier pointed out the formation of acids by the combination of water with the oxides of the non-metals, and therefore there was reason for thinking that hydrochloric acid was formed by the combination of water with the oxide of some element. Hence when Scheele obtained chlorine by the action of hydrochloric acid on manganese peroxide he considered it as the acid contained in common salt. When it became known that chlorine gives hydrochloric acid with hydrogen, Lavoisier and Berthollet supposed it to be a compound with oxygen of an anhydride contained in hydrochloric acid. They supposed that hydrochloric acid contained water and the oxide of a particular radicle, and that chlorine was a higher degree of oxidation of this radicle _muvias_ (from the Latin neme of hydrochloric acid, _acidum muriaticum_). It was only in 1811 that Gay-Lussac and Thénard in France and Davy in England arrived at the conclusion that the substance obtained by Scheele does not contain oxygen, nor under any conditions give water with hydrogen, and that there is no water in hydrochloric acid gas, and therefore concluded that chlorine is an elementary substance. They named it 'chlorine' from the Greek word [Greek: chlôros], signifying a green colour, because of the peculiar colour by which this gas is characterised. An aqueous solution of hydrochloric acid is generally employed for t he evolution of chlorine. The hydrogen has to be abstracted from the hydrochloric acid. This is accomplished by nearly all oxidising substances, and especially by those which are able to evolve oxygen at a red heat (besides bases, such as mercury and silver oxides, which are able to give salts with hydrogen chloride); for example, manganese peroxide, potassium chlorate, chromic acid, &c. The decomposition essentially consists in the oxygen of the oxidising substance displacing the chlorine from 2HCl, forming water, H_{2}O, and setting the chlorine free, 2HCl + O (disengaged by the oxidising substances) = H_{2}O + Cl_{2}. Even nitric acid partially produces a like reaction; but as we shall afterwards see its action is more complicated, and it is therefore not suitable for the preparation of pure chlorine.[3] But other oxidising substances which do not give any other volatile products with hydrochloric acid may be employed for the preparation of chlorine. Among these may be mentioned: potassium chlorate, acid potassium chromate, sodium manganate, manganese peroxide, &c. Manganese peroxide is commonly employed in the laboratory, and on a large scale, for the preparation of chlorine. The chemical process in this case may be represented as follows: an exchange takes place between 4HCl and MnO_{2}, in which the manganese takes the place of the four atoms of hydrogen, or the chlorine and oxygen exchange places--that is, MnCl_{4} and 2H_{2}O are produced. The chlorine compound, MnCl_{4}, obtained is very unstable; it splits up into chlorine, which as a gas passes from the sphere of action, and a lower compound containing less chlorine than the substance first formed, which remains in the apparatus in which the mixture is heated, MnCl_{4} = MnCl_{2} + Cl_{2}.[3 bis] The action of hydrochloric acid requires a temperature of about 100°. In the laboratory the _preparation of chlorine_ is carried on in flasks, heated over a water-bath, by acting on manganese peroxide with hydrochloric acid or a mixture of common salt and sulphuric acid[4] and washing the gas with water to remove hydrochloric acid.[5] Chlorine cannot be collected over mercury, because it combines with it as with many other metals, and it is soluble in water; however, it is but slightly soluble in hot water or brine. Owing to its great weight, chlorine may be directly collected in a dry vessel by carrying the gas-conducting tube down to the bottom of the vessel. The chlorine will lie in a heavy layer at the bottom of the vessel, displace the air, and the extent to which it fills the vessel may be followed by its colour.[6] [3] However, nitric acid has been proposed as a means for obtaining chlorine, but by methods which have the drawback of being very complicated [3 bis] This representation of the process of the reaction is most natural. However, this decomposition is generally represented as if chlorine gave only one degree of combination with manganese, MnCl_{2}, and therefore directly reacts in the following manner--MnO_{2} + 4HCl = MnCl_{2} + 2H_{2}O + Cl_{2}, in which case it is supposed that manganese peroxide, MnO_{2}, breaks up, as it were, into manganous oxide, MnO and oxygen, both of which react with hydrochloric acid, the manganous oxide acting upon HCl as a base, giving MnCl_{2} and at the same time 2HCl + O = H_{2}O + Cl_{2}. In reality, a mixture of oxygen and hydrochloric acid does give chlorine at a red heat, and this reaction may also take place at the moment of its evolution in this case. All the oxides of manganese (Mn_{2}O_{3}, MnO_{2}, MnO_{3}, Mn_{2}O_{7}), with the exception of manganous oxide, MnO, disengage chlorine from hydrochloric acid, because manganous chloride, MnCl_{2}, is the only compound of chlorine and manganese which exists as a stable compound, all the higher chlorides of manganese being unstable and evolving chlorine. Hence we here take note of two separate changes: (1) an exchange between oxygen and chlorine, and (2) the instability of the higher chlorine compounds. As (according to the law of substitution) in the substitution of oxygen by chlorine, Cl_{2} takes the place of O, the chlorine compounds will contain more atoms than the corresponding oxygen compounds. It is not surprising, therefore, that certain of the chlorine compounds corresponding with oxygen compounds do not exist, or if they are formed are very unstable. And furthermore, an atom of chlorine is heavier than an atom of oxygen, and therefore a given element would have to retain a large mass of chlorine if in the higher oxides the oxygen were replaced by chlorine. For this reason equivalent compounds of chlorine do not exist for all oxygen compounds. Many of the former are immediately decomposed, when formed, with the evolution of chlorine. From this it is evident that there should exist such chlorine compounds as would evolve chlorine as peroxides evolve oxygen, and indeed a large number of such compounds are known. Amongst them may be mentioned antimony pentachloride, SbCl_{5}, which splits up into chlorine and antimony trichloride when heated. Cupric chloride, corresponding with copper oxide, and having a composition CuCl_{2}, similar to CuO, when heated parts with half its chlorine, just as barium peroxide evolves half its oxygen. This method may even be taken advantage of for the preparation of chlorine and cuprous chloride, CuCl. The latter attracts oxygen from the atmosphere, and in so doing is converted from a colourless substance into a green compound whose composition is Cu_{2}Cl_{2}O. With hydrochloric acid this substance gives cupric chloride (Cu_{2}Cl_{2}O + 2HCl = H_{2}O + 2CuCl_{2}), which has only to be dried and heated in order again to obtain chlorine. Thus, in solution, and at the ordinary temperature, the compound CuCl_{2} is stable, but when heated it splits up. On this property is founded Deacon's process for the preparation of chlorine from hydrochloric acid with the aid of air and copper salts, by passing a mixture of air and hydrochloric acid at about 440° over bricks saturated with a solution of a copper salt (a mixture of solutions of CuSO_{4} and Na_{2}SO_{4}). CuCl_{2} is then formed by the double decomposition of the salt of copper and the hydrochloric acid; the CuCl_{2} liberates chlorine, and the CuCl forms Cu_{2}Cl_{2}O with the oxygen of the air, which again gives CuCl_{2} with 2HCl, and so on. Magnesium chloride, which is obtained from sea-water, carnallite, &c., may serve not only as a means for the preparation of hydrochloric acid, but also of chlorine, because its basic salt (magnesium oxychloride) when heated in the air gives magnesium oxide and chlorine (Weldon-Pechiney's process, 1888). Chlorine is now prepared on a large scale by this method. Several new methods based upon this reaction have been proposed for procuring chlorine from the bye-products of other chemical processes. Thus, Lyte and Tattars (1891) obtained up to 67 p.c. of chlorine from CaCl_{2} in this manner. A solution of CaCl_{2}, containing a certain amount of common salt, is evaporated and oxide of magnesium added to it. When the solution attains a density of 1·2445 (at 15°), it is treated with carbonic acid, which precipitates carbonate of calcium, while chloride of magnesium remains in solution. After adding ammonium chloride, the solution is evaporated to dryness and the double chloride of magnesium and ammonium formed is ignited, which drives off the chloride of ammonium. The chloride of magnesium which remains behind is used in the Weldon-Pechiney process. The De Wilde-Reychler (1892) process for the manufacture of chlorine consists in passing alternate currents of hot air and hydrochloric acid gas through a cylinder containing a mixture of the chlorides of magnesium and manganese. A certain amount of sulphate of magnesium which does not participate in any way in the reaction, is added to the mixture to prevent its fusing. The reactions may be expressed by the following equations: (1) 3MgCl_{2} + 3MnCl_{2} + 8O = Mg_{3}Mn_{3}O_{8} + 12Cl; (2) Mg_{3}Mn_{3}O_{8} + 16HCl = 3MgCl_{2} + 3MnCl_{2} + 8H_{2}O + 4Cl. As nitric acid is able to take up the hydrogen from hydrochloric acid, a heated mixture of these acids is also employed for the preparation of chlorine. The resultant mixture of chlorine and lower oxides of nitrogen is mixed with air and steam which regenerates the HNO_{3}, while the chlorine remains as a gas together with nitrogen, in which form it is quite capable of bleaching, forming chloride of lime, &c. Besides these, Solvay and Mond's methods of preparing chlorine must be mentioned. The first is based upon the reaction CaCl_{2} + SiO_{2} + O(air) = CaOSiO_{2} + Cl_{2}, the second on the action of the oxygen of the air (heated) upon MgCl_{2} (and certain similar chlorides) MgCl_{2} + O = MgO + Cl_{2} The remaining MgO is treated with sal-ammoniac to re-form MgCl_{2} (MgO + 2NH_{4}Cl = MgCl_{2} + H_{2}O + 2NH_{3}) and the resultant NH_{3} again converted into sal-ammoniac, so that hydrochloric acid is the only substance consumed. The latter processes have not yet found much application. [4] The following proportions are accordingly taken by weight: 5 parts of powdered manganese peroxide, 11 parts of salt (best fused, to prevent its frothing), and 14 parts of sulphuric acid previously mixed with an equal volume of water. The mixture is heated in a salt bath, so as to obtain a temperature above 100°. The corks in the apparatus must be soaked in paraffin (otherwise they are corroded by the chlorine), and black india-rubber tubing smeared with vaseline must be used, and not vulcanised rubber (which contains sulphur, and becomes brittle under the action of the chlorine). The reaction which proceeds may be expressed thus: MnO_{2} + 2NaCl + 2H_{2}SO_{4} = MnSO_{4} + Na_{2}SO_{4} + 2H_{2}O + Cl_{2}. The method of preparation of Cl_{2} from manganese peroxide and hydrochloric acid was discovered by Scheele, and from sodium chloride by Berthollet. [5] The reaction of hydrochloric acid upon bleaching powder gives chlorine without the aid of heat, CaCl_{2}O_{2} + 4HCl = CaCl_{2} + 2H_{2}O + 2Cl_{2} and is therefore also used for the preparation of chlorine. This reaction is very violent if all the acid be added at once; it should be poured in drop by drop (Mermé, Kämmerer). C. Winkler proposed to mix bleaching powder with one quarter of burnt and powdered gypsum, and having damped the mixture with water, to press and cut it up into cubes and dry at the ordinary temperature. These cubes can be used for the preparation of chlorine in the same apparatus as that used for the evolution of hydrogen and carbonic anhydride--the disengagement of the chlorine proceeds uniformly. A mixture of potassium dichromate and hydrochloric acid evolves chlorine perfectly free from oxygen (V. Meyer and Langer). [6] [Illustration: FIG. 66.--Clay retort for the preparation of chlorine on a large scale.] Chlorine is manufactured on a _large scale_ from manganese peroxide and hydrochloric acid. It is most conveniently prepared in the apparatus shown in fig. 66, which consists of a three-necked earthenware vessel whose central orifice is the largest. A clay or lead funnel, furnished with a number of orifices, is placed in the central wide neck of the vessel. Roughly-ground lumps of natural manganese peroxide are placed in the funnel, which is then closed by the cover N, and luted with clay. One orifice is closed by a clay stopper, and is used for the introduction of the hydrochloric acid and withdrawal of the residues. The chlorine disengaged passes along a leaden gas-conducting tube placed in the other orifice. A row of these vessels is surrounded by a water-bath to ensure their being uniformly heated. Manganese chloride is found in the residue. In Weldon's process lime is added to the acid solution of manganese chloride. A double decomposition takes place, resulting in the formation of manganous hydroxide and calcium chloride. When the insoluble manganous hydroxide has settled, a further excess of milk of lime is added (to make a mixture 2Mn(OH)_{2} + CaO + _x_CaCl_{2}, which is found to be the best proportion, judging from experiment), and then air is forced through the mixture. The hydroxide is thus converted from a colourless to a brown substance, containing peroxide, MnO_{2}, and oxide of manganese, Mn_{2}O_{3}. This is due to the manganous oxide absorbing oxygen from the air. Under the action of hydrochloric acid this mixture evolves chlorine, because of all the compounds of chlorine and manganese the chloride MnCl_{2} is the only one which is stable (_see_ Note 3). Thus one and the same mass of manganese may be repeatedly used for the preparation of chlorine. The same result is attained in other ways. If manganous oxide be subjected to the action of oxides of nitrogen and air (Coleman's process), then manganese nitrate is formed, which at a red heat gives oxides of nitrogen (which are again used in the process) and manganese peroxide, which is thus renewed for the fresh evolution of chlorine. Chlorine is a _gas_ of a yellowish green colour, and has a very suffocating and characteristic odour. On lowering the temperature to -50° or increasing the pressure to six atmospheres (at 0°) chlorine condenses[7] into a liquid which has a yellowish-green colour, a density of 1·3, and boils at -34°. The density and atomic weight of chlorine is 35·5 times greater than that of hydrogen, hence the molecule contains Cl_{2}[8]. At 0° one volume of water dissolves about 1-1/2 volume of chlorine, at 10° about 3 volumes, at 50° again 1-1/2 volume.[9] Such a solution of chlorine is termed 'chlorine water;' and is employed in a diluted form in medicine and as a laboratory reagent. It is prepared by passing chlorine through a series of Woulfe's bottles or into an inverted retort filled with water. Under the action of light, chlorine water gives oxygen and hydrochloric acid. At 0° a saturated solution of chlorine yields a crystallo-hydrate, Cl_{2},8H_{2}O, which easily splits up into chlorine and water when heated, so that if it be sealed up in a tube and heated to 35°, two layers of liquid are formed--a lower stratum of chlorine containing a small quantity of water, and an upper stratum of water containing a small quantity of chlorine.[10] [7] Davy and Faraday liquefied chlorine in 1823 by heating the crystallo-hydrate Cl_{2}8H_{2}O in a bent tube (as with NH_{3}), surrounded by warm water, while the other end of the tube was immersed in a freezing mixture. Meselan condensed chlorine in freshly-burnt charcoal (placed in a glass tube), which when cold absorbs an equal weight of chlorine. The tube was then fused up, the bent end cooled, and the charcoal heated, by which means the chlorine was expelled from the charcoal, and the pressure increased. [8] Judging from Ludwig's observations (1868), and from the fact that the coefficient of expansion of gases increases with their molecular weight (Chapter II., Note 26, for hydrogen = 0·367, carbonic anhydride = 0·373, hydrogen bromide = 0·386), it might be expected that the expansion of chlorine would be greater than that of air or of the gases composing it. V. Meyer and Langer (1885) having remarked that at 1,400° the density of chlorine (taking its expansion as equal to that of nitrogen) = 29, consider that the molecules of chlorine split up and partially give molecules Cl, but it might be maintained that the decrease in density observed only depends on the increase of the coefficient of expansion. [9] Investigations on the solubility of chlorine in water (the solutions evolve all their chlorine on boiling and passing air through them) show many different peculiarities. First Gay-Lussac, and subsequently Pelouze, determined that the solubility increases between 0° and 8°-10° (from 1-1/2 to 2 vols. of chlorine per 100 vols. of water at 0° up to 3 to 2-3/4 at 10°). In the following note we shall see that this is not due to the breaking-up of the hydrate at about 8° to 10°, but to its formation below 9°. Roscoe observed an increase in the solubility of chlorine in the presence of hydrogen--even in the dark. Berthelot determined an increase of solubility with the progress of time. Schönbein and others suppose that chlorine acts on water, forming hypochlorous and hypochloric acids, (HClO + HCl). The equilibrium between chlorine and steam as gases and between water, liquid chlorine, ice, and the solid crystallo-hydrate of chlorine is evidently very complex. Gibbs, Guldberg (1870) and others gave a theory for similar states of equilibrium, which was afterwards developed by Roozeboom (1887), but it would be inopportune here to enter into its details. It will be sufficient in the first place to mention that there is now no doubt (according to the theory of heat, and the direct observations of Ramsay and Young) that the vapour tensions at one and the same temperature are different for the liquid and solid states of substances; secondly, to call attention to the following note; and, thirdly, to state that, in the presence of the crystallo-hydrate, water between O°·24 and +28°·7 (when the hydrate and a solution may occur simultaneously) dissolves a different amount of chlorine than it does in the absence of the crystallo-hydrate. [10] According to Faraday's data the hydrate of chlorine contains Cl_{2},10H_{2}O, but Roozeboom (1885) showed that it is poorer in water and = Cl_{2},8H_{2}O. At first small, almost colourless, crystals are obtained, but they gradually form (if the temperature be below their critical point 28°·7, above which they do not exist) large yellow crystals, like those of potassium chromate. The specific gravity is 1·23. The hydrate is formed if there be more chlorine in a solution than it is able to dissolve under the dissociation pressure corresponding with a given temperature. _In the presence of the hydrate_ the percentage amount of chlorine at 0° = 0·5, at 9° = 0·9, and at 20° = 1·82. At temperatures below 9° the solubility (determined by Gay-Lussac and Pelouze, _see_ Note 9) is dependent on the formation of the hydrate; whilst at higher temperatures under the ordinary pressure the hydrate cannot be formed, and the solubility of chlorine falls, as it does for all gases (Chapter I.). If the crystallo-hydrate is not formed, then below 9° the solubility follows the same rule (6° 1·07 p.c. Cl, 9° 0·95 p.c.). According to Roozeboom, the chlorine evolved by the hydrate presents the following tensions of dissociation: at 0° = 249 mm., at 4° = 398, at 8° = 620, at 10° = 797, at 14° = 1,400 mm. In this case a portion of the crystallo-hydrate remains solid. At 9°·6 the tension of dissociation is equal to the atmospheric pressure. At a higher pressure the crystallo-hydrate may form at temperatures above 9° up to 28°·7, when the vapour tension of the hydrate equals the tension of the chlorine. It is evident that the equilibrium which is established is on the one hand a case of a complex heterogeneous system, and on the other hand a case of the solution of solid and gaseous substances in water. The crystallo-hydrate or chlorine water must be kept in the dark, or the access of light be prevented by coloured glass, otherwise oxygen is evolved and hydrochloric acid formed. Chlorine explodes _with hydrogen_, if a mixture of equal volumes be exposed to the direct action of the sun's rays[11] or brought into contact with spongy platinum, or a strongly heated substance, or when subjected to the action of an electric spark. The explosion in this case takes place for exactly the same reasons--_i.e._ the evolution of heat and expansion of the resultant product--as in the case of detonating gas (Chapter III.) Diffused light acts in the same way, but slowly, whilst direct sunlight causes an explosion.[12] The hydrochloric acid gas produced by the reaction of chlorine on hydrogen occupies (at the original temperature and pressure) a volume equal to the sum of the original volumes; that is, a reaction of substitution here takes place: H_{2} + Cl_{2} = HCl + HCl. In this reaction twenty-two thousand heat units are evolved for one part by weight [1 gram] of hydrogen.[13] [11] The chemical action of light on a mixture of chlorine and hydrogen was discovered by Gay-Lussac and Thénard (1809). It has been investigated by many savants, and especially by Draper, Bunsen, and Roscoe. Electric or magnesium light, or the light emitted by the combustion of carbon bisulphide in nitric oxide, and actinic light in general, acts in the same manner as sunlight, in proportion to its intensity. At temperatures below -12° light no longer brings about reaction, or at all events does not give an explosion. It was long supposed that chlorine that had been subjected to the action of light was afterwards able to act on hydrogen in the dark, but it was shown that this only takes place with moist chlorine, and depends on the formation of oxides of chlorine. The presence of foreign gases, and even of excess of chlorine or of hydrogen, very much enfeebles the explosion, and therefore the experiment is conducted with a detonating mixture prepared by the action of an electric current on a strong solution (sp. gr. 1·15) of hydrochloric acid, in which case the water is not decomposed--that is, no oxygen becomes mixed with the chlorine. [12] The quantity of chlorine and hydrogen which combine is proportional to the intensity of the light--not of all the rays, but only those so-termed chemical (actinic) rays which produce chemical action. Hence a mixture of chlorine and hydrogen, when exposed to the action of light in vessels of known capacity and surface, may be employed as an actinometer--that is, as a means for estimating the intensity of the chemical rays, the influence of the heat rays being previously destroyed, which may be done by passing the rays through water. Investigations of this kind (photo-chemical) showed that chemical action is chiefly limited to the violet end of the spectrum, and that even the invisible ultra-violet rays produce this action. A colourless gas flame contains no chemically active rays; the flame coloured green by a salt of copper evinces more chemical action than the colourless flame, but the flame brightly coloured yellow by salts of sodium has no more chemical action than that of the colourless flame. As the chemical action of light becomes evident in plants, photography, the bleaching of tissues, and the fading of colours in the sunlight, and as a means for studying the phenomenon is given in the reaction of chlorine on hydrogen, this subject has been the most fully investigated in _photo-chemistry_. The researches of Bunsen and Roscoe in the fifties and sixties are the most complete in this respect. Their actinometer contains hydrogen and chlorine, and is surrounded by a solution of chlorine in water. The hydrochloric acid is absorbed as it forms, and therefore the variation in volume indicates the progress of the combination. As was to be expected, the action of light proved to be proportional to the time of exposure and intensity of the light, so that it was possible to conduct detailed photometrical investigations respecting the time of day and season of the year, various sources of light, its absorption, &c. This subject is considered in detail in special works, and we only stop to mention one circumstance, that a small quantity of a foreign gas decreases the action of light; for example, 1/330 of hydrogen by 38 p.c., 1/200 of oxygen by 10 p.c., 1/100 of chlorine by 60 p.c., &c. According to the researches of Klimenko and Pekatoros (1889), the photo-chemical alteration of chlorine water is retarded by the presence of traces of metallic chlorides, and this influence varies with different metals. As much heat is evolved in the reaction of chlorine on hydrogen, and as this reaction, being exothermal, may proceed by itself, the action of light is essentially the same as that of heat--that is, it brings the chlorine and hydrogen into the condition necessary for the reaction--it, as we may say, disturbs the original equilibrium; this is the work done by the luminous energy. It seems to me that the action of light on the mixed gases should be understood in this sense, as Pringsheim (1877) pointed out. [13] In the formation of steam (from one part by weight [1 gram] of hydrogen) 29,000 heat units are evolved. The following are the quantities of heat (thousands of units) evolved in the formation of various other _corresponding_ compounds of oxygen and of chlorine (from Thomsen's, and, for Na_{2}O, Beketoff's results): {2NaCl, 195; CaCl_{2}, 170; HgCl_{2}, 63; 2AgCl, 59. { Na_{2}O, 100; CaO, 131; HgO, 42; Ag_{2}O, 6. {2AsCl_{3}, 143; 2PCl_{5}, 210; CCl_{4}, 21; 2HCl, 44 (gas). { As_{2}O_{3}, 155; P_{2}O_{5}, 370; CO_{2}, 97; H_{2}O, 58 (gas). With the first four elements the formation of the chlorine compound gives the most heat, and with the four following the formation of the oxygen compound evolves the greater amount of heat. The first four chlorides are true salts formed from HCl and the oxide, whilst the remainder have other properties, as is seen from the fact that they are not formed from hydrochloric acid and the oxide, but give hydrochloric acid with water. These relations show that the affinity of chlorine for hydrogen is very great and analogous to the affinity between hydrogen and oxygen. Thus[14] on the one hand by passing a mixture of steam and chlorine through a red-hot tube, or by exposing water and chlorine to the sunlight, oxygen is disengaged, whilst on the other hand, as we saw above, oxygen in many cases displaces chlorine from its compound with hydrogen, and therefore the reaction H_{2}O + Cl_{2} = 2HCl + O belongs to the number of reversible reactions, and hydrogen will distribute itself between oxygen and chlorine. This determines the relation of Cl to substances containing hydrogen and its reactions in the presence of water, to which we shall turn our attention after having pointed out the relation of chlorine to other elements. [14] This has been already pointed out in Chapter III., Note 5. Many _metals_ when brought into contact with chlorine immediately combine with it, and form those metallic chlorides which correspond with hydrogen chloride and with the oxide of the metal taken. This combination may proceed rapidly with the evolution of heat and light; that is, metals are able to burn in chlorine. Thus, for example, sodium[15] burns in chlorine, synthesising common salt. Metals in the form of powders burn without the aid of heat, and become highly incandescent in the process; for instance, antimony, which is a metal easily converted into a powder.[16] Even such metals as gold and platinum,[17] which do not combine directly with oxygen and give very unstable compounds with it, unite directly with chlorine to form metallic chlorides. Either chlorine water or aqua regia may be employed for this purpose instead of gaseous chlorine. These dissolve gold and platinum, converting them into metallic chlorides. _Aqua regia_ is a mixture of 1 part of nitric acid with 2 to 3 parts of hydrochloric acid. This mixture converts into soluble chlorides not only those metals which are acted on by hydrochloric and nitric acids, but also gold and platinum, which are insoluble in either acid separately. This action of aqua regia depends on the fact that nitric acid in acting on hydrochloric acid evolves chlorine. If the chlorine evolved be transferred to a metal, then a fresh quantity is formed from the remaining acids and also combines with the metal.[18] Thus the aqua regia acts by virtue of the chlorine which it contains and disengages. [15] Sodium remains unaltered in perfectly dry chlorine at the ordinary temperature, and even when slightly warmed; but the combination is exceedingly violent at a red heat. [16] An instructive experiment on combustion in chlorine may be conducted as follows: leaves of Dutch metal (used instead of gold for gilding) are placed in a glass globe, and a gas-conducting tube furnished with a glass cock is placed in the cork closing it, and the air is pumped out of the globe. The gas-conducting tube is then connected with a vessel containing chlorine, and the cock opened; the chlorine rushes in, and the metallic leaves are consumed. [17] The behaviour of platinum to chlorine at a high temperature (1,400°) is very remarkable, because platinous chloride, PtCl_{2}, is then formed, whilst this substance decomposes at a much lower temperature into chlorine and platinum. Hence, when chlorine comes into contact with platinum at such high temperatures, it forms fumes of platinous chloride, and they on cooling decompose, with the liberation of platinum, so that the phenomenon appears to be dependent on the volatility of platinum. Deville proved the formation of platinous chloride by inserting a cold tube inside a red-hot one (as in the experiment on carbonic oxide). However, V. Meyer was able to observe the density of chlorine in a platinum vessel at 1,690°, at which temperature chlorine does not exert this action on platinum, or at least only to an insignificant degree. [18] When left exposed to the air aqua regia disengages chlorine, and afterwards it no longer acts on gold. Gay-Lussac, in explaining the action of aqua regia, showed that when heated it evolves, besides chlorine, the vapours of two chloranhydrides--that of nitric acid, NO_{2}Cl (nitric acid, NO_{2}OH, in which HO is replaced by chlorine; _see_ Chapter on Phosphorus), and that of nitrous acid, NOCl--but these do not act on gold. The formation of aqua regia may therefore be expressed by 4NHO_{3} + 8HCl = 2NO_{2}Cl + 2NOCl + 6H_{2}O + 2Cl_{2}. The formation of the chlorides NO_{2}Cl and NOCl is explained by the fact that the nitric acid is deoxidised, gives the oxides NO and NO_{2}, and they directly combine with chlorine to form the above anhydrides. The majority of _non-metals_ also react directly on chlorine; hot sulphur and phosphorus burn in it and combine with it at the ordinary temperature. Only nitrogen, carbon, and oxygen do not combine directly with it. The chlorine compounds formed by the non-metals--for instance, phosphorus trichloride, PCl_{3}, and sulphurous chloride, &c., do not have the properties of salts, and, as we shall afterwards see more fully, correspond to acid anhydrides and acids; for example, PCl_{3}--to phosphorous acid, P(OH)_{3}: NaCl FeCl_{2} SnCl_{4} PCl_{3} HCl Na(HO) Fe(HO)_{2} Sn(HO)_{4} P(HO)_{3} H(HO) As the above-mentioned relation in composition--_i.e._ substitution of Cl by the aqueous residue--exists between many chlorine compounds and their corresponding hydrates, and as furthermore some (acid) hydrates are obtained from chlorine compounds by the action of water, for instance, PCl_{3} + 3H_{2}0 = P(HO)_{3} + 3HCl Phosphorus Water Phosphorous Hydrochloric trichloride acid acid whilst other chlorine compounds are formed from hydroxides and hydrochloric acid, with the liberation of water, for example, NaHO + HCl = NaCl + H_{2}O we endeavour to express this intimate connection between the hydrates and chlorine compounds by calling the latter _chloranhydrides_. In general terms, if the hydrate be basic, then, M(HO) + HCl = MCl + H_{2}O hydrate + hydrochloric acid = chloranhydride + water and if the hydrate ROH be acid, then, RCl + H_{2}O = R(HO) + HCl Chloranhydride + water = hydrate + hydrochloric acid The chloranhydrides MCl corresponding to the bases are evidently metallic chlorides or salts corresponding to HCl. In this manner a distinct equivalency is marked between the compounds of chlorine and the so-called hydroxyl radicle (HO), which is also expressed in the analogy existing between chlorine, Cl_{2}, and hydrogen peroxide, (HO)_{2}. As regards the chloranhydrides corresponding to acids and non-metals, they bear but little resemblance to metallic salts. They are nearly all volatile, and have a powerful suffocating smell which irritates the eyes and respiratory organs. They react on water like many anhydrides of the acids, with the evolution of heat and liberation of hydrochloric acid, forming acid hydrates. For this reason they cannot usually be obtained from hydrates--that is, acids--by the action of hydrochloric acid, as in that case water would be formed together with them, and water decomposes them, converting them into hydrates. There are many intermediate chlorine compounds between true saline metallic chlorides like sodium chloride and true acid chloranhydrides, just as there are all kinds of transitions between bases and acids. Acid chloranhydrides are not only obtained from chlorine and non-metals, but also from many lower oxides, by the aid of chlorine. Thus, for example, CO, NO, NO_{2}, SO_{2}, and other lower oxides which are capable of combining with oxygen may also combine with a corresponding quantity of chlorine. Thus COCl_{2}, NOCl, NO_{2}Cl, SO_{2}Cl_{2}, &c., are obtained. They correspond with the hydrates CO(OH)_{2}, NO(OH), NO_{2}(OH), SO_{2}(OH)_{2}, &c., and to the anhydrides CO_{2}, N_{2}O_{3}, N_{2}O_{5}, SO_{3}, &c. Here we should notice two aspects of the matter: (1) chlorine combines with that with which oxygen is able to combine, because it is in many respects equally if not more energetic than oxygen and replaces it in the proportion Cl_{2} : O; (2) that highest limit of possible combination which is proper to a given element or grouping of elements is very easily and often attained by combination with chlorine. If phosphorus gives PCl_{3} and PCl_{5}, it is evident that PCl_{5} is the higher form of combination compared with PCl_{3}. To the form PCl_{5}, or in general PX_{5}, correspond PH_{4}I, PO(OH)_{3}, POCl_{3}, &c. If chlorine does not always directly give compounds of the highest possible forms for a given element, then generally the lower forms combine with it in order to reach or approach the limit. This is particularly clear in hydrocarbons, where we see the limit C_{_n_}H_{2_n_+2} very distinctly. The unsaturated hydrocarbons are sometimes able to combine with chlorine with the greatest ease and thus reach the limit. Thus ethylene, C_{2}H_{4}, combines with Cl_{2}, forming the so-called Dutch liquid or ethylene chloride, C_{2}H_{4}Cl_{2}, because it then reaches the limit C_{_n_}X_{2_n_+2}. In this and all similar cases the combined chlorine is able by reactions of substitution to give a hydroxide and a whole series of other derivatives. Thus a hydroxide called glycol, C_{2}H_{4}(OH)_{2}, is obtained from C_{2}H_{4}Cl_{2}. Chlorine _in the presence of water_ very often acts directly _as an oxidising agent_. A substance A combines with chlorine and gives, for example, ACl_{2}, and this in turn a hydroxide, A(OH)_{2}, which on losing water forms AO. Here the chlorine has oxidised the substance A. This frequently happens in the simultaneous action of water and chlorine: A + H_{2}O + Cl_{2} = 2HCl + AO. Examples of this oxidising action of chlorine may frequently be observed both in practical chemistry and technical processes. Thus, for instance, chlorine in the presence of water oxidises sulphur and metallic sulphides. In this case the sulphur is converted into sulphuric acid, and the chlorine into hydrochloric acid, or a metallic chloride if a metallic sulphide be taken. A mixture of carbonic oxide and chlorine passed into water gives carbonic anhydride and hydrochloric acid. Sulphurous anhydride is oxidised by chlorine in the presence of water into sulphuric acid, just as it is by the action of nitric acid: SO_{2} + 2H_{2}O + Cl_{2} = H_{2}SO_{4} + 2HCl. The oxidising action of chlorine in the presence of water is taken advantage of in practice for the rapid bleaching of tissues and fibres. The colouring matter of the fibres is altered by oxidation and converted into a colourless substance, but the chlorine afterwards acts on the tissue itself. Bleaching by means of chlorine therefore requires a certain amount of technical skill in order that the chlorine should not act on the fibres themselves, but that its action should be limited to the colouring matter only. The fibre for making writing paper, for instance, is bleached in this manner. The bleaching property of chlorine was discovered by Berthollet, and forms an important acquisition to the arts, because it has in the majority of cases replaced that which before was the universal method of bleaching--namely, exposure to the sun of the fabrics damped with water, which is still employed for linens, &c. Time and great trouble, and therefore money also, have been considerably saved by this change.[19] [19] Ozone and peroxide of hydrogen also bleach tissues. As the action of peroxide of hydrogen is easily controlled by taking a weak solution, and as it has hardly any action upon the tissues themselves, it is replacing chlorine more and more as a bleaching agent. The oxidising property of chlorine is apparent in destroying the majority of organic tissues, and proves fatal to organisms. This action of chlorine is taken advantage of in quarantine stations. But the simple fumigation by chlorine must be carried on with great care in dwelling places, because chlorine disengaged into the atmosphere renders it harmful to the health. The power of chlorine for combination is intimately connected with its capacity for substitution, because, according to the law of substitution, if chlorine combines with hydrogen, then it also replaces hydrogen, and furthermore the combination and substitution are accomplished in the same quantities. Therefore _the atom of chlorine_ which combines with the atom of hydrogen is also able _to replace the atom of hydrogen_. We mention this property of chlorine not only because it illustrates the application of the law of substitution in clear and historically important examples, but more especially because reactions of this kind explain those _indirect methods_ of the formation of many substances which we have often mentioned and to which recourse is had in many cases in chemistry. Thus chlorine does not act on carbon,[20] oxygen, or nitrogen, but nevertheless its compounds with these elements may be obtained by the indirect method of the substitution of hydrogen by chlorine. [20] A certain propensity of carbon to attract chlorine is evidenced in the immense absorption of chlorine by charcoal (Note 7), but, so far as is at present known (if I am not mistaken, no one has tried the aid of light), no combination takes place between the chlorine and carbon. As chlorine easily combines with hydrogen, and does not act on carbon, it decomposes hydrocarbons (and many of their derivatives) at a high temperature, depriving them of their hydrogen and liberating the carbon, as, for example, is clearly seen when a lighted candle is placed in a vessel containing chlorine. The flame becomes smaller, but continues to burn for a certain time, a large amount of soot is obtained, and hydrochloric acid is formed. In this case the gaseous and incandescent substances of the flame are decomposed by the chlorine, the hydrogen combines with it, and the carbon is disengaged as soot.[21] This action of chlorine on hydrocarbons, &c., proceeds otherwise at lower temperatures, as we will now consider. [21] The same reaction takes place under the action of oxygen, with the difference that it burns the carbon, which chlorine is not able to do. If chlorine and oxygen compete together at a high temperature, the oxygen will unite with the carbon, and the chlorine with the hydrogen. A very important epoch in the history of chemistry was inaugurated by the discovery of Dumas and Laurent that chlorine is able to displace and _replace hydrogen_. This discovery is important from the fact that chlorine proved to be an element which combines with great ease simultaneously with both the hydrogen and the element with which the hydrogen was combined. This clearly proved that there is no opposite polarity between elements forming stable compounds. Chlorine does not combine with hydrogen because it has opposite properties, as Dumas and Laurent stated previously, accounting hydrogen to be electro-positive and chlorine electro-negative; this is not the reason of their combining together, for the same chlorine which combines with hydrogen is also able to replace it without altering many of the properties of the resultant substance. This substitution of hydrogen by chlorine is termed _metalepsis_. The mechanism of this substitution is very constant. If we take a hydrogen compound, preferably a hydrocarbon, and if chlorine acts directly on it, then there is produced on the one hand hydrochloric acid and on the other hand a compound containing chlorine in the place of the hydrogen--so that the chlorine divides itself into two equal portions, one portion is evolved as hydrochloric acid, and the other portion takes the place of the hydrogen thus liberated. _Hence this metalepsis is always accompanied by the formation of hydrochloric acid._[22] The scheme of the process is as follows: C_{n}H_{m}X + Cl_{2} = C_{n}H_{m-1}ClX + HCl Hydrocarbon Free Product of Hydrochloric chlorine metalepsis acid Or, in general terms-- RH + Cl_{2} = RCl + HCl. [22] This division of chlorine into two portions may at the same time be taken as a clear confirmation of the conception of molecules. According to Avogadro-Gerhardt's law, the molecule of chlorine (p. 310) contains two atoms of this substance; one atom replaces hydrogen, and the other combines with it. The conditions under which metalepsis takes place are also very constant. In the dark chlorine does not usually act on hydrogen compounds, but the action commences under the influence of light. The direct action of the sun's rays is particularly propitious to metalepsis. It is also remarkable that the presence of traces of certain substances,[23] especially of iodine, aluminium chloride, antimony chloride, &c., promotes the action. A trace of iodine added to the substance subjected to metalepsis often produces the same effect as sunlight.[24] [23] Such carriers or media for the transference of chlorine and the halogens in general were long known to exist in iodine and antimonious chloride, and have been most fully studied by Gustavson and Friedel, of the Petroffsky Academy--the former with respect to aluminium bromide, and the latter with respect to aluminium chloride. Gustavson showed that if a trace of metallic aluminium be dissolved in bromine (it floats on bromine, and when combination takes place much heat and light are evolved), the latter becomes endowed with the property of entering into metalepsis, which it is not able to do of its own accord. When pure, for instance, it acts very slowly on benzene, C_{6}H_{6}, but in the presence of a trace of aluminium bromide the reaction proceeds violently and easily, so that each drop of the hydrocarbon gives a mass of hydrobromic acid, and of the product of metalepsis. Gustavson showed that the _modus operandi_ of this instructive reaction is based on the property of aluminium bromide to enter into combination with hydrocarbons and their derivatives. The details of this and all researches concerning the metalepsis of the hydrocarbons must be looked for in works on organic chemistry. [24] As small admixtures of iodine, aluminium bromide, &c., aid the metalepsis of large quantities of a substance, just as nitric oxide aids the reaction of sulphurous anhydride on oxygen and water, so the principle is essentially the same in both cases. Effects of this kind (which should also be explained by a chemical reaction proceeding at the surfaces) only differ from true contact phenomena in that the latter are produced by solid bodies and are accomplished at their surfaces, whilst in the former all is in solution. Probably the action of iodine is founded on the formation of iodine chloride, which reacts more easily than chlorine. If marsh gas be mixed with chlorine and the mixture ignited, then the hydrogen is entirely taken up from the marsh gas and hydrochloric acid and carbon formed, but there is no metalepsis.[25] But if a mixture of equal volumes of chlorine and marsh gas be exposed to the action of diffused light, then the greenish yellow mixture gradually becomes colourless, and hydrochloric acid and the first product of metalepsis--namely, methyl chloride--are formed: CH_{4} + Cl_{2} = CH_{3}Cl + HCl Marsh gas Chlorine Methyl chloride Hydrochloric acid [25] Metalepsis belongs to the number of delicate reactions--if it may be so expressed--as compared with the energetic reaction of combustion. Many cases of substitution are of this kind. Reactions of metalepsis are accompanied by an evolution of heat, but in a less quantity than that evolved in the formation of the resulting quantity of the halogen acids. Thus the reaction C_{2}H_{6} + Cl_{2} = C_{2}H_{5}Cl + HCl, according to the data given by Thomsen, evolves about 20,000 heat units, whilst the formation of hydrochloric acid evolves 22,000 units. The volume of the mixture remains unaltered. The methyl chloride which is formed is a gas. If it be separated from the hydrochloric acid (it is soluble in acetic acid, in which hydrochloric acid is but sparingly soluble) and be again mixed with chlorine, then it may be subjected to a further metalepsical substitution--the second atom of hydrogen may be substituted by chlorine, and a liquid substance, CH_{2}Cl_{2}, called methylene chloride, will be obtained. In the same manner the substitution may be carried on still further, and CHCl_{3}, or chloroform, and lastly carbon tetrachloride, CCl_{4}, will be produced. Of these substances the best known is chloroform, owing to its being formed from many organic substances (by the action of bleaching powder) and to its being used in medicine as an anæsthetic; chloroform boils at 62° and carbon tetrachloride at 78°. They are both colourless odoriferous liquids, heavier than water. The progressive substitution of hydrogen by chlorine is thus evident, and it can be clearly seen that the double decompositions are accomplished between molecular quantities of the substance--that is, between equal volumes in a gaseous state. _Carbon tetrachloride_, which is obtained by the metalepsis of marsh gas, cannot be obtained directly from chlorine and carbon, but it may be obtained from certain compounds of carbon--for instance, from carbon bisulphide--if its vapour mixed with chlorine be passed through a red-hot tube. Both the sulphur and carbon then combine with the chlorine. It is evident that by ultimate metalepsis a corresponding carbon chloride may be obtained from any hydrocarbon--indeed, the number of chlorides of carbon C_{_n_}Cl_{2_m_} already known is very large. As a rule, the fundamental chemical characters of hydrocarbons are not changed by metalepsis; that is, if a neutral substance be taken, then the product of metalepsis is also a neutral substance, or if an acid be taken the product of metalepsis also has acid properties. Even the crystalline form not unfrequently remains unaltered after metalepsis. The metalepsis of acetic acid, CH_{3}·COOH, is historically the most important. It contains three of the atoms of the hydrogen of marsh gas, the fourth being replaced by carboxyl, and therefore by the action of chlorine it gives three products of metalepsis (according to the amount of the chlorine and conditions under which the reaction takes place), mono-, di-, and tri-chloracetic acids--CH_{2}Cl·COOH, CHCl_{2}·COOH, and CCl_{3}·COOH; they are all, like acetic acid, monobasic. The resulting products of metalepsis, in containing an element which so easily acts on metals as chlorine, possess the possibility of attaining a further complexity of molecules of which the original hydrocarbon is often in no way capable. Thus on treating with an alkali (or first with a salt and then with an alkali, or with a basic oxide and water, &c.) the chlorine forms a salt with its metal, and the hydroxyl radicle takes the place of the chlorine--for example, CH_{3}·OH is obtained from CH_{3}Cl. By the action of metallic derivatives of hydrocarbons--for example, CH_{3}Na--the chlorine also gives a salt, and the hydrocarbon radicle--for instance, CH_{3}--takes the place of the chlorine. In this, or in a similar manner, CH_{3}·CH_{3}, or C_{2}H_{6} is obtained from CH_{3}Cl and C_{6}H_{5}·CH_{3} from C_{6}H_{6}. The products of metalepsis also often react on ammonia, forming hydrochloric acid (and thence NH_{4}Cl) and an amide; that is, the product of metalepsis, with the ammonia radicle NH_{2}, &c. in the place of chlorine. Thus by means of metalepsical substitution methods were found in chemistry for an artificial and general means of the formation of complex carbon compounds from more simple compounds which are often totally incapable of direct reaction. Besides which, this key opened the doors of that secret edifice of complex organic compounds into which man had up to then feared to enter, supposing the hydrocarbon elements to be united only under the influence of those mystic forces acting in organisms.[26] [26] With the predominance of the representation of compound radicles (this doctrine dates from Lavoisier and Gay-Lussac) in organic chemistry, it was a very important moment in its history when it became possible to gain an insight into the structure of the radicles themselves. It was clear, for instance, that ethyl, C_{2}H_{5}, or the radicle of common alcohol, C_{2}H_{5}·OH, passes, without changing, into a number of ethyl derivatives, but its relation to the still simpler hydrocarbons was not clear, and occupied the attention of science in the 'forties' and 'fifties.' Having obtained ethyl hydride, C_{2}H_{5}H = C_{2}H_{6}, it was looked on as containing the same ethyl, just as methyl hydride, CH_{4} = CH_{3}H, was considered as existing in methane. Having obtained free methyl, CH_{3}CH_{3} = C_{2}H_{6}, from it, it was considered as a derivative of methyl alcohol, CH_{3}OH, and as only isomeric with ethyl hydride. By means of the products of metalepsis it was proved that this is not a case of isomerism but of strict identity, and it therefore became clear that ethyl is methylated methyl, C_{2}H_{5} = CH_{2}CH_{3}. In its time a still greater impetus was given by the study of the reactions of monochloracetic acid, CH_{2}Cl·COOH, or CO(CH_{2}Cl)(OH). It appeared that metalepsical chlorine, like the chlorine of chloranhydrides--for instance, of methyl chloride, CH_{3}Cl, or ethyl chloride, C_{2}H_{5}Cl--is capable of substitution; for example, glycollic acid, CH_{2}(OH)(CO_{2}H), or CO(CH_{2}·OH)(OH), was obtained from it, and it appeared that the OH in the group CH_{2}(OH) reacted like that in alcohols, and it became clear, therefore, that it was necessary to examine the radicles themselves by analysing them from the point of view of the bonds connecting the constituent atoms. Whence arose the present doctrine of the structure of the carbon compounds. (_See_ Chapter VIII., Note 42.) It is not only hydrocarbons which are subject to metalepsis. Certain other hydrogen compounds, under the action of chlorine, also give corresponding chlorine derivatives in exactly the same manner; for instance, ammonia, caustic potash, caustic lime, and a whole series of _alkaline_ substances.[27] In fact, just as the hydrogen in marsh gas can be replaced by chlorine and form methyl chloride, so the hydrogen in caustic potash, KHO, ammonia, NH_{3}, and calcium hydroxide, CaH_{2}O_{2} or Ca(OH)_{2}, may be replaced by chlorine and give potassium hypochlorite, KClO, calcium hypochlorite, CaCl_{2}O_{2}, and the so-called chloride of nitrogen, NCl_{3}. For not only is the correlation in composition the same as in the substitution in marsh gas, but the whole mechanism of the reaction is the same. Here also two atoms of chlorine act: one takes the place of the hydrogen whilst the other is evolved as hydrochloric acid, only in the former case the hydrochloric acid evolved remained free, and in the latter, in presence of alkaline substances, it reacts on them. Thus, in the action of chlorine on caustic potash, the hydrochloric acid formed acts on another quantity of caustic potash and gives potassium chloride and water, and therefore not only KHO + Cl_{2} = HCl + KClO, but also KHO + HCl = H_{2}O + KCl, and the result of both simultaneous phases will be 2KHO + Cl_{2} = H_{2}O + KCl + KClO. We will here discuss certain special cases. [27] By including many instances of the action of chlorine under metalepsis we not only explain the indirect formation of CCl_{4}, NCl_{3}, and Cl_{2}O by one method, but we also arrive at the fact that the reactions of the metalepsis of the hydrocarbons lose that exclusiveness which was often ascribed to them. Also by subjecting the chemical representations to the law of substitution we may foretell metalepsis as a particular case of a general law. The action of chlorine on ammonia may either result in the entire breaking up of the ammonia, with the evolution of gaseous nitrogen, or in a product of metalepsis (as with CH_{4}). With an excess of chlorine and the aid of heat the ammonia is decomposed, with the disengagement of free nitrogen.[28] This reaction evidently results in the formation of sal-ammoniac, 8NH_{3} + 3Cl_{2} = 6NH_{4}Cl + N_{2}. But if the ammonium salt be in excess, then the reaction takes the direction of the replacement of the hydrogen in the ammonia by chlorine. The principal result is that NH_{3} + 3Cl_{2} forms NCl_{3} + 3HCl.[29] The resulting product of metalepsis, or _chloride of nitrogen_, NCl_{3}, discovered by Dulong, is a liquid having the property of decomposing with excessive ease not only when heated, but even under the action of mechanical influences, as by a blow or by contact with certain solid substances. The explosion which accompanies the decomposition is due to the fact that the liquid chloride of nitrogen gives gaseous products, nitrogen and chlorine.[29 bis] [28] This may be taken advantage of in the preparation of nitrogen. If a large excess of chlorine water be poured into a beaker, and a small quantity of a solution of ammonia be added, then, after shaking, nitrogen is evolved. If chlorine act on a dilute solution of ammonia, the volume of nitrogen does not correspond with the volume of the chlorine taken, because ammonium hypochlorite is formed. If ammonia gas be passed through a fine orifice into a vessel containing chlorine, the reaction of the formation of nitrogen is accompanied by the emission of light and the appearance of a cloud of sal-ammoniac. In all these instances an excess of chlorine must be present. [29] The hydrochloric acid formed combines with ammonia, and therefore the final result is 4NH_{3} + 3Cl_{2} = NCl_{3} + 3NH_{4}Cl. For this reason, more ammonia must enter into the reaction, but the metalepsical reaction in reality only takes place with an excess of ammonia or its salt. If bubbles of chlorine be passed through a fine tube into a vessel containing ammonia gas, each bubble gives rise to an explosion. If, however, chlorine be passed into a solution of ammonia, the reaction at first brings about the formation of nitrogen, because chloride of nitrogen acts on ammonia like chlorine. But when sal-ammoniac has begun to form, then the reaction directs itself towards the formation of chloride of nitrogen. The first action of chlorine on a solution of sal-ammoniac always causes the formation of chloride of nitrogen, which then reacts on ammonia thus: NCl_{3} + 4NH_{3} = N_{2} + 3NH_{4}Cl. Therefore, so long as the liquid is alkaline from the presence of ammonia the chief product will be nitrogen. The reaction NH_{4}Cl + 3Cl_{2} = NCl_{3} + 4HCl is reversible; with a dilute solution it proceeds in the above-described direction (perhaps owing to the affinity of the hydrochloric acid for the excess of water), but with a strong solution of hydrochloric acid it takes the opposite direction (probably by virtue of the affinity of hydrochloric acid for ammonia). Therefore there must exist a very interesting case of equilibrium between ammonia, hydrochloric acid, chlorine, water, and chloride of nitrogen which has not yet been investigated. The reaction NCl_{3} + 4HCl = NH_{4}Cl + 3Cl_{2} enabled Deville and Hautefeuille to determine the composition of chloride of nitrogen. When slowly decomposed by water, chloride of nitrogen gives, like a chloranhydride, nitrous acid or its anhydride, 2NCl_{3} + 3H_{2}O = N_{2}O_{3} + 6HCl. From these observations it is evident that chloride of nitrogen presents great chemical interest, which is strengthened by its analogy with trichloride of phosphorus. The researches of F. F. Selivanoff (1891-94) prove that NCl_{3} may be regarded as an ammonium derivative of hypochlorous acid. Chloride of nitrogen is decomposed by dilute sulphuric acid in the following manner: NCl_{3} + 3H_{2}O + H_{2}SO_{4} = NH_{4}HSO_{4} + 3HClO. This reaction is reversible and is only complete when some substance, combining with HClO (for instance, succinimide) or decomposing it, is added to the liquid. This is easily understood from the fact that hypochlorous acid itself, HClO, may, according to the view held in this book, be regarded as the product of the metalepsis of water, and consequently bears the same relation to NCl_{3} as H_{2}O does to NH_{3}, or as RHO to RNH_{2}, R_{2}NH, and R_{3}N--that is to say, NCl_{3} corresponds as an ammonium derivative to ClOH and Cl_{2} in exactly the same manner as NR_{3} corresponds to ROH and R_{2}. The connection of NCl_{3} and other similar explosive chloro-nitrogen compounds (called chloryl compounds by Selivanoff; for example, the C_{2}H_{5}NCl_{2} of Wurtz is chloryl ethylamine), such as NRCl_{2} (as NC_{2}H_{5}Cl_{2}), and NR_{2}Cl (for instance, N(CH_{3}CO)HCl, chlorylacetamide, and N(C_{2}H_{5})_{2}Cl, chloryl diethylamine) with HClO is evident from the fact that under certain circumstances these compounds give hypochlorous acid, with water, for instance, NR_{2}Cl + H_{2}O = NR_{2}H + HClO, and frequently act (like NCl_{3} and HClO, or Cl_{2}) in an oxidising and chloridising manner. We may take chloryl succinimide, C_{2}H_{4}(CO)_{2}NCl for example. It was obtained by Bender by the action of HClO upon succinimide, C_{2}H_{4}(CO)_{2}NH, and is decomposed by water with the re-formation of amide and HClO (the reaction is reversible). Selivanoff obtained, investigated, and classified many of the compounds NR_{2}Cl and NRCl_{2}, where R is a residue of organic acids or alcohols, and showed their distinction from the chloranhydrides, and thus supplemented the history of chloride of nitrogen, which is the simplest of the amides containing chlorine, NR_{3}, where R is fully substituted by chlorine. [29 bis] In preparing NCl_{3} every precaution must he used to guard against an explosion, and care should he taken that the NCl_{3} remains under a layer of water. Whenever an ammoniacal substance comes into contact with chlorine great care must be taken, because it may be a case of the formation of such products and a very dangerous explosion may ensue. The liquid product of the metalepsis of ammonia may be most safely prepared in the form of small drops by the action of a galvanic current on a slightly warm solution of sal-ammoniac; chlorine is then evolved at the positive pole, and this chlorine acting on the ammonia gradually forms the product of metalepsis which floats on the surface of the liquid (being carried up by the gas), and if a layer of turpentine be poured on to it these small drops, on coming into contact with the turpentine, give feeble explosions, which are in no way dangerous owing to the small mass of the substance formed. Drops of chloride of nitrogen may with great caution be collected for investigation in the following manner. The neck of a funnel is immersed in a basin containing mercury, and first a saturated solution of common salt is poured into the funnel, and above it a solution of sal-ammoniac in 9 parts of water. Chlorine is then slowly passed through the solutions, when drops of chloride of nitrogen fall into the salt water. Chloride of nitrogen is a yellow oily liquid of sp. gr. 1·65, which boils at 71°, and breaks up into N + Cl_{3} at 97°. The contact of phosphorus, turpentine, india-rubber, &c. causes an explosion, which is sometimes so violent that a small drop will pierce through a thick board. The great ease with which chloride of nitrogen decomposes is dependent upon the fact that it is formed with an absorption of heat, which it evolves when decomposed, to the amount of about 38,000 heat units for NCl_{3}, as Deville and Hautefeuille determined. Chlorine, when absorbed by a solution of caustic soda (and also of other alkalis) at the ordinary temperature, causes the replacement of the hydrogen in the caustic soda by the chlorine, with the formation of sodium chloride by the hydrochloric acid, so that the reaction may be represented in two phases, as described above. In this manner, sodium hypochlorite, NaClO, and sodium chloride are simultaneously formed: 2NaHO + Cl_{2} = NaCl + NaClO + H_{2}O. The resultant solution contains NaClO and is termed 'eau de Javelle.' An exactly similar reaction takes place when chlorine is passed over dry hydrate of lime at the ordinary temperature: 2Ca(HO)_{2} + 2Cl_{2} = CaCl_{2}O_{2} + CaCl_{2} + 2H_{2}O. A mixture of the product of metalepsis with calcium chloride is obtained. This mixture is employed in practice on a large scale, and is termed 'bleaching powder,' owing to its acting, especially when mixed with acids, as a bleaching agent on tissues, so that it resembles chlorine in this respect. It is however preferable to chlorine, because the destructive action of the chlorine can be moderated in this case, and because it is much more convenient to deal with a solid substance than with gaseous chlorine. Bleaching powder is also called _chloride of lime_, because it is obtained from chlorine and hydrate of lime, and contains[30] both these substances. It may be prepared in the laboratory by passing a current of chlorine through a cold mixture of water and lime (milk of lime). The mixture must be kept cold, as otherwise 3Ca(ClO)_{2} passes into 2CaCl_{2} + Ca(ClO_{3})_{2}. In the manufacture of bleaching powder in large quantities at chemical works, the purest possible slaked lime is taken and laid in a thin layer in large flat chambers, M (whose walls are made of Yorkshire flags or tarred wood, on which chlorine has no action), and into which chlorine gas is introduced by lead tubes. The distribution of the plant is shown in the annexed drawing (fig. 67). [Illustration: FIG. 67.--Apparatus for the manufacture of bleaching powder (on a small scale) by the action of chlorine, which is generated in the vessels C, on lime, which is charged into M.] [30] Quicklime, CaO (or calcium carbonate, CaCO_{3}), does not absorb chlorine when cold, but at a red heat, in a current of chlorine, it forms calcium chloride, with the evolution of oxygen. (This was confirmed in 1893 by Wells, at Oxford.) This reaction corresponds with the decomposing action of chlorine on methane, ammonia, and water. Slaked lime (calcium hydroxide, CaH_{2}O_{2}) also, when dry, does not absorb chlorine at 100°. The absorption proceeds at the ordinary temperature (below 40°). The dry mass thus obtained contains not less than three equivalents of calcium hydroxide to four equivalents of chlorine, so that its composition is [Ca(HO)_{2}]_{5}Cl_{4}. In all probability a simple absorption of chlorine by the lime at first takes place in this case, as may be seen from the fact that even carbonic anhydride, when acting on the dry mass obtained as above, disengages all the chlorine from it, leaving only calcium carbonate. But if the bleaching powder be obtained by a wet method, or if it be dissolved in water (in which it is very soluble), and carbonic anhydride be passed into it, then chlorine is no longer disengaged, but chlorine oxide, Cl_{2}O, and only half of the chlorine is converted into this oxide, while the other half remains in the liquid as calcium chloride. From this it may be inferred that calcium chloride is formed by the action of water on bleaching powder, and this is proved to be the case by the fact that small quantities of water extract a considerable amount of calcium chloride from bleaching powder. If a large quantity of water act on bleaching powder an excess of calcium hydroxide remains, a portion of which is not subjected to change. The action of the water may be expressed by the following formulæ: From the dry mass Ca_{3}(HO)_{6}Cl_{4} there is formed lime, Ca(HO)_{2}, calcium chloride, CaCl_{2}, and a saline substance, Ca(ClO)_{2}. Ca_{3}H_{6}O_{6}Cl_{4} = CaH_{2}O_{2} + CaCl_{2}O_{2} + CaCl_{2} + 2H_{2}O. The resulting substances are not equally soluble; water first extracts the calcium chloride, which is the most soluble, then the compound Ca(ClO)_{2} and ultimately calcium hydroxide is left. A mixture of calcium chloride and hypochlorite passes into solution. On evaporation there remains Ca_{2}O_{2}Cl_{4}3H_{2}O. The dry bleaching powder does not absorb more chlorine, but the solution is able to absorb it in considerable quantity. If the liquid be boiled, a considerable amount of chlorine monoxide is evolved. After this calcium chloride alone remains in solution, and the decomposition may be expressed as follows: CaCl_{2} + CaCl_{2}O_{2} + 2Cl_{2} = 2CaCl_{2} + 2Cl_{2}O. Chlorine monoxide may be prepared in this manner. It is sometimes said that bleaching powder contains a substance, Ca(OH)_{2}Cl_{2}, that is calcium peroxide, CaO_{2}, in which one atom of oxygen is replaced by (OH)_{2}, and the other by Cl_{2}; but, judging from what has been said above, this can only be the case in the dry state, and not in solutions. On being kept for some time, bleaching powder sometimes decomposes, with the evolution of oxygen (because CaCl_{2}O_{2} = CaCl_{2} + O_{2}, _see_ p. 163); the same takes place when it is heated. The products of the metalepsis of alkaline hydrates, NaClO and Ca(ClO)_{2}, which are present in solutions of 'Javelle salt' and bleaching powder (they are not obtained free from metallic chlorides), must be counted as salts, because their metals are capable of substitution. But the hydrate HClO corresponding with these salts, or _hypochlorous acid_, is not obtained in a free or pure state, for two reasons: in the first place, because this hydrate, as a very feeble acid, splits up (like H_{2}CO_{3} or HNO_{3}) into water and the anhydride, or _chlorine monoxide_, Cl_{2}O = 2HClO-H_{2}O; and, in the second place, because, in a number of instances, it evolves oxygen with great facility, forming hydrochloric acid: HClO = HCl + O. Both hypochlorous acid and chlorine monoxide may be regarded as products of the metalepsis of water, because HOH corresponds with ClOH and ClOCl. Hence in many instances bleaching salts (a mixture of hypochlorites and chlorides) break up, with the evolution of (1) _chlorine_, under the action of an excess of a powerful acid capable of evolving hydrochloric acid from sodium or calcium chlorides, and this takes place most simply under the action of hydrochloric acid itself, because (p. 462) NaCl + NaClO + 3HCl = 2NaCl + HCl + Cl_{2} + H_{2}O; (2) _oxygen_, as we saw in Chapter III.--The bleaching properties and, in general, _oxidising action_ of bleaching salts is based on this evolution of oxygen (or chlorine); oxygen is also disengaged on heating the dry salts--for instance, NaCl + NaClO = 2NaCl + O; (3) and, lastly, _chlorine monoxide_, which contains both chlorine and oxygen. Thus, if a little sulphuric, nitric, or similar acid (not enough to liberate hydrochloric acid from the CaCl_{2}) be added to a solution of a bleaching salt (which has an alkaline reaction, owing either to an excess of alkali or to the feeble acid properties of HClO), then the hypochlorous acid set free gives water and chlorine monoxide. If carbonic anhydride (or boracic or a similar very feeble acid) act on the solution of a bleaching salt, then hydrochloric acid is not evolved from the sodium or calcium chlorides, but the hypochlorous acid is displaced and gives chlorine monoxide,[31] because hypochlorous acid is one of the most feeble acids. Another method for the preparation of chlorine monoxide is based on these feeble acid properties of hypochlorous acid. Zinc oxide and mercury oxide, under the action of chlorine in the presence of water, do not give a salt of hypochlorous acid, but form a chloride and hypochlorous acid, which fact shows the incapacity of this acid to combine with the bases mentioned. Therefore, if such oxides as those of zinc or mercury be shaken up in water, and chlorine be passed through the turbid liquid,[32] a reaction occurs which may be expressed in the following manner: 2HgO + 2Cl_{2} = Hg_{2}OCl_{2} + Cl_{2}O. In this case, a compound of mercury oxide with mercury chloride, or the so-called mercury oxychloride, is obtained: Hg_{2}OCl_{2} = HgO + HgCl_{2}. This is insoluble in water, and is not affected by hypochlorous anhydride, so that the solution will contain hypochlorous acid only, but the greater part of it splits up into the anhydride and water.[32 bis] [31] For this reason it is necessary that in the preparation of bleaching powder the chlorine should be free from hydrochloric acid, and even the lime from calcium chloride. An excess of chlorine, in acting on a solution of bleaching powder, may also give chlorine monoxide, because calcium carbonate also gives chlorine monoxide under the action of chlorine. This reaction may be brought about by treating freshly precipitated calcium carbonate with a stream of chlorine in water: 2Cl_{2} + CaCO_{3} = CO_{2} + CaCl_{2} + Cl_{2}O. From this we may conclude that, although carbonic anhydride displaces hypochlorous anhydride, it may be itself displaced by an excess of the latter. [32] Dry red mercury oxide acts on chlorine, forming dry hypochlorous anhydride (chlorine monoxide) (Balard); when mixed with water, red mercury oxide acts feebly on chlorine, and when freshly precipitated it evolves oxygen and chlorine. An oxide of mercury which easily and abundantly evolves chlorine monoxide under the action of chlorine in the presence of water may be prepared as follows: the oxide of mercury, precipitated from a mercuric salt by an alkali, is heated to 300° and cooled (Pelouze). If a salt, MClO, be added to a solution of mercuric salt, HgX_{2}, mercuric oxide is liberated, because the hypochlorite is decomposed. [32 bis] A solution of hypochlorous anhydride is also obtained by the action of chlorine on many salts; for example, in the action of chlorine on a solution of sodium sulphate the following reaction takes place: Na_{2}SO_{4} + H_{2}O + Cl_{2} = NaCl + HClO + NaHSO_{4}. Here the hypochlorous acid is formed, together with HCl, at the expense of chlorine and water, for Cl_{2} + H_{2}O = HCl + HClO. If the crystallo-hydrate of chlorine be mixed with mercury oxide, the hydrochloric acid formed in the reaction gives mercury chloride, and hypochlorous acid remains in solution. A dilute solution of hypochlorous acid or chlorine monoxide may be concentrated by distillation, and if a substance which takes up water (without destroying the acid)--for instance, calcium nitrate--be added to the stronger solution, then the anhydride of hypochlorous acid--_i.e._ chlorine monoxide--is disengaged. Chlorine monoxide, which corresponds to bleaching and hypochlorous salts, containing as it does the two elements oxygen and chlorine, forms a characteristic example of a compound of elements which, in the majority of cases, act chemically in an analogous manner. Chlorine monoxide, as prepared from an aqueous solution by the abstraction of water or by the action of dry chlorine on cold mercury oxide, is, at the ordinary temperature, a gas or vapour which condenses into a red liquid boiling at +20° and giving a vapour whose density (43 referred to hydrogen) shows that 2 vols. of chlorine and 1 vol. of oxygen give 2 vols. of chlorine monoxide. In an anhydrous form the gas or liquid easily explodes, splitting up into chlorine and oxygen. This explosiveness is determined by the fact that heat is _evolved_ in the decomposition to the amount of about 15,000 heat units for Cl_{2}O.[33] The explosion may even take place spontaneously, and also in the presence of many oxidisable substances (for instance, sulphur, organic compounds, &c.), but the solution, although unstable and showing a strong oxidising tendency, does not explode.[34] It is evident that the presence of hypochlorous acid, HClO, may be assumed in an aqueous solution of Cl_{2}O, since Cl_{2}O + H_{2}O = 2HClO. [33] All explosive substances are of this kind--ozone, hydrogen peroxide, chloride of nitrogen, nitro-compounds, &c. Hence they cannot be formed directly from the elements or their simplest compounds, but, on the contrary, decompose into them. In a liquid state chlorine monoxide explodes even on contact with powdery substances, or when rapidly agitated--for instance, if a file be rasped over the vessel in which it is contained. [34] A solution of chlorine monoxide, or hypochlorous acid, does not explode, owing to the presence of the mass of water. In dissolving, chlorine monoxide evolves about 9,000 heat units, so that its store of heat becomes less. The capacity of hypochlorous acid (studied by Carius and others) for entering into combination with the unsaturated hydrocarbons is very often taken advantage of in organic chemistry. Thus its solution absorbs ethylene, forming the chlorhydrin C_{2}H_{4}ClOH. The oxidising action of hypochlorous acid and its salts is not only applied to bleaching but also to many reactions of oxidation. Thus it converts the lower oxides of manganese into the peroxide. Hypochlorous acid, its salts, and chlorine monoxide serve as a transition between hydrochloric acid, chlorides, and chlorine, and a whole series of compounds containing the same elements combined with a still greater quantity of oxygen. The higher oxides of chlorine, as their origin indicates, are closely connected with hypochlorous acid and its salts: Cl_{2}, NaCl, HCl, hydrochloric acid. Cl_{2}O, NaClO, HClO, hypochlorous acid. Cl_{2}O_{3}, NaClO_{2}, HClO_{2}, chlorous acid.[35] Cl_{2}O_{5}, NaClO_{3}, HClO_{3}, chloric acid. Cl_{2}O_{7}, NaClO_{4}, HClO_{4}, perchloric acid. When heated, solutions of hypochlorites undergo a remarkable change. Themselves so unstable, they, without any further addition, yield two fresh salts which are both much more stable; one contains more oxygen than MClO, the other contains none at all. 3MClO = MClO_{3} + 2MCl hypochlorite chlorate chloride [35] _Chlorous acid_, HClO_{2} (according to the data given by Millon, Brandau, and others) in many respects resembles hypochlorous acid, HClO, whilst they both differ from chloric and perchloric acids in their degree of stability, which is expressed, for instance, in their bleaching properties; the two higher acids do not bleach, but both the lower ones do so (oxidise at the ordinary temperature). On the other hand, chlorous acid is analogous to nitrous acid, HNO_{2}. The anhydride of chlorous acid, Cl_{2}O_{3}, is not known in a pure state, but it probably occurs in admixture with chlorine dioxide, ClO_{2}, which is obtained by the action of nitric and sulphuric acids on a mixture of potassium chlorate with such reducing substances as nitric oxide, arsenious oxide, sugar, &c. All that is at present known is that pure chlorine dioxide ClO_{2} (_see_ Notes 39-43) is gradually converted into a mixture of hypochlorous and chlorous acids under the action of water (and alkalis); that is, it acts like nitric peroxide, NO_{2} (giving HNO_{3} and HNO_{2}), or as a mixed anhydride, 2ClO_{2} + H_{2}O = HClO_{3} + HClO_{2}. The silver salt, AgClO_{2}, is sparingly soluble in water. The investigations of Garzarolli-Thurnlackh and others seem to show that the anhydride Cl_{2}O_{3} does not exist in a free state. Part of the salt--namely, two-thirds of it--parts with its oxygen in order to oxidise the remaining third.[36] From an intermediate substance, RX, two extremes, R and RX_{3} are formed, just as nitrous anhydride splits up into nitric oxide and nitric anhydride (or nitric acid). The resulting salt, MClO_{3}, corresponds with _chloric acid_ and potassium chlorate, KClO_{3}. It is evident that a similar salt may be obtained directly by the action of chlorine on an alkali if its solution be heated, because RClO will be first formed, and then RClO_{3}; for example, 6KHO + 3Cl_{2} = KClO_{3} + 5KCl + 3H_{2}O. Chlorates are so prepared; for instance, _potassium chlorate_, which is easily separated from potassium chloride, being sparingly soluble in cold water.[37] [36] Hydrochloric acid, which is an example of compounds of this kind, is a saturated substance which does not combine directly with oxygen, but in which, nevertheless, a considerable quantity of oxygen may be inserted between the elements forming it. The same may be observed in a number of other cases. Thus oxygen may be added or inserted between the elements, sometimes in considerable quantities, in the saturated hydrocarbons; for instance, in C_{3}H_{8}, three atoms of oxygen produce an alcohol, glycerin or glycerol, C_{3}H_{5}(OH)_{3}. We shall meet with similar examples hereafter. This is generally explained by regarding oxygen as a bivalent element--that is, as capable of combining with two different elements, such as chlorine, hydrogen, &c. On the basis of this view, it may be inserted between each pair of combined elements; the oxygen will then be combined with one of the elements by one of its affinities and with the other element by its other affinity. This view does not, however, express the entire truth of the matter, even when applied to the compounds of chlorine. Hypochlorous acid, HOCl--that is, hydrochloric acid in which one atom of oxygen is inserted--is, as we have already seen, a substance of small stability; it might therefore be expected that on the addition of a fresh quantity of oxygen, a still less stable substance would be obtained, because, according to the above view, the chlorine and hydrogen, which form such a stable compound together, are then still further removed from each other. But it appears that chloric and perchloric acid, HClO_{3} and HClO_{4}, are much more stable substances. Furthermore, the addition of oxygen has also its limit, it can only be added to a certain extent. If the above representation were true and not merely hypothetical, there would be no limit to the combination of oxygen, and the more it entered into one continuous chain the more unstable would be the resultant compound. But not more than four atoms of oxygen can be added to hydrogen sulphide, nor to hydrochloric acid, nor to hydrogen phosphide. This peculiarity must lie in the properties of oxygen itself; four atoms of oxygen seem to have the power of forming a kind of radicle which retains two or several atoms of various other substances--for example, chlorine and hydrogen, hydrogen and sulphur, sodium and manganese, phosphorus and metals, &c., forming comparatively stable compounds, NaClO_{4}, Na_{2}SO_{4}, NaMnO_{4}, Na_{3}PO_{4}, &c. _See_ Chapter X. Note 1 and Chapter XV. [37] If chlorine be passed through a _cold_ solution of potash, a bleaching compound, potassium chloride and hypochlorite, KCl + KClO, is formed, but if it be passed through a _hot_ solution potassium chlorate is formed. As this is sparingly soluble in water, it chokes the gas-conducting tube, which should therefore be widened out at the end. Potassium chlorate is usually obtained on a large scale from calcium chlorate, which is prepared by passing chlorine (as long as it is absorbed) into water containing lime, the mixture being kept warm. A mixture of calcium chlorate and chloride is thus formed in the solution. Potassium chloride is then added to the warm solution, and on cooling a precipitate of potassium chlorate is formed as a substance which is sparingly soluble in cold water, especially in the presence of other salts. The double decomposition taking place is Ca(ClO_{3})_{2} + 2KCl = CaCl_{2} + 2KClO_{3}. On a small scale in the laboratory potassium chlorate is best prepared from a strong solution of bleaching powder by passing chlorine through it and then adding potassium chloride. KClO_{3} is always formed by the action of an electric current on a solution of KCl, especially at 80° (Häussermann and Naschold, 1894), so that this method is now used on a large scale. Potassium chlorate crystallises easily in large colourless tabular crystals. Its solubility in 100 parts of water at 0° = 3 parts, 20° = 8 parts, 40° = 14 parts, 60° = 25 parts, 80° = 40 parts. For comparison we will cite the following figures showing the solubility of potassium chloride and perchlorate in 100 parts of water: potassium chloride at O° = 28 parts, 20° = 35 parts, 40° = 40 parts, 100° = 57 parts; potassium perchlorate at 0° about 1 part, 20° about 1-3/4 part, 100° about 18 parts. When heated, potassium chlorate melts (the melting point has been given as from 335°-376°; according to the latest determination by Carnelley, 359°) and decomposes with the evolution of oxygen, potassium perchlorate being at first formed, as will afterwards be described (_see_ Note 47). A mixture of potassium chlorate and nitric and hydrochloric acids effects oxidation and chlorination in solutions. It deflagrates when thrown upon incandescent carbon, and when mixed with sulphur (1/3 by weight) it ignites it on being struck, in which case an explosion takes place. The same occurs with many metallic sulphides and organic substances. Such mixtures are also ignited by a drop of sulphuric acid. All these effects are due to the large amount of oxygen contained in potassium chlorate, and to the ease with which it is evolved. A mixture of two parts of potassium chlorate, one part of sugar, and one part of yellow prussiate of potash acts like gunpowder, but burns too rapidly, and therefore bursts the guns, and it also has a very strong oxidising action on their metal. The sodium salt, NaClO_{3}, is much more soluble than the potassium salt, and it is therefore more difficult to free it from sodium chloride, &c. The barium salt is also more soluble than the potassium salt; O° = 24 parts, 20° = 37 parts, 80° = 98 parts of salt per 100 of water. If dilute sulphuric acid be added to a solution of potassium chlorate, _chloric acid_ is liberated, but it cannot be separated by distillation, as it is decomposed in the process. To obtain the free acid, sulphuric acid must be added to a solution of barium chlorate.[38] The sulphuric acid gives a precipitate of barium sulphate, and free chloric acid remains in solution. The solution may be evaporated under the receiver of an air-pump. This solution is colourless, has no smell, and acts as a powerful acid (it neutralises sodium hydroxide, decomposes sodium carbonate, gives hydrogen with zinc, &c.); when heated above 40°, however, it decomposes, forming chlorine, oxygen, and perchloric acid: 4HClO_{3} = 2HClO_{4} + H_{2}O + Cl_{2} + O_{3}. In a concentrated condition the acid acts as an exceedingly energetic oxidiser, so that organic substances brought into contact with it burst into flame. Iodine, sulphurous acid, and similar oxidisable substances form higher oxidation products and reduce the chloric acid to hydrochloric acid. Hydrochloric acid gas gives chlorine with chloric acid (and consequently with KClO_{3} also) acting in the same manner as it acts on the lower acids: HClO_{3} + 5HCl = 3H_{2}O + 3Cl_{2}. [38] Barium chlorate, Ba(ClO_{3})_{2},H_{2}O, is prepared in the following way: impure chloric acid is first prepared and saturated with baryta, and the barium salt purified by crystallisation. The impure free chloric acid is obtained by converting the potassium in potassium chlorate into an insoluble salt. This is done by adding tartaric or hydrofluosilicic acid to a solution of potassium chlorate, because potassium tartrate and potassium silicofluoride are very sparingly soluble in water. Chloric acid is easily soluble in water. By cautiously acting on potassium chlorate with sulphuric acid, the _dioxide_ (_chloric peroxide_), ClO_{2},[39] is obtained (Davy, Millon). This gas is easily liquefied in a freezing mixture, and boils at +10°. The vapour density (about 35 if H = 1) shows that the molecule of this substance is ClO_{2}.[40] In a gaseous or liquid state it very easily explodes (for instance, at 60°, or by contact with organic compounds or finely divided substances, &c.), forming Cl and O_{2}, and in many instances[41] therefore it acts as an oxidising agent, although (like nitric peroxide) it may itself be further oxidised.[42] In dissolving in water or alkalis chloric peroxide gives chlorous and hypochlorous acids--2ClO_{2} + 2KHO = KClO_{3} + KClO_{2} + H_{2}O--and therefore, like nitric peroxide, the dioxide may be regarded as an intermediate oxide between the (unknown) anhydrides of chlorous and chloric acids: 4ClO_{2} = Cl_{2}O_{3} + Cl_{2}O_{3}.[43] [39] To prepare ClO_{2} 100 grams of sulphuric acid are cooled in a mixture of ice and salt, and 15 grams of powdered potassium chlorate are gradually added to the acid, which is then carefully distilled at 20° to 40°, the vapour given off being condensed in a freezing mixture. Potassium perchlorate is then formed: 3KClO_{3} + 2H_{2}SO_{4} = 2KHSO_{4} + KClO_{4} + 2ClO_{2} + H_{2}O. The reaction may result in an explosion. Calvert and Davies obtained chloric peroxide without the least danger by heating a mixture of oxalic acid and potassium chlorate in a test tube in a water-bath. In this case 2KClO_{3} + 3C_{2}H_{2}O_{4},2H_{2}O = 2C_{2}HKO_{4} + 2CO_{2} + 2ClO_{2} + 8H_{2}O. The reaction is still further facilitated by the addition of a small quantity of sulphuric acid. If a solution of HCl acts upon KClO_{3} at the ordinary temperature, a mixture of Cl_{2} and ClO_{2} is formed, but if the temperature be raised to 80° the greater part of the ClO_{2} decomposes, and when passed through a hot solution of MnCl_{2} it oxidises it. Gooch and Kreider proposed (1894) to employ this method for preparing small quantities of chlorine in the laboratory. [40] By analogy with nitric peroxide it might be expected that at low temperatures a doubling of the molecule into Cl_{2}O_{4} would take place, as the reactions of ClO_{2} point to its being a mixed anhydride of HClO_{2} and HClO_{3}. [41] Owing to the formation of this chlorine dioxide, a mixture of potassium chlorate and sugar is ignited by a drop of sulphuric acid. This property was formerly made use of for making matches, and is now sometimes employed for setting fire to explosive charges by means of an arrangement in which the acid is caused to fall on the mixture at the moment required. An interesting experiment on the combustion of phosphorus under water may be conducted with chlorine dioxide. Pieces of phosphorus and of potassium chlorate are placed under water, and sulphuric acid is poured on to them (through a long funnel); the phosphorus then burns at the expense of the chlorine dioxide. [42] Potassium permanganate oxidises chlorine dioxide into chloric acid (Fürst). [43] The euchlorine obtained by Davy by gently heating potassium chlorate with hydrochloric acid is (Pebal) a mixture of chlorine dioxide and free chlorine. The liquid and gaseous chlorine oxide (Note 35), which Millon considered to be Cl_{2}O_{3}, probably contains a mixture of ClO_{2} (vapour density 35), Cl_{2}O_{3} (whose vapour density should be 59), and chlorine (vapour density 35·5), since its vapour density was determined to be about 40. As the salts of chloric acid, HClO_{3}, are produced by the splitting up of the salts of hypochlorous acid, so in the same way the salts of perchloric acid, HClO_{4}, are produced from the salts of chloric acid, HClO_{3}. But this is the highest form of the oxidation of HCl. _Perchloric acid_, HClO_{4}, is the most stable of all the acids of chlorine. When fused potassium chlorate begins to swell up and solidify, after having parted with one-third of its oxygen, potassium chloride and potassium perchlorate have been formed according to the equation 2KClO_{3} = KClO_{4} + KCl + O_{2}. The formation of this salt is easily observed in the preparation of oxygen from potassium chlorate, owing to the fact that the potassium perchlorate fuses with greater difficulty than the chlorate, and therefore appears in the molten salt as solid grains (_see_ Chapter III. Note 12). Under the action of certain acids--for instance, sulphuric and nitric--potassium chlorate also gives potassium perchlorate. This latter may be easily purified, because it is but sparingly soluble in water, although all the other salts of perchloric acid are very soluble and even deliquesce in the air. The perchlorates, although they contain more oxygen than the chlorates, are decomposed with greater difficulty, and even when thrown on ignited charcoal give a much feebler deflagration than the chlorates. Sulphuric acid (at a temperature not below 100°) evolves volatile and to a certain extent stable perchloric acid from potassium perchlorate. Neither sulphuric nor any other acid will further decompose perchloric acid as it decomposes chloric acid. Of all the acids of chlorine, perchloric acid alone can be distilled.[44] The pure hydrate HClO_{4}[45] is a colourless and exceedingly caustic substance which fumes in the air and has a specific gravity 1·78 at 15° (sometimes, after being kept for some time, it decomposes with a violent explosion). It explodes violently when brought into contact with charcoal, paper, wood, and other organic substances. If a small quantity of water be added to this hydrate, and it be cooled, a crystallo-hydrate, ClHO_{4},H_{2}O, separates out. This is much more stable, but the liquid hydrate HClO_{4},2H_{2}O is still more so. The acid dissolves in water in all proportions, and its solutions are distinguished for their stability.[46] When ignited both the acid and its salts are decomposed, with the evolution of oxygen.[47] [44] If a solution of chloric acid, HClO_{3}, be first concentrated over sulphuric acid under the receiver of an air-pump and afterwards distilled, chlorine and oxygen are evolved and perchloric acid is formed: 4HClO_{3} = 2HClO_{4} + Cl_{2} + 3O + H_{2}O. Roscoe accordingly decomposed directly a solution of potassium chlorate by hydrofluosilicic acid, decanted it from the precipitate of potassium silicofluoride, K_{2}SiF_{6}, concentrated the solution of chloric acid, and then distilled it, perchloric acid being then obtained (_see_ following footnote). That chloric acid is capable of passing into perchloric acid is also seen from the fact that potassium permanganate is decolorised, although slowly, by the action of a solution of chloric acid. On decomposing a solution of potassium chlorate by the action of an electric current, potassium perchlorate is obtained at the positive electrode (where the oxygen is evolved). Perchloric acid is also formed by the action of an electric current on solutions of chlorine and chlorine monoxide. Perchloric acid was obtained by Count Stadion and afterwards by Serullas, and was studied by Roscoe and others. [45] Perchloric acid, which is obtained in a free state by the action of sulphuric acid on its salts, may be separated from a solution very easily by distillation, being volatile, although it is partially decomposed by distillation. The solution obtained after distillation may be concentrated by evaporation in open vessels. In the distillation the solution reaches a temperature of 200°, and then a very constant liquid hydrate of the composition HClO_{4},2H_{2}O is obtained in the distillate. If this hydrate be mixed with sulphuric acid, it begins to decompose at 100°, but nevertheless a portion of the acid passes over into the receiver without decomposing, forming a crystalline hydrate HClO_{4},H_{2}O which melts at 50°. On carefully heating this hydrate it breaks up into perchloric acid, which distills over below 100°, and into the liquid hydrate HClO_{4},2H_{2}O. The acid HClO_{4} may also be obtained by adding one-fourth part of strong sulphuric acid to potassium chlorate, carefully distilling and subjecting the crystals of the hydrate HClO_{4},H_{2}O obtained in the distillate to a fresh distillation. Perchloric acid, HClO_{4}, itself does not distil, and is decomposed on distillation until the more stable hydrate HClO_{4}, H_{2}O is formed; this decomposes into HClO_{4} and HClO_{4},2H_{2}O, which latter hydrate distils without decomposition. This forms an excellent example of the influence of water on stability, and of the property of chlorine of giving compounds of the type ClX_{7}, of which all the above hydrates, ClO_{3}(OH), ClO_{2}(OH)_{3}, and ClO(OH)_{5}, are members. Probably further research will lead to the discovery of a hydrate Cl(OH)_{7}. [46] According to Roscoe the specific gravity of perchloric acid = 1·782 and of the hydrate HClO_{4},H_{2}O in a liquid state (50°) 1·811; hence a considerable contraction takes place in the combination of HClO_{4} with H_{2}O. [47] The decomposition of salts analogous to potassium chlorate has been more fully studied in recent years by Potilitzin and P. Frankland. Professor Potilitzin, by decomposing, for example, lithium chlorate LiClO_{3}, found (from the quantity of lithium chloride and oxygen) that at first the decomposition of the fused salt (368°) takes place according to the equation, 3LiClO_{3} = 2LiCl + LiClO_{4} + 5O, and that towards the end the remaining salt is decomposed thus: 5LiClO_{3} = 4LiCl + LiClO_{4} + 10O. The phenomena observed by Potilitzin obliged him to admit that lithium perchlorate is capable of decomposing simultaneously with lithium chlorate, with the formation of the latter salt and oxygen; and this was confirmed by direct experiment, which showed that lithium chlorate is always formed in the decomposition of the perchlorate. Potilitzin drew particular attention to the fact that the decomposition of potassium chlorate and of salts analogous to it, although exothermal (Chapter III., Note 12), not only does not proceed spontaneously, but requires time and a rise of temperature in order to attain completion, which again shows that chemical equilibria are not determined by the heat effects of reactions only. P. Frankland and J. Dingwall (1887) showed that at 448° (in the vapour of sulphur) a mixture of potassium chlorate and powdered glass is decomposed almost in accordance with the equation 2KClO_{3} = KClO_{4} + KCl + O_{2}, whilst the salt by itself evolves about half as much oxygen, in accordance with the equation, 8KClO_{3} = 5KClO_{4} + 3KCl + 2O_{2}. The decomposition of potassium perchlorate in admixture with manganese peroxide proceeds to completion, KClO_{4} = KCl + 2O_{2}. But in decomposing by itself the salt at first gives potassium chlorate, approximately according to the equation 7KClO_{4} = 2KClO_{3} + 5KCl + 11O_{2}. Thus there is now no doubt that when potassium chlorate is heated, the perchlorate is formed, and that this salt, in decomposing with evolution of oxygen, again gives the former salt. In the decomposition of barium hypochlorite, 50 per cent. of the whole amount passes into chlorate, in the decomposition of strontium hypochlorite (Potilitzin, 1890) 12·5 per cent., and of calcium hypochlorite about 2·5 per cent. Besides which Potilitzin showed that the decomposition of the hypochlorites and also of the chlorates is always accompanied by the formation of a certain quantity of the oxides and by the evolution of chlorine, the chlorine being displaced by the oxygen disengaged. Spring and Prost (1889) represent the evolution of oxygen from KClO_{3} as due to the salt first splitting up into base and anhydride, thus (1) 2MClO_{3} = M_{2}O + Cl_{2}O_{5}; (2) Cl_{2}O_{5} = Cl_{2} + O_{3}; and (3) M_{2}O + Cl = 2MCl + O. I may further remark that the decomposition of potassium chlorate as a reaction evolving heat easily lends itself for this very reason to the contact action of manganese peroxide and other similar admixtures; for such very feeble influences as those of contact may become evident either in those cases (for instance, detonating gas, hydrogen peroxide, &c.), when the reaction is accompanied by the evolution of heat, or when (for instance, H_{2} + I_{2}, &c.) little heat is absorbed or evolved. In these cases it is evident that the existing equilibrium is not very stable, and that a small alteration in the conditions at the surfaces of contact may suffice to upset it. In order to conceive the _modus operandi_ of contact phenomena, it is enough to imagine, for instance, that at the surface of contact the movement of the atoms in the molecules changes from a circular to an elliptical path. Momentary and transitory compounds may he formed, but their formation cannot affect the explanation of the phenomena. On comparing chlorine as an element not only with nitrogen and carbon but with all the other non-metallic elements (chlorine has so little analogy with the metals that a comparison with them would be superfluous), we find in it the following fundamental properties of _the halogens_ or salt-producers. With metals chlorine gives salts (such as sodium chloride, &c.); with hydrogen a very energetic and monobasic acid HCl, and the same quantity of chlorine is able by metalepsis to replace the hydrogen; with oxygen it forms unstable oxides of an acid character. These properties of chlorine are possessed by three other elements, bromine, iodine, and fluorine. They are members of one natural family. Each representative has its peculiarities, its individual properties and points of distinction, in combination and in the free state--otherwise they would not be independent elements; but the repetition in all of them of the same chief characteristics of the family enables one more quickly to grasp all their various properties and to classify the elements themselves. In order to have a guiding thread in forming comparisons between the elements, attention must however be turned not only to their points of resemblance but also to those of their properties and characters in which they differ most from each other. And the atomic weights of the elements must be considered as their most elementary property, since this is a quantity which is most firmly established, and must be taken account of in all the reactions of the element. The halogens have the following atomic weights-- F = 19, Cl = 35·5, Br = 80, I = 127. All the properties, physical and chemical, of the elements and their corresponding compounds must evidently be in a certain dependence on this fundamental point, if the grouping in one family be natural.[47 bis] And we find in reality that, for instance, the properties of bromine, whose atomic weight is almost the mean between those of iodine and chlorine, occupy a mean position between those of these two elements. The second measurable property of the elements is their equivalence or their capacity for forming _compounds of definite forms_. Thus carbon or nitrogen in this respect differs widely from the halogens. Although the form ClO_{2} corresponds with NO_{2} and CO_{2}, yet the last is the highest oxide of carbon, whilst that of nitrogen is N_{2}O_{5}, and for chlorine, if there were an anhydride of perchloric acid, its composition would be Cl_{2}O_{7}, which is quite different from that of carbon. In respect to the forms of their compounds the halogens, like all elements of one family or group, are perfectly analogous to each other, as is seen from their hydrogen compounds: HF, HCl, HBr, HI. [47 bis] See, for example the melting point of NaCl, NaBr, NaI in Chapter II. Note 27. According to F. Freyer and V. Meyer (1892), the following are the boiling points of some of the corresponding compounds of chlorine and bromine: BCl_{5} 17° BBr_{3} 90° SiCl_{3} 59° SiBr_{4} 153° PCl_{3} 76° PBr_{3} 175° SbCl_{3} 223° SbBr_{3} 275° BiCl_{3} 447° BiBr_{3} 453° SnCl_{4} 606° SnBr_{4} 619° ZnCl_{2} 730° ZnBr_{2} 650° Thus for all the more volatile compounds the replacement of chlorine by bromine raises the boiling point, but in the ease of ZnX_{2} it lowers it (Chapter XV. Note 19). Their oxygen compounds exhibit a similar analogy. Only fluorine does not give any oxygen compounds. The iodine and bromine compounds corresponding with HClO_{3} and HClO_{4} are HBrO_{3} and HBrO_{4}, HIO_{3} and HIO_{4}. On comparing the properties of these acids we can even predict that fluorine will not form any oxygen compound. For iodine is easily oxidised--for instance, by nitric acid--whilst chlorine is not directly oxidised. The oxygen acids of iodine are comparatively more stable than those of chlorine; and, generally speaking, the affinity of iodine for oxygen is much greater than that of chlorine. Here also bromine occupies an intermediate position. In fluorine we may therefore expect a still smaller affinity for oxygen than in chlorine--and up to now it has not been combined with oxygen. If any oxygen compounds of fluorine should be obtained, they will naturally be exceedingly unstable. The relation of these elements to hydrogen is the reverse of the above. Fluorine has so great an affinity for hydrogen that it decomposes water at the ordinary temperature; whilst iodine has so little affinity for hydrogen that hydriodic acid, HI, is formed with difficulty, is easily decomposed, and acts as a reducing agent in a number of cases. From the form of their compounds the halogens are _univalent elements_ with respect to hydrogen and septivalent with respect to oxygen, N being trivalent to hydrogen (it gives NH_{3}) and quinqui-valent to oxygen (it gives N_{2}O_{5}), and C being quadrivalent to both H and O as it forms CH_{4} and CO_{2}. And as not only their oxygen compounds, but also their hydrogen compounds, have acid properties, the halogens are _elements_ of an exclusively _acid character_. Such metals as sodium, potassium, barium only give basic oxides. In the case of nitrogen, although it forms acid oxides, still in ammonia we find that capacity to give an alkali with hydrogen which indicates a less distinctly acid character than in the halogens. In no other elements is the acid-giving property so strongly developed as in the halogens. In describing certain peculiarities characterising the halogens, we shall at every step encounter a confirmation of the above-mentioned general relations. As _fluorine_ decomposes water with the evolution of oxygen, F_{2} + H_{2}O = 2HF + O, for a long time all efforts to obtain it in free state by means of methods similar to those for the preparation of chlorine proved fruitless.[48] Thus by the action of hydrofluoric acid on manganese peroxide, or by decomposing a solution of hydrofluoric acid by an electric current, either oxygen or a mixture of oxygen and fluorine were obtained instead of fluorine. Probably a certain quantity of fluorine[48 bis] was set free by the action of oxygen or an electric current on incandescent and fused calcium fluoride, but at a high temperature fluorine acts even on platinum, and therefore it was not obtained. When chlorine acted on silver fluoride, AgF, in a vessel of natural fluor spar, CaF_{2}, fluorine was also liberated; but it was mixed with chlorine, and it was impossible to study the properties of the resultant gas. Brauner (1881) also obtained fluorine by igniting cerium fluoride, 2CeF_{4} = 2CeF_{3} + F_{2}; but this, like all preceding efforts, only showed fluorine to be a gas which decomposes water, and is capable of acting in a number of instances like chlorine, but gave no possibility of testing its properties. It was evident that it was necessary to avoid as far as possible the presence of water and a rise of temperature; this Moissan succeeded in doing in 1886. He decomposed anhydrous hydrofluoric acid, liquefied at a temperature of -23° and contained in a U-shaped tube (to which a small quantity of potassium fluoride had been added to make it a better conductor), by the action of a powerful electric current (twenty Bunsen's elements in series). Hydrogen was then evolved at the negative pole, and fluorine appeared at the positive pole (of iridium platinum) as a pale green gas which decomposed water with the formation of ozone and hydrofluoric acid, and combined directly with silicon (forming silicon fluoride, SiF_{4}), boron (forming BF_{3}), sulphur, &c. Its density (H = 1) is 18, so that its molecule is F_{2}. But the action of fluorine on metals at the ordinary temperature is comparatively feeble, because the metallic fluoride formed coats the remaining mass of the metals; it is, however, completely absorbed by iron. Hydrocarbons (such as naphtha), alcohol, &c., immediately absorb fluorine, with the formation of hydrofluoric acid. Fluorine when mixed with hydrogen can easily be made to explode violently, forming hydrofluoric acid.[49] [48] Even before free fluorine was obtained (1886) it was evident from experience gained in the efforts made to obtain it, and from analogy, that it would decompose water (_see_ first Russian edition of the _Principles of Chemistry_). [48 bis] It is most likely that in this experiment of Fremy's, which corresponds with the action of oxygen on calcium chloride, fluorine was set free, but that a converse reaction also proceeded, CaO + F_{2} = CaF_{2} + O--that is, the calcium distributed itself between the oxygen and fluorine. MnF_{4}, which is capable of splitting up into MnF_{2} and F_{2}, is without doubt formed by the action of a strong solution of hydrofluoric acid on manganese peroxide, but under the action of water the fluorine gives hydrofluoric acid, and probably this is aided by the affinity of the manganese fluoride and hydrofluoric acid. In all the attempts made (by Davy, Knox, Louget, Fremy, Gore, and others) to decompose fluorides (those of lead, silver, calcium, and others) by chlorine, there were doubtless also cases of distribution, a portion of the metal combined with chlorine and a portion of the fluorine was evolved; but it is improbable that any decisive results were obtained. Fremy probably obtained fluorine, but not in a pure state. [49] According to Moissan, fluorine is disengaged by the action of an electric current on fused hydrogen potassium fluoride, KHF_{2}. The present state of chemical knowledge is such that the knowledge of the properties of an element is much more general than the knowledge of the free element itself. It is useful and satisfactory to learn that even fluorine in the free state has not succeeded in eluding experiment and research, that the efforts to isolate it have been crowned with success, but the sum total of chemical data concerning fluorine as an element gains but little by this achievement. The gain will, however, be augmented if it be now possible to subject fluorine to a comparative study in relation to oxygen and chlorine. There is particular interest in the phenomena of the distribution of fluorine and oxygen, or fluorine and chlorine, competing under different conditions and relations. We may add that Moissan (1892) found that free fluorine decomposes H_{2}S, HCl, HBr, CS_{2}, and CNH with a flash; it does not act upon O_{2}, N_{2}, CO, and CO_{2}; Mg, Al, Ag, and Ni, when heated, burn in it, as also do S, Se, P (forms PF_{5}); it reacts upon H_{2} even in the dark, with the evolution of 366·00 units of heat. At a temperature of -95°, F_{2} still retains its gaseous state. Soot and carbon in general (but not the diamond) when heated in gaseous fluorine form _fluoride of carbon_, CF_{4} (Moissan, 1890); this compound is also formed at 300° by the double decomposition of CCl_{4} and AgF; it is a gas which liquefies at 10° under a pressure of 5 atmospheres. With an alcoholic solution of KHO, CF_{4} gives K_{2}CO_{3}, according to the equation CF_{4} + 6KHO = K_{2}CO_{3} + 4KF + 3H_{2}O. CF_{4} is not soluble in water, but it is easily soluble in CCl_{4} and alcohol. In 1894 Brauner obtained fluorine directly by igniting the easily formed[49 bis] double lead salt HF,3KF,PbF_{4}, which first, at 230°, decomposes with the evolution of HF, and then splits up forming 3KF,PbF_{2} and fluorine F_{2}, which is recognised by the fact that it liberates iodine from KI and easily combines with silicon, forming SiF_{4}. This method gives chemically pure fluorine, and is based upon the breaking up of the higher compound--tetrafluoride of lead, PbF_{4}, corresponding to PbO_{2}, into free fluorine, F_{2}, and the lower more stable form--bifluoride of lead, PbF_{2}, which corresponds to PbO; that is, this method resembles the ordinary method of obtaining chlorine by means of MnO_{2}, as MnCl_{4} here breaks up into MnCl_{2} and chlorine, just as PbF_{4} splits up into PbF_{2} and fluorine. [49 bis] T. Nikolukin (1885) and subsequently Friedrich and Classen obtained PbCl_{4} and a double ammonium salt of tetrachloride of lead (starting from the binoxide), PbCl_{4}2NH_{4}Cl; Hutchinson and Pallard obtained a similar salt of acetic acid (1893) corresponding to PbX_{4} by treating red lead with strong acetic acid; the composition of this salt is Pb(C_{2}H_{3}O_{2})_{4}; it melts (and decomposes) at about 175°. Brauner (1894) obtained a salt corresponding to tetrafluoride of lead, PbF_{4}, and the acid corresponding to it, H_{4}PbF_{8}. For example, by treating potassium plumbate (Chapter XVIII. Note 55) with strong HF, and also the above-mentioned tetra-acetate with a solution of KHF_{2}, Brauner obtained crystalline HK_{3}PbF_{8}--i.e. the salt from which he obtained fluorine. Among the compounds of fluorine, calcium fluoride, CaF_{2}, is somewhat widely distributed in nature as fluor spar,[50] whilst _cryolite_, or aluminium sodium fluoride, Na_{3}AlF_{6}, is found more rarely (in large masses in Greenland). Cryolite, like fluor spar, is also insoluble in water, and gives hydrofluoric acid with sulphuric acid. Small quantities of fluorine have also in a number of cases been found in the bodies of animals, in the blood, urine, and bones. If fluorides occur in the bodies of animals, they must have been introduced in food, and must occur in plants and in water. And as a matter of fact river, and especially sea, water always contains a certain, although small, quantity of fluorine compounds. [50] It is called spar because it very frequently occurs as crystals of a clearly laminar structure, and is therefore easily split up into pieces bounded by planes. It is called fluor spar because when used as a flux it renders ores fusible, owing to its reacting with silica, SiO_{2} + 2CaF_{2} = 2CaO + SiF_{4}; the silicon fluoride escapes as a gas and the lime combines with a further quantity of silica, and gives a vitreous slag. Fluor spar occurs in mineral veins and rocks, sometimes in considerable quantities. It always crystallises in the cubic system, sometimes in very large semi-transparent cubic crystals, which are colourless or of different colours. It is insoluble in water. It melts under the action of heat, and crystallises on cooling. The specific gravity is 3·1. When steam is passed over incandescent fluor spar, lime and hydrofluoric acid are formed: CaF_{2} + H_{2}O = CaO + 2HF. A double decomposition is also easily produced by fusing fluor spar with sodium or potassium hydroxides, or potash, or even with their carbonates; the fluorine then passes over to the potassium or sodium, and the oxygen to the calcium. In solutions--for example, Ca(NO_{3})_{2} + 2KF = CaF_{2} (precipitate) + 2KNO_{3} (in solution)--the formation of calcium fluoride takes place, owing to its very sparing solubility. 26,000 parts of water dissolve one part of fluor spar. Hydrifluoric acid, HF, cannot be obtained from fluor spar in glass retorts, because glass is acted on by and destroys the acid. It is prepared in lead vessels, and when it is required pure, in platinum vessels, because lead also acts on hydrofluoric acid, although only very feebly on the surface, and when once a coating of fluoride and sulphate of lead is formed no further action takes place. Powdered fluor spar and sulphuric acid evolve hydrofluoric acid (which fumes in the air) even at the ordinary temperature, CaF_{2} + H_{2}SO_{4} = CaSO_{4} + 2HF. At 130° fluor spar is completely decomposed by sulphuric acid. The acid is then evolved as vapour, which may be condensed by a freezing mixture into an anhydrous acid. The condensation is aided by pouring water into the receiver of the condenser, as the acid is easily soluble in cold water. In the liquid anhydrous form hydrofluoric acid boils at +19°, and its specific gravity at 12·8° = 0·9849.[51] It dissolves in water with the evolution of a considerable amount of heat, and gives a solution of constant boiling point which distils over at 120°; showing that the acid is able to combine with water. The specific gravity of the compound is 1·15, and its composition HF,2H_{2}O.[52] With an excess of water a dilute solution distils over first. The aqueous solution and the acid itself must be kept in platinum vessels, but the dilute acid may be conveniently preserved in vessels made of various organic materials, such as gutta-percha, or even in glass vessels having an interior coating of paraffin. Hydrofluoric acid does not act on hydrocarbons and many other substances, but it acts in a highly corrosive manner on metals, glass, porcelain, and the majority of rock substances.[53] It also attacks the skin, and is distinguished by its poisonous properties, so that in working with the acid a strong draught must be kept up, to prevent the possibility of the fumes being inhaled. The non-metals do not act on hydrofluoric acid, but all metals--with the exception of mercury, silver, gold, and platinum, and, to a certain degree, lead--decompose it with the evolution of hydrogen. With bases it gives directly metallic fluorides, and behaves in many respects like hydrochloric acid. There are, however, several distinct individual differences, which are furthermore much greater than those between hydrochloric, hydrobromic, and hydriodic acids. Thus the silver compounds of the latter are insoluble in water, whilst silver fluoride is soluble. Calcium fluoride, on the contrary, is insoluble in water, whilst calcium chloride, bromide, and iodide are not only soluble, but attract water with great energy. Neither hydrochloric, hydrobromic, nor hydriodic acid acts on sand and glass, whilst hydrofluoric acid corrodes them, forming gaseous silicon fluoride. The other halogen acids only form normal salts, KCl, NaCl, with Na or K, whilst hydrofluoric acid gives acid salts, for instance HKF_{2} (and by dissolving KF in liquid HF, KHF_{2}2HF is obtained). This latter property is in close connection with the fact that at the ordinary temperature the vapour density of hydrofluoric acid is nearly 20, which corresponds with a formula H_{2}F_{2}, as Mallet (1881) showed; but a depolymerisation occurs with a rise of temperature, and the density approaches 10, which answers to the formula HF.[54] [51] According to Gore. Fremy obtained anhydrous hydrofluoric acid by decomposing lead fluoride at a red heat, by hydrogen, or by beating the double salt HKF_{2}, which easily crystallises (in cubes) from a solution of hydrofluoric acid, half of which has been saturated with potassium hydroxide. Its vapour density corresponds to the formula HF. [52] This composition corresponds to the crystallo-hydrate HCl,2H_{2}O. All the properties of hydrofluoric acid recall those of hydrochloric acid, and therefore the comparative ease with which hydrofluoric acid is liquefied (it boils at +19°, hydrochloric acid at -35°) must be explained by a polymerisation taking place at low temperatures, as will be afterwards explained, H_{2}F_{2} being formed, and therefore in a liquid state it differs from hydrochloric acid, in which a phenomenon of a similar kind has not yet been observed. [53] The corrosive action of hydrofluoric acid on glass and similar siliceous compounds is based upon the fact that it acts on silica, SiO_{2}, as we shall consider more fully in describing that compound, forming gaseous silicon fluoride, SiO_{2} + 4HF = SiF_{4} + 2H_{2}O. Silica, on the other hand, forms the binding (acid) element of glass and of the mass of mineral substances forming the salts of silica. When it is removed the cohesion is destroyed. This is made use of in the arts, and in the laboratory, for etching designs and scales, &c., on glass. In _engraving on glass_ the surface is covered with a varnish composed of four parts of wax and one part of turpentine. This varnish is not acted on by hydrofluoric acid, and it is soft enough to allow of designs being drawn upon it whose lines lay bare the glass. The drawing is made with a steel point, and the glass is afterwards laid in a lead trough in which a mixture of fluor spar and sulphuric acid is placed. The sulphuric acid must be used in considerable excess, as otherwise transparent lines are obtained (owing to the formation of hydrofluosilicic acid). After being exposed for some time, the varnish is removed (melted) and the design drawn by the steel point is found reproduced in dull lines. The drawing may be also made by the direct application of a mixture of a silicofluoride and sulphuric acid, which forms hydrofluoric acid. [54] Mallet (1881) determined the density at 30° and 100°, previous to which Gore (1869) had determined the vapour density at 100°, whilst Thorpe and Hambly (1888) made fourteen determinations between 26° and 88°, and showed that within this limit of temperature the density gradually diminishes, just like the vapour of acetic acid, nitrogen dioxide, and others. The tendency of HF to polymerise into H_{2}F_{2} is probably connected with the property of many fluorides of forming acid salts--for example, KHF_{2} and H_{2}SiF_{6}. We saw above that HCl has the same property (forming, for instance, H_{2}PtCl_{6}, &c., p. 457), and hence this property of hydrofluoric acid does not stand isolated from the properties of the other halogens. The analogy between chlorine and the other two halogens, bromine and iodine, is much more perfect. Not only have their hydrates or halogen acids much in common, but they themselves resemble chlorine in many respects,[55] and even the properties of the corresponding metallic compounds of bromine and iodine are very much alike. Thus, the chlorides, bromides, and iodides of sodium and potassium crystallise in the cubic system, and are soluble in water; the chlorides of calcium, aluminium, magnesium, and barium are just as soluble in water as the bromides and iodides of these metals. The iodides and bromides of silver and lead are sparingly soluble in water, like the chlorides of these metals. The oxygen compounds of bromine and iodine also present a very strong analogy to the corresponding compounds of chlorine. A hypobromous acid is known corresponding with hypochlorous acid. The salts of this acid have the same bleaching property as the salts of hypochlorous acid. Iodine was discovered in 1811 by Courtois in kelp, and was shortly afterwards investigated by Clement, Gay-Lussac, and Davy. Bromine was discovered in 1826 by Balard in the mother liquor of sea water. [55] For instance, the experiment with Dutch metal foil (Note 16) may be made with bromine just as well as with chlorine. A very instructive experiment on the direct combination of the halogens with metals maybe made by throwing a small piece (a shaving) of aluminium into a vessel containing liquid bromine; the aluminium, being lighter, floats on the bromine, and after a certain time reaction sets in accompanied by the evolution of heat, light, and fumes of bromine. The incandescent piece of metal moves rapidly over the surface of the bromine in which the resultant aluminium bromide dissolves. For the sake of comparison we will proceed to cite several thermochemical data (Thomsen) for analogous actions of (1) chlorine, (2) bromine, and (3) iodine, with respect to metals; the halogen being expressed by the symbol X, and the plus sign connecting the reacting substances. All the figures are given in thousands of calories, and refer to molecular quantities in grams and to the ordinary temperature:-- 1 2 3 K_{2} + X_{2} 211 191 160 Na_{2} + X_{2} 195 172 138 Ag_{2} + X_{2} 59 45 28 Hg_{2} + X_{2} 83 68 48 Hg + X_{2} 63 51 34 Ca + X_{2} 170 141 -- Ba + X_{2} 195 170 -- Zn + X_{2} 97 76 49 Pb + X_{2} 83 64 40 Al + X_{2} 161 120 70 We may remark that the latent heat of vaporisation of the molecular weight Br_{2} is about 7·2, and of iodine 6·0 thousand heat units, whilst the latent heat of fusion of Br_{2} is about 0·3, and of I_{2} about 3·0 thousand heat units. From this it is evident that the difference between the amounts of heat evolved does not depend on the difference in physical state. For instance, the vapour of iodine in combining with Zn to form ZnI_{2} would give 48 + 8 + 3, or about sixty thousand heat units, or 1-1/2 times less than Zn + Cl_{2}. _Bromine_ and iodine, like chlorine, occur in sea water in combination with metals. However, the amount of bromides, and especially of iodides, in sea water is so small that their presence can only be discovered by means of sensitive reactions.[56] In the extraction of salt from sea water the bromides remain in the mother liquor. Iodine and bromine also occur combined with silver, in admixture with silver chloride, as a rare ore which is mainly found in America. Certain mineral waters (those of Kreuznach and Staro-rossüsk) contain metallic bromides and iodides, always in admixture with an excess of sodium chloride. Those upper strata of the Stassfurt rock salt (Chapter X.) which are a source of potassium salts also contain metallic bromides,[57] which collect in the mother liquors left after the crystallisation of the potassium salts; and this now forms the chief source (together with certain American springs) of the bromine in common use. Bromine may be easily liberated from a mixture of bromides and chlorides, owing to the fact that chlorine displaces bromine from its compounds with sodium, magnesium, calcium, &c. A colourless solution of bromides and chlorides turns an orange colour after the passage of chlorine, owing to the disengagement of bromine.[58] Bromine may be extracted on a large scale by a similar method, but it is simpler to add a small quantity of manganese peroxide and sulphuric acid to the mother liquid direct. This sets free a portion of the chlorine, and this chlorine liberates the bromine. [56] One litre of sea-water contains about 20 grams of chlorine, and about 0·07 gram of bromine. The Dead Sea contains about ten times as much bromine. [57] But there is no iodine in Stassfurt carnallite. [58] The chlorine must not, however, be in large excess, as otherwise the bromine would contain chlorine. Commercial bromine not unfrequently contains chlorine, as bromine chloride; this is more soluble in water than bromine, from which it may thus be freed. To obtain pure bromine the commercial bromine is washed with water, dried by sulphuric acid, and distilled, the portion coming over at 58° being collected; the greater part is then converted into potassium bromide and dissolved, and the remainder is added to the solution in order to separate iodine, which is removed by shaking with carbon bisulphide. By heating the potassium bromide thus obtained with manganese peroxide and sulphuric acid, bromine is obtained quite free from iodine, which, however, is not present in certain kinds of commercial bromine (the Stassfurt, for instance). By treatment with potash, the bromine is then converted into a mixture of potassium bromide and bromate, and the mixture (which is in the proportion given in the equation) is distilled with sulphuric acid, bromine being then evolved: 5KBr + KBrO_{3} + 6H_{2}SO_{4} = 6KHSO_{4} + 3H_{2}O + 3Br_{2}. After dissolving the bromine in a strong solution of calcium bromide and precipitating with an excess of water, it loses all the chlorine it contained, because chlorine forms calcium chloride with CaBr_{2}. Bromine is a _dark brown liquid_, giving brown fumes, and having a poisonous suffocating smell, whence its name (from the Greek [Greek: brômos], signifying evil smelling). The vapour density of bromine shows that its molecule is Br_{2}. In the cold bromine freezes into brown-grey scales like iodine. The melting point of pure bromine is -7°·05.[59] The density of liquid bromide at 0° is 3·187, and at 15° about 3·0. The boiling point of bromine is about 58°·7. Bromine, like chlorine, is soluble in water; 1 part of bromine at 5° requires 27 parts of water, and at 15° 29 parts of water. The aqueous solution of bromine is of an orange colour, and when cooled to -2° yields crystals containing 10 molecules of water to 1 molecule of bromine.[60] Alcohol dissolves a greater quantity of bromine, and ether a still greater amount. But after a certain time products of the action of the bromine on these organic substances are formed in the solutions. Aqueous solutions of the bromides also absorb a large amount of bromine. [59] There has long existed a difference of opinion as to the melting point of pure bromine. By some investigators (Regnault, Pierre) it was given as between -7° and -8°, and by others (Balard, Liebig, Quincke, Baumhauer) as between -20° and -25°. There is now no doubt, thanks more especially to the researches of Ramsay and Young (1885), that pure bromine melts at about -7°. This figure is not only established by direct experiment (Van der Plaats confirmed it), but also by means of the determination of the vapour tensions. For solid bromine the vapour tension _p_ in mm. at _t_ was found to be-- _p_ = 20 25 30 35 40 45 mm. _t_ = -16°·6 -14° -12° -10° -8·5° -7° For liquid bromine-- _p_ = 50 100 200 400 600 760 mm. _t_ = -5°·0 8°·2 23°·4 40°·4 51°·9 58°·7 These curves intersect at -7°·05. Besides which, in comparing the vapour tension of many liquids (for example, those given in Chapter II., Note 27), Ramsay and Young observed that the ratio of the absolute temperatures (_t_ + 273) corresponding with equal tension _varies_ for every pair of substances in rectilinear proportion in dependence upon _t_, and, therefore, for the above pressure _p_, Ramsay and Young determined the ratio of _t_ + 273 for water and bromine, and found that the straight lines expressing these ratios for liquid and solid bromine intersect also at 7°·05; thus, for example, for solid bromine-- _p_ = 20 25 30 35 40 45 273 + _t_ = 256·4 259 261 263 264·6 266 273 + _t_´ = 295·3 299 302·1 304·8 307·2 309·3 _c_ = 1·152 1·154 1·157 1·159 1·161 1·163 where _t_´ indicates the temperature of water corresponding with a vapour tension _p_, and where _c_ is the ratio of 273 + _t_´ to 273 + _t_. The magnitude of _c_ is evidently expressed with great accuracy by the straight line _c_ = 1·1703 + 0·0011_t_. In exactly the same way we find the ratio for liquid bromine and water to be _c__{1} = 1·1585 + 0·00057t. The intersection of these straight lines in fact corresponds with -7°·06, which again confirms the melting point given above for bromine. In this manner it is possible with the existing store of data to accurately establish and _verify_ the melting point of substances. Ramsay and Young established the thermal constants of iodine by exactly the same method. [60] The observations made by Paterno and Nasini (by Raoult's method, Chapter I. Note 49) on the temperature of the formation of ice (-1°·115, with 1·391 gram of bromine in 100 grams of water) in an aqueous solution of bromine, showed that bromine is contained in solutions as the molecule Br_{2}. Similar experiments conducted on iodine (Kloboukoff 1889 and Beckmann 1890) show that in solution the molecule is I_{2}. B. Roozeboom investigated the hydrate of bromine as completely as the hydrate of chlorine (Notes 9, 10). The temperature of the complete decomposition of the hydrate is +6°·2; the density of Br_{2},10H_{2}O = 1·49. With respect to _iodine_, it is almost exclusively extracted from the mother liquors after the crystallisation of natural sodium nitrate (Chili saltpetre) and from the ashes of the sea-weed cast upon the shores of France, Great Britain, and Spain, sometimes in considerable quantities, by the high tides. The majority of these sea-weeds are of the genera _Fucus_, _Laminaria_, &c. The fused ashes of these sea-weeds are called 'kelp' in Scotland and 'varech' in Normandy. A somewhat considerable quantity of iodine is contained in these sea-weeds. After being burnt (or subjected to dry distillation) an ash is left which chiefly contains salts of potassium, sodium, and calcium. The metals occur in the sea-weed as salts of organic acids. On being burnt these organic salts are decomposed, forming carbonates of potassium and sodium. Hence, sodium carbonate is found in the ash of sea plants. The ash is dissolved in hot water, and on evaporation sodium carbonate and other salts separate, but a portion of the substances remains in solution. These mother liquors left after the separation of the sodium carbonate contain chlorine, bromine, and iodine in combination with metals, the chlorine and iodine being in excess of the bromine. 13,000 kilos of kelp give about 1,000 kilos of sodium carbonate and 15 kilos of iodine. The liberation of the iodine from the mother liquor is effected with comparative ease, because chlorine disengages iodine from potassium iodide and its other combinations with the metals. Not only chlorine, but also sulphuric acid, liberates iodine from sodium iodide. Sulphuric acid, in acting on an iodide, sets hydriodic acid free, but the latter easily decomposes, especially in the presence of substances capable of evolving oxygen, such as chromic acid, nitrous acid, and even ferric salts.[61] Owing to its sparing solubility in water, the iodine liberated separates as a precipitate. To obtain pure iodine it is sufficient to distil it, and neglect the first and last portions of the distillate, the middle portion only being collected. Iodine passes directly from a state of vapour into a crystalline form, and settles on the cool portions of the apparatus in tabular crystals, having a black grey colour and metallic lustre.[62] [61] In general, 2HI + O = I_{2} + H_{2}O, if the oxygen proceed from a substance from which it is easily evolved. For this reason compounds corresponding with the higher stages of oxidation or chlorination frequently give a lower stage when treated with hydriodic acid. Ferric oxide, Fe_{2}O_{3}, is a higher oxide, and ferrous oxide, FeO, a lower oxide; the former corresponds with FeX_{3}, and the latter with FeX_{2}, and this passage from the higher to the lower takes place under the action of hydriodic acid. Thus hydrogen peroxide and ozone (Chapter IV.) are able to liberate iodine from hydriodic acid. Compounds of copper oxide, CuO or CuX_{2}, give compounds of the suboxide Cu_{2}O, or CuX. Even sulphuric acid, which corresponds to the higher stage SO_{3}, is able to act thus, forming the lower oxide SO_{2}. The liberation of iodine from hydriodic acid proceeds with still greater ease under the action of substances capable of disengaging oxygen. In practice, many methods are employed for liberating iodine from acid liquids containing, for example, sulphuric acid and hydriodic acid. The higher oxides of nitrogen are most commonly used; they then pass into nitric oxide. Iodine may even be disengaged from hydriodic acid by the action of iodic acid, &c. But there is a limit in these reactions of the oxidation of hydriodic acid because, under certain conditions, especially in dilute solutions, the iodine set free is itself able to act as an oxidising agent--that is, it exhibits the character of chlorine, and of the halogens in general, to which we shall again have occasion to refer. In Chili, where a large quantity of iodine is extracted in the manufacture of Chili nitre, which contains NaIO_{3}, it is mixed with the acid and normal sulphites of sodium in solution; the iodine is then precipitated according to the equation 2NaIO_{3} + 3Na_{2}SO_{3} + 2NaHSO_{3} = 5Na_{2}SO_{4} +I_{2} + H_{2}O. The iodine thus obtained is purified by sublimation. [62] For the final purification of iodine, Stas dissolved it in a strong solution of potassium iodide, and precipitated it by the addition of water (_see_ Note 58). The specific gravity of the crystals of iodine is 4·95. It melts at 114° and boils at 184°. Its vapour is formed at a much lower temperature, and is of a violet colour, whence iodine receives its name ([Greek: ioeidês], violet). The smell of iodine recalls the characteristic smell of hypochlorous acid; it has a sharp sour taste. It destroys the skin and organs of the body, and is therefore frequently employed for cauterising and as an irritant for the skin. In small quantities it turns the skin brown, but the coloration disappears after a certain time, partly owing to the volatility of the iodine. Water dissolves only 1/5000 part of iodine. A brown solution is thus obtained, which bleaches, but much more feebly than bromine and chlorine. Water which contains salts, and especially iodides, in solution dissolves iodine in considerable quantities, and the resultant solution is of a dark brown colour. Pure alcohol dissolves a small amount of iodine, and in so doing acquires a brown colour, but the solubility of iodine is considerably increased by the presence of a small quantity of an iodine compound--for instance, ethyl iodide--in the alcohol.[63] Ether dissolves a larger amount of iodine than alcohol; but iodine is particularly soluble in liquid hydrocarbons, in carbon bisulphide, and in chloroform. A small quantity of iodine dissolved in carbon bisulphide tints it rose-colour, but in a somewhat larger amount it gives a violet colour. Chloroform (quite free from alcohol) is also tinted rose colour by a small amount of iodine. This gives an easy means for detecting the presence of free iodine in small quantities. The blue coloration which free iodine gives with _starch_ may also, as has already been frequently mentioned (_see_ Chapter IV.), serve for the detection of iodine. [63] The solubility of iodine in solutions containing iodides, and compounds of iodine in general, may serve, on the one hand, as an indication that solution is due to a similarity between the solvent and dissolved substance, and, on the other hand, as an indirect proof of that view as to solutions which was cited in Chapter I., because in many instances unstable highly iodised compounds, resembling crystallo-hydrates, have been obtained from such solutions. Thus iodide of tetramethylammonium, N(CH_{3})_{4}I, combines with I_{2}, and I_{4}. Even a solution of iodine in a saturated solution of potassium iodide presents indications of the formation of a definite compound KI_{3}. Thus, an alcoholic solution of KI_{3} does not give up iodine to carbon bisulphide, although this solvent takes up iodine from an alcoholic solution of iodine itself (Girault, Jörgensen, and others). The instability of these compounds resembles the instability of many crystallo-hydrates, for instance of HCl,2H_{2}O. If we compare the four elements, fluorine, chlorine, bromine, and iodine, we see in them an example of analogous substances which arrange themselves by their physical properties in the same order as they stand in respect to their atomic and molecular weights. If the weight of the molecule be large, the substance has a higher specific gravity, a higher melting and boiling point, and a whole series of properties depending on this difference in its fundamental properties. Chlorine in a free state boils at about -35°, bromine boils at 60°, and iodine only above 180°. According to Avogadro-Gerhardt's law, the vapour densities of these elements in a gaseous state are proportional to their atomic weights, and here, at all events approximately, the densities in a liquid (or solid) state are also almost in the ratio of their atomic weights. Dividing the atomic weight of chlorine (35·5) by its specific gravity in a liquid state (1·3), we obtain a volume = 27, for bromine (80/3·1) 26, and for iodine also (127/4·9) 26.[64] [64] The equality of the atomic volumes of the halogens themselves is all the more remarkable because in all the halogen compounds the volume augments with the substitution of fluorine by chlorine, bromine, and iodine. Thus, for example, the volume of sodium fluoride (obtained by dividing the weight expressed by its formula by its specific gravity) is about 15, of sodium chloride 27, of sodium bromide 32, and of sodium iodide 41. The volume of silicon chloroform, SiHCl_{3}, is 82, and those of the corresponding bromine and iodine compounds are 108 and 122 respectively. The same difference also exists in solutions; for example, NaCl + 200H_{2}O has a sp. gr. (at 15°/4°) of 1·0106, consequently the volume of the solution 3,658·5/1·0106 = 3,620, hence the volume of sodium chloride in solution = 3,620-3,603 (this is the volume of 200 H_{2}O) = 17, and in similar solutions, NaBr = 26 and NaI = 35. The metallic bromides and iodides are in the majority of cases, in most respects analogous to the corresponding chlorides,[65] but chlorine displaces the bromine and iodine from them, and bromine liberates iodine from iodides, which is taken advantage of in the preparation of these halogens. However, the researches of Potilitzin showed that a _reverse_ displacement of chlorine by bromine may occur both in solutions and in ignited metallic chlorides in an atmosphere of bromine vapour--that is, a distribution of the metal (according to Berthollet's doctrine) takes place between the halogens, although however the larger portion, still unites with the chlorine, which shows its greater affinity for metals as compared with that of bromine and iodine.[66] The latter, however, sometimes behave with respect to metallic oxides in exactly the same manner as chlorine. Gay-Lussac, by igniting potassium carbonate in iodine vapour, obtained (as with chlorine) an evolution of oxygen and carbonic anhydride, K_{2}CO_{3} + I_{2} = 2KI + CO_{2} + O, only the reactions between the halogens and oxygen are more easily reversible with bromine and iodine than with chlorine. Thus, at a red heat oxygen displaces iodine from barium iodide. Aluminium iodide burns in a current of oxygen (Deville and Troost), and a similar, although not so clearly marked, relation exists for aluminium chloride, and shows that the halogens have a distinctly smaller affinity for those metals which only form feeble bases. This is still more the case with the non-metals, which form acids and evolve much more heat with oxygen than with the halogens (Note 13). But in all these instances the affinity (and amount of heat evolved) of iodine and bromine is less than that of chlorine, probably because the atomic weights are greater. The smaller store of energy in iodine and bromine is seen still more clearly in the relation of the halogens to hydrogen. In a gaseous state they all enter, with more or less ease, into direct combination with gaseous hydrogen--for example, in the presence of spongy platinum, forming halogen acids, HX--but the latter are far from being equally stable; hydrogen chloride is the most stable, hydrogen iodide the least so, and hydrogen bromide occupies an intermediate position. A very high temperature is required to decompose hydrogen chloride even partially, whilst hydrogen iodide is decomposed by light even at the ordinary temperature and very easily by a red heat. Hence the reaction I_{2} + H_{2} = HI + HI is very easily reversible, and consequently has a limit, and hydrogen iodide easily dissociates.[67] Judging by the direct measurement of the heat evolved (22,000 heat units) in the formation of HCl, the conversion of 2HCl into H_{2} + Cl_{2} requires the expenditure of 44,000 heat units. The decomposition of 2HBr into H_{2} + Br_{2} only requires, if the bromine be obtained in a gaseous state, a consumption of about 24,000 units, whilst in the decomposition of 2HI into H_{2} + I_{2} as vapour about 3,000 heat units are _evolved_;[68] these facts, without doubt, stand in causal connection with the great stability of hydrogen chloride, the easy decomposability of hydrogen iodide, and the intermediate properties of hydrogen bromide. From this it would be expected that chlorine is capable of decomposing water with the evolution of oxygen, whilst iodine has not the energy to produce this disengagement,[69] although it is able to liberate the oxygen from the oxides of potassium and sodium, the affinity of these metals for the halogens being very considerable. For this reason oxygen, especially in compounds from which it can be evolved readily (for instance, ClHO, CrO_{3}, &c.), easily decomposes hydrogen iodide. A mixture of hydrogen iodide and oxygen burns in the presence of an ignited substance, forming water and iodine. Drops of nitric acid in an atmosphere of hydrogen iodide cause the disengagement of violet fumes of iodine and brown fumes of nitric peroxide. In the presence of alkalis and an excess of water, however, iodine is able to effect oxidation like chlorine--that is, it decomposes water; the action is here aided by the affinity of hydrogen iodide for the alkali and water, just as sulphuric acid helps zinc to decompose water. But the relative instability of hydriodic acid is best seen in comparing the acids in a gaseous state. If the halogen acids be dissolved in water, they evolve so much heat that they approach much nearer to each other in properties. This is seen from thermochemical data, for in the formation of HX in solution (in a large excess of water) from the _gaseous_ elements there is _evolved_ for HCl 39,000, for HBr 32,000, and for HI 18,000 heat units.[70] But it is especially evident from the fact that solutions of hydrogen bromide and iodide in water have many points in common with solutions of hydrogen chloride, both in their capacity to form hydrates and fuming solutions of constant boiling point, and in their capacity to form haloid salts, &c. by reacting on bases. [65] But the density (and also molecular volume, Note 64) of a bromine compound is always greater than that of a chlorine compound, whilst that of an iodine compound is still greater. The order is the same in many other respects. For example, an iodine compound has a higher boiling point than a bromine compound, &c. [66] A. L. Potilitzin showed that in heating various metallic chlorides in a closed tube, with an equivalent quantity of bromine, a distribution of the metal between the halogens always occurs, and that the amounts of chlorine replaced by the bromine in the ultimate product are proportional to the atomic weights of the metals taken and inversely proportional to their equivalence. Thus, if NaCl + Br be taken, then out of 100 parts of chlorine, 5·54 are replaced by the bromine, whilst with AgCl + Br 27·28 parts are replaced. These figures are in the ratio 1 : 4·9, and the atomic weights Na : Ag = 1 : 4·7. In general terms, if a chloride MCl_{_n_} be taken, it gives with _n_Br a percentage substitution = 4M/_n_^2 where M is the atomic weight of the metal. This law was deduced from observations on the chlorides of Li, K, Na, Ag (_n_ = 1), Ca, Sr, Ba, Co, Ni, Hg, Pb (_n_ = 2), Bi (_n_ = 3), Sn (_n_ = 4), and Fe_{2} (_n_ = 6). In these determinations of Potilitzin we see not only a brilliant confirmation of Berthollet's doctrine, but also the first effort to directly determine the affinities of elements by means of displacement. The chief object of these researches consisted in proving whether a displacement occurs in those cases where heat is absorbed, and in this instance it should be absorbed, because the formation of all metallic bromides is attended with the evolution of less heat than that of the chlorides, as is seen by the figures given in Note 55. If the mass of the bromine be increased, then the amount of chlorine displaced also increases. For example, if masses of bromine of 1 and 4 equivalents act on a molecule of sodium chloride, then the percentages of the chlorine displaced will be 6·08 p.c. and 12·46 p.c.; in the action of 1, 4, 25, and 100 molecules of bromine on a molecule of barium chloride, there will be displaced 7·8, 17·6, 35·0, and 45·0 p.c. of chlorine. If an equivalent quantity of hydrochloric acid act on metallic bromides in closed tubes, and in the absence of water at a temperature of 300°, then the percentages of the substitution of the bromine by the chlorine in the double decomposition taking place between univalent metals are inversely proportional to their atomic weights. For example, NaBr + HCl gives at the limit 21 p.c. of displacement, KCl 12 p.c. and AgCl 4-1/4 p.c. Essentially the same action takes place in an aqueous solution, although the phenomenon is complicated by the participation of the water. The reactions proceed spontaneously in one or the other direction at the ordinary temperature but at different _rates_. In the action of a dilute solution (1 equivalent per 5 litres) of sodium chloride on silver bromide at the ordinary temperature the amount of bromine replaced in six and a half days is 2·07 p.c., and with potassium chloride 1·5 p.c. With an excess of the chloride the magnitude of the substitution increases. These conversions also proceed with the absorption of heat. The reverse reactions evolving heat proceed incomparably more rapidly, but also to a certain limit; for example, in the reaction AgCl + RBr the following percentages of silver bromide are formed in different times: hours 2 3 22 96 120 K 79·82 87·4 88·22 -- 94·21 Na 83·63 90·74 91·70 95·49 -- That is, the conversions which are accompanied by an evolution of heat proceed with very much greater rapidity than the reverse conversions. [67] _The dissociation of hydriodic acid_ has been studied in detail by Hautefeuille and Lemoine, from whose researches we extract the following information. The decomposition of hydriodic acid is decided, but proceeds slowly at 180°; the rate and limit of decomposition increase with a rise of temperature. The reverse action--that is, I_{2} + H_{2} = 2HI--proceeds not only under the influence of spongy platinum (Corenwinder), which also accelerates the decomposition of hydriodic acid, but also by itself, although slowly. The limit of the reverse reaction remains the same with or without spongy platinum. An increase of pressure has a very powerful accelerative effect on the rate of formation of hydriodic acid, and therefore spongy platinum by condensing gases has the same effect as increase of pressure. At the atmospheric pressure the decomposition of hydriodic acid reaches the limit at 250° in several months, and at 440° in several hours. The limit at 250° is about 18 p.c. of decomposition--that is, out of 100 parts of hydrogen previously combined in hydriodic acid, about 18 p.c. may be disengaged at this temperature (this hydrogen may be easily measured, and the measure of dissociation determined), but not more; the limit at 440° is about 26 p.c. If the pressure under which 2HI passes into H_{2} + I_{2} be 4-1/2 atmospheres, then the limit is 24 p.c.; under a pressure of 1/5 atmosphere the limit is 29 p.c. The small influence of pressure on the dissociation of hydriodic acid (compared with N_{2}O_{4}, Chapter VI. Note 46) is due to the fact that the reaction 2HI = I_{2} + H_{2} is not accompanied by a change of volume. In order to show the influence of time, we will cite the following figures referring to 350°: (1) Reaction H_{2} + I_{2}; after 3 hours, 88 p.c. of hydrogen remained free; 8 hours, 69 p.c.; 34 hours, 48 p.c.; 76 hours, 29 p.c.; and 327 hours, 18·5 p.c. (2) The reverse decomposition of 2HI; after 9 hours, 3 p.c. of hydrogen was set free, and after 250 hours 18·6 p.c.--that is, the limit was reached. The addition of extraneous hydrogen diminishes the limit of the reaction of decomposition, or increases the formation of hydriodic acid from iodine and hydrogen, as would be expected from Berthollet's doctrine (Chapter X.). Thus at 440° 26 p.c. of hydriodic acid is decomposed if there be no admixture of hydrogen, while if H_{2} be added, then at the limit only half as large a mass of HI is decomposed. Therefore, if an infinite mass of hydrogen be added there will be no decomposition of the hydriodic acid. Light aids the decomposition of hydriodic acid very powerfully. At the ordinary temperature 80 p.c. is decomposed under the influence of light, whilst under the influence of heat alone this limit corresponds with a very high temperature. The distinct action of light, spongy platinum, and of impurities in glass (especially of sodium sulphate, which decomposes hydriodic acid), not only render the investigations difficult, but also show that in reactions like 2HI = I_{2} + H_{2}, which are accompanied by slight heat effects, all foreign and feeble influences may strongly affect the progress of the action (Note 47). [68] The thermal determinations of Thomsen (at 18°) gave in thousands of calories, Cl + H = +22, HCl + Aq (that is, on dissolving HCl in a large amount of water) = +17·3, and therefore H + Cl + Aq = +39·3. In taking molecules, all these figures must be doubled. Br + H = +8·4; HBr + Aq = 19·9; H + Br + Aq = +28·3. According to Berthelot 7·2 are required for the vaporisation of Br_{2}, hence Br_{2} + H_{2} = 16·8 + 7·2 = +24, if Br_{2} be taken as vapour for comparison with Cl_{2}. H + I =-6·0, HI + Aq = 19·2; H + I + Aq= +13·2, and, according to Berthelot, the heat of fusion of I_{2} = 3·0, and of vaporisation 6·0 thousand heat units, and therefore I_{2} + H_{2} =-2(6·0) + 3 + 6 =-3·0, if the iodine be taken as vapour. Berthelot, on the basis of his determinations, gives, however, +0·8 thousand heat units. Similar contradictory results are often met with in thermochemistry owing to the imperfection of the existing methods, and particularly the necessity of depending on indirect methods for obtaining the fundamental figures. Thus Thomsen decomposed a dilute solution of potassium iodide by gaseous chlorine; the reaction gave +26·2, whence, having first determined the heat effects of the reactions KHO + HCl, KHO + HI and Cl + H in aqueous solutions, it was possible to find H + I + Aq; then, knowing HI + Aq, to find I + H. It is evident that unavoidable errors may accumulate. [69] One can believe, however, on the basis of Berthollet's doctrine, and the observations of Potilitzin (Note 66), that a certain slow decomposition of water by iodine takes place. On this view the observations of Dossios and Weith on the fact that the solubility of iodine in water increases after the lapse of several months will be comprehensible. Hydriodic acid is then formed, and it increases the solubility. If the iodine be extracted from such a solution by carbon bisulphide, then, as the authors showed, after the action of nitrous anhydride iodine may be again detected in the solution by means of starch. It can easily be understood that a number of similar reactions, requiring much time and taking place in small quantities, have up to now eluded the attention of investigators, who even still doubt the universal application of Berthollet's doctrine, or only see the thermochemical side of reactions, or else neglect to pay attention to the element of time and the influence of mass. [70] On the basis of the data in Note 68. In consequence of what has been said above, it follows that _hydrobromic and hydriodic acids_, being substances which are but slightly stable, cannot be evolved in a gaseous state under many of those conditions under which hydrochloric acid is formed. Thus if sulphuric acid in solution acts on sodium iodide, all the same phenomena take place as with sodium chloride (a portion of the sodium iodide gives hydriodic acid, and all remains in solution), but if sodium iodide be mixed with strong sulphuric acid, then the oxygen of the latter decomposes the hydriodic acid set free, with liberation of iodine, H_{2}SO_{4} + 2HI = 2H_{2}O + SO_{2} + I_{2}. This reaction takes place in the reverse direction in the presence of a _large quantity_ of water (2,000 parts of water per 1 part of SO_{2}), in which case not only the affinity of hydriodic acid for water is brought to light but also the action of water in directing chemical reactions in which it participates.[71] Therefore, with a halogen salt, it is easy to obtain gaseous hydrochloric acid by the action of sulphuric acid, but neither hydrobromic nor hydriodic acid can be so obtained in the free state (as gases).[72] Other methods have to be resorted to for their preparation, and recourse must not be had to compounds of oxygen, which are so easily able to destroy these acids. Therefore hydrogen sulphide, phosphorus, &c., which themselves easily take up oxygen, are introduced as means for the conversion of bromine and iodine into hydrobromic and hydriodic acids in the presence of water. For example, in the action of phosphorus the essence of the matter is that the oxygen of the water goes to the phosphorus, and the union of the remaining elements leads to the formation of hydrobromic or hydriodic acid; but the matter is complicated by the reversibility of the reaction, the affinity for water, and other circumstances which are understood by following Berthollet's doctrine. Chlorine (and bromine also) directly decomposes hydrogen sulphide, forming hydrochloric acid and liberating sulphur, both in a gaseous form and in solutions, whilst iodine only decomposes hydrogen sulphide in weak solutions, when its affinity for hydrogen is aided by the affinity of hydrogen iodide for water. In a gaseous state iodine does not act on hydrogen sulphide,[73] whilst sulphur is able to decompose gaseous hydriodic acid, forming hydrogen sulphide and a compound of sulphur and iodine which with water forms hydriodic acid.[74] [71] A number of similar cases confirm what has been said in Chapter X. [72] This is prevented by the reducibility of sulphuric acid. If volatile acids be taken they pass over, together with the hydrobromic and hydriodic acids, when distilled; whilst many non-volatile acids which are not reduced by hydrobromic and hydriodic acids only act feebly (like phosphoric acid), or do not act at all (like boric acid). [73] This is in agreement with the thermochemical data, because if all the substances be taken in the gaseous state (for sulphur the heat of fusion is 0·3, and the heat of vaporisation 2·3) we have H_{2} + S = 4·7; H_{2} + Cl_{2} = 44; H_{2} + Br_{2} = 24, and H_{2} + I_{2} = -3 thousand heat units; hence the formation of H_{2}S gives less heat than that of HCl and HBr, but more than that of HI. In dilute solutions H_{2} + S + Aq = 9·3, and consequently less than the formation of all the halogen acids, as H_{2}S evolves but little heat with water, and therefore in dilute solutions chlorine, bromine, and iodine decompose hydrogen sulphide. [74] Here there are three elements, hydrogen, sulphur, and iodine, each pair of which is able to form a compound, HI, H_{2}S, and SI, besides which the latter may unite in various proportions. The complexity of chemical mechanics is seen in such examples as these. It is evident that only the study of the simplest cases can give the key to the more complex problems, and on the other hand it is evident from the examples cited in the last pages that, without penetrating into the conditions of chemical equilibria, it would be impossible to explain chemical phenomena. By following the footsteps of Berthollet the possibility of unravelling the problems will be reached; but work in this direction has only been begun during the last ten years, and much remains to be done in collecting experimental material, for which occasions present themselves at every step. In speaking of the halogens I wished to turn the reader's attention to problems of this kind. If hydrogen sulphide be passed through water containing iodine, the reaction H_{2}S + I_{2} = 2HI + S proceeds so long as the solution is dilute, but when the mass of free HI increases the reaction stops, because the iodine then passes into solution. A solution having a composition approximating to 2HI + 4I_{2} + 9H_{2}O (according to Bineau) does not react with H_{2}S, notwithstanding the quantity of free iodine. Therefore only weak solutions of hydriodic acid can be obtained by passing hydrogen sulphide into water with iodine.[74 bis] [74 bis] The same essentially takes place when sulphurous anhydride, in a dilute solution, gives hydriodic acid and sulphuric acid with iodine. On concentration a reverse reaction takes place. The equilibrated systems and the part played by water are everywhere distinctly seen. To obtain[75] gaseous hydrobromic and hydriodic acids it is most convenient to take advantage of the reactions between phosphorus, the halogens, and water, the latter being present in small quantity (otherwise the halogen acids formed are dissolved by it); the halogen is gradually added to the phosphorus moistened with water. Thus if red phosphorus be placed in a flask and moistened with water, and bromine be added drop by drop (from a tap funnel), hydrobromic acid is abundantly and uniformly disengaged.[76] Hydrogen iodide is prepared by adding 1 part of common (yellow) dry phosphorus to 10 parts of dry iodine in a glass flask. On shaking the flask, union proceeds quietly between them (light and heat being evolved), and when the mass of iodide of phosphorus which is formed has cooled, water is added drop by drop (from a tap funnel) and hydrogen iodide is evolved directly without the aid of heat. These methods of preparation will be at once understood when it is remembered (p. 468) that phosphorus chloride gives hydrogen chloride with water. It is exactly the same here--the oxygen of the water passes over to the phosphorus, and the hydrogen to the iodine, thus, PI_{3} + 3H_{2}O = PH_{3}O_{3} + 3HI.[77] [75] Methods of formation and preparation are nothing more than particular cases of chemical reaction. If the knowledge of chemical mechanics were more exact and complete than it now is it would be possible to foretell all cases of preparation _with every detail_ (of the quantity of water, temperature, pressure, mass, &c.) The study of practical methods of preparation is therefore one of the paths for the study of chemical mechanics. The reaction of iodine on phosphorus and water is a case like that mentioned in Note 74, and the matter is here further complicated by the possibility of the formation of the compound PH_{3} with HI, as well as the production of PI_{2}, PI_{3}, and the affinity of hydriodic acid and the acids of phosphorus for water. The theoretical interest of equilibria in all their complexity is naturally very great, but it falls into the background in presence of the primary interest of discovering practical methods for the isolation of substances, and the means of employing them for the requirements of man. It is only after the satisfaction of these requirements that interests of the other order arise, which in their turn must exert an influence on the former. For these reasons, whilst considering it opportune to point out the theoretical interest of chemical equilibria, the chief attention of the reader is directed in this work to questions of practical importance. [76] Hydrobromic acid is also obtained by the action of bromine on paraffin heated to 180°. Gustavson proposed to prepare it by the action of bromine (best added in drops together with traces of aluminium bromide) on anthracene (a solid hydrocarbon from coal tar). Balard prepared it by passing bromine vapour over moist pieces of common phosphorus. The liquid tribromide of phosphorus, directly obtained from phosphorus and bromine, also gives hydrobromic acid when treated with water. Bromide of potassium or sodium, when treated with sulphuric acid in the presence of phosphorus, also gives hydrobromic acid, but hydriodic acid is decomposed by this method. In order to free hydrobromic acid from bromine vapour it is passed over moist phosphorus and dried either by phosphoric anhydride or calcium bromide (calcium chloride cannot be used, as hydrochloric acid would be formed). Neither hydrobromic nor hydriodic acids can be collected over mercury, on which they act, but they may be directly collected in a dry vessel by leading the gas-conducting tube to the bottom of the vessel, both gases being much heavier than air. Merz and Holtzmann (1889) proposed to prepare HBr directly from bromine and hydrogen. For this purpose pure dry hydrogen is passed through a flask containing boiling bromine. The mixture of gas and vapour then passes through a tube provided with one or two bulbs, which is heated moderately in the middle. Hydrobromic acid is formed with a series of flashes at the part heated. The resultant HBr, together with traces of bromine, passes into a Woulfe's bottle into which hydrogen is also introduced, and the mixture is then carried through another heated tube, after which it is passed through water which dissolves the hydrobromic acid. According to the method proposed by Newth (1892) a mixture of bromine and hydrogen is led through a tube containing a platinum spiral, which is heated to redness after the air has been displaced from the tube. If the vessel containing the bromine be kept at 60°, the hydrogen takes up almost the theoretical amount of bromine required for the formation of HBr. Although the flame which appears in the neighbourhood of the platinum spiral does not penetrate into the vessel containing the bromine, still, for safety, a tube filled with cotton wool may be interposed. Hydroiodic acid is obtained in the same manner as hydrobromic. The iodine is heated in a small flask, and its vapour is carried over by hydrogen into a strongly heated tube, The gas passing from the tube is found to contain a considerable amount of HI, together with some free iodine. At a low red heat about 17 p.c. of the iodine vapour enters into combination; at a higher temperature, 78 p.c. to 79 p.c.; and at a strong heat about 82 p.c. [77] But generally more phosphorus is taken than is required for the formation of PI_{3}, because otherwise a portion of the iodine distils over. If less than one-tenth part of iodine be taken, much phosphonium iodide, PH_{4}I, is formed. This proportion was established by Gay-Lussac and Kolbe. Hydriodic acid is also prepared in many other ways. Bannoff dissolves two parts of iodine in one part of a previously prepared strong (sp. gr. 1·67) solution of hydriodic acid, and pours it on to red phosphorus in a retort. Personne takes a mixture of fifteen parts of water, ten of iodine, and one of red phosphorus, which, when heated, disengages hydriodic acid mixed with iodine vapour; the latter is removed by passing it over moist phosphorus (Note 76). It must be remembered however that reverse reaction (Oppenheim) may take place between the hydriodic acid and phosphorus, in which the compounds PH_{4}I and PI_{2} are formed. It should be observed that the reaction between phosphorus, iodine and water must be carried out in the above proportions and with caution, as they may react with explosion. With red phosphorus the reaction proceeds quietly, but nevertheless requires care. L. Meyer showed that with an excess of iodine the reaction proceeds without the formation of bye-products (PH_{4}I), according to the equation P + 5I + 4H_{2}O = PH_{3}O_{4} + 5HI. For this purpose 100 grams of iodine and 10 grams of water are placed in a retort, and a paste of 5 grams of red phosphorus and 10 grams of water is added little by little (at first with great care). The hydriodic acid may be obtained free from iodine by directing the neck of the retort upwards and causing the gas to pass through a shallow layer of water (respecting the formation of HI, _see_ also Note 75). In a gaseous form hydrobromic and hydriodic acids are closely analogous to hydrochloric acid; they are liquefied by pressure and cold, they fume in the air, form solutions and hydrates, of constant boiling point, and react on metals, oxides and salts, &c.[78] Only the relatively easy decomposability of hydrobromic acid and especially of hydriodic acid, clearly distinguish these acids from hydrochloric acid. For this reason, hydriodic acid acts in a number of cases as a deoxidiser or reducer, and frequently even serves as a means for the transference of hydrogen. Thus Berthelot, Baeyer, Wreden, and others, by heating unsaturated hydrocarbons in a solution of hydriodic acid, obtained their compounds with hydrogen nearer to the limit C_{_n_}H_{2_n_ + 2} or even the saturated compounds. For example, benzene, C_{6}H_{6}, when heated in a closed tube with a strong solution of hydriodic acid, gives hexylene, C_{6}H_{12}. The easy decomposability of hydriodic acid accounts for the fact that iodine does not act by metalepsis on hydrocarbons, for the hydrogen iodide liberated with the product of metalepsis, RI, formed, gives iodine and the hydrogen compound, RH, back again. And therefore, to obtain the products of iodine substitution, either iodic acid, HIO_{3} (Kekulé), or mercury oxide, HgO (Weselsky), is added, as they immediately react on the hydrogen iodide, thus: HIO_{3} + 5HI = 3H_{2}O + 3I_{2}, or, HgO + 2HI = HgI_{2} + H_{2}O. From these considerations it will be readily understood that iodine acts like chlorine (or bromine) on ammonia and sodium hydroxide, for in these cases the hydriodic acid produced forms NH_{4}I and NaI. With tincture of iodine or even the solid element, a solution of ammonia immediately forms a highly-explosive solid black product of metalepsis, NHI_{2}, generally known as _iodide_ of _nitrogen_, although it still contains hydrogen (this was proved beyond doubt by Szuhay 1893), which may be replaced by silver (with the formation of NAgI_{2}): 3NH_{3} + 2I_{2} = 2NH_{4}I + NHI_{2}. However, the composition of the last product is variable, and with an excess of water NI_{3} seems to be formed. Iodide of nitrogen is just as explosive as nitrogen chloride.[78 bis] In the action of iodine on sodium hydroxide no bleaching compound is formed (whilst bromine gives one), but a direct reaction is always accomplished with the formation of an iodate, 6NaHO + 3I_{2} = 5NaI + 3H_{2}O + NaIO_{3} (Gay-Lussac). Solutions of other alkalis, and even a mixture of water and oxide of mercury, act in the same manner.[79] This direct formation of _iodic acid_, HIO_{3} = IO_{2}(OH), shows the propensity of iodine to give compounds of the type IX_{5}. Indeed, this capacity of iodine to form compounds of a high type emphasises itself in many ways. But it is most important to turn attention to the fact that iodic acid is easily and directly formed by the action of oxidising substances on iodine. Thus, for instance, strong nitric acid directly converts iodine into iodic acid, whilst it has no oxidising action on chlorine.[79 bis] This shows a greater affinity in iodine for oxygen than in chlorine, and this conclusion is confirmed by the fact that iodine displaces chlorine from its oxygen acids,[80] and that in the presence of water chlorine oxidises iodine.[81] Even ozone or a silent discharge passed through a mixture of oxygen and iodine vapour is able to directly oxidise iodine[82] into iodic acid. It is disengaged from solutions as a hydrate, HIO_{3}, which loses water at 170°, and gives an anhydride, I_{2}O_{5}. Both these substances are crystalline (sp. gr. I_{2}O_{5} 5·037, HIO_{3} 4·869 at 0°), colourless and soluble in water;[83] both decompose at a red heat into iodine and oxygen, are in many cases powerfully oxidising--for instance, they oxidise sulphurous anhydride, hydrogen sulphide, carbonic oxide, &c.--form chloride of iodine and water with hydrochloric acid, and with bases form salts, not only normal MIO_{3}, but also acid; for example, KIO_{3}HIO_{3}, KIO_{3}2HIO_{3}.[83 bis] With hydriodic acid iodic acid immediately reacts, disengaging iodine, HIO_{3} + 5HI = 3H_{2}O + 3I_{2}. [78] The specific gravities of their solutions as deduced by me on the basis of Topsöe and Berthelot's determinations for 15°/4° are as follows:-- 10 20 30 40 50 60 p.c. HBr 1·071 1·156 1·258 1·374 1·505 1·650 HI 1·075 1·164 1·267 1·399 1·567 1·769 Hydrobromic acid forms two hydrates, HBr,2H_{2}O and HBr,H_{2}O, which have been studied by Roozeboom with as much completeness as the hydrate of hydrochloric acid (Chapter X. Note 37). With metallic silver, solutions of hydriodic acid give hydrogen with great ease, forming silver iodide. Mercury, lead, and other metals act in a similar manner. [78 bis] Iodide of nitrogen, NHI_{2} is obtained as a brown pulverulent precipitate on adding a solution of iodine (in alcohol, for instance) to a solution of ammonia. If it be collected on a filter-paper, it does not decompose so long as the precipitate is moist; but when dry it explodes violently, so that it can only be experimented upon in small quantities. Usually the filter-paper is torn into bits while moist, and the pieces laid upon a brick; on drying an explosion proceeds not only from friction or a blow, but even spontaneously. The more dilute the solution of ammonia, the greater is the amount of iodine required for the formation of the precipitate of NHI_{2}. A low temperature facilitates its formation. NHI_{2} dissolves in ammonia water, and when heated the solution forms HIO_{3} and iodine. With KI, iodide of nitrogen gives iodine, NH_{3} and KHO. These reactions (Selivanoff) are explained by the formation of HIO from NHI_{2} + 2H_{2}O = NH_{3} + 2HIO--and then KI + HIO = I_{2} + KHO. Selivanoff (_see_ Note 29) usually observed a temporary formation of hypoiodous acid, HIO, in the reaction of ammonia upon iodine, so that here the formation of NHI_{2} is preceded by that of HIO--_i.e._ first I_{2} + H_{2}O = HIO + HI, and then not only the HI combines with NH_{3}, but also 2HIO + NH_{3} = NHI_{2} + 2H_{2}O. With dilute sulphuric acid iodide of nitrogen (like NCl_{3}) forms hypoiodous acid, but it immediately passes into iodic acid, as is expressed by the equation 5HIO = 2I_{2} + HIO_{3} + 2H_{2}O (first 3HIO = HIO_{3} + 2HI, and then HI + HIO = I_{2} + H_{2}O). Moreover, Selivanoff found that iodide of nitrogen, NHI_{2}, dissolves in an excess of ammonia water, and that with potassium iodide the solution gives the reaction for hypoiodous acid (the evolution of iodine in an alkaline solution). This shows that HIO participates in the formation and decomposition of NHI_{2}, and therefore the condition of the iodine (its metaleptic position) in them is analogous, and differs from the condition of the halogens in the haloid-anhydrides (for instance, NO_{2}Cl). The latter are tolerably stable, while (the haloid being designated by X) NHX_{2}, NX_{3}, XOH, RXO (_see_ Chapter XIII. Note 43), &c., are unstable, easily decomposed with the evolution of heat, and, under the action of water, the haloid is easily replaced by hydrogen (Selivanoff), as would be expected in true products of metalepsis. [79] Hypoiodous acid, HIO, is not known, but organic compounds, RIO, of this type are known. To illustrate the peculiarities of their properties we will mention one of these compounds, namely, _iodosobenzol_, C_{6}H_{5}IO. This substance was obtained by Willgerodt (1892), and also by V. Meyer, Wachter, and Askenasy, by the action of caustic alkalis upon phenoldiiodochloride, C_{6}H_{5}ICl_{2} (according to the equation, C_{6}H_{5}ICl_{2} + 2MOH = C_{6}H_{5}IO + 2MCl + H_{2}O). Iodosobenzol is an amorphous yellow substance, whose melting point could not be determined because it explodes at 210°, decomposing with the evolution of iodine vapour. This substance dissolves in hot water and alcohol, but is not soluble in the majority of other neutral organic solvents. If acids do not oxidise C_{6}H_{5}IO, they give saline compounds in which iodosobenzol appears as a basic oxide of a diatomic metal, C_{6}H_{5}I. Thus, for instance, when an acetic acid solution of iodosobenzol is treated with a solution of nitric acid, it gives large monoclinic crystals of a nitric acid salt having the composition C_{6}H_{5}I(NO_{3})_{2} (like Ca(NO_{3})_{2}). In appearing as the analogue of basic oxides, iodosobenzol displaces iodine from potassium iodide (in a solution acidulated with acetic or hydrochloric acid)--_i.e._ it acts with its oxygen like HClO. The action of peroxide of hydrogen, chromic acid, and other similar oxidising agents gives iodoxybenzol, C_{6}H_{5}IO_{2}, which is a neutral substance--_i.e._ incapable of giving salts with acids (compare Chapter XIII. Note 43). [79 bis] The oxidation of iodine by strong nitric acid was discovered by Connell; Millon showed that it is effected, although more slowly, by the action of the hydrates of nitric acid up to HNO_{3},H_{2}O, but that the solution HNO_{3},2H_{2}O, and weaker solutions, do not oxidise, but simply dissolve, iodine. The participation of water in reactions is seen in this instance. It is also seen, for example, in the fact that dry ammonia combines directly with iodine--for instance, at 0° forming the compound I_{2},4NH_{3}--whilst iodide of nitrogen is only formed in presence of water. [80] Bromine also displaces chlorine--for instance, from chloric acid, directly forming bromic acid. If a solution of potassium chlorate be taken (75 parts per 400 parts of water), and iodine be added to it (80 parts), and then a small quantity of nitric acid, chlorine is disengaged on boiling, and potassium iodate is formed in the solution. In this instance the nitric acid first evolves a certain portion of the chloric acid, and the latter, with the iodine, evolves chlorine. The iodic acid thus formed acts on a further quantity of the potassium chlorate, sets a portion of the chloric acid free, and in this manner the action is kept up. Potilitzin (1887) remarked, however, that not only do bromine and iodine displace the chlorine from chloric acid and potassium chlorate, but also chlorine displaces bromine from sodium bromate, and, furthermore, the reaction does not proceed as a direct substitution of the halogens, but is accompanied by the formation of free acids; for example, 5NaClO_{3} + 3Br_{2} + 3H_{2}O = 5NaBr + 5HClO_{3} + HBrO_{3}. [81] If iodine be stirred up in water, and chlorine passed through the mixture, the iodine is dissolved; the liquid becomes colourless, and contains, according to the relative amounts of water and chlorine, either IHCl_{2}, or ICl_{3}, or HIO_{3}. If there be a small amount of water, then the iodic acid may separate out directly as crystals, but a complete conversion (Bornemann) only occurs when not less than ten parts of water are taken to one part of iodine--ICl + 3H_{2}O + 2Cl_{2} = IHO_{3} + 5HCl. [82] Schönbein and Ogier proved this. Ogier found that at 45° ozone immediately oxidises iodine vapour, forming first of all the oxide I_{2}O_{3}, which is decomposed by water or on heating into iodic anhydride and iodine. Iodic acid is formed at the positive pole when a solution of hydriodic acid is decomposed by a galvanic current (Riche). It is also formed in the combustion of hydrogen mixed with a small quantity of hydriodic acid (Salet). [83] Kämmerer showed that a solution of sp. gr. 2·127 at 14°, containing 2HIO_{3},9H_{2}O, solidified completely in the cold. On comparing solutions HI + _m_H_{2}O with HIO_{3} + _m_H_{2}O, we find that the specific gravity increases but the volume decreases, whilst in the passage of solutions HCl + _m_H_{2}O to HClO_{3} + _m_H_{2}O both the specific gravity and the volume increase, which is also observed in certain other cases (for example, H_{3}PO_{3} and H_{3}PO_{4}). [83 bis] Ditte (1890) obtained many iodates of great variety. A neutral salt, 2(LiIO_{3})H_{2}O, is obtained by saturating a solution of lithia with iodic acid. There is an analogous ammonium salt, 2(NH_{4}IO_{3})H_{2}O. He also obtained hydrates of a more complex composition, such as 6(NH_{4}IO_{3})H_{2}O and 6(NH_{4}IO_{3})2H_{2}O. Salts of the alkaline earths, Ba(IO_{3})_{2}H_{2}O and Sr(IO_{3})_{2}H_{2}O, may be obtained by a reaction of double decomposition from the normal salts of the type 2(MeIO_{3})H_{2}O. When evaporated at 70° to 80° with nitric acid these salts lose water. A mixture of solutions of nitrate of zinc and an alkaline iodate precipitates Zn(IO_{3})_{2}2H_{2}O. An anhydrous salt is thrown out if nitric acid be added to the solutions. Analogous salts of cadmium, silver, and copper give compounds of the type 2Me´IO_{3}4NH_{3} and Me´´(IO_{3})_{2}4NH_{3}, with gaseous ammonia (Me´ and Me´´ being elements of the first (Ag) and second (Cd, Zn, Cu) groups). With an aqueous solution of ammonia the above salts give substances of a different composition, such as Zn(IO_{3})_{2}(NH_{4})_{2}O, Cd(IO_{3})_{2}(NH_{4})_{2}O. Copper gives Cu(IO_{3})_{2}4(NH_{4})_{2}O and Cu(IO_{3})_{2}(NH_{4})_{2}O. These salts may be regarded as compounds of I_{2}O_{5}, and MeO and (NH_{4})_{2}O; for example, Zn(IO_{3})_{2}(NH_{4})_{2}O may be regarded as ZnO(NH_{4})_{2}OI_{2}O_{5}, or, as derived from the hydrate, I_{2}O_{5}2H_{2}O = 2(HIO_{3})H_{2}O. As with chlorine, so with iodine, a _periodic acid_, HIO_{4}, is formed. This acid is produced in the form of its salts, by the action of chlorine on alkaline solutions of iodates, and also by the action of iodine on chloric acid.[84] It crystallises from solutions as a hydrate containing 2H_{2}O (corresponding with HClO_{4},2H_{2}O), but as it forms salts containing up to 5 atoms of metals, this water must be counted as water of constitution. Therefore IO(OH)_{5} = HIO_{4},2H_{2}O corresponds with the highest form of halogen compounds, IX_{7}.[85] In decomposing (at 200°) or acting as an oxidiser, periodic acid first gives iodic acid, but it may also be ultimately decomposed. [84] If sodium iodate be mixed with a solution of sodium hydroxide, heated, and chlorine passed through the solution, a sparingly soluble salt separates out, which corresponds with periodic acid, and has the composition Na_{4}I_{2}O_{9},3H_{2}O. 6NaHO + 2NaIO_{3} + 4Cl = 4NaCl + Na_{4}I_{2}O_{9} + 3H_{2}O. This compound is sparingly soluble in water, but dissolves easily in a very dilute solution of nitric acid. If silver nitrate be added to this solution a precipitate is formed which contains the corresponding compound of silver, Ag_{4}I_{2}O_{9},3H_{2}O. If this sparingly soluble silver compound be dissolved in hot nitric acid, orange crystals of a salt having the composition AgIO_{4} separate on evaporation. This salt is formed from the preceding by the nitric acid taking up silver oxide--Ag_{4}I_{2}O_{9} + 2HNO_{3} = 2AgNO_3 + 2AgIO_{4} + H_{2}O. The silver salt is decomposed by water, with the re-formation of the preceding salt, whilst iodic acid remains in solution-- 4AgIO_{4} + H_{2}O = Ag_{4}I_{2}O_{9} + 2HIO_{4}. The structure of the first of these salts, Na_{4}I_{2}O_{9},3H_{2}O, presents itself in a simpler form if the water of crystallisation is regarded as an integral portion of the salt; the formula is then divided in two, and takes the form of IO(OH)_{3}(ONa)_{2}--that is, it answers to the type IOX_{5}, or IX_{7}, like AgIO_{4} which is IO_{3}(OAg). The composition of all the salts of periodic acids are expressed by this type IX_{7}. Kimmins (1889) refers all the salts of periodic acid to four types--the meta-salts of HIO_{4} (salts of Ag, Cu, Pb), the meso-salts of H_{3}IO_{5} (PbH, Ag_{2}H, CdH), the para-salts of H_{5}IO_{6} (Na_{2}H_{3}, Na_{3}H_{2}), and the di-salts of H_{4}I_{2}O_{9} (K_{4}, Ag_{4}, Ni_{2}). The three first are direct compounds of the type IX_{7}, namely, IO_{3}(OH), IO_{2}(OH)_{3}, and IO(OH)_{5}, and the last are types of diperiodic salts, which correspond with the type of the meso-salts, as pyrophosphoric salts correspond with orthophosphoric salts--_i.e._ 2H_{3}IO_{5}-H_{2}O = H_{4}I_{2}O_{9}. [85] Periodic acid, discovered by Magnus and Ammermüller, and whose salts were afterwards studied by Langlois, Rammelsberg, and many others, presents an example of hydrates in which it is evident that there is not that distinction between the water of hydration and of crystallisation which was at first considered to be so clear. In HClO,2H_{2}O the water, 2H_{2}O, is not displaced by bases, and must be regarded as water of crystallisation, whilst in HIO_{4},2H_{2}O it must be regarded as water of hydration. We shall afterwards see that the system of the elements obliges us to consider the halogens as substances giving a highest saline type, _GX__{7}, where _G_ signifies a halogen, and _X_ oxygen (O = _X__{2}), OH, and other like elements. The hydrate IO(OH)_{5} corresponding with many of the salts of periodic acid (for example, the salts of barium, strontium, mercury) does not exhaust all the possible forms. It is evident that various other pyro-, meta-, &c., forms are possible by the loss of water, as will be more fully explained in speaking of phosphoric acid, and as was pointed out in the preceding note. Compounds formed between chlorine and iodine must be classed among the most interesting halogen bodies.[86] These elements combine together directly with evolution of heat, and form _iodine monochloride_, ICl, or _iodine trichloride_, ICl_{3}.[87] As water reacts on these substances, forming iodic acid and iodine, they have to be prepared from dry iodine and chlorine.[88] Both substances are formed in a number of reactions; for example, by the action of aqua regia on iodine, of chlorine on hydriodic acid, of hydrochloric acid on periodic acid, of iodine on potassium chlorate (with the aid of heat, &c.) Trapp obtained iodine monochloride, in beautiful red crystals, by passing a rapid current of chlorine into molten iodine. The monochloride then distils over and solidifies, melting at 27°. By passing chlorine over the crystals of the monochloride, it is easy to obtain iodine trichloride in orange crystals, which melt at 34° and volatilise at 47°, but in so doing decompose (into Cl_{2} and ClI). The chemical properties of these chlorides entirely resemble those of chlorine and iodine, as would be expected, because, in this instance, a combination of similar substances has taken place as in the formation of solutions or alloys. Thus, for instance, the unsaturated hydrocarbons (for example, C_{2}H_{4}), which are capable of directly combining with chlorine and iodine, also directly combine with iodine monochloride. [86] With respect to hydrogen, oxygen, chlorine, and other elements, bromine occupies an intermediate position between chlorine and iodine, and therefore there is no particular need for considering at length the compounds of bromine. This is the great advantage of a natural grouping of the elements. [87] They were both obtained by Gay-Lussac and many others. Recent data respecting iodine monochloride, ICl, entirely confirm the numerous observations of Trapp (1854), and even confirm his statement as to the existence of two isomeric (liquid and crystalline) forms (Stortenbeker). With a small excess of iodine, iodine monochloride remains liquid, but in the presence of traces of iodine trichloride it easily crystallises. Tanatar (1893) showed that of the two modifications of ICl, one is stable, and melts at 27°; while the other, which easily passes into the first, and is formed in the absence of ICl_{3}, melts at 14°. Schützenberger amplified the data concerning the action of water on the chlorides (Note 88), and Christomanos gave the fullest data regarding the trichloride. After being kept for some time, the liquid monochloride of iodine yields red deliquescent octahedra, having the composition ICl_{4}, which are therefore formed from the monochloride with the liberation of free iodine, which dissolves in the remaining quantity of the monochloride. This substance, however, judging by certain observations, is impure iodine trichloride. If 1 part of iodine be stirred up in 20 parts of water, and chlorine be passed through the liquid, then all the iodine is dissolved, and a colourless liquid is ultimately obtained which contains a certain proportion of chlorine, because this compound gives a metallic chloride and iodate with alkalis without evolving any free iodine: ICl_{5} + 6KHO = 5KCl + KIO_{3} + 3H_{2}O. The existence of a pentachloride ICl_{5} is, however, denied, because this substance has not been obtained in a free state. Stortenbeker (1888) investigated the equilibrium of the system containing the molecules I_{2}, ICl, ICl_{3}, and Cl_{2}, in the same way that Roozeboom (Chapter X. Note 38) examined the equilibrium of the molecules HCl, HCl,2H_{2}O, and H_{2}O. He found that iodine monochloride appears in two states, one (the ordinary) is stable and melts at 27°·2, whilst the other is obtained by rapid cooling, and melts at 13°·9, and easily passes into the first form. Iodine trichloride melts at 101° only in a closed tube under a pressure of 16 atmospheres. [88] By the action of water on iodine monochloride and trichloride a compound IHCl_{2} is obtained, which does not seem to be altered by water. Besides this compound, iodine and iodic acid are always formed, 10ICl + 3H_{2}O = HIO_{3} + 5IHCl_{2} + 2I_{2}; and in this respect iodine trichloride may be regarded as a mixture, ICl + ICl_{5} = 2ICl_{3}, but ICl_{5} + 3H_{2}O = IHO_{3} + 5HCl; hence iodic acid, iodine, the compound IHCl_{2}, and hydrochloric acid are also formed by the action of water. CHAPTERR XII SODIUM The neutral salt, sodium sulphate, Na_{2}SO_{4}, obtained when a mixture of sulphuric acid and common salt is strongly heated (Chapter X.),[1] forms a colourless saline mass consisting of fine crystals, soluble in water. It is the product of many other double decompositions, sometimes carried out on a large scale; for example, when ammonium sulphate is heated with common salt, in which case the sal-ammoniac is volatilised, &c. A similar decomposition also takes place when, for instance, a mixture of lead sulphate and common salt is heated; this mixture easily fuses, and if the temperature be further raised heavy vapours of lead chloride appear. When the disengagement of these vapours ceases, the remaining mass, on being treated with water, yields a solution of sodium sulphate mixed with a solution of undecomposed common salt. A considerable quantity, however, of the lead sulphate remains unchanged during this reaction, PbSO_{4} + 2NaCl = PbCl_{2} + Na_{2}SO_{4}, the vapours will contain lead chloride, and the residue will contain the mixture of the three remaining salts. The cause and nature of the reaction are just the same as were pointed out when considering the action of sulphuric acid upon NaCl. Here too it may be shown that the double decomposition is determined by the removal of PbCl_{2} from the sphere of the action of the remaining substances. This is seen from the fact that sodium sulphate, on being dissolved in water and mixed with a solution of any lead salt (and even with a solution of lead chloride, although this latter is but sparingly soluble in water), immediately gives a white precipitate of lead sulphate. In this case the lead takes up the elements of sulphuric acid from the sodium sulphate in the solutions. On heating, the reverse phenomenon is observed. The reaction in the solution depends upon the insolubility of the lead sulphate, and the decomposition which takes place on heating is due to the volatility of the lead chloride. Silver sulphate, Ag_{2}SO_{4}, in solution with common salt, gives silver chloride, because the latter is insoluble in water, Ag_{2}SO_{4} + 2NaCl = Na_{2}SO_{4} + 2AgCl. Sodium carbonate, mixed in solution with the sulphates of iron, copper, manganese, magnesium, &c., gives in solution sodium sulphate, and in the precipitate a carbonate of the corresponding metal, because these salts of carbonic acid are insoluble in water; for instance, MgSO_{4} + Na_{2}CO_{3} = Na_{2}SO_{4} + MgCO_{3}. In precisely the same way sodium hydroxide acts on solutions of the majority of the salts of sulphuric acid containing metals, the hydroxides of which are insoluble in water--for instance, CuSO_{4} + 2NaHO = Cu(HO)_{2} + Na_{2}SO_{4}. Sulphate of magnesium, MgSO_{4}, on being mixed in solution with common salt, forms, although not completely, chloride of magnesium, and sodium sulphate. On cooling the mixture of such (concentrated) solutions sodium sulphate is deposited, as was shown in Chapter X. This is made use of for preparing it on the large scale in works where sea-water is treated. In this case, on cooling, the reaction 2NaCl + MgSO_{4} = MgCl_{2} + Na_{2}SO_{4} takes place. [1] Whilst describing in some detail the properties of sodium chloride, hydrochloric acid, and sodium sulphate, I wish to impart, by separate examples, an idea of the properties of saline substances, but the dimensions of this work and its purpose and aim do not permit of entering into particulars concerning every salt, acid, or other substance. The fundamental object of this work--an account of the characteristics of the elements and an acquaintance with the forces acting between atoms--has nothing to gain from the multiplication of the number of as yet ungeneralised properties and relations. Thus where sulphates and salts of sodium are in contact, it may be expected that sodium sulphate will be formed and separated if the conditions are favourable; for this reason it is not surprising that sodium sulphate is often found in the native state. Some of the springs and salt lakes in the steppes beyond the Volga, and in the Caucasus, contain a considerable quantity of sodium sulphate, and yield it by simple evaporation of the solutions. Beds of this salt are also met with; thus at a depth of only 5 feet, about 38 versts to the east of Tiflis, at the foot of the range of the 'Wolf's mane' (Voltchia griva) mountains, a deep stratum of very pure Glauber's salt, Na_{2}SO_{4},10H_{2}O, has been found.[2] A layer two metres thick of the same salt lies at the bottom of several lakes (an area of about 10 square kilometres) in the Kouban district near Batalpaschinsk, and here its working has been commenced (1887). In Spain, near Arangoulz and in many parts of the Western States of North America, mineral sodium sulphate has likewise been found, and is already being worked. [2] Anhydrous (ignited) sodium sulphate, Na_{2}SO_{4}, is known in trade as 'sulphate' or salt-cake, in mineralogy _thenardite_. Crystalline decahydrated salt is termed in mineralogy _mirabilite_, and in trade Glauber's salt. On fusing it, the monohydrate Na_{2}SO_{4}H_{2}O is obtained, together with a supersaturated solution. The methods of obtaining salts by means of double decomposition from others already prepared are so general, that in describing a given salt there is no necessity to enumerate the cases hitherto observed of its being formed through various double decompositions.[3] The possibility of this occurrence ought to be foreseen according to Berthollet's doctrine from the properties of the salt in question. On this account it is important to know the properties of salts; all the more so because up to the present time those very properties (solubility, formation of crystallo-hydrates, volatility, &c.) which may be made use of for separating them from other salts have not been generalised.[4] These properties as yet remain subjects for investigation, and are rarely to be foreseen. The crystallo-hydrate of the normal sodium sulphate, Na_{2}SO_{4},10H_{2}O, very easily parts with water, and may be obtained in an anhydrous state if it be carefully heated until the weight remains constant; but if heated further, it partly loses the elements of sulphuric anhydride. The normal salt fuses at 843° (red heat), and volatilises to a slight extent when very strongly heated, in which case it naturally decomposes with the evolution of SO_{3}. At 0° 100 parts of water dissolve 5 parts of the anhydrous salt, at 10° 9 parts, at 20° 19·4, at 30° 40, and at 34° 55 parts, the same being the case in the presence of an excess of crystals of Na_{2}SO_{4},10H_{2}O.[5] At 34° the latter fuses, and the solubility decreases at higher temperatures.[6] A concentrated solution at 34° has a composition nearly approaching to Na_{2}SO_{4} + 14H_{2}O, and the decahydrated salt contains 78·9 of the anhydrous salt combined with 100 parts of water. From the above figures it is seen that the decahydrated salt cannot fuse without decomposing,[7] like hydrate of chlorine, Cl_{2},8H_{2}O (Chapter XI., Note 10). Not only the fused decahydrated salt, but also the concentrated solution at 34° (not all at once, but gradually), yields the monohydrated salt, Na_{2}SO_{4},H_{2}O. The heptahydrated salt, Na_{2}SO_{4},7H_{2}O, also splits up, even at low temperatures, with the formation of this monohydrated salt, and therefore from 35° the solubility can be given only for the latter. For 100 parts of water this is as follows: at 40° 48·8, at 50° 46·7, at 80° 43·7, at 100° 42·5 parts of the anhydrous salt. If the decahydrated salt be fused, and the solution allowed to cool in the presence of the monohydrated salt, then at 30° 50·4 parts of anhydrous salt are retained in the solution, and at 20° 52·8 parts. Hence, with respect to the anhydrous and monohydrated salts, the solubility is identical, and falls with increasing temperature, whilst with respect to decahydrated salt, the solubility rises with increasing temperature. So that if in contact with a solution of sodium sulphate there are only crystals of that heptahydrated salt (Chapter I., Note 54), Na_{2}SO_{4},7H_{2}O, which is formed from saturated solutions, then saturation sets in when the solution has the following composition per 100 parts of salt: at 0° 19·6, at 10° 30·5, at 20° 44·7, and at 25° 52·9 parts of anhydrous salt. Above 27° the heptahydrated salt, like the decahydrated salt at 34°, splits up into the monohydrated salt and a saturated solution. Thus sodium sulphate has three curves of solubility: one for Na_{2}SO_{4},7H_{2}O (from 0° to 26°), one for Na_{2}SO_{4},10H_{2}O (from 0° to 34°), and one for Na_{2}SO_{4},H_{2}O (a descending curve beginning at 26°), because there are three of these crystallo-hydrates, and the solubility of a substance only depends upon the particular condition of that portion of it which has separated from the solution or is present in excess.[8] [3] The salts may be obtained not only by methods of substitution of various kinds, but also by many other combinations. Thus sodium sulphate may be formed from sodium oxide and sulphuric anhydride, by oxidising sodium sulphide, Na_{2}S, or sodium sulphite, Na_{2}SO_{3}, &c. When sodium chloride is heated in a mixture of the vapours of water, air, and sulphurous anhydride, sodium sulphate is formed. According to this method (patented by Hargreaves and Robinson), sodium sulphate, Na_{2}SO_{4}, is obtained from NaCl without the preliminary manufacture of H_{2}SO_{4}. Lumps of NaCl pressed into bricks are loosely packed into a cylinder and subjected, at a red heat, to the action of steam, air and SO_{2}. Under these conditions, HCl, sulphate, and a certain amount of unaltered NaCl are obtained. This mixture is converted into soda by Gossage's process (_see_ Note 15) and may have some practical value. [4] Many observations have been made, but little general information has been obtained from particular cases. In addition to which, the properties of a given salt are changed by the presence of other salts. This takes place not only in virtue of mutual decomposition or formation of double salts capable of separate existence, but is determined by the influence which some salts exert on others, or by forces similar to those which act during solution. Here nothing has been generalised to that extent which would render it possible to predict without previous investigation, if there be no close analogy to help us. Let us state one of these numerous cases: 100 parts of water at 20° dissolve 34 parts of potassium nitrate but on the addition of sodium nitrate the solubility of potassium nitrate increases to 48 parts in 10 of water (Carnelley and Thomson). In general, in all cases of which there are accurate observations it appears that the presence of foreign salts changes the properties of any given salt. [5] The information concerning solubility (Chapter I.) is given according to the determinations of Gay-Lussac, Lovell, and Mulder. [6] In Chapter I., Note 24, we have already seen that with many other sulphates the solubility also decreases after a certain temperature is passed. Gypsum, CaSO_{4},2H_{2}O, lime, and many other compounds present such a phenomenon. An observation of Tilden's (1884) is most instructive; he showed that on raising the temperature (in closed vessels) above 140° the solubility of sodium sulphate again begins to increase. At 100° 100 parts of water dissolve about 43 parts of anhydrous salt, at 140° 42 parts, at 160° 43 parts, at 180° 44 parts, at 230° 46 parts. According to Étard (1892) the solubility of 30 parts of Na{2}SO_{4} in 100 of solution (or 43 per 100 of water) corresponds to 80°, and above 240° the solubility again falls, and very rapidly, so that at 320° the solution contains 12 per 100 of solution (about 14 per 100 of water) and a further rise of temperature is followed by a further deposition of the salt. It is evident that the phenomenon of saturation, determined by the presence of an excess of the dissolved substance, is very complex, and therefore that for the theory of solutions considered as liquid indefinite chemical compounds, many useful statements can hardly be given. [7] Already referred to in Chapter I., Note 56. The example of sodium sulphate is historically very important for the theory of solutions. Notwithstanding the number of investigations which have been made, it is still insufficiently studied, especially from the point of the vapour tension of solutions and crystallo-hydrates, so that those processes cannot be applied to it which Guldberg, Roozeboom, Van't Hoff, and others applied to solutions and crystallo-hydrates. It would also be most important to investigate the influence of pressure on the various phenomena corresponding with the combinations of water and sodium sulphate, because when crystals are separated--for instance, of the decahydrated salt--an increase of volume takes place, as can be seen from the following data:--the sp. gr. of the anhydrous salt is 2·66, that of the decahydrated salt = 1·46, but the sp. gr. of solutions at 15°/4° = 9,992 + 90·2_p_ + 0·35_p_^2 where p represents the percentage of anhydrous salt in the solution, and the sp. gr. of water at 4° = 10,000. Hence for solutions containing 20 p.c. of anhydrous salt the sp. gr. = 1·1936; therefore the volume of 100 grams of this solution = 83·8 c.c., and the volume of anhydrous salt contained in it is equal to 20/2·66, or = 7·5 c.c., and the volume of water = 80·1 c.c. Therefore, the solution, on decomposing into anhydrous salt and water, increases in volume (from 83·8 to 87·6); but in the same way 83·8 c.c. of 20 p.c. solution are formed from (45·4/1·46 =) 31·1 c.c. of the decahydrated salt, and 54·6 c.c. of water--that is to say, that during the formation of a solution from 85·7 c.c., 83·8 c.c. are formed. [8] From this example it is evident the solution remains unaltered until from the contact of a solid it becomes either saturated or supersaturated, crystallisation being determined by the attraction to a solid, as the phenomenon of supersaturation clearly demonstrates. This partially explains certain apparently contradictory determinations of solubility. The best investigated example of such complex relations is cited in Chapter XIV., Note 50 (for CaCl_{2}). Thus solutions of sodium sulphate may give crystallo-hydrates of three kinds on cooling the saturated solution: the unstable heptahydrated salt is obtained at temperatures below 26°, the decahydrated salt forms under ordinary conditions at temperatures below 34°, and the monohydrated salt at temperatures above 34°. Both the latter crystallo-hydrates present a stable state of equilibrium, and the heptahydrated salt decomposes into them, probably according to the equation 3Na_{2}SO_{4},7H_{2}0 = 2Na_{2}SO_{4},10H_{2}O + Na_{2}SO_{4},H_{2}O. The ordinary decahydrated salt is called _Glauber's salt_. All forms of these crystallo-hydrates lose their water entirely, and give the anhydrous salt when dried over sulphuric acid.[9] [9] According to Pickering's experiments (1886), the molecular weight in grams (that is, 142 grams) of anhydrous sodium sulphate, on being dissolved in a large mass of water, at 0° absorbs (hence the-sign)-1,100 heat units, at 10°-700, at 15°-275, at 20° gives out +25, at 25° +300 calories. For the decahydrated salt, Na_{2}SO_{4},10H_{2}O, 5°-4,225, 10°-4,000, 15°-3,570, 20°-3,160, 25°-2,775. Hence (just as in Chapter I., Note 56) the heat of the combination Na_{2}SO_{4},10H_{2}O at 5° = +3,125, 10° = +3,250, 20° = +3,200, and 25° = +3,050. It is evident that the decahydrated salt dissolving in water gives a decrease of temperature. Solutions in hydrochloric acid give a still greater decrease, because they contain the water of crystallisation in a solid state--that is, like ice--and this on melting absorbs heat. A mixture of 15 parts of Na_{2}SO_{4},10H_{2}O and 12 parts of strong hydrochloric acid produces sufficient cold to freeze water. During the treatment with hydrochloric acid a certain quantity of sodium chloride is formed. Sodium sulphate, Na_{2}SO_{4}, only enters into a few reactions of combination with other salts, and chiefly with salts of the same acid, forming double sulphates. Thus, for example, if a solution of sodium sulphate be mixed with a solution of aluminium, magnesium, or ferrous sulphate, it gives crystals of a double salt when evaporated. Sulphuric acid itself forms a compound with sodium sulphate, which is exactly like these double salts. It is formed with great ease when sodium sulphate is dissolved in sulphuric acid and the solution evaporated. On evaporation, crystals of the acid salt separate, Na_{2}SO_{4} + H_{2}SO_{4} = 2NaHSO_{4}. This separates from hot solutions, whilst the crystallo-hydrate, NaHSO_{4},H_{2}O,[10] separates from cold solutions. The crystals when exposed to damp air decompose into H_{2}SO_{4}, which deliquesces, and Na_{2}SO_{4} (Graham, Rose); alcohol also extracts sulphuric acid from the acid salt. This shows the feeble force which holds the sulphuric acid to the sodium sulphate.[11] Both acid sodium sulphate and all mixtures of the normal salt and sulphuric acid lose water when heated, and are converted into sodium _pyrosulphate_, Na_{2}S_{2}O_{7}, at a low red heat.[11 bis] This anhydrous salt, at a bright red heat, parts with the elements of sulphuric anhydride, the normal sodium sulphate remaining behind--Na_{2}S_{2}O_{7} = Na_{2}SO_{4} + SO_{3}. From this it is seen that the normal salt is able to combine with water, with other sulphates, and with sulphuric anhydride or acid, &c. [10] The very large and well-formed crystals of this salt resemble the hydrate H_{2}SO_{4},H_{2}O, or SO(OH)_{4}. In general the replacement of hydrogen by sodium modifies many of the properties of acids less than its replacement by other metals. This most probably depends on the volumes being nearly equal. [11] In solution (Berthelot) the acid salt in all probability decomposes most in the greatest mass of water. The specific gravity (according to the determinations of Marignac) of solutions at 15°/4° = 9,992 + 77·92_p_ + 0·231_p_^2 (_see_ Note 7). From these figures, and from the specific gravities of sulphuric acid, it is evident that on mixing solutions of this acid and sodium sulphate _expansion_ will always take place; for instance, H_{2}SO_{4} + 25H_{2}O with Na_{2}SO_{4} + 25H_{2}O increases from 483 volumes to 486. In addition to which, in weak solutions heat is absorbed, as shown in Chapter X., Note 27. Nevertheless, even more acid salts may be formed and obtained in a crystalline form. For instance, on cooling a solution of 1 part of sodium sulphate in 7 parts of sulphuric acid, crystals of the composition NaHSO_{4},H_{2}SO_{4} are separated (Schultz, 1868). This compound fuses at about 100°; the ordinary acid salt, NaHSO_{4}, at 149°. [11 bis] On decreasing the pressure, sodium hydrogen sulphate, NaHSO_{4}, dissociates much more easily than at the ordinary pressure; it loses water and forms the pyrosulphate, Na_{2}S_{2}O_{7}; this reaction is utilised in chemical works. Sodium sulphate may by double decomposition be converted into a sodium salt of any other acid, by means of heat and taking advantage of the volatility, or by means of solution and taking advantage of the different degree of solubility of the different salts. Thus, for instance, owing to the insolubility of barium sulphate, sodium hydroxide or caustic soda may be prepared from sodium sulphate, if barium hydroxide be added to its solution, Na_{2}SO_{4} + Ba(HO)_{2} = BaSO_{4} + 2NaHO. And by taking any salt of barium, BaX_{2}, the corresponding salt of sodium may be obtained, Na_{2}SO_{4} + BaX_{2} = BaSO_{4} + 2NaX. Barium sulphate thus formed, being a very sparingly-soluble salt, is obtained as a precipitate, whilst the sodium hydroxide, or salt, NaX, is obtained in solution, because _all salts of sodium are soluble_. Berthollet's doctrine permits all such cases to be foreseen. The reactions of _decomposition_ of sodium sulphate are above all noticeable by the separation of oxygen. Sodium sulphate by itself is very stable, and it is only at a temperature sufficient to melt iron that it is possible to separate the elements SO_{3} from it, and then only partially. However, the oxygen may be separated from sodium sulphate, as from all other sulphates, by means of many substances which are able to combine with oxygen, such as charcoal and sulphur, but hydrogen is not able to produce this action. If sodium sulphate be heated with charcoal, then carbonic oxide and anhydride are evolved, and there is produced, according to the circumstances, either the lower oxygen compound, sodium sulphite, Na_{2}SO_{3} (for instance, in the formation of glass); or else the decomposition proceeds further, and sodium sulphide, Na_{2}S, is formed, according to the equation Na_{2}SO_{4} + 2C = 2CO_{2} + Na_{2}S. On the basis of this reaction the greater part of the sulphate of sodium prepared at chemical works is converted into _soda ash_--that is, _sodium carbonate_, Na_{2}CO_{3}, which is used for many purposes. In the form of carbonates, the metallic oxides behave in many cases just as they do in the state of oxides or hydroxides, owing to the feeble acid properties of carbonic acid. However, the majority of the salts of carbonic acid are insoluble, whilst sodium carbonate is one of the few soluble salts of this acid, and therefore reacts with facility. Hence sodium carbonate is employed for many purposes, in which its alkaline properties come into play. Thus, even under the action of feeble organic acids it immediately parts with its carbonic acid, and gives a sodium salt of the acid taken. Its solutions exhibit an alkaline reaction on litmus. It aids the passage of certain organic substances (tar, acids) into solution, and is therefore used, like caustic alkalis and soap (which latter also acts by virtue of the alkali it contains), for the removal of certain organic substances, especially in bleaching cotton and similar fabrics. Besides which a considerable quantity of sodium carbonate is used for the preparation of sodium hydroxide or caustic soda, which has also a very wide application. In large chemical works where sodium carbonate is manufactured from Na_{2}SO_{4}, it is usual first to manufacture sulphuric acid, and then by its aid to convert common salt into sodium sulphate, and lastly to convert the sodium sulphate thus obtained into carbonate and caustic soda. Hence these works prepare both alkaline substances (soda ash and caustic soda) and acid substances (sulphuric and hydrochloric acids), the two classes of chemical products which are distinguished for the greatest energy of their reactions and are therefore most frequently applied to technical purposes. Factories manufacturing soda are generally called alkali works. The process of the conversion of sodium sulphate into sodium carbonate consists in strongly heating a mixture of the sulphate with charcoal and calcium carbonate. The following reactions then take place: the sodium sulphate is first deoxidised by the charcoal, forming sodium sulphide and carbonic anhydride, Na_{2}SO_{4} + 2C = Na_{2}S + 2CO_{2}. The sodium sulphide thus formed then enters into double decomposition with the calcium carbonate taken, and gives calcium sulphide and sodium carbonate, Na_{2}S + CaCO_{3} = Na_{2}CO_{3} + CaS. [Illustration: FIG. 68.--Reverberatory furnace for the manufacture of sodium carbonate. F, grate. A, bridge. M, hearth for the ultimate calcination of the mixture of sodium sulphate, coal, and calcium carbonate, which is charged from above into the part of the furnace furthest removed from the fire F. P, P, doors for stirring and bringing the mass towards the grate F by means of stirrers R. At the end of the operation the semifused mass is charged into trucks C.] Besides which, under the action of the heat, a portion of the excess of calcium carbonate is decomposed into lime and carbonic anhydride, CaCO_{3} = CaO + CO_{2}, and the carbonic anhydride with the excess of charcoal forms carbon monoxide, which towards the end of the operation shows itself by the appearance of a blue flame. Thus from a mass containing sodium sulphate we obtain a mass which includes sodium carbonate, calcium sulphide, and calcium oxide, but none of the sodium sulphide which was formed on first heating the mixture. The entire process, which proceeds at a high temperature, may be expressed by a combination of the three above-mentioned formulæ, if it be considered that the product contains one equivalent of calcium oxide to two equivalents of calcium sulphide.[12] The sum of the reactions may then be expressed thus: 2Na_{2}SO_{4} + 3CaCO_{3} + 9C = 2Na_{2}CO_{3} + CaO,2CaS + 10CO. Indeed, the quantities in which the substances are mixed together at chemical works approaches to the proportion required by this equation. The entire process of decomposition is carried on in reverberatory furnaces, into which a mixture of 1,000 parts of sodium sulphate, 1,040 parts of calcium carbonate (as a somewhat porous limestone), and 500 parts of small coal is introduced from above. This mixture is first heated in the portion of the furnace which is furthest removed from the fire-grate; it is then brought to the portion nearest to the fire-grate, when it is stirred during heating. The partially fused mass obtained at the end of the process is cooled, and then subjected to methodical lixiviation[13] to extract the sodium carbonate, the mixture of calcium oxide and sulphide forming the so-called 'soda waste' or 'alkali waste.'[14] [12] Calcium sulphide, CaS, like many metallic sulphides which are soluble in water, is decomposed by it (Chapter X.), CaS + H_{2}O = CaO + H_{2}S, because hydrogen sulphide is a very feeble acid. If calcium sulphide be acted on by a large mass of water, lime may be precipitated, and a state of equilibrium will be reached, when the system CaO + 2CaS remains unchanged. Lime, being a product of the action of water on CaS, limits this action. Therefore, if in black ash the lime were not in excess, a part of the sulphide would be in solution (actually there is but very little). In this manner in the manufacture of sodium carbonate the conditions of equilibrium which enter into double decompositions have been made use of (_see above_), and the aim is to form directly the unchangeable product CaO,2CaS. This was first regarded as a special insoluble compound, but there is no evidence of its independent existence. [13] [Illustration: FIG. 69.--Apparatus for the methodical lixiviation of black ash, &c. Water flows into the tanks from the pipes _r_, _r_, and the saturated liquid is drawn off from _c_, _c_.] _Methodical lixiviation_ is the extraction, by means of water, of a soluble substance from the mass containing it. It is carried on so as not to obtain weak aqueous solutions, and in such a way that the residue shall not contain any of the soluble substance. This problem is practically of great importance in many industries. It is required to extract from the mass all that is soluble in water. This is easily effected if water be first poured on the mass, the strong solution thus obtained decanted, then water again poured on, time being allowed for it to act, then again decanted, and so on until fresh water does not take up anything. But then finally such weak solutions are obtained that it would be very disadvantageous to evaporate them. This is avoided by pouring the fresh hot water destined for the lixiviation, not onto the fresh mass, but upon a mass which has already been subjected to a first lixiviation by weak solutions. In this way the fresh water gives a weak solution. The strong solution which goes to the evaporating pan flows from those parts of the apparatus which contain the fresh, as yet unlixiviated, mass, and thus in the latter parts the weak alkali formed in the other parts of the apparatus becomes saturated as far as possible with the soluble substance. Generally several intercommunicating vessels are constructed (standing at the same level) into which in turn the fresh mass is charged which is intended for lixiviation; the water is poured in, the alkali drawn off, and the lixiviated residue removed. The illustration represents such an apparatus, consisting of four communicating vessels. The water poured into one of them flows through the two nearest and issues from the third. The fresh mass being placed in one of these boxes or vessels, the stream of water passing through the apparatus is directed in such a manner as to finally issue from this vessel containing the fresh unlixiviated mass. The fresh water is added to the vessel containing the material which has been almost completely exhausted. Passing through this vessel it is conveyed by the pipe (syphon passing from the bottom of the first box to the top of the second) communicating with the second; it finally passes (also through a syphon pipe) into the box (the third) containing the fresh material. The water will extract all that is soluble in the first vessel, leaving only an insoluble residue. This vessel is then ready to be emptied, and refilled with fresh material. The levels of the liquids in the various vessels will naturally be different, in consequence of the various strengths of the solutions which they contain. It must not, however, be thought that sodium carbonate alone passes into the solution; there is also a good deal of caustic soda with it, formed by the action of lime on the carbonate of sodium, and there are also certain sodium sulphur compounds with which we shall partly become acquainted hereafter. The sodium carbonate, therefore, is not obtained in a very pure state. The solution is concentrated by evaporation. This is conducted by means of the waste heat from the soda furnaces, together with that of the gases given off. The process in the soda furnaces can only be carried on at a high temperature, and therefore the smoke and gases issuing from them are necessarily very hot. If the heat they contain was not made use of there would be a great waste of fuel; consequently in immediate proximity to these furnaces there is generally a series of pans or evaporating boilers, under which the gases pass, and into which the alkali solution is poured. On evaporating the solution, first of all the undecomposed sodium sulphate separates, then the sodium carbonate or soda crystals. These crystals as they separate are raked out and placed on planks, where the liquid drains away from them. Caustic soda remains in the residue, and also any sodium chloride which was not decomposed in the foregoing process. Part of the sodium carbonate is recrystallised in order to purify it more thoroughly. In order to do this a saturated solution is left to crystallise at a temperature below 30° in a current of air, in order to promote the separation of the water vapour. The large transparent crystals (efflorescent in air) of Na_{2}CO_{3},10H_{2}O are then formed which have already been spoken of (Chapter I.). [14] The whole of the sulphur used in the production of the sulphuric acid employed in decomposing the common salt is contained in this residue. This is the great burden and expense of the soda works which use Leblanc's method. As an instructive example from a chemical point of view, it is worth while mentioning here two of the various methods of recovering the sulphur from the soda waste. Chance's process is treated in Chapter XX., Note 6. Kynaston (1885) treats the soda waste with a solution (sp. gr. l·21) of magnesium chloride, which disengages sulphuretted hydrogen: CaS + MgCl_{2} + 2H_{2}O = CaCl_{2} + Mg(OH)_{2} + H_{2}S. Sulphurous anhydride is passed through the residue in order to form the insoluble calcium sulphite: CaCl_{2} + Mg(OH)_{2} + SO_{2} = CaSO_{3} + MgCl_{2} + H_{2}O. The solution of magnesium chloride obtained is again used, and the washed calcium sulphite is brought into contact at a low temperature with hydrochloric acid (a weak aqueous solution) and hydrogen sulphide, the whole of the sulphur then separating: CaSO_{3} + 2H_{2}S + 2HCl = CaCl_{2} + 3H_{2}O + 3S. But most efforts have been directed towards avoiding the formation of soda waste. The above-mentioned process for making soda was discovered in the year 1808 by the French doctor Leblanc, and is known as the Leblanc process. The particulars of the discovery are somewhat remarkable. Sodium carbonate, having a considerable application in industry, was for a long time prepared exclusively from the ash of marine plants (Chapter XI., page 497). Even up to the present time this process is carried on in Normandy. In France, where for a long time the manufacture of large quantities of soap (so-called Marseilles soap) and various fabrics required a large amount of soda, the quantity prepared at the coast was insufficient to meet the demand. For this reason during the wars at the beginning of the century, when the import of foreign goods into France was interdicted, the want of sodium carbonate was felt. The French Academy offered a prize for the discovery of a profitable method of preparing it from common salt. Leblanc then proposed the above-mentioned process, which is remarkable for its great simplicity.[15] [15] Among the drawbacks of the Leblanc process are the accumulation of 'soda waste' (Note 14) owing to the impossibility at the comparatively low price of sulphur (especially in the form of pyrites) of finding employment for the sulphur and sulphur compounds for which this waste is sometimes treated, and also the insufficient purity of the sodium carbonate for many purposes. The advantages of the Leblanc process, besides its simplicity and cheapness, are that almost the whole of the acids obtained as bye-products have a commercial value; for chlorine and bleaching powder are produced from the large amount of hydrochloric acid which appears as a bye-product; caustic soda also is very easily made, and the demand for it increases every year. In those places where salt, pyrites, charcoal, and limestone (the materials required for alkali works) are found side by side--as, for instance, in the Ural or Don districts--conditions are favourable to the development of the manufacture of sodium carbonate on an enormous scale; and where, as in the Caucasus, sodium sulphate occurs naturally, the conditions are still more favourable. A large amount, however, of the latter salt, even from soda works, is used in making glass. The most important soda works, as regards the quantity of products obtained from them, are the English works. As an example of the other numerous and varied methods of manufacturing soda from sodium chloride, the following may be mentioned: Sodium chloride is decomposed by oxide of lead, PbO, forming lead chloride and sodium oxide, which, with carbonic anhydride, yields sodium carbonate (Scheele's process). In Cornu's method sodium chloride is treated with lime, and then exposed to the air, when it yields a small quantity of sodium carbonate. In E. Kopp's process sodium sulphate (125 parts) is mixed with oxide of iron (80 parts) and charcoal (55 parts), and the mixture is heated in reverberatory furnaces. Here a compound, Na_{6}Fe_{4}S_{3}, is formed, which is insoluble in water absorbs oxygen and carbonic anhydride, and then forms sodium carbonate and ferrous sulphide; this when roasted gives sulphurous anhydride, the indispensable material for the manufacture of sulphuric acid, and ferric oxide which is again used in the process. In Grant's method sodium sulphate is transformed into sodium sulphide, and the latter is decomposed by a stream of carbonic anhydride and steam, when hydrogen sulphide is disengaged and sodium carbonate formed. Gossage prepares Na_{2}S from Na_{2}SO_{4} (by heating it with carbon), dissolves it in water and subjects the solution to the action of an excess of CO_{2} in coke towers, thus obtaining H_{2}S (a gas which gives SO_{2} under perfect combustion, or sulphur when incompletely burnt, Chapter XX., Note 6) and bicarbonate of sodium; Na_{2}S + 2CO_{2} + 2H_{2}O = H_{2}S + 2HNaCO_{3}. The latter gives soda and CO_{2} when ignited. This process quite eliminates the formation of soda-waste (_see_ Note 3) and should in my opinion be suitable for the treatment of native Na_{2}SO_{4}, like that which is found in the Caucasus, all the more since H_{2}S gives sulphur as a bye-product. Repeated efforts have been made in recent times to obtain soda (and chlorine, _see_ Chapter II., Note 1) from strong solutions of salt (Chapter X., Note 23 bis) by the action of an electric current, but until now these methods have not been worked out sufficiently for practical use, probably partly owing to the complicated apparatus needed, and the fact that the chlorine given off at the anode corrodes the electrodes and vessels and has but a limited industrial application. We may mention that according to Hempel (1890) soda in crystals is deposited when an electric current and a stream of carbonic acid gas are passed through a saturated solution of NaCl. Sodium carbonate may likewise be obtained from cryolite (Chapter XVII., Note 23) the method of treating this will be mentioned under Aluminium. Of all other industrial processes for manufacturing sodium carbonate, the _ammonia process_ is the most worthy of mention.[16] In this the vapours of ammonia, and then an excess of carbonic anhydride, are directly introduced into a concentrated solution of sodium chloride in order to form the acid ammonium carbonate, NH_{4}HCO_{3}. Then, by means of the double saline decomposition of this salt, sodium chloride is decomposed, and in virtue of its slight solubility acid sodium carbonate, NaHCO_{3}, is precipitated and ammonium chloride, NH_{4}Cl, is obtained in solution (with a portion of the sodium chloride and acid sodium carbonate). The reaction proceeds in the solution owing to the sparing solubility of the NaHCO_{3} according to the equation NaCl + NH_{4}HCO_{3} = NH_{4}Cl + NaHCO_{3}. The ammonia is recovered from the solution by heating with lime or magnesia,[16 bis] and the precipitated acid sodium carbonate is converted into the normal salt by heating. It is thus obtained in a very pure state.[17] [16] This process (Chapter XVII.) was first pointed out by Turck, worked out by Schloesing, and finally applied industrially by Solvay. The first (1883) large soda factories erected in Russia for working this process are on the banks of the Kama at Berezniak, near Ousolia, and belong to Lubimoff. But Russia, which still imports from abroad a large quantity of bleaching powder and exports a large amount of manganese ore, most of all requires works carrying on the Leblanc process. In 1890 a factory of this kind was erected by P. K. Oushkoff, on the Kama, near Elagoubi. [16 bis] Mond (_see_ Chapter XI., Note 3 bis) separates the NH_{4}Cl from the residual solutions by cooling (Chapter X., Note 44); ignites the sal-ammoniac and passes the vapour over MgO, and so re-obtains the NH_{3}, and forms MgCl_{2}: the former goes back for the manufacture of soda, while the latter is employed either for making HCl or Cl_{2}. [17] Commercial soda ash (calcined, anhydrous) is rarely pure; the crystallised soda is generally purer. In order to purify it further, it is best to boil a concentrated solution of soda ash until two-thirds of the liquid remain, collect the soda which settles, wash with cold water, and then shake up with a strong solution of ammonia, pour off the residue, and heat. The impurities will then remain in the mother liquors, &c. Some numerical data may be given for sodium carbonate. The specific gravity of the anhydrous salt is 2·48, that of the decahydrated salt 1·46. Two varieties are known of the heptahydrated salt (Löwel, Marignac, Rammelsberg), which are formed together by allowing a saturated solution to cool under a layer of alcohol; the one is less stable (like the corresponding sulphate) and at 0° has a solubility of 32 parts (of anhydrous salt) in 100 water; the other is more stable, and its solubility 20 parts (of anhydrous salt) per 100 of water. The solubility of the decahydrated salt in 100 water = at 0°, 7·0; at 20°, 21·7; at 30°, 37·2 parts (of anhydrous salt). At 80° the solubility is only 46·1, at 90° 45·7, at 100°, 45·4 parts (of anhydrous salt). That is, it falls as the temperature rises, like Na_{2}SO_{4}. The specific gravity (Note 7) of the solutions of sodium carbonate, according to the data of Gerlach and Kohlrausch, at 15°/4° is expressed by the formula, _s_ = 9,992 + 104·5_p_ + 0·165_p_^2. Weak solutions occupy a volume not only less than the sum of the volumes of the anhydrous salt and the water, but even less than the water contained in them. For instance, 1,000 grams of a 1 p.c. solution occupy (at 15°) a volume of 990·4 c.c. (sp. gr. 1·0097), but contain 990 grams of water, occupying at 15° a volume of 990·8 c.c. A similar case, which is comparatively rare occurs also with sodium hydroxide, in those dilute solutions for which the factor _A_ is greater than 100 if the sp. gr. of water at 4° = 100,000, and if the sp. gr. of the solution be expressed by the formula _S_ = _S__{0} + _Ap_ + _Bp_^2, where _S__{0} is the specific gravity of the water. For 5 p.c. the sp. gr. 15°/4° = 1·0520; for 10 p.c. 1·1057; for 15 p.c. 1·1603. The changes in the sp. gr. with the temperature are here almost the same as with solutions of sodium chloride with an equal value of _p_. Sodium carbonate, like sodium sulphate, loses all its water on being heated, and when anhydrous fuses at a bright-red heat (1098°). A small quantity of sodium carbonate placed in the loop of a platinum wire volatilises in the heat of a gas flame, and therefore in the furnaces of glass works part of the soda is always transformed into the condition of vapour. Sodium carbonate resembles sodium sulphate in its relation to water.[18] Here also the greatest solubility is at the temperature of 37°; both salts, on crystallising at the ordinary temperature, combine with ten molecules of water, and such crystals of soda, like crystals of Glauber's salt, fuse at 34°. Sodium carbonate also forms a supersaturated solution, and, according to the conditions, gives various combinations with water of crystallisation (mentioned on page 108), &c. [18] The resemblance is so great that, notwithstanding the difference in the molecular composition of Na_{2}SO_{4} and Na_{2}CO_{3}, they ought to be classed under the type (NaO)_{2}R, where R = SO_{2} or CO. Many other sodium salts also contain 10 mol. H_{2}O. At a red heat superheated steam liberates carbonic anhydride from sodium carbonate and forms caustic soda, Na_{2}CO_{3} + H_{2}O = 2NaHO + CO_{2}. Here the carbonic anhydride is replaced by water; this depends on the feebly acid character of carbonic anhydride. By direct heating, sodium carbonate is only slightly decomposed into sodium oxide and carbonic anhydride; thus, when sodium carbonate is fused, about 1 per cent. of carbonic anhydride is disengaged.[19] The carbonates of many other metals--for instance, of calcium, copper, magnesium, iron, &c.--on being heated lose all their carbonic anhydride. This shows the considerable basic energy which sodium possesses. With the soluble salts of most metals, sodium carbonate gives precipitates either of insoluble carbonates of the metals, or else of the hydroxides (in this latter case carbonic anhydride is disengaged); for instance, with barium salts it precipitates an insoluble barium carbonate (BaCl_{2} + Na_{2}CO_{3} = 2NaCl + BaCO_{3}) and with the aluminium salts it precipitates aluminium hydroxide, carbonic anhydride being disengaged: 3Na_{2}CO_{3} + Al_{2}(SO_{4})_{3} + 3H_{2}O = 3Na_{2}SO_{4} + 2Al(OH)_{3} + 3CO_{2}. Sodium carbonate, like all the salts of carbonic acid, evolves carbonic anhydride on treatment with all acids which are to any extent energetic. But if an acid diluted with water be gradually added to a solution of sodium carbonate, _at first_ such an evolution does not take place, because the excess of the carbonic anhydride forms acid sodium carbonate (sodium bicarbonate), NaHCO_{3}.[20] The acid sodium carbonate is an unstable salt. Not only when heated alone, but even on being slightly heated in solution, and also at the ordinary temperature in damp air, it loses carbonic anhydride and forms the normal salt. And at the same time it is easy to obtain it in a pure crystalline form, if a strong solution of sodium carbonate be cooled and a stream of carbonic anhydride gas passed through it. The acid salt is less soluble in water than the normal,[21] and therefore a strong solution of the latter gives crystals of the acid salt if carbonic anhydride be passed through it. The acid salt may be yet more conveniently formed from effloresced crystals of sodium carbonate, which, on being considerably heated, very easily absorb carbonic anhydride.[22] The acid salt crystallises well, but not, however, in such large crystals as the normal salt; it has a brackish and not an alkaline taste like that of the normal salt; its reaction is feebly alkaline, nearly neutral. At 70° its solution begins to lose carbonic anhydride, and on boiling the evolution becomes very abundant. From the preceding remarks it is clear that in most reactions this salt, especially when heated, acts similarly to the normal salt, but has, naturally, some distinction from it. Thus, for example, if a solution of sodium carbonate be added to a normal magnesium salt, a turbidity (precipitate) is formed of magnesium carbonate. MgCO_{3}. No such precipitate is formed by the acid salt, because magnesium carbonate is soluble in the presence of an excess of carbonic anhydride. [19] According to the observations of Pickering. According to Rose, when solutions of sodium carbonate are boiled a certain amount of carbonic anhydride is disengaged. [20] The composition of this salt, however, may be also represented as a combination of carbonic acid, H_{2}CO_{3}, with the normal salt, Na_{2}CO_{3}, just as the latter also combines with water. Such a combination is all the more likely because (1) there exists another salt, Na_{2}CO_{3},2NaHCO_{3},2H_{2}O (sodium sesquicarbonate), obtained by cooling a boiling solution of sodium bicarbonate, or by mixing this salt with the normal salt; but the formula of this salt cannot be derived from that of normal carbonic acid, as the formula of the bicarbonate can. At the same time the sesqui-salt has all the properties of a definite compound; it crystallises in transparent crystals, has a constant composition, its solubility (at 0° in 100 of water, 12·6 of anhydrous salt) differs from the solubility of the normal and acid salts; it is found in nature, and is known by the names of _trona_ and _urao_. The observations of Watts and Richards showed (1886) that on pouring a strong solution of the acid salt into a solution of the normal salt saturated by heating, crystals of the salt NaHCO_{3},Na_{2}CO_{3},2H_{2}O may be easily obtained, as long as the temperature is above 35°. The natural urao (Boussingault) has, according to Laurent, the same composition. This salt is very stable in air, and may be used for purifying sodium carbonate on the large scale. Such compounds have been little studied from a theoretical point of view, although particularly interesting, since in all probability they correspond with ortho-carbonic acid, C(OH)_{4}, and at the same time correspond with double salts like astrakhanite (Chapter XIV., Note 25). (2) Water of crystallisation does not enter into the composition of the crystals of the acid salt, so that on its formation (occurring only at low temperatures, as in the formation of crystalline compounds with water) the water of crystallisation of the normal salt separates and the water is, as it were, replaced by the elements of carbonic acid. If anhydrous sodium carbonate be mixed with the amount of water requisite for the formation of Na_{2}CO_{3},H_{2}O, this salt will, when powdered, absorb CO_{2} as easily at the ordinary temperature as it does water. [21] 100 parts of water at 0° dissolve 7 parts of the acid salt, which corresponds with 4·3 parts of the anhydrous normal salt, but at 0° 100 parts of water dissolve 7 parts of the latter. The solubility of the bi-or acid salt varies with considerable regularity; 100 parts of water dissolves at 15° 9 parts of the salt, at 30° 11 parts. The ammonium, and more especially the calcium, salt, is much more soluble in water. The ammonia process (_see_ p. 524) is founded upon this. Ammonium bicarbonate (acid carbonate) at 0° has a solubility of 12 parts in 100 water, at 30° of 27 parts. The solubility therefore increases very rapidly with the temperature. And its saturated solution is more stable than a solution of sodium bicarbonate. In fact, saturated solutions of these salts have a gaseous tension like that of a mixture of carbonic anhydride and water--namely, at 15° and at 50°, for the sodium salt 120 and 750 millimetres, for the ammonium salt 120 and 563 millimetres. These data are of great importance in understanding the phenomena connected with the ammonia process. They indicate that with an increased pressure the formation of the sodium salt ought to increase if there be an excess of ammonium salt. [22] Crystalline sodium carbonate (broken into lumps) also absorbs carbonic anhydride, but the water contained in the crystals is then disengaged: Na_{2}CO_{3},10H_{2}O + CO_{2} = Na_{2}CO_{3},H_{2}CO_{3} + 9H_{2}O, and dissolves part of the carbonate; therefore part of the sodium carbonate passes into solution together with all the impurities. When it is required to avoid the formation of this solution, a mixture of ignited and crystalline sodium carbonate is taken. Sodium bicarbonate is prepared chiefly for medicinal use, and is then often termed _carbonate of soda_, also, for instance, in the so-called soda powders, for preparing certain artificial mineral waters, for the manufacture of digestive lozenges like those made at Essentuki, Vichy, &c. Sodium carbonate is used for the preparation of _caustic soda_[23]--that is, the hydrate of sodium oxide, or the alkali which corresponds to sodium. For this purpose the action of lime on a solution of sodium carbonate is generally made use of. The process is as follows: a weak, generally 10 per cent., solution of sodium carbonate is taken,[24] and boiled in a cast-iron, wrought-iron, or silver boiler (sodium hydroxide does not act on these metals), and lime is added, little by little, during the boiling. This latter is soluble in water, although but very slightly. The clear solution becomes turbid on the addition of the lime because a precipitate is formed; this precipitate consists of calcium carbonate, almost insoluble in water, whilst caustic soda is formed and remains in solution. The decomposition is effected according to the equation: Na_{2}CO_{3} + Ca(HO)_{2} = CaCO_{3} + 2NaHO. On cooling the solution the calcium carbonate easily settles as a precipitate, and the clear solution or alkali above it contains the easily soluble sodium hydroxide formed in the reaction.[25] After the necessary quantity of lime has been added, the solution is allowed to stand, and is then decanted off and evaporated in cast or wrought iron boilers, or in silver pans if a perfectly pure product is required.[26] The evaporation cannot be conducted in china, glass, or similar vessels, because caustic soda attacks these materials, although but slightly. The solution does not crystallise on evaporation, because the solubility of caustic soda when hot is very great, but crystals containing water of crystallisation may be obtained by cooling. If the evaporation of the alkali be conducted until the specific gravity reaches 1·38, and the liquid is then cooled to 0°, transparent crystals appear containing 2NaHO,7H_{2}O; they fuse at +6°.[27] If the evaporation be conducted so long as water is disengaged, which requires a considerable amount of heat, then, on cooling, the hydroxide, NaHO, solidifies in a semi-transparent crystalline mass,[28] which eagerly absorbs moisture and carbonic anhydride from the air.[29] Its specific gravity is 2·13;[30] it is easily soluble in water, with disengagement of a considerable quantity of heat.[31] A saturated solution at the ordinary temperature has a specific gravity of about 1·5, contains about 45 per cent. of sodium hydroxide, and boils at 130°; at 55° water dissolves an equal weight of it.[32] Caustic soda is not only soluble in water but in alcohol, and even in ether. Dilute solutions of sodium hydroxide produce a soapy feeling on the skin because the active base of soap consists of caustic soda.[33] Strong solutions have a corroding action. [23] In chemistry, sodium oxide is termed 'soda,' which word must be carefully distinguished from the word sodium, meaning the metal. [24] With a small quantity of water, the reaction either does not take place, or even proceeds in the reverse way--that is, sodium and potassium hydroxides remove carbonic anhydride from calcium carbonate (Liebig, Watson, Mitscherlich, and others). The influence of the mass of water is evident. According to Gerberts, however, strong solutions of sodium carbonate are decomposed by lime, which is very interesting if confirmed by further investigation. [25] As long as any undecomposed sodium carbonate remains in solution, excess of acid added to the solution disengages carbonic anhydride, and the solution after dilution gives a white precipitate with a barium salt soluble in acids, showing the presence of a carbonate in solution (if there be sulphate present, it also forms a white precipitate, but this is insoluble in acids). For the decomposition of sodium carbonate, milk of lime--that is, slaked slime suspended in water--is employed. Formerly pure sodium hydroxide was prepared (according to Berthollet's process) by dissolving the impure substance in alcohol (sodium carbonate and sulphate are not soluble), but now that metallic sodium has become cheap and is purified by distillation, _pure caustic soda_ is prepared by acting on a small quantity of water with sodium. Perfectly pure sodium hydroxide may also be obtained by allowing strong solutions to crystallise (in the cold) (Note 27). In alkali works where the Leblanc process is used, caustic soda is prepared directly from the alkali remaining in the mother liquors after the separation of the sodium carbonate by evaporation (Note 14). If excess of lime and charcoal have been used, much sodium hydroxide maybe obtained. After the removal as much as possible of the sodium carbonate, a red liquid (from iron oxide) is left, containing sodium hydroxide mixed with compounds of sulphur and of cyanogen (_see_ Chapter IX.) and also containing iron. This red alkali is evaporated and air is blown through it, which oxidises the impurities (for this purpose sometimes sodium nitrate is added, or bleaching powder, &c.) and leaves fused caustic soda. The fused mass is allowed to settle in order to separate the ferruginous precipitate, and poured into iron drums, where the sodium hydroxide solidifies. Such caustic soda contains about 10 p.c. of water in excess and some saline impurities, but when properly manufactured is almost free from carbonate and from iron. The greater part of the caustic soda, which forms so important an article of commerce, is manufactured in this manner. [26] Löwig gave a method of preparing sodium hydroxide from sodium carbonate by heating it to a dull red heat with an excess of ferric oxide. Carbonic anhydride is given off, and warm water extracts the caustic soda from the remaining mass. This reaction, as experiment shows, proceeds very easily, and is an example of contact action similar to that of ferric oxide on the decomposition of potassium chlorate. The reason of this may be that a small quantity of the sodium carbonate enters into double decomposition with the ferric oxide, and the ferric carbonate produced is decomposed into carbonic anhydride and ferric oxide, the action of which is renewed. Similar explanations expressing the _reason_ for a reaction really adds but little to that elementary conception of contact which, according to my opinion, consists in the change of motion of the atoms in the molecules under the influence of the substance in contact. In order to represent this clearly it is sufficient, for instance, to imagine that in the sodium carbonate the elements CO_{2} move in a circle round the elements Na_{2}O, but at the points of contact with Fe_{2}O_{3} the motion becomes elliptic with a long axis, and at some distance from Na_{2}O the elements of CO_{2} are parted, not having the faculty of attaching themselves to Fe_{2}O_{3}. [27] By allowing strong solutions of sodium hydroxide to crystallise in the cold, impurities--such as, for instance, sodium sulphate--may be separated from them. The fused crystallo-hydrate 2NaHO,7H_{2}O forms a solution having a specific gravity of 1·405 (Hermes). The crystals on dissolving in water produce cold, while NaHO produces heat. Besides which Pickering obtained hydrates with 1, 2, 4, 5, and 7 H_{2}O. [28] In solid caustic soda there is generally an excess of water beyond that required by the formula NaHO. The caustic soda used in laboratories is generally cast in sticks, which are broken into pieces. It must be preserved in carefully closed vessels, because it absorbs water and carbonic anhydride from the air. [29] By the way it changes in air it is easy to distinguish caustic soda from caustic potash, which in general resembles it. Both alkalis absorb water and carbonic anhydride from the air, but caustic potash forms a deliquescent mass of potassium carbonate, whilst caustic soda forms a dry powder of efflorescent salt. [30] As the molecular weight of NaHO = 40, the volume of its molecule = 40/2·13 = 18·5, which very nearly approaches the volume of a molecule of water. The same rule applies to the compounds of sodium in general--for instance, its salts have a molecular volume approaching the volume of the acids from which they are derived. [31] The molecular quantity of sodium hydroxide (40 grams), on being dissolved in a large mass (200 gram molecules) of water, develops, according to Berthelot 9,780, and according to Thomsen 9,940, heat-units, but at 100° about 13,000 (Berthelot). Solutions of NaHO + _n_H_{2}O, on being mixed with water, evolve heat if they contain less than 6H_{2}O, but if more they absorb beat. [32] The specific gravity of solutions of sodium hydroxide at 15°/4° is given in the short table below:-- NaHO, p.c. 5 10 15 20 30 40 Sp. gr. 1·057 1·113 1·169 1·224 1·331 1·436 1,000 grams of a 5 p.c. solution occupies a volume of 946 c.c.; that is, less than the water serving to make the solution (_see_ Note 18). [33] Sodium hydroxide and some other alkalis are capable of hydrolysing--saponifying, as it is termed--the compounds of acids with alcohols. If RHO (or R(HO)_{_n_}) represent the composition of an alcohol--that is, of the hydroxide of a hydrocarbon radicle--and QHO an acid, then the compound of the acid with the alcohol or ethereal salt of the given acid will have the composition RQO. Ethereal salts, therefore, present a likeness to metallic salts, just as alcohols resemble basic hydroxides. Sodium hydroxide acts on ethereal salts in the same way that it acts on the majority of metallic salts--namely, it liberates alcohol, and forms the sodium salt of that acid which was in the ethereal salt. The reaction takes place in the following way:-- RQO + NaHO = NaQO + RHO Ethereal Caustic Sodium Alcohol salt soda salt Such a decomposition is termed saponification; similar reactions were known very long ago for the ethereal salts corresponding with glycerin, C_{3}H_{5}(OH)_{3} (Chapter IX.), found in animals and plants, and composing what are called fats or oils. Caustic soda, acting on fat and oil, forms glycerin, and sodium salts of those acids which were in union with the glycerin in the fat, as Chevreul showed at the beginning of this century. The sodium salts of the fatty acids are commonly known as soaps. That is to say, soap is made from fat and caustic soda, glycerin being separated and a sodium salt or soap formed. As glycerin is usually found in union with certain acids, so also are the sodium salts of the same acids found in soap. The greater part of the acids found in conjunction with glycerin in fats are the solid palmitic and stearic acids, C_{16}H_{32}O_{2} and C_{18}H_{38}O_{2}, and the liquid oleic acid, C_{18}H_{34}O_{2}. In preparing soap the fatty substances are mixed with a solution of caustic soda until an emulsion is formed; the proper quantity of caustic soda is then added in order to produce saponification on heating, the soap being separated from the solution either by means of an excess of caustic soda or else by common salt, which displaces the soap from the aqueous solution (salt water does not dissolve soap, neither does it form a lather). Water acting on soap partly decomposes it (because the acids of the soap are feeble), and the alkali set free acts during the application of soap. Hence it may be replaced by a very feeble alkali. Strong solutions of alkali corrode the skin and tissues. They are not formed from soap, because the reaction is reversible, and the alkali is only set free by the excess of water. Thus we see how the teaching of Berthollet renders it possible to understand many phenomena which occur in every-day experience (_see_ Chapter IX., Note 15). The chemical _reactions of sodium hydroxide_ serve as a type for those of a whole class of alkalis--that is, of soluble basic hydroxides, MOH. The solution of sodium hydroxide is a very caustic liquid--that is to say, it acts in a destructive way on most substances, for instance on most organic tissues--hence caustic soda, like all soluble alkalis, is a poisonous substance; acids, for example hydrochloric, serve as antidotes. The action of caustic soda on bones, fat, starch, and similar vegetable and animal substances explains its action on organisms. Thus bones, when plunged into a weak solution of caustic soda, fall to powder,[34] and evolve a smell of ammonia, owing to the caustic soda changing the gelatinous organic substance of the bones (which contains carbon, hydrogen, nitrogen, oxygen, and sulphur, like albumin), dissolving it and in part destroying it, whence ammonia is disengaged. Fats, tallow, and oils become saponified by a solution of caustic soda--that is to say, they form with it _soaps_ soluble in water, or sodium salts of the organic acids contained in the fats.[35] The most characteristic reactions of sodium hydroxide are determined by the fact that it _saturates all acids, forming salts with them_, which are almost all soluble in water, and in this respect caustic soda is as characteristic amongst the bases as nitric acid is among the acids. It is impossible to detect sodium by means of the formation of precipitates of insoluble sodium salts, as may be done with other metals, many of whose salts are but slightly soluble. The powerful alkaline properties of caustic soda determine its capacity for combining with even the feeblest acids, its property of disengaging ammonia from ammonium salts, its faculty of forming precipitates from solutions of salts whose bases are insoluble in water, &c. If a solution of the salt of almost any metal be mixed with caustic soda, then a soluble sodium salt will be formed, and an insoluble hydroxide of the metal will be separated--for instance, copper nitrate yields copper hydroxide, Cu(NO_{3})_{2} + 2NaHO = Cu(HO)_{2} + 2NaNO_{3}. Even many _basic oxides_ precipitated by caustic soda _are capable_ of _combining_ with it and forming soluble compounds, and therefore caustic soda in the presence of salts of such metals first forms a precipitate of hydroxide, and then, employed in excess, dissolves this precipitate. This phenomenon occurs, for example, when caustic soda is added to the salts of aluminium. This shows the property of such an alkali as caustic soda of combining not only with acids, but also with feeble basic oxides. For this reason caustic soda _acts on most elements_ which are capable of forming acids or oxides similar to them; thus the metal aluminium gives hydrogen with caustic soda in consequence of the formation of alumina, which combines with the caustic soda--that is, in this case, the caustic alkali acts on the metal just as sulphuric acid does on Fe or Zn. If caustic soda acts in this manner on a metalloid capable of combining with the hydrogen evolved (aluminium does not give a compound with hydrogen), then it forms such a hydrogen compound. Thus, for instance, phosphorus acts in this way on caustic soda, yielding hydrogen phosphide. When the hydrogen compound disengaged is capable of combining with the alkali, then, naturally, a salt of the corresponding acid is formed. For example, chlorine and sulphur act in this way on caustic soda. Chlorine, with the hydrogen of the caustic soda, forms hydrochloric acid, and the latter forms common salt with the sodium hydroxide, whilst the other atom in the molecule of chlorine, Cl_{2}, takes the place of the hydrogen, and forms the hypochlorite, NaClO. In the same way, by the action of sodium hydroxide on sulphur, hydrogen sulphide is formed, which acts on the soda forming sodium _sulphide_, in addition to which sodium thiosulphate is formed (_see_ Chapter XX.) By virtue of such reactions, sodium hydroxide acts on many metals and non-metals. Such action is often accelerated by the presence of the oxygen of the air, as by this means the formation of acids and oxides rich in oxygen is facilitated. Thus many metals and their lower oxides, in the presence of an alkali, absorb oxygen and form acids. Even manganese peroxide, when mixed with caustic soda, is capable of absorbing the oxygen of the air, and forming sodium manganate. Organic acids when heated with caustic soda give up to it the elements of carbonic anhydride, forming sodium carbonate, and separating that hydrocarbon group which exists, in combination with carbonic anhydride, in the organic acid. [34] On this is founded the process of Henkoff and Engelhardt for treating bones. The bones are mixed with ashes, lime, and water; it is true that in this case more potassium hydroxide than sodium hydroxide is formed, but their action is almost identical. [35] As explained in Note 33. Thus sodium hydroxide, like the soluble alkalis in general, ranks amongst the most active substances in the chemical sense of the term, and but few substances are capable of resisting it. Even siliceous rocks, as we shall see further on, are transformed by it, forming when fused with it vitreous slags. Sodium hydroxide (like ammonium and potassium hydroxides), as a typical example of the basic hydrates, in distinction from many other basic oxides, easily _forms acid salts_ with acids (for instance, NaHSO_{4}, NaHCO_{3}), and does not form any basic salts at all; whilst many less energetic bases, such as the oxides of copper and lead, easily form basic salts, but acid salts only with difficulty. This capability of forming acid salts, particularly with polybasic acids, may be explained by the energetic basic properties of sodium hydroxide, contrasted with the small development of these properties in the bases which easily form basic salts. An energetic base is capable of retaining a considerable quantity of acid, which a slightly energetic base would not have the power of doing. Also, as will be shown in the subsequent chapters, sodium belongs to the univalent metals, being exchangeable for hydrogen atom for atom--that is, amongst metals sodium may, like chlorine amongst the non-metals, serve as the representative of the univalent properties. Most of the elements which are not capable of forming acid salts are bivalent. Whence it may be understood that in a bibasic acid--for instance, carbonic, H_{2}CO_{3}, or sulphuric, H_{2}SO_{4}--the hydrogen may be exchanged, atom for atom, for sodium, and yield an acid salt by means of the first substitution, and a normal salt by means of the second--for instance, NaHSO_{4}, and Na_{2}SO_{4}, whilst such bivalent metals as calcium and barium do not form acid salts because one of their atoms at once takes the place of both hydrogen atoms, forming, for example, CaCO_{3} and CaSO_{4}.[35 bis] [35 bis] It might be expected, from what has been mentioned above, that bivalent metals would easily form acid salts with acids containing more than two atoms of hydrogen--for instance, with tribasic acids, such as phosphoric acid, H_{3}PO_{4}--and actually such salts do exist; but all such relations are complicated by the fact that the character of the base very often changes and becomes weakened with the increase of valency and the change of atomic weight; the feebler bases (like silver oxide), although corresponding with univalent metals, do not form acid salts, while the feeblest bases (CuO, PbO, &c.) easily form basic salts, and notwithstanding their valency do not form acid salts which are in any degree stable--that is, which are undecomposable by water. Basic and acid salts ought to be regarded rather as compounds similar to crystallo-hydrates, because such acids as sulphuric form with sodium not only an acid and a normal salt, as might be expected from the valency of sodium, but also salts containing a greater quantity of acid. In sodium sesquicarbonate we saw an example of such compounds. Taking all this into consideration, we must say that the property of more or less easily forming acid salts depends more upon the energy of the base than upon its valency, and the best statement is that _the capacity of a base for forming acid and basic salts is characteristic_, just as the faculty of forming compounds with hydrogen is characteristic of elements. We have seen the transformation of common salt into sodium sulphate, of this latter into sodium carbonate, and of sodium carbonate into caustic soda. Lavoisier still regarded sodium hydroxide as an element, because he was unacquainted with its decomposition with the formation of metallic sodium, which separates the hydrogen from water, reforming caustic soda. The preparation of _metallic sodium_ was one of the greatest discoveries in chemistry, not only because through it the conception of elements became broader and more correct, but especially because in sodium, chemical properties were observed which were but feebly shown in the other metals more familiarly known. This discovery was made in 1807 by the English chemist _Davy_ by means of the galvanic current. By connecting with the positive pole (of copper or carbon) a piece of caustic soda (moistened in order to obtain electrical conductivity), and boring a hole in it filled with mercury connected with the negative pole of a strong Volta's pile, Davy observed that on passing the current a peculiar metal dissolved in the mercury, less volatile than mercury, and capable of decomposing water, again forming caustic soda. In this way (by analysis and synthesis) Davy demonstrated the compound nature of alkalis. On being decomposed by the galvanic current, caustic soda disengages hydrogen and sodium at the negative pole and oxygen at the positive pole. Davy showed that the metal formed volatilises at a red heat, and this is its most important physical property in relation to its extraction, all later methods being founded on it. Besides this Davy observed that sodium easily oxidises, its vapour taking fire in air, and the latter circumstance was for a long time an obstacle to the easy preparation of this metal. The properties of sodium were subsequently more thoroughly investigated by Gay-Lussac and Thénard, who observed that metallic iron at a high temperature was capable of reducing caustic soda to sodium.[36] Brunner latterly discovered that not only iron, but also charcoal, has this property, although hydrogen has not.[37] But still the methods of extracting sodium were very troublesome, and consequently it was a great rarity. The principal obstacle to its production was that an endeavour was made to condense the easily-oxidising vapours of sodium in vacuo in complicated apparatus. For this reason, when Donny and Maresca, having thoroughly studied the matter, constructed a specially simple condenser, the production of sodium was much facilitated. Furthermore, in practice the most important epoch in the history of the production of sodium is comprised in the investigation of Sainte-Claire Deville, who avoided the complex methods in vogue up to that time, and furnished those simple means by which the production of sodium is now rendered feasible in chemical works. [36] Deville supposes that such a decomposition of sodium hydroxide by metallic iron depends solely on the dissociation of the alkali at a white heat into sodium, hydrogen, and oxygen. Here the part played by the iron is only that it retains the oxygen formed, otherwise the decomposed elements would again reunite upon cooling, as in other cases of dissociation. If it be supposed that the temperature at the commencement of the dissociation of the iron oxides is higher than that of sodium oxide, then the decomposition may be explained by Deville's hypothesis. Deville demonstrates his views by the following experiment:--An iron bottle, filled with iron borings, was heated in such a way that the upper part became red hot, the lower part remaining cooler; sodium hydroxide was introduced into the upper part. The decomposition was then effected--that is, sodium vapours were produced (this experiment was really performed with potassium hydroxide). On opening the bottle it was found that the iron in the upper part was not oxidised, but only that in the lower part. This may be explained by the decomposition of the alkali into sodium, hydrogen, and oxygen taking place in the upper part, whilst the iron in the lower part absorbed the oxygen set free. If the whole bottle be subjected to the same moderate heat as the lower extremity, no metallic vapours are formed. In that case, according to the hypothesis, the temperature is insufficient for the dissociation of the sodium hydroxide. [37] It has been previously remarked (Chapter II. Note 9) that Beketoff showed the displacement of sodium by hydrogen, not from sodium hydroxide but from the oxide Na_{2}O; then, however, only one half is displaced, with the formation of NaHO. For the production of sodium according to Deville's method, a mixture of anhydrous sodium carbonate (7 parts), charcoal (two parts), and lime or chalk (7 parts) is heated. This latter ingredient is only added in order that the sodium carbonate, on fusing, shall not separate from the charcoal.[38] The chalk on being heated loses carbonic anhydride, leaving infusible lime, which is permeated by the sodium carbonate and forms a thick mass, in which the charcoal is intimately mixed with the sodium carbonate. When the charcoal is heated with the sodium carbonate, at a white heat, carbonic oxide and vapours of sodium are disengaged, according to the equation: Na_{2}CO_{3} + 2C = Na_{2} + 3CO [38] Since the close of the eighties in England, where the preparation of sodium is at present carried out on a large commercial scale (from 1860 to 1870 it was only manufactured in a few works in France), it has been the practice to add to Deville's mixture iron, or iron oxide which with the charcoal gives metallic and carburetted iron, which still further facilitates the decomposition. At present a kilogram of sodium may be purchased for about the same sum (2/-) as a gram cost thirty years ago. Castner, in England, greatly improved the manufacture of sodium in large quantities, and so cheapened it as a reducing agent in the preparation of metallic aluminium. He heated a mixture of 44 parts of NaHO, and 7 parts of carbide of iron in large iron retorts at 1,000° and obtained about 6-1/2 parts of metallic sodium. The reaction proceeds more easily than with carbon or iron alone, and the decomposition of the NaHO proceeds according to the equation: 3NaHO + C = Na_{2}CO_{3} + 3H + Na. Subsequently, in 1891, aluminium was prepared by electrolysis (_see_ Chapter XVII.), and metallic sodium found two new uses; (1) for the manufacture of peroxide of sodium (see later on) which is used in bleaching works, and (2) in the manufacture of potassium and sodium cyanide from yellow prussiate (Chapter XIII., Note 12). [Illustration: FIG. 70.--Manufacture of sodium by Deville's process. A C, iron tube containing a mixture of soda, charcoal, and chalk. B, condenser.] On cooling the vapours and gases disengaged, the vapours condense into molten metal (in this form sodium does not easily oxidise, whilst in vapour it burns) and the carbonic oxide remains as gas. [Illustration: FIG. 71.--Donny and Maresca's sodium condenser, consisting of two cast-iron plates screwed together.] In sodium works an iron tube, about a metre long and a decimeter in diameter, is made out of boiler plate. The pipe is luted into a furnace having a strong draught, capable of giving a high temperature, and the tube is charged with the mixture required for the preparation of sodium. One end of the tube is closed with a cast-iron stopper A with clay luting, and the other with the cast-iron stopper C provided with an aperture. On heating, first of all the moisture contained in the various substances is given off, then carbonic anhydride and the products of the dry distillation of the charcoal, then the latter begins to act on the sodium carbonate, and carbonic oxide and vapours of sodium appear. It is easy to observe the appearance of the latter, because on issuing from the aperture in the stopper C they take fire spontaneously and burn with a very bright yellow flame. A pipe is then introduced into the aperture C, compelling the vapours and gases formed to pass through the condenser B. This condenser consists of two square cast-iron trays, A and A´, fig. 71, with wide edges firmly screwed together. Between these two trays there is a space in which the condensation of the vapours of sodium is effected, the thin metallic walls of the condenser being cooled by the air but remaining hot enough to preserve the sodium in a liquid state, so that it does not choke the apparatus, but continually flows from it. The vapours of sodium, condensing in the cooler, flow in the shape of liquid metal into a vessel containing some non-volatile naphtha or hydrocarbon. This is used in order to prevent the sodium oxidising as it issues from the condenser at a somewhat high temperature. In order to obtain sodium of a pure quality it is necessary to distil it once more, which may even be done in porcelain retorts, but the distillation must be conducted in a stream of some gas on which sodium does not act, for instance in a stream of nitrogen; carbonic anhydride is not applicable, because sodium partially decomposes it, absorbing oxygen from it. Although the above described methods of preparing sodium by chemical means have proved very convenient in practice, still it is now (since 1893) found profitable in England to obtain it (to the amount of several tons a week) by Davy's classical method, _i.e._ by the action of an electric current at a moderately high temperature, because the means for producing an electric current (by motors and dynamos) now render this quite feasible. This may be regarded as a sign that in process of time many other technical methods for producing various substances by _decomposition_ may be profitably carried on by electrolysis. Pure sodium is a lustrous metal, white as silver, soft as wax; it becomes brittle in the cold. In ordinary moist air it quickly tarnishes and becomes covered with a film of hydroxide, NaHO, formed at the expense of the water in the air. In perfectly dry air sodium retains its lustre for an indefinite time. Its density at the ordinary temperature is equal to 0·98, so that it is lighter than water; it fuses very easily at a temperature of 95°, and distils at a bright red heat (742° according to Perman, 1889). Scott (1887) determined the density of sodium vapour and found it to be nearly 12 (if H = 1). This shows that its molecule contains one atom (like mercury and cadmium) Na.[38 bis] It forms alloys with most metals, combining with them, heat being sometimes evolved and sometimes absorbed. Thus, if sodium (having a clean surface) be thrown into mercury, especially when heated, there is a flash, and such a considerable amount of heat is evolved that part of the mercury is transformed into vapour.[39] Compounds or solutions of sodium in mercury, or _amalgams_ of sodium, even when containing 2 parts of sodium to 100 parts of mercury, are solids. Only those amalgams which are the very poorest in sodium are liquid. Such alloys of sodium with mercury are often used instead of sodium in chemical investigations, because in combination with mercury sodium is not easily acted on by air, and is heavier than water, and therefore more convenient to handle, whilst at the same time it retains the principal properties of sodium,[40] for instance it decomposes water, forming NaHO. [38 bis] This is also shown by the fall in the temperature of solidification of tin produced by the addition of sodium (and also Al and Zn). Heycock and Neville (1889). [39] By dissolving sodium amalgams in water and acids, and deducting the heat of solution of the sodium, Berthelot found that _for each atom of the sodium_ in amalgams containing a larger amount of mercury than NaHg_{5}, the amount of heat evolved increases, after which the heat of formation falls, and the heat evolved decreases. In the formation of NaHg_{5} about 18,500 calories are evolved; when NaHg_{3} is formed, about 14,000; and for NaHg about 10,000 calories. Kraft regarded the definite crystalline amalgam as having the composition of NaHg_{6}, but at the present time, in accordance with Grimaldi's results, it is thought to be NaHg_{5}. A similar amalgam is very easily obtained if a 3 p.c. amalgam be left several days in a solution of sodium hydroxide until a crystalline mass is formed, from which the mercury may be removed by strongly pressing in chamois leather. This amalgam with a solution of potassium hydroxide forms a potassium amalgam, KHg_{10}. It may be mentioned here that the latent heat of fusion (of atomic quantities) of Hg = 360 (Personne), Na = 730 (Joannis), and K = 610 calories (Joannis). [40] Alloys are so similar to solutions (exhibiting such complete parallelism in properties) that they are included in the same class of so-called indefinite compounds. But in alloys, as substances passing from the liquid to the solid state, it is easier to discover the formation of definite chemical compounds. Besides the alloys of Na with Hg, those with tin (Bailey 1892 found Na_{2}Sn), lead (NaPb), bismuth (Na_{3}Bi), &c. (Joannis 1892 and others) have been investigated. It is easy to form an alloy of mercury and sodium having a crystalline structure, and a definite atomic composition, NaHg_{5}. The alloy of sodium with hydrogen or _sodium hydride_, Na_{2}H, which has the external appearance of a metal,[41] is a most instructive example of the characteristics of alloys. At the ordinary temperature sodium does not absorb hydrogen, but from 300° to 421° the absorption takes place at the ordinary pressure (and at an increased pressure even at higher temperatures), as shown by Troost and Hautefeuille (1874). One volume of sodium absorbs as much as 238 volumes of hydrogen. The metal increases in volume, and when once formed the alloy can be preserved for some time without change at the ordinary temperature. The appearance of sodium hydride resembles that of sodium itself; it is as soft as this latter, when heated it becomes brittle, and decomposes above 300°, evolving hydrogen. In this decomposition all the phenomena of dissociation are very clearly shown--that is, the hydrogen gas evolved has a definite tension[42] corresponding with each definite temperature. This confirms the fact that the formation of substances capable of dissociation can only be accomplished within the dissociation limits. Sodium hydride melts more easily than sodium itself, and then does not undergo decomposition if it is in an atmosphere of hydrogen. It oxidises easily in air, but not so easily as potassium hydride. The chemical reactions of sodium are retained in its hydride, and, if we may so express it, they are even increased by the addition of hydrogen. At all events, in the properties of sodium hydride[43] we see other properties than in such hydrogen compounds as HCl, H_{2}O, H_{3}N, H_{4}C, or even in the gaseous metallic hydrides AsH_{3}, TeH_{2}. Platinum, palladium, nickel, and iron, in absorbing hydrogen form compounds in which hydrogen is in a similar state. In them, as in sodium hydride, the hydrogen is compressed, absorbed, occluded (Chapter II.)[43 bis] [41] Potassium forms a similar compound, but lithium, under the same circumstances, does not. [42] The tension of dissociation of hydrogen _p_, in millimetres of mercury, is:-- _t_ = 330° 350° 400° 430° for Na_{2}H _p_ = 28 57 447 910 for K_{2}H 45 72 548 1100 [43] In general, during the formation of alloys the volumes change very slightly, and therefore from the volume of Na_{2}H some idea may be formed of the volume of hydrogen in a solid or liquid state. Even Archimedes concluded that there was gold in an alloy of copper and gold by reason of its volume and density. From the fact that the density of Na_{2}H is equal to 0·959, it may be seen that the volume of 47 grams (the gram molecule) of this compound = 49·0 c.c. The volume of 46 grams of sodium contained in the Na_{2}H (the density under the same conditions being 0·97) is equal to 47·4 c.c. Therefore the volume of 1 gram of hydrogen in Na_{2}H is equal to 1·6 c.c., and consequently the density of metallic hydrogen, or the weight of 1 c.c., approaches 0·6 gram. This density is also proper to the hydrogen alloyed with potassium and palladium. Judging from the scanty information which is at present available, liquid hydrogen near its absolute boiling point (Chapter II.) has a much lower density. [43 bis] We may remark that at low temperatures Na absorbs NH_{3} and forms (NH_{3}Na)_{2} (_see_ Chapter VI., Note 14); this substance absorbs CO and gives (NaCO)n (Chapter IX., Note 31), although by itself Na does not combine directly with CO (but K does). The most important chemical property of sodium is its power of easily decomposing water and _evolving hydrogen_ from the majority of the hydrogen compounds, and especially from all acids, and hydrates in which hydroxyl must be recognised. This depends on its power of combining with the elements which are in combination with the hydrogen. We already know that sodium disengages hydrogen, not only from water, hydrochloric acid,[44] and all other acids, but also from ammonia,[44 bis] with the formation of sodamide NH_{2}Na, although it does not displace hydrogen from the hydrocarbons.[45] Sodium burns both in chlorine and in oxygen, evolving much heat. These properties are closely connected with its power of taking up oxygen, chlorine, and similar elements from most of their compounds. Just as it removes the oxygen from the oxides of nitrogen and from carbonic anhydride, so also does it decompose the majority of oxides at definite temperatures. Here the action is essentially the same as in the decomposition of water. Thus, for instance, when acting on magnesium chloride the sodium displaces the magnesium, and when acting on aluminium chloride it displaces metallic aluminium. Sulphur, phosphorus, arsenic and a whole series of other elements, also combine with sodium.[46] [44] H. A. Schmidt remarked that perfectly dry hydrogen chloride is decomposed with great difficulty by sodium, although the decomposition proceeds easily with potassium and with sodium in moist hydrogen chloride. Wanklyn also remarked that sodium burns with great difficulty in dry chlorine. Probably these facts are related to other phenomena observed by Dixon, who found that perfectly dry carbonic oxide does not explode with oxygen on passing an electric spark. [44 bis] Sodamide, NH_{2}Na, (Chapter IV., Note 14), discovered by Gay-Lussac and Thénard, has formed the object of repeated research, but has been most fully investigated by A. W. Titherley (1894). Until recently the following was all that was known about this compound:-- By heating sodium in dry ammonia, Gay-Lussac and Thénard obtained an olive-green, easily-fusible mass, _sodamide_, NH_{2}Na, hydrogen being separated. This substance with water forms sodium hydroxide and ammonia; with carbonic oxide, CO, it forms sodium cyanide, NaCN, and water, H_{2}O; and with dry hydrogen chloride it forms sodium and ammonium chlorides. These and other reactions of sodamide show that the metal in it preserves its energetic properties in reaction, and that this compound of sodium is more stable than the corresponding chlorine amide. When heated, sodamide, NH_{2}Na, only partially decomposes, with evolution of hydrogen, the principal part of it giving ammonia and sodium nitride, Na_{3}N, according to the equation 3NH_{2}Na = 2NH_{3} + NNa_{3}. The latter is an almost black powdery mass, decomposed by water into ammonia and sodium hydroxide. Titherley's researches added the following data:-- Iron or silver vessels should be used in preparing this body, because glass and porcelain are corroded at 300°-400°, at which temperature ammonia gas acts upon sodium and forms the amide with the evolution of hydrogen. The reaction proceeds slowly, but is complete if there be an excess of NH_{3}. Pure NH_{2}Na is colourless (its colouration is due to various impurities), semi-transparent, shows traces of crystallisation, has a conchoidal fracture, and melts at 145°. Judging from the increase in weight of the sodium and the quantity of hydrogen which is disengaged, the composition of the amide is exactly NH_{2}Na. It partially volatilises (sublimes) in vacuo at 200°, and breaks up into 2Na + N_{2} + 2H_{2} at 500°. The same amide is formed when oxide of sodium is heated in NH_{3}: Na_{2}O + 2NH_{3} = 2NaH_{2}N + H_{2}O. NaHO is also formed to some extent by the resultant H_{2}O. Potassium and lithium form similar amides. With water, alcohol, and acids, NH_{2}Na gives NH_{3} and NaHO, which react further. Anhydrous CaO absorbs NH_{2}Na when heated without decomposing it. When sodamide is heated with SiO_{2}, NH_{3} is disengaged, and silicon nitride formed. It acts still more readily upon boric anhydride when heated with it: 2NH_{2}Na + B_{2}O_{3} = 2BN + 2NaHO + H_{2}O. When slightly heated, NH_{2}Na + NOCl = NaCl + N_{2} + H_{2}O (NHNa_{2} and NNa_{3} are apparently not formed at a higher temperature). The halogen organic compounds react with the aid of heat, but with so much energy that the reaction frequently leads to the ultimate destruction of the organic groups and production of carbon. [45] As sodium does not displace hydrogen from the hydrocarbons, _it may be preserved_ in liquid hydrocarbons. Naphtha is generally used for this purpose, as it consists of a mixture of various liquid hydrocarbons. However, in naphtha sodium usually becomes coated with a crust composed of matter produced by the action of the sodium on certain of the substances contained in the mixture composing naphtha. In order that sodium may retain its lustre in naphtha, secondary octyl alcohol is added. (This alcohol is obtained by distilling castor oil with caustic potash.) Sodium keeps well in a mixture of pure benzene and paraffin. [46] If sodium does not directly displace the hydrogen in hydrocarbons, still by indirect means compounds may be obtained which contain sodium and hydrocarbon groups. Some of these compounds have been produced, although not in a pure state. Thus, for instance, zinc ethyl, Zn(C_{2}H_{5})_{2}, when treated with sodium, loses zinc and forms sodium ethyl, C_{2}H_{5}Na, but this decomposition is not complete, and the compound formed cannot be separated by distillation from the remaining zinc ethyl. In this compound the energy of the sodium is clearly manifest, for it reacts with substances containing haloids, oxygen, &c., and directly absorbs carbonic anhydride, forming a salt of a carboxylic acid (propionic). With _oxygen_ sodium unites in three degrees of combination, forming a suboxide Na_{4}O,[46 bis] an oxide, Na_{2}O, and a peroxide, NaO. They are thus termed because Na_{2}O is a stable basic oxide (with water it forms a basic hydroxide), whilst Na_{4}O and NaO do not form corresponding saline hydrates and salts. The suboxide is a grey inflammable substance which easily decomposes water, disengaging hydrogen; it is formed by the slow oxidation of sodium at the ordinary temperature. The peroxide is a greenish yellow substance, fusing at a bright red heat; it is produced by burning sodium in an excess of oxygen, and it yields oxygen when treated with water: Suboxide: Na_{4}O + 3H_{2}O = 4NaHO + H_{2}[47] Oxide: Na_{2}O + H_{2}O = 2NaHO[48] Peroxide: Na_{2}O_{2} + H_{2}O = 2NaHO + O[49] All three oxides form sodium hydroxide with water, but only the oxide Na_{2}O is directly transformed into a hydrate. The other oxides liberate either hydrogen or oxygen; they also present a similar distinction with reference to many other agents. Thus carbonic anhydride combines directly with the oxide Na_{2}O, which when heated in the gas burns, forming sodium carbonate, whilst the peroxide yields oxygen in addition. When treated with acids, sodium and all its oxides only form the salts corresponding with sodium oxide--that is, of the formula or type NaX. Thus the oxide of sodium, Na_{2}O, is _the only salt-forming oxide_ of this metal, as water is in the case of hydrogen. Although the peroxide H_{2}O_{2} is derived from hydrogen, and Na_{2}O_{2} from sodium, yet there are no corresponding salts known, and if they are formed they are probably as unstable as hydrogen peroxide. Although carbon forms carbonic oxide, CO, still it has only one salt-forming oxide--carbonic anhydride, CO_{2}. Nitrogen and chlorine both give several salt-forming oxides and types of salts. But of the oxides of nitrogen, NO and NO_{2} do not form salts, as do N_{2}O_{3}, N_{2}O_{4}, and N_{2}O_{5}, although N_{2}O_{4} does not form special salts, and N_{2}O_{5} corresponds with the highest form of the saline compounds of nitrogen. Such distinctions between the elements, according to their power of giving one or several saline forms, is a radical property of no less importance than the basic or acid properties of their oxides. Sodium as a typical metal does not form any acid oxides, whilst chlorine, as a typical non-metal, does not form bases with oxygen. Therefore sodium _as an element_ may be thus characterised: it forms one very stable salt-forming oxide, Na_{2}O, having powerful basic properties, and its salts are of the general formula, NaX, therefore in its compounds it is, like hydrogen, a basic and univalent element. [46 bis] It is even doubtful whether the suboxide exists (_see_ Note 47). [47] A compound, Na_{2}Cl, which corresponds with the suboxide, is apparently formed when a galvanic current is passed through fused common salt; the sodium liberated dissolves in the common salt, and does not separate from the compound either on cooling or on treatment with mercury. It is therefore supposed to be Na_{2}Cl; the more so as the mass obtained gives hydrogen when treated with water: Na_{2}Cl + H_{2}O = H + NaHO + NaCl, that is, it acts like suboxide of sodium. If Na_{2}Cl really exists as a salt, then the corresponding base Na_{4}O, according to the rule with other bases of the composition M_{4}O, ought to be called a quaternary oxide. According to certain evidence, a suboxide is formed when thin sheets or fine drops of sodium slowly oxidise in moist air. [48] According to observations easily made, sodium when fused in air oxidises but does not burn, the combustion only commencing with the formation of vapour--that is, when considerably heated. Davy and Karsten obtained the oxides of potassium, K_{2}O, and of sodium, Na_{2}O, by heating the metals with their hydroxides, whence NaHO + Na = Na_{2}O + H, but N. N. Beketoff failed to obtain oxides by this means. He prepared them by directly igniting the metals in dry air, and afterwards heating with the metal in order to destroy any peroxide. The oxide produced, Na_{2}O, when heated in an atmosphere of hydrogen, gave a mixture of sodium and its hydroxide: Na_{2}O + H = NaHO + Na (_see_ Chapter II., Note 9). If both the observations mentioned are accurate, then the reaction is reversible. Sodium oxide ought to be formed during the decomposition of sodium carbonate by oxide of iron (_see_ Note 26), and during the decomposition of sodium nitrite. According to Karsten, its specific gravity is 2·8, according to Beketoff 2·3. The difficulty in obtaining it is owing to an excess of sodium forming the suboxide, and an excess of oxygen the peroxide. The grey colour peculiar to the suboxide and oxide perhaps shows that they contain metallic sodium. In addition to this, in the presence of water it may contain sodium hydride and NaHO. [49] Of the oxides of sodium, that easiest to form is the peroxide, NaO or Na_{2}O_{2}; this is obtained when sodium is burnt in an excess of oxygen. If NaNO_{3} be melted, it gives Na_{2}O_{2} with metallic Na. In a fused state the peroxide is reddish yellow, but it becomes almost colourless when cold. When heated with iodine vapour, it loses oxygen: Na_{2}O_{2} +I_{2} = Na_{2}OI_{2} + O. The compound Na_{2}OI_{2} is akin to the compound Cu_{2}OCl_{2} obtained by oxidising CuCl. This reaction is one of the few in which iodine directly displaces oxygen. The substance Na_{2}OI_{2} is soluble in water, and when acidified gives free iodine and a sodium salt. Carbonic oxide is absorbed by heated sodium peroxide with formation of sodium carbonate: Na_{2}CO_{3} = Na_{2}O_{2} + CO, whilst carbonic anhydride liberates oxygen from it. With nitrous oxide it reacts thus: Na_{2}O_{2} +2N_{2}O = 2NaNO_{2} +N_{2}; with nitric oxide it combines directly, forming sodium nitrite, NaO + NO = NaNO_{2}. Sodium peroxide, when treated with water, does not give hydrogen peroxide, because the latter in the presence of the alkali formed (Na_{2}O_{2}+ 2H_{2}O = 2NaHO + H_{2}O_{2}) decomposes into water and oxygen. In the presence of dilute sulphuric acid it forms H_{2}O_{2} (Na_{2}O_{2} + H_{2}SO_{4} = Na_{2}SO_{4} + H_{2}O_{2}). Peroxide of sodium is now prepared on a large scale (by the action of air upon Na at 300°) for bleaching wool, silk &c. (when it acts in virtue of the H_{2}O_{2} formed). The oxidising properties of Na_{2}O_{2} under the action of heat are seen, for instance, in the fact that when heated with I it forms sodium iodate; with PbO, Na_{2}PbO_{3}; with pyrites, sulphates, &c. When peroxide of sodium comes into contact with water, it evolves much heat, forming H_{2}O_{2}, and decomposing with the disengagement of oxygen; but, as a rule, there is no explosion. But if Na_{2}O_{2} be placed in contact with organic matter, such as sawdust, cotton, &c., it gives a violent explosion when heated, ignited, or acted on by water. Peroxide of sodium forms an excellent oxidising agent for the preparation of the higher product of oxidation of Mn, Cr, W, &c., and also for oxidising the metallic sulphides. It should therefore find many applications in chemical analysis. To prepare Na_{2}O_{2} on a large scale, Castner melts Na in an aluminium vessel, and at 300° passes first air deprived of a portion of its oxygen (having been already once used), and then ordinary dry air over it. On comparing sodium and its analogues, which will be described later with other metallic elements, it will be seen that these properties, together with the relative lightness of the metal itself and its compounds, and the magnitude of its atomic weight comprise the most essential properties of this element, clearly distinguishing it from others, and enabling us easily to recognise its analogues. CHAPTER XIII POTASSIUM, RUBIDIUM, CÆSIUM, AND LITHIUM. SPECTRUM ANALYSIS Just as the series of halogens, fluorine, bromine and iodine correspond with the chlorine contained in common salt, so also there exists a corresponding series of elements: lithium, Li = 7, potassium, K = 39, rubidium, Rb = 85, and cæsium, Cs = 133, which are analogous to the sodium in common salt. These elements bear as great a resemblance to sodium, Na = 23, as fluorine, F = 19, bromine, Br = 80, and iodine, I = 127, do to chlorine, Cl = 35·5. Indeed, in a free state, these elements, like sodium, are soft metals which rapidly oxidise in moist air and decompose water at the ordinary temperature, forming soluble hydroxides having clearly-defined basic properties and the composition RHO, like that of caustic soda. The resemblance between these metals is sometimes seen with striking clearness, especially in compounds such as salts.[1] The corresponding salts of nitric, sulphuric, carbonic, and nearly all acids with these metals have many points in common. The metals which resemble sodium so much in their reactions are termed the _metals of the alkalis_. [1] Tutton's researches (1894) upon the analogy of the crystalline forms of K_{2}SO_{4}, Rb_{2}SO_{4} and Cs_{2}SO_{4} may be taken as a typical example of the comparison of analogous compounds. We cite the following data from these excellent researches: the sp. gr. at 20°/4° of K_{2}SO_{4} is 2·6633 of Rb_{2}SO_{4}, 3·6113, and of Cs_{2}SO_{4}, 4·2434. The coefficient of cubical expansion (the mean between 20° and 60°) for the K salt is 0·0053, for the Rb salt 0·0052, for the Cs salt 0·0051. The linear expansion (the maximum for the vertical axis) along the axis of crystallisation is the same for all three salts, within the limits of experimental error. The replacement of potassium by rubidium causes the distance between the centres of the molecules in the direction of the three axes of crystallisation to increase equally, and less than with the replacement of rubidium by cæsium. The index of refraction for all rays and for every crystalline path (direction) is greater for the rubidium salt than for the potassium salt, and less than for the cæsium salt, and the differences are nearly in the ratio 2 : 5. The lengths of the rhombic crystalline axes for K_{2}SO_{4} are in the ratio 0·5727 : 1 : 0·7418, for Rb_{2}SO_{4}, 0·5723 : 1 : 0·7485, and for Cs_{2}SO_{4}, 0·5712 : 1 : 0·7521. The development of the basic and brachy-pinacoids gradually increases in passing from K to Rb and Cs. The optical properties also follow the same order both at the ordinary and at a higher temperature. Tutton draws the general conclusion that the crystallographic properties of the isomorphic rhombic sulphates R_{2}SO_{4} are a function of the atomic weight of the metals contained in them (_see_ Chapter XV.) Such researches as these should do much towards hastening the establishment of a true molecular mechanics of physico-chemical phenomena. Among the metals of the alkalis, the most widely distributed in nature, after sodium, is _potassium_. Like sodium, it does not appear either in a free state or as oxide or hydroxide, but in the form of salts, which present much in common with the salts of sodium in the manner of their occurrence. The compounds of potassium and sodium in the earth's crust occur as mineral compounds of silica. With silica, SiO_{2}, potassium oxide, like sodium oxide, forms saline mineral substances resembling glass. If other oxides, such as lime, CaO, and alumina, Al_{2}O_{3}, combine with these compounds, glass is formed, a vitreous stony mass, distinguished by its great stability, and its very slight variation under the action of water. It is such complex silicious compounds as these which contain potash (potassium oxide), K_{2}O, or soda (sodium oxide), Na_{2}O, and sometimes both together, silica, SiO_{2}, lime, CaO, alumina, Al_{2}O_{3}, and other oxides, that form the chief mass of rocks, out of which, judging by the direction of the strata, the chief mass of the accessible crust (envelope) of the earth is made up. The primary rocks, like granite, porphyry, &c.,[1 bis] are formed of such crystalline silicious rocks as these. The oxides entering into the composition of these rocks do not form a homogeneous amorphous mass like glass, but are distributed in a series of peculiar, and in the majority of cases crystalline, compounds, into which the primary rocks may be divided. Thus a felspar (orthoclase) in granite contains from 8 to 15 per cent. of potassium, whilst another variety (plagioclase) which also occurs in granite contains 1·2 to 6 per cent. of potassium, and 6 to 12 per cent. of sodium. The mica in granite contains 3 to 10 per cent. of potassium. As already mentioned, and further explained in Chapter XVII., the friable, crumbling, and stratified formations which in our times cover a large part of the earth's surface have been formed from these primary rocks by the action of the atmosphere and of water containing carbonic acid. It is evident that in the chemical alteration of the primary rocks by the action of water, the compounds of potassium, as well as the compounds of sodium, must have been dissolved by the water (as they are soluble in water), and that therefore the compounds of potassium must be accumulated together with those of sodium in sea water. And indeed compounds of potassium are always found in _sea water_, as we have already pointed out (Chapters I. and X.). This forms one of the sources from which they are extracted. After the evaporation of sea water, there remains a mother liquor, which contains potassium chloride and a large proportion of magnesium chloride. On cooling this solution crystals separate out which contain chlorides of magnesium and potassium. A double salt of this kind, called _carnallite_, KMgCl_{3},6H_{2}O, occurs at Stassfurt. This carnallite[2] is now employed as a material for the extraction of potassium chloride, and of all the compounds of this element.[3] Besides which, potassium chloride itself is sometimes found at Stassfurt as _sylvine_.[3 bis] By a method of double saline decomposition, the chloride of potassium may be converted into all the other potassium salts,[4] some of which are of practical use. The potassium salts have, however, their greatest importance as an indispensable component of the food of plants.[5] [1 bis] The origin of the primary rocks has been mentioned in Chapter X., Note 2. [2] Carnallite belongs to the number of double salts which are directly decomposed by water, and it only crystallises from solutions which contain an excess of magnesium chloride. It may be prepared artificially by mixing strong solutions of potassium and magnesium chlorides, when colourless crystals of sp. gr. 1·60 separate, whilst the Stassfurt salt is usually of a reddish tint, owing to traces of iron. At the ordinary temperature sixty-five parts of carnallite are soluble in one hundred parts of water in the presence of an excess of the salt. It deliquesces in the air, forming a solution of magnesium chloride and leaving potassium chloride. The quantity of carnallite produced at Stassfurt is now as much as 100,000 tons a year. [3] The method of separating sodium chloride from potassium chloride has been described in Chapter I. On evaporation of a mixture of the saturated solutions, sodium chloride separates; and then, on cooling, potassium chloride separates, owing to the difference of rate of variation of their solubilities with the temperature. The following are the most trustworthy figures for the solubility of _potassium chloride_ in one hundred parts of water (for sodium chloride, _see_ Chapter X., Note 13):-- 10° 20° 40° 60° 100° 32 35 40 46 57 When mixed with solutions of other salts the solubility of potassium chloride naturally varies, but not to any great extent. [3 bis] The specific gravity of the solid salt is 1·99--that is, less than that of sodium chloride. All the salts of sodium are specifically heavier than the corresponding salts of potassium, as are also their solutions for equal percentage compositions. If the specific gravity of water at 4° = 10,000, then at 15° the specific gravity of a solution of _p_ p.c. potassium chloride = 9,992 + 63·29_p_ + 0·226_p_^2, and therefore for 10 p.c. = 1·0647, 20 p.c. = 1·1348, &c. Potassium chloride combines with iodine trichloride to form a compound KCl + ICl_{3} = KICl_{4}, which has a yellow colour, is fusible, loses iodine trichloride at a red heat, and gives potassium iodate and hydrochloric acid with water. It is not only formed by direct combination, but also by many other methods; for instance, by passing chlorine into a solution of potassium iodide so long as the gas is absorbed, KI + 2Cl_{2} = KCl,ICl_{3}. Potassium iodide, when treated with potassium chlorate and strong hydrochloric acid, also gives this compound; another method for its formation is given by the equation KClO_{3} + I + 6HCl = KCl,ICl_{3} + 3Cl + 3H_{2}O. This is a kind of salt corresponding with KIO_{2} (unknown) in which the oxygen is replaced by chlorine. If valency be taken as the starting-point in the study of chemical compounds, and the elements considered as having a constant atomicity (number of bonds)--that is, if K, Cl, and I be taken as univalent elements--then it is impossible to explain the formation of such a compound because, according to this view, univalent elements are only able to form dual compounds with each other; such as, KCl, ClI, KI, &c., whilst here they are grouped together in the molecule KICl_{4}. Wells, Wheeler, and Penfield (1892) obtained a large number of such poly-haloid salts. They may all be divided into two large classes: the tri-haloid and the penta-haloid salts. They have been obtained not only for K but also for Rb and Cs, and partially also for Na and Li. The general method of their formation consists in dissolving the ordinary halogen salt of the metal in water, and treating it with the requisite amount of free halogen. The poly-haloid salt separates out after evaporating the solution at a more or less low temperature. In this manner, among the tri-haloid salts, may be obtained: KI_{3}, KBr_{2}I, KCl_{2}I, and the corresponding salts of rubidium and cæsium, for instance, CsI_{3}, CsBrI_{2}, CsBr_{2}I, CsClBrI,CsCl_{2}I, CsBr_{3}, CsClBr_{2}, CsCl_{2}Br, and in general MX_{3} where X is a halogen. The colour of the crystals varies according to the halogen, thus CsI_{3} is black, CrBr_{3} yellowish red, CrBrI_{2} reddish brown, CsBr_{2}I red, CsCl_{2}Br yellow. The cæsium salts are the most stable, and those of potassium least so, as also those which contain Br and I separately or together; for cæsium no compounds containing Cl and I were obtained. The penta-haloid salts form a smaller class; among these salts potassium forms KCl_{4}I, rubidium RbCl_{4}I, cæsium CsI_{5}, CsBr, CsCl_{4}I, lithium LiCl_{4}I (with 4H_{2}O) and sodium NaCl_{4}I (with 2H_{2}O). The most stable are those salts containing the metal with the greatest atomic weight--cæsium (_see_ Chapter XI., Note 63). [4] It is possible to extract the compounds of potassium directly from the primary rocks which are so widely distributed over the earth's surface and so abundant in some localities. From a chemical point of view this problem presents no difficulty; for instance, by fusing powdered orthoclase with lime and fluor spar (Ward's method) and then extracting the alkali with water (on fusion the silica gives an insoluble compound with lime), or by treating the orthoclase with hydrofluoric acid (in which case silicon fluoride is evolved as a gas) it is possible to transfer the alkali of the orthoclase to an aqueous solution, and to separate it in this manner from the other insoluble oxides. However, as yet there is no profit in, nor necessity for, recourse to this treatment, as carnallite and potash form abundant materials for the extraction of potassium compounds by cheaper methods. Furthermore, the salts of potassium are now in the majority of chemical reactions replaced by salts of sodium, especially since the preparation of sodium carbonate has been facilitated by the Leblanc process. The replacement of potassium compounds by sodium compounds not only has the advantage that the salts of sodium are in general cheaper than those of potassium, but also that a smaller quantity of a sodium salt is needed for a given reaction than of a potassium salt, because the combining weight of sodium (23) is less than that of potassium (39). [5] It has been shown by direct experiment on the cultivation of plants in artificial soils and in solutions that under conditions (physical, chemical, and physiological) otherwise identical plants are able to thrive and become fully developed in the entire absence of sodium salts, but that their development is impossible without potassium salts. The primary rocks contain an almost equal proportion of potassium and sodium. But in sea water the compounds of the latter metal predominate. It may be asked, what became of the compounds of potassium in the disintegration of the primary rocks, if so small a quantity went to the sea water? They remained with the other products of the decomposition of the primary rocks. When granite or any other similar rock formation is disintegrated, there are formed, besides the soluble substances, also insoluble substances--sand and finely-divided clay, containing water, alumina, and silica. This clay is carried away by the water, and is then deposited in strata. It, and especially its admixture with vegetable remains, retain compounds of potassium in a greater quantity than those of sodium. This has been proved with absolute certainty to be the case, and is due to the _absorptive power of the soil_. If a dilute solution of a potassium compound be filtered through common mould used for growing plants, containing clay and the remains of vegetable decomposition, this mould will be found to have retained a somewhat considerable percentage of the potassium compounds. If a salt of potassium be taken, then during the filtration an equivalent quantity of a salt of calcium--which is also found, as a rule, in soils--is set free. Such a process of filtration through finely divided earthy substances proceeds in nature, and the compounds of potassium are everywhere retained by the friable earth in considerable quantity. This explains the presence of so small an amount of potassium salts in the water of rivers, lakes, streams, and oceans, where the lime and soda have accumulated. The compounds of potassium retained by the friable mass of the earth are absorbed as an aqueous solution by the roots of _plants_. Plants, as everyone knows, when burnt leave an ash, and this ash, besides various other substances, without exception contains compounds of potassium. Many land plants contain a very small amount of sodium compounds,[6] whilst potassium and its compounds occur in all kinds of vegetable ash. Among the generally cultivated plants, grass, potatoes, the turnip, and buckwheat are particularly rich in potassium compounds. The ash of plants, and especially of herbaceous plants, buckwheat straw, sunflower and potato leaves are used in practice for the extraction of potassium compounds. There is no doubt that potassium occurs in the plants themselves in the form of complex compounds, and often as salts of organic acids. In certain cases such salts of potassium are even extracted from the juice of plants. Thus, sorrel and oxalis, for example, contain in their juices the acid oxalate of potassium, C_{2}HKO_{4}, which is employed for removing ink stains. Grape juice contains the so-called cream of tartar, which is the acid tartrate of potassium, C_{4}H_{5}KO_{6}.[7] This salt also separates as a sediment from wine. When the plants, containing one or more of the salts of potassium, are burnt, the carbonaceous matter is oxidised, and in consequence the potassium is obtained in the ash as carbonate, K_{2}CO_{3}, which is generally known as _potashes_. Hence potashes occur ready prepared in the ash of plants, and therefore the ash of land plants is employed as a source for the extraction of potassium compounds. Potassium carbonate is extracted by lixiviating the ash with water.[8] Potassium carbonate may also be obtained from the chloride by a method similar to that by which sodium carbonate is prepared from sodium chloride.[8 bis] There is no difficulty in obtaining any salt of potassium--for example, the sulphate,[9] bromide, and iodide[10]--by the action of the corresponding acid on KCl and especially on the carbonate, whilst the hydroxide, _caustic potash_, KHO, which is in many respects analogous to caustic soda, is easily obtained by means of lime in exactly the same manner in which sodium hydroxide is prepared from sodium carbonate.[11] Therefore, in order to complete our knowledge of the alkali metals, we will only describe two salts of potassium which are of practical importance, and whose analogues have not been described in the preceding chapter, potassium cyanide and potassium nitrate. [6] If herbaceous plants contain much sodium salts, it is evident that these salts mainly come from the sodium compounds in the water absorbed by the plants. [7] As plants always contain mineral substances and cannot thrive in a medium which does not contain them, more especially in one which is free from the salts of the four basic oxides, K_{2}O, CaO, MgO, and Fe_{2}O_{3}, and of the four acid oxides, CO_{2}, N_{2}O_{5}, P_{2}O_{5}, and SO_{3}, and as the amount of ash-forming substances in plants is small, the question inevitably arises as to what part these play in the development of plants. With the existing chemical data only one answer is possible to this question, and it is still only a hypothesis. This answer was particularly clearly expressed by Professor Gustavson of the Petroffsky Agricultural Academy. Starting from the fact (Chapter XI., Note 55) that a small quantity of aluminium renders possible or facilitates the reaction of bromine on hydrocarbons at the ordinary temperature, it is easy to arrive at the conclusion, which is very probable and in accordance with many data respecting the reactions of organic compounds, that the addition of mineral substances to organic compounds lowers the temperature of reaction and in general facilitates chemical reactions in plants, and thus aids the conversion of the most simple nourishing substances into the complex component parts of the plant organism. The province of chemical reactions proceeding in organic substances in the presence of a small quantity of mineral substances has as yet been but little investigated, although there are already several disconnected data concerning reactions of this kind, and although a great deal is known with regard to such reactions among inorganic compounds. The essence of the matter may be expressed thus--two substances, A and B, do not react on each other of their own accord, but the addition of a small quantity of a third particularly active substance, C, produces the reaction of A on B, because A combines with C, forming AC, and B reacts on this new compound, which has a different store of chemical energy, forming the compound AB or its products, and setting C free again or retaining it. It may here be remarked that all the mineral substances necessary for plants (those enumerated at the beginning of the note) are the highest saline compounds of their elements, that they enter into the plants as salts, that the lower forms of oxidation of the same elements (for instance, sulphites and phosphites) are harmful to plants (poisonous), and that strong solutions of the salts assimilated by plants (their osmotic pressure being great and contracting the cells, as De Vries showed, (_see_ Chapter I., Note 19)) not only do not enter into the plants but kill them (poison them). [8] Besides which, it will be understood from the preceding paragraph that the salts of potassium may become exhausted from the soil by long cultivation, and that there may therefore be cases when the direct fertilisation by salts of potassium may be profitable. But manure and animal excrements, ashes, and, in general, nearly all refuse which may serve for fertilising the soil, contain a considerable quantity of potassium salts, and therefore, as regards the natural salts of potassium (Stassfurt), and especially potassium sulphate, if they often improve the crops, it is in all probability due to their action on the properties of the soil. The agriculturist cannot therefore be advised to add potassium salts, without making special experiments showing the advantage of such a fertiliser on a given kind of soil and plant. The animal body also contains potassium compounds, which is natural, since animals consume plants. For example, milk, and especially human milk, contains a somewhat considerable quantity of potassium compounds. Cow's milk, however, does not contain much potassium salt. Sodium compounds generally predominate in the bodies of animals. The excrement of animals, and especially of herbivorous animals, on the contrary, often contains a large proportion of potassium salts. Thus sheep's dung is rich in them, and in washing sheep's wool salts of potassium pass into the water. The ash of tree stems, as the already dormant portion of the plant (Chapter VIII., Note 1), contains little potash. For the extraction of potash, which was formerly carried on extensively in the east of Russia (before the discovery of the Stassfurt salt), the ash of grasses, and the green portions of potatoes, buckwheat, &c., are taken and treated with water (lixiviated), the solution is evaporated, and the residue ignited in order to destroy the organic matter present in the extract. The residue thus obtained is composed of raw potash. It is refined by a second dissolution in a small quantity of water, for the potash itself is very soluble in water, whilst the impurities are sparingly soluble. The solution thus obtained is again evaporated, and the residue ignited, and this potash is then called refined potash, or pearlash. This method of treatment cannot give chemically pure potassium carbonate. A certain amount of impurities remain. To obtain chemically pure potassium carbonate, some other salt of potassium is generally taken and purified by crystallisation. Potassium carbonate crystallises with difficulty, and it cannot therefore be purified by this means, whilst other salts, such as the tartrate, acid carbonate, sulphate, or nitrate, &c., crystallise easily and may thus be directly purified. The tartrate is most frequently employed, since it is prepared in large quantities (as a sediment from wine) for medicinal use under the name of cream of tartar. When ignited without access of air, it leaves a mixture of charcoal and potassium carbonate. The charcoal so obtained being in a finely-divided condition, the mixture (called 'black flux'), is sometimes used for reducing metals from their oxides with the aid of heat. A certain quantity of nitre is added to burn the charcoal formed by heating the cream of tartar. Potassium carbonate thus prepared is further purified by converting it into the acid salt, by passing a current of carbonic anhydride through a strong solution. KHCO_{3} is then formed, which is less soluble than the normal salt (as is also the case with the corresponding sodium salts), and therefore crystals of the acid salt separate from the solution on cooling. When ignited, they part with their water and carbonic anhydride, and pure potassium carbonate remains behind. The physical properties of potassium carbonate distinguish it sufficiently from sodium carbonate; it is obtained from solutions as a powdery white mass, having an alkaline taste and reaction, and, as a rule, shows only traces of crystallisation. It also attracts the moisture of the air with great energy. The crystals do not contain water, but absorb it from the air, deliquescing into a saturated solution. It melts at a red heat (1045°), and at a still higher temperature is even converted into vapour, as has been observed at glass works where it is employed. It is very soluble. At the ordinary temperature, water dissolves an equal weight of the salt. Crystals containing two equivalents of water separate from such a saturated solution when strongly cooled (Morel obtained K_{2}CO_{3}3H_{2}O in well-formed crystals at +10°). There is no necessity to describe its reactions, because they are all analogous to those of sodium carbonate. When manufactured sodium carbonate was but little known, the consumption of potassium carbonate was very considerable, and even now washing soda is frequently replaced for household purposes by 'lye'--_i.e._ an aqueous solution obtained from ashes. It contains potassium carbonate, which acts like the sodium salt in washing tissues, linen, &c. A mixture of potassium and sodium carbonates fuses with much greater ease than the separate salts, and a mixture of their solutions gives well-crystallised salts--for instance (Marguerite's salt), K_{2}CO_{3},6H_{2}O,2Na_{2}CO_{3},6H_{2}O. Crystallisation also occurs in other multiple proportions of K and Na (in the above case 1 : 2, but 1 : 1 and 1 : 3 are known), and always with 6 mol. H_{2}O. This is evidently a combination _by similarity_, as in alloys, solutions, &c. [8 bis] About 25,000 tons of potash annually are now prepared from KCl by this method at Stassfurt. [9] _Potassium sulphate_, K_{2}SO_{4}, crystallises from its solutions in an anhydrous condition, in which respect it differs from the corresponding sodium salt, just as potassium carbonate differs from sodium carbonate. In general, it must be observed that the majority of sodium salts combine more easily with water of crystallisation than the potassium salts. The solubility of _potassium sulphate_ does not show the same peculiarities as that of sodium sulphate, because it does not combine with water of crystallisation; at the ordinary temperature 100 parts of water dissolve about 10 parts of the salt, at 0° 8·3 parts, and at 100° about 26 parts. _The acid sulphate_, KHSO_{4}, obtained easily by heating crystals of the normal salt with sulphuric acid, is frequently employed in chemical practice. On heating the mixture of acid and salt, fumes of sulphuric acid are at first given off; when they cease to be evolved, the acid salt is contained in the residue. At a higher temperature (of above 600°) the acid salt parts with all the acid contained in it, the normal salt being re-formed. The definite composition of this acid salt, and the ease with which it decomposes, render it exceedingly valuable for certain chemical transformations accomplished by means of sulphuric acid at a high temperature, because it is possible to take, in the form of this salt, a strictly definite quantity of sulphuric acid, and to cause it to act on a given substance at a high temperature, which it is often necessary to do, more especially in chemical analysis. In this case, the acid salt acts in exactly the same manner as sulphuric acid itself, but the latter is inefficient at temperatures above 400°, because it all evaporates, while at that temperature the acid salt still remains in a fused state, and acts with the elements of sulphuric acid on the substance taken. Hence by its means the boiling-point of sulphuric acid is raised. Thus the acid potassium sulphate is employed, where for conversion of certain oxides, such as those of iron, aluminium, and chromium, into salts, a high temperature is required. Weber, by heating potassium sulphate with an excess of sulphuric acid at 100°, observed the formation of a lower stratum, which was found to contain a definite compound containing eight equivalents of SO_{3} per equivalent of K_{2}O. The salts of rubidium, cæsium, and thallium give a similar result, but those of sodium and lithium do not. (_See_ Note 1.) [10] The _bromide_ and _iodide_ of potassium are used, like the corresponding sodium compounds, in medicine and photography. Potassium iodide is easily obtained in a pure state by saturating a solution of hydriodic acid with caustic potash. In practice, however, this method is rarely had recourse to, other more simple processes being employed although they do not give so pure a product. They aim at the direct formation of hydriodic acid in the liquid in the presence of potassium hydroxide or carbonate. Thus iodine is thrown into a solution of pure potash, and hydrogen sulphide passed through the mixture, the iodine being thus converted into hydriodic acid. Or a solution is prepared from phosphorus, iodine, and water, containing hydriodic and phosphoric acid; lime is then added to this solution, when calcium iodide is obtained in solution, and calcium phosphate as a precipitate. The solution of calcium iodide gives, with potassium carbonate, insoluble calcium carbonate and a solution of potassium iodide. If iodine is added to a slightly-heated solution of caustic potash (free from carbonate--that is, freshly prepared), so long as the solution is not coloured from the presence of an excess of iodine, there is formed (as in the action of chlorine on a solution of caustic potash) a mixture of potassium iodide and iodate. On evaporating the solution thus obtained and igniting the residue, the iodate is destroyed and converted into iodide, the oxygen being disengaged, and potassium iodide only is left behind. On dissolving the residue in water and then evaporating, cubical crystals of the anhydrous salt are obtained, which are soluble in water and alcohol, and on fusion give an alkaline reaction, owing to the fact that when ignited a portion of the salt decomposes, forming potassium oxide. The neutral salt may be obtained by adding hydriodic acid to this alkaline salt until it gives an acid reaction. It is best to add some finely-divided charcoal to the mixture of iodate and iodide before igniting it, as this facilitates the evolution of the oxygen from the iodate. The iodate may also be converted into iodide by the action of certain reducing agents, such as zinc amalgam, which when boiled with a solution containing an iodate converts it into iodide. Potassium iodide may also be prepared by mixing a solution of ferrous iodide (it is best if the solution contain an excess of iodine) and potassium carbonate, in which case ferrous carbonate FeCO_{3}, is precipitated (with an excess of iodine the precipitate is granular, and contains a compound of the suboxide and oxide of iron), while potassium iodide remains in solution. Ferrous iodide, FeI_{2}, is obtained by the direct action of iodine on iron in water. Potassium iodide considerably lowers the temperature (by 24°), when it dissolves in water, 100 parts of the salt dissolve in 73·5 parts of water at 12·5°, in 70 parts at 18°, whilst the saturated solution which boils at 120° contains 100 parts of salt per 45 parts of water. Solutions of potassium iodide dissolve a considerable amount of iodine; strong solutions even dissolving as much or more iodine than they contain as potassium iodide (_see_ Note 3 bis and Chapter XI., Note 64). [11] Caustic potash is not only formed by the action of lime on dilute solutions of potassium carbonate (as sodium hydroxide is prepared from sodium carbonate), but by igniting potassium nitrate with finely-divided copper (_see_ Note 15), and also by mixing solutions of potassium sulphate (or even of alum, KAlS_{2}O_{8}) and barium hydroxide, BaH_{2}O_{2}. It is sometimes purified by dissolving it in alcohol (the impurities, for example, potassium sulphate and carbonate, are not dissolved) and then evaporating the alcohol. The specific gravity of potassium hydroxide is 2·04, but that of its solutions (see Chapter XII., Note 18) at 15° S = 9,992 + 90·4_p_ + 0·28_p_^2 (here _p_^2 is +, and for sodium hydroxide it is-). Strong solutions, when cooled, yield a crystallo-hydrate, KHO,4H_{2}O, which dissolves in water, producing cold (like 2NaHO,7H_{2}O), whilst potassium hydroxide in solution develops a considerable amount of heat. _Potassium cyanide_, which presents in its chemical relations a certain analogy with the halogen salts of potassium, is not only formed according to the equation, KHO + HCN = H_{2}O + KCN, but also whenever a nitrogenous carbon compound--for instance, animal matter--is heated in the presence of metallic potassium, or of a compound of potassium, and even when a mixture of potash and carbon is heated in a stream of nitrogen. Potassium cyanide is obtained from yellow prussiate, which has been already mentioned in Chapter IX., and whose preparation on a large scale will be described in Chapter XXII. If the yellow prussiate be ground to a powder and dried, so that it loses its water of crystallisation, it then melts at a red heat, and decomposes into carbide of iron, nitrogen, and potassium cyanide, FeK_{4}C_{6}N_{6} = 4KCN + FeC_{2} + N_{2}. After the decomposition it is found that the yellow salt has been converted into a white mass of potassium cyanide. The carbide of iron formed collects at the bottom of the vessel. If the mass thus obtained be treated with water, the potassium cyanide is partially decomposed by the water, but if it be treated with alcohol, then the cyanide is dissolved, and on cooling separates in a crystalline form.[12] A solution of potassium cyanide has a powerfully alkaline reaction, a smell like that of bitter almonds, peculiar to prussic acid, and acts as a most powerful poison. Although exceedingly stable in a fused state, potassium cyanide easily changes when in solution. Prussic acid is so very feebly energetic that even water decomposes potassium cyanide. A solution of the salt, even without access of air, easily turns brown and decomposes, and when heated evolves ammonia and forms potassium formate; this is easily comprehensible from the representation of the cyanogen compounds which was developed in Chapter IX., KCN + 2H_{2}O = CHKO_{2} + NH_{3}. Furthermore, as carbonic anhydride acts on potassium cyanide with evolution of prussic acid, and as potassium cyanate, which is also unstable, is formed by the action of air, it will be easily seen that solutions of potassium cyanide are very unstable. Potassium cyanide, containing as it does carbon and potassium, is a substance which can act in a very vigorously reducing manner, especially when fused; it is therefore used as a powerful reducing agent at a red heat.[13] The property of potassium cyanide of giving double salts with other cyanides is very clearly shown by the fact that many metals dissolve in a solution of potassium cyanide, with the evolution of hydrogen. For example, iron, copper, and zinc act in this manner. Thus-- 4KCN + 2H_{2}O + Zn = K_{2}ZnC_{4}N_{4} + 2KHO + H_{2} [12] When the yellow prussiate is heated to redness, all the cyanogen which was in combination with the iron is decomposed into nitrogen, which is evolved as gas, and carbon, which combines with the iron. In order to avoid this, potassium carbonate is added to the yellow prussiate while it is being fused. A mixture of 8 parts of anhydrous yellow prussiate and 3 parts of pure potassium carbonate is generally taken. Double decomposition then takes place, resulting in the formation of ferrous carbonate and potassium cyanide. But by this method, as by the first, a pure salt is not obtained, because a portion of the potassium cyanide is oxidised at the expense of the iron carbonate and forms potassium cyanate, FeCO_{3} + KCN = CO_{2} + Fe + KCNO; and the potassium cyanide very easily forms oxide, which acts on the sides of the vessel in which the mixture is heated (to avoid this iron vessels should be used). By adding one part of charcoal powder to the mixture of 8 parts of anhydrous yellow prussiate and 3 parts of potassium carbonate a mass is obtained which is free from cyanate, because the carbon absorbs the oxygen, but in that case it is impossible to obtain a colourless potassium cyanide by simple fusion, although this may be easily done by dissolving it in alcohol. Cyanide of potassium may also be obtained from potassium thiocyanate, which is formed from ammonium thiocyanate obtained by the action of ammonia upon bisulphide of carbon (_see_ works upon Organic Chemistry). Potassium cyanide is now prepared in large quantities from yellow prussiate for gilding and silvering. When fused in large quantities the action of the oxygen of the air is limited, and with great care the operation may be successfully conducted, and therefore, on a large scale, very pure salt is sometimes obtained. When slowly cooled, the fused salt separates in cubical crystals like potassium chloride. Pure KCN is obtained by passing CNH gas into an alcoholic solution of KHO. The large amount of potassium cyanide which is now required for the extraction of gold from its ores, is being replaced by a mixture (Rossler and Gasslaker, 1892) of KCN and NaCN, prepared by heating powdered and dried yellow prussiate with metallic sodium: K_{4}Fe(CN)_{6} + 2Na = 4KCN + 2NaCN + Fe. This method offers two advantages over the above methods: (1) the whole of the cyanide is obtained, and does not decompose with the formation of N_{2}; and (2) no cyanates are formed, as is the case when carbonate of potash is heated with the prussiate. [13] A considerable quantity of potassium cyanide is used in the arts, more particularly for the preparation of metallic solutions which are decomposed by the action of a galvanic current; thus it is very frequently employed in electro-silvering and gilding. An alkaline solution is prepared, which is moderately stable owing to the fact that potassium cyanide in the form of certain double salts--that is, combined with other cyanides--is far more stable than when alone (yellow prussiate, which contains potassium cyanide in combination with ferrous cyanide, is an example of this). Gold and silver are soluble in potassium cyanide in the presence of air, in which case the hydrogen, which would otherwise be evolved in the reaction, combines with the oxygen of the air, forming water (Eissler, MacLaurin, 1893), for example, 4Au + 4KCN + O + H_{2}O = 2AuKC_{2}N_{2} + 2KHO, which is taken advantage of for extracting gold from its ores (Chapter XXIV.).[13 bis] Platinum, mercury, and tin are not dissolved in a solution of potassium cyanide, even with access of air. [13 bis] A dilute solution of KCN is taken, not containing more than 1 per cent. KCN. MacLaurin explains this by the fact that strong solutions dissolve gold less rapidly, owing to their dissolving less air, whose oxygen is necessary for the reaction. _Potassium nitrate_, or common _nitre_ or _saltpetre_, KNO_{3}, is chiefly used as a component part of gunpowder, in which it cannot be replaced by the sodium salt, because the latter is deliquescent. It is necessary that the nitre in gunpowder should be perfectly pure, as even small traces of sodium, magnesium, and calcium salts, especially chlorides, render the nitre and the gunpowder capable of attracting moisture. Nitre may easily be obtained pure, owing to its great disposition to form crystals both large and small, which aids its separation from other salts. The considerable differences between the solubility of nitre at different temperatures aids this crystallisation. A solution of nitre saturated at its boiling point (116°) contains 335 parts of nitre to 100 parts of water, whilst at the ordinary temperature--for instance, 20°--the solution is only able to retain 32 parts of the salt. Therefore, in the preparation and refining of nitre, its solution, saturated at the boiling point, is cooled, and nearly all the nitre is obtained in the form of crystals. If the solution be quietly and slowly cooled in large quantities then large crystals are formed, but if it be rapidly cooled and agitated then small crystals are obtained. In this manner, if not all, at all events the majority, of the impurities present in small quantities remain in the mother liquor. If an unsaturated solution of nitre be rapidly cooled, so as to prevent the formation of large crystals (in whose crevices the mother liquor, together with the impurities, would remain), the very minute crystals of nitre known as saltpetre flour are obtained. Common nitre occurs in nature, but only in small quantities in admixture with other nitrates, and especially with sodium, magnesium, and calcium nitrates. Such a mixture of salts of nitric acid is formed in nature in fertile earth, and in those localities where, as in _the soil_, nitrogenous organic remains are decomposed in the presence of alkalis or alkaline bases with free access of air. This method of the formation of nitrates requires moisture, besides the free access of air, and takes place principally during warm weather.[14] In warm countries, and in temperate climates during the summer months, fertile soils produce a small quantity of nitre. In this respect India is especially known as affording a considerable supply of nitre extracted from the soil. The nitre-bearing soil after the rainy season sometimes becomes covered during the summer with crystals of nitre, formed by the evaporation of the water in which it was previously dissolved. This soil is collected, subjected to repeated lixiviations, and treated for nitre as will be presently described. In temperate climates nitrates are obtained from the lime rubbish of demolished buildings which have stood for many years, and especially from those portions which have been in contact with the ground. The conditions there are very favourable for the formation of nitre, because the lime used as a cement in buildings contains the base necessary for the formation of nitrates, while the excrement, urine, and animal refuse are sources of nitrogen. By the methodical lixiviation of this kind of rubbish a solution of nitrogenous salts is formed similar to that obtained by the lixiviation of fertile soil. A similar solution is also obtained by the lixiviation of the so-called _nitre plantations_. They are composed of manure interlaid with brushwood, and strewn over with ashes, lime, and other alkaline rubbish. These nitre plantations are set up in those localities where the manure is not required for the fertilisation of the soil, as, for example, in the south-eastern 'black earth' Governments of Russia. The same process of oxidation of nitrogenous matter freely exposed to air and moisture during the warm season in the presence of alkalis takes place in nitre plantations as in fertile soil and in the walls of buildings. From all these sources there is obtained a solution containing various salts of nitric acid mixed with soluble organic matter. The simplest method of treating this impure solution of nitre is to add a solution of potassium carbonate, or to simply treat it with ashes containing this substance. The potassium carbonate enters into double decomposition with the calcium and magnesium salts, forming insoluble carbonates of these bases and leaving the nitre in solution. Thus, for instance, K_{2}CO_{3} + Ca(NO_{3})_{2} = 2KNO_3 + CaCO_{3}. Both calcium and magnesium carbonates are insoluble, and therefore after treatment with potassium carbonate the solution no longer contains salts of these metals but only the salts of sodium and potassium together with organic matter. The latter partially separates on heating in an insoluble form, and is entirely destroyed by heating the nitre to a low red heat. The nitre thus obtained is easily purified by repeated crystallisation. The greater part of the nitre used for making gunpowder is now obtained from the sodium salt _Chili saltpetre_ or _cubic nitre_, which occurs in nature, as already mentioned. The conversion of this salt into common nitre is also carried on by means of a double decomposition. This is done either by adding potassium carbonate (when, on mixing the strong and hot solutions, sodium carbonate is directly obtained as a precipitate), or, as is now most frequent, potassium chloride. When a mixture of strong solutions of potassium chloride and sodium nitrate is evaporated, sodium chloride first separates, because this salt, which is formed by the double decomposition KCl + NaNO_{3} = KNO_{3} + NaCl, is almost equally soluble in hot and cold water; on cooling, therefore, a large amount of potassium nitrate separates from the saturated solution, while the sodium chloride remains dissolved. The nitre is ultimately purified by recrystallisation and by washing with a saturated solution of nitre, which cannot dissolve a further quantity of nitre but only the impurities. [14] Besides which Schloesing and Müntz, by employing similar methods to Pasteur, showed that the formation of nitre in the decomposition of nitrogenous substances is accomplished by the aid of peculiar micro-organisms (ferments), without which the simultaneous action of the other necessary conditions (alkalis, moisture, a temperature of 37°, air, and nitrogenous substances) cannot give nitre. Nitre is a colourless salt having a peculiar cool taste. It crystallises easily in long striated six-sided rhombic prisms terminating in rhombic pyramids. Its crystals (sp. gr. 1·93) do not contain water, but their cavities generally contain a certain quantity of the solution from which they have crystallised. For this reason in refining nitre, the production of large crystals is prevented, _saltpetre flour_ being prepared. At a low red heat (339°) nitre melts to a colourless liquid.[14 bis] Potassium nitrate at the ordinary temperature and in a solid form is inactive and stable, but _at a high temperature_ it acts as a powerful _oxidising agent_, giving up a considerable amount of oxygen to substances mixed with it.[15] When thrown on to incandescent charcoal it brings about its rapid combustion, and a mechanical mixture of powdered charcoal and nitre ignites when brought into contact with a red-hot substance, and continues to burn by itself. In this action, nitrogen is evolved, and the oxygen oxidises the charcoal, in consequence of which potassium carbonate and carbonic anhydride are formed: 4KNO_{3} + 5C = 2K_{2}CO_{3} + 3CO_{2} + 2N_{2}. This phenomenon depends on the fact that oxygen in combining with carbon evolves more heat than it does in combining with nitrogen. Hence, when once the combustion has been started at the expense of the nitre, it is able to go on without requiring the aid of external heat. A similar oxidation or combustion at the expense of the contained oxygen takes place when nitre is heated with different combustible substances. If a mixture of sulphur and nitre be thrown upon a red-hot surface, the sulphur burns, forming potassium sulphate and sulphurous anhydride. In this case, also, the nitrogen of the nitre is evolved as gas: 2KNO_{3} + 2S = K_{2}SO_{4} + N_{2} + SO_{2}. A similar phenomenon occurs when nitre is heated with many metals. The oxidation of those metals which are able to form acid oxides with an excess of oxygen is especially remarkable. In this case they remain in combination with potassium oxide as potassium salts. Manganese, antimony, arsenic, iron, chromium, &c. are instances of this kind. These elements, like carbon and sulphur, displace free nitrogen. The lower oxides of these metals when fused with nitre pass into the higher oxides. Organic substances are also oxidised when heated with nitre--that is, they burn at the expense of the nitre. It will be readily understood from this that nitre is frequently used in practical chemistry and the arts as an oxidising agent at high temperatures. Its application in _gunpowder_ is based on this property; gunpowder consists of a mechanical mixture of finely-ground sulphur, nitre, and charcoal. The relative proportion of these substances varies according to the destination of the powder and to the kind of charcoal employed (a friable, incompletely-burnt charcoal, containing therefore hydrogen and oxygen, is employed). Gases are formed in its combustion, chiefly nitrogen and carbonic anhydride, which create a considerable pressure if their escape be in any way impeded. This action of gunpowder may be expressed by the equation: 2KNO_{3} + 3C + S = K_{2}S + 3CO_{2} + N_{2}. [14 bis] Before fusing, the crystals of potassium nitrate change their form, and take the same form as sodium nitrate--that is, they change into rhombohedra. Nitre crystallises from hot solutions, and in general under the influence of a rise of temperature, in a different form from that given at the ordinary or lower temperatures. Fused nitre solidifies to a radiated crystalline mass; but it does not exhibit this structure if metallic chlorides be present, so that this method may be taken advantage of to determine the degree of purity of nitre. Carnelley and Thomson (1888) determined the fusing point of mixtures of potassium and sodium nitrates. The first salt fuses at 339° and the second at 316°, and if _p_ be the percentage amount of potassium nitrate, then the results obtained were-- _p_ = 10 20 30 40 50 60 70 80 90 298° 283° 268° 242° 231° 231° 242° 284° 306° which confirms Shaffgotsch's observation (1857) that the lowest fusing point (about 231°) is given by mixing molecular quantities (_p_ = 54·3) of the salts--that is, in the formation of the alloy, KNO_{3},NaNO_{3}. A somewhat similar result was discovered by the same observers for the solubility of mixtures of these salts at 20° in 100 parts of water. Thus, if _p_ be the weight of potassium nitrate mixed with 100-_p_ parts by weight of sodium nitrate taken for solution, and _c_ be the quantity of the mixed salts which dissolves in 100, the solubility of sodium nitrate being 85, and of potassium nitrate 34, parts in 100 parts of water, then-- _p_ = 10 20 30 40 50 60 70 80 90 _c_ = 110 136 136 138 106 81 73 54 41 The maximum solubility proved not to correspond with the most fusible mixture, but to one much richer in sodium nitrate. Both these phenomena show that in homogeneous liquid mixtures the chemical forces that act between substances are the same as those that determine the molecular weights of substances, even when the mixture consists of such analogous substances as potassium and sodium nitrates, between which there is no direct chemical interchange. It is instructive to note also that the maximum solubility does not correspond with the minimum fusing point, which naturally depends on the fact that in solution a third substance, namely water, plays a part, although an attraction between the salts, like that which exists between sodium and potassium carbonates (Note 8), also partially acts. [15] Fused nitre, with a further rise of temperature, disengages oxygen and then nitrogen. The nitrite KNO_{2} is first formed and then potassium oxide. The admixture of certain metals--for example, of finely-divided copper--aids the last decomposition. The oxygen in this case naturally passes over to the metal. It is found by this equation that gunpowder should contain thirty-six parts of charcoal (13·3 p.c.), and thirty-two parts (11·9 p.c.) of sulphur, to 202 parts (74·8 p.c.) of nitre, which is very near to its actual composition.[16] [16] In China, where the manufacture of gunpowder has long been carried on, 75·7 parts of nitre, 14·4 of charcoal, and 9·9 of sulphur are used. Ordinary powder for sporting purposes contains 80 parts of nitre, 12 of charcoal, and 8 of sulphur, whilst the gunpowder used in heavy ordnance contains 75 of nitre, 15 of charcoal, and 10 of sulphur. Gunpowder explodes when heated to 300°, when struck, or by contact with a spark. A compact or finely-divided mass of gunpowder burns slowly and has but little disruptive action, because it burns gradually. To act properly the gunpowder must have a definite rate of combustion, so that the pressure should increase during the passage of the projectile along the barrel of the fire-arm. This is done by making the powder in large granules or in the shape of six-sided prisms with holes through them (prismatic powder). The products of combustion are of two kinds: (1) gases which produce the pressure and are the cause of the dynamical action of gunpowder, and (2) a solid residue, usually of a black colour owing to its containing unburnt particles of charcoal. Besides charcoal, the residue generally contains potassium sulphide, K_{2}S, and a whole series of other salts--for instance, carbonate and sulphate. It is apparent from this that the combustion of gunpowder is not so simple as it appears to be from the above formula, and hence the weight of the residue is also greater than indicated by that formula. According to the formula, 270 parts of gunpowder give 110 parts of residue--that is, 100 parts of powder give 37·4 parts of residue, K_{2}S, whilst in reality the weight of the residue varies from 40 p.c. to 70 p.c. (generally 52 p.c.). This difference depends on the fact that so much oxygen (of the nitre) remains in the residue, and it is evident that if the residue varies the composition of the gases evolved by the powder will vary also, and therefore the entire process will be different in different cases. The difference in the composition of the gases and residue depends, as the researches of Gay-Lussac, Shishkoff and Bunsen, Nobel and Abel, Federoff, Debus, &c., show, on the conditions under which the combustion of the powder proceeds. When gunpowder burns in an open space, the gaseous products which are formed do not remain in contact with the residue, and then a considerable portion of the charcoal entering into the composition of the powder remains unburnt, because the charcoal burns after the sulphur at the expense of the oxygen of the nitre. In this extreme case the commencement of the combustion of the gunpowder may be expressed by the equation, 2KNO_{3} + 3C + S = 2C + K_{2}SO_{4} + CO_{2} + N_{2}. The residue in a blank cartridge often consists of a mixture of C, K_{2}SO_{4}, K_{2}CO_{3}, and K_{2}S_{2}O_{3}. If the combustion of the gunpowder be impeded--if it take place in a cartridge in the barrel of a gun--the quantity of potassium sulphate will first be diminished, then the amount of sulphite, whilst the amount of carbonic anhydride in the gases and the amount of potassium sulphide in the residue will increase. The quantity of charcoal entering into the action will then be also increased, and hence the amount in the residue will decrease. Under these circumstances the weight of the residue will be less--for example, 4K_{2}CO_{3} + 4S = K_{2}SO_{4} + 3K_{2}S + 4CO_{2}. Besides which, carbonic oxide has been found in the gases, and potassium bisulphide, K_{2}S_{2}, in the residue of gunpowder. The amount of potassium sulphide, K_{2}S, increases with the completeness of the combustion, and is formed in the residue at the expense of the potassium sulphite. In recent times the knowledge of the action of gunpowder and other explosives has made much progress, and has developed into a vast province of artillery science, which, guided by the discoveries of chemistry, has worked out a 'smokeless powder' which burns without leaving a residue, and does not therefore give any 'powder smoke' (to hinder the rapidity of firing and aiming), and at the same time disengages a greater volume of gas and consequently gives (under proper conditions of combustion) the possibility of communicating to the charge a greater initial velocity, and therefore greater distance, force, and accuracy of aim. Such 'smokeless powder' is prepared either from the varieties of nitrocellulose (Chapter VI., Note 37) or from a mixture of them with nitro-glycerine (_ibid_). In burning they give, besides steam and nitrogen, generally a large amount of oxide of carbon (this is a very serious drawback in all the present forms of smokeless powder, because carbonic oxide is poisonous), and also CO_{2}, H_{2}, &c. _Metallic potassium_ was obtained like sodium; first by the action of a galvanic current, then by reduction of the hydroxide by means of metallic iron, and lastly, by the action of charcoal on the carbonate at a high temperature. The behaviour of metallic potassium differs, however, from that of sodium, because it easily combines with carbonic oxide, forming an explosive and inflammable mass.[17] [17] The substances obtained in this case are mentioned in Chapter IX., Note 31. Potassium is quite as volatile as sodium, if not more so. At the ordinary temperature potassium is even softer than sodium; its freshly-cut surfaces present a whiter colour than sodium, but, like the latter, and with even greater ease, it oxidises in moist air. It is brittle at low temperatures, but is quite soft at 25°, and melts at 58°. At a low red heat (667°, Perkin) it distils without change, forming a green vapour, whose density,[18] according to A. Scott (1887), is equal to 19 (if that of hydrogen = 1). This shows that the molecule of potassium (like that of sodium, mercury, and zinc) contains but one atom. This is also the case with many other metals, judging by recent researches.[19] The specific gravity of potassium at 15° is 0·87, and is therefore less than that of sodium, as is also the case with all its compounds.[20] Potassium decomposes water with great ease at the ordinary temperature, evolving 45,000 heat units per atomic weight in grams. The heat evolved is sufficient to inflame the hydrogen, the flame being coloured violet from the presence of particles of potassium.[21] [18] A. Scott (1887) determined the vapour densities of many of the alkali elements and their compounds in a platinum vessel heated in a furnace and previously filled with nitrogen. But these, the first data concerning a subject of great importance, have not yet been sufficiently fully described, nor have they received as much attention as could be desired. Taking the density of hydrogen as unity, Scott found the vapour densities of the following substances to be-- Na 12·75 (11·5). KI 92 (84). K 19 (19·5). RbCl 70 (60). CsCl 89·5 (84·2). CsI 133 (130). FeCl_{3} 68. AgCl 80 (71·7). In brackets are given the densities corresponding with the formulæ, according to Avogadro-Gerhardt's law. This figure is not given for FeCl_{3}, because in all probability under these conditions (the temperature at which it was determined) a portion of the FeCl_{3} was decomposed. If it was not decomposed, then a density 81 would correspond with the formula FeCl_{3}, and if the decomposition were Fe_{2}Cl_{6} = 2FeCl_{2} + Cl_{2}, then the density should be 54. With regard to the silver chloride, there is reason to think that the platinum decomposed this salt. The majority of Scott's results so closely correspond with the formulæ that a better concord cannot be expected in such determinations. V. Meyer (1887) gives 93 as the density of KI. [19] The molecules of non-metals are more complex--for instance, H_{2}, O_{3}, Cl_{2}, &c. But arsenic, whose superficial appearance recalls that of metals, but whose chemical properties approach more nearly to the non-metals, has a complex molecule containing As_{4}. [20] As the atomic weight of potassium is greater than that of sodium, the volumes of the molecules, or the quotients of the molecular weight by the specific gravity, for potassium compounds are greater than those of sodium compounds, because both the denominator and numerator of the fraction increase. We cite for comparison the volumes of the corresponding compounds-- Na 24 NaHO 18 NaCl 28 NaNO_{3} 37 Na_{2}SO_{4} 54 K 45 KHO 27 KCl 39 KNO_{3} 48 K_{2}SO_{4} 66 [21] The same precautions must be taken in decomposing water by potassium as have to be observed with sodium (Chapter II., Note 8). It must be observed that potassium decomposes carbonic anhydride and carbonic oxide when heated, the carbon being liberated and the oxygen taken up by the metal, whilst on the other hand charcoal takes up oxygen from potassium, as is seen from the preparation of potassium by heating potash with charcoal, hence the reaction K_{2}O + C = K_{2} + CO is reversible and the relation is the same in this case as between hydrogen and zinc. With regard to the relation of potassium to hydrogen and oxygen, it is closely analogous to sodium in this respect. Thus, with hydrogen it forms potassium hydride, K_{2}H (between 200° and 411°), and with oxygen it gives a suboxide K_{4}O, oxide K_{2}O, and peroxide, only more oxygen enters into the composition of the latter than in sodium peroxide; potassium peroxide contains KO_{2}, but it is probable that in the combustion of potassium an oxide KO is also formed. Potassium, like sodium, is soluble in mercury.[22] In a word, the relation between sodium and potassium is as close as that between chlorine and bromine, or, better still, between fluorine and chlorine, as the atomic weight of sodium, 23, is as much greater than that of fluorine, 19, as that of potassium, 39, is greater than that of chlorine, 35·5. [22] _Potassium_ forms _alloys with sodium_ in all proportions. The alloys containing 1 and 3 equivalents of potassium to one equivalent of sodium are _liquids_, like mercury at the ordinary temperature. Joannis, by determining the amount of heat developed by these alloys in decomposing water, found the evolution for Na_{2}K, NaK, NaK_{2} and NaK_{3} to be 44·5, 44·1, 43·8 and 44·4 thousand heat units respectively (for Na 42·6 and for K 45·4). The formation of the alloy NaK_{2} is therefore accompanied by the development of heat, whilst the other alloys may be regarded as solutions of potassium or sodium in this alloy. In any case a fall of the temperature of fusion is evident in this instance as in the alloys of nitre (Note 14). The liquid alloy NaK_{2} is now used for filling thermometers employed for temperatures above 360°, when mercury boils. The resemblance between _potassium_ and _sodium_ is so great that _their compounds_ can only be easily _distinguished_ in the form of certain of their salts. For instance, the acid potassium tartrate, C_{4}H_{5}KO_{6} (cream of tartar), is distinguished by its sparing solubility in water and in alcohol, and in a solution of tartaric acid, whilst the corresponding sodium salt is easily soluble. Therefore, if a solution of tartaric acid be added in considerable excess to the solutions of the majority of potassium salts, a precipitate of the sparingly-soluble acid salt is formed, which does not occur with salts of sodium. The chlorides KCl and NaCl in solutions easily give double salts K_{2}PtCl_{6} and Na_{2}PtCl_{6}, with platinic chloride, PtCl_{4}, and the solubility of these salts is very different, especially in a mixture of alcohol and ether. The sodium salt is easily soluble, whilst the potassium salt is insoluble or almost so, and therefore the reaction with platinic chloride is that most often used for the separation of potassium from sodium, as is more fully described in works on analytical chemistry. It is possible to discover the least traces of these metals in admixture together, by means of their property of imparting different colours to _a flame_. The presence of a salt of sodium in a flame is recognised by a brilliant yellow coloration, and a pure potassium salt colours a colourless flame violet. However, in the presence of a sodium salt the pale violet coloration given by a potassium salt is quite undistinguishable, and it is at first sight impossible in this case to discover the potassium salt in the presence of that of sodium. But by decomposing the light given by a flame coloured by these metals or a mixture of them, by means of a prism, they are both easily distinguishable, because the yellow light emitted by the sodium salt depends on a group of light rays having a definite index of refraction which corresponds with the yellow portion of the solar spectrum, having the index of refraction of the Fraunhofer line (strictly speaking, group of lines) D, whilst the salts of potassium give a light from which these rays are entirely absent, but which contain rays of a red and violet colour. Therefore, if a potassium salt occur in a flame, on decomposing the light (after passing it through a narrow slit) by means of a prism, there will be seen red and violet bands of light situated at a considerable distance from each other; whilst if a sodium salt be present a yellow line will also appear. If both metals simultaneously occur in a flame and emit light, the spectrum lines corresponding to the potassium and the sodium will appear simultaneously. [Illustration: FIG. 72.--Spectroscope. The prism and table are covered with an opaque cover. The spectrum obtained from the flame coloured by a substance introduced on the wire is viewed through B. A light is placed before the scale D in order to illuminate the image of the scale reflected through B by the side of the prism.] For convenience in carrying on this kind of testing, _spectroscopes_ (fig. 72) are constructed,[23] consisting of a refracting prism and three tubes placed in the plane of the refracting angle of the prism. One of the tubes, C, has a vertical slit at the end, giving access to the light to be tested, which then passes into the tube (collimator), containing a lens which gives the rays a parallel direction. The rays of light having passed through the slit, and having become parallel, are refracted and dispersed in the prism, and the spectrum formed is observed through the eye-piece of the other telescope B. The third tube D contains a horizontal transparent scale (at the outer end) which is divided into equal divisions. The light from a source such as a gas burner or candle placed before this tube, passes through the scale, and is reflected on that face of the prism which stands before the telescope B, so that the image of the scale is seen through this telescope simultaneously with the spectrum given by the rays passing through the slit of the tube C. In this manner the image of the scale and the spectrum given by the source of light under investigation are seen simultaneously. If the sun's rays be directed through the slit of the tube C, then the observer looking through the eye-piece of B will see the solar spectrum, and (if the aperture of the slit be narrow and the apparatus correctly adjusted) the dark Fraunhofer lines in it.[24] Small-sized spectroscopes are usually so adjusted that (looking through B) the violet portion of the spectrum is seen to the right and the red portion to the left, and the Fraunhofer line D (in the bright yellow portion of the spectrum) is situated on the 50th division of the scale.[25] If the light emitted by an incandescent solid--for example, the Drummond light--be passed through the spectroscope, then all the colours of the solar spectrum are seen, but not the Fraunhofer lines. To observe the result given by a flame coloured by various salts a Bunsen gas burner (or the pale flame of hydrogen gas issuing from a platinum orifice) giving so pale a flame that its spectrum will be practically invisible is placed before the slit. If any compound of sodium be placed in the flame of the gas burner (for which purpose a platinum wire on whose end sodium chloride is fused is fixed to the stand), then the flame is coloured yellow, and on looking through the spectroscope the observer will see a bright _yellow_ line falling upon the 50th division of the scale, which is seen together with the spectrum in the telescope. No yellow lines of other refractive index, nor any rays of any other colour, will be seen, and, therefore, the spectrum corresponding with sodium compounds consists of yellow rays of that index of refraction which belong to the Fraunhofer (black) line D of the solar spectrum. If a potassium salt be introduced into the flame instead of a sodium salt, then two bands will be seen which are much feebler than the bright sodium band--namely, one red line near the Fraunhofer line A and another violet line. Besides which, a pale, almost continuous, spectrum will be observed in the central portions of the scale. If a mixture of sodium and potassium salts be now introduced into the flame, three lines will be seen simultaneously--namely, the red and pale violet lines of potassium and the yellow line of sodium. In this manner it is possible, by the aid of the spectroscope, to determine the relation between the spectra of metals and known portions of the solar spectrum. The continuity of the latter is interrupted by dark lines (that is, by an absence of light of a definite index of refraction), termed the Fraunhofer lines of the solar spectrum. It has been shown by careful observations (by Fraunhofer, Brewster, Foucault, Ångstrom, Kirchhoff, Cornu, Lockyer, Dewar, and others) that there exists an exact _agreement between the spectra_ of certain _metals_ and certain of the _Fraunhofer_ lines. Thus the bright yellow sodium line exactly corresponds with the dark Fraunhofer line D of the solar spectrum. A similar agreement is observed in the case of many other metals. This is not an approximate or chance correlation. In fact, if a spectroscope having a large number of refracting prisms and a high magnifying power be used, it is seen that the dark line D of the solar spectrum consists of an entire system of closely adjacent but definitely situated fine and wide (sharp, distinct) dark lines,[26] and an exactly similar group of bright lines is obtained when the yellow sodium line is examined through the same apparatus, so that each bright sodium line exactly corresponds with a dark line in the solar spectrum.[26 bis] This conformity of the bright lines formed by sodium with the dark lines of the solar spectrum cannot be accidental. This conclusion is further confirmed by the fact that the bright lines of other metals correspond with dark lines of the solar spectrum. Thus, for example, a series of sparks passing between the iron electrodes of a Ruhmkorff coil gives 450 very distinct lines characterising this metal. All these 450 bright lines, constituting the whole spectrum corresponding with iron, are repeated, as Kirchhoff showed, in the solar spectrum as dark Fraunhofer lines which occur in exactly the same situations as the bright lines in the iron spectrum, just as the sodium lines correspond with the band D in the solar spectrum. Many observers have in this manner studied the solar spectrum and the spectra of different metals simultaneously, and discovered in the former lines which correspond not only with sodium and iron, but also with many other metals.[27] The spectra of such elements as hydrogen, oxygen, nitrogen, and other gases may be observed in the so-called Geissler's tubes--that is, in glass tubes containing rarefied gases, through which the discharge of a Ruhmkorff's coil is passed. Thus hydrogen gives a spectrum composed of three lines--a red line corresponding with the Fraunhofer line C, a green line corresponding with the line F, and a violet line corresponding with one of the lines between G and H. Of these rays the red is the brightest, and therefore the general colour of luminous hydrogen (with an electric discharge through a Geissler tube) is reddish. [23] For accurate measurements and comparative researches more complicated spectroscopes are required which give a greater dispersion, and are furnished for this purpose with several prisms--for example, in Browning's spectroscope the light passes through six prisms, and then, having undergone an internal total reflection, passes through the upper portion of the same six prisms, and again by an internal total reflection passes into the ocular tube. With such a powerful dispersion the relative position of the spectral lines may be determined with accuracy. For the absolute and exact determination of the wave lengths it is particularly important that the spectroscope should be furnished with diffraction gratings. The construction of spectroscopes destined for special purposes (for example, for investigating the light of stars, or for determining the absorption spectra in microscopic preparations, &c.) is exceedingly varied. Details of the subject must be looked for in works on physics and on spectrum analysis. Among the latter the best known for their completeness and merit are those of Roscoe, Kayser, Vogel, and Lecoq de Boisbaudran. [24] The arrangement of all the parts of the apparatus so as to give the clearest possible vision and accuracy of observation must evidently precede every kind of spectroscopic determination. Details concerning the practical use of the spectroscope must be looked for in special works on the subject. In this treatise the reader is supposed to have a certain knowledge of the physical data respecting the refraction of light, and its dispersion and diffraction, and the theory of light, which allows of the determination of the length of the waves of light in absolute measure on the basis of observations with diffraction gratings, the distance between whose divisions may be easily measured in fractions of a millimetre; by such means it is possible to determine the wave-length of any given ray of light. [25] In order to give an idea of the size of the scale, we may observe that the ordinary spectrum extends from the zero of the scale (where the red portion is situated) to the 170th division (where the end of the visible violet portion of the spectrum is situated), and that the Fraunhofer line A (the extreme prominent line in the red) corresponds with the 17th division of the scale; the Fraunhofer line F (at the beginning of the blue, near the green colour) is situated on the 90th division, and the line G, which is clearly seen in the beginning of the violet portion of the spectrum, corresponds with the 127th division of the scale. [26] The two most distinct lines of D, or of sodium, have wave-lengths of 589·5 and 588·9 millionths of a millimeter, besides which fainter and fainter lines are seen whose wave-lengths in millionths of a millimeter are 588·7 and 588·1, 616·0 and 615·4, 515·5 and 515·2, 498·3 and 498·2, &c., according to Liveing and Dewar. [26 bis] In the ordinary spectroscopes which are usually employed in chemical research, one yellow band, which does not split up into thinner lines, is seen instead of the system of sodium lines, owing to the small dispersive power of the prism and the width of the slit of the object tube. [27] The most accurate investigations made in this respect are carried on with spectra obtained by diffraction, because in this case the position of the dark and bright lines does not depend on the index of refraction of the material of the prism, nor on the dispersive power of the apparatus. The best--that is, the most general and accurate--method of expressing the results of such determinations consists in determining the lengths of the waves corresponding to the rays of a definite index of refraction. (Sometimes instead of this the fraction of 1 divided by the square of the wave-length is given.) We will express this _wave-length_ in _millionth parts of a millimetre_ (the ten-millionth parts are already doubtful, and fall within the limits of error). In order to illustrate the relation between the wave-lengths and the positions of the lines of the spectrum, we will cite the wave-lengths corresponding with the chief Fraunhofer lines and colours of the spectrum. Fraunhofer line A B C D E b Wave-length 761·0 687·5 656·6 589·5-588·9 527·3 518·7 +-----------------+ +---------+ +----+ +---+ Colour red orange yellow green Fraunhofer line F G H Wave-length 486·5 431·0 397·2 +----------+ +----+ Colour blue violet In the following table are given the _wave-lengths_ of the light rays (the longest and most distinct, _see_ later) for certain elements, those in black type being the most clearly defined and distinct lines, which are easily obtained either in the flame of a Bunsen's burner, or in Geissler's tubes, or in general, by an electric discharge. These lines refer to the elements (the lines of compounds are different, as will be afterwards explained, but many compounds are decomposed by the flame or by an electric discharge), and moreover to the elements in an incandescent and rarefied gaseous state, for the spectra sometimes vary considerably with a variation of temperature and pressure. It may be mentioned that the _red_ colour corresponds with lines having a wave-length of from 780 (with a greater wave-length the lines are hardly visible, and are ultra red) to 650, the _orange_ from 650 to 590, the _yellow_ from 590 to 520, the _green_ from 520 to 490, the _blue_ from 490 to 420, and the _violet_ from 420 to 380 millionth parts of a millimetre. Beyond 380 the lines are scarcely visible, and belong to the ultra-violet. For fluorine Moissan found as many as 13 bright lines from 744 to 623. In the table (p. 565) which is arranged in conformity with the image of the spectrum as it is seen (the red lines on the left-hand and the violet on the right-hand side), the figures in black type correspond with lines which are so bright and distinctly visible that they may easily be made use of, both in determining the relation between the divisions of the scale and the wave-lengths, and in determining the admixture of a given element with another. Brackets join those lines between which several other lines are clearly visible if the dispersive power of the spectroscope permits distinguishing the neighbouring lines. In the ordinary laboratory spectroscopes with one prism, even with all possible precision of arrangement and with a brilliancy of light permitting the observations being made with a very narrow aperture, the lines whose wave-lengths only differ by 2-3 millionths of a millimetre, are blurred together; and with a wide aperture a series of lines differing by even as much as 20 millionths of a millimetre appear as one wide line. With a faint light (that is, with a small quantity of light entering into the spectroscope) only the most _brilliant_ lines are clearly visible. The _length_ of the lines does not always correspond with their brilliancy. According to Lockyer this length is determined by placing the carbon electrodes (between which the incandescent vapours of the metals are formed), not horizontally to the slit (as they are generally placed, to give more light), but vertically to it. Then certain lines appear long and others short. As a rule (Lockyer, Dewar, Cornu), the longest lines are those with which it is easiest to obtain _reversed_ spectra (_see_ later). Consequently, these lines are the most characteristic. Only the longest and most brilliant are given in our table, which is composed on the basis of a collection of the data at our disposal for _bright_ spectra of the _incandescent and rarefied vapours of the elements_. As the spectra change with great variations of temperature and vapour density (the faint lines become brilliant whilst the bright lines sometimes disappear), which is particularly clear from Ciamician's researches on the halogens, until the method of observation and the theory of the subject are enlarged, particular theoretical importance should not be given to the wave-lengths showing the maximum brilliancy, which only possess a practical significance in the common methods of spectroscopic observations. In general the spectra of metals are simpler than those of the halogens, and the latter are variable; at an increased pressure all spectral lines become broader. +-------+-------+--------+--------+-------+-------+------+------+ | N_{2} | O_{2} | Cl_{2} | Br_{2} | I_{2} | Pb | Sn | Tl | +-------+-------+--------+--------+-------+-------+------+------+ | -- | -- | -- | -- | -- | -- | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | | 662 | -- | -- | -- | -- | -- | -- | -- | | 632} | -- | -- | 636 | -- | -- | 645 | -- | | 620} | 615 | -- | -- | 621 | -- | -- | -- | | 585} | -- | -- | -- | 613 | 605·7 | 580} | -- | | 574} | -- | 546} | -- | 579} | 560·7 | 556} | -- | | 544} | 543 | 539} | 544} | 560} | 554·7 | -- | 549 | | 535} | 533 | 528} | 523} | 545} | 537 | -- | 535 | | 527} | 516 | 519} | 517 | 506} | -- | -- | -- | | 516} | 495} | 494} | 479 | -- | -- | -- | 489 | | -- | 494} | 480} | 470} | -- | -- | -- | -- | | 457 | 470} | -- | 462} | -- | -- | 452 | -- | | 442 | 465} | -- | 454 | 445 | -- | -- | -- | | 436} | 447} | 436} | 437 | -- | -- | -- | -- | | 426} | 432} | 431} | -- | -- | -- | -- | -- | | -- | -- | -- | -- | 421 | -- | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | | 409 | -- | -- | -- | -- | 406 | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | +-------+-------+--------+--------+-------+-------+------+------+ +-----+-----+-----+-------+-----+------+------+-----+-------+-----+ | In | Ga | Al | Ba | Sr | Ca | Mg | Zn | Cd | Hg | |-----+-----+-----+-------+-----|------+------|-----+-------+-----+ | -- | -- | -- | -- | -- | -- | -- | -- | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | -- | -- | | -- | -- | -- | -- | -- | 646 | -- | -- | -- | -- | | -- | -- | 624 | 649·7 | 641 | 644 | -- | 636 | 643·8 | -- | | 619 | -- | 623 | 614 | 606 | -- | -- | -- | -- | 615 | | -- | -- | -- | -- | -- | 612 | -- | -- | -- | 579 | | -- | -- | 572 | 553·5 | -- | -- | -- | -- | -- | 577 | | -- | -- | 570 | 549 | 548 | 559 | -- | -- | 537·7 | 546 | | 525 | -- | -- | -- | 524 | -- | 518 | -- | 533·6 | -- | | -- | -- | -- | -- | -- | -- | 516 | 492 | 508·5 | -- | | -- | -- | -- | 493·3 | -- | -- | -- | 481 | -- | -- | | -- | -- | -- | -- | -- | -- | 471 | 472 | 479·9 | -- | | 451 | -- | 466 | 455 | 460 | -- | -- | 468 | 467·7 | -- | | -- | -- | -- | -- | -- | 445} | 448 | -- | -- | -- | | -- | -- | -- | -- | -- | 442} | -- | -- | -- | 436 | | -- | -- | -- | -- | 430 | -- | -- | -- | -- | -- | | -- | 417 | -- | -- | 421 | 423 | -- | -- | -- | -- | | -- | -- | -- | 413 | -- | -- | -- | -- | -- | -- | | 410 | 403 | 396 | -- | 408 | 397 | 384} | -- | -- | 404 | | -- | -- | 394 | -- | -- | 393 | 383} | - -| -- | -- | +-----+-----+-----+-------+-----+------+------+-----+-------+-----+ +------+------+-----+-------+-----+-------+------+-------+-------+ | Mn | Fe | Cu | Ag | Cs | Rb | K | Na | Li | |------+------+-----+-------+-----+-------+------+-------+-------+ | -- | -- | -- | -- | -- | 780 | 770 | -- | -- | | -- | -- | -- | -- | -- | -- | 766 | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | 670·6 | | -- | 640 | -- | -- | -- | -- | -- | -- | -- | | 602} | -- | -- | -- | 622 | 629·6 | -- | -- | 610 | | 601} | 561} | 578 | -- | 600 | -- | 583} | 589·5 | -- | | 551} | 544} | 570 | 546·4 | -- | -- | 578} | 588·9 | -- | | 534} | 537 | 522 | -- | -- | -- | -- | -- | -- | | -- | 532} | 515 | 520·8 | -- | -- | 535 | -- | -- | | -- | 521} | 511 | -- | -- | -- | 532} | -- | -- | | 482} | 496} | -- | -- | -- | -- | -- | -- | 497 | | 471} | 489} | -- | -- | -- | -- | -- | -- | -- | | -- | -- | -- | -- | 459 | -- | -- | -- | 460·3 | | -- | 441} | -- | -- | 456 | -- | -- | -- | -- | | -- | 430} | -- | -- | -- | -- | -- | -- | -- | | -- | 427 | -- | -- | -- | -- | -- | -- | -- | | 424} | -- | -- | 421 | -- | 420 | -- | -- | -- | | 403} | 407} | -- | -- | -- | -- | -- | -- | -- | | -- | 404} | -- | -- | -- | -- | 404 | -- | -- | | -- | -- | -- | -- | -- | -- | -- | -- | -- | +------+------+-----+-------+-----+-------+------+-------+-------+ +-------+ | H_{2} | +-------+ | -- | | -- | | -- | | 656·2 | | -- | | -- | | -- | | -- | | -- | | -- | | 486·1 | | -- | | -- | | -- | | 434 | | -- | | -- | | -- | | -- | | -- | +-------+ [Illustration: FIG. 73.--Absorption spectrum (Lecoq de Boisbaudran) of salts of didymium in concentrated and dilute solutions.] The correlation of the Fraunhofer lines with the spectra of metals depends on the phenomenon of the so-called _reversal of the spectrum_. This phenomenon consists in this, that instead of the bright spectrum corresponding with a metal, under certain circumstances a similar dark spectrum in the form of Fraunhofer lines may be obtained, as will be explained directly. In order to clearly understand the phenomenon of reversed spectra, it must be known that when light passes through certain transparent substances these substances retain rays of a certain refrangibility. The colour of solutions is a proof of this. Light which has passed through a yellow solution of a uranium salt contains no violet rays, and after having passed through a red solution of a permanganate, does not contain many rays in the yellow, blue, and green portions of the spectrum. Solutions of copper salts absorb nearly all red rays. Sometimes colourless solutions also absorb rays of certain definite refractive indexes, and give _absorption spectra_. Thus solutions of salts of didymium absorb rays of a certain refrangibility, and therefore an impression of black lines is received,[28] as shown in fig. 73. Many vapours (iodine) and gases (nitric peroxide) give similar spectra. Light which has passed through a deep layer of aqueous vapour, oxygen, or nitrogen also gives an absorption spectrum. For this reason the peculiar (winter) dark lines discovered by Brewster are observed in sunlight, especially in the evening and morning, when the sun's rays pass through the atmosphere (containing these substances) by a longer path than at mid-day. It is evident that the Fraunhofer lines may be ascribed to the absorption of certain rays of light in its passage from the luminous mass of the sun to the earth. The remarkable progress made in all spectroscopic research dates from the investigations made by _Kirchhoff_ (1859) on the relation between absorption spectra and the spectra of luminous incandescent gases. It had already been observed long before (by Fraunhofer, Foucault, Ångstrom) that the bright spectrum of the sodium flame gives two bright lines which are in exactly the same position as two black lines known as D in the solar spectrum, which evidently belong to an absorption spectrum. When Kirchhoff caused diffused sunlight to fall upon the slit of a spectroscope, and placed a sodium flame before it, a perfect superposition was observed--the bright sodium lines completely covered the black lines D of the solar spectrum. When further the continuous spectrum of a Drummond light showed the black line D on placing a sodium flame between it and the slit of the spectroscope--that is, when the Fraunhofer line of the solar spectrum was artificially produced--then there was no doubt that its appearance in the solar spectrum was due to the light passing somewhere through incandescent vapours of sodium. Hence a new theory of _reversed spectra_[29] arose--that is, of the relation between the waves of light emitted and absorbed by a substance under given conditions of temperature; this is expressed by Kirchhoff's law, discovered by a careful analysis of the phenomena. This law may be formulated in an elementary way as follows: At a given temperature the relation between the intensity of the light emitted (of a definite wave-length) and the absorptive capacity with respect to the same colour (of the same wave-length) is a constant quantity.[30] As a black dull surface emits and also absorbs a considerable quantity of heat rays whilst a polished metallic surface both absorbs and emits but few, so a flame coloured by sodium emits a considerable quantity of yellow rays of a definite refrangibility, and has the property of absorbing a considerable quantity of the rays of the same refractive index. In general, the medium which emits definite rays also absorbs them. [28] The method of observing absorption spectra consists in taking a continuous spectrum of white light (one which does not show either dark lines or particularly bright luminous bands--for instance, the light of a candle, lamp, or other source). The collimator (that is, the tube with the slit) is directed towards this light, and then all the colours of the spectrum are visible in the ocular tube. A transparent absorptive medium--for instance, a solution or tube containing a gas--is then placed between the source of light and the apparatus (or anywhere inside the apparatus itself in the path of the rays). In this case either the entire spectrum is uniformly fainter, or absorption bands appear on the bright field of the continuous spectrum in definite positions along it. These bands have different lengths and positions, and distinctness and intensity of absorption, according to the properties of the absorptive medium. Like the luminous spectra given by incandescent gases and vapours, the absorption spectra of a number of substances have already been studied, and some with great precision--as, for example, the spectrum of the brown vapours of nitrogen dioxide by Hasselberg (at Pulkowa), the spectra of colouring matters (Eder and others), especially of those applied to orthochromatic photography, the spectra of blood, chlorophyll (the green constituent of leaves), and other similar substances, all the more carefully as by the aid of their spectra the presence of these substances may be discovered in small quantities (even in microscopical quantities, by the aid of special appliances on the microscope), and the changes they undergo investigated. [Illustration: FIG. 74.--Absorption spectra of nitrogen dioxide and iodine.] The absorption spectra, obtained at the ordinary temperature and proper to substances in all physical states, offer a most extensive but as yet little studied field, both for the general theory of spectroscopy, and for gaining an insight into the structure of substances. The investigation of colouring matters has already shown that in certain cases a definite change of composition and structure entails not only a definite change of the colours but also a displacement of the absorption bands by a definite number of wave-lengths. [29] A number of methods have been invented to demonstrate the reversibility of spectra; among these methods we will cite two which are very easily carried out. In Bunsen's method sodium chloride is put into an apparatus for evolving hydrogen (the spray of the salt is then carried off by the hydrogen and colours the flame with the yellow sodium colour), and the hydrogen is ignited in two burners--in one large one with a wide flame giving a bright yellow sodium light, and in another with a small fine orifice whose flame is pale: this flame will throw a dark patch on the large bright flame. In Ladoffsky's method the front tube (p. 561) is unscrewed from a spectroscope directed towards the light of a lamp (a continuous spectrum), and the flame of a spirit lamp coloured by a small quantity of NaCl is placed between the tube and the prism; a black band corresponding to sodium will then be seen on looking through the ocular tube. This experiment is always successful if only there be the requisite relation between the strength of light of the two lamps. [30] The absorptive capacity is the relation between the intensity of the light (of a given wave-length) falling upon and retained by a substance. Bunsen and Roscoe showed by direct experiment that this ratio is a constant quantity for every substance. If _A_ stand for this ratio for a given substance at a given temperature--for instance, for a flame coloured by sodium--and _E_ be the intensity of the light of the same wave-length emitted at the same temperature by the same substance, then Kirchhoff's law, the explanation and deduction of which must be looked for in text-books of physics, states that the fraction _A/E_ is a constant quantity depending on the nature of a substance (as _A_ depends on it) and determined by the temperature and wave-length. [Illustration: FIG. 75.--Bright spectra of copper compounds.] Thus the bright spectral rays characteristic of a given metal may be reversed--that is, converted into dark lines--by passing light which gives a continuous spectrum through a space containing the heated vapours of the given metal. A similar phenomenon to that thus artificially produced is observed in sunlight, which shows dark lines characteristic of known metals--that is, the Fraunhofer lines form an absorption spectrum or depend on a reversed spectrum; it being presupposed that the sun itself, like all known sources of artificial light, gives a continuous spectrum without Fraunhofer lines.[31] We must imagine that the sun, owing to the high temperature which is proper to it, emits a brilliant light which gives a continuous spectrum, and that this light, before reaching our eyes, passes through a space full of the vapours of different metals and their compounds. As the earth's atmosphere[32] contains very little, or no, metallic vapours, and as they cannot be supposed to exist in the celestial space,[32 bis] the only place in which the existence of such vapours can be admitted is in the _atmosphere surrounding the sun itself_. As the cause of the sun's luminosity must be looked for in its high temperature, the existence of an atmosphere containing metallic vapours is readily understood, because at that high temperature such metals as sodium, and even iron, are separated from their compounds and converted into vapour. The sun must be imagined as surrounded by an atmosphere of incandescent vaporous and gaseous matter,[33] including those elements whose reversed spectra correspond with the Fraunhofer lines--namely, sodium, iron, hydrogen, lithium, calcium, magnesium, &c. Thus in spectrum analysis we find a means of determining the composition of the inaccessible heavenly luminaries, and much has been done in this respect since Kirchhoff's theory was formulated. By observations on the spectra of many heavenly bodies, changes have been discovered going on in them,[34] and many of the elements known to us have been found with certainty in them.[35] From this it must be concluded that the same elements which exist on the earth occur throughout the whole universe, and that at that degree of heat which is proper to the sun those simple substances which we accept as the elements in chemistry are still undecomposed and remain unchanged. A high temperature forms one of those conditions under which compounds most easily decompose; and if sodium or a similar element were a compound, in all probability it would be decomposed into component parts at the high temperature of the sun. This may indeed be concluded from the fact that in ordinary spectroscopic experiments the spectra obtained often belong to the metals and not to the compounds taken; this depends on the decomposition of these compounds in the heat of the flame. If common salt be introduced into the flame of a gas-burner, a portion of it is decomposed, first forming, in all probability, with water, hydrochloric acid and sodium hydroxide, and the latter then becoming partially decomposed by the hydrocarbons, giving metallic sodium, whose incandescent vapour emits light of a definite refrangibility. This conclusion is arrived at from the following experiment:--If hydrochloric acid gas be introduced into a flame coloured by sodium it is observed that the sodium spectrum disappears, owing to the fact that metallic sodium cannot remain in the flame in the presence of an excess of hydrochloric acid. The same thing takes place on the addition of sal-ammoniac, which in the heat of the flame gives hydrochloric acid. If a porcelain tube containing sodium chloride (or sodium hydroxide or carbonate), and closed at both ends by glass plates, be so powerfully heated that the salt volatilises, then the sodium spectrum is not observable; but if the salt be replaced by sodium, then either the bright line or the absorption spectra is obtained, according to whether the light emitted by the incandescent vapour be observed, or light passing through the tube. Thus the above spectrum is not given by sodium chloride or other sodium compound, but is proper to the metal sodium itself. This is also the case with other analogous metals. The chlorides and other halogen _compounds_ of barium, calcium, copper, &c., give independent spectra which differ from those of the metals. If barium chloride be introduced into a flame, it gives a mixed spectrum belonging to metallic barium and barium chloride. If besides barium chloride, hydrochloric acid or sal-ammoniac be introduced into the flame, then the spectrum of the metal disappears, and that of the chloride remains, which differs distinctly from the spectrum of barium fluoride, barium bromide, or barium iodide. A certain common resemblance and certain common lines are observed in the spectra of two different compounds of one and the same element obtained in the above-described manner, and also in the spectrum of the metal, but they all have their peculiarities. The independent spectra of the compounds of copper are easily observed (fig. 75). Thus certain compounds which exist in a state of vapour, and are luminous at a high temperature, give their independent spectra. In the majority of cases the spectra of compounds are composed of indistinct luminous lines and complete bright bands, whilst metallic elements generally give a few clearly-defined spectral lines.[36] There is no reason for supposing that the spectrum of a compound is equal to the sum of the spectra of its elements--that is, _every compound_ which is not decomposed by heat _has its own proper spectrum_. This is best proved by absorption spectra, which are essentially only reversed spectra observed at low temperatures. If every salt of sodium, lithium, and potassium gives one and the same spectrum, this must be ascribed to the presence in the flame of the free metals liberated by the decomposition of their salts. Therefore _the phenomena of the spectrum are determined by molecules, and not by atoms_--that is, the molecules of the metal sodium, and not its atoms, produce those particular vibrations which determine the spectrum of a sodium salt. Where there is no free metallic sodium there is no sodium spectrum. [31] Heated metals begin to emit light (only visible in the dark) at about 420° (varying with the metal). On further heating, solids first emit red, then yellow, and lastly white light. Compressed or heavy gases (_see_ Chapter III., Note 44), when strongly heated, also emit white light. Heated liquids (for example, molten steel or platinum) also give a white compound light. This is readily understood. In a dense mass of matter the collisions of the molecules and atoms are so frequent that waves of only a few definite lengths cannot appear; the reverse is possible in rarefied gases or vapours. [32] Brewster, as is mentioned above, first distinguished the atmospheric, cosmical Fraunhofer lines from the solar lines. Janssen showed that the spectrum of the atmosphere contains lines which depend on the absorption produced by aqueous vapour. Egoreff, Olszewski, Janssen, and Liveing and Dewar showed by a series of experiments that the oxygen of the atmosphere gives rise to certain lines of the solar spectrum, especially the line A. Liveing and Dewar took a layer of 165 c.m. of oxygen compressed under a pressure of 85 atmospheres, and determined its absorption spectrum, and found that, besides the Fraunhofer lines A and B, it contained the following groups: 630-622, 581-568, 535, 480-475. The same lines were found for liquid oxygen. [32 bis] If the material of the whole heavenly space formed the absorbent medium, the spectra of the stars would be the same as the solar spectrum; but Huyghens, Lockyer, and others showed not only that this is the case for only a few stars, but that the majority of stars give spectra of a different character with dark and bright lines and bands. [33] Eruptions, like our volcanic eruptions, but on an incomparably larger scale, are of frequent occurrence on the sun. They are seen as protuberances visible during a total eclipse of the sun, in the form of vaporous masses on the edge of the solar disc and emitting a faint light. These protuberances of the sun are now observed at all times by means of the spectroscope (Lockyer's method), because they contain luminous vapours (giving bright lines) of hydrogen and other elements. [34] The great interest and vastness of astro-physical observations concerning the sun, comets, stars, nebulæ, &c., render this new province of natural science very important, and necessitate referring the reader to special works on the subject. The most important astro-physical data since the time of Kellner are those referring to the _displacement_ of the lines of the spectrum. Just as a musical note changes its pitch with the approach or withdrawal of the resonant object or the ear, so the pitch of the luminous note or wave-length of the light varies if the luminous (or absorbent) vapour and the earth from which we observe it approach or recede from each other; this expresses itself in a visible displacement of the spectral lines. The solar eruptions even give broken lines in the spectrum, because the rapidly moving eruptive masses of vapour and gases either travel in the direction of the eye or fall back towards the sun. As the earth travels with the solar system among the stars, so it is possible to determine the direction and velocity with which the sun travels in space by the displacement of the spectral lines and light of the stars. The changes proceeding on the sun in its mass, which must be pronounced as vaporous, and in its atmosphere, are now studied by means of the spectroscope. For this purpose, many special astro-physical observatories now exist where these investigations are carried on. We may remark that if the observer or luminous object moves with a velocity ±_v_, the ray, whose wave-length is [Greek: l], has an apparent wave-length [Greek: l](_n_±_v_)/_n_, where _n_ is the velocity of light. Thus Tolon, Huyghens, and others proved that the star Aldebaran approaches the solar system with a velocity of 30 kilometres per second, while Arcturus is receding with a velocity of 45 kilometres. The majority of stars give a distinct hydrogen spectrum, besides which nebulæ also give the spectrum of nitrogen. Lockyer classes the stars from their spectra, according to their period of formation, showing that some stars are in a period of increasing temperature (of formation or aggregation), whilst others are in a period of cooling. Altogether, in the astro-physical investigation of the spectra of heavenly bodies we find one of the most interesting subjects of recent science. [35] Spectrum analysis has proved the indubitable existence in the sun and stars of a number of elements known in chemistry. Huyghens, Secchi, Lockyer, and others have furnished a large amount of material upon this subject. A compilation of existing information on it has been given by Prof. S. A. Kleiber, in the Journal of the Russian Physico-chemical Society for 1885 (vol. xviii. p. 146). Besides which, a peculiar element called helium has been discovered, which is characterised by a line (whose wave-length is 587·5, situated near D), which is seen very brightly in the projections (protuberances) and spots of the sun, but which does not belong to any known element, and is not reproducible as a reversed, dark line. This may be a right conclusion--that is to say, it is possible that an element may be discovered to which the spectrum of helium corresponds--but it may be that the helium line belongs to one of the known elements, because spectra vary in the brilliancy and position of their lines with changes of temperature and pressure. Thus, for instance, Lockyer could only see the line 423, at the very end of the calcium spectrum, at comparatively low temperatures, whilst the lines 397 and 393 appear at a higher temperature, and at a still higher temperature the line 423 becomes quite invisible. [36] Spectroscopic observations are still further complicated by the fact that one and the same substance gives different spectra at different temperatures. This is especially the case with gases whose spectra are obtained by an electric discharge in tubes. Plücker, Wüllner, Schuster, and others showed that at low temperatures and pressures the spectra of iodine, sulphur, nitrogen, oxygen, &c. are quite different from the spectra of the same elements at high temperatures and pressures. This may either depend on the fact that the elements change their molecular structure with a change of temperature, just as ozone is converted into oxygen (for instance, from N_{2} molecules are obtained containing only one atom of nitrogen), or else it may be because at low temperature certain rays have a greater relative intensity than those which appear at higher temperatures. If we suppose that the molecules of a gas are in continual motion, with a velocity dependent on the temperature, then it must be admitted that they often strike against each other and rebound, and thus communicate peculiar motions to each other and the supposed ether, which express themselves in luminiferous phenomena. A rise of the temperature or an increase in the density of a gas must have an influence on the collision of its molecules and luminiferous motions thus produced, and this may be the cause of the difference of the spectra under these circumstances. It has been shown by direct experiment that gases compressed by pressure, when the collision of the molecules must be frequent and varied, exhibit a more complex spectrum on the passage of an electric spark than rarefied gases, and that even a continuous spectrum appears. In order to show the variability of the spectrum according to the circumstances under which it proceeds, it may be mentioned that potassium sulphate fused on a platinum wire gives, on the passage of a series of sparks, a distinct system of lines, 583-578, whilst when a series of sparks is passed through a solution of this salt this system of lines is faint, and when Roscoe and Schuster observed the absorption spectrum of the vapour of metallic potassium (which is green) they remarked a number of lines of the same intensity as the above system in the red, orange, and yellow portions. [Illustration: FIG. 76.--Method of showing the spectrum of substances in solution.] The spectra of solutions are best observed by means of Lecoq de Boisbaudran's arrangement, shown in fig. 76. A bent capillary tube, D F, inside which a platinum wire, A _a_ (from 0·3 to 0·5 mm. in diameter) is fused, is immersed in a narrow cylinder, C (in which it is firmly held by a cork). The projecting end, _a_, of the wire is covered by a fine capillary tube, _d_, which extends 1-2 mm. beyond the wire. Another straight capillary tube, E, with a platinum wire, B _b_, about 1 mm. in diameter (a finer wire soon becomes hot), is held (by a cork or in a stand) above the end of the tube, D. If the wire A be now connected with the positive, and the wire B with the negative terminal of a Ruhmkorff's coil (if the wires be connected in the opposite order, the spectrum of air is obtained), a series of sparks rapidly following each other appear between _a_ and _b_, and their light may be examined by placing the apparatus in front of the slit of a spectroscope. The variations to which a spectrum is liable may easily be observed by increasing the distance between the wires, altering the direction of the current or strength of the solution, &c. _Spectrum analysis_ has not only endowed science with a knowledge of the composition of distant heavenly bodies (of the sun, stars, nebulæ, comets, &c.), but has also given a new _method_ for studying the matter of the earth's surface. With its help Bunsen discovered two new elements belonging to the group of the alkali metals, and thallium, indium, and gallium were afterwards discovered by the same means. The spectroscope is employed in the study of rare metals (which in solution often give distinct absorption spectra), of dyes, and of many organic substances, &c.[37] With respect to the metals which are analogous to sodium, they all give similar very volatile salts and such very characteristic spectra that the least traces of them[38] are discovered with great ease by means of the spectroscope. For instance, _lithium_ gives a very brilliant red coloration to a flame and a very bright red spectral line (wave-length, 670 millionths mm.), which indicates the presence of this metal in admixture with compounds of other alkali metals. [37] The importance of the spectroscope for the purpose of chemical research was already shown by Gladstone in 1856, but it did not become an accessory to the laboratory until after the discoveries of Kirchhoff and Bunsen. It may be hoped that in time spectroscopic researches will meet certain wants of the theoretical (philosophical) side of chemistry, but as yet all that has been done in this respect can only be regarded as attempts which have not yet led to any trustworthy conclusions. Thus many investigators, by collating the wave-lengths of all the light vibrations excited by a given element, endeavour to find the law governing their mutual relations; others (especially Hartley and Ciamician), by comparing the spectra of analogous elements (for instance, chlorine, bromine, and iodine), have succeeded in noticing definite features of resemblance in them, whilst others (Grünwald) search for relations between the spectra of compounds and their component elements, &c.; but--owing to the multiplicity of the spectral lines proper to many elements, and (especially in the ultra-red and ultra-violet ends of the spectrum) the existence of lines which are undistinguishable owing to their faintness, and also owing to the comparative novelty of spectroscopic research--this subject cannot be considered as in any way perfected. Nevertheless, in certain instances there is evidently some relationship between the wave-lengths of all the spectral lines formed by a given element. Thus, in the hydrogen spectrum the wave-length = 364·542 _m_^2/(_m_^{2}-4), if _m_ varies as a series of whole numbers from 3 to 15 (Walmer, Hagebach, and others). For example, when _m_ = 3, the wave-length of one of the brightest lines of the hydrogen spectrum is obtained (656·2), when _m_ = 7, one of the visible violet lines (396·8), and when _m_ is greater than 9, the ultra-violet lines of the hydrogen spectrum. [38] In order to show the degree of sensitiveness of spectroscopic reactions the following observation of Dr. Bence Jones may be cited: If a solution of 3 grains of a lithium salt be injected under the skin of a guinea-pig, after the lapse of four minutes, lithium can be discovered in the bile and liquids of the eye, and, after ten minutes, in all parts of the animal. [Illustration: FIG. 77.--Preparation of lithium by the action of a galvanic current on fused lithium chloride.] _Lithium_, Li, is, like potassium and sodium, somewhat widely spread in siliceous rocks, but only occurs in small quantities and as mere traces in considerable masses of potassium and sodium salts. Only a very few rather rare minerals contain more than traces of it,[39] for example, spodumene and lithia mica. Many compounds of lithium are in all respects closely analogous to the corresponding compounds of sodium and potassium; but the _carbonate_ is sparingly soluble in cold water, which fact is taken advantage of for separating lithium from potassium and sodium. This salt, Li_{2}CO_{3}, is easily converted into the other compounds of lithium. Thus, for instance, the lithium hydroxide, LiHO, is obtained in exactly the same way as caustic soda, by the action of lime on the carbonate, and it is soluble in water and crystallises (from its solution in alcohol) as LiHO,H_{2}O. Metallic _lithium_ is obtained by the action of a galvanic current on fused lithium chloride; for this purpose a cast-iron crucible, furnished with a stout cover, is filled with lithium chloride, heated until the latter fuses, and a strong galvanic current is then passed through the molten mass. The positive pole (fig. 77) consists of a dense carbon rod C (surrounded by a porcelain tube P fixed in an iron tube BB), and the negative pole of an iron wire, on which the metal is deposited after the current has passed through the molten mass for a certain length of time. Chlorine is evolved at the positive pole. When a somewhat considerable quantity of the metal has accumulated on the wire it is withdrawn, the metal is collected from it, and the experiment is then carried on as before.[39 bis] Lithium is the lightest of all metals, its specific gravity is 0·59, owing to which it floats even on naphtha; it melts at 180°, but does not volatilise at a red heat. Its appearance recalls that of sodium, and, like it, it has a yellow tint. At 200° it burns in air with a very bright flame, forming lithium oxide. In decomposing water it does not ignite the hydrogen. The characteristic test for lithium compounds is the _red coloration_ which they impart to a colourless flame.[40] [39] Thus _spodumene_ contains up to 6 p.c. of lithium oxide, and _petolite_, and _lepidolite_ or lithia mica, about 3 p.c. of lithium oxide. This mica is met with in certain granites in a somewhat considerable quantity, and is therefore most frequently employed for the preparation of lithium compounds. The treatment of lepidolite is carried on on a large scale, because certain salts of lithium are employed in medicine as a remedy for certain diseases (stone, gouty affections), as they have the power of dissolving the insoluble uric acid which is then deposited. Lepidolite, which is unacted on by acids in its natural state, decomposes under the action of strong hydrochloric acid after it has been fused. After being subjected to the action of the hydrochloric acid for several hours all the silica is obtained in an insoluble form, whilst the metallic oxides pass into solution as chlorides. This solution is mixed with nitric acid to convert the ferrous salts into ferric, and sodium carbonate is then added until the liquid becomes neutral, by which means a precipitate is formed of the oxides of iron, alumina, magnesia, &c., as insoluble oxides and carbonates. The solution (with an excess of water) then contains the chlorides of the alkaline metals KCl, NaCl, LiCl, which do not give a precipitate with sodium carbonate in a dilute solution. It is then evaporated, and a strong solution of sodium carbonate added. This precipitates lithium carbonate, which, although soluble in water, is much less so than sodium carbonate, and therefore the latter precipitates lithium from strong solutions as carbonate, 2LiCl + Na_{2}CO_{3} = 2NaCl + Li_{2}CO_{3}. _Lithium carbonate_, which resembles sodium carbonate in many respects, is a substance which is very slightly soluble in cold water and is only moderately soluble in boiling water. In this respect lithium forms a transition between the metals of the alkalis and other metals, especially those of the alkaline earths (magnesium, barium), whose carbonates are only sparingly soluble. Oxide of lithium, Li_{2}O, may be obtained by heating lithium carbonate with charcoal. Lithium oxide in dissolving gives (per gram-molecule) 26,000 heat units; but the combination of Li_{2} with O evolves 140,000 calories--that is, more than Na_{2}O (100,000 calories) and K_{2}O (97,000 calories), as shown by Beketoff (1887). Oeuvrard (1892) heated lithium to redness in nitrogen, and observed the absorption of N and formation of Li_{3}N, like Na_{3}N (_see_ Chapter XII. Note 50). LiCl, LiBr, and LiI form crystallo-hydrates with H_{2}O, 2H_{2}O, and 3H_{2}O. As a rule, LiBr,2H_{2}O crystallises out, but Bogorodsky (1894) showed that a solution containing LiBr + 3·7H_{2}O, cooled to -62°, separates out crystals LiBr,3H_{2}O, which decompose at +4° with the separation of H_{2}O. LiF is but slightly soluble (in 800 parts) in water (and still less so in a solution of NH_{4}F). [39 bis] Guntz (1893) recommends adding KCl to the LiCl in preparing Li by this method, and to act with a current of 10 ampères at 20 volts, and not to heat above 450°, so as to avoid the formation of Li_{2}Cl. [40] In determining the presence of lithium in a given compound, it is best to treat the material under investigation with acid (in the case of mineral silicon compounds hydrofluoric acid must be taken), and to treat the residue with sulphuric acid, evaporate to dryness, and extract with alcohol, which dissolves a certain amount of the lithium sulphate. It is easy to discover lithium in such an alcoholic solution by means of the coloration imparted to the flame on burning it, and in case of doubt by investigating its light in a spectroscope, because lithium gives a red line, which is very characteristic and is found as a dark line in the solar spectrum. Lithium was first discovered in 1817 in petolite by Arfvedson. Bunsen in 1860 tried to determine by means of the spectroscope whether any other as yet unknown metals might not occur in different natural products together with lithium, potassium, and sodium, and he soon discovered two new alkali metals showing independent spectra. They are named after the characteristic coloration which they impart to the flame. One which gives a red and violet band is named _rubidium_, from _rubidius_ (dark red), and the other is called _cæsium_, because it colours a pale flame sky blue, which depends on its containing bright blue rays, which appear in the spectrum of cæsium as two blue bands (table on p. 565). Both metals accompany sodium, potassium, and lithium, but in small quantities; rubidium occurs in larger quantity than cæsium. The amount of the oxides of cæsium and rubidium in lepidolite does not generally exceed one-half per cent. Rubidium has also been found in the ashes of many plants, while the Stassfurt carnallite (the mother-liquor obtained after having been treated for KCl) forms an abundant source for rubidium and also partly for cæsium. Rubidium also occurs, although in very small quantities, in the majority of mineral waters. In a very few cases cæsium is not accompanied by rubidium; thus, in a certain granite on the Isle of Elba, cæsium has been discovered, but not rubidium. This granite contains a very rare mineral called _pollux_, which contains as much as 34 per cent. of cæsium oxide. Guided by the spectroscope, and aided by the fact that the double salts of platinic chloride and rubidium and cæsium chlorides are still less soluble in water than the corresponding potassium salt, K_{2}PtCl_{6},[41] Bunsen succeeded in separating both metals from each other and from potassium, and demonstrated the great resemblance they bear to each other. The isolated metals,[42] rubidium and cæsium, have respectively the specific gravities 1·52 and 2·366, and melting points 39° and 27° as N. N. Beketoff showed (1894), he having obtained cæsium by heating CsAlO_{2} with Mg([42 bis]). [41] The salts of the majority of metals are precipitated as carbonates on the addition of ammonium carbonate--for instance, the salts of calcium, iron, &c. The alkalis whose carbonates are soluble are not, however, precipitated in this case. On evaporating the resultant solution and igniting the residue (to remove the ammonium salts), we obtain salts of the alkali metals. They may he separated by adding hydrochloric acid together with a solution of platinic chloride. The chlorides of lithium and sodium give easily soluble double salts with platinic chloride, whilst the chlorides of potassium, rubidium, and cæsium form double salts which are sparingly soluble. A hundred parts of water at 0° dissolve 0·74 part of the potassium platinochloride; the corresponding rubidium platinochloride is only dissolved to the amount of 0·134 part, and the cæsium salt, 0·024 part; at 100° 5·13 parts of potassium platinochloride, K_{2}PtCl_{6}, are dissolved, 0·634 part of rubidium platinochloride, and 0·177 part of cæsium platinochloride. From this it is clear how the salts of rubidium and cæsium may be isolated. The separation of cæsium from rubidium by this method is very tedious. It can be better effected by taking advantage of the difference of the solubility of their carbonates in alcohol; cæsium carbonate, Cs_{2}CO_{3}, is soluble in alcohol, whilst the corresponding salts of rubidium and potassium are almost insoluble. Setterberg separated these metals as alums, but the best method, that given by Scharples, is founded on the fact that from a mixture of the chlorides of potassium, sodium, cæsium, and rubidium in the presence of hydrochloric acid, stannic chloride precipitates a double salt of cæsium, which is very slightly soluble. The salts of Rb and Cs are closely analogous to those of potassium. [42] Bunsen obtained rubidium by distilling a mixture of the tartrate with soot, and Beketoff (1888) by heating the hydroxide with aluminium, 2RbHO + Al = RbAlO_{2} + H_{2} + Rb. By the action of 85 grams of rubidium on water, 94,000 heat units are evolved. Setterberg obtained cæsium (1882) by the electrolysis of a fused mixture of cyanide of cæsium and of barium. Winkler (1890) showed that metallic magnesium reduces the hydrates and carbonates of Rb and Cs like the other alkaline metals. N. N. Beketoff obtained them with aluminium (see following note). [42 bis] Beketoff (1888) showed that metallic aluminium reduces the hydrates of the alkaline metals at a red heat (they should be perfectly dry) with the formation of aluminates (Chapter XVII.), RAlO_{2}--for example, 2KHO + Al = KAlO_{2} + K + H_{2}. It is evident that in this case only half of the alkaline metal is obtained free. On the other hand, K. Winkler (1889) showed that magnesium powder is also able to reduce the alkaline metals from their hydrates and carbonates. N. N. Beketoff and Tscherbacheff (1894) prepared cæsium upon this principle by heating its aluminate CsAlO_{2} with magnesium powder. In this case aluminate of magnesium is formed, and the whole of the cæsium is obtained as metal: 2CsAlO_{2} + Mg = MgOAl_{2}O_{5} + 2Cs. A certain excess of alumina was taken (in order to obtain a less hygroscopic mass of aluminate), and magnesium powder (in order to decompose the last traces of water); the CsAlO_{2} was prepared by the precipitation of cæsium alums by caustic baryta, and evaporating the resultant solution. We may add that N. N. Beketoff (1887) prepared oxide of potassium, K_{2}O, by heating the peroxide, KO, in the vapour of potassium (disengaged from its alloy with silver), and showed that in dissolving in an excess of water it evolves (for the above-given molecular weight) 67,400 calories (while 2KHO in dissolving in water evolves 24,920 cal.; so that K_{2}O + H_{2}O gives 42,480 cal.), whence (knowing that K_{2} + O+H_{2}O in an excess of water evolves 164,500) it follows that K_{2} + O evolves 97,100 cal. This quantity is somewhat less than that (100,260 cal.) which corresponds to sodium, and the energy of the action of potassium upon water is explained by the fact that K_{2}O evolves more heat than Na_{2}O in combining with water (_see_ Chapter II. Note 9). Just as hydrogen displaces half the Na from Na_{2}O forming NaHO, so also N. N. Beketoff found from experiment and thermochemical reasonings that hydrogen displaces half the potassium from K_{2}O forming KHO and evolving 7,190 calories. Oxide of lithium, Li_{2}O, which is easily formed by igniting Li_{2}CO_{3} with carbon (when Li_{2}O + 2CO is formed), disengages 26,000 cals. with an excess of water, while the reaction Li_{2} + O gives 114,000 cals. and the reaction Li_{2} + H_{2}O gives only 13,000 cals., and metallic lithium cannot be liberated from oxide of lithium with hydrogen (nor with carbon). Thus in the series Li, Na, K, the formation of R_{2}O gives most heat with Li and least with K, while the formation of RCl evolves most heat with K (105,000 cals.) and least of all with Li (93,500 cals.). Rubidium, in forming Rb_{2}O, gives 94,000 cals. (Beketoff). Cæsium, in acting upon an excess of water, evolves 51,500 cals., and the reaction Cs_{2} + O evolves about 100,000 cals.--_i.e._ more than K and Rb, and almost as much as Na--and oxide of cæsium reacts with hydrogen (according to the equation Cs_{2}O + H = CsHO + Cs) more easily than any of the oxides of the alkali metals, and this reaction takes place at the ordinary temperature (the hydrogen is absorbed), as Beketoff showed (1893). He also obtained a mixed oxide, AgCsO, which was easily formed in the presence of silver, and absorbed hydrogen with the formation of CsHO. Judging by the properties of the free metals, and of their corresponding and even very complex compounds, lithium, sodium, potassium, rubidium, and cæsium present an indubitable chemical resemblance. The fact that the metals easily decompose water, and that their hydroxides RHO and carbonates R_{2}CO_{3} are soluble in water, whilst the hydroxides and carbonates of nearly all other metals are insoluble, shows that these metals form a natural group of _alkali metals_. The halogens and the alkali metals form, by their character, the two extremes of the elements. Many of the other elements are metals approaching the alkali metals, both in their capacity of forming salts and in not forming acid compounds, but are not so energetic as the alkali metals, that is, they form less energetic bases. Such are the common metals, silver, iron, copper, &c. Some other elements, in the character of their compounds, approach the halogens, and, like them, combine with hydrogen, but these compounds do not show the energetic property of the halogen acids; in a free state they easily combine with metals, but they do not then form such saline compounds as the halogens do--in a word, the halogen properties are less sharply defined in them than in the halogens themselves. Sulphur, phosphorus, arsenic, &c. belong to this order of elements. The clearest distinction of the properties of the halogens and alkali metals is expressed in the fact that the former give acids and do not form bases, whilst the latter, on the contrary, only give bases. The first are true _acid elements_, the latter clearly-defined _basic or metallic elements_. On combining together, the halogens form, in a chemical sense, unstable compounds, and the alkali metals alloys in which the character of the metals remains unaltered, just as in the compound ICl the character of the halogens remains undisguised; thus both classes of elements on combining with members of their own class form non-characteristic compounds, which have the properties of their components. On the other hand, the halogens on combining with the alkali metals form compounds which are, in all respects, stable, and in which the original characters of the halogens and alkali metals have entirely disappeared. The formation of such compounds is accompanied by evolution of a large amount of heat, and by an entire change of both the physical and chemical properties of the substances originally taken. The alloy of sodium and potassium, although liquid at the ordinary temperature, is perfectly metallic, like both its components. The compound of sodium and chlorine has neither the appearance nor the properties of the original elements; sodium chloride melts at a higher temperature, and is more difficultly volatile, than either sodium or chlorine. With all these qualitative differences there is, however, an important quantitative _resemblance between the halogens and the alkali metals_. This resemblance is clearly expressed by stating that both orders of elements belong to those which are univalent with respect to hydrogen. It is thus correct to say that both the above-named orders of elements replace hydrogen atom for atom. Chlorine is able to take the place of hydrogen by metalepsis, and the alkali metals take the place of hydrogen in water and acids. As it is possible to consecutively replace every equivalent of hydrogen in a hydrocarbon by chlorine, so it is possible in an acid containing several equivalents of hydrogen to replace the hydrogen consecutively equivalent after equivalent by an alkali metal; hence an atom of these elements is analogous to an atom of hydrogen, which is taken, in all cases, as the unit for the comparison of the other elements. In ammonia, and in water, chlorine and sodium are able to bring about a direct replacement. According to the law of substitution, the formation of sodium chloride, NaCl, at once shows the equivalence of the atoms of the alkali metals and the halogens. The halogens and hydrogen and the alkali metals combine with such elements as oxygen, and it is easily proved that in such compounds one atom of oxygen is able to retain two atoms of the halogens, of hydrogen, and of the alkali metals. For this purpose it is enough to compare the compounds KHO, K_{2}O, HClO, and Cl_{2}O, with water. It must not be forgotten, however, that the halogens give, with oxygen, besides compounds of the type R_{2}O, higher acid grades of oxidation, which the alkali metals and hydrogen are not capable of forming. We shall soon see that these relations are also subject to a special law, showing a gradual transition of the properties of the elements from the alkali metals to the halogens.[43] [43] We may here observe that the halogens, and especially iodine, may play the part of metals (hence iodine is more easily replaced by metals than the other halogens, and it approaches nearer to the metals in its physical properties than the other halogens). Schützenberger obtained a compound C_{2}H_{3}O(OCl), which he called chlorine acetate, by acting on acetic anhydride, (C_{2}H_{3}O)_{2}O, with chlorine monoxide, Cl_{2}O. With iodine this compound gives off chlorine and forms iodine acetate, C_{2}H_{3}O(OI), which also is formed by the action of iodine chloride on sodium acetate, C_{2}H_{3}O(ONa). These compounds are evidently nothing else than mixed anhydrides of hypochlorous and hypoiodous acids, or the products of the substitution of hydrogen in RHO by a halogen (_see_ Chapter XI., Notes 29 and 78 bis). Such compounds are very unstable, decompose with an explosion when heated, and are changed by the action of water and of many other reagents, which is in accordance with the fact that they contain very closely allied elements, as does Cl_{2}O itself, or ICl or KNa. By the action of chlorine monoxide on a mixture of iodine and acetic anhydride, Schützenberger also obtained the compound I(C_{2}H_{3}O_{2})_{3}, which is analogous to ICl_{3}, because the group C_{2}H_{3}O_{2} is, like Cl, a halogen, forming salts with the metals. Similar properties are found in iodosobenzene (Chapter XI., Note 79). The atomic weights of the alkali metals, lithium 7, sodium 23, potassium 39, rubidium 85, and cæsium 133, show that here, as in the class of halogens, the elements may be arranged according to their atomic weights in order to compare the properties of the analogous compounds of the members of this group. Thus, for example, the platinochlorides of lithium and sodium are soluble in water; those of potassium, rubidium, and cæsium sparingly soluble, and the greater the atomic weight of the metal the less soluble is the salt. In other cases the reverse is observed--the greater the atomic weight the more soluble are the corresponding salts. The variation of properties with the variation in atomic weights even shows itself in the metals themselves; thus lithium volatilises with difficulty, whilst sodium is obtained by distillation, potassium volatilises more easily than sodium, and rubidium and cæsium as we have seen, are still more volatile. CHAPTER XIV THE VALENCY AND SPECIFIC HEAT OF THE METALS. MAGNESIUM. CALCIUM, STRONTIUM, BARIUM, AND BERYLLIUM It is easy by investigating the composition of corresponding compounds, to establish the _equivalent weights_ of the metals compared with hydrogen--that is, the quantity which replaces one part by weight of hydrogen. If a metal decomposes acids directly, with the evolution of hydrogen, the equivalent weight of the metal may be determined by taking a definite weight of it and measuring the volume of hydrogen evolved by its action on an excess of acid; it is then easy to calculate the weight of the hydrogen from its volume.[1] The same result may be arrived at by determining the composition of the normal salts of the metal; for instance, by finding the weight of metal which combines with 35·5 parts of chlorine or 80 parts of bromine.[2] The equivalent of a metal may be also ascertained by simultaneously (_i.e._ in one circuit) decomposing an acid and a fused salt of a given metal by an electric current and determining the relation between the amounts of hydrogen and metal separated, because, according to Faraday's law, electrolytes (conductors of the second order) are always decomposed in equivalent quantities.[2 bis] The equivalent of a metal may even be found by simply determining the relation between its weight and that of its salt-giving oxide, as by this we know the quantity of the metal which combines with 8 parts by weight of oxygen, and this will be the equivalent, because 8 parts of oxygen combine with 1 part by weight of hydrogen. One method is verified by another, and all the processes for the accurate determination of equivalents require the greatest care to avoid the absorption of moisture, further oxidation, volatility, and other accidental influences which affect exact weighings. The description of the methods necessary for the attainment of exact results belongs to the province of analytical chemistry. [1] Under favourable circumstances (by taking all the requisite precautions), the weight of the equivalent may be accurately determined by this method. Thus Reynolds and Ramsay (1887) determined the equivalent of zinc to be 32·7 by this method (from the average of 29 experiments), whilst by other methods it has been fixed (by different observers) between 32·55 and 33·95. The differences in their equivalents may be demonstrated by taking equal weights of different metals, and collecting the hydrogen evolved by them (under the action of an acid or alkali). [2] The most accurate determinations of this kind were carried on by Stas, and will be described in Chapter XXIV. [2 bis] The amount of electricity in one coulomb according to the present nomenclature of electrical units (_see_ Works on Physics and Electro-technology) disengages 0·00001036 gram of hydrogen, 0·00112 gram of silver, 0·0003263 gram of copper from the salts of the oxide, and 0·0006526 gram from the salts of the suboxide, &c. These amounts stand in the same ratio as the equivalents, _i.e._ as the quantities replaced by one part by weight of hydrogen. The intimate bond which is becoming more and more marked existing between the electrolytic and purely chemical relations of substances (especially in solutions) and the application of electrolysis to the preparation of numerous substances on a large scale, together with the employment of electricity for obtaining high temperatures, &c., makes me regret that the plan and dimensions of this book, and the impossibility of giving a concise and objective exposition of the necessary electrical facts, prevent my entering upon this province of knowledge, although I consider it my duty to recommend its study to all those who desire to take part in the further development of our science. There is only one side of the subject respecting the direct correlation between thermochemical data and electro-motive force, which I think right to mention here, as it justifies the general conception, enunciated by Faraday, that the galvanic current is an aspect of the transference of chemical motion or reaction along the conductors. From experiments conducted by Favre, Thomsen, Garni, Berthelot, Cheltzoff, and others, upon the amount of heat evolved in a closed circuit, it follows that the electro-motive force of the current or its capacity to do a certain work, E, is proportional to the whole amount of heat, Q, disengaged by the reaction forming the source of the current. If E be expressed in volts, and Q in thousands of units of heat referred to equivalent weights, then E = 0·0436Q. For example in a Daniells battery E = 1·09 both by experiment and theory, because in it there takes place the decomposition of CuSO_{4} into Cu + O together with the formation of Zn + O and ZnO + SO_{3}Aq, and these reactions correspond to Q = 25·06 thousand units of heat. So also in all other primary batteries (_e.g._ Bunsen's, Poggendorff's, &c.) and secondary ones (for instance, those acting according to the reaction Pb + H_{2}SO_{4} + PbO_{2}, as Cheltzoff showed) E = 0·0436Q. For univalent metals, like those of the alkalis, the weight of the equivalent is equal to the weight of the atom. For bivalent metals the atomic weight is equal to the weight of two equivalents, for _n_-valent metals it is equal to the weight of _n_ equivalents. Thus aluminium, Al = 27, is trivalent, that is, its equivalent = 9; magnesium, Mg = 24, is bivalent, and its equivalent = 12. Therefore, if potassium or sodium, or in general a univalent metal, M, give compounds M_{2}O, MHO, MCl, MNO_{3}, M_{2}SO_{4}, &c., and in general MX, then for bivalent metals like magnesium or calcium the corresponding compounds will be MgO, Mg(HO)_{2}, MgCl_{2}, Mg(NO_{3})_{2}, MgSO_{4}, &c., or in general MX_{2}. By what are we to be guided in ascribing to some metals univalency and to others bi-, ter-, quadri-, ... _n_-valency? What obliges us to make this difference? Why are not all metals given the same valency--for instance, why is not magnesium considered as univalent? If this be done, taking Mg = 12 (and not 24 as now), not only is a simplicity of expression of the composition of all the compounds of magnesium attained, but we also gain the advantage that their composition will be the same as those of the corresponding compounds of sodium and potassium. These combinations were so expressed formerly--why has this since been changed? These questions could only be answered after the establishment of the idea of multiples of the atomic weights as the minimum quantities of certain elements combining with others to form compounds--in a word, since the time of the establishment of Avogadro-Gerhardt's law (Chapter VII.). By taking such an element as arsenic, which has many volatile compounds, it is easy to determine the density of these compounds, and therefore to establish their molecular weights, and hence to find the indubitable atomic weight, exactly as for oxygen, nitrogen, chlorine, carbon, &c. It appears that As = 75, and its compounds correspond, like the compounds of nitrogen, with the forms AsX_{3}, and AsX_{5}; for example, AsH_{3}, AsCl_{3}, AsF_{5}, As_{2}O_{5}, &c. It is evident that we are here dealing with a metal (or rather element) of two valencies, which moreover is never univalent, but tri- or quinqui-valent. This example alone is sufficient for the recognition of the existence of polyvalent atoms among the metals. And as antimony and bismuth are closely analogous to arsenic in all their compounds, (just as potassium is analogous to rubidium and cæsium); so, although very few volatile compounds of bismuth are known, it was necessary to ascribe to them formulæ corresponding with those ascribed to arsenic. As we shall see in describing them, there are also many analogous metals among the bivalent elements, some of which also give volatile compounds. For example, zinc, which is itself volatile, gives several volatile compounds (for instance, zinc ethyl, ZnC_{4}H_{10}, which boils at 118°, vapour density = 61·3), and in the molecules of all these compounds there is never less than 65 parts of zinc, which is equivalent to H_{2}, because 65 parts of zinc displace 2 parts by weight of hydrogen; so that zinc is just such an example of the bivalent metals as oxygen, whose equivalent = 8 (because H_{2} is replaced by O = 16), is a representative of the bivalent elements, or as arsenic is of the tri- and quinqui-valent elements. And, as we shall afterwards see, magnesium is in many respects closely analogous to zinc, which fact obliges us to regard magnesium as a bivalent metal. Such metals as mercury and copper, which are able to give not one but two bases, are of particular importance for distinguishing univalent and bivalent metals. Thus copper gives the suboxide Cu_{2}O and the oxide CuO--that is, the compounds CuX corresponding with the suboxide are analogous (in the quantitative relations, by their composition) to NaX or AgX, and the compounds of the oxide CuX_{2}, to MgX_{2}, ZnX_{2}, and in general to the bivalent metals. It is clear that in such examples we must make a distinction between atomic weights and equivalents. In this manner the valency, that is, the number of equivalents entering into the atom of the metals may in many cases be established by means of comparatively few volatile metallic compounds, with the aid of a search into their analogies (concerning which see Chapter XV.). _The law of specific heats_ discovered by Dulong and Petit has frequently been applied to the same purpose[3] in the history of chemistry, especially since the development given to this law by the researches of Regnault, and since Cannizzaro (1860) showed the agreement between the deductions of this law and the consequences arising from Avogadro-Gerhardt's law. [3] The chief means by which we determine the valency of the elements, or what multiple of the equivalent should be ascribed to the atom, are: (1) The law of Avogadro-Gerhardt. This method is the most general and trustworthy, and has already been applied to a great number of elements. (2) The different grades of oxidation and their isomorphism or analogy in general; for example, Fe = 56 because the suboxide (ferrous oxide) is isomorphous with magnesium oxide, &c., and the oxide (ferric oxide) contains half as much oxygen again as the suboxide. Berzelius, Marignac, and others took advantage of this method for determining the composition of the compounds of many elements. (3) The specific heat, according to Dulong and Petit's law. Regnault, and more especially Cannizzaro, used this method to distinguish univalent from bivalent metals. (4) The periodic law (_see_ Chapter XV.) has served as a means for the determination of the atomic weights of cerium, uranium, yttrium, &c., and more especially of gallium, scandium, and germanium. The correction of the results of one method by those of others is generally had recourse to, and is quite necessary, because, phenomena of dissociation, polymerisation, &c., may complicate the individual determinations by each method. It will be well to observe that a number of other methods, especially from the province of those physical properties which are clearly dependent on the magnitude of the atom (or equivalent) or of the molecule, may lead to the same result. I may point out, for instance, that even the specific gravity of solutions of the metallic chlorides may serve for this purpose. Thus, if beryllium he taken as trivalent--that is, if the composition of its chloride be taken as BeCl_{3} (or a polymeride of it), then the specific gravity of solutions of beryllium chloride will not fit into the series of the other metallic chlorides. But by ascribing to it an atomic weight Be = 7, or taking Be as bivalent, and the composition of its chloride as BeCl_{2}, we arrive at the general rule given in Chapter VII., Note 28. Thus W. G. Burdakoff determined in my laboratory that the specific gravity at 15°/4° of the solution BeCl_{2} + 200H_{2}O = 1·0138--that is, greater than the corresponding solution KCl + 200H_{2}O (= 1·0121), and less than the solution MgCl_{2} + 200H_{2}O (= 1·0203), as would follow from the magnitude of the molecular weight BeCl_{2} = 80, since KCl = 74·5 and MgCl_{2} = 95. Dulong and Petit, having determined the specific heat of a number of solid elementary substances, observed that as the atomic weights of the elements increase, their specific heats decrease, and that _the product of the specific heat Q into the atomic weight A is an almost constant quantity_. This means that to bring different elements into a known thermal state an equal amount of work is required if atomic quantities of the elements are taken; that is, the amounts of heat expended in heating equal quantities by weight of the elements are far from equal, but are in inverse proportion to the atomic weights. For thermal changes the atom is a unit; all atoms, notwithstanding the difference of weight and nature, are equal. This is the simplest expression of the fact discovered by Dulong and Petit. The specific heat measures that quantity of heat which is required to raise the temperature of _one unit of weight_ of a substance by one degree. If the magnitude of the specific heat of elements be multiplied by the atomic weight, then we obtain the atomic heat--that is, the amount of heat required to raise the temperature of the atomic weight of an element by one degree. It is these products which for the majority of the elements prove to be approximately, if not quite, identical. A complete identity cannot be expected, because the specific heat of one and the same substance varies with the temperature, with its passage from one state into another, and frequently with even a simple mechanical change of density (for instance by hammering), not to speak of allotropic changes, &c. We will cite several figures[4] proving the truth of the conclusions arrived at by Dulong and Petit with respect to solid elementary bodies. Li Na Mg P A = 7 23 24 31 Q = 0·9408 0·2934 0·245 0·202 AQ = 6·59 6·75 5·88 6·26 Fe Cu Zn Br A = 56 63 65 80 Q = 0·112 0·093 0·093 0·0843 AQ = 6·27 5·86 6·04 6·74 Pd Ag Sn I A = 106 108 118 127 Q = 0·0592 0·056 0·055 0·541 AQ = 6·28 6·05 6·49 6·87 Pt Au Hg Pb A = 196 198 200 206 Q = 0·0325 0·0324 0·0333 0·0315 AQ = 6·37 6·41 6·66 6·49 [4] The specific heats here given refer to different limits of temperature, but in the majority of cases between 0° and 100°; only in the case of bromine the specific heat is taken (for the solid state) at a temperature below -7°, according to Regnault's determination. _The variation of the specific heat with a change of temperature_ is a very complex phenomenon, the consideration of which I think would here be out of place. I will only cite a few figures as an example. According to Bystrom, the specific heat of iron at 0° = 0·1116, at 100° = 0·1114, at 200° = 0·1188, at 300° = 0·1267, and at 1,400° = 0·4031. Between these last limits of temperature a change takes place in iron (a spontaneous heating, _recalescence_), as we shall see in Chapter XXII. For quartz SiO_{2} Pionchon gives Q = 0·1737 + 394_t_10^{-6}-27_t_^{2}10^{-9} up to 400°, for metallic aluminium (Richards, 1892) at 0° 0·222, at 20° 0·224, at 100° 0·232; consequently, as a rule, the specific heat varies slightly with the temperature. Still more remarkable are H. E. Weber's observations on the great variation of the specific heat of charcoal, the diamond and boron: 0° 100° 200° 600° 900° Wood charcoal 0·15 0·23 0·29 0·44 0·46 Diamond 0·10 0·19 0·22 0·44 0·45 Boron 0·22 0·29 0·35 -- -- These determinations, which have been verified by Dewar, Le Chatelier (Chapter VIII., Note 13), Moissan, and Gauthier, the latter finding for boron AQ = 6 at 400°, are of especial importance as confirming the universality of Dulong and Petit's law, because the elements mentioned above form exceptions to the general rule when the mean specific heat is taken for temperatures between 0° and 100°. Thus in the case of the diamond the product of A × Q at 0° = 1·2, and for boron = 2·4. But if we take the specific heat towards which there is evidently a tendency with a rise of temperature, we obtain a product approaching to 6 as with other elements. Thus with the diamond and charcoal, it is evident that the specific heat tends towards 0·47, which multiplied by 12 gives 5·6, the same as for magnesium and aluminium. I may here direct the reader's attention to the fact that for solid elements having a small atomic weight, the specific heat varies considerably if we take the average figures for temperatures 0° to 100°: Li = 7 Be = 9 B = 11 C = 12 Q = 0·94 0·42 0·24 0·20 AQ = 6·6 3·8 2·6 2·4 It is therefore clear that the specific heat of beryllium determined at a low temperature cannot serve for establishing its atomicity. On the other hand, the low atomic heat of charcoal, graphite, and the diamond, boron, &c., may perhaps depend on the complexity of the molecules of these elements. The necessity for acknowledging a great complexity of the molecules of carbon was explained in Chapter VIII. In the case of sulphur the molecule contains at least S_{6} and its atomic heat = 32 × 0·163 = 5·22, which is distinctly below the normal. If a large number of atoms of carbon are contained in the molecule of charcoal, this would to a certain extent account for its comparatively small atomic heat. With respect to the specific heat of compounds, it will not be out of place to mention here the conclusion arrived at by Kopp, that the molecular heat (that is, the product of MQ) may be looked on as the sum of the atomic heats of its component elements; but as this rule is not a general one, and can only be applied to give an approximate estimate of the specific heats of substances, I do not think it necessary to go into the details of the conclusions described in Liebig's 'Annalen Supplement-Band,' 1864, which includes a number of determinations made by Kopp. It is seen from this that the product of the specific heat of the element into the atomic weight is an almost constant quantity, which is nearly 6. Hence it is possible to determine the valency by the specific heats of the metals. Thus, for instance, the specific heats of lithium, sodium, and potassium convince us of the fact that their atomic weights are indeed those which we chose, because by multiplying the specific heats found by experiment by the corresponding atomic weights we obtain the following figures: Li, 6·59, Na, 6·75 and K, 6·47. Of the alkaline earth metals the specific heats have been determined: of magnesium = 0·245 (Regnault and Kopp), of calcium = 0·170 (Bunsen), and of barium = 0·05 (Mendeléeff). If the same composition be ascribed to the compounds of magnesium as to the corresponding compounds of potassium, then the equivalent of magnesium will be equal to 12. On multiplying this atomic weight by the specific heat of magnesium, we obtain a figure 2·94, which is half that which is given by the other solid elements and therefore the atomic weight of magnesium must be taken as equal to 24 and not to 12. Then the atomic heat of magnesium = 24 × 0·245 = 5·9; for calcium, giving its compounds a composition CaX_{2}--for example CaCl_{2}, CaSO_{4}, CaO (Ca = 40)--we obtain an atomic heat = 40 × 0·17 = 6·8, and for barium it is equal to 137 × 0·05 = 6·8; that is, they must be counted as bivalent, or that their atom replaces H_{2}, Na_{2}, or K_{2}. This conclusion may be confirmed by a method of analogy, as we shall afterwards see. The application of the principle of specific heats to the determination of the magnitudes of the atomic weights of those metals, the magnitude of whose atomic weights could not be determined by Avogadro-Gerhardt's law, was made about 1860 by the Italian professor Cannizzaro. Exactly the same conclusions respecting the bivalence of magnesium and its analogues are obtained by comparing the specific heats of their compounds, especially of the halogen compounds as the most simple, with the specific heats of the corresponding alkali compounds. Thus, for instance, the specific heats of magnesium and calcium chlorides, MgCl_{2} and CaCl_{2}, are 0·194 and 0·164, and of sodium and potassium chlorides, NaCl and KCl, 0·214 and 0·172, and therefore their molecular heats (or the products QM, where M is the weight of the molecule) are 18·4 and 18·2, 12·5 and 12·8, and hence the atomic heats (or the quotient of QM by the number of atoms) are all nearly 6, as with the elements. Whilst if, instead of the actual atomic weights Mg = 24 and Ca = 40, their equivalents 12 and 20 be taken, then the atomic heats of the chlorides of magnesium and calcium would be about 4·6, whilst those of potassium and sodium chlorides are about 6·3.[5] We must remark, however, that as the specific heat or the amount of heat required to raise the temperature of a unit of weight one degree[6] is a complex quantity--including not only the increase of the energy of a substance with its rise in temperature, but also the external work of expansion[7] and the internal work accomplished in the molecules causing them to decompose according to the rise of temperature[8]--therefore it is impossible to expect in the magnitude of the specific heat the great simplicity of relation to composition which we see, for instance, in the density of gaseous substances. Hence, although the specific heat is one of the important means for determining the atomicity of the elements, still the mainstay for a true judgment of atomicity is only given by Avogadro-Gerhardt's law, _i.e._ this other method can only be accessory or preliminary, and when possible recourse should be had to the determination of the vapour density. [5] It must be remarked that in the case of oxygen (and also hydrogen and carbon) compounds the quotient of MQ/_n_, where _n_ is the number of atoms in the molecule, is always less than 6 for solids; for example, for MgO = 5·0, CuO = 5·1, MnO_{2} = 4·6, ice (Q = 0·504) = 3, SiO_{2} = 3·5, &c. At present it is impossible to say whether this depends on the smaller specific heat of the atom of oxygen in its solid compounds (Kopp, Note 4) or on some other cause; but, nevertheless, taking into account this decrease depending on the presence of oxygen, a reflection of the atomicity of the elements may to a certain extent be seen in the specific heat of the oxides. Thus for alumina, Al_{2}O_{3} (Q = 0·217), MQ = 22·3, and therefore the quotient MQ/_n_ = 4·5, which is nearly that given by magnesium oxide, MgO. But if we ascribe the same composition to alumina, as to magnesia--that is, if aluminium were counted as divalent--we should obtain the figure 3·7, which is much less. In general, in compounds of identical atomic composition and of analogous chemical properties the molecular heats MQ are nearly equal, as many investigators have long remarked. For example, ZnS = 11·7 and HgS = 11·8; MgSO_{4} = 27·0 and ZnSO_{4} = 28·0, &c. [6] If W be the amount of heat contained in a mass _m_ of a substance at a temperature _t_, and _d_W the amount expended in heating it from _t_ to _t_ + _dt_, then the specific heat Q = _d_W(_m_ × _dt_). The specific heat not only varies with the composition and complexity of the molecules of a substance, but also with the temperature, pressure, and physical state of a substance. Even for gases the variation of Q with _t_ is to be observed. Thus it is seen from the experiments of Regnault and Wiedemann that the specific heat of carbonic anhydride at 0° = 0·19, at 100° = 0·22, and at 200° = 0·24. But the variation of the specific heat of permanent gases with the temperature is, as far as we know, very inconsiderable. According to Mallard and Le Chatelier it is = 0·0006/M per 1°, where M is the molecular weight (for instance, for O_{2}, M = 32). Therefore the specific heat of those permanent gases which contain two atoms in the molecule (H_{2}, O_{2}, N_{2}, CO, and NO) may be, as is shown by experiment, taken as not varying with the temperature. The constancy of the specific heat of perfect gases forms one of the fundamental propositions of the whole theory of heat and on it depends the determination of temperatures by means of gas-thermometers containing hydrogen, nitrogen, or air. Le Chatelier (1887), on the basis of existing determinations, concludes that the molecular heat--that is, the product MQ--of all gases varies in proportion to the temperature, and tends to become equal (= 6·8) at the temperature of absolute zero (that is, at -273°); and therefore MQ = 6·8 + _a_(273 + _t_), where _a_ is a constant quantity which increases with the complexity of the gaseous molecule and Q is the specific heat of the gas under a constant pressure. For permanent gases _a_ almost = 0, and therefore MQ = 6·8--that is, the atomic heat (if the molecule contains two atoms) = 3·4, as it is in fact (Chapter IX., Note 17 bis). As regards liquids (as well as the vapours formed by them), the specific heat always rises with the temperature. Thus for benzene it equals 0·38 + 0·0014_t_. R. Schiff (1887) showed that the variation of the specific heat of many organic liquids is proportional to the change of temperature (as in the case of gases, according to Le Chatelier), and reduced these variations into dependence with their composition and absolute boiling point. It is very probable that the theory of liquids will make use of these simple relations which recall the simplicity of the variation of the specific gravity (Chapter II., Note 34), cohesion, and other properties of liquids with the temperature. They are all expressed by the linear function of the temperature, _a_ + _bt_, with the same degree of proximity as the property of gases is expressed by the equation _pv_ = _Rt_. As regards the relation between the specific heats of liquids (or of solids) and of their vapours, the specific heat of the vapour (and also of the solid) is always less than that of the liquid. For example, benzene vapour 0·22, liquid 0·38; chloroform vapour 0·13, liquid 0·23; steam 0·475, liquid water 1·0. But the complexity of the relations existing in specific heat is seen from the fact that the specific heat of ice = 0·502 is less than that of liquid water. According to Regnault, in the case of bromine the specific heat of the vapour = 0·055 at (150°), of the liquid = 0·107 (at 30°), and of solid bromine = 0·084 (at -15°). The specific heat of solid benzoic acid (according to experiment and calculation, Hess, 1888) between 0° and 100° is 0·31, and of liquid benzoic acid 0·50. One of the problems of the present day is the explanation of those complex relations which exist between the composition and such properties as specific heat, latent heat, expansion by heat, compression, internal friction, cohesion, and so forth. They can only be connected by a complete theory of liquids, which may now soon be expected, more especially as many sides of the subject have already been partially explained. [7] According to the above reasons the quantity of heat, Q, required to raise the temperature of one part by weight of a substance by one degree may be expressed by the sum Q = K + B + D, where K is the heat actually expended in heating the substance, or what is termed the absolute specific heat, B the amount of heat expended in the internal work accomplished with the rise of temperature, and D the amount of heat expended in external work. In the case of gases the last quantity may be easily determined, knowing their coefficient of expansion, which is approximately = 0·00368. By applying to this case the same argument given at the end of Note 11, Chapter I., we find that one cubic metre of a gas heated 1° produces an external work of 10333 × 0·00368, or 38·02 kilogrammetres, on which 38·02/424 or 0·0897 heat units are expended. This is the heat expended for the external work produced by one cubic metre of a gas, but the specific heat refers to units of weight, and therefore it is necessary in order to know D to reduce the above quantity to a unit of weight. One cubic metre of hydrogen at 0° and 760 mm. pressure weighs 0·0896 kilo, a gas of molecular weight M has a density M/2, consequently a cubic metre weighs (at 0° and 760 mm.) 0·0448M kilo, and therefore 1 kilogram of the gas occupies a volume 1/0·0448M cubic metres, and hence the external work D in the heating of 1 kilo of the given gas through 1° = 0·0896/0·0448M, or D = 2/M. Taking the magnitude of the internal work B for gases as negligible if permanent gases are taken, and therefore supposing B = 0, we find the specific heat of gases at a constant pressure Q = K + 2 M, where K is the specific heat at a constant volume, or the true specific heat, and M the molecular weight. Hence K = Q-2/M. The magnitude of the specific heat Q is given by direct experiment. According to Regnault's experiments, for oxygen it = 0·2175, for hydrogen 3·405, for nitrogen 0·2438; the molecular weights of these gases are 32, 2, and 28, and therefore for oxygen K = 0·2175-0·0625 = 0·1550, for hydrogen K = 3·4050-1·000 = 2·4050, and for nitrogen K = 0·2438-0·0714 = 0·1724. These true specific heats of elements are in inverse proportion to their atomic weights--that is, their product by the atomic weight is a constant quantity. In fact, for oxygen this product = 0·155 × 16 = 2·48, for hydrogen 2·40, for nitrogen 0·7724 × 14 = 2·414, and therefore if A stand for the atomic weight we obtain the expression K × A = a constant, which may be taken as 2·45. This is the true expression of Dulong and Petit's law, because K is the true specific heat and A the weight of the atom. It should be remarked, moreover, that the product of the observed specific heat Q into A is also a constant quantity (for oxygen = 3·48, for hydrogen = 3·40), because the external work D is also inversely proportional to the atomic weight. In the case of gases we distinguish the specific heat at a constant pressure _c´_ (we designated this quantity above by Q), and at a constant volume _c_. It is evident that _the relation between the two specific heats, k_, judging from the above, is the ratio of Q to K, or equal to the ratio of 2·45_n_ + 2 to 2·45_n_. When _n_ = 1 this ratio _k_ = 1·8; when _n_ = 2, _k_ = 1·4, when _n_ = 3, _k_ = 1·3, and with an exceedingly large number _n_, of atoms in the molecule, _k_ = 1. That is, the ratio between the specific heats decreases from 1·8 to 1·0 as the number of atoms, _n_, contained in the molecule increases. This deduction is verified to a certain extent by direct experiment. For such gases as hydrogen, oxygen, nitrogen, carbonic oxide, air, and others in which _n_ = 2, the magnitude of _k_ is determined by methods described in works on physics (for example, by the change of temperature with an alteration of pressure, by the velocity of sound, &c.) and is found in reality to be nearly 1·4, and for such gases as carbonic anhydride, nitric dioxide, and others it is nearly 1·3. Kundt and Warburg (1875), by means of the approximate method mentioned in Note 29, Chapter VII., determined _k_ for mercury vapour when _n_ = 1, and found it to be = 1·67--that is, a larger quantity than for air, as would be expected from the above. It may be admitted that the true atomic heat of gases = 2·43, only under the condition that they are distant from a liquid state, and do not undergo a chemical change when heated--that is, when no internal work is produced in them (B = 0). Therefore this work may to a certain extent be judged by the observed specific heat. Thus, for instance, for chlorine (Q = 0·12, Regnault; _k_ = 1·33, according to Straker and Martin, and therefore K = 0·09, MK = 6·4), the atomic heat (3·2) is much greater than for other gases containing two atoms in a molecule, and it must be assumed, therefore, that when it is heated some great internal work is accomplished. In order to generalise the facts concerning the specific heat of gases and solids, it appears to me possible to accept the following general proposition: _the atomic heat_ (that is, AQ or QM/_n_, where M is the molecular weight and _n_ the number of molecules) is _smaller_ (in solids it attains its highest value 6·8 and in gases 3·4), _the more complex the molecule_ (i.e. _the greater the number (n) of atoms forming it_) _and so much smaller, up to a certain point_ (in similar physical states) _the smaller the mean atomic weight M/n_. [8] As an example, it will be sufficient to refer to the specific heat of nitrogen tetroxide, N_{2}O_{4}, which, when heated, gradually passes into NO_{2}--that is, chemical work of decomposition proceeds, which consumes heat. Speaking generally, specific heat is a complex quantity, in which it is clear that thermal data (for instance, the heat of reaction) alone cannot give an idea either of chemical or of physical changes individually, but always depend on an association of the one and the other. If a substance be heated from _t__{0} to _t__{1} it cannot but suffer a chemical change (that is, the state of the atoms in the molecules changes more or less in one way or another) if dissociation sets in at a temperature _t__{1}. Even in the case of the elements whose molecules contain only one atom, a true chemical change is possible with a rise of temperature, because more heat is evolved in chemical reactions than that quantity which participates in purely physical changes. One gram of hydrogen (specific heat = 3·4 at a constant pressure) cooled to the temperature of absolute zero will evolve altogether about one thousand units of heat, 8 grams of oxygen half this amount, whilst in combining together they evolve in the formation of 9 grams of water more than thirty times as much heat. Hence the store of chemical energy (that is, of the motion of the atoms, vortex, or other) is much greater than the physical store proper to the molecules, but it is the change accomplished by the former that is the cause of chemical transformations. Here we evidently touch on those limits of existing knowledge beyond which the teaching of science does not yet allow us to pass. Many new scientific discoveries have still to be made before this is possible. Among the bivalent metals the first place, with respect to their distribution in nature, is occupied by _magnesium_ and _calcium_, just as sodium and potassium stand first amongst the univalent metals. The relation which exists between the atomic weights of these four metals confirms the above comparison. In fact, the combining weight of magnesium is equal to 24, and of calcium 40; whilst the combining weights of sodium and potassium are 23 and 39--that is, the latter are one unit less than the former.[9] They all belong to the number of _light metals_, as they have but a small specific gravity, in which respect they differ from the ordinary, generally known heavy, or ore, metals (for instance, iron, copper, silver, and lead), which are distinguished by a much greater specific gravity. There is no doubt that their low specific gravity has a significance, not only as a simple point of distinction, but also as a property which determines the fundamental properties of these metals. Indeed, all the light metals have a series of points of resemblance with the metals of the alkalis; thus both magnesium and calcium, like the metals of the alkalis, decompose water (without the addition of acids), although not so easily as the latter metals. The process of the decomposition is essentially one and the same; for example, Ca + 2H_{2}O = CaH_{2}O_{2} + H_{2}--that is, hydrogen is liberated and a hydroxide of the metal formed. These hydroxides are bases which neutralise nearly all acids. However, the hydroxides RH_{2}O_{2} of calcium and magnesium are in no respect so energetic as the hydroxides of the true metals of the alkalis; thus when heated they lose water, are not so soluble, develop less heat with acids, and form various salts, which are less stable and more easily decomposed by heat than the corresponding salts of sodium and potassium. Thus calcium and magnesium carbonates easily part with carbonic anhydride when ignited; the nitrates are also very easily decomposed by heat, calcium and magnesium oxides, CaO and MgO, being left behind. The chlorides of magnesium and calcium, when heated with water, evolve hydrogen chloride, forming the corresponding hydroxides, and when ignited the oxides themselves. All these points are evidence of a weakening of the alkaline properties. [9] As if NaH = Mg and KH = Ca, which is in accordance with their valency. KH includes two monovalent elements, and is a bivalent group like Ca. These metals have been termed _the metals of the alkaline earths_, because they, like the alkali metals, form energetic bases. They are called alkaline _earths_ because they are met with in nature in a state of combination, forming the insoluble mass of the earth, and because as oxides, RO, they themselves have an earthy appearance. Not a few salts of these metals are known which are insoluble in water, whilst the corresponding salts of the alkali metals are generally soluble--for example, the carbonates, phosphates, borates, and other salts of the alkaline earth metals are nearly insoluble. This enables us to separate the metals of the alkaline earths from the metals of the alkalis. For this purpose a solution of ammonium carbonate is added to a mixed solution of salts of both kinds of metals, when by a double decomposition the insoluble carbonates of the metals of the alkaline earths are formed and fall as a precipitate, whilst the metals of the alkalis remain in solution: RX_{2} + Na_{2}CO_{3} = RCO_{3} + 2NaX. We may here remark that the oxides of the metals of the alkaline earths are frequently called by special names: MgO is called magnesia or bitter earth; CaO, lime; SrO, strontia; and BaO, baryta. In the primary rocks the oxides of calcium and magnesium are combined with silica, sometimes in variable quantities, so that in some cases the lime predominates and in other cases the magnesium. The two oxides, being analogous to each other, replace each other in equivalent quantities. The various forms of _augite_, _hornblende_, or _amphibole_, and of similar minerals, which enter into the composition of nearly all rocks, contain lime and magnesia and silica. The majority of the primary rocks also contain alumina, potash, and soda. These rocks, under the action of water (containing carbonic acid) and air, give up lime and magnesia to the water, and therefore they are contained in all kinds of water, and especially in sea-water. The _carbonates_ CaCO_{3} and MgCO_{3}, frequently met with in nature, _are soluble in an excess of water saturated with carbonic anhydride_,[10] and therefore many natural waters contain these salts, and are able to yield them when evaporated. However, one kilogram of water saturated with carbonic anhydride does not dissolve more than three grams of calcium carbonate. By gradually expelling the carbonic anhydride from such water, an insoluble precipitate of calcium carbonate separates out. It may confidently be stated that the formation of the very widely distributed strata of calcium and magnesium carbonates was of this nature, because these strata are of a sedimentary character--that is, such as would be exhibited by a gradually accumulating deposit on the bottom of the sea, and, moreover, frequently containing the remains of marine plants, and animals, shells, &c. It is very probable that the presence of these organisms in the sea has played the chief part in the precipitation of the carbonates from the sea water, because the plants absorb CO_{2}, and many of the organisms CaCO_{3}, and after death give deposits of carbonate of lime; for instance, chalk, which is almost entirely composed of the minute remains of the calcareous shields of such organisms. These deposits of calcium and magnesium carbonates are the most important sources of these metals. Lime generally predominates, because it is present in rocks and running water in greater quantity than magnesia, and in this case these sedimentary rocks are termed _limestone_. Some common flagstones used for paving, &c., and chalk may be taken as examples of this kind of formation. Those limestones in which a considerable portion of the calcium is replaced by magnesium are termed _dolomites_. The dolomites are distinguished by their hardness, and by their not parting with the whole of their carbonic anhydride so easily as the limestones under the action of acids. Dolomites[11] sometimes contain an equal number of molecules of calcium carbonate and magnesium carbonate, and they also sometimes appear in a crystalline form, which is easily intelligible, because calcium carbonate itself is exceedingly common in this form in nature, and is then known as _calc spar_, whilst natural crystalline magnesium carbonate is termed _magnesite_. The formation of the crystalline varieties of the insoluble carbonates is explained by the possibility of a slow deposition from solutions containing carbonic acid. Besides which (Chapter X.) calcium and magnesium sulphates are obtained from sea water, and therefore they are met with both as deposits and in springs. It must be observed that magnesium is held in considerable quantities in sea water, because the sulphate and chloride of magnesium are very soluble in water, whilst calcium sulphate is but little soluble, and is used in the formation of shells; and therefore if the occurrence of considerable deposits of magnesium sulphate cannot be expected in nature, still, on the other hand, one would expect (and they do actually occur) large masses of calcium sulphate or _gypsum_, CaSO_{4},2H_{2}O. Gypsum sometimes forms strata of immense size, which extend over many hectometres--for example, in Russia on the Volga, and in the Donetz and Baltic provinces. [10] Sodium carbonate and other carbonates of the alkalis give acid salts which are less soluble than the normal; here, on the contrary, with an excess of carbonic anhydride, a salt is formed which is more soluble than the normal, but this acid salt is more unstable than sodium hydrogen carbonate, NaHCO_{3}. [11] The formation of dolomite may be explained, if only we imagine that a solution of a magnesium salt acts on calcium carbonate. Magnesium carbonate may be formed by double decomposition, and it must be supposed that this process ceases at a certain limit (Chapter XII.), when we shall obtain a mixture of the carbonates of calcium and magnesium. Haitinger heated a mixture of calcium carbonate, CaCO_{3}, with a solution of an equivalent quantity of magnesium sulphate, MgSO_{4}, in a closed tube at 200°, and then a portion of the magnesia actually passed into the state of magnesium carbonate, MgCO_{3}, and a portion of the lime was converted into gypsum, CaSO_{4}. Lubavin (1892) showed that MgCO_{3} is more soluble than CaCO_{3} in salt water, which is of some significance in explaining the composition of sea water. Lime and magnesia also, but in much smaller quantities (only to the amount of several fractions of a per cent. and rarely more), enter into the composition of every fertile soil, and without these bases the soil is unable to support vegetation. Lime is particularly important in this respect, and its presence in a larger quantity generally improves the harvest, although purely calcareous soils are as a rule infertile. For this reason the soil is fertilised both with lime[12] itself and with marl--that is, with clay mixed with a certain quantity of calcium carbonate, strata of which are found nearly everywhere. [12] The undoubted action of lime in increasing the fertility of soils--if not in every case, at all events, with ordinary soils which have long been under corn--is based not so much on the need of plants for the lime itself as on those chemical and physical changes which it produces in the soil, as a particularly powerful base which aids the alteration of the mineral and organic elements of the soil. From the soil the lime and magnesia (in a smaller quantity) pass into the substance of _plants_, where they occur as salts. Certain of these salts separate in the interior of plants in a crystalline form--for example, calcium oxalate. The lime occurring in plants serves as the source for the formation of the various calcareous secretions which are so common in _animals_ of all classes. The bones of the highest animal orders, the shells of mollusca, the covering of the sea-urchin, and similar solid secretions of sea animals, contain calcium salts; namely, the shells mainly calcium carbonate, and the bones mainly calcium phosphate. Certain limestones are almost entirely formed of such deposits. Odessa is situated on a limestone of this kind, composed of shells. Thus magnesium and calcium occur throughout the entire realm of nature, but calcium predominates. As lime and magnesia form bases which are in many respects analogous, they were not distinguished from each other for a long time. Magnesia was obtained for the first time in the seventeenth century from Italy, and used as a medicine; and it was only in the last century that Black, Bergmann, and others distinguished magnesia from lime. _Metallic magnesium_ (and calcium also) is not obtained by heating magnesium oxide or the carbonate with charcoal, as the alkali metals are obtained,[13] but is liberated by the action of a galvanic current on fused magnesium chloride (best mixed with potassium chloride); Davy and Bussy obtained metallic magnesium by acting on magnesium chloride with the vapours of potassium. At the present time (Deville's process) magnesium is prepared in rather considerable quantities by a similar process, only the potassium is replaced by sodium. Anhydrous magnesium chloride, together with sodium chloride and calcium fluoride, is fused in a close crucible. The latter substances only serve to facilitate the formation of a fusible mass before and after the reaction, which is indispensable in order to prevent the access and action of air. One part of finely divided sodium to five parts of magnesium chloride is thrown into the strongly heated molten mass, and after stirring the reaction proceeds very quickly, and magnesium separates, MgCl_{2} + Na_{2} = Mg + 2NaCl. In working on a large scale, the powdery metallic magnesium is then subjected to distillation at a white heat. The distillation of the magnesium is necessary, because the undistilled metal is not homogeneous[14] and burns unevenly: the metal is prepared for the purpose of illumination. Magnesium is a white metal, like silver; it is not soft like the alkali metals, but is, on the contrary, hard like the majority of the ordinary metals. This follows from the fact that it melts at a somewhat high temperature--namely, about 500°--and boils at about 1000°. It is malleable and ductile, like the generality of metals, so that it can be drawn into wires and rolled into ribbon; it is most frequently used for lighting purposes in the latter form. Unlike the alkali metals, magnesium does not decompose the atmospheric moisture at the ordinary temperature, so that it is almost unacted on by air; it is not even acted on by water at the ordinary temperature, so that it may be washed to free it from sodium chloride. Magnesium only decomposes water with the evolution of hydrogen at the boiling point of water,[15] and more rapidly at still higher temperatures. This is explained by the fact that in decomposing water magnesium forms an insoluble hydroxide, MgH_{2}O_{2}, which covers the metal and hinders the further action of the water. Magnesium easily displaces hydrogen from acids, forming magnesium salts. When ignited it _burns_, not only in oxygen but in air (and even in carbonic anhydride), forming a white powder of magnesium oxide, or magnesia; in burning it emits a white and exceedingly _brilliant light_. The strength of this light naturally depends on the fact that magnesium (24 parts by weight) in burning evolves about 140 thousand heat units, and that the product of combustion, MgO, is infusible by heat; so that the vapour of the burning magnesium contains an ignited powder of non-volatile and infusible magnesia, and consequently presents all the conditions for the production of a brilliant light. The light emitted by burning magnesium contains many rays which act chemically, and are situated in the violet and ultra-violet parts of the spectrum. For this reason burning magnesium may be employed for producing photographic images.[16] [13] Sodium and potassium only decompose magnesium oxide at a white heat and very feebly, probably for two reasons. In the first place, because the reaction Mg + O develops more heat (about 140 thousand calories) than K_{2} + O or Na_{2} + O (about 100 thousand calories); and, in the second place, because magnesia is not fusible at the heat of a furnace and cannot act on the charcoal, sodium, or potassium--that is, it does not pass into that mobile state which is necessary for reaction. The first reason alone is not sufficient to explain the absence of the reaction between charcoal and magnesia, because iron and charcoal in combining with oxygen evolve less heat than sodium or potassium, yet, nevertheless, they can displace them. With respect to magnesium chloride, it acts on sodium and potassium, not only because their combination with chlorine evolves more heat than the combination of chlorine and magnesium (Mg + Cl_{2} gives 150 and Na_{2} + Cl_{2} about 195 thousand calories), but also because a fusion, both of the magnesium chloride and of the double salt, takes place under the action of heat. It is probable, however, that a reverse reaction will take place. A reverse reaction might probably be expected, and Winkler (1890) showed that Mg reduces the oxides of the alkali metals (Chapter XIII., Note 42). [14] Commercial magnesium generally contains a certain amount of magnesium nitride (Deville and Caron), Mg_{3}N_{2}--that is, a product of substitution of ammonia which is directly formed (as is easily shown by experiment) when magnesium is heated in nitrogen. It is a yellowish green powder, which gives ammonia and magnesia with water, and cyanogen when heated with carbonic anhydride. Pashkoffsky (1893) showed that Mg_{3}N_{2} is easily formed and is the sole product when Mg is heated to redness in a current of NH_{3}. Perfectly pure magnesium may be obtained by the action of a galvanic current. [15] Hydrogen peroxide (Weltzien) dissolves magnesium. The reaction has not been investigated. [16] A special form of apparatus is used for burning magnesium. It is a clockwork arrangement in which a cylinder rotates, round which a ribbon or wire of magnesium is wound. The wire is subjected to a uniform unwinding and burning as the cylinder rotates, and in this manner the combustion may continue uniform for a certain time. The same is attained in special lamps, by causing a mixture of sand and finely divided magnesium to fall from a funnel-shaped reservoir on to the flame. In photography it is best to blow finely divided magnesium into a colourless (spirit or gas) flame, and for instantaneous photography to light a cartridge of a mixture of magnesium and chlorate of potassium by means of a spark from a Ruhmkorff's coil (D. Mendeléeff, 1889). Owing to its great affinity for oxygen, magnesium _reduces_ many metals (zinc, iron, bismuth, antimony, cadmium, tin, lead, copper, silver, and others) from solutions of their salts at the ordinary temperature,[17] and at a red heat finely divided magnesium takes up the oxygen from silica, alumina, boric anhydride, &c.; so that silicon and similar elements may be obtained by directly heating a mixture of powdered silica and magnesium in an infusible glass tube.[18] [17] According to the observations of Maack, Comaille, Böttger, and others. The reduction by heat mentioned further on was pointed out by Geuther, Phipson, Parkinson and Gattermann. [18] This action of metallic magnesium in all probability depends, although only partially (_see_ Note 13), on its volatility, and on the fact that, in combining with a given quantity of oxygen, it evolves more heat than aluminium, silicon, potassium, and other elements. The affinity of magnesium for the halogens is much more feeble than for oxygen,[19] as is at once evident from the fact that a solution of iodine acts feebly on magnesium; still magnesium burns in the vapours of iodine, bromine, and chlorine. The character of magnesium is also seen in the fact that all its salts, especially in the presence of water, are decomposable at a comparatively moderate temperature, the elements of the acid being evolved, and the magnesium oxide, which is non-volatile and unchangeable by heat, being left. This naturally refers to those acids which are themselves volatilised by heat. Even magnesium sulphate is completely decomposed at the temperature at which iron melts, oxide of magnesium remaining behind. This decomposition of magnesium salts by heat proceeds much more easily than that of calcium salts. For example, magnesium carbonate is totally decomposed at 170°, magnesium oxide being left behind. This _magnesia_, or _magnesium oxide_, is met with both in an anhydrous and hydrated state in nature (the anhydrous magnesia as the mineral _periclase_, MgO, and the hydrated magnesia as _brucite_, MgH_{2}O_{2}). Magnesia is a well-known medicine (calcined magnesia--_magnesia usta_). It is a white, extremely fine, and very voluminous powder, of specific gravity 3·4; it is infusible by heat, and only shrinks or shrivels in an oxyhydrogen flame. After long contact the anhydrous magnesia combines with water, although very slowly, forming the hydroxide Mg(HO)_{2}, which, however, parts with its water with great ease when heated even below a red heat, and again yields anhydrous magnesia. This hydroxide is obtained directly as a gelatinous amorphous substance when a soluble alkali is mixed with a solution of any magnesium salt, MgCl_{2} + 2KHO = Mg(HO)_{2} + 2KCl. This decomposition is complete, and nearly all the magnesium passes into the precipitate; and this clearly shows the almost perfect insolubility of magnesia in water. Water dissolves a scarcely perceptible quantity of magnesium hydroxide--namely, one part is dissolved by 55,000 parts of water. Such a solution, however, has an alkaline reaction, and gives, with a salt of phosphoric acid, a precipitate of magnesium phosphate, which is still more insoluble. Magnesia is not only dissolved by acids, forming salts, but it also displaces certain other bases--for example, ammonia from ammonium salts when boiled; and the hydroxide also absorbs carbonic anhydride from the air. The magnesium salts, like those of calcium, potassium, and sodium, are colourless if they are formed from colourless acids. Those which are soluble have a bitter taste, whence magnesia has been termed _bitter-earth_. In comparison with the alkalis magnesia is a feeble base, inasmuch as it forms somewhat unstable salts, easily gives basic salts, forms acid salts with difficulty, and is able to give double salts with the salts of the alkalis, which facts are characteristic of feeble bases, as we shall see in becoming acquainted with the different metals. [19] Davy, on heating magnesia in chlorine, concluded that there was a complete substitution, because the volume of the oxygen was half the volume of the chlorine; it is probable, however, that owing to the formation of chlorine oxide (Chapter XI., Note 30) the decomposition is not complete and is limited by a reverse reaction. The power of magnesium salts to form double and basic salts is very frequently shown in reactions, and is specially marked as regards ammonium salts. If saturated solutions of magnesium and ammonium sulphates are mixed together, a crystalline double salt Mg(NH_{4})_{2}(SO_{4})_{2},6H_{2}O,[20] is immediately precipitated. A strong solution of ordinary ammonium carbonate dissolves magnesium oxide or carbonate, and precipitates crystals of a double salt, Mg(NH_{4})_{2}(CO_{3})_{2},4H_{2}O, from which water extracts the ammonium carbonate. With an excess of an ammonium salt the double salt passes into solution,[21] and therefore if a solution contain a magnesium salt and an excess of an ammonium salt--for instance, sal-ammoniac--then sodium carbonate will no longer precipitate magnesium carbonate. A mixture of solutions of magnesium and ammonium chlorides, on evaporation or refrigeration, gives a double salt, Mg(NH_{4})Cl_{3},6H_{2}O.[22] The salts of potassium, like those of ammonium, are able to enter into combination with the magnesium salts.[23] For instance, the double salt, MgKCl_{3},6H_{2}O, which is known as _carnallite_,[24] and occurs in the salt mines of Stassfurt, may be formed by freezing a saturated solution of potassium chloride with an excess of magnesium chloride. A saturated solution of magnesium sulphate dissolves potassium sulphate, and solid magnesium sulphate is soluble in a saturated solution of potassium sulphate. A double salt, K_{2}Mg(SO_{4})_{2},6H_{2}_O, which closely resembles the above-mentioned ammonium salt, crystallises from these solutions.[25] The nearest analogues of magnesium are able to give exactly similar double salts, both in crystalline form (monoclinic system) and composition; they, like this salt (_see_ Chapter XV.), are easily able (at 140°) to part with all their water of crystallisation, and correspond with the salts of sulphuric acid, whose type may be taken as _magnesium sulphate_, MgSO_{4}.[26] It occurs at Stassfurt as _kieserite_, MgSO_{4},H_{2}O, and generally separates from solutions as a heptahydrated salt, MgSO_{4},7H_{2}O, and from supersaturated solutions as a hexahydrated salt, MgSO_{4},6H_{2}O; at temperatures below 0° it crystallises out as a dodecahydrated salt, MgSO_{4},12H_{2}O, and a solution of the composition MgSO_{4},2H_{2}O solidifies completely at -5°.[27] Thus between water and magnesium sulphate there may exist several definite and more or less stable degrees of equilibrium; the double salt MgSO_{4}K_{2}SO_{4},6H_{2}O may be regarded as one of these equilibrated systems, the more so since it contains 6H_{2}O, whilst MgSO_{4} forms its most stable system with 7H_{2}O, and the double salt may be considered as this crystallo-hydrate in which one molecule of water is replaced by the molecule K_{2}SO_{4}.[28] [20] Even a solution of ammonium chloride gives this salt with magnesium sulphate. Its sp. gr. is 1·72; 100 parts of water at 0° dissolve 9, at 20° 17·9 parts of the anhydrous salt. At about 130° it loses all its water. [21] This is an example of equilibrium and of the influence of mass; the double salt is decomposed by water, but if instead of water we take a solution of that soluble part which is formed in the decomposition of the double salt, then the latter dissolves as a whole. [22] If an excess of ammonia be added to a solution of magnesium chloride, only half the magnesium is thrown down in the precipitate, 2MgCl_{2} + 2NH_{4}.OH = Mg(OH)_{2} + Mg.NH_{4}Cl_{3} + NH_{4}Cl. A solution of ammonium chloride reacts with magnesia, evolving ammonia and forming a solution of the same salt, MgO + 3NH_{4}Cl = MgNH_{4}Cl_{3} + H_{2}O + 2NH_{3}. Among the double salts of ammonium and magnesium, the phosphate, MgNH_{4}PO_{4},6H_{2}O, is almost insoluble in water (0·07 gram is soluble in a litre), even in the presence of ammonia. Magnesia is very frequently precipitated as this salt from solutions in which it is held by ammonium salts. As lime is not retained in solution by the presence of ammonium salts, but is precipitated nevertheless by sodium carbonate, &c., it is very easy to separate calcium from magnesium by taking advantage of these properties. [23] In order to see the nature and cause of formation of double salts, it is sufficient (although this does not embrace the whole essence of the matter) to consider that one of the metals of such salts (for instance, potassium) easily gives acid salts, and the other (in this instance, magnesium) basic salts; the properties of distinctly basic elements predominate in the former, whilst in the latter these properties are enfeebled, and the salts formed by them bear the character of acids--for example, the salts of aluminium or magnesium act in many cases like acids. By their mutual combination these two opposite properties of the salts are both satisfied. [24] Carnallite has been mentioned in Chapter X. (Note 4) and in Chapter XIII. These deposits also contain much _kainite_, KMgCl(SO_{4}),3H_{2}O (sp. gr. 2·13; 100 parts of water dissolve 79·6 parts at 18°). This double salt contains two metals and two haloids. Feit (1889) also obtained a bromide corresponding to carnallite. [25] The component parts of certain double salts diffuse at different rates, and as the diffused solution contains a different proportion of the component salts than the solution taken of the double salt, it shows that such salts are decomposed by water. According to Rüdorff, the double salts, like carnallite, MgK_{2}(SO_{4})_{2},6H_{2}O, and the alums, all belong to this order (1888). But such salts as tartar emetic, the double oxalates, and double cyanides are not separated by diffusion, which in all probability depends both on the relative rate of the diffusion of the component salts and on the degree of affinity acting between them. Those complex states of equilibrium which exist between water, the individual salts MX and NY, and the double salt MNXY, have been already partially analysed (as will be shown hereafter) in that case when the system is heterogeneous (that is, when something separates out in a solid state from the liquid solution), but in the case of equilibria in a homogeneous liquid medium (in a solution) the phenomenon is not so clear, because it concerns that very theory of solution which cannot yet be considered as established (Chapter I., Note 9, and others). As regards the heterogeneous decomposition of double salts, it has long been known that such salts as carnallite and K_{2}Mg(SO_{4})_{2} give up the more soluble salt if an insufficient quantity of water for their complete solution be taken. The complete saturation of 100 parts of water requires at 0° 14·1, at 20° 25, and at 60° 50·2 parts of the latter double salt (anhydrous), while 100 parts of water dissolve 27 parts of magnesium sulphate at 0°, 36 parts at 20°, and 55 parts at 60°, of the anhydrous salt taken. Of all the states of equilibrium exhibited by double salts the most fully investigated as yet is the system containing water, sodium sulphate, magnesium sulphate, and their double salt, Na_{2}Mg(SO_{4})_{2}, which crystallises with 4 and 6 mol. OH_{2}. The first crystallo-hydrate, MgNa_{2}(SO_{4})_{2},4H_{2}O, occurs at Stassfurt, and as a sedimentary deposit in many of the salt lakes near Astrakhan, and is therefore called _astrakhanite_. The specific gravity of the monoclinic prisms of this salt is 2·22. If this salt, in a finely divided state, be mixed with the necessary quantity of water (according to the equation MgNa_{2}(SO_{4})_{2},4H_{2}O + 13H_{2}O = Na_{2}SO_{4},10H_{2}O + MgSO_{4},7H_{2}O), the mixture solidifies like plaster of Paris into a homogeneous mass if the temperature be _below_ 22° (Van't Hoff und Van Deventer, 1886; Bakhuis Roozeboom, 1887); but if the temperature be above this _transition-point_ the water and double salt do not react on each other: that is, they do not solidify or give a mixture of sodium and magnesium sulphates. If a mixture (in equivalent quantities) of solutions of these salts be evaporated, and crystals of astrakhanite and of the individual salts capable of proceeding from it be added to the concentrated solution to avoid the possibility of a supersaturated solution, then at temperatures above 22° astrakhanite is exclusively formed (this is the method of its production), but at lower temperatures the individual salts are alone produced. If equivalent amounts of Glauber's salt and magnesium sulphate be mixed together in a solid state, there is no change at temperatures below 22°, but at higher temperatures astrakhanite and water are formed. The volume occupied by Na_{2}SO_{4},10H_{2}O in grams = 322/1·46 = 220·5 cubic centimetres, and by MgSO_{4},7H_{2}O = 246/1·68 = 146·4 c.c.; hence their mixture in equivalent quantities occupies a volume of 366·9 c.c. The volume of astrakhanite = 334/2·22 = 150·5 c.c., and the volume of 13H_{2}O = 234 c.c., hence their sum = 380·5 c.c., and therefore it is easy to follow the formation of the astrakhanite in a suitable apparatus (a kind of thermometer containing oil and a powdered mixture of sodium and magnesium sulphates), and to see by the variation in volume that below 22° it remains unchanged, and at higher temperatures proceeds the more quickly the higher the temperature. At the transition temperature the solubility of astrakhanite and of the mixture of the component salts is one and the same, whilst at higher temperatures a solution which is saturated for a mixture of the individual salts would be supersaturated for astrakhanite, and at lower temperatures the solution of astrakhanite will be supersaturated for the component salts, as has been shown with especial detail by Karsten, Deacon, and others. Roozeboom showed that there are two limits to the composition of the solutions which can exist for a double salt; these limits are respectively obtained by dissolving a mixture of the double salt with each of its component simple salts. Van't Hoff demonstrated, besides this, that the tendency towards the formation of double salts has a distinct influence on the progress of double decomposition, for at temperatures above 31° the mixture 2MgSO_{4},7H_{2}O + 2NaCl passes into MgNa_{2}(SO_{4})_{2},4H_{2}O + MgCl_{2},6H_{2}O + 4H_{2}O, whilst below 31° there is not this double decomposition, but it proceeds in the opposite direction, as may be demonstrated by the above-described methods. Van der Heyd obtained a potassium astrakhanite, K_{2}SO_{4}MgSO_{4},4H_{2}O, from solutions of the component salts at 100°. From these experiments on double salts we see that there is as close a dependence between the temperature and the formation of substances as there is between the temperature and a change of state. It is a case of Deville's principles of dissociation, extended in the direction of the passage of a solid into a liquid. On the other hand, we see here how essential a _rôle_ water plays in the formation of compounds, and how the affinity for water of crystallisation is essentially analogous to the affinity between salts, and hence also to the affinity of acids for bases, because the formation of double salts does not differ in any essential point (except the degree of affinity--that is, from a quantitative aspect) from the formation of salts themselves. When sodium hydroxide with nitric acid gives sodium nitrate and water the phenomenon is essentially the same as in the formation of astrakhanite from the salts Na_{2}SO_{4},10H_{2}O and MgSO_{4},7H_{2}O. Water is disengaged in both cases, and hence the volumes are altered. [26] This salt, and especially its crystallo-hydrate with 7H_{2}O, is generally known as Epsom salts. It has long been used as a purgative. It is easily obtained from magnesia and sulphuric acid, and it separates on the evaporation of sea water and of many saline springs. When carbonic anhydride is obtained by the action of sulphuric acid on magnesite, magnesium sulphate remains in solution. When dolomite--that is, a mixture of magnesium and calcium carbonates--is subjected to the action of a solution of hydrochloric acid until about half of the salt remains, the calcium carbonate is mostly dissolved and magnesium carbonate is left, which by treatment with sulphuric acid gives a solution of magnesium sulphate. [27] The anhydrous salt, MgSO_{4} (sp. gr. 2·61), attracts moisture (7 mol. H_{2}O) from moist air; when heated in steam or hydrogen chloride it gives sulphuric acid, and when heated with carbon it is decomposed according to the equation 2MgSO_{4} + C = 2SO_{2} + CO_{2} + 2MgO. The monohydrated salt (kieserite), MgSO_{4},H_{2}O (sp. gr. 2·56), dissolves in water with difficulty; it is formed by heating the other crystallo-hydrates to 135°. The hexahydrated salt is dimorphous. If a solution, saturated at the boiling-point, be prepared, and cooled without access of crystals of the heptahydrated salt, then MgSO_{4},6H_{2}O crystallises out in _monoclinic_ prisms (Loewel, Marignac), which are quite as unstable as the salt, Na_{2}SO_{4},7H_{2}O; but if prismatic crystals of the cubic system of the copper-nickel salts of the composition MSO_{4},6H_{2}O be added, then crystals of MgSO_{4},6H_{2}O are deposited on them as prisms of the _cubic_ system (Lecoq de Boisbaudran). The common crystallo-hydrate, MgSO_{4},7H_{2}O, Epsom salts, belongs to the _rhombic_ system, and is obtained by crystallisation below 30°. Its specific gravity is 1·69. In a vacuum, or at 100°, it loses 5H_{2}O, at 132° 6H_{2}O, and at 210° all the 7H_{2}O (Graham). If crystals of ferrous or cobaltic sulphate be placed in a saturated solution, _hexagonal_ crystals of the heptahydrated salt are formed (Lecoq de Boisbaudran); they present an unstable state of equilibrium, and soon become cloudy, probably owing to their transformation into the more stable common form. Fritzsche, by cooling saturated solutions below 0°, obtained a mixture of crystals of ice and of a dodecahydrated salt, which easily split up at temperatures above 0°. Guthrie showed that dilute solutions of magnesium sulphate, when refrigerated, separate ice until the solution attains a composition MgSO_{4},24H_{2}O, which will completely freeze into a crystallo-hydrate at -5·3°. According to Coppet and Rüdorff, the temperature of the formation of ice falls by 0·073° for every part by weight of the heptahydrated salt per 100 of water. This figure gives (Chapter I., Note 49) _i_ = 1 for both the heptahydrated and the anhydrous salt, from which it is evident that it is impossible to judge the state of combination in which a dissolved substance occurs by the temperature of the formation of ice. The solubility of the different crystallo-hydrates of magnesium sulphate, according to Loewel, also varies, like those of sodium sulphate or carbonate (_see_ Chapter XII., Notes 7 and 18). At 0° 100 parts of water dissolves 40·75 MgSO_{4} in the presence of the hexahydrated salt, 34·67 MgSO_{4} in the presence of the hexagonal heptahydrated salt, and only 26 parts of MgSO_{4} in the presence of the ordinary heptahydrated salt--that is, solutions giving the remaining crystallo-hydrates will be supersaturated for the ordinary heptahydrated salt. All this shows how many diverse aspects of more or less stable equilibria may exist between water and a substance dissolved in it; this has already been enlarged on in Chapter I. Carefully purified magnesium sulphate in its aqueous solution gives, according to Stcherbakoff, an alkaline reaction with litmus, and an acid reaction with phenolphthalein. The specific gravity of solutions of certain salts of magnesium and calcium reduced to 15°/4° (see my work cited, Chapter I., Note 19), are, if water at 4° = 10,000, MgSO_{4}: _s_ = 9,992 + 99·89_p_ + 0·553_p_^2 MgCl_{2}: _s_ = 9,992 + 81·31_p_ + 0·372_p_^2 CaCl_{2}: _s_ = 9,992 + 80·24_p_ + 0·476_p_^2 [28] Graham even distinguished the last equivalent of the water of crystallisation of the heptahydrated salt as that which is replaced by other salts, pointing out that double salts like MgK_{2}(SO_{4})_{2},6H_{2}O lose all their water at 135°, whilst MgSO_{4},7H_{2}O only parts with 6H_{2}O. _The power of forming basic salts_ is a very remarkable peculiarity of magnesia and other feeble bases, and especially of those corresponding with polyvalent metals. The very powerful bases corresponding with univalent metals--like potassium and sodium--do not form basic salts, and, indeed, are more prone to give acid salts, whilst magnesium easily and frequently forms basic salts, especially with feeble acids, although there are some oxides--as, for example, copper and lead oxides--which still more frequently give basic salts. If a cold solution of magnesium sulphate be mixed with a solution of sodium carbonate there is formed a gelatinous precipitate of a basic salt, Mg(HO)_{2},4MgCO_{3},9H_{2}O; but all the magnesia is not precipitated in this case, as a portion of it remains in solution as an acid double salt. If sodium carbonate be added to a boiling solution of magnesium sulphate a precipitate of a still more basic salt is formed, 4MgSO_{4} + 4Na_{2}CO_{3} + 4H_{2}O = 4Na_{2}SO_{4} + CO_{2} + Mg(OH)_{2},3MgCO_{3},3H_{2}O. This basic salt forms the ordinary drug _magnesia_ (_magnesia alba_), in the form of light porous lumps. Other basic salts are formed under certain modifications of temperature and conditions of decomposition. But _the normal salt_, MgCO_{3}, which occurs in nature as magnesite in the form of rhombohedra of specific gravity 3·056, cannot be obtained by such a method of precipitation. In fact, the formation of the different basic salts shows the power of water to decompose the normal salt. It is possible, however, to obtain this salt both in an anhydrous and hydrated state. A solution of magnesium carbonate in water containing carbonic acid is taken for this purpose. The reason for this is easily understood--carbonic anhydride is one of the products of the decomposition of magnesium carbonate in the presence of water. If this solution be left to evaporate spontaneously the normal salt separates in a hydrated form, but in the evaporation of a heated solution, through which a stream of carbonic anhydride is passed, the anhydrous salt is formed as a crystalline mass, which remains unaltered in the air, like the natural mineral.[29] The decomposing influence of water on the salts of magnesium, which is directly dependent on the feeble basic properties of magnesia,[30] is most clearly seen in _magnesium chloride_, MgCl_{2}. This salt is contained[31] in the last mother-liquors of the evaporation of sea-water. On cooling a sufficiently concentrated solution, the crystallo-hydrate, MgCl_{2},6H_{2}O, separates;[32] but if it be further heated (above 106°) to remove the water, then hydrochloric acid passes off together with the latter, so that there ultimately remains magnesia with a small quantity of magnesium chloride.[33] From what has been said it is evident that anhydrous magnesium chloride cannot be obtained by simple evaporation. But if sal-ammoniac or sodium chloride be added to a solution of magnesium chloride, then the evolution of hydrochloric acid does not take place, and after complete evaporation the residue is perfectly soluble in water. This renders it possible to obtain anhydrous magnesium chloride from its aqueous solution. Indeed the mixture with sal-ammoniac (in excess) may be dried (the residue consists of an anhydrous double salt, MgCl_{2},2NH_{4}Cl) and then ignited (460°), when the sal-ammoniac is converted into vapour and a fused mass of anhydrous magnesium chloride remains behind. The anhydrous chloride evolves a very considerable amount of heat on the addition of water, which shows the great affinity the salt has for water.[34] Anhydrous magnesium chloride is not only obtained by the above method, but is also formed by the direct combination of chlorine and magnesium, and by the action of chlorine on magnesium oxide, oxygen being evolved; this proceeds still more easily _by heating magnesia with charcoal in a stream of chlorine_, when the charcoal serves to take up the oxygen. This latter method is also employed for the preparation of chlorides which are formed in an anhydrous condition with still greater difficulty than magnesium chloride. Anhydrous magnesium chloride forms a colourless, transparent mass, composed of flexible crystalline plates of a pearly lustre. It fuses at a low red heat (708°) into a colourless liquid, remains unchanged in a dry state, but under the action of moisture is partially decomposed even at the ordinary temperature, with formation of hydrochloric acid. When heated in the presence of oxygen (air) it gives chlorine and the basic salt, which is formed with even greater facility under the action of heat in the presence of steam, when HCl is formed, according to the equation 2MgCl_{2} + H_{2}O = MgOMgCl_{2} + 2HCl.[34 bis] [29] The crystalline form of the anhydrous salt obtained in this manner is not the same as that of the natural salt. The former gives rhombohedra, like those in which calcium carbonate appears as calc spar, whilst the natural salt appears as rhombic prisms, like those sometimes presented by the same carbonate as aragonite, which will shortly be described. [30] Magnesium sulphate enters into certain reactions which are proper to sulphuric acid itself. Thus, for instance, if a carefully prepared mixture of equivalent quantities of hydrated magnesium sulphate and sodium chloride be heated to redness, the evolution of hydrochloric acid is observed just as in the action of sulphuric acid on common salt, MgSO_{4} + 2NaCl + H_{2}O = Na_{2}SO_{4} + MgO + 2HCl. Magnesium sulphate acts in a similar manner on nitrates, with the evolution of nitric acid. A mixture of it with common salt and manganese peroxide gives chlorine. Sulphuric acid is sometimes replaced by magnesium sulphate in galvanic batteries--for example, in the well-known Meidinger battery. In the above-mentioned reactions we see a striking example of the similarity of the reactions of acids and salts, especially of salts which contain such feeble bases as magnesia. [31] As sea-water contains many salts, MCl and MgX_{2}, it follows, according to Berthollet's teaching, that MgCl_{2} is also present. [32] As the crystallo-hydrates of the salts of sodium often contain 10H_{2}O, so many of the salts of magnesium contain 6H_{2}O. [33] This decomposition is most simply defined as the result of the two reverse reactions, MgCl_{2} ÷ H_{2}O = MgO + 2HCl and MgO + 2HCl = MgCl_{2} + H_{2}O, or as a distribution between O and Cl_{2} on the one hand and H_{2} and Mg on the other. (With O, MgCl_{2} gives chlorine, _see_ Chapter X., Note 33, and Chapter II., Note 3 bis and others, where the reactions and applications of MgCl_{2} are given.) It is then clear that, according to Berthollet's doctrine, the mass of the hydrochloric acid converts the magnesium oxide into chloride, and the mass of the water converts the magnesium chloride into oxide. The crystallo-hydrate, MgCl_{2},6H_{2}O, forms the limit of the reversibility. But an intermediate state of equilibrium may exist in the form of basic salts. On mixing ignited magnesia with a solution of magnesium chloride of specific gravity about 1·2, a solid mass is obtained which is scarcely decomposed by water at the ordinary temperature (_see_ Chapter XVI., Note 4). A similar means is employed for cementing sawdust into a solid mass, called cylolite, used for flooring, &c. We may remark that MgBr_{2} crystallises not only with 6H_{2}O (temperature of fusion 152°), but also with 10H_{2}O (temperature of fusion +12°, formed at -18°). (Panfiloff, 1894). [34] According to Thomsen, the combination of MgCl_{2} with 6H_{2}O evolves 33,000 calories, and its solution in an excess of water 36,000. [34 bis] Hence MgCl_{2} may be employed for the preparation of chlorine and hydrochloric acid (Chapters X. and XI.). In general magnesium chloride, which is obtained in large quantities from sea water and Stassfurt carnallite, may find numerous practical uses. _Calcium_ (or the metal of lime) and its compounds in many respects present a great resemblance to magnesium compounds, but are also clearly distinguished from them by many properties.[35] In general, calcium stands to magnesium in the same relation as potassium occupies in respect to sodium. Davy obtained metallic calcium, like potassium, as an amalgam by the action of a galvanic current; but neither charcoal nor iron decomposes calcium oxide, and even sodium decomposes calcium chloride[36] with difficulty. But a galvanic current easily decomposes calcium chloride, and metallic sodium somewhat easily decomposes calcium iodide when heated. As in the case of hydrogen, potassium, and magnesium, the affinity of iodine for calcium is feebler than that of chlorine (and oxygen), and therefore it is not surprising that calcium iodide may be subjected to that decomposition, which the chloride and oxide undergo with difficulty.[37] _Metallic calcium_ is of a yellow colour, and has a considerable lustre, which it preserves in dry air. Its specific gravity is 1·58. Calcium is distinguished by its great ductility; it melts at a red heat and then burns in the air with a very brilliant flame; the brilliancy is due to the formation of finely divided infusible calcium oxide. Judging from the fact that calcium in burning gives a very large flame, it is probable that this metal is volatile. Calcium decomposes water at the ordinary temperature, and is oxidised in moist air, but not so rapidly as sodium. In burning, it gives its oxide or _lime_, CaO, a substance which is familiar to every one, and of which we have already frequently had occasion to speak. This oxide is not met with in nature in a free state, because it is an energetic base which everywhere encounters acid substances forming salts with them. It is generally combined with silica, or occurs as calcium carbonate or sulphate. The carbonate and nitrate are decomposed, at a red heat, with the formation of lime. As a rule, the carbonate, which is so frequently met with in nature, serves as the source of the calcium oxide, both commercial and pure. When heated, calcium carbonate dissociates: CaCO_{3} = CaO + CO_{2}. In practice the decomposition is conducted at a bright red heat, in the presence of steam, or a current of a foreign gas, in heaps or in special kilns.[38] [35] There are many other methods of separating calcium from magnesium besides that mentioned above (Note 22). Among them it will be sufficient to mention the behaviour of these bases towards a solution of sugar; hydrated _lime_ is exceedingly _soluble in an aqueous solution of sugar_, whilst magnesia is but little soluble. All the lime may be extracted from dolomite by burning it, slaking the mixture of oxides thus obtained, and adding a 10 p.c. solution of sugar. Carbonic anhydride precipitates calcium carbonate from this solution. The addition of sugar (molasses) to the lime used for building purposes powerfully increases the binding power of the mortar, as I have myself found. I have been told that in the East (India, Japan) the addition of sugar to cement has long been practised. [36] Moreover Caron obtained an alloy of calcium and zinc by fusing calcium chloride with zinc and sodium. The zinc distilled from this alloy at a white heat, leaving calcium behind (Note 50). [37] Calcium iodide may be prepared by saturating lime with hydriodic acid. It is a very soluble salt (at 20° one part of the salt requires 0·49 part and at 43° 0·35 part of water for solution), is deliquescent in the air, and resembles calcium chloride in many respects. It changes but little when evaporated, and like calcium chloride fuses when heated, and therefore all the water may be driven off by heat. If anhydrous calcium iodide be heated with an equivalent quantity of sodium in a closely covered iron crucible, sodium iodide and metallic calcium are formed (Liés-Bodart). Dumas advises carrying on this reaction in a closed space under pressure. [38] Kilns which act either intermittently or continuously are built for this purpose. Those of the first kind are filled with alternate layers of fuel and limestone; the fuel is lighted, and the heat developed by its combustion serves for decomposing the limestone. When the process is completed the kiln is allowed to cool somewhat, the lime raked out, and the same process repeated. In the continuously acting furnaces, constructed like that shown in fig. 78, the kiln itself only contains limestone, and there are lateral hearths for burning the fuel, whose flame passes through the limestone and serves for its decomposition. Such furnaces are able to work continuously, because the unburnt limestone may be charged from above and the burnt lime raked out from below. It is not every limestone that is suitable for the preparation of lime, because many contain impurities, principally clay, dolomite, and sand. Such limestones when burnt either fuse partially or give an impure lime, called _poor_ lime in distinction from that obtained from purer limestone, which is called _rich_ lime. The latter kind is characterised by its disintegrating into a fine powder when treated with water, and is suitable for the majority of uses to which lime is applied, and for which the poor lime is sometimes quite unfit. However, certain kinds of poor lime (as we shall see in Chapter XVIII., Note 25) are used in the preparation of hydraulic cements, which solidify into a hard mass under water. In order to obtain perfectly pure lime it is necessary to take the purest possible materials. In the laboratory, marble or shells are used for this purpose as a pure form of calcium carbonate. They are first burnt in a furnace, then put in a crucible and moistened with a small quantity of water, and finally strongly ignited, by which means a pure lime is obtained. Pure lime may be more rapidly prepared by taking calcium nitrate, CaN_{2}O_{6}, which is easily obtained by dissolving limestone in nitric acid. The solution obtained is boiled with a small quantity of lime in order to precipitate the foreign oxides which are insoluble in water. The oxides of iron, aluminium, &c., are precipitated by this means. The salt is then crystallised and ignited: CaN_{2}O_{6} = CaO + 2NO_{2} + O. In the decomposition of calcium carbonate the lime preserves the form of the lumps subjected to ignition; this is one of the signs distinguishing quicklime when it is freshly burnt and unaltered by air. It attracts moisture from the air and then disintegrates to a powder; if left long exposed in the air, it also attracts carbonic anhydride and increases in volume; it does not entirely pass into carbonate, but forms a compound of the latter with caustic lime. [Illustration: FIG. 78.--Continually-acting kiln for burning lime. The lime is charged from above and calcined by four lateral grates, R, M. D, fire-bars. B, space for withdrawing the burnt lime. K, stoke-house. M. fire grate. Q, R, under-grate.] Calcium oxide--that is, quicklime--is a substance (sp. gr. 3·15) which is unaffected by heat,[39] and may therefore serve as a fire-resisting material, and was employed by Deville for the construction of furnaces in which platinum was melted, and silver volatilised by the action of the heat evolved by the combustion of detonating gas. The hydrated lime, slaked lime, or calcium hydroxide, CaH_{2}O_{2} (specific gravity 2·07) is a most common alkaline substance, employed largely in building for making mortars or cements, in which case its binding property is mainly due to the absorption of carbonic anhydride.[40] Lime, like other alkalis, acts on many animal and vegetable substances, and for this reason has many practical uses--for example, for removing fats, and in agriculture for accelerating the decomposition of organic substances in the so-called _composts_ or accumulations of vegetable and animal remains used for fertilising land. Calcium hydroxide easily loses its water at a moderate heat (530°), but it does not part with water at 100°. When mixed with water, lime forms a pasty mass known as _slaked lime_ and in a more dilute form as _milk of lime_, because when shaken up in water it remains suspended in it for a long time and presents the appearance of a milky liquid. But, besides this, lime is directly soluble in water, not to any considerable extent, but still in such a quantity that _lime water_ is precipitated by carbonic anhydride, and has clearly distinguishable alkaline properties. One part of lime requires at the ordinary temperature about 800 parts of water for solution. At 100° it requires about 1500 parts of water, and therefore lime-water becomes cloudy when boiled. If lime-water be evaporated in a vacuum, calcium hydroxide separates in six-sided crystals.[41] If lime-water be mixed with hydrogen peroxide minute crystals of _calcium peroxide_, CaO_{2},8H_{2}O, separate; this compound is very unstable and, like barium peroxide, is decomposed by heat. Lime, as a powerful base, combines with all acids, and in this respect presents a transition from the true alkalis to magnesia. Many of the salts of calcium (the carbonate, phosphate, borate, and oxalate) are insoluble in water; besides which the sulphate is only sparingly soluble. As a more energetic base than magnesia, lime forms salts, CaX_{2}, which are distinguished by their stability in comparison with the salts MgX_{2}; neither does lime so easily form basic and double salts as magnesia. [39] Lime, when raised to a white heat in the vapour of potassium, gives calcium, and in chlorine it gives off oxygen. Sulphur, phosphorus, &c., when heated with lime, are absorbed by it. [40] The greater quantity of lime is used in making mortar for binding bricks or stones together, in the form of _lime_ or _cement_, or the so-called _slaked lime_. For this purpose the lime is mixed with water and sand, which serves to separate the particles of lime from each other. If only lime paste were put between two bricks they would not hold firmly together, because after the water had evaporated the lime would occupy a smaller space than before, and therefore cracks and powder would form in its mass, so that it would not at all produce that complete cementation of the bricks which it is desired to attain. Pieces of stone--that is, sand--mixed with the lime hinder this process of disintegration, because the lime binds together the individual grains of sand mixed with it, and forms one concrete mass, in consequence of a process which proceeds after the desiccation or removal of the water. The process of the solidification of lime, taken as slaked lime, consists first in the direct evaporation of the water and crystallisation of the hydrate, so that the lime binds the stones and sand mixed with it, just as glue binds two pieces of wood. But this preliminary binding action of lime is feeble (as is seen by direct experiment) unless there be further alteration of the lime leading to the formation of carbonates, silicates, and other salts of calcium which are distinguished by their great cohesiveness. With the progress of time the cement is partially subjected to the action of the carbonic anhydride in the air, owing to which calcium carbonate is formed, but not more than half the lime is thus converted into carbonate. Besides which, the lime partially acts on the silica of the bricks, and it is owing to these new combinations simultaneously forming in the cement that it gradually becomes stronger and stronger. Hence the binding action of the lime becomes stronger with the lapse of time. This is the reason (and not, as is sometimes said, because the ancients knew how to build stronger than we do) why buildings which have stood for centuries possess a very strongly binding cement. Hydraulic cements will be described later (Chapter XVIII., Note 25). [41] Professor Glinka measured the transparent bright crystals of calcium hydroxide which are formed in common hydraulic (Portland) cement. Anhydrous lime does not absorb dry carbonic anhydride at the ordinary temperature. This was already known by Scheele, and Prof. Schuliachenko showed that there is no absorption even at 360°. It only proceeds at a red heat,[42] and then only leads to the formation of a mixture of calcium oxide and carbonate (Rose). But if the lime be slaked or dissolved, the absorption of carbonic anhydride proceeds rapidly and completely. These phenomena are connected with the _dissociation of calcium carbonate_, studied by Debray (1867) under the influence of the conceptions of dissociation introduced into science by Henri Saint-Claire Deville. Just as there is no vapour tension for non-volatile substances, so there is no dissociation tension of carbonic anhydride for calcium carbonate at the ordinary temperature. Just as every volatile substance has a maximum possible vapour tension for every temperature, so also calcium carbonate has its corresponding _dissociation tension_; this at 770° (the boiling point of cadmium) is about 85 mm. (of the mercury column), and at 930° (the boiling point of Zn) it is about 520 mm. As, if the tension be greater, there will be no evaporation, so also there will he no decomposition. Debray took crystals of calc spar, and could not observe the least change in them at the boiling point of zinc (930°) in an atmosphere of carbonic anhydride taken at the atmospheric pressure (760 mm.), whilst on the other hand calcium carbonate may be completely decomposed at a much lower temperature if the tension of the carbonic anhydride be kept below the dissociation tension, which may be done either by directly pumping away the gas with an air-pump, or by mixing it with some other gas--that is, by diminishing the partial pressure of the carbonic anhydride,[43] just as an object may be dried at the ordinary temperature by removing the aqueous vapour or by carrying it off in a stream of another gas. Thus it is possible to obtain calcium carbonate from lime and carbonic anhydride at a certain temperature above that at which dissociation begins, and conversely to decompose calcium carbonate at the same temperature into lime and carbonic anhydride.[44] At the ordinary temperature the reaction of the first order (combination) cannot proceed because the second (decomposition, dissociation) cannot take place, and thus all the most important phenomena with respect to the behaviour of lime towards carbonic anhydride are explained by starting from one common basis.[45] [42] The act of heating brings the substance into that state of internal motion which is required for reaction. It should be considered that by the act of heating not only is the bond between the parts, or cohesion of the molecules, altered (generally diminished), not only is the motion or store of energy of the whole molecule increased, but also that in all probability the motion of the atoms themselves in molecules undergoes a change. The same kind of change is accomplished by the act of solution, or of combination in general, judging from the fact that a dissolved or combined substance--for instance, lime with water--reacts on carbonic anhydride as it does under the action of heat. For the comprehension of chemical phenomena it is exceedingly useful to recognise clearly this parallelism. Rose's observation on the formation (by the slow diffusion of solutions of calcium chloride and sodium carbonate) of aragonite from dilute, and of calc spar from strong, solutions is easily understood from this point of view. As aragonite is always formed from hot solutions, it appears that dilution with water acts like heat. The following experiment of Kühlmann is particularly instructive in this sense. Anhydrous (perfectly dry) barium oxide does not react with monohydrated sulphuric acid, H_{2}SO_{4} (containing neither free water nor anhydride, SO_{3}). But if either an incandescent object or a moist substance is brought into contact with the mixture a violent reaction immediately begins (it is essentially the same as combustion), and the whole mass reacts. The influence of solution on the process of reaction is instructively illustrated by the following experiment. Lime, or barium oxide, is placed in a flask or retort having an upper orifice and connected with a tube immersed in mercury. A funnel furnished with a stopcock and filled with water is fixed into the upper orifice of the retort, which is then filled with dry carbonic anhydride. There is no absorption. When a constant temperature is arrived at, the unslaked oxide is made to absorb all the carbonic anhydride by carefully admitting water. A vacuum is formed, as is seen by the mercury rising in the neck of the retort. With water the absorption goes on to the end, whilst under the action of heat there remains the dissociating tension of the carbonic anhydride. Furthermore, we here see that, with a certain resemblance, there is also a distinction, depending on the fact that at low temperatures calcium carbonate does not dissociate; this determines the complete absorption of the carbonic anhydride in the aqueous solution. [43] Experience has shown that by moistening partially-burnt lime with water and reheating it, it is easy to drive off the last traces of carbonic anhydride from it, and that, in general, by blowing air or steam through the lime, and even by using moist fuel, it is possible to accelerate the decomposition of the calcium carbonate. The partial pressure is decreased by these means. [44] Before the introduction of Deville's theory of dissociation, the _modus operandi_ of decompositions like that under consideration was understood in the sense that decomposition starts at a certain temperature, and that it is accelerated by a rise of temperature, but it was not considered possible that combination could proceed at the same temperature as that at which decomposition goes on. Berthollet and Deville introduced the conception of equilibrium into chemical science, and elucidated the question of reversible reactions. Naturally the subject is still far from being clear--the questions of the rate and completeness of reaction, of contact, &c., still intrude themselves--but an important step has been made in chemical mechanics, and we have started on a new path which promises further progress, towards which much has been done not only by Deville himself, but more especially by the French chemists Debray, Troost, Lemoine, Hautefeuille, Le Chatelier, and others. Among other things those investigators have shown the close resemblance between the phenomena of evaporation and dissociation, and pointed out that the amount of heat absorbed by a dissociating substance may be calculated according to the law of the variation of dissociation-pressure, in exactly the same manner as it is possible to calculate the latent heat of the evaporation of water, knowing the variation of the tension with the temperature, on the basis of the second law of the mechanical theory of heat. Details of this subject must be looked for in special works on physical chemistry. _One and the same conception_ of the mechanical theory of heat _is applicable to dissociation_ and _evaporation_. [45] But the question as to the formation of a basic calcium carbonate with a rise of temperature still remains undecided. The presence of water complicates all the relations between lime and carbonic anhydride, all the more as the existence of an attraction between calcium carbonate and water is seen from its being able to give a _crystallo-hydrate_, CaCO_{3},5H_{2}O (Pelouze), which crystallises in rhombic prisms of sp. gr. about 1·77 and loses its water at 20°. These crystals are obtained when a solution of lime in sugar and water is left long exposed to the air and slowly attracts carbonic anhydride from it, and also by the evaporation of such a solution at a temperature of about 3°. On the other band, it is probable that an _acid salt_, CaH_{2}(CO_{3})_{2}, is formed in an aqueous solution, not only because water containing carbonic acid dissolves calcium carbonate, but more especially in view of the researches of Schloesing (1872), which showed that at 16° a litre of water in an atmosphere of carbonic anhydride (pressure 0·984 atmosphere) dissolves 1·086 gram of calcium carbonate and 1·778 gram of carbonic anhydride, which corresponds with the formation of calcium hydrogen carbonate, and the solution of carbonic anhydride in the remaining water. Caro showed that a litre of water is able to dissolve as much as 3 grams of calcium carbonate if the pressure be increased to 4 and more atmospheres. The calcium carbonate is precipitated when the carbonic anhydride passes off in the air or in a current of another gas; this also takes place in many natural springs. Tufa, stalactites, and other like formations from waters containing calcium carbonate and carbonic acid in solution are formed in this manner. The solubility of calcium carbonate itself at the ordinary temperature does not exceed 13 milligrams per litre of water. _Calcium carbonate_, CaCO_{3}, is sometimes met with in nature in a crystalline form, and it forms an example of the phenomenon termed _dimorphism_--that is, it appears in two crystalline forms. When it exhibits combinations of forms belonging to the hexagonal system (six-sided prisms, rhombohedra, &c.) it is called _calc spar_. Calc spar has a specific gravity of 2·7, and is further characterised by a distinct cleavage along the planes of the fundamental rhombohedron having an angle of 105°. Perfectly transparent Iceland spar presents a clear example of double refraction (for which reason it is frequently employed in physical apparatus). The other form of calcium carbonate occurs in crystals belonging to the rhombic system, and it is then called _aragonite_; its specific gravity is 3·0. If calcium carbonate be artificially produced by slow crystallisation at the ordinary temperature, it appears in the rhombohedral form, but if the crystallisation be aided by heat it then appears as aragonite. It may therefore be supposed that calc spar presents the form corresponding with a low temperature, and aragonite with a higher temperature during crystallisation.[46] [46] Dimorphous bodies differ from true isomers and polymers in that they do not differ in their chemical reactions, which are determined by a difference in the distribution (motion) of the atoms in the molecules, and therefore dimorphism is usually ascribed to a difference in the distribution of similar molecules, building up a crystal. Although such a hypothesis is quite admissible in the spirit of the atomic and molecular theory, yet, as in such a redistribution of the molecules a perfect conservation of the distribution of the atoms in them cannot be imagined, and in every effort of chemical reaction there must take place a certain motion among the atoms; so in my opinion there is no firm basis for distinguishing dimorphism from the general conception of isomerism, under which the cases of those organic bodies which are dextro and lævo rotatory (with respect to polarised light) have recently been brought with such brilliant success. When calcium carbonate separates out from solutions, it has at first a gelatinous appearance, which leads to the supposition that this salt appears in a colloidal state. It only crystallises with the progress of time. The colloidal state of calcium carbonate is particularly clear from the following observations made by Prof. Famintzin, who showed that when it separates from solutions it is obtained under certain conditions in the form of grains having the peculiar paste-like structure proper to starch, which fact has not only an independent interest, but presents an example of a mineral substance being obtained in a form until then only known in the organic substances elaborated in plants. This shows that the forms (cells, vessels, &c.) in which vegetable and animal substances occur in organisms do not present in themselves anything peculiar to organisms, but are only the result of those particular conditions in which these substances are formed. Traube and afterwards Monnier and Vogt (1882) obtained formations which, under the microscope, were in every respect identical in appearance with vegetable cells, by means of a similar slow formation of precipitates (by reacting on sulphates of different metals with sodium silicate or carbonate). _Calcium sulphate_ in combination with two equivalents of water, CaSO_{4},2H_{2}O, is very widely distributed in nature, and is known as _gypsum_. Gypsum loses one and a half and two equivalents of water at a moderate temperature,[47] and anhydrous or burnt gypsum is then obtained, which is also known as plaster of Paris, and is employed in large quantities for modelling.[48] This use depends on the fact that burnt and finely-divided and sifted gypsum forms a paste when mixed with water; after a certain time this paste becomes slightly heated and solidifies, owing to the fact that the anhydrous calcium sulphate, CaSO_{4}, again combines with water. When the plaster of Paris and water are first made into a paste they form a mechanical mixture, but when the mass solidifies, then a compound of the calcium sulphate with two molecules of water is produced; and this may be regarded as derived from S(OH)_{6} by the substitution of two atoms of hydrogen by one atom of bivalent calcium. Natural gypsum sometimes appears as perfectly colourless, or variegated, marble-like, masses, and sometimes in perfectly colourless crystals, _selenite_, of specific gravity 2·33. The semi-transparent gypsum, or _alabaster_, is often carved into small statues. Besides which an anhydrous calcium sulphate, CaSO_{4}, called _anhydrite_ (specific gravity 2·97), occurs in nature. It sometimes occurs along with gypsum. It is no longer capable of combining directly with water, and differs in this respect from the anhydrous salt obtained by gently igniting gypsum. If gypsum be very strongly heated it shrinks and loses its power of combining with water.[48 bis] One part of calcium sulphate requires at 0° 525 parts of water for solution, at 38° 466 parts, and at 100° 571 parts of water. The maximum solubility of gypsum is at about 36°, which is nearly the same temperature as that at which sodium sulphate is most soluble.[49] [47] According to Le Chatelier (1888), 1-1/2H_{2}O is lost at 120°--that is, H_{2}O,2CaSO_{4} is formed, but at 194° all the water is expelled. According to Shenstone and Cundall (1888) gypsum begins to lose water at 70° in dry air. The semi-hydrated compound H_{2}O,2CaSO_{4} is also formed when gypsum is heated with water in a closed vessel at 150° (Hoppe-Seyler). [48] For stucco-work it is usual to add lime and sand, as the mass is then harder and does not solidify so quickly. For imitating marble, glue is added to the plaster, and the mass is polished when thoroughly dry. Re-burnt gypsum cannot be used over again, as that which has once solidified is, like the natural anhydride, not able to recombine with water. It is evident that the structure of the molecules in the crystallised mass, or in general in any dense mass, exerts an influence on the chemical action, which is more particularly evident in metals in their different forms (powder, crystalline, rolled, &c.) [48 bis] According to MacColeb, gypsum dehydrated at 200° has a specific gravity 2·577, and heated to its point of fusion, 2·654. Potilitzin (1894) also admits the two above-named modifications of anhydrous gypsum, which, moreover, always contain the semi-hydrated hydrate (Note 47), and he explains by their relation to water the phenomena observed in the solidification of a mixture of burnt gypsum and water. [49] As Marignac showed, gypsum, especially when desiccated at 120°, easily gives supersaturated solutions with respect to CaSO_{4},2H_{2}O, which contain as much as 1 part of CaSO_{4} to 110 parts of water. Boiling dilute hydrochloric acid dissolves gypsum, forming calcium chloride. The behaviour of gypsum towards the alkaline carbonates has been described in Chapter X. Alcohol precipitates gypsum from its aqueous solutions, because, like the sulphates in general, it is sparingly soluble in alcohol. Gypsum, like all the sulphates, when heated with charcoal, gives up its oxygen, forming the sulphide, CaS. Calcium ulphate, like magnesium sulphate, is capable of forming double salts, but with difficulty, and they are chemically less stable. They contain, as is always the case with double salts, less water of crystallisation than the component salts. Rose, Struvé, and others obtained the salt CaK_{2}(SO_{4})_{2},H_{2}O; a mixture of gypsum with an equivalent amount of potassium sulphate and water solidifies into a homogeneous mass. Fritzsche obtained the corresponding sodium salt in a hydrated and anhydrous state, by heating a mixture of gypsum with a saturated solution of sodium sulphate. The anhydrous salt occurs in nature as _glauberite_. Fritzsche also obtained _gaylussite_, Na_{2}Ca(CO_{3})_{2},5H_{2}O, by pouring a saturated solution of sodium carbonate on to freshly-precipitated calcium carbonate. Calcium also forms basic salts, but only a few. Veeren (1892) obtained Ca(NO_{3})_{2}Ca(OH)_{2},2-1/2H_{2}O by leaving powdered caustic lime in a saturated solution of Ca(NO_{3})_{2} until it solidified. This salt is decomposed by water. As lime is a more energetic base than magnesia, so _calcium chloride_, CaCl_{2}, is not so easily decomposed by water, and its solutions only disengage a small quantity of hydrochloric acid when evaporated, and when the evaporation is conducted in a stream of hydrochloric acid it easily gives an anhydrous salt which fuses at 719°; otherwise an aqueous solution yields a crystallo-hydrate, CaCl_{2},6H_{2}O, which melts at 30°.[50] [50] Calcium chloride has a specific gravity 2·20, or, when fused, 2·12, and the sp. gr. of the crystallised salt CaCl_{2},6H_{2}O is 1·69. If the volume of the crystals at 0° = 1, then at 29° it is 1·020, and the volume of the fused mass at the same temperature is 1·118 (Kopp) (specific gravity of solutions, _see_ Note 27). The solution containing 50 p.c. CaCl_{2} boils at 130°, 70 p.c. at 158°. Superheated steam decomposes calcium chloride with more difficulty than magnesium chloride and with greater ease than barium chloride (Kuhnheim). Sodium does not decompose fused calcium chloride even on prolonged heating (Liés-Bodart), but an alloy of sodium with zinc, lead, and bismuth decomposes it, forming an alloy of calcium with one of the above-named metals (Caron). The zinc alloy may be obtained with as much as 15 p.c. of calcium. Calcium chloride is soluble in alcohol and absorbs ammonia. A gram molecular weight of calcium chloride in dissolving in an excess of water evolves 18,723 calories, and in dissolving in alcohol 17,555 units of heat, according to Pickering. Roozeboom made detailed researches on the crystallo-hydrates of calcium chloride (1889), and found that CaCl_{2},6H_{2}O melts at 30·2°, and is formed at low temperatures from solutions containing not more than 103 parts of calcium chloride per 100 parts of water; if the amount of salt (always to 100 parts of water) reaches 120 parts, then tabular crystals of CaCl_{2},4H_{2}O[Greek: b] are formed, which at temperatures above 38·4° are converted into the crystallo-hydrates CaCl_{2},2H_{2}O, whilst at temperatures below 18° the [Greek: b] variety passes into the more stable CaCl_{2},4H_{2}O[Greek: a], which process is aided by mechanical friction. Hence, as is the case with magnesium sulphate (Note 27), one and the same crystallo-hydrate appears in two forms--the [Greek: b], which is easily produced but is unstable, and the [Greek: a], which is stable. The solubility of the above-mentioned hydrates of chloride of calcium, or amount of calcium chloride per 100 parts of water, is as follows:-- 0° 20° 30° 40° 60° CaCl_{2},6H_{2}O 60 75 100 (102·8) CaCl_{2},4H_{2}O[Greek: a] -- 90 101 117} (154·2) CaCl_{2},4H_{2}O[Greek: b] -- 104 114 --} CaCl_{2},2H_{2}O -- -- (308·3) 128 137 The amount of calcium chloride to 100 parts of water in the crystallo-hydrate is given in brackets. The point of intersection of the curves of solubility lies at about 30° for the first two salts and about 45° for the salts with 4H_{2}O and 2H_{2}O. The crystals CaCl_{2},2H_{2}O may, however, be obtained (Ditte) at the ordinary temperature from solutions containing hydrochloric acid. The vapour tension of this crystallo-hydrate equals the atmospheric at 165°, and therefore the crystals may be dried in an atmosphere of steam and obtained without a mother liquor, whose vapour tension is greater. This crystallo-hydrate decomposes at about 175° into CaCl_{2},H_{2}O and a solution; this is easily brought about in a closed vessel when the pressure is greater than the atmosphere. This crystallo-hydrate is destroyed at temperatures above 260°, anhydrous calcium chloride being formed. Neglecting the unstable modification CaCl_{2},4H_{2}O[Greek: b], we will give the temperatures _t_ at which the passage of one hydrate into another takes place and at which the solution CaCl_{2} + _n_H_{2}O, the two solids A and B and aqueous vapour, whose tension is given as _p_ in millimetres, are able to exist together in stable equilibrium, according to Roozeboom's determinations: _t_ _n_ A B _p_ -55° 14·5 ice CaCl_{2},6H_{2}O 0 +29·8° 6·1 CaCl_{2},6H_{2}O CaCl_{2},4H_{2}O 6·8 45·3° 4·7 CaCl_{2},4H_{2}O CaCl_{2},2H_{2}O 11·8 175·5° 2·1 CaCl_{2},2H_{2}O CaCl_{2},H_{2}O 842 260° 1·8 CaCl_{2},H_{2}O CaCl_{2} Several atmospheres Solutions of calcium chloride may serve as a convenient example for the study of the supersaturated state, which in this case easily occurs, because different hydrates are formed. Thus at 25° solutions containing more than 83 parts of anhydrous calcium chloride per 100 of water will be supersaturated for the hydrate CaCl_{2},6H_{2}O. On the other hand, Hammerl showed that solutions of calcium chloride, when frozen, deposit ice if they contain less than 43 parts of salt per 100 of water, and if more the crystallo-hydrate CaCl_{2},6H_{2}O separates, and that a solution of the above composition (CaCl_{2},14H_{2}O requires 44·0 parts calcium chloride per 100 of water) solidifies as a cryohydrate at about -55°. Just as for potassium, K = 39 (and sodium, Na = 23), there are the near analogues, Rb = 85 and Cs = 133, and also another, Li = 7, so in exactly the same manner for calcium, Ca = 40 (and magnesium, Mg = 24), there is another analogue of lighter atomic weight, beryllium, Be = 9, besides the near analogues strontium, Sr = 87, and barium, Ba = 137. As rubidium and cæsium are more rarely met with in nature than potassium, so also strontium and barium are rarer than calcium (in the same way that bromine and iodine are rarer than chlorine). Since they exhibit many points of resemblance with calcium, strontium and barium may be characterised after a very short acquaintance with their chief compounds; this shows the important advantages gained by distributing the elements according to their natural groups, to which matter we shall turn our attention in the next chapter. Among the compounds of barium met with in nature the commonest is the _sulphate_, BaSO_{4}, which forms anhydrous crystals of the rhombic system, which are identical in their crystalline form with anhydrite, and generally occur as transparent and semi-transparent masses of tabular crystals having a high specific gravity, namely 4·45, for which reason this salt bears the name of _heavy spar_ or _barytes_. Analogous to it is _celestine_, SrSO_{4}, which is, however, more rarely met with. Heavy spar frequently forms the gangue separated on dressing metallic ores from the vein stuff; this mineral is the source of all other barium compounds; for the carbonate, although more easily transformed into the other compounds (because acids act directly on it, evolving carbonic anhydride), is a comparatively rare mineral (BaCO_{3} forms the mineral _witherite_; SrCO_{3}, _strontianite_; both are rare, the latter is found at Etna). The treatment of barium sulphate is rendered difficult from the fact that it is insoluble both in water and acids, and has therefore to be treated by a method of reduction.[51] Like sodium sulphate and calcium sulphate, heavy spar when heated with charcoal parts with its oxygen and forms barium sulphide, BaS. For this purpose a pasty mixture of powdered heavy spar, charcoal, and tar is subjected to the action of a strong heat, when BaSO_{4} + 4C = BaS + 4CO. The residue is then treated with water, in which the barium sulphide is soluble.[52] When boiled with hydrochloric acid, barium chloride, BaCl_{2}, is obtained in solution, and the sulphur is disengaged as gaseous sulphuretted hydrogen, BaS + 2HCl = BaCl_{2} + H_{2}S. In this manner barium sulphate is converted into barium chloride,[53] and the latter by double decomposition with strong nitric acid or nitre gives the less soluble barium nitrate, Ba(NO_{3})_{2},[54] or with sodium carbonate a precipitate of barium carbonate, BaCO_{3}. Both these salts are able to give _barium oxide_, or _baryta_, BaO, and the hydroxide, Ba(HO)_{2}, which differs from lime by its great solubility in water,[55] and by the ease with which it forms a crystallo-hydrate, BaH_{2}O_{2},8H_{2}O, from its solutions. Owing to its solubility, baryta is frequently employed in manufactures and in practical chemistry as an alkali which has the very important property that it may be always entirely removed from solution by the addition of sulphuric acid, which entirely separates it as the insoluble barium sulphate, BaSO_{4}. It may also be removed whilst it remains in an alkaline state (for example, the excess which may remain when it is used for saturating acids) by means of carbonic anhydride, which also completely precipitates baryta as a sparingly soluble, colourless, and powdery carbonate. Both these reactions show that baryta has such properties as would very greatly extend its use were its compounds as widely distributed as those of sodium and calcium, and were its soluble compounds not poisonous. Barium nitrate is directly decomposed by the action of heat, barium oxide being left behind. The same takes place with barium carbonate, especially that form of it precipitated from solutions, and when mixed with charcoal or ignited in an atmosphere of steam. Barium oxide combines with water with the development of a large amount of heat, and the resultant hydroxide is very stable in its retention of the water, although it parts with it when strongly ignited.[55 bis] With oxygen the anhydrous oxide gives, as already mentioned in Chapters III. and IV., a _peroxide_, BaO_{2}.[56] Neither calcium nor strontium oxides are able to give such a peroxide directly, but they form peroxides under the action of hydrogen peroxide. [51] The action of barium sulphate on sodium and potassium carbonates is given on p. 437. [52] Barium sulphide is decomposed by water, BaS + 2H_{2}O = H_{2}S + Ba(OH)_{2} (the reaction is reversible), but both substances are soluble in water, and their separation is complicated by the fact that barium sulphide absorbs oxygen and gives insoluble barium sulphate. The hydrogen sulphide is sometimes removed from the solution by boiling with the oxides of copper or zinc. If sugar be added to a solution of barium sulphide, barium saccharate is precipitated on heating; it is decomposed by carbonic anhydride, so that barium carbonate is formed. An equivalent mixture of sodium sulphate with barium or strontium sulphates when ignited with charcoal gives a mixture of sodium sulphide and barium or strontium sulphide, and if this mixture be dissolved in water and the solution evaporated, barium or strontium hydroxide crystallises out on cooling, and sodium hydrosulphide, NaHS, is obtained in solution. The hydroxides BaH_{2}O_{2} and SrH_{2}O_{2} are prepared on a large scale, being applied to many reactions; for example, strontium hydroxide is prepared for sugar works for extracting crystallisable sugar from molasses. We may remark that Boussingault, by igniting barium sulphate in hydrochloric acid gas, obtained a complete decomposition, with the formation of barium chloride. Attention should also be turned to the fact that Grouven, by beating a mixture of charcoal and strontium sulphate with magnesium and potassium sulphates, showed the easy decomposability depending on the formation of double salts, such as SrS,K_{2}S, which are easily soluble in water, and give a precipitate of strontium carbonate with carbonic anhydride. In such examples as these we see that the force which binds double salts may play a part in directing the course of reactions, and the number of double salts of silica on the earth's surface shows that nature takes advantage of these forces in her chemical processes. It is worthy of remark that Buchner (1893), by mixing a 40 per cent. solution of barium acetate with a 60 per cent. solution of sulphate of alumina, obtained a thick glutinous mass, which only gave a precipitate of BaSO_{4} after being diluted with water. [53] Barium sulphate is sometimes converted into barium chloride in the following manner: finely-ground barium sulphate is heated with coal and manganese chloride (the residue from the manufacture of chlorine). The mass becomes semi-liquid, and when it evolves carbonic oxide the heating is stopped. The following double decompositions proceed during this operation: first the carbon takes up the oxygen from the barium sulphate, and gives sulphide, BaS, which enters into double decomposition with the chloride of manganese, MnCl_{2}, forming manganese sulphide, MnS, which is insoluble in water, and soluble barium chloride. This solution is easily obtained pure because many foreign impurities, such as iron, remain in the insoluble portion with the manganese. The solution of barium chloride is chiefly used for the preparation of barium sulphate, which is precipitated by sulphuric acid, by which means _barium sulphate_ is re-formed as a powder. This salt is characterised by the fact that it is unacted on by the majority of chemical reagents, is insoluble in water, and is not dissolved by acids. Owing to this, artificial barium sulphate forms a permanent white paint which is used instead of (and mixed with) white lead, and has been termed 'blanc fixé' or 'permanent white.' The solution of one part of calcium chloride at 20° requires 1·36 part of water, the solution of one part of strontium chloride requires 1·88 part of water at the same temperature, and the solution of barium chloride 2·88 parts of water. The solubility of the bromides and iodides varies in the same proportion. The chlorides of barium and strontium crystallise out from solution with great ease in combination with water; they form BaCl_{2},2H_{2}O and SrCl_{2},6H_{2}O. The latter (which separates out at 40°) resembles the salts of Ca and Mg in composition, and Étard (1892) obtained SrCl_{2},2H_{2}O from solutions at 90-130°. We may also observe that the crystallo-hydrates BaBr_{2},H_{2}O and BaI_{2},7H_{2}O are known. [54] The nitrates Sr(NO_{3})_{2} (in the cold its solutions give a crystallo-hydrate containing 4H_{2}O) and Ba(NO_{3})_{2} are so very sparingly soluble in water that they separate in considerable quantities when a solution of sodium nitrate is added to a strong solution of either barium or strontium chloride. They are obtained by the action of nitric acid on the carbonates or oxides. 100 parts of water at 15° dissolve 6·5 parts of strontium nitrate and 8·2 parts of barium nitrate, whilst more than 300 parts of calcium nitrate are soluble at the same temperature. Strontium nitrate communicates a crimson coloration to the flame of burning substances, and is therefore frequently used for Bengal fire, fireworks, and signal lights, for which purpose the salts of lithium are still better fitted. Calcium nitrate is exceedingly hygroscopic. Barium nitrate, on the contrary, does not show this property in the least degree, and in this respect it resembles potassium nitrate, and is therefore used instead of the latter for the preparation of a gunpowder which is called 'saxifragin powder' (76 parts of barium nitrate, 2 parts of nitre, and 22 parts of charcoal). [55] The dissociation of the crystallo-hydrate of baryta is given in Chapter I., Note 65. 100 parts of water dissolve 0° 20° 40° 60° 80° BaO 1·5 3·5 7·4 18·8 90·8 SrO 0·3 0·7 1·4 3 9 Supersaturated solutions are easily formed. The anhydrous oxide BaO fuses in the oxyhydrogen flame. When ignited in the vapour of potassium, the latter takes up the oxygen; whilst in chlorine, oxygen is separated and barium chloride formed. [55 bis] Brugellmann, by heating BaH_{2}O_{2} in a graphite or clay crucible, obtained BaO in needles, sp. gr. 5·32, and by heating in a platinum crucible--in crystals belonging to the cubical system, sp. gr. 5·74. SrO is obtained in the latter form from the nitrate. The following are the specific gravities of the oxides from different sources:-- MgO CaO SrO from RN_{2}O_{6} 3·38 3·25 4·75 " RCO_{3} 3·48 3·26 4·45 " RH_{2}O_{2} 3·41 3·25 4·57 [56] The property of barium oxide of absorbing oxygen when heated, and giving the peroxide, BaO_{2}, is very characteristic for this oxide (_see_ Chapter III., Note 7). It only belongs to the anhydrous oxide. The hydroxide does not absorb oxygen. Peroxides of calcium and strontium may be obtained by means of hydrogen peroxide. Barium peroxide is insoluble in water, but is able to form a hydrate with it, and also to combine with hydrogen peroxide, forming a very unstable compound having the composition BaH_{2}O_{4} (obtained by Professor Schöne), which in course of time evolves oxygen (Chapter IV., Note 21). Barium oxide is decomposed when heated with potassium; fused barium chloride is decomposed, as Davy showed, by the action of a galvanic current, forming metallic _barium_; and Crookes (1862) obtained an amalgam of barium from which the mercury could easily be driven off, by heating sodium amalgam in a saturated solution of barium chloride. Strontium is obtained by the same processes. Both metals are soluble in mercury, and seem to be non-volatile or only very slightly volatile. They are both heavier than water; the specific gravity of barium is 3·6, and of strontium 2·5. They both decompose water at the ordinary temperature, like the metals of the alkalis. Barium and strontium as saline elements are characterised by their powerful basic properties, so that they form acid salts with difficulty, and scarcely form basic salts. On comparing them together and with calcium, it is evident that the alkaline properties in this group (as in the group potassium, rubidium, cæsium) increase with the atomic weight, and this succession clearly shows itself in many of their corresponding compounds. Thus, for instance, the solubility of the hydroxides RH_{2}O_{2} and the specific gravity[57] rise in passing from calcium to strontium and barium, while the solubility of the sulphates decreases,[58] and therefore in the case of magnesium and beryllium, as metals whose atomic weights are still less, we should expect the solubility of the sulphates to be greater, and this is in reality the case. [57] Even in solutions a gradual progression in the increase of the specific gravity shows itself, not only for equivalent solutions (for instance, RCl_{2} + 200H_{2}O), but even with an equal percentage composition, as is seen from the curves giving the specific gravity (water 4° = 10,000) at 15° (for barium chloride, according to Bourdiakoff's determinations): BeCl_{2} : S = 9,992 + 67·21_p_ + 0·111_p_^2 CaCl_{2} : S = 9,992 + 80·24_p_ + 0·476_p_^2 SrCl_{2} : S = 9,992 + 85·57_p_ + 0·733_p_^2 BaCl_{2} : S = 9,992 + 86·56_p_ + 0·813_p_^2 [58] One part of calcium sulphate at the ordinary temperature requires about 500 parts of water for solution, strontium sulphate about 7,000 parts, barium sulphate about 400,000 parts, whilst beryllium sulphate is easily soluble in water. Just as in the series of the alkali metals we saw the metals potassium, rubidium, and cæsium approaching near to each other in their properties, and allied to them two metals having smaller combining weights--namely, sodium, and the lightest of all, lithium, which all exhibited certain peculiar characteristic properties--so also in the case of the metals of the alkaline earths we find, besides calcium, barium, and strontium, the metal magnesium and also _beryllium_ or _glucinum_. In respect to the magnitude of its atomic weight, this last occupies the same position in the series of the metals of the alkaline earths as lithium does in the series of the alkali metals, for the combining weight of beryllium, Be or Gl = 9. This combining weight is greater than that of lithium (7), as the combining weight of magnesium (24) is greater than that of sodium (23), and as that of calcium (40) is greater than that of potassium (39), &c.[59] Beryllium was so named because it occurs in the mineral _beryl_. The metal is also called glucinum (from the Greek word [Greek: glykys], 'sweet'), because its salts have a sweet taste. It occurs in beryl, aquamarine, the emerald, and other minerals, which are generally of a green colour; they are sometimes found in considerable masses, but as a rule are comparatively rare and, as transparent crystals, form precious stones. The composition of beryl and of the emerald is as follows: Al_{2}O_{3},3BeO,6SiO_{2}. The Siberian and Brazilian beryls are the best known. The specific gravity of beryl is about 2·7. Beryllium oxide, from the feebleness of its basic properties, presents an analogy to aluminium oxide in the same way that lithium oxide is analogous to magnesium oxide.[60] Owing to its rare occurrence in nature, to the absence of any especially distinct individual properties, and to the possibility of foretelling them to a certain extent on the basis of the periodic system of the elements given in the following chapter, and owing to the brevity of this treatise, we will not discuss at any length the compounds of beryllium, and will only observe that their individuality was pointed out in 1798 by Vauquelin, and that metallic beryllium was obtained by Wöhler and Bussy. Wöhler obtained _metallic beryllium_ (like magnesium) by acting on beryllium chloride, BeCl_{2}, with potassium (it is best prepared by fusing K_{2}BeF_{4} with Na). Metallic beryllium has a specific gravity 1·64 (Nilson and Pettersson). It is very infusible, melting at nearly the same temperature as silver, which it resembles in its white colour and lustre. It is characterised by the fact that it is very difficultly oxidised, and even in the oxidising flame of the blowpipe is only superficially covered by a coating of oxide; it does not burn in pure oxygen, and does not decompose water at the ordinary temperature or at a red heat, but gaseous hydrochloric acid is decomposed by it when slightly heated, with evolution of hydrogen and development of a considerable amount of heat. Even dilute hydrochloric acid acts in the same manner at the ordinary temperature. Beryllium also acts easily on sulphuric acid, but it is remarkable that neither dilute nor strong nitric acid acts on beryllium, which seems especially able to resist oxidising agents. Potassium hydroxide acts on beryllium as on aluminium, hydrogen being disengaged and the metal dissolved, but ammonia has no action on it. These properties of metallic beryllium seem to isolate it from the series of the other metals described in this chapter, but if we compare the properties of calcium, magnesium, and beryllium we shall see that magnesium occupies a position intermediate between the other two. Whilst calcium decomposes water with great ease, magnesium does so with difficulty, and beryllium not at all. The peculiarities of beryllium among the metals of the alkaline earths recall the fact that in the series of the halogens we saw that fluorine differed from the other halogens in many of its properties and had the smallest atomic weight. The same is the case with regard to beryllium among the other metals of the alkaline earths. [59] We refer beryllium to the class of the bivalent metals of the alkaline earths--that is, we ascribe to its oxide the formula BeO, and do not consider it as trivalent (Be = 13·5, Chapter VII., Note 21), although that view has been upheld by many chemists. The true atomic composition of beryllium oxide was first given by the Russian chemist, Avdéeff (1819), in his researches on the compounds of this metal. He compared the compounds of beryllium to those of magnesium, and refuted the notion prevalent at the time, of the resemblance between the oxides of beryllium and aluminium, by proving that beryllium sulphate presents a greater resemblance to magnesium sulphate than to aluminium sulphate. It was especially noticed that the analogues of alumina give alums, whilst beryllium oxide, although it is a feeble base, easily giving, like magnesia, basic and double salts, does not form true alums. The establishment of the periodic system of the elements (1869), considered in the following chapter, immediately indicated that Avdéeff's view corresponded with the truth--that is, that beryllium is bivalent, which therefore necessitated the denial of its trivalency. This scientific controversy resulted in a long series of researches (1870-80) concerning this element, and ended in Nilson and Pettersson--two of the chief advocates of the trivalency of beryllium--determining the vapour density of BeCl_{2} = 40, (Chapter VII., Note 21), which gave an undoubted proof of its bivalency (_see_ also Note 3). [60] Beryllium oxide, like aluminium oxide, is precipitated from solutions of its salts by alkalis as a gelatinous hydroxide, BeH_{2}O_{2}, which, like alumina, is soluble in an excess of caustic potash or soda. This reaction may be taken advantage of for distinguishing and separating beryllium from aluminium, because when the alkaline solution is diluted with water and boiled, beryllium hydroxide is precipitated, whilst the alumina remains in solution. The solubility of the beryllium oxide at once clearly indicates its feeble basic properties, and, as it were, separates this oxide from the class of the alkaline earths. But on arranging the oxides of the above-described metals of the alkaline earths according to their decreasing atomic weights we have the series BaO, SrO, CaO, MgO, BeO, in which the basic properties and solubility of the oxides consecutively and distinctly decrease until we reach a point when, had we not known of the existence of the beryllium oxide, we should expect to find in its place an oxide insoluble in water and of feeble basic properties. If an alcoholic solution of caustic potash be saturated with the hydrate of BeO, and evaporated under the receiver of an air pump, it forms silky crystals BeK_{2}O_{2}. Another characteristic of the salts of beryllium is that they give with aqueous ammonia a gelatinous precipitate which is soluble in an excess of ammonium carbonate like the precipitate of magnesia; in this beryllium oxide differs from the oxide of aluminium. Beryllium oxide easily forms a carbonate which is insoluble in water, and resembles magnesium carbonate in many respects. Beryllium sulphate is distinguished by its considerable solubility in water--thus, at the ordinary temperature it dissolves in an equal weight of water; it crystallises out from its solutions in well-formed crystals, which do not change in the air, and contain BeSO_{4},4H_{2}O. When ignited it leaves beryllium oxide, but this oxide, after prolonged ignition, is re-dissolved by sulphuric acid, whilst aluminium sulphate, after a similar treatment, leaves aluminium oxide, which is no longer soluble in acids. With a few exceptions, the salts of beryllium crystallise with great difficulty, and to a considerable extent resemble the salts of magnesium; thus, for instance, beryllium chloride is analogous to magnesium chloride. It is volatile in an anhydrous state, and in a hydrated state it decomposes, with the evolution of hydrochloric acid. In addition to the above characteristics of the compounds of the metals of the alkaline earths, we must add that they, like the alkali metals, combine with nitrogen and hydrogen, and while sodium nitride (obtained by igniting the amide of sodium, Chapter XII., Note 44 bis) and lithium nitride (obtained by heating lithium in nitrogen, Chapter XIII., Note 39) have the composition R_{3}N, so the nitrides of magnesium (Note 14), calcium, strontium, and barium have the composition R_{3}N_{2}, for example, Ba_{3}N_{2}, as might be expected from the diatomicity of the metals of the alkaline earths and from the relation of the nitrides to ammonia, which is obtained from all of these compounds by the action of water. The _nitrides_ of Ca, Sr, and Ba are formed directly (Maquenne, 1892) by heating the metals in nitrogen. They all have the appearance of an amorphous powder of dark colour; as regards their reactions, it is known that besides disengaging ammonia with water, they form cyanides when heated with carbonic oxide; for instance, Ba_{3}N_{2} + 2CO = Ba(CN)_{2} + 2BaO.[61] [61] Thus in the nitrides of the metals we have substances by means of which we can easily obtain from the nitrogen of the air, not only ammonia, but also with the aid of CO, by synthesis, a whole series of complex carbon and nitrogen compounds. The metals of the alkaline earths, just like Na and K, absorb hydrogen under certain conditions, and form pulverulent easily oxidisable metallic hydrides, whose composition corresponds exactly to that of Na_{2}H and K_{2}H, with the substitution of K_{2} and Na_{2} by the atoms Be, Mg, Ca, Sr, and Ba. The _hydrides of the metals of the alkaline earths_ were discovered by C. Winkler (1891) in investigating the reducibility of these metals by magnesium. In reducing their oxides by heating them with magnesium powder in a stream of hydrogen, Winkler observed that the hydrogen was absorbed (but very slowly), _i.e._ at the moment of their separation all the metals of the alkaline earths combine with hydrogen. This absorptive power increases in passing from Be to Mg, Ca, Sr, and Ba, and the resultant hydrides retain the combined hydrogen[62] when heated, so that these hydrides are distinguished for their considerable stability under heat, but they oxidise very easily.[63] [62] As the hydrides of calcium, magnesium, &c. are very stable under the action of heat, and these metals and hydrogen occur in the sun, it is likely that the formation of their hydrides may take place there. (Private communication from Prof. Winkler, 1894.) It is probable that in the free metals of the alkaline earths hitherto obtained a portion was frequently in combination with nitrogen and hydrogen. [63] Thus, for instance, a mixture of 56 parts of CaO and 24 parts of magnesium powder is heated in an iron pipe (placed over a row of gas burners as in the combustion furnace used for organic analysis) in a stream of hydrogen. After being heated for 1/2 hour the mixture is found to absorb hydrogen (it no longer passes over the mixture, but is retained by it). The product, which is light grey, and slightly coherent, disengages a mass of hydrogen when water is poured over it, and burns when heated in air. The resultant mass contains 33 per cent. CaH, about 28 per cent. CaO, and about 38 per cent. MgO. Neither CaH nor any other MH has yet been obtained in a pure state. The acetylene derivatives of the metals of the alkaline earths C_{2}M (Chapter VIII., Note 12 bis), for instance, C_{2}Ba, obtained by Maquenne and Moissan, belong to the same class of analogous compounds. It must here be remarked that the oxides MO of the metals of the alkaline earths, although not reducible by carbon at a furnace heat, yet under the action of the heat attained in electrical furnaces, not only give up their oxygen to carbon (probably partly owing to the action of the current), but also combine with carbon. The resultant compounds, C_{2}M, evolve acetylene, C_{2}H_{2}, with HCl, just as N_{2}M_{3} give ammonia. We may remark moreover that the series of compounds of the metals of the alkaline earths with hydrogen, nitrogen and carbon is a discovery of recent years, and that probably further research will give rise to similar unexpected compounds, and by extending our knowledge of their reactions prove to be of great interest. Thus the analogies and correlation of the metals of these two groups are now clearly marked, not only in their behaviour towards oxygen, chlorine, acids, &c., but also in their capability of combining with nitrogen and hydrogen. * * * * * END OF THE FIRST VOLUME PRINTED BY SPOTTISWOODE AND CO., NEW-STREET SQUARE LONDON * * * * * A CLASSIFIED CATALOGUE OF SCIENTIFIC WORKS PUBLISHED BY MESSRS. LONGMANS, GREEN, & CO. LONDON: 39 PATERNOSTER ROW, E.C. NEW YORK: 91 & 93 FIFTH AVENUE. BOMBAY: 32 HORNBY ROAD. CONTENTS. PAGE _ADVANCED SCIENCE MANUALS_ 30 AGRICULTURE 27 ASTRONOMY 14 BACTERIOLOGY 25 BIOLOGY 25 BOTANY 26 BUILDING CONSTRUCTION 10 CHEMISTRY 2 DYNAMICS 6 ELECTRICITY 11 _ELEMENTARY SCIENCE MANUALS_ 30 ENGINEERING 12 GEOLOGY 17 HEALTH AND HYGIENE 17 HEAT 8 HYDROSTATICS 6 LIGHT 8 _LONDON SCIENCE CLASS-BOOKS_ 32 _LONGMANS' CIVIL ENGINEERING SERIES_ 13 MACHINE DRAWING AND DESIGN 13 MAGNETISM 11 MANUFACTURES 17 MECHANICS 6 MEDICINE AND SURGERY 19 METALLURGY 14 MINERALOGY 14 NATURAL HISTORY 18 NAVIGATION 14 OPTICS 8 PHOTOGRAPHY 8 PHYSICS 5 PHYSIOGRAPHY 17 PHYSIOLOGY 25 _PRACTICAL ELEMENTARY SCIENCE SERIES_ 32 _PROCTOR'S (R. A.) 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54210	----	THE PRINCIPLES OF CHEMISTRY By D. MENDELÉEFF TRANSLATED FROM THE RUSSIAN (SIXTH EDITION) BY GEORGE KAMENSKY, A.R.S.M. OF THE IMPERIAL MINT, ST PETERSBURG: MEMBER OF THE RUSSIAN PHYSICO-CHEMICAL SOCIETY EDITED BY T. A. LAWSON, B.Sc. PH.D. EXAMINER IN COAL-TAR PRODUCTS TO THE CITY AND GUILDS OF LONDON INSTITUTE FELLOW OF THE INSTITUTE OF CHEMISTRY IN TWO VOLUMES VOLUME II. LONGMANS, GREEN, AND CO 39 PATERNOSTER ROW, LONDON NEW YORK AND BOMBAY 1897 All rights reserved * * * * * TABLE III. _The periodic dependence of the composition of the simplest compounds and properties of the simple bodies upon the atomic weights of the elements._ +-------------------------+--------------------------------+ | | | |Molecular composition of | | |the higher hydrogen and | Atomic weights of the elements | |metallo-organic compounds| | |-------------------------+--------------------------------+ | | | | | | |E=CH_{3}, C_{2}H_{5}, &c.| | | | | | | | |[1] [2] [3] [4] | [5] [6] | | | | | HH| H 1,005 (mean) | | | Li 7·02 (Stas) | | | Be 9·1 (Nilson Pettersson)| | BE_{3} -- --| B 11·0 (Ramsay Ashton) | | CH_{4} C_{2}H_{6} | | | C_{2}H_{4} C_{2}H_{2} | C 12·00 (Roscoe) | | NH_{3} N_{2}H_{4} --| N 14·04 (Stas) | | OH_{2} --| O 16 (conventional) | | FH| F 19·0 (Christiansen) | | | | | NaE| Na 23·04 (Stas) | | MgE_{2} --| Mg 24·3 (Burton) | | AlE_{3} -- --| Al 27·1 (Mallet) | |SiH_{4} Si_{2}E_{6} -- --| Si 28·4 (Thorpe Young) | | PH_{3} P_{2}H_{4} --| P 31·0 (v. d. Plaats) | | SH_{2} --| S 32·06 (Stas) | | ClH| Cl 35·45 (Stas) | | | | | | K 39·15 (Stas) | | | Ca 40·0 (Dumas) | | | Sc 44·0 (Nilson) | | | Ti 48·1 (Thorpe) | | | V 51·2 (Roscoe) | | | Cr 52·1 (Rawson) | | | Mn 55·1 (Marignac) | | | Fe 56·0 (Dumas) | | | Co 58·9 (Zimmermann) | | | Ni 59·4 (Winkler) | | | Cu 63.6 (Richards) | | ZnE_{2} --| Zn 65·3 (Marignac) | | GaE_{3} -- --| Ga 69·9 (Boisbaudran) | | GeE_{4} -- -- --| Ge 72·3 (Winkler) | | AsH_{3} -- --| As 75·0 (Dumas) | | SeH_{2} --| Se 79·0[A] (Pettersson) | | BrH| Br 79·95 (Stas) | | | | | | Rb 85·5 (Godeffroy) | | | Sr 87·6 (Dumas) | | | Y 89 (Clève) | | | Zr 90·6 (Bailey) | | | Nb 94 (Marignac) | | | Mo 96·1 (Maas) | | | Unknown metal | | | | | | Ru 101·7 (Joly) | | | Rh 102·7 (Seubert) | | | Pd 106·4 (Keller Smith) | | | Ag 107·92 (Stas) | | CdE_{2} --| Cd 112·1 (Lorimer Smith) | | InE_{3} -- --| In 113·6 (Winkler) | | SnE_{4} -- -- --| Sn 119·1 (Classen) | | SbH_{3} -- --| Sb 120·4 (Schneider) | | TeH_{2} --| Te 125·1 (Brauner) | | | | | | Cs 132·7 (Godeffroy) | | | Ba 137·4 (Richards) | | | La 138·2 (Brauner) | | | Ce 140·2 (Brauner) | | | | | | Ta 182·7 (Marignac) | | | W 184·0 (Waddel) | | | Unknown element. | | | | | | Ir 193·3 (Joly) | | | Pt 196·0 (Dittmar McArthur) | | | Au 197·5 (Mallet) | | HgE_{2} --| Hg 200·5 (Erdmann Mar.) | | TlE_{3} -- --| Tl 204·1 (Crookes) | | PbE_{4} -- -- --| Pb 206·90 (Stas) | | BiE_{3} -- --| Bi 208·9 (Classen) | | | Five unknown elements. | | | Th 232·4 (Krüss Nilson) | | | Unknown element. | | | U 239·3 (Zimmermann) | +-------------------------+--------------------------------+ +----------------------------------------------------------------------+ | | | | | Composition of the saline compounds, X = Cl | | | +----------------------------------------------------------------------+ | Br, (NO_{3}), 1/2 O, 1/2 (SO_{4}), OH, (OM) = Z, where M = K, | | 1/2 Ca, 1/3 Al, &c. | |Form RX RX_{2} RX_{3} RX_{4} RX_{5} RX_{6} RX_{7} RX_{8}| |Oxi- R_{2}O RO R_{2}O_{3} RO_{2} R_{2}O_{5} RO_{3} R_{2}O_{7} RO_{4}| |des | | [7] [8] [9] [10] [11] [12] [13] [14] | | | | X or H_{2}O | | iX | | -- BeX_{2} | | -- -- BX_{3} | | | | -- CO -- COZ_{2} | | N_{2}O NO NOZ NO_2 NO_{2}Z | | -- OX_{2} | | FZ | | | | NaX | | -- MgX_{2} | | -- -- AlX_{3} | | -- -- -- SiOZ_{2} | | -- -- PX_{3} -- POZ_{3} | | -- SX_{2} -- SOZ_{2} -- SO_{2}Z_{2} | | ClZ -- ClOZ -- ClO_{2}Z -- ClO_{3}Z | | | | KX | | -- CaX_{2} | | -- -- ScX_{3} | | -- TiX_{2} TiX_{3} TiX_{4} | | -- VO VOX -- VOZ_{3} | | -- CrX_{2} CrX_{3} CrO_{2} -- CrO_{2}Z_{2} | | -- MnX_{2} MnX_{3} MnO_{2} -- MnO_{2}Z_{2} MnO_{3}Z | | -- FeX_{2} FeX_{3} -- -- FeO_{2}Z_{2} | | -- CoX_{2} CoX_{3} CoO_{2} | | -- NiX_{2} NiX_{3} | | CuX CuX_{2} | | -- ZnX_{2} | | -- -- GaX_{3} | | -- GeX_{2} -- GeX_{4} | | -- AsS AsX_{3} AsS_{2} AsO_{2}Z | | -- -- -- SeOZ_{2} -- SeO_{2}Z_{2} | | BrZ -- BrOZ -- BrO_{2}Z -- BrO_{3}Z | | | | RbX | | -- SrX_{2} | | -- -- YX_{3} | | -- -- -- ZrX_{4} | | -- -- NbX_{3} -- NbO_{2}Z | | -- -- MoX_{3} MoX_{4} -- MoO_{2}Z_{2} | |(eka-manganese, Em = 99). EmO_{3}Z | | RuO_{4}| | -- RuX_{2} RuX_{3} RuX_{4} -- RuO_{2}Z_{2} RuO_{3}Z | | -- RhX_{2} RhX_{3} RhX_{4} -- RhO_{2}Z_{2} | | PdX PdX_{2} -- PdX_{4} | | AgX | | -- CdX_{2} | | -- InX_{2} InX_{3} | | -- SnX_{2} -- SnX_{4} | | -- -- SbX_{3} -- SbO_{2}Z | | -- -- -- TeOZ_{2} -- TeO_{2}Z_{2} | | IZ -- IZ_{3} -- IO_{2}Z -- IO_{3}Z | | | | CsX | | -- BaX_{2} | | -- -- LaX_{3} | | -- -- CeX_{3} CeX_{4} | | Little known Di = 142.1 and Yb = 173.2, and over 15 unknown elements.| | -- -- -- -- TaO_{2}Z | | -- -- -- WX_{4} -- WO_{2}Z_{2} | | | | OsO_{4}| | -- -- OsX_{3} OsX_{4} -- OsO_{2}Z_{2} -- | | -- -- IrX_{3} IrX_{4} -- IrO_{2}Z_{2} | | -- PtX_{2} -- PtX_{4} | | AuX -- AuX_{3} | | HgX HgX_{2} | | TlX -- TlX_{3} | | -- PbX_{2} -- PbOZ_{2} | | -- -- BiX_{3} -- BiO_{2}Z | | | | -- -- -- ThX_{4} | | | | -- -- -- UO_{2} -- UO_{2}X_{2} UO_{4}| +----------------------------------------------------------------------+ +-------------------------+------------+---------+---------------------+ | | | Lower | Simple bodies | |Molecular composition of | |hydrogen +-----+-------+-------| |the higher hydrogen and | Peroxides | com- | Sp. | Sp. |Melting| |metallo-organic compounds| | pounds | gr | vol. | point | |-------------------------+------------+---------+-----+-------+-------| | | | | | | | | | | | | | | |E=CH_{3}, C_{2}H_{5}, &c.| | | | | | | | | | | | | | | | | | | | |[1] [2] [3] [4] | [15] | [16] |[17] | [18] | [19] | | | | | | | | | HH|H_{2}O_{2} | -- |*0·05| 20 | -250°?| | | -- | -- | 0·59| 11·9 | 180° | | | -- | BeH | 1·64| 5·5 | 900°?| | BE_{3} -- --| -- | -- | 2·5 | 4·4 |1,300°?| | CH_{4} C_{2}H_{6} | | | | | | | C_{2}H_{4} C_{2}H_{2} |C_{2}O_{5}* | -- |*1·9 | 6·3 |2,600°?| | NH_{3} N_{2}H_{4} --|N_{2}O_{6}* | N_{3}H |*0·6 | 23 | -203° | | OH_{2} --|O_{3} | -- |*0·9 | 18 | -230°?| | FH| -- | -- |?1·0 | 19 | ? | | | | | | | | | NaE|NaO | Na_{2}H | 0·98| 23·5 | 96° | | MgE_{2} --| -- | MgH | 1·74| 14 | 500° | | AlE_{3} -- --| -- | -- | 2·6 | 11 | 600° | |SiH_{4} Si_{2}E_{6} -- --| -- | -- | 2·3 | 12 |1,300°?| | PH_{3} P_{2}H_{4} --| -- | P_2H | 2·2 | 14 | 44° | | SH_{2} --|S_{2}O_{7} | -- | 2·07| 15 | 114° | | ClH| -- | -- |*1·3 | 27 | -75° | | | | | | | | | |KO_{2} | K_{2}H | 0·87| 45 | 58° | | |CaO_{2} | CaH | 1·56| 26 | 800° | | | -- | -- |?2·5 | ?18 |1,200°?| | |TiO_{3} | -- | 3·6 | 13 |2,500°?| | | -- | -- | 5·5 | 9 |3,000°?| | |Cr_{2}O_{7} | -- | 6·7 | 7·7 |2,000°?| | | -- | -- | 7·5 | 7·3 |1,500° | | | -- |Fe_{n}H* | 7·8 | 7·2 |1,450° | | | -- | -- | 8·6 | 6·8 |1,400° | | | -- | Ni_{n}H | 8·7 | 6·8 |1,350° | | |Cu_{2}O_{5}*| CuH | 8·8 | 7·2 |1,054° | | ZnE_{2} --|ZnO_{2} | -- | 7·1 | 9·2 | 418° | | GaE_{3} -- --| -- | -- | 5·96| 11·7 | 30° | | GeE_{4} -- -- --| -- | -- | 5·47| 13·2 | 900° | | AsH_{3} -- --| -- |As_{4}H* | 5·65| 13·3 | 500° | | SeH_{2} --| -- | -- | 4·8 | 16 | 217° | | BrH| -- | -- | 3·1 | 26 | -7° | | | | | | | | | |RbO |Rb_{2}H* | 1·5 | 57 | 39° | | |SrO_{2} | SrH | 2·5 | 35 | 600°?| | | -- | -- |*3·4 | *26 |1,000°?| | | -- |Zr_{4n}H*| 4·1 | 22 |1,500°?| | | -- |Nb_{n}H* | 7·1 | 13 |1,800°?| | |Mo_{2}O_{7} | -- | 8·6 | 11 |2,200°?| | | -- | -- | -- | -- | -- | | | | | | | | | | -- |Ru_{n}H* |12·2 | 8·4 |2,000°?| | | -- |Rh_{n}H* |12·1 | 8·6 |1,900°?| | | -- | Pd_{2}H |11·4 | 8·3 |1,500° | | |AgO | -- |10·5 | 10·3 | 950° | | CdE_{2} --|CdO_{2} | -- | 8·6 | 13 | 320° | | InE_{3} -- --| -- | -- | 7·4 | 14 | 176° | | SnE_{4} -- -- --|SnO_{3} | -- | 7·2 | 16 | 232° | | SbH_{3} -- --| -- | -- | 6·7 | 18 | 432° | | TeH_{2} --| -- | -- | 6·4 | 20 | 455° | | IH| -- | -- | 4·9 | 26 | 114° | | | | | | | | | | -- |Cs_{2}H* | 2·37| 56 | 27° | | |BaO_{2} | BaH | 3·75| 36 | ? | | | -- | -- | 6·1 | 23 | ? | | | -- | -- | 6·6 | 21 | 700°?| | | | | | | | | | -- |Ta_{n}H* |10·4 | 18 | ? | | |W_{2}O_{7} | -- |19·1 | 9·6 |2,600° | | | | | | | | | | | | | | | | | -- | -- |22·5 | 8·5 |2,700°?| | | -- | Ir_nH* |22·4 | 8·6 |2,000° | | | -- |Pt_{n}H* |21·4 | 9·2 |1,775° | | | -- | -- |19·3 | 10 |1,045° | | HgE_{2} --| -- | -- |13·6 | 15 | -39° | | TlE_{3} -- --| -- | -- |11·8 | 17 | 294° | | PbE_{4} -- -- --| -- | -- |11·3 | 18 | 328° | | BiE_{3} -- --| -- | -- | 9·8 | 21 | 269° | | | | | | | | | | -- | -- |11·1 | 21 | ? | | | | | | | | | | -- | -- |18·7 | 13 |2,400°?| +-------------------------+------------+---------+-----+-------+-------+ [A] From analogy there is reason for thinking that the atomic weight of selenium is really slightly less than 79·0. Columns 1, 2, 3, and 4 give the molecular composition of the hydrogen and metallo-organic compounds, exhibiting the most characteristic forms assumed by the elements. The first column contains only those which correspond to the form RX_{4}, the second column those of the form RX_{3}, the third of the form RX_{2}, and the fourth of the form RX, so that the periodicity stands out clearly (see Column 16). Column 5 contains the symbols of all the more or less well-known elements, placed according to the order of the magnitude of their atomic weights. Column 6 contains the atomic weights of the elements according to the most trustworthy determinations. The names of the investigators are given in parenthesis. The atomic weight of oxygen, taken as 16, forms the basis upon which these atomic weights were calculated. Some of these have been recalculated by me on the basis of Stas's most trustworthy data (_see_ Chapter XXIV. and the numbers given by Stas in the table, where they are taken according to van der Plaats and Thomsen's calculations). Columns 7-14 contain the composition of the saline compounds of the elements, placed according to their forms, RX, RX_{2} to RX_{8} (in the 14^{th} column). If the element R has a metallic character like H, Li, Be, &c., then X represents Cl, NO_{3}, 1/2 SO_{4}, &c., haloid radicles, or (OH) if a perfect hydrate is formed (alkali, aqueous base), or 1/2 O, 1/2 S, &c. when an anhydrous oxide, sulphide, &c. is formed. For instance, NaCl, Mg(NO_{3})_{2}, Al_{2}(SO_{4})_{3}, correspond to NaX, MgX_{2}, and AlX_{3}; so also Na(OH), Mg(OH)_{2}, Al(OH)_{3}, Na_{2}O, MgO, Al_{2}O_{3}, &c. But if the element, like C or N, be of a metalloid or acid character, X must be regarded as (OH) in the formation of hydrates; (OM) in the formation of salts, where M is the equivalent of a metal, 1/2 O in the formation of an anhydride, and Cl in the formation of a chloranhydride; and in this case (_i.e._ in the acid compounds) Z is put in the place of X; for example, the formulæ COZ_{2}, NO_{2}Z, MNO_{2}Z, FeO_{2}Z_{2}, and IZ_{3} correspond to CO(NaO)_{2} = Na_{2}CO_{3}, COCl_{2}, CO_{2}, NO_{2}(NaO) = NaNO_{3}, NO_{2}Cl, NO_{2}(OH) = HNO_{3}; MnO_{3}(OK) = KMnO_{4}, ICl, &c. The 15th column gives the compositions of the peroxides of the elements, _taking them as anhydrous_. An asterisk (*) is attached to those of which the composition has not been well established, and a dash (--) shows that for a given element no peroxides have yet been obtained. The peroxides contain more oxygen than the higher saline oxides of the same elements, are powerfully oxidising, and easily give peroxide of hydrogen. This latter circumstance necessitates their being referred to the type of peroxide of hydrogen, if bases and acids are referred to the type of water (see Chapter XV., Note 7 and 11 bis). The 16th column gives the composition of the lower hydrogen compounds like N_{3}H and Na_{2}H. They may often be regarded as alloys of hydrogen, which is frequently disengaged by them at a comparatively moderate temperature. They differ greatly in their nature from the hydrogen compounds given in columns 1-4 (_see_ Note 12). Column 17 gives the specific gravity of the elements in a solid and a liquid state. An asterisk (*) is placed by those which can either only be assumed from analogy (for example, the sp. gr. of fluorine and hydrogen, which have not been obtained in a liquid state), or which vary very rapidly with a variation of temperature and pressure (like oxygen and nitrogen), or physical state (for instance, carbon in passing from the state of charcoal to graphite and diamond). But as the sp. gr. in general varies with the temperature, mechanical condition, &c., the figures given, although chosen from the most trustworthy sources, can only be regarded as approximate, and not as absolutely true. They clearly show a certain periodicity; for instance, the sp. gr. diminishes from Al on both sides (Al, Mg, Na, with decreasing atomic weight; and Al, Si, P, S, Cl, with increasing atomic weight, it also diminishes on both sides from Cu, Ru, and Os.) The same remarks refer to the figures in the 18th column, which gives the so-called atomic volumes of the simple bodies, or the quotient of their atomic weight and specific gravity. For Na, K, Rb, and Cs the atomic volume is greatest among the neighbouring elements. For Ni, Pd, and Os it is least, and this indicates the periodicity of this property of the simple bodies. The last (19th) column gives the melting points of the simple bodies. Here also a periodicity is seen, i.e. a maximum and minimum value between which there are intermediate values, as we see, for instance, in the series Cl, K, Ca, Sc, and Ti, or in the series Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Ge. * * * * * CHAPTER XV THE GROUPING OF THE ELEMENTS AND THE PERIODIC LAW It is seen from the examples given in the preceding chapters that the sum of the data concerning the chemical transformations proper to the elements (for instance, with respect to the formation of acids, salts, and other compounds having definite properties) is insufficient for accurately determining the relationship of the elements, inasmuch as this may be many-sided. Thus, lithium and barium are in some respects analogous to sodium and potassium, and in others to magnesium and calcium. It is evident, therefore, that for a complete judgment it is necessary to have, not only qualitative, but also quantitative, exact and measurable, data. When a property can be measured it ceases to be vague, and becomes quantitative instead of merely qualitative. Among these measurable properties of the elements, or of their corresponding compounds, are: (_a_) isomorphism, or the analogy of crystalline forms; and, connected with it, the power to form crystalline mixtures which are isomorphous; (_b_) the relation of the volumes of analogous compounds of the elements; (_c_) the composition of their saline compounds; and (_d_) the relation of the atomic weights of the elements. In this chapter we shall briefly consider these four aspects of the matter, which are exceedingly important for a natural and fruitful grouping of the elements, facilitating, not only a general acquaintance with them, but also their detailed study. Historically the first, and an important and convincing, method for finding a relationship between the compounds of two different elements is by _isomorphism_. This conception was introduced into chemistry by Mitscherlich (in 1820), who demonstrated that the corresponding salts of arsenic acid, H_{3}AsO_{4}, and phosphoric acid, H_{3}PO_{4}, crystallise with an equal quantity of water, show an exceedingly close resemblance in crystalline form (as regards the angles of their faces and axes), and are able to crystallise together from solutions, forming crystals containing a mixture of the isomorphous compounds. Isomorphous substances are those which, with an equal number of atoms in their molecules, present an analogy in their chemical reactions, a close resemblance in their properties, and a similar or very nearly similar crystalline form: they often contain certain elements in common, from which it is to be concluded that the remaining elements (as in the preceding example of As and P) are analogous to each other. And inasmuch as crystalline forms are capable of exact measurement, the external form, or the relation of the molecules which causes their grouping into a crystalline form, is evidently as great a help in judging of the internal forces acting between the atoms as a comparison of reactions, vapour densities, and other like relations. We have already seen examples of this in the preceding pages.[1] It will be sufficient to call to mind that the compounds of the alkali metals with the halogens RX, in a crystalline form, all belong to the cubic system and crystallise in octahedra or cubes--for example, sodium chloride, potassium chloride, potassium iodide, rubidium chloride, &c. The nitrates of rubidium and cæsium appear in anhydrous crystals of the same form as potassium nitrate. The carbonates of the metals of the alkaline earths are isomorphous with calcium carbonate--that is, they either appear in forms like calc spar or in the rhombic system in crystals analogous to aragonite.[1 bis] Furthermore, sodium nitrate crystallises in rhombohedra, closely resembling the rhombohedra of calc spar (calcium carbonate), CaCO_{3}, whilst potassium nitrate appears in the same form as aragonite, CaCO_{3}, and the number of atoms in both kinds of salts is the same: they all contain one atom of a metal (K, Na, Ca), one atom of a non-metal (C, N), and three atoms of oxygen. The analogy of form evidently coincides with an analogy of atomic composition. But, as we have learnt from the previous description of these salts, there is not any close resemblance in their properties. It is evident that calcium carbonate approaches more nearly to magnesium carbonate than to sodium nitrate, although their crystalline forms are all equally alike. Isomorphous substances which are perfectly analogous to each other are not only characterised by a close resemblance of form (homeomorphism), but also by the faculty of entering into analogous reactions, which is not the case with RNO_{3} and RCO_{3}. The most important and direct method of recognising perfect isomorphism--that is, the absolute analogy of two compounds--is given by that property of analogous compounds of separating from solutions _in homogeneous crystals, containing the most varied proportions_ of the analogous substances which enter into their composition. These quantities do not seem to be in dependence on the molecular or atomic weights, and if they are governed by any laws they must be analogous to those which apply to indefinite chemical compounds.[2] This will be clear from the following examples. Potassium chloride and potassium nitrate are not isomorphous with each other, and are in an atomic sense composed in a different manner. If these salts be mixed in a solution and the solution be evaporated, independent crystals of the two salts will separate, each in that crystalline form which is proper to it. The crystals will not contain a mixture of the two salts. But if we mix the solutions of two isomorphous salts together, then, under certain circumstances, crystals will be obtained which contain both these substances. However, this cannot be taken as an absolute rule, for if we take a solution saturated at a high temperature with a mixture of potassium and sodium chlorides, then on evaporation sodium chloride only will separate, and on cooling only potassium chloride. The first will contain very little potassium chloride, and the latter very little sodium chloride.[3] But if we take, for example, a mixture of solutions of magnesium sulphate and zinc sulphate, they cannot be separated from each other by evaporating the mixture, notwithstanding the rather considerable difference in the solubility of these salts. Again, the isomorphous salts, magnesium carbonate, and calcium carbonate are found together--that is, in one crystal--in nature. The angle of the rhombohedron of these magnesia-lime spars is intermediate between the angles proper to the two spars individually (for calcium carbonate, the angle of the rhombohedron is 105° 8´; magnesium carbonate, 107° 30´; CaMg(CO_{3})_{2}, 106° 10´). Certain of these _isomorphous mixtures_ of calc and magnesia spars appear in well-formed crystals, and in this case there not unfrequently exists a simple molecular proportion of strictly definite chemical combination between the component salts--for instance, CaCO_{3},MgCO_{3}--whilst in other cases, especially in the absence of distinct crystallisation (in dolomites), no such simple molecular proportion is observable: this is also the case in many artificially prepared isomorphous mixtures. The microscopical and crystallo-optical researches of Professor Inostrantzoff and others show that in many cases there is really a mechanical, although microscopically minute, juxtaposition in one whole of the heterogeneous crystals of calcium carbonate (double refracting) and of the compound CaMgC_{2}O_{6}. If we suppose the adjacent parts to be microscopically small (on the basis of the researches of Mallard, Weruboff, and others), we obtain an idea of isomorphous mixtures. A formula of the following kind is given to isomorphous mixtures: for instance, for spars, RCO_{3}, where R = Mg, Ca, and where it may be Fe,Mn ..., &c. This means that the Ca is partially replaced by Mg or another metal. Alums form a common example of the separation of isomorphous mixtures from solutions. They are double sulphates (or seleniates) of alumina (or oxides isomorphous with it) and the alkalis, which crystallise in well-formed crystals. If aluminium sulphate be mixed with potassium sulphate, an alum separates, having the composition KAlS_{2}O_{8},12H_{2}O. If sodium sulphate or ammonium sulphate, or rubidium (or thallium) sulphate be used, we obtain alums having the composition RAlS_{2}O_{8},12H_{2}O. Not only do they all crystallise in the cubic system, but they also contain an equal atomic quantity of water of crystallisation (12H_{2}O). Besides which, if we mix solutions of the potassium and ammonium (NH_{4}AlS_{2}O_{8},12H_{2}O) alums together, then the crystals which separate will contain various proportions of the alkalis taken, and separate crystals of the alums of one or the other kind will not be obtained, but each separate crystal will contain both potassium and ammonium. Nor is this all; if we take a crystal of a potassium alum and immerse it in a solution capable of yielding ammonia alum, the crystal of the potash alum will continue to grow and increase in size in this solution--that is, a layer of the ammonia or other alum will deposit itself upon the planes bounding the crystal of the potash alum. This is very distinctly seen if a colourless crystal of a common alum be immersed in a saturated violet solution of chrome alum, KCrS_{2}O_{8},12H_{2}O, which then deposits itself in a violet layer over the colourless crystal of the alumina alum, as was observed even before Mitscherlich noticed it. If this crystal be then immersed in a solution of an alumina alum, a layer of this salt will form over the layer of chrome alum, so that one alum is able to incite the growth of the other. If the deposition proceed simultaneously, the resultant intermixture may be minute and inseparable, but its nature is understood from the preceding experiments; the attractive force of crystallisation of isomorphous substances is so nearly equal that the attractive power of an isomorphous substance induces a crystalline superstructure exactly the same as would be produced by the attractive force of like crystalline particles. From this it is evident that one isomorphous substance may _induce the crystallisation_[4] of another. Such a phenomenon explains, on the one hand, the aggregation of different isomorphous substances in one crystal, whilst, on the other hand, it serves as a most exact indication of the nearness both of the molecular composition of isomorphous substances and of those forces which are proper to the elements which distinguish the isomorphous substances. Thus, for example, ferrous sulphate or green vitriol crystallises in the monoclinic system and contains seven molecules of water, FeSO_{4},7H_{2}O, whilst copper vitriol crystallises with five molecules of water in the triclinic system, CuSO_{4},5H_{2}O; nevertheless, it may be easily proved that both salts are perfectly isomorphous; that they are able to appear in identically the same forms and with an equal molecular amount of water. For instance, Marignac, by evaporating a mixture of sulphuric acid and ferrous sulphate under the receiver of an air-pump, first obtained crystals of the hepta-hydrated salt, and then of the penta-hydrated salt FeSO_{4},5H_{2}O, which were perfectly similar to the crystals of copper sulphate. Furthermore, Lecoq de Boisbaudran, by immersing crystals of FeSO_{4},7H_{2}O in a supersaturated solution of copper sulphate, caused the latter to deposit in the same form as ferrous sulphate, in crystals of the monoclinic system, CuSO_{4},7H_{2}O. [1] For instance the analogy of the sulphates of K, Rb, and Cs (Chapter XIII., Note 1). [1 bis] The crystalline forms of aragonite, strontianite, and witherite belong to the rhombic system; the angle of the prism of CaCO_{3} is 116° 10´, of SrCO_{3} 117° 19´, and of BaCO_{3} 118° 30´. On the other hand the crystalline forms of calc spar, magnesite, and calamine, which resemble each other quite as closely, belong to the rhombohedral system, with the angle of the rhombohedra for CaCO_{3} 105° 8´, MgCO_{3} 107° 10´, and ZnCO_{3} 107° 40´. From this comparison it is at once evident that zinc is more closely allied to magnesium than magnesium to calcium. [2] Solutions furnish the commonest examples of indefinite chemical compounds. But the isomorphous mixtures which are so common among the crystalline compounds of silica forming the crust of the earth, as well as alloys, which are so important in the application of metals to the arts, are also instances of indefinite compounds. And if in Chapter I., and in many other portions of this work, it has been necessary to admit the presence of definite compounds (in a state of dissociation) in solutions, the same applies with even greater force to isomorphous mixtures and alloys. For this reason in many places in this work I refer to facts which compel us to recognise the existence of definite chemical compounds in all isomorphous mixtures and alloys. This view of mine (which dates from the sixties) upon isomorphous mixtures finds a particularly clear confirmation in B. Roozeboom's researches (1892) upon the solubility and crystallising capacity of mixtures of the chlorates of potassium and thallium, KClO_{3} and TlClO_{3}. He showed that when a solution contains different amounts of these salts, it deposits crystals containing either an excess of the first salt, from 98 p.c. to 100 p.c., or an excess of the second salt, from 63·7 to 100 p.c.; that is, in the crystalline form, either the first salt saturates the second or the second the first, just as in the solution of ether in water (Chapter I.); moreover, the solubility of the mixtures containing 36·3 and 98 p.c. KClO_{3} is similar, just as the vapour tension of a saturated solution of water in ether is equal to that of a saturated solution of ether in water (Chapter I., Note 47). But just as there are solutions miscible in all proportions, so also certain isomorphous bodies can be present in crystals in all possible proportions of their component parts. Van 't Hoff calls such systems 'solid solutions.' These views were subsequently elaborated by Nernst (1892), and Witt (1891) applied them in explaining the phenomena observed in the coloration of tissues. [3] The cause of the difference which is observed in different compounds of the same type, with respect to their property of forming isomorphous mixtures, must not be looked for in the difference of their volumetric composition, as many investigators, including Kopp, affirm. The molecular volumes (found by dividing the molecular weight by the density) of those isomorphous substances which do give intermixtures are not nearer to each other than the volumes of those which do not give mixtures; for example, for magnesium carbonate the combining weight is 84, density 3·06, and volume therefore 27; for calcium carbonate in the form of calc spar the volume is 37, and in the form of aragonite 33; for strontium carbonate 41, for barium carbonate 46; that is, the volume of these closely allied isomorphous substances increases with the combining weight. The same is observed if we compare sodium chloride (molecular volume = 27) with potassium chloride (volume = 37), or sodium sulphate (volume = 55) with potassium sulphate (volume = 66), or sodium nitrate 39 with potassium nitrate 48, although the latter are less capable of giving isomorphous mixtures than the former. It is evident that the cause of isomorphism cannot be explained by an approximation in molecular volumes. It is more likely that, given a similarity in form and composition, the faculty to give isomorphous mixtures is connected with the laws and degree of solubility. [4] A phenomenon of a similar kind is shown for magnesium sulphate in Note 27 of the last chapter. In the same example we see what a complication the phenomena of dimorphism may introduce when the forms of analogous compounds are compared. Hence it is evident that isomorphism--that is, the analogy of forms and the property of inducing crystallisation--may serve as a means for the discovery of analogies in molecular composition. We will take an example in order to render this clear. If, instead of aluminium sulphate, we add magnesium sulphate to potassium sulphate, then, on evaporating the solution, the double salt K_{2}MgS_{2}O_{8},6H_{2}O (Chapter XIV., Note 28) separates instead of an alum, and the ratio of the component parts (in alums one atom of potassium per 2SO_{4}, and here two atoms) and the amount of water of crystallisation (in alums 12, and here 6 equivalents per 2SO_{4}) are quite different; nor is this double salt in any way isomorphous with the alums, nor capable of forming an isomorphous crystalline mixture with them, nor does the one salt provoke the crystallisation of the other. From this we must conclude that although alumina and magnesia, or aluminium and magnesium, resemble each other, they are not isomorphous, and that although they give partially similar double salts, these salts are not analogous to each other. And this is expressed in their chemical formulæ by the fact that the number of atoms in alumina or aluminium oxide, Al_{2}O_{3}, is different from the number in magnesia, MgO. Aluminium is trivalent and magnesium bivalent. Thus, having obtained a double salt from a given metal, it is possible to judge of the analogy of the given metal with aluminium or with magnesium, or of the absence of such an analogy, from the composition and form of this salt. Thus zinc, for example, does not form alums, but forms a double salt with potassium sulphate, which has a composition exactly like that of the corresponding salt of magnesium. It is often possible to distinguish the bivalent metals analogous to magnesium or calcium from the trivalent metals, like aluminium, by such a method. Furthermore, the specific heat and vapour density serve as guides. There are also indirect proofs. Thus iron gives ferrous compounds, FeX_{2}, which are isomorphous with the compounds of magnesium, and ferric compounds, FeX_{3}, which are isomorphous with the compounds of aluminium; in this instance the relative composition is directly determined by analysis, because, for a given amount of iron, FeCl_{2} only contains two-thirds of the amount of chlorine which occurs in FeCl_{3}, and the composition of the corresponding oxygen compounds, _i.e._ of ferrous oxide, FeO, and ferric oxide, Fe_{2}O_{3}, clearly indicates the analogy of the ferrous oxide with MgO and of the ferric oxide with Al_{2}O_{3}. Thus in the building up of similar molecules in crystalline forms we see one of the numerous means for judging of the internal world of molecules and atoms, and one of the weapons for conquests in the invisible world of molecular mechanics which forms the main object of physico-chemical knowledge. This method[5] has more than once been employed for discovering the analogy of elements and of their compounds; and as crystals are measurable, and the capacity to form crystalline mixtures can be experimentally verified, this method is a numerical and measurable one, and in no sense arbitrary. [5] The property of solids of occurring in regular crystalline forms--the occurrence of many substances in the earth's crust in these forms--and those geometrical and simple laws which govern the formation of crystals long ago attracted the attention of the naturalist to crystals. The crystalline form is, without doubt, the expression of the relation in which the atoms occur in the molecules, and in which the molecules occur in the mass, of a substance. Crystallisation is determined by the distribution of the molecules along the direction of greatest cohesion, and therefore those forces must take part in the crystalline distribution of matter which act between the molecules; and, as they depend on the forces binding the atoms together in the molecules, a very close connection must exist between the atomic composition and the distribution of the atoms in the molecule on the one hand, and the crystalline form of a substance on the other hand; and hence an insight into the composition may be arrived at from the crystalline form. Such is the elementary and _a priori_ idea which lies at the base of all researches into _the connection between composition and crystalline form_. Haüy in 1811 established the following fundamental law, which has been worked out by later investigators: That the fundamental crystalline form for a given chemical compound is constant (only the combinations vary), and that with a change of composition the crystalline form also changes, naturally with the exception of such limiting forms as the cube, regular octahedron, &c., which may belong to various substances of the regular system. The fundamental form is determined by the angles of certain fundamental geometric forms (prisms, pyramids, rhombohedra), or the ratio of the crystalline axes, and is connected with the optical and many other properties of crystals. Since the establishment of this law the description of definite compounds in a solid state is accompanied by a description (measurement) of its crystals, which forms an invariable, definite, and measurable character. The most important epochs in the further history of this question were made by the following discoveries:--Klaproth, Vauquelin, and others showed that aragonite has the same composition as calc spar, whilst the former belongs to the rhombic and the latter to the hexagonal system. Haüy at first considered that the composition, and after that the arrangement, of the atoms in the molecules was different. This is dimorphism (_see_ Chapter XIV., Note 46). Beudant, Frankenheim, Laurent, and others found that the forms of the two nitres, KNO_{3} and NaNO_{3}, exactly correspond with the forms of aragonite and calc spar; that they are able, moreover, to pass from one form into another; and that the difference of the forms is accompanied by a small alteration of the angles, for the angle of the prisms of potassium nitrate and aragonite is 119°, and of sodium nitrate and calc spar, 120°; and therefore dimorphism, or the crystallisation of one substance in different forms, does not necessarily imply a great difference in the distribution of the molecules, although some difference clearly exists. The researches of Mitscherlich (1822) on the dimorphism of sulphur confirmed this conclusion, although it cannot yet be affirmed that in dimorphism the arrangement of the atoms remains unaltered, and that only the molecules are distributed differently. Leblanc, Berthier, Wollaston, and others already knew that many substances of different composition appear in the same forms, and crystallise together in one crystal. Gay-Lussac (1816) showed that crystals of potash alum continue to grow in a solution of ammonia alum. Beudant (1817) explained this phenomenon as the _assimilation_ of a foreign substance by a substance having a great force of crystallisation, which he illustrated by many natural and artificial examples. But Mitscherlich, and afterwards Berzelius and Henry Rose and others, showed that such an assimilation only exists with a similarity or approximate similarity of the forms of the individual substances and with a certain degree of chemical analogy. Thus was established the idea of _isomorphism_ as an analogy of forms by reason of a resemblance of atomic composition, and by it was explained the variability of the composition of a number of minerals as isomorphous mixtures. Thus all the garnets are expressed by the general formula: (RO)_{3}M_{2}O_{3}(SiO_{2})_{3}, where R = Ca, Mg, Fe, Mn, and M = Fe, Al, and where we may have either R and M separately, or their equivalent compounds, or their mixtures in all possible proportions. But other facts, which render the correlation of form and composition still more complex, have accumulated side by side with a mass of data which may be accounted for by admitting the conceptions of isomorphism and dimorphism. Foremost among the former stand the phenomena of _homeomorphism_--that is, a nearness of forms with a difference of composition--and then the cases of polymorphism and hemimorphism--that is, a nearness of the fundamental forms or only of certain angles for substances which are near or analogous in their composition. Instances of homeomorphism are very numerous. Many of these, however, may be reduced to a resemblance of atomic composition, although they do not correspond to an isomorphism of the component elements; for example, CdS (greenockite) and AgI, CaCO_{3} (aragonite) and KNO_{3}, CaCO_{3} (calc spar) and NaNO_{3}, BaSO_{4} (heavy spar), KMnO_{4} (potassium permanganate), and KClO_{4} (potassium perchlorate), Al_{2}O_{3} (corundum) and FeTiO_{3} (titanic iron ore), FeS_{2} (marcasite, rhombic system) and FeSAs (arsenical pyrites), NiS and NiAs, &c. But besides these instances there are homeomorphous substances with an absolute dissimilarity of composition. Many such instances were pointed out by Dana. Cinnabar, HgS, and susannite, PbSO_{4}3PbCO_{3} appear in very analogous crystalline forms; the acid potassium sulphate crystallises in the monoclinic system in crystals analogous to felspar, KAlSi_{3}O_{8}; glauberite, Na_{2}Ca(SO_{4})_{2}, augite, RSiO_{3} (R = Ca, Mg), sodium carbonate, Na_{2}CO_{3},10H_{2}O, Glauber's salt, Na_{2}SO_{4},10H_{2}O, and borax, Na_{2}BrO_{7},10H_{2}O, not only belong to the same system (monoclinic), but exhibit an analogy of combinations and a nearness of corresponding angles. These and many other similar cases might appear to be perfectly arbitrary (especially as a _nearness_ of angles and fundamental forms is a relative idea) were there not other cases where a resemblance of properties and a distinct relation in the variation of composition is connected with a resemblance of form. Thus, for example, alumina, Al_{2}O_{3}, and water, H_{2}O, are frequently found in many pyroxenes and amphiboles which only contain silica and magnesia (MgO, CaO, FeO, MnO). Scheerer and Hermann, and many others, endeavoured to explain such instances by _polymetric isomorphism_, stating that MgO may be replaced by 3H_{2}O (for example, olivine and serpentine), SiO_{2} by Al_{2}O_{3} (in the amphiboles, talcs), and so on. A certain number of the instances of this order are subject to doubt, because many of the natural minerals which served as the basis for the establishment of polymeric isomorphism in all probability no longer present their original composition, but one which has been altered under the influence of solutions which have come into contact with them; they therefore belong to the class of _pseudomorphs_, or false crystals. There is, however, no doubt of the existence of a whole series of natural and artificial homeomorphs, which differ from each other by atomic amounts of water, silica, and some other component parts. Thus, Thomsen (1874) showed a very striking instance. The metallic chlorides, RCl_{2}, often crystallise with water, and they do not then contain less than one molecule of water per atom of chlorine. The most familiar representative of the order RCl_{2},2H_{2}O is BaCl_{2},2H_{2}O, which crystallises in the rhombic system. Barium bromide, BaBr_{2},2H_{2}O, and copper chloride, CuCl_{2},2H_{2}O, have nearly the same forms: potassium iodate, KIO_{4}; potassium chlorate, KClO_{4}; potassium permanganate, KMnO_{4}; barium sulphate, BaSO_{4}; calcium sulphate, CaSO_{4}; sodium sulphate, Na_{2}SO_{4}; barium formate, BaC_{2}H_{2}O_{4}, and others have almost the same crystalline form (of the rhombic system). Parallel with this series is that of the metallic chlorides containing RCl_{2},4H_{2}O, of the sulphates of the composition RSO_{4},2H_{2}O, and the formates RC_{2}H_{2}O_{4},2H_{2}O. These compounds belong to the monoclinic system, have a close resemblance of form, and differ from the first series by containing two more molecules of water. The addition of two more molecules of water in all the above series also gives forms of the monoclinic system closely resembling each other; for example, NiCl_{2},6H_{2}O and MnSO_{4},4H_{2}O. Hence we see that not only is RCl_{2},2H_{2}O analogous in form to RSO_{4} and RC_{2}H_{2}O_{4}, but that their compounds with 2H_{2}O and with 4H_{2}O also exhibit closely analogous forms. From these examples it is evident that the conditions which determine a given form may be repeated not only in the presence of an isomorphous exchange--that is, with an equal number of atoms in the molecule--but also in the presence of an unequal number when there are peculiar and as yet ungeneralised relations in composition. Thus ZnO and Al_{2}O_{3} exhibit a close analogy of form. Both oxides belong to the rhombohedral system, and the angle between the pyramid and the terminal plane of the first is 118° 7´, and of the second 118° 49´. Alumina, Al_{2}O_{3}, is also analogous in form to SiO_{2}, and we shall see that these analogies of form are conjoined with a certain analogy in properties. It is not surprising, therefore, that in the complex molecule of a siliceous compound it is sometimes possible to replace SiO_{2} by means of Al_{2}O_{3}, as Scheerer admits. The oxides Cu_{2}O, MgO, NiO, Fe_{3}O_{4}, CeO_{2}, crystallise in the regular system, although they are of very different atomic structure. Marignac demonstrated the perfect analogy of the forms of K_{2}ZrF_{6} and CaCO_{3}, and the former is even dimorphous, like the calcium carbonate. The same salt is isomorphous with R_{2}NbOF_{5} and R_{2}WO_{2}F_{4}, where R is an alkali metal. There is an equivalency between CaCO_{3} and K_{2}ZrF_{6}, because K_{2} is equivalent to Ca, C to Zr, and F_{6} to O_{3}, and with the isomorphism of the other two salts we find besides an equal contents of the alkali metal--an equal number of atoms on the one hand and an analogy to the properties of K_{2}ZrF_{6} on the other. The long-known isomorphism of the corresponding compounds of potassium and ammonium, KX and NH_{4}X, may be taken as the simplest example of the fact that an analogy of form shows itself with an analogy of chemical reaction even without an equality in atomic composition. Therefore the ultimate progress of the entire doctrine of the correlation of composition and crystalline forms will only be arrived at with the accumulation of a sufficient number of facts collected on a plan corresponding with the problems which here present themselves. The first steps have already been made. The researches of the Geneva _savant_, Marignac, on the crystalline form and composition of many of the double fluorides, and the work of Wyruboff on the ferricyanides and other compounds, are particularly important in this respect. It is already evident that, with a definite change of composition, certain angles remain constant, notwithstanding that others are subject to alteration. Such an instance of the relation of forms was observed by Laurent, and named by him _hemimorphism_ (an anomalous term) when the analogy is limited to certain angles, and _paramorphism_ when the forms in general approach each other, but belong to different systems. So, for example, the angle of the planes of a rhombohedron may be greater or less than 90°, and therefore such acute and obtuse rhombohedra may closely approximate to the cube. Hausmannite, Mn_{3}O_{4}, belongs to the tetragonal system, and the planes of its pyramid are inclined at an angle of about 118°, whilst magnetic iron ore, Fe_{3}O_{4}, which resembles hausmannite in many respects, appears in regular octahedra--that is, the pyramidal planes are inclined at an angle of 109° 28´. This is an example of paramorphism; the systems are different, the compositions are analogous, and there is a certain resemblance in form. Hemimorphism has been found in many instances of saline and other substitutions. Thus, Laurent demonstrated, and Hintze confirmed (1873), that naphthalene derivatives of analogous composition are hemimorphous. Nicklès (1849) showed that in ethylene sulphate the angle of the prism is 125° 26´, and in the nitrate of the same radicle 126° 95´. The angle of the prism of methylamine oxalate is 131° 20´, and of fluoride, which is very different in composition from the former, the angle is 132°. Groth (1870) endeavoured to indicate in general what kinds of change of form proceed with the substitution of hydrogen by various other elements and groups, and he observed a regularity which he termed _morphotropy_. The following examples show that morphotropy recalls the hemimorphism of Laurent. Benzene, C_{6}H_{6}, rhombic system, ratio of the axes 0·891 : 1 : 0·799. Phenol, C_{6}H_{5}(OH), and resorcinol, C_{6}H_{4}(OH)_{2}, also rhombic system, but the ratio of one axis is changed--thus, in resorcinol, 0·910 : 1 : 0·540; that is, a portion of the crystalline structure in one direction is the same, but in the other direction it is changed, whilst in the rhombic system dinitrophenol, C_{6}H_{3}(NO_{2})_{2}(OH) = O·833 : 1 : 0·753; trinitrophenol (picric acid), C_{6}H_{2}(NO)_{3}(OH) = 0·937 : 1 : 0·974; and the potassium salt = 0·942 : 1 : 1·354. Here the ratio of the first axis is preserved--that is, certain angles remain constant, and the chemical proximity of the composition of these bodies is undoubted. Laurent compares hemimorphism with architectural style. Thus, Gothic cathedrals differ in many respects, but there is an analogy expressed both in the sum total of their common relations and in certain details--for example, in the windows. It is evident that we may expect many fruitful results for molecular mechanics (which forms a problem common to many provinces of natural science) from the further elaboration of the data concerning those variations which take place in crystalline form when the composition of a substance is subjected to a known change, and therefore I consider it useful to point out to the student of science seeking for matter for independent scientific research this vast field for work which is presented by the correlation of form and composition. The geometrical regularity and varied beauty of crystalline forms offer no small attraction to research of this kind. The regularity and simplicity expressed by the exact laws of crystalline form repeat themselves in the aggregation of the atoms to form molecules. Here, as there, there are but few forms which are essentially different, and their apparent diversity reduces itself to a few fundamental differences of type. There the molecules aggregate themselves into crystalline forms; here, the atoms aggregate themselves into molecular forms or into _the types of compounds_. In both cases the fundamental crystalline or molecular forms are liable to variations, conjunctions, and combinations. If we know that potassium gives compounds of the fundamental type KX, where X is a univalent element (which combines with one atom of hydrogen, and is, according to the law of substitution, able to replace it), then we know the composition of its compounds: K_{2}O, KHO, KCl, NH_{2}K, KNO_{3}, K_{2}SO_{4}, KHSO_{4}, K_{2}Mg(SO_{4})_{2},6H_{2}O, &c. All the possible derivative crystalline forms are not known. So also all the atomic combinations are not known for every element. Thus in the case of potassium, KCH_{3}, K_{3}P, K_{2}Pt, and other like compounds which exist for hydrogen or chlorine, are unknown. Only a few fundamental types exist for the building up of atoms into molecules, and the majority of them are already known to us. If X stand for a univalent element, and R for an element combined with it, then eight atomic types may be observed:-- RX, RX_{2}, RX_{3}, RX_{4}, RX_{5}, RX_{6}, RX_{7}, RX_{8}. Let X be chlorine or hydrogen. Then as examples of the first type we have: H_{2}, Cl_{2}, HCl, KCl, NaCl, &c. The compounds of oxygen or calcium may serve as examples of the type RX_{2}: OH_{2}, OCl_{2}, OHCl, CaO, Ca(OH)_{2}, CaCl_{2}, &c. For the third type RX_{3} we know the representative NH_{3} and the corresponding compounds N_{2}O_{3}, NO(OH), NO(OK), PCl_{3}, P_{2}O_{3}, PH_{3}, SbH_{3}, Sb_{2}O_{3}, B_{2}O_{3}, BCl_{3}, Al_{2}O_{3}, &c. The type RX_{4} is known among the hydrogen compounds. Marsh gas, CH_{4}, and its corresponding saturated hydrocarbons, C_{_n_}H_{2_n_ + 2}, are the best representatives. Also CH_{3}Cl, CCl_{4}, SiCl_{4}, SnCl_{4}, SnO_{2}, CO_{2}, SiO_{2}, and a whole series of other compounds come under this class. The type RX_{5} is also already familiar to us, but there are no purely hydrogen compounds among its representatives. Sal-ammoniac, NH_{4}Cl, and the corresponding NH_{4}(OH), NO_{2}(OH), ClO_{2}(OK), as well as PCl_{5}, POCl_{3}, &c., are representatives of this type. In the higher types also there are no hydrogen compounds, but in the type RX_{6} there is the chlorine compound WCl_{6}. However, there are many oxygen compounds, and among them SO_{3} is the best known representative. To this class also belong SO_{2}(OH)_{2}, SO_{2}Cl_{2}, SO_{2}(OH)Cl, CrO_{3}, &c., all of an acid character. Of the higher types there are in general only oxygen and acid representatives. The type RX_{7} we know in perchloric acid, ClO_{3}(OH), and potassium permanganate, MnO_{3}(OK), is also a member. The type RX_{8} in a free state is very rare; osmic anhydride, OsO_{4}, is the best known representative of it.[6] [6] The still more complex combinations--which are so clearly expressed in the crystallo-hydrates, double salts, and similar compounds--although they may be regarded as independent, are, however, most easily understood with our present knowledge as aggregations of whole molecules to which there are no corresponding double compounds, containing one atom of an element R and many atoms of other elements RX_{_n_}. The above types embrace all cases of direct combinations of atoms, and the formula MgSO_{4},7H_{2}O cannot, without violating known facts, be directly deduced from the types MgX_{_n_} or SX_{_n_}, whilst the formula MgSO_{4} corresponds both with the type of the magnesium compounds MgX_{2} and with the type of the sulphur compounds SO_{2}X_{2}, or in general SX_{6}, where X_{2} is replaced by (OH)_{2}, with the substitution in this case of H_{2} by the atom Mg, which always replaces H_{2}. However, it must be remarked that the sodium crystallo-hydrates often contain 10H_{2}O, the magnesium crystallo-hydrates 6 and 7H_{2}O, and that the type PtM_{2}X_{6} is proper to the double salts of platinum, &c. With the further development of our knowledge concerning crystallo-hydrates, double salts, alloys, solutions, &c., in the _chemical sense_ of feeble compounds (that is, such as are easily destroyed by feeble chemical influences) it will probably be possible to arrive at a perfect generalisation for them. For a long time these subjects were only studied by the way or by chance; our knowledge of them is accidental and destitute of system, and therefore it is impossible to expect as yet any generalisation as to their nature. The days of Gerhardt are not long past when only three types were recognised: RX, RX_{2}, and RX_{3}; the type RX_{4} was afterwards added (by Cooper, Kekulé, Butleroff, and others), mainly for the purpose of generalising the data respecting the carbon compounds. And indeed many are still satisfied with these types, and derive the higher types from them; for instance, RX_{5} from RX_{3}--as, for example, POCl_{3} from PCl_{3}, considering the oxygen to be bound both to the chlorine (as in HClO) and to the phosphorus. But the time has now arrived when it is clearly seen that the forms RX, RX_{2}, RX_{3}, and RX_{4} do not exhaust the whole variety of phenomena. The revolution became evident when Würtz showed that PCl_{5} is not a compound of PCl_{3} + Cl_{2} (although it may decompose into them), but a whole molecule capable of passing into vapour, PCl_{5} like PF_{5} and SiF_{4}. The time for the recognition of types even higher than RX_{8} is in my opinion in the future; that it will come, we can already see in the fact that oxalic acid, C_{2}H_{2}O_{4}, gives a crystallo-hydrate with 2H_{2}O; but it may be referred to the type CH_{4}, or rather to the type of ethane, C_{2}H_{6}, in which all the atoms of hydrogen are replaced by hydroxyl, C_{2}H_{2}O_{4}2H_{2}O = C_{2}(OH)_{6} (_see_ Chapter XXII., Note 35). The four lower types RX, RX_{2}, RX_{3}, and RX_{4} are met with in compounds of the elements R with chlorine and oxygen, and also in their compounds with hydrogen, whilst the four higher types only appear for such acid compounds as are formed by chlorine, oxygen, and similar elements. Among the oxygen compounds the _saline oxides_ which are capable of forming salts either through the function of a base or through the function of an acid anhydride attract the greatest interest in every respect. Certain elements, like calcium and magnesium, only give one saline oxide--for example, MgO, corresponding with the type MgX_{2}. But the majority of the elements appear in several such forms. Thus copper gives CuX and CuX_{2}, or Cu_{2}O and CuO. If an element R gives a higher type RX_{_n_}, then there often also exist, as if by symmetry, lower types, RX_{_n_-2}, RX_{_n_-4}, and in general such types as differ from RX_{_n_} by an even number of X. Thus in the case of sulphur the types SX_{2}, SX_{4}, and SX_{6} are known--for example SH_{2}, SO_{2}, and SO_{3}. The last type is the highest, SX_{6}. The types SX_{5} and SX_{3} do not exist. But even and uneven types sometimes appear for one and the same element. Thus the types RX and RX_{2} are known for copper and mercury. Among the _saline_ oxides only the _eight types_ enumerated below are known to exist. They determine the possible formulæ of the compounds of the elements, if it be taken into consideration that an element which gives a certain type of combination may also give lower types. For this reason the rare type of the _suboxides_ or quaternary oxides R_{4}O (for instance, Ag_{4}O, Ag_{2}Cl) is not characteristic; it is always accompanied by one of the higher grades of oxidation, and the compounds of this type are distinguished by their great chemical instability, and split up into an element and the higher compound (for instance, Ag_{4}O = 2Ag + Ag_{2}O). Many elements, moreover, form transition oxides whose composition is intermediate, which are able, like N_{2}O_{4}, to split up into the lower and higher oxides. Thus iron gives magnetic oxide, Fe_{3}O_{4}, which is in all respects (by its reactions) a compound of the suboxide FeO with the oxide Fe_{2}O_{3}. The independent and more or less stable saline compounds correspond with the following eight types:-- R_{2}O; salts RX, hydroxides ROH. Generally basic like K_{2}O, Na_{2}O, Hg_{2}O, Ag_{2}O, Cu_{2}O; if there are acid oxides of this composition they are very rare, are only formed by distinctly acid elements, and even then have only feeble acid properties; for example, Cl_{2}O and N_{2}O. R_{2}O_{2} or RO; salts RX_{2}, hydroxides R(OH)_{2}. The most simple basic salts R_{2}OX_{2} or R(OH)X; for instance, the chloride Zn_{2}OCl_{2}; also an almost exclusively basic type; but the basic properties are more feebly developed than in the preceding type. For example, CaO, MgO, BaO, PbO, FeO, MnO, &c. R_{2}O_{3}; salts RX_{3}, hydroxides R(OH)_{3}, RO(OH), the most simple basic salts ROX, R(OH)X_{3}. The bases are feeble, like Al_{2}O_{3}, Fe_{2}O_{3}, Tl_{2}O_{3}, Sb_{2}O_{3}. The acid properties are also feebly developed; for instance, in B_{2}O_{3}; but with the non-metals the properties of acids are already clear; for instance, P_{2}O_{3}, P(OH)_{3}. R_{2}O_{4} or RO_{2}; salts RX_{4} or ROX_{2}, hydroxides R(OH)_{4}, RO(OH)_{2}. Rarely bases (feeble), like ZrO_{2}, PtO_{2}; more often acid oxides; but the acid properties are in general feeble, as in CO_{2}, SO_{2}, SnO_{2}. Many intermediate oxides appear in this and the preceding and following types. R_{2}O_{5}; salts principally of the types ROX_{3}, RO_{2}X, RO(OH)_{3}, RO_{2}(OH), rarely RX_{5}. The basic character (X, a halogen, simple or complex; for instance, NO_{3}, Cl, &c.) is feeble; the acid character predominates, as is seen in N_{2}O_{5}, P_{2}O_{5}, Cl_{2}O_{5}; then X = OH, OK, &c., for example NO_{2}(OK). R_{2}O_{6} or RO_{3}; salts and hydroxides generally of the type RO_{2}X_{2}, RO_{2}(OH)_{2}. Oxides of an acid character, as SO_{3}, CrO_{3}, MnO_{3}. Basic properties rare and feebly developed as in UO_{3}. R_{2}O_{7}; salts of the form RO_{3}X, RO_{3}(OH), acid oxides; for instance, Cl_{2}O_{7}, Mn_{2}O_{7}. Basic properties as feebly developed as the acid properties in the oxides R_{2}O. R_{2}O_{8} or RO_{4}. A very rare type, and only known in OsO_{4} and RuO_{4}. It is evident from the circumstance that in all the higher types the _acid hydroxides_ (for example, HClO_{4}, H_{2}SO_{4}, H_{3}PO_{4}) and salts with a single atom of one element contain, like the higher saline type RO_{4}, _not more than four atoms of oxygen_; that the formation of the saline oxides is governed by a certain common principle which is best looked for in the fundamental properties of oxygen, and in general of the most simple compounds. The hydrate of the oxide RO_{2} is of the higher type RO_{2}2H_{2}O = RH_{4}O_{4} = R(HO)_{4}. Such, for example, is the hydrate of silica and the salts (orthosilicates) corresponding with it, Si(MO)_{4}. The oxide R_{2}O_{5}, corresponds with the hydrate R_{2}O_{5}3H_{2}O = 2RH_{3}O_{4} = 2RO(OH)_{3}. Such is orthophosphoric acid, PH_{3}O_{3}. The hydrate of the oxide RO_{3} is RO_{3}H_{2}O = RH_{2}O_{4} = RO_{2}(OH)_{2}--for instance, sulphuric acid. The hydrate corresponding to R_{2}O_{7} is evidently RHO = RO_{3}(OH)--for example, perchloric acid. Here, besides containing O_{4}, it must further be remarked that _the amount of hydrogen in the hydrate is equal to the amount of hydrogen in the hydrogen compound_. Thus silicon gives SiH_{4} and SiH_{4}O_{4}, phosphorus PH_{3} and PH_{3}O_{4}, sulphur SH_{2} and SH_{2}O_{4}, chlorine ClH and ClHO_{4}. This, if it does not explain, at least connects in a harmonious and general system the fact that _the elements are capable of combining with a greater amount of oxygen, the less the amount of hydrogen which they are able to retain_. In this the key to the comprehension of all further deductions must be looked for, and we will therefore formulate this rule in general terms. An element R gives a hydrogen compound RH_{_n_}, the hydrate of its higher oxide will be RH_{_n_}O_{4}, and therefore the higher oxide will contain 2RH_{_n_}O_{4} - _n_H_{2}O = R_{2}O_{8 - _n_}. For example, chlorine gives ClH, hydrate ClHO_{4}, and the higher oxide Cl_{2}O_{7}. Carbon gives CH_{4} and CO_{2}. So also, SiO_{2} and SiH_{4} are the higher compounds of silicon with hydrogen and oxygen, like CO_{2} and CH_{4}. Here the amounts of oxygen and hydrogen are equivalent. Nitrogen combines with a large amount of oxygen, forming N_{2}O_{5}, but, on the other hand, with a small quantity of hydrogen in NH_{3}. _The sum of the equivalents of hydrogen and oxygen_, occurring in combination with an atom of nitrogen, is, as always in the higher types, equal to _eight_. It is the same with the other elements which combine with hydrogen and oxygen. Thus sulphur gives SO_{3}; consequently, six equivalents of oxygen fall to an atom of sulphur, and in SH_{2} two equivalents of hydrogen. The sum is again equal to eight. The relation between Cl_{2}O_{7} and ClH is the same. This shows that the property of elements of combining with such different elements as oxygen and hydrogen is subject to one common law, which is also formulated in the system of the elements presently to be described.[7] [7] The hydrogen compounds, R_{2}H, in equivalency correspond with the type of the suboxides, R_{4}O. Palladium, sodium, and potassium give such hydrogen compounds, and it is worthy of remark that according to the periodic system these elements stand near to each other, and that in those groups where the hydrogen compounds R_{2}H appear, the quaternary oxides R_{4}O are also present. Not wishing to complicate the explanation, I here only touch on the general features of the relation between the hydrates and oxides and of the oxides among themselves. Thus, for instance, the conception of the ortho-acids and of the normal acids will be considered in speaking of phosphoric and phosphorous acids. As in the further explanation of the periodic law only those oxides which give salts will be considered, I think it will not be superfluous to mention here the following facts relative to the peroxides. Of the _peroxides_ corresponding with hydrogen peroxide, the following are at present known: H_{2}O_{2}, Na_{2}O_{2}, S_{2}O_{7} (as HSO_{4}?), K_{2}O_{4}, K_{2}O_{2}, CaO_{2}, TiO_{3}, Cr_{2}O_{7}, CuO_{2}(?), ZnO_{2}, Rb_{2}O_{2}, SrO_{2}, Ag_{2}O_{2}, CdO_{2}, CsO_{2}, Cs_{2}O_{2}, BaO_{2}, Mo_{2}O_{7}, SnO_{3}, W_{2}O_{7}, UO_{4}. It is probable that the number of peroxides will increase with further investigation. A periodicity is seen in those now known, for the elements (excepting Li) of the first group, which give R_{2}O, form peroxides, and then the elements of the sixth group seem also to be particularly inclined to form peroxides, R_{2}O_{7}; but at present it is too early, in my opinion, to enter upon a generalisation of this subject, not only because it is a new and but little studied matter (not investigated for all the elements), but also, and more especially, because in many instances only the hydrates are known--for instance, Mo_{2}H_{2}O_{8}--and they perhaps are only compounds of peroxide of hydrogen--for example, Mo_{2}H_{2}O_{8} = 2MoO_{3} + H_{2}O_{2}--since Prof. Schöne has shown that H_{2}O_{2} and BaO_{2} possess the property of combining together and with other oxides. Nevertheless, I have, in the general table expressing the periodic properties of the elements, endeavoured to sum up the data respecting all the known peroxide compounds whose characteristic property is seen in their capability to form peroxide of hydrogen under many circumstances. In the preceding we see not only the regularity and simplicity which govern the formation and properties of the oxides and of all the compounds of the elements, but also a fresh and exact means for recognising the analogy of elements. Analogous elements give compounds of analogous types, both higher and lower. If CO_{2} and SO_{2} are two gases which closely resemble each other both in their physical and chemical properties, the reason of this must be looked for not in an analogy of sulphur and carbon, but in that identity of the type of combination, RX_{4}, which both oxides assume, and in that influence which a large mass of oxygen always exerts on the properties of its compounds. In fact, there is little resemblance between carbon and sulphur, as is seen not only from the fact that CO_{2} is the _higher form_ of oxidation, whilst SO_{2} is able to further oxidise into SO_{3}, but also from the fact that all the other compounds--for example, SH_{2} and CH_{4}, SCl_{2} and CCl_{4}, &c.--are entirely unlike both in type and in chemical properties. This absence of analogy in carbon and sulphur is especially clearly seen in the fact that the highest saline oxides are of different composition, CO_{2} for carbon, and SO_{3} for sulphur. In Chapter VIII. we considered the limit to which carbon tends in its compounds, and in a similar manner there is for every element in its compounds a tendency to attain a certain highest limit RX_{_n_}. This view was particularly developed in the middle of the present century by Frankland in studying the metallo-organic compounds, _i.e._ those in which X is wholly or partially a hydrocarbon radicle; for instance, X = CH_{3} or C_{2}H_{5} &c. Thus, for example, antimony, Sb (Chapter XIX.) gives, with chlorine, compounds SbCl_{3} and SbCl_{5} and corresponding oxygen compounds Sb_{2}O_{3} and Sb_{2}O_{5}, whilst under the action of CH_{3}I, C_{2}H_{5}I, or in general EI (where E is a hydrocarbon radicle of the paraffin series), upon antimony or its alloy with sodium there are formed SbE_{3} (for example, Sb(CH_{3})_{3}, boiling at about 81°), which, corresponding to the lower form of combination SbX_{3}, are able to combine further with EI, or Cl_{2}, or O, and to form compounds of the limiting type SbX_{5}; for example, SbE_{4}Cl corresponding to NH_{4}Cl with the substitution of nitrogen by antimony, and of hydrogen by the hydrocarbon radicle. The elements which are most chemically analogous are characterised by the fact of their giving compounds of similar form RX_{_n_}. The halogens which are analogous give both higher and lower compounds. So also do the metals of the alkalis and of the alkaline earths. And we saw that this analogy extends to the composition and properties of the nitrogen and hydrogen compounds of these metals, which is best seen in the salts. Many such groups of analogous elements have long been known. Thus there are analogues of oxygen, nitrogen, and carbon, and we shall meet with many such groups. But an acquaintance with them inevitably leads to the questions, what is the cause of analogy and what is the relation of one group to another? If these questions remain unanswered, it is easy to fall into error in the formation of the groups, because the notions of the degree of analogy will always be relative, and will not present any accuracy or distinctness Thus lithium is analogous in some respects to potassium and in others to magnesium; beryllium is analogous to both aluminium and magnesium. Thallium, as we shall afterwards see and as was observed on its discovery, has much kinship with lead and mercury, but some of its properties appertain to lithium and potassium. Naturally, where it is impossible to make measurements one is reluctantly obliged to limit oneself to approximate comparisons, founded on apparent signs which are not distinct and are wanting in exactitude. But in the elements there is one accurately measurable property, which is subject to no doubt--namely, that property which is expressed in their atomic weights. Its magnitude indicates the relative mass of the atom, or, if we avoid the conception of the atom, its magnitude shows the relation between the masses forming the chemical and independent individuals or elements. And according to the teaching of all exact data about the phenomena of nature, the mass of a substance is that property on which all its remaining properties must be dependent, because they are all determined by similar conditions or by those forces which act in the weight of a substance, and this is directly proportional to its mass. Therefore it is most natural to seek for a dependence between the properties and analogies of the elements on the one hand and their atomic weights on the other. This is the fundamental idea which leads _to arranging all the elements according to their atomic weights_. A periodic repetition of properties is then immediately observed in the elements. We are already familiar with examples of this:-- F = 19, Cl = 35·5, Br = 80, I = 127, Na = 23, K = 39, Rb = 85, Cs = 133, Mg = 24, Ca = 40, Sr = 87, Ba = 137. The essence of the matter is seen in these groups. The halogens have smaller atomic weights than the alkali metals, and the latter than the metals of the alkaline earths. Therefore, _if all the elements be arranged in the order of their atomic weights, a periodic repetition of properties is obtained_. This is expressed by the _law of periodicity_, _the properties of the elements, as well as the forms and properties of their compounds, are in periodic dependence or (expressing ourselves algebraically) form a periodic function of the atomic weights of the elements_.[8] Table I. of _the periodic system of the elements_, which is placed at the very beginning of this book, is designed to illustrate this law. It is arranged in conformity with the eight types of oxides described in the preceding pages, and those elements which give the oxides, R_{2}O and consequently salts RX, form the 1st group; the elements giving R_{2}O_{2} or RO as their highest grade of oxidation belong to the 2nd group; those giving R_{2}O_{3} as their highest oxides form the 3rd group, and so on; whilst the elements of all the groups which are nearest in their atomic weights are arranged in series from 1 to 12. The even and uneven series of the same groups present the same forms and limits, but differ in their properties, and therefore two contiguous series, one even and the other uneven--for instance, the 4th and 5th--form a period. Hence the elements of the 4th, 6th, 8th, 10th, and 12th, or of the 3rd, 5th, 7th, 9th, and 11th, series form analogues, like the halogens, the alkali metals, &c. The conjunction of two series, one even and one contiguous uneven series, thus forms one large _period_. These periods, beginning with the alkali metals, end with the halogens. The elements of the first two series have the lowest atomic weights, and in consequence of this very circumstance, although they bear the general properties of a group, they still show many peculiar and independent properties.[9] Thus fluorine, as we know, differs in many points from the other halogens, and lithium from the other alkali metals, and so on. These lightest elements may be termed _typical elements_. They include-- H. Li, Be, B, C, N, O, F. Na, Mg.... In the annexed table all the remaining elements are arranged, not in groups and series, but _according to periods_. In order to understand the essence of the matter, it must be remembered that here the atomic weight gradually increases along a given line; for instance, in the line commencing with K = 39 and ending with Br = 80, the intermediate elements have intermediate atomic weights, as is clearly seen in Table III., where the elements stand in the order of their atomic weights. I. II. III. IV. V. VI. VII. I. II. III. IV. V. VI. VII. { Even Series. } Mg Al Si P S Cl K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Rb Sr Y Zr Nb Mo -- Ru Rh Pd Ag Cd In Sn Sb Te I Cs Ba La Ce Di? -- -- -- -- -- -- -- -- -- -- -- -- -- -- Yb -- Ta W -- Os Ir Pt Au Hg Tl Pb Bi -- -- -- -- -- Th -- U { Uneven Series } The same degree of analogy that we know to exist between potassium, rubidium, and cæsium; or chlorine, bromine, and iodine; or calcium, strontium, and barium, also exists between the elements of the other vertical columns. Thus, for example, zinc, cadmium, and mercury, which are described in the following chapter, present a very close analogy with magnesium. For a true comprehension of the matter[10] it is very important to see that all the aspects of the distribution of the elements according to their atomic weights essentially express one and the same fundamental _dependence_--_periodic properties_.[11] The following points then must be remarked in it. [8] The periodic law and the periodic system of the elements appeared in the same form as here given in the first edition of this work, begun in 1868 and finished in 1871. In laying out the accumulated information respecting the elements, I had occasion to reflect on their mutual relations. At the beginning of 1869 I distributed among many chemists a pamphlet entitled 'An Attempted System of the Elements, based on their Atomic Weights and Chemical Analogies,' and at the March meeting of the Russian Chemical Society, 1869, I communicated a paper 'On the Correlation of the Properties and Atomic Weights of the Elements.' The substance of this paper is embraced in the following conclusions: (1) The elements, if arranged according to their atomic weights, exhibit an evident _periodicity_ of properties. (2) Elements which are similar as regards their chemical properties have atomic weights which are either of nearly the same value (platinum, iridium, osmium) or which increase regularly (_e.g._ potassium, rubidium, cæsium). (3) The arrangement of the elements or of groups of elements in the order of their atomic weights corresponds with their so-called _valencies_. (4) The elements, which are the most widely distributed in nature, have _small_ atomic weights, and all the elements of small atomic weight are characterised by sharply defined properties. They are therefore typical elements. (5) The _magnitude_ of the atomic weight determines the character of an element. (6) The discovery of many yet unknown elements may be expected. For instance, elements analogous to aluminium and silicon, whose atomic weights would be between 65 and 75. (7) The atomic weight of an element may sometimes be corrected by aid of a knowledge of those of the adjacent elements. Thus the combining weight of tellurium must lie between 123 and 126, and cannot be 128. (8) Certain characteristic properties of the elements can be foretold from their atomic weights. The entire periodic law is included in these lines. In the series of subsequent papers (1870-72, for example, in the _Transactions_ of the Russian Chemical Society, of the Moscow Meeting of Naturalists, of the St. Petersburg Academy, and Liebig's _Annalen_) on the same subject we only find applications of the same principles, which were afterwards confirmed by the labours of Roscoe, Carnelley, Thorpe, and others in England; of Rammelsberg (cerium and uranium), L. Meyer (the specific volumes of the elements), Zimmermann (uranium), and more especially of C. Winkler (who discovered germanium, and showed its identity with ekasilicon), and others in Germany; of Lecoq de Boisbaudran in France (the discoverer of gallium = ekaaluminium); of Clève (the atomic weights of the cerium metals), Nilson (discoverer of scandium = ekaboron), and Nilson and Pettersson (determination of the vapour density of beryllium chloride) in Sweden; and of Brauner (who investigated cerium, and determined the combining weight of tellurium = 125) in Austria, and Piccini in Italy. I consider it necessary to state that, in arranging the periodic system of the elements, I made use of the previous researches of Dumas, Gladstone, Pettenkofer, Kremers, and Lenssen on the atomic weights of related elements, but I was not acquainted with the works preceding mine of De Chancourtois (_vis tellurique_, or the spiral of the elements according to their properties and equivalents) in France, and of J. Newlands (Law of Octaves--for instance, H, F, Cl, Co, Br, Pd, I, Pt form the first octave, and O, S, Fe, Se, Rh, Te, Au, Th the last) in England, although certain germs of the periodic law are to be seen in these works. With regard to the work of Prof. Lothar Meyer respecting the periodic law (Notes 12 and 13), it is evident, judging from the method of investigation, and from his statement (Liebig's _Annalen, Supt. Band 7_, 1870, 354), at the very commencement of which he cites my paper of 1869 above mentioned, that he accepted the periodic law in the form which I proposed. In concluding this historical statement I consider it well to observe that no law of nature, however general, has been established all at once; its recognition is always preceded by many hints; the establishment of a law, however, does not take place when its significance is recognised, but only when it has been confirmed by experiment, which the man of science must consider as the only proof of the correctness of his conjectures and opinions. I therefore, for my part, look upon Roscoe, De Boisbaudran, Nilson, Winkler, Brauner, Carnelley, Thorpe, and others who verified the adaptability of the periodic law to chemical facts, as the true founders of the periodic law, the further development of which still awaits fresh workers. [9] This resembles the fact, well known to those having an acquaintance with organic chemistry, that in a series of homologues (Chapter VIII.) the first members, in which there is the least carbon, although showing the general properties of the homologous series, still present certain distinct peculiarities. [10] Besides arranging the elements (_a_) in a successive order according to their atomic weights, with indication of their analogies by showing some of the properties--for instance, their power of giving one or another form of combination--both of the _elements_ and of their compounds (as is done in Table III. and in the table on p. 36), (_b_) according to periods (as in Table I. at the commencement of volume I. after the preface), and (_c_) according to groups and series or small periods (as in the same tables), I am acquainted with the following methods of expressing the periodic relations of the elements: (1) By a curve drawn through points obtained in the following manner: The elements are arranged along the horizontal axis as abscissæ at distances from zero proportional to their atomic weights, whilst the values for all the elements of some property--for example, the specific volumes or the melting points, are expressed by the ordinates. This method, although graphic, has the theoretical disadvantage that it does not in any way indicate the existence of a limited and definite number of elements in each period. There is nothing, for instance, in this method of expressing the law of periodicity to show that between magnesium and aluminium there can be no other element with an atomic weight of, say, 25, atomic volume 13, and in general having properties intermediate between those of these two elements. The actual periodic law does not correspond with a continuous change of properties, with a continuous variation of atomic weight--in a word, it does not express an uninterrupted function--and as the law is purely chemical, starting from the conception of atoms and molecules which combine in multiple proportions, with intervals (not continuously), it _above all_ depends on there being but few types of compounds, which are arithmetically simple, _repeat themselves_, and offer no uninterrupted transitions, so that each period can only contain a definite number of members. For this reason there can be no other elements between magnesium, which gives the chloride MgCl_{2}, and aluminium, which forms AlX_{3}; there is a break in the continuity, according to the law of multiple proportions. The periodic law ought not, therefore, to be expressed by geometrical figures in which continuity is always understood. Owing to these considerations I never have and never will express the periodic relations of the elements by any geometrical figures. (2) _By a plane spiral._ Radii are traced from a centre, proportional to the atomic weights; analogous elements lie along one radius, and the points of intersection are arranged in a spiral. This method, adopted by De Chancourtois, Baumgauer, E. Huth, and others, has many of the imperfections of the preceding, although it removes the indefiniteness as to the number of elements in a period. It is merely an attempt to reduce the complex relations to a simple graphic representation, since the equation to the spiral and the number of radii are not dependent upon anything. (3) _By the lines of atomicity_, either parallel, as in Reynolds's and the Rev. S. Haughton's method, or as in Crookes's method, arranged to the right and left of an axis, along which the magnitudes of the atomic weights are counted, and the position of the elements marked off, on the one side the members of the even series (paramagnetic, like oxygen, potassium, iron), and on the other side the members of the uneven series (diamagnetic, like sulphur, chlorine, zinc, and mercury). On joining up these points a periodic curve is obtained, compared by Crookes to the oscillations of a pendulum, and, according to Haughton, representing a cubical curve. This method would be very graphic did it not require, for instance, that sulphur should be considered as bivalent and manganese as univalent, although neither of these elements gives stable derivatives of these natures, and although the one is taken on the basis of the lowest possible compound SX_{2}, and the other of the highest, because manganese can be referred to the univalent elements only by the analogy of KMnO_{4} to KClO_{4}. Furthermore, Reynolds and Crookes place hydrogen, iron, nickel, cobalt, and others outside the axis of atomicity, and consider uranium as bivalent without the least foundation. (4) Rantsheff endeavoured to classify the elements in their periodic relations by a system dependent on solid geometry. He communicated this mode of expression to the Russian Chemical Society, but his communication, which is apparently not void of interest, has not yet appeared in print. (5) _By algebraic formulæ_: for example, E. J. Mills (1886) endeavours to express all the atomic weights by the logarithmic function A = 15(_n_ - 0·9375_t_), in which the variables _n_ and _t_ are whole numbers. For instance, for oxygen _n_ = 2, _t_ = 1; hence A = 15·94; for antimony _n_ = 9, _t_ = 0; whence A = 120, and so on. _n_ varies from 1 to 16 and _t_ from 0 to 59. The analogues are hardly distinguishable by this method: thus for chlorine the magnitudes of _n_ and _t_ are 3 and 7; for bromine 6 and 6; for iodine 9 and 9; for potassium 3 and 14; for rubidium 6 and 18; for cæsium 9 and 20; but a certain regularity seems to be shown. (6) A more natural method of expressing the dependence of the properties of elements on their atomic weights is obtained by _trigonometrical functions_, because this dependence is periodic like the functions of trigonometrical lines, and therefore Ridberg in Sweden (Lund, 1885) and F. Flavitzky in Russia (Kazan, 1887) have adopted a similar method of expression, which must be considered as worthy of being worked out, although it does not express the absence of intermediate elements--for instance, between magnesium and aluminium, which is essentially the most important part of the matter. (7) The investigations of B. N. Tchitchérin (1888, _Journal of the Russian Physical and Chemical Society_) form the first effort in the latter direction. He carefully studied the alkali metals, and discovered the following simple relation between their atomic volumes: they can all be expressed by A(2 - 0·0428A_n_), where A is the atomic weight and _n_ = 1 for lithium and sodium, 4/8 for potassium, 3/8 for rubidium, and 2/8 for cæsium. If _n_ always = 1, then the volume of the atom would become zero at A = 46-2/3, and would reach its maximum when A = 23-1/3, and the density increases with the growth of A. In order to explain the variation of _n_, and the relation of the atomic weights of the alkali metals to those of the other elements, as also the atomicity itself, Tchitchérin supposes all atoms to be built up of a primary matter; he considers the relation of the central to the peripheric mass, and, guided by mechanical principles, deduces many of the properties of the atoms from the reaction of the internal and peripheric parts of each atom. This endeavour offers many interesting points, but it admits the hypothesis of the building up of all the elements from one primary matter, and at the present time such an hypothesis has not the least support either in theory or in fact. Besides which the starting-point of the theory is the specific gravity of the metals at a definite temperature (it is not known how the above relation would appear at other temperatures), and the specific gravity varies even under mechanical influences. L. Hugo (1884) endeavoured to represent the atomic weights of Li, Na, K, Rb, and Cs by geometrical figures--for instance, Li = 7 represents a central atom = 1 and six atoms on the six terminals of an octahedron; Na, is obtained by applying two such atoms on each edge of an octahedron, and so on. It is evident that such methods can add nothing new to our data respecting the atomic weights of analogous elements. [11] Many natural phenomena exhibit a dependence of a periodic character. Thus the phenomena of day and night and of the seasons of the year, and vibrations of all kinds, exhibit variations of a periodic character in dependence on time and space. But in ordinary periodic functions one variable varies continuously, whilst the other increases to a limit, then a period of decrease begins, and having in turn reached its limit a period of increase again begins. It is otherwise in the periodic function of the elements. Here the mass of the elements does not increase continuously, but abruptly, by steps, as from magnesium to aluminium. So also the valency or atomicity leaps directly from 1 to 2 to 3, &c., without intermediate quantities, and in my opinion it is these properties which are the most important, and it is their periodicity which forms the substance of the periodic law. It expresses _the properties of the real elements_, and not of what may be termed their manifestations visually known to us. The external properties of elements and compounds are in periodic dependence on the atomic weight of the elements only because these external properties are themselves the result of the properties of the real elements which unite to form the 'free' elements and the compounds. To explain and express the periodic law is to explain and express the cause of the law of multiple proportions, of the difference of the elements, and the variation of their atomicity, and at the same time to understand what mass and gravitation are. In my opinion this is still premature. But just as without knowing the cause of gravitation it is possible to make use of the law of gravity, so for the aims of chemistry it is possible to take advantage of the laws discovered by chemistry without being able to explain their causes. The above-mentioned peculiarity of the laws of chemistry respecting definite compounds and the atomic weights leads one to think that the time has not yet come for their full explanation, and I do not think that it will come before the explanation of such a primary law of nature as the law of gravity. It will not be out of place here to turn our attention to the many-sided correlation existing between the undecomposable _elements and the compound carbon radicles_, which has long been remarked (Pettenkofer, Dumas, and others), and reconsidered in recent times by Carnelley (1886), and most originally in Pelopidas's work (1883) on the principles of the periodic system. Pelopidas compares the series containing eight hydrocarbon radicles, C_{_n_}H_{2_n_ + 1}, C_{_n_}H_{2_n_} &c., for instance, C_{6}H_{13}, C_{6}H_{12}, C_{6}H_{11}, C_{6}H_{10}, C_{6}H_{9}, C_{6}H_{8}, C_{6}H_{7}, and C_{6}H_{6}--with the series of the elements arranged in eight groups. The analogy is particularly clear owing to the property of C_{_n_}H_{2_n_+1} to combine with X, thus reaching saturation, and of the following members with X_{2}, X_{3} ... X_{8}, and especially because these are followed by an aromatic radicle--for example, C_{6}H_{5}--in which, as is well known, many of the properties of the saturated radicle C_{6}H_{13} are repeated, and in particular the power of forming a univalent radicle again appears. Pelopidas shows a confirmation of the parallel in the property of the above radicles of giving oxygen compounds corresponding with the groups in the periodic system. Thus the hydrocarbon radicles of the first group--for instance, C_{6}H_{13} or C_{6}H_{5}--give oxides of the form R_{2}O and hydroxides RHO, like the metals of the alkalis; and in the third group they form oxides R_{2}O_{3} and hydrates RO_{2}H. For example, in the series CH_{3} the corresponding compounds of the third group will be the oxide (CH)_{2}O_{3} or C_{2}H_{2}O_{3}--that is, formic anhydride and hydrate, CHO_{2}H, or formic acid. In the sixth group, with a composition of C_{2}, the oxide RO_{3} will be C_{2}O_{3}, and hydrate C_{2}H_{2}O_{4}--that is, also a bibasic acid (oxalic) resembling sulphuric, among the inorganic acids. After applying his views to a number of organic compounds, Pelopidas dwells more particularly on the radicles corresponding with ammonium. With respect to this remarkable parallelism, it must above all be observed that in the elements the atomic weight increases in passing to contiguous members of a higher valency, whilst here it decreases, which should indicate that the periodic variability of elements and compounds is subject to some higher law whose nature, and still more whose cause, cannot at present be determined. It is probably based on the fundamental principles of the internal mechanics of the atoms and molecules, and as the periodic law has only been generally recognised for a few years it is not surprising that any further progress towards its explanation can only be looked for in the development of facts touching on this subject. 1. The composition of the higher oxygen compounds is determined by the groups: the first group gives R_{2}O, the second R_{2}O_{2} or RO, the third R_{2}O_{3}, &c. There are eight types of oxides and therefore eight groups. Two groups give a period, and the same type of oxide is met with twice in a period. For example, in the period beginning with potassium, oxides of the composition RO are formed by calcium and zinc, and of the composition RO_{3} by molybdenum and tellurium. The oxides of the even series, of the same type, have stronger basic properties than the oxides of the uneven series, and the latter as a rule are endowed with an acid character. Therefore the elements which exclusively give bases, like the alkali metals, will be found at the commencement of the period, whilst such purely acid elements as the halogens will be at the end of the period. The interval will be occupied by intermediate elements, whose character and properties we shall afterwards describe. It must be observed that the acid character is chiefly proper to the elements with small atomic weights in the uneven series, whilst the basic character is exhibited by the heavier elements in the even series. Hence elements which give acids chiefly predominate among the lightest (typical) elements, especially in the last groups; whilst the heaviest elements, even in the last groups (for instance, thallium, uranium) have a basic character. Thus the basic and acid characters of the higher oxides are determined (_a_) by the type of oxide, (_b_) by the even or uneven series, and (_c_) by the atomic weight.[11 bis] The groups are indicated by Roman numerals from I. to VIII. 2. _The hydrogen compounds_ being volatile or gaseous substances which are prone to reaction--such as HCl, H_{2}O, H_{3}N, and H_{4}C[12]--are only formed by the elements of the uneven series and higher groups giving oxides of the forms R_{2}O_{_n_}, RO_{3}, R_{2}O_{5}, and RO_{2}. 3. If an element gives a hydrogen compound, RX_{_m_}, it forms an _organo-metallic compound_ of the same composition, where X = C_{_n_}H_{2_n_ + 1}; that is, X is the radicle of a saturated hydrocarbon. The elements of the uneven series, which are incapable of giving hydrogen compounds, and give oxides of the forms RX, RX_{2}, R_{X}3, also give organo-metallic compounds of this form proper to the higher oxides. Thus zinc forms the oxide ZnO, salts ZnX_{2} and zinc ethyl Zn(C_{2}H_{5})_{2}. The elements of the even series do not seem to form organo-metallic compounds at all; at least all efforts for their preparation have as yet been fruitless--for instance, in the case of titanium, zirconium, or iron. 4. The atomic weights of elements belonging to contiguous periods differ approximately by 45; for example, K<Rb, Cr<Mo, Br<I. But the elements of the typical series show much smaller differences. Thus the difference between the atomic weights of Li, Na, and K, between Ca, Mg, and Be, between Si and C, between S and O, and between Cl and F, is 16. As a rule, there is a greater difference between the atomic weights of two elements of one group and belonging to two neighbouring series (Ti-Si = V-P = Cr-S = Mn-Cl = Nb-As, &c. = 20); and this difference attains a maximum with the heaviest elements (for example, Th-Pb = 26, Bi-Ta = 26, Ba-Cd = 25, &c.). Furthermore, the difference between the atomic weights of the elements of even and uneven series also increases. In fact, the differences between Na and K, Mg and Ca, Si and Ti, are less abrupt than those between Pb and Th, Ta and Bi, Cd and Ba, &c. Thus even in the magnitude of the differences of the atomic weights of analogous elements there is observable a certain connection with the gradation of their properties.[12 bis] 5. According to the periodic system every element occupies a certain position, determined by the group (indicated in Roman numerals) and series (Arabic numerals) in which it occurs. These indicate the atomic weight, the analogues, properties, and type of the higher oxide, and of the hydrogen and other compounds--in a word, all the chief quantitative and qualitative features of an element, although there yet remain a whole series of further details and peculiarities whose cause should perhaps be looked for in small differences of the atomic weights. If in a certain group there occur elements, R_{1}, R_{2}, R_{3}, and if in that series which contains one of these elements, for instance R_{2}, an element Q_{2} precedes it and an element T_{2} succeeds it, then the properties of R_{2} are determined by the properties of R_{1}, R_{3}, Q_{2}, and T_{2}. Thus, for instance, the atomic weight of R_{2} = 1/4(R_{1} + R_{3} + Q_{2} + T_{2}). For example, selenium occurs in the same group as sulphur, S = 32, and tellurium, Te = 125, and, in the 7th series As = 75 stands before it and Br = 80 after it. Hence the atomic weight of selenium should be 1/4(32 + 125 + 75 + 80) = 78, which is near to the truth. Other properties of selenium may also be determined in this manner. For example, arsenic forms H_{3}As, bromine gives HBr, and it is evident that selenium, which stands between them, should form H_{2}Se, with properties intermediate between those of H_{3}As and HBr. Even the physical properties of selenium and its compounds, not to speak of their composition, being determined by the group in which it occurs, may be foreseen with a close approach to reality from the properties of sulphur, tellurium, arsenic, and bromine. _In this manner it is possible to foretell the properties of still unknown elements._ For instance in the position IV, 5--that is, in the IVth group and 5th series--an element is still wanting. These unknown elements may be named after the preceding known element of the same group by adding to the first syllable the prefix _eka_-, which means _one_ in Sanskrit. The element IV, 5, follows after IV, 3, and this latter position being occupied by silicon, we call the unknown element ekasilicon and its symbol Es. The following are the properties which this element should have on the basis of the known properties of silicon, tin, zinc, and arsenic. Its atomic weight is nearly 72, higher oxide EsO_{2}, lower oxide EsO, compounds of the general form EsX_{4}, and chemically unstable lower compounds of the form EsX_{2}. Es gives volatile organo-metallic compounds--for instance, Es(CH_{3})_{4}, Es(CH_{3})_{3}Cl, and Es(C_{2}H_{5})_{4}, which boil at about 160°, &c.; also a volatile and liquid chloride, EsCl_{4}, boiling at about 90° and of specific gravity about 1·9. EsO_{2} will be the anhydride of a feeble colloidal acid, metallic Es will be rather easily obtainable from the oxides and from K_{2}EsF_{6} by reduction, EsS_{2} will resemble SnS_{2} and SiS_{2}, and will probably be soluble in ammonium sulphide; the specific gravity of Es will be about 5·5, EsO_{2} will have a density of about 4·7, &c. Such a prediction of the properties of ekasilicon was made by me in 1871, on the basis of the properties of the elements analogous to it: IV, 3, = Si, IV, 7 = Sn, and also II, 5 = Zn and V, 5 = As. And now that this element has been discovered by C. Winkler, of Freiberg, it has been found that its actual properties entirely correspond with those which were foretold.[13] In this we see a most important confirmation of the truth of the periodic law. This element is now called germanium, Ge (_see_ Chapter XVIII.). It is not the only one that has been predicted by the periodic law.[14] We shall see in describing the elements of the third group that properties were foretold of an element ekaaluminium, III, 5, El = 68, and were afterwards verified when the metal termed 'gallium' was discovered by De Boisbaudran. So also the properties of scandium corresponded with those predicted for ekaboron, according to Nilson.[15] [11 bis] True peroxides (_see_ Note 7), like H_{2}O_{2}, BaO_{2}, S_{2}O_{7} (Chapter XX.), must not be confused with true saline oxides even if the latter contain much oxygen (for instance, N_{2}O_{5}, CrO_{3}, &c.) although one and the other easily oxidise. The difference between them is seen in their fundamental properties: the saline oxides correspond to water, while the peroxides correspond in their reactions and origin to peroxide of hydrogen. This is clearly seen in the difference between Na_{2}O and Na_{2}O_{2} (Chapter XII.). Therefore the peroxides should also have their periodicity. An element R, giving a highest degree of oxidation, R_{2}O_{_n_}, may give both a lower degree of oxidation, R_{2}O_{_n_ - _m_} (where _m_ is evidently less than _n_), and peroxides, R_{2}O_{_n_ + 1}, R_{2}O_{_n_ + 2}, or even more oxygen. This class of oxides, to which attention has only recently been turned (Berthelot, Piccini, &c.), may perhaps on further study give the possibility of generalising the capability of the elements to give unstable complex higher forms of combination, such as double salts, and in my opinion should in the near future be the field of new and important discoveries. And in contemporary chemistry, salts, saline oxides, hydrogen compounds, and other combinations of the elements corresponding to them constitute an important and very complex problem for generalisation, which is satisfied by the periodic law in its present form, to which it has risen from its first state, in which it gave the means of foreseeing (_see_ later on) the existence of unknown elements (Ga, Sc, and Ge), their properties, and many details respecting their compounds. Until those improvements in the periodic system which have been proposed by Prof. Flavitzky (of Kazan) and Prof. Harperath (of Cordoba, in the Argentine Republic), Ugo Alvisi (Italy), and others give similar practical results, I think it unnecessary to discuss them further. [12] The hydrides generalised by the periodic law are those to which metallo-organic compounds correspond, and they are themselves either volatile or gaseous. The hydrogen compounds like Na_{2}H, BaH, &c. are distinguished by other signs. They resemble alloys. They show (_see_ end of last chapter) a systematic harmony, but they evidently should not be confused with true hydrides, any more than peroxides with saline oxides. Moreover, such hydrides have, like the peroxides, only recently been subjected to research, and have been but little studied. The best known of these compounds are given in the 16th column of Table III., and it will be seen that they already exhibit a periodicity of properties and composition. [12 bis] The relation between the atomic weights, and especially the difference = 16, was observed in the sixth and seventh decades of this century by Dumas, Pettenkofer, L. Meyer, and others. Thus Lothar Meyer in 1864, following Dumas and others, grouped together the tetravalent elements carbon and silicon; the trivalent elements nitrogen, phosphorus, arsenic, antimony, and bismuth; the bivalent oxygen, sulphur, selenium, and tellurium; the univalent fluorine, chlorine, bromine, and iodine; the univalent metals lithium, sodium, potassium, rubidium, cæsium, and thallium, and the bivalent metals beryllium, magnesium, strontium and barium--observing that in the first the difference is, in general = 16, in the second about = 46, and the last about = 87-90. The first germs of the periodic law are visible in such observations as these. Since its establishment this subject has been most fully worked out by Ridberg (Note 10), who observed a periodicity in the variation of the differences between the atomic weights of two contiguous elements, and its relation to their atomicity. A. Bazaroff (1887) investigated the same subject, taking, not the arithmetical differences of contiguous and analogous elements, but the ratio of their atomic weights; and he also observed that this ratio alternately rises and falls with the rise of the atomic weights. I will here remark that the relation of the eighth group to the others will be considered at the end of this work in Chapter XXII. [13] The laws of nature admit of no exceptions, and in this they clearly differ from such rules and maxims as are found in grammar, and other inventions, methods, and relations of man's creation. The confirmation of a law is only possible by deducing consequences from it, such as could not possibly be foreseen without it, and by verifying those consequences by experiment and further proofs. Therefore, when I conceived the periodic law, I (1869-1871, Note 9) deduced such logical consequences from it as could serve to show whether it were true or not. Among them was the prediction of the properties of undiscovered elements and the correction of the atomic weights of many, and at that time little known, elements. Thus uranium was considered as trivalent, U = 120; but as such it did not correspond with the periodic law. I therefore proposed to double its atomic weight--U = 240, and the researches of Roscoe, Zimmermann, and others justified this alteration (Chapter XXI.). It was the same with cerium (Chapter XVIII.) whose atomic weight it was necessary to change according to the periodic law. I therefore determined its specific heat, and the result I obtained was verified by the new determinations of Hillebrand. I then corrected certain formulæ of the cerium compounds, and the researches of Rammelsberg, Brauner, Clève, and others verified the proposed alteration. It was necessary to do one or the other--either to consider the periodic law as completely true, and as forming a new instrument in chemical research, or to refute it. Acknowledging the method of experiment to be the only true one, I myself verified what I could, and gave every one the possibility of proving or confirming the law, and did not think, like L. Meyer (Liebig's _Annalen, Supt. Band 7_, 1870, 364), when writing about the periodic law that 'it would be rash to change the accepted atomic weights on the basis of so uncertain a starting-point.' ('Es würde voreilig sein, auf so unsichere Anhaltspunkte hin eine Aenderung der bisher angenommenen Atomgewichte vorzunehmen.') In my opinion, the basis offered by the periodic law had to be verified or refuted, and experiment in every case verified it. The starting-point then became general. No law of nature can be established without such a method of testing it. Neither De Chancourtois, to whom the French ascribe the discovery of the periodic law, nor Newlands, who is put forward by the English, nor L. Meyer, who is now cited by many as its founder, ventured to foretell the _properties_ of undiscovered elements, or to alter the 'accepted atomic weights,' or, in general, to regard the periodic law as a new, strictly established law of nature, as I did from the very beginning (1869). [14] When in 1871 I wrote a paper on the application of the periodic law to the determination of the properties of hitherto undiscovered elements, I did not think I should live to see the verification of this consequence of the law, but such was to be the case. Three elements were described--ekaboron, ekaaluminium, and ekasilicon--and now, after the lapse of twenty years, I have had the great pleasure of seeing them discovered and named Gallium, Scandium, and Germanium, after those three countries where the rare minerals containing them are found, and where they were discovered. For my part I regard L. de Boisbaudran, Nilson, and Winkler, who discovered these elements, as the true corroborators of the periodic law. Without them it would not have been accepted to the extent it now is. [15] Taking indium, which occurs together with zinc, as our example, we will show the principle of the method employed. The equivalent of indium to hydrogen in its oxide is 37·7--that is, if we suppose its composition to be like that of water; then In = 37·7, and the oxide of indium is In_{2}O. The atomic weight of indium was taken as double the equivalent--that is, indium was considered to be a bivalent element--and In = 2 × 37·7 = 75·4. If indium only formed an oxide, RO, it should be placed in group II. But in this case it appears that there would be no place for indium in the system of the elements, because the positions II., 5 = Zn = 65 and II., 6 = Sr = 87 were already occupied by known elements, and according to the periodic law an element with an atomic weight 75 could not be bivalent. As neither the vapour density nor the specific heat, nor even the isomorphism (the salts of indium crystallise with great difficulty) of the compounds of indium were known, there was no reason for considering it to be a bivalent metal, and therefore it might be regarded as trivalent, quadrivalent, &c. If it be trivalent, then In = 3 × 37·7 = 113, and the composition of the oxide is In_{2}O_{3}, and of its salts InX_{3}. In this case it at once falls into its place in the system, namely, in group III. and 7th series, between Cd = 112 and Sn = 118, as an analogue of aluminium or dvialuminium (dvi = 2 in Sanskrit). All the properties observed in indium correspond with this position; for example, the density, cadmium = 8·6, indium = 7·4, tin = 7·2; the basic properties of the oxides CdO, In_{2}O_{3}, SnO_{2}, successively vary, so that the properties of In_{2}O_{3} are intermediate between those of CdO and SnO_{2} or Cd_{2}O_{2} and Sn_{2}O_{4}. That indium belongs to group III. has been confirmed by the determination of its specific heat, (0·057 according to Bunsen, and 0·055 according to me) and also by the fact that indium forms alums like aluminium, and therefore belongs to the same group. The same kind of considerations necessitated taking the atomic weight of titanium as nearly 48, and not as 52, the figure derived from many analyses. And both these corrections, made on the basis of the law, have now been confirmed, for Thorpe found, by a series of careful experiments, the atomic weight of titanium to be that foreseen by the periodic law. Notwithstanding that previous analyses gave Os = 199·7, Ir = 198, and Pt = 187, the periodic law shows, as I remarked in 1871, that the atomic weights should rise from osmium to platinum and gold, and not fall. Many recent researches, and especially those of Seubert, have fully verified this statement, based on the law. Thus a true law of nature anticipates facts, foretells magnitudes, gives a hold on nature, and leads to improvements in the methods of research, &c. 6. As a true law of nature is one to which there are no exceptions, the periodic dependence of the properties on the atomic weights of the elements gives a _new means for determining by the equivalent the atomic weight_ or atomicity of imperfectly investigated but known elements, for which no other means could as yet be applied for determining the true atomic weight. At the time (1869) when the periodic law was first proposed there were several such elements. It thus became possible to learn their true atomic weights, and these were verified by later researches. Among the elements thus concerned were indium, uranium, cerium, yttrium, and others. 7. The periodic variability of the properties of the elements in dependence on their masses presents a distinction from other kinds of periodic dependence (as, for example, the sines of angles vary periodically and successively with the growth of the angles, or the temperature of the atmosphere with the course of time), in that the weights of the atoms do not increase gradually, but by leaps; that is, according to Dalton's law of multiple proportions, there not only are not, but there cannot be, any transitive or intermediate elements between two neighbouring ones (for example, between K = 39 and Ca = 40, or Al = 27 and Si = 28, or C = 12 and N = 14, &c.) As in a molecule of a hydrogen compound there may be either one, as in HF, or two, as in H_{2}O, or three, as in NH_{3}, &c., atoms of hydrogen; but as there cannot be molecules containing 2-1/2 atoms of hydrogen to one atom of another element, so there cannot be any element intermediate between N and O, with an atomic weight greater than 14 or less than 16, or between K and Ca. Hence the periodic dependence of the elements cannot be expressed by any algebraical continuous function in the same way that it is possible, for instance, to express the variation of the temperature during the course of a day or year. 8. The essence of the notions giving rise to the periodic law consists in a general physico-mechanical principle which recognises the correlation, transmutability, and equivalence of the forces of nature. Gravitation, attraction at small distances, and many other phenomena are in direct dependence on the mass of matter. It might therefore have been expected that chemical forces would also depend on mass. A dependence is in fact shown, the properties of elements and compounds being determined by the masses of the atoms of which they are formed. The weight of a molecule, or its mass, determines, as we have seen, (Chapter VII. and elsewhere) many of its properties independently of its composition. Thus carbonic oxide, CO, and nitrogen, N_{2}, are two gases having the same molecular weight, and many of their properties (density, liquefaction, specific heat, &c.) are similar or nearly similar. The differences dependent on the nature of a substance play another part, and form magnitudes of another order. But the properties of atoms are mainly determined by their mass or weight, and are in dependence upon it. Only in this case there is a peculiarity in the dependence of the properties on the mass, for this _dependence is determined by a periodic law_. As the mass increases the properties vary, at first successively and regularly, and then return to their original magnitude and recommence a fresh period of variation like the first. Nevertheless here as in other cases a small variation of the mass of the atom generally leads to a small variation of properties, and determines differences of a second order. The atomic weights of cobalt and nickel, of rhodium, ruthenium, and palladium, and of osmium, iridium, and platinum, are very close to each other, and their properties are also very much alike--the differences are not very perceptible. And if the properties of atoms are a function of their weight, many ideas which have more or less rooted themselves in chemistry must suffer change and be developed and worked out in the sense of this deduction. Although at first sight it appears that the chemical elements are perfectly independent and individual, instead of this idea of the nature of the elements, the notion of the dependence of their properties upon _their mass_ must now be established; that is to say, the subjection of the individuality of the elements to a common higher principle which evinces itself in gravity and in all physico-chemical phenomena. Many chemical deductions then acquire a new sense and significance, and a regularity is observed where it would otherwise escape attention. This is more particularly apparent in the physical properties, to the consideration of which we shall afterwards turn, and we will now point out that Gustavson first (Chapter X., Note 28) and subsequently Potilitzin (Chapter XI., Note 66) demonstrated the direct dependence of the reactive power on the atomic weight and that fundamental property which is expressed in the forms of their compounds, whilst in a number of other cases the purely chemical relations of elements proved to be in connection with their periodic properties. As a case in point, it may be mentioned that Carnelley remarked a dependence of the decomposability of the hydrates on the position of the elements in the periodic system; whilst L. Meyer, Willgerodt, and others established a connection between the atomic weight or the position of the elements in the periodic system and their property of serving as media in the transference of the halogens to the hydrocarbons.[16] Bailey pointed out a periodicity in the stability (under the action of heat) of the oxides, namely: (_a_) in the even series (for instance, CrO_{3}, MoO_{3}, WO_{3}, and UO_{3}) the higher oxides of a given group decompose with greater ease the smaller the atomic weight, while in the uneven series (for example, CO_{2}, GeO_{2}, SnO_{2}, and PbO_{2}) the contrary is the case; and (_b_) the stability of the higher saline oxides in the even series (as in the fourth series from K_{2}O to Mn_{2}O_{7}) decreases in passing from the lower to the higher groups, while in the uneven series it increases from the Ist to the IVth group, and then falls from the IVth to the VIIth; for instance, in the series Ag_{2}O, CdO, In_{2}O_{3}, SnO_{2}, and then SnO_{2}, Sb_{2}O_{5}, TeO_{3}, I_{2}O_{7}. K. Winkler looked for and actually found (1890) a dependence between the reducibility of the metals by magnesium and their position in the periodic system of the elements. The greater the attention paid to this field the more often is a distinct connection found between the variation of purely chemical properties of analogous substances and the variation of the atomic weights of the constituent elements and their position in the periodic system. Besides, since the periodic system has become more firmly established, many facts have been gathered, showing that there are many similarities between Sn and Pb, B and Al, Cd and Hg, &c., which had not been previously observed, although foreseen in some cases, and a consequence of the periodic law. Keeping our attention in the same direction, we see that the most widely distributed elements in nature are those with small atomic weights, whilst in organisms the lightest elements exclusively predominate (hydrogen, carbon, nitrogen, oxygen), whose small mass facilitates those transformations which are proper to organisms. Poluta (of Kharkoff), C. C. Botkin, Blake, Brenton, and others even discovered a correlation between the physiological action of salts and other reagents on organisms and the positions occupied in the periodic system by the metals contained in them.[17] [16] Meyer, Willgerodt, and others, guided by the fact that Gustavson and Friedel had remarked that metalepsis rapidly proceeds in the presence of aluminium, investigated the action of nearly all the elements in this respect. For example, they took benzene, added the metals to be experimented on to it, and passed chlorine through the liquid in diffused light. When, for instance, sodium, potassium, barium, &c. are taken, there is no action on the benzene; that is, hydrochloric acid is not disengaged; but if aluminium, gold, or, in general, any metal having this power of aiding chlorination (Halogen-überträger) is employed, then the action is clearly seen from the volumes of hydrochloric acid evolved (especially if the metallic chloride formed is soluble in benzene). Thus, in group I., and in general among the even and light elements, there are none capable of serving as agents of metalepsis; but aluminium, gallium, indium, antimony, tellurium, and iodine, which are contiguous members in the periodic system, are excellent transmitters (carriers) of the halogens. [17] The periodic relations enumerated above appertain to the real elements, and not to the elements in the free state as we know them; and it is very important to note this, because the periodic law refers to the real elements, inasmuch as the atomic weight is proper to the real element, and not to the 'free' element, to which, as to a compound, a molecular weight is proper. Physical properties are chiefly determined by the properties of molecules, and only indirectly depend on the properties of the atoms forming the molecules. For this reason the periods, which are clearly and quite distinctly expressed--for instance, in the forms of combination--become to some extent involved (complicated) in the physical properties of their members. Thus, for instance, besides the _maxima_ and _minima_ corresponding with the periods and groups, new molecules appear; thus, as regards the melting-point of germanium, a local maximum appears, which was, however, foreseen by the periodic law when the properties of germanium (ekasilicon) were forecast. As, from the necessity of the case, the physical properties must be in dependence on the composition of a substance, _i.e._ on the quality and quantity of the elements forming it, so for them also a dependence on the atomic weight of the component elements must be expected, and consequently also on their periodic distribution. We shall meet with repeated proofs of this in the further exposition of our treatise, and for the present will content ourselves with citing the discovery by Carnelley in 1879 of the dependence of the magnetic properties of the elements on the position occupied by them in the periodic system. Carnelley showed that all the elements of the _even series_ (beginning with lithium, potassium, rubidium, cæsium) belong to the number of magnetic (paramagnetic) substances; for example, according to Faraday and others,[17 bis] C, N, O, K, Ti, Cr, Mn, Fe, Co, Ni, Ce, are magnetic; and the elements of the _uneven series are diamagnetic_, H, Na, Si, P, S, Cl, Cu, Zn, As, Se, Br, Ag, Cd, Sn, Sb, I, Au, Hg, Tl, Pb, Bi. [17 bis] The relation of certain elements (for instance, the analogues of Pt) among diamagnetic and paramagnetic bodies is sometimes doubtful (probably partly owing to the imperfect purity of the reagents under investigation). This subject has been studied in some detail by Bachmetieff in 1889. Carnelley also showed that the _melting-point_ of elements varies periodically, as is seen by the figures in Table III. (nineteenth column),[18] where all the most trustworthy data are collected, and predominance is given to those having maximum and minimum values.[19] [18] It is evident that many of the figures, especially those exceeding 1000°, have been determined with but little exactitude, and some, placed in Table III. with the sign (?), I have only given on the basis of rough and comparative determinations, calculated from the melting-points of silver and platinum, now established by many observers. In Table III., besides the large periods whose maxima correspond with carbon, silicon, titanium, ruthenium (?), and osmium (?), there are also small periods in the melting-points, and their maxima correspond with sulphur, arsenic, antimony. The minima correspond with the halogens and metals of the alkalis. A distinct periodicity is also seen in taking the coefficients of linear expansion (chiefly according to Fizeau); for instance, in the vertical series (according to the magnitude of the atomic weight), Fe, Co, Ni, Cu, the linear expansion in millionths of an inch = 12, 13, 17, and 29; for Rh, Pd, Ag, Cd, In, Sn, and Sb the coefficients are 8, 12, 19, 31, 46, 26, and 12, so that a maximum is reached at In. In the series Ir (7), Pt (5), Au (14), Hg (60), Tl (31), Pb (29), and Bi (14), the maximum is at Hg and the minimum at Pt. Raoul Pictet expressed this connection by the fact that he found the product [alpha](_t_ + 273)[3root](A/_d_) to be nearly constant for all elements in the free state, and nearly equal to 0·045, and being the coefficient of linear expansion, _t_ + 273, the melting-point calculated from the absolute zero (-273°), and [3root](A/_d_), the mean distance between the atoms, if A is the atomic weight and _d_ the sp. gr. of an element. Although the above product is not strictly constant, nevertheless Pictet's rule gives an idea of the bond between magnitudes which ought to have a certain connection with each other. De Heen, Nadeschdin, and others also studied this dependence, but their deductions do not give a general and exact law. [19] Carnelley found a similar dependence in comparing the melting-points of the metallic chlorides, many of which he redetermined for this purpose. The melting-points (and boiling-points, in brackets) of the following chlorides are known, and a certain regularity is seen to exist in them, although the number (and degree of accuracy) of the data is insufficient for a generalisation:-- LiCl 598° BeCl_{2} 600° BCl_{3} -20° NaCl 772° MgCl_{2} 708° AlCl_{3} 187° KCl 734° CaCl_{2} 719° ScCl_{3} ? {CuCl 434° ZnCl_{2} 262° GaCl_{3} 76° {(993°) (680°) (217°) AgCl 451° CdCl_{2} 541° InCl_{3} ? {TlCl 427° PbCl_{2} 498° BiCl_{3} 227° {(713°) (908°) We will also enumerate the following data given by Carnelley, which are interesting for comparison: HCl -112° (-102°); RbCl 710°, SrCl_{2} 825°, CsCl 631°, BaCl_{2} 860°, SbCl_{3} 73° (223°), TeCl_{2} 209° (327°), ICl 27°, HgCl_{2} 276° (303°), FeCl_{3} 306°, NbCl_{5} 194° (240°), TaCl_{3} 211° (242°), WCl_{6} 190°. The melting-points of the bromides and iodides are higher or lower than those of the corresponding chlorides, according to the atomic weight of the element and number of atoms of the halogen, as is seen from the following examples:--1. KCl 734°, KBr 699°, KI 634°; 2. AgCl 454°, AgBr 427° AgI 527°; 3. PbCl_{2} 498° (900°), PbBr_{2} 499° (861°), PbI_{2} 383° (906°); 4. SnCl_{4} below -20° (114°), SnBr_{2} 30° (201°), SnI_{4} 146° (295°) (_see_ Chapter II. Note 27, and Chapter XI. Note 47^{bis}, &c.) Laurie (1882) also observed a periodicity in the _quantity of heat_ developed in the formation of the chlorides, bromides, and iodides (fig. 79), as is seen from the following figures, where the heat developed is expressed in thousands of calories, and referred to a molecule of chlorine, Cl_{2}, so that the heat of formation of KCl is doubled, and that of SnCl_{4} halved, &c.: Na 195 (Ag 59, Au 12), Mg 151 (Zn 97, Cd 93, Hg 63), Al 117, Si 79 (Sn 64), K 211 (Li 187), Ca 170 (Sr 185, Ba 194), whence it is seen that the greatest amount of heat is evolved by the metals of the alkalis, and that in each period it falls from them to the halogens, which evolve very little heat in combining together. Richardson, by comparing the heats of formation of the fluorides also came to the conclusion that they are in periodic dependence upon the atomic weights of the combined elements. [Illustration: FIG. 79.--Laurie's diagram for expressing the periodic variation of the heat of formation of the chlorides. The abscissæ give the atomic weights from 0 to 210, and the ordinates the amounts of heat from 0 to 220 thousand calories evolved in the combination with Cl_{2}, (_i.e._ with 71 parts of chlorine). The apices of the curve correspond to Li, Na, K, Rb, Cs, and the lower extremities to F, Cl, Br, and I.] In this respect it may not be superfluous to remark (1) that Thomsen, whose results I have employed above, observed a correlation in the calorific equivalents of analogous elements, although he did not remark their periodic variation; (2) that the uniformity of many thermochemical deductions must gain considerably by the application of the periodic law, which evidently repeats itself in calorimetric data; and if these data frequently lead to true forecasts, this is due to the periodicity of the thermal as well as of many other properties, as Laurie remarked; and (3) that the heat of formation of the oxides is also subject to a periodic dependence which differs from that of the heat of formation of the chlorides, in that the greatest quantity corresponds with the bivalent metals of the alkaline earths (magnesium, calcium, strontium, barium), and not with the univalent metals of the alkalis, as is the case with chlorine, bromine, and iodine. This circumstance is probably connected with the fact that chlorine, bromine, and iodine are univalent elements, and oxygen bivalent (compare, for instance, Chapter XI., Note 13, Chapter XXII., Note 40, Chapter XXIV., Note 28^{bis}, &c.) Keyser (1892), in investigating the spectra of the alkali metals and metals of the alkaline earths, came to the conclusion that in this respect also there is a regularity of a periodic character in dependence upon the atomic weights. Probably a closer and systematic study of many of the properties of the elements and of complex and simple bodies formed by them will more and more frequently lead to similar conclusions, and to extending the range of application of the periodic law. There is no doubt that many other physical properties will, when further studied, also prove to be in periodic dependence on the atomic weights,[19 bis] but at present only a few are known with any completeness, and we will only refer to the one which is the most easily and frequently determined--namely, the _specific gravity_ in a solid and liquid state, the more especially as its connection with the chemical properties and relations of substances is shown at every step. Thus, for instance, of all the metals those of the alkalis, and of all the non-metals the halogens, are the most energetic in their reactions, and they have the lowest specific gravity among the adjacent elements, as is seen in Table III., column 17. Such are sodium, potassium, rubidium, cæsium among the metals, and chlorine, bromine, and iodine among the non-metals; and as such less energetic metals as iridium, platinum, and gold (and even charcoal or the diamond) have the highest specific gravity among the elements near to them in atomic weight; therefore the degree of the condensation of matter evidently influences the course of the transformations proper to a substance, and furthermore this dependence on the atomic weight, although very complex, is of a clearly periodic character. In order to account for this to some extent, it may be imagined that the lightest elements are porous, and, like a sponge, are easily penetrated by other substances, whilst the heavier elements are more compressed, and give way with difficulty to the insertion of other elements. These relations are best understood when, instead of the specific gravities referring to a unit of volume,[20] the _atomic volumes of the elements_--that is, the quotient _A_/_d_ of the atomic weight _A_ by the specific gravity _d_--are taken for comparison. As, according to the entire sense of the atomic theory, the actual matter of a substance does not fill up its whole cubical contents, but is surrounded by a medium (ethereal, as is generally imagined), like the stars and planets which travel in the space of the heavens and fill it, with greater or less intervals, so the quotient _A_/_d_ only expresses the _mean_ volume corresponding to the sphere of the atoms, and therefore [3root]_A_/_d_ _is the mean distance between the centres of the atoms_. For compounds whose molecules weigh _M_, the mean magnitude of the atomic volume is obtained by dividing the mean molecular volume _M_/_d_ by the number of atoms _n_ in the molecule.[21] The above relations may easily be expressed from this point of view by comparing the atomic volumes. Those comparatively light elements which easily and frequently enter into reaction have the greatest atomic volumes: sodium 23, potassium 45, rubidium 57, cæsium 71, and the halogens about 27; whilst with those elements which enter into reaction with difficulty, the mean atomic volume is small; for carbon in the form of a diamond it is less than 4, as charcoal about 6, for nickel and cobalt less than 7, for iridium and platinum about 9. The remaining elements having atomic weights and properties intermediate between those elements mentioned above have also intermediate atomic volumes. Therefore _the specific gravities and specific volumes of solids and liquids stand in periodic dependence on the atomic weights_, as is seen in Table III., where both _A_ (the atomic weight) and _d_ (the specific gravity), and _A_/_d_ (specific volumes of the atoms) are given (column 18). [19 bis] Probably, besides thermo-chemical data (Note 19), the refractive index, cohesion, ductility, and similar properties of corresponding compounds or of the elements themselves will be found to exhibit a dependence of the magnitude of the atomic weight upon the periodic law. [20] Having occupied myself since the fifties (my dissertation for the degree of M.A. concerned the specific volumes, and is printed in part in the _Russian Mining Journal_ for 1856) with the problems concerning the relations between the specific gravities and volumes, and the chemical compositions of substances, I am inclined to think that the direct investigation of specific gravities gives essentially the same results as the investigation of specific volumes, only that the latter are more graphic. Table III. of the periodic properties of the elements clearly illustrates this. Thus, for those members whose volume is the greatest among the contiguous elements, the specific gravity is least--that is, the periodic variation of both properties is equally evident. In passing, for instance, from silver to iodine we have a successive decrease of specific gravity and successive increase of specific volume. The periodic alternation of the rise and fall of the specific gravity and specific volume of the free elements was communicated by me in August 1869 to the Moscow Meeting of Russian Naturalists. In the following year (1870) L. Meyer's paper appeared, which also dealt with the specific volume of the elements. [21] In my opinion the mean volume of the atoms of compounds deserves more attention than has yet been paid to it. I may point out, for instance, that for feebly energetic oxides the mean volume of the atom is generally nearly 7; for example, the oxides SiO_{2}, Sc_{2}O_{3}, TiO_{2}, V_{2}O_{5}, as well as ZnO, Ga_{2}O_{3}, GeO_{2}, ZrO_{2}, In_{2}O_{3}, SnO_{2}, Sb_{2}O_{5}, &c., whilst the mean volume of the atom of the alkali and acid oxides is greater than 7. Thus we find in the magnitudes of the mean volumes of the atom in oxides and salts both a periodic variation and a connection with their energy of essentially the same character as occurs in the case of the free elements. Thus we find that in the large periods beginning with lithium, sodium, potassium, rubidium, cæsium, and ending with fluorine, chlorine, bromine, iodine, the extreme members (energetic elements) have a small density and large volume, whilst the intermediate substances gradually increase in density and decrease in volume--that is, as the atomic weight increases the density rises and falls, again rises and falls, and so on. Furthermore, the energy decreases as the density rises, and the greatest density is proper to the atomically heaviest and least energetic elements; for example, Os, Ir, Pt, Au, U. In order to explain the relation between the volumes of the elements and of their compounds, the densities (column S) and volumes (column M/_s_) of some of the higher saline oxides arranged in the same order as in the case of the elements are given on p. 36. For convenience of comparison the volumes of the oxides are all calculated per two atoms of an element combined with oxygen. For example, the density of Al_{2}O_{3} = 4·0, weight Al_{2}O_{3} = 102, volume Al_{2}O_{3} = 25·5. Whence, knowing the volume of aluminium to be 11, it is at once seen that in the formation of aluminium oxide, 22 volumes of it give 25·5 volumes of oxide. A distinct periodicity may also be observed with respect to the specific gravities and volumes of the higher saline oxides. Thus in each period, beginning with the alkali metals, the specific gravity of the oxides first rises, reaches a maximum, and then falls on passing to the acid oxides, and again becomes a minimum about the halogens. But it is especially important to call attention to the fact that the volume of the alkali oxides is less than that of the metal contained in them, which is also expressed in the last column, giving this difference for each atom of oxygen.[22] Thus 2 atoms of sodium, or 46 volumes, give 24 volumes of Na_{2}O, and about 37 volumes of 2NaHO--that is, the oxygen and hydrogen in distributing themselves in the medium of sodium have not only not increased the distance between its atoms, but have brought them nearer together, have drawn them together by the force of their great affinity, by reason, it may be presumed, of the small mutual attraction of the atoms of sodium. Such metals as aluminium and zinc, in combining with oxygen and forming oxides of feeble salt-forming capacity, hardly vary in volume, but the common metals and non-metals, and especially those forming acid oxides, always give an increased volume when oxidised--that is, the atoms are set further apart in order to make room for the oxygen. The oxygen in them does not compress the molecule as in the alkalis; it is therefore comparatively easily disengaged. [22] The volume of oxygen (judging by the table on p. 36) is evidently a variable quantity, forming a distinctly periodic function of the atomic weight and type of the oxide, and therefore the efforts which were formerly made to find the volume of the atom of oxygen in the volumes of its compounds may be considered to be futile. But since a distinct contraction takes place in the formation of oxides, and the volume of an oxide is frequently less than the volume in the free state of the element contained in it, it might be surmised that the volume of oxygen in a free state is about 15, and therefore the specific gravity of solid oxygen in a free state would be about O·9. S M/_s_ Volume of Oxygen H_{2}O 1·0 18 ?- 22 Li_{2}O 2·0 15 - 9 Be_{2}O_{2} 3·06 16 + 2·6 B_{2}O_{3} 1·8 39 + 10·0 C_{2}O_{4} 1·6 55 + 10·6 N_{2}O_{5} 1·64 66 ?+ 4 Na_{2}O 2·6 24 - 22 Mg_{2}O_{2} 3·5 23 - 4·5 Al_{2}O_{3} 4·0 26 + 1·3 Si_{2}O_{4} 2·65 45 + 5·2 P_{2}O_{5} 2·39 59 + 6·2 S_{2}O_{6} 1·96 82 + 8·7 Cl_{2}O_{7} ?1·92 95 + 6 K_{2}O 2·7 35 - 35 Ca_{2}O_{2} 3·25 34 - 8 Sc_{2}O_{3} 3·86 35 ? 0 Ti_{2}O_{4} 4·2 38 + 3 V_{2}O_{5} 3·49 52 + 6·7 Cr_{2}O_{6} 2·74 73 + 9·5 Cu_{2}O 5·9 24 + 9·6 Zn_{2}O_{2} 5·7 23 + 4·8 Ga_{2}O_{3} ?5·1 36 + 4 Ge_{2}O_{4} 4·7 44 + 4·5 As_{2}O_{5} 4·1 56 + 6·0 Sr_{2}O_{2} 4·7 44 - 13 Y_{2}O_{3} 5·0 45 ?- 2 Zr_{2}O_{4} 5·5 44 0 Nb_{2}O_{5} 4·7 57 + 6 MoO_{6} 4·4 65 + 6·8 Ag_{2}O 7·5 31 + 11 Cd_{2}O_{3} 8·0 32 + 3 In_{2}O_{3} 7·18 38 + 2·7 Sn_{2}O_{4} 7·O 43 + 2·7 Sb_{2}O_{5} 6·5 49 + 2·6 TeO_{6} 5·1 68 + 4·7 Ba_{2}O_{2} 5·7 52 - 10 La_{2}O_{3} 6·5 50 + 1 Ce_{2}O_{4} 6·74 50 + 2 Ta_{2}O_{5} 7·5 59 + 4·6 W_{2}O_{6} 6·8 68 + 8·2 Hg_{2}O_{2} 11·1 39 + 4·5 Pb_{2}O_{4} 8·9 53 + 4·2 Th_{2}O_{4} 9·86 54 + 2 As the volumes of the chlorides, organo-metallic and all other corresponding compounds, also vary in a like periodic succession with a change of elements, it is evidently possible to indicate the properties of substances yet uninvestigated by experimental means, and even those of yet undiscovered elements. It was possible by following this method to foretell, on the basis of the periodic law, many of the properties of scandium, gallium, and germanium, which were verified with great accuracy after these metals had been discovered.[23] The periodic law, therefore, has not only embraced the mutual relations of the elements and expressed their analogy, but has also to a certain extent subjected to law the doctrine of the types of the compounds formed by the elements: it has enabled us to see a regularity in the variation of all chemical and physical properties of elements and compounds, and has rendered it possible to foretell the properties of elements and compounds yet uninvestigated by experimental means; thus it has prepared the ground for the building up of atomic and molecular mechanics.[24] [23] As an example we will take indium oxide, In_{2}O_{3}. Its sp. gr. and sp. vol. should be the mean of those of cadmium oxide, Cd_{2}O_{2}, and stannic oxide, Sn_{2}O_{4}, as indium stands between cadmium and tin. Thus in the seventies it was already evident that the volume of indium oxide should be about 38, and its sp. gr. about 7·2, which was confirmed by the determinations of Nilson and Pettersson (7·179) made in 1880. [24] As the distance between, and the volumes of, the molecules and atoms of solids and liquids certainly enter into the data for the solution of the problems of molecular mechanics, which as yet have only been worked out to any extent for the gaseous state, the study of the specific gravity of solids, and especially of liquids, has long had an extensive literature. With respect to solids, however, a great difficulty is met with, owing to the specific gravity varying not only with a change of isomeric state (for example, for silica in the form of quartz = 2·65, and in tridymite = 2·2) but also directly under mechanical pressure (for example, in a crystalline, cast, and forged metal), and even with the extent to which they are powdered, &c., which influences are imperceptible in liquids. Compare Chapter XIV., Note 55^{bis}. Without going into further details, we may add to what has been said above that the conception of specific volumes and atomic distances has formed the subject of a large number of researches, but as yet it is only possible to lay down a few generalisations given by Dumas, Kopp, and others, which are mentioned and amplified by me in my work cited in Note 20, and in my memoirs on this subject. 1. Analogous compounds and their isomorphs have frequently approximately the same molecular volumes. 2. Other compounds, analogous in their properties, exhibit molecular volumes which increase with the molecular weight. 3. When a contraction takes place in combination in a gaseous state, then contraction is in the majority of instances also to be observed in the solid or liquid state--that is, the sum of the volumes of the reacting substances is greater than the volume of the resultant substance or substances. 4. In decomposition the reverse takes place to that which occurs in combination. 5. In substitution (when the volumes in a state of vapour do not vary) a very small change of volume generally takes place--that is, the sum of the volumes of the reacting substances is almost equal to the sum of the resultant substances. 6. Hence it is impossible to judge the volume of the component substances from the volume of a compound, although it is possible to do so from the product of substitution. 7. The replacement of H_{2} by sodium, Na_{2}, and by barium, Ba, as well as the replacement of SO_{4} by Cl_{2}, scarcely changes the volume, but the volume increases with the replacement of Na by K, and decreases with the replacement of H_{2}, by Li_{2} Cu, and Mg. 8. There is no need for comparing volumes in a solid and liquid state at the so-called corresponding temperatures--that is at temperatures at which vapour tension is equal in each case. The comparison of volumes at the ordinary temperature is sufficient for finding a regularity in the relations of volumes (this deduction was developed with particular detail by me in 1856). 9. Many investigators (Perseau, Schröder, Löwig, Playfair and Joule, Baudrimont, Einhardt) have sought in vain for a multiple proportion in the specific volumes of solids and liquids. 10. The truth of the above is seen very clearly in comparing the volumes of polymeric substances. The volumes of their molecules are equal in a state of vapour, but are very different in a solid and liquid state, as is seen from the close resemblance of the specific gravities of polymeric substances. But as a rule the more complex polymerides are denser than the simpler. 11. We know that the hydroxides of light metals have generally a smaller volume than the metals, whilst that of magnesium hydroxide is considerably greater, which is explained by the stability of the former and instability of the latter. In proof of this we may cite, besides the volumes of the true alkali metals, the volume of barium (36) which is greater than that of its stable hydroxide (sp. gr. 4·5, sp. vol. 30). The volumes of the salts of magnesium and calcium are greater than the volume of the metal, with the single exception of the fluoride of calcium. With the heavy metals the volume of the compound is always greater than the volume of the metal, and, moreover, for such compounds as silver iodide, AgI (_d_ = 5·7), and mercuric iodide, HgI_{2} (_d_ = 6·2, and the volumes of the compounds 41 and 73), the volume of the compound is greater than the sum of the volumes of the component elements. Thus the sum of the volumes Ag + I = 36, and the volume of AgI = 41. This stands out with particular clearness on comparing the volumes K + I = 71 with the volume of KI, which is equal to 54, because its density = 3·06. 12. In such combinations, between solids and liquids, as solutions, alloys, isomorphous mixtures, and similar feeble chemical compounds, the sum of the reacting substances is always very nearly that of the resulting substance, but here the volume is either slightly larger or smaller than the original; speaking generally, the amount of contraction depends on the force of affinity acting between the combining substances. I may here observe that the present data respecting the specific volumes of solid and liquid bodies deserve a fresh and full elaboration to explain many contradictory statements which have accumulated on this subject. CHAPTER XVI ZINC, CADMIUM, AND MERCURY These three metals give, like magnesium, oxides RO, which form feebly energetic bases, and like magnesium they are volatile. The volatility increases with the atomic weight. Magnesium can be distilled at a white heat, zinc at a temperature of about 930°, cadmium about 770°, and mercury about 351°. Their oxides, RO, are more easily reducible than magnesia, and mercuric oxide is the most easily reducible. The properties of their salts RX_{2} are very similar to the properties of MgX_{2}. Their solubility, power of forming double and basic salts, and many other qualities are in many respects identical with those of MgX_{2}. The greater or less ease with which they are oxidised, the instability of their compounds, the density of the metals and their compounds, their scarcity in nature, and many other properties gradually change with the increase of atomic weight, as might be expected from the periodicity of the elements. Their principal characteristics, as contrasted with magnesium, find a general expression in the fact that zinc, cadmium, and mercury are heavy metals. _Zinc_ stands nearest to magnesium in atomic weight and in properties. Thus zinc sulphate, or white vitriol, easily crystallises with seven molecules of water, ZnSO_{4},7H_{2}O. It is isomorphous with Epsom salts, and parts with difficulty with the last molecule of water; it forms double salts--for instance, ZnK_{2}(SO_{4})_{2},6H_{2}O--exactly as magnesium sulphate does.[1] _Zinc oxide_, ZnO, is a white powder, almost insoluble in water,[2] like magnesia, from which, however, it is distinguished by its solubility in solutions of sodium and potassium hydroxides.[3] Zinc chloride[4] is decomposed by water, combines with ammonium chloride, potassium chloride, &c., just like magnesium chloride, forms an oxychloride, and also combines with zinc oxide.[4 bis] [1] Zinc sulphate is often obtained as a by-product--for instance, in the action of galvanic batteries containing zinc and sulphuric acid. When the anhydrous salt is heated it forms zinc oxide, sulphurous anhydride, and oxygen. The solubility in 100 parts of water at O° = 43, 20° = 53, 40° = 63-1/2, 60° = 74, 80° = 84-1/2, 100° = 95 parts of anhydrous zinc sulphate--that is to say, it is closely expressed by the formula 43 + 0·52_t_. An admixture of iron is often found in ordinary sulphate of zinc in the form of ferrous sulphate, FeSO_{4}, isomorphous with the zinc sulphate. In order to separate it, chlorine is passed through the solution of the impure salt (when the ferrous salt is converted into ferric), the solution is then boiled, and zinc oxide is afterwards added, which, after some time has elapsed, precipitates all the ferric oxide. Ferric oxide of the form R_{2}O_{3} is displaced by zinc oxide of the form RO. [2] Zinc oxide is obtained both by the combustion and oxidation of zinc, and by the ignition of some of its salts--for instance, those of carbonic and nitric acids; it is likewise precipitated by alkalis from a solution of ZnX_{2} in the form of a gelatinous hydroxide. The oxide produced by roasting zinc blende (by burning in the air, when the sulphur is converted into sulphurous anhydride) contains various impurities. For purification, the oxide is mixed with water, and the sulphurous anhydride formed by roasting the blende is passed through it. Zinc bisulphite, ZnSO_{3},H_{2}SO_{3}, then passes into solution. If a solution of this salt be evaporated, and the residue ignited, zinc oxide, free from many of its impurities, will remain. Zinc oxide is a light white powder, used as a paint instead of _white lead_; the basic salt, corresponding with magnesia alba, is used for the same purpose. V. Kouriloff (1890) by boiling the hydrate of the oxide with a 3 p.c. solution of peroxide of hydrogen obtained Zn_{2}H_{2}O_{4} or the hydrate of the peroxide (= ZnO_{2}ZnH_{2}O_{2} or a compound of 2ZnO with H_{2}O_{2}), which did not part with its oxygen at 100°, but only above 120°. Cadmium gives a similar compound of a yellow colour. Magnesium, although it does form such a compound, does so with great difficulty. [3] For the solution of one part of the oxide 55,400 parts of water are required. Nevertheless, even in such a weak solution, zinc oxide (hydroxide, ZnH_{2}O_{2}) changes the colour of red litmus paper. Zinc oxide is obtained in the wet way by adding an alkali hydroxide to a solution of a zinc salt--for instance: ZnSO_{4} + 2HKO = K_{2}SO_{4} + ZnH_{2}O_{2}. The gelatinous precipitate of zinc hydroxide is _soluble_ in an excess of alkali, which clearly distinguishes it from magnesia. This solubility of zinc hydroxide in alkalis is due to the power of zinc oxide to form a compound, although an unstable one, with alkalis--that is to say, points to the fact that zinc oxide already partly belongs to the intermediate oxides. The oxides of the metals above mentioned (except BeO) do not show this property. The property which metallic zinc itself has of dissolving in caustic alkali with the disengagement of hydrogen (the solution is facilitated by contact with platinum or iron) depends on the formation of such a compound of the oxides of zinc and the alkali metals. The solution of zinc hydroxide, ZnH_{2}O_{2}, in potash (in a strong solution), proceeds when these hydrates are taken in proportion to ZnH_{2}O_{2} + KHO. If such a solution be evaporated to dryness, water extracts only caustic potash from the fused residue. When a solution of zinc hydroxide in strong alkali is mixed with a large mass of water, nearly all the oxide of zinc is precipitated; and, therefore, in weak solutions, a large quantity of the alkali is required to effect solution, which points to the decomposition of the zinc-alkali compounds by water. If strong alcohol be added to a solution of zinc oxide in sodium hydroxide, the crystallo-hydrate, 2Zn(OH)(ONa),7H_{2}O, separates. [4] _Zinc chloride_, ZnCl_{2}, is generally employed in the arts in the form of a solution obtained by dissolving zinc in hydrochloric acid. This solution is used for soldering metals, impregnating wood, &c. The reason why it is thus employed may be understood from its properties. When evaporated it first parts with its water of crystallisation; on being further heated, however, it loses all traces of water, and forms an oily mass of anhydrous salt which solidifies on cooling. This substance melts at 250°, commences to volatilise at about 400°, and boils at 730°. The soldering of metals--that is, the introduction of an easily fusible metal between two contiguous metallic objects--is hindered by any film of oxide upon them; and, as heated metals easily oxidise, they are naturally difficult to solder. Zinc chloride is used to prevent the oxidation. It fuses on being heated, and, covering the metal with an oily coating, prevents contact with the air; but even if any oxide has formed, the free hydrochloric acid generally existing in the zinc chloride solution dissolves it, and in this way the metallic surface of the metals to be soldered is preserved fit for the adhesion of the liquid solder, which, on cooling, binds the objects together. Much zinc chloride is used also for steeping wood (telegraph-posts and railway-sleepers) in order to preserve it from decaying quickly; this preservative action is in all probability mainly due to the poisonous character of zinc salts (corrosive sublimate is still more poisonous, and a still better agent to preserve wood from decay), since decay is due to the action of lower organisms. The specific gravity of solutions containing _p_ per cent. of zinc chloride, ZnCl_{2}, is as follows: _p_ = 10 20 30 40 50 15°/4° = 1·093 1·184 1·293 1·411 1·554 _ds/dt_ = -3 -5 -7 -8 -9 The last line shows the change of specific gravity for 1° in ten-thousandth parts for temperatures near 15°. More accurate determinations of Cheltzoff, personally communicated by him, led him to conclude that solutions of zinc chloride follow the same laws as the solutions of sulphuric acid, which will be considered in Chapter XX.: (1) from H_{2}O to ZnCl_{2},120H_{2}O _s_ = S_{0} + 92·85_p_ + 0·1748_p_^2; (2) from thence to ZnCl_{2},40H_{2}O _s_ = S_{0} + 93·96_p_ - 0·0126_p_^2; (3) thence to ZnCl_{2},25H_{2}O _s_ = 11481·5 + 96·45(_p_ - 15·89) + 0·4567(_p_ - 15·89)^2; (4) thence to ZnCl_{2},10H_{2}O _s_ = 12212·1 + 104·82(_p_ - 23·21) + 0·7992(_p_ - 23·21)^2; (5) thence to _p_ = 65 p.c. _s_ = 14606·3 + 140·96(_p_ - 43·05) + 1·4905(_p_ - 43·05)^2, where _s_ is the specific gravity of the solution at 15°, containing _p_ p.c. of ZnCl_{2} by weight, taking water at 4° = 10000, and where S_{0} = 9991·6 (specific gravity of water at 15°). The compound of zinc chloride with hydrochloric acid has been mentioned in Vol. I. Chapter X. Zinc chloride has a great affinity for water; it is not only soluble in it, but in alcohol, and on being dissolved in water becomes considerably heated, like magnesium and calcium chlorides. Zinc chloride is capable of taking up water, not only in a free state, but also in chemical combination with many substances. Thus, for instance, it is used in organic researches for removing the elements of water from many of the organic compounds. [4 bis] When mixed with zinc oxide it forms, with remarkable ease, a very hard mass of zinc oxychloride, which is applied in the arts; for instance, in painting, to resist the action of water, or for cementing such objects as are destined to remain in water. Zinc oxychloride, ZnCl_{2},3ZnO,2H_{2}O (= Zn_{2}OCl_{2},2ZnH_{2}O_{2}), is also formed from a solution of zinc chloride by the action of a small quantity of ammonia on it after heating the precipitate obtained with the liquid for a considerable time; the admixture of ammonium salts with a mixture of a strong solution of zinc chloride with its oxide makes a similar mass, which does not solidify so rapidly, and is therefore more useful for some purposes. Moisture and cold do not change the hardened mass of oxychloride, and it also resists the action of many acids, and a temperature of 300°, which makes it a useful cement for many purposes. A solution of magnesium chloride with magnesium oxide forms a similar oxychloride. The mass solidifies best when there are equal quantities by weight of zinc in the chloride and oxide, and therefore when it has the composition Zn_{2}OCl_{2} In preparing such a cement, naturally zinc oxide alone may be taken, and the requisite quantity of hydrochloric acid added to it. The capacity of ZnCl_{2} to combine with water, ZnO, and HCl (and also with other metallic chlorides) indicates its property to combine with molecules of other substances, and therefore its compounds with NH_{3}, and especially a compound, ZnCl_{2}2NH_{3}, similar to sal-ammoniac, might be expected (_i.e._ 2NH_{4}Cl, in which H_{2} is replaced by Zn). And indeed it has long been known that ZnCl_{2} absorbs ammonia and gives solid substances capable of dissociating with the disengagement of NH_{3}. Among these compounds Isambert and V. Kouriloff (1894) obtained ZnCl_{2}6NH_{3}, ZnCl_{2}4NH_{3}, ZnCl_{2}2NH_{3}, and ZnCl_{2}NH_{3}. The dissociation tension of the two last-mentioned compounds at 218° is equal to 43·6 mm. and 6·7 mm. CdCl_{2} also forms similar compounds with NH_{3} (Kouriloff, 1894). Zinc, like many heavy metals, is often _found in nature in combination with sulphur_, forming the so-called _zinc blende_,[5] ZnS. It sometimes occurs in large masses, often crystallised in cubes; it is frequently translucent, and has a metallic lustre, although this is not so clearly developed as in many other metallic sulphides with which we shall hereafter become acquainted. The ores of zinc also comprise the carbonate, calamine, and silicate, _siliceous calamine_. [5] This mineral has been given the name of 'mock-ore,' on account of its having the appearance (considerable density, 4·06, &c.) of ordinary metallic ores; it deceived the first miners, because it did not, like other ores, give metal when simply roasted in air and fused with charcoal. The white zinc oxide, formed by burning the vapours of zinc, was also called 'nihil album,' or 'white nothing,' on account of its lightness. [Illustration: FIG. 80.--Distillation of zinc in a crucible placed in a furnace. _o c_, tube along which the vapour passes and condenses.] Metallic zinc (spelter) is most frequently obtained from the ores containing the carbonate[6]--that is, from calamine, which is sometimes found in thick veins: for instance, in Poland, Galicia, in some places on the banks of the Rhine, and in considerable masses in Belgium and England. In Russia beds of zinc ore are met with in Poland and the Caucasus, but the output is small. In Sweden, as early as the fifteenth century, calamine was worked up into an alloy of zinc and copper (brass), and Paracelsus produced zinc from calamine; but the technical production of the metal itself, long ago practised in China, only commenced in Europe in 1807--in Belgium, when the Abbé Donnet discovered that zinc was volatile. From that time the production increased until it is now about 150 million kilograms in Germany alone. [6] It may be here mentioned that by the word _ore_ is meant a hard, heavy substance dug out of the earth, which is used in metallurgical works for obtaining the usual heavy metals long known and used. The natural compounds of sodium, or magnesium, are not called ores, because magnesium and sodium have not been long obtainable in quantity. The heavy metals, those which are easily reduced and do not easily oxidise, are exclusively those which are directly applied in manufactures. Ores either contain the metals themselves (for instance, ores of silver or bismuth), and the metals are then said to be in a native state, or else their sulphur compounds (blende, mock-ore, pyrites--as, for example, galena, PbS; zinc blende, ZnS; copper pyrites, CuFeS) or oxides (as the ores of iron), or salts (calamine, for instance). Zinc is incomparably rarer than magnesium, and is only well known because it is transformed from its ores into a metal which finds direct use in many branches of industry. The reduction of metallic zinc from its ores is based on the fact that zinc oxide[7] is easily reduced by charcoal at a red heat: ZnO + C = Zn + CO. The zinc thus obtained is in a finely divided state and impure, being mixed with other metals reduced with it, but the greater portion is _converted into vapour_, from which it easily passes into a liquid or solid state. The reduction and distillation are carried on in earthenware retorts, filled with a mixture of the divided ore and charcoal. The vapours of zinc and gases formed during the reaction escape by means of a pipe leading downwards, and are led to a chamber where the vapours are cooled. By this means they do not come into contact with the air, because the neck of the retort is filled with gaseous carbonic oxide, and therefore the zinc does not oxidise; otherwise its vapour would burn in the air.[7 bis] The vapours of zinc, entering into the cooling chamber, condense into white zinc powder or zinc dust. When the neck of the retort is heated the zinc is obtained in a liquid state, and is cast into plates, in which form it is generally sold. [7] Ores, when extracted from the earth by the miners, are often enriched by sorting, washing, and other mechanical operations. The sulphurous ores (and likewise others) are then generally roasted. Roasting an ore means heating it to redness in air. The sulphur then burns, and passes off in the form of sulphurous anhydride, SO_{2}, and the metal oxidises. The roasting is carried on in order to obtain an oxide instead of a sulphur compound, the oxide being reducible by charcoal. These methods, introduced ages ago, are met with in nearly all metallurgical works for practically all ores. For this reason the preparatory treatment of zinc blende furnishes zinc oxide: this is already contained in calamine. [7 bis] with very impure ores, especially such as contain lead (PbS often accompanies zinc), the vapour of the reduced zinc is allowed to pass directly into the air. It burns and gives ZnO, which is used as a pigment. Commercial zinc is generally impure, containing a mixture of lead, particles of carbon, iron, and other metals carried over with the vapours, although they are not volatile at a temperature approaching 1000°. If it be required to obtain pure zinc from the commercial article, it is subjected to a further distillation in a crucible with a pipe passing through the bottom, the vapours formed by the heated zinc only having exit through the pipe cemented into the bottom of the crucible. Passing through this pipe, the vapours condense to a liquid, which is collected in a receiver. Zinc thus purified is generally re-melted and cast into rods, and in this form is often used for physical and chemical researches where a pure article is required.[8] [8] This zinc, although homogeneous, still contains certain impurities, to remove which it is necessary to prepare some salt of zinc in a pure state and transform it into carbonate, which latter is then distilled with charcoal; and, as thin sheets of zinc can only be obtained from very pure metal, they are frequently made use of in cases where pure zinc is required. In order to remove the arsenic from zinc, it was proposed to melt it and mix it with anhydrous magnesium chloride, by which means vapours of zinc chloride and arsenic chloride are formed. Perfectly pure zinc is made (V. Meyer and others) by decomposing, by means of the galvanic current, a solution of zinc sulphate to which an excess of ammonia has been added. The zinc used for Marsh's arsenic test (Chapter XIX.) is purified from As by fusing it with KNO_{3} and then with ZnCl_{2}. Metallic zinc has a bluish-white colour; its lustre, compared with many other metals, is insignificant. When cast it exhibits a crystalline structure. Its specific gravity is about 7--that is, varies from 6·8 to 7·2, according to the degree of compression (by forging, rolling, &c.) to which it has been subjected. It is very ductile, considering its hardness. For this reason it chokes up files when being worked. Its malleability is considerable when pure, but in the ordinary impure condition in which it is sold, it is impossible to roll it at the ordinary temperature, as it easily breaks. At a temperature of 100°, however, it easily undergoes such operations, and can then be drawn into wire or rolled into sheets. If heated further it again becomes brittle, and at 200° may be even crushed into powder, so completely does it lose its molecular cohesion. It melts at 418°, and distils at 930°. Zinc does not undergo any change in the atmosphere. Even in very damp air it only becomes slowly coated with a very thin white coating of oxide. For this reason it is available for all objects which are only in contact with air. Therefore sheet zinc may be used for roofing and many other purposes.[9] This great unchangeability of zinc in the air shows its slight energy with regard to oxygen compared with the metals already mentioned, which are capable of reducing zinc from solutions. But zinc plays this part with regard to the remaining metals--for example, it reduces salts of lead, copper, mercury, &c. Although zinc is an almost unoxidisable metal at the ordinary temperature, it burns in the air on being heated, particularly when in the form of shavings or in the condition of vapour. At the ordinary temperature zinc does not decompose water--at any rate, if the metal be in a dense mass. But even at a temperature of 100° zinc begins little by little to decompose water; it easily displaces the hydrogen of acids at the ordinary temperature, and of alkalis on being heated. [9] Cornices and other architectural ornaments, remarkable for their lightness and beauty, are stamped out of sheet zinc. Zinc-roofing does not require painting, but it melts during a conflagration, and even burns at a strong heat. Many iron vessels, &c., are covered with zinc ('galvanised') in order to prevent them from rusting. In this respect the action of zinc varies a great deal with the degree of its purity. Weak sulphuric acid (corresponding with the composition H_{2}SO_{4},8H_{2}O) at the ordinary temperature does not act at all on chemically pure zinc, and even a stronger solution acts very slowly. If the temperature be raised, and particularly if the zinc be previously slightly heated, so as to cover the surface with a film of oxide, chemically pure zinc acts on sulphuric acid. Thus, for example, one cubic centimetre of zinc in sulphuric acid having a composition H_{2}SO_{4},6H_{2}O at the ordinary temperature in two hours only dissolves to the extent of 0·018 gram, and at a temperature of 100° about 3·5 grams. If we compare this slow action with that rapid evolution of hydrogen which occurs in the case of commercial zinc, we see that the influence of those impurities in the zinc is very great. Every particle of charcoal or iron introduced into the mass of the zinc, and likewise the connection of the zinc with a piece of another electro-negative metal, assists such a dissolution. The slowness of the action of sulphuric acid on pure zinc (and likewise on amalgamated zinc) may also be explained by the fact that a layer of hydrogen[10] collects on the surface of the metal, preventing contact between the acid and the metal.[10 bis] [10] Veeren (1891) proved this by simple experiments, finding that in vacuo the solution proceeds far more rapidly for both pure and commercial zinc, and still more rapidly in the presence of oxidising agents (which absorb the hydrogen) like CrO_{3} and H_{2}O_{2}. [10 bis] The addition of cupric sulphate, or, better still, a few drops of platinic chloride (the metals become reduced), to the sulphuric acid greatly accelerates the evolution of the hydrogen, because in this case, as with commercial zinc, galvanic couples are formed locally by the copper or platinum and the zinc, under the influence of which the zinc rapidly dissolves. The action of acids on metallic zinc of various degrees of purity has been the subject of many investigations, particularly important with reference to the application of zinc in galvanic batteries, whilst some investigations have direct significance for chemical mechanics, although from many points of view the matter is not clear. I consider it useful to mention certain of these investigations. Calvert and Johnson made the following series of observations on the action of sulphuric acid of various degrees of concentration on 2 grams of pure zinc during two hours. In the cold the concentrated acid, H_{2}SO_{4}, does not act, H_{2}SO_{4},2H_{2}O dissolves about 0·002 gram, but principally forms hydrogen sulphide, which is obtained also when the dilution reaches H_{2}SO_{4},7H_{2}O, when 0·035 gram of zinc is dissolved. When largely diluted with water, pure hydrogen begins to be disengaged. H_{2}SO_{4},2H_{2}O at 130° gives a mixture of hydrogen sulphide and sulphurous anhydride dissolving 0·156 gram of zinc. Bouchardat showed that if in a vessel made of glass or sulphur dilute sulphuric acid acting on a piece of zinc liberates one part of hydrogen, then the same acid with the same piece of zinc in the same time will liberate 4 parts of hydrogen if the vessel be made of tin--that is, zinc forms a galvanic couple with tin; in a leaden vessel 9 parts of hydrogen are set free, with a vessel of antimony or bismuth 13 parts, silver or platinum 38 parts, copper 50 parts, iron 43 parts. If a salt of platinum be added to the dilute sulphuric acid (1 part of acid and 12 parts of water), Millon determined that the rapidity of the action on the zinc is increased 149 times, and by the addition of copper sulphate is rendered 45 times greater than the action of pure sulphuric acid. The salts which are added are reduced to metals by the zinc, their contact serving to promote the reaction because they form local galvanic currents. According to the observations of Cailletet, if, at the ordinary pressure, sulphuric acid with zinc liberates 100 parts of hydrogen, then with a pressure of 60 atmospheres 47 parts will be liberated and 1 part at a pressure of 120 atmospheres. With a reduced pressure under the receiver of an air-pump 168 parts are liberated. Helmholtz showed that a reduced pressure also exercises its influence on galvanic elements. Debray, Löwel, and others showed that zinc liberates hydrogen and forms basic salts and zinc oxide with solutions of many salts--for instance, MCl_{_n_}, aluminium sulphate, and alum, Sodium and potassium carbonates scarcely act, because they form carbonates. The salts of ammonia act more strongly than the salts of potassium and sodium; the zinc remains bright. It is evident that this action is founded on the formation of double salts and basic salts. The variation with concentration in the rate of the action of sulphuric acid on zinc (containing impurities) under otherwise uniform conditions is in evident connection with the electrical conductivity of the solution and its viscosity, although, when largely diluted, the action is almost proportional to the amount of acid in a known volume of the solution. Forging, casting the molten metal, and similar mechanical influences change the density and hardness of zinc, and also strongly influence its power of liberating hydrogen from acids. Kayander showed (1881) that when magnesium is submitted to the action of acids: (_a_) the action depends, not on the nature of the acid, but on its basicity; (_b_) the increase of the action is more rapid than the growth of the concentration; and (_c_) there is a decrease of action with the increase of the coefficient of internal friction and electrical conductivity. Spring and Aubel (1887) measured the volume of hydrogen disengaged by an alloy of zinc and a small quantity of lead (0·6 p.c.), because the action of acids is then uniform. In order to deal with a known surface, spheres were taken (9·5 millimetres diameter) and cylinders (17 mm. dia.), the sides of which were covered with wax in order to limit the action to the end surfaces. During the commencement of the action of a definite quantity of acid the rapidity increases, attains a maximum, and then declines as the acid becomes exhausted. The results for 5, 10, and 15 per cent. of hydrochloric acid are given below. H denotes the number of cubic centimetres of hydrogen, D the time in seconds elapsing after the zinc spheres have been plunged into the acid. At 15° were obtained: H = 50 100 200 400 600 800 1000 5 p.c. D = 714 1152 1755 2731 3908 6234 15462 10 p.c. D = 301 455 649 995 1573 2746 6748 15 p.c. D = 106 151 233 440 826 1604 4289 At 35°: 5 p.c. D = 462 705 1058 1700 2525 4132 8499 10 p.c. D = 96 148 239 460 835 1594 3735 15 p.c. D = 44 64 112 255 505 1011 2457 At 55°: 5 p.c. D = 178 276 408 699 1164 2105 5093 10 p.c. D = 34 60 113 258 491 970 2457 15 p.c. D = 24 35 58 136 239 610 1593 In consequence of the complex character of the phenomenon, the authors themselves do not consider their determinations as being conclusive, and only give them a relative significance; and in this connection it is remarkable that hydrobromic acid under similar conditions (with an equivalent strength) gives a greater (from 2 to 5 times) rapidity of action than hydrochloric acid, but sulphuric acid a far smaller velocity (nearly 25 times smaller). It is also remarkable that during the reaction the metal becomes much more heated than the acid. It may be mentioned that zinc dust and zinc itself, when heated with hydrated lime and similar hydrates, disengages hydrogen: this method has even been proposed for obtaining hydrogen for filling war balloons. The action of zinc on acids, and the consequent formation of zinc salts, interferes with its application in many cases, particularly for the preservation of liquids either containing or capable of developing acid. For this reason zinc vessels ought not to be used for the preparation or preservation of food, as this often contains acids which form poisonous salts with the zinc. Even ordinary water, containing carbonic acid, slowly attacks zinc. Finely divided zinc, or _zinc dust_, obtained in the distillation of the metal when the receiver is not heated up to the melting point, on account of its presenting a large surface of contact and containing foreign matter (particularly zinc oxide), has in the highest degree the property of decomposing acids, and even water, which it easily decomposes, particularly if slightly heated. On this account zinc dust is often used in laboratories and factories as a reducing agent. A similar influence of the finely divided state is also noticed in other metals--for instance, copper and silver--which again shows the close connection between chemical and physico-mechanical phenomena. We must first of all turn to this close connection for an explanation of the widely spread application of zinc in galvanic batteries, where the chemical (latent, potential) energy of the acting substances is transformed into (evident, kinetic) galvanic energy, and through this latter into heat, light, or mechanical work. Hermann and Stromeyer, in 1819, showed that _cadmium_ is almost always found with zinc, and in many respects resembles it. When distilled the cadmium volatilises sooner, because it has a lower boiling point. Sometimes the zinc dust obtained by the first distillation of zinc contains as much as 5 per cent. of cadmium. When zinc blende, containing cadmium, is roasted, the zinc passes into the state of oxide, and the cadmium sulphide in the ore oxidises into cadmium sulphate, CdSO_{4}, which resists tolerably well the action of heat; therefore if roasted zinc blende be washed with water, a solution of cadmium sulphate will be obtained, from which it is very easy to prepare metallic cadmium. Hydrogen sulphide may be used for separating cadmium from its solutions; it gives _a yellow precipitate of cadmium sulphide_, CdS (according to the equation CdSO_{4} + H_{2}S = H_{2}SO_{4} + CdS),[11] which, on account of its characteristic colour, is used as a pigment.[11 bis] Cadmium sulphide, when strongly heated in air, leaves cadmium oxide, from which the metal may be obtained in precisely the same way as in the case of zinc. [11] It may be here remarked that sulphate of zinc (especially in the presence of mineral acids) does not give a precipitate of sulphide of zinc, or is only slightly precipitated by sulphuretted hydrogen. [11 bis] Sulphide of cadmium appears in two varieties of a similar chemical but different physical character: one is of a lemon colour, and the other bright red. Kloboukoff (1890) studied the physical properties of these varieties more closely. The sp. gr. of the former is 3·906, and of the latter 4·513. They belong to different crystallographic systems. The first variety may be converted into the second by friction or pressure, but the second cannot be converted into the first variety by these means. Cadmium is a white metal, and when freshly cut is almost as white and lustrous as tin. It is so soft that it may be easily cut with a knife, and so malleable that it can be easily drawn into wire, rolled into sheets, &c. Its specific gravity is 8·67, melting point 320°, boiling point 770°; its vapours burn, forming a brown powder of the oxide.[12] Next to mercury it is the most volatile metal; hence Deville determined the density of its vapours compared with hydrogen, and found it to be equal to 57·1; therefore the molecule contains _one atom_ whose weight = 112. V. Meyer found the like for zinc; the molecule of mercury also contains one atom. [12] Amongst the compounds of cadmium very closely allied to the compounds of zinc, we must mention _cadmium iodide_, CdI_{2}, which is used in medicine and photography. This salt crystallises very well: it is prepared by the direct action of iodine, mixed with water, on metallic cadmium. One part of cadmium iodide at 20° requires for its solution 1·08 part of water. It may be remarked that cadmium chloride at the same temperature requires 0·71 part of water to dissolve it, so that the iodine compound of this metal is less soluble than the chloride, whilst the reverse relation holds in the case of the corresponding compounds of the alkali or alkaline earthy metals. Cadmium sulphate crystallises well, and has the composition 3CdSO_{4},8H_{2}O, thus differing from zinc sulphate. Cadmium oxide is soluble, although sparingly, in alkalis, but in the presence of tartaric and certain other acids the alkaline solution of cadmium oxide does not change when boiled, whilst a _diluted_ solution in that case deposits cadmium oxide: this may also serve for separating zinc compounds from those of cadmium. Cadmium is precipitated from its salts by zinc, which fact may also be taken advantage of for separating cadmium; for this reason, in an alloy of zinc and cadmium, acids first of all extract the zinc. Cadmium is in all respects less energetic than zinc. Thus, for instance, it decomposes water with difficulty, and this only when strongly heated. It even acts but slowly on acids, but then displaces hydrogen from them. It is necessary here to call attention to the fact that for alkali and alkaline earthy metals (of the even series) the highest atomic weight determines the greatest energy; but cadmium (of the uneven series), whilst having a larger atomic weight than zinc, is less energetic. The salts of cadmium are colourless, like those of zinc. De Schulten obtained a crystalline oxychloride, Cd(OH)Cl by heating marble with a solution of cadmium chloride in a sealed tube at 200°. _Mercury_ resembles zinc and cadmium in many respects, but presents that distinction from them which is always noticed in all the heaviest metals (with regard to atomic weight and density) compared with the lighter ones--namely, that it oxidises with more difficulty, and its compounds are more easily decomposed.[12 bis] Besides compounds of the usual type RX_{2}, it also gives those of the lower type, RX, which are unknown for zinc and cadmium.[13] Mercury therefore gives salts of the composition HgX (mercurous salts) and HgX_{2} (mercuric salts), the oxides having the formulæ Hg_{2}O and HgO respectively. [12 bis] According to its atomic weight, mercury follows gold in the periodic system, just as cadmium follows silver and zinc follows copper:-- Ni = 59 Cu = 63 Zn = 65 Pd = 106 Ag = 108 Cd = 112 Pt = 196 Au = 198 Hg = 200 Eventually we shall see the near relation of platinum, palladium, and nickel, and also of gold, silver, and copper, but we will now point out the parallelism between these three groups. The relation between the physical and also chemical properties is here strikingly similar. Nickel, palladium, and platinum are very difficult to fuse (far more so than iron, ruthenium, and osmium, which stand before them). Copper, silver, and gold melt far more easily in a strong heat than the three preceding metals, and zinc, cadmium, and mercury melt still more easily. Nickel, palladium, and platinum are very slightly volatile; copper, silver, and gold are more volatile; and zinc, cadmium, and mercury are among the most volatile metals. Zinc oxidises more easily than copper, and is reduced with more difficulty, and the same is true for mercury as compared with gold. These properties for cadmium and silver are intermediate in the respective groups. Relations of this kind clearly show the nature of the periodic law. [13] Thus thallium, lead, and bismuth, following mercury according to their atomic weights, form, besides compounds of the highest types, TlX_{3}, PbX_{4}, and BiX_{5}, also the lower ones TlX, PbX_{2}, and BiX_{3}. Mercury is found _in nature_ almost exclusively in combination with sulphur (like zinc and cadmium, but is still rarer than them) in the form known as cinnabar, HgS (Chapter XX., Note 29). It is far more rarely met with in the native or metallic condition, and this in all probability has been derived from cinnabar. Mercury ore is found only in a few places--namely, in Spain (in Almaden), in Idria, Japan, Peru, and California. About the year 1880 Minenkoff discovered a rich bed of cinnabar in the Bahmout district (near the station of Nikitovka), in the Government of Ekaterinoslav, so that now Russia even exports mercury to other countries. Cinnabar is now being worked in Daghestan in the Caucasus. Mercury ores are easily reduced to metallic mercury, because the combination between the metal and the sulphur is one of but little stability. Oxygen, iron, lime, and many other substances, when heated, easily destroy the combination. If iron is heated with cinnabar, iron sulphide is formed; if cinnabar is heated with lime, mercury and calcium sulphide and sulphate are formed, 4HgS + 4CaO = 4Hg + 3CaS + CaSO_{4}. On being heated in the air, or roasted, the sulphur burns, oxidises, forming sulphurous anhydride, and vapours of metallic mercury are formed. Mercury is more easily distilled than all other metals, its boiling point being about 351°, and therefore its separation from natural admixtures, decomposed by one of the above-mentioned methods, is effected at the expense of a comparatively small amount of heat. The mixture of mercury vapour, air, and products of combustion obtained is cooled in tubes (by water or air), and the mercury condenses as liquid metal.[14] [14] During the condensation of the vapours of mercury in works, a part forms a black mass of finely-divided particles, which gives metallic mercury when worked up in centrifugal machines, or on pressure, or on re-distillation. In mercury we observe a tendency to easily split up into the finest drops, which are difficult to unite into a dense mass. It is sufficient to shake up mercury with nitric and sulphuric acids in order to produce such a mercury _powder_. The mercury separated (for instance, reduced by substances like sulphurous anhydride) from solutions, forms such a powder. According to the experiments of Nernst, this disintegrated mercury when entering into reactions develops more heat than the dense liquid metal--that is to say, the work of disintegration reappears in the form of heat. This example is instructive in considering thermochemical deductions. Mercury, as everybody knows, is a liquid metal at the ordinary temperature. In its lustre and whiteness it resembles silver.[15] At -39° mercury is transformed into a malleable crystalline metal; at 0° its specific gravity is 13·596, and in the solid state at -40° it is 14·39.[16] Mercury does not change in the air--that is to say, it does not oxidise at the ordinary temperature--but at a temperature approaching the boiling-point, as was stated in the Introduction, it oxidises, forming mercuric oxide. Both metallic mercury and its compounds in general produce salivation, trembling of the hands, and other unhealthy symptoms which are found in the workmen exposed to the influence of mercurial vapours or the dust of its compounds. [15] Mercury may sometimes be obtained in a perfectly pure state from works (in iron bottles holding about 35 kilos), but after being used in laboratories (for baths, calibration, &c.) it contains impurities. It may be purified mechanically in the following way: a paper filter with a fine hole (pricked with a needle) is placed in a glass funnel and mercury is poured into it, which slowly trickles through the hole, leaving the impurities upon the filter. Sometimes it is squeezed through chamois leather or through a block of wood (as in the well-known experiment with the air-pump). It may be purified from many metals by contact with dilute nitric acid, if small drops of mercury are allowed to pass through a long column of it (from the fine end of a funnel); or by shaking it up with sulphuric acid in air. Mercury may be purified by the action of an electric current, if it be covered with a solution of HgNO_{3}. But the complete purification of mercury for barometers and thermometers can only be attained by distillation, best in a vacuum (the vapour-tension of mercury is given in Chapter II., Note 27). For this purpose Weinhold's apparatus is most often used. The principle of this apparatus is very ingenious, the distillation being effected in a Torricellian vacuum continuously supplied with fresh mercury, whilst the condensed mercury is continuously removed. This process of distillation requires very little attention, and gives about one kilo of pure mercury per hour. [16] If the volume of _liquid_ mercury at 0° be taken as 1000000, then, according to the determinations of Regnault (recalculated by me in 1875), at _t_ it will be 1000000 + 180·1_t_ + 0·02_t_^2. As many of the compounds of mercury decompose on being heated--for instance, the oxide or carbonate[17]--and as zinc, cadmium, copper, iron, and other metals separate mercury from its salts,[18] it is evident that mercury has less chemical energy than the metals already described, even than zinc and cadmium. Nitric acid, when acting on _an excess_ of mercury at the ordinary temperature, gives mercurous nitrate, HgNO_{3}.[19] The same acid, under the influence of heat and when in excess (nitric oxide being liberated), forms mercuric nitrate, Hg(NO_{3})_{2}. This,[20] both in its composition and properties, resembles the salts of zinc and cadmium. Dilute sulphuric acid does not act on mercury, but strong sulphuric acid dissolves it, with evolution of _sulphurous anhydride_ (not hydrogen), and on being slightly heated with an excess of mercury it forms the sparingly soluble mercurous sulphate, Hg_{2}SO_{4}; but if mercury be strongly heated with an excess of the acid, the mercuric salt, HgSO_{4},[21] is formed. Alkalis do not act on mercury, but the non-metals chlorine, bromine, sulphur, and phosphorus easily combine with it. They form, like the acids, two series of compounds, HgX and HgX_{2}. The oxygen compound of the first series is the suboxide of mercury, or mercurous oxide, Hg_{2}O, and of the second order the oxide HgO, mercuric oxide. The chlorine compound corresponding with the suboxide is HgCl (calomel), and with the oxide HgCl_{2} (corrosive sublimate or mercuric chloride). In the compounds HgX, mercury resembles the metals of the first group, and more especially silver. In the mercuric compounds there is an evident resemblance to those of magnesium, cadmium, &c. Here the atom of mercury is bivalent, as in the type RX_{2}.[22] Every soluble mercurous compound (corresponding with the type of the suboxide of mercury), HgX, forms a white precipitate of calomel, HgCl, with hydrochloric acid or a metallic chloride, because HgCl is very slightly soluble in water, HgX + MCl = HgCl + MX. In soluble mercuric compounds, HgX_{2}, hydrochloric acid and metallic chlorides do not form a precipitate, because corrosive sublimate, HgCl_{2}, is soluble in water. Alkali hydroxides precipitate the yellow mercuric oxide from a solution of HgX_{2}, and the black mercurous oxide from HgX. Potassium iodide forms a dirty greenish precipitate, HgI, with mercurous salts, HgX, and a red precipitate, HgI_{2}, with the mercuric salts, HgX_{2}. These reactions distinguish the mercuric from the mercurous salts, which latter represent the transition from the mercuric salts to mercury itself, 2HgX = Hg + HgX_{2}. The salts, HgX, as well as HgX_{2}, are reduced by nascent hydrogen (_e.g._ from Zn + H_{2}SO_{4}), by such metals as zinc and copper, and also by many reducing agents--for example, hypophosphorous acid, the lowest grade of oxidation of phosphorus, by sulphurous anhydride, stannous chloride, &c. Under the action of these reagents the mercuric salts are first transformed into the mercurous salts, and the latter are then reduced to metallic mercury. This reaction is so delicate that it serves to detect the smallest quantity of mercury; for instance, in cases of poisoning, the mercury is detected by immersing a copper plate in the solution to be tested, the mercury being then deposited upon it (more readily on passing a galvanic current). The copper plate, on being rubbed, shows a silvery white colour; on being heated, it yields vapours of mercury, and then again assumes its original red colour (if it does not oxidise). The mercurous compounds, HgX, under the action of oxidising agents, even air, pass into mercuric compounds, especially in the presence of acids (otherwise a basic salt is produced), 2HgX + 2HX + O = 2HgX_{2} + H_{2}O; but the mercuric compounds, when in contact with mercury, change more or less readily, and turn into mercurous compounds, HgX_{2} + Hg = 2HgX. For this reason, in order to preserve solutions of mercurous salts, a little mercury is generally added to them. [17] All salts of mercury, when mixed with sodium carbonate and heated, give mercurous or mercuric carbonates; these decompose on being heated, forming carbonic anhydride, oxygen, and vapours of mercury. [18] Spring (1888) showed that, solid dry HgCl is gradually decomposed in contact with metallic copper. According to the determinations of Thomsen, the formation of a gram of mercurial compounds from their elements develops the following amounts of heat (in thousands of units): Hg_{2} + O, 42; Hg + O, 31; Hg + S, 17; Hg + Cl, 41; Hg + Br, 34; Hg + I, 24; Hg + Cl_{2}, 63; Hg + Br_{2}, 51; Hg + I_{2}, 34; Hg + C_{2}N_{2}, 19. These numbers are less than the corresponding ones for potassium, sodium, calcium, barium, and for zinc and cadmium--for instance, Zn + O, 85; Zn + Cl_{2}, 97; Zn + Br_{2}, 76; Zn + I_{2}, 49; Cd + Cl_{2}, 93; Cd + Br_{2}, 75; Cd + I_{2}, 49. [19] This salt easily forms the crystallo-hydrate HgNO_{3},H_{2}O, corresponding with ortho-nitric acid, H_{3}NO_{4} (the terms ortho-, pyro-, and meta-acids are explained in the chapter on Phosphorus), with the substitution of Hg for H. In an aqueous solution this salt can only be preserved in the presence of free mercury, otherwise it forms basic salts, which will be mentioned hereafter (Chapter VI., Note 59). [20] Mercuric nitrate, Hg(NO_{3})_{2},8H_{2}O, crystallises from a concentrated solution of mercury in an excess of boiling nitric acid. Water decomposes this salt; at the ordinary temperature crystals of a basic salt of the composition Hg(NO_{3})_{2},HgO,2H_{2}O are formed, and with an excess of water the insoluble yellow basic salt Hg(NO_{3})_{2},H_{2}O,2HgO. These three salts correspond with the type of ortho-nitric acid, (H_{3}NO_{4})_{2}, in which mercury is substituted for 1, 2 and 3 times H_{2}. As all these salts still contain water, it is possible that they correspond with the tetrahydrate = N_{2}O_{5} + 4H_{2}O = N_{2}O(OH)_{8} if ortho-nitric acid = N_{2}O_{5} + 3H_{2}O = 2NO(OH)_{3}. [21] To obtain the mercuric salt a large excess of strong sulphuric acid must be taken and strongly heated. With a small quantity of water colourless crystals of HgSO_{4},H_{2}O may be obtained. An excess of water, especially when heated, forms the basic salt (as in Note 20), HgSO_{4},2HgO, which corresponds with trihydrated sulphuric acid, SO_{3} + 3H_{2}O = S(OH)_{6}, with the substitution of H_{6} by 3Hg, which in mercuric salts is equivalent to H_{6}. Le Chatelier (1888) gives the following ratio between the amounts of equivalents per litre: HgSO_{4} 0·318 0·890 1·80 2·02 SO_{3} 0·752 1·42 2·10 2·40 --that is, the relative amount of free acid decreases as the strength of the solution increases. [22] The question of the molecular weight of calomel--that is, whether the mercury in the salts of the suboxide is monatomic or diatomic--long occupied the minds of chemists, although it is not of very great importance. It is only recently (1894) that this question can be considered as answered, thanks to the researches of V. Meyer and Harris, in favour of diatomicity--that is, that calomel is analogous to peroxide of hydrogen and contains Hg_{2}Cl_{2} (like O_{2}H_{2}) in its molecule if corrosive sublimate contains HgCl_{2} (like water OH_{2}). As a matter of fact, direct experiment gives the vapour density of calomel as about 118--that is, indicates that its molecule contains HgCl, whilst the molecule of the sublimate, judging also by the vapour density (nearly 136), contains HgCl_{2}; it might therefore be concluded that the mercury in the suboxide is not only monovalent (corresponding to H) but also monatomic, whilst in the oxide it is divalent and diatomic. Instances of a variable atomicity, as shown by the vapour density, are known in N_{2}O, NO, and NH_{3}, CO and CO_{2}, PCl_{3} and PCl_{5}, and it might therefore be supposed that the present was a similar instance. But there are also instances of a variable equivalency which do not correspond to a variation of atomicity--for example, OH_{2} (water) and OH (peroxide of hydrogen), CH_{4} (methane), C_{2}H_{5} (ethyl), and CH_{2} (ethylene), &c. Here, according to the law of substitution, the residues of OH_{2} and CH_{4} combine together and give molecules; OHOH = O_{2}H_{2} (peroxide of hydrogen) and CH_{3}CH_{3} = C_{2}H_{6} (ethane), &c. The same may be assumed also to be the relation of calomel to sublimate; the residue HgCl, which is combined with Cl in sublimate, corresponds to HgCl_{2}, and in calomel it may be supposed that this residue is combined with itself, forming the molecule Hg_{2}Cl_{2}. On this view of the composition of the molecule of calomel it would follow that in the state of vapour it breaks up into two molecules, HgCl_{2} and Hg, when the vapour density would be about 118 (because that of sublimate is about 136 and that of mercury about 100), and that in cooling this mixture (like a mixture of HCl and NH_{3}) again gives Hg_{2}Cl_{2}. It was therefore necessary to prove that calomel is decomposed in the state of vapour. This was not effected for a long time, although Odling, as far back as the thirties, showed that gold becomes amalgamated (_i.e._ absorbs metallic mercury) in the vapour of calomel, but not in the vapour of sublimate. Recently, however, V. Meyer and Harris (1894) have shown that a greater amount of the vapour of mercury than of calomel passes (at about 465°) through a porous clay cell, containing calomel. This proves that the vapour of calomel contains a mixture of the vapours of Hg and HgCl_{2}, as would follow from the second hypothesis. Moreover, on introducing a heated piece of KHO into the vapour of calomel, Meyer observed the formation, not of suboxide (black), but of oxide of mercury (yellow). Therefore the molecular formula of calomel must be taken as Hg_{2}Cl_{2} (and not HgCl). The lowest oxygen compound of mercury--that is, _mercurous oxide_, Hg_{2}O--does not seem to exist, for the substance precipitated in the form of a black mass by the action of alkalis on a solution of mercurous salts gradually separates on keeping into the yellow mercuric oxide and metallic mercury, as does also a simple mechanical mixture of oxide, HgO, with mercury (Guibourt, Barfoed). The other compound of mercury with oxygen is already known to us as _mercuric oxide_, HgO, obtained in the form of a red crystalline substance by the oxidation of mercury in the air, and precipitated as a yellow powder by the action of sodium hydroxide on solutions of salts of the type HgX_{2}. In this case it is amorphous and more amenable to the action of various reagents (Chap. XI., Note 32) than when it is in the crystalline state. Indeed, on trituration, the red oxide is changed into a powder of a yellow colour. It is very sparingly soluble in water, and forms an alkaline solution which precipitates magnesia from the solution of its salts. Mercury combines directly with chlorine, and the first product of combination is _calomel_ or _mercurous chloride_, Hg_{2}Cl_{2}. This is obtained, as above stated, in the form of a white precipitate by mixing solutions of mercurous salts with hydrochloric acid or with metallic chlorides. A precipitate of calomel is also obtained by reducing a boiling aqueous solution of corrosive sublimate, HgCl_{2}, with sulphurous anhydride. It is likewise produced by heating corrosive sublimate with mercury.[22 bis] Calomel may be distilled (although in so doing it decomposes and recombines on cooling from a state of vapour); its vapour density equals 118 compared with hydrogen (= 1) (_see_ Note 23). In the solid state its specific gravity is 7·0; it crystallises in rhombic prisms, is colourless, but has a yellowish tint, turns brown from the action of light, and when boiled with hydrochloric acid decomposes into mercury and corrosive sublimate. It is used as a strong purgative. _Corrosive sublimate or mercuric chloride_, HgCl_{2}, can be obtained from or converted into calomel by many methods.[23] An excess of chlorine (for instance, _aqua regia_) converts calomel and also mercury into corrosive sublimate. It owes its name corrosive sublimate to its volatility, and, in medicine up to the present day, it is termed _Mercurius sublimatus seu corrosivus_. The vapour density, compared with hydrogen (= 1) is 135; therefore its molecule contains HgCl_{2}. It forms colourless prismatic crystals of the rhombic system, boils at 307°, and is soluble in alcohol. It is usually prepared by subliming a mixture of mercuric sulphate with common salt, HgSO_{4} + 2NaCl = Na_{2}SO_{4} + HgCl_{2}. Corrosive sublimate combines with mercuric oxide, forming an oxychloride or basic salt,[23 bis] of the composition HgCl_{2},2HgO (magnesium and zinc form similar compounds). This compound is obtained by mixing a solution of corrosive sublimate with mercuric oxide or with a solution of sodium bicarbonate. In general, with both mercurous and mercuric salts, there is a marked tendency to form basic salts.[24] [22 bis] Calomel (in Japanese 'Keyfun') has been prepared in Japan (and China) for many centuries, by heating mercury in clay crucibles with sea salt, which contains MgCl_{2} and gives HCl. The vapour of the mercury reacts with this HCl and the oxygen of the air and forms calomel: 2Hg + 2HCl + O = Hg_{2}Cl_{2} + H_{2}O. The calomel collects on the lid of the crucible in the form of a sublimate (Divers, 1894). [23] HgCl_{2} is partially converted into calomel even in the act of dissolving in ordinary water, especially under the action of light. [23 bis] As feebly energetic bases (for instance, the oxides MgO, ZnO, PbO, CuO, Al_{2}O_{3}, Bi_{2}O_{3}, &c.), mercuric oxide (_see_ Notes 20, 21) and mercurous oxide easily give basic salts, which are usually directly formed by the action of water on the normal salt, according to the general equation (for mercuric compounds, RX_{2}): _n_RX_{2} + _m_H_{2}O = 2_m_HX + (_n_-_m_)RX_{2}_m_RO neutral salt water acid basic salt or else are produced directly from the normal salt and the oxide or its hydroxide. Thus mercurous nitrate, when treated with water, forms basic salts of the composition 6(HgNO_{3}),Hg_{2}O,H_{2}O, 2(HgNO_{3}),Hg_{2}O,H_{2}O, and 3(HgNO_{3}),Hg_{2}O,H_{2}O, the first two of which crystallise well. Naturally it is possible either to refer similar salts to the type of hydrates--for instance, the second salt to the hydrate N_{2}O_{5},4H_{2}O--or to view it as a compound, HgNO_{3},HgHO, but our present knowledge of basic salts is not sufficiently complete to admit of generalisations. However, it is already possible to view the subject in the following aspects: (1) basic salts are principally formed from feeble bases; (2) certain metals (mentioned above) form them with particular ease, so that one of the causes of the formation of many basic salts must depend on the property of the metal itself; (3) those bases which readily form basic salts as a rule also readily form double salts; (4) in the formation of basic salts, as also everywhere in chemistry, where sufficient facts have accumulated, we clearly see the conditions of equally balanced heterogeneous systems, such as we saw, for instance, in the formation of double salts, crystallo-hydrates, &c. The mercuric salts often form double salts (confirming the third thesis), and mercuric chloride easily combines with ammonia, forming Hg(NH_{4})_{2}Cl_{4}, or in general HgCl_{2}_n_MCl. If a mixture of mercurous and potassium sulphates be dissolved in dilute sulphuric acid, the solution easily yields large colourless crystals of a double salt of the composition K_{2}SO_{4},3HgSO_{4},2H_{2}O. Boullay obtained crystalline compounds of mercuric chloride with hydrochloric acid, and mercuric iodide with hydriodic acid; and Thomsen describes the compound HgBr_{2},HBr,4H_{2}O as a well-crystallised salt, melting at 13°, and having, in a molten state, a specific gravity 3·17 and a high index of refraction. Moreover, the capacity of salts for forming basic compounds has been considerably cleared up since the investigation (by Würtz, Lorenz, and others) of glycol, C_{2}H_{4}(OH)_{2} (and of polyatomic alcohols resembling it), because the ethers C_{2}H_{4}X_{2}, corresponding with it, are capable of forming compounds containing C_{2}H_{4}X_{2}_n_C_{2}H_{4}O. On the other hand, there is reason to think that the property of forming basic salts is connected with the polymerisation of bases, especially colloidal ones (_see_ the chapter on Silica, Lead Salts, and Tungstic Acid). [24] Mercuric iodide, HgI_{2}, is obtained first as a yellow, and then as a red, precipitate on mixing solutions of mercuric salts and potassium iodide, and is soluble in an excess of the latter (in consequence of the formation of the double salt, HgKI_{3}); of ammonium chloride (for a similar reason), &c. It crystallises at the ordinary temperature in square prisms of a red colour. On being heated, these change into yellow rhombic crystals, isomorphous with mercuric chloride. This yellow form of mercuric iodide is very unstable, and when cooled and triturated easily again assumes the more stable red form. When fused, a yellow liquid is obtained. _Mercuric cyanide_, Hg(CN)_{2}, forms one of the most stable metallic cyanides. It is obtained by dissolving mercuric oxide in prussic acid, and by boiling Prussian blue with water and mercuric oxide, ferric oxide being then obtained in the precipitate. Mercuric cyanide is a colourless crystalline substance, soluble in water, and distinguished by its great stability; sulphuric acid does not liberate prussic acid from it, and even caustic potash does not remove the cyanogen (a complex salt is probably produced), but the halogen acids disengage HCN. Like the chloride, it combines with mercuric oxide, forming the oxycyanide, Hg_{2}O(CN)_{2}, and it shows a very marked tendency to form double compounds--for example, K_{2}Hg(CN)_{4}. The alkali chlorides and iodides form similar compounds--for instance, the salt HgKI(CN)_{2} crystallises very well, and is produced by directly mixing solutions of potassium iodide and mercuric cyanide. Wells (1889) and Vare obtained and investigated many such double salts, and showed the possibility of the formation, not only of HgCl_{2}MCl and HgCl_{2}2MCl where M is a metal of the alkalis--for example, Cs--but also of HgCl_{2}3MCl,2(HgCl_{2})MCl, and in general _n_HgX_{2}_m_MX, where X stands for various haloids. Mercury has a remarkable power of forming very unstable compounds with ammonia, in which the mercury replaces the hydrogen, and, if a mercuric compound be taken, its atom occupies the place of two atoms of the hydrogen in the ammonia. Thus Plantamour and Hirtzel showed that precipitated mercuric oxide dried at a gentle heat, when continuously heated (up to 100°-150°) in a stream of dry ammonia, leaves a brown powder of _mercuric nitride_, N_{2}Hg_{3}, according to the equation 3HgO + 2NH_{3} = N_{2}Hg_{3} + 3H_{2}O.[24 bis] This substance, which is attacked by water, acids, and alkalis (giving a white powder), is very explosive when struck or rubbed, evolving nitrogen, proving that the bond between the mercury and the nitrogen is very feeble.[25] By the action of liquefied ammonia on yellow mercuric oxide Weitz also obtained an explosive compound, dimercurammonium hydroxide, N_{2}Hg_{4}O, which corresponds with an ammonium oxide, (NH_{4})_{2}O, in which the whole of the hydrogen is replaced by mercury. A solution of ammonia reacts with mercuric oxide, forming the hydroxide, NHg_{2}.OH, to which a whole series of salts, NHg_{2}X, correspond; these are generally insoluble in water and capable of decomposing with an explosion. But salts of the same type, but with one atom of mercury, NH_{2}HgX, are more frequently and more easily formed; they were principally studied by Kane, although known much earlier. Thus, if ammonia be added to a solution of corrosive sublimate (or, still better, in reverse order), a precipitate is obtained known as white precipitate (_Mercurius præcipitatus albus_) or _mercurammonium chloride_, NH_{2}HgCl, which may also be regarded not only as sal-ammoniac with the substitution of H_{2} by mercury, but also as HgX_{2}, where one X represents Cl and the other X represents the ammonia radicle, HgCl_{2} + 2NH_{3} = NH_{2}.HgCl + NH_{4}Cl. When heated, mercurammonium chloride decomposes, yielding mercurous chloride; when heated with dry hydrochloric acid it forms ammonium chloride and mercuric chloride. Other simple and double salts of mercurammonium, NH_{2}HgX, are also known. Pici (1890) showed that all the compounds HgH_{2}NX may be regarded as compounds of the above-named Hg_{2}NX with NH_{4}X because their sum equals 2HgH_{2}X.[25 bis] [24 bis] _See_ Chapter XIX., Note 6 bis: Hg_{3}P_{2}. In studying the metallic nitrides it is necessary to keep the corresponding phosphides in mind. [25] Hg_{3}N_{2} is similar in composition to Mg_{3}N_{2}, &c. (Chapter XIV.) The readiness with which mercuric nitride explodes shows that the connection between the nitrogen and the mercury is very unstable, and explains the circumstance that the so-called _mercury fulminate_, or _fulminating mercury_, is an exceedingly explosive substance. This substance is prepared in large quantities for explosive mixtures; it enters into the composition of percussion caps, which explode when struck, and ignite gunpowder. Mercury fulminate was discovered by Howard, and from that time has been prepared in the following way: one part of mercury is dissolved in twelve parts of nitric acid, of sp. gr. 1·36, and when the whole of the mercury is dissolved, 5·5 parts of 90 p.c. alcohol are added, and the mass is shaken. A reaction then commences, accompanied by a rise in temperature due to the oxidation of the alcohol. As a matter of fact, many oxidation products are produced during the action of the nitric acid on the alcohol (glycolic acid, ethers, &c.) When the reaction becomes tolerably vigorous, the same quantity of alcohol is added as at the commencement, when a grey precipitate of the fulminate separates. This salt has the composition C_{2}Hg(NO_{2})N. It explodes when struck or heated. The mercury in it may be replaced by other metals--for instance, copper or zinc, and also silver. The silver salt, C_{2}Ag_{2}(NO_{2})N, is obtained in a precisely analogous manner, and is even more explosive. Under the action of alkali chlorides, only half the silver is replaced by the alkali metal, but if the whole of the silver be replaced by an alkali metal, then the salt decomposes. This is evidently because combinations of this kind proceed in virtue of the formation of substances in which mercury, and metals akin to it, are connected in an unstable way with nitrogen. Potassium and other light metals are incapable of entering into such connection and therefore, the substitution of potassium for mercury entails the splitting-up of the combination. Investigations of the fulminates were carried on by Gay-Lussac and Liebig, but only the investigations of L. N. Shishkoff fully cleared up the composition and relation of these substances to the other carbon compounds. Shishkoff showed that fulminates correspond with the nitro-acid, C_{2}H_{2}(NO_{2})N. The explosiveness of the group depends partly on its containing at the same time NO_{2} and carbon; we already know that all such nitrogen compounds are explosive. If we imagine that the NO_{2} is replaced by hydrogen, we shall have a substance of the composition C_{2}H_{3}N. This is acetonitrile--that is, acetic acid + NH_{3} - 2H_{2}O, or ethenyl nitrile, as shown in Chapter VI. The formation of an acetic compound by the action of nitric acid on alcohol is easily understood, because acetic acid is produced by the oxidation of alcohol, and the production of the elements of ammonia, indispensable for the formation of a nitrile, is accounted for by the fact that nitric acid under the action of reducing substances in many cases forms ammonia. Moreover a certain analogy has been found between fulminating acid and hydroxylamine, but details upon this subject must be looked for in works on organic chemistry. The explosiveness of fulminating mercury, the rapidity of its decomposition (gunpowder, and even guncotton, burn more slowly and explode less violently), and the force of its explosion, are such that a small quantity (loosely covered) will shatter massive objects. The investigations of Abel on the communication of explosion from one substance to another are remarkable. If guncotton be ignited in an open space, it burns quietly; but if fulminating mercury be exploded by the side of it, the decomposition of the guncotton is effected instantaneously, and it then shatters the objects upon which it lies, so rapid is the decomposition. Abel explains this by supposing that the explosion of the fulminating salt brings the molecules of guncotton into a uniform or as it were harmonious state of vibration, which causes the rapid decomposition of the whole mass. This rapid decomposition of explosive substances defines the distinction between explosion and combustion. Besides this, Berthelot showed that from that form of powerful molecular concussion which takes place during the explosion of fulminating mercury, the state of strain and stability of equilibrium of substances which are endothermal, or capable of decomposing with the disengagement of heat--for instance, cyanogen, nitro compounds, nitrous oxide, &c.--is generally destroyed. Thorpe showed that carbon bisulphide, CS_{2}, also an endothermal substance, decomposes into sulphur and charcoal, when fulminating mercury is exploded in contact with it. [25 bis] The capacity for replacing hydrogen in chloride of ammonium by metals also belongs to Zn and Cd. Kvasnik (1892), by the action of ammonia upon alcoholic solutions of CdCl_{2} and ZnCl_{2}, obtained substances of the general formula M(NH_{3}Cl)_{2}, formed as it were from two molecules of sal-ammoniac by the substitution of two atoms of hydrogen by a diatomic metal. These substances appear as white, finely crystalline powders. Under the action of heat half the ammonia passes off, and a compound of the composition MClNH_{3}Cl is formed. The compounds of cadmium and zinc are distinguished from each other by the former being more volatile than the latter. We may further remark that in the series Mg, Zn, Cd, and Hg the capacity to form double salts of diverse composition increases with the atomic weight. Thus, according to Wells and Walden's observations (1893), the ratio _n_ : _m_ for the type _n_MCl_m_RCl_{2} (M = K, Li, Na ... R = Mg, Zn ...) is for Mg 1 : 1, for Zn 3 : 1, 2 : 1, and 1 : 1; for Cd, besides this, salts are known with the ratio 4 : 1, and for Hg 3 : 1, 2 : 1, 1 : 1, 2 : 3, 1 : 2, and 1 : 5. Mercury as a liquid metal is capable of dissolving other metals and forming metallic solutions. These are generally called 'amalgams.' The formation of these solutions is often accompanied by the development of a large amount of heat--for instance, when potassium and sodium are dissolved (Chapter XII., Note 39); but sometimes heat is absorbed, as, for instance, when lead is dissolved. It is evident that phenomena of this kind are exceedingly similar to the phenomena accompanying the dissolution of salts and other substances in water, but here it is easy to demonstrate that which is far more difficult to observe in the case of salts: the solution of metals in mercury is accompanied by the formation of definite chemical compounds of the mercury with the metals dissolved. This is shown by the fact that when pressed (best of all in chamois leather) such solutions leave solid, definite compounds of mercury with metals. It is, however, very difficult to obtain them in a pure state, on account of the difficulty of separating the last traces of mercury, which is mechanically distributed between the crystals of the compounds. Nevertheless, in many cases such compounds have undoubtedly been obtained, and their existence is clearly shown by the evident crystalline structure and characteristic appearance of many amalgams. Thus, for instance, if about 2-1/2 p.c. of sodium be dissolved in mercury, a hard, crystalline amalgam is obtained, very friable and little changeable in air. It contains the compound NaHg_{5} (Chapter XII., Note 39). Water decomposes it, with the evolution of hydrogen, but more slowly than other sodium amalgams, and this action of water only shows that the bond between the sodium and the mercury is weak, just like the connection between mercury and many other elements--for instance, nitrogen. Mercury directly and easily dissolves potassium, sodium, zinc, cadmium, tin, gold, bismuth, lead, &c., and from such solutions or alloys it is in most cases easy to extract definite compounds--thus, for instance, the compounds of mercury and silver have the compositions HgAg and Ag_{2}Hg_{3}. Objects made of copper when rubbed with mercury become covered with a white coating of that metal, which slowly forms an amalgam; silver acts in the same way, but more slowly, and platinum combines with mercury with still greater difficulty. This metal only readily forms an amalgam when in the form of a fine powder. If salts of platinum in solution are poured on to an amalgam of sodium, the latter element reduces the platinum, and the platinum separated is dissolved by the mercury. Almost all metals readily form amalgams if their solutions are decomposed by a galvanic current, where mercury forms the negative pole. In this way an amalgam may even be made with iron, although iron in a mass does not dissolve in mercury. Some amalgams are found in nature--for instance, silver amalgams. Amalgams are used in considerable quantities in the arts. Thus the solubility of silver in mercury is taken advantage of for extracting that metal from the ore by means of amalgamation, and for silvering by fire. The same is the case with gold. Tin amalgam, which is incapable of crystallising and is obtained by dissolving tin in mercury, composes the brilliant coating of ordinary looking-glasses, which is made to adhere to the surface of the polished glass by simply pressing by mechanical means sheets of tin foil bathed in mercury on to the cleansed surface of the glass.[26] (_See_ 'The Nature of Amalgams,' by W. L. Dudley; Toronto, 1889.) [26] I consider it appropriate here to call attention to the want of an element (ekacadmium) between cadmium and mercury in the periodic system (Chapter XV.) But as in the ninth series there is not a single known element, it may be that this series is entirely composed of elements incapable of existing under present conditions. However, until this is proved in one way or another, it may be concluded that the properties of ekacadmium will be between those of cadmium and mercury. It ought to have an atomic weight of about 155, to form an oxide EcO, a slightly stable oxide Ec_{2}O. Both ought to be feeble bases, easily forming double and basic salts. The volume of the oxide will be nearly 17·5, because the volume of cadmium oxide is about 16, and that of mercuric oxide 19. Therefore the density of the oxide will approach 171 ÷ 17·5 = 9·7. The metal ought to be easily fusible, oxidising when heated, of a grey colour, with a specific volume, about 14 (cadmium = 13, mercury = 15), and, therefore, its specific gravity (155 ÷ 14) will nearly = 11. Such a metal is unknown. But in 1879 Dahl, in Norway, discovered in the island of Oterö, not far from Kragerö, in a vein of Iceland spar in a nickel mine, traces of a new metal which he called norwegium, and which presented a certain resemblance to ekacadmium. Perfect purity of the metal was not attained, and therefore the properties ascribed to norwegium must be regarded as approximate, and likely to undergo considerable alteration on further study. A solution of the roasted mineral in acid was twice precipitated by sulphuretted hydrogen, and again ignited; the oxide obtained was easily reduced. When the metal was dissolved in hydrochloric acid largely diluted with water, and the solution boiled, the basic salt was precipitated, and thus freed from the copper which remained in the solution. The reduced metal had a density 9·44, and easily oxidised. If the composition NgO be assigned to the oxide, then Ng = 145·9. It fused at 254°; the hydroxide was soluble in alkalis and potassium carbonate. In any case, if norwegium is not a mixture of other metals, it belongs to the uneven series, because the heavy metals of the even series are not easily reducible. Brauner thinks that norwegium oxide is Ng_{2}O_{3}, the atom Ng = 219, and places it in Group VI., series 11, but then the feebly acid higher oxide, NgO_{3}, ought to be formed. Amongst the metals accompanying zinc which have been named, but not authentically separated, must be included the _actinium_ of Phipson (1881). He remarked that certain sorts of zinc give a white precipitate of zinc sulphide which blackens on exposure to light and then becomes white in the dark again. Its oxide, closely resembling in many ways cadmium oxide, is insoluble in alkalis, and it forms a white metallic sulphide, blackening on exposure to light. As no further mention has been made of it since 1882, its existence must be regarded as doubtful. CHAPTER XVII BORON, ALUMINIUM, AND THE ANALOGOUS METALS OF THE THIRD GROUP If the elements of small atomic weight which we have hitherto discussed be placed in order, it will be clearly seen that, judging by the formulæ of their higher compounds, one element is wanting between beryllium and carbon. For lithium gives LiX, beryllium forms BeX_{2}, and then comes carbon giving CX_{4}. Evidently to complete the series we must look for an element forming RX_{3}, and having an atomic weight greater than 9 and less than 12. And _boron_ is such a one; its atomic weight is 11, and its compounds are expressed by BX_{3}. Lithium and beryllium are metals; carbon has no metallic properties; boron appears in a free state in several forms which are intermediate between the metals and non-metals. Lithium gives an energetic caustic oxide, beryllium forms a very feeble base; hence one would expect to find that the oxide of boron, B_{2}O_{3}, has still more feeble basic properties and some acid properties, all the more as CO_{2} and N_{2}O_{5}, which follow after B_{2}O_{3} in their composition and in the periodic system, are acid oxides. And, indeed, the only known _oxide of boron_ exhibits a feeble basic character, together with the properties of a feeble acid oxide. This is even seen from the fact that a solution of boron oxide reddens blue litmus and acts on turmeric paper as an alkali, and these reactions may be used for determining the presence of B_{2}O_{3} in solutions. By themselves the alkali borates have an alkaline reaction, which clearly indicates the feeble acid character of boric acid. If they are mixed in solution with hydrochloric acid, boric acid is liberated, and if a piece of turmeric paper be immersed in this solution and then dried, the excess of hydrochloric acid volatilises, while the boric acid remains on the paper and communicates a _brown coloration_ to it, just like alkalis. Boron trioxide or boric anhydride enters into the composition of many minerals, in the majority of cases in small quantities as an isomorphous admixture, not replacing acids but bases, and most frequently alumina (Al_{2}O_{3}), for as a rule the amount of alumina decreases as that of the boric anhydride increases in them. This substitution is explained by the similarity between the atomic composition of the oxides of aluminium (alumina) and boron. The subdivision of oxides into basic and acid can in no way be sharply defined, and here we meet with the most conclusive proof of the fact, for the oxides of boron and aluminium belong to the number of intermediate oxides, closely approaching the limit separating the basic from the acid oxides. Their type (Chapter XV.) R_{2}O_{3} is intermediate between those of the basic oxides R_{2}O and RO and those of the acid oxides R_{2}O_{5} and RO_{3}. If we turn our attention to the chlorides, we remark that lithium chloride is soluble in water, is not volatile, and is not decomposed by water; the chlorides of beryllium and magnesium are more volatile, and although not entirely, still are decomposed by water; whilst the chlorides of boron and aluminium are still more volatile and are decomposed by water. Thus the position of boron and aluminium in the series of the other elements is clearly defined by their atomic weights, and shows us that we must not expect any new and distinct functions in these elements. Boron was originally known in the form of sodium borate, Na_{2}B_{4}O_{7},10H_{2}O, or _borax_, or _tincal_, which was exported from Asia, where it is met with in solution in certain lakes of Thibet; it has also been discovered in California and Nevada, U.S.A.[1] Boric acid was afterwards found in sea-water and in certain mineral springs.[2] Its presence may be discovered by means of the green coloration which it communicates to the flame of alcohol, which is capable of dissolving free boric acid.[3] Many of the boron compounds employed in the arts are obtained from the impure boric acid which is extracted in Tuscany from the so-called _suffioni_. In these localities, which present the remains of volcanic action, steam mixed with nitrogen, hydrogen sulphide, small quantities of boric acid, ammonia, and other substances, issue from the earth.[3 bis] The boric acid partially volatilises with the steam, for if a solution of boric acid be boiled, the distillate will always contain a certain amount of this substance.[4] [1] Borax is either directly obtained from lakes (the American lakes give about 2,000 tons and the lakes of Thibet about 1,000 tons per annum), or by heating native calcium borate (_see_ Note 2) with sodium carbonate (about 4,000 tons per annum), or it is obtained (up to 2,000 tons) from the Tuscan impure boric acid and sodium carbonate (carbonic anhydride is evolved). Borax gives supersaturated solutions with comparative ease (Gernez), from which it crystallises, both at the ordinary and higher temperatures, in octahedra, containing Na_{2}B_{4}O_{7},5H_{2}O. Its sp. gr. is 1·81. But if the crystallisation proceeds in open vessels, then at temperatures below 56°, the ordinary prismatic crystallo-hydrate B_{4}Na_{2}O_{7},10H_{2}O is obtained. Its sp. gr. is 1·71, it effloresces in dry air at the ordinary temperature, and at 0° 100 parts of water dissolve about 8 parts of this crystallo-hydrate, at 50° 27 parts, and at 100° 201 parts. Borax fuses when heated, loses its water and gives an anhydrous salt which at a red heat fuses into a mobile liquid and solidifies into a transparent amorphous _glass_ (sp. gr. 2·37), which before hardening acquires the pasty condition peculiar to common molten glass. Molten borax dissolves many oxides and on solidifying acquires characteristic tints with the different oxides; thus oxide of cobalt gives a dark blue glass, nickel a yellow, chromium a green, manganese an amethyst, uranium a bright yellow, &c. Owing to its fusibility and property of dissolving oxides, borax is employed in soldering and brazing metals. Borax frequently enters into the composition of strass and fusible glasses. [2] We may mention the following among the minerals which contain boron: calcium borate, (CaO)_{3}(B_{2}O_{3})(H_{2}O)_{6}, found and extracted in Asia Minor, near Brusa; _boracite_ (stassfurtite), (MgO)_{6}(B_{2}O_{3})_{8},MgCl_{2}, at Stassfurt, in the regular system, large crystals and amorphous masses (specific gravity 2·95), used in the arts; _ereméeffite_ (Damour), AlBO_{3} or Al_{2}O_{3}B_{2}O_{3}, found in the Adulchalonsk mountains in colourless, transparent prisms (specific gravity 3·28) resembling apatite; _datholite_, (CaO)_{2}(SiO_{2})_{2}B_{2}O_{3},H_{2}O; and ulksite, or the boron-sodium carbonate from which a large quantity of borax is now extracted in America (Note 1). As much as 10 p.c. of boric anhydride sometimes enters into the composition of tourmalin and axinite. [3] This green coloration is best seen by taking an alcoholic solution of volatile ethyl borate, which is easily obtained by the action of boron chloride on alcohol. [3 bis] P. Chigeffsky showed in 1884 (at Geneva) that in the evaporation of saline solutions many salts are carried off by the vapour--for instance, if a solution of potash containing about 17-20 grams of K_{2}CO_{3} per litre be boiled, about 5 milligrams of salt are carried off for every litre of water evaporated. With Li_{2}CO_{3} the amount of salt carried over is infinitesimal, and with Na_{2}CO_{3} it is half that given by K_{2}CO_{3}. The volatilisation of B_{2}O_{3} under these circumstances is incomparably greater--for instance, when a solution containing 14 grams of B_{2}O_{3} per litre is boiled, every litre of water evaporated carries over about 350 milligrams of B_{2}O_{3}. When Chigeffsky passed steam through a tube containing B_{2}O_{3} at 400°, it carried over so much of this substance that the flame of a Bunsen's burner into which the steam was led gave a distinct green coloration; but when, instead of steam, air was passed through the tube there was no coloration whatever. By placing a tube with a cold surface in steam containing B_{2}O_{3}, Chigeffsky obtained a crystalline deposit of the hydrate B(OH)_{3} on the surface of the tube. Besides this, he found that the amount of B_{2}O_{3} carried over by steam increases with the temperature, and that crystals of B(OH)_{3} placed in an atmosphere of steam (although perfectly still) volatilise, which shows that this is not a matter of mechanical transfer, but is based on the capacity of B_{2}O_{3} and B(OH)_{3} to pass into a state of vapour in an atmosphere of steam. [4] How it is that these vapours containing boric acid are formed in the interior of the earth is at present unknown. Dumas supposes that it depends on the presence of _boron sulphide_, B_{2}S_{3} (others think boron nitride), at a certain depth in the earth. This substance may be artificially prepared by heating a mixture of boric acid and charcoal in a stream of carbon bisulphide vapour, and by the direct combination of boron and the vapour of sulphur at a white heat. The almost non-crystalline compound B_{2}S_{3}, sp. gr. 1·55, thus obtained is somewhat volatile, has an unpleasant smell, and is very easily decomposed by water, forming boric acid and hydrogen sulphide, B_{2}S_{3} + 3H_{2}O = B_{2}O_{3} + 3H_{2}S. It is supposed that a bed of boron sulphide lying at a certain depth below the surface of the earth comes into contact with sea water which has percolated through the upper strata, becomes very hot, and gives steam, hydrogen sulphide, and boric acid. This also explains the presence of ammonia in the vapours, because the sea water certainly passes through crevices containing a certain amount of animal matter, which is decomposed by the action of heat and evolves ammonia. There are several other hypotheses for explaining the presence of the vapours of boric acid, but owing to the want of other known localities the comparison of these hypotheses is at present hardly possible. The amount of boric anhydride in the vapours which escape from the Tuscan fumerolles and suffioni is very inconsiderable, less than one-tenth per cent., and therefore the direct extraction of the acid would be very uneconomical, hence the heat contained in the discharged vapours is made use of for evaporating the water. This is done in the following manner. Reservoirs are constructed over the crevices evolving the vapours, and the water of some neighbouring spring is passed into them. The vapours are caused to pass through these reservoirs, and in so doing they give up all their boric acid to the water and heat it, so that after about twenty-four hours it even boils; still this water only forms a very weak solution of boric acid. This solution is then passed into lower basins and again saturated by the vapours discharged from the earth, by which means a certain amount of the water is evaporated and a fresh quantity of boric acid absorbed; the same process is repeated in another reservoir, and so on until the water has collected a somewhat considerable amount of boric acid. The solution is drawn from the last reservoir A into settling vessels B D, and then into a series of vessels _a_, _b_, _c_. In these vessels, which are made of lead, the solution is also evaporated by the vapours escaping from the earth, and attains a density of 10° to 11° Baumé. It is allowed to settle in the vessel C, in which it cools and crystallises, yielding (not quite pure) crystalline boric acid. At temperatures above 100°, for instance, with superheated steam, boric acid volatilises with steam very easily. [Illustration: FIG. 81.--Extraction of boric acid in Tuscany.] If boric acid be introduced into an excess of a strong hot solution of sodium hydroxide, then, on slowly cooling, the salt NaBO_{2},4H_{2}O crystallises out. This salt contains an equivalent of Na_{2}O to one equivalent B_{2}O_{3}. It might be termed a neutral salt did it not possess strongly alkaline reactions and easily split up into the alkali and the more stable borax or biborate of sodium mentioned above, which contains 2B_{2}O_{3} to Na_{2}O.[5] This salt is prepared by the action of boric acid on a solution of sodium carbonate. Borax may be perfectly purified by crystallisation. If a saturated and hot solution of borax be mixed with strong hydrochloric acid, common salt and a normal crystalline hydrate of _boric acid_ are formed. The composition of this hydrate is B(HO)_{3}, according to the form BX_{3}--that is, of the composition B_{2}O_{3},3H_{2}O. This is the easiest method of obtaining pure boric acid. The water is easily expelled from this hydrate; it loses half at 100° and the remainder on further heating, and the remaining B_{2}O_{3} or boric anhydride fuses at 580° (according to Carnelley), forming at first a ductile (easily drawn out into threads), tenacious mass and then a colourless liquid solidifying to a transparent glass, which absorbs moisture from the atmosphere and then becomes cloudy.[6] Only the alkaline salts of boric acid are soluble in water, but all borates are soluble in acids, owing to their easy decomposability and the solubility of boric acid itself. Although boric anhydride, B_{2}O_{3}, absorbs 3H_{2}O from damp air, still in the presence of water it always[7] combines with a less quantity of bases (borax only contains 1/6). However, fused boric anhydride forms a crystalline compound with magnesium of the same type as the hydrate (MgO)_{3}B_{2}O_{3} (Ebelmann), and even with sodium it forms (Na_{2}O)_{3}B_{2}O_{3} or Na_{3}BO_{3} (Benedict). As a rule, the salts of boric acid contain less base, although they are all able to form saline compounds with bases when fused. Generally, vitreous fluxes are formed by this means,[8] which when fused recall ordinary aqueous solutions in many respects. Some of them crystallise on solidifying, and then they have, like salts, a definite composition. The property of boric anhydride of forming higher grades of combination with basic oxides when fused explains the power of fused borax to dissolve metallic oxides, and the experiments of Ebelmann on the preparation of artificial crystals of the precious stones by means of boric anhydride. Boric anhydride is, although with difficulty, volatile at a high temperature, and therefore if it dissolves an oxide, it may be partially driven off from such a solution by prolonged and powerful ignition; in which case the oxides previously in solution separate out in a crystalline form, and frequently in the same forms as those in which they occur in nature--for example, crystals of alumina, which by itself fuses with difficulty, have been obtained in this manner. It dissolves in molten boric anhydride, and separates out in natural rhombohedric crystals. In this way Ebelmann also obtained _spinel_--that is, a compound of magnesium and aluminium oxides which occurs in nature.[9] [5] Metals, like Na, K, Li, give salts of the type of borax, MBO_{2} or MH_{2}BO_{3}. A solution of borax, Na_{2}B_{4}O_{7}, has an alkaline reaction, decomposes ammonia salts with the liberation of ammonia (Bolley), absorbs carbonic anhydride like an alkali, dissolves iodine like an alkali (Georgiewics), and seems to be decomposed by water. Thus Rose showed that strong solutions of borax give a precipitate of silver borate with silver nitrate, whilst dilute solutions precipitate silver oxide, like an alkali. Georgiewics even supposes (1888) boric anhydride to be entirely void of acid properties; for all acids, on acting on a mixture of solutions of potassium iodide and iodate, evolve iodine, but boric acid does not do this. With dilute solutions of sodium hydroxide Berthelot obtained a development of heat equal to 11-1/2 thousand calories per equivalent of alkali (40 grams sodium hydroxide) when the ratio Na_{2}O : 2B_{2}O_{3} (as in borax) was taken, and only 4 thousand calories when the ratio was Na_{2}O : B_{2}O_{3}, whence he concludes that water powerfully decomposes those sodium borates in which there is more alkali than in borax. Laurent (1849) obtained a sodium compound, Na_{2}O,4B_{2}O_{3},10H_{2}O, containing twice as much boric anhydride as borax, by boiling a mixture of borax with an equivalent quantity of sal-ammoniac until the evolution of ammonia entirely ceased. Hence it is evident that feeble acids are as prone to, and as easily, form acid salts (that is, salts containing much acid oxide) as feeble bases are to give basic salts. These relations become still clearer on an acquaintance with such feeble acids as silicic, molybdic, &c. This variety of the proportions in which bases are able to form salts recalls exactly the variety of the proportions in which water combines with crystallo-hydrates. But the want of sufficient data in the study of these relations does not yet permit of their being generalised under any common laws. With respect to the feeble acid energy of boric anhydride I think it useful to add the following remarks. Carbonic anhydride is absorbed by a solution of borax, and displaces boric anhydride; but it is also displaced by it, not only on fusion, but also on solution, as the preparation of borax itself shows. Sulphuric anhydride is absorbed by boric acid, forming a compound B(HSO_{4})_{3}, where HSO_{4} is the radicle of sulphuric acid (D'Ally). With phosphoric acid, boric acid forms a stable compound, BPO_{4}, or B_{2}O_{3}P_{2}O_{5}, undecomposable by water, as Gustavson and others have shown. With respect to tartaric acid, boric anhydride is able to play the same part as antimonious oxide. Mannitol, glycerol, and similar polyhydric alcohols also seem able to form particularly characteristic compounds with boric anhydride. All these aspects of the subject require still further explanation by a method of fresh and detailed research. [6] Ditte determined the sp. gr.:-- 0° 12° 80° B_{2}O_{3} 1·8766 1·8470 1·6988 B(OH)_{3} 1·5463 1·5172 1·3828 Solubility 1·95 2·92 16·82 The last line gives the solubility, in grams, of boric acid, B(OH)_{3}, per 100 c.c. of water, also according to the determinations of Ditte. [7] It is evident that, in the presence of basic oxides, water competes with them, which fact in all probability determines both the amount of water in the salts of boric acid as well as their decomposition by an excess of water. In confirmation of the above-mentioned competing action between water and bases, I think it useful to point out that the crystallo-hydrate of borax containing 5H_{2}O may be represented as B(HO)_{3}, or rather as B_{2}(OH)_{6}, with the substitution of one atom of hydrogen by sodium, since Na_{2}B_{4}O_{7},5H_{2}O = 2B_{2}(OH)_{5}(ONa). The composition of the acid boric salts is very varied, as is seen from the fact that Reychler (1893) obtained (Cs_{2}O)3B_{2}O_{3}, (Rb_{2}O)2B_{2}O_{3} (corresponding to borax) and (Li_{2}O)B_{2}O_{3}, and that Le Chatelier and Ditte obtained, for CaO, MgO, &c., (RO)B_{2}O_{3}, (RO)_{2}3B_{2}O_{3}, (RO)2B_{2}O_{3}, (RO)_{2}B_{2}O_{3}, and even (RO)_{3}B_{2}O_{3}. [8] A glass can only be formed by those slightly volatile oxides which correspond with feeble acids, like silica, phosphoric and boric anhydrides, &c., which themselves give glassy masses, like quartz, glacial phosphoric acid, and boric anhydride. They are able, like aqueous solutions and like metallic alloys, to solidify either in an amorphous form or to yield (or even be wholly converted into) definite crystalline compounds. This view illustrates the position of solutions amongst the other chemical compounds, and allows all alloys to be regarded from the aspect of the common laws of chemical reactions. I have therefore frequently recurred to it in this work, and have since the year 1850 introduced it into various provinces of chemistry. [9] If boric acid in its aqueous solutions proves to be exceedingly feeble, unenergetic, and easily displaced from its salts by other acids, yet in an anhydrous state, as anhydride, it exhibits the properties of an energetic acid oxide, and it _displaces_ the anhydrides of other acids. This of course does not mean that the acid then acquires new chemical properties, but only depends on the fact that the anhydrides of the majority of acids are much more volatile than boric anhydride, and therefore the salts of many acids--even of sulphuric acid--are decomposed when fused with boric anhydride. By itself boric acid is used in the arts in small quantity, chiefly for the preservation of meat and fish (which must be afterwards well washed in water) and of milk, and for soaking the wicks of stearin candles; the latter application is based on the fact that the wicks, which are made of cotton twist, contain an ash which is infusible by itself but which fuses when mixed with boric acid. Free _boron_ was obtained (1809) by Davy, Gay-Lussac, and Thénard when they obtained the metals of the alkalis, for boric anhydride when fused with sodium gives up its oxygen to the sodium, and free boron is liberated as an _amorphous_ powder like charcoal.[10] It is of a brown colour, specific gravity 2·45 (Moissan), and when dry does not alter in the air at the ordinary temperature; but it burns when ignited to 700°, and in so doing combines not only with the oxygen of the air, but also with the nitrogen. However, the combustion is never complete, because the boric anhydride formed on the surface covers the remaining mass of the boron, and so preserves it from the action of the oxygen. Acids, even sulphuric (forming SO_{2}) and phosphoric (forming phosphorus), easily oxidise amorphous boron, especially when heated, converting it into boric acid. Alkalis have the same action on it, only in this case hydrogen is evolved. Boron decomposes steam at a red heat, also with evolution of hydrogen. [10] _Amorphous boron_ is prepared by mixing 100 parts of powdered boric anhydride with 50 parts of sodium in small lumps; this mixture is thrown into a powerfully heated cast-iron crucible, covered with a layer of ignited salt, and the crucible covered. Reaction proceeds rapidly; the mass is stirred with an iron rod, and poured directly into water containing hydrochloric acid. The action is naturally accompanied by the formation of sodium borate, which is dissolved, together with the salt, by the water, whilst the boron settles at the bottom of the vessel as an insoluble powder. It is washed in water, and dried at the ordinary temperature. Magnesium, and even charcoal and phosphorus, are also able to reduce boron from its oxide. Boron, in the form of an amorphous powder, very easily passes through filter-paper, remains suspended in water, and colours it brown, so that it appears to be soluble in water. Sulphur precipitated from solutions shows the same (colloidal) property. When borax is fused with magnesium powder, it gives a brown powder of a compound of boron and magnesium, Mg_{2}B (Winkler, 1890), but when a mixture of 1 part of magnesium and 3 parts of B_{2}O_{3} is heated to redness (Moissan, 1892), it forms amorphous boron in the form of a chestnut-coloured powder, which, after being washed with water, hydrochloric and hydrofluoric acids, is fused again with B_{2}O_{3} in an atmosphere of hydrogen in order to prevent the access of the nitrogen of the air, which is easily absorbed by incandescent amorphous boron. Sabatier (1891) considers that a certain amount of gaseous hydride of boron is evolved in the action of hydrochloric acid upon the alloys of magnesium and boron, because the gas disengaged burns with a green flame. Still, the existence of hydride of boron cannot be regarded as certain. Under the action of the heat of the electric furnace boron forms with carbon a _carbide_, BC, as Mühlhäuser and Moissan showed in 1893. Amorphous boron, like charcoal, dissolves in certain molten metals. The property of fused _aluminium of dissolving boron_ in considerable quantity is very striking; on cooling such a solution, the boron partially combined with the aluminium separates out in a crystalline form, and its properties are then exceedingly remarkable. The crystalline boron may be obtained by heating (to 1,300°) the pulverulent boron with aluminium in a well-closed crucible, the access of air being prevented as far as possible. After cooling, crystals are observed on the surface of the aluminium, and may easily be separated by dissolving the latter in hydrochloric acid, which does not act on the crystals. The specific gravity of the crystals is 2·68; they are partially transparent, but are for the most part coloured dark brown; they contain about 4 p.c. of carbon and up to 7 p.c. of aluminium, so that they cannot be considered as pure boron. Nevertheless, the properties of this _crystalline_ substance, which was obtained by Wöhler and Deville, are very remarkable. It most closely resembles _the diamond in its properties_--in fact, these crystals have the lustre and high refracting power proper to the diamond only, whilst their hardness competes with that of the diamond. Their powder polishes even the diamond, and like the diamond scratches the sapphire and corundum. Crystalline boron is much more stable with respect to chemical reagents than the amorphous variety, and as it resembles the diamond, so amorphous boron, on the other hand, distinctly recalls certain of the properties of charcoal; thus a certain resemblance exists between boron and carbon in a free state, which is further justified by the proximity of their positions in the periodic system. Among the other compounds of boron, those with nitrogen and the halogens are the most remarkable. As already mentioned above, amorphous boron combines directly with _nitrogen_ at a red heat. If it be heated in a glass tube in a stream of nitric oxide, perfect combustion takes place, 5B + 3NO = B_{2}O_{3} + 3BN. If the residue be treated with nitric acid, the boric anhydride dissolves, whilst the _boron nitride_ remains[11] as an extremely light white powder, which is sometimes partially crystalline and greasy to the touch, like talc. It is infusible and unchanged, even at the melting-point of nickel. In general, it is remarkable for its great stability with respect to chemical reagents. Nitric and hydrochloric acids, as well as alkaline solutions, and hydrogen and chlorine at a red heat, have no action on it. When fused with potash, it evolves ammonia, and when ignited in steam it also yields ammonia: 2BN + 3H_{2}O = B_{2}O_{3} + 2NH_{3}.[12] [11] At first boron nitride was obtained by heating boric acid with potassium cyanide or other cyanogen compounds. It may be more simply prepared by heating anhydrous borax with potassium ferrocyanide, or by heating borax with ammonium chloride. For this purpose one part of borax is intimately mixed with two parts of dry ammonium chloride, and the mixture heated in a platinum crucible. A porous mass is formed, which after crushing and treating with water and hydrochloric acid, leaves boron nitride. _Boron fluoride_, BF, is known, corresponding to BN; this body was obtained by Besson and Moissan (1891). The action of phosphorus upon iodide of boron, BI_{3}, forms PBI_{2}, and when heated to 500° in hydrogen it forms BP, which gives PH_{3} with fused KHO. [12] When fused with potassium carbonate it forms potassium cyanate, BN + K_{2}CO_{3} = KBO_{2} + KCNO. All this shows that boron nitride is a nitrile of boric acid, BO(OH) + NH_{3} - 2H_{2}O = BN. The same is expressed by saying that boron nitride is a compound of the type of the boron compounds BX_{3}, with the substitution of X_{3} by nitrogen, as the trivalent radicle of ammonia, NH_{3}. No less remarkable is the compound of boron with fluorine--_boron fluoride_, BF_{3}. It is produced in many instances when compounds of boron and of fluorine are brought together.[13] The most convenient method of preparing it is by heating a mixture of calcium fluoride with boric anhydride and sulphuric acid, 3CaF_{2} + B_{2}O_{3} + 3H_{2}SO_{4} = 3CaSO_{4} + 3H_{2}O + 2BF_{3}.[14] It is a colourless liquefiable _gas_ (the liquid boils at -100°), which on coming into contact with damp air forms white fumes, owing to its combining with water. One volume of water dissolves as much as 1,050 volumes of this gas (Bazaroff), forming a liquid which disengages boron fluoride when heated, and distils over unaltered. Boron fluoride chars organic matter, owing to its taking up the water from it, and in this respect it acts like sulphuric acid. The behaviour of boron fluoride with water must be understood as a reversible reaction, since with water it yields hydrofluoric and boric acids, whilst they, acting on one another, re-form boron fluoride and water. A state of equilibrium is set up between these four substances (and between two reversible reactions) which is distinctly dependent on the mass of the water.[14 bis] When boron fluoride is in great excess, the equilibrated system, which is capable of distilling over (sp. gr. of the liquid 1·77), has a composition BF_{3},2H_{2}O (or B_{2}O_{3},H_{2}O,6HF). It has also its corresponding salts.[15] It is a caustic liquid, having the properties of a powerful acid; but it does not act on glass, which shows that there is no free hydrofluoric acid present. Under the action of water this system changes, with the formation of boric acid and hydroborofluoric acid (HBF_{4}) according to the equation 4BF_{3}H_{4}O_{2} = 3HBF_{4} + BH_{3}O_{3} + 5H_{2}O.[16] This hydroborofluoric acid has its corresponding salts--for instance, KBF_{4}. On evaporating the aqueous solution this free acid decomposes, with the evolution of hydrofluoric acid, and a stable system is again obtained: 2HBF_{4} + 5H_{2}O = B_{2}F_{6}H_{10}O_{5} + 2HF. The resultant solution (containing 2BF_{3},5H_{2}O, sp. gr. 1·58), which is identical with that formed by the evaporation of a solution of boric acid with hydrofluoric acid, again only contains a compound of boron fluoride with water. Probably there are various other possible and more or less stable states of equilibrium and definite compounds of boron fluoride, hydrofluoric acid, and water. [13] Boron fluoride is frequently evolved on heating certain compounds occurring in nature containing both boron and fluorine. If calcium fluoride is heated with boric anhydride, calcium borate and boron fluoride are formed, and the latter, as a gas, is volatilised: 2B_{2}O_{3} + 3CaF_{2} = 2BF_{3} + Ca_{3}B_{2}O_{6}. The calcium borate, however, retains a certain amount of calcium fluoride. [14] In order to avoid the formation of silicon fluoride the decomposition should not be carried on in glass vessels, which contain silica, but in lead or platinum vessels. Boron fluoride by itself does not corrode glass, but the hydrofluoric acid liberated in the reaction may bring a part of the silica into reaction. Boron fluoride should be collected over mercury, as water acts on it, as we shall see afterwards. [14 bis] It appears to me that from this point of view it is possible to understand the apparently contradictory results of different investigators, especially those of Gay-Lussac (and Thénard), Davy, Berzelius, and Bazaroff. In the form in which the reaction of BF_{3} on water is given here, it is evident that the act of solution in water is accompanied by complex but direct chemical transformations, and I think that this example should prove the justness of those observations upon the nature of solutions which are given in Chapter I. [15] They are called fluoborates. They may be prepared directly from fluorides and borates. Such compounds of halogens with oxygen salts are known in nature (for instance, apatite and boracite), and may be artificially prepared. The composition of the fluoborates--for example, K_{4}BF_{3}O_{2}--may be expressed as that of a double salt, BO(OK),3KF. If an excess of water decomposes them (Bazaroff), this does not prove that they do not exist as such, for many double salts are decomposed by water. [16] Fluoboric acid contains boron fluoride and water, hydrofluoboric acid, boron fluoride, and hydrofluoric acid. It is evident that on the one side the competition between water and hydrofluoric acid, and, on the other hand, their power to combine, are among the forces which act here. From the fact that hydroborofluoric acid, HBF_{4}, can only exist in an aqueous solution, it must be assumed that it forms a somewhat stable system only in the presence of 3H_{2}O. Nothing of this kind occurs with boron chloride, because hydrochloric acid does not act on boric acid. However, amorphous boron at 400° burns in chlorine, and at 410° forms _boron chloride_, BCl_{3}. The boron burns in the chlorine, forming a gas which, in a freezing mixture, condenses into a liquid boiling at 17°, and gives up its excess of chlorine, if there be any, to mercury. The specific gravity of this liquid is 1·42 at 6°. Boron chloride may also be directly obtained from boric anhydride by the simultaneous action of charcoal and chlorine at a high temperature: B_{2}O_{3} + 3C + 3Cl_{2} = 2BCl_{3} + 3CO. It is also obtained by the action of phosphoric chloride on boric anhydride in a closed tube at 200° It is completely decomposed by water, like the chloranhydride of an acid, boric acid being formed; hence it fumes in the air: 2BCl_{3} + 6H_{2}O = 2BH_{3}O_{3} + 6HCl. Boron forms with bromine a similar compound, BBr_{3}, specific gravity at 6° = 2·64, boiling at 90°. The vapour densities of the fluoride, chloride, and bromide of boron show that they contain three atoms of the halogen in the molecule--that is, that boron is a trivalent element forming BX_{3}.[16 bis] [16 bis] Iodide of boron, BI_{3}, was obtained by Moissan (1891), by heating a mixture of the vapours of HI and BCl_{3} in a tube, or by the action of iodine vapour (at 750°) or HI upon amorphous boron. BI_{3} is a solid substance which dissolves in benzol and CS_{2}, reacts with water, melts at 43°, boils at 210°, has a density 3·3 at 50°, and partially decomposes in the light. Besson (1891) obtained BIBr_{2} (boiling at 125°), and BI_{2}Br (boiling at 180°) by heating (300-400°) a mixture of the vapours of HI and BBr_{3}, and showed that NH_{3} combines with BBr_{3} and BI_{3} in various proportions. As in the first group lithium is followed by sodium, giving a more basic oxide, so in the second group beryllium is followed by magnesium, and so also in the third group there is, besides the lightest element, boron, whose basic character is scarcely defined, _aluminium_, Al = 27, whose oxide, alumina, has somewhat distinct basic properties, which, although not so powerful as in magnesium oxide, are more distinct than in boric anhydride. Among the elements of the third group, aluminium is the most widely distributed in nature; it will be sufficient to mention that it enters into the composition of clay to demonstrate the universal distribution of aluminium in the earth's crust. Alumina is so named from its being the metal of alums (_alumen_). _Clay_, which is so widely distributed and familiar to everybody, is the insoluble residue obtained after the action of water containing carbonic acid on many rocks, and especially on the felspars contained in some of them. Felspar is a compound containing potash or soda, alumina, and silica. The primary rocks, like granite, contain many similar compounds (_see_ Chapter XVIII.: Felspars). Felspar is acted on by water containing carbonic acid, all the alkalis (potash and soda), and a portion of the silica passing into the water as substances which are soluble and carried away by it, whilst the alumina and silica left from the felspar remain on the spot where the solution has taken place. This is the original method of the formation of clay in its primary deposits among rocks along whose crevices the atmospheric water has permeated. Such primary deposits often contain a white pure clay, termed _kaolin_ or _porcelain clay_. But such clay is a rarity, because the conditions for its formation are rarely met with. The water, whilst acting chemically on rocks, at the same time destroys them _mechanically_, and carries off the finely divided residues of disintegration with it. Clay is most easily subjected to this mechanical action of water, because it is composed of grains of exceedingly small size and void of any visible crystalline structure, which easily remain suspended in water. The cloudy water of running mountain streams generally contains particles of clay in suspension, owing to the above-described chemical and mechanical action of the water on the minerals contained in the mountain rocks. Together with these minute particles of clay the water carries away the coarser components on which it is not able to act--for example, splinters of rock, grains of mica, quartz, &c. They were originally held together by those minerals which form clay. When the water acts on these binding minerals, a sandy mass is formed which water bears away. The cloudy water in which the particles of clay and sand are held in suspension carries them to, and deposits them at, the estuaries of rivers, lakes, seas, and oceans. The coarser particles are first deposited and form sand and similar disintegrated rocky matter, whilst the clay, owing to its finely divided state, is carried on further, and is only deposited in the still parts of the rivers, lakes, &c. Such disintegrations of rocks and separations of clay from sand have been gradually going on during the millions of years of the earth's existence, and are now proceeding, and have been the cause of the formation of the immense deposits of sandstone and clay now forming a part of the earth's strata. Such beds of clay may have been transferred by currents and streams from one locality to another, so that we must distinguish between primary and secondary deposits of clay. In places these beds of clay have, owing to long exposure under water, and perhaps partially owing to the action of heat, undergone compression, and have formed the rocky masses known as clay slates and schists, which sometimes form entire mountains. Roofing slates belong to this class of rocks. From what has been said above it will be evident that these deposits can never consist of a chemically pure and homogeneous substance, but will contain all kinds of extraneous insoluble finely divided matter, and especially sand--that is, fragments of rock, chiefly quartz (SiO_{2}). It is, however, possible to considerably purify clay from these impurities, owing to the fact that they are the result of mechanical disintegration, whilst the clay has been formed as a residue of the chemical alteration of rocky matter, and therefore its particles are incomparably more minute than the particles of sand and other rock fragments mixed with it. This difference in the size of the grains causes the clay to remain longer in suspension when shaken up in water than the coarser grains of sand. If clay be shaken up in water, and especially if it be previously boiled in it, and if after the first portion has settled the cloudy water be decanted, it will give a deposit of a very much purer clay than the original. This method is employed for purifying kaolin designed for the manufacture of the best kinds of china, earthenware, &c. A similar method is also employed in the investigation of earths for determining the _composition of soils_ chiefly composed of a mixture of sand, clay, limestone, and mould. The limestone is soluble in dilute acids, but neither the clay nor sand passes into solution by this means, and therefore the limestone is easily separated in the investigation of soils. The clay is separated from the sand by a mechanical method similar to that described above, and termed _levigation_.[17] [17] The process of _levigation_ is based on the difference in the diameters of the particles of clay and sand. In density these particles differ but little from each other, and therefore a stream of water of a certain velocity can only carry away the particles of a certain diameter, whilst the particles of a larger diameter cannot be borne away by it. This is due to the resistance to falling offered by the water. This resistance to substances moving in it increases with the velocity, and therefore a substance falling into water will only move with an increasing velocity until its weight equals the resistance offered by the water, and then the velocity will be uniform. And as the weight of the minute particles of clay is small, the maximum velocity attained by them in falling is also small. A detailed account of the theory of falling bodies in liquid, and of the experiments bearing on this subject, may be found in my work, _Concerning the Resistance of Liquids and Aeronautics_, 1880. The minute particles of clay remain suspended longer in water, and take longer to fall to the bottom. Heavy particles, although of small dimensions, fall more quickly, and are borne away by water with greater difficulty than the lighter. In this way gold and other heavy ores are washed free from sand and clay, and the coarser portions and heavier particles are left behind. A current of water of a certain velocity cannot carry away with it particles of more than a definite diameter and density, but by increasing the velocity of the current a point may be arrived at when it will bear away larger particles. A description of apparatus for the observation of phenomena of this kind is given by Schöne in his memoir in the Transactions of the Moscow Society of Natural Sciences for 1867. In order to be able accurately to vary the velocity of the current of water, a cylinder is employed in which the earth to be experimented on is placed, and water is introduced through the conical bottom of the cylinder. The rate at which the water rises in the cylinder will vary according to the quantity of water flowing per unit of time into the vessel, and consequently particles of various sizes will be carried away by the water flowing over the upper edges of the vessel. Schöne showed by direct experiment that a current of water having a velocity of 0·1 mm. per second will carry away particles having a diameter of not more than 0·0075 mm., that is, only the most minute; with a velocity _v_ = 0·2 mm. per second, particles having a diameter _d_ = 0·011 mm. are carried away; with _v_ = 0·3 mm., _d_ = 0·0146 mm.; with _v_ = 0·4 mm., _d_ = 0·017 mm.; with _v_ = 0·5 mm., _d_ = 0·02 mm.; with _v_ = 1 mm., _d_ = 0·03 mm.; with _v_ = 4 mm., _d_ = 0·07 mm.; with _v_ = 10 mm., _d_ = 0·137 mm.; with _v_ = 12 mm., _d_ = 0·15 mm.; and therefore if the current does not exceed one of these velocities, it will only carry away or wash away particles having a diameter less than that indicated. The sand and other particles mixed with the clay will then remain in the vessel. The very minute particles obtained after levigation are all considered as clay, although not only clay but other rock residue may also exist in it as very fine particles. However, this is very seldom the case, and the fine mud separated from all clays has practically the same composition as the purest kinds of kaolin. The relation between the amounts of clay and sand in soils used for the cultivation of plants is very important, because a soil rich in clay is denser, heavier, shrinks up under the action of heat, and does not readily yield to the plough in dry or wet weather, whilst a soil rich in sand is friable, crumbling, easily parts with its moisture and dries rapidly, but is comparatively easily worked. Neither crumbling sand nor pure clay can be regarded as a good _cultivating soil_. The difference in the amounts of clay and sand in a soil has also a purely chemical signification. Sand is easily permeated by the air, because its particles are not closely packed together. Hence the chemical change of manures proceeds very easily in sandy soils. But on the other hand such soils do not retain the nutritious principles contained in the manure, nor the water necessary for the nourishment of plants by means of their roots. Solutions of nutritious substances, containing salts of potassium, phosphoric acid, &c., when passed through sand only leave a portion moistening the surface of its particles. The sand has only to be washed with pure water and all the adhering films of solution are washed away. It is not so with clay. If the above solutions be passed through a layer of clay the retention of the nutritive substances of these solutions will be very marked; this is partly because of the very large surface which the minute particles of clay expose. The nutritive elements dissolved in water are retained by the particles of clay in a peculiar manner--that is, the absorptive power of clay is very great compared to that of sand--and this has a great significance in the economy of nature (Chapter XIII., p. 547). It is evident that for cultivation the most convenient soils in every respect will be those containing a definite mixture of clay and sand, and indeed the most fertile soils have this composition. The study of fertile soils, which is so important for a knowledge of the natural conditions for the application of fertilisers, belongs, strictly speaking, to the province of agriculture. In Russia the first foundation of a scientific fertilisation has been laid by Dokuchaeff. As an example only, we will give the composition of four soils; (1) The black earth of the Simbirsk Government; (2) a clay soil from the Smolensk Government; (3) a more sandy soil from the Moscow Government; and (4) a peaty soil from near St. Petersburg. These analyses were made in the laboratory of the St. Petersburg University about 1860, in connection with experiments on fertilisation (conducted by me) by the Imperial Free Economical Society. 10,000 grams of air-dried soil contain the following quantities (in grams) of substances capable of dissolving in acids, and of serving for the nourishment of plants. (1) (2) (3) (4) Na_{2}O 11 5 4 4 K_{2}O 58 10 7 5 MgO 92 33 19 7 CaO 134 17 14 11 P_{2}O_{5} 7 1 7 3 N 44 11 13 16 S 13 7 7 6 Fe_{2}O_{3} 341 155 111 46 By chemical and mechanical analysis, the chief component parts per 100 parts of air-dried soil are Clay 46 29 12 10 Sand 40 67 86 84 Organic matter 3·7 1·7 0·6 4·1 Hygroscopic water 6·3 1·3 0·8 1·9 Weight of a litre in grams 1150 1270 1350 960 The black earth excels the other soils in many respects, but naturally its stores are also exhausted by cultivation if nothing be returned to it in the form of fertilisers; and the improvement of a soil (for instance, by the addition of marl or peat, and by drainage and watering), and its fertilisation, if carried on in conformity with its composition and with the properties of the plants to be cultivated, are capable of rendering not only every soil fit for cultivation, but also of improving its value, so that in the course of time whole countries (like Holland) may clearly improve their agricultural position, whilst under the ordinary _régime_ of continued exhaustion of the soil, entire regions (as, for instance, many parts of Central Asia) may be rendered unfit for any agriculture. By treating clay with strong sulphuric acid, which dissolves the alumina in it, and then (by means of an alkaline carbonate) dissolving the silica which was combined with the alumina in the clay (but not that occurring in the form of sand, &c., which is hardly dissolved by carbonate of soda solution at all even on boiling), we may form an idea of the proportion between the component parts of a clay; and by igniting it at a high temperature, we may determine the amount of water held in it. In the purer sorts of clay dried at 100° (sp. gr. of pure kaolin is about 2·5) this proportion is about 2SiO_{2} : 2H_{2}O : Al_{2}O_{3}. In this case the conversion of felspar into kaolin is expressed by the equation:-- K_{2}O,Al_{2}O_{3},6SiO_{2} = Al_{2}O_{3},2SiO_{2} + K_{2}O,4SiO_{2}; Felspar Kaolin the compound K_{2}O,4SiO_{2} passes into solution. But as a rule clays contain from 45 to 60 p.c. of silica, from 20 to 30 p.c. of alumina, and about 12 p.c. of water; and it cannot be supposed that clays are always homogeneous, because they are an aggregation of residues (of silico-aluminous compounds) which are unacted on by water. Nevertheless, clays always contain a hydrous compound of alumina and silica, which is able to give up the alumina contained by it as a base to strong sulphuric acid, forming aluminium sulphate, which is soluble in water. After this treatment the silica remains, and is soluble in a solution of an alkaline carbonate.[18] [18] Everyone knows that a mixture of clay and water is endowed with the property of taking a given form when subjected to a moderate pressure. This plasticity of clay renders it an invaluable material for practical purposes. From clay are moulded and manufactured a variety of objects, beginning with the common brick and ending with the most delicate china works of art. This _plasticity of clay_ increases with its purity. When articles made of clay are dried, the well-known hard mass is obtained; but water washes it away, and furthermore, the cohesion of its particles is not sufficiently great for it to resist the impression of blows, shocks, &c. If such an article be subjected to the action of heat, its volume first decreases, then it begins to lose water, and it shrinks still further (in the case of a compact mass approximately by 1/5 of its linear measurement). On the other hand, a great coherence of particles is obtained, and thus burnt clay has the hardness of stone. Pure clay, however, shrinks so considerably when burnt that the form given to it is destroyed and cracks easily form; such vessels are also porous, so that they will not hold water. The addition of sand--that is, silica in fine particles--or of _chamotte_--that is, already burnt and crushed clay--renders the mass much more dense and incapable of cracking in the furnace. Nevertheless, such clay articles (bricks, earthenware vessels, &c.) are still porous to liquids after being burnt, because the clay in the furnace is only baked and does not fuse. In order to obtain articles impervious to water the clay must either be mixed with substances which form a glassy mass in the furnace, permeating the clay and filling up its pores, or else only the surface of the article is covered with such a glassy fusible substance. In the first case the purest kinds of clay give what is known as china, in the second case porcelain or 'faïence.' So, for instance, by covering the surface of clay articles with a layer of the oxides of lead and tin, the well-known white glaze is obtained, because the oxides of these metals give a white gloss when fused with silica and clay. In the preparation of china, fluor spar and finely ground silica is mixed up into the clay; these ingredients give a mass which is infusible but softens in the furnace, so that all the particles of the clay cohere in this softened mass, which hardens on cooling. A glaze composed of glassy substances, which only fuse at a high temperature, is also applied to the surface of china articles. Clay is the source from which alumina, Al_{2}O_{3}, and the majority of the compounds of aluminium are prepared. Among these compounds the most important are the alums--that is, the double sulphates of potassium (and allied metals) and aluminium, AlK(SO_{4})_{2},12H_{2}O. When clay is treated with sulphuric acid diluted with a certain amount of water, aluminium sulphate, Al_{2}(SO_{4})_{3}, is formed; and if potassium carbonate or sulphate be added to this solution, a double salt or alum is obtained in solution. The alums crystallise easily, and are prepared on a very large manufacturing scale owing to their being employed in the process of dyeing. Alums are soluble in water, and, on the addition of ammonia to their solutions, they give _hydrous alumina_, or _aluminium hydroxide_, as a white gelatinous precipitate, which is insoluble in water but easily soluble in acids, even when dilute, and in aqueous soda or potash. The solubility of alumina in acids indicates the basic character of the oxide, and its solubility in alkalis and its power of forming compounds with them shows the weakness of this basic character. However, the feeblest acids, even carbonic acid, take up the alkali from such a solution, and the alumina then separates out in a precipitate as the hydroxide. It must also be remembered as characteristic of the salt-forming properties of alumina that it does not combine with such feeble acids as carbonic, sulphurous, or hypochlorous, &c.--that is, its compounds with these acids are decomposed by water. It is also important to observe that the hydroxide is not soluble in aqueous ammonia. _Alumina_, Al_{2}O_{3}--that is, the anhydrous aluminium oxide--is met with in nature, sometimes in a somewhat pure state, having crystallised in transparent crystals, which are often coloured by impurities (chromic, cobaltic, and ferric compounds). Such are the ruby and sapphire, the former red and the latter blue. They have a specific gravity 4·0, are distinguished by their very great hardness, which is second only to that of the diamond, and they represent the purest form of alumina. They are found in Ceylon and other islands of the Indian Archipelago, embedded in a rock matrix.[18 bis] _Corundum_ is the same crystallised anhydrous alumina coloured brown by a trace of oxide of iron. A very much larger portion of this impurity occurs in _emery_, which is found in crystalline masses in Asia Minor and in Massachusetts, and owing to its extreme hardness is employed for polishing stones and metals. In this anhydrous and crystalline state the aluminium oxide is a substance which very powerfully resists the action of reagents, and is insoluble both in solutions of the alkalis and in strong acids. It is only capable of passing into solution after being fused with alkalis.[19] Alumina may be obtained in this form by artificial means if the hydroxide be ignited and then fused in the oxyhydrogen flame.[20] Alumina also occurs in nature in combination with water--as, for instance, in the rather rare minerals _hydrargillite_ (sp. gr. 2·3), Al_{2}O_{3},3H_{2}O = 2Al(HO)_{3}, and _diaspore_, Al_{2}O_3,H_{2}O = 2AlO(HO) (sp. gr. 3·4). A less pure hydrate, mixed with ferric oxide, sometimes occurs in masses (at Baux in the south of France) and is termed _bauxite_; it contains Al_{2}O_{3},2H_{2}O = Al_{2}O(HO)_{4} (sp. gr. 2·6). When bauxite is ignited with sodium carbonate, carbonic anhydride is liberated and the alumina then combines with the sodium oxide, forming a saline aluminate of the oxides of aluminium and sodium. This is taken advantage of in practice for the preparation of pure alumina compounds on a large scale, for bauxite is found in large masses (in the South of France, in Austria, and in Carolina in South America), and the resultant compound of alumina and sodium is soluble in water and does not contain ferric oxide. This solution when subjected to the action of carbonic anhydride gives a precipitate of aluminium hydroxide,[21] which with acids forms aluminium salts. If aqueous ammonia be added to a solution of aluminium sulphate a gelatinous precipitate is formed, which at first remains suspended in the liquid and then on settling forms a gelatinous mass, which itself indicates the _colloidal property of aluminium hydroxide_. The following points are characteristic of this colloidal state: (1) in an anhydrous state such a colloidal substance is insoluble in water, as alumina is; (2) in the hydrated state, it is gelatinous and insoluble in water; and (3) it is also capable of existing in solutions, from which it separates out in a non-crystalline state, forming a substance resembling glue. These different states of colloids were distinguished by Graham, who gave them the following very characteristic names. He called the gelatinous form of the hydrate _hydrogel_, _i.e._ a gelatinous hydrate, and the soluble form of the aqueous compound, _hydrosol_, from the Latin for a soluble hydrate. Alumina readily and frequently assumes these states. The gelatinous hydrate of alumina is its hydrogel. It is, as has been already mentioned, insoluble in water, and, like all similar hydrogels, shows not the faintest sign of crystallisation; it is apt to vary in many of its properties with the amount of water it contains, and loses its water on ignition, leaving a white powder of the anhydrous oxide. The hydrogel of alumina is soluble both in acids and alkalis. It may also be obtained by the evaporation of its solutions in such feebly energetic acids as volatile acetic acid. These properties are very frequently made use of in the arts, and especially in _the processes of dyeing_, because the hydrogel of alumina in precipitating attracts a number of colouring matters from their solutions, the precipitate being thus coloured by the dyes attracted.[22] The preparation of fixed dyes and the employment of aluminous compounds (mordants) in the processes of dyeing are founded on this fact.[23] When precipitated upon the fibres of tissues (calicoes, linens, &c.) the aluminium hydroxide renders them impermeable to water; this may be taken advantage of for the preparation of waterproof tissues. [18 bis] Frémy (1890) obtained transparent rubies, which crystallised in rhombohedra, and resembled natural rubies in their hardness, colour, size, and other properties. He heated together a mixture of anhydrous alumina containing more or less caustic potash, with barium fluoride and bichromate of potassium. The latter is added to give the ruby its colour, and is taken in small quantity (not more than 4 parts by weight to 100 parts of alumina). The mixture is put into a clay crucible, and heated (for from 100 hours to 8 days) in a reverberatory furnace at a temperature approaching 1,500°. At the end of the experiment the crucible was found to contain a crystalline mass, and the walls were covered with crystals of the ruby of a beautiful rose colour. It was found that the access of moist air was indispensable for the reaction. According to Frémy, the formation of the ruby may be here explained by the formation of fluoride of aluminium which under the action of the moist air at the high temperature of the furnace gives the ruby and hydrofluoric acid gas. [19] The effects of purely mechanical subdivision on the solubility of alumina are evident from the fact that native anhydrous alumina, when converted into an exceedingly fine powder by means of levigation, dissolves in a mixture of strong sulphuric acid and a small quantity of water, especially when heated in a closed tube at 200°, or when fused with acid sulphate of potassium (_see_ Chapter XIII., Note 9). [20] The preparation of crystallised alumina is given on p. 65, and in Note 18 bis. When alumina, moistened with a solution of cobalt salt, is ignited, it forms a blue mass called Thénard's salt. This coloration is taken advantage of not only in the arts, but also for distinguishing alumina from other earthy substances resembling it. [21] The treatment of bauxite is carried on on a large scale, chiefly in order to obtain alumina from alkaline solutions, free from ferric oxide, because in dyeing it is necessary to have salts of aluminium which do not contain iron. But this end, it would seem, may also be obtained by igniting alumina containing ferric oxide in a stream of chlorine mixed with hydrocarbon vapours, as ferric chloride then volatilises. K. Bayer observed that in the treatment of bauxite with soda, about 4 molecules of sodium hydroxide pass into solution to 1 molecule of alumina, and that on agitating this solution (especially in the presence of some already precipitated aluminium hydroxide), about two-thirds of the alumina is precipitated, so that only 1 molecule of alumina to 12 molecules of sodium hydroxide remains in solution. This solution is evaporated directly, and used again. He therefore treats bauxite directly with a solution of NaHO at 170° in a closed boiler, and on cooling adds hydrated alumina to the resultant solution. The greater part of the dissolved alumina then precipitates on this hydrated alumina, and the solution is used over again. The hydroxide which separates from the alkaline solution contains Al(OH)_{3}. All these properties bear a great resemblance to those of boric acid. It may be taken for granted that the relation between sodium hydroxide and alumina in solution varies with the mass of water. If lime be added to a solution of alumina in alkali (sodium aluminate) calcium aluminate is precipitated, from which acids first extract the lime, leaving aluminium hydroxide, which is easily soluble in acids (Loewig). When sodium aluminate is mixed with a solution of sodium bicarbonate, a double carbonate of the alkali and aluminium is precipitated, which is easily soluble in acids. [22] These coloured precipitates of alumina are termed _lakes_, and are employed in dyeing tissues and in the formation of various pigments--such as pastels, oil colours, &c. Thus, if organic colouring matters, such as logwood, madder, &c., are added to a solution of any aluminium salt, and then an alkali is added, so that alumina may be precipitated, these pigments, which are by themselves soluble in water, will come down with the precipitate. This shows that alumina is able to combine with the colouring matter, and that this compound is not decomposed by water. The dyes then become insoluble in water. If a dye be mixed with starch paste and aluminium acetate, and then, by means of engraved blocks having a design in relief, we transfer this mixture to a fabric which is then heated, the aluminium acetate will leave the hydrogel of alumina which binds the colouring matter, and water will no longer be able to wash the pigment from the material--that is, a so-called 'fixed' dye is obtained. In the case of dyeing a fabric a uniform tint, it is first soaked in a solution of aluminium acetate and then dried, by which means the acetic acid is driven off, while the hydrogel of alumina adheres to the fibres of the material. If the latter be then passed through a solution of a dye in water, the former will be attracted to the portions covered with alumina, and closely adhere to them. If certain parts of the material be protected by the application of an acid, such as tartaric, C_{4}H_{6}O_{6}, oxalic, citric, &c. (these acids being non-volatile), the alumina will be dissolved in those parts, and the pigment will not adhere, so that after washing, a white design will be obtained on those parts which have been so protected. In dye-works the aluminium acetate is generally obtained in solution by taking a solution of alum, and mixing it with a solution of lead acetate. In this case lead sulphate is precipitated and aluminium acetate remains in solution, together with either acetate or sulphate of potassium, according to the amount of acetate of lead first taken. The complete decomposition will be as follows: KAl(SO_{4})_{2} + 2Pb(C_{2}H_{3}O_{2})_{2} = KC_{2}H_{3}O_{2} + Al(C_{2}H_{3}O_{2})_{3} + 2PbSO_{4}, or the less complete decomposition, 2KAl(SO_{4})_{2} + 3Pb(C_{2}H_{3}O_{2})_{2} = 2Al(C_{2}H_{3}O_{2})_{3} + K_{2}SO_{4} + 3PbSO_{4}. If the resultant solution of aluminium acetate be evaporated or further boiled, the acetic acid passes off and the hydrogel of alumina remains. As the salt of potassium obtained in the solution passes away with the water used for washing, and the salt of lead precipitated has no practical use, this method for the preparation of aluminium acetate cannot be considered economical; it is retained in the process of dyeing mainly because both the salts employed, alum and sugar of lead, easily crystallise, and it is easy to judge of their degree of purity in this form. Indeed, it is very important to employ pure reagents in dyeing, because if impurity is present--such as a small quantity of an iron compound--the tint of the dye changes; thus madders give a red colour with alumina, but if oxide of iron be present the red changes into a violet tint. The aluminium hydroxide is soluble in alkalis, whilst ferric oxide is not. Therefore sodium aluminate--that is, the dissolved compound of alumina and caustic soda--obtained, as already described, from bauxite, is sometimes employed in dyeing. Every aluminium salt gives a solution containing sodium aluminate free from iron, when it is mixed with excess of caustic soda. This solution, when mixed with a solution of ammonium chloride, gives a precipitate of the hydrogel of alumina: Al(OH)_{3} + 3NaHO + 3NH_{4}Cl = Al(OH)_{3} + 3NaCl + 3NH_{4}OH. There was originally free soda, and on the addition of sal-ammoniac there is free ammonia, and this does not dissolve alumina, therefore the hydrogel of the latter is precipitated. [23] Another direct method for the preparation of pure aluminium compounds consists in the treatment of _cryolite_ containing aluminium fluoride together with sodium fluoride, AlNa_{3}F_{6}. This mineral is exported from Greenland, and is also found in the Urals. It is crushed and heated in reverberatory furnaces with lime, and the resultant mass is treated with water; sodium aluminate is then obtained in solution, and calcium fluoride in the precipitate AlNa_{3}F_{6} + 3CaO = 3CaF_{2} + AlNa_{3}O_{3}. _The hydrosol_ of alumina--_i.e._ the soluble aluminium hydroxide--is more difficult to obtain.[24] In order to obtain this soluble variety of alumina, Graham took a solution of its hydrogel in hydrochloric acid--that is, a solution of aluminium chloride, which is able to dissolve a still further quantity of the hydrogel of alumina, forming a basic salt having probably one of the compositions Al(HO)Cl_{2} or Al(HO)_{2}Cl. When such a solution, considerably diluted with water, is subjected to dialysis--that is, to diffusion through a membrane[25]--the hydrochloric acid diffuses through the membrane and leaves the alumina in the form of hydrosol. The resultant solution, even when only containing two or three per cent. of alumina, passes into the hydrogel state with such facility that it is sufficient to transfer it from one vessel to another which has not been previously washed with water, for the entire mass to solidify into a jelly. But a solution containing not more than one-half per cent. of alumina may even be boiled without coagulating; however, after the lapse of several days this solution will of its own accord yield the hydrogel of alumina.[25 bis] [24] Crum first prepared a solution of basic acetate of alumina--that is, a salt containing as large as possible an excess of aluminium hydroxide with as small as possible a quantity of acetic acid. The solution must be dilute--that is, not contain more than one part of alumina per 200 of water--and if this solution be heated in a closed vessel (so that the acetic acid cannot evaporate) to the boiling point of water, for one and a half to two days, then the solution, which apparently remains unaltered, loses its original astringent taste, proper to solutions of all the salts of alumina, and has instead the purely acid taste of vinegar. The solution then no longer contains the salt, but acetic acid and the hydrosol of alumina in an uncombined state; they may be isolated from each other by evaporating the acetic acid in shallow vessels at the ordinary temperature, and with a thin layer of liquid the alumina does not separate as a precipitate. When the acid vapours cease to come off there remains a solution of the hydrosol of alumina, which is tasteless and has no action on litmus paper. When concentrated, this solution acquires a more and more gluey consistency, and when completely evaporated over a water-bath it leaves a non-crystalline glue-like hydrate, whose composition is Al_{2}H_{4}O_{5} = Al_{2}O_{3},2H_{2}O. The smallest quantity of alkalis, and of many acids and salts, will convert the hydrosol into the hydrogel of alumina--that is, convert the aluminium hydroxide from a soluble into an insoluble form, or, as it is said, cause the hydrate to coagulate or gelatinise. The smallest amount of sulphuric acid and its salts will cause the alumina to gelatinise--that is, cause the hydrogel to separate. Many such colloidal solutions are known (Vol. I. p. 98, Note 57). [25] In a dialyser, Vol. I. p. 63, Note 18. [25 bis] The different states in which the hydrates of alumina occur and are prepared resemble similar varieties of the hydrates of the oxides of iron and chromium, of molybdic and tungstic acids, as well as of phosphoric and silicic acids, of many sulphides, proteid substances, &c. We shall therefore have occasion to recur to this subject in the further course of this work. The most remarkable peculiarity of Graham's solution is that it solidifies on litmus paper, and leaves a blue ring on it, which shows the alkaline--that is, basic--character of the alumina in such a solution. If in the dialysis the basic hydrochloric acid salt be replaced by a similar acetic acid salt, a hydrosol of alumina is obtained which does not act upon litmus. With respect to alumina as a base, it is very important to observe that it is not only capable of combining with other bases[26] but that it does not give salts with feeble volatile acids (like carbonic and hypochlorous); it forms salts which are easily decomposed by water, especially when heated,[27] as well as double and basic salts,[28] _so that it forms a clear example of a feeble base_.[29] To these characteristics of alumina we must add that it not only gives compounds of the type AlX_{3}, but also the polymeric type Al_{2}X_{6}, even when X is a simple univalent haloid like chlorine. Deville and Troost showed (1857) that the vapour density of aluminium chloride (at about 400°) is 9·37 with respect to air--that is, nearly 135 with respect to hydrogen, and therefore the formula of its molecule is expressed by Al_{2}Cl_{6}, and not AlCl_{3},[30] although in the case of boron, arsenic, and antimony, which give oxides R_{2}O_{3} of the same composition as Al_{2}O_{3}, the chlorine compounds form non-polymeric molecules, BCl_{3}, AsCl_{3}, SbCl_{3}.[31] This duplication (polymerisation) of the form AlX_{3} is connected with the facility with which the salts of aluminium combine with other salts to form double salts and with aluminium hydroxide itself to form basic salts. [26] Compounds of alumina with bases (aluminates, _see_ Note 21) are sometimes met with in nature. Such are spinel (_see_ p. 65), MgO,Al_{2}O_{3} = MgAl_{2}O_{4}, chrysoberyl, BeAl_{2}O_{4}, and others. Magnetic oxide of iron, FeO,Fe_{2}O_{3} = Fe_{3}O_{4}, and compounds like it, belong to the same class. Here we evidently have a case of combination 'by analogy,' as in solutions and alloys, accompanied by the formation of strictly definite saline compounds, and such instances form a clear transition from so-called solutions and certain mixtures to the type of true salts. [27] Not only aluminium acetate (Note 24), but also every other aluminium salt with a volatile acid, parts with its acid on heating an aqueous solution--that is, is decomposed by water, and forms either basic salts or a hydrate of alumina. By dissolving aluminium hydroxide in nitric acid we may easily obtain a well-crystallising _aluminium nitrate_, Al(NO_{3})_{3},9H_{2}O, which fuses at 73° without decomposing (Ordway), gives a basic salt, 2Al_{2}O_{3},6HNO_{3}, at 100°, and at 140° leaves the aluminium hydroxide perfectly free from the elements of nitric acid. But the solutions of this salt, like those of the acetate, are also able to yield aluminium hydroxide. From all this it is evident that we must suppose that the solutions of this and similar salts contain an equilibrated dissociated system, containing the salt, the acid, and the base, and their compounds with water, as well as partly the molecules of water itself. Such examples much more clearly confirm those conceptions of solutions which are given in the first chapter than a general preliminary acquaintance with the subject can do. [28] As an example of native basic salts we may cite _alunite_, or alum-stone (sp. gr. 2·6), which sometimes occurs in crystals, but more frequently in fibrous masses. It has been found in masses in the Caucasus (at Zaglik, forty versts distance from Elizabetpol), and at Tolfa, near Rome. Its composition is K_{2}O,3Al_{2}O_{3},4SO_{3},6H_{2}O (alunite contains 9H_{2}O). It is soluble in water but not decomposed by it, but after being slightly ignited it gives up alum to it. It may be artificially prepared by heating a mixture of alum with aluminium sulphate in a closed tube at 230°. [29] As the colloidal properties are particularly sharply developed in those oxides (Al_{2}O_{3}, SiO_{2}, MoO_{3}, SnO_{2}, &c.) which show (like water also) the properties of feeble bases and feeble acids, there is probably some causal reason for this coincidence, all the more so since among organic substances--gelatins, albumins, &c.--the representatives of the colloids also have the property of feebly combining with bases and acids. [30] Since Deville's experiments the question of the density of aluminium chloride has been frequently re-investigated. The subject has more especially occupied the attention of Nilson, Pettersson, Friedel and Crafts, and V. Meyer and his collaborators. In general, it has been found that at low temperatures (up to 440°) the density is constant, and indicates a molecule Al_{2}Cl_{6}; whilst depolymerisation probably (although it is not yet certain) takes place at higher temperatures, and the molecule AlCl_{3} is obtained. Along with this there has been, and still is, a difference of opinion as to the vapour density of aluminium ethyl and methyl--whether for instance, Al(CH_{3})_{3} or Al_{2}(CH_{3})_{6} expresses the molecule of the latter. The interest of these researches is intimately connected with the question of the valency of aluminium, if we hold to the opinion that elements in their various compounds have a constant and strictly definite valency. In this case the formula AlCl_{3} or Al(CH_{3})_{3} would show that Al is trivalent, and that consequently the compounds of aluminium are Al(OH)_{3}, AlO_{3}Al, and, in general, AlX_{3}. But if the molecule be Al_{2}Cl_{6}, it is--for the followers of the doctrine of the invariable valency of the elements--incompatible with the idea of the trivalency of aluminium, and they assume it to be quadrivalent like carbon, likening Al_{2}Cl_{6} to ethane C_{2}H_{6} = CH_{3}CH_{3}, although this does not explain why Al does not form AlCl_{4}, or, in general, AlX_{4}. In this work another supposition is introduced; according to this, although aluminium, as an element of group III., gives compounds of the type AlX_{5}, this does not exclude the possibility of these molecules combining with others, and consequently with _each other_--that is, forming Al_{2}X_{6}; just as the molecules of univalent elements exist either as H_{2}, Cl_{2}, &c., or as Na, and the molecules of bivalent elements either as Zn, or as S_{2}, or even S_{6}. In the first place it must be recognised that the limiting form does not exhaust all power of combination, it only exhausts the capacity of the element for combining with X's, but the saturated substance may afterwards combine with _whole molecules_, which fact is best proved by the capacity of substances to form crystalline compounds with water, ammonia, &c. But in some substances this faculty for further combinations is less developed (for instance, in carbon tetrachloride, CCl_{4}), whilst in others it is more so. AlX_{3} combines with many other molecules. Now if a limiting form, which does not combine with new X's, nevertheless combines with other whole molecules, it will naturally in some instances combine with itself, will polymerise. In this manner the mind clearly grasps the idea that the same forces which cause S_{2} to unite itself to Cl_{2}, or C_{2}H_{4} to Cl_{2}, &c., also unite molecules of a similar kind together; thus _polymerisation_ ceases to be an isolated fragmentary phenomenon, and chemical combinations 'by analogy' acquire a particular and important interest. In conformity with these views the following proposition may be made concerning the compounds of aluminium. They are of the type AlX_{3} in the limit, like BX_{3}, but those limiting forms are still able to combine to form AlX_{3},RZ, and the aluminium chloride is a compound of this kind--_i.e._ (AlX_{3})_{2}. In boron, for example, in BCl_{3}, this tendency to form further compounds is less developed. Hence boron chloride appears as BCl_{3}, and not (BCl_{3})_{2}. Polymerisation is not only possible when a substance has not attained the limit (although it is more probable then), but also when the limiting form has been reached, if only the latter has the faculty of combining with other whole molecules. We may therefore conclude that aluminium, like boron, is trivalent in the same sense that lithium and sodium are univalent, magnesium bivalent, and carbon tetravalent. In a word, there is no reason to consider that aluminium is capable of forming compounds AlX_{4}, and in that way to explain the existence of the molecule Al_{2}Cl_{6}. Furthermore, there are many reasons for thinking that AlF_{3}, Al_{2}O_{3}, and other empirical formulæ do not express the molecular weights of these compounds, but that they are much higher: Al_{_n_}F_{3_n_}, Al_{2_n_}O_{3_n_}. In recent years convincing proofs of the truth of the above statements have been obtained, and of the independent existence of AlX_{3} in a state of vapour; for Comb has determined the vapour density of the volatile acetyl of aluminium acetate Al(C_{3}H_{7}O_{2})_{3} (which melts at 193°, boils at 315°, and distils without a trace of decomposition), and has found that it exactly corresponds to the above molecular composition. On the other hand, Louise and Roux (1889) by employing the method of 'freezing point depression' of solutions (Chapter I., Note 49) found that the molecules Al_{2}(C_{2}H_{5})_{6} and Al_{2}(C_{5}H_{11})_{6}, &c., correspond to the type Al_{2}X_{6}. Thus it may now be accepted that the molecular composition of the compounds of aluminium in their simplest form is AlX_{3}, but that they may polymerise and give Al_{2}X_{6} or, in general, Al_{2}X_{3_n_}. [31] In the case of gallium, as a close analogue of aluminium, Lecoq de Boisbaudran (1880) showed that probably the molecule gallium chloride contains Ga_{2}Cl_{6} at low temperatures and high pressures, and that it dissociates into GaCl_{3} at high temperatures and low pressures. The molecule of indium chloride seems to exist only in the simplest form, InCl_{3}. _Aluminium sulphate_, Al_{2}(SO_{4})_{3}, which is obtained by treating clay or the hydrates of alumina with sulphuric acid, crystallises in the cold with 27H_{2}O, or at the ordinary temperature in pearly crystals, which are greasy to the touch and contain 16H_{2}O.[32] Its solutions act like sulphuric acid--for instance, they evolve hydrogen with zinc, forming basic salts, which are sometimes met with in nature (_aluminite_, Al_{2}O_{3},SO_{3},9H_{2}O, _alumiane_, Al_{2}O_{3},2SO_{3}, and others), and may be obtained by the decomposition of normal salts and by the direct solution of the hydroxide in normal salts: these exhibit a varying composition, (Al_{2}O_{3})_{_n_}(SO_{3})_{_m_}(H_{2}O)_{_q_}, where _m/n_ is less than 3. Aluminium sulphate is now prepared (from the pure hydrate obtained from bauxite, Note 21) in large quantities for dyeing purposes (instead of alums) as a mordant. With solutions of the alkali sulphates (potassium, sodium, ammonium, rubidium, and cæsium sulphates), the normal salt easily forms double salts, termed _alums_--for example, the ordinary crystalline alum contains KAl(SO_{4})_{2},12H_{2}O, or K_{2}SO_{4},Al_{2}(SO_{4})_{3},24H_{2}O. In the ammonium alums (which leave a residue of alumina when ignited) the potassium is replaced by ammonium (NH_{4}). Alums are used in large quantities, because there is scarcely any other salt which crystallises so easily. In this respect the alums formed by potassium and ammonium are equally convenient to purify, because they present a considerable difference in their solubility at the ordinary and higher temperatures. If the crystallisation be conducted rapidly, the salt separates in minute crystals, but if it be slowly deposited, especially in large masses, as in factories, then crystals several centimetres long are sometimes obtained. At a higher temperature alums are very much more soluble, and crystallise with greater difficulty, and are therefore less easily freed from impurities; at 0° 100 parts of water dissolve 3 parts, at 30° 22 parts, at 70° 90 parts, and at 100° 357 parts of potassium alum.[33] The solubility of ammonium alum is slightly less. The specific gravity of potassium alum is 1·74, of ammonium alum 1·63, and of sodium alum 1·60. Alums easily part with their water of crystallisation; thus potash alum partially effloresces when exposed to the air, and loses 9 mol. H_{2}O under the receiver of an air-pump. At 100°, dry air passed over alums takes up nearly all their water. As we have already mentioned (Chapter XV.), the law of isomorphous substitutions exhibits itself more clearly in the alums than in any other salts, and all alums not only contain the same amount of water of crystallisation, MR(SO_{4})_{2},12H_{2}O (where M = K, NH_{4}, Na; R = Al, Fe, Cr), and appear in crystals whose planes are inclined at equal angles, but they also give every possible kind of isomorphous mixture. The aluminium in them is easily replaced by iron, chromium, indium and sometimes by other metals, whilst the potassium may be substituted by sodium, rubidium, ammonium, and thallium, and the sulphuric acid may be replaced by selenic and chromic acids. [32] The pure salt (16H_{2}O) is not hygroscopic. In the presence of impurities the amount of water increases to 18H_{2}O, and the salt becomes hygroscopic. [33] The common form of crystals of alums is octahedral, but if this solution contains a certain small excess of alumina above the ratio 2Al(OH)_{3} to K_{2}SO_{4}, and not more sulphuric acid than 3H_{2}SO_{4} to 2Al(OH)_{3}, then it easily forms combinations of the cube and octahedron, and these alums are called 'cubic' alums. They are valued by the dyer because they can contain no iron in solution, for oxide of iron is precipitated before alumina, and if the latter be in excess there can be no oxide of iron present. These alums were long exported from Italy, where they were prepared from alunite (Note 28). _Aluminium chloride_, Al_{2}Cl_{6}, is obtained, like other similar chlorides, (for instance MgCl_{2}) either directly from chlorine and the metal, or by heating to redness an intimate mixture of the amorphous anhydrous oxide and charcoal in a stream of dry chlorine.[33 bis] The resultant sublimate is very volatile,[34] and forms a crystalline, easily fusible mass, which deliquesces in the air and easily dissolves in water, with the evolution of a large amount of heat.[34 bis] On evaporating this solution, hydrochloric acid and aluminium hydroxide are liberated. But if the solution be heated in a closed tube, with an excess of hydrochloric acid, then, on cooling, crystals of AlCl_{3},6H_{2}O are obtained--that is, aluminium chloride both combines with water and is decomposed by it. And the faculty of the type AlX_{3} for combining with other molecules is seen in the compounds of AlCl_{3} with many other chlorine compounds. Thus, for example, a mixture of aluminium chloride with sulphur tetrachloride gives Al_{2}Cl_{6},SCl_{4}, under the action of chlorine, whilst with phosphorus pentachloride it forms AlCl_{3},PCl_{5}; it also combines with NOCl. Thus, the compounds AlCl_{3},NOCl, AlCl_{3},POCl_{3}, AlCl_{3},3NH_{3}, AlCl_{3},KCl, AlCl_{3},NaCl are known.[35] The compound of aluminium and sodium chlorides, AlNaCl_{4}, is very fusible and much more stable in the air than aluminium chloride itself. It seems to be of the same type as the alums. This compound, AlNaCl_{4}, is employed in the extraction of metallic aluminium, as we shall presently proceed to describe. Aluminium bromide, which is obtained by the direct combination of metallic aluminium with bromine, closely resembles the chloride; it melts at 90°, volatilises at 270°, and its vapour density indicates the formula Al_{2}Br_{6}. Aluminium iodide is obtained by heating iodine with finely divided aluminium in a closed tube; it is so easily decomposed by oxygen that its vapour even explodes when mixed with it.[36] [33 bis] It is also formed by the action of hydrochloric acid upon metallic aluminium (Nilson and Pettersson), by heating alumina in a mixture of the vapours of naphthaline and HCl (Faure, 1889), and by the action of dry HCl upon an alloy of 14 p.c., or more of Al and copper (Mobery). [34] Aluminium chloride fuses at 178°, boils at 183° (pressure 755 mm., at 168° under a pressure of 250 mm., and at 213° under 2,278 mm.), according to Friedel and Crafts, so that it boils immediately after fusion. According to Seubert and Pallard (1892), Al_{2}Cl_{6} fuses at 193°. Aluminium bromide fuses at about 92°, and the iodide at 185° according to Weber, at 125° according to Deville and Troost. All these halogen compounds of aluminium are soluble in water. _Aluminium fluoride_, AlF_{3} (Al_{_n_}F_{3_n_}), is insoluble in water. It is obtained by dissolving alumina in hydrofluoric acid; a solution is then formed, but it contains an excess of hydrofluoric acid. When this solution is evaporated, crystals containing Al_{2}F_{6},HF,H_{2}O are obtained. They are also insoluble in water. By saturating the above solution with a large quantity of alumina, and then evaporating, we obtain crystals having the composition Al_{2}F_{6},7H_{2}O. All these compounds, when ignited, leave insoluble anhydrous aluminium fluoride. It forms colourless rhombohedra, which are non-volatile, of sp. gr. 3·1, and are decomposed by steam into alumina and hydrofluoric acid. The acid solution apparently contains a compound which has its corresponding salts; by the addition of a solution of potassium fluoride, a gelatinous precipitate of AlK_{3}F_{6} is obtained. A similar compound occurs in nature--namely, AlNa_{3}F_{6}, or _cryolite_, sp. gr. 3·0. [34 bis] In this respect aluminium chloride resembles the chloranhydrides of the acids, and probably in the aqueous solution the elements of the hydrochloric acid are already separated, at least partially, from the aluminium hydroxide. The solution may also be obtained by the action of aluminium hydroxide on hydrochloric acid. [35] Here we see an instance in confirmation of what has been said in Note 30--_i.e._ the action of the molecule AlCl_{3}. We will cite still another instance confirming the power of alumina to enter into complex combinations. Alumina, moistened with a solution of calcium chloride, gives, when ignited, an anhydrous crystalline substance (tetrahedral), which is soluble in acids, and contains (Al_{2}O_{3})_{6}(CaO)_{10}CaCl_{2}. Even clay forms a similar stony substance, which might be of practical use. Among the most complex compounds of aluminium, _ultramarine_, or _lapis lazuli_, must be mentioned. It occurs in nature near Lake Baikal, in crystals, some colourless and others of various tints--green, blue, and violet. When heated it becomes dull and acquires a very brilliant blue colour. In this form it is used for ornaments (like malachite), and as a brilliant blue pigment. At the present time ultramarine is prepared artificially in large quantities, and this process is one of the most important conquests of science; for the blue tint of ultramarine has been the object of many scientific researches, which have culminated in the manufacture of this native substance. The most characteristic property of ultramarine is that when placed in sulphuric acid it evolves hydrogen sulphide and becomes colourless. This shows that the blue colour of ultramarine is due to the presence of sulphides. If clay be heated in a furnace with sodium sulphate and charcoal (forming sodium sulphide) without access of air, a white mass is obtained, which becomes green when heated in the air, and when treated with water leaves a colourless substance known as 'white ultramarine.' When ignited in the air it absorbs oxygen and turns blue. The coloration is ascribed to the presence of metallic sulphides or polysulphides, but it is most probable that silicon sulphide, or its oxysulphide, SiOS, is present. At all events the sulphides play an important part, but the problem is not yet quite settled. The formula Na_{8}Al_{6}Si_{6}O_{24}S is ascribed to white ultramarine. The green probably contains more sulphur, and the blue a still larger quantity. The last is supposed to contain Na_{8}Al_{6}Si_{6}O_{24}S_{3}. It is more probable (according to Guckelberger, 1882) that the composition of the blue varies between Si_{18}Al_{18}Na_{20}S_{6}O_{71} and Si_{18}Al_{12}Na_{20}S_{6}O_{69}. The latter may be expressed as (Al_{2}O_{3})_{6}(SiO_{2})_{18}(Na_{2}O)_{10}S_{6}O_{5}, which would indicate the presence of insufficiently-oxidised sulphur in ultramarine. [36] At the ordinary temperature aluminium does not decompose water, but if a small quantity of iodine, or of hydriodic acid and iodine, or of aluminium iodide and iodine, is added to the water, then hydrogen is abundantly evolved. It is evident that here the reaction proceeds at the expense of the formation of Al_{2}I_{6}, and that this substance, with water, gives aluminium hydroxide and hydriodic acid, which, with aluminium, evolves hydrogen. Aluminium probably belongs to those metals having a greater affinity for oxygen than for the halogens (Note 36 tri). _Metallic Aluminium_ was first prepared by Wöhler in 1822 as a grey powder by the action of potassium on aluminium chloride. He afterwards (in 1845) obtained it as a white compact metal, unoxidisable in the air, and only slowly attacked by acids. Owing to the vast and wide occurrence of clay, many efforts have been made in investigating in detail the methods for the extraction of this metal. These efforts were brought to a successful issue (1854) by Sainte-Claire Deville, who is also renowned for his doctrine of dissociation. Experiments on a large scale have proved that metallic aluminium, although possessed of great lightness, strength, and durability, is not so generally suitable for technical purposes as was at first thought. Nitric and many other acids, indeed, do not act on it, but the alkalis, alkaline substances, and even salts--for instance, moist table salt--humidity, &c.,[36 bis] tarnish it, and hence objects made of aluminium suffer at the surfaces, alter, and cannot, as was hoped, replace the precious metals, from which it differs in its extreme lightness. But the alloys made with aluminium (especially with copper, for example aluminium bronze) are very valuable in their properties and applications. [36 bis] As an example we may mention that if mercury comes in contact with metallic aluminium and especially if it be rubbed upon the surface of aluminium moistened with a dilute acid, the Al becomes rapidly oxidised (Al_{2}O_{3} being formed). The oxidation is accompanied by a very curious appearance, as it were of wool (or fur) formed by threads of oxide of aluminium growing upon the metal. This was first pointed out by Cass in 1870, and subsequently by A. Sokoleff in 1892. This interesting and curious phenomenon has not to my knowledge been further studied. I think it necessary, however, to add that according to Lubbert and Rascher's researches (1891), wine, coffee, milk, oil, urine, earth, &c., have no more action upon aluminium vessels than upon copper, tin, and other similar articles. In the course of four months ordinary vinegar dissolved 0·35 grm. of Al per sq. centimetre, whilst a 5 per cent. solution of common salt dissolved about 0·05 grm. of aluminium. Ditte (1890) showed that Al is acted upon by nitric and sulphuric acids, although only slowly (owing to the formation of a layer of gas, as in Chapter XVI., Note 10) and that the reaction proceeds much more rapidly in vacuo or in the presence of oxidising agents. Al is even oxidised by water on the surface, but the thin coating of alumina formed prevents further action. In the course of twelve hours nitric acid sp. gr. 1·383 dissolved at 17° about 20 grms. of aluminium (containing only a small amount of Si, 1-1/4 p.c.) from a sq. metre of surface (Le Rouart, 1891). The Deville method for the preparation of metallic aluminium is based on the decomposition of the above-mentioned compound of sodium and aluminium chlorides by metallic sodium. The compound is obtained by passing the vapour of aluminium chloride (evolved from a mixture of alumina, extracted from bauxite or cryolite, with charcoal ignited in a stream of chlorine) over red-hot salt, when the compound AlNaCl_{4}, is itself volatilised, and may in this manner be obtained pure. A mixture of this compound with salt and fluor spar, or with cryolite, is heated with a certain excess of sodium, cut into small lumps. On a large scale this operation is carried on in special furnaces with a small access of air and at a high temperature. The decomposition takes place chiefly according to the equation NaAlCl_{4} + 3Na = 4NaCl + Al. Neither charcoal nor zinc will reduce the oxygen compounds of aluminium; even sodium and potassium do not act on alumina. Moreover, metallic aluminium, like magnesium, is able to reduce even the metals of the alkalis from their oxygen compounds. This is connected with the fact that the atom of oxygen evolves more heat in combining with Al (and Mg) than it does in combining with other metals; whilst on the other hand, chlorine (and the other halogens) evolve more heat in combining with the metals of the alkalis.[36 tri] [36 tri] In addition to the data given in Chapters XI., XIII., and in Chapter XV., Note 19, the following are the amounts of heat in thousands of units, evolved in the formation of the oxides and chlorides from the metals taken in gram-atomic quantities: Na_{2}O 100; MgO 140*; 1/3Al_{2}O_{3} 120*; 1/3Fe_{2}O_{3} 63*; Na_{2}Cl_{2} 195; MgCl_{2} 151; 1/3Al_{2}Cl_{6} 107; 1/3Fe_{2}Cl_{6} 64. The asterisks following the oxides of Mg, Al and Fe call attention to the fact that the existing data refer to the formation of the hydrates of these metals, from which the heat of formation of the anhydrous oxides may easily be assumed, because the heat of hydration (for example, MgO + H_{2}O) has not yet been determined. Since the close of the eighties the metallurgy of aluminium has taken a new direction, based upon the action of an electric current upon cryolite at a high temperature,[37] and the solution of oxide of aluminium (obtained from bauxite or in the form of corundum) in it; under these conditions metallic aluminium is reduced at the negative pole (cathode) in a sufficiently pure state, and if the cathode be copper, forms alloys with it. Such are Hall's and Cowle's (both in the United States) and the Neuhausen process (where the current is obtained from a dynamo worked by the Falls of the Rhine at Schaffhausen). As an example, we will describe (in the words of Prof. D. P. Konovaloff, who became acquainted with this process at the Chicago Exhibition), Hall's process as applied near Pittsburg, where it gives about 1,500 kilos of Al a day. An iron box (about 1 metre long and 1/2 metre wide), provided with a well rammed down charcoal lining, is charged with a mixture of cryolite and Al_{2}O_{3} (from bauxite), over which salt is strewn, and a current of 5,000 ampères at 20 volts is passed through the mixture. The anode is composed of a carbon cylinder (about 9 cm. in diameter), while the charcoal lining forms the cathode. When the temperature inside the box is raised to a red heat by the current, the mixture fuses and the Al_{2}O_{3} begins to decompose. The Al liberated collects at the bottom of the box, whilst the oxygen evolved burns the charcoal anode. When the decomposition is at an end, and the resistance of the mass increases, a fresh quantity of Al_{2}O_{3} is added, and this is continued until the amount of impurities accumulated in the furnace and passing into the metal becomes too great.[37 bis] [37] Cryolite under the action of the current at about 1,000° gives off the vapour of Na which reduces the Al, but it recombines with the liberated fluorine and again passes into the fused mass. It is important to obtain aluminium at as low a temperature as possible, but the action proceeds far more easily with the solution (alloy) of oxide of aluminium in cryolite. [37 bis] The cost of working this process can be brought as low as 20 cents per lb. or about 2-1/2 fcs. per kilo. In England, Castner, prior to the introduction of the electric method, obtained Al by taking a mixture of 1,200 parts of the double salt NaAlCl_{4}, 600 parts of cryolite, and 350 parts of Na, and obtained about 120 parts of Al, so that the cost of this process is about 1-1/2 time that of the electric method. Buchner found that sulphide of aluminium, Al_{2}S_{3}, is more suitable for the preparation of Al by the electrolytic method than Al_{2}O_{3}, but since the formation of Al_{2}S_{3} by heating a mixture of Al_{2}O_{3}, and charcoal in sulphur vapour proceeds with difficulty, Gray (1894) proposed to prepare Al_{2}S_{3} by heating a mixture of charcoal, sulphate of aluminium, and sodium fluoride. The resultant molten mixture of NaF and Al_{2}S_{3} gives aluminium directly under the action of an electric current. Aluminium has a white colour resembling that of tin--that is, it is greyer than silver and has the feebly dull lustre of tin, but compared to tin and pure silver, aluminium is very hard. Its density is 2·67--that is, it is nearly four times lighter than silver and three times lighter than copper. It melts at an incipient red heat (600°), and in so doing is but slightly oxidised. At the ordinary temperature it does not alter in the air, and in a compact mass it burns with great difficulty at a white heat, but in thin sheets, into which it may be rolled, or as a very fine wire, it burns with a brilliant white light, since it forms an infusible and non-volatile oxide. Aluminium itself is non-volatile at a furnace heat. These properties render Al a very good reducing agent, and N. N. Beketoff showed that it reduces the oxides of the alkali metals (Chapter XIII., Note 42 bis). Dilute sulphuric acid has scarcely any action on it, but the strong acid dissolves it, especially with the aid of heat. Nitric acid, dilute or strong, has no action whatever on it. On the other hand, hydrochloric acid dissolves aluminium with great ease, as do also solutions of caustic soda and potash. In the latter cases hydrogen is evolved.[38] [38] Aluminium, when heated to the high temperature of the electric furnace, dissolves carbon and forms an alloy which, according to Moissan, when rapidly treated with _cold_ hydrochloric acid leaves a compound C_{3}Al_{4} in the form of a yellow crystalline transparent powder, sp. gr. 2·36 (_see_ Chapter VIII. Note 12 bis). This _carbide of aluminium_ C_{3}Al_{4} corresponds to methane CH_{4}, for Al replaces H_{3} and carbon O_{2} or H_{4}, that is, it is equal to three molecules of CH_{4} with the substitution of twelve atoms of H in it by four of Al, or, what is the same thing, it is the duplicated molecule of Al_{2}O_{3} with the substitution of O_{6} by C_{3}. And indeed C_{3}Al_{4} under the action of water forms marsh gas and hydrate of alumina: C_{3}Al_{4} + 12H_{2}O = 3CH_{4} + 4Al(OH)_{3}. This decomposition gives a new aspect of the synthesis of hydrocarbons, and quite agrees with what should follow from the action of water upon the metallic carbides as applied by me for explaining the origin of naphtha (Chapter VIII., Notes 57, 58, and 59). Frank (1894) by heating Al with carbon obtained a similar although not quite pure compound, which (like CaC_{2}) evolves acetylene with hydrochloric acid _i.e._ probably has the composition AlC_{3}. Aluminium forms alloys with different metals with great ease. Among them the copper alloy is of practical use. It is called _aluminium bronze_. This alloy is prepared by dissolving 11 p.c. by weight of metallic aluminium in molten copper at a white heat. The formation of the alloy is accompanied by the development of a considerable quantity of heat, so that it glows to a bright white heat. This alloy, which corresponds with the formula AlCu_{3}, presents an exceedingly homogeneous mass, especially if perfectly pure copper be taken. It is distinguished for its capacity to fill up the most minute impressions of the mould into which it may be cast, and by its extraordinary elasticity and toughness, so that objects cast from it may be hammered, drawn, &c., and at the same time it is fine-grained and exceedingly hard, takes an excellent polish, and, what is most important, its surface then remains almost unchangeable in the air, and has a colour and lustre which may be compared to that of gold alloys. Hence aluminium bronze is much used in the arts for making spoons, watches, vessels, forks, knives, and for ornaments, &c. No less important is the fact that the admixture of one-thousandth part of aluminium with steel renders its castings homogeneous (free from cavities) to an extent that could not be arrived at by other means, nor does the quality of the steel in any respect deteriorate by this admixture, but rather is it improved. In a pure state, aluminium is only employed for such objects as require the hardness of metals with comparative lightness, such as telescopes and various physical apparatus and small articles. According to the periodic system of the elements, the analogues of magnesium are zinc, cadmium, and mercury in the second group. So also in the third group, to which aluminium belongs, we find its corresponding analogues _gallium_, _indium_, and _thallium_. They are all three so rarely and sparingly met with in nature that they could only be discovered by means of the spectroscope. This fact shows that they are partially volatile, as should be the case according to the property of their nearest neighbours, the very volatile zinc, cadmium and mercury. As with them, in gallium, indium, and thallium the density of the metal, decomposability of compounds, &c., rises with the atomic weight. But here we find a peculiarity which does not exist in the second group. In the latter, the fusibility increases with the atomic weight of magnesium, zinc, cadmium, and mercury; indeed, the heaviest metal--mercury--is a liquid. In the third group it is not so. In order to understand this it is sufficient to turn our attention to the elements of the further groups of the uneven series--for instance, to group V., containing phosphorus, arsenic, and antimony, or to group VI., with sulphur, selenium, and tellurium, and also to group VII., where chlorine, bromine and iodine are situated. In all these instances the fusibility decreases with a rise of atomic weight; the members of the higher series, the elements of a high atomic weight, fuse with greater difficulty than the lighter elements. The representatives of the uneven series of group III., aluminium, gallium, indium, thallium, forming, as they do, a transition, all show an intermediate behaviour. Here the most fusible of all is the medium metal gallium,[38 bis] which fuses at the heat of the hand; whilst indium, thallium, and aluminium fuse at much higher temperatures. [38 bis] The same is the case in group IV. of the uneven series, where tin is the most fusible. Thus the temperature of fusion rises on both sides of tin (silicon is very infusible; germanium, 900°; tin, 230°; lead, 326°); as it also does in group III., starting from gallium, for indium fuses at 176°, less easily than gallium but more easily than thallium (294°). Aluminium also fuses with greater difficulty than gallium. Zinc (group II.), which has an atomic weight 65, should be followed in group III. by an element with an atomic weight of about 69. It will be in the same group as Al and should consequently give R_{2}O_{3}, RCl_{3}, R_{2}(SO_{4})_{3}, alums and similar compounds analogous to those of aluminium. Its oxide should be more easily reducible to metal than alumina, just as zinc oxide is more easily reduced than magnesia. The oxide R_{2}O_{3} should, like alumina, have feeble but clearly expressed basic properties. The metal reduced from its compounds should have a greater atomic volume than zinc, because in the fifth series, proceeding from zinc to bromine, the volume increases. And as the volume of zinc = 9·2, and of arsenic = 18, that of our metal should be near to 12. This is also evident from the fact that the volume of aluminium = 11, and of indium = 14, and our metal is situated in group III., between aluminium and indium. If its volume = 11·5 and its atomic weight be about 69, then its density will be nearly 5·9. The fact that zinc is more volatile than magnesium gives reason for thinking that the metal in question will be more volatile than aluminium, and therefore for expecting its discovery by the aid of the spectroscope, &c. These properties were indicated by me for the analogue of aluminium in 1871, and I named it (_see_ Chapter XV.) eka-aluminium. In 1875, Lecoq de Boisbaudran, who had done much work in spectrum analysis, discovered a new metal in a zinc blende from the Pyrenees (Pierrefitte). He recognised its individuality and difference from zinc, cadmium, indium, and the other companions of zinc by means of the spectroscope; but he only obtained some fractions of a centigram of it in a free state. Consequently only a few of its reactions were determined, as, for instance, that barium carbonate precipitates the new oxide from its salts (alumina, as is known, is also precipitated). Lecoq de Boisbaudran named the newly discovered metal _gallium_. As one would expect the same properties for eka-aluminium as were observed in gallium, I pointed out this fact at the time in the Memoirs of the Paris Academy of Sciences. All the subsequent observations of Lecoq de Boisbaudran confirmed the identity between the properties of gallium and those indicated for eka-aluminium. Immediately after this the ammonium alum of gallium was obtained, but the most convincing proof of all was found in the fact that the density of gallium although first apparently different (4·7) from that indicated above, afterwards, when the metal was carefully purified from sodium (which was first used as a reducing agent), proved to be just that (5·9) which would have been looked for in the analogue of aluminium; and, what was very important, the equivalent (23·3) and atomic weight (69·8) determined by the specific heat (0·08) were shown by experiment to be such as would be expected. These facts confirmed the universality and applicability of the periodic system of the elements. It must be remarked that previous to it there was no means of either foretelling the properties or even the existence of undiscovered elements.[39] [39] The spectrum of gallium is characterised by a brilliant violet line of wave-length = 417 millionths of a millimetre. The metal can be separated from the solution, containing a mixture of the many metals occurring in the zinc blende, by making use of the following reactions: it is precipitated by sodium carbonate in the first portions; it gives a sulphate which, on boiling, easily decomposes into a basic salt, very slightly soluble in water; and it is deposited in a metallic state from its solutions by the action of a galvanic current. It fuses at +30°, and, when once fused, remains liquid for some time. It oxidises with difficulty, evolves hydrogen from hydrochloric acid and from potassium hydroxide, and, like all feeble bases (for instance, alumina and indium oxide), it easily forms basic salts. The hydroxide is soluble in a solution of caustic potash, and slightly so in caustic ammonia. Gallium forms volatile GaCl_{3} and GaCl_{2} (Nilson and Pettersson). Much more light has been thrown on that element of the aluminium group which follows after cadmium (its position in the periodic system is III., 7, that is, it is in group III. in the 7th series). This is _indium_, In, which also occurs in small quantities in certain zinc ores. It was discovered (1863) by Reich and Richter (and more fully investigated by Winkler) in the Freiberg zinc ores, and was named indium from the fact that it gives to the flame of a gas-burner a blue coloration, owing to the indigo blue spectral lines proper to it. The equivalent (_see_ Chapter XV., Note 15), specific heat, and other properties of the metal confirm the atomic weight In = 113.[40] [40] The vapour density of indium chloride, InCl_{3} (Note 31), determined by Nilson and Pettersson, confirms this atomic weight. Indium is separated from zinc and cadmium, with which it occurs, by taking advantage of the fact that its hydroxide is insoluble in ammonia, that the solutions of its salts give indium when treated with zinc (hence indium is dissolved after zinc by acids) and that they give a precipitate with hydrogen sulphide even in acid solutions. Metallic indium is grey, has a sp. gr. of 7·42, fuses at 176°, and does not oxidise in the air; when ignited, it first gives a black suboxide, In_{4}O_{3}, then volatilises and gives a brown oxide, In_{2}O_{3}, whose salts, InX_{3}, are also formed by the direct action of acids on the metal, hydrogen being evolved. Caustic alkalis do not act on indium, from which it is evident that it is less capable of forming alkaline compounds than aluminium is; however, with potassium and sodium hydroxides, solutions of indium salts give a colourless precipitate of the hydroxide, which is soluble in an excess of the alkali, like the hydroxides of aluminium and zinc. Its salts do not crystallise. Nilson and Pettersson (1889), by the action of HCl upon In, obtained volatile crystalline, InCl_{2}, and by treating this compound with In, InCl also. Inasmuch as we found among the analogues of magnesium in group II. a metal, mercury, heavier and more easily reduced than the rest, and giving two grades of oxidation, so we should expect to find a metal among the analogues of aluminium in group III. which would be heavy, easily reduced, and give two grades of oxidation, and would have an atomic weight greater than 200. Such is _thallium_. It forms compounds of a lower type, TlX, besides the higher unstable type TlX_{3}, just as mercury gives HgX_{2} and HgX. In the form of the thallic oxide, Tl_{2}O_{3}, the base is but feebly energetic, as would be expected by analogy with the oxides Al_{2}O_{3}, Ga_{2}O_{3}, and In_{2}O_{3}, whilst in thallous oxide, Tl_{2}O, the basic properties are sharply defined, as might be expected according to the properties of the type R_{2}O (Chapter XV.). _Thallium_ was discovered in 1861 by Crookes and by Lamy in certain pyrites. When pyrites are employed in the manufacture of sulphuric acid, they are burned, and give besides sulphurous anhydride the vapours of various substances which accompany the sulphur, and are volatile. Among these substances arsenic and selenium are found, and together with them, thallium. These substances accumulate in a more or less considerable quantity in the tubes through which the vapours formed in the combustion of the pyrites have to pass. When the methods of spectrum analysis were discovered (1860), a great number of substances were subjected to spectroscopic research, and it was observed that those sublimations which are obtained in the combustion of certain pyrites contained an element having a very sharply-defined and characteristic spectrum--namely, in the green portion of the spectra it gave a well-defined band (wave-length 535 millionth millimetres) which did not correspond with any then known element.[41] [41] Thallium was afterwards found in certain micas and in the rare mineral crookesite, containing lead, silver, thallium, and selenium. Its isolation depends on the fact that in the presence of acids thallium forms thallous compounds, TlX. Among these compounds the chloride and sulphate are only slightly soluble, and give with hydrogen sulphide a black precipitate of the sulphide Tl_{2}S, which is soluble in an excess of acid, but insoluble in ammonium sulphide. Under the action of a galvanic current solutions of thallium salts deposit the metal in the form of a heavy powder. It is of a grey colour like tin, is soft like sodium, and has a metallic lustre. Its specific gravity is 11·8, it melts at 290°, and volatilises at a high temperature. When heated slightly above its melting point it forms an insoluble (in water) higher oxide, Tl_{2}O_{3}, as a dark-coloured powder, generally however accompanied by the lower oxide Tl_{2}O, which is also black but soluble in water and alcohol. This solution has a distinctly alkaline reaction. This _thallous oxide_, melts at 300°, and is easily obtained from the hydroxide TlHO by igniting it without access of air (in the presence of air the incandescent thallous oxide partly passes into thallic oxide). _Thallous hydroxide_, TlOH, crystallises with one molecule H_{2}O in yellow prisms which are very easily soluble in water. Metallic thallium may be used for its preparation, as the metal in the presence of water attracts oxygen from the air and forms the hydroxide. But metallic thallium does not decompose water, although it gives a hydroxide which is soluble in water.[41 bis] All the other data for the chemical and physical properties of thallium, of its two grades of oxidation and of their corresponding salts, are expressed by the position occupied by this metal in virtue of its atomic weight Tl = 204, between mercury Hg = 200, and lead Pb = 206. [41 bis] The best method of preparing thallous hydroxide, TlOH, is by the decomposition of the requisite quantity of baryta by thallous sulphate, which is slightly soluble in water; barium sulphate is then obtained in the precipitate and thallous hydroxide in solution. This solubility of the hydroxide is exceedingly characteristic, and forms one of the most important properties of thallium. These lower (thallous) compounds are of the type TlX, and recall the salts of the alkalis. The salts TlX are colourless, do not give a precipitate with the alkalis or ammonia, but are precipitated by ammonium carbonate, because thallous carbonate, Tl_{2}CO_{3}, is sparingly soluble in water. Platinic chloride gives the same kind of precipitate as it does with the salts of potassium--that is, thallous platinochloride, PtTl_{2}Cl_{6}. All these facts, together with the isomorphism of the salts TlX with those of potassium, again point out what an important significance the types of compounds have in the determination of the character of a given series of substances. Although thallium has a greater atomic weight and greater density than potassium, and although it has a less atomic volume, nevertheless thallous oxide is analogous to potassium oxide in many respects, for they both give compounds of the same type, RX. We may further remark that thallous fluoride, TlF, is easily soluble in water as well as thallous silicofluoride, SiTl_{2}F_{6}, but that thallous cyanide, TlCN, is sparingly soluble in water. This, together with the slight solubility of thallous chloride, TlCl, and sulphate, Tl_{2}SO_{4}, indicates an analogy between TlX and the salts of silver, AgX. As regards the higher oxide or the _thallic oxide_, Tl_{2}O_{3}, the thallium is trivalent in it--that is, it forms compounds of the type TlX_{3}. The hydroxide, TlO(OH), is formed by the action of hydrogen peroxide on thallous oxide, or by the action of ammonia on a solution of thallic chloride, TlCl_{3}. It is obtained as a brown precipitate, insoluble in water but easily soluble in acids, with which it gives thallic salts, TlX_{3}. Thallic chloride, which is obtained by cautiously heating the metal in a stream of chlorine, forms an easily fusible white mass, which is soluble in water and able to part with two-thirds of its chlorine when heated. An aqueous solution of this salt yields colourless crystals containing one equivalent of water. It is evident from the above that all the thallic salts can easily be reduced to thallous salts by reducing agents such as sulphurous anhydride, zinc, &c. Besides these salts, thallic sulphate, Tl_{2}(SO_{4})_{3},7H_{2}O, thallic nitrate Tl(NO_{3})_{3},4H_{2}O, &c., are known. These salts are decomposed by water, like the salts of many feeble basic metals--for example, aluminium. Gallium, indium, and thallium belong to the uneven series, and there should be elements of the even series in group III. corresponding with calcium, strontium, and barium in group II. These elements should in their oxides R_{2}O_{3} present basic characters of a more energetic kind than those shown by alumina, just as calcium, strontium, and barium give more energetic bases than magnesium, zinc, and cadmium. Such are _yttrium_ and _ytterbium_, which occur in a rare Swedish mineral called _gadolinite_, and are therefore termed the gadolinite metals. To these belong also the metal _lanthanum_, which accompanies the two other metals _cerium_ and _didymium_ in the mineral _cerite_, and it therefore belongs to the cerite metals. All these metals and certain others accompanying them, give basic oxides R_{2}O_{3}. At first their formula was supposed to be RO, but the application of the periodic system required their being counted as elements of groups III. and IV., which was also confirmed by the determination of the specific heats of these metals,[42] and better still by the fact that Nilson and Clève, in their researches on the gadolinite metals (1879), discovered that they contain a peculiar and very rare element, _scandium_, which by the magnitude of its atomic weight, Sc = 44, and in all its properties, exactly corresponds with the metal (previously foretold on the basis of the periodic system) _ekaboron_, whose properties were determined by taking the cerite and gadolinite metals as forming oxides R_{2}O_{3}.[43] [42] The specific heat of cerium determined (1870) by me, and afterwards confirmed by Hillebrand, corresponds with that atomic weight of cerium according to which the composition of two oxides should be Ce_{2}O_{3} and CeO_{2}. Hillebrand also obtained metallic lanthanum and didymium by decomposing their salts by a galvanic current, and he found their specific heats to be near that of cerium and about 0·04, and it is therefore justifiable to give them an atomic weight near that of cerium, as was done on the basis of the periodic law. Up to 1870 yttrium oxide was also given the formula RO. Having re-determined the equivalent of yttrium oxide (with respect to water), and found it to be 74·6, I considered it necessary to also ascribe to it the composition Y_{2}O_{3}, because then it falls into its proper place in the periodic system. If the equivalent of the oxide to water be 74·6, it contains 58·6 of metal per 16 of oxygen, and consequently one part by weight of hydrogen replaces 29·3 of yttrium, and if it be regarded as bivalent (oxide RO), it would not, by its atomic weight 58·6, find a place in the second group. But if it be taken as trivalent--that is, if the formula of its oxide be R_{2}O_{3} and salts RX_{3}--then Y = 88, and a position is open for it in the third group in the sixth series after rubidium and strontium. These alterations in the atomic weights of the cerite and gadolinite metals were afterwards accepted by Clève and other investigators, who now ascribe a formula R_{2}O_{3} to all the newly discovered oxides of these metals. But still the position in the periodic system of certain elements--for example of holmium, thulium, samarium, and others--has not yet been determined for want of a sufficient knowledge of their properties in a state of purity. [43] So, for example, in 1871, in the _Journal of the Russian Physico-Chemical Society_ (p. 45) and in Liebig's _Annalen_, Supt. Band viii. 198, I deduced, on the basis of the periodic law, an atomic weight 44 for ekaboron, and Nilson in 1888 found that of scandium, which is ekaboron, to be Sc = 44·03, The periodic law showed that the specific gravity of the ekaboron oxide would be about 8·5, that it would have decided but feeble basic properties and that it would give colourless salts. And this proved to be the case with scandium oxide. In describing scandium, Clève and Nilson acknowledge that the particular interest attached to this element is due to its complete identity with the expected element ekaboron. And this accurate foretelling of properties could only be arrived at by admitting that alteration of the atomic weights of the cerite and gadolinite metals which was one of the first results of the application of the periodic system of the elements to the interpretation of chemical facts. In my first memoirs, namely, in the _Bulletin of the St. Petersburg Academy of Sciences_, vol. viii. (1870), and in Liebig's _Annalen_ (_l. c._ p. 168) and others, I particularly insisted on the necessity of altering the then accepted atomic weights of cerium, lanthanum, and didymium. Clève, Höglund, Hillebrand and Norton, and more especially Brauner, and others accepted the proposed alteration, and gave fresh proofs in favour of the proposed alterations of these atomic weights. The study of the fluorides was particularly important. Placing cerium in the fourth group, the composition of its highest oxide would then be CeO_{2}, and its compounds CeX_{4} and the lower oxide, Ce_{2}O_{3} or CeX_{3}. Brauner obtained the fluoride CeF_{4},H_{2}O corresponding with the first, and a double crystalline salt, 3KF,2CeF_{4},2H_{2}O, without any admixture of compound of the lower grade CeX_{3}, which generally occur together with the majority of salts corresponding with CeX_{4}. It will be seen from these formulæ and from the tables of the elements, that cerium and didymium do not belong to the third group, which is now being described, but we mention them here for convenience, as all the cerite and gadolinite metals have much in common. These metals, which are rare in nature, resemble each other in many respects, always accompany each other, are with difficulty isolated from each other, and stand together in the periodic system of the elements; they have acquired a peculiar interest owing to their having been in 1870 the objects of the study of Marignac, Delafontaine, Soret, Lecoq de Boisbaudran, Brauner, Clève, Nilson, the professors of Upsala, and others. The cerite and gadolinite metals occur in rare siliceous minerals from Sweden, America, the Urals, and Baikal, such as cerite (in Sweden), gadolinite, and orthite; and in still rarer minerals formed by titanic, niobic, and tantalic acids, such as euxenite in Norway and America, and samarskite in Norway, the Urals and America, and in a few rare fluorides and phosphates. Among the latter, monazite is found in somewhat considerable quantities in Brazil and North Carolina; this contains the phosphate of cerium, CePO_{4} (= Ce_{2}O_{3}P_{2}O_{3}), together with didymium, thorium and lanthanum (according to W. Edron and Shapleigh's analyses), and is now used for preparing that mixture of the oxides of the rare metals (especially ThO_{2}, Ce_{2}O_{3}, La_{2}O_{3}, &c.), which is employed for incandescent burners (Auer von Welsbach), as it has been found by experiment that these oxides when raised to incandescence in a non-luminous gas flame, give a far more brilliant flame with a smaller consumption of gas, besides being suitable for such non-luminous gases as water gas. The insufficiency of material to work upon, and the difficulty of separating the oxides from each other, are the chief reasons why the composition of the compounds of these rare metals is so imperfectly known. Cerite is the most accessible of these minerals. Besides silica it contains more than 50 p.c. of the oxides of cerium, lanthanum (from 4 p.c.), and didymium. The decomposition of its powder by sulphuric acid gives sulphates, all of which are soluble in water. The other minerals mentioned above are also decomposed in the same manner. The solution of sulphates is precipitated with free oxalic acid, which forms salts insoluble in water and dilute acids with all the cerite and gadolinite oxides. The oxides themselves are obtained by igniting the oxalates. When ignited in the air the cerium passes from its ordinary oxide Ce_{2}O_{3} into the higher oxide CeO_{2}, which is so feeble a base that its salts are decomposed by water, and it is insoluble in dilute nitric acid. Therefore it is always possible to remove all the cerium oxide by repeated ignitions and solutions in sulphuric acid. The further separation of the metals is mainly based on four methods employed by many investigators. (_a_) A solution of the mixed salts is treated with an excess of solid potassium sulphate. Double salts, such as Ce_{2}(SO_{4})_{3},3K_{2}SO_{4}, are thus formed. The gadolinite metals, namely yttrium, ytterbium, and erbium, then remain in solution--that is, their double salts are soluble in a solution of potassium sulphate, whilst the cerite metals--namely, cerium, lanthanum, and didymium--are precipitated, that is, their double salts are insoluble in a saturated solution of potassium sulphate. This ordinary method of separation, however, appears from the researches of Marignac to be so untrustworthy that a considerable amount of didymium and the other metals remain in the soluble portion, owing to the fact that, although individually insoluble, they are dissolved when mixed together. Thus erbium and terbium occur both in the solution and precipitate. Nevertheless, beryllium, yttrium, erbium, and ytterbium belong to the soluble, and scandium, cerium, lanthanum, didymium, and thorium to the insoluble portion. The insoluble salt of scandium, for example (_i.e._ insoluble in a solution of potassium sulphate), has a composition Sc_{2}(SO_{4})_{3},3K_{2}SO_{4}. (_b_) The oxides obtained by the ignition of the oxalates are dissolved in nitric acid (the nitrates of the cerite metals easily form double salts with those of the alkali metals, and as some--for example, the ammonio-lanthanum salt--crystallise very well, they should be studied and applied to the analytical separation of these metals), the solution is then evaporated to dryness, and the residue fused. All nitrates are destroyed by heat; those of aluminium and iron, &c., very easily, those of the cerite and gadolinite metals also easily (although not so easily as the above) but in different degrees and sequence; so that by carrying on the decomposition carefully from the beginning it is possible to destroy the nitrate of only one metal without touching the others, or leaving them as insoluble basic salts. This method, like the preceding and the two following, must be repeated as many as seventy times to attain a really constant product of fixed properties, that is, one in which the decomposed and undecomposed portions contain one and the same oxide. This method, due to Berlin and worked out by Bunsen, has given in the hands of Marignac and Nilson the best results, especially for the separation of the gadolinite metals, ytterbium and scandium. (_c_) A solution of the salts is partially precipitated by ammonia; that is, the solution is mixed with a small quantity of ammonia insufficient for the precipitation of the entire quantity of the bases (fractional precipitation). Thus, the didymium hydroxide is first precipitated from a mixture of the salts of didymium and lanthanum. A partial separation may be effected by repeating the solution of the precipitate and fractional precipitation, but a perfectly pure product is scarcely attainable. (_d_) The formates having different degrees of solubility (lanthanum formate 420 parts of water per one of salt, didymium formate 221, cerium formate 360, yttrium and erbium formates easily soluble) give a possible means of separating certain of the gadolinite metals from each other by a method of fractional solution and precipitation, as Bunsen, Bahr, Clève, and others have pointed out. (_e_) Crookes (1893) took advantage of the fractional precipitation of alcoholic solutions of the chlorides by amylene, and by this means separated, for example, erbium, terbium, and others. (_f_) Lastly, oxide of thorium ThO_{2} (Chapter VIII., Note 59) is separated by means of its solubility in a solution of sodium carbonate. A good method of separating these metals is not known, for they are so like each other. There are also only a few _methods of distinguishing_ them from each other, and we can only add the following four to the above. ^a The faculty of oxidising into a higher oxide. This is very characteristic for cerium, which gives the oxides Ce_{2}O_{3} and CeO_{2} or Ce_{2}O_{4}. Didymium also gives one colourless oxide, Di_{2}O_{3}, which is capable of forming salts (of a lilac colour), and another, according to Brauner, Di_{2}O_{5} which is dark brown and does not form salts, so far as is known, and (like ceric oxide) acts as an oxidising agent, like the higher oxides of tellurium, manganese, lead, and others. Lanthanum, yttrium, and many others are not capable of such oxidation. The presence of the higher oxides may be recognised by ignition in a stream of hydrogen, by which means the higher oxides are reduced to the lower, which then remain unaltered. ^b The majority of the salts of the gadolinite and cerite metals are colourless, but those of didymium and erbium are rose-coloured, the salts of the higher oxide of cerium, CeX_{4}, yellow, of the higher oxide of terbium, yellow, &c. Thus, the first metals obtained from gadolinite were yttrium, giving colourless, and erbium, giving rose-coloured, salts. Afterwards it was found that the salts of erbium of former investigators contained numerous colourless salts of scandium, ytterbium, &c., so that a coloration sometimes indicates the presence of a small impurity, as was long known to be the case in minerals, and therefore this point of distinction cannot be considered trustworthy. ^c In a solid state and in solutions, the salts of didymium, samarium, holmium, &c., give characteristic absorption spectra, as we pointed out in Chapter XIII., and this naturally is connected with the colour of these salts. The most important point is, that those metals which do not give an absorption spectrum--for example, lanthanum, yttrium, scandium, and ytterbium--may be obtained free from didymium, samarium, and the other metals giving absorption spectra, because the presence of the latter may be easily recognised by means of the spectroscope, whilst the presence of the former in the latter cannot be distinguished, and therefore the purification of the former can be carried further than that of the latter. We may further remark that the sensitiveness of the spectrum reaction for didymium is so great that it is possible with a layer of solution half a metre thick to recognise the presence of 1 part of didymium oxide (as salt) in 40,000 parts of water. Cossa determined the presence of didymium (together with cerium and lanthanum) in apatites, limestones, bones, and the ashes of plants by this method. The main group of dark lines of didymium correspond with wave-lengths of from 580 to 570 millionths mm.; and the secondary to about 520, 730, 480, &c. The chief absorption bands of samarium are 472-486, 417, 500, and 559. Besides which, Crookes applied the investigation of the spectra of the phosphorescent light which is emitted by certain earths in an almost perfect vacuum, when an electric discharge is passed through it, to the discovery and characterisation of these rare metals. But it would seem that the smallest admixture of other oxides (for example, bismuth, uranium) so powerfully influences these spectra that the fundamental distinctions of the oxides cannot be determined by this method. Besides which, the spectra obtained by the passage of sparks through solutions or powders of the salts are determined and applied to distinguishing the elements, but as spectra vary with the temperature and elasticity (concentration) this method cannot be considered as trustworthy. ^d The most important point of distinction of individual metallic oxides is given by the direct _determination of their equivalent with respect to water_--that is, the amount of the oxide by weight which combines (like water) with 80 parts by weight of sulphuric anhydride, SO_{3}, for the formation of a normal salt. For this purpose the oxide is weighed and dissolved in nitric acid, sulphuric acid is then added, and the whole is evaporated to dryness over a water-bath and then heated over a naked flame sufficiently strongly to drive off the excess of sulphuric acid, but so as not to decompose the salt (the product would in that case not be perfectly soluble in water); then, knowing the weight of the oxide and of the anhydrous sulphate, we can find the equivalent of the oxide. The following are the most trustworthy figures in this connection: scandium oxide 45·35 (Nilson), yttrium oxide 75·7 (Clève; according to my determination, 1871--74·6), cerous oxide--that is, the lower form of oxidation of cerium, according to various investigators (Bunsen, Brauner, and others) from 108 to 111, the higher oxide of cerium from 85 to 87, lanthanum oxide, according to Brauner, 108, didymium oxide (in salts of the ordinary lower form of oxidation) about 112 (Marignac, Brauner, Clève), samarium oxide about 116 (Clève), ytterbium oxide 131·3 (Nilson). It may not be superfluous here to draw attention to the fact that the equivalent of the oxides of all the gadolinite and cerite metals for water distribute themselves into four groups with a somewhat constant difference of nearly 30. In the first group is scandium oxide with equivalent 45, in the second, yttrium oxide 76, in the third, lanthanum, cerium, didymium, and samarium oxides with equivalent about 110, and, in the fourth, erbium, ytterbium, and thorium oxides with equivalent about 131. The common difference of period is nearly 45. And if we ascribe the type R_{2}O_{3} to all the oxides--that is, if we triple the weight of the equivalent of the oxide--we shall obtain a difference of the groups nearly equal to 90, which, for two atoms of the metal, forms the ordinary periodic difference of 45. If one and the same type of oxide R_{2}O_{3} be ascribed to all these elements (as now generally accepted, in many cases there being insufficiently trustworthy data), then the atomic weights should be Sc = 44, Y = 89, La = 138, Ce = 140, Di = 144, (neodymium 140, praseodymium 144), Sm = 150, Yb = 173, also terbium 147, holmium 162, alphayttrium 157, erbium 166, thulium 170, decipium 171. It should be observed that there may be instances of basic salts. If, for example, an element with an atomic weight 90 gave an oxide RO_{2}, but salts ROX_{2}, then by counting its oxide as R_{2}O_{3} its atomic weight would be 159. All the points distinguishing many gadolinite and cerite elements have not been sufficiently well established in certain cases (for example, with decipium, thulium, holmium, and others). At present the most certain are yttrium, scandium, cerium, and lanthanum. In the case of didymium, for example, there is still much that is doubtful. Didymium, discovered in 1842 by Mosander after lanthanum, differs from the latter in its absorption spectrum and the lilac-rose colour of its salts. Delafontaine (1878) separated samarium from it. Welsbach showed that it contains two particular elements, neodymium (salts bluish-red) and praseodymium (salts apple-green), and Becquerel (1887) by investigating the spectra of crystals, recognised the presence of six individual elements. Probably, therefore, many of the now recognised elements contain a mixture of various others, and as yet there is not enough confirmation of their individuality. As regards yttrium, scandium, cerium, and lanthanum, which have been established without doubt, I think that, owing to their great rarity in nature and chemical art, it would be superfluous to describe them further in so elementary a work as the present. We may add that Winkler (1891) obtained a hydrogen compound of lanthanum, whose composition (according to Brauner) is La_{2}H_{3}, as would be expected from the composition of Na_{2}H, Mg_{2}H_{2}, &c. C. Winkler (1891), on reducing CeO_{2} with magnesium, also remarked a rapid absorption of hydrogen, and showed that a _hydride of cerium_, CeH_{2}, corresponding to CaH, and the other similar hydrides of metals of the alkaline earths, is formed (Chapter XIV., Note 63). The brevity of this work and the great rarity of the above-mentioned elements will give me the right to exclude their description, all the more as the principles of the periodic system enable many of their properties to be foreseen, and as their practical uses (cerium oxalate is used in medicine, and didymium oxide in the manufacture of glass, a mixture of the oxides of lanthanum and similar metals is employed for giving a bright light, as this mixture emits a brilliant white light when brought to incandescence) are very limited, by reason of their great rarity in nature, and the difficulty of separating them from one another. CHAPTER XVIII SILICON AND THE OTHER ELEMENTS OF THE FOURTH GROUP Carbon, which gives the compounds CH_{4}, and CO_{2}, belongs to the fourth group of elements. The nearest element to carbon is silicon, which forms the compounds SiH_{4} and SiO_{2}; its relation to carbon is like that of aluminium to boron or phosphorus to nitrogen. As carbon composes the principal and most essential part of animal and vegetable substances, so is silicon almost an invariable component part of the rocky formations of the earth's crust. Silicon hydride, SiH_{4}, like CH_{4}, has no acid properties, but silica, SiO_{2}, shows feeble acid properties like carbonic anhydride. In a free state silicon is also a non-volatile, slightly energetic non-metal, like carbon. Therefore the form and nature of the compounds of carbon and silicon are very similar. In addition to this resemblance, silicon presents one exceedingly important distinction from carbon: namely, the nature of the higher degree of oxidation. That is, silica, silicon dioxide, or silicic anhydride, SiO_{2} is a solid, non-volatile, and exceedingly infusible substance, very unlike carbonic anhydride, CO_{2}, which is a gas. This expresses the essential peculiarity of silicon. The cause of this distinction may be most probably sought for in the polymeric composition of silica compared with carbonic anhydride. The molecule of carbonic anhydride contains CO_{2}, as seen by the density of this gas. The molecular weight and vapour density of silica, were it volatile, would probably correspond with the formula SiO_{2}, but it might be imagined that it would correspond to a far higher atomic weight of Si_{_n_}O_{2_n_}, principally from the fact that SiH_{4} is a gas like CH_{4}, and SiCl_{4} is a liquid and volatile, boiling at 57°--that is, even lower than CCl_{4}, which boils at 76°. In general, analogous compounds of silicon and carbon have nearly the same boiling points if they are liquid and volatile.[1] From this it might be expected that silicic anhydride, SiO_{2}, would be a gas like carbonic anhydride, whilst in reality silica is a hard non-volatile substance,[1 bis] and therefore it may with great certainty be considered that in this condition it is polymeric with SiO_{2}, as on polymerisation--for instance, when cyanogen passes into paracyanogen, or hydrocyanic acid into cyanuric acid (Chapter IX.)--very frequently gaseous or volatile substances change into solid, non-volatile, and physically denser and more complex substances.[2] We will first make acquaintance with free silicon and its volatile compounds, as substances in which the analogy of silicon with carbon is shown, not only in a chemical but also in a physical sense.[3] [1] Chloroform, CHCl_{3}, boils at 60°, and silicon chloroform, SiHCl_{3}, at 34°; silicon ethyl, Si(C_{2}H_{5})_{4}, boils at about 150°, and its corresponding carbon compound, C(C_{2}H_{5})_{4}, at about 120°; ethyl orthosilicate, Si(OC_{2}H_{5})_{4}, boils at 160°, and ethyl orthocarbonate, C(OC_{2}H_{5})_{4}, at 158°. The specific volumes in a liquid state--that is, those of the silicon compounds--generally are slightly greater than those of the carbon compounds; for example, the volumes of CCl_{4} = 94, SiCl_{4} = 112, CHCl_{3} = 81, SiHCl_{3} = 82, of C(OC_{2}H_{5})_{4} = 186, and Si(OC_{2}H_{5})_{4} = 201. The corresponding salts have also nearly equal specific volumes; for example, CaCO_{3} = 37, CaSiO_{3} = 41. It is impossible to compare SiO_{2} and CO_{2}, because their physical states are so widely different. [1 bis] But silica fuses and volatilises (Moissan) in the heat of the electric furnace, about 3000°, SiO_{2} is also partially volatile at the temperature attained in the flame of detonating gas (Cremer, 1892). [2] A property of intercombination is observable in the atoms of carbon, and a faculty for intercombination, or polymerisation, is also seen in the unsaturated hydrocarbons and carbon compounds in general. In silicon a property of the same nature is found to be particularly developed in silica, SiO_{2}, which is not the case with carbonic anhydride. The faculty of the molecules of silica for combining both with other molecules and among themselves is exhibited in the formation of most varied compounds with bases, in the formation of hydrates with a gradually decreasing proportion of water down to anhydrous silica, in the colloid nature of the hydrate (the molecules of colloids are always complex), in the formation of polymeric ethereal salts, and in many other properties which will be considered in the sequel. Having come to this conclusion as to the polymeric state of silica since the years 1850-1860, I have found it to be confirmed by all subsequent researches on the compounds of silica, and, if I mistake not, this view has now been very generally accepted. [3] It was only after Gerhardt, and in general subsequently to the establishment of the true atomic weights of the elements (Chapter VII.), that a true idea of the atomic weight of silicon and of the composition of silica was arrived at from the fact that the molecules of SiCl_{4}, SiF_{4}, Si(OC_{2}H_{5})_{4}, &c., never contain less than 28 parts of silicon. The question _of the composition of silica_ was long the subject of the most contradictory statements in the history of science. In the last century Pott, Bergmann, and Scheele distinguished silica from alumina and lime. In the beginning of the present century Smithson for the first time expressed the opinion that silica was an acid, and the minerals of rocks salts of this acid. Berzelius determined the presence of oxygen in silica--namely, that 8 parts of oxygen were united with 7 of silicon. The composition of silica was first expressed as SiO (and for the sake of shortness S only was sometimes written instead). An investigation in the amount of silica present in crystalline minerals showed that the amount of oxygen in the bases bears a very varied proportion to the amount of oxygen in the silica, and that this ratio varies from 2 : 1 to 1 : 3. The ratio 1 : 1 is also met with, but the majority of these minerals are rare. Other more common minerals contain a larger proportion of silica, the ratio between the oxygen of the bases and the oxygen of the silica being equal to 1 : 2, or thereabouts; such are the augites, labradorites, oligoclase, talc, &c. The higher ratio 1 : 3 is known for a widely distributed series of natural silicates--for example, the felspars. Those silicates in which the amount of oxygen in the bases is equal to that in the silica are termed _monosilicates_; their general formula will be (RO)_{2}SiO_{2} or (R_{2}O_{3})_{2}(SiO_{2})_{3}. Those in which the ratio of the oxygen is equal to 1 : 2 are termed _bisilicates_, and their general formula will be ROSiO_{2} or R_{2}O_{3}(SiO_{2})_{3}. Those in which the ratio is 1 : 3 will be _trisilicates_, and their general formula (RO)_{2}(SiO_{2})_{3} or (R_{2}O_{3})_{2}(SiO_{2})_{9}. In these formulæ the now established composition of SiO_{2}--that is, that in which the atom of Si = 28--is employed. Berzelius, who made an accurate analysis of the composition of felspar, and recognised it as a trisilicate formed by the union of potassium oxide and alumina with silica, in just the same manner as the alums are formed by sulphuric acid, gave silica the same formula as sulphuric anhydride--that is, SiO_{3}. In this case the formula of felspar would be exactly similar to that of the alums--that is, KAl(SiO_{4})_{2}, like the alums, KAl(SO_{4})_{2}. If the composition of silica be represented as SiO_{3}, the atom of silicon must be recognised as equal to 42 (if O = 16; or if O = 8, as it was before taken to be, Si = 21). The former formulæ of silica, SiO (Si = 14) and SiO_{3} (Si = 42), were first changed into the present one, SiO_{2} (Si = 28), on the basis of the following arguments:--An excess of silica occurs in nature, and in siliceous rocks free silica is generally found side by side with the silicates, and one is therefore led to the conclusion that it has formed acid salts. It would therefore be incorrect to consider the trisilicates as normal salts of silica, for they contain the largest proportion of silica; it is much better to admit another formula with a smaller proportion of oxygen for silica, and it then appears that the majority of minerals are normal or slightly basic salts, whilst some of the minerals predominating in nature contain an excess of silica--that is, belong to the order of acid salts. At the present time, when there is a general method (Chapter VII.) for the determination of atomic weights, the volumes of the volatile compounds of silica show that its atomic weight Si = 28, and therefore silica is SiO_{2}. Thus, for example, the vapour density of silicon chloride with respect to air is, as Dumas showed (1862), 5·94, and hence with respect to hydrogen it is 85·5, and consequently its molecular weight will be 171 (instead of 170 as indicated by theory). This weight contains 28 parts of silicon and 142 parts of chlorine, and as an atom of the latter is equal to 35·5, the molecule of silicon chloride contains SiCl_{4}. As two atoms of chlorine are equivalent to one of oxygen, the composition of silica will be SiO_{2}--that is, the same as stannic oxide, SnO_{2}, or titanic oxide, TiO_{2}, and the like, and also as carbonic and sulphurous anhydrides, CO_{2} and SO_{2}. But silica bears but little physical resemblance to the latter compounds, whilst stannic and titanic oxides resemble silica both physically and chemically. They are non-volatile, crystalline insoluble, are colloids, also form feeble acids like silica, &c., and they might therefore be expected to form analogous compounds, and be isomorphous with silica, as Marignac (1859) found actually to be the case. He obtained stannofluorides, for example an easily soluble strontium salt, SrSnF_{6},2H_{2}O, corresponding with the already long known silicofluorides, such as SrSiF_{6},2H_{2}O. These two salts are almost identical in crystalline form (monoclinic; angle of the prism, 83° for the former and 84° for the latter; inclination of the axes, 103° 46´ for the latter and 103° 30´ for the former), that is, they are isomorphous. We may here add that the specific volume of silica in a solid form is 22·6, and of stannic oxide 21·5. Free silicon can be obtained in an amorphous or crystalline state. Amorphous silicon is produced, like aluminium, by decomposing the double fluoride of sodium and silicon (sodium silicofluoride) by means of sodium: Na_{2}SiF_{6} + 4Na = 6NaF + Si. By treating the mass thus obtained with water the sodium fluoride may be extracted and the residue will consist of brown, powdery silicon. In order to free it from any silica which might be formed, it is treated with hydrofluoric acid. This silicon powder is not lustrous; when heated it easily ignites, but does not completely burn. It fuses when very strongly heated, and has then the appearance of carbon.[4] Crystalline silicon is obtained in a similar way, but by substituting an excess of aluminium for the sodium: 3Na_{2}SiF_{6} + 4Al = 6NaF + 4AlF_{3} + 3Si. The part of the aluminium remaining in the metallic state dissolves the silicon, and the latter separates from the solution on cooling in a crystalline form. The excess of aluminium after the fusion is removed by means of hydrochloric and hydrofluoric acid. The best silicon crystals are obtained from molten zinc; 15 parts of sodium silicofluoride are mixed with 20 parts of zinc and 4 parts of sodium, and the mixture is thrown into a strongly heated crucible, a layer of common salt being used to cover it; when the mass fuses it is stirred, cooled, treated with hydrochloric acid, and then washed with nitric acid. Silicon, especially when crystalline, like graphite and charcoal, does not in any way act on the above-mentioned acids. It forms black, very brilliant, regular octahedra having a specific gravity of 2·49; it is a bad conductor of electricity, and does not burn even in pure oxygen (but it burns in gaseous fluorine). The only acid which acts on it is a mixture of hydrofluoric and nitric acids; but caustic alkalis dissolve in it like aluminium, with evolution of hydrogen, thus showing its acid character. In general silicon strongly resists the action of reagents, as do also boron and carbon. Crystalline silicon was obtained in 1855 by Deville, and amorphous silicon in 1826 by Berzelius.[4 bis] [4] A similar form of silicon is obtained by fusing SiO_{2} with magnesium, when an alloy of Si and Mg is also formed (Gattermann). Warren (1888) by heating magnesium in a stream of SiF_{4} obtained silicon and its alloy with magnesium. Winkler (1890) found that Mg_{5}Si_{3} and Mg_{2}Si are formed when SiO_{2} and Mg are heated together at lower temperatures, whilst at a high temperature Si only is formed. [4 bis] It is very remarkable that silicon decomposes carbonic anhydride at a white heat, forming a white mass which, after being treated with potassium hydroxide and hydrofluoric acid, leaves a very stable yellow substance of the formula SiCO, which is formed according to the equation, 3Si + 2CO_{2} = SiO_{2} + 2SiCO. It is also slowly formed when silicon is heated with carbonic oxide. It is not oxidised when heated in oxygen. A mixture of silicon and carbon when heated in nitrogen gives the compound Si_{2}C_{2}N, which is also very stable. On this basis Schützenberger recognises a group, C_{2}Si_{2}, as capable of combining with O_{2} and N, like C. We may add that Troost and Hautefeuille, by heating amorphous silicon in the vapour of SiCl_{4}, obtained crystalline silicon, and probably at the same time lower compounds of Si and Cl were temporarily formed. In the vapour of TiCl_{4} under the same conditions crystalline titanium is formed (Levy, 1892). Silicon hydride, SiH_{4}, analogous to marsh gas was obtained first of all in an impure state, mixed with hydrogen, by two methods: by the action of an alloy of silicon and magnesium on hydrochloric acid,[5] and by the action of the galvanic current on dilute sulphuric acid, using electrodes of aluminium, containing silicon. In these cases silicon hydride is set free, together with hydrogen, and the presence of the hydride is shown by the fact that the hydrogen separated ignites spontaneously on coming into contact with the air, forming water and silica. The formation of silicon hydride by the action of hydrochloric acid on magnesium silicide is perfectly akin to the formation of phosphuretted hydrogen by the action of hydrochloric acid on calcium phosphide, to the formation of hydrogen sulphide by the action of acids on many metallic sulphides, and to the formation of hydrocarbons by the action of hydrochloric acid on white cast iron. On heating silicon hydride--that is, on passing it through an incandescent tube, it is decomposed into silicon and hydrogen, just like the hydrocarbons, but the caustic alkalis, although without action on the latter, react with silicon hydride according to the equation: SiH_{4} + 2KHO + H_{2}O = SiK_{2}O_{3} + 4H_{2}. [5] This alloy, as Beketoff and Cherikoff showed, is easily obtained by directly heating finely divided silica (the experiment may be conducted in a test tube) with magnesium powder (Chapter XIV., Notes 17, 18). The substance formed, when thrown into a solution of hydrochloric acid, evolves spontaneously inflammable and impure silicon hydride, so that the self-inflammability of the gas is easily demonstrated by this means. In 1850-60 Wöhler and Buff obtained an alloy of silicon and magnesium by the action of sodium on a molten mixture of magnesium chloride, sodium silicofluoride, and sodium chloride. The sodium then simultaneously reduces the silicon and magnesium. Friedel and Ladenburg subsequently prepared silicon hydride in a pure state, and showed that it is not spontaneously inflammable in air, at the ordinary pressure, but that, like PH_{3}, and like the mixture prepared by the above methods, it easily takes fire in air under a lower pressure or when mixed with hydrogen. They prepared the pure compound in the following manner: Wöhler showed that when dry hydrochloric acid gas is passed through a slightly heated tube containing silicon it forms a very volatile colourless liquid, which fumes strongly in air; this is a mixture of silicon chloride, SiCl_{4}, and _silicon chloroform_, SiHCl_{3}, which corresponds with ordinary chloroform, CHCl_{3}. This mixture is easily separated by distillation, because silicon chloride boils at 57°, and silicon chloroform at 36°. The formation of the latter will be understood from the equation Si + 3HCl = H_{2} + SiHCl_{3}. It is an anhydrous inflammable liquid of specific gravity 1·6. It forms a transition product between SiH_{4} and SiCl_{4}, and may be obtained from silicon hydride by the action of chlorine and SbCl_{5}, and is itself also transformed into silicon chloride by the action of chlorine. Gattermann obtained SiHCl_{3} by heating the mass obtained after the action (Note 4) of Mg upon SiO_{2}, in a stream of chlorine (with HCl) at about 470°. Friedel and Ladenburg, by acting on anhydrous alcohol with silicon chloroform, obtained an ethereal compound having the composition SiH(OC_{2}H_{5})_{3}. This ether boils at 136°, and when acted on by sodium disengages silicon hydride, and is converted into ethyl orthosilicate, Si(OC_{2}H_{5})_{4}, according to the equation 4SiH(OC_{2}H_{5})_{3} = SiH_{4} + 3Si(OC_{2}H_{5})_{4} (the sodium seems to be unchanged), which is exactly similar to the decomposition of the lower oxides of phosphorus, with the evolution of phosphuretted hydrogen. If we designate the group C_{2}H_{5}, contained in the silicon ethers by Et, the parallel is found to be exact: 4PHO(OH)_{2} = PH_{3} + 3PO(OH)_{3}; 4SiH(OEt)_{3} = SiH_{4} + 3Si(OEt)_{4}. _Silicon chloride_, SiCl_{4}, is obtained from amorphous anhydrous silica (made by igniting the hydrate) mixed with charcoal,[6] heated to a white heat in a stream of dry chlorine--that is, by that general method by which many other chloranhydrides having acid properties are obtained. Silicon chloride is purified from free chlorine by distillation over metallic mercury. Free silicon forms the same substance when treated with dry chlorine. It is a volatile colourless liquid, which boils at 59° and has a specific gravity of 1·52. It fumes strongly in air, has a pungent smell, and in general has the characteristic properties of the acid chloranhydrides. It is completely decomposed by water, forming hydrochloric acid and silicic acid, according to the equation: SiCl_{4} + 4H_{2}O = Si(OH)_{4} + 4HCl.[7] [6] The amorphous silica is mixed with starch, dried, and then charred by heating the mixture in a closed crucible. A very intimate mixture of silica and charcoal is thus formed. In Chapter XI., Note 13, we saw that elements like silicon disengage more heat with oxygen than with chlorine, and therefore their oxygen compounds cannot be directly decomposed by chlorine, but that this can be effected when the affinity of carbon for oxygen is utilised to aid the action. When the mass obtained by the action of Mg upon SiO_{2} is heated to 300° in a current of chlorine, it easily forms SiCl_{4} (Gattermann): besides which two other compounds, corresponding to SiCl_{4}, are formed, namely: Si_{2}Cl_{6}, which boils at 145° and solidifies at -1°, and Si_{3}Cl_{8}, which boils at about 212°. These substances, which answer to corresponding carbon compounds (C_{2}H_{6} and C_{3}H_{8}), act upon water and form corresponding oxygen compounds; for instance, Si_{2}Cl_{6} + 4H_{2}O = (SiO_{2}H)_{2} + 6HCl gives the analogue of oxalic acid (CO_{2}H)_{2}. This substance is insoluble in water, decomposes under the action of friction and heat with an explosion, and should be called _silico-oxalic acid_, Si_{2}H_{2}O_{4} (_see_ later, Note 11 ^{bis}). [7] Silicon chloride shows a similar behaviour with alcohol. This is accompanied by a very characteristic phenomenon; on pouring silicon chloride into anhydrous alcohol a momentary evolution of heat is observed, owing to a reaction of double decomposition, but this is immediately followed by a powerful cooling effect, due to the disengagement of a large amount of hydrochloric acid--that is, there is an absorption of heat from the formation of gaseous hydrochloric acid. This is a very instructive example in this respect; here two processes occurring simultaneously--one chemical and the other physical--are divided from each other by time, the latter process showing itself by a distinct fall in temperature. In the majority of cases the two processes proceed simultaneously, and we only observe the difference between the heat developed and absorbed. In acting on alcohol, silicon chloride forms ethyl orthosilicate, SiCl_{4} + 4HOC_{2}H_{5} = 4HCl + Si(OC_{2}H_{5})_{4}. This substance boils at 160°, and has a specific gravity 0·94. Another salt, ethyl metasilicate, SiO(OC_{2}H_{5})_{2}, is also formed by the action of silicon chloride on anhydrous alcohol; it volatilises above 300°, having a sp. gr. 1·08. It is exceedingly interesting that these two ethereal salts are both volatile, and both correspond with silica, SiO_{2}: the first ether corresponds to the hydrate Si(OH)_{4}, orthosilic acid, and the second to the hydrate SiO(OH)_{2}, metasilicic acid. As the nature of hydrates may be judged from the composition of salts, so also, with equal right, can ethereal salts serve the same purpose. The composition of an ethereal salt corresponds with that of an acid in which the hydrogen is replaced by a hydrocarbon radicle--for instance, by C_{2}H_{5}. And, therefore, it may be truly said that there exist at least the two silicic acids above mentioned. We shall afterwards see that there are really several such hydrates; that these ethereal salts actually correspond with hydrates of silica is clearly shown from the fact that they are decomposed by water, and that in moist air they give alcohol and the corresponding hydrate, although the hydrate which is obtained in the residue always corresponds with the second ethereal salt only--that is, it has the composition SiO(OH)_{2}; this form corresponds also to carbonic acid in its ordinary salts. This hydrate is formed as a vitreous mass when the ethyl silicates are exposed to air, owing to the action of the atmospheric moisture on them. Its specific gravity is 1·77. _Silicon bromide_, SiBr_{4}, as well as silicon bromoform, SiHBr_{3}, are substances closely resembling the chlorine compounds in their reactions, and they are obtained in the same manner. Silicon iodoform, SiHI_{3}, boils at about 220°, has a specific gravity of 3·4, reacts in the same manner as silicon chloroform, and is formed, together with silicon iodide, SiI_{4}, by the action of a mixture of hydrogen and hydriodic acid on heated silicon. Silicon iodide is a solid at the ordinary temperature, fusing at about 120°; it may be distilled in a stream of carbonic anhydride, but easily takes fire in air, and behaves with water and other reagents just like silicon chloride. It may be obtained by the direct action of the vapour of iodine on heated silicon. Besson (1891) also obtained SiCl_{3}I (boils at 113°), SiCl_{2}I_{2} (172°), and SiClI_{3} (220°), and the corresponding bromine compounds. All the halogen compounds of Si are capable of absorbing 6NH_{3} and more. Besides which Besson obtained SiSCl_{2} by heating Si in the vapour of chloride of sulphur; this compound melts at 74°, boils at 185°, and gives with water the hydrate of SiO_{2}, HCl, and H_{2}S. The most remarkable of the haloid compounds of silicon is _silicon fluoride_, SiF_{4}. It is a gaseous substance only liquefied by intense cold, -100°, and is obtained (Chapter XI.) directly by the action of hydrofluoric acid on silica and its compounds (SiO_{2} + 4HF = 2H_{2}O + SiF_{4}), and also by heating fluorspar with silica (2CaF_{2} + 3SiO_{2} = 2CaSiO_{3} + SiF_{4}).[8] In order to prepare silicon fluoride, sand or broken glass is mixed with an equal quantity by weight of fluorspar and 6 parts by weight of strong sulphuric acid, and the mixture is gently heated. It fumes strongly in air, reacting with the aqueous vapours, although it is produced from silica and hydrofluoric acid with the separation of water. It is evident that a reverse reaction occurs here; that is to say, the water reacts with the silicon fluoride, but the reaction is not complete. This phenomenon is similar to that which occurs when water decomposes aluminium chloride, but at the same time hydrochloric acid dissolves aluminium hydroxide and forms the same aluminium chloride. The relative amount of water present (together with the temperature) determines the limit and direction of the reaction. The faculty which silicon fluoride has of reacting with water is so great that it takes up the elements of water from many substances--for instance, like sulphuric acid, it chars paper. Water dissolves about 300 volumes of this gas, but in this case it is not a common dissolution which takes place, but a reaction. During the first absorption of silicon fluoride by water, silicic acid is separated in the form of a jelly, but a certain quantity of the silicon fluoride also remains in the liquid, because the hydrofluoric acid formed dissolves the other part of the silica[9] and forms the so-called _hydrofluosilicic acid_: H_{2}SiF_{6} = SiF_{4} + 2HF = SiH_{2}O_{3} + 6HF - 3H_{2}O. That is to say, a metasilicic acid, SiH_{2}O_{3}, in which O_{3} is replaced by F_{6}. This view of the composition of hydrofluosilicic acid may be admitted, because it forms a whole series of crystallisable and well defined salts. In general, the whole reaction of water on silicon fluoride may be expressed by the equation: 3SiF_{4} + 3H_{2}O = SiO(OH)_{2} + 2SiH_{2}F_{6}. Hydrofluosilicic acid and silicic acid resemble each other as much, and differ as much, in their chemical character as water and hydrofluoric acid. For this reason silicic acid is a feebler acid than hydrofluosilicic acid, and in addition to this the former is insoluble, and the latter soluble, in water.[10] Hydrofluosilicic acid is also formed if silicic acid be dissolved in a solution of hydrofluoric acid. It is incapable of volatilising without decomposition, and on heating the concentrated acid silicon fluoride is evolved, leaving an aqueous solution of hydrofluoric acid. This is the reason why solutions of hydrofluosilicic acid corrode glass. This decomposition may be further accelerated by the addition of sulphuric acid, or even of other acids. Hydrofluosilicic acid, when acting on potassium and barium salts, gives precipitates, because the salts of these metals are but sparingly soluble in water: thus 2KX + H_{2}SiF_{6} = 2HX + K_{2}SiF_{6}. The potassium salt is obtained in the form of very fine octahedra, but the precipitate does not form quickly, and at first appears as a jelly. Nevertheless, the decomposition is complete, and it is taken advantage of for obtaining their corresponding acids from salts of potassium.[10 bis] [8] This property of calcium fluoride of converting silica into a gas and a vitreous fusible slag of calcium silicate is frequently taken advantage of in the laboratory and in practice in order to remove silica. The same reaction is employed for preparing silicon fluoride on a large scale in the manufacture of hydrofluosilicic acid (see sequel). [9] The amount of heat developed by the solution of silicic acid, SiO_{2}_n_H_{2}O, in aqueous hydrofluoric acid, _x_HF_n_H_{2}O, increases with the magnitude of _x_ and normally equals _x_5,600 heat units, where _x_ varies between 1 and 8. However, when _x_ = 10 the maximum amount of heat is developed (= 49,500 units), and beyond that the amount decreases (Thomsen). [10] In reality, however, it would seem that the reaction is still more complex, because the aqueous solution of silicon fluoride does not yield a hydrate of silica, but a fluo-hydrate (Schiff), Si_{2}O_{3}(OH)F, corresponding to the (pyro) hydrate Si_{2}O_{3}(OH)_{2}, equal to SiO(OH)_{2}SiO_{2}, so that the reaction of silicon fluoride on water is expressed by the equation: 5SiF_{4} + 4H_{2}O = 3SiH_{2}F_{6} + Si_{2}O_{3}(OH)F + HF. However, Berzelius states that the hydrate, when well washed with water, contains no fluorine, which is probably due to the fact that an excess of water decomposes Si_{2}O_{3}(OH)F, forming hydrofluoric acid and the compound Si_{2}O_{3}(OH)_{2}. Water saturated with silicon fluoride disengages silicon fluoride and hydrofluoric acid when treated with hydrochloric acid, the gelatinous precipitate being simultaneously dissolved. It may be further remarked that hydrofluosilicic acid has been frequently regarded as SiO_{2},6HF, because it is formed by the solution of silica in hydrofluoric acid, but only two of these six hydrogens are replaced by metals. On concentration, solutions of the acid begin to decompose when they reach a strength of 6H_{2}O per H_{2}SiF_{6}, and therefore the acid may be regarded as Si(OH)_{4},2H_{2}O,6HF, but the corresponding salts contain less water, and there are even anhydrous salts, R_{2}SiF_{6}, so that the acid itself is most simply represented as H_{2}SiF_{6}. If gaseous silicon fluoride be passed directly into water, the gas-conducting tube becomes clogged with the precipitated silicic acid. This is best prevented by immersing the end of the tube under mercury, and then pouring water over the mercury; the silicon fluoride then passes through the mercury, and only comes into contact with the water at its surface, and consequently the gas-conducting tube remains unobstructed. The silicic acid thus obtained soon settles, and a colourless solution with a pleasant but distinctly acid taste is procured. Mackintosh, by taking 9 p.c. of hydrofluoric acid, observed that in the course of an hour its action on opal attained 77 p.c. of the possible, and did not exceed 1-1/2 p.c. of its possible action on quartz during the same time. This shows the difference of the structure of these two modifications of silica, which will be more fully described in the sequel. [10 bis] The sodium salt is far more soluble in water, and crystallises in the hexagonal system. The magnesium salt, MgSiF_{6}, and calcium salt are soluble in water. The salts of hydrofluosilicic acid may be obtained not only by the action of the acid on bases or by double decompositions, but also by the action of hydrofluoric acid on metallic silicates. Sulphuric acid decomposes them, with evolution of hydrofluoric acid and silicon fluoride, and the salts when heated evolve silicon fluoride, leaving a residue of metallic fluoride, R_{2}F_{2}. Silicon, having so much in common with carbon, is also able to combine with it in the proportion given by the law of substitution, that is, it forms a carbide of silicon CSi, called _carborundum_ and obtained by Mühlhäuser and Acheson in the United States, and by Moissan in France (1891), and others, by reducing silica with carbon in the electrical furnace at a temperature of about 2500°[11], _i.e._ by the action of an electrical current upon a mixture of carbon and SiO_{2} with NaCl. After treating the resultant mass with acids and washing with water, carborundum is obtained in transparent, lustrous grains of a greenish color, possessing great hardness (greater than corundum) and therefore used for polishing the hardest kinds of steel and stones. The specific gravity is about 3·1. Carborundum does not alter at a red heat, does not burn, and apparently approaches the diamond in its properties. (Moissan obtained, 1894, a similar very hard compound for boron, B_{6}C, sp. gr. 2·5.) [11] _See_ Note 4 bis. Probably Schützenberger had already obtained CSi in his researches together with other silicon compounds. An amorphous, less hard compound of the same alloy is also obtained together with the hard crystalline CSi. According to the principle of substitution, if silicon forms SiH_{4}, a series of hydrates, or hydroxyl derivatives, ought to exist corresponding to it. The first hydrate of an alcoholic character ought to have the composition SiH_{3}(OH); the second hydrate SiH_{2}(OH)_{2}; the third, SiH(OH)_{3};[11 bis] and the last, Si(OH)_{4}. The last is a hydrate of silica, because it is equal to SiO_{2} + 2H_{2}O); and it is formed by the action of water on silicon chloride, when all four atoms of chlorine are replaced by four hydroxyl groups. It does not, however, remain in this state, but easily loses part of its water. [11 bis] The following consideration is very important in explaining the nature of the lower hydrates which are known for silicon. If we suppose water to be taken up from the first hydrates (just as formic acid is CH(OH)_{3}, _minus_ water), we shall obtain the various lower hydrates corresponding with silicon hydride. When ignited they should, like phosphorous and hypophosphorous acids, disengage silicon hydride, and leave a residue of silica behind--_i.e._ of the oxide corresponding to the highest hydrate--just as organic hydrates (for example, formic acid with an alkali) form carbonic anhydride as the highest oxygen compound. Such imperfect hydrates of silicon, or, more correctly speaking, of silicon hydride, were first obtained by Wöhler (1863) and studied by Geuther (1865), and were named after their characteristic colours. (_See_ Note 6). _Leucone_ is a white hydrate of the composition SiH(OH)_{3}. It is obtained by slowly passing the vapour of silicon chloroform into cold water: SiHCl_{3} + 3H_{2}O = SiH(OH)_{3} + 3HCl. But this hydrate, like the corresponding hydrate of phosphorus or carbon, does not remain in this state of hydration, but loses a portion of its water. The carbon hydrate of this nature, CH(OH)_{3}, loses water and forms formic acid, CHO(OH); but the silicon hydrate loses a still greater proportion of water, 2SiH(OH)_{3}, parting with 3H_{2}O, and consequently leaving Si_{2}H_{2}O_{3}. This substance must be an anhydride; all the hydrogen previously in the form of hydroxyl has been disengaged, two remaining hydrogens being left from SiH_{4}. The other similar hydrate is also white, and has the composition Si_{3}H_{2}O (nearly). It may be regarded as the above white hydrate + SiO_{2}. A yellow hydrate, known as _chryseone_ (silicone), is obtained by the action of hydrochloric acid on an alloy of silicon and calcium; its composition is about Si_{6}H_{4}O_{3}. Most probably, however, chryseone has a more complex composition, and stands in the same relation to the hydrate SiH_{2}(OH)_{3} as leucone does to the hydrate SiH(OH)_{3}, because this very simply expresses the transition of the first compound into the second with the loss of water, SiH_{2}(OH)_{3} - H_{2} + H_{2}O = SiH(OH)_{3}. When these lower hydrates are ignited without access of air, they are decomposed into hydrogen, silicon, and silica--that is, it may be supposed that they form silicon hydride (which decomposes into silicon and hydrogen) and silica (just as phosphorous and hypophosphorous acids give phosphoric acid and phosphuretted hydrogen). When ignited in air, they burn, forming silica. They are none of them acted on by acids, but when treated with alkalis they evolve hydrogen and give silicates; for example, leucone: SiH_{2}O_{3} + 4KHO = 2SiK_{2}O_{3} + H_{2}O + 2H_{2}. They have no acid properties. Silica or silicic anhydride, both in the free state and in combination with other oxides, enters into the composition of most of the rocky formations of the earth's crust. These silicious compounds are substances varying so much in their properties, crystalline forms, and relations to one another that they are comprised in a special branch of natural science (like the carbon compounds), and are treated of in works on mineralogy; so that, in dealing with them further, we shall only give a short description of these various compounds. It is first of all necessary to turn to the description of silica itself, especially as it is not unfrequently met with in nature in a separate state, and often forms whole masses of rocky formations, called 'quartz.' In an anhydrous condition silica appears in the greatest variety of natural forms--sometimes in well-formed crystals, hexagonal prisms, terminated by hexagonal pyramids. If the crystals are colourless and transparent, they are called _rock crystal_. This is the purest form of silica. Prismatic crystals of rock crystal sometimes attain considerable size, and as they are remarkable for their unchangeability, great hardness, and high index of refraction, they are used for ornaments, for seals, making necklaces, &c.[12] Rock crystal coloured with organic matter in contact with which it has been produced has a brown or greyish colour, and then bears the name of _cairngorm_ or _smoky quartz_. In this form it has the same uses as rock crystal, especially as it is often found in large masses. The same mineral, frequently occurs, coloured red or pink by manganese or iron oxides, especially in aqueous formations, and is then known as _amethyst_. When finely coloured the amethyst is used as a precious stone, but amethysts most frequently occur as small crystals in the cavities formed in other rocky formations, and especially in those formed in silica itself. A similar anhydrous silica is often found in transparent non-crystalline masses, having the same specific gravity as rock crystal itself (2·66). In this case it is called _quartz_. Sometimes it forms complete rocky formations, but more often penetrates or is interspersed through other rocky formations, together with other siliceous compounds. Thus, in granite, quartz is mixed with felspar and similar substances. Sometimes the colouring of quartz is so considerable that it is hardly transparent in thin sheets, but it is often found in transparent masses slightly coloured with various tints. The existence in nature of enormous masses of quartz proves that it resists the action of water. When water destroys rocky formations, the siliceous minerals which they contain are partly dissolved and partly transformed into clay, &c. But the quartz remains untouched, in the form of grains in which it existed in the rocky formation; sometimes, when crushed, it is carried away by the water and deposited. This is the nature of _sand_. Naturally, sometimes other rocky substances which are not changed by water, or only slightly acted on by it, are found in sand; but as these latter are more or less changed by the continuous action of water, it is not unusual to find sand which consists almost entirely of pure quartz. Common sand is generally coloured yellow or reddish-brown by foreign mineral matter, consisting principally of ferruginous minerals and clays. The purest or so-called quartz sand is, however, rarely found, and is recognised by the absence of colour, and also by the test that when shaken in water it does not form any turbidity: this shows the absence of clay; when fused with bases it forms a colourless glass, and on this account is a valuable material for the manufacture of glass. Sands were formed at all periods of the earth's existence; the ancient ones, compressed by strata of more recent formation and permeated with various substances (deposited from the infiltrating water), are sometimes solidified into rock, called _sandstone_, composing, in some places, whole mountain chains, and serviceable as a most excellent building material, on account of the slight change it undergoes under the influence of atmospheric agencies, and on account of the facility with which it may be wrought from rocky formations into immense regularly-shaped flags--the latter property is due to the primary laminar structure of the sand formations deposited, as above-mentioned, by water. Many grindstones and whetstones are made from such rocks. [12] Two modifications of rock crystal are known. They are very easily distinguished from each other by their relation to polarised light; one rotates the plane of polarisation to the right and the other to the left--in the one the hemihedral faces are right and in the other they are left; this opposite rotatory power is taken advantage of in the construction of polarisers. But, with this physical difference--which is naturally dependent on a certain difference in the distribution of the molecules--there is not only no observable difference in the chemical properties, but not even in the density of the mass. Perfectly pure rock crystal is a substance which is most invariable with respect to its specific gravity. The numerous and accurate determinations made by Steinheil on the specific gravity of rock crystal show that (if the crystal be free from flaws) it is very constant and is equal to 2·66. Perfectly pure anhydrous silica is not only known in the condition of rock crystal and quartz having a specific gravity of 2·6, but also in another special form, having other chemical and physical properties. This variety of silica has a specific gravity of 2·2, and is formed by fusing rock crystal or heating silicic acid.[12 bis] Silicic acid, when heated to a dull red heat, parts entirely with the water it contains, and leaves an exceedingly fine amorphous mass of silica (easily levigated, but difficult to moisten); it is characterised by such excessive friability that, when lightly blown on, a large mass of it rises into the air like a cloud of dust. A mass of anhydrous silica maybe poured in this way from one vessel to another like a liquid, and like the latter it takes a horizontal position in the vessel containing it.[13] Anhydrous silica, like quartz, does not fuse in the heat of a furnace, but it fuses in the oxyhydrogen flame to a colourless glassy mass exactly similar to that formed in the same way from rock crystal. In this condition silica has a specific gravity of 2·2.[13 bis] Both forms of silica are insoluble in ordinary acids, and even when they are in the state of powder, alkalis in solution act very slowly and feebly on them; rock crystal offers much greater resistance to the action of alkalis than the powder obtained by heating the hydrate. The latter is quite soluble, although but slowly, in hot alkaline solutions. This last property appertains in a greater degree to anhydrous silica having a specific gravity of 2·2 than to that which has a specific gravity of 2·6. Hydrofluoric acid more easily transforms the former into silicon fluoride than it does the latter. Both varieties of silica, when taken in the form of powder, easily combine with bases, forming, on being fused with an alkali, a vitreous slag, which is a salt corresponding with silica. Glass is such a salt, formed of alkalis and alkaline earthy bases; if the glass does not contain any of the latter--that is, if only alkaline glass be taken--a mass soluble in water is obtained. In order to obtain such _soluble glass_, potassium or sodium carbonates, or better a mixture of the two (fusion mixture), is fused with fine sand. A still better and further saturation of the alkalis with silica is effected by the action of alkaline solutions on the silicon hydrate met with in nature; for instance, an alkaline solution is often made use of to act on the so-called _tripoli_, or collection of siliceous skeletons of the lowest microscopical infusoria, which is sometimes found in considerable layers in the form of a sandy mass. Tripoli is used for polishing, not only on account of the considerable hardness of the silica, but also because the microscopic bodies of the infusoria have a pointed shape, which, however, is not angular, so that they do not scratch metals like sand.[14] The alkaline solutions of silica obtained by boiling tripoli with caustic soda under pressure contain various proportions of silica and alkali.[14 bis] In order that it may contain the greatest amount of silica, silicic acid should be added to the heated solution. Silicic acid is formed by taking any solution containing silica and alkali, and adding to it, by degrees, some acid--for instance, sulphuric or hydrochloric; if the experiment be carried on carefully and the solution be concentrated, the whole mass thickens to a jelly, due to the gelatinous form of the _silicic acid_ separated from the salt by the action of the acid. The decomposition may be expressed by the following equation: Si(ONa)_{4} + 4HCl = 4NaCl + Si(OH)_{4}. The hydrate separated, Si(OH)_{4}, easily loses part of the water and forms a jelly, the whole mass gelatinising if the solution be strong enough.[15] [12 bis] Several other modifications are known as minute crystals. For example, there is a particular mineral first found in Styria and known as _tridymite_. Its specific gravity 2·3 and form of crystals clearly distinguish it from rock crystal; its hardness is the same as that of quartz--that is, slightly below that of the ruby and diamond. [13] There is a distinct rise of temperature (about 4°) when amorphous silica is moistened with water. Benzene and amyl alcohol also give an observable rise of temperature. Charcoal and sand give the same result, although to a less extent. [13 bis] Silica also occurs in nature in two modifications. The opal and tripoli (infusorial earth) have a specific gravity of about 2·2, and are comparatively easily soluble in alkalis and hydrofluoric acid. Chalcedony and flint (tinted quartzose concretions of aqueous origin), agate and similar forms of silica of undoubted aqueous origin, although still containing a certain amount of water, have a specific gravity of 2·6, and correspond with quartz in the difficulty with which they dissolve. This form of silica sometimes permeates the cellulose of wood, forming one of the ordinary kinds of petrified wood. The silica may be extracted from it by the action of hydrofluoric acid, and the cellulose remains behind, which clearly shows that silica in a soluble form (see sequel) has permeated into the cells, where it has deposited the hydrate, which has lost water, and given a silica of sp. gr. 2·6. The quartzose stalactites found in certain caves are also evidently of a similar aqueous origin; their sp. gr. is also 2·6. As crystals of amethyst are frequently found among chalcedonies, and as Friedau and Sarrau (1879) obtained crystals of rock crystal by heating soluble glass with an excess of hydrate of silica in a closed vessel, there is no doubt but that rock crystal itself is formed in the wet way from the gelatinous hydrate. Chroustchoff obtained it directly from soluble silica. Thus this hydrate is able to form not only the variety having the specific gravity 2·2 but also the more stable variety of sp. gr. 2·6; and both exist with a small proportion of water and in a perfectly anhydrous state in an amorphous and crystalline form. All these facts are expressed by recognising silica as dimorphous, and their cause must be looked for in a difference in the degree of polymerisation. [14] Deposits of perfectly white tripoli have been discovered near Batoum, and might prove of some commercial importance. [14 bis] Alkaline solutions, saturated with silica and known as _soluble glass_, are prepared on a large scale for technical purposes by the action of potassium (or sodium) hydroxide in a steam boiler on tripoli or infusorial earth, which contains a large proportion of amorphous silica. All solutions of the alkaline silicates have an alkaline reaction, and are even decomposed by carbonic acid. They are chiefly used by the dyer, for the same purposes as sodium aluminate, and also for giving a hardness and polish to stucco and other cements, and in general to substances which contain lime. A lump of chalk when immersed in soluble glass, or better still when moistened with a solution and afterwards washed in water (or better in hydrofluosilicic acid, in order to bind together the free alkali and make it insoluble), becomes exceedingly hard, loses its friability, is rendered cohesive, and cannot be levigated in water. This transformation is due to the fact that the hydrate of silica present in the solution acts upon the lime, forming a stony mass of calcium silicate, whilst the carbonic acid previously in combination with the lime enters into combination with the alkali and is washed away by the water. [15] The equation given above does not express the actual reaction, for in the first place silica has the faculty of forming compounds with bases, and therefore the formula SiNa_{4}O_{4} is not rightly deduced, if one may so express oneself. And, in the second place, silica gives several hydrates. In consequence of this, the hydrate precipitated does not actually contain so high a proportion of water as Si(OH)_{4}, but always less. The insoluble gelatinous hydrate which separates out is able (before, but not after, having been dried) to dissolve in a solution of sodium carbonate. When dried in air its composition corresponds with the ordinary salts of carbonic acid--that is, SiH_{2}O_{3}, or SiO(OH)_{2}. If gradually heated it loses water by degrees, and, in so doing, gives various degrees of combination with it. The existence of these degrees of hydration, having the composition SiH_{2}O_{3}_n_SiO_{2}, or, in general, _n_SiO_{2}_m_H_{2}O, where _m_ < _n_, must be recognised, because most varied degrees of combination of silica with bases are known. The hydrate of silica, when not dried above 30°, has a composition of nearly H_{4}Si_{3}O_{8} = (H_{2}SiO_{3})_{2}SiO_{2}, but at 60° contains a greater proportion of silica--that is, it loses still more water; and at 100° a hydrate of the composition SiH_{2}O_{3}2SiO_{2}, and at 250° a hydrate having approximately a composition SiH_{2}O_{3}7SiO_{2} is obtained. These data show the complexity of the molecules of anhydrous silica. The hydrates of silica easily lose water and give the hydrates (SiO_{2})_{_n_}(H_{2}O)_{_m_}, where _m_ becomes smaller and smaller than _n_. In the natural hydrates, this decrement of water proceeds quite consecutively, and, so to say, imperceptibly, until _n_ becomes incomparably greater than _m_, and when the ratio becomes very large, anhydrous silica of the two modifications 2·6 and 2·2 is obtained. The composition (SiO_{2})_{10},H_{2}O still corresponds with 2·9 p.c. of water, and natural hydrates often contain still less water than this. Thus some opals are known which contain only 1 p.c. of water, whilst others contain 7 and even 10 p.c. As the artificially prepared gelatinous hydrate of silica when dried has many of the properties of native opals, and as this hydrate always loses water easily and continually, there can be no doubt that the transition of (SiO_{2})_{_n_}(H_{2}O)_{_m_} into anhydrous silica, both amorphous and crystalline (in nature, chalcedony), is accomplished gradually. This can only be the case if the magnitude of _n_ be considerable, and therefore the molecule of silica in the hydrate is undoubtedly complex, and hence the anhydrous silica of sp. gr. 2·2 and 2·6 does not contain SiO_{2}, but a complex molecule, Si_{_n_}O_{2_n_}--that is, the structure of silica is polymeric and complex, and not simple as represented above by the formula SiO_{2}. Neither of the two varieties of anhydrous silica, nor the various natural gelatinous hydrates, are directly soluble in water. There is, however, a condition of silica known which is soluble in water, _soluble silica_, and silica is found in this state in nature. Small quantities of soluble silica are met with in all waters. Certain mineral springs, and especially hot springs--of which the best known are the Geysers of Iceland and those in the North American National Park (Yellowstone Valley)--contain a considerable amount of silica in solution. Such water, permeating the objects it meets with--for instance, wood--penetrates into them and deposits silica inside them, that is, transforms them into a petrified condition. Siliceous stalactites, and also many (if not all) forms of silica are formed by such water. The absorption of silica by plants by means of their roots, and also by the lower organisms having siliceous bodies, is due also to their nourishing themselves with the solutions containing silica continually formed in nature. Thus, in plants, in the straws of the grasses, in hard shave-grass, and especially in the knots of bamboo and other straw-like plants, a considerable quantity of silica is deposited, which must previously have been absorbed by the plants. Silicic acid is a colloid. The gelatinous silicon hydrate is its hydrogel, the soluble hydrate is the hydrosol (Chapter XII.) Both varieties may be easily obtained from the alkaline silicates and from water-glass. The very same substances--that is, aqueous solutions of soluble glass and acid--taken in the same proportion, may produce either the gelatinous or the soluble silica, according to the way these solutions are mixed together. If the acid be added little by little to the _alkaline silicate_, with continuous stirring, a moment arrives when the whole mass thickens to a jelly, hydrogel; in this case the silicic acid is formed in the midst of the alkaline solution and becomes insoluble. But if the mixing be done in the reverse order--that is, if the soluble glass be added to the acid, or if a quantity of acid be rapidly poured into the solution of the salt--then the separation of the silica takes place in the midst of the acid liquid, and it is obtained in the form of the soluble hydrate, the hydrosol.[16] [16] The presence of an excess of acid aids the retention of the silica in the solution, because the gelatinous silica obtained in the above manner, but not heated to 60°--that is, containing more water than the hydrate H_{2}SiO_{3}--is more soluble in water containing acid than in pure water. This would seem to indicate a feeble tendency of silica to combine with acids, and it might even have been imagined that in such a solution the hydrate of silica is held in combination by an excess of acid, had Graham not obtained soluble silica perfectly free from acid, and if there were not solutions of silica free from any acid in nature. At all events a tolerably strong solution of free silica or silicic acid may be obtained from soluble glass diluted with water. The solution, besides silica, will contain sodium chloride and an excess of the acid taken. If this solution remains for some time exposed to the air, or in a closed vessel, and under various other conditions, it is found that, after a time, insoluble gelatinous silica separates out--that is, the soluble form of silica is unstable, like the soluble form of alumina. The analogous forms of molybdic or tungstic acids may be heated, evaporated, and kept for a long period of time without the soluble form being converted into the insoluble. The hydrosol of silica prepared by mixing an excess of hydrochloric acid with a solution of sodium silicate, may be freed from the admixtures both of hydrochloric acid and salt, sodium chloride, _by means of dialysis_,[17] as Graham showed (in 1861) in enquiring into the nature of colloids (Chapter I.), and making many other important chemical investigations. The solution, containing the acid, salt, and silica, all dissolved in water, is poured into a dialyser--that is, a vessel with a porous diaphragm surrounded by water. Certain substances pass more easily through the diaphragm than others. This may be represented thus: the passage through the diaphragm proceeds in both directions, and if the solutions on each side of the diaphragm be equally strong, there will be equal numbers of molecules of the soluble substance passing into either side in a given time, some passing quickly and others slowly. The metallic chlorides and hydrochloric acid belong to the series of crystalloids which easily pass through a diaphragm, and therefore the hydrochloric acid and sodium chloride contained in the above-mentioned dialyser pass from the solution through the diaphragm into the water of the external vessel with considerable rapidity. The aqueous solution of colloidal silica also penetrates through the diaphragm, but very much more slowly. But if the amount of the substance dissolved is not equal on either side of the diaphragm, the whole system strives to attain a state of equilibrium; that is, the given substance penetrates through the diaphragm from the side where it is in excess to the part where there is a smaller quantity of it. All substances which are soluble in water have the faculty of penetrating through a membrane swollen in water, but the velocity of penetration is not equal, and in this respect the dialyser separates substances like a sieve. The silica passes less rapidly through the diaphragm than the sodium chloride and hydrochloric acid, so that by repeatedly changing the external water it is easy to effect the extraction of the chlorine compounds from the dialyser, which will finally only contain a solution of silica. This extraction (of HCl and NaCl) may be so complete that the liquid taken from the dialyser will not give any precipitate with a solution of silver nitrate. Graham obtained in this way soluble silica having a distinctly acid reaction, which, however, disappeared on the addition of a very minute quantity of alkali; for ten parts of silica in the solution it was sufficient to take one part of alkali in order to give the liquid an alkaline reaction, so slightly energetic are the acid properties of silicic acid. The solution of silica obtained by this method becomes gelatinous on standing, on being heated, or on evaporation under the receiver of an air-pump, &c. The hydrosol is transformed into the hydrogel, the soluble hydrate into the gelatinous. [17] _See_ Chapter I., Note 18. A solution of water-glass mixed with an excess of hydrochloric acid is poured into the dialyser, and the outer vessel is filled with water, which is continually renewed. The water carries off the sodium chloride and hydrochloric acid, and the hydrosol remains in the dialyser. Thus in addition to the gelatinous form of the silicic acid, there exists also a variety of this substance, soluble in water, as is the case with alumina. Such variation in properties and exactly the same relations with regard to water characterise an immense series of other substances having a great significance in nature. The number of such substances is especially great among organic compounds, and particularly in those classes of them which compose the principal material of the bodies of animals and plants. It is sufficient to mention, for instance, the gelatin which is familiar to all as carpenter's and other glues, and in the form of size and jelly. The same substance is also known in the solution which is used to join objects together. In a peculiar insoluble condition it enters into the composition of hides and bones. These various forms of gelatin differ in the same way as the different varieties of silica. The property of forming a jelly is exactly the same as in silica, and the adhesiveness of the solutions of both substances is identical; soluble silica adheres like a solution of gelatin. The same properties are again shown by starch, rosin, and albumin, and by a series of similar substances. The diaphragms used in dialysis are also insoluble, gelatinous, forms of colloids. The bodies of animals and plants consist largely of similar matter, insoluble in water, corresponding with the gelatinous or insoluble silicon hydrate, or with glue. The albumin which coagulates when eggs are boiled is a typical form of the gelatinous condition of such substances in the body. These slight indications are sufficient in order to show how great is the significance of those transformations which are so well marked in silica. The facts discovered by _Graham_ in 1861-1864 comprise the most essential acquisitions in the general association of these phenomena of nature in the history of organic forms. The facility of transit from hydrogel to hydrosol is the first condition of the possibility of the development of organisms. The blood contains hydrosols, and the hydrogels of the same substances are contained in the muscles and tissues, and especially on the surface, of the body. All tissues are formed from the blood, and in that case the hydrosols are converted into hydrogels.[18] The absence of crystallisation, the property, apparently under the influence of feeble agencies, of passing from the soluble condition to the insoluble, to the gelatinous condition of the hydrogel, constitute the fundamental properties of all colloids.[19] [18] A similar process occurs in plants--for example, when they secrete a store of material for the following year in their bulbs, roots, &c. (for instance, the potato in its tubers), the solutions from the leaves and stems penetrate into the roots and other parts in the form of hydrosols, where they are converted into hydrogels--that is, into an insoluble form, which is acted on with difficulty and is easily kept unaltered until the period of growth--for example, until the following spring--when they are reconverted into hydrosols, and the insoluble substance re-enters into the sap, and serves as a source of the hydrogels in the leaves and other portions of plants. [19] As regards their chemical composition the colloids are very complex--that is, they have a high molecular weight and a large molecular volume--in consequence of which they do not penetrate through membranes, and are easily subject to variation in their physical and chemical properties (owing to their complex structure and polymerism?) They have but little chemical energy, and are generally feeble acids, if belonging to the order of oxides or hydrates, such as the hydrates of molybdic and tungstic acids (Chapter XXI.). But now the number of substances capable, like colloids, of passing into aqueous solutions and of easily separating out from them, as well as of appearing in an insoluble form, must be supplemented by various other substances, among which soluble gold and silver (Chapter XXIV.) are of particular interest. So that now it may be said that the capacity of forming colloid solutions is not limited to a definite class of compounds, but is, if not a general, at all events, an exceedingly widely distributed phenomenon. Silica, as regards its _salt forming properties_, stands in the series of oxides on the boundary line on the side of the acids in just such a place as alumina occupies on the side of the bases--that is, aluminium hydroxide is the representative of the feeblest bases and silicic acid is the least energetic of acids (at least in the presence of water--that is, in aqueous solutions); in alumina, however, the basic properties are distinctly expressed, while in silica the acid properties preponderate. Like all feeble acid oxides it is capable of forming, with other acids, saline compounds which are but slightly stable and are very easily decomposed in the presence of water. The chief peculiarity of the silicates consists in the number of their types. The salts formed with nitric or sulphuric acid exist in one, two, and three tolerably stable forms, but for acids like silicic acid the number of forms is very great, almost unlimited. The natural silicates in particular furnish proof of this fact; they contain various bases in combination with silica, and for one and the same base there often exist various degrees of combination. As feeble bases are capable of forming basic salts in addition to normal salts--that is, a compound of a normal salt with a feeble base (either the hydroxide or the oxide)--so the feeble acid oxides (although not all) form, in addition to normal salts, highly acid salts--that is, normal salts _plus_ acid (hydrate or anhydride). Such acids are boric, phosphoric, molybdic, chromic, and especially silicic, acid. In order to explain these relations it is necessary first to recollect the existence of the various hydrates of silica, or silicic acids,[20] and then to turn our attention to the similarity between silicon compounds and metallic alloys. Silica is an oxide having the appearance of, and in many respects the same properties as, those oxides which combine with it, and if two metals are capable of forming homogeneous alloys in which there exist definite or indefinite compounds, it is permissible to assume a similar power of forming alloys in the case of analogous oxides. Such alloys are found in indefinite, amorphous masses in the form of glass, lava, slags, and a number of similar siliceous compounds which do not contain any definite types of combination, but nevertheless are homogeneous throughout their mass. By slow cooling, or under other circumstances, definite crystalline compounds may--and sometimes do--separate from this homogeneous mass, as also sometimes definite crystalline alloys separate from metallic alloys. [20] This is in accordance with the generally-accepted representation of the relations between salts and the hydrates of acids, but it is of little help in the study of siliceous compounds. Generally speaking, it becomes necessary to explain the property of (SiO_{2})_{_n_} to combine with (RO)_{_m_}, where _n_ may be greater than _m_, and where R may be H_{2}, Ca, &c. Here we are aided by those facts which have been attained by the investigation of carbon compounds, especially with respect to glycol. Glycol is a compound having the composition C_{2}H_{6}O_{2}, only differing from alcohol, C_{2}H_{6}O, by an extra atom of oxygen. This hydrate contains two hydroxyl groups, which may be successively replaced by chlorine, &c. Hence the composition of glycol should be represented as C_{2}H_{4}(OH)_{2}. It has been found that glycol forms so-called polyglycols. Their origin will be understood from the fact that glycol as a hydrate has a corresponding anhydride of the composition C_{2}H_{4}O, known as ethylene oxide. This substance is ethane, C_{2}H_{6}, in which two hydrogens are replaced by one atom of oxygen. Ethylene oxide is not the only anhydride of glycol, although it is the simplest one, because C_{2}H_{4}O = C_{2}H_{4}(OH)_{2} - H_{2}O. Various other anhydrides of glycol are possible, and have actually been obtained, of the composition _n_C_{2}H_{4}(OH)_{2} - (_n_ - 1)H_{2}O = (C_{2}H_{4})_{_n_}O_{_n_ - 1}(OH)_{2}. These imperfect anhydrides of glycol, or _polyglycols_, still contain hydroxyls like glycol itself, and therefore are of an alcoholic character in the same sense as glycol itself. They are obtained by various methods, and, amongst others, by the direct combination of ethylene oxide with glycol, because C_{2}H_{4}(OH)_{2} + (_n_ - 1)C_{2}H_{4}O = (C_{2}H_{4})_{_n_}O_{_n_ - 1}(OH)_{2}. The most important circumstance, from a theoretical point of view, is that these polyglycols may be distilled without undergoing decomposition, and that the general formula given above expresses their actual molecular composition. Hence we have here a direct combination of the anhydride with the hydrate, and, moreover, a repeated one. The formula A_{_n_}H_{2}O may be used to express the composition of glycol and polyglycols with respect to ethylene oxide in the most simple manner, if A stand for ethylene oxide. When _n_ = 1 we have glycol, when _n_ is greater than 1 a polyglycol. Such also is the relationship of the salts of hydrate of silica, if A stand for silica, and if we imagine that H_{2}O may also be taken _m_ times. Such a representation of the _polysilicic acids_ corresponds with the representation of the polymerism of silica. Laurent supposed the existence of several polymeric forms, Si_{2}O_{4}, Si_{3}O_{6}, &c., besides silica, SiO_{2}. The formation of crystalline rocks in nature is partly of such a nature. By aqueous or igneous agency, but in any case in a liquid condition, those oxides which form the earth's crust and her crystalline minerals came into mutual contact. First of all they formed a shapeless mass, of which lava, glass, slags and solutions are examples, but little by little, or else suddenly, some definite compounds of certain oxides existing in this alloy or in the shapeless mass were formed. This is entirely similar to two metals forming a homogeneous alloy,[21] and under known circumstances (for instance, on cooling the alloy, or in the case of aqueous solution when the two metals are simultaneously liberated from the solution), definite crystalline compounds are separated. In any case there is no doubt that there is less distinction between silica and bases, than between bases and such anhydrides as, for instance, sulphuric or nitric, or even carbonic, as is seen on comparing the physical and chemical properties of silica and various kinds of oxides. Alumina, especially, is exceedingly near akin to silica; not only in the hydrated state, but also in the anhydrous condition, there exists a certain similarity between the crystalline forms of alumina and silica, in the uncombined state. Both are very hard, transparent, inactive, non-volatile, infusible, and crystallise in the hexagonal system--in a word, they are remarkably similar, and for this reason they are capable, like two kindred metals, of entering into many different degrees of combination. Isomorphous mixtures--that is, differing by the substitution of oxides akin both in their physical and chemical characters--are very frequently met with among minerals, and the study of the latter gave the principal impetus to the study of isomorphism. Thus, in a whole series of minerals, lime and magnesia are found in variable and interchangeable proportions. Exactly the same may be said of potassium and sodium, of alumina and ferric oxide, of manganous, ferrous, magnesium oxides, &c. Such isomorphism does not, however, extend without change of form and properties beyond certain rather narrow limits.[22] What I mean by this is that lime is not always replaced totally, but often only in small quantities, by magnesia, or by the manganous and ferrous oxides, without changing the crystalline form. The same may be observed with regard to potassium and lithium, which may be in part, but not completely, replaced by sodium. On the total substitution of one metal for another, often (although not invariably) the entire nature of the substance is changed; for instance, _enstatite_ (or bronzite) is a magnesium bisilicate with a small isomorphous substitution of calcium for magnesium; its composition is expressed by the formula MgSiO_{3}, it belongs to the rhombic system. On the entire substitution of calcium, _wollastonite_, CaSiO_{3}, of the monoclinic system, is obtained; when manganese is substituted, _rhodonite_, of the triclinic system, is produced; but in all of them the angles of the prism are 86° to 88°.[23] [21] For us the latter have not a saline character, only because they are not regarded from this point of view, but an alloy of sodium and zinc is, in a broad sense, a salt in many of its reactions, for it is subject to the same double decompositions as sodium phosphide or sulphide, which clearly have saline properties. The latter (sodium phosphide), when heated with ethyl iodide, forms ethyl phosphide, and the former--_i.e._ the alloy of zinc and sodium--gives zinc ethyl; that is, the element (P, S, Zn) which was united with the sodium passes into combination with the ethyl: RNa + EtI = REt + NaI. By combining sodium successively with chlorine, sulphur, phosphorus, arsenic, antimony, tin, and zinc, we obtain substances having less and less the ordinary appearance of salts, but if the alloy of sodium and zinc cannot be termed a salt, then perhaps this name cannot be given to sodium sulphide, and the compounds of sodium with phosphorus. The following circumstance may also be observed: with chlorine, sodium gives only one compound (with oxygen, at the most three), with sulphur five, with phosphorus probably still more, with antimony naturally still more, and the more analogous an element is to sodium, the more varied are the proportions in which it is able to combine with it, the less are the alterations in the properties which take place by this combination, and the nearer does the compound formed approach to the class of compounds known as indefinite chemical compounds. In this sense a siliceous alloy, containing silica and other acids, is a salt. The oxide to a certain extent plays the same part as the sodium, whilst the silica plays the part of the acid element which was taken up successively by zinc, phosphorus, sulphur, &c., in the above examples. Such a comparison of the silica compounds with alloys presents the great advantage of including under one category the definite and indefinite silica compounds which are so analogous in composition--that is, brings under one head such crystalline substances as certain minerals, and such amorphous substances as are frequently met with in nature, and are artificially prepared, as glass, slags, enamels, &c. If the compounds of silica are substances like the metallic alloys, then (1) the chemical union between the oxides of which they are composed must be a feeble one, as it is in all compounds formed between analogous substances. In reality such feeble agencies as water and carbonic acid are able, although slowly, to act on and destroy the majority of the complex silica compounds in rocks, as we saw in the preceding chapter; (2) their formation, like that of alloys, should not be accompanied by a considerable alteration of volume; and this is actually the case. For example, felspar has a specific gravity of about 2·6, and therefore, taking its composition to be K_{2}O,Al_{2}O_{3},6SiO_{2}, we find its volume, corresponding with this formula, to be 556·8. 2·6 = 214, the volume of K_{2}O = 35, of Al_{2}O_{3} = 26, and of SiO_{2} = 22·6. Hence the sum of the volumes of the component oxides, 35 + 26 + 6 × 22·6 = 196, which is very nearly equal to that of the felspar; that is, its formation is attended by a slight expansion, and not by contraction, as is the case in the majority of other cases when combinations determined by strong affinities are accomplished. In the case in question the same phenomenon is observed as in solutions and alloys--that is, as in cases of feeble affinities. So also the specific gravity of glass is directly dependent on the amount of those oxides which enter into its composition. If in the preceding example we take the sp. gr. of silica to be, not 2·65, but 2·2, its volume = 27·3, and the sum of the volumes will be = 224--that is, greater than that of orthoclase. [22] It is, however, easy to imagine, and experience confirms the supposition, that in a complex siliceous compound containing for instance sodium and calcium, the whole of the sodium may be replaced by potassium, and _at the same time_ the whole of the calcium by magnesium, because then the substitution of potassium for the sodium will produce a change in the nature of the substance contrary to that which will occur from the calcium being replaced by magnesium. That increase in weight, decrease in density, increase of chemical energy, which accompanies the exchange of sodium for potassium will, so to speak, be compensated by the exchange of calcium for magnesium, because both in weight and in properties the sum of Na + Ca is very near to the sum of K + Mg. _Pyroxene_ or _augite_ can be taken as an example; its composition may be expressed by the formula CaMgSi_{2}O_{6}; that is, it corresponds with the acid H_{2}SiO_{3}; it is a bisilicate. In many respects it closely resembles another mineral called '_spodumene_' (they are both monoclinic). This latter has the composition Li_{6}Al_{8}Si_{15}O_{45}. On reducing both formulæ to an equal contents of silica the following distinction will be observed between them: spodumene (Li_{2}O)_{6}(Al_{2}O_{3})_{8}30SiO_{2}; augite (CaO)_{15}(MgO)_{15}30SiO_{2}. That is, the difference between them consists in the sum of the magnesia and lime (MgO)_{15} + (CaO)_{15} replacing the sum of the lithium oxide and alumina (Li_{2}O)_{6} + (Al_{2}O_{3})_{8}; and in the chemical relation these sums are near to one another, because magnesium and calcium, both in forms of oxidation and in energy (as bases), in all respects occupy a position intermediate between lithium and aluminium, and therefore the sum of the first may be replaced by the sum of the second. If we take the composition of spodumene, as it is often represented to be, Li_{2}O,Al_{2}O_{3},4SiO_{2}, the corresponding formula of augite will be (CaO)_{2},(MgO)_{2},4SiO_{2}, and also the amount of oxygen in the sum of Li_{2}OAl_{2}O_{3} will be the same as in (CaO)_{2}(MgO)_{2}. I may remark, for the sake of clearness, that lithium belongs to the first, aluminium to the third group, and calcium and magnesium to the intermediate second group; lithium, like calcium, belongs to the even series, and magnesium and aluminium to the uneven. The representation of the substitutions of analogous compounds here introduced was first deduced by me in 1856. It finds much confirmation in facts which have been subsequently discovered--for example, with respect to tourmalin. Wülfing (1888), on the basis of a number of analyses (especially of those by Röggs), states that all varieties contain an isomorphous mixture of alkali and magnesia tourmalin; into the composition of the former there enters 12SiO_{2},3B_{2}O_{3},8Al_{2}O_{3},2Na_{2}O,4H_{2}O, and of the latter 12SiO_{2},3B_{2}O_{3},5Al_{2}O_{3},12MgO,3H_{2}O. Hence it is seen that the former contains in addition the sum of 3Al_{2}O_{3},2Na_{2}O,H_{2}O, whilst in the latter this sum of oxides is replaced by 12MgO, in which there is as much oxygen as in the sum of the more clearly-defined base 2Na_{2}O and less basic 3Al_{2}O_{3}H_{2}O--that is, the relation is just the same here as between augite and spodumene. [23] With respect to the silica compounds of the various oxides, it must be observed that only the _alkali salts_ are known in a soluble form; all the others only exist in an insoluble form, so that a solution of the alkali compounds of silica, or soluble glass, gives a precipitate with a solution of the salts of the majority of other metals, and this precipitate will contain the silica compounds of the other bases. The maximum amount of the gelatinous hydrate of silica, which dissolves in caustic potash, corresponds with the formation of a compound, 2K_{2}O,9SiO_{2}. But this compound is partially decomposed, with the precipitation of hydrate of silica, on cooling the solution. Solutions containing a smaller amount of silica may be kept for an indefinite time without decomposing, and silica does not separate out from the solution; but such compounds crystallise from the solutions with difficulty. However, a crystalline bisilicate (with water) has been obtained for sodium having the composition Na_{2}O,SiO_{2}--_i.e._ corresponding to sodium carbonate. The whole of the carbonic acid is evolved, and a similar soluble sodium metasilicate is obtained on fusing 3·5 parts of sodium carbonate with 2 parts of silica. If less silica be taken a portion of the sodium carbonate remains undecomposed; however, a substance may then be obtained of the composition Si(ONa)_{4}, corresponding with orthosilicic acid. It contains the maximum amount of sodium oxide capable of combining with silica under fusion. It is a sodium orthosilicate, (Na_{2}O)_{2},SiO_{2}. Calcium carbonate, and the carbonates of the alkaline earths in general, also evolve all their carbonic acid when heated with silica, and in some instances even form somewhat fusible compounds. Lime forms a fusible slag of _calcium silicate_, of the composition CaO,SiO_{2} and 2CaO,3SiO_{2}. With a larger proportion of silica the slags are infusible in a furnace. The magnesium _slags_ are less fusible than those with lime, and are often formed in smelting metals. Many compounds of the metals of the alkaline earths with silica are also met with in nature. For instance, among the magnesium compounds there is _olivine_, (MgO)_{2},SiO_{2}, sp. gr. 3·4, which occurs in meteorites, and sometimes forms a precious stone (peridote), and occurs in slags and basalts. It is decomposed by acids, is infusible before the blow-pipe, and crystallises in the rhombic system. _Serpentine_ has the composition 3MgO,2SiO_{2},2H_{2}O; it sometimes forms whole mountains, and is distinguished for its great cohesiveness, and is therefore used in the arts. It is generally tinted green; its specific gravity is 2·5; it is exceedingly infusible, even before the blowpipe. It is acted on by acids. Among the magnesium compounds of silica, _talc_ is very widely used. It is frequently met with in rocks which are widely distributed in nature, and sometimes in compact masses; it can be used for writing like a slate pencil or chalk, and being greasy to the touch, is also known as _steatite_. It crystallises in the rhombic system, and resembles mica in many respects; like it, it is divisible into laminæ, greasy to the touch, and having a sp. gr. 2·7. These laminæ are very soft, lustrous, and transparent, and are infusible and insoluble in acids. The composition of talc approaches nearly to 6MgO,5SiO_{2},2H_{2}O. Among the crystalline silicates the following minerals are known:--_Wollastonite_ (tabular-spar), crystallises in the monoclinic system; sp. gr. 2·8; it is semi-transparent, difficultly fusible, decomposed by acids, and has the composition of a metasilicate, CaOSiO_{2}. But isomorphous mixtures of calcium and magnesium silicates occur with particular frequency in nature. The _augites_ (sp. gr. 3·3), diallages, hypersthenes, hornblendes (sp. gr. 3·1), amphiboles, common asbestos, and many similar minerals, sometimes forming the essential parts of entire rock formations, contain various relative proportions of the bisilicates of calcium and magnesium partially mixed with other metallic silicates, and generally anhydrous, or only containing a small amount of water. In the pyroxenes, as a rule, lime predominates, and in the amphiboles (also of the monoclinic system) magnesia predominates. Details upon this subject must be looked for in works upon mineralogy. The most remarkable complex siliceous compounds are the _felspars_, which enter into nearly all the primary rocks like porphyry, granite, gneiss, &c. These felspars always contain, in addition to silica and alumina, oxides presenting more marked basic properties, such as potash, soda, and lime. Thus the _orthoclase_ (adularia), or ordinary felspar (monoclinic) of the granites, contains K_{2}O,Al_{2}O_{3},6SiO_{2}; _albite_ contains the same substances, only with Na_{2}O instead of K_{2}O (it already appertains to the triclinic system); _anorthite_ contains lime, and its composition is CaO,Al_{2}O_{3},2SiO_{2}. On expressing the two last as containing equal quantities of oxygen, we have:-- Albite Na_{2} Al_{2} Si_{6} O_{16} Anorthite Ca_{2} Al_{4} Si_{4} O_{16} It is then evident that on the conversion of albite into anorthite, Na_{2}Si_{2} is replaced by Ca_{2}Al_{2}, and this sum, both in chemical energy and in the form of oxide, may be considered as corresponding with the first, because sodium and silicon are extreme elements in chemical character (from groups I. and IV.), and calcium and aluminium are means between them (from groups II. and III.), and actually both these felspar minerals are not only of one (triclinic) system, but form (Tchermak, Schuster) all possible kinds of definite compounds (isomorphous mixtures) between themselves, as indicated by their composition and all their properties. Thus oligoclase, andesine, labradorite, &c. (plagioclases), are nothing more than mutual combinations of albite and anorthite. Labradorite consists of albite, in combination with 1 to 2 molecules of anorthite. The class of _zeolites_ corresponds to the felspars; they are hydrated compounds of a similar composition to the felspars. Thus _natrolite_ contains Na_{2}O,Al_{2}O_{3},3SiO_{2},2H_{2}O, and _analcime_ presents the same composition, but contains 4SiO_{2} instead of 3SiO_{2}. In general, the felspars and zeolites contain RO,Al_{2}O_{3},_n_SiO_{2}, where _n_ varies considerably.[24] [24] The majority of the siliceous minerals have now been obtained artificially under various conditions. Thus N. N. Sokoloff showed that slags very frequently contain peridote. Hautefeuille, Chroustchoff, Friedel, and Sarasin obtained felspar identical in all respects with the natural minerals. The details of the methods here employed must be looked for in special works on mineralogy; but, as an example, we will describe the method of the preparation of felspar employed by Friedel and Sarasin (1881). From the fact that felspar gives up potassium silicate to water even at the ordinary temperature (Debray's experiments), they concluded that the felspar in granites had an aqueous origin (and this may be supposed to be the case from geological data); then, in the first place, its formation could not be accomplished unless in the presence of an excess of a solution of potassium silicate. In order to render this argument clear I may mention, as an example, that carnallite is decomposed by water into easily soluble magnesium chloride and potassium chloride, and therefore if it is of aqueous origin it could not be formed otherwise than from a solution containing an excess of magnesium chloride, and, in the second place, from a strongly-heated solution; again, felspar itself and its fellow-components in granites are anhydrous. On these facts were based experiments of heating hydrates of silica with alumina and a solution of potassium silicate in a closed vessel. The mixture was placed in a sealed platinum tube, which was enclosed in a steel tube and heated to dull redness. When the mixture contained an excess of silica the residue contained many crystals of rock crystal and tridymite, together with a powder of felspar, which formed the main product of the reaction when the proportion of hydrate of silica was decreased, and a mixture of a solution of potassium silicate with alumina precipitated together with the silica by mixing soluble glass with aluminium chloride was employed. The composition, properties, and forms of the resultant felspar proved it to be identical with that found in nature. The experiments approach very nearly to the natural conditions, all the more as felspar and quartz are obtained together in one mixture, as they so often occur in nature. Such complex silicates are generally insoluble in water,[25] and if they undergo change in it, it is but very slow, and more often only in the presence of carbonic acid. Some of the silicates which are insoluble in water are easily and directly decomposed by acids; for instance, the zeolites and those fused silicates which contain a large quantity of energetic bases--such as lime. Many of the silicates, like glass,[26] are hardly changed by acids, particularly if they contain much silica, whilst fusion with alkalis leads to the formation of compounds rich in bases, after which acids decompose the alloys formed.[27] [25] The application of _cements_ is based on this principle; they are those sorts of 'hydraulic' lime which generally form a stony mass, which hardens even under water, when mixed with sand and water. The hydraulic properties of cements are due to their containing calcareous and silico-aluminous compounds which are able to combine with water and form hydrates, which are then unacted on by water. This is best proved, in the first place, by the fact that certain slags containing lime and silica, and obtained by fusion (for example, in blast-furnaces), solidify like cements when finely ground and mixed with water; and, in the second place, by the method now employed for the manufacture of artificial cements (formerly only peculiar and comparatively rare natural products were used). For this purpose a mixture of lime and clay is taken, containing about 25 p.c. of the latter; this mixture is then heated, not to fusion, but until both the carbonic anhydride and water contained in the clay are expelled. This mass when finely ground forms Portland cement, which hardens under water. The process of hardening is based on the formation of chemical compounds between the lime, silica, alumina, and water. These substances are also found combined together in various natural minerals--for example, in the zeolites, as we saw above. In all cases cement which has set contains a considerable amount of water, and its hardening is naturally due to hydration--that is, to the formation of compounds with water. Well-prepared and very finely-ground cement hardens comparatively quickly (in several days, especially after being rammed down), with 3 parts (and even more) of coarse sand and with water, into a stony mass which is as hard and durable as many stones, and more so than bricks and limestone. Hence not only all maritime constructions (docks, ports, bridges, &c.), but also ordinary buildings, are made of Portland cement, and are distinguished for their great durability. A combination of ironwork (ties, girders) and cement is particularly suitable for the construction of aqueducts, arches, reservoirs, &c. Arches and walls made of such cements may be much less thick than those built up of ordinary stone. Hence the production and use of cement rapidly increases from year to year. The origin of accurate data respecting cements is chiefly due to Vicat. In Russia Professor Schuliachenko has greatly aided the extension of accurate data concerning Portland cement. Many works for the manufacture of cement have already been established in various parts of Russia, and this industry promises a great future in the arts of construction. [26] _Glass_ presents a similar complex composition, like that of many minerals. The ordinary sorts of white glass contain about 75 p.c. of silica, 13 p.c. of sodium oxide, and 12 p.c of lime; but the inferior sorts of glass sometimes contain up to 10 p.c. of alumina. The mixtures which are used for the manufacture of glass are also most varied. For example, about 300 parts of pure sand, about 100 parts of sodium carbonate, and 50 of limestone are taken, and sometimes double the proportion of the latter. Ordinary _soda-glass_ contains sodium oxide, lime, and silica as the chief component parts. It is generally prepared from sodium sulphate mixed with charcoal, silica, and lime (Chapter XII.), in which case the following reaction takes place at a high temperature: Na_{2}SO_{4} + C + SiO_{2} = Na_{2}SiO_{3} + SO_{2} + CO. Sometimes potassium carbonate is taken for the preparation of the better qualities of glass. In this case a glass, _potash-glass_, is obtained containing potassium oxide instead of sodium oxide. The best-known of these glasses is the so-called Bohemian glass or crystal, which is prepared by the fusion of 50 parts of potassium carbonate, 15 parts of lime, and 100 parts of quartz. The preceding kinds of glass contain lime, whilst crystal glass contains lead oxide instead. Flint glass--that is, the lead glass used for optical instruments--is prepared in this manner, naturally from the purest possible materials. _Crystal-glass_--_i.e._ glass containing lead oxide--is softer than ordinary glass, more fusible and has a higher index of refraction. However, although the materials for the preparation of glass be most carefully sorted, a certain amount of iron oxides falls into the glass and renders it greenish. This coloration may be destroyed by adding a number of substances to the vitreous mass, which are able to convert the ferrous oxide into ferric oxide; for example, manganese peroxide (because the peroxide is deoxidised to manganous oxide, which only gives a pale violet tint to the glass) and arsenious anhydride, which is deoxidised to arsenic, and this is volatilised. The manufacture of glass is carried on in furnaces giving a very high temperature (often in regenerative furnaces, Chapter IX.). Large clay crucibles are placed in these furnaces, and the mixture destined for the preparation of the glass, having been first roasted, is charged into the crucibles. The temperature of the furnace is then gradually raised. The process takes place in three separate stages. At first the mass intermixes and begins to react; then it fuses, evolves carbonic acid gas, and forms a molten mass; and, lastly, at the highest temperature, it becomes homogeneous and quite liquid, which is necessary for the ultimate elimination of the carbonic anhydride and solid impurities, which latter collect at the bottom of the crucible. The temperature is then somewhat lowered, and the glass is taken out on tubes and blown into objects of various shapes. In the manufacture of window-glass it is blown into large cylinders, which are then cut at the ends and across, and afterwards bent back in a furnace into the ordinary sheets. After being worked up, all glass objects have to be subjected to a slow cooling (_annealing_) in special furnaces, otherwise they are very brittle, as is seen in the so-called 'Rupert's drops,' formed by dropping molten glass into water; although these drops preserve their form, they are so brittle that they break up into a fine powder if a small piece be knocked off them. Glass objects have frequently to be polished and chased. In the manufacture of mirrors and many massive objects the glass is cast and then ground and polished. Coloured glasses are either made by directly introducing into the glass itself various oxides, which give their characteristic tints, or else a thin layer of a coloured glass is laid on the surface of ordinary glass. Green glasses are formed by the oxides of chromium and copper, blue by cobalt oxide, violet by manganese oxide, and red glass by cuprous oxide and by the so-called purple of Cassius--_i.e._ a compound of gold and tin--which will be described later. A yellow coloration is obtained by means of the oxides of iron, silver, or antimony, and also by means of carbon, especially for the brown tints for certain kinds of bottle-glass. From what has been said about glass it will be understood that it is impossible to give a definite formula for it, because it is a non-crystalline or amorphous alloy of silicates; but such an alloy can only be formed within certain limits in the proportions between the component oxides. With a large proportion of silica the glass very easily becomes clouded when heated; with a considerable proportion of alkalis it is easily acted on by moisture, and becomes cloudy in time on exposure to the air; with a large proportion of lime it becomes infusible and opaque, owing to the formation of crystalline compounds in it; in a word, a certain proportion is practically attained among the component oxides in order that the glass formed may have suitable properties. Nevertheless, it may be well to remark that the composition of common glass approaches to the formula Na_{2}O,CaO,4SiO_{2}. The coefficient of cubical expansion of glass is nearly equal to that of platinum and iron, being approximately 0·000027. The specific heat of glass is nearly 0·18, and the specific gravity of common soda glass is nearly 2·5, of Bohemian glass 2·4, and of bottle glass 2·7. Flint glass is much heavier than common glass, because it contains the heavier oxide of lead, its specific gravity being 2·9 to 3·2. [27] It must be recollected that although acids seem to act only feebly on the majority of silicates, nevertheless a finely-levigated powder of siliceous compounds is acted on by strong acids, especially with the aid of heat, the basic oxides being taken up and gelatinous silica left behind. In this respect sulphuric acid heated to 200° with finely-divided siliceous compounds in a closed tube acts very energetically. According to the periodic law, the nearest analogues of silicon ought to be elements of the uneven series, because silicon, like sodium, magnesium, and aluminium, belongs to the uneven series.[28] Immediately after silicon follows ekasilicon or _germanium_, Ge = 72, whose properties were predicted (1871) before Winkler (1886) in Freiberg, Saxony (Chapter XV. § 5), discovered this element in a peculiar silver ore called _argyrodite_, Ag_{6}GeS_{5}.[29] Easily reduced from the oxide by heating with hydrogen and charcoal, and separated from its solutions by zinc, metallic germanium proved to be greyish white, easily crystallisable (in octahedra), brittle, fusible (under a coating of fused borax) at about 900°, and easily oxidisable; the specific gravity = 5·469, the atomic weight = 72·3, and the specific heat = 0·076,[30] as might be expected for this element according to the periodic law. The corresponding _germanium dioxide_, GeO_{2}, is a white powder having a specific gravity of 4·703; water, especially when boiling, dissolves this dioxide (1 part of GeO_{2} requires for solution 247 parts of water at 20°, 95 parts at 100°). It forms soluble salts with alkalis and is but sparingly soluble in acids.[31] In a stream of chlorine the metal forms _germanium chloride_, GeCl_{4}, which boils at 86°, and has a specific gravity of 1·887 at 18°; water decomposes it, forming the oxide. All these properties[32] of germanium, showing its analogy to silicon and tin, form a most beautiful demonstration of the truth of the periodic law.[33] [28] Such elements as silicon, tin, and lead were only brought together under one common group by means of the periodic law, although the quadrivalency of tin and lead was known much earlier. Generally silicon was placed among the non-metals, and tin and lead among the metals. [29] At first (February 1886) the want of material to work on, the absence of a spectrum in the Bunsen's flame, and the solubility of many of the compounds of germanium, presented difficulties in the researches of Professor Winkler, who, on analysing argyrodite by the usual method, obtained a constant loss of 7 p.c., and was thus led to search for a new element. The presence of arsenic and antimony in the accompanying minerals also impeded the separation of the new metal. After fusion with sulphur and sodium carbonate, argyrodite gives a solution of a sulphide which is precipitated by an _excess_ of hydrochloric acid; germanium sulphide is soluble in ammonia and then precipitated by hydrochloric acid, as a _white_ precipitate, which is dissolved (or decomposed) by water. After being oxidised by nitric acid, dried and ignited germanium sulphide leaves the oxide GeO_{2}, which is reduced to the metal when ignited in a stream of hydrogen. [30] G. Kobb determined the spectrum of germanium, when the metal was taken as one of the electrodes of a powerful Ruhmkorff's coil. The wave-lengths of the most distinct lines are 602, 583, 518, 513, 481, 474, millionths of a millimetre. [31] If germanium or germanium sulphide be heated in a stream of hydrochloric acid, it forms a volatile liquid, boiling at 72°, which Winkler regarded as germanium chloride, GeCl_{2}, or germanium chloroform, GeHCl_{3}. It is decomposed by water, forming a white substance, which may perhaps be the hydrate of germanious oxide, GeO, and acts as a powerfully reducing agent in a hydrochloric acid solution. [32] Under certain circumstances germanium gives a blue coloration like that of ultramarine, as Winkler showed, which might have been expected from the analogy of germanium with silicon. [33] Winkler expressed this in the following words (_Jour. f. pract. Chemie_, 1886 [2], 34, 182-183): '... es kann keinem Zweifel mehr unterliegen, dass das neue Element nichts Anderes, als das vor fünfzehn Jahren von _Mendeléeff_ prognosticirte _Ekasilicium_ ist.' 'Denn einen schlagenderen Beweis für die Richtigkeit der Lehre von der Periodicität der Elemente, als den, welchen die Verkörperung des bisher hypothetischen "Ekasilicium" in sich schliesst, kann es kaum geben, und er bildet in Wahrheit mehr, als die blosse Bestätigung einer kühn aufgestellten Theorie, er bedeutet eine eminente Erweiterung des chemischen Gesichtfeldes, einen mächtigen Schritt in's Reich der Erkenntniss.' The increase of atomic weight from silicon 28 to germanium 72 is 44--that is, about the same difference as there is in the atomic weights of chlorine and bromine; between germanium and its next analogue, _tin_ (Sn = 118), the difference is 46--that is, almost as much as the amount by which the atomic weight of iodine exceeds that of bromine. Metallic tin is rarely met with in _nature_; it occurs in the veins of ancient formations, almost exclusively in the form of oxide, SnO_{2}, called _tin-stone_. The best known tin deposits are in Cornwall and in Malacca. In Russia, tin ores have been found in small quantities on the shores of Lake Ladoga, in Pitkarand. The crushed ore may easily be separated from the earthy matter accompanying it by washing on inclined tables, as the tin-stone has a specific gravity of 6·9, whilst the impurities are much lighter. _Tin oxide is very easily reduced_ to metallic tin by heating with charcoal. For this reason tin was known in ancient times, and the Ph[oe]nicians brought it from England. Metallic tin is cast into ingots of considerable weight or into thin sticks or rods. Tin has a white colour, rather duller than that of silver. It fuses easily at 232°, and crystallises on cooling. Its specific gravity is 7·29. The crystalline structure of ordinary tin is noticed in bending tin rods, when a peculiar sound is heard, produced by the fracture of the particles of tin along the surfaces of crystalline structure. When pure tin is cooled to a low temperature it splits up into separate crystals, the bond between the particles is lost, the tin assumes a grey colour, becomes less brilliant--in a word, its properties become changed, as Fritzsche showed. This depends on the peculiar structure which the tin then acquires, and is particularly remarkable because it is effected by cold in a solid.[33 bis] If such tin be fused, or even simply heated, it becomes like ordinary tin, but is again changed when cooled. When in this condition tin has a specific gravity of 7·19. Similarly, tin is obtained by the action of the galvanic current on a solution of tin chloride; it then appears in crystals of the cubic system, and has a specific gravity of 7·18--that is, the same as when cooled.[34] [33 bis] Emilianoff (1890) states that in the cold of the Russian winter 30 out of 200 tin moulds for candles were spoilt through becoming quite brittle. [34] The tin deposited by an electric current from a neutral solution of SnCl_{2} easily oxidises and becomes coated with SnO (Vignon, 1889). Tin is softer than silver and gold, and is only surpassed by lead in this respect. In addition to this it is very ductile, but its tenacity is very slight, so that wire made from it will bear but little strain. In consequence of its ductility it is easily worked, by forging and rolling into very thin sheets (tin foil), which are used for wrapping many articles to preserve them from moisture, &c. In this case, however, and in many others, lead is mixed with the tin, which, within certain limits, does not alter the ductility. Whilst so soft at the ordinary temperatures tin becomes brittle at 200°, before fusing. Tin powder may be easily obtained if the metal be fused and then stirred whilst cooling. At a white heat tin may be distilled, but with more difficulty than zinc. If molten tin comes into contact with oxygen, it oxidises, forming stannic oxide, SnO_{2}, _and its vapour burns_ with a white flame. _At ordinary temperatures tin does not oxidise_, and this very important property of tin allows it to be applied in many cases for covering other metals to prevent their oxidising. This is termed _tinning_. Iron and copper are frequently tinned. Iron and steel sheets, coated with tin, bear the name of tin plate (for the most part made in England), and are used for numerous purposes. Tin plate is prepared by immersing iron sheets, previously thoroughly cleansed by acid and mechanical means, into molten tin.[34 bis] [34 bis] If after this the coating of tin be rapidly cooled--for instance, by dashing water over it--it crystallises into diverse star-shaped figures, which become visible when the sheets are first immersed in dilute aqua regia and then in a solution of caustic soda. The coating of iron by tin, guards it against the direct access of air, but it only preserves the iron from oxidation so long as it forms a perfectly continuous coating. If the iron is left bare in certain places, it will be powerfully oxidised at these spots, because the tin is electro-negative with respect to the iron, and thus the oxidation is confined entirely to the iron in the presence of tin. Hence a coating of tin over iron objects only partially preserves them from rusting. In this respect a coating of zinc is more effectual. However, a dense and invariable alloy is formed over the surface of contact of the iron and tin, which binds the coating of tin to the remaining mass of the iron. Tin may be fused with cast iron, and gives a greyish-white alloy, which is very easily cast, and is used for casting many objects for which iron by itself would be unsuitable owing to its ready oxidisability and porosity. The coating of copper objects by tin is generally done to preserve the copper from the action of acid liquids, which would attack the copper in the presence of air and convert it into soluble salts. Tin is not acted on in this manner, and therefore copper vessels for the preparation of food should be tinned. Tin with copper forms _bronze_, an alloy which is most extensively used in the arts. Bronze has various colours and a variety of physical properties, according to the relative amount of copper and tin which it contains. With an excess of copper the alloy has a yellow colour; the admixture of tin imparts considerable hardness and elasticity to the copper. An alloy containing 78 parts of copper and about 22 per cent. of tin is so elastic that it is used for casting bells, which naturally require a very elastic and hard alloy.[35] For casting statues and various large or small ornamental articles alloys containing 2 to 5 p.c. of tin, 10 to 30 p.c. of zinc, and 65 to 85 p.c. of copper are used.[36] Tin is also often used alloyed with lead, for making various objects--for instance, drinking vessels. [35] The ancient Chinese alloys, containing about 20 p.c. of tin (specific gravity of alloys about 8·9), which have been rapidly cooled, are distinguished for their resonance and elasticity. These alloys were formerly manufactured in large quantities in China for the musical instruments known as _tom-toms_. Owing to their hardness, alloys of this nature are also employed for casting guns, bearings, &c., and an alloy containing about 11 p.c. of tin (corresponding with the ratio Cu_{15}Sn) is known as gun-metal. The addition of a small quantity of phosphorus, up to 2 p.c., renders bronze still harder and more elastic, and the alloy so formed is now used under the name of phosphor-bronze. The alloy SnCu_{3} is brittle, of a bluish colour, and has nothing in common with either copper or tin in its appearance or properties. It remains perfectly homogeneous on cooling, and acquires a crystalline structure (Riche). All these signs clearly indicate that the alloy SnCu_{3} is a product of chemical combination, which is also seen to be the case from its density, 8·91. Had there been no contraction, the density of the alloy would be 8·21. It is the heaviest of all the alloys of tin and copper, because the density of tin is 7·29 and of copper 8·8. The alloy SnCu_{4}, specific gravity 8·77, has similar properties. All the alloys except SnCu_{3} and SnCu_{4} split up on cooling; a portion richer in copper solidifies first (this phenomenon is termed the _liquation_ of an alloy), but the above two alloys do not split up on cooling. In these and many similar facts we can clearly distinguish a _chemical union between the metals_ forming an alloy. The alloys of tin and copper were known in very remote ages, before iron was used. The alloys of zinc and tin are less used, but alloys composed of zinc, tin, and copper frequently replace the more costly bronze. Concerning the alloys of lead _see_ Note 46. [36] An excellent proof of the fact that alloys and solutions are subject to law is given, amongst others, by the application of Raoult's method (Chapter I., Note 49) to solutions of different metals in tin. Thus Heycock and Neville (1889) showed that the temperature of solidification of molten tin (226°·4) is lowered by the presence of a small quantity of other metals in proportion to the concentration of the solution. The following were the reductions of the temperature of solidification of tin obtained by dissolving in it atomic proportions of different metals (for example, 65 parts of zinc in 11,800 parts of tin); Zn 2°·53, Cu 2°·47, Ag 2°·67, Cd 2°·16, Pb 2°·22, Hg 2°·3, Sb 2° [rise], Al 1°·34. As Raoult's method (Chapter VII.) enables the molecular weight to be determined, the almost perfect identity of the resultant figures (except for aluminium) shows that the molecules of copper, silver, lead, and antimony contain _one atom in the molecule_, like zinc, mercury, and cadmium. They obtained the same result (1890) for Mg, Na, Ni, Au, Pd, Bi and In. It should here be mentioned that Ramsay (1889) for the same purpose (the determination of the molecular weight of metals on the basis of their mutual solution) took advantage of the variation of the vapour tension of mercury (_see_ Vol. I., p. 134), containing various metals in solution, and he also found that the above-mentioned metals contain but one atom in the molecule. Tin decomposes the vapour of water when heated with it, liberating the hydrogen and forming stannic oxide. Sulphuric acid, diluted with a considerable quantity of water, does not act, or at all events acts very slightly, on tin, but tin reduces hot strong sulphuric acid, when not only sulphurous anhydride but also sulphuretted hydrogen is evolved. Hydrochloric acid acts very easily on tin, with evolution of hydrogen and formation of stannous chloride, SnCl_{2}, in solution, which, with an excess of hydrochloric acid and access of air, is converted into stannic chloride: SnCl_{2} + 2HCl + O = SnCl_{4} + H_{2}O.[36 bis] Nitric acid diluted with a considerable quantity of water dissolves tin at the ordinary temperature, whilst the nitric acid itself is reduced, forming, amongst other products, ammonia and hydroxylamine. Here the tin passes into solution in the form of stannous nitrate. Stronger nitric acid (also more dilute, when heated) transforms the tin into its highest grade of oxidation, SnO_{2}, but the latter then appears as the so-called metastannic acid, which does not dissolve in nitric acid, and therefore the tin does not pass into solution. Feeble acids--for instance, carbonic and organic acids--do not act on tin even in the presence of oxygen, because tin does not form any powerful bases. [36 bis] The action of a mixture of hydrochloric acid and tin forms an excellent means of reducing, wherein both the hydrogen liberated by the mixture (at the moment of separation) and the stannous chloride act as powerful reducing and deoxidising agents. Thus, for instance, by this mixture nitro-compounds are transformed into amido-compounds--that is, the elements of the group NO_{2} are reduced to NH_{2}. It is important to remark as a characteristic of tin that it is reduced from its solutions by many metals which are more easily oxidised, as, for instance, by zinc. _In combination_, _tin_ appears in the two types, SnX_{4} and SnX_{2},[37] compounds of the intermediate type, Sn_{2}X_{6}, being also known, but these latter pass with remarkable facility in most cases into compounds of the higher and lower types, and therefore the form SnX_{3} cannot be considered as independent. [37] Many volatile compounds of tin are known, whose molecular weights can therefore be established from their vapour densities. Among these may be mentioned stannic chloride, SnCl_{4}, and stannic ethide, Sn(C_{2}H_{5})_{4} (the latter boils at about 150°). But V. Meyer found the vapour density of stannous chloride, SnCl_{2}, to be variable between its boiling point (606°) and 1100°, owing, it would seem, to the fact that the molecule then varies from Sn_{2}Cl_{4} to SnCl_{2}, but the vapour density proved to be less than that indicated by the first and greater than that shown by the second formula, although it approaches to the latter as the temperature rises--that is, it presents a similar phenomenon to that observed in the passage of N_{2}O_{4} into NO_{2}. _Stannous oxide_, SnO, in an anhydrous condition is obtained by boiling solutions of stannous salts with alkalis, the first action of the alkali being to precipitate a white hydrate of stannous oxide, Sn(OH)_{2}SnO. The latter when heated parts with water as easily as the hydrate of copper oxide. In this form stannous oxide is a black crystalline powder (specific gravity 6·7) capable of further oxidation when heated. The hydrate is freely soluble in acids, and also in potassium and sodium hydroxides, but not in aqueous ammonia.[38] This property indicates the feeble basic properties of this lower oxide, which acts in many cases as a reducing agent.[39] Among the compounds corresponding with stannous oxide the most remarkable and the one most frequently used is stannous chloride or _chloride of tin_, SnCl_{2}, also called proto-chloride of tin (because it is the lowest chloride, containing half as much Cl as SnCl_{4}). It is a transparent, colourless, crystalline substance, melting at 250° and boiling at 606°. Water dissolves it, without visible change (in reality partial decomposition occurs, as we shall see presently). It is also soluble in alcohol. It is obtained by heating tin in dry hydrochloric acid gas, the hydrogen being then liberated, or by dissolving metallic tin in hot strong hydrochloric acid and then evaporating quickly. On cooling, crystals of the monoclinic system are obtained having the composition SnCl_{2},2H_{2}O. An aqueous solution of this substance absorbs oxygen from the atmosphere, and gives a precipitate containing stannic oxide. From this it follows that a solution of stannous chloride will act as a reducing agent, a fact frequently made use of in chemical investigations--for example, for reducing metals from their solutions--since even mercury may be reduced to a metallic state from its salts by means of stannous chloride. This reducing property is also employed in the arts, especially in the dyeing industry, where this substance in the form of a crystalline salt finds an extensive application, and is known as _tin salt_ or tin crystals. [38] When rapidly boiled, an alkaline solution of stannous oxide deposits tin and forms stannic oxide, 2SnO = Sn + SnO_{4}, which remains in the alkaline solution. [39] Weber (1882) by precipitating a solution of stannous chloride with sodium sulphite (this salt as a reducing agent prevents the oxidation of the stannous compound) and dissolving the washed precipitate in nitric acid, obtained crystals of _stannous nitrate_, Sn(NO_{3})_{2},20H_{2}O, on refrigerating the solution. This crystallo-hydrate easily melts, and is deliquescent. Besides this, a more stable anhydrous basic salt, Sn(NO_{3})_{2},SnO, is easily formed. In general, stannous oxide as a feeble base easily forms basic salts, just as cupric and lead oxides do. For the same reason SnX_{2} easily forms double salts. Thus a potassium salt, SnK_{2}Cl_{4},H_{2}O, and especially an ammonium salt, Sn(NH_{4})_{2}Cl_{4},H_{2}O, called _pink salt_, are known. Some of these salts are used in the arts, owing to their being more stable than tin salts alone. Stannous bromide and iodide, SnBr_{2} and SnI_{2}, resemble the chloride in many respects. Among other stannous salts a sulphate, SnSO_{4}, is known. It is formed as a crystalline powder when a solution of stannous oxide in sulphuric acid is evaporated under the receiver of an air-pump. The feeble basic character of the stannous oxide is clearly seen in this salt. It decomposes with extreme facility, when heated, into stannic oxide and sulphurous anhydride, but it easily forms double salts with the salts of the alkali metals. In gaseous hydrochloric acid, stannous chloride, SnCl_{2},2H_{2}O, forms a liquid having the composition SnCl_{2},HCl,3H_{2}O (sp gr. 2·2, freezes at -27°), and a solid salt, SnCl_{2},H_{2}O (Engel). _Stannic oxide_, SnO_{2}, occurring in nature as _tinstone_, or _cassiterite_, is formed during the oxidation or combustion of heated tin in air as a white or yellowish powder which fuses with difficulty. It is prepared in large quantities, being used as a white vitreous mixture for coating ordinary tiles and similar earthenware objects with a layer of easily fusible glass or enamel. Acid solutions of stannic oxide treated with alkalis, and alkaline solutions treated with acids, give a precipitate of stannic hydroxide, Sn(OH)_{4}, also known as stannic acid, which, when heated, gives up water and leaves the anhydride, SnO_{2}, which is insoluble in acids, clearly showing the feebleness of its basic character. When fused with alkali hydroxides (not with their carbonates or acid sulphates), an alkaline compound is obtained which is soluble in water. Stannic hydroxide, like the hydrates of silica, is a colloidal substance, and presents several different modifications, depending on the method of preparation, but having an identical composition; the various hydroxides have also a different appearance, and act differently with reagents. For instance, a distinction is made between ordinary stannic acid and metastannic acid. _Stannic acid_ is produced by precipitation by soda or ammonia from a freshly-prepared solution of stannic chloride, SnCl_{4}, in water; on drying the precipitate thus obtained, a non-crystalline mass is formed, which is freely soluble in strong hydrochloric or nitric acids, and also in potassium and sodium hydroxides. This ordinary stannic acid may be still better obtained from sodium stannate by the action of acids. _Metastannic acid_ is insoluble in sulphuric and nitric acids. It is obtained in the form of a heavy white powder by treating tin with nitric acid; hydrochloric acid does not dissolve it immediately, but changes it to such an extent that, after pouring off the acid, water extracts the stannic chloride, SnCl_{4}, already formed. Dilute alkalis not only dissolve metastannic acid, but also transform it into salts, which, slowly, yet completely, dissolve in _pure water_, but are insoluble even in dilute alkali hydroxides. Dilute hydrochloric acid, especially when boiling, changes the ordinary hydrate into metastannic acid. On this depends, by the way, the formation of a white precipitate, stannic hydroxide, from solutions of stannous and stannic chlorides diluted with water. The stannic oxide first dissolved changes under the influence of hydrochloric acid into metastannic acid, which is insoluble in water in the presence of hydrochloric acid. Solutions of metastannic acid differ from solutions of ordinary stannic acid, and in the presence of alkali they change into solutions of ordinary acid, so that metastannic acid corresponds principally with the acid compounds of stannic oxide, and ordinary stannic acid with the alkaline compounds.[40] Graham obtained a soluble colloidal hydroxide; it is subject to the same transformations that are in general peculiar to colloids. [40] Frémy supposes the cause of the difference to consist in a difference of polymerisation, and considers that the ordinary acid corresponds with the oxide SnO_{2}, and the meta-acid with the oxide Sn_{5}O_{10}, but it is more probable that both are polymeric but in a different degree. Stannic acid with sodium carbonate gives a salt of the composition Na_{2}SnO_{3}. The same salt is also obtained by fusing metastannic acid with sodium hydroxide, whilst metastannic acid gives a salt, Na_{2}SnO_{3},4SnO_{2} (Frémy), when treated with a dilute solution of alkali; moreover, stannic acid is also soluble in the ordinary stannate, Na_{2}SnO_{3} (Weber), so that both stannic acids (like both forms of silica) are capable of polymerisation, and probably only differ in its degree. In general, there is here a great resemblance to silica, and Graham obtained a solution of stannic acid by the direct dialysis of its alkaline solution. The main difference between these acids is that the meta-acid is soluble in hydrochloric acid, and gives a precipitate with sulphuric acid and stannous chloride, which do not precipitate the ordinary acid. Vignon (1889) found that more heat is evolved in dissolving stannic acid in KHO than metastannic. Stannic oxide shows the properties of a slightly energetic and intermediate oxide (like water, silica, &c.); that is to say, it forms saline compounds both with bases and with acids, but both are easily decomposed, and are but slightly stable. But still the acid character is more clearly developed than the basic, as in silica, germanic oxide, and lead dioxide. This determines the character of the compounds SnX_{4}, corresponding to stannic chloride, SnCl_{4} (also called tetrachloride of tin). It is obtained in an anhydrous condition by the direct action of chlorine on tin, and is then easily purified, because it is a liquid boiling at 114°, and therefore can be easily distilled. Its specific gravity is 2·28 (at 0°), and it fumes in the open air (spiritus fumans libavii), reacting on the moisture of the air, thus showing the properties of a chloranhydride. Water however does not at first decompose it, but dissolves it, and on evaporation gives the crystallo-hydrate SnCl_{4},5H_{2}O. If but little water be taken, crystals containing SnCl_{4},3H_{2}O are formed, which part with one-third of the water when placed under the receiver of the air-pump. A large quantity of water however, especially on heating, causes a precipitate of metastannic acid[41] and formation of HCl. [41] The formation of the compound SnCl_{4},3H_{2}O is accompanied by so great a contraction that these crystals, although they contain water, are heavier than the anhydrous chloride SnCl_{4}. The penta-hydrated crystallo-hydrate absorbs dry hydrochloric acid, and gives a liquid of specific gravity 1·971, which at 0° yields crystals of the compound SnCl_{4},2HCl,6H_{2}O (it corresponds with the similar platinum compound), which melt at 20° into a liquid of specific gravity 1·925 (Engel). Stannic chloride combines with ammonia (SnCl_{4},4NH_{3}), hydrocyanic acid, phosphoretted hydrogen, phosphorus pentachloride (SnCl_{4},PCl_{5}), nitrous anhydride and its chloranhydride (SnCl_{4},N_{2}O_{3} and SnCl_{4},2NOCl), and with metallic chlorides (for example, K_{2}SnCl_{6}, (NH_{4})_{2}SnCl_{6}, &c.) In general, a highly-developed faculty for combination is observed in it. Tin does not combine directly with iodine, but if its filings be heated in a closed tube with a solution of iodine in carbon bisulphide, it forms stannic iodide, SnI_{4}, in the form of red octahedra which fuse at 142° and volatilise at 295°. The fluorine compounds of tin have a special interest in the history of chemistry, because they give a series of double salts which are isomorphous with the salts of hydrofluosilicic acid, SiR_{2}F_{6}, and this fact served to confirm the formula SiO_{2} for silica, as the formula SnO_{2} was indubitable. Although _stannic fluoride_, SnF_{4}, is almost unknown in the free state, its corresponding double salts are very easily formed by the action of hydrofluoric acid on alkaline solutions of stannic oxide; thus, for example, a crystalline salt of the composition SnK_{2}F_{6},H_{2}O is obtained by dissolving stannic oxide in potassium hydroxide and then adding hydrofluoric acid to the solution. The barium salt, SnBaF_{6},3H_{2}O, is sparingly soluble like its corresponding silicofluoride. The more soluble salt of strontium, SnSrF_{6},2H_{2}O, crystallises very well, and is therefore more important for the purposes of research; it is isomorphous with the corresponding salt of silicon (and titanium); the magnesium salt contains 6H_{2}O. Stannic sulphide, SnS_{2}, is formed, as a yellow precipitate, by the action of sulphuretted hydrogen on acid solutions of stannic salts; it is easily soluble in ammonium and potassium sulphides, because it has an acid character, and then forms thiostannates (see Chapter XX.). In an anhydrous state it has the form of brilliant golden yellow plates, which may be obtained by heating a mixture of finely-divided tin, sulphur, and sal-ammoniac for a considerable time. It is sometimes used in this form under the name of mosaic gold, as a cheap substitute for gold-leaf in gilding wood articles. On ignition it parts with a portion of its sulphur, and is converted into stannous sulphide SnS. It is soluble in caustic alkalis. Hydrochloric acid does not dissolve the anhydrous crystalline compound, but the precipitated powdery sulphide is soluble in boiling strong hydrochloric acid, with the evolution of hydrogen sulphide. _The alkali compounds of stannic oxide_--that is, the compounds in which it plays the part of an acid, corresponding in this respect to the compounds of silica and other anhydrides of the composition RO_{2}--are very easily formed and are used in the arts. Their composition in most cases corresponds with the formula SnM_{2}O_{3}--that is, SnO(MO)_{2}, similar to CO(MO)_{2}, where M = K, Na. Acids, even feeble acids like carbonic, decompose the salts, like the corresponding compounds of alumina or silica. In order to obtain _potassium stannate_, which crystallises in rhombohedra, and has the composition SnK_{2}O_{3},3H_{2}O, potassium hydroxide (8 parts) is fused, and metastannic acid (3 parts) gradually added. _Sodium stannate_ is prepared in practice in large quantities by heating a solution of caustic soda with lead oxide and metallic tin. In this last case an alkaline solution of lead oxide is formed, and the tin acts on the solution in such a way as to reduce the lead to the metallic state, and itself passes into solution. It is very remarkable that lead displaces tin when in combination with acids, whilst tin, on the contrary, displaces lead from its alkali compounds. By dissolving the mass obtained in water, and adding alcohol, sodium stannate is precipitated, which may then be dissolved in water and purified by re-crystallisation. In this case it has the composition SnNa_{2}O_{3},3H_{2}O if separated from strong solutions, and SnNa_{2}O_{3},10H_{2}O when crystallised at a low temperature from dilute solutions. In the arts this salt is used as a mordant in dyeing operations. With a cold solution of sodium hydroxide metastannic acid forms a salt of the composition (NaHO)_{2},5SnO_{2},3H_{2}O, from which Frémy drew his conclusions concerning the polymerism of metastannic acid. Tin, like other metals and many metalloids, gives a peroxide form of combination or _perstannic oxide_. This substance was obtained by Spring (1889) in the form of a hydrate, H_{2}Sn_{2}O_{7} = 2(SnO_{3})H_{2}O, by mixing a solution of SnCl_{2}, containing an excess of HCl, with freshly prepared peroxide of barium. A cloudy liquid is then obtained, and this after being subjected to dialysis leaves a gelatinous mass which on drying is found to have the composition Sn_{2}H_{2}O_{7}. Above 100° this substance gives off oxygen and leaves SnO_{2}. It is evident that SnO_{3} bears the same relation to SnO_{2} as H_{2}O_{2} to H_{2}O or ZnO_{2} to ZnO, &c. Tin occupies the same position amongst the analogues of silicon as cadmium and indium amongst the analogues of magnesium and aluminium respectively, and as in each of these cases the heavier analogues with a high atomic weight and a special combination of properties--namely, mercury and thallium--are known, so also for silicon we have _lead_ as the heaviest analogue (Pb = 206), with a series of both kindred and special properties. The higher type, PbX_{4}--for instance, PbO_{2}--is in a chemical sense far less stable than the lower type, PbX. The ordinary compounds of lead correspond with the latter, and in addition to this, PbO, although not particularly energetic, is still a decided base easily forming basic salts, PbX_{2}(PbO)_{n}. Although the compounds PbX_{4}, are unstable they offer many points of analogy with the corresponding compounds of tin SnO_{2}; this is seen, for instance, in the fact that PbO_{2} is a feeble acid, giving the salt PbK_{2}O_{3}, that PbCl_{4} is a liquid like SnCl_{4} which is not affected by sulphuric acid, and that PbF_{4} gives double salts, like SnF_{4} or SiF_{4} (Brauner 1894. See Chapter II., Note 49 bis); Pb(C_{2}H_{5})_{4} also resembles Sn(C_{2}H_{5})_{4} &c. All this shows that lead is a true analogue of tin, as Hg is of cadmium.[41 bis] [41 bis] Although this has long been generally recognised from the resemblance between the two metals, still from a chemical point of view it has only been demonstrated by means of the periodic law. _Lead_ is found in nature in considerable masses, in the form of galena, _lead sulphide_, PbS.[42] The specific gravity of galena is 7·58, colour grey; it crystallises in the regular system, and has a fine metallic lustre. Both the native and artificial sulphides are insoluble in acids (hydrogen sulphide gives a black precipitate with the salts PbX_{2}).[42 bis] When heated, lead melts, and in the open air is either totally or partially transformed into white lead sulphate, PbSO_{4}, as it also is by many oxidising agents (hydrogen peroxide, potassium nitrate). Lead sulphate is also insoluble in water,[43] and lead is but rarely met with in this form in nature. The chromates, vanadates, phosphates, and similar salts of lead are also somewhat rare. The carbonate, PbCO_{2}, is sometimes found in large masses, especially in the Altai region. Lead sulphide is often worked for extracting the silver which it contains; and as the lead itself also finds manifold industrial applications, this work is carried out on an exceedingly large scale. Many methods are employed. Sometimes the lead sulphide is decomposed by heating it with cast iron. The iron takes up the sulphur from the lead and forms easily-fusible iron sulphide, which does not mix with the heavier reduced lead. But another process is more frequently used: the lead ore (it must be clean; that is, free from earthy matter, which may be easily removed by washing) is heated in a reverberatory furnace to a moderate temperature with a free access of air. During this operation part of the lead sulphide oxidises and forms lead sulphate, PbSO_{4}, and lead oxide. When the oxidation of part of the lead has been attained, it is necessary to shut off the air supply and increase the temperature, then the oxidised compounds of the lead enter into reaction with the remaining lead sulphide, with formation of sulphurous anhydride and metallic lead. At first from PbS + O_{3}, PbO + SO_{2} are formed, and also from PbS + O_{4} lead sulphate PbSO_{4}, and then PbO and PbSO_{4} react with the remaining PbS, according to the equations 2PbO + PbS = 3Pb + SO_{2} and also PbSO_{4} + PbS = 2Pb + 2SO_{2}.[44] [42] Mixed ores of copper compounds together with PbS and ZnS are frequently found in the most ancient primary rocks. As the separation of the metals themselves is difficult, the ores are separated by a method of selection or mechanical sorting. Such mixed ores occur in Russia, in many parts of the Caucasus, and in the Donetz district (at Nagolchik). [42 bis] Lead sulphide in the presence of zinc and hydrochloric acid is completely reduced to metallic lead, all the sulphur being given off as hydrogen sulphide. [43] Lead sulphate, PbSO_{4}, occurs in nature (_anglesite_) in transparent brilliant crystals which are isomorphous with barium sulphate, and have a specific gravity of 6·3. The same salt is formed on mixing sulphuric acid or its soluble salts with solutions of lead salts, as a heavy white precipitate, which is insoluble in water and acids, but dissolves in a solution of ammonium tartrate in the presence of an excess of ammonia. This test serves to distinguish this salt from the similar salts of strontium and barium. [44] According to J. B. Hannay (1894) the last named decomposition (PbS + PbSO_{4} = 2Pb + 2SO_{2}) is really much more complicated, and in fact a portion of the PbS is dissolved in the Pb, forming a slag containing PbO, PbS and PbSO_{4}, whilst a portion of the lead volatilises with the SO_{2} in the form of a compound PbS_{2}O_{2}, which is also formed in other cases, but has not yet been thoroughly studied. Besides these methods for extracting lead from PBS in its ores, roasting (the removal of the S in the form of SO_{2}) and smelting with charcoal with a blast in the same manner as in the manufacture of pig iron (Chapter XXII.) are also employed. We may add that PbS in contact with Zn and hydrochloric acid (which has no action upon PbS alone) entirely decomposes, forming H_{2}S and metallic lead: PbS + Zn + 2HCl = Pb + ZnCl_{2} + H_{2}S. As lead is easily reduced from its ores, and the ore itself has a metallic appearance, it is not surprising that it was known to the ancients, and that its properties were familiar to the alchemists, who called it 'Saturn.' Hence metallic lead, reduced from its salts in solution by zinc, having the appearance of a tree-like mass of crystals, is called 'arbor saturni,' &c. The appearance of lead is well known; its specific gravity is 11·3; the bluish colour and well-marked metallic lustre of freshly-cut lead quickly disappear when exposed to the air, because it becomes coated with a layer--although a very thin layer--of oxide and salts formed by the moisture and acids in the atmosphere. It melts at 320°, and crystallises in octahedra on cooling. Its softness is apparent from the flexibility of lead pipes and sheets, and also from the fact that it may be cut with a knife, and also that it leaves a grey streak when rubbed on paper. On account of its being so soft, lead naturally cannot be applied in many cases where most metals may be used; but on the other hand it is a metal which is not easily changed by chemical reagents, and as it is capable of being soldered and drawn into sheets, &c., lead is most valuable for many technical uses. Lead pipes are used for conveying water[45] and many other liquids, and sheet lead is used for lining all kinds of vessels containing liquids--(acids, for instance) which act on other metals. This particularly refers to sulphuric and hydrochloric acids, because at a low temperature they do not act on lead, and if they form lead sulphate, PbSO_{4}, and chloride, PbCl_{2}, these salts being insoluble in water and in acids, cover the lead and protect it from further corrosion.[46] All soluble preparations of lead are poisonous. At a white heat lead may be partially distilled; the vapours oxidise and burn. Lead may also be easily oxidised at low temperatures. Lead only decomposes water at a white heat, and does not liberate hydrogen from acids, with the exception only of very strong hydrochloric acid and then only when boiling. Sulphuric acid diluted with water does not act on it, or only acts very feebly at the surface; but strong sulphuric acid, when heated, is decomposed by it, with the evolution of sulphurous anhydride. The best solvent for lead is nitric acid, which transforms it into a soluble salt, Pb(NO_{3})_{2}. [45] Freshly laid new lead pipes contaminate the water with a certain amount of lead salts, arising from the presence of oxygen, carbonic acid, &c., in the water. But the lead pipes under the action of running water soon become coated with a film of salts--lead sulphate, carbonate, chloride, &c.--which are insoluble in water, and the water pipes then become harmless. [46] Lead is used in the arts, and owing to its considerable density, it is cast, mixed with small quantities of other metals, into shot. A considerable amount is employed (together with mercury) in extracting gold and silver from poor ores, and in the manufacture of chemical reagents, and especially of lead chromate. _Lead chromate_, PbCrO_{4}, is distinguished for its brilliant yellow colour, owing to which it is employed in considerable quantities as a dye, mainly for dyeing cotton tissues yellow. It is formed on the tissue itself, by causing a soluble salt of lead to react on potassium chromate. Lead chromate is met with in nature as 'red lead ore.' It is insoluble in water and acetic acid, hut it dissolves in aqueous potash. The so-called pewter vessels often consist of an alloy of 5 parts of tin and 1 part of lead, and solder is composed of 1 to 2 parts of tin with 1/2 part of lead. Amongst the alloys of lead and tin, Rudberg states that the alloy PbSn_{3} stands out from the rest, since, according to his observations, the temperature of solidification of the alloy is 187°. Although acids thus have directly but little effect on lead, and this is one of its most important practical properties, _yet when air has free access, lead (like copper) very easily reacts with many acids_, even with those which are comparatively feeble. The action of acetic acid on lead is particularly striking and often applied in practice. If lead be plunged into acetic acid it does not change at all and does not pass into solution, but if part of the lead be immersed in the acid, and the other part remain in contact with the air, or if lead be merely covered with a thin layer of acetic acid in such a way that the air is practically in contact with the metal, then it unites with the oxygen of the air to form oxide, which combines with the acetic acid and forms lead acetate, soluble in water. The formation of lead oxide is especially marked from the fact that with a sufficient quantity of air not only is the normal lead acetate formed but also the basic salts.[47] [47] The normal lead acetate, known in trade as _sugar of lead_, owing to its having a sweetish taste, has the formula Pb(C_{2}H_{3}O_{2})_{2},3H_{2}O. This salt only crystallises from acid solutions. It is capable of dissolving a further quantity of lead oxide or of metallic lead in the presence of air. A basic salt of the composition Pb(C_{2}H_{3}O_{2})_{2},PbH_{2}O_{2} is then formed which is soluble in water and alcohol. As in this salt the number of atoms is even and the same as in the hydrate of acetic acid, C_{2}H_{4}O_{2},H_{2}O = C_{2}H_{3}(OH)_{3}, it may be represented as this hydrate in which two of hydrogen are replaced by lead--that is, as C_{2}H_{3}(OH)(O_{2}Pb). This basic salt is used in medicine as a remedy for inflammation, for bandaging wounds, &c., and also in the manufacture of white lead. Other basic acetates of lead, containing a still greater amount of lead oxide, are known. According to the above representation of the composition of the preceding lead acetate, a basic salt of the composition (C_{2}H_{3})_{2}(O_{2}Pb)_{3} would be also possible, but what appear to be still more basic salts are known. As the character of a salt also depends on the property of the base from which it is formed, it would seem that lead forms a hydroxide of the composition HOPbOH, containing two water residues, one or both of which may be replaced by the acid residues. If both water residues are replaced, a normal salt, XPbX, is obtained, whilst if only one is replaced a basic salt, XPbOH, is formed. But lead does not only give this normal hydroxide, but also polyhydroxides, Pb(OH),_n_PbO, and if we may imagine that in these polyhydroxides there is a substitution of both the water residues by acid residues, then the power of lead for forming basic salts is explained by the properties of the base which enters into their composition. When oxidising in the presence of air,[48] when heated or in the presence of an acid at the ordinary temperature, lead forms compounds of the type PbX_{2}. _Lead oxide_, PbO, known in industry as _litharge_, silberglätte (this name is due to the fact that silver is extracted from the lead ores of this kind) and massicot. If the lead is oxidised in air at a high temperature, the oxide which is formed fuses, and on cooling is easily obtained in fused masses which split up into scales of a yellowish colour, having a specific gravity of 9·3; in this form it bears the name of litharge. Litharge is principally used for making lead salts, for the extraction of metallic lead, and also for the preparation of drying oils--for instance, from linseed oil.[49] When oxidised carefully and slightly heated, lead forms a powdery (not fused) oxide known under the name of _massicot_. It is best prepared in the laboratory by heating lead nitrate, or lead hydroxide. It has a yellow colour, and differs from litharge in the greater difficulty with which it forms lead salts with acids. Thus, for instance, when massicot is moistened with water it does not attract the carbonic acid of the air so easily as litharge does. It may, however, be imagined that the cause of the difference depends only on the formation of dioxide on the surface of the lead oxide, on which the acids do not act. In any case lead oxide is comparatively easily soluble in nitric and acetic acids. It is but slightly soluble in water, but communicates an alkaline reaction to it, since it forms the hydroxide. This hydroxide is obtained in the shape of a white precipitate by the action of a small quantity of an alkali hydroxide on a solution of a lead salt. An excess of alkali dissolves the hydroxide separated, which fact demonstrates the comparatively indistinct basic properties of lead oxide. The normal lead hydroxide, which should have the composition Pb(OH)_{2}, is unknown in a separate state, but it is known in combination with lead oxide as Pb(OH)_{2},2PbO or Pb_{3}O_{2}(OH)_{2}. The latter is obtained in the form of brilliant, white, octahedral crystals when basic lead acetate is mixed with ammonia and gently heated. The basic qualities of this hydroxide are shown distinctly by its absorbing the carbonic anhydride of the air. When an alkaline solution of the hydroxide is boiled, it deposits lead oxide in the form of a crystalline powder. [48] Few compounds are known of the lower type PbX, and still fewer of the intermediate type PbX_{3}. To the first type belongs the so-called lead suboxide, Pb_{2}O, obtained by the ignition of lead oxalate, C_{2}PbO_{4}, without access of air. It is a black powder, which easily breaks up under the action of acids, and even by the simple action of heat, into metallic lead and lead oxide. This is the character of all suboxides. They cannot be regarded as independent salt-forming oxides, neither can those forms of oxidation of lead which contain more oxygen than the oxide of lead, PbO, and less than the dioxide, PbO_{2}. As we shall see, at least two such compounds are formed. Thus, for example, an oxide having the composition Pb_{2}O_{3} is known, but it is decomposed by the action of acids into lead oxide, which passes into solution, and lead dioxide, which remains behind. Such is red lead. (See further on.) [49] In the boiling of drying oils, the lead oxide partially passes into solution, forming a saponified compound capable of attracting oxygen and solidifying into a tar-like mass, which forms the oil paint. Perhaps, however, glycerine partially acts in the process. Ossovetsky by saturating drying oil with the salts of certain metals obtained oil colours of great durability. A mixture of very finely-divided litharge with glycerine (50 parts of litharge to 5 c.c. of anhydrous glycerine) forms a very quick (two minutes) setting cement, which is insoluble in water and oils, and is very useful in setting up chemical apparatus. The hardening is based on the reaction of the lead oxide with glycerine (Moraffsky). Lead oxide forms but few soluble salts--for instance, the nitrate and the acetate. The majority of its salts (sulphate, PbSO_{4}; carbonate, PbCO_{3}; iodide, PbI_{2}, &c.) are insoluble in water. These salts are colourless or light yellow if the acid be colourless. In lead oxide _the faculty of forming basic salts_, PbX_{2}_n_PbO or PbX_{2}_n_PbH_{2}O_{2}, is strongly developed. A similar property was observed in magnesium and also in the salts of mercury, but lead oxide forms basic salts with still greater facility, although double salts are in this case more rarely formed.[50] [50] It is very instructive to observe that lead not only easily forms basic salts, but also salts containing several acid groups. Thus, for example, lead carbonate occurs in nature and forms compounds with lead chloride and sulphate. The first compound, known as _corneous lead_, _phosgenite_, has the composition PbCO_{3},PbCl_{2}; it occurs in nature in bright cubical crystals, and is prepared artificially by simply boiling lead chloride with lead carbonate. A similar compound of normal salts, PbSO_{4},PbCO_{3}, occurs in nature as _lanarkite_ in monoclinic crystals. _Leadhillite_ contains PbSO_{4},3PbCO_{3}, and also occurs in yellowish, monoclinic, tabular crystals. We will turn our attention to these salts of lead, because it is very probable that their formation is allied to the formation of the basic salts, and the following considerations may lead to the explanation of the existence of both. In describing silica we carefully developed the conception of polymerisation, which it is _also indispensable to recognise in the composition of many other oxides_. Thus it may be supposed that PbO_{2} is a similar polymerised compound to SiO_{2}--_i.e._ that the composition of lead peroxide will be Pb_{_n_}O_{2_n_}, because lead methyl, PbMe_{4}, and lead ethyl, PbEt_{4}, are volatile compounds, whilst PbO_{2} is non-volatile, and is very like silica in this respect, and not in the least like carbonic anhydride. Still more should a polymeric structure, Pb_{_n_}O_{_n_}, be ascribed to lead oxide, since it differs as little from lead dioxide in its physical properties as carbonic oxide does from carbonic anhydride, and being an unsaturated compound is more likely to be capable of intercombination (polymerisation) than lead dioxide. These considerations respecting the complexity of lead oxide could have no real significance, and could not be accepted, were it not for the existence of the above-mentioned basic and mixed salts. The oxide apparently corresponds with the composition Pb_{_n_}X_{2_n_}, and since, according to this representation, the number of X's in the salts of lead is considerable, it is obvious that they may be diverse. When a part of these X's is replaced by the water residue (OH) or by oxygen, X_{2} = O, and the other parts by an _acid residue_, X, then basic salts are obtained, but if a part of the X's is replaced by acid residues of one kind, and the other part by acid residues of another kind, then those mixed salts about which we are now speaking are formed. Thus, for example, we may suppose, for a comparison of the composition of the majority of the salts of lead, that _n_ = 12, and then the above-mentioned compounds will present themselves in the following form:--Lead oxide, Pb_{12}O_{12}, its crystalline hydrate, Pb_{12}O_{8}(OH)_{8}, lead chloride, Pb_{12}Cl_{24}, lead oxychloride, Pb_{12}Cl_{12}O_{6}, the other oxychloride, Pb_{12}(OH)_{8}Cl_{6}O_{6}, mendipite (_see_ Note 51), Pb_{12}Cl_{8}O_{8}, normal lead carbonate, Pb_{12}(CO_{3})_{12}, crystalline basic salt, Pb_{12}(OH)_{6}(CO_{3})_{6}, white lead, Pb_{12}(CO_{3})_{8}(HO)_{8}, corneous lead, Pb_{12}Cl_{12}(CO_{3})_{6}, lanarkite, Pb_{12}(CO_{3})_{6}(SO_{4})_{6}, leadhillite, Pb_{12}(CO_{3})_{9}(SO_{4})_{3}, &c. The number 12 is only taken to avoid fractional quantities. Possibly the polymerisation is much higher than this. The theory of the polymerisation of oxides introduced by me in the first edition of this work (1869) is now beginning to be generally accepted. Amongst the soluble lead salts, that best known and most often applied in practical chemistry is _lead nitrate_, obtained directly by dissolving lead or its oxide in nitric acid. The normal salt, Pb(NO_{3})_{2}, crystallises in octahedra, dissolves in water, and has a specific gravity of 4·5. When a solution of this salt acts on white lead or is boiled with litharge, the basic salt, having a composition Pb(OH)(NO_{3}), is formed in crystalline needles, sparingly soluble in cold water but easily dissolved in hot water, and therefore in many respects resembling lead chloride. When the nitrate is heated, either lead oxide is obtained or else the oxide in combination with peroxide. _Lead chloride_, PbCl_{2}, is precipitated from the soluble salts of lead when a strong solution is treated with hydrochloric acid or a metallic chloride. It is soluble in considerable quantities in hot water, and therefore if the solutions be dilute or hot, the precipitation of lead chloride does not occur, and if a hot solution be cooled, the salt separates in brilliant prismatic crystals. It fuses when heated (like silver chloride), but is insoluble in ammonia. This salt is sometimes met with in nature, and when heated in air is capable of exchanging half its chlorine for oxygen, forming the basic salt or lead oxychloride, PbCl_{2}PbO, which may also be obtained by fusing PbCl_{2} and PbO together. The reaction of lead chloride with water vapour leads to the same conclusion, showing the feeble basic character of lead 2PbCl_{2} + H_{2}O = PbCl_{2},PbO + 2HCl. When ammonia is added to an aqueous solution of lead chloride a white precipitate is formed, which parts with water on being heated, and has the composition Pb(OH)Cl,PbO. This compound is also formed by the action of metallic chlorides on other soluble basic salts of lead.[51] [51] A similar basic salt having a white colour, and therefore used as a substitute for white lead, is also obtained by mixing a solution of basic lead acetate with a solution of lead chloride. Its formation is expressed by the equation: 2PbX(OH),PbO + PbCl_{2} = 2Pb(OH)Cl,PbO + PbX_{2}. Similar basic compounds of lead are met with in nature--for instance, _mendipite_, PbCl,2PbO, which appears in brilliant yellowish-white masses. The ignition of red lead with sal-ammoniac results in similar polybasic compounds of lead chloride, forming the _Cassel's_, or _mineral yellow_ of the composition PbCl_{2}_n_PbO. _Lead iodide_, PbI_{2}, is still less soluble than the chloride, and is therefore obtained by mixing potassium iodide with a solution of a lead salt. It separates as a yellow powder, which may be dissolved in boiling water, and on cooling separates in very brilliant crystalline scales of a golden yellow colour. The salts PbBr_{2}, PbF_{2}, Pb(CN)_{2}, Pb_{2}Fe(CN)_{6} are also insoluble in water, and form white precipitates. Lead carbonate, or _white lead_, is the most extensively used basic lead salt. It has the valuable property of 'covering,' which only to a certain extent appertains to lead sulphate and other white powdery substances used as pigments. This faculty of 'covering' consists in the fact that a small quantity of white lead mixed with oil spreads uniformly, and if such a mixture be spread over a surface (for instance, of wood or metal) the surface is quickly covered--that is, light does not penetrate through even a very thin layer of superposed white lead; thus, for example, the grain of the wood remains invisible.[52] White lead, or _basic lead carbonate_, after being dried at 120°, has a composition Pb(OH)_{2},2PbCO_{3}.[53] It may be obtained by adding a solution of sodium carbonate to a solution of one of the basic salts of lead--for instance, the basic acetate--and likewise by treating this latter with carbonic acid. For this purpose the solution of basic acetate is poured into the vessel _f_; it is prepared in the vat A, containing litharge, into which the pump P delivers the solution of the acetate, which remains after the action of carbonic anhydride on the basic salt. In A a basic salt is formed having a composition approaching to Pb_{4}(OH)_{6}(C_{2}H_{3}O_{2})_{2}; carbonic anhydride, 2CO_{2}, is passed through this solution and precipitates white lead, Pb_{2}(OH)_{2}(CO_{3})_{2}, and normal lead acetate, Pb(C_{2}H_{3}O_{2})_{2}, remains in the solution, and is pumped back into the vat A containing lead oxide, where the normal salt is again (on being agitated) converted into the basic salt. This is run into the vessel E, and thence into _f_. Into the latter carbonic anhydride is delivered from the generator D, and forms a precipitate of white lead.[53 bis] [52] It is remarkable that a peculiar kind of attraction exists between boiled linseed oil and white lead, as is seen from the following experiments. White lead is triturated in water. Although it is heavier than water, it remains in suspension in it for some time and is thoroughly moistened by it, so that the trituration may be made perfect; boiled linseed oil is then added, and shaken up with it. A mixture of the oil and white lead is then found to settle at the bottom of the vessel. Although the oil is much lighter than the water it does not float on the top, but is retained by the white lead and sinks under the water together with it. There is not, however, any more perfect combination nor even any solution. If the resultant mass be then treated with ether or any other liquid capable of dissolving the oil, the latter passes into solution and leaves the white lead unaltered. [53] It may be regarded as a salt corresponding with the normal hydrate of carbonic acid, C(OH)_{4}, in which three-quarters of the hydrogen is replaced by lead. A salt is also known in which all the hydrogen of this hydrate of carbonic acid is replaced by lead--namely, the salt containing CO_{4}Pb_{2}. This salt is obtained as a white crystalline substance by the action of water and carbonic acid on lead. The normal salt, PbCO_{3}, occurs in nature under the name of white lead ore (sp. gr. 6·47), in crystals, isomorphous with aragonite, and is formed by the double decomposition of lead nitrate with sodium carbonate, as a heavy white precipitate. Thus both these salts resemble white lead, but the first-named salt is exclusively used in practice, owing to its being very conveniently prepared, and being characterised by its great covering capacity, or 'body,' due to its fine state of division. [53 bis] One of the many methods by which white lead is prepared consists in mixing massicot with acetic acid or sugar of lead, and leaving the mixture exposed to air (and re-mixing from time to time), containing carbonic acid, which is absorbed from the surface by the basic salt formed. After repeated mixings (with the addition of water), the entire mass is converted into white lead, which is thus obtained very finely divided. [Illustration: FIG. 82.--Manufacture of white lead.] In order to mark the transition from lead oxide, PbO, into lead dioxide PbO_{2} (plumbic anhydride), it is necessary to direct our attention to the intermediate oxide, or _red lead_, Pb_{3}O_{4}.[54] In the arts it is used in considerable quantities, because it forms a very durable yellowish-red paint used for colouring the resins (shellac, colophony, &c.) composing sealing wax. It also forms a very good cheap oil paint, used especially for painting metals, more particularly because drying oils--for instance, hemp seed, linseed oils--very quickly dry with red lead and with lead salts. Red lead is prepared by slightly heating massicot, for which purpose two-storied stoves are used. In the lower story the lead is turned into massicot, and in the higher one, having the lower temperature (about 300°), the massicot is transformed into red lead. Frémy and others showed the instability of red lead prepared by various methods, and its decomposition by acids, with formation of lead dioxide, which is insoluble in acids, and a solution of the salts of lead oxide. The artificial production (synthesis) of red lead by double decomposition was most important. For this purpose Frémy mixed an alkaline solution of potassium plumbate, K_{2}PbO_{3} (prepared by dissolving the dioxide in fused potash),[54 bis] with an alkaline solution of lead oxide. In this way a yellow precipitate of minium hydrate is formed, which, when slightly heated, loses water and turns into bright red anhydrous minium Pb_{3}O_{4}. [54] If lead hydroxide be dissolved in potash and sodium hypochlorite be added to the solution, the oxygen of the latter acts on the dissolved lead oxide, and partially converts it into dioxide, so that the so-called lead sesquioxide is obtained; its empirical formula is Pb_{2}O_{3}. Probably it is nothing but a lead salt--_i.e._ is referable to the type of dioxide of lead, or its hydroxide, PbO(OH)_{2}, in which two atoms of hydrogen are replaced by lead, PbO(O_{2}Pb). The brown compound precipitated by the action of dilute acids--for example, nitric--splits up, even at the ordinary temperature, into insoluble lead dioxide and a solution of a lead salt. This compound evolves oxygen when it is heated. It dissolves in hydrochloric acid, forming a yellow liquid, which probably contains compounds of the composition PbCl_{2} and PbCl_{4}, but even at the ordinary temperature the latter soon loses the excess of chlorine, and then only lead chloride, PbCl_{2}, remains. In order to see the relation between red lead and lead sesquioxide, it must be observed that they only differ by an extra quantity of lead oxide--that is, red lead is a basic salt of the preceding compound, and if the compound Pb_{2}O_{3} may be regarded as PbO_{3}Pb, then red lead should be looked on as PbO_{3}Pb,PbO--that is, as basic lead plumbate. [54 bis] Frémy obtained potassium plumbate in the following manner. Pure lead dioxide is placed in a silver crucible, and a strong solution of pure caustic potash is poured over it. The mixture is heated and small quantities are removed from time to time for testing, which consists in dissolving in a small quantity of water and decomposing the resultant solution with nitric acid. There is a certain moment during the heating when a considerable amount of insoluble lead dioxide is precipitated on the addition of the nitric acid; the solution then contains the salt in question, and the heating must be stopped, and a small amount of water added to dissolve the potassium plumbate formed. On cooling the salt separates in somewhat large crystals, which have the same composition as the stannate--that is, PbO(KO)_{2},3H_{2}O. Minium is the first and most ordinary means of producing _lead dioxide_, or plumbic anhydride, PbO_{2},[55] because when red lead is treated with dilute nitric acid it gives up lead oxide, and PbO_{2} remains, on which dilute nitric acid does not act. The composition of minium is Pb_{3}O_{4}, and therefore the action of nitric acid on it is expressed by the equation: Pb_{3}O_{4} + 4HNO_{3} = PbO_{2} + 2Pb(NO_{3})_{2} + 2H_{2}O. The dioxide may also be obtained by treating lead hydroxide suspended in water with a stream of chlorine. Under these conditions the chlorine takes up the hydrogen from the water, and the oxygen passes over to the lead oxide.[56] When a strong solution of lead nitrate is decomposed by the electric current, the appearance of crystalline lead dioxide is also observed upon the positive pole; it is also found in nature in the form of a black crystalline substance having a specific gravity of 9·4. When artificially produced it is a fine dark powder, resisting the action of acids, but nevertheless when treated with strong sulphuric acid it evolves oxygen and forms lead sulphate, and with hydrochloric acid it evolves chlorine. The oxidising property of lead dioxide depends of course on the facility of its transition into the more stable lead oxide, which is easily understood from the whole history of lead compounds. In the presence of alkalis it transforms chromium oxide into chromic acid, whilst lead chromate, PbCrO_{4}, is formed, remaining, however, in solution, on account of its being soluble in caustic alkalis. The oxidising action of lead dioxide on sulphurous anhydride is most striking, as it immediately absorbs it, with formation of lead sulphate. This is accompanied by a change of colour and development of heat, PbO_{2} + SO_{2} = PbSO_{4}. When triturated with sulphur the mixture explodes, the sulphur burning at the expense of the oxygen of the lead dioxide. _Tetrachloride of lead_, PbCl_{4}, belongs to the same class of lead compounds as PbO_{2}. This chloride is formed by the action of strong hydrochloric acid upon PbO_{2}, or, in the cold, by passing a stream of chlorine through water containing PbCl_{2} in suspension. The resultant yellow solution gives off chlorine when heated. With a solution of sal ammoniac (Nicolukin, 1885) it gives a precipitate of a double salt, (NH_{4})_{2}PbCl_{6} (very slightly soluble in a solution of sal ammoniac), which when treated with strong sulphuric acid (Friedrich, 1890) gives PbCl_{4} as a yellow liquid sp. gr. 3·18, which solidifies at -18°, and when heated gives PbCl_{2} + Cl_{2}. It is not acted upon by H_{2}SO_{4} like SnCl_{4}. Tetrafluoride of lead (Brauner) belongs to the same class of compounds, it easily forms double salts and decomposes with the evolution of fluorine (Chapter II., Note 49 bis).[56 bis] [55] Lead dioxide is often called lead peroxide, but this name leads to error, because PbO_{2} does not show the properties of true peroxides, like hydrogen or barium peroxides, but is endowed with acid properties--that is, it is able to form true salts with bases, which is not the case with true peroxides. Lead dioxide is a normal salt-forming compound of lead, as Bi_{2}O_{5} is for bismuth, CeO_{2} for cerium, and TeO_{3} for tellurium, &c. They all evolve chlorine when treated with hydrochloric acid, whilst true peroxides form hydrogen peroxide. The true lead peroxide, if it were obtained, would probably have the composition Pb_{2}O_{5}, or, in combination with peroxide of hydrogen, H_{2}Pb_{2}O_{7} = H_{2}O_{2} + Pb_{2}O_{5}, judging from the peroxides corresponding with sulphuric, chromic, and other acids, which we shall afterwards consider. As a proof of the fact, that the form PbO_{2}, or PbX_{4}, is the highest normal form of any combination of lead, it is most important to remark that it might be expected that the action of lead chloride, PbCl_{2}, on zinc-ethyl, ZnEt_{2}, would result in the formation of zinc chloride, ZnCl_{2}, and lead-ethyl, PbEt_{2}, but that in reality the reaction proceeds otherwise. Half of the lead is set free, and lead tetrethyl, PbEt_{4}, is formed as a colourless liquid, boiling at about 200° (Butleroff, Frankland, Buckton, Cahours, and others). The type PbX_{4} is not only expressed in PbEt_{4} and PbO_{2}, but also in PbF_{4}, obtained by Brauner. [56] According to Carnelley and Walker, the hydrate (PbO_{2})_{3},H_{2}O is then formed; it loses water at 230°. The anhydrous dioxide remains unchanged up to 280°, and is then converted into the sesquioxide, Pb_{2}O_{3}, which again loses oxygen at about 400°, and forms red lead, Pb_{3}O_{4}. Red lead also loses oxygen at about 550°, forming lead oxide, PbO, which fuses without change at about 600°, and remains constant as far as the limit of the observations made (about 800°). The best method for preparing pure lead dioxide consists in mixing a hot solution of lead chloride with a solution of bleaching powder (Fehrman). [56 bis] The plumbates of Ca and other similar metals, mentioned in Chapter III., Note 7, also belong to the form PbX_{4}. Amongst the elements of the second and third groups it was observed that the elements were more basic in the even than in the uneven series. It is sufficient to remember calcium, strontium, and barium in the even, and magnesium, zinc, and cadmium in the uneven series. In addition to this, in the even series, as the atomic weight increases, in the same type of oxidation the basic properties increase (the acid properties decrease); for example, in the second group, calcium, strontium, barium. The same also appears in the fourth and all the following groups. In the even series of the fourth group titanium, zirconium, cerium, and thorium are found. All their highest oxides, RO_{2}, even the lightest, titanic oxide, TiO_{2}, have more highly developed basic properties than silica, SiO_{2}, and in addition to this the basic properties are more distinctly seen in zirconium dioxide, ZrO_{2}, than in titanic oxide, TiO_{2}, although the acid property of combining with bases still remains. In the heaviest oxides, cerium dioxide, CeO_{2}, and thorium dioxide, ThO_{2}, no acid properties are observed, these being both purely basic oxides. In Chapter XVII. (Note 43) we already pointed out this higher oxide of cerium. As the above-mentioned elements are rather rare in nature, have but little practical application, and do not present any new forms of combination, it is unadvisable to dwell on them in this treatise. _Titanium_ is found in nature in the form of its anhydride or oxide, TiO_{2}, mixed with silicon in many minerals, but the oxide is also found separately in the form of semi-metallic _rutile_ (sp. gr. 4·2). Another titanic mineral is found as a mixture in other ores, known as _titanic iron ore_ (in the Thuensky mountains of the southern Ural; it is known as _thuenite_), FeTiO_{3}. This is a salt of ferrous oxide and titanic anhydride. It crystallises in the rhombohedric system, has a metallic lustre, grey colour, sp. gr. 4·5. The third mineral in which titanium is found in considerable quantities in nature is _sphene_ or _titanite_, CaTiSiO_{5} = CaO,SiO_{2},TiO_{2}, sp. gr. 3·5, colour yellow, green, or the like, crystallises in tablets. The fourth, but rare, titanic mineral is _peroffskite_, calcium titanate, CaTiO_{3}; it forms blackish-grey or brown cubic crystals, sp. gr. 4·02, and occurs in the Ural and other localities. It may be prepared artificially by fusing sphene in an atmosphere of water vapour and carbonic anhydride. At the end of the last century Klaproth showed the distinction between titanic compounds and all others then known.[57] [57] The compounds of titanium are generally obtained from rutile; the finely-ground ore is fused with a considerable amount of acid potassium sulphate, until the titanic anhydride, as a feeble base, passes into solution. After cooling, the resultant mass is ground up, dissolved in cold water, and treated with ammonium hydrosulphide; a black precipitate then separates out from the solution. This precipitate contains TiO_{2} (as hydrate) and various metallic sulphides--for example, iron sulphide. It is first washed with water and then with a solution of sulphurous anhydride until it becomes colourless. This is due to the iron sulphide contained in the precipitate, and rendering it black, being converted into dithionate by the action of the sulphurous acid. The titanic acid left behind is nearly pure. The considerable volatility of titanium chloride may also be taken advantage of in preparing the compounds of titanium from rutile. It is formed by heating a mixture of rutile and charcoal in dry chlorine; the distillate then contains _titanium chloride_, TiCl_{4}. It may be easily purified, owing to its having a constant boiling point of 136°. Its specific gravity is 1·76; it is a colourless liquid, which fumes in the air, and is perfectly soluble in water if it be not heated. When hot water acts on titanic chloride, a large proportion of titanic acid separates out from the solution and passes into metatitanic acid. A similar decomposition of acid solutions of titanic acid is accomplished whenever they are heated, and especially in the presence of sulphuric acid, just as with metastannic acid, which titanic acid resembles in many respects. On igniting the titanic acid a colourless powder of the anhydride, TiO_{2}, is obtained. In this form it is no longer soluble in acids or alkalis, and only fuses in the oxyhydrogen flame; but, like silica, it dissolves when fused with alkalis and their carbonates; as already mentioned, it dissolves when fused with a considerable excess of acid potassium sulphate--that is, it then reacts as a feeble base. This shows the basic character of titanic anhydride; it has at once, although feebly developed, both basic and acid properties. The fused mass, obtained from titanic anhydride and alkali when treated with water, parts with its alkali, and a residue is obtained of a sparingly-soluble poly-titanate, K_{2}TiO_{3}_n_TiO_{2}. The hydrate, which is precipitated by ammonia from the solutions obtained by the fusion of TiO_{2} with acid potassium sulphate, when dried forms an amorphous mass of the composition Ti(OH)_{4}. But it loses water over sulphuric acid, gradually passing into a hydrate of the composition TiO(OH)_{2}, and when heated it parts with a still larger proportion of water; at 100° the hydrate Ti_{2}O_{3}(OH)_{2} is obtained, and at 300° the anhydride itself. The higher hydrate, Ti(OH)_{4}, is soluble in dilute acid, and the solution may be diluted with water; but on boiling the sulphuric acid solution (though not the solution in hydrochloric acid), all the titanic acid separates in a modified form, which is, however, not only insoluble in dilute acids, but even in strong sulphuric acid. This hydrate has the composition Ti_{2}O_{3}(OH)_{2}, but shows different properties from those of the hydrate of the same composition described above, and therefore this modified hydrate is called _metatitanic acid_. It is most important to note the property of the ordinary gelatinous hydrate (that precipitated from acid solutions by ammonia) of dissolving in acids, the more so since silica does not show this property. In this property a transition apparently appears between the cases of common solution (based on a capacity for unstable combination) and the case of the formation of a hydrosol (the solubility of germanium oxide, GeO_{2}, perhaps presents another such instance). If titanium chloride be added drop by drop to a dilute solution of alcohol and hydrogen peroxide, and then ammonia be added to the resultant solution, a yellow precipitate of _titanium trioxide_, TiO_{3}H_{2}O, separates out, as Piccini, Weller, and Classen showed. This substance apparently belongs to the category of true peroxides. Titanium chloride absorbs ammonia and forms a compound, TiCl_{4},4NH_{3}, as a red-brown powder which attracts moisture from the air and when ignited forms _titanium nitride_, Ti_{3}N_{4}. Phosphuretted hydrogen, hydrocyanic acid, and many similar compounds are also absorbed by titanium chloride, with the evolution of a considerable amount of heat. Thus, for example, a yellow crystalline powder of the composition TiCl_{4},2HCN is obtained by passing dry hydrocyanic acid vapour into cold titanium chloride. Titanium chloride combines in a similar manner with cyanogen chloride, phosphorus pentachloride, and phosphorus oxychloride, forming molecular compounds, for example TiCl_{4},POCl_{3}. This faculty for further combination probably stands in connection, on the one hand, with the capacity of titanium oxide to give polytitanates, TiO(MO)_{2},_n_TiO_{2}; on the other hand, it corresponds with the kindred faculty of stannic chloride for the formation of poly-compounds (Note 41), and lastly it is probably related to the remarkable behaviour of titanium towards nitrogen. Metallic titanium, obtained as a grey powder by reducing potassium titanofluoride, K_{2}TiF_{6}, (sp. gr. 3·55 K. Hofman 1893), with iron in a charcoal crucible, combines directly with nitrogen at a red heat. If titanic anhydride be ignited in a stream of ammonia, all the oxygen of the titanic oxide is disengaged, and the compound TiN_{2} is formed as a dark violet substance having a copper-red lustre. A compound Ti_{5}N_{6} is also known; it is obtained by igniting the compound Ti_{3}N_{4} in a stream of hydrogen, and is of a golden-yellow colour with a metallic lustre. To this order of compounds also belongs the well-known and chemically historical compound known as _titanium nitrocyanide_; its composition is Ti_{5}CN_{4}. This substance appears as infusible, sometimes well-formed, cubical crystals of sp. gr, 4·3, and having a red copper colour and metallic lustre; it is found in blast furnace slag. It is insoluble in acids but is acted on by chlorine at a red heat, forming titanium chloride. It was at first regarded as metallic titanium; it is formed in the blast furnace at the expense of those cyanogen compounds (potassium cyanide and others) which are always present, and at the expense of the titanium compounds which accompany the ores of iron. Wöhler, who investigated this compound, obtained it artificially by heating a mixture of titanic oxide with a small quantity of charcoal, in a stream of nitrogen, and thus proved the direct power for combination between nitrogen and titanium. When fused with caustic potash, all the nitrogen compounds of titanium evolve ammonia and form potassium titanate. Like metals they are able to reduce many oxides--for example, oxides of copper--at a red heat. Among the alloys of titanium, the crystalline compound Al_{4}Ti is remarkable. It is obtained by directly dissolving titanium in fused aluminium; its specific gravity is 3·11. The crystals are very stable, and are only soluble in aqua regia and alkalis. The comparatively rare element _zirconium_, Zr = 90, is very similar to titanium, but has a more basic character. It is rarer in nature than titanium, and is found principally in a mineral called _zircon_, ZrSiO_{4} = ZrO_{2}.SiO_{2}, crystallising in square prisms, sp. gr. 4·5. It has considerable hardness and a characteristic brownish-yellow colour, and is occasionally found in the form of transparent crystals, as a precious stone called hyacinth.[58] Metallic zirconium was obtained, by Berzelius and Troost, by the action of aluminium on potassium zirconofluoride in the same way that silicon is prepared; it forms a crystalline powder, similar in appearance to graphite and antimony, but having a very considerable hardness, not much lustre, sp. gr. 4·15. In many respects it resembles silicon; it does not fuse when heated, and even oxidises with difficulty, but liberates hydrogen when fused with potash. When fused with silica it liberates silicon. With carbon in the electrical furnace it forms ZrC_{2}, with hydrogen it gives ZrH_{2} (like CaH_{2}, Winkler, Vol. I., p. 621); hydrochloric and nitric acids act feebly on it, but aqua regia easily dissolves it. It is distinguished from silicon by the fact that hydrofluoric acid acts on it with great facility, even in the cold and when diluted, whilst this acid does not act on silicon at all. [58] The formula ZrO was first given to the oxide of zirconium as a base, in this case Zr = 45 whilst the present atomic weight is Zr = 90--that is, the formula of the oxide is now recognised as being ZrO_{2}. The reasons for ascribing this formula to the compounds of zirconium are as follows. In the first place, the investigation of the crystalline forms of the zirconofluorides--for example, K_{2}ZrF_{6}, MgZrF_{6},5H_{2}O--which proved to be analogous in composition and crystalline form with the corresponding compounds of titanium, tin, and silicon. In the second place, the specific heat of Zr is 0·067, which corresponds with the combining weight 90. The third and most important reason for doubling the combining weight of zirconium was given by Deville's determination of the vapour density of _zirconium chloride_, ZrCl_{4}. This substance is obtained by igniting zirconium oxide mixed with charcoal in a stream of dry chlorine, and is a colourless, saline substance which is easily volatile at 440°. Its density referred to air was found to be 8·15, that is 117 in relation to hydrogen, as it should be according to the molecular formula of this substance above-cited. It exhibits, however, in many respects, a saline character and that of an acid chloranhydride, for zirconium oxide itself presents very feebly developed acid properties but clearly marked basic properties. Thus zirconium chloride dissolves in water, and on evaporation the solution only partially disengages hydrochloric acid--resembling magnesium chloride, for example. Zirconium was discovered and characterised as an individual element by Klaproth. Pure compounds of zirconium are generally prepared from zircon, which is finely ground, but as it is very hard it is first heated and thrown into cold water, by which means it is disintegrated. Zircon is decomposed or dissolved when fused with acid potassium sulphate, or still more easily when fused with acid potassium fluoride (a double soluble salt, K_{2}ZrF_{6}, is then formed); however, zirconium compounds are generally prepared from powdered zircon by fusing it with sodium carbonate and then boiling in water. An insoluble white residue is obtained consisting of a compound of the oxides of sodium and zirconium, which is then treated with hydrochloric acid and the solution evaporated to dryness. The silica is thus converted into an insoluble form, and zirconium chloride obtained in solution. Ammonia precipitates _zirconium hydroxide_ from this solution, as a white gelatinous precipitate, ZrO(OH)_{2}. When ignited this hydroxide loses water and in so doing undergoes a spontaneous recalescence and leaves a white infusible and exceedingly hard mass of _zirconium oxide_, ZrO_{2}, having a specific gravity of 5·4 (in the electrical furnace ZrO_{2} fuses and volatilises like SiO_{2}, Moissan). Owing to its infusibility, zirconium oxide is used as a substitute for lime and magnesia in the Drummond light. This oxide, in contradistinction to titanium oxide, is soluble, even after prolonged ignition, in hot strong sulphuric acid. The hydroxide is easily soluble in acids. The composition of the salts is ZrX_{4}, or ZrOX_{2}, or ZrOX_{2},ZrO_{2}, just as with those of its analogues. But although zirconium oxide forms salts in the same way with acids, it also gives salts with bases. Thus it liberates carbonic anhydride when fused with sodium carbonate, forming the salts Zr(NaO)_{4}, ZrO(NaO)_{2}, &c. Water, however, destroys these salts and extracts the soda. The very similar element _thorium_ (Th = 232) was distinguished by Berzelius from zirconium. It is very rarely met with, in _thorite_ and _orangeite_, ThSiO_{4},2H_{2}O. The latter is isomorphous with zircon (sp. gr. 4·8).[59] [59] Thorium has also been found in the form of oxide in certain pyrochlores, euxenites, monazites, and other rare minerals containing salts of niobium and phosphates. The compounds of thorium are prepared by decomposing thorite or orangeite with strong sulphuric acid at its boiling point; this renders the silica insoluble, and the thorium oxide passes into solution when the residue is treated with cold water, after having been previously boiled with water (boiling water does not dissolve the oxide of thorium). Lead and other impurities are separated by passing sulphuretted hydrogen through the solution, and the thorium hydroxide is then precipitated by ammonia. If this hydroxide be dissolved in the smallest possible amount of hydrochloric acid, and oxalic acid be then added, thorium oxalate is obtained as a white precipitate, which is insoluble in an excess of oxalic acid; this reaction is taken advantage of for separating this metal from many others. It, however, resembles the cerite metals (Chapter XVII., Note 43) in this and many other respects. The thorium hydroxide is gelatinous; on ignition it leaves an infusible oxide, ThO_{2}, which, when fused with borax, gives crystals of the same form as stannic oxide or titanic anhydride; sp. gr. 9·86. But the basic properties are much more developed in thorium oxide than in the preceding oxides, and it does not even disengage carbonic acid when fused with sodium carbonate--that is, it is a much more energetic base than zirconium oxide. The hydrate, ThO_{2}, however, is soluble in a solution of Na_{2}CO_{3} (Chapter XVII., Note 43). Thorium chloride, ThCl_{4} is obtained as a distinctly crystalline sublimate when thorium oxide, mixed with charcoal, is ignited in a stream of dry chlorine. When heated with potassium, thorium chloride gives a metallic powder of thorium having a sp. gr. 11·1. It burns in air, and is but slightly soluble in dilute acids. The atomic weight of thorium was established by Chydenius and Delafontaine on the basis of the ismorphism of the double fluorides. CHAPTER XIX PHOSPHORUS AND THE OTHER ELEMENTS OF THE FIFTH GROUP Nitrogen is the lightest and most widely distributed representative of the elements of the fifth group, which form a higher saline oxide of the form R_{2}O_{5}, and a hydrogen compound of the form RH_{3}. Phosphorus, arsenic, bismuth, and antimony belong to the uneven series of this group. _Phosphorus_ is the most widely distributed of these elements. There is hardly any mineral substance composing the mass of the earth's crust which does not contain some--it may be a small--amount of phosphorus compounds in the form of the salts of phosphoric acid. The soil and earthy substances in general usually contain from one to ten parts of phosphoric acid in 10,000 parts. This amount, which appears so small, has, however, a very important significance in nature. No plant can attain its natural growth if it be planted in an artificial soil completely free from phosphoric acid. Plants equally require the presence of potash, magnesia, lime, and ferric oxide, among basic, and of carbonic, sulphuric, nitric, and phosphoric anhydrides, among acid oxides. In order to increase the fertility of a more or less poor soil, the above-named nutritive elements are introduced into it by means of fertilisers. Direct experiment has proved that these substances are undoubtedly necessary to plants, but that they must be all present simultaneously and in small quantities, and that an excess, like an insufficiency, of one of these elements is necessarily followed by a bad harvest, or an imperfect growth, even if all the other conditions (light, heat, water, air) are normal. The phosphoric compounds of the soil accumulated by plants pass into the organism of animals, in which these substances are assimilated in many instances in large quantities. Thus the chief component part of bones is calcium phosphate, Ca_{3}P_{2}O_{8}, and it is on this that their hardness depends.[1] [1] Dry bones contain about one-third of gelatinous matter and about two-thirds of ash, chiefly calcium phosphate. The salts of phosphoric acid are also found in the mass of the earth as separate minerals; for example, the _apatites_ contain this salt in a crystalline form, combined with calcium chloride or fluoride, CaR_{2},3Ca_{3}(PO_{4})_{2}, where R = F or Cl, sometimes in a state of isomorphous mixture. This mineral often crystallises in fine hexagonal prisms; sp. gr. 3·17 to 3·22. Vivianite is a hydrated ferrous phosphate, Fe_{3}(PO_{4})_{2},8H_{2}O. Phosphates of copper are frequently found in copper mines; for example, _tagilite_, Cu_{3}(PO_{4})_{2},Cu(OH)_{2},2H_{2}O. Lead and aluminium form similar salts. They are nearly all insoluble in water. The turquoise, for instance, is hydrated phosphate of alumina, (Al_{2}O_{3})_{2},P_{2}O_{5}5H_{2}O, coloured with a salt of copper. Sea and other waters always contain a small amount of phosphates. The ash of sea-plants, as well as of land-plants, always contains phosphates. Deposits of calcium phosphate are often met with; they are termed _phosphorites_ and _osteolites_, and are composed of the fossil remains of the bones of animals; they are used for manure. Of the same nature are the so-called guano deposits from Baker's Island, and entire strata in Spain, France, and in the Governments of Orloff and Kursk in Russia. It is evident that if a soil destined for cultivation contain very little phosphoric acid, the fertilisation by means of these minerals will be beneficial, but, naturally, only if the other elements necessary to plants be present in the soil. Phosphorus was first extracted by Brand in 1669, by the ignition of evaporated urine. After the lapse of a century Scheele, who knew of the existence of a more abundant source of phosphorus in bones, pointed out the method which is now employed for the extraction of this element. Calcium phosphate in bones permeates a nitrogenous organic substance, which is called ossein, and forms a gelatin. When bones are treated exclusively for the extraction of phosphorus, neglecting the gelatin, they are burnt, in which case all the ossein is burnt away. When, however, it is desired to preserve the gelatin, the bones are immersed in cold dilute hydrochloric acid, which dissolves the calcium phosphate and leaves the gelatin untouched; calcium chloride and acid calcium phosphate, CaH_{4}(PO_{4})_{2}, are then obtained in the solution. When the bones are directly burnt in an open fire their mineral components only are left as an ash, containing about 90 per cent. of calcium phosphate, Ca_{3}(PO_{4})_{2}, mixed with a small amount of calcium carbonate and other salts. This mass is treated with sulphuric acid, and then the same substance is obtained in the solution as was obtained from the unburnt bones immersed in hydrochloric acid--_i.e._ the acid calcium phosphate soluble in water, in which reaction naturally the chief part of the sulphuric acid is converted into calcium sulphate: Ca_{3}(PO_{4})_{2} + 2H_{2}SO_{4} = 2CaSO_{4} + CaH_{4}(PO_{4})_{2}. Ca_{3}(PO_{4})_{2} + 4HCl = 2CaCl_{2} + CaH_{4}(PO_{4})_{2}. On evaporating the solution, crystallisable acid calcium phosphate is obtained. The extraction of the phosphorus from this salt consists in _heating it with charcoal to a white heat_. When heated, the acid phosphate, CaH_{4}(PO_{4})_{2}, first parts with water, and forms the metaphosphate, Ca(PO_{3})_{2}, which for the sake of simplicity may be regarded, like the acid salt, as composed of pyrophosphate and phosphoric anhydride, 2Ca(PO_{3})_{2} = Ca_{2}P_{2}O_{7} + P_{2}O_{5}. The latter, with charcoal, gives phosphorus and carbonic oxide, P_{2}O_{5} + 5C = P_{2} + 5CO. So that in reality a somewhat complicated process takes place here, yielding ultimately products according to the following equation: 2CaH_{4}(PO_{4})_{2} + 5C = 4H_{2}O + Ca_{2}P_{2}O_{7} + P_{2} + 5CO. After the steam has come over, phosphorus and carbonic oxide distil over from the retort and calcium pyrophosphate remains behind.[1 bis] [1 bis] By subjecting the pyrophosphate to the action of sulphuric or hydrochloric acid it is possible to obtain a fresh quantity of the acid salt from the residue, and in this manner to extract all the phosphorus. It is usual to take burnt bones, but mineral phosphorites, osteolites, and apatites may also be employed as materials for the extraction of phosphorus. Its extraction for the manufacture of matches is everywhere extending, and in Russia, in the Urals, in the Government of Perm, it has attained such proportions that the district is able to supply other countries with phosphorus. A great many methods have been proposed for facilitating the extraction of phosphorus, but none of them differ essentially from the usual one, because the problem is dependent on the liberation of phosphoric acid by the action of acids, and on its ultimate reduction by charcoal. Thus the calcium phosphate may be mixed directly with charcoal and sand, and phosphorus will be liberated on heating the mixture, because the silica displaces the phosphoric anhydride, which gives carbonic oxide and phosphorus with the charcoal. It has also been proposed to pass hydrochloric acid over an incandescent mixture of calcium phosphate and charcoal; the acid then acts just as the silica does, liberating phosphoric anhydride, which is reduced by the charcoal. It is necessary to prevent the access of air in the condensation of the vapours of phosphorus, because they take fire very easily; hence they are condensed under water by causing the gaseous products to pass through a vessel full of water. For this purpose the condenser shown in fig. 83 is usually employed. [Illustration: FIG. 83.--Preparation of phosphorus. The mixture is calcined in the retort _c_. The vapours of phosphorus pass through _a_ into water without coming into contact with air. The phosphorus condenses in the water, and the gases accompanying it escape through _i_.] As phosphorus melts at about 40°, it condenses at the bottom of the receiver in a molten liquid mass, which is cast under water in tubes, and is sold in the form of sticks. This is common or _yellow phosphorus_. It is a transparent, yellowish, waxy substance, which is not brittle, almost insoluble in water, and easily undergoes change in its external appearance and properties under the action of light, heat, and of various substances. It crystallises (by sublimation or from its solution in carbon bisulphide) in the regular system, and[2] (in contradistinction to the other varieties) is easily soluble in carbon bisulphide, and also partially in other oily liquids. In this it recalls common sulphur. Its specific gravity is 1·84. It fuses at 44°, and passes into vapour at 290°; it is easily inflammable, and must therefore be handled with great caution; careless rubbing is enough to cause phosphorus to ignite. Its application in the manufacture of matches is based on this.[2 bis] It emits light in the air owing to its slow[3] oxidation, and is therefore kept under water (such water is phosphorescent in the dark, like phosphorus itself). It is also very easily oxidised by various oxidising agents and takes up the oxygen from many substances.[3 bis] Phosphorus enters into direct combination with many metals and with sulphur, chlorine, &c., with development of a considerable amount of heat. It is very poisonous although not soluble in water. [2] Vernon (1891) observed that ordinary (yellow) phosphorus is dimorphous. If it be melted and by careful cooling be brought in a liquid form to as low a temperature as possible, it gives a variety which melts at 45°·3 (the ordinary variety fuses at 44°·3), sp. gr. 1·827 (that of the ordinary variety is 1·818) at 13°, crystallises in rhombic prisms (instead of in forms belonging to the cubical system). This is similar to the relation between octahedral and prismatic sulphur (Chapter XX.). [2 bis] According to Herr Irinyi (an Hungarian student), the first phosphorus matches were made in Austria at Roemer's works in 1835. [3] The absorption of the oxygen of the atmosphere at a constant ordinary temperature by a large surface of phosphorus proceeds so uniformly, regularly, and rapidly, that it may serve, as Ikeda (Tokio, 1893) has shown, for demonstrating the law of the velocity (rate) of reaction, which is considered in theoretical chemistry, and shows that the rate of reaction is proportional to the active mass of a substance--_i.e._ _dx_/_dt_ = _k_(A - _x_) where _t_ is the time, A the initial mass of the reacting substance--in this case oxygen--_x_ the amount of it which has entered into reaction, and _k_ the coefficient of proportionality. Ikeda took a test-tube (diameter about 10 mm.), and covered its outer surface with a coating of phosphorus (by melting it in a test-tube of large diameter, inserting the smaller test-tube, and, when the phosphorus had solidified, breaking away the outer test-tube), and introduced it into a definite volume of air, contained in a Woulfe's bottle (immersed in a water bath to maintain a constant temperature), one of whose orifices was connected with a mercury manometer showing the fall of pressure, _x_. Knowing that the initial pressure of the oxygen (in air nearly 750 × ·0209) was about 155 mm. = A, the coefficient of the rate of reaction _k_ is given, by the law of the variation of the rate of reaction with the mass of the reacting substance, by the equation: _k_ = (1/_t_)log(A/(A - _x_)), where _t_ is the time, counting from the commencement, of the experiment in minutes. When the surface of the phosphorus was about 11 sq. cm., the following results were actually obtained. _t_ = 10 20 30 40 50 60 minutes _x_ = 10·5 21·5 31·1 40·7 49·1 57·3 mm 10,000 _k_ = 32 32 32 33 33 33 The constancy of _k_ is well shown in this case. The determination takes a comparatively short time, so that it may serve as a lecture experiment, and demonstrates one of the most important laws of chemical mechanics. [3 bis] Not only do oxidising agents like nitric, chromic, and similar acids act upon phosphorus, but even the alkalis are attacked--that is, phosphorus acts as a reducing agent. In fact it reduces many substances, for instance, copper from its salts. When phosphorus is heated with sodium carbonate, the latter is partially reduced to carbon. If phosphorus be placed under water slightly warmed, and a stream of oxygen be passed over it, it will burn under the water. Besides this, there is a red variety of phosphorus, which differs considerably from the above. _Red phosphorus_ (sometimes wrongly called _amorphous phosphorus_) is partially formed when ordinary phosphorus remains exposed to the action of light for a long time. It is also formed in many reactions; for example, when ordinary phosphorus combines with chlorine, bromine, iodine, or oxygen, a portion of it is converted into red phosphorus. Schrötter, in Vienna, investigated this variety of phosphorus, and pointed out by what methods it may be produced in considerable quantities. Red phosphorus is a powdery red-brown opaque substance of specific gravity 2·14. It does not combine so energetically with oxygen and other substances as yellow phosphorus, and evolves less heat in combining with them.[4] Common phosphorus easily oxidises in the air; red phosphorus does not oxidise at all at the ordinary temperature; hence it does not phosphoresce in the air, and may be very conveniently kept in the form of powder. It does not, like yellow phosphorus, fuse at 44°. After being converted into vapour at 290° or 300°, it again passes into the ordinary variety when slowly cooled. Red phosphorus is not soluble in carbon bisulphide and other oily liquids, which permits of its being freed from any admixture of the ordinary phosphorus. It is not poisonous, and is used in many cases for which the ordinary phosphorus is unsuitable or dangerous; for example, in the manufacture of matches, which are then not poisonous or inflammable by accidental friction, and therefore the red variety has now replaced the ordinary phosphorus.[4 bis] [4] The thermochemical determinations for phosphorus and its compounds date from the last century, when Lavoisier and Laplace burnt phosphorus in oxygen in an ice calorimeter. Andrews, Despretz, Favre, and others have studied the same subject. The most accurate and complete data are due to Thomsen. To determine the heat of combustion of yellow phosphorus, Thomsen oxidised it in a calorimeter with iodic acid in the presence of water, and a mixture of phosphorous and phosphoric acids was thus formed (was not any hypophosphoric acid formed?--Salzer), and the iodic acid converted into hydriodic acid. It was first necessary to introduce two corrections into the calorimetric result obtained, one for the oxidation of the phosphorous into phosphoric acid, knowing their relative amounts by analysis, and the other for the deoxidation of the iodic acid. The result then obtained expresses the conversion of phosphorous into hydrated phosphoric acid. This must be corrected for the heat of solution of the hydrate in water, and for the heat of combination of the anhydride with water, before we can obtain the heat evolved in the reaction of P_{2} with O_{5} in the proportion for the formation of P_{2}O_{5}. It is natural that with so complex a method there is a possibility of many small errors, and the resultant figures will only present a certain degree of accuracy after repeated corrections by various methods. Of such a kind are the following figures determined by Thomsen, which we express in thousands of calories:--P_{2} + O_{5} = 370; P_{2} + O_{3} + 3H_{2}O = 400; P_{2} + O_{5} + a mass of water = 405. Hence we see that P_{2}O_{5} + 3H_{2}O = 30; 2PH_{3}O_{4} + an excess of water = 5. Experiment further showed that crystallised PH_{3}O_{4}, in dissolving in water, evolves 2·7 thousand calories, and that fused (39°) PH_{3}O_{4} evolves 5·2 thousand calories, whence the heat of fusion of H_{3}PO_{4} = 2·5 thousand calories. For phosphorous acid, H_{3}PO_{3}, Thomsen obtained P_{2} + O_{3} + 3H_{2}O = 250, and the solution of crystallised H_{3}PO_{3} in water = -0·13, and of fused H_{3}PO_{3} = +2·9. For hypophosphorous acid, H_{3}PO_{2}, the heats of solution are nearly the same (-0·17 and +2·1), and the heat of formation P_{2} + O + 3H_{2}O = 75; hence its conversion into 2H_{3}PO_{3} evolves 175 thousand calories, and the conversion of 2H_{3}PO_{3} into 2H_{3}PO_{4} = 150 thousand calories. For the sake of comparison we will take the combination of chlorine with phosphorus, also according to Thomsen, per 2 atoms of phosphorus, P_{2} + 3Cl_{2} = 151, P_{2} + 5Cl_{2} = 210 thousand calories. In their reaction on an excess of water (with the formation of a solution), 2PCl_{3} = 130, 2PCl_{5} = 247, and 2POCl_{3} = 142 thousand calories. Besides which we will cite the following data given by various observers: heat of fusion for P (that is, for 31 parts of phosphorus by weight) -0·15 thousand calories; the conversion of yellow into red phosphorus for P, from +19 to +27 thousand calories; P + H_{3} = 4·3, HI + PH_{3} = 24, PH_{3} + HBr = 22 thousand calories. At the ordinary temperature (20° C.) phosphorus is not oxidised by pure oxygen; oxidation only takes place with a slight rise of temperature, or the dilution of the oxygen with other gases (especially nitrogen or hydrogen), or a decrease of pressure. [4 bis] Ordinary phosphorus takes fire at a temperature (60°) at which no other known substance will burn. Its application to the manufacture of matches is based on this property. In order to illustrate the easy inflammability of common (yellow) phosphorus, its solution in carbon bisulphide may be poured over paper; this solvent quickly evaporates, and the free phosphorus spread over a large surface takes fire spontaneously, notwithstanding the cooling effect produced by the evaporation of the bisulphide. The majority of _phosphorus matches_ are composed of common phosphorus mixed with some oxidising substance which easily gives up oxygen, such as lead dioxide, potassium chlorate, nitre, &c. For this purpose common phosphorus is carefully triturated under warm water containing a little gum; lead dioxide and potassium nitrate are then added to the resultant emulsion, and the match ends, previously coated with sulphur or paraffin, are dipped into this preparation. After this the matches are dipped into a solution of gum and shellac, in order to preserve the phosphorus from the action of the air. When such a match containing particles of yellow phosphorus is rubbed over a rough surface, it becomes (especially at the point of rupture of the brittle gummy coating) slightly heated, and this is sufficient to cause the phosphorus to take fire and burn at the expense of the oxygen of the other ingredients. The heads of the 'safety' matches do not contain any phosphorus, but only substances capable of burning and of supporting combustion. Red phosphorus is spread over a surface on the box, and it is the friction against this phosphorus which ignites the matches. There is no danger of the matches taking fire accidentally, nor are they poisonous.[5] This red phosphorus is prepared by heating the ordinary phosphorus at 230° to 270°; it is evident that this must be done in an atmosphere incapable of supporting combustion--for example, in nitrogen, carbonic anhydride, steam, &c. On a large scale, ordinary phosphorus is placed in closed iron vessels,[5 bis] and immersed in a bath of different proportions of tin and lead, by which means the temperature of 250° necessary for the conversion is easily attained. It is kept at this temperature for some time. The temperature is at first cautiously raised, and the air is thus partially expelled by the heat, and also by the evolution of steam (the phosphorus is damp when put in), whilst the remaining oxygen is also partially absorbed by the phosphorus, so that an atmosphere of nitrogen is produced in the iron vessel. Red phosphorus enters into all the reactions proper to yellow phosphorus, only with greater difficulty and more slowly;[6] and, as its vapour tension (volatility) is less than that of the yellow variety, it may be supposed that a polymerisation takes place in the passage of the yellow into the red modification, just as in the passage of cyanogen into paracyanogen, or of cyanic acid into cyanuric acid (Chapter IX. Notes 39 bis and 48). [5] In the so-called 'safety' or Swedish matches (which are not poisonous, and do not take fire from accidental friction) a mixture of red phosphorus and glass forms the surface on which the matches are struck, and the matches themselves do not contain any phosphorus at all, but a mixture of antimonious sulphide, Sb_{2}S_{3} (or similar combustible substances) and potassium chlorate (or other oxidising agents). The combustion, when once started by contact with the red phosphorus, proceeds by itself at the expense of the inflammatory and combustible elements contained in the tip of the match. The mixture applied on the match itself must not be liable to take fire from a blow or friction. The mixture forming the heads of the 'safety' matches has the following approximate composition: 55-60 parts of chlorate of potassium, 5-10 parts of peroxide of manganese (or of K_{2}Cr_{2}O_{7}), about 1 part of sulphur or charcoal, about 1 part of pentasulphide of antimony, Sb_{2}S_{5}, and 30-40 parts of rouge and powdered glass. This mixture is stirred up in gum or glue, and the matches are dipped into it. The paper on which the matches are struck is coated with a mixture of red phosphorus and trisulphide of antimony, Sb_{2}S_{3}, stirred up in dextrine. [5 bis] Phosphorus only acts on iron at a red heat. The boiler is provided with a safety valve and gas-conducting tube, which is immersed in mercury or other liquid to prevent the admission of air into the boiler. [6] The specific heat of the yellow variety is 0·189--that is, greater than that of the red variety, which is 0·170. The sp. gr. of the yellow is 1·84, and of the red prepared at 260° 2·15, and of that prepared at 580° and above (_i.e._ 'metallic' phosphorus, _see_ below) = 2·34. At 230° the pressure of the vapour of ordinary phosphorus = 514 millimetres of mercury, and of the red = 0--that is to say, the red phosphorus does not form any vapour at this temperature; at 447° the vapour tension of ordinary phosphorus is at first = 5500 mm., but it gradually diminishes, whilst that of red phosphorus is equal to 1636 mm. Hittorf, by heating the lower portion of a closed tube containing red phosphorus to 530° and the upper portion to 447°, obtained crystals of the so-called 'metallic' phosphorus at the upper extremity. As the vapour tensions (according to Hittorf, at 530° the vapour tension of yellow phosphorus = 8040 mm., of red = 6139 mm., and of metallic = 4130 mm.) and reactions are different, _metallic phosphorus_ may be regarded as a distinct variety. It is still less energetic in its chemical reaction than red phosphorus, and it is denser than the two preceding varieties: sp. gr. = 2·34. It does not oxidise in the air; is crystalline, and has a metallic lustre. It is obtained when ordinary phosphorus is heated with lead for several hours at 400° in a closed vessel, from which the air has been exhausted. The resultant mass is then treated with dilute nitric acid, which first dissolves the lead (phosphorus is electro-negative to lead, and does not, therefore, act on the nitric acid at first) and leaves brilliant rhombohedral crystals of phosphorus of a dark violet colour with a slight metallic lustre, which conduct an electric current incomparably better than the yellow variety; this also is characteristic of the metallic state of phosphorus. The researches of Lemoine partially explain the passage of yellow (ordinary) phosphorus into its other varieties. He heated a closed glass globe containing either ordinary or red phosphorus, in the vapour of sulphur (440°), and then determined the amount of the red and yellow varieties after various periods of time, by treating the mixture with carbon bisulphide. It appeared that after the lapse of a certain time a mixture of definite and equal composition is obtained from both--that is, between the red and yellow varieties a state of equilibrium sets in like that of dissociation, or that observed in double decompositions. But at the same time, the progress of the transformation appeared to be dependent on the relative quantity of phosphorus taken per volume of the globe (_i.e._ upon the pressure). Neglecting the latter, we will cite as an example the amounts of the red phosphorus transformed into the ordinary, and of the ordinary not converted into red, per 30 grams of red or yellow taken per litre capacity of the globe, heated to 440°. When red phosphorus was taken, 4·75 grams of yellow phosphorus were formed after two hours, four grams after eight hours, three grams after twenty-four hours, and the last limit remained constant on further heating. When thirty grams of yellow phosphorus were taken, five grams remained unaltered after two hours, four grams after eight hours, and after twenty-four hours and more three grams as before. Troost and Hautefeuille showed that liquid phosphorus in general changes more easily into the red than does phosphorus vapour, which, however, is able, although slowly, to deposit red phosphorus. The question presents itself as to whether phosphorus in a state of vapour is the ordinary or some other variety? Hittorf (1865) collected many data for the solution of this problem, which leave no doubt that (as experimental figures show) the density of the vapour of phosphorus is always the same, although the vapour tension of the different varieties and their mixtures is very variable. This shows that the different varieties of phosphorus only occur in a liquid and solid state, as indeed is implied in the idea of polymerisation. Strictly speaking, the vapour of phosphorus is a particular state of this substance, and the molecular formula P_{4} refers only to it, and not to any other definite state of phosphorus. But Raoult's solution method showed that in a benzene solution the fall of the freezing point indicates for ordinary phosphorus a molecule P_{4}, judging by the determinations of Paterno and Nasini (1888), Hirtz (1890), and Beckmann (1891), who obtained for sulphur by the same method a molecular weight = S_{6}, in conformity with the vapour density. Further research in this direction will perhaps show the possibility of finding the molecular weight of red phosphorus, if a means be discovered for dissolving it without converting it into the yellow variety. I think it will not be out of place here to draw the reader's attention to the fact that red phosphorus, which we must recognise as polymeric with the yellow, stands nearer to nitrogen, whose molecule is N_{2}, in its small inclination towards chemical reactions, although judging by its small vapour tension it must be more complex than ordinary (yellow and white) phosphorus. The vapour of phosphorus is colourless; its density remains constant between 300° and 1000° (Dumas, 1833; Mitscherlich, Deville, and Troost, 1859, and others). The density with respect to air has been determined as from 4·3 to 4·5. Hence, referred to hydrogen, it is 4·4 × 14·4 = 63, corresponding with a molecular weight 124, _i.e._ the molecule of phosphorus in a state of vapour contains P_{4}. The reader will remember that the molecule of nitrogen contains N_{2}, of sulphur S_{6} or S_{2}, and of oxygen O_{2} or O_{3}. The chemical energy of phosphorus in a free state more nearly approaches that of sulphur than nitrogen. Phosphorus is combustible and inflames at 60°; but having in the act of combination parted with a portion of its energy in the form of heat it becomes analogous to nitrogen, so long as there is no question of its reduction back again into phosphorus. Nitric acid is easily reduced to nitrogen, whilst phosphoric acid is reduced with very much greater difficulty. All the compounds of phosphorus are less volatile than those of nitrogen. Nitric acid, HNO_{3}, is easily distilled; metaphosphoric acid, HPO_{3}, is generally said to be non-volatile; triethylamine, N(C_{2}H_{5})_{3}, boils at 90°, and triethylphosphine, P(C_{2}H_{5})_{3}, at 127°. Phosphorus not only combines easily and directly with oxygen, but also with chlorine, bromine, iodine, sulphur, and with certain metals, and red phosphorus when heated combines with hydrogen also.[6 bis] So, for instance, when fused with sodium under naphtha, phosphorus gives the compound Na_{3}P_{2}. Zinc, absorbing the vapour of phosphorus, gives the phosphide Zn_{3}P_{2} (sp. gr. 4·76); tin, SnP; copper, Cu_{2}P; even platinum combines with phosphorus (PtP_{2}, sp. gr. 8·77).[6 tri] Iron, when combined even with a small quantity of phosphorus, becomes brittle.[7] Some of these compounds of phosphorus are obtained by the action of phosphorus on the solutions of metallic salts, and by the ignition of metallic oxides in the vapour of phosphorus, or by heating mixtures of phosphates with charcoal and metals. Phosphides do not exhibit the external properties of salts, which are so clearly seen in the chlorides and still distinctly observable in the sulphides. _The phosphides of the metals_ of the alkalis and of the alkaline earths are even immediately and very easily decomposed by water, whereas this is found to be the case with only a very few sulphides, and still more rarely and indistinctly with the chlorides. We may take calcium phosphide as an example.[7 bis] Phosphorus is laid in a deep crucible, and covered with a clay plug, over which lime is strewn. At a red heat the vapours of phosphorus combine with the oxygen of the lime and form phosphoric anhydride, which forms a salt with another portion of the lime, whilst the liberated calcium combines with the phosphorus and forms calcium phosphide. Its composition is not quite certain; it may be CaP (corresponding with liquid phosphuretted hydrogen). This substance is remarkable for the following reaction: if we take water--or, better still, a dilute solution of hydrochloric acid--and throw calcium phosphide into it, bubbles of gas are evolved, which take fire spontaneously in the air and form white rings. This is owing to the fact that the liquid hydrogen phosphide, PH_{2}, is first formed, thus, CaP + 2HCl = CaCl_{2} + PH_{2}, which, owing to its instability, very easily splits up into the solid phosphide, P_{2}H, and gaseous phosphide, PH_{3}; 5PH_{2} = P_{2}H + 3PH_{3}; the latter corresponds with ammonia. The mixture of the gaseous and liquid phosphides takes fire spontaneously in the air, forming phosphoric acid. The same hydrogen phosphides are formed when water acts on sodium phosphide (P_{2}Na_{3}). A similar mixture of gaseous liquid and solid phosphuretted hydrogen (Retgers 1894) is formed by heating (in a glass tube) red phosphorus in a stream of dry hydrogen. Hence we see that there are _three compounds of phosphorus with hydrogen_. (1) The first or solid yellow phosphide, P_{2}H (more probably P_{4}H_{2}), is obtained by the action of strong hydrochloric acid on sodium phosphide; it takes fire when struck or at 175°. (2) The liquid, PH_{2}, or more correctly expressed as the molecule, P_{2}H_{4}, is a colourless liquid which takes fire spontaneously in the air, boils at 30°, is very unstable, and is easily decomposed (by light or hydrochloric acid) into the two other phosphides of hydrogen. It is prepared by passing the gases evolved by the action of water on calcium phosphide through a freezing mixture.[8] And, lastly, (3), gaseous hydrogen phosphide, _phosphine_, PH_{3}, which is distinguished as being the most stable. It is a colourless gas, which does not take fire in the air. It has an odour of garlic, and is very poisonous. It resembles ammonia in many of its properties.[8 bis] It is easily decomposed by heat, like ammonia, forming phosphorus and hydrogen; but it is very slightly soluble in water, and does not saturate acids, although it forms compounds with some of them which resemble ammonium salts in their form and properties. Among them the _compound with hydriodic acid_, PH_{4}I, analogous to ammonium iodide, is remarkable. This compound crystallises on sublimation in well-formed cubes, like sal-ammoniac, which it resembles in many respects. However, this compound does not enter into those reactions of double decomposition which are proper to sal-ammoniac, because its saline properties are very feebly developed. Phosphuretted hydrogen also combines, like ammonia, with certain chloranhydrides; but they are decomposed by water, with the evolution of phosphine. Ogier (1880) showed that hydrochloric acid also combines with phosphine under a pressure of 20 atmospheres at +18°, and under the ordinary pressure at -35°, forming the crystalline phosphonium chloride PH_{4}Cl, corresponding to sal-ammoniac. Hydrobromic acid does the same with greater ease, and hydriodic acid with still greater facility, forming phosphonium iodide, PH_{4}I.[9] [6 bis] Retgers (see further on) showed this in 1894, and observed that As when heated also combines with hydrogen. [6 tri] The capacity of mercury (Chapter XVI., Note 25 bis) to give unstable compounds with nitrogen gives rise to the supposition that similar compounds exist with phosphorus also. Such a compound was obtained by Granger (1892) by heating mercury with iodide of phosphorus in a closed tube at 275°-300°. After removing the iodide of mercury formed, there remain fine rhombic crystals having a metallic lustre, and composition Hg_{3}P_{2}. This compound is stable, does not alter at the ordinary temperature and only decomposes at a red heat; when heated in air it burns with a flame. Nitric and hydrochloric acids do not act upon it, but it is easily decomposed by aqua regia. A phosphide of copper, Cu_{2}P_{2}, was obtained by Granger (1893) by heating a mixture of water, finely divided copper and red phosphorus in a sealed tube to 130°. The excess of copper was afterwards washed away by a solution of NH_{3} in the presence of air. [7] The metallic compounds of phosphorus possess a great chemical interest, because they show a transition from metallic alloys (for instance, of Sb, As) to the sulphides, halogen salts, and oxides, and on the other hand to the nitrides. Although there are already many fragmentary data on the subject, the interesting province of the metallic phosphides cannot yet be regarded as in any way generalised. The varied applications (phosphor-iron, phosphor-bronze, &c.), which the phosphides have recently acquired should give a strong incentive to the complete and detailed study of this subject, which would, in my opinion, help to the explanation of chemical relations beginning with alloys (solutions) and ending with salts and the compounds of hydrogen (hydrides), because the phosphor-metals, as is proved by direct experiment, stand in the same relation to phosphuretted hydrogen as the sulphides do towards sulphuretted hydrogen, or as the metallic chlorides to hydrochloric acid. [7 bis] Many other compounds of phosphorus are also capable of forming phosphuretted hydrogen. Thus BP also gives PH_{3} (_see_ Chapter XVII., Note 12). According to Lüpke (1890) phosphuretted hydrogen is formed by phosphide of tin. The latter is prepared by treating molten tin covered with a layer of carbonate of ammonium, with red phosphorus; 200-300 c.c. of water are then poured into a flask, 3-5 grams of this phosphide of tin dropped in, and after driving out the air by a stream of carbonic acid, hydrochloric acid (sp. gr. 1·104) is poured in. The disengagement of phosphuretted hydrogen takes place on heating the flask in a water bath. The following is another easy method for preparing PH_{3}. A mixture of 1 part of zinc dust (fume) and 2 parts of red phosphorus are heated in an atmosphere of hydrogen (the mixture burns in air). Combination takes place accompanied by a flash, and a grey mass of Zn_{3}P_{2} is formed which gives PH_{3} when treated with dilute H_{2}SO_{4}. [8] The spontaneous inflammability of the hydride PH_{2} in air is very remarkable, and it is particularly interesting that its analogues in composition, P(C_{2}H_{5})_{2} (the formula must be doubled) and Zn(C_{2}H_{5})_{2}, also take fire spontaneously in air. [8 bis] The analogy between PH_{3} and NH_{3} is particularly clear in the hydrocarbon derivatives. Just as NH_{2}R, NHR_{2}, and NR_{3}, where R is CH_{3}, and other hydrocarbon radicles, correspond to NH_{3}, so there are actually similar compounds corresponding to PH_{3}. These compounds form a branch of organic chemistry. [9] The periodic law and direct experiment (the molecular weight) show that PH_{3} is the normal compound of P and H and that it is more simple than PH_{2} or P_{2}H_{4}, just as methane, CH_{4}, is more simple than ethane, C_{2}H_{6}, whose empirical composition is CH_{3}. The formation of liquid phosphuretted hydrogen may be understood from the law of substitution. The univalent radicle of PH_{3} is PH_{2}, and if it is combined with H in PH_{3} it replaces H in liquid phosphuretted hydrogen, which thus gives P_{2}H_{4}. This substance corresponds with free amidogen (hydrazine), N_{2}H_{4} (Chapter VI.) Probably P_{2}H_{4} is able to combine with HI, and perhaps also with 2HI, or other molecules--that is, to give a substance corresponding to phosphonium iodide. _Phosphonium iodide_, PH_{4}I, may be prepared, according to Baeyer, in large quantities in the following manner:--100 parts of phosphorus are dissolved in dry carbon bisulphide in a tubulated retort: when the mixture has cooled, 175 parts of iodide are added little by little, and the carbon bisulphide is then distilled off, this being done towards the end of the operation in a current of dry carbonic anhydride at a moderate temperature. The neck of the retort is then connected with a wide glass tube, and the tubulure with a funnel furnished with a stopcock, and containing 50 parts of water. This water is added drop by drop to the phosphorous iodide, and a violent reaction takes place, with the evolution of hydriodic acid and phosphonium iodide. The latter collects as crystals in the glass tube and the retort itself. It is purified by further distillations; more than 100 parts may be obtained. Baeyer expresses the reaction by the equation P_{2}I + 2H_{2}O = PH_{4}I + PO_{2}; and the compound PO_{2} may be represented as phosphorous phosphoric anhydride: P_{2}O_{5} + P_{2}O_{3} = 4PO_{2}. As a better proportion we may take 400 grams of phosphorus, 680 grams of iodine, and 240 grams of water, and express the formation thus: 13P + 9I + 21H_{2}O = 3H_{4}P_{2}O_{7} + 7PH_{4}I + 2HI (Chapter XI., Note 77). Phosphonium iodide and even phosphine act as reducing agents in solutions of many metallic salts. Cavazzi showed that with a solution of sulphurous anhydride phosphine gives sulphur and phosphoric acid. _Phosphuretted hydrogen, or phosphine_, PH_{3}, is generally prepared by the action of caustic potash on phosphorus.[10] Small pieces of phosphorus are dropped into a flask containing a strong solution of caustic potash and heated. Potassium hypophosphite, H_{2}KPO_{2}, is then obtained in solution; gaseous phosphuretted hydrogen is evolved: P_{4} + 3KHO + 3H_{2}O = 3(KH_{2}PO_{2}) + PH_{3}. Liquid phosphuretted hydrogen (and free hydrogen) is also formed, together with the phosphine, so that the gaseous product, on escaping from the water into the air, takes fire spontaneously, forming beautiful white rings of phosphoric acid. In this experiment, as in that with calcium phosphide, it is the liquid, P_{2}H_{4}, that takes fire; but the phosphine set light to by it also burns, PH_{3} + O_{4} = PH_{3}O_{4}. The same phosphuretted hydrogen, PH_{3}, may be obtained pure, and not spontaneously combustible, by igniting the hydrates of phosphorous acid (4PH_{3}O_{3} = PH_{3} + 3PH_{3}O_{4}) and hypophosphorous acid (2PH_{3}O_{2} = PH_{3} + PH_{3}O_{4}); or, more simply, by the decomposition of calcium phosphide by hydrochloric acid, because then all the liquid phosphide, P_{2}H_{4}, is decomposed into non-volatile P_{2}H and gaseous PH_{3}. Pure phosphine liquefies when cooled to -90°, boils at -85°, and solidifies at -135° (Olszewski). When phosphorus burns in an excess[10 bis] of _dry_ oxygen, then only _phosphoric anhydride_, P_{2}O_{5} is formed. It is prepared by dropping pieces of phosphorus through a wide tube, fixed into the upper neck of a large glass globe, on to a cup suspended in the centre of the globe. These lumps are set alight by touching them with a hot wire, and the phosphorus burns into P_{2}O_{5}. The dry air necessary for its combustion is forced into the globe through a lateral neck, and the white flakes of phosphoric anhydride formed are carried by the current of air through a second lateral neck into a series of Woulfe's bottles, where they settle as friable white flakes. Phosphoric anhydride may also be formed by passing dry air through a solution of phosphorus in carbon bisulphide. All the materials for the preparation of this substance must be carefully dried, because it _combines_ with great eagerness _with water_, at the same time developing a large amount of heat and forming metaphosphoric acid, HPO_{3}, from which the water cannot be separated by heat. Phosphoric anhydride is a colourless snow-like substance, which attracts moisture from the air with the utmost avidity. It fuses at a red heat, and then _volatilises_. Its affinity for water is so great that it takes it up from many substances. Thus it converts sulphuric acid into sulphuric anhydride, and carbohydrates (wood, paper) are carbonised, and give up the elements of water when brought into contact with it. [10] The air must first be expelled from the flask by hydrogen, or some other gas which will not support combustion, as otherwise an explosion might take place owing to the spontaneous inflammability of the phosphuretted hydrogen. The combustion of phosphuretted hydrogen in oxygen also takes place under water when the bubbles of both gases meet, and it is very brilliant. The phosphuretted hydrogen obtained by the action of phosphorus on caustic potash always contains free hydrogen, and often even the greater part of the gas evolved consists of hydrogen. _Pure phosphuretted hydrogen_ (not containing hydrogen or liquid or solid phosphides) is obtained by the action of a solution of potash on phosphonium iodide: PH_{4}I + KHO = PH_{3} + KI + H_{2}O (in just the same way as ammonia is liberated from ammonium chloride). The reaction proceeds easily, and the purity of the gas is seen from the fact that it is entirely absorbed by bleaching powder and is not spontaneously inflammable. Its mixture with oxygen explodes when the pressure is diminished (Chapter XVIII., Note 8). The vapours of bromine, nitric acid, &c., cause it to again acquire the property of inflaming in the air; that is, they partially decompose it, forming the liquid hydride, P_{2}H_{4}. Oppenheim showed that when red phosphorus is heated at 200° with hydrochloric acid in a closed tube it forms the compound PCl_{3}(H_{3}PO_{3}), together with phosphine. [10 bis] If there be a deficiency of oxygen, _phosphorous anhydride_ P_{2}O_{3} is formed. It was obtained by Thorpe and Tutton (1890) and is easily volatilised, melts at 22°·5, boils without change (in an atmosphere of N_{2} or CO_{2}) at 173°, and is therefore easily separated from P_{2}O_{3}, which volatilises with difficulty. The vapour density shows that the molecular weight is double, _i.e._ P_{4}O_{6} (like As_{2}O_{3}). Although colourless, phosphorous anhydride (its density in a state of fusion at 24° = 1·936) turns yellow and reddens in sun-light (possibly red phosphorus separates out ?), and decomposes at 400° forming hypophosphorous anhydride P_{2}O_{4} (Note 11) and phosphorus. It passes into P_{2}O_{5} in air and oxygen, and when slightly heated in oxygen becomes luminous, and ultimately takes fire. Cold water slowly transforms P_{2}O_{3} into phosphoric acid, but hot water gives an explosion and leads to the formation of PH_{3}, (P_{4}O_{6} + 6H_{2}O = PH_{3} + 3PH_{3}O_{4}). Alkalis act in the same manner. It takes fire in chlorine and forms POCl_{3} and PO_{2}Cl, and combines with sulphur at 160°, forming P_{2}S_{2}O_{3} (the molecular formula is double this) a substance which volatilises in vacuo and is decomposed by water into H_{2}S and phosphoric acid, _i.e._ it may be regarded as P_{2}O_{5}, in which O_{2} has been replaced by two atoms of sulphur. Judging from the above, the mixture of P_{2}O_{3} and P_{2}O_{5} formed in the combustion of phosphorus in air is transformed into P_{2}O_{5} in an excess of oxygen. When moist phosphorus slowly oxidises in the air, it not only forms phosphorous and phosphoric acids, but also _hypophosphoric acid_, H_{4}P_{2}O_{6}, which when in a dry state easily splits up at 60° into phosphorous and metaphosphoric acids (H_{4}P_{2}O_{6} = H_{3}PO_{3} + HPO_{3}), but differs from a mixture of these acids in that it forms well-characterised salts, of which the sodium salt, H_{2}Na_{2}P_{2}O_{6}, is but slightly soluble in water (the sodium salts of phosphoric and phosphorous acids are easily soluble), and that it does not act as a reducing agent, like mixtures containing phosphorous acid.[11] [11] Salzer proved the existence of hypophosphoric acid (it is also called subphosphoric acid), in which many chemists did not believe. Drawe (1888) and Rammelsberg (1892) investigated its salts. It may be obtained in a free state by the following method. The solution of acid produced by the slow oxidation of moist phosphorus is mixed with a solution (25 p.c.) of sodium acetate. A salt, Na_{2}H_{2}P_{2}O_{6},6H_{2}O, crystallises out on cooling; it is soluble in 45 parts of water, and gives a precipitate of Pb_{2}P_{2}O_{6} with lead salts (Ag_{4}P_{2}O_{6} with salts of silver). The lead salt is decomposed by a current of hydrogen sulphide, when lead sulphide is precipitated, while the solution, evaporated under the receiver of an air-pump, gives crystals of H_{4}P_{2}O_{6},2H_{2}O, which easily lose water and give H_{4}P_{2}O_{6}. The salts in which the H_{4} is replaced by Ni_{2}, or NiNa_{2}, or CdNa_{2}, &c., are insoluble in water. In order to see the relation between phosphoric acid and hypophosphoric acid which does not contain the elements of phosphorous acid (because it does not reduce either gold or mercury from their solutions), but which nevertheless is capable of being oxidised (for example, by potassium permanganate) into phosphoric acid, it is simplest to apply the law of substitution. This clearly indicates the relation between oxalic acid, (COOH)_{2}, and carbonic acid, OH(COOH). The relation between the above acids is exactly the same if we express phosphoric acid as OH(POO_{2}H_{2}), because in this case P_{2}H_{4}O_{6}, or (POO_{2}H_{2})_{3}, will correspond with it just as oxalic does with carbonic acid. A similar relationship exists between hyposulphuric or dithionic acid, (SO_{2}OH)_{2}, and sulphuric acid, OH(SO_{2}OH), as we shall find in the following chapter. Dithionic acid corresponds with the anhydride S_{2}O_{5}, intermediate between SO_{2} and SO_{3}; oxalic acid with C_{2}O_{3}, intermediate between CO and CO_{2}; hypophosphoric acid corresponds with the anhydride P_{2}O_{4}, intermediate between P_{2}O_{3} and P_{2}O_{5}, and the analogue of N_{2}O_{4}. Judging by the general law of the formation of acids (Chapter XV.), the series of phosphorus compounds should include the following _ortho-acids_ and their corresponding anhydrides, answering to phosphuretted hydrogen, H_{3}P:-- H_{3}PO_{4}, phosphoric acid, and P_{2}O_{5}, anhydride, H_{3}PO_{3}, phosphorous acid, and P_{2}O_{3}, anhydride, H_{3}PO_{2}, hypophosphorous acid, and P_{2}O, anhydride.[12] The last of these (the analogue of N_{2}O) is almost unknown. Phosphoric anhydride (P_{2}O_{5}) with a small quantity of water does not at first give orthophosphoric acid, PH_{3}O_{4}, but a compound P_{2}O_{5},H_{2}O, or PHO_{3}, whose composition corresponds with that of nitric acid; this is _metaphosphoric acid_. Even with an excess of water, combining with phosphoric anhydride, this metaphosphoric acid, and not the ortho-, passes at first into solution. Metaphosphoric acid in solution only passes into orthophosphoric acid when the solution is heated or after a lapse of time. [12] Besides the hydrates enumerated, a compound, PH_{3}O, should correspond with PH_{3}. This hydrate, which is analogous to hydroxylamine, is not known in a free state, but it is known as triethylphosphine oxide, P(C_{2}H_{5})_{3}O, which is obtained by the oxidation of triethylphosphine, P(C_{2}H_{5})_{3}. It must be observed that there may also be lower oxides of phosphorus corresponding with PH_{3}, like N_{2}O and NO, and there are even indications of the formation of such compounds, but the data concerning them cannot be considered as firmly established. _Orthophosphoric acid_[13] is obtained by oxidising phosphorus with nitric acid until the phosphorus entirely passes into solution and the lower oxides of nitrogen cease to be evolved. The reaction takes place best with dilute nitric acid, and when aided by heat. The resultant solution is evaporated to a syrup. If a weighed quantity of phosphorus (dried in a current of dry carbonic anhydride) be taken, a crystalline mass of the acid can be obtained by evaporating the solution until it consists only of the quantity[14] of phosphoric acid corresponding with the amount of phosphorus taken (from 31 parts of P, 98 parts of solution). The acid fuses at +39°; specific gravity of the liquid 1·88. Phosphorus pentachloride, PCl_{5}, and oxychloride, POCl_{3} (see further on), give orthophosphoric acid and hydrochloric acid with water. The two other varieties of phosphoric acid, with which we shall presently become acquainted, give the same ortho-acid when under the influence of acids, with particular ease when boiled and more slowly in the cold. By itself orthophosphoric acid (either in solution or when dry) does not pass into the other varieties; it does not oxidise, and therefore presents the limiting and stable form. When heated to 300°, it loses water and passes into pyrophosphoric acid, 2H_{3}PO_{4} = H_{2}O + H_{4}P_{2}O_{7}, whilst at a red heat it loses twice as much water and is converted into metaphosphoric acid, H_{3}PO_{4} = H_{2}O + HPO_{3}. In aqueous solution orthophosphoric acid differs clearly from pyro- or metaphosphoric acids, because the solutions of these latter acids give different reactions: thus orthophosphoric acid does not precipitate albumin, does not give a precipitate with barium chloride, and forms a yellow precipitate of silver orthophosphate, Ag_{3}PO_{4}, with silver nitrate (in the presence of alkalis, but not otherwise); whilst a solution of pyrophosphoric acid, H_{4}P_{2}O_{7}, although it does not precipitate albumin or barium chloride, gives a white precipitate of silver pyrophosphate, Ag_{4}P_{2}O_{7}, with silver nitrate; and a solution of metaphosphoric acid, HPO_{3}, precipitates both albumin and barium chloride, and gives a white precipitate of silver metaphosphate, AgPO_{3}, with silver nitrate. These points of distinction were studied by Graham, and are exceedingly instructive. They show that the solution of a substance does not determine the maximum of chemical combination with water, that solutions may contain various degrees of combination with water, and that there is a clear difference between the water serving for solution and that entering into chemical combination. Graham's experiments also showed that the water whose removal or combination determines the conversion of ortho- into meta- and pyrophosphoric acids differs distinctly from water of crystallisation, for he obtained the salts of ortho-, meta-, and pyrophosphoric acids with water of crystallisation, and they differed in their reactions, like the acids themselves. This water of crystallisation was expelled with greater ease than the water of constitution of the hydrates in question.[14 bis] [13] Phosphoric acid, being a soluble and almost non-volatile substance, cannot be prepared like hydrochloric and nitric acids by the action of sulphuric acid on the alkali phosphates, although it is partially liberated in the process. For this purpose the salts of barium or lead may be taken, because they give insoluble salts, thus Ba_{3}(PO_{4})_{2} + 3H_{2}SO_{4} = 3BaSO_{4} + 2H_{3}PO_{4}. Bone ash contains, besides calcium phosphate, sodium and magnesium phosphates, and fluorides and other salts, so that it cannot give directly a pure phosphoric acid. [14] If this is not done the orthophosphoric acid, PH_{3}O_{4}, loses a portion of its water, and then, as with an excess of water, it does not crystallise. [14 bis] The difference between the reactions of ortho-, meta- and pyrophosphoric acids, established by Graham (_see_ p. 163), is of such importance for the theory of hydrates and for explaining the nature of solutions, that in my opinion its influence upon chemical thought has been far from exhausted. At the present time many such instances are known both in organic (for instance, the difference between the reactions of the solutions of certain anhydrides and hydrates of acids), and inorganic chemistry (for example, the difference between the rose and purple cobalt compounds, Chapter XXII. &c.) They essentially recall the long known and generalised difference between C_{2}H_{4} (ethylene), C_{2}H_{6}O (ethyl alcohol = ethylene + water), and C_{4}H_{10}O (ethyl ether = 2 ethylene + water = 2 alcohol - water); but to the present day the numerous analogous phenomena existing among inorganic substances are only considered as a simple difference in degrees of affinity, distinguishing the water of constitution (hydration), crystallisation, and solution without penetrating into the difference of the structure or distribution of the elements, which exists here and gives rise to a distinct isomerism of solutions. In my opinion the progress of chemistry, especially with regard to solutions, should make rapid strides when the cause of the isomerism of solutions, for instance, of ortho- and pyrophosphoric acids, has become as clear to us as the cause of many well-studied instances of the isomerism, polymerism, and metamerism of organic compounds. Here it forms one of those many important problems which remain for the chemistry of the future in a state of only indistinct presentiments and in the form of facts empirically known but insufficiently comprehended. Orthophosphoric acid has a pleasant acid taste and a distinctly acid reaction; it is used as a medicine, and is not poisonous (phosphorous acid is poisonous). Alkalis, like sodium, potassium, and ammonium hydroxides, saturate the acid properties of phosphoric acid when taken in the ratio 2NaHO : H_{3}PO_{4}--that is, when salts of the composition HNa_{2}PO_{4} are formed. When taken in the ratio NaHO : H_{3}PO_{4}, a solution having an acid reaction is obtained, and when 3NaHO : H_{3}PO_{4}--that is, when the salt Na_{3}PO_{4} is formed--an alkaline reaction is obtained. Hence many chemists (Berzelius) even regarded the salts of composition R_{2}HPO_{4} as normal, and considered phosphoric acid to be bibasic. But the salt Na_{2}HPO_{4} also shows a feeble alkaline reaction, so that it is impossible to judge the characteristic peculiarities of acids by the reactions on litmus paper, as we already know from many examples. Orthophosphoric acid is tribasic, because it contains three equivalents of hydrogen replaceable by metals, forming salts, such as NaH_{2}PO_{4}, Na_{2}HPO_{4}, and Na_{3}PO_{4}. It is also tribasic, because with silver nitrate its soluble salts always give Ag_{3}PO_{4},[15] a salt with three equivalents of silver, and because by double decomposition with barium chloride it forms a salt of the composition Ba_{3}(PO_{4})_{2}, and silver and barium hardly ever give basic salts. With the metals of the alkalis, phosphoric acid forms soluble salts, but the normal salts of the metals of the alkaline earths, R_{3}(PO_{4})_{2} and even R_{2}H_{2}(PO_{4}), are insoluble in water, but dissolve in feeble acids, such as phosphoric and acetic, because they then form soluble acid salts, especially RH_{4}(PO_{4})_{2}.[16] [15] Silver orthophosphate, Ag_{3}PO_{4}, is yellow, sp. gr. 7·32, and insoluble in water. When heated it fuses like silver chloride, and if kept fused for some length of time it gives a white pyrophosphate (the decomposition which causes this is not known). It is soluble in aqueous solutions of phosphoric, nitric, and even acetic acids, of ammonia, and many of its salts. If silver nitrate acts on a dimetallic orthophosphate--for instance, Na_{2}HPO_{4}--it still gives Ag_{3}PO_{4}, nitric acid being disengaged: Na_{2}HPO_{4} + 3AgNO_{3} = Ag_{3}PO_{4} + 2NaNO_{3} + HNO_{3}. When alcohol is added to silver orthophosphate, Ag_{3}PO_{4}, dissolved in syrupy phosphoric acid, it precipitates a white salt (the alcohol takes up the free phosphoric acid) having the composition Ag_{2}HPO_{4}, which is immediately decomposed by water into the normal salt and phosphoric acid. [16] The researches of Thomsen showed that in very dilute aqueous solutions the majority of monobasic acids--nitric, acetic, hydrochloric, &c. (but hydrofluoric acid more and hydrocyanic less)--HX evolve the following amounts of heat (in thousands of calories) with caustic soda: NaHO + 2HX = 14; NaHO + HX = 14; 2NaHO + HX = 14; that is, if _n_ be a whole number _n_NaHO + HX = 14 and NaHO + _n_HX = 14. Hence reaction here only takes place between one molecule of NaHO and one molecule of acid, and the remaining quantity of acid or alkali does not enter into the reaction. In the case of bibasic acids, H_{2}R´´ (sulphuric, dithionic, oxalic, sulphuretted hydrogen, &c.), NaHO + 2H_{2}R´´ = 14; NaHO + H_{2}R´´ = 14; 2NaHO + H_{2}R´´ = 28; _n_NaHO + H_{2}R´´ = 28; that is, with an excess of acid (NaHO + 2H´_{2}R´´) 14 thousand units of heat are developed, and with an excess of alkali 28. When phosphoric acid is taken (but not all tribasic acids--for instance, not citric) the general character of the phenomenon is similar to the preceding, namely, NaHO + 2H_{3}PO_{4} = 14·7; NaHO + H_{3}PO_{4} = 14·8; 2NaHO + H_{3}PO_{4} = 27·1; 3NaHO + H_{3}PO_{4} = 34·0; 6NaHO + H_{3}PO_{4} = 35·3; or, in general terms, NaHO + _n_H_{3}PO_{4} = 14 (approximately) and _n_NaHO + H_{3}PO_{4} = 35 and not 42, which shows a peculiarity of phosphoric acid. In the case of energetic acids, when one equivalent (23 grams) of sodium (in the form of hydroxide) replaces one equivalent (1 gram) of hydrogen (with the formation of water and in dilute solutions), 14,000 heat units are evolved; and this is true for phosphoric acid when in H_{3}PO_{4}, Na or Na_{2} replaces H or H_{2}, but when Na_{3} replaces H_{3} less heat is developed. This will be seen from the following scheme based on the preceding figures: H_{3}PO_{4} + NaHO = 14·8; NaH_{2}PO_{4} + NaHO = 12·3; Na_{2}HPO_{4} + NaHO = 5·9; with Na_{3}PO_{4} + NaHO, a very small amount of heat is evolved, as may be judged from the fact that Na_{3}PO_{4} + 3NaHO = 1·3, but still heat is evolved. It must be supposed that in acting on phosphoric acid in the presence of a large quantity of water, a certain portion of the sodium hydroxide remains as alkali uncombined with the acid. Thus, on increasing the mass of the alkali, heat is still evolved, and a fresh interchange between Na and H takes place. Hence water shows a decomposing action on the alkali phosphates. The same decomposing action of water is seen, but to a less extent, with Na_{2}HPO_{4}, as may be judged both from the reactions of this salt and from the amount of heat developed by NaH_{2}PO_{4} with NaHO. Such an explanation is in accordance with many facts concerning the decomposition of salts by water already known to us. Recent researches made by Berthelot and Louguinine have confirmed the above deductions made by me in the first edition (1871) of this work. At the present time views of this nature are somewhat generally accepted, although they are not sufficiently strictly applied in other cases. As regards PH_{3}O_{4} it may be said that: on the substitution of the first hydrogen this acid acts as a powerful acid (like HCl, HNO_{3}, H_{2}SO_{4}); on the substitution of the second hydrogen as a weaker acid (like an organic acid); and on the substitution of the third, as an alcohol, for instance phenol, having the properties of a feeble acid. Phosphoric anhydride, or any of its hydrates, when ignited with an excess of sodium hydroxide, carbonate, &c., forms normal or _trisodium orthophosphate_, Na_{3}PO_{4}, but when a solution of sodium carbonate is decomposed by orthophosphoric acid, only the salt Na_{2}HPO_{4} is formed; and when an excess of sodium chloride is ignited with orthophosphoric acid, hydrochloric acid is evolved, and the acid salt H_{2}NaPO_{4} alone is formed. These facts clearly indicate the small energy of phosphoric acid with respect to the formation of the tri-metallic salt, which is seen further from the fact that the salt Na_{3}PO_{4} has an alkaline reaction, decomposes in the presence of water and carbonic acid, forming Na_{2}HPO_{4}, corrodes glass vessels in which it is boiled or evaporated, just like solutions of the alkalis, disengages, like them, ammonia from ammonium chloride, and crystallises from solutions, as Na_{3}PO_{4},12H_{2}O, only in the presence of an excess of alkali. At 15° the crystals of this salt require five parts of water for solution; they fuse at 77°. _Disodium orthophosphate_, or common sodium phosphate, Na_{2}HPO_{4}, is more stable both in solution and in the solid state. As it is used in medicine and in dyeing, it is prepared in considerable quantities, most frequently from the impure phosphoric acid obtained by the action of sulphuric acid on bone ash. The solution thus formed--which contains, besides phosphoric and sulphuric acids, salts of sodium, calcium, and magnesium--is heated, and sodium carbonate added so long as carbonic anhydride is disengaged. A precipitate is formed containing the insoluble salts of magnesium and calcium, whilst the solution contains sodium phosphate, Na_{2}HPO_{4}, with a small quantity of other salts, from which it may be easily purified by crystallisation. At the ordinary temperature its solutions, especially in the presence of a small amount of sodium carbonate, give finely-formed inclined prismatic crystals, Na_{2}HPO_{4},12H_{2}O; when the crystallisation takes place above 30° they only contain 7H_{2}O. The former crystals even lose a portion of their water of crystallisation at the ordinary temperature (the salt effloresces), and form the second salt with 7H_{2}O; whilst under the receiver of an air-pump and over sulphuric acid they also part with this water.[17] When ignited they lose the last molecule of water of constitution, and give sodium pyrophosphate, Na_{4}P_{2}O_{7}. [17] Na_{2}HPO_{4},12H_{2}O has a sp. gr. 1·53. Poggiale determined the solubility in 100 parts of water (1) of the anhydrous ortho-salt Na_{2}HPO_{4}, and (2) of the corresponding pyro-salt Na_{4}P_{2}O_{7}:-- 0° 20° 40° 80° 100° I. 1·5 11·1 30·9 81 108 II. 3·2 6·2 13·5 30 40 At temperatures of 20° to 100° the ortho-salt is so very much less soluble that this difference alone already indicates the deeply-seated alteration in constitution which takes place in the passage from the ortho- to the pyro-salts. _Monosodium orthophosphate_, NaH_{2}PO_{4}, crystallises with one equivalent of water; its solution has an acid reaction. At 100° the salt only loses this water of crystallisation, and at about 200° it parts with all its water, forming the metaphosphate NaPO_{3}. It is prepared from ordinary sodium phosphate by adding phosphoric acid until the solution does not give a precipitate with barium chloride, and then evaporating and crystallising the solution. The solution of this salt does not absorb carbonic anhydride, and does not give a precipitate with salts of calcium, barium, &c.[18] [18] The _ammonium orthophosphates_ resemble the sodium salts in many respects, but the instability of the di- and tri-metallic salts is seen in them still more clearly than in the sodium salts; thus (NH_{4})_{3}PO_{4}, and even (NH_{4})_{2}HPO_{4}, lose ammonia in the air (especially when heated, even in solutions); NH_{4}H_{2}PO_{4} alone does not disengage ammonia and has an acid reaction. The crystals of the first salt contain 3H_{2}O, and are only formed in the presence of an excess of ammonia; both the others are anhydrous, and may be obtained like the sodium salts. When ignited these salts leave metaphosphoric acid behind; for example, (NH_{4})_{2}HPO_{4} = 2NH_{3 + H_{2}O + HPO_{3}. Ammonia also enters into the composition of many double phosphates. Ammonium sodium orthophosphate, or simply phosphate, NH_{4}NaHPO_{4},4H_{2}O, crystallises in large transparent crystals from a mixture of the solutions of disodium phosphate and ammonium chloride (in which case sodium chloride is obtained in the mother liquid), or, better still, from a solution of monosodium phosphate saturated with ammonia. It is also formed from the phosphates in urine when it ferments. This salt is frequently used in testing metallic compounds by the blow-pipe, because when ignited it leaves a vitreous metaphosphate, NaPO_{3}, which, like borax, dissolves metallic oxides, forming characteristic tinted glasses. When a solution of trisodium phosphate is added to a solution of a magnesium salt it gives a white precipitate of the normal orthophosphate Mg_{2}(PO_{4})_{2},7H_{2}O. If the trisodium salt be replaced by the ordinary salt, Na_{2}HPO_{4}, a precipitate is also formed, and MgHPO_{4},7H_{2}O is obtained. It might be thought that the normal salt Mg_{3}(PO_{4})_{2} would be precipitated if disodium phosphate was added to ammonia and a salt of magnesium, but in reality _ammonium magnesium orthophosphate_, MgNH_{4}PO_{4},6H_{2}O, is precipitated as a crystalline powder, which loses ammonia and water when ignited, and gives a pyrophosphate, Mg_{2}P_{2}O_{7}. This salt occurs in nature as the mineral struvite, and in various products of the changes of animal matter. If we consider that the above salt parts with ammonia with difficulty, and that the corresponding salt of sodium is not formed under the same conditions (MgNaPO_{4},9H_{2}O is obtained by the action of magnesia on disodium phosphate), if we turn our attention to the fact that the salts of calcium and barium do not form double salts as easily as magnesium, and remember that the salts of magnesium in general easily form double ammonium salts, we are led to think that this salt is not really a normal, but an acid salt, corresponding with Na_{2}HPO_{4}, in which Na_{2} is replaced by the equivalent group NH_{3}Mg. The common normal _calcium phosphate_, Ca_{3}(PO_{4})_{2}, occurs in minerals, in animals, especially in bones, and also probably in plants, although the ash of many portions of plants, as a rule, contains less lime than the formation of the normal salt requires. Thus 100 parts of the ash (from 5,000 parts of grain) of rye grain contain 47·5 of phosphoric anhydride and only 2·7 of lime, and even the ash of the whole of the rye (including the straw) contains twice as much phosphoric anhydride as lime, and the normal salt contains almost equal weights of these substances. Only the ash of grasses, and especially of clover, and of trees, contains in the majority of cases more lime than is required for the formation of Ca_{3}P_{2}O_{8}. This salt, which is insoluble in water, dissolves even in such feeble acids as acetic and sulphurous, and even in water containing carbonic acid. The latter fact is of immense importance in nature, since by reason of it rain water is able to transfer the calcium phosphates in the soil into solutions which are absorbed by plants. The solubility of the normal salt in acids takes place by virtue of the formation of an acid salt, which is evident from the quantity of acid required for its solution, and more especially from the fact that the acid solutions when evaporated give crystalline scales of the acid calcium phosphate, CaH_{4}(PO_{4})_{2}, soluble in water. This solubility of the acid salt forms the basis of the treatment by acids of bones, phosphorites, guano, and other natural products containing the normal salt and employed for fertilising the soil. The perfect decomposition requires at least 2H_{2}SO_{4} to Ca_{3}(PO_{4})_{2}, but in reality less is taken, so that only a portion of the normal salt is converted into the acid salt. Hydrochloric acid is sometimes used. (In practice such mixtures are known as _superphosphates_). Certain experiments, however, show that a thorough grinding, the presence of organic, and especially of nitrogenous, substances, and the porous structure of some calcium phosphates (for example, in burnt bones), render the treatment of phosphoric manures by acids superfluous--that is, the crop is not improved by it. As a hydrate, orthophosphoric acid should be expressed, after the fashion of other hydrates, as containing three water residues (hydroxyl groups), _i.e._ as PO(OH)_{3}. This method of expression indicates that the type PX_{5}, seen in PH_{4}I, is here preserved, with the substitution of X_{2} by oxygen and X_{3} by three hydroxyl groups. The same type appears in POCl_{3}, PCl_{5}, PF_{5}, &c. And if we recognise phosphoric acid as PO(OH)_{3}, we should expect to find three anhydrides corresponding with it: (1) [PO(OH)_{2}]_{2}O, in which two of the three hydroxyls are preserved; this is pyrophosphoric acid, H_{4}P_{2}O_{7}. (2) PO(OH)O, where only one hydroxyl is preserved. This is metaphosphoric acid. (3) (PO)_{2}O_{3} or P_{2}O_{5}, that is, perfect phosphoric anhydride. Therefore, _pyro- and metaphosphoric acids are imperfect anhydrides_ (or anhydro-acids) _of orthophosphoric acid_.[19] [19] In this sense the ortho-acid itself might be regarded as an anhydro-acid, counting P(HO)_{5} as the perfect hydrate, if PH_{5} existed; but as in general the normal hydrates correspond with the existing hydrogen compounds with the addition of up to 4 atoms of oxygen, therefore PH_{3}O_{4} is the normal acid, just as SH_{2}O_{4} and ClHO_{4}; while NHO_{3}, CH_{2}O_{3} are meta-acids, or higher normal acids (NH_{3}O_{4} and CH_{4}O_{4}) with the loss of a molecule of water. In order to see the relation between the ortho-, pyro-, and metaphosphoric acids, the first thing to remark in them is that the anhydride P_{2}O_{5} is combined with 3, 2, and 1 molecules of water. In the absence of data for the molecular weight of ortho- and pyrophosphoric acids it is necessary to mention that all existing data for metaphosphoric acid indicate (Note 21) that its molecule is much more complex and contains at least H_{3}P_{3}O_{9} or H_{6}P_{6}O_{18}. The explanation of the problems which here present themselves can, it seems to me, be only looked for after a detailed study of the phenomena of the polymerisations of mineral substances, and of those complex acids, such as phosphomolybdic, which we shall hereafter describe (Chapter XXI.) A similar instance is exhibited in the solubility of hydrate of silica (produced by the action of silicon fluoride on water) in fused metaphosphoric acid, with the formation, on cooling, of an octahedral compound (sp. gr., 3·1) containing SiO_{2},P_{2}O_{5}. A certain indication (but no proof) that ordinary orthophosphoric acid is polymerised is given by Staudenmaier (1893), who obtained a salt, K_{5}H_{4}P_{3}O_{12}, by the action of a solution of KH_{2}PO_{4} upon K_{2}CO_{3}; and a compound, KH_{3}P_{2}O_{8}, corresponding to the doubled molecule of H_{3}PO_{4}, by the action of KH_{2}PO_{4} upon H_{3}PO_{4} itself. _Pyrophosphoric acid_, H_{4}P_{2}O_{7}, is formed by heating orthophosphoric acid to 250° when it loses water.[19 bis] Its normal salts are formed by igniting the dimetallic salts of orthophosphoric acid of the types HM_{2}PO_{4}. Thus from the disodium salt we obtain sodium pyrophosphate, Na_{4}P_{2}O_{7} (it crystallises from water with 10H_{2}O, is very stable, fuses when heated, has an alkaline reaction, and does not form ortho-salts when its solution is boiled): and from the monosodium salt NaH_{2}PO_{4} the acid salt Na_{2}H_{2}P_{2}O_{7} (easily soluble in water) is formed; this has an acid reaction, and when ignited further gives the meta-salt.[20] [19 bis] According to Watson (1893) the ortho-acid is partially transformed into the pyro-acid at 230°, whilst at 260° the latter begins to volatilise. At 300° the meta-acid only is formed. [20] The method of preparation of the acid itself consists in converting the sodium salt, Na_{4}P_{2}O_{7}, by double decomposition with water and a salt of lead, into insoluble lead pyrophosphate, Pb_{2}P_{2}O_{7}, which is then suspended in water and decomposed by sulphuretted hydrogen; lead sulphide is thus precipitated, and pyrophosphoric acid remains in solution. This solution cannot be heated, or the pyro-acid will pass into the ortho-, but must be evaporated under the receiver of an air-pump. It concentrates to a syrup and crystallises, and when ignited in this form loses water, and forms metaphosphoric acid. It resembles orthophosphoric acid in many respects; its salts with the alkalis are also soluble, and the others insoluble in water but soluble in acids. When heated in solution with acid it gives orthophosphoric acid, as well as when fused with an excess of alkali. Witt heated ammonium chloride with phosphoric acid (hydrochloric acid was evolved), ignited the residue to drive off ammonia, and obtained pyrophosphoric acid in the residue. _Metaphosphoric acid_, HPO_{3} (the analogue of nitric acid), is formed by the ignition of the pyro- and ortho-acids (or, better, of their ammonium salts), as a vitreous, hygroscopic, fused mass (glacial phosphoric acid, _acidum phosphoricum glaciale_), soluble in water and volatilising without decomposition. It is also formed in the first slow action of cold water on the anhydride, but metaphosphoric acid gradually changes into the ortho-acid when its solution is boiled, or when it is kept for any length of time, especially in the presence of acids.[21] [21] As when using phenolphthalein as an indicator in neutralising by an alkali metaphosphoric acid is monobasic, and orthophosphoric acid is bibasic, it is possible by means of this difference to follow the transition of meta- into orthophosphoric acid. Sabatier (1888) carried on an investigation of this nature, and found that the rate of transformation is dependent on the temperature, and is subject to the general laws of the rate of chemical transformations which belongs to physical chemistry. Metaphosphoric acid has a particular interest in respect to the variations to which its salts are subject. The metaphosphates are formed by the ignition of the acid orthophosphates, MH_{2}PO_{4}, or MNH_{4}HPO_{4}, or of the acid pyrophosphates, M_{2}H_{2}P_{2}O_{7}, or M_{2}(NH_{4})_{2}P_{2}O_{7}, water and ammonia being given off in the process. The properties of the metaphosphates, which have a similar composition to nitrates--for instance, NaPO_{3}, or Ba(PO_{3})_{2}--vary according to the duration of the ignition to which the ortho-, or pyrophosphates from which they are prepared have been subjected. When the salts NaH_{2}PO_{4} or NH_{4}NaHPO_{4} are strongly ignited, a salt NaPO_{3} is formed, which deliquesces in the air, and gives a gelatinous precipitate with salts of the alkaline earths. But, as Graham (in 1830-40), and many others, especially Fleitmann and Henneberg (in 1840-50), and Tamman (in the nineties), observed, under other conditions the salts of the same composition acquire other properties. The above chemists recognise five polymeric forms of metaphosphates, (HPO_{3})_{_n_}. We will follow the nomenclature and researches of Fleitmann. _Monometaphosphoric acid._ The salts are distinguished for their insolubility in water; even the salts NaPO_{3}, KPO_{3}, are insoluble. They are obtained by igniting the monometallic orthophosphates--for example, RH_{2}PO_{4}--up to the temperature at which all water is evolved (316°), but not to fusion. No double salts are known. _Dimetaphosphoric acid_, on the contrary, easily forms double salts--for example, KNaP_{2}O_{6}, and also the copper potassium salt, &c. The copper salt is obtained by evaporating a solution of copper oxide in orthophosphoric acid. A blue ortho-salt, CuRHO_{4}, first separates from the solution, then a light-blue pyro-salt, Cu_{2}P_{2}O_{7}; and above 350°, when metaphosphoric acid itself begins to volatilise, the dimetaphosphate, CuP_{2}O_{6}, is formed. The residue is washed with water, and decomposed with a hot solution of sodium sulphide, when the sodium salt, Na_{2}P_{2}O_{6}, is obtained in solution. This salt, when evaporated with alcohol, gives crystals containing 2 mol. H_{2}O, which, however, retain their solubility (in 7 parts of water) after the water is driven off at 100°. When fused, these crystals give a deliquescent salt (hexa-metaphosphate). The solution of the salt has a neutral reaction, which only after prolonged boiling becomes acid, owing to the formation of orthophosphate, NaH_{2}PO_{4}. The soluble salts of dimetaphosphoric acid give the insoluble silver salt, Ag_{2}P_{2}O_{6}, with silver nitrate, and a precipitate of BaP_{2}O_{6}2H_{2}O with barium chloride. _Trimetaphosphoric acid_ is obtained as the sodium salt Na_{3}P_{3}O_{9} when any other metaphosphate of sodium is fused and _slowly_ cooled, then dissolved in a slight excess of warm water, and the resultant solution evaporated. The crystals contain 6 mol. H_{2}O, and dissolve in four parts of water. An acid reaction is only obtained, as with the preceding salt, after prolonged boiling with water. The acid is a true analogue of nitric acid, because _all its metallic salts are soluble_. _Hexametaphosphoric acid._ Fleitmann so named the ordinary metaphosphoric acid (glacial) which attracts moisture. The deliquescent sodium salt is obtained, like the trimetaphosphate, only by _rapid_ cooling. It is also formed by fusing silver oxide with an excess of phosphoric acid. The sodium salt is soluble in water, and gives viscous, elastic precipitates with salts of Ba, Ca, and Mg. Lubert (1893) obtained salts of Ag, Pb, &c. Jawein and Thillot (1889), who investigated the sodium salts of metaphosphoric acid by Raoult's method, came to the conclusion that the salts of di- and tri-metaphosphoric acid behave in such a manner that their molecule must be represented as non-polymerised NaPO_{3}, whilst those of hexametaphosphoric acid behave as (NaPO_{3})_{4}. At all events, the series of salts which Fleitmann and Henneberg regard as monometaphosphates--_i.e._ as non-polymerised--are most probably the most polymerised, because they are insoluble. According to Tamman's researches, vitreous metaphosphoric acid contains a mixture consisting chiefly of two varieties, differing in the solubility and degree of stability of their salts. The least stable corresponds to Fleitmann's hexa-acid, and gives three isomeric salts. Tamman came to the conclusion that there exist polymers also in the form of penta-, ortho-, and deca-metaphosphoric acids. Without going into details upon this subject, I do not think it superfluous to point out that the undoubted capability of metaphosphoric acid to polymerise should be connected with its faculty of combining with water, whilst the degree of polymerisation and the number of polymeric forms cannot yet be considered as sufficiently explained. In order to see the relation between phosphoric acid and the lower acids of phosphorus, it is simplest to imagine the substitution of hydroxyl in H_{3}PO_{4} or PO(OH)_{3} by hydrogen. Then from orthophosphoric acid, PO(OH)_{3}, we shall obtain phosphorous acid, POH(OH)_{2}, and hypophosphorous acid, POH(OH); and, furthermore, phosphorous acid should be bibasic if orthophosphoric acid was tribasic, and hypophosphorous acid should be monobasic. This conclusion[21 bis] is, in fact, true, and hence all the acids of phosphorus may be referred to one common type, PX_{5}, whose representatives are PH_{4}I and PCl_{5}, POCl_{3}, PCl_{2}F_{3}, &c. [21 bis] The bibasity of H_{3}PO_{3}, established by Würtz, has been proved by many direct experiments (see, for instance, Note 22), among which we may mention that Amat (1892) took a mixture of the aqueous solutions of Na_{2}HPO_{3} and NaHO and added absolute alcohol to it. Two layers were formed; the upper, alcoholic, contained all the excess of NaHO, whilst the lower only contained the salt Na_{2}HPO_{3}, which was therefore unable to react with the excess of NaHO. Amat also obtained NaH_{2}PO_{3} by saturating H_{3}PO_{3} with soda until he obtained a neutral reaction with methyl-orange. The replacement of one atom of H by sodium here, as in phosphoric acid (Note 16), gives more heat than the replacement of the second atom. For the third atom there is no formation of a salt, and therefore no evolution of heat. The monometallic salts--for example, NaH_{2}PO_{3}--or the ammonia salts, when heated to 160°, give, as Amat had previously shown, a salt of bibasic pyrophosphorous acid, Na_{2}H_{2}P_{2}O_{5}. _Phosphorous acid_, PH_{3}O_{3}, is generally obtained from phosphorus trichloride, PCl_{3}, by the action of water: PCl_{3} + 3H_{2}O = 3HCl + PH_{3}O_{3}. Both acids formed are soluble in water, but are easily separated, because hydrochloric acid is volatile whilst phosphorous acid volatilises with difficulty, and if a small amount of water be originally taken the hydrochloric acid nearly all passes off directly. Concentrated solutions of phosphorous acid give crystals of H_{3}PO_{3}, which fuse at 70°, attract moisture from the air, and deliquesce when ignited, giving phosphine and phosphoric acid,[22] and are oxidised into orthophosphoric acid by many oxidising agents. In its salts only two hydrogen atoms are replaced by metals (Würtz); the salts of the alkaline metals are soluble, and give precipitates with salts of the majority of other metals. [22] Phosphorous acid, when subjected to the action of nascent hydrogen (zinc and sulphuric acid), evolves phosphine, and when boiled with an excess of alkali it evolves hydrogen (PH_{3}O_{3} + 3KHO = PK_{3}O_{4} + 2H_{2}O + H_{2}); owing to its liability to oxidation, it is a reducing agent--for instance, it reduces cupric chloride to cuprous chloride, and precipitates silver from the nitrate and mercury from its salts. These reactions are perhaps connected with the fact that in this acid one atom of hydrogen should be considered as in the same condition as in phosphuretted hydrogen, which is expressed by the formula PHO(OH)_{2}, if we represent it as PH_{4}X, with the substitution of two of the hydrogen atoms by oxygen and of HX by two of hydroxyl. The direct passage of phosphorous chloride into phosphorous acid would, however, indicate that all the three atoms of hydrogen in it occur in the form of hydroxyl, because no difference is known between the three atoms of chlorine in PCl_{3}--they all react alike, as a rule. However, Menschutkin, by acting on alcohol, C_{2}H_{5}OH, with phosphorous chloride, obtained hydrochloric acid and a substance P(C_{2}H_{5}O)Cl_{2}, and from it by the action of bromine he obtained ethyl bromide, C_{2}H_{5}Br, and a compound PBrOCl_{2}, which proves, to a certain extent, the existence of a difference between the three atoms of chlorine in phosphorous chloride. If we turn our attention to the formation of phosphine by the ignition of phosphorous acid, we see that 4PH_{3}O_{3} only evolve 3H in the form of PH_{3}, and therefore the residue--that is, 3PH_{3}O_{4}--will still contain one hydrogen of the same nature as in phosphine, because in 4PH_{3}O_{3} we should recognise four such hydrogens as in phosphine. We arrive at the same conclusion by examining the decomposition of hypophosphorous acid, 2PH_{3}O_{2} = PH_{3} + PH_{3}O_{4}. In the two molecules of the monobasic hypophosphorous acid taken, there are only two atoms of hydrogen replaceable by metals, whilst in the molecule of the resultant phosphoric acid there are three. Perhaps relations of this nature determine the relative stability of the dimetallic salts of orthophosphoric acid. The monobasic _hypophosphorous acid_, PH_{3}O_{2}, gives salts PH_{2}O_{2}Na, (PH_{2}O_{2})_{2}Ba, &c.; the two remaining atoms of hydrogen (which exist in the same form as in phosphine, PH_{3}) are not replaceable by metals, and this determines the property of these salts of evolving phosphuretted hydrogen when heated (especially with alkalis). In acting on substances liable to reduction it is this hydrogen which acts, and, for example, _reduces_ gold and mercury from the solutions of their salts, or converts cupric into cuprous salts. In all these instances the hypophosphorous acid is converted into phosphoric acid. Under the action of zinc and sulphuric acid it gives phosphine, PH_{3}. Nevertheless, neither hypophosphorous acid nor its dry salts absorb oxygen from the air. The salts of hypophosphorous acid are more soluble than those of the preceding acids of phosphorus. Thus the sodium salt PNaH_{2}O_{2} does not give a precipitate with barium chloride, and the salts of calcium, barium, and many other metals are soluble.[23] The hypophosphites are prepared by boiling an alkali with phosphorus so long as phosphuretted hydrogen is evolved. The acid itself is obtained from barium hypophosphite (prepared in the same manner by boiling phosphorus in baryta water), by decomposing its solution with sulphuric acid. By concentration of the solution of hypophosphorous acid (it must not be heated above 130°, at which temperature it decomposes) a syrup is formed which is able to crystallise. In the solid state hypophosphorous acid fuses at +17°, and has the properties of a clearly defined acid. [23] Calcium hypophosphite is used in medicine. According to Cavazzi, a mixture of sodium hypophosphite, NaH_{2}PO_{2}, and sodium nitrate explodes violently. The types PX_{3} and PX_{5}, which are evident for the hydrogen and oxygen compounds of phosphorus, are most clearly seen in its halogen compounds,[24] to the consideration of which we will proceed, fixing our attention more especially on the chlorine compounds, as being the most important from the historical, theoretical, and practical point of view. [24] Fluorine and bromine give PX_{3} and PX_{5}, like chlorine. With respect to iodine PI_{5} is, in a chemical sense, a very unstable substance, and generally _phosphorus tri-iodide_ only is formed (from yellow or red phosphorus and iodine in the requisite proportions). It is a red crystalline substance, fuses at 55°, is easily decomposed by water, forming phosphorous and hydriodic acids, and when heated it evolves iodine vapours and forms phosphorus di-iodide, PI_{2}. This substance may be obtained in the same manner as the preceding by taking a smaller proportion of iodine (8 parts of iodine to 1 part of phosphorus, whilst the tri-iodide requires 12·3); it also forms red crystals, which melt at 110°. When decomposed by water it not only gives phosphorous and hydriodic acids, but also phosphine and a yellow substance (a lower oxide of phosphorus). In its composition di-iodide of phosphorus corresponds with liquid phosphuretted hydrogen, PH_{2}, and probably its molecular weight is much higher: P_{2}I_{4} or P_{3}I_{6}, &c. As the iodine compounds of phosphorus give hydriodic and phosphorous acids with water, and as both these substances are reducing agents in the presence of water (and hydrates), iodide of phosphorus also acts as a reducing agent. Phosphorus burns in chlorine, forming phosphorous chloride, PCl_{3}, and with an excess of chlorine, phosphoric chloride, PCl_{5}. The oxychloride, POCl_{3}, as the simplest chloranhydride according to the type PX_{5}, and also phosphoric chloride, correspond with orthophosphoric acid, PO(OH)_{3}, while phosphorous chloride, PCl_{3}, corresponds with phosphorous acid and the type PX_{3}. Phosphoric oxychloride, POCl_{3}, is a colourless liquid, boiling at 110°. Phosphorus trichloride is also a colourless liquid, boiling at 76°,[25] whilst phosphoric chloride is a solid yellowish substance, which volatilises without melting at about 168°. They are all heavier than water, and form types of the _chloranhydrides_ or chlorine compounds of the non-metallic elements whose hydrates are acids, just as NaCl or BaCl_{2} are types of halogen metallic salts. [25] In a liquid state the density of phosphorous chloride at 10° = 1·597, and therefore its molecular volume = 137·5/1·597 = 86·0, and that of phosphorus oxychloride is equal to 153·5/1·693 = 90·7; hence the addition of oxygen has produced considerable increase in volume, just as in the conversion of sulphur dichloride, SCl_{2}, into sulphuryl chloride, SOCl_{2}, the volume changes from 64 to 71. It is the same with the boiling-points; phosphorus trichloride boils at 70°, the oxychloride at 100°, sulphur dichloride at 64°, and sulphuryl chloride at 78°--that is, the addition of oxygen raises the boiling points. _The vapour density_ of phosphorus trichloride and oxychloride corresponds with their formulæ (Cahours, Würtz)--namely, is equal to half the molecular weight referred to hydrogen. But it is not so with phosphorus pentachloride. Cahours showed that the vapour density of phosphorus pentachloride referred to air = 3·65, to hydrogen = 52·6, whilst according to the formula PCl_{5} it should be = 104·2. Hence this formula corresponds with four, and not with two, molecules. This shows that the vapour of phosphoric chloride contains two and not one molecule, that in a state of vapour it splits up, like sal-ammoniac, sulphuric acid, &c. The products of disruption must here be phosphorous chloride, PCl_{3}, and chlorine, Cl_{2}, bodies which easily re-form phosphoric chloride, PCl_{5}, at a lower temperature. This decomposition of phosphoric chloride in its conversion into vapour is confirmed by the fact that the vapour of this almost colourless substance shows the greenish-yellow colour proper to chlorine. This dissociation of phosphoric chloride has been considered by some chemists as a sign that phosphorus, like nitrogen, does not give volatile compounds of the type PX_{5}, and that such substances are only obtained as unstable molecular compounds which break up when distilled; for example, PH_{3},HI, PCl_{3},Cl_{2}, NH_{3},HCl, &c. To prove that the molecule PCl_{5} actually exists, Würtz in 1870 observed that when mixed with the vapour of phosphorous chloride the vapour of phosphoric chloride distils over (from 160° to 190°) perfectly colourless, and has a density which is really near to the formula--namely, to 104--and the same density was determined for the pentachloride in an atmosphere of chlorine. Hence at low temperatures and in admixture with one of the products of dissociation, there is no longer that decomposition which occurs at higher temperatures--that is, we have here a case of dissociation proceeding at moderate temperatures. An important proof in favour of the type PX_{5} is exhibited by phosphorus pentafluoride PF_{5}, obtained by Thorpe as a colourless gas which only corrodes glass after the lapse of time; it may be kept over mercury, and has a normal density. It is formed when liquid arsenic trifluoride, AsF_{3}, is added to phosphoric chloride surrounded by a freezing mixture: 3PCl_{5} + 5AsF_{3} = 3PF_{5} + 5AsCl_{3}. In general, fluorine and phosphorus give stable compounds: PF_{3}, POF_{3}, and PF_{5}, as would be expected from the fact that in passing from Cl to I (_i.e._ as the atomic weight of the halogen increases) the stability of the compounds with P and the tendency to give PX_{5} (Note 24) decreases. _Phosphorus trifluoride_ is obtained by heating a mixture of ZnF_{2} and PBr_{3}, by the action of AsF_{3} upon PCl_{3}, by heating phosphide of copper with PbF_{2}, &c. It is a strong-smelling gas, which liquefies at -10° under a pressure of 40 atmospheres, giving a colourless liquid. It dissolves easily in (is absorbed by, reacts with) water, and acts upon glass; when mixed with Cl_{2} it combines with it (Poulenc, 1891), forming PCl_{2}F_{3}, a colourless gas of normal density, which is transformed into a liquid at 8°, decomposes into PF_{3} + Cl_{2} at 250°, and, with a small amount of water, gives _oxy-fluoride_ of phosphorus, POF_{3} (with a large amount of water it gives PH_{3}O_{4}), which Moissan (1891) obtained by the action of dry HF upon P_{2}O_{5}, and Thorpe and Tutton (1890) by heating a mixture of cryolite and P_{2}O_{5}. It is a gas of normal density, like PF_{3}, and was obtained by Moissan by the action of fluorine upon PF_{3} (PSF_{3}, _see_ Chapter XX., Note 20). Thus the forms PX_{3} and PX_{5} not only exist in many solid and non-volatile substances, but also as vapours. If a piece of phosphorus be dropped into a flask containing chlorine, it burns when touched with a red-hot wire, and combines with the chlorine. If the phosphorus be in excess, liquid _phosphorus trichloride_, PCl_{3}, is always formed, but if the chlorine be in excess the solid pentachloride is obtained. The trichloride is generally prepared in the following manner. Dry chlorine (passed through a series of Woulfe's bottles containing sulphuric acid) is led into a retort containing sand and phosphorus. The retort is heated, the phosphorus melts, spreads through the sand, and gradually forms the trichloride, which distils over into a receiver, where it condenses. _Phosphoric chloride_ or _phosphorus pentachloride_, PCl_{5}, is prepared by passing dry chlorine into a vessel containing phosphorus trichloride (purified by distillation). Phosphorous chloride combines directly with oxygen, but more rapidly with ozone or with the oxygen of potassium chlorate (3PCl_{3} + KClO_{3} = 3POCl_{3} + KCl), forming _phosphorus oxychloride_, POCl_{3} (Brodie). This compound is also formed by the first action of water on phosphoric chloride; for example, if two vessels, one containing phosphoric chloride and the other water, are placed under a bell jar, after a certain time the crystals of the chloride disappear and hydrochloric acid passes into the water. The aqueous vapour acts on the pentachloride, and the following reaction occurs: PCl_{5} + H_{2}O = POCl_{3} + 2HCl, the result being that liquid phosphorus oxychloride is found in one vessel, and a solution of hydrochloric acid in the other. However, an excess of water directly transforms phosphoric chloride into orthophosphoric acid, PCl_{5} + 4H_{2}O = PH_{3}O_{4} + 5HCl,[26] since POCl_{3} reacts with water (3H_{2}O), forming 3HCl and phosphoric acid PO(OH)_{3}. [26] Phosphorus oxychloride is obtained by the action of phosphoric chloride on hydrates of acids (because alkalis decompose phosphorus oxychloride), according to the equation PCl_{5} + RHO = POCl_{3} + RCl + HCl, where RHO is an acid. The reaction only proceeds according to this equation with monobasic acids, but then RCl is volatile, and therefore a mixture is obtained of two volatile substances, the acid chloride and phosphorus oxychloride, which are sometimes difficult to separate; whilst if the hydrate be polybasic the reaction frequently proceeds so that an anhydride is formed: RH_{2}O_{2} + PCl_{5} = RO + POCl_{3} + 2HCl. If the anhydride be non-volatile (like boric), or easily decomposed (like oxalic), it is easy to obtain pure oxychloride. Thus phosphorus oxychloride is often prepared by acting on boric or oxalic acid with phosphoric chloride. It is also formed when the vapour of phosphoric chloride is passed over phosphoric anhydride, P_{2}O_{5} + 3PCl_{5} = 5POCl_{3}. This forms an excellent example in proof of the fact that the formation of one substance from two does not necessarily show that the resultant compound contains the molecules of these substances in its molecule. But other oxychlorides of phosphorus are also formed by the interaction of phosphoric anhydride and chloride; thus at 200° the chloranhydride, PO_{2}Cl, or chloranhydride of metaphosphoric acid, is formed (Gustavson). The chloranhydride of pyrophosphoric acid, P_{2}O_{3}Cl_{4}, was obtained (Hayter and Michaelis), together with NOCl, &c., by the action of NO upon cold PCl_{3}, as a fuming liquid boiling at 210°. The above chlorine compounds serve not only as a type of the chloranhydrides, but also as a means for the preparation of other _acid chloranhydrides_. Thus the conversion of acids XHO into chloranhydrides, XCl, is generally accomplished by means of _phosphorus pentachloride_. This fact was discovered by Chancel, and adopted by Gerhardt as an important method for studying organic acids. By this means organic acids, containing, as we know, RCOOH (where R is a hydrocarbon group, and where carboxyl may repeat itself several times by replacing the hydrogen of hydrocarbon compounds), are converted into their chloranhydrides, RCOCl. With water they again form the acid, and resemble the chloranhydrides of mineral acids in their general properties. Since carbonic acid, CO(OH)_{2}, contains two hydroxyl groups, its perfect chloranhydride, COCl_{2}, _carbonic oxychloride_, _carbonyl chloride_ or _phosgene gas_, contains two atoms of chlorine, and differs from the chloranhydrides of organic acids in that in them one atom of chlorine is replaced by the hydrocarbon radicle RCOCl, if R be a monatomic radicle giving a hydrocarbon RH. It is evident, on the one hand, that in RCOCl the hydrogen is replaced by the radicle COCl, which is also able to replace several atoms of hydrogen (for example, C_{2}H_{4}(COCl)_{2} corresponds with the bibasic succinic acid); and, on the other hand, that the reactions of the chloranhydrides of organic acids will answer to the reactions of carbonyl chloride, as the reactions of the acids themselves answer to those of carbonic acid. Carbonyl chloride is obtained directly from dry carbon monoxide and chlorine[27] exposed to the action of light, and forms a colourless gas, which easily condenses into a liquid, boiling at +8°, specific gravity 1·43, and having the suffocating odour belonging to all chloranhydrides. Like all chloranhydrides, it is immediately decomposed by water, forming carbonic anhydride, according to the equation COCl_{2} + H_{2}O = CO_{2} + 2HCl, and thus expresses the type proper to all chloranhydrides of both mineral and organic acids.[28] [27] The direct action of the sun's rays, or of magnesium light, is necessary to start the reaction between carbonic oxide and chlorine, but when once started it will proceed rapidly in diffused light. An excess of chlorine (which gives its coloration to the colourless phosgene) aids the completion of the reaction, and may afterwards be removed by metallic antimony. Porous substances, like charcoal, aid the reaction. Phosgene may be prepared by passing a mixture of carbonic anhydride and chlorine over incandescent charcoal. Lead or silver chloride, when heated in a current of carbonic oxide, also partially form phosgene gas. Carbon tetrachloride, CCl_{4}, also forms it when heated with carbonic anhydride (at 400°), with phosphoric anhydride (200°), and most easily of all with sulphuric anhydride (2SO_{3} + CCl_{4} = COCl_{2} + S_{2}O_{5}Cl_{2}, this is pyrosulphuryl chloride). Chloroform, CHCl_{3}, is converted into carbonyl chloride when heated with SO_{2}(OH)Cl (the first chloranhydride of sulphuric acid); CHCl_{3} + SO_{3}HCl = COCl_{2} + SO_{2} + 2HCl (Dewar), and when oxidised by chromic acid. Among the reactions of phosgene we may mention the formation of urea with ammonia, and of carbonic oxide when heated with metals. [28] We are already acquainted with some of the chloranhydrides of the inorganic acids--for instance, BCl_{3}, and SiCl_{4}--and here we shall describe those which correspond with sulphuric acid in the following chapter. It may be mentioned here that when hydrochloric acts on nitric acid (aqua regia, Vol. I. p. 467) there is formed, besides chlorine, the oxychlorides NOCl and NO_{2}Cl, which may be regarded as chloranhydrides of nitric and nitrous acids (nitrogen chloride, Vol. I. p. 476). The former boils at -5°, the latter at +5°, the specific gravity of the first at -12° = 1·416, and at -18° = 1·433 (Geuther), and of the second = 1·3; the first is obtained from nitric oxide and chlorine, the second from nitric peroxide and chlorine, and also by the action of phosphoric chloride on nitric acid. If the gases evolved by aqua regia be passed into cold and strong sulphuric acid, they form crystals of the composition NHSO_{3} (like chamber crystals), which melt at 86°, and with sodium chloride form acid sodium sulphate and the oxychloride NOCl. This chloranhydride of nitric acid is termed _nitrosyl chloride_. _Cyanogen chloride_, CNCl, is the gaseous chloranhydride of cyanic acid; it is formed by the action of chlorine on aqueous mercury cyanide, Hg(CN)_{2} + 2Cl_{2} = HgCl_{2} + 2CNCl. When chlorine acts on cyanic acid, it forms not only this cyanogen chloride, but also polymerides of it--a liquid, boiling at 18°, and a solid, boiling at 190°. The latter corresponds with cyanuric acid, and consequently contains C_{3}N_{3}Cl_{3}. Details concerning these substances must be looked for in works on organic chemistry. In order to show the general method for the preparation of acid chloranhydrides, we will take that of acetic acid, CH_{3}·COOH, as an example. Phosphorus pentachloride is placed in a glass retort, and acetic acid poured over it; hydrochloric acid is then evolved, and the substance distilling over directly after is a very volatile liquid, boiling at 50°, and having all the properties of the chloranhydrides. With water it forms hydrochloric and acetic acids. The reaction here taking place may be explained thus: the substitution of the oxygen taken from the acetic acid (from its carboxyl) by two atoms of chlorine from the PCl_{5} should be as follows: CH_{3}·COOH + PCl_{5} = CH_{3}·COHCl_{2} + POCl_{3}. But the compound CH_{3}·COHCl_{2} does not exist in a free state (because it would indicate the possibility of the formation of compounds of the type CX_{6}, and carbon only gives those of the type CX_{4}); it therefore splits up into HCl and the chloranhydride CH_{3}·COCl. The general scheme for the reaction of phosphorus pentachloride with hydrates ROH is exactly the same as with water; namely, ROH with PCl_{5}, gives POCl_{3} + HCl + RCl--that is a chloranhydride.[28 bis] [28 bis] This reaction indeed proceeds very easily and completely with a number of hydroxides, if they do not react on hydrochloric acid and phosphorus oxychloride, which is the case when they have alkaline properties. When the hydroxide is bibasic and is present in excess, it not unfrequently happens that the elements of water are taken up: R(OH)_{2} + PCl_{5} = RO + 2HCl + POCl_{3}. The anhydride RO may then be converted into chloranhydride, RO + PCl_{5} = RCl_{2} + POCl_{3}--that is, phosphorus pentachloride brings about the substitution of O by Cl_{2}. Thus carbonyl chloride, COCl_{2}, boron chloride, 2BCl_{3}, and succinic chloride, C_{4}H_{4}O_{2}Cl_{2}, &c., are respectively obtained by the action of phosphoric chloride on carbonic, boric, and succinic anhydrides. Phosphorus pentachloride reacts in a similar manner on the aldehydes, RCHO, forming RCHCl_{2}, and on the chloranhydrides themselves--for example, with acetic chloride, CH_{3}.COCl (when heated in a closed tube), it forms a substance having the composition CH_{3}CCl_{3}. Phosphorus trichloride and oxychloride act in a similar manner to phosphoric chloride. When phosphorus trichloride acts on an acid, 3RHO + PCl_{3} = 3RCl + P(HO)_{3}. If a salt is taken, then by the action of phosphorus oxychloride a corresponding chloranhydride and salt of orthophosphoric acid are easily formed: 3R(KO) + POCl_{3} = 3RCl + PO(KO)_{3}. The chloranhydride RCl is always more volatile than its corresponding acid, and distils over before the hydrate RHO. Thus acetic acid boils at 117°, and its chloranhydride at 50°. Phosphoric and phosphorous acids are very slightly volatile, whilst their chloranhydrides are comparatively easily converted into vapour. The faculty of the chloranhydrides to react at the expense of their own chlorine determines their great importance in chemistry. For instance, suppose we require to know the molecular formula of some hydrate which does not pass into a state of vapour and does not give a chloranhydride with hydrochloric acid--that is, which has not any basic or alkaline properties; we must then endeavour to obtain this chloranhydride by means of phosphoric chloride, and it frequently happens that the corresponding chloranhydride is volatile. The resultant chloranhydride is then converted into vapour, and its composition is determined; and if we know its composition we are able to decide that of its corresponding hydrate. Thus, for example, from the formula of silicon chloride, SiCl_{4}, or of boron chloride, BCl_{3}, we can judge the composition of their corresponding hydrates, Si(HO)_{4}, B(HO)_{3}. Having obtained the chloranhydride RCl or RCl_{_n_}, it is possible by its means to obtain many other compounds of the same radicle R according to the equation MX + RCl = MCl + RX. M may be = H, K, Ag, or other metal. The reaction proceeds thus if M forms a stable compound with chlorine--for example, silver chloride, hydrochloric acid, and R, an unstable substance. Hence, a chloranhydride is frequently employed for the formation of other compounds of a given radicle; for instance, with ammonia they form amides RNH_{2}, and with salts ROK, with anhydrides R_{2}O, &c. Containing, as they do, chlorine, which easily reacts with hydrogen, phosphorus pentachloride, trichloride, and oxychloride enter into reaction with ammonia, and give a series of amide and nitrile compounds of phosphorus. Thus, for example, when ammonia acts on the oxychloride we obtain sal-ammoniac (which is afterwards removed by water) and an orthophosphoric triamide, PO(NH_{2})_{3}, as a white insoluble powder on which dilute acids and alkalis do not act, but which, when fused with potassium hydroxide, gives potassium phosphate and ammonia like other amides. When ignited, the triamide liberates ammonia and forms the nitrile PON, just as urea, CO(NH_{2})_{2}, gives off ammonia and forms the nitrile CONH. This nitrile, called _monophosphamide_, PON, naturally corresponds with metaphosphoric acid, namely, with its ammonium salt. NH_{4}PO_{3} - H_{2}O = PO_{2}·NH_{2}, an as yet unknown amide, and PO_{2}·NH_{2} - H_{2}O gives the nitrile PON. This relation is confirmed by the fact that PON, moistened with water, gives metaphosphoric acid when ignited. It is the analogue of nitrous oxide, NON. It is a very stable compound, more so than the preceding.[29] [29] The reaction of ammonia on phosphorus pentachloride is more complex than the preceding. This is readily understood: to the oxychloride, POCl_{3}, tere corresponds a hydrate PO(OH)_{3}, and a salt PO(NH_{4}O)_{3}, and consequently also an amide PO(NH_{2})_{3}, whilst the pentachloride, PCl_{5}, has no corresponding hydrate P(OH)_{5}, and therefore there is no amide P(NH_{2})_{5}. The reaction with ammonia will be of two kinds: either instead of 5 mol. NH_{3}, only 3 mol. NH_{3} or still less will act; _i.e._ PCl_{2}(NH_{2})_{3}, PCl_{3}(NH_{2})_{2}, &c. are formed; or else the pentachloride will act like a mixture of chlorine with the trichloride, and then as the result there will be obtained the products of the action of chlorine on those amides which are formed from phosphorus trichloride and ammonia. It would appear that both kinds of reaction proceed simultaneously, but both kinds of products are unstable, at all events complex, and in the result there is obtained a mixture containing sal-ammoniac, &c. The products of the first kind should react with water, and we should obtain, for example, PCl_{3}(NH_{2})_{2} + 2H_{2}O = 3HCl and PO(HO)(NH_{2})_{2}. This substance has not actually been obtained, but the compound PONH(NH_{2}) derived from it by elimination of the elements of water is known, and is termed _diphosphamide_; it is, however, more probable that it is a nitrile than an amide, because only amides contain the group NH_{2}. It is a colourless, stable, insoluble powder, which possibly corresponds with pyrophosphoric acid, more especially since when heated it evolves ammonia and gives and leaves phosphoryl nitride, PON--that is, the nitrile of metaphosphoric acid. The amide corresponding with the pyrophosphate P_{2}O_{3}(NH_{4}O)_{4} should be P_{2}O_{3}(NH_{2})_{4}, and the nitriles corresponding to the latter would be P_{2}O_{2}N(NH_{2})_{3}, P_{2}ON_{2}(NH_{2})_{2}, and P_{2}N_{3}(NH_{2}). The composition of the first is the same as that of the above diphosphamide. The third pyrophosphoric nitrile has a formula P_{2}N_{4}H_{2}, and this is the composition of the body known as _phospham_, PHN_{2} (in a certain sense this is the analogue of N_{3}H polymerised, Chapter VI.) Indeed, phospham has been obtained by heating the products of the action of ammonia on phosphoric chloride, as an insoluble and alkaline powder, which gives ammonia and phosphoric acid when subjected to the action of water. The same substance is obtained by the action of ammonium chloride on phosphoric chloride (PNCl_{2} is first formed, and reacts further with ammonia, forming phospham), and by igniting the mass which is formed by the action of ammonia on phosphorus trichloride. Formerly the composition of phospham was supposed to be PHN_{2}, now there is reason to think that its molecular weight is P_{3}H_{3}N_{6}. The above compounds correspond with normal salts, but nitriles and amides corresponding to acid salts are also possible, and they will be acids. For example, the amide PO(HO)_{2}(NH_{2}), and its nitrile, will be either PN(HO)_{2} or PO(HO)(NH), but at all events of the composition PNH_{2}O_{2}, and having acid properties. The ammonium salt of this _phosphonitrilic acid_ (it is called phosphamic acid), PNH(NH_{4})O_{2}, is obtained by the action of ammonia on phosphoric anhydride, P_{2}O_{5} + 4NH_3 = H_{2}O + 2PNH(NH_{4})O_{2}. A non-crystalline soluble mass is thus formed, which is dissolved in a dilute solution of ammonia and precipitated with barium chloride, and the resultant barium salt is then decomposed with sulphuric acid, and thus a solution of the acid of the above composition is obtained. It is evident from the theory of the formation of amides and nitriles (Chapter IX.) that very many compounds of this kind can correspond with the acids of phosphorus; but as yet only a few are known. The easy transitions of the ortho-, meta-, and pyrophosphoric acids, by means of the hydrogen of ammonia, into the lower acids, and conversely, tend to complicate the study of this very large class of compounds, and it is rarely that the nature of a product thus obtained can be judged from its composition; and this all the more that instances of isomerism and polymerism, of mixture between water of crystallisation and of constitution, &c., are here possible. Many data are yet needed to enable us to form a true judgment as to the composition and structure of such compounds. As the best proof of this we will describe the very interesting and most fully investigated compound of this class, PNCl_{2}, called _chlorophosphamide_, or nitrogen chlorophosphorite. It is formed in small quantities when the vapour of phosphoric chloride is passed over ignited sal-ammoniac. Besson (1892) heated the compound PCl_{5}8NH_{3} (which is easily and directly formed from PCl_{5} and NH_{3}) under a pressure of about 50 mm. (of mercury) to 200°, and obtained brilliant crystals of PNCl_{2}, which melted at 106° (in the residue after the distillation of sal-ammoniacal phospham). The chlorine in it is very stable--quite different from that in phosphoric chloride. Indeed, the resultant substance is not only insoluble in water (though soluble in alcohol and ether), but it is not even moistened by it, and distils over, together with steam, without being decomposed. In a free state it easily crystallises in colourless prisms, fuses at 114°, boils at 250° (Gladstone, Wichelhaus), and when fused with potash gives potassium chloride and the amidonitrile of phosphoric acid. Judging from its formula and the simplicity of its composition and reactions, it might be thought that the molecular weight of this substance would be expressed by the formula PCl_{2}N, that it corresponds with PON and with PCl_{5} (like POCl_3), with the substitution of Cl_3 by N, just as in POCl_3 two atoms of chlorine are replaced by oxygen; but all these surmises are incorrect, because its vapour density (referred to hydrogen--Gladstone, Wichelhaus) = 182--that is, the molecular formula must be three times greater, P_{3}N_{3}Cl_{6}. The polymerisation (tripling) is here of exactly the same kind as with the nitriles. The most important analogue of phosphorus is _arsenic_, the metallic aspect of which and the general character of its compounds of the types AsX_{3} and AsX_{5} at once recall the metals. The hydrate of its highest oxide, arsenic acid (ortho-arsenic acid), H_{3}AsO_{4}, is an oxidising agent, and gives up a portion of its oxygen to many other substances; but, nevertheless, it is very like phosphoric acid. Mitscherlich established the conception of isomorphism by comparing the salts of these acids.[30] [30] It is necessary to remark that, although arsenic is so closely analogous to phosphorus (especially in the higher forms of combination, RX_{3} and RX_{5}), at the same time it exhibits a certain resemblance and even isomorphism with the corresponding compounds of sulphur (especially the metallic compounds of the type MAs, corresponding with MS). Thus compounds containing metals, arsenic, and sulphur are very frequently met with in nature. Sometimes the relative amounts of arsenic and sulphur vary, so that an isomorphous substitution between the arsenides and sulphides must be recognised. Besides FeS_{2} (ordinary pyrites), and FeAs_{2}, iron forms an arsenical pyrites containing both sulphur and arsenic, which from its composition, FeAsS or FeS_{2}FeAs_{2}, resembles the two preceding. Arsenic occurs _in nature_, not only combined with metals, but also, although rarely, native and also in combination with sulphur in two minerals--one red, _realgar_, As_{2}S_{2}, and the other yellow, _orpiment_, As_{2}S_{3} (Chapter XX., Note 29). Arsenic occurs, but more rarely, in the form of salts of arsenic acid--for instance, the so-called cobalt and nickel blooms, two minerals which are found accompanying other cobalt ores, are the arsenates of these metals. Arsenic is also found in certain clays (ochres) and has been discovered in small quantities in some mineral springs, but it is in general of rarer occurrence in nature than phosphorus. Arsenic is most frequently extracted from arsenical pyrites, FeSAs, which, when roasted without access of air, evolves the vapour of arsenic, ferrous sulphide being left behind. It is also obtained by heating arsenious anhydride with charcoal, in which case carbonic oxide is evolved. In general, the oxides and other compounds are very easily reduced. Solid _arsenic_ is a steel-grey brittle _metal_, having a bright lustre and scaly structure. Its specific gravity is 5·7. It is opaque and infusible, but volatilises as a yellow vapour which on cooling deposits rhombohedral crystals.[30 bis] The vapour density of arsenic is 150 times greater than that of hydrogen--that is, its molecule, like that of phosphorus, contains 4 atoms, As_{4}. When heated in the air, arsenic easily oxidises into white arsenious anhydride, As_{2}O_{3}, but even at the ordinary temperature it loses its lustre (becomes dull), owing to the formation of a coating of a lower oxide. The latter appears to be as volatile as arsenious anhydride, and it is probable that it is owing to the presence of this compound that the vapours of arsenious compounds, when heated with charcoal (for example, in the reducing flame of a blow-pipe), have the characteristic smell of garlic, because the vapour of arsenic itself has not this odour. [30 bis] According to Retgers (1893) the arsenic mirror (see further on) is an unstable variety of metallic arsenic, whilst the brown product which is formed together with it in Marsh's apparatus is a lower hydride AsH. Schuller and McLeod (1894), however, recognise a peculiar yellow variety of arsenic. Arsenic easily combines with bromine and chlorine;[31] nitric acid and aqua regia also oxidise it into the higher oxide, or rather its hydrate, arsenic acid.[32] As far as is known, it does not decompose steam, and it acts exceedingly slowly on those acids, like hydrochloric, which are not capable of oxidising. [31] Hydrochloric acid dissolves arsenious anhydride in considerable quantities, and this is probably owing to the formation of unstable compounds in which the arsenious anhydride plays the part of a base. A compound called _arsenious oxychloride_, having the composition AsOCl, is even known. It is formed when arsenious anhydride is added little by little to boiling arsenic trichloride, As_{2}O_{3} + AsCl_{3} = 3AsOCl. It is a transparent substance, which fumes in air, and combines with water to form a crystalline mass having the composition As_{2}(OH)_{4}Cl_{2}. When heated it decomposes into arsenious chloride and a fresh oxychloride of a more complex composition, As_{6}O_{8}Cl_{2}· Arsenic trichloride, when treated with a small quantity of water, forms the crystalline compound, As_{2}(HO)_{4}Cl_{2}, mentioned above. These compounds resemble the basic salts of bismuth and aluminium. The existence of these compounds shows that arsenic is of a more metallic or basic character than phosphorus. Nevertheless _arsenic trichloride_, AsCl_{3}, resembles phosphorus trichloride in many respects. It is obtained by the direct action of chlorine on arsenic, or by distilling a mixture of common salt, sulphuric acid, and arsenious anhydride. The latter mode of preparation already indicates the basic properties of the oxide. Arsenious chloride is a colourless oily liquid, boiling at 130°, and having a sp. gr. of 2·20. It fumes in air like other chloranhydrides, but it is much more slowly and imperfectly decomposed by water than phosphorus trichloride. A considerable quantity of water is required for its complete decomposition into hydrochloric acid and arsenious anhydride. It forms an excellent example of the transition from true metallic chlorides to true chloranhydrides of the acids. It hardly combines with chlorine, _i.e._ if AsCl_{5} is formed it is very unstable. _Arsenic tribromide_, AsBr_{3}, is formed as a crystalline substance, fusing at 20° and boiling at 220°, by the direct action of metallic arsenic on a solution of bromine in carbon bisulphide, the latter being then evaporated. The specific gravity of arsenic tribromide is 3·36. Crystalline arsenic tri-iodide, AsI_{3}, having a sp. gr. 4·39, may be obtained in a like manner; it may be dissolved in water, and on evaporation separates out from the solution in an anhydrous state--that is, it is not decomposed--and consequently behaves like metallic salts. _Arsenic trifluoride_, AsF_{3}, is obtained by heating fluor spar and arsenious anhydride with sulphuric acid. It is a fuming, colourless, and very poisonous liquid, which boils at 63° and has a sp. gr. of 2·73. It is decomposed by water. It is very remarkable that fluorine forms a pentafluoride of arsenic also, although this compound has not yet been obtained in a separate state, but only in combination with potassium fluoride. This compound, K_{3}AsF_{8}, is formed as prismatic crystals when potassium arsenate, K_{3}AsO_{4}, is dissolved in hydrofluoric acid. [32] _Arsenic acid_, H_{3}AsO_{4}, corresponding with orthophosphoric acid, is formed by oxidising arsenious anhydride with nitric acid, and evaporating the resultant solution until it attains a sp. gr. of 2·2; on cooling it separates in crystals having the above composition. This hydrate corresponds with the normal salts of arsenic acid; but on dissolving in water (without heating), and on cooling a strong solution, crystals containing a greater amount of water, namely, (AsH_{3}O_{4})_{2},H_{2}O, separate. This water, like water of crystallisation, is very easily expelled at 100°. At 120° crystals having a composition identical with that of pyrophosphoric acid, As_{2}H_{4}O_{7}, separate, but water, on dissolving this hydrate with the development of heat, forms a solution in no way differing from a solution of ordinary arsenic acid, so that it is not an independent pyroarsenic acid that is formed. Neither is there any true analogue of metaphosphoric acid, although the compound AsHO_{3} is formed at 200°, and on solidifying forms a mass having a pearly lustre and sparingly soluble in cold water; but on coming into contact with warm water it becomes very hot, and gives ordinary orthoarsenic acid in solution. Arsenic acid forms three series of salts, which are perfectly analogous to the three series of orthophosphates. Thus the normal salt, K_{3}AsO_{4}, is formed by fusing the other potassium arsenates with potassium carbonate; it is soluble in water and crystallises in needles which do not contain water. Di-potassium arsenate, K_{2}HAsO_{4}, is formed in solution by mixing potassium carbonate and arsenic acid until carbonic anhydride ceases to be evolved; it does not crystallise, and has an alkaline reaction; hence it corresponds perfectly with the sodium phosphate. As was mentioned above, arsenic acid itself acts as an oxidising agent; for example, it is used in the manufacture of aniline dyes for oxidising the aniline, and it is prepared in large quantities for this purpose. When sulphuretted hydrogen is passed through its solution, sulphuric acid and arsenious anhydride are obtained in solution. Arsenic acid is very easily soluble in water, and its solution has an exceedingly acid reaction, and when boiled with hydrochloric acid evolves chlorine, like selenic, chromic, manganic, and certain other higher metallic acids. _Arsenic anhydride_, As_{2}O_{5}, is produced when arsenic acid is heated to redness. It must be carefully heated, as at a bright red heat it decomposes into oxygen and arsenious anhydride. Arsenic anhydride is an amorphous substance almost entirely insoluble in water, but it attracts moisture from the air, deliquesces, and passes into the acid. Hot water produces this transformation with great ease. _Arseniuretted hydrogen_, _arsine_, AsH_{3}, resembles phosphuretted hydrogen in many respects. This colourless gas, which liquefies into a mobile liquid at -40°, has a disagreeable garlic-like odour, is only slightly soluble in water, and is exceedingly poisonous. Even in a small quantity it causes great suffering, and if present to any considerable amount in air it even causes death. The other compounds of arsenic are also poisonous, with the exception of the insoluble sulphur compound and some compounds of arsenic acid. Arseniuretted hydrogen, AsH_{3}, is obtained by the action of water on the alloy of arsenic and sodium, sodium hydroxide and arseniuretted hydrogen being formed. It is also formed by the action of sulphuric acid on the alloy of arsenic and zinc: Zn_{3}As_{2} + 3H_{2}SO_{4} = 2AsH_{3} + 3ZnSO_{4}.[33] The oxygen compounds of arsenic are very easily reduced by the action of hydrogen at the moment of its evolution from acids, and the reduced arsenic then combines with the hydrogen; hence, if a certain amount of an oxygen compound of arsenic be put into an apparatus containing zinc and sulphuric acid (and thus serving for the evolution of hydrogen), the hydrogen evolved will contain arseniuretted hydrogen. In this case it is diluted with a considerable amount of hydrogen. But its presence in the most minute quantities may be easily recognised from the fact that it is _easily decomposed_ by heat (200° according to Brunn) into metallic arsenic and hydrogen, and therefore if such impure hydrogen he passed through a moderately-heated tube metallic arsenic will be deposited as a bright layer on the part of the tube which was heated (_see_ Note 30 bis). This reaction is so sensitive that it enables the most minute traces of arsenic to be discovered; hence it is employed in medical jurisprudence, as a test in poisoning cases. It is easy to discover the presence of arsenic in common zinc, copper, sulphuric and hydrochloric acids, _&c._ by this method. It is obvious that in testing for poison by Marsh's apparatus it is necessary to take zinc and sulphuric acid quite free from arsenic. The arsenic deposited in the tube may be driven as a volatile metal from one place to another in the current of hydrogen evolved, owing to its volatility. This forms a distinction between arseniuretted and antimoniuretted hydrogen, which is decomposed by heat in just the same way as arseniuretted hydrogen, but the mirror given by Sb is not so volatile as that formed by As. [Illustration: FIG. 84.--Formation and decomposition of arseniuretted hydrogen. Hydrogen is evolved in the Woulfe's bottle, and when the gas comes off, a solution containing arsenic is poured through the funnel. The presence of AsH_{3} is recognised from the deposition of a mirror of arsenic when the gas-conducting tube is heated. If the escaping hydrogen be lighted, and a porcelain dish be held in the flame, a film of arsenic is deposited on it. The gas is dried by passing through the tube containing calcium chloride. This apparatus is used for the detection of arsenic by Marsh's test.] [33] The formation of arseniuretted hydrogen is accompanied by the absorption of 37,000 heat units, while phosphine evolves 18,000 (Ogier), and ammonia 27,000. Sodium (0·6 p.c.) amalgam, with a strong solution of As_{2}O_{3}, gives a gas containing 86 vols. of arsenic and 14 vols. of hydrogen (Cavazzi). If hydrogen contains arseniuretted hydrogen, it also gives metallic arsenic when it burns, because in the reducing flame of hydrogen the oxygen attracted combines entirely with the hydrogen and not with the arsenic, so that if a cold object, such as a piece of china, be held in the hydrogen flame the arsenic will be deposited upon it as a metallic spot.[34] [34] This spot, or the metallic ring which is deposited on the heated tube, may easily be tested as to whether it is really due to arsenic or proceeds from some other substance reduced in the hydrogen flame--for instance, carbon or antimony. The necessity for distinguishing arsenic from antimony is all the more frequently encountered in medical jurisprudence, from the fact that preparations of antimony are very frequently used as medicine, and antimony behaves in the hydrogen apparatus just like arsenic, and therefore in making an investigation for poisoning by arsenic it is easy to mistake it for antimony. The best method to distinguish between the metallic spots of arsenic and antimony is to test them with a solution of sodium hypochlorite, free from chlorine, because this will dissolve arsenic and not antimony. Such a solution is easily obtained by the double decomposition of solutions of sodium carbonate and bleaching powder. A solution of potassium chlorate acts in the same manner, only more slowly. Further particulars must be looked for in analytical works. Arseniuretted hydrogen, like phosphuretted hydrogen, is only slightly soluble in water, has no alkaline properties--that is, it does not combine with acids--and acts as a reducing agent. When passed into a solution of silver nitrate it gives a blackish brown precipitate of metallic silver, the arsenic being oxidised. If acting on copper sulphate and similar salts, arseniuretted hydrogen sometimes forms arsenides--_i.e._ it reduces the metallic salt with its hydrogen, and is itself reduced to arsenic. Sulphuric, and even hydrochloric, acid reduces arseniuretted hydrogen to arsenic, and it is still more easily decomposed by arsenious chloride, and with phosphorous chloride it gives the compound PAs. Arseniuretted hydrogen gives metallic arsenic with an acid solution of arsenious anhydride (Tivoli). The most common compound of arsenic is the solid and volatile _arsenious anhydride_, As_{2}O_{3}, which corresponds with phosphorous and nitrous anhydrides. This very poisonous, colourless, and sweet-tasting substance is generally known under the name of arsenic, or _white arsenic_. The corresponding hydrate is as yet unknown; its solutions, when evaporated, yield crystals of arsenious anhydride. It is chiefly prepared for the dyer, and is also used as a vermin killer, and sometimes in medicine; it is a product from which all other compounds of arsenic can be prepared. It is obtained as a by-product in roasting cobalt and other ores containing arsenic. Arsenical pyrites are sometimes purposely roasted for the extraction of arsenious anhydride. When arsenical ores are burnt in the air, the sulphur and arsenic are converted into the oxides As_{2}O_{3} and SO_{2}. The former is a solid at the ordinary temperature, and the latter gaseous, and therefore the arsenious anhydride is deposited as a sublimate in the cooler portion of the flues through which the vapours escape from the furnace. It collects in condensing chambers especially constructed in the flues. The deposit is collected, and after being distilled gives arsenious anhydride in the form of a vitreous non-crystalline mass. This is one of the varieties of arsenious anhydride, which is also known in two crystalline forms. When sublimed--_i.e._ when it rapidly passes from the state of vapour to the solid state--it appears in the regular system in the form of octahedra.[35] It is obtained in the same form when it is crystallised from acid solutions. The specific gravity of the crystals is 3·7. The other crystalline form (in prisms) belongs to the rhombohedral system, and is also formed by sublimation when the crystals are deposited on a heated surface, or when it is crystallised from alkaline solutions.[36] [35] According to Mitscherlich's determination, the vapour density of arsenious anhydride is 199 (H = 1)--that is, it answers to the molecular formula As_{4}O_{6}. Probably this is connected with the fact that the molecule of free arsenic contains As_{4}. V. Meyer and Biltz, however, showed (1889) that at a temperature of about 1,700° the vapour density of arsenic corresponds with the molecule As_{2}, and not As_{4}, as at lower temperatures. [36] Arsenious anhydride is obtained in an amorphous form after prolonged heating at a temperature near to that at which it volatilises, or, better still, by heating it in a closed vessel. It then fuses to a colourless liquid, which on cooling forms a transparent vitreous mass, whose specific gravity is only slightly less than that of the crystalline anhydride. On cooling, this vitreous mass undergoes an internal change, in which it crystallises and becomes opaque, and acquires the appearance of porcelain. The following difference between the vitreous and opaque varieties is very remarkable: when the vitreous variety is dissolved in strong and hot hydrochloric acid it gives crystals of the anhydride on cooling, and this crystallisation _is accompanied by the emission of light_ (which is visible in the dark), and the entire liquid glows as the crystals begin to separate. The opaque variety does not emit light when the crystals separate from its hydrochloric acid solution. It is also remarkable that the vitreous variety passes into the opaque form when it is pounded--that is, under the action of a series of blows. Thus, several varieties of arsenious anhydride are known, but as yet they are not characterised by any special chemical distinctions, and even differ but little in their specific gravities, so that it cannot be said that the above differences are due to any isomeric transformation--that is, to an arrangement of the atoms in the molecule--but probably only depend on a difference in the distribution of the molecules, or, in other terms, are physical and not chemical variations. One part of the vitreous anhydride requires twelve parts of boiling water for its solution, or twenty-five parts at the ordinary temperature. The opaque variety is less soluble, and at the ordinary temperature requires about seventy parts of water for its solution. Solutions of arsenious anhydride have a sweet metallic taste, and give _a feeble acid reaction_. Its solubility increases with the admixture of acids and alkalis. This shows the property of arsenious anhydride of forming salts with acids and alkalis. And in fact compounds of it with hydrochloric acid (Note 31), sulphuric anhydride (_see_ further on), and with the alkali oxides are known.[37] If silver nitrate be added to a solution of arsenious anhydride, it does not give any precipitate unless a certain amount of the arsenious anhydride is saturated with an alkali--for instance, ammonia. It then gives a precipitate of silver arsenite, Ag_{3}AsO_{3}. This is yellow, soluble in an excess of ammonia, and anhydrous; it distinctly shows that arsenious acid is tribasic, and that it differs in this respect from phosphorous acid, in which only two atoms of hydrogen can be replaced by metals.[38] The feeble acid character of arsenious anhydride is confirmed by the formation of saline compounds with acids. In this respect the most remarkable example is the anhydrous compound with sulphuric acid, having the composition As_{2}O_{3},SO_{3}. It is formed in the roasting of arsenical pyrites in those spaces where the arsenious anhydride condenses, a portion of the sulphurous anhydride being converted into sulphuric anhydride, SO_{3}, at the expense of the oxygen of the air. The compound in question forms colourless tabular crystals, which are decomposed by water with formation of sulphuric acid and arsenious anhydride.[39] [37] Arsenious anhydride does not oxidise in air, either in a dry state or in solution, but in the presence of alkalis it absorbs oxygen from the air, and acts as an excellent reducing agent. This probably is connected with the fact that arsenic acid is much more energetic than arsenious acid, and that it is arsenic acid which is formed by the oxidation of the latter in the presence of alkalis. Arsenious anhydride is easily reduced to arsenic by many metals, even by copper. [38] The feebleness of the acid properties of arsenious anhydride is seen in the fact that if it be dissolved in ammonia water, and then a still stronger solution of ammonia be added, prismatic crystals separate having the composition of ammonium metarsenite, NH_{4}AsO_{3}. This ammonium salt deliquesces in air, and loses all its ammonia. The magnesium salt is tri-metallic, Mg_{3}(AsO_{3})_{2}; it is insoluble in water, and is formed by mixing an ammoniacal solution of arsenious anhydride with an ammoniacal solution of a magnesium salt. It is insoluble even in ammonia, although it dissolves in an excess of acids. Magnesium hydroxide gives the same salt with arsenious solutions, and hence magnesia is one of the best antidotes for arsenic poisoning. _The arsenites of copper_ are much used in the manufacture of colours, more especially of pigments. They are distinguished by their insolubility in water and by their remarkably vivid green colour, but at the same time by their poisonous character. Not only do such pigments applied to wall papers or other materials easily dust off from them, but they give exhalations containing AsH_{3}. The cupric salts, CuX_{2}, when mixed with an alkaline solution of arsenious acid, give a green precipitate of a copper salt called _Scheele's green_. Its composition is probably CuHAsO_{3}. Ammonia dissolves it, and gives a colourless solution, containing cuprous arsenate--that is, the cupric compound is reduced and the arsenic subjected to a further oxidation. The so-called _Schweinfurt green_ was still more used, especially in former times; it is an insoluble green cupric salt, which resembles the preceding in many respects, but has a different tint. It is prepared by mixing boiling solutions of arsenious acid and cupric acetate. Arsenious acid forms an insoluble compound with ferric hydroxide, resembling the phosphate; and this is the reason why freshly precipitated oxide of iron is employed as an _antidote for arsenic_. The freshly precipitated oxide of iron, taken immediately after poisoning by arsenic, converts the arsenious acid into an insoluble state, by forming a compound on which the acids of the stomach have no action, so that the poisoning cannot proceed. It is remarkable that the inhabitants of certain mountainous countries accustom themselves to taking arsenic, as a means which, according to their experience, helps to overcome the fatigue of mountain ascents. Arsenious anhydride and certain of its salts are also used in medicine, naturally only in small quantities. When taken internally arsenic passes into the blood, and is mainly excreted by the urine. [39] Adie (1889) obtained compounds of As_{2}O_{3} with 1, 2, 4, and 8 SO_{3} by the direct action of ordinary and Nordhausen sulphuric acid upon As_{2}O_{3}. Weber had previously obtained As_{2}O_{3}SO_{3} (which disengages SO_{3} at 225°), and also other As_{2}O_{3}_n_SO_{3} (where _n_ = 3, 6, and 8), by the action of the vapours of SO_{3} upon As_{2}O_{3} at a definite temperature. The compound As_{2}O_{3},8SO_{3} loses SO_{3} at 100°. Oxide of antimony, Sb_{2}O_{3}, gives similar compounds. Adie (1891) also obtained (by the action of SO_{3} upon H_{3}PO_{4}) a compound H_{3}PO_{4}3SO_{3} in the form of a viscous liquid decomposed by water. _Antimony_ (stibium), Sb = 120, is another analogue of phosphorus. In its external appearance and the properties of its compounds it resembles the metals still more closely than arsenic. In fact, antimony has the appearance, lustre, and many of the characteristic properties of the metals. Its oxide, Sb_{2}O_{3}, exhibits the earthy appearance of rust or of lime, and has distinctly basic properties, although it corresponds with nitrous and phosphorous anhydride, and is able, like them, to give saline compounds with bases. At the same time antimony presents, in the majority of its compounds, an entire analogy with phosphorus and arsenic. Its compounds belong to the type SbX_{3} and SbX_{5}. It is found in nature chiefly in the form of sulphide, Sb_{2}S_{3}. This substance sometimes occurs in large masses in mineral veins and is known in mineralogy under the name of antimony glance or _stibnite_, and commercially as _antimony_ (Chapter XX., Note 29). The most abundant deposits of antimony ore occur in Portugal (near Oporto on the Douro). Besides which antimony partially or totally replaces arsenic in some minerals; thus, for example, a compound of antimony sulphide and arsenic sulphide with silver sulphide is found in red silver ore. But in every case antimony is a rather rare metal found in few localities. In Russia it is known to occur in Daghestan in the Caucasus. It is extracted chiefly for the preparation of alloys with lead and tin, which are used for casting printing type.[40] Some of its compounds are also used in medicine, the most important in this respect being antimony pentasulphide, Sb_{2}S_{5} (_sulfur auratum antimonii_), and tartar emetic, which is a double salt derived from tartaric acid and has the composition C_{4}H_{4}K(SbO)O_{6}. Even the native antimony sulphide is used in large quantities as a purgative for horses and dogs. Metallic antimony is extracted from the glance, Sb_{2}S_{2}, by roasting, when the sulphur burns away and the antimony oxidises, forming the oxide Sb_{2}O_{3}, which is then heated with charcoal, and thus reduced to a _metallic state_. The reduction may be carried on in the laboratory on a small scale by fusing the sulphide with iron which takes up the sulphur.[40 bis] [40] Printers' type consists of an alloy known as 'type-metal,' containing usually about 15 parts of antimony to 85 parts of lead; sometimes (for example, for stereotypes) from 10 to 15 per cent. Bi or 8 per cent. Sn and even Cu is added. The hardness of the alloy, which is essential for printing, evidently depends upon the presence of antimony, but an excess must be avoided, since this renders the alloy brittle, and the type after a time loses its sharpness. [40 bis] Antimony is prepared in a state of greater purity by heating with charcoal the oxide obtained by the action of nitric acid on the impure commercial metallic antimony. This is based on the fact that by the action of the acid, antimony forms the oxide Sb_{2}O_{3}, which is but slightly soluble in water. The arsenic, which is nearly always present, forms soluble arsenious and arsenic acids, and remains in solution. The purest antimony is easily obtained from tartar emetic, by heating it with a small quantity of nitre. Metallic antimony also occurs, although rarely, native; and as it is very easily obtained, it was known to the alchemists of the fifteenth century. Very pure metallic antimony may be deposited by the electric current from a solution of antimonious sulphide in sodium sulphide after the addition of sodium chloride to the solution. Metallic antimony has a white colour and a brilliant lustre; it remains untarnished in the air, for the metal does not oxidise at the ordinary temperature. It crystallises in rhombohedra, and always shows a distinctly crystalline structure which gives it quite a different aspect from the majority of the metals yet known. It is most like tellurium in this respect. Antimony is brittle, so that it is very easily powdered; its specific gravity is 6·7, it melts at about 432°, but only volatilises at a bright red heat. When heated in the air--for instance, before the blow-pipe--it burns and gives white odourless fumes, consisting of the oxide. This oxide is termed antimonious oxide, although it might as well be termed antimonious anhydride. It is given the first name because in the majority of cases its compounds with acids are used, but it forms compounds with the alkalis just as easily. Antimonious oxide, like arsenious anhydride, crystallises either in regular octahedra or in rhombic prisms; its specific gravity is 5·56; when heated it becomes yellow and then fuses, and when further heated in air it oxidises, forming an oxide of the composition Sb_{2}O_{4}. Antimonious oxide is insoluble in water and in nitric acid, but it easily dissolves in strong hydrochloric acid and in alkalis, as well as in tartaric acid or solutions of its acid salts. When dissolved in the latter it forms tartar emetic. It is precipitated from its solutions in alkalis and acids (by the action of acids on the former and alkalis on the latter). It occurs native but rarely. As a base it gives salts of the type SbOX (as if the basic salts = SbX_{3}, Sb_{2}O_{3}) and hardly ever forms salts, SbX_{3}. In the antimonyl salts, SbOX, the group SbO is univalent, like potassium or silver. The oxide itself is (SbO)_{2}O, the hydroxide, SbO(OH), &c.; tartar emetic is a salt in which one hydrogen of tartaric acid is replaced by potassium and the other by antimonyl, SbO. Antimonious oxide is very easily separated from its salts by any base, but it must be observed that this separation does not take place in the presence of tartaric acid, owing to the property of tartaric acid of forming a soluble double salt--_i.e._ tartar emetic.[41] [41] As antimonious oxide answers to the type SbX_{3}, it is evident that compounds may exist in which antimony will replace three atoms of hydrogen; such compounds have been to some extent obtained, but they are easily converted by water into substances corresponding with the ordinary formulæ of the compounds of antimony. Thus tartar emetic, C_{4}H_{4}(SbO)KO_{6}, loses water when heated, and forms C_{4}H_{2}SbKO_{6}--that is, tartaric acid, C_{2}H_{6}O_{6}, in which one atom of hydrogen is replaced by potassium and three by antimony. But this substance is reconverted into tartar emetic by the action of water. A similar compound is seen in that _intermediate oxide of antimony_ which is formed when antimonious oxide is heated in air: its composition is SbO_{2} or Sb_{2}O_{4}. This oxide may be regarded as orthantimonic acid, SbO(HO)_{3}, in which three atoms of hydrogen are replaced by antimony in that state in which it occurs in oxide of antimony--_i.e._ SbO(SbO_{3}) = Sb_{2}O_{4}. Oxide of antimony is also formed when antimonic acid is ignited; it then loses water and oxygen, and gives this intermediate oxide as a white infusible powder, of sp. gr. 6·7. It is somewhat soluble in water, and gives a solution which turns litmus paper red. If metallic antimony, or antimonious oxide, be oxidised by an excess of nitric acid and the resultant mass be carefully evaporated to dryness, _metantimonic acid_, SbHO_{3}, is formed. Its corresponding potassium salt, 2SbKO_{3},5H_{2}O, is prepared by fusing metallic antimony with one-fourth its weight of nitre and washing the resultant mass with cold water. This potassium salt is only slightly soluble in water (in 50 parts) and the sodium salt is still less so. An ortho-acid, SbH_{3}O_{4}, also appears to exist;[41 bis] it is obtained by the action of water on antimony pentachloride, but it is very unstable, like the pentachloride, SbCl_{5}, itself, which easily gives up Cl_{2}, leaving antimony trichloride, SbCl_{3}, and this is decomposed by water, forming an oxychloride--SbOCl, only slightly soluble in water. When antimonic acid is heated to an incipient red heat, it parts with water and forms the anhydride, Sb_{2}O_{5}, of a yellow colour and specific gravity 6·5.[42] [41 bis] Beilstein and Blaese (1889), after preparing many salts of antimonic acid, came to the conclusion that it is monobasic, but all the salts still contain water, so that their general type is mostly: MSbO_{3}3H_{2}O, for example, M = Li, Hg (salts of the suboxide), 1/2 Pb, &c. The type of the ortho-salts, M_{2}SbO_{4}, is quite unknown, although it is reproduced in the thio-compounds, for instance, Schlippe's salt, Na_{2}SbS_{4}, but this salt also contains water of crystallisation, 9H_{2}O (Chapter XX., Note 29). [42] Among the other compounds of antimony, _antimoniuretted hydrogen_, SbH_{3}, resembles arseniuretted hydrogen in its mode of formation and properties (it splits up at 150°, Brunn 1890; when liquified, it boils at -65° and solidifies at -92°), whilst the halogen compounds differ in many respects from those of arsenic. When chlorine is passed over an excess of antimony powder, it forms _antimony trichloride_, SbCl_{3}, but if the chlorine be in excess it forms the _pentachloride_, SbCl_{5}. The trichloride is a crystalline substance which melts at 72° and distils at 230°, whilst the pentachloride is a yellow liquid, which splits up into chlorine and the trichloride when heated; at 140° it begins to give off chlorine abundantly, carrying away the vapour of the trichloride with it; and at 200° the decomposition is complete, and pure antimonious chloride only passes over. This property of antimony pentachloride has caused it to be applied in many cases for the transference of chlorine; all the more that when it has given up its chlorine, it leaves the trichloride, which is able to absorb a fresh amount of chlorine; and therefore many substances which are unable to react directly with gaseous chlorine do so with antimony pentachloride, and in the presence of a small quantity of it chlorine will act on them, just as oxygen is able, in the presence of nitrogen oxides, to oxidise substances which could not be oxidised by means of free oxygen. Thus carbon bisulphide is not acted on by chlorine at low temperatures--this reaction requires a high temperature--but in the presence of antimony pentachloride its conversion into carbon tetrachloride takes place at low temperatures. Antimony tri- and pentachloride, having the character of chloranhydrides, fume in air, attract moisture, and are decomposed by water, forming antimonious and antimonic acids. But in the first action of water the trichloride does not evolve all its chlorine as hydrochloric acid, which is intelligible in view of the fact that antimonious anhydride is also a base, and is therefore able to react with acids; indeed antimony sulphide dissolved in an excess of hydrochloric acid (hydrogen sulphide is evolved) gives an aqueous solution of antimony trichloride, which, when carefully distilled, even gives the anhydrous compound. Antimony trichloride is only decomposed by an excess of water, and then not completely, for with a large quantity of water it forms _powder of algaroth_--_i.e._ antimony oxychloride. The first action of water consists in the formation of _oxychloride_, SbOCl--that is, a salt corresponding to oxide of antimony as a base. If antimony oxide or antimony chloride be dissolved in an excess of hydrochloric acid, and the solution diluted with a considerable amount of water, then this same powder of algaroth is precipitated. The composition varies with the relative amount of water; namely, between the limits SbOCl and Sb_{4}O_{5}Cl_{2}. The latter compound is, as it were, a basic salt of the former, because its composition = 2(SbOCl)Sb_{2}O_{3}. With bromine and iodine, antimony forms compounds similar to those with chlorine. Antimonious bromide, SbBr_{3}, crystallises in colourless prisms, melts at 94°, and boils at 270°; antimonious iodide, SbI_{3}, forms red crystals of sp. gr. 5·0; antimony trifluoride, SbF_{3} separates from a solution of antimonious oxide in hydrofluoric acid, and SbF_{5} is formed by a similar treatment of antimonic acid. The latter gives easily-soluble double salts with the fluorides of the metals of the alkalis. De Haën (1887) obtained very stable double soluble salts, SbF_{3},KCl (100 parts of water dissolve 57 parts of salt), SbF_{3},K_{2}SO_{4}, &c., which he proposed to make use of in the arts as very easily crystallisable and soluble salts of antimony. Engel, by passing hydrochloric acid gas into a saturated solution of antimonious chloride at 0°, obtained a compound HCl,2SbCl_{3},2H_{2}O, and with the pentachloride a compound SbCl_{5},5HCl,10H_{2}O. Bismuth trichloride, BiCl_{3}, gives a similar compound. Saunders (1892) obtained 5RbCl,3SbCl_{3} and RbCl,SbCl_{3}. Ditte and Metzner (1892) showed that Sb and Bi dissolve in hydrochloric acid only owing to the participation of the oxygen of the air or of that dissolved in the acid. The heaviest analogue of nitrogen and phosphorus is _bismuth_, Bi = 208. Here, as in the other groups, the basic, metallic, properties increase with the atomic weight. Bismuth does not give any hydrogen compound and the highest oxide, Bi_{2}O_{5}, is a very feeble acid oxide. Bismuthous oxide, Bi_{2}O_{3}, is a base, and bismuth itself a perfect metal. To explain the other properties of bismuth it must further be remarked that in the eleventh series it follows mercury, thallium and lead, whose atomic weights are near to that of bismuth, and that therefore it resembles them and more especially its nearest neighbour, lead. Although PbO and PbO_{2}, represent types different from Bi_{2}O_{3} and Bi_{2}O_{5}, they resemble them in many respects, even in their external appearance, moreover the lower oxides both of Pb and Bi are basic and the higher acid, which easily evolve oxygen. But judging by the formula, Bi_{2}O_{3} is a more feeble base than PbO. They both easily give basic salts. Bismuth forms compounds of two types, BiX_{3} and BiX_{5},[43] which entirely recall the two types we have already established for the compounds of lead. Just as in the case of lead, the type PbX_{2}, is basic, stable, easily formed, and passes with difficulty into the higher and lower types, which are unstable, so also in the case of bismuth the type of combination BiX_{3} is the usual basic form. The higher type of combination, BiX_{5},[44] in fact behaves toward this stable type, BiX_{3}, in exactly the same manner as lead dioxide does to the monoxide; and bismuthic acid is obtained by the action of chlorine on bismuth oxide suspended in water, in exactly the same way as lead dioxide is obtained from lead oxide. It is an oxidising agent like lead dioxide, and even the acid character in bismuthic acid is only slightly more developed than in lead dioxide. Here, as in the case of lead (minium), intermediate compounds are easily formed in which the bismuth of the lower oxide plays the part of a base combined with the acid which is formed by the higher form of the oxidation of bismuth. [43] Metallic bismuth is very easily obtained when the compounds of the oxide are reduced by powerful reducing agents, but when less powerful reducing agents--for example, stannous oxide--are taken, bismuth suboxide is formed as a black crystalline powder. It is a compound of the type BiX_{2}, its composition being BiO; it is decomposed by acids into the metal and oxide, which passes into solution. [44] The type BiX_{5} is represented by the pentoxide, Bi_{2}O_{5}, its metahydrate, Bi_{2}O_{5},H_{2}O, or BiHO_{3}, known as bismuthic acid, and the pyrohydrate, Bi_{2}H_{4}O_{7}. _Bismuth pentoxide_ is obtained by the prolonged passage of chlorine through a boiling solution of potassium hydroxide (sp. gr. 1·38), containing bismuth oxide in suspension; the precipitate is washed with water, with boiling nitric acid (but not for long, as otherwise the bismuthic acid is decomposed), then again with water, and finally the resultant bright red powder of the hydrate BiHO_{3} is dried at 125°. The prolonged action of nitric acid on bismuthic anhydride, Bi_{2}O_{5}, results in the formation of the compound Bi_{2}O_{4},H_{2}O, which decomposes in moist air, forming Bi_{2}O_{3}. The density of bismuthic anhydride is 5·10, of the tetroxide, Bi_{2}O_{4}, 3·60, and of bismuthic acid, BiHO_{3}, 5·75. _Pyrobismuthic acid_, Bi_{2}H_{4}O_{7}, forms a brown powder, which loses a portion of its water at 150°, and decomposes on further heating, with the evolution of oxygen and water. It is obtained by the action of potassium cyanide on a solution of bismuth nitrate. The meta-salts of bismuthic acid are known, for example KBiO_{3}. They generally occur, however, in combinations with metabismuthic acid itself. Thus André (1891) took a solution of the double salt of BiBr_{3} and KBr, treated it with bromine after adding ammonia, and obtained a red-brown precipitate, which after being washed (for several weeks) had the composition KBiO_{3},HBiO_{3} When washed with dilute nitric acid this salt gave bismuthic acid. [Illustration: FIG. 85.--Furnace used for the extraction of bismuth from its ores.] In nature, bismuth occurs in only a few localities and in small quantities, most frequently in a native state, and more rarely as oxide and as a compound of bismuth sulphide with the sulphides of other metals, and sometimes in gold ores. It is extracted from its native ores by simple fusion in the furnace shown in fig. 85. This furnace contains an inclined iron retort, into the upper extremity of which the ore is charged, and the molten _metal_ flows from the lower extremity. It is refined by re-melting, and the pure metal may be obtained by dissolving in nitric acid, decomposing the resultant salt with water, and reducing the precipitate by heating it with charcoal. Bismuth is a metal which crystallises very well from a molten state. Its specific gravity is 9·8; it melts at 269°, and if it be melted in a crucible, allowed to cool slowly, and the crust broken and the remaining molten liquid poured out, perfect rhombohedral crystals of bismuth are obtained on the sides of the crucible.[44 bis] It is brittle, has a grey-coloured fracture with a reddish lustre, is not hard, and is but very slightly ductile and malleable; it volatilises at a white heat and easily oxidises. It recalls antimony and lead in many of its properties. When oxidised in air, or when the nitrate is ignited, bismuth forms the _oxide_, Bi_{2}O_{3}, as a white powder which fuses when heated and resembles massicot. The addition of an excess of caustic potash to a solution of a bismuthous salt gives a white precipitate of the hydroxide, BiO(OH), which loses its water and gives the anhydrous oxide when boiled with a solution of caustic potash. Both the hydroxide and oxide easily dissolve in acids and form bismuthous salts. [44 bis] Hérard (1889) obtained a peculiar variety of bismuth by heating pure crystalline bismuth to a bright red heat in a stream of nitrogen. A greenish vapour was deposited in the cooler portions of the apparatus in the form of a grey powder, which under the microscope had the appearance of minute globules. An atmosphere of nitrogen is necessary for this transformation, other gases such as hydrogen and carbonic oxide do not favour the transition. The resultant amorphous bismuth fuses at 410° (the crystalline variety at 269°), sp. gr. 9·483. (Does it not contain a nitride?) _Bismuthous oxide_, Bi_{2}O_{3}, is a feeble and unenergetic base. The normal hydroxide of the oxide Bi_{2}O_{3} is Bi(OH)_{3}; it parts with water and forms a metahydroxide (bismuthyl hydroxide), BiO(OH). Both of these hydroxides have their corresponding saline compounds of the composition BiX_{3} and BiOX. And the form BiOX is nothing else but the type of the basic salt, because 3ROX = RX + R_{2}O_{3}. It is evident that in the type BiX_{3} the bismuth replaces three atoms of hydrogen. And indeed with phosphoric acid solutions of the bismuthous salts give a precipitate of the composition BiPO_{4}. On the other hand, in the form of compounds BiOX or Bi(OH)_{2}X, the univalent group (BiO) or (BiH_{2}O_{2}) is combined with X. Many bismuth salts are formed according to the type BiOX. For instance the carbonate, (BiO)_{2}CO_{3}, which corresponds with the other carbonates M_{2}CO_{3}. It is obtained as a white precipitate when a solution of sodium carbonate is added to a solution of a bismuth salt.[45] The compound radicle BiO is not a special natural grouping, as it was formerly represented to be; it is simply a mode of expression for showing the relation between the compound in question and the compounds of other oxides. [45] Basic bismuth carbonate is employed for whitening the skin (veloutine, &c.) Three _salts of nitric acid_ are known containing bismuthous oxide. If metallic bismuth or its oxide be dissolved in nitric acid, it forms a colourless transparent solution containing a salt which separates in large transparent crystals containing Bi(NO_{3})_{3},5H_{2}O. When heated at 80° these crystals melt in their water of crystallisation, and in so doing lose a portion of their nitric acid together with water, forming a salt whose empirical formula is Bi_{2}N_{2}H_{2}O_{9}. If the preceding salt belongs to the type BiX_{3}, this one should belong to the form BiOX, because it = BiO(NO_{3}) + Bi(H_{2}O_{2})(NO_{3}). This salt may be heated to 150° without change. When the first colourless crystalline salt dissolves in water _it is decomposed_. There is no decomposition if an excess of acid be added to the water--that is to say, the salt is able to exist in an acid solution without decomposing, without separation of the so-called basic salt--but by itself it cannot be kept in solution; water decomposes this salt, acting on it like an alkali. In other words the basic properties of bismuthic oxide are so feeble that even water acts by taking up a portion of the acid from it. Here we see one of the most striking facts, long since observed, confirming that action of water on salts about which we have spoken in Chapter X. and elsewhere. This action on water may be expressed thus:--BiX_{3} + 2H_{2}O = Bi(OH)_{2}X + 2XH. A salt of the type Bi(OH)_{2}X is obtained in the precipitate. But if the quantity of acid, HX, be increased, the salt BiX_{3} is again formed and passes into solution. The quantity of the salt BiOX which passes into solution on the addition of a given quantity of acid depends indisputably on the amount (mass) of water (Muir). The solution, which is perfectly transparent with a small amount of water, becomes cloudy and deposits the salt of the type BiOX, when diluted. The white flaky precipitate of Bi(OH)_{2}NO_{3} formed from the normal salt Bi(NO_{3})_{3} by mixing it with five parts of water, and in general with a small amount of water, is used in medicine under the name of magistery of bismuth.[46] [46] With an excess of water a further quantity of acid is separated and a still more basic salt formed. The ultimate product, on which an excess of water has apparently no action whatever, is a substance having the composition BiO(NO_{3}).BiO(OH). In the latter salt we see the limit of change, and this limit appears to show that the type of the saline compounds of bismuthic oxide is of the form Bi_{2}X_{6}, and not BiX_{3}; but it is very probable, on the basis of the examples which we considered in the case of lead, that this type should be still further polymerised in order to give a correct idea of the type of the bismuthous compounds. If we refer all the bismuthous compounds to this type, Bi_{2}X_{6}, we shall obtain the following expression for the composition of the nitrates: normal salt, Bi_{2}(NO_{3})_{6}, first basic salt, Bi_{2}O(OH)_{2}(NO_{3})_{2}, magistery of bismuth, Bi_{2}(OH)_{4}(NO_{3})_{2}, and the limiting form Bi_{2}O_{2}(OH)(NO_{3}). The general character of bismuthous oxide in its compounds is well exemplified in the nitrate; bismuthous chloride, BiCl_{3}, which is obtained by heating bismuth in chlorine, or by dissolving it in aqua regia, and then distilling without access of air, is also decomposed by water in exactly the same manner, and forms basic salts--for instance, first, BiOCl, like the above salt of nitric acid. Bismuth chloride boils at 447° and probably its formula is BiCl_{3}. Polymerisation may take place in some compounds and not in others. A volatile compound of the composition Bi(C_{2}H_{5})_{3} is also known as a liquid which is insoluble in water and decomposes with explosion when heated at 130°. Double salts containing chloride of bismuth are: 2(KCl)BiCl_{3}2H_{2}O (from a solution of Bi_{2}O_{3} and KCl in hydrochloric acid) and KClBiCl_{3}H_{2}O. Bigham (1892) also obtained KBr(SO_{4})_{2} in tabular crystals by treating the above-named double salt with strong sulphuric acid. The composition of this salt recalls that of alum. Metallic bismuth is used in the preparation of fusible alloys. The addition of bismuth to many metals renders them very hard, and at the same time generally lowers their melting point to a considerable extent. Thus Wood's metal, which contains one part of cadmium, one part of tin, two parts of lead, and four parts of bismuth, fuses at about 60°, and in general many alloys composed of bismuth, tin, lead, and antimony melt below or about the boiling point of water.[47] [47] As the metals contained in alloys like the above (bismuth, lead, tin, cadmium) are difficultly volatile and their alloys are fusible, they may be employed in the place of mercury in many physical experiments conducted at or above 70°, and they offer the advantage that they do not give any vapour having an appreciable tension (mercury at 100°, 0·75 mm.) Bismuth expands in passing into a molten state, but it has a temperature of maximum density. According to Luedeking the mean coefficient of expansion of liquid bismuth is 0·0000442 (between 270° and 303°), and of solid bismuth 0·0000411. Just as in group II., side by side with the elements zinc, cadmium, and mercury in the uneven series, we found calcium, strontium, and barium in the even series; and as in group IV., parallel to silicon, germanium, tin, and lead, we noticed thallium, zirconium, cerium, and thorium; so also in group V. we find, beside those elements of the uneven series just considered by us, a series of analogues in the even series, which, with a certain degree of similarity (mainly quantitative, or relative to the atomic weights), also present a series of particular (qualitative) independent points of distinction. In the even series are known _vanadium_, which stands between titanium and chromium, _niobium_, between zirconium and molybdenum, and _tantalum_, situated near tungsten (an element of group VI. like chromium and molybdenum). Just as bismuth is similar in many respects to its neighbour lead, so also do these neighbouring elements resemble each other, even in their external appearance, not to mention the quality of their compounds, naturally taking into account the differences of type corresponding with the different groups. The occurrence in group V. determines the type of the oxides, R_{2}O_{3} and R_{2}O_{5}, and the development of an acid character in the higher oxides. The occurrence in the even series determines the absence of volatile compounds, RH_{3}, for these metals, and a more basic character of the oxides of a given composition than in the uneven series, &c.[48] Vanadium, niobium, and tantalum belong to the category of rare metals, and are exceedingly difficult to obtain pure, more especially owing to their similarity to, and occurrence with, chromium, tungsten and other metals, and also in combination among themselves; therefore it is natural that they have been far from completely studied, although since 1860 chemists have devoted not a little time to their investigation. The researches carried out by Marignac, at Geneva, on niobium, and by Sir Henry Roscoe, at Manchester, on vanadium deserve special attention. The undoubted external resemblance of the compounds of chromium and vanadium, as well as the want of completeness in the knowledge of the compounds of vanadium, long caused its oxides to be considered analogous in atomic composition to those formed by chromium. The higher oxide of vanadium was therefore supposed to have the formula VO_{3}. But the fact of the matter is, that the chemical analogy of the elements does not hold in one direction only; vanadium is at one and the same time the analogue of chromium, and consequently of the elements like sulphur of group VI, and also the analogue of phosphorus, arsenic, and antimony; just as bismuth stands in respect to lead and antimony. Investigation has shown that the compounds of vanadium are always accompanied by those of phosphorus as well as of iron, and that it is even more difficult to separate it from the compounds of phosphorus than from those of iron and tungsten. We should have to extend our description considerably if we wished to give the complete history, even of vanadium alone, not to mention niobium and tantalum, all the more as questions would not unfrequently arise concerning the compounds of these elements which have not yet been fully elucidated. We shall therefore limit ourselves to pointing out the most important features in the history of these elements, the more so since the minerals themselves in which they occur are exceedingly rare and only accessible to a few investigators. [48] Although, guided by Brauner, who showed that didymium gives a higher oxide, Di_{2}O_{5}, I place this element in the fifth group, still I am not certain as to its position, because I consider that the questions relating to this metal are still far from being definitely answered. An important point in the history of the members of this group is the circumstance that they form volatile compounds with chlorine, similar to the compounds of the elements of the phosphorus group, namely, of the type RX_{5}. The vapour densities of the compounds of this kind were determined, and served as the most important basis for the explanation of the atomic composition of these molecules. In this we see the power of general and fundamental laws, like the law of Avogadro-Gerhardt. An oxychloride, VOCl_{3}, is known for vanadium, which is the perfect analogue of phosphorus oxychloride. It was formerly considered to be vanadium chloride, for just as in the case of uranium (Chapter XXI.), its lower oxide, VO, was considered to be the metal, because it is exceedingly difficultly reduced--even potassium does not remove all the oxygen, besides which it has a metallic appearance, and decomposes acids like a metal; in a word, it simulates a metal in every respect. _Vanadium oxychloride_ is obtained by heating the trioxide, V_{2}O_{3}, mixed with charcoal, in a current of hydrogen; the lower oxide of vanadium is then formed, and this, when heated in a current of dry chlorine, gives the oxychloride VOCl_{3} as a reddish liquid which does not act on sodium and may be purified by distillation over this metal. It fumes in the air, giving reddish vapours; it reacts on water, forming hydrochloric and vanadic acids; hence, on the one hand it is very similar to phosphorus oxychloride, and on the other hand to chromium oxychloride, CrO_{2}Cl_{2} (Chapter XXI.). It is of a yellow colour, its specific gravity is 1·83, it boils at 120°, and its vapour density is 86 with respect to hydrogen; therefore the above formula expresses its molecular weight.[49] [49] When the vapours of vanadium oxychloride are heated with zinc in a closed tube at 400°, they lose a portion of their chlorine and form a green crystalline mass of sp. gr. 2·88, which is deliquescent in air and has the composition VOCl_{2}. Only its vapour density is unknown, and it would be extremely important to determine whether its molecular composition is that given above, or whether it corresponds with the formula V_{2}O_{2}Cl_{4}. Another less volatile oxychloride, VOCl, is formed with it as a brown insoluble substance, which is, however, soluble in nitric acid like the preceding. Roscoe obtained a still less chlorinated substance, namely, (VO)_{2}Cl; but it may only consist of a mixture of VO and VOCl. At all events, we here find a graduated series such as is met with in the compounds of very few other elements. _Vanadic anhydride_, V_{2}O_{5}, is obtained either in small quantities from certain clays where it accompanies the oxides of iron (hence some sorts of iron contain vanadium) and phosphoric acid, or from the rare minerals: _volborthite_, CuHVO_{4}, or basic vanadate of copper; _vanadinite_, PbCl_{2}3Pb_{3}(VO_{4})_{2}; lead vanadate, Pb_{3}(VO_{4})_{2}, &c. The latter salts are carefully ignited for some time with one-third of their weight of nitre; the fused mass thus formed is powdered and boiled in water: the yellow solution obtained contains potassium vanadate. The solution is neutralised with acid, and barium chloride added; a meta-salt, Ba(VO_{3})_{2}, is then precipitated as an almost insoluble white powder, which gives a solution of vanadic acid when boiled with sulphuric acid. (The precipitate is at first yellow, as long as it remains amorphous, but it afterwards becomes crystalline and white.) The solution thus obtained is neutralised with ammonia, which thus forms ammonium (meta) vanadate, NH_{4}VO_{3}, which, when evaporated, gives colourless crystals, insoluble in water containing sal-ammoniac; hence this salt is precipitated by adding solid sal-ammoniac to the solution. Ammonium vanadate, when ignited, leaves vanadic acid behind. In this it differs from the corresponding chromium salt, which is deoxidised into chromium oxide when ignited. In general, vanadic acid has but a small oxidising action. It is reduced with difficulty, like phosphoric or sulphuric acid, and in this differs from arsenic and chromic acids. Vanadic acid, like chromic acid, separates from its solution as the anhydride V_{2}O_{5}, and not in a hydrous state. Vanadic anhydride, V_{2}O_{5}, forms a reddish-brown mass, which easily fuses and re-solidifies into transparent crystals having a violet lustre (another point of resemblance to chromic acid); it dissolves in water, forming a yellow solution with a slightly acid reaction.[50] [50] Strong acids and alkalis dissolve vanadic anhydride in considerable quantities, forming yellow solutions. When it is ignited, especially in a current of hydrogen, it evolves oxygen and forms the lower oxides; V_{2}O_{4} (acid solutions of a green colour, like the salts of chromic oxide), V_{2}O_{3}, and the lowest oxide, VO. The latter is the metallic powder which is obtained when the vanadium oxychloride is heated in an excess of hydrogen, and was formerly mistaken for metallic vanadium. When a solution of vanadic acid is treated with metallic zinc it forms a blue solution, which seems to contain this oxide. It acts as a reducing agent (and forms a close analogue to chromous oxide, CrO). Metallic _vanadium_ can only be obtained from vanadium chloride which is quite free from oxygen. Moissan (1893) obtained it by reducing the oxide with carbon in the electric furnace, and considered it to be most infusible of the metals in the series Pt, Cr, Mo, U, W, and V (he also obtained a compound of vanadium and carbon). The specific gravity of this metal is 5·5. It is of a grey-white colour, is not decomposed by water, and is not oxidised in air, but burns when strongly heated, and can be fused in a current of hydrogen (forming perhaps a compound with hydrogen). It is insoluble in hydrochloric acid, but easily dissolves in nitric acid, and when fused with caustic soda it forms sodium vanadate. As regards the salts of vanadic acid, three different classes are known; the first correspond with metavanadic acid, VMO_{3} = M_{2}OV_{2}O_{5}, the second correspond with the dichromates--that is, have the composition V_{4}M_{2}O_{11}, which is equal to M_{2}O + 2V_{2}O_{5}--and the third correspond with orthovanadic acid, VM_{3}O_{4} or 3M_{2}O + V_{2}O_{5}. The latter are formed when vanadic anhydride is fused with an excess of an alkaline carbonate. Vanadic acid gives the so-called 'complex' acids (which are considered more fully in Chapter XXI. in speaking of Mo and W)--_i.e._ acids formed of two acids assimilated into one. Thus Friedheim (1890) obtained phosphor-vanadic acid, and Schmitz-Dumont (1890) a similar arseno-vanadic acid. The former is obtained by heating V_{2}O_{5} with sirupy phosphoric acid. The resultant golden-yellow tabular crystals have the composition H_{2}OV_{2}O_{5}P_{2}O_{5}9H_{2}O, and there are corresponding salts--for example, (NH_{4})_{2}V_{2}O_{5}P_{2}O_{5} with 3 and 7H_{2}O, &c. These salts cannot be separated by crystallisation, so that there are 'complexes' of these acids in a whole series of salts (and also in nature). It may be supposed (Friedheim) that V_{2}O_{5} here, as it were, plays the part of a base, or that those acids may be looked upon as double salts. Among the true double salts of vanadium (Nb and Ta) very many are known among the fluorides, such as VF_{3}2NH_{4}F, VOF_{2}2NH_{4}F, VO_{2}F,3NH_{4}F, &c. (Pettersson, Piccini, and Georgi, 1890-92). Vanadium was discovered at the beginning of this century by Del-Rio, and afterwards investigated by Sefström, but it was only in 1868 that Roscoe established the above formulæ of the vanadic compounds. _Niobium and tantalum_[51] occur as acids in rare minerals, and are mainly extracted from _tantalite_ and _columbite_, which are found in Bavaria, Finland, North America, and in the Urals. These minerals are composed of the ferrous salts of niobic and tantalic acids; they contain about 15 per cent. of ferrous oxide in isomorphous mixture with manganous oxide, in combination with various proportions of tantalic and niobic anhydrides. These minerals are first fused with a considerable amount of potassium bisulphate, and the fused mass is boiled in water, which dissolves the ferrous and potassium salts and leaves an insoluble residue of impure niobic and tantalic acids. This raw product is then treated with ammonium sulphide, in order to extract the tin and tungsten, which pass into solution. The residue containing the acids (according to Marignac) is then treated with hydrofluoric acid, in which it entirely dissolves, and potassium fluoride is added to the resultant hot solution; on cooling, a sparingly soluble double fluoride of potassium and tantalum separates out in fine crystals, while the much more soluble niobium salt remains in solution. The difference in the solubility of these double salts in water acidified with hydrofluoric acid (in pure water the solution becomes cloudy after a certain time) is so great that the tantalum compound requires 150 parts of water for its solution, and the niobium compound only 13 parts. The Greenland columbite (specific gravity 5·36) only contains niobic acid, and that from Bodenmais, Bavaria (specific gravity 6·06) almost equal quantities of tantalic and niobic acids. Having isolated tantalic and niobic salts, Marignac found that the relation between the potassium and fluorine in them is very variable--that is, that there exist various double salts of fluoride of potassium, and of the fluorides of the metals of this group, but that with an excess of hydrofluoric acid both the tantalum and niobium compounds contain seven atoms of fluorine to two of potassium, whence it must be concluded that the simplest formula for these double salts will be K_{2}RF_{7} = RF_{5},2KF; that is, that the type of the higher compounds of niobium and tantalum is RX_{5}, and hence is similar to phosphoric acid. A chloride, TaCl_{5}, may be obtained from pure tantalic acid by heating it with charcoal in a current of chlorine. This is a yellow crystalline substance, which melts at 211°, and boils at 241°; its vapour density with respect to hydrogen is 180, as would follow from the formula TaCl_{5}. It is completely decomposed by water into tantalic and hydrochloric acids. _Niobium pentachloride_ may be prepared in the same manner; it fuses at 194°, and boils at 240°. When treated with water this substance gives a solution containing niobic acid, which only separates out on boiling the solution. Delafontaine and Deville found its vapour density to be 9·3 (air = 1), as is shown by its formula NbCl_{5}.[52] [51] The researches made by Roscoe were preceded by those of Marignac in 1865, on the _compounds_ of _niobium_ and _tantalum_, to which were also ascribed different formulæ from those now recognised. Tantalum was discovered simultaneously with vanadium by Hatchett and Ekeberg, and was afterwards studied by Rose, who in 1844 discovered niobium in it. Notwithstanding the numerous researches of Hermann (in Moscow), Kobell, Rose, and Marignac, still there is not yet any certainty as to the purity of, and the properties ascribed to, the compounds of these elements. They are difficult to separate from each other, and especially from the cerite metals and titanium, &c., which accompany them. Before the investigations of Rose the highest oxide of tantalum was supposed to belong to the type TaX_{6}--that is, its composition was taken as TaO_{3}, and to the lower oxide was ascribed a formula TaO_{2}. Rose gave the formula TaO_{2} to the higher oxide, and discovered a new element called niobium in the substance previously supposed to be the lower oxide. He even admitted the existence of a third element occurring together with tantalum and niobium, which he named pelopium, but he afterwards found that pelopic acid was only another oxide of niobium, and he considered it probable that the higher oxide of this element is NbO_{2}, and the lower Nb_{2}O_{3}. Hermann found that niobic acid which was considered pure contained a considerable quantity of tantalic acid, and besides this he admitted the existence of another special metallic acid, which he called ilmenic acid, after the locality (the Ilmen mountains of the Urals) of the mineral from which he obtained it. V. Kobell recognised still another acid, which he called dianic acid, and these diverse statements were only brought into agreement in the sixties by Marignac. He first of all indicated an accurate method for the separation of tantalic and niobic compounds, which are always obtained in admixture. [52] If niobic acid be mixed with a small quantity of charcoal and ignited in a stream of chlorine, a difficultly-fusible and difficultly-volatile oxychloride, NbOCl_{3} separates. The vapour density of this compound with respect to air is 7·5, and this vapour density perfectly confirms the accuracy of the formulæ given by Marignac, and indicates the quantitative analogy between the compounds of niobium and tantalum, and those of phosphorus and arsenic, and consequently also of vanadium. In their qualitative relations (as is evident also from the correspondence of the atomic weights), the compounds of tantalum and niobium exhibit a great analogy with the compounds of molybdenum and tungsten. Thus zinc, when acting on acid solutions of tantalic and niobic compounds, gives a blue coloration, exactly as it does with those of tungsten and molybdenum (also titanium). These acids form the same large number of salts as those of tungsten and molybdenum. The anhydrides of the acids are also insoluble in water, but as colloids are sometimes held in solution, just like those of titanic and molybdic acids. Furthermore, niobium is in every respect the nearest analogue of molybdenum, and tantalum of tungsten. _Niobium_ is obtained by reducing the double fluoride of niobium and sodium, with sodium. It is difficult to obtain in a pure state. It is a metal on which hydrochloric acid acts with some energy, as also does hydrofluoric acid mixed with nitric acid, and also a boiling solution of caustic potash. _Tantalum_, which is obtained in exactly the same way, is a much heavier metal. It is infusible, and is only acted on by a mixture of hydrofluoric and nitric acids. Rose in 1868 showed that in the reduction of the double fluoride, NbF_{5},2KF, by sodium, a greyish powder is obtained after treating with water. The specific gravity of this powder is 6·8, and he considers it to be niobium hydride, NbH. Neither did he obtain metallic niobium when he reduced with magnesium and aluminium, but an alloy, Al_{3}Nb, having a sp. gr. of 4·5. Niobium, so far as is known, unites in three proportions with oxygen. NbO, which is formed when NbOF_{3},2KF is reduced by sodium; NbO_{2}, which is formed by igniting niobic acid in a stream of hydrogen, and niobic anhydride, Nb_{2}O_{5}, a white infusible substance, which is insoluble in acids, and has a specific gravity of 4·5. Tantalic anhydride closely resembles niobic anhydride, and has a specific gravity of 7·2. _The tantalates and niobates_ present the type of ortho-salts--for example, Na_{2}HNbO_{4},6H_{2}O, and also of pyro-salts, such as K_{3}HNb_{2}O_{7},6H_{2}O, and of meta-salts--for example, KNbO_{3},2H_{2}O. And, besides these, they give salts of a more complex type, containing a larger amount of the elements of the anhydride; thus, for instance, when niobic anhydride is fused with caustic potash it forms a salt which is soluble in water, and crystallises in monoclinic prisms, having the composition K_{8}Nb_{6}O_{19},16H_{2}O. There is a perfectly similar isomorphous salt of tantalic acid. Tantalite is a salt of the type of metatantalic acid, Fe(TaO_{3})_{2}. The composition of Yttrotantalite appears to correspond with orthotantalic acid. CHAPTER XX SULPHUR, SELENIUM, AND TELLURIUM The acid character of the higher oxides RO_{3} of the elements of group VI. is still more clearly defined than that of the higher oxides of the preceding groups, whilst feeble basic properties only appear in the oxides RO_{3} of the elements of the even series, and then only for those elements having a high atomic weight--that is, under those two conditions in which, as a rule, the basic characters increase. Even the lower types RO_{2} and R_{2}O_{3}, &c., formed by the elements of group VI., are acid anhydrides in the uneven series, and only those of the elements of the even series have the properties of peroxides or even of bases. _Sulphur_ is the typical representative of group VI., both on account of the fact that the acid properties of the group are clearly defined in it, and also because it is more widely distributed in nature than any of the other elements belonging to this group. As an element of the uneven series of group VI., sulphur gives H_{2}S, sulphuretted hydrogen, SO_{3}, sulphuric anhydride, and SO_{2}, sulphurous anhydride. And in all of them we find acid properties--SO_{3} and SO_{2} are anhydrides of acids, and H_{2}S is an acid, although a feeble one. As an element sulphur has all the properties of a true non-metal; it has not a metallic lustre, does not conduct electricity, is a bad conductor of heat, is transparent, and combines directly with metals--in short it has all the properties of the non-metals, like oxygen and chlorine. Furthermore, sulphur exhibits a great qualitative and quantitative _resemblance to oxygen_, especially in the fact that, like oxygen, it combines _with two atoms of hydrogen_, and forms compounds resembling oxides with metals and non-metals. From this point of view sulphur is bivalent, if the halogens are univalent.[1] The chemical character of sulphur is expressed by the fact that it forms a very slightly stable and feebly energetic acid with hydrogen. The salts corresponding with this acid are the sulphides, just as the oxides correspond to water and the chlorides to hydrochloric acid. However, as we shall afterwards see more fully, the sulphides are more analogous to the former than to the latter. But although combining with metals, like oxygen, sulphur also forms chemically stable compounds with oxygen, and this fact impresses a peculiar character on all the relations of this element.[2] [1] The character of sulphur is very clearly defined in the organo-metallic compounds. Not to dwell on this vast subject, which belongs to the province of organic chemistry, I think it will be sufficient for our purpose to compare the physical properties of the ethyl compounds of mercury, zinc, sulphur and oxygen. The composition of all of them is expressed by the general formula (C_{2}H_{5})_{2}R, where R = Hg, Zn, S, or O. They are all volatile: mercury ethyl, Hg(C_{2}H_{5})_{2}, boils at 159°, its sp. gr. is 2·444, molecular volume = 106; zinc ethyl boils at 118°, sp. gr. 1·882, volume 101; ethyl sulphide, S(C_{2}H_{5})_{2}, boils at 90°, sp. gr. 0·825, volume 107; common ether, or ethyl oxide, O(C_{2}H_{5})_{2}, boils at 35°, sp. gr. 0·736, volume 101, in addition to which diethyl itself, (C_{2}H_{5})_{2} = C_{4}H_{10}, boils about 0°, sp. gr. about 0·62, volume about 94. Thus the substitution of Hg, S, and O scarcely changes the volume, notwithstanding the difference of the weights; the physical influence, if one may so express oneself, of these elements, which are so very different in their atomic weights, is almost alike. [2] Therefore in former times sulphur was known as an amphid element. Although the analogy between the compounds of sulphur and oxygen has been recognised from the very birth of modern chemistry (owing, amongst other things, to the fact that the oxides and sulphides are the most widely spread metallic ores in nature), still it has only been clearly expressed by the periodic system, which places both these elements in group VI. Here, moreover, stands out that parallelism which exists between SO_{2} and ozone OO_{2}, between K_{2}SO_{3} and peroxide of potassium K_{2}O_{4} (Volkovitch in 1893 again drew attention to this parallelism). Sulphur belongs to the number of those elements which _are very widely distributed in nature_, and occurs both free and combined in various forms. The atmosphere, however, is almost entirely free from compounds of sulphur, although a certain amount of them should be present, if only from the fact that sulphurous anhydride is emitted from the earth in volcanic eruptions, and in the air of cities, where much coal is burnt, since this always contains FeS_{2}. Sea and river water generally contain more or less sulphur in the form of sulphates. The beds of gypsum, sodium sulphate, magnesium sulphate, and the like are formations of undoubtedly aqueous origin. The sulphates contained in the soil are the source of the sulphur found in plants, and are indispensable to their growth. Among vegetable substances, the proteïds always contain from one to two per cent. of sulphur. From plants the albuminous substances, together with their sulphur, pass into the animal organism, and therefore the decomposition of animal matter is accompanied by the odour of sulphuretted hydrogen, as the product into which the sulphur passes in the decomposition of the albuminous substances. Thus a rotten egg emits sulphuretted hydrogen. Sulphur occurs largely in nature, as the various insoluble sulphides of the metals. Iron, copper, zinc, lead, antimony, arsenic, &c., occur in nature combined with sulphur. These _sulphides_ frequently have a metallic lustre, and in the majority of cases occur crystallised, and also very often several sulphides occur combined or mixed together in these crystalline compounds. If they are yellow and have a metallic lustre they are called pyrites. Such are, for example, copper pyrites, CuFeS_{2}, and iron pyrites, FeS_{2}, which is the commonest of all. They are all also known as glances or blendes if they are greyish and have a metallic lustre--for example, zinc blende, lead glance, PbS, antimony glance, Sb_{2}S_{3}, &c. And, lastly, sulphur occurs _native_. It occurs in this form in the most recent geological formations in admixture with limestone and gypsum, and most frequently in the vicinity of active or extinct volcanoes. As the gases of volcanoes contain sulphur compounds--namely, sulphuretted hydrogen and sulphurous anhydride, which by reacting on one another may produce sulphur, which also frequently appears in the craters of volcanoes as a sublimate--it might be imagined that the sulphur was of volcanic origin. But on a nearer acquaintance with its mode of occurrence, and more especially considering its relation to gypsum, CaSO_{4}, and limestone, the present general opinion leads to the conclusion that the 'native' sulphur has been formed by the reduction of the gypsum by organic matter and that its occurrence is only indirectly connected with volcanic agencies. Near Tetush, on the Volga, there are beds containing gypsum, sulphur, and asphalt (mineral tar). In Europe the most important deposits of sulphur are in the south of Sicily from Catania to Girgenti.[3] There are very rich deposits of sulphur in Daghestan near Cherkai and Cherkat in Khyut, near Mount Kanabour-bam, near Petrovsk, and in the Kira Koumski steppes in the Trans-Caspian provinces, which are able to supply the whole of Russia with this mineral. Abundant deposits of sulphur have also been found in Kamtchatka in the neighbourhood of the volcanoes. The method of separation of the sulphur from its earthy impurities is based on the fact that sulphur melts when it is heated. The fusion is carried on at the expense of a portion of the sulphur, which is burnt, so that the remainder may melt and run from the mass of the earth. This is carried on in special furnaces called calcaroni, built up of unhewn stone in the neighbourhood of the mines.[4] [3] When in Sicily, I found, near Caltanisetta, a specimen of sulphur with mineral tar. In the same neighbourhood there are naphtha springs and mud volcanoes. It may be that these substances have reduced the sulphur from gypsum. The chief proof in favour of the origin of sulphur from gypsum is that in treating the deposits for the extraction of the sulphur it is found that the proportion of sulphur to calcium carbonate never exceeds that which it would be had they both been derived from calcium sulphate. [4] Naturally only those ores of sulphur which contain a considerable amount of sulphur can be treated by this method. With poor ores it is necessary to have recourse to distillation or mechanical treatment in order to separate the sulphur, but its price is so low that this method in most cases is not profitable. The sulphur obtained by the above-described method still contains some impurities, but it is frequently made use of in this form for many purposes, and especially in considerable quantities for the manufacture of sulphuric acid, and for strewing over grapes. For other purposes, and especially in the preparation of gunpowder, a purer sulphur is required. Sulphur may be purified by distillation. The crude sulphur is called _rough_, and the distilled sulphur _refined_. The arrangement given in fig. 86 is employed for refining sulphur. The rough sulphur is melted in the boiler _d_, and as it melts it is run through the tube F into an iron retort B heated by the naked flame of the furnace. Here the sulphur is converted into vapour, which passes through a wide tube into the chamber G, surrounded by stone walls and furnished with a safety-valve S. [Illustration: FIG. 86.--Refining sulphur by sublimation.] Sulphur is purified by distillation in special retorts (see fig. 86) by passing the vapour into a chamber G built of stone. The first portions of the vapour entering into the condensing chamber are condensed straightway from the vapour into a solid state, and form a fine powder known as _flowers of sulphur_.[5] But when the temperature of the receiver attains the melting point of sulphur, it passes into a liquid state and is cast into moulds (like sealing wax), and is then known under the name of _roll sulphur_.[6] [5] Flowers of sulphur always contain a certain amount of the oxides of sulphur. [6] Sulphur may be extracted by various other means. It may be extracted from iron pyrites, FeS_{2}, which is very widely distributed in nature. From 100 parts of iron pyrites about half the sulphur contained, namely, about 25 parts, may be extracted by heating without the access of air, a lower sulphide of iron, which is more stable under the action of heat, being left behind. Alkali waste (Chapter XII.), containing calcium sulphide and gypsum, CaSO_{4}, may be used for the same purpose, but native sulphur is so cheap that recourse can only be had to these sources when the calcium sulphide appears as a worthless by-product. The most simple process for the extraction of sulphur from alkali waste, in a chemical sense, consists in evolving sulphuretted hydrogen from the calcium sulphide by the action of hydrochloric acid. The sulphuretted hydrogen when burnt gives water and sulphurous anhydride, which reacts on fresh sulphuretted hydrogen with the separation of sulphur. The combustion of the sulphuretted hydrogen may be so conducted that a mixture of 2H_{2}S and SO_{2} is straightway formed, and this mixture will deposit sulphur (Chapter XII., Note 14). Gossage and Chance treat alkali waste with carbonic anhydride, and subject the sulphuretted hydrogen evolved to incomplete combustion (this is best done by passing a mixture of sulphuretted hydrogen and air, taken in the requisite proportions, over red-hot ferric oxide), by which means water and the vapour of sulphur are formed: H_{2}S + O = H_{2}O + S. In an uncombined state sulphur exists in _several modifications_, and forms a good example of the facility with which an alteration of properties can take place without a change of composition--that is, as regards the material of a substance. Common sulphur has the well-known yellow colour. This colour fades as the temperature falls, and at -50° sulphur is almost colourless. It is very brittle, so that it may be easily converted into a powder, and it presents a crystalline structure, which, by the way, shows itself in the unequal expansion of lumps of sulphur by heat. Hence when a piece of sulphur is heated by the warmth of the hand, it emits sounds and sometimes cracks, which probably also depends on the bad heat-conducting power of this substance. It is easily obtained in a crystalline form by artificial means, because although insoluble in water it dissolves in carbon bisulphide, and in certain oils.[7] Solutions of sulphur in carbon bisulphide when evaporated at the ordinary temperature yield well-formed transparent crystals of sulphur in the form of rhombic octahedra, in which form it occurs native. The specific gravity of these crystals is 2·045. Fused sulphur, cast into moulds and cooled, has, after being kept a long time, a specific gravity 2·066; almost the same as that of the crystalline sulphur of the above form, which shows that common sulphur is the same as that which crystallises in octahedra. The specific heat of octahedral sulphur is 0·17; it melts at 114°, and forms a bright yellow mobile liquid. On further heating, the fused sulphur undergoes an alteration, which we shall presently describe, first observing that the above octahedral state of sulphur is its most stable form. Sulphur may be kept at the ordinary temperature in this form for an indefinite length of time, and many other modifications of sulphur pass into this form after being left for a certain time at ordinary temperature. [7] One hundred parts of liquid carbon bisulphide, CS_{2}, dissolve 16·5 parts of sulphur at -11°, 24 parts at 0°, 37 parts at 15°, 46 parts at 22°, and 181 parts at 55°. The saturated solution boils at 55°, whilst pure carbon bisulphide boils at 47°. The solution of sulphur in carbon bisulphide reduces the temperature, just as in the solution of salts in water. Thus the solution of 20 parts of sulphur in 50 parts of carbon bisulphide at 22° lowers the temperature by 5°; 100 parts of benzene, C_{6}H_{6}, dissolves 0·965 part of sulphur at 26°, and 4·377 parts at 71°; chloroform, CHCl_{3}, dissolves 1·2 part of sulphur at 22°, and 16·35 parts at 174°. If sulphur be melted and then slightly cooled, so that it forms a crust on the surface and over the sides of the crucible, while the internal mass remains liquid, then the sulphur takes another crystalline form as it solidifies. This may be seen by breaking the crust, and pouring out the remaining molten sulphur.[8] It is then found that the sides of the crucible are covered with _prismatic crystals_ of the monoclinic system; they have a totally different appearance from the above-described crystals of rhombic sulphur. The prismatic crystals are brown, transparent, and less dense than the crystals of rhombic sulphur, their specific gravity being only 1·93, and their melting point higher--about 120°. These crystals of sulphur cannot be kept at the ordinary temperature, which is indeed evident from the fact that in time they turn yellow; the specific gravity also changes, and they pass completely into the ordinary modification. This is accompanied by a considerable development of heat, so that the temperature of the mass may rise 12°. Thus sulphur is _dimorphous_--that is, it exists in two crystalline forms, and in both forms it has independent physical properties. However, no chemical reactions are known which distinguish the two modifications of sulphur, just as there are none distinguishing aragonite from calcspar.[9] [8] If the experiment be made in a vessel with a narrow capillary tube, the sulphur fuses at a lower temperature (occurs, as it were, in a supersaturated state), and solidifying at 90°, appears in a rhombic form (Schützenberger). [9] If sulphur be cautiously melted in a U tube immersed in a salt bath, and then gradually cooled, it is possible for all the sulphur to remain liquid at 100°. It will now be in a state of superfusion; thus also by careful refrigeration water may be obtained in a liquid state at -10°, and a lump of ice then causes such water to form ice, and the temperature rises to 0°. If a prismatic crystal of sulphur be thrown into one branch of the U tube containing the liquid sulphur at 100°, and an octahedral crystal be thrown into the other branch, then, as Gernez showed, the sulphur in each branch will crystallise in the corresponding form, and both forms are obtained at the same temperature; therefore it is not the influence of temperature only which causes the molecules of sulphur to distribute themselves in one or another form, but also the influence of the crystalline parts already formed. This phenomenon is essentially analogous to the phenomena of supersaturated solutions. If molten sulphur be heated to 158° it loses its mobility and becomes thick and very dark-coloured, so that the crucible in which it is heated may be inverted without the sulphur running out. When heated above this temperature the sulphur again becomes liquid, and at 250° it is very mobile, although it does not acquire its original colour, and at 440° it boils. These modifications in the properties of sulphur depend not only on the variations of temperature, but also on a change of structure. If sulphur, heated to about 350°, be poured in a thin stream into cold water, it does not solidify into a solid mass, but retains its brown colour and _remains soft_, may be stretched out into threads, and is elastic, like guttapercha. But in this soft and ductile state, also, it does not remain for a long time. After the lapse of a certain period this soft transparent sulphur hardens, becomes opaque, passes into the ordinary yellow modification of sulphur, and in so doing develops heat, just as in the conversion of the prismatic into the octahedral variety. The soft sulphur is characterised by the fact that a certain portion of it is insoluble in carbon bisulphide. When soft sulphur is immersed in this liquid, only a portion of common sulphur passes into solution, whilst a certain portion is quite insoluble and remains so for a long time. The maximum proportion of insoluble sulphur is obtained by heating slightly above 170°. It melts at 114°. An exactly similar _insoluble amorphous sulphur_ is obtained in certain reactions in the wet way, when sulphur separates out from solutions. Thus sodium thiosulphate, Na_{2}S_{2}O_{3}, when treated with acids, gives a precipitate of sulphur, which is insoluble in carbon bisulphide. The action of water on sulphur chloride also gives a similar modification of sulphur. Certain sulphides, when treated with nitric acid, also yield sulphur in this form.[10] [10] A certain amount of insoluble sulphur remains for a long time in the mass of soft sulphur, changing into the ordinary variety. Freshly-cooled soft sulphur contains about one-third of insoluble sulphur, and after the lapse of two years it still contains about 15 p.c. Flowers of sulphur, obtained by the rapid condensation of sulphur from a state of vapour, also contains a certain amount of insoluble sulphur. _Rapidly distilled and condensed sulphur_ also contains some insoluble sulphur. Hence a certain amount of insoluble sulphur is frequently found in roll sulphur. The action of light on a solution of sulphur converts a certain portion into the insoluble modification. Insoluble sulphur is of a lighter colour than the ordinary variety. It is best prepared by vaporising sulphur in a stream of carbonic anhydride, hydrochloric acid, &c., and collecting the vapour in cold water. When condensed in this manner it is nearly all insoluble in carbon bisulphide. It then has the form of hollow spheroids, and is therefore lighter than the common variety: sp. gr. 1·82. An idea of the modifications taking place in sulphur between 110° and 250° may be formed from the fact that at 150° liquid sulphur has a coefficient of expansion of about 0·0005, whilst between 150° and 250° it is less than 0·0003. Engel (1891), by decomposing a saturated solution of hyposulphite of sodium (Note 42) with HCl in the cold (the sulphur is not precipitated directly in this case), obtained, after shaking up with chloroform and evaporation, crystals of sulphur (sp. gr. 2·135), which, after several hours, passed into the insoluble (in CS_{2}) state, and in so doing became opaque, and increased in volume. But if a mixture of solution of Na_{2}S_{2}O_{3} and HCl be allowed to stand, it deposits sulphur, which, after sufficient washing, is able to dissolve in water (like the colloid varieties of the metallic sulphides, alumina, boron, and silver), but this colloid _solution of sulphur_ soon deposits sulphur insoluble in CS_{2}. When a solution of sulphuretted hydrogen in water is decomposed by an electric current the sulphur is deposited on the positive pole, and has therefore an electro-negative character, and this sulphur is soluble in carbon bisulphide. When a solution of sulphurous acid is decomposed in the same manner, the sulphur is deposited on the negative pole, and is therefore electro-positive, and the sulphur so deposited is insoluble in carbon bisulphide. The sulphur which is combined with metals must have the properties of the sulphur contained in sulphuretted hydrogen, whilst the sulphur combined with chlorine is like that which is combined with oxygen in sulphurous anhydride. Hence Berthelot recognises the presence of soluble sulphur in metallic sulphides, and of the insoluble modification of amorphous sulphur in sulphur chloride. Cloez showed that the sulphur precipitated from solutions is either soluble or insoluble, according to whether it separates from an alkaline or acid solution. If sulphur be melted with a small quantity of iodine or bromine, then on pouring out the molten mass it forms amorphous sulphur, which keeps so for a very long time, and is insoluble, or nearly so, in carbon bisulphide. This is taken advantage of in casting certain articles in sulphur, which by this means retain their tenacity for a long time; for example, the discs of electrical machines. At temperatures of 440° to 700° the vapour density of sulphur is 6·6 referred to air--_i.e._ about 96 referred to hydrogen. Hence, at these temperatures _the molecule of sulphur contains six atoms_, it has the composition S_{6}. The agreement between the observations of Dumas, Mitscherlich, Bineau, and Deville confirms the accuracy of this result. But in this respect the properties of sulphur were found to be variable. When heated to higher temperatures, that is to say, _above_ 800°, the vapour density of sulphur is found to be one-third of this quantity, _i.e._ about 32 referred to hydrogen. At this temperature _the molecule of sulphur_, like that of hydrogen, oxygen, nitrogen, and chlorine, _contains two atoms_; hence the molecular formula is then S_{2}. This variation in the vapour density of sulphur evidently corresponds with a polymeric modification, and may be likened to the transformation of ozone, O_{3}, into oxygen, O_{2}, or better still, of benzene, C_{6}H_{6}, into acetylene, C_{2}H_{2}.[11] [11] Here, however, it is very important to remark that both benzene and acetylene can exist at the ordinary temperature, whilst the sulphur molecule S_{2} only exists at high temperatures; and if this sulphur be allowed to cool, it passes first into S_{6} and then into a liquid state. Were it possible to have sulphur at the ordinary temperature in both the above modifications, then in all probability the sulphur in the state S_{2} would present totally different properties from those which it has in the form S_{6}, just as the properties of gaseous acetylene are far from being similar to those of liquid benzene. Sulphur, in the form of S_{2}, is probably a substance which boils at a much lower temperature than the variety with which we are now dealing. Paterno and Nasini (1888), following the method of depression or fall of the freezing-point in a benzene solution, found that the molecule of sulphur in solution contains S_{6}. One must here call attention to the fact that sulphur, with all its analogy to oxygen (which also shows itself in its faculty to give the modification S_{2}), is also able to give a series of compounds containing more atoms of sulphur than the analogous oxygen compounds do of oxygen. Thus, for instance, compounds of 5 atoms of sulphur with 1 atom of barium, BaS_{5}, are known, whereas with oxygen only BaO_{2} is known. On every side one cannot but see in sulphur a faculty for the union of a greater number of atoms than with oxygen. With oxygen the form of ozone, O_{3}, is very unstable, the stable form is O_{2}; whilst with sulphur S_{6} is the stable form, and S_{2} is exceedingly unstable. Furthermore, it is remarkable that sulphur gives a higher degree of oxidation, H_{2}SO_{4}, corresponding, as it were, with its complex composition, if we suppose that in S_{6} four atoms of sulphur are replaced by oxygen and one by two atoms of hydrogen. The formulæ of its compounds, K_{2}SO_{4}, K_{2}S_{2}O_{3}, K_{2}S_{5}, BaS_{5}, and many others, have no analogues among the compounds of oxygen. They all correspond with the form S_{6} (one portion of the sulphur being replaced by oxygen and another by metals), which is not attained by oxygen. In this faculty of sulphur to hold many atoms of other substances the same forces appear which cause many atoms of sulphur to form one complex molecule. _In its faculty for combination_, sulphur most closely resembles oxygen and chlorine; like them, it combines with nearly all elements, with the development of heat and light, forming sulphur compounds, but as a rule this only takes place at a high temperature. At the ordinary temperature it does not enter into reactions, owing, amongst other things, to the fact that it is a solid. In a molten state it acts on most metals and on the halogens. It burns in air at about 300°, and with carbon at a red heat, but it does not combine with nitrogen. Fine wires, or the powders of the greater number of metals, burn in the vapour of sulphur. The direct combination of hydrogen with sulphur is restricted by a limit--that is, at a given temperature and under other given conditions it does not proceed unrestrictedly; there is no explosion or recalescence. Sulphuretted hydrogen, H_{2}S, decomposes at its temperature of combination--that is, it is easily dissociated.[12] The same phenomenon is repeated here as with water, except that the temperatures at which the attraction of hydrogen for sulphur begins and ceases are much lower than in the case of oxygen and hydrogen. The temperature at which combination takes place is here, as in many other instances, nearly the same as that at which dissociation begins. Hence _sulphuretted hydrogen_ is formed in a small quantity by the direct ignition of a mixture of the vapour of sulphur and hydrogen. However, the temperature must not be high, because otherwise the whole of the sulphuretted hydrogen is decomposed; but at lower temperatures a small amount of sulphuretted hydrogen is formed by direct combination.[13] Sulphuretted hydrogen however, like all other hydrogen compounds, may be easily obtained by the double decomposition of its corresponding metallic compounds, the replacement of the metal by hydrogen being effected by the action of acids on the sulphides. The metallic sulphides are, as a rule, easily formed. A sulphide, when mixed with a non-volatile acid, may give, by double decomposition, a salt of the acid taken and sulphuretted hydrogen, M_{2}S + H_{2}SO_{4} = H_{2}S + M_{2}SO_{4}. However, it is not all sulphides nor solutions of all acids that will evolve sulphuretted hydrogen, which fact is exceedingly characteristic, because, for example, all carbonates evolve carbonic anhydride when treated with any acid. Sulphuric acid will only evolve sulphuretted hydrogen from those sulphides which contain a metal capable of decomposing the acid with the evolution of hydrogen. Thus zinc, iron, calcium, magnesium, manganese, potassium, sodium, &c., form sulphides which evolve sulphuretted hydrogen when treated with sulphuric acid, and the metals themselves evolve hydrogen with acids.[14] The sulphides of those metals which do not liberate hydrogen from acids do not generally act on acids--that is, do not form sulphuretted hydrogen with them; such are, for example, the sulphides of lead, silver, copper, mercury, tin, &c. Therefore, the _modus operandi_ of the formation of sulphuretted hydrogen by the action of acids on metallic sulphides may be looked on as a phenomenon of the combination of hydrogen, at the moment of its evolution, with the sulphur, which is combined with the metal. Such a representation is all the more simple as all the circumstances under which sulphuretted hydrogen is formed are exactly similar to the conditions of the formation of hydrogen itself. Thus the usual mode of preparing sulphuretted hydrogen is by the action of _sulphuric acid on ferrous sulphide_, in which the same apparatus and method are employed as in the preparation of hydrogen, only replacing the metallic iron or zinc by ferrous sulphide or zinc sulphide. The reaction between sulphide of iron and sulphuric acid takes place at the ordinary temperature, and is accompanied by just as small a development of heat as in the liberation of hydrogen itself, FeS + H_{2}SO_{4} = FeSO_{4} + H_{2}S.[15] [12] In the formation of potassium sulphide, K_{2}S (that is, in the combination of 32 parts of sulphur with 78 parts of potassium), about 100 thousand heat units are developed. Nearly as much heat is developed in the combination of an equivalent quantity of sodium; about 90 thousand heat units in the formation of calcium or strontium sulphide; about 40 thousand for zinc or cadmium sulphide, and about 20 thousand for iron, cobalt, or nickel sulphide. Less heat is evolved in the combination of sulphur with copper, lead, and silver. According to Thomsen, sulphur develops heat with hydrogen in solutions. The reaction I_{2},Aq,H_{2}S = 21,830 calories. But, as the reaction I_{2} + H_{2} + Aq develops 26,842 calories, it follows that the reaction H_{2} + S develops 4,512 calories. [13] If sulphur be melted in a flask and heated nearly to its boiling point, as Lidoff showed, the addition, drop by drop (from a funnel with a stopcock) of heavy (0·9) naphtha oil (of lubricating oleonaphtha), &c., is followed by a regular evolution of sulphuretted hydrogen. This is analogous to the action of bromine or iodine on paraffin and other oils, because hydrobromic or hydriodic acid is then formed (Chapter XI.) A certain amount of hydrogen sulphide is even formed when sulphur is boiled with water. [14] However, the matter is really much more complicated. Thus zinc sulphide evolves sulphuretted hydrogen with sulphuric or hydrochloric acids, but does not react with acetic acid and is oxidised by nitric acid. Ferrous sulphide evolves sulphuretted hydrogen with acids, whilst the bisulphide, FeS_{2}, does not react with acids of ordinary strength. This absence of action depends, among other things, on the form in which the native iron pyrites occurs; it is a crystalline, compact, and very dense substance; and acids in general react with great difficulty on such metallic sulphides. This is seen very clearly in the case of zinc sulphide; if this substance is obtained by double decomposition, it separates as a white precipitate, which evolves sulphuretted hydrogen with great ease when treated with acids. Zinc sulphide is obtained in the same form when zinc is fused with sulphur, but native zinc sulphide--which occurs in compact masses of zinc blende, and has a metallic lustre--is not decomposed or scarcely decomposed by sulphuric acid. Another source of complication in the behaviour of the metallic sulphides towards acids depends on the action of water, and is shown in the fact that the action varies with different degrees of dilution or proportion of water present. The best known example of this is antimonious sulphide, Sb_{2}S_{3}, for strong hydrochloric acid, containing not more water than corresponds with HCl,6H_{2}O, even decomposes native antimony glance, with evolution of sulphuretted hydrogen, whilst dilute acid has no action, and in the presence of an excess of water the reaction 2SbCl_{3} + 3H_{2}S = Sb_{2}S_{3} + 6HCl occurs, whilst in the presence of a small amount of water the reaction proceeds in exactly the opposite direction. Here the participation of water in the reaction and its affinity are evident. The facts that lead sulphide is insoluble in acids, that zinc sulphide is soluble in hydrochloric acid but insoluble in acetic acid, that calcium sulphide is even decomposed by carbonic acid, &c.--all these peculiarities of the sulphides are in correlation with the amount of heat evolved in the reaction of the oxides with hydrogen sulphide and with acids, as is seen from the observations of Favre and Silberman, and from the comparisons made by Berthelot in the Proceedings of the Paris Academy of Sciences, 1870, to which we refer the reader for further details. [15] _Ferrous sulphide_ is formed by heating a piece of iron to an incipient white heat, and then removing it from the furnace and bringing it into contact with a piece of sulphur. Combination then proceeds, accompanied by the development of heat, and the ferrous sulphide formed fuses. The sulphide of iron thus formed is a black, easily-fusible substance, insoluble in water. When damp it attracts oxygen from the air, and is converted into green vitriol, FeSO_{4}. If all the iron does not combine with the sulphur in the method described above, the action of sulphuric acid will evolve hydrogen as well as hydrogen sulphide. We will not describe the details of the preparation of sulphuretted hydrogen employed as a reagent in the laboratory, because, in the first place, the methods are essentially the same as in the preparation of hydrogen, and, in the second place, because the apparatus and methods employed are always described in text-books of analytical chemistry. Ferrous sulphide may be advantageously replaced by calcium sulphide or a mixture of calcium and magnesium sulphides. A solution of magnesium hydrosulphide, MgS,H_{2}S, is very convenient, as at 60° it evolves a stream of pure hydrogen sulphide. A paste, consisting of CuS with crystals of MgCl_{2} and water, may also be employed, since it only evolves H_{2}S when heated (Habermann). _In nature_ sulphuretted hydrogen is formed in many ways. The most usual mode of its formation is by the decomposition of albuminous substances containing sulphur, as mentioned above. Another method is by the reducing action of organic matter on sulphates, and by the action of water and carbonic acid on the sulphides formed by this reduction. Volcanic eruptions are a third source of sulphuretted hydrogen in nature. Although sulphuretted hydrogen is formed in small quantities everywhere, it nevertheless soon disappears from the atmosphere, owing to its being easily decomposed by oxidising agencies. Many mineral waters contain sulphuretted hydrogen, and smell of it; they are called 'sulphur waters.' Sulphuretted hydrogen, at the ordinary temperature, is a colourless gas, having a very unpleasant odour. It has, as its composition H_{2}S shows, a specific gravity seventeen times greater than hydrogen, and therefore it is somewhat heavier than air. Sulphuretted hydrogen _liquefies_ at about -74°, and at the ordinary temperature when subjected to a pressure of 10 to 15 atmospheres; at -85° it is converted into a solid crystalline mass.[15 bis] The easy liquefaction of sulphuretted hydrogen is evidently allied to its solubility. One volume of water at 0° dissolves 4·37 volumes of sulphuretted hydrogen, at 10° 3·58 volumes, and at 20° 2·9 volumes.[16] The solutions impart a very feeble red coloration to litmus paper. This gas is poisonous. One part in fifteen hundred parts of air will kill birds. Mammalia die in an atmosphere containing 1/200 of this gas. [15 bis] Liquid sulphuretted hydrogen is most easily obtained by the decomposition of hydrogen polysulphide, which we shall presently describe, by the action of heat, and in the presence of a small amount of water. If poured into a bent tube, like that described for the liquefaction of ammonia (Chapter VI.), the hydrogen polysulphide is decomposed by heat, in the presence of water, into sulphur and sulphuretted hydrogen, which condenses in the cold end of the tube into a colourless liquid. [16] Sulphuretted hydrogen is still more soluble in alcohol than in water; one volume at the ordinary temperature dissolves as much as eight volumes of the gas. The solutions in water and alcohol undergo change, especially in open vessels, owing to the fact that the water and alcohol dissolve oxygen from the atmosphere, which, acting on the sulphuretted hydrogen, forms water and sulphur. The solution may be so altered in this manner that every trace of sulphuretted hydrogen disappears. Solutions of sulphuretted hydrogen in glycerine change much more slowly, and may therefore be kept for a long time as reagents. De Forcrand obtained a hydrate, H_{2}S,16H_{2}O, resembling the hydrates given by many gases. Sulphuretted hydrogen is very easily _decomposed_ into its component parts by the action of heat or a series of electric sparks. Hence it is not surprising that sulphuretted hydrogen undergoes change under the action of many substances having a considerable affinity for hydrogen and oxygen. Very many metals[17] evolve hydrogen with sulphuretted hydrogen, so that in this respect it presents the property of an acid; for instance, 2H_{2}S + Sn = 2H_{2} + SnS_{2}. This may be taken advantage of for determining the composition of sulphuretted hydrogen, because a given volume then leaves the same volume of hydrogen. On the other hand, oxygen,[18] chlorine,[19] and even iodine decompose sulphuretted hydrogen, removing the hydrogen from it and leaving free sulphur, so that in this reaction the sulphur is replaced by the above-named elements; for example, H_{2}S + Br_{2} = 2HBr + S. In no other hydrogen compound is it so easy to show the _substitution_, both of hydrogen and of the element combined with it, as in hydrogen sulphide. This clearly proves the feeble union between the elements forming this gas. Compounds containing a considerable amount of oxygen, with which they easily part, can accomplish the separation of the sulphur very easily. Such are, for instance, nitrous acid, chromic acid, and even ferric oxide and the higher oxides like it. Thus, if sulphuretted hydrogen be passed into a solution of chromic acid or an acid solution of ferric oxide, water is formed, _and the sulphur is separated in a free state_. Thus, sulphuretted hydrogen acts as a _reducing agent_, in virtue of the hydrogen it contains. Salts of iodic, chlorous, chloric, and other acids are reduced by sulphuretted hydrogen, their oxygen acting mainly on its hydrogen; but in the presence of an excess of a powerful oxidising agent a portion of the sulphur may also be oxidised to sulphurous anhydride. The reducing action of sulphuretted hydrogen is frequently applied in chemical manipulations for the preparation of lower oxides, and for the conversion of certain oxygen compounds into hydrogen compounds: thus, the higher oxides of nitrogen are converted into ammonia by it, and in the presence of alkalis the nitro-compounds are converted into ammonia derivatives. The reaction of sulphuretted hydrogen on sulphurous anhydride belongs to this class of phenomena, the chief products of which are sulphur and water, 2H_{2}S + SO_{2} = 2H_{2}O + S_{3}. [17] Some metals evolve hydrogen from sulphuretted hydrogen at the ordinary temperature. For example, the light metals, and copper and silver (especially with the access of air?) among the heavy metals. Hence articles made of silver turn black in the presence of vapours containing sulphuretted hydrogen, because silver sulphide is black. Zinc and cadmium act at a red heat, but not completely. [18] If sulphuretted hydrogen escapes from a fine orifice into the air, it will burn when lighted, and be transformed into sulphurous anhydride and water. But if it burns in a limited supply of air--for instance, when a cylinder is filled with it and lighted--then only the hydrogen burns, which has, judging from the amount of heat developed in its combustion and from all its properties, a greater affinity for oxygen than sulphur. In this respect the combustion of sulphuretted hydrogen resembles that of hydrocarbons. [19] Hence bleaching powder and chlorine destroy the disagreeable smell of sulphuretted hydrogen. (For the reaction of hydrogen sulphide and iodine, _see_ Chapter XI. p. 504.) The acid character of sulphuretted hydrogen is clearly seen in its action on alkalis and salts.[19 bis] Thus lead oxide and its salts in the presence of sulphuretted hydrogen form water or an acid, and sulphide of lead: PbX_{2} + H_{2}S = PbS + 2HX. This reaction takes place even in the presence of powerful acids, because lead sulphide is one of those sulphides which are unacted on by acids, and in solutions the reaction is a complete one. This reaction is taken advantage of for the preparation of many acids, by first converting into a lead salt, and then submitting this salt to the action of sulphuretted hydrogen. For example, lead formate with sulphuretted hydrogen gives formic acid. Sulphuretted hydrogen in acting on a number of metallic acid substances in solution or in an anhydrous state also forms corresponding sulphates: (1) if it does not reduce the acid; (2) if the sulphur compound corresponding with the anhydride of the acid be insoluble in water, the reaction proceeds in solutions; (3) if the sulphuretted hydrogen and the acid taken do not come in contact with an alkali, on which they would be able to act first; and (4) if the sulphur compound be not decomposed by water. Thus solutions of arsenious acid give a precipitate of arsenious sulphide, As_{2}S_{3}, with sulphuretted hydrogen. This reaction proceeds not only in the presence of water, but also of acids, because the latter do not decompose the resultant sulphur compounds. The type of the decomposition is the same as with bases--that is, the sulphur and oxygen change places: RO_{_n_} + _n_H_{2}S = RS_{_n_} + _n_H_{2}O. Some sulphides corresponding with acid anhydrides are decomposed by water, and therefore are not formed in the presence of water. Such, for example, are the sulphides of phosphorus.[20] [19 bis] Perfectly dry H_{2}S (Hughes 1892) has no action upon perfectly dry salts, just as dry HCl does not react with dry NH_{3} or metals (Chapter IX., Note 29). [20] The sulphide P_{4}S is obtained by cautiously fusing the requisite proportions of common phosphorus and sulphur under water; it is a liquid which solidifies at 0°, and may be distilled without undergoing change, but it fumes in air and easily takes fire. The higher sulphide, P_{2}S, has similar properties. But little heat is evolved in the formation of these compounds, and it may be supposed that they are formed by the direct conjunction of whole molecules of phosphorus and sulphur; but if the proportion of sulphur be increased, the reaction is accompanied by so considerable a rise of temperature that an explosion takes place, and for the sake of safety red phosphorus must be used, mixed as intimately as possible with powdered sulphur and heated in an atmosphere of carbonic anhydride. The higher compounds are decomposed by water. By increasing the proportion of sulphur, the following compounds have been obtained: P_{4}S_{3} as prisms (fuses at 165°, Rebs), soluble in carbon bisulphide, and unaltered by air and water; _phosphorus trisulphide_, P_{2}S_{3}, is the analogue of P_{2}O_{3}; it is a light yellow crystalline compound only slightly soluble in carbon bisulphide, fusible and volatile, decomposed into hydrogen sulphide and phosphorous acid by water, and, like the highest compound of sulphur and phosphorus, P_{2}S_{5}, it forms thio-salts with potassium sulphide, &c. This _phosphorus pentasulphide_ corresponds with phosphoric anhydride; like the trisulphide it gives hydrogen sulphide and phosphoric acid with an excess of water. It reacts in many respects like phosphoric chloride. The sulphide PS_{2} is also known; the vapour density of this compound seems to indicate a molecule P_{3}S_{6}. _Phosphorus sulphochloride_, PSCl_{3}, corresponds with phosphorus oxychloride. It is a colourless, pleasant-smelling liquid, boiling at 124°, and of sp. gr. 1·63; it fumes in air and is decomposed by water: PSCl_{3} + 4H_{2}O = PH_{3}O_{4} + H_{2}S + 3HCl. It is obtained when phosphoric chloride is treated with hydrogen sulphide, hydrochloric acid being also formed; it is also produced by the action of phosphoric chloride on certain sulphides--for example, on antimonious sulphide, also by the (cautious) action of phosphorus on sulphur chloride: 2P + 3S_{2}Cl_{2} = 2PSCl_{3} + 4S, by the action of PCl_{5} upon certain sulphides, for example, Sb_{2}S_{3}, by the reaction: 3MCl + P_{2}S_{5} = PSCl_{3} + M_{3}PS_{4} (Glatzel, 1893), and in the reaction 3PCl_{3} + SOCl_{2} = PCl_{5} + POCl_{3} + PSCl_{3}, showing the reducing action of phosphorus trichloride, which is especially clear in the reaction SO_{3} + PCl_{3} = SO_{2} + POCl_{3}. Thorpe and Rodger (1889), by heating 3PbF_{2} or BiF_{3} with phosphorus pentasulphide (and also by heating AsF_{3} and PSCl_{3} to 150°), obtained thiophosphoryl fluoride as a colourless, spontaneously inflammable gas (see further on, Note 74 bis, and Chapter XIX., Note 25). The action of PSCl_{3} upon NaHO gives a salt of monothiophosphoric acid (Würtz, Kubierschky), H_{3}PSO_{3}, which gives soluble salts of the alkalis. The metallic sulphides corresponding with the metallic oxides have either a feeble alkaline or a feeble acid character, according to the character of the corresponding oxide, and therefore by combining together they are able to form saline substances--that is, salts in which the oxygen is replaced by sulphur. Thus sulphuretted hydrogen having the properties of a feeble acid[21] has, at the same time, the properties of water, and forms the type of the sulphur derivatives, which may also be formed by means of sulphuretted hydrogen, just as the oxides may be formed by the aid of water. But as sulphuretted hydrogen has acid properties, it combines more easily with the basic metallic sulphides. Hence, for instance, there exists a compound of sulphuretted hydrogen with potassium sulphide, potassium hydrosulphide, 2KHS = K_{2}S + H_{2}S, just as there are potassium hydroxides; but there are scarcely any compounds of sulphuretted hydrogen with the sulphides corresponding with acids. Thus the sulphides of the metals may be regarded either as salts of sulphuretted hydrogen or as oxides of the metals in which the oxygen is replaced by sulphur. In general terms the sulphides exhibit the same degrees of difference with respect to their solubility in water as do the oxides. Thus the oxides of the alkali metals, and of some of the metals of the alkaline earths, are soluble in water, whilst those of nearly all the other metals are insoluble. The same may be said as to the sulphides; the sulphides of the metals of the alkalis and certain of the alkaline earths are soluble in water, whilst those of the other metals are insoluble. Those metals, like aluminium, whose oxides--for example, Al_{2}O_{3}--have intermediate properties and do not form compounds with feeble acids, at least in a wet way, also do not form sulphides by this method, although these may be obtained indirectly. And in general the sulphides of the metals are easily formed in a wet way, and with particular ease if they are insoluble in water. In this case their salts enter into double decomposition with sulphuretted hydrogen, or with soluble sulphides, and give an insoluble sulphide--for instance, a salt of lead gives lead sulphide with sulphuretted hydrogen. By the action of sulphuretted hydrogen on a salt of a metal, a free acid must be formed besides the metallic sulphide. Thus if a metal M be in a state of combination MX_{2}, then by the action of sulphuretted hydrogen there will be formed, besides MS,[22] an acid 2HX. It is evident that sulphuretted hydrogen will not precipitate an insoluble sulphide from the salts of those metals whose sulphides react with free acid, such as zinc, iron, manganese, &c. The reaction FeCl_{2} + H_{2}S = FeS + 2HCl, and the like, do not take place because the acid acts on the ferrous sulphide. Antimonious sulphide is not acted on by dilute hydrochloric acid, but it is decomposed by strong acid, and therefore in presence of an excess of hydrochloric acid antimonious chloride does not entirely react with hydrogen sulphide, whilst the reaction 2SbCl_{3} + 3H_{2}S = Sb_{2}S_{3} + 6HCl is a complete one in a dilute solution and with a small quantity of acid. Those metallic sulphides which are decomposed by acids may be obtained in a wet way by the double decomposition of the salts of the metals, not with hydrogen sulphide, but with soluble metallic sulphides, such as sulphide of ammonium or of potassium, because then no free acid is formed, but a salt of the metal (potassium or ammonium) which was taken as a soluble sulphide. So, for example, FeCl_{2} + K_{2}S = FeS + 2KCl.[23] [21] Sulphuretted hydrogen does not saturate the alkaline properties of alkali hydroxides, so that a solution of potassium hydroxide will not under any circumstances give a neutral liquid with sulphuretted hydrogen. In this case the sulphuretted hydrogen forms in solution only an acid salt with the potassium: KHO + H_{2}S = KHS + H_{2}O. It must be supposed that the normal salt is not formed in the solution--that is, that the reaction 2KHO + H_{2}S = K_{2}S + 2H_{2}O does not take place. This is seen from the fact that a development of heat, depending on the formation of potassium hydrosulphide, KHS, is remarked when as much hydrogen sulphide is passed into a solution of potassium hydroxide as it will absorb. But if a further quantity of potassium hydroxide be added to the resultant solution, heat is not developed, whilst if alkali be added to potassium acid sulphate or sodium acid carbonate, heat is developed. It must not be concluded from this that H_{2}S is a monobasic acid, for here there is a question of the decomposing action of water upon K_{2}S; K_{2}S and H_{2}O in reacting on each other should absorb heat if the reaction of KHS upon KHO evolves heat. Furthermore, it must be taken into account that potassium oxide, K_{2}O, and the anhydrous oxides like it, also do not exist in solutions, for whenever they are formed they immediately react with the water, forming caustic potash, KHO, &c. In the same way, directly potassium sulphide, K_{2}S, is formed in water it is decomposed into potassium hydroxide and hydrosulphide: K_{2}S + H_{2}O = KHO + KHS. Potassium sulphide, K_{2}S, in a solid state corresponds with K_{2}O, although neither can exist in solution. [22] During recent years (beginning with Schulze, 1882) it has been found that many metallic sulphides which were considered totally insoluble do, under certain circumstances, form very unstable solutions in water, as already mentioned in Chapter I., Note 57. Arsenic sulphide is very easily obtained in the form of a solution (hydrosol). Solutions of copper and cadmium sulphides may also be easily obtained by precipitating their salts CuX_{2}, or CdX_{2}, with ammonium sulphide, and washing the precipitate; but they are re-precipitated by the addition of foreign salts. [23] In reality the preceding reaction should be expressed thus: FeCl_{2} + 2KHS = FeS + 2KCl + H_{2}S (Note 21), because in the presence of water not K_{2}S but KHS reacts. But as the sulphuretted hydrogen takes no part in the reaction, it is usual to express the formation of such sulphides without taking the hydrogen sulphide proceeding from the potassium or ammonium hydrosulphides into account. It is not usual to employ potassium sulphide but ammonium sulphide--or, to speak more accurately, ammonium hydrosulphide--in order to avoid the formation of a non-volatile salt of potassium and to have, together with the formation of the sulphide, a salt of ammonium which can always be driven off by evaporating the solution and igniting the residue--for instance: FeCl_{2} + (NH_{4})_{2}S = FeS + 2NH_{4}Cl. Thus the metallic sulphides may be divided into three chief classes: (1) _those soluble in water_, (2) _those insoluble in water but reacting with acids_, and (3) _those insoluble both in water and acids_. The third class may be easily subdivided into two groups; to the first group belong those sulphides which correspond with bases or basic oxides, and are therefore unable to play the part of an acid with the sulphides of the alkalis, and are insoluble in NH_{4}HS, whilst the sulphides of the second group are of an acid character, and give soluble thio-salts with the sulphides of the alkaline metals, in which they play the part of an acid. To this group belong those metals whose corresponding oxides have acid properties. It must be observed, however, that not all metallic acids have corresponding sulphides, partly owing to the fact that certain acids are reducible by sulphuretted hydrogen, especially when their lower degrees of oxidation are of a basic character. Such are, for instance, the acids of chromium, manganese, &c. Sulphuretted hydrogen converts them into lower oxides, having the properties of bases. Those bases which do not combine with feeble acids, such as carbonic acid and hydrogen sulphide, give a precipitate of hydroxide with ammonium sulphide--for example, aluminium salts react in this manner. This difference of the metals in their behaviour towards sulphuretted hydrogen gives a very valuable means of separating them from each other, and _is taken advantage of in analytical chemistry_. If, for instance, the metals of the first and third groups occur together, it is only necessary to convert them into soluble salts, and to act on the solution of the salts with sulphuretted hydrogen; this will precipitate the metals of the third group in the form of sulphides, whilst the metals of the first group will not be in the least acted on. Such a method of separating the metals is considered more fully in analytical chemistry, and we will therefore limit ourselves here to pointing out to which groups the most common metals belong, and the colour which is proper to the sulphide precipitated. _Metals which are precipitated by sulphuretted hydrogen_, as sulphides from a solution of their salts, even in the presence of free acid: The precipitate is soluble in ammonium sulphide: _Platinum_ (dark brown) | _Antimony_ (orange) _Gold_ (dark brown) | _Arsenic_ (yellow) _Tin_ (yellow and brown) | The precipitate is insoluble in ammonium sulphide: _Copper_ (black) | _Mercury_ (black) _Silver_ (black) | _Lead_ (black) _Cadmium_ (yellow) | _Metals which are precipitated by ammonium sulphide_ from neutral solutions, but not precipitated from acid solutions by sulphuretted hydrogen: The sulphide precipitated is soluble in hydrochloric acid: _Zinc_ (white) | _Manganese_ (rose colour) | _Iron_ (black) The sulphide precipitated is not soluble in dilute hydrochloric acid: _Nickel_ (black) | _Cobalt_ (black) A hydroxide, and not a sulphide, is precipitated: _Chromium_ (green) | _Aluminium_ (white) The metals of the alkalis and of the alkaline earths are not precipitated either by sulphuretted hydrogen or ammonium sulphide. The metals of the alkaline earths when in acid solutions in the form of phosphates and many other salts are precipitated by ammonium sulphide, because the latter neutralises the free acid, with formation of an ammonium salt of the acid and evolution of sulphuretted hydrogen. Metallic sulphides may be obtained by many other means besides the action of sulphuretted hydrogen on salts and oxides, or by the simple combination of metals with sulphur when heated or fused. Thus they may also be formed by the reduction of sulphates by heating them with charcoal or other means. Charcoal takes up the oxygen from many sulphates, leaving corresponding sulphides. Thus sodium sulphate, Na_{2}SO_{4}, when heated with charcoal, forms sodium sulphide, Na_{2}S. Besides which metallic sulphides are also obtained by heating metals or their oxides in the vapours of many sulphur compounds--for example, in the vapour of carbon bisulphide, CS_{2}, when the carbon takes up the oxygen and the sulphur combines with the metal. The sulphides formed in this manner are often crystalline, and often appear with those properties and in that crystalline form in which they occur in nature. Besides which we must mention that many of the sulphides of the metals are oxidised in air at the ordinary, and especially at a higher, temperature, forming either SO_{2} and the oxide of the metal or sulphates. This oxidation proceeds with particular ease, even at the ordinary temperature, when a metallic sulphide is precipitated from its solutions, as a fine powder containing water. The sulphides of iron and manganese, &c., are very easily oxidised in this manner. But if these hydrates be ignited, they lose their water (the ignition must be carried on in a stream of hydrogen to prevent their oxidation during the process), become denser, and are no longer oxidised at the ordinary temperature. Those sulphides whose corresponding sulphates are decomposed by heat part with their sulphur in the form of sulphurous anhydride when they are ignited in air, and the metal, as a rule, remains behind as oxide. This is taken advantage of in the treatment of sulphurous ores. The process is called _roasting_. Hydrogen not only forms sulphuretted hydrogen with sulphur, but it also combines with it in several other proportions, just as it combines with oxygen, forming not only water but also hydrogen peroxide. Moreover these _polysulphides of hydrogen_ are also unstable, like hydrogen peroxide, and are also obtained from the corresponding polysulphides of the metals of the alkaline earths, just as hydrogen peroxide is obtained from barium peroxide. Thus calcium forms not only calcium sulphide, CaS, but also as bi-, tri-, and pentasulphide, CaS_{5}, and all these compounds are soluble in water. Sodium also combines with sulphur in the same proportions, forming sulphides from Na_{2}S to Na_{2}S_{5}. If an acid be added to a solution of a polysulphide, it gives sulphur, sulphuretted hydrogen, and a salt of the metal. For instance, MS_{5}, + 2HCl = MCl_{2} + H_{2}S + 4S. If we reverse the operation, and pour a solution of a polysulphide into an acid, sulphur is not precipitated, but an oily liquid is formed which is heavier than water and insoluble in it. This is the polysulphide of hydrogen: MS_{5} + 2HCl = MCl_{2} + H_{2}S_{5}. As Rebs showed (1888), whatever polysulphide be taken--of sodium, for instance--it always gives one and the same _hydrogen pentasulphide_,[24] of specific gravity 1·71 (15°). It can only be preserved in the absence of water and at low temperatures, and then not for long: for, especially in the presence of alkalis and when slightly warmed, it splits up very easily into sulphuretted hydrogen and sulphur.[25] [24] Rebs took di-, tri-, tetra-, and pentasulphides of sodium, potassium, and barium, which he prepared by dissolving sulphur in solutions of the normal sulphides; on adding hydrochloric acid he always obtained hydrogen pentasulphide, whence it is evident that 4H_{2}S_{n} = (_n_ - 1)H_{2}S_{5} + (5 - _n_)H_{2}S. For example, if H_{2}S_{2} were formed, it would decompose according to the equation 4H_{2}S_{2} = H_{2}S_{5} + 3H_{2}S. The hydrogen pentasulphide formed breaks up into hydrogen sulphide and sulphur when brought into contact with water. Previous to Rebs' researches many chemists stated that all polysulphides gave the bisulphide H_{2}S_{2}, and Hofmann recognised only hydrogen trisulphide, H_{2}S_{3}. [25] The formation of the polysulphides of hydrogen, H_{2}S_{n} is easily understood from the law of substitution, like that of the saturated hydrocarbons, C_{n}H_{2n + 2}, knowing that sulphur gives H_{2}S, because the molecule of sulphuretted hydrogen may be divided into H and HS. This radicle, HS, is equivalent to H. By substituting this radicle for hydrogen in H_{2}S we obtain (HS)HS = H_{2}S_{2}, (HS)(HS)S = H_{2}S_{3}, &c., in general H_{2}S_{n}. The homologues of CH_{4}, C_{n}H_{2n + 2} are formed in this manner from CH_{4}, and consequently the polysulphides H_{2}S_{n} are the homologues of H_{2}S. The question arises why in H_{2}S_{n} the apparent limit of _n_ is 5--that is, why does the substitution end with the formation of H_{2}S_{5}? The answer appears to me to be clearly because in the molecule of sulphur, S_{6}, there are six atoms of sulphur (Note 11). The forces in one and the other case are the same. In the one case they hold S_{6} together, in the other S_{5} and H_{2}; and, judging from H_{2}S, the two atoms of hydrogen are equal in power and significance to the atom of sulphur. Just as hydrogen peroxide, H_{2}O_{2}, expresses the composition of ozone, O_{3}, in which O is replaced by H_{2}, so also H_{2}S_{5} corresponds with S_{6}. The soluble sulphides and polysulphides of the metals of the alkalis and alkaline earths--for example, of ammonium,[26] potassium,[27] and calcium,[28]--have the appearance and properties of salts, just as the hydrated oxides have, whilst the sulphides of the metals of the higher groups resemble their oxides and have not at all the appearance of salts, and this is more especially the case with regard to the crystalline forms in which they frequently occur in nature.[29] [26] _Ammonium sulphide_, (NH_{4})_{2}S, may be prepared by passing sulphuretted hydrogen into a vessel full of dry ammonia, or by passing both dry gases together into a very cold receiver. In the latter case it is necessary to prevent the access of air, and to have an excess of ammonia. Under these circumstances, two volumes of ammonia combine with one volume of sulphuretted hydrogen, and form a colourless, very volatile, crystalline substance, having a very unpleasant odour, which is very poisonous and exceedingly unstable. When exposed to the air it absorbs oxygen and acquires a yellow colour, and then contains oxygen and polysulphide compounds (because a portion of the hydrogen sulphide gives water and sulphur). It is soluble in water and forms a colourless solution, which, however, in all probability contains free ammonia and the acid salt--that is, ammonium hydrosulphide, NH_{4}HS, or (NH_{4})_{2},S,H_{2}S. This salt is formed when dry ammonia is mixed with an excess of dry sulphuretted hydrogen. The compound contains equal volumes of the components NH_{3} + H_{2}S = (NH_{4})HS. It crystallises in an anhydrous state in colourless plates, and may be easily volatilised (dissociating like ammonium chloride), even at the ordinary temperature; it has an alkaline reaction, absorbs oxygen from the air, is soluble in water, and its solution is usually prepared by saturating an aqueous solution of ammonia with sulphuretted hydrogen. According to the ordinary rule, these salts, like other ammonium salts, split up into ammonia and sulphuretted hydrogen when they are distilled. A solution of ammonium sulphide is able to dissolve sulphur, and it then contains compounds of hydrogen polysulphide and ammonia. Some of these compounds may be obtained in a crystalline form. Thus Fritzsche obtained a compound of ammonia with hydrogen pentasulphide, or ammonium pentasulphide, (NH_{4})_{2}S_{5}, in the following manner: He saturated an aqueous solution of ammonia with sulphuretted hydrogen, added powdered sulphur to it, and passed ammonia gas into the solution, which then absorbed a fresh amount. After this he again passed sulphuretted hydrogen into the solution, and then added sulphur, and then again ammonia. After repeating this several times, orange-yellow crystals of (NH_{4})_{2}S_{5} separated out from the liquid. These crystals melted at 40° to 50°, and were very unstable. When a solution of ammonium hydrosulphide, prepared by saturating a solution of ammonia with sulphuretted hydrogen, is exposed to the air, it turns yellow, owing to the presence of an ammonium polysulphide, whose formation is due to the sulphuretted hydrogen being oxidised by the air and converted into water and sulphur, which is dissolved by the ammonium sulphide. In certain analytical reactions it is usual to employ a solution of ammonium sulphide which has been kept for some time and acquired a yellow colour. This yellow sulphide of ammonium deposits sulphur when saturated with acids, whilst a freshly-prepared solution only evolves sulphuretted hydrogen. The yellow solution furthermore contains ammonium thiosulphate, which is derived not only from the oxidation of the ammonium sulphide, but also from the action of the liberated sulphur on the ammonia, just as an alkaline salt of thiosulphuric acid and a sulphide are formed by the action of sulphur on a solution of a caustic alkali. [27] _Potassium sulphide_, K_{2}S, is obtained by heating a mixture of potassium sulphate and charcoal to a bright-red heat. It may be prepared in solution by taking a solution of potassium hydroxide, dividing it into two equal parts, and saturating one portion with sulphuretted hydrogen so long as it is absorbed. This portion will then contain the acid salt KHS (Note 21). The two portions are then mixed together, and potassium sulphide will then be obtained in the solution. This solution has a strongly alkaline reaction, and is colourless when freshly prepared, but it very easily undergoes change when exposed to the air, forming potassium thiosulphate and polysulphides. When the solution is evaporated at low temperatures under the receiver of an air-pump, it yields crystals containing K_{2}S,5H_{2}O (heated at 150°, they part with 3 mol. H_{2}O, and at higher temperatures they lose nearly all their water without evolving sulphuretted hydrogen). When they are ignited in glass vessels they corrode the glass. When a solution of caustic potash, completely saturated with sulphuretted hydrogen, is evaporated under the receiver of an air-pump it forms colourless rhombohedra of _potassium hydrosulphide_, 2(KHS),H_{2}O,K_{2}S,H_{2}S,H_{2}O. These crystals are deliquescent in the air, but do not change in a vacuum when heated up to 170°, and at higher temperatures they lose water but do not evolve sulphuretted hydrogen. The anhydrous compound, KHS, fuses at a dark-red heat into a very mobile yellow liquid, which gradually becomes darker in colour and solidifies to a red mass. It is remarkable that when a solution of the compound KHS is boiled it somewhat easily evolves half its sulphuretted hydrogen, leaving potassium sulphide, K_{2}S, in solution; and a solution of the latter in water is also able to evolve sulphuretted hydrogen on prolonged boiling, but the evolution cannot be rendered complete, and, therefore, at a certain temperature, a solution of potassium sulphide will not be capable of absorbing sulphuretted hydrogen at all. From this we must conclude that potassium hydroxide, water, and sulphuretted hydrogen form a system whose complex equilibrium is subject to the laws of dissociation, depends on the relative mass of each substance, on the temperature, and the dissociation pressure of the component elements. Potassium sulphide is not only soluble in water, but also in alcohol. Berzelius showed that in addition to potassium sulphide there also exist potassium bisulphide, K_{2}S_{2}; trisulphide, K_{2}S_{3}; tetrasulphide, K_{2}S_{4}; and pentasulphide, K_{2}S_{5}. According to the researches of Schöne, the last three are the most stable. These different compounds of potassium and sulphur may be prepared by fusing potassium hydroxide or carbonate with an excess of sulphur in a porcelain crucible in a stream of carbonic anhydride. At about 600° potassium pentasulphide is formed; this is the highest sulphur compound of potassium. When heated to 800° it loses one-fifth of its sulphur and gives the tetrasulphide, which at this temperature is stable. At a bright-red heat--namely, at about 900°--the trisulphide is formed. This compound may be also formed by igniting potassium carbonate in a stream of carbon bisulphide, in which case a compound, K_{2}CS_{3}, is first formed corresponding to potassium carbonate, and carbonic anhydride is evolved. On further ignition this compound splits up into carbon and potassium trisulphide, K_{2}S_{3}. The tetrasulphide may also be obtained in solution if a solution of potassium sulphide be boiled with the requisite amount of sulphur without access of air. This solution yields red crystals of the composition K_{2}S_{4},2H_{2}O when it is evaporated in a vacuum. These crystals are very hygroscopic, easily soluble in water, but very sparingly in alcohol; when ignited they give off water, sulphuretted hydrogen, and sulphur. If a solution of potassium sulphide be boiled with an excess of sulphur it forms the pentasulphide, which, however, is decomposed on prolonged boiling into sulphuretted hydrogen and potassium thiosulphate: K_{2}S_{5} + 3H_{2}O = K_{2}S_{2}O_{3} + 3H_{2}S. A substance called _liver of sulphur_ was formerly frequently used in chemistry and medicine. Under this name is known the substance which is formed by boiling a solution of caustic potash with an excess of flowers of sulphur. This solution contains a mixture of potassium pentasulphide and thiosulphate, 6KHO + 12S = 2K_{2}S_{5} + K_{2}S_{2}O_{3} + 3H_{2}O. The substance obtained by fusing potassium carbonate with an excess of sulphur was also known as liver of sulphur. If this mixture be heated to an incipient dark-red heat it will contain potassium thiosulphate, but at higher temperatures potassium sulphate is formed. In either case a polysulphide of potassium is also present. The sulphides of sodium, for example Na_{2}S, NaHS, &c., in many respects closely resemble the corresponding potassium compounds. [28] The metals of the alkaline earths, like those of the alkalis, form several compounds with sulphur; thus calcium forms compounds with one and with five atoms of sulphur. There are doubtless also intermediate sulphides. If sulphuretted hydrogen be passed over ignited lime it forms water and _calcium sulphide_, which may also be formed by heating calcium sulphate with charcoal, whilst if sulphur be heated with lime or with calcium carbonate, then naturally oxygen compounds (calcium thiosulphate and sulphate) are formed at the same time as calcium sulphide. The prolonged action of the vapour of carbon bisulphide, especially when mixed with carbonic anhydride, on strongly ignited calcium carbonate entirely converts it into sulphide. Calcium sulphide is generally obtained as an almost colourless, opaque, brittle mass, which is infusible at a white heat, and is soluble in water. The act of solution (as with K_{2}S, Note 21) is partly accompanied by a double decomposition with the water. When heated, dry calcium sulphide does not absorb oxygen from the air. An excess of water decomposes it, like many other metallic sulphides, precipitating lime (as a product of the decomposition the lime hinders the action of the water upon the CaS; see soda refuse, Chapter XII., Note 12), and forming a hydrosulphide, CaH_{2}S_{2}, in solution. This compound is also formed by passing sulphuretted hydrogen through an aqueous solution of calcium sulphide or lime. Its solution, like that of calcium sulphide, has an alkaline reaction. It decomposes when evaporated, and absorbs oxygen from the air. _Calcium pentasulphide_, CaS_{5}, is not known in a pure state, but may be obtained in admixture with calcium thiosulphate by boiling a solution of lime or calcium sulphide with sulphur: 3CaH_{2}O_{2} + 12S = 2CaS_{5} + CaS_{2}O_{3} + 3H_{2}O. A similar compound in an impure form is formed by the action of air on alkali waste, and is used for the preparation of thiosulphates. Many of the sulphides of the metals of the alkaline earths are phosphorescent--that is, they have the faculty of _emitting light_, after having been subjected to the action of sunlight, or of any bright source of light (Canton phosphorus, &c.). The luminosity lasts some time, but it is not permanent, and gradually disappears. This phosphorescent property is inherent, in a greater or less degree, to nearly all substances (Becquerel), but for a very short time, whilst with calcium sulphide it is comparatively durable, lasting for several hours, and Dewar (1894) showed that it is far more intense at very low temperatures (for instance, in bodies cooled in liquid oxygen to -182°). It is due to the excitation of the surfaces of substances by the action of light, and is determined by those rays which exhibit a chemical action. Hence daylight or the light of burning magnesium, &c., acts more powerfully than the light of a lamp, &c. Warnerke has shown that a small quantity of magnesium lighted near the surface of a phosphorescent substance rapidly excites the greatest possible intensity of luminosity; this enabled him to found a method of measuring the intensity of light--_i.e._ to obtain a constant unit of light--and to apply it to photography. The nature of the change which is accomplished on the surface of the luminous substance is at present unknown, but in any case it is a renewable one, because the experiment may be repeated for an infinite number of times and takes place in a vacuum. The intensity and tint of the light emitted depend on the method of preparation of the calcium sulphide, and on the degree of ignition and purity of the calcium carbonate taken. According to the observations of Becquerel, the presence of compounds of manganese, bismuth, &c., sodium sulphide (but not potassium sulphide), &c., although in minute traces, is perfectly indispensable. This gives reason for thinking that the formation (in the dark) and decomposition (in light) of double salts like MnS,Na_{2}S perhaps form the chemical cause of the phenomena. Compounds of strontium and barium have this property to even a greater extent than calcium sulphide. These compounds may be prepared as in the following example: A mixture of sodium thiosulphate and strontium chloride is prepared; a double decomposition takes place between the salts, and, on the addition of alcohol, strontium thiosulphate, SrS_{2}O_{3}, is precipitated, which, when ignited, leaves strontium sulphide behind. The strontium sulphide thus prepared emits (when dry) a greenish yellow light. It contains a certain amount of sulphur, sodium sulphide, and strontium sulphate. By ignition at various temperatures, and by different methods of preparation, it is possible to obtain mixtures which emit different coloured lights. [29] As examples, we will describe the sulphides of arsenic, antimony, and mercury. Arsenic trisulphide, or _orpiment_, As_{2}S_{3}, occurs native, and is obtained pure when a solution of arsenious anhydride in the presence of hydrochloric acid comes into contact with sulphuretted hydrogen (there is no precipitate in the absence of free acid). A beautiful yellow precipitate is then obtained: As_{2}O_{3} + 3H_{2}S = 3H_{2}O + As_{2}S_{3}; it fuses when heated, and volatilises without decomposition. As_{2}S_{3} is easily obtained in a colloid form (Chapter I., Note 57). When fused it forms a semi-transparent, yellow mass, and it is thus that it enters the market. The specific gravity of native orpiment is 3·4, and that of the artificially-fused mass is 2·7. It is used as a yellow pigment, and owing to its insolubility in water and acids it is less injurious than the other compounds corresponding to arsenious acid. According to the type AsX_{2}, realgar, AsS, is known, but it is probable that the true composition of this compound is As_{4}S_{4}--that is, it presents the same relation to orpiment as liquid phosphuretted hydrogen does to gaseous. _Realgar_ (_Sandaraca_) occurs native as brilliant red crystals of specific gravity 3·59, and may be prepared artificially by fusing arsenic and sulphur in the proportions indicated by its formulæ. It is prepared in large quantities by distilling a mixture of sulphur and arsenical pyrites. Like orpiment it dissolves in calcium sulphide, and even in caustic potash. It is used for signal lights and fireworks, because it deflagrates and gives a large and very brilliant white flame with nitre. With antimony, sulphur gives a tri- and a pentasulphide. The former, Sb_{2}S_{3}, which corresponds with antimonious oxide, occurs native (Chapter XIX.) in a crystalline form; its sp. gr. is then 4·9, and it presents brilliant rhombic crystals of a grey colour, which fuse when heated. A substance of the same composition is obtained as an amorphous orange powder by passing sulphuretted hydrogen into an acid solution of antimonious oxide. In this respect antimonious oxide again reacts like arsenious acid, and the sulphides of both are soluble in ammonium and potassium sulphides, and, especially in the case of arsenious sulphide, are easily obtained in colloidal solutions. By prolonged boiling with water, antimonious sulphide may be entirely converted into the oxide, hydrogen sulphide being evolved (Elbers). Native antimony sulphide, or the orange precipitated trisulphide when fused with dry, or boiled with dissolved, alkalis, forms a dark-coloured mass (Kermes mineral) formerly much used in medicine, which contains a mixture of antimonious sulphide and oxide. There are also compounds of these substances. A so-called antimony vermilion is much used as a dye; it is prepared by boiling sodium thiosulphate (six parts) with antimony trichloride (five parts) and water (fifty parts). This substance probably contains an oxysulphide of antimony--that is, a portion of the oxygen in the oxide of antimony in it is replaced by sulphur. Red antimony ore, and antimony glass, which is obtained by fusing the trisulphide with antimonious oxide, have a similar composition, Sb_{2}OS_{2}. In the arts, the _antimony pentasulphide_, Sb_{2}S_{5}, is the most frequently used of the sulphur compounds of antimony. It is formed by the action of acids on the so-called Schlippe's salt, which is a _sodium thiorthantimonate_, SbS(NaS)_{3}, corresponding with (Chapter XIX., Note 41 bis) orthantimonic acid, SbO(OH)_{3}, with the replacement of oxygen by sulphur. It is obtained by boiling finely-powdered native antimony trisulphide with twice its weight of sodium carbonate, and half its weight of sulphur and lime, in the presence of a considerable quantity of water. The processes taking place are as follows:--The sodium carbonate is converted into hydroxide by the lime, and then forms sodium sulphide with the sulphur; the sodium sulphide then dissolves the antimony sulphide, which in this form already combines with the greatest amount of sulphur, so that a compound is formed corresponding with antimony pentasulphide dissolved in sodium sulphide. The solution is filtered and crystallised, care being taken to prevent access of air, which oxidises the sodium sulphide. This salt crystallises in large, yellowish crystals, which are easily soluble in water and have the composition Na_{3}SbS_{4},9H_{2}O. When heated they lose their water of crystallisation and then fuse without alteration; but when in solution, and even in crystalline form, this salt turns brown in air, owing to the oxidation of the sulphur and the breaking up of the compound. As it is used in medicine, especially in the preparation of antimony pentasulphide, it is kept under a layer of alcohol, in which it is insoluble. Acids precipitate antimony pentasulphide from a solution of this salt, as an orange powder, insoluble in acids and very frequently used in medicine (_sulfur auratum antimonii_). This substance when heated evolves vapours of sulphur, and leaves antimony trisulphide behind. Mercury forms compounds with sulphur of the same types as it does with oxygen. Mercurous sulphide, Hg_{2}S, easily splits up into mercury and mercuric sulphide. It is obtained by the action of potassium sulphide on mercurous chloride, and also by the action of sulphuretted hydrogen on solutions of salts of the type HgX. Mercuric sulphide, HgS, corresponding with the oxide, is cinnabar; it is obtained as a black precipitate by the action of an excess of sulphuretted hydrogen on solutions of mercuric salts. It is insoluble in acids, and is therefore precipitated in their presence. If a certain amount of water containing sulphuretted hydrogen be added to a solution of mercuric chloride, it first gives a white precipitate of the composition Hg_{3}S_{2}Cl_{2}--that is, a compound HgCl,2HgS, a sulphochloride of mercury like the oxychloride. But in the presence of an excess of sulphuretted hydrogen, the black precipitate of mercuric sulphide is formed. In this state it is not crystalline (the red variety is formed by the prolonged action of polysulphides of ammonium upon the black HgS), but if it be heated to its temperature of volatilisation it forms a red crystalline sublimate which is identical with native cinnabar. In this form its specific gravity is 8·0, and it forms a red powder, owing to which it is used as a red pigment (vermilion) in oil, pastel, and other paints. It is so little attacked by reagents that even nitric acid has no action on it, and the gastric juices do not dissolve it, so that it is not poisonous. When heated in air, the sulphur burns away and leaves metallic mercury. On a large scale cinnabar is usually prepared in the following manner: 300 parts of mercury and 115 parts of sulphur are mixed together as intimately as possible and poured into a solution of 75 parts of caustic potash in 425 parts of water, and the mixture is heated at 50° for several hours. Red mercury sulphide is thus formed, and separates out from the solution. The reaction which takes place is as follows: A soluble compound, K_{2}HgS_{2}, is first formed; this compound is able to separate in colourless silky needles, which are soluble in the caustic potash, but are decomposed by water, and at 50°; this solution (perhaps by attracting oxygen from the air) slowly deposits HgS in a crystalline form. Spring conducted an interesting research (at Liège, 1894) upon the conversion of the black amorphous sulphide of mercury, HgS, into red crystalline cinnabar. This research formed a sequel to Spring's classical researches on the influence of high pressures upon the properties of solids and their capacity for mutual combination. He showed, among other things, that ordinary solids and even metals (for instance, Pb), after being considerably compressed under a pressure of 20,000 atmospheres, return on removal of the pressure to their original density like gases. But this is only true when the compressed solid is not liable to an allotropic variation, and does not give a denser variety. Thus prismatic sulphur (sp. gr. 1·9) passes under pressure into the octahedral (sp. gr. 2·05) variety. Black HgS (precipitated from solution) has a sp. gr. 7·6, while that of the red variety is 8·2, and therefore it might be expected that the former would pass into the latter under pressure, but experiments both at the ordinary and a higher temperature did not give the looked-for result, because even at a pressure of 20,000 atmospheres the black sulphide was not compressed to the density of cinnabar (a pressure of as much as 35,000 atmospheres was necessary, which could not be attained in the experiment). But Spring prepared a black HgS, which had a sp. gr. of 8·0, and this, under a pressure of 2,500 atmospheres, passed into cinnabar. He obtained this peculiar black variety of HgS (sp. gr. 8·0) by distilling cinnabar in an atmosphere of CO_{2}, when the greater portion of the HgS is redeposited in the form of cinnabar. Under the action of a solution of polysulphide of ammonium, this variety of HgS passes more slowly into the red variety than the precipitated variety does, while under pressure the conversion is comparatively easy. It is worthy of remark, that Linder and Picton obtained complex compounds of many of the sulphides of the heavy metals (Ca, Hg, Sb, Zn, Cd, Ag, Au) with H_{2}S, for example H_{2}S,7CuS (by the action of H_{2}S upon the hydrate of oxide of copper), H_{2}S,9CuS (in the presence of acetic acid and with an excess of H_{2}S), &c. Probably we have here a sort of 'solid' solution of H_{2}S in the metallic sulphides. As the acids derived from chlorine, phosphorus, and carbon are the oxidised hydrogen compounds of these elements, so also we can form an idea of the acid hydrates of sulphur, or of _the normal acids of sulphur_, by representing them as the oxidised products of sulphuretted hydrogen-- HCl H_{2}S H_{3}P H_{4}C HClO H_{2}SO(?) H_{3}PO(?) H_{4}CO HClO_{2} H_{2}SO_{2}(?) H_{3}PO_{2} H_{4}CO_{2} HClO_{3} H_{2}SO_{3} H_{3}PO_{3} H_{4}CO_{3} HClO_{4} H_{2}SO_{4} H_{3}PO_{4} H_{4}CO_{4}[30] In the case of chlorine, if not all the hydrates, at all events salts of all the normal hydrates are known, whilst in the case of sulphur only the acids H_{2}S, H_{2}SO_{3} and H_{2}SO_{4} are known. But, on the other hand, the latter are obtained not only as hydrates but also as stable anhydrides, SO_{2} and SO_{3}, which are formed with the evolution of heat from sulphur and oxygen; 32 parts of sulphur in combining with 32 parts of oxygen--that is, in forming SO_{2}--evolve 71,000 heat units,[31] and if the oxidation proceeds to the formation of SO_{3}, 103,000 heat units are evolved. These figures may be compared with those which correspond with the passage of carbon into CO and CO_{2}, when 29,000 and 97,000 units of heat are evolved. This determines the stability of the higher oxides of sulphur, and also expresses the peculiarity of sulphur as an element which, although an analogue of oxygen, forms stable compounds with it, and thus fundamentally differs from chlorine. The higher and lower oxides of chlorine are powerful oxidising agents, whilst the higher oxide of sulphur, SO_{3}, has but feeble oxidising powers, and the lower oxide, SO_{2}, frequently acts as a reducing agent, and is formed by the direct combustion of sulphur, just as carbonic anhydride, CO_{2}, proceeds from the combustion of carbon. In the combustion of sulphur, and also in the oxidation (roasting) of the sulphides and polysulphides by their ignition in air, _sulphurous oxide_, or _sulphurous anhydride_, or _sulphur dioxide_, SO_{2},[31 bis] is exclusively formed. It is prepared on a large scale by burning sulphur or roasting iron pyrites or other sulphides[32] for the manufacture of sulphuric acid (Chapter VI.), and for direct application in the manufacture of wine or for bleaching tissues and other purposes. In the latter instances its application is based on the fact that sulphurous anhydride acts on certain vegetable matters, and has the property of a reducing and feeble acid.[32 bis] [30] CH_{4} gives CH_{4}O or CH_{3}(OH), wood spirit; CH_{4}O_{2} or CH_{2}(OH)_{2}, which decomposes into water and CH_{2}O--that is, methylene oxide or formaldehyde; CH_{4}O_{3} = CH(OH)_{3} = H_{2}O + CHO(OH), or formic acid; and CH_{4}O_{4} = C(OH)_{4} = 2H_{2}O + CO_{2}. There are four typical hydrogen compounds, RH, RH_{2}, RH_{3}, and RH_{4}, and each of them has its typical oxide. Beyond H_{4} and O_{4} combination does not proceed. [31] Rhombic sulphur, 71,080 heat units; monoclinic sulphur, 71,720 units, according to Thomsen. [31 bis] However, when sulphur or metallic sulphides burn in an excess of air, there is always formed a certain, although small, amount of SO_{3}, which gives sulphuric acid with the moisture of the air. [32] The enormous amount of sulphuric acid now manufactured is chiefly prepared by roasting native pyrites, but a considerable amount of the SO_{2} for this purpose is obtained by roasting zinc blende (ZnS) and copper and lead sulphides. A certain amount is also procured from soda refuse (Note 6) and the residues obtained from the purification of coal gas. [32 bis] Sulphurous anhydride is also obtained by the decomposition of many sulphates, especially of the heavy metals, by the action of heat; but this requires a very powerful heat. This formation of sulphurous anhydride from sulphates is based on the decomposition proper to sulphuric acid itself. When sulphuric acid is strongly heated (for instance, by dropping it upon an incandescent surface) it is decomposed into water, oxygen, and sulphurous anhydride--that is, into those compounds from which it is formed. A similar decomposition proceeds during the ignition of many sulphates. Even so stable a sulphate as gypsum does not resist the action of very high temperatures, but is decomposed in the same manner, lime being left behind. The decomposition of sulphates by heat is accomplished with still greater facility in the presence of sulphur, because in this case the liberated oxygen combines with the sulphur and the metal is able to form a sulphide. Thus when ferrous sulphate (green vitriol) is ignited with sulphur, it gives ferrous sulphide and sulphurous anhydride: FeSO_{4} + 2S = FeS + 2SO_{2}, and this reaction may even be used for the preparation of this gas. At 400° sulphuric acid and sulphur give an extremely uniform stream of pure sulphurous anhydride, so that it is best prepared on a manufacturing scale by this method. Iron pyrites, FeS_{2}, when heated to 150° with sulphuric acid (sp. gr. 1·75) in cast-iron vessels also gives an abundant and uniform supply of sulphurous anhydride. In the laboratory--that is, on a small scale--sulphurous anhydride is best prepared by deoxidising sulphuric acid by heating it with charcoal, or copper, sulphur, mercury, &c. Charcoal produces this decomposition of sulphuric acid at but moderately high temperatures; it is itself converted into carbonic anhydride,[32 tri] and therefore when sulphuric acid is heated with charcoal it evolves a mixture of sulphurous and carbonic anhydrides: C + 2H_{2}SO_{4} = CO_{2} + 2SO_{2} + 2H_{2}O. The metals which are unable to decompose water, and which do not, therefore, expel hydrogen from sulphuric acid, are frequently capable of decomposing sulphuric acid, with the evolution of sulphurous anhydride, just as they decompose nitric acid, forming the lower oxides of nitrogen. These metals are silver, mercury, copper, lead, and others. Thus, for example, the action of copper on sulphuric acid may be expressed by the following equation: Cu + 2H_{2}SO_{4} = CuSO_{4} + SO_{2} + 2H_{2}O. In the laboratory this reaction is carried on in a flask with a gas-conducting tube, and does not take place unless aided by heat.[33] [32 tri] Mellitic acid is formed at the same time (Verneuille). [33] The thermochemical data connected with this reaction are as follows: A molecule of hydrogen H_{2}, in combining with oxygen (O = 16) develops about 69,000 heat units, whilst the molecule of SO_{2}, in combining with oxygen only develops about 32,000 heat units--that is, about half as much--and therefore those metals which cannot decompose water may still be able to deoxidise sulphuric into sulphurous acid. Those metals which decompose water and sulphuric acid with the evolution of hydrogen, evolve in combining with sixteen parts by weight of oxygen more heat than hydrogen does--for example, K_{2}, Na_{2}, Ca develop about or more than 100,000 heat units; Fe, Zn, Mn about 70,000 to 80,000 heat units; whilst those metals which neither decompose water nor evolve hydrogen from sulphuric acid, but are still capable of evolving sulphurous anhydride from it, develop less heat with oxygen than hydrogen, but nearly the same amount, if not more than, sulphurous anhydride develops--for example, Cu and Hg develop about 40,000 and Pb about 50,000 heat units. In its physical and chemical properties sulphurous anhydride presents a great _resemblance to carbonic anhydride_. It is a heavy gas, somewhat considerably soluble in water, very easily condensed into a liquid; it forms normal and acid salts, does not evolve oxygen under the direct action of heat,[34] although such metals as sodium and magnesium burn in it, just as in carbonic anhydride. It has a suffocating odour, which is well known owing to its being evolved when sulphur or sulphur matches are burnt. In characterising the properties of sulphurous anhydride, it is very important to remember (Chapter II.) also that it is more easily liquefied (at -10°, or at 0° under two atmospheres pressure) than carbonic anhydride (thirty-six atmospheres at 0°),[35] that it is more soluble than carbonic anhydride (Vol. I. p. 79); at 0°, 100 vols. of water dissolve 180 vols. of carbonic anhydride and 688 vols. of sulphuric anhydride), that the molecular weight of SO_{2} = 64 and of CO_{2} = 44, and that the density of liquid sulphurous anhydride at 0° = 1·43 (molecular volume = 45) and of carbonic anhydride = 0·95 (molecular volume = 49). Although sulphur dioxide is the anhydride of an acid, nevertheless, like carbonic anhydride, it does not form any stable compounds with water, but gives a solution from which it may be entirely expelled by the action of heat.[36] The acid character of sulphurous anhydride is clearly expressed by the fact that it is entirely absorbed by alkalis, with which it forms acid and normal salts easily soluble in water. With salts of barium, calcium, and the heavy metals, the normal salts of the alkalis, M_{2}SO_{3}, give precipitates exactly like those formed by the carbonates. In general, the salts of sulphurous acid are closely analogous to the corresponding carbonates. [34] That is, it only dissociates and re-forms the original product on cooling. [35] At a given temperature the pressure of this gas evolved from any salt will be less than that of carbonic anhydride, if we compare the separation of a gas from its salts with the phenomenon of evaporation, as was done in discussing the decomposition of calcium carbonate. Liquid sulphurous anhydride is used on a large scale (Pictet) for the production of cold. [36] De la Rive, Pierre, and more especially Roozeboom, have investigated the crystallo-hydrate which is formed by sulphurous anhydride and water at temperatures below 7° under the ordinary pressure, and in closed vessels (at temperatures below 12°). Its composition is SO_{2},7H_{2}O, and density 1·2. This hydrate corresponds with the similar hydrate CO_{2},8H_{2}O obtained by Wroblewsky. _Acid sodium sulphite_, NaHSO_{3}, may be obtained by passing sulphurous anhydride into a solution of sodium hydroxide. It is also formed by saturating a solution of sodium carbonate with the gas (carbonic anhydride is then given off), and as the solubility of the acid sulphite is much greater than that of the carbonate, a further quantity of the latter may be dissolved after the passage of the sulphurous anhydride, so that ultimately a very strong solution of the sulphite may be formed in this manner, from which it may be obtained in a crystalline form, either by cooling and evaporating (without heating, for then the salt would give off sulphurous anhydride) or by adding alcohol to the solution. When exposed to the air this salt loses sulphurous anhydride and attracts oxygen, which converts it into sodium sulphate. The acid sulphites of the alkali metals are able to combine not only with oxygen, but also with many other substances--for example, a solution of the sodium salt dissolves sulphur, forming sodium thiosulphate, gives crystalline compounds with the aldehydes and ketones, and dissolves many bases, converting them into double sulphites. Having the faculty of attracting or absorbing oxygen, acid sodium sulphite is also able to absorb chlorine, and is therefore employed, like sodium thiosulphate, for the removal of chloride (as an antichlor), especially in the bleaching of fabrics, when it is necessary to remove the last traces of the chlorine held in the tissues, which might otherwise have an injurious effect on them. If a solution of an alkali hydroxide be divided into two parts, and one half is saturated with sulphurous anhydride, and then the other half added to it, a normal salt will be obtained in the solution, having an alkaline reaction, like a solution of sodium carbonate. The acid salt has a neutral reaction.[36 bis] Like sodium carbonate, _normal sodium sulphite_ has the composition Na_{2}SO_{3},10H_{2}O, and its maximum solubility is at 33°--in a word, it very closely resembles sodium carbonate. Although this salt does not give off sulphurous anhydride from its solution, it is able, like the acid salt, to absorb oxygen from the air, and is then converted into sodium sulphate.[37] [36 bis] Schwicker (1889) by saturating NaHSO_{3} with potash, or KHSO_{3} with soda, obtained NaKSO_{3}, in the first instance with H_{2}O, and in the second instance with 2H_{2}O, probably owing to the different media in which the crystals are formed. In general sulphurous acid easily forms double salts. [37] The normal salts of calcium and magnesium are slightly, and the acid salts easily, soluble in water. These acid sulphites are much used in practice; thus calcium bisulphite is employed in the manufacture of cellulose from sawdust, for mixing with fibrous matter in the manufacture of paper. Besides the acid character we must also point out the reducing character of sulphurous anhydride. The reducing action of sulphurous acid, its anhydride and salts, is due to their faculty of passing into sulphuric acid and sulphates. The reducing action of the sulphites is particularly energetic, so that they even convert nitric oxide into nitrous oxide: K_{2}SO_{3} + 2NO = K_{2}SO_{4} + N_{2}O. The salts of many of the higher oxides are converted into those of the lower--for example, FeX_{3} into FeX_{2}, CuX_{2} into CuX, HgX_{2} into HgX; thus 2FeX_{3} + SO_{2} + 2H_{2}O = 2FeX_{2} + H_{2}SO_{4} + 2HX. In the presence of water, sulphurous anhydride is oxidised by chlorine (SO_{2} + 2H_{2}O + Cl_{2} = H_{2}SO_{4} + 2HCl), iodine, nitrous acid, hydrogen peroxide, hypochlorous acid, chloric acid, and other oxygen compounds of the halogens, chromic, manganic, and many other metallic acids and higher oxides, as well as all peroxides. Free oxygen in the presence of spongy platinum is able to oxidise sulphurous anhydride even in the absence of water, in which case sulphuric anhydride SO_{3} is formed, so that the latter may be prepared by passing a mixture of sulphurous anhydride and oxygen over incandescent spongy platinum, or, as it is now prepared on a large scale in chemical works, by passing this mixture over asbestos or pumice stone moistened with a solution of platinum salt and ignited. Sulphurous anhydride is completely absorbed by certain higher oxides--for instance, by barium peroxide and lead dioxide (PbO_{2} + SO_{2} = PbSO_{4}).[38] [38] This reaction is taken advantage of in removing sulphurous anhydride from a mixture of gases. Lead dioxide, PbO_{2}, is brown, and when combined with sulphurous anhydride it forms lead sulphate, PbSO_{4}, which is white, so that the reaction is evident both from the change in colour and development of heat. Sulphurous anhydride is slowly decomposed by the action of light, with the separation of sulphur and formation of sulphuric anhydride. This explains the fact that sulphurous anhydride prepared in the dark gives a white precipitate of silver sulphite, Ag_{2}SO_{3}, with silver chlorate, AgClO_{4}, but when prepared in the light, even in diffused light, it gives a dark precipitate. This naturally depends on the fact that the sulphur liberated then forms silver sulphide, which is black. There are, however, cases where sulphurous anhydride acts as an oxidising agent--that is, it is _deoxidised_ in the presence of substances which are capable of absorbing oxygen with still greater energy than the sulphurous anhydride itself. This oxidising action proceeds with the formation of sulphuretted hydrogen or of sulphides, while the reducing agent is oxidised at the expense of the oxygen of the sulphurous anhydride. In this respect, the action of stannous salts is particularly remarkable. Stannous chloride, SnCl_{2}, in an aqueous solution gives a precipitate of stannic sulphide, SnS_{2}, with sulphurous anhydride--that is, the latter is deoxidised to sulphuretted hydrogen, while SnX_{2} is oxidised into SnX_{4}. A solution of sulphurous anhydride has also an oxidising action on zinc. The zinc passes into solution, but no hydrogen is evolved,[39] because a salt of _hydrosulphurous acid_, ZnS_{2}O_{4}, is formed. The free acid is still less stable than the salt. [39] Schönebein observed that the liquid turns yellow, and acquires the faculty of decolorising litmus and indigo. Schützenberger showed that this depends on the formation of a zinc salt of a peculiar and very powerfully-reducing acid, for with cupric salts the yellow solution gives a red precipitate of cuprous hydrate or metallic copper, and it reduces salts of silver and mercury entirely. An exactly similar solution is obtained by the action of zinc on sodium bisulphite without access of air and in the cold. The yellow liquid absorbs oxygen from the air with great avidity, and forms a sulphate. If the solution be mixed with alcohol, it deposits a double sulphite of zinc and sodium, ZnNa_{2}(SO_{3})_{2}, which does not decolorise litmus or indigo. The remaining alcoholic solution deposits colourless crystals in the cold, which absorb oxygen with great energy in the presence of water, but are tolerably stable when dried under the receiver of an air-pump. The solution of these crystals has the above-mentioned decolorising and reducing properties. These crystals contain a sodium salt of a lower acid; their composition was at first supposed to be HNaSO_{2}, but it was afterwards proved that they do not contain hydrogen, and present the composition Na_{2}S_{2}O_{4} (Bernthsen). The same salt is formed by the action of a galvanic current on a solution of sodium bisulphite, owing to the action of the hydrogen at the moment of its liberation. If SO_{2} resembles CO_{2} in its composition, then hyposulphurous acid H_{2}S_{2}O_{4} resembles oxalic acid H_{2}C_{2}O_{4}. Perhaps an analogue of formic acid SH_{2}O_{2} will be discovered. The faculty of sulphurous anhydride of combining with various substances is evident from the above-cited reactions, where it combines with hydrogen and with oxygen, and this faculty also appears in the fact that, like carbonic oxide, it combines with chlorine, forming a chloranhydride of sulphuric acid, SO_{2}Cl_{2}, to which we shall afterwards return. The same faculty for combination also appears in the salts of sulphurous acid, in their liability to oxidation and in the exceedingly characteristic formation of a peculiar series of salts obtained by Pelouze and Frémy. At a temperature of -10° or below, nitric oxide NO is absorbed by alkaline solutions of the alkali sulphites, forming a peculiar series of _nitrosulphates_. At a higher temperature these salts are not formed but the nitric oxide is reduced to nitrous oxide. But in the cold the liquid saturated with nitric oxide after a certain time gives prismatic crystals resembling those of nitre. The composition of the potassium salt is K_{2}SN_{2}O_{3}--that is, the salt contains the elements of potassium sulphite and of nitric oxide.[40] [40] The instability of this salt is very great, and may be compared to that of the compound of ferrous sulphate with nitric oxide, for when heated under the contact influence of spongy platinum, charcoal, &c., it splits up into potassium sulphate and nitrous oxide. At 130° the dry salt gives off nitric oxide, and re-forms potassium sulphite. The free acid has not yet been obtained. These salts resemble the series of _sulphonitrites_ discovered by Frémy in 1845. They are obtained by passing sulphurous anhydride through a concentrated and strongly alkaline aqueous solution of potassium nitrite. They are soluble in water, but are precipitated by an excess of alkali. The first product of the action has the composition K_{3}NS_{3}HO_{9}. It is then converted by the further action of sulphurous anhydride, cold water, and other reagents into a series of similar complex salts, many of which give well-formed crystals. One must suppose that the chief cause of the formation of these very complex compounds is that they contain unsaturated compounds, NO, KNO_{2}, and KHSO_{3}, all of which are subject to oxidation and further combination, and therefore easily combine among each other. The decomposition of these compounds, with the evolution of ammonia, when their solutions are heated is due to the fact that the molecule contains the deoxidant, sulphurous anhydride, which reduces the nitrous acid, NO(OH), to ammonia. In my opinion the composition of the sulphonitrites may be very simply referred to the composition of ammonia, in which the hydrogen is partly replaced by the radicle of the sulphates. If we represent the composition of potassium sulphate as KO.KSO_{3}, the group KSO_{3} will be equivalent (according to the law of substitution) to HO and to hydrogen. It combines with hydrogen, forming the potassium acid sulphite, KHSO_{3}. Hence the group KSO_{3} may also replace the hydrogen in ammonia. Judging by my analysis (1870) the extreme limit of this substitution, N(HSO_{3})_{3}, agrees with that of the sulphonitrite, which is easily formed, simultaneously with alkali, by the action of potassium sulphite on potassium nitrite, according to the equation 3K(KSO_{3}) + KNO_{2} + 2H_{2}O = N(KSO_{3})_{3} + 4HKO. The researches of Berglund, and especially of Raschig (1887), fully verified my conclusions, and showed that we must distinguish the following types of salts, corresponding with ammonia, where X stands for the sulphonic group, HSO_{3}, in which the hydrogen is replaced by potassium; hence X = KSO_{3}: (1) NH_{2}X, (2) NHX_{2}, (3) NH_{3}, (4) N(OH)XH, (5) N(OH)X_{2}, (6) N(OH)_{2}X, just as NH_{2}(OH) is hydroxylamine, NH(OH)_{2}, is the hydrate of nitrous oxide, and N(OH)_{3} is orthonitrous acid, as follows from the law of substitution. This class of compounds is in most intimate relation with the series of sulphonitrous compounds, corresponding with 'chamber crystals' and their acids, which we shall consider later. There are also several other substances, formed by the oxides of nitrogen and sulphur, which belong to this class of complex and, under some circumstances, unstable compounds. In the manufacture of sulphuric acid, both these classes of oxides come into contact with each other in the lead chambers, and if there be insufficient water for the formation of sulphuric acid they give crystalline compounds, termed _chamber crystals_. As a rule, the composition of the crystals is expressed by the formula NHSO_{3}. This is a compound of the radicles NO_{2} of nitric acid, and HSO_{3} of sulphuric acid, or nitro-sulphuric acid, NO_{2}.SHO_{3}, if sulphuric acid be expressed as OH.SHO_{3} and nitric by NO_{2}.OH. The tabular crystals of this substance fuse at about 70°, are formed both by the direct action of nitrous anhydride or nitric peroxide (but not NO, which is not absorbed by sulphuric acid) on sulphuric acid (Weltzien and others), and especially on sulphuric acid containing an anhydride and the lower oxides of sulphur and nitric acid.[41] [41] In the sulphuric acid chambers the lower oxides of nitrogen and sulphur take part in the reaction. They are oxidised by the oxygen of the air, and form nitro-sulphuric acid--for example, 2SO_{2} + N_{2}O_{3} + O_{2} + H_{2}O = 2NHSO_{5}. This compound dissolves in strong sulphuric acid without changing, and when this solution is diluted (when the sp. gr. falls to 1·5), it splits up into sulphuric acid and nitrous anhydride, and by the action of sulphurous anhydride is converted into nitric oxide, which by itself (in the absence of nitric acid or oxygen) is insoluble in sulphuric acid. These reactions are taken advantage of in retaining the oxides of nitrogen in the Gay-Lussac coke-towers, and for extracting the absorbed oxides of nitrogen from the resultant solution in the Glover tower. Although nitric oxide is not absorbed by sulphuric acid, it reacts (Rose, Brüning) on its anhydride, and forms sulphurous anhydride and a crystalline substance, N_{2}S_{2}O_{9} = 2NO + 3SO_{3} - SO_{2} = N_{2}O_{3}2SO_{3}. This may be regarded as the anhydride of nitro-sulphuric acid, because N_{2}S_{2}O_{9} = 2NHSO_{5} - H_{2}O; like nitro-sulphuric acid, it is decomposed by water into nitro-sulphuric acid and nitrous anhydride. Since boric and arsenious anhydrides, alumina and other oxides of the form R_{2}O_{3} are able to combine with sulphuric anhydride to form similar compounds decomposable by water, the above compound does not present any exceptional phenomenon. The substance NOClSO_{3} obtained by Weber by the action of nitrosyl chloride upon sulphuric anhydride belongs to this class of compounds. _Thiosulphuric acid_, H_{2}S_{2}O_{3}--that is, a compound of sulphurous acid and sulphur--also belongs to the products of combination of sulphurous acid. In the same way that sulphurous acid, H_{2}SO_{3}, gives H_{2}SO_{4} with oxygen, so it gives H_{2}S_{2}O_{3} with sulphur. In a free state it is very unstable, and it is only known in the form of its salts proceeding from the direct action of sulphur on the normal sulphites; if endeavours be made to separate it in a free state, it immediately splits up into those elements from which it might be formed--that is, into sulphur and sulphurous acid. The most important of its salts is the _sodium thiosulphate_ (known as hyposulphite), Na_{2}S_{2}O_{3},5H_{2}O, which occurs in colourless crystals, and is unacted on by atmospheric oxygen either when in a dry state or in solution. Many other salts of this acid are easily formed by means of this salt,[41 bis] although this cannot be done with all bases, for such bases as alumina, ferric oxide, chromium oxide, and others do not give compounds with thiosulphuric acid, just as they do not form stable compounds with carbonic acid. Whenever these salts might be formed, they (like the acid) split up into sulphurous acid and sulphur, and furthermore the elements of thiosulphuric acid in many cases act in a reducing manner, forming sulphuric acid and taking up the oxygen from reducible oxides. Thus when treated with a thiosulphate the soluble ferric salts give a precipitate of sulphur and form ferrous salts. The thiosulphates of the metals of the alkalis are obtained directly by boiling a solution of their sulphites with sulphur: Na_{2}SO_{3} + S = Na_{2}S_{2}O_{3}. The same salts are formed by the action of sulphurous anhydride on solutions of the sulphides; thus sodium sulphide dissolved in water gives sulphur and sodium thiosulphate when a stream of sulphurous anhydride is passed through it: 2Na_{2}S + 3SO_{2} = 2Na_{2}S_{2}O_{3} + S. The polysulphides of the alkali metals when left exposed to the air attract oxygen and also form thiosulphates.[42] [41 bis] Many double salts of thiosulphuric acid are known, for instance, PbS_{2}O_{3},3Na_{2}S_{2}O_{3},12H_{2}O; CaS_{2}O_{3},3K_{2}S_{2}O_{3},5H_{2}O, &c. (Fortman, Schwicker, Fock, and others). [42] Thus when alkali waste, which contains calcium sulphide, undergoes oxidation in the air it first forms a calcium polysulphide, and then calcium thiosulphate, CaS_{2}O_{3}. When iron or zinc acts on a solution of sulphurous acid, besides the hyposulphurous acid first formed, a mixture of sulphite and thiosulphate is obtained (Note 39), 3SO_{2} + Zn_{2} = ZnSO_{3} + ZnS_{2}O_{3}. In this case, as in the formation of hyposulphurous acid, there is no hydrogen liberated. One of the most common methods for preparing thiosulphates consists in the _action of sulphur on the alkalis_. The reaction is accomplished by the formation of sulphides and thiosulphates, just as the reaction of chlorine on alkalis is accompanied by the formation of hypochlorites and chlorides; hence in this respect the thiosulphates hold the same position in the order of the compounds of sulphur as the hypochlorites do among the chlorine compounds. The reaction of caustic soda on an excess of sulphur may be expressed thus: 6NaHO + 12S = 2Na_{2}S_{5} + Na_{2}S_{2}O_{3} + 3H_{2}O. Thus sulphur is soluble in alkalis. On a large scale sodium thiosulphate, Na_{2}S_{2}O_{3}, is prepared by first heating sodium sulphate with charcoal, to form sodium sulphide, which is then dissolved in water and treated with sulphurous anhydride. The reaction is complete when the solution has become slightly acid. A certain amount of caustic alkali is added to the slightly acid solution; a portion of the sulphur is thus precipitated, and the solution is then boiled and evaporated when the salt crystallises out. The saturation of the solution of sodium sulphide by sulphurous anhydride is carried on in different ways--for example, by means of coke-towers, by causing the solution of sulphide to trickle over the coke, and the sulphurous anhydride, obtained by burning sulphur, to pass up the coke-tower from below. An excess of sulphurous anhydride must be avoided, as otherwise sodium trithionate is formed. Sodium thiophosphate is also prepared by the double decomposition of the soluble calcium thiosulphate with sodium sulphate or carbonate, in which case calcium sulphate or carbonate is precipitated. The calcium thiosulphate is prepared by the action of sulphurous anhydride on either calcium sulphide or alkali waste. A dilute solution of calcium thiosulphate may be obtained by treating alkali waste which has been exposed to the action of air with water. On evaporation, this solution gives crystals of the salt containing CaS_{2}O_{3},5H_{2}O. A solution of calcium thiosulphate must be evaporated with great care, because otherwise the salt breaks up into sulphur and calcium sulphide. Even the crystallised salt sometimes undergoes this change. The crystals of sodium thiosulphate are stable, do not effloresce and at 0° dissolve in one part of water, and at 20° in 0·6 part. The solution of this salt does not undergo any change when boiled for a short time, but after prolonged boiling it deposits sulphur. The crystals fuse at 56°, and lose all their water at 100°. When the dry salt is ignited it gives sodium sulphide and sulphate. With acids, a solution of the thiosulphate soon becomes cloudy and deposits an exceedingly fine powder of sulphur (Note 10). If the amount of acid added be considerable, it also evolves sulphurous anhydride: H_{2}S_{2}O_{3} = H_{2}O + S + SO_{2}. Sodium thiosulphate has many practical uses; it is used in photography for dissolving silver chloride and bromide. Its solvent action on silver chloride may be taken advantage of in extracting this metal as chloride from its ores. In dissolving, it forms a double salt of silver and sodium: AgCl + Na_{2}S_{2}O_{3} = NaCl + AgNaS_{2}O_{3}. Sodium thiosulphate is an _antichlor_--that is, a substance which hinders the destructive action of free chlorine owing to its being very easily oxidised by chlorine into sulphuric acid and sodium chloride. The reaction with iodine is different, and is remarkable for the accuracy with which it proceeds. The iodine takes up half the sodium from the salt and converts it into a tetrathionate; 2Na_{2}S_{2}O_{3} + I_{2} = 2NaI + Na_{2}S_{4}O_{6}, and hence this reaction is employed for the determination of free iodine. As iodine is expelled from potassium iodide by chlorine, it is possible also to determine the amount of chlorine by this method if potassium iodide be added to a solution containing chlorine. And as many of the higher oxides are able to evolve iodine from potassium iodide, or chlorine from hydrochloric acid (for example, the higher oxides of manganese, chromium, &c.), it is also possible to determine the amounts of these higher oxides by means of sodium thiosulphate and liberated iodine. This forms the basis of the iodometric method of volumetric analysis. The details of these methods will be found in works on analytical chemistry. On adding a solution of a _lead salt_ gradually to a solution of sodium thiosulphate a white precipitate of lead thiosulphate, PbS_{2}O_{3}, is formed (a soluble double salt is first formed, and if the action be rapid, lead sulphide). When this substance is heated at 200°, it undergoes a change and takes fire. Sodium thiosulphate in solution rapidly reduces cupric salts to cuprous salts by means of the sulphurous acid contained in the thiosulphate, but the resultant cuprous oxide is not precipitated, because it passes into the state of a thiosulphate and forms a double salt. These double cuprous salts are excellent reducing agents. The solution when heated gives a black precipitate of copper sulphide. The following formulæ sufficiently explain the position held by thiosulphuric acid among the other acids of sulphur: Sulphurous acid SO_{2}H(OH) Sulphuric acid SO_{2}OH(OH) Thiosulphuric acid SO_{2}SH(OH) Hyposulphurous acid SO_{2}H(SO_{2}H) Dithionic acid SO_{2}OH(SO_{2}OH) At one time it was thought that all the salts of thiosulphuric acid only existed in combination with water, and it was then supposed that their composition was H_{4}S_{2}O_{4}, or H_{2}SO_{2}, but Popp obtained the anhydrous salts. Although sulphur, oxidising at a high temperature, only forms a small quantity of sulphuric anhydride, SO_{3}, and nearly all passes into sulphurous anhydride, still the latter may be converted into the higher oxide, or _sulphuric anhydride_, SO_{3}, by many methods. Sulphuric anhydride is a solid crystalline substance at the ordinary temperature; it is easily fusible (15°), and volatile (46°), and rapidly attracts moisture. Although it is formed by the combination of sulphurous anhydride with oxygen, it is capable of further combination. Thus it combines with water, hydrochloric acid, ammonia, with many hydrocarbons, and even with sulphuric acid, boric and nitrous anhydrides, &c., and also with bases which burn directly in its vapour, forming sulphates in the presence of traces of moisture (_see_ Chapter IX., Note 29). The oxidation of sulphurous anhydride, SO_{2}, into sulphuric anhydride, SO_{3}, is effected by passing a mixture of the former and dry oxygen or air over incandescent spongy platinum. An increase of pressure accelerates the reaction (Hanisch). If the product be passed into a cold vessel, crystalline sulphuric anhydride is deposited upon the sides of the vessel, but as it is difficult to avoid all traces of moisture it always contains compounds of its hydrates: H_{2}S_{2}O_{7} and H_{2}S_{4}O_{13}, whose presence so modifies the properties of the anhydride (Weber) that formerly two modifications of the anhydride were recognised. The same sulphuric anhydride may be obtained from certain anhydrous sulphates, or those which are almost so, which are decomposed by heat, whilst an impure but perfectly anhydrous anhydride is formed by distillation over phosphoric anhydride. For instance, acid sodium sulphate, NaHSO_{4}, and the pyro- or di-sulphate, Na_{2}S_{2}O_{7} (Chapter XII.) formed from it, when ignited evolve sulphuric anhydride. Green vitriol--that is, ferrous sulphate, FeSO_{4}--belongs to the number of those sulphates which easily give off sulphuric anhydride under the action of heat. It contains water of crystallisation and parts with it when it is heated, but the last equivalent of water is driven off with difficulty, just as is the case with magnesium sulphate, MgSO_{4}7H_{2}O; however, when thoroughly heated, this evolution of sulphuric anhydride does take place, although not completely, because at a high temperature a portion of it is decomposed by the ferrous oxide (SO_{3} + 2FeO), which is converted into ferric oxide, Fe_{2}O_{3}, and in consequence part of the sulphuric anhydride is converted into sulphurous anhydride. Thus the products of the decomposition of ferrous sulphate will be: ferric oxide, Fe_{2}O_{3}, sulphurous anhydride, SO_{2}, and sulphuric anhydride, SO_{3}, according to the equation: 2FeSO_{4} = Fe_{2}O_{3} + SO_{2} + SO_{3}. As water still remains with the ferrous sulphate when it is heated, the result will partially consist of the hydrate H_{2}SO_{4}, with anhydride, SO_{3}, dissolved in it. Sulphuric acid was for a long time prepared in this manner; the process was formerly carried on on a large scale in the neighbourhood of Nordhausen, and hence the sulphuric acid prepared from ferrous sulphate is called _fuming Nordhausen acid_. At the present time the fuming acid is prepared by passing the volatile products of the decomposition of ferrous sulphate through strong sulphuric acid prepared by the ordinary method. The sulphurous anhydride is insoluble in it, but it absorbs the sulphuric anhydride. Sulphuric anhydride may be prepared not only by igniting FeSO_{4} or sodium pyrosulphate, Na_{2}S_{2}O_{7} (the decomposition proceeds at 600°), but also by heating a mixture of the latter and MgSO_{4} (Walters); in the former case a stable double salt MgNa_{2}(SO_{4})_{2} finally remains. It is also obtained by the direct combination of SO_{2} and O under the action of spongy platinum or asbestos coated with platinum black (C. Winkler's process). Nordhausen sulphuric acid fumes in air, owing to its containing and easily giving off sulphuric anhydride, and it is therefore also called _fuming sulphuric acid_; these fumes are nothing but the vapour of sulphuric anhydride combining with the moisture in the air and forming non-volatile sulphuric acid (hydrate).[43] [43] Nordhausen sulphuric acid may serve as a very simple means for the preparation of sulphuric anhydride. For this purpose the Nordhausen acid is heated in a glass retort, whose neck is firmly fixed in the mouth of a well-cooled flask. The access of moisture is prevented by connecting the receiver with a drying-tube. On heating the retort the vapours of sulphuric anhydride will pass over into the receiver, where they condense; the crystals of anhydride thus prepared will, however, contain traces of sulphuric acid--that is, of the hydrate. By repeatedly distilling over phosphoric anhydride, it is possible to obtain the pure anhydride, SO_{3}, especially if the process be carried on without access of air in a closed vessel. The ordinary sulphuric anhydride, which is imperfectly freed from the hydrate, is a snow-white, exceedingly volatile substance, which crystallises (generally by sublimation) in long silky prisms, and only gives the pure anhydride when carefully distilled over P_{2}O_{5}. Freshly prepared crystals of almost pure anhydride fuse at 16° into a colourless liquid having a specific gravity at 26° = 1·91, and at 47° = 1·81; it volatilises at 46°. After being kept for some time the anhydride, even containing only small traces of water, undergoes a change of the following nature: A small quantity of sulphuric acid combines by degrees with a large proportion of the anhydride, forming polysulphuric acids, H_{2}SO_{4},_n_SO_{3}, which fuse with difficulty (even at 100°, Marignac), but decompose when heated. In the entire absence of water this rise in the fusing point does not occur (Weber), and then the anhydride long remains liquid, and solidifies at about +15°, volatilises at 40°, and has a specific gravity 1·94 at 16°. We may add that Weber (1881), by treating sulphuric anhydride with sulphur, obtained a blue lower oxide of sulphur, S_{2}O_{3}. Selenium and tellurium also give similar products with SO_{3}, SeSO_{3}, and TeSO_{3}. Water does not act upon them. Nordhausen sulphuric acid contains a peculiar compound of SO_{3} and H_{2}SO_{4}, or _pyrosulphuric acid_; an imperfect anhydride of sulphuric acid, H_{2}S_{2}O_{7}, analogous in composition with the salts Na_{2}S_{2}O_{7}, K_{2}Cr_{2}O_{7}, and bearing the same relation to H_{2}SO_{4} that pyrophosphoric acid does to H_{3}PO_{4}. The bond holding the sulphuric acid and anhydride together is unstable. This is obvious from the fact that the anhydride may easily be separated from this compound, by the action of heat. In order to obtain the definite compound, the Nordhausen acid is cooled to 5°, or, better still, a portion of it is distilled until all the anhydride and a certain amount of sulphuric acid have passed over into the distillate, which will then solidify at the ordinary temperature, because the compound H_{2}SO_{4},SO_{3} fuses at 35°. Although this substance reacts on water, bases, &c., like a mixture of SO_{3} + H_{2}SO_{4}, still since a definite compound, H_{2}S_{2}O_{7}, exists in a free state and gives salts and a chloranhydride, S_{2}O_{5}Cl_{2},[44] we must admit the existence of a definite pyrosulphuric acid, like pyrophosphoric acid, only that the latter has a far greater stability and is not even converted into a perfect hydrate by water. Further, the salts M_{2}S_{2}O_{7} dissolved in water react in the same manner as the acid salts MHSO_{4}, whilst the imperfect hydrates of phosphoric acid (for example, PHO_{3}, H_{4}P_{2}O_{7}) have independent reactions even in an aqueous solution which distinguish them and their salts from the perfect hydrates. [44] Pyrosulphuric chloranhydride, or _pyrosulphuryl chloride_, S_{2}O_{5}Cl_{2}, corresponds to pyrosulphuric acid, in the same way that sulphuryl chloride, SO_{2}Cl_{2}, corresponds to sulphuric acid. The composition S_{2}O_{5}Cl_{2} = SO_{2}Cl_{2} + SO_{3}. It is obtained by the action of the vapour of sulphuric anhydride on sulphur chloride: S_{2}Cl_{2} + 5SO_{3} = 5SO_{2} + S_{2}O_{5}Cl_{2}. It is also formed (and not sulphuryl chloride, SO_{2}Cl_{2}, Michaelis) by the action of phosphorus pentachloride in excess on sulphuric acid (or its first chloranhydride, SHO_{3}Cl). It is an oily liquid, boiling at about 150°, and of sp. gr. 1·8. According to Konovaloff (Chapter VII.), its vapour density is normal. It should be noticed that the same substance is obtained by the action of sulphuric anhydride on sulphur tetrachloride, and also on carbon tetrachloride, and this substance is the last product of the metalepsis of CH_{4}, and therefore the comparison of SCl_{2} and S_{2}Cl_{2} with products of metalepsis (_see_ later) also finds confirmation in particular reactions. Rose, who obtained pyrosulphuryl chloride, S_{2}O_{5}Cl_{2}, regarded it as SCl_{6},5SO_{3}, for at that time an endeavour was always made to find two component parts of opposite polarity, and this substance was cited as a proof of the existence of a hexachloride, SCl_{6}. Pyrosulphuryl chloride is decomposed by cold water, but more slowly than chlorosulphuric acid and the other chloranhydrides. The relation between pyrosulphuric acid and the normal acid will be obvious if we express the latter by the formula OH(SO_{3}H), because the sulphonic group (SO_{3}H) is then evidently equivalent to OH, and consequently to H, and if we replace both the hydrogens in water by this radicle we shall obtain (SO_{3}H)_{2}O--that is, pyrosulphuric acid. [Illustration: FIG. 87.--Concentration of sulphuric acid in glass retorts. The neck of each retort is attached to a bent glass tube, whose vertical arm is lowered into a glass or earthenware vessel acting as a receiver for the steam which comes over from the acid, as the former still contains a certain amount of acid.] _Sulphuric acid_, H_{2}SO_{4}, is formed by the combination of its anhydride, SO_{3}, and water, with the evolution of a large amount of heat; the reaction SO_{3} + H_{2}O develops 21,300 heat units. The method of its preparation on a large scale, and most of the methods employed for its formation, are dependent on the oxidation of sulphurous anhydride, and the formation of sulphuric anhydride, which forms sulphuric acid under the action of water. The technical method of its manufacture has been described in Chapter VI. The acid obtained _from the lead chambers_ contains a considerable amount of water, and is also impure owing to the presence of oxides of nitrogen, lead compounds, and certain impurities from the burnt sulphur which have come over in a gaseous and vaporous state (for example, arsenic compounds). For practical purposes, hardly any notice is taken of the majority of these impurities, because they do not interfere with its general qualities. Most frequently endeavours are only made to remove, as far as possible, all the water which can be expelled.[45] That is, the object is to obtain the hydrate, H_{2}SO_{4}, from the dilute acid (60 per cent.), and this is effected by evaporation by means of heat. Every given mixture of water and sulphuric acid begins to part with a certain amount of aqueous vapour when heated to a certain definite temperature. At a low temperature either there is no evaporation of water, or there can even be an absorption of moisture from the air. As the removal of the water proceeds, the vapour tension of the residue decreases for the same temperature, and therefore the more dilute the acid the lower the temperature at which it gives up a portion of its water. In consequence of this, the removal of water from dilute solutions of sulphuric acid may be easily carried on (up to 75 p.c. H_{2}SO_{4}) in lead vessels, because at low temperatures dilute sulphuric acid does not attack lead. But as the acid becomes more concentrated the temperature at which the water comes over becomes higher and higher, and then the acid begins to act on lead (with the evolution of sulphuretted hydrogen and conversion of the lead into sulphate), and therefore lead vessels cannot be employed for the complete removal of the water. For this purpose the evaporation is generally carried on in glass or platinum retorts, like those depicted in figs. 87 and 88. [45] The removal of the water, or concentration to almost the real acid, H_{2}SO_{4}, is effected for two reasons: in the first place to avoid the expense of transit (it is cheaper to remove the water than to pay for its transit), and in the second place because many processes--for instance, the refining of petroleum--require a strong acid free from an excess of water, the weak acid having no action. When in the manufacture of chamber acid, both the Gay-Lussac tower (cold, situated at the end of the chambers) and the Glover tower (hot, situated at the beginning of the plant, between the chambers and ovens for the production of SO_{2}) are employed, a mixture of nitrose (_i.e._ the product of the Gay-Lussac tower) and chamber acid containing about 60 p.c. H_{2}SO_{4}, is poured into the Glover tower, where under the action of the hot furnace gases containing SO_{2}, and the water held in the chamber acid (1) N_{2}O_{3} is evolved from the nitrose; (2) water is expelled from the chamber acid; (3) a portion of the SO_{2} is converted into H_{2}SO_{4}; and (4) the furnace gases are cooled. Thus, amongst other things, the Glover tower facilitates the concentration of the chamber acid (removal of H_{2}O), but the product generally contains many impurities. [Illustration: FIG. 88.--Concentration of sulphuric acid in platinum retorts.] _The concentration of sulphuric acid_ in glass retorts is not a continuous process, and consists of heating the dilute 75 per cent. acid until it ceases to give off aqueous vapour, and until acid containing 93-98 per cent. H_{2}SO_{4} (66° Baumé) is obtained--and this takes place when the temperature reaches 320° and the density of the residue reaches 1·847 (66° Baumé).[46] The platinum vessels designed for the continuous concentration of sulphuric acid consist of a still _B_, furnished with a still head _E_, a connecting pipe _E F_, and a syphon tube _H R_, which draws off the sulphuric acid concentrated in the boiler. A stream of sulphuric acid previously concentrated in lead retorts to a density of about 60° Baumé--_i.e._ to 75 per cent. or a sp. gr. of 1·7--runs continuously into the retort through a syphon funnel _E´_. The apparatus is fed from above, because the acid freshly supplied is lighter than that which has already lost water, and also because the water is more easily evaporated from the freshly supplied acid at the surface. The platinum retort is heated, and the steam coming off[47] is condensed in a worm _F G_, whilst as fresh dilute acid is supplied to the boiler the acid already concentrated is drawn off through the syphon tube _H B_, which is furnished with a regulating cock by means of which the outflow of the concentrated acid from the bottom of the retort can be so regulated that it will always present one and the same specific gravity, corresponding with the strength required. For this purpose the acid flowing from the syphon is collected in a receiver _R_, in which a hydrometer, indicating its density, floats; if its density be less than 66° Baumé, the regulating cock is closed sufficiently to retard the outflow of sulphuric acid, so as to lengthen the time of its evaporation in the retort.[48] [46] The difficulty with which the last portions of water are removed is seen from the fact that the boiling becomes very irregular, totally ceasing at one moment, then suddenly starting again, with the rapid formation of a considerable amount of steam, and at the same time bumping and even overturning the vessel in which it is held. Hence it is not a rare occurrence for the glass retorts to break during the distillation; this causes platinum retorts to be preferred, as the boiling then proceeds quite uniformly. [47] According to Regnault, the vapour tensions (in millimetres of mercury) of the water given off by the hydrates of sulphuric acid, H_{2}SO_{4},_n_H_{2}O, are-- _t_=5° 15° 30° _n_ = 1 0·1 0·1 0·2 2 0·4 0·7 1·5 3 0·9 1·6 4·1 4 1·3 2·8 7·0 5 2·1 4·2 10·7 7 3·2 6·2 15·6 9 4·1 8·0 19·6 11 4·4 9·0 22·2 17 5·5 10·6 26·1 According to Lunge, the vapour tension of the aqueous vapour given off from solutions of sulphuric acid containing _p_ per cent. H_{2}SO_{4}, at _t_°, equals the barometric pressure 720 to 730 mm. _p_= 10 20 30 40 50 60 70 80 85 90 95 _t_= 102° 105° 108° 114° 124° 141° 170° 207° 233° 262° 295° The latter figures give the temperature at which water is easily expelled from solutions of sulphuric acid of different strengths. But the evaporation begins sooner, and concentration may be carried on at lower temperatures if a stream of air be passed through the acid. Kessler's process is based upon this (Note 48). [48] The greatest part of the sulphuric acid is used in the soda manufacture, in the conversion of the common salt into sulphate. For this purpose an acid having a density of 60° Baumé is amply sufficient. Chamber acid has a density up to 1·57 = 50° to 51° Baumé; it contains about 35 per cent. of water. About 15 per cent. of this water can be removed in leaden stills, and nearly all the remainder may be expelled in glass or platinum vessels. Acid of 66° Baumé, = 1·847, contains about 96 per cent. of the hydrate H_{2}SO_{4}. The density falls with a greater or less proportion of water, the maximum density corresponding with 97-1/2 per cent. of the hydrate H_{2}SO_{4}. The concentration of H_{2}SO_{4} in platinum retorts has the disadvantage that sulphuric acid, upwards of 90 per cent. in strength, does corrode platinum, although but slightly (a few grams per tens of tons of acid). The retorts therefore require repairing, and the cost of the platinum exceeds the price obtained for concentrating the acid from 90 per cent. to 98 per cent. (in factories the acid is not concentrated beyond this by evaporation in the air). This inconvenience has lately (1891, by Mathey) been eliminated by coating the inside of the platinum retorts with a thin (0·1 to 0·02 mm.) layer of gold which is 40 times less corroded by sulphuric acid than platinum. Négrier (1890) carries on the distillation in porcelain dishes, Blond by heating a thin platinum wire immersed in the acid by means of an electric current, but the most promising method is that of Kessler (1891), which consists in passing hot air over sulphuric acid flowing in a thin stream in stone vessels, so that there is no boiling but only evaporation at moderate temperatures: the transference of the heat is direct (and not through the sides of the vessels), which economises the fuel and prevents the distilling vessels being damaged. When, by evaporation of the water, sulphuric acid attains a density of 66° Baumé (sp. gr. 1·84), it is impossible to concentrate it further, because it then distils over unchanged. _The distillation of sulphuric acid_ is not generally carried on on a large scale, but forms a laboratory process, employed when particularly pure acid is required. The distillation is effected either in platinum retorts furnished with corresponding condensers and receivers, or in glass retorts. In the latter case, great caution is necessary, because the boiling of sulphuric acid itself is accompanied by still more violent jerks and greater irregularity than even the evaporation of the last portions of water contained in the acid. If the glass retort which holds the strong sulphuric acid to be distilled be heated directly from below, it frequently jerks and breaks. For greater safety the heating is not effected from below, but at the sides of the retort. The evaporation then does not proceed in the whole mass, but only from the upper portions of the liquid, and therefore goes on much more quietly. The acid may be made to boil quietly also by surrounding the retort with good conductors of heat--for example, iron filings, or by immersing a bunch of platinum wires in the acid, as the bubbles of sulphuric acid vapour then form on the extremities of the wires. Strictly speaking, _sulphuric acid is not volatile_, and at its so-called boiling-point it really decomposes into its anhydride and water; its boiling-point (338°) being nothing else but its temperature of decomposition. The products of this decomposition are substances boiling much below the temperature of the decomposition of sulphuric acid. This conclusion with regard to the process of the distillation of sulphuric acid may be deduced from Bineau's observations on the vapour-density of sulphuric acid. This density referred to hydrogen proved to be half that which sulphuric acid should have according to its molecular weight, H_{2}SO_{4}, in which case it should be 49, whilst the observed density was equal to 24·5. Besides which, Marignac showed that the first portions of the sulphuric acid distilling over contain less of the elements of water than the portion which remains behind, or which distils over towards the end. This is explained by the fact that on distillation the sulphuric acid is decomposed, but a portion of the water proceeding from its decomposition is retained by the remaining mass of sulphuric acid, and therefore at first a mixture of sulphuric acid and sulphuric anhydride--_i.e._ fuming sulphuric acid--is obtained in the distillate. It is possible by repeating the distillation several times and only collecting the first portions of the distillate, to obtain a distinctly fuming acid. To obtain the definite hydrate H_{2}SO_{4} it is necessary to refrigerate a highly concentrated acid, of as great a purity as possible, to which a small quantity of sulphuric anhydride has been previously added. Sulphuric acid containing a small quantity (a fraction of a per cent. by weight) of water only freezes at a very low temperature, while the pure normal acid, H_{2}SO_{4}, solidifies when it is cooled below 0°, and therefore the normal acid first crystallises out from the concentrated sulphuric acid. By repeating the refrigeration several times, and pouring off the unsolidified portion, it is possible to obtain a pure _normal hydrate_, H_{2}SO_{4}, which melts at 10°·4. Even at 40° it gives off distinct fumes--that is, it begins to evolve sulphuric anhydride, which volatilises, and therefore even in a dry atmosphere the hydrate H_{2}SO_{4} becomes weaker, until it contains 1-1/2 p.c. of water.[49] [49] Thus it appears that so common, and apparently so stable, a compound as sulphuric acid decomposes even at a low temperature with separation of the anhydride, but this decomposition is restricted by a limit, corresponding to the presence of about 1-1/2 p.c. of water, or to a composition of nearly H_{2}O,12H_{2}SO_{4}. Now there is no reason for thinking that this substance is a definite compound; it is an equilibrated system which does not decompose under ordinary circumstances below 338°. Dittmar carried on the distillation under pressures varying between 30 and 2,140 millimetres (of mercury), and he found that the composition of the residue hardly varies, and contains from 99·2 to 98·2 per cent. of the normal hydrate, although at 30 mm. the temperature of distillation is about 210° and at 2,140 mm. it is 382°. Furthermore, it is a fact of practical importance that under a pressure of two atmospheres the distillation of sulphuric acid proceeds very quietly. Sulphuric acid may be _purified_ from the majority of its impurities by distillation, if the first and last portions of the distillate be rejected. The first portions will contain the oxides of nitrogen, hydrochloric acid, &c., and the last portions the less volatile impurities. The oxides of nitrogen may be removed by heating the acid with charcoal, which converts them into volatile gases. Sulphuric acid may be freed from arsenic by heating it with manganese dioxide and then distilling. This oxidises all the arsenic into non-volatile arsenic acid. Without a preliminary oxidation it would partially remain as volatile arsenious acid, and might pass over into the distillate. The arsenic may also be driven off by first reducing it to arsenious acid, and then passing hydrochloric acid gas through the heated acid. It is then converted into arsenious chloride, which volatilises. In a concentrated form sulphuric acid is commercially known as _oil of vitriol_, because for a long time it was obtained from green vitriol and because it has an oily appearance and flows from one vessel into another in a thick and somewhat sluggish stream, like the majority of oily substances, and in this clearly differs from such liquids as water, spirit, ether, and the like, which exhibit a far greater mobility. Among its reactions the first to be remarked is its faculty for the formation of many compounds. We already know that it combines with its anhydride, and with the sulphates of the alkali metals; that it is soluble in water, with which it forms more or less stable compounds. Sulphuric acid, when mixed with water, develops a very considerable amount of heat.[50] [50] The amount of heat developed by the mixture of sulphuric acid with water is expressed in the diagram on p. 77, Volume I., by the middle curve, whose abscissæ are the percentage amounts of acid (H_{2}SO_{4}) in the resultant solution, and ordinates the number of units of heat corresponding with the formation of 100 cubic centimetres of the solution (at 18°). The calculations on which the curve is designed are based on Thomsen's determinations, which show that 98 grams or a molecular amount of sulphuric acid, in combining with _m_ molecules of water (that is, with _m_=18 grams of water), develop the following number of units of heat, R:-- _m_ = 1 2 3 5 9 R = 6379 9418 11137 13108 14952 _c_ = 0·432 0·470 0·500 0·576 0·701 T = 127° 149° 146° 121° 82° _m_ = 19 49 100 200 R = 16256 16684 16859 17066 _c_ = 0·821 0·914 0·954 0·975 T = 145° 19° 9° 5° _c_ stands for the specific heat of H_{2}SO_{4}_m_H_{2}O (according to Marignac and Pfaundler), and T for the rise in temperature which proceeds from the mixture of H_{2}SO_{4} with _m_H_{2}O. The diagram shows that contraction and rise of temperature proceed almost parallel with each other. Besides the normal hydrate H_{2}SO_{4}, _another definite hydrate_, H_{2}SO_{4},H_{2}O (84·48 per cent. of the normal hydrate, and 15·52 per cent. of water) is known; it crystallises[50 bis] extremely easily in large six-sided prisms, which form above 0°--namely, at about +8°·5; when heated to 210° it loses water.[51] If the hydrates H_{2}SO_{4} and H_{2}SO_{4},H_{2}O exist at low temperatures as definite crystalline compounds, and if pyrosulphuric acid, H_{2}SO_{4}SO_{3}, has the same property, and if they all decompose with more or less ease on a rise of temperature, with the disengagement of either SO_{3} or H_{2}O, and in their ordinary form present all the properties of simple solutions, it follows that between sulphuric anhydride, SO_{3}, and water, H_{2}O, there exists a consecutive series of homogeneous liquids or solutions, among which we must distinguish _definite compounds_, and therefore it is quite justifiable to look for other definite compounds between SO_{3} and H_{2}O, beyond the conditions for a change of state. In this respect we may be guided by the variation of properties of any kind, proceeding concurrently with a variation in the composition of a solution. [50 bis] Pickering (1890) showed (_a_) that dilute solutions of sulphuric acid containing up to H_{2}SO_{4} + 10H_{2}O deposit ice (at -0°·12 when there is 2,000H_{2}O per H_{2}SO_{4}, at -0°·23 when there is 1,000H_{2}O, at -1°·04 when there is 200H_{2}O, at -2°·12 when there is 100H_{2}O, at -4°·5 when there is 50H_{2}O, at -15°·7 when there is 20H_{2}O, and at -61° when the composition of the solution is H_{2}SO_{4} + 10H_{2}O); (_b_) that for higher concentrations crystals separate out at a considerable degree of cold, having the composition H_{2}SO_{4}4H_{2}O, which melt at -24°·5, and if either water or H_{2}SO_{4} be added to this compound the temperature of crystallisation falls, so that a solution of the composition 12H_{2}SO_{4} + 100H_{2}O gives crystals of the above hydrate at -70°, 15H_{2}SO_{4} + 100H_{2}O at -47°, 30H_{2}SO_{4} + 100H_{2}O at -32°, 40H_{2}SO_{4} + 100H_{2}O at -52°; (_c_) that if the amount of H_{2}SO_{4} be still greater, then a hydrate H_{2}SO_{4}H_{2}O separates out and melts at +8°·5, while the addition of water or sulphuric acid to it lowers the temperature of crystallisation so that the crystallisation of H_{2}SO_{4}H_{2}O from a solution of the composition H_{2}SO_{4} + 1·73H_{2}O takes place at -22°, H_{2}SO_{4} + 1·5H_{2}O at -6°·5, H_{2}SO_{4} + 1·2H_{2}O at +3°·7, H_{2}SO_{4} + 0·75H_{2}O at +2°·8, H_{2}SO_{4} + 0·5H_{2}O at -16°; (_d_) that when there is less than 40H_{2}O per 100H_{2}SO_{4}, refrigeration separates out the normal hydrate H_{2}SO_{4}, which melts at +10°·35, and that a solution of the composition H_{2}SO_{4} + 0·35H_{2}O deposits crystals of this hydrate at -34°, H_{2}SO_{4} + 0·1H_{2}O at -4°·1, H_{2}SO_{4} + 0·05H_{2}O at +4°·9, while fuming acid of the composition H_{2}SO_{4} + 0·05SO_{3} deposits H_{2}SO_{4} at about +7°. Thus the temperature of the separation of crystals clearly distinguishes the above four regions of solutions, and in the space between H_{2}SO_{4} + H_{2}O and +25H_{2}O a particular hydrate H_{2}SO_{4}4H_{2}O separates out, discovered by Pickering, the isolation of which deserves full attention and further research. I may add here that the existence of a hydrate H_{2}SO_{4}4H_{2}O was pointed out in my work, _The Investigation of Aqueous Solutions_, p. 120 (1887), upon the basis that it has at all temperatures a smaller value for the coefficient of expansion _k_ in the formula S_{_t_} = S_{0}/(1 - _kt_) than the adjacent (in composition) solutions of sulphuric acid. And for solutions approximating to H_{2}SO_{4}10H_{2}O in their composition, _k_ is constant at all temperatures (for more dilute solutions the value of _k_ increases with _t_ and for more concentrated solutions it decreases). This solution (with 10H_{2}O) forms the point of transition between more dilute solutions which deposit ice (water) when refrigerated and those which give crystals of H_{2}SO_{4}4H_{2}O. According to R. Pictet (1894) the solution H_{2}SO_{4}10H_{2}O freezes at -88° (but no reference is made as to what separates out), _i.e._ at a lower temperature than all the other solutions of sulphuric acid. However, in respect to these last researches of R. Pictet (for 88·88 p.c. H_{2}SO_{4} -55°, for H_{2}SO_{4}H_{2}O +3·5°, for H_{2}SO_{4}2H_{2}O -70°, for H_{2}SO_{4}4H_{2}O -40°, &c.) it should be remarked that they offer some quite improbable data; for example, for H_{2}SO_{4}75H_{2}O they give the freezing point as 0°, for H_{2}SO_{4}300H_{2}O +4°·5, and even for H_{2}SO_{4}1000H_{2}O +0°·5, although it is well known that a small amount of sulphuric acid lowers the temperature of the formation of ice. I have found by direct experiment that a frozen solidified solution of H_{2}SO_{4} + 300H_{2}O melted completely at 0°. [51] With an excess of snow, the hydrate H_{2}SO_{4},H_{2}O, like the normal hydrate, gives a freezing mixture, owing to the absorption of a large amount of heat (the latent heat of fusion). In melting, the molecule H_{2}SO_{4} absorbs 960 heat units, and the molecule H_{2}SO_{4}H_{2}O 3,680 heat units. If therefore we mix one gram molecule of this hydrate with seventeen gram molecules of snow, there is an absorption of 18,080 heat units, because 17H_{2}O absorbs 17 × 1,430 heat units, and the combination of the monohydrate with water evolves 9,800 heat units. As the specific heat of the resultant compound H_{2}SO_{4},18H_{2}O = 0·813, the fall of temperature will be -52°·6. And, in fact, a very low temperature may be obtained by means of sulphuric acid. But only a few properties have been determined with sufficient accuracy. In those properties which have been determined for many solutions of sulphuric acid, it is actually seen that the above-mentioned definite compounds are distinguished by distinctive marks of change. As an example we may cite the variation of the specific gravity with a variation of temperature (namely K = _ds/dt_, if _s_ be the sp. gr. and _t_ the temperature). For the normal hydrate, H_{2}SO_{4}, this factor is easily determined from the fact that-- _s_ = 18528 - 10·65_t_ + 0·013_t_^2, where _s_ is the specific gravity at _t_ (degrees Celsius) if the sp. gr. of water at 4° = 10,000. Therefore K = 10·65 - 0·026_t_. This means that at 0° the sp. gr. of the acid H_{2}SO_{4} decreases by 10·65 for every rise of a degree of temperature, at 10° by 10·39, at 20° by 10·13, at 30° by 9·87.[52] And for solutions containing slightly more anhydride than the acid H_{2}SO_{4} (_i.e._ for fuming sulphuric acid), as well as for solutions containing more water, K is greater than for the acid H_{2}SO_{4}. Thus for the solution SO_{3},2H_{2}SO_{4}, at 10° K = 11·0. On diluting the acid H_{2}SO_{4} K again increases until the formation of the solution H_{2}SO_{4},H_{2}O (K = 11·1 at 10°), and then, on further dilution with water, it again decreases. Consequently both hydrates H_{2}SO_{4} and H_{2}SO_{4},H_{2}O are here expressed by an alteration of the magnitude of K. [52] For example, if it be taken that at 19° the sp. gr. of pure sulphuric acid is 1·8330, then at 20° it is 1·8330 - (20 - 19)10·13 = 1·8320. [Illustration: FIG. 89.--Diagram showing the variation of the factor (_ds/dp_) of the specific gravity of solutions of sulphuric acid. The percentage quantities of the acid, H_{2}SO_{4}, are laid out on the axes of abscissæ. The ordinates are the factors or rises in sp. gr. (water at 4 = 10,000) with the increase in the quantity of H_{2}SO_{4}.] This shows that in liquid solutions it is possible by studying the variation of their properties (without a change of physical state) to recognise the presence or formation of definite hydrate compounds, and therefore an exact investigation of the properties of solutions, of their specific gravity for instance, should give direct indications of such compounds.[53] The mean result of the most trustworthy determinations of this nature is given in the following tables. The first of these tables gives the specific gravities (in vacuo, taking the sp. gr. of water at 4° = 1), at 0° (column 3), 15° (column 4), and 30° (column 5),[53 bis] for solutions having the composition H_{2}SO_{4} + _n_H_{2}O (the value of _n_ is given in the first column), and containing _p_ (column 2) per cent. (by weight in vacuo) of H_{2}SO_{4}.[53 tri] _n_ _p_ 0° 15° 30° 100 5·16 1·0374 1·0341 1·0292 50 9·82 1·0717 1·0666 1·0603 25 17·88 1·1337 1·1257 1·1173 15 26·63 1·2040 1·1939 1·1837 10 35·25 1·2758 1·2649 1·2540 8 40·50 1·3223 1·3110 1·2998 6 47·57 1·3865 1·3748 1·3622 5 52·13 1·4301 1·4180 1·4062 4 57·65 1·4881 1·4755 1·4631 3 64·47 1·5635 1·5501 1·5370 2 73·13 1·6648 1·6500 1·6359 1 84·48 1·7940 1·7772 1·7608 0·5 91·59 1·8445 1·8284 1·8128 H_{2}SO_{4} 100 1·8529 1·8372 1·8221 [53] Unfortunately, notwithstanding the great number of fragmentary and systematic researches which have been made (by Parks, Ure, Bineau, Kolbe, Lunge, Marignac, Kremers, Thomsen, Perkin, and others) for determining the relation between the sp. gr. and composition of solutions of sulphuric acid, they contain discrepancies which amount to, and even exceed, 0·002 in the sp. gr. For instance, at 15°·4 the solution of composition H_{2}SO_{4}3H_{2}O has a sp. gr. 1·5493 according to Perkin (1886), 1·5501 according to Pickering (1890), and 1·5525 according to Lunge (1890). The cause of these discrepancies must be looked for in the methods employed for determining the composition of the solutions--_i.e._ in the inaccuracy with which the percentage amount of H_{2}SO_{4} is determined, for a difference of 1 p.c. corresponds to a difference of from 0·0070 (for very weak solutions) to 0·0118 (for a solution containing about 73 p.c.) in the specific gravity (that is the factor _ds/dp_) at 15°. As it is possible to determine the specific gravity with an accuracy even exceeding 0·0002, the specific gravities given in the adjoining tables are only averages and most probable data in which the error, especially for the 30-80 p.c. solutions cannot be less than 0·0010 (taking water at 4° as 1). [53 bis] Judging from the best existing determinations (of Marignac, Kremers, and Pickering) for solutions of sulphuric acid (especially those containing more than 5 p.c. H_{2}SO_{4}) within the limits of 0° and 30° (and even to 40°), the variation of the sp. gr. with the temperature _t_ may (within the accuracy of the existing determinations) be perfectly expressed by the equation S_{_t_} = S_{_0_} + A_t_ + B_t_^2. It must be added that (1) three specific gravities fully determine the variation of the density with _t_; (2) _ds/dt_ = A + 2B_t_--_i.e._ the factor of the temperature is expressed by a straight line; (3) the value of A (if _p_ be greater than 5 p.c.) is negative, and numerically much greater than B; (4) the value of B for dilute solutions containing less than 25 p.c. is negative; for solutions approximating to H_{2}SO_{4}3H_{2}O in their composition it is equal to 0, and for solutions of greater concentration B is positive; (5) the factor _ds/dp_ for all temperatures attains a maximum value about H_{2}SO_{4}H_{2}O; (6) on dividing _ds/dt_ by S_{_0_}, and so obtaining the coefficient of expansion _k_ (_see_ Note 53), a minimum is obtained near H_{2}SO_{4} and H_{2}SO_{4}4H_{2}O, and a maximum at H_{2}SO_{4}H_{2}O for all temperatures. [53 tri] These data (as well as those in the following table) have been recalculated by me chiefly upon the basis of Kremer's, Pickering's, Perkin's, and my own determinations; all the requisite corrections have been introduced, and I have reason for thinking that in each of them the probable error (or difference from the true figures, now unknown) of the specific gravity does not exceed ±0·0007 (if water at 4° = 1) for the 25-80 p.c. solutions, and ±0·0002 for the more dilute or concentrated solutions. In the second table the first column gives the percentage amount _p_ (by weight) of H_{2}SO_{4}, the second column the weight in grams (S_{15}) of a litre of the solution at 15° (at 4° the weight of a litre of water = 1,000 grams), the third column, the variation (_d_S/_dt_) of this weight for a rise of 1°, the fourth column, the variation _d_S/_dp_ of this weight (at 15°) for a rise of 1 per cent. of H_{2}SO_{4}, the fifth column, the difference between the weight of a litre at 0° and 15° (S_{0} - S_{15}), and the sixth column, the difference between the weight of a litre at 15° and 30° (S_{15} - S_{30}). _p_ _S__{15} _dS__{15}/_dt_ _dS__{15}/_dp_ _S__{0}- _S__{15}- _S__{15} _S__{30} 0 999·15 0·148 7·0 0·7 3·4 5 1033·0 0·27 6·8 3·1 5·0 10 1067·7 0·38 7·1 5·2 6·4 20 1141·9 0·58 7·7 8·6 8·9 30 1221·3 0·69 8·2 10·4 10·4 40 1306·6 0·75 8·8 11·3 11·2 50 1397·9 0·79 9·9 11·9 11·8 60 1501·2 0·86 10·8 13·0 12·7 70 1613·1 0·93 11·6 14·1 13·8 80 1731·4 1·04 11·0 15·8 15·4 90 1819·9 1·08 5·4 16·4 16·0 95 1837·6 1·03 +1·7 15·8 15·1 100 1837·2 1·03 -1·9[54] 15·7 15·1 The figures in these tables give the means of finding the amount of H_{2}SO_{4} contained in a solution from its specific gravity,[55] and also show that 'special points' in the lines of variation of the specific gravity with the temperature and percentage composition correspond to certain definite compounds of H_{2}SO_{4} with OH_{2}. This is best seen in the variation of the factors (_d_S/_dt_ and _d_S/_dp_) with the temperature and composition (columns 3, 4, second table). We have already mentioned how the factor of temperature points to the existence of hydrates, H_{2}SO_{4} and H_{2}SO_{4},H_{2}O. As regards the factor _d_S/_dp_ (giving the increase of sp. gr. with an increase of 1 per cent. H_{2}SO_{4}) the following are the three most salient points: (1) In passing from 98 per cent. to 100 per cent. the factor is negative, and at 100 per cent. about -0·0019 (_i.e._ at 99 per cent. the sp. gr. is about 1·8391, and at 100 per cent. about 1·8372, at 15°, the amount of H_{2}SO_{4} has increased whilst the sp. gr. has decreased), but as soon as a certain amount of SO_{3} is added to the definite compound H_{2}SO_{4} (and 'fuming' acid formed) the specific gravity rises (for example, for H_{2}SO_{4} 0·136 SO_{3} the sp. gr. at 15° = 1·866), that is the factor becomes positive (and, in fact, greater by +0·01), so that the formation of the definite hydrate H_{2}SO_{4} is accompanied by a distinct and considerable break in the continuity of the factor[55 bis]; (2) The factor (_d_S/_dp_) in increasing in its passage from dilute to concentrated solutions, attains a maximum value (at 15° about 0·012) about H_{2}SO_{4}2H_{2}O, _i.e._ at about the hydrate corresponding to the form SX_{6}; proper to the compounds of sulphur, for S(OH)_{6} = H_{2}SO_{4}2H_{2}O; the same hydrate corresponds to the composition of gypsum CaSO_{4}2H_{2}O, and to it also corresponds the greatest contraction and rise of temperature in mixing H_{2}SO_{4} with H_{2}O (_see_ Chapter I., Note 28); (3) The variation of the factor (_d_S/_dp_) under certain variations in the composition proceeds so uniformly and regularly, and is so different from the variation given under other proportions of H_{2}SO_{4} and H_{2}O, that the sum of the variations of _d_S/_dp_ is expressed by a series of straight lines, if the values of _p_ be laid along the axis of abscissæ and those of _d_S/_dp_ along the ordinates.[56] Thus, for instance, for 15°, at 10 per cent. _d_S/_dp_ = 0·0071, at 20 per cent. = 0·0077, at 30 per cent. = 0·0082, at 40 per cent. = 0·0088, that is, for each 10 per cent. the factor increases by about 0·0006 for the whole of the above range, but beyond this it becomes larger, and then, after passing H_{2}SO_{4}2H_{2}O, it begins to fall rapidly. Such changes in the variation of the factor take place apparently about definite hydrates,[56 bis] and especially about H_{2}SO_{4}4H_{2}O, H_{2}SO_{4}2H_{2}O and H_{2}SO_{4}H_{2}O. All this indicating as it does the special chemical affinity of sulphuric acid for water, although of no small significance for comprehending the nature of solutions (_see_ Chapter I. and Chapter VII.), contains many special points which require detailed investigation, the chief difficulty being that it requires great accuracy in a large number of experimental data. [54] The factor _d_S/_dp_ passes through 0, that is, the specific gravity attains a maximum value at about 98 p.c. This was discovered by Kohlrausch, and confirmed by Chertel, Pickering, and others. [55] Naturally under the condition that there is no other ingredient besides water, which is sufficiently true. For commercial acid, whose specific gravity is usually expressed in degrees of Baumé's hydrometer, we may add that at 15° Specific gravity 1 1·1 1·2 1·3 1·4 1·5 1·6 1·7 1·8 Degree Baumé 0 13 24 33·3 41·2 48·1 54·1 59·5 64·2 66° Baumé (the strongest commercial acid or oil of vitriol) corresponds to a sp. gr. 1·84. By employing the second table (by the method of interpolation) the specific gravity, at a given temperature (from 0° to 30°) can be found for any percentage amount of H_{2}SO_{4}, and therefore conversely the percentage of H_{2}SO_{4} can be found from the specific gravity. [55 bis] Whether similar (even small) breaks in the continuity of the factor _dS_/_dp_ exist or not, for other hydrates (for instance, for H_{2}SO_{4}H_{2}O and H_{2}SO_{4}4H_{2}O) cannot as yet be affirmed owing to the want of accurate data (Note 53). In my investigation of this subject (1887) I admit their possibility, but only conditionally; and now, without insisting upon a similar opinion, I only hold to the existence of a distinct break in the factor at H_{2}SO_{4}, being guided by C. Winkler's observations ond the specific gravities of fuming sulphuric acid. [56] In 1887, on considering all the existent observations for a temperature 0°, I gave the accompanying scheme (p. 243) of the variation of the factor _ds_/_dp_ at 0°. I did not then (1887) give this scheme an absolute value, and now after the appearance of two series of new determinations (Lunge and Pickering in 1890), which disagree in many points, I think it well to state quite clearly: (1) that Lunge's and Pickering's new determinations have not added to the accuracy of our data respecting the variation of the specific gravity of solutions of sulphuric acid; (2) that the sum total of existing data does not negative (within the limit of experimental accuracy) the possibility of a rectilinear and broken form for the factors _ds_/_dp_; (3) that the supposition of 'special points' in _ds_/_dp_, indicating definite hydrates, finds confirmation in all the latest determinations; (4) that the supposition respecting the existence of hydrates determining a break of the factor _ds_/_dp_ is in in way altered if, instead of a series of broken straight lines, there be a continuous series of curves, nearly approaching straight lines; and (5) that this subject deserves (as I mentioned in 1887) new and careful elaboration, because it concerns that foremost problem in our science--solutions--and introduces a special method into it--that is, the study of differential variations in a property which is so easily observed as the specific gravity of a liquid. [56 bis] These hydrates are: (_a_) H_{2}SO_{4} = SO_{3}H_{2}O (melts at + 10°·4); (_b_) H_{2}SO_{4}H_{2}O = SO_{3}2H_{2}O (crystallo-hydrate, melts at +8°·5); (_c_) H_{2}SO_{4}2H_{2}O (is apparently not crystallisable); (_d_) one of the hydrates between H_{2}SO_{4}6H_{2}O and H_{2}SO_{4}3H_{2}O, most probably H_{2}SO_{4}4H_{2}O = SO_{3}5H_{2}O, for it crystallises at -24°·5 (Note 50 bis); and (_e_) a certain hydrate with a large proportion of water, about H_{2}SO_{4}150H_{2}O. The existence of the last is inferred from the fact that the factor _ds_/_dp_ first falls, starting from water, and then rises, and this change takes place when _p_ is less than 5 p.c. Certainly a change in the variation of _ds_/_dp_ or _ds_/_dt_ does take place in the neighbourhood of these five hydrates (Pickering, 1890, recognised a far greater number of hydrates). I think it well to add that if the composition of the solutions be expressed by the percentage amount of molecules--_r__{1}SO_{3} + (100 - _r__{1})H_{2}O we find that for H_{2}SO_{4}, _r__{1} = 50, for H_{2}SO_{4}2H_{2}O _r__{1} = 25 = 50/2, for H_{2}SO_{4}H_{2}O, _r__{1} = 33·333 = 50 · 2/3, while for H_{2}SO_{4}4H_{2}O, _r__{1} = 16·666 = 50 · 1/3--_i.e._ that the chief hydrates are distributed symmetrically between H_{2}O and H_{2}SO_{4}. Besides which I may mention that my researches (1887) upon the abrupt changes in the factor for solutions of sulphuric acid, and upon the correspondence of the breaks of _ds_/_dp_ with definite hydrates, received an indirect confirmation not only in the solutions of HNO_{3}, HCl, C_{2}H_{6}O, C_{3}H_{8}O, &c., which I investigated (in my work cited in Chapter I., Note 19), but also in the careful observations made by Professor Cheltzoff on the solutions of FeCl_{3} and ZnCl_{2} (Chapter XVI., Note 4) which showed the existence in these solutions of an almost similar change in _ds_/_dp_ as is found in sulphuric acid. The detailed researches (1893) made by Tourbaba on the solutions of many organic substances are of a similar nature. Besides which, H. Crompton (1888), in his researches on the electrical conductivity of solutions of sulphuric acid, and Tammann, in his observations on their vapour tension, found a correlation with the hydrates indicated as above by the investigation of their specific gravities. The influence of mixtures of a definite composition upon the chemical relations of solutions is even exhibited in such a complex process as electrolysis. V. Kouriloff (1891) showed that mixtures containing about 3 p.c., 47 p.c. and 73 p.c. of sulphuric acid--_i.e._ whose composition approaches that of the hydrates H_{2}SO_{4}150H_{2}O, H_{2}SO_{4}6H_{2}O and H_{2}SO_{4}2H_{2}O--exhibit certain peculiarities in respect to the amount of peroxide of hydrogen formed during electrolysis. Thus a 3 p.c. solution gives a maximum amount of peroxide of hydrogen at the negative pole, as compared with that given by other neighbouring concentrations. Starting from 3 p.c., the formation of peroxide of hydrogen ceases until a concentration of 47 p.c. is reached. The great affinity of sulphuric acid for water is also seen from the fact that when the strong acid acts on the majority of _organic substances_ containing hydrogen and oxygen (especially on heating) it very frequently _takes up these elements in the form of water_. Thus strong sulphuric acid acting on alcohol, C_{2}H_{6}O, removes the elements of water from it, and converts it into olefiant gas, C_{2}H_{4}. It acts in a similar manner on wood and other vegetable tissues, which it chars. If a piece of wood be immersed in strong sulphuric acid it turns black. This is owing to the fact that the wood contains carbohydrates which give up hydrogen and oxygen as water to the sulphuric acid, leaving charcoal, or a black mass very rich in it. For example, cellulose, C_{6}H_{10}O_{5}, acts in this manner.[57] [57] Cellulose, for instance unsized paper or calico, is dissolved by strong sulphuric acid. Acid diluted with about half its volume of water converts it (if the action be of short duration) into vegetable parchment (Chapter I., Note 18). The action of dilute solutions of sulphuric acid converts it into hydro-cellulose, and the fibre loses its coherent quality and becomes brittle. The prolonged action of strong sulphuric acid chars the cellulose while dilute acid converts it into glucose. If sulphuric acid be kept in an open vessel, the organic matter of the dust held in the atmosphere falls into it and blackens the acid. The same thing happens if sulphuric acid be kept in a bottle closed by a cork; the cork becomes charred, and the acid turns black. However, the chemical properties of the acid undergo only a very slight change when it turns black. Sulphuric acid which is considerably diluted with water does not produce the above effects, which clearly shows their dependence on the affinity of the sulphuric acid for water. It is evident from the preceding that strong sulphuric acid will act as a powerful poison; whilst, on the other hand, when very dilute it is employed in certain medicines and as a fertiliser for plants. We have already had frequent occasion to notice the very _energetic acid properties_ of sulphuric acid, and therefore we will now only consider a few of their aspects. First of all we must remember that, with calcium, strontium, and especially with barium and lead, sulphuric acid forms very slightly soluble salts, whilst with the majority of other metals it gives more easily soluble salts, which in the majority of cases are able, like sulphuric acid itself, to combine with water to form crystallo-hydrates. Normal sulphuric acid, containing two atoms of hydrogen in its molecule, is able for this reason alone to form two classes of salts, _normal_ and _acid_, which it does with great facility _with the alkali metals_. The metals of the alkaline earths and the majority of other metals, if they do form acid sulphates, do so under exceptional conditions (with an excess of strong sulphuric acid), and these salts when formed are decomposable by water--that is, although having a certain degree of physical stability they have no chemical stability. Besides the acid salts RHSO_{4}, sulphuric acid also gives other forms of acid salts. An entire series of salts having the composition RHSO_{4},H_{2}SO_{4}, or for bivalent metals RSO_{4},3H_{2}SO_{4},[58] has been prepared. Such salts have been obtained for potassium, sodium, nickel, calcium, silver, magnesium, manganese. They are prepared by dissolving the sulphates in an excess of sulphuric acid and heating the solution until the excess of sulphuric acid is driven off; on cooling, the mass solidifies to a crystalline salt. Besides which, Rose obtained a salt having the composition Na_{2}SO_{4},NaHSO_{4}, and if HNaSO_{4} be heated it easily forms a salt Na_{2}S_{2}O_{7} = Na_{2}SO_{4},SO_{3}; hence it is clear that sulphuric anhydride combines with various proportions of bases, just as it combines with various proportions of water. [58] Weber (1884) obtained a series of salts R_{2}O,8SO_{3}_n_H_{2}O for K, Rb, Cs, and Tl. We have already learned that sulphuric acid displaces the acid from the salts of nitric, carbonic, and many other volatile acids. Berthollet's laws (Chapter X.) explain this by the small volatility of sulphuric acid; and, indeed, in an aqueous solution sulphuric acid displaces the much less soluble boric acid from its compounds--for instance, from borax, and it also displaces silica from its compounds with bases; but both boric anhydride and silica, when fused with sulphates, decompose them, displacing sulphuric anhydride, SO_{3}, because they are less volatile than sulphuric anhydride. It is also well known that with metals, sulphuric acid forms salts giving off hydrogen (Fe, Zn, &c.), or sulphur dioxide (Cu, Hg, &c.).[58 bis] [58 bis] Ditte (1890) divides all the metals into two groups with respect to sulphuric acid; the first group includes silver, mercury, copper, lead, and bismuth, which are only acted upon by hot concentrated acid. In this case sulphurous anhydride is evolved without any by-reactions. The second group contains manganese, nickel, cobalt, iron, zinc, cadmium, aluminium, tin, thallium, and the alkali metals. They react with sulphuric acid of any concentration at any temperature. At a low temperature hydrogen is disengaged, and at higher temperatures (and with very concentrated acid) hydrogen and sulphurous anhydride are simultaneously evolved. The reactions of sulphuric acid _with respect to organic substances_ are generally determined by its acid character, when the direct extraction of water, or oxidation at the expense of the oxygen of the sulphuric acid,[59] or disintegration does not take place. Thus the majority of the saturated hydrocarbons, C_{_n_}H_{2_m_}, form with sulphuric acid a special class of _sulphonic acids_, C_{_n_}H_{2_m_-1}(HSO_{3}); for example, benzene, C_{6}H_{6}, forms benzenesulphonic acid, C_{6}H_{5}.SO_{3}H, water being separated, for the formation of which oxygen is taken up from the sulphuric acid, for the product contains less oxygen than the sulphuric acid. It is evident from the existence of these acids that the hydrogen in organic compounds is replaceable by the group SO_{3}H, just as it may be replaced by the radicles Cl, NO_{2}, CO_{2}H and others. As the radicle of sulphuric acid or _sulphoxyl_, SO_{2}OH or SHO_{3}, contains, like carboxyl (Vol. I., p. 395), one hydrogen (hydroxyl) of sulphuric acid, the resultant substances are acids whose basicity is equal to the number of hydrogens replaced by sulphoxyl. Since also sulphoxyl takes the place of hydrogen, and itself contains hydrogen, the sulpho-acids are equal to a hydrocarbon + SO_{3}, just as every organic (carboxylic) acid is equal to a hydrocarbon + CO_{2}. Moreover, here this relation corresponds with actual fact, because many sulphonic acids are obtained by the direct combination of sulphuric anhydride: C_{6}H_{5},(SO_{3}H) = C_{6}H_{6} + SO_{3}. The sulphonic acids give soluble barium salts, and are therefore easily distinguished from sulphuric acid. They are soluble in water, are not volatile, and when distilled give sulphurous anhydride (whilst the hydroxyl previously in combination with the sulphurous anhydride remains in the hydrocarbon group; thus phenol, C_{6}H_{5}.OH, is obtained from benzenesulphonic acid), and they are very energetic, because the hydrogen acting in them is of the same nature as in sulphuric acid itself.[60] [59] For example, the action of hot sulphuric acid on nitrogenous compounds, as applied in Kjeldahl's method for the estimation of nitrogen (Volume I. p. 249). It is obvious that when sulphuric acid acts as an oxidising agent it forms sulphurous anhydride. The action of sulphuric acid on the alcohols is exactly similar to its action on alkalis, because the alcohols, like alkalis, react on acids; a molecule of alcohol with a molecule of sulphuric acid separates water and forms an _acid_ ethereal salt--that is there is produced an ethereal compound corresponding with acid salts. Thus, for example, the action of sulphuric acid, H_{2}SO_{4}, on ordinary alcohol, C_{2}H_{5}OH, gives water and sulphovinic acid, C_{2}H_{5}HSO_{4}--that is, sulphuric acid in which one atom of hydrogen is replaced by the radicle C_{2}H_{5} of ethyl alcohol, SO_{2}(OH)(OC_{2}H_{5}), or, what is the same thing, the hydrogen in alcohol is replaced by the radicle (sulphoxyl) of sulphuric acid, C_{2}H_{5}O.SO_{2}(OH). [60] We will mention the following difference between the sulphonic acids and the ethereal acid sulphates (Note 59): the former re-form sulphuric acid with difficulty and the latter easily. Thus sulphovinic acid when heated with an excess of water is reconverted into alcohol and sulphuric acid. This is explained in the following manner. Both these classes of acids are produced by the substitution of hydrogen by SO_{3}H, or the univalent radicle of sulphuric acid, but in the formation of ethereal acid sulphates the SO_{3}H replaces the hydrogen of the hydroxyl in the alcohol, whilst in the formation of the sulphonic acids the SO_{3}H replaces the hydrogen of a hydrocarbon. This difference is clearly evidenced in the existence of two acids of the composition SO_{4}C_{2}H_{6}. The one, mentioned above, is sulphovinic acid or alcohol, C_{2}H_{5}.OH, in which the hydrogen of the hydroxyl is replaced by sulphoxyl = C_{2}H_{5}.OSO_{3}H, whilst the other is alcohol, in which one atom of the hydrogen in ethyl, C_{2}H_{5}, is replaced by the sulphonic group--that is = (C_{2}H_{4})SO_{3}H·OH. The latter is called isethionic acid. It is more stable than sulphovinic acid. The details as to these interesting compounds must be looked for in works on organic chemistry, but I think it necessary to note one of the general methods of formation of these acids. The sulphites of the alkalis--for example, K_{2}SO_{3}--when heated with the halogen products of metalepsis, give a halogen salt and a salt of a sulphonic acid. Thus methyl iodide, CH_{3}I, derived from marsh gas, CH_{4}, when heated to 100° with a solution of potassium sulphite, K_{2}SO_{3}, gives potassium iodide, KI, and potassium methylsulphonate, CH_{3}SO_{3}K--that is a salt of the sulphonic acid. This shows that the sulphonic acid may be referred to sulphurous acid, and that there is a resemblance between sulphuric and sulphurous acid, which clearly reveals itself here in the formation of one product from them both. Sulphuric acid, as containing a large proportion of oxygen, is a substance which frequently acts as an oxidising agent: in which case it is _deoxidised, forming sulphurous anhydride_ and water (or even, although more rarely, sulphuretted hydrogen and sulphur). Sulphuric acid acts in this manner on charcoal, copper, mercury, silver, organic and other substances, which are unable to evolve hydrogen from it directly, as we saw in describing sulphurous anhydride. Although the hydrate of a higher saline form of oxidation (Chapter XV.), sulphuric anhydride is capable of further oxidation, and forms a kind of peroxide, just as hydrogen gives hydrogen peroxide in addition to water, or as sodium and potassium, besides the oxides Na_{2}O and K_{2}O, give their peroxides, compounds which are in a chemical sense unstable, powerfully oxidising, and not directly able to enter into saline combinations. If the oxides of potassium, barium, &c., be compared to water, then their peroxides must in like manner correspond to hydrogen peroxide,[61] not only because the oxygen contained in them is very mobile and easily liberated, and because their reactions are similar, but also because they can be mutually transformed into each other, and are able to form compounds with each other, with bases and with water, and indeed form a kind of peroxide salts.[62] This is also the character of _persulphuric acid_, discovered in 1878 by Berthelot, and its corresponding anhydride or peroxide of sulphur S_{2}O_{7}. It is formed from 2SO_{3} + O with the absorption of heat (-27 thousand heat units), like ozone from O_{2} + O (-29 thousand units of heat), or hydrogen peroxide from H_{2}O + O (-21 thousand heat units). [61] The reaction BaO + O develops 12,000 heat units, whilst the reaction H_{2}O + O absorbs 21,000 heat units. [62] Schöne obtained a compound of peroxide of barium with peroxide of hydrogen. If barium peroxide be dissolved in hydrochloric (or acetic) acid, or if a solution of hydrogen peroxide be diluted with a solution of barium hydroxide, a pure hydrate is precipitated having the composition BaO_{2},8H_{2}O (sometimes the composition is taken as BaO_{2},6H_{2}O). This fact was already known to Thénard. Schöne showed that if hydrogen peroxide be in excess, a crystalline compound of the two peroxides, BaO_{2}H_{2}O_{2}, is precipitated. Schöne also obtained small well-formed crystals of the same composition by adding a solution of ammonia to an acid solution of barium peroxide (containing a barium salt and hydrogen peroxide or a compound of BaO_{2} with the acid). Thus barium peroxide combines with both water and hydrogen peroxide. This is a very important fact for the comprehension of the composition of other peroxides. Moreover, if the peroxides are able to give hydrates they can also form corresponding salts, _i.e._ they can combine with bases and acids, as was afterwards found to be the case on further research into this subject. Peroxide of sulphur is produced by the action of a silent discharge upon a mixture of oxygen and sulphurous anhydride.[63] With water S_{2}O_{7} gives persulphuric acid, H_{2}S_{2}O_{8}. The latter is obtained more simply by mixing strong sulphuric acid (not weaker than H_{2}SO_{4},2H_{2}O) directly with hydrogen peroxide, or by the action of a galvanic current on sulphuric acid mixed with a certain amount of water, and cooled, the electrodes being platinum wires, when persulphuric acid naturally appears at the positive pole.[64] When an acid of the strength H_{2}SO_{4},6H_{2}O is taken, at first the hydrate of the sulphuric peroxide, S_{2}O_{7},H_{2}O only is formed; but when the concentration about the positive pole reaches H_{2}SO_{4},3H_{2}O, a mixture of hydrogen peroxide and the hydrate of sulphuric peroxide begins to be formed. Dilute solutions of sulphuric peroxide can be kept better than more concentrated solutions, but the latter may be obtained containing as much as 123 grams of the peroxide to a litre. It is a very instructive fact that hydrogen peroxide is always formed when strong solutions of persulphuric acid break up on keeping. So that the bond between the two peroxides is established both by analysis and synthesis: hydrogen peroxide is able to produce S_{2}H_{2}O_{8}, and the latter to produce hydrogen peroxide. A mixture of sulphuric peroxide with sulphuric acid or water is immediately decomposed, with the evolution of oxygen, either when heated or under the action of spongy platinum. The same thing takes place with a solution of baryta, although at first no precipitate is formed and the decomposition of the barium salt, BaS_{2}O_{8}, with the formation of BaSO_{4}, only proceeds slowly, so that the solution may be filtered (the barium salt of persulphuric acid is soluble in water). Mercury, ferrous oxide, and the stannous salts, are oxidised by S_{2}H_{2}O_{8}. These are all distinct signs of true peroxides. The same common properties (capacity for oxidising, property of forming peroxide of hydrogen, &c.) are possessed by the alkali salts of persulphuric acid, which are obtained by the action of an electric current upon certain sulphates, for instance ammonium or potassium sulphate. The ammonium salt of persulphuric acid, (NH_{4})_{2}S_{2}O_{8}, is especially easily formed by this means, and is now prepared on a large scale and used (like Na_{2}O_{2} and H_{2}O_{2}) for bleaching tissues and fibres.[65] [63] Anhydrous _sulphuric peroxide_, S_{2}O_{7}, is obtained by the prolonged (8 to 10 hours) action of a silent discharge of considerable intensity on a mixture of oxygen and sulphurous anhydride; the vapour of sulphuric peroxide, S_{2}O_{7}, condenses as liquid drops, or after being cooled to 0° in the form of long prismatic crystals, resembling those of sulphuric anhydride. The anhydrous compound S_{2}O_{7} (and also the hydrated compound) cannot be preserved long, as it splits up into oxygen and sulphuric anhydride. Direct experiment shows that a mixture of equal volumes of sulphurous anhydride and oxygen leaves a residue of a quarter of the oxygen taken, or half of the whole volume, which indicates the formula S_{2}O_{7}. This substance is soluble in water, and it then gives a hydrate, probably having the composition S_{2}O_{7},H_{2}O = 2SHO_{4}. This solution oxidises the salts SnX_{2}, potassium iodide, and others, which renders it possible to prove that the solution actually contains one atom of oxygen capable of effecting oxidation to two molecules of sulphuric anhydride. In order to fully demonstrate the reality of a peroxide form for acids, it should be mentioned that some years ago Brodie obtained the so-called _acetic peroxide_, (C_{2}H_{2}O)_{2}O_{2}, by the action of barium peroxide on acetic anhydride, (C_{2}H_{3}O)_{2}O. Its corresponding hydrate is also known. This shows that true peroxides and their hydrates, with reactions similar to those of hydrogen peroxide, are possible for acids. A similar higher oxide has long been known for chromium, and Berthelot obtained a like compound for nitric acid (Chapter VI., Note 26). [64] When an acid of the strength H_{2}SO_{4}6H_{2}O is taken, at first only the hydrate of the sulphuric peroxide, S_{2}O_{7}H_{2}O, is formed, but when the concentration at the positive pole reaches H_{2}SO_{4}3H_{2}O, a mixture of hydrogen peroxide and the hydrate of sulphuric peroxide begins to be formed. A state of equilibrium is ultimately arrived at when the amounts of these substances correspond to the proportion S_{2}O_{7} : 2H_{2}O_{2}, which, as it were, answers to a new hydrate, S_{2}O_{9}2H_{2}O. But its existence cannot be admitted because the sulphuric peroxide can be easily distinguished from the hydrogen peroxide in the solution owing to the fact that the former does not act on an acid solution of potassium permanganate, whilst the hydrogen peroxide disengages both its own oxygen and that of the permanganic acid, converting it into manganous oxide. Their common property of liberating iodine from an acid solution of the potassium iodide enables the sum of the active oxygen in them both to be determined. [65] If a solution of sulphuric acid which has been first subjected to electrolysis be neutralised with potash or baryta, the salt which is formed begins to decompose rapidly with the evolution of oxygen (Berthelot, 1890). On saturating with caustic baryta, the solution of the salt formed may be separated from the sulphate of barium, and then the composition of the resultant compound, BaS_{2}O_{8}, may be determined from the amount of oxygen disengaged. Marshall (1891) studied the formation of this class of compounds more fully; he subjected a saturated solution of bisulphate of potassium to electrolysis with a current of 3-3-1/2 ampères; before electrolysis dilute sulphuric acid is added to the liquid surrounding the negative pole, and during electrolysis the solution at the anode is cooled. The electrolysis is continued without interruption for two days, and a white crystalline deposit separates at the anode. To avoid decomposition, the latter is not filtered through paper, but through a perforated platinum plate, and dried on a porous tile. The mother liquor, with the addition of a fresh solution of bisulphate of potassium, is again subjected to electrolysis and the crystals formed at the anode are again collected, &c. The salt so obtained may be recrystallised by dissolving it in hot water and rapidly cooling the solution after filtration; a small proportion of the salt is decomposed by this treatment. Rapid cooling is followed by the formation of small columnar crystals; slow cooling gives large prismatic crystals. The composition of the salt is determined either by igniting it, when it forms sulphate of potassium, or else by titrating the active oxygen with permanganate: its composition was found to correspond to the salt of persulphuric acid, K_{2}S_{2}O_{8}. The solution of the salt has a neutral reaction, and does not give a precipitate with salts of other metals. K_{2}S_{2}O_{8} is the most insoluble of the salts of persulphuric acid. With nitrate of silver it forms persulphate of silver, which gives peroxide of silver under the action of water according to the equation Ag_{2}S_{2}O_{8} + 2H_{2}O = Ag_{2}O_{2} + 2H_{2}SO_{4}. With an alkaline solution of a cupric salt (Fehling's solution) it forms a red precipitate of peroxide of copper. Manganese and cobalt salts give precipitates of MnO_{2} and Co_{2}O_{3}. Ferrous salts are rapidly oxidised, potassium iodide slowly disengages iodine at the ordinary temperature. All these reactions indicate the powerful oxidising properties of K_{2}S_{2}O_{8}. In oxidising in the presence of water it gives a residue of KHSO_{4}. The decomposition of the dry salt begins at 100° but is not complete even at 250°. The freshly prepared salt is inodorous, but after being kept in a closed vessel it evolves a peculiar smell different from that of ozone. The ammonium salt of persulphuric acid, (NH_{4})_{2}S_{2}O_{8}, is obtained in a similar manner. It is soluble to the extent of 58 parts per 100 parts by weight of water. The decomposition of the ammonium salt by the hydrated oxide of barium gives the barium salt, BaS_{2}O_{8}4H_{2}O, which is soluble to the extent of 52·2 parts in 100 parts of water at 0°. The crystals do not deliquesce in the air and decompose in the course of several days; they decompose most rapidly in perfectly dry air. Solutions of the pure salt decompose slowly at the ordinary temperature; on boiling barium sulphate is gradually precipitated, oxygen being liberated simultaneously. To completely decompose this salt it is necessary to boil its solution for a long time. Alcohol dissolves the solid salt; the anhydrous salt does not separate from the alcoholic solution, but a hydrate containing one molecule of water, BaS_{2}O_{8}H_{2}O, which is soluble in water but insoluble in absolute alcohol. Solid barium persulphate decomposes even when slightly heated. The free acid, which may serve for the preparation of other salts, is obtained by treating the barium salt with sulphuric acid. The lead salt, PbS_{2}O_{8}, has been obtained from the free acid; it crystallises with two or three molecules of water. It is soluble in water, deliquesces in the air, and with alkalis gives a precipitate of the hydrated oxide which rapidly oxidises into the binoxide. Traube, before Marshall's researches, thought that the electrolysis of solutions of sulphuric acid did not give persulphuric acid but a persulphuric oxide having the composition SO_{4}. On repeating his former researches (1892) Traube obtained a persulphuric oxide by the electrolysis of a 70 per cent. solution of sulphuric acid, and he separated it from the solution by means of barium phosphate. Analysis showed that this substance corresponded to the above composition SO_{4}, and therefore Traube considers it very likely that the salts obtained by Marshall corresponded to an acid H_{2}SO_{4} + SO_{4}, _i.e._ that the indifferent oxide, SO_{4}, can combine with sulphuric acid and form peculiar saline compounds. In order to understand the relation of sulphuric peroxide to sulphuric acid we must first remark that hydrogen peroxide is to be considered, in accordance with the law of substitution, as water, H(OH), in which H is replaced by (OH). Now the relation of H_{2}S_{2}O_{8} to H_{2}SO_{4} is exactly similar. The radicle of sulphuric acid, equivalent to hydrogen, is HSO_{4};[65 bis] it corresponds with the (OH) of water, and therefore sulphuric acid, H(SHO_{4}), gives (SHO_{4})_{2} or S_{2}H_{2}O_{8}, in exactly the same manner as water gives (HO)_{2}--_i.e._ H_{2}O_{2}.[66] [65 bis] Or one of those supposed ions which appear at the positive pole in the decomposition of sulphuric acid by the action of a galvanic current. [66] If this be true one would expect the following peroxide hydrates: for phosphoric acid, (H_{2}PO_{4})_{2} = H_{4}P_{2}O_{8} = 2H_{2}O + 2PO_{3}; for carbonic acid, (HCO_{3})_{2} = H_{2}C_{2}O_{6} = H_{2}O + C_{2}O_{5}; and for lead the true peroxide will be also Pb_{2}O_{5}, &c. Judging from the example of barium peroxide (Note 62), these peroxide forms will probably combine together. It seems to me that the compounds obtained by Fairley for uranium are very instructive as elucidating the peroxides. In the action of hydrogen peroxide in an acid solution on uranium oxide, UO_{3}, there is formed a uranium peroxide, UO_{4},4H_{2}O (U = 240), but hydrogen peroxide acts on uranium oxide in the presence of caustic soda; on the addition of alcohol a crystalline compound containing Na_{4}UO_{8},4H_{2}O is precipitated, which is doubtless a compound of the peroxides of sodium, Na_{2}O_{2}, and uranium, UO_{4}. It is very possible that the first peroxide, UO_{4},4H_{2}O, contains the elements of hydrogen peroxide and uranium peroxide, U_{2}O_{7}, or even U(OH)_{6},H_{2}O_{2}, just as the peroxide form lately discovered by Spring for tin perhaps contains Sn_{2}O_{3},H_{2}O_{2}. The largest part _of the sulphuric acid made_ is used for reacting on sodium chloride in the manufacture of sodium carbonate; for the manufacture of the volatile acids, like nitric, hydrochloric, &c., from their corresponding salts; for the preparation of ammonium sulphate, alums, vitriols (copper and iron), artificial manures, superphosphate (Chapter XIX., Note 18) and other salts of sulphuric acid; in the treatment of bone ash for the preparation of phosphorus, and for the solution of metals--for example, of silver in its separation from gold--for cleaning metals from rust, &c. A large amount of oil of vitriol is also used in treatment of organic substances; it is used for the extraction of stearin, or stearic acid, from tallow, for refining petroleum and various vegetable oils, in the preparation of nitro-glycerine (Chapter VI., Notes 37 and 37 bis), for dissolving indigo and other colouring matters, for the conversion of paper into vegetable parchment, for the preparation of ether from alcohol, for the preparation of various artificial scents from fusel oil, for the preparation of vegetable acids, such as oxalic, tartaric, citric, for the conversion of non-fermentable starchy substances into fermentable glucose, and in a number of other processes. It would be difficult to find another artificially-prepared substance which is so frequently applied in the arts as sulphuric acid. Where there are not works for its manufacture, the economical production of many other substances of great technical importance is impossible. In those localities which have arrived at a high technical activity the amount of sulphuric acid consumed is proportionally large; sulphuric acid, sodium carbonate, and lime are the most important of the artificially-prepared agents employed in factories. Besides the normal acids of sulphur, H_{2}SO_{3}, H_{2}SO_{3}S, and H_{2}SO_{4}, corresponding with sulphuretted hydrogen, H_{2}S, in the same way that the oxy-acids of chlorine correspond with hydrochloric acid, HCl, there exists a peculiar series of acids which are termed _thionic acids_. Their general composition is S_{_n_}H_{2}O_{6}, where _n_ varies from 2 to 5. If _n_ = 2, the acid is called dithionic acid. The others are distinguished as trithionic, tetrathionic, and pentathionic acids. Their composition, existence, and reactions are very easily understood if they be referred to the class of the sulphonic acids--that is, if their relation to sulphuric acid be expressed in just the same manner as the relation of the organic acids to carbonic acid. The organic acids, as we saw (Chapter IX.), proceed from the hydrocarbons by the substitution of their hydrogen by carboxyl--that is, by the radicle of carbonic acid, CH_{2}O_{3} - HO = CHO_{2}. The formation of the acids of sulphur by means of sulphoxyl may be represented in the same manner, HSO_{3} = H_{2}SO_{4} - HO. Therefore to hydrogen H_{2}, there should correspond the acids H.SHO_{3}, sulphurous, and SHO_{3}.SHO_{3} = S_{2}H_{2}O_{6}, or dithionic; to SH_{2} there should correspond the acids SH(SHO_{3}) = H_{2}S_{2}O_{3} (thiosulphuric), and S(SHO_{3})_{2} = H_{2}S_{3}O_{6} (trithionic); to S_{2}H_{2} the acids S_{2}H(SHO_{3}) = H_{2}S_{3}O_{2} (unknown), and S_{2}(SHO_{3})_{2} = H_{2}S_{4}O_{6} (tetrathionic); to S_{3}H_{2} the acids S_{3}H(SHO_{3}) and S_{3}(SHO_{3})_{2} = H_{2}S_{5}O_{6} (pentathionic). We know that iodine reacts directly with the hydrogen of sulphuretted hydrogen and combines with it, and if thiosulphuric acid contains the radicle of sulphuretted hydrogen (or hydrogen united with sulphur) of the same nature as in sulphuretted hydrogen, it is not surprising that iodine reacts with sodium thiosulphate and forms sodium tetrathionate. Thus, thiosulphuric acid, HS(SHO_{3}), when deprived of H, gives a radicle which immediately combines with another similar radicle, forming the tetrathionate S_{2}(SO_{2}HO)_{2}. On this view[67] of the structure of the thionic acids and salts, it is also clear how all the thionic acids, like thiosulphuric acid, easily give sulphur and sulphides, with the exception only of dithionic acid, H_{2}S_{2}O_{6}, which, judging from the above, stands apart from the series of the other thionic acids. Dithionic acid stands in the same relation to sulphuric acid as oxalic acid does to carbonic acid. Oxalic acid is dicarboxyl, (CHO_{2})_{2} = C_{2}H_{2}O_{4}, and so also dithionic acid is disulphoxyl, (SHO_{3})_{2} = S_{2}H_{2}O_{6}. Oxalic acid when ignited decomposes into carbonic anhydride and carbonic oxide, CO, and dithionic acid when heated decomposes into sulphuric anhydride and sulphurous anhydride, SO_{2}, and SO_{2} stands in the same relation to SO_{3} as CO to CO_{2}. This also explains the peculiarity of the calcium, barium, and lead, &c. salts of the thionic acids being easily soluble (although the corresponding salts of H_{2}SO_{3}, H_{2}SO_{4}, and H_{2}S dissolve with difficulty), because the former are similar to the salts of the sulphonic acids, which are also soluble in water. Thus the thionic acids are _disulphonic acids_, just as many dicarboxylic acids are known--for example, CH_{2}(CO_{2}H)_{2}, C_{6}H_{4}(CO_{2}H)_{2}.[68] [67] This view was communicated by me in 1870 to the Russian Chemical Society. [68] _Dithionic acid_, H_{2}S_{2}O_{6}, is distinguished among the thionic acids as containing the least proportion of sulphur. It is also called hyposulphuric acid, because its supposed anhydride, S_{2}O_{5}, contains more O than sulphurous oxide, SO_{2} or S_{2}O_{4}, and less than sulphuric anhydride, SO_{3} or S_{2}O_{6}. Dithionic acid, discovered by Gay-Lussac and Welter, is known as a hydrate and as salts, but not as anhydride. The method for preparing dithionic acid usually employed is by the action of finely-powdered manganese dioxide on a solution of sulphurous anhydride. On shaking, the smell of the latter disappears, and the manganese salt of the acid in question passes into solution; MnO_{2} + 2SO_{2} = MnS_{2}O_{6}. If the temperature be raised, the dithionate splits up into sulphurous anhydride and manganese sulphate, MnSO_{4}. Generally owing to this a mixture of manganese sulphate and dithionate is obtained in the solution. They may be separated by mixing the solution of the manganese salts with a solution of barium hydroxide, when a precipitate of manganese hydroxide and barium sulphate is obtained. In this manner barium dithionate only is obtained in solution. It is purified by crystallisation, and separates as BaS_{2}O_{6},2H_{2}O; this is then dissolved in water, and decomposed with the requisite amount of sulphuric acid. Dithionic acid, H_{2}S_{2}O_{6}, then remains in solution. By concentrating the resultant solution under the receiver of an air-pump it is possible to obtain a liquid of sp. gr. 1·347, but it still contains water, and on further evaporation the acid decomposes into sulphuric acid and sulphurous anhydride: H_{2}S_{2}O_{6} = H_{2}SO_{4} + SO_{2}. The same decomposition takes place if the solution be slightly heated. Like all the thionic acids, dithionic acid is readily attacked by oxidising agents, and passes into sulphurous acid. No dithionate is able to withstand the action of heat, even when very slight, without giving off sulphurous anhydride: K_{2}S_{2}O_{6} = K_{2}SO_{4} + SO_{2}. The alkali dithionates have a neutral reaction (which indicates the energetic nature of the acid) are soluble in water, and in this respect present a certain resemblance to the salts of nitric acid (their anhydrides are: N_{2}O_{5} and S_{2}O_{5}). Klüss (1888) described many of the salts of dithionic acid. Langlois, about 1840, obtained a peculiar thionic acid by heating a strong solution of acid potassium sulphite with flowers of sulphur to about 60°, until the disappearance of the yellow coloration first produced by the solution of the sulphur. On cooling, a portion of the sulphur was precipitated, and crystals of a salt of _trithionic acid_, K_{2}S_{3}O_{6} (partly mixed with potassium sulphate), separated out. Plessy afterwards showed that the action of sulphurous acid on a thiosulphate also gives sulphur and trithionic acid: 2K_{2}S_{2}O_{3} + 3SO_{2} = 2K_{2}S_{3}O_{6} + S. A mixture of potassium acid sulphite and thiosulphate also gives a trithionate. It is very possible that a reaction of the same kind occurs in the formation of trithionic acid by Langloid's method, because potassium sulphite and sulphur yield potassium thiosulphate. The potassium thiosulphate may also be replaced by potassium sulphide, and on passing sulphurous anhydride through the solution thiosulphate is first formed and then trithionate: 4KHSO_{3} + K_{2}S + 4SO_{2} = 3K_{2}S_{3}O_{6} + 2H_{2}O. The sodium salt is not formed under the same circumstances as the corresponding potassium salt. The sodium salt does not crystallise and is very unstable: the barium salt is, however, more stable. The barium and potassium salts are anhydrous, they give neutral solutions and decompose when ignited, with the evolution of sulphur and sulphurous anhydride, a sulphate being left behind, K_{2}S_{3}O_{6} = K_{2}SO_{4} + SO_{2} + S. If a solution of the potassium salt be decomposed by means of hydrofluosilicic or chloric acid, the insoluble salts of these acids are precipitated and trithionic acid is obtained in solution, which however very easily breaks up on concentration. The addition of salts of copper, mercury, silver, &c., to a solution of a trithionate is followed, either immediately or after a certain time, by the formation of a black precipitate of the sulphides whose formation is due to the decomposition of the trithionic acid with the transference of its sulphur to the metal. _Tetrathionic acid_, H_{2}S_{4}O_{6}, in contradistinction to the preceding acids, is much more stable in the free state than in the form of salts. In the latter form it is easily converted into trithionate, with liberation of sulphur. Sodium tetrathionate was obtained by Fordos and Gélis, by the action of iodine on a solution of sodium thiosulphate. The reaction essentially consists in the iodine taking up half the sodium of the thiosulphate, inasmuch as the latter contains Na_{2}S_{2}O_{3}, whilst the tetrathionate contains NaS_{2}O_{3} or Na_{2}S_{4}O_{6}, so that the reaction is as follows: 2Na_{2}S_{2}O_{3} + I_{2} = 2NaI + Na_{2}S_{4}O_{6}. It is evident that tetrathionic acid stands to thiosulphuric acid in exactly the same relation as dithionic acid does to sulphurous acid; for the same amount of the other elements in dithionate, KSO_{3}, and tetrathionate, KS_{2}O_{3}, there is half as much metal as in sulphite, K_{2}SO_{3}, and thiosulphate, K_{2}S_{2}O_{3}. If in the above reaction the sodium thiosulphate be replaced by the lead salt PbS_{2}O_{3}, the sparingly-soluble lead iodide PbI_{2} and the soluble salt PbS_{4}O_{6} are obtained. Moreover the lead salt easily gives tetrathionic acid itself (PbSO_{4} is precipitated). The solution of tetrathionic acid may be evaporated over a water-bath, and afterwards in a vacuum, when it gives a colourless liquid, which has no smell and a very acid reaction. When dilute it may be heated to its boiling-point, but in a concentrated form it decomposes into sulphuric acid, sulphurous anhydride, and sulphur: H_{2}S_{4}O_{6} = H_{2}SO_{4} + SO_{2} + S_{2}. _Pentathionic acid_, H_{2}S_{5}O_{6}, also belongs to this series of acids. But little is known concerning it, either as hydrate or in salts. It is formed, together with tetrathionic acid, by the direct action of sulphurous acid on sulphuretted hydrogen in an aqueous solution; a large proportion of sulphur being precipitated at the same time: 5SO_{2} + 5H_{2}S = H_{2}S_{5}O_{6} + 5S + 4H_{2}O. If, as was shown above, the thionic acids are disulphonic acids, they may be obtained, like other sulphonic acids, by means of potassium sulphite and sulphur chloride. Thus Spring demonstrated the formation of potassium trithionate by the action of sulphur dichloride on a strong solution of potassium sulphite: 2KSO_{3}K + SCl_{2} = S(SO_{3}K)_{2} + 2KCl. If sulphur chloride be taken, sulphur also is precipitated. The same trithionate is formed by heating a solution of double thiosulphates; for example, of AgKS_{2}O_{3}. Two molecules of the salts then form silver sulphide and potassium trithionate. If the thiosulphate be the potassium silver salt SO_{3}K(AgS), then the structure of the trithionate must necessarily be (SO_{3}K)_{2}S. Previous to Spring's researches, the action of iodine on sodium thiosulphate was an isolated accidentally discovered reaction; he, however, showed its general significance by testing the action of iodine on mixtures of different sulphur compounds. Thus with iodine, I_{2}, the mixture Na_{2}S + Na_{2}SO_{3} forms 2NaI + Na_{2}S_{2}O_{3}, whilst the mixture Na_{2}S_{2}O_{3} + Na_{2}SO_{3} + I_{2} gives 2NaI + Na_{2}S_{3}O_{6}--that is, trithionic acid stands in the same relation to thiosulphuric acid as the latter does to sulphuretted hydrogen. We adopt the same mode of representation: by replacing one hydrogen in H_{2}S by sulphuryl we obtain thiosulphuric acid, HSO_{3}.HS, and by replacing a second hydrogen in the latter again by sulphuryl we obtain trithionic acid, (HSO_{3})_{2}S. Furthermore, Spring showed that the action of sodium amalgam on the thionic acids causes reverse reactions to those above indicated for iodine. Thus sodium thiosulphate with Na_{2} gives Na_{2}S + Na_{2}SO_{3}, and Spring showed that the sodium here is not a simple element taking up sulphur, but itself enters into double decomposition, replacing sulphur; for on taking a potassium salt and acting on it with sodium, KSO_{3}(SK) + NaNa = KSO_{3}Na + (SK)Na. In a similar way sodium dithionate with sodium gives sodium sulphite: (NaSO_{3})_{2} + Na_{2} = 2NaSO_{3}Na; sodium trithionate forms NaSO_{3}Na and NaSO_{3}.SNa, and tetrathionate forms sodium thiosulphate, (NaSO_{3})S_{2}(NaSO_{3}) + Na_{2} = 2(NaSO_{3})(NaS). In all the oxidised compounds of sulphur we may note the presence of the elements of sulphurous anhydride, SO_{2}, the only product of the combustion of sulphur, and in this sense the compounds of sulphur containing one SO_{2} are-- H HO C_{6}H_{5} HS SO_{2} SO_{2} SO_{2} SO_{2} HO HO HO HO Sulphurous Sulphuric Benzene sulphonic Thiosulphuric acid acid acid acid while, according to this mode of representation, the thionic acids are-- HO HO HO HO SO_{2} SO_{2} SO_{2} SO_{2} S S_{2} S_{3} SO_{2} SO_{2} SO_{2} SO_{2} HO HO HO HO Dithionic Trithionic Tetrathionic Pentathionic Hence it is evident that SO_{2} has (whilst CO_{2} has not) the faculty for combination, and aims at forming SO_{2}X_{2}. These X_{2} can = O, and the question naturally suggests itself as to whether the O_{2} which occurs in SO_{2} is not of the same nature as this oxygen which adds itself to SO_{2}--that is, whether SO_{2} does not correspond with the more general type SX_{4}, and its compounds with the type SX_{6}? To this we may answer 'Yes' and 'No'--'Yes' in the general sense which proceeds from the investigation of the majority of compounds, especially metals, where RO corresponds with RCl_{2}, RX_{2}; 'No' in the sense that sulphur does not give either SH_{4}, SH_{6}, or SCl_{6}, and therefore the stages SX_{4} and SX_{6} are only observable in oxygen compounds. With reference to the type SX_{6} a hydrate, S(HO)_{6}, might be expected, if not SCl_{6}. And we must recognise this hydrate from a study of the compounds of sulphuric acid with water. In addition to what has been already said respecting the complex acids formed by sulphur, I think it well to mention that, according to the above view, still more complex oxygen acids and salts of sulphur may be looked for. For instance, the salt Na_{2}S_{4}O_{8} obtained by Villiers (1888) is of this kind. It is formed together with sodium trithionate and sulphur, when SO_{2} is passed through a cold solution of Na_{2}S_{2}O_{3}, which is then allowed to stand for several days at the ordinary temperature: 2Na_{2}S_{2}O_{3} + 4SO_{2} = Na_{2}S_{4}O_{8} + Na_{2}S_{3}O_{6} + S. It may be assumed here, as in the thionic acids, that there are two sulphoxyls, bound together not only by S, but also by SO_{2}, or what is almost the same thing, that the sulphoxyl is combined with the residue of trithionic acid, _i.e._ replaces one aqueous residue in trithionic acid. Sulphur exhibits an acid character, not only in its compounds with hydrogen and oxygen, but also in those with other elements. The compound of sulphur and carbon has been particularly well investigated. It presents a great analogy to carbonic anhydride, both in its elementary composition and chemical character. This substance is the so-called carbon bisulphide, CS_{2}, and corresponds with CO_{2}. The first endeavours to obtain a compound of sulphur with carbon were unsuccessful, for although sulphur does combine directly with carbon, yet the formation of this compound requires distinctly definite conditions. If sulphur be mixed with charcoal and heated, it is simply driven off from the latter, and not the smallest trace of carbon bisulphide is obtained. The formation of this compound requires that the charcoal should be first heated to a red heat, but not above, and then either the vapour of sulphur passed over it or lumps of sulphur thrown on to the red-hot charcoal, but in small quantities, so as not to lower the temperature of the latter. If the charcoal be heated to a white heat, the amount of carbon bisulphide formed is less. This depends, in the first place, on the carbon bisulphide dissociating at a high temperature.[69] In the second place, Favre and Silberman showed that in the combustion of one gram of carbon bisulphide (the products will be CO_{2} + 2SO_{2}) 3,400 heat units are evolved--that is, the combustion of a molecular quantity of carbon bisulphide evolves 258,400 heat units (according to Berthelot, 246,000). From a molecule of carbon bisulphide in grams we may obtain 12 grams of carbon, whose combustion evolves 96,000 heat units, and 64 grams of sulphur, evolving by combustion (into SO_{2}) 140,800 heat units. Hence we see that the component elements separately evolve less heat by their combustion (237,000 heat units) than carbon bisulphide itself--that is, that heat should be evolved (at the ordinary temperature) and not absorbed in its decomposition, and therefore that the formation of carbon bisulphide from charcoal and sulphur is in all probability accompanied by an absorption of heat.[70] It is therefore not surprising that, like other compounds produced with an absorption of heat (ozone, nitrous oxide, hydrogen peroxide, &c.), carbon bisulphide is unstable and easily converted into the original substances from which it is obtained. And indeed if the vapour of carbon bisulphide be passed through a red-hot tube, it is decomposed--that is, it dissociates--into sulphur and carbon. And this takes place at the temperature at which this substance is formed, just as water decomposes into hydrogen and oxygen at the temperature of its formation. In this absorption of heat in the formation of carbon bisulphide is explained the facility with which it suffers reactions of decomposition, which we shall see in the sequel, and its main difference from the closely analogous carbonic anhydride. [Illustration: FIG. 90.--Apparatus for the manufacture of carbon bisulphide. [69] Even light decomposes carbon bisulphide, but not to the extent of separating carbon; under the action of the sun's rays it is decomposed into sulphur and solid substance which is considered to be carbon monosulphide; it is of a red colour, and its sp. gr. is 1·66. (The formation of a red liquid compound C_{3}S_{2} has also been remarked.) Thorpe (1889) observed a complete decomposition of carbon bisulphide under the action of a liquid alloy of potassium and sodium; it is accompanied by an explosion and the deposition of carbon and sulphur. A similar complete decomposition of carbon bisulphide is also accomplished by the action of mercury fulminate (Chapter XVI., Note 26), and is due to the fact that _at the ordinary temperature_ (at which carbon bisulphide is not produced) _the decomposition_ of carbon bisulphide takes place with the development of heat--that is, it presents an exothermal reaction, like the decomposition of all explosives. It is very possible that at a higher temperature, when carbon bisulphide is formed, the _combination_ of carbon with sulphur is also an exothermal reaction--that is, heat is developed. If this should be the case, carbon bisulphide would present a most instructive example in thermochemistry. [70] The fact should not be lost sight of that sulphur and charcoal are solids at the ordinary temperature, whilst carbon bisulphide is a very volatile liquid, and consequently, in the act of combination, referred to the ordinary temperature (Note 69), there is, as it were, a passage into a liquid state, and this requires the absorption of heat. And furthermore, the molecule of sulphur contains at least six atoms, and the molecule of carbon in all probability (Chapter VIII.) a very considerable number of atoms; thus the reaction of sulphur on charcoal may be expressed in the following manner: 3C_{_n_} + _n_S_{6} = 3_n_CS_{2}--that is, from _n_ + 3 molecules there proceed 3_n_ molecules, and as _n_ must be very considerable, 3_n_ must be greater than 3 + _n_, which indicates a decomposition in the formation of carbon bisulphide, although the reaction at first sight appears as one of combination. This decomposition is seen also from the volumes in the solid and liquid states. Carbon bisulphide has a sp. gr. of 1·29; hence its molecular volume is 59. But the volume of carbon, even in the form of charcoal, is not more than 6, and the volume of S_{2} is 30; hence 36 volumes after combination give 59 volumes--an expansion takes place, as in decompositions. In the laboratory carbon bisulphide is prepared as follows: A porcelain tube is luted into a furnace in an inclined position, the upper extremity of the tube being closed by a cork, and the lower end connected with a condenser. The tube contains charcoal, which is raised to a red heat, and then pieces of sulphur are placed in the upper end. The sulphur melts, and its vapour comes into contact with the red-hot charcoal, when combination takes place; the vapours condense in the condenser, carbon bisulphide being a liquid boiling at 48°. On a large scale the apparatus depicted in fig. 90 is employed. A cast-iron cylinder rests on a stand in a furnace. Wood charcoal is charged into the cylinder through the upper tube closed by a clay stopper, whilst the sulphur is introduced through a tube reaching to the bottom of the cylinder. Pieces of sulphur thrown into this tube fall on to the bottom of the cylinder, and are converted into vapour, which passes through the entire layer of charcoal in the cylinder. The vapour of carbon bisulphide thus formed passes through the exit tube first into a Woulfe's bottle (where the sulphur which has not entered into the reaction is condensed), and then into a strongly-cooled condenser or worm.[71] [71] Carbon bisulphide, as prepared on a large scale, is generally very impure, and contains not only sulphur, but, more especially, other impurities which give it a very disagreeable odour. The best method of purifying this malodorous carbon bisulphide is to shake it up with a certain amount of mercuric chloride, or even simply with mercury, until the surface of the metal ceases to turn black. After this the carbon bisulphide must be poured off and distilled over a water-bath, after mixing with some oil to retain the impurities. Pure carbon bisulphide is a colourless liquid, which refracts light strongly, and has a pure ethereal smell; at 0° its specific gravity is 1·293, and at 15° 1·271. If kept for a long time it seems to undergo a change, especially when it is kept under water, in which it is insoluble. It boils at 48°, and the tension of its vapour is so great that it evaporates very easily, producing cold,[72] and therefore it has to be kept in well-stoppered vessels; it is generally kept under a layer of water, which hinders its evaporation and does not dissolve it.[73] [72] If carbon bisulphide be evaporated under the receiver of an air-pump, or by means of a current of air, it is possible to obtain a temperature as low as -60°, and the carbon bisulphide does not solidify at this temperature. However, if a series of air-bubbles be passed through it by means of bellows, a crystalline white substance remains which volatilises below 0°: this a hydrate, H_{2}O,2CS_{2}; it easily decomposes into water and carbon bisulphide. It is formed in the above experiment by the moisture held in the air passed through the carbon bisulphide, and the fall of temperature. [73] Strong alcohol is miscible in all proportions with carbon bisulphide, but dilute alcohol only in a definite amount, owing to its diminished solubility from the presence of the water in it. Ether, hydrocarbons, fatty oils, and many other organic substances are soluble with great ease in carbon bisulphide. This is taken advantage of in practice for extracting the fatty oils from vegetable seeds, such as linseed, palm-nuts, or from bones, &c. The preparation of vegetable oils is usually done by pressing the seeds under a press, but the residue always contains a certain amount of oil. These traces of oil can, however, be removed by treatment with carbon bisulphide. In this manner a solution is obtained which when heated easily parts with all the carbon bisulphide, leaving the non-volatile fatty oil behind, so that the same carbon bisulphide may be condensed and used over again for the same purpose. It also dissolves iodine, bromine, indiarubber, sulphur, and tars. Carbon bisulphide, especially at high temperatures, very often acts by its elements in a manner in which carbon and sulphur alone are not able to react, which will be understood from what has been said above respecting its endothermal origin. If it be passed over red-hot metals--even over copper, for instance, not to mention sodium, &c.--it forms a sulphide of the metal and deposits charcoal, and if the vapour be passed over incandescent metallic oxides it forms metallic sulphides and carbonic anhydride (and sometimes a certain amount of sulphurous anhydride). Lime and similar oxides give under these circumstances a carbonate and a sulphide--for example, CS_{2} +3CaO = 2CaS + CaCO_{3}. The sulphides obtained by this means are often well crystallised, like those found in nature--for example, lead and antimony sulphides. Carbon bisulphide enters into many combinations, which are frequently closely analogous to the compounds of carbonic anhydride. In this respect it is a _thio-anhydride_--_i.e._ it has the character of the acid anhydrides,[73 bis] like carbonic anhydride, with the difference that the oxygen of the latter is replaced by sulphur. By thio-compounds in general are understood those compounds of sulphur which differ from the compounds of oxygen as carbon bisulphide does from carbonic anhydride--that is, which correspond with the oxygen compounds, but with substitution of sulphur for oxygen. Thus thiosulphuric acid is monothiosulphuric acid--that is, sulphuric acid in which one atom of sulphur replaces one atom of oxygen. With the sulphides of the alkalis and alkaline earths, it forms saline substances corresponding with the carbonates, and these compounds may be termed _thiocarbonates_. For example, the composition of the sodium salt Na_{2}CS_{3} is exactly like that of sodium carbonate. They are formed by the direct solution of carbon bisulphide in aqueous solutions of the sulphides; but they are difficult to obtain in a crystalline form, because they are easily decomposable. When the solutions of these salts are highly concentrated they begin to decompose, with the evolution of sulphuretted hydrogen and the formation of a carbonate, water taking part in the reaction--for example, K_{2}CS_{3} + 3H_{2}O = K_{2}CO_{3} + 3H_{2}S.[74] [73 bis] And just as COCl_{2} corresponds to CO_{2}, so also the chloranhydride, CSCl_{2}, or _thiophosgene_, corresponds to CS_{2}. [74] If instead of a sulphide we take an alkali hydroxide, a thiocarbonate is also formed, together with a carbonate--thus, 3BaH_{2}O_{2} + 3CS_{2} = 2BaCS_{3} + BaCO_{3} + 3H_{2}O. From the instability of the thiocarbonates of the alkaline metals we can clearly see the reason of the difficulty with which the salts of the heavier metals are formed, whose basic properties are incomparably weaker than those of the alkali metals. However, these salts may be obtained by double decomposition. Ammonia in reacting on carbon bisulphide gives, besides products like those formed by other alkalis, a whole series of products of as complex a structure as those substances which are produced by the action of carbonic anhydride on ammonia. In the ninth chapter we examined the formation of the ammonium carbonates, and saw the transition from them into the cyanides. It is not surprising after this that the action of carbon bisulphide on ammonia not only produces the above-mentioned salts, but also amidic compounds corresponding with them, in which the oxygen is wholly or partially replaced by sulphur. Thus ammonium dithiocarbamate is very easily obtained if carbon bisulphide be added to an alcoholic solution of ammonia, and the mixture cooled in a closed vessel. The salt then separates out in minute yellow crystals, CN_{2}H_{6}S_{2}. Carbon bisulphide not only forms compounds with the metallic sulphides, but also with sulphuretted hydrogen--that is, it forms _thiocarbonic acid_, H_{2}CS_{3}. This is obtained by carefully mixing solutions of thiocarbonates with dilute hydrochloric acid. It then separates in an oily layer, which easily decomposes in the presence of water into sulphuretted hydrogen and carbon bisulphide, just as the corresponding carbonic acid (hydrate) decomposes into water and carbonic anhydride. Carbon bisulphide combines not only with sodium sulphide, but also with the bisulphide, Na_{2}S_{2}, not, however, with the trisulphide, Na_{2}S_{3}. The relation of carbon bisulphide to the other carbon compounds presents many most interesting features which are considered in organic chemistry. We will here only turn our attention to one of the compounds of this class. Ethyl sulphide, (C_{2}H_{5})_{2}S, combines with ethyl iodide, C_{2}H_{5}I, forming a new molecule, S(C_{2}H_{5})_{3}I. If we designate the hydrocarbon group, for instance ethyl, C_{2}H_{5}, by Et, the reaction would be expressed by the following equation : Et_{2}S + EtI = SEt_{3}I. This compound is of a saline character, corresponds with salts of the alkalis, and is closely analogous to ammonium chloride. It is soluble in water; when heated it again splits up into its components EtI and Et_{2}S, and with silver hydroxide gives a hydroxide, Et_{3}S·OH, having the property of a distinct and energetic alkali, resembling caustic ammonia. Thus the compound group SEt_{3} combines, like potassium or ammonium, with iodine, hydroxyl, chlorine, &c. The hydroxide SEt_{3}·OH is soluble in water, precipitates metallic salts, saturates acids, &c. Hence sulphur here enters into a relation towards other elements similar to that of nitrogen in ammonia and ammonium salts, with only this difference, that nitrogen retains, besides iodine, hydroxyl, and other groups, also H_{4} or Et_{4} (for example, NH_{4}Cl, NEt_{3}HI, NEt_{4}I), whilst sulphur only retains Et_{3}. Compounds of the formula SH_{3}X are however unknown, only the products of substitution SEt_{3}X, &c. are known. The distinctly alkaline properties of the hydroxide, triethylsulphine hydroxide, SEt_{3}OH, and also the sharply-defined properties of the corresponding hydroxide, tetraethylammonium hydroxide, NEt_{4}OH, depend naturally not only on the properties of the nitrogen and sulphur entering into their composition, but also on the large proportion of hydrocarbon groups they contain. Judging from the existence of the ethylsulphine compounds, it might be imagined that sulphur forms a compound, SH_{4}, with hydrogen; but no such compound is known, just as NH_{5} is unknown, although NH_{4}Cl exists. A remarkable example[74 bis] of the thio-compounds is found in _thiocyanic acid_--_i.e._ cyanic acid in which the oxygen is replaced by sulphur, HCNS. We know (Chapter IX.) that with oxygen the cyanides of the alkaline metals RCN give cyanates RCNO; but they also combine with sulphur, and therefore if yellow prussiate of potash be treated as in the preparation of potassium cyanide, and sulphur be added to the mass, potassium thiocyanate, KNCS, is obtained in solution. This salt is much more stable than potassium cyanate; it dissolves without change in water and alcohol, forming colourless solutions from which it easily crystallises on evaporation. It may be kept exposed to air even when in solution; in dissolving in water it absorbs a considerable amount of heat, and forms a starting-point for the preparation of all the thiocyanates, RCNS, and organic compounds in which the metals are replaced by hydrocarbon groups. Such, for example, is volatile mustard oil, C_{3}H_{5}CSN (allyl thiocyanate),[75] which gives to mustard its caustic properties. With ferric salts the thiocyanates give an exceedingly brilliant red coloration, which serves for detecting the smallest traces of ferric salts in solution. Thiocyanic acid, HCNS, may be obtained by a method of double decomposition, by distilling potassium thiocyanate with dilute sulphuric acid. It is a volatile colourless liquid, having a smell recalling that of vinegar, is soluble in water, and may be kept in solution without change.[75 bis] [74 bis] Thorpe and Rodger (1889), by heating a mixture of lead fluoride and phosphorus pentasulphide to 250° in an atmosphere of dry nitrogen, obtained gaseous _phosphorus fluosulphide_, or _thiophosphoryl fluoride_, PSF_{3}, corresponding with POCl_{3}. This colourless gas is converted into a colourless liquid by a pressure of eleven atmospheres; it does not act on dry mercury, and takes fire spontaneously in air or oxygen, forming phosphorus pentafluoride, phosphoric anhydride, and sulphurous anhydride. It is soluble in ether, but is decomposed by water: PSF_{3} + 4H_{2}O = H_{2}S + H_{3}PO_{4} + 3HF (Note 20). [75] Although mustard oil may be obtained from the thiocyanates, it is only an isomer of allyl thiocyanate proper, as is explained in Organic Chemistry. [75 bis] Sulphur can only replace half the oxygen in CO_{2}, as is seen in _carbon oxysulphide_, or monothiocarbonic anhydride COS. This substance was obtained by Than, and is formed in many reactions. A certain amount is obtained if a mixture of carbonic oxide and the vapour of sulphur be passed through a red-hot tube. When carbon tetrachloride is heated with sulphurous anhydride, this substance is also formed; but it is best obtained in a pure form by decomposing potassium thiocyanate with a mixture of equal volumes of water and sulphuric acid. A gas is then evolved containing a certain amount of hydrocyanic acid, from which it may be freed by passing it over wool containing moistened mercuric oxide, which retains the hydrocyanic acid. The reaction is expressed by the equation: 2KCNS + 2H_{2}SO_{4} + 2H_{2}O = K_{2}SO_{4} + (NH_{4})_{2}SO_{4} + 2COS. It is also formed by passing the vapour of carbon bisulphide over alumina or clay heated to redness (Gautier; silicon sulphide is then formed). COS is also formed by passing phosgene over a long layer of asbestos mixed with cadmium sulphide at 270°; CdS + COCl_{3} = CdCl_{2} + COS (Nuricsán, 1892). The pure gas has an aromatic odour, is soluble in an equal volume of water, which, however, acts on it, so that it must be collected over mercury. When slightly heated, carbon oxysulphide decomposes into sulphur and carbonic oxide. It burns in air with a pale blue flame, explodes with oxygen, and yields potassium sulphide and carbonate with potassium hydroxide: COS + 4KHO = K_{2}CO_{3} + K_{2}S + 2H_{2}O. The sulphur compounds of chlorine Cl_{2}S and Cl_{2}S_{2} may be regarded on the one hand as products of the metalepsis of the sulphides of hydrogen, H_{2}S and H_{2}S_{2}; and on the other hand of the oxygen compounds of chlorine, because chloride of sulphur, Cl_{2}S, resembles chlorine oxide, Cl_{2}O, whilst Cl_{2}S_{2} corresponds with the higher oxide of chlorine; or thirdly, we may see in these compounds the type of the acid chloranhydrides, because they are all decomposed by water, forming hydrochloric acid, and sulphur tetrachloride, SCl_{4}, is decomposed with the formation of sulphurous anhydride.[76] [76] There is no reason for seeing any contradiction or mutual incompatibility in these three views, because every analogy is more or less modified by a change of elements. Thus, for instance, it cannot be expected that the product of the metalepsis of hydrogen sulphide would resemble the corresponding products of water in all respects, because water has not the acid properties of hydrogen sulphide. In the days of dualism and electrical polarity it was supposed that the sulphur varied in its nature: in hydrogen sulphide or potassium sulphide it was considered to be negative, and in sulphurous anhydride or sulphur dichloride positive. It then appeared evident that sulphur dichloride would have no point of analogy with potassium sulphide. But metalepsis, or its expression in the law of substitution, necessitates such opinions being laid aside. If we can compare CO_{2}, CH_{4}, CCl_{4}, CHCl_{3}, CH_{3}(OH) with each other, we cannot recognise any difference in the sulphur in SH_{2}, SCl_{2}, SK_{2}, or in general SX_{2}, for otherwise we should have to acknowledge as many different states of sulphur, carbon, or hydrogen as there are compounds of sulphur, carbon, or hydrogen. The essential truth of the matter is that all the elements in a molecule play their part in the reactions into which it enters. Often this appears to be contradicted in the result--for example, hydrogen alone may be replaced; but it is not this hydrogen alone that has determined the reaction; all the elements present have participated in it. This may be made clearer by the following rough illustration. Supposing two regiments of soldiers were fighting against each other, and that several men were lost by one of the regiments; no one could say that it was only these men who took part in the engagement. The other men fired and the bullets flew over the heads of their opponents. It was not only those who fell who fought, although they only were removed from the field of battle; the fighting proceeded among the masses, but only those few were disabled who went forward and were more conspicuous &c.; not that the remainder did not take part in the action; they also fought and were an object of attack, only they remained sound and unhurt. Hydrogen is lighter than other elements and its atoms more mobile; it subjects itself more frequently and easily to reactions; but it is not it alone which reacts, it is even less liable to attack than other elements. It participates in exceedingly diverse reactions, not indeed because the hydrogen itself varies, but because one atom of it puts itself forward, another is hidden, one is united with carbon, another feebly held by sulphur, one stands or moves in the neighbourhood of oxygen, another is joined to a hydrocarbon. All hydrogen atoms are equal, and equally serve as an object of attack for the atoms of molecules encountering them, but those only are removed from the sphere of action which are nearer the surface of a molecule, which are more mobile, or held by a less sum of forces. So also sulphur is one and the same in sulphur dichloride, in sulphurous or sulphuric anhydride, in hydrogen sulphide, in potassium sulphide, but it reacts differently, and those elements which are with it also vary in their reactions because they are with it, and it varies its reactions because it is with them. It is possible to seize on a character common to substances quantitatively and qualitatively analogous to each other. It may be admitted that an element in certain forms is not able to enter into reactions into which in other forms it enters willingly, if only the requisite conditions are encountered; but it must not therefore be concluded that an element changes its essential quality in these different cases. The preceding remarks touch on questions which are subject to much argument among chemists, and I mention them here in order to show the treatment of those most important problems of chemistry which lie at the basis of this treatise. [Illustration: FIG. 91.--Apparatus for the preparation of sulphur chloride, and similar volatile compounds prepared by combustion in a stream of chlorine.] The compounds of sulphur with chlorine are prepared in the apparatus depicted in fig. 91. As sulphur chloride is decomposed by water, the chlorine evolved in the flask C must be dried before coming into contact with the sulphur. It is therefore first passed through a Woulfe's bottle, B, containing sulphuric acid, and then through the cylinder D containing pumice stone moistened with sulphuric acid, and then led into the retort E, in which the sulphur is heated. The compound which is formed distils over into the receiver R. A certain amount of sulphur passes over with the sulphur chloride, but if the resultant distillate be re-saturated with chlorine and distilled no free sulphur remains, the boiling-point rises to 144°, and pure sulphur chloride, S_{2}Cl_{2}, is obtained. It has this formula because its vapour density referred to hydrogen is 68. It is also obtained by heating certain metallic chlorides (stannous, mercuric) with sulphur; both the metal and chlorine then combine with the sulphur. Sulphur chloride is a yellowish-brown liquid, which boils at 144°, and has a specific gravity of 1·70 at 0°. It fumes strongly in the air, reacting on the moisture contained therein, and has a heavy chloranhydrous odour. It dissolves sulphur, is miscible with carbon bisulphide, and falls to the bottom of a vessel containing water, by which it is decomposed, forming sulphurous anhydride and hydrochloric acid; but it first forms various lower stages of oxidation of sulphur, because the addition of silver nitrate to the solution gives a black precipitate. With hydrogen sulphide it gives sulphur and hydrochloric acid, and it reacts directly with metals--especially arsenic, antimony, and tin--forming sulphides and chlorides. In the cold, it absorbs chlorine and gives _sulphur dichloride_, SCl_{2}. The entire conversion into this substance requires the prolonged passage of dry chlorine through sulphur chloride surrounded by a freezing mixture. The distillation of the dichloride must be conducted in a stream of chlorine, as otherwise it partially decomposes into sulphur chloride and chlorine. Pure sulphur dichloride is a reddish-brown liquid, which resembles the lower chloride in many respects; its specific gravity is 1·62; its odour is more suffocating than that of sulphur chloride; it volatilises at 64°.[77] [77] The observed vapour density of sulphur dichloride referred to hydrogen is 53·3, and that given by the formula is 51·5. The smaller molecular weight explains its boiling point being lower than that of sulphur chloride, S_{2}Cl_{2}. The reactions of both these compounds are very similar. Sulphur converts the dichloride, SCl_{2}, into the monochloride, S_{2}Cl_{2}. In one point the dichloride differs distinctly from the monochloride--that is, in its capacity for easily giving up chlorine and decomposing. Even light decomposes it into chlorine and the monochloride. Hence it acts on many substances in the same manner as chlorine, or substances which easily part with the latter, such as phosphoric or antimonic chloride. In distinction to these, however, sulphur dichloride would appear to distil without any considerable decomposition, judging by the vapour density. But this is not a valid conclusion, for if there be a decomposition, then 2SCl_{2} = S_{2}Cl_{2} + Cl_{2}; now the density of sulphur chloride = 67·5, and of chlorine = 35·5, and consequently a mixture of equal volumes of the two = 51·5, just the same as an equal volume of sulphur dichloride. _Therefore the distillation of sulphur dichloride is probably nothing but its decomposition._ Hence the compound SCl_{2}, which is stable at the ordinary temperature, decomposes at 64°. In the cold it absorbs a further amount of chlorine, corresponding to SCl_{4}, but even at -10° a portion of the absorbed chlorine is given off--that is, dissociation takes place. Thus the tetrachloride is even less stable than the dichloride. _Thionyl chloride_, SOCl_{2}, may be regarded as oxidised sulphur dichloride; it corresponds with sulphur chloride, S_{2}Cl_{2}, in which one atom of sulphur is replaced by oxygen. At the same time it is chlorine oxide (hypochlorous anhydride, Cl_{2}O) combined with sulphur, and also the chloranhydride of sulphurous acid--that is, SO(HO)_{2}, in which the two hydroxyl groups are replaced by two atoms of chlorine, or sulphurous anhydride, SO_{2}, in which one atom of oxygen is replaced by two atoms of chlorine. All these representations are confirmed by reactions of formation, or decompositions; they all agree with our notions of the other compounds of sulphur, oxygen, and chlorine; hence these definitions are not contradictory to each other. Thus, for instance, thionyl chloride was first obtained by Schiff, by the action of dry sulphurous anhydride on phosphorus pentachloride. On distilling the resultant liquid, thionyl chloride comes over first at 80°, and on continuing the distillation phosphorus oxychloride distils over at above 100°, PCl_{5} + SO_{2} = POCl_{3} + SOCl_{2}. This mode of preparation is direct evidence of the oxychloride character of SOCl_{2}. Würtz obtained the same substance by passing a stream of chlorine oxide through a cold solution of sulphur in sulphur chloride; the chlorine oxide then combined directly with the sulphur, S + Cl_{2}O = SOCl_{2}, whilst the sulphur chloride remained unchanged (sulphur cannot be combined directly with chlorine oxide, as an explosion takes place). Thionyl chloride is a colourless liquid, with a suffocating acrid smell; it has a specific gravity at 0° of 1·675, and boils at 78°. It sinks in water, by which it is immediately decomposed, like all chloranhydrides--for example, like carbonyl chloride, which corresponds with it: SOCl_{2} + H_{2}O = SO_{2} + 2HCl.[77 bis] [77 bis] Hartog and Sims (1893) obtained thionyl bromide, SOBr_{2}, by treating SOCl_{2} with sodium bromide; it is a red liquid, sp. gr. 2·62, and decomposes at 150°. Normal _sulphuric acid has two corresponding chloranhydrides_; the first, SO_{2}(OH)Cl, is sulphuric acid, SO_{2}(HO)_{2}, in which one equivalent of HO is replaced by chlorine; the second has the composition SO_{2}Cl_{2}--that is, two HO groups are substituted by two of chlorine. The second chloranhydride, or the compound SO_{2}Cl_{2}, is called sulphuryl chloride, and the first chloranhydride, SO_{2}HOCl, may be called chlorosulphonic acid, because it is really an acid; it still retains one hydroxyl of sulphuric acid, and its corresponding salts are known. Thus, potassium chloride absorbs the vapour of sulphuric anhydride, forming a salt, SO_{3}KCl, corresponding with SO_{3}HCl as acid. In acting on sodium chloride it forms hydrochloric acid and the salt NaSO_{3}Cl. This first chloranhydride of sulphuric acid, SO_{2}HOCl, discovered by Williamson, is obtained either by the action of phosphorus pentachloride on sulphuric acid (PCl_{5} + H_{2}SO_{4} = POCl_{3} + HCl + HSO_{3}Cl), or directly by the action of dry hydrochloric acid on sulphuric anhydride, SO_{3} + HCl = HSO_{3}Cl. The most easy and rapid method of its formation is by direct saturation of cold Nordhausen acid with dry hydrochloric acid gas (SO_{3} + HCl = HSO_{3}Cl), and distillation of the resultant solution; the distillate then contains HSO_{3}Cl. It is a colourless fuming liquid, having an acrid odour; it boils at 153° (according to my determination, confirmed by Konovaloff), and its specific gravity at 19° is 1·776. It is immediately decomposed by water, forming hydrochloric and sulphuric acids, as should be the case with a true chloranhydride. In the reactions of this chloranhydride we find the easiest means of introducing the sulphonic group HSO_{3} into other compounds, because it is here combined with chlorine. The second chloranhydride of sulphuric acid, or _sulphuryl chloride_, SO_{2}Cl_{2}, was obtained by Regnault by the direct action of the sun's ray on a mixture of equal volumes of chlorine and sulphurous oxide. The gases gradually condense into a liquid, combining together as carbonic oxide does with chlorine. It is also obtained when a mixture of the two gases in acetic acid is allowed to stand for some time. The first chloranhydride, SO_{3}HCl, decomposes when heated at 200° in a closed tube into sulphuric acid and sulphuryl chloride. It boils at 70°, its specific gravity is 1·7, it gives hydrochloric and sulphuric acids with water, fumes in the air, and, judging by its vapour density, does not decompose when distilled.[78] [78] Pyrosulphuryl chloride, S_{2}O_{5}Cl_{2}. See Note 44. Thorpe and Kirman, by treating SO_{3} with HF, obtained SO_{2}(OH)F, as a liquid boiling at 163°, but which decomposed with greater facility and then gave SO_{2}F_{2}. The acids of sulphur naturally have their corresponding ammonium salts, and the latter their amides and nitriles. It will be readily understood how vast a field for research is presented by the series of compounds of sulphur and nitrogen, if we only remember that to carbonic and formic acids there corresponds, as we saw (Chapter IX.), a vast series of derivatives corresponding with their ammonium salts. To sulphuric acid there correspond two ammonium salts, SO_{2}(HO)(NH_{4}O) and SO_{2}(NH_{4}O)_{2}; three amides: the acid amide SO_{2}(HO)(NH_{2}), or sulphamic acid, the normal saline compound SO_{2}(NH_{4}O)(NH_{2}), or ammonium sulphamate, and the normal amide SO_{2}(NH_{2})_{2}, or sulphamide (the analogue of urea); then the acid nitrile, SON(HO), and two neutral nitriles, SON(NH_{2}) and SN_{2}. There are similar compounds corresponding with sulphurous acid, and therefore its nitriles will be, an acid, SN(HO), its salt, and the normal compound, SN(NH_{2}). Dithionic and the other acids of sulphur should also have their corresponding amides and nitriles. Only a few examples are known, which we will briefly describe. Sulphuric acid forms salts of very great stability with ammonia, and ammonium sulphate is one of the commonest ammoniacal compounds. It is obtained by the direct action of ammonia on sulphuric acid, or by the action of the latter on ammonium carbonate; it separates from its solutions in an anhydrous state, like potassium sulphate, with which it is isomorphous. Hence, the composition of crystals of ammonium sulphate is (NH_{4})_{2}SO_{4}. This salt fuses at 140°, and does not undergo any change when heated up to 180°. At higher temperatures it does not lose water, but parts with half its ammonia, and is converted into the acid salt, HNH_{4}SO_{4}; and this acid salt, on further heating, undergoes a further decomposition, and splits up into nitrogen, water, and acid ammonium sulphite, HNH_{4}SO_{3}. At the ordinary temperature the normal salt is soluble in twice its weight of water and at the boiling-point of water in an equal weight. In its faculty for combinations this salt exhibits a great resemblance to potassium sulphate, and, like it, easily forms a number of double salts; the most remarkable of which are the ammonia alums, NH_{4}AlS_{2}O_{8},12H_{2}O, and the double salts formed by the metals of the magnesium group, having, for example, the composition (NH_{4})_{2}MgS_{2}O_{8},6H_{2}O. Ammonium sulphate does not give an amide when heated, perhaps owing to the faculty of sulphuric anhydride to retain the water combined with it with great force. But the amides of sulphuric acid may be very conveniently prepared from sulphuric anhydride. Their formation by this method is very easily understood because an amide is equal to an ammonium salt less water, and if the anhydride be taken it will give an amide directly with ammonia. Thus, if dry ammonia be passed into a vessel surrounded by a freezing mixture and containing sulphuric anhydride, it forms a white powdery mass called sulphatammon, having the composition SO_{3},2H_{3}N, and resembling the similar compound of carbonic acid, CO_{2},2NH_{3}. This substance is naturally the ammonium salt of sulphamic acid, SO_{2}(NH_{4}O)NH_{2}. It is slowly acted on by water, and may therefore be obtained in solution, in which it slowly reacts with barium chloride, which proves that with water it still forms ammonium sulphate. If this substance be carefully dissolved in water and evaporated, it yields well-formed crystals, whose solution no longer gives a precipitate with barium chloride. This is not due to the presence of impurities, but to a change in the nature of the substance, and therefore Rose calls the crystalline modification _parasulphatammon_. Platinum chloride only precipitates half the nitrogen as platinochloride from solutions of sulphat- and parasulphatammon, which shows that they are ammonium salts, SO_{2}(NH_{4}O)(NH_{2}). It may be that the reason of the difference in the two modifications is connected with the fact that two different substances of the composition N_{2}H_{4}SO_{2} are possible: one is the amide SO_{2}(NH_{2})_{2} corresponding with the normal salt, and the other is the salt of the nitrile acid corresponding with acid ammonium sulphate--that is, SON(ONH_{4}) corresponds with the acid SON(OH) = SO_{2}(NH_{4}O)OH - 2H_{2}O. Hence there may here be a difference of the same nature as between urea and ammonium cyanate. Up to the present, the isomerism indicated above has been but little investigated, and might be the subject of interesting researches. If in the preceding experiment the ammonia, and not the sulphuric anhydride, be taken in excess, a soluble substance of the composition 2SO_{2},3NH_{3} is formed. This compound, obtained by Jacqueline and investigated by Voronin, doubtless also contains a salt of sulphamic acid--that is, of the amide corresponding with the acid ammonium sulphate = HNH_{4}SO_{4} - H_{2}O = (NH_{2})SO_{2}(OH). Probably it is a compound of sulphatammon with sulphamic acid. Thus it has an acid reaction, and does not give a precipitate with barium chloride. With normal sulphate of ammonium, an amide of the composition N_{2}H_{4}SO_{2} should correspond, which should bear the same relation to sulphuric acid as urea bears to carbonic acid. This amide, known as _sulphamide_, is obtained by the action of dry ammonia on the sulphuryl chloride, SO_{2}Cl_{2}, just as urea is obtained by the action of ammonia on carbonyl chloride, SO_{2}Cl_{2} + 4NH_{3} = N_{2}H_{4}SO_{2} + 2NH_{4}Cl. The ammonium chloride is separated from the resultant sulphamide with great difficulty. Cold water, acting on the mixture, dissolves them both; the cold solution does not gives precipitate with barium chloride. Alkalis act on it slowly, as they do on urea; but on boiling, especially in the presence of alkalis or acids, it easily recombines with water, and gives an ammonium salt. V. Traube (1892) obtained sulphamide by the reaction of sulphuryl, dissolved in chloroform, upon ammonia. The resultant precipitate dissolves when shaken up with water, and the solution (after boiling with the oxides or lead or silver) is evaporated, when a syrupy liquid remains. With nitrate of silver the latter gives a solid compound, which, when decomposed by hydrochloric acid, gives free sulphamide in large colourless crystals, having the composition SO_{2}(NH_{2})_{2}. This substance fuses at 81°, begins to decompose below 100°, and is entirely decomposed above 250°; it is soluble in water, and the solution has a neutral reaction and bitter taste. When heated with acids, sulphamide gradually decomposes, forming sulphuric acid and ammonia. If the silver compound obtained by the action of sulphamide on nitrate of silver be heated at 170°-180° until ammonia is no longer evolved, and the residue be extracted with water acidulated with nitric acid, a salt separates out from the solution, answering in its composition to sulphamide, SO_{2}NAg, which = the amide - NH_{3} = SO_{2}N_{2}H_{4} - NH_{3} = SO_{2}NH. The action of sulphuryl chloride (and of the other chloranhydrides of sulphur) on ammonium carbonate always, as Mente showed (1888), results in the formation of the salt NH(SO_{3}NH_{4})_{2}. The nitriles corresponding with sulphuric acid are not as yet known with any certainty. The most simple nitrile corresponding with sulphuric acid should have the composition N_{2}H_{8}SO_{4} - 4H_{2}O = N_{2}S. This would be a kind of cyanogen corresponding with sulphuric acid. On comparing sulphurous acid with carbonic acid, we saw that they present a great analogy in many respects, and therefore it might be expected that nitrile compounds having the composition NHS and N_{2}S_{2} would be found. The latter of these compounds is well known, and was obtained by Soubeiron, by the action of dry ammonia on sulphur chloride. This substance corresponds with cyanogen (paracyanogen), and is known as _nitrogen sulphide_, N_{2}S_{2}. It is formed according to the equation 3SCl_{2} + 8NH_{3} = N_{2}S_{2} + S + 6NH_{4}Cl. The free sulphur and nitrogen sulphide are dissolved by acting on the product with carbon bisulphide, the nitrogen sulphide being much less soluble than the sulphur. It is a yellow substance, which is excessively irritating to the eyes and nostrils. It explodes when rubbed with a hard substance, being naturally decomposed with the evolution of nitrogen; but when heated it fuses without decomposing, and only decomposes with explosion at 157°. It is insoluble in water, and only slightly so in alcohol, ether, and carbon bisulphide; 100 parts of the latter dissolve 1·5 part of nitrogen sulphide at the boiling point. This solution on cooling deposits it in minute transparent prisms of a golden yellow colour. In the group of the halogens we saw four closely analogous elements--fluorine, chlorine, bromine, and iodine--and we meet with the same number of closely allied analogues in the oxygen group; for besides sulphur this group also includes _selenium_ and _tellurium_: O, S, Se, Te. These two groups are very closely allied, both in respect to the magnitudes of their atomic weights and also in the faculty of the elements of both groups for combining with metals. The distinct analogy and definite degree of variance known to us for the halogens, also repeat themselves in the same degree for the elements of the oxygen group. Amongst the halogens fluorine has many peculiarities compared to Cl, Br and I which are more closely analogous, whilst oxygen differs in many respects from S, Se, Te, which possess greater similarities. The analogy in a quantitative respect is perfect in both cases. Thus the halogens combine with H, and the elements of the oxygen group with H_{2}, forming H_{2}O, H_{2}S, H_{2}Se, H_{2}Te. The hydrogen compounds of selenium and tellurium are acids like hydrogen sulphide. Selenium, by simple heating in a stream of hydrogen, partially combines with it directly, but seleniuretted hydrogen is more readily decomposable by heat than sulphuretted hydrogen, and this property is still more developed in telluretted hydrogen. Hydrogen selenide and telluride are gases like sulphuretted hydrogen, and, like it, are soluble in water, form saline compounds with alkalis, precipitate metallic salts, are obtained by the action of acids on their compounds with metals, &c. Selenium and tellurium, like sulphur, give two normal grades of combination with oxygen, both of an acid character, of which only the forms corresponding to sulphurous anhydride--namely, selenious anhydride, SeO_{2}, and tellurous anhydride, TeO_{2}[79]--are formed directly. These are both solids, obtained by the combustion of the elements themselves and by the action of oxidising agents on them. They form feebly energetic acids, having distinct bibasic properties; however, a characteristic difference from SO_{2} is observable both in the physical properties of these compounds and in their stability and capacity for further oxidation, just as in the series of the halogens already known to us, only in an inverse order; in the latter we saw that iodine combines more easily than bromine or chlorine with oxygen, forming more stable oxygen compounds, whereas here, on the contrary, sulphurous anhydride, as we know, is difficultly decomposed, parts with its sulphur with difficulty, and is easily oxidised and especially in its salts, while selenious and tellurous anhydrides are oxidised with difficulty and easily reduced, even by means of sulphurous acid. [79] _Selenious anhydride_, SeO_{2}, is a volatile solid, which crystallises in prisms soluble in water. It is best procured by the action of nitric acid on selenium. The well-known researches of Nilson (1874) showed that the salts of selenious acid easily form acid salts, and are so characteristic in many respects that they may even serve for judging the analogy of types of oxides. Thus the oxides of the composition RO give normal salts of the composition RSeO_{3},2H_{2}O, where R = Mn, Co, Ni, Cu, Zn. The salts of magnesium, barium, and calcium contain a different quantity of water, as do also the salts of the oxides R_{2}O_{3}. We here turn attention to the fact that beryllium gives a normal salt, BeSeO_{3},2H_{2}O, and not a salt analogous to those of aluminium, scandium, Sc_{2}(SeO_{3})_{3},H_{2}O, yttrium, Y_{2}(SeO_{3})_{2},12H_{2}O, and other oxides of the form R_{2}O_{3}, which speaks in favour of the formula BeO. _Tellurous anhydride_ is also a colourless solid, which crystallises in octahedra; it also, when heated, first fuses and then volatilises. It is insoluble in water, and the decomposition of its salts gives a hydrate, H_{2}TeO_{3}, which is insoluble. It is a very characteristic circumstance that selenious and tellurous anhydrides are very easily _reduced_ to selenium and tellurium. This is not only effected by metals like zinc, or by sulphuretted hydrogen, which are powerful deoxidisers, but even by sulphurous anhydride, which is able to precipitate selenium and tellurium from solutions of the selenites and tellurites, and even of the acids themselves, which is taken advantage of in obtaining these elements and separating them from sulphur. Sulphuric acid, as we know, rarely acts as an oxidising agent. It is otherwise with selenic and telluric acids, H_{2}SeO_{4} and H_{2}TeO_{4}, which are powerful oxidising agents--that is, are easily reduced in many circumstances either into the lower oxide or even to selenium and tellurium. A powerful oxidising agent is required in order to convert selenious and tellurous anhydrides into selenic and telluric anhydrides, and, moreover, it must be employed in excess. If chlorine be passed through a solution of potassium selenide, K_{2}Se, telluride, K_{2}Te, selenite, K_{2}SeO_{3}, or tellurite, K_{2}TeO_{3}, it acts as an oxidiser in the presence of the water, forming potassium selenate, K_{2}SeO_{4}, or tellurate, K_{2}TeO_{4}. The same salts are formed by fusing the lower oxides with nitre. These salts are isomorphous with the corresponding sulphates, and cannot therefore be separated from them by crystallisation. The salts of potassium, sodium, magnesium, copper, cadmium, &c. are soluble like the sulphates, but those of barium and calcium are insoluble, in perfect analogy with the sulphates. When copper selenate, CuSeO_{4}, is treated with sulphuretted hydrogen (CuS is precipitated), _selenic acid_ remains in solution. On evaporation and drying in vacuo at 180° it gives a syrupy liquid, which may be concentrated to almost the pure acid, H_{2}SeO_{4}, having a specific gravity of 2·6. Cameron and Macallan (1891) showed that pure H_{2}SeO_{4} only remains liquid in a state of superfusion whilst the solidified acid melts at +58°, the solid acid crystallises well, its sp. gr. is then 2·95. The hydrate H_{2}SeO_{4},H_{2}O melts at +25°. The acid in a superfused state has a sp. gr. 2·36 and the solid 2·63. Like sulphuric acid strong selenic acid attracts moisture from the atmosphere; it is not decomposed by sulphurous acid, but oxidises hydrochloric acid (like nitric, chromic, and manganic acids), evolving chlorine and forming selenious acid, H_{2}SeO_{4} + 2HCl = H_{2}SeO_{3} + H_{2}O + Cl_{2}. _Telluric acid_, H_{2}TeO_{4}, is obtained by fusing tellurous anhydride with potassium hydroxide and chlorate; the solution, containing potassium tellurate, is then precipitated with barium chloride, and the barium tellurate, BaTeO_{4} obtained in the precipitate is decomposed by sulphuric acid. A solution of telluric acid is thus obtained, which on evaporation yields colourless prisms, soluble in water, and containing TeH_{2}O_{4},2H_{2}O. Two equivalents of water are driven off at 160°; on further heating the last equivalent of water is expelled, and then oxygen is given off. It also gives chlorine with hydrochloric acid, like selenic acid. Its salts also correspond with those of sulphuric acid. It must, however, be remarked that telluric and selenic acids are able to give poly-acid salts with much greater ease than sulphuric acid. Thus, for example, there are known for telluric acid not only K_{2}TeO_{4},5H_{2}O and KHTeO_{4},3H_{2}O, but also KHTeO_{4},H_{2}TeO_{4},H_{2}O = K_{2}TeO_{4},3H_{2}TeO_{4},2H_{2}O. This salt is easily obtained from acid solutions of the preceding salts and is less soluble in water. As selenious anhydride is volatile and gives similar poly-salts, it may be surmised that selenious, tellurous, selenic, and telluric anhydrides are polymeric as compared with sulphurous and sulphuric anhydrides, for which reason it would be desirable to determine the vapour density of selenious anhydride. It would probably correspond with Se_{2}O_{4} or Se_{3}O_{6}. In order to show the very close analogy of selenium to sulphur, I will quote two examples. Potassium cyanide dissolves selenium, as it does sulphur, forming potassium selenocyanate, KCNSe, corresponding with potassium thiocyanate. Acids precipitate selenium from this solution, because selenocyanic acid, H_{2}CNSe, when in a free state is immediately decomposed. A boiling solution of sodium sulphite dissolves selenium, just as it would sulphur, forming a salt analogous to thiosulphate of sodium, namely, sodium selenosulphate, Na_{2}SSeO_{3}. Selenium is separated from a solution of this salt by the action of acid. _Selenium_ was obtained in 1817 by Berzelius from the sublimate which collects in the first chamber in the preparation of sulphuric acid from Fahlun pyrites. Certain other pyrites also contain small quantities of selenium. Some native selenides, especially those of lead, mercury, and copper, have been found in the Hartz Mountains, but only in small quantities. Pyrites and blendes, in which the sulphur is partially replaced by selenium, still remain the chief source for its extraction. When these pyrites are roasted they evolve selenious anhydride, which condenses in the cooler portions of the apparatus in which the pyrites are roasted, and is partially or wholly reduced by the sulphurous anhydride simultaneously formed. The presence of selenium in ores and sublimates is most simply tested by heating them before the blowpipe, when they evolve the characteristic odour of garlic. Selenium exhibits two modifications, like sulphur: one amorphous and insoluble in carbon bisulphide, the other crystalline and slightly soluble in carbon bisulphide (in 1,000 parts at 45° and 6,000 at 0°), and separating from its solutions in monoclinic prisms. If the red precipitate obtained by the action of sulphurous anhydride on selenious anhydride be dried, it gives a brown powder, having a specific gravity of 4·26, which when heated changes colour and fuses to a metallic mass, which gains lustre as it cools. The selenium acquires different properties according to the rate at which it is cooled from a fused state; if rapidly cooled, it remains amorphous and has the same specific gravity (4·28) as the powder, but if slowly cooled it becomes crystalline and opaque, soluble in carbon bisulphide, and has a specific gravity of 4·80. In this form it fuses at 214° and remains unchanged, whilst the amorphous form, especially above 80°, gradually passes into the crystalline variety. The transition is accompanied by the evolution of heat, as in the case of sulphur; thus the analogy between sulphur and selenium is clearly shown here. In the fused amorphous form selenium presents a brown mass, slightly translucent, with a vitreous fracture, whilst in the crystalline form it has the appearance of a grey metal, with a feeble lustre and a crystalline fracture.[79 bis] Selenium boils at 700°, forming a vapour whose density is only constant at a temperature of about 1,400°, when it is equal to 79·4 (referred to hydrogen)--that is, the molecular formula is then Se_{2}, like sulphur at an equally high temperature. [79 bis] Muthmann, in his researches upon the allotropic forms of selenium, pointed out (1889) a peculiar modification, which appears, as it were, as a transition between crystalline and amorphous selenium. It is obtained together with the crystalline variety by slowly evaporating a solution of selenium in bisulphide of carbon, and differs from the crystalline variety in the form of its crystals; it passes into the latter modification when heated. Schultz also obtained selenium (like Ag, _see_ Chapter XXIV.) in a soluble form, but these researches are not so conclusive as those upon soluble silver, and we shall therefore not consider them more fully. _Tellurium_ is met with still more rarely than selenium (it is known in Saxony) in combination with gold, silver, lead, and antimony in the so-called foliated tellurium ore. Bismuth telluride and silver telluride have been found in Hungary and in the Altai. Tellurium is extracted from bismuth telluride by mixing the finely-powdered ore with potassium and charcoal in as intimate a mixture as possible, and then heating in a covered crucible. Potassium telluride, K_{2}Te, is then formed, because the charcoal reduces potassium tellurite. As potassium telluride is soluble in water, forming a red-brown solution which is decomposed by the oxygen of the atmosphere (K_{2}Te + O + H_{2}O = 2KHO + Te), the mass formed in the crucible is treated with boiling water and filtered as rapidly as possible, and the resultant solution exposed to the air, by which means the tellurium is precipitated.[80] In a free state tellurium has a perfectly _metallic appearance_; it is of a silver-white colour, crystallises very easily in long brilliant needles; is very brittle, so that it can be easily reduced to powder; but it is a bad conductor of heat and electricity, and in this respect, as in many others, it forms a transition from the metals to the non-metals. Its specific gravity is 6·18, it melts at an incipient red heat, and takes fire when heated in air, like selenium and sulphur, burning with a blue flame, evolving white fumes of tellurous anhydride, TeO_{2}, and emitting an acrid smell if no selenium be present; but if it be, the odour of the latter preponderates. Alkalis dissolve tellurium when boiled with it, potassium telluride, K_{2}Te, and potassium tellurite, K_{2}TeO_{3}, being formed. The solution is of a red colour, owing to the presence of the telluride, K_{2}Te; but the colour disappears when the solution is cooled or diluted, the tellurium being all precipitated: 2K_{2}Te + K_{2}TeO_{3} + 3H_{2}O = 6KHO + 3Te.[81] [80] The tellurium thus prepared is impure, and contains a large amount of selenium. The latter may be removed by converting the mixture into the salts of potassium, and treating this with nitric acid and barium nitrate, when barium selenate only is precipitated, whilst the barium tellurate remains in solution. This method does not, however, give a pure product, and it appears to be best to separate the selenium from the tellurium in a metallic form; this is done by boiling the impure potassium tellurate with hydrochloric acid, which converts it into potassium tellurite, from which the tellurium is reduced by sulphurous anhydride. The metal thus obtained is then fused and distilled in a stream of hydrogen; the selenium volatilises first, and then the tellurium, owing to its being much less volatile than the former. Nevertheless, tellurium is also volatile, and may be separated in this manner from less volatile metals, such as antimony. Brauner determined the atomic weight of pure tellurium, and found it to be 125, but showed (1889) that tellurium purified by the usual method, even after distillation, contains a large amount of impurities. [81] The decomposition proceeds in the above order in the cold, but in a hot solution with an excess of potassium hydroxide it proceeds inversely. A similar phenomenon takes place when tellurium is fused with alkalis, and it is therefore necessary in order to obtain potassium telluride to add charcoal. Selenium and tellurium form higher compounds with chlorine with comparative ease. For selenium, SeCl_{2} and SeCl_{4} are known, and for tellurium TeCl_{2} and TeCl_{4}. The tetrachlorides of selenium and tellurium are formed by passing chlorine over these elements. Selenium tetrachloride, SeCl_{4}, is a crystalline, volatile mass which gives selenious anhydride and hydrochloric acid with water. Tellurium tetrachloride is much less volatile, fuses easily, and is also decomposed by water. Both elements form similar compounds with bromine. Tellurium tetrabromide is red, fuses to a brown liquid, volatilises, and gives a crystalline salt, K_{2}TeBr_{6},3H_{2}O, with an aqueous solution of potassium bromide. CHAPTER XXI CHROMIUM, MOLYBDENUM, TUNGSTEN, URANIUM, AND MANGANESE Sulphur, selenium, and tellurium belong to the uneven series of the sixth group. In the even series of this group there are known _chromium, molybdenum, tungsten, and uranium_; these give acid oxides of the type RO_{3}, like SO_{3}. Their acid properties are less sharply defined than those of sulphur, selenium, and tellurium, as is the case with all elements of the even series as compared with those of the uneven series in the same group. But still the oxides CrO_{3}, MoO_{3}, WO_{3}, and even UO_{3}, have clearly defined acid properties, and form salts of the composition MO,_n_RO_{3} with bases MO. In the case of the heavy elements, and especially of uranium, the type of oxide, UO_{3}, is less acid and more basic, because in the even series of oxides the element with the highest atomic weight always acquires a more and more pronounced basic character. Hence UO_{3} shows the properties of a base, and gives salts UO_{2}X_{2}. The basic properties of chromium, molybdenum, tungsten, and uranium are most clearly expressed in the lower oxides, which they all form. Thus chromic oxide, Cr_{2}O_{3}, is as distinct a base as alumina, Al_{2}O_{3}. Of all these elements _chromium_ is the most widely distributed and the most frequently used. It gives chromic anhydride, CrO_{3}, and chromic oxide, Cr_{2}O_{3}--two compounds whose relative amounts of oxygen stand in the ratio 2 : 1. Chromium is, although somewhat rarely, met with in nature as a compound of one or the other type. The red chromium ore of the Urals, lead chromate or crocoisite PbCrO_{4}, was the source in which chromium was discovered by Vauquelin, who gave it this name (from the Greek word signifying colour) owing to the brilliant colours of its compounds; the chromates (salts of chromic anhydride) are red and yellow, and the chromic salts (from Cr_{2}O_{3}) green and violet. The red lead chromate is, however, a rare chromium ore found only in the Urals and in a few other localities. Chromic oxide, Cr_{2}O_{3}, is more frequently met with. In small quantities it forms the colouring matter of many minerals and rocks--for example, of some serpentines. The commonest ore, and the chief source of the chromium compounds, is the _chrome iron ore_ or chromite, which occurs in the Urals[1] and Asia Minor, California, Australia, and other localities. This is magnetic iron ore, FeO,Fe_{2}O_{3}, in which the ferric oxide is replaced by chromic oxide, its composition being FeO,Cr_{2}O_{3}. Chrome iron ore crystallises in octahedra of sp. gr. 4·4; it has a feeble metallic lustre, is of a greyish-black colour, and gives a brown powder. It is very feebly acted on by acids, but when fused with potassium acid sulphate it gives a soluble mass, which contains a chromic salt, besides potassium sulphate and ferrous sulphate. In practice the treatment of chrome iron ore is mainly carried on for the preparation of chromates, and not of chromic salts, and therefore we will trace the history of the element by beginning with chromic acid, and especially with the working up of the chrome iron ore into _potassium dichromate_, K_{2}Cr_{2}O_{7}, as the most common salt of this acid. It must be remarked that chromic anhydride, CrO_{3}, is only obtained in an anhydrous state, and is distinguished for its capacity for easily giving anhydro-salts with the alkalis, containing one, two, and even three equivalents of the anhydride to one equivalent of base. Thus among the potassium salts there is known the normal or yellow chromate, K_{2}CrO_{4}, which corresponds to, and is perfectly isomorphous with, potassium sulphate, easily forms isomorphous mixtures with it, and is not therefore suitable for a process in which it is necessary to separate the salt from a mixture containing sulphates. As in the presence of a certain excess of acid, the dichromate, K_{2}Cr_{2}O_{7} = 2K_{2}CrO_{4} + 2HX - 2KX - H_{2}O, is easily formed from K_{2}CrO_{4}, the object of the manufacturer is to produce such a dichromate, the more so as it contains a larger proportion of the elements of chromic acid than the normal salt. Finely-ground chrome iron ore, when heated with an alkali, absorbs oxygen almost as easily (Chapter III., Note 7) as a mixture of the oxides of manganese with an alkali. This absorption is due to the presence of chromic oxide, which is oxidised into the anhydride, and then combines with the alkali Cr_{2}O_{3} + O_{3} = 2CrO_{3}. As the oxidation and formation of the chromate proceeds, the mass turns _yellow_. The iron is also oxidised, but does not give ferric acid, because the capacity of the chromium for oxidation is incomparably greater than that of the iron. [1] The working of the Ural chrome iron ore into chromium compounds has been firmly established in Russia, thanks to the endeavours of P. K. Ushakoff, who constructed large works for this purpose on the river Kama, near Elabougi, where as much as 2,000 tons of ore are treated yearly, owing to which the importation of chromium preparations into Russia has ceased. A mixture of lime (sometimes with potash) and chrome iron ore is heated in a reverberatory furnace, with free access of air and at a red heat for several hours, until the mass becomes yellow; it then contains normal calcium chromate, CaCr_O_{4}, which is insoluble in water in the presence of an excess of lime.[1 bis] The resultant mass is ground up, and treated with water and sulphuric acid. The excess of lime forms gypsum, and the soluble calcium dichromate, CaCr_{2}O_{7}, together with a certain amount of iron, pass into solution. The solution is poured off, and chalk added to it; this precipitates the ferric oxide (the ferrous oxide is converted into ferric oxide in the furnace) and forms a fresh quantity of gypsum, while the chromic acid remains in solution--that is, it does not form the sparingly-soluble normal salt (1 part soluble in 240 parts of water). The solution then contains a fairly pure calcium dichromate, which by double decomposition gives other chromates; for example, with a solution of potassium sulphate it gives a precipitate of calcium sulphate and a solution of potassium dichromate, which crystallises when evaporated.[2] [1 bis] But the calcium chromate is soluble in water in the presence of an excess of chromic acid, as may be seen from the fact that a solution of chromic acid dissolves lime. [2] There are many variations in the details of the manufacturing processes, and these must be looked for in works on technical chemistry. But we may add that the chromate may also be obtained by slightly roasting briquettes of a mixture of chrome iron and lime, and then leaving the resultant mass to the action of moist air (oxygen is absorbed, and the mass turns yellow). _Potassium dichromate_, K_{2}Cr_{2}O_{7}, easily crystallises from acid solutions in red, well-formed prismatic crystals, which fuse at a red heat and evolve oxygen at a very high temperature, leaving chromic oxide and the normal salt, which undergoes no further change: 2K_{2}Cr_{2}O_{7} = 2K_{2}CrO_{4} + Cr_{2}O_{3} + O_{3}. At the ordinary temperature 100 parts of water dissolve 10 parts of this salt, and the solubility increases as the temperature rises. It is most important to note that the dichromate does not contain water, it is K_{2}CrO_{4} + CrO_{3}; the acid salt corresponding to potassium acid sulphate, KHSO_{4}, does not exist. It does not even evolve heat when dissolving in water, but on the contrary produces cold, _i.e._ it does not form a very stable compound with water. The solution and the salt itself are poisonous, and act as powerful oxidising agents, which is the character of chromic acid in general. When heated with sulphur or organic substances, with sulphurous anhydride, hydrogen sulphide, &c., this salt is deoxidised, yielding chromic compounds.[2 bis] Potassium dichromate[3] is used in the arts and in chemistry as a source for the preparation of all other chromium compounds. It is converted into yellow pigments by means of double decomposition with salts of lead, barium, and zinc. When solutions of the salts of these metals are mixed with potassium dichromate (in dyeing generally mixed with soda, in order to obtain normal salts), they are precipitated as insoluble normal salts; for example, 2BaCl_{2} + K_{2}Cr_{2}O_{7} + H_{2}O = 2BaCrO_{4} + 2KCl + 2HCl. It follows from this that these salts are insoluble in dilute acids, but the precipitation is not complete (as it would be with the normal salt). The barium and zinc salts are of a lemon yellow colour; the lead salt has a still more intense colour passing into orange. Yellow cotton prints are dyed with this pigment. The silver salt, Ag_{2}CrO_{4}, is of a bright red colour. [2 bis] The oxidising action of potassium dichromate on organic substances at the ordinary temperature is especially marked under the action of light. Thus it acts on gelatin, as Poutven discovered; this is applied to photography in the processes of photogravure, photo-lithography, pigment printing, &c. Under the action of light this gelatin is oxidised, and the chromic anhydride deoxidised into chromic oxide, which unites with the gelatin and forms a compound insoluble in warm water, whilst where the light has not acted, the gelatin remains soluble, its properties being unaffected by the presence of chromic acid or potassium dichromate. [3] Ammonium and sodium dichromates are now also prepared on a large scale. The sodium salts may be prepared in exactly the same manner as those of potassium. The normal salt combines with ten equivalents of water, like Glauber's salt, with which it is isomorphous. Its solution above 30° deposits the anhydrous salt. Sodium dichromate crystals contain Na_{2}Cr_{2}O_{7},2H_{2}O. The _ammonium salts of chromic acid_ are obtained by saturating the anhydride itself with ammonia. The dichromate is obtained by saturating one part of the anhydride with ammonia, and then adding a second part of anhydride and evaporating under the receiver of an air-pump. On ignition, the normal and acid salts leave chromic oxide. Potassium ammonium chromate, NH_{4}KCrO_{4}, is obtained in yellow needles from a solution of potassium dichromate in aqueous ammonia; it not only loses ammonia and becomes converted into potassium dichromate when ignited, but also by degrees at the ordinary temperature. This shows the feeble energy of chromic acid, and its tendency to form stable dichromates. Magnesium chromate is soluble in water, as also is the strontium salt. The calcium salt is also somewhat soluble, but the barium salt is almost insoluble. The isomorphism with sulphuric acid is shown in the chromates by the fact that the magnesium and ammonium salts form double salts containing six equivalents of water, which are perfectly isomorphous with the corresponding sulphates. The magnesium salt crystallises in large crystals containing seven equivalents of water. The beryllium, cerium, and cobalt salts are insoluble in water. Chromic acid dissolves manganous carbonate, but on evaporation the solution deposits manganese dioxide, formed at the expense of the oxygen of the chromic acid. Chromic acid also oxidises ferrous oxide, and ferric oxide is soluble in chromic acid. One of the chromates most used by the dyer is the insoluble yellow lead chromate, PbCrO_{4} (Chapter XVIII., Note 46), which is precipitated on mixing solutions of PbX_{2} with soluble chromates. It easily forms a basic salt, having the composition PbO,PbCrO_{4}, as a crystalline powder, obtained by fusing the normal salt with nitre and then rapidly washing in water. The same substance is obtained, although impure and in small quantity, by treating lead chromate with neutral potassium chromate, especially on boiling the mixture; and this gives the possibility of attaining, by means of these materials, various tints of lead chromate, from yellow to red, passing through different orange shades. The decomposition which takes place (incompletely) in this case is as follows: 2PbCrO_{4} + K_{2}CrO_{4} = PbCrO_{4},PbO + K_{2}Cr_{2}O_{7}--that is, potassium dichromate is formed in solution. When potassium dichromate is mixed with potassium hydroxide or carbonate (carbonic anhydride being disengaged in the latter case) it forms the _normal_ salt, K_{2}CrO_{4}, known as _yellow chromate of potassium_. Its specific gravity is 2·7, being almost the same as that of the dichromate. It absorbs heat in dissolving; one part of the salt dissolves in 1·75 part of water at the ordinary temperature, forming a yellow solution. When mixed even with such feeble acids as acetic, and more especially with the ordinary acids, it gives the dichromate, and Graham obtained a trichromate, K_{2}Cr_{3}O_{10} = K_{2}CrO_{4},2CrO_{3}, by mixing a solution of the latter salt with an excess of nitric acid. _Chromic anhydride_ is obtained by preparing a saturated solution of potassium dichromate at the ordinary temperature, and pouring it in a thin stream into an equal volume of pure sulphuric acid.[4] On mixing, the temperature naturally rises; when slowly cooled, the solution deposits chromic anhydride in needle-shaped crystals of a red colour sometimes several centimetres long. The crystals are freed from the mother liquor by placing them on a porous tile.[4 bis] It is very important at this point to call attention to the fact that a hydrate of chromic anhydride is never obtained in the decomposition of chromic compounds, but always the _anhydride_, CrO_{3}. The corresponding hydrate, CrO_{4}H_{2}, or any other hydrate, is not even known. Nevertheless, it must be admitted that chromic acid is bibasic, because it forms salts isomorphous or perfectly analogous with the salts formed by sulphuric acid, which is the best example of a bibasic acid. A clear proof of the bibasicity of CrO_{3} is seen in the fact that the anhydride and salts give (when heated with sodium chloride and sulphuric acid) a volatile chloranhydride, CrO_{2}Cl_{2}, containing two atoms of chlorine as a bibasic acid should.[5] Chromic anhydride is a red crystalline substance, which is converted into a black mass by heat; it fuses at 190°, and disengages oxygen above 250°, leaving a residue of chromium dioxide, CrO_{2},[6] and, on still further heating, chromic oxide, Cr_{2}O_{3}. Chromic anhydride is exceedingly soluble in water, and even attracts moisture from the air, but, as was mentioned above, it does not form any definite compound with water. The specific gravity of its crystals is 2·7, and when fused it has a specific gravity 2·6. The solution presents perfectly defined acid properties. It liberates carbonic anhydride from carbonates; gives insoluble precipitates of the chromates with salts of barium, lead, silver, and mercury. [4] The sulphuric acid should not contain any lower oxides of nitrogen, because they reduce chromic anhydride into chromic oxide. If a solution of a chromate be heated with an excess of acid--for instance, sulphuric or hydrochloric acid--oxygen or chlorine is evolved, and a solution of a chromic salt is formed. Hence, under these circumstances, chromic acid cannot be obtained from its salts. One of the first methods employed consisted in converting its salts into volatile _chromium hexafluoride_, CrF_{6}. This compound, obtained by Unverdorben, may be prepared by mixing lead chromate with fluor spar in a dry state, and treating the mixture with fuming sulphuric acid in a platinum vessel: PbCrO_{4} + 3CaF_{2} + 4H_{2}SO_{4} = PbSO_{4} + 3CaSO_{4} + 4H_{2}O + CrF_{6}. Fuming sulphuric acid is taken, and in considerable excess, because the chromium fluoride which is formed is very easily decomposed by water. It is volatile, and forms a very caustic, poisonous vapour, which condenses when cooled in a dry platinum vessel into a red, exceedingly volatile liquid, which fumes powerfully in air. The vapours of this substance when introduced into water are decomposed into hydrofluoric acid and chromic anhydride: CrF_{6} + 3H_{2}O = CrO_{3} + 6HF. If very little water be taken the hydrofluoric acid volatilises, and chromic anhydride separates directly in crystals. The chloranhydride of chromic acid, CrO_{2}Cl_{2} (Note 5), is also decomposed in the same manner. A solution of chromic acid and a precipitate of barium sulphate are formed by treating the insoluble barium chromate with an equivalent quantity of sulphuric acid. If carefully evaporated, the solution yields crystals of chromic anhydride. Fritzsche gave a very convenient method of preparing chromic anhydride, based on the relation of chromic to sulphuric acid. At the ordinary temperature the strong acid dissolves both chromic anhydride and potassium chromate, but if a certain amount of water is added to the solution the chromic anhydride separates, and if the amount of water be increased the precipitated chromic anhydride is again dissolved. The chromic anhydride is almost all separated from the solution when it contains two equivalents of water to one equivalent of sulphuric acid. Many methods for the preparation of chromic anhydride are based on this fact. [4 bis] They cannot be filtered through paper or washed, because the chromic anhydride is reduced by the filter-paper, and is dissolved during the process of washing. [5] Berzelius observed, and Rose carefully investigated, this remarkable reaction, which occurs between chromic acid and sodium chloride in the presence of sulphuric acid. If 10 parts of common salt be mixed with 12 parts of potassium dichromate, fused, cooled, and broken up into lumps, and placed in a retort with 20 parts of fuming sulphuric acid, it gives rise to a violent reaction, accompanied by the formation of brown fumes of _chromic chloranhydride_, or _chromyl chloride_, CrO_{2}Cl_{2}, according to the reaction: CrO_{3} + 2NaCl + H_{2}SO_{4} = Na_{2}SO_{4} + H_{2}O + CrO_{2}Cl_{2}. The addition of an excess of sulphuric acid is necessary in order to retain the water. The same substance is always formed when a metallic chloride is heated with chromic acid, or any of its salts, in the presence of sulphuric acid. The formation of this volatile substance is easily observed from the brown colour which is proper to its vapour. On condensing the vapour in a dry receiver a liquid is obtained having a sp. gr. of 1·9, boiling at 118°, and giving a vapour whose density, compared with hydrogen, is 78, which corresponds with the above formula. Chromyl chloride is decomposed by heat into chromic oxide, oxygen, and chlorine: 2CrO_{2}Cl_{2} = Cr_{2}O_{3} + 2Cl_{2} + O; so that it is able to act simultaneously as a powerful oxidising and chlorinating agent, which is taken advantage of in the investigation of many, and especially of organic, substances. When treated with water, this substance first falls to the bottom, and is then decomposed into hydrochloric and chromic acids, like all chloranhydrides: CrO_{2}Cl_{2} + H_{2}O = CrO_{3} + 2HCl. When brought into contact with inflammable substances it sets fire to them; it acts thus, for instance, on phosphorus, sulphur, oil of turpentine, ammonia, hydrogen, and other substances. It attracts moisture from the atmosphere with great energy, and must therefore be kept in closed vessels. It dissolves iodine and chlorine, and even forms a solid compound with the latter, which depends upon the faculty of chromium to form its higher oxide, Cr_{2}O_{7}. The close analogy in the physical properties of the chloranhydrides, CrO_{2}Cl_{2} and SO_{2}Cl_{2}, is very remarkable, although sulphurous anhydride is a gas, and the corresponding oxide, CrO_{2}, is a non-volatile solid. It may be imagined, therefore, that chromium dioxide (which will be mentioned in the following note) presents a polymerised modification of the substance having the composition CrO_{2}; in fact, this is obvious from the method of its formation. If three parts of potassium dichromate be mixed with four parts of strong hydrochloric acid and a small quantity of water, and gently warmed, it all passes into solution, and no chlorine is evolved; on cooling, the liquid deposits red prismatic crystals, known as _Peligot's salt_, very stable in air. This has the composition KCl,CrO_{3}, and is formed according to the equation K_{2}Cr_{2}O_{7} + 2HCl = 2KCl,CrO_{3} + H_{2}O. It is evident that this is the first chloranhydride of chromic acid, HCrO_{3}Cl, in which the hydrogen is replaced by potassium. It is decomposed by water, and on evaporation the solution yields potassium dichromate and hydrochloric acid. This is a fresh instance of the reversible reactions so frequently encountered. With sulphuric acid Peligot's salt forms chromyl chloride. The latter circumstance, and the fact that Geuther produced Peligot's salt from potassium chromate and chromyl chloride, give reason for thinking that it is a compound of these two substances: 2KCl,CrO_{3} = K_{2}CrO_{4} + CrO_{2}Cl_{2}. It is also sometimes regarded as potassium dichromate in which one atom of oxygen is replaced by chlorine--that is, K_{2}Cr_{2}O_{6}Cl_{2}, corresponding with K_{2}Cr_{2}O_{7}. When heated it parts with all its chlorine, and on further heating gives chromic oxide. [6] This intermediate degree of oxidation, CrO_{2}, may also be obtained by mixing solutions of chromic salts with solutions of chromates. The brown precipitate formed contains a compound, Cr_{2}O_{3},CrO_{3}, consisting of equivalent amounts of chromic oxide and anhydride. The brown precipitate of chromium dioxide contains water. The same substance is formed by the imperfect deoxidation of chromic anhydride by various reducing agents. Chromic oxide, when heated, absorbs oxygen, and appears to give the same substance. Chromic nitrate, when ignited, also gives this substance. When this substance is heated it first disengages water and then oxygen, chromic oxide being left. It corresponds with manganese dioxide, Cr_{2}O_{3},CrO_{3} = 3CrO_{2}. Krüger treated chromium dioxide with a mixture of sodium chloride and sulphuric acid, and found that chlorine gas was evolved, but that chromyl chloride was not formed. Under the action of light, a solution of chromic acid also deposits the brown dioxide. At the ordinary temperature chromic anhydride leaves a brown stain upon the skin and tissues, which probably proceeds from a decomposition of the same kind. Chromic anhydride is soluble in alcohol containing water, and this solution is decomposed in a similar manner by light. Chromium dioxide forms K_{2}CrO_{4} when treated with H_{2}O_{2} in the presence of KHO. The action of hydrogen peroxide on a solution of chromic acid or of potassium dichromate gives a blue solution, which very quickly becomes colourless with the disengagement of oxygen. Barreswill showed that this is due to the formation of a _perchromic anhydride_, Cr_{2}O_{7}, corresponding with sulphur peroxide. This peroxide is remarkable from the fact that it very easily dissolves in ether and is much more stable in this solution, so that, by shaking up hydrogen peroxide mixed with a small quantity of chromic acid, with ether, it is possible to transfer all the blue substance formed to the ether.[6 bis] [6 bis] Now that persulphuric acid H_{2}S_{2}O_{8} is well known it might be supposed that perchromic anhydride, Cr_{2}O_{7}, would correspond to perchromic acid, H_{2}Cr_{2}O_{8}, but as yet it is not certain whether corresponding salts are formed. Péchard (1891) on adding an excess of H_{2}O_{2} and baryta water to a dilute solution of CrO_{2} (8 grm. per litre), observed the formation of a yellow precipitate, but oxygen was disengaged at the same time and the precipitate (which easily exploded when dried) was found to contain, besides an admixture of BaO_{2}, a compound BaCrO_{5}, and this = BaO_{2} + CrO_{3}, and does not correspond to perchromic acid. The fact of its decomposing with an explosion, and the mode of its preparation, proves, however, that this is a similar derivative of peroxide of hydrogen to persulphuric acid (Chapter XX.) With oxygen acids, chromic acid evolves oxygen; for example, with sulphuric acid the following reaction takes place: 2CrO_{3} + 3H_{2}SO_{4} = Cr_{2}(SO_{4})_{3} + O_{3} + 3H_{2}O. It will be readily understood from this that _a mixture of chromic acid_ or _of its salts with sulphuric acid_ forms an excellent _oxidising agent_, which is frequently employed in chemical laboratories and even for technical purposes as a means of oxidation. Thus hydrogen sulphide and sulphurous anhydride are converted into sulphuric acid by this means. Chromic acid is able to act as a powerful oxidising agent because it passes into chromic oxide, and in so doing disengages half of the oxygen contained in it: 2CrO_{3} = Cr_{2}O_{3} + O_{3}. Thus chromic anhydride itself is a powerful oxidising agent, and is therefore employed instead of nitric acid in galvanic batteries (as a depolariser), the hydrogen evolved at the carbon being then oxidised, and the chromic acid converted into a non-volatile product of deoxidation, instead of yielding, as nitric acid does, volatile lower oxides of offensive odour. Organic substances are more or less perfectly oxidised by means of chromic anhydride, although this generally requires the aid of heat, and does not proceed in the presence of alkalis, but generally _in the presence of acids_. In acting on a solution of potassium iodide, chromic acid, like many oxidising agents, liberates iodine; the reaction proceeds in proportion to the amount of CrO_{3} present, and may serve for determining the amount of CrO_{3}, since the amount of iodine liberated can be accurately determined by the iodometric method (Chapter XX., Note 42). If chromic anhydride be ignited in a stream of ammonia, it gives chromic oxide, water, and nitrogen. In all cases when chromic acid acts as an oxidising agent in the presence of acids and under the action of heat, the product of its deoxidation is a chromic salt, CrX_{3}, which is characterised by the green colour of its solution, so that the _red_ or yellow _solution_ of a salt of chromic acid is then transformed into a _green solution_ of a chromic salt, derived from chromic oxide, Cr_{2}O_{3}, which is closely analogous to Al_{2}O_{3}, Fe_{2}O_{3}, and other bases of the composition R_{2}O_{3}. This analogy is seen in the insolubility of the anhydrous oxide, in the gelatinous form of the colloidal hydrate, in the formation of alums,[7] of a volatile chloride of chromium, &c.[7 bis] [7] As a mixture of potassium dichromate and sulphuric acid is usually employed for oxidation, the resultant solution generally contains a double sulphate of potassium and chromium--that is, _chrome alum_, isomorphous with ordinary alum--K_{2}Cr_{2}O_{7} + 4H_{2}SO_{4} + 20H_{2}O = O_{3} + K_{2}Cr_{2}(SO_{4})_{4},24H_{2}O or 2(KCr(SO_{4})_{2},12H_{2}O). It is prepared by dissolving potassium dichromate in dilute sulphuric acid; alcohol is then added and the solution slightly heated, or sulphurous anhydride is passed through it. On the addition of alcohol to a cold mixture of potassium dichromate and sulphuric acid, the gradual disengagement of pleasant-smelling volatile products of the oxidation of alcohol, and especially of aldehyde, C_{2}H_{4}O, is remarked. If the temperature of decomposition does not exceed 35°, a _violet_ solution of chrome alum is obtained, but if the temperature be higher, a solution of the same alum is obtained of a _green_ colour. As chrome alum requires for solution 7 parts of water at the ordinary temperature, it follows that if a somewhat strong solution of potassium dichromate be taken (4 parts of water and 1-1/2 of sulphuric acid to 1 part of dichromate), it will give so concentrated a solution of chrome alum that on cooling, the salt will separate without further evaporation. _If the liquid_, prepared as above or in any instance of the deoxidation of chromic acid, _be heated_ (the oxidation naturally proceeds more rapidly) somewhat strongly, for instance, to the boiling-point of water, or if the violet solution already formed be raised to the same temperature, it acquires a bright _green colour_, and on evaporation the same mixture, which at lower temperatures so easily gives cubical crystals of chrome alum, _does not give any crystals whatever_. _If the green solution be kept_, however, _for several weeks_ at the ordinary temperature, it deposits _violet crystals_ of chrome alum. The green solution, when evaporated, gives a non-crystalline mass, and the violet crystals lose water at 100° and turn green. It must be remarked that the transition of the green modification into the violet is accompanied by a decrease in volume (Lecoq de Boisbaudran, Favre). If the green mass formed at the higher temperature be evaporated to dryness and heated at 30° in a current of air, it does not retain more then 6 equivalents of water. Hence Löwel, and also Schrötter, concluded that the green and violet modifications of the alum depend on different degrees of combination with water, which may be likened to the different compounds of sodium sulphate with water and to the different hydrates of ferric oxide. However, the question in this case is not so simple, as we shall afterwards see. Not chrome alum alone, but _all the chromic salts_, give two, if not three, _varieties_. At least, there is no doubt about the existence of two--a _green_ and a _violet modification_. The green chromic salts are obtained by heating solutions of the violet salts, the violet solutions are produced on keeping solutions of the green salts for a long time. The conversion of the violet salts into green by the action of heat is itself an indication of the possibility of explaining the different modifications by their containing different proportions (or states) of water, and, moreover, by the green salts having a less amount of water than the violet. However, there are other explanations. Chromic oxide is a base like alumina, and is therefore able to give both acid and basic salts. It is supposed that the difference between the green and violet salts is due to this fact. This opinion of Krüger is based on the fact that alcohol separates out a salt from the green solution which contains less sulphuric acid than the normal violet salt. On the other hand, Löwel showed that all the acid cannot be separated from the green chromic salts by suitable reagents, as easily as it can be from the same solution of the violet salts; thus barium salts do not precipitate all the sulphuric acid from solutions of the green salts. According to other researches the cause of the varieties of the chromic salts lies in a difference in the bases they contain--that is, it is connected with a modification of the properties of the oxide of chromium itself. This only refers to the hydroxides, but as hydroxides themselves are only special forms of salts, the differences observed as yet in this direction between the hydroxides only confirm the generality of the difference observed in the chromic compounds (_see_ Note 7 bis). The salts of chromic oxide, like those of alumina, are easily decomposed, give basic and double salts, and have an acid reaction, as chromic oxide is a feeble base. Potassium and sodium hydroxides give a _precipitate_ of the hydroxide with chromic salts, CrX_{3}. The violet and green salts give a _hydroxide soluble in an excess of the reagent_; but the hydroxide is held in solution by very feeble affinities, so that it is partially separated by heat and dilution with water, and completely so on boiling. In an alkaline solution, chromic hydroxide is easily converted into chromic acid by the action of lead dioxide, chlorine, and other oxidising agents. If the chromic oxide occurs together with such oxides as magnesia, or zinc oxide, then on precipitation it separates out from its solution in combination with these oxides, forming, for example, ZnO,Cr_{2}O_{3}. Viard obtained compounds of Cr_{2}O_{3} with the oxides of Mg, Zn, Cd, &c.) On precipitating the violet solution of chrome alum with ammonia, a precipitate containing Cr_{2}O_{3},6H_{2}O is obtained, whilst the precipitate from the boiling solution with caustic potash was a hydrate containing four equivalents of water. When fused with borax chromic salts give a green glass. The same coloration is communicated to ordinary glass by the presence of traces of chromic oxide. A chrome glass containing a large amount of chromic oxide may be ground up and used as a green pigment. Among the hydrates of oxide of chromium _Guignet's green_ forms one of the widely-used green pigments which have been substituted for the poisonous arsenical copper pigments, such as Schweinfurt green, which formerly was much used. Guignet's green has an extremely bright green colour, and is distinguished for its great stability, not only under the action of light but also towards reagents; thus it is not altered by alkaline solutions, and even nitric acid does not act on it. This pigment remains unchanged up to a temperature of 250°; it contains Cr_{2}O_{3},2H_{2}O, and generally a small amount of alkali. It is prepared by fusing 3 parts of boric acid with 1 part of potassium dichromate; oxygen is disengaged, and a green glass, containing a mixture of the borates of chromium and potassium, is obtained. When cool this glass is ground up and treated with water, which extracts the boric acid and alkali and leaves the above-named chromic hydroxide behind. This hydroxide only parts with its water at a red heat, leaving the anhydrous oxide. The chromic hydroxides lose their water by ignition, and in so doing become spontaneously incandescent, like the ordinary ferric hydroxide (Chapter XXII.). It is not known, however, whether all the modifications of chromic oxide show this phenomenon. The anhydrous _chromic oxide_, Cr_{2}O_{3}, is exceedingly difficultly soluble in acids, if it has passed through the above recalescence. But if it has parted with its water, or the greater part of it, and not yet undergone this self-induced incandescence (has not lost a portion of its energy), then it is soluble in acids. It is not reduced by hydrogen. It is easily obtained in various crystalline forms by many methods. The chromates of mercury and ammonium give a very convenient method for its preparation, because when ignited they leave chromic oxide behind. In the first instance oxygen and mercury are disengaged, and in the second case nitrogen and water: 2Hg_{2}CrO_{4} = Cr_{2}O_{3} + O_{5} + 4Hg or (NH_{4})_{2}Cr_{2}O_{7} = Cr_{2}O_{3} + 4H_{2}O + N_{2}. The second reaction is very energetic, and the mass of salt burns spontaneously if the temperature be sufficiently high. A mixture of potassium sulphate and chromic oxide is formed by heating potassium dichromate with an equal weight of sulphur: K_{2}Cr_{2}O_{7} + S = K_{2}SO_{4} + Cr_{2}O_{3}. The sulphate is easily extracted by water, and there remains a bright green residue of the oxide, whose colour is more brilliant the lower the temperature of the decomposition. The oxide thus obtained is used as a green pigment for china and enamel. The anhydrous chromic oxide obtained from chromyl chloride, CrO_{2}Cl_{2}, has a specific gravity of 5·21, and forms almost black crystals, which give a green powder. They are hard enough to scratch glass, and have a metallic lustre. The crystalline form of chromic oxide is identical with that of the oxide of iron and alumina, with which it is isomorphous. [7 bis] The most important of the compounds corresponding with chromic oxide is _chromic chloride_, Cr_{2}Cl_{6}, which is known in an anhydrous and in a hydrated form. It resembles ferric and aluminic chlorides in many respects. There is a great difference between the anhydrous and the hydrated chlorides; the former is insoluble in water, the latter easily dissolves, and on evaporation its solution forms a hygroscopic mass which is very unstable and easily evolves hydrochloric acid when heated with water. The anhydrous form is of a violet colour, and Wöhler gives the following method for its preparation: an intimate mixture is prepared of the anhydrous chromic oxide with carbon and organic matter, and charged into a wide infusible glass or porcelain tube which is heated in a combustion furnace; one extremity of the tube communicates with an apparatus generating chlorine which is passed through several bottles containing sulphuric acid in order to dry it perfectly before it reaches the tube. On heating the portion of the tube in which the mixture is placed and passing chlorine through, a slightly volatile sublimate of chromic chloride, CrCl_{3} or Cr_{2}Cl_{6}, is formed. This substance forms _violet tabular crystals_, which may be distilled in dry chlorine without change, but which, however, require a red heat for their volatilisation. These crystals are greasy to the touch and insoluble in water, but if they be powdered and boiled in water for a long time they pass into _a green solution_. Strong sulphuric acid does not act on the anhydrous salt, or only acts with exceeding slowness, like water. Even aqua regia and other acids do not act on the crystals, and alkalis only show a very feeble action. The specific gravity of the crystals is 2·99. When fused with sodium carbonate and nitre they give sodium chloride and potassium chromate, and when ignited in air they form green chromic oxide and evolve chlorine. On ignition in a stream of ammonia, chromic chloride forms sal-ammoniac and chromium nitride, CrN (analogous to the nitrides BN, AlN). Mosberg and Peligot showed that when chromic chloride is ignited in hydrogen, it parts with one-third of its chlorine, forming chromous chloride, CrCl_{2}--that is, there is formed from a compound corresponding with chromic oxide, Cr_{2}O_{3}, a compound answering to the _suboxide_, chromous oxide, CrO--just as hydrogen converts ferric chloride into ferrous chloride with the aid of heat. _Chromous chloride_, CrCl_{2}, forms colourless crystals easily soluble in water, which in dissolving evolve a considerable amount of heat, and form a blue liquid, capable of absorbing oxygen from the air with great facility, being converted thereby into a chromic compound. The blue solution of chromous chloride may also be obtained by the action of metallic zinc on the green solution of the hydrated chromic chloride; the zinc in this case takes up chlorine just as the hydrogen did. It must be employed in a large excess. Chromic oxide is also formed in the action of zinc on chromic chloride, and if the solution remain for a long time in contact with the zinc the whole of the chromium is converted into chromic oxychloride. Other chromic salts are also reduced by zinc into _chromous salts_, CrX_{2}, just as the ferric salts FeX_{3} are converted into ferrous salts FeX_{2} by it. The chromous salts are exceedingly unstable and easily oxidise and pass into chromic salts; hence the reducing power of these salts is very great. From cupric salts they separate cuprous salts, from stannous salts they precipitate metallic tin, they reduce mercuric salts into mercurous and ferric into ferrous salts. Moreover, they absorb oxygen from the air directly. With potassium chromate they give a brown precipitate of chromium dioxide or of chromic oxide, according to the relative amounts of the substances taken: CrO_{3} + CrO = 2CrO_{2} or CrO_{3} + 3CrO = 2Cr_{2}O_{3}. Aqueous ammonia gives a blue precipitate, and in the presence of ammoniacal salts a blue liquid is obtained which turns red in the air from oxidation. This is accompanied by the formation of compounds analogous to those given by cobalt (Chapter XXII.). A solution of chromous chloride with a hot saturated solution of sodium acetate, C_{2}H_{3}NaO_{2}, gives, on cooling, transparent red crystals of chromous acetate, C_{4}H_{6}CrO_{4},H_{2}O. This salt is also a powerful reducing agent, but may be kept for a long time in a vessel full of carbonic anhydride. The insoluble anhydrous _chromic chloride_ CrCl_{3} very easily _passes into solution_ in the presence of a trace (0·004) of _chromous chloride_ CrCl_{2}. This remarkable phenomenon was observed by Peligot and explained by Löwel in the following manner: chromous chloride, as a lower stage of oxidation, is capable of absorbing both oxygen and chlorine, combining with various substances. It is able to decompose many chlorides by taking up chlorine from them; thus it precipitates mercurous chloride from a solution of mercuric chloride, and in so doing passes into chromic chloride: 2CrCl_{2} + 2HgCl_{2} = Cr_{2}Cl_{6} + 2HgCl. Let us suppose that the same phenomenon takes place when the anhydrous chromic chloride is mixed with a solution of chromous chloride. The latter will then take up a portion of the chlorine of the former, and pass into a soluble hydrate of chromic chloride (hydrochloride of oxide of chromium), and the original anhydrous chromic chloride will pass into chromous chloride. The chromous chloride re-formed in this manner will then act on a fresh quantity of the chromic chloride, and in this manner transfer it entirely into solution as hydrate. This view is confirmed by the fact that other chlorides, capable of absorbing chlorine like chromous chloride, also induce the solution of the insoluble chromic chloride--for example, ferrous chloride, FeCl_{2}, and cuprous chloride. The presence of zinc also aids the solution of chromic chloride, owing to its converting a portion of it into chromous chloride. The solution of chromic chloride in water obtained by these methods is perfectly identical with that which is formed by dissolving chromic hydroxide in hydrochloric acid. On evaporating the _green solution_ obtained in this manner, it gives a green mass, containing water. On further heating it leaves a soluble chromic oxychloride, and when ignited it first forms an insoluble oxychloride and then chromic oxide; but no anhydrous chromic chloride, Cr_{2}Cl_{6}, is formed by heating the aqueous solution of chromic chloride, which forms an important fact in support of the view that the green solution of chromic chloride is nothing else but hydrochloride of oxide of chromium. At 100° the composition of the green hydrate is Cr_{2}Cl_{6},9H_{2}O, and on evaporation at the ordinary temperature over H_{2}SO_{4} crystals are obtained with 12 equivalents of water; the red mass obtained at 120° contains Cr_{2}O_{3},4Cr_{2}Cl_{6},24H_{2}O. The greater portion of it is soluble in water, like the mass which is formed at 150°. The latter contains Cr_{2}O_{3},2Cr_{2}Cl_{6},9H_{2}O = 3(Cr_{2}OCl_{4},3H_{2}O)--that is, it presents the same composition as chromic chloride in which one atom of oxygen replaces two of chlorine. And if the hydrate of chromic chloride be regarded as Cr_{2}O_{3},6HCl, the substance which is obtained should be regarded as Cr_{2}O_{3},4HCl combined with water, H_{2}O. The addition of alkalis--for example, baryta--to a solution of chromic chloride immediately produces a precipitate, which, however, re-dissolves on shaking, owing to the formation of one of the oxychlorides just mentioned, which may be regarded as _basic salts_. Thus we may represent the product of the change produced on chromic chloride under the influence of water and heat by the following formulæ: first Cr_{2}O_{3},6HCl or Cr_{2}Cl_{6},3H_{2}O is formed, then Cr_{2}O_{3},4HCl,H_{2}O or Cr_{2}OCl_{4},3H_{2}O, and lastly Cr_{2}O_{3},2HCl,2H_{2}O or Cr_{2}O_{2}Cl_{2},3H_{2}O. In all three cases there are 2 equivalents of chromium to at least 3 equivalents of water. These compounds may be regarded as being intermediate between chromic hydroxide and chloride; chromic chloride is Cr_{2}Cl_{6}, the first oxychloride Cr_{2}(OH)_{2}Cl_{4}, the second Cr_{2}(OH)_{4}Cl_{2}, and the hydrate Cr_{2}(OH)_{6}--that is, the chlorine is replaced by hydroxyl. It is very important to remark two circumstances in respect to this: (1) That the whole of the chlorine in the above compounds is not precipitated from their solutions by silver nitrate; thus the normal salt of the composition Cr_{2}Cl_{6},9H_{2}O only gives up two-thirds of its chlorine; therefore Peligot supposes that the normal salt contains the oxychloride combined with hydrochloric acid: Cr_{2}Cl_{6} + 2H_{2}O = Cr_{2}O_{2}Cl_{2},4HCl, and that the chlorine held as hydrochloric acid reacts with the silver, whilst that held in the oxychloride does not enter into reaction, just as we observe a very feebly-developed faculty for reaction in the anhydrous chromic chloride; and (2) if the green aqueous solution of CrCl_{3} be left to stand for some time, it ultimately turns violet; in this form the whole of the chlorine is precipitated by AgNO_{3}, whilst boiling re-converts it into the green variety. Löwel obtained the violet solution of hydrochloride of chromic oxide by decomposing the violet chromic sulphate with barium chloride. Silver nitrate precipitates all the chlorine from this violet modification; but if the violet solution be boiled and so converted into the green modification, silver nitrate then only precipitates a portion of the chlorine. Recoura (1890-1893) obtained a crystallohydrate of violet chromium sulphate, Cr_{2}(SO_{4})_{3}, with 18 or 15 H_{2}O. By boiling a solution of this crystallohydrate, he converted it into the green salt, which, when treated with alkalis, gave a precipitate of Cr_{2}O_{3},2H_{2}O, soluble in 2H_{2}SO_{4} (and not 3), and only forming the basic salt, Cr_{2}(OH)_{2}(SO_{4})_{2}. He therefore concludes that the green salts are basic salts. The cryoscopic determinations made by A. Speransky (1892) and Marchetti (1892) give a greater 'depression' for the violet than the green salts, that is, indicate a greater molecular weight for the green salts. But as Étard, by heating the violet sulphate to 100°, converted it into a green salt of the same composition, but with a smaller amount of H_{2}O, it follows that the formation of a basic salt alone is insufficient to explain the difference between the green and violet varieties, and this is also shown by the fact that BaCl_{2} precipitates the whole of the sulphuric acid of the violet salt, and only a portion of that of the green salt. A. Speransky also showed that the molecular electro-conductivity of the green solutions is less than that of the violet. It is also known that the passage of the former into the latter is accompanied by an increase of volume, and, according to Recoura, by an evolution of heat also. Piccini's researches (1894) throw an important light upon the peculiarities of the green chromium trichloride (or chromic chloride); he showed (1) that AgF (in contradistinction to the other salts of silver) precipitates all the chlorine from an aqueous solution of the green variety; (2) that solutions of green CrCl_{3},6H_{2}O in ethyl alcohol and acetone precipitate all their chlorine when mixed with a similar solution of AgNO_{3}; (3) that the rise of the boiling-point of the ethyl alcohol and acetone green solutions of CrCl_{3},6H_{2}O (Chapter VII., Note 27 bis) shows that i in this case (as in the aqueous solutions of MgSO_{4} and HgCl_{2}) is nearly equal to 1, that is, that they are like solutions of non-conductors; (4) that a solution of green CrCl_{3} in methyl alcohol at first precipitates about 7/8 of its chlorine (an aqueous solution about 2/3) when treated with AgNO_{3}, but after a time the whole of the chlorine is precipitated; and (5) that an aqueous solution of the green variety gradually passes into the violet, while a methyl alcoholic solution preserves its green colour, both of itself and also after the whole of the chlorine has been precipitated by AgNO_{3}. If, however, in an aqueous or methyl alcoholic solution only a portion of the chlorine be precipitated, the solution gradually turns violet. In my opinion the general meaning of all these observations requires further elucidation and explanation, which should be in harmony with the theory of solutions. Recoura, moreover, obtained compounds of the green salt, Cr_{2}(SO_{4})_{3}, with 1, 2, and 3 molecules of H_{2}SO_{4}, K_{2}SO_{4}, and even a compound Cr_{2}(SO_{4})_{3}H_{2}CrO_{4}. By neutralising the sulphuric acid of the compounds of Cr_{2}(SO_{4})_{3} and H_{2}SO_{4} with caustic soda, Recoura obtained an evolution of 33 thousand calories per each 2NaHO, while free H_{2}SO_{4} only gives 30·8 thousand calories. Recoura is of opinion that special _chromo sulphuric acids_, for instance (CrSO_{4})H_{2}SO_{4} = 1/2Cr_{2}(SO_{4})_{3}H_{2}SO_{4}, are formed. With a still larger excess of sulphuric acid, Recoura obtained salts containing a still greater number of sulphuric acid radicles, but even this method does not explain the difference between the green and violet salts. These facts must naturally be taken into consideration in order to arrive at any complete decision as to the cause of the different modifications of the chromic salts. We may observe that the green modification of chromic chloride does not give double salts with the metallic chlorides, whilst the violet variety forms compounds Cr_{2}Cl_{6},2RCl (where R = an alkali metal), which are obtained by heating the chromates with an excess of hydrochloric acid and evaporating the solution until it acquires a violet colour. As the result of all the existing researches on the green and violet chromic salts, it appears to me most probable that their difference is determined by the feeble basic character of chromic oxide, by its faculty of giving basic salts, and by the colloidal properties of its hydroxide (these three properties are mutually connected), and moreover, it seems to me that the relation between the green and violet salts of chromic oxide best answers to the relation of the purpureo to the luteo cobaltic salts (Chapter XXII., Note 35). This subject cannot yet be considered as exhausted (_see_ Note 7). We may here observe that with tin the chromic salts, CrX_{3}, give at low temperatures CrX_{2} and SnX_{2}, whilst at high temperatures, on the contrary, CrX_{2} reduces the metal from its salts SnX_{2}. The reaction, therefore, belongs to the class of reversible reactions (Beketoff). Poulenc obtained anhydrous CrF_{3} (sp. gr. 3·78) and CrF_{2} (sp. gr. 4·11) by the action of gaseous HF upon CrCl_{2}. A solution of fluoride of chromium is employed as a mordant in dyeing. Recoura (1890) obtained green and violet varieties of Cr_{2}Br_{6},6H_{2}O. The green variety can only be kept in the presence of an excess of HBr in the solution; if alone its solution easily passes into the violet variety with evolution of heat. _Chromic oxide_, Cr_{2}O_{3}, rarely found, and in small quantities, in chrome ochre, is formed by the oxidation of chromium and its lower oxides, by the reduction of chromates (for example, of ammonium or mercuric chromate) and by the decomposition (splitting up) of the saline compounds of the oxide itself, CrX_{3} or Cr_{2}X_{6}, like alumina, which it resembles in forming a feeble base easily giving double and basic salts, which are either green or violet. The reduction of chromic oxide--for instance, in a solution by zinc and sulphuric acid--leads to the formation of chromous oxide, CrO, and its salts, CrX_{2}, of a blue colour (_see_ Notes 7 and 7 ^{bis}). The further reduction[8] of oxide of chromium and its corresponding compounds gives _metallic chromium_. Deville obtained it (probably containing carbon) by reducing chromic oxide with carbon, at a temperature near the melting point of platinum, about 1750°, but the metal itself does not fuse at this temperature. Chromium has a steel-grey colour and is very hard (sp. gr. 5·9), takes a good polish, and dissolves in hydrochloric acid, but cold dilute sulphuric and nitric acids have no action upon it. Bunsen obtained metallic chromium by decomposing a solution of chromic chloride, Cr_{2}Cl_{6}, by a galvanic current, as scales of a grey colour (sp. gr. 7·3). Wöhler obtained crystalline chromium by igniting a mixture of the anhydrous chromic chloride Cr_{2}Cl_{6} (_see_ Note 7 bis) with finely-divided zinc, and sodium and potassium chlorides, at the boiling-point of zinc. When the resultant mass has cooled the zinc may be dissolved in dilute nitric acid, and grey crystalline chromium (sp. gr. 6·81) is left behind. Frémy also prepared crystalline chromium by the action of the vapour of sodium on anhydrous chromic chloride in a stream of hydrogen, using the apparatus shown in the accompanying drawing, and placing the sodium and the chromic chloride in separate porcelain boats. The tube containing these boats is only heated when it is quite full of dry hydrogen. The crystals of metallic chromium obtained in the tube are grey cubes having a considerable hardness and withstanding the action of powerful acids, and even of aqua regia. The chromium obtained by Wöhler by the action of a galvanic current is, on the contrary, acted on under these conditions. The reason of this difference must be looked for in the presence of impurities, and in the crystalline structure. But in any case, among the properties of metallic chromium, the following may be considered established: it is white in colour, with a specific gravity of about 6·7, is extremely hard in a crystalline form, is not oxidised by air at the ordinary temperature, and with carbon it forms alloys like cast iron and steel. [8] The reduction of metallic chromium proceeds with comparative ease in aqueous solutions. Thus the action of sodium amalgams upon a strong solution of Cr_{2}Cl_{6} gives (first CrCl_{2}) an amalgam of chromium from which the mercury may be easily driven off by heating (in hydrogen to avoid oxidation), and there remains a spongy mass of easily oxidizable chromium. Plaset (1891), by passing an electric current through a solution of chrome alum mixed with a small amount of H_{2}SO_{4} and K_{2}SO_{4}, obtained hard scales of chromium of a bluish-white colour possessing great hardness and stability (under the action of water, air, and acids). Glatzel (1890) reduced a mixture of 2KCl + Cr_{2}Cl_{6} by heating it to redness with shavings of magnesium. The metallic chromium thus obtained has the appearance of a fine light-grey powder which is seen to be crystalline under the microscope; its sp. gr. at 16° is 6·7284. It fuses (with anhydrous borax) only at the highest temperatures, and after fusion presents a silver-white fracture. The strongest magnet has no action upon it. Moissan (1893) obtained chromium by reducing the oxide Cr_{2}O_{3} with carbon in the electrical furnace (Chapter VIII., Note 17) in 9-10 minutes with a current of 350 ampères and 50 volts. The mixture of oxide and carbon gives a bright ingot weighing 100-110 grams. A current of 100 ampères and 50 volts completes the experiment upon a smaller quantity of material in 15 minutes; a current of 30 ampères and 50 volts gave an ingot of 10 grams in 30-40 minutes. The resultant carbon alloy is more or less rich in chromium (from 87·37-91·7 p.c.). To obtain the metal free from carbon, the alloy is broken into large lumps, mixed with oxide of chromium, put into a crucible and covered with a layer of oxide. This mixture is then heated in the electric furnace and the pure metal is obtained. This reduction can also be carried on with chrome iron ore FeOCr_{2}O_{3} which occurs in nature. In this case a homogeneous alloy of iron and chromium is obtained. If this alloy be thrown in lumps into molten nitre, it forms insoluble sesquioxide of iron and a soluble alkaline chromate. This alloy of iron and chromium dissolved in molten steel (chrome steel) renders it hard and tough, so that such steel has many valuable applications. The alloy, containing about 3 p.c. Cr and about 1·3 p.c. carbon, is even harder than the ordinary kinds of tempered steel and has a fine granular fracture. The usual mode of preparing the ferrochromes for adding to steel is by fusing powdered chrome iron ore under fluxes in a graphite crucible. [Illustration: FIG. 92.--Apparatus for the preparation of metallic chromium by igniting chromic chloride and sodium in a stream of hydrogen.] The two analogues of chromium, _molybdenum_ and _tungsten_ (or wolfram), are of still rarer occurrence in nature, and form acid oxides, RO_{3}, which are still less energetic than CrO_{3}. Tungsten occurs in the somewhat rare minerals, _scheelite_, CaWO_{4}, and _wolfram_; the latter being an isomorphous mixture of the normal tungstates of iron and manganese, (MnFe)WO_{4}. Molybdenum is most frequently met with as _molybdenite_, MoS_{2}, which presents a certain resemblance to graphite in its physical properties and softness. It also occurs, but much more rarely, as a yellow lead ore, PbMoO_{4}. In both these forms molybdenum occurs in the primary rocks, in granites, gneiss, &c., and in iron and copper ores in Saxony, Sweden, and Finland. Tungsten ores are sometimes met with in considerable masses in the primary rocks of Bohemia and Saxony, and also in England, America, and the Urals. The preliminary treatment of the ore is very simple; for example, the sulphide, MoS_{2}, is roasted, and thus converted into sulphurous anhydride and molybdic anhydride, MoO_{3}, which is then dissolved in alkalis, generally in ammonia. The ammonium molybdate is then treated with acids, when the sparingly soluble molybdic acid is precipitated. Wolfram is treated in a different manner. Most frequently the finely-ground ore is repeatedly boiled with hydrochloric and nitric acids, and the resultant solutions (of salts of manganese and iron) poured off, until the dark brown mass of ore disappears, whilst the tungstic acid remains, mixed with silica, as an insoluble residue; it is treated also with ammonia, and is thus converted into soluble ammonium tungstate, which passes into solution and yields tungstic acid when treated with acids. This hydrate is then ignited, and leaves tungstic anhydride. The general character of molybdic and tungstic anhydrides is analogous to that of chromic anhydride; they are anhydrides of a feebly acid character, which easily give polyacid salts and colloid solutions.[8 bis] [8 bis] The atomic composition of the tungsten and molybdenum compounds is taken as being identical with that of the compounds of sulphur and chromium, because (1) both these metals give two oxides in which the amounts of oxygen per given amount of metal stand in the ratio 2 : 3; (2) the higher oxide is of the latter kind, and, like chromic and sulphuric anhydrides, it has an acid character; (3) certain of the molybdates are isomorphous with the sulphates; (4) the specific heat of tungsten is 0·0334, consequently the product of the atomic weight and specific heat is 6·15, like that of the other elements--it is the same with molybdenum, 96·0 × 0·0722 = 6·9; (5) tungsten forms with chlorine not only compounds WCl_{6}, WCl_{5}, and WOCl_{4}, but also WO_{2}Cl_{2}, a volatile substance the analogue of chromyl chloride, CrO_{2}Cl_{2}, and sulphuryl chloride, SO_{2}Cl_{2}. Molybdenum gives the chlorine compounds, MOCl_{2}, MOCl_{3}(?), MOCl_{4} (fuses at 194°, boils at 268°; according to Debray it contains MOCl_{5}), MoOCl_{4}, MoO_{2}Cl_{2}, and MoO_{2}(OH)Cl. The existence of tungsten hexachloride, WCl_{6}, is an excellent proof of the fact that the type SX_{6} appears in the analogues of sulphur as in SO_{3}; (6) the vapour density accurately determined for the chlorine compounds MoCl_{4}, WCl_{6}, WCl_{5}, WOCl_{4} (Roscoe) leaves no doubt as to the molecular composition of the compounds of tungsten and molybdenum, for the observed and calculated results entirely agree. Tungsten is sometimes called scheele in honour of Scheele, who discovered it in 1781 and molybdenum in 1778. Tungsten is also known as wolfram; the former name was the name given to it by Scheele, because he extracted it from the mineral then known as tungsten and now called scheelite, CaWO_{4}. The researches of Roscoe, Blomstrand and others have subsequently thrown considerable light on the whole history of the compounds of molybdenum and tungsten. The ammonium salts of tungsten and molybdic acids when ignited leave the anhydrides, which resemble each other in many respects. _Tungsten anhydride_, WO_{3}, is a yellowish substance, which only fuses at a strong heat, and has a sp. gr. of 6·8. It is insoluble both in water and acid, but solutions of the alkalis, and even of the alkali carbonates, dissolve it, especially when heated, forming alkaline salts. _Molybdic anhydride_, MoO_{3}, is obtained by igniting the acid (hydrate) or the ammonium salt, and forms a white mass which fuses at a red heat, and solidifies to a yellow crystalline mass of sp. gr. 4·4; whilst on further heating in open vessels or in a stream of air this anhydride _sublimes_ in pearly scales--this enables it to be obtained in a tolerably pure state. Water dissolves it in small quantities--namely, 1 part requires 600 parts of water for its solution. The hydrates of molybdic anhydride are _soluble also in acids_ (a hydrate, H_{2}MoO_{4}, is obtained from the nitric acid solution of the ammonium salt), which forms one of their distinctions from the tungstic acids. But after ignition molybdic anhydride is insoluble in acids, like tungstic anhydride; alkalis dissolve this anhydride, easily forming molybdates. Potassium bitartrate dissolves the anhydride with the aid of heat. None of the acids yet considered by us form so many different salts with one and the same base (alkali) as molybdic and tungstic acids. The composition of these salts, and their properties also, vary considerably. The most important discovery in this respect was made by Marguerite and Laurent, who showed that the salts which contain a large proportion of tungstic acid are easily soluble in water, and ascribed this property to the fact that tungstic acid may be obtained _in several states_. The common tungstates, obtained with an excess of alkali, have an alkaline reaction, and on the addition of sulphuric or hydrochloric acid first deposit an acid salt and then a hydrate of tungstic acid, which is insoluble both in water and acids; but if instead of sulphuric or hydrochloric acids, we add acetic or phosphoric acid, or if the tungstate be saturated with a fresh quantity of tungstic acid, which may be done by boiling the solution of the alkali salt with the precipitated tungstic acid, a solution is obtained which, on the addition of sulphuric or a similar acid, does not give a precipitate of tungstic acid at the ordinary or at higher temperatures. The solution then contains peculiar salts of tungstic acid, and if there be an excess of acid it also contains tungstic acid itself; Laurent, Riche, and others called it _metatungstic acid_, and it is still known by this name. Those salts which with acids immediately give the insoluble tungstic acid have the composition R_{2}WO_{4},RHWO_{4}, whilst those which give the soluble metatungstic acid contain a far greater proportion of the acid elements. Scheibler obtained the (soluble) metatungstic acid itself by treating the soluble barium (meta) tetratungstate, BaO,4WO_{3}, with sulphuric acid. Subsequent research showed the existence of a similar phenomenon for molybdic acid. There is no doubt that this is a case of colloidal modifications. Many chemists have worked on the various salts formed by molybdic and tungstic acids. The tungstates have been investigated by Marguerite, Laurent, Marignac, Riche, Scheibler, Anthon, and others. The molybdates were partially studied by the same chemists, but chiefly by Struvé and Svanberg, Delafontaine, and others. It appears that for a given amount of base the salts contain one to eight equivalents of molybdic or tungstic anhydride; _i.e._ if the base have the composition RO, then the highest proportion of base will be contained by the salts of the composition ROWO_{3} or ROMoO_{3}--that is, by those salts which correspond with the normal acids H_{2}WO_{4} and H_{2}MoO_{4}, of the same nature as sulphuric acid; but there also exist salts of the composition RO,2WO_{3}, RO,3WO_{3} ... RO,8WO_{3}. The water contained in the composition of many of the acid salts is often not taken into account in the above. The properties of the salts holding different proportions of acids vary considerably, but one salt may be converted into another by the addition of acid or base with great facility, and the greater the proportion of the elements of the acid in a salt, the more stable, within a certain limit, is its solution and the salt itself. The most common ammonium molybdate has the composition (NH_{4}HO)_{6},H_{2}O,7MoO_{3} (or, according to Marignac and others, NH_{4}HMoO_{4}), and is prepared by evaporating an ammoniacal solution of molybdic acid. It is used in the laboratory for precipitating phosphoric acid, and is purified for this purpose by mixing its solution with a small quantity of magnesium nitrate, in order to precipitate any phosphoric acid present, filtering, and then adding nitric acid and evaporating to dryness. A pure ammonium molybdate free from phosphoric acid may then be extracted from the residue. Phosphoric acid forms insoluble compounds with the oxides of uranium and iron, tin, bismuth, &c., having feeble basic and even acid properties. This perhaps depends on the fact that the atoms of hydrogen in phosphoric acid are of a very different character, as we saw above. Those atoms of hydrogen which are replaced with difficulty by ammonium, sodium, &c., are probably easily replaced by feebly energetic acid groups--that is, the formation of particular complex substances may be expected to take place at the expense of these atoms of the hydrogen of phosphoric acid and of certain feeble metallic acids; and these substances will still be acids, because the hydrogen of the phosphoric acids and metallic acids, which is easily replaced by metals, is not removed by their mutual combination, but remains in the resultant compound. Such a conclusion is verified in the _phosphomolybdic acids_ obtained (1888) by Debray. If a solution of ammonium molybdate be acidified, and a small amount of a solution (it may be acid) containing orthophosphoric acid or its salts be added to it (so that there are at least 40 parts of molybdic acid present to 1 part of phosphoric acid), then after a period of twenty-four hours the whole of the phosphoric acid is separated as a yellow precipitate, containing, however, not more than 3 to 4 p.c. of phosphoric anhydride, about 3 p.c. of ammonia, about 90 p.c. of molybdic anhydride, and about 4 p.c. of water. The formation of this precipitate is so distinct and so complete that this method is employed for the discovery and separation of the smallest quantities of phosphoric acid. Phosphoric acid was found to be present in the majority of rocks by this means. The precipitate is soluble in ammonia and its salts, in alkalis and phosphates, but is perfectly insoluble in nitric, sulphuric, and hydrochloric acids in the presence of ammonium molybdate. The composition of the precipitate appears to vary under the conditions of its precipitation, but its nature became clear when the acid corresponding with it was obtained. If the above-described yellow precipitate be boiled in aqua regia, the ammonia is destroyed, and an acid is obtained in solution, which, when evaporated in the air, crystallises out in yellow oblique prisms of approximately the composition P_{2}O_{5},20MoO_{3},26H_{2}O. Such an unusual proportion of component parts is explained by the above-mentioned considerations. We saw above that molybdic acid easily gives salts R_{2}O_n_MoO_{3}_m_H_{2}O, which we may imagine to correspond to a hydrate MoO_{2}(HO)_{2}_n_Mo_{3}_m_H_{2}O. And suppose that such a hydrate reacts on orthophosphoric acid, forming water and compounds of the composition MoO_{2}(HPO_{4})_n_MoO_{3}_m_H_{2}O or MoO_{3}(H_{2}PO_{4})_{2}_n_MoO_{3}_m_H_{2}O; this is actually the composition of phosphomolybdic acid. Probably it contains a portion of the hydrogen replaceable by metals of both the acids H_{3}PO_{4} and of H_{2}MoO_{4}. The crystalline acid above is probably H_{3}MoPO_{7},9MoO_{3},12H_{2}O. This acid is really tribasic, because its aqueous solution precipitates salts of potassium, ammonium, rubidium (but not lithium and sodium) _from acid solutions_, and gives a _yellow_ precipitate of the composition R_{3}MoPO_{7},9MoO_{3},8H_{2}O, where R = NH_{4}. Besides these, salts of another composition may be obtained, as would be expected from the preceding. These salts are only stable in acid solutions (which is naturally due to their containing an excess of acid oxides), whilst under the action of alkalis they give _colourless_ phosphomolybdates of the composition R_{3}MoPO_{3},MoO_{2},3H_{2}O. The corresponding salts of potassium, silver, ammonium, are easily soluble in water and crystalline. Phosphomolybdic acid is an example of the _complex inorganic acids_ first obtained by Marignac and afterwards generalised and studied in detail by Gibbs. We shall afterwards meet with several examples of such acids, and we will now turn attention to the fact that they are usually formed by weak polybasic acids (boric, silicic, molybdic, &c.), and in certain respects resemble the cobaltic and such similar complex compounds, with which we shall become acquainted in the following chapter. As an example we will here mention certain complex compounds containing molybdic and tungstic acids, as they will illustrate the possibility of a considerable complexity in the composition of salts. The action of ammonium molybdate upon a dilute solution of purpureocobaltic salts (_see_ Chapter XXII.) acidulated with acetic acid gives a salt which after drying at 100° has the composition Co_{2}O_{3}10NH_{3}7MoO_{3}3H_{2}O. After ignition this salt leaves a residue having the composition 2CoO_{7}MoO_{3}. An analogous compound is also obtained for tungstic acid, having the composition Co_{2}O_{3}10NH_{3}10WO_{3}9H_{2}O. In this case after ignition there remains a salt of the composition CoO_{5}WO_{3} (Carnot, 1889). Professor Kournakoff, by treating a solution of potassium and sodium molybdates, containing a certain amount of suboxide of cobalt, with bromine obtained salts having the composition: 3K_{2}OCo_{2}O_{3}12MoO_{3}20H_{2}O (light green) and 3K_{2}OCo_{2}O_{3}10Mo_{3}10H_{2}O (dark green). Péchard (1893) obtained salts of the four complex phosphotungstic acids by evaporating equivalent mixtures of solutions of phosphoric acid and metatungstic acid (_see_ further on): phosphotrimetatungstic acid P_{2}O_{5}12WO_{3}48H_{2}O, phosphotetrametatungstic acid P_{2}O_{5}16WO_{3}69H_{2}O, phosphopentametatungstic acid P_{2}O_{5}20WO_{3}H_{2}O, and phosphohexametatungstic acid P_{2}O_{5}24WO_{3}59H_{2}O. Kehrmann and Frankel described still more complex salts, such as: 3Ag_{2}O_{4}BaOP_{2}O_{5}22WO_{3}H_{2}O,5BaO_{2} K_{2}OP_{2}O_{3}22WO_{3}48H_{2}O. Analogous double salts with 22WO_{3} were also obtained with KSr, KHg, BaHg, and NH_{4}Pb. Kehrmann (1892) considers the possibility of obtaining an unlimited number of such salts to be a general characteristic of such compounds. Mahom and Friedheim (1892) obtained compounds of similar complexity for molybdic and arsenic acids. For tungstic acid there are known: (1) Normal salts--for example, K_{2}WO_{4}; (2) the so-called acid salts have a composition like 3K_{2}O,7WO_{3},6H_{2}O or K_{6}H_{8}(WO_{4})_{7},2H_{2}O; (3) the tritungstates like Na_{3}O,3WO_{3},3H_{2}O = Na_{2}H_{4}(WO_{4})_{3},H_{2}O. All these three classes of salts are soluble in water, but are precipitated by barium chloride, and with acids in solution give an insoluble hydrate of tungstic acid; whilst those salts which are enumerated below do not give a precipitate either with acids or with the salts of the heavy metals, because they form soluble salts even with barium and lead. They are generally called metatungstates. They all contain water and a larger proportion of acid elements than the preceding salts; (4) the tetratungstates, like Na_{2}O,4WO_{3},10H_{2}O and BaO,4WO_{3},9H_{2}O for example; (5) the octatungstates--for example, Na_{2}O,8WO_{3},24H_{2}O. Since the metatungstates lose so much water at 100° that they leave salts whose composition corresponds with an acid, 3H_{2}O,4WO_{3}--that is, H_{6}W_{4}O_{15}--whilst in the meta salts only 2 hydrogens are replaced by metals, it is assumed, although without much ground, that these salts contain a particular soluble metatungstic acid of the composition H_{6}W_{4}O_{15}. As an example we will give a short description of the sodium salts. The normal salt, Na_{2}WO_{4}, is obtained by heating a strong solution of sodium carbonate with tungstic acid to a temperature of 80°; if the solution be filtered hot, it crystallises in rhombic tabular crystals, having the composition Na_{2}WO_{4},2H_{2}O, which remain unchanged in the air and are easily soluble in water. When this salt is fused with a fresh quantity of tungstic acid, it gives a ditungstate, which is soluble in water and separates from its solution in crystals containing water. The same salt is obtained by carefully adding hydrochloric acid to the solution of the normal salt so long as a precipitate does not appear, and the liquid still has an alkaline reaction. This salt was first supposed to have the composition Na_{2}W_{2}O_{7},4H_{2}O, but it has since been found to contain (at 100°) Na_{6}W_{7}O_{24},16H_{2}O--that is, it corresponds with the similar salt of molybdic acid. (If this salt be heated to a red heat in a stream of hydrogen, it loses a portion of its oxygen, acquires a metallic lustre, and turns a golden yellow colour, and, after being treated with water, alkali, and acid, leaves golden yellow leaflets and cubes which are very like gold. This very remarkable substance, discovered by Wöhler, has, according to Malaguti's analysis, the composition Na_{2}W_{3}O_{9}; that is, it, as it were, contains a double tungstate of tungsten oxide, WO_{2}, and of sodium, Na_{2}WO_{4},WO_{2}WO_{3}. The decomposition of the fused sodium salt is best effected by finely-divided tin. This substance has a sp. gr. 6·6; it conducts electricity like metals, and like them has a metallic lustre. When brought into contact with zinc and sulphuric acid it disengages hydrogen, and it becomes covered with a coating of copper in a solution of copper sulphate in the presence of zinc--that is, notwithstanding its complex composition it presents to a certain extent the appearance and reactions of the metals. It is not acted on by aqua regia or alkaline solutions, but it is oxidised when ignited in air.) The ditungstate mentioned above, deprived of water (having undergone a modification similar to that of metaphosphoric acid), after being treated with water, leaves an anhydrous, sparingly soluble tetratungstate, Na_{2}WO_{4},3WO_{3}, which, when heated at 120° in a closed tube with water, passes into an easily soluble metatungstate. It may therefore be said that the metatungstates are hydrated compounds. On boiling a solution of the above-mentioned salts of sodium with the yellow hydrate of tungstic acid they give a solution of metatungstate, which is the hydrated tetratungstate. Its crystals contain Na_{2}W_{4}O_{13},10H_{2}O. After the hydrate of tungstic acid (obtained from the ordinary tungstates by precipitation with an acid) has stood a long time in contact with a solution (hot or cold) of sodium tungstate, it gives a solution which is not precipitated by hydrochloric acid; this must be filtered and evaporated over sulphuric acid in a desiccator (it is decomposed by boiling). It first forms a very dense solution (aluminium floats in it) of sp. gr. 3·0, and octahedral crystals of _sodium metatungstate_, Na_{2}W_{4}O_{13},10H_{2}O, sp. gr. 3·85, then separate. It effloresces and loses water, and at 100° only two out of the ten equivalents of water remain, but the properties of the salt remain unaltered. If the salt be deprived of water by further heating, it becomes insoluble. At the ordinary temperature one part of water dissolves ten parts of the metatungstate. The other metatungstates are easily obtained from this salt. Thus a strong and hot solution, mixed with a like solution of barium chloride, gives on cooling crystals of barium metatungstate, BaW_{4}O_{13},9H_{2}O. These crystals are dissolved without change in water containing hydrochloric acid, and also in hot water, but they are partially decomposed by cold water, with the formation of a solution of metatungstic acid and of the normal barium salt BaWO_{4}. In order to explain the difference in the properties of the salts of tungstic acid, we may add that a mixture of a solution of tungstic acid with a solution of silicic acid does not coagulate when heated, although the silicic acid alone would do so; this is due to the formation of a silicotungstic acid, discovered by Marignac, which presents a fresh example of a complex acid. A solution of a tungstate dissolves gelatinous silica, just as it does gelatinous tungstic acid, and when evaporated deposits a crystalline salt of silicotungstic acid. This solution is not precipitated either by acids (a clear analogy to the metatungstates) or by sulphuretted hydrogen, and corresponds with a series of salts. These salts contain one equivalent of silica and 8 equivalents of hydrogen or metals, in the same form as in salts, to 12 or 10 equivalents of tungstic anhydride; for example the crystalline potassium salt has the composition K_{8}W_{12}SiO_{42},14H_{2}O = 4K_{2}O,12WO_{3},SiO_{2},14H_{2}O. Acid salts are also known in which half of the metal is replaced by hydrogen. The complexity of the composition of such complex acids (for example, of the phosphomolybdic acid) involuntarily leads to the idea of polymerisation, which we were obliged to recognise for silica, lead oxide, and other compounds. This polymerisation, it seems to me, may be understood thus: a hydrate A (for example, tungstic acid) is capable of combining with a hydrate B (for example, silica or phosphoric acid, with or without the disengagement of water), and by reason of this faculty it is capable of polymerisation--that is, A combines with A--combines with itself--just as aldehyde, C_{2}H_{4}O, or the cyanogen compounds are able to combine with hydrogen, oxygen, &c., and are liable to polymerisation. On this view the molecule of tungstic acid is probably much more complex than we represent it; this agrees with the easy volatility of such compounds as the chloranhydrides, CrO_{2}Cl_{2}, MoO_{2}Cl_{2}, the analogues of the volatile sulphuryl chloride, SO_{2}Cl_{2}, and with the non-volatility, or difficult volatility, of chromic and molybdic anhydrides, the analogues of the volatile sulphuric anhydride. Such a view also finds a certain confirmation in the researches made by Graham on the _colloidal_ state of tungstic acid, because colloidal properties only appertain to compounds of a very complex composition. The observations made by Graham on the colloidal state of tungstic and molybdic acids introduced much new matter into the history of these substances. When sodium tungstate, mixed in a dilute solution with an equivalent quantity of dilute hydrochloric acid, is placed in a dialyser, hydrochloric acid and sodium chloride pass through the membrane, and a solution of tungstic acid remains in the dialyser. Out of 100 parts of tungstic acid about 80 parts remain in the dialyser. The solution has a bitter, astringent taste, and does not yield gelatinous tungstic acid (hydrogel) either when heated or on the addition of acids or salts. It may also be evaporated to dryness; it then forms a vitreous mass of the _hydrosol_ of _tungstic acid_, which adheres strongly to the walls of the vessel in which it has been evaporated, and is perfectly soluble in water. It does not even lose its solubility after having been heated to 200°, and only becomes insoluble when heated to a red heat, when it loses about 2-1/2 p.c. of water. The dry acid, dissolved in a small quantity of water, forms a gluey mass, just like gum arabic, which is one of the representatives of the hydrosols of colloidal substances. The solution, containing 5 p.c of the anhydride, has a sp. gr. of 1·047; with 20 p.c., of 1·217; with 50 p.c., of 1·80; and with 80 p.c., of 3·24. The presence of a polymerised trioxide in the form of hydrate, H_{2}OW_{3}O_{9} or H_{2}O_{4}WO_{3}, must then be recognised in the solution: this is confirmed by Sabaneeff's cryoscopic determinations (1889). A similar stable solution of molybdic acid is obtained by the dialysis of a mixture of a strong solution of sodium molybdate with hydrochloric acid (the precipitate which is formed is re-dissolved). If MoCl_{4} be precipitated by ammonia and washed with water, a point is reached at which perfect solution takes place, and the molybdic acid forms a colloid solution which is precipitated by the addition of ammonia (Muthmann). The addition of alkali to the solutions of the hydrosols of tungstic and molybdic acids immediately results in the re-formation of the ordinary tungstates and molybdates. There appears to be no doubt but that the same transformation is accomplished in the passage of the ordinary tungstates into the metatungstates as takes place in the passage of tungstic acid itself from an insoluble into a soluble state; but this may be even actually proved to be the case, because Scheibler obtained a solution of tungstic acid, before Graham, by decomposing barium metatungstate (BaO_{4}WO_{3},9H_{2}O) with sulphuric acid. By treating this salt with sulphuric acid in the amount required for the precipitation of the baryta, Scheibler obtained a solution of metatungstic acid which, when containing 43·75 p.c. of acid, had a sp. gr. of 1·634, and with 27·61 p.c. a sp. gr. of 1·327--that is, specific gravities corresponding with those found by Graham. Péchard found that as much heat is evolved by neutralising metatungstic acid as with sulphuric acid. Questions connected with the metamorphoses or modifications of tungstic and molybdic acids, and the polymerisation and colloidal state of substances, as well as the formation of complex acids, belong to that class of problems the solution of which will do much towards attaining a true comprehension of the mechanism of a number of chemical reactions. I think, moreover, that questions of this kind stand in intimate connection with the theory of the formation of solutions and alloys and other so-called indefinite compounds. Hydrogen (which does not directly form compounds with Cr, Mo, and W) reduces molybdic and tungstic anhydride at a red heat; and this forms the means of obtaining metallic molybdenum and tungsten. _Both metals_ are infusible, and both under the action of heat form compounds with carbon and iron (the addition of tungsten to steel renders the latter ductile and hard).[9] Molybdenum forms a grey powder, which scarcely aggregates under a most powerful heat, and has a specific gravity of 8·5. It is not acted on by the air at the ordinary temperature, but when ignited it is first converted into a brown, and then into a blue oxide, and lastly into molybdic anhydride. Acids do not act on it--that is, it does not liberate hydrogen from them, not even from hydrochloric acid--but strong sulphuric acid disengages sulphurous anhydride, forming a brown mass, containing a lower oxide of molybdenum. Alkalis in solution do not act on molybdenum, but when fused with it hydrogen is given off, which shows, as does its whole character, the acid properties of the metal. The properties of tungsten are almost identical; it is infusible, has an iron-grey colour, is exceedingly hard, so that it even scratches glass. Its specific gravity is 19·1 (according to Roscoe), so that, like uranium, platinum, &c., it is one of the heaviest metals.[9 bis] Just as sulphur and chromium have their corresponding persulphuric and perchromic acids, H_{2}S_{2}O_{8} and H_{2}CrO_{8}, having the properties of peroxides, and corresponding to peroxide of hydrogen, so also molybdenum and tungsten are known to give _permolybdic_ and _pertungstic_ acids, H_{2}Mo_{2}O_{8} and H_{2}W_{2}O_{8}, which have the properties of true peroxides, _i.e._ easily disengage iodine from KI and chlorine from HCl, easily part with their oxygen, and are formed by the action of peroxide of hydrogen, into which they are readily reconverted (hence they may be regarded as compounds of H_{2}O_{2} with 2MoO_{3} and 2WO_{3}), &c. Their formation (Boerwald 1884, Kemmerer 1891) is at once seen in the coloration (not destroyed by boiling), which is obtained on mixing a solution of the salts with peroxide of hydrogen, and on treating, for instance, molybdic acid with a solution of peroxide of hydrogen (Péchard 1892). The acid then forms an orange-coloured solution, which after evaporation in vacuo leaves Mo_{2}H_{2}O_{8}4H_{2}O as a crystalline powder, and loses 4H_{2}O at 100°, beyond which it decomposes with the evolution of oxygen.[9 tri] [9] Moissan (1893) studied the compounds of Mo and W formed with carbon in the electrical furnace (they are extremely hard) from a mixture of the anhydrides and carbon. Poleck and Grützner obtained definite compounds FeW_{2} and FeW_{2}C_{3} for tungsten. Metallic W and Mo displace Ag from its solutions but not Pb. There is reason for believing that the sp. gr. of pure molybdenum is higher than that (8·5) generally ascribed to it. [9 bis] We may conclude our description of tungsten and molybdenum by stating that their sulphur compounds have an acid character, like carbon bisulphide or stannic sulphide. If sulphuretted hydrogen be passed through a solution of a molybdate it does not give a precipitate unless sulphuric acid be present, when a dark brown precipitate of _molybdenum trisulphide_, MoS_{3}, is formed. When this sulphide is ignited without access of air it gives the bisulphide MoS_{2}; the latter is not able to combine with potassium sulphide like the trisulphide MoS_{3}, which forms a salt, K_{2}MoS_{4}, corresponding with K_{2}MoO_{4}. This is soluble in water, and separates out from its solution in red crystals, which have a metallic lustre and reflect a green light. It is easily obtained by heating the native bisulphide, MoS_{2}, with potash, sulphur, and a small amount of charcoal, which serves for deoxidising the oxygen compounds. Tungsten gives similar compounds, R_{2}WS_{4}, where R = NH_{4}, K, Na. They are decomposed by acids, with the separation of tungsten trisulphide, WS_{3}, and molybdenum trisulphide, MoS_{3}. Rideal (1892) obtained W_{2}N_{3} by heating WO_{3} in NH_{3}. This compound exhibited the general properties of metallic nitrides. [9 tri] When peroxide of hydrogen acts upon a solution of potassium molybdate well-formed yellow crystals belonging to the triclinic system separate out in the cold. When these crystals are heated in vacuo they first lose water and then decompose, leaving a residue composed of the salt originally taken. They are soluble in water but insoluble in alcohol. Their composition is represented by the formula K_{2}Mo_{2}O_{8}2H_{2}O. An ammonium salt is obtained by evaporating peroxide of hydrogen with ammonium molybdate. The following salts have also been obtained by the action of peroxide of hydrogen upon the corresponding molybdates: Na_{2}Mo_{2}O_{6}6H_{2}O--in yellow prismatic crystals; MgMo_{2}O_{8}10H_{2}O--stellar needles; BaMoO_{8}2H_{2}O--in microscopic yellow octahedra. A corresponding sodium pertungstate has been obtained by Péchard by boiling sodium tungstate with a solution of peroxide of hydrogen for several minutes. The solution rapidly turns yellow, and no longer gives a precipitate of tungstic anhydride when treated with nitric acid. When evaporated in vacuo the solution leaves a thick syrupy liquid from which ray-like crystals separate out; these crystals are more soluble in water than the salt originally taken. When heated they also lose water and oxygen. Their composition answers to the formula M_{2}W_{2}O_{8}2H_{2}O, where M = Na, NH_{4}, &c. The permolybdates and pertungstates have similar properties. When treated with oxygen acids they give peroxide of hydrogen, and disengage chlorine and iodine from hydrochloric acid and potassium iodide. Piccini (1891) showed that peroxide of hydrogen not only combines with the oxygen compounds of Mo and W, but also with their fluo-compounds, among which ammonium fluo-molybdate MoO_{2}F_{2}2NH_{4} and others have long been known. (A few new salts of similar composition have been obtained by F. Moureu in 1893.) The action of peroxide of hydrogen upon these compounds gives salts containing a larger amount of oxygen; for instance, a solution of MoO_{2}F_{2}2KFH_{2}O with peroxide of hydrogen gives a yellow solution which after cooling separates out yellow crystalline flakes of MoO_{3}F_{2}2KFH_{2}O, resembling the salt originally taken in their external appearance. By employing a similar method Piccini also obtained: MoO_{3}F_{2}2RbFH_{2}O--yellow monoclinic crystals; MoO_{3}F_{2},2CsFH_{2}O,--yellow flakes, and the corresponding tungstic compounds. All these salts react like peroxide of hydrogen. In speaking of these compounds I for my part think it may be well to call attention to the fact that, in the first place, the composition of Piccini's oxy-fluo compounds does not correspond to that of permolybdic and pertungstic acid. If the latter be expressed by formulæ with one equivalent of an element, they will be HMoO_{4} and HWO_{4}, and the oxy-fluo form corresponding to them should have the composition MoO_{3}F and WO_{3}F while it contains MO_{3}F_{2} and WO_{3}F_{2}, _i.e._ answers as it were to a higher degree of oxidation, MoH_{2}O_{3} and W_{3}HO_{3}. But if permolybdic acid be regarded as 2MoO_{3} + H_{2}O_{2}, _i.e._ as containing the elements of peroxide of hydrogen, then Piccini's compound will also be found to contain the original salts + H_{2}O; for example, from MoO_{2}F_{2}2KFH_{2}O there is obtained a compound MoO_{2}F_{2}2KFH_{2}O_{2}, _i.e._ instead of H_{2}O they contain H_{2}O_{2}. In the second place the capacity of the salts of molybdenum and tungsten to retain a further amount of oxygen or H_{2}O_{2} probably bears some relation to their property of giving complex acids and of polymerising which has been considered in Note 8 bis. There is, however, a great chemical interest in the accumulation of data respecting these high peroxide compounds corresponding to molybdic and tungstic acids. With regard to the peroxide form of uranium, _see_ Chapter XX., Note 66. _Uranium_, U = 240, has the highest atomic weight of all the analogues of chromium, and indeed of all the elements yet known. Its highest salt-forming oxide, UO_{3}, shows very feeble acid properties. Although it gives sparingly-soluble yellow compounds with alkalis, which fully correspond with the dichromates--for example, Na_{2}U_{2}O_{7} = Na_{2}O,2UO_{3},[10]--yet it more frequently and easily reacts with acids, HX, forming fluorescent yellowish-green salts of the composition UO_{2}X_{2}, and in this respect uranic trioxide, UO_{3}, differs from chromic anhydride, CrO_{3}, although the latter is able to give the oxychloride, CrO_{2}Cl_{2}. In molybdenum and tungsten, however, we see a clear transition from chromium to uranium. Thus, for example, chromyl chloride, CrO_{2}Cl_{2}, is a brown liquid which volatilises without change, and is completely decomposed by water; molybdenum oxychloride, MoO_{2}Cl_{2}, is a crystalline substance of a yellow colour, which is volatile and soluble in water (Blomstrand), like many salts. Tungsten oxychloride, WO_{2}Cl_{2}, stands still nearer to uranyl chloride in its properties; it forms yellow scales on which water and alkalis act, as they do on many salts (zinc chloride, ferric chloride, aluminium chloride, stannic chloride, &c.), and perfectly corresponds with the difficultly volatile salt, UO_{2}Cl_{2} (obtained by Peligot by the action of chlorine on ignited uranium dioxide, UO_{2}), which is also yellow and gives a yellow solution with water, like all the salts UO_{2}X_{2}. The property of uranic oxide, UO_{3}, of forming salts UO_{2}X_{2} is shown in the fact that the hydrated oxide of uranium, UO_{2}(HO)_{2}, which is obtained from the nitrate, carbonate, and other salts by the loss of the elements of the acid, is easily soluble in acids, as well as in the fact that the lower grades of oxidation of uranium are able, when treated with nitric acid, to form an easily crystallisable uranyl nitrate, UO_{2}(NO_{3})_{2},6H_{2}O; this is the most commonly occurring uranium salt.[11] [10] Uranium trioxide, or uranic oxide, shows its feeble basic and acid properties in a great number of its reactions. (1) Solutions of uranic salts give yellow precipitates with alkalis, but these precipitates do not contain the hydrate of the oxide, but compounds of it with bases; for example, 2UO_{2}(NO_{3})_{2} + 6KHO = 4KNO_{3} + 3H_{2}O + K_{2}U_{2}O_{7}. There are other _urano-alkali compounds_ of the same constitution; for example, (NH_{4})_{2}U_{2}O_{7} (known commercially as uranic oxide), MgU_{2}O_{7}, BaU_{2}O_{7}. They are the analogues of the dichromates. Sodium uranate is the most generally used under the name of uranium yellow, Na_{2}U_{2}O_{7}. It is used for imparting the characteristic yellow-green tint to glass and porcelain. Neither heat nor water nor acids are able to extract the alkali from sodium uranate, Na_{2}U_{2}O_{7}, and therefore it is a true insoluble salt, of a yellow colour, and clearly indicates the acid character (although feeble) of uranic oxide. (2) The carbonates of the alkaline earths (for instance, barium carbonate) precipitate uranic oxide from its salts, as they do all the salts of feeble bases; for example, R_{2}O_{3}. (3) The _alkaline carbonates_, when added to solutions of uranic salts, give a _precipitate, which is soluble in_ _an excess of the reagent_, and particularly so if the acid carbonates be taken. This is due to the fact that (4) the uranyl salts _easily form double salts_ with the salts of the alkali metals, including the salts of ammonium. Uranium, in the form of these double salts, often gives salts of well-defined crystalline form, although the simple salts are little prone to appear in crystals. Such, for example, are the salts obtained by dissolving potassium uranate, K_{2}U_{2}O_{7}, in acids, with the addition of potassium salts of the same acids. Thus, with hydrochloric acid and potassium chloride a well-formed crystalline salt, K_{2}(UO_{2})Cl_{4},2H_{2}O, belonging to the monoclinic system, is produced. This salt decomposes in dissolving in pure water. Among these double salts we may mention the double carbonate with the alkalis, R_{4}(UO_{2})(CO_{3})_{3} (equal to 2R_{2}CO_{3} + UO_{2}CO_{3}); the acetates, R(UO_{2})(C_{2}H_{3}O_{2})_{3}--for instance, the sodium salt, Na(UO_{2})(C_{2}H_{3}O_{2})_{3}, and the potassium salt, K(UO_{2})(C_{2}H_{3}O_{2})_{3},H_{2}O; the sulphates, R_{2}(UO_{2})(SO_{4})_{3},2H_{2}O, &c. In the preceding formula R = K, Na, NH_{4}, or R_{2} = Mg, Ba, &c. _This property of giving comparatively stable double salts indicates feebly developed basic properties_, because double salts are mainly formed by salts of distinctly basic metals (these form, as it were, the basic element of a double salt) and salts of feebly energetic bases (these form the acid element of a double salt), just as the former also give acid salts; the acid of the acid salts is replaced in the double salts by the salt of the feebly energetic base, which, like water, belongs to the class of intermediate bases. For this reason barium does not give double salts with alkalis as magnesium does, and this is why double salts are more easily formed by potassium than by lithium in the series of the alkali metals. (5) The most remarkable property, proving the feeble energy of uranic oxide as a base, is seen in the fact that when their composition is compared with that of other salts those of uranic oxide _always appear as basic salts_. It is well known that a normal salt, R_{2}X_{6}, corresponds with the oxide R_{2}O_{3}, where X = Cl, NO_{3}, &c., or X_{2} = SO_{4}, CO_{3}, &c.; but there also exist basic salts of the same type where X = HO or X_{2} = O. We saw salts of all kinds among the salts of aluminium, chromium, and others. With uranic oxide no salts are known of the types UX_{6} (UCl_{6}, U(SO_{4})_{3}, alums, &c., are not known), nor even salts, U(HO)_{2}X_{4} or UOX_{4}, but it always forms salts of the type U(HO)_{4}X_{2}, or UO_{2}X_{2}. Judging from the fact that nearly all the salts of uranic oxide retain water in crystallising from their solutions, and that this water is difficult to separate from them, it may be thought to be water of hydration. This is seen in part from the fact that the composition of many of the salts of uranic oxide may then be expressed without the presence of water of crystallisation; for instance, U(HO)_{4}K_{2}Cl_{4} (and the salt of NH_{4}, U(HO)_{4}K_{2}(SO_{4})_{2}, U(HO)_{4}(C_{2}H_{3}O_{2})_{2}. Sodium uranyl acetate however does not contain water. [11] _Uranyl nitrate_, or uranium nitrate, UO_{2}(NO_{3})_{2},6H_{2}O, crystallises from its solutions in transparent yellowish-green prisms (from an acid solution), or in tabular crystals (from a neutral solution), which effloresce in the air and are easily soluble in water, alcohol, and ether, have a sp. gr. of 2·8, and fuse when heated, losing nitric acid and water in the process. If the salt itself (Berzelius) or its alcoholic solution (Malaguti) be heated up to the temperature at which oxides of nitrogen are evolved, there then remains a mass which, after being evaporated with water, leaves uranyl hydroxide, UO_{2}(HO)_{2} (sp. gr. 5·93), whilst if the salt be ignited there remains the dioxide, UO_{2}, as a brick-red powder, which on further heating loses oxygen and forms the dark olive uranoso-uranic oxide, U_{3}O_{8}. The solution of the nitrate obtained from the ore is purified in the following manner: sulphurous anhydride is first passed through it in order to reduce the arsenic acid present into arsenious acid; the solution is then heated to 60°, and sulphuretted hydrogen passed through it; this precipitates the lead, arsenic, and tin, and certain other metals, as sulphides, insoluble in water and dilute nitric acid. This liquid is then filtered and evaporated with nitric acid to crystallisation, and the crystals are dissolved in ether. Or else the solution is first treated with chlorine in order to convert the ferrous chloride (produced by the action of the hydrogen sulphide) into ferric chloride, the oxides are then precipitated by ammonia, and the resultant precipitate, containing the oxides Fe_{2}O_{3}, UO_{3}, and compounds of the latter with potash, lime, ammonia, and other bases present in the solution (the latter being due to the property of uranic oxide of combining with bases), is washed and dissolved in a strong, slightly-heated solution of ammonium carbonate, which dissolves the uranic oxide but not the ferric oxide. The solution is filtered, and on cooling deposits a well-crystallising _uranyl ammonium carbonate_, UO_{2}(NH_{4})_{4}(CO_{3})_{3}, in brilliant monoclinic crystals which on exposure to air slowly give off water, carbonic anhydride, and ammonia; the same decomposition is readily effected at 300°, the residue then consisting of uranic oxide. This salt is not very soluble in water, but is readily so in ammonium carbonate; it is obvious that it may readily be converted into all the other salts of oxides of uranium. Uranium salts are also purified in the form of _acetate_, which is very sparingly soluble, and is therefore directly precipitated from a strong solution of the nitrate by mixing it with acetic acid. We may also mention the _uranyl phosphate_, HUPO_{6}, which must be regarded as an orthophosphate in which two hydrogens are replaced by the radicle uranyl, UO_{2}, _i.e._ as H(UO_{2})PO_{4}. This salt is formed as a hydrated gelatinous yellow precipitate, on mixing a solution of uranyl nitrate with disodium phosphate. The precipitation occurs in the presence of acetic acid, but not in the presence of hydrochloric acid. If moreover an excess of an ammonium salt be present, the ammonia enters into the composition of the bright yellow gelatinous precipitate formed, in the proportion UO_{2}NH_{4}PO_{4}. This precipitate is not soluble in water and acetic acid, and its solution in inorganic acids when boiled entirely expels all the phosphoric acid. This fact is taken advantage of for removing phosphoric acids from solutions--for instance, from those containing salts of calcium and magnesium. _Uranium_, which gives an oxide, UO_{3}, and the corresponding salt UO_{2}X_{2} and dioxide UO_{2}, to which the salts UX_{4} correspond, is rarely met with in nature. Uranite or the double orthophosphate of uranic oxide, R(UO_{2})H_{2}P_{2}O_{8},7H_{2}O, where R = Cu or Ca, uranium-vitriol U(SO_{4})_{2},H_{2}O, samarakite, and æschynite, are very rarely found, and then only in small quantities. Of more frequent and abundant occurrence is the non-crystalline, earthy brown uranium ore known as _pitchblende_ (sp. gr. 7·2), which is mainly composed of the intermediate oxide, U_{3}O_{8} = UO_{2},2UO_{3}. This ore is found at Joachimsthal in Bohemia and in Cornwall. It usually contains a number of different impurities, chiefly sulphides and arsenides of lead and iron, as well as lime and silica compounds. In order to expel the arsenic and sulphur it is roasted, ground, washed with dilute hydrochloric acid, which does not dissolve the uranoso-uranic oxide, U_{3}O_{8}, and the residue is dissolved in nitric acid, which transforms the uranium oxide into the nitrate, UO_{2}(NO_{3})_{2}. It must be observed that the oxide of uranium, first distinguished by Klaproth (1789), was for a long time regarded as able to give metallic uranium under the action of charcoal and other reducing agents (with the aid of heat). But the substance thus obtained was only the _uranium dioxide_, UO_{2}. The compound nature of this dioxide,[12] or the presence of oxygen in it, was demonstrated by Peligot (1841), by igniting it with charcoal in a stream of chlorine. He thus obtained a volatile _uranium tetrachloride_, UCl_{4},[13] which, when heated with sodium, gave _metallic uranium_ as a grey metal, having a specific gravity of 18·7, and liberating hydrogen from acids, with the formation of green uranous salts, UX_{4}, which act as powerful reducing agents.[14] [12] Uranium dioxide, or _uranyl_, UO_{2}, which is contained in the salts UO_{2}X_{2}, has the appearance and many of the properties of a metal. Uranic oxide may be regarded as uranyl oxide, (UO_{2})O, its salts as salts of this uranyl; its hydroxide, (UO_{2})H_{2}O_{2}, is constituted like CaH_{2}O_{2}. The green oxide of uranium, uranoso-uranic oxide (easily formed from uranic salts by the loss of oxygen), U_{3}O_{8} = UO_{2},2UO_{3}, when ignited with charcoal or hydrogen (dry) gives a brilliant crystalline substance of sp. gr. about 11·0 (Urlaub), whose appearance resembles that of metals, and decomposes steam at a red heat with the evolution of hydrogen; it does not, however, decompose hydrochloric or sulphuric acid, but is oxidised by nitric acid. The same substance (i.e. uranium dioxide UO_{2}) is also obtained by igniting the compound (UO_{2})K_{2}Cl_{4} in a stream of hydrogen, according to the equation UO_{2}K_{4}Cl_{4} + H_{2} = UO_{2} + 2HCl + 2KCl. It was at first regarded as the metal. In 1841 Peligot found that it contained oxygen, because carbonic oxide and anhydride were evolved when it was ignited with charcoal in a stream of chlorine, and from 272 parts of the substance which was considered to be metal he obtained 382 parts of a volatile product containing 142 parts of chlorine. From this it was concluded that the substance taken contained an equivalent amount of oxygen. As 142 parts of chlorine correspond with 32 parts of oxygen, it followed that 272 - 32 = 240 parts of metal were combined in the substance with 32 parts of oxygen, and also in the chlorine compound obtained with 142 parts of chlorine. These calculations have been made for the now accepted atomic weight of uranium (U = 240, _see_ Note 14). Peligot took another atomic weight, but this does not alter the principle of the argument. [13] _Uranium tetrachloride_, uranous chloride, UCl_{4}, corresponds with uranous oxide as a base. It was obtained by Peligot by igniting uranic oxide mixed with charcoal in a stream of _dry_ chlorine: UO_{3} + 3C + 2Cl_{2} = UCl_{4} + 3CO. This green volatile compound (Note 12) crystallises in regular octahedra, is very hygroscopic, easily soluble in water, with the development of a considerable amount of heat, and no longer separates out from its solution in an anhydrous state, but disengages hydrochloric acid when evaporated. The solution of uranous chloride in water is green. It is also formed by the action of zinc and copper (forming cuprous chloride) on a solution of uranyl chloride, UO_{2}Cl_{2}, especially in the presence of hydrochloric acid and sal-ammoniac. Solutions of uranyl salts are converted into uranous salts by the action of various reducing agents, and among others by organic substances or by the action of light, whilst the salts UX_{4} are converted into uranyl salts, UO_{2}X_{2}, by exposure to air or by oxidising agents. Solutions of the green uranyl salts act as powerful reducing agents, and give a brown precipitate of the uranous hydroxide, UH_{4}O_{4}, with potash and other alkalis. This hydroxide is easily soluble in acids but not in alkalis. On ignition it does not form the oxide UO_{2}, because it decomposes water, but when the higher oxides of uranium are ignited in a stream of hydrogen or with charcoal they yield uranous oxide. Both it and the chloride UCl_{4}, dissolve in strong sulphuric acid, forming a green salt, U(SO_{4})_{2},2H_{2}O. The same salt, together with uranyl sulphate, UO_{2}(SO_{4}), is formed when the green oxide, U_{3}O_{8}, is dissolved in hot sulphuric acid. The salts obtained in the latter instance may be separated by adding alcohol to the solution, which is left exposed to the light; the alcohol reduces the uranyl salt to uranous salt, an excess of acid being required. An excess of water decomposes this salt, forming a basic salt, which is also easily produced under other circumstances, and contains UO(SO_{4}),2H_{2}O (which corresponds to the uranic salt). [14] The atomic weight of uranium was formerly taken as half the present one, U = 120, and the oxides U_{2}O_{3}, suboxide UO, and green oxide U_{3}O_{4}, were of the same types as the oxides of iron. With a certain resemblance to the elements of the iron group, uranium presents many points of distinction which do not permit its being grouped with them. Thus uranium forms a very stable oxide, U_{2}O_{3}(U = 120), but does not give the corresponding chloride U_{2}Cl_{6} (Roscoe, however, in 1874 obtained UCl_{5}, like MoCl_{5} and WCl_{5}), and under those circumstances (the ignition of oxide of uranium mixed with charcoal, in a stream of chlorine), when the formation of this compound might be expected, it gives (U = 120) the chloride UCl_{2}, which is characterised by its volatility; this is not a property, to such an extent, of any of the bichlorides, RCl_{2}, of the iron group. The alteration or doubling of the atomic weight of uranium--_i.e._ the recognition of U = 240--was made for the first time in the first (Russian) edition of this work (1871), and in my memoir of the same year in Liebig's _Annalen_, on the ground that with an atomic weight 120, uranium could not be placed in the periodic system. I think it will not be superfluous to add the following remarks on this subject: (1) In the other groups (K--Rb--Cs, Ca--Sr--Ba, Cl--Br--I) the acid character of the oxides decreases and their basic character increases with the rise of atomic weight, and therefore we should expect to find the same in the group Cr--Mo--W--U, and if CrO_{3}, MoO_{3}, WO_{3} be the anhydrides of acids then we indeed find a decrease in their acid character, and therefore uranium trioxide, UO_{3}, should be a very feeble anhydride, but its basic properties should also be very feeble. Uranic oxide does indeed show these properties, as was pointed out above (Note 10). (2) Chromium and its analogues, besides the oxides RO_{3}, also form lower grades of oxidation RO_{2}, R_{2}O_{3}, and the same is seen in uranium; it forms UO_{3}, UO_{2}, U_{2}O_{3} and their compounds. (3) Molybdenum and tungsten, in being reduced from RO_{3}, easily and frequently give an intermediate oxide of a blue colour, and uranium shows the same property; giving the so-called green oxide which, according to present views, must be regarded as U_{3}O_{8} = UO_{2}2UO_{3}, analogous to Mo_{3}O_{8}. (4) The higher chlorides, RCl_{6}, possible for the elements of this group, are either unstable (WCl_{6}) or do not exist at all (Cr); but there is one single lower volatile compound, which is decomposed by water, and liable to further reduction into a non-volatile chlorine product and the metal. The same is observed in uranium, which forms an easily volatile chloride, UCl_{4}, decomposed by water. (5) The high sp. gr. of uranium (18·6) is explained by its analogy to tungsten (sp. gr. 19·1). (6) For uranium, as for chromium and tungsten, yellow tints predominate in the form RO_{3}, whilst the lower forms are green and blue. (7) Zimmermann (1881) determined the vapour densities of uranous bromide, UBr_{4}, and chloride, UCl_{4} (19·4 and 13·2), and they were found to correspond to the formulæ given above--that is, they confirmed the higher atomic weight U = 240. Roscoe, a great authority on the metals of this group, was the first to accept the proposed atomic weight of uranium, U = 240, which since Zimmermann's work has been generally recognised. As the salts of uranic oxide are reduced in the absence of organic matter by the action of light, and as they impart a characteristic coloration to glass,[15] they find a certain application in photography and glass work. [15] Uranium glass, obtained by the addition of the yellow salt K_{2}U_{2}O_{7} to glass, has a green yellow fluorescence, and is sometimes employed for ornaments; it absorbs the violet rays, like the other salts of uranic oxide--that is, it possesses an absorption spectrum in which the violet rays are absent. The index of refraction of the absorbed rays is altered, and they are given out again as greenish-yellow rays; hence, compounds of uranic acid, when placed in the violet portion of the spectrum, emit a greenish-yellow light, and this forms one of the best examples (another is found in a solution of quinine sulphate) of the phenomenon of fluorescence. The rays of light which pass through uranic compounds do not contain the rays which excite the phenomena of fluorescence and of chemical transformation, as the researches of Stokes prove. If we compare together the highly acid elements, sulphur, selenium, and tellurium, of the uneven series, with chromium, molybdenum, tungsten, and uranium of the even series, we find that the resemblance of the properties of the higher form RO_{3} does not extend to the lower forms, and even entirely disappears in the elements, for there is not the smallest resemblance between sulphur and chromium and their analogues in a free state. In other words, this means that the small periods, like Na, Mg, Al, Si, P, S, Cl, containing seven elements, do not contain any near analogues of chromium, molybdenum, &c., and therefore their true position among the other elements must be looked for only in those large periods which contain two small periods, and whose type is seen in the period containing: K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br. These large periods contain Ca and Zn, giving RO, Sc, and Ga of the third group, Ti and Ge giving RO_{2}, V and As forming R_{2}O_{5}, Cr and Se of the sixth group, Mn and Br of the seventh group, and the remaining elements, Fe, Co, Ni, form connective members of the intermediate eighth group, to the description of the representatives of which we shall turn in the following chapters. We will now proceed to describe _manganese_, Mn = 55, as an element of the seventh group of the even series, directly following after Cr = 52, which corresponds with Br = 80 to the same degree that Cr does with Se = 79. For chromium, selenium, and bromine very close analogues are known, but for manganese as yet none have been obtained--that is, it is the only representative of the even series in the seventh group. In placing manganese with the halogens in one group, the periodic system of the elements only requires that it should bear an analogy to the halogens in the higher type of oxidation--_i.e._ in the salts and acids--whilst it requires that as great a difference should be expected in the lower types and elements as there exists between chromium or molybdenum and sulphur or selenium. And this is actually the case. The elements of the seventh group form a higher salt-forming oxide, R_{2}O_{7}, and its corresponding hydrate, HRO_{4}, and salts--for example, KClO_{4}. Manganese in the form of potassium permanganate, KMnO_{4}, actually presents a great analogy in many respects to potassium perchlorate, KClO_{4}. The analogy of the crystalline form of both salts was shown by Mitscherlich. The salts of permanganic acid are also nearly all soluble in water, like those of perchloric acid, and if the silver salt of the latter, AgClO_{4}, be sparingly soluble in water, so also is silver permanganate, AgMnO_{4}. The specific volume of potassium perchlorate is equal to 55, because its specific gravity = 2·54; the specific volume of potassium permanganate is equal to 58, because its specific gravity = 2·71. So that the volumes of equivalent quantities are in this instance approximately the same whilst the atomic volumes of chlorine (35·5/1·3 = 27) and manganese (55/7·5) are in the ratio 4 : 1. In a free state the higher acids HClO_{4} and HMnO_{4} are both soluble in water and volatile, both are powerful oxidisers--in a word, their analogy is still closer than that of chromic and sulphuric acids, and those points of distinction which they present also appear among the nearest analogues--for example, in sulphuric and telluric acids, in hydrochloric and hydriodic acids, &c. Besides Mn_{2}O_{7} manganese gives a lower grade of oxidation, MnO_{3}, analogous to sulphuric and chromic trioxides, and with it corresponds potassium manganate, K_{2}MnO_{4}, isomorphous with potassium sulphate.[16] In the still lower grades of oxidation, Mn_{2}O_{3} and MnO, there is hardly any similarity to chlorine, whilst every point of resemblance disappears when we come to the elements themselves--_i.e._ to manganese and chlorine--for manganese is a metal, like iron, which combines directly with chlorine to form a saline compound, MnCl_{2}, analogous to magnesium chloride.[17] [16] The comparison of potassium permanganate with potassium perchlorate, or of potassium manganate with potassium sulphate, shows directly that many of the physical and chemical properties of substances do not depend on the nature of the elements, but on the atomic types in which they appear, on the kind of movements, or on the positions in which the atoms forming the molecule occur. [17] If, however, we compare the spectra (Vol. I. p. 565) of chlorine, bromine, and iodine with that of manganese, a certain resemblance or analogy is to be found connecting manganese both to iron and to chlorine, bromine, and iodine. Manganese belongs to the number of metals widely distributed in nature, especially in those localities where iron occurs, whose ores frequently contain compounds of manganous oxide, MnO, which presents a resemblance to ferrous oxide, FeO, and to magnesia. In many minerals magnesia and the oxides allied to it are replaced by manganous oxide; calcspars and magnesites--_i.e._ R´´CO_{3} in general--are frequently met with containing manganous carbonate, which also occurs in a separate state, although but rarely. The soil also and the ash of plants generally contain a small quantity of manganese. In the analysis of minerals it is generally found that manganese occurs together with magnesia, because, like it, manganous oxide remains in solution in the presence of ammoniacal salts, not being precipitated by reagents. The property of this manganous oxide, MnO, of passing into the higher grades of oxidation under the influence of heat, alkalis, and air, gives an easy means not only of discovering the presence of manganese in admixture with magnesia, but also of separating these two analogous bases. Magnesia is not able to give higher grades of oxidation, whilst manganese gives them with great facility. Thus, for instance, an _alkaline_ solution of sodium hypochlorite produces a precipitate of manganese dioxide in a solution of a manganous salt: MnCl_{2} + NaClO + 2NaHO = MnO_{2} + H_{2}O + 3NaCl; whilst magnesia is not changed under these circumstances, and remains in the form of MgCl_{2}. If the magnesia be precipitated owing to the presence of alkali, it may be dissolved in acetic acid, in which manganese dioxide is insoluble. The presence of small quantities of manganese may also be recognised by the green coloration which alkalis acquire when heated with manganese compounds in the air. This green coloration depends on the property of manganese of giving a green alkaline manganate: MnCl_{2} + 4KHO + O_{2} = K_{2}MnO_{4} + 2KCl + 2H_{2}O. Thus _the faculty of oxidising in the presence of alkalis_ forms an essential character of manganese. The higher grades of oxidation containing Mn_{2}O_{7} and MnO_{3} are quite unknown in nature, and even MnO_{2} is not so widely spread in nature as the ores composed of manganous compounds which are met with nearly everywhere. The most important ore of manganese is its dioxide, or so-called _peroxide_, MnO_{2}, which is known in mineralogy as _pyrolusite_. Manganese also occurs as an oxide corresponding with magnetic iron ore, MnO,Mn_{2}O_{3} = Mn_{3}O_{4}, forming the mineral known as _hausmannite_. The oxide Mn_{2}O_{3} also occurs in nature as the anhydrous mineral _braunite_, and in a hydrated form, Mn_{2}O_{3},H_{2}O, called _manganite_. Both of these often occur as an admixture in pyrolusite. Besides which, manganese is met with in nature as a rose-coloured mineral, _rhodonite_, or silicate, MnSiO_{3}. Very fine and rich deposits of manganese ores have been found in the Caucasus, the Urals, and along the Dnieper. Those at the Sharapansky district of the Government of Kutais and at Nicopol on the Dnieper are particularly rich. A large quantity of the ore (as much as 100,000 tons yearly) is exported from these localities. Thus manganese gives oxides of the following forms: MnO, manganous oxide, and manganous salts, MnX_{2}, corresponding with the base, which resembles magnesia and ferrous oxide in many respects; Mn_{2}O_{3}, a very feeble base, giving salts, MnX_{3}, analogous to the aluminium and ferric salts, easily reduced to MnX_{2}; MnO_{2}, dioxide, generally called peroxide, an almost indifferent oxide, or feebly acid;[18] MnO_{3}, manganic anhydride, which forms salts resembling potassium sulphate;[18 bis] Mn_{2}O_{7}, permanganic anhydride, giving salts analogous to the perchlorates. [18] The name 'peroxide' should only be retained for those _highest_ oxides (and MnO_{2} stands between MnO and MnO_{3}) which either by a direct method of double decomposition are able to give hydrogen peroxide or contain a larger proportion of oxygen than the base or the acid, just as hydrogen peroxide contains more oxygen than water. Their type will be H_{2}O_{2}, and they are exemplified by barium peroxide, BaO_{2}, and sulphur peroxide, S_{2}O_{7}, &c. Such a dioxide as MnO_{2} is, in all probability, a salt--that is, a manganous manganate, MnO_{3}MnO, and also, as a basic salt of a feeble base, capable of combining with alkalis and acids. Hence the name of manganese peroxide should be abandoned, and replaced by manganese dioxide. PbO_{2} is better termed lead dioxide than peroxide. Bisulphide of manganese, MnS_{2}, corresponding to iron pyrites, FeS_{2}, sometimes occurs in nature in fine octahedra (and cube combinations), for instance, in Sicily; it is called Hauerite. [18 bis] On comparing the manganates with the permanganates--for example, K_{2}MnO_{4} with KMnO_{4}--we find that they differ in composition by the abstraction of one equivalent of the metal. Such a relation in composition produced by oxidation is of frequent occurrence--for instance, K_{4}Fe(CN)_{6} in oxidising gives K_{3}Fe(CN)_{6}; H_{2}SO_{4} in oxidising gives persulphuric acid, HSO_{4}, or H_{2}S_{7}O_{8}; H_{2}O forms HO or H_{2}O_{2}, &c. _All the oxides of manganese when heated with acids give salts_, MnX_{2}, corresponding with the lower grade of oxidation, _manganous oxide_, MnO. Manganic oxide, Mn_{2}O_{3}, is a feebly energetic base; it is true that it dissolves in hydrochloric acid and gives a dark solution containing the salt MnCl_{3}, but the latter when heated evolves chlorine and gives a salt corresponding with manganous oxide MnCl_{2}--_i.e._ at first: Mn_{2}O_{3} + 6HCl = 3H_{2}O + Mn_{2}Cl_{6}, and then the Mn_{2}Cl_{6} decomposes into 2MnCl_{2} + Cl_{2}. None of the remaining higher grades of oxidation have a basic character, but _act as oxidising agents in the presence of acids_, disengaging oxygen and passing into salts of the lower grade of oxidation of manganese, MnO. Owing to this circumstance, _the manganous salts_ are often obtained; they are, for instance, left in the residue when the dioxide is used for the preparation of oxygen and chlorine.[19] [19] In the preparation of oxygen from the dioxide by means of H_{2}SO_{4}, MnSO_{4} is formed; in the preparation of chlorine from HCl and MnO_{2}, MnCl_{2} is obtained. These two manganous salts may be taken as examples of compounds MnX_{2}. Manganous sulphate generally contains various impurities, and also a large amount of iron salt (from the native MnO_{2}), from which it cannot be freed by crystallisation. Their removal may, however, be effected by mixing a portion of the liquid with a solution of sodium carbonate; a precipitate of manganous carbonate is then formed. This precipitate is collected and washed, and then added to the remaining mass of the impure solution of manganous sulphate; on heating the solution with this precipitate, the whole of the iron is precipitated as oxide. This is due to the fact that in the solution of the manganese dioxide in sulphuric acid the whole of the iron is converted into the ferric state (because the dioxide acts as an oxidising agent), which, as an exceedingly feeble base precipitated by calcium carbonate and other kindred salts, is also precipitated by manganous carbonate. After being treated in this manner, the solution of manganous sulphate is further purified by crystallisation. If it be a bright red colour, it is due to the presence of higher grades of oxidation of manganese; they may be destroyed by boiling the solution, when the oxygen from the oxides of manganese is evolved and a very faintly coloured solution of manganous sulphate is obtained. This salt is remarkable for the facility with which it gives various combinations with water. By evaporating the almost colourless solution of _manganous sulphate_ at very low temperatures, and by cooling the saturated solution at about 0°, crystals are obtained containing 7 atoms of water of crystallisation, MnSO_{4},7H_{2}O, which are isomorphous with cobaltous and ferrous sulphates. These crystals, even at 10°, lose 5 p.c. of water, and completely effloresce at 15°, losing about 20 p.c. of water. By evaporating a solution of the salt at the ordinary temperature, but not above 20°, crystals are obtained containing 5 mol. H_{2}O, which are isomorphous with copper sulphate; whilst if the crystallisation be carried on between 20° and 30°, large transparent prismatic crystals are formed containing 4 mol. H_{2}O (see Nickel). A boiling solution also deposits these crystals together with crystals containing 3 mol. H_{2}O, whilst the first salt, when fused and boiled with alcohol, gives crystals containing 2 mol. H_{2}O. Graham obtained a monohydrated salt by drying the salt at about 200°. The last atom of water is eliminated with difficulty, as is the case with all salts like MnSO_{4}nH_{2}O. The crystals containing a considerable amount of water are rose-coloured, and the anhydrous crystals are colourless. The solubility of MnSO_{4},4H_{2}O (Chapter I., Note 24) per 100 parts of water is: at 10°, 127 parts; at 37°·5, 149 parts; at 75°, 145 parts; and at 101°, 92 parts. Whence it is seen that at the boiling-point this salt is less soluble than at lower temperatures, and therefore a solution saturated at the ordinary temperature becomes turbid when boiled. Manganous sulphate, being analogous to magnesium sulphate, is decomposed, like the latter, when ignited, but it does not then leave manganous oxide, but the intermediate oxide, Mn_{3}O_{4}. It gives double salts with the alkali sulphates. With aluminium sulphate it forms fine radiated crystals, whose composition resembles that of the alums--namely, MnAl_{2}(SO_{4})_{4},24H_{2}O. This salt is easily soluble in water, and occurs in nature. _Manganous chloride_, MCl_{2}, crystallises with 4 mol. H_{2}O, like the ferrous salt, and not with 6 mol. H_{2}O like many kindred salts--for example, those of cobalt, calcium, and magnesium; 100 parts of water dissolve 38 parts of the anhydrous salt at 10° and 55 parts at 62°. Alcohol also dissolves manganous chloride, and the alcoholic solution burns with a red flame. This salt, like magnesium chloride, readily forms double salts. A solution of borax gives a dirty rose-coloured precipitate having the composition MnH_{4}(BO_{3})_{2}H_{2}O, which is used as a drier in paint-making. Potassium cyanide produces a yellowish-grey precipitate, MnC_{2}N_{2}, with manganous salts, soluble in an excess of the reagent, a double salt, K_{4}MnC_{6}N_{6}, corresponding with potassium ferrocyanide, being formed. On evaporation of this solution, a portion of the manganese is oxidised and precipitated, whilst a salt corresponding to Gmelin's red salt, K_{3},MnC_{6}N_{6} (_see_ Chapter XXII.), remains in solution. Sulphuretted hydrogen does not precipitate salts of manganese, not even the acetate, but ammonium sulphide gives a flesh-coloured precipitate, MnS; at 320° this sulphide of manganese passes into a green variety (Antony). Oxalic acid in strong solutions of manganous salts gives a white precipitate of the oxalate, MnC_{2}O_{4}. This precipitate is insoluble in water, and is used for the preparation of manganous oxide itself because it decomposes like oxalic acid when ignited (in a tube without access of air), with the formation of carbonic anhydride, carbonic oxide, and manganous oxide. _Manganous oxide_ thus obtained is a green powder, which however oxidises with such facility that it burns in air when brought into contact with an incandescent substance, and passes into the red intermediate oxide Mn_{3}O_{4}. In solutions of manganous salts, alkalis produce a precipitate of the hydroxide MnH_{2}O_{2}, which rapidly absorbs oxygen in the presence of air and gives the brown intermediate oxide, or, more correctly speaking, its hydrate. Manganous oxide, besides being obtained by the above-described method from manganous oxalate, may also be obtained by igniting the higher oxides in a stream of hydrogen, and also from manganese carbonate. The manganous oxide ignited in the presence of hydrogen acquires a great density, and is no longer so easily oxidised. It may also be obtained in a crystalline form, if during the ignition of the carbonate or higher oxide a trace of dry hydrochloric acid gas be passed into the current of hydrogen. It is thus obtained in the form of transparent emerald green crystals of the regular system, and in this state is easily soluble in acids. Manganous oxide in oxidising gives the _red oxide of manganese_, Mn_{5}O_{4}. This is the most stable of all the oxides of manganese; it is not only stable at the ordinary but also at a high temperature--that is, it does not absorb or disengage oxygen spontaneously. When ignited, all the higher oxides of manganese pass into it by losing oxygen, and manganous oxide by absorbing oxygen. This oxide does not give any distinct salts, but it dissolves in sulphuric acid, forming a dark red solution, which contains both manganous and manganic (of the _oxide_, Mn_{2}O_{3}) sulphates. The latter with potassium sulphate gives a manganese alum, in which the alumina is replaced by its isomorphous oxide of manganese. But this alum, like the solution of the intermediate oxide in sulphuric acid, evolves oxygen and leaves a manganous salt when slightly heated. _Manganese dioxide_ is still less basic than the oxide, and disengages oxygen or a halogen in the presence of acids, forming manganous salts, like the oxide. However, if it be suspended in ether, and hydrochloric acid gas passed into the mixture, which is kept cool, the ether acquires a green colour, owing to the formation of tetrachloride of manganese, MnCl_{4}, corresponding with the dioxide which passes into solution. It is however very unstable, being exceedingly easily decomposed with the evolution of chlorine. The corresponding fluoride, MnF_{4}, obtained by Nicklés is much more stable. At all events, manganese dioxide does not exhibit any well-defined basic character, but has rather an acid character, which is particularly shown in the compounds MnF_{4} and MnCl_{4} just mentioned, and in the property of manganese dioxide of combining with alkalis. If the higher grades of oxidation of manganese be deoxidised in the presence of alkalis, they frequently give the dioxide combined with the alkali--for example, in the presence of potash a compound is formed which contains K_{2}O,5MnO_{2}, which shows the weak acid character of this oxide. When ignited in the presence of sodium compounds manganese dioxide frequently forms Na_{2}O,8MnO_{2} and Na_{2}O,12MnO_{2}, and lime when heated with MnO_{2} gives from CaO,3MnO_{2} to (CaO)_{2},MnO_{2} (Rousseau) according to the temperature. Besides which, perhaps, MnO_{2} is a saline compound, containing MnOMnO_{3} or (MnO)_{3}Mn_{2}O_{7}, and there are reactions which support such a view (Spring, Richards, Traube, and others); for instance it is known that manganous chloride and potassium permanganate give the dioxide in the presence of alkalis. Manganese dioxide may be obtained from manganous salts by the action of oxidising agents. If manganous hydroxide or carbonate be shaken up in water through which chlorine is passed, the hypochlorite of the metal is not formed, as is the case with certain other oxides, but manganese dioxide is precipitated: 2MnO_{2}H_{2} + Cl_{2} = MnCl_{2} + MnO_{2},H_{2}O + H_{2}O. Owing to this fact, hypochlorites in the presence of alkalis and acetic acid when added to a solution of manganous salts give hydrated manganese dioxide, as was mentioned above. Manganous nitrate also leaves manganese dioxide when heated to 200°. It is also obtained from manganous and manganic salts of the alkalis, when they are decomposed in the presence of a small amount of acid; the practical method of converting the salts MnX_{2} into the higher grades of oxidation is given in Chapter II., Note 6. As the salts of manganous oxide MnX_{2} closely resemble (and are isomorphous with) the salts of magnesia MgX_{2} in many respects (with the exception of the fact that MnX_{2} are rose coloured and are easily oxidised in the presence of alkalis), we will not dwell upon them, but limit ourselves to illustrating the chemical character of manganese by describing the metal and its corresponding acids. The fact alone that the oxides of manganese are not reduced to the metal when ignited in hydrogen (whilst the oxides of iron give metallic iron under these circumstances), but only to manganous oxide, MnO, shows that manganese has a considerable affinity for oxygen--that is, it is difficult to reduce. This may be effected, however, by means of charcoal or sodium at a very high temperature. A mixture of one of the oxides of manganese with charcoal or organic matter gives fused _metallic manganese_ under the powerful heat developed by coke with an artificial draught. The metal was obtained for the first time in this manner by Gahn, after Pott, and more especially Scheele, had in the last century shown the difference between the compounds of iron and manganese (they were previously regarded as being the same). Manganese is prepared by mixing one of its oxides in a finely-divided state with oil and soot; the resultant mass is then first ignited in order to decompose the organic matter, and afterwards strongly heated in a charcoal crucible. The manganese thus obtained, however, contains, as a rule, a considerable amount of silicon and other impurities. Its specific gravity varies between 7·2 and 8·0. It has a light grey colour, a feebly metallic lustre, and although it is very hard it can be scratched by a file. It rapidly oxidises in air, being converted into a black oxide; water acts on it with the evolution of hydrogen--this decomposition proceeds very rapidly with boiling water, and if the metal contain carbon.[20] [20] Other chemists have obtained manganese by different methods, and attributed different properties to it. This difference probably depends on the presence of carbon in different proportions. Deville obtained manganese by subjecting the pure dioxide, mixed with pure charcoal (from burnt sugar), to a strong heat in a lime crucible until the resultant metal fused. The metal obtained had a rose tint, like bismuth, and like it was very brittle, although exceedingly hard. It decomposed water at the ordinary temperature. Brunner obtained manganese having a specific gravity of about 7·2, which decomposed water very feebly at the ordinary temperature, did not oxidise in air, and was capable of taking a bright polish, like steel; it had the grey colour of cast iron, was very brittle, and hard enough to scratch steel and glass, like a diamond. Brunner's method was as follows: He decomposed the manganese fluoride (obtained as a soluble compound by the action of hydrofluoric acid on manganese carbonate) with sodium, by mixing these substances together in a crucible and covering the mixture with a layer of salt and fluor spar; after which the crucible was first gradually heated until the reaction began, and then strongly heated in order to fuse the metal separated. Glatzel (1889) obtained 25 grms. of manganese, having a grey colour and sp. gr. 7·39, by heating a mixture of 100 grms. of MnCl_{2} with 200 grms. KCl and 15 grms. Mg to a bright white heat. Moissan and others, by heating the oxides of manganese with carbon in the electric furnace, obtained carbides of manganese--for example, Mn_{3}C--and remarked that the metal volatilised in the heat of the voltaic arc. Metallic manganese is, however, not prepared on a large scale, but only its alloys with carbon (they readily and rapidly oxidise) and _ferro-manganese_ or a coarsely crystalline alloy of iron, manganese and carbon, which is smelted in blast-furnaces like pig-iron (_see_ Chapter XXII.) This ferro-manganese is employed in the manufacture of steel by Bessemer's and other processes (see Chapter XXII.) and for the manufacture of manganese bronze. However, in America, Green and Wahl (1895) obtained almost pure metallic manganese on a large scale. They first treat the ore of MnO_{2} with 30 p.c. sulphuric acid (which extracts all the oxides of iron present in the ore), and then heat it in a reducing flame to convert it into MnO, which they mix with a powder of Al, lime and CaF_{2} (as a flux), and heat the mixture in a crucible lined with magnesia; a reaction immediately takes place at a certain temperature, and a metal of specific gravity 7·3 is obtained, which only contains a small trace of iron. Manganese gives two compounds with _nitrogen_, Mn_{5}N_{2} and Mn_{3}N_{2}. They were obtained by Prelinger (1894) from the amalgam of manganese Mn_{2}Hg_{5} (obtained on a mercury anode by the action of an electric current upon a solution of MnCl_{2}); the mercury may be removed from this amalgam by heating it in an atmosphere of hydrogen, and then metallic manganese is obtained as a grey porous mass of specific gravity 7·42. If this amalgam be heated in dry nitrogen it gives Mn_{5}N_{2} (grey powder, sp. gr. 6·58), but if heated in an atmosphere of NH_{3} it gives (as also does Mn_{5}N_{2}) Mn_{3}N_{2}, (a dark mass with a metallic lustre, sp. gr. 6·21), which, when heated in nitrogen is converted into Mn_{5}N_{2}, and if heated in hydrogen evolves NH_{3} and disengages hydrogen from a solution of NH_{4}Cl. At all events, manganese is a metal which decomposes water more easily than iron, nickel, and cobalt. It has been shown above that if manganese dioxide, or any lower oxide of manganese, be heated with an alkali in the presence of air, the mixture absorbs oxygen,[21] and forms an alkaline manganate of a green colour: 2KHO + MnO_{2} + O = K_{2}MnO_{4} + H_{2}O. Steam is disengaged during the ignition of the mixture, and if this does not take place there is no absorption of oxygen. The oxidation proceeds much more rapidly if, before igniting in air, potassium chlorate or nitre be added to the mixture, and this is the method of preparing _potassium manganate_, K_{2}MnO_{4}. The resultant mass dissolved in a small quantity of water gives a dark green solution, which, when evaporated under the receiver of an air-pump over sulphuric acid, deposits green crystals of exactly the same form as potassium sulphate--namely, six-sided prisms and pyramids. The composition of the product is not changed by being redissolved, if perfectly pure water free from air and carbonic acid be taken. But in the presence of even very feeble acids the solution of this salt changes its colour and becomes red, and deposits manganese dioxide. The same decomposition takes place when the salt is heated with water, but when diluted with a large quantity of unboiled water manganese dioxide does not separate, although the solution turns red. This change of colour depends on the fact that potassium manganate, K_{2}MnO_{4}, whose solution is green, is transformed into potassium permanganate, KMnO_{4}, whose solution is of a red colour. The reaction proceeding under the influence of acids and a large quantity of water is expressed in the following manner: 3K_{2}MnO_{4} + 2H_{2}O = 2KMnO_{4} + MnO_{2} + 4KHO. If there is a large proportion of acid and the decomposition is aided by heat, the manganese dioxide and potassium permanganate are also decomposed, with formation of manganous salt. Exactly the same decomposition as takes place under the action of acids is also accomplished by magnesium sulphate, which reacts in many cases like an acid. When water holding atmospheric oxygen in solution acts on a solution of potassium manganate, the oxygen combines directly with the manganate and forms potassium permanganate, without precipitating manganese dioxide, 2K_{2}MnO_{4} + O + H_{2}O = 2KMnO_{4} + 2KHO. Thus a solution of potassium manganate undergoes a very characteristic change in colour and passes from green to red; hence this salt received the name of _chameleon mineral_.[22] [21] Volume I. p. 157, Note 7. [22] It was known to the alchemists by this name, but the true explanation of the change in colour is due to the researches of Chevillot, Edwards, Mitscherlich, and Forchhammer. The change in colour of potassium manganate is due to its instability and to its splitting up into two other manganese compounds, a higher and a lower: 3MnO_{3} = Mn_{2}O_{7} + MnO_{2}. Manganese trioxide is really decomposed in this manner by the action of water (see later): 3MnO_{3} + H_{2}O = 2MnHO_{4} + MnO_{2} (Franke, Thorpe, and Humbly). The instability of the salt is proved by the fact of its being deoxidised by organic matter, with the formation of manganese dioxide and alkali, so that, for instance, a solution of this salt cannot be filtered through paper. The presence of an excess of alkali increases the stability of the salt; when heated it breaks up in the presence of water, with the evolution of oxygen. The method of preparing _potassium permanganate_ will be understood from the above. There are many recipes for preparing this substance, as it is now used in considerable quantities both for technical and laboratory purposes. But in all cases the essence of the methods is one and the same: a mixture of alkali with any oxide of manganese (even manganous hydroxide, which may be obtained from manganous chloride) is first heated in the presence of air or of an oxidising substance (for the sake of rapidity, with potassium chlorate); the resultant mass is then treated with water and heated, when manganese dioxide is precipitated and potassium permanganate remains in solution. This solution may be boiled, as the liquid will contain free alkali; but the solution cannot be evaporated to dryness, because a strong solution, as well as the solid salt, is decomposed by heat. By adding a dilute solution of manganous sulphate to a boiling mixture of lead dioxide and dilute nitric acid, the whole of the manganese may be converted into permanganic acid (Crum). _Potassium permanganate_, KMnO_{4}, crystallises in well-formed, long red prisms with a bright green metallic lustre. In the arts the potash is frequently replaced by soda, and by other alkaline bases, but no salt of permanganic acid crystallises so well as the potassium salt, and therefore this salt is exclusively used in chemical laboratories. One part of the crystalline salt dissolves in 15 parts of water at the ordinary temperature. The solution is of a very deep _red colour_, which is so intense that it is still clearly observable after being highly diluted with water. In a solid state it is decomposed by heat, with evolution of oxygen, a residue consisting of the lower oxides of manganese and potassium oxide being left.[22 bis] A mixture of permanganate of potassium, phosphorous and sulphur takes fire when struck or rubbed, a mixture of the permanganate with carbon only takes fire when heated, not when struck. The instability of the salt is also seen in the fact that its solution is decomposed by peroxide of hydrogen, which at the same time it decomposes. A number of substances reduce potassium permanganate to manganese dioxide (in which case the red solution becomes colourless).[23] Many organic substances (although far from all, even when boiled in a solution of permanganate) act in this manner, being oxidised at the expense of a portion of its oxygen. Thus, a solution of sugar decomposes a cold solution of potassium permanganate. In the presence of an excess of alkali, with a small quantity of sugar, the reduction leads to the formation of potassium manganate, because 2KMnO_{4} + 2KHO = O + 2K_{2}MnO_{4} + H_{2}O. With a considerable amount of sugar and a more prolonged action, the solution turns brown and precipitates manganese dioxide or even oxide. In the oxidation of many organic bodies by an alkaline solution of KMnO_{4} generally three-eighths of the oxygen in the salt are utilised for oxidation: 2KMnO_{4} = K_{2}O + 2MnO_{2} + O_{3}. A portion of the alkali liberated is retained by the manganese dioxide, and the other portion generally combines with the substance oxidised, because the latter most frequently gives an acid with an excess of alkali. A solution of potassium iodide acts in a similar manner, being converted into potassium iodate at the expense of the three atoms of oxygen disengaged by two molecules of potassium permanganate. [22 bis] The solution of this salt with an excess of impure commercial alkali generally acquires a green tint. [23] A solution of potassium permanganate gives a beautiful absorption spectrum (Chapter XIII.) If the light in passing through this solution loses a portion of its rays in it (if one may so account for it), this is partially explained by the increased oxidising power which the solution then acquires. We may here also remark that a dilute solution of permanganate of potassium forms a colourless solution with nickel salts, because the green colour of the solution of nickel salts is complementary to the red. Such a decolorised solution, containing a large proportion of nickel and a small proportion of manganese, decomposes after a time, throws down a precipitate, and re-acquires the green colour proper to the nickel salts. The addition of a solution of a cobalt salt (rose-red) to the nickel salt also destroys the colour of both salts. _In the presence of acids, potassium permanganate acts as an oxidising agent_ with still greater energy than in the presence of alkalis. At any rate, a greater proportion of oxygen is then available for oxidation, namely, not 3/8, as in the presence of alkalis, but 5/8, because in the first instance manganese dioxide is formed, and in the second case manganous oxide, or rather the salt, MnX_{2}, corresponding with it. Thus, for instance, in the presence of an excess of sulphuric acid, the decomposition is accomplished in the following manner: 2KMnO_{4} + 3H_{2}SO_{4} = K_{2}SO_{4} + 2MnSO_{4} + 3H_{2}O + 5O. This decomposition, however, does not proceed directly on mixing a solution of the salt with sulphuric acid, and crystals of the salt even dissolve in oil of vitriol without the evolution of oxygen, and this solution only decomposes by degrees after a certain time. This is due to the fact that sulphuric acid liberates free permanganic acid from the permanganate,[24] which acid is stable in solution. But if, in the presence of acids and a permanganate, there is a substance capable of absorbing oxygen--for instance, capable of passing into a higher grade of oxidation--then the reduction of the permanganic acid into manganous oxides sometimes proceeds directly at the ordinary temperature. This reduction is very clearly seen, because the solutions of potassium permanganate are red whilst the manganous salts are almost colourless. Thus, for instance, nitrous acid and its salts are converted into nitric acid and decolorise the acid solution of the permanganate. Sulphurous anhydride and its salts immediately decolorise potassium permanganate, forming sulphuric acid. Ferrous salts, and in general salts of lower grades of oxidation capable of being oxidised in solution, act in exactly the same manner. Sulphuretted hydrogen is also oxidised to sulphuric acid; even mercury is oxidised at the expense of permanganic acid, and decolorises its solution, being converted into mercuric oxide. Moreover, the end point of these reactions may easily be seen, and therefore, having first determined the amount of active oxygen in one volume of a solution of potassium permanganate, and knowing how many volumes are required to effect a given oxidation, it is easy to determine the amount of an oxidisable substance in a solution from the amount of permanganate expended (Marguerite's method). [24] If sulphuric acid is allowed to act on potassium permanganate without any special precautions, a large amount of oxygen is evolved (it may even explode and inflame), and a violet spray of the decomposing permanganic acid is given off. But if the pure salt (_i.e._ free from chlorine) be dissolved in pure well-cooled sulphuric acid, without any rise in temperature, a green-coloured liquid settles at the bottom of the vessel. This liquid does not contain any sulphuric acid, and consists of permanganic anhydride, Mn_{2}O_{7} (Aschoff, Terreil). It is impossible to prepare any considerable quantity of the anhydride by this method, as it decomposes with an explosion as it collects, evolving oxygen and leaving red oxide of manganese. _Permanganic anhydride_, Mn_{2}O_{7}, in dissolving in sulphuric acid, gives a green solution, which (according to Franke, 1887) contains a compound Mn_{2}SO_{10} = (MnO_{3})_{2}SO_{4}--that is, sulphuric acid in which both hydrogens are replaced by the group MnO_{3}, which is combined with OK in permanganate of potassium. This mixture with a small quantity of water gives Mn_{2}O_{7}, according to the equation: (MnO_{3})_{2}SO_{4} + H_{2}O = H_{2}SO_{4} + Mn_{2}O_{7}, and when heated to 30° it gives _manganese trioxide_, (MnO_{3})_{2}SO_{4} + H_{2}O = 2MnO_{2} + H_{2}SO_{4} + O. Pure manganese trioxide is obtained if the solution of (MnO_{3})_{2}SO_{4} be poured in drops on to sodium carbonate. Then, together with carbonic anhydride, a spray of manganese trioxide passes over, which may be collected in a well-cooled receiver, and this shows that the reaction proceeds according to the equation: (MnO_{3})_{2}SO_{4} + Na_{2}CO_{3} = Na_{2}SO_{4} + 2MnO_{3} + CO_{2} + O (Thorpe). The trioxide is decomposed by water, forming manganese dioxide and a solution of _permanganic acid_: 3MnO_{3} + H_{2}O = MnO_{2} + 2HMnO_{4}. The same acid is obtained by dissolving permanganic anhydride in water. Barium permanganate when treated with sulphuric acid gives the same acid. This barium salt may be prepared by the action of barium chloride on the difficultly soluble silver permanganate, AgMnO_{4}, which is precipitated on mixing a strong solution of the potassium salt with silver nitrate. The solution of permanganic acid forms a bright red liquid which reflects a dark violet tint. A dilute solution has exactly the same colour as that of the potassium salt. It deposits manganese dioxide when exposed to the action of light, and also when heated above 60°, and this proceeds the more rapidly the more dilute the solution. It shows its oxidising properties in many cases, as already mentioned. Even hydrogen gas is absorbed by a solution of permanganic acid; and charcoal and sulphur are also oxidised by it, as they are by potassium permanganate. This may be taken advantage of in analysing gunpowder, because when it is treated with a solution of potassium permanganate, all the sulphur is converted into sulphuric acid and all the charcoal into carbonic anhydride. Finely-divided platinum immediately decomposes permanganic acid. With potassium iodide it liberates iodine (which may afterwards be oxidised into iodic acid) (Mitscherlich, Fromherz, Aschoff, and others). Ammonia does not form a corresponding salt with free permanganic acid, because it is oxidised with evolution of nitrogen. The oxidising action of permanganic acid in a strong solution may be accompanied by flame and the formation of violet fumes of permanganic acid; thus a strong solution of it takes fire when brought into contact with paper, alcohol, alkaline sulphides, fats, &c. We may add that, according to Franke, 1 part of potassium permanganate with 13 parts of sulphuric acid at 100° gives brown crystals of the salt Mn_{2}(SO_{4})_{3},H_{2}SO_{4},4H_{2}O, which gives a precipitate of hydrated manganese dioxide, H_{2}MnO_{3} = MnO_{2}H_{2}O, when treated with water. Spring, by precipitating potassium permanganate with sodium sulphite and washing the precipitate by decantation, obtained a soluble colloidal manganese oxide, whose composition was the mean between Mn_{2}O_{3} and MnO_{2}--namely, Mn_{2}O_{3},4(MnO_{2}H_{2}O). The oxidising action of KMnO_{4}, like all other chemical reactions, is not accomplished instantaneously, but only gradually. And, as the course of the reaction is here easily followed by determining the amount of salt unchanged in a sample taken at a given moment,[25] the oxidising reaction of potassium permanganate, in an acid liquid, was employed by Harcourt and Esson (1865) as one of the first cases for the investigation of the laws of the _rate of chemical change_[26] as a subject of great importance in chemical mechanics. In their experiments they took oxalic acid, C_{2}H_{2}O_{4}, which in oxidising gives carbonic anhydride, whilst, with an excess of sulphuric acid, the potassium permanganate is converted into manganous sulphate, MnSO_{4}, so that the ultimate oxidation will be expressed by the equation: 5C_{2}H_{2}O_{4} + 2MnKO_{4} + 3H_{2}SO_{4} = 10CO_{2} + K_{2}SO_{4} + 2MnSO_{4} + 8H_{2}O. The influence of the relative amount of sulphuric acid is seen from the annexed table, which gives the measure of reaction _p_ per 100 parts of potassium permanganate, taken four minutes after mixing, using n molecules of sulphuric acid, H_{2}SO_{4}, per 2KMnO_{4} + 5C_{2}H_{2}O_{4}: _n_ = 2 4 6 8 12 16 22 _p_ = 22 36 51 63 77 86 92 showing that in a given time (4 minutes) the oxidation is the more perfect the greater the amount of sulphuric acid taken for given amounts of KMnO_{4} and C_{2}H_{2}O_{4}. It is obvious also that the temperature and relative amount of every one of the acting and resulting substances should show its influence on the relative velocity of reaction; thus, for instance, direct experiment showed the influence of the admixture of manganous sulphate. When a large proportion of oxalic acid (108 molecules) was taken to a large mass of water and to 2 molecules of permanganate 14 molecules of manganous sulphate were added, the quantity x of the potassium permanganate acted on (in percentages of the potassium permanganate taken) in t minutes (at 16°) was as follows: _t_ = 2 5 8 11 14 44 47 53 61 68 _x_ = 5·2 12·1 18·7 25·1 31·3 68·4 71·7 75·8 79·8 83·0 These figures show that the rate of reaction--that is, the quantity of permanganate changed in one minute--decreases proportionally to the decrease in the amount of unchanged potassium permanganate. At the commencement, about 2·6 per cent. of the salt taken was decomposed in the course of one minute, whilst after an hour the rate was about 0·5 per cent. The same phenomena are observed in every case which has been investigated, and this branch of theoretical or physical chemistry, now studied by many,[27] promises to explain the course of chemical transformations from a fresh point of view, which is closely allied to the doctrine of affinity, because the rate of reaction, without doubt, is connected with the magnitude of the affinities acting between the reacting substances. [25] For rapid and accurate determinations of this kind, advantage is taken of those methods of chemical analysis which are known as 'titrations' (volumetric analysis), and consist in measuring the volume of solutions of known strength required for the complete conversion of a given substance. Details respecting the theory and practice of titration, in which potassium permanganate is very frequently employed, must be looked for in works on analytical chemistry. [26] The measurements of velocity and acceleration serve for determining the measure of forces in mechanics, but in that case the velocities are magnitudes of length or paths passed over in a unit of time. The velocity of chemical change embodies a conception of quite another kind. In the first place, the velocities of reactions are magnitudes of the masses which have entered into chemical transformations; in the second place, these velocities can only be relative quantities. Hence the conception of 'velocity' has quite a different meaning in chemistry from what it has in mechanics. Their only common factor is time. If _dt_ be the increment of time and _dx_ the quantity of a substance changed in this space of time, then the fraction (or quotient) _dx/dt_ will express the rate of the reaction. The natural conclusion, come to both by Harcourt and Esson, and previously to them (1850) by Wilhelmj (who investigated the rate of conversion, or inversion, of sugar in its passage into glucose), consists in establishing that this velocity is proportional to the quantity of substances still unchanged--_i.e._ that _dx/dt_ = C(A - _x_), where C is a constant coefficient of proportionality, and where A is the quantity of a substance taken for reaction at the moment when _t_ = 0 and _x_ = 0--that is, at the beginning of the experiment, from which the time _t_ and quantity _x_ of substance changed is counted. On integrating the preceding equation we obtain log(A/(A - _x_)) = _kt_, where _k_ is a new constant, if we take ordinary (and not natural) logarithms. Hence, knowing A, _x_, and _t_, for each reaction, we find _k_, and it proves to be a constant quantity. Thus from the figures cited in the text for the reaction 2KMnO_{4} + 108C_{2}H_{2}O_{4} + 14MnSO_{4}, it may be calculated that _k_ = 0·0114; for example, _t_ = 44, _x_ = 68·4 (A = 100), whence _kt_ = 0·5004 and _k_ = 0·0114, (_see also_ Chapter XIV., Note 3, and Chapter XVII., Note 25 bis). [27] The researches made by Hood, Van't Hoff, Ostwald, Warder, Menschutkin, Konovaloff, and others have a particular significance in this direction. Owing to the comparative novelty of this subject, and the absence of applicable as well as indubitable deductions, I consider it impossible to enter into this province of theoretical chemistry, although I am quite confident that its development should lead to very important results, especially in respect to chemical equilibria, for Van't Hoff has already shown that the limit of reaction in reversible reactions is determined by the attainment of equal velocities for the opposite reactions. CHAPTER XXII IRON, COBALT, AND NICKEL Judging from the atomic weights, and the forms of the higher oxides of the elements already considered, it is easy to form an idea of the seven groups of the periodic system. Such are, for instance, the typical series Li, Be, B, C, N, O, F, or the third series, Na, Mg, Al, Si, P, S, Cl. The seven usual types of oxides from R_{2}O to R_{2}O_{7} correspond with them (Chapter XV.) The position of the eighth group is quite separate, and is determined by the fact that, as we have already seen, in each group of metals having a greater atomic weight than potassium a distinction ought to be made between the elements of the even and uneven series. The series of even elements, commencing with a strikingly alkaline element (potassium, rubidium, cæsium), together with the uneven series following it, and concluding with a haloid (chlorine, bromine, iodine), forms a large period, the properties of whose members repeat themselves in other similar periods. The elements of the eighth group are situated between the elements of the even series and the elements of the uneven series following them. And for this reason elements of the eighth group are found in the middle of each large period. The properties of the elements belonging to it, in many respects independent and striking, are shown with typical clearness in the case of iron, the well-known representative of this group. _Iron_ is one of those elements which are not only widely diffused in the crust of the earth, but also throughout the entire universe. Its oxides and their various compounds are found in the most diverse portions of the earth's crust; but here iron is always found combined with some other element. Iron is not found on the earth's surface in a free state, because it easily oxidises under the action of air. It is occasionally found in the native state in meteorites, or aerolites, which fall upon the earth. _Meteoric iron_ is formed outside the earth.[1] Meteorites are fragments which are carried round the sun in orbits, and fall upon the earth when coming into proximity with it during their motion in space. The meteoric dust, on passing through the upper parts of the atmosphere, and becoming incandescent from friction with the gases, produces that phenomenon which is familiar under the name of falling stars.[2] Such is the doctrine concerning meteorites, and therefore the fact of their containing rocky (siliceous) matter and metallic iron shows that outside the earth the elements and their aggregation are in some degree the same as upon the earth itself. [1] The composition of meteoric iron is variable. It generally contains nickel, phosphorus, carbon, &c. The schreibersite of meteoric stones contains Fe_{4}Ni_{2}P. [2] Comets and the rings of Saturn ought now to be considered as consisting of an accumulation of such meteoric cosmic particles. Perhaps the part played by these minute bodies scattered throughout space is much more important in the formation of the largest celestial bodies than has hitherto been imagined. The investigation of this branch of astronomy, due to Schiaparelli, has a bearing on the whole of natural science. The question arises as to why the iron in meteorites is in a free state, whilst on earth it is in a state of combination. Does not this tend to show that the condition of our globe is very different from that of the rest? My answer to this question has been already given in Volume I. p. 377, Note 57. It is my opinion that inside the earth there is a mass similar in composition to meteorites--that is, containing rocky matter and metallic iron, partly carburetted. In conclusion, I consider it will not be out of place to add the following explanations. According to the theory of the distribution of pressures (see my treatise, _On Barometrical Levelling_, 1876, pages 48 _et seq._) in an atmosphere of mixed gases, it follows that two gases, whose densities are _d_ and _d__{1}, and whose relative quantities or partial pressures at a certain distance from the centre of gravity are _h_ and _h__{1}, will, when at a greater distance from the centre of attraction, present a different ratio of their masses _x_ : _x__{1}--that is, of their partial pressures--which may be found by the equation _d__{1}(log(_h_) - log(_x_)) = _d_(log(_h__{1}) - log(_x__{1})). If, for instance, _d_ : _d__{1} = 2 : 1, and _h_ = _h__{1} (that is to say, the masses are equal at the lower height) = 1000, then when _x_ = 10 the magnitude of _x__{1} will not be 10 (_i.e._ the mass of a gas at a higher level whose density = 1 will not be equal to the mass of a gas whose density = 2, as was the case at a lower level), but much greater--namely, _x__{1} = 100--that is, the lighter gas will predominate over a heavier one at a higher level. Therefore, when the whole mass of the earth was in a state of vapour, the substances having a greater vapour density accumulated about the centre and those with a lesser vapour density at the surface. And as the vapour densities depend on the atomic and molecular weights, those substances which have small atomic and molecular weights ought to have accumulated at the surface, and those with high atomic and molecular weights, which are the least volatile and the easiest to condense, at the centre. Thus it becomes apparent why such light elements as hydrogen, carbon, nitrogen, oxygen, sodium, magnesium, aluminium, silicon, phosphorus, sulphur, chlorine, potassium, calcium, and their compounds predominate at the surface and largely form the earth's crust. There is also now much iron in the sun, as spectrum analysis shows, and therefore it must have entered into the composition of the earth and other planets, but would have accumulated at the centre, because the density of its vapour is certainly large and it easily condenses. There was also oxygen near the centre of the earth, but not sufficient to combine with the iron. The former, as a much lighter element, principally accumulated at the surface, where we at the present time find all oxidised compounds and even a remnant of free oxygen. This gives the possibility not only of explaining in accordance with cosmogonic theories the predominance of oxygen compounds on the surface of the earth, with the occurrence of unoxidised iron in the interior of the earth and in meteorites, but also of understanding why the density of the whole earth (over 5) is far greater than that of the rocks (1 to 3) composing its crust. And if all the preceding arguments and theories (for instance the supposition that the sun, earth, and all the planets were formed of an elementary homogeneous mass, formerly composed of vapours and gases) be true, it must be admitted that the interior of the earth and other planets contains metallic (unoxidised) iron, which, however, is only found on the surface as aerolites. And then assuming that aerolites are the fragments of planets which have crumbled to pieces so to say during cooling (this has been held to be the case by astronomers, judging from the paths of aerolites), it is readily understood why they should be composed of metallic iron, and this would explain its occurrence in the depths of the earth, which we assumed as the basis of our theory of the formation of naphtha (Chapter VIII., Notes 57-60). The most widely diffused terrestrial compound of iron is iron bisulphide, FeS_{2}, or _iron pyrites_. It occurs in formations of both aqueous and igneous origin, and sometimes in enormous masses. It is a substance having a greyish-yellow colour, with a metallic lustre, and a specific gravity of 5·0; it crystallises in the regular system.[2 bis] [2 bis] Immense deposits of iron pyrites are known in various parts of Russia. On the river Msta, near Borovitsi, thousands of tons are yearly collected from the detritus of the neighbouring rocks. In the Governments of Toula, Riazan, and in the Donets district continuous layers of pyrites occur among the coal seams. Very thick beds of pyrites are also known in many parts of the Caucasus. But the deposits of the Urals are particularly vast, and have been worked for a long time. Amongst these I will only indicate the deposits on the Soymensky estate near the Kishteimsky works; the Kaletinsky deposits near the Virhny-Isetsky works (containing 1-2 p.c. Cu); on the banks of the river Koushaivi near Koushvi (3-5 p.c. Cu), and the deposits near the Bogoslovsky works (3-5 p.c. Cu). Iron pyrites (especially that containing copper which is extracted after roasting) is now chiefly employed for roasting, as a source of SO_{2}, for the manufacture of chamber sulphuric acid (Vol. I. p. 291), but the remaining oxide of iron is perfectly suitable for smelting into pig iron, although it gives a sulphurous pig iron (the sulphur may be easily removed by subsequent treatment, especially with the aid of ferro-manganese in Bessemer's process). The great technical importance of iron pyrites leads to its sometimes being imported from great distances; for instance, into England from Spain. Besides which, when heated in closed retorts FeS_{2} gives sulphur, and if allowed to oxidise in damp air, green vitriol, FeSO_{4}. The oxides are the principal ores used for producing metallic iron. The majority of the ores contain ferric oxide, Fe_{2}O_{3}, either in a free state or combined with water, or else in combination with ferrous oxide, FeO. The species and varieties of iron ores are numerous and diverse. Ferric oxide in a separate form appears sometimes as crystals of the rhombohedric system, having a metallic lustre and greyish steel colour; they are brittle, and form a red powder, specific gravity about 5·25. Ferric oxide in type of oxidation and properties resembles alumina; it is, however, although with difficulty, soluble in acids even when anhydrous. The crystalline oxide bears the name of _specular iron ore_, but ferric oxide most often occurs in a non-crystalline form, in masses having a red fracture, and is then known as _red hæmatite_. In this form, however, it is rather a rare ore, and is principally found in veins. The hydrates of ferric oxide, ferric hydroxides,[3] are most often found in aqueous or stratified formations, and are known as _brown hæmatites_; they generally have a brown colour, form a yellowish-brown powder, and have no metallic lustre but an earthy appearance. They easily dissolve in acids and diffuse through other formations, especially clays (for instance, ochre); they sometimes occur in reniform and similar masses, evidently of aqueous origin. Such are, for instance, the so-called bog or lake and peat ores found at the bottom of marshes and lakes, and also under and in peat beds. This ore is formed from water containing ferrous carbonate in solution, which, after absorbing oxygen, deposits ferric hydroxide. In rivers and springs, iron is found in solution as ferrous carbonate through the agency of carbonic acid: hence the existence of chalybeate springs containing FeCO_{3}. This ferrous carbonate, or _siderite_, is either found as a non-crystalline product of evidently aqueous origin, or as a crystalline spar called _spathic iron ore_. The reniform deposits of the former are most remarkable; they are called spherosiderites, and sometimes form whole strata in the jurassic and carboniferous formations. _Magnetic iron ore_, Fe_{3}O_{4} = FeO,Fe_{2}O_{3}, in virtue of its purity and practical uses, is a very important ore; it is a compound of the ferrous and ferric oxides, is naturally magnetic, has a specific gravity of 5·1, crystallises in well-formed crystals of the regular system, is with difficulty soluble in acids, and sometimes forms enormous masses, as, for instance, Mount Blagodat in the Ural. However, in most cases--for instance, at Korsak-Mogila (to the north of Berdiansk and Nogaiska, near the Sea of Azov), or at Krivoi Rog (to the west of Ekaterinoslav)--the magnetic iron ore is mixed with other iron ores. In the Urals, the Caucasus (without mentioning Siberia), and in the districts adjoining the basin of the Don, Russia possesses the richest iron ores in the world. To the south of Moscow, in the Governments of Toula and Nijninovgorod, in the Olonetz district, and in the Government of Orloffsky (near Zinovieff in the district of Kromsky), and in many other places, there are likewise abundant supplies of iron ores amongst the deposited aqueous formations; the siderite of Orloffsky, for instance, is distinguished by its great purity.[4] [3] The hydrated ferric oxide is found in nature in a dual form. It is somewhat rarely met with in the form of a crystalline mineral called _göthite_, whose specific gravity is 4·4 and composition Fe_{2}H_{3}O_{4}, or FeHO_{2}--that is, one of oxide of iron to one of water, Fe_{2}O_{3},H_{2}O; frequently found as brown ironstone, forming a dense mass of fibrous, reniform deposits containing 2Fe_{2}O_{3},3H_{2}O--that is, having a composition Fe_{4}H_{6}O_{9}. In bog ore and other similar ores we most often find a mixture of this hydrated ferric oxide with clay and other impurities. The specific gravity of such formations is rarely as high as 4·0. [4] The ores of iron, similarly to all substances extracted from veins and deposits, are worked according to mining practice by means of vertical, horizontal, or inclined shafts which reach and penetrate the veins and strata containing the ore deposits. The mass of ore excavated is raised to the surface, then sorted either by hand or else in special sorting apparatus (generally acting with water to wash the ore), and is subjected to roasting and other treatment. In every case the ore contains foreign matter. In the extraction of iron, which is one of the cheapest metals, the dressing of an ore is in most cases unprofitable, and only ores rich in metal are worked--namely, those containing at least 20 p.c. It is often profitable to transport very rich and pure ores (with as much as 70 p.c. of iron) from long distances. The details concerning the working and extraction of metals will be found in special treatises on metallurgy and mining. Iron is also found in the form of various other compounds--for instance, in certain silicates, and also in some phosphates; but these forms are comparatively rare in nature in a pure state, and have not the industrial importance of those natural compounds of iron previously mentioned. In small quantities iron enters into the composition of every kind of _soil_ and all rocky formations. As ferrous oxide, FeO, is isomorphous with magnesia, and ferric oxide, Fe_{2}O_{3}, with alumina, isomorphous substitution is possible here, and hence minerals are not unfrequently found in which the quantity of iron varies considerably; such, for instance, are pyroxene, amphibole, certain varieties of mica, &c. Although much iron oxide is deleterious to the growth of vegetation, still plants do not flourish without iron; it enters as an indispensable component into the composition of all higher _organisms_; in the ash of plants we always find more or less of its compounds. It also occurs in blood, and forms one of the colouring matters in it; 100 parts of the blood of the highest organisms contain about 0·05 of iron. The _reduction_ of the ores of iron into metallic iron is in principle very simple, because when the oxides of iron are strongly heated with charcoal, hydrogen, carbonic oxide, and other reducing agents,[5] they easily give metallic iron. But the matter is rendered more difficult by the fact that the iron does not melt at the heat developed by the combustion of the charcoal, and therefore it does not separate from those mechanically mixed impurities which are found in the iron ore. This is obviated by the following very remarkable property of iron: at a high temperature it is capable of combining with a small quantity (from 2 to 5 p.c.) of carbon, and then forms _cast iron_, which easily _melts_ in the heat developed by the combustion of charcoal in air. For this reason metallic iron is not obtained directly from the ore, but is only formed after the further treatment of the cast iron; the first product extracted from the ore being cast iron. The fused mass disposes itself in the furnace below the slag--that is, the impurities of the ore fused by the heat of the furnace. If these impurities did not fuse they would block up the furnace in which the ore was being smelted, and the continuous smelting of the cast iron would not be possible;[6] it would be necessary periodically to cool the furnace and heat it up again, which means a wasteful expenditure of fuel, and hence in the production of cast iron, the object in view is to obtain all the earthy impurities of the ore in the shape of a fused mass or slag. Only in rare cases does the ore itself form a mass which fuses at the temperature employed, and these cases are objectionable if much iron oxide is carried away in the slag. The impurities of the ores most often consist of certain mixtures--for instance, a mixture of clay and sand, or a mixture of limestone and clay, or quartz, &c. These impurities do not separate of themselves, or do not fuse. The difficulty of the industry lies in forming an easily-fusible slag, into which the whole of the foreign matter of the ore would pass and flow down to the bottom of the furnace above the heavier cast iron. This is effected by mixing certain _fluxes_ with the ore and charcoal. A flux is a substance which, when mixed with the foreign matter of the ore, forms a fusible vitreous mass or slag. The flux used for silica is limestone with clay; for limestone a definite quantity of silica is used, the best procedure having been arrived at by experiment and by long practice in iron smelting and other metallurgical processes.[7] [5] The reduction of iron oxides by hydrogen belongs to the order of reversible reactions (Chapter II.), and is therefore determined by a limit which is here expressed by the attainment of the same pressure as in the case where hydrogen acts on iron oxides, and as in the case where (at the same temperature) water is decomposed by metallic iron. The calculations referring to this matter were made by Henri Sainte-Claire Deville (1870). Spongy iron was placed in a tube having a temperature _t_, one end of which was connected with a vessel containing water at 0° (vapour tension = 4·6 mm.) and the other end with a mercury pump and pressure gauge which determined the limiting tension attained by the dry hydrogen _p_ (subtracting the tension of the water vapour from the tension observed). A tube was then taken containing an excess of iron oxide. It was filled with hydrogen, and the tension _p__{1} observed of the residual hydrogen when the water was condensed at 0°. _t_ = 200° 440° 860° 1040° _p_ = 95·9 25·8 12·8 9·2 mm. _p_{1} = -- -- 12·8 9·4 mm. The equality of the pressure (tension) of the hydrogen in the two cases is evident. The hydrogen here behaves like the vapour of iron or of its oxide. By taking ferric oxide, Fe_{2}O_{3}, Moissan observed that at 350° it passed into magnetic oxide, Fe_{3}O_{4}, at 500° into ferrous oxide, FeO, and at 600° into metallic iron. Wright and Luff (1878), whilst investigating the reduction of oxides, found that (_a_) the temperature of reaction depends on the condition of the oxide taken--for instance, precipitated ferric oxide is reduced by hydrogen at 85°, that obtained by oxidising the metal or from its nitrate at 175°; (_b_) when other conditions are the same, the reduction by carbonic oxide commences earlier than that by hydrogen, and the reduction by hydrogen still earlier than that by charcoal; (_c_) the reduction is effected with greater facility when a greater quantity of heat is evolved during the reaction. Ferric oxide obtained by heating ferrous sulphate to a red heat begins to be reduced by carbonic oxide at 202°, by hydrogen at 260°, by charcoal at 430°, whilst for magnetic oxide, Fe_{3}O_{4}, the temperatures are 200°, 290°, and 450° respectively. [6] The primitive methods of iron manufacture were conducted by intermittent processes in hearths resembling smiths' fires. As evidenced by the uninterrupted action of the steam boiler, or the process of lime burning, and the continuous preparation and condensation of sulphuric acid or the uninterrupted smelting of iron, every industrial process becomes increasingly profitable and complete under the condition of the continuous action, as far as possible, of all agencies concerned in the production. This continuous method of production is the first condition for the profitable production on the large scale of nearly all industrial products. This method lessens the cost of labour, simplifies the supervision of the work, renders the product uniform, and frequently introduces a very great economy in the expenditure of fuel and at the same time presents the simplicity and perfection of an equilibrated system. Hence every manufacturing operation should be a continuous one, and the manufacture of pig iron and sulphuric acid, which have long since become so, may be taken as examples in many respects. A study of these two manufactures should form the commencement of an acquaintance with all the contemporary methods of manufacturing both from a technical and economical point of view. [7] The composition of slag suitable for iron smelting most often approaches the following: 50 to 60 p.c. SiO_{2}, 5 to 20 Al_{2}O_{3}, the rest of the mass consisting of MgO, CaO, MnO, FeO. Thus the most fusible slag (according to the observations of Bodeman) contains the alloy Al_{2}O_{3},4CaO,7SiO_{2}. On altering the quantity of magnesia and lime, and especially of the alkalis (which increases the fusibility) and of silica (which decreases it), the temperature of fusion changes with the relation between the total quantity of oxygen and that in the silica. Slags of the composition RO,SiO_{2} are easily fusible, have a vitreous appearance, and are very common. Basic slags approach the composition 2RO,SiO_{2}. Hence, knowing the composition and quantity of the foreign matter in the ore, it is at once easy to find the quantity and quality of the flux which must be added to form a suitable slag. The smelting of iron is rendered more complex by the fact that the silica, SiO_{2}, which enters into the slag and fluxes is capable of forming a slag with the iron oxides. In order that the least quantity of iron may pass into the slag, it is necessary for it to be reduced before the temperature is attained at which the slags are formed (about 1000°), which is effected by reducing the iron, not with charcoal itself, but with carbonic oxide. From this it will be understood how the progress of the whole treatment may be judged by the properties of the slags. Details of this complicated and well-studied subject will be found in works on metallurgy. Thus the following materials have to be introduced into the furnace where the smelting of the iron ore is carried on: (1) the iron ore, composed of oxide of iron and foreign matter; (2) the flux required to form a fusible slag with the foreign matter; (3) the carbon which is necessary (_a_) for reducing, (_b_) for combining with the reduced iron to form cast iron, (_c_) principally for the purpose of combustion and the heat generated thereby, necessary not only for reducing the iron and transforming it into cast iron, but also for melting the slag, as well as the cast iron--and (4) the air necessary for the combustion of the charcoal. The air is introduced after a preparatory heating in order to economise fuel and to obtain the highest temperature. The air is forced in under pressure by means of a special blast arrangement. This permits of an exact regulation of the heat and rate of smelting. All these component parts necessary for the smelting of iron must be contained in a vertical, that is, _shaft furnace_, which at the base must have a receptacle for the accumulation of the slag and cast iron formed, in order that the operation may proceed without interruption. The walls of such a furnace ought to be built of fireproof materials if it be designed to serve for the continuous production of cast iron by charging the ore, fuel, and flux into the mouth of the furnace, forcing a blast of air into the lower part, and running out the molten iron and slag from below. The whole operation is conducted in furnaces known as _blast furnaces_. The annexed illustration, fig. 93 (which is taken by kind permission from Thorpe's Dictionary of Applied Chemistry), represents the vertical section of such a furnace. These furnaces are generally of large dimensions--varying from 50 to 90 feet in height. They are sometimes built against rising ground in order to afford easy access to the top where the ore, flux, and charcoal or coke are charged.[8] [8] The section of a blast furnace is represented by two truncated cones joined at their bases, the upper cone being longer than the lower one; the lower cone is terminated by the hearth, or almost cylindrical cavity in which the cast iron and slag collect, one side being provided with apertures for drawing off the iron and slag. The air is blown into the blast furnace through special pipes, situated over the hearth, as shown in the section. The air previously passes through a series of cast-iron pipes, heated by the combustion of the carbonic oxide obtained from the upper parts of the furnace, where it is formed as in a 'gas-producer.' The blast furnace acts continuously until it is worn out; the iron is tapped off twice a day, and the furnace is allowed to cool a little from time to time so as not to be spoilt by the increasing heat, and to enable it to withstand long usage. Blast furnaces worked with charcoal fuel are not so high, and in general give a smaller yield than those using coke, because the latter are worked with heavier charges than those in which charcoal is employed. Coke furnaces yield 20,000 tons and over of pig iron a year. In the United States there are blast furnaces 30 metres high, and upwards of 600 cubic metres capacity, yielding as much as 130,000 tons of pig iron, requiring a blast of about 750 cubic metres of air per minute, heated to 600°, and consuming about 0·85 part of coke per 1 part of pig iron produced. At the present time the world produces as much as 30 million tons of pig iron a year, about 9/10 of which is converted into wrought iron and steel. The chief producers are the United States (about 10 million tons a year) and England (about 9 million tons a year); Russia yields about 1-1/5 million tons a year. The world's production has doubled during the last 20 years, and in this respect the United States have outrun all other countries. The reason of this increase of production must be looked for in the increased demand for iron and steel for railway purposes, for structures (especially ship-building), and in the fact that: (_a_) the cost of pig iron has fallen, thanks to the erection of large furnaces and a fuller study of the processes taking place in them, and (_b_) that every kind of iron ore (even sulphurous and phosphoritic) can now be converted into a homogeneous steel. [Illustration: FIG. 93.--Vertical section of a modern Cleveland blast furnace capable of producing 300 to 1,000 tons of pig iron weekly. The outer casing is of riveted iron plates, the furnace being lined with refractory fire-brick. It is closed at the top by a 'cap and cone' arrangement, by means of which the charge can be fed into the furnace at suitable intervals by lowering the moveable cone.] In order to more thoroughly grasp the chemical process which takes place in blast furnaces, it is necessary to follow the course of the material charged in at the top and of the air passing through the furnace. From 50 to 200 parts of carbon are expended on 100 parts of iron. The ore, flux, and coke are charged into the top of the furnace, in layers, as the cast iron is formed in the lower parts and flowing down to the bottom causes the whole contents of the furnace to subside, thus forming an empty space at the top, which is again filled up with the afore-mentioned mixture. During its downward course this mixture is subjected to increasing heat. This rise of temperature first drives off the moisture of the ore mixture, and then leads to the formation of the products of the dry distillation of coal or charcoal. Little by little the subsiding mass attains a temperature at which the heated carbon reacts with the carbonic anhydride passing upwards through the furnace and transforms it into carbonic oxide. This is the reason why carbonic anhydride is not evolved from the furnace, but only carbonic oxide. As regards the ore itself, on being heated to about 600° to 800° it is reduced at the expense of the carbonic oxide ascending the furnace, and formed by the contact of the carbonic anhydride with the incandescent charcoal, so that the reduction in the blast furnace is without doubt brought about _by_ the formation and decomposition of _carbonic oxide_ and not by carbon itself--thus, Fe_{2}O_{3} + 3CO = Fe_{2} + 3CO_{2}. The reduced iron, on further subsidence and contact with carbon, forms cast iron, which flows to the bottom of the furnace. In these lower layers, where the temperature is highest (about 1,300°), the foreign matter of the ore finally forms slag, which also is fusible, with the aid of fluxes. The air blown in from below, through the so-called _tuyeres_, encounters carbon in the lower layers of the furnace, and burns it, converting it into carbonic anhydride. It is evident that this develops the highest temperature in these lower layers of the furnace, because here the combustion of the carbon is effected by heated and compressed air. This is very essential, for it is by virtue of this high temperature that the process of forming the slag and of forming and fusing the cast iron are effected simultaneously in these lower portions of the furnace. The carbonic acid formed in these parts rises higher, encounters incandescent carbon, and forms with it carbonic oxide. This heated carbonic oxide acts as a reducing agent on the iron ore, and is reconverted by it into carbonic anhydride; this gas meets with more carbon, and again forms carbonic oxide, which again acts as a reducing agent. The final transformation of the carbonic anhydride into carbonic oxide is effected in those parts of the furnace where the reduction of the oxides of iron does not take place, but where the temperature is still high enough to reduce the carbonic anhydride. The ascending mixture of carbonic oxide and nitrogen, CO_{2}, &c., is then withdrawn through special lateral apertures formed in the upper cold parts of the furnace walls, and is conducted through pipes to those stoves which are used for heating the air, and also sometimes into other furnaces used for the further processes of iron manufacture. The fuel of blast furnaces consists of wood charcoal (this is the most expensive material, but the pig iron produced is the purest, because charcoal does not contain any sulphur, while coke does), anthracite (for instance, in Pennsylvania, and in Russia at Pastouhoff's works in the Don district), coke, coal, and even wood and peat. It must be borne in mind that the utilisation of naphtha and naphtha refuse would probably give very profitable results in metallurgical processes. The process just described is accompanied by a series of other processes. Thus, for instance, in the blast furnace a considerable quantity of cyanogen compounds are formed. This takes place because the nitrogen of the air blast comes into contact with incandescent carbon and various alkaline matters contained in the foreign matter of the ores. A considerable quantity of potassium cyanide is formed when wood charcoal is employed for iron smelting, as its ash is rich in potash. The _cast iron_ formed in blast furnaces is not always of the same quality. When slowly cooled it is soft, has a grey colour, and is not completely soluble in acids. When treated with acids a residue of graphite remains; it is known as _grey_ or soft cast iron. This is the general form of the ordinary cast iron used for casting various objects, because in this state it is not so brittle as in the shape of _white cast iron_, which does not leave particles of graphite when dissolved, but yields its carbon in the form of hydrocarbons. This white cast iron is characterised by its whitish-grey colour, dull lustre, the crystalline structure of its fracture (more homogeneous than that of grey iron), and such hardness that a file will hardly cut it. When white cast iron is produced (from manganese ore) at high temperatures (and with an excess of lime), and containing little sulphur and silica but a considerable amount of carbon (as much as 5 p.c.), it acquires a coarse crystalline structure which increases in proportion to the amount of manganese, and it is then known under the name of 'spiegeleisen' (and 'ferro-manganese').[9] [9] The specific gravity of white cast iron is about 7·5. Grey cast iron has a much lower specific gravity, namely, 7·0. Grey cast iron generally contains less manganese and more silica than white; but both contain from 2 to 3 p.c. of carbon. The difference between the varieties of cast iron depends on the condition of the carbon which enters into the composition of the iron. In white cast iron the carbon is in combination with the iron--in all probability, as the compound CFe_{4} (Abel and Osmond and others extracted this compound, which is sometimes called 'carbide,' from tempered steel, which stands to unannealed steel as white cast iron does to grey), but perhaps in the state of an indefinite chemical compound resembling a solution. In any case the compound of the iron and carbon in white cast iron is chemically very unstable, because when slowly cooled it decomposes, with separation of graphite, just as a solution when slowly cooled yields a portion of the substance dissolved. The separation of carbon in the form of graphite on the conversion of white cast iron into grey is never complete, however slowly the separation be carried on; part of the carbon remains in combination with the iron in the same state in which it exists in white cast iron. Hence when grey cast iron is treated with acids, the whole of the carbon does not remain in the form of graphite, but a part of it is separated as hydrocarbons, which proves the existence of chemically-combined carbon in grey cast iron. It is sufficient to re-melt grey cast iron and to cool it quickly to transform it into white cast iron. It is not carbon alone that influences the properties of cast iron; when it contains a considerable amount of sulphur, cast iron remains white even after having been slowly cooled. The same is observed in cast iron very rich in manganese (5 to 7 p.c.), and in this latter case the fracture is very distinctly crystalline and brilliant. When cast iron contains a large amount of manganese, the quantity of carbon may also be increased. Crystalline varieties of cast iron rich in manganese are in practice called ferro-manganese (p. 310), and are prepared for the Bessemer process. Grey cast iron not having an uniform structure is much more liable to various changes than dense and thoroughly uniform white cast iron, and the latter oxidises much more slowly in air than the former. White cast iron is not only used for conversion into wrought iron and steel, but also in those cases where great hardness is required, although it be accompanied by a certain brittleness; for instance, for making rollers, plough-shares, &c. Cast iron is a material which is either suitable for direct application for casting in moulds or else for working up into _wrought iron_ and _steel_. The latter principally differ from cast iron in their containing less carbon--thus, steel contains from 1 p.c. to 0·5 p.c. of carbon and far less silicon and manganese than cast iron; wrought iron does not generally contain more than 0·25 p.c. of carbon and not more than 0·25 p.c. of the other impurities. Thus the essence of the working up of cast iron into steel and wrought iron consists in the removal of the greater part of the carbon and other elements, S, P, Mn, Si, &c. This is effected by means of oxidation, because the oxygen of the atmosphere, oxidising the iron at a high temperature, forms solid oxides with it; and the latter, coming into contact with the carbon contained in the cast iron, are deoxidised, forming wrought iron and carbonic oxide, which is evolved from the mass in a gaseous form. It is evident that the oxidation must be carried on with a molten mass in a state of agitation, so that the oxygen of the air may be brought into contact with the whole mass of carbon contained in the cast iron, or else the operation is effected by means of the addition of oxygen compounds of iron (oxides, ores, as in Martin's process). Cast iron melts much more easily than wrought iron and steel, and, therefore, as the carbon separates, the mass in the furnace (in puddling) or hearth (in the bloomery process) becomes more and more solid; moreover the degree of hardness forms, to a certain extent, a measure of the amount of carbon separated, and the operation may terminate either in the formation of steel or wrought iron.[10] In any case, the iron used for industrial purposes contains impurities. _Chemically pure iron_ may be obtained by precipitating iron from a solution (a mixture of ferrous sulphate with magnesium sulphate or ammonium chloride) by the prolonged action of a feeble galvanic current; the iron may be then obtained as a dense mass. This method, proposed by Böttcher and applied by Klein, gives, as R. Lenz showed, iron containing occluded hydrogen, which is disengaged on heating. This galvanic deposition of iron is used for making galvanoplastic _clichés_, which are distinguished for their great hardness. Electro-deposited iron is brittle, but if heated (after the separation of the hydrogen) it becomes soft. If pure ferric hydroxide, which is easily prepared by the precipitation of solutions of ferric salts by means of ammonia, be heated in a stream of hydrogen, it forms, first of all, a dull black powder which ignites spontaneously in air (pyrophoric iron), and then a grey powder of pure iron. The powdery substance first obtained is an iron suboxide; when thrown into the air it ignites, forming the oxide Fe_{3}O_{4}. If the heating in hydrogen be continued, more water and pure iron, which does not ignite spontaneously, will be obtained. If a small quantity of iron be fused in the oxyhydrogen flame (with an excess of oxygen) in a piece of lime and mixed with powdered glass, pure molten iron will be formed, because in the oxyhydrogen flame iron melts and burns, but the substances mixed with the iron oxidise first. The oxidised impurities here either disappear (carbonic anhydride) in a gaseous form, or turn into slag (silica, manganese, oxide, and others)--that is, fuse with the glass. Pure iron has a silvery white colour and a specific gravity of 7·84; it melts at a temperature higher than the melting-points of silver, gold, nickel, and steel, _i.e._ about 1400°-1500° and below the melting point of platinum (1750°).[11] But pure iron becomes soft at a temperature considerably below that at which it melts, and may then be easily forged, welded, and rolled or drawn into sheets and wire.[11 bis] Pure iron may be rolled into an exceedingly thin sheet, weighing less than a sheet of ordinary paper of the same size. This ductility is the most important property of iron in all its forms, and is most marked with sheet iron, and least so with cast iron, whose ductility, compared with wrought iron, is small, but it is still very considerable when compared with other substances--such, for instance, as rocks.[12] [10] This direct process of separating the carbon from cast iron is termed _puddling_. It is conducted in reverberatory furnaces. The cast iron is placed on the bed of the furnace and melted; through a special aperture, the puddler stirs up the oxidising mass of cast iron, pressing the oxides into the molten iron. This resembles kneading dough, and the process introduced in England became known as puddling. It is evident that the puddled mass, or bloom, is a heterogeneous substance obtained by mixing, and hence one part of the mass will still be rich in carbon, another will be poor, some parts will contain oxide not reduced, &c. The further treatment of the puddled mass consists in hammering and drawing it out into flat pieces, which on being hammered become more homogeneous, and when several pieces are welded together and again hammered out a still more homogeneous mass is obtained. The quality of the steel and iron thus formed depends principally on their uniformity. The want of uniformity depends on the oxides remaining inside the mass, and on the variable distribution of the carbon throughout the mass. In order to obtain a more homogeneous metal for manufacturing articles out of steel, it is drawn into thin rods, which are tied together in bundles and then again hammered out. As an example of what may be attained in this direction, imitation Damascus steel may be cited; it consists of twisted and plaited wire, which is then hammered into a dense mass. (Real damascened wootz steel may be made by melting a mixture of the best iron with graphite (1/12) and iron rust; the article is then corroded with acid, and the carbon remains in the form of a pattern.) Steel and wrought iron are manufactured from cast iron by puddling. They are, however, obtained not only by this method but also by the _bloomery process_, which is carried out in a fire similar to a blacksmith's forge, fed with charcoal and provided with a blast; a pig of cast iron is gradually pushed into the fire, and portions of it melt and fall to the bottom of the hearth, coming into contact with an air blast, and are thus oxidised. The bloom thus formed is then squeezed and hammered. It is evident that this process is only available when the charcoal used in the fire does not contain any foreign matter which might injure the quality of the iron or steel--for instance, sulphur or phosphorus--and therefore only wood charcoal may be used with impunity, from which it follows that this process can only be carried on where the manufacture of iron can be conducted with this fuel. Coal and coke contain the above-mentioned impurities, and would therefore produce iron of a brittle nature, and thus it would be necessary to have recourse to puddling, where the fuel is burnt on a special hearth, separate from the cast iron, whereby the impurities of the fuel do not come into contact with it. The manufacture of steel from cast iron may also be conducted in fires; but, in addition to this, it is also now prepared by many other methods. One of the long-known processes is called _cementation_, by which steel is prepared from wrought iron but not from cast iron. For this process strips of iron are heated red-hot for a considerable time whilst immersed in powdered charcoal; during this operation the iron at the surface combines with the charcoal, which however does not penetrate; after this the iron strips are re-forged, drawn out again, and cemented anew, repeating this process until a steel of the desired quality is formed--that is, containing the requisite proportion of carbon. The _Bessemer_ process occupies the front rank among the newer methods (since 1856); it is so called from the name of its inventor. This process consists in running melted cast iron into converters (holding about 6 tons of cast iron)--that is, egg-shaped receivers, fig. 94, capable of revolving on trunnions (in order to charge in the cast iron and discharge the steel), and forcing a stream of air through small apertures at a considerable pressure. Combustion of the iron and carbon at an elevated temperature then takes place, resulting from the bubbles of oxygen thus penetrating the mass of the cast iron. The carbon, however, burns to a greater extent than the iron, and therefore a mass is obtained which is much poorer in carbon than cast iron. As the combustion proceeds very rapidly in the mass of metal, the temperature rises to such an extent that even the wrought iron which may be formed remains in a molten condition, whilst the steel, being more fusible than the wrought iron, remains very liquid. In half an hour the mass is ready. The purest possible cast iron is used in the Bessemer process, because sulphur and phosphorus do not burn out like carbon, silicon, and manganese. [Illustration: FIG. 94.--Bessemer converter, constructed of iron plate and lined with ganister. The air is carried by the tubes, L, O, D to the bottom, M, from which it passes by a number of holes into the converter. The converter is rotated on the trunnion _d_ by means of the rack and pinion H, when it is required either to receive molten cast iron from the melting furnaces or to pour out the steel.] The presence of manganese enables the sulphur to be removed with the slag, and the presence of lime or magnesia, which are introduced into the lining of the converter, facilitates the removal of the phosphorus. This basic Bessemer process, or _Thomas Gilchrist process_, introduced about 1880, enables ores containing a considerable amount of phosphorus, which had hitherto only been used for cast iron, to be used for making wrought iron and steel. Naturally the greatest uniformity will be obtained by re-melting the metal. Steel is re-melted in small wind furnaces, in masses not exceeding 30 kilos; a liquid metal is formed, which may be cast in moulds. A mixture of wrought and cast iron is often used for making cast steel (the addition of a small amount of metallic Al improves the homogeneity of the castings, by facilitating the passage of the impurities into slag). Large steel castings are made by simultaneous fusion in several furnaces and crucibles; in this way, castings up to 80 tons or more, such as large ordnance, may be made. This molten, and therefore homogeneous, steel is called _cast steel_. Of late years the _Martin's process_ for the manufacture of steel has come largely into use; it was invented in France about 1860, and with the use of regenerative furnaces it enables large quantities of cast steel to be made at a time. It is based on the melting of cast iron with iron oxides and iron itself--for instance, pure ores, scrap, &c. There the carbon of the cast iron and the oxygen of the oxide form carbonic oxide, and the carbon therefore burns out, and thus cast steel is obtained from cast iron, providing, naturally, that there is a requisite proportion and corresponding degree of heat. The advantage of this process is that not only do the carbon, silicon, and manganese, but also a great part of the sulphur and phosphorus of the cast iron burn out at the expense of the oxygen of the iron oxides. During the last decade the manufacture of steel and its application for rails, armour plate, guns, boilers, &c., has developed to an enormous extent, thanks to the invention of cheap processes for the manufacture of large masses of homogeneous cast steel. Wrought iron may also be melted, but the heat of a blast furnace is insufficient for this. It easily melts in the oxyhydrogen flame. It may be obtained in a molten state directly from cast iron, if the latter be melted with nitre and sufficiently stirred up. Considerable oxidation then takes place inside the mass of cast iron, and the temperature rises to such an extent that the wrought iron formed remains liquid. A method is also known for obtaining wrought iron directly from rich iron ores by the action of carbonic oxide: the wrought iron is then formed as a spongy mass (which forms an excellent filter for purifying water), and may be worked up into wrought iron or steel either by forging or by dissolving in molten cast iron. Everybody is more or less familiar with the _difference in the properties of steel and wrought iron_. Iron is remarkable for its softness, pliability, and small elasticity, whilst steel may be characterised by its capability of attaining elasticity and hardness if it be cooled suddenly after having been heated to a definite temperature, or, as it is termed, _tempered_. But if tempered steel be re-heated and slowly cooled, it becomes as soft as wrought iron, and can then be cut with the file and forged, and in general can be made to assume any shape, like wrought iron. In this soft condition it is called _annealed steel_. The transition from tempered to annealed steel thus takes place in a similar way to the transition from white to grey cast iron. Steel, when homogeneous, has considerable lustre, and such a fine granular structure that it takes a very high polish. Its fracture clearly shows the granular nature of its structure. The possibility of tempering steel enables it to be used for making all kinds of cutting instruments, because annealed steel can be forged, turned, drawn (under rollers, for instance, for making rails, bars, &c.), filed, &c., and it may then be tempered, ground and polished. The method and temperature of tempering and annealing steel determine its hardness and other qualities. Steel is generally tempered to the required degree of hardness in the following manner: It is first strongly heated (for instance, up to 600°), and then plunged into water--that is, hardened by rapid cooling (it then becomes as brittle as glass). It is then heated until the surface assumes a definite colour, and finally cooled either quickly or slowly. When steel is heated up to 220°, its surface acquires a yellow colour (surgical instruments); it first of all becomes straw-coloured (razors, &c.), and then gold-coloured; then at a temperature of 250° it becomes brown (scissors), then red, then light blue at 285° (springs), then indigo at 300° (files), and finally sea-green at about 340°. These colours are only the tints of thin films, like the hues of soap bubbles, and appear on the steel because a thin layer of oxides is formed over its surface. Steel rusts more slowly than wrought iron, and is more soluble in acids than cast iron, but less so than wrought iron. Its specific gravity is about 7·6 to 7·9. As regards the formation of steel, it was a long time before the process of cementation was thoroughly understood, because in this case infusible charcoal permeates unfused wrought iron. Caron showed that this permeation depends on the fact that the charcoal used in the process contains alkalis, which, in the presence of the nitrogen of the air, form metallic cyanides; these being volatile and fusible, permeate the iron, and, giving up their carbon to it, serve as the material for the formation of steel. This explanation is confirmed by the fact that charcoal without alkalis or without nitrogen will not cement iron. The charcoal used for cementation acts badly when used over again, as it has lost alkali. The very volatile ammonium cyanide easily conduces to the formation of steel. Although steel is also formed by the action of cyanogen compounds, nevertheless it does not contain more nitrogen than cast or wrought iron (0·01 p.c.), and these latter contain it because their ores contain titanium, which combines directly with nitrogen. Hence the part played by nitrogen in steel is but an insignificant one. It may be useful here to add some information taken from Caron's treatise concerning the influence of foreign matter on the quality of steel. The principal properties of steel are those of tempering and annealing. The compounds of iron with silicon and boron have not these properties. They are more stable than the carbon compound, and this latter is capable of changing its properties; because the carbon in it either enters into combination or else is disengaged, which determines the condition of hardness or softness of steel, as in white and grey cast iron. When slowly cooled, steel splits up into a mixture of soft and carburetted iron; but, nevertheless, the carbon does not separate from the iron. If such steel be again heated, it forms a uniform compound, and hardens when rapidly cooled. If the same steel as before be taken and heated a long time, then, after being slowly cooled, it becomes much more soluble in acid, and leaves a residue of pure carbon. This shows that the combination between the carbon and iron in steel becomes destroyed when subjected to heat, and the steel becomes iron mixed with carbon. Such _burnt_ steel cannot be tempered, but may be corrected by continued forging in a heated condition, which has the effect of redistributing the carbon equally throughout the whole mass. After the forging, if the iron is pure and the carbon has not been burnt out, steel is again formed, which may be tempered. If steel be repeatedly or strongly heated, it becomes burnt through and cannot be tempered or annealed; the carbon separates from the iron, and this is effected more easily if the steel contains other impurities which are capable of forming stable combinations with iron, such as silicon, sulphur, or phosphorus. If there be much silicon, it occupies the place of the carbon, and then continued forging will not induce the carbon once separated to re-enter into combination. Such steel is easily burnt through and cannot be corrected; when burnt through, it is hard and cannot be annealed--this is tough steel, an inferior kind. Iron which contains sulphur and phosphorus cements badly, combines but little with carbon, and steel of this kind is brittle, both hot and cold. Iron in combination with the above-mentioned substances cannot be annealed by slow cooling, showing that these compounds are more stable than those of carbon and iron, and therefore they prevent the formation of the latter. Such metals as tin and zinc combine with iron, but not with carbon, and form a brittle mass which cannot be annealed and is deleterious to steel. Manganese and tungsten, on the contrary, are capable of combining with charcoal; they do not hinder the formation of steel, but even remove the injurious effects of other admixtures (by transforming these admixed substances into new compounds and slags), and are therefore ranked with the substances which act beneficially on steel; but, nevertheless, the best steel, which is capable of renewing most often its primitive qualities after burning or hot forging, is the purest. The addition of Ni, Cr, W, and certain other metals to steel renders it very suitable for certain special purposes, and is therefore frequently made use of. It is worthy of attention that steel, besides temper, possesses many variable properties, a review of which may be made in the classification of the _sorts of steel_ (1878, Cockerell). (1) _Very mild steel_ contains from 0·05 to 0·20 p.c. of carbon, breaks with a weight of 40 to 50 kilos per square millimetre, and has an extension of 20 to 30 p.c.; it may be welded, like wrought iron, but cannot be tempered; is used in sheets for boilers, armour plate and bridges, nails, rivets, &c., as a substitute for wrought iron; (2) _mild steel_, from 0·20 to 0·35 p.c. of carbon, resistance to tension 50 to 60 kilos, extension 15 to 20 p.c., not easily welded, and tempers badly, used for axles, rails, and railway tyres, for cannons and guns, and for parts of machines destined to resist bending and torsion; (3) _hard steel_, carbon 0·35 to 0·50 p.c., breaking weight 60 to 70 kilos per square millimetre, extension 10 to 15 p.c., cannot be welded, takes a temper; used for rails, all kinds of springs, swords, parts of machinery in motion subjected to friction, spindles of looms, hammers, spades, hoes, &c.; (4) _very hard steel_, carbon 0·5 to 0·65 p.c., tensile breaking weight 70 to 80 kilos, extension 5 to 10 p.c., does not weld, but tempers easily; used for small springs, saws, files, knives and similar instruments. The properties of ordinary _wrought iron_ are well known. The best iron is the most tenacious--that is to say, that which does not break up when struck with the hammer or bent, and yet at the same time is sufficiently hard. There is, however, a distinction between hard and soft iron. Generally the softest iron is the most tenacious, and can best be welded, drawn into wire, sheets, &c. Hard, especially tough, iron is often characterised by its breaking when bent, and is therefore very difficult to work, and objects made from it are less serviceable in many respects. Soft iron is most adapted for making wire and sheet iron and such small objects as nails. Soft iron is characterised by its attaining a fibrous fracture after forging, whilst tough iron preserves its granular structure after this operation. Certain sorts of iron, although fairly soft at the ordinary temperature, become brittle when heated and are difficult to weld. These sorts are less suitable for being worked up into small objects. The variety of the properties of iron depends on the impurities which it contains. In general, the iron used in the arts still contains carbon and always a certain quantity of silicon, manganese, sulphur, phosphorus, &c. A variety in the proportion of these component parts changes the quality of the iron. In addition to this the change which soft wrought iron, having a fibrous structure, undergoes when subjected to repeated blows and vibrations is considerable; it then becomes granular and brittle. This to a certain degree explains the want of stability of some iron objects--such as truck axles, which must be renewed after a certain term of service, otherwise they become brittle. It is evident that there are innumerable intermediate transitions from wrought iron to steel and cast iron. At the present day the greater part of the cast iron manufactured is converted into steel, generally cast steel (Bessemer's and Martin's). I may add the Urals, Donetz district, and other parts of Russia offer the greatest advantages for the development of an iron industry, because these localities not only contain vast supplies of excellent iron ore, but also coal, which is necessary for smelting it. [11] According to information supplied by A. T. Skinder's experiments at the Oboukoff Steel Works, 140 volumes of liquid molten steel give 128 volumes of solid metal. By means of a galvanic current of great intensity and dense charcoal as one electrode, and iron as the other, Bernadoss welded iron and fused holes through sheet iron. Soft wrought iron, like steel and soft malleable cast iron, may be melted in Siemens' regenerative furnaces, and in furnaces heated with naphtha. [11 bis] Gore (1869), Tait, Barret, Tchernoff, Osmond, and others observed that at a temperature approaching 600°--that is, between dark and bright red heat--all kinds of wrought iron undergo a peculiar change called _recalescence_, _i.e._ a spontaneous rise of temperature. If iron be considerably heated and allowed to cool, it may be observed that at this temperature the cooling stops--that is, latent heat is disengaged, corresponding with a change in condition. The specific heat, electrical conductivity, magnetic, and other properties then also change. In tempering, the temperature of recalescence must not be reached, and so also in annealing, &c. It is evident that a change of the internal condition is here encountered, exactly similar to the transition from a solid to a liquid, although there is no evident physical change. It is probable that attentive study would lead to the discovery of a similar change in other substances. [12] The particles of steel are linked together or connected more closely than those of the other metals; this is shown by the fact that it only breaks with a tensile strain of 50-80 kilos per sq. mm., whilst wrought iron only withstands about 30 kilos, cast iron 10, copper 35, silver 23, platinum 30, wood 8. The elasticity of iron, steel, and other metals is expressed by the so-called _coefficient of elasticity_. Let a rod be taken whose length is L; if a weight, P, be hung from the extremity of it, it will lengthen to _l_. The less it lengthens under other equal conditions, the more elastic the material, if it resumes its original length when the weight is removed. It has been shown by experiment that the increase in length _l_, due to elasticity, is directly proportional to the length L and the weight P, and inversely proportional to the section, but changes with the material. The coefficient of elasticity expresses that weight (in kilos per sq. mm.) under which a rod having a square section taken as 1 (we take 1 sq. mm.) acquires double the length by tension. Naturally in practice materials do not withstand such a lengthening, under a certain weight they attain a limit of elasticity, _i.e._ they stretch permanently (undergo deformation). Neglecting fractions (as the elasticity of metals varies not only with the temperature, but also with forging, purity, &c.), the coefficient of elasticity of steel and iron is 20,000, copper and brass 10,000, silver 7,000, glass 6,000, lead 2,000, and wood 1,200. _The chemical properties of iron_ have been already repeatedly mentioned in preceding chapters. Iron _rusts_ in air at the ordinary temperature--that is to say, it becomes covered with a layer of iron oxides. Here, without doubt, the moisture of the air plays a part, because in dry air iron does not oxidise at all, and also because, more particularly, ammonia is always found in iron rust; the ammonia must arise from the action of the hydrogen of the water, at the moment of its separation, on the nitrogen of the air. Highly-polished steel does not rust nearly so readily, but if moistened with water, it easily becomes coated with rust. As rust depends on the access of moisture, iron may be preserved from rust by coating it with substances which prevent the moisture having access to it. Thus arises the practice of covering iron objects with paraffin,[13] varnish, oil, paints, or enamelling it with a glassy-looking flux possessing the same coefficient of expansion as iron, or with a dense scoria (formed by the heat of superheated steam), or with a compact coating of various metals. Wrought iron (both as sheet iron and in other forms), cast iron, and steel are often coated with tin, copper, lead, nickel, and similar metals, which prevent contact with the air. These metals preserve iron very effectually from rust if they form a completely compact surface, but in those places where the iron becomes exposed, either accidentally or from wear, rust appears much more quickly than on a uniform iron surface, because, towards these metals (and also towards the rust), the iron will then behave as an electro-positive pole in a galvanic couple, and hence will attract oxygen. A coating of zinc does not produce this inconvenience, because iron is electro-negative with reference to zinc, in consequence of which galvanised iron does not easily rust, and even an iron boiler containing some lumps of zinc rusts less than one without zinc.[14] Iron oxidises at a high temperature, forming _iron scale_, Fe_{3}O_{4}, composed of ferrous and ferric oxides, and, as has been seen, decomposes water and acids with the evolution of hydrogen. It is also capable of decomposing salts and oxides of other metals, which property is applied in the arts for the extraction of copper, silver, lead, tin, &c. For this reason iron is soluble in the solutions of many salts--for instance, in cupric sulphate, with precipitation of copper and formation of ferrous sulphate.[15] When iron _acts on acids_ it always _forms compounds_ FeX_{2}--that is, corresponding to the suboxide FeO--and answering to magnesium compounds--and hence two atoms of hydrogen are replaced by one atom of iron. Strongly oxidising acids like nitric acid may transform the ferrous salt which is forming into the higher degree of oxidation or ferric salt (corresponding with the sesquioxide, Fe_{2}O_{3}), but this is a secondary reaction. Iron, although easily soluble in dilute nitric acid, loses this property when plunged into strong fuming nitric acid; after this operation it even loses the property of solubility in other acids until the external coating formed by the action of the strong nitric acid is mechanically removed. This condition of iron is termed the passive state. _The passive condition_ of iron depends on the formation, on its surface, of a coating of oxide due to the iron being acted on by the lower oxides of nitrogen contained in the fuming nitric acid.[16] Strong nitric acid which does not contain these lower oxides, does not render iron passive, but it is only necessary to add some alcohol or other reducing agent which forms these lower oxides in the nitric acid, and the iron will assume the passive state. [13] Paraffin is one of the best preservatives for iron against oxidation in the air. I found this by experiments about 1860, and immediately published the fact. This method is now very generally applied. [14] See Chapter XVIII., Note 34 bis. Based on the rapid oxidation of iron and its increase in volume in the presence of water and salts of ammonium, a packing is used for water mains and steam pipes which is tightly hammered into the socket joints. This packing consists of a mixture of iron filings and a small quantity of sal-ammoniac (and sulphur) moistened with water; after a certain lapse of time, especially after the pipes have been used, this mass swells to such an extent that it hermetically seals the joints of the pipes. [15] Here, however, a ferric salt may also be formed (when all the iron has dissolved and the cupric salt is still in excess), because the cupric salts are reduced by ferrous salts. Cast iron is also dissolved. [16] Powdery reduced iron is passive with regard to nitric acid of a specific gravity of 1·37, but when heated the acid acts on it. This passiveness disappears in the magnetic field. Saint-Edme attributes the passiveness of iron (and nickel) to the formation of nitride of iron on the surface of the metal, because he observed that when heated in dry hydrogen ammonia is evolved by passive iron. Remsen observed that if a strip of iron be immersed in acid and placed in the magnetic field, it is principally dissolved at its middle part--that is, the acid acts more feebly at the poles. According to Étard (1891) strong nitric acid dissolves iron in making it passive, although the action is a very slow one. Iron readily combines with non-metals--for instance, with chlorine, iodine, bromine, sulphur, and even with phosphorus and carbon; but on the other hand the property of combining with metals is but little developed in it--that is to say, it does not easily form alloys. Mercury, which acts on most metals, does not act directly on iron, and the _iron amalgam_, or solution of iron in mercury, which is used for electrical machines, is only obtained in a particular way--namely, with the co-operation of a sodium amalgam, in which the iron dissolves and by means of which it is reduced from solutions of its salts. When iron acts on acids it forms ferrous salts of the type FeX_{2}, and in the presence of air and oxidising agents they change by degrees into ferric salts of the type FeX_{3}. This faculty of passing from the ferrous to the ferric state is still further developed in ferrous hydroxide. If sodium hydroxide be added to a solution of ferrous sulphate or green vitriol, FeSO_{4},[17] a white precipitate of ferrous hydroxide, FeH_{2}O_{2}, is obtained; but on exposure to the air, even under water, it turns green, becomes grey, and finally turns brown, which is due to the oxidation that it undergoes. Ferrous hydroxide is very sparingly soluble in water; the solution has, however, a distinct alkaline reaction, which is due to its being a fairly energetic basic oxide. In any case, ferrous oxide is far more energetic than ferric oxide, so that if ammonia be added to a solution containing a mixture of a ferrous and ferric salt, at first ferric hydroxide only will be precipitated. If barium carbonate, BaCO_{3}, be shaken up in the cold with ferrous salts, it does not precipitate them--that is, does not change them into ferrous carbonate; but it completely separates all the iron from the ferric salts in the cold, according to the equation Fe_{2}Cl_{6} + 3BaCO_{3} + 3H_{2}O = Fe_{2}O_{3},3H_{2}O + 3BaCl_{2} + 3CO_{2}. If ferrous hydroxide be boiled with a solution of potash, the water is decomposed, hydrogen is evolved, and the ferrous hydroxide is oxidised. The ferrous salts are in all respects similar to the salts of magnesium and zinc; they are isomorphous with them, but differ from them in that the ferrous hydroxide is not soluble either in aqueous potash or ammonia. In the presence of an excess of ammonium salts, however, a certain proportion of the iron is not precipitated by alkalis and alkali carbonates, which fact points to the formation of double ammonium salts.[18] The ferrous salts have a dull _greenish_ colour, and form solutions also of a pale green colour, whilst the ferric salts have a _brown_ or reddish-brown colour. The ferrous salts, being capable of oxidation, form very active reducing agents--for instance, under their action gold chloride, AuCl_{3}, deposits metallic gold, nitric acid is transformed into lower oxides, and the highest oxides of manganese also pass into the lower forms of oxidation. All these reactions take place with especial ease in the presence of an excess of acid. This depends on the fact that the ferrous oxide, FeO (or salt), acting as a reducing agent, turns into ferric oxide, Fe_{2}O_{3} (or salt), and in the ferric state it requires more acid for the formation of a normal salt than in the ferrous condition. Thus in the normal ferrous sulphate, FeSO_{4}, there is one equivalent of iron to one equivalent of sulphur (in the sulphuric radicle), but in the neutral ferric salt, Fe_{2}(SO_{4})_{3}, there is one equivalent of iron to one and a half of sulphur in the form of the elements of sulphuric acid.[19] [17] _Iron vitriol_ or _green vitriol_, sulphate of iron or ferrous sulphate, generally crystallises from solutions, like magnesium sulphate, with seven molecules of water, FeSO_{4},7H_{2}O. This salt is not only formed by the action of iron on sulphuric acid, but also by the action of moisture and air on iron pyrites, especially when previously roasted (FeS_{2} + O_{2} = FeS + SO_{2}), and in this condition it easily absorbs the oxygen of damp air (FeS + O_{4} = FeSO_{4}). Green vitriol is obtained in many processes as a by-product. Ferrous sulphate, like all the ferrous salts, has a pale greenish colour hardly perceptible in solution. If it be desired to preserve it without change--that is, so as not to contain ferric compounds--it is necessary to keep it hermetically sealed. This is best done by expelling the air by means of sulphurous anhydride or ether; sulphurous anhydride, SO_{2}, removes oxygen from ferric compounds, which might be formed, and is itself changed into sulphuric acid, and hence the oxidation of the ferrous compound does not take place in its presence. Unless these precautions are taken, green vitriol turns brown, partly changing into the ferric salt. When turned brown, it is not completely soluble in water, because during its oxidation a certain amount of free insoluble ferric oxide is formed: 6FeSO_{4} + O_{3} = 2Fe_{2}(SO_{4})_{3} + Fe_{2}O_{3}. In order to cleanse such mixed green vitriol from the oxide, it is necessary to add some sulphuric acid and iron and boil the mixture; the ferric salt is then transformed into the ferrous state: Fe_{2}(SO_{4})_{3} + Fe = 3FeSO_{4}. Green vitriol is used for the manufacture of Nordhausen sulphuric acid (Chapter XX.), for preparing ferric oxide, in many dye works (for preparing the indigo vats and reducing blue indigo to white), and in many other processes; it is also a very good disinfectant, and is the cheapest salt from which other compounds of iron may be obtained. The other ferrous salts (excepting the yellow prussiate, which will be mentioned later) are but little used, and it is therefore unnecessary to dwell upon them. We will only mention _ferrous chloride_, which, in the crystalline state, has the composition FeCl_{2},4H_{2}O. It is easily prepared; for instance, by the action of hydrochloric acid on iron, and in the anhydrous state by the action of hydrochloric acid gas on metallic iron at a red heat. The anhydrous ferrous chloride then volatilises in the form of colourless cubic crystals. Ferrous oxalate (or the double potassium salt) acts as a powerful reducing agent, and is frequently employed in photography (as a developer). [18] Ferrous sulphate, like magnesium sulphate, easily forms double salts--for instance, (NH_{4})_{2}SO_{4},FeSO_{4},6H_{2}O. This salt does not oxidise in air so readily as green vitriol, and is therefore used for standardising KMnO_{4}. [19] The transformation of ferrous oxide into ferric oxide is not completely effected in air, as then only a part of the suboxide is converted into ferric oxide. Under these circumstances the so-called magnetic oxide of iron is generally produced, which contains atomic quantities of the suboxide and oxide--namely, FeO,Fe_{2}O_{3} = Fe_{3}O_{4}. This substance, as already mentioned, is found in nature and in iron scale. It is also formed when most ferrous and ferric salts are heated in air; thus, for instance, when ferrous carbonate, FeCO_{3} (native or the precipitate given by soda in a solution of FeX_{2}), is heated it loses the elements of carbonic anhydride, and magnetic oxide remains. This oxide of iron is attracted by the magnet, and is on this account called magnetic oxide, although it does not always show magnetic properties. If magnetic oxide be dissolved in any acid--for instance, hydrochloric--which does not act as an oxidising agent, a ferrous salt is first formed and ferric oxide remains, which is also capable of passing into solution. The best way of preparing the hydrate of the magnetic oxide is by decomposing a mixture of ferrous and ferric salts with ammonia; it is, however, indispensable to pour this mixture into the ammonia, and not _vice versâ_, as in that case the ferrous oxide would at first be precipitated alone, and then the ferric oxide. The compound thus formed has a bright green colour, and when dried forms a black powder. Other combinations of ferrous with ferric oxide are known, as are also compounds of ferric oxide with other bases. Thus, for instance, compounds are known containing 4 molecules of ferrous oxide to 1 of ferric oxide, and also 6 of ferrous to 1 of ferric oxide. These are also magnetic, and are formed by heating iron in air. The magnesium compound MgO,Fe_{2}O_{3} is prepared by passing gaseous hydrochloric acid over a heated mixture of magnesia and ferric oxide. Crystalline magnesium oxide is then formed, and black, shiny, octahedral crystals of the above-mentioned composition. This compound is analogous to the aluminates--for instance, to spinel. Bernheim (1888) and Rousseau (1891) obtained many similar compounds of ferric oxide, and their composition apparently corresponds to the hydrates (Note 22) known for the oxide. The most simple oxidising agent for transforming ferrous into ferric salts is chlorine in the presence of water--for instance, 2FeCl_{2} + Cl_{2} = Fe_{2}Cl_{6}, or, generally speaking, 2FeO + Cl_{2} + H_{2}O = Fe_{2}O_{3} + 2HCl. When such a transformation is required it is best to add potassium chlorate and hydrochloric acid to the ferrous solution; chlorine is formed by their mutual reaction and acts as an oxidising agent. Nitric acid produces a similar effect, although more slowly. Ferrous salts may be completely and rapidly oxidised into ferric salts by means of chromic acid or permanganic acid, HMnO_{4}, in the presence of acids--for example, 10FeSO_{4} + 2KMnO_{4} + 8H_{2}SO_{4} = 5Fe_{2}(SO_{4})_{3} + 2MnSO_{4} + K_{2}SO_{4} + 8H_{2}O. This reaction is easily observed by the change of colour, and its termination is easily seen, because potassium permanganate forms solutions of a bright red colour, and when added to a solution of a ferrous salt the above reaction immediately takes place _in the presence of acid_, and the solution then becomes colourless, because all the substances formed are only faintly coloured in solution. Directly all the ferrous compound has passed into the ferric state, any excess of permanganate which is added communicates a red colour to the liquid (see Chapter XXI.) Thus when ferrous salts are acted on by oxidising agents, they pass into the ferric form, and under the action of reducing agents the reverse reaction occurs. Sulphuretted hydrogen may, for instance, be used for this complete transformation, for under its influence ferric salts are reduced with separation of sulphur--for example, Fe_{2}Cl_{6} + H_{2}S = 2FeCl_{2} + 2HCl + S. Sodium thiosulphate acts in a similar way: Fe_{2}Cl_{6} + Na_{2}S_{2}O_{3} + H_{2}O = 2FeCl_{2} + Na_{2}SO_{4} + 2HCl + S. Metallic iron or zinc,[20] in the presence, of acids, or sodium amalgam, &c., acts like hydrogen, and has also a similar reducing action, and this furnishes the best method for reducing ferric salts to ferrous salts--for instance, Fe_{2}Cl_{6} + Zn = 2FeCl_{2} + ZnCl_{2}. Thus _the transition from ferrous salts to ferric salts and vice versâ is always possible_.[21] [20] Copper and cuprous salts also reduce ferric oxide to ferrous oxide, and are themselves turned into cupric salts. The essence of the reactions is expressed by the following equations: Fe_{2}O_{3} + Cu_{2}O = 2FeO + 2CuO; Fe_{2}O_{3} + Cu = 2FeO + CuO. This fact is made use of in analysing copper compounds, the quantity of copper being ascertained by the amount of ferrous salt obtained. An excess of ferric salt is required to complete the reaction. Here we have an example of reverse reaction; the ferrous oxide or its salt in the presence of alkali transforms the cupric oxide into cuprous oxide and metallic copper, as observed by Lovel, Knopp, and others. [21] We will here mention the reactions by means of which it may be ascertained whether the ferrous compound has been entirely converted into a ferric compound or _vice versâ_. There are two substances which are best employed for this purpose: potassium ferricyanide, FeK_{3}C_{6}N_{6}, and potassium thiocyanate, KCNS. The first salt gives with ferrous salts a blue precipitate of an insoluble salt, having a composition Fe_{5}C_{12}N_{12}; but with ferric salts it does not form any precipitate, and only gives a brown colour, and therefore when transforming a ferrous salt into a ferric salt, the completion of the transformation may be detected by taking a drop of the liquid on paper or on a porcelain plate and adding a drop of the ferricyanide solution. If a blue precipitate be formed, then part of the ferrous salt still remains; if there is none, the transformation is complete. The thiocyanate does not give any marked coloration with ferrous salts; but with ferric salts in the most diluted state it forms a bright red soluble compound, and therefore when transforming a ferric salt into a ferrous salt we must proceed as before, testing a drop of the solution with thiocyanate, when the absence of a red colour will prove the total transformation of the ferric salt into the ferrous state, and if a red colour is apparent it shows that the transformation is not yet complete. _Ferric oxide_, or _sesquioxide of iron_, Fe_{2}O_{3}, is found in nature, and is artificially prepared in the form of a red powder by many methods. Thus after heating green vitriol a red oxide of iron remains, called colcothar, which is used as an oil paint, principally for painting wood. The same substance in the form of a very fine powder (rouge) is used for polishing glass, steel, and other objects. If a mixture of ferrous sulphate with an excess of common salt be strongly heated, crystalline ferric oxide will be formed, having a dark violet colour, and resembling some natural varieties of this substance. When iron pyrites is heated for preparing sulphurous anhydride, ferric oxide also remains behind; it is used as a pigment. On the addition of alkalis to a solution of ferric salts, a brown precipitate of ferric hydroxide is formed, which when heated (even when boiled in water, that is, at about 100°, according to Tomassi) easily parts with the water, and leaves red anhydrous ferric oxide. Pure ferric oxide does not show any magnetic properties, but when heated to a white heat it loses oxygen and is converted into the magnetic oxide. Anhydrous ferric oxide which has been heated to a high temperature is with difficulty soluble in acids (but it is soluble when heated in strong acids, and also when fused with potassium hydrogen sulphate), whilst ferric hydroxide, at all events that which is precipitated from salts by means of alkalis, is very readily soluble in acids. The precipitated _ferric hydroxide_ has the composition 2Fe_{2}O_{3}3H_{2}O, or Fe_{4}H_{6}O_{9}. If this ordinary hydroxide be rendered anhydrous (at 100°), at a certain moment it becomes incandescent--that is, loses a certain quantity of heat. This self-incandescence depends on internal displacement produced by the transition of the easily-soluble (in acids) variety into the difficultly-soluble variety, and does not depend on the loss of water, since the anhydrous oxide undergoes the same change. In addition to this there exists a ferric hydroxide, or hydrated oxide of iron, which, like the strongly-heated anhydrous iron oxide, is difficultly soluble in acids. This hydroxide on losing water, or after the loss of water, does not undergo such self-incandescence, because no such state of internal displacement occurs (loss of energy or heat) with it as that which is peculiar to the ordinary oxide of iron. The ferric hydroxide which is difficultly soluble in acids has the composition Fe_{2}O_{3},H_{2}O. This hydroxide is obtained by a prolonged ebullition of water in which ferric hydroxide prepared by the oxidation of ferrous oxide is suspended, and also sometimes by similar treatment of the ordinary hydroxide after it has been for a long time in contact with water. The transition of one hydroxide to another is apparent by a change of colour; the easily-soluble hydroxide is redder, and the sparingly-soluble hydroxide more yellow in colour.[22] [22] The two ferric hydroxides are not only characterised by the above-mentioned properties, but also by the fact that the first hydroxide forms immediately with potassium ferrocyanide, K_{4}FeC_{6}N_{6}, a blue colour depending on the formation of Prussian blue, whilst the second hydroxide does not give any reaction whatever with this salt. The first hydroxide is entirely soluble in nitric, hydrochloric, and all other acids; whilst the second sometimes (not always) forms a brick-coloured liquid, which appears turbid and does not give the reactions peculiar to the ferric salts (Péan de Saint-Gilles, Scheurer-Kestner). In addition to this, when the smallest quantity of an alkaline salt is added to this liquid, ferric oxide is precipitated. Thus a colloidal solution is formed (hydrosol), which is exactly similar to silica hydrosol (Chapter XVII.), according to which example the hydrosol of ferric oxide may be obtained. If ordinary ferric hydroxide be dissolved in acetic acid, a solution of the colour of red wine is obtained, which has all the reactions characteristic of ferric salts. But if this solution (formed in the cold) be heated to the boiling-point, its colour is very rapidly intensified, a smell of acetic acid becomes apparent, and the solution then contains a new variety of ferric oxide. If the boiling of the solution be continued, acetic acid is evolved, and the modified ferric oxide is precipitated. If the evaporation of the acetic acid be prevented (in a closed or sealed vessel), and the liquid be heated for some time, the whole of the ferric hydroxide then passes into the insoluble form, and if some alkaline salt be added (to the hydrosol formed), the whole of the ferric oxide is then precipitated in its insoluble form. This method may be applied for separating ferric oxide from solutions of its salts. All phenomena observed respecting ferric oxide (colloidal properties, various forms, formation of double basic salts) demonstrate that this substance, like silica, alumina, lead hydroxide, &c., is polymerised, that the composition is represented by (Fe_{2}O_{3})_{_n_}. The normal salts of the composition Fe_{2}X_{6} or FeX_{3} correspond with ferric oxide--for example, the exceedingly volatile _ferric chloride_, Fe_{2}Cl_{6}, which is easily prepared in the anhydrous state by the action of chlorine on heated iron.[23] Such also is the _normal ferric nitrate_, Fe_{2}(NO_{3})_{6}; it is obtained by dissolving iron in an excess of nitric acid, taking care as far as possible to prevent any rise of temperature.[24] The normal salt separates from the brown solution when it is concentrated under a bell jar over sulphuric acid. This salt, Fe_{2}(NO_{3})_{6},9H_{2}O, then crystallises in well-formed and perfectly colourless crystals,[25] which deliquesce in air, melt at 35°, and are soluble in and decomposed by water. The decomposition may be seen from the fact that the solution is brown and does not yield the whole of the salt again, but gives partly basic salt. The normal salt (only stable in the presence of an excess of HNO_{3}) is completely decomposed with great facility by heating with water, even at 130°, and this is made use of for removing iron (and also certain other oxides of the form R_{2}O_{3}) from many other bases (of the form RO) whose nitrates are far more stable. The ferric salts, FeX_{3}, in passing into ferrous salts, act as oxidising agents, as is seen from the fact that they not only liberate S from SH_{2}, but also iodine from KI like many oxidising agents.[25 bis] [23] The ferric compound which is most used in practice (for instance, in medicine, for cauterising, stopping bleeding, &c.--Oleum Martis) is _ferric chloride_, Fe_{2}Cl_{6}, easily obtained by dissolving the ordinary hydrated oxide of iron in hydrochloric acid. It is obtained in the anhydrous state by the action of chlorine on heated iron. The experiment is carried on in a porcelain tube, and a solid _volatile substance_ is then formed in the shape of brilliant violet scales which very readily absorb moisture from the air, and when heated with water decompose into crystalline ferric oxide and hydrochloric acid: Fe_{2}Cl_{6} + 3H_{2}O = 6HCl + Fe_{2}O_{3}. Ferric chloride is so volatile that the density of its vapour may be determined. At 440° it is equal to 164·0 referred to hydrogen; the formula Fe_{2}Cl_{6} corresponds with a density of 162·5. An aqueous solution of this salt has a brown colour. On evaporating and cooling this solution, crystals separate containing 6 or 12 molecules of H_{2}O. Ferric chloride is not only soluble in water, but also in alcohol (similarly to magnesium chloride, &c.) and in ether. If the latter solutions are exposed to the rays of the sun they become colourless, and deposit ferrous chloride, FeCl_{2}, chlorine being disengaged. After a certain lapse of time, the aqueous solutions of ferric chloride decompose with precipitation of a basic salt, thus demonstrating the instability of ferric chloride, like the other salts of ferric oxide (Note 22). This salt is much more stable in the form of double salts, like all the ferric salts and also the salts of many other feeble bases. Potassium or ammonium chloride forms with it very beautiful red crystals of a double salt, having the composition Fe_{2}Cl_{6},4KCl,2H_{2}O. When a solution of this salt is evaporated it decomposes, with separation of potassium chloride. B. Roozeboom (1892) studied in detail (as for CaCl_{2}, Chapter XIV., Note 50) the separation of different hydrates from saturated solutions of Fe_{2}Cl_{6} at various concentrations and temperatures; he found that there are 4 crystallohydrates with 12, 7, 5, and 4 molecules of water. An orange yellow only slightly hygroscopic hydrate, Fe_{2}Cl_{6},12H_{2}O, is most easily and usually obtained, which melts at 37°; its solubility at different temperatures is represented by the curve BCD in the accompanying figure, where the point B corresponds to the formation, at -55°, of a cryohydrate containing about Fe_{2}Cl_{6} + 36H_{2}O, the point C corresponds to the melting-point (+37°) of the hydrate Fe_{2}Cl_{6},12H_{2}O, and the curve CD to the fall in the temperature of crystallisation with an increase in the amount of salt, or decrease in the amount of water (in the figure the temperatures are taken along the axis of abscissæ, and the amount of _n_ in the formula _n_Fe_{2}Cl_{6} + 100H_{2}O along the axis of ordinates). When anhydrous Fe_{2}Cl_{6} is added to the above hydrate (12H_{2}O), or some of the water is evaporated from the latter, very hygroscopic crystals of Fe_{2}Cl_{6},5H_{2}O (Fritsche) are formed; they melt at 56°, their solubility is expressed by the curve HJ, which also presents a small branch at the end J. This again gives the fall in the temperature of crystallisation with an increase in the amount of Fe_{2}Cl_{6}. Besides these curves and the solubility of the anhydrous salt expressed by the line KL (up to 100°, beyond which chlorine is liberated), Roozeboom also gives the two curves, EFG and JK, corresponding to the crystallohydrates, Fe_{2}Cl_{6},7H_{2}O (melts at +32°·5, that is lower than any of the others) and Fe_{2}Cl_{6},4H_{2}O (melts at 73°·5), which he discovered by a systematic research on the solutions of ferric chloride. The curve AB represents the separation of ice from dilute solutions of the salt. [Illustration: FIG. 95.--Diagram of the solubility of Fe_{2}Cl_{6}.] The researches of the same Dutch chemist upon the conditions of the formation of crystals from the double salt (NH_{4}Cl)_{4}Fe_{2}Cl_{6},2H_{2}O are even more perfect. This salt was obtained in 1839 by Fritsche, and is easily formed from a strong solution of Fe_{2}Cl_{6} by adding sal-ammoniac, when it separates in crimson rhombic crystals, which, after dissolving in water, only deposit again on evaporation, together with the sal-ammoniac. Roozeboom (1892) found that when the solution contains _b_ molecules of Fe_{2}Cl_{6}, and _a_ molecules of NH_{4}Cl, per 100 molecules H_{2}O, then at 15° one of the following separations takes place: (1) crystals, Fe_{2}Cl_{6},12H_{2}O, when _a_ varies between 0 and 11, and _b_ between 4·65 and 4·8, or (2) a mixture of these crystals and the double salt, when _a_ = 1·36, and _b_ = 4·47, or (3) the double salt, Fe_{2}Cl_{6},4NH_{4}Cl,2H_{2}O, when _a_ varies between 2 and 11·8, and _b_ between 3·1 and 4·56, or (4) a mixture of sal-ammoniac with the iron salt (it crystallises in separate cubes, Retgers, Lehmann), when _a_ varies between 7·7 and 10·9, and _b_ is less than 3·38, or (5) sal-ammoniac, when _a_ = 11·88. And as in the double salt, _a_ : _b_ :: 4 : 1 it is evident that the double salt only separates out when the ratio _a_ : _b_ is less than 4 : 1 (_i.e._ when Fe_{2}Cl_{6} predominates). The above is seen more clearly in the accompanying figure, where _a_, or the number of molecules of NH_{4}Cl per 100H_{2}O, is taken along the axis of abscissæ, and _b_, or the number of molecules of Fe_{2}Cl_{6}, along the ordinates. The curves ABCD correspond to saturation and present an iso-therm of 15°. The portion AB corresponds to the separation of chloride of iron (the ascending nature of this curve shows that the solubility of Fe_{2}Cl_{6} is increased by the presence of NH_{4}Cl, while that of NH_{4}Cl decreases in the presence of Fe_{2}Cl_{6}), the portion BC to the double salt, and the portion CD to a mixture of sal-ammoniac and ferric chloride, while the straight line OF corresponds to the ratio Fe_{2}Cl_{6},4NH_{4}Cl, or _a_ : _b_ :: 4 : 1. The portion CE shows that more double salt may be introduced into the solution without decomposition, but then the solution deposits a mixture of sal-ammoniac and ferric chloride (_see_ Chapter XXIV. Note 9 ^{bis}). If there were more such well-investigated cases of solutions, our knowledge of double salts, solutions, the influence of water, equilibria, isomorphous mixtures, and such-like provinces of chemical relations might be considerably advanced. [Illustration: FIG. 96.--Diagram of the formation, at 15°, of the double salt Fe_{2}Cl_{6}4NH_{4}Cl_{2}H_{2}O or Fe(NH_{4})_{2}Cl_{5}H_{2}O. (After Roozeboom.)] [24] The normal ferric salts are decomposed by heat and even by water, forming basic salts, which may be prepared in various ways. Generally ferric hydroxide is dissolved in solutions of ferric nitrate; if it contains a double quantity of iron the basic salt is formed which contains Fe_{2}O_{3} (in the form of hydroxide) + 2Fe_{2}(NO_{3})_{6} = 3Fe_{2}O(NO_{3})_{4}, a salt of the type Fe_{2}OX_{4}. Probably water enters into its composition. With considerable quantities of ferric oxide, insoluble basic salts are obtained containing various amounts of ferric hydroxide. Thus when a solution of the above-mentioned basic acid is boiled, a precipitate is formed containing 4(Fe_{2}O_{3})_{8},2(N_{2}O_{5}),3H_{2}O, which probably contains 2Fe_{2}O_{2}(NO_{3})_{2} + 2Fe_{2}O_{3},3H_{2}O. If a solution of basic nitrate be sealed in a tube and then immersed in boiling water, the colour of the solution changes just in the same way as if a solution of ferric acetate had been employed (Note 22). The solution obtained smells strongly of nitric acid, and on adding a drop of sulphuric or hydrochloric acid the insoluble variety of hydrated ferric oxide is precipitated. Normal ferric _orthophosphate_ is soluble in sulphuric, hydrochloric, and nitric acids, but insoluble in others, such as, for instance, acetic acid. The composition of this salt in the anhydrous state is FePO_{4}, because in orthophosphoric acid there are three atoms of hydrogen, and iron, in the ferric state, replaces the three atoms of hydrogen. This salt is obtained from ferric acetate, which, with disodium phosphate, forms a _white precipitate_ of FePO_{4}, containing water. If a solution of ferric chloride (yellowish-red colour) be mixed with a solution of sodium acetate in excess, the liquid assumes an intense brown colour which demonstrates the formation of a certain quantity of ferric acetate; then the disodium phosphate directly forms a white gelatinous precipitate of ferric phosphate. By this means the whole of the iron may be precipitated, and the liquid which was brown then becomes colourless. If this normal salt be dissolved in orthophosphoric acid, the crystalline acid salt FeH_{3}(PO_{4})_{2} is formed. If there be an excess of ferric oxide in the solution, the precipitate will consist of the basic salt. If ferric phosphate be dissolved in hydrochloric acid, and ammonia be added, a salt is precipitated on heating which, after continued washing in water and heating (to remove the water), has the composition Fe_{4}P_{2}O_{11}--that is, 2Fe_{2}O_{3},P_{2}O_{5}. In an aqueous condition this salt may be considered as ferric hydroxide, Fe_{2}(OH)_{6}, in which (OH)_{3} is replaced by the equivalent group PO_{4}. Whenever ammonia is added to a solution containing an excess of ferric salt and a certain amount of phosphoric acid, a precipitate is formed containing the whole of the phosphoric acid in the mass of the ferric oxide. Ferric oxide is characterised as a feeble base, and also by the fact of its forming double salts--for instance, _potassium iron alum_, which has a composition Fe_{2}(SO_{4})_{3},K_{2}SO_{4},24H_{2}O or FeK(SO_{4})_{2},12H_{2}O. It is obtained in the form of almost colourless or light rose-coloured large octahedra of the regular system by simply mixing solutions of potassium sulphate and the ferric sulphate obtained by dissolving ferric oxide in sulphuric acid. [25] It would seem that all normal ferric salts are colourless, and that the brown colour which is peculiar to the solutions is really due to basic ferric salts. A remarkable example of the apparent change of colour of salts is represented by the ferrous and ferric oxalates. The former in a dry state has a yellow colour, although as a rule the ferrous salts are green, and the latter is colourless or pale green. When the normal ferric salt is dissolved in water it is, like many salts, probably decomposed by the water into acid and basic salts, and the latter communicates a brown colour to the solution. Iron alum is almost colourless, is easily decomposed by water, and is the best proof of our assertion. The study of the phenomena peculiar to ferric nitrate might, in my opinion, give a very useful addition to our knowledge of the aqueous solutions of salts in general. [25 bis] The reaction FeX_{3} + KI = FeX_{2} + KX + I proceeds comparatively slowly in solutions, is not complete (depends upon the mass), and is reversible. In this connection we may cite the following data from Seubert and Rohrer's (1894) comprehensive researches. The investigations were conducted with solutions containing 1/10 gram--equivalent weights of Fe_{2}(SO_{4})_{3} (_i.e._ containing 20 grams of salt per litre), and a corresponding solution of KI; the amount of iodine liberated being determined (after the addition of starch) by a solution (also 1/10 normal) of Na_{2}S_{2}O_{3} (_see_ Chapter XX., Note 42). The progress of the reaction was expressed by the amount of liberated iodine in percentages of the theoretical amount. For instance, the following amount of iodide of potassium was decomposed when Fe_{2}(SO_{4})_{3} + 2_n_KI was taken: _n_ = 1 2 3 6 10 20 After 15´ 11·4 26·3 40·6 73·5 91·6 96·0 " 30´ 14·0 35·8 47·8 78·5 94·3 97·4 " 1 hour 19·0 42·7 56·0 84·0 95·7 97·6 " 10 " 32·6 56·0 75·7 93·2 96·5 97·6 " 48 " 39·4 67·7 82·6 93·4 96·6 97·6 Similar results were obtained for FeCl_{3}, but then the amount of iodine liberated was somewhat greater. Similar results were also obtained by increasing the mass of FeX_{3} per KI, and by replacing it by HI (_see_ Chapter XXI., Note 26). Iron forms one other oxide besides the ferric and ferrous oxides; this contains twice as much oxygen as the former, but is so very unstable that it can neither be obtained in the free state nor as a hydrate. Whenever such conditions of double decomposition occur as should allow of its separation in the free state, it decomposes into oxygen and ferric oxide. It is known in the state of salts, and is only stable in the presence of alkalis, and forms salts with them which have a decidedly alkaline reaction; it is therefore a feebly acid oxide. Thus when small pieces of iron are heated with nitre or potassium chlorate a potassium salt of the composition K_{2}FeO_{4} is formed, and therefore the hydrate corresponding with this salt should have the composition H_{2}FeO_{4}. It is called _ferric acid_. Its anhydride ought to contain FeO_{3} or Fe_{2}O_{6}--twice as much oxygen as ferric oxide. If a solution of potassium ferrate be mixed with acid, the free hydrate ought to be formed, but it immediately decomposes (2K_{2}FeO_{4} + 5H_{2}SO_{4} = 2K_{2}SO_{4} + Fe_{2}(SO_{4})_{3} + 5H_{2}O + O_{3}), oxygen being evolved. If a small quantity of acid be taken, or if a solution of potassium ferrate be heated with solutions of other metallic salts, ferric oxide is separated--for instance: 2CuSO_{4} + 2K_{2}FeO_{4} = 2K_{2}SO_{4} + O_{3} + Fe_{2}O_{3} + 2CuO. Both these oxides are of course deposited in the form of hydrates. This shows that not only the hydrate H_{2}FeO_{4}, but also the salts of the heavy metals corresponding with this higher oxide of iron, are not formed by reactions of double decomposition. The solution of potassium ferrate naturally acts as a powerful oxidising agent; for instance, it transforms manganous oxide into the dioxide, sulphurous into sulphuric acid, oxalic acid into carbonic anhydride and water, &c.[26] [26] If chlorine be passed through a strong solution of potassium hydroxide in which hydrated ferric oxide is suspended, the turbid liquid acquires a dark pomegranate-red colour and contains potassium ferrate: 10KHO + Fe_{2}O_{3} + 3Cl_{2} = 2K_{2}FeO_{4} + 6KCl + 5H_{2}O. The chlorine must not be in excess, otherwise the salt is again decomposed, although the mode of decomposition is unknown; however, ferric chloride and potassium chlorate are probably formed. Another way in which the above-described salt is formed is also remarkable; a galvanic current (from 6 Grove elements) is passed through cast-iron and platinum electrodes into a strong solution of potassium hydroxide. The cast-iron electrode is connected with the positive pole, and the platinum electrode is surrounded by a porous earthenware cylinder. Oxygen would be evolved at the cast-iron electrode, but it is used up in oxidation, and a dark solution of potassium ferrate is therefore formed about it. It is remarkable that the cast iron cannot be replaced by wrought iron. Iron thus combines with oxygen in three proportions: RO, R_{2}O_{3}, and RO_{3}. It might have been expected that there would be intermediate stages RO_{2} (corresponding to pyrites FeS_{2}) and R_{2}O_{5}, but for iron these are unknown.[26 bis] The lower oxide has a distinctly basic character, the higher is feebly acid. The only one which is stable in the free state is ferric oxide, Fe_{2}O_{3}; the suboxide, FeO, absorbs oxygen, and ferric anhydride, FeO_{3}, evolves it. It is also the same for other elements; the character of each is determined by the relative degree of stability of the known oxides. The salts FeX_{2} correspond with the suboxide, the salts FeX_{3} or Fe_{2}X_{6} with the sesquioxide, and FeX_{6} represents those of ferric acid, as its potassium salt is FeO_{2}(OK)_{2}, corresponding with K_{2}SO_{4}, K_{2}MnO_{4}, K_{2}CrO_{4}, &c. Iron therefore forms compounds of the types FeX_{2}, FeX_{3}, and FeX_{6}, but this latter, like the type NX_{5}, does not appear separately, but only when X represents heterogeneous elements or groups; for instance, for nitrogen in the form of NO_{2}(OH), NH_{4}Cl, &c., for iron in the form of FeO_{2}(OK)_{2}. But still the type FeX_{6} exists, and therefore FeX_{2} and FeX_{3} are compounds which, like ammonia, NH_{3}, are capable of further combinations up to FeX_{6}; this is also seen in the property of ferrous and ferric salts of forming compounds with water of crystallisation, besides double and basic salts, whose stability is determined by the quality of the elements included in the types FeX_{2} and FeX_{3}.[26 tri] It is therefore to be expected that there should be complex compounds derived from ferrous and ferric oxides. Amongst these the series of cyanogen compounds is particularly interesting; their formation and character is not only determined by the property which iron possesses of forming complex types, but also by the similar faculty of the cyanogen compounds, which, like nitriles (Chapter IX.), have clearly developed properties of polymerisation and in general of forming complex compounds.[27] [26 bis] When Mond and his assistants obtained the remarkable volatile compound Ni(CO)_{4} (described later, Chapter XXII.), it was shown subsequently by Mond and Quincke (1891), and also by Berthelot, that iron, under certain conditions, in a stream of carbonic oxide, also volatilises and forms a compound like that given by nickel. Roscoe and Scudder then showed that when water gas is passed through and kept under pressure (8 atmospheres) in iron vessels a portion of the iron volatilises from the sides of the vessel, and that when the gas is burnt it deposits a certain amount of oxides of iron (the same result is obtained with ordinary coal gas which contains a small amount of CO). To obtain the _volatile compound of iron with carbonic oxide_, Mond prepared a finely divided iron by heating the oxalate in a stream of hydrogen, and after cooling it to 80°-45° he passed CO over the powder. The iron then formed (although very slowly) a volatile compound containing Fe(CO)_{5} (as though it answered to a very high type, FeX_{10}), which when cooled condenses into a liquid (slightly coloured, probably owing to incipient decomposition), sp. gr. 1·47, which solidifies at -21°, boils at about 103°, and has a vapour density (about 6·5 with respect to air) corresponding to the above formula; it decomposes at 180°. Water and dilute acids do not act upon it, but it decomposes under the action of light and forms a hard, non-volatile crystalline yellow compound Fe_{2}(CO)_{7} which decomposes at 80° and again forms Fe(CO)_{5}. [26 tri] When the molecular Fe_{2}Cl_{6} is produced instead of FeCl_{3} this complication of the type also occurs. [27] Some light may be thrown upon the faculty of Fe of forming various compounds with CN, by the fact that Fe not only combines with carbon but also with nitrogen. _Nitride of iron_ Fe_{2}N was obtained by Fowler by heating finely powdered iron in a stream of NH_{3} at the temperature of melting lead. _In the cyanogen compounds of iron_, two degrees might be expected: Fe(CN)_{2}, corresponding with ferrous oxide, and Fe(CN)_{3}, corresponding with ferric oxide. There are actually, however, many other known compounds, intermediate and far more complex. They correspond with the double salts so easily formed by metallic cyanides. The two following double salts are particularly well known, very stable, often used, and easily prepared. _Potassium ferrocyanide_ or _yellow prussiate of potash_, a double salt of cyanide of potassium and ferrous cyanide, has the composition FeC_{2}N_{2},4KCN; its crystals contain 3 mol. of water: K_{4}FeC_{6}N_{6},3H_{2}O. The other is _potassium ferricyanide_ or _red prussiate of potash_. It is also known as _Gmelin's salt_, and contains cyanide of potassium with ferric cyanide; its composition is Fe(CN)_{3},3KCN or K_{3}FeC_{6}N_{6}. Its crystals do not contain water. It is obtained from the first by the action of chlorine, which removes one atom of the potassium. A whole series of other ferrocyanic compounds correspond with these ordinary salts. Before treating of the preparation and properties of these two remarkable and very stable salts, it must be observed that with ordinary reagents neither of them gives the same double decompositions as the other ferrous and ferric salts, and they both present a series of remarkable properties. Thus these salts have a neutral reaction, are unchanged by air, dilute acids, or water, unlike potassium cyanide and even some of its double salts. When solutions of these salts are treated with caustic alkalis, they do not give a precipitate of ferrous or ferric hydroxides, neither are they precipitated by sodium carbonate. This led the earlier investigators to recognise special independent groupings in them. The yellow prussiate was considered to contain the complex radicle FeC_{6}N_{6} combined with potassium, namely with K_{4}, and K_{3} was attributed to the red prussiate. This was confirmed by the fact that whilst in both salts any other metal, even hydrogen, might be substituted for potassium, the iron remained unchangeable, just as nitrogen in cyanogen, ammonium, and nitrates does not enter into double decomposition, being in the state of the complex radicles CN, NH_{4}, NO_{2}. Such a representation is, however, completely superfluous for the explanation of the peculiarities in the reactions of such compounds as double salts. If a magnesium salt which can be precipitated by potassium hydroxide does not form a precipitate in the presence of ammonium chloride, it is very clear that it is owing to the formation of a soluble double salt which is not decomposed by alkalis. And there is no necessity to account for the peculiarity of reaction of a double salt by the formation of a new complex radicle. In the same way also, in the presence of an excess of tartaric acid, cupric salts do not form a precipitate with potassium hydroxide, because a double salt is formed. These peculiarities are more easily understood in the case of cyanogen compounds than in all others, because all cyanogen compounds, as unsaturated compounds, show a marked tendency to complexity. This tendency is satisfied in double salts. The appearance of a peculiar character in double cyanides is the more easily understood since in the case of potassium cyanide itself, and also in hydrocyanic acid, a great many peculiarities have been observed which are not encountered in those haloid compounds, potassium chloride and hydrochloric acid, with which it was usual to compare cyanogen compounds. These peculiarities become more comprehensible on comparing cyanogen compounds with ammonium compounds. Thus in the presence of ammonia the reactions of many compounds change considerably. If in addition to this it is remembered that the presence of many carbon (organic) compounds frequently completely disturbs the reaction of salts, the peculiarities of certain double cyanides will appear still less strange, because they contain carbon. The fact that the presence of carbon or another element in the compound produces a change in the reactions, may be compared to the action of oxygen, which, when entering into a combination, also very materially changes the nature of reactions. Chlorine is not detected by silver nitrate when it is in the form of potassium chlorate, KClO_{3}, as it is detected in potassium chloride, KCl. The iron in ferrous and ferric compounds varies in its reactions. In addition to the above-mentioned facts, consideration ought to be given to the circumstance that the easy mutability of nitric acid undergoes modification in its alkali salts, and in general the properties of a salt often differ much from those of the acid. Every double salt ought to be regarded as a peculiar kind of saline compound: potassium cyanide is, as it were, a basic, and ferrous cyanide an acid, element. They may be unstable in the separate state, but form a stable double compound when combined together; the act of combination disengages the energy of the elements, and they, so to speak, saturate each other. Of course, all this is not a definite explanation, but then the supposition of a special complex radicle can even less be regarded as such. Potassium ferrocyanide, K_{4}FeC_{6}N_{6}, is very easily formed by mixing solutions of ferrous sulphate and potassium cyanide. First, a white precipitate of ferrous cyanide, FeC_{2}N_{2}, is formed, which becomes blue on exposure to air, but is soluble in an excess of potassium cyanide, forming the ferrocyanide. The same yellow prussiate is obtained on heating animal nitrogenous charcoal or animal matters--such as horn, leather cuttings, &c.--with potassium carbonate in iron vessels,[27 bis] the mass formed being afterwards boiled with water with exposure to air, potassium cyanide first appearing, which gives yellow prussiate. The animal charcoal may be exchanged for wood charcoal, permeated with potassium carbonate and heated in nitrogen or ammonia; the mass thus produced is then boiled in water with ferric oxide.[28] In this manner it is manufactured on the large scale, and is called 'yellow prussiate' ('prussiate de potasse,' Blutlaugensalz). [27 bis] The sulphur of the animal refuse here forms the compound FeKS_{2}, which by the action of potassium cyanide yields potassium sulphide, thiocyanate, and ferrocyanide. [28] Potassium ferrocyanide may also be obtained from Prussian blue by boiling with a solution of potassium hydroxide, and from the ferricyanide by the action of alkalis and reducing substances (because the red prussiate is a product of oxidation produced by the action of chlorine: a ferric salt is reduced to a ferrous salt), &c. In many works (especially in Germany and France) yellow prussiate is prepared from the mass, containing oxide of iron, and employed for purifying coal gas (Vol. I., p. 361), which generally contains cyanogen compounds. About 2 p.c. of the nitrogen contained in coal is converted into cyanogen, which forms Prussian blue and thiocyanates in the mass used for purifying the gas. On evaporation the solution yields large yellow crystals containing 3 molecules of water, which is easily expelled by heating above 100°. 100 parts of water at the ordinary temperature are capable of dissolving 25 parts of this salt; its sp. gr. is 1·83. When ignited it forms potassium cyanide and iron carbide, FeC_{2} (Chapter XIII., Note 12). Oxidising substances change it into potassium ferricyanide. With strong sulphuric acid it gives carbonic oxide, and with dilute sulphuric acid, when heated, prussic acid is evolved according to the equation: 2K_{4}FeC_{6}N_{6} + 3H_{2}SO_{4} = K_{2}Fe_{2}C_{6}N_{6} + 3K_{2}SO_{4} + 6HCN; hence in the yellow prussiate K_{2} replaces Fe. It is easy to substitute other metals for the potassium in the yellow prussiate. The hydrogen salt or hydroferrocyanic acid, H_{4}FeC_{6}N_{6}, is obtained by mixing strong solutions of yellow prussiate and hydrochloric acid. If ether be added and the air excluded, the acid is obtained directly in the form of a white scarcely crystalline precipitate which becomes blue on exposure to air (as ferrous cyanide does from the formation of blue compounds of ferrous and ferric cyanides, and it is on this account used in cotton printing). It is soluble in water and alcohol, but not in ether, has marked acid properties, and decomposes carbonates, which renders it easily possible to prepare ferrocyanides of the metals of the alkalis and alkaline earths; these are readily soluble, have a neutral reaction, and resemble the yellow prussiate. Solutions of these salts form precipitates with the salts of other metals, because the ferrocyanides of the heavy metals are insoluble. Here either the whole of the potassium of the yellow prussiate, or only a part of it, is exchanged for an equivalent quantity of the heavy metal. Thus, when a cupric salt is added to a solution of yellow prussiate, a red precipitate is obtained which still contains half the potassium of the yellow prussiate: K_{4}FeC_{6}N_{6} + CuSO_{4} = K_{2}CuFeC_{6}N_{6} + K_{2}SO_{4}. But if the process be reversed (the salt of copper being then in excess) the whole of the potassium will be exchanged for copper, forming a reddish-brown precipitate, Cu_{2}FeC_{6}N_{6},9H_{2}O. This reaction and those similar to it are very sensitive and may be used for detecting metals in solution, more especially as the colour of the precipitate very often shows a marked difference when one metal is exchanged for another. Zinc, cadmium, lead, antimony, tin, silver, cuprous and aurous salts form _white_ precipitates; cupric, uranium, titanium and molybdenum salts _reddish-brown_; those of nickel, cobalt, and chromium, _green_ precipitates; _with ferrous salts_, ferrocyanide forms, as has been already mentioned, a _white_ precipitate--namely, Fe_{2}FeC_{6}N_{6}, or FeC_{2}N_{2}--which turns blue on exposure to air, and with ferric salts a _blue precipitate_ called _Prussian blue_. Here the potassium is replaced by iron, the reaction being expressed thus: 2Fe_{2}Cl_{6} + 3K_{4}FeC_{6}N_{6} = 12KCl + Fe_{4}Fe_{3}C_{18}N_{18}, the latter formula expressing the composition of Prussian blue. It is therefore the compound 4Fe(CN)_{3} + 3Fe(CN)_{2}. The yellow prussiate is prepared in chemical works on a large scale especially for the manufacture of this blue pigment, which is used for dyeing cloth and other fabrics and also as one of the ordinary blue paints. It is insoluble in water, and the stuffs are therefore dyed by first soaking them in a solution of a ferric salt and then in a solution of yellow prussiate. If however an excess of yellow prussiate be present complete substitution between potassium and iron does not occur, and _soluble Prussian blue_ is formed; KFe_{2}(CN)_{6} = KCN,Fe(CN)_{2},Fe(CN)_{3}. This blue salt is colloidal, is soluble in pure water, but insoluble and precipitated when other salts--for instance, potassium or sodium chloride--are present even in small quantities, and is therefore first obtained as a precipitate.[29] [29] Skraup obtained this salt both from potassium ferrocyanide with ferric chloride and from ferricyanide with ferrous chloride, which evidently shows that it contains iron in both the ferric and ferrous states. With ferrous chloride it forms Prussian blue, and with ferric chloride Turnbull's blue. Prussian blue was discovered in the beginning of the last century by a Berlin manufacturer, Diesbach. It was then prepared, as it sometimes is also at present, directly from potassium cyanide obtained by heating animal charcoal with potassium carbonate. The mass thus obtained is dissolved in water, alum is added to the solution in order to saturate the free alkali, and then a solution of green vitriol is added which has previously been sufficiently exposed to the air to contain both ferric and ferrous salts. If the solution of potassium cyanide be mixed with a solution containing both salts, Prussian blue will be formed, because it is a compound of ferrous cyanide, FeC_{2}N_{2}, and ferric cyanide, Fe_{2}C_{6}N_{6}. A ferric salt with potassium ferrocyanide forms a blue colour, because ferrous cyanide is obtained from the first salt and ferric cyanide from the second. During the preparation of this compound alkali must be avoided, as otherwise the precipitate would contain oxides of iron. Prussian blue has not a crystalline structure; it forms a blue mass with a copper-red metallic lustre. Both acids and alkalis act on it. The action is at first confined to the ferric salt it contains. Thus alkalis form ferric oxide and ferrocyanide in solution: 2Fe_{2}C_{6}N_{6},3FeC_{2}N_{2} + 12KHO = 2(Fe_{2}O_{3},3H_{2}O) + 3K_{4}FeC_{6}N_{6}. Various ferrocyanides may thus be prepared. Prussian blue is soluble in an aqueous solution of oxalic acid, forming blue ink. In air, when exposed to the action of light, it fades; but in the dark again absorbs oxygen and becomes blue, which fact is also sometimes noticed in blue cloth. An excess of potassium ferrocyanide renders Prussian blue soluble in water, although insoluble in various saline solutions--that is, it converts it into the soluble variety. Strong hydrochloric acid also dissolves Prussian blue. Potassium ferricyanide, or _red prussiate_ of potash, K_{3}FeC_{6}N_{6}, is called 'Gmelin's salt,' because this savant obtained it by the action of chlorine on a solution of the yellow prussiate: K_{4}FeC_{6}N_{6} + Cl = K_{3}FeC_{6}N_{6} + KCl. The reaction is due to the ferrous salt being changed by the action of the chlorine into a ferric salt. It separates from solutions in anhydrous, well-formed prisms of a red colour, but the solution has an olive colour; 100 parts of water, at 10°, dissolve 37 parts of the salt, and at 100°, 78 parts.[30] The red prussiate gives a blue precipitate with ferrous salts, called _Turnbull's blue_, very much like Prussian blue (and the soluble variety), because it also contains ferrous cyanide and ferric cyanide, although in another proportion, being formed according to the equation: 3FeCl_{2} + 2K_{3}FeC_{6}N_{6} = 6KCl + Fe_{3}Fe_{2}C_{12}N_{12}, or 3FeC_{2}N_{2},Fe_{2}C_{6}N_{6}; in Prussian blue we have Fe_{7}Cy_{18}, and here Fe_{5}Cy_{12}. A ferric salt ought to form ferric cyanide Fe_{2}C_{6}N_{6}, with red prussiate, but ferric cyanide is soluble, and therefore no precipitate is obtained, and the liquid only becomes brown.[31] [30] An excess of chlorine must not be employed in preparing this compound, otherwise the reaction goes further. It is easy to find out when the action of the chlorine on potassium ferrocyanide must cease; it is only necessary to take a sample of the liquid and add a solution of a ferric salt to it. If a precipitate of Prussian blue is formed, more chlorine must be added, as there is still some undecomposed ferrocyanide, for the ferricyanide does not give a precipitate with ferric salts. Potassium ferricyanide, like the ferrocyanide, easily exchanges its potassium for hydrogen and various metals by double decomposition. With the salts of tin, silver, and mercury it forms yellow precipitates, and with those of uranium, nickel, cobalt, copper, and bismuth brown precipitates. The lead salt under the action of sulphuretted hydrogen forms lead sulphide and a hydrogen salt or acid, H_{3}FeC_{6}N_{6}, corresponding with potassium ferricyanide, which is soluble, crystallises in red needles, and resembles hydroferrocyanic acid, H_{4}FeC_{6}N_{6}. Under the action of reducing agents--for instance, sulphuretted hydrogen, copper--potassium ferricyanide is changed into ferrocyanide, especially in the presence of alkalis, and thus forms a rather energetic _oxidising agent_--capable, for instance, of changing manganous oxide into dioxide, bleaching tissues, &c. [31] It is important to mention a series of readily crystallisable salts formed by the action of nitric acid on potassium and other ferrocyanides and ferricyanides. These salt contain the elements of nitric oxide, and are therefore called _nitro-(nitroso) ferricyanides_ (_nitroprussides_). Generally a crystalline sodium salt is obtained, Na_{2}FeC_{5}N_{6}O,2H_{2}O. In its composition this salt differs from the red sodium salt, Na_{3}FeC_{6}N_{6}, by the fact that in it one molecule of sodium cyanide, NaCN, is replaced by nitric oxide, NO. In order to prepare it, potassium ferrocyanide in powder is mixed with five-sevenths of its weight of nitric acid diluted with an equal volume of water. The mixture is at first left at the ordinary temperature, and then heated on a water-bath. Here ferricyanide is first of all formed (as shown by the liquid giving a precipitate with ferrous chloride), which then disappears (no precipitate with ferrous chloride), and forms a green precipitate. The liquid, when cooled, deposits crystals of nitre. The liquid is then strained off and mixed with sodium carbonate, boiled, filtered, and evaporated; sodium nitrate and the salt described are deposited in crystals. It separates in prisms of a red colour. Alkalis and salts of the alkaline earths do not give precipitates: they are soluble, but the salts of iron, zinc, copper, and silver form precipitates where sodium is exchanged with these metals. It is remarkable that the sulphides of the alkali metals give with this salt an intense bright purple coloration. This series of compounds was discovered by Gmelin and studied by Playfair and others (1849). This series to a certain extent resembles the nitro-sulphide series described by Roussin. Here the primary compound consists of black crystals, which are obtained as follows:--Solutions of potassium hydrosulphide and nitrate are mixed, and the mixture is agitated whilst ferric chloride is added, then boiled and filtered; on cooling, _black crystals_ are deposited, having the composition Fe_{6}S_{3}(NO)_{10},H_{2}O (Rosenberg), or, according to Demel, FeNO_{2},NH_{2}S. They have a slightly metallic lustre, and are soluble in water, alcohol, and ether. They absorb the latter as easily as calcium chloride absorbs water. In the presence of alkalis these crystals remain unchanged, but with acids they evolve nitric oxides. There are several compounds which are capable of interchanging, and correspond with Roussin's salt. Here we enter into the series of the nitrogen compounds which have been as yet but little investigated, and will most probably in time form most instructive material for studying the nature of that element. These series of compounds are as unlike the usual saline compounds of inorganic chemistry as are organic hydrocarbons. There is no necessity to describe these series in detail, because their connection with other compounds is not yet clear, and they have not yet any application. If chlorine and sodium are representatives of independent groups of elements, the same may also be said of iron. Its nearest analogues show, besides a similarity in character, a likeness as regards physical properties and a proximity in atomic weight. Iron occupies a medium position amongst its nearest analogues, both with respect to properties and faculty of forming saline oxides, and also as regards atomic weight. On the one hand, cobalt, 58, and nickel, 59, approach iron, 56; they are metals of a more basic character, they do not form stable acids or higher degrees of oxidation, and are a transition to copper, 63, and zinc, 65. On the other hand, manganese, 55, and chromium, 52, are the nearest to iron; they form both basic and acid oxides, and are a transition to the metals possessing acid properties. In addition to having atomic weights approximately alike, chromium, manganese, iron, cobalt, nickel, and copper have also nearly the same specific gravity, so that the atomic volumes and the molecules of their analogous compounds are also near to one another (see table at the beginning of this volume). Besides this, the likeness between the above-mentioned elements is also seen from the following: They form suboxides, RO, fairly energetic bases, isomorphous with magnesia--for instance, the salt RSO_{4},7H_{2}O, akin to MgSO_{4},7H_{2}O, and FeSO_{4},7H_{2}O, or to sulphates containing less water; with alkali sulphates all form double salts crystallising with 6H_{2}O; all are capable of forming ammonium salts, &c. The lower oxides, in the cases of nickel and cobalt, are tolerably stable, are not easily oxidised (the nickel compound with more difficulty than cobalt, a transition to copper); with manganese, and especially with chromium, they are more easily oxidised than with iron and pass into higher oxides. They also form oxides of the form R_{2}O_{3}, and with nickel, cobalt, and manganese this oxide is very unstable, and is more easily reduced than ferric oxide; but, in the case of chromium, it is very stable, and forms the ordinary kind of salts. It is isomorphous with ferric oxide, forms alums, is a feeble base, &c. Chromium, manganese, and iron are oxidised by alkali and oxidising agents, forming salts like Na_{2}SO_{4}; but cobalt and nickel are difficult to oxidise; their acids are not known with any certainty, and are, in all probability, still less stable than the ferrates. Cr, Mn and Fe form compounds R_{2}Cl_{6} which are like Fe_{2}Cl_{6} in many respects; in Co this faculty is weaker and in Ni it has almost disappeared. The cyanogen compounds, especially of manganese and cobalt, are very near akin to the corresponding ferrocyanides. The oxides of nickel and cobalt are more easily reduced to metal than those of iron, but those of manganese and chromium are not reduced so easily as iron, and the metals themselves are not easily obtained in a pure state; they are capable of forming varieties resembling cast iron. The metals Cr, Mn, Fe, Co, and Ni have a grey iron colour and are very difficult to melt, but nickel and cobalt can be melted in the reverberatory furnace and are more fusible than iron, whilst chromium is more difficult to melt than platinum (Deville). These metals decompose water, but with greater difficulty as the atomic weight rises, forming a transition to copper, which does not decompose water. All the compounds of these metals have various colours, which are sometimes very bright, especially in the higher stages of oxidation. These metals of the iron group are often met with together in nature. Manganese nearly everywhere accompanies iron, and iron is always an ingredient in the ores of manganese. Chromium is found principally as chrome ironstone--that is, a peculiar kind of magnetic oxide in which Fe_{2}O_{3} is replaced by Cr_{2}O_{3}. Nickel and cobalt are as inseparable companions as iron and manganese. The similarity between them even extends to such remote properties as magnetic qualities. In this series of metals we find those which are the most magnetic: iron, cobalt, and nickel. There is even a magnetic oxide among the chromium compounds, such being unknown in the other series. Nickel easily becomes passive in strong nitric acid. It absorbs hydrogen in just the same way as iron. In short, in the series Cr, Mn, Fe, Co, and Ni, there are many points in common although there are many differences, as will be seen still more clearly on becoming acquainted with cobalt and nickel. In nature _cobalt_ is principally found in combination with arsenic and sulphur. _Cobalt arsenide_, or _cobalt speiss_, CoAs_{2}, is found in brilliant crystals of the regular system, principally in Saxony. _Cobalt glance_, CoAs_{2}CoS_{2}, resembles it very much, and also belongs to the regular system; it is found in Sweden, Norway, and the Caucasus. _Kupfernickel_ is a nickel ore in combination with arsenic, but of a different composition from cobalt arsenide, having the formula NiAs; it is found in Bohemia and Saxony. It has a copper-red colour and is rarely crystalline; it is so called because the miners of Saxony first mistook it for an ore of copper (_Kupfer_), but were unable to extract copper from it. _Nickel glance_, NiS_{2},NiAs_{2}, corresponding with cobalt glance, is also known. Nickel accompanies the ores of cobalt and cobalt those of nickel, so that both metals are found together. The ores of cobalt are worked in the Caucasus in the Government of Elizavetopolsk. Nickel ores containing aqueous hydrated nickel silicate are found in the Ural (Revdansk). Large quantities of a similar ore are exported into Europe from New Caledonia. Both ores contain about 12 per cent. Ni. _Garnierite_, (RO)_{5}(SiO_{2})_{4}1-1/2H_{2}O, where R = Ni and Mg, predominates in the New Caledonian ore. Large deposits of nickel have been discovered in Canada, where the ore (as nickelous pyrites) is free from arsenic. Cobalt is principally worked up into cobalt compounds, but nickel is generally reduced to the metallic state, in which it is now often used for alloys--for instance, for coinage in many European States, and for plating other metals, because it does not oxidise. Cobalt arsenide and cobalt glance are principally used for the preparation of cobalt compounds; they are first sorted by discarding the rocky matter, and then roasted. During this process most of the sulphur and arsenic disappears; the arsenious anhydride volatilises with the sulphurous anhydride and the metal also oxidises.[32] It is a simple matter to obtain nickel and cobalt from their oxides. In order to obtain the latter, solutions of their salts are treated with sodium carbonate and the precipitated carbonates are heated; the suboxides are thus obtained, and these latter are reduced in a stream of hydrogen, or even by heating with ammonium chloride. They easily oxidise when in the state of powder. When the chlorides of nickel and cobalt are heated in a stream of hydrogen, the metal is deposited in brilliant scales. _Nickel is always much more easily and quickly reduced than cobalt._ Nickel melts more easily than cobalt, and this even furnishes a means of testing the heating powers of a reverberatory furnace. Cobalt fuses at a temperature only a little lower than that at which iron does. In general, cobalt is nearer to iron than nickel, nickel being nearer to copper.[32 bis] Both nickel and cobalt have magnetic properties like iron, but Co is less magnetic than Fe, and Ni still less so. The specific gravity of nickel reduced by hydrogen is 9·1 and that of cobalt 8·9. Fused cobalt has a specific gravity of 8·5, the density of ordinary nickel being almost the same. Nickel has a greyish silvery-white colour; it is brilliant and very ductile, so that the finest wire may be easily drawn from it. This wire has a resistance to tension equal to iron wire. The beautiful colour of nickel, and the high polish which it is capable of receiving and retaining, as it does not oxidise, render it a useful metal for many purposes, and in many ways it resembles silver.[32 tri] It is now very common to cover other metals with a layer of nickel (nickel plating). This is done by a process of electro-plating, using a solution of a nickel salt. The colour of cobalt is dark and redder; it is also ductile, and has a greater tensile resistance than iron. Dilute acids act very slowly on nickel and cobalt; nitric acid may be considered as the best solvent for them. The solutions in every case contain salts corresponding with the ferrous salts--that is, the _salts_ CoX_{2}, NiX_{2}, _correspond with the suboxides_ of these metals. These salts in their types are similar to the magnesium salts. The salts of nickel when crystallising with water have a green colour, and form bright green solutions, but in the anhydrous state they most frequently have a yellow colour. The salts of cobalt are generally rose-coloured, and generally blue when in the anhydrous state. Their aqueous solutions are rose-coloured. Cobaltous chloride is easily soluble in alcohol, and forms a solution of an intense blue colour.[33] [32] The residue from the roasting of cobalt ores is called _zafflor_, and is often met with in commerce. From this the purer compounds of cobalt may be prepared. The ores of nickel are also first roasted, and the oxides dissolved in acid, nickelous salts being then obtained. The further treatment of cobalt and nickel ores is facilitated if the arsenic can be almost entirely removed, which may be effected by roasting the ore a second time with a small addition of nitre and sodium carbonate; the nitre combines with the arsenic, forming an arsenious salt, which may be extracted with water. The remaining mass is dissolved in hydrochloric acid, mixed with a small quantity of nitric acid. Copper, iron, manganese, nickel, cobalt, &c., pass into solution. By passing hydrogen sulphide through the solution, copper, bismuth, lead, and arsenic are deposited as metallic sulphides; but iron, cobalt, nickel, and manganese remain in solution. If an alkaline solution of bleaching powder be then added to the remaining solution, the whole of the manganese will first be deposited in the form of dioxide, then the cobalt as hydrated cobaltic oxide, and finally the nickel also. It is, however, impossible to rely on this method for effecting a complete separation, the more so since the higher oxides of the three above-mentioned metals have all a black colour; but, after a few trials, it will be easy to find how much bleaching powder is required to precipitate the manganese, and the amount which will precipitate all the cobalt. The manganese may also be separated from cobalt by precipitation from a mixture of the solutions of both metals (in the form of the 'ous' salts) with ammonium sulphide, and then treating the precipitate with acetic acid or dilute hydrochloric acid, in which manganese sulphide is easily soluble and cobalt sulphide almost insoluble. Further particulars relating to the separation of cobalt from nickel may be found in treatises on analytical chemistry. In practice it is usual to rely on the rough method of separation founded on the fact that nickel is more easily reduced and more difficult to oxidise than cobalt. The New Caledonian ore is smelted with CaSO_{4} and CaCO_{3} on coke, and a metallic regulus is obtained containing all the Ni, Fe, and S. This is roasted with SiO_{2}, which converts all the iron into slag, whilst the Ni remains combined with the S; this residue on further roasting gives NiO, which is reduced by the carbon to metallic Ni. The Canadian ore (a pyrites containing 11 p.c. Ni) is frequently treated in America (after a preliminary dressing) by smelting it with Na_{2}SO_{4} and charcoal; the resultant fusible Na_{2}S then dissolves the CuS and FeS_{2}, while the NiS is obtained in a bottom layer (Bartlett and Thomson's process) from which Ni is obtained in the manner described above. For manufacturing purposes somewhat impure cobalt compounds are frequently used, which are converted into _smalt_. This is glass containing a certain amount of cobalt oxide; the glass acquires a bright blue colour from this addition, so that when powdered it may be used as a blue pigment; it is also unaltered at high temperatures, so that it used to take the place now occupied by Prussian blue, ultramarine, &c. At present smalt is almost exclusively used for colouring glass and china. To prepare smalt, ordinary impure cobalt ore (zaffre) is fused in a crucible with quartz and potassium carbonate. A fused mass of cobalt glass is thus formed, containing silica, cobalt oxide, and potassium oxide, and a metallic mass remains at the bottom of the crucible, containing almost all the other metals, arsenic, nickel, copper, silver, &c. This metallic mass is called _speiss_, and is used as nickel ore for the extraction of nickel. Smalt usually contains 70 p.c. of silica, 20 p.c. of potash and soda, and about 5 to 6 p.c. of cobaltous oxide; the remainder consisting of other metallic oxides. [32 bis] All we know respecting the relations of Co and Ni to Fe and Cu confirms the fact that Co is more closely related to Fe and Ni to Cu; and as the atomic weight of Fe = 56 and of Cu = 63, then according to the principles of the periodic system it would be expected that the atomic weight of Co would be about 59-60, whilst that of Ni should be greater than that of Co but less than that of Cu, _i.e._ about 50·5-60·5. However, as yet the majority of the determinations of the atomic weights of Co and Ni give a different result and show that a lower atomic weight is obtained for Ni than for Co. Thus K. Winkler (1894) obtained (employing metals deposited electrolytically and determining the amount of iodine which combined with them) Ni = 58·72 and Co = 59·37 (if H = 1 and I = 126·53). In my opinion this should not be regarded as proving that the principles of the periodic system cannot be applied in this instance, nor as a reason for altering the position of these elements in the system (_i.e._ by placing Ni after Fe, and Co next to Cu), because in the first place the figures given by different chemists (for instance, Zimmermann, Krüss, and others) are somewhat divergent, and in the second place the majority of the latest modes of determining the atomic weights of Co and Ni aim at finding what weights of these metals react with known weights of other elements without taking into account the faculty they have of absorbing hydrogen; since this faculty is more developed in Ni than in Co the hydrogen (occluded in Ni) should lower the atomic weight of Ni more than that of Co. On the whole, the question of the atomic weights of Co and Ni cannot yet be considered as decided, notwithstanding the numerous researches which have been made; still there can be no doubt that the atomic weights of these two metals are very nearly equal, and greater than that of Fe, but less than that of Cu. This question is of great interest, not only for completing our knowledge of these metals, but also for perfecting our knowledge of the periodic system of the elements. [32 tri] For instance, the alkalis may be fused in nickel vessels as well as in silver, because they have no action upon either metal. Nickel, like silver, is not acted upon by dilute acids. Only nitric acid dissolves both metals well. Nickel is harder, and fuses at a higher temperature than silver. For castings, a small quantity of magnesium (0·001 part by weight) is added to nickel to render it more homogeneous (just as aluminium is added to steel). Nickel forms many valuable alloys. Steel containing 3 p.c. Ni is particularly valuable, its limit of elasticity is higher and its hardness is greater; it is used for armour plate and other large pieces. The alloys of nickel, especially with copper and zinc (melchior, _see_ later), aluminium and silver, although used in certain cases, are now replaced by nickel-plated or nickel-deposited goods (deposited by electricity from a solution of the ammonium salts). [33] The change of colour is dependent in all probability on the combination with water, or according to others on polymeric transformation. It enables a solution of cobalt chloride to be used as sympathetic ink. If something be written with cobalt chloride on white paper, it will be invisible on account of the feeble colour of the solution, and when dry nothing can be distinguished. If, however, the paper be heated before the fire, the rose-coloured salt will be changed into a less hydrous blue salt, and the writing will become quite visible, but fade away when cool. The change of colour which takes place in solutions of CoCl_{2} under the influence not only of solution in water or alcohol, but also of a change of temperature, is a characteristic of all the halogen salts of cobalt. Crystalline iodide of cobalt, CoI_{2}6H_{2}O, gives a dark red solution between -22° and +20°; above +20° the solution turns brown and passes from olive to green, from +35° to 320° the solution remains green. According to Étard the change of colour is due to the fact that at first the solution contains the hydrate CoI_{2}H_{2}O, and that above 35° it contains CoI_{2}4H_{2}O. These hydrates can be crystallised from the solutions; the former at ordinary temperature and the latter on heating the solution. The intermediate olive colour of the solutions corresponds to the incipient decomposition of the hexahydrated salt and its passage into CoI_{2}4H_{2}O. A solution of the hexahydrated chloride of cobalt, CoCl_{2}6H_{2}O, is rose-coloured between -22° and +25°; but the colour changes starting from +25°, and passes through all the tints between red and blue right up to 50°; a true blue solution is only obtained at 55° and remains up to 300°. This true blue solution contains another hydrate, CoCl_{2}2H_{2}O. The dependence between the solubility of the iodide and chloride of cobalt and the temperature is expressed by two almost straight lines corresponding to the hexa- and di-hydrates; the passage of the one into the other hydrate being expressed by a curve. The same character of phenomena is seen also in the variation of the vapour tension of solutions of chloride of cobalt with the temperature. We have repeatedly seen that aqueous solutions (for instance, Chapter XXII., Note 23 for Fe_{2}Cl_{6}) deposit different crystallo-hydrates at different temperatures, and that the amount of water in the hydrate decreases as the temperature _t_ rises, so that it is not surprising that CoCl_{2}2H_{2}O (or according to Potilitzin CoCl_{2}H_{2}O) should separate out above 55° and CoCl_{2}6H_{2}O at 25° and below. Nor is it exceptional that the colour of a salt varies according as it contains different amounts of H_{2}O. But in this instance it is characteristic that the change of colour takes place in solution in the presence of an excess of water. This apparently shows that the actual solution may contain either CoCl_{2}6H_{2}O or CoCl_{2}2H_{2}O. And as we know that a solution may contain both metaphosphoric PHO_{3} and orthophosphoric acid H_{3}PO_{4} = HPO_{3} + H_{2}O, as well as certain other anhydrides, the question of the state of substances in solutions becomes still more complicated. Nickel sulphate crystallises from neutral solutions at a temperature of from 15° to 20° in _rhombic_ crystals containing 7H_{2}O. Its form approaches very closely to that of the salts of zinc and magnesium. The planes of a vertical prism for magnesium salts are inclined at an angle of 90° 30´, for zinc salts at an angle of 91° 7´, and for nickel salts at an angle of 91° 10´. Such is also the form of the zinc and magnesium selenates and chromates. Cobalt sulphate containing 7 molecules of water is deposited in crystals of the _monoclinic_ system, like the corresponding salts of iron and manganese. The angle of a vertical prism for the iron salt = 82° 20´, for cobalt = 82° 22´, and the inclination of the horizontal pinacoid to the vertical prism for the iron salt = 99° 2´, and for the cobalt salt 99° 36´. All the isomorphous mixtures of the salts of magnesium, iron, cobalt, nickel and manganese have the same form if they contain 7 mol. H_{2}O and iron or cobalt predominate, whilst if there is a preponderance of magnesium, zinc, or nickel, the crystals have a rhombic form like magnesium sulphate. Hence these sulphates are _dimorphous_, but for some the one form is more stable and for others the other. Brooke, Moss, Mitscherlich, Rammelsberg, and Marignac have explained these relations. Brooke and Mitscherlich also supposed that NiSO_{4},7H_{2}O is not only capable of assuming these forms, but also that of the _tetragonal_ system, because it is deposited in this form from acid, and especially from slightly-heated solutions (30° to 40°). But Marignac demonstrated that the tetragonal crystals do not contain 7, but 6, molecules of water, NiSO_{4},6H_{2}O. He also observed that a solution evaporated at 50° to 70° deposits monoclinic crystals, but of a different form from ferrous sulphate, FeSO_{4},7H_{2}O--namely, the angle of the prism is 71° 52´, that of the pinacoid 95° 6´. This salt appears to be the same with 6 molecules of water as the tetragonal. Marignac also obtained magnesium and zinc salts with 6 molecules of water by evaporating their solutions at a higher temperature, and these salts were found to be isomorphous with the monoclinic nickel salt. In addition to this it must be observed that the rhombic crystals of nickel sulphate with 7H_{2}O become turbid under the influence of heat and light, lose water, and change into the tetragonal salt. The monoclinic crystals in time also become turbid, and change their structure, so that the tetragonal form of this salt is the most stable. Let us also add that nickel sulphate in all its shapes forms very beautiful emerald green crystals, which, when heated to 230°, assume a dirty greenish-yellow hue and then contain one molecule of water. Klobb (1891) and Langlot and Lenoir obtained anhydrous CoSO_{4} and NiSO_{4} by igniting the hydrated salt with (NH_{4})_{2}SO_{4} until the ammonium salt had completely volatilised and decomposed. We may add that when equivalent aqueous solutions of NiX_{2} (green) and CoX_{2} (red) are mixed together they give an almost colourless (grey) solution, in which the green and red colour of the component parts disappears owing to the combination of the complementary colours. A double salt NiKF_{3} is obtained by heating NiCl_{2} with KFHF in a platinum crucible; KCoF_{3} is formed in a similar manner. The nickel salt occurs in fine green plates, easily soluble in water but scarcely soluble in ethyl and methyl alcohol. They decompose into green oxide of nickel and potassium fluoride when heated in a current of air. The analogous salt of cobalt crystallises in crimson flakes. If instead of potassium fluoride, CoCl_{2} or NiCl_{2} be fused with ammonium fluoride, they also form double salts with the latter. This gives the possibility of obtaining anhydrous fluorides NiF_{2} and CoF_{2}. Crystalline fluoride of nickel, obtained by heating the amorphous powder formed by decomposing the double ammonium salt in a stream of hydrofluoric acid, occurs in beautiful green prisms, sp. gr. 4·63, which are insoluble in water, alcohol, and ether; sulphuric, hydrochloric, and nitric acids also have no action upon them, even when heated; NiF_{2} is decomposed by steam, with the formation of black oxide, which retains the crystalline structure of the salt. Fluoride of cobalt, obtained as a rose-coloured powder by decomposing the double ammonium salt with the aid of heat in a stream of hydrofluoric acid, fuses into a ruby-coloured mass which bears distinct signs of a crystalline structure; sp. gr. 4·43. The molten salt only volatilises at about 1400°, which forms a clear distinction between CoF_{2} and the volatile NiF_{2}. Hydrochloric, sulphuric, and nitric acids act upon CoF_{2} even in the cold, although slowly, while when heated the reaction proceeds rapidly (Poulenc, 1892). If a solution of potassium hydroxide be added to a solution of a cobalt salt, a blue precipitate of the basic salt will be formed. If a solution of a cobalt salt be heated almost to the boiling-point, and the solution be then mixed with a boiling solution of an alkali hydroxide, a _pink precipitate of cobaltous hydroxide_, CoH_{2}O_{2}, will be formed. If air be not completely excluded during the precipitation by boiling, the precipitate will also contain brown cobaltic hydroxide formed by the further oxidation of the cobaltous oxide.[34] Under similar circumstances nickel salts form _a green precipitate of nickelous hydroxide_, the formation of which is not hindered by the presence of ammonium salts, but in that case only requires more alkali to completely separate the nickel. The nickelous oxide obtained by heating the hydroxide, or from the carbonate or nitrate, is a grey powder, easily soluble in acids and easily reduced, but the same substance may be obtained in the crystalline form as an ordinary product from the ores; it crystallises in regular octahedra, with a metallic lustre, and is of a grey colour. In this state the nickelous oxide almost resists the action of acids.[34 bis] [34] Hydrated suboxide of cobalt (de Schulten, 1889) is obtained in the following manner. A solution of 10 grams of CoCl_{2}6H_{2}O in 60 c.c. of water is heated in a flask with 250 grams of caustic potash and a stream of coal gas is passed through the solution. When heated the hydrate of the suboxide of cobalt which separates out, dissolves in the caustic potash and forms a dark blue solution. This solution is allowed to stand for 24 hours in an atmosphere of coal gas (in order to prevent oxidation). The crystalline mass which separates out has a composition Co(OH)_{2}, and to the naked eye appears as a violet powder, which is seen to be crystalline under the microscope. The specific gravity of this hydrate is 3·597 at 15°. It does not undergo change in the air; warm acetic acid dissolves it, but it is insoluble in warm and cold solutions of ammonia and sal-ammoniac. [34 bis] The following reaction may be added to those of the cobaltous and nickelous salts: potassium cyanide forms a precipitate with cobalt salts which is soluble in an excess of the reagent and forms a green solution. On heating this and adding a certain quantity of acid, a double _cobalt cyanide_ is formed which corresponds with potassium ferricyanide. Its formation is accompanied with the evolution of hydrogen, and is founded upon the property which cobalt has of oxidising in an alkaline solution, the development of which has been observed in such a considerable measure in the cobaltamine salts. The process which goes on here may be expressed by the following equation; CoC_{2}N_{2} + 4KCN first forms CoK_{4}C_{6}N_{6}, which salt with water, H_{2}O, forms potassium hydroxide, KHO, hydrogen, H, and the salt, K_{3}CoC_{6}N_{6}. Here naturally the presence of the acid is indispensable in consequence of its being required to combine with the alkali. From aqueous solutions this salt crystallises in transparent, hexagonal prisms of a yellow colour, easily soluble in water. The reactions of double decomposition, and even the formation of the corresponding acid, are here completely the same as in the case of the ferricyanide. If a nickelous salt be treated in precisely the same manner as that just described for a salt of cobalt, decomposition will occur. It is interesting to note _the relation_ of the cobaltous and nickelous hydroxides _to ammonia_; aqueous ammonia dissolves the precipitate of cobaltous and nickelous hydroxide. The blue ammoniacal solution of nickel resembles the same solution of cupric oxide, but has a somewhat reddish tint. It is characterised by the fact that it dissolves silk in the same way as the ammoniacal cupric oxide dissolves cellulose. Ammonia likewise dissolves the precipitate of cobaltous hydroxide, forming a brownish liquid, which becomes darker in air and finally assumes a bright red hue, absorbing oxygen. The admixture of ammonium chloride prevents the precipitation of cobalt salts by ammonia; when the ammonia is added, a brown solution is obtained from which, as in the case of the preceding solution, potassium hydroxide does not separate the cobaltous oxide. Peculiar compounds are produced in this solution; they are comparatively stable, containing ammonia and an excess of oxygen; they bear the name cobaltoamine and cobaltiamine salts. They have been principally investigated by Genth, Frémy, Jörgenson and others. Genth found that when a cobalt salt, mixed with an excess of ammonium chloride, is treated with ammonia and exposed to the air, after a certain lapse of time, on adding hydrochloric acid and boiling, a red powder is precipitated and the remaining solution contains an orange salt. The study of these compounds led to the discovery of a whole series of similar salts, some of which correspond with particular higher degrees of oxidation of cobalt, which are described later.[35] Nickel does not possess this property of absorbing the oxygen of the air when in an ammoniacal solution. In order to understand this distinction, and in general the relation of nickel, it is important to observe that cobalt more easily forms a higher degree of oxidation--namely, _sesquioxide of cobalt_, _cobaltic oxide_, Co_{2}O_{3}--than nickel, especially in the presence of hypochlorous acid. If a solution of a cobalt salt be mixed with barium carbonate and an excess of hypochlorous acid be added, or chlorine gas be passed through it, then at the ordinary temperature on shaking, the whole of the cobalt will be separated in the form of black cobaltic oxide: 2CoSO_{4} + ClHO + 2BaCO_{3} = Co_{2}O_{3} + 2BaSO_{4} + HCl + 2CO_{2}. Under these circumstances nickelous oxide does not immediately form black sesquioxide, but after a considerable space of time it also separates in the form of sesquioxide, Ni_{2}O_{3}, but always later than cobalt. This is due to the relative difficulty of further oxidation of the nickelous oxide. It is, however, possible to oxidise it; if, for instance, the hydroxide NiH_{2}O_{2} be shaken in water and chlorine gas be passed through it, then nickel chloride will be formed, which is soluble in water, and insoluble nickelic oxide in the form of a black precipitate: 3NiH_{2}O_{2} + Cl_{2} = NiCl_{2} + Ni_{2}O_{3},3H_{2}O. Nickelic oxide may also be obtained by adding sodium hypochlorite mixed with alkali to a solution of a nickel salt. Nickelic and cobaltic hydrates are black. Nickelic oxide evolves oxygen with all acids, and in consequence of this it is not separated as a precipitate in the presence of acids; thus it evolves chlorine with hydrochloric acid, exactly like manganese dioxide. When nickelic oxide is dissolved in aqueous ammonia it liberates nitrogen, and an ammoniacal solution of nickelous oxide is formed. When heated, nickelic oxide loses oxygen, forming nickelous oxide. Cobaltic oxide, Co_{2}O_{3}, exhibits more stability than nickelic oxide, and shows feeble basic properties; thus it is dissolved in acetic acid without the evolution of oxygen.[35 bis] But ordinary acids, especially on heating, evolve oxygen, forming a solution of a cobaltous salt. The presence of a cobaltic salt in a solution of a cobaltous salt may be detected by the brown colour of the solution and the black precipitate formed by the addition of alkali, and also from the fact that such solutions evolve chlorine when heated with hydrochloric acid. Cobaltic oxide may not only be prepared by the above-mentioned methods, but also by heating cobalt nitrate, after which a steel-coloured mass remains which retains traces of nitric acid, but when heated further to incandescence evolves oxygen, leaving a compound of cobaltic and cobaltous oxides, similar to magnetic ironstone. Cobalt (but not nickel) undoubtedly forms besides Co_{2}O_{3} a _dioxide_ CoO_{2}. This is obtained[36] when the cobaltous oxide is oxidised by iodine or peroxide of barium.[37] [35] The cobalt salts may be divided into at least the following classes, which repeat themselves for Cr, Ir, Rh (we shall not stop to consider the latter, particularly as they closely resemble the cobalt salts):-- (_a_) _Ammonium cobalt salts_, which are simply direct compounds of the cobaltous salts CoX_{2} with ammonia, similar to various other compounds of the salts of silver, copper, and even calcium and magnesium, with ammonia. They are easily crystallised from an ammoniacal solution, and have a pink colour. Thus, for instance, when cobaltous chloride in solution is mixed with sufficient ammonia to redissolve the precipitate first formed, octahedral crystals are deposited which have a composition CoCl_{2},H_{2}O,6NH_{3}. These salts are nothing else but combinations with ammonia of crystallisation--if it may be so termed--likening them in this way to combinations with water of crystallisation. This similarity is evident both from their composition and from their capability of giving off ammonia at various temperatures. The most important point to observe is that all these salts contain 6 molecules of ammonia to 1 atom of cobalt, and this ammonia is held in fairly stable connection. Water decomposes these salts. (Nickel behaves similarly without forming other compounds corresponding to the true cobaltic.) (_b_) The solutions of the above-mentioned salts are rendered turbid by the action of the air; they absorb oxygen and become covered with a crust of _oxycobaltamine salts_. The latter are sparingly soluble in aqueous ammonia, have a brown colour, and are characterised by the fact that with warm water _they evolve oxygen_, forming salts of the following category: The nitrate may be taken as an example of this kind of salt; its composition is CoN_{2}O_{7},5NH_{3},H_{2}O. It differs from cobaltous nitrate, Co(NO_{3})_{2}, in containing an extra atom of oxygen--that is, it corresponds with cobalt dioxide, CoO_{2}, in the same way that the first salts correspond with cobaltous oxide; they contain 5, and not 6, molecules of ammonia, as if NH_{3} had been replaced by O, but we shall afterwards meet compounds containing either 5NH_{3} or 6NH_{3} to each atom of cobalt. (_c_) _The luteocobaltic salts_ are thus called because they have a yellow (luteus) colour. They are obtained from the salts of the first kind by submitting them in dilute solution to the action of the air; in this case salts of the second kind are not formed, because they are decomposed by an excess of water, with the evolution of oxygen and the formation of luteocobaltic salts. By the action of ammonia the salts of the fifth kind (roseocobaltic) are also converted into luteocobaltic salts. These last-named salts generally crystallise readily, and have a yellow colour; they are comparatively much more stable than the preceding ones, and even for a certain time resist the action of boiling water. Boiling aqueous potash liberates ammonia and precipitates hydrated cobaltic oxide, Co_{2}O_{3},3H_{2}O, from them. This shows that the luteocobaltic salts correspond with cobaltic oxide, Co_{2}O_{3}, and those of the second kind with the dioxide. When a solution of luteocobaltic sulphate, Co_{2}(SO_{4})_{3},12NH_{3},4H_{2}O, is treated with baryta, barium sulphate is precipitated, and the solution contains luteocobaltic hydroxide, Co(OH)_{3},6NH_{3}, which is soluble in water, is powerfully alkaline, absorbs the oxygen of the air, and when heated is decomposed with the evolution of ammonia. This compound therefore corresponds to a solution of cobaltic hydroxide in ammonia. The luteocobaltic salts contain 2 atoms of cobalt and 12 molecules of ammonia--that is, 6NH_{3} to each atom of cobalt, like the salts of the first kind. The CoX_{2} salts have a metallic taste, whilst those of luteocobalt and others have a purely saline taste, like the salts of the alkali metals. In the luteo-salts all the X's react (are ionised, as some chemists say) as in ordinary salts--for instance, all the Cl_{2} is precipitated by a solution of AgNO_{3}; all the (SO_{4})_{3} gives a precipitate with BaX_{2}, &c. The double salt formed with PtCl_{4} is composed in the same manner as the potassium salt, K_{2}PtCl_{4} = 2KCl + PtCl_{4}, that is, contains (CoCl_{3},6NH_{3})_{2},3PtCl_{4}, or the amount of chlorine in the PtCl_{4} is double that in the alkaline salt. In the rosepentamine (_e_), and rosetetramine (_f_), salts, also all the X's react or are ionised, but in the (_g_) and (_h_) salts only a portion of the X's react, and they are equal to the (_e_) and (_f_) salts minus water; this means that although the water dissolves them it is not combined with them, as PHO_{3} differs from PH_{3}O_{3}; phenomena of this class correspond exactly to what has been already (Chapter XXI., Note 7) mentioned respecting the green and violet salts of oxide of chromium. (_d_) _The fuscocobaltic salts._ An ammoniacal solution of cobalt salts acquires a brown colour in the air, due to the formation of these salts. They are also produced by the decomposition of salts of the second kind; they crystallise badly, and are separated from their solutions by addition of alcohol or an excess of ammonia. When boiled they give up the ammonia and cobaltic oxide which they contain. Hydrochloric and nitric acids give a yellow precipitate with these salts, which turns red when boiled, forming salts of the next category. The following is an example of the composition of two of the fuscocobaltic salts, Co_{2}O(SO_{4})_{2},8NH_{3},4H_{2}O and Co_{2}OCl_{4},8NH_{3},3H_{2}O. It is evident that the fuscocobaltic salts are ammoniacal compounds of basic cobaltic salts. The normal cobaltic sulphate ought to have the composition Co_{2}(SO_{4})_{3} = Co_{2}O_{3},3SO_{3}; the simplest basic salts will be Co_{2}O(SO_{4})_{2} = Co_{2}O_{3})2SO_{3}, and Co_{2}O_{2}(SO_{4}) = Co_{2}O_{3},SO_{3}. The fuscocobaltic salts correspond with the first type of basic salts. They are changed (in concentrated solutions) into oxycobaltamine salts by absorption of one atom of oxygen, Co_{2}O_{2}(SO_{4})_{2}. The whole process of oxidation will be as follows: first of all Co_{2}X_{4}, a cobaltous salt, is in the solution (X a univalent haloid, 2 molecules of the salt being taken), then Co_{2}OX_{4}, the basic cobaltic salt (4th series), then Co_{2}O_{2}X_{4}, the salt of the dioxide (2nd series). The series of basic salts with an acid, 2HX, forms water and a normal salt, Co_{2}X_{6} (in 3, 5, 6 series). These salts are combined with various amounts of water and ammonia. Under many conditions the salts of fuscocobalt are easily transformed into salts of the next series. The salts of the series that has just been described contain 4 molecules of ammonia to 1 atom of cobalt. (_e_) _The roseocobaltic_ (or rosepentamine), CoX_{2}H_{2}O,5NH_{3}, _salts_, like the luteocobaltic, correspond with the normal cobaltic salts, but contain less ammonia, and an extra molecule of water. Thus the sulphate is obtained from cobaltous sulphate dissolved in ammonia and left exposed to the air until transformed into a brown solution of the fuscocobaltic salt; when this is treated with sulphuric acid a crystalline powder of the roseocobaltic salt, Co_{2}(SO_{4})_{3},10NH_{3},5H_{2}O, separates. The formation of this salt is easily understood: cobaltous sulphate in the presence of ammonia absorbs oxygen, and the solution of the fuscocobaltic salt will therefore contain, like cobaltous sulphate, one part of sulphuric acid to every part of cobalt, so that the whole process of formation may be expressed by the equation: 10NH_{3} + 2CoSO_{4} + H_{2}SO_{4} + 4H_{2}O + O = Co_{2}(SO_{4})_{3},10NH_{3},5H_{2}O. This salt forms tetragonal crystals of a red colour, slightly soluble in cold, but readily soluble in warm water. When the sulphate is treated with baryta, roseocobaltic hydroxide is formed in the solution, which absorbs the carbonic anhydride of the air. It is obtained from the next series by the action of alkalis. (_f_) The _rosetetramine cobaltic salts_ CoCl_{2},2H_{2}O,4NH_{3} were obtained by Jörgenson, and belong to the type of the luteo-salts, only with the substitution of 2NH_{3} for H_{2}O. Like the luteo- and roseo-salts they give double salts with PtCl_{4}, similar to the alkaline double salts, for instance (Co_{2}H_{2}O,4NH_{3})2(SO_{4})_{2}Cl_{2}PtCl_{4}. They are darker in colour than the preceding, but also crystallise well. They are formed by dissolving CoCO_{3} in sulphuric acid (of a given strength), and after NH_{3} and carbonate of ammonium have been added, air is passed through the solution (for oxidation) until the latter turns red. It is then evaporated with lumps of carbonate of ammonium, filtered from the precipitate and crystallised. A salt of the composition Co_{2}(CO_{3})_{2}(SO_{4}),(2H_{2}O,4NH_{3})_{2} is thus obtained, from which the other salts may be easily prepared. (_g_) The _purpureocobaltic salts_, CoX_{3},5NH_{3}, are also products of the direct oxidation of ammoniacal solutions of cobalt salts. They are easily obtained by heating the roseocobaltic and luteo-salts with strong acids. They are to all effects the same as the roseocobaltic salts, only anhydrous. Thus, for instance, the purpureocobaltic chloride, Co_{2}Cl_{6},10NH_{3}, or CoCl_{3},5NH_{3}, is obtained by boiling the oxycobaltamine salts with ammonia. There is the same distinction between these salts and the preceding ones as between the various compounds of cobaltous chloride with water. In the purpureocobaltic only X_{2} out of the X_{3} react (are ionised). To the rosetetramine salts (_f_) there correspond the _purpureotetramine_ salts, CoX_{3}H_{2}O,4NH_{3}. The corresponding chromium purpureopentamine salt, CrCl_{3},5NH_{3} is obtained with particular ease (Christensen, 1893). Dry anhydrous chromium chloride is treated with anhydrous liquid ammonia in a freezing mixture composed of liquid CO_{2} and chlorine, and after some time the mixture is taken out of the freezing mixture, so that the excess of NH_{3} boils away; the violet crystals then immediately acquire the red colour of the salt, CrCl_{3},5NH_{3}, which is formed. The product is washed with water (to extract the luteo-salt, CrCl_{3},6NH_{3}), which does not dissolve the salt, and it is then recrystallised from a hot solution of hydrochloric acid. (_h_) The _praseocobaltic salts_, CoX_{3},4NH_{3}, are green, and form, with respect to the rosetetramine salts (_f_), the products of ultimate dehydration (for example, like metaphosphoric acid with respect to orthophosphoric acid, but in dissolving in water they give neither rosetetramine nor tetramine salts. (In my opinion one should expect salts with a still smaller amount of NH_{3}, of the blue colour proper to the low hydrated compounds of cobalt; the green colour of the prazeo-salts already forms a step towards the blue.) Jörgenson obtained salts for ethylene-diamine, N_{2}H_{4}C_{2}H_{4} which replaces 2NH_{3}. After being kept a long time in aqueous solution they give rosetetramine salts, just as metaphosphoric acid gives orthophosphoric acid, while the rosetetramine salts are converted into prazeo-salts by Ag_{2}O and NaHO. Here only one X is ionised out of the X_{3}. There are also basic salts of the same type; but the best known is the chromium salt called the rhodozochromic salt, Cr_{2}(OH)_{3}Cl_{3},6NH_{3},2H_{2}O, which is formed by the prolonged action of water upon the corresponding roseo-salt. The cobaltamine compounds differ essentially but little from the ammoniacal compounds of other metals. The only difference is that here the cobaltic oxide is obtained from the cobaltous oxide in the presence of ammonia. In any case it is a simpler question than that of the double cyanides. Those forces in virtue of which such a considerable number of ammonia molecules are united with a molecule of a cobalt compound, appertain naturally to the series of those slightly investigated forces which exist even in the highest degrees of combination of the majority of elements. They are the same forces which lead to the formation of compounds containing water of crystallisation, double salts, isomorphous mixtures and complex acids (Chapter XXI., Note 8 bis). The simplest conception, according to my opinion, of cobalt compounds (much more so than by assuming special complex radicles, with Schiff, Weltzien, Claus, and others), may be formed by comparing them with other ammoniacal products. Ammonia, like water, combines in various proportions with a multitude of molecules. Silver chloride and calcium chloride, just like cobalt chloride, absorb ammonia, forming compounds which are sometimes slightly stable, and easily dissociated, sometimes more stable, in exactly the same way as water combines with certain substances, forming fairly stable compounds called hydroxides or hydrates, or less stable compounds which are called compounds with water of crystallisation. Naturally the difference in the properties in both cases depends on the properties of those elements which enter into the composition of the given substance, and on those kinds of affinity towards which chemists have not as yet turned their attention. If boron fluoride, silicon fluoride, &c., combine with hydrofluoric acid, if platinic chloride, and even cadmium chloride, combine with hydrochloric acid, these compounds may be regarded as double salts, because acids are salts of hydrogen. But evidently water and ammonia have the same saline faculty, more especially as they, like haloid acids, contain hydrogen, and are both capable of further combination--for instance, ammonia with hydrochloric acid. Hence it is simpler to compare complex ammoniacal with double salts, hydrates, and similar compounds, but _the ammonio-metallic salts_ present a most complete qualitative and quantitative resemblance to _the hydrated salts of metals_. The composition of the latter is MX_{_n_}_m_H_{2}O, where M = metal, X = the haloid, simple or complex, and _n_ and _m_ the quantities of the haloid and so-called water of crystallisation respectively. The composition of the ammoniacal salts of metals is MX_{_n_}_m_NH_{3}. The water of crystallisation is held by the salt with more or less stability, and some salts even do not retain it at all; some part with water easily when exposed to the air, others when heated, and then with difficulty. In the case of some metals all the salts combine with water, whilst with others only a few, and the water so combined may then be easily disengaged. All this applies equally well to the ammoniacal salts, and therefore the combination of ammonia may be termed _the ammonia of crystallisation_. Just as the water which is combined with a salt is held by it with different degrees of force, so it is with ammonia. In combining with 2NH_{3},PtCl_{2} evolves 31,000 cals.; while CaCl_{2} only evolves 14,000 cals.; and the former compound parts with its NH_{3} (together with HCl in this case) with more difficulty, only above 200°, while the latter disengages ammonia at 180°. ZnCl_{2},2NH_{3} in forming ZnCl_{2},4NH_{3} evolves only 11,000 cals., and splits up again into its components at 80°. The amount of combined ammonia is as variable as the amount of water of crystallisation--for instance, SnI_{4}8NH_{3}, CrCl_{2}8NH_{3}, CrCl_{3}6NH_{3}, CrCl_{3}5NH_{3},PtCl_{2},4NH_{3}, &c. are known. Very often NH_{3} is replaceable by OH_{2} and conversely. A colourless, anhydrous cupric salt--for instance, cupric sulphate--when combined with water forms blue and green salts, and violet when combined with ammonia. If steam be passed through anhydrous copper sulphate the salt absorbs water and becomes heated; if ammonia be substituted for the water the heating becomes much more intense, and the salt breaks up into a fine violet powder. With water CuSO_{4},5H_{2}O is formed, and with ammonia CuSO_{4},5NH_{3}, the number of water and ammonia molecules retained by the salt being the same in each case, and as a proof of this, and that it is not an isolated coincidence, the remarkable fact must be borne in mind that water and ammonia consecutively, molecule for molecule, are capable of supplanting each other, and forming the compounds CuSO_{4},5H_{2}O, CuSO_{4},4H_{2}O,NH_{3}; CuSO_{4},3H_{2}O,2NH_{3}; CuSO_{4},2H_{2}O,3NH_{3}; CuSO_{4},H_{2}O,4NH_{3}, and CuSO_{4},5NH_{3}. The last of these compounds was obtained by Henry Rose, and my experiments have shown that more ammonia than this cannot be retained. By adding to a strong solution of cupric sulphate sufficient ammonia to dissolve the whole of the oxide precipitated, and then adding alcohol, Berzelius obtained the compound CuSO_{4},H_{2}O,4NH_{3}, &c. The law of substitution also assists in rendering these phenomena clearer, because a compound of ammonia with water forms ammonium hydroxide, NH_{4}HO, and therefore these molecules combining with one another may also interchange, as being of equal value. In general, those salts form stable ammoniacal compounds which are capable of forming stable compounds with water of crystallisation; and as ammonia is capable of combining with acids, and as some of the salts formed by slightly energetic bases in their properties more closely resemble acids (that is, salts of hydrogen) than those salts containing more energetic bases, we might expect to find more stable and more easily-formed ammonio-metallic salts with metals and their oxides having weaker basic properties than with those which form energetic bases. This explains why the salts of potassium, barium, &c., do not form ammonio-metallic salts, whilst the salts of silver, copper, zinc, &c., easily form them, and the salts RX_{3} still more easily and with greater stability. This consideration also accounts for the great stability of the ammoniacal compounds of cupric oxide compared with those of silver oxide, since the former is displaced by the latter. It also enables us to see clearly the distinction which exists in the stability of the cobaltamine salts containing salts corresponding with cobaltous oxide, and those corresponding with higher oxides of cobalt, for the latter are weaker bases than cobaltous oxides. _The nature of the forces and quality of the phenomena occurring during the formation of the most stable substances, and of such compounds as crystallisable compounds, are one and the same, although perhaps exhibited in a different degree._ This, in my opinion, may be best confirmed by examining the compounds of carbon, because for this element the nature of the forces acting during the formation of its compounds is well known. Let us take as an example two unstable compounds of carbon. Acetic acid, C_{2}H_{4}O_{2} (specific gravity 1·06), with water forms the hydrate, C_{2}H_{4}O_{2},H_{2}O, denser (1·07) than either of the components, but unstable and easily decomposed, generally simply referred to as a solution. Such also is the crystalline compound of oxalic acid, C_{2}H_{2}O_{4}, with water, C_{2}H_{2}O_{4},2H_{2}O. Their formation might be predicted as starting from the hydrocarbon C_{2}H_{6}, in which, as in any other, the hydrogen may be exchanged for chlorine, the water residue (hydroxyl), &c. The first substitution product with hydroxyl, C_{2}H_{5}(HO), is stable; it can be distilled without alteration, resists a temperature higher than 100°, and then does not give off water. This is ordinary alcohol. The second, C_{2}H_{4}(HO)_{2}, can also be distilled without change, but can be decomposed into water and C_{2}H_{4}O (ethylene oxide or aldehyde); it boils at about 197°, whilst the first hydrate boils at 78°, a difference of about 100°. The compound C_{2}H_{3}(HO)_{3} will be the third product of such substitution; it ought to boil at about 300°, but does not resist this temperature--it decomposes into H_{2}O and C_{2}H_{4}O_{2}, where only one hydroxyl group remains, and the other atom of oxygen is left in the same condition as in ethylene oxide, C_{2}H_{4}O. There is a proof of this. Glycol, C_{2}H_{4}(HO)_{2}, boils at 197°, and forms water and ethylene oxide, which boils at 13° (aldehyde, its isomeride, boils at 21°); therefore the product disengaged by the splitting up of the hydrate boils at 184° lower than the hydrate C_{2}H_{4}(HO)_{2}. Thus the hydrate C_{2}H_{3}(HO)_{3}, which ought to boil at about 300°, splits up in exactly the same way into water and the product C_{2}H_{4}O_{2}, which boils at 117°--that is, nearly 183° lower than the hydrate, C_{2}H_{3}(HO)_{3}. But this hydrate splits up before distillation. The above-mentioned hydrate of acetic acid is such a decomposable hydrate--that is to say, what is called a solution. Still less stability may be expected from the following hydrates. C_{2}H_{2}(HO)_{4} also splits up into water and a hydrate (it contains two hydroxyl groups) called glycolic acid, C_{2}H_{2}O(HO)_{2} = C_{2}H_{4}O_{3}. The next product of substitution will be C_{2}H(HO)_{5}; it splits up into water, H_{2}O, and glyoxylic acid, C_{2}H_{4}O_{4} (three hydroxyl groups). The last hydrate which ought to be obtained from C_{2}H_{6}, and ought to contain C_{2}(HO)_{6}, is the crystalline compound of oxalic acid, C_{2}H_{2}O_{4} (two hydroxyl groups), and water, 2H_{2}O, which has been already mentioned. The hydrate C_{2}(HO)_{6} = C_{2}H_{2}O_{4},2H_{2}O, ought, according to the foregoing reasoning, to boil at about 600° (because the hydrate, C_{2}H_{4}(HO)_{2}, boils at about 200°, and the substitution of 4 hydroxyl groups for 4 atoms of hydrogen will raise the boiling-point 400°). It does not resist this temperature, but at a much lower point splits up into water, 2H_{2}O, and the hydrate C_{2}O_{2}(HO)_{2}, which is also capable of yielding water. Without going into further discussion of this subject, it may be observed that the formation of the hydrates, or compounds with water of crystallisation, of acetic and oxalic acids has thus received an accurate explanation, illustrating the point we desired to prove in affirming that compounds with water of crystallisation are held together by the same forces as those which act in the formation of other complex substances, and that the easy displaceability of the water of crystallisation is only a peculiarity of a local character, and not a radical point of distinction. All the above-mentioned hydrates, C_{2}X_{6}, or products of their destruction, are actually obtained by the oxidation of the first hydrate, C_{2}H_{3}(HO), or common alcohol, by nitric acid (Sokoloff and others). Hence the forces which induce salts to combine with _n_H_{2}O or with NH_{3} are undoubtedly of the same order as the forces which govern the formation of ordinary 'atomic' and saline compounds. (A great impediment in the study of the former was caused by the conviction which reigned in the sixties and seventies, that 'atomic' were essentially different from 'molecular' compounds like crystallohydrates, in which it was assumed that there was a combination of entire molecules, as though without the participation of the atomic forces.) If the bond between chlorine and different metals is not equally strong, so also the bond uniting _n_H_{2}O and _n_NH_{3} is exceeding variable; there is nothing very surprising in this. And in the fact that the combination of different amounts of NH_{3} and H_{2}O alters the capacity of the haloids X of the salts RX_{2} for reaction (for instance, in the luteo-salts all the X_{3}, while in the purpureo, only 2 out of the 3, and in the prazeo-salts only 1 of the 3 X's reacts), we should see in the first place a phenomenon similar to what we met with in Cr_{2}Cl_{6} (Chapter XXI., Note 7 bis), for in both instances the essence of the difference lies in the removal of water; a molecule RCl_{3},6H_{2}O or RCl_{3},6NH_{3} contains the halogen in a perfectly mobile (ionised) state, while in the molecule RCl_{3},5H_{2}O or RCl_{3},5NH_{3} a portion of the halogen has almost lost its faculty for reacting with AgNO_{3}, just as metalepsical chlorine has lost this faculty which is fully developed in the chloranhydride. Until the reason of this difference be clear, we cannot expect that ordinary points of view and generalisation can give a clear answer. However, we may assume that here the explanation lies in the nature and kind of motion of the atoms in the molecules, although as yet it is not clear how. Nevertheless, I think it well to call attention again (Chapter I.) to the fact that the combination of water, and hence, also, of any other element, leads to most diverse consequences; the water in the gelatinous hydrate of alumina or in the decahydrated Glauber salt is very mobile, and easily reacts like water in a free state; but the same water combined with oxide of calcium, or C_{2}H_{4} (for instance, in C_{2}H_{6}O and in C_{4}H_{10}O), or with P_{2}O_{5}, has become quite different, and no longer acts like water in a free state. We see the same phenomenon in many other cases--for example, the chlorine in chlorates no longer gives a precipitate of chloride of silver with AgNO_{3}. Thus, although the instance which is found in the difference between the roseo- and purpureo-salts deserves to be fully studied on account of its simplicity, still it is far from being exceptional, and we cannot expect it to be thoroughly explained unless a mass of similar instances, which are exceedingly common among chemical compounds, be conjointly explained. (Among the researches which add to our knowledge respecting the complex ammoniacal compounds, I think it indispensable to call the reader's attention to Prof. Kournakoff's dissertation 'On complex metallic bases,' 1893.) Kournakoff (1894) showed that the solubility of the luteo-salt, CoCl_{3},6NH_{3}, at 0° = 4·30 (per 100 of water), at 20° = 7·7, that in passing into the roseo-salt, CoCl_{3}H_{2}O_{5}NH_{3}, the solubility rises considerably, and at 0° = 16·4, and at 20° = about 27, whilst the passage into the purpureo-salt, CoCl_{3},5NH_{3}, is accompanied by a great fall in the solubility, namely, at 0° = 0·23, and at 20° = about 0·5. And as crystallohydrates with a smaller amount of water are usually more soluble than the higher crystallohydrates (Le Chatelier), whilst here we find that the solubility falls (in the purpureo-salt) with a loss of water, that water which is contained in the roseo-salt cannot be compared with the water of crystallisation. Kournakoff, therefore, connects the fall in solubility (in the passage of the roseo- into the purpureo-salts) with the accompanying loss in the reactive capacity of the chlorine. In conclusion, it may be observed that the elements of the eighth group--that is, the analogues of iron and platinum--according to my opinion, will yield most fruitful results when studied as to combinations with whole molecules, as already shown by the examples of complex ammoniacal, cyanogen, nitro-, and other compounds, which are easily formed in this eighth group, and are remarkable for their stability. This faculty of the elements of the eighth group for forming the complex compounds alluded to, is in all probability connected with the position which the eighth group occupies with regard to the others. Following the seventh, which forms the type RX_{7}, it might be expected to contain the most complex type, RX_{8}. This is met with in OsO_{4}. The other elements of the eighth group, however, only form the lower types RX_{2}, RX_{3}, RX_{4} ... and these accordingly should be expected to aggregate themselves into the higher types, which is accomplished in the formation of the above-mentioned complex compounds. [35 bis] Marshall (1891) obtained cobaltic sulphate, Co_{2}(SO_{4})_{3},18H_{2}O, by the action of an electric current upon a strong solution of CoSO_{4}. [36] The action of an alkaline hypochlorite or hypobromite upon a boiling solution of cobaltous salts, according to Schroederer (1889), produces oxides, whose composition varies between Co_{3}O_{5} (Rose's compound) and Co_{2}O_{3}, and also between Co_{5}O_{8} and Co_{12}O_{19}. If caustic potash and then bromine be added to the liquid, only Co_{2}O_{3} is formed. The action of alkaline hypochlorites or hypo-bromites, or of iodine, upon cobaltic salts, gives a highly-coloured precipitate which has a different colour to the hydrate of the oxide Co_{2}(OH)_{6}. According to Carnot the precipitate produced by the hypochlorites has a composition Co_{10}O_{16}, whilst that given by iodine in the presence of an alkali contains a larger amount of oxygen. Fortmann (1891) reinvestigated the composition of the higher oxygen oxide obtained by iodine in the presence of alkali, and found that the greenish precipitate (which disengages oxygen when heated to 100°) corresponds to the formula CoO_{2}. The reaction must be expressed by the equation: CoX_{2} + I_{2} + 4KHO = CoO_{2} + 2KX + 2KI + 2H_{2}O. [37] Prior to Fortmann, Rousseau (1889) endeavoured to solve the question as to whether CoO_{2} was able to combine with bases. He succeeded in obtaining a barium compound corresponding to this oxide. Fifteen grams of BaCl_{2} or BaBr_{2} are triturated with 5-6 grams of oxide of barium, and the mixture heated to redness in a closed platinum crucible; 1 gram of oxide of cobalt is then gradually added to the fused mass. Each addition of oxide is accompanied by a violent disengagement of oxygen. After a short time, however, the mass fuses quietly, and a salt settles at the bottom of the crucible, which, when freed from the residue, appears as black hexagonal, very brilliant crystals. In dissolving in water this substance evolves chlorine; its composition corresponds to the formula 2(CoO_{2})BaO. If the original mass be heated for a long time (40 hours), the amount of dioxide in the resultant mass decreases. The author obtained a neutral salt having the composition CoO_{2}BaO (this compound = BaO_{2}CoO) by breaking up the mass as it agglomerates together, and bringing the pieces into contact with the more heated surface of the crucible. This salt is formed between the somewhat narrow limits of temperature 1,000°-1,100°; above and below these limits compounds richer or poorer in CoO_{2} are formed. The formation of CoO_{2} by the action of BaO_{2}, and the easy decomposition of CoO_{2} with the evolution of oxygen, give reason for thinking that it belongs to the class of peroxides (like Cr_{2}O_{7}, CaO_{2}, &c.); it is not yet known whether they give peroxide of hydrogen like the true peroxides. The fact that it is obtained by means of iodine (probably through HIO), and its great resemblance to MnO_{2}, leads rather to the supposition that CoO_{2} is a very feeble saline oxide. The form CoO_{2} is repeated in the cobaltic compounds (Note 35), and the existence of CoO_{2} should have long ago been recognised upon this basis. Nickel alloys possess qualities which render them valuable for technical purposes, the alloy of nickel with iron being particularly remarkable. This alloy is met with in nature as _meteoric iron_. The Pallasoffsky mass of meteoric iron, preserved in the St. Petersburg Academy, fell in Siberia in the last century; it weighs about 15 cwt. and contains 88 p.c. of iron and about 10 p.c. of nickel, with a small admixture of other metals. In the arts _German silver_ is most extensively used; it is an alloy containing nickel, copper, and zinc in various proportions. It generally consists of about 50 parts of copper, 25 parts of zinc, and 25 parts of nickel. This alloy is characterised by its white colour resembling that of silver, and, like this latter metal, it does not rust, and therefore furnishes an excellent substitute for silver in the majority of cases where it is used. Alloys which contain silver in addition to nickel show the properties of silver to a still greater extent. Alloys of nickel are used for currency, and if rich deposits of nickel are discovered a wide field of application lies before it, not only in a pure state (because it is a beautiful metal and does not rust) but also for use in alloys. Steel vessels (pressed or forged out of sheet steel) covered with nickel have such practical merits that their manufacture, which has not long commenced, will most probably be rapidly developed, whilst nickel steel, which exceeds ordinary steel in its tenacity, has already proved its excellent qualities for many purposes (for instance, for armour plate). Until 1890 no compound of cobalt or nickel was known of sufficient volatility to determine the molecular weights of the compounds of these metals; but in 1890 Mr. L. Mond, in conducting (together with Langer and Quincke) his researches on the action of nickel upon carbonic oxide (Chapter IX., Note 24 bis), observed that nickel gradually volatilises in a stream of carbonic oxide; this only takes place at low temperatures, and is seen by the coloration of the flame of the carbonic oxide. This observation led to the discovery of a remarkable volatile _compound of nickel and carbonic oxide_, having as molecular composition Ni(CO)_{4},[38] as determined by the vapour density and depression of the freezing point. Cobalt and many other metals do not form volatile compounds under these conditions, but iron gives a similar product (Note 26 bis). Ni(CO)_{4} is prepared by taking finely divided Ni (obtained by reducing NiO by heating it in a stream of hydrogen, or by igniting the oxalate NiC_{2}O_{4})[39] and passing (at a temperature below 50°, for even at 60° decomposition may take place and an explosion) a stream of CO over it; the latter carries over the vapour of the compound, which condenses (in a well-cooled receiver) into a perfectly colourless extremely mobile liquid, boiling without decomposition at 43°, and crystallising in needles at -25° (Mond and Nasini, 1891). Liquid Ni(CO)_{4} has a sp. gr. 1·356 at 0°, is insoluble in water, dissolves in alcohol and benzene, and burns with a very smoky flame due to the liberation of Ni. The vapour when passed through a tube heated to 180° and above deposits a brilliant coating of metal, and disengages CO. If the tube be strongly heated the decomposition is accompanied by an explosion. If Ni(CO)_{4} as vapour be passed through a solution of CuCl_{2}, it reduces the latter to metal; it has the same action upon an ammoniacal solution of AgCl, strong nitric acid oxidises Ni(CO)_{4}, dilute solutions of acids have no action; if the vapour be passed through strong sulphuric acid, CO is liberated, chlorine gives NiCl and COCl_{2}; no simple reactions of double decomposition are yet known for Ni(CO)_{4}, however, so that its connection with other carbon compounds is not clear. Probably the formation of this compound could be applied for extracting nickel from its ores.[40] [38] This compound is known as nickel tetra-carbonyl. It appears to me yet premature to judge of the structure of such an extraordinary compound as Ni(CO)_{4}. It has long been known that potassium combines with CO forming K_{_n_}(CO)_{_n_} (Chapter IX., Note 31), but this substance is apparently saline and non-volatile, and has as little in common with Ni(CO)_{4} as Na_{2}H has with SbH_{3}. However, Berthelot observed that when NiC_{4}O_{4} is kept in air, it oxidises and gives a colourless compound, Ni_{3}C_{2}O_{3},10H_{2}O, having apparently saline properties. We may add that Schützenberger, on reducing NiCl_{2} by heating it in a current of hydrogen, observed that a nickel compound partially volatilises with the HCl and gives metallic nickel when heated again. The platinum compound, PtCl_{2}(CO)_{3} (Chapter XXIII., Note 11), offers the greatest analogy to Ni(CO)_{4}. This compound was obtained as a volatile substance by Schützenberger by moderately heating (to 235°) metallic platinum in a mixture of chlorine and carbonic oxide. If we designate CO by Y, and an atom of chlorine by X, then taking into account that, according to the periodic system, Ni is an analogue of Pt, a certain degree of correspondence is seen in the composition NiY_{4} and PtX_{2}Y_{2}. It would be interesting to compare the reactions of the two compounds. [39] According to its empirical formula oxalate of nickel also contains nickel and carbonic oxide. [40] The following are the thermo-chemical data (according to Thomsen, and referred to gram weights expressed by the formula, in large calories or thousand units of heat) for the formation of corresponding compounds of Mn, Fe, Co, Ni, and Cu (+ Aq signifies that the reaction proceeds in an excess of water): R = Mn Fe Co Ni Cu R + Cl_{2} + Aq 128 100 95 94 63 R + Br_{2} + Aq 106 78 73 72 41 R + I_{2} + Aq 76 48 43 41 32 R + O + H_{2}O 95 68 63 61 38 R + O_{2} + SO_{2} + _n_H_{2}O 193 169 163 163 130 RCl_{2} + Aq +16 18 18 19 11 These examples show that for analogous reactions the amount of heat evolved in passing from Mn to Fe, Co, Ni, and Cu varies in regular sequences as the atomic weight increases. A similar difference is to be found in other groups and series, and proves that thermo-chemical phenomena are subject to the periodic law. CHAPTER XXIII THE PLATINUM METALS The six metals: ruthenium, Ru, rhodium, Rh, palladium, Pd, osmium, Os, iridium, Ir, and platinum, Pt, are met with associated together in nature. Platinum always predominates over the others, and hence they are known as the _platinum metals_. By their chemical character their position in the periodic system is in the eighth group, corresponding with iron, cobalt, and nickel. The natural transition from titanium and vanadium to copper and zinc by means of the elements of the iron group is demonstrated by all the properties of these elements, and in exactly the same manner a transition from zirconium, niobium, and molybdenum to silver, cadmium, and indium, through ruthenium, rhodium, and palladium, is in perfect accordance with fact and with the magnitude of the atomic weights, as also is the position of osmium, iridium, and platinum between tantalum and tungsten on the one side, and gold and mercury on the other. In all these three cases the elements of smaller atomic weight (chromium, molybdenum, and tungsten) are able, in their higher grades of oxidation, to give acid oxides having the properties of distinct but feebly energetic acids (in the lower oxides they give bases), whilst the elements of greater atomic weight (zinc, cadmium, mercury), even in their higher grades of oxidation, only give bases, although with feebly developed basic properties. The platinum metals present the same intermediate properties such as we have already seen in iron and the elements of the eighth group. In the platinum metals the intermediate properties _of feebly acid and feebly basic metals_ are developed with great clearness, so that there is not one sharply-defined acid anhydride among their oxides, although there is a great diversity in the grades of oxidation from the type RO_{4} to R_{2}O. The feebleness of the chemical forces observed in the platinum metals is connected with the ready decomposability of their compounds, with the small atomic volume of the metals themselves, and with their large atomic weight. The oxides of platinum, iridium, and osmium can scarcely be termed either basic or acid; they are capable of combinations of both kinds, each of which is feeble. They are all intermediate oxides. The atomic weights of platinum, iridium, and osmium are nearly 191 to 196, and of palladium, rhodium, and ruthenium, 104 to 106. Thus, strictly speaking, we have here two series of metals, which are, moreover, perfectly parallel to each other; three members in the first series, and three members in the second--namely, platinum presents an analogy to palladium, iridium to rhodium, and osmium to ruthenium. As a matter of fact, however, the whole _group_ of the platinum metals is characterised by _a number of common properties_, both physical and chemical, and, moreover, there are several points of resemblance between the members of this group and those of the _iron_ group (Chapter XXII.) The atomic volumes (Table III., column 18) of the elements of this group are _nearly equal_ and _very small_. The iron metals have atomic volumes of nearly 7, whilst that of the metals allied to palladium is nearly 9, and of those adjacent to platinum (Pt, Ir, Os) nearly 9·4. This comparatively small atomic volume corresponds with the great infusibility and tenacity proper to all the iron and platinum metals, and to their small chemical energy, which stands out very clearly in the heavy platinum metals. All the platinum metals are very _easily reduced_ by ignition and by the action of various reducing agents, in which process oxygen, or a haloid group, is disengaged from their compounds and the metal left behind. This is a property of the platinum metals which determines many of their reactions, and the circumstance of their always being found in nature _in a native state_. In Russia in the Urals (discovered in 1819) and in Brazil (1735) platinum is obtained from alluvial deposits, but in 1892 Professor Inostrantseff discovered a vein deposit of platinum in serpentine near Tagil in the Urals.[1] The facility with which they are reduced is so great that their chlorides are even decomposed by gaseous hydrogen, especially when shaken up and heated under a certain pressure. Hence it will be readily understood that such metals as zinc, iron, &c., separate them from solutions with great ease, which fact is taken advantage of in practice and in the chemical treatment of the platinum metals.[1 bis] [1] Wells and Penfield (1888) have described a mineral sperryllite found in the Canadian gold-bearing quartz and consisting of platinum diarsenide, PtAs_{2}. It is a noticeable fact that this mineral clearly confirms the position of platinum in the same group as iron, because it corresponds in crystalline form (regular octahedron) and chemical composition with iron pyrites, FeS_{2}. [1 bis] Some light is thrown upon the facility with which the platinum compounds decompose by Thomsen's data, showing that in an excess of water (+ Aq) the formation from platinum, of such a double salt as PtCl_{2},2KCl, is accompanied by a comparatively small evolution of heat (_see_ Chapter XXI., Note 40), for instance, Pt + Cl_{2} + 2KCl + Aq only evolves about 33,000 calories (hence the reaction, Pt + Cl_{2} + Aq, will evidently disengage still less, because PtCl_{2} + 2KCl evolves a certain amount of heat), whilst on the other hand, Fe + Cl_{2} + Aq gives 100,000 calories, and even the reaction with copper (for the formation of the double salt) evolves 63,000 calories. All the platinum metals, like those of the iron group, are grey, with a comparatively feeble metallic lustre, and are very infusible. In this respect they stand in the same order as the metals of the iron series; nickel is more fusible and whiter than cobalt and iron, so also palladium is whiter and more fusible than rhodium and ruthenium, and platinum is comparatively more fusible and whiter than iridium or osmium. The saline compounds of these metals are red or yellow, like those of the majority of the metals of the iron series, and like the latter, the different forms of oxidation present different colours. Moreover, certain complex compounds of the platinum metals, like certain complex compounds of the iron series, either have particular characteristic tints or else are colourless. The platinum metals are found _in nature associated together in alluvial deposits_ in a few localities, from which they are washed, owing to their very considerable density, which enables a stream of water to wash away the sand and clay with which they are mixed. Platinum deposits are chiefly known in the Urals, and also in Brazil and a few other localities. The platinum ore washed from these alluvial deposits presents the appearance of more or less coarse grains, and sometimes, as it were, of semi-fused nuggets.[2] [2] The largest amount of platinum is extracted in the Urals, about five tons annually. A certain amount of gold is extracted from the washed platinum by means of mercury, which does not dissolve the platinum metals but dissolves the gold accompanying the platinum in its ores. Moreover, the ores of platinum always contain metals of the iron series associated with them. The washed and mechanically sorted ore in the majority of cases contains about 70 to 80 p.c. of platinum, about 5 to 8 p.c. of iridium, and a somewhat smaller quantity of osmium. The other platinum metals--palladium, rhodium, and ruthenium--occur in smaller proportions than the three above named. Sometimes grains of almost pure osmium-iridium, containing only a small quantity of other metals, are found in platinum ores. This _osmium-iridium_ may be easily separated from the other platinum metals, owing to its being nearly insoluble in aqua regia, by which the latter are easily dissolved. There are grains of platinum which are magnetic. The grains of osmium-iridium are very hard and malleable, and are therefore used for certain purposes, for instance, for the tips of gold pens. All the platinum metals give compounds with the halogens, and the highest haloid type of combination for all is RX_{4}. For the majority of the platinum metals this type is exceedingly unstable; the lower compounds corresponding to the type RX_{2}, which are formed by the separation of X_{2}, are more stable. In the type RX_{2} the platinum metals form more stable salts, which offer no little resemblance to the kindred compounds of the iron series--for example, to nickelous chloride, NiCl_{2}, cobaltous chloride, CoCl_{2}, &c. This even expresses itself in a similarity of volume (platinous chloride, PtCl_{2}, volume, 46; nickelous chloride, NiCl_{2} = 50), although in the type RX_{2} the true iron metals give very stable compounds, whilst the platinum metals frequently react after the manner of suboxides, decomposing into the metal and higher types, 2RX_{2} = R + RX_{4}. This probably depends on the facility with which RX_{2} decomposes into R and X_{2}, when X_{2} combines with the remaining portion of RX_{2}. As in the series iron, cobalt, nickel, nickel gives NiO and Ni_{2}O_{3}, whilst cobalt and iron give higher and varied forms of oxidation, so also among the platinum metals, platinum and palladium only give the forms RX_{2} and RX_{4}, whilst rhodium and iridium form another and intermediate type, RX_{3}, also met with in cobalt, corresponding with the oxide, having the composition R_{2}O_{3}, besides which they form an acid oxide, like ferric acid, which is also known in the form of salts, but is in every respect unstable. _Osmium_ and _ruthenium_, like manganese, form still higher oxides, and in this respect exhibit the greatest diversity. They not only give RX_{2}, RX_{3}, RX_{4}, and RX_{6}, but also a still _higher form of oxidation_, RO_{4}, which is not met with in any other series. This form is exceedingly characteristic, owing to the fact that the oxides, OsO_{4} and RuO_{4}, are volatile and have feebly acid properties. In this respect they most resemble permanganic anhydride, which is also somewhat volatile.[3] [3] In characterising the platinum metals according to their relation to the iron metals, it is very important to add two more very remarkable points. The platinum metals are capable of forming a sort of unstable compound with _hydrogen_; they absorb it and only part with it when somewhat strongly heated. This faculty is especially developed in platinum and palladium, and it is very characteristic that nickel, which exactly corresponds with platinum and palladium in the periodic system, should exhibit the same faculty for retaining a considerable quantity of hydrogen (Graham's and Raoult's experiments). Another characteristic property of the platinum metals consists in their easily giving (like cobalt which forms the cobaltic salts) stable and characteristic saline _compounds with ammonia_, and like Fe and Co, double salts with the cyanides of the alkali metals, especially in their lower forms of combination. All the above so clearly brings the elements of the iron series in close relation to the platinum metals, that the eighth group acquires as natural a character as can be required, with a certain originality or individuality for each element. When dissolved in aqua regia (PtCl_{4} is formed) and liberated from the solution by sal-ammoniac ((NH_{4})_{2}PtCl_{6} is formed) and reduced by ignition (which may be done by Zn and other reducing agents, direct from a solution of PtCl_{4}) platinum[3 bis] forms a powdery mass, known as spongy platinum or platinum black. If this powder of platinum be heated and pressed, or hammered in a cylinder, the grains aggregate or forge together, and form a continuous, though of course not entirely homogeneous, mass. Platinum was formerly, and is even now, worked up in this manner. The platinum money formerly used in Russia was made in this way. Sainte-Claire Deville, in the fifties, for the first time melted platinum in considerable quantities by employing a special furnace made in the form of a small reverberatory furnace, and composed of two pieces of lime, on which the heat of the oxyhydrogen flame has no action. Into this furnace (shown in fig. 34, Vol. I. p. 175)--or, more strictly speaking, into the cavity made in the pieces of lime--the platinum is introduced, and two orifices are made in the lime; through one, the upper, or side orifice, is introduced an oxyhydrogen gas burner, in which either detonating gas or a mixture of oxygen and coal-gas is burnt, whilst the other orifice serves for the escape of the products of combustion and certain impurities which are more volatile than the platinum, and especially the oxidised compounds of osmium, ruthenium, and palladium, which are comparatively easily volatilised by heat. In this manner the platinum is converted into a continuous metallic form by means of fusion, and this method is now used for melting considerable masses of platinum[4] and its alloys with iridium. [3 bis] Platinum was first obtained in the last century from Brazil, where it was called silver (platinus). Watson in 1750 characterised platinum as a separate independent metal. In 1803 Wollaston discovered palladium and rhodium in crude platinum, and at about the same time Tennant distinguished iridium and osmium in it. Professor Claus, of Kazan, in his researches on the platinum metals (about 1840) discovered ruthenium in them, and to him are due many important discoveries with regard to these elements, such as the indication of the remarkable analogy between the series Pd--Rh--Ru and Pt--Ir--Os. _The treatment of platinum ore_ is chiefly carried on for the extraction of the platinum itself and its alloys with iridium, because these metals offer a greater resistance to the action of chemical reagents and high temperatures than any of the other malleable and ductile metals, and therefore the wire so often used in the laboratory and for technical purposes is made from them, as also are various vessels used for chemical purposes in the laboratory and in works. Thus sulphuric acid is distilled in platinum retorts, and many substances are fused, ignited, and evaporated in the laboratory in platinum crucibles and on platinum foil. Gold and many other substances are dissolved in dishes made of iridium-platinum, because the alloys of platinum and iridium are but slightly attacked when subjected to the action of aqua regia. The comparatively high density (about 21·5), hardness, ductility, and infusibility (it does not melt at a furnace heat, but only in the oxyhydrogen flame or electric furnace), as well as the fact of its resisting the action of water, air, and other reagents, renders an alloy of 90 parts of platinum and 10 parts of iridium (Deville's platinum-iridium alloy) a most valuable material for making standard weights and measures, such as the metre, kilogram, and pound, and therefore all the newest standards of most countries are made of this alloy. [4] This process has altered the technical treatment of platinum to a considerable extent. It has in particular facilitated the manufacture of alloys of platinum with iridium and rhodium from the pure platinum ores, since it is sufficient to fuse the ore in order for the greater amount of the osmium to burn off, and for the mass to fuse into a homogeneous, malleable alloy, which can be directly made use of. There is very little ruthenium in the ores of platinum. If during fusion lead be added, it dissolves the platinum (and other platinum metals) owing to its being able to form a very characteristic alloy containing PtPb. If an alloy of the two metals be left exposed to moist air, the excess of lead is converted into carbonate (white lead) in the presence of the water and carbonic acid of the air, whilst the above platinum alloy remains unchanged. The white lead may be extracted by dilute acid, and the alloy PtPb remains unaltered. The other platinum metals also give similar alloys with lead. The fusibility of these alloys enables the platinum metals to be separated from the gangue of the ore, and they may afterwards be separated from the lead by subjecting the alloy to oxidation in furnaces furnished with a bone ash bed, because the lead is then oxidised and absorbed by the bone ash, leaving the platinum metals untouched. This method of treatment was proposed by H. Sainte-Claire Deville in the sixties, and is also used in the analysis of these metals (_see_ further on). To obtain pure platinum, the ore is treated with aqua regia in which only the osmium and iridium are insoluble. The solution contains the platinum metals in the form RCl_{4}, and in the lower forms of chlorination, RCl_{3} and RCl_{2}, because some of these metals--for instance, palladium and rhodium--form such unstable chlorides of the type RX_{4} that they partially decompose even when diluted with water, and pass into the stable lower type of combination; in addition to which the chlorine is very easily disengaged if it comes in contact with substances on which it can act. In this respect platinum resists the action of heat and reducing agents better than any of its companions--that is, it passes with greater difficulty from PtCl_{4} to the lower compound PtCl_{2}. On this is based the method of preparation of more or less pure platinum. Lime or sodium hydroxide is added to the solution in aqua regia until neutralised, or only containing a very slight excess of alkali. It is best to first evaporate and slightly ignite the solution, in order to remove the excess of acid, and by heating it to partially convert the higher chlorides of the palladium, &c., into the lower. The addition of alkalis completes the reduction, because the chlorine held in the compounds RX_{4} acts on the alkali like free chlorine, converting it into a hypochlorite. Thus palladium chloride, PdCl_{4}, for example, is converted into palladious chloride, PdCl_{2}, by this means, according to the equation PdCl_{4} + 2NaHO = PdCl_{2} + NaCl + NaClO + H_{2}O. In a similar manner iridic chloride, IrCl_{4}, is converted into the trichloride, IrCl_{3}, by this method. When this conversion takes place the platinum still remains in the form of platinic chloride, PtCl_{4}. It is then possible to take advantage of a certain difference in the properties of the higher and lower chlorides of the platinum metals. Thus lime precipitates the lower chlorides of the members of the platinum metals occurring in solution without acting on the platinic chloride, PtCl_{4}, and hence the addition of a large proportion of lime immediately precipitates the associated metals, leaving the platinum itself in solution in the form of a soluble double salt, PtCl_{4},CaCl_{2}. A far better and more perfect _separation_ is effected _by means of ammonium chloride_, which gives, with platinic chloride, an insoluble yellow precipitate, PtCl_{4},2NH_{4}Cl, whilst it forms soluble double salts with the lower chlorides RCl_{2} and RCl_{3}, so that ammonium chloride precipitates the platinum only from the solution obtained by the preceding method. These methods are employed for preparing the platinum which is used for the manufacture of platinum articles, because, having platinum in solution as calcium platinochloride, PtCaCl_{6}, or as the insoluble ammonium platinochloride, Pt(NH_{4})_{2}Cl_{6}, the platinum compound in every case, after drying or ignition, loses all the chlorine from the platinic chloride and leaves finely-divided metallic platinum, which may be converted into homogeneous metal by compression and forging, or by fusion.[5] [5] For the ultimate purification of platinum from palladium and iridium the metals must be re-dissolved in aqua regia, and the solution evaporated until the residue begins to evolve chlorine. The residue is then re-precipitated with ammonium or potassium chloride. The precipitate may still contain a certain amount of iridium, which passes with greater difficulty from the tetrachloride, IrCl_{4}, into the trichloride, IrCl_{3}, but it will be quite free from palladium, because the latter easily loses its chlorine and passes into palladious chloride, PdCl_{2}, which gives an easily-soluble salt with potassium chloride. The precipitate, containing a small quantity of iridium, is then heated with sodium carbonate in a crucible, when the mass decomposes, giving metallic platinum and iridium oxide. If potassium chloride has been employed, the residue after ignition is washed with water and treated with aqua regia. The iridium oxide remains undissolved, and the platinum easily passes into solution. Only cold and dilute aqua regia must be used. The solution will then contain pure platinic chloride, which forms the starting-point for the preparation of all platinum compounds. Pure platinum for accurate researches (for instance, for the unit of light, according to Violle's method) may be obtained (Mylius and Foerster, 1892) by Finkener's method, by dissolving the impure metal in aqua regia (it should be evaporated to drive off the nitrogen compounds), and adding NaCl so as to form a double sodium salt, which is purified by crystallising with a small amount of caustic soda, washing the crystals with a strong solution of NaCl, and then dissolving them in a hot 1 p.c. solution of soda, repeating the above and ultimately igniting the double salt, previously dried at 120°, in a stream of hydrogen; platinum black and NaCl are then formed. The three following are very sensitive tests (to thousandths of a per cent.) for the presence of Ir, Ru, Rh, Pd (osmium is not usually present in platinum which has once been purified, since it easily volatilises with Cl_{2} and CO_{2}, and in the first treatment of the crude platinum either passes off as OsO_{4} or remains undissolved), Fe, Cu, Ag, and Pb: (1) the assay is alloyed with 10 parts of pure lead, the alloy treated with dilute nitric acid (to remove the greater part of the Pb), and dissolved in aqua regia; the residue will consist of Ir and Ru; the Pb is precipitated from the nitric acid solution by sulphuric acid, whilst the remaining platinum metals are reduced from the evaporated solution by formic acid, and the resultant precipitate fused with KHSO_{4}; the Pd and Rh are thus converted into soluble salts, and the former is then precipitated by HgC_{2}N_{2}. (2) Iron may be detected by the usual reagents, if the crude platinum be dissolved in aqua regia, and the platinum metals precipitated from the solution by formic acid. (3) If crude platinum (as foil or sponge) be heated in a mixture of chlorine and carbonic oxide it volatilises (with a certain amount of Ir, Pd, Fe, &c.) as PtCl_{2},2CO (Note 11), whilst the whole of the Rh, Ag, and Cu it may contain remains behind. Among other characteristic reactions for the platinum metals, we may mention: (1) that rhodium is precipitated from the solution obtained after fusion with KHSO_{4} (in which Pt does not dissolve) by NH_{3}, acetic and formic acids; (2) that dilute aqua regia dissolves precipitated Pt, but not Rh; (3) that if the insoluble residue of the platinum metals (Ir, Ru, Os) obtained, after treating with aqua regia, be fused with a mixture of 1 part of KNO_{3} and 3 parts of K_{2}CO_{3} (in a gold crucible), and then treated with water, it gives a solution containing the Ru (and a portion of the Ir), but which throws it all down when saturated with chlorine and boiled; (4) that if iridium be fused with a mixture of KHO and KNO_{3}, it gives a soluble potassium salt, IrK_{2}O_{4} (the solution is blue), which, when saturated with chlorine, gives IrCl_{4}, which is precipitated by NH_{4}Cl (the precipitate is black), forming a double salt, leaving metallic Ir after ignition; (5) that rhodium mixed with NaCl and ignited in a current of chlorine gives a soluble double salt (from which sal-ammoniac separates Pt and Ir), which gives (according to Jörgensen) a difficultly soluble purpureo-salt (Chapter XXII., Note 35), Rh_{2}Cl_{3},5NH_{3}, when treated with NH_{3}; in this form the Rh may be easily purified and obtained in a metallic form by igniting in hydrogen; and (6) that palladium, dissolved in aqua regia and dried (NH_{4}Cl throws down any Pt), gives soluble PdCl_{2}, which forms an easily crystallisable yellow salt, PdCl_{2}NH_{3}, with ammonia; this salt (Wilm) may be easily purified by crystallisation, and gives metallic Pd when ignited. These reactions illustrate the method of separating the platinum metals from each other. Metallic _platinum_ in a fused state has a specific gravity of 21; it is grey, softer than iron but harder than copper, exceedingly ductile, and therefore easily drawn into wire and rolled into thin sheets, and may be hammered into crucibles and drawn into thin tubes, &c. In the state in which it is obtained by the ignition of its compounds, it forms a spongy mass, known as spongy platinum, or else as powder (platinum black).[6] In either case it is dull grey, and is characterised, as we already know, by the faculty of absorbing hydrogen and other gases. Platinum is not acted on by hydrochloric, hydriodic, nitric, and sulphuric acids, or a mixture of hydrofluoric and nitric acids. Aqua regia, and any liquid containing chlorine or able to evolve chlorine or bromine, dissolves platinum. Alkalis are decomposed by platinum at a red heat, owing to the faculty of the platinum oxide, PtO_{2}, formed to combine with alkaline bases, inasmuch as it has a feebly-developed acid character (_see_ Note 8). Sulphur, phosphorus (the phosphide, PtP_{2}, is formed), arsenic and silicon all act more or less rapidly on platinum, under the influence of heat. Many of the metals form alloys with it. Even charcoal combines with platinum when it is ignited with it, and therefore carbonaceous matter cannot be subjected to prolonged and powerful ignition in platinum vessels. Hence a platinum crucible soon becomes dull on the surface in a smoky flame. Platinum also forms alloys with zinc, lead, tin, copper, gold, and silver.[7] Although mercury does not directly dissolve platinum, still it forms a solution or amalgam with spongy platinum in the presence of sodium amalgam; a similar amalgam is also formed by the action of sodium amalgam on a solution of platinum chloride, and is used for physical experiments. [6] We have already become acquainted with the effect of finely-divided platinum on many gaseous substances. It is best seen in the so-called _platinum black_, which is a coal-black powder left by the action of sulphuric acid on the alloy of zinc and platinum, or which is precipitated by metallic zinc from a dilute solution of platinum. In any case, finely-divided platinum absorbs gases more powerfully and rapidly the more finely divided and porous it is. Sulphurous anhydride, hydrogen, alcohol, and many organic substances in the presence of such platinum are easily oxidised by the oxygen of the air, although they do not combine with it directly. The absorption of oxygen is as much as several hundred volumes per one volume of platinum, and the oxidising power of such absorbed oxygen is taken advantage of not only in the laboratory but even in manufacturing processes. Asbestos or charcoal, soaked in a solution of platinic chloride and ignited, is very useful for this purpose, because by this means it becomes coated with platinum black. If 50 grams of PtCl_{4} be dissolved in 60 c.c. of water, and 70 c.c. of a strong (40 p.c.) solution of formic aldehyde added, the mixture cooled, and then a solution of 50 grams of NaHO in 50 grams of water added, the platinum is precipitated. After washing with water the precipitate passes into solution and forms a black liquid containing _soluble colloidal platinum_ (Loew, 1890). If the precipitated platinum be allowed to absorb oxygen on the filter, the temperature rises 40°, and a very porous _platinum black_ is obtained which vigorously facilitates oxidation. [7] It is necessary to remark that platinum when alloyed with silver, or as amalgam, is soluble in nitric acid, and in this respect it differs from gold, so that it is possible, by alloying gold with silver, and acting on the alloy with nitric acid, to recognise the presence of platinum in the gold, because nitric acid does not act on gold alloyed with silver. There are _two kinds_ of _platinum compounds_, PtX_{4} and PtX_{2}. The former are produced by an excess of halogen in the cold, and the latter by the aid of heat or by the splitting up of the former. The starting-point for the platinum compounds is _platinum tetrachloride_, _platinic chloride_, PtCl_{4}, obtained by dissolving platinum in aqua regia.[7 bis] The solution crystallises in the cold, in a desiccator, in the form of reddish-brown deliquescent crystals which contain hydrochloric acid, PtCl_{4},2HCl,6H_{2}O, and behave like a true acid whose salts correspond to the formula R_{2}PtCl_{6}--ammonium platinochloride, for example.[7 tri] The hydrochloric acid is liberated from these crystals by gently heating or evaporating the solution to dryness; or, better still, after treatment with silver nitrate a reddish-brown mass remains behind, which dissolves in water, and forms a yellowish-red solution which on cooling deposits crystals of the composition PtCl_{4},8H_{2}O. The _tendency_ of PtCl_{4} _to combine_ with hydrochloric acid and water--that is, _to form higher crystalline compounds_--is evident in the platinum compounds, and must be taken into account in explaining the properties of platinum and the formation of many other of its complex compounds. Dilute solutions of platinic chloride are yellow, and are completely reduced by hydrogen, sulphurous anhydride, and many reducing agents, which first convert the platinic chloride into the lower compound platinous chloride, PtCl_{2}. That faculty which reveals itself in platinum tetrachloride of combining with water of crystallisation and hydrochloric acid is distinctly marked in its property, with which we are already acquainted, of giving precipitates with the salts of potassium, ammonium, rubidium, &c. In general it _readily forms double salts_, R_{2}PtCl_{6} = PtCl_{4} + 2RCl, where R is a univalent metal such as potassium or NH_{4}. Hence the addition of a solution of potassium or ammonium chloride to a solution of platinic chloride is followed by the formation of a yellow precipitate, which is sparingly soluble in water and almost entirely insoluble in alcohol and ether (platinic chloride is soluble in alcohol, potassium iridiochloride, IrK_{3}Cl_{6}, _i.e._ a compound of IrCl_{3}, is soluble in water but not in alcohol). It is especially remarkable in this case, that the potassium compounds here, as in a number of other instances, separate in an anhydrous form, whilst the sodium compounds, which are soluble in water and alcohol, form red crystals containing water. The composition Na_{2}PtCl_{6},6H_{2}O exactly corresponds with the above-mentioned hydrochloric compound. The compounds with barium, BaPtCl_{6},4H_{2}O, strontium, SrPtCl_{6},8H_{2}O, calcium, magnesium, iron, manganese, and many other metals are all soluble in water.[8] [7 bis] PtCl_{4} is also formed by the action of a mixture of HCl vapour and air, and by the action of gaseous chlorine upon platinum. [7 tri] Pigeon (1891) obtained fine yellow crystals of PtH_{2}Cl_{6},4H_{2}O by adding strong sulphuric acid to a strong solution of PtH_{2}Cl_{6},6H_{2}O. If crystals of H_{2}PtCl_{6},6H_{2}O be melted in vacuo (60°) in the presence of anhydrous potash, a red-brown solid hydrate is obtained containing less water and HCl, which parts with the remainder at 200°, leaving anhydrous PtCl_{4}. The latter does not disengage chlorine before 220°, and is perfectly soluble in water. [8] Nilson (1877), who investigated the platinochlorides of various metals subsequently to Bonsdorff, Topsöe, Clève, Marignac, and others, found that univalent and bivalent metals--such as hydrogen, potassium, ammonium ... beryllium, calcium, barium--give compounds of such a composition that there is always twice as much chlorine in the platinic chloride as in the combined metallic chloride; for example, K_{2}Cl_{2},PtCl_{4}; BeCl_{2},PtCl_{4},8H_{2}O, &c. Such trivalent metals as aluminium, iron (ferric), chromium, didymium, cerium (cerous) form compounds of the type RCl_{3}PtCl_{4}, in which the amounts of chlorine are in the ratio 3:4. Only indium and yttrium give salts of a different composition--namely, 2InCl_{3},5PtCl_{4},36H_{2}O and 4YCl_{3},5PtCl_{4},51H_{2}O. Such quadrivalent metals as thorium, tin, zirconium give compounds of the type RCl_{4},PtCl_{4}, in which the ratio of the chlorine is 1:1. In this manner the valency of a metal may, to a certain extent, be judged from the composition of the double salts formed with platinic chloride. Platinic bromide, PtBr_{4}, and iodide, PtI_{4}, are analogous to the tetrachloride, but the iodide is decomposed still more easily than the chloride. If sulphuric acid be added to platinic chloride, and the solution evaporated, it forms a black porous mass like charcoal, which deliquesces in the air, and has the composition Pt(SO_{4})_{2}. But this, the only oxygen salt of the type PtX_{4}, is exceedingly unstable. This is due to the fact that _platinum oxide_, the oxide of the type PtO_{2}, has a feeble acid character. This is shown in a number of instances. Thus if a strong solution of platinic chloride treated with sodium carbonate be exposed to the action of light or evaporated to dryness and then washed with water, a sodium platinate, Pt_{3}Na_{2}O_{7},6H_{2}O, remains. The composition of this salt, if we regard it in the same sense as we did the salts of silicic, titanic, molybdic and other acids, will be PtO(ONa)_{2},2PtO_{2},6H_{2}O--that is, the same type is repeated as we saw in the crystalline compounds of platinum tetrachloride with sodium chloride, or with hydrochloric acid--namely, the type PtX_{4}8Y, where Y is the molecule H_{2}O,HCl, &c. Similar compounds are also obtained with other alkalis. They will be platinates of the alkalis in which the platinic oxide, PtO_{2}, plays the part of an acid oxide. Rousseau (1889) obtained different grades of combination BaOPtO_{2}, 3(BaO)2PtO_{2}, &c., by igniting a mixture of PtCl_{4} and caustic baryta. If such an alkaline compound of platinum be treated with acetic acid, the alkali combines with the latter, and a _platinic hydroxide_, Pt(OH)_{4}, remains as a brown mass, which loses water and oxygen when ignited, and in so doing decomposes with a slight explosion. When slightly ignited this hydroxide first loses water and gives the very unstable oxide PtO_{2}. Platinic sulphide, PtS_{2}, belongs to the same type; it is precipitated by the action of sulphuretted hydrogen on a solution of platinum tetrachloride. The moist precipitate is capable of attracting oxygen, and is then converted into the sulphate above mentioned, which is soluble in water. This absorption of oxygen and conversion into sulphate is another illustration of the basic nature of PtO_{2}, so that it clearly exhibits both basic and acid properties. The latter appear, for instance, in the fact that platinic sulphide, PtS_{2}, gives crystalline compounds with the alkali sulphides. _Platinous chloride_, PtCl_{2}, is formed when hydrogen platinochloride, PtH_{2}Cl_{6}, is ignited at 300°, or when potassium is heated at 230° in a stream of chlorine. The undecomposed tetrachloride is extracted from the residue by washing it with water, and a greenish-grey or brown insoluble mass of the dichloride (sp. gr. 5·9) is then obtained. It is soluble in hydrochloric acid, giving an acid solution of the composition PtCl_{2},2HCl, corresponding with the type of double salts PtR_{2}Cl_{4}. Although platinous chloride decomposes below 500°, still it is formed to a small extent at higher temperatures. Troost and Hautefeuille, and Seelheim observed that when platinum was strongly ignited in a stream of chlorine, the metal, as it were, slowly volatilised and was deposited in crystals; a volatile chloride, probably platinous chloride, was evidently formed in this case, and decomposed subsequently to its formation, depositing crystals of platinum. The properties of platinum above-described are repeated more or less distinctly, or sometimes with certain modifications, in the above-mentioned associates and analogues of this metal. Thus although palladium forms PdCl_{4}, this form passes into PdCl_{2} with extreme ease.[9] Whilst rhodium and iridium in dissolving in aqua regia also form RhCl_{4} and IrCl_{4}, but they pass into RhCl_{3} and IrCl_{3}[9 bis] very easily when heated or when acted upon by substances capable of taking up chlorine (even alkalis, which form bleaching salts). Among the platinum metals, ruthenium and osmium have the most acid character, and although they give RuCl_{4} and OsCl_{4} they are easily oxidised to RuO_{4}, and OsO_{4} by the action of chlorine in the presence of water; the latter are volatile and may be distilled with the water and hydrochloric acid, from a solution containing other platinum metals.[9 tri] Thus with respect to the types of combination, all the platinum metals, under certain circumstances, give compounds of the type RX_{4}--for instance, RO_{2}, RCl_{4}, &c. But this is the highest form for only platinum and palladium. The remaining platinum metals further, _like iron, give acids_ of the type RO_{3} or hydrates, H_{2}RO_{4} = RO_{2}(HO)_{2} (the type of sulphuric acid); but they, like ferric and manganic acids, are chiefly known in the form of salts of the composition K_{2}RO_{4} or K_{2}R_{2}O_{7} (like the dichromate). These salts are obtained, like the manganates and ferrates, by fusing the oxides, or even the metals themselves, with nitric, or, better still, with potassium peroxide. They are soluble in water, are easily deoxidised and do not yield the acid anhydrides under the action of acids, but break up, either (like the ferrate) forming oxygen and a basic oxide (iridium and rhodium react in this manner, as they do not give higher forms of oxidation), or passing into a lower and higher form of oxidation--that is, reacting like a manganate (or partly like nitrite or phosphite). Osmium and ruthenium react according to the latter form, as they are capable of giving _higher forms of oxidation_, OsO_{4} and RuO_{4}, and therefore their reactions of decomposition may be essentially represented by the equation: 2OsO_{3} = OsO_{2} + OsO_{4}.[10] [9] In comparing the characteristics of the platinum metals, it must be observed that palladium in its form of combination PdX_{2} gives saline compounds of considerable stability. Amongst them _palladous chloride_ is formed by the direct action of chlorine or aqua regia (not in excess or in dilute solutions) on palladium. It forms a brown solution, which gives a black insoluble precipitate of _palladous iodide_, PdI_{2}, with solutions of iodides (in this respect, as in many others, palladium resembles mercury in the mercuric compounds HgX_{2}). With a solution of mercuric cyanide it gives a yellowish white precipitate, palladous cyanide, PdC_{2}N_{2}, which is soluble in potassium cyanide, and gives other double salts, M_{2}PdC_{4}N_{4}. That portion of the platinum ore which dissolves in aqua regia and is precipitated by ammonium or potassium chloride does not contain palladium. It remains in solution, because the palladic chloride, PdCl_{4}, is decomposed and the palladous chloride formed is not precipitated by ammonium chloride; the same holds good for all the other lower chlorides of the platinum metals. Zinc (and iron) separates out all the unprecipitated platinum metals (and also copper, &c.) from the solution. The palladium is found in these platinum residues precipitated by zinc. If this mixture of metals be treated with aqua regia, all the palladium will pass into solution as palladous chloride with some platinic chloride. By this treatment the main portion of the iridium, rhodium, &c. remains almost undissolved, the platinum is separated from the mixture of palladous and platinic chlorides by a solution of ammonium chloride, and the solution of palladium is precipitated by potassium iodide or mercuric cyanide. Wilm (1881) showed that palladium may be separated from an impure solution by saturating it with ammonia; all the iron present is thus precipitated, and, after filtering, the addition of hydrochloric acid to the filtrate gives a yellow precipitate of an ammonio-palladium compound, PdCl_{2},2NH_{3}, whilst nearly all the other metals remain in solution. _Metallic palladium_ is obtained by igniting the ammonio-compound or the cyanide, PdC_{2}N_{2}. It occurs native, although rarely, and is a metal of a whiter colour than platinum, sp. gr. 11·4, melts at about 1,500°; it is much more volatile than platinum, partially oxidises on the surface when heated (Wilm obtained spongy palladium by igniting PdCl_{2},2NH_{3}, and observed that it gives PdO when ignited in oxygen, and that on further ignition this oxide forms a mixture of Pd_{2}O and Pd), and loses its absorbed oxygen on a further rise of temperature. It does not blacken or tarnish (does not absorb sulphur) in the air at the ordinary temperature, and is therefore better suited than silver for astronomical and other instruments in which fine divisions have to be engraved on a white metal, in order that the fine lines should be clearly visible. The most remarkable property of palladium, discovered by Graham, consists in its capacity for _absorbing_ a large amount of _hydrogen_. Ignited palladium absorbs as much as 940 volumes of hydrogen, or about 0·7 p.c. of its own weight, which closely approaches to the formation of the compound Pd_{3}H_{2}, and probably indicates the formation of _palladium hydride_, Pd_{2}H. This absorption also takes place at the ordinary temperature--for example, when palladium serves as an electrode at which hydrogen is evolved. In absorbing the hydrogen, the palladium does not change in appearance, and retains all its metallic properties, only its volume increases by about 10 p.c.--that is, the hydrogen pushes out and separates the atoms of the palladium from each other, and is itself compressed to 1/900 of its volume. This compression indicates a great force of chemical attraction, and is accompanied by the evolution of heat (Chapter II., Note 38). The absorption of 1 grm. of hydrogen by metallic palladium (Favre) is accompanied by the evolution of 4·2 thousand calories (for Pt 20, for Na 13, for K 10 thousand units of heat). Troost showed that the dissociation pressure of palladium hydride is inconsiderable at the ordinary temperature, but reaches the atmospheric pressure at about 140°. This subject was subsequently investigated by A. A. Cracow of St. Petersburg (1894), who showed that at first the absorption of hydrogen by the palladium proceeds like solution, according to the law of Dalton and Henry, but that towards the end it proceeds like a dissociation phenomenon in definite compounds; this forms another link between the phenomenon of solution and of the formation of definite atomic compounds. Cracow's observations for a temperature 18°, showed that the electro-conductivity and tension vary until a compound Pd_{2}H is reached, and namely, that the tension _p_ rises with the volume _v_ of hydrogen absorbed, according to the law of Dalton and Henry--for instance, for _p_ = 2·1 3·2 5·5 7·7 mm. _v_ = 14 20 34 47 The maximum tension at 18° is 9 mm. At a temperature of about 140° (in the vapour of xylene) the maximum tension is about 760 mm., and when _v_ = 10-50 vols. the tension (according to Cracow's experiments) stands at 90-450 mm.--that is, increases in proportion to the volume of hydrogen absorbed. But from the point of view of chemical mechanics it is especially important to remark that Moutier clearly showed, through palladium hydride, the similarity of the phenomena which proceed in evaporation and dissociation, which fact Henri Sainte-Claire Deville placed as a fundamental proposition in the theory of dissociation. It is possible upon the basis of the second law of the theory of heat, according to the law of the variation of the tension _p_ of evaporation with the temperature T (counted from -273°), to calculate the latent heat of evaporation L (_see_ works on physics) because 424L = T(1/_d_ - 1/D)_dp_/_dt_, where _d_ and D are the weights of cubic measures of the gas (vapour) and liquid. (Thus, for instance, for water, when _t_ = 100°, T = 373, _d_ = 0·605, D = 960, _dp_/_dt_ = 0·027 m., 13,596 = 367, L = 536, whence 424L = 227,264, and the second portion of the equation 226,144, which is sufficiently near, within the limits of experimental error, _see_ Chapter I., Note 11.) The same equation is applicable to the dissociation of Na_{2}H and K_{2}H--(Chapter XII., Note 42)--but it has only been verified in this respect for Pd_{2}H, since Moutier, by calculating the amount of heat L evolved, for _t_ = 20, according to the variation of the tension (_dp_/_dt_) obtained 4·1 thousand calories, which is very near the figure obtained experimentally by Favre (_see_ Chapter XII., Note 44). The absorbed hydrogen is easily disengaged by ignition or decreased pressure. The resultant compound does not decompose at the ordinary temperature, but when exposed to air the metal sometimes glows spontaneously, owing to the hydrogen burning at the expense of the atmospheric oxygen. The hydrogen absorbed by palladium acts towards many solutions as a reducing agent; in a word, everything here points to the formation of a definite compound and at the same time of a physically-compressed gas, and forms one of the best examples of the bond existing between chemical and physical processes, to which we have many times drawn attention. It must be again remembered that the other metals of the eighth group, even copper, are, like palladium and platinum, able to combine with hydrogen. The permeability of iron and platinum tubes to hydrogen is naturally due to the formation of similar compounds, but palladium is the most permeable. [9 bis] _Rhodium_ is generally separated, together with iridium, from the residues left after the treatment of native platinum, because the palladium is entirely separated from them, and the ruthenium is present in them in very small traces, whilst the osmium at any rate is easily separated, as we shall soon see. The mixture of rhodium and iridium which is left undissolved in dilute aqua regia is dissolved in chlorine water, or by the action of chlorine on a mixture of the metals with sodium chloride. In either case both metals pass into solution. They may be separated by many methods. In either case (if the action be aided by heat) the rhodium is obtained in the form of the chloride RhCl_{3}, and the iridium as iridious chloride, IrCl_{3}. They both form double salts with sodium chloride which are soluble in water, but the iridium salt is also partially soluble in alcohol, whilst the rhodium salt is not. A mixture of the chlorides, when treated with dilute aqua regia, gives iridic chloride, IrCl_{4}, whilst the rhodium chloride, RhCl_{3}, remains unaltered; ammonium chloride then precipitates the iridium as ammonium iridiochloride, Ir(NH_{4})2Cl_{6}, and on evaporating the rose-coloured filtrate the rhodium gives a crystalline salt, Rh(NH_{4})_{3}Cl_{6}. Rhodium and its various oxides are dissolved when fused with potassium hydrogen sulphate, and give a soluble double sulphate (whilst iridium remains unacted on); this fact is very characteristic for this metal, which offers in its properties many points of resemblance with the iron metals. When fused with potassium hydroxide and chlorate it is oxidised like iridium, but it is not afterwards soluble in water, in which respect it differs from ruthenium. This is taken advantage of for separating rhodium, ruthenium, and iridium. In any case, rhodium under ordinary conditions always gives salts of the type RX_{3}, and not of any other type; and not only halogen salts, but also oxygen salts, are known in this type, which is rare among the platinum metals. Rhodium chloride, RhCl_{3}, is known in an insoluble anhydrous and also in a soluble form (like CrX_{3} or salts of chromic oxides), in which it easily gives double salts, compounds with water of crystallisation, and forms rose-coloured solutions. In this form rhodium easily gives double salts of the two types RhM_{3}Cl_{6} and RhM_{2}Cl_{3}--for example, K_{5}RhCl_{6},3H_{2}O and K_{2}RhCl_{5},H_{2}O. Solutions of the salts (at least, the ammonium salt) of the first kind give salts of the second kind when they are boiled. If a strong solution of potash be added to a red solution of rhodium chloride and boiled, a black precipitate of the hydroxide Rh(OH)_{3} is formed; but if the solution of potash is added little by little, it gives a yellow precipitate containing more water. This yellow hydrate of rhodium oxide gives a yellow solution when it is dissolved in acids, which only becomes rose-coloured after being boiled. It is obvious a change here takes place, like the transmutations of the salts of chromic oxide. It is also a remarkable fact that the black hydroxide, like many other oxidised compounds of the platinoid metals, does not dissolve in the ordinary oxygen acids, whilst the yellow hydroxide is easily soluble and gives yellow solutions, which deposit imperfectly crystallised salts. Metallic rhodium is easily obtained by igniting its oxygen and other compounds in hydrogen, or by precipitation with zinc. It resembles platinum, and has a sp. gr. of 12·1. At the ordinary temperature it decomposes formic acid into hydrogen and carbonic anhydride, with development of heat (Deville). With the alkali sulphites, the salts of rhodium and iridium of the type RX_{3} give sparingly-soluble precipitates of double sulphites of the composition R(SO_{3}Na)_{3},H_{2}O, by means of which these metals may be separated from solution, and also may be separated from each other, for a mixture of these salts when treated with strong sulphuric acid gives a soluble iridium sulphate and leaves a red insoluble double salt of rhodium and sodium. It may be remarked that the oxides Ir_{2}O_{3} and Rh_{2}O_{3} are comparatively stable and are easily formed, and that they also form different double salts (for instance, IrCl_{3},3KCl_{3}H_{2}O, RhCl_{3},2NH_{4}Cl_{4}H_{2}O, RhCl_{3},3NH_{4}Cl1-1/2H_{2}O) and compounds like the cobaltia compounds (for instance, luteo-salts RhX_{3},6NH_{3}, roseo-salts, RhX_{3}H_{2}O_{5}NH_{3}, and purpureo-salts IrX_{3},5NH_{3}, &c.) _Iridious oxide_, Ir_{2}O_{3}, is obtained by fusing iridious chloride and its compounds with sodium carbonate, and treating the mass with water. The oxide is then left as a black powder, which, when strongly heated, is decomposed into iridium and oxygen; it is easily reduced, and is insoluble in acids, which indicates the feeble basic character of this oxide, in many respects resembling such oxides as cobaltic oxide, ceric or lead dioxide, &c. It does not dissolve when fused with potassium hydrogen sulphate. Rhodium oxide, Rh_{2}O_{3}, is a far more energetic base. It dissolves when fused with potassium hydrogen sulphate. From what has been said respecting the separation of platinum and rhodium it will be understood how the compounds of _iridium_, which is the main associate of platinum, are obtained. In describing the treatment of osmiridium we shall again have an opportunity of learning the method of extraction of the compounds of this metal, which has in recent times found a technical application in the form of its oxide, Ir_{2}O_{3}; this is obtained from many of the compounds of iridium by ignition with water, is easily reduced by hydrogen, and is insoluble in acids. It is used in painting on china, for giving a black colour. Iridium itself is more difficultly fusible than platinum, and when fused it does not decompose acids or even aqua regia; it is extremely hard, and is not malleable; its sp. gr. is 22·4. In the form of powder it dissolves in aqua regia, and is even partially oxidised when heated in air, sets fire to hydrogen, and, in a word, closely resembles platinum. Heated in an excess of chlorine it gives iridic chloride, IrCl_{4}, but this loses chlorine at 50°; it is, however, more stable in the form of double salts, which have a characteristic _black_ colour--for instance, Ir(NH_{4})_{2}Cl_{6}--but they give iridious chloride, IrCl_{3}, when treated with sulphuric acid. [9 tri] We have yet to become acquainted with the two remaining associates of platinum--ruthenium and osmium--whose most important property is that they are oxidised even when heated in air, and that they are able to give _volatile_ oxides of the form RuO_{4} and OsO_{4}; these have a powerful odour (like iodine and nitrous anhydride). Both these higher oxides are solids; they volatilise with great ease at 100°; the former is yellow and the latter white. They are known as _ruthenic_ and _osmic anhydrides_, although their aqueous solutions (they both slowly dissolve in water) do not show an acid reaction, and although they do not even expel carbonic anhydride from potassium carbonate, do not give crystalline salts with bases, and their alkaline solutions partially deposit them again when boiled (an excess of water decomposes the salts). The formulæ OsO_{4} and RuO_{4} correspond with the vapour density of these oxides. Thus Deville found the vapour density of osmic anhydride to be 128 (by the formula 127·5) referred to hydrogen. Tennant and Vauquelin discovered this compound, and Berzelius, Wöhler, Fritzsche, Struvé, Deville, Claus, Joly, and others helped in its investigation; nevertheless there are still many questions concerning it which remain unsolved. It should be observed that RO_{4} is the highest known form for an oxygen compound, and RH_{4} is the highest known form for a compound of hydrogen; whilst the highest forms of acid hydrates contain SiH_{4}O_{4}, PH_{3}O_{4}, SH_{2}O_{4}, ClHO_{4}--all with four atoms of oxygen, and therefore in this number there is apparently the limit for the simple forms of combination of hydrogen and oxygen. In combination with _several_ atoms of an element, or several elements, there may be more than O_{4} or H_{4}, but a molecule never contains more than four atoms of either O or H to one atom of another element. Thus the simplest forms of combination of hydrogen and oxygen are exhausted by the list RH_{4}, RH_{3}, RH_{2}, RH, RO, RO_{2}, RO_{3}, RO_{4}. The extreme members are RH_{4} and RO_{4}, and are only met with for such elements as carbon, silicon, osmium, ruthenium, which also give RCl_{4} with chlorine. In these extreme forms, RH_{4} and RO_{4}, the compounds are the least stable (compare SiH_{4}, PH_{3}, SH_{2}, ClH, or RuO_{4}, MoO_{3}, ZrO_{2}, SrO), and easily give up part, or even all, their oxygen or hydrogen. The primary source from which the compounds of ruthenium and osmium are obtained is either _osmiridium_ (the osmium predominates, from IrOs to IrOs_{4}, sp. gr. from 16 to 21), which occurs in platinum ores (it is distinguished from the grains of platinum by its crystalline structure, hardness, and insolubility in aqua regia), or else those insoluble residues which are obtained, as we saw above, after treating platinum with aqua regia. Osmium predominates in these materials, which sometimes contain from 30 p.c. to 40 p.c. of it, and rarely more than 4 p.c. to 5 p.c. of ruthenium. The process for their treatment is as follows: they are first fused with 6 parts of zinc, and the zinc is then extracted with dilute hydrochloric acid. The osmiridium thus treated is, according to Fritzsche and Struvé's method, then added to a fused mixture of potassium hydroxide and chlorate in an iron crucible; the mass as it begins to evolve oxygen acts on the metal, and the reaction afterwards proceeds spontaneously. The dark product is treated with water, and gives a solution of osmium and ruthenium in the form of soluble salts, R_{2}OsO_{4} and R_{2}RuO_{4}, whilst the insoluble residue contains a mixture of oxides of iridium (and some osmium, rhodium, and ruthenium), and grains of metallic iridium still unacted on. According to Frémy's method the lumps of osmiridium are straightway heated to whiteness in a porcelain tube in a stream of air or oxygen, when the very volatile osmic anhydride is obtained directly, and is collected in a well-cooled receiver, whilst the ruthenium gives a crystalline sublimate of the dioxide, RuO_{2}, which is, however, very difficultly volatile (it volatilises together with osmic anhydride), and therefore remains in the cooler portions of the tube; this method does not give volatile ruthenic anhydride, and the iridium and other metals are not oxidised or give non-volatile products. This method is simple, and at once gives dry, pure osmic anhydride in the receiver, and ruthenium dioxide in the sublimate. The air which passes through the tube should be previously passed through sulphuric acid, not only in order to dry it, but also to remove the organic and reducing dust. The vapour of osmic anhydride must be powerfully cooled, and ultimately passed over caustic potash. A third mode of treatment, which is most frequently employed, was proposed by Wöhler, and consists in slightly heating (in order that the sodium chloride should not melt) an intimate mixture of osmiridium and common salt in a stream of moist chlorine. The metals then form compounds with chlorine and sodium chloride, whilst the osmium forms the chloride, OsCl_{4}, which reacts with the moisture, and gives osmic anhydride, which is condensed. The ruthenium in this, as in the other processes, does not directly give ruthenic anhydride, but is always extracted as the soluble ruthenium salt, K_{2}RuO_{4}, obtained by fusion with potassium hydroxide and chlorate or nitrate. When the orange-coloured ruthenate, K_{2}RuO_{4}, is mixed with acids, the liberated ruthenic acid immediately decomposes into the volatile ruthenic anhydride and the insoluble ruthenic oxide: 2K_{2}RuO_{4} + 4HNO_{3} = RuO_{4} + RuO_{2},2H_{2}O + 4KNO_{3}. When once one of the above compounds of ruthenium or osmium is procured it is easy to obtain all the remaining compounds, and by reduction (by metals, hydrogen, formic acid, &c.) the metals themselves. Osmic anhydride, OsO_{4}, is very easily deoxidised by many methods. It blackens organic substances, owing to reduction, and is therefore used in investigating vegetable and animal, and especially nerve, preparations under the microscope. Although osmic anhydride may be distilled in hydrogen, still complete reduction is accomplished when a mixture of hydrogen and osmic anhydride is slightly ignited (just before it inflames). If osmium be placed in the flame it is oxidised, and gives vapours of osmic anhydride, which become reduced, and the flame gives a brilliant light. Osmic anhydride deflagrates like nitre on red-hot charcoal; zinc, and even mercury and silver, reduce osmic anhydride from its aqueous solutions into the lower oxides or metal; such reducing agents as hydrogen sulphide, ferrous sulphate, or sulphurous anhydride, alcohol, &c., act in the same manner with great ease. The lower oxides of osmium, ruthenium, and of the other elements of the platinum series are not volatile, and it is noteworthy that the other elements behave differently. On comparing SO_{2}, SO_{3}; As_{2}O_{3}, As_{2}O_{5}; P_{2}O_{3}, P_{2}O_{5}; CO, CO_{2}, &c., we observe a converse phenomenon; the higher oxides are less volatile than the lower. In the case of osmium all the oxides, with the exception of the highest, are non-volatile, and it may therefore be thought that this higher form is more simply constituted than the lower. It is possible that osmic oxide, OsO_{2}, stands in the same relation to the anhydride as C_{2}H_{4} to CH_{4}--_i.e._ the lower oxide is perhaps Os_{2}O_{4}, or is still more polymerised, which would explain why the lower oxides, having a greater molecular weight, are less volatile than the higher oxides, just as we saw in the case of the nitrogen oxides, N_{2}O and NO. _Ruthenium and osmium_, obtained by the ignition or reduction of their compounds in the form of powder, have a density considerably less than in the fused form, and differ in this condition in their capacity for reaction; they are much more difficultly fused than platinum and iridium, although ruthenium is more fusible than osmium. Ruthenium in powder has a specific gravity of 8·5, the fused metal of 12·2; osmium in powder has a specific gravity of 20·0, and when semi-fused--or, more strictly speaking, agglomerated--in the oxyhydrogen flame, of 21·4, and fused 22·5. The powder of slightly-heated osmium oxidises very easily in the air, and when ignited burns like tinder, directly forming the odoriferous osmic anhydride (hence its name, from the Greek word signifying odour); ruthenium also oxidises when heated in air, but with more difficulty, forming the oxide RuO_{2}. The oxides of the types RO, R_{2}O_{3}, and RO_{2} (and their hydrates) obtained by reduction from the higher oxides, and also from the chlorides, are analogous to those given by the other platinum metals, in which respect osmium and ruthenium closely resemble them. We may also remark that ruthenium has been found in the platinum deposits of Borneo in the form of _laurite_, Ru_{2}S_{3}, in grey octahedra of sp. gr. 7·0. For osmium, Moraht and Wischin (1893) obtained free osmic acid, H_{2}OsO_{4}, by decomposing K_{2}OsO_{4} with water, and precipitating with alcohol in a current of hydrogen (because in air volatile OsO_{4} is formed); with H_{2}S, osmic acid gives OsO_{3}(HS)_{2} at the ordinary temperature. Debray and Joly showed that ruthenic anhydride, RuO_{4}, fuses at 25°, boils at 100°, and evolves oxygen when dissolved in potash, forming the salt KRuO_{4} (not isomorphous with potassium permanganate). Joly (1891), who studied the ruthenium compounds in greater detail, showed that the easily-formed KRuO_{4} gives RuKO_{4}RuO_{3} when ignited, but it resembles KMnO_{4} in many respects. In general, Ru has much in common with Mn. Joly (1889) also showed that if KNO_{3} be added to a solution of RuCl_{3} containing HCl, the solution becomes hot, and a salt, RuCl_{3}NO_{2}KCl, is formed, which enters into double decomposition and is very stable. Moreover, if RuCl_{3} be treated with an excess of nitric acid, it forms a salt, RuCl_{3}NOH_{2}O, after being heated (to boiling) and the addition of HCl. The vapour density of RuO_{4}, determined by Debray and Joly, corresponds to that formula. [10] Although palladium gives the same types of combination (with chlorine) as platinum, its reduction to RX_{2} is incomparably easier than that of platinic chloride, and in the case of iridium it is also very easy. Iridic chloride, IrCl_{4}, acts as an oxidising agent, readily parts with a fourth of its chlorine to a number of substances, readily evolves chlorine when heated, and it is only at low temperatures that chlorine and aqua regia convert iridium into iridic chloride. In disengaging chlorine iridium more often and easily gives the very stable iridious chloride, IrCl_{3} (perhaps this substance is Ir_{2}Cl_{6} = IrCl_{2},IrCl_{4}, insoluble in water, but soluble in potassium chloride, because it forms the double salt K_{3}IrCl_{6}), than the dichloride, IrCl_2. This compound, corresponding to IrX_{2}, is very stable, and corresponds with the _basic oxide_, Ir_{2}O_{3}, resembling the oxides Fe_{2}O_{3}, Co_{2}O_{3}. To this form there correspond ammoniacal compounds similar to those given by cobaltic oxide. Although iridium also gives an acid in the form of the salt K_{2}Ir_{2}O_{7}, it does not, like iron (and chromium), form the corresponding chloride, IrCl_{6}. In general, in this as in the other elements, it is impossible to predict the chlorine compounds from those of oxygen. Just as there is no chloride SCl_{6}, but only SCl_{2}, so also, although IrO_{3} exists, IrCl_{6} is wanting, the only chloride being IrCl_{4}, and this is unstable, like SCl_{2}, and easily parts with its chlorine. In this respect rhodium is very much like iridium (as platinum is like palladium). For RhCl_{4} decomposes with extreme ease, whilst rhodium chloride, RhCl_{3}, is very stable, like many of the salts of the type RhX_{3}, although like the platinum elements these salts are easily reduced to metal by the action of heat and powerful reagents. There is as close a resemblance between osmium and ruthenium. Osmium when submitted to the action of dry chlorine gives osmic chloride, OsCl_{4}, but the latter is converted by water (as is osmium by moist chlorine) into osmic anhydride, although the greater portion is then decomposed into Os(HO)_{4} and 4HCl, like a chloranhydride of an acid. In general this acid character is more developed in osmium than in platinum and iridium. Having parted with chlorine, osmic chloride, OsCl_{4}, gives the unstable trichloride, OsCl_{3}, and the stable soluble dichloride, OsCl_{2}, which corresponds with platinous chloride in its properties and reactions. The relation of ruthenium to the halogens is of the same nature. Platinum and its analogues, like iron and its analogues, are able to form complex and comparatively stable cyanogen and ammonia compounds, corresponding with the ferrocyanides and the ammoniacal compounds of cobalt, which we have already considered in the preceding chapter. If platinous chloride, PtCl_{2} (insoluble in water), be added by degrees to a solution of potassium cyanide, it is completely dissolved (like silver chloride), and on evaporating the solution deposits rhombic prisms of _potassium platinocyanide_, PtK_{2}(CN)_{4},3H_{2}O. This salt, like all those corresponding with it, has a remarkable play of colours, due to the phenomena of dichromism, and even polychromism, natural to all the platinocyanides. Thus it is yellow and reflects a bright blue light. It is easily soluble in water, effloresces in air, then turns red, and at 100° orange, when it loses all its water. The loss of water does not destroy its stability--that is, it still remains unchanged, and its stability is further shown by the fact that it is formed when potassium ferrocyanide, K_{4}Fe(CN)_{6}, is heated with platinum black. This salt, first obtained by Gmelin, shows a neutral reaction with litmus; it is exceedingly stable under the action of air, like potassium ferrocyanide, which it resembles in many respects. Thus the platinum in it cannot be detected by reagents such as sulphuretted hydrogen; the potassium may be replaced by other metals by the action of their salts, so that it corresponds with a whole series of compounds, R_{2}Pt(CN)_{4}, and it is stable, although the potassium cyanide and platinous salts, of which it is composed, individually easily undergo change. When treated with oxidising agents it passes, like the ferrocyanide, into a higher form of combination of platinum. If salts of silver be added to its solution, it gives a heavy white precipitate of silver platinocyanide, PtAg_{2}(CN)_{4}, which when suspended in water and treated with sulphuretted hydrogen, enters into double decomposition with the latter and forms insoluble silver sulphide, Ag_{2}S, and soluble _hydroplatinocyanic acid_, H_{2}Pt(CN)_{4}. If potassium platinocyanide be mixed with an equivalent quantity of sulphuric acid, the hydroplatinocyanic acid liberated may be extracted by a mixture of alcohol and ether. The ethereal solution, when evaporated in a desiccator, deposits bright red crystals of the composition PtH_{2}(CN)_{4},5H_{2}O. This acid colours litmus paper, liberates carbonic anhydride from sodium carbonate, and saturates alkalis, so that it presents an analogy to hydroferrocyanic acid.[11] [11] This acid character is explained by the influence of the platinum on the hydrogen, and by the attachment of the cyanogen groups. Thus cyanuric acid, H_{3}(CN)_{3}O_{3}, is an energetic acid compared with cyanic acid, HCNO. And the formation of a compound with five molecules of water of crystallisation, (PtH_{2}(CN)_{4},5H_{2}O), confirms the opinion that platinum is able to form compounds of still higher types than that expressed in its saline compounds, and, moreover, the combination of hydroplatinocyanic acid with water does not reach the limit of the compounds which appears in PtCl_{4},2HCl,6H_{2}O. A whole series of _platinocyanides_ of the common type PtR_{2}(CN)_{4}_n_H_{2}O is obtained by means of double decomposition with the potassium or hydrogen or silver salts. For example, the salts of sodium and lithium contain, like the potassium salt, three molecules of water. The sodium salt is soluble in water and alcohol. The ammonium salt has the composition Pt(NH_{4})_{2}(CN)_{4},2H_{2}O and gives crystals which reflect blue and rose-coloured light. This ammonium salt decomposes at 300°, with evolution of water and ammonium cyanide, leaving a greenish _platinum dicyanide_, Pt(CN)_{2}, which is insoluble in water and acid but dissolves in potassium cyanide, hydrocyanic acid, and other cyanides. The same platinous cyanide is obtained by the action of sulphuric acid on the potassium salts in the form of a reddish-brown amorphous precipitate. The most characteristic of the platinocyanides are those of the alkaline earths. The magnesium salt PtMg(CN)_{4},7H_{2}O crystallises in regular prisms, whose side faces are of a metallic green colour and terminal planes dark blue. It shows a carmine-red colour along the main axis, and dark red along the lateral axes; it easily loses water, (2H_{2}O), at 40°, and then turns blue (it then contains 5H_{2}O, which is frequently the case with the platinocyanides). Its aqueous solution is colourless, and an alcoholic solution deposits yellow crystals. The remainder of the water is given off at 230°. It is obtained by saturating platinocyanic acid with magnesia, or else by double decomposition between the barium salt and magnesium sulphate. The strontium salt, SrPt(CN)_{4},4H_{2}O crystallises in milk-white plates having a violet and green iridescence. When it effloresces in a desiccator, its surfaces have a violet and metallic green iridescence. A colourless solution of the barium salt PtBa(CN)_{4},4H_{2}O is obtained by saturating a solution of hydroplatinocyanic acid with baryta, or by boiling the insoluble copper platinocyanide in baryta water. It crystallises in monoclinic prisms of a yellow colour, with blue and green iridescence; it loses half its water at 100°, and the whole at 150°. The ethyl salt, Pt(C_{2}H_{5})_{2}(CN)_{4},2H_{2}0, is also very characteristic; its crystals are isomorphous with those of the potassium salt, and are obtained by passing hydrochloric acid into an alcoholic solution of hydroplatinocyanic acid. The facility with which they crystallise, the regularity of their forms, and their remarkable play of colours, renders the preparation of the platinocyanides one of the most attractive lessons of the laboratory. By the action of chlorine or dilute nitric acid, the platinocyanides are converted into salts of the composition PtM_{2}(CN)_{5}, which corresponds with Pt(CN)_{3},2KCN--that is, they express the type of a non-existent form of oxidation of platinum, PtX_{3} (_i.e._ oxide Pt_{2}O_{3}), just as potassium ferricyanide (FeCy_{3},3KCy) corresponds with ferric oxide, and the ferrocyanide corresponds with the ferrous oxide. The potassium salt of this series contains PtK_{2}(CN)_{5},3H_{2}O, and forms brown regular prisms with a metallic lustre, and is soluble in water but insoluble in alcohol. Alkalis re-convert this compound into the ordinary platinocyanide K_{2}Pt(CN)_{4}, taking up the excess of cyanogen. It is remarkable that the salts of the type PtM_{2}Cy_{5} contain the same amount of water of crystallisation as those of the type PtM_{2}Cy_{4}. Thus the salts of potassium and lithium contain three, and the salt of magnesium seven, molecules of water, like the corresponding salts of the type of platinous oxide. Moreover, neither platinum nor any of its associates gives any cyanogen compound corresponding with the oxide, _i.e._ having the composition PtK_{2}Cy_{6}, just as there are no compounds higher than those which correspond to RCy_{3}_n_MCy_{3} for cobalt or iron. This would appear to indicate the absence of any such cyanides, and indeed, for no element are there yet known any poly-cyanides containing more than three equivalents of cyanogen for one equivalent of the element. The phenomenon is perhaps connected with the faculty of cyanogen of giving tricyanogen polymerides, such as cyanuric acid, solid cyanogen chloride, &c. Under the action of an excess of chlorine, a solution of PtK_{2}(CN)_{4} gives (besides PtK_{2}Cy_{5}) a product PtK_{2}Cy_{4}Cl_{2}, which evidently contains the form PtX_{4}, but at first the action of the chlorine (or the electrolysis of, or addition of dilute peroxide of hydrogen to, a solution of PtK_{2}Cy_{4}, acidulated with hydrochloric acid) produces an easily soluble intermediate salt which crystallises in thin copper-red needles (Wilm, Hadow, 1889). It only contains a small amount of chlorine, and apparently corresponds to a compound 5PtK_{2}Cy_{4} + PtK_{2}Cy_{4}Cl_{2} + 24H_{2}O. Under the action of an excess of ammonia both these chlorine products are converted either completely or in part (according to Wilm ammonia does not act upon PtK_{2}Cy_{4}) into PtCy_{2},2NH_{3}, _i.e._ a platino-ammonia compound (_see_ further on). It is also necessary to pay attention to the fact that ruthenium and osmium--which, as we know, give higher forms of oxidation than platinum--are also able to combine with a larger proportion of potassium cyanide (but not of cyanogen) than platinum. Thus ruthenium forms a crystalline _hydroruthenocyanic acid_, RuH_{4}(CN)_{6}, which is soluble in water and alcohol, and corresponds with the salts M_{4}Ru(CN)_{6}. There are exactly similar osmic compounds--for example, K_{4}Os(CN)_{6},3H_{2}O. The latter is obtained in the form of colourless, sparingly-soluble regular tablets on evaporating the solution obtained from a fused mixture of potassium osmiochloride, K_{2}OsCl_{6}, and potassium cyanide. These osmic and ruthenic compounds fully correspond with potassium ferrocyanide, K_{4}Fe(CN)_{6},3H_{2}O, not only in their composition but also in their crystalline form and reactions, which again demonstrates the close analogy between iron, ruthenium, and osmium, which we have shown by giving these three elements a similar position (in the eighth group) in the periodic system. For rhodium and iridium only salts of the same type as the ferricyanides, M_{3}RCy_{6}, are known, and for palladium only of the type M_{2}PdCy_{4}, which are analogous to the platinum salts. In all these examples a _constancy of the types_ of the double cyanides is apparent. In the eighth group we have iron, cobalt, nickel, copper, and their analogues ruthenium, rhodium, palladium, silver, and also osmium, iridium, platinum, gold. The double cyanides of iron, ruthenium, osmium have the type K_{4}R(CN)_{6}; of cobalt, rhodium, iridium, the type K_{3}R(CN)_{6}; of nickel, palladium, platinum the type K_{2}R(CN)_{4} and K_{2}R(CN)_{5}; and for copper, silver, gold there are known KR(CN)_{2}, so that the presence of 4, 3, 2, and 1 atoms of potassium corresponds with the order of the elements in the periodic system. Those types which we have seen in the ferrocyanides and ferricyanides of iron repeat themselves in all the platinoid metals, and this naturally leads to the conclusion that the formation of similar so-called double salts is of exactly the same nature as that of the ordinary salts. If, in expressing the union of the elements in the oxygen salts, the existence of an _aqueous residue_ (hydroxyl group) be admitted, in which the hydrogen is replaced by a metal, we have then only to apply this mode of expression to the double salts and the analogy will be obvious, if only we remember that Cl_{2}, (CN)_{2}, SO_{4}, &c., are equivalent to O, as we see in RO, RCl_{2}, RSO_{4}, &c. They all = X_{2}, and, therefore, in point of fact, wherever X (= Cl or OH, &c.) can be placed, there (Cl_{2}H), (SO_{4}H), &c., can also stand. And as Cl_{2}H = Cl + HCl and SO_{4}H = OH + SO_{3}, &c., it follows that molecules HCl or SO_{3}, or, in general, whole molecules--for instance, NH_{3}, H_{2}O, salts, &c., can annex themselves to a compound containing X. (This is an indirect consequence of the law of substitution which explains the origin of double salts, ammonia compounds, compounds with water of crystallisation, &c., by one general method.) Thus the double salt MgSO_{4},K_{2}SO_{4}, according to this reasoning, _may be_ considered as a substance of the same type as MgCl_{2}, namely, as = Mg(SO_{4}K)_{2}, and the alums as derived from Al(OH)(SO_{4}), namely, as Al(SO_{4}K)(SO_{4}). Without stopping to pursue this digression further, we will apply these considerations to the type of the ferrocyanides and ferricyanides and their platinum analogues. Such a salt as K_{2}PtCy_{4} may accordingly be regarded as Pt(Cy_{2}K)_{2}, like Pt(OH)_{2}; and such a salt as PtK_{2}Cy_{5} as PtCy(Cy_{2}K)_{2}, the analogue of PtX(OH)_{2}, or AlX(OH)_{2}, and other compounds of the type RX_{3}. Potassium ferricyanide and the analogous compounds of cobalt, iridium, and rhodium, belong to the same type, with the same difference as there is between RX(OH)_{2} and R(OH)_{3}, since FeK_{3}Cy_{6} = Fe(Cy_{2}K)_{3}. Limiting myself to these considerations, which may partially elucidate the nature of double salts, I will now pass again to the complex saline compounds known for platinum. (_A_) On mixing a solution of potassium thiocyanate with a solution of potassium platinosochloride, K_{2}PtCl_{4}, they form a double thiocyanate, PtK_{2}(CNS)_{4}, which is easily soluble in water and alcohol, crystallises in red prisms, and gives an orange-coloured solution, which precipitates salts of the heavy metals. The action of sulphuric acid on the lead salt of the same type gives the acid itself, PtH_{2}(SCN)_{4}, which corresponds with these salts. The type of these compounds is evidently the same as that of the cyanides. (_B_) _Platinous chloride_, PtCl_{2}, which is insoluble in water, forms _double salts with the metallic chlorides_. These double chlorides are soluble in water, and capable of crystallising. Hence when a hydrochloric acid solution of platinous chloride is mixed with solutions of metallic salts and evaporated it forms crystalline salts of a red or yellow colour. Thus, for example, the potassium salt, PtK_{2}Cl_{4}, is red, and easily soluble in water; the sodium salt is also soluble in alcohol; the barium salt, PtBaCl_{4},3H_{2}O, is soluble in water, but the silver salt, PtAg_{2}Cl_{4}, is insoluble in water, and may be used for obtaining the remaining salts by means of double decomposition with their chlorides. (_C_) A remarkable example of the complex compounds of platinum was observed by Schützenberger (1868). He showed that finely-divided platinum in the presence of chlorine and carbonic oxide at 250°-300° gives phosgene and a volatile compound containing platinum. The same substance is formed by the action of carbonic oxide on platinous chloride. It decomposes with an explosion in contact with water. Carbon tetrachloride dissolves a portion of this substance, and on evaporation gives crystals of 2PtCl_{2},3CO, whilst the compound PtCl_{2},2CO remains undissolved. When fused and sublimed it gives yellow needles of PtCl_{2},CO, and in the presence of an excess of carbonic oxide PtCl_{2},2CO is formed. These compounds are fusible (the first at 250°, the second at 142°, and the third at 195°). In this case (as in the double cyanides) combination takes place, because both carbonic oxide and platinous chloride are unsaturated compounds capable of further combination. The carbon tetrachloride solution absorbs NH_{3} and gives PtCl_{2},CO,2NH_{3}, and PtCl_{2},2CO,2NH_{3}, and these substances are analogous (Foerster, Zeisel, Jörgensen) to similar compounds containing complex amines (for instance, pyridine, C_{5}H_{5}N), instead of NH_{3}, and ethylene, &c., instead of CO, so that here we have a whole series of complex platino-compounds. The compound PtCl_{2}CO dissolves in hydrochloric acid without change, and the solution disengages all the carbonic oxide when KCN is added to it, which shows that those forces which bind 2 molecules of KCN to PtCl_{2} can also bind the molecule CO, or 2 molecules of CO. When the hydrochloric acid solution of PtCl_{2}CO is mixed with a solution of sodium acetate or acetic acid, it gives a precipitate of PtOCO, _i.e._ the Cl_{2} is replaced by oxygen (probably because the acetate is decomposed by water). This oxide, PtOCO, splits up into Pt + CO_{2} at 350°. PtSCO is obtained by the action of sulphuretted hydrogen upon PtCl_{2}CO. All this leads to the conclusion that the group PtCO is able to assimilate X_{2} = Cl_{2}, S, O, &c. (Mylius, Foerster, 1891). Pullinger (1891), by igniting spongy platinum at 250°, first in a stream of chlorine, and then in a stream of carbonic oxide, obtained (besides volatile products) a non-volatile yellow substance which remained unchanged in air and disengaged chlorine and phosgene gas when ignited; its composition was PtCl_{6}(CO)_{2}, which apparently proves it to be a compound of PtCl_{2} and 2COCl_{2}, as PtCl_{2} is able to combine with oxychlorides, and forms somewhat stable compounds. (_D_) The faculty of platinous chloride for forming stable compounds with divers substances shows itself in the formation of the compound PtCl_{2},PCl_{3} by the action of phosphorus pentachloride at 250° on platinum powder (Pd reacts in a similar manner, according to Fink, 1892). The product contains both phosphorus pentachloride and platinum, whilst the presence of PtCl_{2} is shown in the fact that the action of water produces _chlorplatino-phosphorous acid_, PtCl_{2}P(OH)_{3}. (_E_) After the cyanides, the _double salts_ of platinum _formed by sulphurous acid_ are most distinguished for their stability and characteristic properties. This is all the more instructive, as sulphurous acid is only feebly energetic, and, moreover, in these, as in all its compounds, it exhibits a dual reaction. The salts of sulphurous acid, R_{2}SO_{3}, either react as salts of a feeble bibasic acid, where the group SO_{3} presents itself as bivalent, and consequently equal to X_{2}, or else they react after the manner of salts of a monobasic acid containing the same residue, RSO_{3}, as occurs in the salts of sulphuric acid. In sulphurous acid this residue is combined with hydrogen, H(SO_{3}H), whilst in sulphuric acid it is united with the aqueous residue (hydroxyl), OH(SO_{3}H). These two forms of action of the sulphites appear in their reactions with the platinum salts--that is to say, salts of both kinds are formed, and they both correspond with the type PtH_{2}X_{4}. The one series of salts contain PtH_{2}(SO_{3})_{2}, and their reactions are due to the bivalent residue of sulphurous acid, which replaces X_{2}. The others, which have the composition PtR_{2}(SO_{3}H)_{4}, contain sulphoxyl. The latter salts will evidently react like acids; they are formed simultaneously with the salts of the first kind, and pass into them. These salts are obtained either by directly dissolving platinous oxide in water containing sulphurous acid, or by passing sulphurous anhydride into a solution of platinous chloride in hydrochloric acid. If a solution of platinous chloride or platinous oxide in sulphurous acid be saturated with sodium carbonate, it forms a white, sparingly soluble precipitate containing PtNa_{2}(SO_{3}Na)_{4},7H_{2}O. If this precipitate be dissolved in a small quantity of hydrochloric acid and left to evaporate at the ordinary temperature, it deposits a salt of the other type, PtNa_{2}(SO_{3})_{2},H_{2}O, in the form of a yellow powder, which is sparingly soluble in water. The potassium salt analogous to the first salt, PtK_{2}(SO_{3}K)_{4},2H_{2}O, is precipitated by passing sulphurous anhydride into a solution of potassium sulphite in which platinous oxide is suspended. A similar salt is known for ammonium, and with hydrochloric acid it gives a salt of the second kind, Pt(NH_{4})_{2}(SO_{3})_{2},H_{2}O. If ammonio-chloride of platinum be added to an aqueous solution of sulphurous anhydride, it is first deoxidised, and chlorine is evolved, forming a salt of the type PtX_{2}; a double decomposition then takes place with the ammonium sulphite, and a salt of the composition Pt(NH_{4})_{2}Cl_{3}(SO_{3}H) is formed (in a desiccator). The acid character of this substance is explained by the fact that it contains the elements SO_{3}H--sulphoxyl, with the hydrogen not yet displaced by a metal. On saturating a solution of this acid with potassium carbonate it gives orange-coloured crystals of a potassium salt of the composition Pt(NH_{4})_{2}Cl_{3}(SO_{3}K). Here it is evident that an equivalent of chlorine in Pt(NH_{4})_{2})Cl_{4} is replaced by the univalent residue of sulphurous acid. Among these salts, that of the composition Pt(NH_{4})_{2})Cl_{2}(SO_{3}H)_{2},H_{2}O is very readily formed, and crystallises in well-formed colourless crystals; it is obtained by dissolving ammonium platinosochloride, Pt(NH_{4})_{2}Cl_{4}, in an aqueous solution of sulphurous acid. The difficulty with which sulphurous anhydride and platinum are separated from these salts indicates the same basic character in these compounds as is seen in the double cyanides of platinum. In their passage into a complex salt, the metal platinum and the group SO_{2} modify their relations (compared with those of PtX_{2} or SO_{2}X_{2}), just as the chlorine in the salts KClO, KClO_{3}, and KClO_{4} is modified in its relations as compared with hydrochloric acid or potassium chloride. (_F_) No less characteristic are the _platinonitrites_ formed by platinous oxide. They correspond with nitrous acid, whose salts, RNO_{2}, contain the univalent radicle, NO_{2}, which is capable of replacing chlorine, and therefore the salts of this kind should form a common type PtR_{2}(NO_{2})_{4}, and such a salt of potassium has actually been obtained by mixing a solution of potassium platinosochloride with a solution of potassium nitrite, when the liquid becomes colourless, especially if it be heated, which indicates the change in the chemical distribution of the elements. As the liquid decolorises it gradually deposits sparingly soluble, colourless prisms of the potassium salt K_{2}Pt(NO_{2})_{4}, which does not contain any water. With silver nitrate a solution of this salt gives a precipitate of silver platinonitrite, PtAg_{2}(NO_{2})_{4}. The silver of this salt may be replaced by other metals by means of double decomposition with metallic chlorides. The sparingly soluble barium salt, when treated with an equivalent quantity of sulphuric acid, gives a soluble acid, which separates, under the receiver of an air-pump, in red crystals; this acid has the composition PtH_{2}(NO_{2})_{4}. To the potassium salt, K_{2}Pt(NO_{2})_{4}, there correspond (Vèzes, 1892) K_{2}Pt(NO_{2})_{4}Br_{2} and K_{2}Pt(NO_{2})_{4}Cl_{2} and other compounds of the same type K_{2}PtX_{6}, where X is partly replaced by Cl or Br and partly by (NO_{2}), showing a transition towards the type of the double salts like the platino-ammoniacal salts. (The corresponding double sodium nitrite salt of cobalt is soluble in water, while the K,NH_{4} and many other salts are insoluble in water, as I was informed by Prof. K. Winkler in 1894). In all the preceding complex compounds of Pt we see a common type PtX_{2},2MX (_i.e._ of double salts corresponding to PtO) or PtM_{2}X_{4} = Pt(MX_{2})_{2}, corresponding to Pt(HO)_{2} with the replacement of O by its equivalent X_{2}. Two other facts must also be noted. In the first place these X's generally correspond to elements (like chlorine) or groups (like CN, NO_{2}, SO_{3}, &c.), which are capable of further combination. In the second place all the compounds of the type PtM_{2}X_{4} are capable of combining with chlorine or similar elements, and thus passing into compounds of the types PtX_{3} or PtX_{4}. Ammonia, like potassium cyanide, has the faculty of easily reacting with platinum dichloride, forming compounds similar to the platinocyanide and cobaltia compounds, which are comparatively stable. But as ammonia does not contain any hydrogen easily replaceable by metals, and as ammonia itself is able to combine with acids, the PtX_{2} plays, as it were, the part of an acid with reference to the ammonia. Owing to the influence of the ammonia, the X_{2} in the resultant compound will represent the same character as it has in ammoniacal salts; consequently, the ammoniacal compounds produced from PtX_{2} will be salts in which X will be replaceable by various other haloids, just as the metal is replaced in the cyanogen salts; such is the nature of the _platino-ammonium compounds_. PtX_{2} forms compounds with 2NH_{3} and with 4NH_{3}, and so also PtX_{4} gives (not directly from PtX_{4} and ammonia, but from the compounds of PtX_{2} by the action of chlorine, &c.) similar compounds with 2NH_{3} and with 4NH_{3}.[12] [12] The platinum salt and ammonia, when once combined together, are no longer subject to their ordinary reactions but form compounds which are comparatively very stable. The question at once suggests itself to all who are acquainted with these phenomena, as to what is the relation of the elements contained in these compounds. The first explanation is that these compounds are salts of ammonium in which the hydrogen is partially replaced by platinum. This is the view, with certain shades of difference, held by many respecting the platino-ammonium compounds. They were regarded in this light by Gerhardt, Schiff, Kolbe, Weltzien, and many others. If we suppose the hydrogen in 2NH_{4}X to be replaced by bivalent platinum (as in the salts PtX_{2}), we shall obtain NH_{3} X Pt NH_{3} X --that is, the compound PtX_{2},2NH_{3}. The compound with 4NH_{3} will then be represented by a further substitution of the hydrogen in ammonia by ammonium itself--_i.e._ as NH_{2}(NH_{4}X)_{2}Pt or PtX_{2},4NH_{3}. A modification of this view is found in that representation of compounds of this kind which is based on atomicity. As platinum in PtX_{2} is bivalent, has two affinities, and ammonia, NH_{3}, is also bivalent, because nitrogen is quinquivalent and is here only combined with H_{3}, it is evident what bonds should be represented in PtX_{2},2NH_{3} and in PtX_{2},4NH_{3}. In the former, Pt(NH_{3}Cl)_{2}, the nitrogen of each atom of ammonia is united by three affinities with H_{3}, by one with platinum, and by the fifth with chlorine. The other compound is Pt(NH_{3}.NH_{3}Cl)_{2}--that is, the N is united by one affinity with the other N, whilst the remaining bonds are the same as in the first salt. It is evident that this union or chain of ammonias has no obvious limit, and the most essential fault of such a mode of representation is that it does not indicate at all what number of ammonias are capable of being retained by platinum. Moreover, it is hardly possible to admit the bond between nitrogen and platinum in such stable compounds, for these kinds of affinities are, at all events, feeble, and cannot lead to stability, but would rather indicate explosive and easily-decomposed compounds. Moreover, it is not clear why this platinum, which is capable of giving PtX_{4}, does not act with its remaining affinities when the addition of ammonia to PtX_{2} takes place. These, and certain other considerations which indicate the imperfection of this representation of the structure of the platino-ammonium salts, cause many chemists to incline more to the representations of Berzelius, Claus, Gibbs, and others, who suppose that NH_{3} is able to combine with substances, to adjoin itself or pair itself with them (this kind of combination is called 'Paarung') without altering the fundamental capacity of a substance for further combinations. Thus, in PtX_{2},2NH_{3}, the ammonia is the associate of PtX_{2}, as is expressed by the formula N_{2}H_{6}PtX_{2}. Without enlarging on the exposition of the details of this doctrine, we will only mention that it, like the first, does not render it possible to foresee a limit to the compounds with ammonia; it isolates compounds of this kind into a special and artificial class; does not show the connection between compounds of this and of other kinds, and therefore it essentially only expresses the fact of the combination with ammonia and the modification in its ordinary reactions. For these reasons we do not hold to either of these proposed representations of the ammonio-platinum compounds, but regard them from the point of view cited above with reference to double salts and water of crystallisation--that is, we embrace all these compounds under the representation of compounds of complex types. The type of the compound PtX_{2},2NH_{3} is far more probably the same as that of PtX_{2},2Z--_i.e._ as PtX_{4}, or, still more accurately and truly, it is a compound of the same type as PtX_{2},2KX or PtX_{2},2H_{2}O, &c. Although the platinum first entered into PtK_{2}X_{4} as the type PtX_{2}, yet its character has changed in the same manner as the character of sulphur changes when from SO_{2} the compound SO_{2}(OH)_{2} is obtained, or when KClO_{4}, the higher form, is obtained from KCl. For us as yet there is no question as to _what_ affinities hold X_{2} and what hold 2NH_{3}, because this is a question which arises from the supposition of the existence of different affinities in the atoms, which there is no reason for taking as a common phenomenon. It seems to me that it is most important _as a commencement_ to render clear the analogy in the formation of various complex compounds, and it is this analogy of the ammonia compounds with those of water of crystallisation and double salts that forms the main object of the primary generalisation. We recognise in platinum, at all events, not only the four affinities expressed in the compound PtCl_{4}, but a much larger number of them, if only the _summation of affinities_ is actually possible. Thus, in sulphur we recognise not two but a much greater number of affinities; it is clear that at least six affinities can act. So also among the analogues of platinum: osmic anhydride, OsO_{4}, Ni(CO)_{4}, PtH_{2}Cl_{6}, &c. indicate the existence of at least eight affinities; whilst, in chlorine, judging from the compound KClO_{4} = ClO_{3}(OK) = ClX_{7}, we must recognise at least seven affinities, instead of the one which is accepted. The latter mode of calculating affinities is a tribute to that period of the development of science when only the simplest hydrogen compounds were considered, and when all complex compounds were entirely neglected (they were placed under the class of molecular compounds). This is insufficient for the present state of knowledge, because we find that, in complex compounds as in the most simple, the same constant types or modes of equilibrium are repeated, and the character of certain elements is greatly modified in the passage from the most simple into very complex compounds. Judging from the most complex platino-ammonium compounds PtCl_{4},4NH_{3}, we should admit the possibility of the formation of compounds of the type PtX_{4}Y_{4}, where Y_{4} = 4X_{2} = 4NH_{3}, and this shows that those forces which form such a characteristic series of double platinocyanides PtK_{2}(CN)_{4},3H_{2}O, probably also determine the formation of the higher ammonia derivatives, as is seen on comparing-- PtCl_{2} NH_{3} Cl_{2} 3NH_{3} Pt(CN)_{2} KCN KCN 3H_{2}O. Moreover, it is obviously much more natural to ascribe the faculty for combination with _n_Y to the whole of the acting elements--that is, to PtX_{2} or PtX_{4}, and not to platinum alone. Naturally such compounds are not produced with any Y. With certain X's there only combine certain Y's. The best known and most frequently-formed compounds of this kind are those with water--that is, compounds with water of crystallisation. Compounds with salts are double salts; also we know that similar compounds are also frequently formed by means of ammonia. Salts of zinc, ZnX_{2}, copper, CuX_{2}, silver, AgX, and many others give similar compounds, but these and many other _ammonio-metallic_ saline compounds are unstable, and readily part with their combined ammonia, and it is only in the elements of the platinum group and in the group of the analogues of iron, that we observe the faculty to form stable ammonio-metallic compounds. It must be remembered that the metals of the platinum and iron groups are able to form several high grades of oxidation which have an acid character, and consequently in the lower degrees of combination there yet remain affinities capable of retaining other elements, and they probably retain ammonia, and hold it the more stably, because all the properties of the platinum compounds are rather acid than basic--that is, PtX_{n} recalls rather HX or SnX_{n} or CX_{n} than KX, CaX_{2}, BaX_{2}, &c., and ammonia naturally will rather combine with an acid than with a basic substance. Further, a dependence, or certain connection of the forms of oxidation with the ammonia compounds, is seen on comparing the following compounds: PdCl_{2},2NH_{3},H_{2}O PdCl_{2},4NH_{3},H_{2}O PtCl_{2},2NH_{3} PtCl_{4},4NH_{3} RhCl_{3},5NH_{3} RuCl_{2},4NH_{3},3H_{2}O IrCl_{3},5NH_{3} OsCl_{2},4NH_{3},2H_{2}O We know that platinum and palladium give compounds of lower types than iridium and rhodium, whilst ruthenium and osmium give the highest forms of oxidation; this shows itself in this case also. We have purposely cited the same compounds with 4NH_{3} for osmium and ruthenium as we have for platinum and palladium, and it is then seen that Ru and Os are capable of retaining 2H_{2}O and 3H_{2}O, besides Cl_{2} and NH_{3}, which the compounds of platinum and palladium are unable to do. The same ideas which were developed in Note 35, Chapter XXII. respecting the cobaltia compounds are perfectly applicable to the present case, _i.e._ to the _platinia_ compounds or ammonia compounds of the platinum metals, among which Rh and Ir give compounds which are perfectly analogous to the cobaltia compounds. Iridium and rhodium, which easily give compounds of the type RX_{3}, give compounds (Claus) of the type IrX_{3},5NH_{3}, of a rose colour, and RhX_{3},5NH_{3}, of a yellow colour. Jörgensen, in his researches on these compounds, showed their entire analogy with the cobalt compounds, as was to be expected from the periodic system. If ammonia acts on a boiling solution of platinous chloride in hydrochloric acid, it produces the green _salt of Magnus_ (1829), PtCl_{2},2NH_{3}, insoluble in water and hydrochloric acid. But, judging by its reactions, this salt has twice this formula. Thus, Gros (1837), on boiling Magnus's salt with nitric acid, observed that half the chlorine was replaced by the residue of nitric acid and half the platinum was disengaged: 2PtCl_{2}(NH_{3})_{2} + 2HNO_{3} = PtCl_{2}(NO_{3})_{2}(NH_{3})_{4} + 2PtCl_{2}. The Gros's salt thus obtained, PtCl_{2}(NO_{3})_{2}4NH_{3} (if Magnus's salt belongs to the type PtX_{2}, then Gros's salt belongs to the type PtX_{4}), is soluble in water, and the elements of nitric acid, but not the chlorine, contained in it are capable of easily submitting themselves to double saline decomposition. Thus silver nitrate does not enter into double decomposition with the chlorine of Gros's salt. Most instructive was the circumstance that Gros, by acting on his salt with hydrochloric acid, succeeded in substituting the residue of nitric acid in it by chlorine, and the chlorine thus introduced, easily reacted with silver nitrate. Thus it appeared that Gros's salt contained two varieties of chlorine--one which reacts readily, and the other which reacts with difficulty. The composition of Gros's first salt is PtCl_{2}(NH_{3})_{4}(NO_{3})_{2}; it may be converted into PtCl_{2}(NH_{3})_{4}(SO_{4}), and in general into PtCl_{2}(NH_{3})_{4}X_{2}.[13] [13] Subsequently, a whole series of such compounds was obtained with various elements in the place of the (non-reacting) chlorine, and nevertheless they, like the chlorine, reacted with difficulty, whilst the second portion of the X's introduced into such salts easily underwent reaction. This formed the most important reason for the interest which the study of the composition and structure of the platino-ammonium salts subsequently presented to many chemists, such as Reiset, Blomstrand, Peyrone, Raeffski, Gerhardt, Buckton, Clève, Thomsen, Jörgensen, Kournakoff, Verner, and others. The salts PtX_{4},2NH_{3}, discovered by Gerhardt, also exhibited several different properties in the two pairs of X's. In the remaining platino-ammonium salts all the X's appear to react alike. The quality of the X's, retainable in the platino-ammonium salts, may be considerably modified, and they may frequently be wholly or partially replaced by hydroxyl. For example, the action of ammonia on the nitrate of Gerhardt's base, Pt(NO_{3})_{4},2NH_{3}, in a boiling solution, gradually produces a yellow crystalline precipitate which is nothing else than a _basic hydrate_ or _alkali_, Pt(OH)_{4},2NH_{3}. It is sparingly soluble in water, but gives directly soluble salts PtX_{4},2NH_{3} with acids. The stability of this hydroxide is such that potash does not expel ammonia from it, even on boiling, and it does not change below 130°. Similar properties are shown by the hydroxide Pt(OH)_{2},2NH_{3} and the oxide PtO,2NH_{3} of Reiset's second base. But the hydroxides of the compounds containing 4NH_{3} are particularly remarkable. The presence of ammonia renders them soluble and energetic. The brevity of this work does not permit us, however, to mention many interesting particulars in connection with this subject. The salt of Magnus when boiled with a solution of ammonia gives the salt (of Reiset's first base) PtCl_{2}(NH_{3})_{4}, and this, when treated with bromine, forms the salt PtCl_{2}Br_{2}(NH_{3})_{4}, which has the same composition and reactions as Gros's salt. To Reiset's salts there corresponds a soluble, colourless, crystalline _hydroxide_, Pt(OH)_{2}(NH_{3})_{4}, having the properties of a powerful and very energetic _alkali_; it attracts carbonic anhydride from the atmosphere, precipitates metallic salts like potash, saturates active acids, even sulphuric, forming colourless (with nitric, carbonic, and hydrochloric acids), or yellow (with sulphuric acid), salts of the type PtX_{2}(NH_{3})_{4}.[14] The comparative stability (for instance, as compared with AgCl and NH_{3}) of such compounds, and the existence of many other compounds analogous to them, endows them with a particular chemical interest. Thus Kournakoff (1889) obtained a series of corresponding compounds containing thiocarbamide, CSN_{2}H_{4}, in the place of ammonia, PtCl_{2},4CSN_{2}H_{4}, and others corresponding with Reiset's salts. Hydroxylamine, and other substances corresponding with ammonia, also give similar compounds. The common properties and composition of such compounds show their entire analogy to the cobaltia compounds (especially for ruthenium and iridium) and correspond to the fact that both the platinum metals and cobalt occur in the same, eighth, group. [14] Hydroxides are known corresponding with Gros's salts, which contain one hydroxyl group in the place of that chlorine or haloid which in Gros's salts reacts with difficulty, and these hydroxides do not at once show the properties of alkalis, just as the chlorine which stands in the same place does not react distinctly; but still, after the prolonged action of acids, this hydroxyl group is also replaced by acids. Thus, for example, the action of nitric acid on Pt(NO_{3})_{2}Cl_{2},4NH_{3} causes the non-active chlorine to react, but in the product all the chlorine is not replaced by NO_{3}, but only half, and the other half is replaced by the hydroxyl group: Pt(NO_{3})_{2}Cl_{2},4NH_{3} + HNO_{3} + H_{2}O = Pt(NO_{3})_{3}(OH),4NH_{3} + 2HCl; and this is particularly characteristic, because here the hydroxyl group has not reacted with the acid--an evident sign of the non-alkaline character of this residue. I think it may be well to call attention to the fact that the composition of the ammonio-metallosalts very often exhibits a correspondence between the amount of X's and the amount of NH_{3}, of such a nature that we find they contain either XNH_{3} or the grouping X_{2}NH_{3}; for example, Pt(XNH_{3})_{2} and Pt(X_{2}NH_{3})_{2}, Co(X_{2}NH_{3})_{3}, Pt(XNH_{3})_{4}, &c. Judging from this, the view of the constitution of the double cyanides of platinum given in Note 11 finds some confirmation here, but, in my opinion, all questions respecting the composition (and structure) of the ammoniacal, double, complex, and crystallisation compounds stand connected with the solution of questions respecting the formation of compounds of various degrees of stability, among which a theory of solutions must be included, and therefore I think that the time has not yet come for a complete generalisation of the data which exist for these compounds; and here I again refer the reader to Prof. Kournakoff's work cited in Chapter XXII., Note 35. However, we may add a few individual remarks concerning the platinia compounds. To the common properties of the platino-ammonium salts, we must add not only their _stability_ (feeble acids and alkalis do not decompose them, the ammonia is not evolved by heating, &c.), but also the fact that the ordinary reactions of platinum are concealed in them to as great an extent as those of iron in the ferricyanides. Thus neither alkalis nor hydrogen sulphide will separate the platinum from them. For example, sulphuretted hydrogen in acting on Gros's salts gives sulphur, removes half the chlorine by means of its hydrogen, and forms salts of Reiset's first base. This may be understood or explained by considering the platinum in the molecule as covered, walled up by the ammonia, or situated in the centre of the molecule, and therefore inaccessible to reagents. On this assumption, however, we should expect to find clearly-expressed ammoniacal properties, and this is not the case. Thus ammonia is easily decomposed by chlorine, whilst in acting on the platino-ammonium salts containing PtX_{2} and 2NH_{3} or 4NH_{3}, chlorine combines and does not destroy the ammonia; it converts Reiset's salts into those of Gros and Gerhardt. Thus from PtX_{2},2NH_{3} there is formed PtX_{2}Cl_{2},2NH_{3}, and from PtX_{2},4NH_{3} the salt of Gros's base PtX_{2}Cl_{2},4NH_{3}. This shows that the amount of chlorine which combines is not dependent on the amount of ammonia present, but is due to the basic properties of platinum. Owing to this some chemists suppose the ammonia to be inactive or passive in certain compounds. It appears to me that these relations, these modifications, in the usual properties of ammonia and platinum are explained directly by their mutual combination. Sulphur, in sulphurous anhydride, SO_{2}, and hydrogen sulphide, SH_{2}, is naturally one and the same, but if we only knew of it in the form of hydrogen sulphide, then, having obtained it in the form of sulphurous anhydride, we should consider its properties as hidden. The oxygen in magnesia, MgO, and in nitric peroxide, NO_{2}, is so different that there is no resemblance. Arsenic no longer reacts in its compounds with hydrogen as it reacts in its compounds with chlorine, and in their compounds with nitrogen all metals modify both their reactions and their physical properties. We are accustomed to judge the metals by their saline compounds with haloid groups, and ammonia by its compounds with acid substances, and here, in the platino-compounds, if we assume the platinum to be bound to the entire mass of the ammonia--to its hydrogen and nitrogen--we shall understand that both the platinum and ammonia modify their characters. Far more complicated is the question why a portion of the chlorine (and other haloid simple and complex groups) in Gros's salts acts in a different manner from the other portion, and why only half of it acts in the usual way. But this also is not an exclusive case. The chlorine in potassium chlorate or in carbon tetrachloride does not react with the same ease with metals as the chlorine in the salts corresponding with hydrochloric acid. In this case it is united to oxygen and carbon, whilst in the platino-ammonium compounds it is united partly to platinum and partly to the platino-ammonium group. Many chemists, moreover, suppose that a part of the chlorine is united directly to the platinum and the other part to the nitrogen of the ammonia, and thus explain the difference of the reactions; but chlorine united to platinum reacts as well with a silver salt as the chlorine of ammonium chloride, NH_{4}Cl, or nitrosyl chloride, NOCl, although there is no doubt that in this case there is a union between the chlorine and nitrogen. Hence it is necessary to explain the absence of a facile reactive capacity in a portion of the chlorine by the conjoint influence of the platinum and ammonia on it, whilst the other portion may be admitted as being under the influence of the platinum only, and therefore as reacting as in other salts. By admitting a certain kind of stable union in the platino-ammonium grouping, it is possible to imagine that the chlorine does not react with its customary facility, because access to a portion of the atoms of chlorine in this complex grouping is difficult, and the chlorine union is not the same as we usually meet in the saline compounds of chlorine. These are the grounds on which we, in refuting the now accepted explanations of the reactions and formation of the platino-compounds, pronounce the following opinion as to their structure. In characterising the platino-ammonium compounds, it is necessary to bear in mind that compounds which already contain PtX_{4} do not combine directly with NH_{3}, and that such compounds as PtX_{4},4NH_{3} only proceed from PtX_{2}, and therefore it is natural to conclude that those affinities and forces which cause PtX_{2} to combine with X_{2} also cause it to combine with 2NH_{3}. And having the compound PtX_{2},2NH_{3}, and supposing that in subsequently combining with Cl_{2} it reacts with those affinities which produce the compounds of platinic chloride, PtCl_{4}, with water, potassium chloride, potassium cyanide, hydrochloric acid, and the like, we explain not only the fact of combination, but also many of the reactions occurring in the transition of one kind of platino-ammonium salts into another. Thus by this means we explain the fact that (1) PtX_{2},2NH_{3} combines with 2NH_{3}, forming salts of Reiset's first base; (2) and the fact that this compound (represented as follows for distinctness), PtX_{2},2NH_{3},2NH_{3}, when heated, or even when boiled in solution, again passes into PtX_{2},2NH_{3} (which resembles the easy disengagement of water of crystallisation, &c.); (3) the fact that PtX_{2},2NH_{3} is capable of absorbing, under the action of the same forces, a molecule of chlorine, PtX_{2},2NH_{3},Cl_{2}, which it then retains with energy, because it is attracted, not only by the platinum, but also by the hydrogen of the ammonia; (4) the fact that this chlorine held in this compound (of Gerhardt) will have a position unusual in salts, which will explain a certain (although very feebly-marked) difficulty of reaction; (5) the fact that this does not exhaust the faculty of platinum for further combination (we need only recall the compound PtCl_{4},2HCl,16H_{2}O), and that therefore both PtX_{2},2NH_{3},Cl_{2} and PtX_{2},2NH_{3},2NH_{3} are still capable of combination, whence the latter, with chlorine, gives PtX_{2},2NH_{3},2NH_{3},Cl_{2}, after the type of PtX_{4}Y_{4} (and perhaps higher); (6) the fact that Gros's compounds thus formed are readily reconverted into the salts of Reiset's first base when acted on by reducing agents; (7) the fact that in Gros's salts, PtX_{2},2NH_{3}(NH_{3}X)_{2}, the newly-attached chlorine or haloid will react with difficulty with salts of silver, &c., because it is attached both to the platinum and to the ammonia, for both of which it has an attraction; (8) the fact that the faculty for further combination is not even yet exhausted in the type of Gros's salts, and that we actually have a compound of Gros's chlorine salt with platinous chloride and with platinic chloride; the salt PtSO_{4},2NH_{3},2NH_{3},SO_{4} combines further also with H_{2}O; (9) the fact that such a faculty of combination with new molecules is naturally more developed in the lower forms of combination than in the higher. Hence the salts of Reiset's first base--for example, PtCl_{2},2NH_{3},2NH_{3}--both combine with water and give precipitates (soluble in water but not in hydrochloric acid) of double salts with many salts of the heavy metals--for example, with lead chloride, cupric chloride, and also with platinic and platinous chlorides (Buckton's salts). The latter compounds will have the composition PtCl_{2},2NH_{3},2NH_{3},PtCl_{2}--that is, the same composition as the salts of Reiset's second base, but it cannot be identical with it. Such an interesting case does actually exist. The first salt, PtCl_{2},4NH_{3},PtCl_{2}, is green, insoluble in water and in hydrochloric acid, and is known as _Magnus's salt_, and the second, PtCl_{2},2NH_{3}, is Reiset's yellow, sparingly soluble (in water). They are polymeric, namely, the first contains twice the number of elements held in the second, and at the same time they easily pass into each other. If ammonia be added to a hot hydrochloric acid solution of platinous chloride, it forms the salt PtCl_{2},4NH_{3}, but in the presence of an excess of platinous chloride it gives Magnus's salt. On boiling the latter in ammonia it gives a colourless soluble salt of Reiset's first base, PtCl_{2},4NH_{3}, and if this be boiled with water, ammonia is disengaged, and a salt of Reiset's second base, PtCl_{2},2NH_{3}, is obtained. A class of platino-ammonium isomerides (obtained by Millon and Thomsen) are also known. Buckton's salts--for example, the copper salt--were obtained by them from the salts of Reiset's first base, PtCl_{2},4NH_{3}, by treatment with a solution of cupric chloride, &c., and therefore, according to our method of expression, Buckton's copper salt will be PtCl_{2},4NH_{3},CuCl_{2}. This salt is soluble in water, but not in hydrochloric acid. In it the ammonia must be considered as united to the platinum. But if cupric chloride be dissolved in ammonia, and a solution of platinous chloride in ammonium chloride is added to it, a violet precipitate is obtained of the same composition as Buckton's salt, which, however, is insoluble in water, but soluble in hydrochloric acid. In this a portion, if not all, of the ammonia must be regarded as united to the copper, and it must therefore be represented as CuCl_{2},4NH_{3},PtCl_{2}. This form is identical in composition but different in properties (is isomeric) with the preceding salt (Buckton's). The salt of Magnus is intermediate between them, PtCl_{2},4NH_{3},PtCl_{2}; it is insoluble in water and hydrochloric acid. These and certain other instances of isomeric compounds in the series of the platino-ammonium salts throw a light on the nature of the compounds in question, just as the study of the isomerides of the carbon compounds has served and still serves as the chief cause of the rapid progress of organic chemistry. In conclusion, we may add that (according to the law of substitution) we must necessarily expect all kinds of intermediate compounds between the platino and analogous ammonia derivatives on the one hand, and the complex compounds of nitrous acid on the other. Perhaps the instance of the reaction of ammonia upon osmic anhydride, OsO_{4}, observed by Fritsche, Frémy, and others, and more fully studied by Joly (1891), belongs to this class. The latter showed that when ammonia acts upon an alkaline solution of OsO_{4} the reaction proceeds according to the equation: OsO_{4} + KHO + NH_{3} = OsNKO_{3} + 2H_{2}O. It might be imagined that in this case the ammonia is oxidised, probably forming the residue of nitrous acid (NO), while the type OsO_{4} is deoxidised into OsO_{2}, and a salt, OsO(NO)(KO), of the type OsX_{4} is formed. This salt crystallises well in light yellow octahedra. It corresponds to _osmiamic acid_, OsO(ON)(HO), whose anhydride [OsO(NO)]_{2}, has the composition Os_{2}N_{2}O_{5}, which equals 2Os + N_{2}O_{5} to the same extent as the above-mentioned compound PtCO_{2} equals Pt + CO_{2} (_see_ Note 11). CHAPTER XXIV COPPER, SILVER, AND GOLD That degree of analogy and difference which exists between iron, cobalt, and nickel repeats itself in the corresponding triad ruthenium, rhodium, and palladium, and also in the heavy platinum metals, osmium, iridium, and platinum. These nine metals form Group VIII. of the elements in the periodic system, being the intermediate group between the even elements of the large periods and the uneven, among which we know zinc, cadmium, and mercury in Group II. Copper, silver, and gold complete[1] this transition, because their properties place them in proximity to nickel, palladium, and platinum on the one hand, and to zinc, cadmium, and mercury on the other. Just as Zn, Cd, and Hg; Fe, Ru, and Os; Co, Rh, and Ir; Ni, Pd, and Pt, resemble each other in many respects, so also do Cu, Ag, and Au. Thus, for example, the atomic weight of copper Cu = 63, and in all its properties it stands between Ni = 59 and Zn = 65. But as the transition from Group VIII. to Group II., where zinc is situated, cannot be otherwise than through Group I., so in copper there are certain properties of the elements of Group I. Thus it gives a suboxide, Cu_{2}O, and salts, CuX, like the elements of Group I., although at the same time it forms an oxide, CuO, and salts CuX_{2}, like nickel and zinc. In the state of the oxide, CuO, and the salts, CuX_{2}, copper is analogous to zinc, judging from the insolubility of the carbonates, phosphates, and similar salts, and by the isomorphism, and other characters.[2] In the cuprous salts there is undoubtedly a great resemblance to the silver salts--thus, for example, silver chloride, AgCl, is characterised by its insolubility and capacity of combining with ammonia, and in this respect cuprous chloride closely resembles it, for it is also insoluble in water, and combines with ammonia and dissolves in it, &c. Its composition is also RCl, the same as AgCl, NaCl, KCl, &c., and silver in many compounds resembles, and is even isomorphous with, sodium, so that this again justifies their being brought together. Silver chloride, cuprous chloride, and sodium chloride crystallise in the regular system. Besides which, the specific heats of copper and silver require that they should have the atomic weights ascribed to them. To the oxides Cu_{2}O and Ag_{2}O there are corresponding sulphides Ag_{2}S and Cu_{2}S. They both occur in nature in crystals of the rhombic system, and, what is most important, copper glance contains an isomorphous mixture of them both, and retains the form of copper glance with various proportions of copper and silver, and therefore has the composition R_{2}S where R = Cu, Ag. [1] The perfectly unique position held by copper, silver, and gold in the periodic system of the elements, and the degree of affinity which is found between them, is all the more remarkable, as nature and practice have long isolated these metals from all others by having employed them--for example, for coinage--and determined their relative importance and value in conformity with the order (silver between copper and gold) of their atomic weights, &c. [2] Cupric sulphate contains 5 molecules of water, CuSO_{4},5H_{2}O, and the isomorphous mixtures with ZnSO_{4},7H_{2}O contain either 5 or 7 equivalents, according to whether copper or zinc predominates (Vol. II. p. 6). If there be a large proportion of copper, and if the mixture contain 5H_{2}O, the form of the isomorphous mixture (triclinic) will be isomorphous with cupric sulphate, CuSO_{4},5H_{2}O, but if a large amount of zinc (or magnesium, iron, nickel, or cobalt) be present the form (rhombic or monoclinic) will be nearly the same as that of zinc sulphate, ZnSO_{4},7H_{2}O. Supersaturated solutions of each of these salts crystallise in that form and with that amount of water which is contained in a crystal of one or other of the salts brought in contact with the solution (Chapter XIV., Note 27). Notwithstanding the resemblance in the atomic composition of the cuprous compounds, CuX, and silver compounds, AgX, with the compounds of the alkali metals KX, NaX, there is a considerable degree of difference between these two series of elements. This difference is clearly seen in the fact that the alkali metals belong to those elements which combine with extreme facility with oxygen, decompose water, and form the most alkaline bases; whilst silver and copper are oxidised with difficulty, form less energetic oxides, and do not decompose water, even at a rather high temperature. Moreover, they only displace hydrogen from very few acids. The difference between them is also seen in the dissimilarity of the properties of many of the corresponding compounds. Thus cuprous oxide, Cu_{2}O, and silver oxide, Ag_{2}O, are insoluble in water: the cuprous and silver carbonates, chlorides, and sulphates are also sparingly soluble in water. The oxides of silver and copper are also easily reduced to metal. This difference in properties is in intimate relation with that difference in the density of the metals which exists in this case. The alkali metals belong to the lightest, and copper and silver to the heaviest, and therefore the distance between the molecules in these metals is very dissimilar--it is greater for the former than the latter (tables in Chapter XV.). From the point of view of the periodic law, this difference between copper and silver and such elements of Group I. as potassium and rubidium, is clearly seen from the fact that copper and silver stand in the middle of those large periods (for example, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br) which start with the true metals of the alkalis--that is to say, the analogy and difference between potassium and copper are of the same nature as that between chromium and selenium, or vanadium and arsenic. _Copper_ is one of the few metals which have long been known in a metallic form. The Greeks and Romans imported copper chiefly from the island of Cyprus--whence its Latin name, _cuprum_. It was known to the ancients before iron, and was used, especially when alloyed with other metals, for arms and domestic utensils. That copper was known to the ancients will be understood from the fact that it occurs, although rarely, in a _native state_, and is easily extracted from its other natural compounds. Among the latter are the oxygen compounds of copper. When ignited with charcoal, they easily give up their oxygen to it, and yield metallic copper; hydrogen also easily takes up the oxygen from copper oxide when heated. Copper occurs in a native state, sometimes in association with other ores, in many parts of the Urals and in Sweden, and in considerable masses in America, especially in the neighbourhood of the great American lakes; and also in Chili, Japan, and China. The oxygen compounds of copper are also of somewhat common occurrence in certain localities; in this respect certain deposits of the Urals are especially famous. The geological period of the Urals (Permian) is characterised by a considerable distribution of copper ores. Copper is met with in the form of _cuprous oxide_, or _suboxide of copper_, Cu_{2}O, and is then known as _red copper ore_, because it forms red masses which not unfrequently are crystallised in the regular system. It is found much more rarely in the state of _cupric oxide_, CuO, and is then called _black copper ore_. The most common of the oxygenised compounds of copper are the _basic carbonates_ corresponding with the oxides. That these compounds are undoubtedly of aqueous origin is apparent, not only from the fact that specimens are frequently found of a gradual transition from the metallic, sulphuretted, and oxidised copper into its various carbonates, but also from the presence of water in their composition, and from the laminar, reniform structure which many of them present. In this respect _malachite_ is particularly well known; it is used as a green paint and also for ornaments, owing to the diversity of the shades of colour presented by the different layers of deposited malachite. The composition of malachite corresponds with the basic carbonate containing one molecule of cupric carbonate to one of hydroxide: CuCO_{3},CuH_{2}O_{2}. In this form the copper frequently occurs in admixture with various sedimentary rocks, forming large strata, which confirms the aqueous origin of these compounds. There are many such localities in the Perm and other Governments bounding the Urals. _Blue carbonate of copper_, or _azurite_, is also often met with in the same localities; it contains the same ingredients as malachite, but in a different proportion, its composition being CuH_{2}O_{2},2CuCO_{3}. Both these substances may be obtained artificially by the action of the alkali carbonates on solutions of cupric salts at various temperatures. These native carbonates are often used for the extraction of copper, all the more as they very readily give metallic copper, evolving water and carbonic anhydride when ignited, and leaving the easily-reducible cupric oxide. Copper is, however, still more often met with in the form of the sulphides. The sulphides of copper generally occur in chemical combination with the sulphides of iron.[3] These copper-sulphur compounds (copper pyrites CuFeS_{2}, variegated copper ore Cu_{3}FeS_{3}, &c.) generally occur in veins in a rock gangue. [3] Iron pyrites, FeS_{2}, very often contain a small quantity of copper sulphide (_see_ Chapter XXII., Note 2 bis), and on burning the iron pyrites for sulphurous anhydride the copper oxide remains in the residue, from which the copper is often extracted with profit. For this purpose the whole of the sulphur is not burnt off from the iron pyrites, but a portion is left behind in the ore, which is then slowly ignited (roasted) with access of air. Cupric sulphate is then formed, and is extracted by water; or what is better and more frequently done, the residue from the roasting of the pyrites is roasted with common salt, and the solution of cupric chloride obtained by lixiviating is precipitated with iron. A far greater amount of copper is obtained from other sulphuretted ores. Among these _copper glance_, Cu_{2}S, is more rarely met with. It has a metallic lustre, is grey, generally crystalline, and is obtained in admixture with organic matter; so that there is no doubt that its origin is due to the reducing action of the latter on solutions of cupric sulphate. _Variegated copper ore_, which crystallises in octahedra, not infrequently forms an admixture in copper glance; it has a metallic lustre, and is reddish-brown; it has a superficial play of colours, due to oxidation proceeding on its surface. Its composition is Cu_{3}FeS_{3}. But the most common and widely-distributed copper ore is _copper pyrites_, which crystallises in regular octahedra; it has a metallic lustre, a sp. gr. of 4·0, and yellow colour. Its composition is CuFeS_{2}. It must be remarked that the sulphurous ores of copper are oxidised in the presence of water containing oxygen in solution, and form cupric sulphate, blue vitriol, which is easily soluble in water. If this water contains calcium carbonate, gypsum and cupric carbonate are formed by double decomposition: CuSO_{4} + CaCO_{3} = CuCO_{3} + CaSO_{4}. Hence copper sulphide in the form of different ores must be considered as the primary product, and the many other copper ores as secondary products, formed by water. This is confirmed by the fact that at the present time the water extracted from many copper mines contains cupric sulphate in solution. From this liquid it is easy to extract cupric oxide by the action of organic matter and various impurities of water. Hence metallic copper is sometimes found in natural products of the modification of copper sulphide and is probably deposited by the action of organic matter present in the water. _The extraction of copper from its oxide ores_ does not present any difficulty, because the copper, when ignited with charcoal and melted, is reduced from the impurities which accompany it. This mode of smelting copper ores is carried on in cupola or cylindrical furnaces, fluxes forming a slag being added to the mixture of ore and charcoal. The smelted copper still contains sulphur, iron, and other metallic impurities, from which it is freed by fusion in reverberatory furnaces, with access of air to the surface of the molten metal, as the iron and sulphur are more easily oxidised than the copper. The iron then separates as oxides, which collect in the slag.[4] [4] Copper ores rich in oxygen are very rare; the sulphur ores are of more common occurrence, but the extraction of the copper from them is much more difficult. The problem here not only consists in the removal of the sulphur, but also in the removal of the iron combined with the sulphur and copper. This is attained by a whole series of operations, after which there still sometimes remains the extraction of the metallic silver which generally accompanies the copper, although in but small quantity. These processes commence with the roasting--_i.e._ calcination--of the ore with access of air, by which means the sulphur is converted into sulphurous anhydride. It should here be remarked that iron sulphide is more easily oxidised than copper sulphide, and therefore the greater part of the iron in the residue from roasting is no longer in the form of sulphide but of oxide of iron. The roasted ore is mixed with charcoal, and siliceous fluxes, and smelted in a cupola furnace. The iron then passes into the slag, because its oxide gives an easily-fusible mass with the silica, whilst the copper, in the form of sulphide, fuses and collects under the slag. The greater part of the iron is removed from the mass by this smelting. The resultant _coarse metal_ is again roasted in order to remove the greater part of the sulphur from the copper sulphide, and to convert the metal into oxide, after which the mass is again smelted. These processes are repeated several times, according to the richness of the ore. During these smeltings a portion of the copper is already obtained in a metallic form, because copper sulphide gives metallic copper with the oxide (CuS + 2CuO = 3Cu + SO_{2}). We will not here describe the furnaces used or the details of this process, but the above remarks include the explanation of those chemical processes which are accomplished in the various technical operations which are made use of in the process (for details _see_ works on metallurgy). Besides the smelting of copper there also exist methods for its extraction from solutions in the wet way, as it is called. Recourse is generally had to these methods for poor copper ores. The copper is brought into solution, from which it is separated by means of metallic iron or by other methods (by the action of an electric current). The sulphides are roasted in such a manner that the greater part of the copper is oxidised into cupric sulphate, whilst at the same time the corresponding iron salts are as far as possible decomposed. This process is based on the fact that the copper sulphides absorb oxygen when they are calcined in the presence of air, forming cupric sulphate. The roasted ore is treated with water, to which acid is sometimes added, and after lixiviation the resultant solution containing copper is treated either with metallic iron or with milk of lime, which precipitates cupric hydroxide from the solution. Copper oxide ores poor in metal may be treated with dilute acids in order to obtain the copper oxides in solution, from which the copper is then easily precipitated either by iron or as hydroxide by lime. According to Hunt and Douglas's method, the copper in the ore is converted by calcination into the cupric oxide, which is brought into solution by the action of a mixture of solutions of ferrous sulphate and sodium chloride; the oxide converts the ferrous chloride into ferric oxide, forming copper chlorides, according to the equation 3CuO + 2FeCl_{2} = CuCl_{2} + 2CuCl + Fe_{2}O_{3}. The cupric chloride is soluble in water, whilst the cuprous chloride is dissolved in the solution of sodium chloride, and therefore all the copper passes into solution, from which it is precipitated by iron. The same American metallurgists give the following wet method for extracting the Ag and Au occurring in many copper ores, especially in sulphurous ores: (1) The Cu_{2}S is first converted into oxide by roasting in a calciner; (2) the CuO is extracted by the dilute sulphuric acid obtained in the fourth process, the Cu then passes into solution, while the Ag, Au and oxides of iron remain behind in the residue (from which the noble metals may be extracted); (3) a portion of the copper in solution is converted into CuCl_{2} (and CaSO_{4} precipitated) by means of the CaCl_{2} obtained in the fifth process; (4) the mixture of solutions of CuSO_{4} and CuCl_{2} is converted into the insoluble CuCl (salt of the suboxide) by the action of the SO_{2} obtained by roasting the ore (in the first operation), sulphuric acid is then formed in the solution, according to the equation: CuSO_{4} + CuCl_{2} + SO_{2} + 2H_{2}O = 2H_{2}SO_{4} + 2CuCl; (5) the precipitated CuCl is treated with lime and water, and gives CuCl_{2} in solution and CuO in the residue; and lastly (6) the Cu_{2}O is reduced to metallic Cu by carbon in a furnace. According to Crooke's method the impure copper regulus obtained by roasting and smelting the ore is broken up and immersed repeatedly in molten lead, which extracts the Ag and Au occurring in the regulus. The regulus is then heated in a reverberatory furnace to run off the lead, and is then smelted for Cu. The copper brought into the market often contains small quantities of various impurities. Among these there are generally present iron, lead, silver, arsenic, and sometimes small quantities of oxides of copper. As copper, when mixed with a small amount of foreign substances, loses its tenacity to a certain degree, the manufacture of very thin sheet copper requires the use of Chili copper, which is distinguished for its great softness, and therefore when it is desired to have pure copper, it is best to take thin sheet copper, like that which is used in the manufacture of cartridges. But the purest copper is electrolytic copper--that is, that which is deposited from a solution by the action of an electric current. If the copper contains silver, as is often the case, it is used in gold refineries for the precipitation of silver from its solutions in sulphuric acid. Iron and zinc reduce copper salts, but copper reduces mercury and silver salts. The precipitate contains not only the silver which was previously in solution, but also all that which was in the copper. The silver solutions in sulphuric acid are obtained in the separation of silver from gold by treating their alloys with sulphuric acid, which only dissolves the silver. Copper is characterised by its red colour, which distinguishes it from all other metals. Pure copper is soft, and may be beaten out by a hammer at the ordinary temperature, and when hot may be rolled into very thin sheets. Extremely thin leaves of copper transmit a green light. The tenacity of copper is also considerable, and next to iron it is one of the most durable metals in this respect. Copper wire of 1 sq. millimetre in section only breaks under a weight of 45 kilograms. The specific gravity of copper is 8·8, unless it contains cavities due to the fact that molten copper absorbs oxygen from the air, which is disengaged on cooling, and therefore gives a porous mass whose density is much less. Rolled copper, and also that which is deposited by the electric current, has a comparatively high density. Copper melts at a bright red heat, about 1050°, although below the temperature at which many kinds of cast iron melt. At a high temperature it is converted into vapour, which communicates a green colour to the flame. Both native copper and that cooled from a molten state crystallise in regular octahedra. Copper is not oxidised in dry air at the ordinary temperature, but when calcined it becomes coated with a layer of oxide, and it does not burn even at the highest temperature. Copper, when calcined in air, forms either the red cuprous oxide or the black cupric oxide, according to the temperature and quantity of air supplied. In air at the ordinary temperature, copper--as everyone knows--becomes coated with a brown layer of oxides or a green coating of basic salts, due to the action of the damp air containing carbonic acid. If this action continue for a prolonged time, the copper is covered with a thick coating of basic carbonate, or the so-called verdigris (the _ærugo nobilis_ of ancient statues). This is due to the fact that copper, although scarcely capable of oxidising by itself,[5] _in the presence of water and acids_--even very feeble acids, like carbonic acid--_absorbs oxygen from the air and forms salts_, which is a very characteristic property of it (and of lead).[6] _Copper does not decompose water_, and therefore does not disengage hydrogen from it either at the ordinary or at high temperatures. Nor does copper liberate hydrogen from the oxygen acids; these act on it in two ways: they either give up a portion of their oxygen, forming lower grades of oxidation, or else only react in the presence of air. Thus, when nitric acid acts on copper it evolves nitric oxide, the copper being oxidised at the expense of the nitric acid. In the same way copper converts sulphuric acid into the lower grade of oxidation--into sulphurous anhydride, SO_{2}. In these cases the copper is oxidised to copper oxide, which combines with the excess of acid taken, and therefore forms a cupric salt, CuX_{2}. Dilute nitric acid does not act on copper at the ordinary temperature, but when heated it reacts with great ease; dilute sulphuric acid does not act on copper except in presence of air. [5] Schützenberger showed that when the basic carbonate of copper is decomposed by an electric current it gives, besides the ordinary copper, an allotropic form which grows on the negative platinum electrode, if its surface be smaller than that of the positive copper electrode, in the form of brittle crystalline growths of sp. gr. 8·1. It differs from ordinary copper by giving not nitric oxide but nitrous oxide when treated with nitric acid, and in being very easily oxidised in air, and coated with red shades of colour. It is possible that this is copper hydride, or copper which has occluded hydrogen. Spring (1892) observed that copper reduced from the oxide by hydrogen at the lowest possible temperature was pulverulent, while that reduced from CuCl_{2} at a somewhat high temperature appeared in bright crystals. The same difference occurs with many other metals, and is probably partly due to the volatility of the metallic chlorides. [6] This is taken advantage of in practice; for instance, by pouring dilute acids over copper turnings on revolving tables in the preparation of copper salts, such as verdigris, or the basic acetate 2C_{4}H_{6}CuO_{4},CuH_{2}O_{2},5H_{2}O, which is so much used as an oil paint (_i.e._ with boiled oil). The capacity of copper for absorbing oxygen in the presence of acids is so great that it is possible by this means (by taking, for example, thin copper shavings moistened with sulphuric acid) to take up all the oxygen from a given volume of air, and this is even employed for the analysis of air. The combination of copper with oxygen is not only aided by acids but also by alkalis, although cupric oxide does not appear to have an acid character. Alkalis do not act on copper except in the presence of air, when they produce cupric oxide, which does not appear to combine with such alkalis as caustic potash or soda. But the _action of ammonia_ is particularly distinct (Chapter V., Note 2). In the action of a solution of ammonia not only is oxygen absorbed by the copper, but it also acts on the ammonia, and a definite quantity of ammonia is always acted on simultaneously with the passage of the copper into solution. The ammonia is then converted into nitrous acid, according to the reaction: NH_{3} + O_{3} = NHO_{2} + H_{2}O, and the nitrous acid thus formed passes into the state of ammonium nitrite, NH_{4}NO_{2}. In this manner three equivalents of oxygen are expended on the oxidation of the ammonia, and six equivalents of oxygen pass over to the copper, forming six atoms of cupric oxide. The latter does not remain in the state of oxide, but combines with the ammonia. A strong solution of common salt does not act on copper, but a dilute solution of the salt corrodes copper, converting it into oxychloride--that is, in the presence of air. This action of salt water is evident in those cases where the bottoms of ships are coated with sheet copper. From what has been said above it will be evident that copper vessels should not be employed in the preparation of food, because this contains salts and acids which act on copper in the presence of air, and give copper salts, which are poisonous, and therefore the food prepared in untinned copper vessels may be poisonous. Hence tinned vessels are employed for this purpose--that is, copper vessels coated with a thin layer of tin, on which acid and saline solutions do not act. Both the oxides of copper, Cu_{2}O and CuO, are unacted on by air, and, as already mentioned, they both occur in nature.[6 bis] However, in the majority of cases copper is obtained in the form of cupric oxide and its salts--and the copper compounds used industrially generally belong to this type. This is due to the fact that the _cuprous compounds absorb oxygen_ from the air and pass into cupric compounds. The cupric compounds may serve as the source for the preparation of cuprous oxide, because many reducing agents are capable of deoxidising the oxide into the suboxide. Organic substances are most generally employed for this purpose, and especially saccharine substances, which are able, in the presence of alkalis, to undergo oxidation at the expense of the oxygen of the cupric oxide, and to give acids which combine with the alkali: 2CuO - O = Cu_{2}O. In this case the deoxidation of the copper may be carried further and metallic copper obtained, if only the reaction be aided by heat. Thus, for example, a fine powder of metallic copper may be obtained by heating an ammoniacal solution of cupric oxide with caustic potash and grape sugar. But if the reducing action of the saccharine substance proceed in the presence of a sufficient quantity of alkali in solution, and at not too high a temperature, cuprous oxide is obtained. To see this reaction clearly, it is not sufficient to take any cupric salt, because the alkali necessary for the reaction might precipitate cupric oxide--it is necessary to add previously some substance which will prevent this precipitation. Among such substances, tartaric acid, C_{4}H_{6}O_{6}, is one of the best. In the presence of a sufficient quantity of tartaric acid, any amount of alkali may be added to a solution of cupric salt without producing a precipitate, because a soluble double salt of cupric oxide and alkali is then formed. If glucose (for instance, honey or molasses) be added to such an alkaline tartaric solution, and the temperature be slightly raised, it first gives a yellow precipitate (this is cuprous hydroxide, CuHO), and then, on boiling, a red precipitate of (anhydrous) cuprous oxide. If such a mixture be left for a long time at the ordinary temperature, it deposits well-formed crystals of anhydrous cuprous oxide belonging to the regular system.[7] [6 bis] Copper, besides the cuprous oxide, Cu_{2}O, and cupric oxide, CuO, gives two known higher forms of oxidation, but they have scarcely been investigated, and even their composition is not well known. _Copper dioxide_ (CuO_{2}, or CuO_{2},H_{2}O, perhaps CuOH_{2}O_{2}) is obtained by the action of hydrogen peroxide on cupric hydroxide, when the green colour of the latter is changed to yellow. It is very unstable, and is decomposed even by boiling water, with the evolution of oxygen, whilst the action of acids gives cupric salts, oxygen being also disengaged. A still higher _copper peroxide_ is formed by heating a mixture of caustic potash, nitre, and metallic copper to a red heat, and by dissolving cupric hydroxide in solutions of the hypochlorites of the alkali metals. A slight heating of the soluble salt formed is enough for it to be decomposed into oxygen and copper dioxide, which is precipitated. Judging from Frémy's researches, the composition of the copper-potassic compound should be K_{2}CuO_{4}. Perhaps this is a compound of the peroxides of potassium, K_{2}O_{2}, and of copper, CuO_{2}. [7] Colourless solutions of cuprous salts may also be obtained by the action of sulphurous or phosphorous acid and similar lower grades of oxidation on the blue solutions of the cupric salts. This is very clearly and easily effected by means of sodium thiosulphate, Na_{2}S_{2}O_{3}, which is oxidised in the process. Cuprous oxide can not only be obtained by the deoxidation of cupric oxide, but also directly from metallic copper itself, because the latter, in oxidising at a red heat in air, first gives cuprous oxide. It is prepared in this manner on a large scale by heating sheet copper rolled into spirals in reverberatory furnaces. Care must be taken that the air is not in great excess, and that the coating of red cuprous oxide formed does not begin to pass into the black cupric oxide. If the oxidised spiral sheet is then unbent, the brittle cuprous oxide falls away from the soft metal. The suboxide obtained in this manner fuses with ease. It is necessary to prevent the access of air during the fusion, and if the mass contains cupric oxide it must be mixed with charcoal, which reduces the latter. Cuprous chloride, CuCl, corresponding with cuprous oxide (as sodium chloride corresponds with sodium oxide), when calcined with sodium carbonate, gives sodium chloride and cuprous oxide, carbonic anhydride being evolved, because it does not combine with the cuprous oxide under these conditions. The reaction can be expressed by the following equation: 2CuCl + Na_{2}CO_{3} = Cu_{2}O + 2NaCl + CO_{2}. The cupric oxide itself, when calcined with finely-divided copper, this copper powder may be obtained by many methods--for instance, by immersing zinc in a solution of a copper salt, or by igniting cupric oxide in hydrogen), gives the fusible cuprous oxide: Cu + CuO = Cu_{2}O. Both the native and artificial cuprous oxide have a sp. gr. of 5·6. It is insoluble in water, and is not acted on by (dry) air. When heated with acids the suboxide forms a solution of a cupric salt and metallic copper--for example, Cu_{2}O + H_{2}SO_{4} = Cu + CuSO_{4} + H_{2}O. However, strong hydrochloric acid does not separate metallic copper on dissolving cuprous oxide, which is due to the fact that the cuprous chloride formed is soluble in strong hydrochloric acid. Cuprous oxide also dissolves in a solution of ammonia, and in the absence of air gives a colourless solution, which turns blue in the air, absorbing oxygen, owing to the conversion of the cuprous oxide into cupric oxide. The blue solution thus formed may be again reconverted into a colourless cuprous solution by immersing a copper strip in it, because the metallic copper then deoxidises the cupric oxide in the solution into cuprous oxide. Cuprous oxide is characterised by the fact that it gives red glasses when fused with glass or with salts forming vitreous alloys. Glass tinted with cuprous oxide is used for ornaments. The access of air must be avoided during its preparation, because the colour then becomes green, owing to the formation of cupric oxide, which colours glass blue. This may even be taken advantage of in testing for copper under the blow-pipe by heating the copper compound with borax in the flame of a blow-pipe; a red glass is obtained in the reducing flame, and a blue glass in the oxidising flame, owing to the conversion of the cuprous into cupric oxide. Étard (1882), by passing sulphurous anhydride into a solution of cupric acetate, obtained a white precipitate of cuprous sulphite, Cu_{2}SO_{3},H_{2}O, whilst he obtained the same salt, of a red colour, from the double salt of sodium and copper; but there are not any convincing proofs of isomerism in this case. Cupric chloride, CuCl_{2}, when ignited, gives _cuprous chloride_, CuCl--_i.e._ the salt corresponding with suboxide of copper--and therefore cuprous chloride is always formed when copper enters into reaction with chlorine at a high temperature. Thus, for example, when copper is calcined with mercuric chloride, it forms cuprous chloride and vapours of mercury. The same substance is obtained on heating metallic copper in hydrochloric acid, hydrogen being disengaged; but this reaction only proceeds with finely-divided copper, as hydrochloric acid acts very feebly on compact masses of copper, and, in the presence of air, gives cupric chloride. The green solution of cupric chloride is decolorised by metallic copper, cuprous chloride being formed; but this reaction is only accomplished with ease when the solution is very concentrated and in the presence of an excess of hydrochloric acid to dissolve the cuprous chloride. The addition of water to the solution precipitates the cuprous chloride, because it is less soluble in dilute than in strong hydrochloric acid. Many reducing agents which are able to take up half the oxygen from cupric oxide are able, in the presence of hydrochloric acid, to form cuprous chloride. Stannous salts, sulphurous anhydride, alkali sulphites, phosphorous and hypophosphorous acids, and many similar reducing agents, act in this manner. The usual method of preparing cuprous chloride consists in passing sulphurous anhydride into a very strong solution of cupric chloride: 2CuCl_{2} + SO_{2} + 2H_{2}O = 2CuCl + 2HCl + H_{2}SO_{4}. Cuprous chloride forms colourless cubic crystals which are insoluble in water. It is easily fusible, and even volatile. Under the action of oxidising agents, it passes into the cupric salt, and it absorbs oxygen from moist air, forming cupric oxychloride, Cu_{2}Cl_{2}O. _Aqueous ammonia_ easily _dissolves_ cuprous chloride as well as cuprous oxide; the solution also turns blue on exposure to the air. Thus an ammoniacal solution of cuprous chloride serves as an excellent absorbent for oxygen; but this solution absorbs not only oxygen, but also certain other gases--for example, carbonic oxide and acetylene.[8] [8] The solubility of cuprous chloride in ammonia is due to the formation of compounds between the ammonia and the chloride. In a warm solution the compound NH_{3},2CuCl is formed, and at the ordinary temperature CuCl,NH_{3}. This salt is soluble in hydrochloric acid, and then forms a corresponding double salt of cuprous chloride and ammonium chloride. By the action of a certain excess of ammonia on a hydrochloric acid solution of cuprous chloride, very well formed crystals, having the composition CuCl,NH_{3},H_{2}O, are obtained. Cuprous chloride is not only soluble in ammonia and hydrochloric acid, but it also dissolves in solutions of certain other salts--for example, in sodium chloride, potassium chloride, sodium thiosulphate, and certain others. All the solutions of cuprous chloride act in many cases as very powerful deoxidising substances; for example, it is easy, by means of these solutions, to precipitate gold from its solutions in a metallic form, according to the equation AuCl_{3} + 3CuCl = Au + 3CuCl_{2}. Among the other compounds corresponding with cuprous oxide, _cuprous iodide_, CuI, is worthy of remark. It is a colourless substance which is insoluble in water and sparingly soluble in ammonia (like silver iodide), but capable of absorbing it, and in this respect it resembles cuprous chloride. It is remarkable from the fact that it is exceedingly easily formed from the corresponding cupric compound CuI_{2}. A solution of cupric iodide easily decomposes into iodine and cuprous iodide, even at the ordinary temperature, whilst cupric chloride only suffers a similar change on ignition. If a solution of a cupric salt be mixed with a solution of potassium iodide the cupric iodide formed immediately decomposes into free iodine and cuprous iodide, which separates out as a precipitate. In this case the cupric salt acts in an oxidising manner, like, for example, nitrous acid, ozone, and other substances which liberate iodine from iodides, but with this difference, that it only liberates half, whilst they set free the whole of the iodine from potassium iodide: 2KI + CuCl_{2} = 2KCl + CuI + I. It must also be remarked that cuprous oxide, when treated with hydrofluoric acid, gives an insoluble cuprous fluoride, CuF. Cuprous cyanide is also insoluble in water, and is obtained by the addition of hydrocyanic acid to a solution of cupric chloride saturated with sulphurous anhydride. This cuprous cyanide, like silver cyanide, gives a double soluble salt with potassium cyanide. The double cyanide of copper and potassium is tolerably stable in the air, and enters into double decompositions with various other salts, like those double cyanides of iron with which we are already acquainted. _Copper hydride_, CuH, also belongs to the number of the cuprous compounds. It was obtained by Würtz by mixing a hot (70°) solution of cupric sulphate with a solution of hypophosphorous acid, H_{3}PO_{2}. The addition of the reducing hypophosphorous acid must be stopped when a brown precipitate makes its appearance, and when gas begins to be evolved. The brown precipitate is the hydrated cuprous hydride. When gently heated it disengages hydrogen; it gives cuprous oxide when exposed to the air, burns in a stream of chlorine, and liberates hydrogen with hydrochloric acid: CuH + HCl = CuCl + H_{2}. Zinc, silver, mercury, lead, and many other heavy metals do not form such a compound with hydrogen, neither under these circumstances nor under the action of hydrogen at the moment of the decomposition of salts by a galvanic current. The greatest resemblance is seen between cuprous hydride and the hydrogen compounds of potassium, sodium, Pd, Ca, and Ba. When copper is oxidised with a considerable quantity of oxygen at a high temperature, or at the ordinary temperature in the presence of acids, and also when it decomposes acids, converting them into lower grades of oxidation (for example, when submitted to the action of nitric and sulphuric acids), it forms _cupric oxide_, CuO, or, in the presence of acids, cupric salts. Copper rust, or that black mass which forms on the surface of copper when it is calcined, consists of cupric oxide. The coating of the oxidised copper is very easily separated from the metallic copper, because it is brittle and very easily peels off, when it is struck or immersed in water. Many copper salts (for instance, the nitrite and carbonate) leave oxide of copper[8 bis] in the form of friable black powder, after being ignited. If the ignition be carried further, Cu_{2}O may be formed from the CuO.[8 tri] Anhydrous cupric oxide is very easily dissolved in acids, forming cupric salts, CuX_{2}. They are analogous to the salts MgX_{2}, ZnX_{2}, NiX_{2}, FeX_{2}, in many respects. On adding potassium or ammonium hydroxide to a solution of a cupric salt, it forms a gelatinous blue precipitate of the hydrated oxide of copper, CuH_{2}O_{2}, insoluble in water. The resultant precipitate _is redissolved by an excess of ammonia_, and gives a very beautiful azure blue solution, of so intense a colour that the presence of small traces of cupric salts may be discovered by this means.[9] An excess of potassium or sodium hydroxide does not dissolve cupric hydroxide. A hot solution gives a black precipitate of the anhydrous oxide instead of the blue precipitate, and the precipitate of the hydroxide of copper becomes granular, and turns black when the solution is heated. This is due to the fact that the blue hydroxide is exceedingly unstable, and when slightly heated it loses the elements of water and gives the black anhydrous cupric oxide: CuH_{2}O_{2} = CuO + H_{2}O. [8 bis] The oxide of copper obtained by igniting the nitrate is frequently used for organic analyses. It is hygroscopic and retains nitrogen (1·5 c.c. per gram) when the nitrate is heated in vacuo (Richards and Rogers, 1893). [8 tri] Oxide of copper is also capable of dissociating when heated. Debray and Joannis showed that it then disengages oxygen, whose maximum tension is constant for a given temperature, providing that fusion does not take place (the CuO then dissolves in the molten Cu_{2}O); that this loss of oxygen is followed by the formation of suboxide, and that on cooling, the oxygen is again absorbed, forming CuO. [9] Cupric oxide and many of its salts are able to give definite, although unstable, _compounds with ammonia_. This faculty already shows itself in the fact that cupric oxide, as well as the salts of copper, dissolves in aqueous ammonia, and also in the fact that salts of copper absorb ammonia gas. If ammonia be added to a solution of any cupric salt, it first forms a precipitate of cupric hydroxide, which then dissolves in an excess of ammonia. The solution thus formed, when evaporated or on the addition of alcohol, frequently deposits crystals of salts containing both the elements of the salt of copper taken and of ammonia. Several such compounds are generally formed. Thus cupric chloride, CuCl_{2}, according to Deherain, forms four compounds with ammonia--namely, with one, two, four, and six molecules of ammonia. Thus, for example, if ammonia gas be passed into a boiling saturated solution of cupric chloride, on cooling, small octahedral crystals of a blue colour separate out, containing CuCl_{2},2NH_{3},H_{2}O. At 150° this substance loses half the ammonia and all the water contained in it, leaving the compound CuCl_{2},NH_{3}. Nitrate of copper forms the compound Cu(NO_{3})_{2},2NH_{3}· This compound remains unchanged on evaporation. Dry cupric sulphate absorbs ammonia gas, and gives a compound containing five molecules of ammonia to one of sulphate (Vol. I., p. 257, and Chapter XXII., Note 35). If this compound is dissolved in aqueous ammonia, on evaporation it deposits a crystalline substance containing CuSO_{4},4NH_{3},H_{2}O. At 150° this substance loses the molecule of water and one-fourth of its ammonia. On ignition all these compounds part with the remaining ammonia in the form of an ammoniacal salt, so that the residue consists of cupric oxide. Both the hydrated and anhydrous cupric oxide are soluble in aqueous ammonia. The solution obtained by the action of aqueous ammonia and air on copper turnings (Note 6) is remarkable for its faculty of _dissolving cellulose_, which is insoluble in water, dilute acids, and alkalis. Paper soaked in such a solution acquires the property of not rotting, of being difficultly combustible, and waterproof, &c. It has therefore been applied, especially in England, to many practical purposes--for example, to the construction of temporary buildings, for covering roofs, &c. The composition of the substance held in solution is Cu(HO)_{2},4NH_{3}. If dry ammonia gas be passed over cupric oxide heated to 265°, a portion of the oxide of copper remains unaltered, whilst the other portion gives _copper nitride_, the oxygen of the copper oxide combining with the hydrogen and forming water. The oxide of copper which remains unchanged is easily removed by washing the resultant product with aqueous ammonia. Copper nitride is very stable, and is insoluble; it has the composition Cu_{3}N (_i.e._ the copper is monatomic here as in Cu_{2}O), and is an amorphous green powder, which is decomposed when strongly ignited, and gives cuprous chloride and ammonium chloride when treated with hydrochloric acid. Like the other nitrides, copper nitride, Cu_{3}N, has scarcely been investigated. Granger (1892), by heating copper in the vapour of phosphorus, obtained hexagonal prisms of Cu_{5}P, which passed into Cu_{6}P (previously obtained by Abel) when heated in nitrogen. Arsenic is easily absorbed by copper, and its presence (like P), even in small quantities, has a great influence upon the properties of copper--for instance, pure copper wire 1 sq. mm. in section breaks under a load of 35 kilos, while the presence of O·22 p.c. of arsenic raises the breaking load to 42 kilos. Cupric oxide fuses at a strong heat, and on cooling forms a heavy crystalline mass, which is black, opaque, and somewhat tenacious. It is a feebly energetic base, so that not only do the oxides of the metals of the alkalis and alkaline earths displace it from its compounds, but even such oxides as those of lead and silver precipitate it from solutions, which is partially due to these oxides being soluble, although but slightly so, in water. However, cupric oxide, and especially the hydroxide, easily combines with even the least energetic acids, and does not give any compounds with bases; but, on the other hand, _it easily forms basic salts_,[9 bis] and in this respect outstrips magnesium and recalls the oxides of lead or mercury. Hence the hydroxide of copper dissolves in solutions of neutral cupric salts. The cupric salts are generally blue or green, because cupric hydroxide itself is coloured. But some of the salts in the anhydrous state are colourless.[10] [9 bis] As a comparatively feeble base, oxide of copper easily forms both basic and double salts. As an instance we may mention the double salts composed of the dichloride CuCl_{2},2H_{2}O and potassium chloride. The double salt CuK_{2}Cl_{4},2H_{2}O crystallises from solutions in _blue_ plates, but when heated alone or with substances taking up water easily gives _brown_ needles CuKCl_{3} and at the same time KCl, and this reaction is reversible at 92° as Meyerhoffer (1889) showed (_i.e._ above 92° the simpler double salt is formed and below 92° the more complex salt). With an excess of the copper salt, KCl gives another double salt, Cu_{2}KCl_{5},4H_{2}O, the transition temperature of which is 55°. The instances of equilibria which are encountered in such complex relations (_see_ Chapter XIV., Note 25, astrakhanite, and Chapter XXII., Note 23) are embraced by the _law of phases_ given by Gibbs (Transactions of the Connecticut Academy of Sciences, 1875-1878, in J. Willard Gibbs' memoir 'On the equilibrium of heterogeneous substances:' and in a clearer and more accessible form in H. W. Bakhuis Roozeboom's papers, Rec. trav. chim., Vol. VI., and in W. Meyerhoffer's memoir _Die Phasenregel und ihre Anwendungen_, 1893, to which sources we refer those desiring fuller information respecting this law). Gibbs calls '_bodies_' substances (simple or compound) capable of forming homogeneous complexes (for instance, solutions or intercombinations) of a varied composition; a _phase_--a mechanically separable portion of such bodies or of their homogeneous complexes (for instance, a vapour, liquid or precipitated solid), _perfect equilibrium_--such a state of bodies and of their complexes as is characterised by a constant pressure at a constant temperature even under a change in the amount of one of the component parts (for instance, of a salt in a saturated solution), while an _imperfect equilibrium_ is such a one for which such a change corresponds with a change of pressure (for instance, an unsaturated solution). The law of phases consists in the fact that: _n bodies only give a perfect equilibrium when n + 1 phases participate in that equilibrium_--for example, in the equilibrium of a salt in its saturated solution in water there are two bodies (the salt and water) and three phases, namely, the salt, solution, and vapour, which can be mechanically separated from each other, and to this equilibrium there corresponds a definite tension. At the same time, _n bodies may occur in n + 2 phases, but only at one definite temperature and one pressure_; a change of one of these may bring about another state (perfect or not--equilibrium stable or unstable). Thus water when liquid at the ordinary temperature offers two phases (liquid and vapour) and is in perfect equilibrium (as also is ice below 0°), but water, ice, and vapour (three phases and only one body) can only be in equilibrium at 0°, and at the ordinary pressure; with a change of _t_ there will remain either only ice and vapour or only liquid water and vapour; whilst with a rise of pressure not only will the vapour pass into the liquid (there again only remain two phases) but also the temperature of the formation of ice will fall (by about 7° per 1000 atmospheres). The same laws of phases are applicable to the consideration of the formation of simple or double salts from saturated solutions and to a number of other purely chemical relations. Thus, for example, in the above-mentioned instance, when the bodies are KCl, CuCl_{2}, and H_{2}O, perfect equilibrium (which here has reference to the solubility) consisting of four phases, corresponds to the following seven cases, considering only the phases (above 0°) A = CuCl_{2},2KCl,2H_{2}O; B = CuCl_{2}KCl; C = CuCl_{2},2H_{2}O,KCl, solution and vapour: (1) A + B + solution + vapour; (2) A + C + solution + vapour; (3) A + KCl + solution + vapour; (4) A + B + C + vapour (it follows that B + KCl + solution gives A); (5) A + C + KCl + vapour; (6) B + C + solution + vapour; and (7) B + KCl + solution + vapour. Thus above 92° A gives B + KCl. The law of phases by bringing complex instances of chemical reaction under simple physical schemes, facilitates their study in detail and gives the means of seeking the simplest chemical relations dealing with solutions, dissociation, double decompositions and similar cases, and therefore deserves consideration, but a detailed exposition of this subject must be looked for in works on physical chemistry. [10] The normal _cupric nitrate_, CuN_{2}O_{6},3H_{2}O, is obtained as a deliquescent salt of a blue colour (soluble in water and in alcohol) by dissolving copper or cupric oxide in nitric acid. It is so easily decomposed by the action of heat that it is impossible to drive off the water of crystallisation from it before it begins to decompose. During the ignition of the normal salt the cupric oxide formed enters into combination with the remaining undecomposed normal salt, and gives a basic salt, CuN_{2}O_{6},2CuH_{2}O_{2}. The same basic salt is obtained if a certain quantity of alkali or cupric hydroxide or carbonate be added to the solution of the normal salt, which is even decomposed when boiled with metallic copper, and forms the basic salt as a green powder, which easily decomposes under the action of heat and leaves a residue of cupric oxide. The basic salt, having the composition CuN_{2}O_{6},3CuH_{2}O_{2}, is nearly insoluble in water. The normal _carbonate of copper_, CuCO_{3}, occurs in nature, although extremely rarely. If solutions of cupric salts be mixed with solutions of alkali carbonates, then, as in the case of magnesium, carbonic anhydride is evolved and basic salts are formed, which vary in composition according to the temperature and conditions of the reaction. By mixing cold solutions, a voluminous blue precipitate is formed, containing an equivalent proportion of cupric hydroxide and carbonate (after standing or heating, its composition is the same as malachite, sp. gr. 3·51: 2CuSO_{4} + 2Na_{2}CO_{3} + H_{2}O = CuCO_{3},CuH_{2}O_{2} + 2Na_{2}SO_{4} + CO_{2}. If the resultant blue precipitate be heated in the liquid, it loses water and is transformed into a granular green mass of the composition Cu_{2}CO_{4}--_i.e._ into a compound of the normal salt with anhydrous cupric oxide. This salt of the oxide corresponds with orthocarbonic acid, C(OH)_{4} = CH_{4}O_{4} where 4H is replaced by 2Cu. On further boiling this salt loses a portion of the carbonic acid, forming black cupric oxide, so unstable is the compound of copper with carbonic anhydride. Another basic salt which occurs in nature, 2CuCO_{3},CuH_{2}O_{2}, is known as azurite, or blue carbonate of copper; it also loses carbonic acid when boiled with water. On mixing a solution of cupric sulphate with sodium sesquicarbonate no precipitate is at first obtained, but after boiling a precipitate is formed having the composition of malachite. Debray obtained artificial azurite by heating cupric nitrate with chalk. The commonest normal salt is _blue vitriol_--_i.e._ the normal cupric sulphate. It generally contains five molecules of water of crystallisation, CuSO_{4},5H_{2}O. It forms the product of the action of strong sulphuric acid on copper, sulphurous anhydride being evolved. The same salt is obtained in practice by carefully roasting sulphuretted ores of copper, and also by the action of water holding oxygen in solution on them: CuS + O_{4} = CuSO_{4}. This salt forms a by-product, obtained in gold refineries, when the silver is precipitated from the sulphuric acid solution by means of copper. It is also obtained by pouring dilute sulphuric acid over sheet copper in the presence of air, or by heating cupric oxide or carbonate in sulphuric acid. The crystals of this salt belong to the triclinic system, have a specific gravity of 2·19, are of a beautiful blue colour, and give a solution of the same colour. 100 parts of water at 0° dissolve 15, at 25° 23, and at 100° about 45 parts of cupric sulphate, CuSO_{4}.[10 bis] At 100° this salt loses a portion of its water of crystallisation, which it only parts with entirely at a high temperature (220°) and then gives a white powder of the anhydrous sulphate; and the latter, on further calcination, loses the elements of sulphuric anhydride, leaving cupric oxide, like all the cupric salts. The anhydrous (colourless) cupric sulphate is sometimes used for absorbing water; it turns blue in the process. It offers the advantage that it retains both hydrochloric acid and water, but not carbonic anhydride.[11] Cupric sulphate is used for steeping seed corn; this is said to prevent the growth of certain parasites on the plants. In the arts a considerable quantity of cupric sulphate is also used in the preparation of other copper salts--for instance, of certain pigments[11 bis]--and a particularly large quantity is used _in the galvanoplastic process_, which consists in the deposition of copper from a solution of cupric sulphate by the action of a galvanic current, when the metallic copper is deposited on the negative pole and takes the shape of the latter. The description of the processes of galvanoplastic art introduced by Jacobi in St. Petersburg forms a part of applied physics, and will not be touched on here, and we will only mention that, although first introduced for small articles, it is now used for such articles as type moulds (_clichés_), for maps, prints, &c., and also for large statues, and for the deposition of iron, zinc, nickel, gold, silver, &c. on other metals and materials. The beginning of the application of the galvanic current to the practical extraction of metals from solutions has also been established, especially since the dynamo-electric machines of Gramme, Siemens, and others have rendered it possible to cheaply convert the mechanical motion of the steam engine into an electric current. It is to be expected that the application of the electric current, which has long since given such important results in chemistry, will, in the near future, play an important part in technical processes, the example being shown by electric lighting. [10 bis] Although sulphate of copper usually crystallises with 5H_{2}O, that is, differently to the sulphates of Mg, Fe, and Mn, it is nevertheless perfectly isomorphous with them, as is seen not only in the fact that it gives isomorphous mixtures with them, containing a similar amount of water of crystallisation, but also in the ease with which it forms, like all bases analogous to MgO, double salts, R_{2}Cu(SO_{4})_{2},6H_{2}O, where R = K, Rb, Cs, of the monoclinic system. Salts of this kind, like CuCl_{2},2KCl,2H_{2}O,PtK_{2}Cy_{4}, &c., present a composition CuX_{2} if the representation of double salts given in Chapter XXIII., Note 11, be admitted, because they, like Cu(HO)_{2}, contain Cu(X_{2}K)_{2}, where X_{2} = SO_{4}, _i.e._ the residue of sulphuric acid, which combines with H_{2}, and is therefore able to replace the H_{2} by X_{2} or O. A detailed study of the crystalline forms of these salts, made by Tutton (1893) (_see_ Chapter XIII., Note 1), showed: (1) that 22 investigated salts of the composition R_{2}M(SO_{4}),6H_{2}O, where R = K, Rb, Cs, and M = Mg, Zn, Cd, Mn, Fe, Co, Ni, Cu, present a complete crystallographic resemblance; (2) that in all respects the Rb salts present a transition between the K and Cs salts; (3) that the Cs salts form crystals most easily, and the K salts the most difficultly, and that for the K salts of Cd and Mn it was even impossible to obtain well-formed crystals; (4) that notwithstanding the closeness of their angles, the general appearance (habit) of the potassium compound differs very clearly from the Cs salts, while the Rb salts present a distinct transition in this respect; (5) that the angle of the inclination of one of the axes to the plane of the two other axes showed that in the K salts (angle from 75° to 75° 38´) the inclination is least, in the Cs salts (from 72° 52´ to 73° 50´) greatest, and in the Rb salts (from 73° 57´ to 74° 42´) intermediate between the two; the replacement of Mg ... Cu produces but a very small change in this angle; (6) that the other angles and the ratio of the axes of the crystals exhibit a similar variation; and (7) that thus the variation of the form is chiefly determined by the atomic weight of the alkaline metal. As an example we cite the magnitude of the inclination of the axes of R_{2}M(SO_{4})_{2},6H_{2}O. R = K Rb Cs M = Mg 75° 12´ 74° 1´ 72° 54´ Zn 75° 12´ 74° 7´ 72° 59´ Cd -- 74° 7´ 72° 49´ Mn -- 73° 3´ 72° 53´ Fe 75° 28´ 74° 16´ 73° 8´ Co 75° 5´ 73° 59´ 72° 52´ Ni 75° 0´ 73° 57´ 72° 58´ Cu 75° 32´ 74° 42´ 73° 50´ This shows clearly (within the limits of possible error, which may be as much as 30´) the almost perfect identity of the independent crystalline forms notwithstanding the difference of the atomic weights of the diatomic elements, M = Mg, Cu. [11] In addition to what has been said (Chapter I., Note 65, and Chapter XXII., Note 35) respecting the combination of CuSO_{4} with water and ammonia, we may add that Lachinoff (1893) showed that CuSO_{4},5H_{2}O loses 4-3/4H_{2}O at 180°, that CuSO_{4},5NH_{3} also loses 4-3/4NH_{3} at 320°, and that only 1/4H_{2}O and 1/4NH_{3} remain in combination with the CuSO_{4}. The last 1/4H_{2}O can only be driven off by heating to 200°, and the last 1/4NH_{3} by heating to 360°. Ammonia displaces water from CuSO_{4},5H_{2}O, but water cannot displace the ammonia from CuSO_{4},5NH_{3}. If hydrochloric acid gas be passed over CuSO_{4},5H_{2}O at the ordinary temperature, it first forms CuSO_{4},5H_{2}O,3HCl, and then CuSO_{4},2H_{2}O,2HCl. When air is passed over the latter compound it passes into CuSO_{4}H_{2}O with a small amount of HCl (about 1/8HCl). At 100° CuSO_{4},5H_{2}O in a stream of hydrochloric acid gas gives CuSO_{4},1/4H_{2}O,2HCl, and then CuSO_{4},1/4H_{2}O,HCl, whilst after prolonged heating CuSO_{4} remains, which rapidly passes into CuSO_{4},5H_{2}O when placed under a bell jar over water. Over sulphuric acid, however, CuSO_{4},5H_{2}O only parts with 3H_{2}O, and if CuSO_{4},2H_{2}O be placed over water it again forms CuSO_{4},5H_{2}O, and so on. [11 bis] Commercial blue vitriol generally contains ferrous sulphate. The salt is purified by converting the ferrous salt into a ferric salt by heating the solution with chlorine or nitric acid. The solution is then evaporated to dryness, and the unchanged cupric sulphate extracted from the residue, which will contain the larger portion of the ferric oxide. The remainder will be separated if cupric hydroxide is added to the solution and boiled; the cupric oxide, CuO, then precipitates the ferric oxide, Fe_{2}O_{3}, just as it is itself precipitated by silver oxide. But the solution will contain a small proportion of a basic salt of copper, and therefore sulphuric acid must be added to the filtered solution, and the salt allowed to crystallise. Acid salts are not formed, and cupric sulphate itself has an acid reaction on litmus paper. _The alloys of copper_ with certain metals, and especially with zinc and tin, are easily formed by directly melting the metals together. They are easily cast into moulds, forged, and worked like copper, whilst they are much more durable in the air, and are therefore frequently used in the arts. Even the ancients used exclusively alloys of copper, and not pure copper, but its alloys with tin or different kinds of bronze (Chapter XVIII., Note 35). The alloys of copper with zinc are called _brass_ or 'yellow metal.' Brass contains about 32 p.c. of zinc; generally, however, it does not contain more than 65 p.c. of copper. The remainder is composed of lead and tin, which usually occur, although in small quantities, in brass. Yellow metal contains about 40 p.c. of zinc.[12] The addition of zinc to copper changes the colour of the latter to a considerable degree; with a certain amount of zinc the colour of the copper becomes yellow, and with a still larger proportion of zinc an alloy is formed which has a greenish tint. In those alloys of zinc and copper which contain a larger amount of zinc than of copper, the yellow colour disappears and is replaced by a greyish colour. But when the amount of zinc is diminished to about 20 p.c., the alloy is red and hard, and is called 'tombac.' A contraction takes place in alloying copper with zinc, so that the volume of the alloy is less than that of either metal individually. The zinc volatilises on prolonged heating at a high temperature and the excess of metallic copper remains behind. When heated in the air, the zinc oxidises before the copper, so that all the zinc alloyed with copper may be removed from the copper by this means. An important property of brass containing about 30 p.c. of zinc is that it is soft and malleable in the cold, but becomes somewhat brittle when heated. We may also mention that ordinary copper coins contain, in order to render them hard, tin, zinc, and iron (Cu = 95 p.c.); that it is now customary to add a small amount of phosphorus to copper and bronze, for the same purpose; and also that copper is added to silver and gold in coining, &c. to render it hard; moreover, in Germany, Switzerland, and Belgium, and other countries, a silver-white alloy (melchior, German silver, &c.), for base coinage and other purposes, is prepared from brass and nickel (from 10 to 20 p.c. of nickel; 20 to 30 p.c. zinc: 50 to 70 p.c. copper), or directly from copper and nickel, or, more rarely, from an alloy containing silver, nickel, and copper.[12 bis] [12] Among the alloys of copper resembling brass, _delta metal_, invented by A. Dick (London) is largely used (since 1883). It contains 55 p.c. Cu, and 41 p.c. Zn, the remaining 4 p.c. being composed of iron (as much as 3-1/2 p.c., which is first alloyed with zinc), or of cobalt, and manganese, and certain other metals. The sp. gr. of delta metal is 8·4. It melts at 950°, and then becomes so fluid that it fills up all the cavities in a mould and forms excellent castings. It has a tensile strength of 70 kilos per sq. mm. (gun metal about 20, phosphor bronze about 30). It is very soft, especially when heated to 600°, but after forging and rolling it becomes very hard; it is more difficultly acted upon by air and water than other kinds of brass, and preserves its golden yellow colour for any length of time, especially if well polished. It is used for making bearings, screw propellers, valves, and many other articles. In general the alloys of Cu and Zn containing about 2/3 p.c. by weight of copper were for a long time almost exclusively made in Sweden and England (Bristol, Birmingham). These alloys for the most part are cheaper, harder, and more fusible than copper alone, and form good castings. The alloys containing 45-80 p.c. Cu crystallise in cubes if slowly cooled (Bi also gives crystals). By washing the surface of brass with dilute sulphuric acid, Zn is removed and the article acquires the colour of copper. The alloys approaching Zn_{2}Cu_{3} in their composition exhibit the greatest resistance (under other equal conditions; of purity, forging, rolling, &c.) The addition of 3 p.c. Al, or 5 p.c. Sn, improves the quality of brass. Respecting aluminium bronze _see_ Chapter XVII. p. 88. [12 bis] Ball (also Kamensky), 1888, by investigating the electrical conductivity of the alloys of antimony and copper with lead, came to the conclusion that only two definite compounds of antimony and copper exist, whilst the other alloys are either alloys of these two together or with antimony or with copper. These compounds are Cu_{2}Sb and Cu_{4}Sb--one corresponds with the maximum, and the other with the minimum, electrical resistance. In general, the resistance offered to an electrical current forms one of the methods by which the composition of definite alloys (for example, Pb_{2}Zn_{7}) is often established, whilst the electromotive force of alloys affords (Laurie, 1888) a still more accurate method--for instance, several definite compounds were discovered by this method among the alloys of copper with zinc and tin; but we will not enter into any details of this subject, because we avoid all references to electricity, although the reader is recommended to make himself acquainted with this branch of science, which has many points in common with chemistry. The study of alloys regarded as solid solutions should, in my opinion, throw much light upon the question of solutions, which is still obscure in many aspects and in many branches of chemistry. Copper, in its cuprous compounds, is so analogous to _silver_, that were there no cupric compounds, or if silver gave stable compounds of the higher oxide, AgO, the resemblance would be as close as that between chlorine and bromine or zinc and cadmium; but silver compounds corresponding to AgO are quite unknown. Although silver peroxide--which was regarded as AgO, but which Berthelot (1880) recognised as the sesquioxide Ag_{2}O_{3}--is known, still it does not form any true salts, and consequently cannot be placed along with cupric oxide. In distinction to copper, silver as a metal does not oxidise under the influence of heat; and its oxides, Ag_{2}O and Ag_{2}O_{3}, easily lose oxygen (_see_ Note 8 tri). Silver does _not oxidise_ in air at the ordinary pressure, and is therefore classed among the so-called _noble metals_. It has a white colour, which is much purer than that of any other known metal, especially when the metal is chemically pure. In the arts silver is always used alloyed, because chemically-pure silver is so soft that it wears exceedingly easily, whilst when fused with a small amount of copper, it becomes very hard, without losing its colour.[13] [13] There are not many soft metals; lead, tin, copper, silver, iron, and gold are somewhat soft, and potassium and sodium very soft. The metals of the alkaline earths are sonorous and hard, and many other metals are even brittle, especially bismuth and antimony. But the very slight significance which these properties have in determining the fundamental chemical properties of substances (although, however, of immense importance in the practical applications of metals) is seen from the example shown by zinc, which is hard at the ordinary temperature, soft at 100°, and brittle at 200°. [Illustration: FIG. 95.--Cupel for silver assaying.] [Illustration: FIG. 96.--Clay muffle.] [Illustration: FIG. 97.--Portable muffle furnace.] As the value of silver depends exclusively on its purity, and as there is no possibility of telling the amount of impurities alloyed with it from its external appearance, it is customary in most countries to mark an article with the amount of pure silver it contains after an accurately-made analysis known as the assay of the silver. In France the assay of silver shows the amount of pure silver in 1,000 parts by weight; in Russia the amount of pure silver in 96 parts--that is, the assay shows the number of zolotniks (4·26 grams) of pure silver in one pound (410 grams) of alloyed silver. Russian silver is generally 84 assay--that is, contains 84 parts by weight of pure silver and 12 parts of copper and other metals. French money contains 90 p.c. (in the Russian system this will be 86·4 assay) by weight of silver [English coins and jewellery contain 92·5 p.c. of silver]; the silver rouble is of 83-1/3 assay--that is, it contains 86·8 p.c. of silver--and the smaller Russian silver coinage is of 48 assay, and therefore contains 50 p.c. of silver. Silver ornaments and articles are usually made in Russia of 84 and 72 assay. As the alloys of silver and copper, especially after being subjected to the action of heat, are not so white as pure silver, they generally undergo a process known as 'blanching' (or 'pickling') after being worked up. This consists in removing the copper from the surface of the article by subjecting it to a dark-red heat and then immersing it in dilute acid. During the calcination the copper on the surface is oxidised, whilst the silver remains unchanged; the dilute acid then dissolves the copper oxides formed, and pure silver is left on the surface. The surface is dull after this treatment, owing to the removal of a portion of the metal by the acid. After being polished the article acquires the desired lustre and colour, so as to be indistinguishable from a pure silver object. In order to test a silver article, a portion of its mass must be taken, not from the surface, but to a certain depth. The methods of assay used in practice are very varied. The commonest and most often used is that known as _cupellation_. It is based on the difference in the oxidisability of copper, lead, and silver. The cupel is a porous cup with thick sides, made by compressing bone ash. The porous mass of bone ash absorbs the fused oxides, especially the lead oxide, which is easily fusible, but it does not absorb the unoxidised metal. The latter collects into a globule under the action of a strong heat in the cupel, and on cooling solidifies into a button, which may then be weighed. Several cupels are placed in a muffle. A muffle is a semi-cylindrical clay vessel, shown in the accompanying drawing. The sides of the muffle are pierced with several orifices, which allow the access of air into it. The muffle is placed in a furnace, where it is strongly heated. Under the action of the air entering the muffle the copper of the silver alloy is oxidised, but as the oxide of copper is infusible, or, more strictly speaking, difficultly fusible, a certain quantity of lead is added to the alloy; the lead is also oxidised by the air at the high temperature of the muffle, and gives the very fusible lead oxide. The copper oxide then fuses with the lead oxide, and is absorbed by the cupel, whilst the silver remains as a bright white globule. If the weight of the alloy taken and of the silver left on the cupel be determined, it is possible to calculate the composition of the alloy. Thus the essence of cupellation consists in the separation of the oxidisable metals from silver, which does not oxidise under the action of heat. A more accurate method, based on the precipitation of silver from its solutions in the form of silver chloride, is described in detail in works on analytical chemistry. Silver occurs in _nature_, both in a native state and in certain compounds. Native silver, however, is of rather rare occurrence. A far greater quantity of silver occurs in combination with sulphur, and especially in the form of _silver sulphide_, Ag_{2}S, with lead sulphide or copper sulphide, or the ores of various other metals. The largest amount of silver is extracted from the lead in which it occurs. If this lead be calcined in the presence of air, it oxidises, and the resultant lead oxide, PbO ('litharge' or 'silberglätte,' as it is called), melts into a mobile liquid, which is easily removed. The silver remains in an unoxidised metallic state.[14] This process is called _cupellation_. [14] In America, whence the largest amount of silver is now obtained, ores are worked containing not more than 1/5 p.c. of silver, whilst at 1/2 p.c. its extraction is very profitable. Moreover, the extraction of silver from ores containing not more than 0·01 p.c. of this metal is sometimes profitable. The majority of the lead smelted from galena contains silver, which is extracted from it. Thus near Arras, in France, an ore is worked which contains about 65 parts of lead and 0·088 part of silver in 100 parts of ore, which corresponds with 136 parts of silver in 100,000 parts of lead. At Freiberg, in Saxony, the ore used (enriched by mechanical dressing) contains about 0·9 of silver, 160 of lead, and 2 of copper in 10,000 parts. In every case the lead is first extracted in the manner described in Chapter XVIII., and this lead will contain all the silver. Not unfrequently other ores of silver are mixed with lead ores, in order to obtain an argentiferous lead as the product. The extraction of small quantities of silver from lead is facilitated by the fact (Pattinson's process) that molten argentiferous lead in cooling first deposits crystals of pure lead, which fall to the bottom of the cooling vessel, whilst the proportion of silver in the unsolidified mass increases owing to the removal of the crystals of lead. The lead is enriched in this manner until it contains 1/400 part of silver, and is then subjected to cupellation on a larger scale. According to Park's process, zinc is added to the molten argentiferous lead, and the alloy of Pb and Zn, which first separates out on cooling, is collected. This alloy is found to contain all the silver previously contained in the lead. The addition of 0·5 p.c. of aluminium to the zinc (Rossler and Edelman) facilitates the extraction of the Ag from the resultant alloy besides preventing oxidation; for, after re-melting, nearly all the lead easily runs off (remains fluid), and leaves an alloy containing about 30 p.c. Ag and about 70 p.c. Zn. This alloy may be used as an anode in a solution of ZnCl_{2}, when the Zn is deposited on the cathode, leaving the silver with a small amount of Pb, &c. behind. The silver can be easily obtained pure by treating it with dilute acids and cupelling. The ores of silver which contain a larger amount of it are: silver glance, Ag_{2}S (sp. gr. 7·2); argentiferous-copper glance, CuAgS; horn silver or chloride of silver, AgCl; argentiferous grey copper ore; polybasite, M_{9}RS_{6} (where M = Ag, Cu, and R = Sb, As), and argentiferous gold. The latter is the usual form in which gold is found in alluvial deposits and ores. The crystals of gold from the Berezoffsky mines in the Urals contain 90 to 95 of gold and 5 to 9 of silver, and the Altai gold contains 50 to 65 of gold and 36 to 38 of silver. The proportion of silver in native gold varies between these limits in other localities. Silver ores, which generally occur in veins, usually contain native silver and various sulphur compounds. The most famous mines in Europe are in Saxony (Freiberg), which has a yearly output of as much as 26 tons of silver, Hungary, and Bohemia (41 tons). In Russia, silver is extracted in the Altai and at Nerchinsk (17 tons). The richest silver mines known are in America, especially in Chili (as much as 70 tons), Mexico (200 tons), and more particularly in the Western States of North America. The richness of these mines may be judged from the fact that one mine in the State of Nevada (Comstock, near Washoe and the cities of Gold Hill and Virginia), which was discovered in 1859, gave an output of 400 tons in 1866. In place of cupellation, chlorination may also be employed for extracting silver from its ores. The method of chlorination consists in converting the silver in an ore into silver chloride. This is either done by a wet or by a dry method, roasting the ore with NaCl. When the silver chloride is formed, the extraction of the metal is also done by two methods. The first consists in the silver chloride being reduced to metal by means of iron in rotating barrels, with the subsequent addition of mercury which dissolves the silver, but does not act on the other metals. The mercury holding the silver in solution is distilled, when the silver remains behind. This method is called _amalgamation_. The other method is less frequently used, and consists in dissolving the silver chloride in sodium chloride or in sodium thiosulphate, and then precipitating the silver from the solution. The amalgamation is then carried on in rotating barrels containing the roasted ore mixed with water, iron, and mercury. The iron reduces the silver chloride by taking up the chlorine from it. The technical details of these processes are described in works on metallurgy. The extraction of AgCl by the wet method is carried on (Patera's process) by means of a solution of hyposulphite of sodium which dissolves AgCl (_see_ Note 23), or by lixiviating with a 2 p.c. solution of a double hyposulphite of Na and Cu (obtained by adding CuSO_{4} to Na_{2}S_{2}O_{3}). The resultant solution of AgCl is first treated with soda to precipitate PbCO_{3}, and then with Na_{2}S, which precipitates the Ag and Au. The process should be carried on rapidly to prevent the precipitation of Cu_{2}S from the solution of CuSO_{4} and Na_{2}S_{2}O_{3}. Commercial silver generally contains copper, and, more rarely, other metallic impurities also. Chemically _pure silver_ is obtained either by cupellation or by subjecting ordinary silver to the following treatment. The silver is first dissolved in nitric acid, which converts it and the copper into nitrates, Cu(NO_{3})_{2} and AgNO_{3}; hydrochloric acid is then added to the resultant solution (green, owing to the presence of the cupric salt), which is considerably diluted with water in order to retain the lead chloride in solution if the silver contained lead. The copper and many other metals remain in solution, whilst the silver is precipitated as silver chloride. The precipitate is allowed to settle, and the liquid is decanted off; the precipitate is then washed and fused with sodium carbonate. A double decomposition then takes place, sodium chloride and silver carbonate being formed; but the latter decomposes into metallic silver, because the silver oxide is decomposed by heat: Ag_{2}CO_{3} = Ag_{2} + O + CO_{2}. The silver chloride may also be mixed with metallic zinc, sulphuric acid, and water, and left for some time, when the zinc removes the chlorine from the silver chloride and precipitates the silver as a powder. This finely-divided silver is called 'molecular silver.'[15] [15] There is another practical method which is also suitable for separating the silver from the solutions obtained in photography, and consists in precipitating the silver by oxalic acid. In this case the amount of silver in the solution must be known, and 23 grams of oxalic acid dissolved in 400 grams of water must be added for every 60 grams of silver in solution in a litre of water. A precipitate of silver oxalate, Ag_{2}C_{2}O_{4}, is then obtained, which is insoluble in water but soluble in acids. Hence, if the liquid contain any free acid it must be previously freed from it by the addition of sodium carbonate. The resultant precipitate of silver oxalate is dried, mixed with an equal weight of dry sodium carbonate, and thrown into a gently-heated crucible. The separation of the silver then proceeds without an explosion, whilst the silver oxalate if heated alone decomposes with explosion. According to Stas, the best method for obtaining silver from its solutions is by the reduction of silver chloride dissolved in ammonia by means of an ammoniacal solution of cuprous thiosulphate; the silver is then precipitated in a crystalline form. A solution of ammonium sulphite may be used instead of the cuprous salt. Chemically-pure silver has an exceeding pure white colour, and a specific gravity of 10·5. Solid silver is lighter than the molten metal, and therefore a piece of silver floats on the latter. The fusing-point of silver is about 950° C., and at the high temperature attained by the combustion of detonating gas it volatilises.[16] By employing silver reduced from silver chloride by milk sugar and caustic potash, and distilling it, Stas obtained silver purer than that obtained by any other means; in fact, this was perfectly pure silver. The vapour of silver has a very beautiful green colour, which is seen when a silver wire is placed in an oxyhydrogen flame.[17] [16] Silver is very malleable and ductile; it may be beaten into leaves 0·002 mm. in thickness. Silver wire may be made so fine that 1 gram is drawn into a wire 2-1/2 kilometres long. In this respect silver is second only to gold. A wire of 2 mm. diameter breaks under a strain of 20 kilograms. [17] In melting, silver absorbs a considerable amount of oxygen, which is disengaged on solidifying. One volume of molten silver absorbs as much as 22 volumes of oxygen. In solidifying, the silver forms cavities like the craters of a volcano, and throws off metal, owing to the evolution of the gas; all these phenomena recall a volcano on a miniature scale (Dumas). Silver which contains a small quantity of copper or gold, &c., does not show this property of dissolving oxygen. The absorption of oxygen by molten silver is, however, an oxidation, but it is at the same time a phenomenon of solution. One cubic centimetre of molten silver can dissolve twenty-two cubic centimetres of oxygen, which, even at 0°, only weighs 0·03 gram, whilst 1 cubic centimetre of silver weighs at least 10 grams, and therefore it is impossible to suppose that the absorption of the oxygen is attended by the formation of any definite compound (rich in oxygen) of silver and oxygen (about 45 atoms of silver to 1 of oxygen) in any other but a dissociated form, and this is the state in which substances in solution must be regarded (Chapter I.) Le Chatelier showed that at 300° and 15 atmospheres pressure silver absorbs so much oxygen that it may be regarded as having formed the compound Ag_{4}O, or a mixture of Ag_{2} and Ag_{2}O. Moreover, silver oxide, Ag_{2}O, only decomposes at 300° under low pressures, whilst at pressures above 10 atmospheres there is no decomposition at 300° but only at 400°. Stas showed that silver is oxidised by air in the presence of acids. V. d. Pfordten confirmed this, and showed that an acidified solution of potassium permanganate rapidly dissolves silver in the presence of air. It has long been known (Wöhler) that when nitrate of silver, AgNO_{3}, reacts as an oxidising agent upon citrates and tartrates, it is able under certain conditions to give either a salt of suboxide of silver (see Note 19) or a red solution, or to give a precipitate of metallic silver reduced at the expense of the organic substances. In 1889 Carey Lea, in his researches on this class of reactions, showed that _soluble silver_ is here formed, which he called _allotropic silver_. It may be obtained by taking 200 c.c. of a 10 per cent. solution of AgNO_{3} and quickly adding a mixture (neutralised with NaHO) of 200 c.c. of a 30 per cent. solution of FeSO_{4} and 200 c.c. of a 40 per cent. solution of sodium citrate. A lilac precipitate is obtained, which is collected on a filter (the precipitate becomes blue) and washed with a solution of NH_{4}NO_{3}. It then becomes soluble in pure water, forming a red perfectly transparent solution from which the dissolved silver is precipitated on the addition of many soluble foreign bodies. Some of the latter--for instance, NH_{4}NO_{3}, alkaline sulphates, nitrates, and citrates--give a precipitate which redissolves in pure water, whilst others--for instance, MgSO_{4}, FeSO_{4}, K_{2}Cr_{2}O_{7}, AgNO_{3}, Ba(NO_{3})_{2} and many others--convert the precipitated silver into a new variety, which, although no longer soluble in water, regains its solubility in a solution of borax and is soluble in ammonia. Both the soluble and insoluble silver are rapidly converted into the ordinary grey-metallic variety by sulphuric acid, although nothing is given off in the reaction; the same change takes place on ignition, but in this case CO_{2} is disengaged; the latter is formed from the organic substances which remain (to the amount of 3 per cent.) in the modified silver (they are not removed by soaking in alcohol or water). If the precipitated silver be slightly washed and laid in a smooth thin layer on paper or glass, it is seen that the soluble variety is red when moist and a fine blue colour when dry, whilst the insoluble variety has a blue reflex. Besides these, under special conditions[18] a golden yellow variety may be obtained, which gives a brilliant golden yellow coating on glass; but it is easily converted into the ordinary grey-metallic state by friction or trituration. There is no doubt[18 bis] that there is the same relation between ordinary silver which is perfectly insoluble in water and the varieties of silver obtained by Carey Lea[18 tri] as there is between quartz and soluble silica or between CuS and As_{2}S_{2} in their ordinary insoluble forms and in the state of the colloid solution of their hydrosols (_see_ Chapter I., Note 57, and Chapter XVII., Note 25 bis). Here, however, an important step in advance has been made in this respect, that we are dealing with the solution of a simple body, and moreover of a metal--_i.e._ of a particularly characteristic state of matter. And as boron, gold, and certain other simple bodies have already been obtained in a soluble (colloid) form, and as numerous organic compounds (albuminous substances, gum, cellulose, starch, &c.) and inorganic substances are also known in this form, it might be said that the colloid state (of hydrogels and hydrosols) can be acquired, if not by every substance, at all events by substances of most varied chemical character under particular conditions of formation from solutions. And this being the case, we may hope that a further study of soluble colloid compounds, which apparently present various transitions towards emulsions, may throw a new light upon the complex question of solutions, which forms one of the problems of the present epoch of chemical science. Moreover, we may remark that Spring (1890) clearly proved the colloid state of soluble silver by means of dialysis as it did not pass through the membrane. [18] When solutions of AgNO_{3}, FeSO_{4}, sodium citrate, and NaHO are mixed together in the manner described above, they throw down a precipitate of a beautiful lilac colour; when transferred to a filter paper the precipitate soon changes colour, and becomes dark blue. To obtain the substance as pure as possible it is washed with a 5-10 p.c. solution of ammonium nitrate; the liquid is decanted, and 150 c.c. of water poured over the precipitate. It then dissolves entirely in the water. A small quantity of a saturated solution of ammonium nitrate is added to the solution, and the silver in solution again separates out as a precipitate. These alternate solutions and precipitations are repeated seven or eight times, after which the precipitate is transferred to a filter and washed with 95 p.c. alcohol until the filtrate gives no residue on evaporation. An analysis of the substance so obtained showed that it contained from 97·18 p.c. to 97·31 p.c. of metallic silver. It remained to discover what the remaining 2-3 p.c. were composed of. Are they merely impurities, or is the substance some compound of silver with oxygen or hydrogen, or does it contain citric acid in combination which might account for its solubility? The first supposition is set aside by the fact that no gases are disengaged by the precipitate of silver, either under the action of gases or when heated. The second supposition is shown to be impossible by the fact that there is no definite relation between the silver and citric acid. A determination of the amount of silver in solution showed that the amount of citric acid varies greatly for one and the same amount of silver, and there is no simple ratio between them. Among other methods of preparing soluble silver given by Carey Lea, we may mention the method published by him in 1891. AgNO_{3} is added to a solution of dextrine in caustic soda or potash; at first a precipitate of brown oxide of silver is thrown down, but the brown colour then changes into a reddish chocolate, owing to the reduction of the silver by the dextrine, and the solution turns a deep red. A few drops of this solution turn water bright red, and give a perfectly transparent liquid. The dextrine solution is prepared by dissolving 40 grams of caustic soda and the same amount of ordinary brown dextrine in two litres of water. To this solution is gradually added 28 grams of AgNO_{3} dissolved in a small quantity of water. The insoluble allotropic silver is obtained, as was mentioned above, from a solution of silver prepared in the manner described, by the addition of sulphate of copper, iron, barium, magnesium, &c. In one experiment Lea succeeded in obtaining the insoluble allotropic Ag in a crystalline form. The red solution, described above, after standing several weeks, deposits crystals spontaneously in the form of short black needles and thin prisms, the liquid becoming colourless. This insoluble variety, when rubbed upon paper, has the appearance of bright shining green flakes, which polarise light. The gold variety is obtained in a different manner to the two other varieties. A solution is prepared containing 200 c.c. of a 10 p.c. solution of nitrate of silver, 200 c.c. of a 20 p.c. solution of Rochelle salt, and 800 c.c. of water. Just as in the previous case the reaction consisted in the reduction of the citrate of silver, so in this case it consists in the reduction of the tartrate, which here first forms a red, and then a black precipitate of allotropic Ag, which, when transferred to the filter, appears of a beautiful bronze colour. After washing and drying, this precipitate acquires the lustre and colour peculiar to polished gold, and this is especially remarked where the precipitate comes into contact with glass or china. An analysis of the golden variety gave a percentage composition of 98·750 to 98·749 Ag. Both the insoluble varieties (the blue and gold) have a different specific gravity from ordinary silver. Whilst that of fused silver is 10·50, and of finely-divided silver 10·62, the specific gravity of the blue insoluble variety is 9·58, and of the gold variety 8·51. The gold variety passes into ordinary Ag with great ease. This transition may even be remarked on the filter in those places which have accidentally not been moistened with water. A simple shock, and therefore friction of one particle upon another, is enough to convert the gold variety into normal white silver. Carey Lea sent samples of the gold variety for a long distance by rail packed in three tubes, in which the silver occupied about the quarter of their volume; in one tube only he filled up this space with cotton-wool. It was afterwards found that the shaking of the particles of Ag had completely converted it into ordinary white silver, and that only the tube containing the cotton-wool had preserved the golden variety intact. The soluble variety of Ag also passes into the ordinary state with great ease, the heat of conversion being, as Prange showed in 1890, about +60 calories. [18 bis] The opinion of the nature of soluble silver given below was first enunciated in the _Journal of the Russian Chemical Society_, February 1, 1890, Vol. XXII., Note 73. This view is, at the present time, generally accepted, and this silver is frequently known as the 'colloid' variety. I may add that Carey Lea observed the solution of ordinary molecular silver in ammonia without the access of air. [18 tri] It is, however, noteworthy that ordinary metallic lead has long been considered soluble in water, that boron has been repeatedly obtained in a brown solution, and that observations upon the development of certain bacteria have shown that the latter die in water which has been for some time in contact with metals. This seems to indicate the passage of small quantities of metals into water (however, the formation of peroxide of hydrogen may be supposed to have some influence in these cases). As regards the capacity of silver for chemical reactions, it is remarkable for its small capacity for combination with oxygen and for its considerable energy of combination with sulphur, iodine, and certain kindred non-metals. _Silver does not oxidise_ at any temperature, and its oxide, Ag_{2}O, is decomposed by heat. It is also a very important fact that silver is not oxidised by oxygen either in the presence of alkalis, even at exceedingly high temperatures, or in the presence of acids--at least, of dilute acids--which properties render it a very important metal in chemical industry for the fusion of alkalis, and also for many purposes in everyday life; for instance, for making spoons, salt-cellars, &c. Ozone, however, oxidises it. Of all acids nitric acid has the greatest action on silver. The reaction is accompanied by the formation of oxides of nitrogen and silver nitrate, AgNO_{3}, which dissolves in water and does not, therefore, hinder the further action of the acid on the metal. The halogen acids, especially hydriodic acid, act on silver, hydrogen being evolved; but this action soon stops, owing to the halogen compounds of silver being insoluble in water and only very slightly soluble in acids; they therefore preserve the remaining mass of metal from the further action of the acid; in consequence of this the action of the halogen acids is only distinctly seen with finely-divided silver. Sulphuric acid acts on silver in the same manner that it does on copper, only it must be concentrated and at a higher temperature. Sulphurous anhydride, and not hydrogen, is then evolved, but there is no action at the ordinary temperature, even in the presence of air. Among the various salts, sodium chloride (in the presence of moisture, air, and carbonic acid) and potassium cyanide (in the presence of air) act on silver more decidedly than any others, converting it respectively into silver chloride and a double cyanide. Although silver does not directly combine with oxygen, still three different grades of combination with oxygen may be obtained indirectly from the salts of silver. They are all, however, unstable, and decompose into oxygen and metallic silver when ignited. These three oxides of silver have the following composition: _silver suboxide_, Ag_{4}O,[19] corresponding with the (little investigated) suboxides of the alkali metals; _silver oxide_, Ag_{2}O, corresponding with the oxides of the alkali metals and the ordinary salts of silver, AgX; and _silver peroxide_, AgO,[19 bis] or, judging from Berthelot's researches, Ag_{2}O_{3}. _Silver oxide_ is obtained as a brown precipitate (which when dried does not contain water) by adding potassium hydroxide to a solution of a silver salt--for example, of silver nitrate. The precipitate formed seems, however, to be an hydroxide, AgHO, _i.e._ AgNO_{3} + KHO = KNO_{3} + AgHO, and the formation of the anhydrous oxide, 2AgHO = Ag_{2}O + H_{2}O, may be compared with the formation of the anhydrous cupric oxide by the action of potassium hydroxide on hot cupric solutions. Silver hydroxide decomposes into water and silver oxide, even at low temperatures; at least, the hydroxide no longer exists at 60°, but forms the anhydrous oxide, Ag_{2}O.[19 tri] Silver oxide is almost insoluble in water; but, nevertheless, it is undoubtedly a rather powerful basic oxide, because it displaces the oxides of many metals from their soluble salts, and saturates such acids as nitric acid, forming with them neutral salts, which do not act on litmus paper.[20] Undoubtedly water dissolves a small quantity of silver oxide, which explains the possibility of its action on solutions of salts--for example, on solutions of cupric salts. Water in which silver oxide is shaken up has a distinctly alkaline reaction. The oxide is distinguished by its great instability when heated, so that it loses all its oxygen when slightly heated. Hydrogen reduces it at about 80°.[20 bis] The feebleness of the affinity of silver for oxygen is shown by the fact that silver oxide decomposes under the action of light, so that it must be kept in opaque vessels. The silver _salts_ are colourless and decompose when heated, leaving metallic silver if the elements of the acid are volatile.[20 tri] They have a peculiar metallic taste, and are exceedingly poisonous; the majority of them are acted on by light, especially in the presence of organic substances, which are then oxidised. The alkaline carbonates give a white precipitate of silver carbonate, Ag_{2}CO_{3}, which is insoluble in water, but soluble in ammonia and ammonium carbonate. Aqueous ammonia, added to a solution of a normal silver salt, first acts like potassium hydroxide, but the precipitate dissolves in an excess of the reagent, like the precipitate of cupric hydroxide.[21] Silver oxalate and the halogen compounds of silver are insoluble in water; hydrochloric acid and soluble chlorides give, as already repeatedly observed, a white precipitate of silver chloride in solutions of silver salts. Potassium iodide gives a yellowish precipitate of silver iodide. Zinc separates all the silver in a metallic form from solutions of silver salts. Many other metals and reducing agents--for example, organic substances--also reduce silver from the solutions of its salts. [19] Silver suboxide (Ag_{4}O) or argentous oxide is obtained from argentic citrate by heating it to 100° in a stream of hydrogen. Water and argentous citrate are then formed, and the latter, although but slightly soluble in water, gives a reddish-brown solution of colloid silver (Note 18), and when boiled this solution becomes colourless and deposits metallic silver, the argentic salt being again formed. Wöhler, who discovered this oxide, obtained it as a black precipitate by adding potassium hydroxide to the above solution of argentous citrate. With hydrochloric acid the suboxide gives a brown compound, Ag_{2}Cl. Since the discovery of soluble silver the above data cannot be regarded as perfectly trustworthy; it is probable that a mixture of Ag_{2} and Ag_{2}O was being dealt with, so that the actual existence of Ag_{4}O is now doubtful, but there can be no doubt as to the formation of a subchloride, Ag_{2}Cl (_see_ Note 25), corresponding to the suboxide. The same compound is obtained by the action of light on the higher chloride. Other acids do not combine with silver suboxide, but convert it into an argentic salt and metallic silver. In this respect cuprous oxide presents a certain resemblance to these suboxides. But copper forms a suboxide of the composition Cu_{4}O, which is obtained by the action of an alkaline solution of stannous oxide on cupric hydroxide, and is decomposed by acids into cupric salts and metallic copper. The problems offered by the suboxides, as well as by the peroxides, cannot be considered as fully solved. [19 bis] _Silver peroxide_, AgO or Ag_{2}O_{3}, is obtained by the decomposition of a dilute (10 p.c.) solution of silver nitrate by the action of a galvanic current (Ritter). On the positive pole, where oxygen is usually evolved in the decomposition of salts, brittle grey needles with a metallic lustre, which occasionally attain a somewhat considerable size, are then formed. They are insoluble in water, and decompose with the evolution of oxygen when they are dried and heated, especially up to 150°, and, like lead dioxide, barium peroxide, &c., their action is strongly oxidising. When treated with acids, oxygen is evolved and a salt of the oxide formed. Silver peroxide absorbs sulphurous anhydride and forms silver sulphate. Hydrochloric acid evolves chlorine; ammonia reduces the silver, and is itself oxidised, forming water and gaseous nitrogen. Analyses of the above-mentioned crystals show that they contain silver nitrate, peroxide, and water. According to Fisher, they have the composition 4AgO,AgNO_{3},H_{2}O, and, according to Berthelot, 4Ag_{2}O_{5},2AgNO_{3},H_{2}O. [19 tri] According to Carey Lea, however, oxide of silver still retains water even at 100°, and only parts with it together with the oxygen. Oxide of silver is used for colouring glass yellow. [20] The reaction of Pb(OH)_{2} upon AgHO in the presence of NaHO leads to the formation of a compound of both oxides, PbO_n_Ag_{2}O, from which the oxide of lead cannot be removed by alkalies (Wöhler, Leton). Wöhler, Welch, and others obtained crystalline double salts, R_{2}AgX_{3}, by the action of strong solutions of RX of the halogen salts of the alkaline metals upon AgX, where R = Cs, Rb, K. [20 bis] According to Müller, ferric oxide is reduced by hydrogen (_see_ Chapter XXII., Note 5) at 295° (into what ?), cupric oxide at 140°, Ni_{2}O_{3} at 150°; nickelous oxide, NiO, is reduced to the suboxide, Ni_{2}O, at 195°, and to nickel at 270°; zinc oxide requires so high a temperature for its reduction that the glass tube in which Müller conducted the experiment did not stand the heat; antimony oxide requires a temperature of 215° for its reduction; yellow mercuric oxide is reduced at 130° and the red oxide at 230°; silver oxide at 85°, and platinum oxide even at the ordinary temperature. [20 tri] A silica compound, Ag_{2}OSiO_{2} is obtained by fusing AgNO_{3} with silica; this salt is able to decompose with the evolution of oxygen, leaving Ag + SiO_{2}. [21] If a solution of a silver salt be precipitated by sodium hydroxide, and aqueous ammonia is added drop by drop until the precipitate is completely dissolved, the liquid when evaporated deposits a violet mass of crystalline silver oxide. If moist silver oxide be left in a strong solution of ammonia it gives a black mass, which easily decomposes with a loud explosion, especially when struck. This black substance is called fulminating silver. Probably this is a compound like the other compounds of oxides with ammonia, and in exploding the oxygen of the silver oxide forms water with the hydrogen of the ammonia, which is naturally accompanied by the evolution of heat and formation of gaseous nitrogen, or, as Raschig states, fulminating silver contains NAg_{3} or one of the amides (for instance, NHAg_{2} = NH_{3} + Ag_{2}O - H_{2}O). Fulminating silver is also formed when potassium hydroxide is added to a solution of silver nitrate in ammonia. The dangerous explosions which are produced by this compound render it needful that great care be taken when salts of silver come into contact with ammonia and alkalis (_see_ Chapter XVI., Note 26). _Silver nitrate_, AgNO_{3}, is known by the name of lunar caustic (or _lapis infernalis_); it is obtained by dissolving metallic silver in nitric acid. If the silver be impure, the resultant solution will contain a mixture of the nitrates of copper and silver. If this mixture be evaporated to dryness and the residue carefully fused at an incipient red heat, all the cupric nitrate is decomposed, whilst the greater part of the silver nitrate remains unchanged. On treating the fused mass with water the latter is dissolved, whilst the cupric oxide remains insoluble. If a certain amount of silver oxide be added to the solution containing the nitrates of silver and copper, it displaces all the cupric oxide. In this case it is of course not necessary to take pure silver oxide, but only to pour off some of the solution and to add potassium hydroxide to one portion, and to mix the resultant precipitate of the hydroxides, Cu(OH)_{2} and AgOH, with the remaining portion.[22] By these methods all the copper can be easily removed and pure silver nitrate obtained (its solution is colourless, while the presence of Cu renders it blue), which may be ultimately purified by crystallisation. It crystallises in colourless transparent prismatic plates, which are not acted on by air. They are anhydrous. Its sp. gr. is 4·34; it dissolves in half its weight of water at the ordinary temperature.[22 bis] The pure salt is not acted on by light, but it easily acts in an oxidising manner on the majority of organic substances, which it generally blackens. This is due to the fact that the organic substance is oxidised by the silver nitrate, which is reduced to metallic silver; the latter is thus obtained in a finely-divided state, which causes the black stain. This peculiarity is taken advantage of for marking linen. Silver nitrate is for the same reason used for _cauterising wounds_ and various growths on the body. Here again it acts by virtue of its oxidising capacity in destroying the organic matter, which it oxidises, as is seen from the separation of a coating of black metallic powdery silver from the part cauterised.[22 tri] From the description of the preparation of silver nitrate it will have been seen that this salt, which fuses at 218°, does not decompose at an incipient red heat; when cast into sticks it is usually employed for cauterising. On further heating, the fused salt undergoes decomposition, first forming silver nitrite and then metallic silver. With ammonia, silver nitrate forms, on evaporation of the solution, colourless crystals containing AgNO_{3},2HN_{3} (Marignac). In general the salts of silver, like cuprous, cupric, zinc, &c. salts, are able to give several compounds with ammonia; for example, silver nitrate in a dry state absorbs three molecules (Rose). The ammonia is generally easily expelled from these compounds by the action of heat. [22] So that we here encounter the following phenomena: copper displaces silver from the solutions of its salts, and silver oxide displaces copper oxide from cupric salts. Guided by the conceptions enunciated in Chapter XV., we can account for this in the following manner: The atomic volume of silver = 10·3, and of copper = 7·2, of silver oxide = 32, and of copper oxide = 13. A greater contraction has taken place in the formation of cupric oxide, CuO, than in the formation of silver oxide, Ag_{2}O, since in the former (13 - 7 = 6) the volume after combination with the oxygen has increased by very little, whilst the volume of silver oxide is considerably greater than that of the metal it contains [32 - (2 × 10·3) = 11·4]. Hence silver oxide is less compact than cupric oxide, and is therefore less stable; but, on the other hand, there are greater intervals between the atoms in silver oxide than in cupric oxide, and therefore silver oxide is able to give more stable compounds than those of copper oxide. This is verified by the figures and data of their reactions. It is impossible to calculate for cupric nitrate, because this salt has not yet been obtained in an anhydrous state; but the sulphates of both oxides are known. The specific gravity of copper sulphate in an anhydrous state is 3·53, and of silver sulphate 5·36; the molecular volume of the former is 45, and of the latter 58. The group SO_{3} in the copper occupies, as it were, a volume 45 - 13 = 32, and in the silver salt a volume 58 - 32 = 26; hence a smaller contraction has taken place in the formation of the copper salt from the oxide than in the formation of the silver salt, and consequently the latter should be more stable than the former. Hence silver oxide is able to decompose the salt of copper oxide, whilst with respect to the metals both salts have been formed with an almost identical contraction, since 58 volumes of the silver salt contain 21 volumes of metal (difference = 37), and 45 volumes of the copper salt contain 7 volumes of copper (difference = 38). Besides which, it must be observed that copper oxide displaces iron oxide, just as silver oxide displaces copper oxide. Silver, copper, and iron, in the form of oxides, displace each other in the above order, but in the form of metals in a reverse order (iron, copper, silver). The cause of this order of the displacement of the oxides lies, amongst other things, in their composition. They have the composition Ag_{2}O, Cu_{2}O_{2}, Fe_{2}O_{3}; the oxide containing a less proportion of oxygen displaces that containing a larger proportion, because the basic character diminishes with the increase of contained oxygen. Copper also displaces mercury from its salts. It may here be remarked that Spring (1888), on leaving a mixture of dry mercurous chloride and copper for two hours, observed a distinct reduction, which belongs to the category of those phenomena which demonstrate the existence of a mobility of parts (_i.e._ atoms and molecules) in solid substances. [22 bis] The reaction of 1 part by weight of AgNO_{3} requires (according to Kremers) the following amounts of water: at 0°, 0·82 part, at 19°·5, 0·41 part, at 54°, 0·20 part, at 110°, 0·09 part, and, according to Tilden, at 125°, 0·0617 part, and at 133°, 0·0515 part. [22 tri] It may be remarked that the black stain produced by the reduction of metallic silver disappears under the action of a solution of mercuric chloride or of potassium cyanide, because these salts act on finely-divided silver. Nitrate of silver easily forms double salts like AgNO_{3}2NaNO_{3} and AgNO_{3}KNO_{3}. Silver nitrate under the action of water and a halogen gives nitric acid (_see_ Vol. I. p. 280, formation of N_{2}O_{5}), a halogen salt of silver, and a silver salt of an oxygen acid of the halogen. Thus, for example, a solution of chlorine in water, when mixed with a solution of silver nitrate, gives silver chloride and chlorate. It is here evident that the reaction of the silver nitrate is identical with the reaction of the caustic alkalis, as the nitric acid is all set free and the silver oxide only reacts in exactly the same way in which aqueous potash acts on free chlorine. Hence the reaction may be expressed in the following manner: 6AgNO_{3} + 3Cl_{2} + 3H_{2}O = 5AgCl + AgClO_{3} + 6NHO_{3}. Silver nitrate, like the nitrates of the alkalis, does not contain any water of crystallisation. Moreover the other salts of silver almost always separate out without any water of crystallisation. The silver salts are further characterised by the fact that they _give neither basic nor acid salts_, owing to which the formation of silver salts generally forms the means of determining the true composition of acids--thus, to any acid H_{n}X there corresponds a salt Ag_{n}X--for instance, Ag_{3}PO_{4} (Chapter XIX., Note 15). _Silver_ gives insoluble and exceedingly stable _compounds with the halogens_. They are obtained by double decomposition with great facility whenever a silver salt comes in contact with halogen salts. Solutions of nitrate, sulphate, and all other kindred salts of silver give a precipitate of silver chloride or iodide in solutions of chlorides and iodides and of the halogen acids, because the halogen salts of silver are insoluble both in water[23] and in other acids. _Silver chloride_, AgCl, is then obtained as a white flocculent precipitate, silver bromide forms a yellowish precipitate, and silver iodide has a very distinct yellow colour. These halogen compounds sometimes occur in nature; they are formed by a dry method--by the action of halogen compounds on silver compounds, especially under the influence of heat. Silver chloride easily fuses at 451° on cooling from a molten state; it forms a somewhat soft horn-like mass which can be cut with a knife and is known as _horn silver_. It volatilises at a higher temperature. Its ammoniacal solution, on the evaporation of the ammonia, deposits crystalline chloride of silver, in octahedra. Bromide and iodide of silver also appear in forms of the regular system, so that in this respect the halogen salts of silver resemble the halogen salts of the alkali metals.[24] [23] Silver chloride is almost perfectly insoluble in water, but is somewhat soluble in water containing sodium chloride or hydrochloric acid, or other chlorides, and many salts, in solution. Thus at 100°, 100 parts of water saturated with sodium chloride dissolve 0·4 part of silver chloride. Bromide and iodide of silver are less soluble in this respect, as also in regard to other solvents. It should be remarked that _silver chloride dissolves in solutions of ammonia, potassium cyanide, and of sodium thiosulphate_, Na_{2}S_{2}O_{3}. Silver bromide is almost perfectly analogous to the chloride, but silver iodide is nearly insoluble in a solution of ammonia. Silver chloride even absorbs dry ammonia gas, forming very unstable ammoniacal compounds. When heated, these compounds (Vol. I. p. 250, Note 8) evolve the ammonia, as they also do under the action of all acids. Silver chloride enters into double decomposition with potassium cyanide, forming a soluble double cyanide, which we shall presently describe; it also forms a soluble double salt, NaAgS_{2}O_{3}, with sodium thiosulphate. Silver chloride offers different modifications in the structure of its molecule, as is seen in the variations in the consistency of the precipitate, and in the differences in the action of light which partially decomposes AgCl (_see_ Note 25). Stas and Carey Lea investigated this subject, which has a particular importance in photography, because silver bromide also gives _photo-salts_. There is still much to be discovered in this respect, since Abney showed that perfectly dry AgCl placed in a vacuum in the dark is not in the least acted upon when subsequently exposed to light. [24] _Silver bromide_ and _iodide_ (which occur as the minerals bromite and iodite) resemble the chloride in many respects, but the degree of affinity of silver for iodine is greater than that for chlorine and bromine, although less heat is evolved (_see_ Note 28 bis). Deville deduced this fact from a number of experiments. Thus silver chloride, when treated with hydriodic acid, evolves hydrochloric acid, and forms silver iodide. Finely-divided silver easily liberates hydrogen when treated with hydriodic acid; it produces the same decomposition with hydrochloric acid, but in a considerably less degree and only on the surface. The difference between silver chloride and iodide is especially remarkable, since the formation of the former is attended with a greater contraction than that of the latter. The volume of AgCl = 26; of chlorine 27, of silver 10, the sum = 37, hence a contraction has ensued; and in the formation of silver iodide an expansion takes place, for the volume of Ag is 10, of I 26, and of AgI 39 instead of 36 (density, AgCl, 5·59; AgI, 5·67). The atoms of chlorine have united with the atoms of silver without moving asunder, whilst the atoms of iodine must have moved apart in combining with the silver. It is otherwise with respect to the metal; the distance between its atoms in the metal = 2·2, in silver chloride = 3·0, and in silver iodide = 3·5; hence its atoms have moved asunder considerably in both cases. It is also very remarkable, as Fizeau observed, that the density of silver iodide increases with a rise of temperature--that is, a contraction takes place when it is heated and an expansion when it is cooled. In order to explain the fact that in silver compounds the iodide is more stable than the chloride and oxide, Professor N. N. Beketoff, in his 'Researches on the Phenomena of Substitutions' (Kharkoff, 1865), proposed the following original hypothesis, which we will give in almost the words of the author:--In the case of aluminium, the oxide, Al_{2}O_{3}, is more stable than the chloride, Al_{2}Cl_{6}, and the iodide, Al_{2}I_{6}. In the oxide the amount of the metal is to the amount of the element combined with it as 54·8 (Al = 27·3) is to 48, or in the ratio 112 : 100; for the chloride the ratio is = 25 : 100; for the iodide it = 7 : 100. In the case of silver the oxide (ratio = 1350 : 100) is less stable than the chloride (ratio = 304 : 100), and the iodide (ratio of the weight of metal to the weight of the halogen = 85 : 100) is the most stable. From these and similar examples it follows that the most stable compounds are those in which the weights of the combined substances are equal. This may be partly explained by the attraction of similar molecules even after their having passed into combination with others. This attraction is proportional to the product of the acting masses. In silver oxide the attraction of Ag_{2} for Ag_{2} = 216 × 216 = 46,656, and the attraction of Ag_{2} for O = 216 × 16 = 3,456. The attraction of like molecules thus counteracts the attraction of the unlike molecules. The former naturally does not overcome the latter, otherwise there would be a disruption, but it nevertheless diminishes the stability. In the case of an equality or proximity of the magnitude of the combining masses, the attraction of the like parts will counteract the stability of the compound to the least extent--in other words, with an inequality of the combined masses, the molecules have an inclination to return to an elementary state, to decompose, which does not exist to such an extent where the combined masses are equal. There is, therefore, a tendency for large masses to combine with large, and for small masses to combine with small. Hence Ag_{2}O + 2KI gives K_{2}O + 2AgI. The influence of an equality of masses on the stability is seen particularly clearly in the effect of a rise of temperature. Argentic, mercuric, auric and other oxides composed of unequal masses, are somewhat readily decomposed by heat, whilst the oxides of the lighter metals (like water) are not so easily decomposed by heat. Silver chloride and iodide approach the condition of equality, and are not decomposed by heat. The most stable oxides under the action of heat are those of magnesium, calcium, silicon, and aluminium, since they also approach the condition of equality. For the same reason hydriodic acid decomposes with greater facility than hydrochloric acid. Chlorine does not act on magnesia or alumina, but it acts on lime and silver oxide, &c. This is partially explained by the fact that by considering heat as a mode of motion, and knowing that the atomic heats of the free elements are equal, it must be supposed that the amount of the motion of atoms (their _vis viva_) is equal, and as it is equal to the product of the mass (atomic weight) into the square of the velocity, it follows that the greater the combining weight the smaller will be the square of the velocity, and if the combining weights be nearly equal, then the velocities also will be nearly equal. Hence the greater the difference between the weights of the combined atoms the greater will be the difference between their velocities. The difference between the velocities will increase with the temperature, and therefore the temperature of decomposition will be the sooner attained the greater be the original difference--that is, the greater the difference of the weights of the combined substances. The nearer these weights are to each other, the more analogous the motion of the unlike atoms, and consequently, the more stable the resultant compound. The instability of cupric chloride and nitric oxide, the absence of compounds of fluorine with oxygen, whilst there are compounds of oxygen with chlorine, the greater stability of the oxygen compounds of iodine than those of chlorine, the stability of boron nitride, and the instability of cyanogen, and a number of similar instances, where, judging from the above argument, one would expect (owing to the closeness of the atomic weights) a stability, show that Beketoff's addition to the mechanical theory of chemical phenomena is still far from sufficient for explaining the true relations of affinities. Nevertheless, in his mode of explaining the relative stabilities of compounds, we find an exceedingly interesting treatment of questions of primary importance. Without such efforts it would be impossible to generalise the complex data of experimental knowledge. _Fluoride of silver_, AgF, is obtained by dissolving Ag_{2}O or Ag_{2}CO_{3} in hydrofluoric acid. It differs from the other halogen salts of silver in being soluble in water (1 part of salt in 0·55 of water). It crystallises from its solution in prisms, AgFH_{2}O (Marignac), or AgF_{2}H_{2}O (Pfaundler), which lose their water in vacuo. Güntz (1891), by electrolising a saturated solution of Ag_{2}F, obtained _polyfluoride of silver_, Ag_{2}F, which is decomposed by water into AgF + Ag. It is also formed by the action of a strong solution of AgF upon finely-divided (precipitated) silver. Silver chloride may be decomposed, with the separation of silver oxide, by heating it with a solution of an alkali, and if an organic substance be added to the alkali the chloride can easily be reduced o metallic silver, the silver oxide being reduced in the oxidation of the organic substance. Iron, zinc, and many other metals reduce silver chloride in the presence of water. Cuprous and mercurous chlorides and many organic substances are also able to reduce the silver from chloride of silver. This shows the rather easy decomposability of the halogen compounds of silver. Silver iodide is much more stable in this respect than the chloride. The same is also observed with respect to the _action of light_ upon moist AgCl. White silver chloride soon acquires a violet colour when exposed to the action of light, and especially under the direct action of the sun's rays. After being acted upon by light it is no longer entirely soluble in ammonia, but leaves metallic silver undissolved, from which it might be assumed that the action of light consisted in the decomposition of the silver chloride into chlorine and metallic silver and in fact the silver chloride becomes in time darker and darker. Silver bromide and iodide are much more slowly acted on by light, and, according to certain observations, when pure they are even quite unacted on; at least they do not change in weight,[24 bis] so that if they are acted on by light, the change they undergo must be one of a change in the structure of their parts and not of decomposition, as it is in silver chloride. The silver chloride under the action of light changes in weight, which indicates the formation of a volatile product, and the deposition of metallic silver on dissolving in ammonia shows the loss of chlorine. The change does actually occur under the action of light, but the decomposition does not go as far as into chlorine and silver, but only to the formation of a subchloride of silver, Ag_{2}Cl, which is of a brown colour and is easily decomposed into metallic silver and silver chloride, Ag_{2}Cl = AgCl + Ag. This change of the chemical composition and structure of the halogen salts of silver under the action of light forms the basis of _photography_, because the halogen compounds of silver, after having been exposed to light, give a precipitate of finely-divided silver, of a black colour, when treated with reducing agents.[25] [24 bis] The changes brought about by the action of light necessitate distinguishing the photo-salts of silver. [25] In photography these are called 'developers.' The most common developers are: solutions of ferrous sulphate, pyrogallol, ferrous oxalate, hydroxylamine, potassium sulphite, hydroquinone (the last acts particularly well and is very convenient to use), &c. The chemical processes of photography are of great practical and theoretical interest; but it would be impossible in this work to enter into this special branch of chemistry, which has as yet been very little worked out from a theoretical point of view. Nevertheless, we will pause to consider certain aspects of this subject which are of a purely chemical interest, and especially the facts concerning _subchloride of silver_, Ag_{2}Cl (_see_ Note 19), and the photo-salts (Note 23). There is no doubt that under the action of light, AgCl becomes darker in colour, decreases in weight, and probably forms a mixture of AgCl, Ag_{2}Cl, and Ag. But the isolation of the subchloride has only been recently accomplished by Güntz by means of the Ag_{2}F, discovered by him (_see_ Note 24). Many chemists (and among them Hodgkinson) assumed that an oxychloride of silver was formed by the decomposition of AgCl under the action of light. Carey Lea's (1889) and A. Richardson's (1891) experiments showed that the product formed does not, however, contain any oxygen at all, and the change in colour produced by the action of light upon AgCl is most probably due to the formation of Ag_{2}Cl. This substance was isolated by Güntz (1891) by passing HCl over crystals of Ag_{2}F. He also obtained Ag_{2}I in a similar manner by passing HI, and Ag_{2}S by passing H_{2}S over Ag_{2}F. Ag_{2}Cl is best prepared by the action of phosphorus trichloride upon Ag_{2}F. At the temperature of its formation Ag_{2}Cl has an easily changeable tint, with shades of violet red to violet black. Under the action of light a similar (isomeric) substance is obtained, which splits up into AgCl + Ag when heated. With potassium cyanide Ag_{2}Cl gives Ag + AgCN + KCl, whence it is possible to calculate the heat of formation of Ag_{2}Cl; it = 29·7, whilst the heat of formation of AgCl = 29·2--_i.e._ the reaction 2AgCl = Ag_{2}Cl + Cl corresponds to an absorption of 28·7 major calories. If we admit the formation of such a compound by the action of light, it is evident that the energy of the light is consumed in the above reaction. Carey Lea (1892) subjected AgCl, AgBr, and AgI to a pressure (of course in the dark) of 3,000 atmospheres, and to trituration with water in a mortar, and observed a change of colour indicating incipient decomposition, which is facilitated under the action of light by the molecular currents set up (Lermontoff, Egoroff). The change of colour of the halogen salts of silver under the action of light, and their faculty of subsequently giving a visible photographic image under the action of 'developers,' must now be regarded as connected with the decomposition of AgX, leading to the formation of Ag_{2}X, and the different tinted photo-salts must be considered as systems containing such Ag_{2}X's. Carey Lea obtained photo-salts of this kind not only by the action of light but also in many other ways, which we will enumerate to prove that they contain the products of an incomplete combination of Ag with the halogens, (for the salts Ag_{2}X must be regarded as such). The photo-salts have been obtained (1) by the imperfect chlorination of silver; (2) by the incomplete decomposition of Ag_{2}O or Ag_{2}CO_{3} by alternately heating and treating with a halogen acid; (3) by the action of nitric acid or Na_{2}S_{2}O_{3} upon Ag_{2}Cl; (4) by mixing a solution of AgNO_{3} with the hydrates of FeO, MnO and CrO, and precipitating by HCl; (5) by the action of HCl upon the product obtained by the reduction of citrate of silver in hydrogen (Note 19), and (6) by the action of milk sugar upon AgNO_{3} together with soda and afterwards acidulating with HCl. All these reactions should lead to the formation of products of imperfect combination with the halogens and give photo-salts of a similar diversity of colour to those produced by the action of developers upon the halogen salts of silver after exposure to light. The insolubility of the halogen compounds of silver forms the basis of many methods used in practical chemistry. Thus by means of this reaction it is possible to obtain salts of other acids from a halogen salt of a given metal, for instance, RCl_{2} + 2AgNO_{3} = R(NO_{3})_{2} + 2AgCl. The formation of the halogen compounds of silver is very frequently used in the investigation of organic substances; for example, if any product of metalepsis containing iodine or chlorine be heated with a silver salt or silver oxide, the silver combines with the halogen and gives a halogen salt, whilst the elements previously combined with the silver replace the halogen. For instance, ethylene dibromide, C_{2}H_{4}Br_{2}, is transformed into ethylene diacetate, C_{2}H_{4}(C_{2}H_{3}O_{2})_{2}, and silver bromide by heating it with silver acetate, 2C_{2}H_{3}O_{2}Ag. The insolubility of the halogen compounds of silver is still more frequently taken advantage of in determining the amount of silver and halogen in a given solution. If it is required, for instance, to determine the quantity of chlorine present in the form of a metallic chloride in a given solution, a solution of silver nitrate is added to it so long as it gives a precipitate. On _shaking or stirring_ the liquid, the silver chloride easily settles in the form of heavy flakes. It is possible in this way to precipitate the whole of the chlorine from a solution, without adding an excess of silver nitrate, since it can be easily seen whether the addition of a fresh quantity of silver nitrate produces a precipitate in the clear liquid. In this manner it is possible to add to a solution containing chlorine, as much silver as is required for its entire precipitation, and to calculate the amount of chlorine previously in solution from the amount of the solution of silver nitrate consumed, if the quantity of silver nitrate in this solution has been previously determined.[25 bis] The atomic proportions and preliminary experiments with a pure salt--for example, with sodium chloride--will give the amount of chlorine from the quantity of silver nitrate. Details of these methods will be found in works on analytical chemistry.[25 tri] [25 bis] In order to determine when the reaction is at an end, a few drops of a solution of K_{2}CrO_{4} are added to the solution of the chloride. Before all the chlorine is precipitated as AgCl, the precipitate (after shaking) is white (since Ag_{2}CrO_{4} with 2RCl gives 2AgCl); but when all the chlorine is thrown down Ag_{2}CrO_{4} is formed, which colours the precipitate reddish-brown. In order to obtain accurate results the liquid should be neutral to litmus. [25 tri] _Silver cyanide_, AgCN, is closely analogous to the haloid salts of silver. It is obtained, in similar manner to silver chloride, by the addition of potassium cyanide to silver nitrate. A white precipitate is then formed, which is almost insoluble in boiling water. It is also, like silver chloride, insoluble in dilute acids. However, it is dissolved when heated with nitric acid, and both hydriodic and hydrochloric acids act on it, converting it into silver chloride and iodide. Alkalis, however, do not act on silver cyanide, although they act on the other haloid salts of silver. Ammonia and solutions of the cyanides of the alkali metals dissolve silver cyanide, as they do the chloride. In the latter case double cyanides are formed--for example, KAgC_{2}N_{2}. This salt is obtained in a crystalline state on evaporating a solution of silver cyanide in potassium cyanide. It is much more stable than silver cyanide itself. It has a neutral reaction, does not change in the air, and does not smell of hydrocyanic acid. Many acids, in acting on a solution of this double salt, precipitate the insoluble silver cyanide. Metallic silver dissolves in a solution of potassium cyanide in the presence of air, with formation of the same double salt and potassium hydroxide, and when silver chloride dissolves in potassium cyanide it forms potassium chloride, besides the salt KAgC_{2}N_{2}. This double salt of silver is used in silver plating. For this purpose potassium cyanide is added to its solution, as otherwise silver cyanide, and not metallic silver, is deposited by the electric current. If two electrodes--one positive (silver) and the other negative (copper)--be immersed in such a solution, silver will be deposited upon the latter, and the silver of the positive electrode will be dissolved by the liquid, which will thus preserve the same amount of metal in solution as it originally contained. If instead of the negative electrode a copper object be taken, well cleaned from all dirt, the silver will be deposited in an even coating; this, indeed, forms the mode of _silver plating by the wet method_, which is most often used in practice. A solution of one part of silver nitrate in 30 to 50 parts of water, and mixed with a sufficient quantity of a solution of potassium cyanide to redissolve the precipitate of silver cyanide formed, gives a dull coating of silver, but if twice as much water be used the same mixture gives a bright coating. Silver plating in the wet way has now replaced to a considerable extent the old process of _dry silvering_, because this process, which consists in dissolving silver in mercury and applying the amalgam to the surface of the objects, and then vaporising the mercury, offers the great disadvantage of the poisonous mercury fumes. Besides these, there is another method of silver plating, based on the direct displacement of silver from its salts by other metals--for example, by copper. The copper reduces the silver from its compounds, and the silver separated is deposited upon the copper. Thus a solution of silver chloride in sodium thiosulphate deposits a coating of silver upon a strip of copper immersed in it. It is best for this purpose to take pure _silver sulphite_. This is prepared by mixing a solution of silver nitrate with an excess of ammonia, and adding a saturated solution of sodium sulphite and then alcohol, which precipitates silver sulphite from the solution. The latter and its solutions are very easily decomposed by copper. Metallic iron produces the same decomposition, and iron and steel articles may be very readily silver-plated by means of the thiosulphate solution of silver chloride. Indeed, copper and similar metals may even be silver-plated by means of silver chloride; if the chloride of silver, with a small amount of acid, be rubbed upon the surface of the copper, the latter becomes covered with a coating of silver, which it has reduced. Silver plating is not only applicable to metallic objects, but also to glass, china, &c. Glass is silvered for various purposes--for example, glass globes silvered internally are used for ornamentation, and have a mirrored surface. Common looking-glass silvered upon one side forms a mirror which is better than the ordinary mercury mirrors, owing to the truer colours of the image due to the whiteness of the silver. For optical instruments--for example, telescopes--concave mirrors are now made of silvered glass, which has first been ground and polished into the required form. The _silvering of glass_ is based on the fact that silver which is reduced from certain solutions deposits itself uniformly in a perfectly homogeneous and continuous but very thin layer, forming a bright reflecting surface. Certain organic substances have the property of reducing silver in this form. The best known among these are certain aldehydes--for instance, ordinary acetaldehyde, C_{2}H_{4}O, which easily oxidises in the air and forms acetic acid, C_{2}H_{4}O_{2}. This oxidation also easily takes place at the expense of silver oxide, when a certain amount of ammonia is added to the mixture. The oxide of silver gives up its oxygen to the aldehyde, and the silver reduced from it is deposited in a metallic state in a uniform bright coating. The same action is produced by certain saccharine substances and certain organic acids, such as tartaric acid, &c. Accurate experiments, and more especially the _researches of Stas_ at Brussels, show the proportion in which silver reacts with metallic chlorides. These researches have led to the determination of the _combining weights_ of silver, sodium, potassium, chlorine, bromine, iodine, and other elements, and are distinguished for their model exactitude, and we will therefore describe them in some detail. As sodium chloride is the chloride most generally used for the precipitation of silver, since it can most easily be obtained in a pure state, we will here cite the quantitative observations made by Stas for showing the co-relation between the quantities of chloride of sodium and silver which react together. In order to obtain perfectly pure sodium chloride, he took pure rock salt, containing only a small quantity of magnesium and calcium compounds and a small amount of potassium salts. This salt was dissolved in water, and the saturated solution evaporated by boiling. The sodium chloride separated out during the boiling, and the mother liquor containing the impurities was poured off. Alcohol of 65 p.c. strength and platinic chloride were added to the resultant salt, in order to precipitate all the potassium and a certain part of the sodium salts. The resultant alcoholic solution, containing the sodium and platinum chlorides, was then mixed with a solution of pure ammonium chloride in order to remove the platinic chloride. After this precipitation, the solution was evaporated in a platinum retort, and then separate portions of this purified sodium chloride were collected as they crystallised. The same salt was prepared from sodium sulphate, tartrate, nitrate, and from the platinochloride, in order to have sodium chloride prepared by different methods and from different sources, and in this manner ten samples of sodium chloride thus prepared were purified and investigated in their relation to silver. After being dried, weighed quantities of all ten samples of sodium chloride were dissolved in water and mixed with a solution in nitric acid of a weighed quantity of perfectly pure silver. A slightly greater quantity of silver was taken than would be required for the decomposition of the sodium chloride, and when, after pouring in all the silver solution, the silver chloride had settled, the amount of silver remaining in excess was determined by means of a solution of sodium chloride of known strength. This solution of sodium chloride was added so long as it formed a precipitate. In this manner Stas determined how many parts of sodium chloride correspond to 100 parts by weight of silver. The result of ten determinations was that for the entire precipitation of 100 parts of silver, from 54·2060 to 54·2093 parts of sodium chloride were required. The difference is so inconsiderable that it has no perceptible influence on the subsequent calculations. The mean of ten experiments was that 100 parts of silver react with 54·2078 parts of sodium chloride. In order to learn from this the relation between the chlorine and silver, it was necessary to determine the quantity of chlorine contained in 54·2078 parts of sodium chloride, or, what is the same thing, the quantity of chlorine which combines with 100 parts of silver. For this purpose Stas made a series of observations on the quantity of silver chloride obtained from 100 parts of silver. Four syntheses were made by him for this purpose. The first synthesis consisted in the formation of silver chloride by the action of chlorine on silver at a red heat. This experiment showed that 100 parts of silver give 132·841, 132·843 and 132·843 of silver chloride. The second method consisted in dissolving a given quantity of silver in nitric acid and precipitating it by means of gaseous hydrochloric acid passed over the surface of the liquid; the resultant mass was evaporated in the dark to drive off the nitric acid and excess of hydrochloric acid, and the remaining silver chloride was fused first in an atmosphere of hydrochloric acid gas and then in air. In this process the silver chloride was not washed, and therefore there could be no loss from solution. Two experiments made by this method showed that 100 parts of silver give 132·849 and 132·846 parts of silver chloride. A third series of determinations was also made by precipitating a solution of silver nitrate with a certain excess of gaseous hydrochloric acid. The amount of silver chloride obtained was altogether 132·848. Lastly, a fourth determination was made by precipitating dissolved silver with a solution of ammonium chloride, when it was found that a considerable amount of silver (0·3175) had passed into solution in the washing; for 100 parts of silver there was obtained altogether 132·8417 of silver chloride. Thus from the mean of seven determinations it appears that 100 parts of silver give 132·8445 parts of silver chloride--that is, that 32·8445 parts of chlorine are able to combine with 100 parts of silver and with that quantity of sodium which is contained in 54·2078 parts of sodium chloride. These observations show that 32·8445 parts of chlorine combine with 100 parts of silver and with 21·3633 parts of sodium. From these figures expressing the relation between the combining weights of chlorine, silver, and sodium, it would be possible to determine their atomic weights--that is, the combining quantity of these elements with respect to one part by weight of hydrogen or 16 parts of oxygen, if there existed a series of similarly accurate determinations for the reactions between hydrogen or oxygen and one of these elements--chlorine, sodium, or silver. If we determine the quantity of silver chloride which is obtained from silver chlorate, AgClO_{3}, we shall know the relation between the combining weights of silver chloride and oxygen, so that, taking the quantity of oxygen as a constant magnitude, we can learn from this reaction the combining weight of silver chloride, and from the preceding numbers the combining weights of chlorine and silver. For this purpose it was first necessary to obtain pure silver chlorate. This Stas did by acting on silver oxide or carbonate, suspended in water, with gaseous chlorine.[26] [26] The phenomenon which then takes place is described by Stas as follows, in a manner which is perfect in its clearness and accuracy: if silver oxide or carbonate be suspended in water, and an excess of water saturated with chlorine be added, all the silver is converted into chloride, just as is the case with oxide or carbonate of mercury, and the water then contains, besides the excess of chlorine, only pure hypochlorous acid without the least trace of chloric or chlorous acid. If a stream of chlorine be passed into water containing _an excess of silver oxide_ or silver carbonate while the liquid is continually agitated, the reaction is the same as the preceding; silver chloride and hypochlorous acid are formed. But this acid does not long remain in a free state: it gradually acts on the silver oxide and gives silver hypochlorite, _i.e._ AgClO. If, after some time, the current of chlorine be stopped but the shaking continued, the liquid loses its characteristic odour of hypochlorous acid, while preserving its energetic decolorising property, because the silver hypochlorite which is formed is easily soluble in water. In the presence of an excess of silver oxide this salt can be kept for several days without decomposition, but it is exceedingly unstable when no excess of silver oxide or carbonate is present. So long as the solution of silver hypochlorite is shaken up with the silver oxide, it preserves its transparency and bleaching property, but directly it is allowed to stand, and the silver oxide settles, it becomes rapidly cloudy and deposits large flakes of silver chloride, so that the black silver oxide which had settled becomes covered with the white precipitate. The liquid then loses its bleaching properties and contains silver chlorate, _i.e._ AgClO_{3}, in solution, which has a slightly alkaline reaction, owing to the presence of a small amount of dissolved oxide. In this manner the reactions which are consecutively accomplished may be expressed by the equations: 6Cl_{2} + 3Ag_{2}O + 3H_{2}O = 6AgCl + 6HClO; 6HClO + 3Ag_{2}O = 3H_{2}O + 6AgClO; 6AgClO = 4AgCl + 2AgClO_{3}. Hence, Stas gives the following method for the preparation of silver chlorate: A slow current of chlorine is caused to act on oxide of silver, suspended in water which is kept in a state of continual agitation. The shaking is continued after the supply of chlorine has been stopped, in order that the free hypochlorous acid should pass into silver hypochlorite, and the resultant solution of the hypochlorite is drawn off from the sediment of the excess of silver oxide. This solution decomposes spontaneously into silver chloride and chlorate. The pure silver chlorate, AgClO_{3}, does not change under the action of light. The salt is prepared for further use by drying it in dry air at 150°. It is necessary during drying to prevent the access of any organic matter; this is done by filtering the air through cotton wool, and passing it over a layer of red-hot copper oxide. The decomposition of the silver chlorate thus obtained was accomplished by the action of a solution of sulphurous anhydride on it. The salt was first fused by carefully heating it at 243°. The solution of sulphurous anhydride used was one saturated at 0°. Sulphurous anhydride in dilute solutions is oxidised at the expense of silver chlorate, even at low temperatures, with great ease if the liquid be continually shaken, sulphuric acid and silver chloride being formed: AgClO_{3} + 3SO_{2} + 3H_{2}O = AgCl + 3H_{2}SO_{4}. After decomposition, the resultant liquid was evaporated, and the residue of silver chloride weighed. Thus the process consisted in taking a known weight of silver chlorate, converting it into silver chloride, and determining the weight of the latter. The analysis conducted in this manner gave the following results, which, like the preceding, designate the weight in a vacuum calculated from the weights obtained in air: In the first experiment it appeared that 138·7890 grams of silver chlorate gave 103·9795 parts of silver chloride, and in the second experiment that 259·5287 grains of chlorate gave 194·44515 grams of silver chloride, and after fusion 194·4435 grams. The mean result of both experiments, converted into percentages, shows that 100 parts of silver chlorate contain 74·9205 of silver chloride and 25·0795 parts of oxygen. From this it is possible to calculate the combining weight of silver chloride, because in the decomposition of silver chlorate there are obtained three atoms of oxygen and one molecule of silver chloride: AgClO_{3} = AgCl + 3O. Taking the weight of an atom of oxygen to be 16, we find from the mean result that the equivalent weight of silver chloride is equal to 143·395. Thus if O = 16, AgCl = 143·395, and as the preceding experiments show that silver chloride contains 32·8445 parts of chlorine per 100 parts of silver, the weight of the atom of silver[26 bis] must be 107·94 and that of chlorine 35·45. The weight of the atom of sodium is determined from the fact that 21·3633 parts of sodium chloride combine with 32·8445 parts of chlorine; consequently Na = 23·05. This conclusion, arrived at by the analysis of silver chlorate, was verified by means of the analysis of potassium chlorate by decomposing it by heat and determining the weight of the potassium chloride formed, and also by effecting the same decomposition by igniting the chlorate in a stream of hydrochloric acid. The combining weight of potassium chloride was thus determined, and another series of determinations confirmed the relation between chlorine, potassium, and silver, in the same manner as the relation between sodium, chlorine, and silver was determined above. Consequently, the combining weights of sodium, chlorine, and potassium could be deduced by combining these data with the analysis of silver chlorate and the synthesis of silver chloride. The agreement between the results showed that the determinations made by the last method were perfectly correct, and did not depend in any considerable degree on the methods which were employed in the preceding determinations, as the combining weights of chlorine and silver obtained were the same as before. There was naturally a difference, but so small a one that it undoubtedly depended on the errors incidental to every process of weighing and experiment. The atomic weight of silver was also determined by Stas by means of the synthesis of silver sulphide and the analysis of silver sulphate. The combining weight obtained by this method was 107·920. The synthesis of silver iodide and the analysis of silver iodate gave the figure 107·928. The synthesis of silver bromide with the analysis of silver bromate gave the figure 107·921. The synthesis of silver chloride and the analysis of silver chlorate gave a mean result of 107·937. Hence there is no doubt that the combining weight of silver is at least as much as 107·9--greater than 107·90 and less than 107·95, and probably equal to the mean = 107·92. Stas determined the combining weights of many other elements in this manner, such as lithium, potassium, sodium, bromine, chlorine, iodine, and also nitrogen, for the determination of the amount of silver nitrate obtained from a given amount of silver gives directly the combining weight of nitrogen. Taking that of oxygen as 16, he obtained the following combining weights for these elements: nitrogen 14·04, silver 107·93, chlorine 35·46, bromine 79·95, iodine 126·85, lithium 7·02, sodium 23·04, potassium 39·15. These figures differ slightly from those which are usually employed in chemical investigations. They must be regarded as the result of the best observations, whilst the figures usually used in practical chemistry are only approximate--are, so to speak, round numbers for the atomic weights which differ so little from the exact figures (for instance, for Ag 108 instead of 107·92, for Na 23 instead of 23·04) that in ordinary determinations and calculations the difference falls within the limits of experimental error inseparable from such determinations. [26 bis] The results given by Stas' determinations have recently been recalculated and certain corrections have been introduced. We give in the context the average results of van der Plaats and Thomsen's calculations, as well as in Table III. neglecting the doubtful thousandths. The exhaustive investigations conducted by Stas on the atomic weights of the above-named elements have great significance in the solution of the problem as to whether the atomic weights of the elements can be expressed in whole numbers if the unit taken be the atomic weight of hydrogen. Prout, at the beginning of this century, stated that this was the case, and held that the atomic weights of the elements are multiples of the atomic weight of hydrogen. The subsequent determinations of Berzelius, Penny, Marchand, Marignac, Dumas, and more especially of Stas, proved this conclusion to be untenable; since a whole series of elements proved to have fractional atomic weights--for example, chlorine, about 35·5. On account of this, Marignac and Dumas stated that the atomic weights of the elements are expressed in relation to hydrogen, either by whole numbers or by numbers with simple fractions of the magnitudes 1/2 and 1/4. But Stas's researches refute this supposition also. Even between the combining weight of hydrogen and oxygen, there is not, so far as is yet known, that simple relation which is required by _Prout's hypothesis_,[27] _i.e._, taking O = 16, the atomic weight of hydrogen is equal not to 1 but to a greater number somewhere between 1·002 and 1·008 or mean 1·005. Such a conclusion arrived at by direct experiment cannot but be regarded as having greater weight than Prout's supposition (hypothesis) that the atomic weights of the elements are in multiple proportion to each other, which would give reason for surmising (but not asserting) a complexity of nature in the elements, and their common origin from a single primary material, and for expecting their mutual conversion into each other. All such ideas and hopes must now, thanks more especially to Stas, be placed in a region void of any experimental support whatever, and therefore not subject to the discipline of the positive data of science. [27] This hypothesis, for the establishment or refutation of which so many researches have been made, is exceedingly important, and fully deserves the attention which has been given to it. Indeed, if it appeared that the atomic weights of all the elements could be expressed in whole numbers with reference to hydrogen, or if they at least proved to be commensurable with one another, then it could be affirmed with confidence that the elements, with all their diversity, were formed of one material condensed or grouped in various manners into the stable, and, under known conditions, undecomposable groups which we call the atoms of the elements. At first it was supposed that all the elements were nothing else but condensed hydrogen, but when it appeared that the atomic weights of the elements could not be expressed in whole numbers in relation to hydrogen, it was still possible to imagine the existence of a certain material from which both hydrogen and all the other elements were formed. If it should transpire that four atoms of this material form an atom of hydrogen, then the atom of chlorine would present itself as consisting of 142 atoms of this substance, the weight of whose atom would be equal to 0·25. But in this case the atoms of all the elements should be expressed in whole numbers with respect to the weight of the atom of this original material. Let us suppose that the atomic weight of this material is equal to unity, then all the atomic weights should be expressible in whole numbers relatively to this unit. Thus the atom of one element, let us suppose, would weigh _m_, and of another _n_, but, as both _m_ and _n_ must be whole numbers, it follows that the atomic weights of all the elements would be commensurable. But it is sufficient to glance over the results obtained by Stas, and to be assured of their accuracy, especially for silver, in order to entirely destroy, or at least strongly undermine, this attractive hypothesis. We must therefore refuse our assent to the doctrine of the building up from a single substance of the elements known to us. This hypothesis is not supported either by any known transformation (for one element has never been converted into another element), or by the commensurability of the atomic weights of the elements. Although the hypothesis of the formation of all the elements from a single substance (for which Crookes has suggested the name protyle) is most attractive in its comprehensiveness, it can neither be denied nor accepted for want of sufficient data. Marignac endeavoured, however, to overcome Stas's conclusions as to the incommensurability of the atomic weights by supposing that in his, as in the determinations of all other observers, there were unperceived errors which were quite independent of the mode of observation--for example, silver nitrate might be supposed to be an unstable substance which changes, under the heatings, evaporations, and other processes to which it is subjected in the reactions for the determination of the combining weight of silver. It might be supposed, for instance, that silver nitrate contains some impurity which cannot be removed by any means; it might also be supposed that a portion of the elements of the nitric acid are disengaged in the evaporation of the solution of silver nitrate (owing to the decomposing action of water), and in its fusion, and that we have not to deal with normal silver nitrate, but with a slightly basic salt, or perhaps an excess of nitric acid which cannot be removed from the salt. In this case the observed combining weight will not refer to an actually definite chemical compound, but to some mixture for which there does not exist any perfectly exact combining relations. Marignac upholds this proposition by the fact that the conclusions of Stas and other observers respecting the combining weights determined with the greatest exactitude very nearly agree with the proposition of the commensurability of the atomic weights--for example, the combining weight of silver was shown to be equal to 107·93, so that it only differs by 0·08 from the whole number 108, which is generally accepted for silver. The combining weight of iodine proved to be equal to 126·85--that is, it differs from 127 by 0·15. The combining weights of sodium, nitrogen, bromine, chlorine, and lithium are still nearer to the whole or round numbers which are generally accepted. But Marignac's proposition will hardly bear criticism. Indeed if we express the combining weights of the elements determined by Stas in relation to hydrogen, the approximation of these weights to whole numbers disappears, because one part of hydrogen in reality does not combine with 16 parts of oxygen, but with 15·92 parts, and therefore we shall obtain, taking H = 1, not the above-cited figures, but for silver 107·38, for bromine 79·55, magnitudes which are still further removed from whole numbers. Besides which, if Marignac's proposition were true the combining weight of silver determined by one method--_e.g._ by the analysis of silver chlorate combined with the synthesis of silver chloride--would not agree well with the combining weight determined by another method--_e.g._ by means of the analysis of silver iodate and the synthesis of silver iodide. If in one case a basic salt could be obtained, in the other case an acid salt might be obtained. Then the analysis of the acid salt would give different results from that of the basic salt. Thus Marignac's arguments cannot serve as a support for the vindication of Prout's hypothesis. In conclusion, I think it will not be out of place to cite the following passage from a paper I read before the Chemical Society of London in 1889 (Appendix II.), referring to the hypothesis of the complexity of the elements recognised in chemistry, owing to the fact that many have endeavoured to apply the periodic law to the justification of this idea 'dating from a remote antiquity, when it was found convenient to admit the existence of many gods but only one matter.' 'When we try to explain the origin of the idea of a unique primary matter, we easily trace that, in the absence of deductions from experiment, it derives its origin from the scientifically philosophical attempt at discovering some kind of unity in the immense diversity of individualities which we see around. In classical times such a tendency could only be satisfied by conceptions about the immaterial world. As to the material world, our ancestors were compelled to resort to some hypothesis, and they adopted the idea of unity in the formative material, because they were not able to evolve the conception of any other possible unity in order to connect the multifarious relations of matter. Responding to the same legitimate scientific tendency, natural science has discovered throughout the universe a unity of plan, a unity of forces, and a unity of matter; and the convincing conclusions of modern science compel every one to admit these kinds of unity. But while we admit unity in many things, we none the less must also explain the individuality and the apparent diversity which we cannot fail to trace everywhere. It was said of old "Give us a fulcrum and it will become easy to displace the earth." So also we must say, "Give us something that is individualised, and the apparent diversity will be easily understood." Otherwise, how could unity result in a multitude. 'After a long and painstaking research, natural science has discovered the individualities of the chemical elements, and therefore it is now capable, not only of analysing, but also of synthesising; it can understand and grasp generality and unity, as well as the individualised and multifarious. The general and universal, like time and space, like force and motion, vary uniformly. The uniform admit of interpolations, revealing every intermediate phase; but the multitudinous, the individualised--such as ourselves, or the chemical elements, or the members of a peculiar periodic function of the elements, or Dalton's multiple proportions--is characterised in another way. We see in it--side by side with a general connecting principle--leaps, breaks of continuity, points which escape from the analysis of the infinitely small--an absence of complete intermediate links. Chemistry has found an answer to the question as to the causes of multitudes, and while retaining the conception of many elements, all submitted to the discipline of a general law, it offers an escape from the Indian Nirvana--the absorption in the universal--replacing it by the individualised. However, the place for individuality is so limited by the all-grasping, all-powerful universal, that it is merely a point of support for the understanding of multitude in unity.' Among the platinum metals ruthenium, rhodium, and palladium, by their atomic weights and properties, approach silver, just as iron and its analogues (cobalt and nickel) approach copper in all respects. _Gold_ stands in exactly the same position in relation to the heavy platinum metals, osmium, iridium, and platinum, as copper and silver do to the two preceding series. The atomic weight of gold is nearly equal to their atomic weights;[28] it is dense like these metals. It also gives various grades of oxidation, which are feeble, both in a basic and an acid sense. Whilst near to osmium, iridium, and platinum, gold at the same time is able, like copper and silver, to form compounds which answer to the type RX--that is, oxides of the composition R_{2}O. Cuprous chloride, CuCl, silver chloride, AgCl, and aurous chloride, AuCl, are substances which are very much alike in their physical and chemical properties.[28 bis] They are insoluble in water, but dissolve in hydrochloric acid and ammonia, in potassium cyanide, sodium thiosulphate, &c. Just as copper forms a link between the iron metals and zinc, and as silver unites the light platinum metals with cadmium, so also gold presents a transition from the heavy platinum metals to mercury. Copper gives saline compounds of the types CuX and CuX_{2}, silver of the type AgX, whilst gold, besides compounds of the type AuX, very easily and most frequently forms those of the type AuCl_{3}. The compounds of this type frequently pass into those of the lower type, just as PtX_{4} passes into PtX_{2}, and the same is observable in the elements which, in their atomic weights, follow gold. Mercury gives HgX_{2} and HgX, thallium gives TlX_{3} and TlX, lead gives PbX_{4} and PbX_{2}. On the other hand, gold in a qualitative respect differs from silver and copper in the _extreme ease_ with which all its compounds are _reduced to metal_ by many means. This is not only accomplished by many reducing agents, but also by the action of heat. Thus its chlorides and oxides lose their chlorine and oxygen when heated, and, if the temperature be sufficiently high, these elements are entirely expelled and metallic gold alone remains. Its compounds, therefore, act as oxidising agents.[29] [28] It might be expected from the periodic law and analogies with the series iron, cobalt, nickel, copper, zinc, that the atomic weights of the elements of the series osmium, iridium, platinum, gold, mercury, would rise in this order, and at the time of the establishment of the periodic law (1869), the determinations of Berzelius, Rose, and others gave the following values for the atomic weights: Os = 200, Ir = 197, Pt = 198, Au = 196, Hg = 200. The fulfilment of the expectations of the periodic law was given in the first place by the fresh determinations (Seubert, Dittmar, and Arthur) of the atomic weight of platinum, which proved to be nearly 196, if O = 16 (as Marignac, Brauner, and others propose); in the second place, by the fact that Seubert proved that the atomic weight of osmium is really less than that of platinum, and approximately Os = 191; and, in the third place, by the fact that after the researches of Krüss, Thorpe, and Laurie there was no doubt that the atomic weight of gold is greater than that of platinum--namely, nearly 197. [28 bis] In Chapter XXII., Note 40, we gave the thermal data for certain of the compounds of copper of the type CuX_{2}; we will now cite certain data for the cuprous compounds of the type CuX, which present an analogy to the corresponding compounds AgX and AuX, some of which were investigated by Thomsen in his classical work, 'Thermochemische Untersuchungen' (Vol. iii., 1883). The data are given in the same manner as in the above-mentioned note: R = Cu Ag Au R + Cl +33 +29 +6 R + Br +25 +23 0 R + I +16 +14 -6 R + O +41 + 6 -? Thus we see in the first place that gold, which possesses a much smaller affinity than Ag, evolves far less heat than an equivalent amount of copper, giving the same compound, and in the second place that the combination of copper with one atom of oxygen disengages more heat than its combination with one atom of a halogen, whilst with silver the reverse is the case. This is connected with the fact that Cu_{2}O is more stable under the action of heat than Ag_{2}O. [29] Heavy atoms and molecules, although they may present many points of analogy, are more easily isolated; thus C_{16}H_{32}, although, like C_{2}H_{4}, it combines with Br_{2}, and has a similar composition, yet reacts with much greater difficulty than C_{2}H_{4}, and in this it resembles gold; the heavy atoms and molecules are, so to say, inert, and already saturated by themselves. Gold in its higher grade of oxidation, Au_{2}O_{3}, presents feeble basic properties and weakly-developed acid properties, so that this oxide of gold, Au_{2}O_{3}, may be referred to the class of feeble acid oxides, like platinic oxide. This is not the case in the highest known oxides of copper and silver. But in the lower grade of oxidation, aurous oxide, Au_{2}O, gold, like silver and copper, presents basic properties, although they are not very pronounced. In this respect it stands very close in its properties, although not in its types of combination (AuX and AuX_{3}), to platinum (PtX_{2} and PtX_{4}) and its analogues. As yet the general chemical characteristics of gold and its compounds have not been fully investigated. This is partly due to the fact that very few researches have been undertaken on the compounds of this metal, owing to its inaccessibility for working in large quantities. As the atomic weight of gold is high (Au = 197), the preparation of its compounds requires that it should be taken in large quantities, which forms an obstacle to its being fully studied. Hence the facts concerning the history of this metal are rarely distinguished by that exactitude with which many facts have been established concerning other elements more accessible, and long known in use. _In nature_ gold occurs in the primary and chiefly in quartzose rocks, and especially in quartz veins, as in the Urals (at Berezoffsk), in Australia, and in California. The native gold is extracted from these rocks by subjecting them to a mechanical treatment consisting of crushing and washing.[29 bis] Nature has already accomplished a similar disintegration of the hard rocky matter containing gold.[30] These disintegrated rocks, washed by rain and other water, have formed gold-bearing deposits, which are known as _alluvial gold deposits_. Gold-bearing soil is sometimes met with on the surface and sometimes under the upper soil, but more frequently along the banks of dried-up water-courses and running streams. The sand of many rivers contains, however, a very small amount of gold, which it is not profitable to work; for example, that of the Alpine rivers contains 5 parts of gold in 10,000,000 parts of sand. The richest gold deposits are those of Siberia, especially in the southern parts of the Government of Yeniseisk, the South Urals, Mexico, California, South Africa, and Australia, and then the comparatively poorer alluvial deposits of many countries (Hungary, the Alps, and Spain in Europe). The extraction of the gold from alluvial deposits is based on the principle of levigation; the earth is washed, while constantly agitated, by a stream of water, which carries away the lighter portion of the earth, and leaves the coarser particles of the rock and heavier particles of the gold, together with certain substances which accompany it, in the washing apparatus. The extraction of this _washed_ gold only necessitates mechanical appliances,[31] and it is not therefore surprising that gold was known to savages and in the most remote period of history. It sometimes occurs in crystals belonging to the regular system, but in the majority of cases in nuggets or grains of greater or less magnitude. It always contains silver (from very small quantities up to 30 p.c., when it is called 'electrum') and certain other metals, among which lead and rhodium are sometimes found. [29 bis] Sonstadt (1872) showed that sea water, besides silver, always contains gold. Munster (1892) showed that the water of the Norwegian fiords contains about 5 milligrams of gold per ton (or 5 milliardths)--_i.e._ a quantity deserving practical attention, and I think it may be already said that, considering the immeasurable amount of sea water, in time means will be discovered for profitably extracting gold from sea water by bringing it into contact with substances capable of depositing gold upon their surface. The first efforts might be made upon the extraction of salt from sea water, and as the total amount of sea water may be taken as about 2,000,000,000,000,000,000 tons, it follows that it contains about 10,000 million tons of gold. The yearly production of gold is about 200 tons for the whole world, of which about one quarter is extracted in Russia. It is supposed that gold is dissolved in sea water owing to the presence of iodides, which, under the action of animal organisms, yield free iodine. It is thought (as Professor Konovaloff mentions in his work upon 'The Industries of the United States,' 1894) that iodine facilitates the solution of the gold, and the organic matter its precipitation. These facts and considerations to a certain extent explain the distribution of gold in veins or rock fissures, chiefly filled with quartz, because there is sufficient reason for supposing that these rocks once formed the ocean bottom. R. Dentrie, and subsequently Wilkinson, showed that organic matter--for instance, cork--and pyrites are able to precipitate gold from its solutions in that metallic form and state in which it occurs in quartz veins, where (especially in the deeper parts of vein deposits) gold is frequently found on the surface of pyrites, chiefly arsenical pyrites. Kazantseff (in Ekaterinburg, 1891) even supposes, from the distribution of the gold in these pyrites, that it occurred in solution as a compound of sulphide of gold and sulphide of arsenic when it penetrated into the veins. It is from such considerations that the origin of vein and pyritic gold is, at the present time, attributed to the reaction of solutions of this metal, the remains of which are seen in the gold still present in sea water. [30] However, in recent times, especially since about 1870, when chlorine (either as a solution of the gas or as bleaching powder) and bromine began to be applied to the extraction of finely-divided gold from poor ores (previously roasted in order to drive off arsenic and sulphur, and oxidise the iron), the extraction of gold from quartz and pyrites, by the wet method, increases from year to year, and begins to equal the amount extracted from alluvial deposits. Since the nineties the _cyanide process_ (Chapter XIII., Note 13 bis) has taken an important place among the wet methods for extracting gold from its ores. It consists in pouring a dilute solution of cyanide of potassium (about 500 parts of water and 1 to 4 parts of cyanide of potassium per 1,000 parts of ore, the amount of cyanide depending upon the richness of the ore) and a mixture of it with NaCN, (_see_ Chapter XIII., Note 12) over the crushed ore (which need not be roasted, whilst roasting is indispensable in the chlorination process, as otherwise the chlorine is used up in oxidising the sulphur, arsenic, &c.) The gold is dissolved very rapidly even from pyrites, where it generally occurs on the surface in such fine and adherent particles that it either cannot be mechanically washed away, or, more frequently is carried away by the stream of water, and cannot be caught by mechanical means or by the mercury used for catching the gold in the sluices. Chlorination had already given the possibility of extracting the finest particles of gold; but the cyanide process enables such pyrites to be treated as could be scarcely worked by other means. The treatment of the crushed ore by the KCN is carried on in simple wooden vats (coated with paraffin or tar) with the greatest possible rapidity (in order that the KCN solution should not have time to change) by a method of systematic lixiviation, and is completed in 10 to 12 hours. The resultant solution of gold, containing AuK(CN)_{2}, is decomposed either with freshly-made zinc filings (but when the gold settles on the Zn, the cyanide solution reacts upon the Zn with the evolution of H_{2} and formation of ZnH_{2}O_{2}) or by sodium amalgam prepared at the moment of reaction by the action of an electric current upon a solution of NaHO poured into a vessel partially immersed in mercury (the NaCN is renewed continually by this means). The silver in the ore passes into solution, together with the gold, as in amalgamation. [31] But the particles of gold are sometimes so small that a large amount is lost during the washing. It is then profitable to have recourse to the extraction by chlorine and KCN (Note 30). In speaking of the extraction of gold the following remarks may not be out of place: In California advantage is taken of water supplied from high altitudes in order to have a powerful head of water, with which the rocks are directly washed away, thus avoiding the greater portion of the mechanical labour required for the exploitation of these deposits. The last residues of gold are sometimes extracted from sand by washing them with mercury, which dissolves the gold. The sand mixed with water is caused to come into contact with mercury during the washing. The mercury is then distilled. Many sulphurous ores, even pyrites, contain a small amount of gold. Compounds of gold with bismuth, BiAu_{2}, tellurium, AuTe_{2} (calverite), &c., have been found, although rarely. Among the minerals which accompany gold, and from which the presence of gold may be expected, we may mention white quartz, titanic and magnetic iron ores, and also the following, which are of rarer occurrence: zircon, topaz, garnet, and such like. The concentrated gold washings first undergo a mechanical treatment, and the impure gold obtained is treated for pure gold by various methods. If the gold contain a considerable amount of foreign metals, especially lead and copper, it is sometimes cupelled, like silver, so that the oxidisable metals may be absorbed by the cupel in the form of oxides, but in every case the gold is obtained together with silver, because the latter metal also is not oxidised. Sometimes the gold is extracted by means of mercury, that is, by amalgamation (and the mercury subsequently driven off by distillation), or by smelting it with lead (which is afterwards removed by oxidation) and processes like those employed for the extraction of silver, because gold, like silver, does not oxidise, is dissolved by lead and mercury, and is non-volatile. If copper or any other metal contain gold and it be employed as an anode, pure copper will be deposited upon the cathode, while all the gold will remain at the anode as a slime. This method often amply repays the whole cost of the process, since it gives, besides the gold, a pure electrolytic copper. _The separation of the silver_ from gold is generally carried on with great precision, as the presence of the silver in the gold does not increase its value for exchange, and it can be substituted by other less valuable metals, so that the extraction of the silver, as a precious metal, from its alloy with gold, is a profitable operation. This separation is conducted by different methods. Sometimes the argentiferous gold is melted in crucibles, together with a mixture of common salt and powdered bricks. The greater portion of the silver is thus converted into the chloride, which fuses and is absorbed by the slags, from which it may be extracted by the usual methods. The silver is also extracted from gold by treating it with boiling sulphuric acid, which does not act on the gold but dissolves the silver. But if the alloy does not contain a large proportion of silver it cannot be extracted by this method or at all events the separation will be imperfect, and therefore a fresh amount of silver is added (by fusion) to the gold, in such quantity that the alloy contains twice as much silver as gold. The silver which is added is preferably such as contains gold, which is very frequently the case. The alloy thus formed is poured in a thin stream into water, by which means it is obtained in a granulated form; it is then boiled with strong sulphuric acid, three parts of acid being used to one part of alloy. The sulphuric acid extracts all the silver without acting on the gold. It is best, however, to pour off the first portion of the acid, which has dissolved the silver, and then treat the residue of still imperfectly pure gold with a fresh quantity of sulphuric acid. The gold is thus obtained in the form of powder, which is washed with water until it is quite free from silver. The silver is precipitated from the solution by means of copper, so that cupric sulphate and metallic silver are obtained. This process is carried out in many countries, as in Russia, at the Government mints. Gold is generally used alloyed with copper; since pure gold, like pure silver, is very soft, and therefore soon worn away. In assaying or determining the amount of pure gold in such an alloy it is usual to add silver to the gold in order to make up an alloy containing three parts of silver to one of gold (this is known as quartation because the alloy contains 1/4 of gold), and the resultant alloy is treated with nitric acid. If the silver be not in excess over the gold, it is not all dissolved by the nitric acid, and this is the reason for the quartation. The amount of pure gold (assay) is determined by weighing the gold which remains after this treatment. English gold (= 22 carats) coinage is composed of an alloy containing 91·66 p.c. of gold, but for many articles gold is frequently used containing a larger amount of foreign metals. _Pure gold_ may be obtained from gold alloys by dissolving in aqua regia, and then adding ferrous sulphate to the solution or heating it with a solution of oxalic acid. These deoxidising agents reduce the gold, but not the other metals. The chlorine combined with the gold then acts like free chlorine. The gold, thus reduced, is precipitated as an exceedingly fine brown powder.[31 bis] It is then washed with water, and fused with nitre or borax. Pure gold reflects a yellow light, and in the form of very thin sheets (gold leaf), into which it can be hammered and rolled,[31 tri] it transmits a bluish-green light. The specific gravity of gold is about 19·5, the sp. gr. of gold coin is about 17·1. It fuses at 1090°--at a higher temperature than silver--and can be drawn into exceedingly fine wires or hammered into thin sheets. With its softness and ductility, gold is distinguished for its tenacity, and a gold wire two millimetres thick breaks only under a load of 68 kilograms. Gold vaporises even at a furnace heat, and imparts a greenish colour to a flame passing over it in a furnace. Gold alloys with copper almost without changing its volume.[32] In its chemical aspect, gold presents, as is already seen from its general characteristics given above, an example of the so-called noble metals--_i.e._ it is incapable of being oxidised at any temperature, and its oxide is decomposed when calcined. Only chlorine and bromine combine directly with it at the ordinary temperature, but many other metals and non-metals combine with it at a red heat--for example, sulphur, phosphorus, and arsenic. Mercury dissolves it with great ease. It dissolves in potassium cyanide in the presence of air; a mixture of sulphuric acid with nitric acid dissolves it with the aid of heat, although in small quantity. It is also soluble in aqua regia and in selenic acid. Sulphuric, hydrochloric, nitric, and hydrofluoric acids and the caustic alkalis do not act on gold, but a mixture of hydrochloric acid with such oxidising agents as evolve chlorine naturally dissolves it like aqua regia.[32 bis] [31 bis] Schottländer (1893) obtained gold in a soluble colloid form (the solution is violet) by the action of a mixture of solutions of cerium acetate and NaHO upon a solution of AuCl_{3}. The gold separates out from such a solution in exactly the same manner as Ag does from the solution of colloid silver mentioned above. There always remains a certain amount of a higher oxide of cerium, CeO_{2}, in the solution--_i.e._ the gold is reduced by converting the cerium into a higher grade of oxidation. Besides which Krüss and Hofmann showed that sulphide of gold precipitated by the action of H_{2}S upon a solution of AuKCy_{2} mixed with HCl easily passes into a colloid solution after being properly washed (like As_{2}S_{3}, CuS, &c., Chapter I., Note 57). [31 tri] Gold-leaf is used for gilding wood (leather, cardboard, and suchlike, upon which it is glued by means of varnish, &c.), and is about 0·003 millimetre thick. It is obtained from thin sheets (weighing at first about 1/4 grm. to a square inch), rolled between gold rollers, by gradually hammering them (in packets of a number at once) between sheets of moist (but not wet) parchment, and then, after cutting them into four pieces, between a specially prepared membrane, which, when at the right degree of moisture, does not tear or stick together under the blows of the hammer. [32] The formation of the alloys Cu + Zn, Cu + Sn, Cu + Bi, Cu + Sb, Pb + Sb, Ag + Pb, Ag + Sn, Au + Zn, Au + Sn, &c., is accompanied by a contraction (and evolution of heat). The formation of the alloys Fe + Sb, Fe + Pb, Cu + Pb, Pb + Sn, Pb + Sb, Zn + Sb, Ag + Cu, Au + Cu, Au + Pb, takes place with a certain increase in volume. With regard to the alloys of gold, it may be mentioned that gold is only slightly dissolved by mercury (about 0·06 p.c., Dudley, 1890); the remaining portion forms a granular alloy, whose composition has not been definitely determined. Aluminium (and silicon) also have the capacity of forming alloys with gold. The presence of a small amount of aluminium lowers the melting point of gold considerably (Roberts-Austen, 1892); thus the addition of 4 p.c. of aluminium lowers it by 14°·28, the addition of 10 p.c. Al by 41°·7. The latter alloy is white. The alloy AuAl_{2} has a characteristic purple colour, and its melting point is 32°·5 above that of gold, which shows it to be a definite compound of the two metals. The melting points of alloys richer in Al gradually fall to 660°--that is, below that of aluminium (665°). Heycock and Neville (1892), in studying the triple alloys of Au, Cd, and Sn, observed a tendency in the gold to give compounds with Cd, and by sealing a mixture of Au and Cd in a tube, from which the air had been exhausted, and heating it, they obtained a grey crystalline brittle definite alloy AuCd. [32 bis] Calderon (1892), at the request of some jewellers, investigated the cause of a peculiar alteration sometimes found on the surface of dead-gold articles, there appearing brownish and blackish spots, which widen and alter their form in course of time. He came to the conclusion that these spots are due to the appearance and development of peculiar micro-organisms (Aspergillus niger and Micrococcus cimbareus) on the gold, spores of which were found in abundance on the cotton-wool in which the gold articles had been kept. As regards the compounds of gold, they belong, as was said above, to the types AuX_{3} and AuX. _Auric chloride_ or _gold trichloride_, AuCl_{3}, which is formed when gold is dissolved in aqua regia, belongs to the former and higher of these types. The solution of this substance in water has a yellow colour, and it may be obtained pure by evaporating the solution in aqua regia to dryness, but not to the point of decomposition. If the evaporation proceed to the point of crystallisation, a compound of gold chloride and hydrochloric acid, AuHCl_{4}, is obtained, like the allied compounds of platinum; but it easily parts with the acid and leaves auric chloride, which fuses into a red-brown liquid, and then solidifies to a crystalline mass. If dry chlorine be passed over gold in powder it forms a mixture of aurous and auric chlorides, but the aurous chloride is also decomposed by water into gold and auric chloride. Auric chloride crystallises from its solutions as AuCl_{3},2H_{2}O, which easily loses water, and the dry chloride loses two-thirds of its chlorine at 185°, forming aurous chloride, whilst above 300° the latter chloride also loses its chlorine and leaves metallic gold. Auric chloride is the usual form in which gold occurs in solutions, and in which its salts are used in the arts and for chemical purposes. It is soluble in water, alcohol, and ether. Light has a reducing action on these solutions, and after a time metallic gold is deposited upon the sides of vessels containing the solution. Hydrogen when nascent, and even in a gaseous form, reduces gold from this solution to a metallic state. The reduction is more conveniently and usually effected by ferrous sulphate, and in general by the action of ferrous salts.[33] [33] Stannous chloride as a reducing agent also acts on auric chloride, and gives a red precipitate known as _purple of Cassius_. This substance, which probably contains a mixture or compound of aurous oxide and tin oxide, is used as a red pigment for china and glass. Oxalic acid, on heating, reduces metallic gold from its salts, and this property may be taken advantage of for separating it from its solutions. The oxidation which then takes place in the presence of water may be expressed by the following equation: 2AuCl_{3} + 3C_{2}H_{2}O_{4} = 2Au + 6HCl + 6CO_{2}. Nearly all organic substances have a reducing action on gold, and solutions of gold leave a violet stain on the skin. Auric chloride, like platinic chloride, is distinguished for its clearly-developed property of forming double salts. These double salts, as a rule, belong to the type AuMCl_{4}. The compound of auric chloride with hydrochloric acid mentioned above evidently belongs to the same type. The compounds 2KAuCl_{4},5H_{2}O, NaAuCl_{4},2H_{2}O, AuNH_{4}Cl_{4},H_{2}O, Mg(AuCl_{4})_{2},2H_{2}O, and the like are easily crystallised in well-formed crystals. Wells, Wheeler, and Penfield (1892) obtained RbAuCl_{4} (reddish yellow) and CsAuCl_{4} (golden yellow), and corresponding bromides (dark coloured). AuBr_{3} is extremely like the chloride. Auric cyanide is obtained easily in the form of a double salt of potassium, KAu(CN)_{4} by mixing saturated and hot solutions of potassium cyanide with auric chloride and then cooling. If a solution of potassium hydroxide be added to a solution of auric chloride, a precipitate is first formed, which re-dissolves in an excess of the alkali. On being evaporated under the receiver of an air-pump, this solution yields yellow crystals, which present the same composition as the double salts AuMCl_{4}, with the substitution of the chlorine by oxygen--that is to say, _potassium aurate_, AuKO_{2}, is formed in crystals containing 3H_{2}O. The solution has a distinctly alkaline reaction. _Auric oxide_, Au_{2}O_{3}, separates when this alkaline solution is boiled with an excess of sulphuric acid. But it then still retains some alkali; however, it may be obtained in a pure state as a brown powder by dissolving in nitric acid and diluting with water. The brown powder decomposes below 250° into gold and oxygen. It is insoluble in water and in many acids, but it dissolves in alkalis, which shows the acid character of this oxide. An hydroxide, Au(OH)_{3} may be obtained as a brown powder by adding magnesium oxide to a solution of auric chloride and treating the resultant precipitate of magnesium aurate with nitric acid. This hydroxide loses water at 100°, and gives auric oxide.[34] [34] If ammonia be added to a solution of auric chloride, it forms a yellow precipitate of the so-called fulminating gold, which contains gold, chlorine, hydrogen, nitrogen, and oxygen, but its formula is not known with certainty. It is probably a sort of ammonio-metallic compound, Au_{2}O_{3},4NH_{3}, or amide (like the mercury compound). This precipitate explodes at 140°, but when left in the presence of solutions containing ammonia it loses all its chlorine and becomes non-explosive. In this form the composition Au_{2}O_{3},2NH_{3},H_{2}O is ascribed to it, but this is uncertain. Auric sulphide, Au_{2}S_{3}, is obtained by the action of hydrogen sulphide on a solution of auric chloride, and also directly by fusing sulphur with gold. It has an acid character, and therefore dissolves in sodium and ammonium sulphides. The starting-point of the compounds of the type AuX[35] is _gold monochloride_ or _aurous chloride_, AuCl, which is formed, as mentioned above, by heating auric chloride at 185°. Aurous chloride forms a yellowish-white powder; this, when heated with water, is decomposed into metallic gold and auric chloride, which passes into solution: 3AuCl = AuCl_{3} + 2Au. This decomposition is accelerated by the action of light. Hence it is obvious that the compounds corresponding with aurous oxide are comparatively unstable. But this only refers to the simple compounds AuX; some of the complex compounds, on the contrary, form the most stable compounds of gold. Such, for example, is the cyanide of gold and potassium, AuK(CN)_{2}. It is formed, for instance, when finely-divided gold dissolves in the presence of air in a solution of potassium cyanide: 4KCN + 2Au + H_{2}O + O = 2KAu(CN)_{2} + 2KHO (this reaction also proceeds with solid pieces of gold, although very slowly). The same compound is formed in solution when many compounds of gold are mixed with potassium cyanide, because if a higher compound of gold be taken, it is reduced by the potassium cyanide into aurous oxide, which dissolves in potassium cyanide and forms KAu(CN)_{2}. This substance is soluble in water, and gives a colourless solution, which can be kept for a long time, and is employed in electro-gilding--that is, for coating other metallic objects with a layer of gold, which is deposited if the object be connected with the negative pole of a battery and the positive pole consist of a gold plate. When an electric current is passed between them, the gold from the latter will dissolve, whilst a coating of gold from the solution will be deposited on the object. [35] Many double salts of suboxide of gold belong to the type AuX--for instance, the cyanide corresponding to the type AuKX_{2}, like PtK_{2}X_{4}, with which we became acquainted in the last chapter. We will enumerate several of the representatives of this class of compounds. If auric chloride, AuCl_{3}, be mixed with a solution of sodium thiosulphate, the gold passes into a colourless solution, which deposits colourless crystals, containing a double thiosulphate of gold and sodium, which are easily soluble in water but are precipitated by alcohol. The composition of this salt is Na_{3}Au(S_{2}O_{3})_{2},2H_{2}O. If the sodium thiosulphate be represented as NaS_{2}O_{3}Na, the double salt in question will be AuNa(S_{2}O_{3}Na)_{2},2H_{2}O, according to the type AuNaX_{2}. The solution of this colourless and easily crystallisable salt has a sweet taste, and the gold is not separated from it either by ferrous sulphate or oxalic acid. This salt, which is known as _Fordos and Gelis's salt_, is used in medicine and photography. In general, aurous oxide exhibits a distinct inclination to the formation of similar double salts, as we saw also with PtX_{2}--for example, it forms similar salts with sulphurous acid. Thus if a solution of sodium sulphite be gradually added to a solution of oxide of gold in sodium hydroxide, the precipitate at first formed re-dissolves to a colourless solution, which contains the double salt Na_{3}Au(SO_{3})_{2} = AuNa(SO_{3}Na)_{2}. The solution of this salt, when mixed with barium chloride, first forms a precipitate of barium sulphite, and then a red barium double salt which corresponds with the above sodium salt. The oxygen compound of the type AuX, _aurous oxide_, Au_{2}O, is obtained as a greenish violet powder on mixing aurous chloride with potassium chloride in the cold. With hydrochloric acid this oxide gives gold and auric chloride, and when heated it easily splits up into oxygen and metallic gold. APPENDIX I AN ATTEMPT TO APPLY TO CHEMISTRY ONE OF THE PRINCIPLES OF NEWTON'S NATURAL PHILOSOPHY BY PROFESSOR MENDELÉEFF A LECTURE DELIVERED AT THE ROYAL INSTITUTION OF GREAT BRITAIN ON FRIDAY, MAY 31, 1889 Nature, inert to the eyes of the ancients, has been revealed to us as full of life and activity. The conviction that motion pervaded all things, which was first realised with respect to the stellar universe, has now extended to the unseen world of atoms. No sooner had the human understanding denied to the earth a fixed position and launched it along its path in space, than it was sought to fix immovably the sun and the stars. But astronomy has demonstrated that the sun moves with unswerving regularity through the star-set universe at the rate of about 50 kilometres per second. Among the so-called fixed stars are now discerned manifold changes and various orders of movement. Light, heat, electricity--like sound--have been proved to be modes of motion; to the realisation of this fact modern science is indebted for powers which have been used with such brilliant success, and which have been expounded so clearly at this lecture table by Faraday and by his successors. As, in the imagination of Dante, the invisible air became peopled with spiritual beings, so before the eyes of earnest investigators, and especially before those of Clerk Maxwell, the invisible mass of gases became peopled with particles: their rapid movements, their collisions, and impacts became so manifest that it seemed almost possible to count the impacts and determine many of the peculiarities or laws of their collisions. The fact of the existence of these invisible motions may at once be made apparent by demonstrating the difference in the rate of diffusion through porous bodies of the light and rapidly moving atoms of hydrogen and the heavier and more sluggish particles of air. Within the masses of liquid and of solid bodies we have been forced to acknowledge the existence of persistent though limited motion of their ultimate particles, for otherwise it would be impossible to explain, for example, the celebrated experiments of Graham on diffusion through liquid and colloidal substances. If there were, in our times, no belief in the molecular motion in solid bodies, could the famous Spring have hoped to attain any result by mixing carefully-dried powders of potash, saltpetre and sodium acetate, in order to produce, by pressure, a chemical reaction between these substances through the interchange of their metals, and have derived, for the conviction of the incredulous, a mixture of two hygroscopic though solid salts--sodium nitrate and potassium acetate? In these invisible and apparently chaotic movements, reaching from the stars to the minutest atoms, there reigns, however, a harmonious order which is commonly mistaken for complete rest, but which is really a consequence of the conservation of that dynamic equilibrium which was first discerned by the genius of Newton, and which has been traced by his successors in the detailed analysis of the particular consequences of the great generalisation, namely, relative immovability in the midst of universal and active movement. But the unseen world of chemical changes is closely analogous to the visible world of the heavenly bodies, since our atoms form distinct portions of an invisible world, as planets, satellites, and comets form distinct portions of the astronomer's universe; our atoms may therefore be compared to the solar systems, or to the systems of double or of single stars: for example, ammonia (NH_{3}) may be represented in the simplest manner by supposing the sun, nitrogen, surrounded by its planets of hydrogen; and common salt (NaCl) may be looked on as a double star formed of sodium and chlorine. Besides, now that the indestructibility of the elements has been acknowledged, chemical changes cannot otherwise be explained than as changes of motion, and the production by chemical reactions of galvanic currents, of light, of heat, of pressure, or of steam power, demonstrates visibly that the processes of chemical reaction are inevitably connected with enormous though unseen displacements, originating in the movements of atoms in molecules. Astronomers and natural philosophers, in studying the visible motions of the heavenly bodies and of matter on the earth, have understood and have estimated the value of this store of energy. But the chemist has had to pursue a contrary course. Observing in the physical and mechanical phenomena which accompany chemical reactions the quantity of energy manifested by the atoms and molecules, he is constrained to acknowledge that within the molecules there exist atoms in motion, endowed with an energy which, like matter itself, is neither being created nor capable of being destroyed. Therefore, in chemistry, we must seek dynamic equilibrium not only between the molecules, but also in their midst among their component atoms. Many conditions of such equilibrium have been determined, but much remains to be done, and it is not uncommon, even in these days, to find that some chemists forget that there is the possibility of motion in the interior of molecules, and therefore represent them as being in a condition of death-like inactivity. Chemical combinations take place with so much ease and rapidity, possess so many special characteristics, and are so numerous, that their simplicity and order were for a long time hidden from investigators. Sympathy, relationship, all the caprices or all the fancifulness of human intercourse, seemed to have found complete analogies in chemical combinations, but with this difference, that the characteristics of the material substances--such as silver, for example, or of any other body--remain unchanged in every subdivision from the largest masses to the smallest particles, and consequently these characteristics must be properties of the particles. But the world of heavenly luminaries appeared equally fanciful at man's first acquaintance with it, so much so, that the astrologers imagined a connection between the individualities of men and the conjunctions of planets. Thanks to the genius of Lavoisier and of Dalton, man has been able, in the unseen world of chemical combinations, to recognise laws of the same simple order as those which Copernicus and Kepler proved to exist in the planetary universe. Man discovered, and continues every hour to discover, _what_ remains unchanged in chemical evolution, and _how_ changes take place in combinations of the unchangeable. He has learned to predict, not only what possible combinations may take place, but also the very existence of atoms of unknown elementary substances, and has besides succeeded in making innumerable practical applications of his knowledge to the great advantage of his race, and has accomplished this notwithstanding that notions of sympathy and affinity still preserve a strong vitality in science. At present we cannot apply Newton's principles to chemistry, because the soil is only being now prepared. The invisible world of chemical atoms is still waiting for the creator of chemical mechanics. For him our age is collecting a mass of materials, the inductions of well-digested facts, and many-sided inferences similar to those which existed for Astronomy and Mechanics in the days of Newton. It is well also to remember that Newton devoted much time to chemical experiments, and while considering questions of celestial mechanics, persistently kept in view the mutual action of those infinitely small worlds which are concerned in chemical evolutions. For this reason, and also to maintain the unity of laws, it seems to me that we must, in the first instance, seek to harmonise the various phases of contemporary chemical theories with the immortal principles of the Newtonian natural philosophy, and so hasten the advent of true chemical mechanics. Let the above considerations serve as my justification for the attempt which I propose to make to act as a champion of the universality of the Newtonian principles, which I believe are competent to embrace every phenomenon in the universe, from the rotation of the fixed stars to the interchanges of chemical atoms. In the first place I consider it indispensable to bear in mind that, up to quite recent times, only a one-sided affinity has been recognised in chemical reactions. Thus, for example, from the circumstance that red-hot iron decomposes water with the evolution of hydrogen, it was concluded that oxygen had a greater affinity for iron than for hydrogen. But hydrogen, in presence of red-hot iron scale, appropriates its oxygen and forms water, whence an exactly opposite conclusion may be formed. During the last ten years a gradual, scarcely perceptible, but most important change has taken place in the views, and consequently in the researches, of chemists. They have sought everywhere, and have always found, systems of conservation or dynamic equilibrium substantially similar to those which natural philosophers have long since discovered in the visible world, and in virtue of which the position of the heavenly bodies in the universe is determined. There where one-sided affinities only were at first detected, not only secondary or lateral ones have been found, but even those which are diametrically opposite; yet among these, dynamical equilibrium establishes itself not by excluding one or other of the forces, but regulating them all. So the chemist finds in the flame of the blast furnace, in the formation of every salt, and, with especial clearness, in double salts and in the crystallisation of solutions, not a fight ending in the victory of one side, as used to be supposed, but the conjunction of forces; the peace of dynamic equilibrium resulting from the action of many forces and affinities. Carbonaceous matters, for example, burn at the expense of the oxygen of the air, yielding a quantity of heat, and forming products of combustion, in which it was thought that the affinities of the oxygen with the combustible elements were satisfied. But it appeared that the heat of combustion was competent to decompose these products, to dissociate the oxygen from the combustible elements, and therefore to explain combustion fully it is necessary to take into account the equilibrium between opposite reactions, between those which evolve and those which absorb heat. In the same way, in the case of the solution of common salt in water, it is necessary to take into account, on the one hand, the formation of compound particles generated by the combination of salt with water, and, on the other, the disintegration or scattering of the new particles formed, as well as of these originally contained. At present we find two currents of thought, apparently antagonistic to each other, dominating the study of solutions: according to the one, solution seems a mere act of building up or association; according to the other, it is only dissociation or disintegration. The truth lies, evidently, between these views; it lies, as I have endeavoured to prove by my investigations into aqueous solutions, in the dynamic equilibrium of particles tending to combine and also to fall asunder. The large majority of chemical reactions which appeared to act victoriously along one line have been proved capable of acting as victoriously even along an exactly opposite line. Elements which utterly decline to combine directly may often be formed into comparatively stable compounds by indirect means, as, for example, in the case of chlorine and carbon; and consequently the sympathies and antipathies which it was thought to transfer from human relations to those of atoms should be laid aside until the mechanism of chemical relations is explained. Let us remember, however, that chlorine, which does not form with carbon the chloride of carbon, is strongly absorbed, or, as it were, dissolved, by carbon, which leads us to suspect incipient chemical action even in an external and purely surface contact, and involuntarily gives rise to conceptions of that unity of the forces of nature which has been so energetically insisted on by Sir William Grove and formulated in his famous paradox. Grove noticed that platinum, when fused in the oxyhydrogen flame, during which operation water is formed, when allowed to drop into water decomposes the latter and produces the explosive oxyhydrogen mixture. The explanation of this paradox, as of many others which arose during the period of chemical renaissance, has led, in our time, to the promulgation by Henri Sainte-Claire Deville of the conception of dissociation and of equilibrium, and has recalled the teaching of Berthollet, which, notwithstanding its brilliant confirmation by Heinrich Rose and Dr. Gladstone, had not, up to that period, been included in received chemical views. Chemical equilibrium in general, and dissociation in particular, are now being so fully worked out in detail, and supplied in such various ways, that I do not allude to them to develop, but only use them as examples by which to indicate the correctness of a tendency to regard chemical combinations from points of view differing from those expressed by the term hitherto appropriated to define chemical forces, namely, 'affinity.' Chemical equilibria, dissociation, the speed of chemical reactions, thermochemistry, spectroscopy, and, more than all, the determination of the influence of masses and the search for a connection between the properties and weights of atoms and molecules--in one word, the vast mass of the most important chemical researches of the present day--clearly indicate the near approach of the time when chemical doctrines will submit fully and completely to the doctrine which was first announced in the _Principia_ of Newton. In order that the application of these principles may bear fruit it is evidently insufficient to assume that statical equilibrium reigns alone in chemical systems or chemical molecules: it is necessary to grasp the conditions of possible states of dynamical equilibria, and to apply to them kinetic principles. Numerous considerations compel us to renounce the idea of statical equilibrium in molecules, and the recent yet strongly-supported appeals to dynamic principles constitute, in my opinion, the foundation of the modern teaching relating to atomicity, or the valency of the elements, which usually forms the basis of investigations into organic or carbon compounds. This teaching has led to brilliant explanations of very many chemical relations and to cases of isomerism, or the difference in the properties of substances having the same composition. It has been so fruitful in its many applications and in the foreshadowing of remote consequences, especially respecting carbon compounds, that it is impossible to deny its claims to be ranked as a great achievement of chemical science. Its practical application to the synthesis of many substances of the most complicated composition entering into the structure of organised bodies, and to the creation of an unlimited number of carbon compounds, among which the colours derived from coal tar stand prominently forward, surpass the synthetical powers of Nature itself. Yet this teaching, as applied to the structure of carbon compounds, is not on the face of it directly applicable to the investigation of other elements, because in examining the first it is possible to assume that the atoms of carbon have always a definite and equal number of affinities, whilst in the combinations of other elements this is evidently inadmissible. Thus, for example, an atom of carbon yields only one compound with four atoms of hydrogen and one with four atoms of chlorine in the molecule, whilst the atoms of chlorine and hydrogen unite only in the proportions of one to one. Simplicity is here evident, and forms a point of departure from which it is easy to move forward with firm and secure tread. Other elements are of a different nature. Phosphorus unites with three and with five atoms of chlorine, and consequently the simplicity and sharpness of the application of structural conceptions are lost. Sulphur unites only with two atoms of hydrogen, but with oxygen it enters into higher orders of combination. The periodic relationship which exists among all the properties of the elements--such, for example, as their ability to enter into various combinations--and their atomic weights, indicate that this variation in atomicity is subject to one perfectly exact and general law, and it is only carbon and its near analogues which constitute cases of permanently preserved atomicity. It is impossible to recognise as constant and fundamental properties of atoms, powers which, in substance, have proved to be variable. But by abandoning the idea of permanence, and of the constant saturation of affinities--that is to say, by acknowledging the possibility of free affinities--many retain a comprehension of the atomicity of the elements 'under given conditions;' and on this frail foundation they build up structures composed of chemical molecules, evidently only because the conception of manifold affinities gives, at once, a simple statical method of estimating the composition of the most complicated molecules. I shall enter neither into details, nor into the various consequences following from these views, nor into the disputes which have sprung up respecting them (and relating especially to the number of isomerides possible on the assumption of free affinities), because the foundation or origin of theories of this nature suffers from the radical defect of being in opposition to dynamics. The molecule, as even Laurent expressed himself, is represented as an architectural structure, the style of which is determined by the fundamental arrangement of a few atoms, whilst the decorative details, which are capable of being varied by the same forces, are formed by the elements entering into the combination. It is on this account that the term 'structural' is so appropriate to the contemporary views of the above order, and that the 'structuralists' seek to justify the tetrahedric, plane, or prismatic disposition of the atoms of carbon in benzene. It is evident that the consideration relates to the statical position of atoms and molecules and not to their kinetic relations. The atoms of the structural type are like the lifeless pieces on a chess board: they are endowed but with the voices of living beings, and are not those living beings themselves; acting, indeed, according to laws, yet each possessed of a store of energy which, in the present state of our knowledge, must be taken into account. In the days of Haüy, crystals were considered in the same statical and structural light, but modern crystallographers, having become more thoroughly acquainted with their physical properties and their actual formation, have abandoned the earlier views, and have made their doctrines dependent on dynamics. The immediate object of this lecture is to show that, starting with Newton's third law of motion, it is possible to preserve to chemistry all the advantages arising from structural teaching, without being obliged to build up molecules in solid and motionless figures, or to ascribe to atoms definite limited valencies, directions of cohesion, or affinities. The wide extent of the subject obliges me to treat only a small portion of it, namely of _substitutions_, without specially considering combinations and decompositions, and even then limiting myself to the simplest examples, which, however, will throw open prospects embracing all the natural complexity of chemical relations. For this reason, if it should prove possible to form groups similar, for example, to H_{4} or CH_{6} as the remnants of molecules CH_{4} or C_{2}H_{7} we shall not pause to consider them, because, as far as we know, they fall asunder into two parts, H_{2} + H_{2} or CH_{4} + H_{2}, as soon as they are even temporarily formed, and are incapable of separate existence, and therefore can take no part in the elementary act of substitution. With respect to the simplest molecules which we shall select--that is to say, those of which the parts have no separate existence, and therefore cannot appear in substitutions--we shall consider them according to the periodic law, arranging them in direct dependence on the atomic weight of the elements. Thus, for example, the molecules of the simplest hydrogen compounds-- HF H_{2}O H_{3}N H_{4}C hydrofluoric acid water ammonia methane correspond with elements the atomic weights of which decrease consecutively F = 19, O = 16, N = 14, C = 12. Neither the arithmetical order (1, 2, 3, 4 atoms of hydrogen) nor the total information we possess respecting the elements will permit us to interpolate into this typical series one more additional element; and therefore we have here, for hydrogen compounds, a natural base on which are built up those simple chemical combinations which we take as typical. But even they are competent to unite with each other, as we see, for instance, in the property which hydrofluoric acid has of forming a hydrate--that is, of combining with water; and a similar attribute of ammonia, resulting in the formation of a caustic alkali, NH_{3},H_{2}O, or NH_{4}OH. Having made these indispensable preliminary observations, I may now attack the problem itself and attempt to explain the so-called structure or rather construction, of molecules--that is to say, their constitution and transformations--without having recourse to the teaching of 'structuralists,' but on Newton's dynamical principles. Of Newton's three laws of motion, only the third can be applied directly to chemical molecules when regarded as systems of atoms among which it must be supposed that there exist common influences or forces, and resulting compounded relative motions. Chemical reactions of every kind are undoubtedly accomplished by changes in these internal movements, respecting the nature of which nothing is known at present, but the existence of which the mass of evidence collected in modern times forces us to acknowledge as forming part of the common motion of the universe, and as a fact further established by the circumstance that chemical reactions are always characterised by changes of volume or the relations between the atoms or the molecules. Newton's third law, which is applicable to every system, declares that, 'action is also associated with reaction, and is equal to it.' The brevity of conciseness of this axiom was, however, qualified by Newton in a more expanded statement, 'the action of bodies one upon another are always equal, and in opposite directions.' This simple fact constitutes the point of departure for explaining dynamic equilibrium--that is to say, systems of conservancy. It is capable of satisfying even the dualists, and of explaining, without additional assumptions, the preservation of those chemical types which Dumas, Laurent, and Gerhardt created unit types, and those views of atomic combinations which the structuralists express by atomicity or the valency of the elements, and, in connection with them, the various numbers of affinities. In reality, if a system of atoms or a molecule be given, then in it, according to the third law of Newton, each portion of atoms acts on the remaining portion in the same manner, and with the same force as the second set of atoms acts on the first. We infer directly from this consideration that both sets of atoms, forming a molecule, are not only equivalent with regard to themselves, as they must be according to Dalton's law, but also that they may, if united, replace each other. Let there be a molecule containing atoms A B C, it is clear that, according to Newton's law, the action of A on B C must be equal to the action of B C on A, and if the first action is directed on B C, then the second must be directed on A, and consequently then, where A can exist in dynamic equilibrium, B C may take its place and act in a like manner. In the same way the action of C is equal to the action of A B. In one word every two sets of atoms forming a molecule are equivalent to each other, and may take each other's place in other molecules, or, having the power of balancing each other, the atoms or their complements are endowed with the power of replacing each other. Let us call this consequence of an evident axiom 'the principle of substitution,' and let us apply it to those typical forms of hydrogen compounds which we have already discussed, and which, on account of their simplicity, and regularity, have served as starting-points of chemical argument long before the appearance of the doctrine of structure. In the type of hydrofluoric acid, HF, or in systems of double stars, are included a multitude of the simplest molecules. It will be sufficient for our purpose to recall a few: for example, the molecules of chlorine, Cl_{2}, and of hydrogen, H_{2}, and hydrochloric acid, HCl, which is familiar to all in aqueous solution as spirits of salt, and which has many points of resemblance with HF, HBr, HI. In these cases division into two parts can only be made in one way, and therefore the principle of substitution renders it probable that exchanges between the chlorine and the hydrogen can take place, if they are competent to unite with each other. There was a time when no chemist would even admit the idea of any such action; it was then thought that the power of combination indicated a polar difference of the molecules in combination, and this thought set aside all idea of the substitution of one component element by another. Thanks to the observations and experiments of Dumas and Laurent fifty years ago, such fallacies were dispelled, and in this manner the principle of substitution was exhibited. Chlorine and bromine acting on many hydrogen compounds, occupy immediately the place of their hydrogen, and the displaced hydrogen, with another atom of chlorine or bromine, forms hydrochloric acid or bromide of hydrogen. This takes place in all typical hydrogen compounds. Thus chlorine acts on this principle on gaseous hydrogen--reaction, under the influence of light, resulting in the formation of hydrochloric acid. Chlorine acting on the alkalis, constituted similarly to water, and even on water itself--only, however, under the influence of light and only partially because of the instability of HClO--forms by this principle bleaching salts, which are the same as the alkalis, but with their hydrogen replaced by chlorine. In ammonia and in methane, chlorine can also replace the hydrogen. From ammonia is formed in this manner the so-called chloride of nitrogen, NCl_{3}, which decomposes very readily with violent explosion on account of the evolved gases, and falls asunder as chlorine and nitrogen. Out of marsh gas, or methane, CH_{4}, may be obtained consecutively, by this method, every possible substitution, of which chloroform, CHCl_{3}, is the best known, and carbon tetrachloride, CCl_{4}, the most instructive. But by virtue of the fact that chlorine and bromine act, in the manner shown, on the simplest typical hydrogen compounds, their action on the more complicated ones may be assumed to be the same. This can be easily demonstrated. The hydrogen of benzene, C_{6}H_{6}, reacts feebly under the influence of light on liquid bromine, but Gustavson has shown that the addition of the smallest quantity of metallic aluminium causes energetic action and the evolution of large volumes of hydrogen bromide. If we pass on to the second typical hydrogen compound--that is to say, water--its molecule, HOH, may be split up in two ways: either into an atom of hydrogen and a semi-molecule of hydrogen peroxide, HO, or into oxygen, O, and two atoms of hydrogen, H; and therefore, according to the principle of substitution, it is evident that one atom of hydrogen can exchange with hydrogen oxide, HO, and two atoms of hydrogen, H, with one atom of oxygen, O. Both these forms of substitution will constitute methods of oxidation--that is to say, of the entrance of oxygen into the compound--a reaction which is so common in nature as well as in the arts, taking place at the expense of the oxygen of the air or by the aid of various oxidising substances or bodies which part easily with their oxygen. There is no occasion to reckon up the unlimited number of cases of such oxidising reactions. It is sufficient to state that in the first of these oxygen is directly transferred, and the position, the chemical function, which hydrogen originally occupied, is, after the substitution, occupied by the hydroxyl. Thus ammonia, NH_{3}, yields hydroxylamine, NH_{2}(OH), a substance which retains many of the properties of ammonia. Methane and a number of other hydrocarbons yield, by substitution of the hydrogen by its oxide, methyl alcohol, CH_{3}(OH), and other alcohols. The substitution of one atom of oxygen for two atoms of hydrogen is equally common with hydrogen compounds. By this means alcoholic liquids containing ethyl alcohol, or spirits of wine, C_{2}H_{5}(OH), are oxidised until they become vinegar, or acetic acid, C_{2}H_{3}O(OH). In the same way caustic ammonia, or the combination of ammonia with water, NH_{3},H_{2}O, or NH_{4}(OH), which contains a great deal of hydrogen, by oxidation exchanges four atoms of hydrogen for two atoms of oxygen, and becomes converted into nitric acid, NO_{2}(OH). This process of conversion of ammonium salts into saltpetre goes on in the fields every summer, and with especial rapidity in tropical countries. The method by which this is accomplished, though complex, though involving the agency of all-permeating micro-organisms, is, in substance, the same as that by which alcohol is converted into acetic acid, or glycol, C_{2}H_{4}(OH)_{2}, into oxalic acid, if we view the process of oxidation in the light of the Newtonian principles. But while speaking of the application of the principle of substitution to water, we need not multiply instances, but must turn our attention to two special circumstances which are closely connected with the very mechanism of substitutions. In the first place, the replacement of two atoms of hydrogen by one atom of oxygen may take place in two ways, because the hydrogen molecule is composed of two atoms, and therefore, under the influence of oxygen, the molecule forming water may separate before the oxygen has time to take its place. It is for this reason that we find, during the conversion of alcohol into acetic acid, that there is an interval during which is formed aldehyde, C_{2}H_{4}O, which, as its very name implies, is 'alcohol dehydrogenatum,' or alcohol deprived of hydrogen. Hence aldehyde combined with hydrogen yields alcohol; and united to oxygen, acetic acid. For the same reason there should be, and there actually are, intermediate products between ammonia and nitric acid, NO_{2}(HO), containing either less hydrogen than ammonia, less oxygen than nitric acid, or less water than caustic ammonia. Accordingly we find, among the products of the deoxidation of nitric acid and the oxidation of ammonia, not only hydroxylamine, but also nitrous oxide, nitrous and nitric anhydrides. Thus, the production of nitrous acid results from the removal of two atoms of hydrogen from caustic ammonia and the substitution of the oxygen for the hydrogen, NO(OH); or by the substitution, in ammonia, of three atoms of hydrogen by hydroxyl, N(OH)_{3}, and by the removal of water: N(OH)_{3} - H_{2}O = NO(OH). The peculiarities and properties of nitrous acid--as, for instance, its action on ammonia and its conversion, by oxidation, into nitric acid--are thus clearly revealed. On the other hand, in speaking of the principle of substitution as applied to water, it is necessary to observe that hydrogen and hydroxyl, H and OH, are not only competent to unite, but also to form combinations with themselves, and thus become H_{2} and H_{2}O_{2}; and such are hydrogen and the peroxide thereof. In general, if a molecule A B exists, then molecules A A and B B can exist also. A direct reaction of this kind does not, however, take place in water, therefore undoubtedly, at the moment of formation, hydrogen reacts on hydrogen peroxide, as we can show at once by experiment; and further because hydrogen peroxide, H_{2}O_{2}, exhibits a structure containing a molecule of hydrogen, H_{2}, and one of oxygen, O_{2}, either of which is capable of separate existence. The fact, however, may now be taken as thoroughly established, that, at the moment of combustion of hydrogen or of the hydrogen compounds, hydrogen peroxide is always formed, and not only so, but in all probability its formation invariably precedes the formation of water. This was to be expected as a consequence of the law of Avogadro and Gerhardt, which leads us to expect this sequence in the case of equal interactions of volumes of vapours and gases; and in hydrogen peroxide we actually have such equal volumes of the elementary gases. The instability of hydrogen peroxide--that is to say, the ease with which it decomposes into water and oxygen, even at the mere contact of porous substances--accounts for the circumstance that it does not form a permanent product of combustion, and is not produced during the decomposition of water. I may mention this additional consideration that, with respect to hydrogen peroxide, we may look for its effecting still further substitutions of hydrogen by means of which we may expect to obtain still more highly oxidised water compounds, such as H_{2}O_{3} and H_{2}O_{4}. These Schönbein and Bunsen have long been seeking, and Berthelot is investigating them at present. It is probable, however, that the reaction will stop at the last compound, because we find that, in a number of cases, the addition of four atoms of oxygen seems to form a limit. Thus, OsO_{4}, KClO_{4}, KMnO_{4}, K_{2}SO_{4}, Na_{3}PO_{4}, and such like, represent the highest grades of oxidation.[1] [1] Because more than four atoms of hydrogen never unite with one atom of the elements, and because the hydrogen compounds (_e.g._ HCl, H_{2}S, H_{3}P, H_{4}Si) always form their highest oxides with four atoms of oxygen, and as the highest forms of oxides (OsO_{4}, RuO_{4}) also contain four of oxygen, and eight groups of the periodic system, corresponding to the highest basic oxides R_{2}O, RO, R_{2}O_{3}, RO_{2}, R_{2}O_{5}, RO_{3}, R_{2}O_{7}, and RO_{4}, imply the above relationship, and because of the nearest analogues among the elements--such as Mg, Zn, Cd, and Hg; or Cr, Mo, W, and U; or Si, Ge, Sn, and Pt; or F, Cl, Br, and I, and so forth--not more than four are known, it seems to me that in these relationships there lies a deep interest and meaning with regard to chemical mechanics. But because, to my imagination, the idea of unity of design in Nature, either acting in complex celestial systems or among chemical molecules, is very attractive, especially because the atomic teaching at once acquires its true meaning, I will recall the following facts relating to the solar system. There are eight major planets, of which the four inner ones are not only separated from the four outer by asteroids, but differ from them in many respects, as, for example, in the smallness of their diameters and their greater density. Saturn with his ring has eight satellites, Jupiter and Uranus have each four. It is evident that in the solar systems also we meet with these higher numbers four and eight which appear in the combination of chemical molecules. As for the last forty years, from the times of Berzelius, Dumas, Liebig, Gerhardt, Williamson, Frankland, Kolbe, Kekulé, and Butleroff, most theoretical generalisations have centred round organic or carbon compounds, we will, for the sake of brevity, leave out the discussion of ammonia derivatives, notwithstanding their simplicity with respect to the doctrine of substitutions; we will dwell more especially on its application to carbon compounds, starting from methane, CH_{4}, as the simplest of the hydrocarbons, containing in its molecule one atom of carbon. According to the principles enumerated we may derive from CH_{4} every combination of the form CH_{3}X, CH_{2}X_{2}, CHX_{3}, and CX_{4}, in which X is an element, or radicle, equivalent to hydrogen--that is to say, competent to take its place or to combine with it. Such are the chlorine substitutes already mentioned, such is wood-spirit, CH_{3}(OH), in which X is represented by the residue of water, and such are numerous other carbon derivatives. If we continue, with the aid of hydroxyl, further substitutions of the hydrogen of methane we shall obtain successively CH_{2}(OH)_{2}, CH(OH)_{3}, and C(OH)_{4}. But if, in proceeding thus, we bear in mind that CH_{2}(OH)_{2} contains two hydroxyls in the same form as hydrogen peroxide, H_{2}O_{2} or (OH)_{2}, contains them--and moreover not only in one molecule, but together, attached to one and the same atom of carbon--so here we must look for the same decomposition as that which we find in hydrogen peroxide, and accompanied also by the formation of water as an independently existing molecule; therefore CH_{2}(OH)_{2} should yield, as it actually does, immediately water and the oxide of methylene, CH_{2}O, which is methane with oxygen substituted for two atoms of hydrogen. Exactly in the same manner out of CH(OH)_{3} are formed water and formic acid, CHO(OH), and out of C(OH)_{4} is produced water and carbonic acid, or directly carbonic anhydride, CO_{2}, which will therefore be nothing else than methane with the double replacement of pairs of hydrogen by oxygen. As nothing leads to the supposition that the four atoms of hydrogen in methane differ one from the other, so it does not matter by what means we obtain any one of the combinations indicated--they will be identical; that is to say, there will be no case of actual isomerism, although there may easily be such cases of isomerism as have been distinguished by the term metamerism. Formic acid, for example, has two atoms of hydrogen, one attached to the carbon left from the methane, and the other attached to the oxygen which has entered in the form of hydroxyl, and if one of them be replaced by some substance X it is evident that we shall obtain substances of the same composition, but of different construction, or of different orders of movement among the molecules, and therefore endowed with other properties and reactions. If X be methyl, CH_{4}--that is to say, a group capable of replacing hydrogen because it is actually contained with hydrogen in methane itself--then by substituting this group for the original hydrogen we obtain acetic acid, CCH_{3}O(OH), out of formic, and by substitution of the hydrogen in its oxide or hydroxyl we obtain methyl formate, CHO(OCH_{3}). These substances differ so much from each other physically and chemically that at first sight it is hardly possible to admit that they contain the same atoms in identically the same proportions. Acetic acid, for example, boils at a higher temperature than water, and has a higher specific gravity than it, whilst its metameride, methyl formate, is lighter than water, and boils at 30°--that is to say, it evaporates very easily. Let us now turn to carbon compounds containing two atoms of carbon to the molecule, as in acetic acid, and proceed to evolve them from methane by the principle of substitution. This principle declares at once that methane can only be split up in the four following ways:-- 1. Into a group CH_{3} equivalent with H. Let us call changes of this nature methylation. 2. Into a group CH_{2} and H_{2}. We will call this order of substitutions methylenation. 3. Into CH and H_{3}, which commutations we will call acetylenation. 4. Into C and H_{4}, which may be called carbonation. It is evident that hydrocarbon compounds containing two atoms of carbon can only proceed from methane, CH_{4}, which contains four atoms of hydrogen by the first three methods of substitution; carbonation would yield free carbon if it could take place directly, and if the molecule of free carbon--which is in reality very complex, that is to say strongly polyatomic, as I have long since been proving by various means--could contain only C_{2} like the molecules O_{2}, H_{2}, N_{2}, and so on. By methylation we should evidently obtain from marsh gas, ethane, CH_{3}CH_{3} = C_{2}H_{6}. By methylenation--that is, by substituting group CH_{2} for H_{2}--methane forms ethylene, CH_{2}CH_{2} = C_{2}H_{4}. By acetylenation--that is, by substituting three atoms of hydrogen, H_{3}, in methane--by the remnant CH, we get acetylene, CHCH = C_{2}H_{2}. If we have applied the principles of Newton correctly, there should not be any other hydrocarbons containing two atoms of carbon in the molecule. All these combinations have long been known, and in each of them we can not only produce those substitutions of which an example has been given in the case of methane, but also all the phases of other substitutions, as we shall find from a few more instances, by the aid of which I trust that I shall be able to show the great complexity of those derivatives which, on the principle of substitution, can be obtained from each hydrocarbon. Let us content ourselves with the case of ethane, CH_{3}CH_{3}, and the substitution of the hydrogen by hydroxyl. The following are the possible changes:-- 1. CH_{3}CH_{2}(OH): this is nothing more than spirit of wine, or ethyl alcohol, C_{2}H_{5}(OH) or C_{2}H_{6}O. 2. CH_{2}(OH)CH_{2}(OH): this is the glycol of Würtz, which has shed so much light on the history of alcohol. Its isomeride may be CH_{3}CH(OH)_{2}, but as we have seen in the case of CH(OH)_{2}, it decomposes, giving off water, and forming aldehyde, CH_{3}CHO, a substance capable of yielding alcohol by uniting with hydrogen, and of yielding acetic acid by uniting with oxygen. If glycol, CH_{2}(OH)CH_{2}(OH), loses its water, it may be seen at once that it will not now yield aldehyde, CH_{3}CHO, but its isomeride, CH_{2}CH_{2}/O, the oxide of ethylene. I have here indicated in a special manner the oxygen which has taken the place of two atoms of the hydrogen of ethane taken from different atoms of the carbon. 3. CH_{3}C(OH)_{3} decomposed as CH(OH)_{3}, forming water and acetic acid, CH_{3}CO(OH). It is evident that this acid is nothing else than formic acid, CHO(OH), with its hydrogen replaced by methyl. Without examining further the vast number of possible derivatives, I will direct your attention to the circumstance that in dissolving acetic acid in water we obtain the maximum contraction and the greatest viscosity when to the molecule CH_{3}CO(OH) is added a molecule of water, which is the proportion which would form the hydrate CH_{3}C(OH)_{3}. It is probable that the doubling of the molecule of acetic acid at temperatures approaching its boiling-point has some connection with this power of uniting with one molecule of water. 4. CH_{2}(OH)C(OH)_{3} is evidently an alcoholic acid, and indeed this compound, after losing water, answers to glycolic acid, CH_{2}(OH)CO(OH). Without investigating all the possible isomerides, we will note only that the hydrate CH(OH)_{2}CH(OH)_{2} has the same composition as CH_{2}(OH)C(OH)_{3}, and although corresponding to glycol, and being a symmetrical substance, it becomes, on parting with its water, the aldehyde of oxalic acid, or the glyoxal of Debus, CHOCHO. 5. CH(OH)_{2}C(OH_{3}), from the tendency of all the preceding, corresponds with glyoxylic acid, an aldehyde acid, CHOCO(OH), because the group CO(OH), or carboxyl, enters into the compositions of organic acids, and the group CHO defines the aldehyde function. 6. C(OH)_{3}C(OH)_{3} through the loss of 2H_{2}O yields the bibasic oxalic acid CO(OH)CO(OH), which generally crystallises with 2H_{2}O, following thus the normal type of hydration characteristic of ethane.[2] [2] One more isomeride, CH_{2}CH(OH), is possible--that is, secondary vinyl alcohol, which is related to ethylene, CH_{2}CH_{2}, but derived by the principle of substitution from CH_{4}. Other isomerides, of the composition C_{2}H_{4}O, such, for example, as CCH_{3}(OH), are impossible, because it would correspond with the hydrocarbon CHCH_{3} = C_{2}H_{4}, which is isomeric with ethylene, and it cannot be derived from methane. If such an isomeride existed it would be derived from CH_{2}, but such products are, up to the present, unknown. In such cases the insufficiency of the points of departure of the statical structural teaching is shown. It first admits constant atomicity and then rejects it, the facts serving to establish either one or the other view; and therefore it seems to me that we must come to the conclusion that the structural method of reasoning, having done a service to science, has outlived the age, and must be regenerated, as in their time was the teaching of the electro-chemists, the radicalists, and the adherents of the doctrine of types. As we cannot now lean on the views above stated, it is time to abandon the structural theory. They will all be united in chemical mechanics, and the principle of substitution must be looked on only as a preparation for the coming epoch in chemistry, where such cases as the isomerism of fumaric and maleic acids, when explained dynamically, as proposed by Le Bel and Van't Hoff, may yield points of departure. Thus, by applying the principle of substitution, we can, in the simplest manner, derive not only every kind of hydrocarbon compound, such as the alcohols, the aldehyde-alcohols, aldehydes, alcohol-acids, and the acids, but also combinations analogous to hydrated crystals which usually are disregarded. But even those unsaturated substances, of which ethylene, CH_{2}CH_{2}, and acetylene, CHCH, are types, may be evolved with equal simplicity. With respect to the phenomena of isomerism, there are many possibilities among the hydrocarbon compounds containing two atoms of carbon, and without going into details it will be sufficient to indicate that the following formulæ, though not identical, will be isomeric substantially among themselves:--CH_{3}CHX_{2} and CH_{2}XCH_{2}X, although both contain C_{2}H_{4}X_{2}; or CH_{2}CX_{2} and CHXCHX, although both contain C_{2}H_{2}X_{2}, if by X we indicate chlorine or generally an element capable of replacing one atom of hydrogen, or capable of uniting with it. To isomerism of this kind belongs the case of aldehyde and the oxide of ethylene, to which we have already referred, because both have the composition C_{2}H_{4}O. What I have said appears to me sufficient to show that the principle of substitution adequately explains the composition, the isomerism, and all the diversity of combination of the hydrocarbons, and I shall limit the further development of these views to preparing a complete list of every possible hydrocarbon compound containing three atoms of carbon in the molecule. There are eight in all, of which only five are known at present.[3] [3] Conceding variable atomicity, the structuralists must expect an incomparably larger number of isomerides, and they cannot now decline to acknowledge the change of atomicity, were it only for the examples HgCl and HgCl_{2}, CO and CO_{2}, PCl_{3} and PCl_{5}. Among those possible for C_{3}H_{6} there should be two isomerides, propylene and trimethylene, and they are both already known. For C_{3}H_{4} there should be three isomerides: allylene and allene are known, but the third has not yet been discovered; and for C_{3}H_{2} there should be two isomerides, though neither of them is known as yet. Their composition and structure are easily deduced from ethane, ethylene, and acetylene, by methylation, by methylenation, by acetylenation and by carbonation. 1. C_{3}H_{8} = CH_{3}CH_{2}CH_{3} out of CH_{3}CH_{3} by methylation. This hydrocarbon is named propane. 2. C_{3}H_{6} = CH_{3}CHCH_{2} out of CH_{3}CH_{3} by methylenation. This substance is propylene. 3. C_{3}H_{6} = CH_{2}CH_{2}CH_{2} out of CH_{3}CH_{3} by methylenation. This substance is trimethylene. 4. C_{3}H_{4} = CH_{3}CCH out of CH_{3}CH_{3} by acetylenation or from CHCH by methylation. This hydrocarbon is named allylene. 5. C_{3}H_{4} = CHCH/CH_{2} out of CH_{3}CH_{3} by acetylenation, or from CH_{2}CH_{2} by methylenation, because CH_{2}CH/CH = CHCH/CH_{2}. This body is as yet unknown. 6. C_{3}H_{4} = CH_{2}CCH_{2} out of CH_{2}CH_{2} by methylenation. This hydrocarbon is named allene, or iso-allylene. 7. C_{3}H_{2} = CHCH/C out of CH_{3}CH_{3} by symmetrical carbonation, or out of CH_{2}CH_{2} by acetylenation. This compound is unknown. 8. C_{3}H_{2} = CC/CH_{2} out of CH_{3}CH_{3} by carbonation, or out of CHCH by methylenation. This compound is unknown. If we bear in mind that for each hydrocarbon serving as a type in the above tables there are a number of corresponding derivatives, and that every compound obtained may, by further methylation, methylenation, acetylenation, and carbonation, produce new hydrocarbons, and these may be followed by a numerous suite of derivatives and an immense number of isomeric substances, it is possible to understand the limitless number of carbon compounds, although they all have the one substance, methane, for their origin. The number of substances is so enormous that it is no longer a question of enlarging the possibilities of discovery, but rather of finding some means of testing them analogous to the well-known two which for a long time have served as gauges for all carbon compounds. I refer to the law of even numbers and to that of limits, the first enunciated by Gerhardt some forty years ago, with respect to hydrocarbons, namely, that their molecules always contain an even number of atoms of hydrogen. But by the method which I have used of deriving all the hydrocarbons from methane, CH_{4}, this law may be deduced as a direct consequence of the principle of substitutions. Accordingly, in methylation, CH_{3} takes the place of H, and therefore CH_{2} is added. In methylenation the number of atoms of hydrogen remains unchanged, and at each acetylenation it is reduced by two, and in carbonation by four, atoms--that is to say, an even number of atoms of hydrogen is always added or removed. And because the fundamental hydrocarbon, methane, CH_{4}, contains an even number of atoms of hydrogen, all its derivative hydrocarbons will also contain even numbers of hydrogen, and this constitutes the law of even numbers. The principle of substitutions explains with equal simplicity the conception of the limiting compositions of hydrocarbons C_{_n_}H_{2_n_ + 2}, which I derived, in 1861,[4] in an empirical manner from accumulated materials available at that time, and on the basis of the limits to combinations worked out by Dr. Frankland for other elements. [4] 'Essai d'une théorie sur les limites des combinaisons organiques,' par D. Mendeléeff, 2/11 août 1861, _Bulletin de l'Académie i. d. Sc. de St. Pétersbourg_, t. v Of all the various substitutions the highest proportion of hydrogen is yielded by methylation, because in that operation alone does the quantity of hydrogen increase; hence, taking methane as a point of departure, if we imagine methylation effected (_n_ - 1) times we obtain hydrocarbon compounds containing the highest quantities of hydrogen. It is evident that they will contain CH_{4} + (_n_ - 1)CH_{2}, or C_{_n_}H_{2_n_} + {2}, because methylation leads to the addition of CH_{2} to the compound. It will thus be seen that by the principle of substitution--that is to say, by the third law of Newton--we are able to deduce, in the simplest manner, not only the individual composition, the isomerism, and relations of substances, but also the general laws which govern their most complex combinations without having recourse either to statical constructions, to the definition of atomicities, to the exclusion of free affinities, or to the recognition of those single, double or treble bonds which are so indispensable to structuralists in the explanation of the composition and construction of hydrocarbon compounds. And yet, by the application of the dynamical principles of Newton, we can attain to that chief and fundamental object, the comprehension of isomerism in hydrocarbon compounds, and the forecasting of the existence of combinations as yet unknown, by which the edifice raised by structural teaching is strengthened and supported. Besides--and I count this for a circumstance of special importance--the process which I advocate will make no difference in those special cases which have been already so well worked out, such as, for example, the isomerism of the hydrocarbons and alcohols, even to the extent of not interfering with the nomenclature which has been adopted, and the structural system will retain all the glory of having worked up, in a thoroughly scientific manner, the store of information which Gerhardt had accumulated about the middle of the fifties, and the still higher glory of establishing the rational synthesis of organic substances. Nothing will be lost to the structural doctrine except its statical origin; and as soon as it will embrace the dynamic principles of Newton, and suffer itself to be guided by them, I believe that we shall attain for chemistry that unity of principle which is now wanting. Many an adept will be attracted to that brilliant and fascinating enterprise, the penetration into the unseen world of the kinetic relations of atoms, to the study of which the last twenty-five years have contributed so much labour and such high inventive faculties. D'Alembert found in mechanics that if inertia be taken to represent force, dynamic equations may be applied to statical questions, which are thereby rendered more simple and more easily understood. The structural doctrine in chemistry has unconsciously followed the same course, and therefore its terms are easily adopted; they may retain their present forms provided that a truly dynamical--that is to say, Newtonian--meaning be ascribed to them. Before finishing my task and demonstrating the possibility of adapting structural doctrines to the dynamics of Newton, I consider it indispensable to touch on one question which naturally arises, and which I have heard discussed more than once. If bromine, the atom of which is eighty times heavier than that of hydrogen, takes the place of hydrogen, it would seem that the whole system of dynamic equilibrium must be destroyed. Without entering into the minute analysis of this question, I think it will be sufficient to examine it by the light of two well-known phenomena, one of which will be found in the department of chemistry and the other in that of celestial mechanics, and both will serve to demonstrate the existence of that unity in the plan of creation which is a consequence of the Newtonian doctrines. Experiments demonstrate that when a heavy element is substituted for a light one in a chemical compound--for example, for magnesium, in the oxide of that metal, an atom of mercury, which is 8-1/3 times heavier--the chief chemical characteristics or properties are generally, though not always, preserved. The substitution of silver for hydrogen, than which it is 108 times heavier, does not affect all the properties of the substance, though it does some. Therefore chemical substitutions of this kind--the substitution of light for heavy atoms--need not necessarily entail changes in the original equilibrium; and this point is still further elucidated by the consideration that the periodic law indicates the degree of influence of an increment of weight in the atom as affecting the possible equilibria, and also what degree of increase in the weight of the atoms reproduces some, though not all, of the properties of the substance. This tendency to repetition--these periods--may be likened to those annual or diurnal periods with which we are so familiar on the earth. Days and years follow each other, but, as they do so, many things change; and in like manner chemical evolutions, changes in the masses of the elements, permit of much remaining undisturbed, though many properties undergo alteration. The system is maintained according to the laws of conservation in nature, but the motions are altered in consequence of the change of parts. Next, let us take an astronomical case--such, for example, as the earth and the moon--and let us imagine that the mass of the latter is constantly increasing. The question is, what will then occur? The path of the moon in space is a wave-line similar to that which geometricians have named epicycloidal, or the locus of a point in a circle rolling round another circle. But in consequence of the influence of the moon it is evident that the path of the earth itself cannot be a geometric ellipse, even supposing the sun to be immovably fixed; it must be an epicycloidal curve, though not very far removed from the true ellipse--that is to say, it will be impressed with but faint undulations. It is only the common centre of gravity of the earth and the moon which describes a true ellipse round the sun. If the moon were to increase, the relative undulations of the earth's path would increase in amplitude, those of the moon would also change, and when the mass of the moon had increased to an equality with that of the earth, the path would consist of epicycloidal curves crossing each other, and having opposite phases. But a similar relation exists between the sun and the earth, because the former is also moving in space. We may apply these views to the world of atoms, and suppose that in their movements, when heavy ones take the place of those that are lighter, similar changes take place, provided that the system or the molecule is preserved throughout the change. It seems probable that in the heavenly systems, during incalculable astronomical periods, changes have taken place and are still going on similar to those which pass rapidly before our eyes during the chemical reaction of molecules, and the progress of molecular mechanics may--we hope will--in course of time permit us to explain those changes in the stellar world which have more than once been noticed by astronomers, and which are now so carefully studied. A coming Newton will discover the laws of these changes. Those laws, when applied to chemistry, may exhibit peculiarities, but these will certainly be mere variations on the grand harmonious theme which reigns in nature. The discovery of the laws which produce this harmony in chemical evolution will only be possible, it seems to me, under the banner of Newtonian dynamics, which has so long waved over the domains of mechanics, astronomy, and physics. In calling chemists to take their stand under its peaceful and catholic shadow I imagine that I am aiding in establishing that scientific union which the managers of the Royal Institution wish to effect, who have shown their desire to do so by the flattering invitation which has given me--a Russian--the opportunity of laying before the countrymen of Newton an attempt to apply to chemistry one of his immortal principles. APPENDIX II THE PERIODIC LAW OF THE CHEMICAL ELEMENTS BY PROFESSOR MENDELÉEFF FARADAY LECTURE DELIVERED BEFORE THE FELLOWS OF THE CHEMICAL SOCIETY IN THE THEATRE OF THE ROYAL INSTITUTION, ON TUESDAY, JUNE 4, 1889 The high honour bestowed by the Chemical Society in inviting me to pay a tribute to the world-famed name of Faraday by delivering this lecture has induced me to take for its subject the Periodic Law of the Elements--this being a generalisation in chemistry which has of late attracted much attention. While science is pursuing a steady onward movement, it is convenient from time to time to cast a glance back on the route already traversed, and especially to consider the new conceptions which aim at discovering the general meaning of the stock of facts accumulated from day to day in our laboratories. Owing to the possession of laboratories, modern science now bears a new character, quite unknown, not only to antiquity, but even to the preceding century. Bacon's and Descartes' idea of submitting the mechanism of science simultaneously to experiment and reasoning has been fully realised in the case of chemistry, it having become not only possible but always customary to experiment. Under the all-penetrating control of experiment, a new theory, even if crude, is quickly strengthened, provided it be founded on a sufficient basis; the asperities are removed, it is amended by degrees, and soon loses the phantom light of a shadowy form or of one founded on mere prejudice; it is able to lead to logical conclusions, and to submit to experimental proof. Willingly or not, in science we all must submit not to what seems to us attractive from one point of view or from another, but to what represents an agreement between theory and experiment; in other words, to demonstrated generalisation and to the approved experiment. Is it long since many refused to accept the generalisations involved in the law of Avogadro and Ampère, so widely extended by Gerhardt? We still may hear the voices of its opponents; they enjoy perfect freedom, but vainly will their voices rise so long as they do not use the language of demonstrated facts The striking observations with the spectroscope which have permitted us to analyse the chemical constitution of distant worlds, seemed, at first, applicable to the task of determining the nature of the atoms themselves; but the working out of the idea in the laboratory soon demonstrated that the characters of spectra are determined, not directly by the atoms, but by the molecules into which the atoms are packed; and so it became evident that more verified facts must be collected before it will be possible to formulate new generalisations capable of taking their place beside those ordinary ones based upon the conception of simple substances and atoms. But as the shade of the leaves and roots of living plants, together with the relics of a decayed vegetation, favour the growth of the seedling and serve to promote its luxurious development, in like manner sound generalisations--together with the relics of those which have proved to be untenable--promote scientific productivity, and ensure the luxurious growth of science under the influence of rays emanating from the centres of scientific energy. Such centres are scientific associations and societies. Before one of the oldest and most powerful of these I am about to take the liberty of passing in review the twenty years' life of a generalisation which is known under the name of the Periodic Law. It was in March 1869 that I ventured to lay before the then youthful Russian Chemical Society the ideas upon the same subject which I had expressed in my just written 'Principles of Chemistry.' Without entering into details, I will give the conclusions I then arrived at in the very words I used:-- '1. The elements, if arranged according to their atomic weights, exhibit an evident _periodicity_ of properties. '2. Elements which are similar as regards their chemical properties have atomic weights which are either of nearly the same value (_e.g._ platinum, iridium, osmium) or which increase regularly (_e.g._ potassium, rubidium, cæsium). '3. The arrangement of the elements, or of groups of elements, in the order of their atomic weights, corresponds to their so-called _valencies_ as well as, to some extent, to their distinctive chemical properties--as is apparent, among other series, in that of lithium, beryllium, barium, carbon, nitrogen, oxygen, and iron. '4. The elements which are the most widely diffused have _small_ atomic weights. '5. The _magnitude_ of the atomic weight determines the character of the element, just as the magnitude of the molecule determines the character of a compound. '6. We must expect the discovery of many yet _unknown_ elements--for example, elements analogous to aluminium and silicon, whose atomic weight would be between 65 and 75. '7. The atomic weight of an element may sometimes be amended by a knowledge of those of the contiguous elements. Thus, the atomic weight of tellurium must lie between 123 and 126, and cannot be 128. '8. Certain characteristic properties of the elements can be foretold from their atomic weights. 'The aim of this communication will be fully attained if I succeed in drawing the attention of investigators to those relations which exist between the atomic weights of dissimilar elements, which, so far as I know, have hitherto been almost completely neglected. I believe that the solution of some of the most important problems of our science lies in researches of this kind.' To-day, twenty years after the above conclusions were formulated, they may still be considered as expressing the essence of the now well-known periodic law. Reverting to the epoch terminating with the sixties, it is proper to indicate three series of data without the knowledge of which the periodic law could not have been discovered, and which rendered its appearance natural and intelligible. In the first place, it was at that time that the numerical value of atomic weights became definitely known. Ten years earlier such knowledge did not exist, as may be gathered from the fact that in 1860 chemists from all parts of the world met at Karlsruhe in order to come to some agreement, if not with respect to views relating to atoms, at any rate as regards their definite representation. Many of those present probably remember how vain were the hopes of coming to an understanding, and how much ground was gained at that Congress by the followers of the unitary theory so brilliantly represented by Cannizzaro. I vividly remember the impression produced by his speeches, which admitted of no compromise, and seemed to advocate truth itself, based on the conceptions of Avogadro, Gerhardt, and Regnault, which at that time were far from being generally recognised. And though no understanding could be arrived at, yet the objects of the meeting were attained, for the ideas of Cannizzaro proved, after a few years, to be the only ones which could stand criticism, and which represented an atom as--'the smallest portion of an element which enters into a molecule of its compound.' Only such real atomic weights--not conventional ones--could afford a basis for generalisation. It is sufficient, by way of example, to indicate the following cases in which the relation is seen at once and is perfectly clear:-- K = 39 Rb = 85 Cs = 133 Ca = 40 Sr = 87 Ba = 137 whereas with the equivalents then in use-- K = 39 Rb = 85 Cs = 133 Ca = 20 Sr = 43·5 Ba = 68·5 the consecutiveness of change in atomic weight, which with the true values is so evident, completely disappears. Secondly, it had become evident during the period 1860-70, and even during the preceding decade, that the relations between the atomic weights of analogous elements were governed by some general and simple laws. Cooke, Cremers, Gladstone, Gmelin, Lenssen, Pettenkofer, and especially Dumas, had already established many facts bearing on that view. Thus Dumas compared the following groups of analogous elements with organic radicles:-- Diff. Diff. Diff. Diff. Mg = 12} P = 31} O = 8} }8 }44 }8 Li = 7 } Ca = 20} As= 75} S = 16} }16 }3 × 8 }44 }3 × 8 Na = 23} Sr = 44} Sb = 119} Se = 40} }16 }3 × 8 }2 × 44 }3 × 8 K = 39 } Ba = 68} Bi = 207} Te = 64} and pointed out some really striking relationships, such as the following:-- F = 19. Cl = 35·5 = 19 + 16·5. Br = 80 = 19 + 2 × 16·5 + 28. I = 127 = 2 x 19 + 2 × 16·5 + 2 × 28. A. Strecker, in his work 'Theorien und Experimente zur Bestimmung der Atomgewichte der Elemente' (Braunschweig, 1859), after summarising the data relating to the subject, and pointing out the remarkable series of equivalents-- Cr = 26·2 Mn = 27·6 Fe = 28 Ni = 29 Co = 30 Cu = 31·7 Zn = 32·5 remarks that: 'It is hardly probable that all the above-mentioned relations between the atomic weights (or equivalents) of chemically analogous elements are merely accidental. We must, however, leave to the future the discovery of the _law_ of the relations which appears in these figures.'[1] [1] 'Es ist wohl kaum anzunehmen, dass alle im Vorhergehenden hervorgehobenen Beziehungen zwischen den Atomgewichten (oder Aequivalenten) in chemischen Verhältnissen einander ähnliche Elemente bloss zufällig sind. Die Auffindung der in diesen Zahlen _gesetzlichen_ Beziehungen müssen wir jedoch der Zukunft überlassen.' In such attempts at arrangement and in such views are to be recognised the real forerunners of the periodic law; the ground was prepared for it between 1860 and 1870, and that it was not expressed in a determinate form before the end of the decade may, I suppose, be ascribed to the fact that only analogous elements had been compared. The idea of seeking for a relation between the atomic weights of all the elements was foreign to the ideas then current, so that neither the _vis tellurique_ of De Chancourtois, nor the _law of octaves_ of Newlands, could secure anybody's attention. And yet both De Chancourtois and Newlands like Dumas and Strecker, more than Lenssen and Pettenkofer, had made an approach to the periodic law and had discovered its germs. The solution of the problem advanced but slowly, because the facts, but not the law, stood foremost in all attempts; and the law could not awaken a general interest so long as elements, having no apparent connection with each other, were included in the same octave, as for example:-- 1st octave of | | | | | | | | Newlands | H | F | Cl | Co & Ni | Br | Pd | I | Pt & Ir 7th Ditto | O | S | Fe | Se | Rh & Ru | Te | Au | Os or Th Analogies of the above order seemed quite accidental, and the more so as the octave contained occasionally ten elements instead of eight, and when two such elements as Ba and V, Co and Ni, or Rh and Ru, occupied one place in the octave.[2] Nevertheless, the fruit was ripening, and I now see clearly that Strecker, De Chancourtois, and Newlands stood foremost in the way towards the discovery of the periodic law, and that they merely wanted the boldness necessary to place the whole question at such a height that its reflection on the facts could be clearly seen. [2] To judge from J. A. R. Newlands's work, _On the Discovery of the Periodic Law_, London, 1884, p. 149; 'On the Law of Octaves' (from the _Chemical News_, 12, 83, August 18, 1865). A third circumstance which revealed the periodicity of chemical elements was the accumulation, by the end of the sixties, of new information respecting the rare elements, disclosing their many-sided relations to the other elements and to each other. The researches of Marignac on niobium, and those of Roscoe on vanadium, were of special moment. The striking analogies between vanadium and phosphorus on the one hand, and between vanadium and chromium on the other, which became so apparent in the investigations connected with that element, naturally induced the comparison of V = 51 with Cr = 52, Nb = 94 with Mo = 96, and Ta = 192 with W = 194; while, on the other hand, P = 31 could be compared with S = 32, As = 75 with Se = 79, and Sb = 120 with Te = 125. From such approximations there remained but one step to the discovery of the law of periodicity. The law of periodicity was thus a direct outcome of the stock of generalisations and established facts which had accumulated by the end of the decade 1860-1870; it is an embodiment of those data in a more or less systematic expression. Where, then, lies the secret of the special importance which has since been attached to the periodic law, and has raised it to the position of a generalisation which has already given to chemistry unexpected aid, and which promises to be far more fruitful in the future and to impress upon several branches of chemical research a peculiar and original stamp? The remaining part of my communication will be an attempt to answer this question. In the first place we have the circumstance that, as soon as the law made its appearance, it demanded a revision of many facts which were considered by chemists as fully established by existing experience. I shall return, later on, briefly to this subject, but I wish now to remind you that the periodic law, by insisting on the necessity for a revision of supposed facts, exposed itself at once to destruction in its very origin. Its first requirements, however, have been almost entirely satisfied during the last 20 years; the supposed facts have yielded to the law, thus proving that the law itself was a legitimate induction from the verified facts. But our inductions from data have often to do with such details of a science so rich in facts, that only generalisations which cover a wide range of important phenomena can attract general attention. What were the regions touched on by the periodic law? This is what we shall now consider. The most important point to notice is, that periodic functions, used for the purpose of expressing changes which are dependent on variations of time and space, have been long known. They are familiar to the mind when we have to deal with motion in closed cycles, or with any kind of deviation from a stable position, such as occurs in pendulum-oscillations. A like periodic function became evident in the case of the elements, depending on the mass of the atom. The primary conception of the masses of bodies, or of the masses of atoms, belongs to a category which the present state of science forbids us to discuss, because as yet we have no means of dissecting or analysing the conception. All that was known of functions dependent on masses derived its origin from Galileo and Newton, and indicated that such functions either decrease or increase with the increase of mass, like the attraction of celestial bodies. The numerical expression of the phenomena was always found to be proportional to the mass, and in no case was an increase of mass followed by a recurrence of properties such as is disclosed by the periodic law of the elements. This constituted such a novelty in the study of the phenomena of nature that, although it did not lift the veil which conceals the true conception of mass, it nevertheless indicated that the explanation of that conception must be searched for in the masses of the atoms; the more so, as all masses are nothing but aggregations, or additions, of chemical atoms which would be best described as chemical individuals. Let me remark, by the way, that though the Latin word 'individual' is merely a translation of the Greek word 'atom,' nevertheless history and custom have drawn a sharp distinction between the two words, and the present chemical conception of atoms is nearer to that defined by the Latin word than by the Greek, although this latter also has acquired a special meaning which was unknown to the classics. The periodic law has shown that our chemical individuals display a harmonic periodicity of properties dependent on their masses. Now natural science has long been accustomed to deal with periodicities observed in nature, to seize them with the vice of mathematical analysis, to submit them to the rasp of experiment. And these instruments of scientific thought would surely, long since, have mastered the problem connected with the chemical elements, were it not for a new feature which was brought to light by the periodic law, and which gave a peculiar and original character to the periodic function. If we mark on an axis of abscissæ a series of lengths proportional to angles, and trace ordinates which are proportional to sines or other trigonometrical functions, we get periodic curves of a harmonic character. So it might seem, at first sight, that with the increase of atomic weights the function of the properties of the elements should also vary in the same harmonious way. But in this case there is no such continuous change as in the curves just referred to, because the periods do not contain the infinite number of points constituting a curve, but a _finite_ number only of such points. An example will better illustrate this view. The atomic weights-- Ag = 108 Cd = 112 In = 113 Sn = 118 Sb = 120 Te = 125 I = 127 steadily increase, and their increase is accompanied by a modification of many properties which constitutes the essence of the periodic law. Thus, for example, the densities of the above elements decrease steadily, being respectively-- 10·5 8·6 7·4 7·2 6·7 6·4 4·9 while their oxides contain an increasing quantity of oxygen-- Ag_{2}O Cd_{2}O_{2} In_{2}O_{3} Sn_{2}O_{4} Sb_{2}O_{5} Te_{2}O_{6} I_{2}O_{7} But to connect by a curve the summits of the ordinates expressing any of these properties would involve the rejection of Dalton's law of multiple proportions. Not only are there no intermediate elements between silver, which gives AgCl, and cadmium, which gives CdCl_{2}, but, according to the very essence of the periodic law, there can be none; in fact a uniform curve would be inapplicable in such a case, as it would lead us to expect elements possessed of special properties at any point of the curve. The periods of the elements have thus a character very different from those which are so simply represented by geometers. They correspond to points, to numbers, to sudden changes of the masses, and not to a continuous evolution. In these sudden changes destitute of intermediate steps or positions, in the absence of elements intermediate between, say, silver and cadmium, or aluminium and silicon, we must recognise a problem to which no direct application of the analysis of the infinitely small can be made. Therefore, neither the trigonometrical functions proposed by Ridberg and Flavitzky, nor the pendulum-oscillations suggested by Crookes, nor the cubical curves of the Rev. Mr. Haughton, which have been proposed for expressing the periodic law, from the nature of the case, can represent the periods of the chemical elements. If geometrical analysis is to be applied to this subject, it will require to be modified in a special manner. It must find the means of representing in a special way, not only such long periods as that comprising K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br, but short periods like the following:-- Na Mg Al Si P S Cl. In the theory of numbers only do we find problems analogous to ours, and two attempts at expressing the atomic weights of the elements by algebraic formulæ seem to be deserving of attention, although neither of them can be considered as a complete theory, nor as promising finally to solve the problem of the periodic law. The attempt of E. J. Mills (1886) does not even aspire to attain this end. He considers that all atomic weights can be expressed by a logarithmic function, 15(_n_ - 0·9375^_t_), in which the variables _n_ and _t_ are _whole numbers_. Thus, for oxygen, _n_ = 2, and _t_ = 1, whence its atomic weight is = 15·94; in the case of chlorine, bromine, and iodine, _n_ has respective values of 3, 6, and 9, whilst _t_ = 7, 6, and 9; in the case of potassium, rubidium, and cæsium, _n_ = 4, 6, and 9, and _t_ = 14, 18, and 20. Another attempt was made in 1888 by B. N. Tchitchérin. Its author places the problem of the periodic law in the first rank, but as yet he has investigated the alkali metals only. Tchitchérin first noticed the simple relations existing between the atomic volumes of all alkali metals; they can be expressed, according to his views, by the formula A(2 - 0·00535A_n_), where A is the atomic weight, and _n_ is equal to 8 for lithium and sodium, to 4 for potassium, to 3 for rubidium, and to 2 for cæsium. If _n_ remained equal to 8 during the increase of A, the volume would become zero at A = 46-2/3, and it would reach its maximum at A = 23-1/3. The close approximation of the number 46-2/3 to the differences between the atomic weights of analogous elements (such as Cs - Rb, I - Br, and so on); the close correspondence of the number 23-1/3 to the atomic weight of sodium; the fact of _n_ being necessarily a whole number, and several other aspects of the question, induce Tchitchérin to believe that they afford a clue to the understanding of the nature of the elements; we must, however, await the full development of his theory before pronouncing judgment on it. What we can at present only be certain of is this: that attempts like the two above named must be repeated and multiplied, because the periodic law has clearly shown that the masses of the atoms increase abruptly, by steps, which are clearly connected in some way with Dalton's law of multiple proportions; and because the periodicity of the elements finds expression in the transition from RX to RX_{2}, RX_{3}, RX_{4}, and so on till RX_{8}, at which point, the energy of the combining forces being exhausted, the series begins anew from RX to RX_{2}, and so on. While connecting by new bonds the theory of the chemical elements with Dalton's theory of multiple proportions, or atomic structure of bodies, the periodic law opened for natural philosophy a new and wide field for speculation. Kant said that there are in the world 'two things which never cease to call for the admiration and reverence of man: the moral law within ourselves, and the stellar sky above us.' But when we turn our thoughts towards the nature of the elements and the periodic law, we must add a third subject, namely, 'the nature of the elementary individuals which we discover everywhere around us.' Without them the stellar sky itself is inconceivable; and in the atoms we see at once their peculiar individualities, the infinite multiplicity of the individuals, and the submission of their seeming freedom to the general harmony of Nature. Having thus indicated a new mystery of Nature, which does not yet yield to rational conception, the periodic law, together with the revelations of spectrum analysis, have contributed to again revive an old but remarkably long-lived hope--that of discovering, if not by experiment, at least by a mental effort, the _primary matter_--which had its genesis in the minds of the Grecian philosophers, and has been transmitted, together with many other ideas of the classic period, to the heirs of their civilisation. Having grown, during the times of the alchemists up to the period when experimental proof was required, the idea has rendered good service; it induced those careful observations and experiments which later on called into being the works of Scheele, Lavoisier, Priestley, and Cavendish. It then slumbered awhile, but was soon awakened by the attempts either to confirm or to refute the ideas of Prout as to the multiple proportion relationship of the atomic weights of all the elements. And once again the inductive or experimental method of studying Nature gained a direct advantage from the old Pythagorean idea: because atomic weights were determined with an accuracy formerly unknown. But again the idea could not stand the ordeal of experimental test, yet the prejudice remains and has not been uprooted, even by Stas; nay, it has gained a new vigour, for we see that all which is imperfectly worked out, new and unexplained, from the still scarcely studied rare metals to the hardly perceptible nebulæ, have been used to justify it. As soon as spectrum analysis appears as a new and powerful weapon of chemistry, the idea of a primary matter is immediately attached to it. From all sides we see attempts to constitute the imaginary substance _helium_[3] the so much longed for primary matter. No attention is paid to the circumstance that the helium line is only seen in the spectrum of the solar protuberances, so that its universality in Nature remains as problematic as the primary matter itself; nor to the fact that the helium line is wanting amongst the Fraunhofer lines of the solar spectrum, and thus does not answer to the brilliant fundamental conception which gives its real force to spectrum analysis. [3] That is, a substance having a wave-length equal to 0·0005875 millimetre. And finally, no notice is even taken of the indubitable fact that the brilliancies of the spectral lines of the simple substances vary under different temperatures and pressures; so that all probabilities are in favour of the helium line simply belonging to some long since known element placed under such conditions of temperature, pressure, and gravity as have not yet been realised in our experiments. Again, the idea that the excellent investigations of Lockyer of the spectrum of iron can be interpreted in favour of the compound nature of that element, evidently must have arisen from some misunderstanding. The spectrum of a compound certainly does not appear as a sum of the spectra of its components; and therefore the observations of Lockyer can be considered precisely as a proof that iron undergoes no other changes at the temperature of the sun than those which it experiences in the voltaic arc--provided the spectrum of iron is preserved. As to the shifting of some of the lines of the spectrum of iron while the other lines maintain their positions, it can be explained, as shown by M. Kleiber ('Journal of the Russian Chemical and Physical Society,' 1885, 147), by the relative motion of the various strata of the sun's atmosphere, and by Zöllner's laws of the relative brilliancies of different lines of the spectrum. Moreover, it ought not to be forgotten that if iron were really proved to consist of two or more unknown elements, we should simply have an increase in the number of our elements--not a reduction, and still less a reduction of all of them to one single primary matter. Feeling that spectrum analysis will not yield a support to the Pythagorean conception, its modern promoters are so bent upon its being confirmed by the periodic law, that the illustrious Berthelot, in his work 'Les origines de l'Alchimie,' 1885, 313, has simply mixed up the fundamental idea of the law of periodicity with the ideas of Prout, the alchemists, and Democritus about primary matter.[4] But the periodic law, based as it is on the solid and wholesome ground of experimental research, has been evolved independently of any conception as to the nature of the elements; it does not in the least originate in the idea of a unique matter; and it has no historical connection with that relic of the torments of classical thought, and therefore it affords no more indication of the unity of matter or of the compound character of our elements, than the law of Avogadro, or the law of specific heats, or even the conclusions of spectrum analysis. None of the advocates of a unique matter have ever tried to explain the law from the standpoint of ideas taken from a remote antiquity when it was found convenient to admit the existence of many gods--and of a unique matter. [4] He maintains (on p. 309) that the periodic law requires two new analogous elements, having atomic weights of 48 and 64, occupying positions between sulphur and selenium, although nothing of the kind results from any of the different readings of the law. When we try to explain the origin of the idea of a unique primary matter, we easily trace that in the absence of inductions from experiment it derives its origin from the scientifically philosophical attempt at discovering some kind of unity in the immense diversity of individualities which we see around. In classical times such a tendency could only be satisfied by conceptions about the immaterial world. As to the material world, our ancestors were compelled to resort to some hypothesis, and they adopted the idea of unity in the formative material, because they were not able to evolve the conception of any other possible unity in order to connect the multifarious relations of matter. Responding to the same legitimate scientific tendency, natural science has discovered throughout the universe a unity of plan, a unity of forces, and a unity of matter, and the convincing conclusions of modern science compel every one to admit these kinds of unity. But while we admit unity in many things, we none the less must also explain the individuality and the apparent diversity which we cannot fail to trace everywhere. It has been said of old, 'Give us a fulcrum, and it will become easy to displace the earth.' So also we must say, 'Give us something that is individualised, and the apparent diversity will be easily understood.' Otherwise, how could unity result in a multitude? After a long and painstaking research, natural science has discovered the individualities of the chemical elements, and therefore it is now capable not only of analysing, but also of synthesising; it can understand and grasp generality and unity, as well as the individualised and the multifarious. The general and universal, like time and space, like force and motion, vary uniformly; the uniform admit of interpolations, revealing every intermediate phase. But the multitudinous, the individualised--such as ourselves, or the chemical elements, or the members of a peculiar periodic function of the elements, or Dalton's multiple proportions--is characterised in another way: we see in it, side by side with a connecting general principle, leaps, breaks of continuity, points which escape from the analysis of the infinitely small--an absence of complete intermediate links. Chemistry has found an answer to the question as to the causes of multitudes; and while retaining the conception of many elements, all submitted to the discipline of a general law, it offers an escape from the Indian Nirvana--the absorption in the universal, replacing it by the individualised. However, the place for individuality is so limited by the all-grasping, all-powerful universal, that it is merely a point of support for the understanding of multitude in unity. Having touched upon the metaphysical bases of the conception of a unique matter which is supposed to enter into the composition of all bodies. I think it necessary to dwell upon another theory, akin to the above conception--the theory of the compound character of the elements now admitted by some--and especially upon one particular circumstance which, being related to the periodic law, is considered to be an argument in favour of that hypothesis. Dr. Pelopidas, in 1883, made a communication to the Russian Chemical and Physical Society on the periodicity of the hydrocarbon radicles, pointing out the remarkable parallelism which was to be noticed in the change of properties of hydrocarbon radicles and elements when classed in groups. Professor Carnelley, in 1886, developed a similar parallelism. The idea of M. Pelopidas will be easily understood if we consider the series of hydrocarbon radicles which contain, say, 6 atoms of carbon:-- I. II. III. IV. V. C_{6}H_{13} C_{6}H_{12} C_{6}H_{11} C_{6}H_{10} C_{6}H_{9} VI. VII. VIII. C_{6}H_{8} C_{6}H_{7} C_{6}H_{6} The first of these radicles, like the elements of the 1st group, combines with Cl, OH, and so on, and gives the derivatives of hexyl alcohol, C_{6}H_{13}(OH); but, in proportion as the number of hydrogen atoms decreases, the capacity of the radicles of combining with, say, the halogens increases. C_{6}H_{12} already combines with 2 atoms of chlorine; C_{6}H_{11}, with 3 atoms, and so on. The last members of the series comprise the radicles of acids: thus C_{6}H_{8}, which belongs to the 6th group, gives, like sulphur, a bibasic acid, C_{6}H_{8}O_{2}(OH)_{2}, which is homologous with oxalic acid. The parallelism can be traced still further, because C_{6}H_{5} appears as a monovalent radicle of benzene, and with it begins a new series of aromatic derivatives, so analogous to the derivatives of the aliphatic series. Let me also mention another example from among those which have been given by M. Pelopidas. Starting from the alkaline radicle of monomethylammonium, N(CH_{3})H_{3}, or NCH_{6}, which presents many analogies with the alkaline metals of the 1st group, he arrives, by successively diminishing the number of the atoms of hydrogen, at a 7th group which contains cyanogen, CN, which has long since been compared to the halogens of the 7th group. The most important consequence which, in my opinion, can be drawn from the above comparison is that the periodic law, so apparent in the elements, has a wider application than might appear at first sight; it opens up a new vista of chemical evolutions. But, while admitting the fullest parallelism between the periodicity of the elements and that of the compound radicles, we must not forget that in the periods of the hydrocarbon radicles we have a _decrease_ of mass as we pass from the representatives of the first group to the next, while in the periods of the elements the mass _increases_ during the progression. It thus becomes evident that we cannot speak of an identity of periodicity in both cases, unless we put aside the ideas of mass and attraction, which are the real corner-stones of the whole of natural science, and even enter into those very conceptions of simple substances which came to light a full hundred years later than the immortal principles of Newton.[5] [5] It is noteworthy that the year in which Lavoisier was born (1743)--the author of the idea of elements and of the indestructibility of matter--is later by exactly one century than the year in which the author of the theory of gravitation and mass was born (1643 N.S.). The affiliation of the ideas of Lavoisier and those of Newton is beyond doubt. From the foregoing, as well as from the failures of so many attempts at finding in experiment and speculation a proof of the compound character of the elements and of the existence of primordial matter, it is evident, in my opinion, that this theory must be classed among mere utopias. But utopias can only be combated by freedom of opinion, by experiment, and by new utopias. In the republic of scientific theories freedom of opinions is guaranteed. It is precisely that freedom which permits me to criticise openly the widely-diffused idea as to the unity of matter in the elements. Experiments and attempts at confirming that idea have been so numerous that it really would be instructive to have them all collected together, if only to serve as a warning against the repetition of old failures. And now as to new utopias which may be helpful in the struggle against the old ones, I do not think it quite useless to mention a _phantasy_ of one of my students who imagined that the weight of bodies does not depend upon their mass, but upon the character of the motion of their atoms. The atoms, according to this new utopian, may all be homogeneous or heterogeneous, we know not which; we know them in motion only, and that motion they maintain with the same persistence as the stellar bodies maintain theirs. The weights of atoms differ only in consequence of their various modes and quantity of motion; the heaviest atoms may be much simpler than the lighter ones: thus an atom of mercury may be simpler than an atom of hydrogen--the manner in which it moves causes it to be heavier. My interlocutor even suggested that the view which attributes the greater complexity to the lighter elements finds confirmation in the fact that the hydrocarbon radicles mentioned by Pelopidas, while becoming lighter as they lose hydrogen, change their properties periodically in the same manner as the elements change theirs, according as the atoms grow heavier. The French proverb, _La critique est facile, mais l'art est difficile_, however, may well be reversed in the case of all such ideal views, as it is much easier to formulate than to criticise them. Arising from the virgin soil of newly-established facts, the knowledge relating to the elements, to their masses, and to the periodic changes of their properties has given a motive for the formation of utopian hypotheses, probably because they could not be foreseen by the aid of any of the various metaphysical systems, and exist, like the idea of gravitation, as an independent outcome of natural science, requiring the acknowledgment of general laws, when these have been established with the same degree of persistency as is indispensable for the acceptance of a thoroughly established fact. Two centuries have elapsed since the theory of gravitation was enunciated, and although we do not understand its cause, we still must regard gravitation as a fundamental conception of natural philosophy, a conception which has enabled us to perceive much more than the metaphysicians did or could with their seeming omniscience. A hundred years later the conception of the elements arose; it made chemistry what it now is; and yet we have advanced as little in our comprehension of simple substances since the times of Lavoisier and Dalton as we have in our understanding of gravitation. The periodic law of the elements is only twenty years old; it is not surprising, therefore, that, knowing nothing about the causes of gravitation and mass, or about the nature of the elements, we do not comprehend the _rationale_ of the periodic law. It is only by collecting established laws--that is, by working at the acquirement of truth--that we can hope gradually to lift the veil which conceals from us the causes of the mysteries of Nature and to discover their mutual dependency. Like the telescope and the microscope, laws founded on the basis of experiment are the instruments and means of enlarging our mental horizon. In the remaining part of my communication I shall endeavour to show, and as briefly as possible, in how far the periodic law contributes to enlarge our range of vision. Before the promulgation of this law the chemical elements were mere fragmentary, incidental facts in Nature; there was no special reason to expect the discovery of new elements, and the new ones which were discovered from time to time appeared to be possessed of quite novel properties. The law of periodicity first enabled us to perceive undiscovered elements at a distance which formerly was inaccessible to chemical vision; and long ere they were discovered new elements appeared before our eyes possessed of a number of well-defined properties. We now know three cases of elements whose existence and properties were foreseen by the instrumentality of the periodic law. I need but mention the brilliant discovery of _gallium_, which proved to correspond to eka-aluminium of the periodic law, by Lecoq de Boisbaudran; of _scandium_, corresponding to ekaboron, by Nilson; and of _germanium_, which proved to correspond in all respects to ekasilicon, by Winkler. When, in 1871, I described to the Russian Chemical Society the properties, clearly defined by the periodic law, which such elements ought to possess, I never hoped that I should live to mention their discovery to the Chemical Society of Great Britain as a confirmation of the exactitude and the generality of the periodic law. Now that I have had the happiness of doing so, I unhesitatingly say that, although greatly enlarging our vision, even now the periodic law needs further improvements in order that it may become a trustworthy instrument in further discoveries.[6] [6] I foresee some more new elements, but not with the same certitude as before. I shall give one example, and yet I do not see it quite distinctly. In the series which contains Hg = 204, Pb = 206, and Bi = 208, we can imagine the existence (at the place VI-11) of an element analogous to tellurium, which we can describe as dvi-tellurium, Dt, having an atomic weight of 212, and the property of forming the oxide DtO_{3}. If this element really exists, it ought in the free state to be an easily fusible, crystalline, non-volatile metal of a grey colour, having a density of about 9·3, capable of giving a dioxide, DtO_{2}, equally endowed with feeble acid and basic properties. This dioxide must give on active oxidation an unstable higher oxide, DtO_{3}, which should resemble in its properties PbO_{2} and Bi_{2}O_{5}. Dvi-tellurium hydride, if it be found to exist, will be a less stable compound than even H_{2}Te. The compounds of dvi-tellurium will be easily reduced, and it will form characteristic definite alloys with other metals. I will venture to allude to some other matters which chemistry has discerned by means of its new instrument, and which it could not have made out without a knowledge of the law of periodicity, and I will confine myself to simple substances and to oxides. Before the periodic law was formulated the atomic weights of the elements were purely empirical numbers, so that the magnitude of the equivalent, and the atomicity, or the value in substitution possessed by an atom, could only be tested by critically examining the methods of determination, but never directly by considering the numerical values themselves; in short, we were compelled to move in the dark, to submit to the facts, instead of being masters of them. I need not recount the methods which permitted the periodic law at last to master the facts relating to atomic weights, and I would merely call to mind that it compelled us to modify the valencies of _indium_ and _cerium_, and to assign to their compounds a different molecular composition. Determinations of the specific heats of these two metals fully confirmed the change. The trivalency of _yttrium_, which makes us now represent its oxide as Y_{2}O_{3} instead of as YO, was also foreseen (in 1870) by the periodic law, and it has now become so probable that Clève, and all other subsequent investigators of the rare metals, have not only adopted it, but have also applied it without any new demonstration to substances so imperfectly known as those of the cerite and gadolinite group, especially since Hillebrand determined the specific heats of lanthanum and didymium and confirmed the expectations suggested by the periodic law. But here, especially in the case of didymium, we meet with a series of difficulties long since foreseen through the periodic law, but only now becoming evident, and chiefly arising from the relative rarity and insufficient knowledge of the elements which usually accompany didymium. Passing to the results obtained in the case of the rare elements _beryllium_, _scandium_, and _thorium_, it is found that these have many points of contact with the periodic law. Although Avdéeff long since proposed the magnesia formula to represent beryllium oxide, yet there was so much to be said in favour of the alumina formula, on account of the specific heat of the metals and the isomorphism of the two oxides, that it became generally adopted and seemed to be well established. The periodic law, however, as Brauner repeatedly insisted ('Berichte,' 1878, 872; 1881, 53), was against the formula Be_{2}O_{3}; it required the magnesia formula BeO--that is, an atomic weight of 9--because there was no place in the system for an element like beryllium having an atomic weight of 13·5. This divergence of opinion lasted for years, and I often heard that the question as to the atomic weight of beryllium threatened to disturb the generality of the periodic law, or, at any rate, to require some important modifications of it. Many forces were operating in the controversy regarding beryllium, evidently because a much more important question was at issue than merely that involved in the discussion of the atomic weight of a relatively rare element: and during the controversy the periodic law became better understood, and the mutual relations of the elements became more apparent than ever before. It is most remarkable that the victory of the periodic law was won by the researches of the very observers who previously had discovered a number of facts in support of the trivalency of beryllium. Applying the higher law of Avogadro, Nilson and Petterson have finally shown that the density of the vapour of the beryllium chloride, BeCl_{2}, obliges us to regard beryllium as bivalent in conformity with the periodic law.[7] I consider the confirmation of Avdéeff's and Brauner's view as important in the history of the periodic law as the discovery of scandium, which, in Nilson's hands, confirmed the existence of ekaboron. [7] Let me mention another proof of the bivalency of beryllium which may have passed unnoticed, as it was only published in the Russian chemical literature. Having remarked (in 1884) that the density of such solutions of chlorides of metals, MCl_{_n_}, as contain 200 mols. of water (or a large and constant amount of water) regularly increases as the molecular weight of the dissolved salt increases, I proposed to one of our young chemists, M. Burdakoff, that he should investigate beryllium chloride. If its molecule be BeCl_{2} its weight must be = 80; and in such a case it must be heavier than the molecule of KCl = 74·5, and lighter than that of MgCl_{2}, = 93. On the contrary, if beryllium chloride is a trichloride, BeCl_{3} = 120, its molecule must be heavier than that of CaCl_{2} = 111, and lighter than that of MnCl_{2} = 126. Experiment has shown the correctness of the former formula, the solution BeCl_{2} + 200H_{2}O having (at 15°/4°) a density of 1·0138, this being a higher density than that of the solution KCl + 200H_{2}O (= 1·0121), and lower than that of MgCl_{2} + 200H_{2}O (= 1·0203). The bivalency of beryllium was thus confirmed in the case both of the dissolved and the vaporised chloride. The circumstance that _thorium_ proved to be quadrivalent, and Th = 232, in accordance with the views of Chydenius and the requirements of the periodic law, passed almost unnoticed, and was accepted without opposition, and yet both thorium and uranium are of great importance in the periodic system, as they are its last members, and have the highest atomic weights of all the elements. The alteration of the atomic weight of _uranium_ from U = 120 into U = 240 attracted more attention, the change having been made on account of the periodic law, and for no other reason. Now that Roscoe, Rammelsberg, Zimmermann, and several others have admitted the various claims of the periodic law in the case of uranium, its high atomic weight is received without objection, and it endows that element with a special interest. While thus demonstrating the necessity for modifying the atomic weights of several insufficiently known elements, the periodic law enabled us also to detect errors in the determination of the atomic weights of several elements whose valencies and true position among other elements were already well known. Three such cases are especially noteworthy: those of tellurium, titanium and platinum. Berzelius had determined the atomic weight of _tellurium_ to be 128, while the periodic law claimed for it an atomic weight below that of iodine, which had been fixed by Stas at 126·5, and which was certainly not higher than 127. Brauner then undertook the investigation, and he has shown that the true atomic weight of tellurium is lower than that of iodine, being near to 125. For _titanium_ the extensive researches of Thorpe have confirmed the atomic weight of Ti = 48, indicated by the law, and already foreseen by Rose, but contradicted by the analyses of Pierre and several other chemists. An equally brilliant confirmation of the expectations based on the periodic law has been given in the case of the series osmium, iridium, platinum, and gold. At the time of the promulgation of the periodic law, the determinations of Berzelius, Rose, and many others gave the following figures:-- Os = 200; Ir = 197; Pt = 198; Au = 196. The expectations of the periodic law[8] have been confirmed, first, by new determinations of the atomic weight of _platinum_ (by Seubert, Dittmar, and M'Arthur, which proved to be near to 196 (taking O = 16, as proposed by Marignac, Brauner, and others); secondly, by Seubert having proved that the atomic weight of _osmium_ is really lower than that of platinum, being near to 191; and thirdly, by the investigations of Krüss, Thorpe and Laurie, proving that the atomic weight of _gold_ exceeds that of platinum, and approximates to 197. The atomic weights which were thus found to require correction were precisely those which the periodic law had indicated as affected with errors; and it has been proved, therefore, that the periodic law affords a means of testing experimental results. If we succeed in discovering the exact character of the periodic relationships between the increments in atomic weights of allied elements discussed by Ridberg in 1885, and again by Bazaroff in 1887, we may expect that our instrument will give us the means of still more closely controlling the experimental data relating to atomic weights. [8] I pointed them out in the _Liebig's Annalen_, Supplement Band., viii. 1871, p. 211. Let me next call to mind that, while disclosing the variation of chemical properties,[9] the periodic law, has also enabled us to systematically discuss many of the physical properties of elementary bodies, and to show that these properties are also subject to the law of periodicity. At the Moscow Congress of Russian Naturalists in August, 1869, I dwelt upon the relations which existed between density and the atomic weight of the elements. The following year Professor Lothar Meyer, in his well-known paper,[10] studied the same subject in more detail, and thus contributed to spread information about the periodic law. Later on, Carnelley, Laurie, L. Meyer, Roberts-Austen, and several others applied the periodic system to represent the order in the changes of the magnetic properties of the elements, their melting points, the heats of formation of their haloid compounds, and even of such mechanical properties as the coefficient of elasticity, the breaking stress, &c., &c. These deductions, which have received further support in the discovery of new elements endowed not only with chemical but even with physical properties, which were foreseen by the law of periodicity, are well known; so I need not dwell upon the subject, and may pass to the consideration of oxides.[11] [9] Thus, in the typical small period of Li, Be, B, C, N, O, F, we see at once the progression from the alkali metals to the acid non-metals, such as are the halogens. [10] _Liebig's Annalen_, Supplement Band., vii. 1870. [11] A distinct periodicity can also be discovered in the spectra of the elements. Thus the researches of Hartley, Ciamician, and others have disclosed, first, the homology of the spectra of analogous elements: secondly, that the alkali metals have simpler spectra than the metals of the following groups; and thirdly, that there is a certain likeness between the complicated spectra of manganese and iron on the one hand, and the no less complicated spectra of chlorine and bromine on the other hand, and their likeness corresponds to the degree of analogy between those elements which is indicated by the periodic law. In indicating that the gradual increase of the power of elements of combining with oxygen is accompanied by a corresponding decrease in their power of combining with hydrogen, the periodic law has shown that there is a limit of oxidation, just as there is a well-known limit to the capacity of elements for combining with hydrogen. A single atom of an element combines with at most four atoms of either hydrogen or oxygen; and while CH_{4} and SiH_{4} represent the highest hydrides, so RuO_{4} and OsO_{4} are the highest oxides. We are thus led to recognise types of oxides, just as we have had to recognise types of hydrides.[12] [12] Formerly it was supposed that, being a bivalent element, oxygen can enter into any grouping of the atoms, and there was no limit foreseen as to the extent to which it could further enter into combination. We could not explain why bivalent sulphur, which forms compounds such as O O / \ / \ S | and S O, \ / \ / O O could not also form oxides such as-- O--O O--O / \ / \ S | or S O, \ / \ / O--O O--O while other elements, as, for instance, chlorine, form compounds such as-- Cl--O--O--O--O--K The periodic law has demonstrated that the maximum extent to which different non-metals enter into combination with oxygen is determined by the extent to which they combine with hydrogen, and that the sum of the number of equivalents of both must be equal to 8. Thus chlorine, which combines with 1 atom or 1 equivalent of hydrogen, cannot fix more than 7 equivalents of oxygen, giving Cl_{2}O_{7}; while sulphur, which fixes 2 equivalents of hydrogen, cannot combine with more than 6 equivalents or 3 atoms of oxygen. It thus becomes evident that we cannot recognise as a fundamental property of the elements the atomic valencies deduced from their hydrides; and that we must modify, to a certain extent, the theory of atomicity if we desire to raise it to the dignity of a general principle capable of affording an insight into the constitution of all compound molecules. In other words, it is only to carbon, which is quadrivalent with regard both to oxygen and hydrogen, that we can apply the theory of constant valency and of bond, by means of which so many still endeavour to explain the structure of compound molecules. But I should go too far if I ventured to explain in detail the conclusions which can be drawn from the above considerations. Still, I think it necessary to dwell upon one particular fact which must be explained from the point of view of the periodic law in order to clear the way to its extension in that particular direction. The higher oxides yielding salts the formation of which was foreseen by the periodic system--for instance, in the short series beginning with sodium-- Na_{2}O, MgO, Al_{2}O_{3}, SiO_{2}, P_{2}O_{5}, SO_{3}, Cl_{2}O_{7}, must be clearly distinguished from the higher degrees of oxidation which correspond to hydrogen peroxide and bear the true character of peroxides. Peroxides such as Na_{2}O_{2}, BaO_{2}, and the like have long been known. Similar peroxides have also recently become known in the case of chromium, sulphur, titanium, and many other elements, and I have sometimes heard it said that discoveries of this kind weaken the conclusions of the periodic law in so far as it concerns the oxides. I do not think so in the least, and I may remark, in the first place, that all these peroxides are endowed with certain properties obviously common to all of them, which distinguish them from the actual, higher, salt-forming oxides, especially their easy decomposition by means of simple contact agencies; their incapability of forming salts of the common type; and their capability of combining with other peroxides (like the faculty which hydrogen peroxide possesses of combining with barium peroxide, discovered by Schoene). Again, we remark that some groups are especially characterised by their capacity of generating peroxides. Such is, for instance, the case in the sixth group, where we find the well-known peroxides of sulphur, chromium, and uranium; so that further investigation of peroxides will probably establish a new periodic function, foreshadowing that molybdenum and tungsten will assume peroxide forms with comparative readiness. To appreciate the constitution of such peroxides, it is enough to notice that the peroxide form of sulphur (so-called persulphuric acid) stands in the same relation to sulphuric acid as hydrogen peroxide stands to water:-- H(OH), or H_{2}O, responds to (OH)(OH), or H_{2}O_{2}, and so also-- H(HSO_{4}), or H_{2}SO_{4}, responds to (HSO_{4})(HSO_{4}), or H_{2}S_{2}O_{8}. Similar relations are seen everywhere, and they correspond to the principle of substitutions which I long since endeavoured to represent as one of the chemical generalisations called into life by the periodic law. So also sulphuric acid, if considered with reference to hydroxyl, and represented as follows:-- HO(SO_{2}OH), has its corresponding compound in dithionic acid-- (SO_{2}OH)(SO_{2}OH), or H_{2}S_{2}O_{6}. Therefore, also, phosphoric acid, HO(POH_{2}O_{2}), has, in the same sense, its corresponding compound in the subphosphoric acid of Saltzer:-- (POH_{2}O_{2})(POH_{2}O_{2}), or H_{4}P_{2}O_{6}; and we must suppose that the peroxide compound corresponding to phosphoric acid, if it be discovered, will have the following structure:-- (H_{2}PO_{4})_{2} or H_{4}P_{2}O_{8} = 2H_{2}O + 2PO_{3}.[13] So far as is known at present, the highest form of peroxides is met with in the peroxide of uranium, UO_{4}, prepared by Fairley;[14] while OsO_{4} is the highest oxide giving salts. The line of argument which is inspired by the periodic law, so far from being weakened by the discovery of peroxides, is thus actually strengthened, and we must hope that a further exploration of the region under consideration will confirm the applicability to chemistry generally of the principles deduced from the periodic law. [13] In this sense, oxalic acid, (COOH)_{2}, also corresponds to carbonic acid, OH(COOH), in the same way that dithionic acid corresponds to sulphuric acid, and subphosphoric acid to phosphoric; hence, if a peroxide corresponding to carbonic acid be obtained, it will have the structure of (HCO_{3})_{2}, or H_{2}C_{2}O_{6} = H_{2}O + C_{2}O_{5}. So also lead must have a real peroxide, Pb_{2}O_{5}. [14] The compounds of uranium prepared by Fairley seem to me especially instructive in understanding the peroxides. By the action of hydrogen peroxide on uranium oxide, UO_{3}, a peroxide of uranium, UO_{4},4H_{2}O, is obtained (U = 240) if the solution be acid; but if hydrogen peroxide act on uranium oxide in the presence of caustic soda, a crystalline deposit is obtained which has the composition Na_{4}UO_{8},4H_{2}O, and evidently is a combination of sodium peroxide, Na_{2}O_{2}, with uranium peroxide, UO_{4}. It is possible that the former peroxide, UO_{4},4H_{2}O, contains the elements of hydrogen peroxide and uranium peroxide, U_{2}O_{7}, or even U(OH)_{6},H_{2}O_{2}, like the peroxide of tin recently discovered by Spring, which has the constitution Sn_{2}O_{5},H_{2}O_{2}. Permit me now to conclude my rapid sketch of the oxygen compounds by the observation that the periodic law is especially brought into evidence in the case of the oxides which constitute the immense majority of bodies at our disposal on the surface of the earth. The oxides are evidently subject to the law, both as regards their chemical and their physical properties, especially if we take into account the cases of polymerism which are so obvious when comparing CO_{2}, with Si_{_n_}O_{2_n_}. In order to prove this I give the densities s and the specific volumes v of the higher oxides of two short periods. To render comparison easier, the oxides are all represented as of the form R_{2}O_{_n_}. In the column headed [Delta] the differences are given between the volume of the oxygen compound and that of the parent element, divided by _n_--that is, by the number of atoms of oxygen in the compound:--[15] _s._ _v._ [Delta] Na_{2}O 2·6 24 -22 Mg_{2}O_{2} 3·6 22 -3 Al_{2}O_{3} 4·0 26 +1·3 Si_{2}O_{4} 2·65 45 5·2 P_{2}O_{5} 2·39 59 6·2 S_{2}O_{6} 1·96 82 8·7 K_{2}O 2·7 35 -55 Sc_{2}O_{3} 3·86 35 0 Li_{2}O_{4} 4·2 38 +5 V_{2}O_{5} 3·49 52 6·7 Cr_{2}O_{6} 2·74 73 9·5 [15] [Delta] thus represents the average increase of volume for each atom of oxygen contained in the higher salt-forming oxide. The acid oxides give, as a rule, a higher value of [Delta], while in the case of the strongly alkaline oxides its value is usually negative. I have nothing to add to these figures, except that like relations appear in other periods as well. The above relations were precisely those which made it possible for me to be certain that the relative density of ekasilicon oxide would be about 4·7; germanium oxide, actually obtained by Winkler, proved, in fact, to have the relative density 4·703. The foregoing account is far from being an exhaustive one of all that has already been discovered by means of the periodic law telescope in the boundless realms of chemical evolution. Still less is it an exhaustive account of all that may yet be seen, but I trust that the little which I have said will account for the philosophical interest attached in chemistry to this law. Although but a recent scientific generalisation, it has already stood the test of laboratory verification, and appears as an instrument of thought which has not yet been compelled to undergo modification; but it needs not only new applications, but also improvements, further development, and plenty of fresh energy. All this will surely come, seeing that such an assembly of men of science as the Chemical Society of Great Britain has expressed the desire to have the history of the periodic law described in a lecture dedicated to the glorious name of Faraday. APPENDIX III ARGON, A NEW CONSTITUENT OF THE ATMOSPHERE WRITTEN BY PROFESSOR MENDELÉEFF IN FEBRUARY 1895 The remarks made in Chapter V., Note 16 bis respecting the newly discovered constituent of the atmosphere are here supplemented by data (taken from the publications of the Royal Society of London) given by the discoverers Lord Rayleigh and Professor Ramsay in January 1895, together with observations made by Crookes and Olszewsky upon the same subject. This gas, which was discovered by Rayleigh and Ramsay in atmospheric nitrogen, was named _argon_[1] by them, and upon the supposition of its being an element, they gave it the symbol A. But its true chemical nature is not yet fully known, for not only has no compound of it been yet obtained, but it has not even been brought into any reaction. From all that is known about it at the present time, we may conclude with the discoverers that argon belongs to those gases which are permanent constituents of the atmosphere, and that it is a new element. The latter statement, however, requires confirmation. We shall presently see, however, that the negative chemical character of argon (its incapacity to react with any substance), and the small amount of it present in the atmosphere (about 1-1/4 per cent. by volume in the nitrogen of air, and consequently about 1 per cent. by volume in air), as well as the recent date of its discovery (1894) and the difficulty of its preparation, are quite sufficient reasons for the incompleteness of the existing knowledge respecting this element. But since, so far as is yet known, we are dealing with a normal constituent of the atmosphere[1 bis], the existing data, notwithstanding their insufficiently definite nature, should find a place even in such an elementary work as the present, all the more as the names of Rayleigh, Ramsay, Crookes and Olszewsky, who have worked upon argon, are among the highest in our science, and their researches among the most difficult.[2] These researches, moreover, were directed straight to the goal, which was only partly reached owing to the unusual properties of argon itself. [1] From the Greek [Greek: Argon]--inert. [1 bis] In Note 16 bis, Chapter V., I mentioned that, judging from the specific gravity of argon, it might possibly be polymerised nitrogen, N_{3}, bearing the same relationship to nitrogen, N_{2}, that ozone, O_{3}, bears to ordinary oxygen. If this idea were confirmed, still one would not imagine that argon was formed from the atmospheric nitrogen by those reactions by which it was obtained by Rayleigh and Ramsay, but rather that it arises from the nitrogen of the atmosphere under natural conditions. Although this proposition is not quite destroyed by the more recent results, still it is contradicted by the fact that the ratio of the specific heats of argon was found to be 1·66, which, as far as is now known, could not be the case for a gas containing 3 atoms in its molecule, since such gases (_see_ Chapter XIV., Note 7) give the ratio approximately 1·3 (for example, CO_{2}). In abstaining from further conclusions, for they must inevitably be purely conjectural, I consider it advisable to suggest that in conducting further researches upon argon it might be well to subject it to as high a temperature as possible. And the possibility of nitrogen polymerising is all the more admissible from the fact that the aggregation of its atoms in the molecule is not at all unlikely, and that polymerised nitrogen, judging from many examples, might be inert if the polymerisation were accompanied by the evolution of heat. In the following footnotes I frequently return to this hypothesis, not only because I have not yet met any facts definitely contradictory to it, but also because the chief properties of argon agree with it to a certain extent. [2] The chief difficulty in investigating argon lies in the fact that its preparation requires the employment of a large quantity of air, which has to be treated with a number of different reagents, whose perfect purity (especially that of magnesium) will always be doubtful, and argon has not yet been transferred to a substance in which it could be easily purified. Perhaps the considerable solubility of argon in water (or in other suitable liquids, which have not apparently yet been tried) may give the means of doing so, and it may be possible, by collecting the air expelled from boiling water, to obtain a richer source of argon than ordinary air. When it became known (Chapter V., Note 4 bis) that the nitrogen obtained from air (by removing the oxygen, moisture and CO_{2}, by various reagents) has a greater density than that obtained from the various (oxygen, hydrogen and metallic) compounds of nitrogen, it was a plausible explanation that the latter contained an admixture of hydrogen, or of some other light gas lowering the density of the mixture. But such an assumption is refuted not only by the fact that the nitrogen obtained from its various compounds (after purification) has always the same density (although the supposed impurities mixed with it should vary), but also by Rayleigh and Ramsay's experiment of artificially adding hydrogen to nitrogen, and then passing the mixture over red-hot oxide of copper, when it was found that the nitrogen regained its original density, _i.e._ that the whole of the hydrogen was removed by this treatment. Therefore the difference in the density of the two varieties of nitrogen had to be explained by the presence of a heavier gas in admixture with the nitrogen obtained from the atmosphere. This hypothesis was confirmed by the fact that Rayleigh and Ramsay having obtained purified nitrogen (by removing the O_{2}, CO_{2}, and H_{2}O), both from ordinary air and from air which had been previously subjected to atmolysis, that is which had been passed through porous tubes (of burnt clay, _e.g._ pipe-stem), surrounded by a rarefied space, and so deprived of its lighter constituents (chiefly nitrogen), found that the nitrogen from the air which had been subjected to atmolysis was heavier than that obtained from air which had not been so treated. This experiment showed that the nitrogen of air contains an admixture of a gas which, being heavier than nitrogen itself,[3] diffuses more slowly than nitrogen through the porous material. It remained, therefore, to separate this impurity from the nitrogen. To do this Rayleigh and Ramsay adopted two methods, converting the nitrogen into solid and liquid substances, either by absorbing the nitrogen by heated magnesium (Chapter V., Note 6, and Chapter XIV., Note 14), with the formation of nitride of magnesium, or else by converting it into nitric acid by the action of electric sparks or the presence of an excess of air and alkali, as in Cavendish's method.[3 bis] In both cases the nitrogen entered into reaction, while the heavier gas mixed with it remained inert, and was thus able to be isolated. That is, the argon could be separated by these means from the excess of atmospheric nitrogen accompanying it.[4] As an illustration we will describe how argon was obtained from the atmospheric nitrogen by means of magnesium.[5] To begin with, it was discovered that when atmospheric nitrogen was passed through a tube containing metallic magnesium heated to redness, its specific gravity rose to 14·88. As this showed that part of the gas was absorbed by the magnesium, a mercury gasometer filled with atmospheric nitrogen was taken, and the gas drawn over soda-lime, P_{2}O_{5}, heated magnesium[6] and then through tubes containing red-hot copper oxide, soda-lime and phosphoric anhydride to a second mercury gasometer. Every time the gas was repassed through the tubes, it decreased in volume and increased in density. After repeating this for ten days 1,500 c.c. of gas were reduced to 200 cc., and the density increased to 16·1 (if that of H_{2} = 1 and N_{2} = 14). Further treatment of the remainder brought the density up to 19·09. After adding a small quantity of oxygen and repassing the gas through the apparatus, the density rose to 20·0. To obtain argon by this process Ramsay and Rayleigh (employing a mercury air pump and mercury gasometers) once treated about 150 litres of atmospheric nitrogen. On another occasion they treated 7,925 c.c. of air by the oxidation method and obtained 65 c.c. of argon, which corresponds to 0·82 per cent. The density of the argon obtained by this means was nearly 19·7, while that obtained by the magnesium method varied between 19·09 and 20·38. [3] It might also be supposed that this heavy gas is separated by the copper when the latter absorbs the oxygen of the air; but such a supposition is not only improbable in itself, but does not agree with the fact that nitrogen may be obtained from air by absorbing the oxygen by various other substances in solution (for instance, by the lower oxides of the metals, like FeO) besides red-hot copper, and that the nitrogen obtained is always just as heavy. Besides which, nitrogen is also set free from its oxides by copper, and the nitrogen thus obtained is lighter. Therefore it is not the copper which produces the heavy gas--_i.e._ argon. [3 bis] It is worthy of note that Cavendish obtained a small residue of gas in converting nitrogen into nitric acid; but he paid no attention to it, although probably he had in his hands the very argon recently discovered. [4] When in these experiments, instead of atmospheric nitrogen the gas obtained from its compound was taken, an inert residue of a heavy gas, having the properties of argon, was also remarked, but its amount was very small. Rayleigh and Ramsay ascribe the formation of this residue to the fact that the gas in these experiments was collected over water, and a portion of the dissolved argon in it might have passed into the nitrogen. As the authors of this supposition did not prove it by any special experiments, it forms a weak point in their classical research. If it be admitted that argon is N_{3}, the fact of its being obtained from the nitrogen of compounds might be explained by the polymerisation of a portion of the nitrogen in the act of reaction, although it is impossible to refute Rayleigh and Ramsay's hypothesis of its being evolved from the water employed in the manipulation of the gases. Three thousand volumes of nitrogen extracted from its compounds gave about three volumes of argon, while thirty volumes were yielded by the same amount of atmospheric nitrogen. [5] The preparation of argon by the conversion of nitrogen into nitric acid is complicated by the necessity of adding a large proportion of oxygen and alkali, of passing an electric discharge through the mixture for a long period, and then removing the remaining oxygen. All this was repeatedly done by the authors, but this method is far more complex, both in practice and theory, than the preparation of argon by means of magnesium. From 100 volumes of air subjected to conversion into HNO_{3}, 0·76 volume of argon were obtained after absorbing the excess of oxygen. [6] In these and the following experiments the magnesium was placed in an ordinary hard glass tube, and heated in a gas furnace to a temperature almost sufficient to soften the glass. The current of gas must be very slow (a tube containing a small quantity of sulphuric acid served as a meter), as otherwise the heat evolved in the formation of the Mg_{3}N_{2} (Chapter XIV., Note 14) will melt the tube. Thus the first positive and very important fact respecting argon is that its specific gravity is nearly 20--that is, that it is 20 times heavier than hydrogen, while nitrogen is only 14 times and oxygen 16 times heavier than hydrogen. This explains the difference observed by Rayleigh between the densities of nitrogen obtained from its compounds and from the atmosphere (Chapter V., Note 4 bis). At 0° and 760 mm. a litre of the former gas weighs 1·2505 grm., while a litre of the latter weighs 1·2572, or taking H = 1, the density of the first = 13·916, and of the latter = 13·991. If the density of argon be taken as 20, it is contained in atmospheric nitrogen to the extent of about 1·23 per cent. by volume, whilst air contains about 0·97 per cent. by volume. When argon had been isolated the question naturally arose, was it a new homogeneous substance having definite properties or was it a mixture of gases? The former may now be positively asserted, namely, that argon is a peculiar gas previously unknown to chemistry. Such a conviction is in the first place established by the fact that argon has a greater number of negative properties, a smaller capacity for reaction, than any other simple or compound body known. The most inert gas known is nitrogen, but argon far exceeds it in this respect. Thus nitrogen is absorbed at a red heat by many metals, with the formation of nitrides, while argon, as is seen in the mode of its preparation and by direct experiment, does not possess this property. Nitrogen, under the action of electric sparks, combines with hydrogen in the presence of acids and with oxygen in the presence of alkalis, while argon is unable to do so, as is seen from the method of separation from nitrogen. Rayleigh and Ramsay also proved that argon is unable to react with chlorine (dry or moist) either directly or under the action of an electric discharge, or with phosphorus or sulphur, at a red heat. Sodium, potassium, and tellurium may be distilled in an atmosphere of argon without change. Fused caustic soda, incandescent soda-lime, molten nitre, red-hot peroxide of sodium, and the polysulphides of calcium and sodium also do not react with argon. Platinum black does not absorb it, and spongy platinum is unable to excite its reaction with oxygen or chlorine. Aqua regia, bromine water, and a mixture of hydrochloric acid and KMnO_{4} were also without action upon argon. Besides which it is evident from the method of its preparation that it is not acted upon by red-hot oxide of copper. All these facts exclude any possibility of argon containing any already known body, and prove it to be the most inert of all the gases known. But besides these negative points, the independency of argon is confirmed by four observed positive properties possessed by it, which are:-- 1. The spectrum of argon observed by Crookes under a low pressure (in Geissler-Plücker tubes) distinguishes it from other gases.[7] It was proved by this means that the argon obtained by means of magnesium is identical with that which remains after the conversion of the atmospheric nitrogen into nitric acid. Like nitrogen, argon presents two spectra produced at different potentials of the induced current, one being orange-red, the other steel-blue; the latter is obtained under a higher degree of rarefaction and with a battery of Leyden jars. Both the spectra of argon (in contradistinction to those of nitrogen) are distinguished by clearly defined lines.[8] The red (ordinary) spectrum of argon has two particularly brilliant and characteristic red lines (not far from the bright red line of lithium, on the opposite side to the orange band) having wave-lengths 705·64 and 696·56 (_see_ Vol. I., p. 565). Between these bright lines there are in addition lines with wave lengths 603·8, 565·1, 561·0, 555·7, 518·58, 516·5, 450·95, 420·10, 415·95 and 394·85. Altogether 80 lines have been observed in this spectrum and 119 in the blue spectrum, of which 26 are common to both spectra.[9] [7] The greatest brilliancy of the spectrum of argon is obtained at a tension of 3 mm., while for nitrogen it is about 75 mm. (Crookes). In Chapter V., Note 16 bis, it is said that the same blue line observed in the spectrum of argon is also observed in the spectrum of nitrogen. This is a mistake, since there is no coincidence between the blue lines of the argon and nitrogen spectra. However, we may add that for nitrogen the following moderately bright lines are known of wave-lengths 585, 574, 544, 516, 457, 442, 436, and 426, which are repeated in the spectra (red and blue) of argon, judging by Crookes' researches (1895); but it is naturally impossible to assert that there is perfect identity until some special comparative work has been done in this subject, which is very desirable, and more especially for the bluish-violet portion of the spectrum, more particularly between the lines 442-436, as these lines are distinguished by their brilliancy in both the argon and nitrogen spectra. The above-mentioned supposition of argon being polymerised nitrogen (N_{3}), formed from nitrogen (N_{2}), with the evolution of heat, might find some support should it be found after careful comparison that even a limited number of spectral lines coincided. [8] At first the spectrum of argon exhibits the nitrogen lines, but after a certain time these lines disappear (under the influence of the platinum, and also of Al and Mg, but with the latter the spectrum of hydrogen appears) and leave a pure argon spectrum. It does not appear clear to me whether a polymerisation here takes place or a simple absorption. Perhaps the elucidation of this question would prove important in the history of argon. It would be desirable to know, for instance, whether the volume of argon changes when it is first subjected to the action of the electric discharge. [9] Crookes supposes that argon contains a mixture of two gases, but as he gives no reasons for this, beyond certain peculiarities of a spectroscopic character, we will not consider this hypothesis further. 2. According to Rayleigh and Ramsay the solubility of argon in water is approximately 4 volumes in 100 volumes of water at 13°. Thus argon is nearly 2-1/2 times more soluble than nitrogen, and its solubility approaches that of oxygen. Direct experiment proves that nitrogen obtained from air from boiled water is heavier than that obtained straight from the atmosphere. This again is an indirect proof of the presence of argon in air. 3. The ratio _k_ of the two specific heats (at a constant pressure and at a constant volume) of argon was determined by Rayleigh and Ramsay by the method of the velocity of sound (_see_ Chapter XIV., Note 7 and Chapter VII., Note 26) and was found to be nearly 1·66, that is greater than for those gases whose molecules contain two atoms (for instance, CO, H_{2}, N_{2}, air, &c., for which _k_ is nearly 1·4) or those whose molecules contain three atoms (for instance, CO_{2}, N_{2}O, &c., for which _k_ is about 1·3), but closely approximate to the ratio of the specific heats of mercury vapour (Kundt and Warburg, _k_ = 1·67). And as the molecule of mercury vapour contains one atom, so it may be said that argon is a simple gaseous body whose molecule contains one atom.[10] A compound body should give a smaller ratio. The experiments upon the liquefaction of argon, which we shall presently describe, speak against the supposition that argon is a mixture of two gases. The importance of the results in question makes one wish that the determinations of the ratio of the specific heats (and other physical properties) might be confirmed with all possible accuracy.[11] If we admit, as we are obliged to do for the present, that argon is a new element, its density shows that its atomic weight must be nearly 40, that is, near to that of K = 39 and Ca = 40, which does not correspond to the existing data respecting the periodicity of the properties of the elements in dependence upon their atomic weights, for there is no reason on the basis of existing data for admitting any intermediate elements between Cl = 35·5 and K = 39, and all the positions above potassium in the periodic system are occupied. This renders it very desirable that the velocity of sound in argon should be re-determined.[12] [10] This portion of Rayleigh and Ramsay's researches deserves particular attention as, so far, no gaseous substance is known whose molecule contains but one atom. Were it not for the above determinations, it might be thought that argon, having a density 20, has a complex molecule, and may be a compound or polymerised body, for instance, N_{3} or NX_{_n_}, or in general X_{_n_}; but as the matter stands, it can only be said that either (1) argon is a new, peculiar, and quite unusual elementary substance, since there is no reason for assuming it to contain two simple gases, or (2) the magnitude, _k_ (the ratio of the specific heats) does not only depend upon the number of atoms contained in the molecules, but also upon the store of internal energy (internal motion of the atoms in the molecule). Should the latter be admitted, it would follow that the molecules of very active gaseous elements would correspond to a smaller _k_ than those of other gases having an equal number of atoms in their molecule. Such a gas is chlorine, for which _k_ = 1·33 (Chapter XIV., Note 7). For gases having a small chemical energy, on the contrary, a larger magnitude would be expected for _k_. I think these questions might be partially settled by determining _k_ for ozone (O_{3}) and sulphur (S_{6}) (at about 500°). In other words, I would suggest, though only provisionally, that the magnitude, _k_ = 1·6, obtained for argon might prove to agree with the hypothesis that argon is N_{3}, formed from N_{2} with the evolution of heat or loss of energy. Here argon gives rise to questions of primary importance, and it is to be hoped that further research will throw some light upon them. In making these remarks, I only wish to clear the road for further progress in the study of argon, and of the questions depending on it. I may also remark that if argon is N_{3} formed with the evolution of heat, its conversion into nitrogen, N_{2}, and into nitride compounds (for instance, boron nitride or nitride of titanium) might only take place at a very high temperature. [11] Without having the slightest reason for doubting the accuracy of Rayleigh and Ramsay's determinations, I think it necessary to say that as yet (February 1895) I am only acquainted with the short memoir of the above chemists in the 'Proceedings of the Royal Society,' which does not give any description of the methods employed and results obtained, while at the end (in the general conclusions) the authors themselves express some doubt as to the simple nature of argon. Moreover, it seems to me that (Note 10) there must be a dependence of _k_ upon the chemical energy. Besides which, it is not clear what density of the gas Rayleigh and Ramsay took in determining _k_. (If argon be N_{3}, its density would be near to 21.) Hence I permit myself to express some doubt as to whether the molecule of argon contains but one atom. [12] If it should be found that _k_ for argon is less than 1·4, or that _k_ is dependent upon the chemical energy, it would be possible to admit that the molecule of argon contains not one, but several atoms--for instance, either N_{3} (then the density would be 21, which is near to the observed density) or X_{6}, if X stand for an element with an atomic weight near to 6·7. No elements are known between H = 1 and Li = 7, but perhaps they may exist. The hypothesis A = 40 does not admit argon into the periodic system. If the molecule of argon be taken as A_{2}--_i.e._ the atomic weight as A = 20--argon apparently finds a place in Group VIII., between F = 19 and Na = 23; but such a position could only be justified by the consideration that elements of small atomic weight belong to the category of typical elements which offer many peculiarities in their properties, as is seen on comparing N with the other elements of Group V., or O with those of Group VI. Apart from this there appears to me to be little probability, in the light of the periodic law, in the position of an inert substance like argon in Group VIII., between such active elements as fluorine and sodium, as the representatives of this group by their atomic weights and also by their properties show distinct transitions from the elements of the last groups of the uneven series to the elements of the first groups of the even series--for instance, Group VI. VII. VIII. I. II. Cr Mn Fe, Co, Ni Cu Zn While if we place argon in a similar manner, VI. VII. VIII. I. II. O = 16 F = 19 A = 20 Na = 23 Mg = 24 although from a numerical point of view there is a similar sequence to the above, still from a chemical and physical point of view the result is quite different, as there is no such resemblance between the properties of O, F and Na, Mg, as between Cr, Mn, and Cu, Zn. I repeat that only the typical character of the elements with small atomic weights can justify the atomic weight A = 20, and the placing of argon in Group VIII. amongst the typical elements; then N, O, F, A are a series of gases. It appears to me simpler to assume that argon contains N_{3}, especially as argon is present in nitrogen and accompanies it, and, as a matter of fact, none of the observed properties of argon are contradictory to this hypothesis. These observations were written by me in the beginning of February 1895, and on the 29th of that month I received a letter, dated February 25, from Professor Ramsay informing me that 'the periodic classification entirely corresponds to its (argon's) atomic weight, and that it even gives a fresh proof of the periodic law,' judging from the researches of my English friends. But in what these researches consisted, and how the above agreement between the atomic weight of argon and the periodic system was arrived at, is not referred to in the letter, and we remain in expectation of a first publication of the work of Lord Rayleigh and Professor Ramsey. [For more complete information see papers read before the Royal Society, January 31, 1895, February 13, March 10, and May 21, 1896, and a paper published in the Chemical Society's Transactions, 1895, p. 684. For abstracts of these and other papers on argon and helium, and correspondence, see 'Nature,' 1895 and 1896. 4. Argon was liquefied by Professor Olszewsky, who is well known for his classical researches upon liquefied gases. These researches have an especial interest since they show that argon exhibits a perfect constancy in its properties in the liquid and critical states, which almost[13] disposes of the supposition that it contains a mixture of two or more unknown gases. As the first experiments showed, argon remains a gas under a pressure of 100 atmospheres and at a temperature of -90°; this indicated that its critical temperature was probably below this temperature, as was indeed found to be the case when the temperature was lowered to -128°·6[14] by means of liquid ethylene. At this temperature argon easily liquefies to a colourless liquid under 38 atmospheres. The meniscus begins to disappear at between -119°·8 and -121°·6, mean -121° at a pressure of 50·6 atmospheres. The vapour tension of liquid argon at -128°·6, is 38·0 atmospheres, at -187° it is one atmosphere, and at -189°·6 it solidifies to a colourless substance like ice. The specific gravity of liquid argon at about -187° is nearly 1·5, which is far above that of other liquefied gases of very low absolute boiling point. The discovery of argon is one of the most remarkable chemical acquisitions of recent times, and we trust that Lord Rayleigh and Professor Ramsay, who made this wonderful discovery, will further elucidate the true nature of argon, as this should widen the fundamental principles of chemistry, to which the chemists of Great Britain have from early times made such valuable contributions. It would be premature now to give any definite opinions upon so new a subject. Only one thing can be said; argon is so inert that its rôle in nature cannot be considerable, notwithstanding its presence in the atmosphere. But as the atmosphere itself plays such a vast part in the life of the surface of the earth, every addition to our knowledge of its composition must directly or indirectly react upon the sum total of our knowledge of nature. [13] There only remains the very remote possibility that argon consists of a mixture of two gases having very nearly the same properties. [14] The following data, given by Olszewsky, supplement the data given in Chapter II., Note 29, upon liquefied gases. (_tc_) (_pc_) _t_ _t__{1} _s_ N_{2} -146° 35 -194°·4 -214° 0·885 CO -139°·5 35·5 -190° -207 ? A -121° 50·6 -187° -189°·6 1·5 O_{2} -118°·8 50·8 -182°·7 ? 1·124 NO -93°·5 71·2 -153°·6 -167° ? CH_{4} -81°·8 54·9 -164° -158°·8 0·415 where _tc_ is the absolute (critical) boiling point, _pc_ the pressure (critical) in atmospheres corresponding to it, _t_ the boiling point (under a pressure of 760 mm.), _t_{1}_ the melting point, and _s_ the specific gravity in a liquid state at _t_. The above shows that argon in its properties in a liquid state stands near to oxygen (as it also does in its solubility), but that all the temperatures relating to it (_tc_, _t_, and _t_{1}_) are higher than for nitrogen. This fully answers, not only to the higher density of argon, but also to the hypothesis that it contains N_{3}. And as the boiling point of argon differs from that of nitrogen and oxygen by less than 10°, and its amount is small, it is easy to understand how Dewar (1894), who tried to separate it from liquid air and nitrogen by fractional distillation, was unable to do so. The first and last portions were identical, and nitrogen from air showed no difference in its liquefaction from that obtained from its compounds, or from that which had been passed through a tube containing incandescent magnesium. Still, it is not quite clear why both kinds of nitrogen, after being passed over the magnesium in Dewar's experiments, exhibited an almost similar alteration in their properties, independent of the appearance of a small quantity of hydrogen in them. _Concluding Remarks_ (March 31, 1895).--The 'Comptes rendus' of the Paris Academy of Sciences of March 18, 1895, contains a memoir by Berthelot upon the reaction of argon with the vapour of benzene under the action of a silent discharge. In his experiments, Berthelot succeeded in treating 83 per cent. of the argon taken for the purpose, and supplied to him by Ramsay (37 c.c. in all). The composition of the product could not be determined owing to the small amount obtained, but in its outward appearance it quite resembled the product formed under similar conditions by nitrogen. This observation of the famous French chemist to some extent supports the supposition that argon is a polymerised variety of nitrogen whose molecule contains N_{3}, while ordinary nitrogen contains N_{2}. Should this supposition be eventually verified, the interest in argon will not only not lessen, but become greater. For this, however, we must wait for further observations and detailed experimental data from Rayleigh and Ramsay. The latest information obtained by me from London is that Professor Ramsay, by treating cleveite (containing PbO, UO_{3}, Y_{2}O_{3}, &c.) with sulphuric acid, obtained argon, and, judging by the spectrum, helium also. The accumulation of similar data may, after detailed and diversified research, considerably increase the stock of chemical knowledge which, constantly widening, cannot be exhaustively treated in these 'Principles of Chemistry,' although very probably furnishing fresh proof of the 'periodicity of the elements.' * * * * * INDEX OF AUTHORITIES Abasheff, i. 75 Abel, ii. 56, 326, 410 Acheson, ii. 107 Adie, ii. 186 Alexéeff, i. 75, 94 Alluard, i. 458 Amagat, i. 132, 135, 140 Amat, ii. 171 Ammermüller, i. 504 Ampère, i. 309 Andréeff, i. 251 Andrews, i. 136, 203 Angeli, i. 266 Ansdell, i. 451 Arfvedson, i. 575 Arrhenius, i. 89, 92, 389 Aschoff, ii. 313 Askenasy, i. 508 Aubel, ii. 45 Aubin, i. 238 Avdéeff, i. 618; ii. 484 Avogadro, i. 309 Babo, v., i. 93, 200, 203 Bach, i. 394 Bachmetieff, ii. 31 Baeyer, v., i. 507 Bagouski, i. 384 Bailey, i. 449; ii. 29 Baker, i. 318, 403 Balard, i. 480, 494, 495, 505 Ball, ii. 414 Bannoff, i. 506 Barfoed, ii. 53 Baroni, i. 331 Barreswill, ii. 282 Baudrimont, ii. 35 Baumé, i. 193 Baumgauer, ii. 20 Baumhauer, i. 495 Bayer, ii. 76, 159 Bazaroff, i. 409; ii. 24, 68, 486 Becher, i. 17 Becker, i. 16 Beckmann, i. 91, 496; ii. 156 Becquerel, i. 228; ii. 97, 220 Beilby, i. 71 Beilstein, i. 373; ii. 188 Beketoff, i. 120, 122, 124, 146, 403, 459, 466, 534, 541, 574, 577; ii. 87, 102, 289, 429 Bender, i. 476 Benedict, ii. 65 Berglund, ii. 229 Bergman, i. 27, 435; ii. 100 Berlin, i. 95 Bernouilli, i. 81 Bernthsen, ii. 228 Bert, i. 86, 153 Bertheim, ii. 337 Berthelot, i. 171, 173, 189, 199, 229, 230, 258, 264, 266, 267, 272, 83, 289, 351, 372, 393, 394, 405, 415, 424, 438, 457, 463, 502, 506, 507, 518, 529, 537, 582; ii. 23, 57, 207, 209, 251, 253, 259, 345, 367 Berthier, ii. 8 Berthollet, i. 27, 31, 105, 433, 434, 459, 470, 502, 609 Berzelius, i. 131, 148, 194, 255, 379; ii. 8, 100, 102, 147, 148, 219, 281, 300, 485 Besson, i. 288; ii. 67, 70, 105, 179 Beudant, ii. 7, 8 Bineau, i. 100, 271, 452, 504; ii. 239 Binget, i. 75 Blaese, ii. 188 Blagden, i. 91, 428 Blake, ii. 30 Blitz, ii. 184 Blomstrand, ii. 299 Boerwald, ii. 279 Böttger, i. 595 Bogorodsky, i. 574 Boilleau, i. 415 Boisbaudran, L. de, i. 97, 102, 572, 600; ii. 6, 26, 90, 82, 284, 483 Bornemann, i. 509 Botkin, ii. 30 Bouchardat, ii. 45 Boullay, ii. 55 Bourdiakoff, i. 584, 617 Boussingault, i. 131, 157, 233, 235, 525, 615 Boyle, i. 124 Brand, ii. 150 Brandau, i. 481 Brandes, i. 72 Bravais, i. 233 Brauner, i. 490, 491; ii. 26, 59, 94, 96, 97, 134, 144, 194, 271, 483 Brewster, i. 569 Brigham, ii. 193 Brodie, i. 212, 351, 405; ii. 252 Brooke, ii. 357 Brown, i. 81, 88 Brugellmann, i. 616 Brunn, ii. 182, 189 Bruyn, i. 262 Brühl, i. 263, 337 Brunner, i. 124, 146, 263; ii. 230, 309, 534 Buchner, i. 615 Buckton, ii. 143 Buff, ii. 103 Bunge, i. 288 Bunsen, i. 43, 69, 78, 117, 180, 465, 568, 575, 576, 577; ii. 27, 289 Bussy, i. 75, 594, 619 Butleroff, i. 143 Bystrom, i. 585 Cagniard de Latour, i. 135, 345 Cahours, ii. 143, 173 Cailletet, i. 132, 138; ii. 45 Calderon, i. 596 Callender, i. 134 Calvert, i. 484; ii. 45 Cannizzaro, i. 584, 587 Carey-Lea, ii. 420, 424, 425, 432 Carius, i. 69, 481 Carnelley, i. 483, 515, 555; ii. 22, 29, 30, 31, 64, 143, 486 Carnot, ii. 294, 361 Caron, i. 595, 604, 610; ii. 336 Carrara, i. 213 Cass, ii. 85 Castner, i. 431, 535, 541 Cavazzi, ii. 160, 172, 182 Cavendish, i. 113, 125, 228; ii. 493 Chabrié, i. 229 Chappuis, i. 50, 199, 205, 264 Chapuy, i. 59 Cheltzoff, i. 393, 457, 582; ii. 41, 247 Cherikoff, ii. 102 Chertel, ii. 245 Chevillot, ii. 311 Chevreul, i. 530 Chigeffsky, ii. 62 Christomanos, i. 511 Chroustchoff, i. 353, 444; ii. 122 Chydenius, ii. 148, 485 Ciamician, i. 565, 573; ii. 486 Clark, i. 26 Classen, ii. 146 Clausius, i. 81, 93, 140, 142, 212, 309, 491 Clement, i. 494 Clève, ii. 26, 94, 97, 484 Cloez, i. 207, 246, 377 Clowes, i. 242 Collendar, i. 134 Comaille, i. 596 Comb, ii. 81 Connell, i. 508 Coppet, i. 91, 428, 601 Corenwinder, i. 501 Cornu, i. 565 Courtois, i. 494 Cracow, ii. 380 Crafts, i. 380 ; ii. 80, 83 Cremers, ii. 100 Croissier, i. 251 Crompton, i. 247 Crookes, i. 229, 617; ii. 20, 91, 96, 440, 491 Crum, ii. 79, 311 Cundall, i. 611 Curtius, i. 258, 265 Dahl, ii. 59 Dalton, i. 29, 78, 81, 109, 206, 271, 322 Dana, ii. 8 Davies, i. 484 Davy, i. 37, 114, 195, 255, 364, 460, 463, 484, 489, 494, 533, 541, 594, 604, 617 Deacon, i. 599 Debray, i. 609; ii. 45, 122, 291, 293, 384, 385 De Chancourtois, ii. 20, 26 De Forcrand, ii. 106, 211 De Haën, ii. 189 De Heen, i. 140 Delafontaine, ii. 97, 148, 198 De la Rive, i. 198; ii. 226 Del-Rio, ii. 197 De Saussure, i. 235, 240 De Schulten, ii. 48 Deville, St.-Claire, i. 4, 36, 118, 143, 179, 180, 227, 239, 280, 281, 301, 320, 392, 393, 399, 459, 467, 476, 477, 500, 534, 595, 608, 609; ii. 48, 80, 83, 85, 102, 147, 156, 198, 289, 309, 321, 352, 373, 374, 429 De Vries, i. 62, 64, 429 Dewar, i. 3, 5, 135, 139, 163, 297, 563, 565, 569, 585; ii. 176, 220 Dick, ii. 414 Dingwall, i. 486 Ditte, i. 72, 403, 430, 457, 509, 539, 618; ii. 64, 65, 85, 189, 249 Dittmar, i. 100, 452; ii. 240 Divers, i. 274, 294; ii. 54 Dixon, i. 171 Döbereiner, i. 145 Dokouchaeff, i. 344 Donny, i. 534 Dossios, i. 502 Draper, i. 465 Drawe, ii. 161 Drebbel, i. 294 Dulong, i. 131, 148, 437 Dumas, i. 28, 131, 148, 150, 233, 302, 320, 379, 471, 476, 584, 586, 604; ii. 22, 37, 62, 101, 156, 420 Dumont, ii. 197 Ebelmann, ii. 65 Eder, i. 566 Edron, ii. 95 Edwards, ii. 311 Egoreff, i. 569 Eissler, i. 553 Elbers, ii. 221 Emich, i. 286, 287 Emilianoff, ii. 126 Engel, i. 457; ii. 130, 132, 189, 206 Engelhardt, i. 530 Eötvös, i. 333 Erdmann, i. 150 Ernst, i. 399 Eroféeff, i. 352 Esson, ii. 314 Étard, i. 72, 516, 615; ii. 288, 335, 356 Ettinger, i. 53, 312 Famintzin, i. 611 Faraday, i. 134, 177, 296, 385, 463, 464 Favorsky, i. 373 Favre, i. 120, 172, 267, 582; ii. 83, 259, 284, 380 Fick, i. 62 Fisher, ii. 424 Fizeau, ii. 31, 429 Flavitzky, i. 21 Fleitmann, ii. 170 Foerster, ii. 375, 389 Forchhammer, ii. 311 Fordos, ii. 257 Fortmann, ii. 230, 366 Fourcroy, i. 114 Fowler, i. 449 Frank, ii. 88 Franke, ii. 311, 313 Frankel, ii. 294 Frankenheim, ii. 7 Frankland, i. 178, 357, 486; ii. 16, 143 Fraunhofer, i. 563 Frémy, i. 228, 489, 492; ii. 74, 131, 133, 142, 229, 290, 359 Freyer, i. 171, 488 Friedheim, ii. 197, 294 Friedel, i. 353, 472; ii. 80, 83, 103, 122 Friedrich, i. 49; ii. 144 Fritzsche, i. 94, 285, 600, 612; ii. 125, 218, 280, 341 Fromherz, ii. 313 Fürst, i. 484 Galileo, i. 7 Garni, i. 582 Garzarolli-Thurnlackh, i. 481 Gattermann, i. 596; ii. 102, 104 Gautier, i. 585 Gavaloffsky, i. 160 Gay-Lussac, i. 40, 61, 71, 93, 170, 302, 307, 406, 412, 460, 463, 464, 467, 500, 506, 508, 511, 515, 534, 539; ii. 8, 56, 256 Geber, i. 17 Gélis, ii. 257 Genth, ii. 359 Georgi, ii. 197 Georgiewics, ii. 64 Gerberts, i. 528 Gerhardt, i. 196, 309, 357, 388 Gerlach, i. 525 Gernez, i. 97; ii. 205 Geuther, i. 281, 283, 285; ii. 176 Gibbs, i. 140, 464; ii. 293, 410 Girault, i. 498 Gladstone, i. 337, 438, 573; ii. 213 Glatzel, ii. 213, 289, 309 Glauber, i. 17, 26, 193, 432 Glinka, i. 607 Goldberg, i. 93 Gooch, i. 484 Gore, i. 489, 492, 493 Graham, i. 62, 63, 98, 143, 155, 388, 429, 518, 601; ii. 77, 114, 131, 163, 170, 296, 307 Granger, ii. 157, 410 Grassi, i. 88 Green, ii. 310 Greshoff, i. 403 Griffiths, i. 135 Grimaldi, i. 537 Groth, ii. 10 Grouven, i. 615 Grove, i. 118, 119 Grünwald, i. 573 Grützner, ii. 296 Guckelberger, ii. 84 Guibourt, ii. 53 Guldberg, i. 439, 464 Güntz, i. 575; ii. 430 Gustavson, i. 443, 444, 472, 505, 547; ii. 29, 175 Guthrie, i. 99, 428, 601 Guy, i. 136 Habermann, ii. 210 Hagebach, i. 573 Hagen, i. 337 Haitinger, i. 593 Hammerl, i. 613 Hanisch, ii. 233 Hannay, i. 352; ii. 135 Harcourt, ii. 314 Hargreaves, i. 515 Harris, ii. 52 Hartley, i. 573; ii. 486 Hartog, ii. 268 Hasselberg, i. 566 Haüy, ii. 7 Haughton, ii. 20 Häussermann, i. 483 Hautefeuille, i. 199, 205, 264, 409, 414, 476, 477, 501, 538; ii. 102, 122, 379 Hayter, ii. 175 Hemilian, i. 132 Hempel, i. 59, 524 Henkoff, i. 530 Henneberg, ii. 170 Henning, ii. 3 Henry, i. 78, 81 Hérard, ii. 191 Hermann, ii. 8, 47, 197 Hermes, i. 529 Hertz, ii. 156 Hess, i. 178, 588 Heycock, i. 537; ii. 128, 448 Hillebrand, ii. 26, 93, 94, 484 Hintze, ii. 10 Hirtzel, ii. 55 Hittorf, ii. 155 Hodgkinson, ii. 432 Höglund, ii. 94 Hofmann, i. 302; ii. 146, 218, 447 Holtzmann, i. 505 Hoppé-Seyler, i. 611 Horstmann, i. 408 Houzeau, i. 202 Hughes, ii. 212 Hugo, ii. 21 Humboldt, i. 170 Humbly, i. 493; ii. 311 Hutchinson, i. 491 Huth, ii. 20 Huyghens, i. 569 Ikeda, ii. 152 Ilosva, i. 202 Inostrantzeff, i. 345; ii. 4 Isambert, i. 250, 257, 408; ii. 41 Ittner, i. 412 Janssen, i. 569 Jawein, ii. 170 Jay, i. 258 Jeannel, i. 104 Joannis, i. 251, 255, 405, 537, 559 Jörgensen, i. 498; ii. 359, 361, 376 Johnson, ii. 45 Jolly, i. 233 Joly, ii. 384, 385 Kamensky, ii. 414 Kammerer, i. 286, 462, 509; ii. 297 Kane, ii. 57 Kapoustin, i. 403 Karsten, i. 427, 428, 541, 599 Kassner, i. 158 Kayander, i. 133, 384; ii. 46 Keiser, i. 150 Kekulé, i. 358, 369, 507; ii. 294 Keyser, ii. 33 Khichinsky, i. 440 Kimmins, i. 510 Kirchhoff, i. 567 Kirmann, ii. 268 Kirpicheff, i. 132 Kjeldahl, i. 249; ii. 249 Klaproth, ii. 7, 145, 147, 301 Kleiber, i. 570 Klimenko, i. 465 Klobb, ii. 357 Klodt, i. 426 Knopp, ii. 338 Knox, i. 489 Kobb, ii. 125 Kobell, ii. 197 Koch, i. 44 Kohlrausch, i. 245, 525 Kolbe, i. 506 Kolotoff, i. 263 Konovaloff, i. 39, 65, 90, 93, 100, 140, 142, 172, 322; ii. 235, 268 Kopp, i. 586, 587, 612; ii. 3, 37 Koucheroff, i. 373 Kouriloff, i. 209, 247, 274; ii. 41 Kournakoff, i. 393; ii. 294, 365, 396 Kraevitch, i. 133, 134 Kraft, i. 65, 88, 537 Krafts, i. 393 Kreisler, i. 233 Kremers, i. 87, 443; ii. 244, 427 Kreider, i. 484 Krönig, i. 81 Krüger, ii. 282, 284 Krüss, ii. 355, 442, 447, 486 Kubierschky, ii. 213 Kühlmann, i. 608 Kuhnheim, i. 612 Kundt, i. 328, 589; ii. 496 Kvasnik, ii. 57 Kynaston, i. 522 Lachinoff, i. 116, 457; ii. 410 Ladenburg, ii, 103 Lamy, ii. 91 Landolt, i. 7, 337 Lang, i. 399 Langer, i. 226, 459, 462 Langlois, i. 570 ; ii. 257 Latchinoff (_see_ Lachinoff), i. 103, 352 Laurent, i. 28, 196, 388, 471, 526; ii. 7, 9, 10, 117, 292 Laurie, i. 106; ii. 32, 442, 486 Lavenig, i. 140 Lavoisier, i. 7, 29, 49, 114, 131, 155, 379, 459 Leblanc, ii. 8 Le Chatelier, i. 158, 172, 350, 393, 399, 585, 588, 611; ii. 51, 65, 420 Le Duc, i. 131, 170 Lémery, i. 125 Lemoine, i. 501; ii. 155 Lerch, i. 405 Leroy, i. 285 Lesc[oe]ur, i. 103 Leton, ii. 425 Levy, ii. 102 Lewes, i. 371 Lewy, i. 232 Lidoff, ii. 209 Liebig, i. 195, 388, 495, 527; ii. 56 Linder, ii. 223 Liés-Bodart, i. 604, 612 Lisenko, i. 373 Liveing, i. 563, 569 Lockyer, i. 565, 569 Loew, ii. 376 Löwel, i. 525, 600; ii. 45, 284, 286 Loewig, i. 528; ii. 77 Loewitz, i. 96 Lossen, i. 262 Louget, i. 489 Louguinine, i. 360 Louise, ii. 81 Lovel, i. 515; ii. 338 Lubavin, i. 593 Lubbert, ii. 85, 170 Ludwig, i. 463 Luedeking, ii. 194 Luff, ii. 321 Lunge, ii. 244, 246 Lüpke, ii. 157 Lvoff, i. 358 Maack, i. 596 Mac Cobb, i. 612 Mac Laurin, i. 553 McLeod, ii. 180 Magnus, i. 93, 510 Mailfert, i. 199 Malaguti, i. 437; ii. 300 Mallard, i. 172, 393, 588; ii. 4 Mallet, i. 493 Maquenne, i. 349, 620, 621 Marchand, i. 150 Marchetti, ii. 288 Maresca, i. 534 Marguerite, ii. 292 Marignac, i. 198, 233, 428, 430, 453, 454, 518, 525, 600, 601; ii. 6, 9, 95, 101, 194, 197, 198, 199, 234, 239, 241, 244, 292, 293, 295, 357, 440, 486 Markleffsky, i. 273 Markovnikoff, i. 373 Maroffsky, ii. 138 Marshall, ii. 253, 365 Matigon, i. 258, 266 Maumené, i. 258 Maxwell, i. 81 Mayow, i. 17 Mendeléeff, i. 99, 132, 133, 136, 141, 275, 321, 357, 373, 377, 406, 426, 427, 428, 506, 587, 596; ii. 27, 33, 93, 94 Menschutkin, i. 171 Mente, ii. 270 Mermé, i. 462 Merz, i. 505 Meselan, i. 463 Metzner, ii. 189 Metchikoff, i. 44 Meusnier, i. 114 Meyer (Lothar), i. 226, 321, 403; ii. 21, 24, 26, 29, 33, 486 Meyer (Victor), i. 135, 171, 294, 303, 320, 427, 459, 462, 467, 488, 506, 508, 558; ii. 43, 48, 52, 80, 129, 184 Meyerhoffer, ii. 410 Miasnikoff, i. 372 Michaelis, ii. 175 Michel, i. 65, 88 Millon, i. 481, 484, 508 Mills, ii. 20 Mitchell, i. 156 Mitscherlich, i. 428, 527; ii. 1, 5, 8, 156, 184, 311, 313 Moissan, i. 202, 349, 353, 490, 564, 585, 621; ii. 66, 67, 70, 88, 100, 107, 147, 174, 196, 289, 295, 309, 311, 313, 321 Mond, i. 129, 400, 405; ii. 345, 367 Monge, i. 114 Monnier, i. 611 Montemartini, i. 279 Moraht, ii. 384 Moreau, ii. 298 Morel, i. 549 Mosander, ii. 97 Mühlhäuser, ii. 66, 107 Muir, ii. 193 Mulder, i. 515 Müller-Erzbach, i. 103 Müller, i. 427; ii. 425 Munster, ii. 443 Müntz, i. 238, 241, 420, 553 Muthmann, ii. 273 Mylius, ii. 375, 389 Naschold, i. 483 Nasini, i. 496; ii. 156 Natanson, i. 282, 409 Natterer, i. 132, 135, 141, 385 Naumann, i. 399, 408 Nernst, i. 62, 148; ii. 3, 50 Nensky, i. 245 Neville, i. 537; ii. 128, 448 Newlands, ii. 21, 26 Newth, i. 505 Newton, i. 7, 29 Nicklès, ii. 10 Nikolukin, i. 491; ii. 144 Nilson, i. 618; ii. 26, 37, 80, 83, 91, 94, 95, 271, 378, 483 Nordenskiöld, i. 241 Norton, i. 76; ii. 94 Nuricsán, ii. 264 Odling, ii. 52 Offer, i. 99 Ogier, i. 321, 509; ii. 159, 182 Olszewski, i. 139, 569; ii. 491, 497 Oppenheim, i. 506 Ordway, ii. 80 Osmond, ii. 326 Ossovetsky, ii. 137 Ostwald, i. 89, 92, 389, 441, 443 Oumoff, i. 62 Pallard, i. 491; ii. 83 Panfeloff, i. 603 Paracelsus, i. 17, 125, 129, 379 Parkinson, i. 596, Pashkoffsky, i. 595 Pasteur, i. 44, 241, 242 Paterno, i. 496; ii. 156 Pattison Muir, i. 436 Pebal, i. 315, 484 Péchard, ii. 282, 294, 296, 297 Pekatoros, i. 465 Peligot, ii. 299, 301 Pelopidas, ii. 22, 481 Pelouze, i. 463, 464, 480, 610; ii. 229 Penfield, i. 545; ii. 370 Perkin, i. 558; ii. 244 Perman, i. 537 Personne, i. 75, 506, 537 Petit, i. 584, 586 Petrieff, i. 440 Pettenkofer, ii. 22 Pettersson, i. 618, 619; ii. 37, 80, 83, 91, 197, 484 Pfaundler, i. 445; ii. 241, 430 Pfeiffer, i. 64 Pfordten, V. der, ii. 420 Phipson, i. 596; ii. 59 Piccini, ii. 23, 146, 197, 288, 298 Pici, ii. 57 Pickering, i. 88, 91, 99, 104, 106, 272, 333, 452, 517, 525, 529, 613; ii. 241, 245, 246, 247 Pictet, i. 81, 129, 137; ii. 31, 241 Picton, ii. 223 Pierre, i. 452, 495; ii. 226, 485 Pierson, i. 93 Pigeon, ii. 377 Pionchon, i. 585 Pistor, i. 399 Plantamour, ii. 5 Plaset, ii. 289 Plessy, ii. 257 Plücker, i. 572 Poggiale, i. 427 Poiseuille, i. 355 Poleck, ii. 296 Poluta, ii. 30 Popp, ii. 232 Potilitzin, i. 96, 97, 98, 445, 486, 499, 502, 509, 612; ii. 29, 357 Pott, ii. 100 Poulenc, ii. 174, 289 Prange, ii. 422 Prelinger, ii. 310 Priestley, i. 17, 154, 159, 297, 379, 402 Pringsheim, i. 465 Prost, i. 98, 486 Prout, i. 31; ii. 439 Puchot, i. 452 Pullinger, ii. 389 Quincke, i. 427, 495 Rammelsberg, i. 430, 510, 525; ii. 26, 161, 485 Ramsay, i. 133, 140, 141, 232, 247, 333, 495, 496, 581; ii. 128, 491 Rantsheff, ii. 20 Raoult, i. 91, 274, 330, 331, 332, 429 Rascher, ii. 85 Raschig, i. 263; ii. 229 Rathke, i. 399 Ray, i. 17 Rayleigh, i. 226, 232, 491 Rebs, ii. 213, 217 Recoura, i. 332; ii. 289 Regnault, i. 40, 53, 54, 90, 93, 131, 133, 297, 443, 495, 584, 587, 588; ii. 50, 208, 238 Reich, ii. 91 Reiset, i. 238 Remsen, ii. 335 Retgers, ii. 157, 158, 180 Reychler, ii. 65 Reynolds, i. 581 Richards, i. 526, 585; ii. 32, 432 Riche, i. 509; ii. 127, 292 Richter, i. 193, 194; ii. 91 Ridberg, ii. 21, 24, 486 Riddle, i. 135 Rideal, ii. 297 Roberts-Austen, ii. 486 Robinson, i. 515 Rodger, ii. 213, 263 Rodwell, i. 17 Roebuck, i. 294 Röggs, ii. 119 Rohrer, ii. 343 Roozeboom, i. 106, 452, 453, 464, 496, 506, 511, 599, 613; ii. 3, 226, 341, 410 Roscoe, i. 80, 100, 101, 379, 452, 463, 485, 486, 568, 572; ii. 26, 194, 196, 197, 297, 303, 485 Rose, i. 436, 437, 518, 525, 608, 612; ii. 8, 230, 235, 248, 281, 363, 428, 485 Rosenberg, ii. 351 Rossetti, i. 428 Rouart, Le, ii. 86 Rousseau, i. 354; ii. 337, 366, 378 Roux, ii. 81 Rudberg, ii. 136 Rücker, i. 142 Rüdorff, i. 91, 428, 598, 601 Rybalkin, i. 455 Sabanéeff, i. 371 Sabatier, i. 284; ii. 66 Saint Edmé, ii. 335 Saint Gilles, i. 431 Sakurai, i. 331 Salzer, ii. 161 Sarasin, ii. 122 Sarrau, i. 140, 142 Saunders, ii. 189 Scharples, i. 576 Scheele, i. 155, 161, 412, 459, 462, 608; ii. 100, 150, 291 Scheffer, i. 453 Scheibler, ii. 292, 296 Scherer, ii. 8 Schiaparelli, ii. 318 Schidloffsky, i. 238 Schiloff, i. 212 Schlamp, i. 332 Schiff, i. 430, 588; ii. 106, 267 Schloesing, i. 238, 239, 240, 553, 610 Schmidt, i. 539 Schneider, i. 89 Schöne, i. 208, 209, 211, 394, 617; ii. 15, 72, 219, 251, 488 Schönebein, i. 198, 202, 208, 212, 509; ii. 228, 463 Schottländer, ii. 447 Schröder, i. 75 Schroederer, ii. 366 Schrötter, ii. 153, 284 Schützenberger, i. 511, 579; ii. 102, 107, 228, 367, 389 Schuliachenko, i. 608 Schuller, ii. 180 Schultz, i. 518; ii. 273 Schulze, i. 98; ii. 215 Schuster, i. 572 Schwicker, ii. 227, 230 Scott, i. 405, 537, 558 Sechenoff, i. 80, 86 Seelheim, ii. 379 Sefström, ii. 197 Selivanoff, i. 476, 507, 508 Senderens, i. 284 Serullas, i. 485 Setterberg, i. 576 Seubert, ii. 27, 83, 343, 442 Sewitsch, i. 372 Shaffgotsch, i. 555 Shapleigh, ii. 95 Shenstone, i. 611 Shields, i. 333 Shishkoff, i. 276; ii. 56 Silberman, i. 120, 172; ii. 259 Sims, ii. 268 Skraup, ii. 346 Smith, i. 271 Smithson, ii. 100 Snyders, ii. 100 Sokoloff, ii. 85, 122 Solet, i. 509 Sonstadt, ii. 443 Sorby, i. 88 Soret, i. 66, 202, 203, 427 Spring, i. 38, 98, 434, 486; ii. 45, 50, 133, 223, 258, 288, 314, 423, 427 Stadion, i. 485 Stahl, i. 16 Stas, i. 7, 233, 379, 428, 498, 581; ii. 420, 434, 485 Staudenmaier, ii. 168 Stcherbakoff, i. 97, 428, 458, 601 Stohmann, i. 359, 360, 396 Stokes, i. 355 Stortenbeker, i. 511 Stromeyer, ii. 47 Struvé, i. 208, 612 Tait, i. 203 Tammann, i. 91, 148; ii. 170, 247 Tanatar, i. 511 Tchitchérin, ii. 21 Terreil, ii. 313 Than, i. 317 Thénard, i. 207, 229, 460, 464, 534, 539; ii. 251 Thillot, ii. 170 Thilorier, i. 385 Thomsen, i. 111, 120, 124, 131, 173, 189, 267, 359, 389, 396, 441, 453, 466, 472, 494, 502, 515, 529, 555, 582; ii. 9, 32, 50, 55, 105, 165, 208, 224, 264, 368, 370, 438, 442 Thorpe, i. 142, 285, 445, 493; ii. 27, 160, 173, 213, 259, 263, 268, 301, 313, 442, 486 Thoune, i. 294, 295 Tiemman, i. 213 Tilden, i. 516 Timeraséeff, i. 170 Timoféeff, i. 78 Tessié du Motay, i. 158 Tissandier, i. 78 Titherley, i. 539 Tivoli, ii. 183 Tomassi, ii. 339 Topsöe, i. 506 Tourbaba, i. 88; ii. 247 Trapp, i. 511 Traubé, i. 312, 611; ii. 270 Troost, i. 64, 274, 281, 320, 409, 414, 500, 538; ii. 80, 83, 102, 147, 156, 254, 379 Tscherbacheff, i. 577 Tutton, i. 543; ii. 160, 174, 412 Umoff, i. 429 Unverdorben, ii. 280 Urlaub, ii. 301 Valentine, i. 17 Van der Heyd, i. 599 Van der Plaats, i. 496; ii. 438 Van der Waals, i. 82, 140 Van Deventer, i. 599 Van Helmont, i. 379 Van Marum, i. 198 Van't Hoff, i. 64, 65, 331, 599; ii. 3 Vare, ii. 55 Vauquelin, i. 114, 619; ii. 7 Veeren, i. 612; ii. 45 Veley, i. 279 Verneuille, ii. 225 Vernon, ii. 151 Vèzes, ii. 391 Viard, ii. 285 Vignon, ii. 126, 131 Villard, i. 106, 296, 297 Villiers, ii. 259 Violette, i. 342, 345 Violle, i. 301 Vogt, i. 611 Volkovitch, ii. 201 Voskresensky, i. 345 Waage, i. 439 Wachter, i. 508 Wagner, i. 357 Wahl, ii. 310 Walden, ii. 57 Walker, ii. 143 Walmer, i. 573 Walter, ii. 256 Walters, ii. 234 Wanklyn, i. 100, 539 Warburg, i. 589; ii. 496 Warder, i. 450 Warren, ii. 102 Watson, i. 527; ii. 169 Watts, i. 526 Weber, i. 280, 583; ii. 83, 129, 131, 186, 230, 233, 234, 249 Weith, i. 502 Weitz, ii. 57 Welch, ii. 425 Weller, ii. 146 Wells, i. 477, 545; ii. 57, 370 Welsbach, ii. 96, 97 Weltzien, i. 204, 595 Wenzel, i. 193 Weruboff (_see_ Wyruboff), ii. 4 Weselski, i. 507 Weyl, i. 255 Wheeler, i. 545 Wichelhaus, ii. 179 Wiedemann, i. 439, 588 Wilhelmj, ii. 315 Willgerodt, i. 508; ii. 29 Williamson, ii. 268 Wilm, ii. 376, 388 Winkler, i. 78, 79, 577, 594, 621; ii. 25, 30, 66, 97, 102, 124, 125, 147, 234, 246, 355, 483 Wischin, ii. 384 Wislicenus, i. 267, 294 Witt, ii. 3 Wöhler, i. 410, 619; ii. 85, 103, 107, 146, 285, 289, 420, 425 Wollaston, i. 8 Wreden, i. 507 Wright, ii. 321 Wroblewski, i. 79, 80, 106, 139, 387; ii. 226 Wülfing, ii. 119 Wülner, i. 91, 572 Würtz, i. 301, 476; ii. 171, 173, 213, 267 Wyruboff, ii. 4, 9 Young, i. 134, 136, 140, 141, 247, 495, 496 Zaboudsky, i. 354 Zaencheffsky, i. 140 Zimmermann, ii. 26, 303, 355, 485 Zinin, i. 276 Zörensen, i. 284 Zorn, i. 295 * * * * * SUBJECT INDEX Acid, acetic sp. gr. of solutions of, i. 59 -- arsenic, ii. 181 -- bismuthic, ii. 190 -- boric, ii. 64 -- carbamic, i. 408 -- chamber, i. 294 -- chloric, i. 482 -- chloroplatino-phosphorous, ii. 390 -- chlorosulphonic, ii. 268 -- chlorous, i. 481 -- chromic, i. 208; ii. 282 -- chromo-sulphuric, ii. 288 -- cyanic, i. 409 -- cyanuric, i. 409 -- dithionic, ii. 256 -- ferric, ii. 344 -- fluoboric, ii. 69 -- graphitic, i. 351 -- hydriodic, i. 501, 503, 505, 506 -- hydroborofluoric, ii. 69 -- hydrobromic, i. 80, 503, 505, 506 -- hydrochloric, i. 448, 451, 453 -- hydrocyanic, i. 406, 411 -- hydroferrocyanic, ii. 348 -- hydrofluoric, i. 49 -- hydrofluosilic, ii. 106 -- hydroplatinocyanic, ii. 386 -- hydrosulphurous, ii. 228 -- hydroruthenocyanic, ii. 388 -- hypochlorous, i. 479, 481 -- hyponitrous, i. 265, 294 -- hypophosphoric, ii. 161 -- hypophosphorous, ii. 172 -- iodic, i. 100, 508 -- isethionic, ii. 250 -- metantimonic, ii. 188 -- metaphosphoric, ii. 162, 169 -- metastannic, ii. 131 -- molybdic, ii. 292 -- nitric, i. 268, 272 -- Nordhausen, ii. 233 -- orthophosphoric, ii. 162 -- osmic, ii. 384 -- pentathionic, ii. 257 -- percarbonic, i. 394 -- perchloric, i. 484 -- periodic, i. 510 -- permanganic, ii. 313 -- permolybdic, ii. 297 -- pernitric, i. 264 -- persulphuric, ii. 251 -- pertungstic, ii. 297 -- phosphamic, ii. 179 -- phosphamolybdic, ii. 293 -- phosphorous, ii. 171 -- polysilicic, ii. 117 -- pyrophosphoric, ii. 169 -- pyrosulphuric, ii. 234 -- silenic, ii. 272 -- silicotungstic, ii. 295 -- stannic, ii. 130 -- sulphonic, ii. 249 -- sulphuric, i. 76, 77, 89, 111, 290, 294; ii. 235, 238, 241 -- telluric, ii. 272 -- tetrathionic, ii. 257 -- thiocarbonic, ii. 263 -- thiocyanic, ii. 263 -- thionic, ii. 255 -- thiosulphuric, ii. 230 -- trithionic, ii. 257 -- tungstic, ii. 292, 294 -- vanadic, ii. 196 Acids, i. 185 -- avidity of, i. 389, 442 -- basicity of, i. 387 -- complex, i. 197; ii. 293 -- fuming, i. 102 -- organic, i. 394, 396, 405 Acetylene, i. 372 Actinium, ii. 59 Affinity, chemical, i. 26, 389 Air, i. 131, 231, 233 Alchemy, i. 14 Alcohol, i. 53, 88 Alkali, metals, i. 558, 577 -- waste, ii. 204 Alkalis, i. 186 Allotropism, i. 207 Alloys, i. 537; ii. 128 Alumina, ii. 75 Aluminium, ii. 70, 85 -- bromide, ii. 84 -- bronze, ii. 88 -- carbide, ii. 88 -- chloride, ii. 80, 83 -- double chlorides, ii. 84 -- fluoride, ii. 83 -- hydroxide, ii. 75 -- iodide, ii. 85 -- nitrate, ii. 80 -- sulphate, ii. 82 Alums, ii. 5, 82, 343 Alunite, ii. 80 Amalgams, ii. 58 Amides, i. 258, 406 Amidogen, i. 258 -- hydrate, i. 258 Amines, i. 416 Ammonia, i. 229, 246 -- of crystallisation, i. 257 -- heat of solution of, i. 74 -- in air, i. 240 -- liquefaction of, i. 250 -- salts, i. 254 -- soda process, i. 524 -- solutions of, i. 80, 252 Ammonium, i. 254 -- amalgam, i. 255 -- bicarbonate, i. 527 -- carbamate, i. 407, 408 -- carbonate, i. 407 -- cobalt salts, ii. 359 -- dichromate, ii. 279 -- molybdate, ii. 292 -- nitrate, i. 273, 274 -- nitrite, i. 284 -- phosphates, ii. 167 -- sulphate, ii. 269 -- sulphide, ii. 218 Analogy of elements, i. 573, 578 Anthracite, i. 345 Antimoniuretted hydrogen, ii. 189 Antimony, ii. 186 -- chlorides, ii. 189 -- oxides, ii. 187, 188 -- sulphides, ii. 221 Aqua Regia, i. 467 Aqueous radicle, i. 213 Argon, i. 226, 232; App. III. Arsenic, ii. 179 -- anhydride, ii. 181 -- sulphides, ii. 221 -- tribromide, ii. 181 -- trichloride, ii. 180 -- trifluoride, ii. 181 Arsenious anhydride, ii. 184 -- oxychloride, ii. 180 Arsenites, ii. 185 Arseniuretted hydrogen, ii. 182 Astrakhanite, i. 59 Atmolysis, i. 156 Atomic theory, i. 216 -- volumes, ii. 33 -- weights, i. 21 Atoms and molecules, i. 322 Barium, i. 614, 617 -- chlorate, i. 483 -- chloride, i. 615 -- hydroxide, i. 616 -- metatungstate, ii. 295 -- nitrate, i. 615 -- oxide, i. 616 -- peroxide, i. 157, 160, 209, 617 -- sulphate, i. 614, 615 Bauxite, ii. 76 Benzalazine, i. 258 Berthollet's doctrine, i. 433 Beryllium, i. 618 -- atomic weight of, i. 325, 618 -- chloride, i. 584 -- oxide, i. 619 Binary theory, i. 195 Bismuth, ii. 189 -- nitrates, ii. 192 -- oxides, ii. 190, 191 Blast furnace, ii. 324 Bleaching, i. 469 -- powder, i. 162, 477 Boiling point, absolute, i. 130 Borates, ii. 63 Borax, ii. 61 Boric anhydride, ii. 64 Boron, ii. 60, 66 -- chloride, ii. 69 -- fluoride, ii. 67, 68 -- iodide, ii. 70 -- nitride, i. 227; ii. 67 -- oxide, ii. 60 -- specific heat of, i. 585 -- sulphide, ii. 62 Bromides, ii. 32 Bromine, i. 494 Bronze, ii. 127 Butyl alcohol, solubility of, i. 75 Cadmium, ii. 47 -- iodide, ii. 48 -- oxide, ii. 48 -- sulphide, ii. 47 Cæsium, i. 576 Calcium, i. 590, 604 -- carbonate, i. 592, 608, 609, 610 -- chloride, i. 237, 612 -- -- crystallohydrates of, i. 613 -- fluoride, i. 491 -- hypochlorite, i. 162 -- iodide, i. 604 -- peroxide, i. 607 -- phosphate, ii. 167 -- sulphate, i. 611 -- sulphide, ii. 220 Calomel, ii. 54 Carbamide, i. 409 Carbides, i. 349, 353 Carbon, i. 338 -- bisulphide, ii. 258 -- molecule of, i. 354 -- oxysulphide, ii. 264 -- tetrachloride, i. 473 Carbonic anhydride, i. 379 -- -- assimilation of by plants, i. 393 -- -- dissociation of, i. 392, 393, 399 -- -- in air, i. 238, 242 -- -- liquid, i. 385 -- -- solutions of, i. 80, 86 -- -- specific heat of, i. 393 Carbonic oxide, i. 396 -- -- and nickel, i. 405 Carborundum, ii. 107 Carboxyl, i. 395 Carnallite, i. 421, 544, 560 Catalytic phenomena, i. 211 Caustic potash, i. 550 -- soda, i. 529 Cements, ii. 122 Cerite metals, ii. 93 Cerium, ii. 93 Chamber crystals, i. 290; ii. 230 Charcoal, i. 343 Chemical change, rate of, ii. 314 -- transformations, i. 3 Chloranhydrides, i. 468; ii. 174, 175, 177 Chlorates, i. 482 Chlorides, i. 455, 466; ii. 31 Chlorine, i. 463 -- compounds, heat of formation of, i. 44 -- crystallohydrates of, i. 464 -- oxides, i. 479 -- preparation of, i. 460 -- solubility of, i. 463 Chloroform, i. 473 Chlorophosphamide, ii. 179 Chloryl compounds, i. 476 Chrome alum, ii. 283 Chromic acid, i. 208 -- anhydride, ii. 280 -- oxide, ii. 284, 285 Chromium, ii. 276, 289 -- chlorides, ii. 285 -- fluorides, ii. 280, 289 Chromyl chloride, ii. 281 Chryseone, ii. 108 Clay, ii. 70 Coal, i. 345 Cobalt, ii. 353 -- dioxide, ii. 366 -- fluoride, ii. 358 Cobaltamine salts, ii. 359 Cobaltic oxide, ii. 362 Cobalto-amine, ii. 359 Cobaltous hydroxide, ii. 358 Cohesion of liquids, i. 52 Coke, i. 345 Collodion cotton, i. 275 Colloids, i. 63; ii. 77, 423 Combination, chemical, i. 3 Combining weights, i. 21; ii. 439 Combustion, imperfect, i. 341 -- heat of, i. 172, 176, 399, 400 Compounds, definite and indefinite, i. 31 -- types of, ii. 10 Compressibility of solutions, i. 88 Conductivity, electro-molecular, i. 389 Contact reactions, i. 163, 290 Copper, ii. 400 -- carbonate, ii. 411 -- complex salts of, ii. 412 -- nitrate, ii. 411 -- nitride, ii. 409 -- sulphate, ii. 413 Corundum, ii. 75 Critical points, i. 141 Cryohydrates, i. 99 Cryoscopic investigations of solutions, i. 90, 332 Crystals, i. 51 Crystalline form, ii. 7 Crystallo-hydrates, i. 102 Crystalloids, i. 63 Cupellation, ii. 417 Cyanides, i. 406 Cyanogen, i. 406, 414 -- chloride, ii. 176 Decomposition, chemical, i. 4 Deliquescence, i. 104 Delta metal, ii. 414 Desiccator, i. 58 Detonating gas, i. 115, 170, 173 Depression of freezing point of solutions, i. 90, 92, 330 Dialysis, i. 63; ii. 114 Diamond, i. 350, 353 Didymium, ii. 93 Diffusion, rate of, i. 63 Dimorphism, i. 610, ii. 178 Disinfectants, i. 245 Disodium orthophosphate, ii. 166 Dissociation, i. 36, 282, 608 Distillation, dry, i. 4, 247, 342 Dust, atmospheric, i. 241 Efflorescence, i. 103 Ekacadmium, ii. 59 Ekasilicon, ii. 25 Electro-chemical theory, i. 195 Electric energy and thermal units, i. 582 Electrolysis, i. 116 Elements, i. 20 -- grouping of, ii. 1 -- typical, ii. 19 Emulsions, i. 98 Energy, chemical, i. 29 Equations, chemical, i. 278 Equivalents, law of, i. 194 Equivalent weights, i. 581 Ethane, i. 366 Ether, critical points of, i. 141 Ethylene, i. 370 Ethyl silicates, i. 104 Euchlorine, i. 484 Eudiometer, i. 169 Expansion, linear, of elements, ii. 31 Explosion, rate of transmission of, i. 171 Explosives, i. 275, 276 Felspar, ii. 122 Fermentation, i. 242 Ferric chloride, i. 558; ii. 340 -- hydrates, ii. 339 -- nitrate, ii. 340 -- orthophosphate, ii. 342 -- oxide, ii. 339 Ferrous chloride, ii. 335 -- sulphate, ii. 335 -- -- solubility of, i. 72 -- sulphide, ii. 210 Flame, i. 177, 179 Fluoborates, ii. 69 Fluorides, i. 491, 493 Fluorine, i. 203, 489 Fluorspar, i. 491 Formula, chemical, i. 151, 326 Freezing mixtures, i. 76 Fuel, calorific capacity of, i. 360 Furnace, electrical, i. 352 Fusco-cobaltic salts, ii. 360 Gadolinite metals, ii. 93 Gallium, ii. 88, 90 Gas, illuminating, i. 361 -- producers, i. 397 Gases, absorption of, i. 348 -- diffusion of, i. 83 -- expansion of, i. 133 -- liquefaction of, i. 134, 135, 137 -- measurement of, i. 78, 300 -- solution of, i. 68, 78, 86 -- theory of, i. 81, 83, 140 Germanium, ii. 26, 124 -- chloride, ii. 125 -- oxide, ii. 125 Glass, i. 123 -- soluble, ii. 110 Glauber's salt, i. 517 Glycols, ii. 117 Gold, ii. 442 -- alloys, i. 446, 447 -- chlorides, ii. 448, 450 -- colloid, ii. 447 -- cyanide, ii. 450 -- extraction of, ii. 444, 445 -- fulminating, ii. 450 -- oxides, ii. 448 -- refining, ii. 446 Graduators, i. 424 Graphite, i. 350, 351 Gros' salt, ii. 393 Guignet's green, ii. 285 Gunpowder, i. 557 Gypsum, i. 593, 611 Halogens, i. 445, 487, 499 Halogen compounds, heat of formation of, i. 494, 502; ii. 32 -- -- boiling-points of, i. 502 Hausmannite, ii. 10 Helium, i. 570; ii. 498 Hemimorphism, ii. 9 Homeomorphism, ii. 8 Homologous compounds, i. 358 Humus, i. 344 Hydrates, i. 109, 185 Hydrazine, i. 258 Hydrides, i. 621; ii. 23 Hydrocarbons, i. 355, 359 Hydrogen, i. 123, 129, 130, 142, 143, 146 -- pentasulphide, ii. 217 -- peroxide, i. 207, 312 Hydrosols, i. 98 Hydroxyl, i. 192, 213 Hydroxylamine, i. 262 Hypochlorites, i. 481 Hyponitrites, i. 294 Imides, i. 258 Indium, ii. 27, 37, 88, 97 Iodates, i. 509 Iodides, ii. 32 -- of nitrogen, i. 507 Iodine, i. 320, 321, 496, 497, 498 -- chlorides of, i. 511 Iodosobenzol, i. 508 Iridious oxide, ii. 382 Iridium, ii. 382 Iron, i. 585; ii. 317, 322 -- and carbonic oxide, ii. 345 -- cast, ii. 325 -- nitride, ii. 346 -- ores, ii. 319 -- sulphate, ii. 335 Isethionic acid, ii. 250 Isomorphism, i. 203, 368; ii. 1, 4, 8 Kaolin, ii. 70 Lakes, ii. 77 Lanthanum, ii. 93 Laughing gas, ii. 297 Law of Avogadro-Gerhardt, i. 309 -- -- Berthollet, i. 445 -- -- Boyle and Mariotte, i. 132 -- -- combining weights, i. 221 -- -- Dulong and Petit, i. 584 -- -- equivalents, i. 194 -- -- even numbers, i. 357 -- -- Gay Lussac, i. 133, 304, 307 -- -- Guldberg and Waage, i. 441 -- -- Henry and Dalton, i. 78 -- -- indestructibility of matter, i. 6 -- -- Kirchoff, i. 568 -- -- limits, i. 357 -- -- maximum work, i. 120 -- -- multiple proportions, i. 109, 214 -- -- partial pressures, i. 82 -- -- periodic, ii. 17 -- -- phases, ii. 410 -- -- reversed spectra, i. 568 -- -- specific heats, i. 584 -- -- substitution, i. 260, 365 -- -- volumes, i. 304 Lead, ii. 134 -- acetate, ii. 137 -- carbonate, ii. 140 -- chloride, ii. 139 -- chromate, ii. 136, 279 -- dioxide, ii. 142 -- nitrate, ii. 139 -- oxide, ii. 137 -- red, ii. 142 -- salts of, i. 491 -- tetrachloride, ii. 144 -- tetrafluoride, ii. 144 -- white, ii. 140 Leucone, ii. 107 Levigation, ii. 72 Light, chemical action of, i. 465 Lime, i. 605 Liquids, boiling points of, i. 135 Lithium, i. 574 -- carbonate, i. 575 Litharge, ii. 137 Litmus, i. 185 Lixiviation, methodical, i. 521 Luteocobaltic salts, ii. 359 Magnus' salt, ii. 392 Magnesia, i. 597 Magnesium, i. 590, 594 -- carbonate, i. 592, 602 -- chloride, i. 602 -- crystallohydrates of, i. 601 -- double salts of, i. 597 -- nitride, i. 595 -- silicide, ii. 102 -- sulphate, i. 600 Manganese, ii. 303 -- nitrides, ii. 310 -- oxides, ii. 306, 307, 308, 313 -- peroxide, i. 159; ii. 305 -- sulphate, ii. 307 Mass, influence of, i. 32, 436 Matches, ii. 154 Matter, primary, ii. 440 -- transmutability of, i. 14 Mercury, ii. 48 -- ammonia compounds, ii. 57 -- basic salts of, ii. 54 -- chlorides, ii. 52, 53, 54 -- compounds, heat of formation, ii. 50 -- cyanide, ii. 55 -- fulminating, ii. 56 -- iodide, ii. 55 -- nitrates, ii. 51 -- nitrides, ii. 56 -- oxides, ii. 53 -- sulphate, ii. 57 -- sulphides, ii. 221 Metalepsis, i. 28, 471 Metalloids, i. 23 Metals, i. 23 -- of alkaline earths, i. 64, 590, 591 -- of alkalis, i. 543 -- displacement of, ii. 427 Methane, i. 360 Moisture, determination of, in gases, i. 40 -- influence upon reaction, i. 403 Molecular volumes, ii. 37 -- weight and boiling point, i. 331 -- -- -- coefficient of refraction, i. 336 -- -- -- latent heat, i. 329 -- -- -- specific gravity of solutions, i. 335 -- -- -- surface tension, i. 334 Molecules, i. 319, 322 Molybdates, ii. 292 Molybdenum, ii. 290 -- anhydride, ii. 291 -- fluo-compounds, ii. 298 -- sulphides, ii. 297 Monophosphamide, ii. 178 Monosodium orthophosphate, ii. 167 Morphotropy, ii. 10 Naphtha, i. 373, 377 Nascent state, i. 33, 145, 146 Neodymium, ii. 97 Nickel, ii. 353 -- alloys, ii. 367 -- and carbonic oxide, ii. 367 -- fluoride, ii. 358 -- hydroxide, ii. 358 -- oxide, ii. 365 -- sulphate, i. 97; ii. 359 -- tetra-carboxyl, ii. 367 Niobium, i. 199; ii. 194, 198 Nitrates, i. 273 Nitres, i. 268, 555 Nitric anhydride, i. 280 -- oxide, i. 286 Nitrides, i. 227, 258, 620 Nitriles, i. 406 Nitrites, i. 284 Nitro-cellulose, i. 275 Nitro-compounds, i. 274 Nitrogen, i. 223, 225, 475 -- chloride, i. 476 -- iodide, i. 507 -- oxides of, i. 267, 280, 284, 294, 295 -- sulphide, ii. 270 Nitro-prussides, ii. 351 Nitroso-compounds, i. 288 Nitrosulphates, ii. 229 Nitrosyl chloride, ii. 176 Norwegium, ii. 59 Occlusion, i. 143 Olefiant gas, i. 370 Organo-metallic compounds, i. 356 Osmium, ii. 372, 382, 384 Osmotic pressure, i. 64 Osmuridium, ii. 383 Oxamide, i. 406 Oxidation, i. 16 Oxides, i. 183; ii. 36 Oxycobaltamine salts, ii. 359 Oxygen, i. 152, 157, 158, 163 -- compounds, heat of formation of, i. 120, 466 Ozone, i. 198, 229 Palladium, ii. 369 -- hydride, i. 143; ii. 380 Palladous chloride, ii. 379 -- iodide, ii. 379 Paracyanogen, i. 414 Paramorphism, ii. 9 Parasulphatammon, ii. 269 Peat, i. 344 Peligot's salt, ii. 281 Percentage composition, i. 326 Perchloric anhydride, ii. 282 Periodates, i. 510 Permanganic anhydride, ii. 313 Permolybdates, ii. 297 Peroxide, chloric, i. 484 Peroxides, i. 159; ii. 15, 23 Perstannic oxide, ii. 133 Persulphates, ii. 253 Petroleum, i. 373 Phenol, solubility of, i. 75 Phlogiston, i. 17 Phosgene gas, ii. 175 Phospham, ii. 178 Phosphides, ii. 157 Phosphine, ii. 158, 160 Phosphonium iodide, ii. 159 Phosphoric anhydride, ii. 161 Phosphorous anhydride, ii. 160 Phosphorus, ii. 149 -- ammonium compounds, ii. 178 -- chlorides, ii. 174 -- fluorides, ii. 173 -- iodides, i. 505, 506; ii. 172 -- oxychlorides, ii. 175 -- sulphides, ii. 213 -- sulphochloride, ii. 213 -- thermo-chemical data for, ii. 153 Phosphuretted hydrogen, ii. 158, 160 Photography, ii. 431 Photo-salts, ii. 432 Plants, chemical reactions in, i. 547 -- and nitrogen, i. 230 Platinic chloride, ii. 377 -- hydroxide, ii. 379 Platino-ammonium compounds, ii. 391 -- chlorides, i. 467; ii. 378 -- cyanides, ii. 386 -- nitrites, ii. 390 -- sulphites, ii. 390 Platinous chloride, ii. 379 Platinum, ii. 376 -- alloys, ii. 373 -- black, ii. 376 -- metals, ii. 369, 375 -- oxide, ii. 378 Poly-haloid salts, i. 545 Polymerism, i. 207, 367 Polysulphides, ii. 217 Potassium, i. 544, 558 -- aurate, ii. 449 -- bromide, i. 550 -- carbonate, i. 549 -- chlorate, i. 161, 482 -- chloride, i. 72, 543 -- chromate, ii. 280 -- cyanide, i. 412, 551 -- dichromate, ii. 278 -- ferricyanide, ii. 346 -- ferrocyanide, i. 346, 412 -- hydrosulphide, ii. 219 -- hydroxide, i. 548 -- iodide, i. 550 -- manganate, ii. 310 -- nitrate, i. 553 -- oxides, i. 559 -- permanganate, ii. 311 -- stannate, ii. 133 -- sulphate, i. 72, 549 -- sulphide, ii. 219 -- telluride, ii. 274 Praseocobaltic salts, ii. 361 Praseodidymium, ii. 97 Proteid substances, i. 224 Prout's hypothesis, ii. 439 Prussian blue, i. 419; ii. 349 Purpureocobaltic salts, ii. 361 Purpureotetramine salts, ii. 361 Pyrocollodion, i. 275 Pyronaphtha, i. 375 Pyrosulphuryl chloride, i. 321; ii. 235 Reactions, chemical, i. 3 -- -- conditions for, i. 34 -- -- contact, i. 39 -- -- endothermal, i. 30 -- -- exothermal, i. 30 -- -- limit of, i. 437 -- -- rate of, ii. 152 Recalescence, ii. 333 Reduction, i. 16 Refraction equivalent, i. 336 Regenerative furnaces, i. 398 Reiset's salts, ii. 394 Respiration, i. 152, 154, 387 Rhodium, ii. 381 Rock salt, i. 421 Roseocobaltic salts, ii. 360 Rosetetramine salts, ii. 361 Rubidium, i. 576 Ruthenium, ii. 372, 382, 384 Sal-ammoniac, i. 248, 318, 457 -- solubility of, i. 458 -- vapour density of, i. 317 Salts, i. 187, 419 -- acid, i. 193, 533 -- basic, i. 193, 533; ii. 54 -- double, i. 598 -- electrolysis of, i. 191 -- heat of formation, i. 189 -- melting points of, i. 135 -- pyro, i. 193 -- theory of, i. 193 Saponification, i. 530 Scandium, ii. 94 Selenium, ii. 273 -- chlorides, ii. 275 Selenious anhydride, ii. 271 Silica, i. 100; ii. 108 -- soluble, ii. 113 Silicates, i. 544; ii. 116 Silicon, ii. 99 -- chloride, ii. 103, 104 -- chloroform, ii. 103 -- bromide, ii. 104 -- fluoride, ii. 105 -- hydride, ii. 102, 103 -- iodide, ii. 105 -- iodoform, ii. 105 Silver, ii. 418 -- allotropic varieties of, ii. 421 -- bromide, ii. 429 -- chlorate, ii. 437 -- chloride, ii. 429 -- cyanide, ii. 433 -- fluoride, ii. 430 -- fulminating, ii. 426 -- hyponitrite, i. 294 -- iodide, ii. 429 -- nitrate, ii. 426 -- nitrite, i. 284 -- orthophosphate, ii. 164 -- oxides, ii. 424 -- peroxide, ii. 422 -- plating, ii. 434 -- soluble, ii. 420 -- subchloride, ii. 432 Slags, ii. 323 Smalt, ii. 354 Soaps, i. 531 Soda ash, i. 519 -- caustic, i. 527 -- manufacture of, i. 459 -- waste, i. 522 Soda lime, i. 237 Sodamide, i. 539 Sodium, i. 513, 533 -- alloys, i. 559 -- amalgams, i. 537 -- bicarbonate, i. 526 -- carbonate, i. 519, 525 -- -- crystallohydrates of, i. 108 -- -- manufacture of, i. 523 -- -- solutions of, i. 525 -- chloride, i. 419 -- -- double salts of, i. 430 -- -- solutions of, i. 88, 99, 429 -- hydride, i. 537 -- hydroxide, i. 528, 529 -- -- solutions of, i. 529 -- nitrate, i. 269 -- -- solutions of, i. 72 -- organo compounds of, i. 540 -- oxides, i. 540, 541 -- phosphates, ii. 166 -- platinate, ii. 378 -- pyrosulphate, i. 518 -- sesquicarbonate, i. 526 -- stannate, ii. 133 -- subchloride, i. 540 -- sulphate, i. 513 -- -- acid salt, i. 518 -- -- crystallohydrates of, i. 515 -- -- solutions of, i. 73, 515, 516 -- sulphite, ii. 226 -- thiosulphate, ii. 230 -- -- solutions of, i. 74 -- tungstate, ii. 294 Soils, i. 344; ii. 73 Solubility, coefficient of, i. 67, 71 Solutions, i. 330 -- aqueous, i. 59 -- boiling points of, i. 94, 100 -- crystallisation of, i. 427 -- colour of, i. 95 -- diffusion of, i. 61, 429 -- of double salts, i. 599 -- formation of ice from, i. 91, 428 -- heat of formation of, i. 74, 75, 76 -- of gases, i. 68 -- isotonic, i. 64 -- saturated, i. 65 -- specific gravity of, i. 429, 584 -- supersaturated, i. 96 -- theory of, i. 64, 89, 92, 97, 106, 215, 323, 608; ii. 3, 164 -- vapour tension of, i. 90, 92 -- volumes of, i. 87 -- Specific heat, i. 585, 586, 588 Spectra absorption, i. 566 Spectrum analysis, i. 560, 561 Stannic chloride, ii. 132 -- fluoride, ii. 132 -- oxide, ii. 130 -- sulphide, ii. 132 Stannous chloride, ii. 130 -- oxide, ii. 129 -- salts, ii. 129 Steam, vapour tension of, i. 54 Steel, ii. 327, 328, 330 Strontium, i. 615 -- chloride, i. 615 -- hydroxide, i. 615 -- nitrate, i. 615 -- oxide, i. 617 Substitution chemical, i. 5 Sulphamide, ii. 270 Sulphatammon, ii. 269 Sulphates, ii. 248 Sulphides, i. 98; ii. 213 Sulphonitrites, ii. 229 Sulphoxyl, ii. 250 Sulphur, ii. 200 -- chlorides of, ii. 264 Sulphuretted hydrogen, ii. 208 Sulphuric anhydride, ii. 232 -- peroxide, ii. 251 Sulphurous anhydride, ii. 224 Sulphuryl chloride, ii. 268 Superphosphates, ii. 168 Tantalum, ii. 194, 198 Tellurium, ii. 274 -- bromide, ii. 275 -- chlorides, ii. 275 Tellurous anhydride, ii. 271 Temperature, critical, i. 131 Test papers, i. 185 Thallium, ii. 88, 91 Thallic oxide, ii. 93 Thallous hydroxide, ii. 92 -- oxide, ii. 92 Thiocarbonates, ii. 262 Thionyl chloride, ii. 267 Thiophosgene, ii. 262 Thiophosphoryl fluoride, ii. 263 Theory, atomic, i. 216 -- unitary, i. 195 -- vortex, i. 217 Thermochemistry, i. 173 Thorium, ii. 148 Tin, ii. 125 -- alloys, ii. 127 Titanium, ii. 144 -- chloride, ii. 145 -- nitride, ii. 146 -- nitrocyanide, ii. 146 -- oxides, ii. 145 Tripoli, ii. 110 Trisodium orthophosphate, ii. 166 Tungstates, ii. 292 Tungsten, ii. 290 -- anhydride, ii. 291 -- nitride, ii. 297 -- sulphide, ii. 297 Turnbull's blue, ii. 350 Types of combination, ii. 10 Ultramarine, ii. 84 Uranium, ii. 30, 297 -- atomic weight of, ii. 26 -- dioxide, ii. 301 -- oxides, ii. 298 -- tetrachloride, ii. 301 Urano-alkali compounds, ii. 298 Uranyl, ii. 301 -- ammonium carbonate, ii. 300 -- nitrate, ii. 300 -- phosphate, ii. 300 Urea, i. 409 Valency of elements, i. 404, 418, 581 Van der Waal's formula, i. 82, 140 Vanadic anhydride, ii. 196 Vanadium, ii. 194 -- oxychloride, ii. 195 Vapour density, determination of, i. 301 Ventilation, i. 244 Viscosity, i. 355 Volumes, molecular, ii. 4 -- gases, i. 300 Water, i. 40 -- composition of, i. 114, 118, 148, 169, 305, 333 -- compressibility of, i. 53 -- of constitution, i. 109 -- of crystallisation, i. 95, 510 -- dissociation of, i. 118 -- expansion of, i. 53 -- gas, i. 129, 400, 401 -- hard, i. 47 -- hygroscopic, i. 56 -- mineral, i. 45 -- rain, i. 43 -- river, i. 43 -- sea, i. 46 -- specific heat of, i. 52 -- -- gravity of, i. 50 -- spring, i. 44 Wave lengths, i. 564 Wood, i. 339 Ytterbium, ii. 93 Yttrium, ii. 93 Zinc, ii. 39 -- ammonia-chlorides, ii. 41 -- chloride, ii. 40, 41 -- compounds, heat of formation of, ii. 51 -- oxide, ii. 39, 40 -- sulphate, ii. 39 Zirconium, ii. 146 -- chloride, ii. 147 -- hydroxide, ii. 147 -- oxide, ii. 147 * * * * * PRINTED BY SPOTTISWOODE AND CO., NEW-STREET SQUARE LONDON * * * * * A CLASSIFIED CATALOGUE OF SCIENTIFIC WORKS PUBLISHED BY MESSRS. 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The ligature oe has been marked as [oe]. The asterism sign has been marked as [asterism]. The 3root sign has been marked as [3root]. The sign ^ has been used as a superscript. 
46998	----	ELEMENTS OF THE THEORY AND PRACTICE OF CHYMISTRY· Translated from the FRENCH of M. MACQUER, Member of the Royal Academy of Sciences, and Professor of Medicine in the University of PARIS. The FIFTH EDITION. EDINBURGH: Printed for ALEXANDER DONALDSON; and sold at his Shop, No. 48, East Corner of St. Paul's Church-Yard, London; and at Edinburgh. M. DCC. LXXVII. THE AUTHOR's PREFACE. An hundred and fifty years are scarce elapsed since the clouds of prejudice, which had long overspread the world, began to clear up, and men were convinced, by cultivating the Sciences, and attending to Nature, that no fanciful hypotheses would ever lead them to the true causes of those various phenomena that incessantly and every where meet the observer's eye; but that the narrow limits of the human understanding confine the course of our researches to one single path; namely, that of Experiment, or the Use of our Senses. Yet, in this short period, Natural Philosophy hath risen to a high pitch of improvement, and may with truth be said to have made much greater advances towards perfection, since the experimental method was introduced, than in the many ages before. This is true with regard to every branch of Natural Philosophy; but more particularly with regard to Chymistry. Though this Science cannot be said to have ever existed without experiments, yet it laboured under the same disadvantages with the rest; because those who studied it made all their experiments with a view to confirm their own Hypotheses, and in consequence of principles which had no foundation whatever, but in their wild imaginations. Hence arose that enormous heap, that incongruous jumble of facts, which some time ago constituted all the knowledge of Chymists. Most of them, and especially those who assumed the pompous title of Alchymists, were persuaded that all the Metals were no other than Nature's rude unfinished essays towards making Gold; which, by means of due coction in the bowels of the earth, advanced gradually towards maturity, till at last they were perfectly converted into that beautiful and precious Metal. On this principle, which, if not demonstrably false, is at least utterly destitute of proof, and unsupported by a single observation, they attempted to finish what Nature had begun, by procuring to the imperfect Metals this much desired coction. To attain it they made an infinite number of experiments and trials; which all conspired to detect the falsity of their system, and to satisfy men of sense, that the methods they employed were very far from answering the purpose. However, as facts always promote the knowledge of Nature, it happened that those experiments, though quite useless with regard to the end for which they were originally made, proved the occasion of several curious discoveries. These lucky consequences of their mistaken labours raised the courage of the Chymists, or rather Alchymists, who looked upon every such instance of success as a new step towards the Grand Work, and greatly increased the fond opinion they entertained of themselves, and of their Art, which, on that account, they set up very high above all other Sciences. Nay, they carried this notion of superiority so far, as to hold the rest of mankind unworthy, or incapable, of rising to such sublime knowledge. In consequence thereof Chymistry became an occult and mysterious Science; its expressions were all tropes and figures, its phrases metaphorical, and its axioms so many enigmas: in short, an obscure unintelligible jargon is the justest character of the Alchymistic Language. Thus, by endeavouring to conceal their secrets, those gentlemen rendered their Art useless to mankind, and brought it into deserved contempt. But at length the genius of true philosophy prevailed in Chymistry, as well as in the other Sciences. Some great men arose, who had generosity enough to think their knowledge no otherways valuable than as it proved of service to Society. They did their utmost to introduce both the knowledge and the practice of many important secrets, till then of no use; they drew aside the veil which hid the charms of Chymistry; and that Science emerging from the profound obscurity, in which it had for many ages lain concealed, gained the admiration of the world as soon as it appeared in open day. Several societies of ingenious men were formed in the most learned countries of Europe, who vied with one another in their labours to execute the noble scheme, and assisted each other by mutually communicating their discoveries. Chymistry made the most rapid progress, enriching and perfecting the Arts derived from, or depending on it. In a word, it put on a new face, and became truly worthy of the title of Science; founding its principles and its processes on solid experiments, and on just consequences deduced from them. Since that time the Art is become so extensive, by the numerous discoveries which Chymists have already made, and are daily making, that large volumes are required to contain a complete Treatise on the subject. In short, Chymistry may now, in some degree, be compared to Geometry: each of these Sciences takes in a most ample field of inquiry, which every day enlarges very considerably; from each are derived several Arts, not only useful but even necessary to Society; each hath its Axioms and its undeniable principles, either demonstrated from internal evidence, or founded on constant experience; so that the one, as well as the other, may be reduced to certain fundamental truths, on which all the rest are built. These fundamental truths connected together, and laid down with order and precision, form what we call the Elements of a Science. It is well known that there are many such works relating to Geometry, but it is not so with regard to Chymistry; there being very few books which treat of this Science in an Elementary manner. Yet it must be owned, that performances of this kind are exceedingly useful. Many who have a relish for the Sciences, but have not leisure to read elaborate Works which treat of them minutely, are glad to meet with a book from which, without sacrificing too much of their time, or neglecting their ordinary business, they may obtain a taste or just notion of a Science that is not their principal study. Those who incline to go farther, and learn more, may, by reading an elementary tract, be enabled to understand Authors, who, as they commonly write only for proficients in the Art, are obscure and hardly intelligible to mere beginners. Nay, I presume to say, that an Elementary Treatise of Chymistry may prove a very useful book, even to those who have made some progress in the Science: for as it contains only the fundamental propositions, and indeed is an abstract of the whole Art, it may help them to recollect the most important parts of what they have read in many different works, and fix in their memoirs the most essential truths, which might else be either confounded with others, or entirely forgot. And these are the motives which determined me to compose the Work which I now offer to the Public. The general Plan on which I proceed is to suppose my Reader an absolute Novice in Chymistry; to lead him from the most simple truths, and such as imply the lowest degree of knowledge, to such as are more complex, and require a greater acquaintance with Nature. This order, which I have laid down for my rule, hath obliged me to begin with examining the most simple substances that we know, and which we consider as the elements whereof others are composed; as, by knowing the properties of these elementary parts, we are naturally led to those of their several combinations; and, on the other hand, in order to know the properties of compound bodies, it is necessary we should be first acquainted with the properties of their principles. The same reason induced me, when enquiring into the properties of one substance, to take no notice of those which relate to any other substance not treated of before. For example: as I treat of Acids before Metals, I say nothing under the head of those Acids concerning their power of dissolving metals; that I defer till I come to the subject of Metals: and thus I avoid speaking prematurely of a substance with which I suppose my Reader wholly unacquainted. And this method I was so much the more easily induced to follow, that I know of no Chymical book written on the same Plan. After discoursing of Elements in general, I treat next of such substances as are immediately composed of them, and are, next to them, the most simple: such are all saline substances. This head comprehends mineral Acids, fixed Alkalis, and their several combinations; the volatile sulphureous spirit, sulphur, phosphorus, and the Neutral salts which have an earth or fixed Alkali for their basis: those which have for their basis either a volatile Alkali, or some metallic substance, are referred, according to my general Plan, to the heads under which I treat of those substances. Metallic substances are scarcely more compounded than the saline; which induces me to consider them next. I begin with those which are the most simple, or at least seem to be so; because their principles, being very strongly connected together, are separated with the greatest difficulty: such are the Metals properly so called; namely, Gold, Silver, Copper, Iron, Tin, and Lead. After these come the Semi-metals in order; to wit, Regulus of Antimony, Zinc, Bismuth, and Regulus of Arsenic. Mercury being a doubtful substance, which some Chymists rank with the Metals, and others with the Semi-metals, because it actually possesses certain properties in common with each, I have treated of it in a separate Chapter, which stands between the Metals and Semi-metals. I next proceed to examine the several sorts of Oils, whether Vegetable, which are divided into fat, essential, and empyreumatic; or Animal, and Mineral Oils. By examining these substances we obtain ideas of all the principles which enter into the composition of Vegetable and Animal bodies; that is, of those substances that are capable of fermentation: this enables me to treat of fermentation in general; of its three different degrees or kinds, the spirituous, acetous, and putrid; and of the products of those fermentations, ardent spirits, acids analogous to those of vegetables and animals, and volatile alkalis. The order in which I treat of all those substances being different from that in which they are obtained from compound bodies, I give, in a distinct Chapter, a general idea of Chymical Decomposition, with a view to shew the order in which they are separated, from the several bodies in the composition whereof they are found. This brings them a second time under review, and gives me an opportunity of distinguishing those which exist naturally in compound bodies, from those which are only the result of a new combination of some of their principles produced by the fire. The succeeding Chapter explains the late Mr Geoffroy's Table of Affinities; which I take to be of great use at the end of an Elementary tract like this, as it collects into one point of view the most essential and fundamental doctrines which are dispersed through the work. I conclude with an account of the Construction of such Vessels and Furnaces as are usually employed in Chymistry. In this Part I say nothing of any manual operations, or the several ways of performing Chymical processes; reserving these particulars for my Treatise of Practical Chymistry, to which this must be considered as an Introduction. CONTENTS. Elements of the THEORY of CHYMISTRY. CHAP. I. _Of the Principles of Bodies_ Page 1 Sect. 1. Of Air 2 Sect. 2. Of Water 3 Sect. 3. Of Earth 4 Sect. 4. Of Fire 5 Sect. 5. Of the Phlogiston 7 CHAP. II. _A general View of the Relations or Affinities between Bodies_ 9 CHAP. III. _Of Saline Substances in general_ 11 Sect. 1. Of Acids 12 Sect. 2. Of Alkalis 14 Sect. 3. Of Neutral Salts 15 CHAP. IV. _Of the Several Sorts of Saline Substances._ Sect. 1. Of the Universal Acid 18 Sect. 2. Of the Nitrous Acid 22 Sect. 3. Of the Marine Acid 25 CHAP. V. _Of Lime_ 29 CHAP. VI. _Of Metallic Substances in general_ 34 CHAP. VII. _Of Metals_ 37 Sect. 1. Of Gold _ib._ Sect. 2. Of Silver 39 Sect. 3. Of Copper 44 Sect. 4. Of Iron 47 Sect. 5. Of Tin 52 Sect. 6. Of Lead 53 CHAP. VIII. _Of Quick-Silver_ 58 CHAP. IX. _Of the Semi-Metals._ Sect. 1. Of Regulus of Antimony 62 Sect. 2. Of Bismuth 69 Sect. 3. Of Zinc 70 Sect. 4. Of Regulus of Arsenic 72 CHAP. X. _Of Oil in general_ 76 Sect. 1. Of Charcoal 77 Sect. 2. Of Soap 78 CHAP. XI. _Of the Several Sorts of Oils._ Sect. 1. Of Mineral Oils 79 Sect. 2. Of Vegetable Oils 80 Sect. 3. Of Animal Oils 82 CHAP. XII. _Of Fermentation in general_ 83 CHAP. XIII. _Of the Spirituous Fermentation_ 84 CHAP. XIV. _Of the Acetous Fermentation_ 90 Sect. 1. Of Vinegar 91 Sect. 2. Of Tartar 93 CHAP. XV. _Of the Putrid Fermentation, or Putrefaction_ 96 CHAP. XVI. _A general View of Chymical Decomposition_ 101 Sect. 1. The Analysis of Vegetable Substances 102 Emulsions 104 Sect. 2. The Analysis of Animal Substances 106 Sect. 3. The Analysis of Mineral Substances 108 Of the Pyrites 110 Of Ores 112 CHAP. XVII. _Explanation of the Table of Affinities_ 119 CHAP. XVIII. _The Theory of Constructing the Vessels most commonly used in Chymistry_ 126 CHAP. XIX. _The Theory of Constructing the Furnaces most commonly used in Chymistry_ 133 _Of Lutes_ 147 Elements of the PRACTICE of CHYMISTRY. Introduction 153 PART I. OF MINERALS. SECTION I. Operations performed on Saline Mineral Substances. CHAP. I. _Of the Vitriolic Acid._ 1. PROCESS. To extract Vitriol from the Pyrites 159 2. To extract Sulphur from the Pyrites, and other Sulphureous Minerals 162 3. To extract Alum from aluminous Minerals 165 4. To extract the Vitriolic Acid from Copperas or Green Vitriol 170 5. To decompose Sulphur, and extract its Acid, by burning it 174 6. To concentrate the Vitriolic Acid 176 7. To decompound Vitriolated Tartar by means of the Phlogiston; or to compose Sulphur by combining the Vitriolic Acid with the Phlogiston 179 CHAP. II. _Of the Nitrous Acid._ 1. PROCESS. To Extract Nitre out of Nitrous Earths and Stones. The Purification of Salt-Petre. Mother of Nitre. Magnesia 181 2. To decompose Nitre by means of the Phlogiston. Nitre fixed by Charcoal. _Clyssus_ of Nitre. _Sal Polychrestum_ 186 3. To decompose Nitre by means of the Vitriolic Acid. The Smoking Spirit of Nitre. _Sal de duobus._ The Purification of Spirit of Nitre 191 CHAP. III. _Of the Marine Acid._ 1. PROCESS. To extract Sea-salt from Sea-water, and from Brine-springs. Epsom Salt 195 2. Experiments concerning the Decomposition of Sea-salt by means of the Phlogiston. Kunckel's Phosphorus 197 3. To decompose Sea-salt by means of the Vitriolic Acid. Glauber's Salt. The Purification and Concentration of Spirit of Salt 211 4. To decompose Sea-salt by means of the Nitrous Acid. _Aqua regis._ Quadrangular Nitre 217 CHAP. IV. _Of Borax._ 218 SECTION II. Of Operations on Minerals. CHAP. I. _Of Gold._ 1. PROCESS. To separate Gold, by Amalgamation with Mercury, from the Earths and Stones with which it is found mixed 223 2. To dissolve Gold in _Aqua Regis_, and by that means separate it from Silver. _Aurum Fulminans._ _Aurum Fulminans_ reduced 227 3. To dissolve Gold by Liver of Sulphur 232 4. To separate Gold from all other Metalline substances by means of Antimony 233 CHAP. II. _Of Silver._ 1. PROCESS. To separate Silver from its Ore, by means of Scorification with Lead 238 2. The refining of Silver by the Cupel 243 3. To purify Silver by Nitre 248 4. To dissolve Silver in _Aqua Fortis_, and thereby separate it from every other Metalline substance. The Purification of _Aqua Fortis_. Silver precipitated by Copper 250 5. To separate Silver from the Nitrous Acid by Distillation. Crystals of Silver. The Infernal Stone 254 6. To separate Silver from the Nitrous Acid by Precipitation. _Luna Cornea._ _Luna Cornea_ reduced 256 7. To dissolve Silver, and separate it from Gold, by Cementation 258 CHAP. III. _Of Copper._ 1. PROCESS. To separate Copper from its Ore 262 2. To purify Black Copper, and render it malleable 264 3. To deprive Copper of its Phlogiston by Calcination 266 4. To resuscitate the Calx of Copper, and reduce it to Metal, by restoring its Phlogiston 267 5. To dissolve Copper in the Mineral Acids 268 CHAP. IV. _Of Iron._ 1. PROCESS. To separate Iron from its Ore 270 2. To render Pig-iron and brittle Iron malleable 273 3. To convert Iron into Steel 274 4. The Calcination of Iron. Sundry Saffrons of Mars 276 5. Iron dissolved by the mineral Acids 277 CHAP V. _Of Tin._ 1. PROCESS. To extract Tin from its Ore 279 2. The Calcination of Tin 280 3. The Dissolution of Tin by Acids 284 CHAP. VI. _Of Lead._ 1. PROCESS. To extract Lead from its Ore 286 2. To separate Lead from Copper 289 3. The Calcination of Lead 292 4. To prepare Glass of Lead 293 5. Lead dissolved by the Nitrous Acid 295 CHAP. VII. _Of Mercury._ 1. PROCESS. To extract Mercury from its Ore, or to revivify it from Cinabar 298 2. To give Mercury, by the action of Fire, the appearance of a Metalline Calx 301 3. To dissolve Mercury in the Vitriolic Acid. Turbith Mineral 302 4. To combine Mercury with Sulphur. Æthiop's Mineral 304 5. To sublime the Combination of Mercury and Sulphur into Cinabar 306 6. To dissolve Mercury in the Nitrous Acid. Sundry Mercurial Precipitates 307 7. To combine Mercury with the Acid of Sea-salt. Corrosive Sublimate 308 8. Sweet Sublimate 312 9. The Panacea of Mercury 314 SECTION III. Of Operations on the Semi-Metals. CHAP. I. _Of Antimony._ 1. PROCESS. To separate Antimony from its Ore 315 2. The common Regulus of Antimony 316 3. Regulus of Antimony precipitated by Metals 318 4. The Calcination of Antimony 321 5. Calx of Antimony reduced to a Regulus 323 6. Antimony calcined with Nitre. Liver of Antimony. _Crocus Metallorum_ 325 7. Another Calcination of Antimony with Nitre. Diaphoretic Antimony. _Materia Perlata_. _Clyssus_ of Antimony 326 8. Calx of Antimony vitrified 330 9. Kermes Mineral 331 10. Regulus of Antimony dissolved in the Mineral Acids 335 11. Regulus of Antimony combined with the Acid of Sea-salt Butter of Antimony. Cinabar of Antimony 338 12. Butter of Antimony decompounded by means of Water only. _Pulvis Algaroth_, or _Mercurius Vitæ_. The Philosophic Spirit of Vitriol 342 13. Bezoar Mineral. The Bezoartic Spirit of Nitre 343 14. Flowers of Antimony 347 15. Regulus of Antimony converted into Flowers 348 CHAP. II. _Of Bismuth._ 1. PROCESS. To extract Bismuth from its Ore 350 2. Bismuth dissolved by Acids. Magistery of Bismuth. Sympathetic Ink 352 CHAP. III. _Of Zinc._ 1. PROCESS. To extract Zinc from its Ore, or Calamine 357 2. To sublime Zinc into Flowers 359 3. To combine Zinc with Copper. Brass. Prince's Metal, &c. 361 4. Zinc dissolved in the Mineral Acids 365 CHAP. IV. _Of Arsenic._ 1. PROCESS. To extract Arsenic from its matrix. Zafre or Smalt 367 2. To separate Arsenic from Sulphur 371 3. To give Arsenic the Metalline Form. Regulus of Arsenic 374 4. To distil the Nitrous Acid by the interposition of Arsenic. Blue _Aqua Fortis_. A new Neutral Salt of Arsenic 377 5. To alkalizate Nitre by Arsenic 379 PART II. OF VEGETABLES. SECTION I. Operations on unfermented Vegetables. CHAP. I. _Of the Substances obtained from Vegetables by Expression only._ 1. PROCESS. To express and depurate the juice of a Plant, containing its Essential Salt. The crystallization of that Salt 383 2. To draw the Oils out of Kernels, Seeds, and Fruits, by Expression 386 3. To draw the Essential Oils of certain Fruits by Expression 387 CHAP. II. _Of the Substances obtained from Vegetables by Triture._ 1. PROCESS. To make the Extract of a Plant by Trituration 389 2. To extract from Seeds and Kernels, by Trituration, the matter of Emulsions 392 CHAP. III. _Of Operations on Fat Oils._ 1. PROCESS. To attenuate Fat Oils, and change their nature, by exposing them to the action of fire, and distilling them 395 2. To combine Fat Oils with Acids. The decomposition of this combination 398 3. To combine Fat Oils with Fixed Alkalis. Hard and Soft Soap. The decomposition of Soap 400 4. To combine Fat Oils with Sulphur 405 5. To combine Fat Oils with Lead, and the Calces of Lead. The Basis of Plasters. The decomposition of this combination 406 CHAP. IV. _Of the substances obtained from Vegetables with a degree of heat not exceeding that of boiling water._ 1. PROCESS. To obtain from Plants, by distilling them with the mean degree of heat between freezing and boiling water, a liquor impregnated with their Principle of Odour 408 2. To extract the Fat Oils of Plants by Decoction in boiling water. Cacao-Butter 410 3. To extract the Essential Oils of Plants by Distillation with the heat of boiling water. Distilled Water 412 4. To extract the Essential Oils of Plants by distillation _per descensum_ 418 5. Infusions, Decoctions, and Extracts of Plants 419 CHAP. V. _Of Operations on Essential Oils._ 1. PROCESS. The Rectification of Essential Oils 422 2. To fire Oils by combining them with highly concentrated Acids: instanced in Oil of Turpentine 426 3. To combine Essential Oils with mineral Sulphur. Balsam of Sulphur. This composition decompounded 434 4. To combine Essential Oils with Fixed Alkalis. Starkey's Soap 438 CHAP. VI. _Of the Substances obtained from Vegetables by means of a graduated heat, from that of boiling water, to the strongest that can be applied to them in close vessels._ 1. PROCESS. To analyze vegetable substances that yield neither a Fat nor an Essential Oil: instanced in Guaiacum-Wood 440 2. To analyze a vegetable substance which yields the same principles as are obtained from Animal matters: instanced in Mustard-seed 445 CHAP. VII. _Of the Substances obtained from Vegetables by Combustion._ 1. PROCESS. To procure a Fixed, Caustic, Alkaline Salt from a vegetable substance, by burning it in the open air 448 2. To procure the Fixed Salt of a Plant, by burning it after the manner of Tachenius 453 3. To render Fixed Alkalis very Caustic by means of Lime. The Caustic Stone 455 4. The Analysis of Soot 457 CHAP. VIII. _The Analyses of some particular substances belonging to the Vegetable Kingdom._ 1. PROCESS. Analysis of the Native Balsams: instanced in Turpentine 460 2. The Analysis of Resins: instanced in Benjamin. The Flowers and Oil of Benjamin 463 Reflections on the Nature and Properties of Camphor 465 3. The Analysis of Bitumens: instanced in Amber. The Volatile Salt and Oil of Amber 467 4. The Analysis of Bee's Wax, and such Oily Compounds as are analogous to it 472 5. The Saccharine juices of Plants analyzed: instanced in Honey 474 6. Gummy substances analyzed: instanced in Gum Arabic 476 SECTION II. Of Operations on Fermented Vegetable Substances. CHAP. I. _Of the Product of Spirituous Fermentation._ 1. PROCESS. To make Wine of Vegetable Substances that are susceptible of Spirituous Fermentation 478 2. To draw an Ardent Spirit from substances that have undergone the Spirituous Fermentation. The Analysis of Wine 482 3. To dephlegmate Spirit of Wine by the means of Fixed Alkalis. Spirit of Wine analyzed 486 CHAP. II. _Spirit of Wine combined with different Substances._ 1. PROCESS. To combine Spirit of Wine with the Vitriolic Acid. This combination decompounded. Rabel's Water. Æther. Sweet Oil of Vitriol. Hoffman's Anodyne Mineral Liquor 492 2. Spirit of Wine combined with Spirit of Nitre. Sweet Spirit of Nitre 503 3. Spirit of Wine combined with the Acid of Sea-salt. Dulcified Spirit of Salt 508 4. Oils, or Oily matters, that are soluble in Spirit of Wine, separated from Vegetables, and dissolved, by means of that Menstruum. Tinctures; Elixirs; Varnishes. Aromatic Strong Waters 510 CHAP. III. _Of Tartar._ 1. PROCESS. Tartar analyzed by distillation. The Spirit, Oil, and Alkaline Salt of Tartar 514 2. The depuration of Tartar. Cream and Crystals of Tartar 517 CHAP. IV. _Crystal of Tartar combined with several substances._ 1. PROCESS. Crystal of Tartar combined with Absorbent Earths. Soluble Tartars 519 2. Crystal of Tartar combined with Fixed Alkalis. The Vegetable Salt. Saignette's Salt. The decomposition of Soluble Tartar 524 3. Crystal of Tartar combined with Iron. Chalybeated Tartar. Tincture of Steel with Tartar. Soluble Chalybeated Tartar 528 4. Crystal of Tartar combined with the reguline part of Antimony. Stibiated or Emetic Tartar 534 CHAP. V. _Of the Product of Acetous Fermentation._ 1. PROCESS. Substances susceptible of the Acetous Fermentation turned into Vinegar 536 2. To concentrate Vinegar by Frost 540 3. Vinegar analyzed by distillation 542 CHAP. VI. _The Acid of Vinegar combined with different Substances._ 1. PROCESS. The Acid of Vinegar combined with Alkaline Substances. Foliated Salt of Tartar, or Regenerated Tartar. Decomposition of that Salt 547 2. The Acid of Vinegar combined with Copper. Verdegris. Crystals of Copper. This combination decompounded. Spirit of Verdegris 550 3. The Acid of Vinegar combined with Lead. Ceruse. Salt or Sugar of Lead. This combination decompounded 552 CHAP. VII. _Of the Putrid Fermentation of Vegetable Substances._ 1. PROCESS. The Putrefaction of Vegetables 557 2. Putrefied Vegetable substances analyzed 559 PART III. Of Operations on Animal Substances. CHAP. I. _Of Milk._ 1. PROCESS. Milk separated into Butter, Curd, and Whey: instanced in Cow's Milk 562 2. Butter analyzed by distillation 566 3. The Curd of Milk analyzed by distillation 569 4. Whey analyzed 571 CHAP. II. _Of the Substances which compose an Animal Body._ 1. PROCESS. Blood analyzed: instanced in Bullock's Blood 574 2. Flesh analyzed: instanced in Beef 580 3. Bones analyzed: instanced in Ox-bones 583 4. Animal Fat analyzed: instanced in Mutton-Suet 584 5. Eggs analyzed: instanced in Pullet's Eggs 586 CHAP. III. _Of Animal Excrements._ 1. PROCESS. Dung analyzed: instanced in Human Excrement. Mr. Homberg's Phosphorus 588 2. Human Urine analyzed 596 CHAP. IV. _Of Volatile Alkalis._ 1. PROCESS. Volatile Alkalis rectified and depurated 599 2. Volatile Alkalis combined with Acids. Sundry Ammoniacal Salts. Sal Ammoniac 602 3. Sal Ammoniac decompounded by Acids 607 4. Sal Ammoniac decompounded by Fixed Alkalis. Volatile Salt. The Febrifuge of Sylvius 608 5. Sal Ammoniac decompounded by Absorbent Earths and Lime. Volatile Spirit of Sal Ammoniac. Fixed Sal Ammoniac. Oil of Lime 611 6. Volatile Alkalis combined with oily matters. A Volatile Oily Aromatic Salt 616 [Illustration: Decorative Scroll] ELEMENTS OF THE THEORY OF CHYMISTRY. CHAP. I. _Of the_ PRINCIPLES _of_ BODIES. The object and principal end of Chymistry, is to separate the different substances that enter into the composition of bodies; to examine each of them apart; to discover their properties and relations; to decompose, if possible, those very substances; to compare them together, and combine them with others; to re-unite them again into one body, so as to reproduce the original compound with all its properties; or even to produce new compounds that never existed among the works of nature, from mixtures of other matters differently combined. But this Analysis, or Decomposition, of bodies is finite; we being unable to carry it beyond a certain limit. In whatever way we attempt to go further, we are always stopped by substances in which we can produce no change, which will not admit of being resolved into others, and which stand as so many firm barriers obstructing our progress. To these substances we may, in my opinion, give the title of Principles or Elements: at least, with regard to us, they are really such. Of this sort the principal are Earth, Water, Air, and Fire. For though there is ground to believe that these are not the primary component parts, or the most simple elements, of matter; yet, as we know by experience, that our senses cannot possibly discover the principles of which they are composed, it seems more reasonable to fix upon them, and consider them as simple homogeneous bodies, and the principles of the rest, than to fatigue our minds with vain conjectures about the parts or elements of which they may consist; seeing there is no criterion by which we can know whether we have hit upon the truth, or whether the notions we have formed are mere fancies. We shall therefore consider these four substances as the principles or elements of all the various compounds which nature presents to our inquiries: because, of all those we have as yet discovered, they are in fact the most simple; and because all our decompositions, all our experiments on other bodies, plainly prove that they are at last resolvable into these primary parts. These principles do not enter in the same proportion into all bodies: there are even some mixts in the composition of which this or that particular principle is not to be found. Thus Air and Water seem to be wholly excluded from the texture of Metals; at least all the experiments that have hitherto been made on them seem to confirm this opinion. The substances composed immediately of these _first_ Elements we shall call _secondary_ Principles; because in reality their several combinations with each other, the interchangeable coalitions that take place between them, constitute the different natures of all other bodies; which, as they result from the union both of primary and secondary principles, are properly entitled to the name of Compounds or Mixts. Before we enter upon the examination of Compound Substances, it is necessary to consider with some attention the most Simple ones, or our four first principles, in order to discover their chief properties. SECTION I. _Of_ AIR. Air is that Fluid which we constantly breathe, and which surrounds the whole surface of the terrestrial globe. Being heavy, like all other bodies, it penetrates into all places that are not either absolutely inaccessible, or filled with some other body heavier than itself. Its principal property is to be susceptible of condensation and rarefaction; so that the very same quantity of Air may occupy a much greater, or a much smaller space, according to the different state it is in. Heat and cold, or, if you will, the presence and the absence of the particles of Fire, are the most usual causes, and indeed the measures, of its condensation and rarefaction: for if a certain quantity of Air be heated, its bulk enlarges in proportion to the degree of heat applied to it; the consequence of which is, that the same space now contains fewer particles of Air than it did before. Cold again produces just the opposite effect. On this property which Air has, of being condensed and rarefied by heat, its elasticity or springiness chiefly depends. For if Air were forced by condensation into a less compass than it took up before, and then exposed to a very considerable degree of cold, it would remain quite inactive, without exerting such an effort as it usually makes against the compressing body. On the other hand, the elasticity of heated Air arises only from hence, that being rarefied by the action of Fire, it requires much more space than it occupied before. Air enters into the composition of many substances, especially vegetable and animal bodies: for by analysing most of them such a considerable quantity thereof is extricated, that some naturalists have suspected it to be altogether destitute of elasticity when thus combined with the other principles in the composition of bodies. According to them, the efficacy of the elastic power of the Air is so prodigious, and its force when compressed so excessive, that it is not possible the other component parts of bodies should be able to confine so much of it, in that state of compression which it must needs undergo, if retaining its elasticity it were pent up among them. However that be, this elastic property of the Air produces the most singular and important phenomena, observable in the resolution and composition of bodies. SECTION II. _Of_ WATER. Water is a thing so well known, that it is almost needless to attempt giving a general idea of it here. Every one knows that it is a transparent, insipid substance, and usually fluid. I say it is usually so; for being exposed to a certain degree of cold it becomes solid: solidity therefore seems to be its most natural state. Water exposed to the Fire grows hot; but only to a limited degree, beyond which its heat never rises, be the force of Fire applied to it ever so violent: it is known to have acquired this degree of heat by its boiling up with great tumult. Water cannot be made hotter, because it is volatile, and incapable of enduring the heat, without being evaporated and entirely dissipated. If such a violent and sudden heat be applied to Water, as will not allow it time to exhale gently in vapours, as when, for instance, a small quantity thereof is thrown upon a metal in fusion, it is dissipated at once with vast impetuosity, producing a most terrible and dangerous explosion. This surprising effect may be deduced from the instantaneous dilatation of the parts of the Water itself, or rather of the Air it contains. Moreover, Water enters into the texture of many bodies, both compounds and secondary principles; but, like Air, it seems to be excluded from the composition of all metals and most minerals. For although an immense quantity of Water exists in the bowels of the Earth, moistening all its contents, it cannot be thence inferred, that it is one of the principles of minerals. It is only interposed between their parts; for they may be entirely divested of it, without any sort of decomposition: indeed it is not capable of an intimate connection with them. SECTION III. _Of_ EARTH. We observed that the two principles above treated of are volatile; that is, the action of Fire separates them from the bodies they help to compose, carrying them quite off, and dissipating them. That of which we are now to speak, namely Earth, is fixed, and, when it is absolutely pure, resists the utmost force of Fire. So that, whatever remains of a body, after it hath been exposed to the power of the fiercest Fire, must be considered as containing nearly all its earthy principle, and consisting chiefly thereof. I qualify my expression thus for two reasons: the first is, because it often happens, that this remainder does not actually contain all the Earth which existed originally in the mixt body decomposed by Fire; since it will afterwards appear that Earth, though in its own nature fixed, may be rendered volatile by being intimately united with other substances which are so; and that, in fact, it is common enough for part of the Earth of a body to be thus volatilized by its other principles: the second is, that what remains after the calcination of a body is not generally its earth in perfect purity, but combined with some of its other principles, which, though volatile in their own natures, have been fixed by the union contracted between it and them. We shall, in the sequel, produce some examples to illustrate this theory. Earth, therefore, properly so called, is a fixed principle, which is permanent in the Fire. There is reason to think it very difficult, if not impossible, to obtain the earthy principle entirely free from every other substance: for after our utmost endeavours to purify them, the Earths we obtain from different compounds are found to have different properties, according to the different bodies from which they are procured; or else, if those Earths be pure, we must allow them to be essentially different, seeing they have different properties. Earth, in general, with regard to its properties, may be distributed into _fusible_, and _unfusible_; that is, into Earth that is capable of melting or becoming fluid in the Fire, and Earth that constantly remains in a solid form, never melting in the strongest degree of heat to which we can expose it. The former is also called _vitrifiable_, and the second _unvitrifiable_ Earth; because, when Earth is melted by the force of Fire, it becomes what we call _Glass_, which is nothing but the parts of Earth brought into nearer contact, and more closely united by the means of fusion. Perhaps the Earth, which we look upon as incapable of vitrification, might be fused if we could apply to it a sufficient degree of heat. It is at least certain, that some Earths, or stones, which separately resist the force of Fire, so that they cannot be melted, become fusible when mixed together. Experience convinced Mr. du Hamel that lime-stone and slate are of this kind. It is however undoubtedly true, that one Earth differs from another in its degree of fusibility: and this gives ground to believe, that there may be a species of Earth absolutely unvitrifiable in its nature, which, being mixed in different proportions with fusible Earths, renders them difficult to melt. Whatever may be in this, as there are Earths which we are absolutely unable to vitrify, that is a sufficient reason for our division of them. Unvitrifiable Earths seem to be porous, for they imbibe Water; whence they have also got the name of _Absorbent Earths_. SECTION IV. _Of_ FIRE. The Matter of the Sun, or of Light, the Phlogiston, Fire, the Sulphureous Principle, the Inflammable Matter, are all of them names by which the Element of Fire is usually denoted. But it should seem, that an accurate distinction hath not yet been made between the different states in which it exists; that is, between the phenomena of Fire actually existing as a principle in the composition of bodies, and those which it exhibits when existing separately and in its natural state: nor have proper distinct appellations been assigned to it in those different circumstances. In the latter state we may properly give it the names of Fire, Matter of the Sun, of Light, and of Heat; and may consider it as a substance composed of infinitely small particles, continually agitated by a most rapid motion, and, of consequence, essentially fluid. This substance, of which the sun may be called the general reservoir, seems to flow incessantly from that source, diffusing itself over the world, and through all the bodies we know; but not as a principle, or essential part of them, since they may be deprived thereof, at least in a great measure, without suffering any decomposition. The greatest change produced on them, by its presence or its absence, is the rendering them fluid or solid: so that all other bodies may be deemed naturally solid; Fire alone essentially fluid, and the principle of fluidity in others. This being presupposed, Air itself might become solid, if it could be entirely deprived of the Fire it contains; as bodies of most difficult fusion become fluid, when penetrated by a sufficient quantity of the particles of Fire. One of the chief properties of this pure Fire is to penetrate easily into all bodies, and to diffuse itself among them with a sort of uniformity and equality: for if a heated body be contiguous to a cold one, the former communicates to the latter all its excess of heat, cooling in exact proportion as the other warms, till both come to have the very same degree of heat. Heat, however, is naturally communicable soonest to the upper parts of a body; and consequently, when a body cools, the under parts become soonest cold. It hath been observed, for instance, that the lower extremity of a heated body, freely suspended in the air, grows cold sooner than the upper; and that, when a bar of iron is red-hot at one end, and cold at the other, the cold end is much sooner heated by placing the bar so that the hot end may be undermost, than, when that end is turned uppermost. The levity of the matter of Fire, and the vicinity of the Earth, may possibly be the causes of this phenomenon. Another property of Fire is to dilate all bodies into which it penetrates. This hath already been shewn with regard to Air and Water; and it produces the same effect on Earth. Fire is the most powerful agent we can employ to decompose bodies; and the greatest degree of heat producible by man, is that excited by the rays of the sun collected in the focus of a large burning-glass. SECTION V. _Of the_ PHLOGISTON. From what hath been said concerning the nature of Fire, it is evidently impossible for us to fix and confine it in any body. Yet the phenomena attending the combustion of inflammable bodies shew, that they really contain the matter of Fire as a constituent principle. By what mechanism then is this fluid, which is so subtle, so active, so difficult to confine, so capable of penetrating into every other substance in nature; how comes it, I say, to be so fixed as to make a component part of the most solid bodies? It is no easy matter to give a satisfactory answer to this question. But, without pretending to guess the cause of the phenomenon, let us rest contented with the certainty of the fact, the knowledge of which will undoubtedly procure us considerable advantages. Let us therefore examine the properties of Fire thus fixed, and become a principle of bodies. To this substance, in order to distinguish it from pure and unfixed Fire, the Chymists have assigned the peculiar title of the _Phlogiston_, which indeed is no other than a Greek word for the Inflammable Matter; by which latter name, as well as by that of the Sulphureous Principle, it is also sometimes called. It differs from elementary Fire in the following particulars. 1. When united to a body, it communicates to it neither heat nor light. 2. It produces no change in its state, whether of solidity or fluidity; so that a solid body does not become fluid by the accession of the Phlogiston, and _vice versa_; the solid bodies to which it is joined being only rendered thereby more apt to be fused by the force of the culinary fire. 3. We can convey it from the body with which it is joined into another body, so that it shall enter into the composition thereof, and remain fixed in it. On this occasion both these bodies, that which is deprived of the Phlogiston and that which receives it, undergo very considerable alterations; and it is this last circumstance, in particular, that obliges us to distinguish the Phlogiston from pure Fire, and to consider it as the element of Fire combined with some other substance, which serves it as a basis for constituting a kind of secondary principle. For if there were no difference between them, we should be able to introduce and fix pure Fire itself, wherever we can introduce and fix the Phlogiston: yet this is what we can by no means do, as will appear from experiments to be afterwards produced. Hitherto, Chymists have never been able to obtain the Phlogiston quite pure, and free from every other substance: for there are but two ways of separating it from a body of which it makes a part; to wit, either by applying some other body with which it may unite the moment it quits the former; or else by calcining and burning the compound from which you desire to sever it. In the former case it is evident that we do not get the Phlogiston by itself, because it only passes from one combination into another; and in the latter, it is entirely dissipated in the decomposition, so that no part of it can possibly be secured. The inflammability of a body is an infallible sign that it contains a Phlogiston; but from a body's not being inflammable, it cannot be inferred that it contains none; for experiments have demonstrated that certain metals abound with it, which yet are by no means inflammable. We have now delivered what is most necessary to be known concerning the principles of bodies in general. They have many other qualities besides those above-mentioned; but we cannot properly take notice of them here, because they presuppose an acquaintance with some other things relating to bodies, of which we have hitherto said nothing; intending to treat of them in the sequel as occasion shall offer. We shall only observe in this place, that when animal and vegetable matters are burnt, in such a manner as to hinder them from flaming, some part of the Phlogiston contained in them unites intimately with their most fixed earthy parts, and with them forms a compound, that can be consumed only by making it red-hot in the open air, where it sparkles and wastes away, without emitting any flame. This compound is called a _Coal_. We shall inquire into the properties of this Coal under the head of Oils: at present it suffices that we know in general what it is, and that it readily communicates to other bodies the Phlogiston it contains. CHAP. II. _A general View of the Relations or Affinities between Bodies._ Before we can reduce compound Bodies to the first principles above pointed out, we obtain, by analysing them, certain substances which are indeed more simple than the bodies they helped to compose, yet are themselves composed of our primary principles. They are therefore at one and the same time both principles and compounds; for which reason we shall, as was before said, call them by the name of Secondary Principles. Saline and oily matters chiefly constitute this class. But before we enter upon an examination of their properties, it is fit we lay before the reader a general view of what Chymists understand by the Relations or Affinities of Bodies; because it is necessary to know these, in order to a distinct conception of the different combinations we are to treat of. All the experiments hitherto made concur with daily observation to prove, that different bodies, whether principles or compounds, have such a mutual Conformity, Relation, Affinity, or Attraction, if you will call it so, as disposes some of them to join and unite together, while they are incapable of contracting any union with others. This effect, whatever be its cause, will enable us to account for, and connect together, all the phenomena that Chymistry produces. The nature of this universal affection of matter is distinctly laid down in the following propositions. First, If any substance hath any Affinity or conformity with another, the two will unite together, and form one compound. Secondly, It may be laid down as a general rule, that all similar substances have an Affinity with each other, and are consequently disposed to unite; as water with water, earth with earth, _&c._ Thirdly, Substances that unite together lose some of their separate properties; and the compounds resulting from their union partake of the properties of those substances which serve as their principles. Fourthly, The simpler any substances are, the more perceptible and considerable are their Affinities: whence it follows, that the less bodies are compounded, the more difficult it is to analyse them; that is, to separate from each other the principles of which they consist. Fifthly, If a body consist of two substances, and to this compound be presented a third substance, that has no Affinity at all with one of the two primary substances aforesaid, but has a greater Affinity with the other than those two substances have with each other, there will ensue a decomposition, and a new union; that is, the third substance will separate the two compounding substances from each other, coalesce with that which has an Affinity with it, form therewith a new combination, and disengage the other, which will then be left at liberty, and such as it was before it had contracted any union. Sixthly, It happens sometimes that when a third substance is presented to a body consisting of two substances, no decomposition follows; but the two compounding substances, without quitting each other, unite with the substance presented to them, and form a combination of three principles: and this comes to pass when that third substance has an equal, or nearly equal, Affinity with each of the compounding substances. The same thing may also happen even when the third substance hath no Affinity but with one of the compounding substances only. To produce such an effect, it is sufficient that one of the two compounding substances have to the third body a Relation equal, or nearly equal, to that which it has to the other compounding substance with which it is already combined. Thence it follows, that two substances, which, when apart from all others, are incapable of contracting any union, may be rendered capable of incorporating together in some measure, and becoming parts of the same compound, by combining with a third substance with which each of them has an equal Affinity. Seventhly, A body, which of itself cannot decompose a compound consisting of two substances, because, as we just now said, they have a greater affinity with each other than it has with either of them, becomes nevertheless capable of separating the two by uniting with one of them, when it is itself combined with another body, having a degree of Affinity with that one, sufficient to compensate its own want thereof. In that case there are two Affinities, and thence ensues a double decomposition and a double combination. These fundamental truths, from which we shall deduce an explanation of all the phenomena in Chymistry, will be confirmed and illustrated by applying them, as we shall do, to the several cases, of which our design in this treatise obliges us to give a circumstantial account. CHAP. III. _Of Saline Substances in general._ If a particle of water be intimately united with a particle of earth, the result will be a new compound, which, according to our third proposition of Affinities, will partake of the properties of earth and of water; and this combination principally forms what is called a _Saline Substance_. Consequently every Saline Substance must have an affinity with earth and with water, and be capable of uniting with both or either of them, whether they be separate or mixed together: and accordingly this property characterizes all Salts, or Saline Substances, in general. Water being volatile and Earth fixed, Salts in general are less volatile than the former, and less fixed than the latter; that is, fire, which cannot volatilize and carry off pure earth, is capable of rarefying and volatilizing a Saline Substance; but then this requires a greater degree of heat than is necessary for producing the same effects on pure water. There are several sorts of Salts, differing from one another, in respect either of the quantity, or the quality of the earth in their composition; or, lastly, they differ on account of some additional principles, which not being combined with them in sufficient quantity to hinder their Saline properties from appearing, permit them to retain the name of Salts, though they render them very different from the simplest Saline Substances. It is easy to infer, from what has been said of Salts in general, that some of them must be more, some less, fixed or volatile than others, and some more, some less, disposed to unite with water, with earth, or with particular sorts of earth, according to the nature or the proportion of their principles. Before we proceed further, it is proper just to mention the principle reasons, which induce us to think that every Saline Substance is actually a combination of earth and water, as we supposed at our entering on this subject. The first is, the conformity Salts have with earth and water, or the properties they possess in common with both. Of these properties we shall treat fully, as occasion offers to consider them, in examining the several sorts of Salts. The second is, that all Salts may be actually resolved into earth and water by sundry processes; particularly by repeated dissolution in water, evaporation, desiccation, and calcination. Indeed the Chymists have not yet been able to procure a Saline Substance, by combining earth and water together. This favours a suspicion, that, besides these two, there is some other principle in the composition of salts, which escapes our researches, because we cannot preserve it when we decompose them; but it is sufficient to our purpose, that water and earth are demonstrably amongst the real principles of Saline Substances, and that no experiment hath ever shewn us any other. SECTION I. _Of_ ACIDS. Of all Saline Substances, the simplest is that called an _Acid_, on account of its taste; which is like that of verjuice, sorrel, vinegar, and other sour things, which, for the same reason, are also called Acids. By this peculiar taste are Acids chiefly known. They have moreover the property of turning all the blue and violet colours of vegetables red, which distinguishes them from all other salts. The form, under which Acids most commonly appear, is that of a transparent liquor; though solidity is rather their natural state. This is owing to their affinity with water; which is so great, that, when they contain but just as much of it as is necessary to constitute them Salts, and consequently have a solid form, they rapidly unite therewith the moment they come into contact with it: and as the air is always loaded with moisture and aqueous vapours, its contact alone is sufficient to liquify them; because they unite with its humidity, imbibe it greedily, and by that means become fluid. We therefore say, they attract the moisture of the air. This change of a salt from a solid to a fluid state, by the sole contact of the air, is also called _Deliquium_; so that when a salt changes in this manner from a solid into a fluid form, it is said to run _per deliquium_. Acids being the simplest species of Saline bodies, their affinities with different substances are stronger than those of any other sort of salt with the same substances; which is agreeable to our fourth proposition concerning Affinities. Acids in general have a great affinity with earths: that with which they most readily unite is the unvitrifiable earth to which we gave the name of absorbent earth. They seem, not to act at all upon vitrifiable earths, such as sand; nor yet upon some other kinds of earths, at least while they are in their natural state. Yet the nature of these earths may be in some measure changed, by making them red-hot in the fire, and then quenching them suddenly in cold water: for, by repeating this often, they are brought nearer to the nature of absorbent earths, and rendered capable of uniting with Acids. When an acid liquor is mixed with an absorbent earth, for instance with chalk, these two substances instantly rush into union, with so much impetuosity, especially if the acid liquor be as much dephlegmated, or contain as little water, as may be, that a great ebullition is immediately produced, attended with considerable hissing, heat, and vapours, which rise the very instant of their conjunction. From the combination of an acid with an absorbent earth there arises a new compound, which some Chymists have called _Sal Salsum_; because the Acid by uniting with the earth loses its sour taste, and acquires another not unlike that of the common sea-salt used in our kitchens; yet varying according to the different sorts of Acids and earths combined together. The Acid at the same time loses its property of turning vegetable blues and violet colours red. If we inquire what is become of its propensity to unite with water, we shall find that the earth, which of itself is not soluble in water, hath, by its union with the Acid, acquired a facility of dissolving therein; so that our _Sal Salsum_ is soluble in water. But, on the other hand, the Acid hath, by its union with the earth, lost part of the affinity it had with water; so that if a _Sal Salsum_ be dried, and freed of all superfluous humidity, it will remain, in that dry solid form, instead of attracting the moisture of the air, and running _per deliquium_, as the Acid would do if it were pure and unmixed with earth. However, this general rule admits of some exceptions; and we shall have occasion in another place to take notice of certain combinations of Acids with earths, which still continue to attract the moisture of the air, though not so strongly as a pure Acid. ACIDS have likewise a great affinity with the Phlogiston. When we come to treat of each Acid in particular, we shall examine the combinations of each with the Phlogiston: they differ so widely from one another, and many of them are so little known, that we cannot at present give any general idea of them. SECTION II. _Of_ ALKALIS. Alkalis are Saline combinations, in which there is a greater proportion of earth than in Acids. The principal arguments that may be adduced to prove this fact are these: First; if they be treated in the manner proposed above for analyzing Saline Substances, we obtain from them a much greater quantity of earth than we do from Acids. Secondly; by combining certain Acids with certain earths we can produce Alkalis; or at least such saline compounds as greatly resemble them. Our third and last argument is drawn from the properties of those Alkalis which, when pure and unadulterated with any other principle, have less affinity with water than Acids have, and are also more fixed, resisting the utmost force of fire. On this account it is that they have obtained the title of _Fixed_, as well as to distinguish them from another species of Alkali, to be considered hereafter, which is impure and volatile. Though fixed Alkalis, when dry, sustain the utmost violence of fire without flying off in vapours, it is remarkable that, being boiled with water in an open vessel, considerable quantities of them rise with the steam: an effect which must be attributed to the great affinity between these two substances, by means whereof water communicates some part of its volatility to the fixed salt. Alkalis freed of their superfluous humidity by calcination attract the moisture of the air, but not so strongly as Acids: so that it is easier to procure and preserve them in a solid form. They flow in the fire, and are then capable of uniting with vitrifiable earths, and of forming therewith true glass, which, however, will partake of their properties, if they be used in sufficient quantity. As they melt more readily than vitrifiable earth, they facilitate its fusion; so that a weaker fire will reduce it to glass, when a fixed Alkali is joined with it, than will melt it without that addition. Alkalis are known by their taste, which is acrid and fiery; and by the properties they possess of turning vegetable blues and violet colours green; particularly syrop of violets. Their affinity with acids is greater than that of absorbent earths; and hence it comes to pass, that if an Alkali be presented to a combination of an Acid with an absorbent earth, the earth will be separated from the Acid by the Alkali, and a new union between the Acid and the Alkali will take place. This is both an instance and a proof of our fifth proposition concerning Affinities. If a pure Alkali be presented to a pure Acid, they rush together with violence, and produce the same phenomena as were observed in the union of an absorbent earth with an Acid; but in a greater and more remarkable degree. Fixed Alkalis may in general be divided into two sorts: one of these hath all the above-recited properties; but the other possesses some that are peculiar to itself. We shall consider this latter sort more particularly under the head of Sea-Salt. SECTION III. _Of_ NEUTRAL SALTS. The Acid and the Alkali thus uniting mutually rob each other of their characteristic properties; so that the compound resulting from their union produces no change in the blue colours of vegetables, and has a taste which is neither sour nor acrid, but saltish. A saline combination of this kind is for that reason named _Sal Salsum_, _Sal Medium_, of a _Neutral Salt_. Such combinations are also called by the plain general name of _Salts_. It must be observed that, in order to make these Salts perfectly Neutral, it is necessary that neither of the two saline principles of which they are compounded be predominant over the other; for in that case they will have the properties of the prevailing principle. The reason is this: neither of these saline substances can unite with the other but in a limited proportion, beyond which there can be no further coalition between them. The action by which this perfect union is accomplished is termed _Saturation_; and the instant when such proportions of the two saline substances are mixed together, that the one is incorporated with as much of the other as it can possibly take up, is called the _Point of Saturation_. All this is equally applicable to the combination of an Acid with an absorbent earth. The combination is known to be perfect, that is, the Point of Saturation is known to be obtained, when, after repeated affusions of an Acid in small quantities to an Alkali, or an absorbent earth, we find those phenomena cease, which in such cases constantly attend the conflict of union, as we said above, namely, ebullition, hissing, _&c._ and we may be assured the Saturation is complete when the new compound hath neither an acid nor an acrid taste, nor in the least changes the blue colours of vegetables. Neutral salts have not so great an affinity with water as either Acids or Alkalis have; because they are more compounded: for we observed before, that the affinities of the most compounded bodies are generally weaker than those of the most simple. In consequence hereof few Neutral Salts, when dried, attract the moisture of the air; and those that do, attract it more slowly, and in less quantity, than either Acids or Alkalis do. All Neutral Salts are soluble in water; but more or less readily, and in a greater or smaller quantity, according to the nature of their component principles. Water made boiling hot dissolves a greater quantity of those salts which do not attract the moisture of the air, than when it is cold; and indeed it must be boiling hot to take up as much of them as it is capable of dissolving: but as for those which run in the air, the difference, if there be any, is imperceptible. Some Neutral Salts have the property of shooting into crystals, and others have it not. The nature of Crystallization is this: Water cannot dissolve, nor keep in solution, more than a determinate quantity of any particular Salt: when therefore such a quantity of water is evaporated from the solution of a Salt capable of crystallization, that the remainder contains just as much Salt as it can dissolve, then by continuing the evaporation the Salt gradually recovers its solid form, and concretes into several little transparent masses called Crystals. These crystals have regular figures, all differing from one another according to the species of salt of which they are formed. Different methods of evaporating saline solutions have different effects on the figure and regularity of the crystals; and each particular sort of salt requires a peculiar method of evaporation to make its crystals perfectly regular. A solution of salt designed for crystallization is usually evaporated by means of fire to a pellicle; that is, till the Salt begin to concrete; which is perceived by a kind of thin dark skin that gathers on the surface of the liquor, and is formed of the crystallized particles of Salt. When this pellicle appears the solution is suffered to cool, and the crystals form therein faster or slower, according to the sort of salt in hand. If the evaporation be carried on briskly to perfect dryness, no crystals will be formed, and only an irregular mass of salt will be obtained. The reasons why no crystals appear when the evaporation is hastily performed, and carried on to dryness, are, first, that the particles of salt, being always in motion while the solution is hot, have not time to exert their mutual affinities, and to unite together as crystallization requires: Secondly, that a certain quantity of water enters into the very composition of crystals; which is therefore absolutely necessary to their formation, and in a greater or smaller proportion according to the nature of the Salt[1]. [1] Those who have the curiosity to see a more particular account of the Crystallization of Neutral Salts, may read Mr. _Rouelle_'s excellent Memoir on that subject, among those of the Academy of Sciences for 1744. If these crystallized salts be exposed to the fire, they first part with that moisture which is not necessary to a saline concretion, and which they retained only by means of their crystallization: afterwards they begin to flow, but with different degrees of fusibility. It must be observed, that certain salts melt as soon as they are exposed to the fire; namely, those which retain a great deal of water in crystallizing. But this fluor which they so readily acquire must be carefully distinguished from actual fusion: for it is owing only to their superfluous humidity, which heat renders capable of dissolving and liquifying them; so that when it is evaporated the Salt ceases to be fluid, and requires a much greater degree of fire to bring it into real fusion. The Neutral Salts that do not crystallize may, indeed, be dried by evaporating the water which keeps them fluid; but by becoming solid they acquire no regular form; they again attract the moisture of the air, and are thereby melted into a liquor. These may be called _Liquescent Salts_. Most of the Neutral Salts, that consist of an Acid joined with a fixed Alkali, or with an absorbent earth, are themselves fixed and resist the force of fire; yet several of them, if they be dissolved in water, and the solution boiled and evaporated, fly off along with the steams. CHAP. IV. _Of the several Sorts of Saline Substances._ SECTION I. _Of the_ UNIVERSAL ACID. The Universal Acid is so called, because it is in fact the Acid which is most universally diffused through all nature, in waters, in the atmosphere, and in the bowels of the earth. But it is seldom pure; being almost always combined with some other substance. That from which we obtain it with most ease, and in the greatest quantity, is Vitriol, a mineral which we shall consider afterwards: and this is the reason why it is called the _Vitriolic Acid_; the name by which it is best known. When the Vitriolic Acid contains but little phlegm, yet enough to give it a fluid form, it is called _Oil of Vitriol_, on account of a certain unctuosity belonging to it. In truth this name is very improperly bestowed on it; for we shall afterwards see that, bating this unctuousness, it has none of the properties of oils. But this is not the only impropriety in names that we shall have occasion to censure. If the Vitriolic Acid contain much water, it is then called _Spirit of Vitriol_. When it does not contain enough to render it fluid, and so is in a solid form, it is named the _Icy Oil of Vitriol_. When Oil of Vitriol highly concentrated is mixed with water, they rush into union with such impetuosity, that, the moment they touch each other, there arises a hissing noise, like that of red-hot iron plunged in cold water, together with a very considerable degree of heat, proportioned to the degree to which the Acid was concentrated. If, instead of mixing this concentrated Acid with water, you only leave it exposed to the air for some time, it attracts the moisture thereof, and imbibes it most greedily. Both its bulk and its weight are increased by this accession; and if it be under an icy form, that is, if it be concreted, the phlegm thus acquired will soon resolve it into a fluid. The addition of water renders the Vitriolic Acid, and indeed all other Acids, weaker in one sense; which is, that when they are very aqueous they leave on the tongue a much fainter taste of acidity, and are less active in the solution of some particular bodies: but that occasions no change in the strength of their affinities, but in some cases rather enables them to dissolve several substances, which, when well dephlegmated, they are not capable of attacking. The Vitriolic Acid combined to the point of saturation with a particular absorbent earth, the nature of which is not yet well known, forms a Neutral Salt that crystallizes. This Salt is called _Alum_, and the figure of its crystals is that of an octahedron, or solid of eight sides. These octahedra are triangular pyramids, the angles of which are so cut off that four of the surfaces are hexagons, and the other four triangles. There are several sorts of Alum, which differ according to the earths combined with the Vitriolic Acid. Alum dissolves easily in water, and in crystallization retains a considerable quantity of it; which is the reason that being exposed to the fire it readily melts, swelling and puffing up as its superfluous moisture exhales. When that is quite evaporated, the remainder is called _Burnt Alum_, and is very difficult to fuse. The Acid of the Alum is partly dissipated by this calcination. Its taste is saltish, with a degree of roughness and astringency. The Vitriolic Acid combined with certain earths forms a kind of Neutral Salt called _Selenites_, which crystallizes in different forms according to the nature of its earth. There are numberless springs of water infected with dissolved Selenites; but when this Salt is once crystallized, it is exceeding difficult to dissolve it in water a second time. For that purpose a very great quantity of water is necessary, and moreover it must boil; for as it cools most of the dissolved Selenites takes a solid form, and falls in a powder to the bottom of the vessel. If an Alkali be presented to the Selenites, or to Alum, these Salts, according to the principles we have laid down, will be thereby decomposed; that is, the Acid will quit the earths, and join the Alkali, with which it hath a greater affinity. And from this conjunction of the Vitriolic Acid with a fixed Alkali there results another sort of Neutral Salt, which is called _Arcanum duplicatum_, _Sal de duobus_, and _Vitriolated Tartar_, because one of the fixed Alkalis most in use is called Salt of Tartar. Vitriolated Tartar is almost as hard to dissolve in water as the Selenites. It shoots into eight-sided crystals, having the apices of the pyramids pretty obtuse. Its taste is saltish, inclining to bitter; and it decrepitates on burning coals. It requires a very great degree of fire to make it flow. The Vitriolic Acid is capable of uniting with the Phlogiston, or rather it has a greater affinity with it than with any other body: whence it follows, that all compounds, of which it makes a part, may be decomposed by means of the Phlogiston. From the conjunction of the Vitriolic Acid with the Phlogiston arises a compound called _Mineral Sulphur_, because it is found perfectly formed in the bowels of the earth. It is also called _Sulphur vivum_, or simply _Sulphur_. Sulphur is absolutely insoluble in water, and incapable of contracting any sort of union with it. It melts with a very moderate degree of heat, and sublimes in fine light downy tufts called _Flowers of Sulphur_. By being thus sublimed, it suffers no decomposition, let the operation be repeated ever so often; so that Sublimed Sulphur, or Flower of Sulphur, hath exactly the same properties as Sulphur that has never been sublimed. If Sulphur be exposed to a brisk heat in the open air, it takes fire, burns, and is wholly consumed. This deflagration of Sulphur is the only means we have of decomposing it, in order to obtain its Acid in purity. The Phlogiston is destroyed by the flame, and the Acid exhales in vapours: these vapours collected have all the properties of the Vitriolic Acid, and differ from it only as they still retain some portion of the Phlogiston; which, however, soon quits them of its own accord, if the free access of the common air be not precluded. The portion of Phlogiston retained by the Acid of Sulphur is much more considerable when that mineral is burnt gradually and slowly: in that case the vapours which rise from it have such a penetrating odour, that they instantaneously suffocate any person who draws in a certain quantity of them with his breath. These vapours constitute what is called the _Volatile Spirit of Sulphur_. There is reason to think this portion of Phlogiston which the Acid retains is combined therewith in a manner different from that in which these two are united in the Sulphur itself; for, as has just been observed, nothing but actual burning is capable of separating the Vitriolic Acid and the Phlogiston, which by their union form Sulphur; whereas in the Volatile Spirit of Sulphur they separate spontaneously when exposed to the open air; that is, the Phlogiston flies off and leaves the Acid, which then becomes in every respect similar to the Vitriolic Acid. That the Volatile Spirit of Sulphur is a compound, as we have asserted it to be, appears evidently from hence, that whenever the Vitriolic Acid touches any substance containing the Phlogiston, provided that Phlogiston be disengaged or opened to a certain degree, a Volatile Spirit of Sulphur is infallibly and immediately generated. This Spirit hath all the properties of Acids, but considerably weakened, and of course less perceptible. It unites with absorbent earths or fixed Alkalis; and with them forms Neutral Salts; but when combined therewith it may be separated from them by the Vitriolic Acid, and indeed by any of the mineral Acids, because its affinities are weaker. Sulphur hath the property of uniting with absorbent earths, but not near so intimately as with fixed Alkalis. If equal parts of Sulphur and an Alkali be melted together, they incorporate with each other; and from their conjunction proceeds a compound of a most unpleasant smell, much like that of rotten eggs, and of a red colour nearly resembling that of an animal liver, which has occasioned it to bear the name of _Hepar Sulphuris_, or _Liver of Sulphur_. In this composition the fixed Alkali communicates to the Sulphur the property of dissolving in water: and hence it comes that Liver of Sulphur may be made as well when the Alkali is dissolved by water into a fluid, as when it is fused by the action of fire. Sulphur has less affinity than any Acid with the fixed Alkalis: and therefore Liver of Sulphur may be decompounded by any Acid whatever; which will unite with the fixed Alkali, form therewith a Neutral Salt, and separate the Sulphur. If Liver of Sulphur be dissolved in water, and an Acid poured thereon, the liquor, which was transparent before, instantly turns to an opaque white; because the Sulphur, being forced to quit its union with the Alkali, loses at the same time the property of dissolving in water, and appears again in its own opaque form. The liquor thus made white by the Sulphur is called _Milk of Sulphur_. If this liquor be suffered to stand still for some time, the particles of Sulphur, now most minutely divided, gradually approach each other, unite, and fall insensibly to the bottom of the vessel; and then the liquor recovers its transparency. The Sulphur thus deposited on the bottom of the vessel is called the _Magistery_ or _Precipitate of Sulphur_. The names of Magistery and Precipitate are also given to all substances whatever, that are separated from another by this method; which is the reason that we use the expression of precipitating one substance by another, to signify the separating one of them by means of the other. SECTION II. _Of the_ NITROUS ACID. It is not certainly known what constitutes the difference between the Nitrous Acid and the Vitriolic Acid, with regard to the constituent principles of each. The most probable opinion is, that the Nitrous Acid is no other than the Vitriolic Acid combined with a certain quantity of Phlogiston by the means of putrefaction. If it be so, the Phlogiston must be united with the Universal Acid in another manner than it is in sulphur, and in its volatile spirit: for the Nitrous Acid differs from them both in its properties. What gives ground for this opinion is, that the Nitrous Acid is never found but in earths and stones which have been impregnated with matters subject to putrefaction, and which therefore must contain the Phlogiston. For it is necessary just to observe here, though it be not yet proper to enter particularly into the subject, that all substances susceptible of putrefaction really contain the Phlogiston. The Nitrous Acid combined with certain absorbent earths, such as chalk, marle, boles, forms Neutral Salts which do not crystallize; and which, after being dried, run in the air _per deliquium_. All those Neutral Salts which consist of the Nitrous Acid joined to an earth, may be decomposed by a fixed Alkali, with which the Acid unites, and deserts the earth; and from this union of the Nitrous Acid with a fixed Alkali results a new Neutral Salt which is called _Nitre_, or _Salt-peter_. This latter name signifies the _Salt of Stone_; and, in fact, Nitre is extracted from the stones and plaster, in which it forms, by boiling them in water saturated with a fixed Alkali. Nitre shoots in long crystals adhering sideways to each other; it has a saltish taste, which produces a sensation of cold on the tongue. This Salt easily dissolves in water; which, when boiling hot, takes up still a greater quantity thereof. It flows with a pretty moderate degree of heat, and continues fixed therein; but being urged by a brisk fire, and in the open air, it lets go some part of its Acid, and indeed flies off itself in part. The most remarkable property of Nitre, and that which characterizes it, is its fulmination or explosion; the nature of which is as follows: When Nitre touches any substance containing a Phlogiston, and actually ignited, that is, actually on fire, it bursts out into a flame, burns, and is decompounded with much noise. In this deflagration the Acid is dissipated, and totally separated from the Alkali, which now remains by itself. Indeed the Acid, at least the greatest part of it, is by this means quite destroyed. The Alkali which is left when Nitre is decompounded by deflagration, is called in general _Fixed Nitre_, and, more particularly, Nitre fixed by such and such a substance as was used in the operation. But if Nitre be deflagrated with an inflammable substance containing the vitriolic Acid, as sulphur, for instance, the fixed Salt produced by the deflagration is not a pure Alkali, but retains a good deal of the vitriolic Acid, and, by combining therewith, hath now formed a neutral Salt. Hitherto Chymists have been at a loss for the reason why Nitre flames, and is decompounded in the manner above-mentioned, when it comes in contact with a Phlogiston properly circumstanced. For my part, I conjecture it to be for the same reason that vitriolated tartar is also decompounded by the addition of a Phlogiston; _viz._ the Nitrous Acid, having a greater affinity with the Phlogiston than with the fixed Alkali, naturally quits the latter to join with the former, and so produces a kind of sulphur, differing probably from the common sulphur, formed by the vitriolic Acid, in that it is combustible to such a degree, as to take fire and be consumed in the very moment of its production; so that it is impossible to prevent its being thus destroyed, and consequently impossible to save it. In support of this opinion let it be considered, that the concurrence of the Phlogiston is absolutely necessary to produce this deflagration, and that the matter of pure fire is altogether incapable of effecting it: for though Nitre be exposed to the most violent degree of fire, even that in the focus of the most powerful burning-glass, it will not flame; nor will that effect ever happen till the Nitre be brought into contact with a Phlogiston properly so called, that is, the matter of fire existing as a principle of some body; and it is moreover necessary that this Phlogiston be actually on fire, and agitated with the igneous motion, or else that the Nitre itself be red hot, and so penetrated with fire as to kindle any inflammable matter that touches it. This experiment, among others, helps to shew the distinction that ought to be made between pure elementary fire, and fire become a principle of bodies, to which we have given the name of Phlogiston. Before we leave this subject, we shall observe, that Nitre deflagrates only with such substances as contain the Phlogiston in its simplest and purest form; such as charcoal, sulphur, and the metalline substances; and that, though it will not deflagrate without the addition of some combustible matter, it is nevertheless the only known body that will burn, and make other combustibles burn with it, in close vessels, without the admission of fresh air. The Nitrous Acid hath not so great an affinity with earths and Alkalis as the vitriolic Acid hath with the same substances; whence it follows that the vitriolic Acid decomposes all neutral salts arising from a combination of the Nitrous Acid with an earth or an Alkali. The vitriolic Acids expells the Nitrous Acid, unites with the substance which served it for a basis, and therewith forms a neutral salt, which is an Alum, a Selenites, or a vitriolated Tartar, according to the nature of that basis. The Nitrous Acid, when thus separated from its basis by the vitriolic Acid, is named _Spirit of Nitre_, or _Aqua Fortis_. If it be dephlegmated, or contain but little superfluous water, it exhales in reddish vapours; these vapours, being condensed and collected, form a liquor of a brownish yellow, that incessantly emits vapours of the same colour, and of a pungent disagreeable smell. These characters have procured it the names of _Smoaking Spirit of Nitre_, and _Yellow Aqua Fortis_. This property in the Nitrous Acid, of exhaling in vapours, shews it to be less fixed than the vitriolic Acid; for the latter, though ever so thoroughly dephlegmated, never yields any vapours, nor has it any smell. SECTION III. _Of the_ ACID OF SEA-SALT. The Acid of Sea-salt is so called because it is in fact obtained from such Sea-salt as is used in our kitchens. It is not certainly known in what this Acid differs from the vitriolic and the nitrous, with regard to its constituent parts. Several of the ablest Chymists, such as Becher and Stahl, are of opinion that the Marine Acid is no other than the Universal Acid united to a particular principle which they call a Mercurial Earth. Concerning this earth we shall have occasion to say more, when we come to treat of metallic substances: but in the mean time it must be owned, that the truth of this opinion is so far from being proved by a sufficient number of experiments, that the very existence of such a mercurial earth is not yet well established; and therefore, that we may not exceed the bounds of our knowledge, we shall content ourselves with delivering here the properties which characterize the Acid in question, and by which it is distinguished from the two others considered above. When it is combined with absorbent earths, such as lime and chalk, it forms a neutral salt that does not crystallize, and, when dried, attracts the moisture of the air. If the absorbent earth be not fully saturated with the Marine Acid, the salt thereby formed has the properties of a fixed Alkali: and this is what made us say, when we were on the subject of those salts, that they might be imitated by combining an earth with an Acid. The Marine Acid, like the rest, hath not so great an affinity with earths as with fixed Alkalis. When it is combined with the latter, it forms a neutral salt which shoots into cubical crystals. This salt is inclined to grow moist in the air, and is consequently one of those which water dissolves in equal quantities, at least as to sense, whether it be boiling hot or quite cold. The affinity of this Acid with Alkalis and absorbent Earths is not so great as that of the vitriolic and nitrous Acids with the same substances: whence it follows, that, when combined therewith, it may be separated from them by either of those Acids. The Acid of Sea-salt, thus disengaged from the substance which served it for a basis, is called _Spirit of Salt_. When it contains but little phlegm it is of a lemon colour, and continually emits many white, very dense, and very elastic vapours; on which account it is named the _Smoaking Spirit of Salt_. Its smell is not disagreeable, nor much unlike that of saffron; but extremely quick and suffocating when it smokes. The Acid of Sea-salt, like the other two, seems to have a greater affinity with the Phlogiston, than with fixed Alkalis. We are led to this opinion by a very curious operation, which gives ground to think that Sea-salt may be decomposed by the proper application of a substance containing the Phlogiston. From the Marine Acid combined with a Phlogiston results a kind of Sulphur, differing from the common sort in many respects; but particularly in this property, that it takes fire of itself upon being exposed to the open air. This combination is called _English Phosphorus_, _Phosphorus of Urine_, because it is generally prepared from urine; or, only _Phosphorus_. This combination of the Marine Acid with a Phlogiston is not easily effected; because it requires a difficult operation in appropriated vessels. For these reasons it does not always succeed; and Phosphorus is so scarce and dear, that hitherto Chymists have not been able to make on it the experiments necessary to discover all its properties. If Phosphorus be suffered to burn away in the air, a small quantity of an acid liquor may be obtained from it, which seems to be spirit of salt, but either altered, or combined with some adventitious matter; for it has several properties that are not to be found in the pure Marine Acid; such as, leaving a fixed fusible substance behind it when exposed to a strong fire, and being easily combined with the Phlogiston so as to reproduce a Phosphorus. Phosphorus resembles sulphur in several of its properties: it is soluble in oils; it melts with a gentle heat; it is very combustible; it burns without producing soot; and its flame is vivid and bluish. From what has been said of the union of the Acid of Sea-salt with a fixed Alkali, and of the neutral salt resulting therefrom, it may be concluded that this neutral salt is no other than the common kitchen-salt. But it must be observed, that the fixed Alkali, which is the natural basis of the common salt obtained from sea-water, is of a sort somewhat differing from fixed Alkalis in general, and hath certain properties peculiar to itself. For, 1. The basis of Sea-salt differs from other fixed Alkalis in this, that it crystallizes like a neutral salt. 2. It does not grow moist in the air; on the contrary, when exposed to the air, it loses part of the water that united with it in crystallization, by which means its crystals lose their transparency, become, as it were, mealy, and fall into a fine flour. 3. When combined with the vitriolic Acid to the point of saturation, it forms a neutral salt differing from vitriolated tartar, first, in the figure of its crystals, which are oblong six-sided solids; secondly, in its quantity of water, which in crystallization unites therewith in a much greater proportion than with vitriolated tartar; whence it follows, that this salt dissolves in water more readily than vitriolated tartar; thirdly, in that it flows with a very moderate degree of heat, whereas vitriolated tartar requires a very fierce one. If the Acid of Sea-salt be separated from its basis by means of the vitriolic Acid, it is easy to see that, when the operation is finished, the salt we have been speaking of must be the result. A famous Chymist, named Glauber, was the first who extracted the Spirit of Salt in this manner, examined the neutral salt resulting from his process, and, finding it to have some singular properties, called it his _Sal mirabile_, or wonderful Salt: on this account it is still called Glauber's _Sal mirabile_, or plainly _Glauber's Salt_. 4. When the basis of Sea-salt is combined with the nitrous Acid to the point of saturation, there results a neutral salt, or a sort of nitre, differing from the common nitre, first, in that it attracts the moisture of the air pretty strongly; and this makes it difficult to crystallize; secondly, in the figure of its crystals, which are parallelopipeds; and this has procured it the name of _Quadrangular Nitre_. Common salt, or the neutral salt formed by combining the Marine Acid with this particular sort of fixed Alkali, has a taste well known to every body. The figure of its crystals is exactly cubical. It grows moist in the air, and, when exposed to the fire, it bursts, before it melts, into many little fragments, with a crackling noise; which is called the _Decrepitation_ of Sea-salt. That neutral salt mentioned above, which is formed by combining the Marine Acid with a common fixed Alkali, and called _Sal febrifugum Sylvii_, hath also this property. India furnishes us with a saline substance, known by the name of _Borax_, which flows very easily, and then takes the form of glass. It is of great use in facilitating the fusion of metallic substances. It possesses some of the properties of fixed Alkalis, which has induced certain Chymists to represent it, through mistake, as a pure fixed Alkali. By mixing borax with the vitriolic Acid, Mr. Homberg obtained from it a salt, which sublimes in a certain degree of heat, whenever such a mixture is made. This salt has very singular properties; but its nature is not yet thoroughly understood. It dissolves in water with great difficulty; it is not volatile, though it rises by sublimation from the borax. According to Mr. Rouelle's observation, it rises then only by means of the water which carries it up: for, when once made, it abides the fiercest fire, flows and vitrifies just as borax does: provided care be taken to free it previously from moisture by drying it properly. Mr. Homberg called it _Sedative Salt_, on account of its medical effects. The sedative salt hath the appearance, and some of the properties, of a neutral salt; for it shoots into crystals, and does not change the colour of violets; but it acts the part of an Acid with regard to Alkalis, uniting with them to the point of saturation, and thereby forming a true neutral salt. It also acts, like the Acid of vitriol on all neutral salts; that is, it discharges the Acid of such as have not the vitriolic Acid in their composition. Since Mr. Homberg's time it hath been discovered, that a sedative salt may be made either with the nitrous or with the marine Acid; and that sublimation is not necessary to extract it from the borax, but that it may be obtained by crystallization only. For this latter discovery we are indebted to Mr. Geoffry, as we are to Mr. Lemery for the former. Since that time M. Baron d'Henouville, an able Chymist, hath shewn that a sedative salt may be obtained by the means of vegetable Acids; and hath lately demonstrated, in some excellent papers published in the collection of Memoirs written by the correspondents of the Academy of Sciences, that the sedative salt exists actually and perfectly in the borax, and that it is not produced by mixing Acids with that saline substance, as it seems all the Chymists before him imagined. This he proves convincingly from his analysis of borax, (which thereby appears to be nothing else but the sedative salt united with that fixed Alkali which is the basis of Sea-salt) and from his regenerating the same borax by uniting together that Alkali and the sedative salt: a proof the most complete that can possibly be produced in natural philosophy, and equivalent to demonstration itself. In order to finish what remains to be said upon the several sorts of saline substances, we should now speak of the Acids obtained from vegetables and animals, and also of the volatile Alkalis: but, seeing these saline substances differ from those of which we have already treated, only as they are variously altered by the unions they have contracted with certain principles of vegetables and animals, of which nothing has been yet said, it is proper to defer being particular concerning them, till we have explained those principles. CHAP. V. _Of_ LIME. Any substance whatever, that has been roasted a considerable time in a strong fire without melting, is commonly called a _Calx_. Stones and metals are the principal subjects that have the property of being converted into _Calces_. We shall treat of Metalline _Calces_ in a subsequent chapter, and in this confine ourselves to the _Calx_ of _Stone_, known by the name of _Lime_. In treating of earths in general we observed that they may be divided into two principal kinds; one of which actually and properly flows when exposed to the action of fire, and turns to glass; whence it is called a _fusible_ or _vitrifiable_ earth; the other resists the utmost force of fire, and is therefore said to be an _unfusible_ or _unvitrifiable_ earth. The latter is also not uncommonly called _calcinable_ earth; though sundry sorts of unfusible earths are incapable of acquiring by the action of fire all the qualities of _calcined_ earth, or _Lime_ properly so called: such earths are particularly distinguished by the denomination of _refractory_ earths. As the different sorts of stones are nothing more than compounds of different earths, they have the same properties with the earths of which they are composed, and may, like them, be divided into fusible or vitrifiable, and unfusible or calcinable. The fusible stones are generally denoted by the name of _Flints_; the calcinable stones, again, are the several sorts of marbles, cretaceous stones, those commonly called free-stones, _&c._ some of which, as they make the best Lime, are, by way of eminence, called _Lime-stones_. Sea-shells, also, and stones that abound with fossile shells, are capable of being burnt to Lime. All these substances, being exposed, for a longer or shorter time, as the nature of each requires, to the violent action of fire, are said to be _calcined_. By calcination they lose a considerable part of their weight, acquire a white colour, and become friable though ever so solid before; as, for instance, the very hardest marbles. These substances, when thus calcined, take the name of _Quick Lime_. Water penetrates Quick Lime, and rushes into it with vast activity. If a lump of newly calcined Lime be thrown into water, it instantly excites almost as great a noise, ebullition, and smoke, as would be produced by a piece of red-hot iron; with such a degree of heat too, that, if the Lime be in due proportion to the water, it will set fire to combustible bodies; as hath unfortunately happened to vessels laden with Quick Lime, on their springing a small leak. As soon as Quick Lime is put into water, it swells, and falls asunder into an infinite number of minute particles: in a word, it is in a manner dissolved by the water, which forms therewith a sort of white paste called _Slacked Lime_. If the quantity of water be considerable enough for the Lime to form with it a white liquor, this liquor is called _Lac Calcis_; which, being left some time to settle, grows clear and transparent, the Lime which was suspended therein, and occasioned its opacity, subsiding to the bottom of the vessel. Then there forms on the surface of the liquor a crystalline pellicle, somewhat opaque and dark-coloured, which being skimmed off is reproduced from time to time. This matter is called _Cremor Calcis_. Slacked Lime gradually grows dry, and takes the form of a solid body, but full of cracks and destitute of firmness. The event is different when you mix it up, while yet a paste, with a certain quantity of uncalcined stony matter, such as sand, for example: then it takes the name of _Mortar_, and gradually acquires, as it grows drier and older, a hardness equal to that of the best stones. This is a very singular property of Lime, nor is it easy to account for it: but it is a beneficial one; for every body knows the use of Mortar in building. Quick Lime attracts the moisture of the air, in the same manner as concentrated acids, and dry fixed alkalis; but not in such quantities as to render it fluid: it only falls into extremely small particles, takes the form of a fine powder, and the title of _Lime slacked in the air_. Lime once slacked, however dry it may afterwards appear, always retains a large portion of the water it had imbibed; which cannot be separated from it again but by means of a violent calcination. Being so recalcined it returns to be Quick Lime, recovering all its properties. Besides this great affinity of Quick Lime with water, which discovers a saline character, it has several other saline properties, to be afterwards examined, much resembling those of fixed alkalis. In Chymistry it acts very nearly as those salts do, and may be considered as holding the middle rank between a pure absorbent earth and a fixed alkali: and this hath induced many Chymists to think that Lime contains a true salt, to which all the properties it possesses in common with salts may be attributed. But as the chymical examination of this subject hath long been neglected, the existence of a saline substance in Lime hath been long doubtful. Mr. du Fay, author of some excellent chymical experiments, was one of the first who obtained a salt from Lime, by lixiviating it with a great deal of water, which he afterwards evaporated. But the quantity of salt he obtained by that means was very small; nor was it of an alkaline nature, as one would think it should have been, considering the properties of Lime. Mr. du Fay did not carry his experiments on this subject any further, probably for want of time; nor did he determine of what nature the salt was. Mr. Malouin had the curiosity to examine this salt of Lime, and soon found that it was nothing else but what was above called _Cremor Calcis_. He found, moreover, that, by mixing a fixed alkali with lime-water, a vitriolated tartar was formed; that, by mixing therewith an alkali like the basis of sea-salt, a Glauber's salt was produced; and, lastly, by combining lime with a substance abounding in phlogiston, he obtained a true sulphur. These very ingenious experiments prove to a demonstration, that the vitriolic acid constitutes the salt of Lime: for, as hath been shewn, no other acid is capable of forming such combinations. On the other hand, Mr. Malouin, having forced the vitriolic acid of this salt to combine with a phlogiston, found its basis to be earthy, and analogous to that of the selenites: whence he concluded, that the salt of Lime is a true neutral salt, of the same kind as the selenites. Mr. Malouin tells us he found several other salts in Lime. But as none of them was a fixed alkali, and as all the saline properties of Lime have an affinity with those of that kind of salt, there is great reason to think that all those salts are foreign to Lime, and that their union with it is merely accidental. I myself have made several experiments in order to get some insight into the saline nature of Lime, and shall here produce the result with all possible conciseness. I took several stones of different kinds, some of which produced by calcination a very strong Lime, and others but a very weak one. These I impregnated with different saline substances, acids, alkalis, and neutrals, and then exposed them all to the same degree of fire, which was a pretty strong one, and long enough continued to have made very good Lime of stones the most difficult to calcine. The consequence was, that, in the first place, those stones which naturally made but a weak Lime were not, by this process, converted into a stronger Lime; and, moreover, that none of these stones, even such as would naturally have produced the most active Lime, had acquired the properties of Lime. These experiments I varied many ways, employing different proportions of saline matters, and almost every possible degree of fire, and constantly observed, after calcination, that all those stones were so much the farther from the nature of Lime, as they had been combined with larger doses of salts. Among those which were impregnated with the greatest proportion of salts, and had suffered the greatest violence of fire, I observed some that had begun to flow, and were in a manner vitrified. Now, as the same subject cannot be, at one and the same time, in the state of glass and of Lime too; as a body cannot approach to one of these states but in proportion as it recedes from the other; and as salts in general dispose those bodies to fusion and vitrification which are in themselves the most averse to either, I concluded from my experiments, that the saline substances I used, had, by acting as fluxes upon the stones, prevented their calcination; that consequently we may suspect there is no saline matter in the composition of Lime, as Lime; and that Lime does not owe its saline and alkaline properties to any salt; or at least that, if it does owe those properties to a salt, such salt must be naturally and originally combined with the matter of the stone in so just a proportion, that it is impossible to increase the quantity thereof without prejudicing the Lime, and depriving it in some measure of its virtue. This theory agrees perfectly with the illustrious Stahl's opinion; for he thinks, as we observed in discoursing of salts in general, that every saline substance is but an earth combined in a certain manner with water. This notion he applies to Lime, and says, that fire only subtilizes and attenuates the earthy matter, and thereby renders it capable of uniting with water in such a manner, that the result of their combination shall be a substance having saline properties; and that Lime accordingly never acquires these properties till it be combined with water. I have dwelt longer on the Salt of Lime than I shall on any other particular; because the subject, though in itself of great importance, has hitherto been but little attended to, and because the experiments here recited are entirely new. Lime unites with all acids, and in conjunction with them exhibits various phenomena. The vitriolic acid poured upon Lime dissolves it with effervescence and heat. From this mixture there exhales a great quantity of vapours, in smell and colour perfectly like those of sea-salt; from which, however, they are found to be very different when collected into a liquor. From this combination of the vitriolic acid with Lime arises a neutral salt, which shoots into crystals, and is of the same kind with the selenetic salt obtained from Lime by Mr. Malouin. The nitrous acid poured upon Lime dissolves it in like manner with effervescence and heat: but the solution is transparent, and therein differs from the former, which is opaque. From this mixture there arises a neutral salt, which does not crystallize, and has withal the very singular property of being volatile, and rising wholly by distillation in a liquid form. This phenomenon is so much the more remarkable, as Lime, the basis of this salt, is one of the most fixed bodies known in Chymistry. With the acid of sea-salt Lime forms also a singular sort of salt, which greedily imbibes the moisture of the air. We shall have occasion to take further notice of it in another place. These experiments made on Lime with acids are likewise quite new. We are indebted for them to Mr. Du Hamel of the Academy of Sciences, whose admirable Memoirs on several subjects shew his extensive knowledge in all parts of Natural Philosophy. Lime applied to fixed alkalis adds considerably to their caustic quality, and makes them more penetrating and active. An alkaline lixivium in which Lime hath been boiled, being evaporated to dryness, forms a very caustic substance, which flows in the fire much more easily, attracts and retains moisture much more strongly, than fixed alkalis that have not been so treated. An alkali thus acuated by Lime is called the _Caustic Stone_, or _Potential Cautery_; because it is employed by surgeons to produce eschars on the skin and cauterize it. CHAP. VI. _Of Metallic Substances in general._ Metallic Substances are heavy, glittering, opaque, fusible bodies. They consist chiefly of a vitrifiable earth united with the phlogiston. Several Chymists insist on a third principle in these bodies, and have given it the name of _Mercurial Earth_; which, according to Becher and Stahl, is the very same that being combined with the vitriolic acid forms and characterizes the acid of sea-salt. The existence of this principle hath not yet been demonstrated by any decisive experiment; but we shall shew that there are pretty strong reasons for admitting it. We shall begin with mentioning the experiments which prove Metallic Substances to consist of a vitrifiable earth united with the phlogiston. The first is this: if they be calcined in such a manner as to have no communication with any inflammable matter, they will be spoiled of all their properties, and reduced to an earth or calx, that has neither the splendour nor the ductility of a metal, and in a strong fire turns to an actual glass, instead of flowing like a metal. The second is, that the calx or the glass resulting from a metal thus decomposed, recovers all its metalline properties by being fused in immediate contact with an inflammable substance, capable of restoring the phlogiston of which calcination had deprived it. On this occasion we must observe, that Chymists have not yet been able, by adding the phlogiston, to give the properties of metals to all sorts of vitrifiable earths indiscriminately; but to such only as originally made a part of some metallic body. For example, a compound cannot be made with the phlogiston and sand that shall have the least resemblance of a metal: and this is what seems to point out the reality of a third principle, as necessary to form the metalline combination. This principle may probably remain united with the vitrifiable earth of a metallic substance, when reduced to a glass; whence it follows, that such vitrified metals require only the addition of a phlogiston to enable them to appear again in their pristine form. It may be inferred from another experiment, that the calx and the glass of a metal are not its pure vitrifiable earth, properly so called: for by repeated or long-continued calcinations, such a calx or glass may be rendered incapable of ever resuming the metalline form, in whatever manner the phlogiston be afterwards applied to it; so that by this means it is brought into the condition of a pure vitrifiable earth, absolutely free from any mixture. Those Chymists who patronize the Mercurial earth, produce many other proofs of the existence of that principle in Metallic Substances; but they would be misplaced in an elementary treatise like this. When by adding the phlogiston to a metallic glass we restore it to the form of a metal, we are said to _reduce_, _resuscitate_, or _revivify_ that metal. Metallic Substances are of different kinds, and are divided into _Metals_ and _Semi-metals_. Those are called Metals which, besides their metalline splendour and appearance, are also malleable; that is, have the property of stretching under the hammer, and by that means of being wrought into different forms without breaking. Those which have only the metalline splendour and appearance, without malleability, are called Semi-metals. Metals are also further subdivided into two sorts; _viz._ _Perfect_ and _Imperfect_ Metals. The Perfect Metals are those which suffer no damage or change whatever by the most violent and most lasting action of fire. The Imperfect Metals are those which by the force of fire, may be deprived of their phlogiston, and consequently of their metalline form. When but a moderate degree of fire is employed to deprive a Metal of its phlogiston, the metal is said to be _calcined_; and then it appears in the form of a powdered earth, which is called a _Calx_: and this metalline calx being exposed to a more violent degree of fire melts and turns to glass. Metallic Substances have an affinity with acids: but not equally with all; that is, every Metallic Substance is not capable of uniting and joining with every acid. When an acid unites with a Metallic Substance there commonly arises an ebullition, attended with a kind of hissing noise and fuming exhalations. By degrees, as the union becomes more perfect, the particles of the metal combining with the acid become invisible: this is termed _Dissolution_; and when a metalline mass thus appears in an acid, the metal is said to be _dissolved_ by that acid. It is proper to observe, that acids act upon Metalline Substances, in one respect, just as they do upon alkalis and absorbent earths: for an acid cannot take up above such a certain proportion thereof as is sufficient to saturate it, to destroy several of its properties, and weaken others. For example, when an acid is combined with a metal to the point of saturation, it loses its taste, does not turn the blue colour of a vegetable red, and its affinity with water is considerably impaired. On the other hand, Metalline Substances, which when pure are incapable of uniting with water, by being joined with an acid acquire the property of dissolving in water. These combinations of Metalline Substances with acids form different sorts of neutral salts; some of which have the property of shooting into crystals, while others have it not: most of them, when thoroughly dried, attract the moisture of the air. The affinity which Metalline Substances have with acids is less than that which absorbent earths and fixed alkalis have with the same acids; so that all metalline salts may be decompounded by one of these substances, which will unite with the acid, and precipitate the metal. Metalline Substances thus separated from an acid solvent are called _Magisteries_ and _Precipitates_ of metals. None of these precipitates, except those of the perfect metals, retain the metalline form: most of their phlogiston hath been destroyed by the solution and precipitation, and must be restored before they can recover their properties. In short, they are nearly in the same state with Metalline Substances deprived of their phlogiston by calcination; and accordingly such a precipitate is called a _Calx_. A metalline calx prepared in this manner loses a greater or a less portion of its phlogiston, the more or less effectually and thoroughly the Metalline Substance, of which it made a part, was dissolved by the acid. Metallic Substances have affinities with each other which differ according to their different kinds: but this is not universal; for some of them are incapable of any sort of union with some others. It must be observed, that Metallic Substances will not unite, except they be both in a similar state; that is, both in a Metalline form, or both in the form of a Glass; for a Metalline Substance retaining its phlogiston cannot contract an union with any metallic glass, even its own. CHAP. VII. _Of_ METALS. There are six Metals, of which two are Perfect and four Imperfect. The perfect Metals are Gold and Silver; the others are Copper, Tin, Lead, and Iron. Some Chymists admit a seventh Metal, to wit, Quick-silver: but as it is not malleable, it has been generally considered as a metallic body of a particular kind. We shall soon have occasion to examine it more minutely. The ancient Chymists, or rather the Alchymists, who fancied a certain relation or analogy between Metals and the Heavenly Bodies, bestowed on the seven Metals, reckoning Quick-silver one of them, the names of the seven Planets of the Ancients, according to the affinity which they imagined they observed between those several bodies. Thus Gold was called _Sol_, Silver _Luna_, Copper _Venus_, Tin _Jupiter_, Lead _Saturn_, Iron _Mars_, and Quick-silver _Mercury_. Though these names were assigned for reasons merely chimerical, yet they still keep their ground; so that it is not uncommon to find the Metals called by the names, and denoted by the characters, of the Planets, in the writings even of the best Chymists. Metals are the heaviest bodies known in nature. SECTION I. _Of_ GOLD. Gold is the heaviest of all Metals. The arts of wire-drawing and gold-beating shew its wonderful ductility. The greatest violence of fire is not able to produce any alteration in it. Indeed Mr. Homberg, a famous Chymist, pretended that he had made this metal fume, and even vitrified it, by exposing it to the focus of one of the best burning-glasses, known by the name of the Lens of the _Palais Royal_: but, there are very good reasons for calling in question the experiments he made on this occasion, or rather for thinking that he was quite mistaken. For, 1. No man hath since been able to vitrify Gold, though several good Experimenters have assiduously tried to effect it, by exposing it to the focus of the same lens, and of other burning-glasses still stronger. 2. It hath been observed, that though Gold, when exposed to the focus of those glasses, did indeed emit some vapours and decrease in weight; yet, those vapours being carefully collected on a piece of paper, proved to be true Gold, in no degree vitrified, and which consequently had suffered no change but that of being carried away by the violence of the heat, its nature not being in the least altered. 3. The small portion of vitrified matter, which was formed on the arm that supported the Gold in Mr. Homberg's experiment, may have come either from the arm itself, or rather from some heterogeneous particles contained in the Gold; for it is almost impossible to have it perfectly pure. 4. Neither Mr. Homberg, nor any that have repeated his experiment, ever reduced this pretended glass of Gold by restoring its Phlogiston, as is done with other metallic glasses. 5. To render the experiment decisive, the whole mass of Gold employed ought to have been vitrified; which was not the case. Nevertheless, I do not pretend that this metal is in its own nature absolutely indestructible, and unvitrifiable: but there is reason to think that no body hath hitherto found the means of producing those effects on it, probably for want of a sufficient degree of fire; at least the point is very doubtful. Gold cannot be dissolved by any pure acid: but if the acid of nitre be mixed with the acid of sea-salt, there results a compound acid liquor, with which it has so great an affinity that it is capable of being perfectly dissolved thereby. The Chymists have called this solvent _Aqua Regis_, on account of its being the only acid that can dissolve Gold, which they consider as the King of Metals. The solution of gold is of a beautiful orange colour. If Gold dissolved in _aqua regis_ be precipitated by an alkali or an absorbent earth, the precipitate gently dried, and then exposed to a certain degree of heat, is instantly dispersed into the air, with a most violent explosion and noise: Gold thus precipitated is therefore called _Aurum Fulminans_. But if the precipitated Gold be carefully washed in plenty of water, so as to clear it of all the adhering saline particles, it will not fulminate, but may be melted in a crucible without any additament, and will then appear in its usual form. The acid of vitriol being poured on _aurum fulminans_ likewise deprives it of its fulminating quality. Gold does not begin to flow till it be red-hot like a live coal. Though it be the most malleable and most ductile of all metals, it has the singular property of losing its ductility more easily than any of them: even the fumes of charcoal are sufficient to deprive it thereof, if they come in contact with it while it is in fusion. The malleability of this metal, and indeed of all the rest, is also considerably diminished by exposing it suddenly to cold when it is red-hot; for example, by quenching it in water, or even barely exposing it to the cold air. The way to restore ductility to gold, when lost by its coming in contact with the vapour of coals, and in general to any metal rendered less malleable by being suddenly cooled, is to heat it again, to keep it red hot a considerable time, and then to let it cool very slowly and gradually; this operation frequently repeated will by degrees much increase the malleability of a metal. Pure sulphur hath no effect on Gold; but being combined with an alkali into a _hepar sulphuris_, it unites therewith very readily. Nay, so intimate is their union, that the Gold, by means thereof, becomes soluble in water; and this new compound of Gold and liver of sulphur, being dissolved in water, will pass through the pores of brown paper without suffering any decomposition; which does not happen, at least in such a manifest degree, to other metallic substances dissolved by liver of sulphur. _Aurum fulminans_, mixed and melted with flower of sulphur, loses its fulminating quality: which arises from hence, that on this occasion the sulphur burns, and its acid, which is the same with the vitriolic, being thereby set at liberty becomes capable of acting upon the Gold as a vitriolic acid would; which, as was said above, deprives the Gold of its fulminating quality. SECTION II. _Of_ SILVER. Next to Gold, Silver is the most perfect metal. Like Gold it resists the utmost violence of fire, even that in the focus of a burning-glass. However, it holds only the second place among metals; because it is lighter than Gold by almost one half; is also somewhat less ductile; and, lastly, because it is acted upon by a greater number of solvents. Yet Silver hath one advantage over gold, namely that of being a little harder; which makes it also more sonorous. This metal, like Gold, begins to flow when it is so thoroughly penetrated by the fire as to appear ignited like a live coal. While this metal is in fusion, the immediate contact of the vapour of burning coals deprives it almost entirely of its malleability, in the same manner as we observed happens to Gold: but both these metals easily recover that property by being melted with nitre. The nitrous acid is the true solvent of Silver, and being somewhat dephlegmated will very readily and easily take up a quantity of Silver equal in weight to itself. Silver thus combined with the nitrous acid forms a metallic salt which shoots into crystals, called by the name of _Lunar Crystals_, or _Crystals of Silver_. These crystals are most violently caustic: applied to the skin they quickly affect it much as a live coal would; they produce a blackish eschar, corroding and entirely destroying the parts they touch. Surgeons use them to eat away the proud fungous flesh of ulcers. As Silver united with the nitrous acid hath the property of blackening all animal substances, a solution of this metallic salt is employed to dye hair, or other animal matters, of a beautiful and durable black. These crystals flow with a very moderate heat, and even before they grow red. Being thus melted they form a blackish mass; and in this form they are used by Surgeons, under the title of _Lapis Infernalis_, _Infernal Stone_, or _Lunar Caustic._ Silver is also dissolved by the vitriolic acid: but then the acid must be concentrated, and in quantity double the weight of the Silver; nor will the solution succeed without a considerable degree of heat. Spirit of salt and _aqua regis_, as well as the other acids, are incapable of dissolving this metal; at least in the ordinary way. Though Silver be not soluble in the acid of sea-salt, nor easily in the acid of vitriol, as hath just been observed, it doth not follow that it hath but a weak affinity with the latter, and none at all with the former: on the contrary, it appears from experiment that it hath with these two acids a much greater affinity than with the acid of nitre: which is singular enough, considering the facility with which this last acid dissolves it. The experiment which proves the fact, is this. To a solution of Silver in the nitrous acid, add the acid either of vitriol or of sea-salt, and the Silver will instantly quit its nitrous solvent to join with the superadded acid. Silver thus united with the vitriolic or the marine acid is less soluble in water than when combined with the nitrous acid; and for this reason it is, that when either of these two acids is added to a solution of Silver, the liquor immediately becomes white, and a precipitate is formed, which is no other than the Silver united with the precipitating acid. If the precipitation be effected by the vitriolic acid, the precipitate will disappear upon adding a sufficient quantity of water, because there will then be water enough to dissolve it. But the case is not the same when the precipitation is made by the marine acid; for Silver combined therewith is scarce soluble in water. This Precipitate of Silver, procured by means of the marine acid, is very easily fused, and when fused changes to a substance in some measure transparent and flexible, which hath occasioned it to be called by the name of _Luna Cornea_. If it be proposed to decompound this _luna cornea_, that is, to separate the marine acid from the Silver with which it is united, the _luna cornea_ must be melted along with fatty and absorbent matters, with which the acid will unite, and leave the metal exceeding pure. It must be observed, that if, instead of the marine acid, sea-salt in substance be added to a solution of Silver in the nitrous acid, a Precipitate is also produced, which by fusion appears to be a true _luna cornea_. The reason is, that the sea-salt is decomposed by the nitrous acid, which seizes its basis, as having a greater affinity therewith than its own acid hath; and this acid being consequently disengaged and set at liberty unites with the Silver, which, as has been shewn, has a greater affinity with it than with the nitrous acid. This is an instance of decomposition effected by means of one of those double affinities mentioned by us in our seventh proposition concerning Affinities. From what hath been already said it is clear, that all these combinations of Silver with acids may be decompounded by absorbent earths and by fixed alkalis; it being a general law with regard to all metallic substances. We shall not therefore repeat this observation when we come to treat of the other metals; unless some particular occasion require it. With regard to Silver I must take notice that, when separated by these means from the acids in which it was dissolved, it requires nothing but simple fusion to restore it to its usual form; because it does not, any more than Gold, lose its Phlogiston by those solutions and precipitations. Silver unites with sulphur in fusion. If this metal be only made red-hot in a crucible, and sulphur be then added, it immediately flows; the sulphur acting as a flux to it. Silver thus united with sulphur forms a mass that may be cut, is half malleable, and hath nearly the colour and consistence of Lead. If this sulphurated Silver be kept a long time in fusion, and in a great degree of heat, the sulphur flies off and leaves the Silver pure. But if the sulphur be evaporated by a violent heat, it carries off with it part of the Silver. Silver unites and mixes perfectly with Gold in fusion. The two metals thus mixed form a compound with properties partaking of both. Metallurgists have hitherto sought in vain for a perfectly good and easy method of separating these two metals by the _dry way_ only: (this term is used to signify all operations performed by fusion): but they are conveniently enough parted by the _moist way_, that is, by acid solvents. This method is founded on the above-mentioned properties of Gold and Silver with respect to acids. It hath been shewn that _aqua regis_ only will dissolve Gold; that Silver, on the contrary, is not soluble by _aqua regis_, and that its proper solvent is the acid of nitre; consequently, when Gold and Silver are mixed together, if the compound mass be put into _aqua fortis_, this acid will take up all the Silver, without dissolving a particle of the Gold, which will therefore remain pure; and by this means the desired separation is effected. This method, which is commonly made use of by Goldsmiths, and in Mints, is called the _Parting Assay_. It is plain, that if _aqua regis_ were employed instead of _aqua fortis_, the separation would be equally effected; and that the only difference between this process and the former would consist in this, that now the Gold would be dissolved, and the Silver remain pure. But the operation by _aqua fortis_ is preferable; because _aqua regis_ does take up a little Silver, whereas _aqua fortis_ hath not the least effect on Gold. It must be observed, that, when Gold and Silver are mixed together in equal parts, they cannot be parted by the means of _aqua fortis_. To enable the _aqua fortis_ to act duly on the Silver, this metal must be, at least, in a triple proportion to the Gold. If it be in a less proportion, you must either employ _aqua regis_ to make the separation, or, if you prefer the use of _aqua fortis_, melt the metalline mass, and add as much Silver as is necessary to make up the proportion above-mentioned: and hence this Process is called _Quartation_. This effect, which is pretty singular, probably arises from hence, that when the Gold exceeds or even equals the Silver in quantity, the parts of both being intimately united, the former are capable of coating over the latter, and covering them so as to defend them from the action of the _aqua fortis_; which is not the case when there is thrice as much Silver as Gold. There is one thing more to be taken notice of with regard to this process; which is, that perfectly pure _aqua fortis_ is rarely to be met with, for two reasons; first, it is difficult in making it wholly to prevent the rising of the medium employed to disengage the nitrous acid; that is, a little of the vitriolic acid will mix with the vapours of the _aqua fortis_: secondly, unless the salt-petre be very well purified it will always hold some small portion of sea-salt, the acid of which, we know, is very readily set loose by the vitriolic acid, and consequently rises together with the vapours of the _aqua fortis_. It is easy to see that _aqua fortis_ mixed either with the one or the other is not proper for the Parting Process; because, as has just been said, the vitriolic and the marine acid equally precipitate Silver dissolved in the nitrous acid; by which means, when they are united with that acid, they weaken its action upon the Silver, and hinder the dissolution. Add, that _aqua fortis_ adulterated with a mixture of spirit of salt becomes an _aqua regis_, and consequently is rendered capable of dissolving Gold, in proportion as its action upon Silver is diminished. In order to remedy this inconvenience, and free _aqua fortis_ from the vitriolic or marine acid with which it is tainted, Silver must be dissolved therein: by degrees as the metal dissolves, those heterogeneous acids lay hold of it, and precipitate with it in the form of a white powder, as we observed before. This precipitate being wholly fallen, the liquor grows clear; after which, if it be found capable of dissolving more silver, without turning milky, it may be depended on as a perfectly pure _aqua fortis_. Then filtre it, dissolve more Silver in it, as long as it will take up any, and you will have a solution of Silver in a very pure _aqua fortis_. By means of this solution may other _aqua fortis_ be purified: for pour a few drops thereof into a very impure _aqua fortis_, and immediately the vitriolic or marine acid, with which that _aqua fortis_ is contaminated, will join the Silver and fall therewith to the bottom. When the solution of Silver, prepared as above, does not in the least affect the transparency of the _aqua fortis_, it is then very pure, and fit for the purposes of Quartation. This operation of purifying _aqua fortis_ by a solution of Silver is called the _Precipitation_ of _Aqua Fortis_, and _aqua fortis_ thus purified is called _Precipitated Aqua Fortis_. When Silver is dissolved in _aqua fortis_ it may be separated therefrom, as hath been shewn, by absorbent earths and fixed alkalis. We shall see by and by that there are other means of effecting this: but whatever way it be separated from its solvent it recovers its metalline form, as Gold does, by being simply fused without any additament. SECTION III. _Of_ COPPER. Of all the imperfect metals Copper comes the nearest to Gold and Silver. Its natural colour is a deep-red yellow. It resists a very violent degree of fire for a considerable time; but losing its phlogiston at last, it changes its metalline form for that of a calx, or a pure reddish earth. This calx is hardly, if at all, reducible to glass, without the addition of something to promote its fusion; all that the fiercest heat can do being only to render it soft. Copper, even while it retains its metalline form, and is very pure, requires a considerable degree of fire to melt it, and does not begin to flow till long after it is red-hot. When in fusion, it communicates a greenish colour to the flame of the coals. This metal is inferior to Silver in point of gravity; nor is its ductility so great, though it be pretty considerable: but, on the other hand, it exceeds that metal in hardness. It unites readily with Gold and Silver; nor does it greatly lessen their beauty when added to them in a small quantity: nay, it even procures them some advantages; such as making them harder, and less subject to lose their ductility, of which those metals are often liable to be deprived, by the mixture of the smallest heterogeneous particle. This may probably arise from hence, that the ductility of Copper has the peculiarity of resisting most of those causes which rob the perfect metals of theirs. The property, which other metalline substances have in common with Copper, of losing the phlogiston by calcining and then vitrifying, furnishes us with a method of separating them from Gold and Silver, when they are combined therewith. Nothing more is required than to expose the mass compounded of the perfect metals and other metalline substances to a degree of heat sufficient to calcine whatever is not either Gold or Silver. It is evident, that, by this means, these two metals will be obtained as pure as is possible; for, as hath already been said, no metalline calx or glass is capable of uniting with metals possessed of their phlogiston. On this principle is formed the whole business of refining Gold and Silver. When the perfect metals have no other alloy but Copper, as this metal is not to be calcined or vitrified without great difficulty, which is increased by its union with the unvitrifiable metals, it is easy to see that it is almost impossible to separate them without adding something to facilitate the vitrification of the Copper. Such metals as have the property of turning easily to glass are very fit for this purpose; and it is necessary to add a certain quantity thereof, when Gold or Silver is to be purified from the alloy of Copper. We shall have occasion to be more particular on this subject when we come to treat of Lead. Copper is soluble in all the acids, to which it communicates a green colour, and sometimes a blue. Even the neutral salts, and water itself, act upon this metal. With regard to water indeed, as the procuring it absolutely pure and free from any saline mixture is next to an impossibility, it remains a question whether the effect it produces on Copper be not owing to certain saline particles contained in it. It is this great facility of being dissolved that renders Copper so subject to rust; which is nothing else but some parts of its surface corroded by saline particles contained in the surrounding air and water. The rust of Copper is always green or blue, or of a colour between these two. Internally used it is very noxious, being a real poison, as are all the solutions of this metal made by any acid whatever. The blue colour which Copper constantly assumes, when corroded by any saline substance, is a sure sign by which it may be discovered wherever it exists, even in a very small quantity. Copper dissolved in the vitriolic acid forms a kind of metalline salt, which shoots into rhomboidal crystals of a most beautiful blue colour. These crystals are called _Blue Vitriol_, or _Vitriol of Copper_. They are sometimes found ready formed in the bowels of the earth; and may be artificially made by dissolving Copper in the vitriolic acid; but the solution will not succeed unless the acid be well dephlegmated. The taste of this vitriol is saltish and astringent. It retains a considerable quantity of water in crystallizing, on which account it is easily rendered fluid by fire. It must be observed, that, when it is exposed to a certain degree of heat, in order to free it of its humidity, a great part of its acid flies off at the same time: and hence it is that, after calcination, there remains only a kind of earth, or metalline calx, of a red colour, which contains but very little acid. This earth cannot be brought to flow but with the greatest difficulty. A solution of Copper in the nitrous acid forms a salt which does not crystallize, but, when dried, powerfully attracts the moisture of the air. The same thing happens when it is dissolved in the spirit of salt, or in _aqua regis_. If the Copper thus dissolved by any of these acids be precipitated by an earth or an alkali, it retains nearly the colour it had in the solution: but these precipitates are scarce any thing more than the earth of Copper, or Copper deprived of most of its phlogiston; so that if they were exposed to a violent fire, without any additament, a great part of them would be converted into an earth that could never be reduced to a metalline form. Therefore, when we intend to reduce these precipitates to Copper, it is necessary to add a certain quantity of a substance capable of restoring to them the phlogiston they have lost. The substance which hath been found fittest for such reductions is charcoal-dust; because charcoal is nothing but a phlogiston closely combined with an earth, which renders it exceedingly fixed, and capable of resisting a violent force of fire. But as charcoal will not melt, and consequently is capable of preventing rather than forwarding the flux of a metalline calx or glass, which nevertheless is essentially necessary to complete the reduction, it hath been contrived to mix it, or any other substance containing the phlogiston, with such fixed alkalis as easily flow, and are fit to promote the flux of other bodies. These mixtures are called _Reducing Fluxes_; because the general name of _Fluxes_ is given to all salts or mixtures of salts, which facilitate fusion. If Sulphur be applied to Copper made perfectly red-hot, the metal immediately runs; and these two substances uniting form a new compound much more fusible than pure Copper. This compound is destroyed by the sole force of fire, for two reasons: the first is, that, sulphur being volatile, the fire is capable of subliming a great part of it, especially when it is in a great proportion to the Copper with which it is joined; the second is, that the portion of sulphur which remains, being more intimately united with the Copper, though it be rendered less combustible by that union, is nevertheless burnt and consumed in time. Copper being combined with sulphur, and together with it exposed to the force of fire, is found to be partly changed into a blue vitriol; because the vitriolic acid, being disengaged by burning the sulphur, is by that means qualified to dissolve the Copper. The affinity of Copper with sulphur is greater than that of Silver. This metal, as well as the other imperfect metals and the semi-metals, being mingled with nitre and exposed to the fire, is decomposed and calcined much sooner than by itself; because the phlogiston which it contains occasions the deflagration of the nitre, and consequently the two substances mutually decompose each other. There are certain metalline substances whose phlogiston is so abundant, and so weakly connected with their earth, that when they are thus treated with nitre, there arises immediately a detonation, accompanied with flame, and as violent as if sulphur or charcoal-dust had been employed; so that in a moment the metalline substance loses its phlogiston, and is calcined. The nitre, after these detonations, always assumes an alkaline character. SECTION IV. _Of_ IRON. Iron is lighter and less ductile than Copper; but it is much harder, and of more difficult fusion. It is the only body that has the property of being attracted by the magnet, which therefore serves to discover it wherever it is. But it must be observed, that it hath this property only when in its metalline state, and loses it when converted to an earth or calx. Hence very few Iron-ores are attracted by the load-stone: because, for the most part, they are only sorts of earths, which require a phlogiston to be added before they can be brought to the form of true Iron. When Iron hath undergone no other preparation but the fusion which is necessary to smelt it from its ore, it is usually quite brittle, and flies to pieces under the hammer: which arises in some measure from its containing a certain portion of unmetallic earth interposed between its parts. This we call _Pig Iron_. By melting this a second time it is rendered purer, and more free from heterogeneous matters: but still, as its proper parts are probably not brought sufficiently near, or closely enough united, till the Iron hath undergone some further preparation besides that of fusion, it seldom hath any degree of malleability. The way to give it this property is to make it just red-hot, and then hammer it for some time in all directions; to the end that its parts may be properly united, incorporated, and welded together, and that the heterogeneous matters which keep them asunder may be separated. Iron made by this means as malleable as possible we call _Bar Iron_, or _Forged Iron_. Bar Iron is still harder to fuse than Pig Iron: to make it flow requires the utmost force of fire. Iron has the property of imbibing a greater quantity of phlogiston than is necessary to give it the metalline form. It may be made to take in this super-abundant phlogiston two ways: the first is by fusing it again with matters that contain the phlogiston; the second is, by encompassing it with a quantity of such matters, charcoal-dust, for instance, and then exposing it so encompassed, for a certain time, to a degree of fire barely sufficient to keep it red-hot. This second method, whereby one substance is incorporated with another by means of fire, but without fusing either of them, is in general called _Cementation_. Iron thus impregnated with an additional quantity of phlogiston is called _Steel_. The hardness of Steel may be considerably augmented by _tempering_ it; that is, by making it red-hot, and suddenly quenching it in some cold liquor. The hotter the metal, and the colder the liquor in which it is quenched, the harder will the Steel be. By this means tools are made, such as files and sheers, capable of cutting and dividing the hardest bodies, as glass, pebbles, and Iron itself. The colour of Steel is darker than that of Iron, and the facets which appear on breaking it are smaller. It is also less ductile and more brittle, especially when tempered. As Iron may be impregnated with an additional quantity of phlogiston, and thereby converted into Steel, so may Steel be again deprived of that super-abundant phlogiston, and brought back to the condition of Iron. This is effected by cementing it with poor earths, such as calcined bones and chalk. By the same operation Steel may be _untempered_; nay, it will lose the hardness it had acquired by tempering, if it be but made red-hot, and left to cool gradually. As Iron and Steel differ only in the respects we have here taken notice of, their properties being in all other respects the same, what follows is equally applicable to both. Iron being exposed to the action of fire for some time, especially when divided into small particles, such as filings, is calcined and loses its phlogiston. By this means it turns to a kind of reddish yellow earth, which, on account of its colour, is called _Crocus Martis_, or _Saffron of Mars_. This calx of Iron has the singular property of flowing in the fire with somewhat less difficulty than Iron itself; whereas every other metalline calx flows with less ease than the metal that produced it. It has moreover the remarkable property of uniting with the phlogiston, and of being reduced to Iron without fusion; requiring for that purpose only to be made red-hot. Iron may be incorporated with Silver, and even with Gold, by means of certain operations. Under the article of Lead we shall see how it may be separated from these metals. The acids produce on it much the same effects as on Copper; every one of them acts upon it. Certain neutral salts, alkalis, and even water itself, are capable of dissolving it; and hence it is also very subject to rust. The vitriolic acid dissolves it with the greater ease: but the circumstances which attend the solution thereof are different from those with which the same Acid dissolves Copper: for, 1. whereas the vitriolic acid must be concentrated to dissolve Copper, it must on the contrary be diluted with water to dissolve Iron, which it will not touch when well dephlegmated. 2. The vapours which rise in this dissolution are inflammable; so that if it be made in a small-necked bottle, and the flame of a candle be applied to the mouth thereof, the vapours in the bottle take fire with such rapidity as to produce a considerable explosion. This solution is of a beautiful green colour; and from this union of the vitriolic acid with Iron there results a neutral metalline salt, which has the property of shooting into crystals of a rhomboidal figure, and a green colour. These crystals are called _Green Vitriol_, _Vitriol of Mars_, and _Copperas_. Green Vitriol hath a saltish and astringent taste. As it retains a great deal of water in crystallizing, it quickly flows by the action of fire: but this fluidity is owing to its water only, and is not a real fusion; for, as soon as its moisture is evaporated, it resumes a solid form. Its green transparent colour is now changed into an opaque white: and, if the calcination be continued, its acid also exhales and is dissipated in vapours; and as it loses that, it turns gradually to a yellow colour, which comes so much the nearer to a red the longer the calcination is continued, or the higher the force of the fire is raised; which being driven to the utmost, what remains is of a very deep red. This remainder is nothing but the body of the Iron, which having lost its phlogiston is now no more than an earth, nearly of the same nature with that which is left after calcining the metal itself. Green Vitriol dissolved in water spontaneously lets fall a yellowish earthy sediment. If this solution be defecated by filtration, it still continues to deposite some of the same substance, till the vitriol be wholly decomposed. This sediment is nothing but the earth of Iron, which is then called _Ochre_. The nitrous acid dissolves Iron with great ease. This solution is of a yellow colour, inclining more or less to a russet, or dark-brown, as it is more or less saturated with Iron. Iron dissolved by this acid, also, falls spontaneously in a kind of calx, which is incapable of being dissolved a second time; for the nitrous acid will not act upon Iron that has lost its phlogiston. This solution does not crystallize, and if evaporated to dryness attracts the moisture of the air. Spirit of salt likewise dissolves Iron, and this solution is green. The vapours which rise during the dissolution are inflammable, like those which ascend when this metal is attacked by the vitriolic acid. _Aqua regis_ makes a solution of Iron, which is of a yellow colour. Iron hath a greater affinity than either Silver or Copper with the nitrous and vitriolic acids: so that if iron be presented to a solution of either in one of these two acids, the dissolved metal will be precipitated; because the acid quits it for the Iron, with which it has a greater affinity. On this occasion it must be observed, that if a solution of Copper in the vitriolic acid be precipitated by means of Iron, the precipitate has the form and splendour of a metal, and does not require the addition of a phlogiston to reduce it to true Copper; which is not the case, as has been shewn, when the precipitation is effected by earths or alkaline salts. The colour of this metalline precipitate hath deceived several persons, who being unacquainted with such phenomena, and with the nature of blue vitriol, imagined that Iron was transmuted into Copper, when they saw a bit of Iron laid in a solution of that vitriol become, in form and external appearance, exactly like Copper: whereas the surface only of the Iron was crusted over with the particles of Copper contained in the vitriol, which had gradually fallen upon and adhered to the Iron, as they were precipitated out of the solution. Among the solvents of Iron we mentioned fixed alkalis; and that they have such a power is proved by the following phenomenon. If a large proportion of alkaline salts be suddenly mixed with a solution of Iron in an acid, no precipitation ensues, and the liquor remains clear and pellucid; or if at first it look a little turbid, that appearance lasts but a moment, and the liquor presently recovers its transparency. The reason is, that the quantity of alkali is more than sufficient to saturate all the acid of the solution, and the super-abundant portion thereof, meeting with the Iron already finely divided by the acid, dissolves it with ease as fast as it falls, and so prevents its muddying the liquor. To evince that this is so in fact, let the alkali be applied in a quantity that is not sufficient, or but barely sufficient, to saturate the acid, and the Iron will then precipitate like any other metal. Water also acts upon Iron; and therefore Iron exposed to moisture grows rusty. If iron-filings be exposed to the dew, they turn wholly to a rust, which is called _Crocus Martis Aperiens_. Iron exposed to the fire together with nitre makes it detonate pretty briskly, sets it in a flame, and decomposes it with rapidity. This metal hath a greater affinity than any other metalline substance with sulphur; on which account it is successfully used to precipitate and separate all metalline substances combined with sulphur. Sulphur uniting with Iron communicates to it such a degree of fusibility, that if a mass of this metal heated red-hot be rubbed with a bit of sulphur, it incessantly runs into as perfect a fusion as a metal exposed to the focus of a large burning-glass. SECTION V. _Of_ TIN. Tin is the lightest of all metals. Though it yields easily to the impression of hard bodies, it has but little ductility. Being bent backwards and forwards it makes a small crackling noise. It flows with a very moderate degree of fire, and long before it comes to be red-hot. When it is in fusion, its surface soon grows dusty, and there forms upon it a thin dark-coloured dusty pellicle, which is no other than a part of the Tin that has lost its phlogiston, or a calx of Tin. The metal thus calcined easily recovers its metalline form on the addition of a phlogiston. If the calx of Tin be urged by a strong fire it grows white, but the greatest violence of heat will not fuse it; which makes some Chymists consider it as a calcinable or absorbent earth, rather than a vitrifiable one. Yet it turns to glass, in some sort, when mixed with any other substance that vitrifies easily. However, it always produces an imperfect glass only, which is not at all transparent, but of an opaque white. The calx of Tin thus vitrified is called _Enamel_. Enamels are made of several colours by the addition of this or that metalline calx. Tin unites easily with all the metals; but it destroys the ductility and malleability of every one of them, Lead excepted. Nay, it possesses this property of making metals brittle in such an eminent degree, that the very vapour of it, when in fusion, is capable of producing this effect. Moreover, which is very singular, the most ductile metals, even Gold and Silver, are those on which it works this change with the most ease, and in the greatest degree. It has also the property of making Silver mixed with it flow over a very small fire. It adheres to, and in some measure incorporates with, the surface of Copper and of Iron; whence arose the practice of coating over those metals with Tin. Tin plates are no other than thin plates of Iron tinned over. If to twenty parts of Tin one part of Copper be added, this alloy renders it much more solid, and the mixed mass continues tolerably ductile. If, on the contrary, to one part of Tin ten parts of Copper be added, together with a little Zink, a semi-metal to be considered hereafter, from this combination there results a metalline compound which is hard, brittle, and very sonorous; so that it is used for casting bells: this composition is called _Bronze_ and _Bell-metal_. Tin hath an affinity with the vitriolic, nitrous, and marine acids. All of them attack and corrode it; yet none of them is able to dissolve it without great difficulty: so that if a clear solution thereof be desired, particular methods must be employed for that purpose; for the acids do but in a manner calcine it, and convert it to a kind of white calx or precipitate. The solvent which has the greatest power over it is _aqua regis_, which has even a greater affinity therewith than with Gold itself; whence it follows, that Gold dissolved in _aqua regis_ may be precipitated by means of Tin; but then the _aqua regis_ must be weakened. Gold thus precipitated by Tin is of a most beautiful colour, and is used for a red in enameling and painting on porcelain, as also to give a red colour to artificial gems. If the _aqua regis_ be not lowered, the precipitate will not have the purple colour. Tin hath the property of giving a great lustre to all red colours in general; on which account it is used by the dyers for striking a beautiful scarlet, and tin vessels are employed in making fine syrup of violets. Water does not act upon this metal, as it does upon Iron and Copper; for which reason it is not subject to rust: nevertheless, when it is exposed to the air, its surface soon loses its polish and splendour. Tin mixed with nitre and exposed to the fire deflagrates with it, makes it detonate, and is immediately converted to a _refractory calx_: for so all substances are called which are incapable of fusion. Tin readily unites with sulphur, and with it becomes a brittle and friable mass. SECTION VI. _Of_ LEAD. Next to Gold and Mercury Lead is the heaviest of all metalline substances, but in hardness is exceeded by every one of them. Of all metals also it melts the easiest except Tin. While it is in fusion there gathers incessantly on its surface, as on that of Tin, a blackish dusty pellicle, which is nothing but a calx of Lead. This calx further calcined by a moderate fire, the flame being reverberated on it, soon grows white. If the calcination be continued it becomes yellow, and at last of a beautiful red. In this state it is called _Minium_, and is used as a pigment. _Minium_ is not easily made, and the operation succeeds well in large manufactures only. To convert Lead into _Litharge_, which is the metal in a manner half vitrified, you need only keep it melted by a pretty strong fire; for then as its surface gradually calcines, it tends more and more to fusion and vitrification. All these preparations of Lead are greatly disposed to perfect fusion and vitrification, and for that purpose require but a moderate degree of fire; the calx or earth of Lead being of all metalline earths that which vitrifies the most easily. Lead hath not only the property of turning into glass with the greatest facility, but it hath also that of promoting greatly the vitrification of all the other imperfect metals; and, when it is actually vitrified, procures the ready fusion of all earths and stones in general, even those which are refractory, that is, which could not be fused without its help. Glass of Lead, besides its great fusibility, hath also the singular property of being so subtile and active as to corrode and penetrate the crucibles in which it is melted, unless they be of an earth that is exceeding hard, compact, and withal very refractory: for Glass of Lead being one of the most powerful fluxes that we know, if the earth of the crucible in which it is melted be in the smallest degree fusible, it will be immediately vitrified; especially if there be any metallic matter in its composition. The great activity of Glass of Lead may be weakened by joining it with other vitrifiable matters: but unless these be added in a very great proportion, it will still remain powerful enough to penetrate common earths, and carry off the matters combined with it. On these properties of Lead, and of the Glass of Lead, depends the whole business of refining Gold and Silver. It hath been shewn, that as these two metals are indestructible by fire, and the only ones which have that advantage, they may be separated from the imperfect metals, when mixed therewith, by exposing the compound to a degree of fire sufficiently strong to vitrify the latter; which, when once converted into glass, can no longer remain united with any metal that has its metalline form. But it is very difficult to procure this vitrification of the imperfect metals, when united with Gold and Silver; nay, it is in a manner impossible to vitrify them entirely, for two reasons: first, because most of them are naturally very difficult to vitrify; secondly, because the union they have contracted with the perfect metals defends them, in a manner, from the action of the fire, and that so much the more effectually as the proportion of the perfect metals is greater; which being indestructible, and in some sort coating over those with which they are alloyed, serve them as a preservative and impenetrable shield against the utmost violence of fire. It is therefore clear, that a great deal of labour may be saved, and that Gold and Silver may be refined to a much greater degree of purity than can otherwise be obtained, if to a mixture of these metals with Copper, for instance, or any other imperfect metal be added a certain quantity of Lead. For the Lead, by its known property, will infallibly produce the desired vitrification; and as it likewise increases the proportion of the imperfect metals, and so lessens that of the perfect metals, in the mass, it evidently deprives the former of a part of their guard, and so effects a more complete vitrification. In conclusion, as the Glass of Lead hath the property of running through the crucible, and carrying with it the matters which it has vitrified, it follows, that, when the vitrification of the imperfect metals is effected by its means, all those vitrified matters together penetrate the vessel containing the fused metalline mass, disappear, and leave only the Gold and Silver perfectly pure, and freed, as far as is possible, from all admixture of heterogeneous parts. The better to promote the separation of such parts it is usual to employ, in this process, a particular sort of small crucibles, made of the ashes of calcined bones, which are exceedingly porous and easily pervaded. They are called _cupels_, on account of their figure, which is that of a wide-mouthed cup: and from hence the operation takes its name; for when we refine Gold and Silver in this manner we are said to _cupel_ those metals. It is easy to perceive that the more Lead is added the more accurately will the Gold and Silver be refined; and that so much the more Lead ought to be added as the perfect metals are alloyed with a greater proportion of the imperfect. This is the most severe trial to which a perfect metal can be put; and consequently any metal that stands it may be fairly considered as such. In order to denote the fineness of Gold, it is supposed to be divided into twenty-four parts called _carats_; and Gold which is quite pure and free from all alloy is said to be twenty-four _carats fine_; that which contains 1/24 part of alloy is called Gold of twenty-three carats; that which contains 2/24 of alloy is but twenty-two carats; and so on. Silver again is supposed to be divided into twelve parts only, which are called _penny-weights_: so that when absolutely pure it is said to be twelve _penny-weights fine_; when it contains 1/12 of alloy, it is then called eleven penny-weights fine; when it contains 2/12 of alloy, it is called ten penny-weights fine, and so on. In treating of Copper we promised to shew, under the article of Lead, how to separate it from Iron. The process is founded on that property of Lead which renders it incapable of mixing and uniting with Iron, though it readily dissolves all other metalline substances. Therefore, if you have a mass compounded of Copper and Iron, it must be fused with a certain quantity of Lead, and then the Copper, having a greater affinity with Lead than with Iron, will desert the latter and join the former, which being incapable of any union with Iron, as was said, will wholly exclude it from the new compound. The next point is to separate the Lead from the Copper; which is done by exposing the mass compounded of these two metals to a degree of fire strong enough to deprive the Lead of its metalline form, but too weak to have the same effect on the Copper: and this may be done; since, of all the imperfect metals, Lead is, next to Tin, the easiest to be calcined, and Copper on the contrary resists the greatest force of fire longest, without losing its metalline form. Now what we gain by this exchange, viz. by separating Copper from Iron and uniting it with Lead, consists in this, that as Lead is calcined with less fire than Iron, the Copper is less exposed to be destroyed: for it must be observed that, however moderate the fire be, it is hardly possible to prevent a certain quantity thereof from being calcined in the operation. Lead melted with a third part of Tin forms a compound, which being exposed to a fire capable of making it thoroughly red-hot, swells, puffs up, seems in some sort to take fire, and is presently calcined. These two metals mixed together are much sooner calcined than either of them separately. Both Lead and Tin are in some measure affected by water, and by a moist air; but they are both much less subject than Iron or Copper to be corroded by these solvents, and of course are much less liable to rust. The vitriolic acid acts upon and dissolves Lead, much in the same manner as it doth Silver. The nitrous acid dissolves this metal with much ease, and in great quantities; and from this solution a small portion of Mercury may be obtained. On this subject see our _Elements of the Practice of Chymistry_. When this solution of Lead is diluted with a good deal of water, the Lead precipitates in the form of a white powder; which happens because the acid is rendered too weak to keep the Lead dissolved. If this solution of Lead be evaporated to a certain degree, it shoots into crystals formed like regular pyramids with square bases. These crystals are of a yellowish colour, and a saccharine taste: they do not easily dissolve in water. This nitrous metalline salt has the singular property of detonating in a crucible, without any additament, or the contact of any other inflammable substance. This property it derives from the great quantity of phlogiston contained in, and but loosely connected with, the Lead which is one of its principles. If spirit of salt, or even sea-salt in substance, be added to a solution of Lead in the nitrous acid, a white precipitate immediately falls; which is no other than the Lead united with the marine acid. This precipitate is extremely like the precipitate of Silver made in the same manner, and that being called _Luna cornea_ hath occasioned this to be named _Plumbum corneum_. Like the _luna cornea_ it is very fusible, and being melted hardens like it into a kind of horny substance: it is volatile, and may be reduced by means of inflammable matters combined with alkalis. But it differs from the _luna cornea_ in this chiefly, that it dissolves easily in water; whereas the _luna cornea_, on the contrary, dissolves therein with great difficulty, and in a very small quantity. As this precipitation of Lead from its solution in spirit of nitre is procured by the marine acid, Lead is thereby proved to have a greater affinity with the latter acid than with the former. Yet, if you attempt to dissolve Lead directly by the acid of sea-salt, the solution is not so easily effected as by the spirit of nitre, and it is always imperfect; for it wants one of the conditions essential to every solution in a liquor, namely transparency. If Lead be boiled for a long time in a lixivium of fixed alkali, part of it will be dissolved. Sulphur renders this metal refractory and scarce fusible; and the mass they form when united together is friable. Hence it appears that sulphur acts upon Lead much in the same manner as upon Tin; that is, it renders both these metals less fusible, which are naturally the most fusible of any, while it exceedingly facilitates the fusion of Silver, Copper, and Iron, metals which of themselves flow with the greatest difficulty. CHAP. VIII. _Of_ QUICK-SILVER. We treat of Quick-silver in a chapter apart, because this metallic substance cannot be classed with the metals properly so called, and yet has some properties which will not allow us to confound it with the semi-metals. The reason why Quick-silver, by the Chymists commonly called Mercury, is not reputed a metal, is, that it wants one of the essential properties thereof, to wit, malleability. When it is pure and unadulterated with any mixture, it is always fluid, and of course unmalleable. But as, on the other hand, it eminently possesses the opacity, the splendour, and, above all, the gravity of a metal, being next to Gold the heaviest of all bodies, it may be considered as a true metal, differing from the rest no otherwise than by being constantly in fusion; which we may suppose arises from its aptness to flow with such a small degree of heat, that be there ever so little warmth on earth, there is still more than enough to keep Mercury in fusion; which would become solid and malleable if it were possible to apply to it a degree of cold considerable enough for that purpose. These properties will not allow us to confound it with the semi-metals. Add, that we are not yet assured by any undoubted experiment that it can be wholly deprived of its phlogiston, as the imperfect metals may. Indeed we cannot apply the force of fire to it as could be wished: for it is so volatile that it flies off and exhales in vapours, with a much less degree of fire than is necessary to make it red-hot. The vapours of Mercury thus raised by the action of fire, being collected and united in a certain quantity, appear to be no other than true Mercury, retaining every one of its properties; and no experiment hath ever been able to shew the least change thus produced in its nature. If Mercury be exposed to the greatest heat that it can bear without sublimation, and continued in it for several months, or even a whole year together, it turns to a red powder, which the Chymists call _Mercurius Præcipitatus per se_. But, to succeed in this operation, it is absolutely necessary that the heat be such as is above-specified; for this metallic substance may remain exposed to a weaker heat for a considerable number of years, without undergoing any sensible alteration. Some Chymists fancied, that by this operation they had fixed Mercury and changed its nature; but without any reason: for if the Mercury thus seemingly transmuted be exposed to a somewhat stronger degree of fire, it sublimes and exhales in vapours as usual; and those vapours collected are nothing else but running Mercury, which has recovered all its properties without the help of any additament. Mercury has the property of dissolving all the metals, Iron only excepted. But it is a condition absolutely necessary to the success of such dissolution, that the metalline substances be possessed of their phlogiston; for if they be calcined, Mercury cannot touch them: and hence it follows, that Mercury doth not unite with substances that are purely earthy. Such a combination of a metal with Mercury is called an _Amalgam_. Trituration alone is sufficient to effect it; however, a proper degree of heat also is of use. Mercury amalgamated with a metal gives it a consistence more or less soft, and even fluid, according to the greater or smaller proportion of Mercury employed. All amalgams are softened by heat, and hardened by cold. Mercury is very volatile; vastly more so than the most unfixed metals; moreover, the union it contracts with any metal is not sufficiently intimate to entitle the new compound resulting from that union to all the properties of the two substances united: at least with regard to their degree of fixity and volatility. From all which it follows, that the best and surest method of separating it from metals dissolved by it, is to expose the amalgam to a degree of heat sufficient to make all the Quick-silver rise and evaporate; after which the metal remains in the form of a powder, and being fused recovers its malleability. If it be thought proper to save the Quick-silver, the operation must be performed in close vessels, which will confine and collect the mercurial vapours. This operation is most frequently employed to separate Gold and Silver from the several sorts of earths and sands with which they are mixed in the ore; because these two metals, Gold especially, are of sufficient value to compensate the loss of Mercury, which is inevitable in this process: besides, as they very readily amalgamate with it, this way of separating them from every thing unmetallic is very facile and commodious. Mercury is dissolved by acids; but with circumstances peculiar to each particular sort of acid. The vitriolic acid, concentrated and made boiling hot, seizes on it, and presently reduces it to a kind of white powder, which turns yellow by the affusion of water, but does not dissolve in it; it is called _Turbith Mineral_. However, the vitriolic acid on this occasion unites with a great part of the Mercury, in such a manner that the compound is soluble in water. For if to the water which was used to wash the Turbith a fixed alkali be added, there falls instantly a russet-coloured precipitate, which is no other than Mercury separated from the vitriolic acid by the intervention of the alkali. This dissolution of Mercury by the vitriolic acid is accompanied with a very remarkable phenomenon; which is, that the acid contracts a strong smell of volatile spirit of sulphur: a notable proof that part of the phlogiston of the Mercury hath united therewith. And yet, if the Mercury be separated by means of a fixed alkali, it does not appear to have suffered any alteration. Turbith mineral is not so volatile as pure Mercury. The nitrous acid dissolves Mercury with ease. The solution is limpid and transparent, and as it grows cold shoots into crystals, which are a nitrous mercurial salt. If this solution be evaporated to dryness, the Mercury remains impregnated with a little of the acid, under the form of a red powder, which hath obtained the names of _Red Precipitate_, and _Arcanum Corallinum_. This Precipitate, as well as Turbith, is less volatile than pure Mercury. If this solution of Mercury be mixed with a solution of Copper, made likewise in the nitrous acid, and the mixture evaporated to dryness, there will remain a green powder called _Green Precipitate_. These precipitates are caustic and corrosive; and are used as such in surgery. Though Mercury be dissolved more easily and completely by the nitrous acid than by the vitriolic, yet it has a greater affinity with the latter than with the former: for if a vitriolic acid be poured into a solution of Mercury in spirit of nitre, the Mercury will quit the latter acid in which it was dissolved, and join the other which was added. The same thing happens when the marine acid is employed instead of the vitriolic. Mercury combined with spirit of salt forms a singular body; a metalline salt which shoots into long crystals, pointed like daggers. This salt is volatile, and sublimes easily without decomposition. It is moreover the most violent of all the corrosives hitherto discovered by Chymistry. It is called _Corrosive Sublimate_, because it must absolutely be sublimed to make the combination perfect. There are several ways of doing this: but the operation will never fail, if the Mercury be rarefied into vapours, and meet with the marine acid in a similar state. Corrosive Sublimate is dissolved by water, but in very small quantities only. It is decompounded by fixed alkalis, which precipitate the Mercury in a reddish yellow powder, called, on account of its colour, _Yellow Precipitate_. If Corrosive Sublimate be mixed with tin, and the compound distilled, a liquor comes over which continually emits abundance of dense fumes, and, from the name of its inventor, is called the _Smoking Liquor of Libavius_. This liquor is no other than the tin combined with the marine acid of the Corrosive Sublimate, which therefore it hath actually decompounded: whence it follows, that this acid hath a greater affinity with tin than with Mercury. The marine acid in Corrosive Sublimate is not quite saturated with Mercury; but is capable of taking up a much greater quantity thereof. For if Corrosive Sublimate be mixed with fresh Mercury, and sublimed a second time, another compound will be produced containing much more Mercury, and less acrimonious; for which reason it is named _Sweet Sublimate of Mercury_, _Mercurius dulcis_, _Aquila alba_. This compound may be taken internally, and is purgative or emetic according to the dose administered. It may be rendered still more gentle by repeated sublimations, and then it takes the title of _Panacea Mercurialis_. No way hath hitherto been found to dissolve Mercury in _aqua regis_ without great difficulty, and even then it is but imperfectly dissolved. Mercury unites easily and intimately with sulphur. If these two substances be only rubbed together in a gentle heat, or even without any heat, they will contract an union, though but an incomplete one. This combination takes the form of a black powder, which has procured it the name of _Æthiops Mineral_. If a more intimate and perfect union be desired, this compound must be exposed to a stronger heat; and then a red ponderous substance will be sublimed, appearing like a mass of shining needles: this is the combination desired, and is called _Cinabar_. In this form chiefly is Mercury found in the bowels of the earth. Cinabar finely levigated acquires a much brighter red colour, and is known to painters by the name of _Vermilion_. Cinabar rises wholly by sublimation, without suffering any decomposition; because the two substances of which it consists, _viz._ Mercury and Sulphur, are both volatile. Though Mercury unites and combines very well with sulphur, as hath been said, yet it hath less affinity with that mineral than any other metal, Gold only excepted: whence it follows, that any of the other metals will decompound Cinabar, by uniting with its sulphur, and so setting the Mercury at liberty to appear in its usual form. Mercury thus separated from sulphur is esteemed the purest, and bears the name of _Mercury revivified from Cinabar_. Iron is generally used in this operation, preferably to the other metals, because among them all it has the greatest affinity with sulphur, and is the only one that has none with Mercury. Cinabar may also be decompounded by means of fixed alkalis; the affinity of these salts with sulphur being generally greater than that of any metalline substance whatever. CHAP. IX. _Of the_ SEMI-METALS. SECTION I. _Of_ REGULUS OF ANTIMONY. Regulus of Antimony is a metallic substance of a pretty bright white colour. It has the splendour, opacity, and gravity of a metal: but it is quite unmalleable, and crumbles to dust, instead of yielding or stretching, under the hammer; on which account it is classed with the Semi-metals. It begins to flow as soon as it is moderately red; but, like the other Semi-metals, it cannot stand a violent degree of fire; being thereby dissipated into smoke and white vapours, which adhere to such cold bodies as they meet with, and so are collected into a kind of _farina_ called _Flowers of Antimony_. If Regulus of Antimony, instead of being exposed to a strong fire, be only heated so moderately that it shall not even melt, it will calcine, lose its phlogiston, and take the form of a greyish powder destitute of all splendour: this powder is called _Calx of Antimony_. This calx is not volatile like the Regulus, but will endure a very violent fire; and being exposed thereto will flow, and turn to a glass of the yellowish colour of a hyacinth. It is to be observed, that the more the Regulus is deprived of its phlogiston by continued calcination, the more refractory is the calx obtained from it. The glass thereof has also so much the less colour, and comes the nearer to common glass. The calx and the Glass of Antimony will recover their metalline form, like every other Calx and Glass of a metal, if reduced by restoring to them their lost phlogiston. Yet if the calcination be carried too far, their reduction will become much more difficult, and a much smaller quantity of Regulus will be resuscitated. Regulus of Antimony is capable of dissolving the metals: but its affinities with them are various, and differ according to the following order. It affects Iron the most powerfully, next Copper, then Tin, Lead, and Silver. It promotes the fusion of metals, but makes them all brittle and unmalleable. It will not amalgamate with Mercury; and though by certain processes, particularly the addition of water and continued trituration, a sort of union between these two substances may be produced, yet it is but apparent and momentary; for, being left to themselves and undisturbed, they quickly disunite and separate[2]. [2] M. Malouin, however, hath found a way to unite these two metallic substances: but then he does it by the interposition of sulphur; that is, he combines crude Antimony with Mercury. This combination is brought about in the same way that Æthiops Mineral is made; _viz._ either by fusion, or by trituration only without fire. It resembles the common Æthiops, and M. Malouin calls it _Æthiops of Antimony_. He observed that Mercury unites with Antimony much more intimately, by melting, than by rubbing them together. The vitriolic acid, assisted by heat, and even by distillation, dissolves Regulus of Antimony. The nitrous acid likewise attacks it: but the solution can by no art be made clear and limpid: so that the Regulus is only calcined, in a manner, by this acid. The marine acid dissolves it well enough; but then it must be exceedingly concentrated, and applied in a peculiar manner, and especially by distillation. One of the best methods of procuring a perfect union between the acid of sea-salt and Regulus of Antimony, is to pulverize the latter, mix it with corrosive sublimate, and distil the whole. There rises in the operation a white matter, thick, and scarce fluid, which is no other than the Regulus of Antimony united and combined with the acid of sea-salt. This compound is extremely corrosive, and is called _Butter of Antimony_. It is plain that the corrosive sublimate is here decompounded; that the Mercury is revivified, and that the acid which was combined therewith hath quitted it to join the Regulus of Antimony, with which its affinity is greater. This Butter of Antimony by repeated distillations acquires a considerable degree of fluidity and limpidness. If the acid of nitre be mixed with Butter of Antimony, and the whole distilled, there rises an acid liquor, or a sort of _aqua regis_, which still retains some of the dissolved Regulus, and is called _Bezoardic Spirit of Nitre_. After the distillation there remains a white matter, from which fresh spirit of nitre is again abstracted, and which being then washed with water is called _Bezoar Mineral_. This Bezoar Mineral is neither so volatile nor so caustic as Butter of Antimony; because the nitrous acid hath not the property of volatilizing metallic substances, as the marine acid does, and because it remains much more intimately combined with the reguline part. If Butter of Antimony be mixed with water, the liquor immediately becomes turbid and milky, and a precipitate falls, which is nothing but the metallic matter partly separated from its acid, which is too much weakened by the addition of water to keep it dissolved. Yet this precipitate still retains a good deal of acid; for which reason it continues to be a violent emetic, and in some degree corrosive. It hath therefore been very improperly called _Mercurius Vitæ_. The proper solvent of Regulus of Antimony is _aqua regis_; by means whereof a clear and limpid solution of this Semi-metal may be obtained. Regulus of Antimony mixed with nitre, and projected into a red-hot crucible, sets the nitre in a flame, and makes it detonate. As it produces this effect by means of its phlogiston, it must needs at the same time be calcined, and lose its metallic properties, which accordingly happens, and when the nitre is in a triple proportion to the Regulus, the latter is so perfectly calcined as to leave only a white powder, which is fused with great difficulty, and then turns to a faintly coloured glass, not very different from common glass, and which is not reducible to a Regulus by the addition of inflammable matter; at least it yields but a very small quantity thereof. If less nitre be used, the calx is not so white; the glass it produces is more like a metalline glass, and is more easily reduced. The calx of the Regulus thus prepared by nitre is called, on account of the medicinal virtue ascribed to it, _Diaphoretic Antimony_, or _Diaphoretic Mineral_. Nitre always becomes an alkali by deflagration, and in the present case retains part of the calx, which it even renders soluble in water. This calx may be separated from the alkali, if an acid be employed to precipitate it; and then it is called _Materia Perlata_. This pearly matter is a calx of Antimony, so completely deprived of its phlogiston as to be altogether incapable of reduction to a Regulus. Regulus of Antimony readily joins and unites with sulphur, forming therewith a compound which has a very faint metallic splendour. This compound appears like a mass of long needles adhering together laterally; and under this form it is usually found in the ore, or at least when only separated by fusion from the stones and earthy matters with which the ore is mixed. It is called _Crude Antimony_. Antimony flows with a moderate heat, and becomes even more fluid than other metallic substances. The action of fire dissipates or consumes the sulphur it contains, and its phlogiston also, so as to convert it into a calx and a glass, as it does the Regulus. _Aqua regis_, which we observed to be the proper solvent of the Regulus, being poured on Antimony, attacks and dissolves the reguline part, but touches not the sulphur; in consequence whereof it decomposes the Antimony, and separates its sulphur from its Regulus. There are several other ways of effecting this decomposition, and obtaining the reguline part of Antimony by itself: they consist either in destroying the sulphureous part of the Antimony by combustion, or in melting the Antimony with some substance which has a greater affinity than its reguline part with sulphur. Most metals are very fit for this latter purpose: for though the Regulus has a considerable affinity with sulphur, yet all the metals, except Gold and Mercury, have a greater. If therefore Iron, Copper, Lead, Silver, or Tin, be melted with Antimony, the metal employed will unite with the sulphur, and separate it from the Regulus. It must be observed, that, as these metals have some affinity with the Regulus of Antimony, the Regulus will be joined in the operation by some of the metal employed as a _Precipitant_, (so those substances are called which serve as the means of separating two bodies from each other); and therefore the Regulus procured in this manner will not be absolutely pure: on this account care is taken to distinguish each by adding the name of the metal employed in its precipitation; and thence come these titles, _Martial Regulus of Antimony_, or only _Martial Regulus_, _Regulus Veneris_; and so of the rest. Antimony is employed with advantage to separate Gold from all the other metals with which it may be alloyed. It has been shewn, that all the metals have a greater affinity than the reguline part of Antimony with sulphur, Gold only excepted; which is incapable of contracting any union therewith: and therefore, if a mass compounded of Gold and several other metals be melted with Antimony, every thing in that mass which is not Gold will unite with the sulphur of the Antimony. This union occasions two separations, to wit, that of the sulphur of the Antimony from its reguline part, and that of the Gold from the metals with which it was adulterated; and from the whole two new compounds arise; namely, a combination of the metals with the sulphur, which being lightest rises to the surface in fusion; and a metalline mass, formed of the Gold and the reguline part of the Antimony united together, which being much the heaviest sinks to the bottom. There is no difficulty in parting the Gold from the Regulus of Antimony with which it is alloyed: for the metalline mass needs only be exposed to a degree of fire capable of dissipating into vapours all the Semi-metal it contains; which being very volatile, the operation is much easier, and more expeditiously finished, than if the metals with which the Gold was debased were to be vitrified on the cupel; without taking into the account, that, if Silver were one of them, recourse must needs be had to the process of quartation after that of the cupel. If equal parts of nitre and Antimony be mixed together, and the mixture exposed to the action of fire, a violent detonation ensues; the nitre deflagrating consumes the sulphur of the Antimony, and even a part of its phlogiston. After the detonation there remains a greyish matter which contains fixed nitre, vitriolated tartar, and the reguline part of the Antimony in some measure deprived of its phlogiston, and half vitrified by the action of the fire, which is considerably increased by the deflagration. This matter is called _Liver of Antimony_. If, instead of equal parts of nitre and Antimony, two parts of the former be used to one of the latter, then the reguline part loses much more of its phlogiston, and remains in the form of a yellowish powder. Again, if three parts of nitre be taken to one of Antimony, the Regulus is thereby entirely robbed of its phlogiston, and converted to a white calx, which bears the name of _Diaphoretic Antimony_, or _Diaphoretic Mineral_. The pearly matter may be precipitated by pouring an acid on the saline substances which here remain after the detonation, in the same manner as we shewed above was to be done with regard to the Regulus. In the two last operations, where the nitre is in a double or triple proportion to the Antimony, the reguline part is found after the detonation to be converted into a calx, and not into a half-vitrified matter, which we have seen is the effect when equal parts only of nitre and Antimony are used. The reason of this difference is, that in these two cases the reguline part, being wholly, or almost wholly, deprived of its phlogiston, becomes, as was observed, more difficult to fuse, and consequently cannot begin to vitrify in the same degree of heat as that which hath not lost so much of its phlogiston. If, instead of performing the operation with equal parts of nitre and Antimony alone, a portion of some substance which abounds with phlogiston be added, in that case the sulphur only of the Antimony will be consumed, and the Regulus will remain united with its phlogiston and separated from its sulphur. The Regulus prepared in this manner is absolutely pure, because no metalline substance being employed, none can mix with and adulterate it. It is called _Regulus of Antimony per se_, or only _Regulus of Antimony_. It is true indeed that in this operation much of the reguline part unavoidably loses its phlogiston and is calcined, and consequently a much smaller quantity of Regulus is obtained than when metalline precipitants are employed: but this loss is easily repaired, if it be thought proper, by restoring to the calcined part its lost phlogiston. Antimony melted with two parts of fixed alkali yields no Regulus, but is entirely dissolved by the salt, and forms with it a mass of a reddish yellow colour. The reason why no precipitate is produced on this occasion is, that the alkali uniting with the sulphur of the Antimony forms therewith the combination called Liver of Sulphur, which by its nature is qualified to keep the reguline part dissolved. This mass formed by the union of the Antimony with the alkali is soluble in water. If any acid whatever be dropt into this solution, there falls a precipitate of a reddish yellow colour; because the acid unites with the alkali, and forces it to quit the matters with which it was combined. This precipitate is called _Golden Sulphur of Antimony_. As in the operation for preparing _Regulus of Antimony per se_, some of the nitre is, by the inflammable matters added thereto, turned to an alkali, this alkali seizes on part of the Antimony, and therewith forms a compound like that just described. Hence it comes, that if the scoria formed in this process be dissolved in water, and an acid dropped into the solution, a true golden sulphur of Antimony is thereby separated. This union of Antimony with an alkali may also be brought about by the humid way; that is, by making use of an alkali resolved into a liquor, and boiling the mineral in it. The alkaline liquor, in proportion as it acts upon the Antimony, gradually becomes reddish and turbid. If left to settle and cool when well saturated therewith, it gradually deposites the Antimony it had taken up, which precipitates in the form of a red powder; and this precipitate is the celebrated remedy known by the name of _Kermes Mineral_. It is plain that the kermes is nearly the same thing with the golden sulphur: yet it differs from it in some respects; and especially in this, that being taken inwardly it operates much more gently than the golden sulphur, which is a violent emetic. Nitre fixed by charcoal, and resolved into a liquor, is the only alkali employed in preparing the kermes. It was shewn above, that Regulus of Antimony mixed and distilled with corrosive sublimate decompounds it, disengages the Mercury, and joining itself to the marine acid forms therewith a new combination, called Butter of Antimony. If the same operation be performed with crude Antimony instead of its Regulus, the same effects are produced: but then the Antimony itself is also decomposed; that is, the reguline part is separated from the sulphur, which being set free unites with the Mercury, now also at liberty, and these two together form a true cinabar, called _Cinabar of Antimony_. SECTION II. _Of_ BISMUTH. Bismuth, known also by the name of Tin-glass, is a semi-metal, having almost the same appearance as Regulus of Antimony; yet it has a more dusky cast, inclining somewhat to red, and even presents some changeable streaks, especially after lying long in the air. When exposed to the fire it melts long before it is red, and consequently with less heat than Regulus of Antimony, which does not flow, as was shewn above, till it begin to be red-hot. It becomes volatile, like all the other semi-metals, when acted on by a violent fire: being kept in fusion by a proper degree of heat it loses its phlogiston with its metallic form, and turns to a powder or a calx; and that again is converted into glass by the continued action of fire. The calx and glass of Bismuth may be reduced, like any other metallic calx, by restoring their phlogiston. Bismuth mixes with all the metals in fusion, and even facilitates the fusion of such as do not otherwise flow readily. It whitens them by its union, and destroys their malleability. It amalgamates with Mercury, if they be rubbed together with the addition of water: yet after some time these two metalline substances desert each other, and the Bismuth appears again in the form of a powder. Hence it is plain, that the union it contracts with Mercury is not perfect; and yet it has the singular property of attenuating Lead, and altering it in such a manner that it afterwards amalgamates with Mercury much more perfectly, so as even to pass with it through shamoy leather without any separation. The Bismuth employed in making this amalgama afterwards separates from it spontaneously, as usual; but the Lead still continues united with the Mercury, and always retains the property thus acquired. The vitriolic acid does not dissolve Bismuth: its proper solvent is the nitrous acid, which dissolves it with violence, and abundance of fumes. Bismuth dissolved in the nitrous acid is precipitated not only by alkalis, but even by the bare addition of water. This precipitate is extremely white, and known by the name of _Magistery of Bismuth_. The acid of sea-salt and _aqua regis_ likewise act upon Bismuth, but with less violence. This semi-metal does not sensibly deflagrate with nitre; yet it is quickly deprived of its phlogiston, and turned into a vitrifiable calx, when exposed with it to the action of fire. It readily unites with sulphur in fusion, and forms therewith a compound which appears to consist of needles adhering laterally to each other. It may be separated from the sulphur with which is combined, by only exposing it to the fire, without any additament; for the sulphur is either consumed or sublimed, and leaves the Bismuth behind. SECTION III. _Of_ ZINC. Zinc to appearance differs but little from Bismuth, and has even been confounded with it by several authors. Nevertheless, besides that it has something of a blueish cast, and is harder than Bismuth, it differs from it essentially in its properties, as will presently be shewn. These two metallic substances scarce resemble each other in any thing, but the qualities common to all semi-metals. Zinc melts the moment it grows red in the fire, and then also begins to turn to a calx, which, like any other metallic calx, may be reduced by means of the phlogiston: but if the fire be considerably increased, it sublimes, flames, and burns like an oily matter; which is a proof of the great quantity of phlogiston in its composition. At the same time abundance of flowers rise from it in the form of white flakes, flying about in the air like very light bodies; and into this form may the whole substance of the Zinc be converted. Several names have been given to these flowers, such as Pompholyx, Philosophic Wool. They are supposed to be no other than the Zinc itself deprived of its phlogiston; yet no body has hitherto been able to resuscitate them in the form of Zinc, by restoring their phlogiston according to the methods used in the reduction of metals. Though they rise in the air with very great ease while the Zinc is calcining, yet when once formed they are very fixed; for they withstand the utmost violence of fire, and are capable of being vitrified, especially if joined with a fixed alkali. They are soluble in acids. Zinc unites with all metalline substances, except Bismuth. It has this singular property, that being mixed with Copper, even in a considerable quantity, such as a fourth part, it does not greatly lessen the ductility thereof, and at the same time communicates to it a very beautiful colour not unlike that of Gold: on which account the composition is frequently made, and produces what is called _Brass_. This metal melts much more easily than Copper alone, because of the Zinc with which it is alloyed. If it be exposed to a great degree of heat, the Zinc which it contains takes fire, and sublimes in white flowers, just as when it is pure. It is to be observed, that Brass is ductile only while it is cold, and not then, unless the Zinc used in making it was very pure; otherwise the composition will prove but a _Tombac_ or _Prince's Metal_, having very little malleability. Zinc is very volatile, and carries off with it any metallic substance with which it is fused, making a kind of sublimate thereof. In the furnaces where they smelt ores containing Zinc, the matter thus sublimed is called _Cadmia Fornacum_, to distinguish it from the native _Cadmia_ called also _Calamine_, or _Lapis Calaminaris_; which, properly speaking, is an ore of Zinc, containing a great deal of that semi-metal, together with some Iron, and a stony substance. The name of _Cadmia Fornacum_ is not appropriated solely to the metallic sublimates procured by means of Zinc, but is given in general to all the metallic sublimates found in smelting houses. If a violent and sudden heat be applied to Zinc, it sublimes in its metalline form; there not being time for it to burn and be resolved into flowers. This semi-metal is soluble in all the acids, but especially in spirit of nitre, which attacks and dissolves it with very great violence. Zinc has a greater affinity than iron or copper with the vitriolic acid; and therefore it decompounds the green and blue vitriols, precipitating those two metals by uniting with the vitriolic acid, with which it forms a metallic salt, or vitriol, called _White Vitriol_, or _Vitriol of Zinc_. Nitre mixed with Zinc, and projected into a red-hot crucible, detonates with violence, and during the detonation there rises a great quantity of white flowers, like those which appear when it is calcined by itself. Sulphur has no power over Zinc. Even liver of sulphur, which dissolves all other metallic substances, contracts no union with this semi-metal. Messrs. Hellot and Malouin have bestowed a great deal of pains on this semi-metal. An account of their experiments is to be found in the Memoirs of the Academy of Sciences. SECTION IV. _Of_ REGULUS OF ARSENIC. Regulus of Arsenic is the most volatile of all the semi-metals. A very moderate heat makes it wholly evaporate, and fly off in fumes; on which account it cannot be brought to fusion, nor can any considerable masses thereof be obtained. It has a metallic colour, somewhat resembling Lead; but it soon loses its splendour when exposed to the air. It unites readily enough with metallic substances, having the same affinities with them as Regulus of Antimony hath. It makes them brittle, and unmalleable. It hath also the property of rendering them volatile, and greatly facilitates their scorification. It very easily parts with its phlogiston and its metallic form. When exposed to the fire it rises in a kind of shining crystalline calx, which, on that account, looks more like a saline matter than a metallic calx. To this calx or these flowers are given the names of _White Arsenic_, _Crystalline Arsenic_, and most commonly plain _Arsenic_. The properties of this substance are very singular, and extremely different from those of any other metallic calx. Hitherto it hath been but little examined; and this led me to make some attempts towards discovering its nature, which may be seen in the Memoirs of the Academy of Sciences. Arsenic differs from every other metalline calx, first, in being volatile; whereas the calces of all other metallic substances, not excepting those of the most volatile semi-metals, such as Regulus of Antimony and Zinc, are exceeding fixed; and, secondly, in having a saline character, which is not found in any other metalline calx. The saline character of Arsenic appears, first, from its being soluble in water; secondly, from its corrosive quality, which makes it one of the most violent poisons: a quality from which the other metallic substances are free, when they are not combined with some saline matter. Regulus of Antimony must however be excepted. But then the best Chymists agree that this semi-metal is either nearly of the same nature with Arsenic, or contains a portion thereof in its composition: besides, its noxious qualities never discover themselves so plainly as when it is combined with some acid. Lastly, Arsenic acts just like the vitriolic acid upon nitre; that is, it decompounds that neutral salt, by expelling its acid from its alkaline basis, of which it takes possession, and therewith forms a new saline compound. This combination is a species of salt that is perfectly neutral. When the operation is performed in a close vessel, the salt shoots into crystals in the form of right-angled quadrangular prisms, terminated at each extremity by pyramids that are also quadrangular and right angled; some of which however, instead of ending in a point, are obtuse as if truncated. The consequence is different when the operation is performed in an open vessel; for then nothing is obtained but an alkaline salt impregnated with Arsenic, which cannot be crystallized. The cause of this different effect is, that, when the Arsenic is once engaged in the alkaline basis of the nitre, it can never be separated from it by the utmost force of fire, so long as it is kept in a close vessel; whereas, if you expose it to the fire without that precaution, it readily separates from it. This property of arsenic was never before observed by any Chymist, and therefore this our new species of Neutral arsenical salt was absolutely unknown till lately. This new salt possesses many singular properties, the chief of which are these. First, it cannot be decompounded by the intervention of any acid, even the strongest acid of vitriol; and this, joined to its property of expelling the nitrous acid from its basis, shews that it has a very great affinity with fixed alkalis. Secondly, this very salt, on which pure acids have no effect, is decompounded with the greatest ease by acids united with metallic substances. The reason of this phenomenon is curious, and furnishes us with an instance of what we advanced concerning double affinities. If to a resolution of any metallic substance whatever, made by any acid whatever, (except that of Mercury by the marine acid, and that of Gold by _aqua regis_), a certain quantity of our New Salt dissolved in water be added, the metallic substance is instantaneously separated from the acid in which it was dissolved, and falls to the bottom of the liquor. All metallic precipitates obtained in this manner are found to be a combination of the metal with Arsenic; whence it necessarily follows that the new Neutral Salt is by this means decompounded, its arsenical part uniting with the metallic substance, and its alkaline basis with the acid in which that substance was dissolved. The affinities of these several bodies must be considered as operating on this occasion in the following manner: The acids which tend to decompound the Neutral Salt of Arsenic, by virtue of their affinity with its alkaline basis, are not able to accomplish it, because this affinity is powerfully counteracted by that which the Arsenic has with the same alkaline basis, and which is equal or even superior to theirs. But if these acids happen to be united with a substance which naturally has a very great affinity with the arsenical part of the Neutral Salt, then, the two parts of which this Salt consists being drawn different ways by two several affinities tending to separate them from each other, the Salt will undergo a decomposition, which could not have been effected without the help of this second affinity. Now, as metallic substances have a great affinity with Arsenic, it is not surprising that the Neutral Salt of Arsenic, which cannot be decompounded by a pure acid, should nevertheless yield to an acid combined with a metal. The decomposition of this Salt, therefore, and the precipitation which of course it produces in metallic solutions, are brought about by the means of a double affinity; namely, that of the acid with the alkaline basis of the Neutral Salt, and that of the metal with the arsenical part of that salt. Arsenic has not the same effect on sea-salt as on nitre, and cannot expel its acid: a very singular phenomenon, for which it is hard to assign a reason; for the nitrous acid is known to have a greater affinity than the marine acid with alkalis, and even with the basis of sea-salt itself. Yet Arsenic may be combined with the basis of sea-salt, and a Neutral Salt thereby obtained, like that which results from the decomposition of nitre by Arsenic: but for that purpose a quadrangular nitre must be first prepared, and Arsenic applied thereto as to common nitre. The Salt produced by uniting Arsenic with the basis of sea-salt very much resembles the Neutral Salt of Arsenic above treated of as well in the figure of its crystals as in its several properties. Arsenic presents another singular phenomenon, both with the alkali of nitre and with that of sea-salt; which is, that if it be combined with these salts in a fluid state, it forms with them a saline compound, quite different from the Neutral Salts of Arsenic which result from the decomposition of nitrous salts. This saline compound, which I call _Liver of Arsenic_, takes up a much greater quantity of Arsenic than is necessary for the perfect saturation of the alkali. It has the appearance of a glue, which is so much the thicker the more Arsenic it contains. Its smell is disagreeable; it attracts the moisture of the air, and does not crystallize; it is easily decompounded by any acid whatever, which precipitates the Arsenic and unites with the alkali. Lastly, the effects it produces on metallic solutions are different from those of our neutral arsenical salts. But the bounds which I have set myself in this treatise will not allow me to be more particular. Such as have the curiosity to inquire further into the subject may consult my Dissertations on Arsenic, published among the Memoirs of the Academy of Sciences. Arsenic is easily reduced to a Regulus. It need only be mixed with any matter containing the phlogiston, and by the help of a moderate heat a true Regulus will sublime. This Regulus, as was said, is very volatile, and calcines with the greatest ease; which is the reason why it cannot be obtained but in small quantities, and also why, in order to obtain masses of it, some have thought of adding thereto some metal with which it has a great affinity, such as Copper or Iron; because, by joining with the metal, it is partly fixed and restrained from flying off. But it is plain the Regulus obtained by this means is not pure, as it must partake considerably of the metal employed. Arsenic readily unites with sulphur, and rises with it in a yellow compound, called _Orpiment_. Sulphur cannot be separated from Arsenic but by the intervention of two bodies only; to wit, a fixed alkali and Mercury. The property which Mercury possesses of separating sulphur from Arsenic is founded on this, that these two metallic substances are incapable of contracting any union; whereas, though most of the other metals and semi-metals have a greater affinity with sulphur than Mercury hath, as was shewn in treating of the decomposition of Cinabar, nevertheless they are all unable to decompound Orpiment; because some of them have as great an affinity with Arsenic as with sulphur; others have no affinity with either; and lastly, sulphur hath as great an affinity with Arsenic as with any of them. It must be observed that, if fixed alkalis be employed to purify Arsenic in this manner, no more must be used than is necessary to absorb the sulphur or the phlogiston, of which also it is their nature to deprive Arsenic; for otherwise, as it has been shewn that Arsenic readily unites with alkalis, they would absorb a considerable quantity thereof. CHAP. X. _Of_ OIL _in general_. Oil is an unctuous body, which burns and consumes with flame and smoke, and is not soluble in water. It consists of the phlogiston united with water by means of an acid. There is, moreover, in its composition a certain proportion of earth, more or less, according to each several sort of Oil. The inflammability of Oil evidently proves that it contains the phlogiston. That an acid is one of its constituent principles many experiments demonstrate, of which these are the chief: If certain Oils be long triturated with an alkaline salt, and the alkali afterwards dissolved in water, crystals of a true neutral salt will be produced: some metals, and particularly Copper, are corroded and rusted by Oils, just as they are by acids: again, acid crystals are found in some Oils that have been long kept. This acid in Oil serves undoubtedly to unite its phlogiston with its water; because these two substances having no affinity with each other cannot be united without the intervention of such a medium as an acid, which has an affinity with both. As to the existence of water in Oils, it appears plainly when they are decomposed by repeated distillations, especially after mixing them with absorbent earths. Lastly, when an Oil is destroyed by burning, a certain quantity of earth is constantly left behind. We are very sure that the above-mentioned principles enter into the composition of Oils; for they may be obtained from every one of them: but it is not absolutely certain that they consist of these only, and that they do not contain some other principle which may escape our notice in decomposing them; for hitherto it doth not appear, by any experiment we can depend on, that Oil was ever produced by combining together the principles here specified: yet such redintegrations are the only means we have of satisfying ourselves that we know all the principles which constitute a body. Oils exposed to the fire in close vessels pass over almost wholly from the containing vessel into any other applied to receive them. There remains, however, a small quantity of black matter, which is extremely fixed, and continues unalterable as long as it hath no communication with the external air, be the force of the fire ever so violent. This matter is no other than part of the phlogiston of the Oil united with its most fixed and grossest earth; and this is what we called _Charcoal_, or plainly a _Coal_. SECTION I. _Of_ CHARCOAL. When Oil happens to be united to much earth, as it is in vegetable and animal bodies, it leaves a considerable quantity of _Coal_ or charred matter. This Coal, exposed to the fire in the open air, burns and wastes, but without blazing like other combustible matters: there appears only a small blueish flame, but not the least smoke. Most commonly it only glows and sparkles, and so gradually falls into ashes, which are nothing but the earth of the body, combined with an alkaline salt in burning. This alkaline salt may be separated from the earth, by lixiviating the ashes with water, which dissolves all the salt, and leaves the earth quite pure. Charcoal is unalterable and indestructible by any other body but fire; whence it follows, that when it is not actually kindled and ignited, the most powerful agents, such as the acids, though ever so strong and concentrated, have not the least effect on it. The case is otherwise when it is lighted, that is, when its phlogiston begins to separate from its earth; for then the pure acid of vitriol being joined therewith, contracts an instantaneous union with its phlogiston, and evaporates in a volatile sulphureous spirit. If the vitriolic acid, instead of being applied quite pure, be first clogged with some basis, especially an alkaline one, it quits that basis, enters into a more intimate union with the phlogiston of the burning Coal, and so forms an actual sulphur, with which the alkali now unites and forms a hepar. The pure acid of sea-salt hath not been observed to act in the least upon Charcoal, especially when it is not on fire. But when this acid is incorporated with an alkaline or metallic basis, and combined according to a peculiar process with burning Charcoal, it in like manner quits its basis, unites with the phlogiston, and therewith forms a phosphorus, of which we have already taken notice. Nor has the pure nitrous acid any effect on a charred Coal, even when ignited: and so far is it from being able to kindle a cold one, that when poured on a live one, it extinguishes it like water. But when this acid is united with a basis, it quits it rapidly as soon as it touches a burning coal, and rushes violently into an union with the phlogiston thereof. From this union there probably arises, as we said before, a kind of sulphur or phosphorus, which is so inflammable as to be destroyed by the fire the very moment it is generated. The acids of nitre and vitriol act upon Oils; but very differently, according to the quantity of phlegm they contain. If they be weakened with much water, they have no effect at all upon Oils; if they contain little water, or be dephlegmated to a certain degree, they dissolve them with heat, and with them form compounds of a thick consistence. Acids, thus combined in a considerable proportion with Oils, render them soluble in water. SECTION II. _Of_ SOAP. Alkalis also have the same property. When an Oil is combined with an acid or an alkali in such a manner, that the compound resulting from their union is soluble in water; such a compound may in general be called a _Soap_. Soap itself hath the property of rendering fat bodies in some measure soluble in water; on which account it is very useful for scouring or cleansing any thing greasy. Oily and saline substances, combined together, observe the same general rules as all other combinations; that is, they mutually communicate the properties belonging to each: thus Oils, which naturally are not soluble in water, acquire, by their union with saline matters, the property of dissolving therein; and salts lose, by their conjunction with Oils, part of their natural tendency to incorporate with water; so that, while they serve to constitute soap, they do not, as before, attract the moisture of the air, _&c._ and, in like manner, as they are not inflammable, they considerably lessen the inflammability of the Oils combined with them. Acid Soaps are decompounded by alkalis, as alkaline Soaps are by acids, according to the general rules of affinities. The acids of nitre and vitriol, when highly concentrated, dissolve Oils with such violence as to heat them, make them black, burn them, and even set them on fire. How sea-salt affects Oils is not yet sufficiently ascertained. All Oils have the property of dissolving sulphur; which is not at all surprising, seeing each of its component principles hath an affinity with Oil. It is also a property common to all Oils to become more fluid, subtile, light, and limpid, the oftener they are distilled. On the contrary, by being incorporated with saline substances they acquire a greater consistence, and sometimes form compounds that are most solid. CHAP. XI. _Of the several Sorts of_ OILS. Oils are distinguished by the substances from which they are drawn: and as Oils are extracted from minerals, from vegetables, and from animals, there are of course Mineral, Vegetable, and Animal Oils. SECTION I. _Of_ MINERAL OILS. In the bowels of the earth we find but one sort of Oil, called _Petroleum_: its smell is strong and not disagreeable, and its colour sometimes more sometimes less yellow. There are certain mineral substances which yield by distillation a great deal of Oil very like Petroleum. This sort of substance is called a _Bitumen_, and is, indeed, nothing but an Oil rendered consistent and solid by being combined with an acid; as appears from hence, that by uniting Petroleum with the acid of vitriol we can produce an artificial Bitumen very like the native. SECTION II. _Of_ VEGETABLE OILS. Vegetable substances yield a very great quantity and variety of oils: for there is not a plant, or part of a plant, that does not contain one or more sorts thereof, generally peculiar to itself, and different from all others. By expression only, that is, by bruising and squeezing vegetable substances, particularly certain fruits and seeds, a sort of oil is obtained which has scarce any smell or taste. Oils of this sort are very mild and unctuous; and, because in this respect they resemble animal fat more than the rest do, they are called _Fat Oils_. These Oils, being exposed to the air for some time, sooner or latter grow thick, acquire an acrid taste, and a strong disagreeable smell. Some of them congeal with the smallest degree of cold. This sort of Oil is well adapted to dissolve those preparations of Lead called Litharge and Minium, with which they form a thick tenacious substance, that is used for the basis of almost all plasters. They also dissolve Lead in its metalline form; but not so easily as the sorts of calx above-mentioned; probably because its body is not so much opened, nor its parts so divided. By expression alone we also procure from certain vegetable substances another sort of Oil, which is thin, limpid, volatile, of a pungent taste, and retains the smell of the vegetable that yielded it; on which account it is called an _Essential Oil_. Of this there are several sorts, differing from one another, like the Fat Oils, according to the subjects from which they are obtained. We must observe, that it is very difficult, or rather in most cases impossible, to force from the greatest part of vegetables, by expression only, all the essential Oil they contain. For this purpose therefore recourse must be had to fire: a gentle heat, not exceeding that of boiling water, will extract all the essential Oils of vegetables; and this is the most usual and most convenient way of procuring them. The fat Oils cannot be obtained by the same method: these being much less volatile than the essential Oils, require a much greater degree of heat to raise them; which nevertheless they cannot bear without being much spoiled and entirely changed in their nature, as shall presently be shewn. All Oils, therefore, which rise with the heat of boiling water, and such alone, should be called Essential Oils. Essential Oils, in a longer or shorter time, according to the nature of each, lose the fragrant smell they had when newly distilled, and acquire another, which is strong, rancid, and much less agreeable: they also lose their tenuity, becoming thick and viscid; and in this state they greatly resemble those substances abounding in Oil which flow from certain trees, and which are called _Balsams_ or _Resins_, according as they are less or more consistent. Balsams and Resins are not soluble in water. But there are other Oily compounds which likewise run from trees; and, though not unlike Resins, are however soluble in water. These are called _Gums_; and their property of dissolving in water arises from their containing more water and more salt than Resins have; or at least their saline parts are less clogged and more disengaged. Balsams and Resins distilled with the heat of boiling water yield great quantities of a limpid, subtile, odoriferous, and, in one word, essential Oil. In the still there remains a substance thicker and more consistent than the Balsam or Resin was before distillation. The same thing happens to essential Oils which by length of time have acquired a consistence and are grown resinous. If they be re-distilled, they recover their former tenuity, leaving behind them a remainder thicker and more resinous than they themselves were. This second distillation is called the _Rectification_ of an Oil. It must be observed, that an essential Oil, combined with an acid strong enough to dissolve it, immediately becomes as thick and resinous, in consequence of this union, as if it had been long exposed to the air: which proves the consistence an Oil acquires by long keeping to be owing to this, that its lightest and less acid parts being evaporated, the proportion of its acid to the remainder is so increased, that it produces therein the same change, as an additional acid mixed with the Oil would have wrought before the evaporation. This also shews us, that Balsams and Resins are only essential Oils combined with a great proportion of acid, and thereby thickened. If vegetable substances, from which no more essential Oil can be drawn by the heat of boiling water, be exposed to a stronger heat, they yield an additional quantity of Oil; but it is thicker and heavier than the essential Oil. These Oils are black, and have a very disagreeable burnt smell, which hath made them be called _Fetid_ or _Empyreumatic_ Oils. They are moreover very acrid. It must be observed, that, if a vegetable substance be exposed to a degree of heat greater than that of boiling water, before the fat or the essential Oil is extracted from it, an empyreumatic Oil only will then be obtained; because both the fat and essential Oils, when exposed to the force of fire, are thereby burnt, rendered acrid, acquire a smell of the fire, and, in a word, become truly empyreumatic. There is ground to think, that an empyreumatic Oil is nothing else but an essential or fat Oil burnt and spoiled by the fire, and that no other Oil besides these two exists naturally in vegetables. Empyreumatic Oils, distilled and rectified several times by a gentle heat, acquire by every distillation a greater degree of tenuity, lightness, and limpidity. By this means also they lose something of their disagreeable odour; so that they gradually come nearer and nearer to the nature of essential Oils: and if the rectifications be often enough repeated, ten or twelve times for instance, they become perfectly like those Oils; except that their smell will never be so agreeable, nor like that of the substances from which they were obtained. Fat Oils may also be brought by the same means to resemble essential Oils: but neither essential nor empyreumatic Oils are capable of acquiring the properties of fat Oils. SECTION III. _Of_ ANIMAL OILS. Distillation procures us considerable quantities of Oil from all the parts of animal bodies, and especially from their fat. This Oil at first is not very fluid, and is extremely fetid: but by many rectifications it gradually acquires a great degree of clearness and tenuity, and at the same time loses much of its disagreeable odour. Animal Oils, thus rendered thin and fluid by a great number of rectifications, have the reputation of being an excellent medicine, and a specific in the epilepsy. CHAP. XII. _Of_ FERMENTATION _in general_. By Fermentation is meant an intestine motion, which, arising spontaneously among the insensible parts of a body, produces a new disposition and a different combination of those parts. To excite a Fermentation in a mixt body, it is necessary, first, that there be in the composition of that mixt a certain proportion of watery, saline, oily, and earthy parts: but this proportion is not yet sufficiently ascertained. Secondly, it is requisite that the body to be fermented be placed in a certain degree of temperate heat: for much cold obstructs fermentation; and too much heat decomposes bodies. Lastly, the concurrence of the air is also necessary to fermentation. All vegetable and animal substances are susceptible of Fermentation, because all of them contain in a due proportion the principles above specified. However, many of them want the proper quantity of water, and cannot ferment while they remain in such a state of dryness. But it is easy to supply that defect, and so render them very apt to ferment. With respect to minerals properly so called, (that is, excluding such vegetable and animal substances as may have lain long buried in the earth), they are not subject to any Fermentation; at least, that our senses can perceive. There are three sorts of Fermentation, distinguished from one another by their several productions. The first produces wines and spirituous liquors; for which reason it is called the _Vinous_ or _Spirituous Fermentation_: the result of the second is an acid liquor; and therefore it is called the _Acetous Fermentation_: and the third generates an alkaline salt; which, however, differs from the alkaline salts hitherto treated of, in this respect chiefly, that, instead of being fixed, it is extremely volatile: this last sort takes the name of the _Putrid_ or _Putrefactive Fermentation_. We shall now consider these three sorts of Fermentation and their effects a little more particularly. These three sorts of Fermentation may take place successively in the same subject; which proves them to be only three different degrees of fermentation, all proceeding from one and the same cause, rather than three distinct fermentations. These degrees of fermentation always follow the order in which we have here placed them. CHAP. XIII. _Of the_ SPIRITUOUS FERMENTATION. The juices of almost all fruits, all saccharine vegetable matters, all farinaceous seeds and grains of every kind, being diluted with a sufficient quantity of water, are proper subjects of Spirituous Fermentation. If such liquors be exposed, in vessels slightly stopped, to a moderate degree of heat, they begin in some time to grow turbid; there arises insensibly a small commotion among their parts, attended with a hissing noise; this by little and little increases, till the grosser parts appear, like little seeds or grains, moving to and fro, agitated among themselves, and thrown up to the surface. At the same time some air bubbles rise, and the liquor acquires a pungent, penetrating smell, occasioned by the very subtile vapours which exhale from it. These vapours have never yet been collected, in order to examine their nature; and they are known only by their noxious effects. They are so actively pernicious, that if a man comes rashly into a close place, where large quantities of liquors are fermenting, he suddenly drops down and expires, as if he were knocked on the head. When these several phenomena, begin to go off, it is proper to stop the fermentation, if a very spirituous liquor be required: for if it be suffered to continue longer, the liquor will become acid, and from thence proceed to its last stage, that is, to putrefaction. This is done by stopping the containing vessels very close, and removing them into a cooler place. Then the impurities precipitate, and settling at the bottom leave the liquor clear and transparent: and now the palate discovers that the sweet saccharine taste it had before fermentation is changed to an agreeable pungency, which is not acid. Liquors thus fermented are in general called _Wines_: for though in common life that word properly signifies the fermented juice of grapes only, and particular names are given to the fermented juices of other vegetable substances; as that obtained from Apples is called _Cyder_; that made from malt is called _Beer_: yet in Chymistry it is of use to have one general term denoting every liquor that has undergone this first degree of fermentation. By distillation we draw from Wine an inflammable liquor, of a yellowish white colour, light, and of a penetrating, pleasant smell. This liquor is the truly spirituous part of the wine, and the product of fermentation. That which comes off in the first distillation is commonly loaded with much phlegm and some oily parts, from which it may be afterwards freed. In this state it goes by the name of _Brandy_; but when freed from these heterogeneous matters by repeated distillations, it becomes still clearer, lighter, more fragrant, and much more inflammable, and then is called _Spirit of Wine_, and _Rectified Spirit of Wine_, or an _Ardent Spirit_, if considerably purified. The properties which distinguish an Ardent Spirit from all other substances are its being inflammable; its burning and consuming entirely, without the least appearance of smoke or fuliginosity; its containing no particles reducible to a coal; and its being perfectly miscible with water. Ardent Spirits are lighter and more volatile than any of the principles of the mixts from which they were produced, and consequently more so than the phlegm, the acid, and the oil of which they themselves consist. This arises from a particular disposition of these principles, which are in a singular manner attenuated by fermentation, and thereby rendered more susceptible of expansion and rarefaction. Ardent spirits are supposed to be the natural solvents of oils and oily matters. But it is very remarkable that they dissolve essential oils only, without touching the fat of animals, or the fat oils obtained from vegetables by expression; yet when these oils have once undergone the action of fire, they become soluble in spirit of wine, and even acquire a new degree of solubility every time they are distilled. It is not so with essential oils, which can never be rendered more soluble in ardent spirits than they are at first; and are so far from acquiring a new degree of solubility every time they are distilled, that on the contrary they even in some measure lose that property by repeated rectifications. I have taken some pains to find out the causes of these singular effects, and the result of my inquiries is published among the Memoirs of the Academy of Sciences for the year 1745. I therein consider ardent spirits as consisting of an oil, or at least a phlogiston, mixed with a portion of water, in which it is rendered soluble by means of an acid. This being laid down, I shew that the inability of spirit of wine to dissolve some oils must be imputed to its aqueous part, in which oils are not naturally soluble without the intervention of a salt: and that the power which this spirit exerts in dissolving other oils with ease, such as essential oils, must in all probability be owing to this, that in these oils it meets with the necessary saline medium, that is, with an acid, which numberless experiments shew they actually contain. On the other hand, I there prove, that the acid in essential oils is super-abundant, and in some sort foreign to their nature, or that it is but slightly connected with them, and in part deserts them every time they are distilled; which renders them less soluble after every new rectification: whereas, on the contrary, the fat expressed oils in their natural state give not the least sign of acidity, but the action of fire upon them discovers an acid which was not perceivable before. Hence I conjecture, that these oils contain no more acid than is just necessary to constitute them oils; that this acid is intimately blended with their other component parts; that it is so sheathed and entangled by these parts as to be incapable of exerting any of its properties; and that on this account these oils in their natural state are not soluble in spirit of wine: but that the disposition of their parts being gradually changed by the fire, and their acid, being by that means set more and more at liberty, at length recovers its properties, and particularly that of rendering the oily parts soluble in an aqueous menstruum: and hence it follows, that the fat oils become so much the more soluble in spirit of wine the oftener they are exposed to the action of fire. Spirit of wine doth not dissolve fixed alkalis; or at least it takes up but a very small quantity thereof; and hence ardent spirits may be freed from much of their phlegm by means of these salts thoroughly dried: for as they strongly imbibe moisture, and have even a greater affinity than ardent spirits with water, if a fixed alkali, well exsiccated, be mixed with spirit of wine that is not perfectly dephlegmated, the alkali immediately attracts its superfluous moisture, and is thereby resolved into a liquor, which, on account of its gravity, descends to the bottom of the vessel. The spirit of wine, which swims at top, is by this means as much dephlegmated, and as dry, as if it had been rectified by several distillations. As it takes up some alkaline particles in this operation, it is thereby qualified to dissolve oily matters with the greater facility. When rectified in this manner, it is called _Alcoholized Spirit of Wine_. Yet spirit of wine, even when rectified to an alcohol, is not capable of dissolving all oily matters. Those named Gums will by no means enter into any sort of union therewith; but it readily dissolves most of those which are known by the appellation of Resins. When it has dissolved a certain proportion of resinous particles it acquires a greater consistence, and forms what is called a _Spirit Varnish_, or a _Drying Varnish_, because it soon dries. This Varnish is subject to be damaged by water. Many sorts thereof are prepared, differing from each other according to the different resins employed, or the proportions in which they are used. Most of these Varnishes are transparent and colourless. Such bitumens or resins, as spirit of wine will not touch, are dissolved in oils by means of fire, and then form another kind of Varnish, which water does not hurt. These Varnishes are usually coloured, and require much longer time to dry than the Spirit Varnishes: they are called _Oil Varnishes_. Spirit of wine hath a much greater affinity with water than with oily matters: and therefore if a solution of any oil or resin in spirit of wine be mixed with water, the liquor immediately grows turbid, and acquires a whitish milky colour, owing entirely to the oily parts being separated from the spirituous menstruum by the accession of water, and too finely divided to appear in their natural form. But if the liquor stand some time quiet, several of these particles unite together, and gradually acquire a bulk sufficient to render them very perceptible to the eye. Acids have an affinity with spirit of wine, and may be combined with it. By this union they lose most of their acidity, and on that account are said to be _Dulcified_. But as these combinations of acids, especially of the vitriolic acid, with spirit of wine furnish some new productions of very singular properties, and as an examination thereof may throw much light on the nature of ardent spirits, it will not be amiss to take notice of them in this place, and consider each of them particularly. One part of highly concentrated oil of vitriol being mixed with four parts of well dephlegmated spirit of wine, there arises immediately a considerable ebullition and effervescence, attended with great heat, and abundance of vapours, which smell pleasantly, but are hurtful to the lungs. At the same time is heard a hissing like that produced by a piece of red-hot iron plunged into water. Indeed it is proper to mix the liquors very gradually; for otherwise the vessels in which the operation is performed will be in great danger of breaking. If the two liquors thus mixed be distilled with a very gentle heat, there rises first a spirit of wine of a most penetrating and grateful odour: when about half thereof is come over, what follows has a quicker and more sulphureous smell, and is also more loaded with phlegm. When the liquor begins to boil a little, there comes off a phlegm which smells very strong of sulphur, and grows gradually more acid. On this phlegm floats a small quantity of a very light and very limpid oil. In the still there remains a thick blackish substance, somewhat like a resin or bitumen. From this substance may be separated a good deal of a vitriolic but sulphureous acid. When that is extracted, there remains a black mass like a charred coal, which being put into a crucible, and exposed to a violent heat, leaves a small portion of earth, very fixed, and even vitrifiable. By rectifying the ardent spirit, which came over in distilling the above-mentioned mixture, a very singular liquor is obtained, which differs essentially both from oils and from ardent spirits, though in certain respects it resembles them both. This liquor is known in Chymistry by the name of _Æther_, and its chief properties are as follow. Æther is lighter, more volatile, and more inflammable, than the most highly rectified spirit of wine. It quickly flies off when exposed to the air, and suddenly catches fire when any flame approaches it. It burns like spirit of wine without the least smoke, and consumes entirely without leaving the smallest appearance of a coal or of ashes. It dissolves oils and oily matters with great ease and rapidity. These properties it has in common with an ardent spirit. But it resembles an oil in that it is not miscible with water; and this makes it essentially different from spirit of wine, the nature of which is to be miscible with all aqueous liquors. Another very singular property of Æther is its great affinity with gold, exceeding even that of _aqua regis_. It does not indeed dissolve gold when in a mass, and in its metalline form; but if a small quantity of Æther be added to a solution of gold in _aqua regis_, and the whole shaken together, the gold separates from the _aqua regis_, joins the Æther, and remains dissolved therein. The reason of all the phenomena above-mentioned, resulting from the mixture of spirit of wine with oil of vitriol, is founded on the great affinity between this acid and water. For if the vitriolic acid be weak, and as it were over-dosed with watery parts, neither oil nor Æther can be obtained by means thereof: but when highly concentrated, it attracts the aqueous parts very powerfully; and therefore, being mixed with spirit of wine, lays hold of most of the water contained in it, and even robs it of some portion of that which is essential to its nature, and necessary to constitute it spirit of wine: whence it comes to pass, that a certain quantity of the oily particles in its composition being separated from the watery particles, and so brought nearer to each other, they unite and assume their natural form; and thus the oil that swims at top of the sulphureous phlegm is produced. The vitriolic acid moreover thickens and even burns some of this oil; and hence comes the bituminous residuum left at the bottom of the still, which looks like the result of a vitriolic acid combined with common oil. Lastly, the vitriolic acid becomes sulphureous, as it always doth when united with oily matters, and also very aqueous, on account of the quantity of phlegm which it attracts from the spirit of wine. Æther may be considered as a spirit of wine exceedingly dephlegmated, even to such a degree that its nature is thereby changed; so that the few aqueous particles left in it are not sufficient to dissolve the oily particles and keep them asunder; which therefore being now much nearer to one another than in common spirit of wine, the liquor hath lost its property of being miscible with water. Spirit of nitre well dephlegmated, and combined with spirit of wine, presents likewise some very singular appearances. First, in the very instant of its mixture with spirit of wine, it produces a greater and more violent effervescence than the vitriolic acid occasions. Secondly, this mixture, without the help of distillation, and only by stopping the bottle in which the liquors are contained, affords a sort of Æther, produced probably by the vapours which ascend from, and swim at top of the mixture. This is a very singular liquor. Dr. Navier was the first that took notice of it, and gave a description thereof, which may be seen in the Memoirs of the Academy of Sciences. Thirdly, some authors pretend that, by distilling the mixture under consideration, an oil is obtained greatly resembling that which, as we observed above, rises from spirit of wine combined with the vitriolic acid: others again deny this. For my part, I believe the thing depends on the different concentration of the spirit of nitre, as well as on the quality of the spirit of wine, which is sometimes more sometimes less oily. Fourthly, the two liquors we are speaking of, being intimately mixed by distillation, form a liquor slightly acid, used in medicine, and known by the name of _Sweet_ or _Dulcified Spirit of Nitre_: a very proper name, seeing the nitrous acid, by uniting with the spirit of wine, actually loses almost all its acidity and corrosive quality. Fifthly and lastly, when the distillation is finished, there remains in the bottom of the vessel a thick blackish substance, nearly resembling that which is found after distilling oil of vitriol and spirit of wine. Spirit of salt hath likewise been combined with spirit of wine; but it does not unite therewith so easily or so intimately as the two acids above-mentioned. To mix them thoroughly, the spirit of salt must be highly concentrated, and smoking, and moreover the assistance of the still must be called in. Some authors pretend that from this mixture also a small quantity of oil may be obtained; which probably happens when the liquors have the qualities above-specified. The marine acid likewise, by uniting with spirit of wine, loses most of its acidity; on which account it is in like manner called _Sweet_ or _Dulcified Spirit of Salt_. A thick residuum is also found here after distillation. CHAP. XIV. _Of the_ ACETOUS FERMENTATION. Besides an ardent spirit, wine affords a great deal of water, oil, earth, and a sort of acid which shall be considered presently. When the spirituous part is separated from these other matters, they undergo no further change. But if all the constituent parts of wine remain combined together, then, after some time, shorter or longer as the degree of heat in which the wine stands is greater or less, the fermentation begins afresh, or rather arrives at its second stage. The liquor once more grows turbid, a new intestine motion arises, and, after some days, it is found changed into an acid; which, however, is very different from those hitherto treated of. The liquor then takes the name of _Vinegar_. The acetous fermentation differs from the spirituous, not only in its effect, but also in several of its concomitant circumstances. Moderate motion is of service to this, whereas it obstructs the spirituous; and it is attended with much more warmth than the spirituous. The vapours it produces are not noxious, like those of fermenting wine. Lastly, Vinegar deposites no tartar, even when the wine employed in this operation is quite new, and hath not had time to discharge its tartar: instead of tartar, Vinegar deposites a viscid matter which is very apt to putrify. It must be observed, that wine is not the only substance that is susceptible of the acetous fermentation: for several vegetable and even animal matters, which are not subject to the spirituous fermentation, turn sour before they putrify. But as vinous liquors possess in a very eminent degree the property of being susceptible of the acetous fermentation, and likewise of producing the strongest acids that can result from such fermentation, their acid shall be more particularly considered in this place. SECTION I. _Of_ VINEGAR. If wine, which has gone through this second stage of fermentation, be distilled, instead of an ardent spirit, only an acid liquor is obtained, which is called _Distilled Vinegar_. This acid has the same properties as the mineral acids of which we have already treated; that is, it unites with alkaline salts, absorbent earths, and metallic substances, and therewith forms neutral saline combinations. Its affinity with these substances observes the same order as that observed by the mineral acids with regard to the same substances; but in general it is weaker; that is, any mineral acid is capable of expelling the acid of Vinegar out of all matters with which it is united. Vinegar hath likewise a greater affinity than sulphur with alkalis: whence it follows, that it is capable of decompounding that combination of sulphur with an alkali called Liver of Sulphur, and of precipitating the sulphur it contains. The acid of Vinegar is always clogged with a certain proportion of oily parts, which greatly weaken it, and deprive it of much of its activity; and for this reason it is not near so strong as the mineral acids, which are not entangled with any oil. By distillation, indeed, it may be freed from this oil, and at the same time from the great quantity of water which in a manner suffocates it, and by that means may be brought much nearer to the nature of the mineral acids: but this attempt hath not yet been prosecuted with the assiduity it deserves. Besides distillation, there is another way of freeing Vinegar from a good deal of its phlegm; and that is, by exposing it to a hard frost, which readily congeals the watery part into ice, while the acid retains its fluidity. Vinegar, saturated with a fixed alkali, forms a neutral oily salt, of a dark colour, which is semi-volatile, melts with a very gentle heat, flames when thrown upon burning coals, and dissolves in spirit of wine, of which, however, it requires six parts to complete the solution. This solution being evaporated to dryness leaves a matter in the form of leaves lying on each other; on which account it hath obtained the name of _Terra Foliata_. The same foliated matter will be obtained, though the salt be not previously dissolved in spirit of wine; but not so readily. This salt is also called _Regenerated Tartar_. Under the head of Tartar we shall see the reason of these different appellations. Regenerated Tartar is also in some degree capable of crystallizing: for this purpose a solution thereof in water must be slowly evaporated to the consistence of a syrup, and then suffered to stand quiet in a cool place; by which means it will shoot into clusters of crystals, lying one upon another, not unlike the feathers on a quill. With Vinegar and several absorbent earths, such as calcined pearls, coral, shells of fish, _&c._ are also formed neutral saline compounds, each of which takes the name of the particular earth employed in its composition. Vinegar perfectly dissolves Lead, and converts it to a neutral metallic salt, which shoots into crystals, and has a sweet saccharine taste. This compound is called _Sugar of Lead_, or _Sal Saturni_. If Lead be exposed to the bare vapour of Vinegar, it will be thereby corroded, calcined, and converted into a white matter much used in painting, and known by the name of _Ceruse_; or, when it is finer than ordinary, _White Lead_. Vinegar corrodes Copper likewise, and converts it into a beautiful green rust, which also is used in painting; and distinguished by the name of _Verdegris_. However, Vinegar is not commonly employed to make Verdegris: for this purpose they use wine, or the rape of wine, from which fire extricates an acid analogous to that of Vinegar. In treating of the several substances which constitute wine, we mentioned an acid matter, but did not then enter into a particular examination thereof; because as that matter greatly resembles the acid of Vinegar, we thought it more proper to defer the consideration of its properties till we had treated of the acetous fermentation, and its effects. SECTION II. _Of_ TARTAR. This substance is a saline compound, consisting of earthy, oily, and especially acid parts. It is found in the form of crusts, adhering to the inner sides of vessels in which wines have stood for some time, particularly acid wines, such as those of Germany. Tartar derives its origin from the super-abundant quantity of acid contained in the juice of the grape. This superfluous acid, being more than is requisite to constitute the ardent spirit, unites with some of the oil and earth contained in the fermented liquor, and forms a kind of salt; which for some time continues suspended in that liquor, but, when the wine stands undisturbed in a cool place, is deposited, as hath been said, on the sides of the cask. Tartar in this state contains many earthy parts, which are superfluous, and foreign to its nature. From these it may be freed by boiling it repeatedly with a sort of earth found in the neighbourhood of Montpelier, as may be seen in the Memoirs of the Academy of Sciences. When it is purified, there appears on the surface of the liquor a sort of white, crystalline pellicle, which is skimmed off as it forms. This matter is called _Cream of Tartar_. The same liquor which produces this Cream, and in which the purified Tartar is dissolved, being set to cool, yields a great number of white semi-transparent crystals, which are called _Crystals of Tartar_. The Cream and the Crystals of Tartar are therefore no other than purified Tartar, and differ from each other in their form only. Though the Crystals of Tartar have every appearance of a neutral salt, yet they are far from being such; for they have all the properties of a true acid, which scarce differs from that of vinegar, except that it contains less water, and more earth and oil; to which it owes its solid form, as well as its property of not being soluble in water without much difficulty: for a very great quantity of water is requisite to keep the Crystals of Tartar in solution; and it must moreover be boiling hot; otherwise as soon as it cools most of the Tartar dissolved in it separates from the liquor, and falls to the bottom in the form of a white powder. Tartar is decomposed by calcination in the open fire. All its oily parts are consumed or dissipated in smoke, together with most of its acid. The other part of its acid, uniting intimately with its earth, forms a very strong and very pure fixed alkali, called _Salt of Tartar_. It will be shewn in its proper place, that almost every vegetable matter, as well as Tartar, leaves a fixed alkali in its ashes: yet Tartar has these peculiar properties; first, it assumes an alkaline character even when burnt or calcined in close vessels, whereas other substances acquire it only by being burnt in the open air; secondly, the alkali of Tartar is stronger and more saline than almost any that is obtained from other matters. This alkali, when thoroughly calcined, powerfully attracts the moisture of the air, and melts into an unctuous alkaline liquor, improperly called _Oil of Tartar per deliquium_. This is the alkali generally used in making the _Terra Foliata_, mentioned under the head of Vinegar; for which reason this combination is called _Terra Foliata Tartari_; a name suitable enough. But the same cannot be said of the other name, _Regenerated Tartar_, which is also given it. It is true, that on this occasion an oily acid is restored to the earth of the Tartar, analagous to that of which the fire had deprived it: but the compound thence resulting is a neutral salt which very readily dissolves in water; whereas Tartar is manifestly acid, and not soluble, or at least hardly soluble, in water. Crystals of Tartar combined with alkali of Tartar produce a great effervescence while they are mixing, as all acids usually do; and if the combination be brought exactly up to the point of saturation, a perfectly neutral salt is formed, which shoots into crystals, and easily dissolves in water; and this hath procured it the name of _Soluble Tartar_. It is also called the _Vegetable Salt_, as being obtained from vegetables only; and again, _Tartarised Tartar_, because it consists of the acid and the alkali of Tartar combined together. Crystals of Tartar combined with alkalis procured from the ashes of maritime plants, such as Soda, which alkalis resemble the basis of sea-salt, form likewise a neutral salt, which crystallizes well, and dissolves easily in water. This salt is another sort of soluble Tartar. It is called _Saignette's Salt_, from the inventor's name. Both the Vegetable Salt and Saignette's Salt are gently purgative soaps, and much used in Medicine. Tartar likewise dissolves the absorbent earths, as lime, chalk, _&c._ and with them forms neutral salts which are soluble in water[3]. It even attacks metallic bodies, and when combined with them becomes soluble. A soluble Tartar for medical use is prepared with Crystals of Tartar and Iron: the metallic salt thereby produced hath the name of _Chalybeated Soluble Tartar_. This salt attracts the moisture of the air, and is one of those which do not crystallize. [3] See Mr. Duhamel's Essays on this subject in the Memoirs of the Academy of Sciences. Crystallized Tartar acts also upon several other metallic substances: for instance, it dissolves the Regulus, Liver, and Glass of Antimony, and thence acquires an emetic quality: it is then called _Stibiated_ or _Emetic Tartar_. It likewise dissolves Lead, and therewith forms a salt which, in the figure of its crystals, resembles Tartarised Tartar. It is very extraordinary that Tartar, which of itself is not soluble in water, should be soluble therein when become a neutral salt by uniting either with alkalis or with absorbent earths, or even with metals. With respect to alkalis, indeed, it may be urged, that, having themselves a great affinity with water, they communicate to Tartar some of that facility with which they naturally unite therewith: but the same cannot be alledged concerning absorbent earths, and metallic substances, which water dissolves not at all, or at least with great difficulty, and in small quantity. This effect, therefore, must be attributed wholly to some change in the disposition of its parts which is to us unknown. All the Soluble Tartars are easily decompounded by exposing them to a certain degree of heat. In distillation they yield the same principles which are obtained from Tartar; and what remains fixed in the fire, after they are thoroughly burnt, is a compound of the alkali which Tartar naturally produces, and of the alkaline or metallic substance with which it was converted into a neutral salt. As Crystal of Tartar is the weakest of all acids, on account of the oily and earthy matters with which it is combined, Soluble Tartars are decompounded by all the acids; by any of which crystal of Tartar may be separated from the substance that serves it for a basis and renders it a neutral salt. The other acids which are procured from vegetables, and even those which are obtainable from some animal substances, may all be referred to and compared with either Vinegar or Tartar, according to the quantities of oil or earth with which they are combined. After all, these acids have not yet been thoroughly examined. There is great reason to think that they are no other than the mineral acids, which, in passing through the bodies of vegetables, and even of animals, undergo a considerable change, especially by contracting an union with oily matters. For, as we said before in treating of Vinegar, by freeing them from their oil they are brought very near to the nature of mineral acids; and so likewise the mineral acids acquire many of the properties of vegetable acids by being combined with oils. CHAP. XV. _Of the_ PUTRID FERMENTATION, _or_ PUTREFACTION. Every body which hath gone through the two stages of fermentation above described, that is, the spirituous and the acetous fermentation, being left to itself in a due degree of warmth, which varies according to the subject, advances to the last stage of fermentation; that is, to putrefaction. It is proper to observe, before we go any further, that the converse of this proposition is not true; that is, it is not necessary that a body should successively pass through the spirituous and the acetous fermentation, before it can arrive at the putrid; but that, as certain substances fall into the acetous without having gone through the spirituous fermentation, so others begin to putrify without having undergone either the spirituous or the acetous fermentation; of which last kind are, for instance, most animal substances. When therefore we represented these three sorts of fermentation as three different degrees or stages of one and the same fermentation, we supposed it to be excited in a body susceptible of fermentation in its full extent. However, there is still room to think that every substance which is capable of fermenting always passes necessarily through these three different stages; but that the substances most disposed thereto pass with such rapidity through the first, and even the second, that they arrive at the third before our senses can perceive the least signs of either of the two former. This opinion is not destitute of probability: yet it is not supported by proofs sufficiently strong and numerous to compel our assent. When a body is in a putrefying state it is easy to discover (as in the two sorts of fermentation already treated of) by the vapours which rise from it, by the opacity which invades it, if a pellucid liquor, and frequently even by a greater degree of heat than is found in the two other sorts of fermentation, that an intestine motion is begun among its constituent parts, which lasts till the whole be entirely putrefied. The effect of this intestine motion is in this, as in the two other sorts of fermentation, to break the union, and change the disposition, of the particles constituting the body in which it is excited, and to produce a new combination. This is brought about by a mechanism to which we are strangers, and concerning which nothing beyond conjectures can be advanced: but these we neglect, resolving to keep wholly to facts, as the only things in Natural Philosophy that are positively certain. If, then, we examine a substance that has undergone putrefaction, we shall soon perceive that it contains a principle which did not exist in it before. If this substance be distilled, there rises, first, by means of a very gentle heat, a saline matter which is exceedingly volatile, and affects the organ of smelling briskly and disagreeably. Nor is the aid of distillation necessary to discover the presence of this product of putrefaction: it readily manifests itself in most substances where it exists, as any one may soon be convinced by observing the different smell of fresh and of putrefied urine; for the latter not only affects the nose, but even makes the eyes smart, and irritates them so as to draw tears from them in abundance. This saline principle which is the product of putrefaction, when separated from the other principles of the body which affords it, and collected by itself, appears either in the form of a liquor, or in that of a concrete salt, according to the different methods used to obtain it. In the former state it is called a _Volatile Urinous Spirit_; and in the latter a _Volatile Urinous Salt_. The qualification of urinous is given it, because, as was said, a great deal thereof is generated in putrefied urine, to which it communicates its smell. It goes also by the general name of a _Volatile Alkali_, whether in a concrete or in a liquid form. The enumeration of its properties will shew why it is called an alkali. Volatile Alkalis, from whatever substance obtained, are all alike, and have all the same properties; differing only according to their degrees of purity. The Volatile Alkali, as well as the Fixed, consists of a certain quantity of acid combined with and entangled by a portion of the earth of the mixt body from which it was obtained; and on that account it has many properties like those of a Fixed Alkali. But there is moreover in its composition a considerable quantity of a fat or oily matter, of which there is none in a Fixed Alkali; and on this account again there is a great difference between them. Thus the Volatility of the Alkali produced by putrefaction, which is the principal difference between it and the other kind of Alkali whose nature it is to be Fixed, must be attributed to the portion of oil which it contains: for there is a certain method of volatilizing Fixed Alkalis by means of a fatty substance. Volatile Alkalis have a great affinity with acids, unite therewith rapidly and with ebullition, and form with them neutral salts, which shoot into crystals, but differ from one another according to the kind of acid employed in the combination. The neutral salts which have a Volatile Alkali for their basis are in general called _Ammoniacal Salts_. That whose acid is the acid of sea-salt is called _Sal Ammoniac_. As this was the first known, it gave name to all the rest. Great quantities of this salt are made in Egypt, and thence brought to us. They sublime it from the soot of cow's dung, which is the fuel of that country, and contains sea-salt, together with a Volatile Alkali, or at least the materials proper for forming it; and consequently all the ingredients that enter into the composition of Sal Ammoniac. See the Memoirs of the Academy of Sciences. The neutral salts formed by combining the acids of nitre and of vitriol with a Volatile Alkali are called, after their acids, _Nitrous Sal Ammoniac_, and _Vitriolic Sal Ammoniac_: the latter, from the name of its inventor, is also called Glauber's _Secret Sal Ammoniac_. A Volatile Alkali, then, has the same property as a Fixed Alkali with regard to acids: yet they differ in this, that the affinity of the former with acids is weaker than that of the latter: and hence it follows, that any Sal Ammoniac may be decompounded by a Fixed Alkali, which will lay hold of the acid, and discharge the Volatile Alkali. A Volatile Alkali will decompound any neutral salt which has not a Fixed Alkali for its basis; that is, all such as consist of an acid combined with an absorbent earth or a metallic substance. By joining with the acids in which they are dissolved, it disengages the earths or metallic substances, takes their place, and, in conjunction with their acids, forms Ammoniac Salts. Hence it might be concluded, that, of all substances, next to the Phlogiston and the Fixed Alkalis, Volatile Alkalis have the greatest affinity with acids in general. Yet there is some difficulty in this matter: for absorbent earths, and several metallic substances, are also capable of decompounding Ammoniacal Salts, discharging their volatile Alkali, and forming new compounds by uniting with their acids. This might induce us to think, that these substances have nearly the same affinity with acids. But it is proper to observe, that a Volatile Alkali decompounds such neutral salts as have for their basis either an absorbent earth or a metallic substance, without the aid of fire; whereas absorbent earths or metallic substances will not decompound an Ammoniacal Salt, unless they be assisted by a certain degree of heat. Now, as all these matters are extremely fixed, at least in comparison with a Volatile Alkali, they have the advantage of being able to resist the force of fire, and so of acting in conjunction therewith; and fire greatly promotes the natural action of substances upon one another: whereas the Volatile Alkali in the Ammoniacal Salt, being unable to abide the force of fire, is compelled to desert its acid; and that so much the more quickly, as its affinity therewith is considerably weakened by the presence of an earthy or metallic substance, both of which have a great affinity with acids. These considerations oblige us to conclude, that Volatile Alkalis have a somewhat greater affinity, than absorbent earths and metallic substances, with acids. Ammoniacal Salts projected upon nitre in fusion make it detonate; and the Nitrous Sal Ammoniac detonates by itself, without the addition of any inflammable matter. This singular effect evidently demonstrates the existence of an oily matter in Volatile Alkalis; for it is certain that nitre will never deflagrate without the concurrence, and even the immediate contact, of some combustible matter. This oily substance is often found combined with Volatile Alkalis in such a large proportion as to disguise it, in some measure, and render it exceedingly foul. The salt may be freed from its superfluous oil by repeated sublimations; and particularly by subliming it from absorbent earths, which readily drink up oils. This is called the _Rectification_ of a Volatile Alkali. The salt, which before was of a yellowish or dirty colour, by being thus rectified becomes very white, and acquires an odour more pungent and less fetid than it had at first, that is, when obtained by one single distillation from a putrid substance. It is proper to observe, that the rectification of a Volatile Alkali must not be carried too far, or repeated too often; for by that means it may be entirely decomposed at length; and particularly if an absorbent earth, and especially chalk, be employed for that purpose, the salt may be converted into an oil, an earth, and water. Volatile Alkalis act upon several metallic substances, and particularly on copper; of which they make a most beautiful blue solution. On this property depends a pretty singular effect, which happens sometimes when we attempt, by means of a Volatile Alkali, to separate copper from any acid with which it is combined. Instead of seeing the liquor grow turbid, and the metal fall, both which generally happen when any Alkali whatever is mixed with a metallic solution, we are surprised to observe the solution of copper, upon adding a Volatile Alkali, retain its limpidity, and let fall no precipitate; or at least, if the liquor does grow turbid, it remains so but for a moment, and instantly recovers its transparency. This is occasioned by adding such a quantity of Volatile Alkali as is more than sufficient fully to saturate the acid of the solution, and considerable enough to dissolve all the copper as fast as it is separated from the acid. On this occasion the liquor acquires a deeper blue than it had before; which arises from the property which Volatile Alkalis have of giving this metal, when combined with them, a fuller blue than any other solvent can: hence we have a touchstone to discover copper wherever it is; for let the quantity of this metal combined with other metals be ever so small, a Volatile Alkali never fails to discover it, by making it appear of a blue colour. Though a Volatile Alkali be constantly the result of putrefaction, yet it must not therefore be imagined that none can be produced by any other means; on the contrary, most of those substances which contain the ingredients necessary to form it, yield no inconsiderable quantity thereof in distillation. Tartar, for example, which by being burnt in an open fire is converted, as was shewn, into a Fixed Alkali, yields a Volatile Alkali when it is decomposed in close vessels; that is, when it is distilled; because, in this latter case, the oily part is not dissipated or burnt, as it is by calcination in a naked fire, but has time to unite with some of the earth and acid of the mixt, in such a manner as to form a true Volatile Alkali. To prove that on this occasion, as well as on all others, where unputrefied bodies yield a Volatile Alkali, this salt is the product of the fire, we need only observe, that in these distillations it never rises till after some part of the phlegm, of the acid, and even of the thick oil of the mixt, is come over; which never is the case when it is formed beforehand in the body which is the subject of the operation, as it is in those which have undergone putrefaction: for this salt, being much lighter and more volatile than those other substances, rises of course before them in distillation. CHAP. XVI. _A General View of_ CHYMICAL DECOMPOSITION. Though we have considered all the substances which enter into the composition of Vegetables, Animals, and Minerals, whether as primary or as secondary principles, it will not be improper to shew in what order we obtain these principles from the several mixts; and especially from Vegetables and Animals, because they are much more complicated than Minerals. This is called _Analysing_ a compound. The method most commonly taken to decompose bodies is by applying to them successive degrees of heat, from the gentlest to the most violent, in appropriated vessels, so contrived as to collect what exhales from them. By this means the principles are gradually separated from each other; the most volatile rise first, and the rest follow in order, as they come to be acted on by the proper degree of heat: and this is called _Distillation_. But it being observed that fire, applied to the decomposition of bodies, most commonly alters their secondary principles very sensibly, by combining them in a different manner with each other, or even partly decomposing them, and reducing them to their primitive principles; other means have been used to separate those principles without the help of fire. With this view the mixts to be decomposed are forcibly compressed, in order to squeeze out of them all such parts of their substance as they will by this means part with: or else those mixts are for a long time triturated, either along with water, which carries off all their saline and saponaceous contents, or with solvents, such as ardent spirits, capable of taking up every thing in them that is of an oily or resinous nature. We shall here give a succinct account of the effects of these different methods, as applied to the principal substances among Vegetables and Animals, and likewise to some Minerals. SECTION I. _The_ ANALYSIS _of_ VEGETABLE SUBSTANCES. A vast many vegetable substances, such as kernels and seeds, yield, by strong compression, great quantities of mild, fat, unctuous Oils, which are not soluble in ardent spirits: these are what we called _Expressed Oils_. They are also sometimes called _Fat Oils_, on account of their unctuousness, in which they exceed all other sorts of Oil. As these oils are obtained without the aid of fire, it is certain that they existed in the mixt just as we see them, and that they are not in the least altered: which could not have been the case had they been obtained by distillation; for that never produces any Oils but such as are acrid and soluble in spirit of wine. Some vegetable matters, such as the rind of citrons, lemons, oranges, _&c._ also yield, only by being squeezed between the fingers, a great deal of Oil. This spirts out in fine small jets, which being received upon any polished surface, such as a looking glass, run together and form a liquor that is a real Oil. But it must be carefully noted, that this sort of Oil, though obtained by expression only, is nevertheless very different from the Oils mentioned before, to which the title of _Expressed Oils_ peculiarly belongs: for this is far lighter and thinner; moreover, it retains the perfect odour of the fruit which yields it, and is soluble in spirit of wine; in a word, it is a true essential Oil, but abounds so in the fruits which produce it, and is lodged therein in such a manner, occupying a vast number of little cells provided in the peel for its reception, that a very slight pressure discharges it; which is not the case with many other vegetables that contain an essential Oil. Succulent and green plants yield by compression a great deal of liquor or juice, which consists of most of the phlegm, of the salts, and a small portion of the oil and earth of the plant. These juices, being set in a cool place for some time, deposite saline crystals, which are a combination of the acid of the plant with part of its oil and earth, wherein the acid is always predominant. These salts, as is evident from the description here given, bear a great resemblance to the tartar of wine treated of above. They are called _Essential Salts_; so that Tartar might likewise be called the _Essential Salt of Wine_. Dried plants, and such as are of a ligneous, or acid nature, require to be long triturated with water, before they will yield their essential salts. Trituration with water is an excellent way to get out of them all their saline and saponaceous contents. A vegetable matter that is very oily yields its essential salt with much difficulty, if at all; because the excessive quantity of oil entangles the salt so that it cannot extricate itself or shoot into crystals. Mr. Gerike, in his _Principles of Chymistry_, says, that if part of the oil of a plant be extracted by spirit of wine, its essential salt may be afterwards obtained with more ease and in greater quantity. This must be a very good method for such plants as have an excessive proportion of essential oil; but will not succeed if the essential salt be hindered from crystallizing by a redundancy of fat oil, because fat oils are not soluble in spirit of wine. Essential Salts are among those substances which cannot be extracted from mixts by distillation: for the first impression of fire decomposes them. Though the acid which predominates in the Essential Salts of plants, be most commonly analogous to the vegetable acid, properly so called, that is, to the acid of vinegar and tartar, which is probably no other than the vitriolic acid disguised; yet it sometimes differs therefrom, and somewhat resembles the nitrous or the marine acid. This depends on the places where the plants grow which produce these salts: if they be maritime plants, their acid is akin to the acid of sea-salt; if on the contrary they grow upon walls, or in nitrous grounds, their acid is like that of nitre. Sometimes one and the same plant contains salts analogous to all the three mineral acids; which shews that the vegetable acids are no other than the mineral acids variously changed by circulating through plants. Liquors containing the Essential Salts of plants being evaporated by a gentle heat to the consistence of honey, or even further, are called _Extracts_. Hence it is plain, that an Extract is nothing but the essential salt of a plant, combined with some particles of its oil and earth, that remained suspended in the liquor, and are now incorporated by evaporation. Extracts of plants are also prepared by boiling them long in water, and then evaporating some part of it. But these Extracts are of inferior virtue; because the fire dissipates many of the oily and saline parts. EMULSIONS. Substances which abound much in Oil, being bruised and triturated with water for some time, afford a liquor of an opaque dead-white colour, like milk. This liquor consists of such juices as the water is capable of dissolving, together with a portion of the oil, which being naturally indissoluble in water, is only divided and dispersed in the liquor, the limpidity whereof is by that means destroyed. This sort of oily liquor, in which the oil is only divided, not dissolved, is called an _Emulsion_. The oily particles in Emulsions spontaneously separate from the water, when left at rest, and uniting into greater masses rise, on account of their lightness, to the surface of the liquor, which by that means recovers a degree of transparency. If vegetables abounding in essential oils and resins be digested in spirit of wine, the menstruum takes up these oily matters, as being capable of dissolving them; and they may afterwards be easily separated from it by the affusion of water. The water, with which spirit of wine has a greater affinity than with oily matters, separates them by this means from their solvent, agreeably to the common laws of affinities. Without the help of fire, scarce any thing, besides the substances already mentioned, can be obtained from a plant: but, by the means of distillation, we are enabled to analyse them more completely. In prosecuting this method of extracting from a plant the several principles of which it consists, the following order is to be observed. A plant being exposed to a very gentle heat, in a distilling vessel set in the _balneum mariæ_, yields a water which retains the perfect smell thereof. Some Chymists, and particularly the illustrious Boerhaave, have called this liquor the _Spiritus Rector_. The nature of this odoriferous part of plants is not yet thoroughly known; because it is so very volatile that it is difficult to subject it to the experiments necessary for discovering all its properties. If, instead of distilling the plant in the _balneum mariæ_, it be distilled over a naked fire, with the precaution of putting a certain quantity of water into the distilling vessel along with it, to prevent its suffering a greater heat than that of boiling water, all the essential oil contained in that plant will rise together with that water, and with the same degree of heat. On this occasion it must be observed, that no essential oil can be obtained from a plant after the _Spiritus Rector_ hath been drawn off; which gives ground to think that the volatility of these oils is owing to that spirit. The heat of boiling water is also sufficient to separate from vegetable matters the fat oils which they contain. That, however, is to be done by the way of decoction only, and not by distillation: because, though these oils will swim on water, yet they will not rise in vapours without a greater degree of heat. When the essential oil is come over, if the plant be exposed to a naked fire, without the addition of water, and the heat be increased a little, a phlegm will rise that gradually grows acid; after which, if the heat be increased as occasion requires, there will come over a thicker and heavier oil; from some a volatile alkali; and last of all, a very thick, black, empyreumatic oil. When nothing more rises with the strongest degree of heat, there remains of the plant a mere coal only, called the _Caput Mortuum_, or _Terra Damnata_. This coal when burnt falls into ashes, which, being lixiviated with water, give a fixed alkali. It is observable, that in the distillation of plants which yield an acid and a volatile alkali, these two salts are often found quite distinct and separate in the same receiver; which seems very extraordinary, considering that they are naturally disposed to unite, and have a great affinity with one another. The reason of this phenomenon is, that they are both combined with much oil, which embarrasses them so that they cannot unite to form a neutral salt, as they would not fail to do were it not for that impediment. All vegetables, except such as yield a great deal of volatile alkali, being burnt in an open fire, and so as to flame, leave in their ashes a large quantity of an acrid, caustic, fixed alkali. But if care be taken to smother them, so as to prevent their flaming while they burn, by covering them with something that may continually beat down again what exhales, the salt obtained from their ashes will be much less acrid and caustic; the cause whereof is, that some part of the acid and oil of the plant being detained in the burning, and stopped from being dissipated by the fire, combines with its alkali. These salts crystallize, and, being much milder than the common fixed alkalis, may be used in medicine, and taken internally. They are called _Tachenius's Salts_, because invented by that Chymist. Marine plants yield a fixed alkali analogous to that of sea-salt. As for all other plants or vegetable substances, the fixed alkalis obtained from them, if rightly prepared and thoroughly calcined, are all perfectly alike, and of the very same nature. The last observation I have to make on the production of fixed alkalis is, that if the plant you intend to work upon be steeped or boiled in water before you burn it, a much smaller quantity of salt will be obtained from it; nay, it will yield none at all, if repeated boilings have robbed it entirely of those saline particles which must necessarily concur with its earth to form a fixed Alkali. SECTION II. _The_ ANALYSIS _of_ ANIMAL SUBSTANCES. Succulent animal substances, such as new-killed flesh, yield by expression a juice or liquid, which is no other than the phlegm, replete with all the principles of the animal body, except the earth, of which it contains but little. The hard or dry parts, such as the horns, bones, _&c._ yield a similar juice, by boiling them in water. These juices become thick, like a glue or jelly, when their watery parts are evaporated; and, in this state, they are truly extracts of animal matters. These juices afford no crystals of essential salt, like those obtained from vegetables, and shew no sign either of an acid or an alkali. Great part of the oil which is in the flesh of animals may be easily separated without the help of fire; for it lies in a manner by itself: it is commonly in a concrete form, and is called _Fat_. This oil somewhat resembles the fat oils of vegetables; for like them it is mild, unctuous, indissoluble in spirit of wine, and is subtilized and attenuated by the action of fire. But there is not in animals, as in vegetables, any light essential oil, which rises with the heat of boiling water; so that, properly speaking, animals contain but one sort of oil. Few animal substances yield a perceptible acid. Ants and bees are almost the only ones from which any can be obtained: and indeed the quantity they yield is very small, as the acid itself is extremely weak. The reason thereof is, that as animals do not draw their nourishment immediately from the earth, but feed wholly either on vegetables or on the flesh of other animals, the mineral acids, which have already undergone a great change by the union contracted between them and the oily matters of the vegetable kingdom, enter into a closer union and combination with these oily parts while they are passing through the organs and strainers of animals; whereby their properties are destroyed, or at least so impaired, that they are no longer sensible. Animal matters yield in distillation, first, a phlegm, and then, on increasing the fire, a pretty clear oil, which gradually becomes thicker, blacker, more fetid, and empyreumatic. It is accompanied with a great deal of volatile alkali; and if the fire be raised and kept up till nothing more comes over, there will remain in the distilling vessel a coal like that of vegetables; except that when it is reduced to ashes, no fixed alkali, or at least very little, can be obtained from them, as from the ashes of vegetables. This arises from hence, that, as we said before, the saline principle in animals being more intimately united with the oil than it is in plants, and being consequently more attenuated and subtilized, is too volatile to enter into the combination of a fixed alkali; on the contrary, it is more disposed to join in forming a volatile alkali, which on this occasion does not rise till after the oil, and therefore must certainly be the production of the fire. It must be observed, that all we have hitherto said concerning the analysis of bodies must be understood of such matters only as have not undergone any sort of Fermentation. The chyle and milk of animals which feed on plants still retain some likeness to vegetables; because the principles of which these liquors are composed have not gone through all the changes which they must suffer before they enter into the animal combination. Urine and sweat are excrementitious aqueous liquors, loaded chiefly with the saline particles which are of no service towards the nourishment of the animal, but pass through its strainers without receiving any alteration; such as the neutral salts which have a fixed alkali for their basis, and particularly the sea-salt, which happens to be in the food of animals, whether it exist therein naturally, as it does in some plants, or whether the animals eat it to please their palates. The saliva, the pancreatic juice, and especially the bile, are saponaceous liquors, that is, they consist of saline and oily particles combined together: so that being themselves dissolved in an aqueous liquor, they are capable of dissolving likewise the oily parts, and of rendering them miscible with water. Lastly, the blood being the receptacle of all these liquors partakes of the nature of each, more or less in proportion to the quantity thereof which it contains. SECTION III. _The_ ANALYSIS _of_ MINERAL SUBSTANCES. Minerals differ greatly from vegetables, and from animals; they are not near so complex as those organized bodies, and their principles are much more simple; whence it follows, that these principles are much more closely connected, and that they cannot be separated without the help of fire; which not having on their parts the same action and the same power as on organized bodies, hath not the same ill effect on them; I mean the effect of changing their principles, or even destroying them entirely. I do not here speak of pure, vitrifiable, or refractory earths; of mere metals and semi-metals; of pure acids; or even of their simplest combinations, such as sulphur, vitriol, alum, sea-salt: of all these we have said enough. We are now to treat of bodies that are more complex, and therefore more susceptible of decomposition. These bodies are compound masses, or combinations of those above-mentioned; that is, metallic substances as they are found in the bowels of the earth, united with several sorts of sand, stones, earths, semi-metals, sulphur, _&c._ When the metallic matter is combined with other matters, in such a proportion to the rest that it may be separated from them with advantage and profit, these compounds are called _Ores_; when the case is otherwise, they are called _Pyrites_, and _Marcasites_; especially if sulphur or arsenic be predominant therein, which often happens. In order to analyse an ore, and get out of it the metal it contains, the first step is to free it from a great deal of earth and stones, which commonly adhere to it very slightly and superficially. This is effected by pounding the ore, and then washing it in water; to the bottom of which the metalline parts presently sink, as being the heaviest, while the small particles of earth and stone remain suspended some time longer. Thus the metallic part is left combined with such matters only as are most intimately complicated with it. These substances are most commonly sulphur and arsenic. Now, as they are much more volatile than other mineral matters, they may be dissipated in vapours, or the sulphur may be consumed, by exposing the ore which contains them to a proper degree of heat. If the sulphur and arsenic be desired by themselves, the fumes thereof may be catched and collected in proper vessels and places. This operation is called _Roasting_ an Ore. The metal thus depurated is now fit to be exposed to a greater force of fire, capable of melting it. On this occasion the semi-metals and the imperfect metals require the addition of some matter abounding in phlogiston, particularly charcoal-dust; because these metallic substances lose their phlogiston by the action of the fire, or of the fluxes joined with them, and therefore without this precaution would never acquire either the splendour or the ductility of a metal. By this means the metallic substance is more accurately separated from the earthy and stony parts, of which some portion always remains combined therewith till it is brought to fusion. For, as we observed before, a metallic glass or calx only will contract an union with such matters; a metal possessed of its phlogiston and metalline form being utterly incapable thereof. We took notice of the cause of this separation above, where we shewed that a metal possessed of its phlogiston and metalline form will not remain intimately united with any calcined or vitrified matter, not even with its own calx or glass. The metal therefore on this occasion gathers into a mass, and lies at the bottom of the vessel, as being most ponderous; while the heterogeneous matters float upon it in the form of a glass, or a semi-vitrification. These floating matters take the name of _Scoriæ_, and the metalline substance at bottom is called the _Regulus_. It frequently happens, that the metalline regulus thus precipitated is itself a compound of several metals mixed together, which are afterwards to be separated. We cannot at present enter into a detail of the operations necessary for that purpose: they will appear in our Treatise of _Practical Chymistry_: but the principles on which they are founded may be deduced from what we have said above, concerning the properties of the several metals and of acids. It is proper to observe, before we quit this subject, that the rules here laid down for analysing ores are not absolutely general: for example, it is often adviseable to roast the ore before you wash it; for by that means some ores are opened, attenuated, and made very friable, which would cost much trouble and expence, on account of their excessive hardness, if you should attempt to pound them without a previous torrefaction. It is also frequently necessary to separate the ore from part only of its stone; sometimes to leave the whole; and sometimes to add more to it, before you smelt it. This depends on the quality of the stone, which always helps to promote fusion when it is in its own nature fusible and vitrifiable. It is then called the _Fluor_ of the ore: but of this we must say, as we did of the preceding article, it is sufficient for our present purpose to lay down the fundamental principles on which the reason of every process is built; the description of the operations themselves being reserved for our second Part. We shall now give a succinct account of the principal ores and mineral bodies, contenting ourselves with just pointing out the particulars of which they severally consist. _Of the_ PYRITES. _The yellow Pyrites._ The yellow Pyrites is a mineral consisting of sulphur, iron, an unmetallic earth, and frequently a little copper: the sulphur, which is the only one of these principles that is volatile, may be separated from the rest by sublimation: it usually makes a fourth, and sometimes a third, of the whole weight of these Pyrites. The other principles are separated from one another by fusion and reduction with the phlogiston, which, by metallizing the ferruginous and cupreous earths, parts them from the unmetallic earth: for this earth vitrifies, and cannot afterwards continue united with metallic matters possessed of their metalline form, as hath been said before. There is yet another way of decomposing the yellow Pyrites, which is to let it ly till it effloresces, or begins to shoot into flowers; which is nothing but a sort of slow accension of the sulphur it contains. The sulphur being by this means decomposed, its acid unites with the ferruginous and cupreous parts of the Pyrites, and therewith forms green and blue vitriols; which may be extracted by steeping in water the Pyrites which has effloresced or been burnt, and then evaporating the lixivium to a pellicle; for by this means the vitriol will shoot into crystals. Sometimes the Pyrites contains also an earth of the same nature with that of alum; a Pyrites of this sort, after flowering, yields alum as well as vitriol. _The white Pyrites._ The white Pyrites contains much arsenic, a ferruginous earth, and an unmetallic earth. The arsenic, being a volatile principle, may be separated by sublimation or distillation from the rest, which are fixed: and these again may be disjoined from each other by fusion and reduction, as was said in relation to the yellow Pyrites. _The Copper Pyrites._ The Copper Pyrites contains sulphur, copper, and an unmetallic earth. A great deal thereof likewise holds arsenic, and its colour approaches more or less to orange, yellow, or white, according to the quantity of arsenic in it. It may be decomposed by the same means as the yellow and white Pyrites. _Of_ ORES. _Of Gold Ores._ Gold being constantly found in its metalline form, and never combined with sulphur and arsenic, its matrices are not, properly speaking, ores; because the metal contained in them is not mineralized. The gold is only lodged between particles of stone, earth, or sand, from which it is easily separated by lotion, and by amalgamation with quick-silver. The gold thus found is seldom pure, but is frequently alloyed with more or less silver, from which it is to be separated by quartation. It is also very common to find gold in most ores of other metals or semi-metals, and even in the Pyrites; but the quantity contained therein is generally so small, that it would not pay the cost of extracting it. However, if any should incline to attempt it, merely out of curiosity, it would be necessary to begin with treating these ores in the manner proper for separating their metalline part; then to cupel the metalline regulus so obtained; and, lastly, to refine it by quartation. _Of Silver Ores._ It is no rare thing to find silver, as well as gold, in its metalline form, only lodged in sundry earths and stony matters, from which it may be separated in the same manner as gold. But the greatest quantities of this metal are usually dug out of the bowels of the earth in a truly mineral state: that is, combined with different substances, and particularly with sulphur and arsenic. Several silver ores are distinguished by peculiar characteristics, and are accordingly denoted by particular names. That which is called the _Vitreous Silver Ore_, is scarce any thing else but a combination of silver and sulphur. Another is known by the name of the _Horny Silver Ore_, because when in thin plates it is semi-transparent: in this ore the silver is mineralized by sulphur and a little arsenic. The _Red Silver Ore_ is of the colour which its name imports, sometimes more, sometimes less vivid; and is chiefly composed of silver, arsenic, and sulphur: it also contains a little iron. These three ores are very rich in silver: the first contains nearly three fourths of its weight, and the others about two thirds of theirs. There is a fourth, called the _White Silver Ore_, which, though it be heavier, is not so rich in silver, because it contains much copper. Many other minerals contain silver, yet are not, properly speaking, silver ores; because a much greater quantity of other metals than of silver is found in them. When a silver ore is to be decomposed, in order to have the silver pure, or when silver is to be extracted out of any ore that contains it, the first thing to be done is to roast the ore, in order to clear it of the volatile minerals: and as silver cannot be had pure without the operation of the cupel, which requires more or less lead to be joined with it, it is usual to mix with the torrified silver ore a quantity of lead, proportioned to that of the heterogeneous matters combined with the silver, and to melt the whole together. Part of the added lead vitrifies during the fusion, and at the same time converts some of the heterogeneous matters also into glass, with which it forms a scoria that rises to the surface of the matter. The other part of the lead, with which the silver is mixed, falls to the bottom in the form of a regulus, which must be cupelled in order to have the silver pure. _Of Copper Ores._ Copper is much seldomer found in a metalline form than gold or silver: it is commonly in a mineral state: it is mineralized by sulphur and arsenic: almost all its ores contain also more or less of iron; sometimes a little silver, or even gold, together with unmetallic earths and stones, as all ores do. Most copper ores are of a beautiful green or blue, or else in shades blended of these two colours. The minerals called _mountain green_, and _mountain blue_, are true copper ores; not in the form of hard stones, like other ores, but crumbly and friable like earth. Nevertheless, there are several copper ores of different colours, as ash-coloured, whitish, and shaded with yellow or orange; which colours arise from the different proportions of arsenic, sulphur, and iron, which these ores contain. In order to decompose a copper ore, and to extract the copper it contains, it is first of all to be freed from as many of its earthy, stony, sulphureous, and arsenical parts, as is possible, by roasting and washing; then what remains is to be mixed with a flux, compounded of a fixed alkali and some inflammable matter; a little sea-salt is to be put over all, and the whole melted by a strong fire. The salts facilitate the fusion and scorification of the unmetallic matters, and therewith form a slag, which being the lightest rises to the surface. The metalline matters are collected below in the form of a shining regulus of copper; which, however, is not usually fine copper, but requires to be purified in the manner to be shewn in our second part. In order to separate the copper from the unmetallic matters, it is absolutely necessary to melt its ore along with inflammable substances abounding in phlogiston. For, as this metal is not possessed of its metalline form while it is in a mineral state, as it is destitute of the true quantity of phlogiston, and, though it were not, would lose it by the action of the fire, it would come to pass, that if its ore were melted without the addition of any inflammable matter, the cupreous earth or calx would be scorified and confounded with the unmetallic matters; and as all metallic matters, except gold and silver, are subject to this inconvenience as well as copper, the addition of an inflammable substance, in fluxing all ores that contain them, is a general rule that ought constantly to be observed. _Of Iron Ores._ Iron is seldom found pure and malleable in the earth; yet it is much seldomer found in the mineral state, properly so called, than any of the other metals: for most iron ores are scarce any thing more than a ferruginous earth mixed in different proportions with unmetallic earths and stones. Some of them, however, contain also volatile minerals, such as sulphur and arsenic; and therefore it is necessary to roast the iron ores, like all others, before you attempt to extract the metal out of them. That being done, they are to be smelted with a flux consisting of fusible and inflammable matters, as the general rule directs. Iron is the commonest of all metals: nay, it is so universally diffused through the earth, that it is difficult to find any stone, earth, or sand, that does not contain some of it; and therefore none of these are usually considered and treated as iron ores, except such as contain a great deal of that metal, and melt easily. The hematites, emery, yellow pyrites, calamine, all contain a pretty considerable quantity of iron; but no body attempts to extract it from them, because they are very hard to melt. Ferruginous earth being naturally of an orange colour, a stone or earth may be judged to contain iron, if either naturally, or after roasting, it appears to have one shade of yellow or red. The singular property which iron has of being attracted by the magnet, and of being the only body, exclusive of all others, that is so, likewise affords us an easy method of discovering the presence of this metal among other matters, where it often exists in such a small quantity that it could not otherwise be found out. For this purpose the body in which iron is suspected to lurk, must be pulverised and torrefied with some inflammable matter; and then the powder thus roasted being touched with a magnet, or an animated bar, if it contains any particles of iron they will infallibly adhere to the magnet or bar. _Of Tin Ores._ Tin is never found in the earth pure and malleable, but always in a mineral state, and always mineralized by arsenic. Tin ores are not sulphureous; whence it comes, that though tin be the lightest of all metals, its ores are nevertheless heavier than those of other metals, as arsenic greatly exceeds sulphur in gravity. Some tin ores contain also a little iron. The ores of tin are to be washed, roasted, and smelted with a reducing flux, according to the general rules. _Of Lead Ores._ Lead, like tin, is never found but in a mineral state. It is most commonly mineralized by sulphur; yet there are some lead ores which also contain arsenic. Lead ores, as well as others, must be roasted and smelted with a reducing flux: however, as it is difficult to free them from all their sulphur by torrefaction only, the reducing flux employed in their fusion may be made up with a quantity of iron filings, which being incapable of any union with lead, and having a much greater affinity than that metal with sulphur, will, on this occasion, be of great service by interposing between them. _Of Quick-silver Ores._ Running Mercury is sometimes found in certain earths, or grey, friable stones; but most commonly in a mineral state. It is always mineralized by sulphur, and by sulphur alone: so that cinabar is the only ore of quick-silver that we know of; and a very rich one it is, seeing it contains six or seven times as much mercury as sulphur. Roasting can be of no use towards decomposing the ore of mercury, and separating its sulphur; because mercury being itself very volatile would be carried off by the fire together with the sulphur. In order, therefore, to part the two substances of which cinabar consists, recourse must necessarily be had to some third body, which will unite with one of them, and by that means separate it from the other. Now all the metals, except gold, having a greater affinity than mercury with sulphur, such a body is easily found: any metal but gold may be employed with success in this decomposition; but as iron hath a greater affinity with sulphur than any of the rest, and is moreover the only one that cannot unite with mercury, it must, on account of these two qualities, be preferred to all the rest. Fixed alkalis are also well qualified to absorb the sulphur of cinabar. Cinabar must be decomposed in close vessels, and by the way of distillation; otherwise the mercury, as soon as it separates from the sulphur, will be dissipated in vapours and entirely lost. In this operation it is needless to add either flux or phlogiston; because the cinabar is decomposed without melting, and the mercury, though in a mineral state, contains, like gold and silver, all the phlogiston requisite to secure its metalline properties. _Of the Ores of Regulus of Antimony._ Regulus of Antimony is always found in a mineral state: it is mineralized by sulphur; but sometimes, though rarely, it is also combined with a little arsenic. When the ore of regulus of antimony is to be decomposed, the first thing to be done is to expose it to a degree of heat too weak to melt its earthy and stony parts, but strong enough to fuse its reguline, together with its sulphureous parts, which by this means are separated from the earth, and united into one mass, known by the name of Antimony. It is plain that this first operation, which is founded on the great fusibility of antimony, produces, with regard to the ore of regulus of antimony, the same effect that washing hath on other ores: so that after this first fusion nothing more is requisite to the obtaining of a pure regulus of antimony, but to separate it from its sulphur by roasting, and to melt it with some matter abounding in phlogiston, in the same manner as other metallic matters are treated. The term _Calcination_ is generally used to express this torrefaction of antimony, by means whereof the metallic earth of the regulus of antimony is separated from its sulphur. As regulus of Antimony hath, like Mercury, much less affinity with sulphur than the other metals have, it follows that antimony may be decomposed by the same means as cinabar; but the regulus, so obtained, is adulterated with a portion of the additament made use of, which combines therewith. There is still another process employed for obtaining the regulus of antimony: it consists, as was mentioned in its place, in detonating the mineral with a mixture of nitre and tartar, applied in such a proportion that, after the detonation has consumed the sulphur, there may remain so much inflammable matter as will be sufficient to furnish the metalline earth of the antimony with the phlogiston necessary to preserve its metallic properties. But by this method less regulus is produced, than by calcining, or torrefying, and reducing as usual. _Of the Ores of Bismuth._ The ore of Bismuth consists of the semi-metal mineralized by arsenic, and of an unmetallic earth. It is very easy to decompose this ore, and to extract the bismuth it contains: for this purpose it need only be exposed to a moderate heat, whereby the arsenic will be dissipated in vapours, and the bismuth melted, which will then separate from the unmetallic earth. This earth, at least, in several ores of bismuth, possesses the property of tinging all vitrifiable matters, with which it is melted, of a beautiful blue colour. To decompose the ore of bismuth no flux or inflammable matter is used; because this semi-metal is possessed, even in its mineral state, of all the phlogiston requisite to maintain its metalline properties; and its great fusibility makes it unnecessary to melt the unmetallic earth contained in its ore. _Of the Ores of Zinc._ Zinc is not generally obtained from a particular ore of its own; but sublimes during the fusion of a mineral, or rather a confused mass of minerals, that contains this semi-metal together with iron, copper, lead, sulphur, arsenic, and, like all other ores, an unmetallic earth. Nevertheless, there is a substance which may be considered as the proper ore of zinc, because it contains a pretty large quantity of that semi-metal, a little iron, and an unmetallic earth. It is called _Calamine_, or _Lapis Calaminaris_; but hitherto the art of procuring zinc directly from this mineral hath no where been practised. Calamine is commonly employed only to convert copper into brass, or a yellow metal, by cementing it therewith. Indeed, till lately, no easy or practicable method of obtaining pure zinc from calamine was publicly known; for that semi-metal being volatile and very inflammable, its ore cannot be fused like others. Mr. Margraaf was the first who, by mixing powdered charcoal with calamine in close vessels, obtained a perfect zinc from it, by the means of distillation or sublimation, as shall be shewn in our Practical Chymistry. _Of Arsenical Minerals._ Arsenic, as well as sulphur, is naturally combined with almost all ores, or minerals containing metallic substances. As it is very volatile, while the matters with which it is united are fixed, at least in comparison therewith, it is easily separated by sublimation. The minerals that contain most arsenic are the white pyrites, orpiment, and cobalt. We have already considered the white pyrites: as to orpiment, it consists of sulphur and arsenic. Both these substances being very volatile, it is difficult to separate them by sublimation: yet, with proper management, and a due regulation of the fire, this separation may be effected; because sulphur sublimes a little more easily than arsenic. But it is more convenient, as well as more expeditious, to make use of some additament that hath a greater affinity with one of those substances than with the other. Fixed alkalis and mercury, both of which have more affinity with sulphur than with arsenic, may be very properly employed on this occasion. Cobalt is a mineral composed of arsenic, an unmetallic earth, and frequently bismuth: and as none of these are very volatile, except the arsenic, this may be easily separated from the rest by sublimation. The unmetallic earth which remains has, like that of the ore of bismuth, the property of giving a blue colour to any vitrifiable matters melted with it; whence it is conjectured, that cobalt and the ore of bismuth have a great resemblance, or are often blended with each other. Nevertheless, Mr. Brant, an ingenious Swedish Chymist, insists that they are very different: he pretends that the metallic substance contained in the true cobalt is a semi-metal of a peculiar nature, which hath been erroneously confounded with bismuth: and indeed he proves by a great number of curious experiments, related in the Memoirs of the Academy of Upsal, that these two metallic substances have properties that are essentially different: to that which is obtained from cobalt, he gives the name of _Regulus of Cobalt_. Besides the minerals already recited, there is found in the bowels of the earth another species of compound body, of which we have already taken notice; but which is supposed, with some degree of probability, to belong as much to the vegetable as to the mineral kingdom: I mean the _Bitumens_; which the best observations oblige us to consider as vegetable oils, that by lying long in the earth have contracted an union with the mineral acids, and by that means acquired the thickness, consistence, and other properties observable in them. By distillation they yield an oil, and an acid not unlike a mineral acid. Mr. Bourdelin has even demonstrated, by a very artful and ingenious process, that amber contains a manifest acid of sea-salt. See the Memoirs of the Royal Academy of Sciences. CHAP. XVII. _Explanation of the Table of Affinities_. It hath been shewn in the course of this work, that the causes of almost all the phenomena, which Chymistry exhibits, are deducible from the mutual affinities of different substances, especially the simplest. We have already explained (Chap. II.) what is meant by affinities, and have laid down the principal laws to which the relations of different bodies are subject. The late Mr. Geoffroy, one of the best Chymists we have had, being convinced of the advantages which all who cultivate Chymistry would receive from having constantly before their eyes a state of the best ascertained relations between the chief agents in Chymistry, was the first who undertook to reduce them into order, and unite them all in one point of view, by means of a table. We are of opinion, with that great man, that this Table will be of considerable use to such as are beginning to study Chymistry, in helping them to form a just idea of the relations which different substances have with one another; and that the practical Chymist will thereby be enabled to account for what passes in several of his operations, otherwise difficult to be understood, as well as to judge what may be expected to result from mixtures of different compounds. These reasons have induced us to insert it at the end of this Elementary Treatise, and to give a short explanation of it here; especially as it will serve, at the same time, for a recapitulation of the whole work, in which the several axioms of this Table are dispersed. You have it here just as it was drawn up by Mr. Geoffroy, without any addition or alteration. I own, however, that it might be improved both ways: for since the death of that great Chymist many experiments have been made, some of which have discovered new affinities, and others have raised exceptions to some of those laid down by him. But several reasons dissuade me from publishing a new Table of Affinities, containing all the emendations and innovations that might be made in the old one. The first is, that many of the affinities lately discovered are not yet sufficiently verified, but, on the contrary, subject to be contested: in short, they are perhaps liable to more considerable objections, and exceptions, than the other. The second is, that as Mr. Geoffroy's Table contains all the fundamental affinities, it is more suitable to an Elementary Treatise than a much fuller one would be; seeing this would necessarily suppose the knowledge of many things not treated of by us, and of which it was not proper to say any thing in such a book as this. However, as it is essential to our purpose that we lead none into error, we shall take care in explaining the affinities delivered by Mr. Geoffroy, to mention the principal objections and exceptions to which they are liable: we shall, moreover, add a very few new ones, confining ourselves to such only as are elementary and well ascertained. The upper line of Mr. Geoffroy's Table, comprehends several substances used in Chymistry. Under each of those substances are ranged in distinct columns several matters compared with them, in the order of their relation to that first substance; so as that which is the nearest to it is that which hath the greatest affinity with it, or that which none of the substances standing below it can separate therefrom; but which, on the contrary, separates them all when they are combined with it, and expels them in order to join itself therewith. The same is to be understood of that which occupies the second place of affinity; that is, it has the same property with regard to all below it, yielding only to that which is above it: and so of all the rest. At the top of the first column stands the character which denotes an Acid in general. Immediately under this stands the mark of a Fixed Alkali, being placed there as the substance which has the greatest affinity with an Acid. After the Fixed Alkali appears the Volatile Alkali, whose affinity with Acids yields only to the Fixed Alkali. Next come the Absorbent Earths; and last of all Metallic Substances. Hence it follows, that when a Fixed Alkali is united with an acid it cannot be separated therefrom by any other substance; that a Volatile Alkali united with an Acid cannot be separated from it by any thing but a Fixed Alkali; that an Absorbent Earth combined with an acid may be separated from it either by a Fixed or by a Volatile Alkali; and lastly, that any Metallic Substance combined with an Acid may be separated from it by a Fixed Alkali, a Volatile Alkali, or an Absorbent Earth. There are many important remarks to be made on this first column. First, it is making the rule too general to say that any Acid whatever has a greater affinity with a Fixed Alkali, than with any other substance. And indeed Mr. Geoffroy himself hath made an exception with respect to the Vitriolic Acid; for in the fourth column, at the head of which stands that Acid, we find the sign of the Phlogiston placed above that of the Fixed Alkali, as having a greater affinity than the Fixed Alkali with the Vitriolic Acid. This is founded on the famous experiment, wherein Vitriolated Tartar and Glauber's Salt are decompounded by means of the Phlogiston, which separates the Fixed Alkalis of these Neutral Salts, and uniting with the Vitriolic Acid contained in them forms therewith a Sulphur. Secondly, Nitre deflagrates, and is decomposed, by the contact of any inflammable matter whatever that is actually ignited; and the operation which produces Phosphorus is no other than a decomposition of sea-salt, whose Acid quits its Alkaline basis to join with the Phlogiston: now these facts furnish very strong reasons for believing that both these Acids, as well as the Vitriolic, have a stronger affinity with the Phlogiston than with a Fixed Alkali. Lastly, as several experiments shew the Vegetable Acids to be only the Mineral Acids disguised and mortified, there are sufficient grounds for suspecting that Acids in general have a greater affinity with the Phlogiston than with Fixed Alkalis: so that instead of making an exception with regard to the Vitriolic Acid, it would perhaps be better to lay down this greater affinity as common to all Acids whatever, and to place the Phlogiston in the first column, immediately under the character which denotes an Acid in general. This theory, however, stands in need of confirmation from other experiments[4]. [4] Mr. Margraaf, an able German Chymist, has made several experiments, which induce him to think that the Acid of Phosphorus is of a particular kind, and different from that of sea-salt. May it not be the Marine Acid, but altered by the union it has contracted with the Phlogiston? Or may it not be, with respect to Phosphorus, what the volatile sulphureous spirit is, with respect to Sulphur? See the Memoirs of the Royal Academy of Sciences of Berlin. Thirdly, in this same column the character of a Volatile Alkali is set above that of an Absorbent Earth, as having a greater affinity with Acids; and yet these Absorbent Earths decompose the Ammoniacal salts, drive away the Volatile Alkali from the Acids, and assume its place. This is one of the first objections made against Mr. Geoffroy's Table. His answer thereto is printed in the Memoirs of the Academy of Sciences for 1718, where his Table also is to be found. We have already declared our opinion about this matter in treating of a Volatile Alkali. Fourthly, in 1744, Mr. Geoffroy, brother to the author of the Table, who hath done no less honour to Chymistry than that eminent physician, gave in a Memoir containing an exception to the last affinity in the first column; namely, that which places Absorbent Earths above Metallic substances. He therein shews, that Alum may be converted into Copperas by boiling it in iron vessels; that, on this occasion, the iron precipitates the Earth of the Alum, separates it from its Acid, and assumes its place; so that of course it must have a greater affinity, than the Absorbent Earth of Alum, with the Vitriolic Acid. At the head of the second column stands the character of the Marine Acid, which signifies that the affinities of this Acid are the subject of the column. Immediately below it is placed the mark of Tin. As this is a metalline substance, and as the first column places metalline substances in the lowest degree of affinity with all Acids, it is plain we must suppose Fixed Alkalis, Volatile Alkalis, and Absorbent Earths, to be placed here in order after the Marine Acid, and before Tin. Tin, then, is of all Metalline substances that which has the greatest affinity with the Marine Acid; and then follow Regulus of Antimony, Copper, Silver, Mercury. Gold comes last of all; and there are no less than two vacant places above it. By this means it is in some sort excluded from the rank of substances that have an affinity with the Marine Acid. The reason thereof is, that this Acid alone is not capable of dissolving Gold and combining therewith, necessarily requiring for that purpose the aid of the Nitrous Acid, or at least of the Phlogiston. The third column exhibits the affinities of the Nitrous Acid, the character whereof stands at its head. Immediately below it is the sign of Iron, as the metal which has the greatest affinity with this Acid; and then follow other metals, each according to the degree of its relation; to wit, Copper, Lead, Mercury, and Silver. In this column, as in the preceding one, we must suppose the substances, which in the first column stand above Metallic substances, to be placed in their proper order before Iron. The fourth column is intended to represent the Affinities of the Vitriolic Acid. Here Mr. Geoffroy has placed the Phlogiston as the substance which has the greatest affinity with this Acid, for the reason given in our explanation of the first column. Below it he has ranked Fixed Alkalis, Volatile Alkalis, and Absorbent Earths, to shew that this is an exception to the first column. As to Metalline substances, he has set down but three, being those with which the Vitriolic Acid has the most perceptible affinity: these metals, placed in the order of their affinities, are Iron, Copper, and Silver. The fifth column shews the affinities of Absorbent Earths. As these Earths have no sensible affinity but with Acids, this column contains only the characters of the Acids ranked according to the degree of their strength, or affinity with the Earths; to wit, the Vitriolic, the Nitrous, and the Marine Acids. Underneath this last might be placed the Acid of Vinegar, or the Vegetable Acid. The sixth column expresses the Affinities of Fixed Alkalis with Acids, which are the same with those of Absorbent Earths. Moreover, we find Sulphur placed here below all the Acids; because Liver of Sulphur, which is a combination of Sulphur with a Fixed Alkali, is actually decompounded by any Acid: for any Acid precipitates the Sulphur and unites with the Alkali. Immediately over the Sulphur, or in the same square with it, might be set a mark denoting the Volatile Sulphureous Spirit; because, like Sulphur, it has less affinity than any other Acid with Fixed Alkalis. Oils might also be ranked with Sulphur, because they unite with Fixed Alkalis, and therewith form Soaps, which are decompounded by any acid whatever. The seventh column points out the affinities of Volatile Alkalis, which are likewise the same as those of Absorbent Earths; and the Vegetable Acid might be placed here also under the Marine Acid. The eighth column specifies the affinities of Metallic substances with Acids. The affinities of the Acids, which, with respect to Fixed Alkalis, Volatile Alkalis, and Absorbent Earths, succeeded each other uniformly, do not appear in the same order here. The Marine Acid, instead of being placed below the Vitriolic and Nitrous Acids, stands, on the contrary, at their head; because, in fact, this Acid separates Metalline substances from all the other Acids with which they happen to be united, and, forcing these Acids to quit possession, intrudes into their place. Nevertheless, this is not a general rule; for several Metalline substances must be excepted, particularly Iron and Copper. The ninth column declares the affinities of Sulphur. Fixed Alkalis, Iron, Copper, Lead, Silver, Regulus of Antimony, Mercury, and Gold, stand below it in the order of their affinities. With regard to Gold it must be observed, that it will not unite with pure Sulphur: it suffers itself to be dissolved only by the Liver of Sulphur, which is known to be a composition of Sulphur and Fixed Alkali. At the head of the tenth column appears Mercury, and beneath it several Metalline substances, in the order of their affinities with it. Those Metalline substances are Gold, Silver, Lead, Copper, Zinc, and Regulus of Antimony. It is proper to remark on this column, that Regulus of Antimony, which stands the lowest, unites but very imperfectly with Mercury; and that after a seeming union of these two Metallic substances hath been obtained, by a tedious triture with the addition of water, they do not continue long united, but spontaneously separate from each other in a short time. Iron and Tin are here excluded; the former with great reason, because hitherto it hath not been clearly proved, by any known experiment, that ever Mercury was united with Iron: but the same objection cannot be made to Tin, which amalgamates very well with Mercury, and might therefore be placed in this column nearly between Lead and Copper. I use the word _nearly_, because the different degrees of affinity between Metalline substances and Mercury are not so exactly determined, as the other relations before considered; seeing they generally unite with it, without excluding one another. We can therefore scarce judge of the degree of affinity that belongs to each, but by the greater or less readiness of each to amalgamate therewith. The eleventh column shews, that Lead has a greater affinity with Silver than with Copper. The twelfth, that Copper has a greater affinity with Mercury than with Calamine. The thirteenth, that Silver has a greater affinity with Lead than with Copper. The fourteenth contains the affinities of Iron. Regulus of Antimony stands immediately underneath it, as being the Metallic substance which has the greatest affinity with it. Silver, Copper, and Lead, are placed together in the next square below, because the degrees of affinity which those metals have with Iron are not exactly determined. The same is to be said of the fifteenth column: Regulus of Antimony stands at its head; Iron is immediately below it; and below the Iron the same three metals occupy one square as before. Lastly, the sixteenth column indicates that Water has a greater affinity with Spirit of Wine than with Salts. By this general expression must not be understood any Saline substance whatever; but only the Neutral Salts, which Spirit of Wine frees from the water that kept them in solution. Fixed Alkalis, on the contrary, as well as the Mineral Acids, have a greater affinity than Spirit of Wine with water: so that these Saline substances, being well dephlegmated, and mixed with Spirit of Wine; imbibe the water it contains and rectify it. To these might be added another short column, having Spirit of Wine at its head: immediately below it should be the character of Water, and below that the mark of Oil. This column would shew that the Spirit of Wine has a greater affinity with Water than with Oils; because any Oily matter whatever, that is dissolved in Spirit of Wine, may be actually separated from it by the affusion of Water. This rule admits of no exception but in one case; which is when the oily substance partakes of the nature of soap, by having contracted an union with some saline matter. But as this must be imputed wholly to that adventitious saline matter being superadded to the oily substance, it is no just foundation for an exception, and the affinity in question is nevertheless general. We have now delivered every thing material that we had to say concerning Mr. Geoffroy's Table of Affinities. It is, as we observed before, of exceeding great service, as it collects into one view the principal truths laid down in this Treatise. Indeed the most advantageous way of using it is, not to delay consulting it till you have read the book through, but to turn to it while you are reading, as oft as any affinity between bodies is treated of; which it will imprint more strongly on your mind, by representing it in a manner before your eyes. CHAP. XVIII. _The_ THEORY _of_ CONSTRUCTING _the_ VESSELS _most commonly used in_ CHYMISTRY. Chymists cannot perform the operations of their art without the help of a considerable number of vessels, instruments, and furnaces, adapted to contain the bodies on which they intend to work, and to apply to them the several degrees of heat required by different processes. It is therefore proper, before we advance to the operations themselves, to consider particularly and minutely what relates to the instruments with which they are to be performed. Vessels intended for Chymical Operations should, to be perfect, be able to bear, without breaking, the sudden application of great heat and great cold; be impenetrable to every thing, and unalterable by any solvent; unvitrifiable, and capable of enduring the most violent fire without melting: but hitherto no vessels have been found with all these qualities united. They are made of sundry materials; namely, of metal, of glass, and of earth. Metalline vessels, especially those made of Iron or Copper, are apt to be corroded by almost every saline, oily, or even aqueous substance. For this reason, in order to render the use of them a little more extensive, they are tinned on the inside. But, notwithstanding this precaution, they are on many occasions not to be trusted; and should never be employed in any nice operations which require great accuracy: they are, moreover, incapable of resisting the force of fire. Earthen vessels are of several sorts. Some, that are made of a refractory earth, are capable of being suddenly exposed to a strong fire without breaking, and even of sustaining a great degree of heat for a considerable time: but they generally suffer the vapours of the matters which they contain, as well as vitrified metals, to pass through them, especially the glass of lead, which easily penetrates them and runs through their pores as through a sieve. There are others made of an earth that, when well baked, looks as if it were half vitrified: these being much less porous, are capable of retaining the vapours of the matters which they contain, and even glass of lead in fusion; which is one of the severest trials a vessel can be put to: but then they are more brittle than the other sort. Good glass vessels should constantly be employed in preference to all others, whenever they can possibly be used: and that not only because they are no way injured by the most active solvents, nor suffer any part of what they contain to pass through, but also because their transparency allows the Chymist to observe what passes within them: which is always both curious and useful. But it is pity that vessels of this sort should not be able to endure a fierce fire without melting. We shall take care, when we come to describe the several sorts of chymical instruments, and the manner of using them, to note what vessels are to be preferred to others on different occasions. Distillation, as hath been already said, is an operation by which we separate from a body, by the help of a gradual heat, the several principles of which it consists. There are three methods of distilling. The first is performed by applying the heat over the body whose principles are to be extracted. In this case, as the liquors, when heated and converted into vapours, constantly endeavour to fly from the center of heat, they are forced to re-unite in the lower part of the vessel, that contains the matter in distillation, and so passing through the pores or holes of that vessel, they fall into another cold vessel applied underneath to receive them. This way of distilling is on this account called distilling _per Descensum_. It requires no other apparatus than two vessels figured like segments of hollow spheres, whereof that which is pierced with little holes, and intended to contain the matter to be distilled, should be much less than the other, which is to contain the fire, and to fill its aperture exactly; the whole together to be supported vertically upon a third vessel, which is to serve the purpose of a recipient, admitting into its mouth the convex bottom of the vessel containing the matter to be distilled, which must accurately fill it. This method of distilling is but little used. The second method of distilling is performed by applying the heat underneath the matter to be decomposed. On this occasion the liquors being heated, rarefied, and converted into vapours, rise, and are condensed in a vessel contrived for that purpose, which we shall presently describe. This way of distilling is called distilling _per Ascensum_, and is much used. The vessel in which this distillation _per Ascensum_ is performed we call an _Alembic_. There are several sorts thereof, differing from one another both in the matter of which, and the manner in which, they are made. Those employed to draw the odoriferous waters and essential oils of plants are generally made of copper, and consist of several pieces. The first, which is designed to contain the plant, is formed nearly like a hollow cone, the vertex whereof is drawn out in the shape of a hollow cylinder or tube: this part is named the _Cucurbit_, and its tube the _Neck_ of the _Alembic_. To the upper end of this tube another vessel is soldered: this is called the _Head_, and commonly has likewise the form of a cone, joined to the neck of the alembic by its base, round which, on the inside, is hollowed a small groove, communicating with an orifice that opens at its most depending part. To this orifice is soldered a small pipe in a direction sloping downwards, which is called the _Nose_, _Spout_, or _Beak_ of the alembic. As soon as the matters contained in the alembic grow hot, vapours begin to arise from them, and ascending through the neck of the alembic into the head, are by the sides thereof stopped and condensed: from thence they trickle down in little streams to the groove, which conveys them to the spout; and by that they pass out of the alembic into a glass vessel with a long neck, the end of the spout being introduced into that neck, and luted thereto. To facilitate the refrigeration and condensation of the vapours circulating in the head, all alembics of metal are moreover provided with another piece, which is a kind of large pan of the same metal, fitted and soldered round the head. This piece serves to keep cold water in, which incessantly cools the head, and therefore it is called the _Refrigeratory_. The water in the refrigeratory itself grows hot after some time, and must therefore be changed occasionally; the heated water being first drawn off by means of a cock fixed near the bottom of the refrigeratory. All copper alembics should be tinned on the inside for the reasons already given. When saline spirits are to be distilled, alembics of metal must not be used; because the saline vapours would corrode them. In this case recourse must be had to alembics of glass. These consist of two pieces only; namely, a _Cucurbit_, whose superior orifice is admitted into and exactly luted with its _Head_, which is the second piece. In general, as alembics require that the vapours of the matter to be distilled should rise to a considerable heighth, they ought to be used only when the most volatile principles are to be drawn from bodies: and the lighter and more volatile the substances to be separated by distillation are, the taller must the alembic be; because the most ponderous parts, being unable to rise above a certain heighth, fall back again into the cucurbit as soon as they arrive there, leaving the lighter to mount alone, whose volatility qualifies them to ascend into the head. When a matter is to be distilled, that requires a very tall alembic, and yet does not admit of a metalline vessel, the end will be best answered by a glass vessel of a round or oval shape, having a very long neck, with a small head fitted to its extremity. Such a vessel serves many purposes: it is sometimes employed as a receiver, and at other times as a digesting vessel; on which last occasion it goes under the name of a _Matrass_. When one of these, provided with a head, is applied to the purpose of distilling, it forms a sort of alembic. There are some alembics of glass, blown in such a manner by the workmen, that the body and head form but one continued piece. As these alembics do not stand in need of having their several pieces luted together, they are very useful on some occasions, when such exceeding subtile vapours rise as are capable of transpiring through lutes. The head must have an aperture at the top, provided with a short tube, through which, by means of a funnel with a long pipe, the matter to be distilled may be introduced into the cucurbit. This is to be exactly closed with a glass stopple, the surface whereof must be made to fit the inside of the tube in every point, by rubbing those two pieces well together with emery. Another sort of alembic hath also been invented, which may be used with advantage when _Cohobation_ is required; that is, when the liquor obtained by distillation is to be returned upon the matter in the cucurbit; and especially when it is intended that this cohobation shall be repeated a great number of times. The vessel we are speaking of is constructed exactly in the same manner as that last described; except that its beak, instead of being in a straight line, as in the other alembics, forms a circular arch, and re-enters the cavity of the cucurbit, in order to convey back again the liquor collected in the head. This instrument hath commonly two beaks opposite to each other, both turned in this manner, and is called a _Pelican_: it saves the artist the trouble of frequently unluting and reluting his vessels, as well as the loss of a great many vapours. There are certain substances which in distillation afford matters in a concrete form, or rise wholly in the form of a very light powder, called _Flowers_. When such substances are to be distilled, the cucurbit which contains them is covered with a head without a nose, which is named a _Blind-head_. When the flowers rise in great quantities and very high, a number of heads is employed to collect them; or rather a number of a kind of pots, consisting of a body only without any bottom, which fitting one into the other form a canal, that may be lengthened or shortened at pleasure, according as the flowers to be sublimed are more or less volatile. The last of the heads, which terminates the canal, is quite close at one end, and makes a true blind-head. These vessels are called _Aludels_; they are usually of earthen or stone ware. All the vessels above-mentioned are fit only for distilling such light volatile matters as can be easily raised and brought over; such as phlegm, essential oils, fragrant waters, acid oily spirits, volatile alkalis, _&c._ But when the point is to procure by distillation principles that are much less volatile, and incapable of rising high, such as the thick fetid oils, the vitriolic, the nitrous, and the marine acids, _&c._ we are under a necessity of having recourse to other vessels, and another manner of distilling. It is easy to imagine, that such a vessel must be much lower than the alembic. It is indeed no more than a hollow globe, whose upper part degenerates into a neck or tube, that is bent into a horizontal position; for which reason this instrument is called a _Retort_: it is always of one single piece. The matter to be distilled is introduced into the body of the retort by means of a ladle with a long tubular shank. Then it is set in a furnace built purposely for this use, and so that the neck of the retort coming out of the furnace may, like the nose of the alembic, stand in a sloping position, to facilitate the egress of the liquors, which by its means are conveyed to a receiver, into which it is introduced, and with which it is luted. This way of distilling, in which the vapours seem rather to be driven out of the vessel horizontally and laterally, than raised up and sublimed, is for that reason called Distillation _per Latus_. Retorts are, of all the instruments of distillation, those that must sustain the greatest heat, and resist the strongest solvents; and therefore they must not be made of metal. Some, however, which are made of iron may do well enough on certain occasions: the rest are either of glass or earth. Those of glass, for the reasons above given, are preferable to the other sort, in all cases where they are not to be exposed to such a force of fire as may melt them. The best glass, that which stands both heat and solvents best, is that in which there are fewest alkaline salts. Of this sort is the green German glass: the beautiful white crystal glass is far from being equally serviceable. Retorts, as well as alembics, may be of different forms. For example, some matters are apt to swell, and rise over the neck of the retort in substance, without suffering any decomposition; when such matters are to be distilled in a retort, it is proper that the body of the vessel, instead of being globular, be drawn out into the form of a pear, so as nearly to resemble that of a cucurbit. In a retort of this kind, the distance between the bottom and the neck being much greater than in those whose bodies are spherical, the matters contained have much more room for expansion; so that the inconvenience here mentioned is thereby prevented. Retorts of this form are called English retorts. As they hold the middle place between alembics and common retorts, they may be used to distil such matters as have a mean degree of volatility between the greatest and the least. It is moreover proper to have, in a laboratory, sundry retorts with necks of different diameters. Wide necks will be found the fittest for conveying thick matters, and such as readily become fixed; for instance, some very thick fetid oils, butter of antimony, _&c._; for as these matters acquire a consistence as soon as they are out of the reach of a certain degree of heat, they would soon choak a narrow neck, and by stopping the vapours which rise at the same time from the retort, might occasion the bursting of the vessels. Some retorts are also made with an opening on their upper side, like that of tubulated glass alembics, which is to be closed in the same manner with a glass stopple. These retorts are also called Tubulated retorts, and ought always to be used whenever it is necessary to introduce fresh matter into the retort during the operation; seeing it may be done by means of this invention, without unluting and reluting the vessels; which ought always to be avoided as much as possible. One of the things that most perplexes the Chymists, is the prodigious elasticity of many different vapours, which are frequently discharged with impetuosity during the distillation, and are even capable of bursting the vessels with explosion, and with danger to the artist. On such occasions it is absolutely necessary to give these vapours vent, as we shall direct in its proper place: but as that can never be done without losing a great many of them; as some of them in particular are so elastic that scarce any at all would remain in the vessel; for instance, those of the spirit of nitre, and especially those of the smoking spirit of salt; the practice is to make use of very large receivers, of about eighteen or twenty inches diameter, that the vapours may have sufficient room to circulate in, and by applying to the wide surface presented them by the extensive inside of such a large vessel, may be condensed into drops. These huge receivers are commonly in the form of hollow globes, and are called Ballons. To give these vapours still more room, ballons have been contrived with two open gullets in each, diametrically opposite to one another; whereof one admits the neck of the retort, and the other is received by one of the gullets of a second ballon of the same form, which is joined in like manner to a third, and so on. By this artifice the space may be enlarged at pleasure. These ballons with two necks are called Adopters. Operations on bodies that are absolutely fixed, as metals, stones, sand, _&c._ require only such vessels as are capable of containing those bodies, and resisting the force of fire. These vessels are little hollow pots, of different dimensions, which are called Crucibles. Crucibles can hardly be made of any thing but earth; they ought to have a cover of the same material fitted to shut them close. The best earth we know is that whereof those pots are made in which butter is brought from Bretagne: these pots themselves are exceeding good crucibles; and they are almost the only ones that are capable of holding glass of lead in fusion, without being penetrated by it. For the roasting of ores, that is, freeing them, by the help of fire, from their sulphureous and arsenical parts, little cups of the same material with crucibles are used; but they are made flat, shallow, and wider, above than below, that these volatile matters may the more freely exhale. These vessels are called Tests, or Scorifiers: they are scarce ever used but in the Docimastic art, that is, in making small Assays of ores. CHAP. XIX. _The_ THEORY _of_ CONSTRUCTING _the_ FURNACES _most commonly used in_ CHYMISTRY. Skill in conducting and applying fire properly, and determining its different degrees, is of very great consequence to the success of Chymical operations. As it is exceeding difficult to govern and moderate the action of fire, when the vessels in which any operation is performed are immediately exposed to it, Chymists have contrived to convey heat to their vessels, in nice operations, through different mediums, which they place occasionally between those vessels and the fire. Those intermediate substances in which they plunge their vessels are called Baths. They are either fluid or solid: the fluid baths are water or its vapours. When the distilling vessel is set in water, the bath is called _Balneum Mariæ_, or the _Water Bath_; and the greatest degree of heat of which it is susceptible is that of boiling water. When the vessel is exposed only to the vapours which exhale from water, this forms the _Vapour Bath_; the heat of which is nearly the same with that of the _Balneum Mariæ_. These baths are useful for distilling essential oils, ardent spirits, sweet-scented waters; in a word, all such substances as cannot bear a greater heat, without prejudice either to their odour, or to some of their other qualities. Baths may also be made of any other fluids, such as oils, mercury, _&c._ which are capable of receiving and communicating much more heat: but they are very seldom used. When a more considerable degree of heat is required, a bath is prepared of any solid matter reduced to a fine powder, such as sand, ashes, filings of iron, _&c._ The heat of these baths may be pushed so far as to make the bottom of the vessel become faintly red. By plunging a thermometer into the bath, by the side of the vessel, it is easy to observe the precise degree of heat applied to the substance on which you are working. It is necessary that the thermometers employed on this occasion be constructed on good principles, and so contrived as to be easily compared with those of the most celebrated natural philosophers. Those of the illustrious Réaumur are most used and best known, so that it would not be amiss to give them the preference. When a greater heat is required than any of those baths can give, the vessels must be set immediately on live coals, or in a flaming fire: this is called working with a naked fire; and, in this case it is much more difficult than in the other to determine the degrees of heat. There are several ways of applying a naked fire. When the heat or flame is reflected upon the upper part of a vessel which is exposed to the fire, this is called a Reverberated heat. A Melting heat is that which is strong enough to fuse most bodies. A Forging heat is that of a fire which is forcibly excited by the constant blast of a pair of bellows, or more. There is also another sort of fire which serves very commodiously for many operations, because it does not require to be fed or frequently mended: this is afforded by a lamp with one or more wicks, and may be called a Lamp-heat. It is scarce ever employed but to heat baths, in operations which require a gentle and long continued warmth: if it hath any fault, it is that of growing gradually hotter. All the different ways of applying fire require Furnaces of different constructions: we shall therefore describe such as are of principal and most necessary use. Furnaces must be divided into different parts or stories, each of which has its particular use and name. The lower part of the furnace, designed for receiving the ashes and giving passage to the air, is called the Ash-hole. The ash-hole is terminated above by a grate, the use of which is to support the coals and wood, which are to be burnt thereon: this part is called the Fire-place. The fire-place is in like manner terminated above by several iron bars, which lie quite across it from right to left, in lines parallel to each other: the use of these bars is to sustain the vessels in which the operations are to be performed. The space above these bars to the top of the furnace is the upper story, and may be called the Laboratory of the furnace. Lastly, some furnaces are quite covered above by means of a kind of vaulted roof called the Dome. Furnaces have moreover several apertures: one of these is at the ash-hole, which gives passage to the air, and through which the ashes that fall through the grate are raked out; this aperture is called the ash-hole Door: another is at the fire-place, through which the fire is supplied with fuel, as occasion requires; this is called the mouth or door of the Fire-place, or the Stoke-hole: there is a third in the upper story, through which the neck of the vessel passes; and a fourth in the dome for carrying off the fuliginosities of combustible matters, which is called the Chimney. To conclude, there are several other openings in the several parts of the furnace, the use whereof is to admit the air into those places, and also, as they can be easily shut, to incite or slacken the activity of the fire, and so to regulate it; which has procured them the title of Registers. All the other openings of the furnace should be made to shut very close, the better to assist in governing the fire; by which means they likewise do the office of registers. In order to our forming a just and general idea of the construction of furnaces, and of the disposition of the several apertures in them, with a view to increase or diminish the activity of the fire, it will be proper to lay down, as our ground-work, certain principles of natural philosophy, the truth of which is demonstrated by experience. And first, every body knows that combustible matters will not burn or consume unless they have a free communication with the air; insomuch that if they be deprived thereof, even when burning most rapidly, they will be extinguished at once: that consequently combustion is greatly promoted by the frequent accession of fresh air, and that a stream of air, directed so as to pass with impetuosity through burning fuel, excites the fire to the greatest possible activity. Secondly, it is certain that the air which touches, or comes near ignited bodies is heated, rarefied, and rendered lighter than the air about it, that is, farther distant from the center of heat; and consequently that this air, so heated and become lighter, is necessarily determined thereby to ascend and mount aloft, in order to make room for that which is less heated and not so light, which by its weight and elasticity tends to occupy the place quitted by the other. Another consequence hereof is, that if fire be kindled in a place enclosed every where but above and below, a current of air will be formed in that place, running in a direction from the bottom to the top; so that if any light bodies be applied to the opening below, they will be carried up towards the fire; but, on the contrary, if they be held at the opening above, they will be impelled by a force which will drive them up, and carry them away from the fire. Thirdly and lastly, it is a truth demonstrated in hydraulics, that the velocity of a given quantity of any fluid, determined to flow in any direction whatever, is so much the greater the narrower the channel is to which that fluid is confined; and consequently that the velocity of a fluid will be increased by making it run from a wider through a narrower passage. These principles being established, it is easy to apply them to the construction of furnaces. First, if a fire be kindled in the fire-place of a furnace, which is open on all sides, it burns nearly as if it were in the open air. It has with the surrounding air a free communication; so that fresh air is continually admitted to facilitate the entire combustion of the inflammable matters employed as fuel. But there being nothing to determine that air to pass with rapidity through the fire in this case, it does not at all augment the activity thereof, but suffers it to waste away quietly. Secondly, if the ash-hole or dome of a furnace, in which a fire is burning, be shut quite close, then there is no longer any free communication between the air and the fire: if the ash-hole be shut, the air is debarred from having free access to the fire; if the dome be stopt, the egress of the air rarefied by the fire is prevented; and consequently the fire must in either case burn very faintly and slowly, gradually die away, and at last go quite out. Thirdly, if all the openings of the furnace be wholly closed, it is evident that the fire will be very quickly extinguished. Fourthly, if only the lateral openings of the fire-place be shut, leaving the ash-hole and upper part of the furnace open; it is plain that the air entering by the ash-hole will necessarily be determined to go out at top, and that consequently a current of air will be formed, which will pass through the fire, and make it burn briskly and vigorously. Fifthly, if both the ash-hole and the upper story of the furnace be of some length, and form canals either cylindric or prismatic, then the air being kept in the same direction through a longer space, the course of its stream will be both stronger and better determined, and consequently the fire will be more animated by it. Sixthly and lastly, if the ash-hole and the upper part of the furnace, instead of being cylindric or prismatic canals, have the form of truncated cones or pyramids, standing on their bases, and so ordered that the upper opening of the ash-hole, adjoining to the fire-place, may be wider than the base of the superiour cone or pyramid, then the stream of air, being forced to pass incessantly from a larger channel through a smaller, must be considerably accelerated, and procure to the fire the greatest activity which it can receive from the make of a furnace. The materials fittest for building furnaces are, 1. Bricks, joined together with potters clay mixed with sand and moistened with water. 2. Potters clay mingled with potsherds, moistened with water, and baked in a violent fire. 3. Iron; of which all furnaces may be made, with this precaution, that the inside be provided with a great many prominent points, as fastenings for a coat of earth, with which the internal parts of the furnace must necessarily be covered to defend it from the action of the fire. The reverberating furnace is one of those that are most employed in Chymistry: it is proper for distillations by the retort, and should be constructed in the following manner. First, the use of the ash-hole being, as was said, to give passage to the air and to receive the ashes, no bad consequence can attend its being made pretty high: it may have from twelve to twenty or twenty-four inches in heighth. Its aperture should be wide enough to admit billets of wood, when a great fire is to be made. Secondly, the ash-hole must be terminated at its upper part by an iron grate, the bars of which should be very substantial, that they may resist the action of the fire: this grate is the bottom of the fire-place, and destined to support the coals. In the lateral part of the fire-place, and nearly about the same heighth with the grate, there should be a hole of such a size that it may easily admit charcoal, as well as little tongs and shovels for managing the fire. This aperture or mouth of the fire-place should be perpendicularly over the mouth of the ash-hole. Thirdly, from six to eight or ten inches high above the grate over the ash-hole, little apertures must be made in the walls of the furnace, of eight or ten lines in diameter, an inch from one another, and those in one side must be diametrically opposite to those in the other. The use of these holes is to receive bars of iron for the retort to rest on; which should be, as I said, at different heights, in order to accommodate retorts of different sizes. At the upper extremity of this part of the furnace, which reaches from the iron bars to the top, the heighth whereof should be somewhat less than the width of the furnace, must be cut a semi-circular aperture for the neck of the retort to come through. This hole must by no means be over the doors of the fire-place and ash-hole; for then, as it gives passage to the neck of the retort, it must of course be opposite to the receiver, and in that case the receiver itself would stand over against those two apertures; which would be attended with this double inconvenience, that the receiver would not only grow very hot, but greatly embarrass the operator, whose free access to the fire-place and ash-hole would be thereby obstructed. It is proper therefore that the semi-circular cut we are speaking of be so placed that when the greatest ballons are luted to the retort they may leave an open passage to the fire-place and ash-hole. Fourthly, in order to cover in the laboratory of the reverberating furnace, there must be a roof made for it in the form of a cupola, or concave hemisphere, having the same diameter as the furnace. This dome should have a semi-circular cut in its rim, answering to that above-directed to be made in the upper extremity of the furnace, so that, when adjusted to each other, the two together may form a circular hole for the neck of the retort to pass through. At the top of this dome there must also be a circular hole of three or four inches diameter, carrying a short tapering funnel of the same diameter, and three inches high, which will serve for a chimney to carry off all fuliginosities, and accelerate the current of the air. This passage may be shut at pleasure with a flat cover. Moreover, as it is necessary that the dome should be taken off and put on with ease, it should have two ears or handles for that purpose: a portative or moveable furnace should also have a pair of handles, fixed opposite to each other, between the ash-hole and the fire-place. Sixthly and lastly, a conical canal must be provided of about three feet long, and sufficiently wide at its lower end to admit the funnel of the aperture at the top of the dome. This conical tube is to be applied to the dome when the fire is required to be extremely active: it tapers gradually from its base upwards, and breaks off as if truncated at top, where it should be about two inches wide. Besides the apertures already mentioned as necessary to a reverberating furnace, there must also be many other smaller holes made in its ash-hole, fire-place, laboratory, and dome, which must all be so contrived as to be easily opened and shut with stopples of earth: these holes are the registers of the furnace, and serve to regulate the activity of the fire, according to the principles before laid down. When the action of the fire is required to be exactly uniform and very brisk, it is necessary to stop carefully with moist earth all the little chinks in the juncture of the dome with the furnace, between the neck of the retort and the circular hole through which it passes, and which it never fills exactly, and, lastly, the holes which receive the iron bars that sustain the retort. It is proper to have, in a laboratory, several reverberating furnaces of different magnitudes; because, they must be proportioned to the size of the retorts employed. The retort ought to fill the furnace, so as to leave only the distance of an inch between it and the inside of the furnace. Yet when the retort is to be exposed to a most violent fire, and especially when it is required that the heat shall act with equal force on all parts of the furnace, and as strongly on its vault as on its bottom, a greater distance must be left between the retort and the inside of the furnace; for then the furnace may be filled with coals, even to the upper part of the dome. If moreover some pieces of wood be put into the ash-hole, the conical canal fitted on to the funnel of the dome, and all the apertures of the furnace exactly closed, except the ash-hole and the chimney, the greatest heat will then be excited that this furnace can produce. The furnace now described may also be employed in many other chymical operations. If the dome be laid aside, an alembic may very well be placed therein: but then the space, which will be left between the body of the alembic and the top of the upper part of the furnace, must be carefully filled up with Windsor-loam moistened; for without that precaution the heat will soon reach the very head, which ought to be kept as cool as possible, in order to promote the condensation of the vapours. On this occasion therefore it will be proper to leave no holes open in the fire-place, but the lateral ones; of which also those over-against the receiver must be stopped. A pot, or broad-brimmed earthen pan, may be placed over this furnace, and being so fitted to it as to close the upper part thereof accurately, and filled with sand, may serve for a sand-heat to distil with. The bars designed to support distilling vessels being taken out, a crucible may stand therein, and many operations be performed that do not require the utmost violence of fire. In a word, this furnace is one of the most commodious that can be, and more extensively useful than any other. The Melting furnace is designed for applying the greatest force of heat to the most fixed bodies, such as metals and earths. It is never employed in distilling: it is of no use but for calcination and fusion; and consequently need not admit any vessels but crucibles. The ash-hole of this furnace differs from that of the reverberating furnace only in this, that it must be higher, in order to raise the fire-place to a level with the artist's hand; because in that all the operations of this furnace are performed. The ash-hole therefore must be about three feet high: and this heighth procures it moreover the advantage of a good draught of air. For the same reason, and in consequence of the principles we laid down, it should be so built that its width lessening insensibly from the bottom to the top, it may be narrower where it opens into the fire-place than any where below. The ash-hole is terminated at its upper end, like that of the reverberating furnace, by a grate, which serves for the bottom of the fire-place, and ought to be very substantial, that it may resist the violence of the fire. The inside of this furnace is commonly an elliptic curve; because it is demonstrated by mathematicians that surfaces having that curvature reflect the rays of the sun, or of fire, in such a manner, that meeting in a point, or a line, they produce there a violent heat. But, to answer this purpose, those surfaces must be finely polished; an advantage hardly procurable to the internal surface of this furnace, which can be made of nothing but earth: besides, if it were possible to give it a polish, the violent action of the fire that must be employed in this furnace would presently destroy it. Yet the elliptical figure must not be entirely disregarded: for, if care be taken to keep the internal surface of the furnace as smooth as possible, it will certainly reflect the heat pretty strongly, and collect it about the center. The fire-place of this furnace ought to have but four apertures. First, that of the lower grate, which communicates with the ash-hole. Secondly, a door in its fore-side, through which may be introduced coals, crucibles, and tongs for managing them: this aperture should be made to shut exactly with a plate of iron, having its inside coated with earth, and turning on two hinges fixed to the furnace. Thirdly, over this door a hole slanting downwards, towards the place where the crucible is to stand. The use of this hole is to give the operator an opportunity of examining the condition of the matters contained in his crucible without opening the door of the fire-place: this hole should be made to open and shut easily, by means of a stopple of earth. Fourthly, a circular aperture of about three inches wide in the upper part or vault of the furnace, which should gradually lessen and terminate, like that of the dome of the reverberating furnace, in a short conical funnel of about three inches long, and fitted to enter the conical pipe before described, which is applied when the activity of the fire is to be increased. When this furnace is to be used, and a crucible to be placed in it, care must be taken to set on the grate a cake of baked earth, somewhat broader than the foot of the crucible. The use of this stand is to support the crucible, and raise it above the grate, for which purpose it should be two inches thick. Were it not for this precaution the bottom of the crucible, which would stand immediately on the grate, could never be thoroughly heated, because it would be always exposed to the stream of cold air which enters by the ash-hole. Care should also be taken to heat this earthen bottom red-hot before it be placed in the furnace, in order to free it from any humidity, which might otherwise happen to be driven against the crucible during the operation, and occasion its breaking. We omitted to take notice, in speaking of the ash-hole, that, besides its door, it should have about the middle of its heighth a small hole, capable of receiving the nosel of a good perpetual bellows, which is to be introduced into it and worked, after the door is exactly shut, when it is thought proper to excite the activity of the fire to the utmost violence. The Forge is only a mass of bricks of about three feet high, along whose upper surface is directed the nose or pipe of a pair of large perpetual bellows, so placed that the operator may easily blow the fire with one hand. The coals are laid on the hearth of the forge near the nose of the bellows; they are confined, if necessary, to prevent their being carried away by the wind of the bellows, within a space inclosed by bricks; and then by pulling the bellows the fire is continually kept up in its greatest activity. The forge is of use when there is occasion to apply a great degree of heat suddenly to any substance, or when it is necessary that the operator be at liberty to handle frequently the matters which he proposes to fuse or calcine. The Cupelling furnace is that in which gold and silver are purified, by the means of lead, from all alloy of other metallic substances. This furnace must give a heat strong enough to vitrify lead, and therewith all the alloy which the perfect metals may contain. This furnace is to be built in the following manner. First, of thick iron plates, or of some such composition of earth as we recommended for the construction of furnaces, must be formed a hollow quadrangular prism, whose sides may be about a foot broad, and from ten to eleven inches high; and extending from thence upwards may converge towards the top, so as to form a pyramid truncated at the heighth of seven or eight inches, and terminated by an aperture of the width of seven or eight inches every way. The lower part of the prism is terminated, and closed, by a plate of the same materials of which the furnace is constructed. Secondly, in the fore-side or front of this prism there is an opening of three or four inches in heighth, by five or six inches in breadth: this opening, which should be very near the bottom, is the door of the ash-hole. Immediately over this opening is placed an iron grate, the bars of which are quadrangular prisms of half an inch square, laid parallel to each other, and about eight or nine inches asunder, and so disposed that two of their angles are laterally opposite, the two others looking one directly upwards and the other downwards. As in this situation the bars of the grate present to the fire-place very oblique surfaces, the ashes and very small coals do not accumulate between them, or hinder the free entrance of the air from the ash-hole. This grate terminates the ash-hole at its upper part, and serves for the bottom of the fire-place. Thirdly, three inches, or three and a half, above the grate, there is in the fore-side of the furnace another opening, terminated by an arch for its upper part, which consequently has the figure of a semi-circle: it ought to be four inches wide at bottom, and three inches and an half high at its middle. This opening is the door of the fire-place; yet it is not intended for the same uses as the door of the fire-place in other furnaces: the purpose for which it is actually destined shall be explained when we come to shew how the furnace is to be used. An inch above the door of the fire-place, still in the fore-side of the furnace, are two holes of about an inch diameter, and at the distance of three inches and a half from each other, to which answer two other holes of the same size, made in the hinder part, directly opposite to these. There is, moreover, a fifth hole of the same width about an inch above the door of the fire-place. The design of all these holes shall be explained when we describe the manner in which these furnaces are to be used. Fourthly, the fore-part of the furnace is bound by three iron braces, one of which is fixed just below the door of the ash-hole; the second occupies the whole space between the ash-hole door and the door of the fire-place, and has two holes in it, answering to those which we directed to be made in the furnace itself about this place; and the third is placed immediately over the door of the fire-place. These braces must extend from one corner of the front of the furnace to the other, and be fastened thereto with iron pins, in such a manner that their sides next to the doors may not lie quite close to the body of the furnace, but form a kind of grooves for the iron plates to slide in, that are designed to shut the two doors of the furnace when it is necessary. Each of these iron plates should have a handle, by which it may be conveniently moved; and to each door there should be two plates, which meeting each other, and joining exactly in the middle of the door-place, may shut it very close. Each of the two plates belonging to the door of the fire-place ought to have a hole in its upper part; one of these holes should be a slit of about two lines wide, and half an inch long; the other may be a semi-circular opening of one inch in heighth and two in breadth. These holes should be placed so that neither of them may open into the fire-place when the two plates are joined together in the middle of the door to shut it close. Fifthly, to terminate the furnace above, there must be a pyramid formed of the same materials with the furnace, hollow, quadrangular, three inches high on a base of seven inches, which base must exactly fit the upper opening of the furnace: the top of this pyramidal cover must end in a tube of three inches in diameter and two in heighth, which must be almost cylindrical, and yet a little inclining to the conical form. This tube serves, as in the furnaces already described, to carry the conical funnel, which is fitted to the upper part when a fire of extraordinary activity is wanted. The furnace thus constructed is fit to serve all the purposes for which it is designed: yet before it can be used another piece must be provided, which, though it does not properly belong to the furnace, is nevertheless necessary in all the operations performed by it; and that is a piece contrived to contain the cupels, or other vessels which are to be exposed to the fire in this furnace. It is called a Muffle, and is made in the following manner. On an oblong square, of four inches in breadth, and six or seven in length, a concave semi-cylinder is erected, in the form of a vault, which makes a semi-circular canal, open at both ends. One of these is almost entirely closed, except that near the bottom two small semi-circular holes are left. In each of its sides likewise two such holes are made, and the other end is left quite open. The Muffle is intended to bear and communicate the fiercest heat; and therefore it must be made thin, and of an earth that will resist the violence of fire, such as that of which crucibles are made. The Muffle being thus constructed, and then well baked, is fit for use. When it is to be used it must be put into the furnace by the upper opening, and set upon two iron bars, introduced through the holes made for that purpose below the door of the fire-place. The Muffle must be placed on these bars in the fire-place in such a manner that its open end shall stand next to, and directly against the door of the fire-place, and may be joined to it with lute. Then the cupels are ranged in it, and the furnace is filled up, to the heighth of two or three inches above the Muffle, with small coals not bigger than a walnut, to the end that they may lie close round the Muffle, and procure it an equal heat on every side. The chief use of the Muffle is to prevent the coals and ashes from falling into the cupels, which would be very prejudicial to the operations carrying on in them: for the lead would not vitrify as it ought, because the immediate contact of the coals would continually restore its phlogiston; or else the glass of lead, which ought to penetrate and pass through the cupels, would be rendered incapable of so doing; because the ashes mixing therewith would give it such a consistence and tenacity as would destroy that property, or at least considerably lessen it. The openings, therefore, which are left in the lower part of the Muffle, should not be so high as to admit coals or ashes to get into the cupels; the use of them is to procure an easier passage for the heat and the air to those vessels. The Muffle is left quite open in its fore-part, that the operator may be at liberty to examine what passes in the cupels, to stir their contents, to remove them from one place to another, to convey new matters into them, &c. and also to promote the free access of the air, which must concur with the fire towards the evaporation necessary to the vitrification of lead; which air, if fresh were not often enough admitted, would be incapable of producing that effect; because it would soon be loaded with such a quantity of vapours that it could not take up any more. The government of the fire in this furnace is founded on the general principles above laid down for all furnaces. Yet as there are some little differences, and as it is very essential to the success of the operations for which this furnace is intended, that the artist should be absolutely master of his degree of heat, we shall in few words shew how that may be raised or lowered. When the furnace is filled with coals and kindled, if the door of the ash-hole be set wide open, and that of the fire-place shut very close, the force of the fire is increased; and if, moreover, the pyramidal cover be put on the top, and the conical funnel added to it, the fire will become still more fierce. Seeing the matters contained in this furnace are encompassed with fire on all sides, except in the fore-part opposite to the door of the fire-place, and as there are occasions which require that the force of the fire should be applied to this part also, an iron box, of the shape and size of the door, hath been contrived to answer that purpose. This box is filled with lighted coals, and applied immediately to the door-place, by which means the heat there is considerably augmented. This help may be made use of at the beginning of the operation, in order to accelerate it, and bring the heat sooner to the desired degree; or in case a very fierce heat be required; or at a time when the air being hot and moist will not make the fire burn with the necessary vigour. The heat may be lessened by removing the iron box, and shutting the door of the fire-place quite close. It may be still further and gradually diminished, by taking off the conical funnel from the top; by shutting the door of the fire-place with one of its plates only, that which has the least, or that which has the greatest aperture in it; by taking off the pyramidal cover; by shutting the ash-hole door wholly or in part; and, lastly, by setting the door of the fire-place wide open: but, in this last case, the cold air penetrates into the cavity of the Muffle, and refrigerates the cupels more than is almost ever necessary. If it be observed, during the operation, that the Muffle grows cold in any particular part, it is a sign there is a vacuity left by the coals in that place: in this case an iron wire must be thrust into the furnace, through the hole which is over the door of the fire-place, and the coals stirred therewith, so as to make them fall into their places and fill up the vacant interstices. It is proper to observe, that, besides what has been said concerning the ways of increasing the activity of the fire in the cupelling furnace, several other causes also may concur to procure to the matters contained in the Muffle a greater degree of heat: for example, the smaller the Muffle is, the wider and more numerous the holes in it are; the nearer to its bottom, or further end, the cupels are placed, the more will the matters therein contained be affected with heat. Besides the operations to be performed by the cupel, this furnace is very useful, and even necessary, for many chymical experiments; such, for instance, as those relating to sundry vitrifications and enamelling. As it is pretty low, the best way is to place it, when it is to be used, on a base of brick-work that may raise it to a level with the operator's hand. A Lamp-furnace is exceeding useful for all operations that require only a moderate, but long-continued, degree of heat. The furnace for working with a lamp-heat is very simple: it consists only of a hollow cylinder, from fifteen to eighteen inches high, and five or six in diameter, having at its bottom an aperture large enough for a lamp to be introduced and withdrawn with ease. The lamp must have three or four wicks, to the end that by lighting more or fewer of them a greater or less degree of heat may be produced. The body of the furnace must moreover have several small holes in it, in order to supply the flame of the lamp with air enough to keep it alive. On the top of this furnace stands a bason five or six inches deep, which ought to fill the cavity of the cylinder exactly, and to be supported at its circumference by a rim which may entirely cover and close the furnace: the use of this bason is to contain the sand through which the lamp-heat is usually conveyed. Besides this, there must be a kind of cover or dome made of the same material with the furnace, and of the same diameter with the sand-bath, without any other opening than a hole, nearly circular, cut in its lower extremity. This dome is a sort of reverberatory, which serves to confine the heat and direct it towards the body of the retort; for it is used only when something is to be distilled in a vessel of this fashion; and then the hole at its bottom serves for a passage to the neck of the retort. This dome should have an ear or handle, for the conveniency of putting it on and taking it off with ease. _Of Lutes._ Chymical vessels, especially such as are made of glass, and the earthen vessels commonly called stone-ware, are very subject to break when exposed to sudden heat or cold: whence it comes, that they often crack when they begin to heat, and also when being very hot they happen to be cooled, either by fresh coals thrown into the furnace, or by the access of cold air. There is no way to prevent the former of these accidents, but by taking the pains to warm your vessel very slowly, and by almost insensible degrees. The second may be avoided by coating the body of the vessel with a paste or lute, which being dried will defend it against the attacks of cold. The fittest stuff for coating vessels is a composition of fat earth, Windsor-loam, fine sand, filings of iron, or powdered glass, and chopped cow's hair, mixed and made into a paste with water. This lute serves also to defend glass vessels against the violence of the fire, and to prevent their melting easily. In almost all distillations it is of great consequence, as hath been said, that the neck of the distilling vessel be exactly joined with that of the receiver into which it is introduced, in order to prevent the vapours from escaping into the air and so being lost: and this junction is effected by means of a lute. A few slips of paper applied round the neck of the vessels with common size will be sufficient to keep in such vapours as are aqueous or not very spirituous. If the vapours are more acrid, or more spirituous, recourse may be had to slips of bladder long steeped in water, which containing a sort of natural glue, close the junctures of the vessels very well. If it be required to confine vapours of a still more penetrating nature, it will be proper to employ a lute that quickly grows very hard; particularly a paste made with quick-lime and any sort of jelly, whether vegetable or animal; such as the white of an egg, stiff size, _&c._ This is an excellent lute, and not easily penetrated. It is also used to stop any cracks or fractures that happen to glass vessels. But it is not capable of resisting the vapours of mineral acid spirits, especially when they are strong and smoking: for that purpose it is necessary to incorporate the other ingredients thoroughly with fat earth softened with water; and even then it frequently happens that this lute is penetrated by acid vapours, especially those of the spirit of salt, which of all others are confined with the greatest difficulty. In such cases its place may be supplied with another, which is called Fat Lute, because it is actually worked up with fat liquors. This lute is composed of a very fine cretaceous earth, called tobacco-pipe clay, moistened with equal parts of the drying oil of lint-seed, and a varnish made of amber and gum copal. It must have the consistence of a stiff paste. When the joints of the vessels are closed up with this lute, they may, for greater security, be covered over with slips of linen smeared with the lute made of quick-lime and the white of an egg. Chymical vessels are liable to be broken in an operation by other causes besides the sudden application of heat or cold. It frequently happens, that the vapours of the matters exposed to the action of fire rush out with such impetuosity, and are so elastic, that, finding no passage through the lute with which the joints of the vessels are closed, they burst the vessels themselves, sometimes with explosion and danger to the operator. To prevent this inconvenience, it is necessary that in every receiver there be a small hole, which being stopped only with a little lute may easily be opened and shut again as occasion requires. It serves for a vent-hole to let out the vapours, when the receiver begins to be too much crowded with them. Nothing but practice can teach the artist when it is requisite to open this vent. If he hits the proper time, the vapours commonly rush out with rapidity, and a considerable hissing noise; and the vent should be stopped again as soon as the hissing begins to grow faint. The lute employed to stop this small hole ought always to be kept so ductile, that, by taking the figure of the hole exactly, it may entirely stop it. Besides, if it should harden upon the glass, it would stick so fast that it would be very difficult to remove it without breaking the vessel. This danger is easily avoided by making use of the fat lute, which continues pliant for a long time, when it is not exposed to an excessive heat. This way of stopping the vent-hole of the receiver has yet another advantage: for if the hole be of a proper width, as a line and half, or two lines, in diameter, then, when the vapours are accumulated in too great a quantity, and begin to make a great effort against the sides of the receiver, they push up the stopple, force it out, and make their way through the vent-hole: so that, by this means, the breaking of the vessels may always be certainly prevented. But great care must be taken that the vapours be not suffered to escape in this manner, except when absolute necessity requires it; for it is generally the very strongest and most subtile part of a liquor which is thus dissipated and lost. Heat being the chief cause that puts the elasticity of the vapours in action, and prevents their condensing into a liquor, it is of great consequence in distillation that the receiver be kept as cool as possible. With this view a thick plank should be placed between the receiver and the body of the furnace, to intercept the heat of the latter, and prevent its reaching the former. As the vapours themselves rise very hot from the distilling vessel, they soon communicate their heat to the receiver, and especially to its upper part, against which they strike first. For this reason it is proper that linen cloths, dipt in very cold water, be laid over the receiver, and frequently shifted. By this means the vapours will be considerably cooled, their elasticity weakened, and their condensation promoted. By what hath been said in this first part, concerning the properties of the principal agents in Chymistry, the construction of the most necessary vessels and furnaces, and the manner of using them, we are sufficiently prepared for proceeding directly to the operations, without being obliged to make frequent and long stops, in order to give the necessary explanations on those heads. Nevertheless, we shall take every proper occasion to extend the theory here laid down, and to improve it by the addition of several particulars, which will find their places in our Treatise of Chymical Operations. ELEMENTS OF THE PRACTICE OF CHYMISTRY; WHEREIN The Fundamental Operations are described, and illustrated by Observations on each Process. [Illustration: Decorative Scroll] ELEMENTS OF THE PRACTICE OF CHYMISTRY. INTRODUCTION. AS the Elements of the Theory of Chymistry, delivered in the former part of this work, were intended for the use of persons supposed to be altogether unacquainted with the art, they could not properly admit of any thing more than fundamental principles, so disposed as constantly to lead from the simple to the compound, from things known to things unknown: for which reason I could not therein observe the usual order of Chymical Decomposition, which is not susceptible of such a method. I therefore supposed all the analyses made, and bodies reduced to their simplest principles; to the end that, by observing the chief properties of those primary elements, we might be enabled to trace them through their several combinations, and to form some sort of judgment _a priori_ of the qualities of such compounds as may result from their junctions. But this latter part is of a different nature. It is a practical Treatise, intended to contain the manner of performing the principal Operations of Chymistry; the operations which serve as standards for regulating all the rest, and which confirm the fundamental truths laid down in the Theory. As these operations consist almost wholly of analyses and decompositions, there can be no doubt concerning the order proper to be observed in giving an account of them: it evidently coincides with that of the analysis itself. But as all bodies, which are the subjects of Chymical operations, are divided by nature into three classes or kingdoms, the mineral, the vegetable, and the animal, the analysis thereof may naturally be divided into three branches: some difference may also arise from the different order in which these three may be treated of. As the reasons assigned for beginning with one kingdom rather than with another have never been thoroughly canvassed, and may perhaps seem equally good when viewed in a particular light, Chymical writers differ in their opinions on this point. For my part, without entering into a discussion of the motives which have determined others to follow a different order, I shall only produce the reasons that led me to begin with the mineral kingdom, to examine the vegetable in the second place, and to conclude with the animal. First, then, seeing vegetables draw their nourishment from minerals, and animals derive theirs from vegetables, the bodies which constitute these three kingdoms seem to be generated the one by the other, in a manner that determines their natural rank. Secondly, this disposition procures us the advantage of tracing the principles, from their source in the mineral kingdom, down to the last combinations into which they are capable of entering, that is, into animal matters; and of observing the successive alterations they undergo in passing out of one kingdom into another. Thirdly and lastly, I look upon the analysis of minerals to be the easiest of all; not only because they consist of fewer principles than vegetables and animals, but also because almost all of them are capable of enduring the most violent action of fire, when that is necessary to their decomposition, without any considerable change or diminution of their principles, to which those of other substances are frequently liable. Besides, I am not singular in this distribution of the three classes of bodies, which are the subjects of the chymical analysis: as it is the most natural, it has been adopted by several authors, or rather by most who have published Treatises of Chymistry. But there is something peculiarly my own in the manner wherein I have treated the analysis of each kingdom. In the mineral kingdom, for instance, will be found a considerable number of operations not to be met with in other Treatises of Chymistry; the authors having probably considered them as useless, or in some measure foreign, to the purpose of Elementary Books, and as constituting together a distinct art. I mean the processes for extracting saline and metallic substances from the minerals containing them. Yet, if it be considered that salts, metals, and semi-metals are far from being produced by nature in a state of perfection, or in that degree of purity which they are commonly supposed to have when they are first treated of in Books of Chymistry; but that, on the contrary, these substances are originally blended with each other, and adulterated with mixtures of heterogeneous matters, wherewith they form compound minerals; I imagine it will be allowed, that the operations by which these minerals are decomposed, in order to extract the metals, semi-metals, and other simpler substances, especially as they are founded on the most curious properties of these substances, are so far from being useless or foreign to the purposes of an Elementary Treatise, that they are, on the contrary, absolutely necessary thereto. After I had made these reflections, I could not help thinking that an analysis of minerals, which should treat of saline and metallic substances, without taking any notice of the manner in which their matrices must be analysed, in order to extract them, would be no less defective than a treatise of the analysis of vegetables, in which Oils, essential Salts, fixed and volatile Alkalis, should be amply treated of, without saying one word of the manner of analysing the plants from which these several substances are obtained. I therefore thought myself indispensably obliged to describe the manner of decomposing every ore or mineral, before I attempted to treat of the saline or metallic substance which it yields. For example: as the Vitriolic Acid, with the consideration of which I begin my Mineral Analysis, is originally contained in Vitriol, Sulphur, and Alum; and as these substances again derive their origin from the sulphureous and ferruginous Pyrites, the first operations I describe under this head are the processes for decomposing the Pyrites in order to extract its Vitriol, Sulphur, and Alum. I then proceed to the particular analysis of each of these substances, with a view to extract their Vitriolic Acid; and afterwards deliver, in their order, the other operations usually performed on this Acid. Thus it appears, that this saline substance occasions my describing the analyses of the Pyrites, Vitriol, Sulphur, and Alum. The whole of the Treatise on Minerals proceeds on the same plan. The operations by which we decompose ores and minerals are of two sorts: those employed in working by the great, and those for trying in small the yield of any ore. These two manners of operating are sometimes a little different; yet in the main they are the same, because they are founded on the same principles, and produce the same effects. As my chief design was to describe the operations that may be conveniently performed in a laboratory, I have preferred the processes for small assays: especially as they are usually performed with more care and accuracy than the operations in great works: and here I must acknowledge, that I am obliged to M. Cramer's _Docimasia_, or Art of Assaying, for all the operations of this kind in my analysis of minerals. As M. Hellot's work on that subject did not appear till after I had finished this, M. Cramer's _Docimasia_, in which sound Theory is joined with accurate practice, was the best book of the kind I could at that time consult. I therefore preferred it to all others; and as I have not quoted it in my analysis of minerals, because the quotations would have been too frequent, let what I say here serve for a general quotation. I have been careful to name, as often as occasion required, the other authors whose processes I have borrowed: it is a tribute justly due to those who have communicated their discoveries to the public. Though I have told the reader that in my analysis of minerals he will find the processes for extracting out of each the saline or metallic substances contained in it, yet he must not expect that this book will instruct him in all that is necessary he should know to be able to determine, by an accurate assay, the contents of every mineral. My intention was not to compose a Treatise of Assaying; and I have taken in no more than was absolutely necessary to make the analysis of minerals perfectly understood, and to render it as complete as it ought to be in an Elementary Treatise. I have therefore described only the principal operations relating thereto; the operations which are fundamental, and which, as I said before, are to serve as standards for the rest, abstracted from such additional circumstances as are of consequence only to the Art of Assaying, properly so called. Such therefore as are desirous of being fully instructed in that Art, must have recourse to those works which treat professedly of the subject; and particularly to that published by M. Hellot: a performance most esteemed by such as are best skilled in Chymistry, and rendered so complete by the numerous and valuable observations and discoveries of the Author, that nothing better of the kind can be wished for. I thought it proper to give these notices in relation to my analysis of minerals; and shall now proceed to shew the plan of my analyses of vegetables and of animals. Seeing all vegetable matters are susceptible of fermentation, and when analysed after fermentation, yield principles different from those we obtain from them before they are fermented, I have divided them into two classes; the former including vegetables in their natural state, before they have undergone fermentation; and the latter those only which have been fermented. This analysis opens with the processes by which we extract from vegetables all the principles they will yield without the help of fire: and then follow the operations for decomposing plants by degrees of heat, from the gentlest to the most violent, both in close vessels, and in the open air. I have not made the same division in the animal kingdom, because the substances that compose it are susceptible only of the last degree of fermentation, or putrefaction; and moreover the principles they yield, whether putrefied or unputrefied, are the very same, and differ only with regard to their proportions, and the order in which they are extricated during the analysis. I begin this analysis with an examination of the milk of animals that feed wholly on vegetables; because, though this substance be elaborated in the body of the animal, and by that means brought nearer to the nature of animal matters, yet it still retains a great similitude to the vegetables from which it derives its origin, and is a sort of intermediate substance between the vegetable and animal. Then I proceed to the analysis of animal matters properly so called, those which actually make a part of the animal body. I next examine the excrementitious substances, that are thrown out of the animal body as superfluous and useless. And then I conclude this latter part with operations on the Volatile Alkali; a saline substance of principal consideration in the decomposition of animal matters. Though, in the general view here given of the order observed in this Treatise of Practical Chymistry, I have mentioned only such processes as serve for analysing bodies, yet I have also inserted some other operations of different kinds. The book would be very defective if it contained no more: for the design of Chymistry is not only to analyse the mixts produced by nature, in order to obtain the simplest substances of which they are composed, but moreover to discover by sundry experiments the properties of those elementary principles, and to recombine them in various manners, either with each other, or with different bodies, so as to reproduce the original mixts with all their properties, or even form new compounds which never existed in nature. In this book therefore the reader will find processes for combining and recompounding, as well as for resolving and decomposing bodies. I have placed them next to the processes for decomposition, taking all possible care not to interrupt their order, or break the connection between them. PART I. OF MINERALS. SECTION I. _Operations performed on Saline Mineral Substances._ CHAP. I. _Of the_ VITRIOLIC ACID. PROCESS I. _To extract Vitriol from the Pyrites._ Take any quantity you please of Iron Pyrites; leave them for some time exposed to the air: they will crack, split, lose their brightness, and fall into powder. Put this powder into a glass cucurbit, and pour upon it twice its weight of hot water; stir the whole with a stick, and the liquor will grow turbid. Pour it, while it is yet warm, into a glass funnel lined with brown filtering paper; and having placed your funnel over another glass cucurbit, let the liquor drain into it. Pour more hot water on the powdered Pyrites, filter as before, and so go on, every time lessening the quantity of water, till that which comes off the Pyrites appears to have no astringent vitriolic taste. Put all these waters together into a glass vessel that widens upwards; set it on a sand-bath, and heat the liquor till a considerable smoke arises; but take care not to make it boil. Continue the same degree of fire till the surface of the liquor begins to look dim, as if some dust had fallen into it; then cease evaporating, and remove the vessel into a cool place: in the space of four and twenty hours will be formed therein a quantity of crystals, of a green colour and a rhomboidal figure: these are Vitriol of Mars, or Copperas. Decant the remaining liquor; add thereto twice its weight of water; filter, evaporate, and crystallize as before; repeat these operations till the liquor will yield no more crystals, and keep by themselves the crystals obtained at each crystallization. _OBSERVATIONS._ The Pyrites are minerals which, by their weight and shining colours, frequently impose on such as are not well acquainted with ores. At first sight they may be taken for very rich ones; and yet they consist only of a small quantity of metal combined with much sulphur or arsenic, and sometimes with both. They strike fire with a steel as flints do, and emit a sulphureous smell: so that they may be known by this extemporaneous proof. The metal most commonly and most abundantly found in the Pyrites is iron; the quantity whereof sometimes equals, or even exceeds, that of the sulphur. Besides metallic and sulphureous matters, the Pyrites contain also some unmetallic earth. There are several sorts of Pyrites: some of them contain only iron and arsenic. They have not all the property of efflorescing spontaneously in the air, and turning into vitriol: none do so but such as consist only of iron and sulphur, or at least contain but a very small portion of copper, or of arsenic: and even amongst those that are composed of iron and sulphur alone, there are some that will continue for years together exposed to the air without shooting, and indeed without suffering the least sensible alteration. The efflorescence of the Iron Pyrites, and the changes they undergo, are phenomena well worth our notice. They depend on the singular property which iron possesses of decomposing sulphur by the help of moisture. If very fine iron-filings be accurately mingled with flowers of sulphur, this mixture, being moistened with water, grows very hot, swells up, emits sulphureous vapours, and even takes fire; what remains is found converted into Vitriol of Mars. On this occasion, therefore, the sulphur is decomposed; its inflammable part is dissipated or consumed; its acid combines with the iron, and a Vitriol arises from that conjunction. This is the very case with the Pyrites that consist only of iron and sulphur; yet some of them, as we said before, do not effloresce spontaneously and turn to Vitriol. The reason probably is, that, in such minerals, the particles of iron and sulphur are not intimately mixed together, but separated by some earthy particles. In order to procure Vitriol from Pyrites of this kind, they must be for some time exposed to the action of fire, which, by consuming part of their sulphur, and rendering their texture less compact, makes way for the air and moisture, to which they must be afterwards exposed, to penetrate their substance, and produce in them the changes with which those others are affected that germinate spontaneously. The Pyrites which contain copper and arsenic, and for that reason do not effloresce, must likewise undergo the action of fire; which, besides the effects it produces on Pyrites that consist of iron and sulphur only, dissipates also the greatest part of the arsenic. These Pyrites being first roasted, and then exposed to the air for a year or two, do also yield Vitriol; but then it is not a pure Vitriol of Iron, but is combined with a portion of blue Vitriol, the basis of which is Copper. Sometimes also there is Alum in the vitriolic waters drawn off the Pyrites. It was on account of this mixture of different salts that we recommended the keeping apart the crystals obtained from each different crystallization: for by this means they may be examined separately, and the species to which they belong discovered. When Vitriol of Iron is adulterated with a mixture of the Vitriol of Copper only, it is easy to purify it and bring it to be entirely martial, by dissolving it in water, and setting plates of iron in the solution: for iron having a greater affinity than copper with the vitriolic acid, separates the latter from it, and assuming its place produces a pure Vitriol of Mars. In large works for extracting Vitriol from the Pyrites they proceed thus. They collect a great quantity of Pyrites on a piece of ground exposed to the air, and pile them up in heaps of about three feet high. There they leave them exposed to the action of the air, sun, and rain, for three years together; taking care to turn them every six months, in order to facilitate the efflorescence of those which at first lay undermost. The rain-water which has washed those Pyrites is conveyed by proper channels into a cistern; and when a sufficient quantity thereof is gathered, they evaporate it to a pellicle in large leaden boilers, having first put into it a quantity of iron, some part of which is dissolved by the liquor, because it contains a vitriolic acid that is not fully saturated therewith. When it is sufficiently evaporated, they draw it off into large leaden or wooden coolers, and there leave it to shoot into crystals. In these last vessels several sticks are placed, crossing each other in all manner of directions, in order to multiply the surfaces on which the crystals may fasten. The Pyrites are not the only minerals from which Vitriol may be procured. All the ores of iron and copper that contain sulphur may also be made to yield green or blue Vitriol, according to the nature of each, by torrefying them, and leaving them long exposed to the air: but this use is seldom made of them, as there is more profit to be got by extracting the metals they contain. Besides, it is easier to obtain Vitriol from the Pyrites than from those other mineral substances. PROCESS II. _To extract Sulphur from the Pyrites, and other sulphureous Minerals._ Reduce to a coarse powder any quantity of yellow Pyrites, or other Mineral containing Sulphur. Put this powder into an earthen or glass retort, having a long wide neck, and so large a body that the matter may fill but two thirds of it. Set the retort in a sand-bath fixed over a reverberating furnace: fit to it a receiver half full of water, and so placed that the nose of the retort may be about an inch under the water: give a gradual fire, taking care you do not make it so strong as to melt the matter. Keep the retort moderately red for one hour, or an hour and half, and then let the vessels cool. Almost all the Sulphur separated by this operation from its matrix will be found at the extremity of the neck of the retort, being fixed there by the water. You may get it out either by melting it with such a gentle heat as will not set it on fire, or by breaking the neck of the retort. _OBSERVATIONS._ Of all minerals the Pyrites contain the most Sulphur; those especially which have the colour of fine brass, a regular form, such as round, cubical, hexagonal, and being broken present a number of shining needles, all radiating, as it were, from a center. A very moderate heat is sufficient to separate the Sulphur they contain. We directed that the retort employed should have a long and wide neck, with a view to procure a free passage for the Sulphur: the water set in the receiver detains the Sulphur, fixes it, and prevents it from flying off; so that it is unnecessary to close the joints of the vessels. But it is proper to take notice, that whenever you use an apparatus for distilling, which requires the beak of the retort to be under water, it is of very great consequence that the fire be constantly so regulated, that the retort may not cool in the least; for, in that case, as the rarefied air contained therein would be condensed, the water in the receiver would rise into the retort and break it. If in distilling Sulphur, according to the present process, the matter contained in the retort should happen to melt, the operation would be thereby considerably protracted, and it would require a great deal more time to extract all the Sulphur; because all evaporation is from the surface only, and the matter, while it remains in a coarse powder, presents a much more extensive surface than when it is melted. This remark holds with regard to all other distillations. Any quantity of liquor, set to distil in its fluid state, will take much more time to rise in vapours, and pass from the retort into the receiver, than if it be incorporated with some solid body reduced to minute parts, so that the whole shall make a moist powder; and this though the very same degree of fire be applied in both cases. If the matter from which it is proposed to extract Sulphur be such as will melt with the degree of fire necessary to this operation; that is, with a heat which will make the retort but faintly red, it must be mixed with some substance that is not so fusible. Very pure coarse sand, or clean gravel, may be used with success: but absorbent earths are altogether improper for this purpose, because they will unite with the Sulphur. The sulphureous minerals which are most apt to fuse are the cupreous Pyrites, or yellow copper ores: common lead ores are also very fusible. The Pyrites are by this operation deprived of almost all the Sulphur they contain; and consequently little is left behind, but the particles of iron and copper, together with a portion of unmetallic earth, which we shall shew how to separate from these metals, when we come to treat of them. I say that by this operation the Pyrites are deprived of almost all, and not entirely of all their Sulphur; because, this separation being made in close vessels only, there always remains a certain quantity of Sulphur, which adheres so obstinately to the metals, that it would be almost impossible to get it all out, even though a much stronger fire than that directed in the process were applied for this purpose, and though choice had been, as it ought to be, made of such Pyrites, or other sulphureous Minerals as part most easily with their sulphur. Nothing but a very strong fire in the open air is capable of carrying it wholly off, or consuming it entirely. In several places are found great quantities of native Sulphur. The Volcanoes abound with it, and people gather it at the foot of those burning mountains. Several springs of mineral waters also yield Sulphur, and it is sometimes found sublimed to the vaulted roofs of certain wells, and among others in one at Aix-la-Chapelle. The Germans and Italians have large works for extracting Sulphur in quantities out of Pyrites, and other minerals which abound therewith. The process they work by is the same with that here delivered; but with this difference only, that Sulphur being but of small value they do not use so many precautions. They content themselves with putting the sulphureous minerals into large crucibles, or rather earthen cucurbits, which they place in the furnace in such a manner that, when the sulphureous part melts, it runs into vessels filled with water, and is thereby fixed. The Sulphur obtained, either by distillation or by simple fusion, is not always pure. When it is obtained by distillation, if the matters from which you extract it contain moreover some other minerals of nearly the same volatility, such, for instance, as Arsenic, or Mercury, these minerals will come over with it. This is easily perceived: for pure sublimed Sulphur is always of a beautiful yellow, inclining to a lemon colour. If it look red, or have a reddish cast, it is a sign that some Arsenic hath risen along with it. Mercury sublimed with Sulphur likewise gives it a red colour; but Sulphur is very seldom adulterated with this metallic substance: for Arsenic is frequently found combined with the Pyrites, and other sulphureous minerals; whereas, on the contrary, we very rarely meet with any Mercury in them. But if Mercury should happen to rise with the Sulphur in distillation, it may be discovered by examining the sublimate; which, in that case, will have the properties of Cinabar: on being broken its inside will appear to consist of needles adhering laterally to each other; its weight will be very considerable; and, lastly, the great heat of the place where it is collected will furnish another mark to know it by; for, as Cinabar is less volatile than Arsenic or Sulphur, it fastens on places too hot for either Sulphur or Arsenic to bear. Sulphur may also be adulterated with such fixed matters, either metallic or earthy, as it may have carried up along with it in the distillation, or as may have been sublimed by the Arsenic, which has a still greater power than Sulphur to volatilize fixed bodies. If you desire to free the Sulphur from most of these heterogeneous matters, it must be put into an earthen cucurbit, and set in a sand-bath. To the cucurbit must be fitted one or more aludels, and such a degree of heat applied as shall but just melt the Sulphur; which is much less than that necessary to separate the Sulphur from its matrix. As soon as the Sulphur is melted it will sublime in lemon-coloured flowers, that will stick to the insides of the aludels. When nothing more appears to rise with this degree of heat, the vessels must be suffered to cool. At the bottom of the cucurbit will be found a sulphureous mass, containing the greatest part of the adventitious matters that were mixed with the Sulphur, and more or less red or dark-coloured, according to the nature of those matters. When we come to treat of Arsenic and Mercury, we shall give the methods of separating Sulphur entirely from those metallic substances. PROCESS III. _To extract Alum from aluminous Minerals._ Take such minerals as are known or suspected to contain Alum. Expose them to the air, that they may effloresce. If they remain there a year without any sensible change, calcine them, and then leave them exposed to the air, till a bit thereof being put on the tongue imparts an astringent aluminous taste. When your matters are thus prepared, put them into a leaden or glass vessel; pour upon them thrice their weight of hot water; boil the liquor; filter it; and repeat these operations till the earth be so edulcorated that the water which comes off it hath no taste. Mix all these solutions together, and let them stand four and twenty hours, that the gross and earthy parts may settle to the bottom; or else filter the liquor: then evaporate till it will bear a new-laid egg. Now let it cool, and stand quiet four and twenty hours: in that time some crystals will shoot, which are most commonly vitriolic; for Alum is rarely obtained by the first crystallization. Remove these vitriolic crystals: if any crystals of Alum be found amongst them, these must be dissolved anew, and set to crystallize a second time in order to their purification; because they partake of the nature as well as of the colour of vitriol. By this method extract all the Alum that the liquor will yield. If you get no crystals of Alum by this means, boil your liquor again, and add to it a twentieth part of its weight of a strong alkaline lixivium, or a third part of its weight of putrefied urine, or a small quantity of quick-lime. Experience and repeated trials must teach you which of these three substances is to be preferred, according to the particular nature of the mineral on which you are to operate. Keep your liquor boiling, and if there be any alum in it, there will appear a white precipitate: in that case let it cool and settle. When the white precipitate is entirely fallen, decant the clear, and leave the crystals of Alum to shoot at leisure, till the liquor will yield no more: it will then be exceeding thick. _OBSERVATIONS._ Alum is obtained from several sorts of Minerals. In some parts of Italy, and in sundry other places, it effloresces naturally on the surface of the earth. There it is swept together with brooms, and thrown into pits full of water. This water is impregnated therewith till it can dissolve no more. Then it is filtered, and set to evaporate in large leaden vessels; and when it is sufficiently evaporated, and ready to shoot into crystals, it is drawn off into wooden coolers, and there left for the salt to crystallize. In aluminous soils there are often found springs strongly impregnated with Alum: so that to obtain it, the water need only be evaporated. In the country about Rome there is a very hard stone, which is hewn out of the quarry just like other stones for building; this stone yields a great deal of Alum. In order to extract it, the stones are calcined for twelve or fourteen hours; after which they are exposed to the air in heaps, and carefully watered three or four times a-day for forty days together. In that time they begin to effloresce, and to throw out a reddish matter on their surface. Then they are boiled in water, which dissolves all the Alum they contain, and, being duly evaporated, gives it back in crystals. This is the Alum called _Roman Alum_. Several sorts of Pyrites also yield a great deal of Alum. The English have a stone of this kind, which, in colour, is very like a slate. This stone contains much Sulphur, which they get rid of by roasting it. After this they steep the calcined stone in water, which dissolves the Alum it contains, and to this solution they add a certain quantity of a lye made of the ashes of sea-weeds. The Swedes have a Pyrites of a bright golden colour, variegated with silver spots, from which they procure Sulphur, Vitriol, and Alum. They separate from it the Sulphur and the Vitriol by the methods above prescribed. When the liquor which hath yielded Vitriol is become thick, and no more vitriolic crystals shoot in it, they add an eighth part of its weight of putrefied urine, mixed with a lye made of the ashes of green wood. Upon this there appears and falls to the bottom a copious red sediment. They decant the liquor from this precipitate, and, when it is duly evaporated, find it shoot into beautiful crystals of Alum. What hath been said, concerning the several matrices from which Alum is obtained, sufficiently shews, that it is seldom solitary in the waters with which aluminous subjects have been lixiviated. It is almost always accompanied with a certain quantity of Vitriol, or other saline mineral matters, which obstruct its crystallization, and prevent its being pure. It is with a view to free it from these matters, that the waters impregnated with Alum are mixed with a certain quantity of the lye of some fixed Alkali, or with putrefied urine, which contains much volatile Alkali. These Alkalis have the property of decompounding all the Neutral salts which have for their basis either an absorbent earth or a metallic substance; and such as have a metallic substance for their basis more readily than those whose basis is an earth. Consequently, if they are mixed with a liquor in which both these sorts of salts are dissolved, they must decompound that sort whose basis is metallic sooner than the other whose basis is an earth. This is what comes to pass in a solution of Alum and Vitriol. The metallic part of the latter is separated from its acid by the Alkalis when mixed with that solution; and it is this metallic part, which is generally iron, that appears in the form of a reddish precipitate, as above-mentioned. But because Alkalis decompound also those Neutral salts which have an earth for their basis, care must be taken that too much thereof be not added; else what you put in, more than is necessary to decompound the vitriolic salts in your liquor, will attack the Alum, and decompound it likewise. The Alkali made use of to promote the crystallization of the Alum joins with the Vitriolic Acid, which had dissolved the substances now precipitated, and therewith forms different Neutral salts according to its particular nature. If the Alkali be a lixivium of common wood-ashes, the Neutral salt will be a vitriolated Tartar; if a lixivium of the ashes of a maritime plant like Soda, the Neutral salt will be a Glauber's salt; if putrefied urine, the Neutral salt will be a vitriolic Ammoniacal salt. Some of these salts incorporate with the Alum, which in large works crystallizes in vast lumps: and hence it comes that some sorts of Alum when mixed with a fixed Alkali smell like a volatile Alkali. The crystals of Alum are octaedral, that is, they are solids with eight sides. These octaedral solids are triangular pyramids, having their angles cut away, so that four of their surfaces are hexagons, and the other four triangles. Sulphur, Vitriol, and Alum are the three principal subjects in which we certainly know that the universal or Vitriolic Acid particularly resides, and from which we extract it when we want to have it pure. For this reason we thought it proper, before we treated of the extraction of this Acid, to shew the method of separating those matters themselves from the other minerals out of which we obtain them. Moreover, all the other matrices, in which the Vitriolic Acid is most commonly lodged, may be referred to one or other of the matters which serve as bases to these three minerals. To Sulphur we may refer all combinations of the Vitriolic Acid with an inflammable matter: but we must take care not to confound Sulphur with those Bitumens in which the Vitriolic Acid may be found: for the basis of those bitumens is a real Oil; whereas the basis of Sulphur is the pure Phlogiston. Yet as Oils themselves contain the Phlogiston, which, in union with the Vitriolic Acid forms a true Sulphur, it follows that such bitumens may in a certain respect be classed with Sulphur. The same is to be said of Vitriol. The name is usually given to such combinations only as are formed of the Vitriolic Acid with Iron or Copper, which make the green and blue Vitriol; and to a third species of Vitriol, which is white, and has Zinc for its basis: but as the Vitriolic Acid may, by particular combinations, be united with many other metallic substances, all such Metallic Salts must be referred to the class of Vitriols. The same may also be said of Alum, which is no other than a combination of the Vitriolic Acid with a particular kind of absorbent earth; so that all combinations of this Acid with any earth whatever may be placed in the same class. This last class of mixts is the most extensive of all that contain the Vitriolic Acid; because there are a vast many earths, all differing from one another, with which that Acid may be united. Alum properly so called, the Gypsums, Talcs, Selenites, Boles, and all the other compounds of this kind, differ from each other only in their particular earths. The different properties of these earthy salts depend on the nature of their bases. Those which are of the aluminous kind retain much water in crystallizing, which makes them very soluble in water, and gives them the property of acquiring readily the aqueous fluor when exposed to the fire. Those which are of the nature of the Selenites admit but very little water in their crystals, and consequently are almost insoluble in water; nor does the fire give them an aqueous fluor. Lastly, the Gypsums and Talcs are still more destitute of these properties. The natures of the earths in these several compounds are hitherto but very imperfectly known, and may give the Chymists occasion for inquiries equally curious and useful. The Vitriolic Acid is sometimes found complicated with a fixed alkaline basis. This is almost always the Alkali of Sea-salt; so that the compound is a Glauber's Salt. Some mineral waters are impregnated therewith; which happens when these waters contain Vitriol or Alum, together with Sea-salt. From the principles laid down, in our Elements of the Theory, it appears that the Vitriolic Acid hath not so great an affinity with earthy and metallic substances as with fixed Alkalis; and also that it is stronger than the Marine Acid, and hath a greater affinity with fixed Alkalis. This being allowed, the generation of native Glauber's Salts is easily accounted for. The Acid of aluminous or vitriolic Salts quits the earth or the metal with which it was combined, and expelling the Acid of Sea-salt unites with its basis. Warmth greatly promotes these decompositions. If the common fossil salt, usually called _Sal Gem_, or any other kind of Sea-salt, should happen to be near a Volcano, when it discharges flaming Sulphur, as is frequently the case, and if this Sulphur should run among the Sea-salt, a Glauber's Salt would instantly be formed in that place; because when Sulphur burns, its Acid is separated and set at liberty. Lastly, if aluminous or vitriolic matters, or burning Sulphur, should meet with the ashes of plants or trees consumed by fire, a vitriolated Tartar would be formed, because these ashes contain a fixed Alkali of the same nature with that of Tartar. The Vitriolic Acid when combined with an earthy basis adheres strongly thereto; so that the force of fire is able to expel very little or none of it. There is no way of separating it from such a basis, but by presenting to it an Alkaline Salt, with which it will unite: nor is it ever extracted from such matters when it is required pure. It does not adhere so firmly to metallic substances; but is separated from them by the force of fire: so that it may be obtained from the several sorts of Vitriol. It is usually drawn from Green Vitriol; that being the commonest sort. As to Sulphur, the Phlogiston which is its basis being the substance wherewith the Vitriolic Acid hath the greatest affinity, it would be altogether impossible to decompose it, and to separate its Acid, if it were not inflammable; but by burning it the Phlogiston is destroyed, and leaves the Acid at liberty. By this means therefore it may be separated. We shall now give the processes for extracting the Acid from Vitriol and Sulphur. PROCESS IV. _To extract the Vitriolic Acid from Green Vitriol._ Take any quantity of Green Vitriol: put it in an unglazed earthen vessel, and heat it gradually. Vapours will soon begin to rise. Increase the fire a little, and it will liquefy by means of the water contained in it, and acquire what we called an _aqueous_ fluor. Continue the calcination, and it will become less and less fluid, grow thick, and turn of a greyish colour. Now raise your fire, and keep it up till the salt recover its solidity, acquire an orange colour, and begin to grow red where it immediately touches the sides of the vessel. Then take it out, and reduce it to powder. Put the Vitriol thus calcined and pulverized into a good earthen retort, of which one half at least must remain empty. Set the retort in a reverberatory furnace: fit thereto a large glass receiver, and, having luted the joint well, give fire by degrees. You will soon see white clouds rise into the receiver, which will render it opaque, and heat it. Continue the same degree of fire till these clouds disappear: they will be succeeded by a liquor which will trickle down the sides of the receiver in veins. Still keep up the fire to the same degree as long as these veins appear. When they begin to abate, increase the fire, and push it to the utmost extremity: upon this, there will come over a black, thick liquor: it will even be found congealed, and prove the icy Oil of Vitriol, if care hath been taken to change the receiver, keep the vessels perfectly close, and give a sufficient degree of heat. Proceed thus till nothing more comes over, or at least very little. Let the vessels cool, unlute them, pour the contents of the receiver into a bottle, and seal it hermetically. _OBSERVATIONS._ Green Vitriol retains much water in crystallizing; and, in order to free it from that superfluous phlegm, it must be calcined before you distil it. Without this precaution the operation will be exceedingly protracted, and a great deal of time wasted in distilling such a quantity of water; which will moreover greatly weaken the Acid by commixing with it, unless care be taken to change the recipient as soon as the water is all come over. But there is also another advantage in calcining the Vitriol before you put it into the retort: for otherwise this salt would melt on the first application of heat, and run into a mass; which would prove a great hindrance to its distillation. This inconvenience is avoided by a previous calcination, in consequence whereof the Vitriol is easily reduced to a powder which never becomes fluid. Vitriol calcined as directed in the process grows so hard, and adheres so firmly to the vessel in which the calcination is performed, that it requires no small pains to separate and pulverize it. Care must be taken to put it into the retort as soon as it is pulverized, and to stop that vessel very close if you do not begin the distillation immediately: for otherwise it will naturally attract from the air almost all the moisture it hath lost. The Acid which Vitriol yields by distillation is sulphureous; probably because it still retains some of the Phlogiston, with which it was united when under the form of sulphur in the Pyrites; or else hath laid hold on a portion of that belonging to the iron which served for its basis in Vitriol. But this sulphureous part is volatile, and flies off in time. This decomposition of Vitriol in close vessels is a difficult and laborious process. To carry the operation to its utmost perfection requires a fire of extreme violence, kept up without intermission during four or five days; such in short as few vessels are able to bear. Of course this operation is seldom performed in laboratories. The French Chymists fetch their Oil of Vitriol from Holland, where it is extracted from Vitriol in large quantities, by means of furnaces erected for the purpose, in which many retorts are employed at once. In the Memoirs of the Academy of Sciences M. Hellot hath given us the most material circumstances of a very fine experiment of this kind, in which he pushed the distillation of Green Vitriol to the utmost. Into a German retort[5] he put six pounds of Green English Vitriol calcined to redness, which he exposed to a fire of the extremest violence, constantly kept up during four days and four nights. At the expiration of that time he found in the vessels employed as receivers an Icy Oil of Vitriol, which was altogether in a crystalline form and black. The precautions necessary to make this experiment succeed, he represents, in the following terms. [5] They are much the best, and bear a very fierce heat. "The success of this operation, which produces an Oil of Vitriol perfectly Icy and without any liquor, depends on the care taken to prevent the acid vapours, driven by the fire out of Vitriol calcined to redness, from having any communication with the external air while they are distilling: for otherwise they will attract from it a moisture which will keep them fluid in the receiver. The receiver must be at such a distance from the furnace that it may remain cool enough for the vapours to condense in it. There must also be sufficient room for those vapours to circulate in, and to prevent the sulphureous explosions, which are every now and then discharged out of the retort, from bursting the vessels: for though the previous calcination of the Vitriol hath carried off the most volatile, yet there still remains enough of the inflammable principle, even in the iron itself, to form a Sulphur with the Acid as it is extricated, or at least a mixt that would be as apt to take fire as common Sulphur, if it were not over-dosed with the Acid. "As the best means of gaining these ends, M. Hellot contrived to adapt to the neck of his retort a receiver with two necks, the lowermost of which was inserted into a large ballon. Receivers applied to each other in this manner are called Adopters. "It is no easy matter to get this Icy Oil out of the ballon: for as soon as the air touches it such a thick cloud of sulphureous fumes arises, that it is absolutely necessary to place the vessel on some shelf over head, because a man cannot stand exposed thereto for a single minute without being suffocated." This Icy Acid must be shut up with all possible expedition in a crystal bottle accurately closed with a glass stopple, which should be ground with emery in its neck so as to fit it exactly: for it attracts moisture so powerfully, that, unless exceeding great care be taken to prevent all communication with the external air, it will soon dissolve into a fluid. "The Icy Oil is black; because the acid vapours carry over with them something of a greasy matter, from which Vitriol is seldom free, and which always appears, after repeated solutions and crystallizations of this Salt, in the mother-water which will shoot no more. Now the smallest portion of inflammable matter presently blackens the most highly rectified Oil of Vitriol, which is perfectly clear. "The Vitriolic Acid, when forced over by a violent heat, carries along with it some ferruginous particles also, that want nothing but to be united with a phlogiston to become true iron. They are easily discovered, either in the common black Oil of Vitriol, or in the blackish crystals of the Icy Oil, by only dissolving them in a large quantity of distilled water: for after seven or eight days digestion a light powder or downy sediment precipitates, which being calcined in a violent fire is partly attracted by the magnet; and being again calcined with bees-wax becomes almost entirely iron." The _Caput mortuum_ of this distillation of Vitriol is the ferruginous earth of this Salt, and is called _Colcothar_. When this Colcothar hath undergone a violent fire, as in the experiment now related, scarce any Acid remains therein. Out of six pounds of Vitriol that M. Hellot used, he could recover no more, by lixiviating what was left in the retort, than two ounces of a Vitriolic Salt; and even that was very earthy. If Vitriol be exposed to a fire neither so violent nor so long continued, its Colcothar will yield a greater quantity of Vitriol that hath not been decomposed. A white crystalline salt is also obtained from it, and called _Salt of Colcothar_; which is no other than the small portion of Alum usually contained in Vitriol, and not so easily decomposed by the the action of fire. PROCESS V. _To decompose Sulphur, and extract its Acid, by burning it._ Take any quantity of the purest Sulphur: fill therewith a crucible or other earthen dish: heat it till it melts; then set it on fire, and, when its whole surface is lighted, place it under a large glass head, taking care that the flame of the Sulphur do not touch either its sides or bottom; that the air have free access, in order to make the Sulphur burn clear; and that the head incline a little toward the side on which its beak is, that, as the vapours condense therein, the liquor may run off with ease. To the beak of this vessel fit a receiver: the fumes of the lighted sulphur will be condensed, and gather into drops in the head, out of which they will run into the receiver. There, when the Sulphur has done burning, you will find an Acid liquor, which is the Spirit of Sulphur. _OBSERVATIONS._ In the burning of Sulphur, the Phlogiston which serves for its basis is dissipated, and separated from the acid which is left at liberty. The acid fumes which rise from the lighted sulphur strike against the inside of the head placed over it, are there condensed, and appear in the form of a liquor. But as Sulphur, like all other inflammable bodies, Nitre excepted, will not burn in close vessels, it is necessary that the air be freely admitted here; which occasions the loss of a great deal of the Acid of the Sulphur, as is evident from the pungent suffocating smell perceived in the laboratory during the operation. This Acid, while combined with the Phlogiston, is incapable of contracting any union with water; but when alone is very apt to mix therewith: it is even proper to put some in its way, that it may incorporate therewith as soon as it is discharged from the Sulphur; for it is then very free from phlegm, very volatile, and consequently very little disposed to condense into a liquor, but, on the contrary, very apt to fly off in vapours. The water, which it imbibes with a kind of avidity, fixes and detains it; so that by this means a much greater quantity thereof is obtained from Sulphur, than if it were distilled without this precaution. It is proper, therefore, now and then, to introduce a dish full of hot water under the head which receives the fumes of the Sulphur. The vapours that exhale from the water be-dew the inside of the head, and procure the advantage we are speaking of. The same thing may be effected several other ways: thus, the crucible containing the Sulphur may be set on a foot placed in an earthen dish with some water in it; which, however, must not rise above the foot; for if it should reach the crucible, it might cool and fix the sulphur. The dish thus prepared must be placed on a sand-bath hot enough to make the water smoke continually; and over all is to be placed the head as directed in the process. The size and form of the vessel which immediately receives the sulphureous fumes may also contribute to increase the quantity of the Acid Spirit. A very large vessel, with a hole at bottom no wider than is just sufficient to admit the vapours, is the properest for this operation. After the Sulphur has burnt for some time, it often happens that a sort of skin or crust forms on its surface, which is not inflammable, but gradually lessens the quantity and vigour of the flame as it increases in thickness, and at last puts it quite out. This crust proceeds from the impurities, and heterogeneous uninflammable particles contained in the sulphur. Care must be taken to remove it with an iron wire as fast as it forms. Two quantities of sulphur may also be kept in two crucibles, and heated alternately. That in which the Sulphur is hot and melted may be substituted for the other in which the Sulphur is grown cold and fixed; because cold Sulphur does not burn well. The Spirit of Sulphur is at first pungent and volatile, because it still retains a small portion of the Phlogiston: but that sulphureous part flies off, especially if the bottle in which the Spirit is kept be left for some time unstopped. The Acid obtained from Sulphur appears by all chymical proofs perfectly like that obtained from Vitriol: they differ in this only, that the former is the purest; for the Acid obtained from Vitriol carries over with it some metallic parts, as we observed before, which can never happen to that obtained from Sulphur. If linen rags dipped in a solution of Fixed Alkali be exposed to the fumes of burning brimstone, the Spirit of Sulphur joins with the Alkali, and therewith forms a Vitriolated Tartar. This Salt is known to be formed when the rags grow stiff, and appear spangled with a vast many glittering points, which are nothing but little crystals of the Salt we are speaking of. When the Sulphur burns very gently and slowly the Spirit that exhales from it is so much the more sulphureous and volatile: and hence the Salt formed by the combination of this Spirit with the Alkali exposed to it in linen rags, as in the above-mentioned experiment, is not at first a Vitriolated Tartar; but a Neutral Salt of a particular kind, which is capable of being decomposed by any other Mineral Acid, the sulphureous Acid having less affinity than any of the rest with Alkalis. Nevertheless, this Salt becomes in time a true Vitriolated Tartar, because the sulphureous part which weakened its Acid easily quits it and flies off. PROCESS VI. _To concentrate the Vitriolic Acid._ Take the Vitriolic Acid you intend to concentrate, that is, to dephlegmate and make stronger: pour it into a good glass retort, of such a size that your quantity of Acid may but half fill it: set this retort in the sand-bath of a reverberating furnace: fit to it a receiver; lute it on, and give a gradual fire. There will come over into the receiver a clear liquor, the first drops of which will be but faintly acid: this is the most aqueous part. When the drops begin to follow one another much more slowly, raise your fire, till the liquor begin to bubble a little in the middle. Keep it thus gently boiling, till one half or two thirds thereof be come over into the receiver. Then let your vessels cool; unlute them; what remains in the retort pour into a crystal bottle, and stop it exactly with a glass stopple rubbed with emery. _OBSERVATIONS._ The Acid obtained from Sulphur is generally very aqueous; either because in preparing it water must necessarily be administered, that it may unite therewith as it separates from the Sulphur; or because it is so greedy of moisture as to attract a great deal from the air, which must needs be admitted to make the Sulphur burn. The Acid obtained from Vitriol, excepting that which rises last, is also mixed with a pretty considerable quantity of phlegm; because the Vitriol, though calcined, still retains a great deal thereof, which rises with the Acid in distillation. Now, as there are many chymical experiments that will not succeed without Acids exceedingly dephlegmated, it is proper to have in a laboratory all the Acids thus conditioned; because if they happen to be too strong for particular operations, as is sometimes the case, it is very easy to lower them to the desired degree, by adding a sufficient quantity of water. The Vitriolic Acid is much heavier and much less volatile than water. If therefore a mixture of these two liquors be exposed to the fire, the aqueous part will rise with a degree of heat which is not able to carry up the Acid: by this means they may be separated from each other; and thus is the Vitriolic Acid concentrated. Nevertheless, as this Acid combines most closely with water, and is in a manner strongly connected with it, the water carries up some portion thereof along with it; and hence it comes, that the liquor which rises into the receiver is acid: it is called _Spirit of Vitriol_. As the fire carries off the most aqueous part, the other which remains in the retort increases in specific gravity. The Acid particles are brought nearer together, retain the aqueous particles more obstinately, and therefore to separate them the degree of heat must be increased. It is usual to draw off one half or two thirds of the liquor that was put into the retort: but this depends on the degree of strength the Acid was of before concentration, and the degree of concentration intended to be given it. If the Acid to be concentrated be Oil of Vitriol, from being brown or black it grows clearer as the operation advances, and at last becomes perfectly colourless and transparent; because the fat matter which tinged it black is dissipated during the process. Some of it deposites a white crystalline earth. A sulphureous smell is generally perceived about the vessels in this operation. This arises from a small portion of the Phlogiston from which the Acid is not free; and it is this inflammable matter which gives the Oil of Vitriol its black colour: for the clearest and best rectified Oil of Vitriol will become brown, and even black, in a short time, if any inflammable matter, though in a very small quantity, be dissolved therein. The vessels are luted in this operation, to prevent any loss of the Spirit of Vitriol, which being very acid is of use in many chymical experiments, and may itself also be again concentrated. We observed, that in this operation it is necessary the retort should be of very good glass. Indeed the Acid is so active, and so strong, that if the glass be tender and have a little too much salt in its composition, it will be so corroded thereby that it will fall to pieces. Though we directed the retort to be set in a sand-bath for this operation, it does not follow that it may not also be placed in a naked fire: on the contrary, when the heat is not conveyed through a bath the operation advances faster, and is much less tedious. But then great caution must be used, and the closest attention given to the management of the fire, which must be raised by almost imperceptible degrees, especially at the beginning of the operation; otherwise it is next to a certainty that the vessels will break. In general, a naked fire may be employed in almost all distillations which require a greater degree of heat than that of boiling water, or the _balneum mariæ_: the operation will be sooner finished; but it requires an experienced hand, that has by practice acquired a habit of governing the fire with judgment. There is moreover another advantage in not using the sand-bath; which is, that if in the time of the operation you perceive the fire too fierce, you can quickly check it, either by stopping close all the apertures of the furnace, or by drawing out all or part of the lighted coals. This inconvenience is not near so easily remedied when you use the sand-bath; because when once heated it retains its heat very long after the fire is quite extinguished. PROCESS VII. _To decompose Vitriolated Tartar by means of the Phlogiston; or to compose Sulphur by combining the Vitriolic Acid with the Phlogiston._ Take equal parts of Vitriolated Tartar, and very dry Salt of Tartar, separately reduced to powder; add an eighth part of their weight of charcoal-dust; and mix the whole together very accurately. Throw this mixture into a red-hot crucible, placed in a furnace filled with burning coals. Cover it very close, and keep it very hot; till the mixture melt, which may be known by uncovering the crucible from time to time. There will then appear a blueish flame, accompanied with a pungent smell of Sulphur. Take the crucible out of the fire: dissolve its contents in hot water: filter the solution through brown paper supported by a glass funnel: drop into the filtered liquor by little and little any Acid whatever. As you add the acid the liquor will grow more and more turbid, and let fall a grey precipitate. Continue dropping in more Acid till the liquor will yield no more precipitate. Filter it a second time, to separate it from the precipitate: what remains on the filter is a true inflammable Sulphur, which you may either melt or sublime into flowers. _OBSERVATIONS._ All bodies that contain the Vitriolic Acid may contribute, as well as Vitriolated Tartar, to the generation of Sulphur: so that all the neutral salts in which this Acid is a principle, the Alums, Selenites, Gypsums, Vitriols, may be substituted for it in this experiment. All these matters, with the addition of charcoal-dust only, being fused in a crucible, constantly produce Sulphur; because the Vitriolic Acid having a greater affinity with the Phlogiston than with any thing else, will quit its basis, whatever it be, to join with the Phlogiston of the charcoal, and therewith form a Sulphur. The fixed Alkali added thereto helps to promote the fusion of the ingredients, which is necessary for effecting the desired combination. It also serves to unite with the Sulphur, when formed; and thus makes the combination called _Liver of Sulphur_, which prevents the Sulphur from being consumed as soon as formed: for the fixed Alkalis, which are incombustible, hinder Sulphur from burning so easily as it would do if they were not joined with it. They may afterwards be separated from each other, by the means of any Acid whatever. This process, in which Sulphur is regenerated by recombining together the principles of which it was originally composed, is one of the most beautiful experiments that modern Chymistry hath produced. We are indebted for it to M. Stahl; and Dr. Geoffroy hath given a particular account of it in the Memoirs of the Academy of Sciences. Before these gentlemen Glauber and Boyle had indeed published methods of producing Sulphur, Glauber made use of his _Sal mirabile_ and powdered charcoal: Boyle employed the Vitriolic Acid and Oil of Turpentine. But neither of those Chymists understood the true theory of their operations: they did not thoroughly know the principles of Sulphur: they did not imagine they had composed Sulphur: they thought they only extracted what they supposed to exist previously in the matters they employed in their experiments. M. Stahl was the first who discovered and explained the nature of Sulphur, and proved that in Glauber's and Boyle's experiments Sulphur was actually produced, by uniting together the principles of which it is constituted. This beautiful experiment gives the strongest lustre of evidence to the theory of the composition of that mixt, which acts such a capital part in Chymistry; and it can no longer be doubted, that Sulphur is actually a combination of the Vitriolic Acid with the Phlogiston. Besides this important truth, our process for composing Sulphur by art proves several others that are equally essential and fundamental. The first is, that the Vitriolic Acid hath a greater affinity with the Phlogiston than with any other thing, seeing it quits metallic and earthy substances, as well as Alkaline salts, in order to combine therewith. The second is, that Sulphur combines with fixed Alkalis without suffering any decomposition; seeing it may be separated from them entire and unaltered; and seeing that very Sulphur, which is naturally indissoluble in water, is rendered soluble therein by the union it hath contracted with the fixed alkali. The third is, that the Vitriolic Acid, which, when it is pure, hath the greatest affinity with Alkalis of any Acid whatever, loses a great deal of that affinity by contracting an union with the Phlogiston; seeing the weakest acids are capable of decomposing the Liver of Sulphur, and separating the Sulphur from the Alkali. And this also confirms one of the general propositions concerning affinities advanced in our theory; to wit, that the affinities of compound or mixed substances are weaker than those of the same substances in a purer or more simple state. CHAP. II. _Of the_ NITROUS ACID. PROCESS I. _To extract Nitre out of nitrous Earths and Stones. The Purification of Salt-petre. Mother of Nitre. Magnesia._ Take any quantity of nitrous earths or stones; reduce them to powder; and therewith mix a third part of the ashes of green-wood and quick-lime. Put this mixture into a barrel or vat, and pour on it hot water to about twice the weight of the whole mass. Let it stand thus for twenty-four hours, stirring it from time to time with a stick. Then filter the liquor through brown paper, or pass it through a flannel bag, till it come clear: it will then have a yellowish colour. Boil this liquor, and evaporate till you perceive that a drop of it let fall on any cold body coagulates. Then stop the evaporation, and set your liquor in a cool place. In the space of four and twenty hours crystals will be formed in it, the figure of which is that of an hexagonal prism, having its opposite planes generally equal, and terminated at each extremity by a pyramid of the same number of sides. These crystals will be of a brownish colour, and deflagrate on a live coal. Decant the liquor from these crystals; mix it with twice its weight of hot water; evaporate and crystallize as before. Repeat the same operation till the liquor will yield no more crystals: it will then be very thick, and goes by the name of _Mother of Nitre_. _OBSERVATIONS._ Earths and stones that have been impregnated with animal or vegetable juices susceptible of putrefaction, and have been long exposed to the air, but sheltered from the sun and rain, are those which yield the greatest quantity of Nitre. But all sorts of earths and stones are not equally fit to produce it. None is ever found in flints or sands of a crystalline nature. Some earths and stones abound so with Nitre, that it effloresces spontaneously on their surface, in the form of a crystalline down. This Nitre may be collected with brooms, and accordingly has the name of _Salt-petre Sweepings_. Some of this sort is brought from India. Hitherto we are much in the dark as to the origin and generation of Nitre. Some Chymists pretend that the Nitrous Acid is diffused through the air, and gradually deposited in such earths and stones as are qualified to receive it. Others, considering that none of it is ever obtained but from earths that have been impregnated with vegetable or animal juices, have from thence concluded those two kingdoms to be the general repositories of the Nitrous Acid; that if we do not perceive it to exist in such matters at all, or at least in any great quantity, till they have undergone putrefaction, and are in some measure incorporated with suitable earths and stones, it is because the Acid is so entangled with heterogeneous particles that it requires the assistance of putrefaction, and much more of filtration through an earth, to disengage it, and enable it to appear in its proper nature. Lastly, others are of opinion that this Acid is no other than the universal or Vitriolic Acid; disguised indeed by a portion of the Phlogiston, which is combined with it in a peculiar manner by the means of putrefaction. They ground this opinion chiefly on the analogy or resemblance which they find between the Nitrous Acid and the Volatile Sulphureous Spirit. Its volatility, its pungent smell, its properties of taking fire, and of destroying the blue and violet colours of vegetables, serve them as so many proofs. Their opinion is the more probable on this account, that even though the Nitrous Acid should actually be produced by vegetable and animal substances, yet as these substances themselves draw all their component principles from the earth, and as the Vitriolic Acid is diffused through all the soils which afford them nourishment, there is great reason to think that the Nitrous Acid is no other than the Vitriolic Acid altered by the changes and combinations it hath undergone in its passage into and through those substances. In 1750 the Royal Academy of Sciences at Berlin proposed an account of the generation of Nitre as the subject for their prize, which was conferred on a Memoir wherein this last opinion was supported by some new and very judicious experiments. The process by which our Salt-petre makers extract Nitre in quantities, out of rubbish and nitrous earths, is very nearly the same with that here set down; so that I shall not enter into a particular account of it. I shall only take notice of one thing, which it is of some consequence to know; namely, that there is no nitrous earth which does not contain sea-salt also. The greatest quantities of this salt are to be found in those earths which have been drenched with urine, or other animal excrements. Now as the rubbish of old houses in great cities is in this class, it comes to pass that when the Salt-petre workers evaporate a nitrous lixivium drawn from that rubbish, as soon as the evaporation is brought to a certain pitch, a great many little crystals of sea-salt form in the liquor, and fall to the bottom of the vessel. The Salt-petre workers in France call these saline particles _the Grain_, and take care to separate them from the liquor (which, as long as it continues hot, keeps the salt-petre dissolved) before they set it to crystallize. This fact seems a little singular, considering that sea-salt dissolves in water more easily than salt-petre, and crystallizes with more difficulty. In order to discover the cause of this phenomenon, we must recollect some truths delivered in our theoretical Elements. The first is, that water can keep but a determinate quantity of any salt in solution, and that if water fully saturated with a salt be evaporated, a quantity of salt will crystallize in proportion to the quantity of water evaporated. The second is, that those salts which are the most soluble in water, particularly those which run in the air, will dissolve in cold and in boiling water equally; whereas much greater quantities of the other salts will dissolve in hot and boiling water than in cold water. These things being admitted, when we know that sea-salt is one of the first sort, and salt-petre of the second, the reason why sea-salt precipitates in the preparation of salt-petre appears at once. For, When the solution of Salt-petre and Sea-salt comes to be evaporated to such a degree that it contains as much Sea-salt as it possibly can, this salt must begin to crystallize, and continue to do so gradually as the evaporation advances. But because at the same time it does not contain as much salt-petre as it can hold, seeing it is capable of dissolving a much greater quantity thereof when it is boiling hot than when it is cold, this last-named salt will not crystallize so soon. If the evaporation were continued till the case of the Salt-petre came to be the same with that of the Sea-salt, then the salt-petre also would begin to crystallize gradually in proportion to the water evaporated, and the two salts will continue crystallizing promiscuously together: but it is never carried so far; nor is it ever necessary: for, as the water cools, it becomes more and more incapable of holding in solution the same quantity of salt-petre as when it was boiling hot. And then comes the very reverse, with regard to the crystallizing of the two salts; for then the Salt-petre shoots, and not the Sea-salt. The reason of this fact also is founded on what has just been said. The Sea-salt, of which cold water will dissolve as much as boiling water, and which owed its crystallizing before only to the evaporation, now ceases to crystallize as soon as the evaporation ceases; while the Salt-petre, which the water kept dissolved only because it was boiling hot, is forced to crystallize merely by the cooling of the water. When the solution of Salt-petre has yielded as many crystals of that Salt as it can yield by cooling, it is again evaporated, and being then suffered to cool yields more crystals. And thus they continue evaporating and crystallizing, till the liquor will afford no more crystals. It is plain that as the Salt-petre crystallizes, the proportion of Sea-salt to the dissolving liquor increases; and as a certain quantity of water evaporates also during the time employed in crystallizing the Salt-petre, a quantity of Sea-salt, proportioned to the water so evaporating, must crystallize in that time: and this is the reason why Salt-petre is adulterated with a mixture of Sea-salt. It likewise follows that the last crystals of Nitre, obtained from a solution of Salt-petre and Sea-salt, contain much more Sea-salt than the first. From all that has been said concerning the crystallization of Salt-petre and Sea-salt, it is easy to deduce the proper way of purifying the former of these two Salts from a mixture of the latter. For this purpose the Salt-petre to be refined need only be dissolved in fair water. The proportion between the two salts in this second solution is very different from what it was in the former; for it contains no more Sea-salt than what had crystallized along with the Salt-petre under favour of the evaporation, the rest having been left dissolved in the liquor that refused to yield any more nitrous crystals. As there is therefore a much greater quantity of Salt-petre than of Sea-salt in this second solution, it is easy to evaporate it to such a degree that a great deal of Salt-petre shall crystallize, while much more of the water must necessarily be evaporated before any of the Sea-salt will crystallize. However, the Salt-petre is not yet entirely freed from all mixture of Sea-salt by this first purification; for the crystals obtained from this liquor, in which Sea-salt is dissolved, are still encrusted, and, as it were, infected therewith: hence it comes, that, to refine the Salt-petre thoroughly, these crystallizations must be repeated four or five times. The Salt-petre men commonly content themselves with crystallizing it thrice, and call the produce Salt-petre of the first, second, or third shoot, according to the number of crystallizations it has undergone. But their best refined Salt-petre, even that of the third shooting, is not yet sufficiently pure for Chymical experiments that require much accuracy: so that it must be further purified; but still by the same method. The Nitrous Acid is not pure in the earths and stones from which it is extracted. It is combined partly with the very earth in which it is formed, and partly with the Volatile Alkali produced by the putrefaction of the vegetable or animal matters that concurred to its generation. A Fixed Alkali and Quick-lime are added to the lixivium of a nitrous earth, in order to decompose the nitrous Salt formed in that earth, and to separate the Acid from the Volatile Alkali and the absorbent earth with which it is united: thence comes that copious sediment which appears in the lye at the beginning of the evaporation. These matters form with that Acid a true Nitre, much more capable than the original Nitrous Salts of crystallization, detonation, and the other properties which are essential thereto. The basis of Nitre is therefore a Fixed Alkali mixed with a little lime. The Mother of Nitre, which will yield no more crystals, is brown and thick: by evaporation over a fire it is further inspissated, and becomes a dry, solid body; which, however, being left to itself soon gives, and runs into a liquor. This water still contains a good deal of Nitre, Sea-salt, and the Acids of these Salts united with an absorbent earth. It contains moreover a great deal of a fat, viscid matter, which prevents its crystallizing. All saline solutions in general, after having yielded a certain quantity of crystals, grow thick, and refuse to part with any more, though they still contain much Salt. They are all called _Mother-waters_, as well as that which hath yielded Nitre. The Mother-waters of different Salts may prove the subjects of curious and useful inquiries. If a Fixed Alkali be mixed with the Mother of Nitre, a copious white precipitate immediately falls, which being collected and dried is called _Magnesia_. This precipitate is nothing but the absorbent earth that was united with the Nitrous Acid, together with a good deal of the lime that was added, and was also united with that Acid, from which they are now separated by the Fixed Alkali, according to the usual laws of affinities. The Vitriolic Acid poured upon Mother of Nitre causes many Acid vapours to rise, which are a compound of the Nitrous and Marine Acids, that is, an _Aqua Regia_. On this occasion also there falls a large quantity of a white powder, which is still called _Magnesia_; yet it differs from the former in that it is not, like it, a pure absorbent earth, but combined with the Vitriolic Acid. An _Aqua regis_ may also be drawn from nitrous earths by the force of fire only, without the help of any additament. PROCESS II. _To decompose Nitre by means of the Phlogiston. Nitre fixed by Charcoal._ Clyssus _of Nitre_. Sal Polychrestum. Take the purest Salt-petre in powder; put it into a large crucible, which it may but half fill; set the crucible in a common furnace, and surround it with coals. When it is red-hot the Nitre will melt, and become as fluid as water. Then throw into the crucible a small quantity of charcoal-dust: the Nitre and the Charcoal will immediately deflagrate with violence; and a great commotion will be raised, accompanied with a considerable hissing, and abundance of black smoke. As the charcoal wastes, the detonation will abate, and cease entirely as soon as the coal is quite consumed. Then throw into the crucible the same quantity of charcoal-dust as before, and the same phenomena will be repeated. Let this coal also be consumed: then add more, and go on in the same manner till you can excite no further deflagration; always observing to let the burning coal be entirely consumed before you add any fresh. When no deflagration ensues, the matter contained in the crucible will have lost much of its fluidity. _OBSERVATIONS._ Nitre will not take fire, unless the inflammable matter added to it be actually burning, or the Nitre itself red-hot, and so thoroughly ignited, as immediately to kindle it. Therefore, if you would procure the detonation of Nitre with charcoal, and make use of cold charcoal, as in the process, the Nitre in the crucible must be red-hot, and in perfect fusion: but you may also use live coals, and then the Nitre need not be red-hot. It is proper that the crucible used in this experiment should be only half full; for during the detonation its contents swell, and might run over without this precaution. For the same reason the charcoal-dust is to be thrown in by little and little; and that first put in must be entirely consumed before any fresh be added. The matter remaining in the crucible after the operation is a very strong Fixed Alkali. Being exposed to the air it quickly attracts the moisture thereof, and runs into a liquor. It is called _Alkalizated Nitre_, or, to distinguish it from Nitre alkalizated by other inflammable matters, _Nitre fixed by charcoal_. However, this Alkali is not absolutely pure. It still contains a portion of the Nitre that hath not been decomposed. For when there remains but a little of this salt mixed with a great quantity of Alkali, which is not inflammable, the Alkali in some measure shelters it, coats it over, and obstructs that immediate contact with the inflammable matters applied, which is necessary to make it deflagrate. If the Fixed Alkali be desired perfectly free from any mixture of undecomposed Nitre, the fire about the crucible must be considerably increased as soon as the detonation is entirely over; the matter must be made to flow, which requires a much stronger heat than would melt Nitre, and kept thus in fusion for about an hour. After this no perfect Nitre will be found therein: for the little that was left, being unable to abide the force of the fire, as not being extremely fixed, either is entirely dissipated, or loses its Acid, which is carried off by the violence of the heat. Fixed Nitre contains also a portion of the earth that constituted the basis of the Nitre, which is no other than the lime employed in its crystallization, or else some of the earth with which its Acid was originally combined, and which it retained in crystallizing. When Nitre is deflagrated with such matters as produce ashes, these ashes likewise furnish a certain quantity of earth, which mixes with the Fixed Alkali. To separate these several earths from the Alkali, nothing more is requisite than to let it run _per deliquium_, or to dissolve it in water, and filter the solution through brown paper. Whatever is saline will pass through the filtre with the water, and the earthy part will be left upon it. The Nitrous Acid is not only dissipated during the deflagration of the Nitre, but is even destroyed, and perfectly decomposed. The smoke that rises during the operation has not the least odour of an Acid. Its nature may be accurately examined by catching it in proper vessels, and condensing it into a liquor. Nitre differs from Sulphur, and from all other inflammable bodies whatever, in this, that the free access of the air is indispensably necessary to make any of the others burn; whereas Nitre, and Nitre only, is capable of burning in close vessels: and this property furnishes us with the means of collecting the vapours which it discharges in deflagration. For this purpose, to a tubulated earthen retort you must fit two or three large adopters: set the retort in a furnace; and under it make a fire sufficient to keep its bottom moderately red. Then take a small quantity, two or three pinches for example, of a mixture of three parts of Nitre with one of charcoal-dust, and drop it into the retort through its tube, which must be uppermost, and immediately stopped close. A detonation instantly ensues, and the vapours that rise from the inflamed mixture of Nitre and charcoal, passing out through the neck of the retort into the adopters, circulate therein for a while, and at last condense into a liquor. When the detonation is over, and the vapours condensed, or nearly so, drop into the retort another equal quantity of the mixture; and repeat this till you find there is liquor enough in the recipients to be examined with ease and accuracy. This liquor is almost insipid, and shews no tokens of acidity; or at most but very slight ones. It is called _Clyssus_ of Nitre. It is easy to perceive why several adopters are required in this experiment, and why a very small quantity of the mixture must be introduced into the retort at once. The explosion, and the quantity of air and vapours discharged on this occasion, would quickly burst the vessels, if all these precautions were not attended to. This plainly appears from the terrible effects of gun-powder, which is nothing but a composition of Nitre, Sulphur, and Charcoal. Nitre is also decomposed and takes fire by the means of Sulphur; but the circumstances and the result differ widely from those produced therewith by charcoal, or any other inflammable body. Nitre deflagrates with Sulphur on account of the Phlogiston which the latter contains. If one part of Sulphur be mixed with two or three parts of Nitre, and the mixture thrown by little and little into a red-hot crucible, upon every projection there arises a detonation accompanied with a vivid flame. The vapours discharged on this occasion have the mingled smell of a Sulphureous Spirit and Spirit of Nitre; and if they be collected by means of a tubulated retort, and such an apparatus of vessels as was used in the preceding experiment, the liquor contained in the recipients is found to be an actual mixture of the Acid of Sulphur, the Sulphureous Spirit, and the Acid of Nitre; the first being in greater quantity than the other two, and the second greater than the last. Nor is the remainder after detonation a Fixed Alkali, as in the former experiments; but a Neutral Salt, consisting of the Acid of Sulphur combined with the Alkali of Nitre; a sort of Vitriolated Tartar known in medicine by the name of _Sal Polychrestum_. There are evidently two essential differences between this last experiment and the preceding one. What remains after the deflagration of Nitre with Sulphur is not a Fixed Alkali: and, moreover, the vapours emitted in the operation are impregnated with a quantity of the Nitrous Acid; which is not the case when Nitre is decomposed by any other inflammable matter which contains no Vitriolic Acid. The reason of these differences is naturally deducible from what hath been already said concerning the properties of the Vitriolic and Nitrous Acids. We have seen that by burning Sulphur its Acid is not decomposed, but only separated from its Phlogiston. We also know, that its Acid has a great affinity with Fixed Alkalis. These things being granted, it follows that, as soon as the Nitrous Acid quits its Alkaline basis, by deflagrating with the Phlogiston of the Sulphur, the Acid of this very Sulphur, being set at liberty by that deflagration, must unite with the Alkaline basis deserted by the Acid of Nitre, and therewith form a Neutral Salt. Hence, instead of a Fixed Alkali, we find at the end of the operation a sort of Vitriolated Tartar; the Acids of Sulphur and of Vitriol being the same, as is evident from what hath been above said concerning them. In order to discover the cause of the other phenomenon, we must recollect two things advanced in our Elements of the Theory; to wit, that the affinity of the Vitriolic Acid with Fixed Alkalis is greater than that of the Nitrous Acid; and again, that the Nitrous Acid is not capable of combining and taking fire with the Phlogiston, but when it is in the form of a Neutral Salt, that is, when it is united with some alkaline, earthy, or metallic basis. If these two principles be applied to the effect in question, the solution is easy and natural. For, in the deflagration of Nitre with Sulphur, the Phlogiston is not the only substance capable of separating the Nitrous Acid from its basis: the Acid of the Sulphur, more and more of which is set at liberty as the Phlogiston is consumed, is also capable of producing the same effect; but with this difference, that the portion of the Nitrous Acid which is detached from its Alkali by the Phlogiston is at the same instant set on fire and decomposed by that union; whereas the portion thereof which is separated by the Vitriolic Acid, being when so separated incapable of uniting with the Phlogiston, and of consuming therewith, is preserved entire, and rises in vapours, together with that portion of the Vitriolic Acid which could not unite with the basis of the Nitre. PROCESS III. _To decompose Nitre by means of the Vitriolic Acid. The Smoking Spirit of Nitre._ Sal de duobus. _The Purification of Spirit of Nitre._ Take equal parts of well purified Nitre and Green Vitriol: dry the Nitre thoroughly, and bruise it to a fine powder. Calcine the Vitriol to redness: reduce it likewise to a very fine powder; and mingle these two substances well together. Put the mixture into an earthen long-neck, or a good glass retort coated, of such a size that it may be but half full. Set this vessel in a reverberating furnace covered with its dome; apply a large glass receiver, having a small hole in its body, stopped with a little lute. Let this receiver be accurately luted to the retort with the fat lute, and the joint covered with a slip of canvas smeared with lute made of quick-lime and the white of an egg. Heat the vessels very gradually. The receiver will soon be filled with very dense red vapours, and drops will begin to distil from the nose of the retort. Continue the distillation, increasing the fire a little when you observe the drops to follow each other but slowly, so that above two thirds of a minute passes between them; and, in order to let out the redundant vapours, open the small hole in the receiver from time to time. Towards the end of the operation raise the fire so as to make the retort red. When you find that, even when the retort is red-hot, nothing more comes over, unlute the receiver, and without delay pour the liquor it contains into a crystal bottle, and close it with a crystal stopple ground in its neck with emery. This liquor will be of a reddish yellow colour, smoking exceedingly, and the bottle containing it will be constantly filled with red fumes like those observed in the receiver. _OBSERVATIONS._ The Vitriolic Acid having a greater affinity with Fixed Alkalis than with any other substance, the Phlogiston excepted, and being in the Vitriol united with a ferruginous basis, will naturally quit that basis to join with the Fixed Alkali of the Nitre; the Acid whereof being weaker than the Vitriolic, as we have already observed on several occasions, must needs be thereby expelled from its basis. The Nitre therefore is decomposed by the Vitriol, and its Acid being set at liberty, is carried up by the force of the fire. Indeed the Nitrous Acid, being thus separated from its alkaline basis, might be expected to combine with the ferruginous basis of the Vitriol: but as it has, like all other Acids, much less affinity with Metallic substances than with Alkalis, even a moderate degree of fire is sufficient to separate it from them. Moreover, this Acid hath either no effect, or very little, upon iron that has lost much of its Phlogiston by contracting an union with any Acid; which is the case of the ferruginous basis of Vitriol. By the process here delivered a very strong, perfectly dephlegmated, and vastly smoking Spirit of Nitre is obtained. If the precautions of drying the Nitre and calcining the Vitriol be neglected, the Acid that comes over, greedily attracting the water contained in these salts, will be very aqueous, will not smoke, and will be almost colourless, with a very slight tinge of lemon. The fumes of highly concentrated Spirit of Nitre, such as that obtained by the above process, are light, corrosive, and very dangerous to the lungs; being no other than the most dephlegmated part of the Nitrous Acid. The person therefore who unlutes the vessels, or pours the liquor out of the receiver into the bottle, ought with the greatest caution to avoid drawing them in with his breath; and for that reason ought to place himself so that a current of air, either natural or artificial, may carry them off another way. It is also necessary that care be taken, during the operation, to give the vapours a little vent every now and then, by opening the small hole in the recipient; for they are so elastic, that, if too closely confined, they will burst the vessels. When the operation is over, you will find a red mass at the bottom of the retort, cast, as it were, in a mould. This is a Neutral Salt of the nature of Vitriolated Tartar, resulting from the union of the Acid of the Vitriol with the Alkaline basis of the Nitre. The ferruginous basis of the Vitriol, which is mixed with this salt, gives it the red colour. To separate it therefrom, you must pulverise it, dissolve it in boiling water, and filter the solution several times through brown paper; because the ferruginous earth of the Vitriol is so fine, that some of it will pass through the first time. When the solution is very clear, and deposites no sediment, let it be set to shoot, and it will yield crystals of Vitriolated Tartar; to which Chymists have given the peculiar title of _Sal de duobus_. In this _Caput mortuum_ we frequently find, besides the ferruginous earth of Vitriol, a portion of Nitre and Vitriol not decomposed; either because the two salts were not thoroughly mingled, or because the fire was not raised high enough towards the end of the operation. Nitre may also be decomposed, and its acid obtained, by the interposition of any of the other Vitriols, Alums, Gypsums, Boles, Clays; in short, by means of any compound in which the Vitriolic Acid is found, provided it have not a Fixed Alkali for its basis. The distillers of _Aqua fortis_, who make large quantities at a time, and who use the least chargeable methods, do their business by the means of earths impregnated with the Vitriolic Acid; such as Clays and Boles. With these earths they accurately mix the Nitre from which they intend to draw their Spirit: this mixture they put into large oblong earthen pots, having a very short curved neck, which enters a recipient of the same matter and form. These vessels they place in two rows opposite to each other in long furnaces, and cover them over with bricks cemented with Windsor-loam, which serves for a reverberatory: then they light the fire in the furnace, making it at first very small, only to warm the vessels; after which they throw in wood, and raise the fire till the pots grow quite red-hot, in which degree they keep it up till the distillation is entirely finished. The Acid of Nitre may also be separated from its basis by means of the pure Vitriolic Acid. For this purpose the Nitre from which you mean to extract the Acid must be finely pulverized, put into a glass retort, and a third of its weight of concentrated Oil of Vitriol poured on it: the retort must be placed in a reverberating furnace, and a receiver, like that used in the preceding operation, expeditiously applied. As soon as the Oil of Vitriol touches the Nitre the mixture grows hot, and copious red fumes begin to appear: some drops of the Acid come over even before the fire is kindled in the furnace. On this occasion the fire must be moderate; because the Vitriolic Acid, being clogged by no basis, acts upon the Nitre much more briskly, and with much greater effect, than when it is not pure. This operation may be performed by a sand-heat; which is a speedy and commodious way of obtaining the Nitrous Acid. In other respects the precautions recommended in the preceding experiment must be carefully observed here, both in distilling the Acid and in taking it out of the receiver. The Spirit of Nitre extracted by this method is as strong, and smokes as much, as that obtained by calcined Vitriol, provided the Oil of Vitriol made use of be well concentrated; but it is generally tainted by the admixture of a small portion of the Vitriolic Acid, which, having no basis of its own to restrain it, is carried up by the heat before it can lay hold of the basis of the Nitre. There are several experiments in Chymistry that succeed equally well whether the Nitrous Acid be or be not thus adulterated with a mixture of the Vitriolic Acid; but there are some, as we shall see, that will not succeed without a Spirit of Nitre so mixed. If the Acid be distilled with a view to such experiments, it must be kept as it is. But most experiments require the Spirit of Nitre to be absolutely pure; and if it be intended for such, it must be perfectly cleansed from the Vitriolic taint. This is easily effected by mixing your Spirit with very pure Nitre, and distilling it a second time. The Vitriolic Acid, with which this Spirit of Nitre is adulterated, coming in contact with a great quantity of undecomposed Nitre, unites with its Alkaline basis, and expels a proportionable quantity of the Nitrous Acid. In the retort made use of to distil the Nitrous Acid, by means of the pure Vitriolic Acid, is found a _Caput mortuum_, differing from that left after the distillation of the same Acid by the interposition of Vitriol, in as much as it contains no red ferruginous earth. This is a very white saline mass, moulded in the bottom of the retort: if you pound it, dissolve it in boiling water, and evaporate the solution, it will shoot into crystals of Vitriolated Tartar: sometimes also it contains a portion of undecomposed Nitre, which shoots after the Vitriolated Tartar, because it is much more soluble in water. CHAP. III. _Of the_ MARINE ACID. PROCESS I. _To extract Sea-salt from Sea-water, and from Brine-springs. Epsom Salt._ Filter the salt-water from which you intend to extract the salt: evaporate it by boiling till you see on its surface a dark pellicle: this consists wholly of little crystals of salt just beginning to shoot: now slacken the fire, that the brine may evaporate more slowly, and without any agitation. The crystals, which at first were very small, will become larger, and form hollow truncated pyramids, the apices whereof will point downwards, and their bases be even with the surface of the liquor. These pyramidal crystals are only collections of small cubical crystals concreted into this form. When they have acquired a certain magnitude they fall to the bottom of the liquor. When they come to be in such heaps as almost to reach the surface of the liquor, decant it from them, and continue the evaporation till no more crystals of Sea-salt will shoot. _OBSERVATIONS._ The Acid of Sea-salt is scarce ever found, either in sea-water or in the earth, otherwise than united with a fixed alkali of a particular kind, which is its natural basis; and consequently it is in the form of a Neutral Salt. This salt is plentifully dissolved in the waters of the ocean, and when obtained therefrom bears the name of _Sea-salt_. It is also found in the earth in vast crystalline masses, and is then called _Sal-gem_: so that Sea-salt and Sal-gem are but one and the same sort of salt, differing very little from each other, except as to the places where they are found. In the earth are also found springs and fountains, whose waters are strong brines, a great deal of Sea-salt being dissolved in them. These springs either rise directly from the sea, or run through some mines of Sal-gem, of which they take up a quantity in their passage. As the same, or at least nearly the same, quantity of Sea-salt will continue dissolved in cold water as boiling water will take up, it cannot shoot, as Nitre does, by the mere cooling of the water in which it is dissolved: it crystallizes only by the means of evaporation, which continually lessens the proportion of the water to the salt; so that it is always capable of containing just so much the less Sea-salt the more there is crystallized. The brine should not boil after you perceive the pellicle of little crystals beginning to form on its surface; for the calmness of the liquor allows them to form more regularly, and become larger. Nor after this should the evaporation be hurried on too fast; for a saline crust would form on the liquor, which, by preventing the vapours from being carried off, would obstruct the crystallization. If the evaporation be continued after the liquor ceases to yield any crystals of Sea-salt, other crystals will be obtained of an oblong four-sided form, which have a bitter taste, and are almost always moist. This sort of salt is known by the name of _Epsom Salt_, which it owes to a salt spring in England, from the water of which it was first extracted. This salt, or rather saline compound, is a congeries of Glauber's salt and Sea-salt, in a manner confounded together, and mixed with some of the Mother of Sea-salt, in which is contained a kind of bituminous matter. These two Neutral Salts, which constitute the Epsom Salt, may be easily separated from each other, by means of crystallization only. Epsom Salt is purgative and bitter; and therefore named _Sal Catharticum Amarum_, or bitter purging Salts. There are different methods used in great works for obtaining Sea-salt out of water in which it is dissolved. The simplest and easiest is that practised in France, and in all those countries which are not colder. On the sea-shore they lay out a sort of broad shallow pits, pans, or rather ponds, which the sea fills with the tide of flood. When the ponds are thus filled, they stop their communication with the sea, and leave the water to evaporate by the heat of the sun; by which means all the salt contained in it necessarily crystallizes. These pits are called _Salt Ponds_. Salt can be made in this way in the summer-time only; at least in France, and other countries of the same temperature: for during the winter, when the sun has less power and rains are frequent, this method is not practicable. For this reason, as it often rains in the province of Normandy, the inhabitants take another way to extract Salt from sea-water. The labourers employed for this purpose raise heaps of sand on the shore, so that the tide waters and drenches them when it flows, and leaves the sand dry when it ebbs. During the interval between two tides of flood the sun and the air easily carry off the moisture that was left, and so the sand remains impregnated with all the salt that was contained in the evaporated water. Thus they let it acquire as much salt as it can by several returns of flood, and then wash it out with fresh water, which they evaporate over a fire in leaden boilers. To obtain the Salt from brine-springs, the water need only be evaporated: but as several of these springs contain too little salt to pay the charges that would be incurred, if the evaporation were effected by the force of fire only, the manufacturers have fallen upon a less expensive method of getting rid of the greatest part of the water, and preparing the brine for crystallization, in much less time, and with much less fire, than would otherwise have been necessary. The method consists in making the water fall from a certain heighth on a great many small spars of wood, which divide it into particles like rain. This is performed under sheds open to all the winds, which pass freely through this artificial shower. By this means the water presents to the air a great extent of surface, being indeed reduced almost entirely to surface, and the evaporation is carried on with great ease and expedition. The water is raised by pumps to the heighth from which it is intended to fall[6]. [6] The Marquis de Montalembert, in a Memoir read before the Academy of Sciences, proposes a new method of effecting these evaporations, together with some considerable improvements in the structure and disposition of the buildings necessary for that purpose. They are called by the French _Batiments de Graduation_; which may properly enough be rendered _Brine-houses_. PROCESS II. _Experiments concerning the decomposition of Sea-salt, by means of the Phlogiston._ Kunckel_'s Phosphorus_. "Of pure urine that has fermented five or six days take a quantity in proportion to the quantity of phosphorus you intend to make: it requires about one third part of a hogshead to make a dram of Phosphorus. Evaporate it in iron pans, till it become clotted, hard, black, and nearly like chimney-soot; at which time it will be reduced to about a sixtieth part of its original weight before evaporation. "When the urine is brought to this condition put it in several portions into so many iron pots, under which you must keep a pretty brisk fire so as to make their bottoms red, and stir it incessantly till the volatile salt and the fetid oil be almost wholly dissipated, till the matter cease to emit any smoke, and till it smell like peach-blossoms. Then put out the fire, and pour on the matter, which will now be reduced to a powder, somewhat more than twice its weight of warm water. Stir it about in this water, and leave it to soak therein for twenty-four hours. Pour off the water by inclination; dry the drenched matter, and pulverize it. The previous calcination carries off from the matter about a third of its weight, and the lixiviation washes out half the remainder. "With what remains thus calcined, washed, and dried, mix half its weight of gravel, or yellow freestone rasped, having sifted out and thrown away all the finest particles. River sand is not proper on this occasion, because it flies in a hot fire. Then add to this mixture a sixteenth part of its weight of charcoal, made of beech, or of any other wood except oak, because that also flies. Moisten the whole with as much water as will bring it to a stiff paste, by working and kneading it with your hands: now introduce it into your retort, taking care not to daub its neck. The retort must be of the best earth, and of such a size, that when your matter is in it, a full third thereof shall still be empty. "Place your retort, thus charged, in a reverberating furnace, so proportioned, that there may be an interval of two inches all round between the sides of the furnace and the bowl of the retort, even where it contracts to form the neck, which should stand inclined at an angle of sixty degrees. Stop all the apertures of the furnace, except the doors of the fire-place and ash-hole. "Fit on to the retort a large glass ballon two thirds full of water, and lute them together, as in distilling the Smoking Spirit of Nitre. In the hinder part of this ballon, a little above the surface of the water, a small hole must be bored. This hole is to be stopped with a small peg of birch-wood, which must slip in and out very easily, and have a small knob to prevent its falling into the ballon. This peg is to be pulled out from time to time, that by applying the hand to the hole it may be known whether the air, rarefied by the head of the retort, issues out with too much or too little force. "If the air rushes out with too much rapidity, and with a hissing noise, the door of the ash-hole must be entirely shut, in order to slacken the fire. If it do not strike pretty smartly against the hand, that door must be opened wider, and large coals thrown into the fire-place to quicken the fire immediately. "The operation usually lasts four and twenty hours; and the following signs shew that it will succeed, provided the retort resist the fire. "You must begin the operation with putting some unlighted charcoal in the ash-hole, and a little lighted charcoal at the door thereof, in order to warm the retort very slowly. When the whole is kindled, push it into the ash-hole, and close the door thereof with a tile. This moderate heat brings over the phlegm of the mixture. The same degree of fire must be kept up four hours, after which some coals may be laid on the grate of the fire-place, which the fire underneath will kindle by degrees. With this second heat brought nearer the retort, the ballon grows warm, and is filled with white vapours, which have the smell of fetid oil. In four hours after, this vessel will grow cool and clear; and then you must open the door of the ash-hole one inch, throw fresh coals into the fire-place every three minutes, and every time shut the door of it, lest the cold air from without should strike against the bottom of the retort and crack it. "When the fire has been kept up to this degree for about two hours, the inside of the ballon begins to be netted over with a volatile salt of a singular nature, which cannot be driven up but by a very violent fire, and which smells pretty strong of peach-kernels. Care must be taken that this concrete salt do not stop the little hole in the ballon: for in that case it would burst, the retort being then red-hot, and the air exceedingly rarefied. The water in the ballon, being heated by the vicinity of the furnace, exhales vapours which dissolve this sprigged salt, and the ballon clears up in half an hour after it has ceased rising. "In about three hours from the first appearance of this salt, the ballon is again filled with new vapours, which smell like Sal Ammoniac thrown upon burning coals. They condense on the sides of the receiver into a salt which is not branched like the former, but appears in long perpendicular streaks, which the vapours of the water do not dissolve. These white vapours are the fore-runners of the Phosphorus, and a little before they cease to rise they lose their first smell of Sal Ammoniac, and acquire the odour of garlic. "As they ascend with great rapidity, the little hole must be frequently opened, to observe whether the hissing be not too strong: for, in that case, it would be necessary to shut the door of the ash-hole quite close. These white vapours continue two hours. When you find they cease rising, make a small passage through the dome, by opening some of its registers, that the flame may just begin to draw. Keep up the fire in this mean state till the first volatile Phosphorus begin to appear. "This appears in about three hours after the white vapours first begin to rise. In order to discover it, pull out the little birchen peg once every minute, and rub it against some hot part of the furnace, where it will leave a trail of light, if there be any Phosphorus upon it. "Soon after you observe this sign, there will issue out through the little hole of the ballon a stream of blueish light, which continues of a greater or shorter extent to the end of the operation. This stream or spout of light does not burn. If you hold your finger against it for twenty or thirty seconds, the light will adhere to it; and if you rub that finger over your hand, the light will besmear it, and render it luminous. "But from time to time this streamer darts out to the length of seven or eight inches, snapping and emitting sparks of fire; and then it burns all combustible bodies that come in its way. When you observe this, you must manage the fire very warily, and shut the door of the ash-hole quite close, yet without ceasing to throw coals into the fire-place every two minutes. "The Volatile Phosphorus continues two hours; after which the little spout of light contracts to the length of a line or two: and now is the time for pushing your fire to the utmost: immediately set the door of the ash-hole wide open, throw billets of wood into it, unstop all the registers of the reverberatory, supply the fire-place with large coals every minute: in short, for six or seven hours all the inside of the furnace must be kept of a white heat, so that the retort shall not be distinguishable. "In this fierce extremity of heat the true Phosphorus distils like an oil, or like melted wax: one part thereof floats on the water in the recipient, the other falls to the bottom. At last, the operation is known to be quite over when the upper part of the ballon, in which the volatile Phosphorus appears condensed in a blackish film, begins to grow red: for this shews that the Phosphorus is burnt where the red spot appears. You must now stop all the registers, and shut all the doors of the furnace, in order to smother the fire; and then close up the little hole in the ballon with fat lute or bees-wax. In this condition the whole must be left for two days; because, the vessels must not be separated till they are perfectly cold, lest the Phosphorus should take fire. "As soon as the fire is out, the ballon, which is then in the dark, presents a most agreeable object: all the empty part thereof above the water seems filled with a beautiful blue light: which continues for seven or eight hours, or as long as the ballon keeps warm, never disappearing till it is cooled. "When the furnace is quite cold take out the vessels, and separate them from each other as neatly as possible. With a linen cloth wipe away all the black stuff you find in the mouth of the ballon; for if that filth should mix with the Phosphorus, it would hinder it from being transparent when moulded. This must be done with great expedition: after which pour into the ballon two or three quarts of cold water, to accelerate the precipitation of the Phosphorus that swims at top. Then agitate the water in the ballon, to rinse out all the Phosphorus that may stick to the sides: pour out all the water thus shaken and turbid, into a very clean earthen pan, and let it stand till it grows clear. Then decant this first useless water, and on the blackish sediment, left at the bottom of the pan, pour some boiling water to melt the Phosphorus; which thereupon unites with the fuliginous matter, or volatile Phosphorus, that precipitated with it, both together forming a mass of the colour of slate. When this water, in which you have melted the Phosphorus, is cool enough, take out the Phosphorus, throw it into cold water, and therein break it into little bits in order to mould it. "Then take a matras, having a long neck somewhat wider next the body than at its mouth: cut off half the body, so as to make a funnel of the neck-part, the smaller end of which must be stopped with a cork. The first mould being thus prepared, plunge it endwise, with its mouth uppermost, in a vessel full of boiling water, and fill it with that water. Into this funnel throw the little bits of your slate-like mass, which will melt again in this hot water, and fall so melted to the bottom of the tube. Stir this melted matter with an iron wire, to promote the separation of the Phosphorus from the fuliginous matter with which it is fouled, and which, being less ponderous than the Phosphorus, will gradually rise above it towards the upper part of the cylinder. "Keep the water in the vessel as hot as at first, till, on taking out the tube, you see the Phosphorus clean and transparent. Let the clear tube cool a little, and then set it in cold water, where the Phosphorus will congeal as it cools. When it is perfectly congealed, pull out the cork, and with a small rod, near as big as the tube, push the cylinder of Phosphorus towards the mouth of the funnel, where the feculency lies. Cut off the black part of the cylinder, and keep it apart: for when you have got a quantity thereof, you may melt it over again in the same manner, and separate the clean Phosphorus which it still contains. As to the rest of the cylinder which is clean and transparent, if you intend to mould it into smaller cylinders, you may cut it in slices, and melt it again by the help of boiling water in glass tubes of smaller dimensions." _OBSERVATIONS._ This process for making Phosphorus is copied from the Memoirs of the Academy of Sciences for the Year 1737; where it is described by M. Hellot, with so much accuracy, clearness, and precision, that I thought I could not do better than transcribe it, without departing from the author's own expressions, for the sake of such as may not have those Memoirs. We shall take occasion, in these observations, to point out some essential circumstances which I have omitted in the description of the Process, that I might not break the connection between the phenomena that happen in the course of this experiment. It is proper to observe, in the first place, that one of the most usual causes of miscarriage in this operation is a defect of the requisite qualities in the retort employed. It is absolutely necessary to have that vessel made of the best earth, and so well made that it shall be capable of resisting the utmost violence of fire, continued for a very long time; as appears by the description of the process. The retorts commonly sold by potters, and other earthen-ware men, are not fit for this operation; and M. Hellot was obliged to send to Hesse-Cassel for such as he wanted. We shall, in the second place, observe with M. Hellot, that, "before you set your retort in the furnace, it is proper to make an essay of your matter, to see if there be reason to hope for success. For this purpose put about an ounce thereof into a small crucible, and heat it till the vessel be red. The mixture, after having smoked, ought to chop or crack without puffing up, or even rising in the least. From these cracks will issue undulating flames, white and blueish, darting upwards with rapidity. This is the first volatile Phosphorus, which occasions all the danger of the operation. When these first flashes are over, increase the heat of your matter by laying a large live coal upon the crucible. You will then see the second Phosphorus, like a luminous, steady vapour, of a colour inclining to violet, covering the whole surface of the matter: it continues for a very long time, and diffuses a smell of garlic, which is the distinguishing odour of the Phosphorus you are seeking. "When this luminous vapour is entirely gone, pour the red hot matter out of the crucible upon an iron plate. If you do not find one drop of salt in fusion, but that, on the contrary, the whole falls readily into powder, it is a proof that your matter was sufficiently lixiviated, and that it contains no more fixed Salt, or Sea-salt, if you will, than is requisite. If you find on the plate a drop of salt coagulated, it shews that there is too much left in, and that there is danger of your miscarrying in the operation; because the redundant salt would corrode, and eat through the retort. In this case your matter must be washed again, and then sufficiently dried." Our third observation shall be concerning the furnace proper to be employed in this operation. This furnace must be so constructed, that, within a narrow compass it may give a heat at least equal to that of a glass-house furnace, or rather greater, especially during the last seven or eight hours of the operation. M. Hellot in his Memoir gives an exact description of such a furnace. "As certain accidents may happen in the course of the operation, some precautions are to be taken against them. For instance, if the ballon should break while the Phosphorus is distilling, and any of it should fall on combustible bodies, it would set them on fire, and probably burn the laboratory, because it is not to be extinguished without the greatest difficulty. The furnace must therefore be erected under some vault, or upon a bed of brick-work raised under some chimney that draws well: nor must any furniture or utensil of wood be left near it. If a little flaming Phosphorus should fall on a man's legs or hands, in less than three minutes it would burn its way to the very bone. In such a case nothing but urine will stop its progress. "If the retort crack while the Phosphorus is distilling, there is an unsuccessful end of your operation. It is easy to perceive this by the stink of garlic which you will smell about the furnace; and moreover, the flame that issues through the apertures of the reverberatory will be of a beautiful violet colour. The Acid of Sea-salt always gives this colour to the flame of such matters as are burnt along with it. But if the retort break before the Phosphorus hath made its appearance, its contents may be saved by throwing a number of cold bricks into the fire-place, and upon them a little water to quench the fire at once." All these useful observations we owe also to M. Hellot. The Phosphorus here described was first discovered by a citizen of Hamburgh, named Brandt, who worked upon urine in search of the Philosopher's stone. Afterwards two other skilful Chymists, who knew nothing more of the process, than that Phosphorus was obtained from urine, or, in general, from the human body, likewise endeavoured to discover it; and each of them separately did actually make the discovery. These two Chymists were Kunckel and Boyle. The former perfected the discovery, and found out a method of making it in considerable quantities at a time; which occasioned it to be called _Kunckel's Phosphorus_. The other, who was an English gentleman, had not time to bring his discovery to perfection, and contented himself with lodging a voucher of his having discovered it in the hands of the Secretary of the Royal Society of London, who gave him a certificate thereof. "Though Brandt," says M. Hellot, "who had before this sold his secret to a Chymist named Krafft, sold it afterwards to several other persons, and even at a very low rate; and though Mr. Boyle published the process for making it; yet it is extremely probable that both of them kept in their own hands the master-key; I mean, _the particular management necessary to make the operation succeed_: for, till Kunckel found it out, no other Chymist ever made any considerable quantity thereof, except Mr. Godfrey Hankwitz, an English Chymist, to whom Mr. Boyle revealed the whole mystery. "Nevertheless," continues he, "we are very far from alledging that all those who have described this operation meaned to impose upon the world: but we conceive that most of them having observed luminous vapours in the ballon, and some sparks about the juncture of the vessels, were contented with those appearances. And thus it came to pass, that, after Kunckel and Boyle died, Mr. Godfrey Hankwitz was the only Chymist that could supply Europe therewith; on which account it is likewise very well known by the name of _English Phosphorus_." Almost all the Chymists consider Phosphorus as a substance consisting of the Acid of Sea-salt combined with the Phlogiston, in the same manner as Sulphur consists of the Vitriolic Acid combined with the Phlogiston. This opinion is founded on the following principles. First, Urine abounds with Sea-salt, and contains also a great deal of Phlogiston; now these are the ingredients of which they conjecture Phosphorus to be composed. Secondly, Phosphorus has many of the properties of Sulphur; such as being soluble in oils; melting with a gentle heat; being very combustible; burning without any soot; giving a vivid and blueish flame; and lastly, leaving an acid liquor when burnt: sensible proofs that it differs from Sulphur in nothing but the nature of its Acid. Thirdly, this Acid of Phosphorus, being mixed with a solution of silver in Spirit of Nitre, precipitates the silver, and this precipitate is a true _Luna cornea_, which appears to be more volatile even than the common sort; as M. Hellot tells us, who made the experiment. This fact proves incontestably that the Acid of Phosphorus is of the same nature with that of Sea-salt: for all Chymists know that the property of precipitating silver in a _Luna cornea_ belongs to the Marine Acid only. Fourthly, M. Stahl observes, that, if Sea-salt be cast on live coals, they instantly burn with great activity; then they emit a very vivid flame, and are much sooner consumed than if none of this salt had touched them; that Sea-salt in substance, which will bear the violence of fire a considerable time when fused in a crucible, without sustaining any sensible diminution, yet evaporates very quickly, and is reduced to white flowers, by the immediate contact of burning coals; and, lastly, that the flame which rises on this occasion is of a blue colour inclining to violet, especially if it be not thrown directly on the coals themselves, but kept in fusion amidst burning coals, in a crucible so placed that the vapour of the Salt may join with the enflamed Phlogiston as it rises from the coals. These experiments of M. Stahl's prove, that the Phlogiston acts upon the acid of Sea-salt, even while it is combined with its alkaline basis. The flame that appears on this occasion may be considered as an imperfect Phosphorus: and indeed its colour is exactly like that of Phosphorus. All the facts above related evince, that the Acid of Phosphorus is akin to that of Sea-salt; or rather that it is the very same. But there are other facts which prove that this Acid undergoes some change at least, some peculiar preparation, before it enters into the composition of a true Phosphorus, and that, when extricated therefrom by burning, it is not a pure Acid of Sea-salt, but is still adulterated with a mixture of some other substance, which makes it considerably different from that Acid. For these observations we are obliged to M. Marggraff, of the Academy of Sciences at Berlin, a celebrated Chymist. I shall presently give an account of his principal experiments as succinctly as possible. M. Marggraff hath also published a process for making Phosphorus, and assures us, that by means thereof we may obtain in less time, with less heat, less trouble, and less expence, a greater quantity of Phosphorus than by any other method. His operation is this: He takes two pounds of Sal Ammoniac in powder, which he mixes accurately with four pounds of Minium. This mixture he puts into a glass retort, and with a graduated fire draws off a very sharp, volatile, urinous spirit. We observed in our theoretical Elements, that some metallic substances have the property of decomposing Sal Ammoniac, and separating its volatile Alkali; concerning which phenomenon we there gave our opinion. Minium, which is a calx of lead, is one of those metallic substances. In this experiment it decomposes the Sal Ammoniac, and separates its volatile Alkali; what remains in the retort is a combination of the Minium with the Acid of the Sal Ammoniac, which is well known to be the same with the Marine Acid; and consequently the residue of this operation is a sort of _Plumbum corneum_. The quantity thereof is four pounds eight ounces. Of this he mixes three pounds with nine or ten pounds of urine, that has stood putrefying for two months, evaporated to the consistence of honey. These he mixes by little and little in an iron pan over the fire, stirring the mixture from time to time. Then he adds half a pound of charcoal-dust, and evaporates the matter, kept continually stirring, till the whole be brought to a black powder. He next distils the mixture in a glass retort with degrees of fire, which he raises towards the end so as to make the retort red-hot, in order to expel all the urinous spirit, superfluous oil, and ammoniacal salt. The distillation being finished, there remains nothing in the retort but a very friable _caput mortuum_. This remainder he pulverises again, and throws a pinch thereof on live coals, thereby to discover whether or no the matter be rightly prepared, and in order for yielding Phosphorus. If it be so, it presently emits an arsenical odour, and a blue undulating flame, which passes over the surface of the coals like a wave. Being thus assured of the success of his operation, he puts one half of his matter in three equal parts, into three small earthen German retorts, capable of holding about eighteen ounces of water a-piece. These three retorts, none of which is above three quarters full, he places together in one reverberatory furnace, built much like those we have described, except that it is so constructed as to hold the three retorts disposed in one line. To each retort he lutes a recipient something more than half full of water, ordering the whole in such a manner, that the noses of his retorts almost touch the surface of the water. He begins the distillation with warming the retorts slowly, for about an hour, by a gentle heat. When that time is elapsed he raises the fire gradually, so that in half an hour more the coals begin to touch the bottoms of the retorts. He continues throwing coals into the furnace by little and little, till they rise half way the heighth of the retorts; and in this he employs another half hour. Lastly, in the next half hour he raises the coals above the bowls of the retorts. Then the Phosphorus begins to ascend in clouds: on this he instantly increases the heat of the fire as much as possible, filling the furnace quite up with coals, and making the retorts very red. This degree of fire causes the Phosphorus to distil in drops, which fall to the bottom of the water. He keeps up this intense heat for an hour and half, at the end of which the operation is finished; so that it lasts but four hours and an half in all: nay, he further assures us, that an artist well versed in managing the fire, may perform it in four hours only. In the same manner he distils the second moiety of his mixture in three other such retorts. The advantage he finds in making use of several small retorts, instead of a single large one, is, that the heat penetrates them with more ease, and the operation is performed with less fire, and in less time. He purifies and moulds his Phosphorus much in the same manner as M. Hellot does. From the quantity of ingredients above-mentioned, he obtains two ounces and a half of fine crystalline moulded Phosphorus. M. Marggraff considering, as a consequence of the experiments above related, that a highly concentrated Acid of Sea-salt contributes greatly towards the formation of Phosphorus, proceeded to try several other experiments, in which he employed that Acid in a state of combination with other bases. He mixed, for instance, an ounce of _Luna cornea_ with an ounce and half of putrefied and inspissated urine, and from the mixture obtained a very beautiful Phosphorus. In short, the several experiments mentioned having thoroughly persuaded him that the Acid of Sea-salt, provided it were highly concentrated, would combine with the Phlogiston as readily as the Vitriolic Acid does, he resolved to try whether he could not make Phosphorus with matters containing that Acid and the Phlogiston, without making use of any urine. With this view he made a great number of different trials, wherein he employed Sea-salt in substance, Sal Ammoniac, Plumbum corneum, Luna cornea, fixed Sal Ammoniac, otherwise called _Oil of Lime_. These several substances, all of which contain the Acid of Sea-salt, he mixed with sundry matters abounding in Phlogiston, different vegetable coals, and even animal matters, such as the oil of hartshorn, human blood, _&c._ varying the proportions of these substances many different ways, without ever being able to produce a single atom of Phosphorus: which gave this able Chymist just cause to suspect, that the Marine Acid, while pure and crude, is not capable of combining with the Phlogiston in the manner requisite to form a Phosphorus; that for this purpose it is necessary the Acid would have contracted a previous union with some other matter; and that the Acid found in urine hath probably undergone the necessary change. M. Marggraff is of opinion that the matter, which by its union renders the Marine Acid capable of entering into the composition of Phosphorus, is a sort of exceedingly subtle vitrifiable earth. The experiments he made upon the Acid of Phosphorus, will shew that his notion is not altogether groundless. M. Marggraff having let some urine, evaporated to the consistence of honey, stand quiet in a cool place, obtained from it, by crystallization, a Salt of a singular nature. By distilling this urine afterwards, he satisfied himself that it yielded him much less Phosphorus than urine from which no Salt had been extracted; and as it cannot be entirely deprived of this Salt, he thinks that the small quantity of Phosphorus, which this urine yielded him, came from the Salt that was still left in it. Further, he distilled this salt separately with lamp-black, and obtained from it a considerable quantity of very fine Phosphorus. He even mixed _Luna cornea_ with this Salt, in order to see whether it would not increase the quantity of his Phosphorus; but without success: whence he concluded, that in this Saline matter resides the true Acid that is fit to enter into the composition of Phosphorus. This opinion is confirmed by several experiments on the Acid of Phosphorus, which he found to have some properties resembling those of this Salt. The Acid of Phosphorus seems to be more fixed than any other: and therefore if you would separate it, by burning, from the Phlogiston with which it is united, there is no occasion for such an apparatus of vessels as is employed for obtaining the Spirit of Sulphur. For this Acid will remain at the bottom of the vessel in which you burn your Phosphorus: indeed, if it be urged by the force of fire, its most subtile part evaporates, and the remainder appears in the form of a vitrified matter. This Acid effervesces with fixed and volatile Alkalis, and therewith forms Neutral Salts; but very different from Sea-salt, and from Sal Ammoniac. That which has a fixed Alkali for its basis does not crackle when thrown on burning coals; but swells and vitrifies like Borax. That which has a volatile Alkali for its basis shoots into long pointed crystals; and, being urged by fire in a retort, lets go its volatile alkali, a vitrified matter remaining behind. This Salt is like that above-mentioned, as obtained from urine and yielding Phosphorus. It appears from the experiments adduced, that the Acid of Phosphorus tends always to vitrification; which proves that it is not pure, and gave M. Marggraff cause to think that it is altered by the admixture of a very subtile vitrifiable earth. M. Marggraff also obtained Phosphorus from several vegetable substances which we use every day for food. This gives him occasion to conjecture, that the Salt requisite to the formation of Phosphorus exists in vegetables, and passes from thence into the animals that feed upon them. Lastly, he concludes his dissertation by informing us of a very important truth, _viz._ That the Acid obtained from Phosphorus, by burning it, will serve to form Phosphorus anew; for which purpose it need only be combined with some charred coal, such as lamp-black, and distilled. From what hath been said on this subject it is plain, that the Chymists have a great many curious and interesting inquiries to make concerning Phosphorus, and particularly concerning its Acid. I shall conclude this article with an account of certain properties of Phosphorus which I have not yet mentioned. Phosphorus dissolves by lying exposed to the air. What water cannot effect, says M. Hellot, or at least requires eight or ten years to bring about, the moisture of the air accomplishes in ten or twelve days; whether it be that the Phosphorus takes fire in the air, and the inflammable part evaporating, almost entirely, leaves the Acid of the Phosphorus naked, which, like all other Acids, when exceedingly concentrated, is very greedy of moisture; or else that the moisture of the air, being water divided into infinitely fine particles, is so subtile as to find its way through the pores of the Phosphorus, into which the grosser particles of common water can by no means insinuate themselves. Phosphorus heated by the vicinity of fire, or by being any way rubbed, soon takes fire and burns fiercely. It is soluble in all Oils and in Ether, giving to those liquors the property of appearing luminous when the bottle containing the solution is opened. Being boiled in water, it likewise communicates thereto this luminous quality. M. Morin, Professor at Chartres, is the author of this observation. The late Mr. Grosse, a celebrated Chymist of the Academy of Sciences, observed, that Phosphorus being dissolved in essential oils crystallizes therein. These crystals take fire in the air, either when thrown into a dry vessel, or wrapt up in a piece of paper. If they be dipped in Spirit of Wine, and taken out immediately, they do not afterwards take fire in the air: they smoke a little, and for a very short time, but hardly waste at all. Though some of them were left in a spoon for a fortnight, they did not seem to have lost any thing of their bulk: but when the spoon was warmed a little they took fire, just like common Phosphorus that had never been dissolved and crystallized in an essential Oil. M. Marggraff, having put a dram of Phosphorus, with an ounce of highly concentrated Spirit of Nitre, into a glass retort, observed, that, without the help of fire, the Acid dissolved the Phosphorus; that part of the Acid came over into the recipient which was luted to the retort; that, at the same time, the Phosphorus took fire, burnt furiously, and burst the vessels with explosion. Nothing of this kind happens when any of the other Acids, though concentrated, are applied to Phosphorus. PROCESS III. _To decompose Sea-salt by means of the Vitriolic Acid. Glauber's Salt. The Purification and Concentration of Spirit of Salt._ Put the Sea-salt from which you mean to extract the Acid into an unglazed earthen pipkin, and set it amidst live coals. The Salt will decrepitate, grow dry, and fall into a powder. Put this decrepitated Salt into a tubulated glass retort, leaving two thirds thereof empty. Set the retort in a reverberating furnace; apply a receiver like that used in distilling the Smoking Spirit of Nitre, and lute it on in the same manner, or rather more exactly if possible. Then through the hole, in the upper convexity of the retort, pour a quantity of highly concentrated Oil of Vitriol, equal in weight to about a third part of your Salt, and immediately shut the hole very close with a glass stopple, first ground therein with emery so as to fit it exactly. As soon as the Oil of Vitriol touches the Salt, the retort and receiver will be filled with abundance of white vapours; and soon after, without lighting any fire in the furnace, drops of a yellow liquor will distil from the nose of the retort. Let the distillation proceed in this manner without fire, as long as you perceive any drops come: afterwards kindle a very small fire under the retort, and continue distilling and raising the fire by very slow degrees, and with great caution, to the end of the distillation; which will be finished before you have occasion to make the retort red-hot. Unlute the vessels, and without delay pour the liquor, which is a very smoking Spirit of Salt, out of the receiver into a crystal bottle, like that directed for the smoking Spirit of Nitre. _OBSERVATIONS._ Sea-Salt, as hath been already said, is a Neutral Salt composed of an Acid, which differs from those of Vitriol and Nitre, combined with a fixed Alkali that has some peculiar properties; but does not vary from the others in its affinities. This Salt therefore, as well as Nitre, must be decomposed by the Vitriolic Acid; which accordingly is the case in the process here described. The Vitriolic Acid unites with the Alkaline basis of the Sea-salt, and separates its Acid; and that with much greater facility than it expels the Nitrous Acid from its Alkaline basis, because the Acid of Sea-salt has not so great an affinity as the Nitrous Acid with Fixed Alkalis. As a highly concentrated Oil of Vitriol is used on this occasion, and as the Sea-salt is previously dried and decrepitated, the Acid obtained from it by distillation is very free from phlegm, and always smokes, even more violently than the strongest Acid of Nitre. The vapours of this Acid are also much more elastic and more penetrating than those of the Nitrous Acid: on which account this distillation of the smoking Spirit of Salt is one of the most difficult, most laborious, and most dangerous operations in Chymistry. This process requires a tubulated retort, that the Oil of Vitriol may be mixed with the Sea-salt after the receiver is well luted to the retort, and not before: for, as soon as these two matters come together, the Spirit of Salt rushes out with so much impetuosity, that, if the vessels were not luted at the time, the copious vapours that would issue through the neck of the ballon would so moisten it, as well as the neck of the retort, that it would be impracticable to apply the lute and secure the joint as the operation requires. Moreover, the operator would be exposed to those dangerous fumes, which, on this occasion, rush out, and enter the lungs, with such incredible activity as to threaten instant suffocation. Having said so much of the elasticity and activity of the fumes of Spirit of Salt, it is needless to insist upon the necessity of giving vent to the vessels from time to time, by opening the little hole of the ballon: indeed the best way to prevent the loss of a great many vapours, on this occasion, is to employ adopters, and cover them with wet canvas, which will cool and condense the vapours they contain. When the operation is finished, we find a white, saline mass at the bottom of the retort as in a mould. If this mass be dissolved in water, and the solution crystallized, it yields a considerable quantity of Sea-salt that hath not been decomposed, and a Neutral Salt consisting of the Vitriolic Acid united with the Alkaline basis of that part which hath been decomposed. This Neutral Salt, which bears the name of _Glauber_ its inventor, differs from Vitriolated Tartar, or the _Sal de duobus_, which remains after distilling the Nitrous Acid, especially in that it is more fusible, more soluble in water, and hath its crystals differently figured. But as in these two Salts the Acid is the same, the differences that appear between them must be attributed to the peculiar nature of the basis of Sea-salt. Spirit of Salt drawn by the process above described is tainted with a small mixture of the Vitriolic Acid, carried up by the force of fire before it had time to combine with the Alkali of the Sea-salt; which happens likewise to the Nitrous Acid procured in the same manner. If you desire to have it pure, and absolutely free from the Acid of Vitriol, it must be distilled a second time from Sea-salt, as the Acid of Nitre was before directed to be distilled again from fresh Nitre, in order to purify it from any Vitriolic taint. Sea-salt, as well as Nitre, may be decomposed by any combination of the Vitriolic Acid with a metallic or earthy substance: but it is proper to observe, that if you distil Spirit of Salt by means of Green Vitriol, the operation will not succeed so well as when Spirit of Nitre is distilled in the same manner: less Spirit is obtained, and a much fiercer fire is required. The cause of this lies in the property which the Acid of Sea-salt possesses of dissolving Iron, even when deprived of a part of its Phlogiston by having contracted an union with another Acid; so that it is no sooner dislodged from its own basis by the Vitriolic Acid, than it unites with the ferruginous basis of the Vitriol, from which it cannot be separated but by a most violent fire. This is the consequence more especially when calcined Vitriol is made use of: for moisture, as we shall presently see, greatly facilitates the separation of the Marine Acid from those substances with which it is united. When you do not desire a highly dephlegmated and smoking Spirit of Salt, you may distil with the additament of any earth containing the Vitriolic Acid; as Clay, for instance, or Bole. To this end one part of Sea-salt, slightly dried and reduced to a fine powder, must be accurately mingled with two parts of the earth you intend to employ likewise pulverized; of this mixture make a stiff paste with a proper quantity of rain water, and having formed little balls thereof about the size of a hazel nut, let them dry in the sun; when dry, put them into a stone or coated glass retort, leaving a third part thereof empty; set this vessel in a reverberating furnace, covered with its dome; apply a receiver, which need not be luted on for some time; and heat the vessels very slowly. At first an insipid water will rise, which must be thrown away: afterwards the Spirit of Salt will appear in white clouds. Now lute your vessels, and raise the fire by degrees; which, towards the end must be pushed to the utmost extremity. The operation is known to be finished when no drops fall from the nose of the retort, the receiver cools, and the white vapours that filled it are seen no more. The Spirit of Salt obtained by the process here delivered does not smoke, and contains much more phlegm than that which is distilled by means of the concentrated Oil of Vitriol; because the earth, though dried in the sun, still retains a great deal of moisture, which commixes with the Acid of the Sea-salt. Consequently it is much easier to collect its vapours; so that this operation is attended with much less trouble than the other. Nevertheless it is adviseable to proceed gently; to apply but little heat at first, and to unstop every now and then the small hole of the receiver: for a quantity of the vapours of Spirit of Salt, even when weakened by the admixture of water, is very apt to burst the vessels. A much greater degree of fire is necessary to raise the Spirit of Salt by this latter process, than by that in which the pure Vitriolic Acid is employed: for, as fast as the Spirit of Salt is dislodged from its own basis, by the Vitriolic Acid contained in the earth made use of, part of it joins that earth, and cannot be separated from it without the most violent heat. A Spirit of Salt that shall not smoke may also be obtained by means of the pure Vitriolic Acid. Spirit of Vitriol, or Oil of Vitriol, lowered with a good deal of water, will do the business. Some Chymists direct a little water to be placed in the receiver, when Spirit of Salt is to be distilled by the intermedium of concentrated Oil of Vitriol, in order to make the acid vapours condense more readily. By this means indeed some of the inconveniencies attending the distillation of smoking Spirit of Salt may be avoided: but, on the other hand, the acid vapours being absolutely suffocated by the water as fast as they come over, the Spirit of Salt obtained by this method will be no less aqueous than that procured by the interposition of earths: so that here is an expence to no manner of purpose. Therefore, when a Spirit of Salt is desired that shall not smoke, it is best to employ an additament of earth; and that so much the rather as the Marine Acid obtained by this means is purer and freer from any Vitriolic taint, for the reasons already assigned. Part of the Acid of Sea-salt may be separated from its Alkaline basis by the force of fire alone, without the intervention of any other body. With this view the Salt must be put into the retort without being dried. At first an insipid water rises; but it gradually becomes acid, and hath all the properties of Spirit of Salt. When the Salt in the retort is grown perfectly dry, nothing more can be forced over by any degree of heat whatever. If you would obtain more Acid from the same Salt, you must take it out of the retort, where you will find it in a lump, reduce it to powder, and expose it to the air for some time, that it may attract the moisture thereof; or else wet it at once with some rain water, and distil as before. You will again have an insipid water, and a little Spirit of Salt; which will in like manner cease to rise when the Salt in the retort becomes dry. This operation may be repeated as often as shall be thought proper: and perhaps it may be possible to decompose Sea-salt entirely by means thereof, without the interposition of any other body. The Spirit of Salt thus obtained is exceeding weak, in small quantity, and loaded with much water. This experiment proves, that moisture greatly facilitates the separation of the Acid of Sea-salt from the matters with which it is united: and this is the reason that, in distilling Spirit of Salt with the additament of an earth, the operation requires much less fire at the beginning, while the earth and salt retain a great deal of humidity, than towards the end, when they begin to grow dry. After the operation there remains in the retort a saline and earthy mass, which contains, 1. Some entire Sea-salt that has suffered no decomposition; 2. A Glauber's Salt which is, as we said before, a Neutral Salt consisting of the Vitriolic Acid united with the Alkaline basis of the Sea-salt, from which it hath expelled its proper Acid; 3. Part of the earth used as an intermedium, still retaining a portion of its original Vitriolic Acid, which happening not to lie near enough to any particles of Sea-salt, could not exert its power in decomposing them, and so remains united with its earthy basis; 4. Another part of the same earth, impregnated with some of the Marine Acid, which combined therewith upon being expelled from its Alkaline basis by the Vitriolic Acid, and which the force of fire was unable to separate from it when the matters were grown perfectly dry. In consequence of what remains in this _caput mortuum_, if the whole mass be triturated, moistened with a little water, and distilled a second time, considerably more Spirit of Salt will be obtained from it: and the same is to be said of all distillations of this sort. Spirit of Salt obtained by the means of any other additament than concentrated Oil of Vitriol is generally very weak: but it may be dephlegmated and concentrated, if required, much in the same manner as Oil of Vitriol. For this purpose you must put it into a glass cucurbit, set it in a _balneum mariæ_, fit thereto a head and a receiver, and with a moderate degree of heat draw off one third or one half of the liquor. What comes over into the receiver will be the most aqueous part, which being the lightest will rise first, impregnated however with a little acid: in the cucurbit will be left a concentrated Spirit of Salt, or the most acid part, which being the heaviest will not rise with the degree of heat that is capable of carrying up the phlegm. Spirit of Salt thus concentrated, called also _Oil of Salt_, does not smoke: it is of a yellow colour inclining to green, and an agreeable smell, not unlike that of saffron. PROCESS IV. _To decompose Sea-salt by means of the Nitrous Acid._ Aqua regis. _Quadrangular Nitre._ Take dried Sea-salt; bruise it to powder; put it into a glass retort, leaving one half of the vessel empty. Pour upon it a third of its weight of good Spirit of Nitre. Place your retort in the sand-bath of a reverberating furnace; put on the dome; lute to the retort a receiver having a small hole in it, and heat the vessels very slowly. There will come over into the receiver some vapours, and an acid liquor. Increase the fire gradually till nothing more rises. Then unlute the vessels, and pour the liquor out of the receiver into a crystal bottle, stopped like others containing Acid Spirits. _OBSERVATIONS._ The Nitrous Acid hath a greater affinity than the Marine Acid with fixed Alkalis. When therefore Spirit of Nitre and Sea-salt are mixed together, the same consequences, in some measure, will follow, as when the Vitriolic Acid is mixed with that salt; that is, the Nitrous Acid will, like the Vitriolic, decompose it, by dislodging its Acid from its Alkaline basis, and assuming its place. But as the Nitrous Acid is considerably weaker, and much lighter, than the Vitriolic Acid, a good deal of it rises along with the Acid of Sea-salt during the operation. The liquor found in the receiver is therefore a true _Aqua regis_. If decrepitated Salt, and a right smoking Spirit of Nitre, be employed in this process, the _Aqua regis_ obtained will be very strong; and, during the operation, very elastic vapours will rush out and burst the vessels, if those precautions be not taken which we pointed out as necessary in distilling the Spirit of Nitre, and the smoking Spirit of Salt. The operation being finished, there is left in the retort a saline mass, containing Sea-salt not decomposed, and a new species of Nitre, which having for its basis the Alkali of Sea-salt, that is, as we have several times observed, an Alkali of a peculiar nature, differs from the common Nitre, 1. In the figure of its crystals; which are solids of four sides, formed like lozenges: 2. In that it crystallizes with more difficulty, retains more water in its crystals, attracts the moisture of the air, and dissolves in water with the same circumstances as Sea-salt. CHAP. IV. _Of_ BORAX. PROCESS. _To decompose Borax by the means of Acids, and to separate from it the Sedative Salt by sublimation and by crystallization._ Reduce to a fine powder the Borax from which you intend to extract the Sedative Salt. Put this powder into a wide-necked glass retort. Pour upon it an eighth part of its weight of common water, to moisten the powder; and then add concentrated Oil of Vitriol to the weight of somewhat more than a fourth part of the weight of Borax. Set the retort in a reverberatory, make a moderate fire at first, and augment it gradually till the retort become red-hot. A little phlegm will first come over, and then with the last moisture that the heat expels the Sedative Salt will rise; by which means some of it will be dissolved in this last phlegm, and pass therewith into the receiver; but most of it will adhere in the form of saline flowers to the fore-part of the neck of the retort, just where it is clear of the groove of the furnace. There they collect into a heap, which the succeeding flowers push insensibly forward till they slightly stop the passage. Those which rise after the neck is thus stopped stick to the after-part of it which is hot, vitrify in some measure, and form a circle of fused Salt. In this state the flowers of the Sedative Salt seem to issue out of the circle, as from their basis: they appear like very thin, light, shining scales, and must be brushed off with a feather. At the bottom of the retort will be left a saline mass: dissolve this in a sufficient quantity of hot water; filter the solution in order to free it from a brown earth which it deposites; set the liquor to evaporate, and crystals of Sedative Salt will form in it. _OBSERVATIONS._ Though Borax is of great use in many chymical operations, especially in the fusion of metals, as we shall have occasion to see, yet, till of late years, Chymists were quite ignorant of its nature, as they still are of its origin; concerning which we know nothing with certainty, but that it comes rough from the East Indies, and is purified by the Dutch. M. Homberg was one of the first that attempted to analyse this Salt. He shewed, that on mixing it with the Vitriolic Acid, and distilling the mixture, a salt sublimes in little fine needles. This product of Borax he called by the name of _Sedative Salt_, because he found it had the property of moderating the great tumult and heat of the blood in fevers. After M. Homberg, other Chymists also exercised themselves on Borax. M. Lemery discovered that the Vitriolic is not the only Acid by means of which the Sedative Salt may be obtained from Borax; but that either of the other two Mineral Acids, the Nitrous or the Marine, may be used in its stead. M. Geoffroy hath greatly facilitated the means of obtaining the Sedative Salt from Borax; having shewn that it may be extracted by crystallization as well as by sublimation; and that the Sedative Salt so obtained is in no respect inferior to that which was procured before by sublimation only. To him also we are indebted for the discovery, that in the composition of Borax there is an Alkaline Salt of the same nature as the basis of Sea-salt. This he found by observing that he got a Glauber's Salt from a solution of Borax into which he had poured some Vitriolic Acid with a view to obtain its Sedative Salt. Lastly, M. Baron, whom we mentioned before on occasion of this Salt, hath proved, by a great number of experiments, that a Sedative Salt may be procured from Borax by the help of Vegetable Acids, which was never done by any body before him; that the Sedative Salt is not a combination of an Alkaline matter with the Acid made use of in extracting it, as some of its properties seemed to indicate; but that it exists previously and completely formed in the Borax; that the Acid employed to extract it only helps to disengage it from the Alkali with which it is united; that this Alkali is actually of the same nature as the basis of Sea-salt, because that after extracting the Sedative Salt, which by its union therewith forms the Borax, a Neutral Salt is found, of the same sort with that which would be produced by combining the basis of Sea-salt with the particular Acid made use of; that is, if with the Vitriolic Acid, a Glauber's Salt; if with the Nitrous Acid, a quadrangular Nitre; and if with the Marine Acid, a true Sea-salt; and, lastly, that the Sedative Salt may be re-united to its Alkali, and reproduce a Borax. Nothing therefore now remains, to give us all the insight we can desire into the nature of Borax, but to know what the Sedative Salt is. M. Baron hath already given us certain negative notices concerning it, by shewing what it is not; that is, that the Acid employed in its extraction doth not enter into its composition. We have great reason to hope, that he will carry his inquiries still further, and clear up all our doubts on this subject. The Sedative Salt may be extracted from Borax, not only by the means of pure and simple Acids, but also by the same Acids combined with a metallic basis. Thus Vitriols, for instance, may be employed for this purpose with good success. It is easy to see, that the Vitriol must be decomposed on this occasion, and that its Acid cannot unite with the Alkali in which the Sedative Salt is lodged, without quitting its metallic basis, which must of course precipitate. The Sedative Salt actually sublimes, when a liquid containing it is distilled; but it does not therefore follow, that it is naturally volatile. It rises only by the aid of the water with which it is mixed. The proof of this assertion is, that, when all the humidity of the mixture containing this Salt is dissipated, no more Salt will rise, be the fire ever so violent; and that by adding more water to moisten the dried mass containing it, more Salt will every time be obtained, through many repeated distillations. In the same manner, if some Sedative Salt be moistened, and exposed to a proper degree of heat, a small quantity thereof will rise at first by the help of the water; but as soon as it grows dry it remains exceedingly fixed. This observation we owe to M. Rouelle. The Sedative Salt hath the appearance and the taste of a Neutral Salt: it does not change the colour of the juice of violets; nor does it easily dissolve in water; for it requires a quart of boiling water to dissolve two ounces of it: yet, with regard to Alkalis, it has the properties of an Acid; it unites with those salts, forms therewith a saline compound which crystallizes, and even expels the Acids that happen to be combined with them; so that it decomposes the same Neutral Salts that are decomposed by the Vitriolic Acid. The Sedative Salt, when suddenly exposed to the violent heat of a naked fire, loses near half its weight, melts, puts on and retains the appearance of glass; but its nature still remains unchanged. This glass dissolves in water, and shoots anew into crystals of Sedative Salt. This Salt communicates to the Alkaline salt with which it is united, when in the form of Borax, the property of melting with a moderate heat, and forming a kind of glass; and it is this great fusibility that recommends the frequent use of Borax as a flux for assaying ores. It is also employed sometimes as an ingredient in the composition of glass; but, in time, it always communicates thereto the fault which its own glass hath, namely that of tarnishing with the air. The Sedative Salt hath, moreover, the singular property of dissolving in Spirit of Wine, and of giving to its flame, when set on fire, a beautiful green colour. All these observations we owe to Mess. Geoffroy and Baron. M. Geoffroy prepares the Sedative Salt by crystallization only, in the following manner. "He dissolves four ounces of refined Borax in a sufficient quantity of warm water, and then pours into the solution one ounce and two drams of highly concentrated Oil of Vitriol, which makes a crackling noise as it falls in. When this mixture has stood evaporating for some time, the Sedative Salt begins to make its appearance in little, fine, shining plates floating on the surface of the liquor. The evaporation is then to be stopped, and the plates will by little and little increase in thickness and breadth. They unite together into little tufts, forming with each other sundry different groups. If the vessel be ever so little stirred, the regularity of the crystals will be disturbed; so that it must not be touched till the crystallization appears to be finished. The crystalline clusters, being grown too bulky and too heavy, will then fall of themselves to the bottom of the vessel. This being observed, the saline liquor must be gently decanted from those little crystals, which, as they are not easily dissolved, must be washed clean, by pouring cold water slowly on the sides of the pan, three or four times successively, in order to rinse out all remains of the saline liquor, and then set first to drain, and afterwards to dry in the sun. This Salt, in the form of light flakes of snow, is now soft to the touch, cool in the mouth, slightly bitter, crackling a little between the teeth, and leaving a small impression of acidity on the tongue. It will keep long without giving or calcining, if managed according to the preceding directions; that is, if it be exactly freed from its saline liquor. "It differs from the Sedative Salt obtained by sublimation in this respect only, that notwithstanding its seeming lightness it is a little heavier than the other. M. Geoffroy supposes the cause of this weight to be, that, as several of the thin plates adhere together in crystallizing, they retain between them some small matter of humidity; or, if you will, that, as they form larger crystals, they present less surface to the air which elevates light bodies: whereas, on the contrary, the other Sedative Salt, being driven up by the force of fire, rises into the head of the cucurbit in a more subtile form, having its particles much more expanded and divided. "M. Geoffroy, having put his Sedative Salt made by crystallization to all the same trials with that made by sublimation, satisfied himself that there is no other difference between the two. If the Sedative Salt made by crystallizations happens to calcine in the sun; that is, if its lustre tarnishes, and its surface grows mealy, it is a sign that it still contains either a little Borax or some Glauber's Salt: for these two Salts are apt to calcine in this manner, and pure Sedative Salt should not be subject to this inconvenience. In order to purify it, and free it entirely from those Salts, it must be dissolved once more in boiling water. As soon as the water cools, the Sedative Salt reappears in light, shining, crystalline plates, swimming in the liquor. After standing four and twenty hours, the liquor must be decanted, and the salt washed with fresh water; by which means it will be very pure and beautiful." Glauber's Salt and Borax dissolve in water with vastly more ease than the Sedative Salt, and consequently do not crystallize so readily by much: so that the small portion of those salts which may have been left on the surface of the Sedative Salt, being diffused through a large quantity of water, continues in a state of solution, while the Sedative Salt crystallizes; which being also washed afterwards with fair water, it is impossible that the smallest particle of those other Salts should remain adhering to it; and consequently this must be deemed an excellent way of purifying it. SECTION II. _Of Operations on_ METALS. CHAP. I. _Of_ GOLD. PROCESS I. _To separate Gold, by Amalgamation with Mercury, from the Earth and Stones with which it is found mixed._ Pulverize the earths and stones containing Gold. Put the powder into a little wooden tray; dip this tray in water, gently shaking it and its contents. The water will grow muddy, by taking up the earthy parts of the ore. Continue washing it in this manner till the water cease to appear turbid. Upon the ore thus washed pour strong vinegar, having first dissolved therein, by the help of heat, about a tenth part of its weight of alum. The powder must be quite drenched and covered with this liquor, and so left to stand for twice twenty-four hours. Decant the vinegar, and wash your powder with warm water, till the last that comes off hath no taste: then dry it, and put it into an iron mortar, with four times its weight of Quick-silver: triturate the whole with a heavy wooden pestle, till all the powder be of a blackish colour: then pour in a little water, and continue rubbing for some time longer. More earthy and heterogeneous particles will be separated from the metalline parts by means of this water, which will look dirty: it must then be decanted, and more fair water added. Repeat this several times; then dry what remains in the mortar with a sponge, and by the help of a gentle heat: you will find it an Amalgam of the Mercury with the Gold. Put this Amalgam into a chamoy bag: tie a knot on its neck, and squeeze it hard between your fingers, over some wide-mouthed vessel; there will issue through the pores of the leather numberless little jets of Mercury, forming a sort of shower, that will collect into large globules in the vessel placed underneath. When you can force out no more Mercury by this means, open the bag, and in it you will find the Amalgam freed from the superfluous Mercury; the Gold retaining only about as much thereof as nearly equals itself in weight. Put this Amalgam into a glass retort; set this retort in the sand-bath of a reverberating furnace; cover it quite over with sand; apply a glass receiver half full of water, so that the nose of the retort may be under the water. The receiver need not be luted to the retort. Give a gradual heat, and raise the fire till drops of the sublimed Mercury appear in the neck of the retort, and fall into the water with a hissing noise. If you hear any noise in the retort slacken your fire a little. Lastly, when you observe, that, though you raise the fire still higher than before, nothing more will come over, take out your retort, break it, and there you will find the Gold, which must be melted in a crucible with Borax. _OBSERVATIONS._ Gold is a perfect metal, which can by no means be deprived of its Phlogiston, and on which few, even of the most powerful chymical solvents, have any effect: and therefore it almost always hath its metalline form when found in the earth; from which it may sometimes be separated by simple lotion. The Gold dust found in the sands of certain rivers is of this kind. When it resides in stones, or tenacious earths, it may be extracted by the process here delivered; to wit, by Amalgamation, or combination of Mercury with Gold. Mercury is incapable of uniting with any earthy substances, not even with the metallic earths, when they are deprived of their Phlogiston, and consequently have not the metalline form. Hence it follows, that when Mercury is triturated with particles of Gold, of earth, and of stone, mingled together, it unites with the Gold, and separates it from those heterogeneous matters. Yet, if there be along with the Gold any other metal, in its metalline form, except Iron, the Mercury will amalgamate with that also. This often happens to Silver, which being a perfect metal as well as Gold, is for that reason sometimes dug up in its metalline form, and even incorporated with Gold. When this is the case, the mass that remains in the retort, after abstracting the Mercury of the Amalgama, is a compound of Gold and Silver, which are to be separated from each other by the methods we shall give for that purpose. The present process is therefore applicable to Silver as well as Gold. Sometimes Gold is intimately combined with such mineral matters as hinder the Mercury from acting upon it. In that case the mixed mass must be roasted before you proceed to Amalgamation: for if the matters be volatile, such, for instance, as antimony or arsenic, the fire will carry them off; so that, after roasting, the Amalgamation will succeed. But sometimes these matters are fixed, and require fusion; if so, recourse must be had to some particular methods, which we shall describe when we come to treat of Silver, as these two perfect metals are to be treated in the same manner. Ores containing Gold must be washed before an Amalgam is attempted; that the metalline parts, being freed from the numerous particles of earth with which they are encompassed, may the more readily incorporate with the Mercury. Besides, it is the property of Mercury to take the form of a dark unmetallic powder, after being long rubbed with other matters, so that it cannot be easily distinguished from the particles of earth. And hence, if you still continue to grind the matters together, after the Amalgamation is completed, and wash them again and again, the water that comes off will always look turbid, being impregnated with some particles of the Amalgam. This is easily proved: for if you let the turbid water settle, and distil the sediment, you will obtain Quick-silver from it. The ore is to be steeped in vinegar charged with alum, in order to cleanse the surface of the Gold, which is often covered with a thin coat of earth that obstructs the Amalgamation. Great care must be taken that the Mercury employed in this operation be very pure. If it be adulterated with any metallic substance, it must be freed therefrom by the methods which we shall propose in their proper place. The way of separating Mercury from Gold is founded on the different properties of these two metallic substances; the one being exceedingly fixed, and the other very volatile. The union which Mercury contracts with the metals is not intimate enough, to give the new compound which results therefrom all the properties of either of the two united substances; at least so far as concerns their degrees of fixity and volatility. Hence it comes, that, in our Amalgam, the Gold communicates but very little of its fixity to the Mercury, and the Mercury communicates to the Gold but very little of its volatility. Yet if the Mercury be distilled off with a much greater degree of heat than is necessary to elevate it, a pretty considerable quantity of Gold will most certainly be carried up along with it. It is also of consequence, on another account, that the fire be duly governed on this occasion. For if too great a degree of heat be applied, and the fire afterwards lowered, the water in the receiver, which covers the nose of the retort, will rise into its body, break it to pieces, and spoil the operation. The cause of this phenomenon depends on the property which air possesses of rarefying with heat and condensing with cold, joined to its weight. As soon as the retort is acted on by a less degree of heat than acted on it the instant before, the air contained therein is condensed, and leaves a _vacuum_, which the external air, by virtue of its weight, tends to occupy; but, the orifice of the retort being under water, the external air can no way gain admittance, but by pushing in before it the water which intercepts its passage. This caution, as we observed above, must be applied to all distillations, where the vessels are disposed as they are in this. Care must also be taken that the nose of the retort be not placed too deep under water: for as the neck grows very warm during the operation, because the degree of heat required to raise Mercury is about three times greater than that which raises water, it may easily be broken by the contact of the cold water in the receiver. This method of extracting Gold and Silver from their ores, by Amalgamation with Mercury, is not to be absolutely depended on as a sure proof of the quantity of those metals that may be contained in the earth assayed by this means: for some small part of the Amalgam is always lost in washing it; and, moreover, the Mercury, when squeezed through chamoy, always carries with it a small portion of Gold. So that if you desire to know more exactly, by this method, the quantity of Gold or Silver contained in any earth, the Amalgam must not be squeezed through chamoy, but distilled altogether. Much the surest method of making an accurate assay is that by fusion and scorification, which we shall describe under the head of Silver. In some countries, and especially in America, the method of Amalgamation is used for extracting Gold and Silver in large quantities, from the matrices which contain them in their metalline form. Agricola and other metallurgists have described the machines by means whereof such Amalgamations are managed. PROCESS II. _To dissolve Gold in_ Aqua regis, _and by that means to separate it from Silver_. Aurum Fulminans. Aurum Fulminans _reduced_. Take Gold that is perfectly pure, or alloyed with Silver only. Reduce it to little thin plates, by hammering it on an anvil. If it be not sufficiently tough, neal it till it be red in a moderate, clear fire, quite free from smoking coals, and then let it cool gradually, which will restore its ductility. When the plates are thin enough, make them red hot once more, and cut them into small bits with a pair of sheers. Put these bits into a tall, narrow-mouthed cucurbit, and pour on them twice their weight of good _Aqua regis_, made of one part Sal Ammoniac, or Spirit of Salt, and four parts Spirit of Nitre. Set the cucurbit in a sand-bath moderately heated, stopping its orifice slightly with a paper coffin, to prevent any dirt from falling in. The _Aqua regis_ will presently begin to smoke. Round the little bits of Gold will be formed an infinite number of small bubbles, which will rise to the surface of the liquor. The Gold will totally dissolve, if it be pure, and the solution will be of a beautiful yellow colour: if the Gold be alloyed with a small quantity of Silver, the latter will remain at the bottom of the vessel in the form of a white powder. If the Gold be alloyed with much Silver, when the Gold is dissolved the Silver will retain the form of the little metalline plates put into the vessel. When the dissolution is completed, gently pour off the liquor into another low, wide-mouthed, glass cucurbit, taking care that none of the Silver, which lies at the bottom in the form of a powder, escape with the liquor. On this powder of Silver pour as much fresh _Aqua regis_ as will cover it entirely; and repeat this till you are sure that nothing more can be taken up by it. Lastly, having decanted the _Aqua regis_ from the Silver, wash the Silver with a little Spirit of Salt weakened with water, and add this Spirit of Salt to the _Aqua regis_ in which your Gold is dissolved. Then to the body containing these liquors fit a head and a receiver, and distil with a gentle heat, till the matter contained in the cucurbit become dry. _OBSERVATIONS._ It is certain that _aqua regis_ is the true solvent of Gold, and that it does not touch Silver: so that if the Gold dissolved in it were alloyed with Silver, which is often the case, the two metals would by this means be pretty accurately separated from each other. But if you desire to obtain from this solution a Gold absolutely pure, you must free it, before you dissolve it, from every other metallic substance but Silver; because _aqua regis_ acts upon most of the other metals and the semi-metals. We shall shew under the head of Silver, as we promised before, how to purify a mass of Gold and Silver from every other metallic alloy. Thither also we refer the common parting assay performed by means of _aqua fortis_: because in that operation the Silver is dissolved, and not the Gold. If the Gold put to dissolve in _aqua regis_ be pure, the dissolution is easily and readily effected. But if, on the contrary, it be alloyed with Silver, the _aqua regis_ finds more difficulty in dissolving it. Nay, if the Silver exceed the Gold in quantity, the dissolution will not take place at all, for the reasons adduced in our Theoretical Elements; of which we shall speak more fully when we come to treat of the Parting Assay. In the process we directed the Gold to be dissolved in a tall body. This precaution is necessary to prevent the loss of some part thereof: for it is the property of _aqua regis_ to carry off along with it some of the Gold, especially when there is any Sal Ammoniac in its composition, if the vessel be heated while the dissolution is going on, or if the _aqua regis_ be very strong. Yet it is proper to make use of _aqua regis_ that is too strong rather than too weak: for if it prove too strong, and be observed not to act upon the metal for that reason, it is easy to weaken it, by gradually adding small quantities of pure water, till you perceive it begin to act with vigour. This is a general rule regarding all metallic dissolutions in Acids. When the solution of Gold is evaporated to dryness, if you desire to reduce into a mass the Gold dust left at the bottom of the cucurbit, you must put it into a crucible, and cover it with pulverized borax, mixed with a little nitre and calcined wine-lees; then cover the crucible close, heat it with a moderate fire, which must be afterwards increased so as to melt the contents. At the bottom of the crucible you will find a lump of Gold, over which the salts you added will be as it were vitrified. These salts are added chiefly to promote the fusion of the metal. The Gold may, if you will, be separated from its solvent without evaporating the solution as above directed. You need only mix with the solution a fixed or volatile Alkali by little and little, till you see no more precipitate fall, and then let the liquor stand to settle, at the bottom of which you will find a sediment: filter the whole, and dry what is left on the filter. Both fixed and volatile Alkalis possessing, as hath been frequently repeated, a greater affinity with Acids than metallic substances have, they precipitate the Gold, and separate it from the Acids in which it is dissolved: but it is of great consequence to take notice, that, if you attempt to melt this precipitated Gold in a crucible, it will fulminate as soon as it feels the heat, with such a terrible explosion, that, if the quantity be at all considerable, it may prove fatal to the operator: even rubbing it a little hard will make it blow up. This preparation is therefore called _Aurum Fulminans_. Hitherto no satisfactory explanation hath been given of this phenomenon. Some Chymists considering, that, in the precipitation of the Gold, a Nitre is regenerated by the union of the Alkali with the Nitrous Acid which enters into the composition of the _aqua regis_, imagine that some of this regenerated Nitre, combining with the precipitated Gold, takes fire and detonates, either by means of some small portion of Phlogiston that may be contained in the Alkali, or by means of that which constitutes the Gold itself. But, in the first place, it is well known that Fixed Alkalis do not contain Phlogiston enough to make Nitre detonate. Indeed, if a Volatile Alkali be employed in the precipitation, a Nitrous Ammoniacal Salt will be formed, containing Phlogiston enough to be capable of detonating without the concourse of any additional Phlogiston: but this detonation of the Nitrous Ammoniacal Salt is not to be compared, as to the violence of its effects, with the fulmination of Gold. Besides, we do not find that Gold precipitated by a Volatile Alkali explodes with greater force than that precipitated by a Fixed Alkali. As for the Gold, it is certain that it suffers no decomposition at all by fulminating. When fulminated under a glass bell, in such small quantities as not to endanger the operator, the Gold is found scattered about under the bell in very fine particles, without having undergone any alteration. Others have fancied this fulmination of the Gold to be nothing but the decrepitation of the Sea-salt that is regenerated, in the precipitation of the metal, by the Fixed Alkali uniting with the Acid of Sea-salt which makes part of the _aqua regis_. But to this it may be said, that Gold precipitated by a Volatile Alkali fulminates as violently as that precipitated by a Fixed Alkali; and yet no sea-salt can be formed in the liquor by the addition of a Volatile Alkali, but only a Sal Ammoniac which has not the property of decrepitating. Moreover, there is no comparison, as to the effects, between the decrepitation of Sea-salt and the fulmination of Gold. Nor, lastly, can this fulmination be attributed, as it is by some, to the effort made by the Salts to escape from amidst the particles of Gold, in which they are supposed by them to be imprisoned: for then we might deprive this Gold entirely of its fulminating quality by only boiling it in water, and so washing off all the saline particles, which probably adhere to its surface only. It is plain there is great room for very beautiful discoveries on this subject. In Walerius's Mineralogy we find some observations that may throw a little light on the point before us. "The quantity," says he, "of fulminating Gold precipitated exceeds that of the Gold dissolved: if the _aqua regis_ be made with Sal Ammoniac the explosion will be stronger; it will also be more violent if the solution be precipitated with a Volatile Alkali, than if a Fixed Alkali be used for that purpose." One of the speediest and easiest methods to deprive this Gold of its fulminating quality, is to grind in a mortar twice as much flowers of Sulphur as you have Gold to reduce, mixing your fulminating Gold therewith by little and little, as you grind them together; then to put the mixture into a crucible, and heat it just enough to melt the Sulphur. Part of the Sulphur will be dissipated in vapours, and the rest will burn away. When it is quite consumed, increase the fire so as to make the crucible red-hot. When you perceive no more smell of Sulphur, pour on the Gold a little Borax, previously melted in another crucible with a Fixed Alkali, as calcined Wine-lees, or Nitre fixed with Tartar; and then raise the fire sufficiently to make the whole flow. After the fusion is completed, you will find a button of Gold at the bottom of the crucible under the Salts. Fulminating Gold may also be reduced by pouring on it a sufficient quantity of Fixed Alkali reduced to a liquor, or of oil of Vitriol, evaporating all the moisture, and gradually throwing what remains, mixed up with some pinguinous matter, into a crucible kept red-hot in a furnace. The reason why these substances deprive the Gold of its fulminating quality, depends on the causes that produce the fulmination. Gold may also be separated from _aqua regis_, and precipitated by the means of several metallic substances that have a greater affinity, either with _aqua regis_, or with one of the two Acids that compose it. Mercury is one of the fittest for this purpose. On dropping a solution of Mercury in the Nitrous Acid by little and little into a solution of Gold, the mixture becomes turbid, and a precipitate is formed. Continue dropping in more of the solution of Mercury till no more precipitate falls; then let the liquor stand to settle, and at the bottom of it you will find a sediment, which is the precipitated Gold: pour off the liquor by inclination, and wash the precipitate with fair water. Mercury hath a greater affinity with the Marine than with the Nitrous Acid. The affinity which Mercury hath with the Marine Acid is also greater than that of Gold with the Marine Acid; for unless this Acid be associated either with the Nitrous Acid, or at least with a certain proportion of Phlogiston, it will not dissolve Gold. Hence it comes, that when a solution of Mercury in the Nitrous Acid is dropped into a solution of Gold in _aqua regis_, the Mercury unites with the Acid of Sea-salt, which is an ingredient in the _aqua regis_: but the Marine Acid cannot on this occasion join the Mercury, without deserting the Gold and the Nitrous Acid with which it was united; and then the Gold, which cannot be kept in solution by the Nitrous Acid alone, is forced to quit its solvent and precipitate. The liquor, therefore, that now floats over the Gold thus precipitated, must contain Mercury united with the Acid of Sea-salt: and in fact it yields a true Corrosive Sublimate, which is known to be a combination of Mercury with the Marine Acid. Mercury dissolved in Spirit of Nitre is employed to procure the precipitation we are speaking of; because metallic substances, when so comminuted by an Acid, are much fitter for such experiments than when they are in a concrete form. Gold precipitated in this manner by a metallic substance doth not fulminate. PROCESS III. _To dissolve Gold by Liver of Sulphur._ Mix together equal parts of common Brimstone, and a very strong Fixed Alkali; for instance, Nitre fixed by Charcoal. Put them in a crucible, and melt the mixture, stirring it from time to time with a small rod. There is no occasion to make the fire very brisk; because the Sulphur facilitates the fusion of the Fixed Alkali. Some sulphureous vapours will rise from the crucible; the two substances will mix intimately together, and form a reddish compound. Then throw into the crucible some little pieces of Gold beat into thin plates, so that the whole do not exceed in weight one third part of the Liver of Sulphur: raise the fire a little. As soon as the Liver of Sulphur is perfectly melted, it will begin to dissolve the Gold with ebullition; and will even emit some flashes of fire. In the space of a few minutes the Gold will be entirely dissolved, especially if it was cut and flatted into small thin leaves. _OBSERVATIONS._ The process here delivered is taken from M. Stahl. The design of that ingenious Chymist's inquiry was to discover how Moses could burn the golden calf, which the Israelites had set up and worshipped while he was on the mount; how he could afterwards reduce that calf to powder, throw it into the water which the people used, and make all who had apostatized drink thereof, as related in the Book of Exodus. M. Stahl, having first observed that Gold is absolutely unalterable and indestructible by the force of fire alone, be it ever so violent, concludes, that without a miracle Moses could not possibly perform the above-mentioned operations on the golden calf any way but by mixing with the Gold some matter qualified to alter and dissolve it. He then takes notice, that pure Sulphur does not act upon Gold at all, and that many other substances, which are thought capable of dividing and dissolving it, cannot however do it so completely as is necessary to render that metal susceptible of the effects related. He then gives the method of dissolving it by Liver of Sulphur, described in the process. Liver of Sulphur dissolves likewise all the other metals: but M. Stahl observes, that it attenuates Gold more than any other metallic substance, and unites with it much more intimately than with the rest. This appears from what happens, on attempting to dissolve in water any of the mixts resulting from the union of another metal with the Liver of Sulphur: for then the metal separates, and appears in the form of a powder or fine calx; whereas, when Gold is united with Liver of Sulphur, the whole compound dissolves in water so perfectly, that the Gold even passes with the Liver of Sulphur through the pores of filtering paper. If an Acid be poured into a solution of this combination of Gold with Liver of Sulphur, the Acid unites with the Alkali of the _Hepar_, and the Gold falls to the bottom of the liquor along with the Sulphur, which doth not quit it. The Sulphur thus precipitated with the Gold is easily carried off by a slight torrefaction, after which the Gold remains exceedingly comminuted. The Sulphur of this compound may also be destroyed by torrefaction, without the trouble of a previous solution and precipitation, and then also the Gold remains so attenuated as to be miscible with liquors, and floats on them, or swims in them, in such a manner that it may easily be swallowed with them in drinking. From all this M. Stahl concludes there is great reason to believe it was by means of the Liver of Sulphur that Moses divided, and in a manner calcined, the golden calf, so that he could mingle it with water, and make the Israelites drink it. PROCESS IV. _To separate Gold from all other metallic Substances by means of Antimony._ Having put the Gold you intend to purify into a crucible, set it in a melting furnace, cover it, and make the Gold flow. When the metal is in fusion cast upon it, by a little at a time, twice its weight of pure crude Antimony in powder, and after each projection cover the crucible again immediately: this done keep the matter in fusion for a few minutes. When you perceive that the metallic mixture is perfectly melted, and that its surface begins to sparkle, pour it out into a hollow iron cone, previously heated, and smeared on the inside with tallow. Immediately strike with a hammer the floor on which the cone stands; and when all is cold, or at least sufficiently fixed, invert the cone and strike it: the whole metallic mass will fall out, and the under part thereof, which was at the point of the cone, will be a Regulus more or less yellow as the Gold was more or less pure. On striking the metallic mass the Regulus will freely part from the sulphureous crust at top. Return this Regulus into the crucible, and melt it. Less fire will do now than was required before. Add the same quantity of Antimony, and proceed as at first. Repeat the same operation a third time, if your Gold be very impure. Then put your Regulus into a good crucible, much larger than is necessary to hold it. Set your crucible in a melting furnace, and heat the matter but just enough to make it flow, with a smooth, brilliant surface. When you find it thus conditioned, point towards it the nose of a long-snouted pair of bellows, and therewith keep gently and constantly blowing. There will arise from the crucible a considerable smoke, which will abate greatly when you cease to blow, and increase as soon as you begin again. You must raise the fire gradually as you approach towards the end of the operation. If the surface of the metal lose its brilliant polish, and seem covered with a hard crust, it is a sign the fire is too weak; in which case it must be increased, till the surface recover its shining appearance. At last, when no more smoke rises, and the surface of the Gold looks neat and greenish, cast on it, by little and little, some pulverized Nitre, or a mixture of Nitre and Borax. The matter will swell up. Continue thus adding more Nitre gradually, till no commotion is thereby produced in the crucible; and then let the whole cool. If you find, when the Gold is cold, that it is not tough enough, melt it over again; when it begins to melt, cast in the same Salts as before; and repeat this till it be perfectly ductile. _OBSERVATIONS._ Antimony is a compound, consisting of a semi-metallic part united with about a fourth part of its weight of common Sulphur. It appears, in the ninth column of the Table of Affinities, that all the metals, Mercury and Gold excepted, have a greater affinity than the reguline part of Antimony with Sulphur. If therefore Gold, adulterated with a mixture of Copper, Silver, or any other metal, be melted with Antimony, those metals will unite with the Sulphur of the Antimony, and separate it from the reguline part, which being thus set free will combine and be blended with the Gold. These two metallic substances, forming a mass far heavier than the other metals mixed with the sulphur, fall together to the bottom of the crucible in the form of a Regulus, while the others float over them like a sort of scoria or flag: and thus the Gold is freed from all alloy but the reguline part of the Antimony. As all the other metals have a great affinity with Sulphur, and Gold is the only one that is capable of resisting its action, one would think Sulphur alone might be sufficient to free it from the metals combined with it, and that it would therefore be better to employ pure Sulphur, in this operation, than to make use of Antimony; the reguline part of which remaining united with the Gold requires another long and laborious operation to get rid of it. Indeed, strictly speaking, Sulphur alone would be sufficient to produce the desired separation: but it is proper to observe, that, as Sulphur alone is very combustible, most of it would be consumed in the operation before it could have an opportunity to unite with the metallic substances; whereas, when it is combined with the Regulus of Antimony, it is thereby enabled to bear the action of the fire much longer without burning, and consequently is much fitter for the purpose in question. Besides, if we were to make use of pure Sulphur, a great part of the Gold, which is kept in perfect fusion, and its precipitation facilitated, by the Regulus of Antimony, would remain confounded with the Sulphureous scoria. Nevertheless, seeing the metals with which Gold is alloyed cannot be separated from it by Antimony, but that a quantity of Regulus proportioned to the quantity of the metals so separated will unite with the Gold, and that the more Regulus combines with the Gold, the more tedious, chargeable, and laborious will the operation prove, this consideration ought to have some influence in directing our process. Therefore, if the Gold be very impure, and worse than sixteen carats, we must not mix it with crude Antimony alone, but add two drams of pure Sulphur for every carat the Gold wants of sixteen, and lessen the quantity of Antimony in proportion to that of the real Gold. It is necessary to keep the crucible close covered, after mixing the Antimony with the Gold, to prevent any coals from falling into it: for, if that should happen, the melted mass would puff up considerably, and might perhaps run over. The inside of the cone, into which you pour the melted metallic mass, must be greased with tallow, to prevent its sticking thereto, and that it may come easily out. Striking the floor, on which the cone with the melted metal stands, helps the precipitation and descent of the Regulus of Gold and Antimony to the bottom of the cone. Less fire is requisite to melt this compound Regulus, in order to add fresh Antimony, than was necessary before the Gold was mixed with the reguline part of the Antimony; because this metallic substance, being much more fusible than Gold, promotes its melting. The Antimony is mixed with the Gold by repeated projections, that the separation of the metals may be accomplished with the greater ease and accuracy. Yet the operation might be successfully performed, by putting in all the Antimony at once, and with one melting only. The metalline mass found at the bottom of the cone after all these operations, is a mixture of Gold with the reguline part of the Antimony. All the rest of the process consists only in separating this reguline part from the Gold. As Gold is the most fixed of all metals, and as the Regulus of Antimony cannot bear the violence of fire without flying off in vapours, nothing more is necessary for this purpose but to expose the compound, as directed in the process, to a heat strong enough and long enough continued, to dissipate all the Regulus of Antimony. This semi-metal exhales in the form of a very thick white smoke. It is proper to blow gently into the crucible during the whole operation; because the immediate contact of the fresh air incessantly thrown in promotes and considerably increases the evaporation: and this is a general rule applicable to all evaporations. The fire must be gradually raised as the Regulus of Antimony is dissipated, and the operation draws towards an end; because the mixed mass of Regulus of Antimony and Gold becomes so much the less fusible as the proportion of the Regulus is lessened. Though the Regulus of Antimony be separated from the Gold in this operation, because the latter is of such a fixed nature that it cannot be volatilized by the degree of fire which dissipates the Regulus; yet, as the Regulus is very volatile, it will undoubtedly carry up some of the Gold along with it, especially if you hurry on the evaporation too fast, by applying too great a degree of fire, by blowing too briskly into the crucible, and still more if you evaporate your mixture in a broad flat vessel instead of a crucible. All these things must therefore be avoided, if you would lose no more Gold than you needs must. However, unless the evaporation be carried to the utmost, by the means above pointed out, a small portion of the Regulus of Antimony will always remain combined with the Gold, which defends it from the action of the fire. This small portion of Regulus hinders the Gold from being perfectly pure and ductile. In order therefore to consume and scorify it, we cast Nitre into the crucible when we perceive it to emit no more white vapours. We know that Nitre has the property of reducing all metallic substances to a calx, Gold and Silver excepted; because it deflagrates with the phlogiston to which their metalline form is owing: but as this accension of the Nitre occasions a tumid effervescence, care must be taken to throw it in but by little and little at a time; for if too much be projected at once the melted matter will run over. This operation might be considerably abridged by taking advantage of the property which Nitre possesses of thus consuming the phlogiston of metallic substances; as by means thereof we might destroy all the Regulus of Antimony incorporated with the Gold, without having recourse to a long and tedious evaporation. But then we should at the same time lose a much greater quantity of Gold, by reason of the tumult and ebullition which are inseparable from the detonation of Nitre. On the whole, therefore, if Nitre be made use of to purify Gold, great care must be taken to apply but very little of it at a time. All the Silver that was mixed with the Gold, and indeed a little of the Gold itself, remains confounded with the sulphureous scoria, which floats upon the Golden Regulus after the addition of the Antimony: we shall shew in the Chapter on Silver how these two metals are to be separated from the Sulphur. CHAP. II. _Of_ SILVER. PROCESS I. _To separate Silver from its Ore, by means of Scorification with Lead._ Beat to powder in an iron mortar the ore from which you mean to separate the Silver, having first roasted it well in order to free it from all the Sulphur and Arsenic that it may contain. Weigh it exactly: then weigh out by itself eight times as much granulated Lead. Put one half of this Lead into a test, and spread it equally thereon: upon this Lead lay your ore, and cover it quite over with the remaining half of the Lead. Place the test thus loaded under the further end of the muffle in a cupelling furnace. Light your fire, and increase it by degrees. If you look through one of the apertures in the door of the furnace you will perceive the ore, covered with calcined Lead, swim upon the melted Lead. Presently afterwards it will grow soft, melt, and be thrown towards the sides of the vessel, the surface of the Lead appearing in the midst thereof bright and shining like a luminous disc: the Lead will then begin to boil, and emit fumes. As soon as this happens, the fire must be a little checked, so that the ebullition of the Lead may almost entirely cease, for about a quarter of an hour. After this it must be excited to the degree it was at before, so that the Lead may begin again to boil and smoke. Its shining surface will gradually lessen, and be covered with _scoriæ_. Stir the whole with an iron hook, and draw in towards the middle what you observe towards the sides of the vessel; to the end that, if any part of the ore should still remain undissolved by the Lead, it may be mixed therewith. When you perceive that the matter is in perfect fusion, that the greatest part of what sticks to the iron hook, when you dip it in the melted matter, separates from it again, and drops back into the vessel; and that the extremity of this instrument, when grown cold, appears varnished over with a thin, smooth, shining crust; you may look on these as marks that the business is done, and the more uniform and evenly the colour of the crust is, the more perfect may you judge the scorification to be. Matters being brought to this pass, take the test with a pair of tongs from under the muffle, and pour its whole contents into an iron cone, first heated and greased with tallow. This whole operation lasts about three quarters of an hour. When all is cold, the blow of a hammer will part the Regulus from the scoria; and as it is not possible, how perfect soever the scorification be, to avoid leaving a little Lead containing Silver in the scoria, it is proper to pulverize this scoria, and separate therefrom whatever extends under the hammer, in order to add it to the Regulus. _OBSERVATIONS._ Silver, as well as Gold, is often found quite pure, and under its metalline form, in the bowels of the earth; and in that case it may be separated from the stones or sand in which it is lodged by simple washing, or by Amalgamation with Mercury, in the same manner as before directed for Gold. But it also happens frequently, that Silver is combined in the ore with other metallic substances and minerals, which will not admit of this process, but force us to employ other methods of separating it from them. Sulphur and Arsenic are the substances to which Silver and the other metals usually owe their mineral state. These two matters are never very closely united with Silver; but may be pretty easily separated from it by the action of fire, and the addition of Lead. If Arsenic be predominant in a Silver ore, it will unite with the Lead by the help of a pretty moderate heat, and quickly convert a considerable quantity thereof into a penetrating fusible glass, which has the property of scorifying with ease all substances that are capable of scorification. When Sulphur predominates, the scorification proceeds more slowly, and doth not always succeed; because that mineral combined with Lead lessens its fusibility, and retards its vitrification. In this case, part of the Sulphur must be dissipated by roasting: the other part unites with the Lead; and that, being rendered lighter by this union, floats on the rest of the mixture, which chiefly contains the Silver. At last, the joint action of the air and of the fire dissipates the portion of Sulphur that had united with the Lead: the Lead vitrifies and reduces to a scoria whatever is not either Silver or Gold: and thus the Silver being disentangled from the heterogeneous matters with which it was united, one part thereof being dissipated and the other vitrified, combines with the portion of Lead which is not vitrified, and falls through the scoria, which, to favour its descent, must be in perfect fusion. The whole process, therefore, consists of three distinct operations. The first is Roasting, which dissipates some of the volatile substances found united with the Silver: the second is Scorification, or the Vitrification of the fixed matters also united with the Silver, such as sand, stones, metals, _&c._ and the third is precipitation, or the separation of the Silver from the scoria. The two first are, as hath been shewn, preparatives for the last, and indeed produce it. As every thing we said concerning Gold, when we treated of the process of Amalgamation, is to be applied to Silver, which may be extracted by the same method when it is in its metalline form; in the same manner, all we now advance touching the method of extracting Silver by Scorification, when it is depraved with a mixture of heterogenous matters, is equally applicable to Gold in the same circumstances: and indeed Silver almost always contains more or less Gold naturally. In the process we directed, that the ore should be pulverized before it be exposed to the fire, with a view to enlarge its surface, and by that means facilitate the action of the Lead upon it, as well as the evaporation of its volatile parts. We recommended the precaution of slackening the fire a little at the beginning of the operation, only to prevent the Lead from being too hastily converted into litharge, lest it should penetrate and corrode the test before it had wholly dissolved the ore: but if we were perfectly certain of the vessel's being so good as to be in no danger of penetration by the Lead, this precaution would be needless. It is proper to add eight parts of Lead for one of ore; though so much is not always absolutely necessary, especially when the ore is very fusible. The success of this operation depends chiefly on the completeness of the Scorification; and therefore the addition of more Lead than enough is attended with no inconvenience: for, as it always promotes the Scorification, it can never do any harm. If the ore be mixed with such earthy and stony parts as cannot be separated from it by washing, it is the more difficult of fusion, even though the stones should be such as are most disposed to vitrify; because the most fusible earths and stones are always less so than most metallic substances. In that case it will be necessary, for effecting the Scorification, to mix thoroughly with the pulverized ore an equal quantity of Glass of Lead, to add twelve times as much granulated Lead, and then to proceed as directed for a fusible ore; exposing the mixture to a degree of fire strong enough, and long enough kept up, to give the scoria all the properties above required as signs of a perfect scorification. Silver ore is sometimes mixed with Pyrites, and the ore of Arsenic, or Cobalt, which also make it refractory. As the Pyrites contain a large quantity of Sulphur, which is very volatile as well as Arsenic; in this case it is proper to begin with freeing the ore from these two extraneous substances. This is easily done by roasting: only be sure, when you first expose the ore to the heat, to cover the vessel in which you roast it, for some minutes, with an inverted vessel of the same width; because such sorts of ore are very apt to fly when they first feel the heat. After this uncover it, and leave it exposed to the fire till no more sulphureous or arsenical matters rise. Then mix it with the same quantity of Glass of Lead as we ordered for ores rendered refractory by the admixture of earths or stones, and proceed in the same manner. It is the more necessary to roast Silver ore infected with Sulphur and Arsenic, because, as Sulphur obstructs the fusion of Lead, it cannot but do hurt, and protract the operation; and Arsenic does mischief, on the other hand, by scorifying a very great quantity of Lead too hastily. When the Sulphur and Arsenic are dissipated by roasting, the ore must be treated like that which is rendered refractory by stony and earthy matters; for as the pyrites contain much iron, there remains, after the Sulphur is evaporated, a considerable quantity of martial earth, which is difficult to scorify. The pyrites, as well as the cobalts, contain moreover an unmetallic earth, which is hard to fuse. The general rule therefore is, when the ore is rendered refractory by any cause whatever, to mix it with Glass of Lead, and to add a larger quantity of granulated Lead. Yet some ores are so refractory that Lead alone will not do the business, and recourse must be had to some other flux. That which is fittest for the present purpose is the _Black Flux_, composed of one part of Nitre and two parts of Tartar deflagrated together. The Phlogiston contained in this quantity of Tartar is more than sufficient to alkalizate the Nitre. This Flux, therefore, is nothing more than Nitre alkalizated by Tartar, mixed with some of the same Tartar that hath not lost its Phlogiston, and is only reduced to a sort of coal. The _White Flux_ is also very fit to promote fusion; but on this occasion the Black Flux is preferable, because the Phlogiston of the Black Flux prevents the Lead from being too soon converted to litharge, and so gives it time to dissolve the metallic matters. The White Flux, which is the result of equal parts of Tartar and Nitre alkalizated together, being no more than an Alkali destitute of Phlogiston, or containing but very little, doth not possess this advantage. If Silver should be combined in the ore with Iron in its metalline state, which however does not commonly happen, then, in order to separate them, the Iron must be deprived of its Phlogiston, and converted to a _crocus_ before the mixed mass be melted with Lead; which may be done by dissolving it in the Vitriolic Acid, and then evaporating the Acid. We are necessitated to make use of this contrivance, because Iron in its metalline form cannot be dissolved either by Lead or by the Glass of Lead; but when it is reduced to a calx, litharge unites with it and scorifies it. If you have not at hand the utensils necessary for performing the operation we have been describing in a test, and under the muffle; or if you have a mind to work on a greater quantity of ore at a time, you may make use of a crucible for the purpose, and perform the operation in a melting furnace. In this case the ore must be prepared, as above directed, according to its nature, and mixed with a proper quantity of Lead and Glass of Lead; the whole put into a good crucible, leaving two thirds thereof empty, and covered with a mixture of Sea-salt and a little Borax, both very dry, to the thickness of a full half inch. This being done, set the crucible in the midst of a melting furnace, raise the coals quite to the lip of the crucible; light the fire; cover the furnace with its dome; but do not urge the fire more than is necessary to bring the mixture to perfect fusion: leave it thus in fusion for a good quarter of an hour; stir the whole with a bit of strong iron wire; then let it cool; break the crucible, and separate the Regulus from the scoria. The Salts added on this occasion are fluxes, and their use is to procure a perfect fusion of the scoria. If the melted matters be left exposed to the fire, either in a test or in a crucible, longer than is above prescribed, the portion of Lead, that hath united and precipitated with the Silver, will at last vitrify, and at the same time scorify all the alloy with which that metal may be mixed. But as there are no vessels that can long endure the action of litharge, without being pierced like a sieve, some of the Silver may escape through the holes or fissures of the vessel, and so be lost. It is better, therefore, to complete the purification of your Silver by the operation of the Cupel, the description of which follows. PROCESS II. _The refining of Silver by the Cupel._ Take a cupel capable of containing one third more matter than you have to put into it: set it under the muffle of a furnace, like that described in our Theoretical Elements, as peculiarly appropriated to this sort of operation. Fill the furnace with charcoal; light it; make the cupel red-hot, and keep it so till all its moisture be evaporated; that is, for about a good quarter of an hour, if the cupel be made wholly of the ashes of burnt bones; and for a whole hour, if there be any washed wood-ash in its composition. Reduce the Regulus which remained after the preceding operation to little thin plates, flatting them with a small hammer, and separating them carefully from all the adherent scoria. Wrap these in a bit of paper, and with a small pair of tongs put them gently into the cupel. When the paper is consumed the Regulus will soon melt, and the scoria, which will be gradually produced by the Lead as it turns to litharge, will be driven to the sides of the cupel, and immediately absorbed thereby. At the same time the cupel will assume a yellow, brown, or blackish colour, according to the quantity and nature of the scoria imbibed by it. When you see the matter in the cupel in a violent ebullition, and emitting much smoke, lower the fire by the methods formerly prescribed. Keep up such a degree of heat only that the smoke which ascends from the matter may not rise very high, and that you may be able to distinguish the colour which the cupel acquires from the scoria. Increase the fire by degrees, as more and more litharge is formed and absorbed. If the Regulus examined by this assay contain no Silver, you will see it turn wholly into scoria, and at last disappear. When it contains Silver, and the quantity of Lead is much diminished, you will perceive little vivid irises, or beautiful rain-bow colours, shooting swiftly along its surface, and crossing each other in many different directions. At last, when all the Lead is destroyed, the thin dark skin, that is continually protruded by the Lead while it is turning into litharge, and which hitherto covered the Silver, suddenly disappears; and, if at this moment the fire happen not to be strong enough to keep the Silver in fusion, the surface of that metal will at once dart out a dazzling splendour: but, if the fire be strong enough to keep the Silver in fusion, though freed from all mixture of Lead, this change of colour, which is called its _fulguration_, will not be so perceptible, and the Silver will appear like a bead of fire. These phenomena shew that the operation is finished. But the cupel must still be left a minute or two under the muffle, and then drawn slowly out with the iron hook towards the door of the furnace. When the Silver is so cooled as to be but moderately red, you may take the cupel from under the muffle with your little tongs, and in the middle of its cavity you will find an exceeding white bead of Silver, the lower part whereof will be unequal, and full of little pits. _OBSERVATIONS._ The Regulus obtained by the former process consists altogether of the Silver contained in the ore, alloyed with the other metals that happened to be mixed therewith in its mineral state, and a good deal of the Lead that was added to precipitate the Silver. The operation of the cupel may be considered as the sequel of that process, being intended only to reduce into a scoria whatever is not Gold or Silver. Lead being of all metals that which vitrifies the most easily, which most promotes the vitrification of the rest, and the only one which, when vitrified, penetrates the cupel, and carries along with it the other metals which it hath vitrified, is consequently the fittest for that purpose. We shall see in its place, that Bismuth hath the same properties with Lead, and may be substituted for it in this operation. Care must be taken to chuse a cupel of a proper capacity. Indeed it should rather be too big than too little: because the operation is no way prejudiced by an excess in its size; whereas, if it be too small, it will be over-dosed with Lead, and at last the litharge, which destroys every thing, will corrode its cavity, and eat holes through the very body of the vessel. Add, that the ashes, of which the cupel is made, being once glutted with litharge, absorb it afterwards but slowly, and that the quantity of this vitrified litharge, becoming too great to be contained in the substance of the vessel, exsudes through it, and drops on the floor of the muffle, which it corrodes and renders unequal; and moreover solders to it the vessels set thereon. It may be laid down as a general rule for determining the size of a cupel, that it weigh, at least, half as much as the metallic mass to be refined in it. It is also of the utmost consequence that the cupel be well dried before the metal be put into it. In order to make sure of this point, it must be kept red-hot for a certain time, as is above directed: for though to the sight and to the touch it may appear very dry, it nevertheless obstinately retains a small matter of moisture, sufficient to occasion the loss of some of the metal; which, when it comes to melt, will be thereby spirited up, in the form of little globules, to the very roof of the muffle. The cupels that stand most in need of an intense heat to dry them, are those chiefly in whose composition wood-ashes are employed: for whatever care be taken to lixiviate those ashes before they are used, they will still retain a little alkaline salt; and that, we know, is very greedy of moisture, will not part entirely with it, but by the means of a violent calcination, and presently re-imbibes it when exposed to the air. A little Phlogiston also may still be left in the ashes of which the cupels are made; and that is another reason for calcining them before they are used. By this means the remaining Phlogiston is dissipated, which might otherwise combine with the litharge during the operation, reduce it, and occasion such a ferment in the matter as to make some of it run over; to these inconveniencies, which any remainder of moisture or Phlogiston may produce, we must add the cracks and flaws, which are very incident to cupels not perfectly freed from both those matters. It is of no less importance to the success of this operation, that a due degree of heat be kept up. In the process we have described the marks which shew the heat to be neither too strong nor too weak; when it exceeds in either of these respects it may be known by the following signs. If the fume emitted by the Lead rise like a spout to the roof of the muffle; if the surface of the melted metal be extremely convex, considering the quantity of the mass: if the cupel appear of such a white heat, that the colour communicated thereto by the imbibed scoria cannot be distinguished: all these shew that the heat is too great, and that it ought to be diminished. If, on the contrary, the vapours only hover, as it were, over the surface of the metal; if the melted mass be very flat, considering its quantity; if its ebullition appear but faint; if the _scoriæ_, that appear like little fiery drops of rain, have but a languid motion; if the scoria gather in heaps, and do not penetrate the cupel; if the metal be covered with it as with a glassy coat; and, lastly, if the cupel look dull; these are proofs that the heat is too weak, and ought to be increased. The design of this operation being to convert the Lead into litharge, and to give it sufficient time and opportunity to scorify and carry off with it whatever is not Gold or Silver; the fire must be kept up to such a degree that the Lead may easily be turned into litharge, and yet that litharge not be absorbed too hastily by the cupel, but that a small quantity thereof may all along remain, like a ring, round the melted metal. The fire is to be gradually increased as the operation draws nearer to its end: for, as the proportion of the Lead to the Silver is continually lessening, the metallic mass gradually becomes less fusible; while the Silver defends the Lead mixed with it from the action of the fire, and prevents its being easily converted into litharge. When the operation is finished, the cupel must still be left under the muffle, till it has imbibed all the litharge, to the end that the bead of Silver may be easily taken out: for, without this precaution, it would stick so fast as not to be removed, but by breaking off part of the cupel along with it. Care must also be taken to let this bead of Silver cool gradually, and be perfectly fixed, before you draw it from under the muffle; for if you expose it at once to the cold air, before it be fixed, it will swell, shoot into sprigs, and even dart out several little grains to a considerable distance, which will be lost. If the bead appear to have a yellowish tinge, it is a sign that it contains a great deal of Gold, which must be separated from it by the methods to be hereafter shewn. It is proper to observe, that there is scarce any Lead that does not contain some Silver; too little perhaps to defray the charges necessary to separate it, yet considerable enough to lead us into an error, by mixing with the Silver obtained from an ore, and increasing its weight. And therefore, when the operations above described are applied to the assaying of an ore, in order to know how much Silver it yields, it is previously necessary to examine the Lead to be used, and to ascertain the quantity of Silver it contains, which must be deducted from the total weight of the bead of Silver obtained by purifying it in this manner. Silver may be separated from its ore, and at the same time refined, by the single operation of the cupel, without any previous scorification with Lead. In order to do this, you must pound the ore; roast it, to dissipate all its volatile parts; mix it with an equal quantity of litharge, if it be refractory; divide it into five or six parcels, wrapping each in a bit of paper; weigh out eight parts of granulated Lead for one of ore, if it be fusible, and from twelve to sixteen, if it be refractory; put one half of the Lead into a very large cupel under the muffle; add thereto one of the little parcels of ore, when the Lead begins to smoke and boil; immediately slacken the fire a little; continue the same degree of heat till you perceive that the litharge formed round the metal, and on its surface, begins to look bright; then raise the fire; add a fresh parcel of ore; continue proceeding in the same manner till you have put in all the ore; then add the remaining half of the granulated Lead, and conduct the succeeding part of the operation in the same manner as that of cupelling. In this operation it is necessary that the fire be not too strongly urged, and that it be diminished every time you add a fresh parcel of ore; that so the Lead and the litharge may have time to dissolve, scorify, and carry off into the pores of the cupel, all the adventitious matters with which your Silver may be mixed. Notwithstanding this precaution, when the ore is refractory, there often gathers in the cupel a great quantity of scoria, together also with some of the ore that could not be dissolved and scorified. It is with a view to remedy this inconvenience that the second moiety of the Lead is added towards the end, which completes the dissolution and scorification of the whole; so that by means thereof no scoria, or very little, is left in the cupel at the end of the operation. The operation of the cupel is chiefly used to purify Silver from the alloy of Copper; because this metal, being more fixed and harder to calcine than other metallic substances, is the only one that remains united with Silver and Lead, after roasting and scorification with Lead. It requires no less than sixteen parts of the Lead to destroy it in the cupel, and separate it from Silver. It melts into one mass with the Lead; and the glass produced by these two metals, deprived of their phlogiston, inclines to a brown or a black colour; by which appearance chiefly we know that our Silver was alloyed with Copper. PROCESS III. _To purify Silver by Nitre._ Granulate the Silver you intend to purify, or reduce it to thin plates; put it into a good crucible; add thereto a fourth part in weight of very dry pulverized Nitre, mixed with half the weight of the Nitre of calcined Wine-lees, and about a sixth part of the same weight of common glass in powder. Cover this crucible with another crucible inverted; which must be of such a size that its mouth may enter a little way into that of the lower one, and have its bottom pierced with a hole of about two lines in diameter. Lute the two crucibles together with clay and Windsor-loam. When the lute is dry, place the crucibles in a melting furnace. Fill the furnace with charcoal, taking care however that the fuel do not rise above the upper crucible. Kindle the fire, and make your vessels of a middling-red heat. When they are so, take up with the tongs a live-coal, and hold it over the hole of the upper crucible. If you immediately perceive a vivid splendour round the coal, and at the same time hear a gentle hissing noise, it is a sign that the fire is of a proper strength; and it must be kept up at the same degree till this phenomenon cease. Then increase the fire to the degree requisite to keep pure Silver in fusion; and immediately after take your vessels out of the furnace. You will find the Silver at the bottom of the lower crucible, covered with a mass of Alkaline scoria of a greenish colour. If the metal be not rendered perfectly pure and ductile by this operation, it must be repeated a second time. _OBSERVATIONS._ The purification of Silver by Nitre, as well as the process for refining it on the cupel, is founded on the property which this metal possesses of resisting the force of the strongest fire, and the power of the most active solvents, without losing its phlogiston. The difference between these two operations consists wholly in the substances made use of to procure the scorification of the imperfect metals, or semi-metals, that may be combined with the Silver. In the former this was obtained by Lead, and here it is effected by Nitre. This Salt, as we have shewn, hath the property of calcining and quickly destroying all metallic substances, by consuming their phlogiston, except the perfect metals, Gold and Silver, which alone are able to resist its force. This method may therefore be employed to purify Gold as well as Silver, or indeed both the two mixed together. In this operation the Nitre is gradually alkalizated, as its Acid is consumed with the phlogiston of the metallic substances. The Alkaline Salt and pounded glass are added, with a view to promote the fusion of the metalline calces, as fast as they are formed, and to fix and retain the Nitre, which, as we shall presently see, is apt to fly off in a certain degree of heat. The precaution of covering the crucible with another crucible inverted, which hath only a small hole in its bottom, is designed to prevent any of the Silver from being lost in the operation: for when the Nitre comes to be acted on by a certain degree of heat, and especially when it deflagrates with any inflammable matter, part of it flies off, and so rapidly too as to be capable of carrying off with it a good deal of the Silver. The little hole left in the covering crucible is necessary for giving vent to the vapours, which rise during the deflagration of the Nitre, as they would otherwise open themselves a passage by bursting the vessels. After the operation this vent-hole is found beset with many little particles of Silver, which would have been lost if the crucible had not been covered. If you should observe, during the detonation of the Nitre, that a great many vapours issue through the vent-hole with a considerable hissing noise, even without applying the coal, you must take it for a sign that the fire is too brisk, and accordingly check it; else a great deal of the Nitre will be dissipated, and with it much Silver. You must observe to take the Silver out of the fire as soon as it is in fusion: for if you neglect this, the Nitre being entirely dissipated or alkalizated, the calces of the metals destroyed by it may possibly recover a little phlogiston, communicated either by the vapours of the charcoal, or by little bits of coal accidentally falling into the crucible; by which means some portion of those metals being reduced will mix again with the Silver, prevent its having the desired degree of purity and ductility, and oblige you to begin the operation afresh. PROCESS IV. _To dissolve Silver in_ Aqua Fortis, _and thereby separate it from every other metalline substance. The Purification of_ Aqua Fortis. _Silver precipitated by Copper._ The Silver you intend to dissolve being beaten into thin plates, put it into a glass cucurbit; pour on it twice its weight of good precipitated _aqua fortis_; cover the cucurbit with a piece of paper, and set it on a sand-bath moderately heated. The _aqua fortis_ will begin to dissolve the Silver as soon as it comes to be a little warm. Red vapours will rise; and from the upper surfaces of the Silver there will seem to issue streams of little bubbles, ascending to the top of the liquor, between which and the Silver they will form, as it were, a number of fine chains: this is a sign that the dissolution proceeds duly, and that the degree of heat is such as it ought to be. If the liquor appear to boil and be agitated, a great many red vapours rising at the same time, it is a sign that the heat is too great, and should be lessened till it be reduced to the proper degree indicated above: having obtained that, keep it equally up till no more bubbles or red vapours appear. If your Silver be alloyed with Gold, the Gold will be found, when the dissolution is finished, at the bottom of the vessel in the form of a powder. This solution must now be decanted while it is yet warm; on the powder pour half as much fresh _aqua fortis_ as before, and make it boil; again decant this second _aqua fortis_, and repeat the same a third time; then with fair water wash the remaining powder well: it will be of a brown colour inclining to red. In the observations we shall show how the Silver is to be separated from the _aqua fortis_. _OBSERVATIONS._ All the processes on Silver already delivered, whether for extracting it from its ores, or for refining it, either by the Cupel or by Nitre, are applicable to Gold also. And if Silver be alloyed with Gold before it undergo those several operations, it will still remain alloyed therewith after them, in the same manner, and in the same quantity; because both metals bear them equally. All therefore that can be expected from those several assays, is the separation of every thing that is neither Silver nor Gold from these two metals. But in order to separate these two from each other, recourse must be had either to the process laid down under the head of Gold, or to that here described, which is the most commodious, the most usual, and known by the names of _Quartation_ and the _Parting Assay_. _Aqua fortis_ is the true solvent of Silver, and is utterly incapable of dissolving the least atom of Gold. If therefore a mass consisting of Gold and Silver be exposed to the action of _aqua fortis_, that Acid will dissolve the Silver contained in the compound, without touching the Gold, and the two metals will be separated from each other. This method of parting them is just the reverse of that described before under the head of Gold, which is effected by the means of _aqua regis_. To the success of this separation, by means of _aqua fortis_, several conditions are essentially necessary. The first is, that the Gold and Silver be in due proportion to each other; that is, there must be at least twice as much Silver as Gold in the metalline mass, otherwise the _aqua fortis_ will not be able to dissolve it, for the reason formerly given. If therefore the mass contain too little Silver, it must either be melted down again, and a proper quantity of Silver added; or else, if the Gold be in a sufficient proportion to the Silver, they may be parted by means of _aqua regis_. Secondly, it is necessary that the _aqua fortis_ employed in this operation be absolutely pure, and free from any taint of the Vitriolic or Marine Acid: for, if it be adulterated with the Vitriolic Acid, the Silver will precipitate as fast as it dissolves, and so the precipitated Silver will again mix with the Gold. If the _aqua fortis_ contain any of the Marine Acid, the Silver will be precipitated in that case also; and this inconvenience will be attended with another, namely, that the menstruum, being partly an _aqua regis_, will dissolve some of the Gold. You must therefore be very sure that your _aqua fortis_ is pure, before you set about the operation. In order to discover its quality, you must try it by dissolving, in a small portion thereof, as much Silver as it will take up: if the _aqua fortis_ grow opaque and milky as it dissolves the Silver, it is a sign it contains some foreign Acid, from which it must be purified. In order to effect this, let the portion of _aqua fortis_ used for the above trial stand to settle: the white milky part will gradually fall to the bottom of the vessel. When it is all fallen, gently decant the clear liquor, and pour a few drops of this decanted solution of Silver into the _aqua fortis_ which you want to purify. It will instantly become milky. Let the white particles precipitate as before, and then add a few more drops of your solution of Silver. If the _aqua fortis_ still become milky, let it precipitate again, and repeat this till you find that a drop of your solution of Silver, let fall into this _aqua fortis_, does not make it in the least turbid. Then filter it through brown paper, and you will have an _aqua fortis_ perfectly fit for the Parting Assay. The white particles that appear and settle to the bottom, on dissolving silver in an _aqua fortis_ adulterated with a mixture of some foreign Acid, are no other than that very Silver, which is no sooner dissolved by the Nitrous Acid than it deserts that solvent to unite with the Vitriolic or Marine Acid, wherewith it has a greater affinity, and falls to the bottom with them. And this happens as long as there remains in the _aqua fortis_ a single atom of either of those two Acids. When therefore your _aqua fortis_ hath dissolved as much Silver as it is capable of taking up, and when all the white particles formed during the dissolution are settled to the bottom, you may be assured that the portion which remains clear and limpid is a solution of Silver in an exceeding pure _aqua fortis_. But if the solution of Silver thus depurated be mixed with an _aqua fortis_ adulterated with the Vitriolic or Marine Acid, a like precipitation will immediately ensue, for the reasons above given, till the very last particle of the heterogeneous Acid contained in the _aqua fortis_ be precipitated. _Aqua fortis_ purified by this method contains no extraneous substance whatever, except a small portion of Silver; so that it is very fit for the parting process. But if it be intended for other chymical purposes, it must be rectified in a glass retort with a moderate heat, in order to separate it from the small portion of Silver it contains, which will remain at the bottom of the retort. The third condition necessary to the success of this operation is, that your _aqua fortis_ be neither too aqueous, nor too highly concentrated. If too weak, it will not act upon the Silver: and the consequence will be the same if it be too strong. Both these inconveniencies are easily remedied: for in the former case part of the superfluous phlegm may be drawn off by distillation; or a sufficient quantity of much stronger _aqua fortis_ may be mixed with that which is too weak: and, in the latter case, very pure rain water, or a weaker _aqua fortis_, may be mixed with that which is too strong. You may satisfy yourself whether or no your _aqua fortis_ hath the requisite degree of strength, by dissolving therein a thin plate consisting of one part Gold and two or three parts Silver; which plate must be rolled up in form of a paper coffin. If, when all the Silver contained in the plate is dissolved, the Gold remains in the form of the coffin, it is a sign that your solvent has a due degree of strength. If, on the contrary, the Gold be reduced to a powder, it is a proof that your _aqua fortis_ is too strong, and ought to be weakened. The Gold remaining after the dissolution of the Silver must be melted in a crucible with Nitre and Borax, as hath already been said under the process for parting Gold and Silver by means of _aqua regis_. As to the Silver which remains dissolved in the _aqua fortis_, there are several ways to recover it. The most usual is to precipitate it by the interposition of Copper, which hath a greater affinity than Silver with the Nitrous Acid[7]. For this purpose the solution is weakened by adding twice or thrice as much very pure rain water. The cucurbit containing the solution is set on a sand-bath gently heated, and very clean plates of copper put into it. The surfaces of these plates are soon covered with little white scales, which gradually fall to the bottom of the vessel, as they come to be collected in quantities. It is even proper to strike the cucurbit gently now and then, in order to shake the scales of Silver from the copper plates, and so make room for a new crop. [7] See the Table of Affinities, Column IV. The _aqua fortis_ parts with the Silver by degrees only, as it dissolves the Copper; and therefore the liquor gradually acquires a blueish green colour as the precipitation advances. This precipitation of the Silver is to be continued as long as any remains dissolved in the _aqua fortis_: you may be sure that your liquor contains no more Silver, if the surface of a fresh plate of Copper laid therein remain clean and free from ash-coloured or greyish particles: or if one drop of a solution of Sea-salt let fall into it produce no white or milky cloud. The precipitation being finished, the liquor is to be gently poured off from the precipitated Silver, which must be rinsed in several waters, and even made to boil therewith, in order to free it wholly from the dissolved Copper. The Silver thus well washed must be thoroughly dried, mixed with a fourth part of its weight of a flux compounded of equal parts of Nitre and calcined Borax, and then melted in a crucible. On this occasion care must be taken to raise the fire gently and gradually, till the Silver be brought to fusion. With what accuracy soever the precipitated Silver be washed, in order to free it from the solution of Copper, yet the Silver will always be found alloyed with a small portion of the Copper: but then this Copper is easily destroyed by the Nitre, with which the Silver is afterwards melted; so that the latter metal remains perfectly pure after the operation. Though the Silver be not previously cupelled, but be alloyed with other metallic substances at the time it is thus dissolved, yet the dissolving, precipitating, and fusing it with Nitre, would be sufficient to separate it accurately from them all, and refine it to a degree of purity equal to that obtained by the cupel. The Copper that remains dissolved in the _aqua fortis_, after the precipitation of the Silver, may in like manner be precipitated by Iron, and, as it retains a small portion of Silver, ought not to be neglected when these operations are performed on considerable quantities. In the two next processes we shall shew two other methods of separating Silver from _aqua fortis_. PROCESS V. _To separate Silver from the Nitrous Acid by Distillation. Crystals of Silver. The Infernal Stone._ Into a large, low, glass body put the solution of Silver, from which you intend to separate the Silver by distillation. To this body fit a tubulated head provided with its stopple. Set this alembic in a sand-bath, so that the body may be almost covered with sand: apply a receiver, and distil with a moderate heat, so that the drops may succeed each other at the distance of some seconds. If the receiver grow very hot, check the fire. When red vapours begin to appear, pour into the alembic, through the hole in its head, a fresh quantity of your solution of Silver, first made very hot. Continue distilling in this manner, and repeating the addition of fresh liquor, till all your solution be put into the alembic. When you have no more fresh solution to put in, and when, the phlegm being all come over, red vapours begin again to appear, convey into the alembic half a dram or a dram of tallow, and distil to dryness; which being done, increase your fire so as to make the vessel containing the sand-bath red-hot. In the alembic you will find a calx of Silver, which must be melted in a crucible with some soap and calcined wine-lees. _OBSERVATIONS._ A low cucurbit is recommended for this operation, to the intent that the particles of the Nitrous Acid, which are ponderous, may the more easily be carried up and pass over into the receiver. For the same reason the cucurbit is directed to be almost wholly covered with sand, lest otherwise the acid vapours should be condensed about that part of the cucurbit, which, being out of the sand, would be much cooler than that which is encompassed therewith, and from thence should fall back again to the bottom; by which means the distillation would certainly be retarded, and the vessel probably be broken. Notwithstanding these precautions the vessels are liable to break in such distillations; especially when they contain a great deal of liquor. With a view, therefore, to prevent this accident, we ordered that the whole quantity of the solution of Silver to be distilled should not be put at once into the alembic. The little bit of tallow, added towards the end of the operation, is intended to hinder the metal from adhering closely to the vessel, as it would otherwise do, when all the moisture is dissipated. The Soap and Fixed Alkali mixed with the Silver to flux it, after its separation from the _aqua fortis_ in this way, serve to absorb such of the most fixed particles of the Acid as may still remain united with the metal. If the distillation be stopped when part of the phlegm is drawn off, and the liquor be then suffered to cool, many crystals will shoot therein, which are a Neutral Salt constituted of the Nitrous Acid and Silver. If the distillation be carried further, and stopped when near its conclusion, the liquor being then suffered to cool will wholly coagulate into a blackish mass called the _Infernal Stone_. This way of separating Silver from its solvent is attended with the advantage of saving all the _aqua fortis_, which is excellent, and fit to be employed in other operations. PROCESS VI. _To separate Silver from the Nitrous Acid by Precipitation._ Luna Cornea. Luna Cornea _reduced_. Into your solution of Silver pour about a fourth part in weight of Spirit of Salt, solution of Sea-salt, or solution of Sal Ammoniac. The liquor will instantly become turbid and milky. Add twice or thrice its weight of fair water, and let it stand some hours to settle. It will deposite a white powder. Decant the clear liquor, and on the precipitate pour fresh _aqua fortis_, or Spirit of Salt, and warm the whole on a sand-bath with a gentle heat for some time. Pour off this second liquor, and boil your precipitate in pure water, shifting it several times, till the precipitate and the water be both quite insipid. Filter the whole, and dry the precipitate, which will be a _Luna Cornea_, and must be reduced in the following manner. Smear the inside of a good crucible well with soap. Put your _Luna Cornea_ into it; cover it with half its weight of Salt of Tartar, thoroughly dried and pulverized; press the whole hard down; pour thereon as much oil, or melted tallow, as the powder is capable of imbibing; set the crucible thus charged, and close covered, in a melting furnace, and, for the first quarter of an hour, make no more fire than is necessary to make the crucible moderately red: after that raise it so as to melt the Silver and the Salt, throwing into the crucible from time to time little bits of tallow. When it ceases to smoke, let the whole cool; or pour it into a hollow iron cone, warmed and tallowed. _OBSERVATIONS._ The process here delivered furnishes us with the means of procuring Silver in a degree of purity which is not to be obtained by any other method of treating it whatever. That which is refined on the cupel always retains a small portion of Copper, from which it cannot possibly be separated in that way: but if it be dissolved in _aqua fortis_, and precipitated thence in a _Luna Cornea_ by the Marine Acid, the precipitate will be an absolutely pure Silver, unalloyed with that small portion of Copper which is retained on the cupel. The reason of this effect is, that the Copper remains as perfectly dissolved in Spirit of Salt and in _aqua regia_ as in _aqua fortis_: so that when the Silver, and the Copper with which it is alloyed, are dissolved together in the Nitrous Acid, if the Acid of Sea-salt be mixed with the solution, part of this latter Acid unites with the Silver, and therewith forms a new compound, which not being soluble in the liquor, falls to the bottom. The other part of the Acid mixing with the Nitrous, forms an _aqua regis_, in which the Copper remains dissolved, without separating from it. Fresh Acid is poured on the precipitated calx of Silver, in order to complete the solution of the small portion of Copper that may have escaped the action of the first solvent. It is indifferent whether the Spirit of Salt or the Spirit of Nitre be employed for this purpose, because they both dissolve Copper alike, and because Silver precipitated by Spirit of Salt is not soluble in either. After this it is necessary to wash the precipitate well with pure water, in order to free it entirely from the particles of _aqua fortis_ adhering to the Silver; because they may possibly contain something of Copper, which would mix with the Silver in melting, and taint its purity. If this precipitate of Silver be exposed to the fire, unmixed with any other substance, it melts as soon as it begins to be red; and, if the fire be increased, part thereof will be dissipated in vapours, and the rest will make its way through the crucible. But being poured out as soon as melted, it coagulates into a cake of a purplish red colour, semi-transparent, ponderous, and in some degree pliable, especially if it be very thin. It bears some resemblance to horn, which hath occasioned it to be called _Luna Cornea_. As _Luna Cornea_ is not soluble in water, recourse must be had to fusion, in order to reduce it, by separating from the Silver those acids which give it the above-mentioned properties. Fixed Alkalis and fatty matters are very fit to produce that separation. We directed that the inside of the crucible, in which the reduction is to be made, should be carefully smeared with soap, and that the _Luna Cornea_ should be quite covered with a Fixed Alkali and fat, to the end that when the heat is strong enough to dissipate it in vapours, or to attenuate it so as to render it capable of penetrating the crucible, it may be forced to pass through matters qualified to absorb its Acid, and reduce it. _Luna Cornea_ may also be reduced by being melted with such metalline substances as have a greater affinity than Silver with the Acids wherewith it is impregnated. Of this kind are Tin, Lead, Regulus of Antimony: but the _Luna Cornea_ rushes so impetuously into conjunction with those metalline substances, that a vast many vapours arise, and carry off with them part of the Silver: if therefore you chuse to effect the reduction by the interposition of such metalline substances, you must employ a retort instead of a crucible. But this method is attended with another inconvenience; which is, that some part of those metalline substances may unite with the Silver, and adulterate it: for which reason it is best to keep to the method first proposed. PROCESS VII. _To dissolve Silver, and separate it from Gold, by Cementation._ Mix thoroughly together fine brick-dust four parts, Vitriol calcined to redness one part, and Sea-salt or Nitre one part. Moisten this powder with a little water. With this cement cover the bottom of a crucible half an inch thick; on this first bed lay a thin plate of the mass of Gold and Silver you intend to cement, and which you must previously take care to beat into such thin plates. Cover this plate with a second layer of cement, of the same thickness as the former; on this second bed lay another plate of your metal; cover it in like manner with cement; and so proceed till the crucible be filled to within half an inch of its brim. Fill up the remaining space with cement, and close the crucible with a cover, luted with a paste made of Windsor-loam and water: set your crucible thus charged in a furnace, whose fire-place is deep enough to let it be entirely surrounded with coals, quite up to its mouth. Light some coals in the furnace, taking care not to make the fire very brisk at first; increase it by degrees, but only so far as to make the crucible moderately red; keep up the fire in this degree for eighteen or twenty hours: then let the fire go out; open the crucible when it is cold, and separate the cement from your plates of Gold. Boil the Gold repeatedly in fair water, till the water come off quite insipid. _OBSERVATIONS._ It cannot but seem strange, that, after having so often declared the Acid of Sea-salt to be incapable of dissolving Silver, we should direct either Nitre or Sea-salt indifferently to be employed in composing a cement, which is to produce an Acid capable of eating out all the Silver mixed with Gold. It is easy to conceive how the Nitrous Acid extricated from its basis by means of the Vitriolic Acid may produce this effect: but if Sea-salt instead of Nitre be made an ingredient in the cement, its Acid, though set at liberty in the same manner by the Vitriolic Acid, must at first sight appear unable to answer the end. In order to remove this difficulty, we must here observe, that there are two very essential differences between the Marine Acid collected in a liquor, as it is when distilled in the usual manner, and the same Acid separated from its basis in a crucible, as it is in cementation. The first of these two differences is, that the Acid being reduced into vapours when it acts on the Silver in cementation, its activity is thereby greatly increased: the second is, that in the crucible it sustains a vastly greater degree of heat than it can ever bear when it is in the form of a liquor. For, after it is once distilled and separated from its basis, it cannot sustain any extraordinary degree of heat without being volatilized and entirely dissipated: whereas, while it continues united with its basis, it is much more fixed, and cannot be separated but by a very intense heat. Consequently, if it meet with any body to dissolve, at the very instant of its separation from its basis, while it is actuated by a much fiercer heat than can ever be applied to it on any other occasion, it must operate upon that body with so much the more efficacy: and thus it comes to pass, that in cementation it has the power of dissolving Silver, which it would be incapable of touching if it were not so circumstanced. But herein Gold differs from Silver: for, whatever force the Nitrous or the Marine Acid may exert, when extricated from their bases in the cementing crucible, this metal obstinately refuses to yield to either of those Acids separately, and can never be dissolved by them, unless both be united together. Our cementation, therefore, is actually a parting process in the dry way. The Silver is dissolved, and the Gold remains unaltered. Nay, as the action of the Acids is much stronger when they are applied this way, than when they are used for dissolution in the moist way, the Nitrous Acid, which in the common parting process will not dissolve Silver unless its weight be double that of the Gold, is able in cementation to dissolve a very small quantity of Silver diffused through a large quantity of Gold. It sometimes happens, that after the operation the cement proves extremely hard, so that it is very troublesome to separate it entirely from the Gold. In this case it must be softened by moistening it with hot water. This hardness which the cement acquires is occasioned by the fusion of the Salts, which is the effect of too strong a heat. It was in order to prevent this, and that a due degree of heat might be applied, without the danger of melting the salts, that we directed the cement to be mixed with a considerable quantity of earthy matter incapable of fusion, such as brick-dust. A greater inconvenience will ensue, if the fire be made so strong as to melt the Gold: for then it will partly commix again with the other metalline substances dissolved by the cement, and consequently will not be purified. The crucible is covered, and its cover luted on, to prevent the acid vapours from being too soon dissipated, and to force them to circulate the longer in the crucible. However, it is necessary that those vapours should find a vent at last, otherwise they would burst the vessel: and for this reason we directed the crucible to be luted only with Windsor-loam, which does not grow very hard by the action of fire, and so is capable of yielding and giving passage to the vapours, when a certain quantity of them is collected in the crucible, and they begin to struggle for an escape on every side. When the operation is finished, the Silver dissolved by the Acid of the cement is partly distributed through the cement, and partly in the Gold itself, which is impregnated therewith. For this reason the Gold must be washed several times in boiling water, till the water become absolutely insipid: for, if the Gold be melted without this precaution, it will mix again with the Silver: the cement also may be washed in the same manner to recover the Silver it contains. Though this cementation be, properly speaking, a purification of Gold, yet we have placed it among the processes on Silver, because it is the Silver that is dissolved on this occasion, and because this is a particular way of dissolving that metal. Moreover, most of the processes hitherto delivered, either on Gold or Silver, are equally applicable to both these metals. If the Gold do not appear quite pure after the cementation, the process must be repeated. There are several ways to know the fineness of Gold, the quantity of Silver with which it is alloyed, and the proportion in which these two metals are mixed in a mass purified by the cupel. One of the simplest is the trial by the Touch-stone; which indeed is hardly any more than judging by the eye only, from the colour of the compound metal, what proportion of Gold and Silver it contains. The Touch-stone is a sort of black marble, whose surface ought to be half polished. If the metalline mass which you want to try be rubbed on this stone, it leaves thereon a thin coat of metal, the colour of which may be easily observed. Such as are accustomed to see and handle Gold and Silver can at once judge very nearly from this sample in what proportion the two metals are combined: but, for greater accuracy, those who are in the way of having frequent occasion for this trial are provided with a sufficient number of small bars or needles, of which one is pure Gold, another pure Silver, and all the rest consist of these two metals mixed together in different proportions, varied by carats, or even by fractions of carats, if greater exactness be required. The fineness of each needle being marked on it, that needle whose colour seems to come nearest the colour of the metalline streak on the Touch-stone, is rubbed on the stone by the side of that streak. This needle likewise leaves a mark; and if there appear to be no difference between the two metalline streaks, the metalline mass is judged to be of the same fineness as the needle thus compared with it. If the eye discovers a sensible difference, another needle is sought for whose colour may come nearer to that of the metal to be tried. But though a man be ever so well versed in judging thus of the fineness of Gold by the eye only, he can never be perfectly and accurately sure of it by this means alone. If such certainty be required, recourse must be had to the parting assay; and yet when you have gone through it, there always remains a small quantity of the metal, which should have been dissolved, and yet escaped the action of the solvent. For example, if you make use of _aqua regis_, the Silver that remains after the operation still contains a little Gold; and, if you make use of _aqua fortis_, the Gold that remains after the operation still contains a little Silver. And therefore if you resolve to carry the separation of these two metals still further by solvents, it will be necessary, after you have gone through one parting process, to perform a second the contrary way. For example, if you begin with _aqua fortis_, then, after it has dissolved all the Silver in the metalline mass that it is capable of taking up, dissolve the remaining Gold in _aqua regis_: by which means you will separate the small portion of Silver left in it by the _aqua fortis_. The contrary is to be done if you made use of _aqua regis_ first. CHAP. III. _Of_ COPPER. PROCESS I. _To separate Copper from its Ore._ Beat your Copper ore to a fine powder, having first freed it as accurately as possible, by washing and roasting, from all stony, earthy, sulphureous, and arsenical parts. Mix your ore thus pulverized with thrice its weight of the black flux; put the mixture into a crucible; cover it with common salt to the thickness of half an inch, and press the whole down with your finger. With all this the crucible must be but half full. Set it in a melting furnace; kindle the fire by degrees, and raise it insensibly till you hear the Sea-salt crackle. When the decrepitation is over, make the crucible moderately red-hot for half a quarter of an hour. Then give a considerable degree of heat, exciting the fire with a pair of good perpetual bellows, so that the crucible may become very red-hot, and be perfectly ignited. Keep the fire up to this degree for about a quarter of an hour; then take out the crucible, and with a hammer strike a few blows on the floor whereon you set it. Break it when cold. If the operation hath been rightly and successfully performed, you will find at the bottom of the vessel a hard Regulus, of a bright yellow colour, and semi-malleable; and over it a scoria of a yellowish brown colour, hard and shining, from which you may separate the Regulus with a hammer. _OBSERVATIONS._ Copper in the ore is often blended with several other metallic substances, and with volatile minerals, such as Sulphur and Arsenic. Copper ores also frequently participate of the nature of the pyrites, containing a martial and an unmetallic earth, both of which are entirely refractory, and hinder the ore from melting. In this case you must add equal parts of a very fusile glass, a little borax, and four parts of the black flux, to facilitate the fusion. The black flux is moreover necessary to furnish the Copper with the Phlogiston it wants, or restore so much thereof as it may lose in melting. For the same reason, when any ore, but that of Gold or Silver, is to be smelted, it is a general rule to add some black flux, or other matter abounding with Phlogiston. The Regulus produced by this operation is not malleable, because it is not pure Copper, but a mixture of Copper with all the other metallic substances that were in the ore; except such as were separated from it by roasting, of which it contains but little. According to the nature of the metallic matters that remain combined with the Copper after this fusion, the colour of the Regulus is either like that of pure Copper, or a little more whitish: it is also frequently blackish, which has procured it the name of _Black Copper_. In this state, and even in general, it is usual enough to call this Regulus by the name of Black Copper, when alloyed with other metallic substances that render it unmalleable, whatever its colour be. Hence it appears that there may be several different sorts of Black Copper. Iron, Lead, Tin, Bismuth, and the reguline part of Antimony, are almost always combined with the ores of Copper, in a multitude of different proportions; and all these substances, being reduced by the black flux in the operation, mix and precipitate with the Copper. If the ore contain any Gold or Silver, as is pretty often the case, these two metals also are confounded with the rest in the precipitation, and become part of the Black Copper. Pyritose, sulphureous, and arsenical Copper ores may be fused, in order to get rid of the grosser heterogeneous parts, without previously roasting them: but in this case no alkaline flux must be mixed with the ore; because the Alkali in combination with the Sulphur would produce a Liver of Sulphur, and so dissolve the metalline part; by which means all would be confounded together, and no Regulus, or very little, be precipitated. On this occasion therefore nothing must be added to promote the fusion, but some tender fusile glass, together with a small quantity of borax. This first fusion may also be performed amidst the coals, by casting the ore upon them in the furnace, without using a crucible; and then an earthen vessel, thoroughly heated, or even made red-hot, must be placed under the grate of the fire-place, to receive the metal as it runs from the ore. The Regulus obtained by this means is much more impure and brittle than Black Copper, because it contains moreover a large quantity of Sulphur and Arsenic; as these volatile substances have not time to evaporate during the short space requisite to melt the ore, and as they cannot be carried off by the action of the fire after the ore is once melted, whatever time be allowed for that purpose. However, some part thereof is dissipated; and the Iron which is in pyritose ores, having a much greater affinity than Copper, and indeed than any other metallic substance, with Sulphur and Arsenic, absorbs another part thereof, and separates it from the Regulus. This Regulus, it is plain, still contains all the same parts that were in the ore, but in different proportions; there being more Copper, combined with less Sulphur, Arsenic, and unmetallic earth, which have been either dissipated or turned to slag. Therefore, if you would make it like Black Copper, you must pound it, roast it over and over, to free it from its Sulphur and Arsenic, and then melt it with the black flux. If this Regulus contain much Iron, it will be adviseable to melt it once or twice more, before all the Sulphur and Arsenic are separated from it by roasting; for as the Iron, by uniting with these volatile substances, separates them from the Copper, with which they have not so great an affinity; so also the Sulphur and Arsenic, by uniting with the Iron, help in their turn to separate it from the Copper. PROCESS II. _To purify Black Copper, and render it malleable._ Break into small bits the Black Copper you intend to purify; mix therewith a third part in weight of granulated Lead, and put the whole into a cupel set under the muffle in a cupelling furnace, and previously heated quite red. As soon as the metals are in the cupel raise the fire considerably, making use, if it be needful, of a pair of perpetual bellows, to melt the Copper speedily. When it is thoroughly melted, lower the fire a little, and continue it just high enough to keep the metalline mass in perfect fusion. The melted matter will then boil, and throw up some _scoriæ_, which will be absorbed by the cupel. When most of the Lead is consumed, raise the fire again, till the face of the Copper become bright and shining, thereby shewing that all its alloy is separated. As soon as your Copper comes to this state, cover it with charcoal-dust conveyed into the cupel with an iron ladle: then take the cupel out of the furnace and let it cool. _OBSERVATIONS._ Of all the metals, next to Gold and Silver, Copper bears fusion the longest without losing its phlogiston; and on this property is founded the process here delivered for purifying it. It is necessary the Copper should melt as soon as it is in the cupel, because its nature is to calcine much more easily and much sooner, when it is only red-hot, than when it is in fusion. For this reason the fire is to be considerably raised, immediately on putting the Copper under the muffle, that it may melt as soon as possible. Yet too violent a degree of fire must not be applied to it: for when it is exposed to such a degree of heat only as is but just necessary to keep it in fusion, it is then in the most favourable condition for losing as little as may be of its phlogiston; and if the heat be stronger, a greater quantity thereof will be calcined. As soon therefore as it flows it is proper to weaken the fire, and reduce it to the degree just requisite to keep up the fusion. The Lead added on this occasion is intended to facilitate and expedite the scorification of the metallic substances combined with the Copper. So that the event is here nearly the same as when Gold or Silver is refined on the cupel. The only difference between this refining of Copper, and that of the perfect metals, is that the latter as hath been shewn, absolutely resist the force of fire and the action of Lead, without suffering the least alteration; whereas a good deal of Copper is calcined and destroyed, when it is purified in this manner on the cupel. Indeed it would be wholly destroyed, if a greater quantity of Lead were added, or if it were left too long in the furnace. It is with a view to save as much of it as possible that we order it to be covered with charcoal-dust as soon as the scorification is finished. The Lead serves moreover to free the Copper expeditiously from the Iron with which it may be alloyed. Iron and Lead are incapable of contracting any union together: so that as fast as the Lead unites with the Copper, it separates the Iron, and excludes it out of the mixture. For the same reason if Iron were combined in a large proportion with Copper, it would prevent the Lead from entering into the composition. Now, as it is necessary to give the more heat, and to keep the Copper to be incorporated with Lead the longer in fusion, as that Copper is alloyed with a greater proportion of Iron, some black flux must be added on this occasion, to prevent the Copper and the Lead from being calcined before their association can be effected. Copper purified in the manner here directed is beautiful and malleable. It is now alloyed with no other metalline substance but Gold or Silver, if there were any in the mixed mass. If you desire to extract this Gold or Silver, recourse must be had to the operation of the cupel. The process here given for purifying Copper is not used in large works, because it would be much too chargeable. In order to purify their Black Copper, and render it malleable, the smelters content themselves with roasting it, and melting it repeatedly, that the metallic substances, which are not so fixed as Copper, may be dissipated by sublimation, and the rest scorified by fusion. PROCESS III. _To deprive Copper of its Phlogiston by calcination._ Put your Copper in filings into a test, and set it under the muffle of a cupelling furnace; light the fire, and keep up such a degree of heat as may make the whole quite red, but not enough to melt the Copper. The surface of the Copper will gradually lose its metalline splendour, and put on the appearance of a reddish earth. From time to time stir the filings with a little rod of copper or iron, and leave your metal exposed to the same degree of fire till it be entirely calcined. _OBSERVATIONS._ In our observations on the preceding process we took notice that Copper, in fusion, calcines more slowly, and less easily, than when it is exposed to a degree of fire barely sufficient to keep it red-hot, without melting it; and therefore, the design here being to calcine it, we have directed that degree of heat only to be applied. The cupelling furnace is the fittest for this operation, because the muffle is capable of receiving such a flat vessel as ought to be used on this occasion, and communicating to it a great deal of heat; while, at the same time, it prevents the falling in of any coals, which, by furnishing the Copper with fresh phlogiston, would greatly prejudice and protract the operation. As Copper calcines with great difficulty, this operation is extremely tedious: nay, though Copper hath stood thus exposed to the fire for several days and nights, and seems perfectly calcined, yet it frequently happens that, when you try afterwards to melt it, some of it resumes the form of Copper: a proof that all the Copper had not lost its phlogiston. Copper is much more expeditiously deprived of its phlogiston by calcining it in a crucible with Nitre. The calx of Copper perfectly calcined is with great difficulty brought to fusion: yet, in the focus of a large burning-glass, it melts and turns to a reddish and almost opaque glass. By the process here delivered, you may likewise calcine all other metalline substances, which do not melt till they are thoroughly red-hot. As to those which melt before they grow red, they are easily enough calcined, even while they are in fusion. PROCESS IV. _To resuscitate the Calx of Copper, and reduce it to Copper, by restoring its Phlogiston._ Mix the Calx of Copper with thrice as much of the black flux; put the mixture into a good crucible, so as to fill two thirds thereof, and over it put a layer of Sea-salt a finger thick. Cover the crucible, and set it in a melting furnace; heat it gradually, and keep it moderately red till the decrepitation of the Sea-salt be over. Then raise the fire considerably by means of a good pair of perpetual bellows; satisfy yourself that the matter is in perfect fusion, by dipping into the crucible an iron wire; continue the fire in this degree for half a quarter of an hour. When the crucible is cold, you will find at its bottom a button of very fine Copper, which will easily separate from the saline scoria at top. _OBSERVATIONS._ What hath been said before on the smelting of Copper ores may be applied to this process, as being the very same. The observations there added should therefore be consulted on this occasion. PROCESS V. _To dissolve Copper in the Mineral Acids._ On a sand-bath, in a very gentle heat, set a matrass containing some Copper filings; pour on them twice their weight of Oil of Vitriol. That Acid will presently attack the Copper. Vapours will rise, and issue out of the neck of the matrass. A vast number of bubbles will ascend from the surface of the metal to the top of the liquor, and the liquor will acquire a beautiful blue colour. When the Copper is dissolved, put in a little and a little more, till you perceive the Acid no longer acts upon it. Then decant the liquor, and let it stand quiet in a cool place. In a short time great numbers of beautiful blue crystals will shoot in it. These crystals are called _Vitriol of Copper_, or _Blue Vitriol_. They dissolve easily in water. _OBSERVATIONS._ The Vitriolic Acid perfectly dissolves Copper, which is also soluble in all the Acids, and even in many other menstruums. This Acid may be separated from the Copper which it hath dissolved by distillation only: but the operation requires a fire of the utmost violence. The Copper remaining after it must be fused with the black flux, to make it appear in its natural form; not only because it still retains a portion of the Acid, but also because it hath lost part of its phlogiston by being dissolved therein. The black flux is very well adapted both to absorb the Acid that remains united with the Copper, and to restore the phlogiston which the metal hath lost. The most usual method of separating Copper from the Vitriolic Acid is by presenting to that Acid a metal with which it hath a greater affinity than with Copper. Iron being so qualified is consequently very fit to bring about this separation. When therefore plates of Iron well cleaned are laid in a solution of Blue Vitriol, the Acid soon begins to act upon them, and by degrees, as it dissolves them, deposites on their surfaces a quantity of Copper in proportion to the quantity of Iron it takes up. The Copper thus precipitated hath the appearance of small leaves or scales, exceeding thin, and of a beautiful copper-colour. Care must be taken to shake the Iron-plates now and then, to make the scales of Copper fall off, which will otherwise cover them entirely, hinder the Vitriolic Acid from attacking the Iron, and so put a stop to the precipitation of the remaining Copper. When these scales of Copper cease to settle on the clean Iron plates, you may be sure all the Copper that was in the liquor is precipitated, and that this liquor, which was a solution of Copper before the precipitation, is a solution of Iron after it. So that here two operations are performed at one and the same time; to wit, the precipitation of the Copper, and the dissolution of the Iron. The Copper thus precipitated requires only to be separated from the liquor by filtration, and melted with a little black flux, to become very fine malleable Copper. The Copper may also be precipitated out of a solution of Blue Vitriol by the interposition of a Fixed Alkali. This precipitate is of a greenish blue colour, and requires a much greater quantity of the black flux to reduce it. Copper dissolves in the Nitrous Acid, in the Marine Acid, and in _Aqua regis_; from all of which it may be separated by the same methods as are here ordered with regard to the Vitriolic Acid. CHAP. IV. _Of_ IRON. PROCESS I. _To separate Iron from its Ore._ Pound into a coarse powder the martial stones or earths out of which you design to extract the Iron: roast this powder in a test under the muffle for some minutes, and let your fire be brisk. Then let it cool, beat it very fine, and roast it a second time, keeping it under the muffle till it emit no more smell. Then mix with this powder a flux composed of three parts of Nitre fixed with Tartar, one part of fusile glass, and half a part of Borax and charcoal-dust. The dose of this reducing flux must be thrice the weight of the ore. Put this mixture into a good crucible; cover it with about half a finger thick of Sea-salt; over the crucible put its cover, and lute it on with Windsor-loam made into a paste with water. Having thus prepared your crucible, set it in a melting furnace, which you must fill up with charcoal. Light the fire, and let it kindle by gentle degrees, till the crucible become red-hot. When the decrepitation of the Sea-salt is over, raise your fire to the highest by the blast of a pair of perpetual bellows, or rather several. Keep up this intense degree of heat for three quarters of an hour, or an whole hour, taking care that during all this time the furnace be kept constantly filling up with fresh coals as the former consume. Then take your crucible out of the furnace; strike the pavement on which you set it several times with a hammer, and let it stand to cool: break it, and you will find therein a Regulus of Iron covered with slag. _OBSERVATIONS._ Iron ore, like all others, requires roasting, to separate from it, as much as possible, the volatile minerals, Sulphur and Arsenic, which being mixed with the Iron would render it unmalleable. Indeed it is so much the more necessary to roast these ores, as Iron is, of all metallic substances, that which has the greatest affinity with those volatile minerals; on which account no metallic substance whatever is capable of separating it from them by fusion and precipitation. Fixed Alkalis, it is true, have a greater affinity than Iron with Sulphur; but then the composition which a Fixed Alkali forms with Sulphur is capable of dissolving all metals. Consequently, if you do not dissipate the Sulphur by roasting, but attempt to separate it from the Iron by melting the ore with a Fixed Alkali, the Liver of Sulphur formed in the operation will dissolve the martial part; so that after the fusion you will find little or no Regulus. All Iron ores in general are refractory, and less fusible than any other; for which reason a much greater proportion of flux, and a much more violent degree of fire, is required to smelt them. One principal cause why these ores are so refractory is the property which Iron itself has of being extremely difficult to fuse, and of resisting the action of the fire so much the more as it is purer, and further removed from its mineral state. Among all the metallic substances it is the only one that is less fusible when combined with that portion of phlogiston which gives it the metalline form, than when it is deprived thereof, and in the form of a calx. In smelting-houses Iron ore is fused amidst charcoal, the phlogiston of which combines with the martial earth, and gives it the metalline form. The Iron thus melted runs down to the bottom of the furnace, from whence it is let out into large moulds, in which it takes the shape of oblong blocks, called _Pigs_ of Iron. This Iron is still very impure, and quite unmalleable. Its want of ductility after the first melting arises partly from hence, that, notwithstanding the previous roasting which the ore underwent, there still remains, after this first fusion, a considerable quantity of Sulphur or Arsenic combined with the metal. A certain quantity of quick-lime, or of stones that will burn to lime, is frequently mixed with Iron ore on putting it into the smelting furnace. The lime being an absorbent earth, very apt to unite with Sulphur and Arsenic, is of use to separate those minerals from the Iron. It is also of use to mix some such matters with the ore, when the stones or earths which naturally accompany it are very fusible; for, as the Iron is of difficult fusion, it may happen that the earthy matters mixed with the Iron shall melt as easily as the metal, or perhaps more easily. In such a case there is no separation of the earthy from the metalline part, both of which melt and precipitate together promiscuously; now quick-lime, being extremely refractory, serves on this occasion to check the melting of those matters which are too fusible. Yet quick-lime, notwithstanding its refractory quality, may sometimes be of use as a flux for Iron. This is the case when the ore happens to be combined with substances which, being united with lime, render it fusible: such are all arsenical matters, and even some earthy matters, which being combined with quick-lime make a fusible compound. When the ore of an Iron mine is found difficult to reduce, it is usually neglected even though it be rich: because Iron being very common, people chuse to work those mines only whose ores are smelted with the most ease, and require the least consumption of wood. Yet refractory ores are not to be altogether rejected, when another Iron ore of a different quality is found near them. For it often happens, that two several Iron ores, which being worked separately are very difficult to manage, and yield at last but bad metal, become very tractable, and yield excellent Iron, when smelted together: and accordingly such mixtures are often made at Iron-works. The Iron obtained from ores by the first fusion may be divided into two sorts. The one, when cold, resists the hammer, doth not easily break, and is in some measure extensible on the anvil; but, if struck with a hammer when red-hot, flies into many pieces: this sort of Iron hath always a mixture of Sulphur in it. The other sort, on the contrary, is brittle when cold, but somewhat ductile when red-hot. This Iron is not sulphurated, is naturally of a good quality, and its brittleness arises from its metalline parts not being sufficiently compacted together. Iron abounds so much, and is so universally diffused through the earth, that it is difficult to find a body in which there is none at all: and this hath led several Chymists, even men of great fame, into the error of thinking that they had transmuted into Iron several sorts of earths in which they suspected no Iron, by combining them with an inflammable matter; whereas, in fact, all they did was to give the metalline form to a true martial earth which happened to be mixed with other earths. PROCESS II. _To render Pig-iron and brittle Iron malleable._ Into an earthen vessel widening upwards put some charcoal-dust, and thereon lay the Pig-iron which you propose to render ductile; cover it all over with a quantity of charcoal; excite the fire violently with a pair, or more, of perpetual bellows till the Iron melt. If it do not readily flow and form a great deal of slag on its surface, add some flux, such as a very fusible sand. When the matter is in fusion keep stirring it from time to time, that all the parts thereof may be equally acted on by the air and the fire. On the surface of the melted Iron _scoriæ_ will be formed, which must be taken off as they appear. At the same time you will see a great many sparkles darted up from the surface of the metal, which will form a sort of fiery shower. By degrees, as the Iron grows purer, the number of these sparkles diminishes, though they never vanish entirely. When but few sparkles appear, remove the coals which cover the Iron, and let the slag run out of the vessel; whereupon the metal will grow solid in a moment. Take it out while it is still red-hot, and give it a few strokes with a hammer, to try if it be ductile. If it be not yet malleable, repeat the operation a second time, in the same manner as before. Lastly, when it is thus sufficiently purified by the fire, work it for a long time on the anvil, extending it different ways, and making it red-hot as often as there is occasion. Iron thus brought to the necessary degree of ductility, so as to yield to the hammer, and suffer itself to be extended every way, either hot or cold, without breaking to bits, or even cracking in the least, is very good and very pure. If it cannot be brought to this degree by the method here prescribed, it is a proof that the ore from which this Iron was extracted ought to be mixed with other ores; but it frequently requires a great number of trials to obtain an exact knowledge of the quality and proportion of those other ores with which it is to be mixed. _OBSERVATIONS._ The brittleness and shortness of Pig-iron arises from the heterogeneous parts which it contains, and which could not be separated from it by the first fusion. These extraneous matters are usually Sulphur, Arsenic, and unmetallic earth, and also a ferruginous earth; but such as could not be combined with the phlogiston as it ought to be, in order to have the properties of a metal, and must therefore be considered as heterogeneous, with respect to the other well-conditioned martial particles. The Pig-iron, by undergoing repeated fusions, is freed from those heterogeneous matters; those which are volatile, such as Sulphur and Arsenic, being dissipated, and the unmetallic matters being scorified. As to the ferruginous earth, which did not at first acquire the metalline form, it becomes true Iron at last; because, among the coals with which it is encompassed, it meets with a sufficient quantity of phlogiston to reduce it to metal. Charcoal is also necessary on this occasion, that it may continually furnish phlogiston to the Iron, which would otherways be converted into a calx. Hammering the red-hot Iron, after each fusion, serves to force out from amongst the martial parts such earthy matters as may happen to remain there, and so bring into closer contact the metalline parts which were separated before by the interposition of those heterogeneous matters. PROCESS III. _To convert Iron into Steel._ Take small bars of the best Iron; that is, of such as is malleable both hot and cold; set them on their ends in a cylindrical earthen vessel, whose depth is equal to the length of the bars, and in such a manner that they may be an inch distant from each other, and from the sides of the crucible. Fill the vessel with a cement compounded of two parts of charcoal, one part of bones burnt in a close vessel till they become very black, and one half part of the ashes of green wood; having first pulverized and thoroughly mixed the whole together. Take care to lift up the Iron bars a little, to the end that the cement may cover the bottom of the vessel, and so that there be about the depth of half an inch thereof under every bar: cover the crucible and lute on the cover. Set the crucible thus prepared in a furnace, so contrived that the crucible may be surrounded with coals from top to bottom: for eight or ten hours keep up such a degree of fire that the vessel may be moderately red; after this take it out of the furnace; plunge your little Iron bars into cold water, and you will find them converted into Steel. _OBSERVATIONS._ The principal difference between Iron and Steel consists in this, that the latter is combined with a greater quantity of phlogiston than the former. It appears by this experiment, that, to make Iron unite with an inflammable matter, it is not necessary it should be in fusion; it is sufficient that it be so red-hot as to be opened and softened by the fire. Every kind of charcoal is fit to be an ingredient in the composition of the cement employed to make Steel, provided it contain no Vitriolic Acid. However, it hath been observed, that animal coals produce a speedier effect than others: for which reason it is proper to mix something of that kind with charcoal-dust, as above directed. The following signs shew that the operation hath succeeded, and that the Iron is changed into good Steel. This metal being quenched in cold water, as proposed above, acquires such an extraordinary degree of hardness, that it will by no means yield to any impression of the file or hammer, and will sooner break in pieces than stretch upon the anvil. And here it is proper to observe, that the hardness of Steel varies with the manner in which it is quenched. The general rule is, that the hotter the Steel is when quenched, and the colder the water is in which you quench it, the harder it becomes. It may be deprived of the temper thus acquired, by making it red-hot, and letting it cool slowly; for it is thereby softened, rendered malleable, and the file will bite upon it. For this reason the artisans who work in Steel begin with untempering it, that they may with more ease shape it into the tool they intend to make. They afterwards new-temper the tool when finished, and by this second temper the Steel recovers the same degree of hardness it had acquired by the first temper. The colour of Steel is not so white as that of Iron, but darker, and the grains, facets, or fibres, which appear on breaking it, are finer than those observed in Iron. If the bars of Iron thus cemented in order to convert them into Steel be too thick, or not kept long enough in cementation, they will not be turned into Steel throughout their whole thickness: their surfaces only will be Steel to a certain depth, and the center will be mere Iron; because the phlogiston will not have thoroughly penetrated them. On breaking a bar of this sort, the difference in colour and grain between the Steel and the Iron is very visible. It is easy to deprive Steel of the super-abundant quantity of phlogiston which constitutes it Steel, and thereby reduce it to Iron. For this purpose it need only be kept red-hot some time, observing that no matter approach it all the while that is capable of refunding to it the phlogiston which the fire carries off. The same end is still sooner obtained by cementing it with meagre hungry matters, capable of absorbing the phlogiston; such as bones calcined to whiteness, and cretaceous earths. Steel may also be made by fusion; or Pig-iron may be converted into Steel. For this purpose the same method must be employed as was above directed for reducing Pig-iron into malleable Iron; with this difference, that, as Steel requires more phlogiston than is necessary to Iron, all the means must be made use of that are capable of introducing into the Iron a great deal of phlogiston; such as melting but a small quantity of Iron at a time, and keeping it constantly encompassed with abundance of charcoal; reiterating the fusions; taking care that the blast of the bellows directed along the surface of the metal do not remove the coals that cover it, _&c._ And here it must be observed, that there are some sorts of Pig-iron which it is very difficult to convert into Steel by this method, and that there are others which succeed very readily, and with scarce any trouble at all. The ores which yield the last-mentioned sort of Pig-iron are called _Steel Ores_. Steel made by this means must be tempered in the same manner as that made by cementation[8]. [8] M. Réaumur hath obliged the public with a treatise on the means of converting Iron into Steel, in which he hath exhausted the subject. Such as desire the amplest and most useful instructions on that part of metallurgy, would do well to consult his Work. PROCESS IV. _The Calcination of Iron. Sundry Saffrons of Mars._ Take filings of Iron, in what quantity you please; put them into a broad unglazed earthen vessel; set it under the muffle of a cupelling furnace; make it red-hot; stir the filings frequently; and keep up the same degree of fire till the Iron be wholly turned into a red powder. _OBSERVATIONS._ Iron easily loses its phlogiston by the action of fire. The calx that remains after its calcination is exceeding red; which makes this be thought the natural colour of the earth of that metal. It hath accordingly been observed, that all the earths and stones which either are naturally red, or acquire that colour by calcination, are ferruginous. The yellowish red colour which every calx of Iron hath, in whatever manner it be prepared, hath procured the name of _Crocus_ or _Saffron_ to every preparation of this kind. That made in the manner above directed is called in Medicine _Crocus Martis astringens_. The rust produced on the surface of Iron is a sort of calx of Iron made by way of dissolution. The moisture of the air acts upon the metal, dissolves it, and robs it of some of its phlogiston. This rust is called in Medicine _Crocus Martis Aperiens_; because it is thought that the saline parts, by means whereof the humidity dissolves the Iron, remain united with the metal after its dissolution, and give it an aperitive virtue. The Apothecaries prepare this sort of Saffron of Mars by exposing Iron filings to the dew, till they be turned entirely to rust: which is then called _Saffron of Mars by dew_. Another Saffron of Mars is also prepared in a much shorter manner, by mixing filings of Iron with pulverized Sulphur, and moistening the mixture, which after some time ferments and grows hot. It is then set on the fire; the Sulphur burns away, and the mass is kept stirring till it become a red matter. This Saffron is nothing but Iron dissolved by the Acid of Sulphur, which is known to be of the same nature with that of Vitriol; and consequently this Saffron of Mars is no way differing from Vitriol calcined to redness. PROCESS V. _Iron dissolved by the mineral Acids._ Put any mineral Acid whatever into a matrass with some water; set the matrass on a sand-bath gently heated; drop into the vessel some filings of Iron: the phenomena which usually accompany metalline dissolutions will immediately appear. Add more filings, till you observe the Acid hath lost all sensible action upon them: then remove your matrass from the sand-bath; you will find in it a solution of Iron. _OBSERVATIONS._ Iron is very easily dissolved by all the Acids. If you make use of the Vitriolic Acid, care must be taken to weaken it with water, in case it be concentrated; because the dissolution will succeed the better. The vapours that rise on this occasion are inflammable; and if a lighted paper be held to the mouth of the matrass, especially after keeping it stopt for some time and shaking the whole gently, the sulphureous vapours take fire with such rapidity as to produce a considerable explosion; which is sometimes strong enough to burst the vessel into a thousand pieces. This solution hath a green colour, and is in fact a fluid Green Vitriol, which wants nothing but rest to make it shoot into crystals. If you make use of the Nitrous Acid, you must cease adding more filings when the liquor, after standing still some moments, becomes turbid; for, when this Acid is impregnated with Iron to a certain degree, it lets fall some of that which it had dissolved, and becomes capable of taking up fresh filings. Thus, by constantly adding new supplies of Iron, this Acid may be made to dissolve a much greater quantity thereof than is necessary to saturate it entirely. This solution is of a russet colour, and doth not crystallize. If the weather be not extremely cold, and the Acids have a proper degree of strength, the sand-bath is unnecessary, as the dissolution will succeed very well without it. Iron dissolved by Acids may be separated therefrom, like all other metallic substances in the same circumstances, either by the action of fire, which carries off the Acid and leaves the Martial Earth, or by the interposition of substances which have a greater affinity than metallic substances have with Acids; that is, by Absorbent Earths and Alkaline Salts. By whatever means you separate Iron from an Acid solvent, it constantly appears, after the separation, in the form of a yellowish red powder; because it is then deprived of most of the phlogiston to which it owed its metalline form; whence it is reasonable to think, that this is the proper colour of Martial earth. All these precipitates of Iron are true Saffrons of Mars, which, as well as those prepared by calcination, are so much the further removed from the nature of a metal, the more they are deprived of their phlogiston. Thence it comes that they are more or less soluble by Acids, and more or less attracted by the magnet: as no ferruginous earth, perfectly deprived of all inflammable matter, is at all attracted by the magnet, or soluble by Acids. CHAP. V. _Of_ TIN. PROCESS I. _To extract Tin from its Ore._ Break your Tin ore into a coarse powder, and by washing carefully separate from it all the heterogeneous matters, and ores of a different kind, that may be mixed therewith. Then dry it, and roast it in a strong degree of fire, till no more Arsenical vapour rise from it. When the ore is roasted, reduce it to a fine powder, and mix it thoroughly with twice its weight of the black flux well dried, a fourth part of its weight of clean iron filings, together with as much borax and pitch; put the mixture into a crucible; over all put Sea-salt to the thickness of four fingers, and cover the crucible close. Set the crucible thus prepared in a melting furnace: apply at first a moderate and slow degree of fire, till the flame of the pitch, which will escape through the joint of the cover, disappear entirely. Then suddenly raise your fire, and urge it with rapidity to the degree necessary for melting the whole mixture. As soon as the whole is in fusion take the crucible out of the furnace, and separate the Regulus from the scoria. _OBSERVATIONS._ All Tin ores contain a considerable quantity of Arsenic, and no Sulphur at all, or at most very little. Hence it comes that, though Tin be the lightest of all metals, its ore is nevertheless much heavier than any other; Arsenic being much heavier than Sulphur, of which the ores of every other kind always contain a pretty large proportion. This ore is moreover very hard, and is not brought to a fine powder with so much ease as the rest. These properties of Tin ore furnish us with the means of separating it easily by lotion, not only from earthy and stony parts, but even from the other ores which may be mixed with it. And this is of the greater advantage on two accounts, _viz._ because Tin cannot endure, without the destruction of a great part thereof, the degree of fire necessary to scorify the refractory matters which accompany its ore; and again because this metal unites so easily with Iron and Copper, the ores of which are pretty commonly blended with Tin ore, that, after the reduction, it would be found adulterated with a mixture of these two metals, if they were not separated from it before the fusion. But sometimes the Iron ore confounded with that of Tin is very heavy, and is not easily pulverized; whence it comes to pass that it cannot be separated therefrom by washing only. In that case the magnet must be employed to separate it, after the ore hath been roasted. Roasting is moreover necessary for Tin ore, in order to dissipate the Arsenic which volatilizes, calcines, or destroys one part of the Tin, and reduces the rest to a short, brittle substance, like a Semi-metal. The ore is known to be sufficiently roasted when no more fumes rise from it; when it has lost the smell of garlic; and when it does not whiten a clean plate of Iron held over it. Tin being one of those metals which are most easily calcined, it is necessary in reducing its ore to employ such matters as may furnish it with phlogiston. In order to defend it from the contact of the air, which always accelerates the calcination of metallic substances, the mixture is to be covered with Sea salt; and the addition of pitch helps to increase the quantity of phlogiston. PROCESS II. _The Calcination of Tin._ Into an unglazed earthen dish put the quantity of Tin you intend to calcine; melt it, and keep stirring it from time to time. Its surface will be covered with a greyish white powder: continue the calcination till all your Tin be converted into such a powder, which is the _Calx of Tin_. _OBSERVATIONS._ Though the calcination of metalline substances is promoted by exposing them, in powder, or in filings, to the action of fire, and by ordering it so that they may not melt, because they present a much smaller surface when melted than when unmelted; yet we have not directed this precaution to be used in calcining Tin. The reason is, this metal is so fusible that it cannot endure the degree of fire requisite to destroy its phlogiston without melting, and of course, though Tin calcines easily, the operation is nevertheless tedious, because the melted metal presents but a small surface to be acted on by the fire and the air. This inconvenience may be partly remedied, and the operation greatly expedited, by dividing the quantity of Tin to be calcined into several small parcels, and exposing them to the fire in separate vessels, so that they may not re-unite when melted, and form one single mass. Leaf Tin cast on Nitre in actual fusion causes it to deflagrate and fulminate; and from this mixture there rises a white vapour, which is converted into flowers when it meets with any obstacle to impede its flying off entirely. Mr. Geoffroy, who went through a course of experiments on Tin, an account whereof may be seen in the Memoirs of the Academy of Sciences, found that from the colour of the calx of that metal a judgment may be formed of its degree of purity, and nearly of the quantity and quality of the metallic substances with which it is alloyed. The experiments tried on this subject by that eminent Chymist are very curious. He performed the calcination in a crucible, which he heated to a cherry-red, and kept up the same degree of fire from the beginning to the end of the operation. The calx which formed upon his metal, in that degree of heat, appeared like small white scales, a little reddish on the under side. He pushed it to one side as it formed, to the end that it might not cover the surface of the metal, which, like all others, requires the contact of the air to turn it into a calx. "While he was making these calcinations, he had an opportunity of observing a curious fact, of which no body before him had ever taken notice; probably because no body had ever calcined Tin by the same method. The fact is, that during the calcination of the Tin, whether you break the pellicle which forms on the surface of the metal while in red-hot fusion, or whether you let it remain without touching it, you perceive in several places a small swell of a certain matter, which bursts and makes its way through the pellicle. This matter puffs up, grows red, at the same instant takes fire, and darts out a small whitish flame, as vivid and as brilliant as that of Zinc, when urged by a fire strong enough to sublime it into flowers. The vividness of this flame may be further compared to that of several small grains of phosphorus of urine fired and gently dropped on boiling water. From this bright flame a white vapour exhales; after which the swelled mass partly crumbles down, and turns to a light white powder, sometimes spotted with red, according to the force of the fire. After this momentary ignition, there arise stronger, more numerous, or more frequent heavings of matter, out of which issues a good deal of white fume, that may be intercepted by a cover of tin-plate or copper fitted to the crucible, and appears to be the flowers of Tin, which in some measure corrode these metals. Hence Mr. Geoffroy conjectures, with a great deal of probability, that their sublimation is promoted by a portion of Arsenic. When the crust formed by this calx comes to be too thick, or in too great a quantity, to be pushed on one side, so as to leave part of the metal uncovered, Mr. Geoffroy puts out the fire, because no more calx would be formed: the communication of the external air with the Tin in fusion being absolutely necessary thereto, as hath been already said. In this operation it is to be observed that, if the fire be too slow, neither the inflammation of the sulphureous particles, nor the white fumes that rise, will be so distinctly perceived, as when the fire is of the degree requisite to keep the crucible just of a cherry-red heat. "Mr. Geoffroy having taken off this first calx began the calcination anew. In this second heat the buddings or heavings were more considerable, and shot up in the form of cauli-flowers; but were still composed of little scales. The thoroughly calcined portion of this vegetation was likewise white and red; and the inferior surfaces of some little bits thereof were wholly red. When these calcinations are continued, sulphureous vapours rise seemingly of another kind than those which appeared in the beginning; for all the calx made by the first heat was perfectly white: whereas in the second it begins to be spotted here and there with a tinge of black. Mr. Geoffroy was obliged to go through a course of twelve several calcinations before he could convert two ounces of Tin into a calx. He had the opportunity, during these several calcinations, to observe that after the fourth, and sometimes after the third, the red spots of the calx decrease, and the black increase; that the germinations cease; that the crust of the calx remains flat; that in the twelfth fire the Tin yields no more of this scaly crust; that towards the end the undulations of the fused metal appear no longer; and that the small remainder of calx is mixed with several very minute grains of metal, which seem much harder than Tin. Mr. Geoffroy could not collect a sufficient quantity thereof to cupel them, and satisfy himself whether or no they were Silver." Though Tin, and all the imperfect metals in general, seem converted to a calx, and lose the metalline form, by one single calcination, and that a slight one; yet they are not wholly deprived of their phlogiston: for if the calx of Tin, for instance, prepared according to the process above delivered, be cast upon Nitre in fusion, it will make that salt deflagrate very perceptibly; a convincing proof that it still contains much inflammable matter. If therefore a calx be required absolutely free from phlogiston, this first calx must be recalcined by a more violent fire, and the calcination continued till all the phlogiston be dissipated. "Mr. Geoffroy, being desirous of having his calx of Tin very pure and perfectly calcined, exposed once more to the action of fire the twelve portions of calx obtained by his former calcinations. But, as it would have been too tedious to re-calcine them all separately, he made four parcels of the whole, each consisting of three taken according to the order in which they were first calcined; and gave to each a fire sufficiently strong, and long enough continued, to calcine them as thoroughly as was possible. After this second calcination he found them all of a most beautiful white, except the first parcel: as that consisted of the portions obtained by the three first heats, in all of which there were scales tinged with red, it still retained a stain of carnation, though hardly perceptible. Agreeably to the general rule, the two ounces of Tin gained in weight by being thus calcined; and the increase was two drams and fifty seven grains. "Mr. Geoffroy observes, that no Tin, but what is absolutely pure, will yield a perfectly white calx. He calcined in this manner several other parcels of Tin that were impure and variously alloyed; each of which produced a calx differently coloured, according to the nature and quantity of its alloy: whence he justly concludes, that calcination is a very good method of trying the fineness of Tin, or its degree of purity." The particulars of Mr. Geoffroy's experiments on this subject, which are very curious, may be seen in the Memoirs of the Academy for 1738. It is proper to take notice that a man should be very cautious how he exposes himself to the vapours of Tin, because they are dangerous; this metal being very justly suspected by Chymists of containing something Arsenical. PROCESS III. _The dissolution of Tin by Acids, The Smoking Liquor of_ Libavius. Put into a glass vessel what quantity you please of fine Tin cut into little bits. Pour on it thrice as much _aqua regis_, compounded of two parts _aqua fortis_ weakened with an equal quantity of very pure water, and one part Spirit of Salt. An ebullition will arise, and the Tin will be very rapidly dissolved; especially if the quantities of metal and of _aqua regis_ be considerable. _OBSERVATIONS._ Tin is soluble by all the Acids; but _aqua regis_ dissolves it best of any. Yet in this dissolution it comes to pass that part of the dissolved Tin precipitates of its own accord to the bottom of the vessel, in the form of a white powder. This solution of Tin is very fit for preparing the purple-coloured precipitate of Gold. For this purpose the solution of Tin must be let fall, drop by drop, into a solution of Gold. Spirit of Nitre dissolves Tin nearly as _aqua regis_ does; but it occasions a greater quantity of calx. If two or three parts of Oil of Vitriol be poured on one part of Tin, and if the vessel in which the mixture is made be exposed to such a degree of heat as to evaporate all the moisture, there will remain a tenacious matter sticking to the sides of the vessel. If water be poured on this matter, and it be then exposed a second time to the fire, it will dissolve entirely, excepting a small portion of a glutinous substance, which also may be dissolved in fresh Oil of Vitriol. The Acid of Sea-salt may be combined with Tin by the following process. Mix perfectly, by trituration in a marble mortar, an amalgam of two ounces of fine Tin, and two ounces and a half of Quick-silver, with as much Corrosive Sublimate. As soon as the mixture is completed, put it into a glass retort, and distil with the same precautions as we directed to be used in preparing concentrated and smoking Acids. There will first come over into the receiver some drops of a limpid liquor, which will be soon followed by an elastic spirit that will issue out with impetuosity. At last some flowers, and a saline tenacious matter, will rise into the neck of the retort. Then stop your distillation, and pour into a glass bottle the liquor you will find in the receiver. This liquor continually exhales a considerable quantity of dense, white fumes, as long as it is allowed to have a free communication with the air. The product of this distillation is a combination of the Acid of Sea-salt with Tin. As the affinity of Tin with this Acid is greater than that of Mercury, the Acid contained in the Corrosive Sublimate quits the Mercury, wherewith it was united, to join the Tin; which it volatilizes so as to make it rise with itself in a limpid form. We make use of the amalgam of Tin with Quick-silver, because we are thereby enabled to mix the Corrosive Sublimate perfectly therewith, as the success of the operation requires it should be. In this experiment the Tin is volatilized, and the Acid of Sea-salt, which is exceedingly concentrated, flies off incessantly in the form of white vapours. This compound is known in Chymistry by the name of _Smoking Liquor of Libavius_; a name derived from its quality, and from its Inventor. Tin dissolved by Acids is easily separated from them by Alkalis. It always precipitates in the form of a white calx. CHAP. VI. _Of_ LEAD. PROCESS I. _To extract Lead from its Ore._ Having roasted your Lead ore reduce it to a fine powder; mix it with twice its weight of the black flux, and one fourth of its weight of clean iron filings and borax; put the whole into a crucible capable of containing at least thrice as much; over all put Sea-salt four fingers thick; cover the crucible; lute the juncture; dry the whole with a gentle heat, and set it in a melting furnace. Make the crucible moderately red: you will hear the Sea-salt decrepitate, and after the decrepitation a small hissing in the crucible. Keep up the same degree of fire till that be over. Then throw in as many coals as are necessary to complete the operation entirely, and raise the fire suddenly, so as to bring the whole mixture into perfect fusion. Keep up this degree of fire for a quarter of an hour, which is time sufficient for the precipitation of the Regulus. When the operation is finished, which may be known by the quietness of the matter in the crucible, and by a bright vivid flame that will rise from it, take the crucible out of the furnace, and separate the Regulus from the scoria. _OBSERVATIONS._ All Lead ore contains a good deal of Sulphur, which must be first separated from it by roasting: and as this kind of ore is apt to fly when first exposed to the fire, it is proper to keep it covered till it be thoroughly heated. Another precaution to be used, in roasting this ore, is not to give it too great a heat, but to keep the vessel which contains it just moderately red; because it easily turns clammy, which occasions it to stick to the vessel. The Iron that is added, and mixed with the flux, absorbs the Sulphur which may happen to remain, even after roasting: it helps also to separate from the Lead some portions of semi-metal, especially of Antimony, which are frequently mixed with this ore. There is no fear least the Iron mix with the Lead in fusion, and adulterate it: for these two metals are incapable of contracting any union together, when each has its metalline form. Nor is there any reason to apprehend lest the Iron should, by its refractory quality, obstruct the fusion of the mixture; for though this metal be not fusible when alone, yet, by the union it contracts with the matters it is designed to absorb, it becomes so to such a degree as in some measure to perform, on this occasion, the office of a flux. The government of the fire is a point of great consequence in this operation. It is necessary to apply but a moderate degree of heat at first: for, when the metallic earth of the Lead, combining with the phlogiston, acquires the metalline form, it swells up in such an extraordinary manner, that there is great danger least the matter should overflow, and run all out of the containing vessel. With a view therefore to avoid this inconvenience, we direct a very large crucible to be used. This heaving of the Lead, at the instant of its reduction, is attended with a noise like the whistling of wind. Notwithstanding all the precautions that can be used to prevent the reduction from taking place too hastily, and so occasioning the effusion of the matter, it often happens that, on raising the fire in order to bring the mixture into fusion, the hissing suddenly begins again, and is very loud. In that case all the apertures of the furnace must immediately be shut close, in order to choak and suffocate the fire: for, if this be neglected, the matter in the crucible will swell up, make its way through the luting of the juncture, nay, push up the cover, and run over. This accident is to be apprehended during the first five or six minutes after you raise the fire in order to melt the mixture. This effusion of the matter is accompanied with a dull flame, a thick, grey and yellow smoke, and a noise like that of some boiling liquor. When you observe these several phenomena you may be sure the matter is run out of the crucible, either in the manner above described, or by making its way through some cracks in the vessel, and consequently that the operation is spoiled. Moreover, this event infallibly follows whenever a bit of coal happens to fall into the crucible; and this is one reason why it is necessary to cover it. You may be certain that the operation hath succeeded if the scoria be smooth when cold, and have not in part escaped through the lute; if the Lead be not dispersed in globules through the whole mass of the matter contained in the crucible, but is, on the contrary, collected at the bottom, in the form of a solid Regulus, not very shining, but of a blueish cast, and ductile. Moreover, the scoria ought, in the present case, to be hard and black, and should not appear full of holes like a sieve, except only in that part which was contiguous to the Salt. Here it is proper to observe, that the Sea-salt doth not mix with the scoria, but floats upon it. After the operation it is black; which colour it gets, no doubt, from the charred parts of the flux. The absence of these signs shews the operation to have miscarried. When the ore to be smelted is pyritose and refractory, it may be roasted at first with a much stronger degree of fire than is used for ores that are fusible; because the martial earth, and the unmetallic earth, which are always mixed in pyritose matters, hinder it from growing readily soft in the fire. Besides, such an ore requires a greater quantity of the black flux and of borax to be mixed with it, and a higher degree of fire to fuse it. It is generally needless to mix iron filings with this sort of ore; because the martial earth, with which pyritose matters are always accompanied, is reduced during the operation by the help of the black flux, which for that purpose is mixed with it in a large proportion, and furnishes a quantity of iron sufficient to absorb the heterogeneous minerals mixed with the Lead. Yet, if it should be observed that the pyrites which accompany the Lead ore are arsenical, then, as such pyrites contain but a small quantity of ferruginous earth, iron filings must be added; which are, on this occasion, so much the more necessary for absorbing the Arsenic, as this mineral remains in part confounded with the ore, is reduced to a Regulus during the operation, unites with the Lead, and destroys a great deal of it by procuring its vitrification. The Lead obtained from such pyritose ores is commonly not very pure; it is blackish and scarce ductile; qualities communicated to it by a small mixture of Copper in the pyrites, which always contain more or less thereof. We shall presently shew the method of separating Lead from Copper. Lead ore may also be reduced by melting it amidst coals. For that purpose first kindle a fire in the furnace in which you intend to melt your ore; then put a layer of your ore immediately upon the lighted coals, and cover it with another layer of coals. Though the melting furnace used for this operation be capable of giving a considerable heat, yet it is necessary further to increase the force of the fire by the means of a good pair of perpetual bellows, which will produce an effect like that of a forge. The ore melts, the earth of the Lead unites with the phlogiston of the coals, and so is reduced to metal, which runs through the coals, and falls into an earthen vessel placed at the bottom of the furnace to receive it. Care must be taken to keep this vessel well filled with charcoal-dust, to the end that the Lead may be in no danger of calcination while it continues there; the charcoal-dust constantly furnishing it with phlogiston to preserve its metalline form. The earthy and stony matters that accompany the ore are scorified by this fusion, just as they are by the other which is performed in a close vessel. With regard to the Sulphur and Arsenic, they are supposed to have been first accurately separated from the ore by roasting. This is the method commonly employed for smelting Lead ore at the works. PROCESS II. _To separate Lead from Copper._ With luting earth and charcoal-dust make a flat vessel, widening upwards, and large enough to contain your metalline mass. Set it shelving downwards from the back towards the fore-part; and in the fore-part, at the bottom, make a little gutter communicating with another vessel of the same nature, placed near the former and a little lower. Let the mouth of the gutter within side the upper vessel be narrowed, by means of a small iron plate fixed across it, while the loam is yet soft; so as to leave a very small aperture, in the lower part of this canal, sufficient to discharge the Lead as it melts. Dry the whole by placing lighted coals around it. When this apparatus is dry, put your mixed mass of Copper and Lead into the upper vessel: both in that, and in the other vessel, light a very gentle fire of wood or charcoal, so as not to exceed the degree of heat necessary to melt Lead. In such a degree of heat the Lead contained in the mixed mass will melt, and you will see it run out of the upper vessel into the lower; at the bottom of which it will unite into a Regulus. When in this degree of heat no more Lead flows, increase the fire a little, so as to make the vessel moderately red. When no more will run, collect the Lead contained in the lower vessel. Melt it over again in an iron ladle, with a degree of fire sufficient to make the ladle red; throw into it a little tallow or pitch, and while it burns keep stirring the metal, in order to reduce any part of it that may be calcined. Remove the pellicle or thin crust which will form on the surface; squeeze out all the Lead it contains, and then put it to the mass of Copper left in the upper vessel. Check the fire, and in the same manner take off a second skin that will form on the surface of the Lead. Lastly, when the metal is ready to fix, take off the skin that will then appear on it. The Lead remaining after this will be very pure, and free from all alloy of Copper. With regard to the Copper itself, you will find it in the upper vessel covered with a thin coat of Lead: and if the Lead mixed with it was in the proportion of a fourth or a fifth part only, and the fire applied was gentle and slow, it will retain nearly the same form after the operation that the mixed mass had before. _OBSERVATIONS._ Lead frequently remains mixed with Copper after the reduction of its ore, especially if the ore was pyritose. Though Copper be a much more beautiful and more ductile metal than Lead, yet the latter by being alloyed with the former is rendered eager and brittle. This bad quality is easily discovered by the eye on breaking it: for the surface of the broken part appears all granulated; whereas when it is pure it is more evenly, and resembles a congeries of solid angles. If the Lead be alloyed with a considerable quantity of Copper, its colour hath a yellowish cast. Considering the bad qualities which Copper communicates to Lead, it is necessary to separate these two metals from each other. The method above laid down is the simplest and the best. It is founded on two properties belonging to Lead: the first is that of being much more fusible than Copper; so that it will melt and run in a degree of heat that is not capable of making the Copper even red-hot, which yet is very far from being able to melt it: the second is, that Lead, though it hath an affinity with Copper, and unites very perfectly therewith, yet is not able to dissolve it without a greater heat than the degree barely necessary to fuse Lead. Hence it comes that Lead may be melted in a Copper vessel, provided no greater degree of heat be applied than that purpose requires. But when the Lead becomes so hot as to be red, fume, and boil, it instantly begins to dissolve the Copper. For this reason, it is essential to the success of our operation that a moderate degree of heat only be applied, and no greater than is requisite to keep the Lead in fusion. Charcoal-dust is made an ingredient in the composition of the vessels used on this occasion, in order to prevent the calcination of the Lead. The iron plate, with which the entrance of the gutter within the upper vessel is narrowed, serves to prevent the larger pieces of Copper, which the Lead may carry along with it, from passing through: it stops them, and allows the Lead to run off alone. But as these parcels of Copper may entirely choak the passage, care must be taken, when any happen to be stopt, to remove them from the entrance of the gutter, and push them back into the middle of the vessel. It is also necessary to observe whether or no the Lead fixes any where in the passage; and, if it does, the heat of that part must be increased, in order to melt it and make it run off. Notwithstanding all the precautions that can be taken, to hinder the melted Lead from carrying off any Copper with it, it is impossible to prevent this inconvenience entirely; and therefore the Lead is melted over again, in order to separate the small portion of Copper with which it is still adulterated. As Copper is much lighter than Lead, if these two metals happen to be so blended together that the Copper, without being in fusion and dissolved by the Lead, is only interposed between the parts of the melted Lead, so as to swim therein, it is then precisely in the case of a solid body plunged into a fluid heavier than itself, and must rise to the surface, like wood thrown into water. It is proper to burn some inflammable matter on this melted Lead, in order to reduce such parts thereof as are constantly calcining on its surface while it is in fusion; for without this precaution they would be taken off together with the Copper. The Copper remaining after this separation is, as we took notice before, still mixed with a little Lead. If you desire to separate it entirely therefrom, you must put it into a cupel, and expose it under the muffle to such a degree of fire as may convert all the Lead into litharge. This cannot be so done but that some of the Copper also will be scorified by the heat of the fire, and by the action of the Lead: but as there is a very great difference between the facility and readiness with which these two metals calcine, the portion of Copper that is calcined, while the whole Lead is turning into litharge, is scarce worth considering. The Lead, though carefully separated from the Copper by the process here delivered, is not yet absolutely pure: sometimes it is alloyed with Gold, and almost always contains some Silver. If you would free the Lead as much as possible from any mixture of these two metals, you must convert it into glass, separate the remaining bead, and afterwards reduce this glass of Lead. But, as these two perfect metals are of no prejudice to the Lead, it is not usual to separate them from it, unless they be in a sufficient proportion to defray the charge, and produce some profit besides. When we examine by the cupel the just proportion of Gold and Silver that an ore or a mixed metalline mass will yield, we make a previous assay of the Lead to be employed in the operation, and afterwards, in our estimate, deduct a proper allowance for the quantity of fine metal due to the Lead made use of. PROCESS III. _The Calcination of Lead._ Take what quantity of Lead you please; melt it in one or more unglazed earthen pans: a dark grey powder will be found on its surface. Keep stirring the metal incessantly till it be wholly converted into such a powder, which is the _Calx of Lead_. _OBSERVATIONS._ As Lead is a very fusible metal, and in that respect greatly resembles Tin, most of the observations we made on the calcination of Tin may be applied here. In the calcination of all metals, and particularly in this of Lead, there appears a singular phenomenon which is not easily accounted for. It is this: though these matters lose a great deal of their substance, either by the dissipation of their phlogiston, or because some of the metal, perhaps, exhales in vapours, yet when the calcination is over their calces are found to be increased in weight, and this increase is very considerable. An hundred pounds of Lead, for example, converted into Minium, which is nothing but a calx of Lead brought to a red colour by continuing the calcination, are found to gain ten pounds weight; so that for an hundred pounds of Lead we have one hundred and ten pounds of Minium: a prodigious and almost incredible augmentation, if it be considered that, far from adding any thing to the Lead, we have on the contrary dissipated part of it. To account for this phenomenon Natural Philosophers and Chymists have invented several ingenious hypotheses, but none of them entirely satisfactory. As we have no established theory to proceed upon, we shall not undertake to explain this extraordinary fact. PROCESS IV. _To prepare Glass of Lead._ Take two parts of Litharge, and one part of pure crystalline Sand; mingle them together as exactly as possible, adding a little Nitre and Sea-salt: put this mixture into a crucible of the most solid and most compact earth. Shut the crucible with a cover that may perfectly close it. Set the crucible thus prepared in a melting furnace; fill the furnace with coals; light the fire gradually, so that the whole may be slowly heated: then raise the fire so as to make the crucible very red, and bring the matter it contains into fusion; keep it thus melted for a quarter of an hour. Then take the crucible out of the furnace, and break it: in the bottom thereof you will most commonly find a small button of Lead, and over it a transparent Glass, of a yellow colour nearly resembling that of amber. Separate this Glass from the little button of metal, and from the saline matters which you will find above it. _OBSERVATIONS._ Pure Lead, being exposed to a strong fire without any additament, turns to Litharge; which is a scaly sort of substance, more or less yellowish, shining, and soft to the touch. This is the first advance to the Vitrification of Lead. The large refineries of Gold and Silver by the means of Lead furnish a great quantity of this material. It is sometimes whitish, and is then called _Litharge of Silver_; sometimes yellow, and then bears the name of _Litharge of Gold_. The difference of its colour depends on the degree of fire it hath undergone, and on the metalline substances vitrified with it. Litharge alone is very fusible, and being exposed to the fire is easily converted into glass: but this Glass of Lead, made without additament, is so active, so penetrating, and so apt to swell, that it can scarcely be made use of when pure. We are obliged in some sort to clog it, by uniting it with some vitrifiable matter that is not so subtile, such as sand; and it is for this reason, not to render the mixture more fusible, that we have directed the addition of one third part of Sand to two thirds of Litharge. The Nitre and Sea-salt, prescribed as ingredients in the mixture, are designed to procure an equal fusion of the whole. For, as the sand is lighter and less fusible than the Litharge, it will partly rise towards the upper part of the crucible when that matter first begins to flow; in consequence whereof the contents of the upper part will be much more difficult to melt, and form a Glass much more compact than that below: but the Nitre and Sea-salt possessing the upper part of the crucible, because they are still lighter than the Sand, and being in their own nature very efficacious fluxes, on account of their great fusibility, they quickly bring about the fusion of those particles of sand, which, having escaped the action of the Litharge, may have risen unvitrified to its surface. The most difficult thing to procure, and yet the most necessary to the success of this operation, is a crucible of earth so firm and compact as not to be penetrated by the Glass of Lead, which corrodes and makes its way through every thing. The precaution of chusing a crucible, that shall contain a good deal more than the matter to be vitrified, is a necessary one, because Litharge and Glass of Lead are very apt to swell. The rule to keep the crucible close shut is also indispensably necessary, to prevent any bit of charcoal, or other inflammable matter, from falling into it: for when this happens it occasions a reduction of the Lead, which is always attended with a sort of effervescence, and such a considerable heaving, that commonly most of the mixture runs over the crucible. For the same reason it is very proper, before you expose the mixture to the fire, to examine whether or no it contains any matter capable of furnishing a phlogiston during the operation; and if it does, to remove that matter with great care. The little button of Lead, found at the bottom of the crucible after the operation, comes from a small portion of Lead that is commonly left in Litharge, unless you prepare it carefully yourself, and do not take it from the fire till you are sure of having destroyed all the Lead. Besides, this small portion of Lead can be of no prejudice to the operation, because it cannot communicate its phlogiston to the rest of the matter. The revivifying of Litharge, of the Calx, and of the Glass of Lead, may be obtained by the same processes as the reduction of its ore. PROCESS V. _Lead dissolved by the Nitrous Acid._ Put into a matrass some _aqua fortis_ precipitated like that used to dissolve Silver; weaken it by mixing therewith an equal quantity of common water; set the matrass in a hot sand-bath; throw into it, little by little, small bits of Lead, till you see that no more will dissolve. _Aqua fortis_ thus lowered will dissolve about a fourth of its weight of Lead. There is gradually formed upon the Lead, as it dissolves, first a grey powder, and afterwards a white crust, which at last hinder the solvent from acting on the remaining part of the metal; and therefore the liquor should be made to boil, and the vessel should be shaken to remove those impediments, by which means all the Lead will be dissolved. _OBSERVATIONS._ Lead very much resembles Silver, with respect to the phenomena which attend its dissolution in Acids. For example, the Nitrous Acid must be very pure and uncontaminated with the Vitriolic or Marine Acid, to qualify it for keeping the Lead in solution: for, if it be mixed with either the one or the other of these Acids, the Lead will precipitate in the form of a white powder as fast as it dissolves; which is just the case with Silver. If the Vitriolic Acid be mixed with the Nitrous, the precipitate will be a combination of the Vitriolic Acid with Lead; that is, a Neutral Metallic Salt, or Vitriol of Lead. If the Acid of Sea-salt be mixed therewith, the precipitate will be a _Plumbum corneum_; that is, a Metallic Salt resembling the _Luna cornea_. When all the Lead is dissolved as above described, the liquor appears milky. If it be kept warm over the fire till little crystals begin to appear on its surface, and afterwards left to stand quiet, in a certain time there will be found at the bottom a greyish powder, which being tried on Gold is Mercurial enough to whiten it. Little globules of Quick-silver are even discernible in it. We owe this observation, together with this manner of proving the existence of Mercury in Lead, and of procuring it from thence, to M. Grosse, who hath given an account of his process in the Memoirs of the Academy of Sciences, from whence we have copied the description of the operation in hand. The solution being quickly poured off by inclination from the grey mercurial precipitate is still milky, and deposites another white sediment. When this second precipitate falls the liquor becomes clear and limpid, and is then of a fine yellow colour, like a solution of Gold. On this gold-coloured solution, and on the two precipitates above-mentioned, M. Grosse made several observations, the chief of which we shall here insert. The yellow liquor affects the tongue at first with a taste of sweetness; but afterwards vellicates it very smartly, and leaves on it a strong sensation of acrimony, which continues for a long time. Alkalis precipitate the Lead suspended in this liquor, just as they do all other metals dissolved by Acids; and this precipitate of Lead is white. Sea-salt, or Spirit of Salt, separates the Lead from its solvent, and precipitates it, as we observed before, into a _Plumbum corneum_: but this precipitate differs from the _Luna cornea_, as being very soluble in water; whereas the _Luna cornea_ will not dissolve in it at all; or at least dissolves therein with great difficulty, and in a very small quantity. This _Plumbum corneum_ dissolved in water is again precipitated by the Vitriolic Acid. M. Grosse observes, that this forms an exception to the eighth column of Mr. Geoffroy's Table of Affinities; in which the Acid of Sea-salt is marked as having a greater affinity than any other Acid with Metallic substances. Our solution of Lead is also precipitated in a white powder by several Neutral Salts; such as Vitriolated Tartar, Alum, and common Vitriol. It is by the means of double affinities that these Neutral Salts effect this precipitation. Even pure water alone is capable of precipitating the Lead of our solution, by weakening the Acid, and thereby disabling it from keeping the metal suspended. Lastly, as all the solutions of metals in Acids are nothing but Neutral Metallic Salts in a fluid form, so if the solution of Lead be evaporated over the fire, it will shoot into very beautiful crystals, about the bigness of hemp-seed, shaped like regular pyramids having square bases. These crystals are yellowish, and have a sweet saccharine taste: but what is most singular in them is, that, as they consist of the Nitrous Acid combined with Lead, which manifestly contains a great deal of phlogiston, they constitute a Nitrous Metallic Salt, which has the property of deflagrating in a crucible, without the addition of any other inflammable matter. It is extremely hard to dissolve this Salt in water. The grey mercurial precipitate which whitens Gold, and in which little globules of running Mercury are perceivable, is far from being pure Mercury. This metallic substance makes but a small part thereof: for it is an assemblage, 1. of little crystals of the same nature with those afforded by the evaporated solution; 2. of a portion of the white matter, or powder, which renders the solution milky; 3. of a grey powder, which M. Grosse considers as the only mercurial part; 4. and lastly, of little particles of Lead that have escaped the action of the solvent; especially if a little more Lead than the Acid is capable of dissolving were added with a view to saturate it entirely, as in the present process. By means of motion and heat the small parcels of Mercury may be amalgamated with the Lead. That Mercury should be found entire and in globules in the Spirit of Nitre, which very easily dissolves that metallic substance, will not be surprizing to those who reflect that, in the present case, the Acid is saturated with Lead, with which it has a greater affinity than with Mercury; as appears by M. Geoffroy's Table of Affinities, where, in the column that hath the Nitrous Acid at top, Lead is placed above Mercury. Agreeably to this, if Lead be presented to a solution of Mercury in Spirit of Nitre, the Lead will be dissolved, and as the dissolution thereof advances the Mercury will precipitate. Hence it appears that, in order to find any Mercury in the spontaneous precipitate of Lead dissolved by the Nitrous Acid, it is necessary that the Acid be entirely saturated with Lead; or else that portion of the Acid which remains unsaturated will dissolve the Mercury. With regard to the white powder that renders the solution milky, and afterwards precipitates, it is nothing but a portion of the Lead, which, not being intimately united with the Acid, falls in part of its own accord. It is a sort of calx of Lead, which being exposed to the fire becomes partly glass, and partly Lead, because it still retains some of its phlogiston. CHAP. VII. _Of_ MERCURY. PROCESS I. _To extract Mercury from its Ore, or to revivify it from Cinabar._ Pulverize the Cinabar from which you would extract the Mercury; with this powder mix an equal part of clean iron filings; put the mixture into a retort of glass or iron, leaving at least one third part thereof empty. Set the retort thus prepared in a sand-bath, so that its body may be quite buried in the sand, and its neck decline considerably downwards: fit on a receiver half filled with water, and let the nose of the retort enter about half an inch into the water. Heat the vessels so as to make the retort moderately red. The Mercury will rise in vapours, which will condense into little drops, and fall into the water in the receiver. When you see that nothing more comes over with this degree of heat, increase it, in order to raise what Mercury may still be left. When all the Mercury is thus brought over, take off the receiver, pour out the water contained in it, and collect the Mercury. _OBSERVATIONS._ Mercury is never mineralized in the bowels of the earth by any thing but Sulphur; with which it forms a compound of a brownish red colour, known by the name of _Cinabar_. Sometimes it is only mixed with earthy and stony matters that contain no Sulphur; but, as this metallic substance is never destitute of its phlogiston, it then has its metalline form and properties. When it is found in this condition, nothing is more easy than to separate it from those heterogeneous matters. For that purpose no more is requisite than to distil the whole with a fire strong enough to raise the Mercury in vapours. This mineral is volatile; the earthy and stony matters are fixed; and a certain degree of heat will effect a complete separation of what is volatile from what is fixed. This is not the case when Mercury is combined with Sulphur: for this latter mineral is volatile as well as Mercury; and the compound resulting from the union of them both is also volatile: so that if Cinabar were exposed to the fire in close vessels, as it must be to save the Mercury, it would be sublimed in substance, without being decomposed at all. In order therefore to separate these two substances from each other, we must have recourse to the interposition of some third, which hath a greater affinity with one of them than the other hath, and no affinity with that other. Iron hath all the conditions requisite for this purpose; seeing it hath, as may be seen in the Table, a much greater affinity with Sulphur than Mercury hath, and is incapable of contracting any union with Mercury. Iron, however, is not the only substance that may be employed on this occasion: Fixed Alkalis, Absorbent earths, Copper, Lead, Silver, Regulus of Antimony, have all, as well as Iron, a greater affinity than Mercury with Sulphur. Nay, several of these substances, namely, the saline and earthy Alkalis, as well as Regulus of Antimony, cannot contract any union with Mercury: the rest, to wit, Copper, Lead, and Silver, are indeed capable of amalgamating with Mercury; but then the union which these metals contract with the Sulphur prevents it; and even though they should unite with this metallic substance, the degree of heat to which the whole mixture is exposed would soon carry up the Mercury, and separate it with ease from those fixed substances. In this distillation the same cautions must be observed as in all others: that is, the vessels must be slowly heated, especially if a glass retort be used; the fire must be raised by degrees, and a much stronger one applied at last than at first. This operation particularly requires a very strong degree of fire, when there is but a small quantity of Mercury left. After the operation there remains in the retort a compound of Iron and Sulphur, which may easily be converted into a _crocus_, by calcining it and burning away the Sulphur. If a Fixed Alkali be employed, a Liver of Sulphur will be found in the retort after the distillation. If the Cinabar from which you extract the Mercury be good, you will generally obtain seven eighths of its weight in Quick-silver. In the present operation it is not necessary to lute on the receiver, because the water, in which the nose of the retort is plunged, is sufficient to fix the Mercurial vapours. In case the Cinabar, from which you intend to separate the Mercury, be mixed with a great quantity of heterogeneous, but fixed, matters, such as earths, stones, &c. it may be separated from them by subliming it with a proper degree of heat, because it is volatile. The vapours of Mercury are prejudicial, and may excite a salivation, tremors, and palsies; they should therefore be always avoided by such as work on this mineral. The oldest and richest mine of Mercury is that of Almaden in Spain. It is a singular property of that mine that, though the Mercury found in it is combined with Sulphur, and in the form of Cinabar, yet no additament is required to procure the separation of these two; the earthy and stony matter, with which the particles of the ore are incorporated, being itself an excellent absorbent of Sulphur. In the Quick-silver works carried on at this mine they make no use of retorts. They place lumps of the ore on an iron grate, which stands immediately over the furnace. The furnaces which serve for this operation are closed at the top by a sort of dome, behind which stands the shaft of a chimney that communicates with the fire-place, and gives vent to the smoke. These furnaces have in their fore-side sixteen apertures, to each of which is luted an aludel in a horizontal position, communicating with a long row of other aludels placed likewise in an horizontal direction; which aludels so connected together form one long pipe or canal, the further end whereof opens into a chamber destined to receive and condense all the mercurial vapours. These rows of aludels are supported from end to end by a terrass, which runs from the body of the building, wherein the furnaces are erected, to that where the chambers are built that perform the office of receivers. This is a very ingenious contrivance and saves much labour, expence, and trouble, that would be unavoidable if retorts were employed. That part of the furnace which contains the lumps of ore, serves for the body of the retort; the row of aludels for its neck; and the little chambers in which these canals terminate are actual receivers. The terrass of communication, which reaches from the one building to the other, is formed of two inclined planes, the lower edges of which, meeting in the middle of the terrass, rise from thence insensibly; the one quite to the building where the furnaces are, and the other to that which forms the recipient chambers. By this means, when any Mercury escapes through the joints of the aludels, it naturally runs down along these inclined planes, and so is collected in the middle of the terrass, where the inferior sides of the planes meeting together form a sort of canal, out of which it is easily taken up. The celebrated M. de Jussieu having viewed the whole himself, in a journey he made to this mine, furnished us with this description of the work. PROCESS II. _To give Mercury, by the action of Fire, the appearance of a Metalline Calx._ Put Mercury into several little glass matrasses with long and narrow necks. Stop the matrasses with a little paper, to prevent any dirt from falling into them. Set them all in one sand-bath, so that they may be surrounded with sand as high as two thirds of their length. Apply the strongest degree of heat that Mercury can bear without subliming: continue this heat without interruption, till all the Mercury be turned to a red powder. The operation lasts about three months. _OBSERVATIONS._ Mercury treated according to the process here delivered hath all the appearance of a metalline calx, but it hath no more: for, if it be exposed to a pretty strong degree of fire, it sublimes, and is wholly reduced to running Mercury, without the addition of any other inflammable matter; which proves that during this long calcination it lost none of its phlogiston. The volatile nature of Mercury, which permits it not to bear a heat of any strength without subliming, prevents our examining all the effects that fire is capable of producing on it. Yet there is reason to believe that, as this metallic substance resembles the perfect metals in its weight, its splendour, and a brilliancy which resists all the impressions of the air without alteration, it would like them be unchangeable by the greatest force of fire, if it were fixed enough to bear it. In order to give Mercury the form of a metalline calx, it must necessarily be exposed for about three months together, to the utmost heat it can bear without subliming, as is above directed. Boerhaave kept it digesting in a less heat for fifteen years successively, both in open and in close vessels, without observing it to suffer the least change; except that there was formed upon its surface a small quantity of a black powder, which was reduced to running Mercury by trituration alone. Mercury thus converted to a red powder is known in chymistry and medicine by the name of _Mercury precipitated per se_: a title proper enough, as it is actually reduced to the form of a precipitate, and that without any additament; but very improper on the other hand, considering, that in reality this Mercury is not a precipitate, as not having been separated from any menstruum in which it was dissolved. PROCESS III. _To dissolve Mercury in the Vitriolic Acid. Turbith Mineral._ Put Mercury into a glass retort, and pour on it thrice its weight of good Oil of Vitriol. Set the retort in a sand-bath; fit on a recipient; warm the bath by degrees till the liquor just simmer. With this heat the Mercury will begin to dissolve. Continue the fire in this degree till all the Mercury be dissolved. _OBSERVATIONS._ The Vitriolic Acid dissolves Mercury pretty well: but for this purpose the Acid must be very hot, or even boil; and then too it is a very long time before the dissolution is completed. We have directed the operation to be performed in a retort; because this solution is usually employed to make another preparation called _Turbith Mineral_, which requires that as much as possible of the Acid solvent be abstracted by distillation. Having therefore dissolved your Mercury in the Vitriolic Acid, if you will now prepare the Turbith, you must, by continuing to heat the retort, drive over all the liquor into the receiver, and distil till nothing remains but a white powdery matter: then break the retort; pulverize its contents in a glass mortar, and thereon pour common water, which will immediately turn the white matter of a lemon-colour; wash this yellow matter in five or six warm waters, and it will be what is called in medicine _Turbith Mineral_; that is, a combination of the Vitriolic Acid with Mercury, five or six grains whereof is a violent purgative, and also an emetic; qualities which it possesses in common with the Vegetable Turbith, whose name it hath therefore taken. There rises out of the retort, both while the Mercury is dissolving, and while the solvent is abstracting, a weak Spirit of Vitriol; because a great part of the Acid remains united with the Quick-silver, which at last appears in the form of a white powder: so that, if you do not incline to save the Acid which rises on this occasion, you may, instead of drawing off the liquor in a retort, evaporate it in a glass bason set on a sand-bath, which will be much sooner done. It is very remarkable that, on this occasion, the Mercury may be exposed, without any danger of subliming, to a much greater heat than it is capable of bearing when not combined with the Vitriolic Acid; which shews that this Acid hath the property of fixing Mercury to a certain degree. The white matter, that remains after the evaporation of the fluid, is one of the most violent corrosives, and would prove an actual poison if taken internally. By washing it several times in warm water it is freed from a great deal of its Acid, and so considerably sweetened. The proof is this; if the water used in washing the Turbith be evaporated, there remains after the evaporation a matter in form of a Salt, that being set in a cellar runs into a liquor called _Oil of Mercury_, which is a powerful corrosive. Several authors further direct Spirit of Wine to be burnt on the Turbith, to sweeten it still more. If, instead of washing the white matter that remains after the moisture is drawn off, fresh Oil of Vitriol be poured on it, and then abstracted as before; this treatment being repeated two or three times, there will at last remain in the retort a matter having the appearance of an oil, which resists the action of the fire, and cannot be desiccated: qualities which are owing to the great quantity of Acid particles thus united with the Mercury. This Oil of Mercury is one of the most violent corrosives. The Mercury may be separated therefrom, by precipitating it with an Alkali, or a metallic substance that hath more affinity than Mercury with the Vitriolic Acid: Iron, for instance, may be employed in this precipitation. Mercury thus separated from the Vitriolic Acid need only be distilled to recover the form of Quick-silver. PROCESS IV. _To combine Mercury with Sulphur. Æthiops Mineral._ Mix a dram of Sulphur with three drams of Quick-silver, by triturating the whole in a glass mortar with a glass pestle. By degrees, as you triturate, the Mercury will disappear, and the matter will acquire a black colour. Continue the triture till you cannot perceive the least particle of running Mercury. The black matter you will then have in the mortar is known in medicine by the name of _Æthiops Mineral_. An Æthiops may also be made by fire in the following manner. In a shallow unglazed earthen pan melt one part of flowers of Sulphur: add three parts of running Mercury, making it fall into the pan in the form of small rain, by squeezing it through chamoy leather. Keep stirring the mixture with the shank of a tobacco-pipe all the while the Mercury is falling: you will see the matter grow thick and acquire a black colour. When the whole is thoroughly mixed, set fire to it with a match, and let as much of the Sulphur burn away as will flame. _OBSERVATIONS._ Mercury and Sulphur unite together with great ease; cold triture alone is sufficient to join them. By this means the Mercury is reduced into exceeding small atoms, and combines so perfectly with the Sulphur that the least vestige thereof is not to be seen. Sulphur is not the only matter which being rubbed with Mercury will destroy its form and fluidity: all fat substances that have any degree of consistence, such as the fat of animals, balsams, and resins, are capable of producing the same effect. This metallic substance, being triturated for some time in a mortar with these matters, becomes at last invisible, and communicates to them a black colour. When thus divided by the interposition of heterogeneous particles, it is said to be _Killed_. But Mercury doth not contract such an intimate union with these other matters as it doth with Sulphur. The Æthiops prepared by fusion is a more perfect and accurate combination of Mercury and Sulphur than the other: for, the quantity of Sulphur directed to be used in making it being much greater than is absolutely necessary to fix the Mercury, the redundant Sulphur is destroyed by burning, and none left but what is most intimately united with the Mercury; and hindered by the union it hath contracted with that metallic substance from being so easily consumed. The Æthiops therefore, which is prepared by fusion and burning the Sulphur, contains a much greater proportion of Mercury than that which is made by simple triture; so that in Medicine it ought to be prescribed in different cases, and in smaller doses. If no more Sulphur than is just necessary to kill the Mercury be added to it at first, it will be difficult to obtain a perfect mixture; because that quantity is very small: it is better, therefore, to employ at once the quantity above directed. PROCESS V. _To sublime the Combination of Mercury and Sulphur into Cinabar._ Grind to powder Æthiops mineral prepared by fire. Put it into a cucurbit; fit thereto a head; place it in a sand-bath, and begin with applying such a degree of heat as is requisite to sublime Sulphur. A black matter will rise, and adhere to the sides of the vessel. When nothing more will rise with this degree of heat, raise the fire so as to make the sand and the bottom of the cucurbit red; and then the remaining matter will sublime in the form of a brownish red mass, which is true _Cinabar_. _OBSERVATIONS._ Æthiops Mineral requires nothing but sublimation to become true Cinabar, like that found in Quick-silver mines: but our Æthiops contains still more Sulphur than ought to be in the composition of Cinabar; for which reason we have directed the degree of fire applied at first to be no greater than that which is capable of subliming Sulphur. As Cinabar, though consisting of Mercury and Sulphur, is yet much less volatile than either of these substances alone; which probably arises from the Vitriolic Acid contained in the Sulphur; therefore, if there be any redundant Sulphur in the Æthiops, which hath not contracted an intimate union with the Mercury, it will sublime by itself in this first degree of heat. Some mercurial particles also will rise with it, and give it a black colour. Cinabar contains no more Sulphur than about a sixth or seventh part of its weight: so that, instead of employing the common Æthiops to make it, it would be better to prepare one on purpose that should contain much less Sulphur; because too much Sulphur prevents the success of the operation by blackening the Sublimate. Indeed in whatever manner you go about it, the Cinabar always appears black at first: but when it is well prepared, and contains no more than its due proportion of Sulphur, the blackness is only external. This black coat therefore may be taken off; and then the internal part will appear of a fine red, and, if sublimed a second time, will be very beautiful. As artificial Cinabar hath the same properties with the native, it may be decomposed by the same means: so that, if you want to extract the Mercury out of it, recourse must be had to the process above delivered for working on Cinabar ores. PROCESS VI. _To dissolve Mercury in the Nitrous Acid. Sundry Mercurial Precipitates._ Put into a matrass the quantity of Mercury you intend to dissolve: pour on it an equal quantity of good Spirit of Nitre, and set the matrass in a sand-bath moderately heated. The Mercury will dissolve with the phenomena that usually attend the dissolutions of metals in this Acid. When the dissolution is completed let the liquor cool. You will know that the Acid is perfectly saturated, if there remain at the bottom of the vessel, notwithstanding the heat, a little globule of Mercury that will not dissolve. _OBSERVATIONS._ Mercury dissolves in the Nitrous Acid with much more facility, and in much greater quantity, than in the Vitriolic; so that it is not necessary, on this occasion, to make the liquor boil. This solution when cold yields crystals, which are a Nitrous Mercurial Salt. If you desire to have a clear limpid solution of Mercury, you must employ an _aqua fortis_ that is not tainted with the Vitriolic or Marine Acid: for, the affinity of these two Acids with Mercury being greater than that of the Nitrous Acid, they precipitate it in the form of a white powder, when they are mixed with the solvent. Mercury thus precipitated in a white powder, out of a solution thereof in the Spirit of Nitre, is used in Medicine. To obtain this precipitate, which is known by the name of the _White Precipitate_, Sea-salt dissolved in water together with a little Sal Ammoniac is used; and the precipitate is washed several times in pure water, without which precaution it would be corrosive, on account of the great quantity of the Marine Acid which it would contain. The preparation known by the name of _Red Precipitate_ is also obtained from our solution of Mercury in Spirit of Nitre. It is made by abstracting all the moisture of the solution, either by distillation in a retort, or by evaporation in a glass bason set on a sand-bath. When it begins to grow dry it appears like a white ponderous mass. Then the fire is made strong enough to drive off almost all the Nitrous Acid, which, being now concentrated, rises in the form of red vapours. If these vapours be catched in a receiver, they condense into a liquor, which is a very strong and vastly smoking Spirit of Nitre. By degrees, as the Nitrous Acid is forced up by the fire, the mercurial mass loses its white colour, and becomes first yellow, and at last very red. When it is become entirely of this last colour the operation is finished. The red mass remaining is a Mercury that contains but very little Acid, in comparison of what it did while it was white: and indeed the first white mass is such a violent corrosive, that it cannot be used in Medicine; whereas, when it is become red, it makes an excellent escharotic, which those who know how to use it properly apply with very great success, particularly to venereal ulcers. This preparation is very improperly called a _Precipitate_: for the Mercury is not separated from the Spirit of Nitre by the interposition of any other substance, but only by evaporating the Acid. It is also called _Arcanum Corallinum_. It must be observed that Mercury, by its union with the Nitrous Acid, acquires a certain degree of fixity: for the red precipitate is capable of sustaining, without being volatilized, a stronger degree of heat than pure Mercury can; which, as we observed before, is the property of Turbith Mineral also. PROCESS VII. _To combine Mercury with the Acid of Sea-salt. Corrosive Sublimate._ Evaporate a solution of Mercury in the Nitrous Acid till there remain only a white powder, as mentioned in our observations on the preceding process. With this powder mix as much Green Vitriol calcined to whiteness, and as much decrepitated Sea-salt, as there was Mercury in the solution. Triturate the whole carefully in a glass mortar. Put this mixture into a matrass, so that two thirds thereof may remain empty, having first cut off the neck to half its length: or instead thereof you may use an apothecary's phial. Set your vessel in a sand-bath, and put sand round it as high as the contents can reach. Apply a moderate fire at first, and raise it by slow degrees. Vapours will begin to ascend. Continue the fire in the same degree till they cease. Then stop the mouth of the vessel with paper, and increase the fire till the bottom of the sand-bath be red-hot. With this degree of heat a Sublimate will rise, and adhere to the inside and upper part of the vessel, in the form of white, semi-transparent crystals. Keep up the fire to the same degree till nothing more will sublime. Then let the vessel cool; break it, and take out what is sublimed, which is _Corrosive Sublimate_. _OBSERVATIONS._ In this operation the mineral Acids act, and are acted upon, in a remarkable manner. Every one of the three is at first neutralized, or united with a different basis; the Vitriolic being combined with Iron; the Nitrous with Mercury, forming therewith a Nitrous Mercurial Salt; and the Marine with its natural Alkaline basis. The Vitriolic and Nitrous Acids, which are united with metalline substances, being both stronger than the Acid of Sea-salt, strive to expel it from its basis, in order to combine with it themselves; but the Vitriolic Acid, being the strongest of the two, would take sole possession of this basis exclusive of the Nitrous, which would continue united with the Mercury, if the Marine Acid had not a greater affinity than the Nitrous with this metallic substance. This Acid therefore being expelled from its basis by the Vitriolic Acid, and so set at liberty, must unite with the Mercury, and separate the Nitrous Acid from it; which now hath no resource but to unite with the Iron deserted by the Vitriolic Acid. But as all these changes are brought about by the means of a considerable heat, and as the Nitrous Acid hath not a very firm connection with the Iron, it is driven off by the force of the fire; and this it is which we see rise in vapours during the operation. It also carries off with it some parts of the other two Acids, but in a very small quantity. After the operation therefore there remains, 1. A combination of the Vitriolic Acid with the basis of Sea-salt; that is, a Glauber's Salt: 2. A red martial earth, being that which was the basis of the Vitriol: these two substances are blended together, and remain at the bottom of the vessel because of their fixity: 3. A combination of the Marine Acid with Mercury; both of which being volatile, they ascend together into the upper part of the vessel, and there form a Corrosive Sublimate. If we reflect on this process with attention, and recollect distinctly the affinities of the different substances employed in it, we shall perceive that it is not necessary to make use of all those matters, and that the operation would succeed though several of them were left out. First, the Nitrous Acid may be omitted; since, as hath been shewn, it is not an ingredient in the Sublimate, but is dissipated in vapours during the operation. From an accurate mixture therefore of Vitriol, Sea-salt, and Mercury, a Corrosive Sublimate must be obtained: for as the Acid of the Vitriol will disengage the Acid of Sea-salt, the latter will be at liberty to combine with the Mercury, and so form the compound we are in quest of. Secondly, if we make use of Mercury dissolved by the Nitrous Acid, we may omit the Vitriol; because the Nitrous Acid having a greater affinity than the Marine Acid itself with the basis of Sea-salt, and the Acid of Sea-salt having a greater affinity than the Nitrous Acid with Mercury, these two Acids will naturally make an exchange of the bases with which they are united: the Nitrous will lay hold on the basis of Sea-salt, and form a quadrangular Nitre, while the Marine Acid will join the Mercury, and with it form a Corrosive Sublimate. Thirdly, instead of Sea-salt its Acid only may be employed; which being mixed with the solution of Mercury in the Spirit of Nitre, will, by virtue of its greater affinity with that metallic substance, separate it from the Nitrous Acid, unite with it, and form a white mercurial precipitate, which need only be sublimed to become the combination required. Fourthly, instead of Mercury dissolved in the Nitrous Acid, Mercury dissolved by the Vitriolic Acid, or Turbith, may be used; only mixing Sea-salt therewith: for these two saline substances will mutually decompound each other, by virtue of the affinities of their Acids, and for the same reasons that Sea-salt and the Mercurial Nitrous Salt decompound each other. The Vitriolic Acid quits the Mercury with which it is combined, to unite with the basis of the Sea-salt; and the Acid of this Salt being expelled by the Vitriolic, combines with the Mercury, and consequently forms our Corrosive Sublimate. In this case a Glauber's Salt remains after the sublimation. These several methods of preparing Corrosive Sublimate are never used, because each of them is attended with some inconvenience; such as requiring too long triture, yielding a Sublimate less corrosive than it should be, or a smaller quantity of it. We must, however, except the last; which was invented by the late Mr. Boulduc, of the Academy of Sciences, who found none of these inconveniencies attending it[9]. [9] See the Memoirs of the Academy for 1730. Corrosive Sublimate may also be made only by mixing Mercury with Sea-salt, without any additament. This may appear surprizing when we consider that, as Acids have a greater affinity with Alkalis than with metallic substances, the Acid of Sea-salt ought not to quit its basis, which is Alkaline, to unite with Mercury. In order to explain this phenomenon it must be remembered that Sea-salt, when exposed to the fire without additament, suffers a little of its Acid to escape. Now this portion of the Marine Acid unites with the Mercury, and forms a Corrosive Sublimate. Moreover, as there is a pretty strong affinity between the Marine Acid and Mercury, this may help to detach from the Sea-salt a greater quantity of Acid than it would otherwise part with. Nevertheless, the quantity of Sublimate obtained by this means is not considerable, nor is it very corrosive. On this occasion we must also mention another combination of the Marine Acid with Mercury; which is made by mixing that metallic substance perfectly with Sal Ammoniac, by the means of triture. Mercury, like all other metals except Gold, possesses the property of decompounding Sal Ammoniac, separating the volatile Alkali which serves it for a basis, and combining, by the help of a very gentle heat, with its Acid, which is well known to be the same with that of Sea-salt. This decomposition of Sal Ammoniac, by the metalline substances, is a full exception to the first column of Mr. Geoffroy's Table of Affinities, and is the basis of several new Medicines invented by the late Comte de la Garaye[10]. [10] See the Memoir given in by me on this subject to the Academy of Sciences in the _Memoires l'Acadamie_ 1754. Corrosive Sublimate is the most violent and the most active of all corrosive poisons. It is never used in Medicine, but in external applications. It is a powerful escharotic; it destroys proud flesh, and cleans old ulcers: but it must be used by those only who know how to apply it properly, and requires an able hand to manage it. It is not commonly applied by itself, but mixed in the proportion of half a dram to a pound of lime-water. This mixture is yellowish, and bears the name of _Aqua Phagadenica_. Water dissolves Corrosive Sublimate, but in a small quantity. If a Fixed Alkali be mixed with this solution, the Mercury precipitates in the form of a red powder. If the precipitate be procured by a Volatile Alkali, it is white; if by Lime-water, it is yellow. This Mercurial Salt dissolves pretty easily in boiling Spirit of Wine. PROCESS VIII. _Sweet Sublimate._ Take four parts of Corrosive Sublimate; pulverize it in a glass or marble mortar; add by little and little three parts of Mercury revivified from Cinabar; triturate the whole carefully, till the Mercury be perfectly killed, so that no globule thereof can be perceived. The matter will then be grey. Put this powder into an apothecary's phial, or into a matrass, whose neck is not above four or five inches long, leaving two thirds thereof empty. Set the vessel in a sand-bath, and put sand round it to one third of its heighth. Apply a moderate fire at first; and afterwards raise it gradually till you perceive that the mixture sublimes. Keep it up to this degree till nothing more will rise, and then break the vessel. Reject, as useless, a small quantity of earth which you will find at the bottom; separate also what adheres to the neck of the vessel, and carefully collect the matter in the middle, which will be white. Pulverize it; sublime it a second time, in the same manner as before; and in the same manner separate the earthy matter left at the bottom of the vessel, and what you find sublimed into the neck. Pulverize, and sublime a third time, the white matter you last found in the middle. The white matter of this third sublimation is the _Sweet Sublimate_, called also _Aquila Alba_. _OBSERVATIONS._ The Acid of Sea-salt in the Corrosive Sublimate is very far from being perfectly saturated with Mercury; and thence comes the corrosive quality of this saline compound. But though Mercury, as appears by this combination, is capable of imbibing a much greater quantity of Acid than is necessary to dissolve it; nay, though it naturally takes up this super-abundant quantity of Acid, yet it doth not follow from thence that this redundant Acid may not combine with Mercury to the point of perfect saturation, so as to lose its corrosive acidity. This is the case in the operation here described. A fresh quantity of running Mercury is mixed with Corrosive Sublimate; and the fresh Mercury, combining with the super-abounding Acid, deprives the Sublimate of its acrimony, and forms a compound which comes much nearer the nature of a Neutral Metallic Salt. Trituration alone is not sufficient to produce an union between the newly added Mercury and the Acid of the Corrosive Sublimate: because, generally speaking, the Acid of Sea-salt cannot dissolve Mercury without the help of a certain degree of heat, and unless it be reduced into vapours. Thus, though the newly added Mercury becomes invisible by trituration, and seems actually combined with the Corrosive Sublimate, yet the union is not intimate. There is only an interposition of parts, but no true dissolution of the newly added Mercury by the super-abundant Acid of the Corrosive Sublimate. For this reason the mixture must be sublimed; and by this sublimation only is the true union effected. Nor is one single sublimation sufficient: no less than three are necessary to deprive the Sublimate of the corrosive quality which renders it poisonous. After the third sublimation, the Sublimate being put upon the tongue gives no considerable sensation of acrimony; nor doth it retain any more of its former activity than is requisite to make it a gentle purgative, when administered from six to thirty grains for a dose. If a less quantity of Mercury than that above directed be mixed with the Corrosive Sublimate, the super-abundant Acid will not be sufficiently saturated; and the less Mercury is added, the more of its corrosive virtue will the Sublimate retain. If, on the contrary, a greater quantity of Mercury be added, there will be more than the Acid can possibly dissolve, and the superfluous quantity will remain in its natural form of Quick-silver. It is better therefore to err in the excess than in the defect of the proportion of Mercury to be added; because the Corrosive Sublimate will take up no more than is necessary to dulcify it. Part of the Acid of the Corrosive Sublimate is also dissipated in vapours during the operation; and it is necessary to allow room for these vapours to circulate, and a vent to give them passage, or else they will burst the vessels. These are our reasons for leaving an empty space in the subliming vessels, and for having their necks no more than five or six inches long. The matter which sublimes into the neck of the vessel is always very acrid; for which reason it must be separated from the Sweet Sublimate. There remains also at the bottom of the matrass an earthy, reddish matter; which probably comes from the Vitriol employed in making the Corrosive Sublimate. This matter must likewise be rejected as useless after every sublimation. PROCESS IX. _The Panacea of Mercury._ Pulverize some Sweet Sublimate, and sublime it in the same manner as you did thrice before. Repeat this nine times. After these sublimations it will make no impression on the tongue. Then pour on it aromatic Spirit of Wine, and set the whole in digestion for eight days. After that decant the Spirit of Wine, and dry what remains, which is the _Panacea of Mercury_. _OBSERVATIONS._ The great number of sublimations, which the Sweet Sublimate is made to undergo, sweeten it still more, and to such a degree that it leaves no sensation on the tongue, nor hath any purgative virtue. The Spirit of Wine in which it is digested after all the sublimations, is designed to blunt still more the sharpness of any acid particles that may not have been sufficiently dulcified by the preceding sublimations. As Mercury is the specific remedy for venereal disorders, sundry preparations thereof have been attempted with a view to produce different effects. Sweet Sublimate is purgative; and for that reason is not quite proper for procuring a salivation, because it carries off the humours by stool. The Panacea of Mercury, which, on the contrary, is not purgative, may raise a salivation when taken inwardly. SECTION III. _Of Operations on the_ SEMI-METALS. CHAP. I. _Of_ ANTIMONY. PROCESS I. _To Separate Antimony from its Ore by Fusion._ Having drilled some small holes, of about two lines in diameter, in the bottom of a crucible, put into it your Antimonial Ore broken into little bits, about the size of a hazel nut; lute on its cover; set the crucible thus prepared in the mouth of another crucible, and close the joints with lute. At the distance of half a foot from this compound vessel place bricks all round, so as to form a furnace; the sides of which must rise as high as the brim of the uppermost crucible. Let the bottom of this furnace be filled with ashes, up to the top of the lower crucible, and the rest of the furnace with lighted coals. Blow the fire, if it be necessary, with bellows, till the upper crucible become red. Keep it up in this degree for about a quarter of an hour. Then take your vessels out of the furnace, and you will find the Antimony collected in the bottom of the lower crucible, having run through the holes of the upper one. _OBSERVATIONS._ The ore of Antimony is one of the most fusible: it always contains a great deal of Sulphur, and cannot sustain a fire of any force without being dissipated into vapours. It requires no additament to flux it: for it is not necessary, on this occasion, that the earthy and stony matters mixed therewith be brought to fusion. It is sufficient that the Antimonial part be melted; which, as soon as it becomes fluid, is carried by its weight to the lower part of the crucible. Thus it is separated from all heterogeneous matters; which are left in the upper crucible, while it passes through the holes in its bottom, and forms a mass in the lower. The precaution of closing all the apertures of both crucibles is necessary, on account of the volatility of this mineral: and that the Antimony, when once melted, may not continue exposed to a great heat, it is made to run down into a vessel surrounded with ashes only, and by that means very little affected with heat; ashes being one of those solid mediums that transmit least of it. PROCESS II. _The common Regulus of Antimony._ Reduce crude Antimony to powder. Mix it with three fourths of its weight of white Tartar, and half its weight of refined Salt-petre, both pulverized. Into a large crucible made red-hot in the fire, throw a spoonful of your mixture, and cover it. There will be a very considerable detonation. When it is over, throw in a second spoonful of your mixture, and cover the crucible as before: this will produce a second detonation. Go on thus, till you have thrown in all your mixture. When the whole has thus fulminated, increase the fire so as to bring the matter into fusion; that being done, take the crucible out of the furnace, and immediately pour its contents into an iron cone heated and greased with tallow. Strike the floor and the cone some gentle blows with a hammer, to make the Regulus precipitate: and when the matter is fixed and cold, invert the cone and turn it out. You will see it consist of two distinct substances; the uppermost of which is a saline scoria, and the undermost the reguline part. Strike this mass a blow with a hammer, in the place where these substances join, and you will by this means separate the scoria from the Regulus; the latter of which will have the form of a metallic cone, on whose base you will observe the signature of a bright star. _OBSERVATIONS._ Antimony, though separated by a former fusion from the earthy and stony parts of its ore, must nevertheless be still considered as an ore, on account of the great quantity of Sulphur it contains, which mineralizes the metalline part or Regulus. Therefore, if you desire to have this Regulus pure, you must separate it from the Sulphur that is combined with it. This may be done several ways. The method above proposed is one of the readiest and easiest, though not altogether free from inconveniencies, as we shall shew. The Salt-petre in the mixture detonates by means of the Sulphur of the Antimony, which it consumes, and from which it separates the reguline part: but lest it should also consume some of the phlogiston which gives the Regulus its metalline form, Tartar is added; because it contains a great deal of inflammable matter, and so is capable of furnishing enough for the detonation of the Nitre, or rather for restoring to the metallic earth of the Antimony, the phlogiston that may be consumed by the Nitre. If we consider what passes in this operation we shall soon be convinced that a great deal must be lost in it, and that we do not thereby obtain near the whole of the Regulus that the Antimony is capable of yielding: for, 1. the Regulus of Antimony being a volatile substance, much of it must be dissipated during the detonation; and so much the more as the detonation is frequently repeated, and continued for a considerable time. The flowers that may be collected by presenting cold bodies to the smoke that rises in the operation, and which may be reduced to a Regulus by the addition of a phlogiston, sufficiently prove what is here advanced. 2. All the Sulphur of the Antimony is not consumed by the Nitre on this occasion; and moreover, the Acid of that part thereof which is burnt, uniting with some of the Alkali produced by the deflagration of the Nitre and Tartar, forms a Vitriolated Tartar, which meeting with a sufficient quantity of phlogiston in the mixture produces new Sulphur. Now this Sulphur, whether not consumed, or reproduced, in the operation, combining with the Alkali forms a Liver of Sulphur; and that dissolves part of the Regulus, which by this means remains confounded with the scoria. The proof of this is, that, if the scoria be mixed with filings of iron, and fused a second time, you will find at the bottom of the crucible a button of Regulus, which it contained, and which is separated therefrom by the interposition of the Iron. We shall say more on this subject in the process for making the Martial Regulus, which immediately follows this. If, instead of melting the scoria with iron filings, we pulverize it, boil it in water, and then pour an acid into that water; the liquor will instantly grow turbid, and a Sulphureous Precipitate will fall, commonly called _the Golden Sulphur of Antimony_; which is nothing else but common Sulphur still combined with some particles of the Regulus; a new proof of what we advanced concerning the production of Liver of Sulphur in this operation. As Regulus of Antimony is of no great value, the loss sustained in this process is seldom regarded. However, we shall have occasion, in the sequel, to point out a method of obtaining this Regulus with less disadvantage. PROCESS III. _Regulus of Antimony precipitated by Metals._ Put one part of small iron nails into a crucible, and set it amidst burning coals, in a melting furnace. When the iron is thoroughly red-hot, and begins to grow white, add thereto little by little, and at several times, two parts of crude Antimony in powder. The Antimony will immediately flow and unite with the Iron. When the Antimony is entirely melted, add thereto, at several times, the fourth of its weight of pulverized Nitre: a detonation will ensue, and the whole mixture will be in fusion. After you have kept the matter in this condition for some minutes, pour it into an iron cone, first heated and tallowed. Strike the sides of the cone with a hammer, that the Regulus may fall to the bottom; and, when all is cold, separate it from the scoria by a blow with a hammer. Melt this first Regulus again in another crucible, adding a fourth part of its weight of crude Antimony. Keep the crucible close shut, and give no more heat than is necessary to melt the matter. When it is in perfect fusion, add to it at several times, as you did before, the sixth part of its weight of pulverized Nitre; and, in half a quarter of an hour after this, pour the whole into a cone as you did the first time. Lastly, melt your Regulus over again a third, or even a fourth time, always adding a little Nitre, which will detonate as before. If after all these fusions you pour the Regulus into an iron cone, you will find it very beautiful, and the star well formed: it will be covered with a semi-transparent, lemon-coloured scoria. This scoria is extremely acrid and caustic. _OBSERVATIONS._ Though Regulus of Antimony unites very readily with Sulphur, and is always found combined therewith in the earth, we must not thence conclude that it hath a greater affinity than other substances with that mineral: on the contrary, all the metals, except Gold, have a greater affinity than this Semi-metal with Sulphur. Hence it follows that all the metals, except Gold, are capable of decomposing Antimony, and separating the sulphureous part from the metalline; so that, instead of employing Iron, as in our process, Copper, Lead, Tin, or Silver, may be used, and a Regulus obtained by means thereof. But as Iron is, of all the metallic substances, that which hath the greatest affinity with Sulphur, it is on this occasion preferred to the rest. And from hence two advantages arise: the first is, that the operation is performed sooner and with greater ease: the second, that the Regulus is purer, and contains less of the precipitating metal. For it is a general rule, that, when one metallic substance is employed to precipitate another, the precipitated substance is always a little adulterated by the admixture of some particles of the precipitant. Now, the greater affinity the precipitant hath with the matter united to that which is to be precipitated, the less doth the precipitate retain of the precipitant. In this process the Iron melts very easily by means of the union it contracts with the Sulphur; which, as we observed before, hath the property of rendering this metal very fusible, though of itself the most refractory of all. The scoria found on the Regulus of the first fusion is a combination of Iron with the sulphureous part of the Antimony. This scoria is extremely hard, and not to be separated from the Regulus without some trouble. The Nitre added, being alkalizated and united therewith, renders it a little softer, and gives it the property of relenting in the air. Any Alkaline Salt may be substituted for the Nitre. The Nitre that is alkalizated in the operation, or the Alkali that is added, procures moreover another advantage; namely, that, by uniting with part of the Sulphur of the Antimony, it produces a Liver of Sulphur, which dissolves the Iron, retains it, and hinders that which is not yet combined with pure Sulphur from uniting so readily with the Regulus as it otherwise would do. Lastly, the addition of Nitre, or an Alkali, contributes greatly to promote the fusion, to render it more perfect, and to procure a more complete precipitation of the Regulus. The second fusion which the Regulus is made to undergo is intended to purify it from any mixture of Iron. When the fresh Antimony added on that occasion comes to melt with the Regulus, the Sulphur contained in the Antimony joins with the ferruginous parts in the Regulus; and the Iron becoming lighter by this union is thrown up to the surface of the matter. There it forms a sort of scoria, with which a good deal of Antimony is mixed; the Regulus not being wholly precipitated, because there is not Iron enough in the mixture for that purpose. The Salt-petre added here produces the same effect as in the first fusion. But if, on one hand, the Regulus precipitated in the first fusion be purified, by this addition of fresh Antimony, from most of the Iron with which it was alloyed; on the other hand, this same Regulus cannot be kept from re-uniting with some sulphureous parts. In order therefore to separate it entirely from these, it must be melted over again once or twice more, and a little Nitre added each time, to consume them by deflagration. But this cannot be done without consuming also some of the very phlogiston which gives the Regulus its metalline form: whence it comes to pass that part of the Regulus is converted to a calx, which, by means of the alkalizated Nitre, is turned into glass; and it is this glass which mixing with the scoria gives it the yellow colour observed therein. This yellow colour may also be in part produced by some ferruginous particles, of which a small quantity always remains combined with the Regulus, notwithstanding its former depuration by Antimony. It is of no use to repeat the fusions of the Regulus oftener than is above proposed, or to add fresh Nitre with a view to consume the Sulphur it may still contain: for after the second fusion it contains none at all, and retains only the phlogiston necessary to give it the metalline form. So that, by prosecuting the matter further, you would only calcine and destroy the Regulus to no manner of purpose. From what hath been said it is plain that, even by this process, we do not obtain all the Regulus which our Antimony is capable of yielding; seeing part of it is destroyed by the fusions it must necessarily undergo with Nitre, in order to its purification. We shall give a process for obtaining from Antimony the greatest quantity of Regulus it can possibly be made to yield, after we have treated of its Calcination, which is in some sort the first step of that process. PROCESS IV. _The Calcination of Antimony._ Take an unglazed earthen vessel, wider at top than at bottom; put into it two or three ounces of crude Antimony finely pulverized. Set this vessel over a weak charcoal fire, and increase the heat till you see the Antimony begin to smoke a little. Continue the fire in this degree, and keep incessantly stirring the Antimony with the shank of a tobacco-pipe all the while it is upon the fire. The powder of Antimony, which, before calcination, was of a brilliant colour inclining to black, will become dull, and look like an earth. When it comes to have this appearance raise your fire till the vessel be red-hot, and keep it up in this degree till the matter cease entirely to smoke. _OBSERVATIONS._ Antimony, as hath been already said, is a sort of ore consisting of a metalline or reguline part mineralized by Sulphur. The design of this calcination is, by the action of fire, to dissipate the sulphureous part, which is the most volatile, in order to separate it from the metalline part. It is evidently a real torrefaction; but the operation is very difficult, and requires a good deal of attention; for Antimony very easily melts, while at the same time it is necessary to our success that it do not melt; because when the matter is in fusion the Sulphur requires a much greater degree of heat to carry it off. Now, as Regulus of Antimony itself is very volatile, a good deal of it would be dissipated along with the Sulphur, if it were exposed to the degree of heat necessary to carry off the Sulphur when the mass is melted. Therefore if it happen that the Antimony begin to melt during the calcination, which is easily perceived by its running into clots, it must be taken off the fire, and the clotted parts be again pulverized; after which the calcination is to be prosecuted with a less degree of heat. When the Antimony has lost all its brightness, and is become like an earth, it is time to augment the degree of heat, in order to complete the calcination; because the last portions of the Sulphur are the most difficult to raise. Moreover, the inconveniences just mentioned are not now to be apprehended: for, as the great fusibility of the reguline part is owing to the Sulphur, what remains, after you have dissipated the greatest part of the Sulphur, is much less fusible; and, as the redundant Sulphur of the Antimony cannot be driven off, without dissipating at the same time a good deal of the phlogiston necessary to metallize its Regulus, the matter that remains comes much nearer to the nature of a calx, than to that of a metalline substance; and consequently partakes of the nature of all metallic calces, which is to be very fixed. Antimony may also be calcined by mixing with that mineral an equal quantity of charcoal-dust. As charcoal is incapable of fusion, it prevents the Antimony from clotting, as well as from losing so much of its metallizing phlogiston as it otherwise would: and hence it comes to pass that the calx of Antimony, prepared in this manner, comes nearer to the nature of a Regulus, than that which is prepared without addition. If you happen to raise the fire too much, in this calcination with charcoal-dust, the calx will be partly reduced to a Regulus, by means of the phlogiston which the charcoal furnishes; and then the Regulus will be dissipated in vapours, especially as this calx, which comes very near the nature of a Regulus, is not so fixed as that prepared without addition. For this reason it always continues to smoke, even when it contains no superfluous Sulphur: and therefore you must not wait till it cease to smoke before you put an end to your calcination; for you will lose a great deal of it in vapours. It is time to stop when the vapours that rise from it, while it is moderately red, do not smell of burning Sulphur. PROCESS V. _Calx of Antimony reduced to a Regulus._ Mix the calx of Antimony, which you intend to reduce, with an equal quantity of black soap. This mixture will make a thin paste. Put it little by little into a crucible, previously made red-hot amidst live coals. Thus let the soap burn till it cease to emit any oily smoke. Then cover the crucible; make the fire strong enough to melt the matter, and you will hear it effervesce and boil. When this noise is over let the crucible cool, and then break it: you will find in it a beautiful scoria, marked with circles of several colours; and under that a button of Regulus, which is not yet quite pure, and must be purified in the following manner. Pound this Regulus, and mix it with half its weight of an antimonial calx as perfectly desulphurated as possible. Put it into a crucible, and cover it: melt the whole, so that the surface of the melted matter may be smooth and uniform. Let the crucible cool, and then break it: you will find in it a beautiful button of very pure Regulus, covered with a scoria having the appearance of an opaque glass, or a kind of greyish enamel, moulded on the finely radiated surface of the Regulus. _OBSERVATIONS._ Of all the metalline calces that of Antimony is most easily reduced. Any matter that contains the phlogiston, even charcoal-dust alone, is sufficient to procure it the form of a Regulus, without the addition of any thing to facilitate its fusion; because this calx, which is not of itself altogether refractory, becomes still more fusible as it combines with the phlogiston, and approaches to the reguline state. Though all inflammable matters are capable of procuring the reduction of the calx of Antimony, yet there are some with which the operation succeeds better, and produces a greater quantity of Regulus, than it does with others. Fatty matters, joined with Alkalis, are those which answer best in this reduction, as they do in most others. The black flux, for instance, is very proper for this purpose: but Mr. Geoffroy, who made many experiments on Antimony, found by repeated trials that black soap is still fitter for it, and that a greater quantity of Regulus was obtained by its means, than by any other reducing flux whatever. The process here given is taken from one of the Memoirs on this subject, which he laid before the Academy of Sciences. Black soap is made of the lye of a Fixed Alkali, such as potash for instance, with quick-lime, incorporated by boiling with oil of lint-seed, rape-seed, or hemp-seed, and sometimes also with animal fat. The oily matters, contained in this reducing flux, are first burnt and charred to a coal in the crucible. As soon as they are brought to this state, the crucible is covered, and the fire is increased, till the matters melt. At that instant the reduction begins to take place; and the bubbling noise observed is an effect thereof. The Regulus obtained by this first fusion is not yet very pure, being adulterated with the mixture of some unmetallic earth that was contained in the Antimony, and with a portion of the calcarious earth of the soap. Mr. Geoffroy found that his Regulus was contaminated with this substance, by putting it into water: for on that occasion he observed a very brisk ebullition about the reguline buttons, which sometimes lasted above four and twenty hours; and on examining them with a glass, he discovered some little holes, imperceptible to the naked eye, through which the water entered, to unite with the lime retained in the internal parts of the Regulus, which having been recalcined in the operation required to be slaked. This Regulus may be purified by simple fusion, without any additament, because the particles of lime, being lighter than those of the Regulus, will be thrown up to the surface, on which they will form a sort of scoria. But Mr. Geoffroy took notice that, in this case, the surface of the Regulus is never very neat; that it is always sullied with a very adhesive scoria, and that no star is formed upon it. Besides, the Regulus must be kept a long while in very thin fusion, that the heterogeneous matters, which hinder the perfect re-union of its parts, may have time to rise to the surface by their lightness. But the longer the Regulus is kept in fusion, the more of it evaporates, because of its volatility. He was therefore obliged to have recourse to other means. We have in the process described the method which succeeded best with Mr. Geoffroy. It consists in melting the Regulus over again, with the addition of a little fresh calx of Antimony thoroughly freed from its Sulphur. This calx being in its nature easily vitrifiable, and combining with the earthy parts that deprave the Regulus, and which cannot be vitrified without addition, scorifies these matters, and with them forms the opaque glass, or kind of enamel which is found over the Regulus purified in this manner. The star on that part of the Regulus of Antimony, which was contiguous to the scoria, is a mark of its purity, and a proof that the operation was well performed. This star is nothing but a particular disposition of the parts of the Antimony, which have the property of running naturally into facets and needles. The perfect fusion, both of the Regulus and the scoria that covers it, leaves the parts of the Regulus at liberty to range themselves in this order. This disposition appears not only on the upper surface of the Regulus, but, if you break the button, you find the same in its internal parts. There are some round pyrites whose insides have nearly the same appearance, and seem to consist of rays issuing from a common center. The quantity of Regulus obtained by Mr. Geoffroy's process is more than double of what is procured in the common way, which yields but about four ounces in the pound; whereas this gives from eight to ten ounces. When Antimony is calcined with charcoal-dust, what remains after the dissipation of all the Sulphur is not, properly speaking, a calx of Antimony; but a sort of Regulus quite formed, and differing from the common Regulus only in that its parts are disunited, and not collected into a mass. For if this pretended calx of Antimony be melted, it directly coalesces into a Regulus, without the addition of any inflammable matter fit to procure its reduction. Indeed less Regulus is obtained by this means than when a reductive is added: but nevertheless this experiment still proves what I advanced; seeing Regulus of Antimony cannot be melted without losing more or less thereof, either because some of it is dissipated in vapours, or because part of it loses its phlogiston in the fusion, and so is converted into a calx. PROCESS VI. _Antimony calcined with Nitre. Liver of Antimony. Crocus Metallorum._ Pulverize and mix perfectly together equal parts of Nitre and Antimony: put the mixture into an iron mortar, and cover it with a tile, which however must not shut it quite close. With a live coal set fire to the matter in the mortar, and immediately withdraw it. The mixture will flame, with great detonation; which being over, and the mortar cooled, invert it, and strike its bottom to make all the matter fall out. Then, by a blow with a hammer, separate the scoria from the shining part, which is the _Liver of Antimony_. _OBSERVATIONS._ In this operation the Nitre takes fire and detonates with the Sulphur of the Antimony; and nothing remains but the metallic earth of the mineral, which, meeting with no substance to restore its phlogiston, cannot take the form of a Regulus; but, being combined with a large quantity of fused saline matters, begins itself to flow, and forms a sort of vitrification; which, however, is not a complete one, because the matters do not continue long enough in fusion, but cool too soon. This preparation of Antimony is a violent Emetic. It is used to make Emetic Wine and Tartar Emetic: it is also given in substance to horses. The saline matters found after the operation in the form of a scoria, or perhaps confounded with the Liver of Antimony, are combinations of Fixed Nitre, partly with the Acid of the burnt Sulphur, forming a Neutral Salt of the same kind as Vitriolated Tartar, and partly with some unburnt Sulphur, forming a sort of Liver of Sulphur that contains a little Regulus. It is usual to pulverize this Liver of Antimony and wash it with water, in order to dissolve and carry off all the Salts. When thus pulverized and washed it is called _Crocus Metallorum_. If Liver of Antimony be melted with any inflammable matter, it will be reduced to a Regulus; because it is nothing but a metalline calx half vitrified. PROCESS VII. _Another Calcination of Antimony with Nitre. Diaphoretic Antimony._ Materia Perlata. Clyssus _of Antimony_. Mix one part of Antimony with three parts of Nitre; project this mixture by spoonfuls into a crucible kept red-hot in a furnace. Each projection will be attended with a detonation. Continue doing this till you have used all your mixture: then raise the fire, and keep it up for two hours; after which throw your matter into a pan full of hot water. Let it lie steeping in water kept hot for a whole day. Then pour off the liquor: wash the white powder you find at bottom in warm water; and repeat the ablutions till the powder become insipid. Dry it, and you have _Diaphoretic Antimony_. _OBSERVATIONS._ This operation differs from the preceding one, in respect of the quantity of Nitre deflagrated with the Antimony. In the former we added one part only of Nitre to one part of Antimony; but in this three parts of Nitre are put to one of the mineral; and the calx resulting from this mixture is of course very different from the other. In the first place, Liver of Antimony hath a reddish colour; whereas Diaphoretic Antimony is very white. Secondly, Liver of Antimony is in a manner half vitrified; Diaphoretic Antimony is, on the contrary, in the form of a powder, the parts of which have no connection together. The reason of these differences will easily appear, if we consider, that, Liver of Antimony being the result of calcination with one part of the Nitre only, which is not sufficient to consume all the Sulphur of the mineral, what remains after the detonation is not entirely deprived of its phlogiston; from whence arise the colour it retains and the ease with which it flows in the fire: but that, when three parts of Nitre are added instead of one, this quantity is not only sufficient to consume all the Sulphur and the phlogiston of the Antimony, but even more than enough; seeing that, after the operation, some Nitre is still found undecomposed. The calx of Antimony, prepared by calcining it with three parts of Nitre, is therefore deprived of all its phlogiston. This is the cause of its whiteness, and the reason why it is not half vitrified by the operation, as Liver of Antimony is: for we know that the more a metallic calx is deprived of its phlogiston, the less fusible and the less vitrifiable it is. This calx of Antimony bears the name of _Diaphoretic Antimony_, or _Diaphoretic Mineral_: because, being neither emetic nor purgative, it is thought to have the virtue of promoting perspiration. Antimony may be calcined with various proportions of Nitre, between that used to make Liver of Antimony, and this with which Diaphoretic Antimony is prepared; and from these calcinations will result calces possessed of properties both chymical and medical, of an intermediate nature between the extremes of those two preparations. The nearer the proportion of Nitre comes to that employed in preparing Liver of Antimony, the more will the resulting calx resemble that preparation; and in the same manner, a calx prepared with a greater proportion of Nitre will so much the more resemble Diaphoretic Antimony, as the proportion of Nitre used comes nearer three parts of Nitre for one of Antimony. It is not necessary that Antimony in substance be employed to make the Diaphoretic Mineral: you may, if you please, make use of its Regulus. But as the Regulus contains no Sulphur, nor any more phlogiston than is requisite to secure its metalline form, it is needless to put three parts of Nitre to one of Regulus; an equal quantity thereof being sufficient. The matter is projected by spoonfuls, to the end that, by gradual and repeated detonations, the Antimony may be more perfectly calcined: it is also with a view to destroy entirely the small remainder of phlogiston, which may have escaped the action of the Nitre, that the matter is kept red-hot in the crucible for two hours. The whole is afterwards thrown into hot water, and left steeping therein for several hours, with design to give the water time to dissolve all the saline matters that are mixed with the Diaphoretic Calx. When crude Antimony is used in making this preparation, these saline matters are, 1. an Alkalizated Nitre; 2. a Neutral Salt formed by the union of the Acid of Sulphur with part of that Alkali, as in the preparation of Liver of Antimony; 3. a portion of undecomposed Nitre. The water in which the Diaphoretic is washed takes up moreover a portion of the calx of Antimony, which is exceeding finely attenuated, and continues united with the fixed Nitre, and suspended therewith in the liquor. This matter is to be separated from the Fixed Nitre, by mixing the water wherein it is dissolved with an Acid, which unites with the Alkali, and precipitates this matter in the form of a white powder, to which the name of _Materia Perlata_ hath been given. Because it is precipitated in the same manner as the Golden Sulphur of Antimony, and, like that, is found in the water with which the saline matters are washed out, after the detonation of Nitre with Antimony, some Chymists have given it, though very improperly, the name of the _Fixed Sulphur of Antimony_. This matter is a true Calx of Antimony, and differs from Diaphoretic Antimony in nothing but its being still more perfectly calcined. It is so indeed to such a degree that it is impossible to restore its metalline form, or reduce it to a Regulus, by the addition of an inflammable matter. Diaphoretic Antimony, on the contrary, may be re-metallized, by supplying it with phlogiston: but it must be observed that, in whatever manner you go about this, you will obtain a much smaller quantity of Regulus, than when you use a Calx of Antimony prepared with a smaller quantity of Nitre. If you attempt to reduce either Liver of Antimony or Diaphoretic Antimony, great care must be taken to wash them thoroughly, in order to free them from every thing saline: for, without this precaution, the Acid of the Sulphur, having, as was observed, formed a Neutral Salt with the Alkali of the Nitre, will combine with the inflammable matter added to revivify the calx of Antimony and reproduce a Sulphur; which, uniting afterwards with the same Alkali, will produce a Liver of Sulphur, that will dissolve part of the Regulus, hinder its precipitation, and greatly lessen the quantity which might otherwise be expected. A particular sort of Diaphoretic Antimony is sometimes prepared for Medical uses, which hath a purgative quality: it is not washed at all, and is therefore called _Unwashed Diaphoretic Mineral_. Diaphoretic Antimony may also be prepared in close vessels, by means of which the vapours that rise during the operation are retained. For this purpose a tubulated retort is employed, having a series of adopters fitted to it. The retort is placed in a furnace, and heated till its bottom become red: then a very small quantity of the mixture, for making Diaphoretic Antimony, is introduced through the tube in the upper part of the retort, and the tube immediately stopped. A detonation ensues, and the vapours expand themselves into the adopters, where they condense. This is repeated till the intended quantity of matter be used. After the operation some white flowers are found sublimed in the neck of the retort, and a small quantity of liquor in the recipients. This liquor is acid. It consists of some of the Acid of the Nitre, which the Acid of the Sulphur hath expelled from its basis, and also a little of the Acid of the Sulphur carried up by the heat before it could combine with the basis of the Nitre. This liquor is called _Clyssus of Antimony_. The name of _Clyssus_ is given to all liquors in general that are prepared by this method. The white flowers found in the neck of the retort are flowers of Antimony; that is, a calx of Antimony forced up by the heat, and by the impetus of the detonation. These flowers may be reduced to a Regulus. What remains in the retort is the same with the matter that remains in the crucible, wherein the mixture of Nitre and Antimony for making Diaphoretic Antimony hath been deflagrated. Neither Diaphoretic Antimony nor the Pearly matter are soluble in any Acid. PROCESS VIII. _Calx of Antimony Vitrified._ Take any quantity you please of calx of Antimony, made without addition; put it into a good crucible, which set in a melting furnace: kindle the fire gradually, and leave the crucible uncovered at the beginning. A quarter of an hour after the matter is red-hot, cover the crucible, and excite the fire vigorously till the calx melt. You may know when it is thoroughly melted, by dipping into the crucible an iron wire, to the end of which a little knob of glass will adhere, if the matter be in perfect fusion. Keep it in fusion for a quarter of an hour, or rather longer if your crucible can bear it. Then take it out of the furnace, and immediately pour out the melted matter on a smooth stone, made very hot for the purpose: it will presently fix into a yellow Glass. _OBSERVATIONS._ All the calces of Antimony, when exposed to a violent fire, are converted into Glass; but not all with the same facility. In general, the more of their phlogiston they have lost in the calcination, the more difficult is their vitrification. This causes also a difference in the colour of the Glass; which will be of so much a deeper yellow, and the nearer to a red, the less the Antimony was calcined. It frequently happens, when we employ a calx of Antimony which is not sufficiently deprived of its phlogiston, that we find in the crucible a button of Regulus, which, being heavier than the Glass, always lies at the bottom. With a view to avoid this inconvenience, and to dissipate completely the excess of phlogiston that may still be left in the calx of Antimony, we direct the crucible to be left uncovered for some time, at the beginning of the operation. If, notwithstanding this precaution, any Regulus be still found at the bottom of the crucible, and you resolve to vitrify it, the crucible must be returned to the furnace, and the fusion continued; by which means the Regulus will at last be converted into Glass. If, on the contrary, you meet with any difficulty in effecting the vitrification, on account of your having employed a calx that hath lost too much of its phlogiston, such as Diaphoretic Antimony, or the Pearly matter, the fusion may be greatly facilitated by throwing into the crucible a little crude Antimony. Glass of Antimony is a most violent emetic. This Glass, as well as Liver of Antimony, is employed in preparing Emetic Wine and Emetic Tartar. It may be resuscitated, like the calces of Antimony, into a Regulus, by re-uniting it with a phlogiston. For this purpose it must be finely pulverized, thoroughly mixed with some black flux, and melted in a covered crucible. This Glass, as well as that of Lead, hath the property of greatly promoting the vitrification of matters that are to be scorified. PROCESS IX. _Kermes Mineral._ Break any quantity you will of Hungarian Antimony into little bits: put it into a good earthen coffee-pot: pour on it twice its weight of rain-water, and a fourth part of its weight of well filtered liquor of Nitre fixed by charcoal. Boil the whole briskly for two hours, and then filter the liquor. As it cools it will acquire a red colour, grow turbid, and leave a red powder on the filter. Return your Antimony into the coffee-pot. Pour on it as much rain-water as before, and three fourths of the former quantity of the liquor of Fixed Nitre. Boil it again for two hours, and then filter the liquor. It will again deposite a red sediment. Return your Antimony into the coffee-pot: pour on it the same quantity of rain-water, and half the first quantity of the liquor of Fixed Nitre. Boil it again for two hours, and then filter the liquor as formerly. Wash all these sediments with warm water, till they become insipid; then dry them, and you have the _Kermes Mineral_. _OBSERVATIONS._ If you recollect what we said concerning the property which Fixed Alkalis possess of uniting with Sulphur, both by fusion, and, when those Salts are resolved into a liquor, by boiling, and of forming therewith a Liver of Sulphur, which dissolves all metalline substances, you will readily comprehend the nature of this Kermes. Antimony consists of a sulphureous and a reguline part. Therefore, if this mineral be boiled in a solution of a Fixed Alkali, such as Nitre fixed by charcoal, the Alkali will dissolve the Sulphur of the Antimony, and form therewith a Liver of Sulphur, which, in its turn, will dissolve the reguline part. Now, Kermes Mineral, prepared as above directed, is no other than a Liver of Sulphur combined with a certain quantity of Regulus of Antimony. Mr. Geoffroy hath set this truth in the clearest light, by his accurate analysis of the Kermes Mineral. The experiments he made on that subject are circumstantially related in several Memoirs printed in the volumes of the Academy for 1734 and 1735. By combining Acids with the Kermes he demonstrated, 1. the existence of Sulphur in this compound; having separated from it a burning Sulphur, which cannot be mistaken for any other than the Sulphur of Antimony. In order to obtain this Sulphur pure, an Acid must be employed that will not only absorb the Alkali, but also perfectly dissolve the reguline part that might otherwise remain united with the Sulphur. _Aqua regia_ was the Acid which succeeded best with Mr. Geoffroy. 2. He also proved that there is a Fixed Alkali in the composition of the Kermes; seeing the Acids with which he precipitated the Sulphur became Neutral Salts, and just such as those very Acids combined with a Fixed Alkali would have constituted: that is, the Vitriolic Acid produced a _Sal de duobus_; the Nitrous Acid a regenerated Nitre; and the Marine Acid a regenerated Sea-salt. 3. Mr. Geoffroy demonstrated the reguline part of Antimony to be an ingredient in the Kermes; having procured therefrom an actual Regulus of Antimony, by fusing it with the black flux. In preparing the Kermes it is necessary to renew the liquor from time to time, as above directed; because, when it is once impregnated with Kermes to a certain degree, it can take up no more; and consequently the same liquor cannot operate again on the Antimony. Experience hath shewn, that, if the doses above prescribed be applied, the liquor will after two hours boiling be sufficiently saturated with Kermes. If the liquor in which the Kermes is dissolved be filtered while it is very hot, and almost boiling, it leaves nothing on the filter; the Kermes passing through with it: but as it cools it grows turbid, and gradually deposites the Kermes. Therefore it ought not to be filtered till it be cold; or, if it be filtered while it is boiling hot, in order to separate from it some coarse particles of Antimony not yet converted into Kermes, it must be filtered a second time when it is cold, in order to get the Kermes. Though in the method usually practised for making Kermes, the Antimony is boiled only thrice, yet it does not follow that more Kermes may not be obtained from it, or that but little more would be obtained by a fourth and fifth boiling; on the contrary, it would yield considerably more. Mr. Geoffroy observed, that he got more Kermes by the second boiling than by the first, and still more by the third than by the second; and that the yield goes on increasing in this manner to a very great number of times, which he hath not determined. This increased effect arises from hence, that by multiplying the frictions of the little bits of Antimony against each other, new surfaces are exposed to the action of the Alkaline liquor, and furnish it with more Sulphur; while the addition of this sulphur renders the hepar more active and more penetrating; or, if you please, produces a new hepar every time the matters are boiled. When the Alkaline liquor is once saturated with Kermes, it ceases to act, and forms no new hepar; but it does not follow that its virtue is quite exhausted. To restore its ability of acting as well as at first, or nearly so, you need only let it cool, and deposite the Kermes dissolved in it. We owe this singular observation also to Mr. Geoffroy: he had the patience to go through no less than threescore and ten boilings with the same liquor, without adding any thing but rain water, to supply the place of what was dissipated by evaporation: and he always obtained a pretty considerable quantity of Kermes by each boiling, for the reason given above. Boiling is not the only means of making Kermes. Mr. Geoffroy found the way of making it by fusion. For this purpose you must mix accurately one part of very pure Fixed Alkali, dried and pulverized, with two parts of Hungarian Antimony also pulverized, and melt the mixture. Mr. Geoffroy made use of a retort. When the mass is melted, it must again be pulverized, while it is still hot, and then put into, and kept in, boiling hot water for an hour or two; after which the liquor, now become saline and antimonial, must be filtered into another vessel filled with boiling water. Every ounce of Antimony treated in this manner yields, by thrice boiling the melted mass, from six drams to six drams and a half of Kermes; which differs from the Kermes made by boiling, only in that it is not quite so soft to the touch, having in every other respect the same qualities. As Liver of Sulphur is made two different ways, to wit, by boiling and by fusion, and as the Kermes is nothing but a Liver of Sulphur in which the reguline part is dissolved; it follows that Kermes may be made by fusion as well as by boiling. It is necessary to pulverize the melted mass, and to steep it in boiling hot water for an hour or two, that the water may dissolve and divide it sufficiently to make the Kermes fine and beautiful. With the same view, that is, to make it finer and more perfect, Mr. Geoffroy orders the water saturated with the Kermes made by fusion, to be received, when filtered, in a vessel full of other boiling hot water. He observed, that when the liquor impregnated with Kermes cools too fast, the Kermes that precipitates is much coarser. The warm solution of Kermes is diffused through the boiling-hot water into which it is filtered, and is thereby enabled to retain its heat so much the longer. From what hath been said on the nature of Kermes, it plainly appears that there must be a great resemblance between it and the Golden Sulphur of Antimony, obtained from the scoria, either of plain Regulus of Antimony, or of the Liver of Antimony; this Golden Sulphur being no other than a portion of the Antimony combined with the Nitre alkalizated during the operation. Yet there is a difference in the manner of precipitating these two compounds: for the Kermes precipitates spontaneously, on the bare cooling of the water in which it is dissolved; whereas an Acid is employed to precipitate the Golden Sulphur suspended in the water, with which the scoria of the plain Regulus of Antimony, or that of Liver of Antimony, hath been washed. This gives some ground to suspect that the reguline part is not so intimately united with the Liver of Sulphur in the Kermes, as in the scoriæ from which the Golden Sulphur is obtained. PROCESS X. _Regulus of Antimony dissolved in the Mineral Acids._ Compound an _aqua regis_ by mixing together four measures of Spirit of Nitre, and one measure of Spirit of Salt: on a sand-bath moderately heated place a matrass, into which pour sixteen times as much of this _aqua regis_ as you have Regulus to dissolve. Break your Regulus into little bits; and throw them successively one after another into the matrass, observing not to add a new one till that put in before is entirely dissolved: continue this till your Regulus be all used. By degrees, as the dissolution advances, the liquor will acquire a beautiful golden colour; which, however, will insensibly disappear, as the white fumes that continually ascend from it evaporate. _OBSERVATIONS._ Regulus of Antimony is one of those metalline substances that dissolve with the greatest difficulty. Not but that most of the Acids attack and corrode it; but they do not make a clear, limpid solution thereof: they in some sort only calcine it, and this semi-metal, as fast as it dissolves, precipitates of its own accord in the form of a white magistery. In order to effect a complete dissolution thereof, it is necessary to employ an _aqua regis_ compounded as directed, and in the dose prescribed in the process, which is wholly taken from Mr. Geoffroy's Memoirs on Antimony mentioned above. If, instead of the Regulus, small bits of crude Antimony be thrown into the _aqua regis_, the Acid will attack and dissolve the reguline part, and so separate it from the sulphureous part which it will not touch. When the dissolution is finished, the particles of Sulphur being now become lighter, because no longer united with the metalline part, will float upon the liquor. Being collected they form a true Sulphur, which seems no way different from common brimstone. This operation, you see, is a sort of Parting Process. The Vitriolic Acid, whether concentrated or much weakened with water, does not act when cold either on Antimony or on its Regulus. This Acid only dims the splendour of the facets of the Regulus; but if one part of exceeding pure Regulus of Antimony be put into a retort, and four parts of clear concentrated Oil of Vitriol poured on it, as soon as the Acid is heated it turns brown, and emits a most suffocating smell of Sulphur, which increases as the Regulus is penetrated and corroded by the Acid. On raising the fire, there separates from it a matter that seems mucilaginous; and when the Acid hath boiled some time, the Regulus is converted into a white saline mass, as Mercury is in the preparation of Turbith mineral. At the same time a little Sulphur sublimes into the neck of the retort. At last all the Oil of Vitriol passes over into the receiver, and leaves the Regulus in a white, spungy, saline mass in the retort. When the fire is out, the vessels unluted, and the receiver separated from the retort, there rises a white vapour like that of the smoking liquor of Libavius. The saline mass left in the retort, after the operation, is found increased to near double its weight: this increased weight is owing to the Acid that hath united with the Regulus. This combination of the Vitriolic Acid with the Regulus of Antimony is excessively caustic, and cannot, for that reason, be administered internally. The purest Spirit of Salt hath no sensible effect either on Antimony or its Regulus: but if Antimony be coarsely pounded, it separates therefrom, though slowly, some light, sulphureous flakes. The action of Spirit of Nitre on this metallic substance is more perceptible: by little and little it attacks the plates of the Antimony, which discharge a great number of air-bubbles. As the dissolution advances, the Acid acquires a greenish colour inclining to blue; and if there be not too much of it, it will be almost entirely imbibed by the Antimony, penetrate between its _laminæ_, and exfoliate them in the direction of the needles that compose them. If there be too much of the Acid, that is, if it rise above the Antimony, it will destroy these plates, and reduce them to a white powder. But when the Acid is imbibed slowly, we discover between the swelled _laminæ_ little saline transparent crystals, that vegetate much in the same manner as those of the pyrites, in which small crystals of Vitriol are frequently observed, whose figures are not very well determined. These little crystals between the Antimonial plates are intermixed with yellow particles, which being carefully separated burn like common Sulphur. All these useful observations, concerning the action of the Acids on Antimony and its Regulus, we owe likewise to Mr. Geoffroy; who advises the collecting a quantity of these little crystals in time; because they disappear soon after they are formed, being probably covered by the white powder, or magistery, which is continually produced as fast as the Nitrous Acid disunites and separates the needle-like fibres of the Antimony. Mr. Geoffroy observed the same sort of crystals on the Regulus of Antimony, when substituted for crude Antimony in this experiment; but it requires a great deal of care to separate these crystals; for as soon as the air comes into contact with them they lose their transparency; and if you wait till the Regulus be in some measure converted into a magistery, they are not then to be distinguished. In order therefore to have a good view of these crystals, the Regulus must be broken to pieces; these pieces put in a glass bason, and Spirit of Nitre poured on them to half their heighth, but not to cover them. This Acid penetrates them, exfoliates them in white scales; and on the surface of these scales the crystals shoot of a dead white colour. In two or three days time these crystals vegetate and grow in the form of cauli-flowers: they must then be gathered, to prevent their being confounded in the white magistery which continues to be produced, and would not suffer them to be distinguished. If you attempt to dissolve the reguline part of Antimony by an _aqua regis_ compounded in different proportions, and applied in a different dose from what is prescribed in the process, the Regulus of Antimony will only be calcined, as it is by the other Acids, and will precipitate in the form of a white magistery as fast as it dissolves, so that no part thereof will remain united with the solvent. The proof of this is, that if an alkaline liquor be poured, even to the point of saturation, upon the _aqua regis_ that hath thus dropt the Antimony, no new precipitate will be deposited. PROCESS XI. _Regulus of Antimony combined with the Acid of Sea-salt. Butter of Antimony. Cinabar of Antimony._ Pulverize and mix thoroughly six parts of Regulus of Antimony, and sixteen parts of Corrosive Sublimate. Put this mixture into a glass retort that hath a wide short neck, and let one half of its body at least be left empty. Set it in a reverberatory furnace, and having fitted a recipient thereto, and luted the joint, make a very small fire at first, to heat it slowly. Increase it afterwards by degrees, till you see a liquor ascend from the retort that grows thick as it cools. Keep up the fire to this degree as long as you see any of this matter come over. When no more rises with this degree of fire, unlute your vessels, take off the receiver, and in its place substitute another filled with water. Then increase your fire by degrees till the retort be red-hot. Some running Mercury will fall into the water, which you may dry and keep for use; it being very pure. _OBSERVATIONS._ In our observations on the preceding process, we took notice that the purest Marine Acid, in the form of a liquor, will not dissolve the reguline part of Antimony. Here this very Acid combined with Mercury, and applied in a dry form to the Regulus of Antimony, quits the Mercury with which it was united, in order to join this very Regulus, as having a greater affinity therewith. This operation is a further proof of what we advanced on the subject of Mercury; to wit, that several metallic substances, which are not soluble by certain Acids when in a fluid state, may be dissolved by those Acids when most highly concentrated; as they are when combined with any other substance in a dry form, and are separated from it by the force of fire. Their efficacy is also further promoted by their being reduced, on this occasion, into subtile vapours. The Marine Acid combined with the reguline part of Antimony doth not form a hard, solid compound; but a kind of soft substance, that melts in a very gentle heat, and also becomes fixed by the least cold, much in the same manner as butter; and from this property it hath its name. Soon after mixing the Regulus with the Corrosive Sublimate, the matter sometimes grows considerably hot: this is occasioned by the Marine Acid's beginning to act on the reguline part, and to desert its Mercury. The Butter of Antimony rises with a very moderate heat; because the Acid of Sea salt hath the property of volatilizing, and carrying up along with it, the metallic substances with which it is combined: and for this reason a very gentle heat only is required at the beginning of the operation. It is absolutely necessary that the neck of the retort be wide and short: for otherwise if the Butter of Antimony should fix and be accumulated therein, it might stop up the passage entirely, and occasion the bursting of the vessels. By this operation we obtain eight parts and three quarters of fine Butter of Antimony, and ten parts of running Mercury; there being left in the retort one part and a half of a rarefied matter, black, white, and red. This is probably the most earthy and most impure part of the Regulus of Antimony. It is of the utmost consequence to the operator that he avoid with the greatest care the vapours that issue from the vessels, because they are extremely noxious, and may occasion mortal disorders. The Butter of Antimony is a most violent Corrosive and Caustic. When all the Butter is risen, the receiver is shifted in order to receive the Mercury; which, being disengaged from the Acid that gave it a saline form, appears in its natural form of Quick-silver: but it requires a much greater degree of heat than the Butter of Antimony to raise it by distillation. If crude Antimony, instead of Regulus of Antimony, be mixed with Corrosive Sublimate, a Butter of Antimony will be obtained in the same manner; but, instead of having a running Mercury after the Butter, you will find a Cinabar sublimed into the neck and upper concavity of the retort. The reason of this difference is easily conceived: for when the Regulus is used, the Mercury being deserted by its Acid finds no other substance to unite with, and so rises in the form of Quick-silver; but when crude Antimony is employed instead of its Regulus, as the reguline part thereof cannot combine with the Acid without quitting its Sulphur, so this Sulphur, being at liberty, unites with the Mercury, which is so likewise, and therewith forms a Cinabar; which from its origin is named _Cinabar of Antimony_. When you intend to make both Butter and Cinabar of Antimony at the same time, six parts of Antimony must be mixed with eight of Corrosive Sublimate; and care must be taken, while the Butter is coming over, to warm the neck of the retort by holding some live coals near it, with the precautions necessary to avoid breaking it. This warmth makes the Butter melt and run into the receiver; whereas, being thicker and of a much denser consistence than that made with the Regulus, it would otherwise gather in the neck of the retort, choak it entirely, and burst the vessel. When the Butter is drawn from crude Antimony, more circumspection is necessary to make it of a beautiful white colour, than when it is obtained from the Regulus: for, if the fire be too strong during the distillation, or if the receiver be not soon enough separated from the neck of the retort, certain red sulphureous vapours, the fore-runners of the Cinabar, will at last ascend, and mixing with the Butter give it a brown colour. In order to restore its beauty it must be put into a clean retort, and rectified by distilling it over again with a gentle sand-heat. By this rectification the Butter of Antimony becomes more fluid; and by re-distilling it a second time you may give it the thinness and fluidity of an oil. After the operation there will be found in the receiver three parts and three quarters of Butter of Antimony, and some small crystals adhering to its inside, in the form of sprigs. When you break the retort there exhales from it a sulphureous odour; and you will find in it seven parts of Cinabar of Antimony, the greatest part of which is usually in compact glebes, that are heavy, smooth, shining, blackish throughout most of the mass, but in some places red: another part thereof appears in shining needles, and the rest in powder. When all the Butter of Antimony is come over, and you begin to see the red vapours that predict the approaching ascent of the Cinabar, the receiver containing the Butter must be removed, lest the colour of the Butter should be spoiled by those sulphureous vapours. Another receiver is usually fitted on, without luting; in which a small quantity of running Mercury is sometimes found, when the operation is finished. There remains, at the bottom of the retort, a fixed, shining, crystalline, black mass, which may be reduced to a Regulus by the common method. Butter of Antimony may also be obtained from a mixture of Antimony with any of the other preparations of Mercury in which the Acid of Sea-salt is an ingredient; such as sweet Sublimate, the Mercurial Panacea, and White Precipitate: but as none of these combinations contain so great a proportion of that Acid as is in the Corrosive Sublimate, the Butter obtained by their means is far from being so caustic and so fiery as that which rises from a mixture of Antimony, or its Regulus, with Corrosive Sublimate. Silver precipitated by the Acid of Sea-salt, and ready to be melted into a _Luna cornea_, being mixed with powdered Regulus of Antimony yields likewise a Butter of Antimony. If you propose to make it by this means, you must mingle one part of the Regulus of Antimony in powder with two parts of the Precipitate; put this mixture into a glass retort of such a size that it may fill but one half thereof; set it in a furnace; apply a receiver; begin with a gentle heat, which will make a clear liquor come over; and then increase your fire by degrees. White vapours will rise and condense into a liquid Butter; and in the mean time there will be a slight ebullition in the receiver, attended with a little heat. Continue the fire till nothing more will come over; then let your vessels cool and unlute them. You will find in the receiver an Oil or Butter of Antimony, partly fluid and partly congealed, somewhat inclined to yellow, weighing an eighth part more than the Regulus of Antimony made use of. The inside of the retort will be carpeted over with small white flowers, of a brilliant silver colour, and an acid taste; and in the bottom of the retort will be found a hard, compact, ponderous mass, difficult to break, yet falling of itself to a powder; its colour externally grey, white, and blueish; internally black, and shining much like Regulus of Antimony; having a saltish taste on its surface, and weighing about a sixteenth less than the Precipitate of Silver employed in the operation. This experiment demonstrates that the Acid of Sea-salt hath a greater affinity with Regulus of Antimony than with Silver. The Butter of Antimony prepared by this method is somewhat less caustic than that made with Corrosive Sublimate. It is called the _Lunar Butter of Antimony_. The effervescence that arises in the receiver is remarkable. Probably the Acid of Sea-salt, though reduced into vapours when it ascends out of the retort, is not yet perfectly combined with the reguline part of the Antimony, which it nevertheless carries over with it, and the union is completed in the receiver; which occasions the effervescence observed. The little white silvery flowers, adhering to the inside of the retort, are flowers of Regulus of Antimony, which sublime towards the end of the distillation. The compact mass, found at the bottom of the retort, is no other than the Silver separated from its Acid, and combined with a portion of the Regulus of Antimony. The colours and the saltish taste of its surface are occasioned by a remainder of the Marine Acid. This Silver is rendered brittle and eager by the union it hath contracted with some of the Regulus of Antimony. It is easy to purify it, and restore its ductility, by separating it from the Regulus of Antimony. There are several ways of doing this: one of the most expeditious is to flux it with Nitre, which burns and converts to a calx the semi-metal with which the Silver is adulterated. PROCESS XII. _Butter of Antimony decompounded by means of Water only. The_ Pulvis Algaroth, _or_ Mercurius Vitæ. _The Philosophic Spirit of Vitriol._ Melt with a gentle heat as much Butter of Antimony as you please. When it is melted, pour it into a large quantity of warm water. The water will immediately grow turbid, but whitish, and let fall a great quantity of white powder. When all the precipitate is settled, decant the water: pour on fresh warm water; and having thus edulcorated it by several ablutions, dry it, and you have the _Pulvis Algaroth_, or _Mercurius Vitæ_. _OBSERVATIONS._ In the preceding processes we observed that the Marine Acid will not dissolve the reguline part of Antimony, unless it be very highly concentrated, and more so than it can possibly be while in the form of a liquor. Of this the experiment before us is a further proof. Whilst the Marine Acid is so perfectly dephlegmated, as it is in Corrosive Sublimate and Butter of Antimony, it remains combined with the reguline part of Antimony; but if this combination be dissolved in water, the moment the Acid is weakened by the interposition of the particles of water, it becomes incapable of continuing united with the semi-metal which it had before dissolved; deserts it, and lets it fall in the form of a white powder. The _Pulvis Algaroth_ is therefore no other than the reguline part of Antimony, attenuated and divided by the union it had contracted with the Acid of Sea-salt, and afterwards separated from that Acid by the intervention of water alone. The proof is, that this powder retains none of the properties of the Butter of Antimony: it is neither so fusible nor so volatile; on the contrary, it is capable of sustaining a very strong degree of fire, without subliming and without melting: it may be reduced to a Regulus: it hath not now the same caustic nature: it is only an emetic; which however is extremely violent, and on that account is never prescribed by any prudent physician. Another proof, that the Marine Acid is separated from the Regulus of Antimony in the precipitation of the _Pulvis Algaroth_, is, that the water in which this precipitation is made becomes acid, or a sort of weak Spirit of Salt. If it be evaporated, and concentrated by distillation, a very strong acid liquor may be obtained from it. This Acid goes, very improperly, by the name of the _Philosophic Spirit of Vitriol_; for it is rather a Spirit of Salt. The _Pulvis Algaroth_, made with Butter of Antimony procured from the Regulus, is whiter than that made with Butter of Antimony procured from crude Antimony; probably because the latter always retains some sulphureous particles. Butter of Antimony exposed to the air attracts the moisture thereof, and partly runs into a liquor; but, as fast as this liquor is produced, it deposites a white sediment, which is an actual _Pulvis Algaroth_. This also is very agreeable to what we advanced touching the decomposition of Butter of Antimony by the addition of water. The Butter attracts the moisture of the air, because the Acid it contains is exceedingly concentrated; and this moisture produces the same effect as water purposely added. PROCESS XIII. _Bezoar Mineral. The Bezoartic Spirit of Nitre._ Melt Butter of Antimony over warm ashes, and put it into a phial or matrass. Gradually pour on it good Spirit of Nitre, till the matter be entirely dissolved. This usually requires as much Spirit of Nitre as there is Butter of Antimony. During the dissolution fumes will rise, which must be carefully avoided. Pour your solution, which will be clear and of a reddish colour, into a glass cucurbit, or a pan of stone-ware: set it in a sand-bath, and evaporate to dryness with a moderate heat. There will be left a white mass, weighing a fourth part less than the whole quantity used, both of the Butter and the Spirit of Nitre. Let it cool, and again pour on it as much Spirit of Nitre as you used the first time. Place the vessel again in the sand-bath, and evaporate the moisture as before. You will have a white mass that hath neither gained nor lost in weight. On this pour, for the third time, the same quantity of Spirit of Nitre as you did the first time. Again evaporate the moisture to perfect dryness: then increase your fire, and calcine the matter for half an hour. You will have a dry, friable, light, white matter, of an agreeable acid taste; which will fall into a coarse powder, and must be kept in a phial carefully stopt. This is _Bezoar Mineral_: it is neither caustic nor emetic, and has only a sudorific virtue. It obtained the name it bears, because, like the animal Bezoar, it was imagined to have the property of resisting poison. _OBSERVATIONS._ It is not surprising that the Nitrous Acid poured on Butter of Antimony should dissolve it, and unite with it: for with the Marine Acid, which makes a part of this combination, it forms an _aqua regis_, which we know is the true solvent of the reguline part of Antimony. But in this dissolution, and the changes it produces, there are some things very remarkable and worthy of attention. 1. The Nitrous Acid, by uniting with the Butter of Antimony, deprives it of its property of rising with a very gentle heat, and makes it much more fixed: it can now be dried, and suffer all its moisture to be evaporated; which is not to be done with pure Butter of Antimony: for that, being exposed to a certain degree of heat, instead of letting go its moisture and remaining dry, rises wholly, without the least appearance of any separation of parts. 2. The Butter of Antimony, which, before its combination with the Nitrous Acid, is a most violent Caustic and Corrosive, becomes so mild after it, that it may not only be taken internally without danger, but hath scarce any sensible operation. The following considerations will lead us to a reasonable explanation of these phenomena. 1. The Nitrous Acid, when combined with metallic substances, doth not communicate to them the same volatility as they acquire from the Marine Acid. Hence it follows, that, if the Nitrous Acid be added to any combination of a metallic substance with the Marine Acid, this new compound will be rendered less volatile, and consequently more able, without rising in vapours, to bear a degree of heat sufficient to carry off part of its Acid. This is the case with Butter of Antimony, after Spirit of Nitre is mixed with it; especially considering, 2. That the Nitrous Acid cannot unite with the reguline part of the Butter of Antimony without weakening the connection between it and the Marine Acid; whence it follows, that the combination of the Nitrous Acid further facilitates the separation of the Marine Acid from the Regulus. Now as soon as the Marine Acid quits the reguline part, that part becomes more fixed, and consequently more capable of enduring the degree of heat requisite to discharge all the adhering Acid; and not only the Marine, but even the Nitrous also. It is not therefore surprizing that, after the Antimony which remains combined with the Nitrous Acid is dried, it should not possess that corrosive power which it derives only from the Acids wherewith it is armed. In order to free it more perfectly from all Acid, we order the fire to be increased after the third desiccation; and the remainder of the Butter of Antimony to be calcined for a full half-hour longer. That the Marine Acid is separated from the reguline part of the Butter of Antimony, by the desiccations it undergoes in converting it into Bezoar, is proved by this, that, when these desiccations are performed in close vessels, the liquor drawn off is a true _aqua regis_, known by the name of the _Bezoartic Spirit of Nitre_. It remains to be considered why the Bezoar mineral, though freed from all acid, is not emetic; while the _Pulvis Algaroth_, which is likewise the reguline part of the Butter of Antimony deprived of its Acid, is such a violent emetic, and even to be dreaded for its remaining causticity. In order to discover the reason of this difference, it is proper to observe that, when we say Bezoar mineral and the _Pulvis Algaroth_ contain no Acid, we must not be understood in too strict a sense: on the contrary, there is reason to think that a certain quantity of Acid still remains in each of them; which however is scarce worth notice, in comparison of the quantity each contained at first. This being allowed, it will not be hard to find the difference between these two preparations of Antimony. The _Pulvis Algaroth_ is deprived of its Acid by the addition of water alone, which only carries off all the loose Acid it can take up, without making any change in the nature of that which continues in combination with the reguline part. Now, as the Marine Acid is not intimately united with the reguline part in Butter of Antimony; as it still retains some of its properties, such as attracting the moisture of the air, giving manifest tokens of its Acid nature, &c.; and as the corrosive quality of this compound depends on this last in particular; the small portion of Acid left in the _Pulvis Algaroth_ will in some degree preserve its former character: and hence comes the effect of this powder, which still retains a little of the corrosive quality that belonged to the Butter of Antimony. But this is not the case with the small remainder of Acid, which possibly still continues united with the Bezoar mineral prepared as here directed. This compound hath been exposed to a fire sufficient, not only to dry it, but even to calcine it. Now fire is capable of producing great changes in the texture of bodies. It must have forced off from the Bezoar all the Acid that was not intimately combined with it; and that part which it could not drive off, because of its obstinate adhesion, it must have further united and combined more closely with the metallic earth: for we see that fire greatly promotes the action of solvents on the matters with which they are united. With regard to the properly emetic quality of the _Pulvis Algaroth_, it cannot be imputed to the combination of any Acid with that powder; since we see that the most powerfully emetic preparations of Antimony, _viz._ its Regulus and Glass, contain no Acid: it must therefore be attributed to some cause different from that on which its corrosive quality depends. This cause we shall easily find by attending to the different manners in which the Marine Acid, when alone and in _aqua regia_, operates on the reguline part of Antimony. The Marine Acid alone dissolves the Regulus of Antimony, but with great difficulty; nor doth it effect a complete dissolution thereof, as is evident from what hath been already said: whereas the Marine Acid, combined with the Nitrous Acid, and therewith forming an _aqua regis_, as in the preparation of Bezoar, dissolves the reguline part of Antimony completely and radically. Now, it is certain that, the more efficaciously Acids operate on metallic substances, the more of their phlogiston do they destroy; and we cannot but recollect that the preparations of Antimony are so much the less emetic the less phlogiston they contain, or the further they recede from the nature of a Regulus, and the nearer they approach to that of Diaphoretic Antimony: consequently it is plain how Bezoar mineral, which is a sort of calx of Antimony entirely deprived of its phlogiston by the intimate dissolution thereof made by the Acids of the _aqua regis_, may be in no degree emetic; while the _Pulvis Algaroth_, being a true Regulus of Antimony, on which the Marine Acid hath operated but very superficially, and which still contains a great deal of phlogiston, is a most violent emetic. PROCESS XIV. _Flowers of Antimony._ Take an unglazed earthen pot, having an aperture in its side, with a stopple to shut it close. Set this pot in a furnace, the cavity whereof it may fit as exactly as possible; and fill up with lute the space, if any, left between the vessel and the furnace. Over this vessel fix three aludels, with a blind-head at the top; and light a fire in the furnace under the pot. When the bottom of the pot is thoroughly red, throw into the lateral aperture a small spoonful of powdered Antimony. Stir the matter immediately with an iron spatula made a little bending, in order to spread it over the bottom of the vessel, and then stop the hole. The flowers will rise and adhere to the insides of the aludels. Keep up the fire so that the bottom of the pot may always continue red; and, when nothing more sublimes, put in a like quantity of Antimony, and operate as before. In this manner go on subliming your Antimony, till you have as many flowers as you want. Then let the fire go out; and when the vessels are cold unlute them. You will find flowers adhering all round the insides of the aludels and the head, which you may collect with a feather. _OBSERVATIONS._ Antimony is a volatile mineral, capable of being sublimed into flowers; but this cannot be effected without occasioning a notable change in its parts. The reguline and the sulphureous parts are not united so intimately, or in the same proportion, in the flowers as in the Antimony itself; and accordingly we find these flowers have a strong emetic quality, which Antimony hath not. They are of divers colours; which probably arises from their containing more or less Sulphur. Three or four aludels are placed one over another, not only with a view to provide a greater surface, to which the flowers may adhere, but also to give them room enough to circulate, without which they might burst the vessels. If you introduce the nosle of a pair of bellows into the pot that contains the Antimony, and blow upon it, the sublimation of the flowers will be much sooner effected. This is a general rule with regard to all matters that are to be sublimed or evaporated; the reason of which we have already given. It is proper that no interval be left between the furnace and the pot containing the Antimony, lest the heat should be thereby communicated to the aludels, on which the flowers fasten best when they are cold. After the operation, there remains at the bottom of the pot a portion of Antimony half calcined; which being pulverized, and thoroughly calcined till it emit no fume, may be employed to make the Glass of Antimony. PROCESS XV. _Regulus of Antimony converted into Flowers._ Pulverize your Regulus of Antimony: put the powder into an unglazed earthen pot: three or four fingers breadth above the powder, fit into the pot a little cover, made of the same earth, and having a small hole in its middle, so that it may with ease be placed in the pot, and taken out when there is occasion: cover the mouth of the pot with a common lid; set it in a furnace, and kindle a fire under it sufficient to make the bottom of the pot red, and to melt the Regulus. When it hath been thus kept in fusion for about an hour, let the fire go out, and the whole cool. Then remove the two covers. You will find adhering to the surface of the Regulus, which will be in a mass at the bottom of the pot, white flowers resembling snow, intermixed with beautiful, brilliant, silver-coloured needles. Take them out, and you will find them make about one part in sixty-two of the whole Regulus employed. Put the covers again in their places, and proceed in the same manner as before; when the vessels are cold you will find half as many more flowers as you got the first time. Proceed thus till you have converted all your Regulus into flowers. This will require a considerable number of sublimations, which, as you advance, will always yield you a greater portion of flowers; respect, however, being had to the quantity of Regulus remaining in the pot. _OBSERVATIONS._ We must here repeat what we said just before, in our observations on the preceding process; _viz._ that Regulus of Antimony is capable of being wholly elevated and sublimed by the action of fire; but that it must at the same time undergo a considerable change and alteration. These flowers of Regulus of Antimony are very different from every other Antimonial preparation. They resemble the Pearly Matter in this, that they cannot be reduced to a Regulus by any means whatever: but they differ from it, 1. in that they are not fixed; for, when melted by fire, they fly wholly away in vapours: 2. in that they are capable of being dissolved by _aqua regis_, much in the same manner as the Regulus; whereas the Pearly Matter is known to be indissoluble by any Acid. As soon as Regulus of Antimony is in fusion, it begins to sublime into flowers; so that it is needless to apply a greater degree of heat than is just sufficient to melt it. A pan of some width is preferable to a crucible for this operation; because the upper surface of the Regulus melted therein is larger, and, the larger that surface is, the more considerable is the quantity sublimed from it. The two covers which are applied within and over the pot are designed to check, as much as possible, the dissipation of the melted Regulus; yet without absolutely excluding the free access of the air, the concourse of which is useful in all metallic sublimations. Notwithstanding these precautions, it is impossible to prevent the escape of some of the Regulus, in vapours that cannot be confined. Somewhat less than three fourths of the Regulus made use of is nearly the yield in flowers: the rest evaporates through the interstices left by the covers, which must not be luted for the reason just assigned. CHAP. II. _Of_ BISMUTH. PROCESS I. _To extract Bismuth from its Ore._ Break the ore of Bismuth into small pieces, and therewith fill a crucible either of earth or iron. Set the crucible in a furnace, and light such a fire that the bits of ore may become moderately red. Stir the ore from time to time, and, if you perceive it crackle and fly, keep the crucible covered. At the bottom you will find a button of Bismuth. _OBSERVATIONS._ The extraction of Bismuth from its ore requires nothing but simple fusion, without the addition of any inflammable matter, because it is naturally possessed of its metalline form. Nor does it require any flux; because it is very fusible: which allows us to melt it, and collect it in a mass, without the necessity of fusing likewise the earthy and stony matters in which it is lodged. These matters remain in their first state; and the melted Bismuth descends by its gravity to the bottom of the crucible. No greater degree of heat must be applied, on this occasion, than is necessary to melt the semi-metal: for, as it is volatile, part of it would be dissipated; so that much less thereof would be obtained, if the fire were made too strong, and so much the less as another portion thereof would be converted into a calx. For the same reason, the crucible must be taken out of the furnace as soon as you perceive that all the Bismuth contained in the ore is melted, and that the button doth not increase. The ore of Bismuth may also be treated like the ores of Lead and Tin; that is, it may be reduced into a fine powder, mixed with the black flux, a little Borax, and Sea-salt; put into a close crucible, and fused in a melting furnace. In that case you will find a button of Regulus covered with scoria. By this method rather more Bismuth is obtained; and it is best to make use of it when the ore is poor, because, in such a case, none at all would be obtained by the other process. But here care must be taken to apply at once the degree of fire necessary to melt the mixture: for, if it remain long in the fire, much Bismuth will be lost, on account of the great volatility of this semi-metal, and the facility with which it turns to a calx. Bismuth is pretty frequently found pure in its earthy and stony matrices; and when mineralized it is usually so by Arsenic, which, being still more volatile, flies off in vapours while the ore is melting, provided it be but in a small quantity: if there be much of it, and the ore be smelted by fusing it with the black flux, the Arsenic also is reduced to a Regulus, unites more intimately with the Bismuth, becomes a little more fixed by that union, and increases the quantity of the semi-metallic mass found after the fusion. Though Bismuth be not usually mineralized by Sulphur, that is not because it is incapable of uniting therewith; for, if equal parts of Bismuth and Sulphur be melted together, after the fusion the Bismuth will be found increased near an eighth part, and formed into a mass disposed in needles much like Antimony. When we come to treat of the ore of Arsenic, we shall have occasion to say a good deal more concerning Bismuth and its ore; because these minerals resemble each other very much. Mr. Geoffroy, son of the Academician, hath shewn in a Memoir read before the Academy of Sciences, that there is a great resemblance between Bismuth and Lead. That Memoir, which contains only the beginning of Mr. Geoffroy's course of experiments, proves that the author supports with dignity the glory of his name. It is there demonstrated, by a very great number of experiments, that fire produces the same effects on Bismuth as on Lead. This semi-metal is converted into a calx, into litharge, and into glass, as Lead is; and these productions have the same properties as the preparations of Lead made with the same degree of fire. Bismuth is capable of vitrifying all the imperfect metals, and of carrying them off through the pores of the crucible. So that Gold and Silver may be purified and cupelled by its means, as well as with Lead. You may on this occasion turn to what we have said concerning Lead. PROCESS II. _Bismuth dissolved by Acids. Magistery of Bismuth. Sympathetic Ink._ Into a matrass put Bismuth broken into little bits: pour on it, by little and little, twice as much _aqua fortis_. This Acid will attack the semi-metal briskly, and dissolve it entirely, with heat, effervescence, vapours, and puffing up. The solution will be clear and limpid. _OBSERVATIONS._ Of all Acids the Nitrous is that which best dissolves Bismuth. It is not necessary, on this occasion, to place the phial, in which the dissolution is performed, on a sand-heat, as in most other metallic dissolutions: on the contrary, care must be taken not to pour on all the _aqua fortis_ at once; because it operates with so much activity that the mixture will heave up and run over the vessel. The bare addition of water is sufficient to precipitate the solution of Bismuth. If this solution be mixed with a very large proportion of water, the liquor grows turbid, appears milky, and deposites a precipitate of a very beautiful white. This is that white which the ladies use at their toilets. Water produces this precipitation by weakening the Acid; which probably is incapable of keeping the Bismuth dissolved, unless it have a certain degree of strength. If you would have a Magistery of Bismuth beautifully white, you must perform the dissolution with an _aqua fortis_ that is not tainted with any mixture of the Vitriolic Acid; for this gives the precipitate a dirty white colour, inclining to grey. Several authors advise the use of a solution of Sea-salt, instead of pure water, for precipitating the Bismuth, imagining that this Salt will effect a precipitation here as it does in the cases of Silver and Lead. But Mr. Pott, a German Chymist, who hath published a long dissertation on Bismuth, pretends, on the contrary, that neither Sea-salt, nor its Acid, is capable of precipitating this semi-metal; and that when a precipitation takes place on mixing them with our solution, it is brought about only by means of the water in which those substances are diffused. Bismuth may also be precipitated by the means of Fixed or Volatile Alkalis; but the precipitate is not of so fine a white as when procured by the means of pure water only. If a greater quantity of _aqua fortis_, than that prescribed in the process, be made use of to dissolve the Bismuth, a great deal more water will also be required to precipitate the Magistery; because there will be much more Acid to weaken. This white ought to be well washed, in order to free it from any remainder of acidity; and it should be kept in a bottle well stopped; because the access of the air makes it turn brown, and if any of the Acid be left it will turn it yellow. A solution of Bismuth prepared with the proper quantity of _aqua fortis_, that is, with two parts of the Acid to one of the semi-metal, concretes into little crystals almost as soon as made. _Aqua fortis_ not only acts on Bismuth when separated from its ore, and reduced to a Regulus, but attacks it even in its ore, and likewise dissolves at the same time some portion of the ore itself. With this solution of the ore of Bismuth Mr. Hellot makes a very curious Sympathetic Ink, differing from all that were known before. Mr. Hellot prepares the liquor in the following manner: "He bruises the ore of Bismuth to a coarse powder. On two ounces of this powder he pours a mixture of five ounces of common water with five ounces of _aqua fortis_. He does not heat the vessel till the first ebullitions are over. He then sets it in a gentle sand-heat, and lets it digest there till he sees no more air bubbles rise. When none appear in this heat, he increases it so as to make the solvent boil slightly for a full quarter of an hour. It takes up a tincture nearly of the colour of brown beer. The ore that gives the _aqua fortis_ this colour is the best. He then lets the solution cool, laying the matrass on its side, that he may decant the liquor more conveniently when all is precipitated that is not taken up by the solvent. "The second vessel, into which the liquor is first decanted, he also lays declining, that a new precipitation of the undissolved matters may be obtained; after which he pours the liquor into a third vessel. This liquor must not be filtered, if you would have the rest of the process succeed perfectly; because the _aqua fortis_ would dissolve some of the paper, and that would spoil the colour of your paper. "When this solution, which Mr. Hellot calls the _Impregnation_, is thoroughly clarified by being decanted three or four times, he puts it into a glass bason with two ounces of very pure Sea-salt. The fine white salt made by the sun succeeded best with Mr. Hellot. If that cannot be had, common bay-salt, purified by solution, filtration, and crystallization, may be used instead of it. But as it is rare to meet with any of the sort that is not a little tainted with iron, the white bay-salt is to be preferred. The glass bason he sets in a gentle sand-heat, and keeps it there till the mixture be reduced by evaporation to an almost dry saline mass. "If you desire to save the _aqua regis_, the impregnation must be put into a retort, and distilled with the gentle heat of a sand-bath. But there is an inconveniency, as Mr. Hellot observes, in employing a retort; which is, that, as the saline mass cannot be stirred while it coagulates in the retort, it is reduced to a compact cake of coloured Salt, which presents but one single surface to the water in which it must be dissolved; so that the dissolution thereof takes up sometimes no less than five or six days. In the bason, on the contrary, the saline mass is easily brought to a granulated Salt, by stirring it with a glass rod; and, when thus granulated, it has a great deal more surface; it dissolves more easily, and yields its tincture to water in four hours time. Indeed one is more exposed to the vapours of the solvent, which would be dangerous, if the operation were to be often performed, without proper precautions. "When the bason, or little vessel, containing the mixture of the Impregnation and Sea-salt is heated, the liquor, which was of an orange-coloured red, becomes a crimson red; and, when all the phlegm of the solvent is evaporated, it acquires a beautiful emerald colour. By degrees it thickens, and acquires the colour of a mass of Verdegris. It must then be carefully stirred with the glass rod, in order to granulate the Salt, which must not be kept over the fire till it be perfectly dry; because you run a risk of losing irrecoverably the colour you are seeking. You may be sure you have lost it, if by too much heat the Salt that was of a green colour become of a dirty yellow. If it be once brought to this state, it will continue without changing when cold: but if care be taken to remove it from the fire while it is still green, you will see it gradually grow pale, and become of a beautiful rose colour as it cools. "Mr. Hellot removes it from this vessel, and throws it into another containing distilled rain water: and this second vessel he keeps in gentle digestion till he observes that the powder which falls to the bottom is perfectly white. If, after three or four hours digesting, this powder still continues tinged with a rose colour, it is a proof that water enough was not added to dissolve all the Salt impregnated with the tincture of the solution. In this case, the first tinged liquor must be poured off, and fresh water added, in proportion to the quantity of tinged Salt, that is supposed to remain mixed with the precipitate. "When the ore is pure, and doth not contain a great deal of fusible stone, commonly called _Fluor_ or _Quartz_, an ounce of it generally yields tincture enough for eight or nine ounces of water, and the liquor is of a beautiful colour like that of the lilach or pipe-tree blossom. In order to prove the effect of this tincture, you must write with this lilach-coloured liquor on good well-gummed paper, that does not sink: or you may use it to shade the leaves of some tree or plant, having first drawn the outlines thereof lightly, with China-ink or with a black-lead pencil. Let this coloured drawing, or writing, dry in a warm air. You will perceive no colour while it is cold; but if it be gently warmed before the fire, you will see the writing, or the drawing, gradually acquire a blue or greenish-blue colour, which is visible as long as the paper continues a little warm, and disappears entirely when it cools." The singularity of this sympathetic ink consists in its property of disappearing entirely and becoming invisible, though it be not touched with any thing whatever: and this distinguishes it from all others; which, when once rendered visible by the application of proper means, do not again disappear, or at least not without touching the strokes on the paper with some other liquor. Mr. Hellot made a vast variety of experiments on this subject, and gave his sympathetic ink successively the properties of all others that are known. It follows from Mr. Hellot's experiments, that it is the Acid of Sea-salt which makes this saline _magma_ of a green colour while it is hot: that without this Acid the saline matter continues red; and that the solution of Bismuth-ore in _aqua fortis_ may therefore serve as a touchstone, to discover whether or no any unknown Salt under examination contains Sea-salt, or a portion of the Marine Acid. He also proves, in the Memoirs he hath given in on this subject, that the Nitrous Acid is the true solvent of those ores of Bismuth which contain moreover Smalt and Arsenic. That Acid dissolves all the metallic and colouring matters contained in those ores, sparing nothing but the sulphureous and arsenical portion, the greatest part of which remains precipitated; and from this colouring matter the sympathetic ink derives its virtue. Under the head of Arsenic we shall speak more amply of this matter in Cobalt, or the ore of Arsenic, that gives a blue colour to the sand with which it is vitrified. The Vitriolic Acid does not, properly speaking, dissolve Bismuth. If to one part and an half of this semi-metal you add one part of Oil of Vitriol; distil the whole to dryness; and then lixiviate with water what remains in the retort; the liquor you obtained by this means will be of a reddish yellow colour, but will let nothing fall when mixed with an Alkali: and this shews that the Vitriolic Acid acts only upon the inflammable part of Bismuth, and doth not dissolve its metallic earth. It dissolves the ore of Bismuth more perceptibly than Bismuth itself; because the ore contains, besides the reguline part, an arsenical matter, and a coloured matter, over which perhaps it hath more power. The Acid of Sea-salt attacks and dissolves Bismuth in some small measure, but slowly and with difficulty. That this Acid dissolves a portion of our semi-metal may be proved, by mixing a Fixed or Volatile Alkali with Spirit of Salt in which Bismuth hath lain some time digesting; for then a precipitate falls. But, though the Marine Acid be capable of dissolving Bismuth, it doth not follow that it hath a greater affinity than the Nitrous Acid with this metallic substance, as some Chymists have thought; who imagined that, in the precipitation of the Magistery of Bismuth by a solution of Sea-salt, the Acid of that Salt quits its basis to unite with the Bismuth which it precipitates, as is the case in the precipitations of Lead and of Silver by the same Salt, and that it forms, on this occasion, a _Bismuthum corneum_. On this subject, Mr. Pott observed, 1. that, when only a small quantity of the solution of Sea-salt is mixed with the solution of Bismuth in the Nitrous Acid, no precipitate is formed: now it is certain that when the smallest quantity whatever of Sea-salt is mixed with the solution either of Lead or of Silver, a precipitate is immediately deposited, in a quantity proportioned to that of the Salt used. 2. Mr. Pott, having examined the precipitate of Bismuth thrown down by a solution of Sea-salt, found it not to have the properties of a metallic substance rendered horny: on the contrary, that precipitate being exposed to a very violent fire appeared refractory, and could not be melted. CHAP. III. _Of_ ZINC. PROCESS I. _To extract Zinc from its Ore, or Calamine._ Take eight parts of Calamine reduced to a powder; mix this powder accurately with one part of fine charcoal-dust, previously calcined in a crucible to free it from all moisture: put this mixture into a stone retort coated with lute, leaving a third part of it empty: set your retort in a reverberatory furnace, capable of giving a very fierce heat. To the retort apply a receiver, with a little water in it. Kindle the fire, and raise it by degrees till the heat be strong enough to melt Copper. With this degree of fire the Zinc being metallized will separate from the mixture, and sublime into the neck of the retort, in the form of metallic drops. Break the retort when it is cold, and collect the Zinc. _OBSERVATIONS._ The process here given for smelting Zinc out of Calamine is taken from the Memoirs of the Academy of Sciences at Berlin. The author of it is Mr. Marggraff, a skilful Chymist, whom we have already had occasion to mention under the article of Phosphorus. Till this process was published, we knew no method of obtaining pure Zinc directly from the _Lapis Calaminaris_. Most of the Zinc we have comes from an ore of difficult fusion that is worked at Goslar, and yields, at one and the same time, Lead, Zinc, and another metallic matter called _Cadmia Fornacum_, which also contains much Zinc, as we shall afterwards see. The furnace used for smelting this ore is closed on its fore-side with thin plates or tables of stone, not above an inch thick. This stone is greyish, and bears a violent fire. In this furnace the ore is melted amidst charcoal, by the help of bellows. Each melting takes twelve hours, during which time the Zinc flowing with the Lead is resolved into flowers and vapours, great part of which adheres to the sides of the furnace in the form of a very hard crust of earth. The workmen take care to remove this crust from time to time; for it would otherwise grow so thick at last as to lessen the cavity of the furnace very considerably. There adheres moreover to the fore-part of the furnace, which is formed, as we said before, of thin plates of stone, a metallic matter, which is the Zinc, and is carefully collected at the end of each melting, by removing from this part all the live coals. A quantity of small coal is laid unlighted at the bottom; and on this small coal, by striking the stone plates gently with a hammer, the Zinc is made to fall out of the other matter, known by the Latin name of _Cadmia Fornacum_, among which it appears fixed in a radiated form. To this other matter we may properly enough give the name of _Furnace-Calamine_. The Zinc falls in the form of a melted metal, all on fire, and in a bright flame. It would soon be entirely burnt and reduced to flowers, as we shall see, if it were not extinguished, and easily cooled and fixed, by being hid under the unlighted small-coal placed below on purpose to receive it. The Zinc adheres to the fore-part of the furnace preferably to any other, because that being the thinnest is therefore the coolest: and, in order further to promote its fixing on this part, they take care to keep the thin stone plates cool during the operation, by throwing water on them. Hence it appears, that Zinc is not extracted from its ore by fusion and the precipitation of a Regulus, like other metallic substances. This is owing to the great volatility of our semi-metal, which cannot, without subliming, bear the degree of fire necessary to melt its ore. It is at the same time so combustible, that a great part of it rises in flowers which have not the metalline form. Mr. Marggraff provides against these inconveniences by working the ore of Zinc in close vessels. By this means he prevents the Zinc from taking fire, and being converted into flowers; so that it sublimes in its metalline form. The water in the recipient serves to receive and cool the drops of Zinc that may be forced quite over the helm. As the operation requires a most violent fire, these drops must needs issue exceeding hot, and, without this precaution, break the recipient. Mr. Marggraff by the same process extracted Zinc out of the Furnace-Calamine procured from ores containing Zinc; from Tutty, which is a sort of furnace-calamine; from the flowers and from the calx of Zinc; and from the precipitate of White Vitriol; all of them matters known to be Zinc, that wanted nothing but the phlogiston to give it a semi-metalline form, and from which nevertheless no body could ever before him procure any Zinc. Mr. Marggraff observes, that the Zinc obtained by his process bears being flatted under the hammer into pretty thin plates; which the common Zinc will not do. The cause of this probably is, that the Zinc obtained by his method is more intimately combined with the phlogiston, and contains a greater quantity thereof, than that which is procured in the ordinary way. PROCESS II. _To sublime Zinc into Flowers._ Take a very deep, large crucible: place it in a furnace, so that it may stand inclining in an angle of forty-five degrees nearly. Throw some Zinc into it, and kindle a fire in the furnace somewhat stronger than would be necessary to keep Lead in fusion. The Zinc will melt. Stir it with an iron wire, and there will appear on its surface a very bright white flame: two inches above this flame a thick smoke will be formed, and with this smoke exceeding white Flowers will rise, and remain some time adhering to the sides of the crucible, in the form of a very fine light down. When the flame slackens, stir your melted matter again with the iron wire: you will see the flame renewed, and the flowers begin again to appear in greater abundance. Go on thus till you observe that the matter will not flame, nor any more Flowers rise. _OBSERVATIONS._ Zinc takes fire very easily as soon as it is affected by a certain degree of heat; which proves, that in the composition of this semi-metal there is very much phlogiston, united but slightly with its metallic earth. The Flowers into which Zinc resolves, during its combustion, are of a perfectly singular nature, and differ greatly from all the other productions obtainable out of metallic substances. They may be considered as the very calx of Zinc, or its metallic earth robbed of its phlogiston, and sublimed during the combustion of this semi-metal, being probably carried up by the phlogiston in flying off. For these Flowers, when once sublimed, are afterwards exceedingly fixed: they sustain the greatest violence of fire without rising, and are converted by it into a sort of glass. None of the methods hitherto employed, for restoring to the Flowers of Zinc their metalline form, have ever succeeded. When treated like other metalline calces in a crucible, with every kind of inflammable matter, and different sorts of reducing fluxes, they never can be re-metallized: they only melt with the flux, and produce a kind of Glass. Mr. Marggraff indeed, as mentioned before, obtained Zinc from these Flowers, by treating them as he did Calamine in a retort with charcoal-dust: but as the Flowers often carry up with them little particles of undecomposed Zinc, there still remains some doubt concerning the reduction of these Flowers, even by this method. If the crucible, into which you put the Zinc to be converted into Flowers, instead of being left open, as directed, be covered with another crucible inverted, the two vessels luted together, placed in a melting furnace, and a strong fire immediately kindled and kept up for about half an hour; you will find, when the vessels are cold, that all the Zinc hath left the lower crucible, and is sublimed into the upper one, in its metalline form, without suffering any decomposition. This experiment proves, that Zinc, to be converted into Flowers, must necessarily be set on fire and burnt. As it cannot burn in close vessels, any more than other combustible bodies, and as it is volatile, it sublimes without suffering any decomposition. Regulus of Antimony and Bismuth may be sublimed in the same manner; but not so easily as Zinc, which is still more volatile than those other semi-metals. It is necessary to stir the Zinc in fusion from time to time with an iron wire, when you intend to convert it into Flowers: for there forms on its surface a grey crust that obstructs its deflagration, and beneath which it is gradually converted into a clotted calx. In order, therefore, to promote the rising of the flowers, care must be taken to break this crust, as oft as it begins to form. On this there immediately appears a very bright white flame: two inches above the flame is seen a thick smoke, and with this smoke very white Flowers rise, that continue some time adhering to the inside of the crucible, in the form of a fine down. M. Malouin, who, in sundry Memoirs on Zinc, hath endeavoured to discover what resemblance there is between this semi-metal and Tin, tried to calcine Zinc in the same manner as Tin; but found it somewhat more difficult. Zinc, while it is not in fusion, doth not calcine; but it begins to turn to a calx the moment it begins to melt. M. Malouin, having repeated the fusion of Zinc a great number of times, by that means collected at last a quantity of the calx of this semi-metal, resembling other metalline calces. This calx of Zinc he melted in a crucible with animal fat; whereby the calx was re-metallized, and reduced to Zinc. There is great reason to believe that the calx of Zinc made by this method is not so much burnt as the Flowers, and that it still contains a portion of phlogiston. PROCESS III. _To combine Zinc with Copper. Brass. Prince's Metal_, &c. Pound one part and an half of Calamine, and an equal quantity of charcoal: mingle these two powders together, and moisten them with a little water. Put this mixture into a large crucible, or some other earthen vessel that will bear a melting heat. Amongst and over this mixture put one part of very pure Copper in thin plates, and then put fresh charcoal-dust over all: cover the crucible; set it in a melting furnace; put coals all round it, and let them kindle gradually. Raise the fire so as to make the crucible very red-hot. When you observe that the flame hath acquired a purple or bluish-green colour, uncover the crucible, and dip into it an iron wire, to examine whether or no the copper be in fusion under the charcoal-dust. If you find it is, moderate the force of the fire a little, and let your crucible remain in the furnace for a few minutes. Then take it out and let it cool: you will find your Copper of a gold colour, increased in weight a fourth, or perhaps a third part, and yet very malleable. _OBSERVATIONS._ The _Lapis Calaminaris_ is not the only substance with which Copper may be converted into brass: all other ores containing Zinc, the Furnace-Calamine that sublimes where such ores are worked, Tutty, Zinc in substance, may be substituted for it, and, like it, will make very fine Brass; but, in order to succeed, sundry precautions are necessary which we shall now lay before you. This process is a sort of cementation: for the Calamine doth not melt; only the Zinc is converted into vapours, and then combines with the Copper. On this the success of the operation partly depends, as it is the means of the Copper's preserving its purity and malleability; because the other metallic substances that may be united with the ore of Zinc, or with the Zinc itself, not having the same volatility, cannot be reduced to vapours. If you are apprised that the Calamine, or other ore of Zinc used on this occasion, is contaminated with a mixture of any other metallic matter, you must mingle luting earth with the charcoal-dust and the matter containing the Zinc; make it into stiff paste with water; of this make a bed at the bottom of your crucible, and ram it hard down; lay the Copper plates thereon, cover them with charcoal-dust, and then proceed as before. By this means when the Copper melts it cannot fall to the bottom of the crucible, nor mix with the ore; but is borne up by the mixture, and cannot combine with any thing but the Zinc, that rises in vapours, and, passing through the lute, fixes in the Copper. _Lapis Calaminaris_, or other ore of Zinc, may also be purified before it be used for making Brass; especially if adulterated with Lead ore, which is often the case. For this purpose the ore must be roasted in a fire strong enough to give a small degree of fusion to the leaden matter; which will thereby be reduced into larger, heavier, and tougher masses. The most subtile particles are dissipated in the torrefaction, together with some of the Calamine. The Calamine, on the contrary, is by roasting made more tender, lighter, and much more friable. When it is in this condition, put it into a washing tray or van; dip the tray in a vessel full of water, and bruise the matter it contains. The water will carry off the lightest powder, which is the Calamine, and leave nothing at the bottom of the tray but the heaviest substance; that is the leaden matter, which is to be rejected as useless. The powder of the Calamine will settle at the bottom of the vessel, where, after pouring off the water, it may be found, and used as above directed. In this operation the charcoal-dust serves to prevent both the Copper and the Zinc from being calcined: and for this reason, when you work on a great quantity of materials at once, it is not necessary to use so much charcoal-dust, in proportion, as when you work but on a small quantity; because, the greater the mass of metal, the less easily will it calcine. Though the Copper melts in this operation, yet it is far from being necessary to apply such a strong fire as Copper usually requires to melt it: for the accession of the Zinc, on this occasion, communicates to it a great deal of fusibility. The increase of its weight is also owing to the quantity of Zinc combined with it. Copper acquires still another advantage by its association with this semi-metal; for it remains longer in the fire without calcining. Brass well prepared ought to be malleable when cold. But in whatever manner it be made, and whatever proportion of Zinc there be in it, it is constantly found quite unmalleable when red-hot. Brass melted in a crucible, with a fierce heat, takes fire almost like Zinc, and from its surface many white flowers ascend, dancing about in flakes like the flowers of Zinc. They are indeed the flowers of Zinc, and the flame of Brass urged by a strong fire is no other than the flame of the Zinc that is united with the Copper, and at that time burns. If Brass be thus kept long in fusion it will lose almost all the Zinc it contains. It will also lose much of its weight, and its colour will be nearly that of Copper. It is therefore necessary, towards performing this operation aright, to seize the moment when the Copper is sufficiently impregnated with Zinc, when it hath acquired the most weight and the finest colour, with the least detriment to its ductility, that is possible, and that instant to put out the fire; because, if the Copper be left longer in fusion, it will only lose the Zinc already united with it. Skill acquired by much practice, and an acquaintance with the particular Calamine employed, are necessary to guide the artist surely through this operation; for there are very considerable differences between the sundry ores of Zinc. Some of them contain Lead, as was said above, and in others there is Iron. When these heterogeneous metals come to be mixed with the Copper, they do indeed augment its weight, but they render it at the same time pale, and make it very harsh. Some Calamines require to be roasted before they can be used for this purpose, and in the torrefaction emit vapours of a Volatile Alkali, succeeded by vapours of a Sulphureous Spirit: others exhale no vapours while roasting, and may be employed without any antecedent preparation. These different qualities must evidently produce great differences in the operation. Brass may also be made as Prince's metal and other imitations of Gold are actually made, by using Zinc in substance, instead of the ores that contain it. But these compositions have not, when cold, the ductility of Brass prepared with _Lapis Calaminaris_, because Zinc is seldom pure, or free from a mixture of Lead. Perhaps also the different manner in which the Zinc unites with the Copper may contribute to this variation. To obviate this inconvenience, the Zinc must be refined from all alloy of Lead. The property of being indissoluble by Sulphur, which this semi-metal possesses, points out a very practicable method of doing it. The Zinc must be melted in a crucible, and stirred briskly with a strong iron wire, while tallow and mineral Sulphur are alternately projected upon it; but so that the quantity of Sulphur may greatly exceed that of the tallow. If the Sulphur do not burn entirely away, but form a kind of scoria on the surface of the Zinc, it is a sign that your semi-metal contains Lead. In this case you must continue throwing in more Sulphur, and keep stirring the Zinc incessantly, till you perceive that the Sulphur ceases to unite any more with a metallic substance, but burns freely on the surface of the Zinc. The semi-metal is then refined, because the Sulphur, which cannot dissolve it, unites very readily with the Lead, or other metallic substance, contained in it. If Zinc thus refined be mixed with pure Copper, in the proportion of a fourth or a third part, and the mixture be kept in fusion and constantly stirring for some time, the Brass produced will be as ductile, when cold, as that made by cementation with the _Lapis Calaminaris_. With regard to Prince's metal, and other imitations of Gold, they are made either with Copper or Brass re-combined with more Zinc. As it is necessary, for giving them a fine golden colour, to mix with them other proportions of Zinc than that acquired to make Brass only, they are generally much less ductile. In 1725, M. Geoffroy gave a Memoir on this subject in which he examined the effects of incorporating both Copper and Brass with Zinc, from a small to a very large quantity. PROCESS IV. _Zinc dissolved in the Mineral Acids_. Weaken concentrated Oil of Vitriol by mixing with it an equal quantity of water. Into a matrass put the Zinc you intend to dissolve, first broken to small pieces. Pour on it six times its weight of the Vitriolic Acid, lowered as above directed, and set the matrass in a sand-bath gently heated. The Zinc will dissolve entirely, without any sediment. The Neutral Metallic Salt resulting from this dissolution shoots into crystals, which go by the name of _White Vitriol_, or _Vitriol of Zinc_. _OBSERVATIONS_. Though Zinc be soluble in all the Acids, and when combined with those Acids exhibits some uncommon phenomena, yet M. Hellot is the first that ever gave a particular account of what happens in those dissolutions: so that all we have to say on this head is extracted from that Gentleman's Memoirs. If a solution of Zinc in the Vitriolic Acid, prepared according to the directions in the process, be distilled from a retort placed in a sand-bath with a graduated heat, almost half the liquor presently comes over in pure phlegm. A small quantity of a Sulphureous Acid Spirit rises next. A greater force of fire is now requisite: the retort must therefore be removed into a reverberatory, and the distillation continued with a naked fire. On the first impression of this heat an odour of Liver of Sulphur discovers itself, which becomes sharp and suffocating towards the end of the distillation. In two hours time white vapours begin to appear, as in the rectification of common Oil of Vitriol. If the receiver be then shifted, you will obtain an Oil of Vitriol, in quantity about the eighteenth part of the whole used in the distillation, which, though sulphureous, is yet so concentrated, that, if a few drops thereof be poured into a weak Oil of Vitriol, they fall to the bottom with as much noise as if they were so many bits of red-hot iron, and heat this Oil of Vitriol as much as common Oil of Vitriol heats water. At the bottom of the retort there remains a dry, white, crystalline, saline mass, exceeding in weight the Zinc that was dissolved, about a twelfth part of the whole weight of the liquor. The increase of its weight is owing to a portion of the Vitriolic Acid that remains concentrated in the Zinc, and could not be expelled by the fire. This portion of Acid adheres to it most tenaciously: for, though M. Hellot kept the retort containing it during two whole hours in so violent a fire that the vessel began to melt, the smallest vapour did not rise from it. This saline _caput mortuum_ is in the form of needles, much like the Sedative Salt. It is caustic, grows considerably hot when water is poured on it, and gives in the air, but slowly. Spirit of wine, digested with this Salt for eight or ten days, acquires the same smell as that which is mixed with concentrated Oil of Vitriol in preparing Æther. Zinc is dissolved by the Nitrous and Marine Acids, much in the same manner as by the Vitriolic; except that the Marine Acid does not touch a black, spungy, rarefied matter, which it separates from the Zinc. M. Hellot found upon trial that this matter is not Mercury, and that it cannot be reduced to a metallic substance. That ingenious Chymist distilled likewise Solutions of Zinc in the Nitrous and Marine Acids. There came over at first, as there did from the solution made by the Vitriolic Acid, an aqueous, and then an acidulated liquor. At last, by exciting the fire with great violence, towards the end of the distillation, he obtained a small quantity of the Acid that hath been employed in the dissolution: but the small portion of Acid thus obtained was exceeding strong; and the quantity of the Nitrous much more considerable than that of the Marine Acid. A solution of Zinc in the Marine Acid, being distilled to dryness, yields a Sublimate on applying a violent heat to it. All the Acids dissolve with ease, not only Zinc, but its Flowers also; and that nearly in the same quantity, and with almost all the same phenomena. M. Hellot, observing that the residues of most of the solutions of Zinc have a great resemblance with its flowers, is of opinion that this semi-metal may be reduced, by the means of solvents, to the same state into which it is brought by the fire when sublimed in Flowers. CHAP. IV. _Of_ ARSENIC. PROCESS I. _To extract Arsenic from its Matrices. Zaffre or Smalt._ Powder some Cobalt, white Pyrites, or other Arsenical matters. Put this powder into a retort with a short wide neck, leaving a full third thereof empty. Set your retort in a reverberating furnace; lute on a receiver; heat your vessel by degrees, and increase the fire till you see a powder sublime into the neck of the retort. Keep up the fire in this degree as long as the sublimation continues: when this begins to slacken, raise your fire, and make it as strong as the vessels will bear. When nothing more ascends, let it go out. On unluting the vessels, you will find in the receiver a little Arsenic in the form of a fine light _farina_. The neck of the retort will be full of white flowers, not quite so fine, some of which will appear like little crystals; and if a good deal of Arsenic be sublimed, a ponderous matter, like a white, semi-transparent glass, will be found adhering to that part of the neck of the retort which is next its body. _OBSERVATIONS._ Arsenic is a metallic substance still more volatile than Zinc; so that it cannot be separated from the matters with which it is mixed otherwise than by sublimation. It is proper, however, to take notice, that it is not naturally in a metallic form, and that, properly speaking, the whole Sublimate obtained from Cobalt, as above directed, is nothing but a metallic calx, that cannot be brought to the form and gloss of a metal, till it be worked up with fatty matters, as we shall shew in its place. This calx is of a very singular nature, and differs from every other metallic calx, in that this is volatile, and all the rest extremely fixed; even those procured from the semi-metals: for the Flowers of Zinc, which are justly considered as a calcined Zinc, though obtained by a sort of sublimation, are not for all that of a volatile nature, but rather exceedingly fixed; seeing they are capable of sustaining the most violent fire, and melt instead of subliming. Arsenic, on the contrary, is not only extracted from its ore by sublimation, but when once sublimed continues to be volatile, and flies off in vapours as soon as it is exposed even to a moderate degree of heat. This metallic matter, before it is combined with the phlogiston, is called _White Arsenic_, or plain _Arsenic_: it acquires the title of _Regulus of Arsenic_ when it is united with the phlogiston, and glitters like a metal. Though Arsenic be volatile, yet it requires a pretty strong fire to separate it from the minerals containing it, especially in close vessels; because it adheres very close to earthy and vitrifiable matters. This adhesion is so firm, that, when thus combined, it is capable of bearing a melting heat, and vitrifies with metallic calces, and other fusible matters. On this account it is impossible to extract from Cobalt, or other Arsenical matters, all the Arsenic they contain by working them only in close vessels. If such matters are to be freed from all their Arsenic, you must, after you have extracted all they will yield by distillation, put them into a crucible, and set it uncovered in the midst of a strong fire. Many Arsenical vapours will still rise; and care must be taken to stir the contents of the crucible frequently with an iron rod, to facilitate the discharge of the remaining Arsenic. It often happens that the Arsenic, obtained from minerals by sublimation, is not very white, but of a lighter or darker grey colour. This is owing to some particles of inflammable matter, from which Arsenical minerals are seldom quite free. A very small quantity of phlogiston is sufficient to deprive much Arsenic of its whiteness, and to give it a grey colour. But when fouled in this manner, it may easily be brought to its due degree of whiteness: it need only be sublimed once more, after mixing it with some substance on which it doth not act; Sea-salt, for instance. If the matters from which Arsenic is extracted contain Sulphur also, as some pyrites do, the Arsenic sublimes with much less heat, than when it is united with earthy matters only; because it combines with the Sulphur, wherewith it hath a great affinity, and the Sulphur serves to separate the Arsenic, by this interposition, from the earth. In consequence hereof, Sulphur may be employed to extract Arsenic out of the earths in which it is fixed. In this case, the Sulphur changes the colour of the Arsenic, which it makes of a lighter or deeper yellow, or even red, in proportion to the quantity there is of it, and to the degree of fire that hath acted on both together. The consistence of Arsenic is different, according to the degree of heat applied in subliming it. If the Arsenical vapour meet with a cold place, it gathers there in the form of a powder, as the Flowers of Sulphur do: this is the case with that which falls into the receiver in distilling it. But if it be stopped in a hot place, and cannot escape from that heat, it condenses into a heavy, compact, semi-transparent body, having undergone the first degree of fusion. Yet it cannot be perfectly melted, so as to flow like other fused matters: not that it is refractory; for, on the contrary, the degree of heat in which it begins to melt is very moderate, and it is in its own nature very fit to promote the fusion of refractory matters: but the reason is this; it is necessarily converted into vapours by the degree of heat necessary to fuse it, and these vapours burst the vessels, if they find no vent. Arsenic made yellow by a mixture of Sulphur, which is also called _Orpiment_, is reducible to the form of a solid Sublimate with more ease; because it is alloyed with a twentieth, or perhaps a tenth part, of its weight of Sulphur, which renders it more fusible. Red Arsenic, which contains still more Sulphur, melts also more easily. It then becomes of a transparent red, like a ruby: and hence, when it is in this form, it is called _Ruby of Arsenic_. When a combination of Sulphur and Arsenic is wanted, it is better to mingle and distil together such minerals as contain Sulphur and Arsenic, the white and the yellow pyrites, for instance, than to mingle pure Arsenic with pure Sulphur: for the great volatility of these two substances is a hindrance to their uniting; whereas, when combined with other matters, they are capable of sustaining a much greater degree of heat, which favours and promotes their union. Those who work by the grate do not extract Arsenic out of Cobalt by distillation: they throw the ore mixed promiscuously with wood and charcoal into a great furnace, from whence a flue carries the vapours into a long winding passage, across which beams of wood are fixed at proper distances from each other. The Arsenical vapours being conducted into this passage, adhere both to the sides thereof and to the joists that lye across it. The fuliginous parts of the combustible matters being lighter ascend higher, and go out through a chimney at the farther end of this passage. The Arsenic sublimed by this method is not white, but of a grey colour; owing to the inflammable matter of the wood and charcoal with which the ore is torrefied. When all the Arsenic the Cobalt will yield is thus separated, the earthy fixed matter left behind is mixed with divers fusible matters and vitrified, and produces a glass of a beautiful blue colour. It is called _Smalt_. This glass is to be prepared in the following manner. Take four parts of fine fusible sand, an equal quantity of any Fixed Alkali perfectly depurated, and one part of Cobalt from which the Arsenic hath been sublimed by torrefaction. Pulverize these different substances very finely, and mix them thoroughly together; put the mixture into a good crucible, cover it, and set it in a melting furnace. Make a strong fire, and keep it up constantly in the same degree for some hours. Then dip an iron wire into the crucible; to the end of which a glassy matter will stick, in the form of threads, if the fusion and vitrification be perfect. In this case take the crucible out of the fire; cool it by throwing water on it, and then break it. You will find in it a glass, which will be of an exceeding deep blue, and almost black, if the operation hath succeeded. This glass, when reduced to a fine powder, acquires a much brighter and more lively blue colour. If you find after the operation that the glass hath too little colour, the fusion must be repeated a second time, with twice or thrice the quantity of Cobalt. If, on the contrary, the glass be too dark, less Cobalt must be used. Instead of the mixture here prescribed you may employ a ready-made glass, providing it be white and fusible. But as glass is always hard to melt, and as the mixing Cobalt with it renders it still more refractory, therefore though an Alkaline Salt be one of the ingredients in its composition, it is proper to promote the fusion, by mixing therewith calcined wine-lees, in the quantity of one third part of the weight of the Cobalt. In order to make the assay of a particular Cobalt, with a view to know what quantity of blue glass it will yield, it is necessary to perform the operation in the manner here set down; a great deal of time and trouble may be saved by melting one part of Cobalt with two or three parts of Borax. This Salt is very fusible, and turns, when melted, into a substance which, for a time, possesses all the properties of glass. In this trial the glass of Borax will be nearly of the same colour as the true glass, or Smalt, made with the same Cobalt. The ores of Bismuth, as well as Cobalt, yield a matter that colours glass blue; nay, the Smalt made with these ores is more beautiful than that procured from the ore of pure Arsenic. Some Cobalts yield both Arsenic and Bismuth. When such Cobalts are used, it is common to find at the bottom of the crucible a little button of metallic matter, which is called _Regulus of Cobalt_. This Regulus is a sort of Bismuth, generally adulterated with a mixture of ferruginous and arsenical parts. The heaviest and most fixed Flowers of Arsenic, procured from Cobalt, have likewise the property of giving a blue colour to glass. But this colour is faint: it is owing to a portion of the colouring matter carried up along with the Arsenic. These Flowers may be made an ingredient in the composition of blue glass, not only because of the colouring principle they contain, but also because they greatly promote fusion; Arsenic being one of the most efficacious fluxes known. In short, all those blue glasses, or Smalts, contain a certain quantity of Arsenic; for a portion of this semi-metal always remains united with the fixed matter of the Cobalt, though roasted for a long time, and in a very hot fire. The portion of Arsenic that is thus fixed vitrifies with the colouring matter, and enters into the composition of the Smalt. The blue glass made with the fixed part of Cobalt hath several names, according to the condition in which it is. When it hath undergone the first imperfect degree of fusion only it is called _Zaffre_. It takes the name of _Smalt_ when perfectly vitrified: and this again being pulverized is called _Powder-blue_, or, if finely levigated, _Blue Enamel_; because it is used in enamelling, as well as in painting earthen ware and porcelain. PROCESS II. _To separate Arsenic from Sulphur._ Powder the yellow or red Arsenic which you intend to separate from its Sulphur. Moisten this powder with a Fixed Alkali resolved into a liquor. Dry the mixture gently; put it into a very tall glass cucurbit, and fit on a blind-head. Set this cucurbit in a sand-bath; warm the vessels gently, and increase the fire by degrees, till you perceive that no more Arsenic sublimes. The Arsenic, which before was yellow or red, rises into the head partly in white flowers, and partly in a compact, white, semi-transparent matter, which looks as if it were vitrified. The Sulphur combined with the Fixed Alkali remains at the bottom of the cucurbit. _OBSERVATIONS._ A Fixed Alkali hath more affinity than any metallic substance with Sulphur: so that it is not surprising Sulphur should be separated from Arsenic by its interposition. Yet there is an inconvenience attends the use of it: for it hath a great affinity with the Arsenic also, and so always retains some part thereof, which continues fixed with it. For this reason care should be taken not to mix, with sulphurated Arsenic, a greater quantity of Alkali than is necessary to absorb the Sulphur it contains. Nothing, however, but experience and repeated trials can teach us the exact quantity of Alkali that ought to be employed; because the quantity of Sulphur that may be contained in yellow or red Arsenic is indefinite. The vessel ought to be tall, that the upper part of the head, where the Arsenical particles condense, may be the less exposed to heat. Towards the end of the operation the fire must be strongly excited, so as to make the sand red-hot; because the last portions of Arsenic that rise are strongly retained by the Fixed Alkali. Arsenic that is grey or blackish may be depurated and whitened by the same means; because a Fixed Alkali absorbs the phlogiston likewise with great avidity. Mercury, as well as a Fixed Alkali, is an excellent additament for separating Arsenic from Sulphur. If you will use it for that purpose, reduce the sulphurated Arsenic to a very fine powder, by rubbing it a long time in a glass mortar; when it is well pulverized, let a few drops of Mercury fall upon it, by squeezing it through chamoy, and continue the trituration. The yellow or red colour of the Arsenic will insensibly change, and gradually grow darker as the Mercury incorporates with it. When the Mercury is perfectly killed, add a little more of it than you did the first time, and in the same manner: continue to triturate till it disappear; and thus go on adding more and more till the Mercury you add remain quick, and you can kill no more of it. Neither the red nor the yellow colour will then appear in the mixture; which will be grey, if it contain but a little Sulphur, and black, if a great deal. Put this mixture into a very tall glass cucurbit; fit on a blind-head; set it in a sand-bath, and bury it in the sand as far as the contained mixture reaches. Heat the vessels, and, during the whole operation, keep up a degree of fire a little weaker than that required for subliming Cinabar. White Arsenical Flowers will adhere to the upper part of the head, amongst which will be some beautiful crystals of Arsenic; and underneath them you will find some Cinabar sublimed, but not entirely free from Arsenic. If you desire to have your Cinabar and your Arsenic purer, and more unmixed with each other, separate the upper sublimate, which is Arsenical, from the lower, which consists chiefly of Cinabar. Powder each of them coarsely, and sublime them separately each in a different cucurbit. On this occasion the Mercury separates the Sulphur from the Arsenic, because it hath a greater affinity than Arsenic with that mineral. It is not the only metallic substance of this character: for, as hath been shewn, there are several others that have a greater affinity than Mercury with Sulphur, being able to decompose Cinabar by their interposition. Yet those metallic substances must not be substituted for Mercury in the present operation: because there is none of them but hath at the same time a very great affinity with Arsenic, or even as strong an one as they have with Sulphur; whereas Mercury will by no means unite with Arsenic. This method of separating Arsenic from Sulphur hath two advantages over that in which a Fixed Alkali is the medium. The first is, that by this means all the Arsenic contained in the mixture is extracted out of it; and the second, that, as Mercury doth not absorb Arsenic, we are not put to the trouble of groping out, as it were, by trials the quantity necessary to be added; and that, though more be added than is necessary to absorb all the Sulphur, it will be of no prejudice to the operation. But then it is attended with the inconvenience of being much more tedious and more laborious than the other. For, in the first place, it requires previously a very tiresome trituration, in order to procure an union between the Sulphur and the Mercury, and so to form an Æthiops; without which the Mercury and the sulphurated Arsenic will sublime separately, so that no decomposition will be effected. Secondly, though the Mercury be sufficiently united with the Sulphur of the Arsenic by the long trituration that precedes the sublimation, this doth not prevent, as we took notice above, the sublimed Arsenic and Cinabar from being in some measure blended together; so that each requires a second separate sublimation to render it very pure. These inconveniencies cause a Fixed Alkali to be used preferably to Mercury; the loss of a small quantity of the Arsenic, which remains united with the Alkali, being little regarded; as that metallic substance is neither scarce nor precious. When Arsenic is united with a great quantity of Sulphur, it may be freed from a part thereof without the intervention of any third body: it is sufficient for the purpose to sublime it with a very gentle fire, increased by insensible degrees. The most sulphureous part ascends first; what rises afterwards is more Arsenical, and less sulphureous; and the last flowers of all are pure Arsenic, or at least nearly so. PROCESS III. _To give Arsenic the Metalline Form. Regulus of Arsenic._ Take two parts of white Arsenic in fine powder, one part of the black flux, half a part of Borax, and as much clean iron filings. Rub the whole together, in order to mix them thoroughly. Put this mixture into a good crucible, and over it put Sea-salt three fingers thick. Cover the crucible; set it in a melting furnace; and begin with a gentle fire to heat the crucible equally. When arsenical vapours begin to ascend from the crucible, raise the fire immediately so as to melt the mixture. Examine whether or no the matter be thoroughly melted, by introducing an iron wire into the crucible; and if the fusion be perfect, take the crucible out of the furnace. Let it cool; break it; and you will find in it a Regulus of a white and livid metallic colour, very brittle, scarcely hard, but rather friable. _OBSERVATIONS._ White Arsenic is, as hath been said, a metallic calx; and consequently wants no more, in order to its acquiring the metalline properties, than to be combined with the phlogiston: this is effected by the operation before us. The Iron added doth not serve here, as in making the Regulus of Antimony, to precipitate the Regulus of Arsenic, by separating it from some other substance with which it was united: on this occasion it does nothing but join the Regulus of Arsenic, to which it gives solidity and consistence. This is the only reason of its being made an ingredient in the mixture; as the Regulus of Arsenic, without it, would have such a tender consistence, that it could scarce be handled without falling asunder into little bits. The Iron procures a further advantage in this process; which is, that it prevents a great quantity of Arsenic from being lost in vapours: for the Arsenic, with which it combines, is restrained, and, in some measure, fixed by it. Copper may be substituted for Iron, and procures the same advantages. It is very necessary to remove the crucible from the fire as soon as the matter is melted, and indeed to cool it as expeditiously as possible, to prevent the Arsenic from flying off in vapours: for, when once the Regulus is formed, the proportion of Arsenic, with respect to that of the metal mixed with it, is continually lessening while it stays in the fire; so that, after some time, there will be left in the crucible, not a Regulus of Arsenic, but only Iron or Copper, alloyed with a little Arsenic. On this occasion the Copper turns white, and assumes the colour of Silver; but it soon tarnishes in the air. It is easy to perceive, by what hath been said, that the Regulus of Arsenic made according to this process is never pure, but contains always a considerable quantity of Iron or Copper, whatever precautions be used: but it is difficult to avoid this inconvenience, for the reasons above assigned; and if we attempt to fuse Arsenic alone, with reducing fluxes, the greatest part thereof is dissipated in vapours, long before the very flux begins to melt: and that part of it, which is found metallized, is not collected in one mass at the bottom of the crucible, as in other metallic reductions; but in small particles, dispersed and mixed among the scoriæ. There are nevertheless several expedients for obtaining a Regulus of Arsenic absolutely pure, and unalloyed with any metallic substance. First: into a little low cucurbit, covered with a blind-head, put Regulus of Arsenic made with Iron or Copper; set this cucurbit in a sand-bath; heat it till the sand begins to grow red, and you will see part of the Regulus sublime into the head, still retaining its metalline splendour. The portion of Regulus thus sublimed is pure Arsenic, or at least contains but a very small portion of the adventitious metal, which may have been carried up with it. What is left in the bottom of the cucurbit is the metal that was added, still containing a little Arsenic, which continues obstinately fixed with it, and which the violence of fire is unable to force away from it in close vessels. Secondly: mix your Arsenic in equal parts with the black flux; put the mixture into such a cucurbit as that last mentioned; and apply to it the strongest degree of heat that can be procured by a sand-bath; arsenical flowers, of a blackish grey colour, will first sublime into the head, and after them a Regulus of Arsenic of a white metalline colour, which is pretty glossy, but tarnishes very soon in the air. This Regulus hath no solidity: it is exceedingly friable; but it is pure. Thirdly: I have also made a Regulus of pure Arsenic by another method, which produces a much greater quantity thereof, with a much smaller degree of heat. For this purpose I powder the Arsenic, and mix with it any Fat Oil; so that the mixture may be like a liquid paste: this paste I put into a little phial of thin glass, like one of those used by apothecaries; I set this phial in a sand-bath, and gradually heat it, till the bottom of the pot containing the sand begin to be red. Part of the Oil first rises out of the phial in vapours, which must be suffered to pass off. After this the upper part of the phial is gradually lined, on the inside, with a glittering metallic crust, which makes it look like a quick-silvered glass. This crust is the Regulus of Arsenic. When it begins to sublime, the mouth of the phial must be slightly stopped with a bit of paper, and the heat increased a little, till you see that nothing more rises. If you break the bottle after the operation, you will find its upper part crusted over with a coat of Regulus, thicker or thinner in proportion to the quantity of Arsenic employed. The Regulus is in a mass, of a beautiful brilliant colour, which to me seems to stand the air better than that of any Regulus made by other methods; probably because of the great quantity of fat matter with which it is united, and by which it is defended. This Regulus of Arsenic is absolutely pure, and a much greater quantity thereof is obtained, by this method, than by treating it with the black flux; because the Arsenic is much sooner and more easily combined with the inflammable matter: and hence it comes to pass that part of the Arsenic doth not rise at first in grey flowers, as in operating with the black flux. Moreover, by our process, all the Arsenic is sublimed in Regulus: whereas, when the black flux is employed, a pretty considerable part of the Arsenic unites with the alkaline part of the flux, and remains fixed therewith. In our operation there is nothing left at the bottom of the phial, except an oily, light, but very fixed coal. Regulus of Arsenic, in whatever manner made, may be easily reduced into white, crystalline Arsenic, by the means of a Fixed Alkali, or of Mercury, applied in the same manner as for separating Arsenic from Sulphur. PROCESS IV. _To distil the Nitrous Acid by the interposition of Arsenic. Blue_ Aqua Fortis. _A new Neutral Salt of Arsenic._ Pulverize finely any quantity you please of refined Salt-petre. Mix it accurately with an equal weight of white crystalline Arsenic, well pulverized, or else with very white and very fine flowers of Arsenic. Put this mixture into a glass retort, leaving one half of it empty. Set your retort in a reverberating furnace; apply a receiver having a small hole drilled in it, and containing a little filtered rain-water; lute the receiver to the retort with stiff lute. Begin with putting two or three small live coals in the ash-hole of the furnace, and replace them with others when they are ready to go out. Go on thus warming your vessels by insensible degrees, and put no coals in the fire-place, till the retort begin to be very warm. You will soon see the receiver filled with vapours of a dark-red, inclining to a russet colour. With a bit of lute stop the little hole of the receiver. The vapours will be condensed in the water of this vessel, and give it a very fine blue colour, that will grow deeper and deeper as the distillation advances. If your Salt-petre was not very dry, some drops of Acid will also come over, and falling from the nose of the retort mix with the water in the receiver. Continue your distillation, increasing the fire little by little as it advances, but exceeding slowly, till you see that when the retort is red-hot nothing more comes off; and then let your vessels cool. When the vessels are cold, unlute the receiver, and, as expeditiously as you can, pour the blue _aqua fortis_ it contains into a crystal bottle; which you must seal hermetically, because this colour disappears in a short time when the liquor takes air. You will find in the retort a white saline mass moulded in its bottom, and some flowers of Arsenic sublimed to its upper cavity, and into its neck. Pulverize the saline mass, and dissolve it in warm water. Filter the solution, in order to separate some arsenical parts that will be left on the filter. Let the filtered liquor evaporate of itself in the open air; when it is sufficiently evaporated, crystals will shoot in it representing quadrangular prisms, terminated at each extremity by pyramids, that are also quadrangular. These crystals will be in confused heaps at the bottom of the vessel: over them will be other crystals in the form of needles; a saline vegetation creeping along the sides of the vessel; and the surface of the liquor will be obscured by a thin dusty pellicle. _OBSERVATIONS._ Arsenic, as we took notice in our Elements of the Theory, besides the properties it hath in common with metallic substances, possesses others also in common with saline substances. One of the most remarkable among the latter is that of decomposing Nitre; of expelling the Acid of that Salt from its Alkaline basis, assuming its place, and forming with that Alkali a Neutral Salt, which is very soluble in water, and shoots into regular crystals. To inquire into what passes in the decomposition of Nitre by Arsenic, and into the new Salt resulting from thence, was the design of the first Memoir given in by me to the Academy of Sciences on this subject, and from that the present process is copied. Though the whole quantity of Arsenic prescribed in the process doth not enter into the composition of the new Neutral Salt, seeing some of it sublimes in flowers, that quantity must not therefore be thought too great: for we see, on the other hand, that part of the Nitre is not decomposed. The needle-like Salt is no other than Nitre that hath not suffered any decomposition, and actually deflagrates on live coals like common Nitre. The precaution of putting some water in the receiver is absolutely necessary, to condense the nitrous vapours that rise in the distillation: for they are so elastic, so volatile, so dephlegmated, that a very small part of them will otherwise be condensed into a liquor, while the rest will remain in the form of vapours, to which vent must be given through the small hole in the receiver, as without that they will burst the vessels with impetuosity: and consequently scarce any Acid will be obtained; especially if the Nitre employed be very dry, as it must be to be reducible into a fine powder. The blue colour communicated by the Nitrous Acid to the water is very remarkable. The cause that produces this colour is not yet known. Though the Acid is, on this occasion, mortified by a great quantity of water, yet, when it rises out of the retort, it is so concentrated as to form, even with that water, if too much be not put in, a most active and even smoking _aqua fortis_. It is necessary in this operation, and more so than in any other, to warm the vessels gradually, and to proceed exceeding slowly; otherwise the artist runs the risque of seeing his vessels burst to pieces with violence, and with great danger to his person: for Arsenic acts on Nitre with incredible vivacity; insomuch that, if a mixture of Nitre and Arsenic be heated to a certain degree, the Nitre is decomposed almost as rapidly, and with as great an explosion, as when it is made to fulminate with an inflammable matter. In short, the appearances are such, that one would be almost induced to think the Nitre really takes fire on this occasion: though it be only decomposed just as it is by the Vitriolic Acid. The solution of the _caput mortuum_ of this distillation contains, at the same time, several sorts of Salts: to wit, 1. the Neutral Salt of Arsenic, formed by the union of the Arsenic with the basis of the Nitre; this shoots into the prismatic crystals above-mentioned: 2. some Nitre that hath not been decomposed; this forms the needles and part of the vegetations: 3. a small portion of Arsenic, that is known to be soluble in water; this forms the thin dark pellicle that covers the surface of the liquor when it begins to evaporate. For the properties of this new Neutral Salt of Arsenic you may consult what we have said thereupon in our Elements of the Theory, and in the Memoirs of the Academy of Sciences. PROCESS V. _To alkalizate Nitre by Arsenic._ Melt in a crucible the Nitre you intend to alkalizate. When it is melted, and moderately red, project upon it two or three pinches of pulverized Arsenic. A considerable effervescence and ebullition will immediately be produced in the crucible, attended with a noise like that which Nitre makes, when it detonates with an inflammable matter. At the same time a thick smoke will rise, which at first will smell like garlic, the odour peculiar to Arsenic; it will also smell afterwards like Spirit of Nitre. When the effervescence in the crucible is over, throw again upon the Nitre as much pulverized Arsenic as you did the first time; and all the same phenomena will be repeated. Continue thus throwing in Arsenic in small parcels, till it produce no more effervescence; taking care to stir the matter at every projection with an iron wire, the better to mix the whole together. Then increase your fire, and melt what remains. Keep it thus in fusion for a quarter of an hour, and then take the crucible out of the fire. It will contain a Nitre alkalizated by Arsenic. _OBSERVATIONS._ This operation, as well as the preceding one, is a decomposition of Nitre by Arsenic; yet the result is very different: for, instead of a Salt capable of crystallizing, and discovering no tokens either of Acid or Alkali, we obtain, on this occasion, only a Salt that runs into a liquor by the moisture of the air, doth not crystallize, and hath all the properties of an Alkali. These differences arise only from the different manner in which the decomposition of the Nitre, and the union of the Arsenic with the basis of that Salt, is brought about. When the Nitrous Acid is distilled by the interposition of Arsenic, with a view to obtain the Arsenical Salt, the operation must be performed in close vessels; no greater degree of heat must be applied to the mixture than is necessary for enabling the Arsenic to act; and that heat must be administered very slowly and by insensible degrees. But, when the business is to alkalizate Nitre by the means of Arsenic, the operation is performed in a crucible, in a naked fire, with a strong degree of heat, and that suddenly applied. The violence of the heat, the suddenness with which it is applied, the vivacity wherewith the Arsenic unites with the basis of the Nitre; and, still more than all these, the free access of the air, occasion the greatest part of the Arsenic, which at first combines with the basis of the Nitre after having expelled its Acid, to be presently carried off and dissipated in vapours; and consequently the basis of the Nitre, not being sufficiently saturated, discovers its Alkaline properties. I say, the concurrence of the air contributes, still more than all the rest, to separate the Arsenic from the Alkaline basis of the Nitre; experience having taught me that the Neutral Salt of Arsenic is not to be alkalizated by the most violent force of heat, as long as it continues in close vessels, and the external air hath no communication with it; but that some of the Arsenic contained in that Salt is dissipated, by exposing it to a strong heat in open vessels. The tumult and effervescence that arise, when Arsenic is projected on Nitre fused in a crucible, are so considerable, and so nearly resemble the detonation of Nitre with an inflammable matter, that we should be tempted to think, if we trusted appearances only, that Arsenic furnishes a combustible matter, and that the Alkalization of the Nitre is effected, on this occasion, in the same manner as when it is fixed by charcoal: but, by examining attentively what passes, we easily discover that there is no inflammation at all, and that the Nitre is alkalizated in the manner and by the means above pointed out. The first vapours that rise, when Arsenic is projected on Nitre, are purely arsenical; and, if any cold body be put in their way, they adhere to it in the form of flowers. These vapours are actual particles of Arsenic, carried up by the heat before they could come to act on the Nitre; but they are soon after mixed with Nitrous vapours, consisting of the Acid of the Nitre, which the Arsenic expels from its basis as fast as it comes to act on that Salt. The nearer you come to the end of the operation, the more does the matter in the crucible lose of its fluidity, though an equal fire be constantly kept up in the furnace. At last it becomes quite like a paste, and the fire must be made much stronger to put it again in fusion. The reason of this is, that Nitre when alkalizated is much less fusible than when it is not so. The case is the same when this Salt is alkalizated by deflagration. Though the Nitre, when alkalizated, makes no more effervescence with Arsenic, and though, when kept in fusion, it emits no more arsenical vapours, it doth not thence follow that it is a pure Alkali, and that it contains no Arsenic: it still contains a large quantity thereof, but so strongly united that the force of fire is not able to separate them; which hath led some authors to give this Salt the title of _Fixed Arsenic_. The existence of Arsenic in this saline compound is easily discovered, by fusing it with metallic substances, on which it produces the same effects as Arsenic. With solutions of metals in the Acids, it also presents almost the same phenomena as the Neutral Salt of Arsenic. Particularly it precipitates Silver dissolved by the Nitrous Acid in a red powder, as that Salt does; and the differences observed between the precipitations made by our new Neutral Salt of Arsenic, and those made by Nitre alkalizated with Arsenic, can be attributed only to the alkaline quality of the latter. See the Memoirs of the Academy for 1746. [Illustration: Decorative Scroll.] PART II. OF VEGETABLES. SECTION I. _Operations on unfermented Vegetables._ CHAP. I. _Of the_ SUBSTANCES _obtained from_ VEGETABLES _by_ EXPRESSION _only_. PROCESS I. _To express and depurate the Juice of a Plant, containing its Essential Salt. The Crystallization of that Salt._ Before sun-rise gather a good quantity of the plant from which you design to express the juice, in order to obtain its Salt. Wash it well in running water, to clear it of earth, insects, and other adventitious matters. Bruise it in a marble mortar; put it into a bag of new, strong, thick linen cloth; tye the bag tight, and commit it to a press. By pressing it strongly you will squeeze out a great quantity of green, thick juice, which will have the same taste as the plant. Dilute this juice with six times as much pure rain-water, and filter it repeatedly through a woollen bag, till it pass clear and limpid. Evaporate the filtered juice with a gentle heat, till it be almost as thick as before it was mixed with water. Put this inspissated juice into a jar, or other vessel of earth or glass; on its surface pour olive oil to the depth of a line, and set it in a cellar. Seven or eight months after this, pour off gently the liquor contained in the vessel, the inside of which you will find covered with a crystallized Salt. Separate the crystals gently; wash them quickly with a little fair cold water, and dry them: this is the Essential Salt of the plant. _OBSERVATIONS._ Every plant is not equally disposed to yield its Essential Salt, by the method here proposed. Succulent vegetables only, whose juices are aqueous and not too viscous, are fit for this purpose. Such, for example, as sorrel, brook-lime, succory, fumitory, water-cresses, plantain, &c. An Essential Salt cannot be procured from those that yield thick, viscid, mucilaginous juices, such as the seeds of flea-wort; unless their juices be previously attenuated by fermentation, and that viscosity destroyed which obstructs the Crystallization of this Salt. Nor can the Essential Salt be obtained in any quantity from vegetable matters abounding in Oil. Most kernels and seeds are of this sort: they all contain a great quantity of fat oil, which so entangles and clogs this Salt, that the particles thereof cannot shoot away from the tenacious juices into crystals. The same is to be said of dry aromatic plants; because they contain much essential oil, or resinous matters that produce the same effect. It is true the Essential Salt itself contains a certain portion of oil; for it is no other than the Acid of the plant incorporated and crystallized with part of its oil and of its earth: but then the oil must not be in too great a quantity: because it sheaths the Acid, renders it clammy, as it were, and hinders it from extricating itself, so as to be able to exert its qualities, and appear in the form of Salt. The plants, from which you intend to extract this Salt, should be gathered in the morning before sun-rise; because they are then most succulent, not being yet dried up or withered by the heat of the sun. The juice of plants obtained by expression is very thick; because it contains many particles of the bruised plant, that are unavoidably squeezed out along with it. In order to clear it of these superfluous parts, it is proper to filter it; but as that would be difficult, on account of the thickness of the juice, it must be thinned, by diluting it with a quantity of water, sufficient to give it the requisite degree of fluidity. Instead of thus diluting the expressed juice, the plant may be ground with water, before it is put into the press: it will by this means furnish a more fluid juice, that will easily pass through the filter. This method may be employed with success on dry plants, or such as are not very succulent. For this operation rain-water is to be preferred to any other; because it is the purest: for all waters that have run some time through the earth, or on its surface, are to be suspected of containing some saline or selenetic matter, which would mix with and deprave the Essential Salt. The juice of the plant, when diluted with the quantity of water sufficient to facilitate its filtration, is too aqueous to let the Salt it contains unite into crystals: it must therefore be evaporated, till it hath recovered a somewhat thicker consistence. The heat applied for that purpose must be gentle; lest the acid and oily parts, that are to form the Salt, be spoiled or dissipated, as they are not very fixed. In summer, the heat of the sun is sufficient to effect this evaporation: but if you make use of this method, the juice to be evaporated must be put into several broad flat pans; that, a larger surface being exposed to the action of the air and sun, the evaporation may be the sooner completed: for if the juice should continue too long in the degree of heat requisite for its evaporation, it might begin to ferment; which would be very detrimental. The oil poured on the liquor prevents its fermenting, putrefying, or growing mouldy, during the long space of time required for the crystallization of the Essential Salt. These Salts are excellent medicines, being endued with the same virtues as the plants from which they were obtained. They cannot be procured from plants by distillation, though they consist in a great measure of volatile principles: nor are they obtainable by any other process that requires much heat; because they are easily decomposed, and the fire changes their natures entirely. The oily Acids extracted from plants by distillation do not crystallize, and always have an empyreumatic acrimony, that makes them very different from the Essential Salts, which are very mild and saponaceous. PROCESS II. _To draw the Oils out of Kernels, Seeds, and Fruits, by Expression._ Pound in a marble mortar, or grind in a mill, the kernels, seeds, or fruits, out of which you intend to express the Oil. If your matters be meagre, and grind to meal, suspend that meal in the steam of boiling water, in order to moisten it a little, and then dry it. Tye up your matter thus prepared in a new, strong, thick, canvass bag, and put it into a press, between two iron plates previously heated in boiling water: squeeze it strongly, and you will see the Oil run in streams into the receiving vessel. _OBSERVATIONS._ The Fat Oil of Plants is particularly found in kernels, seeds, and some fruits; some kernels contain such a vast quantity thereof, that, on being very slightly bruised in a mortar, they discharge it in great abundance. Sweet and bitter Almonds, Walnuts, and Lint-seed, are all of this kind; and require no other management but to be pounded and pressed, to make them yield a great deal of Oil. But there are others more meagre, that being ground produce an almost dry flower. In order to facilitate the expression of the Oil out of such, they must be expressed, when ground, to the steam of boiling water. For this purpose the meal may be put into a fine sieve, and that suspended over a pan half-full of water kept boiling on the fire. The ascending vapours will moisten the flower, render it more unctuous, and facilitate the expression of the Oil. It is proper to dry it a little before it be put into the press, that it may yield as little water as possible along with the Oil. Nevertheless, so much water happens now and then to be left in it, that some is expressed together with the Oil: but as oil and water do not incorporate, they are easily separated after the operation is finished. The extraction of the Oil is also greatly facilitated by heating the plates, between which the oleaginous matters are squeezed: but they must not be made too hot, if you mean to have a very mild Oil, designed either for aliment or for medicine; such as the Oil of Olives, and that of sweet almonds. For this reason the plates must be warmed in boiling water only: if you heat them to a greater degree, you run the risk of giving an acrimony to the Oils you express. But, when these Oils are intended for other uses, the plates may be made hotter, because their heat increases the yield of Oil. It is remarkable, that all the Oils obtained by expression, with the precautions above recommended, are constantly very mild; even though the matters from which they are extracted be in themselves very acrid. Mustard-seed, which is so acrid that it is even caustic, yields, by expression, an Oil as mild as that of sweet almonds. But then the kernels, seeds, and fruits, from which the Oils are extracted, must not be old; because these Oils, which are perfectly mild when fresh and new, become intolerably acrid when they grow old, and acquire this acrimony even in the fruit itself; for it is observed that these fruits turn rancid as they grow old. The Fat Oils obtained by expression are used in medicine, both internally and externally, as Lenitives and Emollients. Every body knows the great use of Oil of sweet Almonds, in inflammatory distempers of the breast and intestines. But it must be carefully noted, that these Oils can produce no good effects, unless they be fresh expressed, and from fruits, kernels, or seeds, that have not been long kept: for they not only lose their lenient virtue by growing old, but they even acquire an opposite quality, and contract such a sharp acrimony, that far from procuring any salutary relief or mitigation to the inflamed parts, they are capable of irritating and inflaming the sound. It is therefore of the last importance to administer them only when they are quite fresh: they ought never to be above two or three days old. Those that are old are generally more limpid and transparent than the fresh, which look a little more cloudy. The best way to distinguish them is to taste them, and to try whether or no they leave any sensation of rancidity on the palate and in the throat. PROCESS III. _To draw the Essential Oils of certain Fruits by Expression._ Take the rind of a Citron, Lemon, Orange, Bergamot-pear, or other fruit of that kind; cut it in slices, and, doubling the slices, squeeze them between your fingers, over against a polished glass set upright, with its lower end in a vessel of earth or porcelain. Every time you squeeze the peel in a new ply, there will squirt out of it several fine jets of liquor, which, meeting with the surface of the glass, will be condensed into drops, and trickle down in small streams into the recipient. This liquor is the Essential Oil of the fruit. _OBSERVATIONS._ No fruits but those of the kind above-mentioned will yield an essential Oil by expression. The rind of the fruit is the reservoir of this Oil: it is contained in little vesicles, which may be seen by the naked eye, spread all over the surface of the peel, and which, bursting when the peel is squeezed, discharge the Oil in the form of very fine slender spouts. Every body knows, that these little oily streams instantly take fire, when spirted through the flame of a candle: the Oil in this case is entirely consumed. The Essential Oil, thus obtained by expression, hath a very sweet and most agreeable scent. It is in every respect the same as when it made a part of the fruit that yielded it, seeing it hath not undergone the action of fire. Yet this method, however good it may be, can hardly be practised but in the countries where those fruits are in great plenty; because we cannot by this means obtain any thing near the quantity of Oil they contain. This inconvenience may be remedied by rubbing the rind, which contains the Essential Oil, on the surface of a sugar-loaf. The inequalities of that surface produce the effects of a rasp, by tearing all the oily vesicles. The Oil, which issues in abundance, is imbibed by the sugar and moistens it. When the sugar is sufficiently impregnated therewith, it may be scraped off with a knife, and put into a well-stopped bottle. The sugar does not alter the nature of the Oil; which may be kept in this manner for years, and used, though combined with the sugar, for almost all the same purposes as when in a fluid state; that is, to aromatize the several matters with which you incline to mix it. We owe these observations to Mr. Geoffroy. This experiment, in which the Essential Oil of a vegetable is obtained by expression alone, and without the aid of fire, proves that the Oils of this kind exist naturally in vegetables; and that the Oils of the same kind obtained by distillation, as shall be shewn in its place, are not the product of the fire. Essential Oils drawn by expression do not very sensibly differ from those procured by distillation. CHAP. II. _Of the_ SUBSTANCES _obtained from_ VEGETABLES _by_ TRITURATION. PROCESS I. _To make the Extract of a Plant by Trituration._ Bruise the vegetable substance of which you intend to make the Extract; or, if it be hard and dry, grind it to a powder: put the matter thus prepared, together with seven or eight times as much rain-water, into an earthen vessel; and into this vessel fit a churning staff, so that it may be continually whirled round with a rotatory motion, by means of a cord, a wheel, and a winch. Ply this machine for ten or twelve hours; and then filter the liquor through two linen cloths spread on a hair-sieve. Let your filtered liquor stand quiet for twelve hours more: then pour it off by inclination from the sediment you will find at bottom; and filter it a second time through a flannel bag. Pour fresh water, but in a smaller quantity, on the mass left after trituration with the machine. Triturate it again for four or five hours. Treat the liquor of this second triture just as you did that of the first, and mix them both together. Distribute all the liquor you now have among a sufficient number of shallow earthen plates, and evaporate it by a gentle warmth, such as that of the sun, or of a vapour-bath, to the consistence of an Extract, or even to dryness, as you think proper. _OBSERVATIONS._ In trituration the water takes up, not only the Salts of plants, but also a pretty considerable quantity of their oily and earthy parts, which those Salts have rendered soluble therein, by communicating to them a saponaceous and mucilaginous quality. After trituration, therefore, nothing remains but the grossest particles of oil and earth. Hence it is evident, that the water, in which plants have been triturated, contains nearly the same principles as the juices of those plants drawn by expression; and that it is also impregnated with their Essential Salts: so that, by evaporating it to a due consistence, we have a well made Extract of the triturated plant. The Count de la Garaye, who hath long cultivated with great assiduity those parts of Chymistry by which Medicine may be improved, hath made a great number of experiments for obtaining from plants, by triture with water, the matters in which their virtues chiefly reside, and hath also published a work, entitled Hydraulic Chymistry, in which he gives a particular account of all the processes for making such Extracts of the chief mineral, vegetable, and animal substances, as are most frequently used in the Practice of Physic. His way of evaporating, by a gentle heat, the liquor containing the Extract of a triturated substance is a very good one: for we know that heat, if but a very little too strong, is capable of changing the natures of compound bodies, by disuniting their principles, and exhaling some of them. If all vegetable matters were fat and succulent, as most pot-herbs are, triture would not be necessary for the making an Extract of them, even without the help of fire. We should have nothing to do, for that purpose, but to express their juices, as before, clarify them, and evaporate with a gentle heat to the consistence of an Extract. But many vegetable substances, such as woods, barks, roots, &c. are dry, hard, and compact. These matters will not give out their Extract, without such an application of water as shall dissolve their saline, saponaceous, and mucilaginous parts. Now this must be effected either by triture or by fire. Trituration has the advantage of procuring Extracts, in which the principles are perfectly unaltered, and retain the same proportions, with respect to each other, as in the plant: but then it is attended with the inconveniencies of being very tedious, troublesome, and chargeable. When we come to deliver the methods of making extracts by decoction and by infusion, we shall see what are the advantages and disadvantages of preparing Extracts by heat. The matters, from which an extract is to be made by triture, must be previously bruised and reduced into small parts, in order to facilitate the action of water upon them. The several filtrations and decantations here directed are intended to separate the grosser parts of the plant, that were only suspended in the liquor, but not truly dissolved, by means of the agitation and motion: for this reason also, the longer the liquor is left to settle, the purer will the Extract be. Though the plant be triturated the first time with a great deal of water, and for a good while too, yet it is not by that means wholly exhausted: M. de la Garaye therefore directs the remainder to be triturated again with fresh water: but this second operation requires only half the water used in the former, and need be continued only half the time; the plant having been already opened by the former triture, and having fewer parts to give out. It is better to add fresh water, and triturate a second time, than to triturate but once, and for a greater length of time: for when the water is impregnated with the principles of the plant to a certain degree, it is less capable of acting, and of dissolving more, than when it is pure. As the water impregnated with the principles of the plant by triture must be almost wholly evaporated, in order to bring those principles nearer together, and that the whole may lie in the smallest compass possible; and, moreover, as this evaporation must be effected by the gentlest heat, it is necessary to spread the liquor so, by distributing it among a great number of plates, that it shall be reduced in a manner entirely to surface. By this means the Extract may be evaporated even to dryness; and this is M. de la Garaye's practice. As the Extracts, thus evaporated to dryness, cannot be taken up otherwise than in little scales, the lower surfaces whereof, by adhering to the glazing of the plate, are smooth and shining, they in some measure resemble a crystallized Salt; which led M. de la Garaye into an error, and induced him to give the title of Essential Salts to the Extracts prepared in this manner. The Essential Salt is indeed contained in them; but still they are only Extracts, as Mr. Geoffroy hath shewn, in a memoir on this subject given in by him to the Academy; since, besides the Essential Salt, they contain moreover, as was said before, a great deal of the oil and earth of the matters from which they were extracted. This, in the main, is no objection, but rather an advantage to them; considering that such saline Extracts are, on that account, so much the more like the substances from which they were obtained; especially with regard to their medicinal properties. PROCESS II. _To extract from Seeds and Kernels, by Trituration, the Matter of Emulsions._ Blanch the kernels of which you desire to make an Emulsion; put them into a marble mortar; add a very little water; and pound them with a wooden pestle. Continue pounding and triturating till the matter become like a white paste. From time to time pour on it, by little and little, more fair water warmed, still continuing the trituration; by which means the paste will grow thinner. Go on thus till every particle of your kernels be crushed to pap. Then add, still rubbing the mixture, enough of water to make the whole an actual fluid; and you will have a liquor of a dead-white colour, resembling milk. Strain it through a clean linen cloth; it will leave on the filter some coarse parts, which must be returned to those left in the mortar. Again triturate and rub the remainder of the kernels, with the addition of water as before. This second liquor will not be so white nor so rich as the former: filter it in the same manner, and again grind with water the solid parts remaining. In this manner proceed, repeatedly rubbing and adding fresh water, till it appear no longer milky, but come off clear. The white milky waters thus obtained go by the name of an _Emulsion_. _OBSERVATIONS._ All the matters, from which a Fat Oil is obtainable by expression, produce Emulsions when triturated with water. An Emulsion consists chiefly of two substances. One of these is mucilaginous, and soluble in water. This substance by itself would not give a milky appearance to the Emulsion, which, with it alone, would be limpid. The other is a Fat Oil, which of itself is not soluble in water; but being divided by the means of trituration into very small globules, it is dispersed through the whole liquor, and suspended therein by the aid of the mucilaginous part. It is this oily part that gives the Emulsion its dead-white, milky colour; because it is not actually dissolved in the water, but only diffused through it. If Oil be mixed with water in a phial, and the mixture strongly shaken for some time, with a rapid and continued motion, the Oil will be divided into a vast number of little globules, which intervening between the parts of the water will destroy its transparency, and give it a dead-white colour, like that of our Emulsion. But, as the Oil is not so minutely divided by this means, as by triturating the matters containing it; and again, there being no mucilage in this liquor, as there is in Emulsions, the Oil soon separates from the water when it is left at rest, re-unites into round globules, and these joining together rise to the surface of the liquor, which then recovers its transparency. The case is not exactly the same with Emulsions; but something like it happens to them also. If they be left to stand quiet in a long bottle, the liquor, which at first appeared homogeneous, separates into two manifestly different parts. The upper part retains its dead-white colour, but is thicker and more opaque; while the lower part becomes perfectly transparent. This is the beginning of an entire separation of the oily from the aqueous parts. The former, being the lighter, ascend and gain the upper part of the liquor; while the lower, being freed from that which obstructed its translucence, recovers its proper limpidity: but the oily parts do not re-unite into masses large enough to form one homogeneous whole, with the appearance and limpidness of Oil; their being minutely divided and entangled in the mucilage impeding their natural tendency. Emulsions first begin to spoil, as they grow old, not by turning rancid and acrimonious like the Fat Oils drawn by expression, but by turning sour; which is owing to the great quantity of mucilage they contain. As there is a Fat Oil in their composition, they have the same virtues with that sort of Oil; but they are, moreover, incrassating, cooling, and emollient; qualities which render them extremely useful in acute and inflammatory disorders. They grow sour in a very short time, especially in the heat of summer; nay, they sometimes do so in two hours: and therefore they ought to be prepared from time to time as they are to be used. The matter that is left when all the substance of the Emulsion is extracted, and from which the water comes off clear and limpid, is scarce any thing but the earthy part of the seed or kernel that was triturated; which, however, still retains a portion of tenacious and gross Oil, adhering to it so firmly as not to be separable by water. The chyle and milk of animals resemble an Emulsion in several respects, and particularly in their dead-white colour; which arises, in the same manner, from the very minute particles of Oil contained in them, and distributed through an aqueous gelatinous fluid, but not dissolved therein. In general, whenever any Oil of any kind happens to be lodged in this manner between the parts of an aqueous liquor, it always makes the whole of an opaque white: for Oil will not mix with water, so as to produce a liquor that shall appear homogeneous and transparent, unless it be intimately dissolved in the water; which cannot be effected but by means of an union previously contracted between it and some saline matter: as is the case of mucilages, certain saponaceous matters, and some other combinations of which we shall have occasion to treat in the sequel. The methods we have hitherto proposed, for extracting from vegetable substances all that they will yield without the assistance of fire, are not capable of analyzing those substances accurately, as you may have observed; since by expression and trituration we obtain only the liquid parts, impregnated indeed with almost all the principles of plants, which, however are still combined with each other, and barely separated from the grossest earthy and oily parts. We must therefore necessarily have recourse to a more effectual expedient for carrying our analysis further. This expedient consists in making them undergo the action of fire, successively graduated, from the gentlest to the most violent heat. But, before we enter on this Analysis of Vegetables, it is proper to describe the different operations that may be performed on Oils, the only pure principle we have been able to obtain without the help of fire. As we shall have occasion, when we come to treat of the analysis of plants by fire, to say a great deal more concerning Essential Oils, we reserve till then what relates to the operations that may be performed on them; and confine ourselves here to the operations on Fat Oils. CHAP. III. _Of_ OPERATIONS _on_ FAT OILS. PROCESS I. _To attenuate Fat Oils, and change their Nature, by exposing them to the Action of Fire, and distilling them._ Mix thoroughly three or four pounds of any Fat Oil whatever, with twice its weight of lime flaked in the air. Put this mixture into a large earthen retort, leaving a third part of it empty. Set it in a reverberating furnace, and lute on a receiver. Heat the vessel with a very gentle fire. A little phlegm will rise first, and will soon be followed by an Oil that will fall in drops from the nose of the retort. Continue the distillation very slowly, till you perceive the Oil that comes over begin to be not quite so fluid as before, but rather a little thicker. Then unlute your receiver, and put another in its place. Continue the distillation, increasing your fire by degrees. The Oil that comes over will grow thicker and thicker, its fluidity will decrease, and it will acquire a dark-brown colour, which at last will become blackish. The Oil will then be very thick. Push the operation till nothing more will come off, though the retort be red-hot. During the whole time this distillation lasts, there rises a good deal of water, in company with the Oil. Keep the second thick Oil by itself. Mix the Oil that came over first, in this operation, with an equal part of fresh lime flaked in the air. Put the mixture into an earthen or glass retort, of a size so proportioned to the quantity, that a third part thereof may remain empty. Distil as before. The same phenomena will appear: a clear Oil will first come over, and be succeeded by one a little thicker. Then shift your receiver, and distil off all the rest of the Oil with an increased fire. The first Oil obtained by this second distillation will be clearer and thinner than that of the first distillation; and the second Oil will not be so thick, nor of so deep a colour as before. Distil over again, in the same manner, the thin Oil of this second distillation, and go on thus repeatedly distilling, till the first clear oil come over with a degree of heat not exceeding that of boiling water. Then, instead of mixing your Oil with lime, put it with some water into a glass retort, or into a body with its head fitted on, and distil it, keeping the water just in a simmer. Your Oil will be more and more attenuated, and, after being thus distilled twice or thrice with water, will be so limpid, so thin, and so clear, that you will scarce be able to distinguish it from water itself. _OBSERVATIONS._ Fat Oils, which are naturally mild, unctuous, inodorous, or have at most a scarce perceptible smell, resembling that of the fruit or kernel from which they were extracted, change their natures totally when exposed to the action of fire. If they be but heated so as to boil, they become acrid, lose much of their unctuosity, and acquire a very pungent odour. From several analogies, and by several experiments, recited in a Memoir on Oils which I read to the Academy, I shewed that these alterations of Fat Oils are produced by the fire's extricating an Acid in them, which before lay concealed and inactive. What I advanced on this subject may be seen in the Memoirs of the Academy for 1745, and in my Elements of the Theory of Chymistry. I shall take occasion to add something more, in my Observations on the following process, by which these Oils are combined with Acids. In this place I shall only examine what passes in the repeated distillations they are here made to undergo. Fat Oils do not rise in distillation without a degree of heat greater than that of boiling water; and therefore they must be distilled in a sand-bath, or with a naked fire. We prefer the latter method, for reasons elsewhere assigned, and chiefly because the operator is more master of his fire; it being absolutely necessary, in this operation, that he have it in his power to suppress it in an instant, when he finds it too strong: for, in such a case, it will impetuously raise the thin Oil mixed with the thick; nay, the whole will be burnt, as it were, to a coal, if a degree of fire ever so little too strong be kept up but for a few moments. When this accident happens, it is always predicted by a great quantity of white vapours ascending with impetuosity out of the retort, and by drops of Oil following each other very fast, that are scarce limpid at first, and soon become of a dark colour. All this may be prevented by distilling very slowly, and with great patience. Fat Oils may be distilled and attenuated without any additament: but then the operation, which is tedious and troublesome enough, even when lime is used, as appears from our description of the process, would be much more so if the Oil were distilled alone, without the addition of any thing to divide it, spread it, and enlarge its surface. Lime is one of the best additaments that can be employed on this occasion; not only because it procures the advantages just mentioned, but also by reason that, being an absorbent of fat matters, it unites with the grosser parts of the Oil, retains them, and so allows the thinnest and lightest parts to be readily separated from the rest. By this means it greatly expedites the operation: and, the more of it is added, with respect to the oil, the sooner is a considerable quantity of thin limpid Oil obtained: and this is the reason of our directing a double quantity of lime to be mixed with the Oil in the first distillation. Lime slaked in the air is employed preferably to quick-lime; because it is naturally divided into a very fine powder, and capable of mixing perfectly with all sorts of matters. The water that first appears in the distillation comes from the lime: it is part of the humidity which the lime had imbibed from the air. This water continues to rise with the Oil during the whole distillation, according as the degree of heat is increased: and, if the distillation be finished by keeping the retort red-hot for some time after all is come over, the lime in it will have a greyish cast, and, when water is poured on it, grow almost as hot as quick-lime. If you resolve to carry on these distillations of a Fat Oil, till it becomes as light as an Essential Oil, it is necessary to begin with a pretty large quantity thereof, as three or four pounds: for the quantity of the Oil is considerably lessened by every distillation; not only because the thickest and grossest part is separated from it every time; but also because a portion of the Oil remains so strongly united with the lime, that the force of fire is not able to separate them. Moreover, there is reason to believe that some of it is decomposed every time it is distilled. If Oil be distilled by itself, the thickest and heaviest part remains charred, as it were, in the retort, the inside of which is lined with a crust of coal, that is to the last degree fixed: this therefore always occasions a diminution of the Oil. A Fat Oil must be distilled eight or nine times, even with lime, before it become as light as an Essential Oil, and capable of rising wholly with the heat of boiling water: by that time therefore it must be considerably diminished; and if, at least, the quantity prescribed be not taken at first, there will scarce remain a few ounces capable of being distilled with water. The portion of thick heavy Oil, obtained in the several distillations, may, if you will, be rectified again. For this purpose you must mix it with fresh lime, and distil it as you did the clear Oil. A portion of this also will be attenuated, and come over first. Thus all the Fat Oil may be subtilized by the action of fire; an absolutely charred black part excepted, that remains fixed, and appears susceptible of no change, but by burning it in the open air, and thereby reducing it to ashes, from which a little Fixed Alkali may be obtained. In this fixed part of the Oil the acid and earthy parts are combined therewith, in a greater proportion than they ought to be in pure Oil. The portion of Oil that hath become light and thin is nothing but the purest oily part, separated from the gross acids, and from a certain quantity of earth, which made it thick and heavy. This Oil resembles the Essential Oils in lightness, fluidity, and a penetrating agreeable odour: it dissolves in Spirit of Wine. We shall have occasion in the sequel to enlarge further on the qualities of the several sorts of Oils, and their solubility in Spirit of Wine, when we come to treat of Ardent Spirits and of Æther. PROCESS II. _To combine Fat Oils with Acids. The Decomposition of this Combination._ Put any Fat Oil whatever into a glass bason, and set it in a sand-bath very moderately heated. Pour on this Oil an equal quantity of concentrated Oil of Vitriol, which will immediately dissolve it with violence; a considerable ebullition and effervescence will arise, attended with great heat, and a prodigious quantity of black, thick vapours, in which may be easily perceived the smell of burnt Oil, together with that of a Sulphureous Acid. The mixture will become of a deep-red, black, and thick. Stir it with a small stick, till you observe that all is quiet. _OBSERVATIONS._ The Vitriolic and Nitrous Acids unite with Fat Oils, and dissolve them with violence; but these Acids must be sufficiently strong and concentrated, otherwise they will not act upon the Oils. The Vitriolic Acid, in particular, dissolves them pretty thoroughly. If hot water be poured on the mixture described in our process, this water will become cloudy and milky, by dissolving some of it: so that Oils may be rendered soluble in water by the means of Acids. Spirit of Wine, which doth not attack Fat Oils in their natural state, unites perfectly with them, and makes a clear limpid solution of them, when they are thus combined with Acids. The Acids also suffer a considerable alteration by contracting an union with Oils. They become much milder, and lose almost all their strength. If the mixture described in the process be distilled, there will come over a great quantity of an empyreumatic acidulated phlegm, that smells strong of Sulphureous Spirit; an Oil thinner than the original saponaceous mixture; a weak Oily Acid, and a very thick, black Oil. If the fire be made very strong, when the Oil ceases to rise, it sometimes happens that a little Sulphur sublimes into the neck of the retort. By this analysis it appears, that the strong concentrated Acid, which was an ingredient in the combination, is not now to be found. The Vitriolic Acid hath changed its nature, and is considerably weakened by the union it hath contracted with the principles of the Oil. The aqueous part of this latter substance weakens the other, and loads it with phlegm; the inflammable part thereof renders it sulphureous, and even converts it into Sulphur. Hence it follows, that same part of the Oil is decomposed, by the union it contracts with the Vitriolic Acid; for its phlogiston and its aqueous principle cannot be disunited, so as to form a Sulphureous Spirit, or an actual Sulphur, and an aqueous Acid, without the decomposition of a certain quantity of the Oil, in proportion to the two disjoined principles. Another portion of the Oil remains united with the Vitriolic Acid, without suffering any decomposition, and communicates to that portion of the Acid, with which it is combined, a somewhat saponaceous quality, which makes it resemble the Vegetable Acids. Thus we see, that when the Vitriolic Acid and a Fat Oil are combined together, they both suffer considerable changes; the Acid by the new alliances into which it enters, and the Oil by the decomposition it undergoes. In consequence hereof a much smaller quantity of Oil is obtained, by decompounding this combination, than was at first put in. If the Oil abstracted by distillation be combined again with a fresh quantity of the concentrated Acid, the same effects will again follow; and by this means any quantity of Oil at pleasure may be entirely decomposed. This single experiment affords an evident proof of many important truths advanced in our Elements of the Theory. Spirit of Nitre likewise dissolves expressed Oils. With Oil of Olives it forms a white paste, resembling a fine pomatum. This compound is perfectly soluble in Spirit of Wine. The Acid must be very strong and smoking to unite with this, or with any other Fat Oil: but it dissolves some of them with more rapidity than others; in which number is the Oil of Walnuts. It acts on these Oils with so much vehemence that it burns them, in some measure, making them black and thick. PROCESS III. _To combine Fat Oils with Fixed Alkalis. Hard and soft Soap. The Decomposition of Soap._ Take a lixivium of Alicant kelp made more caustic by lime, as we shall shew when we come to speak of Alkalis. Evaporate this lye till it be capable of bearing a new-laid egg. Divide it into two parts; and to one of these put just water enough to weaken it so, that a new-laid egg will not swim in it, but fall to the bottom. With the lye thus weakened mix an equal quantity of fresh-drawn Olive Oil. Stir and agitate the mixture well, till it become very white. Set it over a gentle fire, and continue stirring it incessantly, that the two ingredients of which it is compounded may gradually combine together, as part of the water evaporates. When you perceive they begin to unite, pour into the mixture thrice as much of the first strong lye as you took of Olive Oil. Continue the coction with a gentle fire, always stirring the matter, till it becomes so thick that a drop of it fixes, as it cools, into the consistence that Soap ought to have. By dissolving a little of this Soap in water, you will discover whether or no it contains more Oil than ought to be in the composition. If it dissolves therein wholly and perfectly, without the appearance of the least little drop of Oil floating on the water, it is a sign that it doth not contain too much Oil. If, on the contrary, you perceive any of these little globules, you must pour into the vessel, containing your matter, a little more of the strong lye, to absorb the redundant Oil. If there be too much of the Alkali it may be discovered by the taste. If the Soap leave on your tongue the sensation of an Alkaline Salt, and produce an urinous savour, it is a sign that there is too much Salt in proportion to the Oil. In this case a little Oil must be added to the mixture, to saturate the super-abundant Alkali. An excess in the quantity of Alkali discovers itself likewise by the Soap's growing moist in the air, on being exposed to it for some time. _OBSERVATIONS._ Fixed Alkalis, even when resolved into a liquor, that is, when loaded with much water, unite easily with Fat Oils, as appears from the experiment just recited, and require but a moderate heat to perfect that union. This combination may even be completely effected without the aid of fire, and by the heat of the sun only, provided sufficient time be allowed for that purpose; as Mr. Geoffroy found upon trial. It only requires the mixture of the Oil and Alkali to be kept five or six days in digestion, and stirred from time to time. A lixivium of pure Alkali, not acuated by lime, may also be used to make Soap: but it is observed, that the combination succeeds better, and that the Alkali unites sooner and more perfectly with the Oil, when it is sharpened by lime. The Oil is first mixed with a weaker and more aqueous lye, to the end that the combination may not take place too hastily, but that all the particles of the two substances to be compounded together may unite equally. But as soon as the Alkali begins to dissolve the Oil gradually and quietly, the dissolution may then be accelerated; and that is done by adding the remaining lye, which is stronger and less diluted than the other. Soap made with Olive Oil is white, hard, and hath not a very disagreeable smell: but as that Oil is dear, others, even the fat and oils of animals, are sometimes substituted for it. The Soaps made with most of these other matters are neither so hard, nor so white, as that made of Olive Oil: they are called _Soft Soaps_. Oils thus associated with Fixed Alkalis are by that means rendered soluble in water; because the Alkaline Salts, having a great affinity with water, communicate part thereof to the Oils with which they are now incorporated. Yet the Oil is not for all that rendered thoroughly miscible with water, or perfectly soluble therein; for the water in which Soap is dissolved hath always a milky cast: now there is no other criterion of a perfect solution but transparency. Alkalis also lose part of their affinity with water, by the union they thus contract with Oils: for, when the combination is properly made, they no longer attract the moisture of the air, nor doth water dissolve them in such quantities as before. The composition of Soap is plainly a saturation of an Alkali with an Oil; and, in order to make perfect Soap, we are forced, as was said in the process, to grope, in a manner, by repeated trials, for this point of saturation; just as when we prepare a Neutral Salt by saturating an Alkali with an Acid. The union which the Oil contracts with the Alkali makes it lose, in part, the readiness with which it naturally takes fire; because the Salt is not inflammable: the water also, which enters in pretty considerable quantities into the composition of Soap, as we shall presently see, contributes a good deal to hinder the accension of the Oil. Soap may be decompounded either by distilling it, or by mixing it with some substance that hath a greater affinity than Oil with Alkalis. If we decompound it by distillation, a phlegm, or transparent spirit, of a somewhat yellowish colour, first comes over. This liquor is the aqueous part of the Soap, quickened by a little of its Alkali, which gives it an acrid taste. It is followed by a red Oil, which at first is pretty thin and limpid, but thickens as the distillation advances, grows black, and has a very disagreeable empyreumatic smell. This Oil is soluble in Spirit of Wine. When the distillation is finished, that is, when the retort being kept red-hot for some time will discharge no more, there is left in it a saline mass; which is the Alkali of the Soap, crusted over with some of the most fixed parts of the Oil, that are charred to a coal. This Salt may be restored to the same degree of purity it had before its combination with the Oil, by calcining it in a crucible with a naked fire, that may consume this burnt part of the Oil, and reduce it to ashes. It is plain that the Oil contained in Soap is affected by distillation, much in the same manner as that which we mixed with lime and distilled. Mr. Geoffroy, by analysing Soap with care, discovered that two ounces thereof contain ninety-six grains of Salt of kelp, freed from all Oil and moisture; or two drams and forty-eight grains of that Salt, as it is used in manufacturing Soap; that is, containing water enough to make it crystallize; one ounce three drams twenty grains of Olive Oil; and about two drams four grains of water. As Acids have a greater affinity than any other substance with Alkalis, they may be very effectually employed to decompound Soap. If you propose to decompound Soap by means thereof, you must first dissolve it in a sufficient quantity of water. Mr. Geoffroy, who made this experiment likewise, dissolved two ounces thereof in about three gallons of warm water, and to the solution added Oil of Vitriol, which he let fall into it drop by drop. Every time a drop of Acid falls into it, a _coagulum_ is formed in the liquor. The vessel in which the solution is contained must then be shaken, that the Acid may equally attack all the Alkali diffused in it. When no new coagulation is produced by a drop of the Acid, it is a sign you have added enough. The liquor then begins to grow clear: and if another quart of water be added, in order to facilitate the separation of the oily particles, you will see them rise and unite together on the surface of the liquor. This is a pure, clear, true Olive Oil, hath its taste, its smell, and, like it, is fluid in warm weather, and becomes fixed by cold. Yet it differs in some respects from that which never hath been united with an Alkali in order to form a Soap; for it burns more vividly and more rapidly, and is soluble in Spirit of Wine. We shall account for these differences when we come to treat of Ardent Spirits. Not only the Vitriolic Acid, but all others, even those obtained from vegetables, are capable of decompounding Soap, and separating the Oil from the Alkali. In the liquor wherein Soap is thus decompounded is found a Neutral Salt, consisting of the Acid made use of, united with the Alkali of the Soap. If the Vitriolic Acid be used, you will have a Glauber's Salt; a quadrangular Nitre, if the Nitrous Acid be used; and so of the rest. The facility with which Acids decompound Soap is the reason that no water, but what is very pure, will dissolve it, or is fit to be used in washing with it. Water that doth not dissolve Soap well is usually called _Hard Water_. Such waters contain a certain quantity of saline matters, washed out of the earths through which they pass. The hardness of water is generally occasioned by selenitic particles. The hardness of all the well-water in and about Paris is owing to a considerable quantity of Selenetic Gypsum with which the Soil abounds. The Selenites, we know, are Neutral Salts, consisting of the Vitriolic Acid united with an earthy basis. If therefore Soap be put into water in which a Salt of this kind is dissolved, it is evident that the Vitriolic Acid in the Selenites, having a greater affinity with the fixed Alkali of the Soap than with its own earthy basis, will quit the latter to unite with the former; and thus the Soap will be decompounded instead of being dissolved. Accordingly we see, that, when we attempt to dissolve Soap in our well-water, the surface of the liquor is in a short time covered with a fat oily pellicle. However, this decomposition of Soap is not complete; at least, but a small part of it is perfectly decompounded; because the great quantity of Selenites, with which the water is impregnated, hinders the Soap from mixing so thoroughly with it, as is requisite to produce a total decomposition thereof. All mineral waters are likewise hard, with regard to Soap; for as most of them owe their virtues to the efflorescences they have washed off from pyrites, that have grown hot and begun to be decomposed, they are impregnated with the saline matters produced by pyrites in that state: that is, with aluminous, vitriolic, and sulphureous substances, which have the same effect on Soap as the Selenites have. Mineral waters containing Neutral Salts only, such as Sea-salt, Epsom Salt, Glauber's Salt, are nevertheless hard with regard to Soap, though the Acids of those Salts, being united with Fixed Alkalis, are incapable of decompounding it. The reason is, that those Neutral Salts are more soluble in water than Soap is; so much indeed as even to exclude it: because each of the two principles that composed them hath a very great affinity with water; whereas only one of the principles of Soap, namely, its Alkali, hath that affinity; the other, to wit, the oily principle, having none at all. Thus water impregnated with an Acid, or with any Neutral Salt, is hard with regard to Soap, and incapable of dissolving it; and hence it follows, that Soap is a sort of touchstone for trying the purity of water. Wine dissolves Soap; but imperfectly, because it contains an acid or tartarous part. Spirit of Wine also dissolves it: but neither is this dissolution perfect; because it contains too little water: for its spirituous part can dissolve nothing but the Oil of the Soap; and the Alkali is not at all, or at least in a very small quantity, soluble in this menstruum. The true solvent of Soap is therefore a liquor that is partly spirituous, partly aqueous, and not acid. Brandy has these qualities: and accordingly it is the solvent that unites best with Soap, dissolves the greatest quantity, and makes the most limpid solution thereof. Yet even this solution hath something of a milky cast, occasioned by its not being entirely free from an Acid, or the tartarous principle. This fault may be easily corrected, by mixing with it a little Alkali to absorb the Acid. A dram of crystallized salt of kelp mixed with three ounces and a half of good brandy, renders it capable of dissolving an ounce and two drams of good hard Soap, into a perfectly limpid liquor. This experiment also we owe to Mr. Geoffroy. Some years ago it was discovered that Soap might be used with great success in Medicine, and that it possesses the property of dissolving the stony concretions that form in several parts of the body, particularly in the kidneys and bladder. Soap is the basis of the composition known by the name of _Mrs. Stephen's Remedy_, and in this one ingredient its whole virtue resides. From what hath been said on the nature of this compound, as well as on the cause and phenomena of its dissolution, it plainly appears to be of the last consequence, in administering it to a patient, that his constitution be considered, and a proper regimen ordered. All Acids should be absolutely forbid him; as we know they hinder the Soap from dissolving, and decompound it; and if the patient have any acidities in the first passages, matters capable of neutralizing them should be prescribed him: as prepared crabs eyes, and other absorbents known in Medicine: in such cases those with which the Soap is compounded in Mrs. Stephen's remedy may be of use. PROCESS IV. _To combine Fat Oils with Sulphur._ Put any Fat Oil whatever into an earthen vessel; add to it about the fourth part of its weight of Flower of Sulphur, and set the vessel in a furnace, with lighted coals under it. When the Oil hath acquired a certain degree of heat, the Sulphur will melt, and you will see it fall immediately to the bottom of the Oil, in the form of a very red fluid. The two substances will remain thus separated, without mixing together, while the heat is no greater than is necessary to keep the Sulphur in fusion. Increase it therefore; but slowly and with circumspection, lest the matter take fire. When the Oil begins to smoke, the two liquors will begin to mix and look turbid: at last they will unite so as to appear one homogeneous whole. If you keep up the heat so that the mixture shall always continue smoking and ready to boil, you may add more Sulphur, which will perfectly incorporate with it: and thus may a pretty considerable quantity thereof be introduced into this composition. _OBSERVATIONS._ The Phlogiston and the Vitriolic Acid have each an affinity with Oils. It is not therefore surprising that Sulphur, which is a compound of these two substances, should be soluble in oily matters. Yet it is remarkable, that Essential Oils, which are much thinner than the Fat Oils, dissolve Sulphur with much more difficulty; as will be shewn when we come to treat of those Oils; and that Spirit of Wine, which contains an exceeding subtile Oil, doth not act upon Sulphur at all. Oil, by contracting an union, with Sulphur, produces a considerable alteration in that mineral: a phenomenon so much the more surprising, that we know it to be in some sort unalterable by any other solvent, of what kind soever, add, that its nature admits of no change but by burning. We shall say more on this subject under the head of Essential Oils. PROCESS V. _To combine Fat Oils with Lead, and the Calces of Lead. The Basis of Plasters. The Decomposition of this Combination._ Into an earthen vessel put granulated Lead, Litharge, Ceruse, or Minium; and pour thereon twice its weight of any Fat Oil whatever. If you set the vessel over a brisk fire, the Lead at bottom will melt before the Oil begin to boil. When it boils, stir the matter with a stick: the Lead, or the Calx of Lead, will gradually disappear, and at last be totally dissolved by the Oil, to which it will give a very thick consistence. _OBSERVATIONS._ Fat Oils dissolve not only Lead, but its calces also: nay, they dissolve the latter more readily than Lead in substance; probably because they are more divided. The result of a combination of these matters is a thick, tenacious mass, that grows in some degree hard in the cold, and soft by heat. This composition is known in Pharmacy by the name of _Plaster_. It is made up with several drugs into plasters, which partake of the virtues of those drugs; so that it is the basis of almost all plasters. Lead itself is seldom used to make plasters: Ceruse, Litharge, or Minium, are preferred to it; because these matters unite, as hath been said, more readily and more easily with Oils. It sometimes happens, that the Oil is burnt in the operation, and that the calx of Lead is partly resuscitated: and this gives the plaster a black colour, which however it ought not to have. This accident is occasioned by an excess of heat: and as it is very difficult to keep the Oil and the Lead in the proper degree of heat, seeing both these matters are apt to grow very hot, it hath been contrived to put into the vessel, in which the coction is to be performed, a pretty large quantity of water; which being susceptible only of a much smaller and a certain degree of heat, that is constantly the same when it boils, procures the advantage of having the composition very uniform and very white. It is necessary to stir the mixture incessantly, in order to prevent the burning of the combined Oil and Lead; which, as they unite, sink in the water by their greater weight. If the water happen to be wasted before the Oil hath dissolved all the Lead, or before the plaster hath acquired a proper degree of consistence, you must remove the vessel from the fire, and let the mixture cool, before you add more: for, if this precaution be neglected, the heat of the matter, which is now much greater than that of boiling water, will occasion a considerable explosion and extravasation thereof, though the water poured into it be as hot as possible. The combination of Fat Oil with a Calx of Lead may be considered as a sort of metallic Soap, having a metalline Calx, instead of a Fixed Alkali, for its basis. Mr. Geoffroy hath observed, that if a pound of Litharge, rubbed very fine and well washed, be incorporated with two pounds of Olive Oil, in the same manner as plaster is made, keeping water enough in the vessel to hinder the mixture from burning, there rises a smoke, while the Oil is uniting with the Calx of Lead, smelling much like that which rises from Soap. The Oil may be separated from the Calx of Lead, by the methods used to separate it from a Fixed Alkali: and when it is so separated, it hath the same properties as that separated from common Soap. This species of metallic Soap, formed by the union of a Fat Oil with the Calx of Lead, is not soluble in water, and communicates nothing to it but a greasy taste. Therefore, if you would decompound it by the means of an Acid, you must pour that Acid immediately on the compound. The Acid will attack and dissolve the Calx of Lead; and the Oil, being thus set at liberty, will rise clear and limpid to the surface of the acid liquor. Distilled vinegar effects this separation better than any other Acid, because it is the true solvent of Lead. CHAP. IV. _Of the_ SUBSTANCES _obtained from_ VEGETABLES _with a Degree of Heat not exceeding that of boiling Water_. PROCESS I. _To obtain from Plants, by distilling them with the mean Degree of Heat between freezing and boiling Water, a Liquor impregnated with their Principle of Odour._ In the morning, before sun-rise, gather the plant from which you design to extract its odoriferous water. Chuse the plant in its full vigour, perfectly sound, and free from all adventitious matters, except dew. Put this plant, without squeezing it, into the body of a tinned copper alembic, and set it in a water-bath. Fit on its head, and to the nose thereof lute a glass receiver with wet bladder. Warm the bath to the mean degree between freezing and boiling water. You will see a liquor distil and fall drop by drop into the receiver. Continue the distillation with this degree of heat, till no more drops fall from the nose of the alembic. Then unlute the vessels; and if you have not as much liquor as you want, take out of the cucurbit the plant already distilled, and put a fresh one in its place. Distil as before, and go on thus till you have a sufficient quantity of odoriferous liquor. Put it into a bottle; stop it close; and set it in a cool place. _OBSERVATIONS._ The liquor obtained from plants, with the degree of heat here prescribed, consists of the dew that was on the plant, and some of the phlegm of the plant itself, together with its odorous principle. Mr. Boerhaave, who examined this odoriferous part of plants with great care, calls it the _Spiritus Rector_. The nature of this Spirit is not yet thoroughly ascertained; because it is so very volatile, that it cannot easily be subjected to the experiments that are necessary to analyze it, and to discover all its properties. If the bottle containing the liquor, which may be considered as the vehicle of this Spirit, be not exceeding carefully stopped, it flies quite off: so that in a few days nothing will be found but an insipid inodorous water. Great part of the virtue of plants resides in this their principle of odour; and to it must be ascribed the most singular and the most wonderful effects we every day see produced by them. Every body knows, that a great number of odorous plants affect, in a particular manner, by their scent only, the brain and the _genus nervosum_, of such especially whose nerves are very sensible, and susceptible of the slightest impression; such as hypochondriacal or melancholy men, and hysterical women. The smell of the Tuberose, for instance, is capable of throwing such persons into fits, so as to make them drop down and swoon away. The smell of Rue, again, which is equally strong and penetrating, but of a different kind, is a specific remedy against the ill effects of the Tuberose; and brings those persons to life again, with as quick and as surprising an efficacy, as that by which they were reduced to a state not unlike death. This is Mr. Boerhaave's observation. The odorous exhalations of plants must be considered as a continual emanation of their _Spiritus Rector_: but as growing plants are in a condition to repair, every instant, the losses they sustain by this means, as well as by transpiration, it is not surprising that they are not soon exhausted, while they continue in vigour. Those, on the contrary, which we distil, having no such resource, are very soon entirely deprived of this principle. The separation of the _Spiritus Rector_ from plants requires but a very gentle heat, equally distant from the freezing point and from the heat of boiling water. Accordingly the heat of the sun in summer is sufficient to dissipate it almost entirely. This shews why it is dangerous to stay long in fields, or woods, where many noxious plants grow. The virtues of plants residing chiefly in their exhalations, which the heat of the sun increases considerably, a sort of atmosphere is formed round them, and carried by the air and the wind to very great distances. For the same reason the air of a country may be rendered salutary and medicinal, by the exhalations of wholesome plants growing therein. From the facility with which the odorous principle of plants evaporates, we learn what care ought to be taken in drying those intended for medical uses, so as to preserve their virtues. They must by no means be exposed to the sun, or laid in a warm place: a cool, dry place, into which the rays of the sun never penetrate, is the properest for drying plants, with as little loss of their virtue as possible. Though there is reason to believe that every vegetable matter hath a _Spiritus Rector_, seeing each hath its particular scent, yet this principle is not very perceptible in any but those which have a very manifest odour: and accordingly it is extracted chiefly from aromatic plants, or the most odoriferous parts of plants. I say the most odoriferous parts; because, in most plants and trees, there are generally certain parts that have a much more sensible, and much stronger scent than the rest. The odour of a plant, or of a tree, hath its principal residence sometimes in the root, sometimes in the leaves, at other times in the bark or wood, and very frequently in the flowers and seeds. Therefore, when you design to extract the principle of odour from a vegetable that is not equally odoriferous in every part, you must chuse those parts that have the most perceptible and strongest scent. PROCESS II. _To extract the Fat Oils of Plants by Decoction in boiling Water. Cacao Butter._ Pound or bruise in a marble mortar your vegetable substances, abounding with the Fat Oil which you intend to extract by decoction: tie them up in a linen cloth; put this packet into a pan, with seven or eight times as much water, and make the water boil. The Oil will be separated by the ebullition, and float on the surface of the water. Skim it off carefully with a ladle, and continue boiling till no more Oil appear. _OBSERVATIONS._ The heat of boiling water is capable of separating the Fat Oils from vegetable matters that contain any: but this is to be effected by actual decoction only, and not by distillation; because these Oils will not rise in an alembic with the heat of boiling water. We are therefore necessitated to collect them from the surface of the water, as above directed. By this means a much greater quantity of Fat Oil may be obtained than by expression alone; because the degree of heat applied greatly facilitates the separation of the Oil. For a convincing proof of this truth, take the remains of any vegetable matters, from which the Oil hath been so thoroughly expressed that they would yield no more; boil them in this manner, and you will obtain a great deal more Oil. The water used in this coction generally becomes milky, like an emulsion; because it contains many oily particles, that are dispersed in it just as in an emulsion. Nevertheless, this way of obtaining the Fat Oils is not generally practised; because the heat, to which they are exposed in the operation, occasions their being less mild than they naturally are: but it is an excellent method, and indeed the only one that can be employed, for extracting from particular vegetables certain concrete oily matters, in the form of Butter or Wax; which matters are no other than Fat Oils in a fixed state. The Cacao yields, by this means, a very mild butter; and in the same manner is a Wax obtained from a certain shrub in America. The heat of boiling water melts these oily matters, which then ascend to the surface of the liquor, and float on it like other Oils. They afterwards fix as they cool, and resume their natural consistence. We shall see in the sequel, that they cannot be extracted in a concrete form by distillation, which requires a greater degree of heat than that of boiling water; because distillation changes their nature, partly decomposes them, and prevents their returning to their proper consistence as they cool. PROCESS III. _To extract Essential Oils of Plants by Distillation with the Heat of boiling Water. Distilled Waters._ Put into a cucurbit the plant from which you design to extract the Essential Oil. Add as much water as will fill two thirds of your vessel, and dissolve therein half an ounce of Sea-salt for every quart of water you use. To this body fit on an alembic-head, and to the nose thereof lute a receiver, with sized paper, or wet bladder. Set it in a furnace, and let the whole digest together, in a very gentle warmth, for twenty-four hours. This being done, light a wood-fire under your vessel, brisk enough to make the water in it boil immediately. Then slacken your fire, and leave it just strong enough to keep the water simmering. There will come over into the receiver a liquor of a whitish colour, somewhat milky; on the surface of which, or at the bottom, will be found an Oil; which is the Essential Oil of the vegetable you put into the cucurbit. Continue your distillation with the same degree of heat, till you perceive the liquor come off clear, and unaccompanied with any Oil. When the distillation is finished, unlute the receiver; and, if the Essential Oil be of that sort that it is lighter than water, fill the vessel up to the top with water. On this occasion a long-necked matrass should be used for a receiver; that the Oil which floats on the water may collect together in its neck, and rise up to its mouth. Then in the neck of this vessel put the end of a thread of cotton-twine, so that the depending part without the vessel may be longer than that in the Oil, and the extremity thereof hang within the mouth of a little phial, just big enough to contain your quantity of Oil. The Oil will rise along the yarn as in a siphon, filter through it, and fall drop by drop into the little phial. When all the Oil is thus come over, stop your little bottle very close, with a cork coated over with a mixture of wax and a little pitch. If your Oil be ponderous, and of the sort that sinks in water, pour the whole contents of the receiver into a glass funnel, the pipe of which must terminate in a very small aperture that may be stopped with your fore-finger. All the Oil will be collected in the lower part of the funnel: then remove your finger, and let the Oil run out into a little bottle through another small funnel. When you see the water ready to come, stop the pipe of the funnel, and cork the bottle containing your Oil. _OBSERVATIONS._ Essential Oils, though they all resemble each other in their principal properties, are nevertheless very different in some respects: for which reason almost every one of them requires a particular management, for obtaining it with the greatest advantage possible, both as to quality and quantity. One of the first things requisite is, to chuse the proper time for distilling the plant, from which you desire to extract the Essential Oil; because the quantity of Oil varies considerably, according to the season of the year, as well as the age of the plant. For example, the most favourable time for obtaining these Oils from the leaves of ever-green plants or trees, such as Thyme, Sage, Rosemary, the Orange, the Bay, the Fir, &c. is the end of Autumn; because these vegetables contain a great deal more Oil at that season than at any other. With regard to annual plants, they must be chosen when in their prime, and just before they begin to decline. The time therefore of gathering them is when they begin to flower: and if you want to extract the Oil from the flowers themselves, you must pull them just when they are newly blown. Secondly, it must be observed, that the Essential Oils of plants are, as it were, the chief residence and reservoir of their odorous principle; that they are to be found wherever that principle exists, and never where it is not: so that what we said concerning the _Spiritus Rector_ of plants is applicable here. It must be remembered, that all the parts of some vegetables are odoriferous. Such plants may be put into the alembic all together, and the Essential Oil distilled from all their parts at once. But others, and indeed the greatest number, have no odour, or at least none that is very perceptible, except in some particular parts; as in their leaves, flowers, roots, or seeds: therefore, when you want to have the Essential Oil of such a plant, you must chuse that part in which the Odour resides. The sense of smelling must be the artist's principal guide on this occasion. Thirdly, all vegetables, and all the parts of vegetables, have not the same texture: some are hard and compact, as woods, barks, and some roots; others are tender and succulent, as most annual plants, and some fruits. For this reason, they must be differently prepared for distillation. It may be laid down as a general rule, that the closer and more compact their texture is, the more they require to be opened and divided, either by comminuting them into small particles, or by digesting them a considerable time in water acuated with Salt. Fourthly, though all Essential Oils be capable of rising in distillation with the heat of boiling water, yet they have not all an equal degree of levity and weight: on the contrary, they vary exceedingly in this respect: some, as, for instance, those of all our European aromatics, being lighter than water, so that they always float on its surface; whereas others, such as those of Cloves, Sassafras, &c. which are Indian aromatics, are heavier than water, and always sink in it by their specific gravity. These differences therefore require different methods of distillation. It is proper, for example, to make use of a low alembic in distilling such Essential Oils as are heavier than water; and, moreover, to facilitate their separation, by applying a degree of heat somewhat stronger than that of boiling water. This is easily done by impregnating the water with a proper quantity of Sea-salt, or the Vitriolic Acid; for, the more saline matters are contained in water, the more will the degree of heat it acquires, by being brought to boil, exceed that of pure boiling water. Fifthly, Essential Oils differ from one another in point of fluidity. Some are as thin and as fluid as Spirit of Wine: of this number is the Essential Oil of Turpentine. Others, again, are thick, and even congeal as they cool: such, for instance, is the Oil of Roses. In distilling Oils of this latter sort, care must be taken that the spout of the alembic head do not grow too cold, but be kept always in such a degree of warmth as may prevent the Oil from fixing in it, and stopping it up; which would interrupt the distillation, and might also occasion some other more considerable inconveniencies, of which we shall take notice presently. From what hath been said it appears, that the distillation of Essential Oils cannot be regulated by any one general rule; but that the manner of operating must be a little varied, according to the nature of the Oil to be distilled, and to that of the vegetable from which it is to be drawn. The time of day fittest to gather plants for this distillation is the morning before sun-rise; because the coolness of the night hath shut all their pores, and concentrated their odour: whereas in the evening, after the plants have been exposed all day to the heat of the sun, their odorous principle is in a great measure dissipated, and they are left almost quite exhausted of it. Now, the more of the odorous principle the plants contain, the more Essential Oil will they yield, and the more virtue will that Oil have. Plants fresh gathered, and as yet full of moisture, do not yield so much Oil in distillation as they do when dried; because the oily particles in a very moist plant are more diffused, and even separated from each other, by the interposition of the aqueous parts: whence it comes to pass that, in distillation, they ascend in a state of separation from each other; so that being dispersed through the water they give it a milky colour, like that of an emulsion; and cannot unite together but in small quantities, which hinders their being easily separated from the water. This inconvenience doth not happen, or at least is considerably less, when the greatest part of the humidity of the plant is evaporated by desiccation: for the oily particles, being thus delivered from the intervening aqueous parts, which kept them separated from each other, are brought nearer together, unite, and form little visible globules of Oil, which easily emerge from the water employed in the distillation. But, in drying plants from which the Essential Oil is to be extracted, great care must be taken that they be neither exposed to the sun, nor laid in a warm place; because the heat would carry off part of their odour, and even, from some plants, a pretty considerable quantity of their Essential Oil. Plants of a loose texture, that easily give out their Essential Oils, need not be comminuted, or macerated in water with Salt. But this method must unavoidably be taken with such as are hard, and do not readily part with their Oil. Woods, barks, roots, for instance, must be first rasped, then set to macerate in water impregnated with Salt, as before directed; and this sometimes for several weeks before they be distilled. On this occasion Salt procures three different advantages. In the first place, it prevents the matters, that must stand in maceration for some time, from running into fermentation: an inconvenience that would considerably diminish the quantity of Essential Oil, or perhaps rob us of the whole, by converting it into an Ardent Spirit, if the fermentation were spirituous; or into a Volatile Alkali, if it went on to the last stage, and as far as putrefaction. In the next place, it acuates the water, and renders it more capable of penetrating and properly dividing, during the maceration, the texture of the plant which requires to be thus prepared. Lastly, it adds a little to the heat of the boiling water, and so promotes the ascent of the heaviest Oils. Nevertheless, when you find it necessary, for the reasons assigned above, to mix Salt with the water to be employed in distilling your Essential Oil, you must be cautious of putting in too much. You will indeed obtain, by means thereof, much more Oil than if you distilled it without Salt: but, as a great quantity of Salt will make the water acquire a much greater degree of heat than that of pure boiling water, a good deal of the heavy Oil of the vegetable will be raised by such a heat, mix with the Essential Oil, deprave it, and make it like those that are adulterated with a mixture of some heterogeneous Oil, as will be afterwards shewn. When every thing is prepared for distillation, it is proper, as directed in the process, to apply at once a flaming fire, brisk enough to make the liquor boil immediately: for, if the water be kept long heating before it be made to boil, the Essential Oil, which cannot rise without the heat of boiling water, will, by a less degree of heat, be only agitated, dashed about every way, and churned as it were; by which means it will be divided into very minute particles, and dispersed in the water, which will thence acquire a milky colour: and consequently we shall fall into the inconvenience that was pointed out above, as happening when we distil plants without having dried them, and while they are loaded with all the moisture and sap that was in them when fresh gathered. When the water in the cucurbit boils, it will be known by the noise that boiling water usually makes, which is produced by the numerous bubbles that rise and burst on its surface. The spout of the alembic is then so hot, that a man cannot lay his finger on it, without such a sensation of burning heat as is not to be endured. With this degree of heat the water distils in drops, which succeed each other so fast, that they seem to form a continued small stream; and this water is replete with much Essential Oil. And now it is proper to weaken the fire considerably, so as to leave it but just strong enough to keep the liquor gently boiling: for if the distillation be urged too precipitately, the aqueous and oily vapours, being forcibly hurried up by too great a heat, may carry along with them some parts of the plant, which may stick in the spout, stop it up, and endanger the bursting of the vessel, or at least the forcing off its head, by the exceedingly rarefied particles of water, oil, and air, all striving to escape at the same time; and these burning hot vapours, being discharged with impetuosity, may not only scald the operator, but injure his lungs. In such distillations it is of consequence to keep constantly cooling the head of the alembic, by frequency renewing the water in the refrigeratory, in order to facilitate the condensation of the oily particles. The water in the cooler ought to be renewed when it begins to smoke very perceptibly. Whatever care be taken to save as much of the Oil as possible, and to prevent its being left dispersed in the water, yet some loss of this kind cannot be totally avoided: and thus the water that rises in distilling the Oil is always more or less milky, and strongly scented, even after it is separated from the Essential Oil. Yet this portion of the Oil and of the odorous principle, which is retained by the water employed in such distillation, is not therefore lost: the water impregnated with these principles partakes of the properties of the plant from which the Essential Oil was drawn, and may be used medicinally: it is known in Pharmacy by the title of the _Distilled Water_ of the plant. The same water may be used again, with advantage, in distilling the Essential Oil of a fresh plant of the same sort; because the oily and odorous particles, with which it is impregnated, joining with those afforded by the fresh plant, form larger _moleculæ_, capable of uniting more easily, and emerging better from the water; and consequently they increase the quantity of Oil. Thus the same water may be always employed in new distillations; and, the oftener it is used, with the greater advantage may it be used again. After all the Essential Oil is risen, if the distillation be continued, and the receiver changed, the liquor that will then come off will not be milky, but limpid. It will have no odour at all of the plant, but a kind of sourish smell; and indeed it is a part of the Acid of the vegetable in the still, which is elevated by the heat of boiling water, after all the Essential Oil is come over. If you intend to keep the distilled water which hath served as a vehicle to the Essential Oil, and design it for medicinal use, great care must be taken to stop the distillation before this acid phlegm begin to rise: for, if it should mix with the distilled water, it would spoil it, and hinder it from keeping; probably because it contains some mucilaginous parts, which are apt to putrify. PROCESS IV. _To extract the Essential Oils of Plants by Distillation_ per Descensum. Reduce to a powder, or a paste, the vegetable substances from which you intend to extract the Essential Oil by the method proposed. Lay this matter about half an inch thick on a fine, close, linen cloth. If it be dry and hard, expose the cloth containing it to the steam of boiling water, till the matter become moist and soft. Then lay the cloth, with its contents, over the mouth of a very tall cylindrical glass vessel, which is to do the office of a receiver in this distillation; and, by means of a piece of small pack-thread, fasten down the extremities of the cloth, by winding the thread several times over them and round the vessel; in such a manner, however, that the cloth be not tight, but may yield to a small weight, and sink about five or six lines deep into the vessel over which it is fastened. Set this recipient in a larger vessel, containing so much cold water as will reach half way up the cylindrical vessel; which, having little in it but air, must be ballasted with as much lead as will sink it to the bottom of the water. On the cloth containing the substance to be distilled set a flat pan of iron or copper, about five or six lines deep, that may just fit the mouth of the glass vessel over which the cloth is fastened, so as to shut it quite close. Fill this pan with hot ashes, and on these lay some live coals. Soon after this, you will see vapours descend from the cloth, which will fill the recipient, and drops of liquor will be formed on the under side of the cloth, from whence they will fall into the vessel. Keep up an equal gentle heat till you perceive nothing more discharged. Then uncover the recipient: you will find in it two distinct liquors; one of which is the phlegm, and the other the Essential Oil of the substance distilled. _OBSERVATIONS._ The apparatus for distilling above described is very convenient, when we have not the vessels necessary for distilling with water, or when we want to obtain the Essential Oil of any vegetable substance in much less time. The aqueous and oily parts of the substances distilled in this manner, being rarefied by the heat of the fire placed over them, cannot ascend upwards, because they are close confined on that side; and, moreover, the fire which rarefies them possessing all the upper part of the vessel in which they are contained, they are forced to fly from it to the place which most favours their condensation: and this determines them to descend in the recipient, where they meet with a coolness that condenses and fixes them. It was with a view to promote this condensation, that we ordered the lower part of the recipient to be sunk in cold water. Cloves are one of those substances whose Essential Oil is best obtained by this method. In the same way also may be drawn the Essential Oil of Lemon-peel, Citron-peel, Orange-peel, Nutmegs, and several other vegetable substances: but you must be cautious of applying too strong a heat; for in that case the Oil, instead of being white and limpid, acquires a red, dark-brown, blackish colour, is burnt, and smells of empyreuma: and, on the other hand, if you do not apply a proper degree of heat, you will scarce get any Oil at all. It is the surest, and therefore the best, way to distil these Oils with water in an alembic. And indeed the distillation _per descensum_ is seldom used, but out of curiosity to try its effect, or on such pressing occasions as allow no choice. PROCESS V. _Infusions, Decoctions, and Extracts of Plants._ Make some water boiling-hot, and then take it off the fire. When it ceases to boil, pour it on the plant of which you desire to have the Infusion; taking care there be enough of it to cover the plant entirely. Cover the vessel, and let your plant lie in the hot water for the space of half an hour, or longer, if it be of a firm close texture. Then pour off the water by inclination: it will have partly acquired the colour, the smell, the taste, and the virtues of the plant. This liquor is called an _Infusion_. To make the Decoction of a vegetable substance, put it into an earthen pan, or into a tinned copper vessel, with a quantity of water sufficient to bear being boiled for several hours, without leaving any part of the plant dry. Boil your plant more or less according to its nature; and then pour off the water by inclination. This water is impregnated with several of the principles of the plant, of which we shall take notice in the following observations. _OBSERVATIONS._ Water, especially when boiling hot, is capable of dissolving not only all that is purely saline in vegetables, but also a pretty considerable quantity of their Oil and of their earth, which, by contracting an union with the saline parts, have formed saponaceous, gummy, and mucilaginous compounds, that are soluble in water. After violent and long-continued boiling, therefore, there remains nothing in the plant but the purest oily part, and such as is the most fixed, that is, the most closely united with the earth of the plant. I say, the most fixed: for some part of the oily matters, though not soluble in water, may be separated by the action of boiling water, when those matters abound greatly in the vegetable decocted; as we have seen happen to the Fat Oils of certain vegetable matters; but in that case these oily matters float upon the Decoction, and do not constitute a part of it. From what we have already said, touching the analysis of plants, it seems evident, that, if those decocted be odoriferous and contain an Essential Oil, the Decoction will contain none, or at most but very little, of their Essential Oil, or their odorous principle; seeing we know that these substances cannot bear the heat of boiling water, without being carried off and entirely dissipated by it. Therefore, when we make a decoction of an aromatic plant, containing an Essential Oil, we may be assured that it will not possess the virtues, either of the odorous part, or of the Essential Oil, and that it will have none but those of the other more fixed principles of the plant, with which it may be impregnated. The Decoction of such a plant perfectly resembles the water left in the cucurbit, after distilling its Essential Oil. But for those plants in which there are no such volatile parts, or whose virtue doth not reside in those principles, such as astringent and emollient plants, for example, that owe their properties wholly to an earthy Salt, or to a mucilage, they are capable of communicating their whole virtue to the water in which they are infused or decocted. If, on one hand, the Salts of plants render some portion of the principles of those plants soluble in water, such as part of their Oil and their earth, which if they were pure would not dissolve therein; on the other hand, these principles, being of their own nature indissoluble in water, hinder the Salts, by the union they have contracted together, from dissolving in it so easily, so soon, and in such quantities, as if they were pure. This is so true, that water, though boiled long and violently, is far from extracting out of plants all those parts that it is capable of dissolving. If, after boiling a plant in water, as directed in the process, this water be poured off, fresh water added, and a second decoction made in the same manner as the first, the water of this latter decoction will, by that means, be almost as strongly impregnated with the principles of the plant as the former was. Mr. Boerhaave was obliged to make twenty successive decoctions of the same plant, to wit, Rosemary, before the water came off the plant colourless and insipid; in a word, just as it was before the plant was boiled in it. Mr. Boerhaave observes, that a plant, after having thus given out all that water can dissolve, still retains exactly the same form that it had before it underwent any of the many boilings necessary to exhaust it; that its colour, from being green at first, becomes brown; and that the plant, which when green is lighter than water, or at least doth not sink in it, is heavier after this operation, and falls to the bottom. This is a proof that the water hath extracted out of the plant its lightest substances, assuming their places itself, and that it hath left nothing but its heaviest principles, namely, its fixed oil and its earth. We shall afterwards examine more particularly these remains of plants exhausted by water. If the Infusions and Decoctions of plants be filtered, and evaporated in a gentle heat, they become Extracts, that may be kept for whole years, especially if they be evaporated to a thick consistence; and better still if they be evaporated to dryness. From what hath been said concerning the Infusions, Decoctions, and Extracts of plants, it follows, 1. That Infusions and Decoctions of aromatic plants do not furnish a complete Extract of those plants; because they do not contain the volatile and odorous parts, in which the principal virtue of such plants usually resides. If therefore you desire to make Extracts of such vegetables, that shall have no defect, you must employ their juices drawn by expression, or water impregnated with their principles by the means of trituration, and evaporate the liquor by spreading it over a great number of plates, in order to enlarge its surface, and quicken the evaporation, which must be effected by the heat of the sun alone, or the well-tempered warmth of a stove. 2. It may also be inferred, that water alone, aided by the degree of heat it is capable of acquiring by being made to boil, is not sufficient to effect the complete analysis of a plant; since not only some of its principles are still left combined in it, though exhausted as much as it can be by boiling water; but also several of the substances extracted from it by water are compounds of some of the principles of the plant, and susceptible of a much more accurate analysis; as we shall be convinced when we come to examine the effects which a degree of heat superior to that of boiling water is able to produce on entire plants, on their Extracts, and on their remains exhausted as much as they can be by boiling water. But before we enter on that part of the analysis, it is proper to consider the experiments and combinations that may be made with the principles we have already obtained; in order to discover their nature, and in some measure analyze even them. Essential Oils in particular deserve to be thus examined. We also obtain from certain plants, with a degree of heat less than that of boiling water, a Volatile Alkali, which exists formally in them: but as these plants, when analyzed, yield principles different from these we obtain out of all other vegetable substances, and as they resemble animal matters, we shall refer their analysis to a distinct chapter. CHAP. V. _Of_ OPERATIONS _on_ ESSENTIAL OILS. PROCESS I. _The Rectification of Essential Oils._ Put into a cucurbit the Essential Oil you propose to rectify. Set the cucurbit in a _balneum mariæ_; fit to it a head of tin, or of copper tinned, together with its refrigeratory; and lute on a receiver. Make the water in the bath boil, and keep up this degree of heat till nothing more will come over. When the distillation is finished, you will find in the receiver a rectified Essential Oil, which will be clearer, thinner, and better scented, than before it was thus re-distilled; and in the bottom of the cucurbit will be left a matter of a deeper colour, more tenacious, more resinous, and of a less grateful smell. _OBSERVATIONS._ Essential Oils, even the purest, the best prepared, and the thinnest, suffer great changes, and are much impaired by growing old: they gradually turn thick and resinous; their sweet grateful scent is lost, and succeeded by a more disagreeable smell, somewhat like that of Turpentine. The cause of these changes is, that their finest and most volatile part, that which contains most of the odorous principle, is dissipated and separated from that which contains least of it; which therefore grows thicker, and comes so much the nearer to the nature of a resin, as the quantity of Acid, that was distributed through the whole Oil before the dissipation of the more volatile part is, after such dissipation, united and concentrated in the heaviest part; the Acid in Oils being much less volatile than the odorous part, to which alone they owe their levity. Hence it appears what precautions are to be used for preserving Essential Oils, as long as possible, without spoiling. They must be kept in a bottle perfectly well stopped, and always in a cool place, because heat quickly dissipates the volatile parts. Some authors direct the bottle to be kept under water. If these Oils should grow thick and resinous by age, yet they are not to be thrown away. We shall shew, in the analysis of Balsams and Resins, that, from these thick and even solid substances, Essential Oils may be drawn, as thin and as limpid as from plants. Essential Oils, thickened by time, may therefore be treated like Balsams, and actually analyzed, by separating all the subtile odorous matter they contain from their thick acid parts. For this purpose they need only be distilled with a degree of heat just sufficient to elevate the thin odorous parts, without raising the thick matter. The residue left at the bottom of the vessel, because it could not rise in distillation, is much thicker and less odorous than the Oil was before rectification. The reason of this is evident, and follows from what hath just been said. This remainder dissolves in Spirit of Wine more readily, and in greater quantity, than the light Oil drawn from it; because it contains more Acid, and because Oils owe their solubility in this menstruum to their Acid part, as is proved in our Memoir on Oils already quoted. When we come to treat of Resins, we shall inquire more particularly what this remainder is, and what principles it yields when analyzed: in this place it is sufficient to take notice, that though all the Oil of which it made a part came over at first with the heat of boiling water, yet it cannot now be raised by the same degree of heat in distillation; because it is not now combined with the principle of odour which gives the Oil its volatility, and because it is rendered sluggish by being clogged with too great a proportion of Acid. From what hath been already said, it must be concluded, that Essential Oils suffer great diminution by being rectified; and that in proportion to the quantity of resinous matter left behind. All this resinous matter, while combined with a proper quantity of the odorous principle of the plant, (that is, at the time of its being distilled, and a little while after), was really an Essential Oil: the change of its nature, therefore, is entirely owing to its having left that principle. An Essential Oil, though rectified, is still as apt to change and be spoiled as before, because it still continues to lose its odorous principle by degrees. After some time, therefore, it requires a second rectification, which again lessens its quantity. In short, it is plain that Oils will, in a number of years, greater or smaller according to their nature, and the manner in which they are kept, be wholly changed, and metamorphosed into a resinous matter, from which no thin Oil can be drawn with the heat of boiling water: and this is a proof of the fugacity of that odorous principle, or _Spiritus Rector_, of plants, which, when united with their lightest Oil, gives it the character of an Essential Oil. This resinous matter, to which Essential Oils are finally reduced, being subjected to repeated distillations, with a degree of heat superior to that of boiling water, is still capable of yielding a certain portion of a thin, limpid, sweet-scented Oil, which is as light as an Essential Oil; as we observed before is the case with Fat Oils drawn by expression: but the thin Oil obtained by this means, though it possesses almost all the properties of an Essential Oil, is not for all that a genuine one; seeing it hath not the same odour with the plant from which it was originally drawn. Essential Oils must be rectified in the _balneum mariæ_, as ordered in the process: for, as some of the Oil touches the sides of the vessel in the operation, if that vessel be made hotter than boiling water, the thick matter will rise with the thin Oil, which therefore will not be rectified. Rectification is of use not only for procuring to Essential Oils the tenuity and levity they may have lost by age, but also to separate them from other oily matters with which they may be adulterated. If, for instance, an Essential Oil be not properly distilled; if, by the addition of too much Salt, the water have acquired a degree of heat greater than that of pure boiling water, and if, in consequence thereof, some of the heavy Oil of the plant have risen with the Essential Oil, and mixed therewith, the Essential Oil may, by rectification, be separated from this heterogeneous Oil; which, being heavier and incapable of rising with the heat of pure boiling water, will remain at the bottom of the vessel. The effect will be the same, if your Essential Oil be falsified with a mixture of any Fat Oil, as is often the case: for, some of them being extremely dear, the vender frequently adds a portion of Fat Oil to increase the quantity. For this purpose Oil of Ben is generally used. When an Essential Oil is thus falsified with a mixture of any Fat Oil, it may be discovered by letting a few drops of it fall into rectified Spirit of Wine; which will dissolve the Essential Oil only, leaving the Fat Oil quite untouched. Essential Oils are sometimes falsified by mixing them with a certain quantity of Spirit of Wine. This fraud doth not render their smell less fragrant: on the contrary, it becomes rather more agreeable and quicker. In order to try an Oil suspected of being falsified in this manner, drop a little of it into very clear water. If a milky cloud appear in the water, be assured the Oil is mixed with Spirit of Wine: for as this liquor unites more readily with water than with Oil, it quits the Oil with which it was mixed to incorporate with the water: mean time a good deal of the Oil that was dissolved by the Spirit of Wine, and is now separated from it by the intervention of water, necessarily remains dispersed through this water in very small particles; and these form the milky cloud produced on this occasion. An Essential Oil may also be adulterated with another Essential Oil that is much more common, and of much less value. Those who practise this fraud generally employ Oil of Turpentine for that purpose, on account of its cheapness and tenuity. The cheat is easily discovered, by moistening a linen rag with the Oil supposed to be thus falsified, and then holding the rag a little before the fire, which presently dissipates the odorous part of the falsified Oil. This odour, which prevented our distinguishing that of the Oil of Turpentine, being vanished, the peculiar smell of the Turpentine, which is much more permanent, remains alone; and is so perceptible that it cannot easily be mistaken. Those who are much accustomed to see and examine Essential Oils, have seldom occasion to make the experiments here proposed for discovering their qualities. A certain degree of thickness, partaking of unctuosity, in an Essential Oil, convinces them that it is falsified with a Fat Oil: on the other hand, a greater degree of tenuity, together with a quicker smell, than a pure Essential Oil ought to have, discovers the admixture of Spirit of Wine. Lastly, any one, whose sense of smelling is not very dull, will easily discover the odour of the Oil of Turpentine, though disguised by that of the Essential Oil with which it is mixed. PROCESS II. _To fire Oils by combining them with highly concentrated Acids: instanced in Oil of Turpentine._ Mix together, in a glass, equal parts of concentrated Oil of Vitriol, and highly smoking fresh-drawn Spirit of Nitre: pour this mixture at several times, but suddenly, on three parts of Oil of Turpentine, set for that purpose in a glass bason. By a part here must be understood a dram at least. A most violent commotion, accompanied with smoke, will immediately be raised in the liquors, and the whole will take fire in an instant, flame, and be consumed. _OBSERVATIONS._ There is not in Chymistry a phenomenon more extraordinary, and more surprising, than the firing of Oils by mixing them with Acids. It could never have been suspected that a mixture of two cold liquors would produce a sudden, violent, bright, and lasting flame, like that we are at present considering. Beccher gave notice, in his _Physica subterranea_, that highly rectified Spirit of Wine would be set on fire by mixing it with highly concentrated Oil of Vitriol. Afterwards Borrichius, a Danish Chymist, published a process for kindling Oil of Turpentine, by mixing it with the Nitrous Acid, as we find in the Philosophical Transactions of Copenhagen for the year 1671. Most Chymists have since tried to repeat those experiments, and particularly to fire the Oil of Turpentine by mixing it with Oil of Vitriol, or Spirit of Nitre; but to no purpose, when they made use of the Oil of Vitriol, till Mr. Homberg told us, in the Memoirs of the Academy of Sciences for 1701, that he had fired Oil of Turpentine by mixing it with Oil of Vitriol. To make the experiment succeed he requires, "That the Oil of Vitriol be dephlegmated as much as possible, and that the Oil of Turpentine be the last that comes over in distillation, which is thick like a syrop, and of a dark-brown colour; for that which is white, and rises at the beginning of the distillation, never takes fire." These are his own words: but no body else hath ever succeeded in making the experiment. Tournefort had succeeded, a little before Homberg, in firing, not Oil of Turpentine indeed, in which he always failed, but the Oil of Sassafras, by mixing it with an equal quantity of well dephlegmated Spirit of Nitre. Homberg came afterwards, as appears by the Memoirs of the Academy for the year 1702, to fire with Spirit of Nitre the Essential Oils of the aromatic plants of India; and in 1706 Mr. Rouviere fired, with Spirit of Nitre, the empyreumatic Oil of Guaiacum. While this Oil of Guaiacum is burning, a porous spongy body rises from the midst of the flame, to the height of about two feet above the vessel. Lastly, several years after all these discoveries, Messrs. Geoffroy and Hoffman, the one at Paris, and the other at Hall in Saxony, found a way to fire the Æthereal Oil of Turpentine, each by a different process; yet agreeing in this, that they both combined the Vitriolic Acid with the Nitrous, and with this compound Acid fired that Æthereal Essential Oil, which is one of the thinnest, and, probably for that very reason, the most unfit to produce a flame with Acids. The most celebrated Chymists, as appears from this short account, have employed themselves in firing Essential Oils; but no body attempted the experiment on Fat Oils. It was not so much as suspected that they were capable of taking fire after this manner, till in 1745 I read before the Academy a Memoir on Oils, which I have already mentioned, and in which I express myself thus: "I put two ounces and a half of Walnut Oil into the bottom part of a broken retort, having the figure of a cap, or concave hemisphere; and poured thereon two ounces of smoking Spirit of Nitre. It was scarce put in when a considerable ebullition arose, with a very thick smoke. As I found it continually increasing, and very fast too, I retired a little, that I might observe the event without danger. This caution was not unnecessary: for immediately the whole mixture blew up as high as the ceiling, with a noise like the discharge of a musket. Nothing was left in the vessel but a black matter, which still continued to boil a little and run over, and at last remained very rare, spungy, and as full of holes as a honeycomb: its consistence also was such that it did not stick to my fingers when I handled it. "As Mr. Geoffroy, who first found the means of firing the natural Balsams, observed in them a similar explosion on that occasion, it appears that my Oil was very near taking fire in this experiment: which makes me presume that we may at last succeed in firing Fat Oils likewise, and consequently all others; seeing these have always been looked upon as the most unlikely to produce that phenomenon. I imagine that, to accomplish this, nothing more is necessary than to make use of sufficiently great quantities, and to order it so that the surfaces of the liquors, where they come into contact, may be of a large extent." Afterwards, in 1747, Mr. Rouelle read before the Academy a Memoir on the accension of Oils by Acids. That Memoir contains a great number of curious experiments, and peculiar manual operations described very distinctly, from which there results a general method of firing without fail, not only Essential Oils, but even any Fat Oil whatever: so that my conjecture, concerning the possibility of firing these latter Oils, mentioned in my above-cited Memoir of 1745, is now changed into a certainty. I shall proceed to explain how I conceive these accensions are brought about, and endeavour to account for the phenomenon from such causes as to me seem the most probable. A due attention to the phenomena produced by mixing Oils with Acids will enable us, I imagine, to discover the natural cause why the Oils take fire. It is certain, and demonstrated by the most decisive experiments, that the friction of several bodies rubbing against each other produces heat; and that when these bodies are combustible, and the heat produced by their friction rises to a certain degree, they take fire. This, in my opinion, is what happens to Oils when mixed with concentrated Acids. When these two sorts of substances rush into union with rapidity, as in the experiments under consideration, there must necessarily be a great friction among their parts. This friction produces the heat observed at the time of their union. The more concentrated the Acids are, with the greater violence and rapidity do they act upon the Oils, and the greater is the heat raised. If the Acids be concentrated to such a degree as to produce, by uniting with the Oils, a heat equal to that of an ignited body, the combustible substances that are exposed to it, which in this case are Oils, must needs take fire and flame. The heat produced on this occasion is so great, that, even when the inflammation doth not take place, if you touch the surface of the Oil with your finger, as soon as the Acid hath had its effect, you will find it burn you like a live coal. Two pieces of wood, rapidly and violently rubbed against each other, take fire. What is it that is kindled in this case? It can be nothing but their Oil: for they contain no other combustible principle. Why doth this Oil take fire? I do not think it possible to assign any reason for it, but the heat produced by the friction of the pieces of wood containing the Oil. If, when Oil is dispersed in a body, of which it is only one component principle, and consequently mixed with many saline, aqueous, and earthy parts, that are not inflammable, but, on the contrary, make the Oil less so, the Oil nevertheless takes fire, and burns when agitated by a sufficient degree of heat; why shall not this very Oil, when separated from the mixt of which it made a part, when united into one distinct mass, and entirely, or almost entirely, freed from the heterogeneous, incombustible parts with which it was combined, and consequently now more inflammable than before; why, I say, shall it not take fire, when exposed to a degree of heat equal, or rather superior, to that which is produced by rubbing two pieces of wood together? Let us now examine the phenomena produced when Oils are fired by Acids, all the circumstances that favour or hinder their accension, and see if they agree with the explanation here offered. First, no sort of Oil will take fire with any Acid whatever that is not highly concentrated; for weak Acids act but feebly on Oils, and dissolve them slowly; so that the friction is neither quick nor violent, and consequently produces too faint a heat, far below the degree of ignition. Secondly, no inflammation is produced when Acids and Oils are mixed in too small quantities; but the more Acid and Oil you mix together, the greater is the certainty of succeeding: for the heat is exactly in proportion to the friction that produces it; and the total quantity, or amount, of this friction is so much the greater, as there are more particles rubbing against each other at the same time. So that if a very small quantity of Acid and Oil be mixed together, there will be but a very small quantity of friction, and consequently a very small quantity of heat; and in that case no inflammation. It was with a view to avoid these inconveniencies, and to procure the opposite advantages in as great a degree as possible, that, in the passage above quoted from my Memoir of Oils, I proposed mixing together large doses of Acid and of Oil, as one of the means by which we might succeed in the accension of Fat Oils. Thirdly, the figure of the vessel, in which the two liquors are mixed together, is not a matter of indifference. A wide-spreading vessel, of a large diameter with respect to the quantity of liquor it is to contain, favours the inflammation much more than one of a small diameter. Nay, it may not succeed at all in too narrow a vessel, though all other circumstances be properly attended to. The reason of this is, that the activity of heat produced by friction is not in proportion to the successive, but to the simultaneous frictions: for the heat actually produced by the frictions of an hundred particles, rubbing successively against each other, with intervals sufficient to let the heat go off, almost as fast as it is generated, would be equal to the friction of a single particle only; whereas the heat actually produced by the friction of the same number of particles, all rubbing against each other at the same instant, would be equal to the frictions of all the particles taken together, and consequently an hundred times more active than the other[11]. This being laid down, it is easy to conceive how a large vessel favours the accension more than a small one. It is certain that two liquors which mutually present large surfaces to each other, at the instant of their being mixed together, touch each other at one and the same time in a much greater number of points, than if each had but a small surface; and consequently that they must unite much sooner, and with greater rapidity, in the former case than in the latter. [11] I believe this proposition is not strictly true: for it appears to me, that, in order to make the heat, produced by the simultaneous frictions of an hundred particles, an hundred times more active than that produced by the successive frictions of the same number of particles, it is necessary that the simultaneous frictions should act all together in one point or center; which is impossible. But, as the particles that rub against each other, in the present case, are very near and contiguous, it is still true that the heat, resulting from their simultaneous frictions, is much more active than that produced by successive frictions only: which is sufficient for our present purpose. With these views, and in order to give the liquors this advantageous disposition, I recommended it as what would greatly promote the inflammation of Fat Oils, to order the liquors so, that, at the moment of their mixture, a large surface of each might come into contact with the other. Fourthly, if we reflect on the experiments hitherto made for kindling Oils by Acids, we shall easily be convinced that all Oils are not equally apt to be fired; and that light, æthereal, very thin, Essential Oils do not produce this phenomenon so readily and so surely, as those of the same kind that are heavy and thick, or at least soon grow thick upon being mixed with Acids. Mr. Homberg says positively in the above-cited passage of his Memoir, that he never could succeed in setting fire with the Acid of Vitriol to the white, æthereal Oil of Turpentine; that is, to the lightest which comes over first in distillation; but that the very same Acid set fire to "that which comes over last in distillation, which is thick like a syrop, and of a dark-brown colour." All the experiments by which Oils have been fired, from those of Beccher and Borrichius down to those of Geoffroy and Hoffman, were made on the Essential Oils of the aromatic plants of India, which are the heaviest we know, and on the empyreumatic Oil of Guaiacum, which, besides being very ponderous, is also very thick. Now these singular effects likewise agree perfectly well with our explanation. It is certain that the parts of a heavy fluid do not yield to any impulse or shock, so easily as those of a lighter fluid; just as the parts of a thick, viscous fluid undoubtedly resist any attempt to separate them, so much the more the nearer the consistence of that fluid is to solidity, or the further it is removed from the state of fluidity. Now, the more resistance the Acid meets with in separating and dividing the parts of the Oil, as it must do to dissolve them, the more considerable will be the force and motion with which it must necessarily act to surmount those obstacles; besides, as experience teaches us that the density and viscidity of the Oils do not, at least to sense, diminish the quickness and activity which the Acid exerts in uniting with them; the greater therefore must be the collisions, frictions, and heat produced: and this plainly shews why heavy, thick Oils take fire, in this case, more readily than those which are fluid and light. It may here be objected, that Fat Oils, which are thicker and heavier than the light Essential Oils, take fire nevertheless with greater difficulty. This objection is easily answered, by observing, that when we say Acids fire heavy thick Oils with more ease than thin light Oils, this position must be restricted to Oils of the same kind, on which Acids have an equal, or nearly equal, action; that is, to such Oils as differ from each other in no other respect but their thickness and weight. For example, Mr. Homberg, who could by no means set fire, with Oil of Vitriol, to the Oil that rises first in the distillation of Turpentine, found that the same Acid would fire the Oil that comes last over: and therefore it is reasonable to attribute his success, in firing this last Oil, to its being thicker and heavier than the former; seeing these two Oils are in other respects of the same nature; that Acids have an equal action on both; and that they differ from each other only in the qualities specified above. But it is evident, that, if the Oils compared together be of different kinds, and differ from each other, not only in weight and thickness, but also by containing different principles, or, at least, the same principles combined differently, and in different proportions, the action of any Acid on those Oils must also be different; and that regard must be had thereto in determining their degrees of inflammability. Now all this is applicable to Fat Oils, when compared with light Essential Oils, in point of inflammability. If all these Oils were of the same nature, and differed from each other in weight and thickness only, the objection drawn from Fat Oils, which though thicker than Essential Oils do not take fire so easily, would be a very good one, and fact would be against our reasoning. But this is far from being the case: the properties, as well as the analysis, of Fat Oils shew their nature to be very different from that of Essential Oils; that there is more water in their composition; and that they are full of a mucilaginous or gummy principle, which must greatly obstruct their inflammability, and the action of Acids upon them. None of the effects, therefore, that attend the firing of Oils with Acids, is repugnant to our way of accounting for the phenomenon, which is one of the most beautiful in all Natural Philosophy. To conclude this important subject, nothing now remains but to consider the effects produced by the Vitriolic Acid in these accensions. This Acid, though of a stronger nature, and capable of being more highly concentrated than the Nitrous Acid, seems however less qualified to produce a flame with Oils. Indeed Mr. Homberg fired Oil of Turpentine by mixing it with Oil of Vitriol: but I do not know that the experiment hath succeeded with any other Chymist; on the contrary, most of those who have tried it affirm, that they never could fire any Oil with that Acid alone. Oils are probably in the same case as metallic substances, with regard to these two Acids. We know that the Nitrous Acid dissolves those substances with vastly more activity and violence than the Vitriolic Acid exerts upon them; which may depend, either on the disposition and configuration of their parts, or on the portion of phlogiston which, according to the opinion of most Chymists, is united with the Nitrous Acid, is its peculiar characteristic, and the cause of the great vivacity with which it dissolves almost all matters that contain the phlogiston. I say _almost_ all matters that contain the phlogiston; because there are some substances that contain a great deal thereof, and yet are not at all acted on by the pure Nitrous Acid. These substances are matters perfectly charred: that is, such as are capable of enduring the greatest violence of fire in close vessels, without yielding a single atom of Oil; that burn almost quite away, yet only grow red hot without flaming; or at least produce but a very small, slight flame, from which it is impossible to obtain the least particle of soot or fuliginosity; in a word, that contain an inflammable matter, but such as is fit to be an ingredient in the composition of metallic substances, to which the peculiar title of the Phlogiston is appropriated. I say, then, that if the Nitrous Acid be poured on a mere coal, perfectly charred, it is impossible for the Acid, be it ever so highly concentrated, to set the coal on fire, though heated before to the greatest degree that it can possibly admit of without kindling; and, which is still more remarkable, if a live coal be plunged into the most highly smoking Spirit of Nitre, it will be extinguished as if dipt in pure water. But to return to the Vitriolic Acid: it is singular enough that this Acid, which attacks Oils with less activity, and for that reason seems less fit to set them on fire, than the Nitrous Acid, yet greatly promotes their accension, when mixed with that very Acid. This may be owing to its rendering the Oils with which it mixes heavier and thicker; or else, as Mr. Rouelle conjectures with great probability, being more concentrated than the Nitrous Acid, and having a greater affinity with water, it dephlegmates the other, and thereby increases its activity; or, lastly, this may arise from some other cause yet unknown to us, and perhaps from that by which the Acids of Nitre and of Sea-salt, which, when separate and perfectly pure, can neither of them dissolve Gold, are enabled, when combined together, to make a perfect solution of that metal. PROCESS III. _To combine Essential Oils with Mineral Sulphur. Balsam of Sulphur. This Composition decompounded._ Put into a matrass one part of Flowers of Sulphur; pour on them six parts of the Essential Oil of Turpentine, for instance; set the matrass in a sand-bath, and heat it gradually till the Oil boil. The Sulphur, which at first lay at the bottom of the matrass, will begin to melt, and appear to dissolve in the Oil. When it hath boiled in this manner for about an hour, take the matrass from the fire, and let the liquor cool. A great deal of the Sulphur that was dissolved therein will separate from it as it cools, and fall to the bottom of the vessel in the form of needles, much like a Salt shooting in water. When the liquor is perfectly cold, decant it from the Sulphur that lies at the bottom of the vessel: to that Sulphur put fresh Oil of Turpentine, and proceed as before: the Sulphur will again disappear, and be dissolved in the Oil: but when the mixture is cold, you will find new crystals of Sulphur deposited at the bottom. Decant once more this Oil from the crystals, and pour on fresh Oil to dissolve them: continue the same method, and you will find that about sixteen parts of Essential Oil are required to keep one part of Sulphur dissolved when cold. This combination is called _Balsamum Sulphuris Terebinthinatum_, if made with Oil of Turpentine; _Anisatum_, if with Oil of Anise-seeds; and so of others. _OBSERVATIONS._ Essential Oils do not dissolve Sulphur, in such quantities, and with so much ease, as Fat Oils do. It was shewn above, that a Fat Oil is capable of keeping a considerable quantity of Sulphur in solution; whereas no less than sixteen parts of Essential Oil are required to dissolve one part only of Sulphur, as in this process. The property which Sulphur hath of separating, in part, from the Essential Oil in which it is dissolved, and falling to the bottom of the vessel in the form of crystals, as the Oil cools, proves that it is a kind of Neutral Salt, which, being insoluble in water, because of the great quantity of inflammable matter that serves it for a basis, is not to be dissolved but by substances that actually contain themselves a great deal of inflammable matter; such as Oils and Metallic substances. Though the latter are almost always solid, it nevertheless unites with several of them into regular forms, resembling saline crystals in every thing but pellucidity; as appears, for example, in several Pyrites, Antimony, and some other sulphureous minerals. But when it is dissolved in Oils, especially in such as are capable of keeping but a small quantity thereof in solution, and consequently drop a good deal of it as they cool, it is precisely in the case of one of those Salts whereof hot water dissolves more than cold; that is, the Oil, that is saturated with as much Sulphur as it can possibly take up when boiling hot, lets some part thereof precipitate as it cools; while the Sulphur thus separated from the Oil unites into little glebes of a regular figure, and actually crystallizes; in the same manner as Nitre, when boiling water hath dissolved as much thereof as it can possibly take up, partly separates from it when it cools, and falls to the bottom of the vessel in small crystalline _moleculæ_, of the form peculiar to that Salt. Mr. Homberg made some very curious experiments on this combination of Sulphur with an Essential Oil. In the Memoirs of the Academy he gives the following analysis thereof. "Put your Sulphur dissolved by Oil of Turpentine into a pretty large retort, because the matter puffs up towards the end, and distil with a very gentle heat for twelve or fifteen days and nights. There will come over about two thirds of the quantity of a colourless Oil of Turpentine, and at the same time _a pretty considerable quantity_ of a whitish ponderous water, as acid as good Spirit of Vitriol. After this, the drops of Oil that come off will begin to be red. Then change your receiver, and increase the fire gradually; and in seven or eight hours time, with a very great heat, force off all that will rise, using a glass retort for your recipient. At last, most of the Oil will come over into the receiver very thick and high-coloured, still accompanied with a whitish and very acid water. In the retort will be left a black _caput mortuum_, spongy, or foliated, shining, and insipid.... This _caput mortuum_ neither grows white, nor flames, nor wastes considerably in a strong fire. "The matter that comes over into the receiver must be distilled again, with a very gentle heat continued for several days and nights, in order to separate once more the colourless Oil and the remaining acid water, till the Oil begin to come off red. Then take the retort from the fire, and on the black gummy matter left in it pour good Spirit of Wine; mix the whole well together, and distil with a very gentle heat. When this Spirit of Wine is come off, pour some fresh on the black gum left in the retort, and distil as before. Repeat this till the Spirit of Wine cease to have a bad smell." There is great reason to believe, that, by the union which the Sulphur contracts with the Oil, the cohesion of the Acid and the Phlogiston, which constitute that mineral, is considerably weakened; and that this is what occasions the decomposition of the Sulphur so manifest in Mr. Homberg's analysis. The inflammable matter of the Sulphur is so incorporated with that of the Oil in the solution, that they form together one homogeneous whole; by which means the Acid of the Sulphur, which is of course dispersed through the whole liquor, is not now combined with the Phlogiston, as it was in the Sulphur before it was blended with the Oil; that is, with the pure Phlogiston; but with that Phlogiston which constitutes the oily mixture, or, which is the same thing, with actual Oil. And this is the reason that a composition of Oil and Sulphur yields, in distillation, nearly the same principles that a combination of the same Oil with the Vitriolic Acid would yield. We have already seen, under the head of Fat Oils, that when Oils are combined with Acids, if this combination be again decompounded by distillation, those two substances cannot be obtained in their original state; but that they are changed and partly decomposed. The case is the same in the experiment before us. We first get, by distillation, a pretty considerable quantity of Oil of Turpentine, that seems to have suffered no change at all. This first Oil is that which the action of fire separates from the Acid; and this it effects with so much the more ease, that, a great quantity thereof having been necessarily used to dissolve a little Sulphur, it greatly exceeds the quantity of Acid in the mixture, and that the distillation is ordered to be made with a very weak degree of heat: for M. Homberg says, it ought to be continued twelve or fifteen days and nights. Now this manner of distilling, with a very gentle heat, is the most effectual means of separating Oils, especially light Essential Oils, from Acids; because these Oils rise in distillation with very little heat; whereas the Acids, being much more ponderous, require a great deal more. The Oil that rises first in distillation, appears indeed to be the same with that which was originally used in the mixture; but the quantity is much smaller: first, because some part of it, being combined with the Acid of the Sulphur, is thereby rendered thick and heavy, which hinders it from rising in this first distillation with a very gentle heat, and is the reason that it cannot be elevated without a much stronger degree of fire. It is this part that afterward comes over in the form of a red liquor upon increasing the fire. The second cause why the quantity of Oil is lessened, is, that part of it is decomposed in the operation. This decomposed part of the Oil furnishes that considerable quantity of water which ascends at the same time with the Oil, or a little after it, and serves for a vehicle to the Acid that rises with it in this first distillation; which Acid, though pretty strong, is now much more loaded with water than when it was an ingredient in the combination of Sulphur. This acid water is of a milky white colour, because many oily particles are suspended and diffused in it, but not perfectly dissolved. The _caput mortuum_ that is left in the retort, after all the red thick Oil is driven up by a very strong degree of fire, is a sort of charred matter, consisting of some of the earth of the Sulphur, and of the decomposed Oil, united with a phlogiston, which is probably furnished by both these substances. This matter contains also a little Acid fixed with it. This Acid reproduces Sulphur, or at least becomes sulphureous, and flies off in vapours, when the coal is urged by a violent forge-heat: for Mr. Homberg observed, that by this means it exhaled an odour of Sulphur, and lost in weight. This charred matter is of a singular nature: for, by being exposed to a forge-heat, and even to the heat in the focus of a burning glass, it seemed to suffer no other change than some loss of weight, occasioned by the evaporation of the acid effluvia carried off by the heat; for it still retained its black colour, and was neither consumed nor vitrified. In order to melt it, Mr. Homberg was forced to mix it with Borax. This Salt converted it into a glass of a dark-grey colour: and, as there appeared a little verdegris on the surface of this glass after keeping it in a moist place, he thereby found that the Sulphur he had used contained a little Copper. We know that the earth of Copper is refractory, and that it communicates a dark colour to matters vitrified along with it: and perhaps it was the cause why the fixed matter in question retained its blackish colour so obstinately, notwithstanding the phlogiston that must have been in it at first was, in all probability, consumed by the violent ignitions it underwent. As to the thick oily matter, called _gummy_ by Mr. Homberg, from which he directs Spirit of Wine to be repeatedly distilled, till it cease to have a disagreeable smell, there is great reason for thinking it to be, as we said before, a portion of the Oil which the Acid hath rendered thick and heavy. The Spirit of Wine dissolves and carries up the most acid part, which always hath a disagreeable smell. Mr. Homberg says, that "the part remaining after this, which he calls the _Gum of common Sulphur_, hath a pleasant balsamic odour; that it partly dissolves in Spirit of Wine, a hard resinous matter being left, which will not dissolve, either in Spirit of Wine, or in the strongest lixivium." Of consequence, therefore, it is neither a resinous matter nor a sulphur; "yet it dissolves perfectly in distilled Oils." What then is this singular body? It is certainly a subject for very curious inquiries. In general, Mr. Homberg's whole process is full of interesting facts, and well deserves to be repeated, carried further, and carefully attended to. PROCESS IV. _To combine Essential Oils with Fixed Alkalis. Starkey's Soap._ Take Salt of Tartar, or any other Alkali, thoroughly calcined. Heat it in a crucible till it be red, and in that condition throw it into a hot iron mortar: rub it quickly with a very hot iron pestle; and as soon as it is powdered pour on it, little by little, nearly an equal quantity of Oil of Turpentine. The Oil will enter into the Salt, and unite intimately with it, so as to form a hard paste. Continue rubbing this composition with the pestle, in order to complete the union of the two substances; and, as your Oil of Turpentine disappears, add more, which will unite in the same manner, and give a softer consistence to the soapy mass. You may add still more Oil, according to the consistence you intend to give your Soap. _OBSERVATIONS._ Essential Oils do not unite near so easily as Fat Oils with Alkalis. For this reason, to make a Soap with an Essential Oil, we must take a method different from that used in common soaperies. For if an Essential Oil be substituted for the Fat Oil, in the ordinary way of making Soap, far from combining with the alkaline lixivium, though ever so strong, it will be wholly dissipated and vanish: so that, after boiling some time, you will find nothing but the lye, just as when first put in, only a little more concentrated. The water, in which the Alkali is dissolved when in the form of a lye, is the principal thing that hinders the Salt from uniting with the Essential Oil. Water is such an enemy to this union, that, if the Alkali be ever so little moist, the operation will not succeed; even though all the other precautions mentioned in the process should be exactly observed. In order, therefore, to free the Alkali from all humidity, it is necessary to begin with making it red-hot; and then, that this Salt, which is very greedy of moisture, may not imbibe any from the air, before it be mixed with the Essential Oil, it must not be suffered to cool; but the mixture must be made in a hot vessel, as soon as the Salt is reduced to powder. When every particle of the Salt is once covered with Oil, you need not fear its attracting any moisture, at least very quickly, because the Oil opposes its admission. Starkey, the first Chymist who found the means of making Soap with an Essential Oil, and by whose name this kind of Soap is therefore called, made use of a much more tedious method than that proposed in our process. He began with mixing a very small quantity of Oil with this Salt, and waited till all the Oil united therewith of its own accord, so as to disappear entirely, before he added any more; and thus protracted his operation exceedingly, though in the main it was the same with ours. The method here proposed is more expeditious, and was invented by Dr. Geoffroy. Starkey's Soap dissolves in water much as common Soap does, without any separation of the Oil: and by this mark it is known to be well made. It may also be decompounded, either by distillation, or by mixing it with an Acid: and its decomposition, in either of these ways, is attended with nearly the same phenomena as the decomposition of common Soap. CHAP. VI. _Of the_ SUBSTANCES _obtained from_ VEGETABLES _by Means of a_ GRADUATED HEAT, _from that of boiling Water, to the strongest that can be applied to them in close Vessels_. PROCESS I. _To analyze Vegetable Substances that yield neither a Fat nor an Essential Oil. Instanced in Guaiacum-Wood._ Take thin shavings of Guaiacum-wood, and put them into a glass or stone retort, leaving one half thereof empty. Set your retort in a reverberating furnace, and lute on a large glass receiver having a small hole drilled in it; such as is used for distilling the Mineral Acids. Put a live coal or two in the furnace, to warm the vessels gently and slowly. With a degree of heat below that of boiling water, you will see drops of a clear insipid phlegm fall into the receiver. If you raise the fire a little, this water will come slightly acid, and begin to have a pungent smell. With a degree of fire somewhat stronger, a water will continue to rise which will be still more acid, smell stronger, and become yellowish. When the heat comes to exceed that of boiling water, the phlegm that rises will be very acid, high coloured, have a strong pungent smell, like that of matters long smoked with wood in a chimney, and will be accompanied with a red, light Oil, that will float on the liquor in the receiver. And now it is necessary that the operation be carried on very cautiously, and vent frequently given to the rarefied air by opening the small hole in the receiver: such an incredible quantity thereof rushing out of the Wood, with this degree of heat, as may burst the vessels to pieces, if not discharged from time to time. When this red, light Oil is come over, and the air ceases to rush out with impetuosity, raise your fire gradually, till the retort begin to redden. The receiver will be filled with dense vapours; and, together with the watery liquor, which will then be extremely acid, there will rise a black, thick, ponderous Oil, which will fall to the bottom of the receiver, and lye under the liquor. Then give the utmost degree of heat; that is, the greatest your furnace will allow, and your vessels bear. With this excessive heat a little more Oil will rise, which will be very ponderous, as thick and black as pitch; and the vessels will continue full of vapours that will not condense. At last, when you have kept the retort exceeding red for a long time in this extremity of heat, so that it begins to melt, if it be of glass, and you perceive nothing more come over, let the fire go out and the vessel cool. Then take off your receiver: from the black oil at bottom decant the acid liquor with the red Oil floating on it, and pour them both into a glass funnel, lined with brown filtering paper, and placed over a bottle. The acid liquor will pass through the filter into the bottle, and the Oil will be left behind, which must be kept by itself in a separate bottle. Lastly, into another funnel, prepared as the former, pour the thick Oil remaining with a little of the acid liquor at the bottom of the receiver. This liquor will filter off in the same manner, and thus be separated from the heavy Oil. In the retort you will find your Guaiacum-shavings, not in the least altered as to their figure, but light, friable, very black, scentless, and tasteless, easily taking fire, and consuming without flame or smoke; in short, you will find them charred to a perfect coal. _OBSERVATIONS._ Hitherto we have examined the substances that may be obtained from vegetables, either without the help of fire, or with a degree of heat not exceeding that of boiling water. The analysis of plants can be carried no further without a greater degree of heat: for, when the principle of odour, and the essential oil of an aromatic plant, are wholly extracted by the preceding processes, if the distillation be afterward continued without increasing the heat, nothing more will be obtained but a little Acid; which will soon cease, as a small part only of the quantity contained in the plant will be elevated; the rest being either too ponderous, or too much entangled with the other principles of the body, to rise with so small a degree of heat. In order, therefore, to carry on the decomposition of a plant, from which you have, by the methods before proposed, extracted all the principles it is capable of yielding when so treated; or, which comes to the same thing, in order to analyze a vegetable matter, which affords neither an expressed nor an essential oil, it must be distilled in a retort with a naked fire, as directed in the process, and be made to undergo all the degrees of heat successively, from that of boiling water, to the highest that can be raised in a reverberating furnace. A heat inferior to that of boiling water, with which we must begin in order to warm the vessel gradually, brings nothing over, as hath been said, but an insipid water, destitute of all acidity. By increasing it nearly to the degree of boiling water, the distilled water comes to be slightly acid. When the heat is made a little stronger than that which is necessary for the elevation of an Essential Oil, the acidity of the water that comes off is much more considerable. It hath now both colour and smell, and there rises with it a red, light Oil, that floats on the liquor in the receiver. This is not an Essential Oil; it hath none of the odour of the plant. Though so light as to float on water, yet it will not rise with the degree of heat that raises Essential Oils; even those that much surpass it in gravity, and will not swim on water as this does. This proves that the ease or difficulty, with which a particular degree of heat raises any substance in distillation, doth not depend altogether on its gravity: its dilatability, or the volatile nature of the matters, with which it is so closely united as not to be separated from them by distillation, may probably contribute greatly to produce this effect. It is very surprising that a substance so hard, so compact, so dry, in appearance, as Guaiacum-wood, should yield such a large quantity of water by distillation; and it is equally so, that it should discharge so much air, and with so much impetuosity, as nothing but experience could render credible. We have, in the process, directed the precautions to be taken when this air, from being prodigiously condensed in the body of which it made a part, is set at large, rushes out of confinement, and expands with all its natural elasticity. From this air arises the greatest danger attending the operation. It hath been remarked, that the heaviest and most compact woods yield the most air in distillation: and accordingly Guaiacum-wood, which we have chosen for an instance, as exceeding almost all others in hardness and weight, discharges a vast quantity of air when analyzed. The thick, burnt, empyreumatic Oil, that comes over last in this distillation, is heavier than water; on account, probably, of the great quantity of Acid with which it is replete. The two kinds of Oil obtained in this analysis may be rectified, by distilling them a second time, or rather several times; by which means they will become lighter and more fluid, as we have seen happen to Fat and Essential Oils. In general, all thick, heavy Oils constantly owe these qualities to an Acid united with them; and it is by being freed from some of that Acid in distillation, that they always acquire a greater degree of lightness and fluidity from that operation. To these laws all vegetable Oils are subject, of what nature soever they be. The analysis of a vegetable substance, exhibited above, shews what may be obtained from them, when distilled in close vessels, with a graduated heat, from that of boiling water, to that which converts the mixt to a perfect coal; viz. Phlegm, an Acid, a light Oil, much Air, and a thick Oil. But this analysis is far from being a complete one: it may be carried much farther, and made more perfect. None of the principles obtained by this analysis are pure, simple, and thoroughly separated from the rest. They are still in some measure blended all together: their separation is but begun; and each requires a second and more accurate analysis, to reduce it to the greatest degree of purity of which it is capable. The Oil and the Acid chiefly merit so much pains. A great deal of the Acid of the plant remains, as was said, combined with the two sorts of Oil here obtained; which we have reason to think differ no otherwise from one another, than as there is more or less Acid united with each. The best way of freeing these Oils from their redundant Acid is to distil them frequently from Alkalis and Absorbents. Some of our best Chymists have taken this pains with several sorts of Oils; but the method might be still extended, and the operation carried further than hath yet been done. The Acid is in the same circumstances nearly as the Oil. The first that rises is mortified with much water, to which it owes a good deal of its volatility. That which comes over last is much more concentrated, and consequently heavier; yet it is still very aqueous. It might be freed in a great measure from this adventitious water, and so rendered much stronger; which would give us a better opportunity to discover its nature and properties, of which we know but very little. Water is not the only heterogeneous substance that disguises the vegetable Acid: a pretty considerable quantity of the Oil of the plant is also combined with it, and contaminates its purity. The proof of this is, that, when these Acids are kept, in the same condition in which they first come over, for any length of time, in a glass vessel, they gradually deposite, on the bottom and sides of the vessel, an oily incrustation, which grows thicker and thicker the longer it stands; and, as this oily matter separates from it, the Acid liquor appears less unctuous and saponaceous. A very good way to separate this Oil more effectually from the Acid is to combine the whole with absorbents, and abstract the Oil again by distillation. By this means a very sensible quantity of Oil may be separated that was not perceived before. On this occasion it is proper to remark, that the Oil thus united with the vegetable Acid is perfectly dissolved by it; seeing it is thereby rendered miscible with water, so that it doth not, like Alkaline soaps, in the least obscure its limpidity, or give it a milky cast: for these aqueous, oily Acids are very transparent, especially after they have stood for some time. The air that is discharged with impetuosity in the operation, and must be let out, is loaded with many particles of Acid and Oil reduced to vapours, which it carries off; and by this means the quantity of the principles extracted from the mixt cannot be accurately determined: nor are the vapours, of which the vessels remain full after the operation, any other than particles of Acid and Oil, which the violence of the fire hath rarefied exceedingly, and which do not easily condense. If we distil in this manner a vegetable aromatic substance, which of course contains an Essential Oil, provided it hath not been previously extracted by the appropriated process, this Essential Oil will rise first, as soon as the distilling vessel acquires the heat of boiling water: but its scent will not be near so sweet or grateful, as if it were distilled in the manner before directed as properest for it. On the contrary, it will have an empyreumatic smell: because in this way it is impossible to avoid scorching and half-burning some of the matter distilled; especially that part of it which touches the sides of the retort. Moreover, the very same equable degree of heat can hardly be kept up with a naked fire. The Essential Oil, therefore, though it rises first, will not be pure, but contaminated with a mixture of the empyreumatic Oil that first comes over, and will be confounded therewith. If a substance abounding with Fat Oil, that hath not been expressed from it, be distilled according to the present process, it will yield no Fat Oil by distillation; but only much more of the first clear Oil, and of the second thick Oil, than if all the Fat Oil it would have afforded had been first drawn off by expression: for as the Fat Oil will not rise in distillation, without a degree of heat greater than that of boiling water, neither can it endure such a degree of heat without changing its nature, without losing that mildness, and, in a great measure, that unctuosity which is natural to it. It will therefore be confounded with the other empyreumatic Oil, which, in all probability, would itself be no other than a Fat Oil, if it could be wholly extracted, without the aid of fire, from the vegetable substances containing it. Most vegetable substances, when distilled with a strong fire, yield the same principles with that which we have chosen for an instance. Entire plants of this kind, those from which the odorous principle, the Essential Oil, or the Fat Oil, hath been drawn, those of which extracts have been made by infusion or decoction, or the extracts themselves; all such matters being distilled yield a Phlegm, an Acid, a thin Oil, Air, and a thick Oil, and the products of their several analyses differ from each other, only on account of the different quantity or proportion that each contains of the principles here enumerated. But there are many other plants, which, besides these substances, yield also a considerable quantity of a Volatile Alkaline Salt. This property is possessed chiefly by that tribe of plants which is distinguished by having cruciform flowers; among which there are some that being analyzed greatly resemble animal matters. We shall now analyze one of these; Mustard-seed, for instance. PROCESS II. _To analyze a vegetable Substance which yields the same Principles as are obtained from Animal Matters; instanced in Mustard-seed._ With an apparatus like that of the preceding process, and with the same fire, distil Mustard-seed. With a degree of heat inferior to that of boiling water, there will come over a phlegm somewhat coloured, and impregnated with a Volatile Alkaline Salt. With a degree of heat greater than that of boiling water, the same kind of phlegm, impregnated with the same Salt, will continue to come over; but it will be much higher coloured, and will be accompanied with a light Oil. At this time a considerable quantity of air is discharged; with regard to which the same precautions must be taken as in distilling Guaiacum. If the fire be gradually raised, there will come over a black thick Oil, lighter however than water; and at the same time vapours will rise, and, condensing on the sides of the receiver, form into sprigs or ramifications. This is a Volatile Alkaline Salt, in a concrete form, like that of animals, as we shall hereafter see. These vapours are much whiter than those of Guaiacum. When you have thus drawn off, with a very strong fire, all the Volatile Alkali and thick Oil contained in the subject, there will be nothing left in the retort but a sort of coal, from which a small quantity of phosphorus may be obtained, provided the retort you employ for that purpose be good enough to stand a very violent heat. _OBSERVATIONS._ Mustard-seed furnishes us with an instance of a vegetable, from which we obtain, by analyzing it, the very same principles that animal matters yield. Instead of getting an Acid from it, we obtain only a Volatile Alkali; probably because the Acid, which originally enters into the composition of this kind of vegetables, as well as of all others, undergoes in passing through their strainers, and mixing with their juices, such alterations as it suffers when it enters into the composition of animals: that is, it combines with some of their Earth and of their Oil, in such a manner as to be changed into a Volatile Alkali, or at least disposed to be converted into one with the aid of fire. We shall not here speak of the manner of separating and depurating the principles obtained by this process; but reserve it for the analysis of animals, which is absolutely the same. We shall content ourselves with observing, that the first Volatile Alkali which rises at the beginning of the operation together with the phlegm, in a degree of heat below that of boiling water, differs from that which doth not come over till towards the end of the distillation, when the last thick Oil ascends. The different times, and different degrees of heat, in which these two Alkalis rise, shew that the former exists actually and perfectly in the plant; but that the latter is generated during the distillation, and is the product of the fire, which combines together the materials whereof it is composed. Vegetables that thus yield a Volatile Alkali with a heat less than that of boiling water, irritate the organ of smelling, affecting it with a sensation of acrimony; and the effluvia, which rise from them when bruised, make the eyes smart so as to draw tears from them in abundance. Several of these matters, being only bruised, effervesce with Acids: effects producible only by a very Volatile Alkaline principle. This is that Alkali, the lightest of all the principles that can be extracted from bodies, which rises first in our distillation along with the phlegm, and with a degree of heat much inferior to that of boiling water. As the phlegm with which it rises is very copious, it is dissolved thereby; which is the reason it doth not appear in a concrete form. To this water it gives a slight yellowish tinge, because it is impure and oily. The saline Alkaline properties of this liquor have procured it the title of a Volatile Spirit. This Volatile Alkali, which exists naturally and perfectly formed in Mustard-seed, Onions, Garlic, Cresses, and other such vegetables, constitutes a difference between them and animal substances, which contain only the materials requisite to form a Volatile Alkali, but none ready formed, unless they have undergone the putrid fermentation. The second Volatile Alkali which rises in our distillation, but not without a very strong degree of fire, and at the same time with the last thick Oil, seems to be a production of the fire; for if it were already formed in the mixt, as the other is, it would rise with the same heat, and at the same time, being equally volatile. It is not impossible, however, that it may exist perfectly formed in the plant; but, having contracted an union with some Acid, and therewith composing an Ammoniacal Salt, it may by that means be hindered from rising so readily as is agreeable to its natural volatility. The Phosphorus obtained by a violent fire, from the _caput mortuum_ of this distillation, seems to throw a light of probability on this conjecture. There is certainly a great deal of Acid in the composition of Phosphorus. Perhaps this Acid was originally combined with our second Volatile Alkali, and formed therewith, as was said, a sort of Sal Ammoniac. Moreover, almost all the plants that yield a Volatile Alkali by distillation, yield also a considerable quantity of Acid: which may perhaps be the remains of such a Sal Ammoniac decomposed by the operation. This is a subject for curious and useful inquiries. This second Volatile Alkali appears in a concrete form, because very little phlegm comes over along with it; so that the vapours thereof are not sufficient to dissolve it, as they did the first. CHAP. VII. _Of the_ SUBSTANCES _obtained from_ VEGETABLES _by_ COMBUSTION. PROCESS I. _To procure a Fixed Caustic Alkaline Salt from a Vegetable Substance, by burning it in the open Air._ Take any vegetable matter whatever; set it on fire, and let it burn in the open air till it be wholly reduced to ashes. On these ashes pour a quantity of boiling water sufficient to drench them thoroughly. Filter the liquor in order to separate the earthy parts; and evaporate your lye to dryness, stirring it incessantly; and you will have a yellowish-white Salt. Put this Salt in a crucible; set it in a melting furnace, and make a moderate fire, so as not to fuse the Salt. It will turn first of a blue-grey colour, afterwards of a blue-green, and at last reddish. Put on the dome of the furnace; fill it with coals; make your fire strong enough to melt the Salt, and keep it in fusion for an hour, or an hour and half. Then pour it into a heated metal mortar; pound it while it is red-hot; put it, as soon as possible, into a glass bottle, first made very hot and dry, and shut it up close with a glass stopple rubbed with emery. By this means you will have the pure Fixed Alkali of the vegetable substance you burnt. _OBSERVATIONS._ Burning a vegetable substance in the open air is a kind of violent and rapid analysis made by fire, which separates, resolves, and decomposes, several of its principles. When any wood or plant is laid on a quick fire, there ascends from it immediately an aqueous smoke, which consists of little more than phlegm; but this smoke soon becomes thicker and blacker: it is then pungent, draws tears from one's eyes, and excites a cough if drawn into the lungs with the breath. These effects arise from its being replete with the Acid, and some of the Oil, of the vegetable converted into vapours. Soon after this the smoke grows exceeding black and thick: it is now still more acrid, and the plant turns black. Its strongest Acid and last thick Oil are now discharged with impetuosity. This rarefied Oil being heated red-hot suddenly takes fire and flames. The vegetable burns and deflagrates rapidly, till all its Oil is consumed. Then the flame ceases; and nothing remains but a coal, like that found in a retort after all the principles of a plant have been extracted by the force of fire. But this coal having a free communication with the air, which is absolutely necessary to keep a combustible burning, continues to be red, sparkles, and wastes, till all its phlogiston is dissipated and destroyed. After this nothing remains but the Earth and Fixed Salt of the vegetable; which, mixed together, form what we call the Ashes. Water, which is the natural solvent of Salts, takes up every thing of that kind that is contained in the ashes; so that, by lixiviating them, as directed, all the Salt is extracted, and nothing left but the pure earth of the mixt which is thus decomposed. The phenomena observed in the burning of a vegetable substance, and the production thereby of a Fixed Alkali, seem to prove that this salt is the work of the fire; that it did not exist in the plant before it was burnt; that the plant only contained materials adapted to form this Salt; and that this Salt is no other than a combination of some of the Acid, united with a portion of Earth, by means of the igneous motion. In the first place; a Fixed Alkali may be obtained by lixiviation from the ashes of all vegetable matters that contain an Acid, Earth, and Phlogiston, in due proportion. Thus Essential Salts; the substance of extracts made by trituration, infusion, or decoction; wood coals burnt to ashes; all yield a quantity of this Salt in proportion to the quantity of Acid and Earth contained in them. Secondly; Fat, Essential, and Empyreumatic Oils afford, when burnt, such a small quantity of Fixed Alkali as is scarce perceptible; because they contain but a little Acid, and still less Earth: and these same Oils, when rectified by repeated distillations, and then burnt, leave still less of this Salt; because they are separated by rectification from most of the Acid, together with, the small matter of Earth contained in them. Thirdly; those vegetable matters which, being analyzed, furnish a great deal of Volatile Alkali, yield but very little Fixed Alkali; because a great deal of their Acid is employed in forming the Volatile Alkali, which is dissipated by burning the plant: and, for the same reason, those which in distillation afford only a Volatile Alkali, and no Acid, leave in their ashes little or no Fixed Alkali, as is also the case with animal matters. Fourthly, and lastly; the ashes of such plants as have been long steeped in water, and from which infusions and decoctions have been made, always contain the less Alkali the longer they have been infused or boiled, and the more water they were infused or boiled in; because water dissolves and carries off their Acid. It is for this reason that the ashes of float-wood are much less saline than those of green wood. Boerhaave assures us, in his Chymistry, that having exhausted Rosemary by repeated decoctions, and having afterwards boiled the plant thus treated, the ashes produced by it shewed not the least sign of a Fixed Alkali. He says, that, in order to exhaust thoroughly all the saline matters contained in Rosemary, he was obliged to decoct it no less than twenty times successively, with fresh water every time, and never ceased boiling it in this manner, till he was sure that the water, by boiling the plant in it for a long time, took up from it no kind of matter whatever that in the least affected its purity: so that the water of his last decoction had absolutely no smell, taste, or colour; but was in short precisely the same as before he used it for the decoction. The same author observes, that his plant, after having been exhausted in this manner, and having suffered such continued boiling, retained nevertheless its perfect external form; that from being green at first it became brown, and sunk to the bottom of the water, instead of floating thereon as it did before decoction. If, in reiterating this beautiful experiment of Mr. Boerhaave's, you should not succeed as you expect, you must not therefore accuse this great man of having been mistaken on this occasion; seeing it is very difficult, not to say impossible, to ascertain exactly, from the account he hath given of his experiment, all that is necessary to its perfect success: for he hath not specified either the duration of the coctions which he made the Rosemary undergo, or the quantity of water he employed in each; whereas a difference in either of these may occasion a vast difference in the result. It is evident, that if five or six pounds of water be used for each coction of a pound of Rosemary, and be kept boiling for two or three hours, the plant will not be near so much exhausted by being so treated, as if the same quantity thereof were kept boiling for several days, in forty or fifty quarts of water. Indeed, these points seem, in some measure, to be determined, by what he says of the quality which the water of the last decoction ought to have. But the same objections occur here also; nay, the two circumstances of the quantity of water and the duration of the boiling, have the greatest influence here: for the more a plant is exhausted of its Salts, the more difficult it becomes for the water to dissolve and separate the small quantity thereof that remains united with the tenacious Oil; and consequently it may happen, that this last water, after the plant hath boiled in it five or six hours, shall appear insipid, scentless, colourless; and yet that a much greater quantity of water, but reduced by longer boiling to the same quantity with that which hath been boiled but five or six hours, shall have acquired both taste and colour; in a word, shew that it hath taken up some of the principles of the plant. It may also happen, that, a small portion of saline matter being diffused through a large quantity of water, after long continued coction, shall not be perceptible either to the taste or to the eye; but that the very same portion of saline matter shall become very sensible, when the quantity of water in which it is lost, as it were, is sufficiently lessened by evaporation. Hence, if we would make sure of fulfilling the conditions required by Mr. Boerhaave, the last decoction of the plant must be made in a much greater quantity of water, and continued for a much longer time, than may perhaps be imagined, or perhaps easily determined; and this decoction being evaporated to any degree you please, must have neither taste, smell, nor colour: in short, it must from first to last remain perfectly like pure water. In other words, it is very difficult to attain to any certainty in this matter. Though what hath hitherto been said, about procuring the Fixed Alkali of plants by combustion, seems to prove that this Salt is wholly the production of the fire, yet it must not be asserted that no part thereof pre-existed formally in the plant before it was burnt. On the contrary, it is certain that, amongst the saline matters found in the composition of plants, there are true Neutral Salts whose basis is a Fixed Alkali; but this Alkali being combined with an Acid discovers none of its properties, and never appears in its true form till the Neutral Salt, of which it makes a part, is decomposed by combustion. The case of Sea-plants, all of which contain Sea-salt, and when burnt yield an Alkaline Salt perfectly resembling the basis of Sea-salt, seems to decide this point. If, in lixiviating the ashes of a plant, to dissolve and wash out its Alkali, you intend that nothing should be left but an absolutely pure earth, fit for making cupels, you must not be contented with one ablution only, even with a large quantity of water; because the ashes continue drenched with the water in which the Salts are dissolved, and consequently, when this water is evaporated, some of the Salts will be left with the earth. Therefore, if this be your view, you must wash it three or four several times, using fresh water every time. The water impregnated with the Alkali cannot be evaporated without a considerable loss of Salt, especially if it be violently boiled; because the water, with which it is closely united, carries off part of it. In consequence of this intimate union, it is very difficult, when the evaporation is near finished, and but a little water left, to dry the Salt perfectly, because it pertinaciously retains this last portion of humidity. The Alkali obtained from the ashes of a burnt plant is not perfectly pure: it is contaminated with a small mixture of fatty matters, which were probably defended thereby against the action of the fire, and which render it somewhat saponaceous. In order to free it from this extraneous matter, and to render it very caustic, it must be calcined a long time in a crucible, but without melting it at first: because it is with this Salt as with most metallic matters, which are sooner and more easily deprived of their phlogiston by being calcined without melting, provided they be comminuted into small particles, than when they are in fusion; all melted matters having but a small surface exposed to the air, by the contact of which the evaporation or anything whatever is exceedingly promoted. It was for this reason we directed the Salt to be calcined for a long time in a crucible before melting it. Mr. Boerhaave was very sensible of the utility of this calcination of the Alkali previous to its being melted, when in his Chymistry he ordered the ashes containing this Salt to be put into a large earthen vessel, kept red-hot for a considerable time, taking great care that the Salt do not melt. He takes notice, that, the longer the ashes are calcined in this manner, the stronger is the Alkali obtained from them. This method is, in the main, the very same with that here prescribed, and produces the same effect; because the Alkali is equally well freed of the extraneous fatty matter, whether it be calcined before or after its separation, provided it be not suffered to melt. Mr. Boerhaave gives another reason for recommending care to be taken that the Fixed Alkali do not melt, while the ashes are calcining to render it stronger and more caustic: for, if that should happen, the melted mixture of the Salt and ashes would produce a vitrified mass, which would have none of the properties of the Salt. PROCESS II. _To procure the Fixed Salt of a Plant by burning it after the manner of Tachenius._ Into an iron pot put the plant whose Salt you desire to obtain in the manner of Tachenius, and set it over a fire, strong enough to make its bottom red-hot; at the same time cover your plant with a plate of iron, that may lie immediately upon it in the pot. The plant will grow black, and smoke considerably; but will not flame, because it hath not a sufficient communication with the air. The black smoke only will escape through the interstice left between the side of the pot and the rim of the plate; which, for that purpose, should be made so as not to fit exactly into the pot. From time to time take up the iron plate, stir the plant, and cover it again immediately, to prevent its taking fire, or to smother it if it should happen to flame: go on thus till the black smoke cease. Then take off the iron plate: the upper part of the half-burnt plant will take fire as soon as the air is admitted, consume gradually, and be reduced to a white ash. Stir your matter with an iron wire, that the undermost parts, which are still black, may be successively brought uppermost, take fire, and burn to white ashes. Go on thus as long as you perceive the least blackness remaining. After this, leave your ashes some time longer on the fire; but stir them frequently, to the end that, if any black particles should still be left, they may be entirely consumed. Your ashes being thus prepared, lixiviate them with seven times their quantity of water, made to simmer over the fire, and keep stirring it with an iron ladle. Then filter the liquor, and evaporate it to dryness in an iron pot, stirring it incessantly towards the end, lest the matter, when it grows stiff, should adhere too closely to the vessel. When all the humidity is evaporated, you will have a Salt of a darkish colour, and alkaline nature; which you may melt in a crucible, and mould into cakes. This is the Fixed Salt of plants, prepared in the manner of Tachenius. _OBSERVATIONS._ The Fixed Salt obtained from plants in the manner invented by Tachenius, and here described, is in many respects different from the Caustic Fixed Alkali extracted out of the ashes of plants that have been consumed by flaming in the open air. Tachenius's Salt is indeed of an Alkaline nature; but much weaker than a pure Fixed Alkali. It is not by far so caustic; it attracts the moisture of the air much more feebly and slowly; it melts with a much smaller degree of heat; and it doth not make so strong an effervescence with Acids. In short, if you dissolve it in water, evaporate the solution to a pellicle, and set it in a cool place, it will shoot into small crystals; which is not the case with a pure Fixed Alkali. These several different effects, which characterize Tachenius's Salt, and distinguish it from the Caustic Fixed Alkali produced by burning a plant in the open air, prove that it is not a pure Alkali, but combined with certain substances that bring it nearer to the nature of a Neutral Salt, and place it, as it were, in the mid-way between such a Salt and a true Alkali. If we reflect on the manner in which it is produced, it is easy to perceive what those substances are that must be combined with it. It hath been shewn that plants, when analyzed, yield a great deal of Oil and of Acid. When they are burnt in the open air, all their Oil is dissipated in smoke, or consumed in flame. Great part of the Acid is likewise dissipated, and the remainder combining with the Earth of the plant forms a Fixed Alkali. When the same plants are analyzed, by distilling them in close vessels, the same principles are carried up by the action of the fire, forced to separate from the fixed parts, and pass over into the receiver in the form of vapours and of a liquid: but, when they are burnt in the manner of Tachenius, the Acid and Oil of the plant, as fast as they are expelled by the action of the fire, are repelled by the iron cover, which, at the same time that it prevents the Oil from being entirely consumed in flame, obliges these two substances to circulate, reverberates them on the rest of the plant, and, in a manner, forces them to re-unite, in part, with that from which they were just before separated. A considerable quantity, therefore, of the Oil and Acid of the plant, must evidently combine, in this operation, with its Fixed Salt, as fast as it is produced; and the properties above specified are owing to these two substances. Tachenius's Salt is, therefore, a Fixed Alkali, partly neutralized by some of the Acid of the plant, and rendered a little saponaceous by a portion of its Oil; whence it is much milder than a pure Fixed Alkali, and proper to be given internally, as an excellent remedy in several disorders. For the medicinal virtues of this Salt Mr. Boerhaave's Chymistry ought to be consulted, as the author was a very good judge of such matters. Tachenius's Salt may be converted into a Caustic Fixed Alkali, by freeing it from the Acid and from the Oil to which its peculiar properties are owing. For this purpose nothing more is requisite than to calcine it for a long time in a crucible, stirring it frequently with an iron wire, and taking care not to melt it, till it have undergone the same changes, and successively acquired the same colours, as our Fixed Alkali; and, when it becomes reddish, melting it and keeping it in fusion for an hour or two. Hitherto no sensible difference hath been observed between the Caustic Fixed Alkalis obtained from different plants, when equally calcined; except that those produced by Sea-plants have, as we said before, the same properties as the Alkaline basis of Sea-salt. Much the same thing may be said of the Fixed Salts obtained from plants by Tachenius's method: for, though they be combined with a portion of the Acid and Oil of the plant, yet, as these principles have-been exposed to the action of a strong fire, they are exceedingly altered, and almost wholly reduced to one and the same condition. PROCESS III. _To render Fixed Alkalis very caustic by means of Lime. The Caustic Stone._ Take a lump of newly burnt quick-lime, that hath not yet begun to flake in the air: put it into a stone pan, and cover it with twice its weight of the unwashed ashes of some plant, that are full of the Salt you design to render caustic. Pour on them a great quantity of hot water; let them steep in it five or six hours, and then boil them gently. Filter the liquor through a thick canvas bag, or through brown filtering paper supported by a linen cloth. Evaporate the filtered liquor in a copper bason set over the fire; and there will remain a Salt, which must be put into a crucible set in the fire. It will melt, and boil for some time; after which it will be still, and look like an Oil, or melted Fat. When it comes to this condition, pour it out on a very hot copper plate, and cut it into oblong tapering slips, before it grow hard by cooling. Put these slips, while they are still hot, into a very dry glass bottle, and seal it hermetically. This is the _Caustic Stone_, or _common Caustic_. _OBSERVATIONS._ The design of this operation is to combine with the Fixed Alkali all the saline acrid parts of the quick-lime. This is to be effected only by dispersing and diffusing both those substances in water, which is the proper solvent of all saline matters. Seeing, therefore, we must have an actual lixivium, it is needless to employ an Alkali already prepared and separated from ashes; for which reason we directed ashes that are still replete with Alkali to be used instead of a pure Alkali. By this means two ends are answered at once: the Salt contained in the ashes is extracted from them, and combined with the most acrid, subtile, and saline parts of the lime. The lye, when saturated with these two saline matters together, is vastly more acrid and caustic than if it contained but one of the two in a quantity equal to both. With this lye Soap is usually made; because the acuated Alkali contained in it hath a much greater effect on Oils than any other kind of Alkali. It also acts with incredible violence on all animal matters; which it dissolves, divides, and, in some measure, destroys, with surprising efficacy and quickness. For this reason it is impossible to filter it through a woollen or silken bag; for it will eat holes in them, or even reduce them to a pap, almost as soon as it touches them. Besides, as the lye would dissolve some part thereof, it would thence acquire a saponaceous quality, and so lose much of its caustic nature. We must, therefore, necessarily use a filter made of vegetable matters, which resist this destroying Salt much better than animal matters. An Alkali thus acuated by quick-lime attracts and retains humidity more strongly than any other kind of Alkali, even the perfectest and best calcined. For this reason it is almost impossible to dry it thoroughly in the bason wherein you evaporate the lixivium. To the moisture still left in it must be attributed its boiling when it begins to melt in the crucible. When all the humidity is dissipated, the fused Salt remains smooth and unruffled, like wax melted with a gentle heat. This caustic Salt is vastly more fusible than the common Alkalis. It scarce grows red before it flows like wax. When it is once in quiet fusion, all the humidity that occasioned the boiling observed at first being dissipated, it is as caustic as it can be made. It is then time to pour it out, and to cut it into long narrow sticks, fit for the use of Surgeons, who apply it to eat away callosities and excrescences, and to open tissues. On this account it is called the _Caustic Stone_. The operation of this Salt is so quick, that, in a very short time, it produces on the skin a sensation like that of fire. As this Salt grows surprisingly soon moist in the air, and loses its virtue when so moistened, it is necessary to shut it up, while it is still hot, in a very dry bottle, which must be immediately stopped with a glass stopple rubbed with emery, or else with a round cork and then dipt in pitch. In spite of all these precautions, it can scarce be kept five or six months in full vigour; especially if the bottle be sometimes opened in the mean while. We shall not attempt to explain here why an Alkali becomes so violently caustic by being combined with quick-lime. This question seems to be one of the most subtile, and the most difficult to answer, in all Chymistry. It depends on the cause of the Alkaline properties of lime; and can hardly be resolved, till we attain a further insight into the nature of that substance than we have yet got. PROCESS IV. _The Analysis of Soot._ Take wood-soot from a chimney under which no animal matter hath been dressed or burnt: put it into a glass retort set in a reverberating furnace; lute on a receiver, and begin to distil with a degree of heat somewhat less than that of boiling water. A considerable quantity of limpid phlegm will come over. Keep the fire in the same degree as long as any of this phlegm rises; but increase it when the drops begin to come slow: and then there will ascend a good deal of a milky water. When this water ceases to run, change the receiver, and increase your fire a little: a yellow Volatile Salt will rise, and stick to the sides of the receiver. The fire ought now to be very fierce, and, if so, will force up at the same time a very thick black Oil. Let the vessels cool: you will find a saline matter risen into the neck of the retort, which could not pass over into the receiver: in the bottom of the retort will be a _caput mortuum_, or black charred substance, the upper part of which will be crusted over with a saline matter, like that in the neck of the retort. _OBSERVATIONS._ The preceding analysis shewed what principles are obtained from vegetable substances without the aid of fire; those which the heat of fire raises and carries over out of one close vessel into another; and, lastly, those that continue fixed after the vegetable hath been thoroughly charred, either in a close vessel, or in the open air: nothing therefore remained, to finish the subject of vegetable principles, but to examine those which fire raises, in the form of vapours, smoke, and flame, from a vegetable matter burnt and consumed in the open air. Every body knows that Soot consists only of these principles, collected in the shafts of chimneys, which serve as alembics for this sort of distillation in the open air. By analysing Wood-soot, therefore, we shall discover the principles we are in quest of. The process we have given for that purpose is taken from Boerhaave's Chymistry, where we find it described with great exactness and precision. As we are at present inquiring into the nature of vegetables only, it is evidently necessary that we chuse a Soot produced by burning vegetables alone. Soot, though dry in appearance, contains nevertheless much humidity, as appears from this analysis; seeing there comes over at first a considerable quantity of phlegm, that doth not seem to be impregnated with any principle, except perhaps an extremely subtile, saline, and oily matter, that communicates to it a disagreeable smell, from which it cannot by any means be entirely freed. The white milky liquor, which follows this first phlegm, is still water, but much, more impregnated with saline and oily parts than the former. By its smell, which is exceeding quick and pungent, we may judge it contains much Volatile Alkali; and accordingly, when re-distilled by itself, it yields a Volatile Spirit, and a Volatile Salt in a concrete form. With regard to its white colour, it is occasioned by the oily parts which are diffused and suspended, but not dissolved, in the water. When this second liquor is come off, there ascends a Volatile Alkali in a dry form, and a very thick black Oil; because there is not moisture enough left to dissolve these principles, or rather to divide and disperse them. The Volatile Alkali obtained from Soot is, in a double respect, the product of the fire. In the first place, though it derives its origin wholly from wood, or other vegetables, which, when distilled in close vessels, yield no Volatile Alkali at all, yet it produces such a Salt when analyzed in the present manner: whence it must be inferred, that the principles of those vegetables are metamorphosed into a Volatile Alkali, by being burnt in the open air, and sublimed in the form of Soot. Secondly, though Soot when analyzed yields a great deal of this Salt, yet this Salt doth not formally pre-exist therein; for it doth not rise till after the phlegm, nor without a very considerable degree of heat: therefore Soot contains only the materials necessary to form this Salt; therefore the perfect combination of this Salt requires that the force of fire be applied a second time; therefore it is, as was said, doubly the product of the fire. The saline matter which we find sublimed into the neck of the retort, and which also forms the crust that covers the _caput mortuum_ of the Soot, appears by all Chymical trials to be an Ammoniacal Salt; that is, a Neutral Salt consisting of an Acid and a Volatile Alkali. This Ammoniacal Salt rises only into the neck of the retort, and doth not come over into the receiver: because it is but semi-volatile. We shall treat more at large of the production of a Volatile Alkali, and of this Ammoniacal Salt, when we come to the analysis of Animals, and the article of Sal Ammoniac. The charred matter that remains in the retort after distillation, being burnt in the open air, is reduced to an exceeding fixed white earth. As this fixed matter was part of that very Soot, which was sublimed to a great height whilst the vegetable was burning; this is a proof of what we advanced before, that the most fixed matters are capable of sublimation, when united with volatile substances; especially when they are exposed at the same time to the combined action of air and of fire. CHAP. VIII. _The_ ANALYSIS _of some particular_ SUBSTANCES _belonging to the_ VEGETABLE KINGDOM. PROCESS I. _Analysis of the natural Balsams: instanced in Turpentine._ Into a cucurbit put as much rain-water as will fill about a fourth part of its cavity, and pour into it the Turpentine you intend to analyze. Cover the cucurbit with its head, and lute it on with slips of sized paper or wet bladder. Set your alembic in a sand-heat; lute on a long-necked receiver; and give a gradual fire till the water in the cucurbit boil. There will come over into the receiver a good deal of phlegm, which, by little and little, will become more and more acid; and at the same time there will rise a great quantity of an æthereal Oil, extremely light, fluid, and as limpid and colourless as water. When you observe that no more Oil comes off, unlute your vessels; and in the receiver you will find an acidulated water, and the æthereal Oil floating on it. These two liquors may be easily separated from each other, by means of a glass funnel. In the cucurbit will be left some of the water you put in, together with the remainder of your turpentine; which, when cold, instead of being fluid as it was before distillation, will be solid, and of the consistence of a resin, and is then called _Rosin_. Put this residuum into a glass retort, and distil it in a reverberatory with a naked fire, gradually increased according to the general rule for all distillations. At first, with a degree of heat a little greater than that of boiling water, you will see two liquors come over into the recipient; one of which will be aqueous and acid, the other will be a transparent, limpid, yellowish Oil, floating on the acid liquor. Continue your distillation, increasing your fire from time to time, by slow degrees. These two liquors will continue to come off together: and the nearer the operation draws to its end, the more acid will the aqueous liquor become, and the thicker and deeper coloured will the Oil grow. At last the Oil will be very thick, and of a deep reddish-yellow colour. When nothing more ascends, unlute your vessels: in the retort you will find only a very small quantity of a charred, light, friable substance. _OBSERVATIONS._ All Natural Balsams, as well as Turpentine, are oily, aromatic matters, which flow in great quantities from the trees containing them, either spontaneously, or through incisions made on purpose. As these matters have a strong scent, it is not surprising that they should greatly abound with Essential Oils. They may even be considered as Essential Oils, that naturally, and of their own accord, separate from the vegetables in which they exist. Indeed these Natural Balsams differ from the Essential Oils obtained out of plants by distillation, in this alone, that the former contain a greater proportion of Acid; and, for that reason, are thicker than Essential Oils distilled with the heat of boiling water. But it hath been shewn, that these same distilled Essential Oils, though ever so fluid and light at first, gradually lose their tenuity as they grow old, and at last become considerably thick. On that occasion we observed that they are thus changed, because the lightest, most fluid, and least acid parts, are little by little dissipated and evaporated; so that at last there remains only the thickest and heaviest part, which owes these qualities to the Acid wherewith it is over-dosed. Hence it follows, that Natural Balsams, and Essential Oils grown thick with age, are exactly one and the same thing. Accordingly we see that fire and distillation produce the same effects on both. The rectification of an Essential Oil, thickened by keeping, is nothing but a decomposition thereof, by separating, with the heat of boiling water, all those parts that are light enough to rise with that degree of heat, from what is so loaded with Acid as to remain fixed therein. This operation is therefore precisely the same as our first distillation of Balsams with the heat of boiling water, by which the Essential Oil contained in them is drawn off. The residues of these two operations are also the same: each of them is a thick Oil, loaded with Acid, that is wholly, or nearly, deprived of the principle of odour peculiar to the original vegetable, and requires a degree of heat greater than that of boiling water to decompose it, by separating part of the Acid from the Oil; which will be rendered still the more fluid, the more the thickening Acid is separated from it by repeated distillations. The newer Natural Balsams are, the thinner they are, and the more Essential Oil do they yield; and this Essential Oil, like all others, grows thick in time, and at last turns again to an actual Balsam. These Balsams, by being long exposed to the heat of the sun, acquire such a consistence as to become solid. They then take another name, and are called _Resins_. Resins yield much less Essential Oil, when distilled, than Balsams do. Hence it follows, that Resins are to Balsams, what Balsams are to Essential Oils. All these effects are produced by the causes assigned above, and confirm the analogy we have established. We have no other observations to make on this analysis of Turpentine, except that when Rosin is distilled in a retort with a naked fire, the operation must be carried on very slowly, and the fire duly governed: for the matter is apt to swell, and to rise in substance into the receiver, without being at all decomposed. In order to avoid this inconvenience, it is adviseable to make use of a long-bodied retort, such as is known by the name of the _English Retort_. If you stop the distillation of Rosin about mid-way, or when the Oil that comes over begins to grow thick, you may, by changing the receiver, keep the first Oil apart: it is pretty fluid, and of a middle nature between the æthereal Oil, obtained with the heat of boiling water, and the last thick Oil, that doth not rise till towards the end of the distillation. This last thick Oil is that which Mr. Homberg fired with concentrated Oil of Vitriol. If we examine the matter contained in the retort, when the distillation is thus stopped short, it appears, when cold, in the form of a solid substance, almost perfectly diaphanous, of a deep reddish-yellow colour, and friable: It is known by the name of _Colophony_. This analysis of boiled Turpentine, is a specimen of the analysis of almost all other resins; so that what hath been said on this occasion is in a manner general, and applicable to other decompositions of the same kind. We shall now proceed to examine some other oily matters, which exhibit peculiar phenomena, and do not come under the general rules. PROCESS II. _The Analysis of Resins: instanced in Benjamin: The Flowers and Oil of Benjamin._ Into a pretty deep earthen pot, having a border or rim round its mouth, put the Benjamin you intend to analyze. Cover the pot with a large conical cap of very thick white paper, and tye it on under the rim. Set your pot in a sand-bath, and warm it gently till the Benjamin melt. Continue the heat in this degree for an hour and half. Then untie the paper cap and take it off, shaking it as little as possible. You will find all the inside of the cap covered with a great quantity of beautiful, white, shining Flowers, in the form of little needles. Brush them off gently with a feather, put them into a bottle, and stop it close. As soon as you take off the first cap, cover your pot immediately with a second like the former. In this manner go on till you perceive the Flowers begin to grow yellowish; and then it is proper to desist. The matter left in the pot will be blackish and friable when cold. Pulverize it; mix it with sand; and distil it in a glass retort with a graduated heat. There will come over a light Oil, of a fragrant scent, but in very small quantity; a little of an acid liquor, and a great quantity of a red thick Oil. There will be left in the retort a charred, spongy substance. _OBSERVATIONS._ All oily matters, that are naturally thick and in a concrete form, resemble each other in this, that they derive these qualities from an Acid combined with them. But they nevertheless differ greatly from one another in many respects. The quality, the quantity, of the Acid to which they owe their consistence, and the manner in which it is united with them, diversify them a thousand ways. In the preceding process we advanced, that Natural Balsams are distinguished from Resins by their containing so much more Oil, in proportion to their Acid, as suffices to render them almost fluid. For this reason they yield an essential Oil: whereas Resins, on the contrary, are solid; all their Oil being loaded and weighed down with a great quantity of Acid, so that no Essential Oil can be drawn from them. We observed at the same time, that, when all the Essential Oil contained in a Natural Balsam is drawn off, with the heat of boiling water, the residue takes a solid consistence, and resembles a Resin. In fact, almost all Resins yield, by distillation, the same principles as that residue; that is, an Oil of a middling nature between Essential Oils and thick Oils, in point of lightness and fluidity; the whole being always accompanied with an Acid diffused in phlegm. In consequence hereof, the analysis of Benjamin, described in the process, appears to vary much from that of other Resins: for here we see a volatile matter in a concrete form; namely, the white Flowers that rise first; which doth not usually occur in the analysis of Resins. Yet, if we examine the matter, we shall be convinced that it is very analagous to one of the principles obtainable from all Resins; that indeed it differs therefrom in some of its properties, particularly in its external form; but that it is in reality the very same. In fact, the Flowers of Benjamin are no other than an Oily Acid, nearly of the same nature with those obtained from all other vegetable substances; but which, instead of being liquid like them, appears in a dry concrete form, and in a manner crystallized. It probably derives this property from its Oil being combined with its Acid, either in greater quantity, or in a more intimate manner, than in the rest, and so strongly united therewith as not to be separated from it by a subliming heat; or from hence, that the compound, of which it is a part, contains too little phlegm to dissolve it; or else, that it is hindered from dissolving therein by the Oil with which it is combined. Perhaps all these causes may concur together in producing its concrete form. The saline character of this substance appears chiefly from its being soluble in water: but the water must be very hot, and even boiling, before it will effect this solution; and when it cools, the Salt shoots into fine needles at the bottom. This phenomenon directs us to a method of separating it from Benjamin without sublimation. For this purpose the Resin must be boiled in water: the water will then dissolve the Salt; and, as it cools, the Salt will crystallize, and may be easily collected. But as the Oil, with which the Acid is combined, hinders the water from dissolving it so easily as it otherwise would, we cannot obtain quite so much of it, from the same quantity of Benjamin, by decoction as by sublimation; the last portions thereof being united with a great quantity of Oil, which defends them against the action of the water. This Salt dissolves readily in Spirit of Wine, on account of the Oil combined with it. A course of well connected experiments might give us a far greater insight into its natural properties than we can now boast of. Benjamin yields a much smaller quantity of fluid Oil by distillation than other Resins do; because the greatest part of its Oil is employed in the composition of its oily, volatile, acid Salt. The thick Oil drawn from this Resin, is thicker than that obtained from any other Resin, and even fixes like butter when cold; nor can we get more than a very small quantity of Acid in a distinct liquor. All these effects depend on what we mentioned above, in relation to its saline flowers: to wit, the peculiar and intimate union between the Acid and Oily part of this Resin, so that the fire cannot so easily or so perfectly disjoin them, as it doth those of other Resins. Benjamin, when distilled, leaves in the retort much more of a charred coal than is left by most other resinous matters. This may be owing to the considerable quantity of earthy matter which it contains, and which, perhaps, may also be one of the causes that contribute to give its Salt a concrete form. REFLECTIONS _On the Nature and Properties of_ CAMPHOR. We do not propose to give an analysis of this singular body; because hitherto there is no process known in Chymistry by which it can be decomposed. We shall therefore content ourselves with reciting its principal properties, and making a few reflections on its nature. Camphor is an oily concrete substance; a kind of Resin, brought to us from the island of Borneo, but chiefly from Japan. This substance resembles Resins, in being inflammable, and burning much as they do; it is not soluble in water, but dissolves entirely and perfectly in Spirit of Wine; it is easily separated again from this menstruum, as all other oily matters are, by the addition of water; it dissolves both in expressed and in distilled Oils; it hath a very strong aromatic smell. These are the chief properties which Camphor possesses in common with Resins: but in other respects it differs totally from them; especially in the following particulars. Camphor takes fire and flames with vastly more ease than any other Resin. It is so very volatile, that it vanishes entirely in the air, without any other heat than that of the atmosphere. In distillation it rises entire, without any decomposition, or even the least alteration. It dissolves in concentrated mineral Acids; but with circumstances very different from those that attend other oily or resinous substances. The dissolution is accompanied with no effervescence, no sensible heat; and consequently can produce no inflammation. Acids do not burn, blacken, or thicken it, as they do other oily matters; on the contrary, it becomes fluid, and runs with them into a liquor that looks like Oil. Camphor doth not, like other oily matters, acquire a disposition to dissolve in water by the union it contracts with Acids; though its union with them seems to be more intimate than that of many oily matters with the same Acids. On the contrary, if a combination of Camphor and an Acid be diluted with water, these two substances instantly separate from each other: the Acid unites with the water, and the Camphor, being entirely disengaged from it, swims on the surface of the liquor. Neither Volatile Alkalis, nor the most caustic Fixed Alkalis, can be brought into union with it; for it always eludes their power. Notwithstanding these wide differences between Camphor and all other oily and resinous substances, the rule, that Acids thicken Oils, seems to be universal, and so constantly observed by nature, that we cannot help thinking this substance, like all the rest, is an Oil thickened by an Acid. But what Oil? What Acid? and how are they united? This is a subject for very curious inquiries. With a yellow Oil drawn from wine, and an acid vinous Spirit, of which we shall say more under the article of Æther, Mr. Hellot made a kind of artificial Camphor; a substance having the odour, favour, and inflammability of Camphor; an imperfect Camphor. True Camphor hath the levity, the volatility, and the inflammability of Æther. Can it be a substance of the same nature with Æther, a kind of solid Æther, an Æther in a concrete form? PROCESS III. _The Analysis of Bitumens: instanced in Amber, The Volatile Salt and Oil of Amber._ Into a glass retort put some small bits of Amber, so as to fill but two thirds of the vessel. Set your retort in a furnace covered with its dome; fit on a large glass receiver; and, beginning with a very gentle heat, distil with degrees of fire. Some phlegm will first come off, which will gradually grow more acid, and be succeeded by a Volatile Salt, figured like fine needles, that will stick to the sides of the receiver. Keep the fire up to this degree, in order to drive over all the Salt. When you perceive that little or none rises, change the receiver, and increase your fire a little. A light, clear, limpid Oil will ascend. As the distillation advances, this Oil will grow higher coloured, less limpid, and thicker, till at last it will be opaque, black, and have the consistence of Turpentine. When you perceive that nothing more comes off, though the retort be red-hot, let the fire go out. You will have in the retort a black, light, spongy coal. If you have taken care to shift the receiver, from time to time, during the distillation of your Oil, you will have sundry separate portions thereof, each of which will have a different degree of tenuity or thickness, according as it came over at the beginning, or towards the end of the distillation. _OBSERVATIONS._ The substance of which we have here given the analysis, together with all others of the same, that is, of the Bituminous kind, is by most Chymists and Naturalists classed with Minerals: and so far they are right, that we actually get these mixts, like other minerals, out of the bowels of the earth, and never procure them immediately from any vegetable or animal compound. Yet we have our reasons for proceeding otherwise, and for thinking that we could not, in this work, place them better, than immediately after those vegetable substances which we call Resins. Several motives determine us to act in this manner. The analysis of Bitumens demonstrates, that, with regard to the principles of which they consist, they are totally different from every other kind of mineral; and that, on the contrary, they greatly resemble vegetable Resins in almost every respect. In short, though they are not immediately procured from vegetables, there is the greatest reason for believing that they were originally of the vegetable kingdom, and that they are no other than resinous and oily parts of trees or plants, which, by lying long in the earth, and there contracting an union with the mineral Acids, have acquired the qualities that distinguish them from Resins. Mineralogists know very well that we find, every where in the earth, many vegetable substances, that have lain very long buried under it, and frequently at a considerable depth. It is not uncommon to find, under ground, vast beds of fossile trees, which seem to be the remains of immense forests: and Bitumens, particularly Amber, are often found among this subterraneous wood. These considerations, joined to proofs drawn from their analysis, make this opinion more than probable: nor are we singular in maintaining it, as it is adopted by many able modern Chymists. The analysis of Amber, above described, may serve as a general specimen of the decomposition of other Bitumens: with this single difference, that Amber is the only one among them which yields the Volatile Salt aforesaid; and this determined us to examine it preferably to any other. As for the rest, they all yield a phlegm, an acid liquor, and an Oil; which is thin at first, but grows thicker and thicker, as the distillation draws towards an end. It must be understood, however, that these Acids and these Oils may differ, according to the nature of the Bitumens from which they are drawn; just as the Phlegm, the Acid, and the Oil, resulting from the decomposition of Resins, differ in quantity and quality, according to the nature of the Resins from which they are procured. The principal differences observed between Resins and Bitumens are these: the latter are less soluble in Spirit of Wine; have a peculiar scent, which cannot be accurately described, and of which the sense of smelling only can judge; and their Acid is stronger and more fixed. This last property is one of the motives which induce us to think, that, besides the vegetable Acid, originally combined with the resinous or oily matter now become a Bitumen, a certain quantity of mineral Acid hath, in a course of time, been superadded to constitute this mixt. We shall presently see that the fact is certainly so, in the case of Amber at least. Almost all authors, who mention the analysis of Amber, have given different accounts of the volatility of its Salt, and of the time of the distillation when it begins to rise. Some make it ascend immediately after the first acid phlegm. Others say, that it doth not begin to appear till after the first thin Oil; and others again affirm, that it comes over with the last thick Oil. Mr. Bourdelin, who hath examined this matter to the bottom, in a Memoir on the analysis of Amber given in to the Academy, very judiciously remarks, that the different results which those Chymists met with in analyzing our mixt, arose wholly from the different manner wherein each conducted his fire during the operation. It is certain that such a cause is capable of producing vast differences: for when fire is hastily applied, or made too violent, it not only confounds and tumultuously mingles the principles of the body to be analyzed, but it even frequently drives up the entire substance itself out of the retort into the receiver, without decomposing it at all. This is really so in the case of Amber, and of almost all compound substances that are not extremely fixed. It ought therefore to be observed, as a general and important rule in every analysis, to administer the fire exceeding slowly and cautiously, as one can never err on that side; and to increase it only by such degrees as appear necessary for carrying on the distillation. By observing this method, an accurate analysis will be attained: by this means the Salt of Amber will rise before the Oil; whereas, if a degree of heat sufficient to raise the thin Oil, or even the thick Oil, be applied at first, the Salt will accordingly come over with the one or the other of these Oils. Chymists remained a long time unacquainted with the nature of this Salt of Amber, and authors of the greatest name agreed as little on this point as on that just mentioned. Some asserted it to be a Volatile Salt of the same kind with that which is obtained from animal substances; that is, a Volatile Alkali: others, on the contrary, pretended that it was an Acid of a singular nature. It is very surprising that such authors should disagree on such a point, considering how easily it may be ascertained whether this Salt be really an Acid or an Alkali. Mr. Bourdelin justly decides the question in favour of those who affirm it to be an Acid. In fact it hath all the properties of an Acid: it hath the taste of one, forms Neutral Salts with Alkalis, and differs from the most unquestionable Acids in this alone, that, being combined with a portion of Oil and a small quantity of earth, these give it a concrete form; which is not a solitary case in Chymistry, as is evident from Cream of Tartar. With regard to its Volatility, there is nothing in that repugnant to the properties of its constituent principles; seeing the Acid and the Oil predominant therein may easily be supposed to communicate their volatile nature to the small portion of earth with which they are combined. Those Chymists who looked upon the Salt of Amber as a Volatile Alkali, either did not examine it thoroughly, but contented themselves with its first appearance, in which it resembles the Volatile Salt of animals, or else were led into the error by some particular circumstances. We know, for example, that animal as well as vegetable substances are dug out of the earth. The insects, sometimes found inclosed in lumps of Amber, sufficiently prove this. Perhaps they made their experiments on such pieces of Amber; or else, that which they used might be mixed with some animal substance not very perceptible. In such a case, it would be no wonder if the Volatile Salt obtained should shew some tokens of an Alkali: for the Volatile Alkali arising from the animal matter would only be mixed, not combined, with the Salt of the Amber; as the great quantity of the Oil, in which both these Salts are entangled, would hinder them from dissolving each other, and forming such a Neutral Salt as would be produced in other circumstances. The acid or alkaline nature of the Salt of Amber was not the only point that remained to be discussed on this occasion. Its acid quality being once clearly ascertained, the nature of this Acid was next to be determined. This is the object chiefly aimed at in Mr. Bourdelin's Memoirs, and his discovery thereof is unquestionably one of the finest, and at the same time one of the most difficult, that could be attempted with regard to this Bitumen. It appears plainly from several experiments, of which we have given an account in the course of this work, that the strongest mineral Acids, by being combined with an oily matter, are so vastly altered, and so strangely disguised, that we not only are incapable of distinguishing what they are, but even can hardly avoid decomposing, and partly destroying them, by those very operations which seem the best adapted to separate them from the Oil in which they are inviscated. Mr. Bourdelin had all these difficulties to surmount, and incessantly met with new obstacles in that troublesome fatty matter, which, like an impenetrable veil, concealed from his view the Acid whose nature he wanted to discover. But at last, by dint of manifold experiments, he happily gained his end. Two parts of pure Nitre, unadulterated with the lead particle of Sea-salt, and one part of Amber, pulverized and mingled together, procured him, by deflagration, a Salt partly neutral and partly alkaline; which being lixiviated, and set to evaporate spontaneously, there formed at the bottom a residue of a mucilaginous, pappy, whitish matter, amongst which he could distinguish crystals, that were very transparent, regularly figured, of a cubical form, but rather oblong; so that they represented little oblong squares most exactly formed, and about half a line thick. As these crystals perfectly resembled, in their figure, the Neutral Salt produced by a combination of the Acid of Sea-salt with the alkaline basis of Nitre; this was a proof to Mr. Bourdelin that the Acid of Amber is of the same kind, or rather exactly the same, with that of Sea-salt. The Nitre being alkalizated by means of the phlogiston of the Amber, the Acid of the Bitumen, finding this Alkali a proper basis to fix in, unites with it, and by that means is enabled to resist the action of the fire, so as not to be carried off by it. On the other hand, it is separated from the fat matter by which it was masked before; for by the help of this fat matter the Nitre is alkalizated. The Acid, having by this means recovered all its properties, begins to discover them, as hath been said, by the figure it constantly gives to the crystals of the Neutral Salt which it helps to constitute. Moreover, this Neutral Salt hath all the essential properties of Sea-salt. It hath its taste; it decrepitates in the same manner on live coals; if Oil of Vitriol be poured on it, white vapours arise, which have the smell of Spirit of Salt, and are an actual Spirit of Salt. Lastly, it makes a white precipitate of Mercury dissolved in Spirit of Nitre, and a _luna cornea_ of Silver dissolved in the same Spirit; which last proofs would alone be sufficient to establish Mr. Bourdelin's opinion, though we had no other. It were to be wished that the experiments which Mr. Bourdelin hath made on Amber were also tried on other Bitumens. There is reason to think they would be found to contain either the Marine or the Vitriolic Acid: for though they do not yield a Volatile Salt, as Amber doth, in distillation, yet the Acids obtained from them are very strong, and appear, as we said before, to have a mineral origin. Mr. Geoffroy observed, that Amber, being pulverized and infused in hot water, parts with its Salt in the same manner as Benjamin does; which gives room to suspect that Amber is to Bitumens what Benjamin is to Resins. PROCESS IV. _The Analysis of Bees-Wax, and such Oily Compounds as are analogous to it._ Melt the Wax you intend to analyze, and mix with it as much fine sand as will make it into stiff paste. Put this paste in little bits into a retort, and distil as usual, with a graduated fire, beginning with a very gentle heat. An acid phlegm will come over, and be followed by a liquor which at first will look like an Oil, but will soon congeal in the receiver, and have the appearance of a butter or grease. Continue the distillation, increasing the fire by insensible degrees, till nothing more will come off. Then separate the butter from the acid phlegm in the receiver, mix it with fresh sand, and distil it again just as you did the Wax before. Some acid phlegm will still come off, and an Oil will ascend, which will not fix in the receiver, though it be still thick. Continue the distillation, with a fire so governed that the drops may succeed each other at the distance of six or seven seconds of time. Do not increase it, till you perceive the drops fall more slowly; and then increase it no more than is necessary to make the drops follow each other as above directed. When the distillation is finished, you will find in the receiver the Oil come wholly over, and a little acid phlegm. Separate the Oil from this liquor; and, if you desire to have it more fluid, re-distil it a third time in the same manner. _OBSERVATIONS._ Bees-Wax, like all other oily matters in a concrete form, is an Oil thickened by an Acid. Its decomposition furnishes us with a very convincing proof of this truth; which, you see, is confirmed more and more, by every new analysis we make of such substances. Wax doth not part with all its Acid in the first distillation: and this is the reason that it doth not then become a fluid Oil, but a butter, which hath only a degree of softness proportioned to the quantity of Acid separated from it. The same thing holds with regard to its butter; which losing, by a second distillation, a great part of the remaining Acid which caused its consistence, is by that means turned to an Oil. Lastly, this Oil, from being thick, becomes very fluid by a third distillation, and so follows the general rule of Oils; which always become the more fluid the oftener they are distilled or rectified. What is here said concerning Wax is applicable to Resins, also; which it further resembles in its consistence, and its refusing to dissolve in water: yet it differs from them essentially in several respects; and for this reason we thought proper to treat of it in particular. The properties in which it differs from Resins are these: First, It hath no aromatic scent, nor acrid taste, as Resins have. Secondly, It doth not yield a thin limpid Oil, in the first distillation, as they do. Thirdly, Its Oil, or its butter, doth not grow sensibly thicker with age. Mr. Boerhaave kept some butter of Bees-Wax for twenty years, in a vessel that was not stopt, but only covered with a bit of paper; yet it did not grow hard. An Essential Oil, though kept much closer shut up, would in much less time have acquired the consistence of a Balsam; and a Balsam, in that time, would have become a Resin. Fourthly, Bees-Wax is not soluble in Spirit of Wine; whereas it is the very nature of Resins to dissolve in that menstruum. Fifthly, I have observed that Spirit of Wine acts faintly on the butter of Bees-Wax; dissolves that butter when distilled to an Oil; unites more readily with that Oil when rectified by a third distillation; and dissolves it still the more readily the oftener it is distilled. Resins, on the contrary, are more soluble in Spirit of Wine than the thin Oils drawn from them; and those Oils acquire the property of resisting that menstruum more and more obstinately the oftener they are rectified. By these differences we may judge whether it be proper to confound Bees-Wax with Resins, or whether it ought not rather to be considered as an oily compound of a singular species, which deserves to be ranked in a different class, or at least in some other division. If we take the most cursory view of the properties of Essential Oils, and compare them with those of Fat Oils, we cannot avoid being struck with a resemblance between the properties of Essential Oils and those of Resins, as well as with the apparent conformity between the properties of Fat Oils and those of Bees-Wax: from all which we may conclude with good reason, in my opinion, that the Oil of Bees-Wax is not of the same nature with that of Resins. The Oil of Resins hath all the properties of an Essential Oil, and is justly allowed to be an Essential Oil rendered thick and ponderous by an Acid. The Oil of Bees-Wax, on the contrary, hath all the properties of Fat Oils; and there is great room to think, that this substance is really no other than a Fat Oil hardened by an Acid. Bees-Wax is not the only oily compound that appears to have a Fat Oil for its basis. Certain shrubs in America yield, by decoction, a substance that hath all the properties of Bees-Wax, differing therefrom only in its colour, which is green. The Butter of Cacao is also a substance analogous to Bees-Wax, and would be really Wax, if it were but as hard; for it contains the same principles, but in different proportions: in short, it is to Bees-Wax what Balsams are to Resins. PROCESS V. _The Saccharine Juices of Plants analyzed: instanced in Honey._ Put into a stone cucurbit the Honey you intend to distil; set it in a moderate sand-heat, and evaporate the greatest part of its humidity, till you perceive the phlegm begin to be acid. Then take out the matter remaining in the cucurbit, put it into a retort, leaving a full third thereof empty, and distil in a reverberatory with degrees of fire. An acid, amber-coloured liquor will come over. As the operation advances, this liquor will continually become deeper coloured and more acid, and at the same time a little black Oil will ascend. When the distillation is over, you will find in the retort a pretty large charred mass, which being burnt in the open air, and lixiviated, affords a Fixed Alkali. _OBSERVATIONS._ If we consider nothing but the nature of the principles obtained from Honey, we may be induced to think that this substance is of the same kind with Resins; for we get from each a Phlegm, an Acid, an Oil, and a Coal. Yet there is a very great difference between these two sorts of compounds. Oily matters of the resinous kind are very inflammable, and by no means soluble in water: Honey, on the contrary, is not inflammable in its natural state; will not flame till it be half consumed, or turned almost to a coal, by the fire; and mixes readily and perfectly with water. Now whence can this difference arise? Since it is not owing to the nature of the principles that constitute these mixts, it must necessarily be attributed to the proportions in which those principles are united. And indeed if we attend to the quantities obtained from each by analyzing them severally, we shall find that, in this respect, there is a very great difference between them. Oily compounds of the nature of Resins, which are not soluble in water, yield in distillation a little phlegm, a quantity of Oil vastly exceeding that of their Acid, and a very small matter of coal, which, when burnt, scarce leaves any token of a Fixed Alkali. Honey, on the contrary, and all other juices of the same nature, give out, when analyzed, a great deal of phlegm, a quantity of Acid much superior to that of their Oil, and a considerable mass of coal; from which, when burnt in the open air and lixiviated, a very perceptible Alkali may be obtained. If the quantity of the principles procured by these two analyses be compared together, it will be easy to deduce from thence the causes of the different properties observed in the mixts that afforded them. In the large quantity of Oil, of which resinous substances consist almost entirely, we see the cause of their being so inflammable, and so indissoluble in water. When such bodies are decomposed, there remains but little coal, and very little Fixed Alkali; because their Oil carries off with it almost all their Acid, leaving a scarce perceptible portion thereof fixed in the coal. Now we know that this Acid is an essential requisite to the formation of an Alkali. Honey, on the contrary, and the analogous mixts, are so unapt to take fire, and mix so readily with water, only because there is very little Oil in their composition, in comparison of the Acid, which is their predominant principle. For the same reason they leave, when decomposed, a greater quantity of coal, which also yields much more Fixed Alkali than we find in the coals of Resins. Perhaps these mixts may also contain a little more earth. The cause of this greater quantity of Fixed Alkali will be found in what we delivered above concerning the combination and production of that Salt. Sugar, Manna, and the Saccharine juices of fruits and plants, are of the same nature as Honey, yield the same principles, and in the same proportions. All these substances must be considered as native Soaps; because they consist of an Oil rendered miscible with water, by means of a saline substance. They differ from the common artificial Soaps in several respects; but chiefly in this, that their saline part is an Acid, whereas that of common Soap is an Alkali. The natural Soaps are not for that reason the less perfect: on the contrary, they dissolve in water without destroying its transparency, and without giving it a milky colour: which proves that Acids are not less proper than Alkalis, or rather that they are more proper additaments, for bringing Oils into a saponaceous state. But it must be owned, that we are not yet able to imitate by art the Acid Soaps which are prepared and so perfectly combined by nature, and that the detersive quality of these is not near so strong as that of the Soaps which have an Alkali for their saline principles. Though Honey, and the other vegetable substances analogous to it, contain much Acid, yet they have no taste of sourness, nor any of the other properties of Acids; but, on the contrary, their taste is soft and saccharine: the cause of this is, that their Acid is intimately mixed and perfectly combined with their Oil, which entirely sheathes and blunts it. PROCESS VI. _Gummy Substances analyzed: instanced in Gum Arabic._ Distil Gum Arabic in a retort with degrees of fire. A limpid, scentless, and tasteless phlegm will first come over; and then a russet-coloured acid liquor, a little Volatile Alkali, and an Oil, which will first be thin and afterwards come thick. In the retort will be left a good deal of a charred substance, which being burnt and lixiviated will give a Fixed Alkali. _OBSERVATIONS._ Gums have at first sight some resemblance of Resins; which hath occasioned many resinous matters to be called Gums, though very improperly: for they are two distinct sorts of substances, of natures absolutely different from each other. It hath been shewn, that Resins have an aromatic odour; that they are indissoluble in water, and soluble in Spirit of Wine; that they are only an Essential Oil grown thick. Gums, on the contrary, have no odour, are soluble in water, indissoluble in Spirit of Wine, and, by being analyzed as in the process, are converted almost wholly into a phlegm and an Acid. The small portion of Oil contained in them is so thoroughly united with their Acid, that it dissolves perfectly in water, and the solution is clear and limpid. In this respect Gums resemble Honey, and the other vegetable juices analogous to it. They are all fluid originally; that is, when they begin to ooze out of their trees. At that time they perfectly resemble mucilages, or rather they are actual mucilages, which grow thick and hard in time by the evaporation of a great part of their moisture: just as Resins are true Oils, which, losing their most fluid parts by evaporation, at last become solid. Infusions or slight decoctions of mucilaginous plants, when evaporated to dryness, become actual Gums. Some trees abound both in Oil and in mucilage: these two substances often mix and flow from the tree blended together. Thus they both grow dry and hard together in one mass, which of course is at the same time both gummy and resinous: and accordingly such mixts are named Gum-resins. But it must be observed, that these resinous and gummy parts suffer no alteration by being thus mixed; but each preserves its properties, as if it were alone. The reason is, that they are not truly united together: Gums being indissoluble by Oils or by Resins, the parts of each are only entangled among those of the other, by means of their viscosity. Hence, if the Gum-resin be put into water, the water will dissolve only the gummy part, without touching the resinous. On the contrary, if the same Gum-resin be put into Spirit of Wine, this menstruum will dissolve the Resin, and leave the Gum. We shall treat more particularly of this dissolution under the head of Spirit of Wine. If a Gum-resin, instead of being only infused in water, be triturated with water, it will be thereby wholly diffused through it: but the resinous part, which is only divided by the triture, and not dissolved in the water, gives the liquor a milky colour, like that of an emulsion. It is indeed an actual emulsion; that which is made with kernels being, like this, no other than a divided oil, dispersed in small particles by triture, and suspended in the water by means of a mucilage. SECTION II. _Of Operations on Fermented Vegetable Substances._ CHAP. I. _Of the_ PRODUCT _of_ SPIRITUOUS FERMENTATION. PROCESS I. _To make Wine of Vegetable Substances that are susceptible of Spirituous Fermentation._ Let a liquor susceptible of, and prepared for, the Spirituous Fermentation be put into a cask. Set this cask in a temperately warm cellar, and cover the bung-hole with a bit of linen cloth only. In more or less time, according to the nature of the liquor to be fermented, and to the degree of heat in the air, the liquor will begin to swell, and be rarefied. There will arise an intestine motion, attended with a small hissing and effervescence, throwing up bubbles to the surface, and discharging vapours: while the gross, viscous, and thick parts, being driven up by the fermenting motion, and rendered lighter by little bubbles of air adhering to them, will rise to the top, and there form a kind of soft, spongy crust, which will cover the liquor all over. The fermenting motion still continuing, this crust will, from time to time, be lifted up and cracked by vapours making their escape through it; but those fissures will presently close again, till, the fermentation gradually going off, and at last entirely ceasing, the crust will fall in pieces to the bottom of the liquor, which will insensibly grow clear. Then stop the cask close with its bung, and set it in a cooler place. _OBSERVATIONS._ Matters that are susceptible of the Spirituous Fermentation are seldom so perfectly prepared for it by nature as they require to be. If we except the juices that flow naturally from certain trees, but oftener from incisions made on purpose in them, all other substances require some previous preparation. Boerhaave, who hath handled this subject excellently well in his Chymistry, divides the substances that are fit for Spirituous Fermentation into five classes. In the first he places all the mealy seeds, the legumens, and the kernels of almost all fruits. The second class includes the juices of all fruits that do not tend to putrefaction. In the third class stand the juices of all the parts of plants which tend rather to acidity than to putrefaction; and consequently those which yield much Volatile Alkali are to be excluded. The fourth class comprehends the juices or saps that spontaneously distil from several trees and plants, or flow from them when wounded. He forms his fifth and last class of the saponaceous, saccharine, and concrete or thick juices of vegetables. Resinous or purely gummy matters are excluded, as not being fermentable. These five classes may be reduced to two; one comprehending all the Juices, and another all the Mealy parts, of vegetables that are susceptible of fermentation. The juices want nothing to fit them for fermentation, but to be expressed out of the substances containing them, and to be diluted with a sufficient quantity of water. If they be very thick, the best way is to add so much water as shall render the mixed liquor just capable of bearing a new-laid egg. With respect to farinaceous substances, as they are almost all either oily or mucilaginous, they require a little more management. The method of brewing malt-liquors will furnish us with examples of such management. It is thus described by Mr. Boerhaave. In warm weather the grain is put into large vats, and a considerable quantity of rain-water, or very clean river-water, is poured thereon, in which it lies till it be well soaked and swelled. This first operation is called the _Steeping_. When the grain is by this means grown very plump, it is taken out of the steep, and laid on great heaps in an open place, yet not too much exposed to the wind. In a very little time those heaps grow hot, the grain begins to sprout, and shoot out little buds of leaves and roots. The art of managing this operation properly consists in seizing the exact point of time when the germination should be stopt: on this in a great measure depends the success of the business. For, if the grain be left too long in this hot bed, it may begin to rot, or else the leaves and roots, by growing too much, may consume most of the mealy substance, which, in this case, is the only subject of fermentation; and, if the germination be checked too soon, the advantage expected from it will be lost; that is, the mucid matters will not be sufficiently attenuated. As soon therefore as the germination is observed to have attained its proper stage, it must be stopt with all possible expedition. For this purpose the grain is carried into an open place exposed to the north wind, where it is spread on a boarded floor and dried; by which means it is hindered from sprouting any more. It is next made to run slowly down through a long tunnel made very hot, which at once dries it thoroughly to the very heart, and in some measure scorches it, though very slightly. Grain thus prepared is called _Malt_. By this germination, exsiccation, and slight torrefaction of the grain, the farinaceous substance is considerably attenuated, and its natural viscosity destroyed, which would otherwise hinder the meal, when boiled in water, from mixing with it and dissolving in it, as it must in some measure do to form a liquor fit for Spirituous Fermentation. Mr. Boerhaave takes notice, that if grain, which hath not been thus prepared, be chewed in the mouth, its meal makes a paste that is not easily attenuated, or entirely dissolved, by the spittle; whereas the meal of the same grain, after malting, mixes immediately and perfectly with the spittle: it hath moreover a sweet agreeable taste, which common grain hath not. The grain being thus malted, is ground: then hot water is poured thereon, in which it is left to infuse for three or four hours. In that time the water takes up all the attenuated flour of the Malt; whereas it would not dissolve the farina of grain that had not undergone the above described preparations. The Wort is then drawn off the grains, and boiled to a proper degree of inspissation; the decoction is suffered to cool, and afterwards put into casks to be fermented as the process directs. As Malt-liquor is apt to grow sour, and will not keep so long as Wine, some bitter plants are usually boiled in the decoction, to make it keep the longer, and hinder it from turning sour so soon as it otherwise would. For this purpose such plants are chosen as have an agreeable bitter taste; and the preference is generally given to Hops. Besides these preparations, relating chiefly to Malt-liquors, there are many other things to be observed relating to Spirituous Fermentation in general, and to all matters susceptible of that fermentation. For example; all grains and fruits designed for that fermentation must be perfectly ripe; for otherways they will not ferment without difficulty, and will produce little or no inflammable Spirit. Such matters as are too austere, too acrid, or astringent, are for the same reason unfit for Spirituous Fermentation; as well as those which abound too much in Oil. In order to make the fermentation succeed perfectly, so as to produce the best Wine that the fermented liquor is capable of affording, it is necessary to let it stand quiet without stirring it, lest the crust that forms on its surface should be broken to little fragments, and mix with the liquor. This crust is a kind of cover, which hinders the spirituous parts from exhaling as fast as they are formed. The free access of the air is another condition necessary to fermentation: and for this reason the vessel that contains the fermenting liquor must not be close stopped; the bung-hole is only to be covered with a linen cloth, to hinder dirt and insects from falling into it. Nor must the bung-hole be too large, lest too much of the spirituous parts should escape and be lost. Lastly, a just degree of warmth is one of the conditions most necessary for fermentation: for in very cold weather there is no fermentation at all; and too much heat precipitates it in such a manner, that the whole liquor becomes turbid, and many fermenting and fermented particles are dissipated. If, notwithstanding the exactest observance of every particular requisite to excite a successful fermentation, the liquor cannot, without difficulty, be brought to effervesce, which scarce ever happens but to Malt-liquor, it may be accelerated by mixing therewith some matter that is very susceptible of fermentation, or actually fermenting. Such matters are called _Ferments_. The crust, or _Yest_, that forms on the surface, of fermenting liquors is a most efficacious ferment, and on that account very much used. It sometimes happens, that there is occasion to check the fermentation excited in the liquor, before it ceases of itself. To effect this, such means must be used as are directly opposite to those mentioned above for promoting fermentation. The end is obtained by mixing with the liquor a quantity of Alkali, sufficient to absorb the Acid contained therein: but this method is seldom made use of, because it spoils the liquor: which, after being thus treated, is incapable of any spirituous fermentation, but on the contrary will certainly putrefy. Spirituous fermentation may also be stopped by mixing with the liquor a great quantity of some mineral Acid. But this likewise alters its nature; because these Acids, being fixed, always remain confounded therewith, and never separate from it. The best method yet found out for checking this fermentation, without injury to the fermenting liquor, is to impregnate it with the fumes of burning sulphur. These fumes are known to be acid, and it is that quality in them which suspends the fermentation. But, at the same time, this Acid is extremely volatile: so that it separates spontaneously from the liquor, after some time, and leaves it in a condition to continue its fermentation. For this reason, when a Wine is desired that shall be but half fermented, and shall partly retain the sweet taste it had in the state of _Must_, (the proper name for the unfermented juice of the grape), it is put into casks in which Sulphur hath been previously burnt, and the vapours thereof confined by stopping the bung-hole. These are called _Matched Wines_. If the same operation be performed on Must, its fermentation will be absolutely prevented: it will retain all its saccharine taste, and is then called _Stum_. As the sulphureous Acid evaporates spontaneously, in no long space, it is necessary to fumigate matched wines, or stums, from time to time, when they are intended to be kept long without fermenting. PROCESS II. _To draw an Ardent Spirit from Substances that have undergone the Spirituous Fermentation. The Analysis of Wine._ Fill a large copper cucurbit half full of Wine. Fit on its head and refrigeratory. Lute on a receiver with wet bladder, and distil with a gentle fire; yet so that the drops which fall from the nose of the alembic may succeed one another pretty quick, and form a sort of small continued stream. Go on thus till you perceive that the liquor which comes over ceases to be inflammable; and then desist. You will find in the receiver a clear liquor, somewhat inclining to an amber-colour, of a pleasant quick smell, and which being thrown into the fire instantly flames. The quantity thereof will be nearly a fourth part of the Wine you put into the alembic; and this is what is called _Brandy_; that is, the Ardent Spirit of Wine loaded with much phlegm. In order to rectify it, and reduce it to Spirit of Wine, put it into a long-necked matrass, capable of holding double the quantity. Fit a head to the matrass, and lute on a receiver: place your matrass over a pot half full of water; set this pot over a moderate fire; and with this vapour-bath distil your Spirit, which will rise pure. Continue this degree of heat till nothing more will come over. You will find in, the receiver a very clear colourless Spirit of Wine, of a quick but agreeable smell, which will catch fire at once by the bare contact of any flaming substance. _OBSERVATIONS._ It hath been shewn, that Honey, and the vegetable juices analogous to it, such as Must, and the juices of all saccharine fruits and plants, yield by distillation no other principles than Phlegm, an Acid, and a small quantity of Oil. The analysis of Wine, and of all substances that have undergone the spirituous fermentation, shews us that this fermentation produces, and in some sense creates, in those mixts, a principle that did not exist in them before; I mean the Ardent Spirit, which is an inflammable liquor that is miscible with water. This liquor results from a closer combination of the Acid and the Oil, which are attenuated and united together by fermentation. To this Oil, which is one of its constituent parts, its inflammability is owing; and the Acid imparts to this Oil the property of mixing with water, more perfectly and more intimately than when it makes a part of any other compound. Nay, there is, in the very composition of an Ardent Spirit, a certain quantity of water which is necessary to it, which is one of its essential parts, and without which it would not have the properties that characterise it. We shall presently have occasion to see, that, when Spirit of Wine is dephlegmated to a certain pitch, we cannot deprive it of any more of its aqueous parts, without decomposing a quantity of the Spirit, proportioned to the quantity of water drawn from it. Ardent Spirits are more volatile than any of the principles of the mixt from which they are produced, and consequently more volatile than the phlegm, the Acid, or the Oil thereof, though they wholly consist of these. This cannot be attributed to any thing but a peculiar disposition of these principles, which are attenuated in a singular manner by the fermenting motion, and thereby rendered more susceptible of expansion and rarefaction. The great volatility of the Ardent Spirit procures us an easy method of separating it from the other principles of Wine, and of dephlegmating it. For this purpose it need only be distilled with such a gentle heat as is just capable of raising the Spirit, but too weak to produce the same effect on the other matters from which you desire to free it. For this reason the more slowly, and with the less heat, you distil your Wine, the stronger and more spirituous will your Brandy be. The same is to be said of the second distillation, by which Brandy is changed into Spirit of Wine, or, in other words, dephlegmated. The Spirit of Wine thus drawn from it will be so much the better, the more exactly you observe the conditions here proposed. If Spirit of Wine be treated in the same manner as Brandy, that is, if it be rectified by distillation with the same precautions, it will be thereby dephlegmated as much as possible; and then it is called _Alkohol_. By this rectification it is not only freed from its redundant phlegm, but also from some particles of Acid and of Oil, which, though much less volatile than itself, yet ascend with it in the first distillation: nor is it possible wholly to avoid this inconvenience. Mr. Boerhaave proposes to dephlegmate Spirit of Wine more easily, and more accurately, by distilling it from decrepitated Sea-salt mixed, while very hot, with the Spirit. This must certainly be a very good method; because decrepitated Sea-salt powerfully attracts moisture, and consequently is very apt to imbibe and retain that which is in the Ardent Spirit: and Spirit of Wine doth not dissolve Sea-salt; so that there is no reason to fear its being in the least contaminated therewith. All fermented liquors do not yield near an equal quantity of Ardent Spirit; because they do not all, before fermentation, equally contain the principles necessary to produce an Ardent Spirit, in the most advantageous proportion or disposition. There are several ways of proving whether or no Spirit of Wine be as highly rectified as it possibly can be, that is, whether or no it contain any more phlegm than is precisely necessary to constitute it Spirit of Wine; and many Chymists have judged that worthy of the title which burns away entirely, without leaving behind it the least token of humidity; or that which, being burnt on gun-powder, fires it at last. But Mr. Boerhaave justly observes, that neither of these is a sufficient proof; because, though there should be a small quantity of unnecessary phlegm in Spirit of Wine, yet it may very well be evaporated and dissipated by the deflagration in either way. He therefore proposes another proof, which is much more to be depended on; that is, by mixing and shaking with the Spirit of Wine a small quantity of a very dry pulverized Alkali. If this Salt, when thus agitated, and even warmed, with Spirit of Wine, continue as dry as it was at first, it is a sign that the Spirit is perfectly dephlegmated. Mr. Boerhaave tried in this manner some Spirit of Wine that had fired gun-powder, and found it to contain so much phlegm that it moistened his Salt very perceptibly: nay, one single drop of water, being mixed with a considerable quantity of Spirit of Wine, which before left the Alkali perfectly dry, discovered itself in this way by the moisture it communicated to the very same Salt. Spirit of Wine may also be contaminated with some heterogeneous substances; such as acid, alkaline, or oily matters. These are to be discovered by very easy experiments proper to each: for an acid or alkalious Spirit of Wine being mixed with syrop of violets will give it a red or a green colour, according to the nature of the saline matter contained in it; and, if it be combined with an Oil, that will shew itself by the white milky colour which a drop of it will give to water. Besides the Ardent Spirit, Wine contains an Acid united with a portion of earth and of Oil, which give the Acid a concrete form. This substance generally separates spontaneously from the Wine, and adheres, in the form of a strong crust, to the sides of the cask. It is called _Tartar_, and is, properly speaking, the Essential Salt of Wine. We shall exhibit the analysis of Tartar, and treat of it more at length, in a chapter apart. Wine-lees consist of the grossest parts of the fermented liquor; which being uncapable of remaining dissolved, sink to the bottom, and form a sediment, which contains also some Tartar and a little Ardent Spirit. The residue left in the cucurbit, after the Spirit is drawn off, is a sort of Extract of Wine. This liquor hath an exceeding rough, or rather acid taste. When distilled it yields an acid phlegm, which comes more and more acid as the distillation advances, and a fetid empyreumatic Oil. From the _caput mortuum_, when burnt, a considerable quantity of a Fixed Alkali may be extracted. From all this it follows, that Wine consists of an Ardent Spirit, and a Tartarous Acid, diffused through a great quantity of water, together with some oily and earthy parts. Malt-liquor contains much less Tartar than Wine; but, instead thereof, it is impregnated with a mucilaginous matter, which becomes very perceptible when any body is smeared with it and dried; for then it makes a kind of Varnish. This mucilaginous matter, which is not sufficiently attenuated, especially when the Malt-liquor is new, makes it very apt to swell up and rise over the helm with rapidity, in the distillation of an Ardent Spirit from it: for which reason it is necessary to proceed more cautiously, and more slowly, in distilling a Spirit from this liquor than from Wine. PROCESS III. _To dephlegmate Spirit of Wine by the means of Fixed Alkalis. Spirit of Wine analyzed._ Into a glass cucurbit pour the Spirit of Wine you intend to dephlegmate, and add to it about a third part of its weight of Fixed Alkali, newly calcined, perfectly dry, heated, and pulverized. Shake the vessel, that the two matters may be mixed and blended together. The Salt will gradually grow moist, and, if the Spirit of Wine be very aqueous, melt into a liquor, that will always lie at the bottom of the vessel, without uniting with the Spirit of Wine which will swim at top. When you perceive that the Alkali attracts no new moisture, and that no more of it melts, decant your Spirit of Wine from the liquor beneath it, and add to your Spirit fresh Salt thoroughly dried as before. This Salt will also imbibe a little moisture; but it will not grow liquid, because the Alkali, with which it was mixed before, hath left too little phlegm to melt this. Decant it from this Salt as at first, and continue to mix and make it in the same manner with fresh Salt, till you observe that the Salt remains as dry after as it was before mixing it with the Spirit of Wine. Then distil your Spirit in a small alembic with a gentle heat, and you will have it as much dephlegmated as it can be. _OBSERVATIONS._ Next to the Mineral Acids, Fixed Alkalis perfectly calcined are the substances which have the greatest affinity with water, and therefore it is no wonder they are so very fit to dephlegmate Spirit of Wine, and to free it from all its redundant humidity. Indeed Spirit of Wine cannot be perfectly dephlegmated without their assistance: for when distillation alone is made use of for that purpose, it is impossible to prevent some phlegm from rising with the Spirit of Wine, whatever precautions we take to avoid it. Hence it comes to pass, that Spirit of Wine, though ever so highly rectified by distillation, always imparts a little moisture to an Alkali, when mixed with it in order to prove its goodness. But, while the Alkali attracts the super-abundant phlegm of the Spirit of Wine, it produces in that liquor, and undergoes itself, remarkable changes. Spirit of wine, when so highly dephlegmated by an Alkali that, being kept in digestion therewith, it leaves the Salt perfectly dry, hath a red colour, an odour somewhat different from that which is peculiar to it when perfectly pure, a taste in which that of the Fixed Alkali may be distinguished; and it makes a slight effervescence with Acids: which manifestly proves, that it is united with a portion of the Alkali employed to rectify it. Mr. Boerhaave thinks, with great probability, that this portion of the Alkali unites with the Spirit of Wine, much in the same manner as with Oils, _viz_. that it forms with the Spirit a kind of liquid Soap. He observes, that this alkalizated Spirit cleans the fingers; and that things wetted with it do not dry so speedily as those wetted with pure Spirit of Wine. This alkalizated Spirit is also called _Tincture of Salt of Tartar_. In making this Alkaline Tincture, great care is to be taken that the Spirit of Wine you use be as highly rectified as possible: for, as long as it communicates any phlegm to the Alkali, it doth not acquire from the Salt mixed with it either the red colour, or the other properties which shew it to have dissolved part thereof. It is also a rule, to throw the Alkali exceeding hot into the Spirit of Wine, which being heated beforehand boils on the addition of the hot Salt. In order to render the Tincture still stronger, they are left to digest together for some time; after which, if part of the Spirit of Wine be drawn off by distillation, the remainder will have a redder colour and a more acrid taste. The Spirit drawn off by distillation is clear, colourless, and doth not give the same tokens of an alkaline quality as the Tincture; and for that reason, as the design of the present process is only to dephlegmate and rectify Spirit of Wine by means of a Fixed Alkali, we have directed it to be distilled as soon as all its phlegm is absorbed by the Salt. However, Spirit of Wine rectified in this manner must not be considered as absolutely pure; for a small degree of an alkaline quality is still perceptible in it: but that doth not hinder its being employed with success in several chymical operations, where the property chiefly required in Spirit of Wine is that it be perfectly dephlegmated. In order to free Spirit of Wine from the small portion of Alkali remaining in it after distillation, Mr. Boerhaave proposes to mix with it a few drops of the Vitriolic Acid, before the last distillation. But there is great reason to apprehend an opposite inconvenience from this practice: that is, instead of an alkaline character, we may give the Spirit an acid taint. Indeed this cannot be avoided, but by mixing with the Spirit of Wine exactly as much Acid, as suffices to saturate the Alkali contained in it, and no more; which is a point very difficult to hit. Van Helmont tells us, that having distilled Spirit of Wine from Salt of Tartar perfectly calcined, half of it came over pure water; and Mr. Boerhaave, to whom this appeared very surprising, resolved to repeat Van Helmont's experiment, in order to satisfy himself of the truth, and see with his own eyes what would be the result. With this view he made a tincture of Salt of Tartar in the manner above described, as strong and as fully impregnated as he possibly could. He set it in digestion with the Alkali for several months, and afterwards let it stand four years without touching it. He then poured the whole into a cucurbit, and drew off the Spirit of Wine from the Salt by distillation. The Spirit of Wine, which was before very red, became clear on being distilled, having left its colour in the Salt which remained at the bottom of the cucurbit. This Spirit he returned upon the Salt, and distilled as before. He observed, that, in this second distillation, the Spirit of Wine rose with a little more difficulty, and that the remaining Salt was of a more saturated colour, and become of a dark red. In this manner he cohobated and distilled his Spirit twenty times, with the same Salt. He then found that the Spirit of Wine had acquired a caustic, fiery taste, and that the saline mass in the bottom of the cucurbit was grown black. This saline residue he distilled with a stronger fire, and obtained from it a liquor, which was water, and not Spirit of Wine. Though Mr. Boerhaave seems, by this tedious labour, to have made Van Helmont's experiment succeed, at least in part, yet that famous and accurate Philosopher did not flatter himself with the notion of having solved the problem. He first observes, that he was far from getting the quantity of water which Van Helmont says he obtained, _viz._ half the weight of the Spirit of Wine. Secondly, he could scarce think that the quantity he did obtain actually came from the Spirit of Wine. The thing appeared to him so singular, and so hard to be accounted for, that he inclined to believe the water was quite extraneous both to his Spirit of Wine and to his Salt, and that it came from the air, which could not but be admitted in the frequent cohobations of the Spirit of Wine with the Alkali. When Mr. Boerhaave undertook this long laborious course of operations, he had it also in his view to try whether he could not, by the same means, solve another problem famed among the Chymists, namely, the Volatilization of the Salt of Tartar. He acquaints us, that in this also he failed; which may easily be believed: but, in my opinion, he was more successful with regard to the first point, than he himself imagined; for I think the water he obtained came immediately from the Spirit of Wine. We shall easily be convinced of this, if we carefully consider all the circumstances attending his experiments. It hath been shewn, that Spirit of Wine consists of an Oil, of an Acid, and of water, with which the Oil is intimately mixed by means of the Acid; that Spirit of Wine, which is not perfectly dephlegmated, may be deprived of a pretty considerable quantity of Water, which is superfluous and unnecessary to its composition; and that it suffers no change thereby, except that it becomes lighter, stronger, more inflammable, in short, more Spirit of Wine: but that, when it is once freed of this super-abundant phlegm, it would be in vain to attempt separating a greater quantity of water from it. All the water then left in it is essential to its composition, and necessary to give it its properties; for, without that, it would not be Spirit of Wine, but only an Oil loaded with an Acid. This being laid down, the water which cannot be separated from Spirit of Wine while it continues Spirit of Wine, must become sensible when it is decomposed. And this actually comes to pass: for if you rob Spirit of Wine of one of its principles, its Oil, for instance, and for that purpose burn it under a glass bell, as you do Sulphur, you will by this means collect a great quantity of water, even though you make use of the most highly rectified Spirit of Wine; which proves that this water was one of the essential parts that constituted the Spirit. If, instead of depriving this mixt of its oily principle, you separate from it one of its other principles, such as its Acid, it is plain that it will in like manner be decomposed, and that then the Oil and the water, which were combined together only by means of that Acid, will separate from one another, and appear each in its natural form. Now this is exactly the case in Van Helmont's experiment, as repeated by Boerhaave. The Fixed Alkali, on which the Spirit of Wine is cohobated, hath a greater affinity with the Acid of this mixt than with its phlegm or its Oil. It therefore unites with part of that Acid; by which means a proportional quantity of its Oil and water must needs separate from each other, and of course a portion of the Spirit of Wine will be decomposed. Accordingly Boerhaave observed, that, in dephlegmating Spirit of Wine by a Fixed Alkali, a portion of Oil is always separated from it, and that the Alkali employed in this operation is impregnated with an Acid, so that, when it hath been several times used for this purpose, it is almost changed into a Neutral Salt, and hath acquired the properties of the Foliated Salt of Tartar. That on which Spirit of Wine hath been cohobated a great number of times must consequently be impregnated with a great quantity of Acid; and, as the Acid carries with it a great deal of water, it is not surprising that when the Alkali, thus impregnated with Acid and phlegm, is exposed to a strong fire, the phlegm should be separated from it: seeing the union between them is but weak. Thus it appears that the water obtained by Mr. Boerhaave, in his experiment, came immediately from the Spirit of Wine, agreeably to Van Helmont's notion; whose most intelligent followers have clearly explained his sentiments on this subject, telling us, as their author's positive assertion, that, "in his experiment, the purest Spirit of Wine deposites one of its principles in the Salt of Tartar; that another of them is turned into water, and so separated from that Spirit, and from the principle attracted by the Salt of Tartar; that consequently Spirit of Wine certainly consists of these two principles, which may be separated from each other; and that the principle which unites with the Alkali of the Tartar changes this Salt into a medicament, or Balsam, of admirable virtue in curing wounds, known by the title of the _Samech_ of _Paracelsus_." It may here be asked, why Boerhaave obtained but a small quantity of water in this experiment, seeing Van Helmont pretends that it ought to be equal to half the weight of the Spirit of Wine. The most natural answer to this question is, that, as Van Helmont did not publish all the circumstances of his experiment, there is reason to think Boerhaave did not go about it in the same manner as Van Helmont did. In my opinion he would have succeeded perfectly, and have obtained from his Spirit of Wine the whole quantity of water he desired, if, instead of cohobating it always on the same Alkali, he had taken fresh Alkali every time; had drawn a tincture from it; had distilled his Spirit of Wine from this Salt; and, after collecting all the parcels of Alkali remaining after those distillations, he had exposed them to a strong fire, in order to separate all the moisture contained in them. Perhaps also such a great number of cohobations and distillations would not have been necessary to decompose the Spirit of Wine totally by this method; especially if he had employed a greater quantity of Alkali in each operation. For it is evident, that a Fixed Alkali, by being impregnated with a certain quantity of the Acid and water of the Spirit of Wine, loses thereby a great deal of its strength and activity, and at last becomes incapable of absorbing any more; so that, when it is entirely saturated, it is no more able to act upon Spirit of Wine, so as to decompose it, than so much Vitriolated Tartar, or common Sand. Hence you see, that there are still many beautiful experiments to be made on this subject, and that we may hope by a regular course of them to obtain a perfect solution of Van Helmont's problem. In the following processes we shall treat of another method of decomposing Spirit of Wine, which consists in depriving it of its essential water, or aqueous principle, by the means of highly concentrated Acids. CHAP. II. SPIRIT OF WINE _combined with_ DIFFERENT SUBSTANCES. PROCESS I. _To combine Spirit of Wine with the Vitriolic Acid. This combination decompounded. Rabel's Water. Æther. Sweet Oil of Vitriol. Hoffman's Anodyne Mineral Liquor._ Into an English glass retort put two pounds of Spirit of Wine perfectly dephlegmated, and pour on it at once two pounds of highly concentrated Oil of Vitriol: shake the retort gently several times, in order to mix the two liquors. This will produce an ebullition, and considerable heat; vapours will ascend, with a pretty loud hissing noise, which will diffuse a very aromatic smell, and the mixture will be of a deeper or lighter red colour, according as the Spirit of Wine was more or less oily. Set the retort on a sand-bath, made nearly as hot as the liquor; lute on a tubulated ballon, and distil the mixture with a fire strong enough to keep the liquor always boiling: a very aromatic Spirit of Wine will first come over into the ballon, after which the Æther will rise. When about five or six ounces of it are come off, you will see in the upper concavity of the retort a vast number of little points in a veined form, which will appear fixed, and which are nevertheless so many little drops of Æther, rolling over one another, and trickling down into the receiver. These little points continue to appear and succeed each other to the end of the operation. Keep up the same degree of fire, till upon opening the little hole in the ballon you perceive that the vapours, which instantly fill the receiver, have the suffocating smell of volatile Spirit of Sulphur[12]. [12] These white vapours do not appear when the vessels are perfectly close. Mr. Hellot, to whom we owe the remark, having performed this operation in a crystal retort procured from London, the neck of which had been rubbed with emery in the mouth of its receiver, so that these two vessels fitted each other exactly, saw the ætherial liquor distil pretty fast, but without white vapours. He then loosened the receiver, by turning it a little upon the neck of the retort, so that the external air might get in; whereupon the white vapours appeared immediately. When the receiver was close fitted on again, the vapours disappeared. He repeated the same thing five times from half hour to half hour, and these vapours as often appeared and disappeared. Then unlute the ballon, pour the liquor it contains into a crystal bottle, and stop it close: there will be about eighteen ounces of it. Lute on your receiver again, and continue the distillation with a greater degree of fire. There will come over an aqueous, acid liquor, smelling strong of a sulphureous spirit, which is not inflammable. It will be accompanied with undulating vapours; which being condensed will form an oil, most commonly yellow, one part of which will float on the surface of the liquor, and another will sink to the bottom. Towards the end of the distillation of this acid liquor, and of the yellow Oil of which it is the vehicle, that part of the mixture, which is left in the retort and grown black, will begin to rise in froth. Then suppress your fire at once: stop the distillation, and change your receiver once more. When the vessels are grown pretty cool, finish your distillation with a lamp-heat, kept up for twelve or fifteen days, which in all that time will raise but a very little sulphureous spirit. Then break your retort, in which you will find a black, solid mass, like a Bitumen. It will have an acid taste, arising from a remainder of the Acid imperfectly combined with Oil. This artificial Bitumen may be freed from its redundant Acid, by washing it in several waters. Then put it into a glass retort, and distil it with a strong reverberated fire. You will obtain a reddish Oil that will swim on water, much like the Oil obtained by distilling the natural Bitumens. This Oil also will be accompanied with an aqueous acid liquor. In the retort will be left a charred matter, which, being put into an ignited crucible in the fire, burns for some time, and, when well calcined, leaves a white earth. The liquors that rise first in this distillation, and which we directed to be kept by themselves, are a mixture consisting, 1. of a highly dephlegmated Spirit of Wine, of a most fragrant smell; 2. of Æther, which the Spirit of Wine wherewith it is united renders miscible with water; 3. of a portion of Oil, which commonly rises with the Æther, towards the end of the operation; 4. and sometimes of a little sulphureous acid, if the receiver be not changed soon enough. In order to separate the Æther from these other substances, put the whole into an English retort, with a little Oil of Tartar _per deliquium_ to absorb the Sulphureous Acid, and distil very slowly in a sand-bath heated by a lamp, till near half the liquor be come over. Then cease distilling; put the liquor in the receiver into a phial with some water and shake it; you will see it rise with rapidity to the upper part of the phial, and float on the surface of the water: this is the Æther. _OBSERVATIONS_. This operation is only a decomposition of Spirit of Wine by means of Oil of Vitriol. In the preceding process we saw that this Spirit, which consists of three essential principles, _viz._ an Oil, an Acid, and Water, cannot be deprived of one of them without being at the same time decomposed; the two others that remain having, by such separation, lost the bond of intimate union and connection that was between them. We saw also that Spirit of Wine, when mixed and digested with a very caustic Fixed Alkali, and several times distilled from it, deposites its Acid in that Salt: and hence it comes that the Oil and the Water, being deprived of the principle which was the bond of their union, separate from each other, and appear in their natural forms. In the present experiment, the Vitriolic Acid decomposes the Spirit of Wine in a different manner. We know that this Acid acts powerfully on Oils; and that, when it is highly concentrated, as the operation requires it should be, it seizes and attracts with surprising force the moisture of all bodies that touch it. So that, when it is mixed with Spirit of Wine, it acts at the same time both on the aqueous and on the oily principle of that mixt. The rapidity and activity, wherewith it rushes into union with these substances, produce the heat, the ebullition, and the hissing noise, which we observe during the first moments after their mixture. The red colour, which the two liquors confounded together acquire after some time, is owing to the combination of the acid with the oily part; for it is known that Oils, as colourless as Spirit of Wine, such as the Essential Oil of Turpentine, become of a brownish red when dissolved by a concentrated Acid: and Kunckel observed, that, the more Oil there is in Spirit of Wine mixed with Oil of Vitriol, the deeper is the red colour it acquires on being so mixed. He even gives this experiment as the certain means of discovering whether Spirit of Wine be more or less oily; and he adds, that Spirit of Wine, which hath lost part of its Oil by being rectified with Lime, acquires less redness than any other by being mixed with Oil of Vitriol. When the mixture hath acquired this colour, and before it undergoes distillation, it appears like a homogeneous liquor. There is yet no decomposition; or at least none that is perceptible; and the Vitriolic Acid is united at the same time with the Oil, the Acid, and the Water of the Spirit of Wine; that is, with the whole Spirit of Wine in substance. This mixture, when made with three parts of Spirit of Wine to one of Oil of Vitriol, is an astringent remedy much used in hemorrhages, and known by the name of _Rabel's Water_. The actual decomposition of the Spirit of Wine is effected by the distillation. The first liquor, or the first portion of the liquor that rises before the rest, hath the smell and all the properties of Spirit of Wine. It is indeed part of the Spirit of Wine employed as an ingredient in the mixture; but, being abstracted from a highly concentrated Oil of Vitriol, which, of all known substances, attracts moisture with the greatest power, it is perfectly freed of all its unnecessary phlegm, and retains no more than what is a constituent part thereof, as one of its principles, without which it would not be Spirit of Wine. The liquor that succeeds this first Spirit of Wine is of a different nature. It may be considered as an Æther: for, though it be not a pure Æther, it contains the whole of it: from this liquor only can it be obtained; it is no other than an Æther mixed with some of the Spirit of Wine that comes over first, and a little of the acid liquor which comes afterward. Now the production of Æther is the effect of a beginning decomposition of the Spirit of Wine: it is Spirit of Wine degenerated, half decomposed; Spirit of Wine too highly dephlegmated; that is, Spirit of Wine which hath lost a part of its essential phlegm, of that phlegm which as a necessary principle made it Spirit of Wine: it is a liquor still composed of oily parts mixed with aqueous parts, and on that account must retain a resemblance of Spirit of Wine; but such that its oily parts, not being dissolved and diffused among a sufficient number of aqueous particles, are brought nearer to each other than they should be to constitute perfect Spirit of Wine; on which account it is not now miscible with water, but is as much nearer to the nature of Oil, as it is removed from the nature of Spirit of Wine: it is a liquor, in short, which, being neither Spirit of Wine nor pure Oil, yet possesses some properties in common with both, and is consequently to be ranked in the middle between them. This explanation of the nature of Æther, which I imagine was never before given by any other, is the same that we proposed in our Elements of the Theory of Chymistry, which may be consulted on this occasion. An objection against this opinion may, perhaps, be drawn from an experiment well known in Chymistry. It may be said, that, if Æther were nothing but depraved Spirit of Wine, which ceases to be miscible with water, because the loss it hath sustained of a portion of the water necessary to its constitution hath disordered the proportion which ought to subsist between its aqueous and oily parts, from which proportion it derives that property, it would be very easy to change Spirit of Wine into Æther by a method quite contrary to the usual one; _viz._ by mixing Spirit of Wine with a sufficient quantity of superfluous Oil: for it seems to be a matter of indifference whether the proportion, between the aqueous and the oily parts of Spirit of Wine, be changed by lessening the quantity of the former, as in the common operation for Æther, or by increasing the quantity of the latter, as is here proposed; and we can, by the last method, put these two principles together in what proportion we please. Now it is certain that, whatever quantity of Oil be dissolved in Spirit of Wine, it will still remain miscible with water; and that, if Spirit of Wine thus replete with Oil be mixed with water, it will unite therewith as usual, and quit the Oil which it had dissolved. This objection, though seemingly a very specious one, will be removed with the utmost ease, if we reflect but ever so little on some of the principles already laid down. We said, and we gave some instances of it, that certain substances may be united together in sundry different manners: so that from these combinations, though made in the same proportions, there shall result compounds of very dissimilar properties. The combination we are now considering is another evidence of this truth. It is allowed that the proportion between the oily and the aqueous parts may be exactly the same in Æther and in Spirit of Wine replete with Oil; but it must also be owned that the manner in which the Oil is combined in these two cases is very different. That Oil, which at first is a constituting part of the Spirit of Wine, and afterwards becomes a part of the Æther, is united with the other principles of those mixts, that is, with their Acid and their Water, by the means of fermentation, whereby it is much more attenuated, and much more closely combined, than that with which Spirit of Wine is impregnated by dissolution only. And accordingly this adventitious Oil is so slightly connected with Spirit of Wine, that it is easily separable from it by barely distilling it, or even mixing it with water: whereas that which makes a part of the Spirit of Wine, as one of its constituent principles, is united therewith in such a manner as not to be separable from it by either of these methods, nor indeed without employing the most vigorous and powerful agents for that purpose. So that the chief differences between Æther and Oily Spirit of Wine must be ascribed to the different manner in which the Oil is combined in these two mixts: and, if a sufficient quantity of superfluous Oil could be united with Spirit of Wine, in such a manner that, without being soapy, it should not be separable therefrom by the affusion of water, I make no doubt but such a Spirit of Wine would be perfectly like Æther, so far as not to be miscible with water. But let us return to our distillation, and trace the decomposition of the Spirit of Wine by the Vitriolic Acid. We have shewn that the Acid begins with attracting part of the Water which constitutes the Spirit of Wine, by which means it changes the nature of this compound, destroys its miscibility with water, and brings it as much nearer to the nature of an Oil as it thereby removes it from the nature of Spirit of Wine. According to the theory laid down it is evident, that, if the Acid continue to act in the same manner on Spirit of Wine thus depraved and become Æther; that is, if it continue to draw from it the small remaining quantity of the aqueous principle, to which it owes the properties it still retains in common with Spirit of Wine, this must produce a total decomposition thereof; so that the oily parts, being no longer dissolved and divided by the aqueous parts, will be collected together, unite, and appear under their natural form, with all their properties. Now this is exactly the case. The Vitriolic Acid rises in the distillation after the Æther; but considerably changed, because it is loaded with the scattered remains of the decomposed Spirit of Wine. It is in a manner suffocated by the Water it hath attracted from the Spirit; which is the reason why it appears in the form of a very aqueous acid liquor. It carries up along with it the Oil which it hath separated from that Water: this is the Oil we took notice of in the process, and it is consequently that very Oily principle which actually constituted the Spirit of Wine. Lastly, by acting on this Oil also, it takes up a portion of phlogiston, which renders it sulphureous. What remains in the retort is also a portion of the Oil, that was contained in the Spirit of Wine, now combined with some of the Acid; which is the reason why it is black and thick. It is a compound much resembling a Bitumen, and when analyzed yields the same principles we obtain from native Bitumens, or from an Essential Oil thickened and half burnt by its combination with concentrated Oil of Vitriol. As to the Acid of the Spirit of Wine, some of it remains combined with the Æther: but there is great reason to think, that, when the Vitriolic Acid robs the Spirit of Wine of its aqueous part, it takes up at the same time most of its Acid, which being itself very aqueous, may be considered as pure water with respect to the concentrated Oil of Vitriol, by which it is attracted, and with which it is confounded. The properties which characterise Æther agree perfectly well with what we have said of its nature, and of the manner in which it is produced. It is one of the lightest liquors we know; it evaporates so suddenly, that, if a little of it be dropt on the palm of your hand, you will scarce perceive the part it touches to be wet by it; it is more volatile than Spirit of Wine; which is not at all surprising, seeing it differs therefrom only by containing less water, which is the heaviest principle in Spirit of Wine. Æther is more inflammable than Spirit of Wine; for, if any flame be brought but near it, it immediately catches fire. The reason of this is, that the oily parts of which it consists are not only as much attenuated, and as subtile, as those of Spirit of Wine, but also in a greater proportion with regard to its aqueous parts. To the same cause must be attributed the facility with which it dissolves any oily matters whatever. Æther burns without smoke, as Spirit of Wine does, and without leaving any coal or earthy matter behind; because the inflammable or oily parts contained in it are, in this respect, disposed like those of Spirit of Wine. The properties of not being miscible with water, and of taking up Gold dissolved in _aqua regis_, it possesses in common with Essential Oils; but the latter property it possesses in a much more sensible degree than any Oil: for Essential Oils sustain the Gold they thus take up but a little while; whereas the Æther never lets it fall. It seems the ancient Chymists were unacquainted with the Æther: or at least, if they did know it, they made a mystery of it, according to custom, and spoke of it only in enigmatical terms. Amongst the moderns Frobenius, a German Chymist, seems to have been the first who brought it to perfection. Godfrey Hankwitz, also a German, but settled in England, made mention of it much about the same time in the Philosophical Transactions. According to the latter, Mr. Boyle and Sir Isaac Newton both knew the preparation of Æther, for which they had each a different process. But none of these Chymists ever published an exact and circumstantial account of a method by which this liquor might be prepared: so that Messrs. Duhamel, Grosse, and Hellot, who have since made several experiments for that purpose, and have discovered, and communicated to the public, easy and certain methods of procuring Æther, had no assistance in their labours but from their own skill and sagacity; which gives them a just title to the honour of the invention. Mr. Beaumé also, a very ingenious Artist in Paris, who hath bestowed a great deal of pains on this subject, lately communicated to the Academy a Memoir, which, among several very important observations, contains the commodious and expeditious process above inserted. As there are many experiments in Mr. Hellot's Memoir, agreeing perfectly well with what hath been said concerning the decomposition of Spirit of Wine by the Vitriolic Acid, we think it will be proper to take notice of them here, and to examine them briefly at least. The quantity, the colour, and the weight of the Oil, which rises in the distillation at the same time with the aqueous acid liquor, are various, according to the different proportions of Spirit of Wine and Oil of Vitriol that are mixed together. Mr. Hellot observed that by increasing the quantity of the Vitriolic Acid he obtained more of this Oil, and less of the Ardent Spirit containing the Æther. The reason is this: the more Oil of Vitriol you put in the mixture, the more Spirit of Wine must be totally decomposed, and consequently the more of this Oil will be obtained; which, as we have shewn, is one of the principles resulting from the decomposition of Spirit of Wine. "This Oil is also lighter or heavier, in proportion to the quantity of Oil of Vitriol poured on the Spirit of Wine. That which arises from mixing six, five, four, or even three parts of Spirit of Wine with one part of concentrated Oil of Vitriol, always floats on the water, and continues white. That which ascends from two parts of Spirit of Wine is yellow, and most commonly sinks; and, lastly, that which is produced from equal parts of these two liquors is greenish, and constantly falls to the bottom." Mr. Hellot remarks, on this occasion, that part of the Acid, by the intervention of which this Oil is separated, unites therewith; and, to the greater or smaller quantity of the Acid thus combined with the Oil, he imputes its being more or less ponderous: which is the more probable, as the heaviest Oil is always obtained from a mixture in which the Acid bears the greatest proportion, and _vice versa_. Perhaps the different specific gravity of Essential Oils is wholly owing to the greater or smaller quantity of Acid they contain. Mr. Hoffman hath made several observations on this Oil, which evidently prove that it contains much Acid. He says, that, if it be kept for some time in a bottle, it grows red, and loses its transparency; that its agreeable aromatic taste becomes acid and corrosive; and that if you hold it over the fire in a silver spoon, it corrodes it, and leaves a black spot on it; and that it also corrodes Mercury, when heated therewith in a matrass. To this Mr. Pott adds, that it makes a very perceptible effervescence with Fixed Alkalis; and that being rectified by those salts it loses all the acid properties observed by Mr. Hoffman. Mr. Hellot obtained a still more considerable quantity of this Oil, by adding three or four ounces of a Fat Oil to the mixture of Spirit of Wine with the Vitriolic Acid. Now, as the Oil we are speaking of hath the properties of Essential Oils, and is soluble in Spirit of Wine, Mr. Hellot observes, that Oil of Vitriol by uniting with Fat Oils converts them into Essential Oils: which agrees very well with our opinion concerning the cause of the solubility of Oils in Spirit of Wine; which, in the Memoir already referred to on other occasions, we attribute to an Acid superficially and slightly united with Oils. The Oil which thus rises, in distilling Spirit of Wine mixed with the Vitriolic Acid, is known by the name of the _Sweet Spirit of Vitriol_. This name is very improper, because it may suggest a notion that this Oil derives its origin from the Vitriolic Acid, as some Chymists have erroneously thought; whereas it comes entirely from the Spirit of Wine, as we have shewn. If any reason can be assigned for keeping up the name, it must be because of the considerable quantity of the Vitriolic Acid that remains in the combination, and is dulcified by its union with the Spirit of Wine. This Oil is an ingredient in Hoffman's famous _Anodyne Mineral Liquor_. That liquor is thought to be nothing but this very Oil dissolved, and combined with the two liquors that rise first in the distillation, and immediately before the sulphureous acid phlegm. It dissolves very easily and quickly in those spirituous menstrua; so that, if you intend to have it by itself, and to prevent its recombining with the liquors that come off before, (which should be prevented, because it hinders the separation of the Æther), you must take great care to change the receiver as soon as the acid phlegm with which it rises begins to appear. We have seen that, by the methods which Mr. Hellot hath pointed out, this Sweet Oil of Vitriol may be increased, both in weight and quantity. In that ingenious Chymist's Memoir we also find some methods of preventing it from rising in the distillation. They consist wholly in the addition of some Absorbent bodies, which, he tells us, divert the action of the Vitriolic Acid, at least in some measure, from the inflammable part of the Spirit of Wine. One of these methods is as follows. "Put into Spirit of Wine as much soft Soap as it can dissolve: filter it, and pour on it some of the heaviest and most concentrated Oil of Vitriol: shake the mixture. The Soap will be instantly decompounded, and its Oil will float on the surface; because the Vitriolic Acid robs it of the Alkali, which renders it miscible with Spirit of Wine. Distil it, and you will obtain but a very little of Rabel's water; which, moreover, will have the disagreeable smell of a most rancid Oil. There will afterwards ascend a great quantity of Spirit of Wine having the same smell; then an aqueous, acid, and sulphureous liquor; but not a drop of yellow Oil. Mean time there forms a bituminous fungus, of some confidence, rising above the Oil of the Soap which floats on the rest of the liquid." Most of the Vitriolic Acid having been absorbed by the Alkali of the Soap, in this experiment, as Mr. Hellot observes, it is not surprising that it should not act upon the Spirit of Wine with so much efficacy as to decompose it, and separate its Oil. For the same reason but a little of Rabel's Water comes over, and almost all the Spirit of Wine rises without undergoing any sensible alteration. The disagreeable smell of those liquors comes from the Oil of the Soap, which, being naturally heavy, remains behind in the retort, where it grows rancid and is partly burnt. The last experiment in Mr. Hellot's Memoir, of which we shall take notice, is a peculiar process for preparing Æther; by means whereof, with the help of an earthy medium, it is easy to distil the vinous acid Spirit containing the Æther, without any sensible change of smell from the beginning to the end of the operation; without its being succeeded by an acid sulphureous liquor, oil, black scum, resin, or bitumen; and without the necessity of taking any great care about the management of the fire, as the liquor may always be kept boiling in the retort, and distilled to dryness without any danger. This medium is common potter's earth. Mr. Hellot puts six ounces thereof, well dried and pulverized, into a large retort, with one pound of Spirit of Wine and eight ounces of Oil of Vitriol. These he digests together three or four days. The mixture acquires no sensible colour. He sets the retort in a sand-bath, and continues the distillation to dryness with a moderate charcoal fire. Excepting a few drops that rise first, and which are pure Spirit of Wine, all the rest of the liquor that distils hath constantly the smell of Æther: which is even somewhat more penetrating than that of the vinous acid Spirit obtained without the intervention of this earthy medium. We have shewn, that the production of the æthereal liquor is owing to a semi-decomposition of the Spirit of Wine effected by the Vitriolic Acid during the distillation; that this Acid continuing to act, produces a total decomposition, or perfect separation of the Oil and Phlegm of the Spirit of Wine from each other; and that the Vitriolic Acid, uniting with these two principles, forms the sulphureous phlegm, the fluid oil, and the bituminous matter, all frequently mentioned above. Why then, in this experiment of Mr. Hellot's, do we obtain only a Spirit of Wine replete with Æther, while none of the other productions appear? The reason is a very natural one, and very clear: it is this; the potter's clay containing an earth of that kind which we called Absorbent, because it possesses the property of uniting with Acids, that earth joins with the Vitriolic Acid in the mixture, reduces it to a Neutral Salt, and thereby prevents its continuing to act upon the Spirit of Wine, as is necessary to the total decomposition thereof. Mr. Hellot says on this occasion, "that part of the Vitriolic Acid turning its action on this soluble earth or bole, which it finds in the potter's clay, ceases to act on the inflammable principle of the Spirit of Wine; that, consequently, as there is not an immediate and continuous combination of these two substances, neither a resin nor a bitumen can result therefrom. This is so true, that a great part of the Oil of Vitriol may be afterwards recovered from the potter's clay as colourless as when it was first used." Mr. Hellot makes use of the following method for procuring the Æther from the acid vinous Spirit obtained by this distillation. "You must," says he, "put all this liquor into a glass body, made of one piece with its head; pour upon it, through the hole in the upper part of the head, twice or thrice as much well-water, the hardest to the taste, and the most impregnated with gypsum, that can be got. Very pure water, he observes, produces much less Æther. "If the vinous acid Spirit have such a sulphureous smell, as to occasion a suspicion that it contains a little too much of a Volatile Vitriolic Acid, you must add to the water two or three drams of Salt of potash to absorb that Acid; and then distil with a lamp-heat. "While any true Æther remains in the mixture, you will see it ascend like a white pillar issuing from the midst of the liquor, and consisting of an infinite number of air bubbles inexpressibly small. Nothing seems to condense in the cavity of the head, which always remains clear, and without any visible humidity. The gutts which light on the sides of the receiver, instead of forming a net-work thereon, as Spirit of Wine doth when it is a little aqueous, spread to the breadth of two inches or more, when they consist of true Æther. As soon as you perceive this track begin to grow considerably narrower, the fire must be put out; for what rises afterwards will be mixed with water, and communicate that fault to the Æther already collected in the receiver. "Then pour this ætherial liquor into a long bottle, and add to it an equal quantity of well-water. Shake the bottle; the liquor will become milky, and the true Æther will instantly separate, float upon the water, and mix no more with it. Separate it then by a siphon, and keep it in a glass bottle shut close with a glass stopple." PROCESS II. _Spirit of Wine combined with Spirit of Nitre. Sweet Spirit of Nitre._ Into an English retort of crystal glass put some highly rectified Spirit of Wine; and, by means of a glass funnel with a long pipe, let fall into your Spirit of Wine a few drops of the Smoking Spirit of Nitre. There will arise in the retort an effervescence attended with heat, red vapours, and a hissing noise like that of a live coal quenched in water. Shake the vessel a little, that the liquors may mix thoroughly, and that the heat may be equally communicated to the whole. Then add more Spirit of Nitre, but in a very small quantity, and with the same precautions as before. Continue thus adding Spirit of Nitre, by little and little at a time, till you have put into the retort a quantity equal to a third part of your Spirit of Wine. Let this mixture stand quiet, in a cool place, for ten or twelve hours; then set it to digest in a very gentle warmth for eight or ten days, having first luted on a receiver to the retort. During this time a small quantity of liquor will come over into the receiver, which must be poured into the retort. Then distil with a somewhat stronger degree of heat, but still very gently, till nothing be left in the retort but a thick matter. In the receiver you will find a spirituous liquor, of a quick grateful smell, which will excite a very smart sensation on the tongue, but without any corrosive acrimony. This is _The Sweet Spirit of Nitre_. _OBSERVATIONS._ By this operation Spirit of Nitre is combined with Spirit of Wine; these two liquors being united with each other, much in the same manner as the Vitriolic Acid is with Spirit of Wine in Rabel's Water. The proportion of the liquors which form this combination is not absolutely determined, and the several authors who have written on the subject differ much about it. Some require equal parts of the ingredients; others again from two as far as ten parts of Spirit of Wine to one of Spirit of Nitre. This depends on the degree to which the Spirit of Nitre made use of is concentrated, and on the greater or less acidity which your dulcified Spirit of Nitre is intended to have. The Dispensatory of the College of Paris orders one part of Spirit of Nitre distilled from dried clay, that is, of Spirit which doth not smoke, to be mixed with two parts of rectified Spirit of Wine, and the whole to stand in digestion for a month, without distilling the mixture at all. This is a very good method: because the long digestion supplies the place of distillation, and the Spirit of Nitre, not being highly concentrated, doth not greatly alter the Spirit of Wine; besides that many inconveniences, to be presently taken notice of, are by this means avoided. But as our design is not to describe such Chymical preparations only as are commonly used in medicine, our plan requiring us to treat particularly of those which may give any light into the fundamental properties of bodies, the process here set down appeared the fittest for our purpose; because the action which Spirit of Nitre exerts upon Spirit of Wine is therein stronger and more perceptible. One of the first particularities attending the mixture of those two liquors, is the great effervescence, accompanied with violent heat, abundance of fumes, and loud hissing, which arises as soon as the Spirit of Nitre and the Spirit of Wine come into contact with each other. There is great reason to think, that these phenomena are produced only by the rapidity and vigour with which the Nitrous Acid rushes into union with the inflammable part of the Spirit of Wine. We observed, in treating of the Æther, that phenomena of the same kind appear at the instant when the Vitriolic Acid unites with Spirit of Wine: but on that occasion, how highly soever the Vitriolic Acid be concentrated, all these effects are in a less degree than those produced in the present experiment; because the Nitrous Acid, though weaker than the Vitriolic, generally acts much more vigorously and violently on the bodies with which it unites, than any other sort of Acid. Concerning these mixtures of Acids with Spirit of Wine, Mr. Pott observes, that it is not a matter of indifference whether you pour the Spirit of Wine upon the Acid, or the Acid on the Spirit of Wine; but that every thing passes much more quietly, when the Acid is poured to the Spirit of Wine, than when the contrary is done: and he gives the true reason thereof; to wit, that when the Acid is poured on the Spirit of Wine it finds in that liquor a great quantity of water, with which it immediately unites; that this weakens it, and hinders it from acting on the inflammable part with so much impetuosity as it otherwise would; and therefore he advises that such mixtures be always made in this manner. But it is evident that this advantage is gained only by mixing the Acid with the Spirit of Wine very gradually, and drop by drop, as directed in the process after Mr. Pott. For, if the two liquors were to be mixed together suddenly, and all at once, it is certain that the Acid would not meet with a single drop of phlegm more or less in that way than in the other. Therefore the chief, and, in some measure, the only precaution necessary to be taken, in the making of such mixtures, to prevent the violent effervescence and other inconveniences that may attend it, such as explosion, and the bursting of the vessels, is to pour but a very small quantity of one liquor into the other at a time, and to add no more till the effervescence, and even the heat, produced by the first portion, be entirely ceased. With these precautions you may proceed either way, and be always sure that the vessels will not burst; because it is in your power to add such a small quantity of liquor at a time, as shall scarce produce a sensible effervescence. We own, however, that Mr. Pott's observation is a very just one. There is even an advantage in pouring the Acid to the Spirit of Wine, as he directs; which is, that the mixture is a little sooner made, and without any danger. We have shewn, that the Vitriolic Acid becomes aqueous and sulphureous by mixing Spirit of Wine with it: the Nitrous Acid is changed by this mixture in a manner no less remarkable. Mr. Pott observes, that when Spirit of Nitre is dulcified, that is, when it is perfectly combined with Spirit of Wine, it loses the disagreeable odour peculiar to it, and acquires another that is quick and fragrant; it doth not afterwards emit any red fumes; it rises with a less degree of heat than when pure; it acts with less vigour on Fixed Alkalis and Absorbent earths. Lastly, we shall here relate an experiment made by that Chymist, which seems to prove that the Nitrous Acid loses its most characteristic properties, and entirely changes its nature, by being combined with Spirit of Wine. Mr. Pott examined the thick liquor left in the retort, when the dulcified Spirit of Nitre is distilled off. By analyzing it he obtained an acid liquor, of a yellow colour, and of a somewhat empyreumatic smell. This Acid was followed by some drops of a red empyreumatic Oil; and there remained, at the bottom of the distilling vessel, a black, shining, charred matter, like that which remains after the rectification of a fetid Oil. The Oil extracted from this residue is a portion of that which helped to constitute the Spirit of Wine; being separated therefrom by the Nitrous Acid, in the same manner as that treated of in the preceding process, and called _Sweet Oil of Vitriol_, is separated by the Vitriolic Acid. But as the Nitrous Acid, which is weaker than the Vitriolic, doth not so effectually decompose the Spirit of Wine, the Oil, obtained in the present experiment, is in smaller quantity than that procured in the distillation of a mixture of the Vitriolic Acid with Spirit of Wine. As to the Acid which Mr. Pott drew off in his experiment, there is great reason to think it a part of that which was an ingredient in the mixture; namely, of the Nitrous Acid. And yet Mr. Pott having saturated with a Fixed Alkali one part of the residuum, which he had a mind to examine before the Acid was separated from it by distillation, and expecting this matter to contain a regenerated Nitre, he threw it on a live coal; but was surprised to see it burn without the least sign of detonation; and thence concluded, that the Nitrous Acid had changed its nature. This experiment, he thinks, may furnish hints for the transmutation of Acids; and he is of opinion, that the Nitrous Acid loses its virtue of detonating, in the present case, only because its inflammable part, to which it owes its distinguishing properties, hath deserted it, and joined with that of the Spirit of Wine. Indeed if the Acid obtained by Mr. Pott, which being reduced to a Neutral Salt doth not detonate, derives its origin from the Nitrous Acid that was combined with the Spirit of Wine, there is no doubt of its being depraved in a peculiar manner, and having entirely changed its nature. But may we not suppose it to have another origin? May it not be the Acid of the Spirit of Wine itself, resulting from the decomposition of that mixt in the distillation? Mr. Navier, whom we mentioned in our Elements of the Theory, extracted a very singular oily liquor from the mixture of Spirit of Wine and Spirit of Nitre, without distillation, and even without the help of fire. He put equal parts of the two liquors, by measure, not by weight, into a bottle, which he stopped close with a good cork, fastened down with pack-thread. Nine days afterwards he found about a sixth part of the mixture separated from, and floating on, the rest of the liquor. This was a very fine æthereal Oil, very limpid, and almost as colourless as water. In another experiment Mr. Navier substituted a solution of Iron in the Nitrous Acid for pure Spirit of Nitre; and with this solution he mixed an equal weight of Spirit of Wine. From the mixture, after a fermentation which appeared in it, he obtained by the same method an æthereal Oil, like that of his former experiment; except that the latter, which was at first as colourless as the other, acquired a redness in the space of about three weeks. He conjectures, with probability, that this colour proceeded from some particles of Iron which were united with it, and which gradually exhaled. If a few drops of Oil of Tartar _per deliquium_ be poured on this Oil, as soon as it is separated, there appears at first no sensible change therein: but after some time needle-like crystals shoot in it, which are a true regenerated Nitre; and if the bottle be then unstopped, the liquor emits a most pungent nitro-sulphureous odour; which leaves no doubt of this Oil's containing a Nitrous Acid. When it is thus freed of its Acid, by means of the Oil of Tartar, it is much more volatile than before. Neither the Vitriolic nor the Marine Acid is capable of separating such an Oil from Spirit of Wine: but the Nitrous Acid always produces it, even when it is not concentrated, and doth not smoke. It is very certain that this Oil derives its origin from the Spirit of Wine: but there are not yet experiments enough made upon it, to enable us to speak very accurately about the manner in which this liquor is formed, or of the cause of its separation from the Spirit of Wine. PROCESS III. _Spirit of Wine combined with the Acid of Sea-salt. Dulcified Spirit of Salt._ Mix together, little by little, in a glass retort, two parts of Spirit of Wine with one part of Spirit of Salt. Set this mixture to digest for a month in a gentle heat, and distil it, till nothing remain in the retort but a thick matter. _OBSERVATIONS._ The Acid of Sea-salt is much less disposed to unite with inflammable matters than the other two mineral Acids; and therefore, though it be ever so highly concentrated, when mixed with Spirit of Wine, it never produces an effervescence comparable to that which is produced by the Spirit of Nitre. Neither the proportion nor strength of the Spirit of Salt, requisite to prepare the Sweet Spirit of Salt, are unanimously agreed upon by Authors. Some direct equal parts of the two liquors; while others prescribe from two to four or five parts of Spirit of Wine to one part of Spirit of Salt. Some use only common Spirit of Salt; others require the Smoking Spirit, distilled by means of Spirit of Vitriol. Lastly, some order the mixture to be distilled, after some days digestion; and others content themselves with barely digesting it. The whole depends on the degree of strength which the Sweet Spirit of Salt is intended to have. This composition, as well as the Sweet Spirit of Nitre, is esteemed in medicine to be very aperitive and diuretic. When the mixture of Spirit of Salt and Spirit of Wine is distilled, there comes over but one liquor, which appears homogeneous. This is the Sweet Spirit of Salt. The nature of the Marine Acid is not changed in this combination: the Acid is only weakened and rendered more mild; but in other respects it retains its characteristic properties. Some authors pretend, that an Oil is obtained by distilling the mixture for the Sweet Spirit of Salt; but others expressly deny the fact. This variety may be occasioned by the quality of the Spirit of Wine employed. It would not be surprising if a Spirit of Wine, which contains much Oil that is unnecessary to its nature, and, as it were, adventitious to it, should yield an Oil when distilled with Spirit of Salt. The thick residue, found in the retort after distillation, contains the most ponderous part of the Acid, united with part of the Spirit of Wine. If the distillation be continued to dryness, there remains in the retort a black charred matter, much like that which is left by the combinations of Spirit of Wine with the other Acids. A sweet Spirit of Salt may also be prepared by digesting Spirit of Wine with, or distilling it from, metallic compositions replete with the Marine Acid adhering but slightly to them; such as Corrosive Sublimate, and Butter of Antimony. Part of this Acid, which is very highly concentrated, quits the metallic substance with which it is but superficially combined, in order to unite with the Spirit of Wine. If Butter of Antimony be used for this purpose, Mr. Pott, the author of these experiments, observes, that a _Mercurius Vitæ_ precipitates; which is nothing else, as we observed in its place, but the reguline part of the Butter of Antimony deserted by its Acid. PROCESS IV. _Oils, or Oily Matters, that are soluble in Spirit of Wine, separated from Vegetables, and dissolved by means of that Menstruum. Tinctures; Elixirs; Varnishes. Aromatic Strong Waters._ Put into a matrass the substances from which you intend to extract a Tincture, having first pounded them, or pulverized them if they are capable of it. Pour upon them Spirit of Wine to the depth of three fingers breadth. Cover the matrass with a piece of wet bladder, and tye it on with pack-thread. Make a little hole in this bit of bladder with a pin, leaving it in the hole to keep it stopped. Set the matrass in a sand-bath very gently heated. If the Spirit of Wine dissolve any part of the body, it will accordingly acquire a deeper or lighter colour. Continue the digestion till you perceive that the Spirit of Wine gains no more colour. From time to time pull out the pin, to give vent to the vapours, or rarefied air, which might otherwise burst the matrass. Decant your Spirit of Wine, and keep it in a bottle well corked. Pour on some fresh Spirit in its stead; digest as before; and go on in this manner, pouring on and off fresh Spirit of Wine, till the last come off colourless. _OBSERVATIONS._ It is commonly said, that Spirit of Wine is the solvent of Oils and oily matters: but this proposition is too general; for there are several sorts of Oils and oily matters which this menstruum will not dissolve. Of this number are the Fat Oils, Bees-Wax, and the other Oily compounds of that kind. Properly speaking, it dissolves but two sorts of oily substances; namely, Essential Oils, and Balsams or Resins, which are matters of the same kind, differing from each other only as they are more or less thick; and Oils that are in a saponaceous state. In our Elements of the Theory we have explained our opinion on this head, from a Memoir on the subject printed among those of the Academy for 1745. To repeat it in a few words: we take the cause of the solubility of Oils in Spirit of Wine to be an Acid, which is but superficially united with them, and so as still to retain its properties. The principal proofs on which we found this opinion are drawn from that property of Essential Oils, Balsams, and Resins, which are naturally soluble in Spirit of Wine, that they become so much the less soluble in this menstruum, the oftener they are distilled or rectified; and from that property which Fat Oils, or other Oily matters, naturally indissoluble in Spirit of Wine, possess, of becoming more and more soluble therein the oftener they are distilled. We shewed that distillation lessens the solubility of Essential Oils, Balsams, and Resins, only by depriving these substances of part of the manifest Acid which they contain, and which is the cause of their solubility; and that Fat Oils, and other oily matters, naturally indissolvable in Spirit of Wine, are by the same operation rendered capable of dissolving therein, only because it discovers, and partly extricates, an Acid, which is naturally combined with them so intimately that it is entirely deprived of action, and all its properties perfectly masked. If these principles be well attended to, and if it be recollected withal, that Spirit of Wine unites with Water preferably to Oils; insomuch that, if it be mixed with water when it hath dissolved an Oil, it quits the Oil to unite with the Water; that for the same reason it is not capable, when very aqueous, of dissolving any Oil, seeing that, as Oil and water are not susceptible of contracting any union, it must then desert its phlegm to unite with the Oil; which it cannot do, because it hath a greater affinity with phlegm than with Oil; and, lastly, that if Oil be combined with any saline substance, which makes it soluble in water; that is, if it be in a saponaceous state, it will then remain dissolved in Spirit of Wine, without being precipitated by water; or will be dissolved by a very aqueous Spirit of Wine, and frequently much better than by a highly rectified Spirit: if these things, I say, be considered, we shall easily perceive what must be the effect of digesting Spirit of Wine with any vegetable substance whatever. Spirit of Wine dissolves all the Essential Oil, Balsam, and Resin contained in any vegetable; and as these matters are not soluble in water, they may be separated from the Spirit in which they are dissolved, by lowering it with much water. It instantly becomes white and opaque, like milk; the oily parts gradually unite, and form considerable masses, especially if they be resinous. This is the method commonly made use of to extract the Resin of Scammony, Jalap, Guaiacum, and several other vegetable substances, which it would be difficult to procure by any other means. If the matters digested with Spirit of Wine contain any saponaceous juices, the Spirit will take up those juices also. But as soaps are soluble in water, as well as in Spirit of Wine, they cannot be separated, by the addition of water, from the Spirit in which they are dissolved. Whatever quantity of water therefore you mix with a Spirit that is impregnated with such juices, no separation thereof will be produced; and for the same reason the saponaceous matters will be dissolved by a very aqueous Spirit of Wine. Spirit of Wine impregnated with such parts of any vegetable substance, as it is capable of dissolving, is commonly called a _Tincture_. Several Tinctures mixed together, or a Tincture drawn from sundry vegetable substances at the same time, and in the same vessel, take the name of an _Elixir_. Tinctures or Elixirs impregnated with Resinous matters only are true _Varnishes_. All these preparations are made in the same manner; to wit, as directed in our process. We shall only add here, that if the substances from which a Tincture or Elixir is to be made contain too much moisture, it is proper to free them from it by a gentle desiccation; especially if you design that the Tincture should be well impregnated with the oily and resinous parts: for their excess of moisture uniting with the Spirit of Wine would weaken it, and render it unable to act on those matters, which it cannot dissolve when it is aqueous. Vegetable substances which have been repeatedly digested with different parcels of Spirit of Wine, till the last would extract nothing, are deemed to be exhausted of all their Essential Oils, and saponaceous juices: but if they contain moreover any Fat Oil, Wax, or Gum, these principles will still remain therein after the digestion, in the same quantity as before; because Spirit of Wine is incapable of dissolving them. With regard to the Fat Oil and Wax, this is not at all surprising: we have explained in another place why these matters are indissoluble by Ardent Spirits: but as for the Gum, it would seem, according to the general principles above-mentioned, that it should be soluble in that menstruum, even with more ease than Resins; as it consists almost entirely of water, with which Spirit of Wine is known to unite more easily than with Oils. Indeed there is also a little Oil in its composition: but this Oil seems to be in a perfectly saponaceous state; for Gum dissolves wholly and easily in water, without lessening its transparency in the least. I own that it is extremely difficult to give a very satisfactory account of this matter. We may however venture to throw out some conjectures concerning it, deduced from what hath been already said, relating to the cause of the solubility of Oils in Spirit of Wine. We shewed that the Oils which dissolve in this menstruum derive that property from a manifest Acid, which is united with them but superficially, and in such a manner as to retain all its virtue; but that if this same Acid be too intimately united with the Oil, so as to have no manifest power, but be in a manner destroyed, and converted as it were into a Neutral Salt, it will not then produce this effect. A modern author[13] relates two experiments which agree very well with this opinion, and indeed confirm it. He mixed together Oil of Vitriol and Oil of Turpentine, with a view to imitate by art a bituminous matter; which, we know, is not at all, or at least scarcely, soluble in water. These two matters being united together produced a red, thick compound, which by evaporation became like a natural Bitumen. [13] Mr. Eadows, in a little English book, entitled _The Modern Apothecary_. The author observes, that when this mixture is just made it dissolves in Alcohol; but that in some time it changes its nature, and communicates scarce any part of its substance to that solvent. Now whence can such a difference arise, but from this, that when the mixture is new, the Acid is as yet but superficially united with the Oil, and combines with it more and more intimately, as the mixture grows older. The same author, having repeated the experiment with Spirit of Vitriol, obtained a compound which continued always very soluble in Spirit of Wine: because Spirit of Vitriol being much weaker and more aqueous than Oil of Vitriol, was incapable of combining so closely with the Oil of Turpentine, as that concentrated Acid did in the former experiment. By the by, there is great reason to believe that the very intimate union of a mineral Acid with an oily matter is the true cause why Bitumens will not dissolve in Spirit of Wine. It seems therefore pretty probable, that the Acid which makes the Oil of Gummy matters soluble in water, and reduces it to a saponaceous state, is so intimately united with that Oil, that it loses its properties, and is in a manner converted into a Neutral Salt. Now we know that such Salts are soluble in water, but are not so, for the most part, in Spirit of Wine. If your Tinctures or Elixirs be not so strong or so saturated as you desire, you may by distillation abstract part of the Spirit of Wine which they contain, and by that means give them such a degree of thickness as you judge proper. But the Spirit of Wine thus drawn off constantly carries along with it a good deal of the aromatic principle. It is a truly _Aromatic Strong Water_. This Spirit of Wine also carries up with it a portion of thin Oil, which is so much the more considerable as the degree of heat employed is greater: and this is the reason why it becomes of a milky colour when mixed with water. If you intend to make an Aromatic Strong Water only, you need not previously extract a Tincture from the vegetable substance with which you mean to prepare your water: you need only put it in a cucurbit, pour Spirit of Wine upon it, and distil with a gentle heat. By this means you will obtain a Spirit of Wine impregnated with all the odour of the plant. CHAP. III. _Of_ TARTAR. PROCESS I. _Tartar analyzed by distillation. The Spirit, Oil, and Alkaline Salt of Tartar._ Into a stone retort, or a glass one coated with lute, put some white Tartar broken into small bits, observing that one half, or at least a full third, of the vessel be left empty. Set your retort in a reverberating furnace. Fit on a large ballon, having a small hole drilled in it; lute it exactly with fat lute, and secure the joint with a linen cloth smeared with lute made of quick-lime and the white of an egg. Apply at first an exceeding gentle heat, which will raise a limpid, sourish, pungent water, having but little smell, and a bitterish taste. When this first phlegm ceases to come off, increase your fire a little, and make the degree of heat nearly equal to that of boiling water. A thin limpid Oil will rise, accompanied with white vapours, and with a prodigious quantity of air, which will issue out with such impetuosity, that if you do not open the little hole in the receiver time enough to give it vent, it will burst the vessels with explosion. An acid liquor will rise at the same time. Continue the distillation, increasing the heat by insensible degrees, and frequently unstopping the little hole of the receiver, till the elastic vapours cease to issue, and the oil to distil. Then raise your fire more boldly. The acid Spirit will continue to rise, and will be accompanied with a black, fetid, empyreumatic, ponderous, and very thick Oil. Urge the fire to the utmost extremity, so that the retort may be of a perfect red heat. This violent fire will raise a little Volatile Alkali, besides a portion of Oil as thick as pitch. When the distillation is finished, you will find in the retort a black, saline, charred matter, which grows hot when wetted, attracts the moisture of the air, runs _per deliquium_, and hath all the properties of a Fixed Alkali. This mass, being exposed to a naked fire in the open air, burns, consumes, and is reduced to a white ash, which is a fiery, caustic, Fixed Alkali. _OBSERVATIONS._ The matters qualified to produce a spirituous liquor by fermentation, do not all contain the just and accurate proportion of Acid necessary to constitute an Ardent Spirit. Many of them, the juices of fruits for instance, and especially that of the Grape, are replete with a super-abundant quantity of Acid, more than concurs to form that product of fermentation. This super-abundant Acid, combined with some of the Oil and earth contained in the fermented liquor, produces a sort of Salt, which hangs for a while suspended in that liquor, but after some time, when the Wine stands quiet in a cool place, separates from it, and forms a stone-like incrustation on the inside of the vat in which the Wine is kept. This matter is called _Tartar_. The Lees of Wine resemble Tartar, in as much as they contain, and yield when analyzed, the same principles; but they differ from it in this, that they contain, moreover, a greater quantity of earth, of phlegm, and a little Ardent Spirit, which are only mixed, but not united, with the tartarous Acid. The residue, or sort of extract, which remains in the cucurbit after Wine hath been deprived of its Ardent Spirit by distillation, hath also a great conformity with Tartar. It even contains that portion of Tartar which remained suspended in the Wine at the time of its distillation: and accordingly this residue of Wine, being analyzed, yields the same principles with Tartar. Hence we see, that liquors, which have undergone the spirituous fermentation, consist of an Ardent Spirit and a Tartarous Acid suspended in a certain quantity of Water. In the analysis of Tartar there are several things worthy of notice. The first is, the vast quantity of Air that this mixt body yields when it begins to be decomposed. The chief difficulty attending its analysis arises from this air; which issues out and exerts its elastic force with such impetuosity, that all the precautions above-mentioned are no more than necessary to prevent the bursting of the vessels. The singular nature of the thin limpid Oil, which rises with this air, after the first acid phlegm, deserves likewise our particular attention. This Oil is one of the most penetrating we know. Boerhaave, who distilled Tartar without having a vent-hole in his receiver, was obliged, in order to prevent its bursting, to apply it to his retort with a lute so weak that most of the elastic vapours might perspire through it; and he observed, that, though the neck of his retort entered above five inches into the mouth of his receiver, and was luted on as closely as possible with such a lute, yet this light Oil of Tartar constantly returned back again, as it were, and pervaded the substance of the lute, so that a good deal of it dropped in a dish placed on the outside on purpose to receive it. This Oil is probably rendered so active and subtile, only by having been exceedingly attenuated by the fermenting motion. This experiment is one of those which sufficiently prove the necessity of employing receivers having a small vent-hole, that may be opened and shut as occasion requires. The last remark we shall make, on the productions of Tartar by distillation, relates to the _caput mortuum_ found in the retort when the operation is finished. This residue is very different from that which other vegetable matters afford: for, when they are decomposed in close vessels, they leave nothing but a mere charred matter, in which no saline property appears, and from which no Fixed Alkali can be obtained, but by carrying their analysis to the utmost; that is, by burning them in the open air. Tartar, on the contrary, only by being distilled in close vessels, without burning it afterwards in the open air, is changed into a substance which hath all the properties of a Fixed Alkali. This is probably owing to the Tartar's containing the principles requisite to form a Fixed Alkali in a much greater quantity than they are to be found in any other substance. As Tartar thus alkalizated in close vessels still contains much inflammable matter, it might be employed with advantage as a reducing flux, in several operations of metallurgy. Of all the vegetable matters we know, calcined Tartar yields the greatest quantity of Fixed Alkali; which is likewise very pure, and therefore much used in Chymistry. Burnt Lees of Wine also afford a great quantity of Fixed Alkali, which is of the same nature with that of Tartar. This Salt is used in different trades, and particularly in Dying. The French Vinegar-makers collect quantities of these Lees, which they make up into cakes and dry: while it is in this state they call it _Gravelle_ or _Gravelée_; and _Cendre Gravelée_ when it is burnt. If the extract of Wine, which remains after the Spirit is drawn off, be gently evaporated to dryness, and that dry matter burnt like Tartar or _Gravelle_, it will make a sort of _Cendre Gravelée_ very rich in alkaline Salt. PROCESS II. _The Depuration of Tartar. Cream and Crystals of Tartar._ Reduce to a fine powder the Tartar you intend to purify, and boil it in twenty-five or thirty times as much water. Filter the boiling liquor through a flannel-bag, and then gently evaporate some part of it: there will soon form on its surface a saline crust, which is the _Cream of Tartar_. Let your liquor cool, and there will adhere to the sides of the vessel a great quantity of a crystallized saline matter, which is _Crystal of Tartar_. _OBSERVATIONS._ Tartar, when taken out of the vats in which it forms, is mixed with a considerable quantity of earthy parts, which are not intimately united therewith, but adulterate it. This extraneous earth makes about two fifths of the whole weight of common Tartar; but white Tartar, which is the best, contains but about a third part of earth. The method of refining Tartar, and freeing it from this adventitious earth, is very simple, as appears from the process. Earthy matters, which are not intimately combined with an Acid in the form of a Neutral Salt, are not dissoluble in water: for which reason the water, in which crude Tartar is boiled, dissolves the saline part only, which passes with it through the filter; but doth not dissolve the earth of the Tartar, because that earth is not combined with the saline part, and so being only suspended in the liquor remains on the filter. The saline parts of the Tartar, though they are now separated from the gross earth with which they were mixed, are not yet perfectly pure. These first Crystals of Tartar have a disagreeable russet colour, and are not transparent: this is owing to their being coated over, as it were, with a fatty matter, which also is foreign to their nature, and may be separated from them without decomposing them in the least. The crystals of Tartar are but seldom perfectly depurated in Chymical Laboratories; because the operation doth not usually succeed well on small quantities: but there are manufactories which do it by the great, and supply the Chymists, as well as the several tradesmen, with very fine and very pure Crystals of Tartar. These manufactories are chiefly set up in the neighbourhood of Montpelier. Mr. Fifes, a celebrated Professor of Medicine, hath in the Memoirs of the Academy for 1725 described the operation as performed in one of these works. He tells us, that having separated the earthy part from the Crystals of Tartar, by boiling and filtering, they dissolve them again, and boil them in large caldrons, mixed with a white saponaceous earth, which cleanses and whitens them to perfection. The saponaceous earth is found near the works; but it is not the only one that may be employed for this purpose; since, as Mr. Fifes observed, they have successively made use of several different earths in that very work, and that the earth they now use hath not been long employed. There is reason to think that most saponaceous earths might answer the purpose of refining Crystal of Tartar: but one necessary condition is, that they be altogether indissoluble by Crystal of Tartar, which being acid dissolves many sorts of earth; for, if they have not this quality, they will form a Neutral Salt with the saline part of the Tartar, the nature of which they will entirely change, and convert it into soluble Tartar, as will appear by the experiments that follow. CHAP. IV. CRYSTAL _of_ TARTAR _combined with several_ SUBSTANCES. PROCESS I. _Crystal of Tartar combined with Absorbent Earths. Soluble Tartars._ Boil an Absorbent Earth, such as Chalk, in a pan with water; and, when you perceive the Earth thoroughly divided, and equally distributed through the water, throw into a pan, from time to time, some pulverized Crystal of Tartar, which will excite a considerable effervescence. Continue those projections, till you observe no effervescence excited thereby. All the Absorbent Earth, which obscured the transparency of the water, and gave it an opaque white colour, will gradually disappear as the Crystal of Tartar combines with it; and when the combination is perfected, the liquor will be clear and limpid. Then filter it, and there will be left on the filter but a very small quantity of earth. Evaporate all the filtered liquor with a gentle heat; and then set it in a cool place to shoot. Crystals will form therein, having the figure of flat quadrangular prisms, with almost always one, sometimes two, of the angles of the prism shaved down, as it were; and then the surfaces at each end are oblique, answering to those depressed angles. These crystals are a Neutral Salt, which readily dissolves in water; a true _Soluble Tartar_. _OBSERVATIONS._ Crystal of Tartar is a saline substance of a singular nature. Though it crystallizes like a Neutral Salt, yet it is not one: it hath only the form of one; its principal properties being those of an Acid. Nevertheless it is not a pure Acid; for it is united with a certain quantity of Oil and of earth, which give it the property of crystallizing, and it is scarce dissolvable in water. It is a middle substance between an Acid and a Neutral Salt. It is an Acid half-neutralized; on which account it is capable of acting like an Acid on all substances soluble by Acids, and so of being converted into a perfectly Neutral Salt by combining with them to the point of saturation. In the experiments made to neutralize Crystal of Tartar, Fixed Alkaline Salts alone were formerly used. Messrs. Duhamel and Grosse were the first who discovered that Absorbent Earths might be substituted for Alkalis, and would produce nearly the same effects on Crystal of Tartar. The experiments made by these two Academicians in conjunction are circumstantially related in two curious Memoirs on this subject, given in by them jointly, and printed with those of the Academy for 1732 and 1733. From these Memoirs we took the process here given, and shall also borrow from thence most of the remarks we are now going to make. Stone-lime holds, as it were, the middle place between mere Absorbent Earths and Fixed Alkalis. Now, seeing Crystal of Tartar may be converted into a Neutral Salt by either of these two substances, it follows, that lime ought to produce the same effect upon it. Accordingly Messrs. Duhamel and Grosse found it to be so upon trial: having formed, with _Lac calcis_ and Crystal of Tartar, a Neutral Salt perfectly like that which results from the union of that saline matter with Chalk. _Cremor calcis_, or that salino-terrene pellicle which forms on lime-water, produced the same effect: but, what is most singular is, that lime-water itself, though it be clear and limpid, and consequently doth not seem to contain any earthy particles, produced nevertheless a great effervescence with Crystal of Tartar, and neutralized it as perfectly as _Cremor calcis_, or water ever so much impregnated with Chalk. This arises from hence, that a great quantity of the salino-terrene matter, which forms the _Cremor calcis_ is dissolved in the lime-water. Though lime-water neutralizes Crystal of Tartar as perfectly as Chalk does, and though the Crystals of soluble Tartar, or neutralized Tartar, thereby produced, be like those which have Chalk for their basis, yet Messrs. Duhamel and Grosse observed some differences, worthy of notice, between the phenomena accompanying the production of these two Neutral Salts, which resemble each other so much that they seem but one and the same species of Salt. The principal difference consists in this, that the water containing the Tartar neutralized by Chalk is very limpid, and leaves but a very small quantity of earth on the filter; whereas the lime-water, with which Tartar hath been neutralized, leaves on the filter a considerable quantity of earth. This must appear the more surprising, that the water replete with Chalk was, before its union with the Crystal of Tartar, turbid and opaque; whereas the Lime water was at first clear and limpid. Messrs. Duhamel and Grosse suspect this to arise from hence, that the effervescence excited, while the Crystal of Tartar dissolves the matter contained in lime-water, is greater than that which is produced by its union with Chalk suspended in water. "If we consider," say they, "that in a great effervescence a considerable quantity of the acid Spirit is evaporated, we shall easily perceive, that, the more of that Spirit escapes, the more of the earth of the Tartar will be precipitated. Now, as the effervescence with lime-water is more considerable, and as there is less alkaline earth to check, as it were, and restrain the Acid, than in the experiment with Chalk, a greater quantity of the acid Spirit may escape; which being entirely lost will cause more earth to precipitate in this case than in the other, where the Acid is all at once attracted by a great deal of alkaline earth: and accordingly this was the reason that our Tartar dissolved by Chalk deposited, in crystallizing, a grey earth, which was scarce perceivable in the experiment made with Lime-water. "Yet perhaps," say they, "an Acid, which we suspect to be contained in lime, may have partly occasioned the precipitation of this earth." The existence of this Acid, which these gentlemen at that time only suspected, hath been since demonstrated by several experiments, and particularly by those which Mr. Malouin hath published. This Acid is the Vitriolic, which, in combination with some of the earth of the lime, forms a sort of Selenitic Salt; which adds greatly to the probability of Messrs. Duhamel and Grosse's last conjecture. I shall now explain how I conceive the Vitriolic Acid in lime may occasion the copious precipitate which falls in lime-water, when Crystal of Tartar is neutralized by it. The quantity of Vitriolic Acid contained in lime is very inconsiderable; so that to convert it into a Neutral Salt requires its intimate union with a very small quantity of the earthy and absorbent parts. Hence it comes to pass, that, when water is poured upon quick-lime, in order to make the Lime-water, it in some sort divides the lime into two parts. All the particles of Absorbent Earth, which had not contracted an union with the Acid, are at first barely suspended in the liquor, the transparency of which they destroy, giving it an opaque white colour; and this is what makes the _Lac calcis_: but they soon separate from it, and fall to the bottom, in the form of a precipitate; because they are not soluble in water. By this precipitation the liquor becomes limpid, and remains impregnated only with such of the earthy parts as are united with the Vitriolic Acid, in the form of a kind of Neutral Salt, and have by that union acquired solubility. But the Vitriolic Acid finding many more Absorbent parts in the lime than were necessary to neutralize it, in a manner over-dosed itself with earthy parts, and thereby exceeded the bounds of a perfect Neutrality. On the other hand, it hath been shewn, that Crystal of Tartar is an imperfect Neutral Salt. Now these two Salts, which are neither of them perfectly Neutral, differ from a perfectly Neutral Salt by properties directly opposite to each other; seeing the Selenitic matter in Lime exceeds in its absorbent or alkaline quality, and Crystal of Tartar exceeds, on the contrary, in acidity. What must be the consequence, therefore, of mixing these two saline matters together? The same as when an Acid is mixed with a Fixed Alkali; that is, the Salt which exceeds in acidity will combine with the super-abundant alkaline earth of the Selenitic Salt; so that these two saline matters will both become perfectly Neutral Salts. Yet these two Neutral Salts have not the same degree of solubility in water. The neutralized Crystal of Tartar dissolves very readily in water, and is for that reason called Soluble Tartar: the Selenitic Salt, on the contrary, is hardly dissolvable in it at all. Now it is a rule that, when two Salts of this nature meet together, the most soluble always remains united with the water, exclusive of the other, which is forced to precipitate. This I imagine to be what happens in the present case; and the precipitate which we see fall, in the lime-water employed to neutralize Crystal of Tartar, seems to me to be no other than the Selenitic Salt of the Lime; which, being less soluble than the neutralized Tartar, gives place to it, and separates from the liquor. Indeed we cannot, in my opinion, account for the precipitate under consideration, any other way, than by supposing it to be a portion either of the earth of the Crystal of Tartar, or a portion of the Lime. Now, either of these earths is dissolvable by Acids; whereas the precipitate in question, according to the observations of Messrs. Duhamel and Grosse, is not so: and this ought to be the case, if the precipitate be nothing but the selenitic Salt of the Lime, which being a Neutralized Salt, partly constituted by the most powerful of all the Acids, must be unalterable by any Acid whatever. Messrs. Duhamel and Grosse made a great many experiments on the combinations of Crystal of Tartar with different sorts of earths. The result of the whole is, that there are some earths which this Acid dissolves, and which contract such an union with Crystal of Tartar, that they not only change its external character, that is, its tendency to crystallize, and its indissolubleness in cold water, but also entirely alter its taste and other qualities. In a word, those earths produce on this Salt all the effects of alkaline Salts. These earths are such as are called Absorbent Earths; stone-lime, animal-lime, cretaceous earths, a portion of calcined gypsum, and of potash; in short, all such as distilled vinegar is capable of dissolving: this is the mark by which those earths, which are qualified to neutralize Crystal of Tartar, and to render it soluble, may be distinguished. Messrs. Duhamel and Grosse found also upon trial, that there are other earths, on the contrary, which are, in a manner, inaccessible to the Acid of Crystal of Tartar; that they take up, indeed, the grossest and redundant Oil of the Tartar, but without affecting its saline part at all: and if these earths are ever observed to form any union with the Crystals of Tartar, as happens in the refineries near Montpelier, that union is only superficial, not intimate; and therefore it alters none of the characters of the Salt. Among these earths are the clayey, bolar, sandy earths, and others of that kind. Hence Messrs. Duhamel and Grosse conclude, that these are the earths which ought to be employed in the purification and whitening of Crystal of Tartar. Vinegar is here also the test by which it may be known whether an earth intended for this purpose be fit for it: for you may be sure that it will form no union with Crystal of Tartar, if the Acid of Vinegar be incapable of dissolving it. PROCESS II. _Crystal of Tartar combined with Fixed Alkalis. The Vegetable Salt. Saignette's Salt. The Decomposition of Soluble Tartars._ In eight parts of water dissolve one part of a very pure alkaline Salt, perfectly freed from the phlogiston by calcination. Heat this lixivium in a stone pan set on a sand-bath, and from time to time throw into it a little powdered Cream or Crystal of Tartar. Each projection will excite a great effervescence, attended with many bubbles, which will rise to a considerable height one over the other. Stir the liquor when the effervescence ceases, and you will see it begin again. When no effervescence appears upon stirring the liquor, add a little more Cream of Tartar, and the same phenomena will be renewed. Go on thus till you have obtained the point of perfect saturation. Then filter your liquor. If the Alkali you made use of was the Salt of Soda, evaporate your liquor quickly to a pellicle, and there will shoot in it crystals of nine sides, resembling a coffin; the bottom part thereof being concave, and streaked with a great many parallel lines; and this is _Saignette's Salt_. If you have employed any other Alkali but Soda, or the basis of Sea-salt, evaporate your liquor slowly to the consistence of a syrup: let it stand quiet, and there will form in it crystals having the figure of slatted parallellopipeds; and this is the _Vegetable Salt_, or _Tartarized Tartar_. _OBSERVATIONS._ Seeing pure Absorbent Earths are capable of neutralizing Crystal of Tartar, and converting it into Soluble Tartar, there is still more reason to expect that Fixed Alkalis should possess the same property, as they have a much greater affinity with Acids: and accordingly Crystal of Tartar always forms, with every species of these salts, a Neutral Salt which is a Soluble Tartar. A Soluble Tartar, formed by the union of Crystal of Tartar with Tartar converted into an Alkali by fire, hath been long used in medicine as a gentle saponaceous purgative, known by the names of _Tartarized Tartar_, or the _Vegetable Salt_. But the Soluble Tartar, prepared by combining Crystal of Tartar with the Alkali of Soda, which, as we remarked before, is analogous to the basis of Sea-salt, and different from all other Alkalis, was not well known to Chymists till the year 1731, when M. Boulduc published the preparation in a Memoir printed in the Academy's collection for that year[14]. [14] It could not be any longer concealed; for M. Geoffroy having made some experiments on the same subject, without knowing any thing of what M. Boulduc had done, likewise discovered it. See the History of the Academy for 1731, p. 35. Not but that it was very much used before that time: for it had been for several years in high reputation, and prescribed instead of Tartarized Tartar, which became almost quite neglected. But M. Saignette, a physician of Rochelle, who was the first inventor and vender of this Salt, did not publish the preparation of it, which he kept as a secret: and this probably contributed not a little to the great esteem which this medicine had acquired; for men are naturally inclined to put a much greater value on secrets, than on what is universally known. He gave it the name of _Sal Polychrestum_; and the public called it also _Saignette's Salt_, and _Rochelle Salt_. Since the discoveries of M. Geoffroy and M. Boulduc were published, the method of preparing this Salt hath been no secret; it was described in Dispensatories, and every apothecary hath made it ever since. Saignette's Salt, as well as every other Soluble Tartar, melts when laid on live coals, boils up, emits smoke, and leaves a black charred matter behind. This resemblance of Saignette's Salt to Tartarized Tartar, joined to the smell of the vapour which exhaled in burning it, and is the same with that of Tartar, were the first notices that led M. Boulduc to suppose this Salt to be a soluble Tartar. On examining the alkaline coal produced by the calcination, and comparing it with that left by Tartarized Tartar, he perceived there was some difference between them. At last his friend, M. Grosse, having advised him, as he tells us in his Memoir, to combine Crystal of Tartar with the Salt of Soda, and to examine the new Salt that would result from their union, M. Boulduc immediately suspected that it must produce a species of Soluble Tartar, which might possibly prove to be the Salt in question. Nor was he mistaken in his conjecture: for with these two saline substances he actually composed a Salt perfectly like Saignette's. Under the head of Borax we remarked that it contains an Alkali like the basis of Sea-salt. This Alkali is not perfectly neutralized by the sedative Salt, which is also contained in Borax: for its alkaline properties are so perceptible as to have led some Chymists to think that Borax was only an Alkali of a particular kind. This induced M. le Fevre, a Physician at Uzes, and one of the Academy's correspondents, to combine Crystal of Tartar with Borax, and to examine the result. He communicated to the Academy his experiments on this subject; by which he found that the combination of these two saline matters forms a Soluble Tartar, but greatly different from Saignette's Salt; especially in that it doth not crystallize, but remains in the form of a gummy matter, and retains all the acidity natural to pure Cream or Crystal of Tartar: a circumstance which is very remarkable. Mr. Lemery had the curiosity to repeat M. le Fevre's experiment, and found that this singular Soluble Tartar had the properties ascribed to it by the inventor. The process he recommends for making the experiment with success is as follows: "Take four ounces of Crystal of Tartar finely pulverized, and two ounces of Borax carefully powdered, and put these two Salts into a flint-glass body. Pour on them two ounces of water, and set the cucurbit into a sand-bath. Warm it with a gentle fire, and then increase the heat so as to make the liquor boil for a quarter of an hour; which will produce a perfect dissolution of the Cream of Tartar and Borax. After the dissolution of these two Salts united together, the liquor will remain clear and limpid, though the boiling hath dissipated a good deal of it. If the liquor be still further evaporated, the remainder will have the consistence of Honey, or Turpentine: and, if the evaporation be carried still farther, with a gentle heat, the matter remaining will in colour resemble the gum of a plumb-tree, and yield to pressure as that does; and, if it be exposed to the air in a damp place, it will grow moist and run, almost like Salt of Tartar:" a new and singular property, which belongs neither to Borax nor to Crystal of Tartar, when they are not combined together. All Soluble Tartars are easily decompounded, by means of a certain degree of heat. They yield in the distillation the same principles as Tartar; and the Alkali that remains, when they are perfectly calcined, consists of that which the Tartar naturally affords, and of the alkaline matter with which it was converted into a Neutral Salt. These Neutral Salts, resulting from the union of Crystal of Tartar with any alkaline matter, are also decompounded by all the Acids, even by vinegar, which nevertheless is an Oily Vegetable Acid, and consequently of the same kind with Crystal of Tartar. The reason of this is that the Acid of Vinegar, though blunted by much phlegm and oil, must be considered as a free and pure Acid, when compared with Crystal of Tartar; which is still more embarrassed with heterogeneous matters, so as to be a semi-neutral Salt. When Soluble Tartar is decompounded by an Acid, the Crystal of Tartar, which helped to constitute the Neutral Salt, is then wholly recovered. This saline matter, being separated from that which rendered it soluble in water, ceases now to be so, and for that reason precipitates to the bottom of the liquor. The Neutral Salts, resulting from the decomposition of Soluble Tartar by an Acid, differ according to the Acid made use of. From Saignette's Salt decompounded by the Vitriolic Acid M. Boulduc obtained a true Glauber's Salt, and a precipitate of Crystal of Tartar: and this he justly adduces as a demonstrative proof, that Saignette's Salt is no other than Crystal of Tartar neutralized by a Fixed Alkali analogous to the basis of Sea-salt. Though all Soluble Tartars may be decompounded by Acids, as hath just been said, yet they do not all forsake their bases with equal facility. Messrs. Duhamel and Grosse found that, in this respect, they observe the following order, beginning with those which afford the readiest and most copious precipitate: viz. Soluble Tartar made 1. with Potash; 2. with Chalk; 3. with uncalcined Oyster-shells; 4. with Stone-Lime; 5. with calcined Oyster-shells; 6. with Salt of Tartar; 7. with Salt of Soda; 8. and lastly, Tartar made soluble with Borax is not precipitated by distilled vinegar. It is not easy to account for this difference between Soluble Tartars. If the Salt of Soda were more alkaline than Salt of Tartar, and Borax more alkaline than the Salt of Soda, it might be conjectured that the more alkaline the matters are with which Crystal of Tartar is neutralized, the closer is the union it contracts with them; since it is plain, from what hath been said on this subject, that though Soluble Tartars, which have for their basis Absorbent Earths only, not converted into Lime, are more easily decompounded than those which are rendered soluble by Limes; and these again more easily than those which have a Fixed Alkali for their basis. But, on the contrary, the Salt of Soda is less alkaline than Salt of Tartar, and Borax still less than the Salt of Soda. PROCESS III. _Crystal of Tartar combined with Iron. Chalybeated Tartar. Tincture of Steel with Tartar. Soluble Chalybeated Tartar._ Mix four ounces of Iron, in filings, with one pound of white Tartar, finely pulverized. Boil the mixture in about twelve times as much water as you took of Tartar. When the saline part of the Tartar is dissolved, filter the liquor boiling-hot through a flannel bag, and then set it in a cool place. In a very little time crystals of a russet colour will shoot therein. Decant the liquor from these crystals; evaporate it to a pellicle, and set it again to crystallize. Go on in this manner till it will shoot no more. Collect all the Salt you have thus obtained, and keep it under the name of _Chalybeated Tartar_. To make the Tincture of Steel with Tartar, mix together six ounces of clean Iron filings, and one pound of white Tartar in powder. Put this mixture into a large iron kettle, and pour thereon as much rain-water as will moisten it. Make a paste of this matter, and leave it thus in a mass for twenty-four hours. Then pour on it twelve pounds of rain-water, and boil the whole for twelve hours at least, stirring the mixture frequently, and adding from time to time some hot water, to supply the place of what evaporates. When you have thus boiled the liquor, let it stand quiet for some time, and then pour it off from the sediment at bottom. Filter, and evaporate to the consistence of a syrup; and you have the _Tincture of Mars with Tartar_. The Dispensatories generally order an ounce of rectified Spirit of Wine to be poured on this Tincture, in order to preserve it, and to keep it from growing mouldy, as it is very apt to do. _Soluble Chalybeated Tartar_ is prepared by mixing four ounces of Tartarized Tartar, with one pound of the Tincture of Mars with Tartar, and evaporating them together in an iron vessel to dryness; after which it is kept in a well stopped phial, to prevent its growing moist in the air. _OBSERVATIONS._ The three preparations of this process are medicines very well known and much used. There is even reason to think that those, who first thought of combining Tartar in this manner with Iron, had it in their view to prepare compositions useful in medicine, rather than merely to produce new combinations for the improvement of Chymistry. Indeed, were we to consider only the account here given of the manner in which these three compositions are made, we should be inclined to think Crystal of Tartar incapable of dissolving Iron so thoroughly and radically, that, from the union of these two substances, a Neutral Metallic Salt should arise, a Tartar neutralized and made soluble by Iron. For it is very certain that the first of these preparations, which is called Chalybeated Tartar, is nothing but the saline part of Tartar dissolved by boiling water, and then precipitated and crystallized along with particles of iron, that are reduced, at most, into a rust, or a _crocus_ only, but have contracted no union with the crystal of Tartar, which remains as Acid and as indissoluble after this preparation as before. Accordingly it is called only _Chalybeated Tartar_, and not _Soluble Chalybeated Tartar_: and, as this latter name hath been given only to the Tartarized Tincture of Mars compounded with Tartarized Tartar; that is, with Tartar rendered soluble by a Fixed Alkali, and not by Iron; there is reason to presume, that the Tincture of Mars alone was not thought worthy of being called a Soluble Chalybeated Tartar; but that the name, importing _Tartar rendered soluble by Mars_, belongs to that Tincture only when compounded with a true Soluble Tartar. It is nevertheless very certain, that the Tincture of Mars made with Tartar contains a true Soluble Chalybeated Tartar; that is, a Neutral Salt consisting of Crystal of Tartar united with Iron, and rendered soluble by that union. The long boiling, necessary to prepare this Tincture, gives the Acid of Tartar time to dissolve the Iron radically, and to unite very closely therewith: but this is not the case in the preparation of Chalybeated Tartar; to make which the Tartar is boiled in water only as long as is necessary for the dissolution of its saline parts; that is, about a quarter or half an hour; in which space the Acid of the Tartar can scarce begin to act on the surface of the Iron: for Acids have not so quick an effect on metals, as on Alkalis and Absorbent Earths. Metallic substances, being vastly more compact, are not near so soon dissolved by Acids, and especially by vegetable Acids, weakened with heterogeneous matters, as the Acid of Tartar is. I thought the dissolution of Iron by Tartar a point of sufficient importance to deserve a little more attention than hath commonly been given to it; and for that reason resolved to examine, and trace with care, the phenomena observable in this operation. As the crude Tartar, employed in making the Tartarized Tincture of Mars, is replete with many oily and earthy parts, which cannot but obstruct the dissolution of the Iron, and prevent our seeing clearly how that dissolution is carried on, I thought it better to make use of Cream, or Crystals, of Tartar, which, being pure and freed from all those heterogeneous parts, dissolve in boiling water without prejudicing its transparency. I therefore pulverized Cream of Tartar, and dissolved as much thereof in boiling water as it would take up. This solution I poured boiling hot into a matrass, at the bottom of which I laid some fine iron wire cut into small pieces. I set the matrass in a sand-bath; and having heated it so as to make the liquor boil, I observed that, the instant before it boiled, the liquor began to act very perceptibly upon the Iron, in the same manner as other Acids act upon metallic substances; that is, there appeared on the surfaces of the little bits of Iron small bubbles, which immediately rose to the surface of the liquor, and succeeded each other so fast, that they formed lines, or jets, seemingly continued from the surface of the Iron to the surface of the liquor, which, little by little, acquired a faint tinge of yellow. When the liquor was heated so as to boil, the dissolution still went on, but much more briskly, and the liquor acquired a deeper colour. After boiling about an hour, the liquor, which at first was very clear, became turbid, and of an opaque white; which made me think, that some of the Cream of Tartar, dissolved therein, began to precipitate. I let the whole boil some time longer, and the white precipitate becoming more considerable, I resolved to filter the liquor, which passed through clear, and tinged with a greenish yellow. There remained on the filter a whitish sediment, which I found to be true Cream of Tartar. The filtered liquor tasted much like a solution of Copperas. I evaporated it in a glass bason, set in a sand-heat, but no pellicle appeared; which made me conclude that it would produce no crystals: accordingly, having taken some of it out of the bason, when it was considerably reduced by evaporation, and set it in a cool place, no crystal shot in it. The rest of the liquor I evaporated to dryness: it left a blackish brown residuum, which had the same taste with the liquor before evaporation, but much stronger. This residuum melts very readily in the mouth, without leaving on the tongue the least gritty particle. Being exposed very dry to the air, it grows moist, and runs into a liquor in a very little time. It dissolves easily and readily in a very small quantity of cold water. This solution being mixed with Fixed Alkalis, in various proportions, doth not grow turbid, nor drops any precipitate; but with a decoction of galls it makes ink. Acids give it a much clearer colour, and at first produce no precipitation; but, in a quarter of an hour, there appears a precipitate much of the same colour with the solution. This precipitate is no other than Cream of Tartar, tinged of a russet colour by the liquor, which grows turbid, and a little whitish, when the precipitate begins to form. These experiments, and the circumstances attending them, will not allow us to doubt the truth of what I advanced concerning the Tincture of Mars made with Tartar, _viz._ that it is nothing but Crystal of Tartar by which Iron is dissolved, and which is rendered soluble by that metal. We see at the very first that Crystal of Tartar acts upon Iron, just as other Acids do. Indeed this metallic solution is not precipitated by Alkalis: but we know that Alkalis possess the property of dissolving Iron, especially when the metal is previously divided by an Acid; so that there is reason to think this may be the case, when an Alkali is mixed with our Soluble Chalybeated Tartar. As this Soluble Tartar is a saponaceous and oily Salt, it is also possible that it may be dissolved entirely by the Alkali, without suffering any decomposition; especially as Alkalis decompound Neutral Metallic Salts, by means only of the stronger affinity which they have with the Acids, than with the Metals, of which those Salts are compounded. Now, as our Soluble Chalybeated Tartar is compounded of that Metal which the Alkali dissolves with the greatest ease, and of that Acid with which it hath the least affinity of any, it is very possible that it may not have a greater affinity with the Acid than with the metallic basis of this Salt, and so be uncapable of decompounding it. However, as this Soluble Chalybeated Tartar makes a black liquor with a decoction of Galls, and as nothing but Iron dissolved by an Acid hath that property, it may be safely concluded, that this Salt really consists of Iron dissolved by the Acid of Tartar. The precipitate which a solution of this Salt lets fall, on the addition of an Acid, is another proof that it consists of these two principles: for this precipitate can be no other than the Tartarous Acid, which, being the weakest of all Acids, is separated from the Iron by the Acid added to the solution; which Acid unites with the Martial basis, and forms another Neutral Metallic Salt, according to the Acid employed. Lastly, the great solubility of the desiccated residuum of the Tincture of Mars, made with Tartar, is a very strong and decisive proof, that this residuum is no other than Iron dissolved by the Acid of Tartar: for what else can it be? Nothing but Iron and Crystal of Tartar is made use of in the operation; and neither of these two substances singly is so soluble as this new body. We know, moreover, that Crystal of Tartar, which itself is indissoluble, forms a Soluble Tartar when combined with pure Absorbent Earths, though these matters be still more indissoluble than it, or rather, are not soluble at all. Hence it is very natural to conclude, that our residuum is a Tartar rendered soluble by Iron. This Chalybeated Tartar is even more soluble than any other sort of Soluble Tartar; for it very readily grows moist in the air, and runs wholly into a liquid; on which account it is not susceptible of crystallization. I return to one of the circumstances attending my experiment, which it is proper I should account for; though I have hitherto only mentioned it, without more particular notice, that I might not break the connection between facts, and the consequences resulting from them. The circumstance I mean is the precipitation of the Cream of Tartar dissolved in the liquor, which, I said, happens when the saline solution hath boiled upon the Iron about an hour. This precipitation of the Cream of Tartar may be partly occasioned by the evaporation of the water in which it is dissolved: for the water having taken up, as was said, as much Cream of Tartar as it was capable of dissolving, when the quantity of water comes to be lessened, a proportional quantity of Cream of Tartar must precipitate. But some other cause must also contribute to produce this precipitation: for, as I boiled my liquor in a matrass, the evaporation of the liquor could not be considerable, and yet the precipitate was very copious. Moreover, I replenished the matrass with much more water than was necessary to replace what had evaporated; yet I could not re-dissolve the precipitated Cream of Tartar, nor even sensibly lessen its quantity. The true cause of this effect I take to be as follows. When the solution of Cream of Tartar hath boiled for some time upon the Iron, and dissolved a certain quantity thereof, a proportional quantity of Soluble Chalybeated Tartar is formed. Now as this Salt is much more soluble in water than Cream of Tartar, and as water always takes up the more soluble Salts, preferably to the less soluble, it is not surprising that Cream of Tartar, being one of those saline substances which dissolve with the greatest difficulty, should on this occasion separate from the liquor, and precipitate; yielding its place to a Salt which hath a much greater affinity with water. Hence it appears, that to re-dissolve the Cream of Tartar, and render it capable of continuing to dissolve the iron as efficaciously as before, it is not sufficient that fresh water be added; but the solution of the Soluble Chalybeated Tartar already formed must be entirely decanted, and fresh water poured on the residue; and then this water, not being impregnated with any Soluble Chalybeated Tartar, will be capable of re-dissolving the Cream of Tartar, and every thing will go on as at the beginning of the operation, till the Cream of Tartar come to precipitate again, for the same reason as before, and make a repetition of the same management necessary. The liquor is far from being saturated with Soluble Chalybeated Tartar, when the precipitation of the Cream of Tartar renders it necessary to decant it: so that the water must be often renewed, if you carry the operation to the utmost; and then all these solutions must be added together, and evaporated, either to dryness, if you desire to have the salt in a dry form, or to any other degree you think proper. This method I followed at first: but as it is exceeding long and tedious, though perhaps the best; and as I wanted to have a moderate quantity of Soluble Chalybeated Tartar, with less trouble, and in less time, if possible, I resolved to try whether or no Cream of Tartar, though separated from the liquor and undissolved, were still capable of acting on the iron with such efficacy as to dissolve it. I therefore continued to boil the tartarous solution on the filings of Iron, notwithstanding the precipitation of the Cream of Tartar, taking care only to add fresh water from time to time, as directed in the process for the Tartarized Tincture of Mars, to replace what evaporated; and I observed that, in fact, the Cream of Tartar, though not perfectly dissolved, but only divided and agitated by the motion of boiling, still continued to act upon the Iron; so that the liquor, after boiling seven or eight hours, was so impregnated as to yield by evaporation a reasonable quantity, in bulk, of Salt in a dry form. PROCESS IV. _Crystal of Tartar combined with the reguline Part of Antimony. Stibiated or Emetic Tartar._ Pulverize and mix together equal parts of the Glass and of the Liver of Antimony. Put this mixture, with the same quantity of pulverized Cream of Tartar, into a vessel capable of containing as much water as will dissolve the Cream of Tartar. Boil the whole for twelve hours, from time to time adding warm water, to replace what is dissipated by evaporation. Having thus boiled your liquor, filter it while boiling hot; evaporate to dryness; and you will have a saline matter which is _Emetic Tartar_. _OBSERVATIONS._ The Glass and Liver of Antimony are no other, as was said in its place, than the metallic earth of Antimony separated from the redundant Sulphur of that mineral; but still retaining such a quantity of phlogiston as to possess, excepting its metalline colour, nearly the same properties with Regulus of Antimony, and especially its emetic quality, and its solubility in Acids. Indeed these two preparations seem to have more of an emetic quality than the Regulus itself, and therefore are employed preferably to all others in the preparation of Emetic Tartar. It is not yet ascertained in which of the principles of Antimony its emetic virtue resides. We are sure, however, that it cannot be ascribed to its earthy part: for the calx of Antimony, when entirely deprived of all phlogiston, is not emetic, nor even purgative; as is evident from the effects of Diaphoretic Antimony and the Pearly Matter. Some authors think Antimony contains an arsenical principle, to which they impute its emetic quality; nor is their opinion altogether void of probability. For this arsenical part seems to be indicated by several of the properties of Antimony, and particularly by its affinities with other metallic substances, in which it very nearly resembles Arsenic. But this doth not amount to a positive proof: for we can draw nothing but probable conjectures, at most, from such analogies. Other Chymists think the emetic virtue of Antimony depends on the union of its metallic earth with its phlogiston. This opinion seems to me much more probable than the other: for by only recombining a phlogiston with the earth of Antimony, deprived by calcination of all its emetic virtue, that virtue is perfectly restored, and the Regulus thus revivified is no less emetic than that which never underwent calcination. However this be, it is certain that Cream of Tartar acquires an emetic quality, not by barely uniting with one of the principles of Antimony, but by dissolving entirely the reguline, or semi-reguline, part thereof; and that its emetic quality is so much the stronger, the more of that substance it hath dissolved. This is the result of several experiments made on the subject by Mr. Geoffroy. That gentleman collected several parcels of Emetic Tartar, having different degrees of strength. "I employed," says he[15], "an ounce of each of those Emetic Tartars: I rubbed them separately with an equal weight, or something more, of a black flux, made of two parts of red Tartar, and one part of Nitre calcined together. These mixtures I put into different crucibles, formed like inverted cones: I kept them in a melting heat till the Salts in fusion sunk, and appeared like a smooth oil at the bottom of each crucible. I then let the fire go out, broke the crucibles when cold, and found the resuscitated Regulus in a mass at bottom. [15] Memoirs of the Academy for 1734, p. 421. "Out of one ounce of the weakest Emetic Tartars I obtained from thirty grains to one dram eighteen grains of Regulus. From one ounce of such as were of a middling strength I got one dram and an half; and the most violent yielded me two drams and ten grains. "The power, therefore, of the strongest Emetic Tartars," continues he, "depends on the quantity of Regulus of Antimony dissolved by the Cream of Tartar, and the nearer the preparations of Antimony, on which the solution of Cream of Tartar is boiled, are to the form of a Regulus or a Glass, the more violent is the Emetic Tartar; because the Vegetable Acid of the Tartar acts then more immediately upon the Emetic part of the Antimony, and dissolves more of it." Mr. Geoffroy found upon trial, that Cream of Tartar boiled for a due time on Crude Antimony, doth indeed dissolve a little of the reguline part thereof; but that the quantity of Regulus dissolved thereby is so very small, that the Emetic Tartar produced is extremely weak. The gross Sulphur, in this case, hinders the Cream of Tartar from acting on the reguline part with so much efficacy, as when the Antimony is properly prepared by freeing it entirely from its redundant Sulphur. Nothing can be added to what Mr. Geoffroy hath said on this subject. His experiments are decisive, and set the truth he intended to prove in the clearest light. Mr. Hoffman affirms, that Emetic Tartar loses part of its virtue by being boiled too long. A very able Chymist goes so far as to say, that Tartar ought not to boil above six or seven minutes with prepared Antimony; because longer boiling destroys part of its Emetic quality. Can this arise from hence, that Cream of Tartar, after dissolving a certain quantity of the reguline substance, separates from it afterwards? Or is the Cream of Tartar itself decomposed by too long boiling? This deserves to be particularly inquired into, as well as the nature of the Metallic Salt, which results from the union of the Acid of Tartar with the Regulus of Antimony. Crystal of Tartar acts also on several other metallic substances, and particularly on Lead; with which it forms a Salt, resembling Tartarized Tartar in the figure of its crystals. CHAP. V. _Of the_ PRODUCT _of_ ACETOUS FERMENTATION. PROCESS I. _Substances susceptible of the Acetous Fermentation turned into Vinegar._ The Wine, the Cyder, or the Malt-liquor, which you intend to convert into Vinegar, being first thoroughly mixed with its lees, and with the Tartar it may have deposited, put your liquor into a vat used before, either for making or for holding Vinegar. This vessel must not be quite full, and the external air must have access to the liquor contained in it. Set it where the air may have a degree of warmth answering nearly to the twentieth degree above 0 in Mr. de Réaumur's Thermometer. Stir the liquor from time to time. There will arise in it a new fermentative motion, accompanied with heat: its vinous odour will gradually change, and turn to a sour smell, which will become stronger and stronger, till the fermentation be finished, and cease of itself. Then stop your vessel close; the liquor it contains will be found converted into Vinegar. _OBSERVATIONS._ All substances that have undergone the spirituous fermentation are capable of being changed into an Acid, by passing through this second fermentation, or this second stage of fermentation. Spirituous liquors, such as Wine, Cyder, Beer, being exposed to a hot air, grow sour in a very short time. Nay, these liquors, though kept with all possible care, in very close vessels, and in a cool place, degenerate at last, change their natures, and insensibly turn sour. Thus the product of spirituous fermentation naturally and spontaneously degenerates to an Acid. For this reason it is of great importance, in making Wine, or any other vinous liquor, to stop the fermentation entirely, if you desire the Wine should contain as much Spirit as possible. It is even more advantageous to check the fermentation a little before it comes to the height, than afterwards: because the fermentation, though slackened, and in appearance totally ceased, still continues in the vessels; but in a manner so much the less perceptible, as it proceeds more slowly. Thus those liquors, in which the fermentation is not quite finished, but checked, continue for some time to gain more Spirit: whereas, on the contrary, they degenerate and gradually turn sour, if you let the spirituous fermentation go on till it be entirely finished. The production of the second fermentation, which we are now to consider, is an Acid of so much the greater strength, the stronger and more generous the spirituous liquor, in which it is excited, originally was. The strength of this Acid, commonly called _Vinegar_, depends likewise, in a great measure, on the methods used in fermenting the vinous liquor, in order to convert it into Vinegar: for if it be fermented in broad, flat vessels, and left to grow sour of itself, the spirituous part will be dissipated, and the liquor, though sour indeed, will be vapid and effete. The Vinegar-makers, to increase the strength of their Vinegar, use certain methods of which they make a mystery, keeping them very secret. However, Mr. Boerhaave gives us, from some Authors, the following description of a process for making Vinegar. "Take two large oaken Vats or Hogsheads, and in each of these place a wooden grate or hurdle, at the distance of a foot from the bottom. Set the vessel upright, and on the grates place a moderately close layer of green twigs, or fresh cuttings of the vine. Then fill up the vessel with the foot-stalks of grapes, commonly called the _Rape_, to within a foot of the top of the vessel, which must be left quite open. "Having thus prepared the two vessels, pour into them the Wine to be converted into Vinegar, so as to fill one of them quite up, and the other but half full. Leave them thus for twenty-four hours, and then fill up the half-filled vessel, with liquor from that which is quite full, and which will now in its turn be left only half-full. Four and twenty hours afterwards repeat the same operation, and thus go on, keeping the vessels alternately full and half-full, during every twenty-four hours, till the Vinegar be made. On the second or third day there will arise, in the half-filled vessel, a fermentative motion, accompanied with a sensible heat, which will gradually increase from day to day. On the contrary, the fermenting motion is almost imperceptible in the full vessel; and as the two vessels are alternately full and half-full, the fermentation is by that means, in some measure, interrupted, and is only renewed every other day, in each vessel. "When this motion appears to be entirely ceased, even in the half-filled vessel, it is a sign that the fermentation is finished; and therefore the vinegar is then to be put into common casks, close stopped, and kept in a cool place. "A greater or less degree of warmth accelerates or checks this, as well as the spirituous fermentation. In France it is finished in about fifteen days, during the summer; but if the heat of the air be very great, and exceed the twenty-fifth degree of Mr. de Réaumur's Thermometer, the half-filled vessel must be filled up every twelve hours; because, if the fermentation be not so checked in that time, it will become so violent, and the liquor will be so heated, that many of the spirituous parts, on which the strength of the Vinegar depends, will be dissipated; so that nothing will remain, after the fermentation, but a vapid wash, sour indeed, but effete. The better to prevent the dissipation of the spirituous parts, it is a proper and usual precaution to close the mouth of the half-filled vessel, in which the liquor ferments, with a cover made also of oak-wood. As to the full vessel, it is always left open, that the air may act freely on the liquor it contains: for it is not liable to the same inconveniencies, because it ferments but very slowly." The vine-cuttings and grape-stalks, which the Vinegar-makers put into their vessels, serve to increase the strength of the liquor. These matters contain a very manifest and perceptible Acid. They also serve as a ferment; that is, they dispose the Wine to become eager more expeditiously, and more vigorously. They are the better, and the more efficacious, for having been once used, because they are thereby thoroughly drenched with the fermented Acid: and therefore the Vinegar-makers lay them by, for preparing other Vinegar, after washing them nimbly in running water, in order to free them from a viscid oily matter, which settles on them during the fermentation. This matter must by all means be removed; because it is disposed to grow mouldy and rot; so that it cannot but be prejudicial to any liquor into which you put it. As the Acetous fermentation differs from the Spirituous in its production, so it doth in many circumstances attending it. 1. Motion and agitation are not prejudicial to the Acetous fermentation, as they are to the Spirituous; on the contrary, moderate stirring, provided it be not continual, is of service to it. 2. This fermentation is accompanied with remarkable heat; whereas, the warmth of the spirituous fermentation is scarce sensible. 3. I do not believe there ever was an instance of the vapour that rises from a liquor in Acetous fermentation proving noxious, and producing either disorders or sudden death, as the vapour of fermenting Wine doth. 4. Vinegar deposites a viscid oily matter, as hath just been observed, very different from the Lees and Tartar of Wine. Vinegar never deposites any Tartar; even though new Wine, that hath not yet deposited its Tartar, should be used in making it. The following processes will give us occasion to treat of the nature of Vinegar, and the principles of which it consists. PROCESS II. _To concentrate Vinegar by Frost._ Expose to the air, in frosty weather, the Vinegar you desire to concentrate. Icicles will form in it; but the whole liquor will not freeze. Take out those icicles: and if you desire a further concentration of your Vinegar by this method, the liquor which did not freeze the first time must be exposed to a stronger frost. More icicles will form therein, which must likewise be separated, and kept by themselves. The liquor which doth not freeze this second time will be a very strong concentrated Vinegar. _OBSERVATIONS._ Liquors, replete with an Acid, freeze with much more difficulty than pure water. Thus, if a very aqueous acid liquor be exposed to frost, some of the water in the liquor will presently freeze; while the rest, being rendered more acid by the separation of the frozen phlegm, will remain fluid, and resist the degree of cold which freezes water. Now Vinegar, being an acid liquor containing much water, may therefore be highly concentrated by freezing its phlegm in this manner; and the more icicles you get from it, the stronger and more active will the remaining Vinegar be. Mr. Stahl was the first, I believe, who thus made use of congelation, for procuring a very strong Acid of Vinegar. Mr. Geoffroy hath since taken the same method. A curious and circumstantial account of his experiments, on this subject, are printed in the Memoirs of the Academy for 1739. As it was excessive cold in the winter of that year, Mr. Geoffroy took the opportunity of exposing to the frost several Vinegars of different strengths; and he determined the degree of Acidity in each, both before and after their concentration, in order to compare them, and discover how much stronger each Vinegar was rendered by the freezing of the aqueous part. To determine the strength of the Vinegars, he made use of the method pointed out by Mr. Homberg and Mr. Stahl. This method consists in combining to the exact point of saturation, a certain quantity of Vinegar with well-dried Salt of Tartar. The more Salt of Tartar is required, to absorb and perfectly neutralize the Vinegar, the stronger it must be reckoned; because the quantity of Alkali necessary to constitute a Neutral Salt is always proportioned to the quantity of Acid in that Salt. One of the Vinegars employed in Mr. Geoffroy's experiments, two drams of which were entirely absorbed by six grains of Salt of Tartar, having been concentrated by once freezing, and thereby reduced from eighteen quarts to six, he found it so increased in strength, that two drams thereof required twenty-four grains of Salt of Tartar to absorb them. The first icicles that separate from Vinegar, in this process, are perfectly clear, and as insipid as water. As the Vinegar becomes more concentrated, the plates of ice becoming thinner, more spongy, and flaky like snow, retain between them some portion of the Acid; and it is proper to begin to save them as soon as they appear to be sensibly acid. Mr. Geoffroy carried the concentration of Vinegar as far as the cold of that winter in 1739 would allow him; and eight quarts of Vinegar, already concentrated by frost in the preceding years, being reduced to two quarts and a half by the frost of the 19th of January, the coldest day of that year, was found to be so strong, that two drams thereof required forty-eight grains of Salt of Tartar to absorb them. The icicles of this Vinegar, being thawed, retain so much strength as to require thirteen grains of the Salt of Tartar to absorb them. Vinegar suffers no decomposition by the congelation of its phlegm, and the consequent concentration of its Acid. What is left still contains all the principles of which Vinegar consists. Its principles are only brought nearer together, and into a smaller compass: and for this reason it grows the thicker the more it is concentrated. When therefore you desire to concentrate the Acid of Vinegar, and at the same time to purify it, that is, to free it from some of its oil and earth, you must have recourse to distillation. Wine, as well as Vinegar, may be concentrated by freezing. Mr. Stahl exposed several sorts of Wine to the frost, and by that means separated from them about two thirds, or three quarters, of almost pure phlegm. The remainders of the Wines so concentrated were of a somewhat thickish consistence. They were very strong, and kept for several years without altering, in places where the free access of the air, alternately cold and hot according to the seasons, would have soured, or spoiled, any other kind of Wine in the space of a few weeks. Wine thus concentrated by freezing is not thereby decomposed, any more than Vinegar: it is only dephlegmated. By the addition of as much water as was separated from it, you may restore it to its former condition; in which respect it differs greatly from the residue of Wine whose spirituous part, with a proportion of its phlegm, hath been drawn off by distillation: for though you mix that residue again with the principles you separated from it, you can never make Wine of it again; the spirituous part being no longer in a capacity to combine with the other principles of the Wine, in the same manner as before that separation. And this shews that heat, besides separating the most volatile parts, produces moreover a considerable change in the disposition of those which did not rise in the first distillation. Since the above experiments were made by Messrs. Stahl and Geoffroy, concentration by freezing is pretty frequently practised in laboratories; but on Vinegar only, seldom on Wine: because, when Vinegar is thus concentrated, a much stronger Acid is more easily and more expeditiously obtained from it, as will be shewn in the following process; whereas the distillation, as well as the quality, of Spirit of Wine is much the same, whether the Wine it is obtained from be concentrated or no. The reason of this difference is, that Spirit of Wine, being very light, rises in distillation before the phlegm; whereas the Acid of Vinegar, being much more ponderous, rises only at the same time with the aqueous part, or even after it. PROCESS III. _Vinegar analyzed by Distillation._ Into a glass or stone cucurbit put the Vinegar to be distilled; fit to it a glass head; place your alembic in the sand-bath of a distilling furnace, and lute on a receiver. Apply a very gentle heat at first. A clear, limpid, light liquor will rise, and fall in distinct drops, like water, from the nose of the alembic. Continue distilling this first liquor, till the vinegar contained in the cucurbit be diminished about a fourth part. Then shift your receiver, and increase the fire a little. A clear liquor will still come over, but heavier and more acid than the former. Distil in this manner, till you have drawn off, into your second receiver, two-thirds of the liquor that was left in the cucurbit. A thick matter will now remain at the bottom of the still: put it into a retort; lute on a receiver; set your retort in a reverberating furnace, and distil with degrees of fire. There will come over a limpid liquor, very acid and sharp, yet ponderous, and requiring a great degree of fire to raise it; on which account it makes the receiver very hot. It hath a strong empyreumatic smell. When the distillation begins to slacken, increase your fire. There will rise an Oil of a fetid, quick smell. At last, when nothing more will rise with the strongest fire, break the retort, and in it you will find a black charred matter: burn it, and from the ashes lixiviated with water you will obtain a Fixed Alkali. _OBSERVATIONS._ None of the liquors that come over in this operation, before the last fetid Oil, seem to have any other properties than those of an oily Acid; none of them is inflammable, none of them resembles Spirit of Wine; but all of them being thrown into the fire extinguish it. Mr. Boerhaave however takes notice, that a Chymist, named Vigani, affirms the first portion of the liquor which rises in the distillation of Vinegar to be inflammable, and no other than Spirit of Wine. Mr. Boerhaave suspected that this might happen from Vigani's having distilled Vinegar too newly made; and found upon trial that Vinegar, being distilled soon after it was made, yielded at first in distillation a certain quantity of an Ardent Spirit; but that the same thing did not happen in the distillation of old Vinegar. And this proves that fermentation hath the same effect on Vinegar as on Wine; that is, that though the fermentation which produces these liquors seems to be over in a certain time, when the violent intestine commotion ceases, yet it still continues in the vessels for a considerable time after, though it be imperceptible. Thus, the portion of Ardent Spirit, obtained from some Vinegars, comes from a small quantity of Wine, which still remains unchanged in these Vinegars, not having had time enough to turn sour. For it is certain, from the experiments of all other Chymists as well as Mr. Boerhaave, that Vinegar, when old enough, yields no Ardent Spirit in distillation. But though old and well-made Vinegar yields no Ardent Spirit in distillation, we cannot thence conclude that it contains none. On the contrary, there are experiments which demonstrate that some of the Ardent Spirit, which was in the Wine before it was turned into Vinegar, still remains; but probably so combined and blended with the acid part, that it cannot be separated and rendered perceptible but by peculiar processes. Mr. Geoffroy obtained an Ardent Spirit from Vinegar, by distilling it as soon as it was concentrated by freezing. "This spirit," says he[16], "is the first liquor that rises. At first it hath only the same degree of inflammability as brandy; but, when re-distilled in the _balneum mariæ_, it fires gun-powder, like the best rectified Spirit of Wine: with this difference, that our Spirit is impregnated with an oil of an acrid taste and empyreumatic smell, which makes it yellow, and imparts its odour to it. This Spirit, at least that which comes over first, retains none of the Acid of the Vinegar; seeing it neither changes the tincture of violets, nor effervesces with Salt of Tartar." [16] Memoirs of the Academy for 1729. Mr. Geoffroy observes, that, if Vinegar concentrated by freezing be afterwards kept for several years, no Ardent Spirit will then be obtained from it by distillation. And this confirms what we said of unconcentrated Vinegar, and gives reason to think that the Ardent Spirit obtained from Vinegar, either by distilling it after concentration by freezing, or by other processes of which we shall treat in the sequel, is foreign to the Vinegar, and is only found therein, as was said above, because Vinegar contains a certain quantity of Wine which hath not altered its nature. For the Spirit of Wine we obtain from Vinegar doth not hinder our obtaining from it a great deal of Acid, which being more ponderous rises after it. Mr. Geoffroy gives the following account of the sequel of his analysis of Vinegar by distillation. "Continuing to distil in a _balneum mariæ_ the concentrated Vinegar, of which I had employed four pounds two ounces, there was left, after the distillation, a residuum of fourteen ounces; which could not rise, because it was too thick. I found it covered with a saline crust, which is the true Essential Salt of Vinegar, and not of the same nature with Tartar: for Tartar of Wine is scentless; whereas the Salt of Vinegar hath a pungent smell, being the Acid of Tartar subtilized by its union with the Sulphureous parts. If a sand-bath be now used, instead of the _balneum mariæ_, to carry on the distillation without burning the matter, part of this Salt will be resolved, and yield the last Acid Spirit, which is the strongest that can be obtained. "After I had, by a sand-heat, extracted all the Acid Spirit that the several residuums put together would yield, I found at the bottom of the cucurbit a brown mass, of the consistence of a pretty solid extract. Of this I put into a retort two pounds, together with six pounds of sand well washed and very dry; and, applying a graduated heat, I first obtained six ounces of an Acid Spirit, that smelt very strong of the empyreuma, and was a little coloured with some portion of oil; seven ounces of Spirit, having a volatile urinous smell, came over next: at last the white vapours appeared more and more dense. A volatile concrete Salt adhered to the sides of the ballon, and I found four ounces of a thick fetid Oil floating on the Spirit. The concrete volatile Salt, when collected, weighed two drams. The black matter remaining in the bottom of the retort, being calcined and lixiviated, yielded a fat alkaline Salt, which it is almost impossible to dry." I have given this account of Mr. Geoffroy's analysis of Vinegar at length, only because it differs in several respects from that described in the process, which is Mr. Boerhaave's, as well as from those delivered by several other Authors, who make no mention either of the saline matter, which Mr. Geoffroy found on the residuum of Vinegar, after its first distillation in the _balneum mariæ_, or of the volatile urinous Spirit and Salt, which he obtained from that residuum. These differences may arise either from the manner of distilling the Vinegar, or from Mr. Geoffroy's Vinegar having been concentrated by freezing, or rather from the quantity, and, above all, from the age of the Vinegar, examined by those different Chymists. The distillation of Vinegar serves not only to separate its Acid from a considerable quantity of earth and oily parts, with which it is entangled, but also to dephlegmate and concentrate it. Yet Mr. Lemeri affirms, that Vinegar is not distilled with a view to dephlegmate it. He condemns the common method of throwing away the first runnings as useless phlegm, and saving only what comes off afterwards; having, he says, observed, that the phlegm of Vinegar cannot be abstracted, like that of many other acid liquors, and that what comes over first is almost as sharp as what rises afterwards, be the fire applied at first ever so small. There is reason to think that Mr. Lemeri did not carefully enough examine the strength of his Spirit of Vinegar, at the different stages of his distillation: for Mr. Geoffroy, in the Memoir above cited, gives an account of a distillation of Vinegar, the product whereof he examined with care, having for that purpose divided it into five different portions: and his experiments put it beyond all doubt, that the first portions of Spirit of Vinegar are far from being so acid as the last. This Vinegar was so strong before distillation, that it required six grains of Salt of Tartar to absorb two drams of it. Two drams of the first portion of his Spirit were absorbed by three grains only of Salt of Tartar: the Acid of the second portion took five grains to absorb it. (Each experiment was made with two drams of Vinegar). The third portion was absorbed by ten grains; the fourth by thirteen, and the fifth took no less than nineteen: which proves that Vinegar, like most other Acids, may be concentrated by distilling off the most aqueous part, which is lighter than the Acid. There are therefore two ways of concentrating Vinegar, and separating its most acid part, namely distillation and congelation. These two methods may be successively applied to the same Vinegar, and a very powerful Acid obtained by their concurrence. Mr. Geoffroy having exposed to the frost, on the 19th of January 1739, the last russet-coloured liquor, drawn from the residuum of distilled Vinegar, found it so concentrated thereby, that it required sixty grains of Salt of Tartar to absorb two drams of it. CHAP. VI. _The_ ACID _of_ VINEGAR _combined with different_ SUBSTANCES. PROCESS I. _The Acid of Vinegar combined with alkaline Substances. Foliated Salt of Tartar, or Regenerated Tartar. Decomposition of that Salt_. Into a glass cucurbit put some very pure and well-dried Salt of Tartar; and pour on it some good distilled Vinegar, by little and little at a time. An effervescence will arise. Pour on more Vinegar, till you attain the point of saturation. Then fit a head to the cucurbit; set it in a sand-bath; and having luted on a receiver, distil with a gentle heat, and very slowly, till nothing remain but a dry matter. On this residuum drop a little of the same Vinegar; and if any effervescence appears, add more Vinegar till you attain the point of saturation, and distil again as before. If you observe no effervescence, the operation was rightly performed. _OBSERVATIONS._ It is not easy to hit the exact point of saturation in preparing this Neutral Salt; because the oily parts, with which the Acid of Vinegar is loaded, hinder it from acting so briskly and readily as it would do, if it were as pure as the Mineral Acids: and for this reason it often happens, that, when we have nearly attained the point of saturation, the addition of an Acid makes no sensible effervescence, though the Alkali be not yet entirely saturated; which deceives the operator, and makes him conclude erroneously that he hath attained the true point of saturation. But he easily perceives his mistake, when, after having separated from this saline compound all its superfluous moisture by distillation, he drops fresh Vinegar upon it: for then the Salts being more concentrated, and consequently more active, produce an effervescence, which would not have been sensible if this last portion of Acid, instead of coming into immediate contact with the dried Alkali, could not have mixed therewith till diffused through, and in a manner suffocated by, that phlegm from which the Acid of the Vinegar, before neutralized, was gradually separated by its combining with the Alkali; that phlegm keeping in solution both the Neutral Salt already formed, and the Alkali not yet saturated. And for this reason it is necessary to try, after the first desiccation of this Salt, which is called _Regenerated Tartar_, whether or no the just point of saturation hath been attained. It may also happen, that, though the point of saturation was exactly hit at first, this compound Salt shall nevertheless, after desiccation, effervesce with fresh Vinegar, and therefore not be in a perfectly neutral state at that time. In this case the Salt must have been dried by too violent a fire, and partly decompounded by an excess of heat carrying off some of the Acid, which does not adhere very strongly to the Alkali. This is one of the reasons why it is necessary that Regenerated Tartar be desiccated with a very gentle heat. From what hath been said, concerning the desiccation of this Neutral Salt, it is plain, that the use of it is only to free the Salt from the great quantity of superfluous moisture wherein it is dissolved: which proves that the Acid of Vinegar, like all other Acids dissolved in much water, is separated from most of this redundant phlegm by being combined with a Fixed Alkali. And hence we must conclude, that the Acid of Vinegar, contained in Regenerated Tartar desiccated, is vastly stronger and more concentrated than it was before: and accordingly Mr. Geoffroy, having decompounded this Salt, by the means of concentrated Oil of Vitriol, obtained a Spirit of Vinegar in white vapours, which was very volatile and very strong, but perhaps somewhat depraved with a taint of the Vitriolic Acid. Though the Acid of Vinegar be freed, by combining with a Fixed Alkali, from a great quantity of superfluous phlegm, as was shewn above; yet the oily parts with which it is entangled still cleave to it: these parts are not separated from it by its conversion into a Neutral Salt, but, without quitting it, combine also with the Fixed Alkali; and this gives Regenerated Tartar a saponaceous quality, and several other peculiar properties. Regenerated Tartar, when dried, is of a brown colour. It is semi-volatile; melts with a very gentle heat, and then resembles an unctuous liquor; which indicates its containing an Oil: when cast upon live coals it flames; and, when distilled with a strong heat, yields an actual oil; all which evidently prove the existence of that Oil. This Salt is soluble in Spirit of Wine; a quality which it probably owes also to its Oil. It requires about six parts of Spirit of Wine to dissolve it; and the dissolution succeeds very well in a matrass, with the help of a gentle warmth. If the Spirit of Wine be abstracted from this solution, by distilling with a small fire, the Salt remains at the bottom of the cucurbit, in the form of a dry substance composed of leaves lying one upon another; which hath procured it the name of _Terra Foliata Tartari_, or _Foliated Salt of Tartar_. It is not absolutely necessary that Regenerated Tartar be dissolved in Spirit of Wine to make the Foliated Salt: for it may be procured in this form, by only evaporating the water in which it is dissolved. But the operation succeeds better with Spirit of Wine; probably because the success thereof depends on using an exceeding gentle warmth: now Spirit of Wine evaporates with much less heat than water. Regenerated Tartar may also be crystallized. If you desire to have it in this form, combine the Acid with the Alkali to the point of saturation; evaporate the liquor slowly to the consistence of a syrop, and set it in a cool place; where it will shoot into clusters of crystals lying one upon another like feathers. Vinegar perfectly dissolves absorbent matters also, and particularly those of the animal kingdom; such as Coral, Crabs-eyes, Pearls, &c. In order to a dissolution of such matters, you must pulverize them, put them into a matrass, and pour on them Spirit of Vinegar to the depth of four fingers breadth: an effervescence will arise: when that is over, set the mixture to digest two or three days in a sand-bath; then decant the liquor, filter it, and evaporate it to dryness with a very gentle heat. The matter which remains is called _Salt of Coral_, _of Pearls_, _of Crabs-eyes_, _&c._ according to the substances dissolved. If, instead of evaporating the liquor, a Fixed Alkali be mixed therewith, the absorbent matter, that was dissolved by the Acid, will precipitate in the form of a white powder, which is called the _Magistery of Coral_, _of Pearls_, _&c._ PROCESS II. _The Acid of Vinegar combined with Copper. Verdegris. Crystals of Copper. This combination decompounded. Spirit of Verdegris._ Into a large matrass put Verdegris in powder. Pour on it distilled Vinegar to the depth of four fingers breadth. Set the matrass in a moderate sand-heat, and leave the whole in digestion, shaking it from time to time. The Vinegar will acquire a very deep blue-green colour. When the liquor is sufficiently coloured, pour it off by inclination. Put some fresh Vinegar into the matrass; digest as before; and decant the liquor again when it is sufficiently coloured. Proceed in this manner till the Vinegar will extract no more colour. There will remain in the matrass a considerable quantity of undissolved matter. The Vinegar thus impregnated with Verdegris is called _Tincture of Copper_. Mix these several Tinctures, and evaporate them with a gentle heat to a pellicle. Then set the liquor in a cool place: in the space of a few days a great many crystals of a most beautiful green colour will shoot therein, and stick to the sides of the vessel. Pour off the liquor from the crystals; evaporate it again to a pellicle, and set it by to crystallize. Continue these evaporations and crystallizations, till no more crystals will shoot in the liquor. These are called _Crystals of Copper_, and are used in painting. To this combination of the Acid of Vinegar with Copper the painters and dealers have given the title of _Distilled Verdigris_. _OBSERVATIONS._ Verdegris is prepared at Montpelier. To make it they take very clean plates of Copper, which they lay, one over another, with husks of grapes between, and after a certain time take them out. Their surfaces are then covered all over with a very beautiful green crust, which is _Verdegris_. This Verdegris is nothing but Copper corroded by the Acid of Tartar, analagous to the Acid of Vinegar, which abounds in the Wines of Languedoc, and especially in the rape, husks, and stones of grapes that have a very austere taste. Verdegris is a sort of rust of Copper; or Copper corroded and opened by the Acid of Wine, but not yet converted intirely into a Neutral Salt: for it is not soluble in water, nor does it crystallize. This arises from its not being united with a sufficient quantity of Acid. The design of the operation here described is to furnish the Verdegris with the quantity of Acid requisite to make it a true Metallic Salt: for which purpose distilled Vinegar is very fit. Crystals of Copper may be obtained, without employing Verdegris, by making use of Copper itself dissolved by the Acid of Vinegar, according to the method practised with respect to Lead, as shall be shewn hereafter. But Verdegris is generally used, because it dissolves soonest; it being a Copper already half-dissolved by an Acid correspondent to that of Vinegar. Crystals of Copper are decompounded by the action of fire alone, without any additament; because the Acid of Vinegar adheres but loosely to Copper. In order to decompound this Salt and extract its Acid, it must be put into a retort, and distilled in a reverbatory furnace with degrees of fire. An insipid phlegm rises first, which is the water retained by the Salt in crystallizing. This phlegm is succeeded by an acid liquor, which rises in the form of white vapours that fill the receiver. Towards the end of the distillation the fire must be violently urged, in order to raise the strongest and most fixed Acid. At last there remains in the retort a black matter, which is nothing but Copper, that may be reduced by melting it in a crucible with one part of Salt-petre and two parts of Tartar. A similar Acid, but more oily, and in a much smaller quantity, may be obtained from Verdegris by distillation. The Acid, which in this distillation comes over after the first phlegm, is an exceeding strong and concentrated Vinegar. It is known by the title of _Spirit of Verdegris_. Zwelfer, and after him M. le Fevre in his Chymistry, bestows extraordinary praises on this Spirit; pretending that it will produce the Salt of Coral, and others of the same kind, without losing any of its virtue, or ceasing to be acid; so as to remain still capable of performing other operations of the same nature. But Mr. Boerhaave and Mr. Lemeri positively deny the fact; and with good reason, having formed their judgments on their own experiments. Yet I can hardly think both Zwelfer and le Fevre would have affirmed a thing of this nature, in such a positive and confident manner, if they had been convinced in their minds that it was false. We must suppose that those Chymists examined the matter with too little attention, and were misled by some fallacious appearance. Probably they may have compared this concentrated Vinegar with common distilled Vinegar; they may have put to their Coral an equal dose thereof; and, after saturation, they may have distilled off the superfluous liquor, which may have effervesced with fresh Coral and dissolved it. Surprised at this effect, they may have imagined that their Acid had lost none of its strength, and that it had the virtue of converting into Salt any quantity of Coral, or such other matters, without any prejudice to its Acidity. A rash conclusion: which certainly they never would have made, if they had carried the experiment far enough; if they had dissolved a third or a fourth quantity of Coral in their Vinegar: for they would have been thereby convinced that the Spirit of Verdegris, like all other acid Spirits, deposites and leaves its Acid in absorbent matters; and that if the liquor, which they drew off by distillation from their first Salt of Coral, was still acid, and capable of dissolving fresh Coral, nothing could be inferred from thence but that Spirit of Verdegris is an exceedingly concentrated Vinegar, which, in the same quantity of liquor, contains much more Acid than the strongest distilled Vinegar prepared in the common way; that therefore a much smaller dose thereof is required to convert a given quantity of Coral into Salt; and that the liquor, which they distilled from their first Salt, still retained some of its virtue, only because it was replete with much more Acid than could be neutralized by the Coral. But a love of the marvellous so prepossesses the mind of man, that it often hinders him from perceiving the most obvious facts. This is the fault of all the ancient Chymists in general: and I believe the only reason why we find their books stuffed with so many unsucceeding experiments was, that their heated imaginations frequently represented things to them otherwise than they really were. PROCESS III. _The Acid of Vinegar combined with Lead. Ceruse. Salt or Sugar of Lead. This combination decompounded._ Into the glass head of a cucurbit, put thin plates of Lead, and secure them so that they may not fall out when the head is put upon the cucurbit. Fit on this head to a wide-mouthed cucurbit containing some Vinegar. Set it in a sand-bath; lute on a receiver, and distil with a gentle heat for ten or twelve hours. Then take off the head: in it you will find the leaden plates covered, and, in a manner, crusted over with a white matter. This being brushed off with a hare's foot is what we call _Ceruse_. The leaden plates thus cleansed may be employed again for the same purpose, till they be wholly converted into Ceruse by repeated distillations. During the operation there will come over into the receiver a liquor somewhat turbid and whitish. This is a distilled Vinegar in which some Lead is dissolved. Reduce a quantity of Ceruse into powder; put it into a matrass; pour on it twelve or fifteen times as much distilled Vinegar; set the matrass in a sand-bath; leave the matter in digestion for a day, shaking it from time to time: then decant your liquor, and keep it apart. Pour fresh Vinegar on what is left in the matrass, and digest as before. Proceed thus till you have dissolved one half, or two thirds, of the Ceruse. Evaporate to a pellicle the liquors you poured off from the Ceruse, and set them in a cool place. Greyish crystals will shoot therein. Decant the liquor from the crystals; evaporate it again to a pellicle, and set it by to crystallize. Proceed thus evaporating and crystallizing, as long as any crystals will shoot. Dissolve your crystals in distilled Vinegar, and evaporate the solution, which will then shoot into whiter and purer crystals. This is the _Salt_ or _Sugar of Lead_. _OBSERVATIONS._ Lead is easily dissolved by the Acid of Vinegar. If it be barely exposed to the vapour of that Acid, its surface is corroded, and converted into a kind of calx or white rust, much used in painting, and known by the name of _Ceruse_ or _White Lead_. But this preparation of Lead is not combined with a sufficient quantity of Acid to convert it into a Salt: it is no more than lead divided and opened by the Acid of Vinegar; a matter which is to Lead what Verdegris is to Copper. And therefore if you desire to combine Ceruse with the quantity of Acid necessary to convert it into a true Neutral Salt, you must treat it in the same manner as we did Verdegris, in order to procure Crystals of Copper; that is, you must dissolve it in distilled Vinegar, as the process directs. The Salt of Lead is not very white when it first shoots; and for this reason it is dissolved again in distilled Vinegar, and crystallized a second time. If salt of Lead be repeatedly dissolved in distilled Vinegar, and the liquor evaporated, it will grow thick; but cannot be desiccated without great difficulty. If the same operation be oftener repeated, this quality will be thereby more and more increased; till at last it will remain on the fire like an Oil, or melted Wax: it coagulates as it cools, and then looks, at first sight, like a metallic mass, somewhat resembling Silver. This matter runs with a very gentle heat, almost as easily as wax. The Salt of Lead hath a saccharine taste, which hath procured it the name also of Sugar of Lead. For this reason when Wine begins to turn sour, the ready way to cure it of that disagreeable taste is, to substitute a sweet one which is not disagreeable to the taste, by mixing therewith Ceruse, Litharge, or some such preparation of Lead: for the Acid of the Wine dissolves the Lead, and therewith forms a Sugar of Lead, which remains mixed with the Wine, and hath a taste which, joined with that of the Wine, is not unpleasant. But, as Lead is one of the most dangerous poisons we know, this method ought never to be practised; and whoever employs such a pernicious drug deserves to be most severely punished. Yet something very like this happens every day, and must needs have very bad consequences; while there is nobody to blame, and those to whom the thing may prove fatal can have no mistrust of it. All the retailers of Wine have a custom of filling their bottles on a counter covered with Lead, having a hole in the middle, into which a leaden pipe is soldered. The Wine which they spill on the counter, in filling the bottles, runs through this pipe into a leaden vessel below. In that it usually stands the whole day, or perhaps several days; after which it is taken out of the leaden vessel, and mixed with other Wine, or put into the bottle of some petty customer. But, alas for the man to whose lot such Wine falls! He must feel the most fatal effects from it; and the danger to which he is exposed is so much the greater, the longer the Wine hath stood in the leaden vessel, and thereby acquired more of a noxious quality. We daily see cruel distempers among the common people, occasioned by such causes, which are not sufficiently attended to. Wine that is not kept in close vessels is apt to turn sour very soon, especially in the summer; and the retailers of Wine have observed that their drippings, thus collected in vessels of Lead, are not liable to this inconvenience. This is what hath established among them the practice I am speaking against. As they see only the good effects thereof, and know nothing of its ill consequences, we cannot be angry with them. It is natural to think, that, as Lead hath the property of keeping Wine cool, it may by that means prevent its growing sour for some time; and persons who are not versed in Chymistry can hardly suspect that Wine is preserved from being pricked, only by being converted into a kind of poison. Yet this is the very case: for Lead doth not hinder the Wine from growing sour; but, uniting with its Acid, as soon as it appears, and forming therewith a Sugar of Lead, changes the taste thereof as hath been said, and hinders the Acid from affecting the palate. Hence it appears how much it were to be wished that the use of those counters covered with Lead were abolished entirely. I am informed, by a Chymist zealous for the public good[17], that he represented this matter to the Magistrates several years ago. It is not to be doubted, that, when the dealers in Wine know the ill consequences attending this practice, they will with pleasure sacrifice the small benefit they receive from it to the public safety. [17] Mr. Rouelle, whom I have had occasion to mention several times in this work with the honour which he deserves, and with whom I went through a course of Chymistry, when I was a Student in Medicine. It must be observed, to the praise of this ingenious Artist, that he is the first Frenchman that ever gave Courses of Chymistry. In these he explains the operations according to the true and sound Theory of the Science, drawn from the writings of Beccher, Stahl, Juncker, Boyle, Boerhaave, Hoffman, and many other excellent Chymists, whom it would be tedious to mention here, as well as from the Memoirs of the most celebrated Academies, particularly those of the Academy of Sciences at Paris. It is easy to prove whether or no a suspected Wine contains Lead. You need only pour into it a little Oil of Tartar _per deliquium_; or, if you have not that at hand, a lye of the ashes of green wood. If there be any Lead dissolved in it, the liquor will immediately grow turbid, and the Lead will precipitate in the form of a white powder; because the Sugar of Lead it contains, being a Neutral Salt, whose basis is a metal, is decompounded by the Fixed Alkali, which separates that metal from the Acid. Lead thus separated from the Acid of Vinegar by an Alkali is called _Magistery of Lead_. Ceruse, or White Lead, is also a very dangerous poison. It is a pigment very much used, being the only White that can be applied with Oil. This White is the most common, or, perhaps, the only cause of those dreadful colics with which painters, and all that work in colours, are frequently afflicted. This induced me to examine all the substances capable of affording a White, in order to find one, if possible, which might be substituted for White Lead: but, after a vast number of experiments, I had the mortification to be convinced, that all Whites, even the brightest and most beautiful, which are not metallic, produce nothing, when ground with Oil, but greys, or dirty yellows. There is still something to be hoped for in Whites obtainable from certain metallic substances: but, as every one of those matters may be suspected of some noxious quality, long experience alone will remove our just apprehensions of danger from every thing afforded by such substances. To return to the Salt of Lead: it may be decompounded by distillation without addittament. In order to perform this, you must put the Salt of Lead into a glass or stone retort, leaving a full third thereof empty, and distil in a reverberating furnace with degrees of fire. A spirit rises, which fills the receiver with clouds. When nothing more will come over with a fire that makes the retort red-hot, let the vessels cool, and then unlute them. You will find in the receiver, an austere liquor, which is inflammable, or, at least, an inflammable Spirit may be obtained from it, if about one half thereof be drawn off by distillation in a glass alembic. The retort in which the Salt of Lead was decompounded contains at the end of the operation, a blackish matter: this is Lead, which will resume its metallic form on being melted in a crucible; because the Acid by which it was dissolved, and from which it hath been separated, being of a very oily nature, hath left in it a sufficient quantity of phlogiston. What is most remarkable in this decomposition of Salt of Lead is the inflammable Spirit which it yields, though the Vinegar which entered into the composition of the Salt seemed to contain none at all. CHAP. VII. _Of the_ PUTRID FERMENTATION _of_ VEGETABLE SUBSTANCES. PROCESS I. _The Putrefaction of Vegetables._ Fill a hogshead with green plants, and tread them down a little; or, if the vegetables be dry and hard substances, divide them into minute parts, and steep them a little in water to moisten them: then leave them, or the green plants, in the vessel, uncovered and exposed to the open air. By degrees a heat will arise in the center of the vessel, which will continue increasing daily, at last grow very strong, and be communicated to the whole mass. As long as the heat is moderate, the plants will retain their natural smell and taste. As the heat increases, both these will gradually alter, and at last become very disagreeable, much like those of putrid animal substances. The plants will then be tender as if they had been boiled; or even be reduced to a kind of pap, more or less liquid according to the quantity of moisture they contained before. _OBSERVATIONS._ Almost all vegetable matters are susceptible of putrefaction; but some of them rot sooner, and others more slowly. As putrefaction is only a species of fermentation, the effect whereof is to change entirely the state of the Acid, by combining it with a portion of the earth and Oil of the mixt, which are so attenuated that from this union there results a new saline substance in which no Acid is discernible; which on the contrary hath the properties of an Alkali, but rendered Volatile; it is plain, that, the nearer the Acid of a plant set to putrefy is to this state, the sooner will the putrefaction of that plant be completed. Accordingly all plants that contain a Volatile Alkali ready formed, or from which it can be obtained by distillation, are the most disposed to putrefaction. Those plants, in which the Acid is very manifest and sensible, are less apt to putrefy; because all their Acid must undergo the change above specified. But vegetable matters, whose Acid is entangled and clogged by several of their other principles, must be still longer elaborated, before they can be reduced to the condition into which complete putrefaction brings all vegetables. The earthy and oily parts, in which the Acids of these substances are sheathed, must be attenuated and divided by a previous fermentation, which, from those parts subtilized and united with the Acid, forms an Ardent Spirit, wherein the Acid is more perceptible than in the almost insipid, or saccharine juices, out of which it is produced. The Acid contained in the Ardent Spirit must be still further disengaged, before it can enter into the combination of a Volatile Alkali: consequently the Ardent Spirit must undergo a sort of decomposition; its Acid must be rendered more sensible, and be brought to the same condition as the Acid of plants in which it manifests all its properties. Hence it appears, that the spirituous and acetous fermentations are only preparatives, which nature makes use of, for bringing certain vegetable matters to putrefaction. These fermentations therefore must be considered as advances towards that putrefaction, in which they terminate, or rather as the first stages of putrefaction itself. This is the opinion of Mr. Stahl, who hath treated this subject with great sagacity, and thrown much light upon it. Mr. Boerhaave is not altogether of the same mind. He considers putrefaction as something foreign to fermentation; as an operation independent of it, and very different from it. He gives the title of fermentation to that intestine and spontaneous motion only which produces an Ardent Spirit, and changes it into an Acid. He founds his opinion on this, that the circumstances attending putrefaction are different from those which accompany spirituous and acetous fermentation; that the product of putrefaction is very different from the products of these fermentations; and lastly, that all vegetable and animal substances are susceptible of putrefaction, whereas only some kinds of them are capable of fermentation properly so called. Mr. Boerhaave is so far right, that we ought not to confound together operations which differ in several respects, and result in different productions; but Mr. Stahl's opinion must nevertheless be looked on as highly probable, or rather absolutely true. For it doth not necessarily follow, from the difference between the circumstances and productions of fermentative motions, that the operations have no relation to, or connection with, each other. They may nevertheless be considered as different steps of one and the same operation: and if all vegetable and animal matters are not susceptible of the three degrees of fermentation, we can only infer from thence that there are mixts, in which the whole work of fermentation is yet to do; and that there are others whose principles are so disposed that they are in the same condition as if they had already undergone the first, or even the second, degree of fermentation; and consequently such mixts are susceptible only of the second, or perhaps of the third, degree of fermentation. Mr. Stahl therefore says very judiciously, that, far from denying putrefaction to be a fermentation, we ought on the contrary to consider all fermentation as no other than putrefaction. Matters susceptible of the spirituous and acetous fermentation do but pass through these previous alterations in their way to complete putrefaction. On this principle, Wine and Vinegar are only liquors that had begun to putrefy, but were stopt at the first or second stage of their putrefaction. This is so true, that, if a fermenting liquor be left to itself in the open air, and in a due degree of heat, it will proceed directly, without any stop, to perfect putrefaction. The acetous fermentation is attended with more heat than the spirituous, and the putrid with still more than the acetous. The heat of putrefying plants is sometimes so considerable, that, when they are not too moist, and are stacked up in great heaps, they take fire and burn violently. Of this there are frequent instances in hay-ricks. PROCESS II. _Putrefied Vegetable Substances analyzed._ Put the putrefied plants you mean to analyze into a glass cucurbit, and set it in a sand-bath. Fit to it a head; lute on a receiver; distil with a gentle fire, and a limpid fetid liquor will come over. Continue the distillation till the matter contained in the retort be almost dry. Then unlute your vessels, and keep the liquor you find in the receiver by itself. Put the matter remaining in the cucurbit into a retort, and distil with a graduated heat. There will rise white vapours; a pretty considerable quantity of liquor nearly like that of the former distillation; a Volatile Salt in a concrete form; and a black oil, which towards the end will be very thick. In the retort there will remain a black charred matter, which being burnt in the open air will fall into ashes, from which no Fixed Alkali can be extracted. By means of a funnel separate your oil from the aqueous liquor. Distil this liquor with a gentle heat. You will by this means obtain a Volatile Salt like that of animals; of which you may also get some, by the same means, from the liquor which came over in the first distillation. _OBSERVATIONS._ This analysis shews the changes which putrefaction produces in vegetable matters. Scarce any of their principles are now to be discerned. They now yield no aromatic liquor; no Essential Oil; no Acid; and consequently no Essential Salt, Ardent Spirit, or Fixed Alkali: in a word, whatever their natures were before putrefaction, they are all alike when they have once undergone this fermentative motion in its full extent. Nothing can then be obtained from them but Phlegm, a Volatile Alkali, a fetid Oil, and an insipid Earth. Almost all these changes are owing to the transmutation of the Acid, which is depraved by putrefaction, and combined with a portion of the Oil and subtilized Earth of the mixt; so that the result of their union is a Volatile Alkali. Now, as the Fixed Alkali, found in the ashes of unputrefied plants, is only the most fixed part of their earth and of their Acid, closely united together by the igneous motion, it is not surprising that, when all the Acid, with a part of the earth, is subtilized and volatilized by putrefaction, no Fixed Alkali can be found in the ashes of putrefied Vegetables. The alteration which the Acid suffers by the putrefactive motion is, in my opinion, the greatest it can undergo, without being entirely destroyed and decomposed, so as to be no longer a Salt. We have seen it, in the Mineral kingdom, in its greatest purity and strength. Its combination with Oil, and the other alterations its undergoes, in the Vegetable kingdom, have shewn it weakened and disguised. The changes it suffers by the spirituous and acetous fermentation, have exhibited it in other forms. And lastly, putrefaction disfigures it completely, and, in some sort, changes its very nature, so that it cannot be distinguished. In the animal kingdom we find it nearly in the same condition: for though the Vegetable substances, on which animals feed, do not undergo direct putrefaction, in its full extent, before they are converted into animal juices, yet they suffer most of the alterations produced by putrefaction; so that when they have acquired the qualities necessary to their becoming an actual nutritious animal juice, they are within one step of complete putrefaction. For this reason all animal substances are very apt to putrefy, and are unsusceptible of the first degrees of fermentation. But this discussion belongs to the animal kingdom, of which we are now going to treat in the third part of these Elements; the theory of putrefaction serving to introduce it, and naturally leading us to it. [Illustration: Decorative Scroll.] PART III. OF OPERATIONS ON ANIMAL SUBSTANCES. CHAP. I. _Of_ MILK. PROCESS I. _Milk separated into Butter, Curd, and Whey; instanced in Cow's Milk._ Put new Cow's milk into a flat earthen pan, and set it in a temperate heat. In ten or twelve hours time there will gather on its surface a thick matter, of a somewhat yellowish white: this is called _Cream_. Gently skim off this Cream with a spoon, letting the milk you take up with it run off. Put all this Cream into another vessel, and keep it. The milk thus skimmed will not be quite so thick as before: nor will it be of such a dead white, but have a little blueish cast. If all the Cream be not separated from it, more will gather on its surface after some time, which must be taken off as the former. In two or three days the skimmed milk will coagulate into a soft mass called _Curd_, and then it tastes and smells sour. Cut this Curd across in several places. It will immediately discharge a large quantity of _Serum_. Put the whole into a clean linen cloth; hang it up, and underneath it set a vessel to receive the Serum as it drops. When the aqueous part hath done dripping, there will remain in the filter a white substance somewhat harder than the curdled milk. This substance is called _Cheese_, and the _Serum_ separated from it is known by the name of _Whey_. _OBSERVATIONS._ The milk of animals, that feed only on vegetables, is of all animal matters the least removed from the vegetable nature. The truth of this will be demonstrated by the experiments we shall produce by and by, for the further analysis of milk. For this reason we judged, with Mr. Boerhaave, that it was proper to begin the analysis of animals by examining this liquor. Most Chymists justly consider Milk as of the same nature with Chyle. Indeed there is great reason to think, that, except some small differences to be afterwards taken notice of, these two matters are nearly the same. They are both of a dead white colour, like that of an emulsion; which proves that, like emulsions, they consist of an oily matter divided, diffused, and suspended, but not perfectly dissolved, in an aqueous liquor. It is not surprising that these liquors should resemble emulsions; for they are produced in the same manner, and may very justly be called _Animal Emulsions_. For how are vegetable substances converted into Chyle and Milk in an animal body? They are bruised, divided, and triturated by mastication and digestion, as perfectly, at least, as the matters pounded in a mortar to make an emulsion; and must thereby undergo the same changes as those matters; that is, their oily parts, being attenuated by those motions, must be mixed with and lodged between the aqueous parts, but not dissolved therein; because they do not, in the bodies of animals, meet with saline matters, sufficiently disentangled and active, to unite intimately with them, and by that means render them soluble in water. Nevertheless Chyle and Milk, though produced in the same manner as emulsions, and very much resembling them, differ greatly from them in some respects; owing chiefly to the time they remain in the bodies of animals, their being heated while there, the elaborations they undergo therein, and the animal juices commixed with them. New Milk hath a mild agreeable taste, without any saline pungency; nor hath any Chymical trial discovered in it either an Acid or an Alkali. Yet it is certain that the juices of plants, out of which milk is formed, contain many saline matters, and especially Acids: accordingly Milk also contains the same; but the Acids are so sheathed and combined, that they are not perceptible. The case is the same with all the other liquors intended to constitute part of an animal body: there is no perceptible Acid in any of them. Hence it may be inferred that one of the principal changes which vegetables undergo, in order to their being converted into an animal substance, consists in this, that their Acids are combined, entangled, and sheathed in such a manner that they become imperceptible, and exert none of their properties. Milk left to itself, without the help of distillation, or any additament whatever, undergoes a sort of decomposition. It runs into a kind of spontaneous analysis; which doth not indeed reduce it to its first principles, yet separates it into three distinct substances, as the process shews; namely, into Cream, or the buttery fat part, into Curd or Cheese, and into Serum or Whey: which shews that those three substances of which Milk consists, are only mixed and blended together, but not intimately united. The first parts, being the lightest, rise gradually to the surface of the liquor as they separate from the rest: and this forms the Cream. Cream, as skimmed from the surface of Milk, is not however the pure buttery or fat part; it is still mixed with many particles of Cheese and Whey, which must be separated in order to reduce it into Butter. The most simple, and at the same time the best method of effecting this, is daily practised by the country people. It consists in beating or churning the Cream, in a vessel contrived for that purpose, with the flat side of a circular piece of wood, in the center of which a staff is fixed. One would think that the motion, impressed on the Cream by this instrument, should rather serve to blend more intimately the particles of Butter, Cheese, and Whey, of which it consists, than to separate them from each other; as this motion seems perfectly adapted to divide and attenuate those particles. But, if we consider what passes on this occasion, we shall soon perceive that the motion by which Butter is churned is nothing like triture: for churning is no other, properly speaking, than a continually repeated compression, the effect whereof is to squeeze out from amongst the buttery particles those of Cheese and Whey mixed therewith; by which means the particles of Butter are brought into contact with each other, unite, and adhere together. Milk, whether skimmed or no, grows sour of itself, and curdles in a few days. When it is newly curdled, the Cheese and Whey seem to be united, and to make but one mass: but these two matters separate spontaneously from each other, with the greatest ease, and in a very short time. The acidity, which Milk naturally contracts in the space of a few days, must be considered as the effect of a fermenting motion, which discovers in that liquor an Acid that was not perceptible before. This, properly speaking, is an acetous fermentation, which Milk passes through in its way to putrefaction; and it soon follows, especially if the Milk be exposed to a hot air. If, instead of leaving Milk to grow sour and curdle of itself, an Acid be mixed therewith, while it is yet sweet and newly milked, it immediately coagulates; which gives reason to think, that its curdling naturally is the effect of the Acid, which discovers itself therein as it grows stale. The coagulation of Milk may also be considerably accelerated, by setting it in a sand-bath gently heated; or by mixing therewith a little of what, in the language of the Dairy, is called _Runnet_; which is nothing but some curdled and half-digested Milk taken from the stomach of a Calf: or both these methods may be employed at once, which will produce the effect still more expeditiously. It is not difficult to find out the cause of these effects. The Runnet, which is Milk already curdled and grown sour, is an actual ferment to sweet Milk, disposing it to turn sour, much more readily: for though Milk, when thus hastily curdled by the Runnet, hath not a manifestly acid taste, yet it is certain that this Acid begins to exert itself. The proof thereof is, that, being exposed to the same degree of heat with Milk equally new, that is not mixed with this ferment, it turns sour much sooner. As to the effect of heat in coagulating Milk, there is nothing extraordinary in it: we know how much it promotes and accelerates all fermentative motion. The whole of this perfectly agrees with what we said before concerning fermentation. Fixed Alkalis also coagulate Milk; but at the same time they separate the Whey from the Cheese, which floats on the liquor in clots. They give the Milk a russet-colour inclining to red; which may arise from their attacking the fat part. The separation of Milk into Butter, Cheese, and Whey, is a kind of imperfect analysis thereof, or rather the beginning of one. In order to render it complete, we must examine each of these substances separately, and find the principles of which they consist. This we shall endeavour to do in the following process. PROCESS II. _Butter analyzed by Distillation._ Into a glass retort put the quantity of fresh Butter you intend to distil. Set the retort in a reverberatory; apply a receiver, and let your fire be very gentle at first. The Butter will melt, and there will come over some drops of clear water, which will have the peculiar smell of fresh Butter, and shew some tokens of Acidity. If the fire be increased a little, the Butter will seem to boil: a froth will gather on its surface, and the phlegm, still continuing to run, will gradually come to smell just like Butter clarefied in order to be preserved. Its Acidity will be stronger and more manifest than that of the first drops that came over. Soon after this, by increasing the fire a little more, there will rise an Oil, having nearly the same degree of fluidity as fat Oils; but it will grow thicker as the distillation advances, and at last will fix in the receiver when it cools. It will be accompanied with some drops of liquor, the Acidity whereof will always increase, while its quantity decreases, as the distillation advances. While this thick Oil is distilling, the Butter contained in the retort, which at first seemed to boil, will be calm and smooth, without the least appearance of ebullition; though the heat be then much greater than when it boiled. Continue the distillation, constantly increasing the fire by degrees as you find it necessary for the elevation of the thick Oil. This Oil, or rather this kind of Butter, will be at last of a russet-colour. There will rise along with it some white vapours exceeding sharp and pungent. When you observe that nothing more comes over, though the retort be quite red-hot, let the vessels cool, and unlute them. You will find in the receiver an aqueous acid liquor, a fluid Oil, and a kind of fixed brown Butter. Break the retort, and you will find therein a charred matter; the surface of which, where it touched the glass, will be of a shining black, and have a fine polish. _OBSERVATIONS._ The analysis of Butter proves that this substance, which is an oily matter in a concrete form, owes its consistence to the Acid only, with which the oily part is combined: that is, it follows the general rule frequently mentioned above in treating of other oily compounds; the consistence whereof we shewed to be so much the firmer, the more Acid they contain. The first portions of Oil that come over in the distillation of Butter are fluid, because a pretty considerable quantity of Acid rose before them, which being mixed with the phlegm gives it the Acidity we took notice of. This Oil, being freed from its Acid, and by that means rendered fluid, rises first; because it is by the same means rendered lighter. The kind of Butter that comes over afterwards, though it be fixed, is nevertheless far from having the same consistence as it had before distillation; because it loses much of its Acid in the operation. This Acid is what rises in the form of white vapours. These vapours are, at least, as pungent and irritating as the Sulphureous Acid or Volatile Alkalis: but their smell is different: it hath a resemblance, or rather is the same, with that which rises from Butter, when it is burnt and browned in an open vessel. But, when concentrated and collected in close vessels, as in the distillation of Butter, they are vastly stronger: they irritate the throat so as to inflame it; they are exceeding sharp and pungent to the smell, and are so hurtful to the eyes that they quickly inflame them, as in an ophthalmy, and make them shed abundance of tears. The great volatility of this Acid is entirely owing to a portion of the phlogiston of the Butter with which it is still combined. It may be asked why Butter, or the oily part of Milk which hath the consistence of a fixed Oil, is more replete with an Acid than the Oils of the vegetables whereof the Milk was formed; as these Oils are almost all fluid, which indicates their containing less Acid before than after they were digested in the body of an animal. This must appear the more extraordinary, because the Acid contained in the liquors of animals is sheathed and imperceptible, and consequently incapable of combining with the Oils of vegetables so as to give them this consistence. I think it will be easy to give a satisfactory answer to this question, if it be considered, that the Oils, which exist in the vegetable juices whereof the Milk is formed, are far from being combined with the whole Acid of those vegetables; because there is hardly a plant that doth not yield a great deal of Acid, even without the help of fire. Now, there is reason to think, that one of the principal effects of digestion is, to combine and unite this Acid, with the oily parts of vegetables, more intimately than it was before. The further we advance in the analysis of animals, the more we shall be convinced, that, in the different elaborations, which vegetable substances undergo in order to their being changed into the nutritious juices of animals, nature employs all her powers to expel, destroy, or at least, weaken and blunt the Acids, so as to render them absolutely imperceptible. One of the best means by which she can effect this, is the combining and uniting them intimately with the oily parts: and this operation she probably begins in digestion. She gets rid of most part of the Acids contained in the aliments, by thus uniting them with the Oils contained in those aliments. Hence arises the consistence of Butter, which is the fat part of Milk, that is, of a liquor half-changed into an animal juice. This explication furnishes us also with the reason why Acids agree so ill with people of weak and delicate constitutions. The motion and heat in their bodies is not sufficient to effect a due combination of the Acids with the Oils. Hence it comes to pass, that, during and after digestion, they find in their bowels the bad effects of those Acids, in the disorder commonly called the _Heart-burn_. Hence also it is that such people receive great benefit from the use of Absorbents, which uniting with the Acids neutralize them, and relieve nature when she has not strength enough herself to get the better of them. To return to our analysis of Butter: we took notice in the process that Butter seems to boil with a very moderate heat at the beginning of the distillation, and that in the course of the operation the ebullition ceases entirely, though the heat be then greatly increased; which is contrary to the general rule. The reason is, that butter, though a seemingly homogeneous mass, contains nevertheless some particles of Cheese and Whey. The particles of Whey, being much the lightest, endeavour, on the first application of heat, to extricate themselves from amongst the particles of Butter, and to rise in distillation. Thus they form the drops of acidulated phlegm which come over at first, and, in struggling to get free, lift up the buttery parts, or actually boil, which occasions the ebullition observable at the beginning of the process. When they are once separated, the melted Butter remains calm and smooth without boiling. If you want to make it boil you must apply a much greater degree of heat; which you cannot do in close vessels, without spoiling the whole operation: because the degree of heat necessary for that purpose would force up the Butter in substance, which would rush over into the receiver, without any decomposition. Indeed if the vessels were luted they would be in danger of bursting. As to the caseous parts, which are mixed with fresh Butter, they also separate at the beginning of the distillation, when the Butter is melted, and gather on its surface in a scum. These particles of Cheese and Whey, which are heterogeneous to Butter, help to make it spoil the sooner. And for this reason those who want to keep Butter a long time, without the use of salt, melt it, and thereby evaporate the aqueous parts. The lightest portion of the particles of Cheese rises to the surface, and is skimmed off; the rest remains at the bottom of the vessel, from which the Butter is easily separated, by decanting it while it is yet fluid. Butter may also be distilled, by incorporating it with some additament which will yield no principle itself, nor retain any of those of the Butter. I have distilled it in this manner with the additament of fine sand: the operation succeeds very well, is sooner finished, and more easily conducted: but I chose to describe here the manner of doing it without additament; because the several changes, which the Butter undergoes in the retort during the operation, may be better observed. If you desire to convert the Butter wholly into Oil, you must take the fixed matter you find in the receiver, and distil it once more, or oftener, according to the degree of fluidity you want to give it. The case is the same with this matter as with all other thick Oils, which, the oftener they are distilled, grow always the more fluid, because in every distillation they are separated from part of the Acid, to which alone they owe their consistence. PROCESS III. _The Curd of Milk analyzed by distillation._ Into a glass retort put some new Curd, having first drained it thoroughly of all its Whey, and even squeezed it in a linen cloth to express all its moisture. Distil it as you did Butter. There will come over at first an acidulated phlegm, smelling like Cheese or Whey. As the distillation advances, the Acidity of this phlegm will increase. When it begins to run but very slowly raise your fire. There will come over a yellow Oil, somewhat empyreumatic. Continue the distillation, still increasing the fire by degrees as occasion requires. The Oil and acid Phlegm will continue to rise; the Phlegm growing gradually more acid, and the Oil deeper coloured, and more empyreumatic. At last, when the retort is almost red-hot, there comes off a second black Oil, of the consistence of Turpentine, very empyreumatic, and so heavy as to sink in water. In the retort will be left a considerable quantity of charred matter. _OBSERVATIONS._ Cheese-curd barely drained, till no more Whey will drip from it, is not entirely freed thereof; and for this reason we directed it to be pressed in a linen cloth, before it be put into the retort to be distilled. Without this precaution, the remaining Whey would rise in a considerable quantity on the first application of heat; and, instead of analyzing the Curd only, we should at the same time analyze the Whey also. This is to be understood of green Curd and new-made Cheese; for, if it be suffered to grow old, it will at length dry of itself: but then we should not obtain from it the same principles by distillation; as it corrupts and begins to grow putrid after some time, especially if it be not mixed with some seasoning to preserve it. The first Phlegm that rises in this distillation, as in that of Butter, is a portion of the Whey that was left in the Cheese, notwithstanding its being well pressed. This Phlegm grows gradually more acid, being the vehicle of the Acids of the Cheese, which are forced up along with it by the fire. The Acid obtained from this matter is less in quantity, and weaker, than that of Butter: and accordingly the Oil distilled from Cheese is not fixed like that of Butter. Yet it is remarkable that the last empyreumatic Oil, which is as thick as Turpentine, is heavier than water: a property which it probably derives from the quantity of Acid it retains. The quantity of charred matter, which remains in the retort after the distillation of Cheese, is much greater than that left by Butter; which proves that the former contains a much greater quantity of earth. These coals are exceeding difficult to burn and reduce to ashes. I have kept them red-hot, in the open air, and in a very strong fire, about six hours, continually stirring them, in order to bring the under parts to the surface, that they might be burnt, yet I could not consume them entirely. They even deflagrated afterwards with Nitre, as if they had not been burnt at all; and yet, during the whole time of their calcination, there appeared constantly a small flame, like that of charcoal, on the surface of the matter. PROCESS IV. _Whey analyzed._ Evaporate two or three quarts of Whey almost to dryness in a _balneum mariæ_; and distil the extract, or residuum, in a retort set in a reverberating furnace, with degrees of fire, according to the general rule. At first some Phlegm will come over; then a lemon-coloured acid Spirit; and afterwards a pretty thick Oil. There will remain in the retort a charred matter, which being exposed to the air grows moist. Lixiviate it with rain water, and evaporate the lixivium: it will yield you crystals of Sea-salt. Dry the charred matter, and burn it in the open air with a strong fire, till it be reduced into ashes. A lixivium of these ashes will shew some tokens of a Fixed Alkali. _OBSERVATIONS._ Milk, as was said before, separates naturally and spontaneously into three sorts of substances, the analyses whereof being put together make a complete analysis of this animal liquor. I know no Author that hath delivered the analyses of Butter and Cheese; so that the processes here given for analyzing these two substances are taken from the experiments I thought proper to make, in order to obtain the necessary lights in this matter. As for the analysis of Whey, it is taken from one of Mr. Geoffroy's Memoirs, containing experiments on several animal substances, which was published in 1732. It is there so particularly and so well described, that it was needless for me to attempt it anew. It will appear, on examining the three analyses of the substances whereof Milk consists, that none of them yields a Volatile Alkali: which I think very worthy of notice; as it is, I believe, the only animal matter from which such a Salt cannot be obtained. It is true, the milk of animals that feed on vegetables may be considered as an intermediate liquor between vegetable and animal substances; as an imperfect animal juice, which still retains much of the vegetable nature: and we actually find that Milk almost always hath, at least in part, the properties of those plants with which the animals that yield it are fed. Yet, as it cannot be formed in the body of the animal, without mixing with several of its juices that are entirely perfected, and become purely animal, it must appear strange that the analysis thereof should not afford the least vestige of that principle, which all other animal matters yield in the greatest plenty. I imagine the reason of this may be found in the use to which Milk is destined. It is intended for the nourishment of animals of the same species with those in whose bodies it is produced. Consequently it ought as much as possible to resemble the juices of the food which is proper for those animals. Now, as animals that live only on vegetables could not be properly nourished by animal matters, for which nature itself hath even given them an aversion, it is not surprising that the Milk of such animals should be free from any mixture of such things as are unsuitable to the young ones whom it is designed to nourish. There is reason therefore to think that nature hath disposed the organs, in which the secretion of Milk is performed, so as to separate it entirely from all the animal juices first mixed with it: and this I take to be the principal difference between Milk and Chyle; the latter being necessarily blended with the saliva, the gastric and pancreatic juices, the bile and lymph, of the animals in which it is formed. Hence it may be concluded, that, if a quantity of Chyle could be collected sufficient to enable us to analyze it, the analysis thereof would differ from that of Milk, in this chiefly that it would yield a great deal of Volatile Alkali, of which Milk, as hath been said, yields none at all. The same thing probably takes place in carnivorous animals. It is certain that those animals chuse to eat the flesh of such others only as feed upon vegetables; and that nothing but extreme hunger, and the absolute want of more agreeable food, will force them to eat the flesh of other carnivorous animals. Wolves, which greedily devour sheep, goats, &c. seldom eat Foxes, Cats, Polecats, &c. though these animals are not strong enough to resist them. Foxes, Cats, and Birds of prey, that make such terrible havock among wild fowl, and other sorts of game, do not devour one another. This being laid down, there is reason to think that the Milk of carnivorous animals is something of the nature of the flesh of those animals that feed on vegetables, and which they chuse to eat, and not of the nature of their own flesh; as the Milk of animals that feed on vegetables is analagous to the juice of vegetables, and when analyzed yields no Volatile Alkali, though every other part of their body does. But whatever be the nature of Milk, and of whatever ingredients it be formed, it always contains the three several substances above-mentioned; namely, the fat, or Buttery part, properly so called, the Cheesy, and the Serous part, the last of which we are now examining. It is, properly speaking, the Phlegm of the Milk, and consists almost entirely of water. For this reason it is proper to lessen the quantity thereof considerably by evaporation, so that its other principles, being concentrated and brought nearer together, may become much more sensible. There is no danger of losing any essential part of the Whey in the evaporation, if it be performed in the _balneum mariæ_, with such a gentle heat as may carry off the aqueous parts only: this greatly shortens the analysis, which will prove exceeding long and tedious, if all the water be distilled off in close vessels. As Whey is chiefly the aqueous part of Milk, as said above, it must contain all the principles thereof that are soluble in water; that is, its saline and saponaceous parts. And accordingly the analysis thereof shews that it contains an Oil, rendered perfectly saponaceous by an Acid; that is, made perfectly miscible with water. This quality of the Oil contained in Whey appears from the perfect transparency of that liquor, which we know is the mark of a complete dissolution. In the distillation of Whey, the saponaceous matter contained therein is decomposed; the saline part rises first, as being the lightest; this is the Acid taken notice of in the process; after which the Oil, now separated from the principle which rendered it miscible with water, comes over in its natural form, and doth not afterwards mix with the aqueous part. Besides the saponaceous matter, Whey contains also another saline substance; namely, Sea-Salt: this is obtained by lixiviating the _caput mortuum_ left in the retort, which, because of its fixedness, cannot rise with the other principles in distillation. To this Salt it is owing that what remains in the retort after distillation grows moist in the air; for we know that Sea-salt thoroughly dried hath this property. The fixed Alkaline Salt, obtained from the _caput mortuum_ burnt to ashes, proves that Milk still retains something of the vegetable nature: for the following analysis will shew us that matters purely animal yield none at all. CHAP. II. _Of the_ SUBSTANCES _which compose an_ ANIMAL BODY. PROCESS I. _Blood analyzed. Instanced in Bullock's Blood._ In a _balneum mariæ_ evaporate all the moisture of the Blood that the heat of boiling water will carry off. There will remain an almost dry matter. Put this dried Blood into a glass retort, and distil with degrees of heat, till nothing more will come over, even when the retort is quite red-hot, and ready to melt. A brownish phlegm will rise at first: this will soon be impregnated with a little Volatile Alkali, and then will come over a yellow Oil, a very pungent Volatile Spirit, a volatile Salt in a concrete form, which will adhere to the sides of the receiver; and, at last, a black Oil, as thick as pitch. There will be left in the retort a charred matter, which being burnt yields no Fixed Alkali. _OBSERVATIONS._ Blood, which is carried by the circulation into all the parts of the animal body, and furnishes the matter of all the secretions, must be considered as a liquor consisting of almost all the fluids necessary to the animal machine: so that the analysis thereof is a sort of general, though imperfect, analysis of an animal. Blood drawn from the body of an animal, and set by in a vessel, coagulates as it grows cold; and sometime afterwards the _coagulum_ discharges a yellowish _Serum_ or lymph; and in the midst thereof swims the red part, which continues curdled. These two substances, when analyzed, yield nearly the same principles; and in that respect seem to differ but little from each other. Though the Serum of Blood be naturally in a fluid form, yet it hath also a great tendency to coagulate, and a certain degree of heat applied to it, either by water, or by a naked fire, will curdle it. Spirit of Wine mixed with this liquor produces on it the same effect as heat. Blood, while circulating in the body of a healthy animal, and when newly taken from it, hath a mild taste, which discovers nothing like either an Acid or an Alkali; nor doth it shew any sign of either the one or the other in Chymical trials. When tasted with attention it betrays something like a savour of Sea-salt; because it actually contains a little thereof, which is found in the charred matter left in the retort after distillation, when carefully examined. We shewed that Milk also contains a little of this Salt. It enters the bodies of animals with the food they eat, which contains more or less thereof according to its nature. It plainly suffers no alteration by undergoing the digestions, and passing through the strainers, of the animal body. The case is the same with the other Neutral Salts which have a Fixed Alkali for their basis: we find them unchanged in the juices of animals into whose bodies they have been introduced. They are incapable of combining, as Acids do, with the oily parts; and so are dissolved by the aqueous fluids, of which nature makes use to free herself from those Salts, and discharge them out of the body; as shall be shewn when we come to speak of Urine and Sweat. Blood, like all other animal matters, is, properly speaking, susceptible of no fermentation but that of putrefaction. Yet it turns somewhat sour before it putrefies. This small degree of acetous fermentation is most sensible in flesh; and especially in the flesh of young animals, such as calves, lambs, chickens, &c. The quantity of pure water, which Blood, in its natural state, contains, is very considerable, and makes almost seven eighths thereof. If it be distilled, without being first dried, the operation will be much longer; because it will be necessary to draw off all this insipid phlegm with a gentle fire. There is no reason to apprehend that, by drying Blood in open vessels as directed, any of its other principles will be carried off with its Phlegm: for it contains no other substance that is volatile enough to rise with the warmth of a _balneum mariæ_. This may be proved by putting some undried Blood into a glass cucurbit, fitting thereto a head and receiver, and distilling, in a _balneum mariæ_, all that the heat of the bath, not exceeding the heat of boiling water, will raise: for, when nothing more will come over, you will find in the receiver an insipid phlegm only, scarce differing from pure water, except in having a faint smell like that of Blood; wherein it resembles all the phlegms that rise first in distillation, which always retain something of the smell of the matters from which they were drawn. That part of the Blood, which remains in the cucurbit after this first distillation, being put into a retort, and distilled with a stronger fire, yields exactly the same principles, and in the same proportion, as Blood dried in open vessels in the _balneum mariæ_: so that, if this Phlegm of Blood contain any principles, the quantity thereof is so small as to be scarce perceptible. The Volatile Alkali that rises with the Oil, when Blood is distilled in a retort with a degree of heat greater than that of boiling water, is either the production of the fire, or arises from the decomposition of an Ammoniacal Salt, of which it made a part. For we shall see, when we come to treat of this saline substance, that it is so extremely volatile as to exceed, in that respect, almost all other bodies that we know: and therefore if this Volatile Alkali pre-existed formally in the Blood, uncombined with any other matter capable, in some measure, of fixing it, it would rise at first almost spontaneously, or at least, on the first application of the gentlest heat. We have an instance of this in Blood, or any other animal matter, that is perfectly putrefied; which containing a Volatile Alkali, either formed or extricated by putrefaction, lets go this principle when distilled, even before the first phlegm: and, for this reason, when putrefied Blood is to be analyzed, it must by no means be dried, like fresh Blood, before distillation; for all the Volatile Alkali would by that means be dissipated and lost at once. The Volatile Alkali obtained from Blood that hath not undergone putrefaction, affords matter of some speculation. Indeed the separation of this Salt from Blood requires a degree of heat, vastly greater than that which is necessary to make it rise, when it is perfectly formed and disentangled: and this gives room to think that it is the result of a combination formed by the fire, during the distillation. But then this same degree of heat neither separates nor forms any Volatile Alkali in a great number of plants, or in milk, as hath been shewn. Yet it cannot be supposed that the blood of animals, which feed only on those plants or on milk, is any other than these very matters digested and rendered perfectly animal substances: whence it must be concluded, that, when vegetable substances are converted into animal substances, they undergo such alterations as render them capable of yielding, when analyzed, a principle that was not discoverable in them before. Now we know that this same principle, that is, the Volatile Alkali, is the product of putrefaction, or, which is the same thing, of the last degree of fermentation: and this, I think, makes the opinion of those more than probable, who believe that trituration and mechanical motion are not the only causes, that effect the conversion of food into an animal juice, but that fermentation hath a great share in this change. It is true, we do not find, in animal matters, any manifest token of an Ardent Spirit, an Acid, or a Volatile Alkali; nor, consequently, any substance that is an evident production of any of the three different degrees of fermentation: and yet, as substances perfectly animalized are exactly in the same state with vegetables that have undergone the first, and even the second, degree of fermentation, so that they are susceptible of putrefaction only, (or, at least, if they shew at first some faint tokens of acidity, they run immediately and rapidly into complete putrefaction); it is nevertheless probable, that vegetable matters, in order to their becoming animal substances, undergo certain changes and alterations, which have some resemblance with those produced by fermentation. This opinion is further confirmed by two other analogies, between animal matters, and vegetables advanced to the last stage of fermentation; which is, that they yield neither an Essential Oil nor a Fixed Alkali: for the coal, that remains in the retort after the distillation of Blood, being burnt in an open fire, discovers no Fixed Alkali in its ashes. The want of a Fixed Alkali in animal matters arises from hence, that their Acid is nearly in the same state with the Acid of vegetable matters which have undergone putrefaction; that is, it is so subtilized and attenuated, as to be fit to enter into the combination of a Volatile Alkali, and is no longer so intimately united with the fixed earth as to produce therewith a Fixed Alkali in the fire. Though Blood and other animal matters afford no Fixed Alkali, but, on the contrary, yield much Volatile Alkali, it doth not therefore follow that all the Acid, which those substances contained before they were analyzed, is employed in the production of a Volatile Alkali. We shall hereafter take notice of an animal matter which contains a great deal of Acid: and, not to depart from our present subject, it doth not appear to me to be a settled point among Chymists, whether or no Blood, when analyzed, yields a portion manifestly acid, and possessing all the properties of an Acid. Mr. Boerhaave, with some other Chymists, makes no mention of any Acid in his analysis of Blood. Mr. Homberg, on the contrary, says[18] expressly, that he constantly obtained an Acid from the Blood and flesh of different sorts of animals, of which he analyzed a great number. Mr. Boerhaave's authority is very respectable, and of great weight: on the other hand, Mr. Homberg's experiments are very conclusive, seem to be made with great care, and are all affirmative. This apparent diversity in the same analysis, delivered by these two great men, determined me to analyze Blood myself, and to examine scrupulously all the principles I could obtain from it. [18] Memoirs of the Academy of Sciences for 1712. I therefore distilled some Bullock's Blood in a retort with degrees of fire. Some Phlegm came over first, and then a Volatile Spirit. I changed my receiver; and on increasing the fire there arose, with the Volatile Spirit, a yellow Oil, a Volatile Salt in a concrete form, a russet liquor which smelled strong of Volatile Alkali, and seemed at first to be only a Spirit impregnated with much of that Salt: at last came a very thick fetid Oil. In this brown liquor, which comes off towards the end of the distillation, Mr. Homberg affirms the Acid to be contained: but, as it certainly is replete with a Volatile Alkali also, he alledges that it contains, at the same time, both a Volatile Alkali and the animal Acid; that these two Salts are distinct from each other, and not combined together in the form of an Ammoniacal Salt; that each of consequence possesses its peculiar properties; and that this liquor is at the same time both Acid and Alkaline; that it effervesces with Acids, and also changes the blue colours of plants to red. The Alkaline quality of this liquor is very evident, and discovers itself in every Chymical trial; but the same cannot be said of its Acid property. I dropped some of it on blue paper, the colour of which did not at first change in the least, nor acquire the faintest shade of redness. This experiment almost determined me to conclude that Mr. Homberg was mistaken: but some time afterwards I perceived that the blue paper began to turn red where it had been wetted, and that the red colour grew deeper and deeper as the paper dried: and this convinced me, that this liquor actually contains an Acid, as Mr. Homberg asserted; but, that the Volatile Alkali in this liquor, being much more copious than the Acid, had first entered the paper, and hindered the Acid from turning it red as usual; and that, as the Alkali evaporated, the Acid began to act, and produce the customary effect. Hence we see that the Acid of Blood, though extricated by distillation, is not easily perceived at first, because of the great proportion of Volatile Alkali, with which the liquor containing it is impregnated. This is probably what prevented its being discovered by several Chymists, who, it seems, did not suspect its existence, and therefore did not look for it. Mr. Homberg takes no notice of this little difficulty in his Memoir: but he relates an experiment which might have given occasion to suspect it. It is in his analysis of Human Blood. As the Acid in Human Blood is in less quantity, and less perceptible, than in the Blood of animals that live wholly on vegetables, he directs a second distillation of the brown liquor, which contains at once both the Volatile Alkali and the Acid, till very little thereof be left in the retort. _This residuum_, says he, _contains a very perceptible and distinct Acid_. There is reason to believe, from Mr. Homberg's directing the saline liquor to be distilled again, that he did not find the Acid sufficiently perceptible in it at first. Now a second distillation is a very good way to render it much more sensible. For though this animal Acid be volatile, the Volatile Alkali is still vastly more so; and therefore if the liquor containing both these saline substances be distilled, the Volatile Alkali must needs rise first, and leave the Acid alone, or almost alone, at the bottom of the retort. This is exactly the case in our experiment on blue paper; the operation being here performed with a small quantity, and much more expeditiously, as appears from our account of it. It is not at all surprising that the Volatile Alkali and animal Acid, though confounded in the same liquor, should not be united together and converted into a Neutral Ammoniacal Salt. Mr. Homberg pretends that these two saline matters do not act upon each other, because they are too much dephlegmated. The oily parts, with which they are both loaded, may also contribute thereto: nor is this unprecedented; the same thing being observed of the Acid and the Volatile Alkali of several vegetable substances. Mr. Homberg, justly suspecting that there might be some difference between the condition of the Acid in the Blood of animals that feed altogether on vegetables, and that in the blood of those that feed only on flesh, examined likewise, by decomposition, the Blood and the flesh of some carnivorous animals. In these also he found an Acid; and it doth not appear that he observed any great difference, in this respect, between their Blood and that of other animals. The difference he found between the Blood of young, and that of grown, or old, animals, with respect to the Acid, seems, by his account, to be more considerable; the Blood of the former containing much more of it than that of the latter: and this is so much the more probable, as we know that the flesh of young animals grows sour, before it putrefies, more sensibly than that of old ones. We shall conclude this head with a remark concerning the management required in distilling Blood. When the operation is advanced to a certain point, the matter contained in the retort often swells so as to stop the neck of that vessel entirely, and by that means makes it burst with an explosion. To avoid this inconvenience, a very small quantity of Blood must be put into the retort, and the fire must be governed very warily. I have also found that this accident may generally be prevented by mixing the Blood with some matter that can afford no principle by distillation; such as pounded glass or fine sand. PROCESS II. _Flesh analyzed. Instanced in Beef._ Into an alembic or retort, placed in a sand-bath, put some lean Beef, from which you have carefully separated all the fat. Distil till nothing more will rise. In this first distillation a phlegm will come over, weighing at least half the mass of the distilled flesh. In the retort you will find a matter almost dry, which you must afterwards distil, with a naked fire, in a reverberating furnace, taking the usual precautions. There will come over at first a little phlegm replete with Volatile Alkali; then a Volatile Alkali in a dry form, which will stick to the sides of the vessel; and also a thick Oil. After the distillation there will be left in the retort a black, shining, light coal. Burn it to ashes in the open air, and lixiviate those ashes: the water of the lixivium will have no Alkaline property, but will shew some tokens of its containing a little Sea-salt. _OBSERVATIONS._ This analysis of Beef is taken from a Memoir given in by Mr. Geoffroy in 1730, the purpose of which was a Chymical examination of the meat commonly used to make broth. The flesh of an animal, as appears from the process, yields much the same principles with its Blood: and it cannot be otherwise; because it is formed all together of materials furnished by the Blood. Mr. Geoffroy observes, that the first phlegm, drawn off from it in the _balneum mariæ_, produces a white precipitate in a solution of Corrosive Sublimate; which shews it to contain a little Volatile Alkali: but the quantity thereof must be very small; seeing the phlegm that contains it smells only like broth, and not like a Volatile Alkali; one particle of which, we know, is capable of affecting the organ of smelling very sensibly. As to the Acid of flesh, there is great reason to believe that it is conditioned exactly like that of Blood. The ashes of the _caput mortuum_ of flesh, burnt in an open fire, attract the moisture of the air, as Mr. Geoffroy remarks, and increase in weight, though they contain no Fixed Alkali. However, this is not at all surprising; since they contain some Sea-salt, the known property whereof is to grow moist in the air. The flesh of animals contains much matter that is soluble in water. Mr. Geoffroy examined separately that part of flesh which water is capable of dissolving. With this view he boiled four ounces of beef with three pints of water, in a very close vessel, and repeated the operation six times with equal quantities of fresh water; in order to extract, as far as possible, all the juices of the meat. These broths he put all together, the last of them having but a faint smell of very weak veal broth: he evaporated them over a slow fire, filtering them towards the end of the evaporation, to separate an earthy part; and there remained in the vessel a moderately solid extract, which soon grew moist in the air. This extract, being analyzed, yielded a dram and two grains of Volatile Salt, which adhered to the sides of the receiver; not in ramifications, as Volatile Salts usually do, but in flat crystals, mostly in the form of parallelopipeds. The Spirit and the Oil, which came over together after the Volatile Salt, weighed thirty-eight grains. Salt of Tartar being mixed with this Volatile Salt seemed to increase its strength; which gives room to suspect that the latter contains an Ammoniacal Salt. The charred matter left in the retort weighed but six grains. Its lixivium gave some tokens of Sea-salt, by making a white precipitate in a solution of quick-silver. The mass of fleshy fibres, that was exhausted by boiling, being dried and analyzed in the same manner, yielded a Volatile Spirit, a Volatile Salt in a concrete form, which stuck to the sides of the receiver in ramifications as usual; and a thick fetid Oil. There now remained in the retort a charred matter, which being burnt in the open air or not burnt, shewed not the least sign of its containing any saline matter. This method of analyzing flesh, by boiling it at first in water, in order to extract all that can be dissolved by this menstruum, shews us that animal flesh contains an Oil, which is in a saponaceous state: for the extract made therefrom, by water, yields in distillation a considerable quantity of Oil, which was perfectly dissolved in the water, while that extract was in the diluted state of broth, and before it was analyzed. It is remarkable that the Volatile Salt, yielded by the extract of flesh, is different from that which is obtained out of the flesh itself, when nothing hath been extracted from it. This Salt, as Mr. Geoffroy observed, differs from the common Volatile Alkalis in the form of its crystals; which made that Chymist justly consider it as a Salt of a somewhat Ammoniacal nature; a kind of Essential Salt of flesh. There is reason to think that this Salt, when dissolved in the water in which we boil flesh, is separated therefrom, by the action of fire, with more ease than while it remains combined with the other principles, in the substance of the flesh; that its separation, in the latter case, requiring a greater degree of heat, it is thereby decomposed; and that the Volatile Alkali, which is obtained from flesh distilled in the usual manner, is only one of the parts that constituted the Ammoniacal Salt thereby decomposed. The charred matter remaining, after the distillation of flesh first exhausted by boiling, yields nothing saline; because the Sea-salt, which is the only Fixed Salt it could contain, was dissolved by the water together with the matter of the extract. Mr. Geoffroy likewise examined what parts of flesh Spirit of Wine is capable of dissolving. For this purpose he took four ounces of Beef, dried in the _balneum mariæ_, poured on it an equal weight of well rectified Spirit of Wine, and left the whole in digestion for a considerable time. The Spirit extracted from the Beef a weak tincture, and separated from it some drops of Oil: it acquired a brown colour, and a faint smell. Mr. Geoffroy found, by several experiments, that the Spirit of Wine had taken up a portion of the Ammoniacal, or Essential, Salt of the flesh. With respect to the Oil, if any at all were dissolved, it could be but very little; for that which the Spirit separated, and which retained its natural form, was certainly not dissolved: seeing in that case it would not have been perceived, but would have made a homogeneous liquor, to appearance, with the Spirit of Wine. PROCESS III. _Bones analyzed. Instanced in Ox-bones._ Cut into pieces the Bones of a leg of beef, carefully separating all the marrow. Put them into a retort, and distil them in a reverberating furnace, as usual. A phlegm will come over first; then a Volatile Spirit, which will become stronger and stronger; afterwards a Volatile Salt in a dry form, with some Oil; and, lastly, a black Oil, with a little more Volatile Salt. There will be left in the retort a charred matter, from which a little Sea salt may be extracted. Reduce this charred matter to ashes, by burning it in the open air. These ashes will give some slight tokens of a Fixed Alkali. _OBSERVATIONS._ The analysis of Bones proves that they consist of the same principles with flesh and blood; and the same may be said, in general, of all matters that are truly animal, or that actually constitute any part of an animal. Nevertheless, we find in the ashes of Bones somewhat of an Alkaline quality; seeing they make a red precipitate in a solution of Corrosive Sublimate: and yet a true Fixed Alkali cannot be obtained from them. These ashes are probably in the same case with quick lime; which hath certain properties of Alkaline Salts, though no Salt of that kind can be extracted from it. Mr. Geoffroy analyzed Bones in the same manner as he did flesh; that is, he at first made a strong decoction of them with water, and then examined and distilled apart the extract afforded him by that decoction, and the Bones deprived of that extract. On this analysis he made two remarkable observations. The first is, that Bones yielded to boiling water their principles and their Volatile Salts, both sooner and more copiously than flesh did: for in the analysis which Mr. Geoffroy made of several sorts of flesh, though he robbed them in a manner of all their principles by boiling, yet their dried fibres afterwards yielded a considerable quantity of Volatile Salt; whereas the Bones, of which he had made an extract by boiling, afforded him but a very small quantity thereof when analyzed. The second observation worthy of notice which Mr. Geoffroy made on his analysis of Bones is this; the Salt, which, as was shewn in the analysis of flesh, was resolved by the water wherein he boiled the flesh, and consequently arose when he distilled the extract obtained from that decoction, and crystallized in the form of parallelopipeds, took a quite different turn in the analysis of Bones. None of it appeared in distilling the extract made by decoction, but arose in distilling the boiled Bones, that were exhausted of almost all their other principles by the decoction with water. These differences probably arise from the different contexture of the animal matters in which they are observed. This analysis of Bones may serve as a pattern for analyzing all the solid parts of animals, such as horns, hoofs, ivory, &c. PROCESS IV. _Animal Fat analyzed. Instanced in Mutton-Suet._ Put as much Mutton-Suet as you please into a glass retort, only taking care that the vessel be but half-full; and distil with degrees of fire as usual. A phlegm smelling of the Suet will rise first, and soon grow very acid. After this some drops of Oil will come over, and be followed by a matter like Oil, in appearance, when it comes over; but it will fix in the receiver, and acquire a consistence somewhat softer than Suet. This kind of Butter of Suet will continue to rise to the end of the distillation; and there will be left in the retort a small quantity of charred matter. _OBSERVATIONS._ Though animal Fat be a substance that hath passed through all the strainers of the body; though it hath undergone all the elaborations necessary to form an animal matter, and become itself part of the animal: it contains, nevertheless, as its analysis shews, principles differing greatly from those of all other animal matters: so that it must be classed, in some sort, by itself. It consists almost entirely of Oil: but this Oil is in a concrete form, and observes the general rule of all concreted oily matters, which owe their consistence wholly to the Acid that is combined with them. The rule is evidently so general, that it extends even to the animal kingdom, where, in all other instances, Acids seem to be almost annihilated. All we said above on the subject of Butter must be applied here: for animal Fat, properly so called, and Butter, do not, in my opinion, differ sensibly from each other, with respect to their analysis. And therefore there is great reason to believe, that what is Butter in Chyle, or Milk, becomes Fat when fixed in the animal body. It is a kind of repository, in which nature lays up and confines the Acid that is unnecessary to the animal composition, and which she could not any other way eliminate. I made choice of Mutton-Suet for an instance of the analysis of Fat; because this Fat, being the firmest of any, must contain a stronger and more perceptible Acid. When it is thus distilled, the part which remains fixed hath much less consistence than the Suet had before; which arises from its having lost part of its Acid. Repeated distillations will deprive it of a much greater quantity thereof, and so reduce it into an Oil that will always remain clear and fluid. Not one particle of Volatile Alkali is obtained by distilling Suet: but then the experiment will not succeed as it ought, unless care be taken to free the Suet perfectly from all the membranes, and all the particles of flesh and blood that may be mixed with it; for, if it should be distilled without this precaution, those heterogeneous matters mingled with it would yield a great deal of Volatile Alkali in distillation; which might impose on the Artist, and make him think the Salt came actually from the Suet. Suet that hath been often melted, as the tallow, for instance, of which candles are made, is sufficiently purified: of this I made use in my analysis, and it yielded me no Volatile Alkali; at least I could perceive none. In conclusion, all that hath been said, on several occasions, touching the properties of concreted oily matters, may be applied to Suet. I shall only observe here, that it is one of those that manifest no Acidity, and consequently that in its natural state it is not soluble in Spirit of Wine, and only becomes soluble in that menstruum by degrees, as its Acid is extricated by repeated distillations: and on this account it ought to be classed with Bees-Wax, and other oily compounds of that kind. PROCESS V. _Eggs analyzed. Instanced in Pullet's Eggs._ Put some Hen's Eggs in water, and boil them till they be hard. Then separate the Yelks from the Whites. Cut the Whites into little bits; put them into a glass cucurbit; fit on a head and receiver; distil in a _balneum mariæ_ with degrees of fire, raising it towards the end to the strongest heat which that bath can give; that is, to the heat of boiling water. There will come over an aqueous liquor, or insipid phlegm; the quantity whereof will be very considerable, seeing it will make about nine-tenths of the whole mass of the Whites of the Eggs. Continue your distillation, and keep the water in the bath constantly boiling, till not a drop more of liquor will ascend from the alembic. Then unlute your vessels. In the cucurbit you will find your Whites of Eggs considerably shrunk in their bulk. They will look like little bits of brown glass, and be hard and brittle. Put this residuum into a glass retort, and distil, as usual, in a reverberating furnace with degrees of heat. There will come over a Volatile Oily Spirit, a yellow Oil, a Volatile Salt in a dry form, and, at last, a black thick Oil. There will be left in the retort a charred matter. Reduce also into the smallest pieces you can the hard Yelks of the Eggs which you separated from the Whites. Set them in a pan over a gentle fire: stir them with a stick till they turn a little brown, and discharge a substance like melted marrow. Then put them into a new strong canvass bag, and press them between two iron plates well heated; whereby you will obtain a considerable quantity of a yellow Oil. Let what remains in the bag be distilled in a retort set in a reverberating furnace: it will give you the same principles as you got from the Whites. _OBSERVATIONS._ Of the two perfectly distinct substances that constitute the Egg, the Yelk contains the embryo of the chick, and is destined to hatch it: the White is to serve for the nourishment of the chick when it is formed. These two matters, though they contain the very same principles, yet differ considerably from each other; and chiefly in this, that their principles are not in the same proportions. The White of an Egg contains so much phlegm, that it seems to consist almost totally thereof. All the aqueous liquor, obtained by distilling it in the _balneum mariæ_, is, properly speaking, nothing but pure water; for no Chymical trial can discover in it either an Acid or a Volatile Alkali; or any very perceptible Oily part. And yet it must contain some Oil, because the liquor that rises last is a little bitterish to the taste, and smells somewhat of empyreuma. But the principles from which it derives these properties are in too small quantities to be distinctly perceived. If, instead of distilling the hard White of an Egg, with a view to draw off the great quantity of water it contains, you leave it some time in an air that is not too dry, the greatest part of its moisture separates spontaneously, and becomes very sensible. In all probability this is the effect of a beginning putrefaction, which attenuates this substance, and breaks its contexture. The liquor thus discharged by the White of an Egg thoroughly dissolves Gum-Resins, and particularly Myrrh. If you desire to dissolve Myrrh in this manner, cut a hard-boiled Egg in halves; take out the Yelk; put the powdered Gum-Resin into the cavity left by the Yelk; join the two halves of the White; fasten them together with a thread, and hang them up in a cellar. In a few days time the Myrrh will be dissolved by the moisture that issues from the White of the Egg, and will drop into the vessel placed underneath to receive it. This liquor is improperly called _Oil of Myrrh per deliquium_. All the properties of the Whites of Eggs, as well as the principles obtained by analyzing them, are the same with those of the lymphatic part of the blood; so that there is a great resemblance between these two substances. As to the Yelk, it is plain from its analysis that Oil is the predominant principle thereof. If the Yelk of an Egg be mixed with water, the Oil with which it is replete, and which is by nature very minutely divided, diffuses itself through the whole liquor, and remains suspended therein by means of its viscosity. The liquor at the same time becomes milk-white like an emulsion, and is in fact a true animal emulsion. In order to obtain the Oil of Eggs by expression with the more ease, care must be taken to chuse Eggs that are seven or eight days old; because they are then a little less viscous. Nevertheless, their viscosity is still so great that they will not easily yield their Oil by expression: and therefore, in order to attenuate and destroy entirely this viscosity, they must be torrefied before they are put to be pressed. The Oil of Eggs, like all other oily animal matter, seems analagous to the Fat Oils of vegetables. It hath all the properties that characterise those Oils. Its colour is yellow, and it smells and tastes a little of the empyreuma, occasioned by torrefying the Yelks. It is rendered somewhat less disagreeable by being exposed to the dew for thirty or forty nights, if care be taken to stir it often in the mean time. To conclude: all the principles, both in the Yelk and the White of an Egg, are the same as those found in Blood, Flesh, and all other matters that are perfectly animal. CHAP. III. _Of the_ EXCREMENTS _of_ ANIMALS. PROCESS I. _Dung analyzed. Instanced in Human Excrement. Mr. Homberg's Phosphorus._ Take any quantity you please of human Excrement, and distil it in a glass alembic set in the _balneum mariæ_. You will obtain an aqueous, clear, insipid liquor; which will nevertheless have a disagreeable odour. Having urged the distillation as far as is possible, with the heat of this bath, unlute your vessels, and you will find at the bottom of the cucurbit a dry matter, making about an eighth part only of what you put into it. Put this residuum into a glass retort, and distil in a reverberating furnace, with degrees of heat. You will obtain a Volatile Spirit, and a Volatile Salt, with a fetid Oil; and a charred matter will be left in the retort. _OBSERVATIONS._ Mr. Homberg made a great many experiments on the dung of animals; concerning which he composed two Memoirs published in the Academy's collection for 1711. That Chymist tells us, that, in distilling Excrement, he aimed not so much at discovering the principles of which it consists, as he was desirous to satisfy a friend of his, who had earnestly entreated him to try whether he could not extract therefrom a clear Oil, having no bad smell; because he had seen, as he said, Mercury fixed into pure Silver by such an Oil. Mr. Homberg's labour had the usual fate of all enterprises of this nature. He actually found the art of drawing from Excrement a clear scentless Oil; but, in whatever way he applied it to Mercury, it produced no change in that metallic substance. However, as Mr. Homberg was a man of sagacity, and knew how to improve every hint offered by his experiments, he made several curious discoveries on this occasion; of which we shall give a concise account, after we have made some remarks on the principles obtained from Excrement by the method described in the process. This substance, consisting of matters subject to putrefaction, hath constantly a fetid smell, like that of all putrid matters; having been for some time confined in a warm, moist place, which we know promotes putrefaction, and even quickly produces it. Yet the analysis thereof proves that it is not putrefied, or at least not entirely so: for all putrefied matters contain a Volatile Alkali perfectly formed and extricated; and, as this principle rises with less heat than that of boiling water, it always comes over first in distillation. Now we have seen that, with the heat of boiling water, it parts with nothing but an insipid phlegm, containing no Volatile Alkali: a sure proof that the fecal matter is not completely putrefied. There is nothing remarkable in the Volatile Salt and fetid Oil, which rise with a degree of heat greater than that of boiling water. They are common productions, of which we have made frequent mention in several of the preceding analyses; and therefore they need not now detain us from proceeding to give a summary account of Mr. Homberg's chief discoveries. One of the methods by which Mr. Homberg endeavoured to obtain from Excrement a clear Oil, without any bad smell, was to separate its earthy and gross parts, by filtering it before he distilled it. "For this purpose he diluted Excrement newly discharged with hot water, using a quart of water to an ounce of feces. Then he let the mixture stand to cool, and, the gross parts falling to the bottom, he poured off the water by inclination. This liquor he filtered through brown paper, and evaporated to a pellicle over a gentle fire. There shot in it long crystals of four, five, and six sides, which Mr. Homberg thinks may be called the Essential Salt of Excrement. They resemble Salt-petre, in some measure, and deflagrate in the fire much like it; with this difference, that their flame is red, and they burn slowly; whereas the flame of Salt-petre is white and very vivid: probably, says Mr. Homberg, because there is too much of an oily matter in the one, and less in the other. "Mr. Homberg distilled this Salt in a glass retort with degrees of fire, and at last with a very violent one. At first there came over an aqueous liquor, sharp and acid, which was followed by a brown fetid oil, smelling very strong of empyreuma. This distillation he attempted four several times; and each time the matter in the retort took fire, just when the Oil began to come off." The Salt which Mr. Homberg obtained from excrement is very remarkable. We shall have occasion to speak of it in another place, and shall only observe here, that its Nitrous character is by no means ambiguous: its deflagrating on live coals convinced Mr. Homberg of its being a true Nitre. But its constantly taking fire in the retort, as oft as distilled, is a sure proof that it is a Nitrous Salt: for Nitre only hath the property of thus taking fire in close vessels, and making other combustible matters burn along with it. The process by which Mr. Homberg at last obtained from Excrement a clear oil without any bad smell is curious, and worthy of a place here; on account of the views and occasions of reflection which it may open. "Mr. Homberg having tried in vain, by distilling Excrement a great many different ways, to obtain from it such an Oil as he wanted, resolved to employ fermentation, the effect whereof is to change the disposition of the principles of mixts. With this view he dried some Excrement in the water-bath, and, having pulverized it, poured thereon six times its weight of phlegm that had been separated from it by distillation, and put the whole into a large glass cucurbit, covered with an inverted vessel that fitted exactly into it, and was close luted. This vessel he set in a _balneum mariæ_ for six weeks, keeping up such a gentle heat as would not burn one's hand; after which he uncovered the cucurbit, and having fitted thereto a head and a receiver, distilled off all the aqueous moisture in the _balneum mariæ_ with a very gentle heat. It had now lost almost all its bad smell, which was changed into a faint one. It came over somewhat turbid, whereas it was very clear when put into the cucurbit. Mr. Homberg found this water to have a cosmetic virtue: He gave some of it to persons whose complexion, neck, and arms, were quite spoiled, being turned brown, dry, rough, and like a goose skin: they washed with it once a day, and, by continuing the use of this water, their skin became very soft and white." The dry matter, that remained in the bottom of the cucurbit after distillation, had lost about a twentieth part of its weight; that is, of twenty ounces, put at one time into the cucurbit, somewhat less than nineteen ounces remained. Mr. Homberg suspects that it was not so dry when put into the cucurbit as when it was taken out. Perhaps also the species of fermentation which the matter underwent had attenuated and volatilized some part of it; so that it came over with the phlegm in distillation. The turbidness of that phlegm, which was clear and limpid before, seems to countenance this conjecture. "The dry matter left in the cucurbit after the first distillation, had not the least smell of feces: on the contrary, it had an agreeable aromatic odour; and the vessel in which Mr. Homberg had digested it, being left open in a corner of his laboratory, acquired in time a strong smell of Ambergris. It is surprising, as Mr. Homberg justly observes, that digestion alone should change the abominable smell of Excrement into an odour as agreeable as that of Ambergris. "This dry matter he powdered coarsely, and put two ounces thereof at once into a glass retort, that would hold about a pound or a pound and half of water. This he distilled in a sand-bath with a very gentle heat. A small quantity of an aqueous liquor came over first, and then an Oil as colourless as spring-water. Mr. Homberg continued the same gentle degree of heat, till the drops began to come off a little reddish; and then he changed the receiver, stopping that which contained the clear Oil very close with a cork. Having carried on the distillation with a fire gradually augmented, there came over a considerable quantity of red Oil; and there remained in the retort a charred matter which burnt very readily." The clear Oil, without any ill smell, which Mr. Homberg obtained from the fecal matter by this process, was the very thing he was in search of, and which he had been assured would convert Mercury into fine fixed Silver: yet he ingenuously owns, that, whatever way he applied it, he could never produce any change in that metallic substance. We shall now proceed to the other discoveries made by Mr. Homberg on this occasion. In his attempt to obtain a clear Oil from Excrement, he distilled it with different additaments, and amongst the rest with Vitriol and Alum. He found that the matters left in the retort, when he made use of these Salts, being exposed to the open air, took fire of themselves; that they kindled combustible matters; in a word, that they were a true Phosphorus, of a species different from all then known. Pursuing these first hints, he sought and found the means of preparing this Phosphorus by a way much more expeditious, certain, and easy. His process is this. "Take four ounces of Feces newly excreted: Mix therewith an equal weight of Roch-Alum coarsely powdered: put the whole into a little iron pan that will hold about a quart of water, and set it over a gentle fire under a chimney. The mixture will melt, and become as liquid as water. Let it boil with a gentle fire, constantly stirring it; breaking it into little crumbs, and scraping off with a spatula whatever sticks to the bottom or sides of the pan, till it be perfectly dry. The pan must from time to time be removed from the fire, that it may not grow red-hot, and the matter must be stirred, even while it is off the fire, to prevent too much of it from sticking to the pan. When the matter is perfectly dried, and in little clots, let it cool, and powder it in a metal mortar. Then put it again into the pan, set it over the fire, and stir it continually. It will again grow a little moist, and adhere together in clots, which must be continually bruised and roasted till they be perfectly dry; after which they must be suffered to cool, and then be pulverized. This powder must be returned a third time to the pan, set on the fire, roasted and perfectly dried: after which it must be reduced to a fine powder, and kept in a paper in a dry place. This is the first or preparatory operation. "Take two or three drams of this powder. Put it into a little matrass, the belly of which will hold an ounce or an ounce and half of water, and having a neck about six or seven inches long. Order it so that your powder shall take up no more than about a third part of the matrass. Stop the neck of the matrass slightly with paper: then take a crucible four or five inches deep: in the bottom of the crucible put three or four spoonfuls of sand: set the matrass on this sand, and in the middle of the crucible, so as not to touch its sides. Then fill up the crucible with sand, so that the belly of the matrass may be quite buried therein. This done, place your crucible, with the matrass, in the midst of a little earthen furnace, commonly called a _Stove_, about eight or ten inches wide above, and six inches deep from the mouth to the grate. Round the crucible put lighted coals about half way up, and when it hath stood thus half an hour, fill up with coals to the very top of the crucible. Keep up this fire a full half-hour longer, or till you see the inside of the matrass begin to be red. Then increase your fire, by raising your coals above the crucible. Continue this strong heat for a full hour, and then let the fire go out. "At the beginning of this operation dense fumes will rise out of the matrass, through the stopple of paper. These fumes issue sometimes in such abundance as to push out the stopple; which you must then replace, and slacken the fire. The fumes cease when the inside of the matrass begins to grow red; and then you may increase the fire without any fear of spoiling your operation. "When the crucible is so cold that it may be safely taken out of the furnace with one's hand, you must gradually draw the matrass out of the sand, that it may cool slowly, and then stop it close with a cork. "If the matter at the bottom of the matrass appear to be in powder when shaken, it is a sign the operation hath succeeded: but if it be in a cake, and doth not fall into powder on shaking the matrass, it shews that your matter was not sufficiently roasted and dried in the iron pan, during the preparatory operation." Since Mr. Homberg, Mr. Lemeri the younger hath made a great many experiments on this Phosphorus, which may be seen in the Memoirs of the Academy for 1714 and 1715. In those Memoirs Mr. Lemeri hath shewn, that Excrement is not the only matter capable of producing this Phosphorus with Alum; but that, on the contrary, almost all animal and even vegetable matters are fit for this combination; that though Mr. Homberg mixed Alum in equal quantities only with the fecal matter, it may be used in a much greater proportion, and, in certain cases, will succeed the better; that, according to the nature of the substances to be worked on, the quantity of that Salt may be more or less increased; and that whatever is added, more than the dose requisite for each matter, serves only to lessen the virtue of the Phosphorus, or even destroys it entirely: that the degree of fire applied must be different according to the nature of those matters; and, lastly, that Salts containing exactly the same Acid with that of Alum, or the Acid of those Salts separated from its basis and reduced into Spirit, do not answer in the present operation: which shews, says Mr. Lemeri, that many sulphureous matters may be substituted for Excrement in this operation; but that there are no Salts, or very few if any, that will succeed in the place of Alum. Nevertheless, a Chymist, who lately communicated to the Academy a great number of experiments on this Phosphorus, found that any Salt containing the Vitriolic Acid may be substituted for Alum. This Phosphorus, made either by Mr. Homberg's or by Mr. Lemeri's method, shines both by day and by night. Besides emitting light, it takes fire soon after it is exposed to the air, and kindles all combustible matters with which it comes in contact; and this without being rubbed or heated. Mess. Homberg and Lemeri have given the most probable and the most natural explanation of the cause of the accension and other phenomena of this Phosphorus. What they say amounts in short to what follows. Alum is known to be a Neutral Salt, consisting of the Vitriolic Acid and a calcareous earth. When this Salt is calcined with the fecal matter, or other substances abounding in Oil, the volatile principles of these substances, such as their Phlegm, their Salts, and their Oils, exhale in the same manner as if they were distilled; and there is nothing left in the matrass, when those principles are dissipated, but a charred matter, like that which is found in retorts wherein such mixts have been decomposed by distillation. This remainder therefore is nothing but a mixture of Alum and charcoal. Now, as the Acid of this Salt, which is the Vitriolic, hath a greater affinity with the phlogiston than with any other substance, it will quit its basis to unite with the phlogiston of the coal, and be converted by that union into a Sulphur. And this is the very case; of which we have certain proofs in the operation for preparing this Phosphorus: for when, after the volatile principles of the oily matter are drawn off, the fire is increased, in order to combine closely together the fixed parts that remain in the matrass, that is, the Alum and the charred matter, we perceive at the mouth of the matrass a small blue sulphureous flame, and a pungent smell of burning Sulphur. Nay, when the operation is finished, we find a real Sulphur sticking in the neck of the matrass; and, while the Phosphorus is burning, it hath plainly a strong sulphureous smell. It is therefore certain that this Phosphorus contains an actual Sulphur; that is, a matter disposed to take fire with the greatest ease. But though Sulphur be very inflammable, it never takes fire of itself, without being either in contact with some matter that is actually ignited, or else being exposed to a considerable degree of heat. Let us then see what may be the cause of its accension, when it is a constituent part of this Phosphorus. We mentioned just now that the Acid of the Alum quits its basis, in order to form a Sulphur by combining with the Phlogiston of the coal. This basis we know to be an earth capable of being converted into Lime; and that it is actually converted into Quick-lime by the calcination necessary to produce the Phosphorus. We know that new-made Lime hath the property of uniting with water so readily, that it thereby contracts a very great degree of heat. Now when this Phosphorus, which is partly constituted of the basis of the Alum converted into Quick-lime, is exposed to the air, the Lime instantly attracts the moisture of which the air is always full, and by this means, probably, grows so hot as to fire the Sulphur with which it is mixed. Perhaps also the Acid of the Alum is not totally changed into Sulphur; some part thereof may be only half disengaged from its basis, and in that condition be capable of attracting strongly the humidity of the air, of growing very hot likewise by imbibing the moisture, and so of contributing to the accension of the Phosphorus. There is also room to think that all the Phlogiston of the charred matter is not employed in the production of Sulphur in this Phosphorus, but that some part of it remains in the state of a true coal. The black colour of the unkindled Phosphorus, and the red sparkles it emits while burning, sufficiently prove this. The explanation of the accension of this Phosphorus, as here given by Mess. Homberg and Lemeri, is very ingenious, and in the main just; but yet, in my opinion, the subject deserves a more thorough examination. PROCESS II. _Human Urine analyzed._ Put some Human Urine into a glass Alembic; set it in a water-bath, and distil till there remain only about a fortieth part of what you put in; or else evaporate the Urine, in a pan set in the _balneum mariæ_, till it be reduced to the same quantity. With this heat nothing will exhale but an insipid Phlegm, smelling however like Urine. The residuum will, as the evaporation advances, become of a darker and darker russet, and at last acquire an almost black colour. Mingle this residuum with thrice its weight of sand, and distil it in a retort set in a reverberating furnace, with the usual precautions. At first there will come over a little more insipid Phlegm like the former. When the matter is almost dry, a Volatile Spirit will rise. After this Spirit, white vapours will appear on increasing the fire; a yellow oily liquor will come off, trickling down in veins; and together with this liquor a concrete Volatile Salt, which will stick to the sides of the receiver. At last there will come over a deep-coloured fetid Oil. In the retort there will remain a saline earthy residuum, which being lixiviated will yield some Sea-salt. _OBSERVATIONS._ Urine must be considered as an aqueous liquor replete with all the saline matters which are of no use to the body, either for nourishment or health: it is a lixivium of animal matters, prepared by nature for dissolving and separating from them all the unnecessary Salts. It contains a very large quantity of almost pure phlegm, which evaporates with the heat of a water-bath. The residue of the Urine, from which this phlegm is separated by the first distillation, though thereby rendered considerably thicker, doth not coagulate, or curdle in the least, like Milk or Blood; which shews that it contains no parts analagous to those of these two nutritious liquors. Yet it contains oily and saline parts, disposed like those of truly animal matters; as appears from the Spirit, the Volatile Salt, and the Oil, obtained from it by distillation; which are, in every respect, perfectly like the same principles yielded by other animal substances. But, if the animal that made the Urine took in with its food any of the Neutral Salts, which cannot be decompounded by digestion; that is, of those chiefly which consist of Acids and Alkalis, the Urine will contain, over and above the other parts of that animal, almost all the Neutral Salt that entered into its body. Accordingly human Urine is replete with a considerable quantity of Sea-salt, because men eat a great deal of it. It is found, after the distillation of the Urine, united with the _caput mortuum_ left in the retort; because, being of a fixed nature, it doth not rise with the volatile principles in distillation. Besides this Sea-salt, Urine contains another Salt of a singular nature, which crystallizes differently from Sea-salt. In this Salt, according to Mr. Marggraff's experiments mentioned on the subject of Phosphorus, is contained the Acid necessary to produce the Phosphorus of Urine. There is reason to think that this Salt is a Sea-salt, disguised by the fat matters with which it combines during its stay in the animal body. Mr. Boerhaave calls it the Essential Salt of Urine. If you desire to have it by itself, you must evaporate the Urine, with a gentle heat, to the consistence of fresh cream, filter it, and let it stand quiet in a cool place. Crystals will at length shoot therein, and adhere to the sides of the vessel. These crystals are the Salt you want: they are brown and oily. If you desire to have them purer, you must dissolve them in warm water, filter the solution, and set it by to shoot. This operation repeated several times will render them clear and transparent. Mr. Schlosser, a young and very promising Chymist, is the last who hath made any experiments on this curious Salt of Urine. Those who are desirous of a particular account of its properties may consult his dissertation, printed at Leyden in 1753, as well as Mr. Marggraff's excellent Memoirs, printed among those of the Academy of Berlin. The chief result of Mr. Schlosser's experiments is, first, that this Salt may be obtained from recent Urine, and even in greater quantities than from putrid Urine, and that too in very little time: seeing it crystallizes in twenty-four hours, after due evaporation. Secondly, that this Salt is a Neutral Ammoniacal Salt, consisting of a Volatile Alkali, (which can never be extracted from it but in a liquid form, like that which is separated from Urine by the addition of Lime); and of an Acid of a very singular nature, the most remarkable property of which is, its being so fixed as to resist the violence of fire, and turn into a sort of glass rather than exhale in vapours. This is that Acid which, according to Mr. Marggraff's experiments, forms the combination of Phosphorus when united with the Phlogiston. The other properties of this singular Acid are the principal objects of Mr. Marggraff's inquiries. It follows, in the third place, from Mr. Schlosser's experiments, that this Acid, being combined to the point of saturation with a common Volatile Alkali, forms a true, regenerated Salt of Urine; and that, by this union, the nature of the Volatile Alkali is so changed, that it cannot afterwards appear by itself in a concrete form, but is always fluid, like that which is extricated by the additament of lime. If Fixed Alkalis be mixed with fresh Urine, they immediately separate from it a Volatile Alkali; and, if the mixture be quickly put into an alembic, and distilled, the first liquor that rises is a Volatile Spirit: or else a Volatile Alkali in a concrete form will rise first, provided the Fixed Alkali made use of be not liquid, and the Urine be dephlegmated. Herein Urine resembles other animal matters: for Fixed Alkalis produce the same effect on them. This affords us good grounds for believing that all animal matters contain a Neutral Salt of an Ammoniacal nature, which the Fixed Alkali decomposes, as it doth all other Ammoniacal Salts. Quick-lime also extricates from Urine a Volatile Alkali, still more quick and pungent than that which is separated by a Fixed Alkali, and which constantly remains liquid without ever putting on a concrete form: and this is another proof of the existence of the Ammoniacal Salt above-mentioned; for quick-lime hath just the same effect on Sal-Ammoniac, as we shall see in its place. Mr. Schlosser's experiments, compared with those now mentioned, seem to shew that the Urine contains several distinct sorts of Ammoniacal Salts. Of all the liquors which animals afford, Urine putrefies the most easily, and by putrefaction parts with, or forms, the greatest quantity of Volatile Alkali. If it be distilled when putrefied, there comes over first a Spirit impregnated with much Volatile Alkali; then an aqueous liquor, which Van Helmont assures us is a medicine of wonderful efficacy in dissolving the stone in the bladder. When all this water is come over, and the remaining matter is almost dry, there ascends, on increasing the fire, a yellow Oil, together with a Volatile Salt. After this there remains in the retort a black charred earthy matter, containing a great deal of Sea-salt. If this matter be calcined in the open air, in order to consume its Phlogiston, and be afterwards lixiviated, all the Sea-salt it contains may by this means be easily separated; nothing but its earth being left behind. This _caput mortuum_ contains also the materials proper for forming Kunckel's Phosphorus; and if, instead of calcining it in the open air, it be urged with a violent fire, in close vessels, it will yield a Phosphorus: but then all the precautions recommended on the subject of Phosphorus must be used; and, in particular, the _caput mortuum_ must be lixiviated before it be distilled, in order to free it from part of the Sea-salt contained therein; because too much of that Salt might defeat the operator, by not only melting itself, but melting also the containing vessel during the operation. CHAP. IV. _Of the_ VOLATILE ALKALI. PROCESS I. _Volatile Alkalis rectified and depurated._ Mix together the Spirit, the Volatile Salt, the Phlegm, and the Oil, obtained from any substance whatever. Put the whole into a large wide-mouthed glass body, and thereto fit a head with a large beak. Set this alembic in a water-bath, lute on a receiver, and distil with a very gentle heat. There will ascend a Spirit, strongly impregnated with a Volatile Alkali, and a Volatile Salt in a concrete form, which must be kept by itself. Then increase your heat to the degree of boiling water; whereupon there will rise a second Volatile Spirit, somewhat more ponderous than the former, with a light Oil that will swim on its surface, and a little concrete Volatile Salt. Proceed till nothing more will rise with this degree of heat. Keep by itself what came over into the receiver. At the bottom of the cucurbit you will find a thick fetid Oil. Into such another distilling vessel put the Spirit and Salt that rose first in this distillation, and distil them in the _balneum mariæ_ with a heat still gentler than before. A whiter, purer, Volatile Salt will sublime. Continue the distillation till an aqueous moisture rise, which will begin to dissolve the Salt. At the bottom of the vessel will be left a phlegm, with a little Oil floating on it. Keep your Salt in a bottle well stopped. _OBSERVATIONS_. In the analysis of any substance that yields a Volatile Alkali, this Salt is generally found in the receiver, blended with the other principles of the mixt; which, ascending from the retort in the form of liquors and vapours, dissolve the Salt, or at least moisten it, and render it very impure. So that, if you desire to have it without any mixture, recourse must be had to a second distillation, in order to separate it from the heterogeneous matters with which it is confounded. It is of consequence in this distillation to apply but a very weak degree of heat; because on that depends the success of the operation, insomuch that, the less heat you employ to sublime the Salt, the purer it will be. For, being far more volatile than any of the other principles with which it is mixed, it must evidently rise by itself, if no more heat be applied than is just necessary to elevate it; such a heat being much too weak to raise the Oil and phlegm with which it is blended. Nevertheless, whatever care be taken to govern the heat, it is not possible to hinder this Volatile Salt from carrying up some portions of the principles mixed with it; those, to wit, with which it is most closely united, and to which it hath by that means communicated a share of its volatility. For this reason it requires a second rectification, which is performed in the same manner as the former. But, seeing it is more volatile and lighter after the first rectification than before, being thereby freed from part of the heterogeneous matters with which it was loaded, a still less degree of heat must be applied in this second rectification. The Oil with which the Volatile Salt is loaded, when but once distilled, is perceivable only by the yellow colour and weight it communicates thereto; because it is closely united therewith, and in a perfectly saponaceous state. This appears from the facility with which Volatile Salts, even the most oily, dissolve in water, without discovering in the solution any separation of the oily parts, and even without giving it a milky colour. But, in the second rectification, this Oil becomes very perceptible; for it then separates, in a great measure, from the Salt, and remains at the bottom of the cucurbit, floating on the phlegm, which is also separated from the Salt. The Salt is then whiter, more volatile, and purer; yet it is still far from being brought to the utmost degree of purity, even by this second rectification. It requires a third, a fourth, and even many more rectifications, to purify it perfectly: every rectification separates from it some oily particles: and if you should resolve to go on rectifying till you can separate no more Oil, there is reason to think this Salt would be entirely decomposed; because there is necessarily a certain quantity of Oil in its composition, without which it would not be a Volatile Alkali. You must therefore desist from rectifying it any further, when you find it very white, and very light; and shut it up in bottles hermetically sealed. It often happens that Volatile Salts, though of a beautiful white after rectification, grow yellow after being kept some time in close bottles. This is occasioned by the Oil they contain disengaging, and discovering itself by degrees. To remedy this inconvenience, Mr. Boerhaave proposes to mingle the Volatile Salt, which you intend to purify, with four times its weight of pulverized chalk, thoroughly dried, and even heated; to put the mixture into a glass alembic, and distil it with a gentle heat. By this means the Salt rises exceeding pure and very white; because the chalk absorbs most of its Oil, and frees it therefrom. He adds, that Volatile Salt thus purified may be kept a long time, and will retain all its whiteness. If a Volatile Alkali thus purified be combined, to the point of saturation, with an Acid, such as the Marine Acid for instance; the result of this union, as we shall afterwards see, will be a Sal Ammoniac, from which the Volatile Alkali may be separated by the intervention of a Fixed Alkali. A Volatile Alkali that hath passed through all these trials will then be in the highest degree of purity that Chymistry can bring it to, and appears constantly the same, from whatever substance it was originally obtained: which proves that if Volatile Alkalis, extracted from different vegetable and animal substances, seem to differ from each other in some respects, this can arise only from the heterogeneous matters with which they are mixed; but that, at bottom, they are all constituted of one single principle, which is constantly the same, and exactly alike in them all. It is of the last consequence, on all occasions where a Volatile Alkali is to be distilled in a concrete form, to make use of subliming vessels with very large necks, that it may have room enough to make its way to the receiver with ease; for otherwise it may choak up the passage, and burst the vessels. PROCESS II. _Volatile Alkalis combined with Acids. Sundry Ammoniacal Salts. Sal Ammoniac._ On a Volatile Spirit or Salt pour gradually any Acid whatever. An effervescence will arise, and be more or less violent according to the nature of the Acid. Go on adding more Acid in the same manner, till no effervescence be thereby excited, or at least till it be very small. The liquor will now contain a semi-volatile Neutral Salt, called an _Ammoniacal Salt_; which may be obtained in a dry form by crystallizing as usual, or by subliming it in close vessels, after the superfluous moisture hath been drawn off. _OBSERVATIONS._ Volatile Alkalis have the same properties with Fixed Alkalis, fixity only excepted: so that a Volatile Alkali must produce an effervescence when mixed with Acids, and form therewith Neutral Salts, differing from each other in nothing but the nature of the Acid in their composition. It must be observed, that, on this occasion, the point of saturation is very difficult to hit; owing probably to the Volatility of the Alkali, which, being much lighter than the Acid, tends always to possess the uppermost part of the mixture, while the Acid sinks to the bottom: whence it comes to pass, that the lower part of the liquor is sometimes over-charged with Acid, while the upper part is still very Alkaline. But it is most eligible that the Alkali should predominate in the mixture; because the excess of this principle easily flies off, while the moisture is evaporating, in order to the crystallization or sublimation of the Ammoniacal Salt; which being only semi-volatile resists the heat longer, and remains perfectly Neutral. If the Vitriolic Acid be combined with a Volatile Alkali, and the mixture distilled in a retort to draw off the superfluous moisture, a liquor comes over into the receiver, which smells strong of a Sulphureous Acid. Now, as the Acid of Vitriol never becomes sulphureous, but when it is combined with an inflammable matter, this experiment is one of those which demonstrate that Volatile Alkalis contain a very sensible quantity of inflammable matter. This same liquor tastes of an Ammoniacal Salt; which proves that it carries up with it some of the Neutral Salt contained in the mixture. The rest of this Salt, which is called _Glauber's Secret Sal Ammoniac_, or _Vitriolic Sal Ammoniac_, sublimes into the neck of the retort. It is very pungent on the tongue; it crackles a little when thrown on a red hot shovel, and then flies off in vapours. The Ammoniacal Salt formed by the Acid of Nitre exhibits much the same phenomena; but it requires greater care in drying and subliming it, because it hath the property of detonating all alone, without the addition of any other inflammable matter: and it will infallibly do so, if too strong a fire be applied towards the end of the operation, when it begins to be very dry. This property of detonating by itself it derives from the inflammable matter contained in the Volatile Alkali which serves for its basis: and this is another demonstrative proof of the existence of such an inflammable matter in the Volatile Alkali. This Salt is called _Nitrous Sal Ammoniac_. With the vegetable Acids, that of Vinegar for instance, is formed an Ammoniacal Salt of a singular nature, and which can scarce be brought to a dry form. A Volatile Alkali, combined to the point of saturation with the Acid of Sea-salt, forms another Neutral Salt, which takes a concrete form either by sublimation or crystallization. The crystals of this Salt are so very soft and fine, that a parcel of it looks like cotton or wool. This is the Salt properly called _Sal Ammoniac_. It is of great use in Chymistry and in manufactures: but that which is daily consumed in great quantities is not made in the manner above mentioned. It would come extremely dear if we had no other way of procuring it, but by forming it thus with the Acid of Sea-salt and a Volatile Alkali. This Salt, or at least the materials of which it is formed, may be found in the fuliginosities and soots of most animal, and of some vegetable substances. The greatest part of what we use comes from Egypt, where vast quantities thereof are made. The method of preparing Sal Ammoniac in Egypt was not known among us, till Mess. Lemaire and Granger, two of the Academy's correspondents, gave in several Memoirs in which that business is described with great accuracy, from their own view on the spot. Their Memoirs inform us, that chimney-soot alone, without any additament, is the matter from which they obtain their Sal Ammoniac; that those chimneys under which nothing is burnt but Cow's-dung furnish the best Soot. Six and twenty pounds of that Soot yield usually six pounds of Sal Ammoniac. "The operation takes up about fifty, or two and fifty hours. The vessels in which they put the soot are ballons of very thin glass, terminating in a neck of fifteen or sixteen lines long, and an inch in diameter: but they are not all of the same size. The least contain twelve pounds of Soot, and the greatest fifty; but they fill them only three quarters full, in order to leave room for the sublimation of the Salt. "The furnace, in which they place these ballons, consists of four walls, built in a quadrangular form. The two front walls are ten, and the sides nine feet long: but they are all five feet high, and ten inches thick. Within the quadrangle formed by these walls three arches run lengthwise from end to end thereof, at the distance of ten inches asunder. The mouth of this furnace is in the middle of one of its fronts, and of an oval form; two feet four inches high, and sixteen inches wide. "The ballons lie in the spaces between the arches of the furnace, which serve instead of a grate to support them. Four of them are usually placed in each interval; which makes sixteen for one furnace. They are set at the distance of about half a foot from each other, and secured in their places with brick and earth. But they leave about four inches on the upper part of the ballon uncovered, with a view to promote the sublimation, as they also do six inches of the inferior part, that the heat may the better act on the matters to be sublimed. Things being thus prepared they first make a fire with straw, which they continue for an hour. Afterwards they throw in Cow's-dung made up in square cakes like bricks. (The want of wood in this country is the reason that they generally make use of this fuel). These cakes of dung add to the violence of the fire, which they continue in this manner for nineteen hours; after which they increase it considerably for fifteen hours more; and then they slacken it by little and little. "When the matter contained in the vessels begins to grow hot, that is, after six or seven hours baking, it emits a very thick and ill-scented smoke, which continues for fifteen hours. Four hours after that, the Sal Ammoniac is observed to rise in white flowers, which adhere to the inside of the neck of the vessel; and those who have the direction of the operation take care, from time to time, to pass an iron rod into the neck of the ballon, in order to preserve a passage through the saline vault, for giving vent to some blueish vapours, which constantly issue out of the vessel during the whole operation." From this history of the preparation of Sal Ammoniac it appears that Soot, and particularly the Soot of animal matters, either contains abundance of this Salt perfectly formed, and waiting only for sublimation to separate it therefrom, or, at least, that it contains the proper materials for forming it; and that during the operation, which is a kind of distillation of Soot, these materials combine together and sublime. We shewed, in our analysis of Soot, that this substance yields by distillation a great deal of Volatile Alkali; and this is an ingredient which makes at least one-half of Sal Ammoniac. As to the other principle of this Salt, I mean the Marine Acid, this also must needs exist in Soot: but it is not so easy to conceive how it should come there. It is very true that vegetable and animal substances, the only ones that produce Soot in burning, contain some portion of Sea-salt: but then this Salt is very fixed, and seems unfit to rise with the Acid, the Oil, and the subtile Earth, of which the Volatile Alkali is formed. Therefore we must suppose either that its elevation is procured by the force of the fire, aided by the volatility of the matters that exhale in burning; or that, being decomposed by the violence of the combustion, its Acid alone rises with the other principles above-mentioned. The latter seems probable enough: for though in the common operations of Chymistry the bare force of fire doth not seem sufficient to decompose Sea salt; yet the example of Sea-plants, which, before burning, contain this Salt in abundance, and whole ashes contain scarce any at all, but are replete with its fixed part, that is, with its Alkaline basis, seems to prove that, when this Salt is intimately mixed with inflammable matters, it may be destroyed by burning; so that its Acid shall desert its basis, and fly off with the Soot. Before the exact method of procuring Sal Ammoniac was known, it was generally imagined that the manufacturers, mixed Sea-salt, and even Urine, with the Soot; because these two substances contain the principles of which this Salt consists. But, besides that the contrary now certainly appears from the above-mentioned Memoirs, it hath been shewn by Mr. Duhamel, who hath published several Memoirs and experiments concerning the composition and decomposition of Sal Ammoniac, from which we have partly taken what we have already said on this subject, and which will furnish us with some more curious observations; it hath been shewn, I say, in the first of Mr. Duhamel's Memoirs, printed with those of the Academy for 1735, that the addition of Sea-salt to the Soot, from which Sal Ammoniac is to be extracted, contributes nothing to its production, and cannot increase its quantity. That alone, therefore, which was originally contained in the matters that produced the Soot, enters as a principle into the composition of Sal Ammoniac. We observed also, in treating of the analysis of Soot, that Mr. Boerhaave obtained from it a considerable quantity of an Ammonical Salt without any additament. Sal Ammoniac is sometimes found perfectly formed in the neighbourhood of Volcanoes. This Salt is probably produced from the fuliginosities of vegetable or animal matters consumed by the fire of the Volcano. Sal Ammoniac is often impure, because it carries up with it, in sublimation, some of the black charred matter which ought to be left at the bottom of the vessel: but it is easily purified. For this purpose you need only dissolve it in water, filter the solution, then evaporate and crystallize; by which means you will have a very white and very pure Sal Ammoniac. You may, if you please, sublime it again in a cucurbit and blind head, with a fire not too brisk. Some of it will rise in the form of a light white powder, called _Flowers of Sal Ammoniac_. These Flowers are no other than true Sal Ammoniac, which hath suffered no decomposition; because the bare action of fire is not capable of separating the Acid and the Volatile Alkali, of which this Neutral Salt consists. When you intend to decompose it, you must use the means to be mentioned hereafter. Though Sal Ammoniac be only semi-volatile, and requires a considerable heat to sublime it, yet it hath the property of carrying up with it matters that are very fixed and ponderous; such as metallic substances, and some kinds of earths. For medicinal uses we sublime therewith Iron, Lapis Hæmatites, the Copper in blue Vitriol, &c. and then it takes different names, as _Martial Flowers of Sal Ammoniac_, _Ens veneris_, and other such denominations, which it borrows from the matters sublimed with it. PROCESS III. _Sal Ammoniac decompounded by Acids._ Into a large tubulated glass retort put a small quantity of Sal Ammoniac in powder: set your retort in a furnace, and lute on a large ballon, as in the distillation of the smoaking Acids of Nitre and Sea-salt. Through the hole in your retort pour a quantity of Oil of Vitriol, or Spirit of Nitre, equal in weight to your Sal Ammoniac. An effervescence will instantly follow. The mixture will swell, and discharge white vapours, which will come over into the receiver. Stop the hole in the retort immediately, and let the first vapours pass over, together with some drops of liquor, which will distil without fire. Then put a few coals into the furnace, and continue the distillation with a very gentle heat; which however must be increased, little by little, till nothing more will come off. When the operation is finished, you will find in the receiver a Spirit of Salt, if you made use of Oil of Vitriol; or an _Aqua regis_, if Spirit of Nitre was employed: and in the retort will be left a saline mass, which will be either a Glauber's Secret Sal Ammoniac, or a Nitrous Sal Ammoniac, according to the nature of the Acid used to decompound the Sal Ammoniac. _OBSERVATIONS._ Sal Ammoniac, which consists of the Marine Acid united to a Volatile Alkali, is, with respect to the Vitriolic and Nitrous Acids, just the same as Sea-salt is with respect to those Acids; that is, the Vitriolic and Nitrous Acids, having a greater affinity, than the Marine Acid, with Volatile as well as Fixed Alkalis, will decompound the Sal Ammoniac, by expelling the Acid from its basis, and assuming its place, just as they do with regard to Sea-salt. Most therefore of what was said concerning the decomposition of Sea-salt, and the distillation of its Acid, by the two other Acids, must be applied here. We shall only observe, that, when the Acid of Sal Ammoniac is to be distilled from it by the interposition of the Vitriolic or Nitrous Acid, great care must be taken to put but a very small quantity of this Salt into the retort; especially if the Acids to be added are concentrated: for, as soon as they mix with the Sal Ammoniac, a great effervescence arises, and the mixture swells to such a degree, that, unless the quantity in the retort be very small, it may run over altogether into the receiver. It is also proper to take notice, that this operation admits of but a small degree of heat, for two reasons; first, because the Acid of the Sal Ammoniac, being very easily dislodged by an Acid stronger than itself, rises also very easily; secondly, because the Sal Ammoniac which is to be decompounded, as well as the Ammoniacal Salts which result from its decomposition, are semi-volatile, and will sublime in substance if they be exposed to the smallest excess of heat. Moreover, the Nitrous Sal Ammoniac would be in danger of taking fire and exploding, for a reason frequently mentioned above. The Nitrous Sal Ammoniac may be decompounded, as well as Sal Ammoniac, by the Vitriolic Acid. But, as the Nitrous Acid contained in the Salt is the strongest of all Acids next to the Vitriolic, no other Acid but this is able to expel it from its basis; in which respect this Salt resembles Nitre. Instead of employing the Acids of Vitriol and Nitre to decompound Sal Ammoniac, we might make use of Neutral Salts consisting of these Acids combined with metallic or earthy bases: but then, as this decomposition cannot be effected without a greater degree of heat, there is reason to apprehend that some of the Sal Ammoniac would be thereby sublimed, before it could be decompounded. PROCESS IV. _Sal Ammoniac decompounded by Fixed Alkalis. Volatile Salt. The Febrifuge of Sylvius._ Into a glass alembic or retort put Sal Ammoniac and Salt of Tartar, pulverized and mixed together in equal quantities. Set your vessel in a proper furnace, and immediately lute on a large receiver. A little volatile Spirit will ascend; and a volatile Alkali, in a concrete form, very white and beautiful, will sublime into the head, and come over into the receiver, in quantity near two thirds or three fourths of the Sal Ammoniac used. Continue the distillation, increasing the fire by degrees, till nothing more will sublime. Then unlute the vessels. Put up your Volatile Salt immediately into a wide-mouthed bottle, and stop it close with a crystal stopple. At the bottom of the retort, or cucurbit, you will find a saline mass, which, being dissolved and crystallized, will form a Salt nearly cubical, having the taste and other properties of Sea-salt. This is the _Sal Febrifugum Sylvii_. _OBSERVATIONS._ This decomposition of Sal Ammoniac is the reverse of that in the preceding process. In the former operation it was shewn that the Acid of Sal Ammoniac may be separated from its basis, by applying to that basis a stronger Acid: in the present operation, on the contrary, the basis of this Salt is separated from its Acid, by presenting to that Acid a Fixed Alkali, wherewith it hath a greater affinity than with the Volatile Alkali which serves it for a basis. The action of Fixed Alkalis upon Sal Ammoniac is so vigorous and sudden, that, as soon as these two matters are mixed together, the Volatile urinous Salt rushes out with great activity, even without the help of heat; so that much of it will be lost, if care be not taken to confine the mixture immediately in those vessels by means of which it is to be distilled. The Volatile Salt obtained by this operation is white, pure, and very active; having been freed from the greatest part of its superfluous fat matter, both by the union it had contracted with the Marine Acid, and by the Fixed Alkali employed to separate it therefrom. This Salt is so quick and volatile, that if, on taking out the receiver, it be left a little too long exposed to the air, before it be put into the bottle in which it is to be kept, a great deal of it will exhale and be lost. For the same reason care should be taken, while the vessels are unluting, that the vapour of this Salt do not strike the organ of smelling, or be drawn into the lungs in respiration; for it affects those organs so powerfully, and makes such a quick impression on them, that the operator would be in danger of suffocation. Yet it is of great service, when cautiously smelled to, for exciting the vibrations of the _Genus Nervosum_, in Apoplexies, Fainting fits, and Hysterical disorders. But it must always be administered with great caution; for it hath a corrosive quality, and is no less caustic than a Fixed Alkali. This is proved by applying it to the bare skin, and keeping it on by means of a pitch-plaster, so that it cannot fly off in vapours: for, as soon as it begins to grow warm, it produces on the skin a smarting sensation, like that of burning, attended with much pain, and in a very short time makes an eschar like a caustic. The Volatile Spirit, obtained in the decomposition of Sal Ammoniac by a Fixed Alkali, derives its origin from the Phlegm contained in the saline matters that are mixed together on that occasion. The moister those matters are, the more Spirit there will be. This also is very active and penetrating. But as it owes these qualities wholly to the Volatile Salt dissolved in it, the more of this Spirit comes off, the less Salt will there be. If you desire to have much Volatile Spirit, a quantity of water, proportioned to the quantity of Spirit you want, must be mixed with the Salts. In this case the distillation begins with a humid vapour, which coagulates on the sides of the receiver into a concrete Salt, almost as soon as it comes over. There rises afterwards an aqueous vapour, not so saline or volatile as the former. This liquor dissolves the Salt that was coagulated before; and, if the water added was in sufficient quantity, it will dissolve the Salt entirely; otherwise it will dissolve but a part thereof, and then it is certain that the liquor is a Volatile Spirit as strongly impregnated with Salt as it can be. The reason why the liquor that rises first contains a great deal more Volatile Salt than the other, in so much that it coagulates and becomes solid, is because the Volatile Salt rises in distillation much more easily than water. In whatever manner the Volatile Spirit or Salt be distilled from Sal Ammoniac, by means of a Fixed Alkali, we always find at the bottom of the retort, or cucurbit, when the operation is finished, a new Neutral Salt compounded of the Acid of the Sal Ammoniac, and of the Alkali used in the distillation. If the Salt of Tartar be used, this new Neutral Salt will be perfectly like that produced by combining this Alkali with the Acid of Sea-salt, to the point of saturation. The figure of the crystals of this Salt, though much like that of the crystals of Sea-salt, is nevertheless a little different. However, this Salt possesses the chief properties of Sea-salt. It bears the name of _Sal Febrifugum Sylvii_, because that Physician attributed to it the virtue of curing intermitting fevers. But its title to this virtue is very doubtful, at least in this country. If the Salt of Soda be used, instead of Salt of Tartar, to decompound Sal Ammoniac, a Volatile Spirit and Salt will in like manner be obtained; and the Neutral Salt left in the retort, after distillation, will be a true regenerated Sea-salt, perfectly like native Sea-salt; because, as we have said before, the Salt of Soda is of the same kind with the natural basis of Sea-salt; and the inconsiderable differences, observable between the _Sal Febrifugum_ and Sea-salt, can be attributed only to such as may be found between the Alkaline bases of those two Salts. PROCESS V. _Sal Ammoniac decompounded by Absorbent Earths and Lime. The Volatile Spirit of Sal Ammoniac. Fixed Sal Ammoniac. Oil of Lime._ Let one part of Sal Ammoniac, and three parts of Lime, slaked in the air, be pulverized separately, and expeditiously mixed together. Put this mixture immediately into a glass retort, so large that half of it may remain empty. Apply thereto a capacious receiver, with a small hole in it to give vent to the vapours, if needful. Let your retort stand in the furnace about a quarter of an hour, without any fire under it. While it stands thus, a great quantity of invisible vapours will rise, condense into drops, and form a liquor in the receiver. Then put two or three live coals in your furnace, and gradually increase the fire till no more liquor will rise. Now unlute your vessels, taking all possible care to avoid the vapours, and quickly pour the liquor out of the receiver into a bottle, which you must stop with a crystal stopple rubbed with emery. There will remain, at the bottom of the retort, a white mass, consisting of the Lime employed in the distillation, together with the Acid of the Sal Ammoniac: this is called _Fixed Sal Ammoniac_. _OBSERVATIONS._ In our Elements of the Theory, we explained how we imagine that Lime and other substances, which, according to the Table, have less affinity than Volatile Alkalis with Acids, are nevertheless capable of decompounding Sal Ammoniac, by uniting with its Acid, after expelling it from its basis, which is a Volatile Alkali. To recapitulate our opinion in two words: we conceive this to depend on the fixedness of these earthy and metallic additaments, which enables them to resist the force of fire, and on the volatility of the basis of Sal Ammoniac, which proves a great disadvantage to it when it comes to struggle, as it were, with those fixed additaments, aided by a considerable degree of heat. We shall only observe, that we are not singular in this opinion, nor indeed did we deliver it as a new one; that several modern Chymists concur with us therein, and particularly Mr. Baron, whom we have already mentioned more than once on the subject of Borax; and who, we think, was the first that ever took particular notice of it in print, viz. in his Memoirs on Borax, communicated to the Academy before the publication of our Elements. For the explanation of this phenomenon, therefore, we refer to those Memoirs, which are actually published, and to what we have already said on the subject in our treatise above-mentioned. Another phenomenon, which is equally singular and curious, furnishes us with matter for several reflections, and gives us occasion to relate, in few words, the result of Mr. Duhamel's most sagacious experiments and speculations tending to discover the cause thereof. The point under consideration is the different forms and properties which the Volatile Alkali assumes, when separated from Sal Ammoniac by the means of a Fixed Alkali, and by the means of Lime. We know that the former is always in a concrete form, unless the mixture, from which it is distilled, be absolutely drenched with water; and that the latter, on the contrary, is always in a fluid form, and constantly liquid, whatever method be taken to distil it. Some Chymists imagine, that the Volatile Salt of Sal Ammoniac appears in a concrete form, only because it still contains some Acid; whence they conclude that the reason why no concrete Volatile Salt can be obtained by the means of Lime is, because it absorbs all the Acid of the Sal Ammoniac; which is not the case, they say, with Fixed Alkalis. Others impute the constant fluidity of the Volatile Spirit of Sal Ammoniac, obtained with Lime, to the particles of fire which they suppose communicated thereto by that substance. Mr. Duhamel equally refutes both these opinions, by proving from experiments that Fixed Alkalis are capable of absorbing as much Acid as Lime can, and even more; and that, having been calcined as long, and with as violent a fire, as Lime, they must contain and communicate as many particles of fire; if indeed it be possible that the particles of fire should actually be lodged, and continue imprisoned, in calcined substances, as these gentlemen suppose. Yet this is contrary to experience; seeing the Volatile Salt distilled by the means of a Fixed Alkali, though ever so long and ever so violently calcined, is always in a concrete form, and doth not resemble the Volatile Spirit of Sal Ammoniac prepared with Lime. In order to throw the necessary lights on this point, Mr. Duhamel had recourse to the only method that can be depended on in Natural Philosophy; namely, Experiments. He accordingly made several, of which these are the chief. First, he distilled a Volatile Salt, by the means of well desiccated Salt of Tartar, and Salt of Soda; and, urging the fire with great violence towards the end of the operation, he thus obtained a quantity of Volatile Salt equal to, or even exceeding, that of the Sal Ammoniac he used: whence he justly concluded that, on this occasion, the Volatile Salt carried up, and volatilized some of the Fixed Salt. Secondly, he found upon trial that the Volatile Spirit, obtained from Sal Ammoniac by the means of Lime, appears in the form of a liquor, only because it is mixed with some water which was contained in the Lime. Of this truth he had the following decisive proof: having attempted to prepare a Volatile Spirit of Sal Ammoniac with Lime, which had not been slaked, either in the air or by water, he could not obtain any Volatile Spirit: or, at least, the quantity was so small that it might be reckoned as nothing; and even that was wholly due to the moisture which Sal Ammoniac necessarily contains, together with that which Lime imbibes from the air, if ever so little exposed thereto. From these two experiments Mr. Duhamel draws the following consequences: viz. that the Volatile Salt cannot be separated from the Sal Ammoniac and sublimed, without carrying along with it some of the additament which serves to extricate it; or, instead thereof, some other body with which it is capable of uniting: that Fixed Alkalis have the property of being thus carried up by the Volatile Alkali, and subliming with it: that the case is not the same with Lime, which therefore cannot, when alone, separate and sublime the Volatile Alkali of the Sal Ammoniac; but becomes capable thereof when it hath imbibed any moisture, which joins with the Volatile Salt, and rises therewith in distillation. And hence it must be concluded, that, seeing the Volatile Salt carries up with it some of the Fixed Alkali, by the means of which it is separated, it will be in a concrete form; what it carries up along with it being dry and solid: whereas, when it is distilled with Lime, it cannot but be liquid; seeing it must needs be dissolved by the moisture it gets from the Lime, without which it would not rise. But to what must we attribute these effects produced by Lime, so different from those produced by Fixed Alkalis? Are they owing to its quality of Lime? or would it produce the same, if it were only a mere Absorbent Earth? Mr. Duhamel hath answered this question by a third sort of experiment. He tried to decompound Sal Ammoniac, and to separate its Volatile Alkali, by a pure Absorbent of Earth, without mixing any water with it, or calcining it. For this purpose he made use of Chalk; and his experiment succeeded. By means of this additament he decompounded Sal Ammoniac, and by the experiment obtained the lights he wanted. The Volatile Alkali, being extricated by the dry but uncalcined Chalk, rose in a concrete form, as with Fixed Alkalis; and in like manner carried up with it some of the earthy additament. The same Chalk when calcined, and converted into Lime, produced the very effect of Lime on Sal Ammoniac. It is therefore from calcination alone that Absorbent Earths derive the property of retaining obstinately the Volatile Alkali, and preventing its sublimation by refusing to rise with it as Fixed Alkalis do. Though these ingenious experiments evidently furnish us with great lights, for discovering the cause of the solidity or fluidity of the Volatile Alkali, when separated from Sal Ammoniac by different additaments, as they fully determine several preliminary questions immediately relating thereto; yet they still leave us, in some measure, at a loss with regard to the chief point. For we do not yet know why Fixed Alkalis and Absorbent Earths, which, in all Chymical trials, shew that they have certainly as much fixity as Lime, are carried up by the Volatile Alkali, while Lime resists, instead of rising with it as those other substances do, obstinately retains it, and even fixes it in some measure, so that it is impossible for it to sublime. This question, in my opinion, depends on the theory of Lime; nor can we hope to resolve it in its full extent, till we get a further insight into the nature of that singular substance than we have at present. On this subject, however, Mr. Duhamel hath offered some conjectures, founded on the known properties of Lime, and supported by experiments. "Lime," says he, "is an earth freed by calcination from almost all its humidity, almost all its Acid, and all the fat it contained; whether that fat came from some animal parts, as is the case of those stones which consist of shells; or whether it were a bituminous fat, as may happen to be the case with some others: this substance is withal acrid and fiery; it is very greedy of moisture, and imbibes it when exposed thereto. It absorbs Acids, and retains them strongly; and, lastly, it unites with fat matters, and therewith makes a kind of soap." All these properties are verified by experiments; and therefore Mr. Duhamel thinks he hath a right to say, that Lime acts not only on the Acid of Sal Ammoniac, but also on the fatty matter which always accompanies Volatile Alkalis, and is essential to their nature; and therefore it decompounds them. Of this Mr. Duhamel gives the following convincing proof, founded on experiment. He took some Volatile Spirit distilled with Lime, and abstracted it several times from a fresh parcel of Quick-Lime. The quantity of the Spirit diminished sensibly every time; and the Lime was at last so replete with fat, that the Vitriolic Acid, when poured thereon, became very sulphureous; and moreover, when calcined in a crucible, it emitted a very perceptible smell of burnt grease. Indeed Fixed Alkalis are also capable of absorbing and retaining fat matters; but not near so strongly as Lime: because these Salts are never entirely freed from that which they contain originally; whereas Lime seems much poorer, and absolutely void of any oily matter. On these principles Mr. Duhamel resolved to try if he could not obtain a Volatile Alkali in a concrete form, by distilling the Volatile Spirit from Lime, brought nearly to the condition of a Fixed Alkali, by imbibing a portion of fat matter. With this view he distilled a great quantity of Volatile Spirit from a little Lime, and actually obtained a small portion of Volatile Salt; because the great quantity of Volatile Spirit had, in some measure, saturated the Lime with fat matter. Mr. Duhamel tried also to bring Lime back to the condition of a pure Absorbent Earth, to _decalcine_ it, if I may use the term; in order to try whether he could not by this means make it produce the same effect as Chalk. For this purpose he lixiviated some Lime four months successively, pouring every day fresh water on it, and removing that of the preceding day, together with the crystalline crust which always formed on it; and after leaving this Lime two years in the shade, he applied it to Sal Ammoniac. It produced a moderate quantity of Volatile Salt, which was very transparent, and seemed to be crystallized in cubes. Thus we see Lime rendered very like Chalk. Yet it was pretty acrid on the tongue, and the Volatile Salt, obtained by its means, was more disposed to run into a liquid than that separated by Chalk: which shews that this Lime still retained some part of its former character, and that its transformation was not complete. To conclude what relates to the Volatile Alkali of Sal Ammoniac, it only remains that we say a word or two of that portion of the earthy or saline additament, which, though fixed in its nature, sublimes nevertheless with the Volatile Alkali, and gives it a concrete form. Mr. Duhamel, who, in every subject that he handles, omits nothing worthy of attention, made several other experiments, with a view to discover whether or no the Salt of Tartar, and the Chalk, carried up by the Volatile Alkali, be truly volatilized; and whether or no there be such a strict union contracted, between the Urinous Salt and these fixed substances, that the whole results in what is called a _Concrete Volatile Salt_; or if those fixed substances be united but superficially with the Urinous Salt, which only carries them up along with itself in sublimation, as Sal Ammoniac carries up several very fixed metallic matters. The result of the experiments made by Mr. Duhamel for this purpose is, that the fixed substances carried up by the Volatile Alkali of the Sal Ammoniac are actually volatilized; that they make, as it were, one whole with it; and are so closely combined therewith, that almost all the most efficacious means of separating fixed from volatile matters are unsuccessful with regard thereto. Nothing, for instance, is fitter to separate a volatile substance from a fixed one, than to mix the compound with a great quantity of water, and to distil the whole, with such a degree of heat as shall be exactly sufficient to elevate the volatile part. In this manner Mr. Duhamel treated Volatile Alkalis replete with Fixed Salt, and with Chalk: but though he applied no more than the gentlest degree of heat; nay, exposed his mixture to the air only, fearing lest he should make the heat too strong if he used fire; yet the fixed part, which the Volatile Salt had carried up with it, continued still united therewith; so that the whole passed over in distillation, or was dissipated by evaporation, without leaving any thing fixed at the bottom of the vessel. He also justly looked on Acids as an effectual means of procuring the separation, or decomposition, he was in quest of. We know that, with the Volatile Alkali, they form Ammoniacal Salts, which, though they are not so light as the Volatile Alkali, sublime nevertheless with a moderate heat; and that, on the contrary, the same Acids with Fixed Alkalis, or Absorbent Earths, form Neutral Salts, which resist the violence of fire. On this principle Mr. Duhamel poured Acids, to the point of saturation, upon Volatile Alkalis containing much Fixed Alkali, or Chalk. But this experiment succeeded no better than the foregoing; for the mixture being put to distil, sublimed wholly in Sal Ammoniac. Indeed a little fixed matter was left at the bottom of the retort; but the quantity thereof was too small to merit notice. At last, the only way Mr. Duhamel could think of, for separating, from a Concrete Volatile Alkali, the fixed parts which that Salt had rendered Volatile, was to expose it to the air, covered with a piece of gauze only; but in its dry state, without dissolving it in water. The Volatile Urinous Salt was by this means dissipated; having deserted the fixed part, which remained at the bottom of the bason, and, being exposed to the fire, retained its fixed nature. But it took more than a year to effect this separation; nor are we sure that it was complete; for it is not certain that all the fixed part was left behind, and that some of it was not dissipated with the Volatile Urinous Salt. This volatilization, this kind of metamorphosis of a Fixed Alkali and an Absorbent Earth into a Volatile Alkali, is a very curious phenomenon, and deserves to be considered by the best Chymists. We shall finish our observations on the decomposition of Sal Ammoniac by Lime, with some reflections on the nature of the _caput mortuum_ that remains after this distillation. This residuum is only Lime impregnated, but not saturated, with the Acid of Sea-salt. If the distillation be urged at last with a violent fire, the _caput mortuum_ will be found formed into a mass, seeming to have been half-melted. This matter is a kind of Phosphorus, and emits light in the dark, when struck with any hard body. Mr. Homberg was the first who discovered it to have this property. Having calcined, and melted together in a crucible, one part of Sal Ammoniac and two parts of Lime, with a design to fix that Salt, he observed the mass remaining after the fusion to have the property just mentioned. Lime, thus impregnated with the Acid of Sal Ammoniac, is very improperly called by the name of _Fixed Sal Ammoniac_. This compound attracts the moisture of the air, and even runs wholly into a liquid, if it be impregnated with much Acid. It hath almost all the properties of Fixed Alkalis. This liquid is called _Oil of Lime_, for the same reason that deliquated Salt of Tartar is called _Oil of Tartar_. PROCESS VI. _Volatile Alkalis combined with Oily matters. A Volatile Oily Aromatic Salt._ Pulverise and mix together equal parts of Sal Ammoniac and Salt of Tartar: put the mixture into a glass or stone cucurbit: pour on it good Spirit of Wine, till it rise half an inch above the matter. Mix the whole with a wooden spatula; apply a head and a receiver, and distil in a sand-bath, gently heated, for two or three hours. A Volatile Salt will rise into the head; and then the Spirit of Wine will distil into the receiver, carrying with it a portion of the Volatile Salt. When nothing more will come over, let your vessels cool; then unlute them, separate the Volatile Salt, and weigh it directly. Return it into a glass cucurbit, and for every ounce thereof add a dram and a half of Essential Oil, drawn from one or more sorts of aromatic plants. Stir the whole with a wooden spatula, that the Essence may incorporate thoroughly with the Volatile Salt. Cover the cucurbit with a head, fit on a receiver, and, having luted it exactly, distil in a sand-bath, as before, with a very gentle heat. All the Volatile Salt will rise, and stick to the head. Let the fire go out, and when the vessels are cooled take your Salt out of the head. It will have an odour compounded of its own proper smell, and the smell of the Essence with which it is combined. This is an _Aromatic Oily Salt_. Put it into a bottle stopped close with a crystal stopple. _OBSERVATIONS._ The design of this operation is to incorporate and unite an Oil with a Volatile Alkali. Spirit of Wine is added in the distillation of the Volatile Salt, intended for this purpose, in order to prepare it for receiving the Oil, and combining more easily therewith. This Salt hath the property, as was shewn in the preceding operation, to carry up with it part of the substances with which it is distilled. On this occasion therefore, it is impregnated with a little of the Spirit of Wine; and this Spirit, which contains in itself an oily matter, and is the solvent of Oils, cannot fail to facilitate the union of the Oil with the Volatile Salt, as it serves for a medium between them. Yet it must not be considered as a necessary one. A Volatile Salt, sublimed with Salt of Tartar alone, would also very readily take up any Oil with which it should be distilled. We have seen that Volatile Alkalis are originally impregnated with much Oil, which is radically dissolved in them; and consequently they have a great affinity with that substance. So that if we distil them with Spirit of Wine, at the beginning of this operation, we do it not out of any necessity, but only with a view to accelerate or facilitate the intended union. In this distillation the Volatile Alkali always rises first, and before the Spirit of Wine; which proves that it is much more volatile, though it be more ponderous than the Spirit. If the Spirit of Wine used in this distillation be very aqueous, it will dissolve the Salt as it comes over, and will reduce it into a Spirit: but if, on the contrary, it be well dephlegmated, the Volatile Alkali will remain in a concrete form, and will not be dissolved in this first distillation. If you desire to have the Volatile Salt entirely dissolved in the Spirit of Wine, though highly dephlegmated, it must be repeatedly distilled a great number of times with the same Spirit of Wine: for, though the small quantity of Spirit of Wine, with which it unites in the first distillation, be not capable of reducing it into a liquid, yet, as it takes up more and more every time it is distilled, it dissolves at last, and then with the Spirit of Wine forms a fluid that appears perfectly homogeneous. The Volatile Alkali is now rendered considerably milder by the union thus contracted, and is accordingly called the _Dulcified Volatile Spirit of Sal Ammoniac_. When well dephlegmated Spirit of Wine is mixed with a Volatile Spirit of Sal Ammoniac, perfectly saturated with Volatile Salt, these two liquors together immediately form a white opaque _coagulum_. But for this purpose you must not use a Volatile Spirit distilled with Lime; for then the experiment will not succeed. This _coagulum_ does not seem to be the effect of an intimate union between the two substances mixed together, like that which results from the union of a Fixed Alkali with an Oil. It hath just now been shewn that Spirit of Wine and a Volatile Alkali do not readily unite together. I believe the effect rather depends on this, that Spirit of Wine hath a greater affinity than the Volatile Salt with water; and therefore the Spirit, which ought to be perfectly dephlegmated, attracts the water wherein the Volatile Salt was dissolved, which thereupon recovers its concrete form; and being at that time mixed with the Spirit of Wine, it keeps that Spirit locked up among its parts, and hinders it from appearing with its natural fluidity. What confirms this notion is, that the _coagulum_, which at first seems to make but one whole, soon separates into two parts, whereof one, which is solid, and nothing but the Volatile Salt concreted, lies at the bottom of the vessel; and the other, which is fluid, cannot be mistaken for any thing but the Spirit of Wine, which, being disengaged from the particles of Salt, recovers the form of a liquid, and, being the lightest, floats over the Salt. Yet these two substances, though now very distinct from each other, are not so pure as before they were mixed together. The Spirit of Wine hath dissolved a little of the Volatile Salt; and, on the other hand, the Volatile Salt retains a little of the Spirit of Wine. They may indeed be perfectly united and blended with each other, by the method above delivered; that is, by being frequently distilled and cohobated together, till they form one mixt; but then that mixt will be in a liquid form. The first time this mixture is distilled, a great deal of Volatile Salt rises first, which is very fit to unite with an Essential Oil, and so to become a Volatile Oily Aromatic Salt. THE END. [Illustration: Pl. I.] [Illustration: Pl. II.] [Illustration: Pl. III.] [Illustration: Pl. IV.] [Illustration: Pl. V. and VI. _GEOFFROY'S TABLE of the COMPARATIVE AFFINITIES observed between sundry substances._] I. Acid Spirits Fixed Alkali Volatile Alkali Absorbent Earths Metallic Substances II. Marine Acid Tin Regulus of Antimony Copper Silver Mercury Gold III. Nitrous Acid Iron Copper Lead Mercury Silver IV. Vitriolic Acid Phlogiston Fixed Alkali Volatile Alkali Absorbent Earths Iron Copper Silver V. Absorbent Earths Vitriolic Acid Nitrous Acid Marine Acid VI. Fixed Alkali Vitriolic Acid Nitrous Acid Marine Acid Spirit of Vinegar Sulphur VII. Volatile Alkali Vitriolic Acid Nitrous Acid Marine Acid VIII. Metallic Substances Marine Acid Vitriolic Acid Nitrous Acid IX. Sulphur Fixed Alkali Iron Copper Lead Silver Regulus of Antimony Mercury Gold X. Mercury Gold Silver Lead Copper Zinc Regulus of Antimony XI. Lead Silver Copper XII. Copper Mercury Calomine XIII. Silver Lead Copper XIV. Iron Regulus of Antimony Silver, Copper, Lead XV. Regulus of Antimony Iron Silver, Copper, Lead XVI. Water Ardent Spirits Neutral Salts EXPLANATION OF THE PLATES. PLATE FIRST. FIG. I. _A Copper Alembic._ A. The Cucurbit or Body. B. The Neck. C. The Head. D. The Beak, Nose, or Spout. E. The Refrigeratory, or Cooler. F. Its Cock. G. The Receiver. FIG. II. _A Glass Alembic._ A. The Cucurbit. B. The Head. C. The Gutter within the Head. D. The Beak. FIG. III. _A long-necked Glass Alembic._ A. The Body of the Matrass. B. The Neck. C. The Head. PLATE SECOND. FIG. I. _A Glass Alembic of one piece._ A. The Cucurbit. B. The Head. C. The Aperture in the Head. D. Its Stopple. E. The Mouth of the Cucurbit. FIG. II. _A Pelican._ A. The Cucurbit. B. The Head. C. The Aperture in the Head, with its Stopple. D. D. The two curved Spouts. FIG. III. _A Row of Aludels._ FIG. IV. _A Retort._ A. Its Bowl. B. Its Neck. FIG. V. _An English Retort._ PLATE THIRD. FIG. I. _A Reverberating Furnace._ A. The Ash-hole Door. B. The Fire-place Door. C. C. C. C. Registers. D. The Dome, or Reverberatory. E. The Conical Funnel. F. The Retort in the Furnace. G. The Receiver. H. H. Iron Bars to sustain the Retort. FIG. II. _The Conical Funnel by itself._ FIG. III. _Back View of a Muffle._ A. The bottom of the Muffle. B. Its Arch. C. C. C. Lateral apertures. FIG. IV. _Fore-View of a Muffle._ FIG. V. _A Melting Furnace._ A. A. The Base of the Furnace. B. The Ash-hole. C. D. The Grate for the Fire. E. The Fire-place. F. G. H. Curvature of the inside of the upper part of the Fire-place. I. The Shaft or Chimney. PLATE FOURTH. _A Cupelling Furnace._ A. The Ash-hole. B. B. Its sliding Doors. C. The Fire-place. D. D. Its sliding Doors. E. F. Small apertures in the Sliders. G. G. Holes for Bars to bear the Muffles. H. H. H. Iron braces in the fore-part of the Furnace, which form grooves for the Doors of the Fire-place and Ash-hole to slide in. I. The upper pyramidal part of the Furnace. K. An aperture therein for managing the Coals. L. The opening at top. M. The Pyramidal Cover. N. The Chimney or end of the Shaft, on which the conical Funnel may be fitted. O. O. O. O. Handles for moving the sliding Doors. P. P. Ears of the Pyramidal Cover. _N. B._ The Furnaces, as represented in the two last Plates, are not in due proportion to each other. The Cupelling Furnace is much larger than it should be, with respect to the Melting Furnace. These dimensions are here given it, only that all its parts might be more distinctly expressed, than could have been done if we had made it less. INDEX. A Absorbent Earths, _Pag._ 5, 512 Acetous Fermentation, 90, 536, 539 Acids in general, 13 the Universal, or Vitriolic, 19, 172 the Nitrous, 12, 170 the Marine, 25, 213 the Vegetable, 90, 440 the Animal, 107, 578 Acids dulcified, 87 Adopters, 132 Æther, 88, 492, 501 Æthiops Mineral, 61, 304 of Antimony, 63 Affinities between Bodies in general, 9 of Acids in general, 121 of the Marine Acid, 122 of the Nitrous Acid, 123 of the Vitriolic Acid, _ib._ of Absorbent Earths, _ib._ of Fixed Alkalis, _ib._ of Volatile Alkalis, 124 of Metallic Substances, _ib._ of Sulphur, _ib._ of Mercury, _ib._ of Lead, 125 of Copper, _ib._ of Silver, _ib._ of Iron, _ib._ of Regulus of Antimony, _ib._ of Water, _ib._ of Spirit of Wine, _ib._ Air, 2 from Guaiacum-Wood, 440 from Tartar, 516 Alembics of Metal, 128 Alembics of Glass, 129 tubulated, _ib._ _Algaroth, Pulvis_, 342 Alkalis, 14 Fixed, 14, 106, 448, 449 from Sea-salt, 26 from maritime plants, 106 from burnt vegetables, 448 from Nitre, 187 from Tartar, 515 from Wine-lees, 517 made more Caustic by quick-lime, 36, 455 Volatile, 98, 107, 446, 599, 609 from plants with cruciform flowers, 445 Alkohol, 88, 484 Aludels, 130 Alum, 19, 165 Roman, 167 Amalgams, 59, 233 Amber, 119, 467 Ammoniacal Salts, 98 Analysis, Chymical, 101 of Vegetables, 102 of Animals, 106 of Minerals, 108 of Guaiacum Wood, 440 of Mustard-seed, 445 of Wood-soot, 457 of Turpentine, 460 of Benzoin, 463 of Amber, 467 of Bees-Wax, 472 of Honey, 474 of Gum-Arabic, 476 of Wine, 480 of Spirit of Wine, 486 of Tartar, 514 of Vinegar, 542 of Putrid Vegetables, 559 of Butter, 566 of Cheese, 569 of Whey, 571 of Bullock's Blood, 574 of Beef, 580 of Ox-bones, 583 of Mutton-Suet, 584 of Pullet's Eggs, 586 of Human Excrement, 588 Urine, 596 Animals, 106, 574 Anodyne Mineral Liquor, 500 Antimony, Crude, 65, 116, 234, 315, 335, 339 Diaphoretic, 67, 326 unwashed, 329 _Aqua Fortis_, 24, 42 purified, 43 blue, 377 _Aqua Phagedenica_, 312 _Aqua Regis_, 38, 42, 217, 227 _Aquila Alba_, 61, 312 _Arcanum Duplicatum_, 19 _Corrallinum_, 60, 308 Ardent Spirits, 85, 481 Aromatic strong Waters, 514 Oily Volatile Salt, 620 Arsenic, 72, 118 Fixed, 381 Assay, parting, 42, 250 Ash-hole, 134 _Aurum Fulminans_, 38, 39, 229 reduced, 38, 39, 230 B Ballons, 132 _Balneum Mariæ_, 133 Balsams, 81, 460 of Sulphur, 434 Bar iron, 48 Basis of Sea-Salt, 26 of Nitre, 185 Baths, Water, Vapour, Sand, 133 Beak of an Alembic, 128 Bee's-wax, 472 Bell-metal, 53 Benjamin, or Benzoin, 463 Bezoar Mineral, 64, 343 Bezoartic Spirit of Nitre, _ib._ Bile, 108 Bismuth, 69, 117, 350 Bitumens, Native, 79, 119, 467 Artificial, 493, 513 Black Copper, 263, 264 Flux, 241 Blind Head, 130 Blood, 108, 574 Blue _Aqua Fortis_, 377 Enamel, 371 Powder, _ib._ Vitriol, 46, 111, 286 Boles, 169 Bones, 583 Borax, 27, 218, 524 Brandy, 85, 483 Brass, 71, 352 Brewing Malt liquor, 479 Bronze, 53 Burnt Alum, 19 Butter of Antimony, 64, 338 Lunar, 341 of Bee's-wax, 472 of Cacao, 410, 473 of Milk, 564, 566, 568 C _Cadmia Fornacum_, 71, 358 Calamine, or _Lapis Calaminaris_, 71, 118, 357 Calcination, 29, 30, 36, 117 Calx of Antimony, 63, 321 reduced, 323 vitrified, 330 of Arsenic, 367 of Bismuth, 69 of Copper, 267 of Lead, 292 Calx of Tin, 52, 280 of Zinc, 361 Camphor, Native, 465 Factitious, 466 _Caput mortuum_, 105 Carat, 55 Caustic Stone, common Caustic, or potential Cautery, 33, 455 Cementation, 48, 258 _Cendre Gravelée_, 517 Ceruse, 92, 553 Chalybeated Tartar, 95, 528 Soluble, 94, 528 Charcoal, 8, 77, 449 Cheese, 562 Churning, 564 Chyle, 108, 393, 563 Chymical Decomposition, 101 Vessels, 126 Furnaces, 133 Chymistry, its Object, 1 Cinabar, 62, 116, 298, 306 of Antimony, 69, 338 _Clyssus_ of Antimony, 330 of Nitre, 189 Coal, 8, 77, 449 Cobalt, 119, 367 Cohobation, 130 Colcothar, 174 its Salt, _ib._ Colophony, 462 Combination of Mercury with Sulphur, 306 with the Marine Acid, 308 of Regulus of Antimony with the Marine Acid, 338 of Zinc with Copper, 361 of Fat Oils with Acids, 398 with Fixed Alkalis, 400 with Sulphur, 405 with Lead, 406 of Essential Oils with Sulphur, 434 with Fixed Alkalis, 438 of Spirit of Wine with the vitriolic Acid, 492 with Spirit of Nitre, 503 with the Marine Acid, 508 of Crystal of Tartar with Absorbent Earths, 519 of Crystal of Tartar with Fixed Alkalis, 524 with Iron, 528 with Regulus of Antimony, 534 of Vinegar with Alkalis, 547 with Copper, 550 with Lead, 552 of a Volatile Alkali with Acids, 602 with oily Matters, 618 Combustion, its effect on Vegetables, 448 Condensation of Air, 3 Cooler of an Alembic, 129 Copper, 44, 113, 247, 253, 262, 289 separated from Iron, 56 from Lead, _ib._ Black, 263 Copperas, or Green Vitriol, 49, 160 Corrosive Sublimate, 61, 308 Cream, of Milk, 562 of Tartar, 93, 517 _Cremor Calcis_, 30, 520 _Crocus Martis_, 49, 276 _Aperiens_, 51, 277 _Astringens_, _ib._ _Metallorum_, 66, 326 Crucibles, 132 Cruciform flowered Plants, 445 Crystallization, 16 Crystals of Antimony, 336 of Arsenic, 72, 377 of Bismuth, 253 of Silver, 40, 254 of Tartar, 93, 517 of Lead, 92, 297 of Mercury, 307 of Venus, or Copper, 550 Cucurbit, 128 Cupel, 55, 243 Cupelling, 243 Curd, 56, 569 D Decoction, 410, 419 Decomposition, Chymical, 101 of Sulphur by burning it, 176 of vitriolated Tartar by means of the Phlogiston, 179 of Nitre by means of the Phlogiston, 186 of the vitriolic Acid, 191 of Arsenic, 377 of Sea-salt by means of the Phlogiston, 197 of the vitriolic Acid, 211 of the Nitrous Acid, 217 of Borax by means of Acids, 218 of Butter of Antimony by means of Water, 342 of Fat Oils combined with Acids, 398 with Fixed Alkalis, 400 with Lead, 406 of Essential Oils combined with Sulphur, 434 with Fixed Alkalis, 438 of Spirit of Wine combined with the vitriolic Acid, 492 of Soluble Tartars, 95, 526 of Regenerated Tartar, 547 of Salt of Coral, Crab's eyes, Pearl, &c., 549 of Verdegris, 550 of Salt or Sugar of Lead, 555 of Sal Ammoniac by Acids, 607 by Fixed Alkalis, 608 by Absorbent Earths and Lime, 611 Decrepitation, 27 _Deliquium_, 12 Diaphoretic Antimony, or Mineral, 65, 67, 326 Unwashed, 329 Dissolution of Metals, 35 Distillation, 101 _per descensum_, 127, 419 _per ascensum_, 128 _per latus_, 131 Distilled Verdegris, 550 Vinegar, 91 Dome of a Furnace, 135 Dry way of parting Metals, 42 Drying varnish, 87 Dulcified Acids, _ib._ Volatile Spirit of Sal Ammoniac, 620 E Earth, 4 fusible or vitrifiable, 5, 29 unfusible or unvitrifiable, _ib._ absorbent, 5 calcinable and uncalcinable, 29 Eggs analyzed, 586 Elasticity of air, 3 Elements of Bodies, 2 Elixirs, 512 Emetic Tartar, 95, 326, 331, 534 Wine, 326, 331 Empyreumatic Oils, 82 Emulsion; vegetable, 104, 392 Animal, 563, 587 Enamel, 52 Blue, 371 _Ens Veneris_, 607 Epsom Salt, 196 Essential Oils, _see_ Oils. Essential Salts, 103, 387 of Vinegar, 545 of Wine, 103 of Flesh, 582 Expressed Juices, of Plants, 103, 383 of Animals, 106 Expressed Oils, 103, 386, 387 Extracts, 104, 106, 419 by Triture, 389 F Falsification of Essential Oils, 425 Fat, Animal, 107, 584 Fat Oils by expression, 103, 386 by decoction, 410 attenuated, 395 Fat Lute, 148 Febrifuge of Sylvius, 608 Ferment, or Yest, 481 Fermentation, 83 Vinous or Spirituous, 83, 478, 481 checked, 481 Acetous, 83, 87, 90, 536 Putrefactive, 83, 557 Fetid or empyreumatic Oils, 82 Fire, element of, 5 how applied, 134 naked, _ib._ Fire-place, of a Furnace, _ib._ Fixed Nitre, 23 Sulphur of Antimony, 68, 329 Sal Ammoniac, 618 Arsenic, 381 Flesh analyzed, 580 Flints, 29 Flowers, 130 of Antimony, 63, 347 of Regulus of Antimony, 348 of Sulphur, 20 of Zinc, 70, 359 of Benzoin, 463 of Sal Ammoniac, 606 Martial, 607 Fluor, of an Ore, 110 aqueous of a Salt, 180 Fluxes, 46, 241 Foliated Salt of Tartar, 549 Forge, 142 Forged Iron, 48 Fulguration in cupelling, 244 Fulmination of Nitre, 23 Furnaces their Construction, 134 Reverberating, 137 Melting, 140 Cupelling, 142 Lamp-heat, 146 Forge-heat, 142 Furnace-Calamine, 358 G Glass, 5 of Lead, 54, 293 of Antimony, 63, 330 of Bismuth, 69, 351 of Zinc, 360 Glauber's Salt, 27, 169, 213 Gold, 37, 112, 223 refined by Cementation, 258 imitated, 71, 364 Golden Sulphur of Antimony, 68, 318, 334 Grain, in Salt Petre working, 183 _Gravelle_, or _Gravellee_, 517 Green Precipitate, 60 Vitriol, 49, 111 fluid, 278 Guaiacum Wood analyzed, 440 Gums, 81 analyzed, 476 Gum Resins, 477 Gypsum, 169, 404 H Head of an Alembic, 128 Blind-head, 130 Heart-burn, 568 Heat, reverberated, melting, forging, lamp-heat, &c., 134 _Hepar Sulphuris_, 21 Hoffman's Anodyne Mineral Liquor, 500 Honey analyzed, 474 Hops, 484 I Icy Oil of Vitriol, 18, 173 Infernal Stone, 40, 255 Infusion, 492 Ink, sympathetic, 353 Iron, 47, 114, 270 red-shire and cold-shire, 272 pig-iron made malleable, 273 converted into Steel, 48, 274 Juices by expression, of Plants, 102, 383 of Animals, 106 K Kermes Mineral, 68, 332 Killed Mercury, 305 L Laboratory, of a Furnace, 135 _Lac Calcis_, 30, 520 _Sulphuris_, 21 _Lapis infernalis_, 40, 255 Calaminaris, 71, 118, 357 purified, 362 Lead, 53, 115, 286 White, 92, 553 Lees of Wine, 515, 517 Libavius, his smoking Liquor, 61, 285 Lime, Lime-stone, 29, 520 slaked in the air, 30 Lime-water, 30, 520 Liquescent Salts, 17 Litharge, 54, 294 Liver of Sulphur, 21, 73 of Antimony, 67, 325 of Arsenic, 75 _Luna Cornea_, 57, 256, 257 Lunar Crystals, 40 Lutes, 147, 148 M Maceration of Plants, 415 Magistery, 22, 36 of Sulphur, 22 of Bismuth, 70, 352 of Coral, Pearl, Crab's-eyes, &c., 549 of Lead, 553 Magnesia, 186 Malt, Malting, Malt-liquor, 479, 486 Manna, 475 Marcasites, 109 Matched Wines, 482 _Materia perlata_, 65, 67, 328 Matrass, 129 Mercury, 58, 115, 298 revivified from Cinabar, 62 obtained from Lead, 296, 298 _Mercurius præcipitatus per se_, 58, 302 _dulcis_, 61, 312 _vitæ_, 64, 342 Mercurial Earth, 25, 34 Metals, 37 perfect and imperfect, 35, 37 Metallic substances, 35 Milk, 108, 393, 562 Minerals, 108 Minium, 53 Moist way of parting Metals, 42 Mortar, 30 Mother-water, 186 Muffle, 144 Must, 482 Mustard-seed analyzed, 446 N Neck of the Alembic, 128 Neutral Salts, 15 having Lime for their basis, 33 Arsenical, 73, 377 of Vinegar with absorbent Earths, 92 Nose of the Alembic, 128 Nitre, 22, 181 its basis, 185 fixed or alkalizated, 23, 187, 379 quadrangular, 27, 220 Nitrous Salts with an earthy basis, 22 with Lead, 297 with Mercury, 307 O Object of Chymistry, 1 Ochre, 50 Oils, in general, 76 Mineral, 79 Vegetable, 80 Animal, 82 Fetid, or Empyreumatic, _ib._ Fat, by expression, 102, 386 by decoction, 410 Essential by expression, 388 by distillation, 412, 444 _per descensum_, 418 rectified, 422 falsified, 425 Oils fired by Acids, 426 Oil of Vitriol, 18 Icy, 18, 173 Oil-varnish, 87 Oil of Tartar _per deliquium_, 94 of Lime, 208, 611 of Salt, 216 of Mercury, 304 of Amber, Volatile, 467 of Eggs, by expression, 586, 588 of Myrrh _per deliquium_, 587 Ores, 109 Orpiment, 75, 118, 369 P Panacea of Mercury, 61, 314 Pancreatic Juice, 108 Parting Process, in the humid way, 42, 250 in the dry way, 258 Pearly matter, 65, 67, 328 Pelican, 130 Penny-weight, 56 _Petroleum_, 79 Philosophic Wool, 70 Spirit of Vitriol, 343 Phlogiston, 7 Phosphorus of Urine, 26, 77, 78, 198, 446, 447 Homberg's, 618 Pig-Iron, 48, 271 Plaster, 407 _Plumbum corneum_, 57 Point of Saturation, 16 _Pompholyx_, 70 Potential cautery, 33 Powder-blue, 371 Precipitant, 66 Precipitation, 22, 36 Precipitate of Sulphur, 22 of Gold, purple, 284 Precipitate, Red, 60, 307 Green, 60 Yellow, 61 White, 307 Precipitated _Aqua Fortis_, 44 Prince's Metal, 71, 364 Principles of Bodies, 2 Principle of Odour, 408, 413 Proof of Spirit of Wine, 484 _Pulvis Algaroth_, 342 Purification of Nitre, 185 of Spirit of Nitre, 194 of Spirit of Salt, 213 of the Sedative Salt, 222 of Silver by Nitre, 248 _Pyrites_, 110, 160 Yellow, 110 White, 111, 118 Copper-coloured, 111 Q Quadrangular Nitre, 27, 217 Quartation, 43, 251 Quartz, 147 Quick-lime, 30 Quick-silver, _see_ Mercury. R Rabel's Water, 495 Rape, of Grapes, 538 Rarefaction of Air, 2 Rectification of Oils, 81, 422 of Volatile Alkalis, 100 Rectified Spirit of Wine, 85 Reducing, a Metal, 35 Reducing Fluxes, 46 Refining Gold and Silver, 45, 55, 66, 351 Refined Salt-petre, 183 Refractory Earth, 29 Calx, 53 Refrigeratory, 129 Regenerated Tartar, 92, 94, 547 Registers of a Furnace, 135 Regulus, 110 of Antimony, 62, 116, 316 pure, or _per se_, 67 with Metals, 234, 318 of Arsenic, 72, 374 of Cobalt, 119, 371 Resins, 81, 462 Resuscitation of Metals, 35 Retort, 131 English, _ib._ Tubulated, 132 Revivify a Metal, 35 Roasting of an Ore, 109 Rochelle Salt, 525 Rosin, 460 Ruby of Arsenic, 369 Runnet, 565 Rust of Copper, 45 S Saccharine Juices of Plants analyzed, 474 Saffrons of Mars, 49, 51, 276, 277 Saignette's Salt, 95, 524 Saline Substances, in general, 11 Saliva, 108 Sal Ammoniac, 98, 602 Native, 606 with Vinegar, 603 Nitrous, 98, 603, 608 Vitriolic, or Glauber's Secret, 607 _Catharticum Amarum_, 196 _De Duobus_, 19, 193 _Febrifugum Sylvii_, 29, 609, 611 _Gem_, 195 _Mirabile_, 27 _Polychrestum_, 189 _Salsum_, 13, 15 _Saturni_, 92, 553, 554 _Sedativum_, 28, 219 Salt of Amber, Volatile, 467, 469 of Benzoin, Volatile, 464 of Colcothar, 174 Common, or Sea-salt, 27, 195 Epsom, 196 of Lime, 31 Petre, 22, 181, 182 Quieting or Sedative, 28, 219 of Soda, or maritime Plants, 94, 524 of Pearl, Coral, Crab's-eyes, &c., 549 of Rochelle, 95, 525 of Tartar, 94 of Urine, which produces Phosphorus, 209 Salts, Neutral, 15 with Lime for their basis, 32 with Arsenic, 73, 377 of Vinegar with absorbent Earths, 91 Nitrous with absorbent Earths, 22 with Lead, 297 with Mercury, 307 from Excrement, 590 Salts, Urinous Volatile, 97 Ammoniacal, 98, 602 Essential, 103, 383 Glauber's, Artificial, 27, 211 Native, 169 Saignette's, 95, 524 Sylvius's Febrifuge, 29, 609, 611 Tachenius's, 106, 453 Samech of Paracelsus, 490 Sand-bath, 133 Saturation, 15 Scoria, 110 Scorifiers, 133 Scorification with lead, 238 Sedative Salt, 28, 219 Selenites, 19, 404 Semi-metals, 35, 62 Serum of Milk, 562 of Blood, 574 Silver, 40, 44, 112, 224, 238, 253 Caustic, 40 Silver rendered very pure, 256 Slaked Lime, 30 Smalt, 370, 371 Smoking liquor of Libavius, 61 Soap, 78, 400 liquid, 404 Starkey's, 438 Metallic, 408 common used in Medicine, 405 Soluble Tartar, 95, 528 chalybeated, 528, 529 Soot of Wood, analyzed, 457 of Cows dung yields Sal Ammoniac, 604 Spirit of Vitriol 18, 177 Philosophic 343 Sweet, 500 Volatile of Sulphur, 20, 485 of Nitre 24 Smoking, 24, 191, 308 Sweet or dulcified, 90, 504 purified, 194 Bezoartic, 64, 345 of Salt, 25 Smoking, 26 Sweet or dulcified, 90, 508 concentrated, 216 of Wine, 85, 483 Alcoholized, 87 dephlegmated, 484, 486 of Verdegris, 551 Spirit Varnish, 87 Spirituous Fermentation, 84, 478 Spirit, Volatile, Urinous, 97 _Spiritus Rector_ of Plants, 105, 409 Spout of the Alembic, 128 Steel, 48, 274 ore, 276 Stibiated, or Emetic Tartar, 95, 534 Stum, 482 Sublimate, Corrosive, 61, 308 Sweet, 61, 312 Sugar, 475 of Lead, 92, 553 Sulphur Mineral, 20 extracted from the Pyrites, &c., 162 Native, 164 factitious, 179, 399 of Antimony, golden, 68, 318 fixed, 329 Sweat, 108 Sweet Sublimate, 61, 312 T Tachenius's Salt, 106, 453 Talc, 169 Tartar, 93, 103, 315, 485, 517 Emetic, 95, 534 Regenerated, 92, 546, 547 Soluble, 95, 519 Tartarized, 95, 177 Stibiated, 95, 534 Vitriolated, 19, 170 Tartarized Spirit of Wine, 87 Tempering of Steel, 48, 275 _Terra damnata_, 105 _Foliata Tartari_, 92, 94, 549 Tests, 133 Tin, 52, 115, 279 Tincture, of Salt of Tartar, 487 of Mars with Tartar, 528 of Copper, 550 Tinctures, Vegetable, 510, 512 Tin-glass, 69 Tin-plates, 52 Tombac, 71 Touch-stone, 261 Trituration, 389 Turbith Mineral, 60, 303 Turpentine analyzed, 460 Tutty, 359 U Urine, 108 Urinous spirit and salt, 97 V Vapour-bath, 133 Varnish, 87, 512 Vegetable-salt, 94, 524 Verdegris, 92, 551 distilled, 550 Vermillion, 62 Vinegar, 91, 523, 537 distilled, 91 concentrated, 540, 545 analyzed, 542 Vinous fermentation, 83, 478, 481 Vitriol, blue, 46, 111, 268 Green, 49, 111, 169 White, 71, 169, 365 extracted from the pyrites, 159 of Lead, 296 Vitriolated Tartar, 19, 170, 192, 194 Vitriolic acid, 18 concentrated, 176 Volatile spirit of sulphur, 20 urinous spirit and salt, 97, 609 Spirit of sal ammoniac, 611 oily aromatic salt, 620 W Water, 3 hard, 403 Water-bath, 133 Waters, odoriferous, 408 distilled, 412 Wax from plants by decoction, 410, 472 Whey, 562 analyzed, 571 White arsenic, 72 Lead, 92, 553 Vitriol, 71, 365 Precipitate, 307 White paint for ladies, 352 White of an egg analyzed, 586 Wines, 84, 478, 486 matched, 482 concentrated, 541 Wine-lees, 485 Wool, philosophic, 70 Y Yelk of an egg, analyzed, 586 Yellow _aqua fortis_, 24 arsenic, 72 precipitate, 61 Yest, or ferment, 481 Z Zaffre, 371 Zinc, 70, 117, 357 purified, 364 FINIS. * * * * * Transcriber's Notes. Obvious typographical errors, including missing punctuation have been corrected and hyphenation has been standardised, but variations in spelling in the original have been retained. Chap. II., Part II., Section I. is wrongly headed Chap. I. in the text. This has been corrected. A reference to Mr. Fifes, on page 518, could possibly be Mr. Fises. On page 547 "fit for the use of Surgeons, who apply it to eat away callosities and excrescences, and to open issues." issues has been changed to tissues. Colophony, 462 has been placed in correct alphabetical order in the index. Pl. V. and VI. GEOFFROY'S TABLE of the COMPARATIVE AFFINITIES, a table using symbols to represent the various substances, has been replaced by a simple list of text descriptions showing the relationships. Words in italics are shown thus _italic_.